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

Xia, Q.-H.; Guo, Z.-F.; Liu, L.; Lv, J.-Q.; Li, B.

doi:10.1107/S160053681204322X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1393

doi:10.1107/S160053681204322X

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

Qiao-Hua Xia,^a Zhong-Fu Guo,^a Li Liu,^a Jian-Quan Lv ^a and Bing Li ^a ^*

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

(Received 6 October 2012; accepted 17 October 2012; online 20 October 2012)

In the title compound, [Ni(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O, the Ni^II ion is located on an inversion centre and is octahedrally coordinated by four O atoms from four water molecules in the equatorial plane and two O atoms of two 6-chloro-3-carboxylate 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 carboxylate O atom. There is one strong intramolecular O—H⋯O hydrogen bond and six intermolecular O—H⋯O and O—H⋯N hydrogen-bonding interactions 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_r = 515.91
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.028
wR(F²) = 0.076
S = 1.06
2371 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.41 e Å⁻³

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⋯N^iv	0.81	2.14	2.850 (2)	147
OW3—H3WB⋯OW4^v	0.80	1.99	2.763 (2)	163
OW3—H3WA⋯OW2^vi	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) -x, -y, -z+1; (ii) x, y-1, z; (iii) -x, -y-1, -z+1; (iv) -x, -y-1, -z+2; (v) x, y+1, z; (vi) -x+1, -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: 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681204322X/bq2376sup1.cif

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

checkCIF report

Comment top

The asymmetric unit of the title complex, contains a half of Ni^II ion lying on a crystallographic inversion center, 6-chloropyridine-3-carboxylate anion, two coordinated water molecules and two lattice water molecules (Fig. 1). The Ni^II ion is six-coordinated within a octahedral, NiO₆ coordination geometry. Six coordination arises from two 6-chloropyridine-3-carboxylate ligands in the apical positions [Ni—O = 2.0335 (12) Å] and four water molecules in the equatorial plane [Ni—O = 2.0742 (16) Å and 2.0814 (12) Å]. The bond angles around the Ni center lie within the range 88.8–91.2° for the formally cis pairs of ligating atoms. The 6-chloropyridine-3-carboxylate carboxylate ligands are bound to the Ni^II ion in a monodentate mode through a carboxylate O atom. There is one strong intramolecular hydrogen bond of type O—H···O, formed by coordinated water atom OW2 and uncoordinated carboxylate atom O2, as well as six strong intermolecular hydrogen bonds of O—H···O type and one of O—H···N type in the packing of the title compound forming a three-dimensional supramolecular structure (Fig.2).

Related literature top

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

Experimental top

All commercially obtained reagent grade chemicals were used without further purification. A mixture of nickelous sulfate hexahydrate (0.5698 g) and 6-chloronicotinic acid (0.1701 g) were added into 20 ml water and with 20 drops of 0.1 mol/L sodium hydroxide solution, and then stirred for 1 h. Finally, 10 ml 95% ethanol carefully layered above-mentioned solution in glass tube. After 1 days, green crystals of the title complex were collected.

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: 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 (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) -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)nickel(II) tetrahydrate top

Crystal data top

[Ni(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O	Z = 1
M_r = 515.91	F(000) = 266
Triclinic, P1	D_x = 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

Data collection top

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

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0344P)² + 0.1122P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2371 reflections	Δρ_max = 0.47 e Å⁻³
134 parameters	Δρ_min = −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)

Crystal data top

[Ni(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O	γ = 64.55 (3)°
M_r = 515.91	V = 525.4 (2) Å³
Triclinic, P1	Z = 1
a = 7.0245 (14) Å	Mo Kα radiation
b = 7.3436 (15) Å	µ = 1.24 mm⁻¹
c = 11.547 (2) Å	T = 293 K
α = 86.35 (3)°	0.39 × 0.29 × 0.16 mm
β = 77.78 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2371 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2170 reflections with I > 2σ(I)
T_min = 0.754, T_max = 0.862	R_int = 0.049
5167 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.06	Δρ_max = 0.47 e Å⁻³
2371 reflections	Δρ_min = −0.41 e Å⁻³
134 parameters

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

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···N^iv	0.81	2.14	2.850 (2)	147
OW3—H3WB···OW4^v	0.80	1.99	2.763 (2)	163
OW3—H3WA···OW2^vi	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) −x, −y, −z+1; (ii) x, y−1, z; (iii) −x, −y−1, −z+1; (iv) −x, −y−1, −z+2; (v) x, y+1, z; (vi) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₃ClNO₂)₂(H₂O)₄]·4H₂O
M_r	515.91
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0245 (14), 7.3436 (15), 11.547 (2)
α, β, γ (°)	86.35 (3), 77.78 (3), 64.55 (3)
V (Å³)	525.4 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.39 × 0.29 × 0.16

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	5167, 2371, 2170
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.076, 1.06
No. of reflections	2371
No. of parameters	134
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.41

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW2—H2WA···O2ⁱ	0.83	1.83	2.6401 (18)	166.5
OW1—H1WB···OW3ⁱⁱ	0.81	2.07	2.869 (2)	166.7
OW1—H1WA···OW4ⁱⁱⁱ	0.82	1.97	2.7915 (19)	179.4
OW4—H4WA···N^iv	0.81	2.14	2.850 (2)	146.9
OW3—H3WB···OW4^v	0.80	1.99	2.763 (2)	162.7
OW3—H3WA···OW2^vi	0.81	2.21	2.933 (2)	148.8
OW2—H2WB···OW3	0.84	1.98	2.819 (2)	177.2
OW4—H4WB···O2	0.82	1.97	2.764 (2)	162.0

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

Acknowledgements

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

References

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