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Acta Cryst. (2008). E64, m446    [ doi:10.1107/S1600536808003140 ]

Tetraaquabis(4-formylbenzoato-[kappa]O)cobalt(II) tetrahydrate

Z.-P. Deng, S. Gao, L.-H. Huo and S. W. Ng

Abstract top

The CoII atom in the title compound, [Co(C8H5O3)2(H2O)4]·4H2O, which exists in an all-trans octahedral coordination geometry, lies on a center of inversion. The coordinated and uncoordinated water molecules engage in extensive hydrogen-bonding interactions, forming a three-dimensional hydrogen-bonded network.

Comment top

Hexaaquacobalt(II) bis(4-formylbenzoate) dihydrate was isolated from the reaction of cobalt(II) acetate and 4-formylbenzoic acid in the presence of sodium hydroxide (Deng et al., 2006b). The reaction with pyridine in place of sodium hydroxide yielded the formybenzoate-coordinated title compound.

Related literature top

Hexaaquacobalt(II) bis(4-formylbenzoate) dihydrate was isolated from the reaction of cobalt(II) acetate and 4-formylbenzoic acid in the presence of sodium hydroxide; see Deng et al. (2006b). The reaction with pyridine in place of sodium hydroxide yielded the formybenzoate-coordinated title compound. This is isostructural with the nickel analog; see Deng et al. (2006a).

Experimental top

Cobalt diacetate dihydrate (2.32 g, 10 mmol) was added to an aqueous solution of 4-formylbenzoic acid (3.0 g, 20 mmol) that was earlier been treated with 1 ml pyridine to give a pH of 6. The solution was allowed to evaporate at room temperature; pink prismatic crystals separated from the filtered solution after several days. C&H elemental analysis. Calc. for C16H26O14Co: C 38.33, H 5.23%. Found: C 38.36, H 5.24%.

Refinement top

The carbon-bound H atoms were placed in calculated positions [C–H 0.93 Å and Uiso(H) 1.2Ueq(C)], and were included in the refinement in the riding-model approximation. The water H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.85±0.01 Å and H···H 1.39±0.01 Å; their displacement parameters were freely refined.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: atomic coordinates taken from the isostructural nickel analog; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Anisotropic displacement parameter plot of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radius.
Tetraaquabis(4-formylbenzoato-κO)cobalt(II) tetrahydrate top
Crystal data top
[Co(C8H5O3)2(H2O)4]·4H2OZ = 1
Mr = 501.30F000 = 261
Triclinic, P1Dx = 1.551 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.1472 (3) ÅCell parameters from 4983 reflections
b = 7.4759 (4) Åθ = 3.1–27.5º
c = 11.5720 (6) ŵ = 0.87 mm−1
α = 77.114 (2)ºT = 295 (2) K
β = 77.905 (2)ºPrism, pink
γ = 63.839 (1)º0.30 × 0.26 × 0.22 mm
V = 536.61 (5) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2426 independent reflections
Radiation source: fine-focus sealed tube2270 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
Detector resolution: 10.000 pixels mm-1θmax = 27.5º
T = 295(2) Kθmin = 3.1º
ω scansh = −9→9
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −9→9
Tmin = 0.666, Tmax = 0.832l = −15→14
5294 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.080  w = 1/[σ2(Fo2) + (0.0481P)2 + 0.1724P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2426 reflectionsΔρmax = 0.36 e Å−3
174 parametersΔρmin = −0.27 e Å−3
12 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Co(C8H5O3)2(H2O)4]·4H2Oγ = 63.839 (1)º
Mr = 501.30V = 536.61 (5) Å3
Triclinic, P1Z = 1
a = 7.1472 (3) ÅMo Kα
b = 7.4759 (4) ŵ = 0.87 mm−1
c = 11.5720 (6) ÅT = 295 (2) K
α = 77.114 (2)º0.30 × 0.26 × 0.22 mm
β = 77.905 (2)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2426 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2270 reflections with I > 2σ(I)
Tmin = 0.666, Tmax = 0.832Rint = 0.016
5294 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02712 restraints
wR(F2) = 0.080H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 0.36 e Å−3
2426 reflectionsΔρmin = −0.27 e Å−3
174 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.50000.50000.50000.02806 (11)
O10.45499 (18)0.39037 (19)0.36093 (10)0.0359 (3)
O20.0927 (2)0.2392 (2)−0.11561 (12)0.0492 (3)
O30.76754 (19)0.3176 (2)0.25021 (12)0.0460 (3)
O1W0.19780 (18)0.52308 (19)0.58061 (11)0.0381 (3)
H1W10.192 (3)0.570 (3)0.6429 (14)0.057 (7)*
H1W20.091 (3)0.602 (3)0.5461 (19)0.071 (8)*
O2W0.3680 (2)0.79054 (18)0.40003 (12)0.0408 (3)
H2W10.329 (4)0.893 (3)0.434 (2)0.067 (8)*
H2W20.271 (3)0.807 (4)0.362 (2)0.069 (8)*
O3W0.2016 (3)1.1588 (2)0.48800 (14)0.0544 (4)
H3W10.152 (3)1.158 (3)0.5610 (10)0.051 (6)*
H3W20.282 (4)1.218 (4)0.470 (2)0.096 (11)*
O4W−0.0173 (2)1.1045 (2)0.71542 (13)0.0534 (4)
H4W10.001 (4)1.159 (3)0.767 (2)0.076 (8)*
H4W20.048 (5)0.9775 (14)0.731 (3)0.096 (11)*
C10.2664 (3)0.2311 (2)−0.11986 (15)0.0384 (4)
H10.35630.2070−0.19100.046*
C20.3455 (2)0.2570 (2)−0.01950 (13)0.0311 (3)
C30.2157 (2)0.3005 (3)0.08787 (15)0.0351 (3)
H30.07790.31390.09670.042*
C40.2921 (2)0.3237 (3)0.18106 (14)0.0344 (3)
H40.20520.35370.25250.041*
C50.4989 (2)0.3026 (2)0.16869 (13)0.0279 (3)
C60.6284 (2)0.2574 (2)0.06149 (14)0.0321 (3)
H60.76680.24200.05280.039*
C70.5514 (3)0.2353 (2)−0.03205 (14)0.0334 (3)
H70.63800.2059−0.10370.040*
C80.5803 (2)0.3383 (2)0.26758 (13)0.0297 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02531 (16)0.03279 (16)0.02910 (16)−0.01180 (12)−0.00411 (10)−0.01027 (11)
O10.0324 (5)0.0492 (6)0.0324 (6)−0.0187 (5)−0.0014 (4)−0.0167 (5)
O20.0491 (8)0.0561 (8)0.0500 (8)−0.0196 (6)−0.0160 (6)−0.0179 (6)
O30.0315 (6)0.0714 (9)0.0433 (7)−0.0231 (6)−0.0004 (5)−0.0248 (6)
O1W0.0298 (6)0.0469 (7)0.0409 (7)−0.0161 (5)−0.0034 (5)−0.0134 (5)
O2W0.0431 (7)0.0362 (6)0.0432 (7)−0.0124 (5)−0.0143 (5)−0.0063 (5)
O3W0.0666 (9)0.0547 (8)0.0556 (9)−0.0350 (8)−0.0125 (7)−0.0084 (7)
O4W0.0528 (8)0.0562 (9)0.0547 (9)−0.0140 (7)−0.0207 (6)−0.0204 (7)
C10.0468 (9)0.0372 (8)0.0326 (8)−0.0149 (7)−0.0078 (7)−0.0104 (6)
C20.0378 (8)0.0278 (7)0.0290 (7)−0.0132 (6)−0.0063 (6)−0.0055 (5)
C30.0300 (7)0.0459 (9)0.0341 (8)−0.0184 (7)−0.0029 (6)−0.0102 (6)
C40.0325 (8)0.0448 (8)0.0276 (7)−0.0171 (7)0.0008 (6)−0.0106 (6)
C50.0300 (7)0.0268 (6)0.0278 (7)−0.0114 (6)−0.0048 (5)−0.0056 (5)
C60.0292 (7)0.0348 (7)0.0331 (8)−0.0137 (6)−0.0007 (6)−0.0084 (6)
C70.0379 (8)0.0340 (7)0.0273 (7)−0.0143 (6)0.0017 (6)−0.0093 (6)
C80.0295 (7)0.0297 (7)0.0305 (7)−0.0110 (6)−0.0050 (6)−0.0071 (5)
Geometric parameters (Å, °) top
Co1—O12.098 (1)O4W—H4W10.847 (10)
Co1—O1i2.098 (1)O4W—H4W20.849 (10)
Co1—O1Wi2.113 (1)C1—C21.475 (2)
Co1—O1w2.113 (1)C1—H10.9300
Co1—O2w2.116 (1)C2—C71.388 (2)
Co1—O2Wi2.116 (1)C2—C31.393 (2)
O1—C81.2630 (18)C3—C41.381 (2)
O2—C11.207 (2)C3—H30.9300
O3—C81.2543 (19)C4—C51.395 (2)
O1W—H1W10.858 (9)C4—H40.9300
O1W—H1W20.844 (9)C5—C61.393 (2)
O2W—H2W10.849 (9)C5—C81.507 (2)
O2W—H2W20.848 (9)C6—C71.382 (2)
O3W—H3W10.845 (9)C6—H60.9300
O3W—H3W20.838 (10)C7—H70.9300
O1—Co1—O1i180.0O2—C1—C2124.23 (16)
O1—Co1—O1Wi93.12 (5)O2—C1—H1117.9
O1i—Co1—O1Wi86.88 (5)C2—C1—H1117.9
O1—Co1—O1W86.88 (5)C7—C2—C3119.95 (14)
O1i—Co1—O1W93.12 (5)C7—C2—C1119.56 (14)
O1Wi—Co1—O1W180.0C3—C2—C1120.49 (14)
O1—Co1—O2W86.82 (5)C4—C3—C2119.79 (14)
O1i—Co1—O2W93.18 (5)C4—C3—H3120.1
O1Wi—Co1—O2W89.23 (5)C2—C3—H3120.1
O1W—Co1—O2W90.77 (5)C3—C4—C5120.42 (14)
O1—Co1—O2Wi93.18 (5)C3—C4—H4119.8
O1i—Co1—O2Wi86.82 (5)C5—C4—H4119.8
O1Wi—Co1—O2Wi90.77 (5)C6—C5—C4119.52 (14)
O1W—Co1—O2Wi89.23 (5)C6—C5—C8119.64 (13)
O2W—Co1—O2Wi180.0C4—C5—C8120.77 (13)
C8—O1—Co1127.37 (10)C7—C6—C5120.04 (14)
Co1—O1W—H1W197.7 (16)C7—C6—H6120.0
Co1—O1W—H1W2120.0 (19)C5—C6—H6120.0
H1W1—O1W—H1W2108.3 (14)C6—C7—C2120.27 (14)
Co1—O2W—H2W1118.7 (17)C6—C7—H7119.9
Co1—O2W—H2W2113.8 (17)C2—C7—H7119.9
H2W1—O2W—H2W2108.9 (15)O3—C8—O1124.60 (14)
H3W1—O3W—H3W2110.9 (15)O3—C8—C5117.39 (13)
H4W1—O4W—H4W2109.2 (15)O1—C8—C5118.00 (13)
O1i—Co1—O1—C80(100)C4—C5—C6—C70.5 (2)
O1Wi—Co1—O1—C8−0.75 (13)C8—C5—C6—C7−176.45 (13)
O1W—Co1—O1—C8179.25 (13)C5—C6—C7—C2−0.4 (2)
O2W—Co1—O1—C888.31 (13)C3—C2—C7—C6−0.2 (2)
O2Wi—Co1—O1—C8−91.69 (13)C1—C2—C7—C6−179.45 (14)
O2—C1—C2—C7176.99 (16)Co1—O1—C8—O310.4 (2)
O2—C1—C2—C3−2.3 (3)Co1—O1—C8—C5−168.27 (9)
C7—C2—C3—C40.6 (2)C6—C5—C8—O3−2.7 (2)
C1—C2—C3—C4179.83 (15)C4—C5—C8—O3−179.67 (15)
C2—C3—C4—C5−0.4 (2)C6—C5—C8—O1176.00 (14)
C3—C4—C5—C6−0.1 (2)C4—C5—C8—O1−0.9 (2)
C3—C4—C5—C8176.80 (15)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O3i0.86 (1)1.77 (1)2.611 (2)166 (2)
O1W—H1W2···O3Wii0.84 (1)2.11 (1)2.925 (2)161 (2)
O2W—H2W1···O3W0.85 (1)1.97 (1)2.808 (2)168 (2)
O2W—H2W2···O4Wii0.85 (1)1.97 (1)2.808 (2)169 (2)
O3W—H3W1···O4W0.85 (1)2.00 (1)2.810 (2)159 (2)
O3W—H3W2···O1iii0.84 (1)2.19 (1)2.992 (2)159 (2)
O4W—H4W1···O2iv0.85 (1)1.93 (1)2.771 (2)169 (3)
O4W—H4W2···O3i0.85 (1)2.00 (1)2.841 (2)172 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) x, y+1, z; (iv) x, y+1, z+1.
Table 1
Selected geometric parameters (Å) top
Co1—O12.098 (1)Co1—O2w2.116 (1)
Co1—O1w2.113 (1)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O3i0.86 (1)1.77 (1)2.611 (2)166 (2)
O1W—H1W2···O3Wii0.84 (1)2.11 (1)2.925 (2)161 (2)
O2W—H2W1···O3W0.85 (1)1.97 (1)2.808 (2)168 (2)
O2W—H2W2···O4Wii0.85 (1)1.97 (1)2.808 (2)169 (2)
O3W—H3W1···O4W0.85 (1)2.00 (1)2.810 (2)159 (2)
O3W—H3W2···O1iii0.84 (1)2.19 (1)2.992 (2)159 (2)
O4W—H4W1···O2iv0.85 (1)1.93 (1)2.771 (2)169 (3)
O4W—H4W2···O3i0.85 (1)2.00 (1)2.841 (2)172 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) x, y+1, z; (iv) x, y+1, z+1.
Acknowledgements top

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this work.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Deng, Z.-P., Gao, S. & Ng, S. W. (2006a). Acta Cryst. E62, m2904–m2905.

Deng, Z.-P., Gao, S. & Ng, S. W. (2006b). Acta Cryst. E62, m3423–m3424.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2008). publCIF. In preparation.