Diaqua­bis[2-(4-bromo­phen­yl)acetato]bis­(N4,N4-dimethyl­pyridin-4-amine)copper(II)

Cui, Y.-M.; Dai, X.-B.; Zha, R.-H.; Zeng, Q.-F.

doi:10.1107/S1600536809034461

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1163

doi:10.1107/S1600536809034461

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Diaquabis[2-(4-bromophenyl)acetato]bis(N⁴,N⁴-dimethylpyridin-4-amine)copper(II)

Yong-Ming Cui,^a Xi-Bin Dai,^a Ru-Hua Zha ^a and Qing-Fu Zeng ^a ^*

^aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: qfzeng@wuse.edu.cn

(Received 24 August 2009; accepted 28 August 2009; online 5 September 2009)

In the title compound, [Cu(C₈H₆BrO₂)₂(C₇H₁₀N₂)₂(H₂O)₂], the Cu^II atom (site symmetry $[\overline{1}]$ ) adopts a Jahn–Teller-distorted trans-CuN₂O₄ octahedral coordination, with the aqua O atoms in axially extended sites. An intramolecular O—H⋯O hydrogen bond helps to establish the conformation and an intermolecular 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_r = 771.99
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.099
S = 1.01
2815 reflections
198 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.71 e Å⁻³

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) x, y-1, z.

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.

Supporting information

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

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

checkCIF report

Comment top

There has been much research interest in the acid and amine metal complexes due to their molecular architectures (Liu et al., 2004; Yang et al., 2004; You et al., 2004). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The Cu^II atom is six-coordinated by two N atoms from N,N-dimethylpyridin-4-amine, two O atoms from 2-(4-bromophenyl)acetic acid and two O atoms from the water molecules, forming a distorted octahedral coordination.

Related literature top

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

Experimental top

A mixture of N,N-dimethylpyridin-4-amine (244 mg, 2 mmol), 2-(4-bromophenyl)acetic acid (428 mg, 2 mmol) and CuCl₂.2H₂O (169 mg, 1 mmol) in methanol (10 ml) was stirred for 3 h. After keeping the filtrate in air for 7 d, green blocks of (I) were formed.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids. Atoms with the suffix A are generated by the symmetry operation (1–x, 1–y, –z).

Diaquabis[2-(4-bromophenyl)acetato]bis(N⁴,N⁴- dimethylpyridin-4-amine)copper(II) top

Crystal data top

[Cu(C₈H₆BrO₂)₂(C₇H₁₀N₂)₂(H₂O)₂]	F(000) = 782
M_r = 771.99	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0539P)² + 0.7463P] where P = (F_o² + 2F_c²)/3
2815 reflections	(Δ/σ)_max < 0.001
198 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

[Cu(C₈H₆BrO₂)₂(C₇H₁₀N₂)₂(H₂O)₂]	V = 1598.7 (3) Å³
M_r = 771.99	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4792 (10) Å	µ = 3.23 mm⁻¹
b = 6.1059 (6) Å	T = 293 K
c = 25.450 (2) Å	0.25 × 0.20 × 0.20 mm
β = 100.958 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2189 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.026
T_min = 0.499, T_max = 0.564	200 standard reflections every 3 reflections
8029 measured reflections	intensity decay: 1%
2815 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.01	Δρ_max = 0.60 e Å⁻³
2815 reflections	Δρ_min = −0.71 e Å⁻³
198 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₆BrO₂)₂(C₇H₁₀N₂)₂(H₂O)₂]
M_r	771.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.4792 (10), 6.1059 (6), 25.450 (2)
β (°)	100.958 (4)
V (Å³)	1598.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.23
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.499, 0.564
No. of measured, independent and observed [I > 2σ(I)] reflections	8029, 2815, 2189
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.099, 1.01
No. of reflections	2815
No. of parameters	198
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.71

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

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) x, y−1, z.

Acknowledgements

The project was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, Educational Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

References

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Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
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