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accesscatena-Poly[[dichloridozinc(II)]-μ-1,4-bis(1H-imidazol-1-yl)benzene]
aTraditional Chinese Medicine College of Ningxia Medical University, Yinchuan, Ningxia Province 750004, People's Republic of China, bPharmacy College of Ningxia Medical University, Yinchuan, Ningxia, Province 750004, People's Republic of China, and cThe Second Hospital of Jilin University, Changchun, Jilin Province 130041, People's Republic of China
*Correspondence e-mail: nanyiailing@yeah.net
In the title one-dimensional coordination polymer, [ZnCl2(C12H10N4)]n, the ZnII atom (site symmetry 2) is coordinated by two chloride ions and two 1,4-bis(imidazol-1-yl)benzene ligands, generating a distorted tetrahedral ZnCl2N2 geometry for the metal ion. The bridging ligand, which is completed by crystallographic inversion symmetry, links the ZnII atoms into zigzag chains propagating in [101]. Within the ligand, the dihedral angle between the central benzene ring and terminal imidazole ring is 27.82 (13)°.
Related literature
For background to coordination polymers containing imidazole-derived ligands, see: Jin et al. (2006![[Jin, C. M., Lu, H., Wu, L. Y. & Huang, J. (2006). Chem. Commun. pp. 5039-5041.]](../../../../../../logos/arrows/e_arr.gif "Jin, C. M., Lu, H., Wu, L. Y. & Huang, J. (2006). Chem. Commun. pp. 5039-5041.")
); Li et al. (2010); Lin et al. (2008).
![[Scheme 1]](hb5712scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810044429/hb5712sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044429/hb5712Isup2.hkl
A mixture of C2H5OH and H2O (1:1, 8 ml), as a buffer layer, was carefully layered over a solution of ZnCl2 (0.02 mmol) in H2O (6 ml). Then a solution of 1,4-Bis(imidazol-1-yl)phenyl (L, 0.06 mmol) in C2H5OH (6 ml) was layered over the buffer layer, and the resultant reaction was left to stand at room temperature. After ca three weeks, colorless blocks of (I) appeared at the boundary. Yield: ~30% (based on L).
C-bound H atoms were positioned geometrically and refined in the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq.
Imidazole derivates has been well used in crystal engineering, and a large number of imidazole-containing flexible ligands have been extensively studied (Jin et al., 2006; Lin et al., 2008). However, to our knowledge, the research on imidazole ligands bearing rigid spacers is still less developed (Li et al., 2010).
Single-crystal X-ray reveals that the title compound (I) crystallizes in the monoclinic C2/c. The geometry of the Zn(II) ion is surrounded by two imidazole rings of distinct L ligands and two chlorine anions, which illustrates a slightly distorted tetrahedral coordination environment (Fig 1). Notably, as shown in Fig 2, the four-coordinated Zn(II) center is connected by the linear ligand L into an infinite one-dimensional zigzag chain.
For background to coordination polymers containing imidazole-derived ligands, see: Jin et al. (2006); Li et al. (2010); Lin et al. (2008).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hb5712fig1thm.gif) | Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius. |
![[Figure 2]](./hb5712fig2thm.gif) | Fig. 2. The crystal packing for (I). |
| [ZnCl2(C12H10N4)] | F(000) = 696 |
| Mr = 346.51 | Dx = 1.668 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 6568 reflections |
| a = 13.196 (3) Å | θ = 6.2–54.8° |
| b = 6.3780 (13) Å | µ = 2.16 mm−1 |
| c = 16.431 (3) Å | T = 293 K |
| β = 93.75 (3)° | Block, colorless |
| V = 1379.9 (5) Å3 | 0.25 × 0.22 × 0.20 mm |
| Z = 4 |
| Rigaku Mercury diffractometer | 1209 independent reflections |
| Radiation source: fine-focus sealed tube | 1136 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 3.1° |
| ω scans | h = −15→15 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −7→7 |
| Tmin = 0.589, Tmax = 0.650 | l = −19→19 |
| 5725 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.058 | H-atom parameters constrained |
| S = 1.18 | w = 1/[σ2(Fo2) + (0.022P)2 + 1.5504P] where P = (Fo2 + 2Fc2)/3 |
| 1209 reflections | (Δ/σ)max < 0.001 |
| 87 parameters | Δρmax = 0.26 e Å−3 |
| 0 restraints | Δρmin = −0.33 e Å−3 |
| [ZnCl2(C12H10N4)] | V = 1379.9 (5) Å3 |
| Mr = 346.51 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 13.196 (3) Å | µ = 2.16 mm−1 |
| b = 6.3780 (13) Å | T = 293 K |
| c = 16.431 (3) Å | 0.25 × 0.22 × 0.20 mm |
| β = 93.75 (3)° |
| Rigaku Mercury diffractometer | 1209 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1136 reflections with I > 2σ(I) |
| Tmin = 0.589, Tmax = 0.650 | Rint = 0.028 |
| 5725 measured reflections |
| R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
| wR(F2) = 0.058 | H-atom parameters constrained |
| S = 1.18 | Δρmax = 0.26 e Å−3 |
| 1209 reflections | Δρmin = −0.33 e Å−3 |
| 87 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Zn1 | 0.5000 | 0.47523 (6) | 0.2500 | 0.02629 (14) | |
| Cl1 | 0.62428 (6) | 0.67534 (12) | 0.20142 (4) | 0.0488 (2) | |
| N1 | 0.45231 (15) | 0.2933 (3) | 0.15401 (11) | 0.0288 (5) | |
| N2 | 0.37084 (14) | 0.0812 (3) | 0.06614 (11) | 0.0275 (5) | |
| C1 | 0.38454 (18) | 0.1419 (4) | 0.14535 (14) | 0.0296 (6) | |
| H1A | 0.3506 | 0.0842 | 0.1878 | 0.036* | |
| C2 | 0.4850 (2) | 0.3299 (4) | 0.07706 (15) | 0.0363 (6) | |
| H2A | 0.5341 | 0.4274 | 0.0648 | 0.044* | |
| C3 | 0.4350 (2) | 0.2028 (4) | 0.02255 (15) | 0.0362 (6) | |
| H3A | 0.4422 | 0.1978 | −0.0333 | 0.043* | |
| C4 | 0.30781 (18) | −0.0863 (4) | 0.03321 (14) | 0.0269 (5) | |
| C5 | 0.2728 (2) | −0.0807 (4) | −0.04871 (15) | 0.0350 (6) | |
| H5A | 0.2882 | 0.0330 | −0.0811 | 0.042* | |
| C6 | 0.28494 (19) | −0.2555 (4) | 0.08161 (15) | 0.0334 (6) | |
| H6A | 0.3084 | −0.2588 | 0.1362 | 0.040* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0337 (2) | 0.0263 (2) | 0.0182 (2) | 0.000 | −0.00328 (15) | 0.000 |
| Cl1 | 0.0571 (5) | 0.0594 (5) | 0.0295 (4) | −0.0279 (4) | 0.0008 (3) | −0.0005 (3) |
| N1 | 0.0349 (12) | 0.0296 (11) | 0.0214 (11) | −0.0060 (9) | −0.0017 (8) | −0.0011 (8) |
| N2 | 0.0336 (11) | 0.0267 (11) | 0.0216 (10) | −0.0062 (9) | −0.0020 (8) | −0.0024 (8) |
| C1 | 0.0340 (13) | 0.0334 (14) | 0.0214 (13) | −0.0070 (11) | 0.0014 (10) | −0.0014 (10) |
| C2 | 0.0478 (16) | 0.0338 (15) | 0.0276 (14) | −0.0150 (12) | 0.0031 (11) | −0.0001 (11) |
| C3 | 0.0529 (17) | 0.0344 (14) | 0.0213 (13) | −0.0146 (13) | 0.0032 (11) | −0.0013 (10) |
| C4 | 0.0299 (13) | 0.0270 (12) | 0.0235 (12) | −0.0032 (10) | −0.0016 (10) | −0.0034 (10) |
| C5 | 0.0477 (16) | 0.0306 (14) | 0.0258 (13) | −0.0086 (12) | −0.0033 (11) | 0.0055 (10) |
| C6 | 0.0431 (15) | 0.0351 (14) | 0.0205 (12) | −0.0067 (12) | −0.0080 (10) | 0.0004 (10) |
| Zn1—N1 | 2.0248 (19) | C2—C3 | 1.348 (3) |
| Zn1—N1i | 2.0248 (19) | C2—H2A | 0.9300 |
| Zn1—Cl1i | 2.2643 (8) | C3—H3A | 0.9300 |
| Zn1—Cl1 | 2.2643 (8) | C4—C6 | 1.385 (3) |
| N1—C1 | 1.317 (3) | C4—C5 | 1.395 (3) |
| N1—C2 | 1.382 (3) | C5—C6ii | 1.382 (3) |
| N2—C1 | 1.359 (3) | C5—H5A | 0.9300 |
| N2—C3 | 1.382 (3) | C6—C5ii | 1.382 (3) |
| N2—C4 | 1.438 (3) | C6—H6A | 0.9300 |
| C1—H1A | 0.9300 | ||
| N1—Zn1—N1i | 110.08 (11) | C3—C2—N1 | 109.7 (2) |
| N1—Zn1—Cl1i | 113.71 (6) | C3—C2—H2A | 125.1 |
| N1i—Zn1—Cl1i | 104.11 (6) | N1—C2—H2A | 125.1 |
| N1—Zn1—Cl1 | 104.11 (6) | C2—C3—N2 | 106.4 (2) |
| N1i—Zn1—Cl1 | 113.71 (6) | C2—C3—H3A | 126.8 |
| Cl1i—Zn1—Cl1 | 111.38 (5) | N2—C3—H3A | 126.8 |
| C1—N1—C2 | 105.98 (19) | C6—C4—C5 | 120.2 (2) |
| C1—N1—Zn1 | 132.71 (16) | C6—C4—N2 | 120.3 (2) |
| C2—N1—Zn1 | 121.06 (16) | C5—C4—N2 | 119.4 (2) |
| C1—N2—C3 | 106.79 (19) | C6ii—C5—C4 | 119.8 (2) |
| C1—N2—C4 | 127.6 (2) | C6ii—C5—H5A | 120.1 |
| C3—N2—C4 | 125.50 (19) | C4—C5—H5A | 120.1 |
| N1—C1—N2 | 111.1 (2) | C5ii—C6—C4 | 120.0 (2) |
| N1—C1—H1A | 124.5 | C5ii—C6—H6A | 120.0 |
| N2—C1—H1A | 124.5 | C4—C6—H6A | 120.0 |
| N1i—Zn1—N1—C1 | 55.1 (2) | N1—C2—C3—N2 | −1.0 (3) |
| Cl1i—Zn1—N1—C1 | −61.2 (2) | C1—N2—C3—C2 | 0.5 (3) |
| Cl1—Zn1—N1—C1 | 177.4 (2) | C4—N2—C3—C2 | −175.6 (2) |
| N1i—Zn1—N1—C2 | −131.4 (2) | C1—N2—C4—C6 | −25.8 (4) |
| Cl1i—Zn1—N1—C2 | 112.23 (19) | C3—N2—C4—C6 | 149.4 (3) |
| Cl1—Zn1—N1—C2 | −9.2 (2) | C1—N2—C4—C5 | 156.4 (2) |
| C2—N1—C1—N2 | −0.9 (3) | C3—N2—C4—C5 | −28.4 (4) |
| Zn1—N1—C1—N2 | 173.23 (16) | C6—C4—C5—C6ii | 0.0 (4) |
| C3—N2—C1—N1 | 0.3 (3) | N2—C4—C5—C6ii | 177.8 (2) |
| C4—N2—C1—N1 | 176.3 (2) | C5—C4—C6—C5ii | 0.0 (4) |
| C1—N1—C2—C3 | 1.2 (3) | N2—C4—C6—C5ii | −177.8 (2) |
| Zn1—N1—C2—C3 | −173.77 (17) |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, −y−1/2, −z. |
Experimental details
| Crystal data | |
| Chemical formula | [ZnCl2(C12H10N4)] |
| Mr | 346.51 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 13.196 (3), 6.3780 (13), 16.431 (3) |
| β (°) | 93.75 (3) |
| V (Å3) | 1379.9 (5) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 2.16 |
| Crystal size (mm) | 0.25 × 0.22 × 0.20 |
| Data collection | |
| Diffractometer | Rigaku Mercury |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
| Tmin, Tmax | 0.589, 0.650 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5725, 1209, 1136 |
| Rint | 0.028 |
| (sin θ/λ)max (Å−1) | 0.594 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.058, 1.18 |
| No. of reflections | 1209 |
| No. of parameters | 87 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.26, −0.33 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This project was supported by a scientific research grant of special talents from Ningxia Medical University (XT200806).
References
Jin, C. M., Lu, H., Wu, L. Y. & Huang, J. (2006). Chem. Commun. pp. 5039–5041. Web of Science CSD CrossRef Google Scholar
Li, Z. X., Hu, T. L., Ma, H., Zeng, Y. F., Li, C. J., Tong, M. L. & Bu, X. H. (2010). Cryst. Growth Des. 10, 1138–1144. Web of Science CSD CrossRef CAS Google Scholar
Lin, J. D., Cheng, J. W. & Du, S. W. (2008). Cryst. Growth Des. 8, 3345–3353. Web of Science CSD CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Imidazole derivates has been well used in crystal engineering, and a large number of imidazole-containing flexible ligands have been extensively studied (Jin et al., 2006; Lin et al., 2008). However, to our knowledge, the research on imidazole ligands bearing rigid spacers is still less developed (Li et al., 2010).
Single-crystal X-ray diffraction analysis reveals that the title compound (I) crystallizes in the monoclinic space group C2/c. The geometry of the Zn(II) ion is surrounded by two imidazole rings of distinct L ligands and two chlorine anions, which illustrates a slightly distorted tetrahedral coordination environment (Fig 1). Notably, as shown in Fig 2, the four-coordinated Zn(II) center is connected by the linear ligand L into an infinite one-dimensional zigzag chain.