Aqua­[2,2′-(propane-1,3-di­yl)bis­(5-car­boxy-1H-imidazole-4-carboxyl­ato)-κ4N3,O4:N3′,O4′](pyridine-κN)cobalt(II)–4,4′-bipyridine (1/1)

Liu, W.; Li, X.

doi:10.1107/S1600536812029856

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1109-m1110

https://doi.org/10.1107/S1600536812029856

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Aqua[2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato)-κ⁴N³,O⁴:N^3′,O^4′](pyridine-κN)cobalt(II)–4,4′-bipyridine (1/1)

Wei Liu ^a ^* and Xia Li ^a

^aDepartment of Chemistry and Chemical Engineering, Henan University of Urban Construction, Pingdingshan, Henan 467044, People's Republic of China
^*Correspondence e-mail: liuwei@hncj.edu.cn

(Received 5 June 2012; accepted 30 June 2012; online 25 July 2012)

In the title compound, [Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂, the asymmetric unit comprises half a Co^II complex located on a mirror plane and half a cocrystallized molecule of 4,4′-bipyridine located on an inversion center. The Co^II ion is six coordinate, with distorted octahedral geometry, ligated by two N atoms and two O atoms from a 2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylate) dianion, one N atom from a pyridine molecule and one coordinating water molecule. The Co—O bond lengths range from 2.076 (2) to 2.1441 (15) Å, while the Co—N bond lengths are 2.138 (3) and 2.1515 (17) Å. A two-dimensional network of N—H⋯O and O—H⋯N hydrogen bonds stabilizes the crystal packing. There are π–π interactions between the bipyridine and imidazole rings [centroid–centroid distance = 3.7694 (4) Å]. The propane-1,3-diyl group is disordered over two conformations, with refined occupancies of 0.755 (8) and 0.245 (8).

Related literature

For complexes based on substituted 4,5-imidazoledicarboxylic acids, see: Zhu et al. (2010 , 2011 ); Lu et al. (2010 ); Song et al. (2010 ); Zhang et al. (2010 ); Wang et al. (2008 ); Feng et al. (2010 ); Liu et al. (2010 ); Zheng et al. (2011 ); Li et al. (2009 , 2010 ).

Experimental

Crystal data

[Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂
M_r = 661.47
Monoclinic, P 2₁ /m
a = 7.9733 (10) Å
b = 20.738 (3) Å
c = 8.2987 (11) Å
β = 91.350 (2)°
V = 1371.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.862, T_max = 0.927
11480 measured reflections
3443 independent reflections
2633 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.105
S = 1.05
3443 reflections
219 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.65	2.473 (2)	177
O5—H1W⋯N4ⁱ	0.82	1.95	2.727 (3)	157
N2—H2⋯O4ⁱⁱ	0.86	1.93	2.763 (3)	162
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+1]$ ; (ii) -x+2, -y+1, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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: https://doi.org/10.1107/S1600536812029856/pk2422sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029856/pk2422Isup2.hkl

checkCIF report

Comment top

It is well known that aromatic polycarboxylates, especially the N-heterocyclic carboxylates, are excellent candidates for preparing novel MOFs, because of their versatile coordination modes and potential hydrogen-bonding donors and acceptors. Recently, 4,5-imidazoledicarboxylic acid (Zhu et al., 2010; Lu et al., 2010) and its 2-position substituent derivatives, such as 2-methyl-1H-imidazole-4,5-dicarboxylic acid (Song et al., 2010), 2-ethyl-1H-imidazole-4,5-dicarboxylic acid (Zhang et al., 2010; Wang et al., 2008), 2-propyl-1H-imidazole-4,5-dicarboxylic acid (Feng et al., 2010; Liu et al., 2010), 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (Zheng et al., 2011), 2-phenyl-1H-imidazole-4,5-dicarboxylic acid (Zhu et al., 2011) and 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid (Li et al., 2009; Li et al., 2010) have attracted great attention in the field of coordination chemistry. Now, our group has strong interest in adopting another imidazole dicarboxylate ligand, 1,3-bis-(1H-imidazole-4,5-dicarboxylate acid) propane to prepare various coordination compounds.

As shown in Fig. 1, the molecule is a discrete neutral monomer, in which the asymmetric unit comprises half a CoII complex located on a mirror plane and half a co-crystallized molecule of 4,4'-bipyridine located on an inversion center. The Co^II ion is six coordinate and has a distorted octahedral geometry. It is ligated by two nitrogen atoms and two oxygen atoms from a 1,3-bis-(1H-imidazole-4,5-dicarboxylate) propane dianion, one nitrogen atom from a pyridine molecule and one oxygen atom from a coordinated water molecule. The Co—O distances range from 2.076 (2) to 2.1441 (15) Å, while Co—N distances are 2.138 (3) and 2.1515 (17) Å, respectively. A two-dimensional network of N—H···O and O—H···N hydrogen bonds help to stabilize the crystal packing. Aromatic π-π interactions between bipyridine rings and imidazole rings [centroid—centroid distance = 3.7694 (4) Å] are also observed.

Related literature top

For complexes based on substituted 4,5-imidazoledicarboxylic acids, see: Zhu et al. (2010, 2011); Lu et al. (2010); Song et al. (2010); Zhang et al. (2010); Wang et al. (2008); Feng et al. (2010); Liu et al. (2010); Zheng et al. (2011); Li et al. (2009, 2010).

Experimental top

A mixture of cobalt chloride hexahydrate (0.0238 g, 0.1 mmol), 1,3-bis-(1H-imidazole-4,5-dicarboxylate acid) propane (0.0352 g, 0.1 mmol), 4,4'-bipyridine (0.0198 g, 0.1 mmol), pyridine (0.8 ml) and H₂O (10 ml) was sealed in a Teflon-lined stainless autoclave and heated at 413 K for 3 days. The bomb was allowed to cool to room temperature gradually and red prismatic crystals were obtained.

Structure description top

For complexes based on substituted 4,5-imidazoledicarboxylic acids, see: Zhu et al. (2010, 2011); Lu et al. (2010); Song et al. (2010); Zhang et al. (2010); Wang et al. (2008); Feng et al. (2010); Liu et al. (2010); Zheng et al. (2011); Li et al. (2009, 2010).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. Unlabelled atoms are related to labelled atoms by the symmetry operations (x, -y+1/2, z for CoII complex; 1-x, 1-y, 1-z for 4,4-bipy).

Aqua[2,2'-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato)- κ⁴N³,O⁴:N^3',O^4'](pyridine- κN)cobalt(II)–4,4'-bipyridine (1/1) top

Crystal data top

[Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂	F(000) = 680
M_r = 661.47	D_x = 1.601 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2701 reflections
a = 7.9733 (10) Å	θ = 2.6–28.3°
b = 20.738 (3) Å	µ = 0.70 mm⁻¹
c = 8.2987 (11) Å	T = 296 K
β = 91.350 (2)°	Prismatic, red
V = 1371.8 (3) Å³	0.22 × 0.18 × 0.11 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	3443 independent reflections
Radiation source: fine-focus sealed tube	2633 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
T_min = 0.862, T_max = 0.927	k = −27→27
11480 measured reflections	l = −11→10

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0442P)² + 0.5516P] where P = (F_o² + 2F_c²)/3
3443 reflections	(Δ/σ)_max < 0.001
219 parameters	Δρ_max = 0.43 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂	V = 1371.8 (3) Å³
M_r = 661.47	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.9733 (10) Å	µ = 0.70 mm⁻¹
b = 20.738 (3) Å	T = 296 K
c = 8.2987 (11) Å	0.22 × 0.18 × 0.11 mm
β = 91.350 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3443 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2633 reflections with I > 2σ(I)
T_min = 0.862, T_max = 0.927	R_int = 0.033
11480 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	Δρ_max = 0.43 e Å⁻³
3443 reflections	Δρ_min = −0.34 e Å⁻³
219 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	Occ. (<1)
Co1	1.06603 (5)	0.2500	0.45178 (5)	0.03122 (13)
O1	1.1510 (2)	0.32701 (7)	0.60553 (18)	0.0383 (4)
O2	1.2252 (2)	0.43073 (8)	0.6011 (2)	0.0522 (5)
O3	1.2037 (3)	0.52310 (8)	0.4133 (2)	0.0529 (5)
H3	1.2128	0.4918	0.4734	0.079*
O4	1.1130 (3)	0.54174 (8)	0.1645 (2)	0.0529 (5)
O5	1.3034 (3)	0.2500	0.3543 (3)	0.0427 (6)
H1W	1.3294	0.2130	0.3301	0.064*	0.50
N1	1.0110 (2)	0.33325 (8)	0.3051 (2)	0.0333 (4)
N2	0.9918 (2)	0.41425 (8)	0.1356 (2)	0.0376 (4)
H2	0.9680	0.4358	0.0494	0.045*
N3	0.8291 (3)	0.2500	0.5671 (3)	0.0362 (6)
N4	0.5482 (3)	0.64535 (11)	0.7813 (3)	0.0581 (6)
C1	1.0812 (3)	0.38718 (10)	0.3751 (3)	0.0323 (5)
C2	1.0707 (3)	0.43808 (10)	0.2707 (3)	0.0339 (5)
C3	0.9574 (3)	0.35140 (10)	0.1597 (3)	0.0391 (5)
C4	1.1577 (3)	0.38108 (10)	0.5396 (3)	0.0352 (5)
C5	1.1307 (3)	0.50565 (11)	0.2790 (3)	0.0389 (5)
C6	0.8845 (10)	0.3117 (3)	0.0277 (8)	0.077 (2)	0.755 (8)
H6A	0.9736	0.2990	−0.0432	0.092*	0.755 (8)
H6B	0.8060	0.3380	−0.0347	0.092*	0.755 (8)
C7	0.7919 (6)	0.2500	0.0846 (6)	0.0417 (13)	0.755 (8)
H7A	0.6779	0.2500	0.0411	0.050*	0.755 (8)
H7B	0.7867	0.2500	0.2012	0.050*	0.755 (8)
C8	0.7494 (3)	0.30506 (12)	0.6012 (3)	0.0432 (6)
H8	0.8032	0.3439	0.5807	0.052*
C9	0.5915 (3)	0.30676 (14)	0.6651 (3)	0.0531 (7)
H9	0.5404	0.3460	0.6869	0.064*
C10	0.5108 (5)	0.2500	0.6959 (5)	0.0564 (10)
H10	0.4033	0.2500	0.7371	0.068*
C11	0.6117 (4)	0.63819 (13)	0.9295 (4)	0.0565 (7)
H11	0.6701	0.6727	0.9751	0.068*
C12	0.5967 (3)	0.58259 (12)	1.0209 (3)	0.0467 (6)
H12	0.6442	0.5802	1.1241	0.056*
C13	0.5101 (3)	0.53088 (11)	0.9558 (3)	0.0378 (5)
C14	0.4429 (4)	0.53878 (13)	0.8010 (4)	0.0604 (8)
H14	0.3829	0.5054	0.7520	0.072*
C15	0.4649 (4)	0.59541 (15)	0.7211 (4)	0.0681 (9)
H15	0.4183	0.5992	0.6177	0.082*
C7'	0.9726 (4)	0.25000 (15)	−0.0032 (4)	0.048 (4)*	0.245 (8)
H7'1	0.9962	0.2500	−0.1173	0.057*	0.245 (8)
H7'2	1.0762	0.2500	0.0604	0.057*	0.245 (8)
C6'	0.841 (2)	0.3086 (7)	0.049 (2)	0.034 (3)*	0.245 (8)
H6'1	0.8001	0.3323	−0.0446	0.041*	0.245 (8)
H6'2	0.7470	0.2917	0.1074	0.041*	0.245 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0391 (2)	0.0229 (2)	0.0313 (2)	0.000	−0.00719 (16)	0.000
O1	0.0514 (10)	0.0286 (8)	0.0344 (9)	−0.0005 (7)	−0.0105 (7)	−0.0007 (7)
O2	0.0784 (13)	0.0338 (9)	0.0434 (10)	−0.0142 (8)	−0.0229 (9)	−0.0026 (7)
O3	0.0842 (14)	0.0277 (9)	0.0458 (11)	−0.0100 (8)	−0.0171 (9)	−0.0005 (7)
O4	0.0819 (13)	0.0294 (9)	0.0466 (11)	−0.0079 (8)	−0.0133 (9)	0.0070 (8)
O5	0.0451 (13)	0.0284 (11)	0.0549 (15)	0.000	0.0038 (11)	0.000
N1	0.0417 (10)	0.0235 (8)	0.0342 (10)	−0.0004 (7)	−0.0091 (8)	−0.0011 (7)
N2	0.0518 (11)	0.0257 (9)	0.0349 (10)	−0.0025 (8)	−0.0109 (8)	0.0041 (8)
N3	0.0409 (15)	0.0319 (14)	0.0356 (15)	0.000	−0.0052 (11)	0.000
N4	0.0629 (15)	0.0422 (13)	0.0696 (17)	0.0037 (11)	0.0090 (12)	0.0145 (11)
C1	0.0381 (11)	0.0237 (10)	0.0349 (12)	0.0008 (9)	−0.0056 (9)	−0.0030 (8)
C2	0.0414 (12)	0.0268 (10)	0.0333 (12)	0.0016 (9)	−0.0040 (9)	−0.0017 (9)
C3	0.0533 (14)	0.0280 (11)	0.0354 (13)	−0.0024 (10)	−0.0111 (10)	0.0007 (9)
C4	0.0427 (12)	0.0288 (11)	0.0336 (12)	0.0000 (9)	−0.0074 (9)	−0.0031 (9)
C5	0.0497 (14)	0.0275 (11)	0.0394 (13)	−0.0007 (10)	−0.0042 (10)	−0.0029 (10)
C6	0.127 (6)	0.053 (3)	0.049 (3)	−0.053 (3)	−0.024 (4)	0.005 (2)
C7	0.049 (3)	0.033 (2)	0.042 (3)	0.000	−0.020 (2)	0.000
C8	0.0486 (14)	0.0405 (13)	0.0402 (14)	0.0048 (11)	−0.0044 (10)	0.0007 (11)
C9	0.0528 (16)	0.0609 (18)	0.0456 (15)	0.0178 (13)	−0.0006 (12)	0.0010 (13)
C10	0.043 (2)	0.084 (3)	0.042 (2)	0.000	−0.0003 (16)	0.000
C11	0.0655 (18)	0.0355 (14)	0.069 (2)	−0.0091 (12)	0.0129 (15)	−0.0069 (13)
C12	0.0578 (16)	0.0388 (13)	0.0433 (14)	−0.0068 (11)	0.0000 (11)	−0.0039 (11)
C13	0.0384 (12)	0.0330 (12)	0.0419 (13)	−0.0018 (9)	−0.0019 (10)	0.0015 (10)
C14	0.076 (2)	0.0456 (15)	0.0580 (18)	−0.0175 (14)	−0.0252 (15)	0.0147 (13)
C15	0.083 (2)	0.0592 (19)	0.061 (2)	−0.0065 (16)	−0.0203 (16)	0.0207 (16)

Geometric parameters (Å, º) top

Co1—O5	2.076 (2)	C6—H6A	0.9700
Co1—N3	2.138 (3)	C6—H6B	0.9700
Co1—O1	2.1441 (15)	C7—C6ⁱ	1.557 (6)
Co1—O1ⁱ	2.1441 (15)	C7—H7A	0.9700
Co1—N1ⁱ	2.1515 (17)	C7—H7B	0.9700
Co1—N1	2.1515 (17)	C8—C9	1.378 (4)
O1—C4	1.249 (3)	C8—H8	0.9300
O2—C4	1.264 (3)	C9—C10	1.369 (3)
O3—C5	1.297 (3)	C9—H9	0.9300
O3—H3	0.8200	C10—C9ⁱ	1.369 (3)
O4—C5	1.215 (3)	C10—H10	0.9300
O5—H1W	0.8200	C11—C12	1.387 (4)
N1—C3	1.326 (3)	C11—H11	0.9300
N1—C1	1.374 (3)	C12—C13	1.378 (3)
N2—C3	1.348 (3)	C12—H12	0.9300
N2—C2	1.366 (3)	C13—C14	1.390 (3)
N2—H2	0.8600	C13—C13ⁱⁱ	1.486 (4)
N3—C8	1.340 (3)	C14—C15	1.362 (4)
N3—C8ⁱ	1.340 (3)	C14—H14	0.9300
N4—C15	1.322 (4)	C15—H15	0.9300
N4—C11	1.327 (4)	C7'—C6'ⁱ	1.667 (13)
C1—C2	1.367 (3)	C7'—C6'	1.667 (13)
C1—C4	1.487 (3)	C7'—H7'1	0.9700
C2—C5	1.482 (3)	C7'—H7'2	0.9700
C3—C6	1.478 (6)	C6'—H6'1	0.9700
C3—C6'	1.565 (19)	C6'—H6'2	0.9700
C6—C7	1.557 (6)

O5—Co1—N3	176.35 (10)	C3—C6—H6A	108.6
O5—Co1—O1	87.35 (7)	C7—C6—H6A	108.6
N3—Co1—O1	90.22 (7)	C3—C6—H6B	108.6
O5—Co1—O1ⁱ	87.35 (7)	C7—C6—H6B	108.6
N3—Co1—O1ⁱ	90.22 (7)	H6A—C6—H6B	107.6
O1—Co1—O1ⁱ	96.30 (8)	C6—C7—C6ⁱ	110.7 (7)
O5—Co1—N1ⁱ	87.43 (7)	C6—C7—H7A	109.5
N3—Co1—N1ⁱ	94.74 (7)	C6ⁱ—C7—H7A	109.5
O1—Co1—N1ⁱ	172.62 (6)	C6—C7—H7B	109.5
O1ⁱ—Co1—N1ⁱ	78.25 (6)	C6ⁱ—C7—H7B	109.5
O5—Co1—N1	87.43 (7)	H7A—C7—H7B	108.1
N3—Co1—N1	94.74 (7)	N3—C8—C9	123.0 (2)
O1—Co1—N1	78.25 (6)	N3—C8—H8	118.5
O1ⁱ—Co1—N1	172.62 (6)	C9—C8—H8	118.5
N1ⁱ—Co1—N1	106.72 (9)	C10—C9—C8	119.2 (3)
C4—O1—Co1	115.09 (14)	C10—C9—H9	120.4
C5—O3—H3	109.5	C8—C9—H9	120.4
Co1—O5—H1W	109.5	C9—C10—C9ⁱ	118.7 (4)
C3—N1—C1	105.87 (18)	C9—C10—H10	120.7
C3—N1—Co1	143.14 (15)	C9ⁱ—C10—H10	120.7
C1—N1—Co1	109.78 (13)	N4—C11—C12	124.3 (3)
C3—N2—C2	108.63 (18)	N4—C11—H11	117.8
C3—N2—H2	125.7	C12—C11—H11	117.8
C2—N2—H2	125.7	C13—C12—C11	118.8 (3)
C8—N3—C8ⁱ	116.9 (3)	C13—C12—H12	120.6
C8—N3—Co1	121.51 (15)	C11—C12—H12	120.6
C8ⁱ—N3—Co1	121.51 (15)	C12—C13—C14	116.7 (2)
C15—N4—C11	116.1 (2)	C12—C13—C13ⁱⁱ	122.5 (3)
C2—C1—N1	110.02 (19)	C14—C13—C13ⁱⁱ	120.9 (3)
C2—C1—C4	131.70 (19)	C15—C14—C13	120.0 (3)
N1—C1—C4	118.24 (18)	C15—C14—H14	120.0
N2—C2—C1	105.15 (18)	C13—C14—H14	120.0
N2—C2—C5	121.5 (2)	N4—C15—C14	124.1 (3)
C1—C2—C5	133.3 (2)	N4—C15—H15	118.0
N1—C3—N2	110.33 (19)	C14—C15—H15	118.0
N1—C3—C6	129.0 (3)	C6'ⁱ—C7'—C6'	93.5 (12)
N2—C3—C6	120.4 (3)	C6'ⁱ—C7'—H7'1	113.0
N1—C3—C6'	123.2 (7)	C6'—C7'—H7'1	113.0
N2—C3—C6'	125.5 (6)	C6'ⁱ—C7'—H7'2	113.0
C6—C3—C6'	14.6 (7)	C6'—C7'—H7'2	113.0
O1—C4—O2	125.2 (2)	H7'1—C7'—H7'2	110.4
O1—C4—C1	117.23 (18)	C3—C6'—C7'	101.5 (9)
O2—C4—C1	117.59 (19)	C3—C6'—H6'1	111.5
O4—C5—O3	122.8 (2)	C7'—C6'—H6'1	111.5
O4—C5—C2	121.0 (2)	C3—C6'—H6'2	111.5
O3—C5—C2	116.2 (2)	C7'—C6'—H6'2	111.5
C3—C6—C7	114.5 (5)	H6'1—C6'—H6'2	109.3

O5—Co1—O1—C4	77.25 (17)	C1—N1—C3—C6	174.5 (5)
N3—Co1—O1—C4	−105.47 (17)	Co1—N1—C3—C6	9.5 (6)
O1ⁱ—Co1—O1—C4	164.28 (13)	C1—N1—C3—C6'	−169.0 (6)
N1ⁱ—Co1—O1—C4	122.3 (5)	Co1—N1—C3—C6'	26.1 (7)
N1—Co1—O1—C4	−10.68 (16)	C2—N2—C3—N1	−0.1 (3)
O5—Co1—N1—C3	86.0 (3)	C2—N2—C3—C6	−174.9 (4)
N3—Co1—N1—C3	−96.9 (3)	C2—N2—C3—C6'	168.9 (7)
O1—Co1—N1—C3	173.8 (3)	Co1—O1—C4—O2	−169.8 (2)
O1ⁱ—Co1—N1—C3	131.0 (5)	Co1—O1—C4—C1	9.7 (3)
N1ⁱ—Co1—N1—C3	−0.5 (3)	C2—C1—C4—O1	−178.4 (2)
O5—Co1—N1—C1	−78.58 (15)	N1—C1—C4—O1	−1.1 (3)
N3—Co1—N1—C1	98.49 (15)	C2—C1—C4—O2	1.1 (4)
O1—Co1—N1—C1	9.25 (14)	N1—C1—C4—O2	178.5 (2)
O1ⁱ—Co1—N1—C1	−33.6 (6)	N2—C2—C5—O4	−0.9 (4)
N1ⁱ—Co1—N1—C1	−165.12 (11)	C1—C2—C5—O4	176.1 (2)
O5—Co1—N3—C8	91.7 (2)	N2—C2—C5—O3	180.0 (2)
O1—Co1—N3—C8	43.6 (2)	C1—C2—C5—O3	−3.1 (4)
O1ⁱ—Co1—N3—C8	139.9 (2)	N1—C3—C6—C7	27.9 (8)
N1ⁱ—Co1—N3—C8	−141.9 (2)	N2—C3—C6—C7	−158.5 (4)
N1—Co1—N3—C8	−34.6 (2)	C6'—C3—C6—C7	−44 (3)
O5—Co1—N3—C8ⁱ	−91.7 (2)	C3—C6—C7—C6ⁱ	−114.7 (5)
O1—Co1—N3—C8ⁱ	−139.9 (2)	C8ⁱ—N3—C8—C9	−1.4 (5)
O1ⁱ—Co1—N3—C8ⁱ	−43.6 (2)	Co1—N3—C8—C9	175.34 (19)
N1ⁱ—Co1—N3—C8ⁱ	34.6 (2)	N3—C8—C9—C10	0.1 (4)
N1—Co1—N3—C8ⁱ	141.9 (2)	C8—C9—C10—C9ⁱ	1.3 (5)
C3—N1—C1—C2	−0.4 (3)	C15—N4—C11—C12	0.6 (4)
Co1—N1—C1—C2	170.09 (15)	N4—C11—C12—C13	−0.2 (4)
C3—N1—C1—C4	−178.2 (2)	C11—C12—C13—C14	−0.2 (4)
Co1—N1—C1—C4	−7.8 (2)	C11—C12—C13—C13ⁱⁱ	179.1 (3)
C3—N2—C2—C1	−0.1 (3)	C12—C13—C14—C15	0.3 (4)
C3—N2—C2—C5	177.6 (2)	C13ⁱⁱ—C13—C14—C15	−179.0 (3)
N1—C1—C2—N2	0.3 (2)	C11—N4—C15—C14	−0.4 (5)
C4—C1—C2—N2	177.8 (2)	C13—C14—C15—N4	0.0 (5)
N1—C1—C2—C5	−177.0 (2)	N1—C3—C6'—C7'	−70.7 (10)
C4—C1—C2—C5	0.5 (4)	N2—C3—C6'—C7'	121.7 (6)
C1—N1—C3—N2	0.3 (3)	C6—C3—C6'—C7'	48 (2)
Co1—N1—C3—N2	−164.64 (19)	C6'ⁱ—C7'—C6'—C3	129.0 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.65	2.473 (2)	177
O5—H1W···N4ⁱⁱⁱ	0.82	1.95	2.727 (3)	157
N2—H2···O4^iv	0.86	1.93	2.763 (3)	162

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂
M_r	661.47
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	296
a, b, c (Å)	7.9733 (10), 20.738 (3), 8.2987 (11)
β (°)	91.350 (2)
V (Å³)	1371.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.22 × 0.18 × 0.11

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.862, 0.927
No. of measured, independent and observed [I > 2σ(I)] reflections	11480, 3443, 2633
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.105, 1.05
No. of reflections	3443
No. of parameters	219
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.34

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
O3—H3···O2	0.82	1.65	2.473 (2)	177.1
O5—H1W···N4ⁱ	0.82	1.95	2.727 (3)	156.8
N2—H2···O4ⁱⁱ	0.86	1.93	2.763 (3)	162.1

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

Acknowledgements

We gratefully acknowledge financial support by the Foundation of Henan Key Science and Technology Research (grant Nos. 122102210414 and 122102210415), the Foundation of Henan Educational Committee (grant Nos. 2010A150003 and 2011B150001), and the Foundation of Henan University of Urban Construction (grant Nos. 2010JYB007 and 2010JYB008).

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