catena-Poly[[[diaqua­diformato­cobalt(II)]-μ-1,4-bis­(1H-benzimidazol-1-yl)benzene] dihydrate]

Abstract

In the title coordination polymer, {[Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]·2H₂O}_n, the Co^II 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

• [Co(CHO₂)₂(C₂₀H₁₄N₄)(H₂O)₂]·2H₂O

• M _r = 531.38

• Triclinic,

• a = 7.497 (4) Å

• b = 9.136 (5) Å

• c = 9.443 (7) Å

• α = 78.289 (19)°

• β = 77.858 (19)°

• γ = 67.72 (2)°

• V = 579.6 (6) ų

• Z = 1

• Mo Kα radiation

• μ = 0.80 mm⁻¹

• T = 293 K

• 0.22 × 0.20 × 0.18 mm

Data collection

• Rigaku Mercury CCD area-detector diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.839, T _max = 0.867

• 4958 measured reflections

• 2012 independent reflections

• 1910 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.106

• S = 1.10

• 2012 reflections

• 162 parameters

• H-atom parameters constrained

• Δρ_max = 1.08 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Co1—O1	2.1110 (19)
Co1—N1	2.136 (2)
Co1—O1W	2.1451 (19)

Table 2. Hydrogen-bond geometry (Å, °).

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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 Co^II 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 Co^II center is bridged by the ligand L to form an infinite one-dimensional architecture.

Experimental

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).

Refinement

C-bound H atoms were positioned geometrically and refined in the riding-model approximation, with C—H = 0.93Å and U_iso(H) = 1.2U_eq (C).

Figures

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).

Crystal data

[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

Data collection

Rigaku Mercury CCD area-detector diffractometer	2012 independent reflections
Radiation source: fine-focus sealed tube	1910 reflections with I > 2σ(I)
graphite	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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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.

Hydrogen-bond geometry (Å, °)

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.