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

In the monomeric centrosymmetric title Ni(II) complex, [Ni(C(7)H(4)BrO(2))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], the Ni(II) ion is located on an inversion center. The asymmetric unit contains one 2-bromo-benzoate ligand, one diethyl-nicotinamide (DENA) ligand and one coordinated water mol-ecule. 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 N atoms of two DENA ligands in the axial positions. The dihedral angle between the benzene ring and the attached carboxyl-ate group is 87.73 (15)°, while the pyridine and benzene rings are oriented at a dihedral angle of 42.48 (7)°. In the crystal structure, O-H⋯O hydrogen bonds link the mol-ecules into a two-dimensional network parallel to (10). In addition, C-H⋯O hydrogen bonds are observed.

Related literature

For general backgroud, see: Antolini et al. (1982 ▶); Bigoli et al. (1972 ▶); Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For related structures, see: Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶); Özbek et al. (2009 ▶); Sertçelik et al. (2009a ▶,b ▶,c ▶); Tercan et al. (2009 ▶).

Experimental

Crystal data

[Ni(C7H4BrO2)2(C10H14N2O)2(H2O)2]

M = 851.22

Monoclinic,

a = 12.8506 (3) Å

b = 10.3448 (2) Å

c = 14.9418 (4) Å

β = 114.004 (2)°

V = 1814.53 (8) Å3

Z = 2

Mo Kα radiation

μ = 2.79 mm−1

T = 100 K

0.34 × 0.25 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.442, T max = 0.710

16814 measured reflections

4528 independent reflections

3603 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.078

S = 1.04

4528 reflections

233 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.78 e Å−3

Δρmin = −0.78 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/S1600536809021795/ci2824sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021795/ci2824Isup2.hkl

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

[Ni(C7H4BrO2)2(C10H14N2O)2(H2O)2]	F(000) = 868
Mr = 851.22	Dx = 1.558 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5301 reflections
a = 12.8506 (3) Å	θ = 2.5–28.3°
b = 10.3448 (2) Å	µ = 2.79 mm−1
c = 14.9418 (4) Å	T = 100 K
β = 114.004 (2)°	Block, blue
V = 1814.53 (8) Å3	0.34 × 0.25 × 0.12 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	4528 independent reflections
Radiation source: fine-focus sealed tube	3603 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 28.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→17
Tmin = 0.442, Tmax = 0.710	k = −13→13
16814 measured reflections	l = −19→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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0334P)2 + 0.7499P] where P = (Fo2 + 2Fc2)/3
4528 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.78 e Å−3
0 restraints	Δρmin = −0.77 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	0.17947 (2)	0.14287 (2)	0.072440 (17)	0.02619 (8)
Ni1	0.5000	0.0000	0.0000	0.01120 (9)
O1	0.46945 (12)	0.05353 (14)	0.11821 (10)	0.0154 (3)
O2	0.37193 (16)	−0.11792 (15)	0.13480 (13)	0.0270 (4)
O3	0.07077 (13)	0.11718 (14)	−0.39530 (10)	0.0173 (3)
O4	0.61679 (13)	0.15121 (15)	0.03504 (12)	0.0146 (3)
H41	0.607 (3)	0.219 (3)	0.056 (2)	0.036 (9)*
H42	0.621 (3)	0.159 (3)	−0.015 (3)	0.040 (9)*
N1	0.36374 (15)	0.12018 (16)	−0.08963 (12)	0.0134 (4)
N2	0.01992 (15)	−0.00539 (17)	−0.29453 (12)	0.0167 (4)
C1	0.41035 (18)	−0.0066 (2)	0.15502 (15)	0.0156 (4)
C2	0.38690 (18)	0.0695 (2)	0.23103 (15)	0.0163 (4)
C3	0.29000 (19)	0.1455 (2)	0.20453 (16)	0.0196 (4)
C4	0.2709 (2)	0.2248 (2)	0.27162 (17)	0.0247 (5)
H4	0.2060	0.2761	0.2521	0.030*
C5	0.3501 (2)	0.2258 (2)	0.36754 (18)	0.0278 (5)
H5	0.3394	0.2799	0.4128	0.033*
C6	0.4451 (2)	0.1473 (2)	0.39693 (18)	0.0269 (5)
H6	0.4967	0.1462	0.4622	0.032*
C7	0.4636 (2)	0.0699 (2)	0.32851 (16)	0.0217 (5)
H7	0.5281	0.0178	0.3484	0.026*
C8	0.36086 (18)	0.2475 (2)	−0.07399 (15)	0.0158 (4)
H8	0.4205	0.2842	−0.0210	0.019*
C9	0.27291 (18)	0.3269 (2)	−0.13331 (16)	0.0173 (4)
H9	0.2747	0.4151	−0.1207	0.021*
C10	0.18249 (17)	0.2735 (2)	−0.21145 (15)	0.0161 (4)
H10	0.1233	0.3249	−0.2531	0.019*
C11	0.18272 (17)	0.1406 (2)	−0.22590 (14)	0.0142 (4)
C12	0.27482 (17)	0.0686 (2)	−0.16478 (14)	0.0142 (4)
H12	0.2753	−0.0197	−0.1762	0.017*
C13	0.08624 (17)	0.08196 (19)	−0.31130 (15)	0.0139 (4)
C14	−0.07886 (18)	−0.0564 (2)	−0.37834 (16)	0.0187 (4)
H14A	−0.0945	−0.1439	−0.3640	0.022*
H14B	−0.0611	−0.0595	−0.4355	0.022*
C15	−0.18402 (19)	0.0266 (2)	−0.40082 (18)	0.0251 (5)
H15A	−0.2463	−0.0081	−0.4566	0.038*
H15B	−0.1687	0.1133	−0.4148	0.038*
H15C	−0.2036	0.0270	−0.3453	0.038*
C16	0.0277 (2)	−0.0429 (2)	−0.19692 (16)	0.0259 (5)
H16A	−0.0472	−0.0364	−0.1961	0.031*
H16B	0.0776	0.0171	−0.1486	0.031*
C17	0.0725 (2)	−0.1794 (3)	−0.16850 (19)	0.0348 (6)
H17A	0.0684	−0.2022	−0.1077	0.052*
H17B	0.1502	−0.1836	−0.1611	0.052*
H17C	0.0271	−0.2385	−0.2187	0.052*

	U11	U22	U33	U12	U13	U23
Br1	0.02396 (13)	0.03283 (15)	0.02130 (13)	0.00577 (10)	0.00871 (9)	0.00345 (10)
Ni1	0.01157 (17)	0.01200 (18)	0.00955 (17)	−0.00007 (13)	0.00379 (13)	−0.00031 (13)
O1	0.0171 (7)	0.0169 (7)	0.0139 (7)	−0.0024 (6)	0.0080 (6)	−0.0022 (6)
O2	0.0446 (11)	0.0170 (8)	0.0312 (9)	−0.0089 (7)	0.0275 (8)	−0.0057 (7)
O3	0.0209 (8)	0.0158 (7)	0.0119 (7)	−0.0003 (6)	0.0032 (6)	0.0022 (6)
O4	0.0173 (7)	0.0128 (8)	0.0139 (8)	−0.0008 (6)	0.0065 (6)	−0.0006 (6)
N1	0.0146 (8)	0.0135 (8)	0.0118 (8)	0.0001 (7)	0.0052 (7)	0.0011 (6)
N2	0.0174 (9)	0.0198 (9)	0.0112 (8)	−0.0032 (7)	0.0041 (7)	−0.0005 (7)
C1	0.0171 (10)	0.0166 (10)	0.0142 (10)	0.0028 (8)	0.0077 (8)	0.0016 (8)
C2	0.0209 (10)	0.0153 (11)	0.0184 (10)	−0.0030 (8)	0.0137 (9)	−0.0019 (8)
C3	0.0225 (11)	0.0203 (11)	0.0185 (11)	−0.0006 (9)	0.0110 (9)	0.0011 (9)
C4	0.0306 (13)	0.0230 (12)	0.0286 (13)	0.0011 (10)	0.0203 (11)	−0.0026 (10)
C5	0.0391 (14)	0.0261 (13)	0.0279 (13)	−0.0078 (11)	0.0237 (11)	−0.0110 (10)
C6	0.0300 (13)	0.0343 (14)	0.0189 (11)	−0.0101 (11)	0.0126 (10)	−0.0063 (10)
C7	0.0194 (11)	0.0260 (12)	0.0215 (11)	−0.0024 (9)	0.0101 (9)	−0.0025 (9)
C8	0.0172 (10)	0.0155 (10)	0.0142 (10)	−0.0013 (8)	0.0058 (8)	−0.0013 (8)
C9	0.0199 (10)	0.0128 (10)	0.0180 (10)	−0.0001 (8)	0.0064 (8)	−0.0002 (8)
C10	0.0159 (10)	0.0175 (10)	0.0135 (10)	0.0029 (8)	0.0046 (8)	0.0027 (8)
C11	0.0153 (10)	0.0159 (10)	0.0111 (9)	−0.0013 (8)	0.0052 (8)	0.0006 (8)
C12	0.0154 (10)	0.0146 (10)	0.0127 (10)	−0.0003 (8)	0.0058 (8)	0.0002 (8)
C13	0.0137 (9)	0.0109 (9)	0.0144 (10)	0.0021 (8)	0.0029 (8)	0.0009 (8)
C14	0.0189 (10)	0.0185 (11)	0.0161 (10)	−0.0049 (9)	0.0043 (8)	−0.0026 (8)
C15	0.0193 (11)	0.0290 (13)	0.0235 (12)	0.0002 (9)	0.0052 (9)	0.0036 (10)
C16	0.0253 (12)	0.0369 (14)	0.0144 (10)	−0.0126 (10)	0.0069 (9)	0.0000 (10)
C17	0.0284 (13)	0.0422 (16)	0.0254 (13)	−0.0081 (12)	0.0022 (11)	0.0177 (11)

Br1—C3	1.906 (2)	C7—H7	0.93
Ni1—O1	2.0359 (14)	C8—N1	1.341 (3)
Ni1—O1i	2.0359 (14)	C8—H8	0.93
Ni1—O4	2.0818 (15)	C9—C8	1.387 (3)
Ni1—O4i	2.0818 (15)	C9—H9	0.93
Ni1—N1	2.1207 (17)	C10—C9	1.384 (3)
Ni1—N1i	2.1207 (17)	C10—H10	0.93
O1—C1	1.267 (3)	C11—C10	1.392 (3)
O2—C1	1.240 (3)	C11—C12	1.382 (3)
O3—C13	1.243 (2)	C11—C13	1.499 (3)
O4—H41	0.80 (3)	C12—N1	1.344 (3)
O4—H42	0.78 (3)	C12—H12	0.93
N2—C13	1.334 (3)	C14—C15	1.519 (3)
N2—C14	1.471 (3)	C14—H14A	0.97
N2—C16	1.473 (3)	C14—H14B	0.97
C2—C1	1.510 (3)	C15—H15A	0.96
C2—C7	1.387 (3)	C15—H15B	0.96
C3—C2	1.387 (3)	C15—H15C	0.96
C3—C4	1.392 (3)	C16—C17	1.518 (4)
C4—C5	1.379 (3)	C16—H16A	0.97
C4—H4	0.93	C16—H16B	0.97
C5—H5	0.93	C17—H17A	0.96
C6—C5	1.381 (4)	C17—H17B	0.96
C6—C7	1.393 (3)	C17—H17C	0.96
C6—H6	0.93
O1—Ni1—O1i	180.00 (7)	C2—C7—H7	119.6
O1—Ni1—O4	87.20 (6)	C6—C7—H7	119.6
O1i—Ni1—O4	92.80 (6)	N1—C8—C9	122.93 (19)
O1—Ni1—O4i	92.80 (6)	N1—C8—H8	118.5
O1i—Ni1—O4i	87.20 (6)	C9—C8—H8	118.5
O1—Ni1—N1	89.27 (6)	C8—C9—H9	120.4
O1i—Ni1—N1	90.73 (6)	C10—C9—C8	119.3 (2)
O1—Ni1—N1i	90.73 (6)	C10—C9—H9	120.4
O1i—Ni1—N1i	89.27 (6)	C9—C10—C11	118.11 (19)
O4i—Ni1—O4	180.00 (9)	C9—C10—H10	120.9
O4—Ni1—N1	92.52 (6)	C11—C10—H10	120.9
O4i—Ni1—N1	87.48 (6)	C10—C11—C13	118.60 (18)
O4—Ni1—N1i	87.48 (6)	C12—C11—C10	119.01 (19)
O4i—Ni1—N1i	92.52 (6)	C12—C11—C13	122.28 (18)
N1i—Ni1—N1	180.00 (16)	N1—C12—C11	123.15 (19)
C1—O1—Ni1	127.15 (13)	N1—C12—H12	118.4
Ni1—O4—H41	123 (2)	C11—C12—H12	118.4
Ni1—O4—H42	99 (2)	O3—C13—N2	122.44 (18)
H41—O4—H42	112 (3)	O3—C13—C11	118.57 (18)
C8—N1—Ni1	122.69 (14)	N2—C13—C11	118.99 (18)
C8—N1—C12	117.44 (18)	N2—C14—C15	111.57 (18)
C12—N1—Ni1	119.87 (14)	N2—C14—H14A	109.3
C13—N2—C14	118.61 (17)	N2—C14—H14B	109.3
C13—N2—C16	124.98 (18)	C15—C14—H14A	109.3
C14—N2—C16	115.85 (18)	C15—C14—H14B	109.3
O1—C1—C2	114.11 (18)	H14A—C14—H14B	108.0
O2—C1—O1	126.8 (2)	C14—C15—H15A	109.5
O2—C1—C2	119.06 (19)	C14—C15—H15B	109.5
C3—C2—C1	120.77 (19)	C14—C15—H15C	109.5
C7—C2—C1	121.2 (2)	H15A—C15—H15B	109.5
C7—C2—C3	118.0 (2)	H15A—C15—H15C	109.5
C2—C3—Br1	119.46 (17)	H15B—C15—H15C	109.5
C2—C3—C4	121.9 (2)	N2—C16—C17	112.8 (2)
C4—C3—Br1	118.60 (18)	N2—C16—H16A	109.0
C3—C4—H4	120.6	N2—C16—H16B	109.0
C5—C4—C3	118.8 (2)	C17—C16—H16A	109.0
C5—C4—H4	120.6	C17—C16—H16B	109.0
C5—C6—C7	119.8 (2)	H16A—C16—H16B	107.8
C5—C6—H6	120.1	C16—C17—H17A	109.5
C7—C6—H6	120.1	C16—C17—H17B	109.5
C4—C5—C6	120.6 (2)	C16—C17—H17C	109.5
C4—C5—H5	119.7	H17A—C17—H17B	109.5
C6—C5—H5	119.7	H17A—C17—H17C	109.5
C2—C7—C6	120.8 (2)	H17B—C17—H17C	109.5
O4i—Ni1—O1—C1	8.54 (17)	C1—C2—C7—C6	175.5 (2)
O4—Ni1—O1—C1	−171.46 (17)	C3—C2—C7—C6	−1.8 (3)
N1i—Ni1—O1—C1	−84.02 (17)	Br1—C3—C2—C1	5.0 (3)
N1—Ni1—O1—C1	95.98 (17)	Br1—C3—C2—C7	−177.63 (16)
O1—Ni1—N1—C8	58.46 (17)	C4—C3—C2—C1	−174.6 (2)
O1i—Ni1—N1—C8	−121.54 (17)	C4—C3—C2—C7	2.7 (3)
O1—Ni1—N1—C12	−120.53 (16)	Br1—C3—C4—C5	179.28 (18)
O1i—Ni1—N1—C12	59.47 (16)	C2—C3—C4—C5	−1.1 (4)
O4i—Ni1—N1—C8	151.29 (17)	C3—C4—C5—C6	−1.5 (4)
O4—Ni1—N1—C8	−28.71 (17)	C5—C6—C7—C2	−0.7 (4)
O4i—Ni1—N1—C12	−27.70 (16)	C7—C6—C5—C4	2.4 (4)
O4—Ni1—N1—C12	152.30 (16)	C9—C8—N1—C12	−2.1 (3)
Ni1—O1—C1—O2	10.3 (3)	C9—C8—N1—Ni1	178.91 (16)
Ni1—O1—C1—C2	−169.71 (13)	C10—C9—C8—N1	1.1 (3)
C14—N2—C13—O3	−3.5 (3)	C11—C10—C9—C8	1.4 (3)
C14—N2—C13—C11	176.21 (18)	C12—C11—C10—C9	−2.8 (3)
C16—N2—C13—O3	−174.5 (2)	C13—C11—C10—C9	−179.0 (2)
C16—N2—C13—C11	5.1 (3)	C10—C11—C12—N1	1.9 (3)
C13—N2—C14—C15	−88.5 (2)	C13—C11—C12—N1	177.95 (19)
C16—N2—C14—C15	83.4 (2)	C10—C11—C13—O3	61.2 (3)
C13—N2—C16—C17	−110.3 (2)	C10—C11—C13—N2	−118.5 (2)
C14—N2—C16—C17	78.4 (2)	C12—C11—C13—O3	−114.9 (2)
C3—C2—C1—O2	−88.9 (3)	C12—C11—C13—N2	65.5 (3)
C7—C2—C1—O2	93.8 (3)	C11—C12—N1—C8	0.5 (3)
C3—C2—C1—O1	91.1 (2)	C11—C12—N1—Ni1	179.58 (16)
C7—C2—C1—O1	−86.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O3ii	0.80 (3)	1.97 (3)	2.770 (2)	176 (4)
O4—H42···O2i	0.78 (4)	1.88 (4)	2.623 (3)	161 (3)
C4—H4···O2iii	0.93	2.54	3.172 (3)	126
C8—H8···O3ii	0.93	2.31	3.241 (3)	177
C10—H10···O1iv	0.93	2.47	3.392 (3)	172
C14—H14A···O2v	0.97	2.50	3.448 (3)	166
C14—H14B···O3vi	0.97	2.55	3.483 (3)	161

Table 1

Selected bond lengths (Å)

Ni1—O1	2.0359 (14)
Ni1—O4	2.0818 (15)
Ni1—N1	2.1207 (17)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O3i	0.80 (3)	1.97 (3)	2.770 (2)	176 (4)
O4—H42⋯O2ii	0.78 (4)	1.88 (4)	2.623 (3)	161 (3)
C4—H4⋯O2iii	0.93	2.54	3.172 (3)	126
C8—H8⋯O3i	0.93	2.31	3.241 (3)	177
C10—H10⋯O1iv	0.93	2.47	3.392 (3)	172
C14—H14A⋯O2v	0.97	2.50	3.448 (3)	166
C14—H14B⋯O3vi	0.97	2.55	3.483 (3)	161

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