Poly[[μ-1,4-bis­(1H-imidazol-4-yl)benzene-κ2N3:N3′](μ-5-methyl­isophthalato-κ2O1:O3)cobalt(II)]

Chen, S.-S.; Yang, S.-L.; Zhang, S.-P.

doi:10.1107/S1600536811025657

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1031-m1032

doi:10.1107/S1600536811025657

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Poly[[μ-1,4-bis(1H-imidazol-4-yl)benzene-κ²N³:N^3′](μ-5-methylisophthalato-κ²O¹:O³)cobalt(II)]

Shui-Sheng Chen,^a ^* Sen-Lin Yang ^a and Shu-Ping Zhang ^a

^aDepartment of Chemistry, Fuyang Normal College, Fuyang, Anhui 236041, People's Republic of China
^*Correspondence e-mail: sscfync@163.com

(Received 10 May 2011; accepted 29 June 2011; online 6 July 2011)

In the title coordination polymer, [Co(C₉H₆O₄)(C₁₂H₁₀N₄)]_n, the Co^II atom is four-coordinated by two O atoms from two different 5-methylisophthalate bivalent anions and two N atoms from two different 1,4-bis(1H-imidazol-4-yl)benzene ligands, forming a four-coordinated tetrahedral coordination geometry. Each 5-methylisophthalate ligand acts as a μ₂-bridge, linking two Co^II atoms and forming chains which are further linked by 1,4-bis(1H-imidazol-4-yl)benzene ligands into a two-dimensional network parallel to ( $[\overline{2}]$ 01). These planes are, in turn, linked by two intermolecular N—H⋯O interactions, forming a three-dimensional structure. Weak C—H⋯O hydrogen bonds are also present in the structure.

Related literature

For background to mixed inorganic-organic hybrid materials, see: Kitagawa & Kondo (1998 ). For examples with mixed organic and N-containing ligands, see: Liu et al. (2007 ); Chen et al. (2010 ).

Experimental

Crystal data

[Co(C₉H₆O₄)(C₁₂H₁₀N₄)]
M_r = 447.31
Monoclinic, P 2₁ /c
a = 7.4608 (5) Å
b = 13.8212 (10) Å
c = 17.8629 (13) Å
β = 90.451 (1)°
V = 1841.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.815, T_max = 0.884
16427 measured reflections
4210 independent reflections
3540 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.100
S = 1.12
4210 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.45 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
N2—H2A⋯O3ⁱ	0.86	2.16	2.825 (3)	134
N3—H3⋯O2ⁱⁱ	0.86	1.96	2.803 (2)	165
C9—H9⋯O2	0.93	2.39	3.274 (3)	158
C11—H11⋯O3ⁱⁱⁱ	0.93	2.56	3.182 (3)	124
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+1, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); 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: 10.1107/S1600536811025657/bg2404sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025657/bg2404Isup2.hkl

checkCIF report

Comment top

In the last decades there has been significant interest in the design and synthesis of mixed inorganic-organic hybrid materials owing to their potential application in catalysis, gas storage and separation, ion exchange and magnetism (Kitagawa & Kondo, 1998)). Recent studies illustrated that mixed organic ligands, especially the mixed polycarboxylate and N-containing ones, with more tunable factors, are good candidates for the construction of novel MOFs (Liu et al., 2007). And based on the mix ligand strategy, we focus our attention in the study of reactions of the 1,4-di(1H-imidazol-4-yl)benzene ligand (L) together with different carboxylate ligands and salts, and made a systematic investigation on the impact of carboxylate ligands on the structure of the resulting complexes; as a result a series of novel structures have been synthesized (Chen et al., 2010). As an extension of the above work we report herein a new metal complex, Co(C₉H₆O₄) (C₁₂H₁₀N₄)]_n (I) based on the organic ligands 1,4-di(1H-imidazol-4-yl)benzene (L) and 5-methylisophthalic acid (H₂pda), together with Co^II salts. In the title compound, the Co ^II atom is tetrahedrally coordinated by two nitrogen atoms from two L molecules and two carboxylic oxygens atoms from two pda^2- ligands (Fig.1). The pda^2- ligand acts in a bidentate fashion (via two monodentate carboxylate groups) to connect Co^II atoms into a one-dimensional chain (Fig.2), while the L ligand acts as a linear bidentate bridge to link chains to form two-dimensional networks paralell to (201) (Fig.3). These planes are in turn linked into a 3D structure by two intermolecular N—H···O interactions and two weaker C-H···O contacts (Table 1)

Related literature top

For background to mixed inorganic-organic hybrid materials, see: Kitagawa & Kondo (1998). For examples with mixed organic and N-containing ligands, see: Liu et al. (2007); Chen et al. (2010).

Experimental top

All reagents and solvents were used as obtained commercially without further purification. A mixture containing CoCl₂.6H₂O (23.8 mg, 0.1 mmol), L (21.1 mg, 0.1 mmol), DMF (N:N'- dimethylformamide, 1 ml), 10 ml H₂O was sealed in a 16 ml Teflon-lined stainless steel container and heated at 393 K for 72 h. After cooling to room temperature within 12 h, block brown crystals of (I) suitable for X-ray diffraction analysis were obtained in 78% Yield.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 ORTEP drawing of the title compound (I). Displacement ellipsoids are drawn at 30% probability level. Symmetry codes: (i) 2 - x, -y, 1 - z, (ii) 1 - x, 1/2 + y, 0.5 - z.
	Fig. 2. An infinite one-dimensional chain formed from Co^II centers and pda^2- anions of the compound (I).
	Fig. 3. The two-dimensional structure built from one-dimension chains connected by L ligands of the compound (I).

Poly[[µ-1,4-bis(1H-imidazol-4-yl)benzene- κ²N³:N^3'](µ-5-methylisophthalato- κ²O¹:O³)cobalt(II)] top

Crystal data top

[Co(C₉H₆O₄)(C₁₂H₁₀N₄)]	F(000) = 916
M_r = 447.31	D_x = 1.613 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5943 reflections
a = 7.4608 (5) Å	θ = 2.2–27.5°
b = 13.8212 (10) Å	µ = 0.97 mm⁻¹
c = 17.8629 (13) Å	T = 296 K
β = 90.451 (1)°	Block, purple
V = 1841.9 (2) Å³	0.22 × 0.18 × 0.13 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	4210 independent reflections
Radiation source: fine-focus sealed tube	3540 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.815, T_max = 0.884	k = −17→17
16427 measured reflections	l = −23→23

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0533P)² + 0.5242P] where P = (F_o² + 2F_c²)/3
4210 reflections	(Δ/σ)_max = 0.010
272 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Co(C₉H₆O₄)(C₁₂H₁₀N₄)]	V = 1841.9 (2) Å³
M_r = 447.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4608 (5) Å	µ = 0.97 mm⁻¹
b = 13.8212 (10) Å	T = 296 K
c = 17.8629 (13) Å	0.22 × 0.18 × 0.13 mm
β = 90.451 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	4210 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3540 reflections with I > 2σ(I)
T_min = 0.815, T_max = 0.884	R_int = 0.032
16427 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.12	Δρ_max = 0.45 e Å⁻³
4210 reflections	Δρ_min = −0.34 e Å⁻³
272 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	0.54880 (4)	0.195950 (18)	0.350426 (14)	0.02058 (10)
C1	0.7795 (3)	0.12914 (15)	0.66061 (11)	0.0255 (4)
H1	0.8186	0.1489	0.7078	0.031*
C2	0.6298 (3)	0.17243 (15)	0.62840 (11)	0.0266 (4)
H2	0.5685	0.2200	0.6547	0.032*
C3	0.5697 (3)	0.14555 (14)	0.55695 (11)	0.0226 (4)
C4	0.6616 (3)	0.07175 (14)	0.52012 (11)	0.0238 (4)
H4	0.6235	0.0524	0.4728	0.029*
C5	0.8076 (3)	0.02726 (14)	0.55266 (11)	0.0241 (4)
H5	0.8643	−0.0229	0.5275	0.029*
C6	0.8721 (3)	0.05623 (14)	0.62299 (10)	0.0218 (4)
C7	0.4104 (3)	0.18914 (13)	0.52141 (11)	0.0231 (4)
C8	0.2542 (3)	0.21709 (16)	0.55384 (12)	0.0295 (5)
H8	0.2285	0.2165	0.6047	0.035*
C9	0.2298 (3)	0.23532 (15)	0.43242 (11)	0.0268 (4)
H9	0.1822	0.2503	0.3856	0.032*
C10	1.0349 (3)	0.00981 (14)	0.65210 (10)	0.0220 (4)
C11	1.1089 (3)	−0.07682 (14)	0.63344 (11)	0.0244 (4)
H11	1.0566	−0.1220	0.6015	0.029*
C12	1.2952 (3)	−0.00842 (15)	0.70919 (11)	0.0279 (4)
H12	1.3949	0.0041	0.7392	0.033*
C13	0.1442 (3)	0.10168 (13)	0.19263 (10)	0.0219 (4)
C14	−0.0230 (3)	0.11928 (14)	0.16014 (11)	0.0248 (4)
H14	−0.0810	0.1775	0.1697	0.030*
C15	−0.1051 (3)	0.05121 (15)	0.11349 (11)	0.0265 (4)
C16	−0.0144 (3)	−0.03479 (15)	0.09966 (11)	0.0270 (4)
H16	−0.0651	−0.0798	0.0671	0.032*
C17	0.1502 (3)	−0.05523 (14)	0.13329 (11)	0.0230 (4)
C18	0.2293 (3)	0.01403 (14)	0.17953 (11)	0.0234 (4)
H18	0.3399	0.0015	0.2018	0.028*
C19	−0.2909 (3)	0.06834 (19)	0.08092 (15)	0.0419 (6)
H19A	−0.3309	0.0110	0.0554	0.063*
H19B	−0.2868	0.1213	0.0462	0.063*
H19C	−0.3724	0.0835	0.1206	0.063*
C20	0.2386 (3)	−0.15191 (15)	0.12306 (11)	0.0251 (4)
C21	0.2327 (3)	0.17620 (14)	0.24256 (11)	0.0237 (4)
N1	0.3928 (2)	0.20055 (12)	0.44391 (9)	0.0231 (4)
N2	0.1423 (3)	0.24621 (13)	0.49691 (10)	0.0295 (4)
H2A	0.0348	0.2677	0.5018	0.035*
N3	1.1559 (2)	0.05179 (12)	0.70134 (9)	0.0258 (4)
H3	1.1438	0.1069	0.7231	0.031*
N4	1.2734 (2)	−0.08794 (12)	0.66891 (9)	0.0244 (4)
O1	0.3807 (2)	0.14966 (11)	0.27237 (9)	0.0342 (4)
O2	0.1604 (2)	0.25623 (10)	0.25192 (9)	0.0353 (4)
O3	0.1867 (2)	−0.21003 (11)	0.07470 (9)	0.0337 (4)
O4	0.3683 (2)	−0.17173 (11)	0.16856 (9)	0.0324 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01940 (16)	0.01927 (15)	0.02303 (15)	0.00030 (10)	−0.00299 (10)	0.00033 (9)
C1	0.0277 (11)	0.0262 (10)	0.0225 (9)	0.0019 (9)	−0.0044 (8)	−0.0028 (7)
C2	0.0287 (12)	0.0236 (9)	0.0273 (10)	0.0052 (9)	−0.0016 (8)	−0.0029 (8)
C3	0.0212 (10)	0.0221 (9)	0.0246 (9)	0.0009 (8)	−0.0017 (7)	0.0037 (7)
C4	0.0232 (10)	0.0266 (10)	0.0216 (9)	−0.0009 (8)	−0.0033 (7)	−0.0009 (7)
C5	0.0231 (10)	0.0253 (10)	0.0240 (9)	0.0030 (8)	−0.0002 (8)	−0.0028 (7)
C6	0.0199 (10)	0.0219 (9)	0.0235 (9)	0.0000 (8)	−0.0016 (7)	0.0036 (7)
C7	0.0249 (11)	0.0207 (9)	0.0237 (9)	0.0000 (8)	−0.0022 (8)	0.0017 (7)
C8	0.0290 (12)	0.0325 (11)	0.0268 (10)	0.0061 (9)	−0.0003 (9)	0.0023 (8)
C9	0.0252 (11)	0.0277 (10)	0.0275 (10)	0.0043 (9)	−0.0028 (8)	0.0032 (8)
C10	0.0210 (10)	0.0239 (9)	0.0211 (9)	0.0003 (8)	−0.0020 (7)	0.0019 (7)
C11	0.0206 (10)	0.0252 (9)	0.0272 (9)	0.0014 (8)	−0.0043 (8)	−0.0016 (8)
C12	0.0241 (11)	0.0303 (10)	0.0292 (10)	0.0013 (9)	−0.0077 (8)	−0.0005 (8)
C13	0.0237 (11)	0.0202 (9)	0.0217 (9)	−0.0015 (8)	−0.0030 (7)	0.0023 (7)
C14	0.0244 (11)	0.0200 (9)	0.0299 (10)	0.0033 (8)	−0.0034 (8)	0.0016 (7)
C15	0.0223 (11)	0.0279 (10)	0.0294 (10)	−0.0009 (9)	−0.0068 (8)	0.0028 (8)
C16	0.0265 (11)	0.0244 (10)	0.0299 (10)	−0.0021 (9)	−0.0071 (8)	−0.0032 (8)
C17	0.0242 (11)	0.0208 (9)	0.0241 (9)	0.0000 (8)	−0.0029 (8)	−0.0008 (7)
C18	0.0210 (10)	0.0227 (9)	0.0264 (9)	0.0007 (8)	−0.0057 (8)	0.0002 (7)
C19	0.0302 (13)	0.0427 (13)	0.0525 (15)	0.0050 (11)	−0.0186 (11)	−0.0027 (11)
C20	0.0234 (11)	0.0227 (10)	0.0291 (10)	−0.0011 (8)	0.0005 (8)	−0.0004 (8)
C21	0.0280 (11)	0.0209 (9)	0.0221 (9)	−0.0014 (8)	−0.0038 (8)	0.0016 (7)
N1	0.0221 (9)	0.0242 (8)	0.0229 (8)	0.0015 (7)	−0.0024 (7)	0.0020 (6)
N2	0.0222 (9)	0.0333 (10)	0.0330 (9)	0.0096 (8)	0.0002 (7)	0.0015 (7)
N3	0.0266 (10)	0.0224 (8)	0.0282 (8)	0.0026 (7)	−0.0059 (7)	−0.0029 (7)
N4	0.0218 (9)	0.0253 (8)	0.0259 (8)	0.0025 (7)	−0.0045 (7)	0.0002 (6)
O1	0.0304 (9)	0.0307 (8)	0.0411 (9)	0.0016 (7)	−0.0150 (7)	−0.0095 (7)
O2	0.0484 (11)	0.0185 (7)	0.0388 (9)	0.0053 (7)	−0.0112 (7)	−0.0024 (6)
O3	0.0338 (9)	0.0255 (7)	0.0419 (9)	−0.0032 (7)	−0.0028 (7)	−0.0104 (6)
O4	0.0343 (9)	0.0277 (7)	0.0352 (8)	0.0100 (7)	−0.0077 (7)	−0.0052 (6)

Geometric parameters (Å, º) top

Co1—O4ⁱ	1.9611 (15)	C12—N4	1.323 (3)
Co1—O1	1.9744 (15)	C12—N3	1.338 (3)
Co1—N4ⁱⁱ	2.0287 (17)	C12—H12	0.9300
Co1—N1	2.0438 (17)	C13—C18	1.388 (3)
C1—C2	1.388 (3)	C13—C14	1.393 (3)
C1—C6	1.397 (3)	C13—C21	1.511 (3)
C1—H1	0.9300	C14—C15	1.395 (3)
C2—C3	1.400 (3)	C14—H14	0.9300
C2—H2	0.9300	C15—C16	1.391 (3)
C3—C4	1.397 (3)	C15—C19	1.517 (3)
C3—C7	1.472 (3)	C16—C17	1.392 (3)
C4—C5	1.375 (3)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.392 (3)
C5—C6	1.400 (3)	C17—C20	1.502 (3)
C5—H5	0.9300	C18—H18	0.9300
C6—C10	1.465 (3)	C19—H19A	0.9600
C7—C8	1.361 (3)	C19—H19B	0.9600
C7—N1	1.398 (2)	C19—H19C	0.9600
C8—N2	1.371 (3)	C20—O3	1.239 (2)
C8—H8	0.9300	C20—O4	1.288 (3)
C9—N1	1.323 (3)	C21—O2	1.242 (2)
C9—N2	1.337 (3)	C21—O1	1.276 (3)
C9—H9	0.9300	N2—H2A	0.8600
C10—C11	1.361 (3)	N3—H3	0.8600
C10—N3	1.383 (3)	N4—Co1ⁱⁱ	2.0287 (17)
C11—N4	1.385 (3)	O4—Co1ⁱⁱⁱ	1.9611 (15)
C11—H11	0.9300

O4ⁱ—Co1—O1	112.31 (7)	C18—C13—C21	119.74 (18)
O4ⁱ—Co1—N4ⁱⁱ	116.69 (7)	C14—C13—C21	120.84 (18)
O1—Co1—N4ⁱⁱ	93.09 (7)	C13—C14—C15	121.23 (19)
O4ⁱ—Co1—N1	107.14 (7)	C13—C14—H14	119.4
O1—Co1—N1	102.97 (7)	C15—C14—H14	119.4
N4ⁱⁱ—Co1—N1	122.64 (7)	C16—C15—C14	118.06 (19)
C2—C1—C6	120.74 (18)	C16—C15—C19	120.63 (19)
C2—C1—H1	119.6	C14—C15—C19	121.3 (2)
C6—C1—H1	119.6	C15—C16—C17	121.72 (19)
C1—C2—C3	120.96 (19)	C15—C16—H16	119.1
C1—C2—H2	119.5	C17—C16—H16	119.1
C3—C2—H2	119.5	C16—C17—C18	118.98 (18)
C4—C3—C2	117.93 (19)	C16—C17—C20	120.98 (18)
C4—C3—C7	119.58 (17)	C18—C17—C20	119.98 (18)
C2—C3—C7	122.44 (18)	C13—C18—C17	120.52 (19)
C5—C4—C3	121.17 (18)	C13—C18—H18	119.7
C5—C4—H4	119.4	C17—C18—H18	119.7
C3—C4—H4	119.4	C15—C19—H19A	109.5
C4—C5—C6	121.12 (18)	C15—C19—H19B	109.5
C4—C5—H5	119.4	H19A—C19—H19B	109.5
C6—C5—H5	119.4	C15—C19—H19C	109.5
C1—C6—C5	118.01 (18)	H19A—C19—H19C	109.5
C1—C6—C10	123.85 (17)	H19B—C19—H19C	109.5
C5—C6—C10	118.13 (18)	O3—C20—O4	122.05 (19)
C8—C7—N1	108.41 (19)	O3—C20—C17	121.79 (19)
C8—C7—C3	128.57 (19)	O4—C20—C17	116.14 (17)
N1—C7—C3	122.82 (18)	O2—C21—O1	125.10 (19)
C7—C8—N2	106.62 (19)	O2—C21—C13	119.87 (19)
C7—C8—H8	126.7	O1—C21—C13	115.03 (17)
N2—C8—H8	126.7	C9—N1—C7	105.86 (17)
N1—C9—N2	111.22 (18)	C9—N1—Co1	114.42 (13)
N1—C9—H9	124.4	C7—N1—Co1	139.11 (15)
N2—C9—H9	124.4	C9—N2—C8	107.89 (18)
C11—C10—N3	105.12 (17)	C9—N2—H2A	126.1
C11—C10—C6	129.41 (18)	C8—N2—H2A	126.1
N3—C10—C6	125.24 (18)	C12—N3—C10	107.96 (17)
C10—C11—N4	110.19 (18)	C12—N3—H3	126.0
C10—C11—H11	124.9	C10—N3—H3	126.0
N4—C11—H11	124.9	C12—N4—C11	105.15 (17)
N4—C12—N3	111.57 (18)	C12—N4—Co1ⁱⁱ	128.76 (15)
N4—C12—H12	124.2	C11—N4—Co1ⁱⁱ	125.59 (13)
N3—C12—H12	124.2	C21—O1—Co1	138.10 (14)
C18—C13—C14	119.42 (18)	C20—O4—Co1ⁱⁱⁱ	109.00 (13)

C6—C1—C2—C3	−1.2 (3)	C18—C17—C20—O3	−169.7 (2)
C1—C2—C3—C4	2.0 (3)	C16—C17—C20—O4	−165.3 (2)
C1—C2—C3—C7	179.3 (2)	C18—C17—C20—O4	11.9 (3)
C2—C3—C4—C5	−0.5 (3)	C18—C13—C21—O2	177.05 (19)
C7—C3—C4—C5	−177.92 (19)	C14—C13—C21—O2	−3.7 (3)
C3—C4—C5—C6	−1.8 (3)	C18—C13—C21—O1	−3.0 (3)
C2—C1—C6—C5	−1.1 (3)	C14—C13—C21—O1	176.23 (19)
C2—C1—C6—C10	177.6 (2)	N2—C9—N1—C7	−0.4 (2)
C4—C5—C6—C1	2.5 (3)	N2—C9—N1—Co1	−173.18 (14)
C4—C5—C6—C10	−176.18 (19)	C8—C7—N1—C9	0.6 (2)
C4—C3—C7—C8	140.6 (2)	C3—C7—N1—C9	175.72 (18)
C2—C3—C7—C8	−36.7 (3)	C8—C7—N1—Co1	170.50 (16)
C4—C3—C7—N1	−33.6 (3)	C3—C7—N1—Co1	−14.3 (3)
C2—C3—C7—N1	149.1 (2)	O4ⁱ—Co1—N1—C9	76.95 (16)
N1—C7—C8—N2	−0.5 (2)	O1—Co1—N1—C9	−41.65 (16)
C3—C7—C8—N2	−175.31 (19)	N4ⁱⁱ—Co1—N1—C9	−143.96 (14)
C1—C6—C10—C11	159.7 (2)	O4ⁱ—Co1—N1—C7	−92.4 (2)
C5—C6—C10—C11	−21.6 (3)	O1—Co1—N1—C7	148.99 (19)
C1—C6—C10—N3	−26.5 (3)	N4ⁱⁱ—Co1—N1—C7	46.7 (2)
C5—C6—C10—N3	152.1 (2)	N1—C9—N2—C8	0.1 (3)
N3—C10—C11—N4	−1.1 (2)	C7—C8—N2—C9	0.3 (2)
C6—C10—C11—N4	173.60 (19)	N4—C12—N3—C10	−0.6 (2)
C18—C13—C14—C15	−1.3 (3)	C11—C10—N3—C12	1.0 (2)
C21—C13—C14—C15	179.49 (18)	C6—C10—N3—C12	−173.96 (19)
C13—C14—C15—C16	−0.6 (3)	N3—C12—N4—C11	−0.1 (2)
C13—C14—C15—C19	177.2 (2)	N3—C12—N4—Co1ⁱⁱ	172.10 (14)
C14—C15—C16—C17	2.6 (3)	C10—C11—N4—C12	0.8 (2)
C19—C15—C16—C17	−175.2 (2)	C10—C11—N4—Co1ⁱⁱ	−171.73 (14)
C15—C16—C17—C18	−2.7 (3)	O2—C21—O1—Co1	10.4 (4)
C15—C16—C17—C20	174.58 (19)	C13—C21—O1—Co1	−169.49 (15)
C14—C13—C18—C17	1.2 (3)	O4ⁱ—Co1—O1—C21	−55.5 (2)
C21—C13—C18—C17	−179.59 (18)	N4ⁱⁱ—Co1—O1—C21	−176.1 (2)
C16—C17—C18—C13	0.8 (3)	N1—Co1—O1—C21	59.4 (2)
C20—C17—C18—C13	−176.52 (18)	O3—C20—O4—Co1ⁱⁱⁱ	−2.4 (3)
C16—C17—C20—O3	13.1 (3)	C17—C20—O4—Co1ⁱⁱⁱ	176.03 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3^iv	0.86	2.16	2.825 (3)	134
N3—H3···O2^v	0.86	1.96	2.803 (2)	165
C9—H9···O2	0.93	2.39	3.274 (3)	158
C11—H11···O3^vi	0.93	2.56	3.182 (3)	124

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

Experimental details

Crystal data
Chemical formula	[Co(C₉H₆O₄)(C₁₂H₁₀N₄)]
M_r	447.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.4608 (5), 13.8212 (10), 17.8629 (13)
β (°)	90.451 (1)
V (Å³)	1841.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.22 × 0.18 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.815, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	16427, 4210, 3540
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.100, 1.12
No. of reflections	4210
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.34

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3ⁱ	0.86	2.16	2.825 (3)	134
N3—H3···O2ⁱⁱ	0.86	1.96	2.803 (2)	165
C9—H9···O2	0.93	2.39	3.274 (3)	158
C11—H11···O3ⁱⁱⁱ	0.93	2.56	3.182 (3)	124

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

Acknowledgements

This work was supported by the Natural Science Foundation of Anhui Provincial Education Commission (Nos. KJ2011B128 and KJ2009A047Z).

References

Bruker (2003). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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