A binuclear cobalt(II) complex of an NO3-donor Schiff base derived from 3-carboxyl­salicylaldehyde and 2-nitro­aniline

Yu, Z.-W.; Chang, L.; Sun, P.; He, M.-H.

doi:10.1107/S1600536808042487

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m119-m120

doi:10.1107/S1600536808042487

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A binuclear cobalt(II) complex of an NO₃-donor Schiff base derived from 3-carboxylsalicylaldehyde and 2-nitroaniline

Zhao-Wen Yu,^a ^* Ling Chang,^a Peng Sun ^a and Min-Hui He ^a

^aInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, Henan, People's Republic of China
^*Correspondence e-mail: zhw@henu.edu.cn

(Received 30 October 2008; accepted 13 December 2008; online 20 December 2008)

In the crystal structure of the centrosymmetric title complex, bis{μ-3-[(2-nitrophenyl)iminomethyl]-2-oxidobenzoato}dicobalt(II), [Co₂(C₁₄H₈N₂O₅)₂], in which the ligand is 3-[(2-nitrophenyl)iminomethyl]-2-oxidobenzoate, a Schiff base synthesized from 2-nitroaniline with 3-carboxylsalicylaldehyde, the two cobalt(II) ions in the molecular unit are bridged by two phenolate O atoms of the ligands. Each metal centre has a distorted square-planar geometry. In the crystal structure, molecules are linked by Co⋯O interactions involving the nitro O atoms, forming a two-dimensional network. There are also C—H⋯O and π–π stacking interactions [centroid–centroid distances of 3.5004 (2), 3.6671 (2) and 3.6677 (2) Å] between adjacent benzene rings of the two-dimensional networks, leading to the formation of a three-dimensional framework.

Related literature

For binuclear cobalt(II) complexes of Schiff base ligands, see: Adams et al. (2002 ); Tone et al. (2007 ). For the design of molecular solids, see: Zheng et al. (2003 ). For bond-valence parameters, see: Brown & Altermatt (1985 ). For luminescence emission, see: Li et al. (2008 ).

Experimental

Crystal data

[Co₂(C₁₄H₈N₂O₅)₂]
M_r = 686.31
Monoclinic, P 2₁ /c
a = 8.3398 (6) Å
b = 11.0454 (8) Å
c = 13.3681 (9) Å
β = 99.6040 (10)°
V = 1214.16 (15) Å³
Z = 2
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 296 (2) K
0.21 × 0.16 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.752, T_max = 0.858
6134 measured reflections
2132 independent reflections
1536 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.00
2132 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O3	1.936 (3)
Co1—N1	1.947 (4)
Co1—O2ⁱ	1.874 (3)
Co1—O3ⁱ	1.929 (3)

Co1⋯O4	2.807 (4)
Co1⋯O5ⁱⁱ	2.867 (5)

O3—Co1—N1	92.51 (14)
O2ⁱ—Co1—O3	171.54 (13)
O3—Co1—O3ⁱ	78.42 (11)
O2ⁱ—Co1—N1	95.83 (14)
O3ⁱ—Co1—N1	170.41 (14)
O2ⁱ—Co1—O3ⁱ	93.33 (12)
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O5ⁱⁱⁱ	0.93	2.55	3.295 (6)	138
C12—H12⋯O1^iv	0.93	2.58	3.230 (7)	128
Symmetry codes: (iii) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y, z-1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042487/su2076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042487/su2076Isup2.hkl

checkCIF report

Comment top

Weak intermolecular forces, such as hydrogen bonding, π—π stacking, dipole—dipole attractions, and van der Waals interactions, have been studied in depth and can be used in the design of molecular solids with specific supramolecular structures and functions (Zheng et al., 2003). Numerous binuclear cobalt(II) complexes of Schiff bases have been studied (Tone et al., 2007). To the best of our knowledge, 2-NA (2-nitroaniline) Schiff bases have not been reported up to now. As a result of our interest in the design of organic systems suitable for the assembly of supramolecular compounds, we have synthesized the Schiff base ligand H₂CSNA, from the condensation reaction of 3-carboxylsalicylaldehyde with 2-nitroaniline, and its binuclear cobalt(II) complex, [Co₂(CSNA)₂], (I) [where CSNA^2- = 3-[(2-nitrophenyl)iminomethyl]-2-oxidobenzoate dianion].

Complex (I), a 2-NA Schiff base cobalt(II) complex, consists of centrosymmetric binuclear molecular units of [Co₂(CSNA)₂], as shown in Fig. 1. Selected bond distances and angles are given in Table 1. Each molecular unit contains two CSNA^2- anions and two Co²⁺ ions. The two CSNA^2- anions act as N1,O2,O3 tridentate ligands to chelate two Co²⁺ ions with the phenolate O-atoms (O3 and O3ⁱ: (i) = -x + 2, -y, -z + 1) as bridging atoms. The distance between the two metal centres is found to be 2.9950 (11) Å. These coordination bonds, forming a basal plane, are of normal strength with average bond length of Co—O 1.914 (3) Å, and Co—N 1.947 (4) Å.

The distances of the nitro group O-atoms O4 and O5ⁱ [symmetry code: (i) -x + 2, -y, -z + 1] to atom Co1 are 2.8066 (44) Å and 2.8667 (44) Å, respectively. Calculated by the formula of s = exp[(r_o-r)/B], (r = bond length, s = bond value) (Brown & Altermatt, 1985), the two bond values are 0.049 and 0.042. Hence, only weak interactions exist between atoms O4 and Co1, and Co1 and O5ⁱ (Tabel 1). Thus every binuclear cobalt unit interacts with four adjacent ones through four nitro groups, forming a two-dimensional network (Fig. 2). The conformation of the ligand has changed obviously after coordination. It can be deduced that the free ligand might be a planar molecule because all the nonhydrogen atoms are in a conjugated system. In order to fulfil the intramolecular axial interaction of the nitro group, distortion has occurred between the two benzene rings of the ligand. In the binuclear molecular unit, the dihedral angle between the two benzene rings is 64.31 (13)°.

In the crystal structure there are C—H···O(nitro) interactions (Table 2), and relatively strong π···π stacking interactions [the distances between the centroids of the adjacent benzene rings are 3.5004 (2) Å, 3.6671 (2) Å and 3.6677 (2) Å] leading to the formation of a three-dimensional framework (Fig. 3).

The emission spectra of ethanol solutions of H₂CSNA and complex (I) were measured at rt. As seen in Fig. 4, the results show that H₂CSNA, exhibits two emissions at 394 nm and 466 nm (ν_ex = 351 nm). Measurement of the complex revealed two emissions at 394 nm and 468 nm (ν_ex = 351 nm). The similarity of the emissions bands of complex (I) and H₂CSNA indicates that the luminescence emission of complex (I) may be assigned to the intraligand emission of the H₂CSNA ligand (Li et al., 2008).

In summary, an unprecedented 2-nitroaniline Schiff base complex, [Co₂(CSNA)₂], has been synthesized and structurally characterized. This successful synthesis provides a feasible and effective synthetic method for searching and exploring other novel 2-nitroaniline Schiff base complexes.

Related literature top

For binuclear cobalt(II) complexes of Schiff base ligands, see: Adams et al. (2002); Tone et al. (2007). For the design of molecular solids, see: Zheng et al. (2003). For bond-valence parameters, see: Brown & Altermatt (1985). For luminescence emmission, see: Li et al. (2008).

Experimental top

0.166 g (1.0 mmol) of 3-carboxylsalicylaldehyde and 0.138 g (1.0 mmol) of 2-nitroaniline were dissolved in 10 ml of methanol. The mixture was stirred at 60°C, and gradually a yellow precipitate (H₂CSNA) was formed. 1 h later, 10 ml of a methanol solution of 0.08 g (2.0 mmol) NaOH, and 10 ml of a methanol solution of 0.285 g (1.2 mmol) CoCl₂.6H₂O were added to the H₂CSNA solution, sequentially. After sirring for 1 h at 60°C the solution was allowed to cool to rt and then filtered. The filtrate was left to slowly evaporate at rt. After 10 d, blue crystals, suitable for X-ray structural analysis, were formed. FT/IR data for compound (I): 1634 cm^-1(s, C=N), 1601 cm^-1(s, benzene ring), 1579 cm^-1(s, ν_as(COO)), 1549 cm^-1 (s, ν_as(NO₂)), 1360 cm^-1 (s, ν_s(COO)), 1299 cm^-1 (s, ν_s(NO₂)).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2003).

Figures top

	Fig. 1. A view of the molecular structure of compound (I), showing the atom-labeling scheme. Atoms labeled (') are generated by the symmetry code -x + 2, -y, -z + 1.
	Fig. 2. View along the a-axis of the two-dimensional network of complex (I).
	Fig. 3. A view down the c axis of the π—π stacking interactions between the two-dimensional networks in compound (I).
	Fig. 4. Emission spectra of the ligand and complex (I) in ethanol solution, λ_ex= 351 nm.

bis{µ-3-[(2-nitrophenyl)iminomethyl]-2-oxidobenzoato}dicopper(II) top

Crystal data top

[Co₂(C₁₄H₈N₂O₅)₂]	F(000) = 692
M_r = 686.31	D_x = 1.877 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1063 reflections
a = 8.3398 (6) Å	θ = 3.1–22.1°
b = 11.0454 (8) Å	µ = 1.44 mm⁻¹
c = 13.3681 (9) Å	T = 296 K
β = 99.604 (1)°	Block, colourless
V = 1214.16 (15) Å³	0.21 × 0.16 × 0.11 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2132 independent reflections
Radiation source: fine-focus sealed tube	1536 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.752, T_max = 0.858	k = −11→13
6134 measured reflections	l = −15→14

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0704P)²] where P = (F_o² + 2F_c²)/3
2132 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Co₂(C₁₄H₈N₂O₅)₂]	V = 1214.16 (15) Å³
M_r = 686.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3398 (6) Å	µ = 1.44 mm⁻¹
b = 11.0454 (8) Å	T = 296 K
c = 13.3681 (9) Å	0.21 × 0.16 × 0.11 mm
β = 99.604 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2132 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1536 reflections with I > 2σ(I)
T_min = 0.752, T_max = 0.858	R_int = 0.045
6134 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	Δρ_max = 0.63 e Å⁻³
2132 reflections	Δρ_min = −0.34 e Å⁻³
199 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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	0.98614 (6)	0.01580 (5)	0.38763 (4)	0.0353 (2)
O1	0.6445 (5)	0.0607 (5)	0.7562 (3)	0.0940 (18)
O2	0.8752 (4)	0.0241 (3)	0.7042 (2)	0.0581 (11)
O3	0.8641 (3)	0.0427 (3)	0.4968 (2)	0.0452 (10)
O4	1.0672 (5)	0.2394 (4)	0.3097 (3)	0.0765 (17)
O5	1.1737 (5)	0.2946 (4)	0.1830 (4)	0.101 (2)
N1	0.8176 (4)	0.0891 (3)	0.2876 (3)	0.0456 (12)
N2	1.0763 (5)	0.2359 (4)	0.2183 (3)	0.0615 (17)
C1	0.7269 (6)	0.0597 (5)	0.6879 (4)	0.0515 (17)
C2	0.6501 (5)	0.1047 (4)	0.5856 (3)	0.0430 (16)
C3	0.7180 (5)	0.0937 (3)	0.4962 (3)	0.0390 (14)
C4	0.6304 (5)	0.1389 (4)	0.4043 (3)	0.0433 (16)
C5	0.6823 (6)	0.1325 (4)	0.3083 (4)	0.0501 (17)
C6	0.4790 (5)	0.1957 (4)	0.4036 (4)	0.0541 (19)
C7	0.4134 (6)	0.2066 (4)	0.4893 (4)	0.0529 (19)
C8	0.4995 (5)	0.1602 (4)	0.5784 (4)	0.0502 (17)
C9	0.8350 (6)	0.0974 (4)	0.1838 (4)	0.0529 (17)
C10	0.7265 (7)	0.0345 (5)	0.1114 (4)	0.0668 (19)
C11	0.7394 (7)	0.0423 (5)	0.0094 (4)	0.069 (2)
C12	0.8596 (7)	0.1094 (5)	−0.0233 (4)	0.065 (2)
C13	0.9691 (7)	0.1698 (5)	0.0476 (4)	0.071 (2)
C14	0.9579 (6)	0.1648 (4)	0.1501 (4)	0.0540 (17)
H5	0.61030	0.16330	0.25350	0.0600*
H6	0.42290	0.22650	0.34290	0.0650*
H7	0.31340	0.24430	0.48820	0.0640*
H8	0.45370	0.16660	0.63700	0.0600*
H10	0.64530	−0.01270	0.13150	0.0800*
H11	0.66480	0.00110	−0.03810	0.0830*
H12	0.86670	0.11380	−0.09190	0.0780*
H13	1.05180	0.21470	0.02670	0.0850*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0287 (3)	0.0470 (4)	0.0303 (3)	0.0063 (3)	0.0052 (2)	0.0036 (3)
O1	0.062 (3)	0.174 (4)	0.049 (2)	0.029 (3)	0.018 (2)	−0.001 (3)
O2	0.048 (2)	0.083 (2)	0.0446 (19)	0.0159 (17)	0.0113 (15)	0.0061 (17)
O3	0.0358 (17)	0.0562 (18)	0.0441 (18)	0.0091 (14)	0.0080 (13)	0.0063 (15)
O4	0.072 (3)	0.091 (3)	0.065 (3)	−0.014 (2)	0.007 (2)	−0.004 (2)
O5	0.084 (3)	0.125 (4)	0.107 (4)	−0.035 (3)	0.052 (3)	0.003 (3)
N1	0.040 (2)	0.059 (2)	0.038 (2)	0.0039 (18)	0.0074 (16)	0.0094 (18)
N2	0.055 (3)	0.075 (3)	0.056 (3)	0.000 (2)	0.014 (2)	0.009 (2)
C1	0.046 (3)	0.067 (3)	0.043 (3)	0.005 (2)	0.012 (2)	−0.006 (2)
C2	0.035 (2)	0.047 (3)	0.048 (3)	−0.002 (2)	0.010 (2)	−0.005 (2)
C3	0.030 (2)	0.038 (2)	0.048 (3)	−0.0018 (18)	0.0033 (19)	−0.001 (2)
C4	0.036 (2)	0.046 (3)	0.049 (3)	−0.004 (2)	0.010 (2)	0.000 (2)
C5	0.040 (3)	0.060 (3)	0.049 (3)	0.003 (2)	0.004 (2)	0.010 (2)
C6	0.037 (3)	0.053 (3)	0.070 (4)	0.004 (2)	0.002 (2)	0.012 (3)
C7	0.033 (3)	0.059 (3)	0.067 (4)	0.006 (2)	0.009 (2)	−0.002 (3)
C8	0.037 (3)	0.057 (3)	0.058 (3)	−0.002 (2)	0.012 (2)	−0.012 (2)
C9	0.043 (3)	0.063 (3)	0.051 (3)	0.006 (2)	0.003 (2)	0.007 (2)
C10	0.060 (3)	0.076 (4)	0.060 (3)	0.001 (3)	−0.003 (3)	0.001 (3)
C11	0.067 (4)	0.084 (4)	0.050 (3)	0.014 (3)	−0.005 (3)	0.003 (3)
C12	0.066 (4)	0.083 (4)	0.045 (3)	0.022 (3)	0.004 (3)	−0.001 (3)
C13	0.071 (4)	0.083 (4)	0.064 (4)	0.023 (3)	0.027 (3)	0.016 (3)
C14	0.054 (3)	0.059 (3)	0.048 (3)	0.011 (2)	0.006 (2)	0.006 (2)

Geometric parameters (Å, º) top

Co1—O3	1.936 (3)	C4—C6	1.409 (6)
Co1—N1	1.947 (4)	C6—C7	1.355 (7)
Co1—O2ⁱ	1.874 (3)	C7—C8	1.383 (7)
Co1—O3ⁱ	1.929 (3)	C9—C10	1.395 (7)
O1—C1	1.231 (7)	C9—C14	1.401 (7)
O2—C1	1.281 (6)	C10—C11	1.388 (8)
O3—C3	1.341 (5)	C11—C12	1.375 (8)
O4—N2	1.237 (6)	C12—C13	1.374 (8)
O5—N2	1.196 (6)	C13—C14	1.390 (7)
N1—C5	1.298 (6)	C5—H5	0.9300
N1—C9	1.422 (7)	C6—H6	0.9300
N2—C14	1.457 (6)	C7—H7	0.9300
C1—C2	1.495 (7)	C8—H8	0.9300
C2—C3	1.411 (6)	C10—H10	0.9300
C2—C8	1.386 (6)	C11—H11	0.9300
C3—C4	1.412 (6)	C12—H12	0.9300
C4—C5	1.423 (7)	C13—H13	0.9300

Co1···O4	2.807 (4)	C3···C8^ix	3.398 (6)
Co1···N2	3.488 (4)	C3···C13^iv	3.347 (7)
Co1···O5ⁱⁱ	2.867 (5)	C4···C8^ix	3.496 (6)
Co1···N2ⁱⁱ	3.404 (4)	C4···C2^ix	3.583 (6)
Co1···C13ⁱⁱ	3.923 (6)	C4···C12^iv	3.421 (7)
O1···C11ⁱⁱⁱ	3.351 (7)	C5···O4	3.417 (7)
O1···C12ⁱⁱⁱ	3.230 (7)	C6···C2^ix	3.499 (6)
O2···N2ⁱ	3.057 (5)	C6···C1^ix	3.421 (7)
O2···C9ⁱ	2.946 (6)	C7···C2^ix	3.596 (6)
O2···C14ⁱ	3.030 (6)	C7···C3^ix	3.509 (6)
O2···O3	2.766 (4)	C8···C3^ix	3.398 (6)
O2···N2^iv	3.126 (5)	C8···O5^x	3.295 (6)
O2···O4ⁱ	2.961 (6)	C8···C4^ix	3.496 (6)
O2···N1ⁱ	2.836 (5)	C11···C13^xi	3.549 (8)
O3···O2	2.766 (4)	C11···O1^xii	3.351 (7)
O3···O3ⁱ	2.444 (4)	C12···C4^viii	3.421 (7)
O3···N1	2.806 (5)	C12···O1^xii	3.230 (7)
O3···C13^iv	3.334 (6)	C12···C3^viii	3.510 (7)
O3···C5	2.891 (6)	C12···C13^xi	3.437 (8)
O4···Co1	2.807 (4)	C12···C12^xi	3.351 (8)
O4···N1	2.640 (5)	C13···C11^xi	3.549 (8)
O4···C5	3.417 (7)	C13···Co1^vi	3.923 (6)
O4···O2ⁱ	2.961 (6)	C13···C3^viii	3.347 (7)
O5···C8^v	3.295 (6)	C13···C12^xi	3.437 (8)
O5···Co1^vi	2.867 (5)	C13···O3^viii	3.334 (6)
O1···H11ⁱⁱⁱ	2.8100	C14···O2ⁱ	3.030 (6)
O1···H8	2.3700	C1···H12ⁱⁱⁱ	3.0400
O1···H12ⁱⁱⁱ	2.5800	C5···H10	2.8300
O2···H12ⁱⁱⁱ	2.9100	C8···H5^iv	3.0700
O4···H7^vii	2.8800	C10···H5	2.6800
O4···H12^iv	2.8100	H5···C10	2.6800
O5···H13	2.3400	H5···H6	2.2300
O5···H6^vii	2.8200	H5···H10	2.5900
O5···H8^v	2.5500	H5···C8^viii	3.0700
N1···O3	2.806 (5)	H6···O5^xiii	2.8200
N1···O4	2.640 (5)	H6···H5	2.2300
N1···N2	2.968 (5)	H7···O4^xiii	2.8800
N1···C3	3.040 (6)	H7···H13^x	2.3700
N1···O2ⁱ	2.836 (5)	H8···O1	2.3700
N2···Co1	3.488 (4)	H8···O5^x	2.5500
N2···N1	2.968 (5)	H10···C5	2.8300
N2···Co1^vi	3.404 (4)	H10···H5	2.5900
N2···O2ⁱ	3.057 (5)	H11···O1^xii	2.8100
N2···O2^viii	3.126 (5)	H12···O1^xii	2.5800
C1···C6^ix	3.421 (7)	H12···O2^xii	2.9100
C2···C6^ix	3.499 (6)	H12···C1^xii	3.0400
C2···C4^ix	3.583 (6)	H12···O4^viii	2.8100
C2···C7^ix	3.596 (6)	H13···O5	2.3400
C3···C12^iv	3.510 (7)	H13···H7^v	2.3700
C3···C7^ix	3.509 (6)

O3—Co1—N1	92.51 (14)	C4—C6—C7	121.5 (5)
O2ⁱ—Co1—O3	171.54 (13)	C6—C7—C8	118.1 (4)
O3—Co1—O3ⁱ	78.42 (11)	C2—C8—C7	123.9 (5)
O2ⁱ—Co1—N1	95.83 (14)	N1—C9—C10	119.0 (4)
O3ⁱ—Co1—N1	170.41 (14)	N1—C9—C14	123.2 (4)
O2ⁱ—Co1—O3ⁱ	93.33 (12)	C10—C9—C14	117.8 (5)
Co1ⁱ—O2—C1	130.1 (3)	C9—C10—C11	120.2 (5)
Co1—O3—C3	130.6 (2)	C10—C11—C12	121.7 (5)
Co1—O3—Co1ⁱ	101.58 (12)	C11—C12—C13	118.6 (5)
Co1ⁱ—O3—C3	127.7 (2)	C12—C13—C14	121.0 (5)
Co1—N1—C5	124.1 (3)	N2—C14—C9	122.8 (5)
Co1—N1—C9	121.2 (3)	N2—C14—C13	116.5 (4)
C5—N1—C9	114.7 (4)	C9—C14—C13	120.8 (5)
O4—N2—O5	122.0 (5)	N1—C5—H5	116.00
O4—N2—C14	119.2 (4)	C4—C5—H5	116.00
O5—N2—C14	118.6 (4)	C4—C6—H6	119.00
O1—C1—O2	121.3 (5)	C7—C6—H6	119.00
O1—C1—C2	117.9 (5)	C6—C7—H7	121.00
O2—C1—C2	120.8 (4)	C8—C7—H7	121.00
C1—C2—C3	125.1 (4)	C2—C8—H8	118.00
C1—C2—C8	117.1 (4)	C7—C8—H8	118.00
C3—C2—C8	117.8 (4)	C9—C10—H10	120.00
O3—C3—C2	121.6 (4)	C11—C10—H10	120.00
O3—C3—C4	119.4 (4)	C10—C11—H11	119.00
C2—C3—C4	119.0 (4)	C12—C11—H11	119.00
C3—C4—C5	125.2 (4)	C11—C12—H12	121.00
C3—C4—C6	119.8 (4)	C13—C12—H12	121.00
C5—C4—C6	115.1 (4)	C12—C13—H13	120.00
N1—C5—C4	128.1 (5)	C14—C13—H13	120.00

N1—Co1—O3—C3	0.1 (3)	O2—C1—C2—C3	11.4 (7)
N1—Co1—O3—Co1ⁱ	−176.86 (15)	O2—C1—C2—C8	−169.5 (4)
O3ⁱ—Co1—O3—C3	176.9 (4)	C1—C2—C3—O3	−1.7 (6)
O3ⁱ—Co1—O3—Co1ⁱ	−0.02 (14)	C1—C2—C3—C4	179.0 (4)
O3—Co1—N1—C5	−0.5 (4)	C8—C2—C3—O3	179.1 (4)
O3—Co1—N1—C9	−179.7 (3)	C8—C2—C3—C4	−0.2 (6)
O2ⁱ—Co1—N1—C5	178.1 (4)	C1—C2—C8—C7	179.9 (4)
O2ⁱ—Co1—N1—C9	−1.2 (3)	C3—C2—C8—C7	−0.9 (7)
N1—Co1—O2ⁱ—C1ⁱ	168.2 (4)	O3—C3—C4—C5	1.8 (6)
O3—Co1—O3ⁱ—Co1ⁱ	0.02 (14)	O3—C3—C4—C6	−178.2 (4)
O3—Co1—O3ⁱ—C3ⁱ	177.1 (3)	C2—C3—C4—C5	−179.0 (4)
Co1ⁱ—O2—C1—O1	166.4 (4)	C2—C3—C4—C6	1.1 (6)
Co1ⁱ—O2—C1—C2	−15.3 (7)	C3—C4—C5—N1	−2.4 (8)
Co1—O3—C3—C2	−179.9 (3)	C6—C4—C5—N1	177.6 (4)
Co1—O3—C3—C4	−0.7 (5)	C3—C4—C6—C7	−1.0 (7)
Co1ⁱ—O3—C3—C2	−3.7 (5)	C5—C4—C6—C7	179.0 (4)
Co1ⁱ—O3—C3—C4	175.5 (3)	C4—C6—C7—C8	0.0 (7)
Co1—N1—C5—C4	1.6 (7)	C6—C7—C8—C2	1.0 (7)
C9—N1—C5—C4	−179.1 (4)	N1—C9—C10—C11	179.2 (5)
Co1—N1—C9—C10	116.1 (4)	C14—C9—C10—C11	−1.7 (8)
Co1—N1—C9—C14	−63.1 (5)	N1—C9—C14—N2	−2.0 (7)
C5—N1—C9—C10	−63.3 (6)	N1—C9—C14—C13	−180.0 (4)
C5—N1—C9—C14	117.6 (5)	C10—C9—C14—N2	178.8 (5)
O4—N2—C14—C9	−1.4 (7)	C10—C9—C14—C13	0.9 (7)
O4—N2—C14—C13	176.6 (5)	C9—C10—C11—C12	1.2 (9)
O5—N2—C14—C9	−177.2 (5)	C10—C11—C12—C13	0.0 (9)
O5—N2—C14—C13	0.8 (7)	C11—C12—C13—C14	−0.8 (8)
O1—C1—C2—C3	−170.3 (5)	C12—C13—C14—N2	−177.7 (5)
O1—C1—C2—C8	8.9 (7)	C12—C13—C14—C9	0.4 (8)

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, y−1/2, −z+1/2; (iii) x, y, z+1; (iv) x, −y+1/2, z+1/2; (v) x+1, −y+1/2, z−1/2; (vi) −x+2, y+1/2, −z+1/2; (vii) x+1, y, z; (viii) x, −y+1/2, z−1/2; (ix) −x+1, −y, −z+1; (x) x−1, −y+1/2, z+1/2; (xi) −x+2, −y, −z; (xii) x, y, z−1; (xiii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1	0.93	2.37	2.713 (7)	102
C8—H8···O5^x	0.93	2.55	3.295 (6)	138
C12—H12···O1^xii	0.93	2.58	3.230 (7)	128
C13—H13···O5	0.93	2.34	2.657 (7)	100

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₁₄H₈N₂O₅)₂]
M_r	686.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.3398 (6), 11.0454 (8), 13.3681 (9)
β (°)	99.604 (1)
V (Å³)	1214.16 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.21 × 0.16 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.752, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	6134, 2132, 1536
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.00
No. of reflections	2132
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.34

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

Co1—O3	1.936 (3)	Co1—O2ⁱ	1.874 (3)
Co1—N1	1.947 (4)	Co1—O3ⁱ	1.929 (3)

Co1···O4	2.807 (4)	Co1···O5ⁱⁱ	2.867 (5)

O3—Co1—N1	92.51 (14)	O2ⁱ—Co1—N1	95.83 (14)
O2ⁱ—Co1—O3	171.54 (13)	O3ⁱ—Co1—N1	170.41 (14)
O3—Co1—O3ⁱ	78.42 (11)	O2ⁱ—Co1—O3ⁱ	93.33 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O5ⁱⁱⁱ	0.93	2.55	3.295 (6)	138
C12—H12···O1^iv	0.93	2.58	3.230 (7)	128

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

Acknowledgements

The authors are grateful for financial support from the Henan Administration of Science and Technology (grant No. 0111030700).

References

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