(μ-4,4′-Bipyridine-κ2N:N′)bis­[triaqua­(4,4′-bipyridine-κN)(3-nitro­phthalato-κO2)cobalt(II)]

Guo, H.-X.; Yao, Z.-L.; Weng, W.; Li, X.-Z.

doi:10.1107/S160053680902875X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m992-m993

doi:10.1107/S160053680902875X

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(μ-4,4′-Bipyridine-κ²N:N′)bis[triaqua(4,4′-bipyridine-κN)(3-nitrophthalato-κO²)cobalt(II)]

Hong-Xu Guo,^a ^* Zhong-Liang Yao,^b Wen Weng ^a and Xi-Zhong Li ^a

^aDepartment of Chemistry and Environmental Science, Zhangzhou Normal University, Zhangzhou, Fujian 363000, People's Republic of China, and ^bDepartment of Biology and Chemical Engineering, Fuqing Branch of Fujian Normal University, Fuqing, Fujian 350300, People's Republic of China
^*Correspondence e-mail: ghx919@yahoo.com.cn

(Received 29 May 2009; accepted 20 July 2009; online 25 July 2009)

The title binuclear complex, [Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆], has been synthesized hydrothermally from 3-nitrophthalic acid (H₂NPA), Co(NO₃)₂·6H₂O and 4,4′-bipyridine (4,4′-bipy). The molecule of the complex occupies a special position on an inversion centre. The Co^II atom has a slightly distorted octahedral environment formed by two N atoms from two 4,4′-bipy ligands, one carboxylate O atom from NPA, and three O atoms of water molecules. An extensive O—H⋯O and N—H⋯O hydrogen-bonding system links molecules of the complex into a three-dimensional network.

Related literature

For background to metal-involved supramolecular compounds, see: Noro (2004 ); Yaghi et al. (2003 ); Rao et al. (2004 ); Huang et al. (2004 ); Zhang et al. (2004 ). For other 3-nitrophthalic derivatives, see: Deng et al. (2007 ); Guo (2004 ); Song et al. (2007 ); Xiong & Qi (2007 ).

Experimental

Crystal data

[Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆]
M_r = 1112.74
Monoclinic, P 2₁ /c
a = 15.672 (3) Å
b = 9.4283 (19) Å
c = 16.063 (3) Å
β = 103.92 (3)°
V = 2303.8 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.21 × 0.15 × 0.12 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.765, T_max = 0.872
21789 measured reflections
5252 independent reflections
3669 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.134
S = 1.01
5252 reflections
352 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O3ⁱ	0.842 (10)	1.960 (11)	2.798 (3)	173 (3)
O7—H7B⋯O4ⁱⁱ	0.845 (10)	1.942 (12)	2.772 (3)	167 (3)
O8—H8A⋯O2	0.854 (10)	1.855 (13)	2.677 (3)	161 (3)
O8—H8B⋯N3ⁱⁱⁱ	0.847 (10)	2.021 (15)	2.830 (4)	159 (3)
O9—H9B⋯O4ⁱ	0.849 (10)	1.810 (13)	2.645 (3)	167 (3)
O9—H9C⋯O3	0.849 (10)	1.968 (13)	2.801 (3)	167 (3)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) -x, -y+2, -z.

Data collection: SMART (Siemens, 1994 ); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902875X/ya2101sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902875X/ya2101Isup2.hkl

checkCIF report

Comment top

Design and assembly of metal-involving supramolecular architectures are currently of great interest in the field of supramolecular chemistry and crystal engineering, because they can provide novel topology and functional materials (Noro, 2004; Yaghi et al., 2003; Rao et al., 2004). During the past decades, extensive efforts have been focused on the design and assembly of supramolecular architectures of this kind (Huang et al., 2004; Zhang et al., 2004). Although the multifunctional ligand, 3-nitrophthalic acid (H₂NPA), has been utilized to build many coordination complexes, such as dinuclear centrosymmetric complexes [LaL(HL)(H₂O)₃]₂.2H₂O (L = NPA) (Deng et al., 2007), [La₂(C₈H₃NO₆)₂(C₈H₄NO₆)₂(H₂O)₆].2H₂O (Xiong & Qi, 2007), and [Na(C₈H₄NO₆)(H₂O)₃].H₂O (Guo, 2004), only a few mixed ligand complexes involving NPA have been reported so far (Song et al., 2007). In this work, we employed NPA and 4,4'-bipy ligands to produce a novel binuclear complex, [Co₂(NPA)₂(bipy)₃(H₂O)₆](I).

Complex (I) occupies a special position in the inversion centre; the asymmetric unit consists of one cobalt(II) atom, one NPA ligand, one terminal and one-half of a bridging 4,4'-bipy groups, as well as three metal-coordinated water molecules.(Fig. 1 and Table 1). The Co1 atom has a a slightly distorted octahedral environment formed by two N atoms from two different bipy ligands, one carboyxlate O atom of the NPA ligand, and three water molecules. The µ₂-4,4'-bipyridine ligand bridges two [Co(NPA)(bipy)(H₂O)₃] units of the binuclear complex.

The extensive system of O—H···O hydrogen bonds links molecules of the complex into a three-dimensional network (Fig. 2; Table 1).

Related literature top

For background to metal-involved supramolecular compounds, see: Noro (2004); Yaghi et al. (2003); Rao et al. (2004); Huang et al. (2004); Zhang et al., (2004). For other 3-nitrophthalic derivatives, see: Deng et al. (2007); Guo (2004); Song et al. (2007); Xiong & Qi (2007).

Experimental top

A solution of Co(NO₃)₂.6H₂O (0.0291 g, 0.1 mmol) in 5 ml of water was added dropwise under continuous stirring to an aqueous solution (5 ml) of 3-nitrophthalic acid (0.0211 g, 0.1 mmol) and 4,4'-bipyridine (0.0156 g, 0.1 mmol). The resulting mixture was then transferred into a Teflon-lined stainless steel vessel, which was sealed and kept at 393 K for 72 h. The vessel was then cooled to room temperature, the reaction mixture was filtered, and single crystals were obtained from the filtrate after a few days of slow evaporation at room temperature.

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level; H-atoms bound to phenyl C atoms are omitted for clarity. H-atoms bound to O are shown as small circles of arbitrary radius. The unlabeled atoms are derived from their labeled counterparts via symmetry transformation (-x + 1,-y + 2,-z + 1).
	Fig. 2. Crystal packing of the title compound viewed down the a axis; H-bonds are shown as dashed lines.

(µ-4,4'-Bipyridine-κ²N:N')bis[triaqua(4,4'-bipyridine- κN)(3-nitrophthalato-κO²)cobalt(II)] top

Crystal data top

[Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆]	F(000) = 1144
M_r = 1112.74	D_x = 1.604 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 21789 reflections
a = 15.672 (3) Å	θ = 3.0–27.5°
b = 9.4283 (19) Å	µ = 0.81 mm⁻¹
c = 16.063 (3) Å	T = 293 K
β = 103.92 (3)°	Prism, pink
V = 2303.8 (8) Å³	0.21 × 0.15 × 0.12 mm
Z = 2

Data collection top

Siemens SMART CCD area-detector diffractometer	5252 independent reflections
Radiation source: fine-focus sealed tube	3669 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: no pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −20→20
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
T_min = 0.765, T_max = 0.872	l = −20→19
21789 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
5252 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 0.38 e Å⁻³
9 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆]	V = 2303.8 (8) Å³
M_r = 1112.74	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.672 (3) Å	µ = 0.81 mm⁻¹
b = 9.4283 (19) Å	T = 293 K
c = 16.063 (3) Å	0.21 × 0.15 × 0.12 mm
β = 103.92 (3)°

Data collection top

Siemens SMART CCD area-detector diffractometer	5252 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3669 reflections with I > 2σ(I)
T_min = 0.765, T_max = 0.872	R_int = 0.079
21789 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	9 restraints
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.38 e Å⁻³
5252 reflections	Δρ_min = −0.45 e Å⁻³
352 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	0.32172 (2)	0.70261 (4)	0.20771 (2)	0.02477 (14)
N1	0.17512 (19)	0.4939 (3)	−0.07320 (18)	0.0434 (7)
N2	0.24471 (16)	0.8547 (3)	0.12309 (15)	0.0299 (6)
N3	−0.0484 (2)	1.2759 (4)	−0.1856 (2)	0.0507 (8)
N4	0.35953 (16)	0.8342 (3)	0.31977 (14)	0.0288 (6)
O1	0.30328 (14)	0.5593 (2)	0.10689 (12)	0.0303 (5)
O2	0.22712 (15)	0.3866 (2)	0.15197 (13)	0.0398 (6)
O3	0.41953 (15)	0.2894 (2)	0.18540 (13)	0.0378 (6)
O4	0.43538 (15)	0.0753 (2)	0.13428 (14)	0.0395 (6)
O5	0.13514 (18)	0.5266 (3)	−0.02137 (16)	0.0565 (7)
O6	0.1662 (2)	0.5543 (4)	−0.14226 (19)	0.0909 (12)
O7	0.43623 (14)	0.7886 (2)	0.17266 (13)	0.0308 (5)
H7A	0.4781 (16)	0.782 (3)	0.2166 (14)	0.037*
H7B	0.4312 (19)	0.8724 (16)	0.1535 (17)	0.037*
O8	0.21785 (14)	0.6093 (3)	0.25287 (13)	0.0337 (5)
H8A	0.2092 (19)	0.534 (2)	0.2224 (18)	0.040*
H8B	0.1712 (13)	0.658 (3)	0.243 (2)	0.040*
O9	0.40189 (14)	0.5401 (2)	0.27330 (13)	0.0331 (5)
H9B	0.4550 (9)	0.560 (3)	0.2970 (18)	0.040*
H9C	0.4003 (18)	0.469 (2)	0.2406 (17)	0.040*
C1	0.28309 (19)	0.3469 (3)	0.02915 (18)	0.0272 (6)
C2	0.23784 (19)	0.3751 (3)	−0.05515 (18)	0.0312 (7)
C3	0.2485 (2)	0.2972 (4)	−0.1248 (2)	0.0386 (8)
H3A	0.2170	0.3202	−0.1800	0.046*
C4	0.3062 (2)	0.1854 (4)	−0.1112 (2)	0.0420 (8)
H4A	0.3132	0.1298	−0.1570	0.050*
C5	0.3537 (2)	0.1565 (3)	−0.02903 (19)	0.0359 (7)
H5A	0.3936	0.0817	−0.0203	0.043*
C6	0.34391 (19)	0.2355 (3)	0.04132 (18)	0.0283 (7)
C7	0.26975 (19)	0.4381 (3)	0.10318 (17)	0.0273 (6)
C8	0.4034 (2)	0.1983 (3)	0.12786 (19)	0.0290 (6)
C9	0.2360 (2)	0.8381 (4)	0.03926 (19)	0.0380 (8)
H9A	0.2676	0.7659	0.0210	0.046*
C10	0.1829 (2)	0.9217 (4)	−0.02198 (19)	0.0378 (8)
H10A	0.1795	0.9052	−0.0798	0.045*
C11	0.1994 (2)	0.9611 (4)	0.1467 (2)	0.0401 (8)
H11A	0.2049	0.9761	0.2050	0.048*
C12	0.1452 (2)	1.0492 (4)	0.0896 (2)	0.0400 (8)
H12A	0.1155	1.1221	0.1096	0.048*
C13	0.0546 (2)	1.0864 (4)	−0.1498 (2)	0.0481 (9)
H13A	0.0827	1.0105	−0.1690	0.058*
C14	−0.0048 (3)	1.1679 (5)	−0.2077 (2)	0.0558 (11)
H14A	−0.0148	1.1454	−0.2656	0.067*
C15	0.0285 (2)	1.2325 (4)	−0.0402 (2)	0.0442 (9)
H15A	0.0388	1.2599	0.0170	0.053*
C16	−0.0308 (3)	1.3064 (4)	−0.1027 (3)	0.0531 (10)
H16A	−0.0603	1.3824	−0.0855	0.064*
C17	0.13452 (19)	1.0300 (3)	0.00195 (19)	0.0300 (7)
C18	0.07229 (19)	1.1180 (4)	−0.06323 (19)	0.0320 (7)
C19	0.3917 (2)	0.9648 (3)	0.31517 (18)	0.0331 (7)
H19A	0.3766	1.0121	0.2629	0.040*
C20	0.4460 (2)	1.0327 (3)	0.38372 (18)	0.0310 (7)
H20A	0.4674	1.1229	0.3769	0.037*
C21	0.46875 (18)	0.9661 (3)	0.46269 (17)	0.0261 (6)
C22	0.4311 (2)	0.8345 (3)	0.46904 (18)	0.0336 (7)
H22A	0.4417	0.7880	0.5216	0.040*
C23	0.3779 (2)	0.7729 (4)	0.39713 (18)	0.0340 (7)
H23A	0.3536	0.6845	0.4027	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0295 (2)	0.0217 (2)	0.0215 (2)	−0.00056 (17)	0.00289 (16)	−0.00077 (15)
N1	0.0390 (16)	0.0472 (19)	0.0376 (15)	0.0047 (14)	−0.0032 (14)	0.0032 (14)
N2	0.0317 (13)	0.0290 (15)	0.0277 (12)	0.0015 (11)	0.0045 (11)	0.0015 (11)
N3	0.0410 (17)	0.055 (2)	0.0513 (18)	0.0092 (15)	0.0009 (15)	0.0066 (15)
N4	0.0353 (14)	0.0283 (15)	0.0223 (11)	−0.0019 (11)	0.0062 (11)	−0.0032 (10)
O1	0.0412 (12)	0.0224 (12)	0.0254 (10)	−0.0036 (9)	0.0044 (9)	−0.0011 (8)
O2	0.0486 (14)	0.0332 (14)	0.0409 (12)	−0.0088 (11)	0.0170 (11)	−0.0025 (10)
O3	0.0447 (13)	0.0299 (13)	0.0323 (11)	0.0056 (10)	−0.0036 (10)	−0.0036 (9)
O4	0.0456 (13)	0.0205 (12)	0.0458 (13)	0.0039 (10)	−0.0020 (10)	0.0026 (9)
O5	0.0578 (16)	0.0590 (19)	0.0494 (15)	0.0215 (14)	0.0065 (13)	−0.0057 (13)
O6	0.103 (3)	0.112 (3)	0.0584 (18)	0.053 (2)	0.0208 (17)	0.0473 (19)
O7	0.0360 (12)	0.0228 (12)	0.0312 (11)	−0.0017 (9)	0.0032 (9)	0.0009 (9)
O8	0.0325 (11)	0.0340 (13)	0.0335 (11)	0.0033 (10)	0.0060 (10)	0.0027 (9)
O9	0.0364 (12)	0.0256 (12)	0.0321 (11)	0.0023 (9)	−0.0017 (10)	−0.0028 (9)
C1	0.0291 (15)	0.0228 (16)	0.0275 (14)	−0.0066 (12)	0.0026 (12)	−0.0011 (12)
C2	0.0311 (16)	0.0282 (18)	0.0309 (15)	−0.0014 (13)	0.0008 (13)	0.0008 (13)
C3	0.0413 (18)	0.045 (2)	0.0258 (15)	−0.0057 (16)	0.0006 (14)	−0.0006 (14)
C4	0.051 (2)	0.045 (2)	0.0306 (16)	−0.0083 (17)	0.0111 (15)	−0.0097 (15)
C5	0.0416 (18)	0.0237 (17)	0.0419 (18)	−0.0010 (14)	0.0091 (15)	−0.0062 (14)
C6	0.0312 (16)	0.0218 (16)	0.0310 (15)	−0.0052 (12)	0.0054 (13)	0.0008 (12)
C7	0.0299 (15)	0.0229 (16)	0.0248 (14)	0.0017 (12)	−0.0020 (12)	−0.0007 (11)
C8	0.0307 (15)	0.0221 (16)	0.0320 (15)	−0.0039 (13)	0.0034 (13)	0.0023 (13)
C9	0.052 (2)	0.0327 (19)	0.0304 (16)	0.0115 (15)	0.0128 (15)	0.0041 (14)
C10	0.0468 (19)	0.041 (2)	0.0246 (15)	0.0107 (16)	0.0062 (14)	0.0040 (14)
C11	0.0445 (19)	0.042 (2)	0.0309 (16)	0.0059 (16)	0.0044 (15)	−0.0068 (15)
C12	0.0460 (19)	0.037 (2)	0.0340 (16)	0.0140 (16)	0.0048 (15)	−0.0081 (14)
C13	0.044 (2)	0.054 (2)	0.0421 (19)	0.0178 (17)	0.0011 (16)	−0.0041 (17)
C14	0.049 (2)	0.073 (3)	0.0392 (19)	0.020 (2)	−0.0007 (18)	−0.0034 (19)
C15	0.048 (2)	0.042 (2)	0.0410 (19)	0.0125 (17)	0.0076 (16)	0.0008 (16)
C16	0.056 (2)	0.042 (2)	0.060 (2)	0.0207 (18)	0.012 (2)	0.0046 (18)
C17	0.0271 (15)	0.0279 (17)	0.0345 (16)	0.0007 (13)	0.0062 (13)	0.0043 (13)
C18	0.0262 (15)	0.0337 (18)	0.0348 (16)	0.0024 (13)	0.0050 (13)	0.0026 (13)
C19	0.0444 (18)	0.0284 (18)	0.0246 (14)	−0.0008 (14)	0.0046 (13)	−0.0019 (12)
C20	0.0388 (17)	0.0259 (17)	0.0275 (14)	−0.0041 (13)	0.0061 (13)	−0.0022 (12)
C21	0.0292 (14)	0.0260 (16)	0.0232 (13)	−0.0017 (12)	0.0064 (12)	−0.0039 (12)
C22	0.0441 (18)	0.0344 (19)	0.0216 (14)	−0.0050 (14)	0.0065 (13)	0.0015 (13)
C23	0.0416 (18)	0.0325 (19)	0.0275 (15)	−0.0122 (14)	0.0077 (14)	−0.0028 (13)

Geometric parameters (Å, º) top

Co1—O1	2.075 (2)	C4—C5	1.378 (4)
Co1—O9	2.097 (2)	C4—H4A	0.9300
Co1—O8	2.126 (2)	C5—C6	1.393 (4)
Co1—N2	2.138 (2)	C5—H5A	0.9300
Co1—N4	2.149 (2)	C6—C8	1.517 (4)
Co1—O7	2.164 (2)	C9—C10	1.374 (4)
N1—O5	1.197 (4)	C9—H9A	0.9300
N1—O6	1.225 (4)	C10—C17	1.380 (4)
N1—C2	1.472 (4)	C10—H10A	0.9300
N2—C9	1.330 (4)	C11—C12	1.370 (4)
N2—C11	1.336 (4)	C11—H11A	0.9300
N3—C14	1.322 (5)	C12—C17	1.388 (4)
N3—C16	1.325 (5)	C12—H12A	0.9300
N4—C23	1.337 (4)	C13—C14	1.380 (5)
N4—C19	1.339 (4)	C13—C18	1.384 (4)
O1—C7	1.253 (4)	C13—H13A	0.9300
O2—C7	1.244 (4)	C14—H14A	0.9300
O3—C8	1.242 (4)	C15—C18	1.376 (5)
O4—C8	1.257 (4)	C15—C16	1.382 (5)
O7—H7A	0.842 (10)	C15—H15A	0.9300
O7—H7B	0.845 (10)	C16—H16A	0.9300
O8—H8A	0.854 (10)	C17—C18	1.498 (4)
O8—H8B	0.847 (10)	C19—C20	1.377 (4)
O9—H9B	0.849 (10)	C19—H19A	0.9300
O9—H9C	0.849 (10)	C20—C21	1.383 (4)
C1—C2	1.395 (4)	C20—H20A	0.9300
C1—C6	1.401 (4)	C21—C22	1.388 (4)
C1—C7	1.522 (4)	C21—C21ⁱ	1.497 (5)
C2—C3	1.382 (4)	C22—C23	1.380 (4)
C3—C4	1.372 (5)	C22—H22A	0.9300
C3—H3A	0.9300	C23—H23A	0.9300

O1—Co1—O9	82.56 (8)	C1—C6—C8	123.3 (3)
O1—Co1—O8	91.30 (9)	O2—C7—O1	127.5 (3)
O9—Co1—O8	86.66 (9)	O2—C7—C1	117.9 (3)
O1—Co1—N2	89.37 (9)	O1—C7—C1	114.7 (3)
O9—Co1—N2	170.96 (9)	O3—C8—O4	124.8 (3)
O8—Co1—N2	97.64 (9)	O3—C8—C6	119.5 (3)
O1—Co1—N4	171.19 (9)	O4—C8—C6	115.7 (3)
O9—Co1—N4	89.42 (9)	N2—C9—C10	123.7 (3)
O8—Co1—N4	91.87 (9)	N2—C9—H9A	118.2
N2—Co1—N4	98.34 (10)	C10—C9—H9A	118.2
O1—Co1—O7	90.54 (8)	C9—C10—C17	120.3 (3)
O9—Co1—O7	88.29 (9)	C9—C10—H10A	119.9
O8—Co1—O7	174.37 (8)	C17—C10—H10A	119.9
N2—Co1—O7	87.70 (9)	N2—C11—C12	123.4 (3)
N4—Co1—O7	85.57 (9)	N2—C11—H11A	118.3
O5—N1—O6	123.1 (3)	C12—C11—H11A	118.3
O5—N1—C2	119.7 (3)	C11—C12—C17	120.3 (3)
O6—N1—C2	117.2 (3)	C11—C12—H12A	119.9
C9—N2—C11	116.3 (3)	C17—C12—H12A	119.9
C9—N2—Co1	118.0 (2)	C14—C13—C18	119.8 (3)
C11—N2—Co1	125.5 (2)	C14—C13—H13A	120.1
C14—N3—C16	116.1 (3)	C18—C13—H13A	120.1
C23—N4—C19	116.7 (3)	N3—C14—C13	123.8 (3)
C23—N4—Co1	118.9 (2)	N3—C14—H14A	118.1
C19—N4—Co1	121.1 (2)	C13—C14—H14A	118.1
C7—O1—Co1	127.50 (19)	C18—C15—C16	119.5 (3)
Co1—O7—H7A	106 (2)	C18—C15—H15A	120.3
Co1—O7—H7B	116 (2)	C16—C15—H15A	120.3
H7A—O7—H7B	110.9 (16)	N3—C16—C15	124.2 (4)
Co1—O8—H8A	100 (2)	N3—C16—H16A	117.9
Co1—O8—H8B	114 (2)	C15—C16—H16A	117.9
H8A—O8—H8B	109.6 (16)	C10—C17—C12	116.0 (3)
Co1—O9—H9B	118 (2)	C10—C17—C18	121.6 (3)
Co1—O9—H9C	110 (2)	C12—C17—C18	122.4 (3)
H9B—O9—H9C	109.4 (16)	C15—C18—C13	116.5 (3)
C2—C1—C6	116.7 (3)	C15—C18—C17	121.9 (3)
C2—C1—C7	121.2 (3)	C13—C18—C17	121.5 (3)
C6—C1—C7	122.1 (2)	N4—C19—C20	123.5 (3)
C3—C2—C1	123.5 (3)	N4—C19—H19A	118.2
C3—C2—N1	116.7 (3)	C20—C19—H19A	118.2
C1—C2—N1	119.7 (3)	C19—C20—C21	119.7 (3)
C4—C3—C2	118.9 (3)	C19—C20—H20A	120.1
C4—C3—H3A	120.6	C21—C20—H20A	120.1
C2—C3—H3A	120.6	C20—C21—C22	116.9 (3)
C3—C4—C5	119.2 (3)	C20—C21—C21ⁱ	121.0 (3)
C3—C4—H4A	120.4	C22—C21—C21ⁱ	122.0 (3)
C5—C4—H4A	120.4	C23—C22—C21	119.8 (3)
C4—C5—C6	122.1 (3)	C23—C22—H22A	120.1
C4—C5—H5A	118.9	C21—C22—H22A	120.1
C6—C5—H5A	118.9	N4—C23—C22	123.2 (3)
C5—C6—C1	119.5 (3)	N4—C23—H23A	118.4
C5—C6—C8	117.2 (3)	C22—C23—H23A	118.4

O1—Co1—N2—C9	−21.2 (2)	C2—C1—C7—O2	106.9 (3)
O8—Co1—N2—C9	−112.4 (2)	C6—C1—C7—O2	−76.2 (4)
N4—Co1—N2—C9	154.5 (2)	C2—C1—C7—O1	−72.5 (4)
O7—Co1—N2—C9	69.3 (2)	C6—C1—C7—O1	104.5 (3)
O1—Co1—N2—C11	154.2 (3)	C5—C6—C8—O3	155.8 (3)
O8—Co1—N2—C11	63.0 (3)	C1—C6—C8—O3	−21.8 (5)
N4—Co1—N2—C11	−30.1 (3)	C5—C6—C8—O4	−21.9 (4)
O7—Co1—N2—C11	−115.2 (3)	C1—C6—C8—O4	160.4 (3)
O9—Co1—N4—C23	−31.5 (2)	C11—N2—C9—C10	−1.1 (5)
O8—Co1—N4—C23	55.1 (2)	Co1—N2—C9—C10	174.7 (3)
N2—Co1—N4—C23	153.1 (2)	N2—C9—C10—C17	−0.1 (5)
O7—Co1—N4—C23	−119.9 (2)	C9—N2—C11—C12	0.9 (5)
O9—Co1—N4—C19	127.1 (2)	Co1—N2—C11—C12	−174.5 (3)
O8—Co1—N4—C19	−146.3 (2)	N2—C11—C12—C17	0.5 (6)
N2—Co1—N4—C19	−48.3 (3)	C16—N3—C14—C13	1.5 (7)
O7—Co1—N4—C19	38.7 (2)	C18—C13—C14—N3	−1.1 (7)
O9—Co1—O1—C7	62.0 (2)	C14—N3—C16—C15	−0.5 (6)
O8—Co1—O1—C7	−24.5 (2)	C18—C15—C16—N3	−1.0 (6)
N2—Co1—O1—C7	−122.1 (2)	C9—C10—C17—C12	1.5 (5)
O7—Co1—O1—C7	150.2 (2)	C9—C10—C17—C18	−176.6 (3)
C6—C1—C2—C3	1.9 (5)	C11—C12—C17—C10	−1.7 (5)
C7—C1—C2—C3	179.0 (3)	C11—C12—C17—C18	176.5 (3)
C6—C1—C2—N1	−177.9 (3)	C16—C15—C18—C13	1.4 (5)
C7—C1—C2—N1	−0.8 (4)	C16—C15—C18—C17	−177.4 (3)
O5—N1—C2—C3	148.7 (3)	C14—C13—C18—C15	−0.5 (6)
O6—N1—C2—C3	−30.8 (5)	C14—C13—C18—C17	178.4 (4)
O5—N1—C2—C1	−31.5 (5)	C10—C17—C18—C15	−175.3 (3)
O6—N1—C2—C1	149.0 (3)	C12—C17—C18—C15	6.7 (5)
C1—C2—C3—C4	0.2 (5)	C10—C17—C18—C13	5.9 (5)
N1—C2—C3—C4	−180.0 (3)	C12—C17—C18—C13	−172.1 (3)
C2—C3—C4—C5	−1.8 (5)	C23—N4—C19—C20	4.3 (5)
C3—C4—C5—C6	1.3 (5)	Co1—N4—C19—C20	−154.8 (3)
C4—C5—C6—C1	0.9 (5)	N4—C19—C20—C21	−1.0 (5)
C4—C5—C6—C8	−176.8 (3)	C19—C20—C21—C22	−3.0 (5)
C2—C1—C6—C5	−2.4 (4)	C19—C20—C21—C21ⁱ	176.9 (3)
C7—C1—C6—C5	−179.5 (3)	C20—C21—C22—C23	3.6 (5)
C2—C1—C6—C8	175.2 (3)	C21ⁱ—C21—C22—C23	−176.3 (3)
C7—C1—C6—C8	−1.9 (5)	C19—N4—C23—C22	−3.6 (5)
Co1—O1—C7—O2	13.2 (4)	Co1—N4—C23—C22	156.0 (3)
Co1—O1—C7—C1	−167.53 (18)	C21—C22—C23—N4	−0.3 (5)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3ⁱⁱ	0.84 (1)	1.96 (1)	2.798 (3)	173 (3)
O7—H7B···O4ⁱⁱⁱ	0.85 (1)	1.94 (1)	2.772 (3)	167 (3)
O8—H8A···O2	0.85 (1)	1.86 (1)	2.677 (3)	161 (3)
O8—H8B···N3^iv	0.85 (1)	2.02 (2)	2.830 (4)	159 (3)
O9—H9B···O4ⁱⁱ	0.85 (1)	1.81 (1)	2.645 (3)	167 (3)
O9—H9C···O3	0.85 (1)	1.97 (1)	2.801 (3)	167 (3)

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆]
M_r	1112.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.672 (3), 9.4283 (19), 16.063 (3)
β (°)	103.92 (3)
V (Å³)	2303.8 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.21 × 0.15 × 0.12

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.765, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	21789, 5252, 3669
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.134, 1.01
No. of reflections	5252
No. of parameters	352
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.45

Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1994), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3ⁱ	0.842 (10)	1.960 (11)	2.798 (3)	173 (3)
O7—H7B···O4ⁱⁱ	0.845 (10)	1.942 (12)	2.772 (3)	167 (3)
O8—H8A···O2	0.854 (10)	1.855 (13)	2.677 (3)	161 (3)
O8—H8B···N3ⁱⁱⁱ	0.847 (10)	2.021 (15)	2.830 (4)	159 (3)
O9—H9B···O4ⁱ	0.849 (10)	1.810 (13)	2.645 (3)	167 (3)
O9—H9C···O3	0.849 (10)	1.968 (13)	2.801 (3)	167 (3)

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

Acknowledgements

This work was supported by the Natural Science Foundation of Fujian Province (No. 2008 J0172) and the National Natural Science Foundation of China (20705031).

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