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

The title Ni(II) complex, [Ni(C(8)H(8)NO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], is centrosymmetric with the Ni atom on an inversion center. The mol-ecule contains two 4-methyl-amino-benzoate (MAB) 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 2.09 (14)°, while the pyridine and benzene rings are oriented at a dihedral angle of 66.15 (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.

Related literature

For general background to transition metal complexes with biochemically active ligands, see: Antolini et al. (1982 ▶); Bigoli et al. (1972 ▶); Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶); Krishnamachari (1974 ▶). For related structures, see: Hökelek et al. (1995 ▶, 1997 ▶, 2007 ▶, 2008 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 2007 ▶).

Experimental

Crystal data

[Ni(C8H8NO2)2(C6H6N2O)2(H2O)2]

M = 639.31

Monoclinic,

a = 10.9331 (6) Å

b = 9.8467 (5) Å

c = 14.1992 (8) Å

β = 107.454 (1)°

V = 1458.23 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.73 mm−1

T = 100 K

0.47 × 0.32 × 0.31 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.755, T max = 0.796

13201 measured reflections

3635 independent reflections

2954 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.085

S = 1.09

3635 reflections

217 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.42 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/S1600536809015633/xu2516sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015633/xu2516Isup2.hkl

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

[Ni(C8H8NO2)2(C6H6N2O)2(H2O)2]	F(000) = 668
Mr = 639.31	Dx = 1.456 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6218 reflections
a = 10.9331 (6) Å	θ = 2.6–28.4°
b = 9.8467 (5) Å	µ = 0.73 mm−1
c = 14.1992 (8) Å	T = 100 K
β = 107.454 (1)°	Block, blue
V = 1458.23 (14) Å3	0.47 × 0.32 × 0.31 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	3635 independent reflections
Radiation source: fine-focus sealed tube	2954 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→13
Tmin = 0.755, Tmax = 0.796	k = −12→13
13201 measured reflections	l = −18→18

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) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0457P)2 + 0.1097P] where P = (Fo2 + 2Fc2)/3
3635 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.41 e Å−3
3 restraints	Δρmin = −0.42 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	0.0000	0.5000	0.0000	0.02520 (9)
O1	−0.05431 (9)	0.42926 (11)	0.11617 (7)	0.0298 (2)
O2	−0.20986 (10)	0.28374 (11)	0.03794 (7)	0.0331 (3)
O3	−0.24476 (12)	0.91313 (14)	−0.21749 (8)	0.0441 (3)
O4	0.18759 (10)	0.52817 (12)	0.08904 (8)	0.0295 (2)
H41	0.209 (2)	0.547 (2)	0.1523 (11)	0.055 (6)*
H42	0.212 (2)	0.600 (2)	0.0608 (16)	0.087 (9)*
N1	−0.05647 (11)	0.69514 (13)	0.02746 (8)	0.0269 (3)
N2	−0.23426 (13)	1.10935 (16)	−0.13262 (11)	0.0354 (3)
H21	−0.217 (2)	1.156 (2)	−0.0742 (16)	0.062 (6)*
H22	−0.2690 (18)	1.1511 (18)	−0.1881 (14)	0.039 (5)*
N3	−0.12888 (14)	0.12206 (18)	0.48807 (10)	0.0422 (4)
H31	−0.190 (2)	0.071 (2)	0.4877 (16)	0.061 (7)*
C1	−0.13324 (13)	0.33378 (16)	0.11561 (10)	0.0290 (3)
C2	−0.13399 (13)	0.28004 (16)	0.21324 (10)	0.0291 (3)
C3	−0.21846 (14)	0.17675 (17)	0.22136 (11)	0.0305 (3)
H3	−0.2773	0.1428	0.1646	0.037*
C4	−0.21573 (14)	0.12488 (17)	0.31176 (11)	0.0328 (3)
H4	−0.2723	0.0559	0.3152	0.039*
C5	−0.12885 (14)	0.17437 (18)	0.39904 (11)	0.0335 (4)
C6	−0.04453 (14)	0.27794 (18)	0.39144 (11)	0.0368 (4)
H6	0.0145	0.3121	0.4481	0.044*
C7	−0.04892 (14)	0.32956 (18)	0.29965 (11)	0.0334 (3)
H7	0.0067	0.3994	0.2959	0.040*
C8	−0.04561 (13)	0.74589 (17)	0.11720 (10)	0.0288 (3)
H8	−0.0069	0.6930	0.1723	0.035*
C9	−0.08955 (14)	0.87357 (17)	0.13112 (11)	0.0321 (3)
H9	−0.0814	0.9052	0.1944	0.039*
C10	−0.14588 (14)	0.95401 (18)	0.04957 (11)	0.0315 (3)
H10	−0.1749	1.0409	0.0571	0.038*
C11	−0.15803 (13)	0.90173 (16)	−0.04382 (10)	0.0287 (3)
C12	−0.11315 (13)	0.77289 (17)	−0.05083 (10)	0.0285 (3)
H12	−0.1227	0.7378	−0.1134	0.034*
C13	−0.21654 (14)	0.97680 (18)	−0.13847 (11)	0.0333 (4)
C14	−0.04606 (17)	0.1690 (2)	0.58153 (12)	0.0495 (5)
H14A	−0.0642	0.1195	0.6340	0.074*
H14B	−0.0605	0.2641	0.5888	0.074*
H14C	0.0417	0.1547	0.5841	0.074*

	U11	U22	U33	U12	U13	U23
Ni1	0.01580 (14)	0.04990 (18)	0.01093 (13)	−0.00137 (10)	0.00555 (10)	−0.00041 (10)
O1	0.0223 (5)	0.0548 (7)	0.0150 (5)	−0.0029 (4)	0.0097 (4)	−0.0004 (4)
O2	0.0224 (5)	0.0601 (7)	0.0174 (5)	−0.0052 (5)	0.0070 (4)	0.0009 (5)
O3	0.0456 (7)	0.0668 (8)	0.0148 (5)	0.0090 (6)	0.0013 (5)	0.0035 (5)
O4	0.0196 (5)	0.0539 (7)	0.0139 (5)	−0.0019 (4)	0.0037 (4)	−0.0018 (4)
N1	0.0163 (5)	0.0507 (7)	0.0146 (6)	−0.0017 (5)	0.0061 (5)	0.0002 (5)
N2	0.0270 (7)	0.0584 (9)	0.0188 (7)	0.0069 (6)	0.0037 (6)	0.0069 (6)
N3	0.0257 (7)	0.0787 (11)	0.0224 (7)	−0.0043 (7)	0.0074 (6)	0.0137 (7)
C1	0.0172 (7)	0.0540 (9)	0.0179 (7)	0.0031 (6)	0.0086 (6)	0.0016 (6)
C2	0.0168 (6)	0.0542 (9)	0.0185 (7)	0.0036 (6)	0.0087 (5)	0.0045 (6)
C3	0.0181 (7)	0.0548 (9)	0.0204 (7)	0.0017 (6)	0.0084 (6)	−0.0003 (6)
C4	0.0203 (7)	0.0547 (10)	0.0267 (8)	0.0006 (6)	0.0119 (6)	0.0055 (7)
C5	0.0190 (7)	0.0630 (10)	0.0206 (7)	0.0058 (6)	0.0092 (6)	0.0100 (7)
C6	0.0200 (7)	0.0717 (11)	0.0175 (7)	−0.0031 (7)	0.0035 (6)	0.0058 (7)
C7	0.0193 (7)	0.0609 (10)	0.0211 (7)	−0.0022 (6)	0.0078 (6)	0.0058 (7)
C8	0.0196 (7)	0.0541 (9)	0.0130 (6)	0.0013 (6)	0.0052 (5)	0.0034 (6)
C9	0.0268 (7)	0.0552 (9)	0.0146 (7)	0.0030 (7)	0.0066 (6)	−0.0005 (6)
C10	0.0226 (7)	0.0537 (9)	0.0188 (7)	0.0038 (6)	0.0072 (6)	0.0012 (6)
C11	0.0151 (6)	0.0558 (9)	0.0148 (7)	0.0000 (6)	0.0038 (5)	0.0027 (6)
C12	0.0172 (6)	0.0556 (9)	0.0128 (6)	−0.0017 (6)	0.0046 (5)	−0.0002 (6)
C13	0.0191 (7)	0.0634 (11)	0.0162 (7)	0.0035 (6)	0.0037 (6)	0.0047 (6)
C14	0.0309 (9)	0.0953 (15)	0.0205 (8)	−0.0025 (9)	0.0053 (7)	0.0164 (9)

Ni1—O1	2.0362 (9)	C3—C4	1.373 (2)
Ni1—O1i	2.0362 (9)	C3—H3	0.9300
Ni1—O4	2.0800 (11)	C4—H4	0.9300
Ni1—O4i	2.0800 (11)	C5—N3	1.3652 (19)
Ni1—N1	2.0903 (13)	C5—C4	1.403 (2)
Ni1—N1i	2.0903 (13)	C5—C6	1.400 (2)
O1—C1	1.2746 (18)	C6—C7	1.386 (2)
O2—C1	1.2675 (17)	C6—H6	0.9300
O3—C13	1.2407 (19)	C7—H7	0.9300
O4—H41	0.878 (14)	C8—C9	1.381 (2)
O4—H42	0.897 (16)	C8—H8	0.9300
N1—C8	1.3404 (17)	C9—C10	1.386 (2)
N1—C12	1.3389 (18)	C9—H9	0.9300
N2—C13	1.326 (2)	C10—H10	0.9300
N2—H21	0.92 (2)	C11—C10	1.391 (2)
N2—H22	0.869 (19)	C11—C12	1.375 (2)
N3—C14	1.440 (2)	C11—C13	1.499 (2)
N3—H31	0.83 (2)	C12—H12	0.9300
C2—C1	1.4861 (19)	C14—H14A	0.9600
C2—C7	1.387 (2)	C14—H14B	0.9600
C3—C2	1.402 (2)	C14—H14C	0.9600
O1i—Ni1—O1	180.0	C3—C4—C5	121.02 (15)
O1—Ni1—O4	91.56 (4)	C3—C4—H4	119.5
O1i—Ni1—O4	88.44 (4)	C5—C4—H4	119.5
O1i—Ni1—O4i	91.56 (4)	N3—C5—C4	119.91 (15)
O1—Ni1—O4i	88.44 (4)	N3—C5—C6	121.94 (15)
O1—Ni1—N1	89.38 (4)	C6—C5—C4	118.14 (13)
O1i—Ni1—N1	90.62 (4)	C5—C6—H6	120.0
O1—Ni1—N1i	90.62 (4)	C7—C6—C5	120.10 (14)
O1i—Ni1—N1i	89.38 (4)	C7—C6—H6	120.0
O4—Ni1—O4i	180.00 (7)	C2—C7—H7	119.1
O4—Ni1—N1	93.24 (4)	C6—C7—C2	121.85 (15)
O4i—Ni1—N1	86.76 (4)	C6—C7—H7	119.1
O4—Ni1—N1i	86.76 (4)	N1—C8—C9	122.69 (13)
O4i—Ni1—N1i	93.24 (4)	N1—C8—H8	118.7
N1i—Ni1—N1	180.00 (6)	C9—C8—H8	118.7
C1—O1—Ni1	127.49 (9)	C8—C9—C10	119.16 (14)
Ni1—O4—H41	123.9 (14)	C8—C9—H9	120.4
Ni1—O4—H42	102.0 (16)	C10—C9—H9	120.4
H41—O4—H42	105.4 (18)	C9—C10—C11	118.46 (15)
C8—N1—Ni1	124.97 (10)	C9—C10—H10	120.8
C12—N1—Ni1	117.37 (9)	C11—C10—H10	120.8
C12—N1—C8	117.58 (13)	C10—C11—C13	124.42 (15)
C13—N2—H21	123.9 (13)	C12—C11—C10	118.45 (13)
C13—N2—H22	116.2 (12)	C12—C11—C13	117.12 (13)
H21—N2—H22	119.8 (18)	N1—C12—C11	123.64 (13)
C5—N3—C14	123.89 (16)	N1—C12—H12	118.2
C5—N3—H31	116.4 (15)	C11—C12—H12	118.2
C14—N3—H31	118.7 (15)	O3—C13—N2	123.55 (15)
O1—C1—C2	116.74 (13)	O3—C13—C11	119.03 (15)
O2—C1—O1	124.17 (13)	N2—C13—C11	117.41 (14)
O2—C1—C2	119.08 (13)	N3—C14—H14A	109.5
C3—C2—C1	121.55 (13)	N3—C14—H14B	109.5
C7—C2—C1	120.67 (13)	N3—C14—H14C	109.5
C7—C2—C3	117.77 (13)	H14A—C14—H14B	109.5
C2—C3—H3	119.4	H14A—C14—H14C	109.5
C4—C3—C2	121.11 (14)	H14B—C14—H14C	109.5
C4—C3—H3	119.4
O4—Ni1—O1—C1	−142.35 (12)	C1—C2—C7—C6	−177.70 (14)
O4i—Ni1—O1—C1	37.65 (12)	C3—C2—C7—C6	1.3 (2)
N1i—Ni1—O1—C1	−55.58 (12)	C4—C3—C2—C1	177.98 (14)
N1—Ni1—O1—C1	124.42 (12)	C4—C3—C2—C7	−1.0 (2)
O1i—Ni1—N1—C8	−145.11 (11)	C2—C3—C4—C5	0.5 (2)
O1—Ni1—N1—C8	34.89 (11)	C4—C5—N3—C14	−178.12 (16)
O1i—Ni1—N1—C12	38.14 (10)	C6—C5—N3—C14	1.4 (3)
O1—Ni1—N1—C12	−141.86 (10)	N3—C5—C4—C3	179.35 (15)
O4—Ni1—N1—C8	−56.63 (11)	N3—C5—C6—C7	−179.07 (16)
O4i—Ni1—N1—C8	123.37 (11)	C4—C5—C6—C7	0.5 (2)
O4—Ni1—N1—C12	126.62 (10)	C6—C5—C4—C3	−0.2 (2)
O4i—Ni1—N1—C12	−53.38 (10)	C5—C6—C7—C2	−1.1 (3)
Ni1—O1—C1—O2	−14.1 (2)	N1—C8—C9—C10	−0.8 (2)
Ni1—O1—C1—C2	166.19 (9)	C8—C9—C10—C11	1.1 (2)
Ni1—N1—C8—C9	−177.10 (11)	C12—C11—C10—C9	−0.2 (2)
C12—N1—C8—C9	−0.4 (2)	C13—C11—C10—C9	−179.89 (14)
Ni1—N1—C12—C11	178.29 (11)	C10—C11—C12—N1	−1.0 (2)
C8—N1—C12—C11	1.3 (2)	C13—C11—C12—N1	178.68 (13)
C3—C2—C1—O1	178.85 (13)	C10—C11—C13—O3	−166.51 (15)
C3—C2—C1—O2	−0.8 (2)	C10—C11—C13—N2	14.0 (2)
C7—C2—C1—O1	−2.2 (2)	C12—C11—C13—O3	13.8 (2)
C7—C2—C1—O2	178.09 (14)	C12—C11—C13—N2	−165.61 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.92 (2)	2.01 (2)	2.9150 (18)	167.9 (18)
N3—H31···O4iii	0.84 (2)	2.44 (2)	3.162 (2)	144.6 (19)
O4—H41···O3iv	0.88 (2)	1.81 (2)	2.6849 (16)	179 (2)
O4—H42···O2i	0.89 (2)	1.80 (2)	2.6464 (15)	156 (2)

Table 1

Selected bond lengths (Å)

Ni1—O1	2.0362 (9)
Ni1—O4	2.0800 (11)
Ni1—N1	2.0903 (13)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2i	0.92 (2)	2.01 (2)	2.9150 (18)	167.9 (18)
N3—H31⋯O4ii	0.84 (2)	2.44 (2)	3.162 (2)	144.6 (19)
O4—H41⋯O3iii	0.877 (15)	1.808 (15)	2.6849 (16)	179 (2)
O4—H42⋯O2iv	0.89 (2)	1.80 (2)	2.6464 (15)	156 (2)

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