Tetra-aqua-bis[4-(methyl-amino)benzoato-κO]nickel(II).

The title complex, [Ni(C(8)H(8)NO(2))(2)(H(2)O)(4)], is centrosymmetric with the Ni(II) ion located on a centre of symmetry. It contains two 4-(methyl-amino)benzoate (PMAB) anions and four coordinated water mol-ecules. The four O atoms in the equatorial plane around the Ni(II) ion form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by two O atoms of the PMAB anions in the axial positions. In the crystal structure, inter-molecular O-H⋯O, O-H⋯N, N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

For structure–function–coordination relationships of the aryl­carboxyl­ate ion in transition-metal complexes of benzoic acid derivatives, see: Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For studies of transition-metal complexes with biochemical model systems, see: Antolini et al. (1982 ▶). For the coordination modes of benzoic acid derivatives, see: Chen & Chen (2002 ▶); Amiraslanov et al. (1979 ▶); Hauptmann et al. (2000 ▶). For related structures, see: Hökelek et al. (2009a ▶,b ▶); Necefoğlu et al. (2010 ▶); Sertçelik et al. (2009 ▶).

Experimental

Crystal data

[Ni(C8H8NO2)2(H2O)4]

M = 431.06

Monoclinic,

a = 7.5466 (2) Å

b = 6.1811 (2) Å

c = 19.4802 (3) Å

β = 98.628 (3)°

V = 898.40 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.13 mm−1

T = 100 K

0.35 × 0.25 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.718, T max = 0.863

8475 measured reflections

2242 independent reflections

2085 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.061

S = 1.06

2242 reflections

145 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.33 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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810014807/ci5081sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014807/ci5081Isup2.hkl

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

[Ni(C8H8NO2)2(H2O)4]	F(000) = 452
Mr = 431.06	Dx = 1.594 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5176 reflections
a = 7.5466 (2) Å	θ = 2.7–28.4°
b = 6.1811 (2) Å	µ = 1.13 mm−1
c = 19.4802 (3) Å	T = 100 K
β = 98.628 (3)°	Block, green
V = 898.40 (4) Å3	0.35 × 0.25 × 0.13 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	2242 independent reflections
Radiation source: fine-focus sealed tube	2085 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.718, Tmax = 0.863	k = −8→8
8475 measured reflections	l = −25→26

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.032P)2 + 0.3955P] where P = (Fo2 + 2Fc2)/3
2242 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.41 e Å−3
6 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.5000	0.0000	0.01094 (9)
O1	0.12315 (14)	0.95272 (17)	0.08266 (5)	0.0166 (2)
O2	−0.00352 (13)	0.63206 (17)	0.09653 (5)	0.0153 (2)
O3	0.23373 (13)	0.34113 (17)	0.03994 (5)	0.0150 (2)
H31	0.327 (2)	0.418 (3)	0.0632 (10)	0.031 (5)*
H32	0.220 (3)	0.227 (3)	0.0651 (11)	0.044 (7)*
O4	−0.15665 (13)	0.25462 (17)	0.03223 (5)	0.0146 (2)
H41	−0.163 (4)	0.167 (4)	−0.0089 (11)	0.070 (9)*
H42	−0.090 (3)	0.178 (4)	0.0679 (10)	0.046 (7)*
N1	−0.05050 (17)	1.0577 (2)	0.39282 (6)	0.0155 (2)
H1	−0.133 (3)	0.984 (3)	0.4069 (11)	0.022 (5)*
C1	0.04946 (17)	0.8156 (2)	0.11841 (7)	0.0130 (3)
C2	0.02308 (17)	0.8804 (2)	0.19011 (7)	0.0126 (3)
C3	−0.05536 (18)	0.7378 (2)	0.23236 (7)	0.0149 (3)
H3	−0.0902	0.6007	0.2159	0.018*
C4	−0.08175 (18)	0.7983 (2)	0.29847 (7)	0.0156 (3)
H4	−0.1342	0.7015	0.3260	0.019*
C5	−0.03016 (18)	1.0039 (2)	0.32435 (7)	0.0137 (3)
C6	0.04875 (18)	1.1470 (2)	0.28224 (7)	0.0147 (3)
H6	0.0840	1.2840	0.2987	0.018*
C7	0.07450 (18)	1.0852 (2)	0.21607 (7)	0.0142 (3)
H7	0.1269	1.1817	0.1885	0.017*
C8	−0.0564 (2)	1.2874 (3)	0.41124 (7)	0.0182 (3)
H8A	−0.0838	1.3009	0.4576	0.027*
H8B	−0.1473	1.3589	0.3795	0.027*
H8C	0.0578	1.3526	0.4087	0.027*

	U11	U22	U33	U12	U13	U23
Ni1	0.01233 (13)	0.00929 (13)	0.01089 (13)	−0.00098 (9)	0.00076 (9)	0.00030 (8)
O1	0.0221 (5)	0.0123 (5)	0.0157 (5)	−0.0032 (4)	0.0035 (4)	0.0001 (4)
O2	0.0192 (5)	0.0124 (5)	0.0140 (4)	−0.0025 (4)	0.0015 (4)	−0.0013 (4)
O3	0.0151 (5)	0.0128 (5)	0.0163 (5)	−0.0011 (4)	−0.0001 (4)	0.0012 (4)
O4	0.0162 (5)	0.0130 (5)	0.0144 (4)	−0.0015 (4)	0.0011 (4)	0.0005 (4)
N1	0.0159 (6)	0.0170 (6)	0.0143 (5)	−0.0006 (5)	0.0043 (4)	0.0006 (5)
C1	0.0118 (6)	0.0125 (6)	0.0138 (6)	0.0023 (5)	−0.0009 (4)	0.0013 (5)
C2	0.0115 (5)	0.0122 (6)	0.0134 (6)	0.0004 (5)	−0.0003 (4)	−0.0003 (5)
C3	0.0145 (6)	0.0122 (6)	0.0171 (6)	−0.0014 (5)	−0.0002 (5)	−0.0003 (5)
C4	0.0159 (6)	0.0151 (7)	0.0160 (6)	−0.0013 (5)	0.0026 (5)	0.0033 (5)
C5	0.0107 (6)	0.0158 (7)	0.0141 (6)	0.0021 (5)	0.0001 (5)	0.0008 (5)
C6	0.0143 (6)	0.0132 (6)	0.0163 (6)	−0.0014 (5)	0.0017 (5)	−0.0014 (5)
C7	0.0142 (6)	0.0134 (7)	0.0151 (6)	−0.0013 (5)	0.0021 (5)	0.0005 (5)
C8	0.0196 (6)	0.0185 (7)	0.0172 (6)	−0.0005 (6)	0.0055 (5)	−0.0018 (5)

Ni1—O2	2.0537 (10)	C2—C3	1.3969 (19)
Ni1—O2i	2.0537 (10)	C3—H3	0.93
Ni1—O3	2.0662 (10)	C4—C3	1.3839 (19)
Ni1—O3i	2.0662 (10)	C4—C5	1.401 (2)
Ni1—O4	2.0772 (10)	C4—H4	0.93
Ni1—O4i	2.0772 (10)	C6—C5	1.3987 (19)
O1—C1	1.2761 (17)	C6—H6	0.93
O2—C1	1.2561 (18)	C7—C2	1.396 (2)
O3—H31	0.909 (16)	C7—C6	1.3858 (19)
O3—H32	0.873 (17)	C7—H7	0.93
O4—H41	0.964 (17)	C8—N1	1.466 (2)
O4—H42	0.926 (17)	C8—H8A	0.96
N1—C5	1.4052 (18)	C8—H8B	0.96
N1—H1	0.85 (2)	C8—H8C	0.96
C2—C1	1.4948 (18)
O2—Ni1—O3	88.38 (4)	O2—C1—O1	123.87 (13)
O2i—Ni1—O3	91.62 (4)	O2—C1—C2	118.61 (12)
O2—Ni1—O2i	180.00 (2)	C3—C2—C1	120.60 (13)
O2—Ni1—O3i	91.62 (4)	C7—C2—C1	120.83 (12)
O2i—Ni1—O3i	88.38 (4)	C7—C2—C3	118.57 (12)
O2—Ni1—O4	85.83 (4)	C2—C3—H3	119.6
O2i—Ni1—O4	94.17 (4)	C4—C3—C2	120.71 (13)
O2—Ni1—O4i	94.17 (4)	C4—C3—H3	119.6
O2i—Ni1—O4i	85.83 (4)	C3—C4—C5	120.60 (13)
O3i—Ni1—O3	180.00 (5)	C3—C4—H4	119.7
O3—Ni1—O4	91.81 (4)	C5—C4—H4	119.7
O3i—Ni1—O4	88.19 (4)	C4—C5—N1	119.48 (13)
O3—Ni1—O4i	88.19 (4)	C6—C5—N1	121.60 (13)
O3i—Ni1—O4i	91.81 (4)	C6—C5—C4	118.84 (13)
O4—Ni1—O4i	180.00 (5)	C5—C6—H6	119.9
C1—O2—Ni1	128.50 (9)	C7—C6—C5	120.18 (13)
Ni1—O3—H31	119.5 (15)	C7—C6—H6	119.9
Ni1—O3—H32	115.3 (16)	C2—C7—H7	119.4
H31—O3—H32	106.7 (19)	C6—C7—C2	121.11 (13)
Ni1—O4—H41	96.8 (18)	C6—C7—H7	119.4
Ni1—O4—H42	109.2 (15)	N1—C8—H8A	109.5
H42—O4—H41	107 (2)	N1—C8—H8B	109.5
C5—N1—C8	118.22 (12)	N1—C8—H8C	109.5
C5—N1—H1	111.6 (14)	H8A—C8—H8B	109.5
C8—N1—H1	113.0 (13)	H8A—C8—H8C	109.5
O1—C1—C2	117.52 (12)	H8B—C8—H8C	109.5
O3—Ni1—O2—C1	98.00 (11)	C7—C2—C1—O2	−177.98 (12)
O3i—Ni1—O2—C1	−82.00 (11)	C1—C2—C3—C4	−179.27 (12)
O4—Ni1—O2—C1	−170.07 (12)	C7—C2—C3—C4	0.1 (2)
O4i—Ni1—O2—C1	9.93 (12)	C5—C4—C3—C2	0.0 (2)
Ni1—O2—C1—O1	−2.6 (2)	C3—C4—C5—N1	−176.96 (13)
Ni1—O2—C1—C2	176.51 (8)	C3—C4—C5—C6	−0.1 (2)
C8—N1—C5—C4	−159.10 (13)	C7—C6—C5—N1	176.96 (13)
C8—N1—C5—C6	24.13 (19)	C7—C6—C5—C4	0.2 (2)
C3—C2—C1—O1	−179.47 (12)	C6—C7—C2—C1	179.34 (12)
C3—C2—C1—O2	1.36 (19)	C6—C7—C2—C3	0.0 (2)
C7—C2—C1—O1	1.19 (19)	C2—C7—C6—C5	−0.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ii	0.85 (2)	2.55 (2)	3.3902 (16)	170 (2)
O3—H31···N1iii	0.91 (2)	1.97 (2)	2.8780 (16)	172 (2)
O3—H32···O1iv	0.87 (2)	1.90 (2)	2.7131 (15)	155 (2)
O4—H41···O1i	0.96 (2)	1.68 (2)	2.6240 (14)	165 (3)
O4—H42···O1iv	0.92 (2)	2.11 (2)	2.8781 (15)	139 (2)
C8—H8A···O3v	0.96	2.43	3.2583 (18)	144
C8—H8C···O1vi	0.96	2.47	3.4105 (19)	168

Table 1

Selected bond lengths (Å)

Ni1—O2	2.0537 (10)
Ni1—O3	2.0662 (10)
Ni1—O4	2.0772 (10)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4i	0.85 (2)	2.55 (2)	3.3902 (16)	170 (2)
O3—H31⋯N1ii	0.91 (2)	1.97 (2)	2.8780 (16)	172 (2)
O3—H32⋯O1iii	0.87 (2)	1.90 (2)	2.7131 (15)	155 (2)
O4—H41⋯O1iv	0.96 (2)	1.68 (2)	2.6240 (14)	165 (3)
O4—H42⋯O1iii	0.92 (2)	2.11 (2)	2.8781 (15)	139 (2)
C8—H8A⋯O3v	0.96	2.43	3.2583 (18)	144
C8—H8C⋯O1vi	0.96	2.47	3.4105 (19)	168

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