Diaqua-bis-(4-bromo-benzoato-κO)bis-(nicotinamide-κN)copper(II).

The asymmetric unit of the title mononuclear Cu(II) complex, [Cu(C(7)H(4)BrO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], contains one half-mol-ecule, the Cu(II) atom being located on an inversion center. The unit cell contains two nicotinamide (NA), two 4-bromo-benzoate (PBB) ligands and two coordinated water mol-ecules. The four O atoms in the equatorial plane around the Cu(II) ion 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 22.17 (16)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.80 (6)°. In the crystal, N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. A weak C-H⋯π inter-action is also observed.

Related literature

For literature on niacin, see: Krishnamachari (1974 ▶). For infomation on the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1996 ▶, 2009a ▶,b ▶); Hökelek & Necefoğlu (1998 ▶, 2007 ▶); Necefoğlu et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

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

M = 743.84

Triclinic,

a = 7.7072 (3) Å

b = 9.7536 (5) Å

c = 9.8471 (4) Å

α = 76.273 (2)°

β = 74.240 (2)°

γ = 85.024 (3)°

V = 691.86 (5) Å3

Z = 1

Mo Kα radiation

μ = 3.73 mm−1

T = 100 K

0.41 × 0.38 × 0.35 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.236, T max = 0.271

11758 measured reflections

3515 independent reflections

3172 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.108

S = 1.13

3515 reflections

203 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.86 e Å−3

Δρmin = −1.29 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: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811021696/su2279sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021696/su2279Isup2.hkl

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

[Cu(C7H4BrO2)2(C6H6N2O)2(H2O)2]	Z = 1
Mr = 743.84	F(000) = 371
Triclinic, P1	Dx = 1.785 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7072 (3) Å	Cell parameters from 7694 reflections
b = 9.7536 (5) Å	θ = 2.2–28.7°
c = 9.8471 (4) Å	µ = 3.73 mm−1
α = 76.273 (2)°	T = 100 K
β = 74.240 (2)°	Block, blue
γ = 85.024 (3)°	0.41 × 0.38 × 0.35 mm
V = 691.86 (5) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	3515 independent reflections
Radiation source: fine-focus sealed tube	3172 reflections with I > 2σ(I)
graphite	Rint = 0.057
φ and ω scans	θmax = 28.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.236, Tmax = 0.271	k = −12→13
11758 measured reflections	l = −13→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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0563P)2 + 0.169P] where P = (Fo2 + 2Fc2)/3
3515 reflections	(Δ/σ)max = 0.001
203 parameters	Δρmax = 0.86 e Å−3
0 restraints	Δρmin = −1.29 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 > 2sigma(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	0.50803 (3)	0.60173 (3)	0.78887 (3)	0.02585 (11)
Cu1	0.0000	0.0000	0.5000	0.00979 (12)
O1	0.1042 (2)	0.17464 (16)	0.50913 (16)	0.0123 (3)
O2	−0.1351 (2)	0.26522 (18)	0.64918 (17)	0.0160 (3)
O3	0.4297 (2)	−0.00851 (18)	0.84131 (16)	0.0182 (4)
O4	0.3099 (2)	−0.0838 (2)	0.43625 (18)	0.0172 (4)
H41	0.271 (5)	−0.146 (4)	0.402 (4)	0.036 (9)*
H42	0.383 (5)	−0.042 (4)	0.371 (4)	0.043 (11)*
N1	−0.0003 (2)	−0.08494 (19)	0.70725 (18)	0.0111 (4)
N2	0.3330 (3)	−0.1428 (2)	1.0661 (2)	0.0176 (4)
H21	0.251 (4)	−0.189 (3)	1.134 (3)	0.028 (10)*
H22	0.417 (4)	−0.110 (3)	1.094 (3)	0.016 (7)*
C1	0.0294 (3)	0.2585 (2)	0.5904 (2)	0.0103 (4)
C2	0.1508 (3)	0.3509 (2)	0.6240 (2)	0.0116 (4)
C3	0.0789 (3)	0.4675 (2)	0.6809 (2)	0.0149 (4)
H3	−0.0442	0.4943	0.6883	0.018*
C4	0.1860 (3)	0.5448 (3)	0.7267 (3)	0.0174 (5)
H4	0.1375	0.6251	0.7644	0.021*
C5	0.3644 (3)	0.5032 (2)	0.7167 (2)	0.0145 (4)
C6	0.4403 (3)	0.3898 (2)	0.6570 (2)	0.0158 (5)
H6	0.5638	0.3638	0.6490	0.019*
C7	0.3328 (3)	0.3151 (2)	0.6094 (2)	0.0144 (4)
H7	0.3837	0.2384	0.5663	0.017*
C8	−0.1393 (3)	−0.1592 (2)	0.8002 (2)	0.0132 (4)
H8	−0.2407	−0.1721	0.7675	0.016*
C9	−0.1386 (3)	−0.2178 (3)	0.9430 (2)	0.0170 (5)
H9	−0.2382	−0.2703	1.0072	0.020*
C10	0.0077 (3)	−0.1992 (2)	0.9903 (2)	0.0150 (4)
H10	0.0101	−0.2388	1.0877	0.018*
C11	0.1524 (3)	−0.1221 (2)	0.8948 (2)	0.0109 (4)
C12	0.1421 (3)	−0.0671 (2)	0.7527 (2)	0.0122 (4)
H12	0.2405	−0.0151	0.6859	0.015*
C13	0.3162 (3)	−0.0880 (2)	0.9325 (2)	0.0137 (5)

	U11	U22	U33	U12	U13	U23
Br1	0.02453 (18)	0.03006 (18)	0.03230 (18)	−0.00115 (12)	−0.01163 (13)	−0.01980 (13)
Cu1	0.0109 (2)	0.0129 (2)	0.00714 (19)	0.00162 (14)	−0.00356 (14)	−0.00453 (14)
O1	0.0122 (7)	0.0149 (8)	0.0112 (7)	−0.0005 (6)	−0.0023 (6)	−0.0064 (6)
O2	0.0104 (8)	0.0214 (9)	0.0164 (8)	0.0013 (6)	−0.0016 (6)	−0.0073 (6)
O3	0.0165 (8)	0.0292 (9)	0.0101 (7)	−0.0054 (7)	−0.0030 (6)	−0.0053 (7)
O4	0.0150 (8)	0.0222 (9)	0.0147 (8)	0.0026 (7)	−0.0015 (7)	−0.0085 (7)
N1	0.0115 (9)	0.0131 (9)	0.0100 (8)	0.0037 (7)	−0.0032 (7)	−0.0062 (7)
N2	0.0172 (10)	0.0277 (11)	0.0090 (9)	−0.0027 (9)	−0.0044 (8)	−0.0043 (8)
C1	0.0091 (9)	0.0127 (10)	0.0087 (9)	−0.0004 (7)	−0.0024 (8)	−0.0014 (8)
C2	0.0141 (10)	0.0129 (10)	0.0083 (9)	0.0016 (8)	−0.0027 (8)	−0.0038 (8)
C3	0.0132 (10)	0.0162 (11)	0.0152 (10)	0.0034 (8)	−0.0025 (8)	−0.0057 (9)
C4	0.0200 (12)	0.0152 (11)	0.0189 (11)	0.0042 (9)	−0.0040 (9)	−0.0102 (9)
C5	0.0151 (11)	0.0175 (11)	0.0139 (10)	−0.0030 (8)	−0.0044 (8)	−0.0075 (8)
C6	0.0117 (10)	0.0192 (11)	0.0179 (10)	0.0029 (8)	−0.0045 (9)	−0.0070 (9)
C7	0.0157 (11)	0.0150 (11)	0.0131 (10)	0.0030 (8)	−0.0024 (8)	−0.0072 (8)
C8	0.0112 (10)	0.0169 (11)	0.0129 (10)	0.0037 (8)	−0.0030 (8)	−0.0073 (8)
C9	0.0175 (12)	0.0190 (11)	0.0129 (10)	0.0011 (9)	0.0000 (9)	−0.0055 (9)
C10	0.0153 (11)	0.0189 (11)	0.0097 (9)	0.0008 (9)	−0.0009 (8)	−0.0045 (8)
C11	0.0107 (10)	0.0140 (10)	0.0094 (9)	0.0019 (8)	−0.0025 (8)	−0.0061 (8)
C12	0.0136 (10)	0.0143 (10)	0.0100 (9)	0.0037 (8)	−0.0030 (8)	−0.0065 (8)
C13	0.0153 (11)	0.0187 (11)	0.0090 (10)	0.0043 (9)	−0.0035 (8)	−0.0082 (8)

Br1—C5	1.895 (2)	C3—H3	0.9500
Cu1—O1	1.9756 (16)	C4—C5	1.383 (3)
Cu1—O1i	1.9756 (16)	C4—H4	0.9500
Cu1—N1	2.0116 (16)	C6—C5	1.386 (3)
Cu1—N1i	2.0116 (16)	C6—C7	1.384 (3)
Cu1—O4	2.4199 (16)	C6—H6	0.9500
Cu1—O4i	2.4199 (16)	C7—H7	0.9500
O1—C1	1.272 (3)	C8—N1	1.340 (3)
O2—C1	1.246 (3)	C8—H8	0.9500
O3—C13	1.238 (3)	C9—C8	1.388 (3)
O4—H41	0.87 (4)	C9—H9	0.9500
O4—H42	0.79 (4)	C10—C9	1.371 (3)
N2—C13	1.334 (3)	C10—C11	1.391 (3)
N2—H21	0.85 (3)	C10—H10	0.9500
N2—H22	0.88 (3)	C11—C12	1.396 (3)
C1—C2	1.502 (3)	C11—C13	1.493 (3)
C2—C7	1.393 (3)	C12—N1	1.331 (3)
C3—C2	1.392 (3)	C12—H12	0.9500
C3—C4	1.387 (3)
O1—Cu1—O1i	180.0	C4—C3—C2	120.4 (2)
O1—Cu1—O4	85.01 (6)	C4—C3—H3	119.8
O1i—Cu1—O4	94.99 (6)	C3—C4—H4	120.5
O1—Cu1—O4i	94.99 (6)	C5—C4—C3	119.0 (2)
O1i—Cu1—O4i	85.01 (6)	C5—C4—H4	120.5
O1—Cu1—N1	90.51 (7)	C4—C5—Br1	119.31 (17)
O1i—Cu1—N1	89.49 (7)	C4—C5—C6	121.7 (2)
O1—Cu1—N1i	89.49 (7)	C6—C5—Br1	119.02 (17)
O1i—Cu1—N1i	90.51 (7)	C5—C6—H6	120.6
O4i—Cu1—O4	180.0	C7—C6—C5	118.7 (2)
N1i—Cu1—N1	180.0	C7—C6—H6	120.6
N1—Cu1—O4	86.82 (6)	C2—C7—H7	119.6
N1i—Cu1—O4	93.18 (6)	C6—C7—C2	120.8 (2)
N1—Cu1—O4i	93.18 (6)	C6—C7—H7	119.6
N1i—Cu1—O4i	86.82 (6)	N1—C8—C9	121.6 (2)
C1—O1—Cu1	125.94 (15)	N1—C8—H8	119.2
Cu1—O4—H41	87 (2)	C9—C8—H8	119.2
Cu1—O4—H42	122 (3)	C8—C9—H9	120.4
H41—O4—H42	105 (3)	C10—C9—C8	119.3 (2)
C8—N1—Cu1	121.83 (14)	C10—C9—H9	120.4
C12—N1—Cu1	118.84 (15)	C9—C10—C11	119.6 (2)
C12—N1—C8	119.33 (18)	C9—C10—H10	120.2
C13—N2—H21	124.3 (19)	C11—C10—H10	120.2
C13—N2—H22	118.4 (19)	C10—C11—C12	117.8 (2)
H22—N2—H21	115 (3)	C10—C11—C13	125.52 (19)
O1—C1—C2	117.12 (18)	C12—C11—C13	116.7 (2)
O2—C1—O1	125.2 (2)	N1—C12—C11	122.5 (2)
O2—C1—C2	117.63 (19)	N1—C12—H12	118.8
C3—C2—C1	119.91 (19)	C11—C12—H12	118.8
C3—C2—C7	119.4 (2)	O3—C13—N2	122.1 (2)
C7—C2—C1	120.53 (19)	O3—C13—C11	119.74 (18)
C2—C3—H3	119.8	N2—C13—C11	118.2 (2)
O4—Cu1—O1—C1	−150.09 (16)	C4—C3—C2—C7	−1.9 (3)
O4i—Cu1—O1—C1	29.91 (16)	C2—C3—C4—C5	−0.8 (3)
N1—Cu1—O1—C1	−63.33 (16)	C3—C4—C5—Br1	−176.52 (17)
N1i—Cu1—O1—C1	116.67 (16)	C3—C4—C5—C6	2.5 (4)
O1—Cu1—N1—C12	−42.00 (15)	C7—C6—C5—Br1	177.63 (17)
O1i—Cu1—N1—C12	138.00 (15)	C7—C6—C5—C4	−1.4 (4)
O1—Cu1—N1—C8	138.32 (16)	C5—C6—C7—C2	−1.4 (3)
O1i—Cu1—N1—C8	−41.68 (16)	C9—C8—N1—Cu1	179.86 (16)
O4—Cu1—N1—C12	42.98 (15)	C9—C8—N1—C12	0.2 (3)
O4i—Cu1—N1—C12	−137.02 (15)	C10—C9—C8—N1	0.1 (3)
O4—Cu1—N1—C8	−136.71 (16)	C11—C10—C9—C8	0.0 (3)
O4i—Cu1—N1—C8	43.29 (16)	C9—C10—C11—C12	−0.4 (3)
Cu1—O1—C1—O2	−19.3 (3)	C9—C10—C11—C13	177.1 (2)
Cu1—O1—C1—C2	157.31 (13)	C10—C11—C12—N1	0.7 (3)
O1—C1—C2—C3	164.19 (19)	C13—C11—C12—N1	−177.08 (18)
O1—C1—C2—C7	−20.9 (3)	C10—C11—C13—O3	−174.0 (2)
O2—C1—C2—C3	−19.0 (3)	C10—C11—C13—N2	4.7 (3)
O2—C1—C2—C7	156.0 (2)	C12—C11—C13—O3	3.6 (3)
C1—C2—C7—C6	−171.9 (2)	C12—C11—C13—N2	−177.76 (19)
C3—C2—C7—C6	3.0 (3)	C11—C12—N1—Cu1	179.75 (15)
C4—C3—C2—C1	173.1 (2)	C11—C12—N1—C8	−0.6 (3)

Cg is the centroid of the N1/C8–C12 pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O2ii	0.85 (3)	2.06 (3)	2.831 (2)	151 (3)
N2—H22···O3iii	0.88 (3)	2.03 (3)	2.893 (3)	166 (3)
O4—H41···O2i	0.87 (4)	1.86 (4)	2.718 (2)	167 (4)
O4—H42···O3iv	0.78 (4)	2.17 (4)	2.911 (2)	159 (4)
C6—H6···O2v	0.95	2.43	3.377 (3)	172
C4—H4···Cgvi	0.95	2.63	3.581 (3)	176

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/C8–C12 pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O2i	0.85 (3)	2.06 (3)	2.831 (2)	151 (3)
N2—H22⋯O3ii	0.88 (3)	2.03 (3)	2.893 (3)	166 (3)
O4—H41⋯O2iii	0.87 (4)	1.86 (4)	2.718 (2)	167 (4)
O4—H42⋯O3iv	0.78 (4)	2.17 (4)	2.911 (2)	159 (4)
C6—H6⋯O2v	0.95	2.43	3.377 (3)	172
C4—H4⋯Cgvi	0.95	2.63	3.581 (3)	176

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