metal-organic compounds Acta Crystallographica Section C
Thus, compounds constructed from metals and sulfaquinoxaline ligands have potential applications in medicine. However, sulfaquinoxaline coordination compounds have not been reported to date. In this paper, using sulfaquinoxaline (HL) as the ligand, we have successfully prepared the title new CdII coordination compound, [Cd(L)2(H2O)]n, (I), and characterized it by single-crystal X-ray diffraction, elemental analysis, fluorescence, IR and thermal analysis.
Crystal Structure Communications ISSN 0108-2701
Synthesis, crystal structure and fluorescence spectrum of a cadmium(II) sulfaquinoxaline complex Xiu-Hua Zhao,a Ya-Yun Zhao,b Jie Zhang,b Jian-Guo Panb and Xing Lib* a
Faculty of Science, Ningbo University, Ningbo, Zhejiang 315211, People’s Republic of China, and bFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People’s Republic of China Correspondence e-mail: [email protected] Received 9 September 2013 Accepted 2 October 2013
catena-Poly[[[4-amino-N-(quinoxalin-2-yl)benzenesulfonamidato]aquacadmium(II)]--4-amino-N-(quinoxalin-2-yl)benzenesulfonamidato], [Cd(C14H11N4O2S)2(H2O)], has been synthesized hydrothermally and characterized by singlecrystal X-ray diffraction, elemental analysis, fluorescence, IR and thermal analysis. Single-crystal X-ray analysis reveals that the complex is a one-dimensional zigzag chain structure, and the CdII cation has a distorted octahedral coordination geometry formed by five N atoms from three different sulfaquinoxaline ligands and one O atom from a water molecule. The fluorescence spectrum reveals that the complex emits strong blue fluorescence and thermal analysis shows that the complex has high thermal stability. Keywords: crystal structure; fluorescence spectrum; cadmium(II) sulfaquinoxaline complex.
2. Experimental 2.1. Synthesis and crystallization
Starting materials were obtained from commercial sources and used as received, unless otherwise stated. All manipulations were carried out under an air atmosphere. Samples of Cd(OAc)22H2O (0.060 g, 0.20 mmol) and sodium sulfaquinoxaline (0.064 g, 0.20 mmol) were dissolved in deionized water (5 ml). The mixture was then sealed in a 25 ml stainless steel autoclave, heated at 373 K for 72 h and cooled slowly to room temperature, precipitating bright-yellow strip crystals of (I) (yield 34%). Elemental analysis calculated for (I) (C28H24CdN8O5S2): C 46.13, H 3.32, N 15.37%; found: C 46.10, H 3.13, N 15.64%. 2.2. Refinement
1. Introduction Supramolecular chemistry and crystal engineering are active fields of research due to the novel structural topologies available and their potential applications in host–guest chemistry, microelectronics, nonlinear optics, molecular selection, ion exchange and catalysis (Noro et al., 2000; Zaworotko, 1994; Yaghi et al., 1998). Recently, many supramolecular assemblies have been achieved by carefully selecting building blocks and organic ligands containing appropriate functional groups, such as sulfaquinoxaline, which is an important highly flexible N-donor bridging ligand (Sun et al., 2003; Eddaoudi et al., 2002). This ligand exhibits a special ability to form complexes and plays an important role in bridging metal cations. Sulfaquinoxaline is mainly used for the prevention or treatment of poultry leucocytozoonosis and coccidiosis in animals (Furusawa, 2003; Nevado et al., 2000).
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Crystal data, data collection and structure refinement details are summarized in Table 1. Atoms C1–C6, C21–C28, N3, N4, N6, O4, O5 and S1 were disordered over two orientations and the site-occupation factor of the major conformation refined to 0.504 (7). The S1—O4, S1—O5, S1A—O4A ˚, and S1A—O5A bond lengths were restrained to 1.45 (1) A and the C1—C6, C6—C5, C1A—C6A and C6A—C5A bond ˚ . Similarity and rigidlengths were restrained to 1.38 (2) A ˚ 2 and bond restraints with effective s.u. values of 0.022 A ˚ , respectively, were applied to neighbouring disordered 0.01 A atoms, with the additional constraint that the displacement parameters for atoms in the pairs C1/C1A, C5/C5A, C6/C6A and C25/C25A were equal. Ordered H atoms bonded to atoms O1, N1 and N6 were located from difference Fourier maps and refined isotropically. The positions of the disordered H atoms on N6/N6A were refined with N6—H22N restrained to
doi:10.1107/S010827011302711X
Acta Cryst. (2013). C69, 1332–1335
metal-organic compounds Table 1
Table 2
Experimental details.
˚ , ). Selected geometric parameters (A
Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A ( ) ˚ 3) V (A Z Radiation type (mm1) Crystal size (mm) Data collection Diffractometer
Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3) max, min (e A
[Cd(C14H11N4O2S)2(H2O)] 729.07 Monoclinic, P21/n 100 8.2871 (2), 30.7094 (6), 12.1783 (2) 107.289 (2) 2959.25 (11) 4 Cu K 7.69 0.06 0.05 0.04
Agilent SuperNova Dual diffractometer with Cu at zero and an Atlas CCD detector Multi-scan (CrysAlis PRO; Agilent, 2013) 0.656, 0.749 13702, 6044, 5543 0.022 0.629
0.025, 0.063, 1.07 6044 578 305 H atoms treated by a mixture of independent and constrained refinement 0.36, 0.61
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXL2013 (Sheldrick, 2008) and SHELXTL (Sheldrick, 2008).
Cd1—O1 Cd1—N5 Cd1—N2i O1—Cd1—N1 N2i—Cd1—N1 N5—Cd1—N7
2.2665 (17) 2.2836 (19) 2.3176 (19) 81.75 (7) 95.07 (7) 57.01 (7)
Cd1—N1 Cd1—N7 Cd1—N4i
2.359 (2) 2.4062 (18) 2.416 (13)
N1—Cd1—N7 N2i—Cd1—N4i N7—Cd1—N4i
114.20 (6) 58.1 (3) 93.1 (3)
Symmetry code: (i) x 12; y þ 12; z þ 12.
3. Results and discussion Complex (I) crystallizes in the monoclinic space group P21/n with Z = 4. The local coordination environment around the CdII cation is shown in Fig. 1: it is coordinated by five N atoms from three different L ligands and one O atom from the coordinated water molecule, forming a distorted octahedral coordination geometry (Table 2). The presence of a – stacking interaction between the C1–C6 and C23i–C28i rings ˚ ; symmetry code: (i) [centroid–centroid distance = 3.832 (9) A 1 1 1 x 2, y + 2, z + 2] enhances the stability of the title complex (Fig. 1). In the structure of (I), the L ligands exibit two coordination modes, a bidentate chelating mode and a chelating–bridging mode linking two CdII cations. The coordination units are extended into a one-dimensional zigzag chain by bridging L ˚ and ligands, with an adjacent Cd Cd distance of 3.9023 (5) A an intrachain Cd Cd Cd angle of the zigzag chain of 126.90 (1) . As shown in Fig. 2, adjacent chains stack on top of one another to give a layer structure.
˚ , while their occupancies were fixed with Uiso(H) = 1.14 (2) A 1.2Ueq(N). C-bound H atoms were added in their calculated ˚ , and refined using a riding positions, with C—H = 0.95 A model, with Uiso(H) = 1.2Ueq(C).
Figure 1 The coordination environment of the CdII cation of (I) (40% probability displacement ellipsoids), showing the atom-numbering scheme and – stacking interactions (dashed lines). The H atoms and minor occupied sites of the disordered atoms of the L ligands have been omitted for clarity. [Symmetry code: (i) x 12, y + 12, z + 12.] Acta Cryst. (2013). C69, 1332–1335
Figure 2 A view of the stacking of the coordination polymer chains in complex (I), with the intrachain Cd Cd vectors highlighted. [Symmetry codes: (i) x 12, y + 12, z + 12; (ii) x 1, y, z + 1; (iii) x + 1, y, z + 1.] Zhao et al.
[Cd(C14H11N4O2S)2(H2O)]
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metal-organic compounds Table 3 ˚ , ). Hydrogen-bond geometry (A D—H A
D—H
H A
D A
D—H A
C2—H2 O4 C8—H8 O5 C17—H17 O3 O1—H2W O4ii O1—H2W O5ii O1—H1W O2ii N1—H3N O3ii N6—H2N N3iii N6—H1N N8iv C19—H19 O4v N1—H4N O2i
0.95 0.95 0.95 0.85 (4) 0.85 (4) 0.86 (4) 0.89 (3) 0.88 (8) 0.86 (5) 0.95 0.87 (3)
2.53 2.56 2.59 2.57 (4) 2.06 (4) 1.93 (4) 2.24 (3) 2.59 (8) 2.20 (5) 2.60 2.24 (3)
2.918 (7) 3.159 (6) 2.944 (3) 3.296 (5) 2.822 (5) 2.769 (2) 3.123 (3) 3.280 (9) 3.039 (6) 3.202 (4) 3.061 (3)
104 121 103 145 (4) 149 (4) 164 (3) 168 (3) 136 (6) 164 (5) 122 158 (3)
Symmetry codes: (i) x 12; y þ 12; z þ 12; (ii) x 1; y; z; (iii) x þ 52; y 12; z þ 12; (iv) x þ 2; y; z; (v) x 12; y þ 12; z 12.
Figure 3 A view of the O—H O, N—H O, N—H N and C—H O interactions (dashed lines) in (I). Only H atoms involved in hydrogen bonding are shown. The minor-occupied sites of the disordered atoms of the L ligands have been omitted for clarity. [Symmetry codes: (ii) x 1, y, z; (iii) x + 52, y 12, z + 12; (iv) x + 2, y, z; (v) x 12, y + 12, z 12.]
Different kinds of hydrogen bonding can be observed in the structure of (I) (Fig. 3). The coordinated water molecules serve as hydrogen-bond donors, contributing H atoms to sulfone atoms O4, O5 and O2, forming O1—H2W O4ii, O1—H2W O5ii and O1—H1W O2ii hydrogen-bonding interactions (see Table 3 for geometric details and symmetry codes). The amino groups act as H-atom donors to atoms O2, O3, N3 and N8, forming N1—H4N O2i, N1—H3N O3ii, N6—H2N N3iii and N6—H1N N8iv hydrogen-bonding interactions (Table 3). The benzene ring acts as a hydrogenbond donor, contributing an H atom to sulfone atom O4, forming a C19—H19 O4v hydrogen-bonding interaction (Table 3). Through the O1—H1W O2ii, O1—H2W O4ii, O1—H2W O5ii, N1—H4N O2i, N1—H3N O3ii and N6—H2N N3iii hydrogen-bonding interactions, the onedimensional zigzag chains are extended into a two-dimensional hydrogen-bonding network in the (011) plane (Fig. 4).
Figure 5 The solid-state fluorescence spectrum of complex (I) (excitation at 290 nm).
The solid-state fluorescence spectrum of (I) was investigated at room temperature, and the result is presented in Fig. 5. Since the free L ligand only exhibits an emission at 448 nm, the emission peak at 450 nm for complex (I) can be attributed to ligand donation, and the broad emission centred at 470 nm
Figure 4 A view in the (011) plane of the two-dimensional hydrogen-bond (dashed lines) network of (I). Only H atoms involved in hydrogen bonding are shown.
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[Cd(C14H11N4O2S)2(H2O)]
Figure 6 The IR spectrum of complex (I). Acta Cryst. (2013). C69, 1332–1335
metal-organic compounds
Figure 7 The thermogravimetric (TG) and differential thermal analysis (DTA) curves of complex (I).
and the peak at 490 nm (excitation at 290 nm) would likely originate from the radiative transition of ligand-to-metal or metal-to-ligand charge transfer (LMCT or MLCT) emission (Li et al., 2009). Thus, this compound may be a candidate for blue-light luminescent materials, and it is believed that more IIB metal–sulfaquinoxaline compounds with excellent luminescent properties can be developed (Chen et al., 2006). As shown in Fig. 6, a strong broad absorption band centred at 3450 cm1 can be assigned to the N—H stretching vibrations of the terminal amine groups and O—H stretching vibrations of the coordinated water molecules (Stola´rova´ et al., 2013). The sharp band at 1593 cm1 is attributed to the N—H deformation vibrations of the coordinating amine groups and the C C stretching vibrations in-plane on the aromatic ring. A further easily identifiable absorption band is observed at 1348 cm1 due to the S O stretching vibrations of the sulfone group, signalling the presence of said groups. The narrow band at 1248 cm1 corresponds to the C—N stretching vibrations of the L ligand. Additionally, several weak and narrow absorption bands in the range 957– 1130 cm1 are attributed to C—H bending vibrations in-plane on the aromatic ring (Qi et al., 2012). Thermal analysis of complex (I) was performed under a flow of nitrogen gas from 308 to 1473 K at a heating rate of 283 K min1 (Fig. 7). The differential thermal analysis (DTA) curve of (I) shows two sharp endothermic peaks at 580 and 663 K, and one broad endothermic peak centred at 1003 K, corresponding to the physical or chemical reactions. The first weight loss of 2.33% (calculated 2.47%) between 403 and
Acta Cryst. (2013). C69, 1332–1335
593 K corresponds to the loss of one coordinated water molecule per [Cd(L)2(H2O)]n formula unit. The second sharp weight loss of 40.14% (calculated 41.06%) with an endothermic peak corresponds to the removal of one L ligand per formula unit between 663 and 779 K, demsontrating that the framework stability of (I) is retained up to 663 K. Upon further heating, DTA shows one broad endothermic peak centred at 1003 K, indicating further decomposition of the framework. In summary, we have synthesized a Cd–sulfaquinoxaline complex with high thermal stability and fine fluorescent performance. It exhibits a one-dimensional zigzag chain structure, which is further extended into a three-dimensional architecture by hydrogen-bonding interactions. This work may provide valuable information for preparing new functional materials. This work was supported financially by the National Natural Science Foundation of China (grant Nos. 20971075 and 61078055), the Natural Science Foundation of Zhejiang province (grant No. LY12B01005), the State Key Laboratory of Structural Chemistry (grant No. 20110010) and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, and was sponsored by the K. C. Wong Magna Fund in Ningbo University. Supplementary data for this paper are available from the IUCr electronic archives (Reference: FG3310). Services for accessing these data are described at the back of the journal.
References Agilent (2013). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Chen, W.-T., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Kuang, H.-M. (2006). Acta Cryst. C62, m571–m573. Eddaoudi, M., Kim, J., O’Keeffe, M. & Yaghi, O. M. (2002). J. Am. Chem. Soc. 124, 376–377. Furusawa, N. (2003). Anal. Chim. Acta, 481, 255–259. Li, X., Wei, D.-Y., Huang, S.-J. & Zheng, Y.-Q. (2009). J. Solid State Chem. 182, 95–101. Nevado, J. J. B., Pen˜alvo, G. C. & Bernardo, F. J. G. (2000). J. Chromatogr. A, 870, 169–177. Noro, S., Kitagawa, S., Kondo, M. & Seki, K. (2000). Angew. Chem. Int. Ed. 39, 2081–2084. Qi, J. L., Xu, W. & Zheng, Y. Q. (2012). Z. Naturforsch. Teil B, 67, 1185–1190. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Stola´rova´, M., Cˇerna´k, J., Toma´s, M. & Falvello, L. R. (2013). Acta Cryst. C69, 565–568. Sun, D.-F., Cao, R., Sun, Y.-Q., Bi, W.-H., Li, X.-J., Wang, Y.-Q., Shi, Q. & Li, X. (2003). Inorg. Chem. 42, 7512–7518. Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. L. (1998). Acc. Chem. Res. 31, 474–484. Zaworotko, M. J. (1994). Chem. Soc. Rev. 23, 283–288.
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supplementary materials
supplementary materials Acta Cryst. (2013). C69, 1332-1335
[doi:10.1107/S010827011302711X]
Synthesis, crystal structure and fluorescence spectrum of a cadmium(II) sulfaquinoxaline complex Xiu-Hua Zhao, Ya-Yun Zhao, Jie Zhang, Jian-Guo Pan and Xing Li Computing details Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). catena-Poly[[[4-amino-N-(quinoxalin-2-\ yl)benzenesulfonamidato]aquacadmium(II)]-µ-4-aminoN-(quinoxalin-2-\ yl)benzenesulfonamidato] Crystal data [Cd(C14H11N4O2S)2(H2O)] Mr = 729.07 Monoclinic, P21/n a = 8.2871 (2) Å b = 30.7094 (6) Å c = 12.1783 (2) Å β = 107.289 (2)° V = 2959.25 (11) Å3 Z=4
F(000) = 1472 Dx = 1.636 Mg m−3 Cu Kα radiation, λ = 1.54184 Å Cell parameters from 8105 reflections θ = 4.1–75.6° µ = 7.69 mm−1 T = 100 K Strip, bright yellow 0.06 × 0.05 × 0.04 mm
Data collection Agilent SuperNova Dual diffractometer with Cu at zero and Atlas CCD detector Radiation source: fine-focus sealed tube Detector resolution: 10.5594 pixels mm-1 φ and ω scans Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) Tmin = 0.656, Tmax = 0.749
13702 measured reflections 6044 independent reflections 5543 reflections with I > 2σ(I) Rint = 0.022 θmax = 75.9°, θmin = 4.1° h = −9→10 k = −34→38 l = −15→9
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.025 wR(F2) = 0.063 S = 1.07 6044 reflections 578 parameters
Acta Cryst. (2013). C69, 1332-1335
305 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites
sup-1
supplementary materials H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0268P)2 + 2.2508P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001 Δρmax = 0.36 e Å−3 Δρmin = −0.61 e Å−3
Special details Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Cd1 S2 O2 O1 N1 N7 C16 H16 C15 C17 H17 C20 C18 H18 N8 C19 H19 C10 C7 C11 H11 C9 C12 H12 C14 H14 C8 H8 O3 N5 N4 C21 C24
x
y
z
Uiso*/Ueq
Occ. (
Thus, compounds constructed from metals and sulfaquinoxaline ligands have potential applications in medicine. However, sulfaquinoxaline coordination compounds have not been reported to date. In this paper, using sulfaquinoxaline (HL) as the ligand, we have successfully prepared the title new CdII coordination compound, [Cd(L)2(H2O)]n, (I), and characterized it by single-crystal X-ray diffraction, elemental analysis, fluorescence, IR and thermal analysis.
Crystal Structure Communications ISSN 0108-2701
Synthesis, crystal structure and fluorescence spectrum of a cadmium(II) sulfaquinoxaline complex Xiu-Hua Zhao,a Ya-Yun Zhao,b Jie Zhang,b Jian-Guo Panb and Xing Lib* a
Faculty of Science, Ningbo University, Ningbo, Zhejiang 315211, People’s Republic of China, and bFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People’s Republic of China Correspondence e-mail: [email protected] Received 9 September 2013 Accepted 2 October 2013
catena-Poly[[[4-amino-N-(quinoxalin-2-yl)benzenesulfonamidato]aquacadmium(II)]--4-amino-N-(quinoxalin-2-yl)benzenesulfonamidato], [Cd(C14H11N4O2S)2(H2O)], has been synthesized hydrothermally and characterized by singlecrystal X-ray diffraction, elemental analysis, fluorescence, IR and thermal analysis. Single-crystal X-ray analysis reveals that the complex is a one-dimensional zigzag chain structure, and the CdII cation has a distorted octahedral coordination geometry formed by five N atoms from three different sulfaquinoxaline ligands and one O atom from a water molecule. The fluorescence spectrum reveals that the complex emits strong blue fluorescence and thermal analysis shows that the complex has high thermal stability. Keywords: crystal structure; fluorescence spectrum; cadmium(II) sulfaquinoxaline complex.
2. Experimental 2.1. Synthesis and crystallization
Starting materials were obtained from commercial sources and used as received, unless otherwise stated. All manipulations were carried out under an air atmosphere. Samples of Cd(OAc)22H2O (0.060 g, 0.20 mmol) and sodium sulfaquinoxaline (0.064 g, 0.20 mmol) were dissolved in deionized water (5 ml). The mixture was then sealed in a 25 ml stainless steel autoclave, heated at 373 K for 72 h and cooled slowly to room temperature, precipitating bright-yellow strip crystals of (I) (yield 34%). Elemental analysis calculated for (I) (C28H24CdN8O5S2): C 46.13, H 3.32, N 15.37%; found: C 46.10, H 3.13, N 15.64%. 2.2. Refinement
1. Introduction Supramolecular chemistry and crystal engineering are active fields of research due to the novel structural topologies available and their potential applications in host–guest chemistry, microelectronics, nonlinear optics, molecular selection, ion exchange and catalysis (Noro et al., 2000; Zaworotko, 1994; Yaghi et al., 1998). Recently, many supramolecular assemblies have been achieved by carefully selecting building blocks and organic ligands containing appropriate functional groups, such as sulfaquinoxaline, which is an important highly flexible N-donor bridging ligand (Sun et al., 2003; Eddaoudi et al., 2002). This ligand exhibits a special ability to form complexes and plays an important role in bridging metal cations. Sulfaquinoxaline is mainly used for the prevention or treatment of poultry leucocytozoonosis and coccidiosis in animals (Furusawa, 2003; Nevado et al., 2000).
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# 2013 International Union of Crystallography
Crystal data, data collection and structure refinement details are summarized in Table 1. Atoms C1–C6, C21–C28, N3, N4, N6, O4, O5 and S1 were disordered over two orientations and the site-occupation factor of the major conformation refined to 0.504 (7). The S1—O4, S1—O5, S1A—O4A ˚, and S1A—O5A bond lengths were restrained to 1.45 (1) A and the C1—C6, C6—C5, C1A—C6A and C6A—C5A bond ˚ . Similarity and rigidlengths were restrained to 1.38 (2) A ˚ 2 and bond restraints with effective s.u. values of 0.022 A ˚ , respectively, were applied to neighbouring disordered 0.01 A atoms, with the additional constraint that the displacement parameters for atoms in the pairs C1/C1A, C5/C5A, C6/C6A and C25/C25A were equal. Ordered H atoms bonded to atoms O1, N1 and N6 were located from difference Fourier maps and refined isotropically. The positions of the disordered H atoms on N6/N6A were refined with N6—H22N restrained to
doi:10.1107/S010827011302711X
Acta Cryst. (2013). C69, 1332–1335
metal-organic compounds Table 1
Table 2
Experimental details.
˚ , ). Selected geometric parameters (A
Crystal data Chemical formula Mr Crystal system, space group Temperature (K) ˚) a, b, c (A ( ) ˚ 3) V (A Z Radiation type (mm1) Crystal size (mm) Data collection Diffractometer
Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint ˚ 1) (sin /)max (A Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment ˚ 3) max, min (e A
[Cd(C14H11N4O2S)2(H2O)] 729.07 Monoclinic, P21/n 100 8.2871 (2), 30.7094 (6), 12.1783 (2) 107.289 (2) 2959.25 (11) 4 Cu K 7.69 0.06 0.05 0.04
Agilent SuperNova Dual diffractometer with Cu at zero and an Atlas CCD detector Multi-scan (CrysAlis PRO; Agilent, 2013) 0.656, 0.749 13702, 6044, 5543 0.022 0.629
0.025, 0.063, 1.07 6044 578 305 H atoms treated by a mixture of independent and constrained refinement 0.36, 0.61
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXL2013 (Sheldrick, 2008) and SHELXTL (Sheldrick, 2008).
Cd1—O1 Cd1—N5 Cd1—N2i O1—Cd1—N1 N2i—Cd1—N1 N5—Cd1—N7
2.2665 (17) 2.2836 (19) 2.3176 (19) 81.75 (7) 95.07 (7) 57.01 (7)
Cd1—N1 Cd1—N7 Cd1—N4i
2.359 (2) 2.4062 (18) 2.416 (13)
N1—Cd1—N7 N2i—Cd1—N4i N7—Cd1—N4i
114.20 (6) 58.1 (3) 93.1 (3)
Symmetry code: (i) x 12; y þ 12; z þ 12.
3. Results and discussion Complex (I) crystallizes in the monoclinic space group P21/n with Z = 4. The local coordination environment around the CdII cation is shown in Fig. 1: it is coordinated by five N atoms from three different L ligands and one O atom from the coordinated water molecule, forming a distorted octahedral coordination geometry (Table 2). The presence of a – stacking interaction between the C1–C6 and C23i–C28i rings ˚ ; symmetry code: (i) [centroid–centroid distance = 3.832 (9) A 1 1 1 x 2, y + 2, z + 2] enhances the stability of the title complex (Fig. 1). In the structure of (I), the L ligands exibit two coordination modes, a bidentate chelating mode and a chelating–bridging mode linking two CdII cations. The coordination units are extended into a one-dimensional zigzag chain by bridging L ˚ and ligands, with an adjacent Cd Cd distance of 3.9023 (5) A an intrachain Cd Cd Cd angle of the zigzag chain of 126.90 (1) . As shown in Fig. 2, adjacent chains stack on top of one another to give a layer structure.
˚ , while their occupancies were fixed with Uiso(H) = 1.14 (2) A 1.2Ueq(N). C-bound H atoms were added in their calculated ˚ , and refined using a riding positions, with C—H = 0.95 A model, with Uiso(H) = 1.2Ueq(C).
Figure 1 The coordination environment of the CdII cation of (I) (40% probability displacement ellipsoids), showing the atom-numbering scheme and – stacking interactions (dashed lines). The H atoms and minor occupied sites of the disordered atoms of the L ligands have been omitted for clarity. [Symmetry code: (i) x 12, y + 12, z + 12.] Acta Cryst. (2013). C69, 1332–1335
Figure 2 A view of the stacking of the coordination polymer chains in complex (I), with the intrachain Cd Cd vectors highlighted. [Symmetry codes: (i) x 12, y + 12, z + 12; (ii) x 1, y, z + 1; (iii) x + 1, y, z + 1.] Zhao et al.
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metal-organic compounds Table 3 ˚ , ). Hydrogen-bond geometry (A D—H A
D—H
H A
D A
D—H A
C2—H2 O4 C8—H8 O5 C17—H17 O3 O1—H2W O4ii O1—H2W O5ii O1—H1W O2ii N1—H3N O3ii N6—H2N N3iii N6—H1N N8iv C19—H19 O4v N1—H4N O2i
0.95 0.95 0.95 0.85 (4) 0.85 (4) 0.86 (4) 0.89 (3) 0.88 (8) 0.86 (5) 0.95 0.87 (3)
2.53 2.56 2.59 2.57 (4) 2.06 (4) 1.93 (4) 2.24 (3) 2.59 (8) 2.20 (5) 2.60 2.24 (3)
2.918 (7) 3.159 (6) 2.944 (3) 3.296 (5) 2.822 (5) 2.769 (2) 3.123 (3) 3.280 (9) 3.039 (6) 3.202 (4) 3.061 (3)
104 121 103 145 (4) 149 (4) 164 (3) 168 (3) 136 (6) 164 (5) 122 158 (3)
Symmetry codes: (i) x 12; y þ 12; z þ 12; (ii) x 1; y; z; (iii) x þ 52; y 12; z þ 12; (iv) x þ 2; y; z; (v) x 12; y þ 12; z 12.
Figure 3 A view of the O—H O, N—H O, N—H N and C—H O interactions (dashed lines) in (I). Only H atoms involved in hydrogen bonding are shown. The minor-occupied sites of the disordered atoms of the L ligands have been omitted for clarity. [Symmetry codes: (ii) x 1, y, z; (iii) x + 52, y 12, z + 12; (iv) x + 2, y, z; (v) x 12, y + 12, z 12.]
Different kinds of hydrogen bonding can be observed in the structure of (I) (Fig. 3). The coordinated water molecules serve as hydrogen-bond donors, contributing H atoms to sulfone atoms O4, O5 and O2, forming O1—H2W O4ii, O1—H2W O5ii and O1—H1W O2ii hydrogen-bonding interactions (see Table 3 for geometric details and symmetry codes). The amino groups act as H-atom donors to atoms O2, O3, N3 and N8, forming N1—H4N O2i, N1—H3N O3ii, N6—H2N N3iii and N6—H1N N8iv hydrogen-bonding interactions (Table 3). The benzene ring acts as a hydrogenbond donor, contributing an H atom to sulfone atom O4, forming a C19—H19 O4v hydrogen-bonding interaction (Table 3). Through the O1—H1W O2ii, O1—H2W O4ii, O1—H2W O5ii, N1—H4N O2i, N1—H3N O3ii and N6—H2N N3iii hydrogen-bonding interactions, the onedimensional zigzag chains are extended into a two-dimensional hydrogen-bonding network in the (011) plane (Fig. 4).
Figure 5 The solid-state fluorescence spectrum of complex (I) (excitation at 290 nm).
The solid-state fluorescence spectrum of (I) was investigated at room temperature, and the result is presented in Fig. 5. Since the free L ligand only exhibits an emission at 448 nm, the emission peak at 450 nm for complex (I) can be attributed to ligand donation, and the broad emission centred at 470 nm
Figure 4 A view in the (011) plane of the two-dimensional hydrogen-bond (dashed lines) network of (I). Only H atoms involved in hydrogen bonding are shown.
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Figure 6 The IR spectrum of complex (I). Acta Cryst. (2013). C69, 1332–1335
metal-organic compounds
Figure 7 The thermogravimetric (TG) and differential thermal analysis (DTA) curves of complex (I).
and the peak at 490 nm (excitation at 290 nm) would likely originate from the radiative transition of ligand-to-metal or metal-to-ligand charge transfer (LMCT or MLCT) emission (Li et al., 2009). Thus, this compound may be a candidate for blue-light luminescent materials, and it is believed that more IIB metal–sulfaquinoxaline compounds with excellent luminescent properties can be developed (Chen et al., 2006). As shown in Fig. 6, a strong broad absorption band centred at 3450 cm1 can be assigned to the N—H stretching vibrations of the terminal amine groups and O—H stretching vibrations of the coordinated water molecules (Stola´rova´ et al., 2013). The sharp band at 1593 cm1 is attributed to the N—H deformation vibrations of the coordinating amine groups and the C C stretching vibrations in-plane on the aromatic ring. A further easily identifiable absorption band is observed at 1348 cm1 due to the S O stretching vibrations of the sulfone group, signalling the presence of said groups. The narrow band at 1248 cm1 corresponds to the C—N stretching vibrations of the L ligand. Additionally, several weak and narrow absorption bands in the range 957– 1130 cm1 are attributed to C—H bending vibrations in-plane on the aromatic ring (Qi et al., 2012). Thermal analysis of complex (I) was performed under a flow of nitrogen gas from 308 to 1473 K at a heating rate of 283 K min1 (Fig. 7). The differential thermal analysis (DTA) curve of (I) shows two sharp endothermic peaks at 580 and 663 K, and one broad endothermic peak centred at 1003 K, corresponding to the physical or chemical reactions. The first weight loss of 2.33% (calculated 2.47%) between 403 and
Acta Cryst. (2013). C69, 1332–1335
593 K corresponds to the loss of one coordinated water molecule per [Cd(L)2(H2O)]n formula unit. The second sharp weight loss of 40.14% (calculated 41.06%) with an endothermic peak corresponds to the removal of one L ligand per formula unit between 663 and 779 K, demsontrating that the framework stability of (I) is retained up to 663 K. Upon further heating, DTA shows one broad endothermic peak centred at 1003 K, indicating further decomposition of the framework. In summary, we have synthesized a Cd–sulfaquinoxaline complex with high thermal stability and fine fluorescent performance. It exhibits a one-dimensional zigzag chain structure, which is further extended into a three-dimensional architecture by hydrogen-bonding interactions. This work may provide valuable information for preparing new functional materials. This work was supported financially by the National Natural Science Foundation of China (grant Nos. 20971075 and 61078055), the Natural Science Foundation of Zhejiang province (grant No. LY12B01005), the State Key Laboratory of Structural Chemistry (grant No. 20110010) and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, and was sponsored by the K. C. Wong Magna Fund in Ningbo University. Supplementary data for this paper are available from the IUCr electronic archives (Reference: FG3310). Services for accessing these data are described at the back of the journal.
References Agilent (2013). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Chen, W.-T., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Kuang, H.-M. (2006). Acta Cryst. C62, m571–m573. Eddaoudi, M., Kim, J., O’Keeffe, M. & Yaghi, O. M. (2002). J. Am. Chem. Soc. 124, 376–377. Furusawa, N. (2003). Anal. Chim. Acta, 481, 255–259. Li, X., Wei, D.-Y., Huang, S.-J. & Zheng, Y.-Q. (2009). J. Solid State Chem. 182, 95–101. Nevado, J. J. B., Pen˜alvo, G. C. & Bernardo, F. J. G. (2000). J. Chromatogr. A, 870, 169–177. Noro, S., Kitagawa, S., Kondo, M. & Seki, K. (2000). Angew. Chem. Int. Ed. 39, 2081–2084. Qi, J. L., Xu, W. & Zheng, Y. Q. (2012). Z. Naturforsch. Teil B, 67, 1185–1190. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Stola´rova´, M., Cˇerna´k, J., Toma´s, M. & Falvello, L. R. (2013). Acta Cryst. C69, 565–568. Sun, D.-F., Cao, R., Sun, Y.-Q., Bi, W.-H., Li, X.-J., Wang, Y.-Q., Shi, Q. & Li, X. (2003). Inorg. Chem. 42, 7512–7518. Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. L. (1998). Acc. Chem. Res. 31, 474–484. Zaworotko, M. J. (1994). Chem. Soc. Rev. 23, 283–288.
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supplementary materials Acta Cryst. (2013). C69, 1332-1335
[doi:10.1107/S010827011302711X]
Synthesis, crystal structure and fluorescence spectrum of a cadmium(II) sulfaquinoxaline complex Xiu-Hua Zhao, Ya-Yun Zhao, Jie Zhang, Jian-Guo Pan and Xing Li Computing details Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). catena-Poly[[[4-amino-N-(quinoxalin-2-\ yl)benzenesulfonamidato]aquacadmium(II)]-µ-4-aminoN-(quinoxalin-2-\ yl)benzenesulfonamidato] Crystal data [Cd(C14H11N4O2S)2(H2O)] Mr = 729.07 Monoclinic, P21/n a = 8.2871 (2) Å b = 30.7094 (6) Å c = 12.1783 (2) Å β = 107.289 (2)° V = 2959.25 (11) Å3 Z=4
F(000) = 1472 Dx = 1.636 Mg m−3 Cu Kα radiation, λ = 1.54184 Å Cell parameters from 8105 reflections θ = 4.1–75.6° µ = 7.69 mm−1 T = 100 K Strip, bright yellow 0.06 × 0.05 × 0.04 mm
Data collection Agilent SuperNova Dual diffractometer with Cu at zero and Atlas CCD detector Radiation source: fine-focus sealed tube Detector resolution: 10.5594 pixels mm-1 φ and ω scans Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) Tmin = 0.656, Tmax = 0.749
13702 measured reflections 6044 independent reflections 5543 reflections with I > 2σ(I) Rint = 0.022 θmax = 75.9°, θmin = 4.1° h = −9→10 k = −34→38 l = −15→9
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.025 wR(F2) = 0.063 S = 1.07 6044 reflections 578 parameters
Acta Cryst. (2013). C69, 1332-1335
305 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites
sup-1
supplementary materials H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0268P)2 + 2.2508P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001 Δρmax = 0.36 e Å−3 Δρmin = −0.61 e Å−3
Special details Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Cd1 S2 O2 O1 N1 N7 C16 H16 C15 C17 H17 C20 C18 H18 N8 C19 H19 C10 C7 C11 H11 C9 C12 H12 C14 H14 C8 H8 O3 N5 N4 C21 C24
x
y
z
Uiso*/Ueq
Occ. (
