catena-Poly[bis­[(1,10-phenanthroline)cobalt(II)]-μ4-3,6-dicarb­oxy­cyclo­hexane-1,2,4,5-tetra­carboxyl­ato]

Xu, W.

doi:10.1107/S1600536811019970

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m832-m833

doi:10.1107/S1600536811019970

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catena-Poly[bis[(1,10-phenanthroline)cobalt(II)]-μ₄-3,6-dicarboxycyclohexane-1,2,4,5-tetracarboxylato]

Wei Xu ^a ^*

^aCenter of Applied Solid State Chemistry Research, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: xuwei@nbu.edu.cn

(Received 24 May 2011; accepted 26 May 2011; online 4 June 2011)

In the title compound, [Co₂(C₁₂H₈O₁₂)(C₁₂H₈N₂)₂]_n, each 3,6-dicarboxycyclohexane-1,2,4,5-tetracarboxylate (H₂chhc⁴⁻) anion has crystallographically imposed C₂ symmetry and bridges four six-coordinate Co atoms, generating polymeric chains running along [010]. These chains are further extended into a three-dimensional network via O—H⋯O hydrogen-bonding interactions and interchain π–π stacking interactions [centroid–centroid distance = 3.662 (2) Å].

Related literature

For the design and synthesis of coordination polymer complexes and their potential applications, see: Biradha et al. (2006 ); Bauer et al. (2007 ); Zacher et al. (2011 ). For the 1,2,3,4,5,6-cyclohexanehexacarboxylate ligand, see: Li et al. (2006 ); Wang et al. (2008 ); Thuéry & Masci (2010 ). For related structures, see: Konar et al. (2004 ); Li et al. (2006).

Experimental

Crystal data

[Co₂(C₁₂H₈O₁₂)(C₁₂H₈N₂)₂]
M_r = 822.46
Monoclinic, C 2/c
a = 22.180 (4) Å
b = 8.9520 (18) Å
c = 16.426 (3) Å
β = 93.33 (3)°
V = 3256.0 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 295 K
0.31 × 0.23 × 0.15 mm

Data collection

Siemens P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ) T_min = 0.702, T_max = 0.784
4566 measured reflections
3753 independent reflections
3312 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.083
S = 1.03
3753 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.2002 (13)
Co1—O2	2.0890 (13)
Co1—O5ⁱ	2.1211 (13)
Co1—O6ⁱ	2.1519 (13)
Co1—N1	2.1012 (15)
Co1—N2	2.1016 (15)
Symmetry code: (i) x, y-1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O2ⁱⁱ	0.79 (3)	1.89 (3)	2.627 (2)	156 (2)
Symmetry code: (ii) -x, -y+2, -z.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811019970/sj5153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019970/sj5153Isup2.hkl

checkCIF report

Comment top

The rational design and construction of metal-organic coordination polymers with flexible multidentate ligands have received more and more attention due to their intriguing structural topologies and novel properties for potential applications (Biradha, et al., 2006; Bauer, et al., 2007; Zacher, et al., 2011). As a typical flexible cycloalkane polycarboxylic acid ligand, we have focused on the 1,2,3,4,5,6-cyclohexanehexacarboxylic acid (H₆chhc) whose coordination chemistry remains practically unexplored. We were particularly aware that the greater flexibility of this ligand would make the prediction and control of the final coordination networks that it generates more difficult. (Wang, et al., 2008; Thuéry & Masci, 2010). Herein, we report a new cobalt coordination polymer, [Co₂(phen)₂(H₂chhc)]_n, resulting from reaction of Co²⁺ cations, phen and H₆chhc under hydrothermal conditions. It is isostructural with the previously reported [Ni₂(phen)₂(H₂chhc)]_n complex (Li, et al., 2006).

The asymmetric unit of the title compound consists of one Co²⁺ cation, one phen ligand and one-half of a H₂chhc^4- anion lying across a twofold rotation axis. The Co atoms are each in an octahedral environment defined by two N atoms of one phen ligand and four O atoms of two carboxylate groups from different H₂chhc^4- anions. The Co-O bond lengths fall in the range 2.089 (1)-2.200 (1) Å and the two Co-N distances are 2.101 (2) and 2.102 (2) Å (Table 1), thus falling in the expected region (Konar, et al., 2004). The octahedral coordination around the Co atoms are strongly distorted since the diametrical and non-diametrical bond angles indicate signficant deviations from 180° and 90°, respectively. The H₂chhc^4- ligands assume an e,e,e,e,e,e-conformation with the central ring adopting a chair-shaped configuration, the carboxylate and carboxyl groups being located at the equatorical sites. Each carboxylate group of the H₂chhc^4- anion chelates one Co atom. As a result, the H₂chhc^4- anions are each coordinated to four [Co(phen)]²⁺ units, leading to polymeric chains [Co₂(phen)₂(H₂chhc)]_n running along the [010] direction with the phen ligands exo-orientated (Fig. 1). The phen ligands of two adjacent supramolecular chains are stacked via the quinoline fragments (centroid-centroid distance = 3.662 (2) Å). Obviously, such π-π stacking interactions are responsible for the supramolecular assembly of the one-dimensional chains into two-dimensional layers parallel to (001) (Fig. 2). The layers are further connected to form a three-dimensional framework via interlayer O-H···O hydrogen bonds (d(O4···O2^#1 = 2.627 (2) Å, <O4-H4A···O2^#1 = 156 (2)°, #1 = -x, 2-y, -z).

Related literature top

For the design and synthesis of coordination polymer complexes and their potential applications, see: Biradha et al. (2006); Bauer et al. (2007); Zacher et al. (2011). For the 1,2,3,4,5,6-cyclohexanehexacarboxylate ligand, see: Li et al. (2006); Wang et al. (2008); Thuéry & Masci (2010). For related structures, see: Konar et al. (2004); Li et al. (2006).

Experimental top

CoCl₂.6H₂O (0.238 g, 1.0 mmol), H₆chhc (0.173 g, 0.5 mmol), phen (0.200 g, 1.0 mmol) and NaOH 1.5 mL (1 M) were stirred in 20 mL H₂O. The resulting mixture was placed in a 23 mL Teflon-lined autoclave and heated at 170 °C for 3 days. The reaction system was cooled to room temperature at a rate of 20 °C/h, and small amount of pink crystals of the title complex was obtained.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the polymer chain [Co₂(phen)₂(H₂chhc)]_n of the title complex. The displacement ellipsoids are drawn at 40% probability level, hydrogen atoms are omitted for clarity.
	Fig. 2. A view of a single layer of the title complex.

catena-Poly[bis[(1,10-phenanthroline)cobalt(II)]-µ₄-3,6- dicarboxycyclohexane-1,2,4,5-tetracarboxylato] top

Crystal data top

[Co₂(C₁₂H₈O₁₂)(C₁₂H₈N₂)₂]	F(000) = 1672
M_r = 822.46	D_x = 1.678 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 22.180 (4) Å	θ = 5.0–12.5°
b = 8.9520 (18) Å	µ = 1.10 mm⁻¹
c = 16.426 (3) Å	T = 295 K
β = 93.33 (3)°	Block, pink
V = 3256.0 (11) Å³	0.31 × 0.23 × 0.15 mm
Z = 4

Data collection top

Siemens P4 diffractometer	3312 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 27.5°, θ_min = 2.5°
θ/2θ scans	h = −28→1
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −1→11
T_min = 0.702, T_max = 0.784	l = −21→21
4566 measured reflections	3 standard reflections every 97 reflections
3753 independent reflections	intensity decay: none

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0413P)² + 2.2781P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3753 reflections	Δρ_max = 0.38 e Å⁻³
248 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00077 (19)

Crystal data top

[Co₂(C₁₂H₈O₁₂)(C₁₂H₈N₂)₂]	V = 3256.0 (11) Å³
M_r = 822.46	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.180 (4) Å	µ = 1.10 mm⁻¹
b = 8.9520 (18) Å	T = 295 K
c = 16.426 (3) Å	0.31 × 0.23 × 0.15 mm
β = 93.33 (3)°

Data collection top

Siemens P4 diffractometer	3312 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	R_int = 0.022
T_min = 0.702, T_max = 0.784	3 standard reflections every 97 reflections
4566 measured reflections	intensity decay: none
3753 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.38 e Å⁻³
3753 reflections	Δρ_min = −0.33 e Å⁻³
248 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.098444 (9)	0.64743 (2)	0.140367 (13)	0.02138 (9)
O1	0.07208 (6)	0.79951 (15)	0.23735 (7)	0.0330 (3)
O2	0.04781 (7)	0.83776 (14)	0.10892 (7)	0.0327 (3)
O3	0.08305 (7)	1.16900 (18)	0.04746 (9)	0.0433 (4)
O4	−0.01738 (6)	1.14637 (17)	0.04776 (8)	0.0363 (3)
H4A	−0.0159 (12)	1.148 (3)	−0.0004 (19)	0.054*
O5	0.09100 (5)	1.45307 (15)	0.21296 (8)	0.0314 (3)
O6	0.01745 (5)	1.51543 (15)	0.12579 (8)	0.0329 (3)
N1	0.13438 (6)	0.55177 (17)	0.03690 (9)	0.0277 (3)
N2	0.18993 (7)	0.70526 (19)	0.16045 (9)	0.0322 (3)
C1	0.10617 (9)	0.4793 (2)	−0.02411 (11)	0.0378 (4)
H1A	0.0642	0.4771	−0.0272	0.045*
C2	0.13708 (13)	0.4053 (3)	−0.08457 (14)	0.0544 (6)
H2A	0.1159	0.3563	−0.1272	0.065*
C3	0.19861 (13)	0.4065 (3)	−0.07970 (15)	0.0591 (7)
H3A	0.2196	0.3561	−0.1186	0.071*
C4	0.23052 (10)	0.4833 (3)	−0.01624 (14)	0.0472 (5)
C5	0.29531 (12)	0.4955 (4)	−0.00706 (19)	0.0673 (8)
H5A	0.3186	0.4468	−0.0441	0.081*
C6	0.32300 (10)	0.5748 (4)	0.05321 (19)	0.0686 (9)
H6A	0.3649	0.5806	0.0569	0.082*
C7	0.28897 (9)	0.6512 (3)	0.11216 (16)	0.0517 (6)
C8	0.31442 (11)	0.7393 (4)	0.17623 (18)	0.0660 (8)
H8A	0.3561	0.7516	0.1821	0.079*
C9	0.27855 (12)	0.8067 (4)	0.22961 (17)	0.0658 (8)
H9A	0.2954	0.8650	0.2719	0.079*
C10	0.21599 (11)	0.7875 (3)	0.22011 (14)	0.0487 (5)
H10A	0.1917	0.8338	0.2568	0.058*
C11	0.22540 (8)	0.6391 (2)	0.10648 (12)	0.0339 (4)
C12	0.19595 (8)	0.5557 (2)	0.04106 (11)	0.0318 (4)
C13	0.00497 (7)	1.00717 (17)	0.20407 (9)	0.0213 (3)
H13A	−0.0344	0.9985	0.1741	0.026*
C14	0.03623 (7)	1.15052 (16)	0.17600 (9)	0.0205 (3)
H14A	0.0778	1.1519	0.1998	0.025*
C15	0.00349 (7)	1.29201 (17)	0.20377 (9)	0.0194 (3)
H15A	−0.0367	1.2958	0.1758	0.023*
C16	0.04335 (8)	0.87293 (17)	0.18323 (10)	0.0234 (3)
C17	0.03790 (8)	1.15477 (18)	0.08330 (10)	0.0256 (3)
C18	0.03920 (7)	1.42928 (17)	0.17948 (9)	0.0209 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02179 (13)	0.01718 (13)	0.02545 (13)	−0.00066 (8)	0.00385 (8)	−0.00008 (8)
O1	0.0451 (7)	0.0284 (6)	0.0258 (6)	0.0125 (6)	0.0031 (5)	0.0002 (5)
O2	0.0497 (8)	0.0259 (6)	0.0228 (6)	0.0115 (6)	0.0048 (5)	−0.0013 (5)
O3	0.0426 (8)	0.0505 (9)	0.0389 (7)	0.0011 (7)	0.0212 (6)	0.0015 (6)
O4	0.0402 (7)	0.0477 (9)	0.0209 (6)	0.0031 (6)	0.0014 (5)	−0.0005 (6)
O5	0.0286 (6)	0.0283 (6)	0.0368 (6)	−0.0066 (5)	−0.0040 (5)	0.0084 (5)
O6	0.0274 (6)	0.0276 (6)	0.0431 (7)	−0.0037 (5)	−0.0031 (5)	0.0141 (6)
N1	0.0265 (7)	0.0298 (7)	0.0272 (7)	0.0006 (6)	0.0044 (5)	−0.0008 (6)
N2	0.0299 (7)	0.0335 (8)	0.0328 (7)	−0.0094 (6)	−0.0004 (6)	0.0029 (7)
C1	0.0407 (10)	0.0412 (11)	0.0313 (9)	−0.0015 (8)	0.0005 (7)	−0.0037 (8)
C2	0.0764 (17)	0.0522 (14)	0.0353 (11)	−0.0025 (13)	0.0089 (10)	−0.0145 (10)
C3	0.0742 (17)	0.0589 (15)	0.0469 (13)	0.0132 (14)	0.0256 (12)	−0.0108 (12)
C4	0.0444 (11)	0.0513 (13)	0.0479 (12)	0.0140 (10)	0.0206 (9)	0.0045 (10)
C5	0.0411 (13)	0.086 (2)	0.0782 (18)	0.0230 (14)	0.0307 (13)	0.0099 (17)
C6	0.0245 (10)	0.096 (2)	0.087 (2)	0.0121 (13)	0.0166 (11)	0.0225 (18)
C7	0.0236 (9)	0.0692 (17)	0.0620 (14)	−0.0055 (9)	0.0005 (9)	0.0216 (12)
C8	0.0310 (11)	0.092 (2)	0.0729 (17)	−0.0238 (13)	−0.0132 (11)	0.0211 (16)
C9	0.0571 (15)	0.081 (2)	0.0564 (15)	−0.0368 (15)	−0.0180 (12)	0.0040 (14)
C10	0.0505 (13)	0.0511 (13)	0.0438 (11)	−0.0208 (11)	−0.0043 (9)	−0.0023 (10)
C11	0.0229 (8)	0.0386 (10)	0.0404 (10)	−0.0019 (7)	0.0025 (7)	0.0106 (8)
C12	0.0278 (8)	0.0337 (9)	0.0348 (9)	0.0038 (7)	0.0091 (7)	0.0062 (8)
C13	0.0275 (7)	0.0155 (7)	0.0213 (7)	−0.0008 (6)	0.0037 (6)	−0.0001 (6)
C14	0.0228 (7)	0.0161 (7)	0.0227 (7)	−0.0001 (6)	0.0036 (5)	0.0001 (6)
C15	0.0209 (7)	0.0157 (7)	0.0217 (7)	0.0000 (5)	0.0020 (5)	0.0003 (6)
C16	0.0302 (8)	0.0168 (7)	0.0238 (7)	−0.0003 (6)	0.0051 (6)	0.0008 (6)
C17	0.0342 (8)	0.0179 (7)	0.0252 (8)	0.0015 (6)	0.0077 (6)	0.0009 (6)
C18	0.0238 (7)	0.0167 (7)	0.0228 (7)	0.0008 (6)	0.0058 (6)	−0.0014 (6)

Geometric parameters (Å, º) top

Co1—O1	2.2002 (13)	C3—H3A	0.9300
Co1—O2	2.0890 (13)	C4—C12	1.406 (3)
Co1—O5ⁱ	2.1211 (13)	C4—C5	1.440 (3)
Co1—O6ⁱ	2.1519 (13)	C5—C6	1.338 (5)
Co1—N1	2.1012 (15)	C5—H5A	0.9300
Co1—N2	2.1016 (15)	C6—C7	1.435 (4)
Co1—C18ⁱ	2.4599 (16)	C6—H6A	0.9300
Co1—C16	2.4827 (16)	C7—C8	1.407 (4)
O1—C16	1.250 (2)	C7—C11	1.412 (3)
O2—C16	1.270 (2)	C8—C9	1.359 (4)
O3—C17	1.198 (2)	C8—H8A	0.9300
O4—C17	1.329 (2)	C9—C10	1.398 (3)
O4—H4A	0.79 (3)	C9—H9A	0.9300
O5—C18	1.263 (2)	C10—H10A	0.9300
O5—Co1ⁱⁱ	2.1211 (13)	C11—C12	1.435 (3)
O6—C18	1.247 (2)	C13—C16	1.523 (2)
O6—Co1ⁱⁱ	2.1519 (13)	C13—C13ⁱⁱⁱ	1.538 (3)
N1—C1	1.321 (2)	C13—C14	1.542 (2)
N1—C12	1.364 (2)	C13—H13A	0.9800
N2—C10	1.330 (3)	C14—C17	1.526 (2)
N2—C11	1.355 (3)	C14—C15	1.542 (2)
C1—C2	1.405 (3)	C14—H14A	0.9800
C1—H1A	0.9300	C15—C18	1.528 (2)
C2—C3	1.363 (4)	C15—C15ⁱⁱⁱ	1.535 (3)
C2—H2A	0.9300	C15—H15A	0.9800
C3—C4	1.405 (4)	C18—Co1ⁱⁱ	2.4599 (16)

O2—Co1—N1	110.87 (6)	C5—C6—C7	121.0 (2)
O2—Co1—N2	109.77 (6)	C5—C6—H6A	119.5
N1—Co1—N2	79.58 (6)	C7—C6—H6A	119.5
O2—Co1—O5ⁱ	138.57 (6)	C8—C7—C11	116.6 (2)
N1—Co1—O5ⁱ	99.55 (6)	C8—C7—C6	124.6 (2)
N2—Co1—O5ⁱ	102.70 (6)	C11—C7—C6	118.8 (2)
O2—Co1—O6ⁱ	89.26 (5)	C9—C8—C7	120.5 (2)
N1—Co1—O6ⁱ	92.27 (6)	C9—C8—H8A	119.8
N2—Co1—O6ⁱ	160.89 (6)	C7—C8—H8A	119.8
O5ⁱ—Co1—O6ⁱ	61.34 (5)	C8—C9—C10	119.2 (2)
O2—Co1—O1	60.84 (5)	C8—C9—H9A	120.4
N1—Co1—O1	165.26 (6)	C10—C9—H9A	120.4
N2—Co1—O1	91.64 (6)	N2—C10—C9	122.4 (2)
O5ⁱ—Co1—O1	93.89 (5)	N2—C10—H10A	118.8
O6ⁱ—Co1—O1	99.50 (6)	C9—C10—H10A	118.8
O2—Co1—C18ⁱ	115.12 (6)	N2—C11—C7	122.6 (2)
N1—Co1—C18ⁱ	96.96 (6)	N2—C11—C12	117.47 (15)
N2—Co1—C18ⁱ	132.85 (6)	C7—C11—C12	119.9 (2)
O5ⁱ—Co1—C18ⁱ	30.88 (5)	N1—C12—C4	122.56 (19)
O6ⁱ—Co1—C18ⁱ	30.46 (5)	N1—C12—C11	117.50 (16)
O1—Co1—C18ⁱ	97.68 (5)	C4—C12—C11	119.94 (18)
O2—Co1—C16	30.74 (5)	C16—C13—C13ⁱⁱⁱ	109.53 (11)
N1—Co1—C16	140.98 (6)	C16—C13—C14	108.82 (12)
N2—Co1—C16	104.00 (6)	C13ⁱⁱⁱ—C13—C14	112.70 (10)
O5ⁱ—Co1—C16	116.86 (6)	C16—C13—H13A	108.6
O6ⁱ—Co1—C16	93.24 (6)	C13ⁱⁱⁱ—C13—H13A	108.6
O1—Co1—C16	30.20 (5)	C14—C13—H13A	108.6
C18ⁱ—Co1—C16	106.99 (5)	C17—C14—C13	110.89 (13)
C16—O1—Co1	87.50 (10)	C17—C14—C15	108.29 (12)
C16—O2—Co1	92.02 (10)	C13—C14—C15	111.56 (12)
C17—O4—H4A	110 (2)	C17—C14—H14A	108.7
C18—O5—Co1ⁱⁱ	89.55 (10)	C13—C14—H14A	108.7
C18—O6—Co1ⁱⁱ	88.55 (10)	C15—C14—H14A	108.7
C1—N1—C12	118.65 (16)	C18—C15—C15ⁱⁱⁱ	109.99 (10)
C1—N1—Co1	128.96 (13)	C18—C15—C14	108.86 (12)
C12—N1—Co1	112.02 (12)	C15ⁱⁱⁱ—C15—C14	111.64 (10)
C10—N2—C11	118.66 (18)	C18—C15—H15A	108.8
C10—N2—Co1	128.76 (15)	C15ⁱⁱⁱ—C15—H15A	108.8
C11—N2—Co1	112.44 (12)	C14—C15—H15A	108.8
N1—C1—C2	122.6 (2)	O1—C16—O2	119.22 (15)
N1—C1—H1A	118.7	O1—C16—C13	121.57 (14)
C2—C1—H1A	118.7	O2—C16—C13	119.17 (14)
C3—C2—C1	118.9 (2)	O1—C16—Co1	62.30 (9)
C3—C2—H2A	120.6	O2—C16—Co1	57.23 (8)
C1—C2—H2A	120.6	C13—C16—Co1	174.86 (12)
C2—C3—C4	120.5 (2)	O3—C17—O4	124.52 (17)
C2—C3—H3A	119.8	O3—C17—C14	124.24 (17)
C4—C3—H3A	119.8	O4—C17—C14	111.20 (14)
C3—C4—C12	116.8 (2)	O6—C18—O5	120.56 (15)
C3—C4—C5	124.8 (2)	O6—C18—C15	119.79 (14)
C12—C4—C5	118.3 (2)	O5—C18—C15	119.64 (14)
C6—C5—C4	122.0 (2)	O6—C18—Co1ⁱⁱ	60.99 (9)
C6—C5—H5A	119.0	O5—C18—Co1ⁱⁱ	59.57 (8)
C4—C5—H5A	119.0	C15—C18—Co1ⁱⁱ	178.92 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2^iv	0.79 (3)	1.89 (3)	2.627 (2)	156 (2)

Symmetry code: (iv) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Co₂(C₁₂H₈O₁₂)(C₁₂H₈N₂)₂]
M_r	822.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	22.180 (4), 8.9520 (18), 16.426 (3)
β (°)	93.33 (3)
V (Å³)	3256.0 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.31 × 0.23 × 0.15

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	ψ scan (XSCANS; Siemens, 1996)
T_min, T_max	0.702, 0.784
No. of measured, independent and observed [I > 2σ(I)] reflections	4566, 3753, 3312
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.03
No. of reflections	3753
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.33

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O1	2.2002 (13)	Co1—O6ⁱ	2.1519 (13)
Co1—O2	2.0890 (13)	Co1—N1	2.1012 (15)
Co1—O5ⁱ	2.1211 (13)	Co1—N2	2.1016 (15)

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2ⁱⁱ	0.79 (3)	1.89 (3)	2.627 (2)	156 (2)

Symmetry code: (ii) −x, −y+2, −z.

Acknowledgements

This project was supported by the Scientific Research Fund of the Zhejiang Provincial Education Department (grant No. Y201017782) and the Scientific Research Fund of Ningbo University (grant No. XKL09078). Grateful thanks are also extended to the K. C. Wong Magna Fund in Ningbo University.

References

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