Poly[[aqua­(μ7-biphenyl-3,3′,4,4′-tetra­carboxyl­ato)(1,10-phenanthroline)dicobalt(II)] monohydrate]

Yin, H.; Yin, F.; Lu, Y.

doi:10.1107/S1600536811028224

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1118

doi:10.1107/S1600536811028224

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Poly[[aqua(μ₇-biphenyl-3,3′,4,4′-tetracarboxylato)(1,10-phenanthroline)dicobalt(II)] monohydrate]

Hailiang Yin,^a ^* Fengjuan Yin ^b and Yukun Lu ^a

^aCollege of Chemistry and Chemical Engineering, China University of Petroleum, Qingdao 255666, People's Republic of China, and ^bEnvironmental Protection Bureau of Dongying, Dongying 257091, People's Republic of China
^*Correspondence e-mail: yinhl2000@163.com

(Received 26 June 2011; accepted 14 July 2011; online 23 July 2011)

In the title compound, {[Co₂(C₁₆H₆O₈)(C₁₂H₈N₂)(H₂O)₂]·H₂O}_n, one Co^II ion has a {CoN₂O₄} distorted octahedral environment defined by two N atoms of one 1,10-phenanthroline (phen) ligand, three O atoms of the carboxylate groups of three biphenyl-3,3′,4,4′-tetracarboxylate (BPTC) ligands, one of which is bidentate, and one O atom from one coordinated water molecule. The other Co^II atom is surrounded by six O atoms from four different BPTC ligands and one coordinated water molecule. Each BPTC ligand forms eight coordination bonds with seven Co^II atoms, leading to a layer structure along the ac plane. Uncoordinated water molecules occupy the space between the layers, and interact via interlayer O—H⋯O hydrogen bonds along the b axis, generating a three-dimensional supramolecular network.

Related literature

For applications of compounds with metal-organic framework structures (MOFs), see: Rowsell & Yaghi (2005 ). For related structures, see: Zhu et al. (2008 ); Konar et al. (2004 ).

Experimental

Crystal data

[Co₂(C₁₆H₆O₈)(C₁₂H₈N₂)(H₂O)₂]·H₂O
M_r = 678.32
Triclinic, $[P \overline 1]$
a = 9.793 (3) Å
b = 10.885 (3) Å
c = 12.453 (3) Å
α = 97.567 (4)°
β = 102.608 (4)°
γ = 95.653 (4)°
V = 1273.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 298 K
0.40 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.609, T_max = 0.810
6716 measured reflections
4641 independent reflections
3194 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.113
S = 0.98
4641 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11B⋯O7ⁱ	0.85	2.04	2.886 (6)	173
O11—H11A⋯O7ⁱⁱ	0.85	2.15	2.931 (5)	152
O10—H10B⋯O7ⁱⁱⁱ	0.85	2.20	2.668 (4)	115
O10—H10A⋯O2^iv	0.85	1.95	2.756 (4)	159
O9—H9A⋯O3	0.85	2.09	2.661 (4)	124
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x, y-1, z-1; (iii) x, y, z-1; (iv) x+1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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 I, global. DOI: 10.1107/S1600536811028224/bg2411sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028224/bg2411Isup2.hkl

checkCIF report

Comment top

The assembly of coordination architectures has attracted much attention in recent years due to their potential applications in separation, sorption, hydrogen storage, and catalysis, as well as due to their intriguing topologies such as molecular ladders, grids, rings, boxes, honeycombs, and diamondoids (Rowsell & Yaghi, 2005). Coordination polymers containing biphenylpolycarboxylate and 1,10-phenanthroline as ligands have played a important role in the area of modern coordination chemistry. A few coordination polymers dealing with 3,3',4,4'-biphenyltetracarboxylate (H₄BPTC) and 1,10-phenanthroline (phen) have been reported (Zhu et al., 2008). Herein, we report a new cobalt coordination polymer, {[Co₂(C₁₆H₆O₈)(C₁₂H₈N₂)(H₂O)₂]H₂O}_n, resulting from reaction of Co²⁺ cations, phen and H₄BPTC under hydrothermal conditions.

As shown in Fig. 1, the asymmetric unit consists of two crystallographically independent Co²⁺ ions, one fully deprotonated BPTC^4- anion, a chelating phen ligand, two coordinated water molecules and one lattice water molecule. The Co1 center is in an octahedral environment defined by two N atoms of one phen ligand, three O atoms of carboxylate groups from three BPTC ligands, and one O atom from one coordinated water molecule. The Co1–O bond lengths fall in the range 2.001 (3)–2.149 (3) Å and the two Co1-N distances are 2.108 (4) and 2.143 (4) Å, thus falling in the expected region (Konar, et al., 2004). The Co2 atom is surrounded by six O atoms from four different BPTC ligands and one coordinated water molecule with Co–O distances in the range 2.025 (3)–2.210 (3) Å, and O–Co–O angles varying from 61.42 (11)°–168.23 (11)°. The octahedral coordination around the Co atoms is strongly distorted since the diametrical and non-diametrical bond angles indicate significant deviations from 180° and 90°, respectively. BPTC^4- forms eight coordination bonds with seven Co centers. Two carboxylates of BPTC^4- act as monodentate bridging and adopt a µ₂-η²:η⁰ coordinated mode, one carboxylate acts as bidentate bridging and adopts a µ₂-η¹:η¹ coordinated mode, while the remaining carboxylate chelates a Co cation. As a result, each BPTC^4- forms eight coordination bonds with seven Co centers, leading to a 2D layer structure parallel to the ac plane. Lattice water molecules occupy the space between 2D layers, and interact via interlayer O–H···O hydrogen bonds along the b-axis to generate a 3D supramolecular network (Table 1 and Fig.2).

Related literature top

For applications of metal-organic frameworks (MOFs), see: Rowsell et al. (2005). For related structures, see: Zhu et al. (2008); Konar et al. (2004).

Experimental top

A mixture of Co(NO₃)₂.6H₂O (146 mg, 0.5 mmol),3,3',4,4' -biphenyltetracarboxylate (74 mg, 0.25 mmol), phen (99 mg, 0.5 mmol), NaOH (40 mg, 1.0 mmol) and water (15 ml) were heated at 393 K for 4 days in a sealed 25 ml Teflon-lined stainless steel vessel under autogenous pressure. Slow cooling of the reaction mixture at 2 K/min to room temperature gave salmon pink block crystals.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. : View of (I), showing 30% displacement ellipsoids. Symmetry codes: (i) x, y, z - 2; (ii) -x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 2 - z.
	Fig. 2. : Crystal packing of (I) as viewed down the crystallographic a axis.

Poly[[aqua(µ₇-biphenyl-3,3',4,4'-tetracarboxylato)(1,10- phenanthroline)dicobalt(II)] monohydrate] top

Crystal data top

[Co₂(C₁₆H₆O₈)(C₁₂H₈N₂)(H₂O)₂]·H₂O	Z = 2
M_r = 678.32	F(000) = 688
Triclinic, P1	D_x = 1.770 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.793 (3) Å	Cell parameters from 1160 reflections
b = 10.885 (3) Å	θ = 2.3–22.3°
c = 12.453 (3) Å	µ = 1.38 mm⁻¹
α = 97.567 (4)°	T = 298 K
β = 102.608 (4)°	Block, red
γ = 95.653 (4)°	0.40 × 0.17 × 0.16 mm
V = 1273.1 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4641 independent reflections
Radiation source: fine-focus sealed tube	3194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→9
T_min = 0.609, T_max = 0.810	k = −9→13
6716 measured reflections	l = −14→15

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0467P)²] where P = (F_o² + 2F_c²)/3
4641 reflections	(Δ/σ)_max = 0.001
388 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Co₂(C₁₆H₆O₈)(C₁₂H₈N₂)(H₂O)₂]·H₂O	γ = 95.653 (4)°
M_r = 678.32	V = 1273.1 (6) Å³
Triclinic, P1	Z = 2
a = 9.793 (3) Å	Mo Kα radiation
b = 10.885 (3) Å	µ = 1.38 mm⁻¹
c = 12.453 (3) Å	T = 298 K
α = 97.567 (4)°	0.40 × 0.17 × 0.16 mm
β = 102.608 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4641 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3194 reflections with I > 2σ(I)
T_min = 0.609, T_max = 0.810	R_int = 0.034
6716 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 0.98	Δρ_max = 0.46 e Å⁻³
4641 reflections	Δρ_min = −0.50 e Å⁻³
388 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
C1	−0.1205 (5)	0.5902 (4)	0.6684 (4)	0.0227 (11)
C2	−0.0391 (5)	0.6133 (4)	0.7872 (3)	0.0209 (10)
C3	−0.0950 (5)	0.6775 (4)	0.8670 (4)	0.0284 (12)
H3	−0.1796	0.7094	0.8450	0.034*
C4	−0.0286 (5)	0.6957 (4)	0.9786 (4)	0.0298 (12)
H4	−0.0699	0.7388	1.0300	0.036*
C5	0.0979 (5)	0.6512 (4)	1.0160 (3)	0.0189 (10)
C6	0.1527 (5)	0.5852 (4)	0.9355 (3)	0.0234 (11)
H6	0.2372	0.5535	0.9583	0.028*
C7	0.0872 (5)	0.5642 (4)	0.8227 (3)	0.0191 (10)
C8	0.1543 (5)	0.4826 (5)	0.7467 (3)	0.0224 (11)
C9	0.1711 (4)	0.6716 (4)	1.1364 (3)	0.0194 (10)
C10	0.1249 (5)	0.7513 (4)	1.2133 (4)	0.0297 (12)
H10	0.0491	0.7939	1.1891	0.036*
C11	0.1904 (5)	0.7684 (5)	1.3263 (4)	0.0317 (12)
H11	0.1585	0.8230	1.3765	0.038*
C12	0.3014 (5)	0.7054 (4)	1.3644 (4)	0.0231 (11)
C13	0.3634 (5)	0.7284 (5)	1.4884 (4)	0.0248 (11)
C14	0.3493 (5)	0.6257 (4)	1.2883 (3)	0.0209 (10)
C15	0.4728 (5)	0.5573 (4)	1.3218 (4)	0.0230 (11)
C16	0.2826 (5)	0.6097 (4)	1.1761 (3)	0.0225 (10)
H16	0.3144	0.5550	1.1260	0.027*
C17	0.5542 (5)	0.7004 (5)	0.9733 (4)	0.0369 (13)
H17	0.6056	0.6388	0.9503	0.044*
C18	0.5861 (6)	0.7519 (5)	1.0863 (4)	0.0459 (15)
H18	0.6582	0.7257	1.1365	0.055*
C19	0.5106 (6)	0.8406 (5)	1.1219 (4)	0.0446 (15)
H19	0.5308	0.8756	1.1968	0.054*
C20	0.4023 (6)	0.8790 (5)	1.0452 (4)	0.0343 (13)
C21	0.3795 (5)	0.8238 (4)	0.9332 (4)	0.0272 (11)
C22	0.2701 (5)	0.8587 (4)	0.8500 (4)	0.0267 (11)
C23	0.1811 (6)	0.9417 (5)	0.8828 (4)	0.0380 (13)
C24	0.2065 (6)	0.9964 (5)	0.9968 (5)	0.0476 (15)
H24	0.1481	1.0524	1.0184	0.057*
C25	0.3128 (7)	0.9689 (5)	1.0736 (5)	0.0475 (15)
H25	0.3290	1.0088	1.1469	0.057*
C26	0.0685 (7)	0.9626 (5)	0.7995 (5)	0.0550 (17)
H26	0.0046	1.0151	0.8173	0.066*
C27	0.0522 (6)	0.9065 (6)	0.6930 (5)	0.0533 (17)
H27	−0.0217	0.9215	0.6373	0.064*
C28	0.1466 (6)	0.8265 (5)	0.6673 (4)	0.0381 (13)
H28	0.1328	0.7869	0.5941	0.046*
Co1	0.39769 (6)	0.67515 (6)	0.72127 (5)	0.02274 (18)
Co2	0.24578 (6)	0.44660 (6)	0.52994 (5)	0.02263 (18)
N1	0.2553 (4)	0.8043 (4)	0.7428 (3)	0.0277 (9)
N2	0.4548 (4)	0.7350 (4)	0.8980 (3)	0.0273 (9)
O1	−0.0796 (3)	0.5208 (3)	0.5955 (2)	0.0285 (8)
O2	−0.2316 (3)	0.6395 (3)	0.6414 (2)	0.0304 (8)
O3	0.1484 (4)	0.3712 (3)	0.7556 (3)	0.0385 (9)
O4	0.2165 (3)	0.5344 (3)	0.6805 (2)	0.0229 (7)
O5	0.4838 (3)	0.4631 (3)	1.2562 (2)	0.0284 (8)
O6	0.5598 (3)	0.6015 (3)	1.4135 (2)	0.0264 (8)
O7	0.4224 (4)	0.8357 (3)	1.5296 (2)	0.0352 (9)
O8	0.3428 (3)	0.6420 (3)	1.5449 (2)	0.0217 (7)
O9	0.1558 (4)	0.2681 (3)	0.5513 (2)	0.0376 (9)
H9A	0.1290	0.2480	0.6078	0.045*
H9B	0.1354	0.2042	0.5007	0.045*
O10	0.5871 (3)	0.7894 (3)	0.7169 (2)	0.0306 (8)
H10A	0.6525	0.7612	0.6901	0.037*
H10B	0.5721	0.8574	0.6925	0.037*
O11	0.3441 (5)	0.0884 (4)	0.5642 (4)	0.0968 (19)
H11A	0.3480	0.0115	0.5697	0.116*
H11B	0.4080	0.1111	0.5312	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.015 (2)	0.028 (3)	0.023 (2)	−0.001 (2)	0.001 (2)	0.003 (2)
C2	0.019 (2)	0.027 (3)	0.014 (2)	0.003 (2)	−0.0016 (19)	0.003 (2)
C3	0.021 (3)	0.041 (3)	0.022 (3)	0.013 (2)	0.001 (2)	0.003 (2)
C4	0.033 (3)	0.038 (3)	0.018 (2)	0.011 (2)	0.006 (2)	−0.002 (2)
C5	0.021 (3)	0.021 (3)	0.015 (2)	0.004 (2)	0.0047 (19)	0.0034 (19)
C6	0.021 (3)	0.028 (3)	0.021 (2)	0.007 (2)	0.002 (2)	0.005 (2)
C7	0.023 (3)	0.025 (3)	0.011 (2)	0.004 (2)	0.0062 (18)	0.0035 (19)
C8	0.016 (2)	0.035 (3)	0.013 (2)	0.008 (2)	−0.0029 (19)	0.000 (2)
C9	0.019 (2)	0.024 (3)	0.015 (2)	0.004 (2)	0.0021 (19)	0.003 (2)
C10	0.034 (3)	0.032 (3)	0.023 (3)	0.017 (2)	0.001 (2)	0.005 (2)
C11	0.040 (3)	0.040 (3)	0.016 (2)	0.022 (3)	0.004 (2)	−0.001 (2)
C12	0.024 (3)	0.022 (3)	0.023 (2)	0.001 (2)	0.004 (2)	0.006 (2)
C13	0.025 (3)	0.034 (3)	0.016 (2)	0.016 (2)	0.001 (2)	0.001 (2)
C14	0.023 (3)	0.025 (3)	0.015 (2)	0.007 (2)	0.0029 (19)	0.005 (2)
C15	0.016 (2)	0.034 (3)	0.022 (2)	0.007 (2)	0.008 (2)	0.010 (2)
C16	0.024 (3)	0.024 (3)	0.019 (2)	0.006 (2)	0.002 (2)	0.002 (2)
C17	0.033 (3)	0.050 (4)	0.026 (3)	0.015 (3)	0.002 (2)	0.004 (3)
C18	0.045 (4)	0.062 (4)	0.024 (3)	0.004 (3)	−0.004 (3)	0.005 (3)
C19	0.055 (4)	0.049 (4)	0.022 (3)	−0.014 (3)	0.007 (3)	−0.003 (3)
C20	0.042 (3)	0.036 (3)	0.023 (3)	−0.006 (3)	0.012 (2)	−0.004 (2)
C21	0.032 (3)	0.027 (3)	0.021 (2)	−0.004 (2)	0.009 (2)	−0.002 (2)
C22	0.031 (3)	0.021 (3)	0.028 (3)	0.003 (2)	0.008 (2)	0.001 (2)
C23	0.052 (4)	0.028 (3)	0.039 (3)	0.012 (3)	0.017 (3)	0.004 (2)
C24	0.066 (4)	0.035 (3)	0.050 (4)	0.017 (3)	0.033 (3)	−0.006 (3)
C25	0.065 (4)	0.039 (4)	0.036 (3)	0.001 (3)	0.019 (3)	−0.012 (3)
C26	0.068 (5)	0.045 (4)	0.063 (4)	0.034 (3)	0.027 (4)	0.012 (3)
C27	0.056 (4)	0.064 (4)	0.047 (4)	0.035 (3)	0.011 (3)	0.017 (3)
C28	0.045 (4)	0.043 (4)	0.028 (3)	0.015 (3)	0.010 (3)	0.004 (3)
Co1	0.0226 (4)	0.0293 (4)	0.0144 (3)	0.0090 (3)	0.0007 (3)	−0.0016 (3)
Co2	0.0197 (4)	0.0316 (4)	0.0136 (3)	0.0072 (3)	−0.0016 (3)	−0.0011 (3)
N1	0.032 (2)	0.030 (2)	0.023 (2)	0.0107 (19)	0.0061 (18)	0.0034 (18)
N2	0.024 (2)	0.035 (3)	0.022 (2)	0.0073 (19)	0.0032 (18)	0.0003 (19)
O1	0.0256 (19)	0.041 (2)	0.0142 (16)	0.0109 (16)	−0.0018 (14)	−0.0061 (15)
O2	0.0232 (19)	0.050 (2)	0.0155 (16)	0.0147 (16)	−0.0021 (14)	0.0003 (15)
O3	0.057 (3)	0.033 (2)	0.032 (2)	0.0186 (19)	0.0175 (18)	0.0101 (17)
O4	0.0182 (17)	0.033 (2)	0.0159 (15)	0.0016 (14)	0.0036 (13)	−0.0008 (14)
O5	0.030 (2)	0.033 (2)	0.0183 (16)	0.0156 (16)	−0.0006 (14)	−0.0055 (15)
O6	0.0196 (18)	0.039 (2)	0.0164 (16)	0.0134 (15)	−0.0035 (14)	−0.0042 (15)
O7	0.047 (2)	0.024 (2)	0.0256 (18)	−0.0012 (17)	−0.0046 (16)	−0.0016 (16)
O8	0.0254 (18)	0.0271 (19)	0.0116 (15)	0.0054 (14)	0.0011 (13)	0.0031 (14)
O9	0.052 (2)	0.033 (2)	0.0264 (18)	−0.0014 (17)	0.0126 (17)	−0.0021 (16)
O10	0.031 (2)	0.030 (2)	0.0276 (18)	0.0052 (15)	0.0039 (15)	−0.0027 (15)
O11	0.104 (4)	0.038 (3)	0.184 (5)	0.023 (3)	0.094 (4)	0.031 (3)

Geometric parameters (Å, º) top

C1—O2	1.260 (5)	C19—H19	0.9300
C1—O1	1.262 (5)	C20—C21	1.404 (6)
C1—C2	1.495 (6)	C20—C25	1.437 (7)
C1—Co2ⁱ	2.467 (4)	C21—N2	1.357 (6)
C2—C3	1.381 (6)	C21—C22	1.437 (6)
C2—C7	1.402 (6)	C22—N1	1.358 (5)
C3—C4	1.379 (6)	C22—C23	1.399 (7)
C3—H3	0.9300	C23—C26	1.398 (7)
C4—C5	1.383 (6)	C23—C24	1.424 (7)
C4—H4	0.9300	C24—C25	1.337 (8)
C5—C6	1.389 (6)	C24—H24	0.9300
C5—C9	1.491 (5)	C25—H25	0.9300
C6—C7	1.390 (6)	C26—C27	1.354 (7)
C6—H6	0.9300	C26—H26	0.9300
C7—C8	1.509 (6)	C27—C28	1.389 (7)
C8—O3	1.229 (5)	C27—H27	0.9300
C8—O4	1.283 (5)	C28—N1	1.322 (6)
C9—C16	1.374 (6)	C28—H28	0.9300
C9—C10	1.386 (6)	Co1—O5ⁱⁱ	2.001 (3)
C10—C11	1.393 (6)	Co1—N1	2.108 (4)
C10—H10	0.9300	Co1—O8ⁱⁱⁱ	2.117 (3)
C11—C12	1.373 (6)	Co1—N2	2.143 (4)
C11—H11	0.9300	Co1—O10	2.144 (3)
C12—C14	1.388 (6)	Co1—O4	2.149 (3)
C12—C13	1.508 (6)	Co2—O6ⁱⁱ	2.025 (3)
C13—O7	1.241 (5)	Co2—O4	2.080 (3)
C13—O8	1.273 (5)	Co2—O1ⁱ	2.088 (3)
C14—C16	1.387 (6)	Co2—O9	2.127 (3)
C14—C15	1.493 (6)	Co2—O2ⁱ	2.184 (3)
C15—O5	1.253 (5)	Co2—O8ⁱⁱⁱ	2.210 (3)
C15—O6	1.269 (5)	Co2—C1ⁱ	2.467 (4)
C16—H16	0.9300	O9—H9A	0.8500
C17—N2	1.318 (6)	O9—H9B	0.8499
C17—C18	1.399 (6)	O10—H10A	0.8499
C17—H17	0.9300	O10—H10B	0.8501
C18—C19	1.359 (8)	O11—H11A	0.8520
C18—H18	0.9300	O11—H11B	0.8548
C19—C20	1.402 (7)

O2—C1—O1	119.9 (4)	C25—C24—H24	119.3
O2—C1—C2	119.5 (4)	C23—C24—H24	119.3
O1—C1—C2	120.6 (4)	C24—C25—C20	121.3 (5)
O2—C1—Co2ⁱ	62.1 (2)	C24—C25—H25	119.3
O1—C1—Co2ⁱ	57.8 (2)	C20—C25—H25	119.3
C2—C1—Co2ⁱ	177.7 (3)	C27—C26—C23	120.1 (5)
C3—C2—C7	118.1 (4)	C27—C26—H26	119.9
C3—C2—C1	119.1 (4)	C23—C26—H26	119.9
C7—C2—C1	122.6 (4)	C26—C27—C28	119.6 (5)
C4—C3—C2	121.7 (4)	C26—C27—H27	120.2
C4—C3—H3	119.1	C28—C27—H27	120.2
C2—C3—H3	119.1	N1—C28—C27	122.6 (5)
C3—C4—C5	121.6 (4)	N1—C28—H28	118.7
C3—C4—H4	119.2	C27—C28—H28	118.7
C5—C4—H4	119.2	O5ⁱⁱ—Co1—N1	161.87 (14)
C4—C5—C6	116.5 (4)	O5ⁱⁱ—Co1—O8ⁱⁱⁱ	97.71 (11)
C4—C5—C9	121.9 (4)	N1—Co1—O8ⁱⁱⁱ	96.93 (13)
C6—C5—C9	121.6 (4)	O5ⁱⁱ—Co1—N2	88.47 (13)
C5—C6—C7	123.2 (4)	N1—Co1—N2	77.93 (14)
C5—C6—H6	118.4	O8ⁱⁱⁱ—Co1—N2	172.24 (13)
C7—C6—H6	118.4	O5ⁱⁱ—Co1—O10	86.77 (13)
C6—C7—C2	118.9 (4)	N1—Co1—O10	104.03 (14)
C6—C7—C8	116.8 (4)	O8ⁱⁱⁱ—Co1—O10	89.41 (11)
C2—C7—C8	124.2 (4)	N2—Co1—O10	86.25 (13)
O3—C8—O4	124.7 (4)	O5ⁱⁱ—Co1—O4	87.22 (13)
O3—C8—C7	117.0 (4)	N1—Co1—O4	86.00 (14)
O4—C8—C7	118.2 (4)	O8ⁱⁱⁱ—Co1—O4	76.00 (11)
C16—C9—C10	117.5 (4)	N2—Co1—O4	109.13 (13)
C16—C9—C5	121.9 (4)	O10—Co1—O4	163.32 (11)
C10—C9—C5	120.6 (4)	O6ⁱⁱ—Co2—O4	98.38 (11)
C9—C10—C11	121.0 (4)	O6ⁱⁱ—Co2—O1ⁱ	153.17 (12)
C9—C10—H10	119.5	O4—Co2—O1ⁱ	107.16 (12)
C11—C10—H10	119.5	O6ⁱⁱ—Co2—O9	89.10 (13)
C12—C11—C10	120.7 (4)	O4—Co2—O9	93.31 (12)
C12—C11—H11	119.7	O1ⁱ—Co2—O9	97.35 (13)
C10—C11—H11	119.7	O6ⁱⁱ—Co2—O2ⁱ	93.38 (11)
C11—C12—C14	119.0 (4)	O4—Co2—O2ⁱ	168.19 (12)
C11—C12—C13	116.7 (4)	O1ⁱ—Co2—O2ⁱ	61.42 (11)
C14—C12—C13	124.3 (4)	O9—Co2—O2ⁱ	85.65 (12)
O7—C13—O8	124.2 (4)	O6ⁱⁱ—Co2—O8ⁱⁱⁱ	89.12 (12)
O7—C13—C12	116.5 (4)	O4—Co2—O8ⁱⁱⁱ	75.45 (11)
O8—C13—C12	119.0 (4)	O1ⁱ—Co2—O8ⁱⁱⁱ	89.44 (12)
C16—C14—C12	119.4 (4)	O9—Co2—O8ⁱⁱⁱ	168.23 (11)
C16—C14—C15	117.9 (4)	O2ⁱ—Co2—O8ⁱⁱⁱ	106.07 (12)
C12—C14—C15	122.6 (4)	O6ⁱⁱ—Co2—C1ⁱ	123.70 (13)
O5—C15—O6	125.4 (4)	O4—Co2—C1ⁱ	137.77 (14)
O5—C15—C14	117.5 (4)	O1ⁱ—Co2—C1ⁱ	30.76 (13)
O6—C15—C14	117.0 (4)	O9—Co2—C1ⁱ	90.96 (13)
C9—C16—C14	122.4 (4)	O2ⁱ—Co2—C1ⁱ	30.68 (13)
C9—C16—H16	118.8	O8ⁱⁱⁱ—Co2—C1ⁱ	99.70 (13)
C14—C16—H16	118.8	C28—N1—C22	117.8 (4)
N2—C17—C18	123.2 (5)	C28—N1—Co1	127.4 (3)
N2—C17—H17	118.4	C22—N1—Co1	114.3 (3)
C18—C17—H17	118.4	C17—N2—C21	117.7 (4)
C19—C18—C17	119.3 (5)	C17—N2—Co1	128.8 (3)
C19—C18—H18	120.4	C21—N2—Co1	113.5 (3)
C17—C18—H18	120.4	C1—O1—Co2ⁱ	91.4 (3)
C18—C19—C20	119.6 (5)	C1—O2—Co2ⁱ	87.2 (3)
C18—C19—H19	120.2	C8—O4—Co2	125.8 (3)
C20—C19—H19	120.2	C8—O4—Co1	128.5 (3)
C19—C20—C21	117.1 (5)	Co2—O4—Co1	98.35 (12)
C19—C20—C25	124.6 (5)	C15—O5—Co1ⁱⁱ	131.1 (3)
C21—C20—C25	118.3 (5)	C15—O6—Co2ⁱⁱ	127.3 (3)
N2—C21—C20	123.1 (5)	C13—O8—Co1^iv	121.5 (3)
N2—C21—C22	116.8 (4)	C13—O8—Co2^iv	142.9 (3)
C20—C21—C22	120.1 (5)	Co1^iv—O8—Co2^iv	95.37 (11)
N1—C22—C23	123.3 (5)	Co2—O9—H9A	128.0
N1—C22—C21	117.4 (4)	Co2—O9—H9B	124.2
C23—C22—C21	119.3 (4)	H9A—O9—H9B	107.7
C26—C23—C22	116.5 (5)	Co1—O10—H10A	123.2
C26—C23—C24	124.1 (5)	Co1—O10—H10B	113.4
C22—C23—C24	119.4 (5)	H10A—O10—H10B	107.7
C25—C24—C23	121.4 (5)	H11A—O11—H11B	107.1

O2—C1—C2—C3	6.6 (7)	C26—C27—C28—N1	−1.6 (9)
O1—C1—C2—C3	−172.6 (4)	C27—C28—N1—C22	2.8 (8)
O2—C1—C2—C7	−178.3 (4)	C27—C28—N1—Co1	174.4 (4)
O1—C1—C2—C7	2.5 (7)	C23—C22—N1—C28	−3.7 (7)
C7—C2—C3—C4	1.1 (7)	C21—C22—N1—C28	173.6 (4)
C1—C2—C3—C4	176.4 (4)	C23—C22—N1—Co1	−176.4 (4)
C2—C3—C4—C5	0.5 (8)	C21—C22—N1—Co1	0.9 (5)
C3—C4—C5—C6	−1.4 (7)	O5ⁱⁱ—Co1—N1—C28	−129.0 (5)
C3—C4—C5—C9	179.3 (4)	O8ⁱⁱⁱ—Co1—N1—C28	14.7 (4)
C4—C5—C6—C7	0.6 (7)	N2—Co1—N1—C28	−171.2 (5)
C9—C5—C6—C7	179.9 (4)	O10—Co1—N1—C28	105.8 (4)
C5—C6—C7—C2	1.0 (7)	O4—Co1—N1—C28	−60.7 (4)
C5—C6—C7—C8	−175.6 (4)	O5ⁱⁱ—Co1—N1—C22	42.8 (6)
C3—C2—C7—C6	−1.9 (7)	O8ⁱⁱⁱ—Co1—N1—C22	−173.5 (3)
C1—C2—C7—C6	−176.9 (4)	N2—Co1—N1—C22	0.6 (3)
C3—C2—C7—C8	174.5 (4)	O10—Co1—N1—C22	−82.4 (3)
C1—C2—C7—C8	−0.6 (7)	O4—Co1—N1—C22	111.2 (3)
C6—C7—C8—O3	68.8 (6)	C18—C17—N2—C21	−0.8 (7)
C2—C7—C8—O3	−107.7 (5)	C18—C17—N2—Co1	176.4 (4)
C6—C7—C8—O4	−109.2 (5)	C20—C21—N2—C17	−0.4 (7)
C2—C7—C8—O4	74.4 (6)	C22—C21—N2—C17	−179.0 (4)
C4—C5—C9—C16	168.3 (5)	C20—C21—N2—Co1	−178.1 (4)
C6—C5—C9—C16	−10.9 (7)	C22—C21—N2—Co1	3.3 (5)
C4—C5—C9—C10	−9.3 (7)	O5ⁱⁱ—Co1—N2—C17	12.6 (4)
C6—C5—C9—C10	171.5 (4)	N1—Co1—N2—C17	−179.5 (5)
C16—C9—C10—C11	0.6 (7)	O10—Co1—N2—C17	−74.3 (4)
C5—C9—C10—C11	178.3 (4)	O4—Co1—N2—C17	99.1 (4)
C9—C10—C11—C12	−0.8 (8)	O5ⁱⁱ—Co1—N2—C21	−170.1 (3)
C10—C11—C12—C14	1.1 (7)	N1—Co1—N2—C21	−2.1 (3)
C10—C11—C12—C13	−178.9 (4)	O10—Co1—N2—C21	103.1 (3)
C11—C12—C13—O7	−65.5 (6)	O4—Co1—N2—C21	−83.5 (3)
C14—C12—C13—O7	114.5 (5)	O2—C1—O1—Co2ⁱ	2.7 (4)
C11—C12—C13—O8	108.9 (5)	C2—C1—O1—Co2ⁱ	−178.1 (4)
C14—C12—C13—O8	−71.1 (6)	O1—C1—O2—Co2ⁱ	−2.6 (4)
C11—C12—C14—C16	−1.2 (7)	C2—C1—O2—Co2ⁱ	178.2 (4)
C13—C12—C14—C16	178.8 (4)	O3—C8—O4—Co2	28.2 (6)
C11—C12—C14—C15	177.6 (4)	C7—C8—O4—Co2	−154.1 (3)
C13—C12—C14—C15	−2.4 (7)	O3—C8—O4—Co1	−115.2 (4)
C16—C14—C15—O5	−21.1 (6)	C7—C8—O4—Co1	62.6 (5)
C12—C14—C15—O5	160.0 (4)	O6ⁱⁱ—Co2—O4—C8	−93.6 (3)
C16—C14—C15—O6	157.3 (4)	O1ⁱ—Co2—O4—C8	94.8 (3)
C12—C14—C15—O6	−21.6 (7)	O9—Co2—O4—C8	−4.0 (3)
C10—C9—C16—C14	−0.8 (7)	O2ⁱ—Co2—O4—C8	80.6 (7)
C5—C9—C16—C14	−178.5 (4)	O8ⁱⁱⁱ—Co2—O4—C8	179.6 (3)
C12—C14—C16—C9	1.1 (7)	C1ⁱ—Co2—O4—C8	91.1 (4)
C15—C14—C16—C9	−177.8 (4)	O6ⁱⁱ—Co2—O4—Co1	58.29 (14)
N2—C17—C18—C19	1.0 (8)	O1ⁱ—Co2—O4—Co1	−113.39 (13)
C17—C18—C19—C20	0.0 (8)	O9—Co2—O4—Co1	147.87 (13)
C18—C19—C20—C21	−1.1 (8)	O2ⁱ—Co2—O4—Co1	−127.6 (6)
C18—C19—C20—C25	177.9 (5)	O8ⁱⁱⁱ—Co2—O4—Co1	−28.59 (11)
C19—C20—C21—N2	1.4 (7)	C1ⁱ—Co2—O4—Co1	−117.05 (18)
C25—C20—C21—N2	−177.8 (5)	O5ⁱⁱ—Co1—O4—C8	82.0 (4)
C19—C20—C21—C22	179.9 (4)	N1—Co1—O4—C8	−81.2 (4)
C25—C20—C21—C22	0.8 (7)	O8ⁱⁱⁱ—Co1—O4—C8	−179.4 (4)
N2—C21—C22—N1	−2.9 (6)	N2—Co1—O4—C8	−5.5 (4)
C20—C21—C22—N1	178.4 (4)	O10—Co1—O4—C8	150.9 (4)
N2—C21—C22—C23	174.5 (5)	O5ⁱⁱ—Co1—O4—Co2	−68.77 (12)
C20—C21—C22—C23	−4.1 (7)	N1—Co1—O4—Co2	128.06 (14)
N1—C22—C23—C26	3.2 (8)	O8ⁱⁱⁱ—Co1—O4—Co2	29.89 (11)
C21—C22—C23—C26	−174.1 (5)	N2—Co1—O4—Co2	−156.19 (13)
N1—C22—C23—C24	−178.6 (5)	O10—Co1—O4—Co2	0.2 (5)
C21—C22—C23—C24	4.2 (8)	O6—C15—O5—Co1ⁱⁱ	16.8 (7)
C26—C23—C24—C25	177.3 (6)	C14—C15—O5—Co1ⁱⁱ	−165.0 (3)
C22—C23—C24—C25	−0.8 (9)	O5—C15—O6—Co2ⁱⁱ	10.6 (7)
C23—C24—C25—C20	−2.6 (9)	C14—C15—O6—Co2ⁱⁱ	−167.6 (3)
C19—C20—C25—C24	−176.4 (5)	O7—C13—O8—Co1^iv	3.7 (6)
C21—C20—C25—C24	2.6 (8)	C12—C13—O8—Co1^iv	−170.3 (3)
C22—C23—C26—C27	−1.8 (9)	O7—C13—O8—Co2^iv	176.9 (3)
C24—C23—C26—C27	−180.0 (6)	C12—C13—O8—Co2^iv	3.0 (7)
C23—C26—C27—C28	1.1 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11B···O7ⁱⁱ	0.85	2.04	2.886 (6)	173
O11—H11A···O7^v	0.85	2.15	2.931 (5)	152
O10—H10B···O7ⁱⁱⁱ	0.85	2.20	2.668 (4)	115
O10—H10A···O2^vi	0.85	1.95	2.756 (4)	159
O9—H9A···O3	0.85	2.09	2.661 (4)	124

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₁₆H₆O₈)(C₁₂H₈N₂)(H₂O)₂]·H₂O
M_r	678.32
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.793 (3), 10.885 (3), 12.453 (3)
α, β, γ (°)	97.567 (4), 102.608 (4), 95.653 (4)
V (Å³)	1273.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.38
Crystal size (mm)	0.40 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.609, 0.810
No. of measured, independent and observed [I > 2σ(I)] reflections	6716, 4641, 3194
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.113, 0.98
No. of reflections	4641
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.50

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11B···O7ⁱ	0.85	2.04	2.886 (6)	172.9
O11—H11A···O7ⁱⁱ	0.85	2.15	2.931 (5)	152.0
O10—H10B···O7ⁱⁱⁱ	0.85	2.20	2.668 (4)	114.9
O10—H10A···O2^iv	0.85	1.95	2.756 (4)	158.5
O9—H9A···O3	0.85	2.09	2.661 (4)	124.1

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

Acknowledgements

The authors thank the National Key Fundamental Research Development Project (973 Project: No. 2010CB226905) and the Fundamental Research Funds for the Central Universities (No. 09CX04045A).

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Konar, S., Zangrando, E., Drew, M. G. B., Ribas, J. & Chaudhuri, N. R. (2004). Dalton Trans. pp. 260–266. Web of Science CSD CrossRef Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, S. R., Zhang, H., Shao, M., Zhao, Y. M. & Li, M. X. (2008). Transition Met. Chem. 33, 669–680. Web of Science CSD CrossRef CAS Google Scholar

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