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Acta Cryst. (2012). E68, m1394    [ doi:10.1107/S160053681204319X ]

Tetraaquabis(6-chloropyridine-3-carboxylato-[kappa]O)cobalt(II) tetrahydrate

Q.-H. Xia, Y. Zhang, L. Liu, L.-F. Shi and B. Li

Abstract top

In the title compound, [Co(C6H3ClNO2)2(H2O)4]·4H2O, the CoII cation is located on an inversion center and is coordinated by four water molecules and two 6-chloropyridine-3-carboxylate anions in a slightly distorted octahedral geometry. In the crystal, complex molecules and lattice water molecules are linked by O-H...O and O-H...N hydrogen bonds into a three-dimensional network.

Comment top

In the crystal of the title compound, the Co(II) ion adopts a slightly distorted octahedral geometry and is located on a crystallographic inversion center. Four oxygen atoms from four coordination water molecules define the equatorial plane, while two oxygen atoms of two 6-chloro-3-carboxylate ligands occupy the axial sites (Figure 1). The Co—O bond lengths are in the range of 2.0723 (14)- 2.1162 (15) Å. The O—Co—O bond angles are 87.98 (6)–92.02 (6)° for the formally cis pairs of ligating atoms. The 6-chloropyridine-3-carboxylate carboxylate ligands are bound to the Co(II) ion in a monodentate mode through a carboxylate O atom. The three-dimensional supramolecular structure is formed by hydrogen bonds between six strong inter-molecular O—H···O and O—H···N hydrogen-bonding interactions and by additional intra-molecular O—H···O hydrogen bonds (Figure 2).

Related literature top

For background and related structures, see: Long et al. (2007); Li et al. (2006).

Experimental top

All commercially obtained reagent grade chemicals were used without further purication. A mixture of cobalt acetate tetrahydrate (0.4062 g) and 6-chloronicotinic acid (0.1310 g) were added into 20 ml water with 8 drops of 0.1 mol/L sodium hydroxide solution, and then stirred for 30 min. Finally, 5 ml 95% ethanol carefully layered above-mentioned solution in glass tube. After 1 day large pink platelet of the title compound suitable for X-ray diffraction were obtained.

Refinement top

H atoms bonded to C atoms were introduced in calculated positions and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms. H atoms belonging to water molecules were found in difference Fourier map and refined isotropically.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, with 50% probability displacement ellipsoids for non-H atoms. [Symmetry codes: (A) 1 - x, -y, 1 - z.]
[Figure 2] Fig. 2. Crystal packing diagram for the title compound. All atoms are shown as isotropic spheres of arbitrary size. H atoms bonded to C atoms are omitted for clarity. The H-bonding interactions are shown as yellow dashed lines.
Tetraaquabis(6-chloropyridine-3-carboxylato-κO)cobalt(II) tetrahydrate top
Crystal data top
[Co(C6H3ClNO2)2(H2O)4]·4H2OZ = 1
Mr = 516.15F(000) = 265
Triclinic, P1Dx = 1.621 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0314 (14) ÅCell parameters from 2394 reflections
b = 7.3569 (15) Åθ = 3.1–27.5°
c = 11.564 (2) ŵ = 1.13 mm1
α = 86.41 (3)°T = 293 K
β = 77.75 (3)°Platelet, pink
γ = 64.80 (3)°0.42 × 0.37 × 0.18 mm
V = 528.7 (2) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2394 independent reflections
Radiation source: fine-focus sealed tube2094 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 98
Tmin = 0.754, Tmax = 0.862k = 99
5250 measured reflectionsl = 1515
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)] = 0.029H-atom parameters constrained
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.0248P)2 + 0.0893P]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max = 0.001
2394 reflectionsΔρmax = 0.45 e Å3
134 parametersΔρmin = 0.48 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.356 (12)
Crystal data top
[Co(C6H3ClNO2)2(H2O)4]·4H2Oγ = 64.80 (3)°
Mr = 516.15V = 528.7 (2) Å3
Triclinic, P1Z = 1
a = 7.0314 (14) ÅMo Kα radiation
b = 7.3569 (15) ŵ = 1.13 mm1
c = 11.564 (2) ÅT = 293 K
α = 86.41 (3)°0.42 × 0.37 × 0.18 mm
β = 77.75 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2394 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
2094 reflections with I > 2σ(I)
Tmin = 0.754, Tmax = 0.862Rint = 0.065
5250 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.45 e Å3
S = 1.16Δρmin = 0.48 e Å3
2394 reflectionsAbsolute structure: ?
134 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Co0.50000.00000.50000.02745 (15)
Cl0.00669 (8)0.29228 (8)0.14887 (5)0.04646 (18)
O10.6093 (2)0.1896 (2)0.23682 (12)0.0371 (3)
O20.3932 (2)0.0600 (2)0.34210 (12)0.0362 (3)
OW10.77755 (19)0.0456 (2)0.42492 (13)0.0368 (3)
H1WA0.74750.09590.35800.055*
H1WB0.80530.12040.46060.055*
OW20.3261 (2)0.3039 (2)0.55709 (14)0.0460 (4)
H2WA0.26020.40210.52010.069*
H2WB0.35310.35270.61660.069*
OW30.5269 (2)0.5885 (2)0.26396 (14)0.0476 (4)
H3WA0.57450.63840.20290.071*
H3WB0.55350.47180.25260.071*
OW40.8332 (2)0.3212 (2)0.55760 (15)0.0482 (4)
H4WB0.74420.32440.62240.072*
H4WA0.96340.26190.56530.072*
N0.3076 (2)0.2781 (2)0.04625 (14)0.0331 (4)
C10.1321 (3)0.2467 (3)0.02902 (17)0.0320 (4)
C20.0458 (3)0.1820 (3)0.07433 (18)0.0361 (4)
H2A0.07910.16380.08130.043*
C30.1507 (3)0.1451 (3)0.16737 (18)0.0347 (4)
H3A0.09890.09920.23840.042*
C40.3362 (3)0.1776 (2)0.15307 (16)0.0275 (4)
C50.4056 (3)0.2444 (3)0.04594 (17)0.0312 (4)
H5A0.52790.26780.03660.037*
C60.4549 (3)0.1400 (2)0.25230 (16)0.0277 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0297 (2)0.0310 (2)0.0229 (2)0.01422 (15)0.00582 (13)0.00395 (15)
Cl0.0562 (3)0.0444 (3)0.0377 (3)0.0138 (2)0.0237 (2)0.0020 (3)
O10.0387 (6)0.0463 (8)0.0343 (8)0.0251 (6)0.0107 (6)0.0093 (7)
O20.0438 (7)0.0453 (7)0.0270 (7)0.0250 (6)0.0123 (5)0.0102 (6)
OW10.0376 (6)0.0474 (8)0.0324 (7)0.0245 (6)0.0085 (5)0.0051 (6)
OW20.0636 (9)0.0306 (7)0.0398 (9)0.0127 (7)0.0177 (7)0.0007 (7)
OW30.0655 (9)0.0427 (8)0.0366 (8)0.0288 (7)0.0013 (7)0.0007 (7)
OW40.0412 (7)0.0517 (9)0.0476 (9)0.0152 (7)0.0116 (7)0.0065 (8)
N0.0375 (8)0.0326 (8)0.0254 (8)0.0124 (7)0.0047 (6)0.0039 (7)
C10.0360 (8)0.0247 (8)0.0290 (10)0.0051 (7)0.0091 (7)0.0034 (8)
C20.0313 (8)0.0437 (10)0.0355 (11)0.0173 (8)0.0081 (8)0.0013 (9)
C30.0342 (8)0.0430 (10)0.0288 (10)0.0201 (8)0.0027 (7)0.0028 (9)
C40.0300 (8)0.0241 (8)0.0246 (9)0.0087 (7)0.0034 (7)0.0003 (7)
C50.0311 (8)0.0331 (9)0.0284 (9)0.0137 (7)0.0046 (7)0.0036 (8)
C60.0312 (8)0.0237 (8)0.0252 (9)0.0090 (7)0.0048 (7)0.0002 (7)
Geometric parameters (Å, º) top
Co—O2i2.0717 (14)OW3—H3WB0.8101
Co—O22.0717 (14)OW4—H4WB0.8629
Co—OW22.1078 (15)OW4—H4WA0.8520
Co—OW2i2.1078 (15)N—C11.322 (2)
Co—OW12.1157 (14)N—C51.344 (2)
Co—OW1i2.1157 (14)C1—C21.375 (3)
Cl—C11.7379 (19)C2—C31.380 (3)
O1—C61.261 (2)C2—H2A0.9300
O2—C61.250 (2)C3—C41.398 (3)
OW1—H1WA0.8642C3—H3A0.9300
OW1—H1WB0.8153C4—C51.373 (3)
OW2—H2WA0.8246C4—C61.504 (2)
OW2—H2WB0.8853C5—H5A0.9300
OW3—H3WA0.8466
O2i—Co—O2180.0H3WA—OW3—H3WB111.9
O2i—Co—OW288.51 (6)H4WB—OW4—H4WA112.2
O2—Co—OW291.49 (6)C1—N—C5116.27 (18)
O2i—Co—OW2i91.49 (6)N—C1—C2125.08 (17)
O2—Co—OW2i88.51 (6)N—C1—Cl115.68 (16)
OW2—Co—OW2i180.0C2—C1—Cl119.24 (14)
O2i—Co—OW188.00 (6)C1—C2—C3117.79 (17)
O2—Co—OW192.00 (6)C1—C2—H2A121.1
OW2—Co—OW191.76 (7)C3—C2—H2A121.1
OW2i—Co—OW188.24 (7)C2—C3—C4118.94 (19)
O2i—Co—OW1i92.00 (6)C2—C3—H3A120.5
O2—Co—OW1i88.00 (6)C4—C3—H3A120.5
OW2—Co—OW1i88.24 (7)C5—C4—C3117.88 (17)
OW2i—Co—OW1i91.76 (7)C5—C4—C6121.45 (15)
OW1—Co—OW1i180.00 (3)C3—C4—C6120.67 (18)
C6—O2—Co128.85 (12)N—C5—C4124.03 (16)
Co—OW1—H1WA100.8N—C5—H5A118.0
Co—OW1—H1WB117.8C4—C5—H5A118.0
H1WA—OW1—H1WB110.1O2—C6—O1125.95 (17)
Co—OW2—H2WA129.2O2—C6—C4116.96 (15)
Co—OW2—H2WB121.6O1—C6—C4117.09 (17)
H2WA—OW2—H2WB105.8
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW1—H1WA···O10.861.812.644 (2)162
OW1—H1WB···OW40.822.012.818 (2)173
OW2—H2WA···OW4ii0.822.072.857 (2)161
OW2—H2WB···OW3ii0.891.922.791 (2)167
OW3—H3WA···Niii0.852.002.842 (2)172
OW3—H3WB···O10.811.952.763 (2)176
OW4—H4WA···OW1iv0.852.232.948 (2)141
OW4—H4WB···OW3ii0.861.942.763 (2)158
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x+1, y+1, z; (iv) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW1—H1WA···O10.861.812.644 (2)162.0
OW1—H1WB···OW40.822.012.818 (2)172.7
OW2—H2WA···OW4i0.822.072.857 (2)160.9
OW2—H2WB···OW3i0.891.922.791 (2)167.4
OW3—H3WA···Nii0.852.002.842 (2)171.9
OW3—H3WB···O10.811.952.763 (2)176.1
OW4—H4WA···OW1iii0.852.232.948 (2)141.2
OW4—H4WB···OW3i0.861.942.763 (2)158.4
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) x+2, y, z+1.
Acknowledgements top

This work was supported by the National Natural Science Foundation (No.21207117), the Zhejiang Provincial Municipal Science and Technology Project (2008 C12055) and the Natural Science Foundation of Zhejiang Province (No. LY12B02013).

references
References top

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

Li, F.-H., Yin, H.-D., Sun, L., Zhao, Q. & Liu, W.-L. (2006). Acta Cryst. E62, m1117–m1118.

Long, S., Siegler, M. & Li, T. (2007). Acta Cryst. E63, o279–o281.

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

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

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