(2,2′-Bipyridine-6,6′-dicarboxyl­ato-κ3N,N′,O6)(6′-carb­oxy-2,2′-bipyridine-6-carboxyl­ato-κ3N,N′,O6)cobalt(III)

Wang, H.; Gu, X.; Zhang, B.; Su, H.

doi:10.1107/S1600536812009816

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m411-m412

doi:10.1107/S1600536812009816

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(2,2′-Bipyridine-6,6′-dicarboxylato-κ³N,N′,O⁶)(6′-carboxy-2,2′-bipyridine-6-carboxylato-κ³N,N′,O⁶)cobalt(III)

Huimin Wang,^a Xiaojun Gu,^b Bingbing Zhang ^a and Haiquan Su ^a,^b ^*

^aCollege of Life Sciences, Inner Mongolia University, Hohhot 010021, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, People's Republic of China
^*Correspondence e-mail: haiquansu@yahoo.com

(Received 2 March 2012; accepted 6 March 2012; online 14 March 2012)

The Co^III atom in the title compound, [Co(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)], is six-coordinated in a distorted octahedral geometry by four N atoms and two O atoms of the chelating 2,2′-bipyridine-6,6′-dicarboxylate and 6′-carboxy-2,2′-bipyridine-6-carboxylate ligands. Intermolecular O—H⋯O hydrogen bonds and face-to-face π-stacking interactions [centroid–centroid distance = 3.6352 (16) Å] between inversion-related pyridine rings link adjacent mononuclear units into a two-dimensional supramolecular structure, and several intermolecular C—H⋯O interactions are also observed.

Related literature

For the structure of a Co^II compound with pyridine-2,6-dicarboxylate and 4,4′-bipyridine, see: Ghosh et al. (2005 ). For the structures and thermal properties of five Ln^III (Ln is a lanthanide) compounds with the title ligand, see: Wang et al. (2010 ), for a related Rh^III compound with the title ligand, see: Wang et al. (2012 ) and for a related Ni^II compound with the title ligand, see: Wang, Su et al. (2009 ). For the structures and magnetic properties of [Gd^III₄Co^IICo^III(μ₃-OH)₃(μ₃-O)(pydc)₆(H₂O)₅]·8H₂O (pydc = 2,5-pyridinedicarboxylate dianion), see: Wang, Yue et al. (2009 ).

Experimental

Crystal data

[Co(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]
M_r = 544.31
Monoclinic, P 2₁ /c
a = 9.3329 (19) Å
b = 13.561 (3) Å
c = 16.894 (3) Å
β = 100.70 (3)°
V = 2101.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 153 K
0.26 × 0.20 × 0.08 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.803, T_max = 0.933
13969 measured reflections
3696 independent reflections
3219 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.091
S = 1.06
3696 reflections
335 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10A⋯O7ⁱ	0.82	1.65	2.445 (3)	164
C15—H15⋯O2ⁱ	0.93	2.58	3.391 (3)	147
C8—H8⋯O10ⁱⁱ	0.93	2.41	3.142 (3)	135
C16—H16⋯O6ⁱⁱⁱ	0.93	2.52	3.044 (3)	116
C20—H20⋯O1^iv	0.93	2.55	3.315 (3)	140
C22—H22⋯O9^v	0.93	2.35	3.091 (3)	136
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+2, -y+1, -z+2; (v) -x+1, -y+1, -z+2.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812009816/qm2056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812009816/qm2056Isup2.hkl

checkCIF report

Comment top

In recent years, many bipyridine dicarboxylic acid ligands such as 2,2'-dipyridine-4,4'-dicarboxylic acid, 2,2'-dipyridine-5,5'-dicarboxylic acid and 2,2'-dipyridine-6,6'-dicarboxylic acid have been used in metal–organic coordination chemistry because of their diverse coordination modes, which leads to more stable and fascinating architectures (Wang et al., 2012). Some X-ray crystal structures constructed from the title ligand and metal ions, such as [NiL₂].4H₂O (Wang, Su et al., 2009), [Ln₃L₄(HL)(H₂O)₂].12H₂O (Ln=Ce, Nd, Pr) (Wang et al., 2010) and [RhL(HL)] (Wang et al., 2012), have been investigated previously. In this work, we report the synthesis and structure of the title compound, and a careful literature survey showed that it is the first compound constructed from Co^III ion and the title ligand.

In the title compound, the Co^III center is six-coordinated in a distorted octahedral geometry by four N atoms and two O atoms of two chelating ligands L and HL (H₂L= 2,2'-bipyridine-6,6'-dicarboxylic acid) (Fig. 1). Support for the assignment of a +3 oxidation state to Co comes from the Co—N and Co—O bond distances [1.8546 (19) and 1.9941 (19) Å for Co—N bonds and 1.9018 (16) and 1.9055 (18) Å for Co—O bonds which are shorter than those reported for Co^II compounds (Ghosh et al., 2005; Wang, Yue et al., 2009). The coordinated bipyridine fragments are nearly coplanar [see torsion angles = 2.0 (3) and 2.2 (3)° in Table 1].

In the structure, the hydrogen-bond donor O10 is connected to the acceptor O7 from adjacent molecule to form a one-dimensional chain along the c-axis (O10—H10A···O7ⁱ = 1.65 Å, i = x, -y+3/2, z-1/2, Table 2). Moreover, the adjacent chains are linked into a two-dimensional layer by π–π contacts between inversion-related pyridine rings with Cg7···Cg8ii distance of 3.6352 Å (Fig. 2). Cg7 and Cg8 are the centroids of the pyridine rings (N3, C14–C18) and (N4, C19–C23), respectively (symmetry code: ii = -x, 1-y, -z). Several intermolecular C—H···O interactions contribute to stabilize the crystal structure.

Related literature top

For the structure of a Co^II compound with pyridine-2,6-dicarboxylate and 4,4'-bipyridine, see: Ghosh et al. (2005). For the structures and thermal properties of five Ln^III (Ln is a lanthanide) compounds with the title ligand, see: Wang et al. (2010), for a related Rh^III compound with the title ligand, see: Wang et al. (2012) and for a related Ni^II compound with the title ligand, see: Wang, Su et al. (2009). For the structures and magnetic properties of [Gd^III₄Co^IICo^III(µ₃-OH)₃(µ₃-O)(pydc)₆(H₂O)₅].8H₂O, see: Wang, Yue et al. (2009).

Experimental top

The title compound was obtained by the reaction of the mixture of Co(NO₃)₂.6H₂O, and 2,2'-dipyridine-6,6'-dicarboxylic acid in a molar ratio of 1:0.8 and 8 ml of water under hydrothermal conditions (at 393 K for 4 days and cooled to room temperature with a 2 K h^-1 rate). The brown block crystals were washed by water (Yield: 30%).

Structure description top

The CoIII center in the title compound,Co(C12H6N2O4)(C12H7N2O4), is six-coordinated in a distorted octahedral geometry by four N atoms and two O atoms of two chelated ligands L and HL (H2L= 2,2'-bipyridine-6,6'-dicarboxylic acid). The intermolecular O—H···O hydrogen bonds and face-to-face π-stacking interactions [centroid···centroid distances of 3.6352?Å] between inversion related pyridine rings link the adjacent mononuclear units into one-dimensional double-chain supramolecular structure along the c-axis. In recent years, many bipyridine dicarboxylic acid ligands such as 2,2'-dipyridine-4,4'-dicarboxylic acid, 2,2'-dipyridine-5,5'-dicarboxylic acid and 2,2'-dipyridine-6,6'-dicarboxylic acid have been used in metal–organic coordination chemistry because of their diverse coordination modes, which leads to more stable and fascinating architectures (Wang et al., 2012). Some X-ray crystal structures constructed from the title ligand and metal ions have been investigated previously, such as [NiL2].4H2O (Wang et al., 2009) and [Ln3L4(HL)(H2O)2].12H2O (Ln=Ce, Nd, Pr) (Wang et al., 2010) and [RhL(HL)] (Wang et al., 2012) . In this work, we report the synthesis and structure of the title compound, and a careful literature survey showed that it is the first compound constructed from CoIII ion and the title ligand. In the title compound, the CoIII center is six-coordinated in a distorted octahedral geometry by four N atoms and two O atoms of two chelated ligands L and HL (H2L= 2,2'-bipyridine-6,6'-dicarboxylic acid) (Fig. 1).The Co atom in the crystal structure exhibit +3 oxidation state, which can also be proved that the Co—O and Co—N bond distances [1.8546 (19) -1.9941 (19)?Å for Co—N bond lengths; 1.9018 (16) and 1.9055 (18) Å for Co—O bond lengths] in our structure are shorter than those in the reported CoII compounds (Ghosh, S., et al., 2005; Wang, N., et al., 2009). The coordinated bipyridine fragments are nearly coplanar [see torsion angles = 2.0 (3) and 2.2 (3)° in Table 1]. The one-dimensional double-chain structure of the title compound via hydrogen bonds and face-to-face π-stacking interactions is illustrated in Fig. 2. The hydrogen-bond donor O10 is connected to the acceptor O7 from adjacent moiety (Table 2) to form a one-dimensional chain along the c-axis. Moreover, two adjacent chains are connected to form the one-dimensional double-chain structure along the c-axis through the face-to-face π-stacking interactions between inversion related pyridine rings with Cg7···Cg8ii distance of 3.64Å (Cg7 and Cg8 are the centroids of the pyridine rings (N3, C14 - C18) and (N4, C19 - C23), respectively. Symmetry codes: (ii) = -x, 1-y, -z, see Fig. 2).

The title compound was obtained by the reaction of the mixture of Co(NO3)2.6H2O, and 2,2'-dipyridine-6,6'-dicarboxylic acid in a molar ratio of 1:0.8 and 8?mL of water under hydrothermal conditions (at 120 °C for 4 days and cooled to room temperature with a 2 °C h-1 rate). The brown block crystals were washed by water (Yield: 30%).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. The two-dimensional layer structure of the title compound via hydrogen bonds and face-to-face π-stacking interactions.

(2,2'-Bipyridine-6,6'-dicarboxylato-κ³N,N',O⁶)(6'- carboxy-2,2'-bipyridine-6-carboxylato- κ³N,N',O⁶)cobalt(III) top

Crystal data top

[Co(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]	Z = 4
M_r = 544.31	F(000) = 1104
Monoclinic, P2₁/c	D_x = 1.721 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.3329 (19) Å	µ = 0.88 mm⁻¹
b = 13.561 (3) Å	T = 153 K
c = 16.894 (3) Å	Block, brown
β = 100.70 (3)°	0.26 × 0.20 × 0.08 mm
V = 2101.0 (7) Å³

Data collection top

Rigaku Saturn CCD area-detector diffractometer	3696 independent reflections
Radiation source: fine-focus sealed tube	3219 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω and φ scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −11→8
T_min = 0.803, T_max = 0.933	k = −16→16
13969 measured reflections	l = −18→20

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0499P)² + 0.3348P] where P = (F_o² + 2F_c²)/3
3696 reflections	(Δ/σ)_max = 0.001
335 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Co(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]	V = 2101.0 (7) Å³
M_r = 544.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3329 (19) Å	µ = 0.88 mm⁻¹
b = 13.561 (3) Å	T = 153 K
c = 16.894 (3) Å	0.26 × 0.20 × 0.08 mm
β = 100.70 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	3696 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	3219 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.933	R_int = 0.043
13969 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
3696 reflections	Δρ_min = −0.47 e Å⁻³
335 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	0.84031 (3)	0.73728 (2)	0.932821 (17)	0.02082 (12)
O1	1.01239 (19)	0.73257 (12)	1.01357 (9)	0.0282 (4)
O2	1.1381 (2)	0.81870 (16)	1.11603 (10)	0.0460 (5)
O5	0.93674 (17)	0.81669 (12)	0.86609 (9)	0.0267 (4)
O6	1.0973 (2)	0.80414 (14)	0.78364 (11)	0.0450 (5)
N1	0.8057 (2)	0.85278 (14)	0.98537 (11)	0.0251 (4)
N2	0.6513 (2)	0.77321 (14)	0.86292 (11)	0.0234 (4)
N3	0.9085 (2)	0.63364 (14)	0.87852 (10)	0.0216 (4)
N4	0.7596 (2)	0.62602 (14)	0.98808 (10)	0.0234 (4)
C1	1.0325 (3)	0.80793 (19)	1.06293 (13)	0.0299 (6)
C2	0.9115 (3)	0.88248 (18)	1.04578 (13)	0.0286 (6)
C3	0.9052 (3)	0.97481 (19)	1.07909 (14)	0.0365 (6)
H3	0.9766	0.9956	1.1218	0.044*
C4	0.7900 (3)	1.0357 (2)	1.04739 (16)	0.0416 (7)
H4	0.7823	1.0975	1.0702	0.050*
C5	0.6856 (3)	1.00621 (19)	0.98213 (17)	0.0382 (7)
H5	0.6106	1.0484	0.9595	0.046*
C6	0.6962 (3)	0.91155 (18)	0.95143 (14)	0.0291 (6)
C7	0.6051 (3)	0.86495 (18)	0.88142 (14)	0.0296 (6)
C8	0.4839 (3)	0.9092 (2)	0.83680 (16)	0.0392 (7)
H8	0.4554	0.9716	0.8505	0.047*
C9	0.4047 (3)	0.8600 (2)	0.77141 (17)	0.0421 (7)
H9	0.3225	0.8888	0.7406	0.051*
C10	0.4492 (3)	0.7678 (2)	0.75259 (17)	0.0396 (7)
H10	0.3971	0.7335	0.7089	0.048*
C11	0.5733 (3)	0.72615 (19)	0.79957 (14)	0.0281 (6)
C12	0.6111 (3)	0.62148 (19)	0.78089 (13)	0.0286 (6)
C13	1.0147 (3)	0.76672 (18)	0.82270 (14)	0.0272 (6)
C14	0.9955 (2)	0.65787 (18)	0.82720 (12)	0.0240 (5)
C15	1.0604 (3)	0.58537 (19)	0.78857 (13)	0.0302 (6)
H15	1.1204	0.6014	0.7523	0.036*
C16	1.0332 (3)	0.48753 (19)	0.80572 (14)	0.0323 (6)
H16	1.0746	0.4373	0.7800	0.039*
C17	0.9449 (3)	0.46388 (18)	0.86091 (13)	0.0286 (6)
H17	0.9271	0.3985	0.8724	0.034*
C18	0.8844 (3)	0.53988 (17)	0.89816 (13)	0.0232 (5)
C19	0.7946 (3)	0.53543 (17)	0.96114 (13)	0.0236 (5)
C20	0.7504 (3)	0.44827 (19)	0.99124 (14)	0.0298 (6)
H20	0.7748	0.3879	0.9712	0.036*
C21	0.6691 (3)	0.4523 (2)	1.05193 (15)	0.0351 (6)
H21	0.6366	0.3947	1.0727	0.042*
C22	0.6372 (3)	0.5430 (2)	1.08100 (14)	0.0336 (6)
H22	0.5850	0.5469	1.1227	0.040*
C23	0.6831 (3)	0.62865 (19)	1.04793 (13)	0.0272 (5)
C24	0.6458 (3)	0.7264 (2)	1.08152 (15)	0.0319 (6)
O9	0.5735 (2)	0.55690 (13)	0.82239 (10)	0.0396 (5)
O7	0.7342 (2)	0.74748 (14)	1.14778 (11)	0.0418 (5)
O10	0.6766 (2)	0.60709 (13)	0.72153 (10)	0.0401 (5)
H10A	0.6806	0.6591	0.6972	0.060*
O8	0.5416 (2)	0.77371 (16)	1.04846 (13)	0.0504 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0249 (2)	0.01599 (19)	0.02186 (19)	0.00158 (13)	0.00513 (13)	0.00048 (12)
O1	0.0310 (10)	0.0244 (9)	0.0281 (9)	0.0023 (7)	0.0025 (7)	−0.0007 (7)
O2	0.0432 (12)	0.0567 (14)	0.0329 (9)	−0.0020 (10)	−0.0064 (9)	−0.0069 (9)
O5	0.0325 (10)	0.0184 (9)	0.0312 (8)	−0.0005 (7)	0.0108 (7)	0.0014 (7)
O6	0.0528 (13)	0.0339 (11)	0.0572 (12)	−0.0022 (9)	0.0331 (10)	0.0083 (9)
N1	0.0325 (12)	0.0199 (11)	0.0246 (9)	0.0003 (9)	0.0097 (9)	−0.0003 (8)
N2	0.0244 (11)	0.0210 (11)	0.0250 (10)	−0.0006 (8)	0.0047 (8)	0.0025 (8)
N3	0.0246 (10)	0.0196 (10)	0.0204 (9)	0.0012 (8)	0.0037 (8)	0.0010 (8)
N4	0.0259 (11)	0.0225 (11)	0.0216 (9)	0.0015 (9)	0.0036 (8)	0.0012 (8)
C1	0.0369 (15)	0.0295 (14)	0.0239 (12)	−0.0025 (12)	0.0076 (11)	0.0032 (10)
C2	0.0384 (15)	0.0260 (13)	0.0239 (12)	−0.0047 (11)	0.0123 (11)	−0.0022 (10)
C3	0.0550 (18)	0.0283 (15)	0.0287 (13)	−0.0095 (13)	0.0143 (12)	−0.0072 (11)
C4	0.0585 (19)	0.0241 (14)	0.0481 (16)	−0.0011 (14)	0.0255 (15)	−0.0100 (12)
C5	0.0461 (17)	0.0222 (14)	0.0509 (16)	0.0084 (12)	0.0211 (14)	0.0005 (12)
C6	0.0319 (14)	0.0241 (13)	0.0345 (13)	0.0029 (11)	0.0143 (11)	0.0010 (11)
C7	0.0301 (14)	0.0255 (14)	0.0354 (13)	0.0058 (11)	0.0118 (11)	0.0073 (11)
C8	0.0365 (16)	0.0324 (16)	0.0497 (16)	0.0108 (13)	0.0103 (13)	0.0089 (13)
C9	0.0304 (15)	0.0444 (18)	0.0502 (16)	0.0071 (13)	0.0041 (13)	0.0218 (14)
C10	0.0317 (16)	0.0448 (18)	0.0384 (15)	−0.0024 (13)	−0.0036 (12)	0.0092 (13)
C11	0.0280 (14)	0.0306 (14)	0.0260 (12)	−0.0044 (11)	0.0057 (11)	0.0071 (10)
C12	0.0307 (14)	0.0304 (14)	0.0222 (12)	−0.0080 (11)	−0.0014 (11)	0.0017 (11)
C13	0.0277 (14)	0.0241 (13)	0.0295 (13)	0.0013 (11)	0.0044 (11)	0.0032 (10)
C14	0.0243 (13)	0.0265 (13)	0.0208 (11)	−0.0005 (10)	0.0032 (10)	0.0004 (10)
C15	0.0344 (15)	0.0339 (15)	0.0241 (12)	0.0030 (12)	0.0099 (11)	−0.0028 (11)
C16	0.0386 (15)	0.0291 (14)	0.0292 (13)	0.0056 (12)	0.0065 (11)	−0.0088 (11)
C17	0.0350 (15)	0.0198 (13)	0.0291 (12)	0.0002 (11)	0.0012 (11)	−0.0022 (10)
C18	0.0240 (13)	0.0201 (12)	0.0236 (11)	−0.0015 (10)	−0.0001 (10)	−0.0001 (9)
C19	0.0245 (13)	0.0206 (12)	0.0241 (11)	−0.0006 (10)	0.0005 (10)	0.0001 (9)
C20	0.0316 (14)	0.0236 (14)	0.0323 (13)	−0.0008 (11)	0.0011 (11)	0.0027 (10)
C21	0.0356 (15)	0.0312 (15)	0.0373 (14)	−0.0088 (12)	0.0040 (12)	0.0105 (12)
C22	0.0339 (15)	0.0387 (16)	0.0299 (13)	−0.0049 (12)	0.0103 (11)	0.0050 (11)
C23	0.0245 (13)	0.0327 (14)	0.0238 (11)	0.0005 (11)	0.0029 (10)	0.0012 (10)
C24	0.0345 (16)	0.0333 (15)	0.0325 (14)	0.0019 (12)	0.0183 (12)	0.0058 (11)
O9	0.0513 (12)	0.0310 (11)	0.0378 (10)	−0.0101 (9)	0.0116 (9)	0.0074 (8)
O7	0.0494 (12)	0.0421 (12)	0.0340 (10)	0.0100 (9)	0.0078 (9)	−0.0072 (8)
O10	0.0612 (13)	0.0283 (10)	0.0332 (10)	−0.0079 (9)	0.0148 (9)	0.0017 (8)
O8	0.0472 (13)	0.0497 (13)	0.0542 (12)	0.0178 (11)	0.0092 (10)	0.0045 (10)

Geometric parameters (Å, º) top

Co1—N3	1.8546 (19)	C8—H8	0.9300
Co1—N1	1.8580 (19)	C9—C10	1.372 (4)
Co1—O5	1.9018 (16)	C9—H9	0.9300
Co1—O1	1.9055 (18)	C10—C11	1.397 (4)
Co1—N2	1.993 (2)	C10—H10	0.9300
Co1—N4	1.9941 (19)	C11—C12	1.510 (4)
O1—C1	1.310 (3)	C12—O9	1.214 (3)
O2—C1	1.212 (3)	C12—O10	1.282 (3)
O5—C13	1.313 (3)	C13—C14	1.491 (3)
O6—C13	1.215 (3)	C14—C15	1.381 (3)
N1—C6	1.338 (3)	C15—C16	1.391 (4)
N1—C2	1.344 (3)	C15—H15	0.9300
N2—C11	1.339 (3)	C16—C17	1.392 (3)
N2—C7	1.372 (3)	C16—H16	0.9300
N3—C14	1.334 (3)	C17—C18	1.382 (3)
N3—C18	1.343 (3)	C17—H17	0.9300
N4—C23	1.342 (3)	C18—C19	1.473 (3)
N4—C19	1.371 (3)	C19—C20	1.380 (3)
C1—C2	1.503 (4)	C20—C21	1.385 (3)
C2—C3	1.378 (3)	C20—H20	0.9300
C3—C4	1.383 (4)	C21—C22	1.377 (4)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.388 (4)	C22—C23	1.391 (3)
C4—H4	0.9300	C22—H22	0.9300
C5—C6	1.395 (3)	C23—C24	1.508 (4)
C5—H5	0.9300	C24—O8	1.211 (3)
C6—C7	1.466 (3)	C24—O7	1.293 (3)
C7—C8	1.375 (3)	O10—H10A	0.8200
C8—C9	1.382 (4)

N3—Co1—N1	168.91 (8)	C7—C8—H8	120.3
N3—Co1—O5	83.81 (8)	C9—C8—H8	120.3
N1—Co1—O5	87.09 (8)	C10—C9—C8	119.0 (2)
N3—Co1—O1	90.43 (8)	C10—C9—H9	120.5
N1—Co1—O1	83.36 (8)	C8—C9—H9	120.5
O5—Co1—O1	90.84 (7)	C9—C10—C11	119.5 (3)
N3—Co1—N2	103.87 (8)	C9—C10—H10	120.3
N1—Co1—N2	82.17 (8)	C11—C10—H10	120.3
O5—Co1—N2	88.54 (7)	N2—C11—C10	122.1 (2)
O1—Co1—N2	165.53 (7)	N2—C11—C12	120.1 (2)
N3—Co1—N4	81.51 (8)	C10—C11—C12	117.6 (2)
N1—Co1—N4	107.45 (8)	O9—C12—O10	125.0 (3)
O5—Co1—N4	165.32 (7)	O9—C12—C11	117.0 (2)
O1—Co1—N4	88.91 (7)	O10—C12—C11	118.0 (2)
N2—Co1—N4	95.32 (8)	O6—C13—O5	124.1 (2)
C1—O1—Co1	115.57 (15)	O6—C13—C14	122.4 (2)
C13—O5—Co1	114.27 (15)	O5—C13—C14	113.5 (2)
C6—N1—C2	122.8 (2)	N3—C14—C15	120.3 (2)
C6—N1—Co1	118.95 (16)	N3—C14—C13	111.7 (2)
C2—N1—Co1	116.55 (16)	C15—C14—C13	127.8 (2)
C11—N2—C7	117.8 (2)	C14—C15—C16	117.9 (2)
C11—N2—Co1	130.32 (17)	C14—C15—H15	121.1
C7—N2—Co1	111.60 (15)	C16—C15—H15	121.1
C14—N3—C18	122.9 (2)	C15—C16—C17	120.9 (2)
C14—N3—Co1	116.17 (16)	C15—C16—H16	119.6
C18—N3—Co1	120.42 (15)	C17—C16—H16	119.6
C23—N4—C19	117.8 (2)	C18—C17—C16	118.4 (2)
C23—N4—Co1	129.24 (17)	C18—C17—H17	120.8
C19—N4—Co1	112.87 (15)	C16—C17—H17	120.8
O2—C1—O1	124.4 (2)	N3—C18—C17	119.5 (2)
O2—C1—C2	122.7 (2)	N3—C18—C19	111.17 (19)
O1—C1—C2	112.8 (2)	C17—C18—C19	129.3 (2)
N1—C2—C3	120.1 (2)	N4—C19—C20	122.6 (2)
N1—C2—C1	111.4 (2)	N4—C19—C18	113.95 (19)
C3—C2—C1	128.3 (2)	C20—C19—C18	123.4 (2)
C2—C3—C4	118.3 (2)	C19—C20—C21	118.8 (2)
C2—C3—H3	120.9	C19—C20—H20	120.6
C4—C3—H3	120.9	C21—C20—H20	120.6
C3—C4—C5	121.1 (2)	C22—C21—C20	118.9 (2)
C3—C4—H4	119.5	C22—C21—H21	120.5
C5—C4—H4	119.5	C20—C21—H21	120.5
C4—C5—C6	118.2 (3)	C21—C22—C23	120.0 (2)
C4—C5—H5	120.9	C21—C22—H22	120.0
C6—C5—H5	120.9	C23—C22—H22	120.0
N1—C6—C5	119.3 (2)	N4—C23—C22	121.8 (2)
N1—C6—C7	111.8 (2)	N4—C23—C24	119.9 (2)
C5—C6—C7	128.8 (2)	C22—C23—C24	118.3 (2)
N2—C7—C8	122.1 (2)	O8—C24—O7	127.6 (3)
N2—C7—C6	114.5 (2)	O8—C24—C23	120.9 (2)
C8—C7—C6	123.3 (2)	O7—C24—C23	111.4 (2)
C7—C8—C9	119.4 (3)	C12—O10—H10A	109.5

N3—Co1—O1—C1	167.56 (17)	Co1—N1—C6—C7	8.9 (3)
N1—Co1—O1—C1	−3.23 (16)	C4—C5—C6—N1	−0.1 (4)
O5—Co1—O1—C1	83.75 (16)	C4—C5—C6—C7	−176.8 (2)
N2—Co1—O1—C1	−3.7 (4)	C11—N2—C7—C8	−0.7 (3)
N4—Co1—O1—C1	−110.93 (17)	Co1—N2—C7—C8	174.33 (19)
N3—Co1—O5—C13	−6.93 (16)	C11—N2—C7—C6	−180.0 (2)
N1—Co1—O5—C13	166.73 (16)	Co1—N2—C7—C6	−5.0 (2)
O1—Co1—O5—C13	83.42 (16)	N1—C6—C7—N2	−2.0 (3)
N2—Co1—O5—C13	−111.04 (16)	C5—C6—C7—N2	174.9 (2)
N4—Co1—O5—C13	−5.5 (4)	N1—C6—C7—C8	178.8 (2)
N3—Co1—N1—C6	114.4 (4)	C5—C6—C7—C8	−4.4 (4)
O5—Co1—N1—C6	79.54 (18)	N2—C7—C8—C9	0.5 (4)
O1—Co1—N1—C6	170.72 (19)	C6—C7—C8—C9	179.7 (2)
N2—Co1—N1—C6	−9.38 (18)	C7—C8—C9—C10	0.0 (4)
N4—Co1—N1—C6	−102.53 (18)	C8—C9—C10—C11	−0.2 (4)
N3—Co1—N1—C2	−51.4 (5)	C7—N2—C11—C10	0.5 (3)
O5—Co1—N1—C2	−86.23 (17)	Co1—N2—C11—C10	−173.46 (18)
O1—Co1—N1—C2	4.96 (16)	C7—N2—C11—C12	−174.5 (2)
N2—Co1—N1—C2	−175.15 (17)	Co1—N2—C11—C12	11.6 (3)
N4—Co1—N1—C2	91.71 (17)	C9—C10—C11—N2	0.0 (4)
N3—Co1—N2—C11	11.2 (2)	C9—C10—C11—C12	175.1 (2)
N1—Co1—N2—C11	−178.3 (2)	N2—C11—C12—O9	77.1 (3)
O5—Co1—N2—C11	94.5 (2)	C10—C11—C12—O9	−98.1 (3)
O1—Co1—N2—C11	−177.8 (3)	N2—C11—C12—O10	−104.8 (3)
N4—Co1—N2—C11	−71.3 (2)	C10—C11—C12—O10	80.0 (3)
N3—Co1—N2—C7	−163.00 (15)	Co1—O5—C13—O6	−171.1 (2)
N1—Co1—N2—C7	7.52 (15)	Co1—O5—C13—C14	7.4 (2)
O5—Co1—N2—C7	−79.74 (16)	C18—N3—C14—C15	3.0 (3)
O1—Co1—N2—C7	8.0 (4)	Co1—N3—C14—C15	175.12 (17)
N4—Co1—N2—C7	114.45 (16)	C18—N3—C14—C13	−174.2 (2)
N1—Co1—N3—C14	−30.2 (5)	Co1—N3—C14—C13	−2.1 (2)
O5—Co1—N3—C14	4.85 (16)	O6—C13—C14—N3	175.0 (2)
O1—Co1—N3—C14	−85.95 (16)	O5—C13—C14—N3	−3.6 (3)
N2—Co1—N3—C14	91.80 (16)	O6—C13—C14—C15	−1.9 (4)
N4—Co1—N3—C14	−174.78 (17)	O5—C13—C14—C15	179.5 (2)
N1—Co1—N3—C18	142.1 (4)	N3—C14—C15—C16	−0.7 (3)
O5—Co1—N3—C18	177.15 (18)	C13—C14—C15—C16	176.0 (2)
O1—Co1—N3—C18	86.35 (18)	C14—C15—C16—C17	−0.9 (4)
N2—Co1—N3—C18	−95.90 (18)	C15—C16—C17—C18	0.2 (4)
N4—Co1—N3—C18	−2.48 (17)	C14—N3—C18—C17	−3.7 (3)
N3—Co1—N4—C23	178.3 (2)	Co1—N3—C18—C17	−175.46 (16)
N1—Co1—N4—C23	5.0 (2)	C14—N3—C18—C19	175.02 (19)
O5—Co1—N4—C23	176.9 (2)	Co1—N3—C18—C19	3.3 (3)
O1—Co1—N4—C23	87.71 (19)	C16—C17—C18—N3	2.0 (3)
N2—Co1—N4—C23	−78.42 (19)	C16—C17—C18—C19	−176.5 (2)
N3—Co1—N4—C19	0.99 (15)	C23—N4—C19—C20	2.2 (3)
N1—Co1—N4—C19	−172.30 (15)	Co1—N4—C19—C20	179.82 (18)
O5—Co1—N4—C19	−0.5 (4)	C23—N4—C19—C18	−177.24 (19)
O1—Co1—N4—C19	−89.61 (16)	Co1—N4—C19—C18	0.4 (2)
N2—Co1—N4—C19	104.26 (16)	N3—C18—C19—N4	−2.2 (3)
Co1—O1—C1—O2	−177.4 (2)	C17—C18—C19—N4	176.4 (2)
Co1—O1—C1—C2	1.1 (2)	N3—C18—C19—C20	178.4 (2)
C6—N1—C2—C3	4.3 (3)	C17—C18—C19—C20	−3.0 (4)
Co1—N1—C2—C3	169.50 (18)	N4—C19—C20—C21	−0.9 (4)
C6—N1—C2—C1	−170.7 (2)	C18—C19—C20—C21	178.4 (2)
Co1—N1—C2—C1	−5.5 (2)	C19—C20—C21—C22	−1.0 (3)
O2—C1—C2—N1	−178.7 (2)	C20—C21—C22—C23	1.8 (4)
O1—C1—C2—N1	2.8 (3)	C19—N4—C23—C22	−1.4 (3)
O2—C1—C2—C3	6.8 (4)	Co1—N4—C23—C22	−178.62 (18)
O1—C1—C2—C3	−171.7 (2)	C19—N4—C23—C24	178.1 (2)
N1—C2—C3—C4	−1.5 (4)	Co1—N4—C23—C24	0.9 (3)
C1—C2—C3—C4	172.5 (2)	C21—C22—C23—N4	−0.5 (4)
C2—C3—C4—C5	−2.0 (4)	C21—C22—C23—C24	180.0 (2)
C3—C4—C5—C6	2.8 (4)	N4—C23—C24—O8	82.6 (3)
C2—N1—C6—C5	−3.5 (3)	C22—C23—C24—O8	−97.9 (3)
Co1—N1—C6—C5	−168.27 (18)	N4—C23—C24—O7	−99.5 (3)
C2—N1—C6—C7	173.7 (2)	C22—C23—C24—O7	80.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O7ⁱ	0.82	1.65	2.445 (3)	164
C15—H15···O2ⁱ	0.93	2.58	3.391 (3)	147
C8—H8···O10ⁱⁱ	0.93	2.41	3.142 (3)	135
C16—H16···O6ⁱⁱⁱ	0.93	2.52	3.044 (3)	116
C20—H20···O1^iv	0.93	2.55	3.315 (3)	140
C22—H22···O9^v	0.93	2.35	3.091 (3)	136

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+2; (v) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₆N₂O₄)(C₁₂H₇N₂O₄)]
M_r	544.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	9.3329 (19), 13.561 (3), 16.894 (3)
β (°)	100.70 (3)
V (Å³)	2101.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.26 × 0.20 × 0.08

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.803, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	13969, 3696, 3219
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.091, 1.06
No. of reflections	3696
No. of parameters	335
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.47

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O7ⁱ	0.82	1.65	2.445 (3)	164.2
C15—H15···O2ⁱ	0.93	2.58	3.391 (3)	146.5
C8—H8···O10ⁱⁱ	0.93	2.41	3.142 (3)	135.3
C16—H16···O6ⁱⁱⁱ	0.93	2.52	3.044 (3)	116.0
C20—H20···O1^iv	0.93	2.55	3.315 (3)	140.0
C22—H22···O9^v	0.93	2.35	3.091 (3)	136.1

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+1, −z+2; (v) −x+1, −y+1, −z+2.

Acknowledgements

This project was supported financially by the National Natural Science Foundation of China (grant No. 21166014) and a Key Grant of the Inner Mongolia Natural Science Foundation of China (grant No. 2010ZD01).

References

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