Poly[[tetraaqua-bis(μ(3)-1H-benzimidazole-5,6-dicarboxyl-ato)dicobalt(II)] trihydrate].

The title complex, {[Co(2)(C(9)H(4)N(2)O(4))(2)(H(2)O)(4)]·3H(2)O}(n), was synthesized hydro-thermally. The unique Co(II) ion is coordin-ated in a distorted octa-hedral coordination environment by two water mol-ecules and three symmetry-related 1H-benzimid-azole-5,6-dicarboxyl-ate (Hbidc) ligands. The Hbidc ligands coordinate via a bis-chelating and mono-chelating carboxyl-ate group and by an imidazole group N atom, bridging the Co(II) ions and forming an extended two-dimensional structure in the ab plane. In the crystal structure, inter-molecular N-H⋯O and O-H⋯O hydrogen bonds connect complex and solvent water mol-ecules, forming a three-dimensional supermolecular network. One of the solvent water mol-ecules lies on a twofold rotation axis.

Related literature

For background information on carboxyl­ate ligands in coordination chemistry, see: Laduca (2009 ▶); Grodzicki et al. (2005 ▶). For the isostructural Ni(II) complex, see: Yao et al. (2008 ▶). For related structures, see: Wei et al. (2008 ▶); Xu & Yu (2009 ▶).

Experimental

Crystal data

[Co2(C9H4N2O4)2(H2O)4]·3H2O

M = 652.26

Monoclinic,

a = 22.4085 (18) Å

b = 9.1564 (7) Å

c = 13.0907 (10) Å

β = 121.006 (4)°

V = 2302.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.53 mm−1

T = 296 K

0.43 × 0.25 × 0.07 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.63, T max = 0.90

9315 measured reflections

2656 independent reflections

2402 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.087

S = 1.03

2656 reflections

174 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.81 e Å−3

Δρmin = −0.63 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536809049083/lh2948sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049083/lh2948Isup2.hkl

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

[Co2(C9H4N2O4)2(H2O)4]·3H2O	F(000) = 1328
Mr = 652.26	Dx = 1.882 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5695 reflections
a = 22.4085 (18) Å	θ = 2.1–27.6°
b = 9.1564 (7) Å	µ = 1.53 mm−1
c = 13.0907 (10) Å	T = 296 K
β = 121.006 (4)°	Block, red
V = 2302.2 (3) Å3	0.43 × 0.25 × 0.07 mm
Z = 4

Bruker APEXII diffractometer	2656 independent reflections
Radiation source: fine-focus sealed tube	2402 reflections with I > 2σ(I)
graphite	Rint = 0.018
ω scans	θmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→27
Tmin = 0.63, Tmax = 0.90	k = −11→11
9315 measured reflections	l = −16→17

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0533P)2 + 3.4124P] where P = (Fo2 + 2Fc2)/3
2656 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.81 e Å−3
6 restraints	Δρmin = −0.63 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	0.199951 (12)	0.14498 (3)	0.12124 (2)	0.01825 (10)
O1	−0.19686 (7)	0.44398 (15)	−0.25564 (13)	0.0239 (3)
O2	−0.20916 (7)	0.22564 (15)	−0.33254 (12)	0.0216 (3)
O3	−0.10064 (8)	−0.07292 (17)	−0.23544 (16)	0.0335 (4)
O3W	0.20211 (8)	0.25089 (16)	0.26967 (13)	0.0277 (3)
H3WA	0.1974	0.3419	0.2690	0.042*
H3WB	0.1706	0.2071	0.2742	0.042*
O4	−0.14121 (7)	0.02445 (15)	−0.12688 (12)	0.0224 (3)
O4W	0.20838 (8)	0.03724 (17)	−0.01154 (13)	0.0302 (3)
H4WA	0.2019	0.0885	−0.0696	0.045*
H4WB	0.1863	−0.0415	−0.0365	0.045*
N1	0.07455 (8)	0.50513 (18)	−0.06630 (15)	0.0222 (3)
H1A	0.0716	0.5976	−0.0794	0.027*
N2	0.12237 (8)	0.28672 (18)	0.00087 (15)	0.0225 (3)
C1	−0.09320 (9)	0.3057 (2)	−0.19386 (16)	0.0181 (4)
C2	−0.06298 (9)	0.1649 (2)	−0.15733 (16)	0.0175 (4)
C3	0.00868 (10)	0.1468 (2)	−0.09321 (18)	0.0207 (4)
H3A	0.0285	0.0544	−0.0700	0.025*
C4	0.05016 (9)	0.2710 (2)	−0.06466 (17)	0.0195 (4)
C5	0.01982 (10)	0.4091 (2)	−0.10514 (17)	0.0189 (4)
C6	−0.05185 (9)	0.4293 (2)	−0.16866 (17)	0.0195 (4)
H6A	−0.0714	0.5216	−0.1933	0.023*
C7	−0.17032 (9)	0.3262 (2)	−0.26428 (16)	0.0177 (3)
C8	−0.10569 (9)	0.0287 (2)	−0.17727 (16)	0.0194 (4)
C9	0.13324 (10)	0.4278 (2)	−0.00439 (18)	0.0240 (4)
H9A	0.1774	0.4691	0.0315	0.029*
O1W	0.0000	0.24202 (17)	0.2500	0.1066 (18)
H1W	−0.0300	0.1917	0.2543	0.160*
O2W	0.1643	0.75912 (17)	0.0016	0.0530 (5)
H2WA	0.1492	0.8072	0.0382	0.080*
H2WB	0.2053	0.7403	0.0558	0.080*

	U11	U22	U33	U12	U13	U23
Co1	0.01193 (15)	0.01637 (16)	0.02247 (16)	−0.00183 (8)	0.00601 (11)	0.00077 (9)
O1	0.0152 (6)	0.0189 (7)	0.0326 (7)	0.0021 (5)	0.0086 (6)	−0.0031 (6)
O2	0.0145 (6)	0.0201 (7)	0.0250 (7)	−0.0001 (5)	0.0064 (5)	−0.0035 (5)
O3	0.0321 (8)	0.0251 (8)	0.0530 (10)	−0.0099 (6)	0.0289 (8)	−0.0140 (7)
O3W	0.0269 (8)	0.0208 (7)	0.0381 (8)	−0.0053 (6)	0.0186 (7)	−0.0047 (6)
O4	0.0197 (6)	0.0207 (7)	0.0290 (7)	−0.0043 (5)	0.0139 (6)	−0.0005 (5)
O4W	0.0398 (9)	0.0241 (7)	0.0287 (7)	−0.0068 (6)	0.0191 (7)	−0.0012 (6)
N1	0.0166 (8)	0.0159 (8)	0.0313 (9)	−0.0036 (6)	0.0104 (7)	−0.0003 (6)
N2	0.0118 (7)	0.0221 (8)	0.0271 (8)	−0.0023 (6)	0.0054 (6)	0.0023 (7)
C1	0.0134 (8)	0.0187 (9)	0.0201 (8)	0.0002 (7)	0.0072 (7)	0.0008 (7)
C2	0.0138 (8)	0.0164 (9)	0.0202 (8)	−0.0008 (6)	0.0072 (7)	0.0011 (7)
C3	0.0148 (9)	0.0162 (9)	0.0263 (9)	0.0010 (6)	0.0072 (7)	0.0029 (7)
C4	0.0123 (8)	0.0212 (9)	0.0219 (9)	−0.0009 (7)	0.0067 (7)	0.0021 (7)
C5	0.0171 (9)	0.0161 (9)	0.0225 (9)	−0.0024 (7)	0.0095 (7)	0.0000 (7)
C6	0.0163 (8)	0.0159 (9)	0.0244 (9)	0.0015 (7)	0.0091 (7)	0.0023 (7)
C7	0.0135 (8)	0.0176 (8)	0.0208 (9)	0.0006 (7)	0.0079 (7)	0.0026 (7)
C8	0.0119 (8)	0.0173 (9)	0.0237 (9)	−0.0013 (7)	0.0054 (7)	0.0017 (7)
C9	0.0150 (9)	0.0241 (10)	0.0289 (10)	−0.0037 (7)	0.0084 (8)	−0.0001 (8)
O1W	0.103 (3)	0.0399 (18)	0.247 (6)	0.000	0.140 (4)	0.000
O2W	0.0709 (14)	0.0310 (10)	0.0514 (11)	−0.0099 (9)	0.0275 (10)	−0.0037 (8)

Co1—O4i	2.0603 (14)	N1—C5	1.376 (2)
Co1—N2	2.0898 (16)	N1—H1A	0.8598
Co1—O4W	2.0901 (15)	N2—C9	1.322 (3)
Co1—O3W	2.1497 (15)	N2—C4	1.395 (2)
Co1—O2ii	2.1560 (13)	C1—C6	1.390 (3)
Co1—O1ii	2.1837 (14)	C1—C2	1.420 (3)
Co1—C7ii	2.5057 (18)	C1—C7	1.493 (2)
O1—C7	1.265 (2)	C2—C3	1.386 (3)
O1—Co1iii	2.1837 (14)	C2—C8	1.511 (2)
O2—C7	1.266 (2)	C3—C4	1.393 (3)
O2—Co1iii	2.1560 (13)	C3—H3A	0.9300
O3—C8	1.244 (2)	C4—C5	1.404 (3)
O3W—H3WA	0.8399	C5—C6	1.389 (3)
O3W—H3WB	0.8399	C6—H6A	0.9300
O4—C8	1.269 (2)	C7—Co1iii	2.5057 (18)
O4—Co1i	2.0603 (14)	C9—H9A	0.9300
O4W—H4WA	0.8401	O1W—H1W	0.8401
O4W—H4WB	0.8393	O2W—H2WA	0.8400
N1—C9	1.338 (3)	O2W—H2WB	0.8401
O4i—Co1—N2	101.30 (6)	C9—N2—Co1	122.80 (13)
O4i—Co1—O4W	90.43 (6)	C4—N2—Co1	130.58 (13)
N2—Co1—O4W	93.58 (7)	C6—C1—C2	121.02 (16)
O4i—Co1—O3W	91.41 (6)	C6—C1—C7	117.55 (16)
N2—Co1—O3W	91.38 (6)	C2—C1—C7	121.40 (16)
O4W—Co1—O3W	174.27 (6)	C3—C2—C1	121.02 (16)
O4i—Co1—O2ii	158.80 (5)	C3—C2—C8	116.03 (16)
N2—Co1—O2ii	99.73 (6)	C1—C2—C8	122.80 (16)
O4W—Co1—O2ii	90.90 (6)	C2—C3—C4	118.00 (17)
O3W—Co1—O2ii	85.43 (5)	C2—C3—H3A	121.0
O4i—Co1—O1ii	98.39 (5)	C4—C3—H3A	121.0
N2—Co1—O1ii	160.30 (6)	C3—C4—N2	130.70 (18)
O4W—Co1—O1ii	85.57 (6)	C3—C4—C5	120.52 (17)
O3W—Co1—O1ii	88.79 (6)	N2—C4—C5	108.77 (16)
O2ii—Co1—O1ii	60.64 (5)	N1—C5—C6	132.21 (18)
O4i—Co1—C7ii	128.59 (6)	N1—C5—C4	105.67 (16)
N2—Co1—C7ii	130.06 (6)	C6—C5—C4	122.11 (17)
O4W—Co1—C7ii	88.46 (6)	C5—C6—C1	117.23 (17)
O3W—Co1—C7ii	86.15 (6)	C5—C6—H6A	121.4
O2ii—Co1—C7ii	30.33 (6)	C1—C6—H6A	121.4
O1ii—Co1—C7ii	30.31 (6)	O1—C7—O2	119.96 (16)
C7—O1—Co1iii	89.07 (11)	O1—C7—C1	119.97 (16)
C7—O2—Co1iii	90.30 (11)	O2—C7—C1	120.07 (16)
Co1—O3W—H3WA	119.7	O1—C7—Co1iii	60.62 (9)
Co1—O3W—H3WB	102.7	O2—C7—Co1iii	59.36 (9)
H3WA—O3W—H3WB	111.6	C1—C7—Co1iii	178.35 (14)
C8—O4—Co1i	128.68 (13)	O3—C8—O4	125.06 (18)
Co1—O4W—H4WA	116.2	O3—C8—C2	118.29 (17)
Co1—O4W—H4WB	116.2	O4—C8—C2	116.53 (17)
H4WA—O4W—H4WB	109.6	N2—C9—N1	113.50 (17)
C9—N1—C5	107.24 (16)	N2—C9—H9A	123.3
C9—N1—H1A	126.4	N1—C9—H9A	123.3
C5—N1—H1A	126.4	H2WA—O2W—H2WB	102.3
C9—N2—C4	104.80 (16)
O4i—Co1—N2—C9	158.93 (16)	C3—C4—C5—N1	−177.40 (18)
O4W—Co1—N2—C9	−109.92 (17)	N2—C4—C5—N1	1.9 (2)
O3W—Co1—N2—C9	67.21 (17)	C3—C4—C5—C6	3.7 (3)
O2ii—Co1—N2—C9	−18.39 (18)	N2—C4—C5—C6	−177.00 (18)
O1ii—Co1—N2—C9	−23.1 (3)	N1—C5—C6—C1	179.8 (2)
C7ii—Co1—N2—C9	−18.9 (2)	C4—C5—C6—C1	−1.6 (3)
O4i—Co1—N2—C4	−3.25 (19)	C2—C1—C6—C5	−0.9 (3)
O4W—Co1—N2—C4	87.90 (18)	C7—C1—C6—C5	−178.77 (17)
O3W—Co1—N2—C4	−94.97 (18)	Co1iii—O1—C7—O2	1.72 (18)
O2ii—Co1—N2—C4	179.43 (17)	Co1iii—O1—C7—C1	−178.23 (15)
O1ii—Co1—N2—C4	174.76 (16)	Co1iii—O2—C7—O1	−1.74 (18)
C7ii—Co1—N2—C4	178.90 (16)	Co1iii—O2—C7—C1	178.21 (15)
C6—C1—C2—C3	1.4 (3)	C6—C1—C7—O1	−30.8 (3)
C7—C1—C2—C3	179.21 (18)	C2—C1—C7—O1	151.34 (18)
C6—C1—C2—C8	176.81 (17)	C6—C1—C7—O2	149.27 (18)
C7—C1—C2—C8	−5.4 (3)	C2—C1—C7—O2	−28.6 (3)
C1—C2—C3—C4	0.6 (3)	Co1i—O4—C8—O3	0.8 (3)
C8—C2—C3—C4	−175.08 (17)	Co1i—O4—C8—C2	−175.08 (12)
C2—C3—C4—N2	177.8 (2)	C3—C2—C8—O3	−62.2 (2)
C2—C3—C4—C5	−3.1 (3)	C1—C2—C8—O3	122.2 (2)
C9—N2—C4—C3	177.6 (2)	C3—C2—C8—O4	114.0 (2)
Co1—N2—C4—C3	−17.9 (3)	C1—C2—C8—O4	−61.7 (2)
C9—N2—C4—C5	−1.6 (2)	C4—N2—C9—N1	0.7 (2)
Co1—N2—C4—C5	162.99 (14)	Co1—N2—C9—N1	−165.38 (14)
C9—N1—C5—C6	177.3 (2)	C5—N1—C9—N2	0.4 (2)
C9—N1—C5—C4	−1.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O1iv	0.84	1.97	2.798 (2)	170
N1—H1A···O1Wiv	0.86	2.45	3.130 (2)	136
O2W—H2WA···O4iv	0.84	1.99	2.78546	157
O3W—H3WB···O3i	0.84	1.85	2.641 (2)	158
O4W—H4WB···O3v	0.84	2.60	3.095 (2)	119
O4W—H4WA···O2v	0.84	1.86	2.679 (2)	165
O4W—H4WB···O2Wvi	0.84	2.02	2.76864	148
N1—H1A···O2W	0.86	2.31	2.89857	125
O1W—H1W···O3vii	0.84	1.98	2.8218 (18)	180
O2W—H2WB···O3Wviii	0.84	2.16	2.94922	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3W—H3WA⋯O1i	0.84	1.97	2.798 (2)	170
N1—H1A⋯O1W i	0.86	2.45	3.130 (2)	136
O2W—H2WA⋯O4i	0.84	1.99	2.786	157
O3W—H3WB⋯O3ii	0.84	1.85	2.641 (2)	158
O4W—H4WB⋯O3iii	0.84	2.60	3.095 (2)	119
O4W—H4WA⋯O2iii	0.84	1.86	2.679 (2)	165
O4W—H4WB⋯O2W iv	0.84	2.02	2.769	148
N1—H1A⋯O2W	0.86	2.31	2.899	125
O1W—H1W⋯O3v	0.84	1.98	2.8218 (18)	180
O2W—H2WB⋯O3W vi	0.84	2.16	2.949	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .