Int. J. Mol. Sci. 2015, 16, 8505-8516; doi:10.3390/ijms16048505 OPEN ACCESS
International Journal of
Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article
Decisive Interactions between the Heterocyclic Moiety and the Cluster Observed in Polyoxometalate-Surfactant Hybrid Crystals Saki Otobe 1, Natsumi Fujioka 1, Takuro Hirano 1, Eri Ishikawa 2, Haruo Naruke 3, Katsuhiko Fujio 1 and Takeru Ito 1,* 1
2
3
Department of Chemistry, School of Science, Tokai University, 4-1-1 Kitakaname, Hiratsuka 259-1292, Japan; E-Mails: [email protected] (S.O.); [email protected] (N.F.); [email protected] (T.H.); [email protected] (K.F.) Department of Applied Chemistry, College of Engineering, Chubu University, 1200 Matsumoto, Kasugai, Aichi 487-8501, Japan; E-Mail: [email protected] Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-23, Nagatsuta, Midori-ku, Yokohama 226-8503, Japan; E-Mail: [email protected]
* Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +81-463-58-1211 (ext. 3737); Fax: +81-463-50-2094. Academic Editor: Habil. Mihai V. Putz Received: 22 December 2014 / Accepted: 1 April 2015 / Published: 16 April 2015
Abstract: Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) surfactants. The decatungstate (W10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10), the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10) had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions. Keywords: inorganic-organic; polyoxometalate; surfactant; heterocyclic; hybrid crystal
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1. Introduction Weak chemical interactions, such as hydrogen bonding or van der Waals interactions, are crucial for the construction and function of biological molecules, such as proteins, DNA or RNA [1]. Employing these weak chemical interactions also provides effective options for building up synthetic molecular architectures [2–5]. To build up such molecular architectures, organic molecules or ligands are often used due to synthetic flexibility to control the directions and intensity of the weak chemical interactions. However, all-organic molecular architectures are less stable in the intermediate temperature (>100 °C) regions. Inorganic-organic hybrid materials are more structurally stable than purely organic compounds owing to inorganic components, and the synergy of inorganic and organic characteristics will benefit constructing functional materials [6]. Conductive hybrid compounds composed of organic cations and inorganic anions have been reported, where the emergence of conductive functions is prompted by precise control of the molecular structures and arrangements of the components [7]. The precisely controlled inorganic-organic materials have been obtained as crystalline materials. As a molecular inorganic component, polyoxometalates (POMs) are promising candidates with respect to their structural and functional controllability [8–16]. POMs with various physicochemical properties have been successfully hybridized by structure-directing surfactants [17–19] to construct inorganic-organic crystalline hybrids [20–24] and single crystals [25–34]. Among several POM-surfactant single crystals, utilizing surfactants with a heterocyclic moiety enables the precise control of the composition and structure [31–33]. However, the variation of the surfactants has been limited to pyridinium and imidazolium cations. Here, we report the syntheses and structures of polyoxotungstate hybrid crystals containing heterocyclic surfactants, including the first example of a POM-surfactant crystal comprised of a pyridazinium surfactant. The decatungstate ([W10O32]4−, W10) anion was hybridized with dodecylpyridazinium ([C4H4N2(C12H25)]+, C12pda) and dodecylpyridinium ([C5H5N(C12H25)]+, C12py) to form the crystals of C12pda-W10 (1) and C12py-W10 (2), respectively, and their chemical interactions and molecular arrangements were compared by X-ray structure analyses. 2. Results and Discussion 2.1. Crystal Structure of C12pda-W10 (1) C12pda-W10 (1) was obtained by the cation exchange reaction of sodium salt of the W10 anion (Na-W10). The retention of the W10 structure before and after the recrystallization was confirmed by infrared (IR) spectra, which exhibited the characteristic peaks in the range of 400–1000 cm−1 (Figure 1a–c). Suitable single crystals for X-ray crystallography were obtained by employing acetone as the crystallization solvent. The X-ray structure and elemental analyses revealed the formula of 1 to be [C4H4N2(C12H25)]4[W10O32]·2(CH3)2CO (Table 1). Four C12pda cations (1+ charge) were associated with one W10 anion (4− charge) due to the charge compensation. Figure 2 shows the crystal structure of 1. The crystal packing consisted of alternating W10 inorganic monolayers and C12pda organic bilayers with a periodicity of 24.5 Å (Figure 2a). The acetone molecules were placed at the interface
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between the W10 and C12pda layers, being excluded from the inorganic layers. Although most C-C bonds of the dodecyl chains of C12pda had the anti conformation, three C-C bonds (C8-C9, C41-C42, C54-C55) had the gauche conformation (Figure 2b), two of which (C8-C9, C41-C42) were located at some methylene groups far away from the hydrophilic head.
Figure 1. IR spectra of W10 compounds. (a) Na-W10 as a starting material; (b) As-prepared sample of 1; (c) 1 after recrystallization; (d) As-prepared sample of 2. Table 1. Crystallographic data. Compound Chemical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z ρcalcd (g·cm−3) T (K) μ (Mo·Kα) (mm−1) No. of reflections measured No. of independent reflections Rint No. of parameters R1 (I > 2σ(I)) wR2 (all data)
1 C70H128N8W10O34 3464.31 triclinic P 1 (No.2) 10.55918(19) 18.7700(3) 25.4318(5) 74.4842(7) 86.5737(7) 85.6363(7) 4838.62(15) 2 2.378 193 11.924 78,035 22,146 0.0900 1106 0.0452 0.1162
2 C76H140N4W10O36 3524.45 triclinic P 1 (No.2) 10.813(7) 11.339(7) 23.610(13) 99.415(9) 91.558(5) 115.588(9) 2560(3) 1 2.286 173 11.272 18,275 11,774 0.1384 563 0.0983 0.3237
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Figure 2. Crystal structure of 1 (C: gray, N: blue; W10 anions in polyhedral representations. H atoms are omitted for clarity). (a) Packing diagram along the a axis. Some acetone molecules are highlighted; (b) View of crystallographically-independent surfactant molecules.
The hydrophilic heads of C12pda penetrated into the W10 inorganic layers and isolated each W10 anion (Figure 3a) in a similar way to that in the crystal of hexadecylpyridinium ([C5H5N(C16H33)]+, C16py) and W10 (C16py-W10, 3) [32]. However, the conformations of the heterocyclic moiety were different. In 1, the pyridazine rings of the C12pda cations were not in the vicinity of each other (Figure 3b), as in the case of the POM crystal comprising the pyridazinium cation without a long alkyl chain [35]. This indicates that there were no interactions, such as π–π stacking or the C-H···π interaction, between the heterocyclic moiety, being different from 2 (see below) and 3. On the other hand, the pyridazine rings of C12pda interacted rather more directly with the W10 anions. The crystals of 1 had several short contacts between of O atoms of W10 and C or N atoms of the pyridazine ring (2.88–3.22 Å (mean: 3.09 Å); Table 2), indicating the direct interactions between W10 and the heterocyclic moiety of C12pda. The alignment of two crystallographically-independent W10 anions was not parallel, and the angle between the molecular C4 axes was 8.3° (Figure 3b).
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Figure 3. Molecular arrangements in the inorganic layers of 1 (C: gray, N: blue; W10 anions in polyhedral representations. H atoms and the dodecyl groups are omitted for clarity). (a) Packing diagram along the c axis; (b) View of crystallographically-independent pyridazinium moieties of surfactants in the vicinity of the W10 anions. Table 2. Short contacts between W10 and the heterocyclic moiety of C12pda in 1. Contact a C20i···O1 C20i···O2 C4···O5 C19i···O5 C33ii···O6 C34ii···O6 C50iii···O7 C51iii···O7 C34iii···O8 C4···O9 C3···O9 N8iii···O12
Distance (Å) 3.206 3.085 3.210 3.147 3.140 3.180 2.876 3.110 3.134 3.183 2.890 3.046
Contact a C2···O13 C51iv···O13 C33i···O20 C49···O22 C4···O24 C17···O25 C3ii···O27 C19ii···O27 C33i···O27 C17i···O28 C20···O29 N6···O30
Distance (Å) 3.118 3.201 3.177 2.914 2.886 2.894 3.216 3.163 3.142 3.135 3.119 2.909
a
Contact between O atoms of W10 and C or N atoms of the pyridazine ring of C12pda. Symmetry codes: (i) 1 + x, y, z; (ii) −x, −y, 2 − z; (iii) 1+x, −1 + y, z; (iv) x, −1 + y, z.
In the crystal of 1, The C12pda cations had weak C-H···O hydrogen bonds [1]. Some C-H···O bonds were present in the vicinity of the gauche C-C bonds. The C···O distances were in the range of 2.89–3.74 Å (mean value: 3.32 Å), being much shorter than those of 2 (see below). In addition, most C-H···O hydrogen bonds were formed between W10 and the hydrophilic head of C12pda, i.e., the pyridazine ring of C12pda. This suggests stronger interactions between W10 and the heterocyclic moiety of the surfactant in 1 than in 2. These hydrogen bonds, as well as the electrostatic interaction between W10 and the heterocyclic moiety of C12pda stabilized the layered crystal structure of C12pda-W10 with rigid packing.
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2.2. Crystal Structure of C12py-W10 (2)
C12py-W10 (2) was also synthesized by the cation exchange reaction of Na-W10 (Figure 1d). The molecular structure of W10 was retained before and after the recrystallization, as in the case of C16py-W10 (3) [32]. Although the recrystallization of 2 was difficult, some crystals obtained from ethanol were able to be analyzed by X-ray crystallography. The formula of 2 was revealed to be [C5H5N(C12H25)]4[W10O32]·4C2H5OH (Table 1). Four C12py cations (1+ charge) were associated with one W10 anion (4− charge), being similar to 1 and 3. The crystal packing of 2 consisted of alternating W10 inorganic monolayers and C12py organic bilayers with a distance of 23.2 Å (Figure 4a). Surprisingly, the cell parameters and the layered distances of 2 and 3 [32] were quite similar, even if the length of the pyridinium surfactants were changed to C12py (2) from C16py (3). The vacant spaces produced by changing to the shorter surfactant for 2 were filled by the ethanol molecules located at the interface between the W10 and C12py layers. This similarity of the layered structures led to the similar molecular arrangements of W10 and the pyridine rings (see below). All C-C bonds in the dodecyl chains showed the anti conformation except one C-C bond (C7-C8) near the hydrophilic head of C12py, being similar to that in 3 (Figure 4b).
Figure 4. Crystal structure of 2 (C: gray, N: blue; W10 anions in polyhedral representations. H atoms are omitted for clarity). (a) Packing diagram along the b axis. Some ethanol molecules are highlighted; (b) View of crystallographically-independent surfactant molecules in 2.
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The hydrophilic heads of C12py penetrated into the W10 inorganic layers in 2 (Figure 5a), which was almost the same manner as observed in 3. The alignment of each W10 anion was parallel, being similar to 3, but different from 1. The penetrated C12py cations formed two crystallographically-independent pairs (Figure 5b). The two C12py cations interacted weakly through the C-H···π interaction, where the shortest interatomic distance was 2.91 Ǻ for C3···H20 (Figure 5b). In the crystal of 2, there were short contacts between W10 and the pyridine ring (2.93–3.22 Å (mean: 3.07 Å), Table 3). 2 also had C-H···O hydrogen bonds at the interface between the W10 and C12py layers (C···O distance: 3.03–3.88 Å; mean value: 3.52 Å), being much longer than those observed in 1. These longer C-H···O hydrogen bonds were formed around W10 and the pyridine ring of C12py, indicating that the interactions between W10 and the heterocyclic moiety in 2 were weaker than in 1. The structure of the heterocyclic moiety in the surfactants is the significant factor to construct the POM-surfactant hybrid crystals.
Figure 5. Molecular arrangements in the inorganic layers of 2 (C: gray, N: blue, H: white; W10 anions in polyhedral representations. The dodecyl groups are omitted for clarity). (a) Packing diagram along the c axis. H atoms are omitted for clarity; (b) View of crystallographically-independent pyridinium moieties of surfactants in the vicinity of the W10 anions. The selected short contact is presented as a pink dotted line.
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Table 3. Short contacts between W10 and the heterocyclic moiety of C12py in 2. Contact a C22···O5 N2i···O9 C18i···O9 C22i···O9 C2···O11
Distance (Å) 3.153 2.929 2.980 3.108 3.220
Contact a C20ii···O11 N1iii···O14 C5iii···O14 C21iv···O14 C18v···O16
Distance (Å) 3.026 2.960 3.203 3.091 3.031
a
Contact between O atoms of W10 and C or N atoms of the pyridine ring of C12py. Symmetry codes: (i) −1 + x, y, z; (ii) 1 − x, 1 − y, −z; (iii) x, −1 + y, z; (iv) 1 − x, −y, −z; (v) −1 + x, −1 + y, z.
3. Experimental Section 3.1. Syntheses and Methods
All chemical reagents were obtained from commercial sources (Wako, Osaka, Japan). [C4H4N2(C12H25)]Br (C12pda·Br) was synthesized by using pyridazine and 1-bromododecane based on the literature [36]. Na4[W10O32] (Na-W10) was synthesized by combining a boiled solution of Na2WO4·2H2O (0.5 M, 25 mL) and boiled HCl (1 M, 25 mL) [37]. C12pda-W10 (1) was synthesized by the cation exchange of Na-W10. Na-W10 (0.50 g, 0.20 mmol) was dissolved in 20 mL of HCl (pH = 2), and ethanol solution containing 0.27 g (0.81 mmol) of C12pda·Br was added. After stirring for 10 min, the obtained white precipitates were filtered and dried. Recrystallization of the crude product from hot acetone gave colorless plates of 1. The crystals of 1 were efflorescent, and its elemental composition was calculated for the formula without the solvent of crystallization. Data for 1: anal. calcd. for C64H116N8W10O32: C, 22.96; H, 3.49; N, 3.35%; found: C, 22.77; H, 3.36; N, 3.33%. IR (KBr disk): 996 (w), 958 (s), 889 (m), 800 (s), 772 (s), 589 (w), 437 (m), 407 (m) cm−1. C12py-W10 (2) was synthesized by a similar procedure as for 1. [C5H5N(C12H25)]Br (C12py·Br, 0.28 g (0.81 mmol)) was employed as the cationic surfactant. The crude product was recrystallized from ethanol to obtain colorless prisms of 2, which were efflorescent. Data for 1: anal. calcd. for C76H120N4W10O32: C, 24.42; H, 3.62; N, 1.68%; found: C, 24.01; H, 3.42; N, 1.62%. IR (KBr disk): 997 (w), 959 (s), 895 (m), 796 (s), 683 (m), 584 (w), 440 (m), 410 (m) cm−1. 3.2. X-ray Diffraction Measurements
Single-crystal X-ray diffraction measurements for 1 were made on a Rigaku RAXIS RAPID imaging plate diffractometer with graphite monochromated Mo-Kα radiation (λ = 0.71075 Å). Diffraction data were collected and processed with PROCESS-AUTO [38]. The structure of 1 was solved by the charge flipping method [39] and expanded using Fourier techniques. The refinement procedure was performed by the full-matrix least-squares using SHELXL97 [40]. The measurements for 2 were made on a Rigaku Saturn70 diffractometer using graphite monochromated Mo-Kα radiation. Diffraction data were collected and processed with CrystalClear [41]. The structure of 2 was solved by direct methods [42] and expanded using Fourier techniques. The refinement procedure was performed by full-matrix least-squares using SHELXL2013 [42]. All calculations were performed using the CrystalStructure [43] software package. In the refinement procedure, all non-hydrogen atoms,
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except for C37 of 2, were refined anisotropically, and the hydrogen atoms on C atoms were located in the calculated positions. The weak reflection intensities from the crystals of 2 may result in relatively high R1 and wR2 values. The results of checking cif files are available as supplementary materials. Further details of the crystal structure investigation may be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336 033; or E-Mail: [email protected] (CCDC 1055676-1055677). 4. Conclusions
Inorganic-organic hybrid crystals comprised of polyoxotungstate and surfactants having a heterocyclic moiety, [C4H4N2(C12H25)]4[W10O32]·2(CH3)2CO (1) and [C5H5N(C12H25)]4[W10O32]·4C2H5OH (2), were successfully synthesized. Dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) were utilized as organic cations, and the decatungstate anion (W10) was used for the inorganic component, which enabled the discussion of the effect of the heterocyclic moiety for the construction of the hybrid crystals. Although both hybrid crystals contained alternate stacking of W10 monolayers and interdigitated surfactant bilayers, pyridazine rings in 1 interacted more strongly with the W10 anions. 1 contained shorter C-H···O hydrogen bonds than those observed in 2, indicating that these hydrogen bonds, as well as the electrostatic interaction between the C12pda cation and the W10 anion stabilized the layered structure of C12pda-W10 with rigid packing. On the other hand, 2 has similar cell parameters and molecular arrangements as those in the crystals of hexadecylpyridinium (C16py) and W10 (3), also indicating the significance of the heterocyclic moiety for the construction of the hybrid crystals. The difference between the heterocyclic moieties led to different arrangements of W10 anions in 1 and 2, which will contribute to the precise control of molecular arrangements and the emergence of characteristic conductivity. Supplementary Materials
Supplementary materials can be found at http://www.mdpi.com/1422-0067/16/04/8505/s1. Acknowledgments
This work was supported in part by the JSPS Grant-in-Aid for Scientific Research (No. 26410245) and the Research and Study Project of Tokai University Educational System General Research Organization. Author Contributions
Saki Otobe and Takeru Ito conceived of and designed the experiments. Saki Otobe, Natsumi Fujioka and Takuro Hirano performed the experiments. Saki Otobe and Takeru Ito analyzed the data. Eri Ishikawa and Haruo Naruke contributed analysis tools. Katsuhiko Fujio contributed materials. Takeru Ito wrote the paper. Conflicts of Interest
The authors declare no conflict of interest.
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Supplementary Information Check Report of cif for 1 (C12pda-W10) CheckCIF/PLATON Report You have not supplied any structure factors. As a result the full set of tests cannot be run. THIS REPORT IS FOR GUIDANCE ONLY. IF USED AS PART OF A REVIEW PROCEDURE FOR PUBLICATION, IT SHOULD NOT REPLACE THE EXPERTISE OF AN EXPERIENCED CRYSTALLOGRAPHIC REFEREE. No syntax errors found. CIF dictionary Interpreting this report Datablock: 140304
Bond precision:
C-C = 0.0183 A
Wavelength=0.71075
Cell:
a=10.55918(19)
b=18.7700(3)
c=25.4318(5)
alpha=74.4842(7) 193 K
beta=86.5737(7)
gamma=85.6363(7)
Temperature:
Calculated
Reported
Volume Space group Hall group
4838.63(15) P -1 -P 1 O32 W10, 4(C16 H29 Moiety formula N2), 2(C3 H6 O) C70 H128 N8 O34 W10 Sum formula 3464.20 Mr 2.378 Dx,g cm-3 2 Z 11.910 Mu (mm-1) 3232.0 F000 3218.05 F000’ 13,24,33 h,k,lmax 22200 Nref Tmin,Tmax 0.249,0.551 Tmin’ 0.001 Correction method= MULTI-SCAN
4838.62(15) P -1 -P 1 C70 H128 N8 O34 W10 C70 H128 N8 O34 W10 3464.31 2.378 2 11.924 3232.0 13,24,33 22146 0.139,0.551
Data completeness= 0.998
Theta(max)= 27.490
R(reflections)= 0.0452( 17651)
wR2(reflections)= 0.1162( 22146)
S = 1.034
Npar= 1106
The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level Click on the hyperlinks for more details of the test.
S2 Alert level C PLAT220_ALERT_2_C PLAT230_ALERT_2_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT241_ALERT_2_C PLAT241_ALERT_2_C PLAT241_ALERT_2_C PLAT241_ALERT_2_C PLAT242_ALERT_2_C PLAT242_ALERT_2_C PLAT244_ALERT_4_C PLAT342_ALERT_3_C PLAT360_ALERT_2_C PLAT362_ALERT_2_C PLAT790_ALERT_4_C O32
Ueq(max)/Ueq(min) Range Large Non-Solvent C N6 .. -- C33 Hirshfeld Test Diff for Large Hirshfeld Difference N5 .. -- N6 Large Hirshfeld Difference N7 .. -- N8 Large Hirshfeld Difference N7 .. -- C52 Large Hirshfeld Difference N8 .. -- C49 Large Hirshfeld Difference C51 .. -- C52 High Ueq as Compared to Neighbors for ..... Ueq as Compared to Neighbors for ..... High High Ueq as Compared to Neighbors for ..... Ueq as Compared to Neighbors for ..... High Low Ueq as Compared to Neighbors for ..... Low Ueq as Compared to Neighbors for ..... Low ’Solvent’ Ueq as Compared to Neighbors of Low Bond Precision on C-C Bonds ............... Short C(sp3)-C(sp3) Bond C44 C45 ... Short C(sp3)-C(sp2) Bond C66 C67 ... Centre of Gravity not Within Unit Cell: Resd. # W10
3.9 Ratio 5.2 su 0.19 Ang. 0.18 Ang. 16. Ang. 17. Ang. 0.20 Ang. N6 Check C47 Check N8 Check C55 Check C33 Check C46 Check C66 Check 0.0183 Ang. 1.42 Ang. 1.40 Ang. 1 Note
Alert level G CHEMS02_ALERT_1_G Please check that you have entered the correct _publ_requested_category classification of your compound; FI or CI or EI for inorganic; FM or CM or EM for metal-organic; FO or CO or EO for organic. From the CIF: _publ_requested_category CHOOSE FI FM FO CI CM CO From the CIF: _chemical_formula_sum:C70 H128 N8 O34 W10 Please PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 23.11 PLAT154_ALERT_1_G The su’s on the Cell Angles are Equal .......... 0.00070 C67 PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety ..... 88. PLAT432_ALERT_2_G Short Inter X...Y Contact O7 .. C50 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O9 89. .. C3 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O22 2.91 .. C49 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O24 2.89 .. C4 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O25 2.89 .. C17 .. 5 PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # C16 H29 N2 8 PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # C3 H6 O 0 0 18 13
ALERT ALERT ALERT ALERT
level level level level
3 16 1 10 1
ALERT ALERT ALERT ALERT ALERT
type type type type type
A B C G
1 2 3 4 5
= = = =
Most likely a serious problem - resolve or explain A potentially serious problem, consider carefully Check. Ensure it is not caused by an omission or oversight General information/check it is not something unexpected
CIF construction/syntax error, inconsistent or missing data Indicator that the structure model may be wrong or deficient Indicator that the structure quality may be low Improvement, methodology, query or suggestion Informative message, check
or Do ! Check Why ? Degree Check Ang. Ang. Ang. Ang. Ang. Note Note
S3 Check report of cif for 2 (C12py-W10) CheckCIF/PLATON Report You have not supplied any structure factors. As a result the full set of tests cannot be run. THIS REPORT IS FOR GUIDANCE ONLY. IF USED AS PART OF A REVIEW PROCEDURE FOR PUBLICATION, IT SHOULD NOT REPLACE THE EXPERTISE OF AN EXPERIENCED CRYSTALLOGRAPHIC REFEREE. No syntax errors found. CIF dictionary Interpreting this report Datablock: TOtobeSaturn4
Bond precision:
C-C = 0.0419 A
Wavelength=0.71075
Cell:
a=10.813(7)
b=11.339(7)
c=23.610(13)
alpha=99.415(9) 173 K
beta=91.558(5)
gamma=115.588(9)
Temperature:
Volume Space group Hall group Moiety formula Sum formula Mr Dx,g cm-3 Z Mu (mm-1) F000 F000’ h,k,lmax Nref Tmin,Tmax Tmin’
Calculated
Reported
2560(3) P -1 -P 1 O32 W10, 4(C17 H30 N), 4(C2 H6 O) C76 H144 N4 O36 W10 3528.35 2.289 1 11.258 1656.0 1649.02 15,16,34 17033 0.131,0.105 0.084
2560(3) P -1 -P 1 C76 H140 N4 O36 W10 C76 H140 N4 O36 W10 3524.45 2.286 1 11.272 1652.0 15,16,34 11774 0.046,0.105
Correction method= MULTI-SCAN Data completeness= 0.691
Theta(max)= 31.493
R(reflections)= 0.0983( 8235)
wR2(reflections)= 0.3237( 11774)
S = 1.058
Npar= 563
The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level Click on the hyperlinks for more details of the test.
S4 Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......
0.812 Note
Author Response: ...This structure intrinsically exhibits many weak reflections at higher theta values. The submitted manuscript mainly reports the packing mode of the decatungstate anions and pyridinium cations. The data obtained had insufficient quality, but was sufficient to elucidate the packing feature of the decatungstate anion and heterocyclic moiety.
Alert level B PLAT342_ALERT_3_B Low Bond Precision on
C-C Bonds ...............
0.0419 Ang.
Alert level C DIFMN02_ALERT_2_C The minimum difference density is < -0.1*ZMAX*0.75 _refine_diff_density_min given = -6.420 Test value = -5.550 DIFMN03_ALERT_1_C The minimum difference density is < -0.1*ZMAX*0.75 The relevant atom site should be identified. RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25 Weighted R factor given 0.324 RINTA01_ALERT_3_C The value of Rint is greater than 0.12 Rint given 0.138 PLAT020_ALERT_3_C The value of Rint is greater than 0.12 ......... PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ PLAT043_ALERT_1_C Calculated and Reported Mol. Weight Differ by .. PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... PLAT084_ALERT_3_C High wR2 Value (i.e. > 0.25) ................... PLAT098_ALERT_2_C Large Reported Min. (Negative) Residual Density PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... PLAT213_ALERT_2_C Atom O1 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C1 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C10 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C14 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C15 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C18 has ADP max/min Ratio ..... Ueq(max)/Ueq(min) Range PLAT220_ALERT_2_C Large Non-Solvent C PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 -- C2 .. PLAT234_ALERT_4_C Large Hirshfeld Difference W1 -- O1 .. PLAT234_ALERT_4_C Large Hirshfeld Difference W3 -- O11 .. PLAT234_ALERT_4_C Large Hirshfeld Difference C3 -- C4 .. PLAT234_ALERT_4_C Large Hirshfeld Difference C8 -- C9 .. PLAT241_ALERT_2_C High Ueq as Compared to Neighbors for ..... PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ..... PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ..... PLAT244_ALERT_4_C Low ’Solvent’ Ueq as Compared to Neighbors of PLAT244_ALERT_4_C Low ’Solvent’ Ueq as Compared to Neighbors of PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C33 C34 ... PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C37 C38 ... PLAT361_ALERT_2_C Long C(sp3)-C(sp3) Bond C29 C30 ... PLAT415_ALERT_2_C Short Inter D-H..H-X H18E .. H23A ..
0.138 Report Please Check 3.90 Check Please Check 0.32 Report -6.42 eA-3 1 3.1 oblate 3.8 prolat 3.7 prolat 3.4 oblate 3.4 prolat 3.2 oblate 3.1 Ratio 6.0 su 0.18 Ang. 0.16 Ang. 0.20 Ang. 0.19 Ang. C1 Check C2 Check C32 Check C35 Check C37 Check 2.4 Note 1.36 Ang. 1.38 Ang. 1.67 Ang. 2.10 Ang.
S5 Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C76 H140 N4 O36 W10 Atom count from the _atom_site data: C76 H144 N4 O36 W10 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: Large difference may be due to a symmetry error - see SYMMG tests From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C76 H140 N4 O36 W10 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 76.00 76.00 0.00 H 140.00 144.00 -4.00 N 4.00 4.00 0.00 O 36.00 36.00 0.00 W 10.00 10.00 0.00 CHEMS02_ALERT_1_G Please check that you have entered the correct _publ_requested_category classification of your compound; FI or CI or EI for inorganic; FM or CM or EM for metal-organic; FO or CO or EO for organic. From the CIF: _publ_requested_category CHOOSE FI FM FO CI CM CO From the CIF: _chemical_formula_sum:C76 H140 N4 O36 W10 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large. 0.20 PLAT432_ALERT_2_G Short Inter X...Y Contact O9 .. C18 .. 2.99
1 1 33 9
ALERT ALERT ALERT ALERT
level level level level
8 21 7 6 2
ALERT ALERT ALERT ALERT ALERT
type type type type type
A B C G
1 2 3 4 5
= = = =
Most likely a serious problem - resolve or explain A potentially serious problem, consider carefully Check. Ensure it is not caused by an omission or oversight General information/check it is not something unexpected
CIF construction/syntax error, inconsistent or missing data Indicator that the structure model may be wrong or deficient Indicator that the structure quality may be low Improvement, methodology, query or suggestion Informative message, check
or Do ! Report Check Report Ang.
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International Journal of
Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article
Decisive Interactions between the Heterocyclic Moiety and the Cluster Observed in Polyoxometalate-Surfactant Hybrid Crystals Saki Otobe 1, Natsumi Fujioka 1, Takuro Hirano 1, Eri Ishikawa 2, Haruo Naruke 3, Katsuhiko Fujio 1 and Takeru Ito 1,* 1
2
3
Department of Chemistry, School of Science, Tokai University, 4-1-1 Kitakaname, Hiratsuka 259-1292, Japan; E-Mails: [email protected] (S.O.); [email protected] (N.F.); [email protected] (T.H.); [email protected] (K.F.) Department of Applied Chemistry, College of Engineering, Chubu University, 1200 Matsumoto, Kasugai, Aichi 487-8501, Japan; E-Mail: [email protected] Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-23, Nagatsuta, Midori-ku, Yokohama 226-8503, Japan; E-Mail: [email protected]
* Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +81-463-58-1211 (ext. 3737); Fax: +81-463-50-2094. Academic Editor: Habil. Mihai V. Putz Received: 22 December 2014 / Accepted: 1 April 2015 / Published: 16 April 2015
Abstract: Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) surfactants. The decatungstate (W10) anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10), the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10) had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions. Keywords: inorganic-organic; polyoxometalate; surfactant; heterocyclic; hybrid crystal
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1. Introduction Weak chemical interactions, such as hydrogen bonding or van der Waals interactions, are crucial for the construction and function of biological molecules, such as proteins, DNA or RNA [1]. Employing these weak chemical interactions also provides effective options for building up synthetic molecular architectures [2–5]. To build up such molecular architectures, organic molecules or ligands are often used due to synthetic flexibility to control the directions and intensity of the weak chemical interactions. However, all-organic molecular architectures are less stable in the intermediate temperature (>100 °C) regions. Inorganic-organic hybrid materials are more structurally stable than purely organic compounds owing to inorganic components, and the synergy of inorganic and organic characteristics will benefit constructing functional materials [6]. Conductive hybrid compounds composed of organic cations and inorganic anions have been reported, where the emergence of conductive functions is prompted by precise control of the molecular structures and arrangements of the components [7]. The precisely controlled inorganic-organic materials have been obtained as crystalline materials. As a molecular inorganic component, polyoxometalates (POMs) are promising candidates with respect to their structural and functional controllability [8–16]. POMs with various physicochemical properties have been successfully hybridized by structure-directing surfactants [17–19] to construct inorganic-organic crystalline hybrids [20–24] and single crystals [25–34]. Among several POM-surfactant single crystals, utilizing surfactants with a heterocyclic moiety enables the precise control of the composition and structure [31–33]. However, the variation of the surfactants has been limited to pyridinium and imidazolium cations. Here, we report the syntheses and structures of polyoxotungstate hybrid crystals containing heterocyclic surfactants, including the first example of a POM-surfactant crystal comprised of a pyridazinium surfactant. The decatungstate ([W10O32]4−, W10) anion was hybridized with dodecylpyridazinium ([C4H4N2(C12H25)]+, C12pda) and dodecylpyridinium ([C5H5N(C12H25)]+, C12py) to form the crystals of C12pda-W10 (1) and C12py-W10 (2), respectively, and their chemical interactions and molecular arrangements were compared by X-ray structure analyses. 2. Results and Discussion 2.1. Crystal Structure of C12pda-W10 (1) C12pda-W10 (1) was obtained by the cation exchange reaction of sodium salt of the W10 anion (Na-W10). The retention of the W10 structure before and after the recrystallization was confirmed by infrared (IR) spectra, which exhibited the characteristic peaks in the range of 400–1000 cm−1 (Figure 1a–c). Suitable single crystals for X-ray crystallography were obtained by employing acetone as the crystallization solvent. The X-ray structure and elemental analyses revealed the formula of 1 to be [C4H4N2(C12H25)]4[W10O32]·2(CH3)2CO (Table 1). Four C12pda cations (1+ charge) were associated with one W10 anion (4− charge) due to the charge compensation. Figure 2 shows the crystal structure of 1. The crystal packing consisted of alternating W10 inorganic monolayers and C12pda organic bilayers with a periodicity of 24.5 Å (Figure 2a). The acetone molecules were placed at the interface
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between the W10 and C12pda layers, being excluded from the inorganic layers. Although most C-C bonds of the dodecyl chains of C12pda had the anti conformation, three C-C bonds (C8-C9, C41-C42, C54-C55) had the gauche conformation (Figure 2b), two of which (C8-C9, C41-C42) were located at some methylene groups far away from the hydrophilic head.
Figure 1. IR spectra of W10 compounds. (a) Na-W10 as a starting material; (b) As-prepared sample of 1; (c) 1 after recrystallization; (d) As-prepared sample of 2. Table 1. Crystallographic data. Compound Chemical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z ρcalcd (g·cm−3) T (K) μ (Mo·Kα) (mm−1) No. of reflections measured No. of independent reflections Rint No. of parameters R1 (I > 2σ(I)) wR2 (all data)
1 C70H128N8W10O34 3464.31 triclinic P 1 (No.2) 10.55918(19) 18.7700(3) 25.4318(5) 74.4842(7) 86.5737(7) 85.6363(7) 4838.62(15) 2 2.378 193 11.924 78,035 22,146 0.0900 1106 0.0452 0.1162
2 C76H140N4W10O36 3524.45 triclinic P 1 (No.2) 10.813(7) 11.339(7) 23.610(13) 99.415(9) 91.558(5) 115.588(9) 2560(3) 1 2.286 173 11.272 18,275 11,774 0.1384 563 0.0983 0.3237
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Figure 2. Crystal structure of 1 (C: gray, N: blue; W10 anions in polyhedral representations. H atoms are omitted for clarity). (a) Packing diagram along the a axis. Some acetone molecules are highlighted; (b) View of crystallographically-independent surfactant molecules.
The hydrophilic heads of C12pda penetrated into the W10 inorganic layers and isolated each W10 anion (Figure 3a) in a similar way to that in the crystal of hexadecylpyridinium ([C5H5N(C16H33)]+, C16py) and W10 (C16py-W10, 3) [32]. However, the conformations of the heterocyclic moiety were different. In 1, the pyridazine rings of the C12pda cations were not in the vicinity of each other (Figure 3b), as in the case of the POM crystal comprising the pyridazinium cation without a long alkyl chain [35]. This indicates that there were no interactions, such as π–π stacking or the C-H···π interaction, between the heterocyclic moiety, being different from 2 (see below) and 3. On the other hand, the pyridazine rings of C12pda interacted rather more directly with the W10 anions. The crystals of 1 had several short contacts between of O atoms of W10 and C or N atoms of the pyridazine ring (2.88–3.22 Å (mean: 3.09 Å); Table 2), indicating the direct interactions between W10 and the heterocyclic moiety of C12pda. The alignment of two crystallographically-independent W10 anions was not parallel, and the angle between the molecular C4 axes was 8.3° (Figure 3b).
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Figure 3. Molecular arrangements in the inorganic layers of 1 (C: gray, N: blue; W10 anions in polyhedral representations. H atoms and the dodecyl groups are omitted for clarity). (a) Packing diagram along the c axis; (b) View of crystallographically-independent pyridazinium moieties of surfactants in the vicinity of the W10 anions. Table 2. Short contacts between W10 and the heterocyclic moiety of C12pda in 1. Contact a C20i···O1 C20i···O2 C4···O5 C19i···O5 C33ii···O6 C34ii···O6 C50iii···O7 C51iii···O7 C34iii···O8 C4···O9 C3···O9 N8iii···O12
Distance (Å) 3.206 3.085 3.210 3.147 3.140 3.180 2.876 3.110 3.134 3.183 2.890 3.046
Contact a C2···O13 C51iv···O13 C33i···O20 C49···O22 C4···O24 C17···O25 C3ii···O27 C19ii···O27 C33i···O27 C17i···O28 C20···O29 N6···O30
Distance (Å) 3.118 3.201 3.177 2.914 2.886 2.894 3.216 3.163 3.142 3.135 3.119 2.909
a
Contact between O atoms of W10 and C or N atoms of the pyridazine ring of C12pda. Symmetry codes: (i) 1 + x, y, z; (ii) −x, −y, 2 − z; (iii) 1+x, −1 + y, z; (iv) x, −1 + y, z.
In the crystal of 1, The C12pda cations had weak C-H···O hydrogen bonds [1]. Some C-H···O bonds were present in the vicinity of the gauche C-C bonds. The C···O distances were in the range of 2.89–3.74 Å (mean value: 3.32 Å), being much shorter than those of 2 (see below). In addition, most C-H···O hydrogen bonds were formed between W10 and the hydrophilic head of C12pda, i.e., the pyridazine ring of C12pda. This suggests stronger interactions between W10 and the heterocyclic moiety of the surfactant in 1 than in 2. These hydrogen bonds, as well as the electrostatic interaction between W10 and the heterocyclic moiety of C12pda stabilized the layered crystal structure of C12pda-W10 with rigid packing.
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2.2. Crystal Structure of C12py-W10 (2)
C12py-W10 (2) was also synthesized by the cation exchange reaction of Na-W10 (Figure 1d). The molecular structure of W10 was retained before and after the recrystallization, as in the case of C16py-W10 (3) [32]. Although the recrystallization of 2 was difficult, some crystals obtained from ethanol were able to be analyzed by X-ray crystallography. The formula of 2 was revealed to be [C5H5N(C12H25)]4[W10O32]·4C2H5OH (Table 1). Four C12py cations (1+ charge) were associated with one W10 anion (4− charge), being similar to 1 and 3. The crystal packing of 2 consisted of alternating W10 inorganic monolayers and C12py organic bilayers with a distance of 23.2 Å (Figure 4a). Surprisingly, the cell parameters and the layered distances of 2 and 3 [32] were quite similar, even if the length of the pyridinium surfactants were changed to C12py (2) from C16py (3). The vacant spaces produced by changing to the shorter surfactant for 2 were filled by the ethanol molecules located at the interface between the W10 and C12py layers. This similarity of the layered structures led to the similar molecular arrangements of W10 and the pyridine rings (see below). All C-C bonds in the dodecyl chains showed the anti conformation except one C-C bond (C7-C8) near the hydrophilic head of C12py, being similar to that in 3 (Figure 4b).
Figure 4. Crystal structure of 2 (C: gray, N: blue; W10 anions in polyhedral representations. H atoms are omitted for clarity). (a) Packing diagram along the b axis. Some ethanol molecules are highlighted; (b) View of crystallographically-independent surfactant molecules in 2.
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The hydrophilic heads of C12py penetrated into the W10 inorganic layers in 2 (Figure 5a), which was almost the same manner as observed in 3. The alignment of each W10 anion was parallel, being similar to 3, but different from 1. The penetrated C12py cations formed two crystallographically-independent pairs (Figure 5b). The two C12py cations interacted weakly through the C-H···π interaction, where the shortest interatomic distance was 2.91 Ǻ for C3···H20 (Figure 5b). In the crystal of 2, there were short contacts between W10 and the pyridine ring (2.93–3.22 Å (mean: 3.07 Å), Table 3). 2 also had C-H···O hydrogen bonds at the interface between the W10 and C12py layers (C···O distance: 3.03–3.88 Å; mean value: 3.52 Å), being much longer than those observed in 1. These longer C-H···O hydrogen bonds were formed around W10 and the pyridine ring of C12py, indicating that the interactions between W10 and the heterocyclic moiety in 2 were weaker than in 1. The structure of the heterocyclic moiety in the surfactants is the significant factor to construct the POM-surfactant hybrid crystals.
Figure 5. Molecular arrangements in the inorganic layers of 2 (C: gray, N: blue, H: white; W10 anions in polyhedral representations. The dodecyl groups are omitted for clarity). (a) Packing diagram along the c axis. H atoms are omitted for clarity; (b) View of crystallographically-independent pyridinium moieties of surfactants in the vicinity of the W10 anions. The selected short contact is presented as a pink dotted line.
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Table 3. Short contacts between W10 and the heterocyclic moiety of C12py in 2. Contact a C22···O5 N2i···O9 C18i···O9 C22i···O9 C2···O11
Distance (Å) 3.153 2.929 2.980 3.108 3.220
Contact a C20ii···O11 N1iii···O14 C5iii···O14 C21iv···O14 C18v···O16
Distance (Å) 3.026 2.960 3.203 3.091 3.031
a
Contact between O atoms of W10 and C or N atoms of the pyridine ring of C12py. Symmetry codes: (i) −1 + x, y, z; (ii) 1 − x, 1 − y, −z; (iii) x, −1 + y, z; (iv) 1 − x, −y, −z; (v) −1 + x, −1 + y, z.
3. Experimental Section 3.1. Syntheses and Methods
All chemical reagents were obtained from commercial sources (Wako, Osaka, Japan). [C4H4N2(C12H25)]Br (C12pda·Br) was synthesized by using pyridazine and 1-bromododecane based on the literature [36]. Na4[W10O32] (Na-W10) was synthesized by combining a boiled solution of Na2WO4·2H2O (0.5 M, 25 mL) and boiled HCl (1 M, 25 mL) [37]. C12pda-W10 (1) was synthesized by the cation exchange of Na-W10. Na-W10 (0.50 g, 0.20 mmol) was dissolved in 20 mL of HCl (pH = 2), and ethanol solution containing 0.27 g (0.81 mmol) of C12pda·Br was added. After stirring for 10 min, the obtained white precipitates were filtered and dried. Recrystallization of the crude product from hot acetone gave colorless plates of 1. The crystals of 1 were efflorescent, and its elemental composition was calculated for the formula without the solvent of crystallization. Data for 1: anal. calcd. for C64H116N8W10O32: C, 22.96; H, 3.49; N, 3.35%; found: C, 22.77; H, 3.36; N, 3.33%. IR (KBr disk): 996 (w), 958 (s), 889 (m), 800 (s), 772 (s), 589 (w), 437 (m), 407 (m) cm−1. C12py-W10 (2) was synthesized by a similar procedure as for 1. [C5H5N(C12H25)]Br (C12py·Br, 0.28 g (0.81 mmol)) was employed as the cationic surfactant. The crude product was recrystallized from ethanol to obtain colorless prisms of 2, which were efflorescent. Data for 1: anal. calcd. for C76H120N4W10O32: C, 24.42; H, 3.62; N, 1.68%; found: C, 24.01; H, 3.42; N, 1.62%. IR (KBr disk): 997 (w), 959 (s), 895 (m), 796 (s), 683 (m), 584 (w), 440 (m), 410 (m) cm−1. 3.2. X-ray Diffraction Measurements
Single-crystal X-ray diffraction measurements for 1 were made on a Rigaku RAXIS RAPID imaging plate diffractometer with graphite monochromated Mo-Kα radiation (λ = 0.71075 Å). Diffraction data were collected and processed with PROCESS-AUTO [38]. The structure of 1 was solved by the charge flipping method [39] and expanded using Fourier techniques. The refinement procedure was performed by the full-matrix least-squares using SHELXL97 [40]. The measurements for 2 were made on a Rigaku Saturn70 diffractometer using graphite monochromated Mo-Kα radiation. Diffraction data were collected and processed with CrystalClear [41]. The structure of 2 was solved by direct methods [42] and expanded using Fourier techniques. The refinement procedure was performed by full-matrix least-squares using SHELXL2013 [42]. All calculations were performed using the CrystalStructure [43] software package. In the refinement procedure, all non-hydrogen atoms,
Int. J. Mol. Sci. 2015, 16
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except for C37 of 2, were refined anisotropically, and the hydrogen atoms on C atoms were located in the calculated positions. The weak reflection intensities from the crystals of 2 may result in relatively high R1 and wR2 values. The results of checking cif files are available as supplementary materials. Further details of the crystal structure investigation may be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336 033; or E-Mail: [email protected] (CCDC 1055676-1055677). 4. Conclusions
Inorganic-organic hybrid crystals comprised of polyoxotungstate and surfactants having a heterocyclic moiety, [C4H4N2(C12H25)]4[W10O32]·2(CH3)2CO (1) and [C5H5N(C12H25)]4[W10O32]·4C2H5OH (2), were successfully synthesized. Dodecylpyridazinium (C12pda) and dodecylpyridinium (C12py) were utilized as organic cations, and the decatungstate anion (W10) was used for the inorganic component, which enabled the discussion of the effect of the heterocyclic moiety for the construction of the hybrid crystals. Although both hybrid crystals contained alternate stacking of W10 monolayers and interdigitated surfactant bilayers, pyridazine rings in 1 interacted more strongly with the W10 anions. 1 contained shorter C-H···O hydrogen bonds than those observed in 2, indicating that these hydrogen bonds, as well as the electrostatic interaction between the C12pda cation and the W10 anion stabilized the layered structure of C12pda-W10 with rigid packing. On the other hand, 2 has similar cell parameters and molecular arrangements as those in the crystals of hexadecylpyridinium (C16py) and W10 (3), also indicating the significance of the heterocyclic moiety for the construction of the hybrid crystals. The difference between the heterocyclic moieties led to different arrangements of W10 anions in 1 and 2, which will contribute to the precise control of molecular arrangements and the emergence of characteristic conductivity. Supplementary Materials
Supplementary materials can be found at http://www.mdpi.com/1422-0067/16/04/8505/s1. Acknowledgments
This work was supported in part by the JSPS Grant-in-Aid for Scientific Research (No. 26410245) and the Research and Study Project of Tokai University Educational System General Research Organization. Author Contributions
Saki Otobe and Takeru Ito conceived of and designed the experiments. Saki Otobe, Natsumi Fujioka and Takuro Hirano performed the experiments. Saki Otobe and Takeru Ito analyzed the data. Eri Ishikawa and Haruo Naruke contributed analysis tools. Katsuhiko Fujio contributed materials. Takeru Ito wrote the paper. Conflicts of Interest
The authors declare no conflict of interest.
Int. J. Mol. Sci. 2015, 16
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37. Renneke, R.F.; Pasquali, M.; Hill. C.L. Polyoxometalate systems for the catalytic selective production of nonthermodynamic alkenes from alkanes nature of excited-state deactivation processes and control of subsequent thermal processes in polyoxometalate photoredox chemistry. J. Am. Chem. Soc. 1990, 112, 6585–6594. 38. Rigaku Corporation. PROCESS-AUTO; Rigaku Corporation: Tokyo, Japan, 2002. 39. Palatinus, L.; Chapuis, G. SUPERFLIP—A computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J. Appl. Cryst. 2007, 40, 786–790. 40. Sheldrick, G.M. SHELX97. A short history of SHELX. Acta Cryst. 2008, A64, 112–122. 41. Rigaku Corporation. CrystalClear; Rigaku Corporation: Tokyo, Japan, 1999. 42. Sheldrick, G.M. SHELX2013. A short history of SHELX. Acta Cryst. 2008, A64, 112–122. 43. Rigaku Corporation. CrystalStructure 4.1; Rigaku Corporation: Tokyo, Japan, 2014. © 2015 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/4.0/).
Supplementary Information Check Report of cif for 1 (C12pda-W10) CheckCIF/PLATON Report You have not supplied any structure factors. As a result the full set of tests cannot be run. THIS REPORT IS FOR GUIDANCE ONLY. IF USED AS PART OF A REVIEW PROCEDURE FOR PUBLICATION, IT SHOULD NOT REPLACE THE EXPERTISE OF AN EXPERIENCED CRYSTALLOGRAPHIC REFEREE. No syntax errors found. CIF dictionary Interpreting this report Datablock: 140304
Bond precision:
C-C = 0.0183 A
Wavelength=0.71075
Cell:
a=10.55918(19)
b=18.7700(3)
c=25.4318(5)
alpha=74.4842(7) 193 K
beta=86.5737(7)
gamma=85.6363(7)
Temperature:
Calculated
Reported
Volume Space group Hall group
4838.63(15) P -1 -P 1 O32 W10, 4(C16 H29 Moiety formula N2), 2(C3 H6 O) C70 H128 N8 O34 W10 Sum formula 3464.20 Mr 2.378 Dx,g cm-3 2 Z 11.910 Mu (mm-1) 3232.0 F000 3218.05 F000’ 13,24,33 h,k,lmax 22200 Nref Tmin,Tmax 0.249,0.551 Tmin’ 0.001 Correction method= MULTI-SCAN
4838.62(15) P -1 -P 1 C70 H128 N8 O34 W10 C70 H128 N8 O34 W10 3464.31 2.378 2 11.924 3232.0 13,24,33 22146 0.139,0.551
Data completeness= 0.998
Theta(max)= 27.490
R(reflections)= 0.0452( 17651)
wR2(reflections)= 0.1162( 22146)
S = 1.034
Npar= 1106
The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level Click on the hyperlinks for more details of the test.
S2 Alert level C PLAT220_ALERT_2_C PLAT230_ALERT_2_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT234_ALERT_4_C PLAT241_ALERT_2_C PLAT241_ALERT_2_C PLAT241_ALERT_2_C PLAT241_ALERT_2_C PLAT242_ALERT_2_C PLAT242_ALERT_2_C PLAT244_ALERT_4_C PLAT342_ALERT_3_C PLAT360_ALERT_2_C PLAT362_ALERT_2_C PLAT790_ALERT_4_C O32
Ueq(max)/Ueq(min) Range Large Non-Solvent C N6 .. -- C33 Hirshfeld Test Diff for Large Hirshfeld Difference N5 .. -- N6 Large Hirshfeld Difference N7 .. -- N8 Large Hirshfeld Difference N7 .. -- C52 Large Hirshfeld Difference N8 .. -- C49 Large Hirshfeld Difference C51 .. -- C52 High Ueq as Compared to Neighbors for ..... Ueq as Compared to Neighbors for ..... High High Ueq as Compared to Neighbors for ..... Ueq as Compared to Neighbors for ..... High Low Ueq as Compared to Neighbors for ..... Low Ueq as Compared to Neighbors for ..... Low ’Solvent’ Ueq as Compared to Neighbors of Low Bond Precision on C-C Bonds ............... Short C(sp3)-C(sp3) Bond C44 C45 ... Short C(sp3)-C(sp2) Bond C66 C67 ... Centre of Gravity not Within Unit Cell: Resd. # W10
3.9 Ratio 5.2 su 0.19 Ang. 0.18 Ang. 16. Ang. 17. Ang. 0.20 Ang. N6 Check C47 Check N8 Check C55 Check C33 Check C46 Check C66 Check 0.0183 Ang. 1.42 Ang. 1.40 Ang. 1 Note
Alert level G CHEMS02_ALERT_1_G Please check that you have entered the correct _publ_requested_category classification of your compound; FI or CI or EI for inorganic; FM or CM or EM for metal-organic; FO or CO or EO for organic. From the CIF: _publ_requested_category CHOOSE FI FM FO CI CM CO From the CIF: _chemical_formula_sum:C70 H128 N8 O34 W10 Please PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 23.11 PLAT154_ALERT_1_G The su’s on the Cell Angles are Equal .......... 0.00070 C67 PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety ..... 88. PLAT432_ALERT_2_G Short Inter X...Y Contact O7 .. C50 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O9 89. .. C3 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O22 2.91 .. C49 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O24 2.89 .. C4 .. PLAT432_ALERT_2_G Short Inter X...Y Contact O25 2.89 .. C17 .. 5 PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # C16 H29 N2 8 PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # C3 H6 O 0 0 18 13
ALERT ALERT ALERT ALERT
level level level level
3 16 1 10 1
ALERT ALERT ALERT ALERT ALERT
type type type type type
A B C G
1 2 3 4 5
= = = =
Most likely a serious problem - resolve or explain A potentially serious problem, consider carefully Check. Ensure it is not caused by an omission or oversight General information/check it is not something unexpected
CIF construction/syntax error, inconsistent or missing data Indicator that the structure model may be wrong or deficient Indicator that the structure quality may be low Improvement, methodology, query or suggestion Informative message, check
or Do ! Check Why ? Degree Check Ang. Ang. Ang. Ang. Ang. Note Note
S3 Check report of cif for 2 (C12py-W10) CheckCIF/PLATON Report You have not supplied any structure factors. As a result the full set of tests cannot be run. THIS REPORT IS FOR GUIDANCE ONLY. IF USED AS PART OF A REVIEW PROCEDURE FOR PUBLICATION, IT SHOULD NOT REPLACE THE EXPERTISE OF AN EXPERIENCED CRYSTALLOGRAPHIC REFEREE. No syntax errors found. CIF dictionary Interpreting this report Datablock: TOtobeSaturn4
Bond precision:
C-C = 0.0419 A
Wavelength=0.71075
Cell:
a=10.813(7)
b=11.339(7)
c=23.610(13)
alpha=99.415(9) 173 K
beta=91.558(5)
gamma=115.588(9)
Temperature:
Volume Space group Hall group Moiety formula Sum formula Mr Dx,g cm-3 Z Mu (mm-1) F000 F000’ h,k,lmax Nref Tmin,Tmax Tmin’
Calculated
Reported
2560(3) P -1 -P 1 O32 W10, 4(C17 H30 N), 4(C2 H6 O) C76 H144 N4 O36 W10 3528.35 2.289 1 11.258 1656.0 1649.02 15,16,34 17033 0.131,0.105 0.084
2560(3) P -1 -P 1 C76 H140 N4 O36 W10 C76 H140 N4 O36 W10 3524.45 2.286 1 11.272 1652.0 15,16,34 11774 0.046,0.105
Correction method= MULTI-SCAN Data completeness= 0.691
Theta(max)= 31.493
R(reflections)= 0.0983( 8235)
wR2(reflections)= 0.3237( 11774)
S = 1.058
Npar= 563
The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level Click on the hyperlinks for more details of the test.
S4 Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......
0.812 Note
Author Response: ...This structure intrinsically exhibits many weak reflections at higher theta values. The submitted manuscript mainly reports the packing mode of the decatungstate anions and pyridinium cations. The data obtained had insufficient quality, but was sufficient to elucidate the packing feature of the decatungstate anion and heterocyclic moiety.
Alert level B PLAT342_ALERT_3_B Low Bond Precision on
C-C Bonds ...............
0.0419 Ang.
Alert level C DIFMN02_ALERT_2_C The minimum difference density is < -0.1*ZMAX*0.75 _refine_diff_density_min given = -6.420 Test value = -5.550 DIFMN03_ALERT_1_C The minimum difference density is < -0.1*ZMAX*0.75 The relevant atom site should be identified. RFACR01_ALERT_3_C The value of the weighted R factor is > 0.25 Weighted R factor given 0.324 RINTA01_ALERT_3_C The value of Rint is greater than 0.12 Rint given 0.138 PLAT020_ALERT_3_C The value of Rint is greater than 0.12 ......... PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ PLAT043_ALERT_1_C Calculated and Reported Mol. Weight Differ by .. PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... PLAT084_ALERT_3_C High wR2 Value (i.e. > 0.25) ................... PLAT098_ALERT_2_C Large Reported Min. (Negative) Residual Density PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... PLAT213_ALERT_2_C Atom O1 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C1 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C10 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C14 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C15 has ADP max/min Ratio ..... PLAT213_ALERT_2_C Atom C18 has ADP max/min Ratio ..... Ueq(max)/Ueq(min) Range PLAT220_ALERT_2_C Large Non-Solvent C PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 -- C2 .. PLAT234_ALERT_4_C Large Hirshfeld Difference W1 -- O1 .. PLAT234_ALERT_4_C Large Hirshfeld Difference W3 -- O11 .. PLAT234_ALERT_4_C Large Hirshfeld Difference C3 -- C4 .. PLAT234_ALERT_4_C Large Hirshfeld Difference C8 -- C9 .. PLAT241_ALERT_2_C High Ueq as Compared to Neighbors for ..... PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ..... PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ..... PLAT244_ALERT_4_C Low ’Solvent’ Ueq as Compared to Neighbors of PLAT244_ALERT_4_C Low ’Solvent’ Ueq as Compared to Neighbors of PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C33 C34 ... PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C37 C38 ... PLAT361_ALERT_2_C Long C(sp3)-C(sp3) Bond C29 C30 ... PLAT415_ALERT_2_C Short Inter D-H..H-X H18E .. H23A ..
0.138 Report Please Check 3.90 Check Please Check 0.32 Report -6.42 eA-3 1 3.1 oblate 3.8 prolat 3.7 prolat 3.4 oblate 3.4 prolat 3.2 oblate 3.1 Ratio 6.0 su 0.18 Ang. 0.16 Ang. 0.20 Ang. 0.19 Ang. C1 Check C2 Check C32 Check C35 Check C37 Check 2.4 Note 1.36 Ang. 1.38 Ang. 1.67 Ang. 2.10 Ang.
S5 Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C76 H140 N4 O36 W10 Atom count from the _atom_site data: C76 H144 N4 O36 W10 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: Large difference may be due to a symmetry error - see SYMMG tests From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C76 H140 N4 O36 W10 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 76.00 76.00 0.00 H 140.00 144.00 -4.00 N 4.00 4.00 0.00 O 36.00 36.00 0.00 W 10.00 10.00 0.00 CHEMS02_ALERT_1_G Please check that you have entered the correct _publ_requested_category classification of your compound; FI or CI or EI for inorganic; FM or CM or EM for metal-organic; FO or CO or EO for organic. From the CIF: _publ_requested_category CHOOSE FI FM FO CI CM CO From the CIF: _chemical_formula_sum:C76 H140 N4 O36 W10 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 2 PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large. 0.20 PLAT432_ALERT_2_G Short Inter X...Y Contact O9 .. C18 .. 2.99
1 1 33 9
ALERT ALERT ALERT ALERT
level level level level
8 21 7 6 2
ALERT ALERT ALERT ALERT ALERT
type type type type type
A B C G
1 2 3 4 5
= = = =
Most likely a serious problem - resolve or explain A potentially serious problem, consider carefully Check. Ensure it is not caused by an omission or oversight General information/check it is not something unexpected
CIF construction/syntax error, inconsistent or missing data Indicator that the structure model may be wrong or deficient Indicator that the structure quality may be low Improvement, methodology, query or suggestion Informative message, check
or Do ! Report Check Report Ang.
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