Tetra-aqua-bis-(6-chloro-pyridine-3-carboxyl-ato-κO)nickel(II) tetra-hydrate.

In the title compound, [Ni(C(6)H(3)ClNO(2))(2)(H(2)O)(4)]·4H(2)O, the Ni(II) ion is located on an inversion centre and is octa-hedrally coordinated by four O atoms from four water mol-ecules in the equatorial plane and two O atoms of two 6-chloro-3-carboxyl-ate ligands in axial positions. There are also four lattice water molecules present. The organic ligands are bound to the Ni(II) ion in a monodentate manner through a carboxyl-ate O atom. There is one strong intra-molecular O-H⋯O hydrogen bond and six inter-molecular O-H⋯O and O-H⋯N hydrogen-bonding inter-actions in the packing, resulting in a complex three-dimensional network structure.

Related literature

For background to complexes based on 6-chloro­nicotinic acid, see: Long et al. (2007 ▶); Li et al. (2006 ▶).

Experimental

Crystal data

[Ni(C6H3ClNO2)2(H2O)4]·4H2O

M = 515.91

Triclinic,

a = 7.0245 (14) Å

b = 7.3436 (15) Å

c = 11.547 (2) Å

α = 86.35 (3)°

β = 77.78 (3)°

γ = 64.55 (3)°

V = 525.4 (2) Å3

Z = 1

Mo Kα radiation

μ = 1.24 mm−1

T = 293 K

0.39 × 0.29 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.754, T max = 0.862

5167 measured reflections

2371 independent reflections

2170 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.076

S = 1.06

2371 reflections

134 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.41 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681204322X/bq2376sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204322X/bq2376Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C6H3ClNO2)2(H2O)4]·4H2O	Z = 1
Mr = 515.91	F(000) = 266
Triclinic, P1	Dx = 1.630 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0245 (14) Å	Cell parameters from 4651 reflections
b = 7.3436 (15) Å	θ = 3.1–27.5°
c = 11.547 (2) Å	µ = 1.24 mm−1
α = 86.35 (3)°	T = 293 K
β = 77.78 (3)°	Block, green
γ = 64.55 (3)°	0.39 × 0.29 × 0.16 mm
V = 525.4 (2) Å3

Rigaku R-AXIS RAPID diffractometer	2371 independent reflections
Radiation source: fine-focus sealed tube	2170 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
Tmin = 0.754, Tmax = 0.862	k = −9→9
5167 measured reflections	l = −14→14

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)] = 0.028	H-atom parameters constrained
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0344P)2 + 0.1122P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2371 reflections	Δρmax = 0.47 e Å−3
134 parameters	Δρmin = −0.41 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.115 (6)

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.

	x	y	z	Uiso*/Ueq
Cl	0.49297 (8)	−0.29064 (8)	1.14788 (4)	0.04615 (15)
Ni	0.0000	0.0000	0.5000	0.02619 (12)
O1	0.1088 (2)	−0.0624 (2)	0.65419 (10)	0.0345 (3)
O2	−0.1079 (2)	−0.1909 (2)	0.76064 (10)	0.0369 (3)
OW1	0.1737 (2)	−0.2994 (2)	0.44232 (11)	0.0438 (3)
H1WB	0.2196	−0.3961	0.4838	0.066*
H1WA	0.1310	−0.3310	0.3897	0.066*
OW2	0.27477 (19)	0.0432 (2)	0.42777 (10)	0.0354 (3)
H2WB	0.2884	0.1261	0.4680	0.053*
H2WA	0.2366	0.0978	0.3668	0.053*
OW3	0.3330 (2)	0.3218 (2)	0.55701 (12)	0.0476 (3)
H3WB	0.2430	0.3539	0.6168	0.071*
H3WA	0.4486	0.2539	0.5747	0.071*
OW4	−0.0265 (2)	−0.5912 (2)	0.73619 (11)	0.0475 (3)
H4WB	−0.0788	−0.4682	0.7463	0.071*
H4WA	−0.0208	−0.6457	0.7992	0.071*
N	0.1923 (2)	−0.2769 (2)	1.04439 (11)	0.0334 (3)
C1	0.3679 (3)	−0.2457 (3)	1.02767 (14)	0.0316 (3)
C2	0.4551 (3)	−0.1812 (3)	0.92311 (15)	0.0362 (4)
H2A	0.5800	−0.1626	0.9159	0.043*
C3	0.3501 (3)	−0.1457 (3)	0.83059 (14)	0.0347 (4)
H3A	0.4023	−0.1003	0.7593	0.042*
C4	0.1653 (2)	−0.1777 (2)	0.84378 (13)	0.0273 (3)
C5	0.0943 (3)	−0.2442 (3)	0.95247 (13)	0.0312 (3)
H5A	−0.0282	−0.2673	0.9620	0.037*
C6	0.0457 (2)	−0.1415 (2)	0.74546 (13)	0.0270 (3)

	U11	U22	U33	U12	U13	U23
Cl	0.0594 (3)	0.0454 (3)	0.0361 (2)	−0.0180 (2)	−0.0256 (2)	0.00447 (19)
Ni	0.03131 (17)	0.03082 (19)	0.02103 (16)	−0.01728 (13)	−0.00745 (11)	0.00611 (10)
O1	0.0433 (6)	0.0454 (8)	0.0255 (5)	−0.0280 (6)	−0.0117 (5)	0.0114 (5)
O2	0.0415 (6)	0.0468 (8)	0.0335 (6)	−0.0283 (6)	−0.0127 (5)	0.0120 (5)
OW1	0.0630 (8)	0.0321 (7)	0.0362 (6)	−0.0166 (6)	−0.0186 (6)	0.0031 (5)
OW2	0.0389 (6)	0.0457 (8)	0.0303 (5)	−0.0251 (6)	−0.0116 (5)	0.0085 (5)
OW3	0.0432 (7)	0.0526 (9)	0.0462 (7)	−0.0186 (7)	−0.0140 (6)	0.0092 (6)
OW4	0.0700 (9)	0.0437 (9)	0.0328 (6)	−0.0308 (7)	−0.0047 (6)	0.0033 (6)
N	0.0412 (8)	0.0352 (9)	0.0235 (6)	−0.0162 (6)	−0.0076 (6)	0.0065 (5)
C1	0.0383 (8)	0.0279 (9)	0.0266 (7)	−0.0102 (7)	−0.0114 (6)	0.0018 (6)
C2	0.0357 (8)	0.0462 (11)	0.0326 (8)	−0.0224 (8)	−0.0093 (7)	0.0054 (7)
C3	0.0387 (9)	0.0428 (11)	0.0264 (7)	−0.0224 (8)	−0.0052 (7)	0.0061 (7)
C4	0.0313 (7)	0.0262 (8)	0.0241 (7)	−0.0125 (6)	−0.0053 (6)	0.0036 (6)
C5	0.0347 (8)	0.0342 (10)	0.0263 (7)	−0.0166 (7)	−0.0067 (6)	0.0062 (6)
C6	0.0330 (8)	0.0245 (8)	0.0232 (7)	−0.0119 (6)	−0.0066 (6)	0.0037 (6)

Cl—C1	1.7369 (16)	OW1—H1WB	0.8140
Ni—O1i	2.0335 (12)	OW1—H1WA	0.8174
Ni—O1	2.0335 (12)	C4—C5	1.389 (2)
Ni—OW1	2.0742 (16)	C4—C3	1.392 (2)
Ni—OW1i	2.0742 (16)	C2—C3	1.374 (2)
Ni—OW2	2.0814 (12)	C2—H2A	0.9300
Ni—OW2i	2.0814 (12)	N—C5	1.339 (2)
O1—C6	1.2607 (18)	C5—H5A	0.9300
C6—O2	1.2550 (19)	C3—H3A	0.9300
C6—C4	1.496 (2)	OW4—H4WB	0.8210
C1—N	1.321 (2)	OW4—H4WA	0.8080
C1—C2	1.386 (2)	OW3—H3WB	0.8000
OW2—H2WB	0.8378	OW3—H3WA	0.8121
OW2—H2WA	0.8252
O1i—Ni—O1	180.00 (2)	Ni—OW2—H2WB	112.2
O1i—Ni—OW1	88.84 (6)	Ni—OW2—H2WA	97.3
O1—Ni—OW1	91.16 (6)	H2WB—OW2—H2WA	108.5
O1i—Ni—OW1i	91.16 (6)	Ni—OW1—H1WB	126.3
O1—Ni—OW1i	88.84 (6)	Ni—OW1—H1WA	114.0
OW1—Ni—OW1i	180.0	H1WB—OW1—H1WA	108.8
O1i—Ni—OW2	93.00 (5)	C5—C4—C3	117.46 (14)
O1—Ni—OW2	87.00 (5)	C5—C4—C6	120.79 (14)
OW1—Ni—OW2	87.71 (6)	C3—C4—C6	121.74 (14)
OW1i—Ni—OW2	92.29 (6)	C3—C2—C1	117.44 (15)
O1i—Ni—OW2i	87.00 (5)	C3—C2—H2A	121.3
O1—Ni—OW2i	93.00 (5)	C1—C2—H2A	121.3
OW1—Ni—OW2i	92.29 (6)	C1—N—C5	116.77 (14)
OW1i—Ni—OW2i	87.71 (6)	N—C5—C4	123.71 (15)
OW2—Ni—OW2i	180.00 (3)	N—C5—H5A	118.1
C6—O1—Ni	128.83 (10)	C4—C5—H5A	118.1
O2—C6—O1	125.72 (14)	C2—C3—C4	119.83 (15)
O2—C6—C4	117.79 (14)	C2—C3—H3A	120.1
O1—C6—C4	116.49 (13)	C4—C3—H3A	120.1
N—C1—C2	124.78 (14)	H4WB—OW4—H4WA	110.3
N—C1—Cl	115.91 (13)	H3WB—OW3—H3WA	107.9
C2—C1—Cl	119.31 (13)

D—H···A	D—H	H···A	D···A	D—H···A
OW2—H2WA···O2i	0.83	1.83	2.6401 (18)	167
OW1—H1WB···OW3ii	0.81	2.07	2.869 (2)	167
OW1—H1WA···OW4iii	0.82	1.97	2.7915 (19)	179
OW4—H4WA···Niv	0.81	2.14	2.850 (2)	147
OW3—H3WB···OW4v	0.80	1.99	2.763 (2)	163
OW3—H3WA···OW2vi	0.81	2.21	2.933 (2)	149
OW2—H2WB···OW3	0.84	1.98	2.819 (2)	177
OW4—H4WB···O2	0.82	1.97	2.764 (2)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW2—H2WA⋯O2i	0.83	1.83	2.6401 (18)	167
OW1—H1WB⋯OW3ii	0.81	2.07	2.869 (2)	167
OW1—H1WA⋯OW4iii	0.82	1.97	2.7915 (19)	179
OW4—H4WA⋯Niv	0.81	2.14	2.850 (2)	147
OW3—H3WB⋯OW4v	0.80	1.99	2.763 (2)	163
OW3—H3WA⋯OW2vi	0.81	2.21	2.933 (2)	149
OW2—H2WB⋯OW3	0.84	1.98	2.819 (2)	177
OW4—H4WB⋯O2	0.82	1.97	2.764 (2)	162

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .