metal-organic compounds
catena-Poly[[[diaquadiformatocobalt(II)]-μ-1,4-bis(1H-benzimidazol-1-yl)benzene] dihydrate]
aCollege of Science, Chang'an University, Xi'an 710064, Shaanxi, People's Republic of China, and bKey Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, People's Republic of China
*Correspondence e-mail: huangpingyun1@163.com
In the title coordination polymer, {[Co(CHO2)2(C20H14N4)(H2O)2]·2H2O}n, the CoII atom (site symmetry ) is coordinated by two formate O atoms, two water O atoms and two N atoms from two 1,4-bis(1H-benzimidazol-1-yl)benzene ligands (L), resulting in a distorted trans-CoN2O4 octahedral coordination environment. The complete L ligand is generated by crystallographic inversion symmetry and serves to bridge the cobalt ions into a chain propagating in [1]. The dihedral angle between the central benzene ring and the imidazole ring system is 38.48 (12)°. O—H⋯O hydrogen bonds involving both the coordinated and uncoordinated water molecules occur and help to link the chains together.
Related literature
For background to coordination polymers containing imidazole-derived ligands, see: Li et al. (2009, 2011).
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
10.1107/S160053681105505X/hb6531sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681105505X/hb6531Isup2.hkl
A mixture of CH3OH and H2O (1:1, 8 ml), as a buffer layer, was carefully layered over a solution of Co(HCO2)2 in H2O (6 ml). Then a solution of 1,4-di(1H-benzimidazol-1-yl)benzene (L, 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 blocks appeared at the boundary. Yield: ~21% (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 (C).
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).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. | |
Fig. 2. The crystal packing for (I). |
[Co(CHO2)2(C20H14N4)(H2O)2]·2H2O | Z = 1 |
Mr = 531.38 | F(000) = 275 |
Triclinic, P1 | Dx = 1.522 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.497 (4) Å | Cell parameters from 6325 reflections |
b = 9.136 (5) Å | θ = 2.9–53.8° |
c = 9.443 (7) Å | µ = 0.80 mm−1 |
α = 78.289 (19)° | T = 293 K |
β = 77.858 (19)° | Block, purple |
γ = 67.72 (2)° | 0.22 × 0.20 × 0.18 mm |
V = 579.6 (6) Å3 |
Rigaku Mercury CCD area-detector diffractometer | 2012 independent reflections |
Radiation source: fine-focus sealed tube | 1910 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −10→10 |
Tmin = 0.839, Tmax = 0.867 | l = −11→11 |
4958 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.3613P] where P = (Fo2 + 2Fc2)/3 |
2012 reflections | (Δ/σ)max < 0.001 |
162 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
[Co(CHO2)2(C20H14N4)(H2O)2]·2H2O | γ = 67.72 (2)° |
Mr = 531.38 | V = 579.6 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.497 (4) Å | Mo Kα radiation |
b = 9.136 (5) Å | µ = 0.80 mm−1 |
c = 9.443 (7) Å | T = 293 K |
α = 78.289 (19)° | 0.22 × 0.20 × 0.18 mm |
β = 77.858 (19)° |
Rigaku Mercury CCD area-detector diffractometer | 2012 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1910 reflections with I > 2σ(I) |
Tmin = 0.839, Tmax = 0.867 | Rint = 0.026 |
4958 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.10 | Δρmax = 1.08 e Å−3 |
2012 reflections | Δρmin = −0.46 e Å−3 |
162 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 | ||
Co1 | 1.0000 | 0.5000 | 0.5000 | 0.02012 (17) | |
O1W | 1.2375 (2) | 0.3098 (2) | 0.58992 (19) | 0.0295 (4) | |
O2W | 0.1838 (4) | 0.0285 (3) | 0.5850 (3) | 0.0609 (7) | |
O1 | 0.8818 (2) | 0.3208 (2) | 0.5127 (2) | 0.0293 (4) | |
O2 | 0.6238 (3) | 0.2504 (2) | 0.5388 (3) | 0.0463 (5) | |
N1 | 0.8569 (3) | 0.5511 (2) | 0.7146 (2) | 0.0265 (4) | |
N2 | 0.7050 (3) | 0.7105 (2) | 0.8865 (2) | 0.0275 (5) | |
C1 | 0.7791 (4) | 0.6984 (3) | 0.7437 (3) | 0.0292 (5) | |
H1 | 0.7751 | 0.7864 | 0.6731 | 0.035* | |
C2 | 0.7396 (3) | 0.5554 (3) | 0.9577 (3) | 0.0262 (5) | |
C3 | 0.8340 (3) | 0.4566 (3) | 0.8486 (3) | 0.0243 (5) | |
C4 | 0.8857 (4) | 0.2915 (3) | 0.8831 (3) | 0.0325 (6) | |
H4 | 0.9466 | 0.2244 | 0.8117 | 0.039* | |
C5 | 0.8430 (4) | 0.2314 (3) | 1.0271 (3) | 0.0414 (7) | |
H5 | 0.8772 | 0.1216 | 1.0531 | 0.050* | |
C6 | 0.7500 (5) | 0.3310 (4) | 1.1347 (3) | 0.0450 (7) | |
H6 | 0.7243 | 0.2857 | 1.2307 | 0.054* | |
C7 | 0.6952 (4) | 0.4944 (3) | 1.1030 (3) | 0.0374 (6) | |
H7 | 0.6319 | 0.5606 | 1.1748 | 0.045* | |
C8 | 0.6007 (3) | 0.8580 (3) | 0.9448 (3) | 0.0257 (5) | |
C9 | 0.6227 (4) | 0.8724 (3) | 1.0825 (3) | 0.0306 (5) | |
H9 | 0.7047 | 0.7868 | 1.1376 | 0.037* | |
C10 | 0.4786 (4) | 0.9844 (3) | 0.8624 (3) | 0.0319 (6) | |
H10 | 0.4644 | 0.9732 | 0.7701 | 0.038* | |
C11 | 0.7062 (4) | 0.3410 (3) | 0.5497 (3) | 0.0295 (5) | |
H11 | 0.6286 | 0.4339 | 0.5897 | 0.035* | |
H1B | 1.3579 | 0.3142 | 0.5608 | 0.044* | |
H1A | 1.2358 | 0.2205 | 0.5863 | 0.044* | |
H2B | 0.2325 | −0.0572 | 0.5401 | 0.105 (17)* | |
H2A | 0.0565 | 0.0927 | 0.5551 | 0.091 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0216 (3) | 0.0196 (3) | 0.0178 (3) | −0.00541 (17) | 0.00065 (16) | −0.00702 (16) |
O1W | 0.0255 (8) | 0.0273 (9) | 0.0346 (10) | −0.0076 (7) | −0.0052 (7) | −0.0045 (7) |
O2W | 0.0647 (15) | 0.0300 (11) | 0.094 (2) | −0.0096 (10) | −0.0345 (14) | −0.0111 (12) |
O1 | 0.0243 (9) | 0.0274 (9) | 0.0365 (10) | −0.0089 (7) | −0.0001 (7) | −0.0098 (7) |
O2 | 0.0294 (10) | 0.0370 (11) | 0.0755 (16) | −0.0147 (9) | −0.0014 (10) | −0.0148 (10) |
N1 | 0.0332 (11) | 0.0229 (10) | 0.0193 (10) | −0.0060 (8) | 0.0009 (8) | −0.0061 (8) |
N2 | 0.0362 (11) | 0.0217 (10) | 0.0195 (10) | −0.0044 (8) | 0.0003 (8) | −0.0076 (8) |
C1 | 0.0421 (14) | 0.0226 (12) | 0.0182 (11) | −0.0081 (10) | 0.0019 (10) | −0.0055 (9) |
C2 | 0.0279 (12) | 0.0229 (12) | 0.0239 (12) | −0.0047 (10) | −0.0010 (9) | −0.0060 (9) |
C3 | 0.0241 (11) | 0.0249 (11) | 0.0214 (12) | −0.0059 (9) | −0.0015 (9) | −0.0052 (9) |
C4 | 0.0347 (13) | 0.0232 (12) | 0.0349 (14) | −0.0053 (10) | −0.0002 (11) | −0.0084 (10) |
C5 | 0.0518 (17) | 0.0252 (13) | 0.0386 (16) | −0.0097 (12) | −0.0016 (13) | 0.0015 (11) |
C6 | 0.0608 (19) | 0.0378 (15) | 0.0274 (15) | −0.0158 (14) | 0.0018 (13) | 0.0036 (12) |
C7 | 0.0493 (16) | 0.0341 (14) | 0.0223 (13) | −0.0104 (12) | 0.0026 (11) | −0.0061 (11) |
C8 | 0.0317 (12) | 0.0215 (11) | 0.0212 (12) | −0.0061 (9) | 0.0013 (9) | −0.0089 (9) |
C9 | 0.0374 (14) | 0.0256 (12) | 0.0241 (12) | −0.0037 (10) | −0.0073 (10) | −0.0047 (10) |
C10 | 0.0434 (14) | 0.0296 (13) | 0.0196 (12) | −0.0060 (11) | −0.0058 (10) | −0.0089 (10) |
C11 | 0.0267 (13) | 0.0265 (12) | 0.0337 (14) | −0.0067 (10) | −0.0042 (10) | −0.0058 (10) |
Co1—O1i | 2.1110 (19) | C2—C7 | 1.394 (4) |
Co1—O1 | 2.1110 (19) | C2—C3 | 1.402 (3) |
Co1—N1 | 2.136 (2) | C3—C4 | 1.393 (4) |
Co1—N1i | 2.136 (2) | C4—C5 | 1.378 (4) |
Co1—O1Wi | 2.1451 (19) | C4—H4 | 0.9300 |
Co1—O1W | 2.1451 (19) | C5—C6 | 1.394 (4) |
O1W—H1B | 0.8998 | C5—H5 | 0.9300 |
O1W—H1A | 0.8288 | C6—C7 | 1.375 (4) |
O2W—H2B | 0.8823 | C6—H6 | 0.9300 |
O2W—H2A | 0.9779 | C7—H7 | 0.9300 |
O1—C11 | 1.240 (3) | C8—C10 | 1.382 (4) |
O2—C11 | 1.236 (3) | C8—C9 | 1.383 (3) |
N1—C1 | 1.309 (3) | C9—C10ii | 1.384 (4) |
N1—C3 | 1.398 (3) | C9—H9 | 0.9300 |
N2—C1 | 1.355 (3) | C10—C9ii | 1.384 (3) |
N2—C2 | 1.391 (3) | C10—H10 | 0.9300 |
N2—C8 | 1.432 (3) | C11—H11 | 0.9300 |
C1—H1 | 0.9300 | ||
O1i—Co1—O1 | 180.000 (1) | N2—C2—C3 | 105.4 (2) |
O1i—Co1—N1 | 88.37 (8) | C7—C2—C3 | 122.2 (2) |
O1—Co1—N1 | 91.63 (8) | C4—C3—N1 | 130.5 (2) |
O1i—Co1—N1i | 91.63 (8) | C4—C3—C2 | 120.3 (2) |
O1—Co1—N1i | 88.37 (8) | N1—C3—C2 | 109.2 (2) |
N1—Co1—N1i | 180.0 | C5—C4—C3 | 117.4 (2) |
O1i—Co1—O1Wi | 84.83 (8) | C5—C4—H4 | 121.3 |
O1—Co1—O1Wi | 95.17 (8) | C3—C4—H4 | 121.3 |
N1—Co1—O1Wi | 89.43 (8) | C4—C5—C6 | 121.8 (3) |
N1i—Co1—O1Wi | 90.57 (8) | C4—C5—H5 | 119.1 |
O1i—Co1—O1W | 95.17 (8) | C6—C5—H5 | 119.1 |
O1—Co1—O1W | 84.83 (8) | C7—C6—C5 | 121.9 (3) |
N1—Co1—O1W | 90.57 (8) | C7—C6—H6 | 119.1 |
N1i—Co1—O1W | 89.43 (8) | C5—C6—H6 | 119.1 |
O1Wi—Co1—O1W | 180.00 (9) | C6—C7—C2 | 116.5 (3) |
Co1—O1W—H1B | 117.7 | C6—C7—H7 | 121.7 |
Co1—O1W—H1A | 112.5 | C2—C7—H7 | 121.7 |
H1B—O1W—H1A | 111.6 | C10—C8—C9 | 120.7 (2) |
H2B—O2W—H2A | 107.9 | C10—C8—N2 | 119.4 (2) |
C11—O1—Co1 | 123.68 (16) | C9—C8—N2 | 119.8 (2) |
C1—N1—C3 | 105.12 (19) | C8—C9—C10ii | 119.3 (2) |
C1—N1—Co1 | 120.75 (16) | C8—C9—H9 | 120.3 |
C3—N1—Co1 | 133.95 (16) | C10ii—C9—H9 | 120.3 |
C1—N2—C2 | 106.57 (19) | C8—C10—C9ii | 119.9 (2) |
C1—N2—C8 | 124.6 (2) | C8—C10—H10 | 120.0 |
C2—N2—C8 | 128.7 (2) | C9ii—C10—H10 | 120.0 |
N1—C1—N2 | 113.7 (2) | O2—C11—O1 | 126.7 (2) |
N1—C1—H1 | 123.2 | O2—C11—H11 | 116.7 |
N2—C1—H1 | 123.2 | O1—C11—H11 | 116.7 |
N2—C2—C7 | 132.4 (2) | ||
O1i—Co1—O1—C11 | 166 (100) | Co1—N1—C3—C4 | −6.5 (4) |
N1—Co1—O1—C11 | 50.3 (2) | C1—N1—C3—C2 | −0.2 (3) |
N1i—Co1—O1—C11 | −129.7 (2) | Co1—N1—C3—C2 | 174.71 (17) |
O1Wi—Co1—O1—C11 | −39.3 (2) | N2—C2—C3—C4 | −178.4 (2) |
O1W—Co1—O1—C11 | 140.7 (2) | C7—C2—C3—C4 | 0.5 (4) |
O1i—Co1—N1—C1 | 39.7 (2) | N2—C2—C3—N1 | 0.5 (3) |
O1—Co1—N1—C1 | −140.3 (2) | C7—C2—C3—N1 | 179.4 (2) |
N1i—Co1—N1—C1 | 178 (100) | N1—C3—C4—C5 | −179.6 (3) |
O1Wi—Co1—N1—C1 | −45.2 (2) | C2—C3—C4—C5 | −1.0 (4) |
O1W—Co1—N1—C1 | 134.8 (2) | C3—C4—C5—C6 | 0.6 (4) |
O1i—Co1—N1—C3 | −134.6 (2) | C4—C5—C6—C7 | 0.2 (5) |
O1—Co1—N1—C3 | 45.4 (2) | C5—C6—C7—C2 | −0.8 (5) |
N1i—Co1—N1—C3 | 3 (100) | N2—C2—C7—C6 | 178.9 (3) |
O1Wi—Co1—N1—C3 | 140.6 (2) | C3—C2—C7—C6 | 0.4 (4) |
O1W—Co1—N1—C3 | −39.4 (2) | C1—N2—C8—C10 | 36.0 (4) |
C3—N1—C1—N2 | −0.3 (3) | C2—N2—C8—C10 | −139.4 (3) |
Co1—N1—C1—N2 | −176.00 (16) | C1—N2—C8—C9 | −144.2 (3) |
C2—N2—C1—N1 | 0.6 (3) | C2—N2—C8—C9 | 40.4 (4) |
C8—N2—C1—N1 | −175.6 (2) | C10—C8—C9—C10ii | −0.3 (4) |
C1—N2—C2—C7 | −179.3 (3) | N2—C8—C9—C10ii | 179.9 (2) |
C8—N2—C2—C7 | −3.3 (5) | C9—C8—C10—C9ii | 0.3 (4) |
C1—N2—C2—C3 | −0.7 (3) | N2—C8—C10—C9ii | −179.9 (2) |
C8—N2—C2—C3 | 175.3 (2) | Co1—O1—C11—O2 | 168.5 (2) |
C1—N1—C3—C4 | 178.6 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2Wiii | 0.83 | 1.94 | 2.759 (4) | 170 |
O1W—H1B···O2iii | 0.90 | 1.83 | 2.691 (4) | 159 |
O2W—H2A···O1iv | 0.98 | 2.01 | 2.837 (4) | 141 |
O2W—H2B···O2v | 0.88 | 1.89 | 2.766 (4) | 170 |
Symmetry codes: (iii) x+1, y, z; (iv) x−1, y, z; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(CHO2)2(C20H14N4)(H2O)2]·2H2O |
Mr | 531.38 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.497 (4), 9.136 (5), 9.443 (7) |
α, β, γ (°) | 78.289 (19), 77.858 (19), 67.72 (2) |
V (Å3) | 579.6 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.839, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4958, 2012, 1910 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.10 |
No. of reflections | 2012 |
No. of parameters | 162 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.08, −0.46 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2Wi | 0.83 | 1.94 | 2.759 (4) | 170 |
O1W—H1B···O2i | 0.90 | 1.83 | 2.691 (4) | 159 |
O2W—H2A···O1ii | 0.98 | 2.01 | 2.837 (4) | 141 |
O2W—H2B···O2iii | 0.88 | 1.89 | 2.766 (4) | 170 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, −y, −z+1. |
References
Li, Z. X., Chu, X., Cui, G. H., Liu, Y., Li, L. & Xue, G. L. (2011). CrystEngComm, 13, 1984–1989. Web of Science CSD CrossRef CAS 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
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Imidazole has been extensively used in crystal engineering, and a large number of imidazole-containing flexible ligands have been extensively studied. However, to our knowledge, the research on imidazole ligands bearing rigid spacers is still less developed (Li et al., 2009; Li et al., 2011). For the title compound, the geometry of the CoII ion is bound by two benzoimidazole rings of individual L ligands, two water molecules and two formate ions forming a slightly distorted octahedral coordination environment(Fig. 1). Notably, as shown in Fig. 2, the six-coordinate CoII center is bridged by the ligand L to form an infinite one-dimensional architecture.