Diaqua-bis[2-(4-bromo-phen-yl)acetato]bis-(N,N-dimethyl-pyridin-4-amine)copper(II).

In the title compound, [Cu(C(8)H(6)BrO(2))(2)(C(7)H(10)N(2))(2)(H(2)O)(2)], the Cu(II) atom (site symmetry ) adopts a Jahn-Teller-distorted trans-CuN(2)O(4) octa-hedral coordination, with the aqua O atoms in axially extended sites. An intra-molecular O-H⋯O hydrogen bond helps to establish the conformation and an inter-molecular O-H⋯O hydrogen bond is seen in the crystal packing.

Related literature

For background to coordination networks, see: Liu & Zhu (2004 ▶); Yang et al. (2004 ▶); You et al. (2004 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C8H6BrO2)2(C7H10N2)2(H2O)2]

M = 771.99

Monoclinic,

a = 10.4792 (10) Å

b = 6.1059 (6) Å

c = 25.450 (2) Å

β = 100.958 (4)°

V = 1598.7 (3) Å3

Z = 2

Mo Kα radiation

μ = 3.23 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.499, T max = 0.564

8029 measured reflections

2815 independent reflections

2189 reflections with I > 2σ(I)

R int = 0.026

200 standard reflections every 3 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.099

S = 1.01

2815 reflections

198 parameters

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.71 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034461/hb5065sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034461/hb5065Isup2.hkl

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

[Cu(C8H6BrO2)2(C7H10N2)2(H2O)2]	F(000) = 782
Mr = 771.99	Dx = 1.604 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.4792 (10) Å	θ = 9–12°
b = 6.1059 (6) Å	µ = 3.23 mm−1
c = 25.450 (2) Å	T = 293 K
β = 100.958 (4)°	Block, green
V = 1598.7 (3) Å3	0.25 × 0.20 × 0.20 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	2189 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
graphite	θmax = 25.0°, θmin = 1.6°
ω/2θ scans	h = −10→12
Absorption correction: ψ scan (North et al., 1968)	k = −7→7
Tmin = 0.499, Tmax = 0.564	l = −30→28
8029 measured reflections	200 standard reflections every 3 reflections
2815 independent reflections	intensity decay: 1%

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0539P)2 + 0.7463P] where P = (Fo2 + 2Fc2)/3
2815 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.71 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	0.10163 (4)	0.98365 (8)	0.229572 (18)	0.0870 (2)
C1	0.4910 (3)	0.8264 (4)	0.17361 (10)	0.0366 (6)
C2	0.3209 (3)	0.7210 (6)	0.21980 (12)	0.0567 (9)
H2	0.2854	0.6195	0.2402	0.068*
C3	0.4355 (3)	0.6766 (5)	0.20345 (11)	0.0479 (8)
H3	0.4767	0.5433	0.2126	0.058*
C4	0.3099 (3)	1.0674 (6)	0.17612 (13)	0.0525 (8)
H4	0.2669	1.1991	0.1668	0.063*
C5	0.4259 (3)	1.0225 (5)	0.15993 (13)	0.0462 (8)
H5	0.4608	1.1250	0.1396	0.055*
C6	0.2591 (3)	0.9156 (6)	0.20593 (12)	0.0492 (8)
C7	0.6186 (3)	0.7783 (5)	0.15678 (10)	0.0411 (7)
H7A	0.6807	0.7252	0.1873	0.049*
H7B	0.6529	0.9121	0.1443	0.049*
C10	0.6013 (3)	0.6071 (5)	0.11224 (10)	0.0354 (6)
C12	0.1011 (3)	0.4106 (5)	0.06736 (10)	0.0354 (6)
C13	0.1512 (3)	0.2454 (5)	0.03830 (11)	0.0410 (7)
H13	0.1083	0.1117	0.0324	0.049*
C14	0.2815 (3)	0.6273 (4)	0.05081 (11)	0.0373 (6)
H14	0.3254	0.7605	0.0548	0.045*
C15	0.2618 (3)	0.2798 (5)	0.01872 (11)	0.0392 (7)
H15	0.2918	0.1658	0.0001	0.047*
C16	0.1726 (3)	0.6080 (5)	0.07202 (11)	0.0393 (7)
H16	0.1447	0.7264	0.0899	0.047*
C17	−0.0511 (4)	0.5523 (6)	0.12039 (17)	0.0694 (11)
H17A	0.0206	0.6143	0.1450	0.104*
H17B	−0.1126	0.4918	0.1399	0.104*
H17C	−0.0924	0.6644	0.0966	0.104*
C19	−0.0777 (3)	0.1795 (6)	0.08259 (15)	0.0640 (10)
H19A	−0.1167	0.1622	0.0455	0.096*
H19B	−0.1445	0.1841	0.1037	0.096*
H19C	−0.0207	0.0583	0.0939	0.096*
Cu1	0.5000	0.5000	0.0000	0.03234 (15)
N1	−0.0042 (2)	0.3814 (4)	0.08968 (10)	0.0462 (6)
N2	0.3302 (2)	0.4658 (3)	0.02439 (9)	0.0331 (5)
O1	0.6222 (2)	0.4143 (4)	0.12444 (8)	0.0570 (6)
O2	0.56545 (17)	0.6809 (3)	0.06509 (7)	0.0372 (4)
O3	0.58520 (19)	0.1416 (3)	0.03998 (7)	0.0469 (5)
H3B	0.5591	0.0050	0.0463	0.056*
H3A	0.6011	0.2105	0.0727	0.056*

	U11	U22	U33	U12	U13	U23
Br1	0.0564 (3)	0.1343 (5)	0.0770 (3)	−0.0039 (2)	0.0294 (2)	−0.0350 (3)
C1	0.0497 (17)	0.0354 (15)	0.0256 (13)	−0.0051 (13)	0.0092 (12)	−0.0073 (11)
C2	0.069 (2)	0.065 (2)	0.0416 (17)	−0.0128 (19)	0.0260 (16)	0.0034 (15)
C3	0.065 (2)	0.0413 (17)	0.0386 (15)	0.0014 (16)	0.0123 (15)	0.0054 (13)
C4	0.061 (2)	0.0482 (18)	0.0505 (18)	0.0102 (17)	0.0149 (16)	−0.0055 (15)
C5	0.060 (2)	0.0394 (18)	0.0421 (16)	−0.0025 (15)	0.0167 (15)	−0.0010 (13)
C6	0.0488 (18)	0.064 (2)	0.0388 (16)	−0.0027 (17)	0.0171 (14)	−0.0152 (15)
C7	0.0470 (17)	0.0440 (17)	0.0323 (14)	−0.0046 (14)	0.0080 (12)	−0.0083 (12)
C10	0.0345 (15)	0.0392 (17)	0.0358 (15)	−0.0073 (13)	0.0155 (12)	−0.0071 (12)
C12	0.0330 (14)	0.0396 (15)	0.0348 (14)	−0.0011 (13)	0.0093 (12)	0.0013 (12)
C13	0.0413 (16)	0.0349 (15)	0.0505 (16)	−0.0085 (13)	0.0177 (13)	−0.0096 (13)
C14	0.0407 (15)	0.0298 (15)	0.0447 (16)	−0.0029 (12)	0.0164 (13)	−0.0063 (12)
C15	0.0437 (16)	0.0334 (15)	0.0452 (16)	−0.0045 (13)	0.0199 (13)	−0.0103 (12)
C16	0.0405 (16)	0.0337 (16)	0.0477 (16)	0.0018 (13)	0.0188 (13)	−0.0063 (13)
C17	0.062 (2)	0.073 (2)	0.087 (3)	−0.0086 (19)	0.048 (2)	−0.017 (2)
C19	0.054 (2)	0.067 (2)	0.079 (2)	−0.0204 (18)	0.0334 (18)	−0.0083 (19)
Cu1	0.0321 (3)	0.0372 (3)	0.0304 (3)	−0.0056 (2)	0.01259 (19)	−0.00735 (18)
N1	0.0408 (14)	0.0468 (15)	0.0572 (15)	−0.0077 (12)	0.0249 (12)	−0.0071 (12)
N2	0.0355 (12)	0.0318 (13)	0.0351 (12)	−0.0014 (10)	0.0143 (10)	−0.0048 (9)
O1	0.0861 (18)	0.0371 (12)	0.0473 (12)	−0.0003 (12)	0.0116 (11)	−0.0025 (10)
O2	0.0436 (11)	0.0381 (11)	0.0317 (10)	−0.0060 (9)	0.0114 (8)	−0.0075 (8)
O3	0.0602 (13)	0.0386 (11)	0.0438 (11)	−0.0036 (10)	0.0146 (9)	−0.0017 (9)

Br1—C6	1.906 (3)	C14—N2	1.347 (3)
C1—C3	1.386 (4)	C14—C16	1.357 (4)
C1—C5	1.389 (4)	C14—H14	0.9300
C1—C7	1.508 (4)	C15—N2	1.336 (3)
C2—C6	1.367 (5)	C15—H15	0.9300
C2—C3	1.371 (4)	C16—H16	0.9300
C2—H2	0.9300	C17—N1	1.445 (4)
C3—H3	0.9300	C17—H17A	0.9600
C4—C6	1.368 (5)	C17—H17B	0.9600
C4—C5	1.384 (5)	C17—H17C	0.9600
C4—H4	0.9300	C19—N1	1.447 (4)
C5—H5	0.9300	C19—H19A	0.9600
C7—C10	1.527 (4)	C19—H19B	0.9600
C7—H7A	0.9700	C19—H19C	0.9600
C7—H7B	0.9700	Cu1—O2i	2.0006 (17)
C10—O1	1.226 (4)	Cu1—O2	2.0006 (17)
C10—O2	1.270 (3)	Cu1—N2	2.004 (2)
C12—N1	1.345 (3)	Cu1—N2i	2.004 (2)
C12—C13	1.410 (4)	Cu1—O3	2.5052 (19)
C12—C16	1.412 (4)	Cu1—O3i	2.5052 (19)
C13—C15	1.362 (4)	O3—H3B	0.9018
C13—H13	0.9300	O3—H3A	0.9200
C3—C1—C5	117.9 (3)	C14—C16—C12	120.9 (3)
C3—C1—C7	121.0 (3)	C14—C16—H16	119.6
C5—C1—C7	121.1 (3)	C12—C16—H16	119.6
C6—C2—C3	119.5 (3)	N1—C17—H17A	109.5
C6—C2—H2	120.2	N1—C17—H17B	109.5
C3—C2—H2	120.2	H17A—C17—H17B	109.5
C2—C3—C1	121.3 (3)	N1—C17—H17C	109.5
C2—C3—H3	119.4	H17A—C17—H17C	109.5
C1—C3—H3	119.4	H17B—C17—H17C	109.5
C6—C4—C5	119.2 (3)	N1—C19—H19A	109.5
C6—C4—H4	120.4	N1—C19—H19B	109.5
C5—C4—H4	120.4	H19A—C19—H19B	109.5
C4—C5—C1	120.9 (3)	N1—C19—H19C	109.5
C4—C5—H5	119.5	H19A—C19—H19C	109.5
C1—C5—H5	119.5	H19B—C19—H19C	109.5
C2—C6—C4	121.1 (3)	O2i—Cu1—O2	180.00 (6)
C2—C6—Br1	120.3 (3)	O2i—Cu1—N2	90.81 (8)
C4—C6—Br1	118.6 (3)	O2—Cu1—N2	89.19 (8)
C1—C7—C10	111.0 (2)	O2i—Cu1—N2i	89.19 (8)
C1—C7—H7A	109.4	O2—Cu1—N2i	90.81 (8)
C10—C7—H7A	109.4	N2—Cu1—N2i	180.00 (11)
C1—C7—H7B	109.4	O2—Cu1—O3	96.11 (7)
C10—C7—H7B	109.4	O2—Cu1—O3i	83.89 (7)
H7A—C7—H7B	108.0	O3—Cu1—N2	92.98 (7)
O1—C10—O2	125.9 (2)	O3—Cu1—O2i	83.89 (7)
O1—C10—C7	118.6 (2)	O3—Cu1—O3i	180.00 (7)
O2—C10—C7	115.5 (2)	O3—Cu1—N2i	87.02 (7)
N1—C12—C13	122.9 (3)	N2—Cu1—O3i	87.02 (7)
N1—C12—C16	122.8 (3)	O2i—Cu1—O3i	96.11 (7)
C13—C12—C16	114.2 (2)	O3i—Cu1—N2i	92.98 (7)
C15—C13—C12	120.6 (3)	C12—N1—C17	121.5 (3)
C15—C13—H13	119.7	C12—N1—C19	121.4 (3)
C12—C13—H13	119.7	C17—N1—C19	117.1 (3)
N2—C14—C16	124.2 (3)	C15—N2—C14	115.4 (2)
N2—C14—H14	117.9	C15—N2—Cu1	123.04 (18)
C16—C14—H14	117.9	C14—N2—Cu1	121.40 (18)
N2—C15—C13	124.6 (2)	C10—O2—Cu1	125.44 (18)
N2—C15—H15	117.7	H3B—O3—H3A	105.6
C13—C15—H15	117.7

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O2ii	0.90	2.03	2.901 (3)	161
O3—H3A···O1	0.92	1.79	2.688 (3)	163

Table 1

Selected bond lengths (Å)

Cu1—O2	2.0006 (17)
Cu1—N2	2.004 (2)
Cu1—O3	2.5052 (19)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O2i	0.90	2.03	2.901 (3)	161
O3—H3A⋯O1	0.92	1.79	2.688 (3)	163

Symmetry code: (i) .