Poly[[aqua­tris­(μ-benzene-1,4-dicarboxyl­ato)tricobalt(II)] methanol monosolvate monohydrate]

Zhou, H.; Chu, C.-X.; Li, Y.-Z.

doi:10.1107/S1600536811020009

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m841-m842

doi:10.1107/S1600536811020009

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Poly[[aquatris(μ-benzene-1,4-dicarboxylato)tricobalt(II)] methanol monosolvate monohydrate]

Hu Zhou,^a ^* Chao-Xia Chu ^a and Yi-Zhi Li ^b

^aSchool of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China, and ^bCoordination Chemistry Institute and the State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: aihuayuan@163.com

(Received 2 May 2011; accepted 26 May 2011; online 4 June 2011)

The asymmetric unit of the title compound, {[Co₃(C₈H₄O₄)₃(H₂O)]·CH₃OH·H₂O}_n, consists of four crystallographically independent Co cations, four benzene-1,4-dicarboxylate (bdc) anions, two water and one methanol solvent molecule. Two of the Co cations and two of the bdc anions are located on centres of inversion, whereas all other atoms are located in general positions. In the crystal, two Co atoms are only fourfold coordinated by three O atoms from three bdc ligands and by one O atom from one coordinated water molecule, while a third Co atom is coordinated by four O atoms from four bdc ligands within a strongly distorted tetrahedral geometry. The other two Co cations are octahedrally coordinated by six O atoms from six bdc anions. The Co cations are linked by the bdc anions into a three-dimensional framework. From this arrangement, cavities are formed in which additional methanol and water molecules are embedded.

Related literature

For related structures, see: Rosi et al. (2005 ); Devic et al. (2005 ); Humphrey et al. (2007 ); Luo et al. (2007 , 2008 ). For general background to benzene-1,4-dicarboxylic acid (H₂bdc), see: Férey et al. (2005 ); Rosi et al. (2003 ). For background to metal-organic frameworks (MOFs), see: Long & Yaghi (2009 ).

Experimental

Crystal data

[Co₃(C₈H₄O₄)₃(H₂O)]·CH₄O·H₂O
M_r = 737.20
Triclinic, $[P \overline 1]$
a = 9.8456 (11) Å
b = 12.0753 (15) Å
c = 13.0039 (16) Å
α = 91.842 (2)°
β = 100.925 (1)°
γ = 101.745 (1)°
V = 1482.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 291 K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.682, T_max = 0.746
11744 measured reflections
5751 independent reflections
4241 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.110
S = 1.04
5751 reflections
392 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.70 e Å⁻³

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: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020009/nc2230sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020009/nc2230Isup2.hkl

checkCIF report

Comment top

Recently, research on metal-organic frameworks (MOFs) has become of increasing interest (Long et al., 2009). In this context compounds based on dicarboxylate ligands are of special importance (Férey et al., 2005; Rosi et al., 2003). In our own investigations we tried to prepare new MOFs based on benzene-1,4-dicarboxylic acid (H₂bdc) and amines as ligands. Within this project we have reacted CoCl₂.6H₂O with H₂bdc and N,N'-bis(4-pyridylmethylidine)-1,4-phenylenediamine and we have obtained crystals of the title compound by accident.

The title compound is a three-dimensional framework the form hex type (Rosi et al., 2005) built from Co cations that are linked by bdc anions. From this arrangement cavities are formed, that are filled with additional uncoordinated methanol and water molecules. Altogether there are four crystallographically independent Co cations of which two (Co2 and Co4) are located on centers of inversion. Co1 is coordinated by three oxygen atoms from three bdc ligands and one oxygen atom from one coordinated water molecule within a strongly distorted tetrahedron. Co3 is also tetrahedrally coordinated but connected only to four oxygen atoms from four bdc ligands. In contrast Co2 and Co4 are 6-fold coordinated by six oxygen atoms from bdc anions within slightly distorted octahedra. Related complexes have been reported recently (Devic et al., 2005; Humphrey et al., 2007; Luo et al., 2007; Luo et al., 2008).

Related literature top

For related structures, see: Rosi et al. (2005); Devic et al. (2005); Humphrey et al. (2007); Luo et al. (2007, 2008). For general background to benzene-1,4-dicarboxylic acid (H₂bdc), see: Férey et al. (2005); Rosi et al. (2003). For background to metal-organic frameworks (MOFs), see: Long & Yaghi (2009).

Experimental top

A mixture of CoCl₂.6H₂O (0.0238 g, 0.1 mmol), benzene-1,4-dicarboxylic acid (0.0166 g, 0.1 mmol), N,N'-bis(4-pyridylmethylidine)-1,4-phenylenediamine (0.0290 g, 0.1 mmol) combined with 5 ml mixed solvent (DMF:CH₃OH = 1:1) was stirred for 20 min at room temperature. Afterwards the solution was heated in a 25 ml Teflon-lined stainless-steel vessel at 140 ^oC for 72 h under autogenous pressure. Slow cooling of the resulting solution to room temperature at the rate of 10 ^oC.h^-1 afforded purple block-shaped crystals suitable for single-crystal X-ray structure analysis. Yield based on CoCl₂.6H₂O: 35%.

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: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP diagram of the title compound. Displacement ellipsoids are drawn at 30% probability level. Hydrogen atoms have been omitted for clarity. Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 3, -y + 2, -z; (iii) -x + 1, -y + 1, -z + 1; (iv) x, y + 1, z - 1; (v) -x + 2, -y + 2, -z + 1; (vi) -x + 2, -y + 1, -z + 1; (vii) -x + 2, -y + 2, -z.

Poly[[aquatris(µ-benzene-1,4-dicarboxylato)tricobalt(II)] methanol monosolvate monohydrate] top

Crystal data top

[Co₃(C₈H₄O₄)₃(H₂O)]·CH₄O·H₂O	Z = 2
M_r = 737.20	F(000) = 742
Triclinic, P1	D_x = 1.652 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8456 (11) Å	Cell parameters from 3571 reflections
b = 12.0753 (15) Å	θ = 2.2–24.1°
c = 13.0039 (16) Å	µ = 1.73 mm⁻¹
α = 91.842 (2)°	T = 291 K
β = 100.925 (1)°	Block, purple
γ = 101.745 (1)°	0.30 × 0.26 × 0.24 mm
V = 1482.2 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	5751 independent reflections
Radiation source: sealed tube	4241 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→12
T_min = 0.682, T_max = 0.746	k = −14→14
11744 measured reflections	l = −15→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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.05P)² + 1.22P] where P = (F_o² + 2F_c²)/3
5751 reflections	(Δ/σ)_max < 0.001
392 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

[Co₃(C₈H₄O₄)₃(H₂O)]·CH₄O·H₂O	γ = 101.745 (1)°
M_r = 737.20	V = 1482.2 (3) Å³
Triclinic, P1	Z = 2
a = 9.8456 (11) Å	Mo Kα radiation
b = 12.0753 (15) Å	µ = 1.73 mm⁻¹
c = 13.0039 (16) Å	T = 291 K
α = 91.842 (2)°	0.30 × 0.26 × 0.24 mm
β = 100.925 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	5751 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	4241 reflections with I > 2σ(I)
T_min = 0.682, T_max = 0.746	R_int = 0.031
11744 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	Δρ_max = 0.36 e Å⁻³
5751 reflections	Δρ_min = −0.70 e Å⁻³
392 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	0.7655 (4)	0.4662 (3)	0.7910 (3)	0.0345 (9)
C2	0.7907 (5)	0.3680 (4)	0.7456 (4)	0.0454 (11)
H2	0.7628	0.3508	0.6719	0.054*
C3	0.8574 (5)	0.2946 (4)	0.8090 (4)	0.0419 (10)
H3	0.8717	0.2262	0.7790	0.050*
C4	0.9021 (5)	0.3234 (3)	0.9161 (3)	0.0398 (10)
C5	0.8818 (5)	0.4247 (4)	0.9588 (4)	0.0485 (12)
H5	0.9157	0.4461	1.0315	0.058*
C6	0.8129 (5)	0.4934 (4)	0.8958 (3)	0.0426 (10)
H6	0.7980	0.5615	0.9261	0.051*
C7	0.6950 (5)	0.5449 (4)	0.7247 (4)	0.0412 (10)
C8	0.9731 (5)	0.2503 (3)	0.9811 (4)	0.0422 (11)
C9	0.7203 (4)	0.8267 (3)	0.4169 (3)	0.0301 (8)
C10	0.6962 (5)	0.7946 (4)	0.3063 (4)	0.0505 (12)
H10	0.6323	0.7266	0.2758	0.061*
C11	0.7716 (5)	0.8688 (4)	0.2457 (4)	0.0429 (10)
H11	0.7599	0.8486	0.1728	0.052*
C12	0.8616 (5)	0.9694 (3)	0.2872 (3)	0.0400 (10)
C13	0.8770 (5)	1.0004 (4)	0.3927 (4)	0.0501 (12)
H13	0.9324	1.0721	0.4222	0.060*
C14	0.8078 (5)	0.9223 (4)	0.4566 (3)	0.0421 (11)
H14	0.8257	0.9401	0.5302	0.051*
C15	0.6447 (4)	0.7483 (3)	0.4814 (3)	0.0317 (8)
C16	0.9373 (4)	1.0442 (4)	0.2203 (3)	0.0375 (9)
C17	0.2859 (4)	0.6297 (4)	0.5711 (3)	0.0371 (10)
C18	0.1060 (5)	0.4418 (4)	0.5392 (4)	0.0426 (10)
H18	0.1803	0.4042	0.5644	0.051*
C19	0.1364 (4)	0.5612 (4)	0.5314 (3)	0.0356 (9)
C20	0.0241 (4)	0.6157 (4)	0.4882 (3)	0.0388 (10)
H20	0.0448	0.6948	0.4795	0.047*
C21	1.3134 (4)	1.1321 (4)	0.0668 (4)	0.0406 (10)
C22	1.5397 (5)	1.1132 (4)	−0.0081 (3)	0.0443 (11)
H22	1.5718	1.1927	−0.0099	0.053*
C23	1.4218 (5)	1.0740 (3)	0.0374 (3)	0.0378 (9)
C24	1.3909 (5)	0.9566 (4)	0.0493 (4)	0.0418 (10)
H24	1.3199	0.9262	0.0871	0.050*
C25	0.2871 (5)	0.4940 (4)	0.8243 (4)	0.0463 (11)
H25A	0.1955	0.4495	0.8330	0.069*
H25C	0.3313	0.4480	0.7826	0.069*
H25D	0.2728	0.5619	0.7881	0.069*
Co1	0.53756 (6)	0.71571 (5)	0.67841 (4)	0.03287 (15)
Co2	0.5000	0.5000	0.5000	0.03250 (18)
Co3	1.15981 (5)	1.21536 (4)	0.17863 (4)	0.02938 (14)
Co4	1.0000	1.0000	0.0000	0.03193 (18)
O1	0.6831 (3)	0.6278 (3)	0.7537 (2)	0.0465 (8)
O2	0.6588 (3)	0.5129 (3)	0.6183 (2)	0.0415 (7)
O3	0.9700 (3)	0.1490 (2)	0.9415 (2)	0.0377 (7)
O4	1.0326 (3)	0.2841 (2)	1.0748 (2)	0.0410 (7)
O5	0.6481 (3)	0.7837 (3)	0.5886 (3)	0.0476 (8)
O6	0.5728 (3)	0.6495 (2)	0.4424 (2)	0.0375 (7)
O7	0.9028 (3)	1.0201 (2)	0.1217 (2)	0.0352 (6)
O8	1.0366 (3)	1.1244 (3)	0.2642 (2)	0.0488 (8)
O9	0.3832 (3)	0.5818 (2)	0.6010 (2)	0.0344 (6)
O10	0.3048 (3)	0.7359 (3)	0.5713 (3)	0.0472 (8)
O11	1.2079 (3)	1.0796 (2)	0.0968 (2)	0.0378 (7)
O12	1.3470 (3)	1.2378 (3)	0.0664 (2)	0.0431 (7)
O13	0.3793 (3)	0.5276 (3)	0.9276 (2)	0.0409 (7)
H15B	0.4504	0.5936	0.9225	0.049*
O1W	0.4003 (3)	0.7587 (3)	0.7928 (3)	0.0458 (7)
H1X	0.3246	0.7899	0.7555	0.055*
H1Y	0.4577	0.8130	0.8474	0.055*
O2W	0.6664 (4)	0.9904 (3)	0.6639 (3)	0.0574 (9)
H2X	0.6605	0.9232	0.6394	0.069*
H2Y	0.7051	0.9975	0.7287	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.035 (2)	0.0287 (19)	0.037 (2)	−0.0018 (16)	0.0105 (17)	0.0053 (16)
C2	0.052 (3)	0.040 (2)	0.049 (3)	0.021 (2)	0.007 (2)	0.010 (2)
C3	0.043 (2)	0.040 (2)	0.042 (2)	0.0108 (19)	0.0044 (19)	−0.0060 (19)
C4	0.043 (2)	0.0248 (19)	0.039 (2)	0.0000 (17)	−0.0150 (19)	0.0038 (17)
C5	0.042 (3)	0.049 (3)	0.051 (3)	0.015 (2)	−0.006 (2)	0.009 (2)
C6	0.046 (3)	0.041 (2)	0.039 (2)	0.014 (2)	−0.001 (2)	0.0028 (19)
C7	0.048 (3)	0.036 (2)	0.039 (2)	0.0143 (19)	−0.0013 (19)	0.0020 (19)
C8	0.042 (2)	0.027 (2)	0.043 (2)	−0.0058 (17)	−0.0123 (19)	0.0003 (18)
C9	0.038 (2)	0.0307 (19)	0.0259 (19)	0.0086 (16)	0.0154 (16)	0.0076 (15)
C10	0.046 (3)	0.049 (3)	0.047 (3)	−0.014 (2)	0.012 (2)	−0.009 (2)
C11	0.039 (2)	0.043 (2)	0.042 (2)	−0.0065 (19)	0.0136 (19)	0.0080 (19)
C12	0.052 (3)	0.030 (2)	0.038 (2)	0.0021 (18)	0.014 (2)	0.0051 (17)
C13	0.039 (3)	0.058 (3)	0.044 (3)	−0.016 (2)	0.017 (2)	−0.006 (2)
C14	0.045 (2)	0.047 (2)	0.029 (2)	−0.0140 (19)	0.0191 (18)	−0.0087 (18)
C15	0.031 (2)	0.033 (2)	0.035 (2)	0.0109 (17)	0.0111 (17)	0.0033 (16)
C16	0.029 (2)	0.043 (2)	0.037 (2)	0.0043 (18)	0.0010 (17)	0.0074 (18)
C17	0.024 (2)	0.047 (2)	0.042 (2)	0.0131 (18)	0.0088 (17)	−0.0194 (19)
C18	0.039 (2)	0.050 (3)	0.040 (2)	0.011 (2)	0.0109 (19)	−0.009 (2)
C19	0.0220 (19)	0.047 (2)	0.040 (2)	0.0097 (17)	0.0076 (16)	0.0106 (18)
C20	0.027 (2)	0.047 (2)	0.045 (2)	0.0127 (18)	0.0089 (18)	0.010 (2)
C21	0.021 (2)	0.046 (3)	0.048 (3)	0.0071 (18)	−0.0085 (18)	−0.012 (2)
C22	0.047 (3)	0.038 (2)	0.040 (2)	−0.009 (2)	0.014 (2)	−0.0141 (19)
C23	0.049 (3)	0.031 (2)	0.039 (2)	0.0132 (18)	0.0160 (19)	0.0091 (17)
C24	0.039 (2)	0.046 (3)	0.041 (2)	0.005 (2)	0.0135 (19)	0.007 (2)
C25	0.052 (3)	0.050 (3)	0.042 (3)	0.020 (2)	0.011 (2)	0.017 (2)
Co1	0.0347 (3)	0.0324 (3)	0.0326 (3)	0.0089 (2)	0.0080 (2)	−0.0003 (2)
Co2	0.0330 (4)	0.0316 (4)	0.0325 (4)	0.0079 (3)	0.0049 (3)	−0.0009 (3)
Co3	0.0267 (3)	0.0323 (3)	0.0271 (3)	0.0056 (2)	0.0015 (2)	0.0005 (2)
Co4	0.0336 (4)	0.0275 (4)	0.0332 (4)	0.0048 (3)	0.0052 (3)	0.0004 (3)
O1	0.0524 (19)	0.0331 (17)	0.0452 (18)	0.0145 (14)	−0.0167 (15)	−0.0057 (14)
O2	0.0440 (17)	0.0429 (17)	0.0382 (16)	0.0121 (14)	0.0057 (13)	0.0069 (13)
O3	0.0389 (16)	0.0433 (16)	0.0391 (16)	0.0201 (13)	0.0150 (13)	0.0105 (13)
O4	0.0444 (17)	0.0395 (16)	0.0288 (15)	0.0059 (13)	−0.0132 (13)	−0.0077 (12)
O5	0.0482 (18)	0.0426 (17)	0.0477 (18)	−0.0097 (14)	0.0222 (15)	−0.0115 (14)
O6	0.0356 (15)	0.0306 (15)	0.0393 (16)	0.0071 (12)	−0.0088 (12)	−0.0015 (12)
O7	0.0272 (14)	0.0441 (16)	0.0321 (16)	0.0020 (12)	0.0061 (12)	0.0048 (12)
O8	0.0491 (19)	0.0430 (18)	0.0435 (18)	−0.0162 (15)	0.0123 (15)	−0.0080 (14)
O9	0.0275 (14)	0.0438 (16)	0.0333 (15)	0.0138 (12)	0.0038 (11)	−0.0045 (12)
O10	0.0519 (19)	0.0427 (18)	0.0460 (18)	0.0149 (15)	0.0051 (15)	−0.0127 (14)
O11	0.0399 (17)	0.0416 (16)	0.0320 (15)	0.0062 (13)	0.0105 (13)	−0.0001 (12)
O12	0.0432 (17)	0.0422 (17)	0.0427 (17)	0.0040 (14)	0.0142 (14)	−0.0160 (14)
O13	0.0421 (17)	0.0412 (17)	0.0441 (17)	0.0105 (13)	0.0165 (14)	0.0129 (13)
O1W	0.0454 (18)	0.0419 (17)	0.0494 (18)	0.0047 (14)	0.0156 (14)	−0.0145 (14)
O2W	0.058 (2)	0.051 (2)	0.053 (2)	−0.0121 (16)	0.0132 (17)	−0.0059 (16)

Geometric parameters (Å, º) top

C1—C6	1.360 (6)	C21—O11	1.239 (5)
C1—C2	1.395 (6)	C21—O12	1.252 (5)
C1—C7	1.491 (6)	C21—C23	1.489 (6)
C2—C3	1.405 (6)	C22—C24ⁱⁱ	1.345 (6)
C2—H2	0.9500	C22—C23	1.406 (6)
C3—C4	1.388 (6)	C22—H22	0.9500
C3—H3	0.9500	C23—C24	1.408 (6)
C4—C5	1.393 (6)	C24—C22ⁱⁱ	1.345 (6)
C4—C8	1.435 (6)	C24—H24	0.9500
C5—C6	1.372 (6)	C25—O13	1.465 (5)
C5—H5	0.9500	C25—H25A	0.9800
C6—H6	0.9500	C25—H25C	0.9800
C7—O1	1.095 (5)	C25—H25D	0.9800
C7—O2	1.383 (5)	Co1—O5	1.845 (3)
C8—O4	1.262 (5)	Co1—O9	2.062 (3)
C8—O3	1.305 (5)	Co1—O1	2.072 (3)
C9—C14	1.315 (6)	Co1—O1W	2.304 (3)
C9—C10	1.440 (6)	Co2—O2	1.952 (3)
C9—C15	1.468 (5)	Co2—O2ⁱⁱⁱ	1.952 (3)
C10—C11	1.404 (6)	Co2—O6	2.024 (3)
C10—H10	0.9500	Co2—O6ⁱⁱⁱ	2.024 (3)
C11—C12	1.376 (6)	Co2—O9	2.230 (3)
C11—H11	0.9500	Co2—O9ⁱⁱⁱ	2.230 (3)
C12—C13	1.381 (6)	Co3—O4^iv	1.984 (3)
C12—C16	1.467 (6)	Co3—O8	1.990 (3)
C13—C14	1.431 (6)	Co3—O11	2.107 (3)
C13—H13	0.9500	Co3—O1^v	2.222 (3)
C14—H14	0.9500	Co4—O3^iv	2.030 (3)
C15—O6	1.289 (5)	Co4—O3^vi	2.030 (3)
C15—O5	1.437 (5)	Co4—O7	2.030 (3)
C16—O8	1.260 (5)	Co4—O7^vii	2.030 (3)
C16—O7	1.271 (5)	Co4—O11	2.201 (3)
C17—O9	1.226 (5)	Co4—O11^vii	2.201 (3)
C17—O10	1.258 (5)	O1—Co3^v	2.222 (3)
C17—C19	1.519 (6)	O3—Co4^viii	2.030 (3)
C18—C20ⁱ	1.304 (6)	O4—Co3^viii	1.984 (3)
C18—C19	1.422 (6)	O13—H15B	0.9600
C18—H18	0.9500	O1W—H1X	0.9601
C19—C20	1.434 (5)	O1W—H1Y	0.9600
C20—C18ⁱ	1.304 (6)	O2W—H2X	0.8501
C20—H20	0.9500	O2W—H2Y	0.8500

C6—C1—C2	119.5 (4)	C23—C24—H24	119.4
C6—C1—C7	119.8 (4)	O13—C25—H25A	109.5
C2—C1—C7	120.6 (4)	O13—C25—H25C	109.5
C1—C2—C3	120.0 (4)	H25A—C25—H25C	109.5
C1—C2—H2	120.0	O13—C25—H25D	109.5
C3—C2—H2	120.0	H25A—C25—H25D	109.5
C4—C3—C2	119.1 (4)	H25C—C25—H25D	109.5
C4—C3—H3	120.5	O5—Co1—O9	110.87 (13)
C2—C3—H3	120.5	O5—Co1—O1	96.16 (16)
C3—C4—C5	119.8 (4)	O9—Co1—O1	99.86 (11)
C3—C4—C8	119.5 (4)	O5—Co1—O1W	140.91 (13)
C5—C4—C8	120.6 (4)	O9—Co1—O1W	93.65 (11)
C6—C5—C4	120.0 (4)	O1—Co1—O1W	109.49 (14)
C6—C5—H5	120.0	O2—Co2—O2ⁱⁱⁱ	180.000 (1)
C4—C5—H5	120.0	O2—Co2—O6	96.10 (12)
C1—C6—C5	121.5 (4)	O2ⁱⁱⁱ—Co2—O6	83.90 (12)
C1—C6—H6	119.3	O2—Co2—O6ⁱⁱⁱ	83.90 (12)
C5—C6—H6	119.3	O2ⁱⁱⁱ—Co2—O6ⁱⁱⁱ	96.10 (12)
O1—C7—O2	120.2 (4)	O6—Co2—O6ⁱⁱⁱ	180.0
O1—C7—C1	124.2 (4)	O2—Co2—O9	90.15 (11)
O2—C7—C1	115.2 (4)	O2ⁱⁱⁱ—Co2—O9	89.85 (11)
O4—C8—O3	122.1 (4)	O6—Co2—O9	91.77 (11)
O4—C8—C4	119.7 (4)	O6ⁱⁱⁱ—Co2—O9	88.23 (11)
O3—C8—C4	118.2 (4)	O2—Co2—O9ⁱⁱⁱ	89.85 (11)
C14—C9—C10	120.2 (4)	O2ⁱⁱⁱ—Co2—O9ⁱⁱⁱ	90.15 (11)
C14—C9—C15	122.6 (4)	O6—Co2—O9ⁱⁱⁱ	88.23 (11)
C10—C9—C15	117.2 (4)	O6ⁱⁱⁱ—Co2—O9ⁱⁱⁱ	91.77 (11)
C11—C10—C9	116.8 (4)	O9—Co2—O9ⁱⁱⁱ	180.000 (1)
C11—C10—H10	121.6	O4^iv—Co3—O8	106.09 (14)
C9—C10—H10	121.6	O4^iv—Co3—O11	106.51 (11)
C12—C11—C10	122.8 (4)	O8—Co3—O11	97.95 (13)
C12—C11—H11	118.6	O4^iv—Co3—O1^v	98.73 (11)
C10—C11—H11	118.6	O8—Co3—O1^v	121.70 (13)
C11—C12—C13	118.9 (4)	O11—Co3—O1^v	124.18 (12)
C11—C12—C16	120.6 (4)	O3^iv—Co4—O3^vi	180.00 (6)
C13—C12—C16	120.4 (4)	O3^iv—Co4—O7	93.55 (11)
C12—C13—C14	118.7 (4)	O3^vi—Co4—O7	86.45 (11)
C12—C13—H13	120.7	O3^iv—Co4—O7^vii	86.45 (11)
C14—C13—H13	120.7	O3^vi—Co4—O7^vii	93.55 (11)
C9—C14—C13	122.3 (4)	O7—Co4—O7^vii	180.000 (1)
C9—C14—H14	118.8	O3^iv—Co4—O11	92.68 (12)
C13—C14—H14	118.8	O3^vi—Co4—O11	87.32 (12)
O6—C15—O5	119.8 (3)	O7—Co4—O11	91.18 (11)
O6—C15—C9	120.9 (4)	O7^vii—Co4—O11	88.82 (11)
O5—C15—C9	119.3 (3)	O3^iv—Co4—O11^vii	87.32 (12)
O8—C16—O7	124.3 (4)	O3^vi—Co4—O11^vii	92.68 (12)
O8—C16—C12	118.2 (4)	O7—Co4—O11^vii	88.82 (11)
O7—C16—C12	117.5 (4)	O7^vii—Co4—O11^vii	91.18 (10)
O9—C17—O10	122.1 (4)	O11—Co4—O11^vii	180.0
O9—C17—C19	120.4 (4)	C7—O1—Co1	124.3 (3)
O10—C17—C19	117.4 (4)	C7—O1—Co3^v	132.2 (3)
C20ⁱ—C18—C19	119.8 (4)	Co1—O1—Co3^v	93.67 (12)
C20ⁱ—C18—H18	120.1	C7—O2—Co2	140.1 (3)
C19—C18—H18	120.1	C8—O3—Co4^viii	135.7 (3)
C18—C19—C20	119.3 (4)	C8—O4—Co3^viii	130.1 (3)
C18—C19—C17	119.9 (4)	C15—O5—Co1	128.3 (3)
C20—C19—C17	120.8 (4)	C15—O6—Co2	136.0 (3)
C18ⁱ—C20—C19	120.8 (4)	C16—O7—Co4	138.1 (3)
C18ⁱ—C20—H20	119.6	C16—O8—Co3	119.8 (3)
C19—C20—H20	119.6	C17—O9—Co1	100.9 (3)
O11—C21—O12	124.7 (4)	C17—O9—Co2	126.7 (3)
O11—C21—C23	122.0 (4)	Co1—O9—Co2	102.39 (11)
O12—C21—C23	113.0 (4)	C21—O11—Co3	98.8 (3)
C24ⁱⁱ—C22—C23	123.1 (4)	C21—O11—Co4	127.7 (3)
C24ⁱⁱ—C22—H22	118.5	Co3—O11—Co4	101.90 (12)
C23—C22—H22	118.5	C25—O13—H15B	109.3
C22—C23—C24	115.3 (4)	Co1—O1W—H1X	109.6
C22—C23—C21	131.7 (4)	Co1—O1W—H1Y	109.4
C24—C23—C21	112.7 (4)	H1X—O1W—H1Y	109.5
C22ⁱⁱ—C24—C23	121.1 (4)	H2X—O2W—H2Y	109.5
C22ⁱⁱ—C24—H24	119.4

C6—C1—C2—C3	3.6 (7)	O6ⁱⁱⁱ—Co2—O2—C7	−82.0 (4)
C7—C1—C2—C3	179.9 (4)	O9—Co2—O2—C7	6.3 (4)
C1—C2—C3—C4	−2.4 (7)	O9ⁱⁱⁱ—Co2—O2—C7	−173.7 (4)
C2—C3—C4—C5	−0.7 (7)	O4—C8—O3—Co4^viii	17.9 (7)
C2—C3—C4—C8	−178.6 (4)	C4—C8—O3—Co4^viii	−160.1 (3)
C3—C4—C5—C6	2.5 (7)	O3—C8—O4—Co3^viii	11.3 (7)
C8—C4—C5—C6	−179.6 (5)	C4—C8—O4—Co3^viii	−170.8 (3)
C2—C1—C6—C5	−1.8 (7)	O6—C15—O5—Co1	−11.2 (5)
C7—C1—C6—C5	−178.1 (4)	C9—C15—O5—Co1	167.2 (3)
C4—C5—C6—C1	−1.3 (8)	O9—Co1—O5—C15	−5.8 (4)
C6—C1—C7—O1	3.7 (8)	O1—Co1—O5—C15	97.2 (3)
C2—C1—C7—O1	−172.6 (5)	O1W—Co1—O5—C15	−131.1 (3)
C6—C1—C7—O2	176.1 (4)	O5—C15—O6—Co2	−22.8 (6)
C2—C1—C7—O2	−0.2 (6)	C9—C15—O6—Co2	158.9 (3)
C3—C4—C8—O4	169.3 (4)	O2—Co2—O6—C15	−33.7 (4)
C5—C4—C8—O4	−8.6 (7)	O2ⁱⁱⁱ—Co2—O6—C15	146.3 (4)
C3—C4—C8—O3	−12.7 (7)	O9—Co2—O6—C15	56.6 (4)
C5—C4—C8—O3	169.4 (4)	O9ⁱⁱⁱ—Co2—O6—C15	−123.4 (4)
C14—C9—C10—C11	1.0 (7)	O8—C16—O7—Co4	46.4 (7)
C15—C9—C10—C11	−178.5 (4)	C12—C16—O7—Co4	−129.9 (4)
C9—C10—C11—C12	−1.9 (7)	O3^iv—Co4—O7—C16	−106.4 (4)
C10—C11—C12—C13	−1.2 (7)	O3^vi—Co4—O7—C16	73.6 (4)
C10—C11—C12—C16	−179.7 (4)	O11—Co4—O7—C16	−13.6 (4)
C11—C12—C13—C14	5.1 (7)	O11^vii—Co4—O7—C16	166.4 (4)
C16—C12—C13—C14	−176.4 (4)	O7—C16—O8—Co3	−4.6 (6)
C10—C9—C14—C13	3.0 (7)	C12—C16—O8—Co3	171.7 (3)
C15—C9—C14—C13	−177.5 (4)	O4^iv—Co3—O8—C16	60.0 (4)
C12—C13—C14—C9	−6.1 (8)	O11—Co3—O8—C16	−49.8 (4)
C14—C9—C15—O6	−171.9 (4)	O1^v—Co3—O8—C16	171.3 (3)
C10—C9—C15—O6	7.7 (6)	O10—C17—O9—Co1	14.7 (5)
C14—C9—C15—O5	9.8 (6)	C19—C17—O9—Co1	−165.7 (3)
C10—C9—C15—O5	−170.7 (4)	O10—C17—O9—Co2	−99.9 (4)
C11—C12—C16—O8	−167.5 (4)	C19—C17—O9—Co2	79.7 (5)
C13—C12—C16—O8	14.1 (7)	O5—Co1—O9—C17	−90.8 (3)
C11—C12—C16—O7	9.0 (6)	O1—Co1—O9—C17	168.6 (3)
C13—C12—C16—O7	−169.4 (4)	O1W—Co1—O9—C17	58.1 (3)
C20ⁱ—C18—C19—C20	−3.2 (7)	O5—Co1—O9—Co2	40.87 (17)
C20ⁱ—C18—C19—C17	175.3 (4)	O1—Co1—O9—Co2	−59.66 (15)
O9—C17—C19—C18	6.7 (6)	O1W—Co1—O9—Co2	−170.18 (12)
O10—C17—C19—C18	−173.7 (4)	O2—Co2—O9—C17	158.8 (4)
O9—C17—C19—C20	−174.8 (4)	O2ⁱⁱⁱ—Co2—O9—C17	−21.2 (4)
O10—C17—C19—C20	4.8 (6)	O6—Co2—O9—C17	62.6 (4)
C18—C19—C20—C18ⁱ	3.2 (7)	O6ⁱⁱⁱ—Co2—O9—C17	−117.4 (4)
C17—C19—C20—C18ⁱ	−175.3 (4)	O2—Co2—O9—Co1	44.79 (13)
C24ⁱⁱ—C22—C23—C24	7.7 (8)	O2ⁱⁱⁱ—Co2—O9—Co1	−135.21 (13)
C24ⁱⁱ—C22—C23—C21	−165.6 (5)	O6—Co2—O9—Co1	−51.32 (12)
O11—C21—C23—C22	172.5 (5)	O6ⁱⁱⁱ—Co2—O9—Co1	128.68 (12)
O12—C21—C23—C22	−13.3 (7)	O12—C21—O11—Co3	−15.7 (5)
O11—C21—C23—C24	−0.9 (6)	C23—C21—O11—Co3	157.8 (4)
O12—C21—C23—C24	173.4 (4)	O12—C21—O11—Co4	96.9 (5)
C22—C23—C24—C22ⁱⁱ	−7.5 (7)	C23—C21—O11—Co4	−89.6 (5)
C21—C23—C24—C22ⁱⁱ	167.0 (4)	O4^iv—Co3—O11—C21	88.6 (3)
O2—C7—O1—Co1	27.2 (7)	O8—Co3—O11—C21	−161.9 (3)
C1—C7—O1—Co1	−160.8 (3)	O1^v—Co3—O11—C21	−24.5 (3)
O2—C7—O1—Co3^v	−109.1 (4)	O4^iv—Co3—O11—Co4	−43.08 (15)
C1—C7—O1—Co3^v	63.0 (7)	O8—Co3—O11—Co4	66.39 (14)
O5—Co1—O1—C7	−84.9 (5)	O1^v—Co3—O11—Co4	−156.19 (11)
O9—Co1—O1—C7	27.6 (5)	O3^iv—Co4—O11—C21	−58.9 (4)
O1W—Co1—O1—C7	125.1 (4)	O3^vi—Co4—O11—C21	121.1 (4)
O5—Co1—O1—Co3^v	64.22 (14)	O7—Co4—O11—C21	−152.6 (4)
O9—Co1—O1—Co3^v	176.70 (12)	O7^vii—Co4—O11—C21	27.4 (4)
O1W—Co1—O1—Co3^v	−85.82 (14)	O3^iv—Co4—O11—Co3	52.20 (13)
O1—C7—O2—Co2	−53.0 (7)	O3^vi—Co4—O11—Co3	−127.80 (13)
C1—C7—O2—Co2	134.3 (4)	O7—Co4—O11—Co3	−41.41 (13)
O6—Co2—O2—C7	98.0 (4)	O7^vii—Co4—O11—Co3	138.59 (13)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+3, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z−1; (v) −x+2, −y+2, −z+1; (vi) −x+2, −y+1, −z+1; (vii) −x+2, −y+2, −z; (viii) x, y−1, z+1.

Experimental details

Crystal data
Chemical formula	[Co₃(C₈H₄O₄)₃(H₂O)]·CH₄O·H₂O
M_r	737.20
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.8456 (11), 12.0753 (15), 13.0039 (16)
α, β, γ (°)	91.842 (2), 100.925 (1), 101.745 (1)
V (Å³)	1482.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.73
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.682, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	11744, 5751, 4241
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.110, 1.04
No. of reflections	5751
No. of parameters	392
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.70

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

Acknowledgements

The work was supported by the Project of the Priority Academic Program Development of Jiangsu Higher Education Institutions and the Project of Jiangsu University of Science and Technology (2009 C L152J).

References

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