Poly[[tetraaqua­bis(μ3-1H-benzimidazole-5,6-dicarboxyl­ato)dicobalt(II)] trihydrate]

Fu, J.-D.; Tang, Z.-W.; Yuan, M.-Y.; Wen, Y.-H.

doi:10.1107/S1600536809049083

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1657

doi:10.1107/S1600536809049083

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Poly[[tetraaquabis(μ₃-1H-benzimidazole-5,6-dicarboxylato)dicobalt(II)] trihydrate]

Jun-Dan Fu,^a Zhi-Wei Tang,^a Ming-Yue Yuan ^a and Yi-Hang Wen ^a ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: wyh@zjnu.edu.cn

(Received 5 November 2009; accepted 18 November 2009; online 21 November 2009)

The title complex, {[Co₂(C₉H₄N₂O₄)₂(H₂O)₄]·3H₂O}_n, was synthesized hydrothermally. The unique Co^II ion is coordinated in a distorted octahedral coordination environment by two water molecules and three symmetry-related 1H-benzimidazole-5,6-dicarboxylate (Hbidc) ligands. The Hbidc ligands coordinate via a bis-chelating and mono-chelating carboxylate 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, intermolecular N—H⋯O and O—H⋯O hydrogen bonds connect complex and solvent water molecules, forming a three-dimensional supermolecular network. One of the solvent water molecules 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_r = 652.26
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.087
S = 1.03
2656 reflections
174 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.63 e Å⁻³

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⋯O1Wⁱ	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⋯O3^v	0.84	1.98	2.8218 (18)	180
O2W—H2WB⋯O3W^vi	0.84	2.16	2.949	157
Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y, -z; (iii) $[-x, y, -z-{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) $[x, -y, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049083/lh2948sup1.cif

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

checkCIF report

Comment top

It is well known that carboxylate ligands play an important role in coordination chemistry (Grodzicki et al. , 2005; Laduca, 2009). In recent years, the interaction of Hbidc with several metal ions has been studied, due to its unique ability to form stable chelates in diverse coordination modes such as bidentate, meridian and bridging (Wei et al., 2008; Yao et al., 2008). Herein we report the synthesis and crystal structure of the title two-dimensional complex of Hbidc (I).

Part of the 2-D structure of (I) is shown in Fig.1. The unique Co^II ion is six-coordinated by one N atom and three O atoms from from three symmetry related Hbidc ligands and two oxygen atoms from two water molecules. Each Hbidc ligand coordinates via a chelating carboxylate group and a single oxygen atom of another carboxylate group bridging two Co^II ions to form a one-dimensional chain along the b-axis with a Co···Co separation of 5.4374 (5) Å. In addition, Hbidc ligands coordinate through a N atom to connect the adjacent chains forming a two-dimensional network with chains separated by ca. 7.06 Å (see Fig. 2a). In the crystal structure, intermolecular N-H···O and O-H···O hydrogen bonds connect complex and solvent water molecules to form a three-dimensional supermolecular network (see Table 1 and Fig. 2b).

Related literature top

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 top

A mixture of CoSO₄.7H₂O(0.141 g, 0.5 mmol), benzimidazole-5,6-dicarboxylic acid(0.103 g, 0.5 mmol), H₂O(16 ml)and 4-sulfophthalic(1 ml)(solution pH = 5) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated at 393 k for 3 d. On completion of the reaction, the reactor was cooled slowly to room temperature and the mixture was filtered, giving red single crystals suitable for X-ray analysis in 30% yield.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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).

Figures top

	Fig. 1. Part of the 2-D structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A)-x, -y, -z; (B)x + 1/2, -y + 1/2, z + 1/2; (c)x - 1/2,-y + 1/2, z - 1/2.
	Fig. 2. (a) Part of the 2-D structure of (I) viewed along the crystallographic c-axis. (b) Part of the crystal structure showing the donor···acceptor atom distances of hydrogen bonds as dashed lines.

Poly[[tetraaquabis(µ₃-1H-benzimidazole-5,6-dicarboxylato)dicobalt(II)] trihydrate] top

Crystal data top

[Co₂(C₉H₄N₂O₄)₂(H₂O)₄]·3H₂O	F(000) = 1328
M_r = 652.26	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0533P)² + 3.4124P] where P = (F_o² + 2F_c²)/3
2656 reflections	(Δ/σ)_max = 0.001
174 parameters	Δρ_max = 0.81 e Å⁻³
6 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Co₂(C₉H₄N₂O₄)₂(H₂O)₄]·3H₂O	V = 2302.2 (3) Å³
M_r = 652.26	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.4085 (18) Å	µ = 1.53 mm⁻¹
b = 9.1564 (7) Å	T = 296 K
c = 13.0907 (10) Å	0.43 × 0.25 × 0.07 mm
β = 121.006 (4)°

Data collection top

Bruker APEXII diffractometer	2656 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2402 reflections with I > 2σ(I)
T_min = 0.63, T_max = 0.90	R_int = 0.018
9315 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	6 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.03	Δρ_max = 0.81 e Å⁻³
2656 reflections	Δρ_min = −0.63 e Å⁻³
174 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) −x, −y, −z; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O1^iv	0.84	1.97	2.798 (2)	170
N1—H1A···O1W^iv	0.86	2.45	3.130 (2)	136
O2W—H2WA···O4^iv	0.84	1.99	2.7855	157
O3W—H3WB···O3ⁱ	0.84	1.85	2.641 (2)	158
O4W—H4WB···O3^v	0.84	2.60	3.095 (2)	119
O4W—H4WA···O2^v	0.84	1.86	2.679 (2)	165
O4W—H4WB···O2W^vi	0.84	2.02	2.7686	148
N1—H1A···O2W	0.86	2.31	2.8986	125
O1W—H1W···O3^vii	0.84	1.98	2.8218 (18)	180
O2W—H2WB···O3W^viii	0.84	2.16	2.9492	157

Symmetry codes: (i) −x, −y, −z; (iv) −x, −y+1, −z; (v) −x, y, −z−1/2; (vi) x, y−1, z; (vii) x, −y, z+1/2; (viii) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Co₂(C₉H₄N₂O₄)₂(H₂O)₄]·3H₂O
M_r	652.26
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	22.4085 (18), 9.1564 (7), 13.0907 (10)
β (°)	121.006 (4)
V (Å³)	2302.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.53
Crystal size (mm)	0.43 × 0.25 × 0.07

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.63, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	9315, 2656, 2402
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.087, 1.03
No. of reflections	2656
No. of parameters	174
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.63

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O1ⁱ	0.84	1.97	2.798 (2)	169.9
N1—H1A···O1Wⁱ	0.86	2.45	3.130 (2)	135.9
O2W—H2WA···O4ⁱ	0.84	1.99	2.78546	157.1
O3W—H3WB···O3ⁱⁱ	0.84	1.85	2.641 (2)	157.5
O4W—H4WB···O3ⁱⁱⁱ	0.84	2.60	3.095 (2)	118.7
O4W—H4WA···O2ⁱⁱⁱ	0.84	1.86	2.679 (2)	164.8
O4W—H4WB···O2W^iv	0.84	2.02	2.76864	148.2
N1—H1A···O2W	0.86	2.31	2.89857	125.4
O1W—H1W···O3^v	0.84	1.98	2.8218 (18)	180.0
O2W—H2WB···O3W^vi	0.84	2.16	2.94922	157.3

Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y, −z; (iii) −x, y, −z−1/2; (iv) x, y−1, z; (v) x, −y, z+1/2; (vi) −x+1/2, y+1/2, −z+1/2.

References

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