Tetra­aqua­bis­(6-chloro­pyridine-3-carboxyl­ato-κO)cobalt(II) tetra­hydrate

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

doi:10.1107/S160053681204319X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1394

doi:10.1107/S160053681204319X

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Tetraaquabis(6-chloropyridine-3-carboxylato-κO)cobalt(II) tetrahydrate

Qiao-Hua Xia,^a Yue Zhang,^b Li Liu,^a Lin-Fang Shi ^a and Bing Li ^a ^*

^aCollege of Sciences, Zhejiang A&F University, Lin'an Hangzhou, Zhejiang 311300, People's Republic of China, and ^bCollege of Engineering, Zhejiang A&F University, Lin'an Hangzhou, Zhejiang 311300, People's Republic of China
^*Correspondence e-mail: libingzjfc@163.com

(Received 7 October 2012; accepted 17 October 2012; online 20 October 2012)

In the title compound, [Co(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O, the Co^II 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.

Related literature

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

Experimental

Crystal data

[Co(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O
M_r = 516.15
Triclinic, $[P \overline 1]$
a = 7.0314 (14) Å
b = 7.3569 (15) Å
c = 11.564 (2) Å
α = 86.41 (3)°
β = 77.75 (3)°
γ = 64.80 (3)°
V = 528.7 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 293 K
0.42 × 0.37 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.754, T_max = 0.862
5250 measured reflections
2394 independent reflections
2094 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.085
S = 1.16
2394 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—H1WA⋯O1	0.86	1.81	2.644 (2)	162
OW1—H1WB⋯OW4	0.82	2.01	2.818 (2)	173
OW2—H2WA⋯OW4ⁱ	0.82	2.07	2.857 (2)	161
OW2—H2WB⋯OW3ⁱ	0.89	1.92	2.791 (2)	167
OW3—H3WA⋯Nⁱⁱ	0.85	2.00	2.842 (2)	172
OW3—H3WB⋯O1	0.81	1.95	2.763 (2)	176
OW4—H4WA⋯OW1ⁱⁱⁱ	0.85	2.23	2.948 (2)	141
OW4—H4WB⋯OW3ⁱ	0.86	1.94	2.763 (2)	158
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) -x+2, -y, -z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681204319X/xu5631sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681204319X/xu5631Isup2.hkl

checkCIF report

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.

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

	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.]
	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]·4H₂O	Z = 1
M_r = 516.15	F(000) = 265
Triclinic, P1	D_x = 1.621 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0314 (14) Å	Cell parameters from 2394 reflections
b = 7.3569 (15) Å	θ = 3.1–27.5°
c = 11.564 (2) Å	µ = 1.13 mm⁻¹
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 tube	2094 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→8
T_min = 0.754, T_max = 0.862	k = −9→9
5250 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0248P)² + 0.0893P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.001
2394 reflections	Δρ_max = 0.45 e Å⁻³
134 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.356 (12)

Crystal data top

[Co(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O	γ = 64.80 (3)°
M_r = 516.15	V = 528.7 (2) Å³
Triclinic, P1	Z = 1
a = 7.0314 (14) Å	Mo Kα radiation
b = 7.3569 (15) Å	µ = 1.13 mm⁻¹
c = 11.564 (2) Å	T = 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)
T_min = 0.754, T_max = 0.862	R_int = 0.065
5250 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.16	Δρ_max = 0.45 e Å⁻³
2394 reflections	Δρ_min = −0.48 e Å⁻³
134 parameters

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

	x	y	z	U_iso*/U_eq
Co	0.5000	0.0000	0.5000	0.02745 (15)
Cl	0.00669 (8)	0.29228 (8)	−0.14887 (5)	0.04646 (18)
O1	0.6093 (2)	0.1896 (2)	0.23682 (12)	0.0371 (3)
O2	0.3932 (2)	0.0600 (2)	0.34210 (12)	0.0362 (3)
OW1	0.77755 (19)	0.0456 (2)	0.42492 (13)	0.0368 (3)
H1WA	0.7475	0.0959	0.3580	0.055*
H1WB	0.8053	0.1204	0.4606	0.055*
OW2	0.3261 (2)	0.3039 (2)	0.55709 (14)	0.0460 (4)
H2WA	0.2602	0.4021	0.5201	0.069*
H2WB	0.3531	0.3527	0.6166	0.069*
OW3	0.5269 (2)	0.5885 (2)	0.26396 (14)	0.0476 (4)
H3WA	0.5745	0.6384	0.2029	0.071*
H3WB	0.5535	0.4718	0.2526	0.071*
OW4	0.8332 (2)	0.3212 (2)	0.55760 (15)	0.0482 (4)
H4WB	0.7442	0.3244	0.6224	0.072*
H4WA	0.9634	0.2619	0.5653	0.072*
N	0.3076 (2)	0.2781 (2)	−0.04625 (14)	0.0331 (4)
C1	0.1321 (3)	0.2467 (3)	−0.02902 (17)	0.0320 (4)
C2	0.0458 (3)	0.1820 (3)	0.07433 (18)	0.0361 (4)
H2A	−0.0791	0.1638	0.0813	0.043*
C3	0.1507 (3)	0.1451 (3)	0.16737 (18)	0.0347 (4)
H3A	0.0989	0.0992	0.2384	0.042*
C4	0.3362 (3)	0.1776 (2)	0.15307 (16)	0.0275 (4)
C5	0.4056 (3)	0.2444 (3)	0.04594 (17)	0.0312 (4)
H5A	0.5279	0.2678	0.0366	0.037*
C6	0.4549 (3)	0.1400 (2)	0.25230 (16)	0.0277 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0297 (2)	0.0310 (2)	0.0229 (2)	−0.01422 (15)	−0.00582 (13)	0.00395 (15)
Cl	0.0562 (3)	0.0444 (3)	0.0377 (3)	−0.0138 (2)	−0.0237 (2)	0.0020 (3)
O1	0.0387 (6)	0.0463 (8)	0.0343 (8)	−0.0251 (6)	−0.0107 (6)	0.0093 (7)
O2	0.0438 (7)	0.0453 (7)	0.0270 (7)	−0.0250 (6)	−0.0123 (5)	0.0102 (6)
OW1	0.0376 (6)	0.0474 (8)	0.0324 (7)	−0.0245 (6)	−0.0085 (5)	0.0051 (6)
OW2	0.0636 (9)	0.0306 (7)	0.0398 (9)	−0.0127 (7)	−0.0177 (7)	−0.0007 (7)
OW3	0.0655 (9)	0.0427 (8)	0.0366 (8)	−0.0288 (7)	−0.0013 (7)	−0.0007 (7)
OW4	0.0412 (7)	0.0517 (9)	0.0476 (9)	−0.0152 (7)	−0.0116 (7)	0.0065 (8)
N	0.0375 (8)	0.0326 (8)	0.0254 (8)	−0.0124 (7)	−0.0047 (6)	0.0039 (7)
C1	0.0360 (8)	0.0247 (8)	0.0290 (10)	−0.0051 (7)	−0.0091 (7)	−0.0034 (8)
C2	0.0313 (8)	0.0437 (10)	0.0355 (11)	−0.0173 (8)	−0.0081 (8)	0.0013 (9)
C3	0.0342 (8)	0.0430 (10)	0.0288 (10)	−0.0201 (8)	−0.0027 (7)	0.0028 (9)
C4	0.0300 (8)	0.0241 (8)	0.0246 (9)	−0.0087 (7)	−0.0034 (7)	−0.0003 (7)
C5	0.0311 (8)	0.0331 (9)	0.0284 (9)	−0.0137 (7)	−0.0046 (7)	0.0036 (8)
C6	0.0312 (8)	0.0237 (8)	0.0252 (9)	−0.0090 (7)	−0.0048 (7)	0.0002 (7)

Geometric parameters (Å, º) top

Co—O2ⁱ	2.0717 (14)	OW3—H3WB	0.8101
Co—O2	2.0717 (14)	OW4—H4WB	0.8629
Co—OW2	2.1078 (15)	OW4—H4WA	0.8520
Co—OW2ⁱ	2.1078 (15)	N—C1	1.322 (2)
Co—OW1	2.1157 (14)	N—C5	1.344 (2)
Co—OW1ⁱ	2.1157 (14)	C1—C2	1.375 (3)
Cl—C1	1.7379 (19)	C2—C3	1.380 (3)
O1—C6	1.261 (2)	C2—H2A	0.9300
O2—C6	1.250 (2)	C3—C4	1.398 (3)
OW1—H1WA	0.8642	C3—H3A	0.9300
OW1—H1WB	0.8153	C4—C5	1.373 (3)
OW2—H2WA	0.8246	C4—C6	1.504 (2)
OW2—H2WB	0.8853	C5—H5A	0.9300
OW3—H3WA	0.8466

O2ⁱ—Co—O2	180.0	H3WA—OW3—H3WB	111.9
O2ⁱ—Co—OW2	88.51 (6)	H4WB—OW4—H4WA	112.2
O2—Co—OW2	91.49 (6)	C1—N—C5	116.27 (18)
O2ⁱ—Co—OW2ⁱ	91.49 (6)	N—C1—C2	125.08 (17)
O2—Co—OW2ⁱ	88.51 (6)	N—C1—Cl	115.68 (16)
OW2—Co—OW2ⁱ	180.0	C2—C1—Cl	119.24 (14)
O2ⁱ—Co—OW1	88.00 (6)	C1—C2—C3	117.79 (17)
O2—Co—OW1	92.00 (6)	C1—C2—H2A	121.1
OW2—Co—OW1	91.76 (7)	C3—C2—H2A	121.1
OW2ⁱ—Co—OW1	88.24 (7)	C2—C3—C4	118.94 (19)
O2ⁱ—Co—OW1ⁱ	92.00 (6)	C2—C3—H3A	120.5
O2—Co—OW1ⁱ	88.00 (6)	C4—C3—H3A	120.5
OW2—Co—OW1ⁱ	88.24 (7)	C5—C4—C3	117.88 (17)
OW2ⁱ—Co—OW1ⁱ	91.76 (7)	C5—C4—C6	121.45 (15)
OW1—Co—OW1ⁱ	180.00 (3)	C3—C4—C6	120.67 (18)
C6—O2—Co	128.85 (12)	N—C5—C4	124.03 (16)
Co—OW1—H1WA	100.8	N—C5—H5A	118.0
Co—OW1—H1WB	117.8	C4—C5—H5A	118.0
H1WA—OW1—H1WB	110.1	O2—C6—O1	125.95 (17)
Co—OW2—H2WA	129.2	O2—C6—C4	116.96 (15)
Co—OW2—H2WB	121.6	O1—C6—C4	117.09 (17)
H2WA—OW2—H2WB	105.8

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1WA···O1	0.86	1.81	2.644 (2)	162
OW1—H1WB···OW4	0.82	2.01	2.818 (2)	173
OW2—H2WA···OW4ⁱⁱ	0.82	2.07	2.857 (2)	161
OW2—H2WB···OW3ⁱⁱ	0.89	1.92	2.791 (2)	167
OW3—H3WA···Nⁱⁱⁱ	0.85	2.00	2.842 (2)	172
OW3—H3WB···O1	0.81	1.95	2.763 (2)	176
OW4—H4WA···OW1^iv	0.85	2.23	2.948 (2)	141
OW4—H4WB···OW3ⁱⁱ	0.86	1.94	2.763 (2)	158

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

Experimental details

Crystal data
Chemical formula	[Co(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O
M_r	516.15
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0314 (14), 7.3569 (15), 11.564 (2)
α, β, γ (°)	86.41 (3), 77.75 (3), 64.80 (3)
V (Å³)	528.7 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.13
Crystal size (mm)	0.42 × 0.37 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.754, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	5250, 2394, 2094
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.085, 1.16
No. of reflections	2394
No. of parameters	134
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.48

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1WA···O1	0.86	1.81	2.644 (2)	162.0
OW1—H1WB···OW4	0.82	2.01	2.818 (2)	172.7
OW2—H2WA···OW4ⁱ	0.82	2.07	2.857 (2)	160.9
OW2—H2WB···OW3ⁱ	0.89	1.92	2.791 (2)	167.4
OW3—H3WA···Nⁱⁱ	0.85	2.00	2.842 (2)	171.9
OW3—H3WB···O1	0.81	1.95	2.763 (2)	176.1
OW4—H4WA···OW1ⁱⁱⁱ	0.85	2.23	2.948 (2)	141.2
OW4—H4WB···OW3ⁱ	0.86	1.94	2.763 (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

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

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