Diaqua-bis(2,2'-biimidazole)cobalt(II) 4,4'-dicarboxy-biphenyl-3,3'-di-car-boxylate.

In the title compound, [Co(C(6)H(6)N(4))(2)(H(2)O)(2)](C(16)H(8)O(8)), the Co(II) cation and the organic anion occupy different crystallographic inversion centres and, as a consequence, the asymmetric unit comprises two half-mol-ecules. The benzene groups are coplanar. The four coordinating N atoms of the two bidentate biimidazole ligands define the equatorial plane of a slightly distorted octa-hedral CoO(2)N(4) geometry, and the water O atoms lie in the axial coordination sites. Translational (a,) and inversion-related symmetry operations link the Co complex mol-ecules and the negatively charged carboxyl-ate anions via inter-molecular N-H⋯O and O-H⋯O hydrogen bonds into sheets parallel to (01). The coordinated water mol-ecules connect the sheets through O-H⋯O hydrogen bonds, forming a three-dimensional framework. In addition, two intra-molecular O-H⋯O hydrogen bonds are observed between the carboxyl and carboxyl-ate groups.

Related literature

For a review on organic–inorganic hybrid materials, see: Hagrman et al. (1999 ▶). For a tetra­nuclear cobalt complex with a 1,2,4-benzene­tricarboxyl­ate linker, see: Jia et al. (2007 ▶). For a highly porous metal-organic framework with a benzene­dicarboxyl­ate linker, see: Li et al. (1999 ▶). For coordination polymers of Ag(I), Cd(II) and Zn(II) with the flexible 2-(1H-imidazole-1-yl)acetic acid linker, see: Wang et al. (2007 ▶). For the structure of 1,1′-biphenyl-2,3,3′,4′-tetra­carboxylic acid monohydrate and related structures cited therein, see: Jiang et al. (2008 ▶).

Experimental

Crystal data

[Co(C6H6N4)2(H2O)2](C16H8O8)

M = 691.48

Triclinic,

a = 8.2272 (16) Å

b = 9.772 (2) Å

c = 10.484 (2) Å

α = 63.81 (3)°

β = 67.93 (3)°

γ = 84.03 (3)°

V = 699.0 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.69 mm−1

T = 293 K

0.42 × 0.26 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.760, T max = 0.874

4982 measured reflections

2603 independent reflections

2527 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.087

S = 1.01

2603 reflections

227 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007764/si2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007764/si2153Isup2.hkl

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

[Co(C6H6N4)2(H2O)2](C16H8O8)	Z = 1
Mr = 691.48	F(000) = 355
Triclinic, P1	Dx = 1.643 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2272 (16) Å	Cell parameters from 2603 reflections
b = 9.772 (2) Å	θ = 3.1–25.8°
c = 10.484 (2) Å	µ = 0.69 mm−1
α = 63.81 (3)°	T = 293 K
β = 67.93 (3)°	Block, colorless
γ = 84.03 (3)°	0.42 × 0.26 × 0.20 mm
V = 699.0 (2) Å3

Bruker APEXII CCD area-detector diffractometer	2603 independent reflections
Radiation source: fine-focus sealed tube	2527 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 25.8°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→9
Tmin = 0.760, Tmax = 0.874	k = −11→11
4982 measured reflections	l = −12→12

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.045P)2 + 0.376P] where P = (Fo2 + 2Fc2)/3
2603 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.31 e Å−3
5 restraints	Δρmin = −0.21 e Å−3

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	0.5000	0.5000	0.5000	0.03059 (13)
C1	0.7400 (3)	0.5910 (2)	0.6513 (3)	0.0388 (5)
H1	0.7036	0.6865	0.6446	0.047*
C2	0.8671 (3)	0.5187 (2)	0.7049 (3)	0.0403 (5)
H2	0.9323	0.5542	0.7415	0.048*
C3	0.7617 (2)	0.3779 (2)	0.6368 (2)	0.0303 (4)
C4	0.7231 (2)	0.2591 (2)	0.6037 (2)	0.0305 (4)
C5	0.5986 (3)	0.1500 (2)	0.5229 (3)	0.0396 (5)
H5	0.5266	0.1311	0.4812	0.047*
C6	0.7143 (3)	0.0532 (2)	0.5751 (3)	0.0428 (5)
H6	0.7355	−0.0425	0.5762	0.051*
C7	0.2215 (3)	0.6649 (2)	0.8670 (2)	0.0355 (4)
C8	0.2957 (2)	0.7806 (2)	0.8950 (2)	0.0300 (4)
C9	0.4327 (3)	0.7276 (2)	0.9485 (2)	0.0372 (5)
H9	0.4710	0.6319	0.9577	0.045*
C10	0.5135 (3)	0.8106 (2)	0.9882 (3)	0.0383 (5)
H10	0.6051	0.7708	1.0222	0.046*
C11	0.4595 (2)	0.9535 (2)	0.9779 (2)	0.0289 (4)
C12	0.3260 (2)	1.0084 (2)	0.9211 (2)	0.0301 (4)
H12	0.2894	1.1046	0.9116	0.036*
C13	0.2436 (2)	0.9278 (2)	0.8777 (2)	0.0279 (4)
C14	0.1084 (2)	1.0170 (2)	0.8107 (2)	0.0330 (4)
N1	0.6735 (2)	0.50249 (18)	0.60857 (19)	0.0340 (4)
N2	0.8799 (2)	0.3839 (2)	0.6943 (2)	0.0365 (4)
H2A	0.951 (3)	0.307 (2)	0.726 (2)	0.044*
N3	0.6043 (2)	0.27901 (17)	0.54115 (19)	0.0335 (4)
N4	0.7934 (2)	0.12422 (19)	0.6258 (2)	0.0371 (4)
H4A	0.869 (2)	0.078 (2)	0.676 (2)	0.045*
O1	0.0983 (2)	1.15279 (16)	0.7860 (2)	0.0492 (4)
O2	0.0097 (2)	0.95144 (19)	0.7838 (2)	0.0552 (5)
O3	0.0823 (2)	0.68970 (19)	0.8329 (2)	0.0546 (4)
H3	0.0513	0.7749	0.8241	0.082*
O4	0.2931 (2)	0.54625 (18)	0.8800 (2)	0.0500 (4)
O5	0.7116 (2)	0.58986 (18)	0.29083 (18)	0.0469 (4)
H1W	0.763 (3)	0.6721 (18)	0.259 (3)	0.056*
H2W	0.730 (3)	0.557 (2)	0.228 (2)	0.056*

	U11	U22	U33	U12	U13	U23
Co1	0.0353 (2)	0.0244 (2)	0.0457 (2)	0.00797 (14)	−0.02832 (17)	−0.01710 (17)
C1	0.0454 (11)	0.0331 (11)	0.0579 (13)	0.0098 (9)	−0.0324 (10)	−0.0271 (10)
C2	0.0445 (11)	0.0408 (12)	0.0564 (13)	0.0074 (9)	−0.0326 (10)	−0.0281 (10)
C3	0.0306 (9)	0.0293 (10)	0.0390 (10)	0.0070 (7)	−0.0211 (8)	−0.0158 (8)
C4	0.0343 (10)	0.0251 (9)	0.0380 (10)	0.0072 (7)	−0.0206 (8)	−0.0140 (8)
C5	0.0514 (12)	0.0301 (10)	0.0528 (12)	0.0054 (9)	−0.0327 (10)	−0.0206 (9)
C6	0.0559 (13)	0.0272 (10)	0.0599 (13)	0.0106 (9)	−0.0321 (11)	−0.0240 (10)
C7	0.0417 (11)	0.0327 (11)	0.0414 (11)	0.0038 (8)	−0.0214 (9)	−0.0194 (9)
C8	0.0341 (9)	0.0292 (10)	0.0327 (9)	0.0033 (7)	−0.0170 (8)	−0.0150 (8)
C9	0.0479 (11)	0.0277 (10)	0.0519 (12)	0.0141 (8)	−0.0317 (10)	−0.0222 (9)
C10	0.0468 (11)	0.0320 (10)	0.0561 (12)	0.0159 (9)	−0.0388 (10)	−0.0227 (9)
C11	0.0341 (9)	0.0250 (9)	0.0348 (9)	0.0058 (7)	−0.0202 (8)	−0.0139 (8)
C12	0.0337 (9)	0.0254 (9)	0.0389 (10)	0.0071 (7)	−0.0210 (8)	−0.0153 (8)
C13	0.0286 (9)	0.0276 (9)	0.0326 (9)	0.0043 (7)	−0.0176 (7)	−0.0126 (8)
C14	0.0321 (10)	0.0332 (11)	0.0443 (11)	0.0072 (8)	−0.0229 (8)	−0.0197 (9)
N1	0.0382 (9)	0.0291 (9)	0.0491 (10)	0.0093 (7)	−0.0287 (8)	−0.0205 (8)
N2	0.0371 (9)	0.0364 (9)	0.0505 (10)	0.0116 (7)	−0.0303 (8)	−0.0215 (8)
N3	0.0399 (9)	0.0260 (8)	0.0451 (9)	0.0066 (7)	−0.0273 (8)	−0.0159 (7)
N4	0.0416 (9)	0.0299 (9)	0.0503 (10)	0.0115 (7)	−0.0286 (8)	−0.0187 (8)
O1	0.0495 (9)	0.0308 (8)	0.0865 (12)	0.0132 (7)	−0.0501 (9)	−0.0234 (8)
O2	0.0614 (10)	0.0485 (9)	0.0989 (13)	0.0239 (8)	−0.0639 (10)	−0.0445 (9)
O3	0.0583 (10)	0.0429 (9)	0.0953 (13)	0.0131 (7)	−0.0519 (10)	−0.0402 (10)
O4	0.0654 (10)	0.0392 (9)	0.0746 (11)	0.0165 (7)	−0.0444 (9)	−0.0368 (8)
O5	0.0579 (10)	0.0382 (9)	0.0516 (9)	−0.0085 (7)	−0.0184 (8)	−0.0244 (7)

Co1—O5i	2.0882 (19)	C7—O4	1.220 (3)
Co1—O5	2.0882 (19)	C7—O3	1.293 (2)
Co1—N1	2.1412 (16)	C7—C8	1.519 (3)
Co1—N1i	2.1412 (16)	C8—C9	1.397 (3)
Co1—N3i	2.1579 (16)	C8—C13	1.410 (3)
Co1—N3	2.1579 (16)	C9—C10	1.375 (3)
C1—C2	1.359 (3)	C9—H9	0.9300
C1—N1	1.369 (2)	C10—C11	1.390 (3)
C1—H1	0.9300	C10—H10	0.9300
C2—N2	1.360 (3)	C11—C12	1.391 (3)
C2—H2	0.9300	C11—C11ii	1.490 (3)
C3—N1	1.325 (2)	C12—C13	1.395 (3)
C3—N2	1.340 (2)	C12—H12	0.9300
C3—C4	1.444 (3)	C13—C14	1.528 (3)
C4—N3	1.324 (2)	C14—O1	1.235 (2)
C4—N4	1.341 (2)	C14—O2	1.261 (2)
C5—C6	1.360 (3)	N2—H2A	0.921 (10)
C5—N3	1.364 (2)	N4—H4A	0.918 (10)
C5—H5	0.9300	O3—H3	0.8200
C6—N4	1.366 (3)	O5—H1W	0.82 (2)
C6—H6	0.9300	O5—H2W	0.81 (2)
O5i—Co1—O5	180	C13—C8—C7	129.44 (17)
O5i—Co1—N1	91.68 (7)	C10—C9—C8	122.91 (18)
O5—Co1—N1	88.32 (7)	C10—C9—H9	118.5
O5i—Co1—N1i	88.32 (7)	C8—C9—H9	118.5
N1—Co1—N1i	180	C9—C10—C11	120.56 (18)
O5i—Co1—N3i	87.82 (7)	C9—C10—H10	119.7
O5—Co1—N3i	92.18 (7)	C11—C10—H10	119.7
N1—Co1—N3i	100.77 (6)	C10—C11—C12	116.73 (17)
N1i—Co1—N3i	79.23 (6)	C10—C11—C11ii	122.6 (2)
O5i—Co1—N3	92.18 (7)	C12—C11—C11ii	120.7 (2)
O5—Co1—N3	87.82 (7)	C11—C12—C13	123.93 (17)
N1—Co1—N3	79.23 (6)	C11—C12—H12	118.0
N3i—Co1—N3	180	C13—C12—H12	118.0
C2—C1—N1	109.90 (17)	C12—C13—C8	118.32 (16)
C2—C1—H1	125.0	C12—C13—C14	113.67 (16)
N1—C1—H1	125.0	C8—C13—C14	127.98 (16)
N2—C2—C1	106.11 (17)	O1—C14—O2	121.81 (18)
N2—C2—H2	126.9	O1—C14—C13	118.10 (17)
C1—C2—H2	126.9	O2—C14—C13	120.09 (17)
N1—C3—N2	111.51 (17)	C3—N1—C1	105.05 (16)
N1—C3—C4	119.29 (16)	C3—N1—Co1	111.21 (12)
N2—C3—C4	129.20 (17)	C1—N1—Co1	143.48 (13)
N3—C4—N4	111.61 (17)	C3—N2—C2	107.42 (17)
N3—C4—C3	119.34 (16)	C3—N2—H2A	125.3 (15)
N4—C4—C3	129.05 (17)	C2—N2—H2A	127.2 (15)
C6—C5—N3	109.48 (18)	C4—N3—C5	105.57 (16)
C6—C5—H5	125.3	C4—N3—Co1	110.75 (12)
N3—C5—H5	125.3	C5—N3—Co1	143.64 (14)
C5—C6—N4	106.57 (17)	C4—N4—C6	106.77 (17)
C5—C6—H6	126.7	C4—N4—H4A	129.4 (15)
N4—C6—H6	126.7	C6—N4—H4A	123.4 (15)
O4—C7—O3	120.13 (18)	C7—O3—H3	109.5
O4—C7—C8	119.10 (18)	Co1—O5—H1W	121.0 (16)
O3—C7—C8	120.75 (17)	Co1—O5—H2W	121.0 (16)
C9—C8—C13	117.47 (17)	H1W—O5—H2W	116.1 (17)
C9—C8—C7	113.08 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1iii	0.92 (2)	1.87 (2)	2.791 (3)	179 (2)
N4—H4A···O2iii	0.92 (2)	1.90 (2)	2.808 (3)	170 (2)
O5—H1W···O1iv	0.82 (2)	1.93 (2)	2.739 (3)	169 (2)
O5—H2W···O4i	0.81 (2)	1.88 (2)	2.673 (3)	163 (2)
O3—H3···O2	0.82	1.62	2.432 (3)	172

Co1—O5	2.0882 (19)
Co1—N1	2.1412 (16)
Co1—N3	2.1579 (16)

O5—Co1—N1	88.32 (7)
N1—Co1—N3i	100.77 (6)
O5—Co1—N3	87.82 (7)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ii	0.92 (2)	1.87 (2)	2.791 (3)	178.8 (18)
N4—H4A⋯O2ii	0.920 (18)	1.897 (19)	2.808 (3)	170.3 (19)
O5—H1W⋯O1iii	0.82 (2)	1.93 (2)	2.739 (3)	169 (2)
O5—H2W⋯O4i	0.81 (2)	1.88 (2)	2.673 (3)	163 (2)
O3—H3⋯O2	0.82	1.62	2.432 (3)	172

Symmetry codes: (i) ; (ii) ; (iii) .