Diaqua­bis­(3-nitro­benzoato-κO1)bis­[1H-5-(3-pyrid­yl)-3-(4-pyrid­yl)-1H-1,2,4-triazole-κN5]cobalt(II) dihydrate

Zhang, Y.-L.; Liu, T.-L.; Sun, S.-J.; Li, J.-H.; Wu, S.-Q.

doi:10.1107/S1600536810046374

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1588

https://doi.org/10.1107/S1600536810046374

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Diaquabis(3-nitrobenzoato-κO¹)bis[1H-5-(3-pyridyl)-3-(4-pyridyl)-1H-1,2,4-triazole-κN⁵]cobalt(II) dihydrate

Yun-Liang Zhang,^a ^* Ti-Lou Liu,^a Shuang-Jiao Sun,^a Jie-Hong Li ^a and Shi-Qing Wu ^a

^aDepartment of Pharmacy, Shaoyang Medical College, Shaoyang, Hunan 422000, People's Republic of China
^*Correspondence e-mail: yunliangz2009@163.com

(Received 6 September 2010; accepted 10 November 2010; online 17 November 2010)

In the centrosymmetric title compound, [Co(C₇H₄NO₄)₂(C₁₂H₉N₅)₂(H₂O)₂]·2H₂O, the Co^II atom, located on an inversion center, is coordinated by two N atoms [Co—N = 2.155 (3) Å] and four O atoms [Co—O = 2.099 (2)–2.117 (3) Å] in a distorted octahedral geometry. Intermolecular N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds link the components into a three-dimensional supramolecular framework.

Related literature

For background to triazole-containing compounds, see: Huang et al. (2010a ); Klingele & Brooker (2003 ); Liu & Zhang (2009 ). For related structures, see: Xie et al. (2009 ); Du et al. (2007 ); Huang et al. (2010b ); Dong (2009 ).

Experimental

Crystal data

[Co(C₇H₄NO₄)₂(C₁₂H₉N₅)₂(H₂O)₂]·2H₂O
M_r = 909.70
Triclinic, $[P \overline 1]$
a = 8.7080 (17) Å
b = 9.850 (2) Å
c = 12.488 (3) Å
α = 81.97 (3)°
β = 85.74 (3)°
γ = 71.36 (3)°
V = 1004.5 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.835, T_max = 0.945
5815 measured reflections
3518 independent reflections
2642 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.146
S = 1.03
3518 reflections
306 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O6ⁱ	0.85 (3)	1.94 (3)	2.778 (5)	169 (3)
O5—H5A⋯N2ⁱⁱ	0.84 (3)	2.02 (3)	2.856 (4)	174 (4)
O5—H5B⋯O2ⁱⁱⁱ	0.87 (3)	1.79 (3)	2.644 (4)	167 (5)
O6—H6A⋯N5^iv	0.85 (4)	2.05 (4)	2.873 (5)	166 (3)
O6—H6B⋯O2^v	0.85 (3)	1.93 (4)	2.735 (4)	158 (4)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z; (iii) -x+2, -y+1, -z+1; (iv) -x, -y, -z+1; (v) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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 global, I. DOI: https://doi.org/10.1107/S1600536810046374/bg2368sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046374/bg2368Isup2.hkl

checkCIF report

Comment top

The attractive biological and pharmacological activity of the complexes with triazole caused a growing interest in the synthesis and characterization of new compounds with 1,2,4-triazole group (Huang et al., 2010a; Klingele & Brooker, 2003; Liu et al., 2009). We report here the synthesis and crystal structure of a new cobalt(II) complex [Co(C₇H₄NO₄)₂(C₁₂H₉N₅)₂(H₂O)₂].2H₂O, (I). The molecule of the title complex, (Fig. 1), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral coordination geometry, cis angles deviating from 90° by less than 4°. with Co—O bond length in the range 2.099–2.117 Å and Co—N bond length 2.155 Å. These bond distances compare well with the bond lenghths in the literatures (Dong, 2009; Du et al., 2007; Huang et al., 2010b).

The intermolecular packing is mainly further controlled by hydrogen bonds (O—H···O, O—H···N and N—H···O, Table 1) among the pyridine N atoms, the triazole N atoms, coordinated water molecules and lattice water molecules. As is well known, a water molecule has two hydrogen atoms and two lone-electron pairs, which enables it to participate in four hydrogen bonds in a tetrahedral configuration, but it also frequently shows a 3-coordinate configuration (Xie et al., 2009). In the title compound, the lattice water O6 also shows a 3-coordinate mode. Through these hydrogen bonds, the molecule is assembled into a three-dimensional supramolecular architecture, as shown in Fig. 2.

Related literature top

For background to triazole-containing compounds, see: Huang et al. (2010a); Klingele & Brooker, (2003); Liu et al. (2009). For related structures, see: Xie et al. (2009); Du et al. (2007); Huang et al. (2010b); Dong (2009).

Experimental top

A mixture of 3-nitrobenzoic acid (0.5 mmol, 0.084 g), CoCl₂.6H₂O (0.5 mmol, 0.112 g), NaOH (1 mmol, 0.040 g), 1H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (0.5 mmol, 0.112 g), and water (12 ml) were placed in a 23-ml Teflon-lined Parr bomb. The bomb was heated at 403 K for 3 d. The red block-shapped crystals were filtered off and washed with water and acetone (yield 65%, based on Co).

Structure description top

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. A view of the molecular structure of (I) with the atom-numbering scheme and 30% displacement ellipsoids (arbitrary spheres for the H atoms). Atoms with the suffix A are generated by the symmetry operation (-x + 2, -y + 1, -z + 1).
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dotted lines.

Diaquabis(3-nitrobenzoato-κO¹)bis[1H-5-(3-pyridyl)- 3-(4-pyridyl)-1H-1,2,4-triazole-κN⁵]cobalt(II) dihydrate top

Crystal data top

[Co(C₇H₄NO₄)₂(C₁₂H₉N₅)₂(H₂O)₂]·2H₂O	Z = 1
M_r = 909.70	F(000) = 469
Triclinic, P1	D_x = 1.504 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7080 (17) Å	Cell parameters from 2567 reflections
b = 9.850 (2) Å	θ = 1.5–25.0°
c = 12.488 (3) Å	µ = 0.51 mm⁻¹
α = 81.97 (3)°	T = 293 K
β = 85.74 (3)°	Block, red
γ = 71.36 (3)°	0.40 × 0.20 × 0.12 mm
V = 1004.5 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3518 independent reflections
Radiation source: fine-focus sealed tube	2642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
phi and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.835, T_max = 0.945	k = −11→11
5815 measured reflections	l = −14→12

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0646P)² + 0.2P] where P = (F_o² + 2F_c²)/3
3518 reflections	(Δ/σ)_max < 0.001
306 parameters	Δρ_max = 0.43 e Å⁻³
7 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

[Co(C₇H₄NO₄)₂(C₁₂H₉N₅)₂(H₂O)₂]·2H₂O	γ = 71.36 (3)°
M_r = 909.70	V = 1004.5 (4) Å³
Triclinic, P1	Z = 1
a = 8.7080 (17) Å	Mo Kα radiation
b = 9.850 (2) Å	µ = 0.51 mm⁻¹
c = 12.488 (3) Å	T = 293 K
α = 81.97 (3)°	0.40 × 0.20 × 0.12 mm
β = 85.74 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3518 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2642 reflections with I > 2σ(I)
T_min = 0.835, T_max = 0.945	R_int = 0.054
5815 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	7 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.43 e Å⁻³
3518 reflections	Δρ_min = −0.68 e Å⁻³
306 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	1.0000	0.5000	0.5000	0.0338 (2)
C1	0.8882 (5)	0.5642 (5)	0.2676 (3)	0.0402 (10)
C2	0.8606 (4)	0.5027 (4)	0.1685 (3)	0.0381 (9)
C3	0.9466 (5)	0.3630 (5)	0.1493 (3)	0.0559 (11)
H3A	1.0224	0.3042	0.1985	0.067*
C4	0.9203 (6)	0.3103 (5)	0.0571 (4)	0.0649 (13)
H4A	0.9803	0.2171	0.0440	0.078*
C5	0.8061 (6)	0.3954 (5)	−0.0147 (3)	0.0567 (12)
H5	0.7877	0.3608	−0.0765	0.068*
C6	0.7193 (5)	0.5333 (5)	0.0068 (3)	0.0429 (10)
C7	0.7445 (4)	0.5889 (4)	0.0965 (3)	0.0397 (9)
H7A	0.6849	0.6826	0.1087	0.048*
C8	0.7649 (4)	0.3339 (4)	0.4794 (3)	0.0364 (9)
H8A	0.8321	0.3094	0.4190	0.044*
C9	0.6321 (4)	0.2837 (4)	0.4974 (3)	0.0328 (8)
C10	0.5367 (4)	0.3156 (4)	0.5896 (3)	0.0382 (9)
H10A	0.4482	0.2822	0.6056	0.046*
C11	0.5751 (4)	0.3979 (4)	0.6575 (3)	0.0426 (10)
H11A	0.5120	0.4214	0.7197	0.051*
C12	0.7069 (4)	0.4449 (4)	0.6328 (3)	0.0372 (9)
H12A	0.7319	0.4998	0.6797	0.045*
C13	0.6008 (4)	0.1986 (4)	0.4186 (3)	0.0352 (9)
C14	0.4831 (4)	0.0989 (4)	0.3271 (3)	0.0361 (9)
C15	0.3665 (4)	0.0439 (4)	0.2817 (3)	0.0371 (9)
C16	0.2248 (4)	0.0407 (4)	0.3380 (3)	0.0424 (10)
H16A	0.2023	0.0715	0.4062	0.051*
C17	0.1174 (5)	−0.0086 (5)	0.2919 (3)	0.0524 (11)
H17A	0.0236	−0.0114	0.3316	0.063*
C18	0.2767 (5)	−0.0503 (5)	0.1408 (3)	0.0558 (12)
H18A	0.2958	−0.0813	0.0726	0.067*
C19	0.3924 (5)	−0.0047 (5)	0.1808 (3)	0.0483 (11)
H19A	0.4871	−0.0063	0.1405	0.058*
N1	0.8013 (3)	0.4154 (3)	0.5443 (2)	0.0338 (7)
N2	0.4570 (3)	0.1725 (3)	0.4117 (2)	0.0357 (7)
N3	0.7120 (3)	0.1453 (4)	0.3446 (2)	0.0440 (8)
N4	0.6339 (4)	0.0816 (4)	0.2875 (3)	0.0431 (8)
N5	0.1390 (4)	−0.0527 (4)	0.1940 (3)	0.0526 (9)
N6	0.5966 (5)	0.6266 (5)	−0.0687 (3)	0.0576 (10)
O1	0.9798 (3)	0.4763 (3)	0.33767 (19)	0.0411 (7)
O2	0.8182 (4)	0.6953 (3)	0.2740 (2)	0.0514 (7)
O3	0.5106 (4)	0.7427 (4)	−0.0446 (3)	0.0811 (11)
O4	0.5802 (4)	0.5808 (5)	−0.1515 (3)	0.0949 (13)
O5	1.1510 (3)	0.2825 (3)	0.5207 (2)	0.0410 (7)
O6	0.1644 (3)	0.0713 (3)	0.8675 (2)	0.0491 (7)
H5A	1.237 (3)	0.253 (4)	0.484 (3)	0.062 (14)*
H4	0.687 (4)	0.042 (4)	0.234 (2)	0.046 (11)*
H6A	0.073 (4)	0.061 (5)	0.861 (4)	0.098 (19)*
H5B	1.177 (6)	0.285 (7)	0.586 (2)	0.13 (3)*
H6B	0.164 (5)	0.155 (3)	0.839 (4)	0.084 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0306 (4)	0.0402 (5)	0.0342 (4)	−0.0127 (3)	0.0013 (3)	−0.0139 (3)
C1	0.046 (2)	0.054 (3)	0.030 (2)	−0.027 (2)	0.0032 (18)	−0.009 (2)
C2	0.041 (2)	0.044 (3)	0.0316 (19)	−0.016 (2)	0.0003 (17)	−0.0089 (18)
C3	0.062 (3)	0.055 (3)	0.045 (2)	−0.009 (3)	−0.011 (2)	−0.009 (2)
C4	0.079 (3)	0.048 (3)	0.063 (3)	−0.004 (3)	−0.002 (3)	−0.030 (2)
C5	0.070 (3)	0.061 (3)	0.043 (2)	−0.018 (3)	−0.005 (2)	−0.020 (2)
C6	0.049 (2)	0.052 (3)	0.032 (2)	−0.020 (2)	−0.0007 (18)	−0.0097 (19)
C7	0.044 (2)	0.041 (3)	0.037 (2)	−0.015 (2)	0.0036 (18)	−0.0104 (18)
C8	0.0296 (18)	0.042 (3)	0.037 (2)	−0.0077 (18)	0.0020 (16)	−0.0117 (18)
C9	0.0306 (18)	0.030 (2)	0.0369 (19)	−0.0078 (17)	−0.0032 (16)	−0.0058 (16)
C10	0.0325 (19)	0.045 (3)	0.040 (2)	−0.0159 (19)	0.0000 (16)	−0.0075 (18)
C11	0.037 (2)	0.054 (3)	0.039 (2)	−0.015 (2)	0.0055 (17)	−0.0135 (19)
C12	0.0339 (19)	0.042 (3)	0.037 (2)	−0.0103 (19)	−0.0002 (16)	−0.0146 (18)
C13	0.0309 (18)	0.036 (2)	0.041 (2)	−0.0124 (18)	0.0007 (16)	−0.0115 (17)
C14	0.0349 (19)	0.033 (2)	0.043 (2)	−0.0107 (18)	0.0012 (17)	−0.0117 (18)
C15	0.0341 (19)	0.035 (2)	0.042 (2)	−0.0078 (18)	−0.0064 (17)	−0.0082 (17)
C16	0.039 (2)	0.040 (3)	0.049 (2)	−0.0102 (19)	0.0005 (18)	−0.0144 (19)
C17	0.035 (2)	0.055 (3)	0.069 (3)	−0.013 (2)	−0.001 (2)	−0.018 (2)
C18	0.059 (3)	0.062 (3)	0.054 (3)	−0.024 (3)	−0.002 (2)	−0.021 (2)
C19	0.045 (2)	0.061 (3)	0.048 (2)	−0.024 (2)	0.0039 (19)	−0.020 (2)
N1	0.0301 (15)	0.037 (2)	0.0351 (16)	−0.0090 (14)	−0.0009 (13)	−0.0116 (14)
N2	0.0330 (15)	0.039 (2)	0.0385 (17)	−0.0128 (15)	0.0000 (13)	−0.0122 (14)
N3	0.0365 (17)	0.054 (2)	0.0498 (19)	−0.0192 (17)	0.0049 (15)	−0.0240 (17)
N4	0.0352 (17)	0.054 (2)	0.0458 (19)	−0.0159 (17)	0.0052 (16)	−0.0251 (17)
N5	0.0453 (19)	0.056 (3)	0.063 (2)	−0.0192 (19)	−0.0048 (18)	−0.0200 (19)
N6	0.066 (2)	0.071 (3)	0.039 (2)	−0.021 (2)	−0.0080 (18)	−0.011 (2)
O1	0.0430 (14)	0.0474 (19)	0.0355 (14)	−0.0159 (14)	−0.0033 (12)	−0.0087 (13)
O2	0.0730 (19)	0.042 (2)	0.0392 (15)	−0.0145 (17)	−0.0036 (14)	−0.0128 (13)
O3	0.095 (3)	0.073 (3)	0.065 (2)	−0.002 (2)	−0.0267 (19)	−0.0183 (19)
O4	0.102 (3)	0.118 (4)	0.056 (2)	−0.006 (3)	−0.0311 (19)	−0.038 (2)
O5	0.0344 (14)	0.0447 (19)	0.0428 (15)	−0.0066 (14)	0.0028 (13)	−0.0178 (13)
O6	0.0490 (17)	0.049 (2)	0.0525 (17)	−0.0168 (16)	−0.0001 (14)	−0.0135 (15)

Geometric parameters (Å, º) top

Co1—O1	2.099 (2)	C11—C12	1.369 (5)
Co1—O1ⁱ	2.099 (2)	C11—H11A	0.9300
Co1—O5ⁱ	2.117 (3)	C12—N1	1.335 (4)
Co1—O5	2.117 (3)	C12—H12A	0.9300
Co1—N1ⁱ	2.155 (3)	C13—N3	1.321 (4)
Co1—N1	2.155 (3)	C13—N2	1.367 (4)
C1—O2	1.251 (5)	C14—N2	1.329 (4)
C1—O1	1.266 (5)	C14—N4	1.335 (4)
C1—C2	1.518 (5)	C14—C15	1.473 (4)
C2—C3	1.385 (6)	C15—C16	1.381 (5)
C2—C7	1.387 (5)	C15—C19	1.387 (5)
C3—C4	1.389 (5)	C16—C17	1.375 (5)
C3—H3A	0.9300	C16—H16A	0.9300
C4—C5	1.373 (6)	C17—N5	1.335 (5)
C4—H4A	0.9300	C17—H17A	0.9300
C5—C6	1.379 (6)	C18—N5	1.332 (5)
C5—H5	0.9300	C18—C19	1.376 (5)
C6—C7	1.374 (5)	C18—H18A	0.9300
C6—N6	1.468 (5)	C19—H19A	0.9300
C7—H7A	0.9300	N3—N4	1.354 (4)
C8—N1	1.335 (4)	N4—H4	0.850 (18)
C8—C9	1.388 (4)	N6—O3	1.214 (5)
C8—H8A	0.9300	N6—O4	1.219 (4)
C9—C10	1.382 (5)	O5—H5A	0.84 (3)
C9—C13	1.470 (5)	O5—H5B	0.87 (3)
C10—C11	1.376 (5)	O6—H6A	0.85 (4)
C10—H10A	0.9300	O6—H6B	0.85 (3)

O1—Co1—O1ⁱ	180.00	C12—C11—C10	119.5 (3)
O1—Co1—O5ⁱ	92.14 (11)	C12—C11—H11A	120.2
O1ⁱ—Co1—O5ⁱ	87.86 (11)	C10—C11—H11A	120.2
O1—Co1—O5	87.86 (11)	N1—C12—C11	122.9 (3)
O1ⁱ—Co1—O5	92.14 (11)	N1—C12—H12A	118.6
O5ⁱ—Co1—O5	180.00	C11—C12—H12A	118.6
O1—Co1—N1ⁱ	90.32 (10)	N3—C13—N2	114.5 (3)
O1ⁱ—Co1—N1ⁱ	89.68 (10)	N3—C13—C9	121.0 (3)
O5ⁱ—Co1—N1ⁱ	86.07 (11)	N2—C13—C9	124.5 (3)
O5—Co1—N1ⁱ	93.93 (11)	N2—C14—N4	109.5 (3)
O1—Co1—N1	89.68 (10)	N2—C14—C15	126.5 (3)
O1ⁱ—Co1—N1	90.32 (10)	N4—C14—C15	124.0 (3)
O5ⁱ—Co1—N1	93.93 (11)	C16—C15—C19	117.3 (3)
O5—Co1—N1	86.07 (11)	C16—C15—C14	120.8 (3)
N1ⁱ—Co1—N1	180.00	C19—C15—C14	121.9 (3)
O2—C1—O1	125.7 (3)	C17—C16—C15	119.1 (3)
O2—C1—C2	118.0 (4)	C17—C16—H16A	120.5
O1—C1—C2	116.3 (4)	C15—C16—H16A	120.5
C3—C2—C7	119.6 (3)	N5—C17—C16	124.3 (4)
C3—C2—C1	121.7 (4)	N5—C17—H17A	117.8
C7—C2—C1	118.7 (4)	C16—C17—H17A	117.8
C2—C3—C4	120.4 (4)	N5—C18—C19	123.9 (4)
C2—C3—H3A	119.8	N5—C18—H18A	118.1
C4—C3—H3A	119.8	C19—C18—H18A	118.1
C5—C4—C3	120.2 (4)	C18—C19—C15	119.4 (3)
C5—C4—H4A	119.9	C18—C19—H19A	120.3
C3—C4—H4A	119.9	C15—C19—H19A	120.3
C4—C5—C6	118.6 (4)	C8—N1—C12	117.4 (3)
C4—C5—H5	120.7	C8—N1—Co1	119.6 (2)
C6—C5—H5	120.7	C12—N1—Co1	123.0 (2)
C7—C6—C5	122.4 (4)	C14—N2—C13	102.9 (3)
C7—C6—N6	117.8 (4)	C13—N3—N4	102.2 (3)
C5—C6—N6	119.8 (4)	C14—N4—N3	110.9 (3)
C6—C7—C2	118.7 (4)	C14—N4—H4	133 (2)
C6—C7—H7A	120.6	N3—N4—H4	116 (2)
C2—C7—H7A	120.6	C18—N5—C17	116.0 (3)
N1—C8—C9	123.5 (3)	O3—N6—O4	122.5 (4)
N1—C8—H8A	118.3	O3—N6—C6	119.4 (3)
C9—C8—H8A	118.3	O4—N6—C6	118.1 (4)
C10—C9—C8	117.8 (3)	C1—O1—Co1	128.0 (2)
C10—C9—C13	123.3 (3)	Co1—O5—H5A	123 (3)
C8—C9—C13	118.8 (3)	Co1—O5—H5B	95 (4)
C11—C10—C9	118.8 (3)	H5A—O5—H5B	108 (3)
C11—C10—H10A	120.6	H6A—O6—H6B	110 (3)
C9—C10—H10A	120.6

O2—C1—C2—C3	172.9 (3)	C9—C8—N1—C12	2.4 (5)
O1—C1—C2—C3	−7.8 (5)	C9—C8—N1—Co1	−175.1 (3)
O2—C1—C2—C7	−8.0 (5)	C11—C12—N1—C8	−1.3 (6)
O1—C1—C2—C7	171.3 (3)	C11—C12—N1—Co1	176.1 (3)
C7—C2—C3—C4	1.7 (6)	O1—Co1—N1—C8	22.1 (3)
C1—C2—C3—C4	−179.1 (3)	O1ⁱ—Co1—N1—C8	−157.9 (3)
C2—C3—C4—C5	−1.4 (7)	O5ⁱ—Co1—N1—C8	114.2 (3)
C3—C4—C5—C6	0.2 (7)	O5—Co1—N1—C8	−65.8 (3)
C4—C5—C6—C7	0.8 (6)	O1—Co1—N1—C12	−155.3 (3)
C4—C5—C6—N6	179.9 (4)	O1ⁱ—Co1—N1—C12	24.7 (3)
C5—C6—C7—C2	−0.5 (5)	O5ⁱ—Co1—N1—C12	−63.2 (3)
N6—C6—C7—C2	−179.7 (3)	O5—Co1—N1—C12	116.8 (3)
C3—C2—C7—C6	−0.7 (5)	N4—C14—N2—C13	0.6 (4)
C1—C2—C7—C6	−179.9 (3)	C15—C14—N2—C13	−179.1 (4)
N1—C8—C9—C10	−2.6 (6)	N3—C13—N2—C14	−0.4 (4)
N1—C8—C9—C13	178.0 (3)	C9—C13—N2—C14	177.1 (4)
C8—C9—C10—C11	1.5 (6)	N2—C13—N3—N4	0.0 (4)
C13—C9—C10—C11	−179.1 (4)	C9—C13—N3—N4	−177.6 (3)
C9—C10—C11—C12	−0.6 (6)	N2—C14—N4—N3	−0.7 (5)
C10—C11—C12—N1	0.5 (6)	C15—C14—N4—N3	179.1 (3)
C10—C9—C13—N3	−165.6 (4)	C13—N3—N4—C14	0.4 (4)
C8—C9—C13—N3	13.7 (6)	C19—C18—N5—C17	−0.6 (7)
C10—C9—C13—N2	17.1 (6)	C16—C17—N5—C18	1.5 (7)
C8—C9—C13—N2	−163.6 (4)	C7—C6—N6—O3	−7.5 (5)
N2—C14—C15—C16	−12.9 (6)	C5—C6—N6—O3	173.4 (4)
N4—C14—C15—C16	167.4 (4)	C7—C6—N6—O4	175.9 (4)
N2—C14—C15—C19	166.2 (4)	C5—C6—N6—O4	−3.3 (5)
N4—C14—C15—C19	−13.6 (6)	O2—C1—O1—Co1	17.2 (5)
C19—C15—C16—C17	−0.4 (6)	C2—C1—O1—Co1	−162.0 (2)
C14—C15—C16—C17	178.7 (4)	O5ⁱ—Co1—O1—C1	−7.9 (3)
C15—C16—C17—N5	−1.0 (7)	O5—Co1—O1—C1	172.1 (3)
N5—C18—C19—C15	−0.8 (7)	N1ⁱ—Co1—O1—C1	−94.0 (3)
C16—C15—C19—C18	1.3 (6)	N1—Co1—O1—C1	86.0 (3)
C14—C15—C19—C18	−177.8 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O6ⁱⁱ	0.85 (3)	1.94 (3)	2.778 (5)	169 (3)
O5—H5A···N2ⁱⁱⁱ	0.84 (3)	2.02 (3)	2.856 (4)	174 (4)
O5—H5B···O2ⁱ	0.87 (3)	1.79 (3)	2.644 (4)	167 (5)
O6—H6A···N5^iv	0.85 (4)	2.05 (4)	2.873 (5)	166 (3)
O6—H6B···O2^v	0.85 (3)	1.93 (4)	2.735 (4)	158 (4)

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

Experimental details

Crystal data
Chemical formula	[Co(C₇H₄NO₄)₂(C₁₂H₉N₅)₂(H₂O)₂]·2H₂O
M_r	909.70
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.7080 (17), 9.850 (2), 12.488 (3)
α, β, γ (°)	81.97 (3), 85.74 (3), 71.36 (3)
V (Å³)	1004.5 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.40 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.835, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	5815, 3518, 2642
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.146, 1.03
No. of reflections	3518
No. of parameters	306
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.68

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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
N4—H4···O6ⁱ	0.85 (3)	1.94 (3)	2.778 (5)	169 (3)
O5—H5A···N2ⁱⁱ	0.84 (3)	2.02 (3)	2.856 (4)	174 (4)
O5—H5B···O2ⁱⁱⁱ	0.87 (3)	1.79 (3)	2.644 (4)	167 (5)
O6—H6A···N5^iv	0.85 (4)	2.05 (4)	2.873 (5)	166 (3)
O6—H6B···O2^v	0.85 (3)	1.93 (4)	2.735 (4)	158 (4)

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

Acknowledgements

We acknowledge financial support from the Science & Technology Foundation of Shaoyang, Hunan, China (grant No. J0966), the Scientific Research Foundation of Hunan Provincial Education Department (grant No. 10C0297) and the Foundation of Shaoyang Medical College, China (grant No. XK200804)

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dong, L. Y. (2009). Acta Cryst. E65, m487–m488. Web of Science CSD CrossRef IUCr Journals Google Scholar
Du, M., Jiang, X.-J. & Zhao, X.-J. (2007). Inorg. Chem. 46, 3984–3995. Web of Science CSD CrossRef PubMed CAS Google Scholar
Huang, F.-P., Tian, J.-L., Gu, W., Yan, S.-P., Liu, X., Liao, D.-Z. & Cheng, P. (2010a). Cryst. Growth Des. 10, 1145–1154. Web of Science CSD CrossRef CAS Google Scholar
Huang, F.-P., Tian, J.-L., Li, D.-D., Chen, G.-J., Gu, W., Yan, S.-P., Liu, X., Liao, D.-Z. & Cheng, P. (2010b). Inorg. Chem. 49, 2525–2529. Web of Science CSD CrossRef CAS PubMed Google Scholar
Klingele, M. H. & Brooker, S. (2003). Coord. Chem. Rev. 241, 119–132. Web of Science CrossRef CAS Google Scholar
Liu, T.-L. & Zhang, Y.-L. (2009). Acta Cryst. E65, m913. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, X.-F., Chen, S.-P., Xia, Z.-Q. & Gao, S.-L. (2009). Polyhedron, 28, 679–688. Web of Science CSD CrossRef CAS Google Scholar

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