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

The title Ni(II) complex, [Ni(C(7)H(4)BrO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], is centrosymmetric. It contains two 2-bromo-benzoate (BB) ligands, two nicotinamide (NA) ligands and two water mol-ecules, all of them 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 30.81 (17)°, while the pyridine and benzene rings are oriented at a dihedral angle of 84.66 (6)°. In the crystal structure, O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules into a supra-molecular structure. A weak C-H⋯π inter-action is also found.

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 et al. (2009a ▶,b ▶,c ▶); Özbek et al. (2009 ▶); Sertçelik et al. (2009a ▶,b ▶,c ▶); Tercan et al. (2009 ▶).

Experimental

Crystal data

[Ni(C7H4BrO2)2(C6H6N2O)2(H2O)2]

M = 739.02

Monoclinic,

a = 7.8851 (2) Å

b = 18.2865 (4) Å

c = 9.7574 (3) Å

β = 106.609 (2)°

V = 1348.23 (6) Å3

Z = 2

Mo Kα radiation

μ = 3.74 mm−1

T = 100 K

0.52 × 0.27 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.306, T max = 0.436

12686 measured reflections

3368 independent reflections

2899 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.090

S = 1.06

3368 reflections

203 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.48 e Å−3

Δρmin = −0.55 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/S1600536809021710/xu2538sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021710/xu2538Isup2.hkl

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

[Ni(C7H4BrO2)2(C6H6N2O)2(H2O)2]	F(000) = 740
Mr = 739.02	Dx = 1.820 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5380 reflections
a = 7.8851 (2) Å	θ = 2.5–28.4°
b = 18.2865 (4) Å	µ = 3.74 mm−1
c = 9.7574 (3) Å	T = 100 K
β = 106.609 (2)°	Block, blue
V = 1348.23 (6) Å3	0.52 × 0.27 × 0.22 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	3368 independent reflections
Radiation source: fine-focus sealed tube	2899 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 28.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.306, Tmax = 0.436	k = −24→21
12686 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0538P)2 + 0.96P] where P = (Fo2 + 2Fc2)/3
3368 reflections	(Δ/σ)max < 0.001
203 parameters	Δρmax = 1.48 e Å−3
0 restraints	Δρmin = −0.55 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
Br1	0.40260 (3)	0.212024 (14)	0.17902 (3)	0.02187 (10)
Ni1	0.5000	0.5000	0.5000	0.01048 (11)
O1	0.6201 (2)	0.40537 (9)	0.45455 (18)	0.0137 (3)
O2	0.3946 (2)	0.36790 (10)	0.27275 (19)	0.0162 (4)
O3	0.9542 (2)	0.51033 (10)	0.17931 (19)	0.0184 (4)
O4	0.7554 (2)	0.54252 (10)	0.58888 (19)	0.0149 (4)
H41	0.724 (6)	0.574 (2)	0.643 (4)	0.045 (11)*
H42	0.838 (5)	0.5193 (19)	0.643 (4)	0.024 (8)*
N1	0.5076 (3)	0.54372 (11)	0.3063 (2)	0.0129 (4)
N2	0.8578 (3)	0.57987 (14)	−0.0186 (2)	0.0194 (5)
H21	0.776 (5)	0.6019 (19)	−0.074 (4)	0.034 (10)*
H22	0.935 (5)	0.5647 (18)	−0.048 (4)	0.023 (8)*
C1	0.5546 (3)	0.36682 (13)	0.3452 (2)	0.0126 (4)
C2	0.6793 (3)	0.31957 (13)	0.2910 (3)	0.0130 (4)
C3	0.6274 (3)	0.25649 (14)	0.2082 (3)	0.0138 (5)
C4	0.7416 (3)	0.22059 (13)	0.1454 (3)	0.0160 (5)
H4	0.7036	0.1793	0.0893	0.019*
C5	0.9119 (3)	0.24655 (15)	0.1666 (3)	0.0176 (5)
H5	0.9876	0.2235	0.1227	0.021*
C6	0.9699 (3)	0.30671 (14)	0.2531 (3)	0.0175 (5)
H6	1.0859	0.3230	0.2705	0.021*
C7	0.8537 (3)	0.34266 (13)	0.3137 (3)	0.0143 (5)
H7	0.8934	0.3833	0.3711	0.017*
C8	0.3703 (3)	0.58033 (13)	0.2194 (3)	0.0143 (5)
H8	0.2668	0.5848	0.2464	0.017*
C9	0.3762 (3)	0.61133 (14)	0.0923 (3)	0.0167 (5)
H9	0.2792	0.6367	0.0354	0.020*
C10	0.5299 (3)	0.60410 (14)	0.0504 (3)	0.0159 (5)
H10	0.5376	0.6246	−0.0348	0.019*
C11	0.6709 (3)	0.56580 (13)	0.1378 (3)	0.0131 (5)
C12	0.6545 (3)	0.53690 (13)	0.2651 (3)	0.0134 (5)
H12	0.7500	0.5117	0.3243	0.016*
C13	0.8401 (3)	0.55041 (14)	0.1008 (3)	0.0152 (5)

	U11	U22	U33	U12	U13	U23
Br1	0.01372 (14)	0.01967 (16)	0.03198 (17)	−0.00559 (9)	0.00611 (11)	−0.00455 (10)
Ni1	0.00719 (19)	0.0141 (2)	0.0102 (2)	0.00053 (14)	0.00254 (15)	0.00033 (15)
O1	0.0115 (8)	0.0168 (9)	0.0122 (8)	0.0021 (6)	0.0022 (6)	−0.0009 (6)
O2	0.0082 (7)	0.0226 (10)	0.0164 (8)	0.0018 (6)	0.0015 (6)	−0.0023 (7)
O3	0.0133 (8)	0.0269 (10)	0.0156 (9)	0.0064 (7)	0.0049 (7)	0.0048 (7)
O4	0.0083 (8)	0.0191 (10)	0.0166 (9)	0.0012 (7)	0.0024 (7)	−0.0005 (7)
N1	0.0108 (9)	0.0138 (10)	0.0142 (10)	0.0004 (7)	0.0036 (8)	−0.0001 (8)
N2	0.0131 (10)	0.0324 (13)	0.0143 (10)	0.0074 (9)	0.0063 (9)	0.0062 (9)
C1	0.0105 (10)	0.0152 (12)	0.0126 (11)	0.0013 (8)	0.0043 (9)	0.0026 (9)
C2	0.0103 (10)	0.0143 (12)	0.0143 (11)	0.0018 (8)	0.0034 (9)	0.0015 (9)
C3	0.0102 (10)	0.0162 (12)	0.0137 (11)	−0.0005 (8)	0.0013 (9)	0.0018 (9)
C4	0.0166 (11)	0.0127 (12)	0.0172 (12)	0.0027 (9)	0.0025 (9)	−0.0012 (9)
C5	0.0165 (12)	0.0207 (14)	0.0166 (12)	0.0065 (9)	0.0064 (10)	0.0025 (10)
C6	0.0113 (11)	0.0205 (13)	0.0209 (12)	−0.0004 (9)	0.0051 (10)	0.0010 (10)
C7	0.0110 (10)	0.0149 (12)	0.0165 (11)	0.0010 (8)	0.0031 (9)	0.0005 (9)
C8	0.0095 (10)	0.0163 (12)	0.0167 (11)	0.0020 (8)	0.0029 (9)	0.0001 (9)
C9	0.0093 (10)	0.0211 (13)	0.0175 (12)	0.0051 (9)	0.0002 (9)	0.0043 (10)
C10	0.0132 (11)	0.0224 (13)	0.0130 (11)	0.0022 (9)	0.0052 (9)	0.0032 (9)
C11	0.0117 (11)	0.0146 (12)	0.0139 (11)	0.0007 (8)	0.0051 (9)	−0.0004 (9)
C12	0.0117 (10)	0.0135 (12)	0.0155 (11)	0.0011 (8)	0.0046 (9)	0.0000 (9)
C13	0.0113 (11)	0.0203 (13)	0.0145 (11)	0.0005 (9)	0.0044 (9)	−0.0019 (9)

Br1—C3	1.896 (2)	C3—C4	1.390 (3)
Ni1—O1i	2.0806 (16)	C4—C5	1.383 (4)
Ni1—O1	2.0806 (16)	C4—H4	0.9300
Ni1—O4	2.1012 (17)	C5—C6	1.382 (4)
Ni1—O4i	2.1012 (17)	C5—H5	0.9300
Ni1—N1	2.068 (2)	C6—C7	1.390 (3)
Ni1—N1i	2.068 (2)	C6—H6	0.9300
O1—C1	1.260 (3)	C7—H7	0.9300
O2—C1	1.258 (3)	C8—H8	0.9300
O3—C13	1.241 (3)	C9—C8	1.377 (3)
O4—H41	0.86 (4)	C9—H9	0.9300
O4—H42	0.83 (4)	C10—C9	1.391 (3)
N1—C8	1.347 (3)	C10—H10	0.9300
N1—C12	1.337 (3)	C11—C10	1.383 (3)
N2—H21	0.82 (4)	C11—C12	1.390 (3)
N2—H22	0.79 (4)	C12—H12	0.9300
C1—C2	1.513 (3)	C13—N2	1.327 (3)
C2—C7	1.394 (3)	C13—C11	1.505 (3)
C3—C2	1.400 (4)
O1i—Ni1—O1	180.000 (1)	C4—C3—Br1	115.24 (18)
O1—Ni1—O4	87.40 (7)	C4—C3—C2	121.6 (2)
O1i—Ni1—O4	92.60 (7)	C3—C4—H4	120.2
O1i—Ni1—O4i	87.40 (7)	C5—C4—C3	119.7 (2)
O1—Ni1—O4i	92.60 (7)	C5—C4—H4	120.2
O4—Ni1—O4i	180.00 (10)	C4—C5—H5	119.9
N1—Ni1—O1	89.60 (7)	C6—C5—C4	120.2 (2)
N1i—Ni1—O1	90.40 (7)	C6—C5—H5	119.9
N1—Ni1—O1i	90.40 (7)	C5—C6—C7	119.5 (2)
N1i—Ni1—O1i	89.60 (7)	C5—C6—H6	120.3
N1—Ni1—O4	87.68 (7)	C7—C6—H6	120.3
N1i—Ni1—O4	92.32 (7)	C2—C7—H7	119.0
N1—Ni1—O4i	92.32 (7)	C6—C7—C2	122.0 (2)
N1i—Ni1—O4i	87.68 (7)	C6—C7—H7	119.0
N1—Ni1—N1i	180.00 (10)	N1—C8—C9	123.0 (2)
C1—O1—Ni1	122.99 (15)	N1—C8—H8	118.5
Ni1—O4—H41	95 (3)	C9—C8—H8	118.5
Ni1—O4—H42	124 (2)	C8—C9—C10	118.8 (2)
H42—O4—H41	105 (4)	C8—C9—H9	120.6
C8—N1—Ni1	122.66 (15)	C10—C9—H9	120.6
C12—N1—Ni1	119.53 (16)	C9—C10—H10	120.6
C12—N1—C8	117.8 (2)	C11—C10—C9	118.8 (2)
C13—N2—H21	121 (3)	C11—C10—H10	120.6
C13—N2—H22	118 (2)	C10—C11—C12	118.7 (2)
H21—N2—H22	118 (3)	C10—C11—C13	124.0 (2)
O1—C1—C2	117.8 (2)	C12—C11—C13	117.3 (2)
O2—C1—O1	124.7 (2)	N1—C12—C11	123.0 (2)
O2—C1—C2	117.4 (2)	N1—C12—H12	118.5
C3—C2—C1	124.1 (2)	C11—C12—H12	118.5
C7—C2—C1	118.8 (2)	O3—C13—N2	122.8 (2)
C7—C2—C3	117.0 (2)	O3—C13—C11	119.9 (2)
C2—C3—Br1	123.11 (17)	N2—C13—C11	117.2 (2)
O4—Ni1—O1—C1	−145.89 (18)	C1—C2—C7—C6	−172.5 (2)
O4i—Ni1—O1—C1	34.11 (18)	C3—C2—C7—C6	2.3 (4)
N1—Ni1—O1—C1	−58.20 (18)	Br1—C3—C2—C1	−10.9 (3)
N1i—Ni1—O1—C1	121.80 (18)	Br1—C3—C2—C7	174.53 (17)
O1—Ni1—N1—C8	137.00 (19)	C4—C3—C2—C1	171.3 (2)
O1i—Ni1—N1—C8	−43.00 (19)	C4—C3—C2—C7	−3.2 (4)
O1—Ni1—N1—C12	−44.08 (18)	Br1—C3—C4—C5	−176.67 (19)
O1i—Ni1—N1—C12	135.92 (18)	C2—C3—C4—C5	1.2 (4)
O4—Ni1—N1—C12	43.33 (18)	C3—C4—C5—C6	1.7 (4)
O4i—Ni1—N1—C12	−136.67 (18)	C4—C5—C6—C7	−2.6 (4)
O4—Ni1—N1—C8	−135.59 (19)	C5—C6—C7—C2	0.5 (4)
O4i—Ni1—N1—C8	44.41 (19)	C10—C9—C8—N1	0.7 (4)
Ni1—O1—C1—O2	−19.9 (3)	C11—C10—C9—C8	0.2 (4)
Ni1—O1—C1—C2	155.74 (16)	C12—C11—C10—C9	−0.9 (4)
Ni1—N1—C8—C9	178.11 (19)	C13—C11—C10—C9	176.4 (2)
C12—N1—C8—C9	−0.8 (4)	C10—C11—C12—N1	0.8 (4)
Ni1—N1—C12—C11	−178.89 (18)	C13—C11—C12—N1	−176.7 (2)
C8—N1—C12—C11	0.1 (4)	O3—C13—C11—C10	−173.8 (2)
O1—C1—C2—C3	156.0 (2)	O3—C13—C11—C12	3.5 (4)
O1—C1—C2—C7	−29.6 (3)	N2—C13—C11—C10	4.7 (4)
O2—C1—C2—C3	−28.0 (4)	N2—C13—C11—C12	−178.0 (2)
O2—C1—C2—C7	146.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.82 (4)	2.09 (4)	2.864 (3)	156 (4)
N2—H22···O3iii	0.79 (4)	2.22 (4)	2.951 (3)	153 (4)
O4—H41···O2i	0.86 (4)	1.77 (4)	2.612 (2)	165 (5)
O4—H42···O3iv	0.83 (4)	2.09 (4)	2.886 (2)	162 (3)
C9—H9···Cg1v	0.93	2.89	3.617 (3)	136

Table 1

Selected bond lengths (Å)

Ni1—O1	2.0806 (16)
Ni1—O4	2.1012 (17)
Ni1—N1	2.068 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2i	0.82 (4)	2.09 (4)	2.864 (3)	156 (4)
N2—H22⋯O3ii	0.79 (4)	2.22 (4)	2.951 (3)	153 (4)
O4—H41⋯O2iii	0.86 (4)	1.77 (4)	2.612 (2)	165 (5)
O4—H42⋯O3iv	0.83 (4)	2.09 (4)	2.886 (2)	162 (3)
C9—H9⋯Cg1v	0.93	2.89	3.617 (3)	136

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) . Cg1 is the centroid of the C2–C7 ring.