Tetra­aqua­bis­[3-(pyridin-4-yl)benzoato-κN]cobalt(II)

Wang, H.-R.; Li, G.-T.

doi:10.1107/S1600536811046496

metal-organic compounds

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Volume 67| Part 12| December 2011| Page m1743

https://doi.org/10.1107/S1600536811046496

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Tetraaquabis[3-(pyridin-4-yl)benzoato-κN]cobalt(II)

Hai-Rong Wang ^a ^* and Guo-Ting Li ^a

^aDepartment of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: wanghairong@ncwu.edu.cn

(Received 23 September 2011; accepted 4 November 2011; online 12 November 2011)

In the title compound, [Co(C₁₂H₈NO₂)₂(H₂O)₄], the Co atom lies on a twofold rotation axis and has an N₂O₄ octahedral coordination environment formed by four O atoms of water molecules in the equatorial plane and two apical N atoms of pyridine groups. An intricate three-dimensional supramolecular network is formed by multiple O—H⋯O hydrogen bonds between the coordinated water molecules and the uncoordinated carboxylate groups.

Related literature

For the design of metal-organic complexes, see: Ruben et al. (2003 ). For pyridyl-multicarboxylate-metal frameworks, see: Huang et al. (2007 ). For similar pyridylbenzoate complexes, see: Luo et al. (2007 ). For self-effacement of carboxylate groups in coordination chemistry, see: Lu et al. (2008 ).

Experimental

Crystal data

[Co(C₁₂H₈NO₂)₂(H₂O)₄]
M_r = 527.38
Monoclinic, C 2/c
a = 24.642 (10) Å
b = 7.128 (3) Å
c = 13.822 (6) Å
β = 112.660 (7)°
V = 2240.4 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 296 K
0.27 × 0.21 × 0.17 mm

Data collection

Siemens SMART CCD diffractometer
4423 measured reflections
1974 independent reflections
1499 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.131
S = 1.02
1974 reflections
171 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O1	2.098 (3)
Co1—O2	2.117 (3)
Co1—N1	2.148 (3)

O1—Co1—O1ⁱ	85.18 (15)
O1—Co1—O2	90.11 (11)
O1ⁱ—Co1—O2	175.22 (10)
O2ⁱ—Co1—O2	94.61 (15)
O1—Co1—N1	90.43 (10)
O1ⁱ—Co1—N1	92.54 (10)
O2ⁱ—Co1—N1	88.98 (10)
O2—Co1—N1	88.28 (10)
O2—Co1—N1ⁱ	88.98 (10)
N1—Co1—N1ⁱ	175.97 (15)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱⁱ	0.84 (1)	1.89 (2)	2.692 (4)	159 (4)
O2—H2A⋯O3ⁱⁱ	0.84 (1)	1.94 (2)	2.741 (4)	160 (4)
O1—H1B⋯O4ⁱⁱⁱ	0.84 (1)	1.91 (1)	2.743 (4)	177 (4)
O2—H2B⋯O4^iv	0.84 (1)	1.89 (1)	2.714 (4)	172 (4)
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1994 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046496/yk2023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046496/yk2023Isup2.hkl

checkCIF report

Comment top

The synthesis and exploration of multifunctional metal-organic complexes is a current topic of chemical research (M. Ruben, et al., 2003). Pyridyl-containing multi-carboxylic acids, a kind of gracious multifunctional spacers, have been widely used to construct various extended metal-organic frameworks with attracting properties (Y. Huang, et al., 2007). Pyridylbenzoate ligands are typical unsymmetrical spacers, but up to now their coordination chemistry has been discussed uncommonly. From our best knowledge, only one coordination compound of 3-(pyridin-4-yl)benzoic acid (PBC) of pyridylbenzoate family was synthesized and characterized up to now (J. Luo, et al., 2007). Herein we report a new Co(II) complex with PBC, namely, [Co(PBC)₂(H₂O)₄] (1).

As showed in Fig. 1, (1) is a mononuclear complex with a twofold axis passing through the Co(II) center along b axis and equally splitting the whole complex molecule. In (1), the Co(II) center is ligated by four O atoms of coordinated water molecules in the equatorial plane, whereas two PBC act as monodentate N-donating ligands with their pyridyl nitrogen atoms occupying the axial positions. Thus the cobalt(II) ion is six-coordinated and has octahedral coordination geometry. The bond distances Co—O and Co—N range from 2.098 (3) to 2.148 (3) Å, while the in-plane and axis-transition angles are 175.22 (10) and 175.97 (15) °, respectively, indicating a slight distortion of the octahedral coordination sphere around the Co(II) center.

Owing to the self-effacement of the versatile carboxyl groups in coordination chemistry (W. G. Lu, et al., 2008), the potential multifunctional PBC ligands in (1) act as terminal ligand only, rather than bridging one, very dissimilar to that in literature structure (J. Luo, et al., 2007). Further aggregation of monomers (1) is performed by the multiple hydrogen bonds between the coordinated water molecules (as donors) and the uncoordinated carboxylate groups (as acceptors) (Table 1). Hydrogen-bonding system among monomers (1) is rather complicated: each coordination water molecule forms two O—H···O hydrogen bonds with carboxylate groups of neighbouring complex molecules, while every carboxylate group of PBC forms three hydrogen bonds. Consequently, every monomer acts as a novel six-connected supramolecular synthon to connect with six adjacent monomers. For example, as shown in Fig. 2, the O4 of the carboxylate group of PBC ligates to two water molecules from two neighboring monomers, and as a result, monomers (1) are regularly arrayed in the ab<ι> plane and linked into 2D layers by strong hydrogen bonding (O1···O4ⁱⁱⁱ, 2.743 (4) Å; O2···O4, 2.714 (4) Å). The layer structure is stabilized by forceful face-to-face π···π stacking interactions between adjacent benzoate and pyridyl groups of PBC with a centroid to centroid distance of 3.60 (1) Å. Intriguingly, the dihedral angle between benzoate and pyridyl groups in PBC is equal to 26.9 (0) ° to meet the formation of hydrogen bonds. The layers are further bound together to create the 3D supramolecular architecture by hydrogen bonds between the O3 atom of the carboxylate group of PBC and two water molecules in the adjacent complex molecule.

Related literature top

For the design of metal-organic complexes, see: Ruben et al. (2003). For pyridyl-multicarboxylicate-metal frameworks, see: Huang et al. (2007). For similar pyridylbenzoate complexes, see: Luo et al. (2007). For self-effacement of carboxylate groups in coordination chemistry, see: Lu et al. (2008).

Experimental top

The title compound, (1), was prepared according to the following process. A mixture of Co(NO₃)₂.6H₂O (0.029 g, 0.1 mmol), PBC (0.040 g, 0.2 mmol) and deionized water (10 ml) was adjusted to the pH value about 7 by adding 0.1 M sodium hydroxide solution and then sealed into a 25 ml Teflon-lined stainless autoclave. The autoclave was heated at 160 °C for 3 days. After cooling to room temperature gradually, dark-red block crystals being characterized as the previously reported complex (J. Luo, et al., 2007) were obtained in 30% yield (based on Co). Allowing the red filtrate to evaporate slowly at ambient temperature for two months, pink crystals of (1) suitable for X-ray analysis were obtained in 58% yield (based on Co).

Structure description top

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); 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 diagram of (1) with atom numbering scheme (30% probability ellipsoids for all non-hydrogen atoms). Symmetry code: (i) -x + 1, y, -z + 1/2.
	Fig. 2. View of regular arrangement of molecules (1) directed by strong hydrogen bonding to form two-dimensional layers and face-to-face π···π stacking interactions between adjacent benzoate and pyridyl groups of PBC. Symmetry codes: (i) -x + 1, y, -z + 1/2; (ii) -x + 1/2, -y + 1/2, -z; (iii) x + 1/2, y - 1/2, z; (iiii) x + 1/2, y + 1/2, z.

Tetraaquabis[3-(pyridin-4-yl)benzoato-κN]cobalt(II) top

Crystal data top

[Co(C₁₂H₈NO₂)₂(H₂O)₄]	F(000) = 1092
M_r = 527.38	D_x = 1.564 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 981 reflections
a = 24.642 (10) Å	θ = 3.0–21.3°
b = 7.128 (3) Å	µ = 0.82 mm⁻¹
c = 13.822 (6) Å	T = 296 K
β = 112.660 (7)°	Block, red
V = 2240.4 (16) Å³	0.27 × 0.21 × 0.17 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	1499 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 25.0°, θ_min = 1.8°
ω scan	h = −23→29
4423 measured reflections	k = −8→8
1974 independent reflections	l = −14→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0755P)²] where P = (F_o² + 2F_c²)/3
1974 reflections	(Δ/σ)_max < 0.001
171 parameters	Δρ_max = 0.63 e Å⁻³
4 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Co(C₁₂H₈NO₂)₂(H₂O)₄]	V = 2240.4 (16) Å³
M_r = 527.38	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.642 (10) Å	µ = 0.82 mm⁻¹
b = 7.128 (3) Å	T = 296 K
c = 13.822 (6) Å	0.27 × 0.21 × 0.17 mm
β = 112.660 (7)°

Data collection top

Siemens SMART CCD diffractometer	1499 reflections with I > 2σ(I)
4423 measured reflections	R_int = 0.043
1974 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	4 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.63 e Å⁻³
1974 reflections	Δρ_min = −0.43 e Å⁻³
171 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	0.5000	0.30197 (9)	0.2500	0.0294 (3)
O1	0.46997 (11)	0.0853 (4)	0.13933 (19)	0.0381 (6)
O2	0.46824 (11)	0.5033 (4)	0.1285 (2)	0.0407 (6)
O3	0.09455 (11)	0.2256 (4)	0.0359 (2)	0.0515 (8)
O4	0.03868 (11)	0.2931 (4)	0.1240 (2)	0.0455 (7)
N1	0.41603 (12)	0.3126 (4)	0.2633 (2)	0.0322 (7)
C1	0.08769 (15)	0.2741 (5)	0.1173 (3)	0.0355 (9)
C2	0.14247 (15)	0.3156 (5)	0.2136 (3)	0.0306 (8)
C3	0.13890 (16)	0.3628 (5)	0.3077 (3)	0.0383 (9)
H3	0.1017	0.3689	0.3134	0.046*
C4	0.18993 (16)	0.4014 (6)	0.3940 (3)	0.0404 (9)
H4	0.1876	0.4354	0.4587	0.049*
C5	0.24431 (15)	0.3905 (5)	0.3862 (3)	0.0365 (8)
H5	0.2790	0.4165	0.4459	0.044*
C6	0.24867 (14)	0.3419 (5)	0.2920 (3)	0.0297 (8)
C7	0.19680 (14)	0.3043 (5)	0.2059 (3)	0.0302 (8)
H7	0.1988	0.2703	0.1409	0.036*
C8	0.30666 (14)	0.3304 (5)	0.2826 (3)	0.0300 (8)
C9	0.35800 (15)	0.2917 (5)	0.3676 (3)	0.0342 (8)
H9	0.3569	0.2698	0.4346	0.041*
C10	0.41091 (15)	0.2848 (5)	0.3551 (3)	0.0347 (8)
H10	0.4456	0.2590	0.4149	0.042*
C11	0.36609 (15)	0.3493 (5)	0.1809 (3)	0.0355 (9)
H11	0.3683	0.3688	0.1144	0.043*
C12	0.31186 (15)	0.3603 (5)	0.1876 (3)	0.0364 (9)
H12	0.2779	0.3884	0.1269	0.044*
H1A	0.4545 (17)	0.127 (6)	0.0779 (15)	0.055*
H1B	0.4919 (15)	−0.001 (4)	0.136 (3)	0.055*
H2B	0.4916 (15)	0.591 (4)	0.133 (3)	0.055*
H2A	0.4530 (17)	0.448 (6)	0.0706 (18)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0181 (4)	0.0332 (4)	0.0371 (4)	0.000	0.0107 (3)	0.000
O1	0.0348 (15)	0.0390 (16)	0.0428 (14)	0.0036 (12)	0.0175 (12)	−0.0014 (12)
O2	0.0293 (14)	0.0402 (17)	0.0484 (15)	−0.0077 (11)	0.0101 (12)	0.0059 (13)
O3	0.0313 (15)	0.074 (2)	0.0434 (15)	0.0003 (13)	0.0077 (12)	−0.0062 (14)
O4	0.0228 (14)	0.0398 (15)	0.0731 (19)	0.0005 (11)	0.0173 (13)	−0.0009 (13)
N1	0.0222 (15)	0.0333 (17)	0.0402 (17)	0.0000 (12)	0.0110 (13)	−0.0020 (13)
C1	0.0241 (19)	0.0287 (19)	0.051 (2)	0.0019 (15)	0.0120 (16)	0.0076 (17)
C2	0.0240 (18)	0.0275 (18)	0.0398 (18)	0.0035 (14)	0.0118 (15)	0.0058 (15)
C3	0.031 (2)	0.043 (2)	0.048 (2)	0.0082 (16)	0.0229 (17)	0.0083 (17)
C4	0.034 (2)	0.054 (3)	0.0377 (19)	0.0040 (18)	0.0179 (16)	−0.0032 (18)
C5	0.0264 (19)	0.043 (2)	0.039 (2)	−0.0014 (16)	0.0107 (15)	−0.0029 (17)
C6	0.0219 (17)	0.0283 (19)	0.0401 (19)	0.0009 (14)	0.0133 (15)	0.0010 (15)
C7	0.0247 (18)	0.0315 (19)	0.0367 (18)	−0.0017 (15)	0.0146 (15)	−0.0006 (15)
C8	0.0210 (17)	0.0280 (19)	0.0416 (19)	−0.0007 (14)	0.0128 (15)	−0.0026 (15)
C9	0.0242 (18)	0.047 (2)	0.0324 (18)	−0.0023 (16)	0.0114 (15)	−0.0004 (16)
C10	0.0222 (18)	0.043 (2)	0.0361 (19)	−0.0020 (15)	0.0081 (15)	−0.0005 (16)
C11	0.0224 (18)	0.048 (2)	0.0370 (19)	−0.0006 (15)	0.0122 (15)	0.0002 (16)
C12	0.0238 (18)	0.044 (2)	0.040 (2)	0.0017 (16)	0.0114 (15)	−0.0008 (17)

Geometric parameters (Å, º) top

Co1—O1	2.098 (3)	C3—C4	1.387 (5)
Co1—O1ⁱ	2.098 (3)	C3—H3	0.9500
Co1—O2ⁱ	2.117 (3)	C4—C5	1.387 (5)
Co1—O2	2.117 (3)	C4—H4	0.9500
Co1—N1	2.148 (3)	C5—C6	1.390 (5)
Co1—N1ⁱ	2.148 (3)	C5—H5	0.9500
O1—H1A	0.840 (10)	C6—C7	1.396 (5)
O1—H1B	0.836 (10)	C6—C8	1.487 (5)
O2—H2B	0.835 (10)	C7—H7	0.9500
O2—H2A	0.840 (10)	C8—C9	1.383 (5)
O3—C1	1.249 (5)	C8—C12	1.383 (5)
O4—C1	1.254 (4)	C9—C10	1.381 (5)
N1—C10	1.337 (4)	C9—H9	0.9500
N1—C11	1.342 (4)	C10—H10	0.9500
C1—C2	1.516 (5)	C11—C12	1.377 (5)
C2—C3	1.378 (5)	C11—H11	0.9500
C2—C7	1.386 (5)	C12—H12	0.9500

O1—Co1—O1ⁱ	85.18 (15)	C2—C3—C4	119.6 (3)
O1—Co1—O2ⁱ	175.22 (10)	C2—C3—H3	120.2
O1ⁱ—Co1—O2ⁱ	90.11 (11)	C4—C3—H3	120.2
O1—Co1—O2	90.11 (11)	C3—C4—C5	120.3 (3)
O1ⁱ—Co1—O2	175.22 (10)	C3—C4—H4	119.8
O2ⁱ—Co1—O2	94.61 (15)	C5—C4—H4	119.8
O1—Co1—N1	90.43 (10)	C4—C5—C6	120.8 (3)
O1ⁱ—Co1—N1	92.54 (10)	C4—C5—H5	119.6
O2ⁱ—Co1—N1	88.98 (10)	C6—C5—H5	119.6
O2—Co1—N1	88.28 (10)	C5—C6—C7	118.0 (3)
O1—Co1—N1ⁱ	92.54 (10)	C5—C6—C8	121.3 (3)
O1ⁱ—Co1—N1ⁱ	90.43 (10)	C7—C6—C8	120.6 (3)
O2ⁱ—Co1—N1ⁱ	88.28 (10)	C2—C7—C6	121.2 (3)
O2—Co1—N1ⁱ	88.98 (10)	C2—C7—H7	119.4
N1—Co1—N1ⁱ	175.97 (15)	C6—C7—H7	119.4
Co1—O1—H1A	112 (3)	C9—C8—C12	116.6 (3)
Co1—O1—H1B	122 (3)	C9—C8—C6	122.1 (3)
H1A—O1—H1B	104 (4)	C12—C8—C6	121.2 (3)
Co1—O2—H2B	114 (3)	C10—C9—C8	119.9 (3)
Co1—O2—H2A	109 (3)	C10—C9—H9	120.0
H2B—O2—H2A	118 (4)	C8—C9—H9	120.0
C10—N1—C11	116.3 (3)	N1—C10—C9	123.5 (3)
C10—N1—Co1	121.5 (2)	N1—C10—H10	118.2
C11—N1—Co1	122.2 (2)	C9—C10—H10	118.2
O3—C1—O4	124.4 (4)	N1—C11—C12	123.3 (3)
O3—C1—C2	117.5 (3)	N1—C11—H11	118.3
O4—C1—C2	118.1 (3)	C12—C11—H11	118.3
C3—C2—C7	120.1 (3)	C11—C12—C8	120.2 (3)
C3—C2—C1	121.1 (3)	C11—C12—H12	119.9
C7—C2—C1	118.8 (3)	C8—C12—H12	119.9

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱⁱ	0.84 (1)	1.89 (2)	2.692 (4)	159 (4)
O2—H2A···O3ⁱⁱ	0.84 (1)	1.94 (2)	2.741 (4)	160 (4)
O1—H1B···O4ⁱⁱⁱ	0.84 (1)	1.91 (1)	2.743 (4)	177 (4)
O2—H2B···O4^iv	0.84 (1)	1.89 (1)	2.714 (4)	172 (4)

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₈NO₂)₂(H₂O)₄]
M_r	527.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	24.642 (10), 7.128 (3), 13.822 (6)
β (°)	112.660 (7)
V (Å³)	2240.4 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.27 × 0.21 × 0.17

Data collection
Diffractometer	Siemens SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4423, 1974, 1499
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.131, 1.02
No. of reflections	1974
No. of parameters	171
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.43

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—O1	2.098 (3)	Co1—N1	2.148 (3)
Co1—O2	2.117 (3)

O1—Co1—O1ⁱ	85.18 (15)	O1ⁱ—Co1—N1	92.54 (10)
O1—Co1—O2	90.11 (11)	O2ⁱ—Co1—N1	88.98 (10)
O1ⁱ—Co1—O2	175.22 (10)	O2—Co1—N1	88.28 (10)
O2ⁱ—Co1—O2	94.61 (15)	O2—Co1—N1ⁱ	88.98 (10)
O1—Co1—N1	90.43 (10)	N1—Co1—N1ⁱ	175.97 (15)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ⁱⁱ	0.840 (10)	1.891 (19)	2.692 (4)	159 (4)
O2—H2A···O3ⁱⁱ	0.840 (10)	1.935 (17)	2.741 (4)	160 (4)
O1—H1B···O4ⁱⁱⁱ	0.836 (10)	1.908 (11)	2.743 (4)	177 (4)
O2—H2B···O4^iv	0.835 (10)	1.885 (12)	2.714 (4)	172 (4)

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

Acknowledgements

This work was supported by the Natural Science Foundation of China.

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