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accesscatena-Poly[[dichloridocopper(II)]-μ-4,4′-bis(benzimidazol-1-yl)biphenyl]
aKey Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), College of Chemistry & Materials Science, Northwest University, Xi'an 710069, People's Republic of China, and bThe College of Life Sciences, Northwest University, Xi'an 710069, People's Republic of China
*Correspondence e-mail: nwuchem@126.com
In the title compound, [CuCl2(C26H18N4)]n, the Cu(II) ion is four-coordinated by two N atoms from two 4,4′-bis(benzoimidazol-1-yl)biphenyl ligands and two chloride anions, in a slightly distorted tetrahedral environment. The biphenyl ligand acts as a linear bidentate ligand, connecting the metal atoms into an infinite chain parallel to [101]. In the biphenyl ligand, the two benzene rings make a dihedral angle of 33.19 (7)°.
Related literature
For background to benzimidazole-based ligands in crystal engineering, 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. (2009); Su et al. (2003).
![[Scheme 1]](fj2406scheme1.gif)
Experimental
Crystal data
|
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: 10.1107/S1600536811011421/fj2406sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811011421/fj2406Isup2.hkl
A mixture of CH3OH and CHCl3 (1:1, 8 ml), as a buffer layer, was carefully layered over a solution of 4,4'-Bis(benzoimidazol-1-yl)terphenyl (L, 0.06 mmol) in CHCl3 (6 ml). Then a solution of CuCl2 (0.06 mmol) in CH3OH (6 ml) was layered over the buffer layer, and the resultant reaction was left to stand at room temperature. After ca three weeks, purple block single crystals appeared at the boundary. Yield: ~35% (based on L).
C-bound H atoms were positioned geometrically and refined in the riding-model approximation, with C—H = 0.93Å and Uiso(H) = 1.2Ueq.
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]](./fj2406fig1thm.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]](./fj2406fig2thm.gif) | Fig. 2. The crystal packing for (I). |
| [CuCl2(C26H18N4)] | F(000) = 1060 |
| Mr = 520.88 | Dx = 1.601 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2903 reflections |
| a = 12.599 (4) Å | θ = 2.1–27.9° |
| b = 15.280 (4) Å | µ = 1.28 mm−1 |
| c = 11.233 (3) Å | T = 293 K |
| β = 91.936 (4)° | Block, brown |
| V = 2161.3 (10) Å3 | 0.04 × 0.03 × 0.02 mm |
| Z = 4 |
| Rigaku Mercury CCD area-detector diffractometer | 1903 independent reflections |
| Radiation source: fine-focus sealed tube | 1761 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.027 |
| Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 3.2° |
| ω scans | h = −14→14 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −18→18 |
| Tmin = 0.955, Tmax = 0.975 | l = −13→13 |
| 6675 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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.066 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0296P)2 + 3.937P] where P = (Fo2 + 2Fc2)/3 |
| 1903 reflections | (Δ/σ)max = 0.002 |
| 151 parameters | Δρmax = 0.50 e Å−3 |
| 0 restraints | Δρmin = −0.27 e Å−3 |
| [CuCl2(C26H18N4)] | V = 2161.3 (10) Å3 |
| Mr = 520.88 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 12.599 (4) Å | µ = 1.28 mm−1 |
| b = 15.280 (4) Å | T = 293 K |
| c = 11.233 (3) Å | 0.04 × 0.03 × 0.02 mm |
| β = 91.936 (4)° |
| Rigaku Mercury CCD area-detector diffractometer | 1903 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1761 reflections with I > 2σ(I) |
| Tmin = 0.955, Tmax = 0.975 | Rint = 0.027 |
| 6675 measured reflections |
| R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
| wR(F2) = 0.066 | H-atom parameters constrained |
| S = 1.06 | Δρmax = 0.50 e Å−3 |
| 1903 reflections | Δρmin = −0.27 e Å−3 |
| 151 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 | ||
| Cu1 | 1.0000 | 1.09184 (2) | 0.7500 | 0.01275 (12) | |
| Cl1 | 0.98903 (4) | 1.18252 (3) | 0.59365 (5) | 0.02221 (15) | |
| N1 | 0.89293 (14) | 1.01051 (11) | 0.81368 (14) | 0.0136 (4) | |
| N2 | 0.75910 (13) | 0.96997 (11) | 0.92601 (15) | 0.0128 (4) | |
| C1 | 0.83320 (16) | 1.03097 (13) | 0.90401 (18) | 0.0138 (4) | |
| H1 | 0.8414 | 1.0822 | 0.9480 | 0.017* | |
| C2 | 0.85403 (16) | 0.92994 (13) | 0.77153 (18) | 0.0121 (4) | |
| C3 | 0.88572 (16) | 0.87841 (13) | 0.67670 (17) | 0.0133 (4) | |
| H3 | 0.9422 | 0.8949 | 0.6304 | 0.016* | |
| C4 | 0.83018 (17) | 0.80212 (13) | 0.65424 (19) | 0.0158 (4) | |
| H4 | 0.8493 | 0.7666 | 0.5913 | 0.019* | |
| C5 | 0.74523 (17) | 0.77700 (13) | 0.72469 (19) | 0.0168 (5) | |
| H5 | 0.7089 | 0.7255 | 0.7064 | 0.020* | |
| C6 | 0.71401 (17) | 0.82661 (13) | 0.82038 (19) | 0.0142 (4) | |
| H6 | 0.6584 | 0.8095 | 0.8676 | 0.017* | |
| C7 | 0.77056 (16) | 0.90357 (13) | 0.84203 (17) | 0.0125 (4) | |
| C8 | 0.68519 (16) | 0.97360 (13) | 1.02045 (18) | 0.0132 (4) | |
| C9 | 0.66932 (17) | 0.89992 (14) | 1.08940 (19) | 0.0177 (5) | |
| H9 | 0.7071 | 0.8488 | 1.0756 | 0.021* | |
| C10 | 0.59681 (17) | 0.90309 (14) | 1.17892 (19) | 0.0177 (5) | |
| H10 | 0.5857 | 0.8533 | 1.2245 | 0.021* | |
| C11 | 0.53980 (16) | 0.97924 (13) | 1.20262 (17) | 0.0129 (4) | |
| C12 | 0.55967 (16) | 1.05353 (13) | 1.13412 (18) | 0.0129 (4) | |
| H12 | 0.5247 | 1.1056 | 1.1502 | 0.015* | |
| C13 | 0.63069 (16) | 1.05066 (13) | 1.04257 (18) | 0.0137 (4) | |
| H13 | 0.6418 | 1.1000 | 0.9962 | 0.016* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0123 (2) | 0.01272 (19) | 0.01364 (19) | 0.000 | 0.00700 (14) | 0.000 |
| Cl1 | 0.0252 (3) | 0.0219 (3) | 0.0202 (3) | 0.0108 (2) | 0.0105 (2) | 0.0070 (2) |
| N1 | 0.0132 (9) | 0.0158 (9) | 0.0121 (9) | −0.0018 (7) | 0.0043 (7) | −0.0008 (7) |
| N2 | 0.0121 (9) | 0.0151 (8) | 0.0114 (8) | −0.0016 (7) | 0.0052 (7) | 0.0000 (7) |
| C1 | 0.0118 (11) | 0.0166 (10) | 0.0131 (10) | −0.0021 (8) | 0.0037 (8) | −0.0004 (8) |
| C2 | 0.0110 (10) | 0.0138 (10) | 0.0114 (10) | −0.0011 (8) | 0.0011 (8) | 0.0014 (8) |
| C3 | 0.0119 (11) | 0.0172 (10) | 0.0108 (10) | 0.0016 (8) | 0.0022 (8) | 0.0018 (8) |
| C4 | 0.0178 (11) | 0.0155 (10) | 0.0141 (10) | 0.0043 (8) | 0.0010 (9) | −0.0024 (8) |
| C5 | 0.0164 (11) | 0.0115 (10) | 0.0226 (11) | −0.0030 (8) | 0.0003 (9) | 0.0013 (9) |
| C6 | 0.0112 (10) | 0.0140 (10) | 0.0177 (11) | −0.0012 (8) | 0.0035 (8) | 0.0036 (8) |
| C7 | 0.0106 (10) | 0.0155 (10) | 0.0114 (10) | 0.0011 (8) | 0.0031 (8) | 0.0018 (8) |
| C8 | 0.0100 (10) | 0.0198 (11) | 0.0099 (10) | −0.0020 (8) | 0.0033 (8) | −0.0003 (8) |
| C9 | 0.0183 (12) | 0.0173 (11) | 0.0181 (11) | 0.0054 (9) | 0.0082 (9) | 0.0019 (9) |
| C10 | 0.0197 (12) | 0.0180 (11) | 0.0160 (11) | 0.0011 (9) | 0.0082 (9) | 0.0055 (9) |
| C11 | 0.0101 (11) | 0.0175 (11) | 0.0112 (10) | −0.0003 (8) | 0.0018 (8) | −0.0009 (8) |
| C12 | 0.0103 (10) | 0.0141 (10) | 0.0142 (10) | −0.0003 (8) | 0.0015 (8) | −0.0028 (8) |
| C13 | 0.0146 (11) | 0.0135 (10) | 0.0130 (10) | −0.0045 (8) | 0.0018 (8) | 0.0016 (8) |
| Cu1—N1i | 1.9851 (17) | C5—C6 | 1.383 (3) |
| Cu1—N1 | 1.9851 (17) | C5—H5 | 0.9300 |
| Cu1—Cl1i | 2.2378 (7) | C6—C7 | 1.392 (3) |
| Cu1—Cl1 | 2.2378 (7) | C6—H6 | 0.9300 |
| N1—C1 | 1.321 (3) | C8—C9 | 1.385 (3) |
| N1—C2 | 1.402 (3) | C8—C13 | 1.390 (3) |
| N2—C1 | 1.348 (3) | C9—C10 | 1.382 (3) |
| N2—C7 | 1.396 (3) | C9—H9 | 0.9300 |
| N2—C8 | 1.436 (3) | C10—C11 | 1.398 (3) |
| C1—H1 | 0.9300 | C10—H10 | 0.9300 |
| C2—C3 | 1.394 (3) | C11—C12 | 1.399 (3) |
| C2—C7 | 1.397 (3) | C11—C11ii | 1.487 (4) |
| C3—C4 | 1.379 (3) | C12—C13 | 1.387 (3) |
| C3—H3 | 0.9300 | C12—H12 | 0.9300 |
| C4—C5 | 1.406 (3) | C13—H13 | 0.9300 |
| C4—H4 | 0.9300 | ||
| N1i—Cu1—N1 | 102.49 (10) | C4—C5—H5 | 119.0 |
| N1i—Cu1—Cl1i | 130.22 (5) | C5—C6—C7 | 116.19 (19) |
| N1—Cu1—Cl1i | 97.44 (5) | C5—C6—H6 | 121.9 |
| N1i—Cu1—Cl1 | 97.44 (5) | C7—C6—H6 | 121.9 |
| N1—Cu1—Cl1 | 130.22 (5) | C6—C7—N2 | 131.90 (19) |
| Cl1i—Cu1—Cl1 | 103.48 (4) | C6—C7—C2 | 122.36 (19) |
| C1—N1—C2 | 105.40 (17) | N2—C7—C2 | 105.69 (17) |
| C1—N1—Cu1 | 122.71 (14) | C9—C8—C13 | 120.48 (19) |
| C2—N1—Cu1 | 131.47 (14) | C9—C8—N2 | 119.42 (18) |
| C1—N2—C7 | 106.89 (17) | C13—C8—N2 | 120.10 (18) |
| C1—N2—C8 | 125.39 (17) | C10—C9—C8 | 119.3 (2) |
| C7—N2—C8 | 127.71 (17) | C10—C9—H9 | 120.3 |
| N1—C1—N2 | 113.16 (18) | C8—C9—H9 | 120.3 |
| N1—C1—H1 | 123.4 | C9—C10—C11 | 121.6 (2) |
| N2—C1—H1 | 123.4 | C9—C10—H10 | 119.2 |
| C3—C2—C7 | 120.72 (18) | C11—C10—H10 | 119.2 |
| C3—C2—N1 | 130.42 (19) | C10—C11—C12 | 117.91 (19) |
| C7—C2—N1 | 108.85 (18) | C10—C11—C11ii | 119.99 (13) |
| C4—C3—C2 | 117.44 (19) | C12—C11—C11ii | 122.10 (13) |
| C4—C3—H3 | 121.3 | C13—C12—C11 | 120.95 (19) |
| C2—C3—H3 | 121.3 | C13—C12—H12 | 119.5 |
| C3—C4—C5 | 121.28 (19) | C11—C12—H12 | 119.5 |
| C3—C4—H4 | 119.4 | C12—C13—C8 | 119.64 (19) |
| C5—C4—H4 | 119.4 | C12—C13—H13 | 120.2 |
| C6—C5—C4 | 121.99 (19) | C8—C13—H13 | 120.2 |
| C6—C5—H5 | 119.0 | ||
| N1i—Cu1—N1—C1 | 151.17 (19) | C8—N2—C7—C6 | 3.6 (3) |
| Cl1i—Cu1—N1—C1 | 17.06 (16) | C1—N2—C7—C2 | −0.2 (2) |
| Cl1—Cu1—N1—C1 | −97.67 (16) | C8—N2—C7—C2 | −178.85 (18) |
| N1i—Cu1—N1—C2 | −37.46 (15) | C3—C2—C7—C6 | −1.3 (3) |
| Cl1i—Cu1—N1—C2 | −171.56 (17) | N1—C2—C7—C6 | 178.54 (18) |
| Cl1—Cu1—N1—C2 | 73.71 (19) | C3—C2—C7—N2 | −179.11 (18) |
| C2—N1—C1—N2 | 0.9 (2) | N1—C2—C7—N2 | 0.7 (2) |
| Cu1—N1—C1—N2 | 174.20 (13) | C1—N2—C8—C9 | −134.1 (2) |
| C7—N2—C1—N1 | −0.4 (2) | C7—N2—C8—C9 | 44.3 (3) |
| C8—N2—C1—N1 | 178.25 (18) | C1—N2—C8—C13 | 45.5 (3) |
| C1—N1—C2—C3 | 178.8 (2) | C7—N2—C8—C13 | −136.1 (2) |
| Cu1—N1—C2—C3 | 6.4 (3) | C13—C8—C9—C10 | 1.5 (3) |
| C1—N1—C2—C7 | −1.0 (2) | N2—C8—C9—C10 | −178.90 (19) |
| Cu1—N1—C2—C7 | −173.47 (14) | C8—C9—C10—C11 | −0.7 (3) |
| C7—C2—C3—C4 | 1.4 (3) | C9—C10—C11—C12 | −1.2 (3) |
| N1—C2—C3—C4 | −178.4 (2) | C9—C10—C11—C11ii | 178.2 (2) |
| C2—C3—C4—C5 | −0.4 (3) | C10—C11—C12—C13 | 2.4 (3) |
| C3—C4—C5—C6 | −0.8 (3) | C11ii—C11—C12—C13 | −176.9 (2) |
| C4—C5—C6—C7 | 0.9 (3) | C11—C12—C13—C8 | −1.8 (3) |
| C5—C6—C7—N2 | 177.3 (2) | C9—C8—C13—C12 | −0.2 (3) |
| C5—C6—C7—C2 | 0.2 (3) | N2—C8—C13—C12 | −179.86 (18) |
| C1—N2—C7—C6 | −177.7 (2) |
| Symmetry codes: (i) −x+2, y, −z+3/2; (ii) −x+1, y, −z+5/2. |
Experimental details
| Crystal data | |
| Chemical formula | [CuCl2(C26H18N4)] |
| Mr | 520.88 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 12.599 (4), 15.280 (4), 11.233 (3) |
| β (°) | 91.936 (4) |
| V (Å3) | 2161.3 (10) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 1.28 |
| Crystal size (mm) | 0.04 × 0.03 × 0.02 |
| Data collection | |
| Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
| Tmin, Tmax | 0.955, 0.975 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6675, 1903, 1761 |
| Rint | 0.027 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.066, 1.06 |
| No. of reflections | 1903 |
| No. of parameters | 151 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.50, −0.27 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
We gratefully acknowledge financial support from the Key Laboratory Foundation of the Education Committee of Shaanxi Province (grant No. 09JS089).
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., Xu, Y., Zuo, Y., Li, L., Pan, Q., Hu, T. L. & Bu, X. H. (2009). Cryst. Growth Des. 9, 3904–3909. 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
Su, C. Y., Cai, Y. P., Chen, C. L., Smith, M. D., Kaim, W. & zur Loye, H. C. (2003). J. Am. Chem. Soc. 125, 8595–8613. Web of Science CSD CrossRef PubMed CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Benzoimidazole has been well used in crystal engineering, and a large number of benzoimidazole-containing flexible ligands have been extensively studied (Su et al.,2003; Jin et al.,2006). However, to our knowledge, the research on benzoimidazole ligands bearing rigid spacers is still less developed (Li et al.,2009).
Single-crystal X-ray diffraction analysis reveals that the title compound (I) crystallizes in the monoclinic space group C2/c. The geometry of the Cu(II) ion is surrounded by two benzoiimidazole 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 Cu(II) center is bridged by the linear ligand L to form an infinite one-dimensional architecture.