Poly[[(μ2-benzene-1,4-dicarboxyl­ato-κ4O1,O1′:O4,O4′)(μ2-di-4-pyridyldiazene-κ2N1:N1′)cobalt(II)] N,N-dimethyl­formamide disolvate hemihydrate]

Chu, C.-X.; Zhang, Y.; Zhou, H.; Yuan, A.-H.

doi:10.1107/S1600536809030189

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Pages m1035-m1036

doi:10.1107/S1600536809030189

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Poly[[(μ₂-benzene-1,4-dicarboxylato-κ⁴O¹,O^1′:O⁴,O^4′)(μ₂-di-4-pyridyldiazene-κ²N¹:N^1′)cobalt(II)] N,N-dimethylformamide disolvate hemihydrate]

Chao-Xia Chu,^a Ying Zhang,^a Hu Zhou ^a and Ai-Hua Yuan ^a ^*

^aSchool of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: aihuayuan@163.com

(Received 5 July 2009; accepted 29 July 2009; online 8 August 2009)

In the title compound, {[Co(C₈H₄O₄)(C₁₀H₈N₄)]·2C₃H₇NO·0.5H₂O}_n, the Co^II atom is six-coordinated by four O atoms from two benzene-1,4-dicarboxylate (H₂bdc²⁻) groups and two N atoms from two 4,4′-azopyridine (4,4′-azpy, or di-4-pyridyldiazene) ligands, leading to a distorted octahedral geometry. The structure consists of two-dimensional corrugated sheets with a 4⁴ topology in an …ABAB… packing pattern stacking along the a axis. The separation of the adjacent corrugated sheets is ca. 8.561 (2) Å (Co⋯Co distance) along the a axis. The uncoordinated water molecule is half-occupied. The crystal structure is stabilized by O—H⋯N and C—H⋯O hydrogen-bonding interactions.

Related literature

For background to metal-organic framework (MOF) materials, see: Halder & Kepert (2002 ); Murray & Cashion (2002 ); Rosi et al. (2003 ); Rowsell et al. (2005 ); Seo et al. (2000 ). For compounds containing H₂bdc or 4,4′-azpy ligands, see: Halder et al. (2005 ); Jia (2007 ).

Experimental

Crystal data

[Co(C₈H₄O₄)(C₁₀H₈N₄)]·2C₃H₇NO·0.5H₂O
M_r = 562.45
Orthorhombic, F d d 2
a = 32.441 (4) Å
b = 34.138 (4) Å
c = 10.1972 (12) Å
V = 11293 (2) Å³
Z = 16
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 291 K
0.25 × 0.20 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.84, T_max = 0.88 (expected range = 0.906–0.949)
21948 measured reflections
5500 independent reflections
4262 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.134
S = 1.07
5500 reflections
335 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 2564 Friedel pairs
Flack parameter: 0.04 (2)

Table 1
Selected geometric parameters (Å, °)

N1—Co1	2.079 (4)
N4—Co1ⁱ	2.062 (4)
O1—Co1	2.153 (3)
O2—Co1	2.153 (3)
O3—Co1^iv	2.059 (3)
O4—Co1^iv	2.353 (3)
Symmetry codes: (i) x, y, z-1; (ii) $[-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (iii) x, y, z+1; (iv) $[-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯N5ⁱⁱ	0.85	2.32	2.932 (7)	129
C7—H7⋯O7	0.93	2.30	3.126 (7)	147
C16—H16⋯O3	0.93	2.48	2.791 (4)	100
C17—H17⋯O1	0.93	2.49	2.800 (4)	100
C19—H19C⋯O1^iv	0.96	2.37	3.150 (6)	138
C23—H23A⋯O6^v	0.96	1.71	2.624 (5)	158
Symmetry codes: (ii) $[-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (iv) $[-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (v) $[-x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030189/at2838sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030189/at2838Isup2.hkl

checkCIF report

Comment top

Metal organic framework (MOF) materials have attracted much attention due to their potential functionalities such as gas storage (Rosi et al., 2003; Rowsell et al., 2005), sensing (Halder et al., 2002), and catalysis (Seo et al., 2000). The organic ligands, especially, benzene-1,4-dicarboxylate (H₂bdc) and 4,4'-azopyridine (4,4'-azpy), play a great role on constructing the topological architectures of MOFs (Jia, 2007; Halder et al., 2005). Here we employed H₂bdc and 4,4'-azpy as mixed ligands to bridge the Co^II atom, obtaining the title compound by solvothermal synthesis.

In the structure of the title compound, each Co^II atom, lying on an inversion center, is coordinated by four oxygen atoms from two H₂BDC groups and two nitrogen atoms from two 4,4'-azpy ligands, exhibiting a slightly distorted octahedral geometry (Fig. 1). The bond lengths of Co—O range from 2.059 (3) to 2.353 (3) Å, while the ones of Co—N are 2.079 (4) Å for Co1—N1 and 2.062 (4) Å for Co1—N4, respectively (Table 1). The Co^II centers are linked by H₂bdc groups into one-dimensional infinite zigzag chains along the b axis in the bc plane. Then, the chains are further linked by 4,4'- azpy ligands along the c axis, resulting in two-dimensional corrugated sheets with 4⁴ topology. These corrugated sheets without interpenetration are stacking along the a axis in an ABAB packing mode (Fig. 2). The torsion angle of the adjacent sheets is ca. 45 ° in the bc plane, while the separation between adjacent corrugated sheets is ca. 8.56 Å (Co···Co distance) along the a axis.

The crystal structure is stabilized by O—H···N and C—H···O hydrogen bonding interactions (Table 2).

Related literature top

For background to metal-organic framework (MOF) materials, see: Halder et al. (2002); Murray & Cashion (2002); Rosi et al. (2003); Rowsell et al. (2005); Seo et al. (2000). For compounds containing H₂bdc or 4,4'-azpy ligands, see: Halder et al. (2005); Jia (2007).

Experimental top

A mixture of CoCl₂.6H₂O (23.8 mg, 0.1 mmol), H₂bdc (16.6 mg, 0.1 mmol), 4,4'-azpy (18.4 mg, 0.1 mmol) and DMF (N, N-dimethylformamide) (10 ml) was stirred for 15 min at room temperature and then transferred into a Teflon-lined stainless-steel vessel. The mixture was heated at 433 K for two days under autogenous pressure. After cooling the resulting solution to room temperature with the rate of 10 °C/h, purple and layer-shaped crystals were obtained. Analysis calculated for Co₂N₁₂O₁₃C₄₈H₅₄: C 51.25, H 4.80, N 14.93%; found: C 51.16, H 4.65, N 14.92%.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP diagram of the title compound. Displacement ellipsoids are drawn at the 30% probablity level. Hydrogen atoms are omitted for clarity.
	Fig. 2. View of the stacking without interpenetration of sheets along the a axis. Hydrogen atoms, solvent DMF molecules and water molecules are not involved for clarity.

Poly[[(µ₂-benzene-1,4-dicarboxylato- κ⁴O¹,O^1':O⁴,O^4')(µ₂-di-4- pyridyldiazene-κ²N¹:N^1')cobalt(II)] N,N-dimethylformamide disolvate hemihydrate] top

Crystal data top

[Co(C₈H₄O₄)(C₁₀H₈N₄)]·2C₃H₇NO·0.5H₂O	F(000) = 4672
M_r = 562.45	D_x = 1.323 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 3875 reflections
a = 32.441 (4) Å	θ = 2.2–24.4°
b = 34.138 (4) Å	µ = 0.66 mm⁻¹
c = 10.1972 (12) Å	T = 291 K
V = 11293 (2) Å³	Pale, purple
Z = 16	0.25 × 0.20 × 0.08 mm

Data collection top

Bruker SMART APEX CCD diffractometer	5500 independent reflections
Radiation source: sealed tube	4262 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −40→40
T_min = 0.84, T_max = 0.88	k = −42→41
21948 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.07P)² + 1.99P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
5500 reflections	Δρ_max = 0.35 e Å⁻³
335 parameters	Δρ_min = −0.36 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2564 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

Crystal data top

[Co(C₈H₄O₄)(C₁₀H₈N₄)]·2C₃H₇NO·0.5H₂O	V = 11293 (2) Å³
M_r = 562.45	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 32.441 (4) Å	µ = 0.66 mm⁻¹
b = 34.138 (4) Å	T = 291 K
c = 10.1972 (12) Å	0.25 × 0.20 × 0.08 mm

Data collection top

Bruker SMART APEX CCD diffractometer	5500 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	4262 reflections with I > 2σ(I)
T_min = 0.84, T_max = 0.88	R_int = 0.062
21948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.134	Δρ_max = 0.35 e Å⁻³
S = 1.07	Δρ_min = −0.36 e Å⁻³
5500 reflections	Absolute structure: Flack (1983), 2564 Freidel pairs
335 parameters	Absolute structure parameter: 0.04 (2)
1 restraint

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)
C1	0.52950 (14)	0.07179 (14)	0.9140 (5)	0.0483 (11)
H1	0.5231	0.0517	0.9724	0.058*
C2	0.55879 (14)	0.06426 (13)	0.8190 (5)	0.0469 (10)
H2	0.5719	0.0401	0.8153	0.056*
C3	0.56831 (13)	0.09346 (13)	0.7291 (5)	0.0440 (10)
C4	0.54745 (14)	0.12918 (13)	0.7419 (5)	0.0460 (11)
H4	0.5529	0.1498	0.6847	0.055*
C5	0.51897 (13)	0.13334 (13)	0.8397 (6)	0.0543 (12)
H5	0.5050	0.1571	0.8452	0.065*
C6	0.51064 (14)	0.08224 (13)	0.3277 (5)	0.0471 (10)
H6	0.4900	0.0634	0.3279	0.057*
C7	0.53796 (13)	0.08165 (13)	0.4260 (5)	0.0447 (11)
H7	0.5355	0.0632	0.4927	0.054*
C8	0.57026 (13)	0.10881 (12)	0.4282 (4)	0.0393 (10)
C9	0.57199 (12)	0.13488 (13)	0.3217 (5)	0.0447 (10)
H9	0.5932	0.1531	0.3151	0.054*
C10	0.54305 (13)	0.13299 (13)	0.2316 (4)	0.0448 (10)
H10	0.5449	0.1507	0.1625	0.054*
C11	0.43039 (14)	0.16957 (14)	1.0169 (4)	0.0438 (10)
C12	0.40496 (7)	0.20614 (7)	0.9897 (3)	0.0409 (10)
C13	0.41490 (7)	0.24214 (8)	1.0450 (3)	0.0467 (11)
H13	0.4377	0.2444	1.0996	0.056*
C14	0.39070 (9)	0.27481 (6)	1.0187 (3)	0.0460 (11)
H14	0.3973	0.2989	1.0557	0.055*
C15	0.35657 (8)	0.27148 (7)	0.9370 (3)	0.0463 (11)
C16	0.34663 (7)	0.23548 (8)	0.8817 (3)	0.0437 (10)
H16	0.3238	0.2333	0.8271	0.052*
C17	0.37083 (8)	0.20281 (6)	0.9081 (3)	0.0419 (10)
H17	0.3642	0.1787	0.8711	0.050*
C18	0.32954 (13)	0.30541 (13)	0.9112 (4)	0.0416 (10)
C19	0.34469 (15)	0.31385 (14)	0.5392 (4)	0.0459 (11)
H19A	0.3659	0.2965	0.5700	0.069*
H19B	0.3189	0.3068	0.5790	0.069*
H19C	0.3516	0.3403	0.5623	0.069*
C20	0.32794 (13)	0.34669 (13)	0.3270 (5)	0.0469 (11)
H20A	0.3427	0.3492	0.2459	0.070*
H20B	0.3336	0.3689	0.3818	0.070*
H20C	0.2989	0.3454	0.3094	0.070*
C21	0.35209 (14)	0.27414 (13)	0.3303 (5)	0.0465 (10)
H21A	0.3777	0.2632	0.3487	0.056*
C22	0.46065 (14)	0.18349 (13)	0.4854 (5)	0.0464 (11)
H22A	0.4494	0.1745	0.4037	0.070*
H22B	0.4432	0.1753	0.5561	0.070*
H22C	0.4877	0.1726	0.4971	0.070*
C23	0.44909 (13)	0.24827 (14)	0.6023 (4)	0.0464 (11)
H23A	0.4725	0.2557	0.6543	0.070*
H23B	0.4313	0.2317	0.6531	0.070*
H23C	0.4343	0.2713	0.5757	0.070*
C24	0.47026 (13)	0.24724 (14)	0.3600 (4)	0.0453 (10)
H24A	0.4547	0.2687	0.3336	0.054*
N1	0.50968 (12)	0.10580 (11)	0.9280 (4)	0.0501 (10)
N2	0.59730 (11)	0.08629 (11)	0.6303 (4)	0.0464 (9)
N3	0.59939 (11)	0.11042 (11)	0.5299 (4)	0.0464 (9)
N4	0.51102 (12)	0.10792 (11)	0.2297 (4)	0.0477 (10)
N5	0.34115 (11)	0.31054 (11)	0.3948 (4)	0.0462 (9)
N6	0.46332 (12)	0.22667 (11)	0.4842 (4)	0.0485 (9)
O1	0.41954 (9)	0.13759 (9)	0.9692 (3)	0.0463 (7)
O2	0.46054 (10)	0.17289 (9)	1.0912 (3)	0.0490 (8)
Co1	0.467820 (19)	0.110280 (18)	1.08164 (6)	0.04633 (17)
O3	0.30051 (9)	0.30257 (8)	0.8275 (3)	0.0450 (7)
O4	0.33472 (10)	0.33757 (9)	0.9713 (3)	0.0470 (7)
O5	0.32930 (9)	0.25672 (9)	0.2523 (3)	0.0490 (8)
O6	0.49957 (10)	0.23314 (9)	0.2912 (3)	0.0495 (8)
O7	0.49198 (17)	0.02737 (16)	0.6249 (6)	0.0438 (15)	0.50
H7A	0.4779	0.0440	0.6677	0.053*	0.50
H7C	0.5147	0.0233	0.6643	0.053*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.055 (3)	0.041 (2)	0.049 (3)	0.003 (2)	0.011 (2)	0.018 (2)
C2	0.052 (2)	0.045 (2)	0.044 (2)	0.0129 (19)	0.004 (2)	0.011 (2)
C3	0.038 (2)	0.045 (2)	0.049 (3)	0.0034 (19)	−0.0015 (19)	0.013 (2)
C4	0.046 (2)	0.034 (2)	0.058 (3)	−0.0052 (19)	0.008 (2)	0.011 (2)
C5	0.039 (2)	0.041 (2)	0.083 (3)	0.0057 (19)	0.018 (3)	0.023 (3)
C6	0.046 (2)	0.051 (3)	0.044 (2)	−0.0026 (19)	−0.014 (2)	0.013 (2)
C7	0.041 (2)	0.044 (3)	0.049 (3)	−0.0074 (19)	−0.0096 (19)	0.0190 (19)
C8	0.034 (2)	0.037 (2)	0.047 (2)	0.0005 (17)	0.0021 (17)	0.0160 (18)
C9	0.046 (2)	0.049 (2)	0.039 (2)	−0.0168 (19)	0.004 (2)	0.016 (2)
C10	0.045 (2)	0.046 (2)	0.043 (2)	−0.002 (2)	−0.001 (2)	0.014 (2)
C11	0.043 (2)	0.049 (3)	0.039 (2)	0.0040 (19)	0.007 (2)	0.0094 (19)
C12	0.036 (2)	0.041 (2)	0.046 (2)	−0.0004 (17)	0.0028 (19)	−0.0029 (19)
C13	0.048 (2)	0.041 (2)	0.051 (3)	0.0011 (19)	−0.019 (2)	−0.0003 (19)
C14	0.042 (2)	0.052 (3)	0.044 (2)	0.011 (2)	−0.0092 (19)	−0.011 (2)
C15	0.053 (3)	0.048 (3)	0.038 (2)	0.006 (2)	−0.015 (2)	0.008 (2)
C16	0.039 (2)	0.053 (3)	0.039 (2)	0.0139 (19)	−0.0165 (18)	−0.002 (2)
C17	0.033 (2)	0.045 (2)	0.048 (3)	0.0103 (18)	0.0037 (18)	0.0088 (19)
C18	0.042 (2)	0.035 (2)	0.048 (3)	−0.0035 (17)	−0.0090 (19)	−0.0017 (19)
C19	0.050 (2)	0.047 (3)	0.040 (2)	0.011 (2)	−0.0153 (19)	−0.0161 (19)
C20	0.048 (2)	0.045 (2)	0.048 (2)	0.0133 (18)	0.025 (2)	0.024 (2)
C21	0.050 (2)	0.048 (2)	0.041 (2)	−0.0162 (19)	0.022 (2)	−0.011 (2)
C22	0.048 (2)	0.045 (2)	0.046 (2)	−0.016 (2)	−0.019 (2)	0.018 (2)
C23	0.041 (2)	0.052 (3)	0.046 (3)	−0.0109 (19)	0.0137 (19)	0.016 (2)
C24	0.044 (2)	0.047 (2)	0.045 (2)	0.0162 (19)	0.0128 (19)	−0.0123 (19)
N1	0.045 (2)	0.047 (2)	0.058 (3)	0.0075 (18)	0.0063 (19)	0.0187 (19)
N2	0.042 (2)	0.042 (2)	0.056 (2)	0.0049 (16)	0.0049 (17)	0.0180 (17)
N3	0.046 (2)	0.049 (2)	0.0442 (19)	−0.0205 (17)	−0.0080 (16)	0.0169 (17)
N4	0.055 (2)	0.049 (2)	0.039 (2)	−0.0110 (18)	0.0065 (18)	0.0142 (17)
N5	0.050 (2)	0.044 (2)	0.045 (2)	−0.0143 (17)	0.0165 (17)	0.0115 (17)
N6	0.048 (2)	0.047 (2)	0.051 (2)	−0.0154 (17)	0.0111 (17)	−0.0098 (18)
O1	0.0475 (17)	0.0440 (18)	0.0475 (18)	0.0113 (13)	0.0030 (14)	0.0084 (15)
O2	0.0545 (19)	0.0475 (17)	0.0449 (17)	0.0085 (14)	−0.0040 (16)	0.0148 (16)
Co1	0.0466 (3)	0.0478 (3)	0.0446 (3)	−0.0004 (3)	−0.0022 (3)	0.0112 (3)
O3	0.0485 (16)	0.0416 (16)	0.0449 (16)	−0.0065 (13)	−0.0155 (15)	0.0075 (15)
O4	0.0540 (18)	0.0358 (16)	0.0512 (18)	−0.0083 (14)	0.0009 (15)	0.0047 (14)
O5	0.0458 (17)	0.0489 (19)	0.0522 (19)	0.0146 (13)	−0.0144 (14)	−0.0177 (15)
O6	0.0505 (17)	0.0525 (18)	0.0456 (18)	−0.0203 (15)	0.0137 (14)	−0.0169 (14)
O7	0.040 (3)	0.038 (3)	0.053 (4)	0.010 (2)	0.015 (3)	0.014 (3)

Geometric parameters (Å, º) top

C1—N1	1.335 (6)	C18—O4	1.268 (5)
C1—C2	1.381 (6)	C18—O3	1.275 (5)
C1—H1	0.9300	C19—N5	1.482 (6)
C2—C3	1.389 (6)	C19—H19A	0.9600
C2—H2	0.9300	C19—H19B	0.9600
C3—N2	1.399 (6)	C19—H19C	0.9600
C3—C4	1.401 (6)	C20—N5	1.478 (5)
C4—C5	1.367 (7)	C20—H20A	0.9600
C4—H4	0.9300	C20—H20B	0.9600
C5—N1	1.336 (6)	C20—H20C	0.9600
C5—H5	0.9300	C21—O5	1.238 (5)
C6—N4	1.329 (6)	C21—N5	1.449 (6)
C6—C7	1.338 (6)	C21—H21A	0.9300
C6—H6	0.9300	C22—N6	1.477 (6)
C7—C8	1.399 (6)	C22—H22A	0.9600
C7—H7	0.9300	C22—H22B	0.9600
C8—N3	1.404 (6)	C22—H22C	0.9600
C8—C9	1.405 (6)	C23—N6	1.486 (6)
C9—C10	1.315 (6)	C23—H23A	0.9600
C9—H9	0.9300	C23—H23B	0.9600
C10—N4	1.346 (6)	C23—H23C	0.9600
C10—H10	0.9300	C24—O6	1.276 (5)
C11—O2	1.242 (6)	C24—N6	1.465 (6)
C11—O1	1.246 (6)	C24—H24A	0.9300
C11—C12	1.522 (5)	N1—Co1	2.079 (4)
C12—C13	1.3900	N2—N3	1.316 (5)
C12—C17	1.3900	N4—Co1ⁱ	2.062 (4)
C13—C14	1.3900	O1—Co1	2.153 (3)
C13—H13	0.9300	O2—Co1	2.153 (3)
C14—C15	1.3900	Co1—O3ⁱⁱ	2.059 (3)
C14—H14	0.9300	Co1—N4ⁱⁱⁱ	2.062 (4)
C15—C16	1.3900	Co1—O4ⁱⁱ	2.353 (3)
C15—C18	1.477 (5)	O3—Co1^iv	2.059 (3)
C16—C17	1.3900	O4—Co1^iv	2.353 (3)
C16—H16	0.9300	O7—H7A	0.8499
C17—H17	0.9300	O7—H7C	0.8501

N1—C1—C2	124.6 (4)	H19A—C19—H19C	109.5
N1—C1—H1	117.7	H19B—C19—H19C	109.5
C2—C1—H1	117.7	N5—C20—H20A	109.5
C1—C2—C3	118.8 (4)	N5—C20—H20B	109.5
C1—C2—H2	120.6	H20A—C20—H20B	109.5
C3—C2—H2	120.6	N5—C20—H20C	109.5
C2—C3—N2	119.9 (4)	H20A—C20—H20C	109.5
C2—C3—C4	117.1 (4)	H20B—C20—H20C	109.5
N2—C3—C4	123.0 (4)	O5—C21—N5	123.8 (4)
C5—C4—C3	119.0 (4)	O5—C21—H21A	118.1
C5—C4—H4	120.5	N5—C21—H21A	118.1
C3—C4—H4	120.5	N6—C22—H22A	109.5
N1—C5—C4	124.8 (4)	N6—C22—H22B	109.5
N1—C5—H5	117.6	H22A—C22—H22B	109.5
C4—C5—H5	117.6	N6—C22—H22C	109.5
N4—C6—C7	124.5 (4)	H22A—C22—H22C	109.5
N4—C6—H6	117.7	H22B—C22—H22C	109.5
C7—C6—H6	117.7	N6—C23—H23A	109.5
C6—C7—C8	119.9 (4)	N6—C23—H23B	109.5
C6—C7—H7	120.1	H23A—C23—H23B	109.5
C8—C7—H7	120.1	N6—C23—H23C	109.5
C7—C8—N3	122.8 (4)	H23A—C23—H23C	109.5
C7—C8—C9	115.9 (4)	H23B—C23—H23C	109.5
N3—C8—C9	121.3 (4)	O6—C24—N6	114.1 (4)
C10—C9—C8	118.7 (4)	O6—C24—H24A	122.9
C10—C9—H9	120.6	N6—C24—H24A	122.9
C8—C9—H9	120.6	C1—N1—C5	115.6 (4)
C9—C10—N4	126.3 (4)	C1—N1—Co1	117.3 (3)
C9—C10—H10	116.9	C5—N1—Co1	127.1 (3)
N4—C10—H10	116.9	N3—N2—C3	119.0 (4)
O2—C11—O1	122.7 (4)	N2—N3—C8	121.1 (3)
O2—C11—C12	117.6 (4)	C6—N4—C10	114.6 (4)
O1—C11—C12	119.6 (4)	C6—N4—Co1ⁱ	124.7 (3)
O2—C11—Co1	61.4 (2)	C10—N4—Co1ⁱ	120.7 (3)
O1—C11—Co1	61.4 (2)	C21—N5—C20	125.1 (4)
C12—C11—Co1	174.3 (3)	C21—N5—C19	119.8 (4)
C13—C12—C17	120.0	C20—N5—C19	115.0 (4)
C13—C12—C11	121.7 (2)	C24—N6—C22	119.6 (4)
C17—C12—C11	118.3 (2)	C24—N6—C23	120.7 (3)
C12—C13—C14	120.0	C22—N6—C23	118.1 (4)
C12—C13—H13	120.0	C11—O1—Co1	88.0 (3)
C14—C13—H13	120.0	C11—O2—Co1	88.2 (3)
C15—C14—C13	120.0	O3ⁱⁱ—Co1—N4ⁱⁱⁱ	100.02 (14)
C15—C14—H14	120.0	O3ⁱⁱ—Co1—N1	95.89 (14)
C13—C14—H14	120.0	N4ⁱⁱⁱ—Co1—N1	96.03 (14)
C16—C15—C14	120.0	O3ⁱⁱ—Co1—O2	156.86 (12)
C16—C15—C18	118.9 (2)	N4ⁱⁱⁱ—Co1—O2	94.61 (14)
C14—C15—C18	121.0 (2)	N1—Co1—O2	100.31 (14)
C17—C16—C15	120.0	O3ⁱⁱ—Co1—O1	101.14 (13)
C17—C16—H16	120.0	N4ⁱⁱⁱ—Co1—O1	154.34 (15)
C15—C16—H16	120.0	N1—Co1—O1	96.06 (14)
C16—C17—C12	120.0	O2—Co1—O1	60.96 (12)
C16—C17—H17	120.0	O3ⁱⁱ—Co1—O4ⁱⁱ	59.18 (11)
C12—C17—H17	120.0	N4ⁱⁱⁱ—Co1—O4ⁱⁱ	92.07 (13)
O4—C18—O3	119.2 (4)	N1—Co1—O4ⁱⁱ	154.85 (14)
O4—C18—C15	120.9 (4)	O2—Co1—O4ⁱⁱ	102.73 (12)
O3—C18—C15	119.9 (3)	O1—Co1—O4ⁱⁱ	86.45 (11)
N5—C19—H19A	109.5	C18—O3—Co1^iv	97.3 (2)
N5—C19—H19B	109.5	C18—O4—Co1^iv	84.1 (3)
H19A—C19—H19B	109.5	H7A—O7—H7C	109.5
N5—C19—H19C	109.5

Symmetry codes: (i) x, y, z−1; (ii) −x+3/4, y−1/4, z+1/4; (iii) x, y, z+1; (iv) −x+3/4, y+1/4, z−1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···N5ⁱⁱ	0.85	2.32	2.932 (7)	129
C7—H7···O7	0.93	2.30	3.126 (7)	147
C16—H16···O3	0.93	2.48	2.791 (4)	100
C17—H17···O1	0.93	2.49	2.800 (4)	100
C19—H19C···O1^iv	0.96	2.37	3.150 (6)	138
C23—H23A···O6^v	0.96	1.71	2.624 (5)	158

Symmetry codes: (ii) −x+3/4, y−1/4, z+1/4; (iv) −x+3/4, y+1/4, z−1/4; (v) −x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₈H₄O₄)(C₁₀H₈N₄)]·2C₃H₇NO·0.5H₂O
M_r	562.45
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	291
a, b, c (Å)	32.441 (4), 34.138 (4), 10.1972 (12)
V (Å³)	11293 (2)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.25 × 0.20 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.84, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	21948, 5500, 4262
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.134, 1.07
No. of reflections	5500
No. of parameters	335
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.36
Absolute structure	Flack (1983), 2564 Freidel pairs
Absolute structure parameter	0.04 (2)

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006).

Selected geometric parameters (Å, º) top

N1—Co1	2.079 (4)	Co1—N4ⁱⁱⁱ	2.062 (4)
N4—Co1ⁱ	2.062 (4)	Co1—O4ⁱⁱ	2.353 (3)
O1—Co1	2.153 (3)	O3—Co1^iv	2.059 (3)
O2—Co1	2.153 (3)	O4—Co1^iv	2.353 (3)
Co1—O3ⁱⁱ	2.059 (3)

N2—N3—C8	121.1 (3)

Symmetry codes: (i) x, y, z−1; (ii) −x+3/4, y−1/4, z+1/4; (iii) x, y, z+1; (iv) −x+3/4, y+1/4, z−1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···N5ⁱⁱ	0.85	2.32	2.932 (7)	129
C7—H7···O7	0.93	2.30	3.126 (7)	147
C16—H16···O3	0.93	2.48	2.791 (4)	100
C17—H17···O1	0.93	2.49	2.800 (4)	100
C19—H19C···O1^iv	0.96	2.37	3.150 (6)	138
C23—H23A···O6^v	0.96	1.71	2.624 (5)	158

Symmetry codes: (ii) −x+3/4, y−1/4, z+1/4; (iv) −x+3/4, y+1/4, z−1/4; (v) −x+1, −y+1/2, z+1/2.

Acknowledgements

The work was supported by the University Natural Science Foundation of Jiangsu Province (No. 07KJB150030).

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