catena-Poly[[[tetra­aqua­cobalt(II)]-μ-4,4′-bipyridine-κ2N:N′] pyridine-3,5-dicarboxyl­ate trihydrate]

Zhu, X.-D.

doi:10.1107/S1600536811023816

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m970-m971

doi:10.1107/S1600536811023816

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catena-Poly[[[tetraaquacobalt(II)]-μ-4,4′-bipyridine-κ²N:N′] pyridine-3,5-dicarboxylate trihydrate]

Xian-Dong Zhu ^a ^*

^aCollege of Biological and Chemical Engineering, Anhui Polytechnic University, Wuhu 241000, People's Republic of China
^*Correspondence e-mail: zhuxd@ahpu.edu.cn

(Received 27 April 2011; accepted 17 June 2011; online 25 June 2011)

The crystal structure of the title compound, {[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O}_n, consists of Co^II polymeric complex cations, uncoordinated pyridine-3,5-dicarboxylate anions and lattice water molecules. The Co^II cation is coordinated by two N atoms from two 4,4′-bipyridine ligands and four water molecules in a distorted octahedral geometry. The 4,4′-bipyridine ligands bridge Co cations, forming a polymeric chain running along the b axis. The two pyridine rings of the 4,4′-biyridine are twisted to each other by a dihedral angle of 8.95 (9)°. Extensive O—H⋯O hydrogen bonding network is present in the crystal structure.

Related literature

For the utility of 4,4′-bipyridine in assembling metal-organic frameworks, see: Briadha & Fujita (2001 ). For related complexes, see: Li et al. (2004 ); Zhang & Zhu (2005 ). For the synthesis, see: Whitfield et al. (2001 ).

Experimental

Crystal data

[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O
M_r = 506.33
Triclinic, $[P \overline 1]$
a = 7.0053 (18) Å
b = 11.449 (3) Å
c = 14.077 (4) Å
α = 105.352 (4)°
β = 92.837 (4)°
γ = 94.624 (2)°
V = 1082.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.669, T_max = 0.842
8332 measured reflections
4863 independent reflections
4345 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.118
S = 0.96
4863 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1W	2.0898 (12)
Co1—O2W	2.0764 (14)
Co1—O3W	2.1245 (13)
Co1—O4W	2.0709 (14)
Co1—N1	2.1692 (14)
Co1—N2ⁱ	2.1543 (14)
Symmetry code: (i) x, y+1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2ⁱⁱ	0.85	1.84	2.6813 (19)	173
O1W—H1B⋯O1ⁱⁱⁱ	0.85	1.96	2.780 (2)	162
O2W—H2A⋯O1	0.85	1.91	2.760 (2)	176
O2W—H2B⋯O6W	0.85	1.87	2.707 (2)	168
O3W—H3A⋯O1ⁱⁱⁱ	0.85	2.12	2.897 (2)	152
O3W—H3B⋯O3^iv	0.85	1.89	2.7408 (19)	176
O4W—H4A⋯O5W	0.85	1.82	2.665 (3)	171
O4W—H4B⋯O7W	0.85	1.90	2.734 (2)	168
O5W—H5A⋯O4ⁱ	0.85	1.90	2.747 (3)	172
O5W—H5B⋯O4^v	0.85	2.19	2.856 (3)	135
O6W—H6A⋯N3ⁱ	0.85	1.98	2.829 (2)	173
O6W—H6B⋯O2^vi	0.85	1.99	2.830 (2)	172
O7W—H7A⋯O3^v	0.85	1.98	2.828 (2)	175
O7W—H7B⋯O3	0.85	1.96	2.800 (2)	168
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+1, -z; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1; (v) -x+2, -y+1, -z+1; (vi) -x+2, -y+1, -z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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/S1600536811023816/xu5203sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023816/xu5203Isup2.hkl

checkCIF report

Comment top

The utility of linear bifunctional ligands, such as 4,4'-bipyridine, has been widely explored in the field of the crystal engineering of metal-organic frameworks (Briadha et al., 2001). Recently, we are interested in the assembly of new compounds which contain not only 4,4'-bipyridine ligand but also carboxylate groups in the crystal structure. In this paper, we report the synthesis and crystal structure of the title compound.

In the title compound, the cation shows a slightly distorted octahedral coordination environment composed of a six-coordinated Co(II) center. The 4,4'-bipyridine units bridge the Co(II) atoms directly to form a one-dimensional chain; similar to a Co^II complex (Li et al., 2004) and and a Ni^II complex (Zhang & Zhu, 2005) reported previously. The pyridine-3,5-dicarboxylate anion does not take part in coordination, but acts as a charge balance with two deprotonated carboxylate groups, and supplies hydrogen-bonding donor and acceptors. O—H···O and N—H···O hydrogen-bonds exist between uncoordinated anion, uncoordinated water and coordinated water molecules, which connect the one-dimensional chain into three-dimensional supramolecular network.

Related literature top

For the utility of 4,4'-bipyridine in assembling metal-organic frameworks, see: Briadha & Fujita (2001). For related complexes, see: Li et al. (2004); Zhang & Zhu (2005). For the synthesis, see: Whitfield et al. (2001).

Experimental top

A mixture of Co(NO₃)₂.6H₂O (0.064 g, 0.2 mmol), 4,4-bipyridine (0.034 g, 0.2 mmol), pyridine-3,5-dicarboxylic acid (0.034 g, 0.2 mmol), NaOH (0.008 g, 0.2 mmol) in water (10 ml) was sealed in a 25 ml Teflon-lined stainless steel autoclave. The mixture was heated at 423 K for 72 h, then slowly cooled to room temperature during 48 h. Two kinds of crystals were obtained from the reaction mixture. One is purple and needle shaped, which structure was reported by Whitfield et al. (2001); the other one is red and prism shaped, the structure is reported here.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. A fragment of one-dimensional chain structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.

catena-Poly[[[tetraaquacobalt(II)]-µ-4,4'-bipyridine- κ²N:N'] pyridine-3,5-dicarboxylate trihydrate] top

Crystal data top

[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O	Z = 2
M_r = 506.33	F(000) = 526
Triclinic, P1	D_x = 1.554 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0053 (18) Å	Cell parameters from 2942 reflections
b = 11.449 (3) Å	θ = 2.1–27.5°
c = 14.077 (4) Å	µ = 0.86 mm⁻¹
α = 105.352 (4)°	T = 293 K
β = 92.837 (4)°	Prism, red
γ = 94.624 (2)°	0.50 × 0.40 × 0.20 mm
V = 1082.2 (5) Å³

Data collection top

Bruker SMART 1000 CCD diffractometer	4863 independent reflections
Radiation source: fine-focus sealed tube	4345 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
T_min = 0.669, T_max = 0.842	k = −14→14
8332 measured reflections	l = −15→18

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
4863 reflections	(Δ/σ)_max = 0.001
289 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O	γ = 94.624 (2)°
M_r = 506.33	V = 1082.2 (5) Å³
Triclinic, P1	Z = 2
a = 7.0053 (18) Å	Mo Kα radiation
b = 11.449 (3) Å	µ = 0.86 mm⁻¹
c = 14.077 (4) Å	T = 293 K
α = 105.352 (4)°	0.50 × 0.40 × 0.20 mm
β = 92.837 (4)°

Data collection top

Bruker SMART 1000 CCD diffractometer	4863 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4345 reflections with I > 2σ(I)
T_min = 0.669, T_max = 0.842	R_int = 0.012
8332 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.96	Δρ_max = 0.51 e Å⁻³
4863 reflections	Δρ_min = −0.28 e Å⁻³
289 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	0.38876 (3)	0.627012 (17)	0.230821 (15)	0.02719 (11)
O1	0.88432 (18)	0.45647 (11)	0.17193 (9)	0.0357 (3)
O2	0.8709 (2)	0.31057 (12)	0.02985 (9)	0.0457 (3)
O3	0.8583 (2)	0.32631 (11)	0.48551 (9)	0.0457 (3)
O4	0.8299 (3)	0.12902 (13)	0.47420 (10)	0.0588 (4)
N1	0.3885 (2)	0.43762 (12)	0.23107 (10)	0.0289 (3)
N2	0.3821 (2)	−0.18489 (12)	0.23179 (10)	0.0302 (3)
N3	0.8803 (2)	0.03959 (13)	0.17180 (11)	0.0377 (3)
C1	0.3827 (3)	0.40339 (14)	0.31469 (12)	0.0331 (4)
H1	0.3823	0.4648	0.3751	0.040*
C2	0.3773 (3)	0.28345 (14)	0.31811 (12)	0.0313 (3)
H2	0.3750	0.2645	0.3798	0.038*
C3	0.3752 (2)	0.19091 (13)	0.23145 (11)	0.0252 (3)
C4	0.3781 (3)	0.22635 (14)	0.14371 (12)	0.0312 (3)
H4	0.3747	0.1666	0.0821	0.037*
C5	0.3860 (3)	0.34851 (15)	0.14656 (12)	0.0326 (3)
H5	0.3898	0.3704	0.0861	0.039*
C6	0.3733 (2)	0.06074 (13)	0.23155 (11)	0.0261 (3)
C7	0.3486 (3)	0.02297 (15)	0.31603 (13)	0.0380 (4)
H7	0.3283	0.0807	0.3761	0.046*
C8	0.3531 (3)	−0.09846 (15)	0.31378 (13)	0.0402 (4)
H8	0.3349	−0.1217	0.3729	0.048*
C9	0.4037 (3)	−0.14903 (14)	0.14960 (13)	0.0331 (4)
H9	0.4233	−0.2086	0.0905	0.040*
C10	0.3990 (3)	−0.02929 (14)	0.14642 (12)	0.0326 (4)
H10	0.4135	−0.0088	0.0859	0.039*
C11	0.8681 (3)	0.07055 (16)	0.26959 (13)	0.0338 (4)
H11	0.8642	0.0075	0.3020	0.041*
C12	0.8609 (2)	0.18844 (15)	0.32658 (11)	0.0288 (3)
C13	0.8678 (2)	0.28087 (14)	0.27885 (11)	0.0274 (3)
H13	0.8659	0.3633	0.3155	0.033*
C14	0.8773 (2)	0.25103 (14)	0.17736 (11)	0.0262 (3)
C15	0.8837 (2)	0.12965 (15)	0.12731 (12)	0.0327 (3)
H15	0.8908	0.1093	0.0577	0.039*
C16	0.8777 (2)	0.34712 (14)	0.12216 (11)	0.0288 (3)
C17	0.8465 (3)	0.21575 (15)	0.43678 (12)	0.0356 (4)
O1W	0.19781 (18)	0.56791 (11)	0.10504 (8)	0.0357 (3)
H1A	0.1813	0.6024	0.0591	0.043*
H1B	0.0898	0.5339	0.1132	0.043*
O2W	0.6205 (2)	0.61273 (12)	0.14338 (12)	0.0472 (3)
H2A	0.7040	0.5672	0.1545	0.057*
H2B	0.6924	0.6702	0.1320	0.057*
O3W	0.14285 (19)	0.63665 (11)	0.31403 (9)	0.0380 (3)
H3A	0.0450	0.5866	0.2905	0.046*
H3B	0.1477	0.6495	0.3764	0.046*
O4W	0.5585 (2)	0.68048 (12)	0.36252 (11)	0.0510 (4)
H4A	0.6317	0.7466	0.3793	0.061*
H4B	0.6193	0.6310	0.3850	0.061*
O5W	0.8025 (3)	0.87961 (16)	0.43207 (17)	0.0859 (7)
H5A	0.7997	0.9560	0.4422	0.103*
H5B	0.9151	0.8574	0.4258	0.103*
O6W	0.8252 (2)	0.78607 (12)	0.08166 (12)	0.0575 (4)
H6A	0.8500	0.8610	0.1118	0.069*
H6B	0.9238	0.7623	0.0522	0.069*
O7W	0.7707 (2)	0.55000 (13)	0.45807 (11)	0.0552 (4)
H7A	0.8792	0.5902	0.4781	0.066*
H7B	0.7806	0.4780	0.4623	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.03388 (16)	0.01625 (15)	0.03333 (15)	0.00209 (9)	0.00055 (10)	0.01041 (10)
O1	0.0457 (7)	0.0266 (6)	0.0370 (6)	0.0041 (5)	0.0037 (5)	0.0123 (5)
O2	0.0725 (10)	0.0417 (7)	0.0278 (6)	0.0085 (7)	0.0049 (6)	0.0165 (5)
O3	0.0727 (10)	0.0329 (7)	0.0310 (6)	−0.0010 (6)	0.0004 (6)	0.0103 (5)
O4	0.1060 (13)	0.0368 (7)	0.0369 (7)	−0.0019 (8)	0.0017 (7)	0.0190 (6)
N1	0.0356 (7)	0.0161 (6)	0.0364 (7)	0.0018 (5)	0.0015 (5)	0.0103 (5)
N2	0.0375 (7)	0.0179 (6)	0.0378 (7)	0.0037 (5)	0.0024 (5)	0.0120 (5)
N3	0.0482 (9)	0.0256 (7)	0.0395 (8)	0.0035 (6)	0.0054 (6)	0.0087 (6)
C1	0.0448 (10)	0.0211 (7)	0.0341 (8)	0.0023 (7)	0.0019 (7)	0.0090 (6)
C2	0.0421 (9)	0.0221 (7)	0.0312 (8)	0.0024 (6)	0.0012 (6)	0.0104 (6)
C3	0.0248 (7)	0.0185 (7)	0.0340 (8)	0.0025 (5)	0.0017 (5)	0.0102 (6)
C4	0.0418 (9)	0.0195 (7)	0.0329 (8)	0.0037 (6)	0.0031 (6)	0.0081 (6)
C5	0.0435 (9)	0.0236 (8)	0.0334 (8)	0.0040 (7)	0.0029 (6)	0.0123 (6)
C6	0.0255 (7)	0.0189 (7)	0.0357 (8)	0.0029 (5)	0.0012 (6)	0.0107 (6)
C7	0.0607 (12)	0.0220 (8)	0.0345 (9)	0.0088 (7)	0.0112 (8)	0.0104 (6)
C8	0.0630 (12)	0.0240 (8)	0.0388 (9)	0.0096 (8)	0.0119 (8)	0.0145 (7)
C9	0.0446 (9)	0.0183 (7)	0.0361 (8)	0.0038 (6)	0.0028 (7)	0.0069 (6)
C10	0.0461 (10)	0.0213 (7)	0.0326 (8)	0.0039 (7)	0.0020 (7)	0.0112 (6)
C11	0.0401 (9)	0.0274 (8)	0.0372 (8)	0.0005 (7)	0.0017 (7)	0.0157 (7)
C12	0.0305 (8)	0.0279 (8)	0.0290 (7)	−0.0004 (6)	−0.0008 (6)	0.0111 (6)
C13	0.0310 (8)	0.0235 (7)	0.0290 (7)	0.0017 (6)	0.0016 (6)	0.0098 (6)
C14	0.0252 (7)	0.0268 (8)	0.0293 (7)	0.0025 (6)	0.0029 (5)	0.0119 (6)
C15	0.0385 (9)	0.0302 (8)	0.0297 (8)	0.0018 (7)	0.0037 (6)	0.0090 (6)
C16	0.0289 (8)	0.0298 (8)	0.0314 (8)	0.0035 (6)	0.0041 (6)	0.0139 (6)
C17	0.0445 (10)	0.0323 (8)	0.0312 (8)	−0.0019 (7)	−0.0030 (7)	0.0135 (7)
O1W	0.0410 (7)	0.0348 (6)	0.0350 (6)	−0.0028 (5)	−0.0033 (5)	0.0192 (5)
O2W	0.0391 (7)	0.0313 (6)	0.0813 (10)	0.0112 (5)	0.0197 (6)	0.0279 (7)
O3W	0.0427 (7)	0.0393 (7)	0.0297 (6)	−0.0022 (5)	0.0051 (5)	0.0066 (5)
O4W	0.0613 (9)	0.0267 (6)	0.0630 (9)	−0.0064 (6)	−0.0266 (7)	0.0171 (6)
O5W	0.0886 (14)	0.0368 (9)	0.1268 (17)	−0.0160 (9)	−0.0430 (12)	0.0281 (10)
O6W	0.0705 (10)	0.0318 (7)	0.0688 (10)	0.0014 (7)	0.0318 (8)	0.0069 (6)
O7W	0.0640 (10)	0.0390 (7)	0.0635 (9)	0.0050 (7)	−0.0161 (7)	0.0190 (7)

Geometric parameters (Å, º) top

Co1—O1W	2.0898 (12)	C7—H7	0.9500
Co1—O2W	2.0764 (14)	C8—H8	0.9500
Co1—O3W	2.1245 (13)	C9—C10	1.386 (2)
Co1—O4W	2.0709 (14)	C9—H9	0.9500
Co1—N1	2.1692 (14)	C10—H10	0.9500
Co1—N2ⁱ	2.1543 (14)	C11—C12	1.382 (2)
O1—C16	1.258 (2)	C11—H11	0.9500
O2—C16	1.252 (2)	C12—C13	1.395 (2)
O3—C17	1.264 (2)	C12—C17	1.509 (2)
O4—C17	1.242 (2)	C13—C14	1.385 (2)
N1—C1	1.337 (2)	C13—H13	0.9500
N1—C5	1.345 (2)	C14—C15	1.387 (2)
N2—C9	1.337 (2)	C14—C16	1.505 (2)
N2—C8	1.343 (2)	C15—H15	0.9500
N3—C11	1.336 (2)	O1W—H1A	0.8501
N3—C15	1.340 (2)	O1W—H1B	0.8499
C1—C2	1.384 (2)	O2W—H2A	0.8501
C1—H1	0.9500	O2W—H2B	0.8499
C2—C3	1.386 (2)	O3W—H3A	0.8500
C2—H2	0.9500	O3W—H3B	0.8500
C3—C4	1.399 (2)	O4W—H4A	0.8498
C3—C6	1.490 (2)	O4W—H4B	0.8499
C4—C5	1.385 (2)	O5W—H5A	0.8500
C4—H4	0.9500	O5W—H5B	0.8500
C5—H5	0.9500	O6W—H6A	0.8499
C6—C7	1.383 (2)	O6W—H6B	0.8499
C6—C10	1.389 (2)	O7W—H7A	0.8501
C7—C8	1.385 (2)	O7W—H7B	0.8499

O4W—Co1—O2W	94.18 (7)	N2—C8—H8	118.5
O4W—Co1—O1W	174.82 (5)	C7—C8—H8	118.5
O2W—Co1—O1W	90.62 (6)	N2—C9—C10	123.27 (16)
O4W—Co1—O3W	88.56 (6)	N2—C9—H9	118.4
O2W—Co1—O3W	177.17 (5)	C10—C9—H9	118.4
O1W—Co1—O3W	86.62 (5)	C9—C10—C6	120.15 (15)
O4W—Co1—N2ⁱ	89.64 (5)	C9—C10—H10	119.9
O2W—Co1—N2ⁱ	90.37 (5)	C6—C10—H10	119.9
O1W—Co1—N2ⁱ	92.30 (5)	N3—C11—C12	124.18 (15)
O3W—Co1—N2ⁱ	90.39 (5)	N3—C11—H11	117.9
O4W—Co1—N1	90.65 (5)	C12—C11—H11	117.9
O2W—Co1—N1	90.96 (5)	C11—C12—C13	117.76 (15)
O1W—Co1—N1	87.30 (5)	C11—C12—C17	120.90 (14)
O3W—Co1—N1	88.27 (5)	C13—C12—C17	121.34 (15)
N2ⁱ—Co1—N1	178.62 (5)	C14—C13—C12	119.21 (15)
C1—N1—C5	116.80 (14)	C14—C13—H13	120.4
C1—N1—Co1	121.68 (11)	C12—C13—H13	120.4
C5—N1—Co1	121.46 (11)	C13—C14—C15	118.25 (14)
C9—N2—C8	116.73 (14)	C13—C14—C16	121.12 (14)
C9—N2—Co1ⁱⁱ	121.19 (11)	C15—C14—C16	120.63 (14)
C8—N2—Co1ⁱⁱ	122.07 (11)	N3—C15—C14	123.56 (15)
C11—N3—C15	117.02 (15)	N3—C15—H15	118.2
N1—C1—C2	123.67 (15)	C14—C15—H15	118.2
N1—C1—H1	118.2	O2—C16—O1	125.59 (15)
C2—C1—H1	118.2	O2—C16—C14	116.60 (14)
C3—C2—C1	120.00 (15)	O1—C16—C14	117.81 (14)
C3—C2—H2	120.0	O4—C17—O3	124.16 (16)
C1—C2—H2	120.0	O4—C17—C12	118.32 (16)
C2—C3—C4	116.44 (14)	O3—C17—C12	117.48 (14)
C2—C3—C6	121.95 (15)	Co1—O1W—H1A	127.7
C4—C3—C6	121.61 (15)	Co1—O1W—H1B	115.7
C5—C4—C3	120.09 (15)	H1A—O1W—H1B	107.9
C5—C4—H4	120.0	Co1—O2W—H2A	116.1
C3—C4—H4	120.0	Co1—O2W—H2B	127.7
N1—C5—C4	122.99 (15)	H2A—O2W—H2B	100.5
N1—C5—H5	118.5	Co1—O3W—H3A	118.3
C4—C5—H5	118.5	Co1—O3W—H3B	124.0
C7—C6—C10	116.35 (14)	H3A—O3W—H3B	107.1
C7—C6—C3	122.19 (15)	Co1—O4W—H4A	122.4
C10—C6—C3	121.46 (15)	Co1—O4W—H4B	122.6
C6—C7—C8	120.48 (16)	H4A—O4W—H4B	104.3
C6—C7—H7	119.8	H5A—O5W—H5B	113.0
C8—C7—H7	119.8	H6A—O6W—H6B	107.7
N2—C8—C7	122.99 (16)	H7A—O7W—H7B	106.9

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2ⁱⁱⁱ	0.85	1.84	2.6813 (19)	173
O1W—H1B···O1^iv	0.85	1.96	2.780 (2)	162
O2W—H2A···O1	0.85	1.91	2.760 (2)	176
O2W—H2B···O6W	0.85	1.87	2.707 (2)	168
O3W—H3A···O1^iv	0.85	2.12	2.897 (2)	152
O3W—H3B···O3^v	0.85	1.89	2.7408 (19)	176
O4W—H4A···O5W	0.85	1.82	2.665 (3)	171
O4W—H4B···O7W	0.85	1.90	2.734 (2)	168
O5W—H5A···O4ⁱ	0.85	1.90	2.747 (3)	172
O5W—H5B···O4^vi	0.85	2.19	2.856 (3)	135
O6W—H6A···N3ⁱ	0.85	1.98	2.829 (2)	173
O6W—H6B···O2^vii	0.85	1.99	2.830 (2)	172
O7W—H7A···O3^vi	0.85	1.98	2.828 (2)	175
O7W—H7B···O3	0.85	1.96	2.800 (2)	168

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₈N₂)(H₂O)₄](C₇H₃NO₄)·3H₂O
M_r	506.33
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0053 (18), 11.449 (3), 14.077 (4)
α, β, γ (°)	105.352 (4), 92.837 (4), 94.624 (2)
V (Å³)	1082.2 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.669, 0.842
No. of measured, independent and observed [I > 2σ(I)] reflections	8332, 4863, 4345
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.118, 0.96
No. of reflections	4863
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.28

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O1W	2.0898 (12)	Co1—O4W	2.0709 (14)
Co1—O2W	2.0764 (14)	Co1—N1	2.1692 (14)
Co1—O3W	2.1245 (13)	Co1—N2ⁱ	2.1543 (14)

Symmetry code: (i) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2ⁱⁱ	0.85	1.84	2.6813 (19)	173
O1W—H1B···O1ⁱⁱⁱ	0.85	1.96	2.780 (2)	162
O2W—H2A···O1	0.85	1.91	2.760 (2)	176
O2W—H2B···O6W	0.85	1.87	2.707 (2)	168
O3W—H3A···O1ⁱⁱⁱ	0.85	2.12	2.897 (2)	152
O3W—H3B···O3^iv	0.85	1.89	2.7408 (19)	176
O4W—H4A···O5W	0.85	1.82	2.665 (3)	171
O4W—H4B···O7W	0.85	1.90	2.734 (2)	168
O5W—H5A···O4ⁱ	0.85	1.90	2.747 (3)	172
O5W—H5B···O4^v	0.85	2.19	2.856 (3)	135
O6W—H6A···N3ⁱ	0.85	1.98	2.829 (2)	173
O6W—H6B···O2^vi	0.85	1.99	2.830 (2)	172
O7W—H7A···O3^v	0.85	1.98	2.828 (2)	175
O7W—H7B···O3	0.85	1.96	2.800 (2)	168

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

Acknowledgements

This work was supported financially by the Science Foundation of the Education Department of Anhui Province (KJ2010B012) and the Funds of Talent Introduction Project of Anhui Polytechnic University, China (2008YQQ010).

References

Briadha, K. & Fujita, M. (2001). Chem. Commun. pp. 15–16. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, F., Wang, Y., Bi, W., Li, X. & Cao, R. (2004). Acta Cryst. E60, m1681–m1683. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Whitfield, T., Zheng, L.-M., Wang, X. & Jacobson, A. J. (2001). Solid State Sci. 3, 829–835. CrossRef CAS Google Scholar
Zhang, L.-P. & Zhu, L.-G. (2005). Acta Cryst. E61, m1264–m1265. Web of Science CSD CrossRef IUCr Journals Google Scholar

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