Diaqua-bis(4-methyl-benzoato-κO)bis-(nicotinamide-κN)nickel(II).

The title Ni(II) complex, [Ni(C(8)H(7)O(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], is centrosymmetric with the Ni atom located on an inversion center. The mol-ecule contains two 4-methyl-benzoate (PMB) and two nicotinamide (NA) ligands and two coordinated 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-ate group and the adjacent benzene ring is 26.15 (10)°, while the pyridine and benzene rings are oriented at a dihedral angle of 87.81 (4)°. In the crystal structure, inter-molecular O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. The π-π contact between the benzene rings [centroid-centroid distance = 3.896 (1) Å] may further stabilize the crystal structure. A weak C-H⋯π inter-action involving the pyridine ring also occurs.

Related literature

For niacin, see: Krishnamachari (1974 ▶) and for the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1996 ▶, 2009a ▶,b ▶,c ▶); Hökelek & Necefoğlu (1998 ▶).

Experimental

Crystal data

[Ni(C8H7O2)2(C6H6N2O)2(H2O)2]

M = 609.26

Triclinic,

a = 7.7324 (2) Å

b = 9.7335 (3) Å

c = 9.8198 (3) Å

α = 78.440 (2)°

β = 86.475 (3)°

γ = 71.662 (2)°

V = 687.31 (4) Å3

Z = 1

Mo Kα radiation

μ = 0.76 mm−1

T = 99 K

0.33 × 0.28 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.889, T max = 0.934

12002 measured reflections

3390 independent reflections

3034 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.068

S = 1.05

3390 reflections

204 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.50 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 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007385/xu2730sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007385/xu2730Isup2.hkl

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

[Ni(C8H7O2)2(C6H6N2O)2(H2O)2]	Z = 1
Mr = 609.26	F(000) = 318
Triclinic, P1	Dx = 1.472 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7324 (2) Å	Cell parameters from 6458 reflections
b = 9.7335 (3) Å	θ = 2.8–28.3°
c = 9.8198 (3) Å	µ = 0.76 mm−1
α = 78.440 (2)°	T = 99 K
β = 86.475 (3)°	Prism, blue
γ = 71.662 (2)°	0.33 × 0.28 × 0.25 mm
V = 687.31 (4) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3390 independent reflections
Radiation source: fine-focus sealed tube	3034 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.889, Tmax = 0.934	k = −12→12
12002 measured reflections	l = −12→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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0238P)2 + 0.4565P] where P = (Fo2 + 2Fc2)/3
3390 reflections	(Δ/σ)max < 0.001
204 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.50 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	0.0000	0.5000	0.00996 (8)
O1	0.12751 (13)	0.01072 (11)	0.67419 (11)	0.0129 (2)
O2	−0.11125 (14)	0.15789 (11)	0.77116 (11)	0.0149 (2)
O3	0.44171 (14)	0.33247 (11)	0.48634 (12)	0.0177 (2)
O4	0.25984 (15)	−0.07089 (12)	0.41538 (12)	0.0136 (2)
H41	0.342 (3)	−0.137 (2)	0.458 (2)	0.034 (6)*
H42	0.228 (3)	−0.103 (2)	0.345 (2)	0.036 (6)*
N1	−0.00159 (16)	0.21391 (13)	0.41144 (13)	0.0116 (2)
N2	0.33786 (19)	0.55995 (15)	0.35530 (15)	0.0176 (3)
H21	0.252 (3)	0.628 (2)	0.307 (2)	0.022 (5)*
H22	0.425 (3)	0.586 (2)	0.390 (2)	0.024 (5)*
C1	0.05766 (19)	0.09453 (16)	0.75988 (15)	0.0120 (3)
C2	0.18258 (19)	0.12691 (15)	0.85126 (15)	0.0121 (3)
C3	0.3601 (2)	0.12032 (16)	0.81040 (16)	0.0139 (3)
H3	0.4070	0.0851	0.7302	0.017*
C4	0.4678 (2)	0.16598 (16)	0.88863 (16)	0.0153 (3)
H4	0.5855	0.1624	0.8593	0.018*
C5	0.4019 (2)	0.21690 (17)	1.00998 (17)	0.0162 (3)
C6	0.2262 (2)	0.21841 (18)	1.05279 (17)	0.0192 (3)
H6	0.1816	0.2488	1.1356	0.023*
C7	0.1171 (2)	0.17547 (17)	0.97424 (16)	0.0164 (3)
H7	−0.0006	0.1790	1.0037	0.020*
C8	0.5187 (2)	0.26752 (19)	1.09414 (19)	0.0239 (4)
H8A	0.4556	0.3664	1.1063	0.036*
H8B	0.6314	0.2651	1.0463	0.036*
H8C	0.5435	0.2033	1.1834	0.036*
C9	−0.13817 (19)	0.31071 (16)	0.33131 (16)	0.0140 (3)
H9	−0.2385	0.2823	0.3163	0.017*
C10	−0.1356 (2)	0.45107 (17)	0.27015 (17)	0.0169 (3)
H10	−0.2326	0.5157	0.2153	0.020*
C11	0.0139 (2)	0.49377 (16)	0.29208 (16)	0.0156 (3)
H11	0.0188	0.5875	0.2521	0.019*
C12	0.15612 (19)	0.39452 (16)	0.37462 (15)	0.0121 (3)
C13	0.14248 (19)	0.25568 (16)	0.43189 (15)	0.0115 (3)
H13	0.2378	0.1888	0.4869	0.014*
C14	0.32352 (19)	0.42736 (16)	0.40920 (16)	0.0131 (3)

	U11	U22	U33	U12	U13	U23
Ni1	0.00972 (13)	0.00810 (13)	0.01255 (14)	−0.00273 (10)	−0.00152 (9)	−0.00267 (10)
O1	0.0132 (5)	0.0108 (5)	0.0144 (5)	−0.0023 (4)	−0.0020 (4)	−0.0036 (4)
O2	0.0120 (5)	0.0152 (5)	0.0175 (6)	−0.0027 (4)	−0.0015 (4)	−0.0050 (4)
O3	0.0162 (5)	0.0107 (5)	0.0257 (6)	−0.0035 (4)	−0.0068 (4)	−0.0016 (5)
O4	0.0114 (5)	0.0124 (5)	0.0163 (6)	−0.0018 (4)	−0.0020 (4)	−0.0038 (5)
N1	0.0122 (6)	0.0100 (6)	0.0128 (6)	−0.0029 (5)	−0.0008 (5)	−0.0035 (5)
N2	0.0172 (7)	0.0113 (6)	0.0254 (8)	−0.0066 (5)	−0.0074 (6)	−0.0003 (6)
C1	0.0134 (7)	0.0098 (7)	0.0124 (7)	−0.0044 (5)	−0.0023 (5)	0.0010 (5)
C2	0.0132 (7)	0.0087 (6)	0.0133 (7)	−0.0021 (5)	−0.0032 (5)	−0.0007 (5)
C3	0.0157 (7)	0.0130 (7)	0.0124 (7)	−0.0033 (6)	−0.0010 (5)	−0.0028 (6)
C4	0.0135 (7)	0.0139 (7)	0.0179 (8)	−0.0040 (6)	−0.0021 (6)	−0.0014 (6)
C5	0.0180 (7)	0.0116 (7)	0.0182 (8)	−0.0024 (6)	−0.0062 (6)	−0.0027 (6)
C6	0.0193 (8)	0.0224 (8)	0.0162 (8)	−0.0028 (6)	−0.0002 (6)	−0.0101 (7)
C7	0.0132 (7)	0.0185 (8)	0.0167 (8)	−0.0030 (6)	−0.0003 (6)	−0.0046 (6)
C8	0.0219 (8)	0.0243 (9)	0.0285 (10)	−0.0062 (7)	−0.0070 (7)	−0.0111 (7)
C9	0.0116 (7)	0.0140 (7)	0.0173 (8)	−0.0039 (6)	−0.0022 (6)	−0.0045 (6)
C10	0.0146 (7)	0.0126 (7)	0.0207 (8)	−0.0008 (6)	−0.0058 (6)	−0.0003 (6)
C11	0.0173 (7)	0.0092 (7)	0.0199 (8)	−0.0040 (6)	−0.0024 (6)	−0.0013 (6)
C12	0.0129 (7)	0.0102 (7)	0.0138 (7)	−0.0028 (5)	−0.0005 (5)	−0.0050 (6)
C13	0.0122 (6)	0.0103 (7)	0.0120 (7)	−0.0025 (5)	−0.0019 (5)	−0.0030 (5)
C14	0.0141 (7)	0.0118 (7)	0.0142 (7)	−0.0032 (6)	0.0000 (5)	−0.0053 (6)

Ni1—O1	2.0621 (10)	C4—C5	1.389 (2)
Ni1—O1i	2.0621 (10)	C4—H4	0.9300
Ni1—O4i	2.0870 (10)	C5—C6	1.394 (2)
Ni1—O4	2.0870 (10)	C5—C8	1.509 (2)
Ni1—N1	2.0859 (12)	C6—H6	0.9300
Ni1—N1i	2.0859 (12)	C7—C2	1.393 (2)
O1—C1	1.2678 (17)	C7—C6	1.383 (2)
O2—C1	1.2654 (17)	C7—H7	0.9300
O3—C14	1.2392 (18)	C8—H8A	0.9600
O4—H41	0.81 (2)	C8—H8B	0.9600
O4—H42	0.88 (2)	C8—H8C	0.9600
N1—C9	1.3421 (19)	C9—C10	1.383 (2)
N1—C13	1.3386 (18)	C9—H9	0.9300
N2—C14	1.3294 (19)	C10—H10	0.9300
N2—H21	0.86 (2)	C11—C10	1.388 (2)
N2—H22	0.89 (2)	C11—H11	0.9300
C1—C2	1.500 (2)	C12—C11	1.388 (2)
C2—C3	1.392 (2)	C12—C13	1.390 (2)
C3—H3	0.9300	C13—H13	0.9300
C4—C3	1.389 (2)	C14—C12	1.500 (2)
O1i—Ni1—O1	180.0	C5—C4—C3	120.87 (14)
O1—Ni1—O4	86.71 (4)	C5—C4—H4	119.6
O1i—Ni1—O4	93.29 (4)	C4—C5—C6	118.33 (14)
O1—Ni1—O4i	93.29 (4)	C4—C5—C8	120.73 (14)
O1i—Ni1—O4i	86.71 (4)	C6—C5—C8	120.93 (14)
O1—Ni1—N1	89.94 (4)	C5—C6—H6	119.4
O1i—Ni1—N1	90.06 (4)	C7—C6—C5	121.11 (14)
O1—Ni1—N1i	90.06 (4)	C7—C6—H6	119.4
O1i—Ni1—N1i	89.94 (4)	C2—C7—H7	119.8
O4i—Ni1—O4	180.0	C6—C7—C2	120.34 (14)
N1—Ni1—O4	86.75 (4)	C6—C7—H7	119.8
N1i—Ni1—O4	93.25 (4)	C5—C8—H8A	109.5
N1—Ni1—O4i	93.25 (4)	C5—C8—H8B	109.5
N1i—Ni1—O4i	86.75 (4)	C5—C8—H8C	109.5
N1i—Ni1—N1	180.0	H8A—C8—H8B	109.5
C1—O1—Ni1	125.51 (9)	H8A—C8—H8C	109.5
Ni1—O4—H41	122.0 (15)	H8B—C8—H8C	109.5
Ni1—O4—H42	97.1 (14)	N1—C9—C10	122.60 (14)
H42—O4—H41	108 (2)	N1—C9—H9	118.7
C9—N1—Ni1	123.09 (10)	C10—C9—H9	118.7
C13—N1—Ni1	118.67 (10)	C9—C10—C11	118.88 (14)
C13—N1—C9	118.21 (12)	C9—C10—H10	120.6
C14—N2—H21	122.3 (13)	C11—C10—H10	120.6
C14—N2—H22	117.1 (12)	C10—C11—C12	119.04 (14)
H21—N2—H22	118.3 (18)	C10—C11—H11	120.5
O1—C1—C2	118.42 (13)	C12—C11—H11	120.5
O2—C1—O1	124.67 (14)	C11—C12—C13	118.29 (13)
O2—C1—C2	116.86 (13)	C11—C12—C14	124.54 (13)
C3—C2—C1	121.08 (13)	C13—C12—C14	117.16 (13)
C3—C2—C7	118.83 (14)	N1—C13—C12	122.98 (13)
C7—C2—C1	119.91 (13)	N1—C13—H13	118.5
C2—C3—H3	119.8	C12—C13—H13	118.5
C4—C3—C2	120.46 (14)	O3—C14—N2	122.43 (14)
C4—C3—H3	119.8	O3—C14—C12	119.86 (13)
C3—C4—H4	119.6	N2—C14—C12	117.70 (13)
O4—Ni1—O1—C1	153.43 (11)	O2—C1—C2—C7	23.4 (2)
O4i—Ni1—O1—C1	−26.57 (11)	C1—C2—C3—C4	172.95 (13)
N1—Ni1—O1—C1	66.68 (11)	C7—C2—C3—C4	−2.1 (2)
N1i—Ni1—O1—C1	−113.32 (11)	C5—C4—C3—C2	1.0 (2)
O1—Ni1—N1—C9	−144.39 (11)	C3—C4—C5—C6	1.2 (2)
O1i—Ni1—N1—C9	35.61 (11)	C3—C4—C5—C8	−179.53 (14)
O1—Ni1—N1—C13	37.62 (11)	C4—C5—C6—C7	−2.3 (2)
O1i—Ni1—N1—C13	−142.38 (11)	C8—C5—C6—C7	178.42 (15)
O4—Ni1—N1—C9	128.90 (12)	C6—C7—C2—C1	−174.10 (14)
O4i—Ni1—N1—C9	−51.10 (12)	C6—C7—C2—C3	1.0 (2)
O4—Ni1—N1—C13	−49.10 (11)	C2—C7—C6—C5	1.2 (2)
O4i—Ni1—N1—C13	130.90 (11)	N1—C9—C10—C11	0.1 (2)
Ni1—O1—C1—O2	17.6 (2)	C12—C11—C10—C9	0.0 (2)
Ni1—O1—C1—C2	−159.77 (9)	C13—C12—C11—C10	0.1 (2)
Ni1—N1—C9—C10	−178.28 (11)	C14—C12—C11—C10	−178.64 (14)
C13—N1—C9—C10	−0.3 (2)	C11—C12—C13—N1	−0.3 (2)
Ni1—N1—C13—C12	178.46 (11)	C14—C12—C13—N1	178.56 (13)
C9—N1—C13—C12	0.4 (2)	O3—C14—C12—C11	178.48 (14)
O1—C1—C2—C3	26.1 (2)	O3—C14—C12—C13	−0.3 (2)
O1—C1—C2—C7	−158.94 (14)	N2—C14—C12—C11	−1.1 (2)
O2—C1—C2—C3	−151.54 (14)	N2—C14—C12—C13	−179.83 (13)

Cg2 is the centroid of the N1/C9–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.86 (2)	2.037 (19)	2.8333 (18)	153.4 (19)
N2—H22···O3iii	0.90 (2)	2.05 (2)	2.9192 (19)	161.5 (18)
O4—H41···O3iv	0.81 (2)	2.10 (2)	2.8864 (16)	162.9 (19)
O4—H42···O2i	0.89 (2)	1.75 (2)	2.6240 (16)	165 (2)
C6—H6···Cg2v	0.93	2.65	3.5737 (18)	171

Table 1

Selected bond lengths (Å)

Ni1—O1	2.0621 (10)
Ni1—O4	2.0870 (10)
Ni1—N1	2.0859 (12)

Table 2

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the N1/C9–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2i	0.86 (2)	2.037 (19)	2.8333 (18)	153.4 (19)
N2—H22⋯O3ii	0.90 (2)	2.05 (2)	2.9192 (19)	161.5 (18)
O4—H41⋯O3iii	0.81 (2)	2.10 (2)	2.8864 (16)	162.9 (19)
O4—H42⋯O2iv	0.89 (2)	1.75 (2)	2.6240 (16)	165 (2)
C6—H6⋯Cg2v	0.93	2.65	3.5737 (18)	171

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