Diaqua-bis(2-chloro-benzoato-κO)bis-(nicotinamide-κN)nickel(II).

The title Ni(II) complex, [Ni(C(7)H(4)ClO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], is centrosymmetric with the Ni atom located on an inversion centre. The mol-ecule contains two 2-chloro-benzoate (CB) and two nicotinamide (NA) ligands and two water mol-ecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Ni atom form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 29.48 (16)°, while the pyridine and benzene rings are oriented at a dihedral angle of 83.16 (5)°. In the crystal structure, O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules into infinite chains. π-π Contacts between the benzene and pyridine rings [centroid-centroid distance = 3.952 (1) Å] may further stabilize the crystal structure. There is also a C-H⋯π inter-action.

Related literature

For general background, see: Antolini et al. (1982 ▶); Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶); Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For related structures, see: Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 2007 ▶); Hökelek et al. (1995 ▶, 1997 ▶, 2007 ▶, 2008 ▶); Özbek et al. (2009 ▶); Sertçelik et al. (2009 ▶,c ▶); Tercan et al. (2009 ▶).

Experimental

Crystal data

[Ni(C7H4ClO2)2(C6H6N2O)2(H2O)2]

M = 650.10

Monoclinic,

a = 7.8602 (3) Å

b = 17.9529 (6) Å

c = 9.8446 (3) Å

β = 106.600 (2)°

V = 1331.31 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.99 mm−1

T = 100 K

0.45 × 0.30 × 0.25 mm

Data collection

Bruker Kappa-APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.710, T max = 0.784

11754 measured reflections

3301 independent reflections

2626 reflections with I > 2σ(I)

R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.107

S = 1.07

3301 reflections

202 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.77 e Å−3

Δρmin = −0.69 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011209/xu2501sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011209/xu2501Isup2.hkl

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

[Ni(C7H4ClO2)2(C6H6N2O)2(H2O)2]	F(000) = 668
Mr = 650.10	Dx = 1.622 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5500 reflections
a = 7.8602 (3) Å	θ = 2.4–28.3°
b = 17.9529 (6) Å	µ = 0.99 mm−1
c = 9.8446 (3) Å	T = 100 K
β = 106.600 (2)°	Block, orange
V = 1331.31 (8) Å3	0.45 × 0.30 × 0.25 mm
Z = 2

Bruker Kappa-APEXII CCD area-detector diffractometer	3301 independent reflections
Radiation source: fine-focus sealed tube	2626 reflections with I > 2σ(I)
graphite	Rint = 0.064
φ and ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→7
Tmin = 0.710, Tmax = 0.784	k = −23→21
11754 measured reflections	l = −11→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0492P)2 + 1.0761P] where P = (Fo2 + 2Fc2)/3
3301 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.77 e Å−3
1 restraint	Δρmin = −0.69 e Å−3

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
Ni1	0.5000	0.0000	0.0000	0.01322 (13)
Cl1	0.40816 (8)	0.28820 (3)	−0.32584 (6)	0.02186 (16)
O1	0.6153 (2)	0.09893 (9)	−0.04613 (15)	0.0135 (3)
O2	0.3868 (2)	0.13652 (10)	−0.22542 (16)	0.0155 (4)
O3	0.0484 (2)	0.00967 (10)	0.32471 (17)	0.0183 (4)
O4	0.2363 (2)	0.04330 (10)	−0.08886 (17)	0.0146 (4)
H41	0.261 (4)	0.0763 (19)	−0.141 (3)	0.030 (9)*
H42	0.153 (3)	0.0172 (16)	−0.141 (3)	0.029*
N1	0.4964 (3)	0.04416 (10)	0.19906 (19)	0.0115 (4)
N2	0.1426 (3)	0.08165 (13)	0.5195 (2)	0.0188 (5)
H21	0.221 (4)	0.1030 (18)	0.573 (3)	0.026 (9)*
H22	0.060 (4)	0.0657 (17)	0.550 (3)	0.023 (8)*
C1	0.5480 (3)	0.13795 (13)	−0.1555 (2)	0.0121 (4)
C2	0.6718 (3)	0.18573 (13)	−0.2104 (2)	0.0124 (5)
C3	0.8477 (3)	0.16293 (13)	−0.1863 (2)	0.0143 (5)
H3	0.8887	0.1224	−0.1271	0.017*
C4	0.9630 (3)	0.19869 (14)	−0.2478 (2)	0.0164 (5)
H4	1.0797	0.1824	−0.2294	0.020*
C5	0.9033 (3)	0.25927 (14)	−0.3375 (2)	0.0166 (5)
H5	0.9789	0.2823	−0.3820	0.020*
C6	0.7319 (3)	0.28498 (14)	−0.3601 (2)	0.0154 (5)
H6	0.6926	0.3262	−0.4179	0.019*
C7	0.6181 (3)	0.24896 (13)	−0.2959 (2)	0.0129 (5)
C8	0.6344 (3)	0.08184 (13)	0.2847 (2)	0.0132 (5)
H8	0.7379	0.0868	0.2577	0.016*
C9	0.6273 (3)	0.11327 (14)	0.4113 (2)	0.0169 (5)
H9	0.7240	0.1393	0.4678	0.020*
C10	0.4743 (3)	0.10541 (13)	0.4526 (2)	0.0152 (5)
H10	0.4668	0.1262	0.5372	0.018*
C11	0.3318 (3)	0.06602 (13)	0.3664 (2)	0.0123 (4)
C12	0.3496 (3)	0.03681 (13)	0.2405 (2)	0.0125 (5)
H12	0.2543	0.0108	0.1819	0.015*
C13	0.1630 (3)	0.05107 (13)	0.4022 (2)	0.0142 (5)

	U11	U22	U33	U12	U13	U23
Ni1	0.0129 (2)	0.0162 (2)	0.00877 (19)	−0.00046 (17)	0.00017 (15)	−0.00017 (15)
Cl1	0.0173 (3)	0.0200 (3)	0.0261 (3)	0.0068 (2)	0.0027 (2)	0.0055 (2)
O1	0.0147 (8)	0.0153 (8)	0.0076 (7)	−0.0023 (6)	−0.0017 (6)	0.0006 (6)
O2	0.0117 (8)	0.0213 (9)	0.0109 (7)	−0.0014 (7)	−0.0013 (6)	0.0023 (6)
O3	0.0149 (9)	0.0267 (10)	0.0116 (7)	−0.0053 (7)	0.0013 (6)	−0.0039 (7)
O4	0.0134 (9)	0.0176 (9)	0.0103 (7)	−0.0009 (7)	−0.0006 (6)	0.0013 (6)
N1	0.0115 (9)	0.0122 (10)	0.0090 (8)	0.0000 (7)	−0.0002 (7)	0.0004 (7)
N2	0.0157 (11)	0.0294 (13)	0.0116 (9)	−0.0060 (9)	0.0043 (8)	−0.0067 (9)
C1	0.0148 (11)	0.0124 (11)	0.0082 (9)	−0.0007 (9)	0.0018 (8)	−0.0030 (8)
C2	0.0154 (11)	0.0129 (11)	0.0072 (9)	−0.0011 (9)	0.0004 (8)	−0.0023 (8)
C3	0.0147 (11)	0.0137 (11)	0.0112 (10)	−0.0007 (9)	−0.0016 (8)	−0.0014 (8)
C4	0.0133 (11)	0.0187 (12)	0.0157 (11)	−0.0020 (9)	0.0016 (9)	−0.0026 (9)
C5	0.0190 (12)	0.0174 (12)	0.0127 (10)	−0.0053 (10)	0.0035 (9)	−0.0016 (9)
C6	0.0189 (12)	0.0145 (12)	0.0099 (10)	−0.0022 (9)	−0.0007 (8)	0.0008 (8)
C7	0.0126 (11)	0.0140 (11)	0.0092 (10)	0.0017 (9)	−0.0013 (8)	−0.0020 (8)
C8	0.0120 (11)	0.0154 (12)	0.0109 (10)	−0.0009 (9)	0.0010 (8)	0.0006 (8)
C9	0.0155 (12)	0.0196 (13)	0.0125 (10)	−0.0047 (10)	−0.0012 (9)	−0.0033 (9)
C10	0.0177 (12)	0.0188 (12)	0.0071 (9)	−0.0023 (9)	0.0005 (8)	−0.0028 (8)
C11	0.0134 (11)	0.0134 (11)	0.0082 (9)	−0.0007 (9)	−0.0001 (8)	0.0007 (8)
C12	0.0131 (11)	0.0123 (11)	0.0091 (9)	−0.0006 (9)	−0.0018 (8)	0.0011 (8)
C13	0.0132 (11)	0.0180 (12)	0.0097 (9)	0.0004 (9)	0.0008 (8)	0.0017 (8)

Ni1—O1i	2.1017 (16)	C3—H3	0.9300
Ni1—O1	2.1017 (16)	C4—C3	1.383 (3)
Ni1—O4	2.1520 (16)	C4—C5	1.395 (3)
Ni1—O4i	2.1520 (16)	C4—H4	0.9300
Ni1—N1i	2.1217 (18)	C5—C6	1.381 (3)
Ni1—N1	2.1217 (18)	C5—H5	0.9300
Cl1—C7	1.740 (2)	C6—H6	0.9300
O1—C1	1.267 (3)	C7—C2	1.404 (3)
O2—C1	1.258 (3)	C7—C6	1.393 (3)
O3—C13	1.246 (3)	C8—C9	1.384 (3)
O4—H41	0.85 (3)	C8—H8	0.9300
O4—H42	0.850 (18)	C9—H9	0.9300
N1—C8	1.350 (3)	C10—C9	1.382 (3)
N1—C12	1.335 (3)	C10—H10	0.9300
N2—C13	1.329 (3)	C11—C10	1.390 (3)
N2—H21	0.79 (3)	C11—C12	1.389 (3)
N2—H22	0.84 (3)	C11—C13	1.492 (3)
C1—C2	1.508 (3)	C12—H12	0.9300
C2—C3	1.396 (3)
O1i—Ni1—O1	180.00 (5)	C4—C3—C2	122.0 (2)
O1i—Ni1—O4	88.18 (6)	C4—C3—H3	119.0
O1—Ni1—O4	91.82 (6)	C3—C4—C5	119.7 (2)
O1i—Ni1—O4i	91.82 (6)	C3—C4—H4	120.2
O1—Ni1—O4i	88.18 (6)	C5—C4—H4	120.2
O4—Ni1—O4i	180.00 (9)	C4—C5—H5	120.1
O1i—Ni1—N1i	90.24 (7)	C6—C5—C4	119.9 (2)
O1—Ni1—N1i	89.76 (7)	C6—C5—H5	120.1
O1i—Ni1—N1	89.76 (7)	C5—C6—C7	119.7 (2)
O1—Ni1—N1	90.24 (7)	C5—C6—H6	120.2
N1i—Ni1—N1	180.00 (14)	C7—C6—H6	120.2
N1i—Ni1—O4	91.44 (7)	C2—C7—Cl1	122.46 (19)
N1—Ni1—O4	88.56 (7)	C6—C7—Cl1	115.85 (18)
N1i—Ni1—O4i	88.56 (7)	C6—C7—C2	121.7 (2)
N1—Ni1—O4i	91.44 (7)	N1—C8—C9	122.3 (2)
Ni1—O4—H41	98 (2)	N1—C8—H8	118.8
Ni1—O4—H42	122 (2)	C9—C8—H8	118.8
H41—O4—H42	107 (3)	C8—C9—H9	120.5
C1—O1—Ni1	123.37 (14)	C10—C9—C8	119.1 (2)
C8—N1—Ni1	122.93 (16)	C10—C9—H9	120.5
C12—N1—Ni1	119.06 (14)	C9—C10—C11	119.3 (2)
C12—N1—C8	117.97 (19)	C9—C10—H10	120.4
C13—N2—H21	121 (2)	C11—C10—H10	120.4
C13—N2—H22	118 (2)	C10—C11—C13	124.3 (2)
H22—N2—H21	118 (3)	C12—C11—C10	117.9 (2)
O1—C1—C2	117.6 (2)	C12—C11—C13	117.80 (19)
O2—C1—O1	124.4 (2)	N1—C12—C11	123.4 (2)
O2—C1—C2	117.89 (19)	N1—C12—H12	118.3
C3—C2—C1	118.8 (2)	C11—C12—H12	118.3
C3—C2—C7	116.9 (2)	O3—C13—N2	122.2 (2)
C7—C2—C1	124.1 (2)	O3—C13—C11	119.9 (2)
C2—C3—H3	119.0	N2—C13—C11	117.9 (2)
O4—Ni1—O1—C1	−35.17 (18)	C1—C2—C3—C4	172.0 (2)
O4i—Ni1—O1—C1	144.83 (18)	C7—C2—C3—C4	−2.5 (3)
N1i—Ni1—O1—C1	56.26 (18)	C5—C4—C3—C2	−0.3 (3)
N1—Ni1—O1—C1	−123.74 (18)	C3—C4—C5—C6	2.5 (3)
O1i—Ni1—N1—C8	136.61 (18)	C4—C5—C6—C7	−1.7 (3)
O1—Ni1—N1—C8	−43.39 (18)	Cl1—C7—C2—C1	10.4 (3)
O1i—Ni1—N1—C12	−45.66 (17)	Cl1—C7—C2—C3	−175.42 (16)
O1—Ni1—N1—C12	134.34 (17)	C6—C7—C2—C1	−170.8 (2)
O4—Ni1—N1—C12	42.53 (17)	C6—C7—C2—C3	3.4 (3)
O4i—Ni1—N1—C12	−137.47 (17)	Cl1—C7—C6—C5	177.53 (17)
O4—Ni1—N1—C8	−135.20 (18)	C2—C7—C6—C5	−1.3 (3)
O4i—Ni1—N1—C8	44.80 (18)	N1—C8—C9—C10	0.6 (4)
Ni1—O1—C1—O2	22.1 (3)	C11—C10—C9—C8	0.2 (4)
Ni1—O1—C1—C2	−154.02 (15)	C12—C11—C10—C9	−0.7 (3)
Ni1—N1—C8—C9	176.99 (17)	C13—C11—C10—C9	177.3 (2)
C12—N1—C8—C9	−0.8 (3)	C10—C11—C12—N1	0.5 (3)
Ni1—N1—C12—C11	−177.65 (17)	C13—C11—C12—N1	−177.6 (2)
C8—N1—C12—C11	0.2 (3)	C10—C11—C13—O3	−173.6 (2)
O1—C1—C2—C3	28.5 (3)	C10—C11—C13—N2	4.8 (4)
O1—C1—C2—C7	−157.4 (2)	C12—C11—C13—O3	4.4 (3)
O2—C1—C2—C3	−147.9 (2)	C12—C11—C13—N2	−177.1 (2)
O2—C1—C2—C7	26.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2	0.84 (4)	1.82 (3)	2.630 (2)	161 (3)
O4—H42···O3ii	0.85 (3)	2.09 (3)	2.887 (2)	156 (3)
N2—H21···O2iii	0.79 (3)	2.13 (3)	2.865 (3)	156 (3)
N2—H22···O3iv	0.84 (3)	2.16 (3)	2.934 (3)	153 (3)
C9—H9···Cg1iii	0.93	2.88	3.596 (2)	135

Table 1

Selected geometric parameters (Å, °)

Ni1—O1	2.1017 (16)
Ni1—O4	2.1520 (16)
Ni1—N1	2.1217 (18)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2	0.84 (4)	1.82 (3)	2.630 (2)	161 (3)
O4—H42⋯O3ii	0.85 (3)	2.09 (3)	2.887 (2)	156 (3)
N2—H21⋯O2iii	0.79 (3)	2.13 (3)	2.865 (3)	156 (3)
N2—H22⋯O3iv	0.84 (3)	2.16 (3)	2.934 (3)	153 (3)
C9—H9⋯Cg1iii	0.93	2.88	3.596 (2)	135

Symmetry codes: (ii) ; (iii) ; (iv) .