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Acta Cryst. (2007). E63, m2214    [ doi:10.1107/S1600536807035295 ]

Diaquabis(5-n-butylpyridine-2-carboxylato)cobalt(II)

R.-Z. Fan, W.-D. Song and X.-M. Hao

Abstract top

The title complex, [Co(C10H12NO2)2(H2O)2], a neutral mononuclear molecule, consists of a CoII ion, two 5-n-butylpyridine-2-carboxylate ligands and two water molecules. The CoII atom, located on a centre of symmetry, displays a distorted octahedral coordination geometry. Intermolecular O-H...O hydrogen bonds form a supramolecular network structure.

Comment top

Some structures of transition metal complexes containing the 5-butyl-pyridyl-2-carboxylic acid (fusaric acid) ligand have been reported. In the structural investigation of these complexes, it has been found that the fusaric acid functions as a multidentate ligand (Okabe, Wada et al., 2002; Okabe, Muranishi et al., 2002), with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Co complex obtained by the reaction of fusaric acid with cobalt chloride in aqueous solution.

As illustrated in Fig. 1, the CoII atom, which is a neutral mononuclear molecule, lies on a centre of symmetry and has a distorted octahedral geometry with six coordinating atoms being two carboxyl O and two N atoms from two different fusaric acid ligands and two water molecules (Table 1). The coordinating O and N atoms and CoII atom are coplanar. The structural components are connected through O—H···O hydrogen bonding involving the coordinating water molecules as donors and the carboxyl O atoms as acceptors, forming neutral layers perpendicular to b axis (Fig. 2; Table 2).

Related literature top

For related literature, see: Okabe, Wada et al. (2002); Okabe, Muranishi et al. (2002).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of cobalt chloride (20 mmol) to a hot aqueous solution (25 ml) of 5-butyl-pyridyl-2-carboxylic acid (fusaric acid, 30 mmol). The pH was then adjusted to 7.0–8.0 with NaOH (30 mmol). The resulting solution was filtered, and red crystals were obtained at room temperature on slow evaporation of the solvent over several days.

Refinement top

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 or 1.5 Ueq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å and H···H = 1.29 Å, each within a standard deviation of 0.01 Å; other H-atoms with Uiso(H) = 1.2 Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. Unlabelled atoms are related to the labelled atoms by the symmetry operator (1 − x, 2 − y, 2 − z).
[Figure 2] Fig. 2. A packing view of (I), showing the intermolecular hydrogen bonding interactions as broken lines.
Diaquabis(5-n-butylpyridine-2-carboxylato)cobalt(II) top
Crystal data top
[Co(C10H12NO2)2(H2O)2]F(000) = 474
Mr = 451.37Dx = 1.366 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2500 reflections
a = 5.1378 (1) Åθ = 1.4–28.0°
b = 34.0034 (9) ŵ = 0.82 mm−1
c = 7.5922 (2) ÅT = 223 K
β = 124.181 (2)°Lamellar, red
V = 1097.27 (5) Å30.25 × 0.12 × 0.10 mm
Z = 2
Data collection top
Bruker APEXII area-detector
diffractometer		2511 independent reflections
Radiation source: fine-focus sealed tube1528 reflections with I > 2σ(I)
graphiteRint = 0.056
φ and ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→6
Tmin = 0.822, Tmax = 0.923k = −43→32
9237 measured reflectionsl = −9→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0454P)2]
where P = (Fo2 + 2Fc2)/3
2511 reflections(Δ/σ)max < 0.001
140 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.70 e Å−3
Crystal data top
[Co(C10H12NO2)2(H2O)2]V = 1097.27 (5) Å3
Mr = 451.37Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.1378 (1) ŵ = 0.82 mm−1
b = 34.0034 (9) ÅT = 223 K
c = 7.5922 (2) Å0.25 × 0.12 × 0.10 mm
β = 124.181 (2)°
Data collection top
Bruker APEXII area-detector
diffractometer		2511 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1528 reflections with I > 2σ(I)
Tmin = 0.822, Tmax = 0.923Rint = 0.056
9237 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.31 e Å−3
S = 1.01Δρmin = −0.70 e Å−3
2511 reflectionsAbsolute structure: ?
140 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Co10.50001.00001.00000.03057 (19)
O10.9434 (4)0.98064 (6)1.2377 (3)0.0348 (5)
O1W0.5780 (5)0.98681 (7)0.7663 (4)0.0454 (6)
H1W0.698 (8)0.9997 (9)0.764 (6)0.068*
H2W0.480 (8)0.9701 (10)0.680 (5)0.068*
O21.1879 (4)0.93289 (6)1.4790 (3)0.0448 (6)
N10.4053 (5)0.94044 (6)1.0289 (4)0.0321 (6)
C10.9548 (6)0.94757 (9)1.3189 (5)0.0336 (7)
C20.6498 (6)0.92409 (8)1.2061 (4)0.0316 (7)
C30.6270 (6)0.88849 (8)1.2802 (5)0.0427 (8)
H30.80220.87761.40470.051*
C40.3432 (7)0.86867 (8)1.1698 (5)0.0458 (8)
H40.32340.84451.22090.055*
C50.0877 (6)0.88440 (8)0.9838 (5)0.0370 (7)
C60.1329 (6)0.92054 (8)0.9207 (5)0.0354 (7)
H6−0.03710.93180.79490.043*
C7−0.2300 (7)0.86463 (8)0.8580 (5)0.0457 (8)
H7A−0.38100.88250.74440.055*
H7B−0.30100.86010.95210.055*
C8−0.2326 (6)0.82584 (8)0.7594 (5)0.0446 (8)
H8A−0.16650.83030.66240.054*
H8B−0.07950.80810.87220.054*
C9−0.5523 (7)0.80628 (10)0.6378 (5)0.0581 (10)
H9A−0.70790.82480.53140.070*
H9B−0.61200.80030.73680.070*
C10−0.5619 (10)0.76872 (12)0.5266 (7)0.0948 (14)
H10A−0.50300.77440.42820.142*
H10B−0.77310.75790.44880.142*
H10C−0.41580.74980.63160.142*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0264 (3)0.0264 (3)0.0351 (3)−0.0030 (2)0.0149 (2)−0.0004 (3)
O10.0269 (10)0.0321 (12)0.0398 (12)−0.0050 (9)0.0153 (9)0.0012 (10)
O1W0.0395 (13)0.0501 (16)0.0516 (16)−0.0185 (10)0.0287 (12)−0.0153 (11)
O20.0362 (11)0.0369 (13)0.0387 (13)0.0003 (9)0.0073 (10)0.0002 (10)
N10.0286 (12)0.0266 (14)0.0389 (14)−0.0026 (10)0.0176 (12)−0.0008 (11)
C10.0320 (15)0.0300 (17)0.0370 (18)−0.0024 (13)0.0183 (15)−0.0058 (14)
C20.0320 (15)0.0258 (16)0.0330 (17)−0.0007 (12)0.0160 (14)−0.0014 (13)
C30.0431 (18)0.0366 (19)0.0394 (19)−0.0018 (15)0.0178 (16)0.0057 (15)
C40.053 (2)0.0317 (18)0.053 (2)−0.0074 (16)0.0297 (18)0.0084 (16)
C50.0409 (17)0.0249 (17)0.050 (2)−0.0058 (13)0.0286 (16)−0.0048 (14)
C60.0320 (15)0.0266 (17)0.0444 (19)−0.0028 (13)0.0194 (14)−0.0041 (14)
C70.0408 (17)0.0341 (18)0.064 (2)−0.0085 (14)0.0308 (18)−0.0058 (16)
C80.0434 (17)0.0375 (19)0.052 (2)−0.0067 (15)0.0261 (16)−0.0041 (16)
C90.055 (2)0.046 (2)0.070 (3)−0.0183 (17)0.033 (2)−0.0118 (19)
C100.106 (3)0.057 (3)0.099 (4)−0.027 (2)0.044 (3)−0.032 (2)
Geometric parameters (Å, °) top
Co1—O1i2.0641 (18)C4—H40.9400
Co1—O12.0641 (18)C5—C61.385 (4)
Co1—O1Wi2.076 (2)C5—C71.509 (4)
Co1—O1W2.076 (2)C6—H60.9400
Co1—N1i2.123 (2)C7—C81.513 (4)
Co1—N12.123 (2)C7—H7A0.9800
O1—C11.268 (3)C7—H7B0.9800
O1W—H1W0.76 (3)C8—C91.513 (4)
O1W—H2W0.80 (3)C8—H8A0.9800
O2—C11.235 (3)C8—H8B0.9800
N1—C21.341 (3)C9—C101.517 (5)
N1—C61.342 (3)C9—H9A0.9800
C1—C21.523 (4)C9—H9B0.9800
C2—C31.367 (4)C10—H10A0.9700
C3—C41.382 (4)C10—H10B0.9700
C3—H30.9400C10—H10C0.9700
C4—C51.386 (4)
O1i—Co1—O1180.000 (1)C3—C4—H4119.9
O1i—Co1—O1Wi91.72 (9)C5—C4—H4119.9
O1—Co1—O1Wi88.28 (8)C6—C5—C4116.6 (3)
O1i—Co1—O1W88.28 (8)C6—C5—C7120.5 (3)
O1—Co1—O1W91.72 (9)C4—C5—C7122.8 (3)
O1Wi—Co1—O1W180.000 (2)N1—C6—C5123.8 (3)
O1i—Co1—N1i79.04 (8)N1—C6—H6118.1
O1—Co1—N1i100.96 (8)C5—C6—H6118.1
O1Wi—Co1—N1i92.73 (9)C5—C7—C8114.0 (2)
O1W—Co1—N1i87.27 (9)C5—C7—H7A108.7
O1i—Co1—N1100.96 (8)C8—C7—H7A108.7
O1—Co1—N179.04 (8)C5—C7—H7B108.7
O1Wi—Co1—N187.27 (9)C8—C7—H7B108.7
O1W—Co1—N192.73 (9)H7A—C7—H7B107.6
N1i—Co1—N1180.000 (1)C9—C8—C7112.9 (2)
C1—O1—Co1115.76 (16)C9—C8—H8A109.0
Co1—O1W—H1W116 (3)C7—C8—H8A109.0
Co1—O1W—H2W121 (3)C9—C8—H8B109.0
H1W—O1W—H2W122 (4)C7—C8—H8B109.0
C2—N1—C6118.2 (2)H8A—C8—H8B107.8
C2—N1—Co1111.06 (17)C8—C9—C10113.2 (3)
C6—N1—Co1129.70 (18)C8—C9—H9A108.9
O2—C1—O1126.2 (3)C10—C9—H9A108.9
O2—C1—C2117.7 (3)C8—C9—H9B108.9
O1—C1—C2116.1 (2)C10—C9—H9B108.9
N1—C2—C3122.1 (2)H9A—C9—H9B107.7
N1—C2—C1115.8 (2)C9—C10—H10A109.5
C3—C2—C1122.1 (3)C9—C10—H10B109.5
C2—C3—C4119.2 (3)H10A—C10—H10B109.5
C2—C3—H3120.4C9—C10—H10C109.5
C4—C3—H3120.4H10A—C10—H10C109.5
C3—C4—C5120.2 (3)H10B—C10—H10C109.5
Symmetry codes: (i) −x+1, −y+2, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H2W···O2ii0.80 (3)1.90 (3)2.688 (3)170 (3)
O1W—H1W···O1iii0.76 (3)1.97 (3)2.712 (3)165 (3)
Symmetry codes: (ii) x−1, y, z−1; (iii) −x+2, −y+2, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Co1—O12.0641 (18)Co1—N12.123 (2)
Co1—O1W2.076 (2)
O1i—Co1—O1Wi91.72 (9)O1i—Co1—N1100.96 (8)
O1—Co1—O1Wi88.28 (8)O1—Co1—N179.04 (8)
O1i—Co1—O1W88.28 (8)O1Wi—Co1—N187.27 (9)
O1—Co1—O1W91.72 (9)O1W—Co1—N192.73 (9)
Symmetry codes: (i) −x+1, −y+2, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H2W···O2ii0.80 (3)1.90 (3)2.688 (3)170 (3)
O1W—H1W···O1iii0.76 (3)1.97 (3)2.712 (3)165 (3)
Symmetry codes: (ii) x−1, y, z−1; (iii) −x+2, −y+2, −z+2.
Acknowledgements top

The authors acknowledge the Scientific and Technical Key Leading Project of Guangdong Province of China (grant No. B05119) and the Foundation for Excellent Person over Introduction of Zhanjiang and Guangdong Ocean University.

references
References top

Bruker (2004). APEX2 (Version 7.23a) and SAINT (Version 7.23a) and SHELXTL (Version ?). Bruker AXS Inc., Madison, Wisconsin, USA.

Okabe, N., Wada, Y. & Muranishi, Y. (2002). Acta Cryst. E58, m372–m374.

Okabe, N., Muranishi, Y. & Wada, Y. (2002). Acta Cryst. C58, m511–m513.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.