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Acta Cryst. (2009). E65, m1163    [ doi:10.1107/S1600536809034461 ]

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

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

Abstract top

In the title compound, [Cu(C8H6BrO2)2(C7H10N2)2(H2O)2], the CuII 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.

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 CuII 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.

Refinement top

All H atoms were positioned geometrically (C—H = 0.93 Å for the aromatic H atoms and C—H = 0.96 Å for the aliphatic H atoms) and were refined as riding, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.2Ueq(N).

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
[Figure 1] 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
Mr = 771.99Dx = 1.604 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 10.4792 (10) Åθ = 9–12°
b = 6.1059 (6) ŵ = 3.23 mm−1
c = 25.450 (2) ÅT = 293 K
β = 100.958 (4)°Block, green
V = 1598.7 (3) Å30.25 × 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 tubeRint = 0.026
graphiteθmax = 25.0°, θmin = 1.6°
ω/2θ scansh = −10→12
Absorption correction: ψ scan
(North et al., 1968)		k = −7→7
Tmin = 0.499, Tmax = 0.564l = −30→28
8029 measured reflections200 standard reflections every 3 reflections
2815 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-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 parametersΔρmax = 0.60 e Å−3
0 restraintsΔρmin = −0.71 e Å−3
Crystal data top
[Cu(C8H6BrO2)2(C7H10N2)2(H2O)2]V = 1598.7 (3) Å3
Mr = 771.99Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.4792 (10) ŵ = 3.23 mm−1
b = 6.1059 (6) ÅT = 293 K
c = 25.450 (2) Å0.25 × 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)		Rint = 0.026
Tmin = 0.499, Tmax = 0.564θmax = 25.0°
8029 measured reflections200 standard reflections every 3 reflections
2815 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.60 e Å−3
S = 1.01Δρmin = −0.71 e Å−3
2815 reflectionsAbsolute structure: ?
198 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Br10.10163 (4)0.98365 (8)0.229572 (18)0.0870 (2)
C10.4910 (3)0.8264 (4)0.17361 (10)0.0366 (6)
C20.3209 (3)0.7210 (6)0.21980 (12)0.0567 (9)
H20.28540.61950.24020.068*
C30.4355 (3)0.6766 (5)0.20345 (11)0.0479 (8)
H30.47670.54330.21260.058*
C40.3099 (3)1.0674 (6)0.17612 (13)0.0525 (8)
H40.26691.19910.16680.063*
C50.4259 (3)1.0225 (5)0.15993 (13)0.0462 (8)
H50.46081.12500.13960.055*
C60.2591 (3)0.9156 (6)0.20593 (12)0.0492 (8)
C70.6186 (3)0.7783 (5)0.15678 (10)0.0411 (7)
H7A0.68070.72520.18730.049*
H7B0.65290.91210.14430.049*
C100.6013 (3)0.6071 (5)0.11224 (10)0.0354 (6)
C120.1011 (3)0.4106 (5)0.06736 (10)0.0354 (6)
C130.1512 (3)0.2454 (5)0.03830 (11)0.0410 (7)
H130.10830.11170.03240.049*
C140.2815 (3)0.6273 (4)0.05081 (11)0.0373 (6)
H140.32540.76050.05480.045*
C150.2618 (3)0.2798 (5)0.01872 (11)0.0392 (7)
H150.29180.16580.00010.047*
C160.1726 (3)0.6080 (5)0.07202 (11)0.0393 (7)
H160.14470.72640.08990.047*
C17−0.0511 (4)0.5523 (6)0.12039 (17)0.0694 (11)
H17A0.02060.61430.14500.104*
H17B−0.11260.49180.13990.104*
H17C−0.09240.66440.09660.104*
C19−0.0777 (3)0.1795 (6)0.08259 (15)0.0640 (10)
H19A−0.11670.16220.04550.096*
H19B−0.14450.18410.10370.096*
H19C−0.02070.05830.09390.096*
Cu10.50000.50000.00000.03234 (15)
N1−0.0042 (2)0.3814 (4)0.08968 (10)0.0462 (6)
N20.3302 (2)0.4658 (3)0.02439 (9)0.0331 (5)
O10.6222 (2)0.4143 (4)0.12444 (8)0.0570 (6)
O20.56545 (17)0.6809 (3)0.06509 (7)0.0372 (4)
O30.58520 (19)0.1416 (3)0.03998 (7)0.0469 (5)
H3B0.55910.00500.04630.056*
H3A0.60110.21050.07270.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0564 (3)0.1343 (5)0.0770 (3)−0.0039 (2)0.0294 (2)−0.0350 (3)
C10.0497 (17)0.0354 (15)0.0256 (13)−0.0051 (13)0.0092 (12)−0.0073 (11)
C20.069 (2)0.065 (2)0.0416 (17)−0.0128 (19)0.0260 (16)0.0034 (15)
C30.065 (2)0.0413 (17)0.0386 (15)0.0014 (16)0.0123 (15)0.0054 (13)
C40.061 (2)0.0482 (18)0.0505 (18)0.0102 (17)0.0149 (16)−0.0055 (15)
C50.060 (2)0.0394 (18)0.0421 (16)−0.0025 (15)0.0167 (15)−0.0010 (13)
C60.0488 (18)0.064 (2)0.0388 (16)−0.0027 (17)0.0171 (14)−0.0152 (15)
C70.0470 (17)0.0440 (17)0.0323 (14)−0.0046 (14)0.0080 (12)−0.0083 (12)
C100.0345 (15)0.0392 (17)0.0358 (15)−0.0073 (13)0.0155 (12)−0.0071 (12)
C120.0330 (14)0.0396 (15)0.0348 (14)−0.0011 (13)0.0093 (12)0.0013 (12)
C130.0413 (16)0.0349 (15)0.0505 (16)−0.0085 (13)0.0177 (13)−0.0096 (13)
C140.0407 (15)0.0298 (15)0.0447 (16)−0.0029 (12)0.0164 (13)−0.0063 (12)
C150.0437 (16)0.0334 (15)0.0452 (16)−0.0045 (13)0.0199 (13)−0.0103 (12)
C160.0405 (16)0.0337 (16)0.0477 (16)0.0018 (13)0.0188 (13)−0.0063 (13)
C170.062 (2)0.073 (2)0.087 (3)−0.0086 (19)0.048 (2)−0.017 (2)
C190.054 (2)0.067 (2)0.079 (2)−0.0204 (18)0.0334 (18)−0.0083 (19)
Cu10.0321 (3)0.0372 (3)0.0304 (3)−0.0056 (2)0.01259 (19)−0.00735 (18)
N10.0408 (14)0.0468 (15)0.0572 (15)−0.0077 (12)0.0249 (12)−0.0071 (12)
N20.0355 (12)0.0318 (13)0.0351 (12)−0.0014 (10)0.0143 (10)−0.0048 (9)
O10.0861 (18)0.0371 (12)0.0473 (12)−0.0003 (12)0.0116 (11)−0.0025 (10)
O20.0436 (11)0.0381 (11)0.0317 (10)−0.0060 (9)0.0114 (8)−0.0075 (8)
O30.0602 (13)0.0386 (11)0.0438 (11)−0.0036 (10)0.0146 (9)−0.0017 (9)
Geometric parameters (Å, °) top
Br1—C61.906 (3)C14—N21.347 (3)
C1—C31.386 (4)C14—C161.357 (4)
C1—C51.389 (4)C14—H140.9300
C1—C71.508 (4)C15—N21.336 (3)
C2—C61.367 (5)C15—H150.9300
C2—C31.371 (4)C16—H160.9300
C2—H20.9300C17—N11.445 (4)
C3—H30.9300C17—H17A0.9600
C4—C61.368 (5)C17—H17B0.9600
C4—C51.384 (5)C17—H17C0.9600
C4—H40.9300C19—N11.447 (4)
C5—H50.9300C19—H19A0.9600
C7—C101.527 (4)C19—H19B0.9600
C7—H7A0.9700C19—H19C0.9600
C7—H7B0.9700Cu1—O2i2.0006 (17)
C10—O11.226 (4)Cu1—O22.0006 (17)
C10—O21.270 (3)Cu1—N22.004 (2)
C12—N11.345 (3)Cu1—N2i2.004 (2)
C12—C131.410 (4)Cu1—O32.5052 (19)
C12—C161.412 (4)Cu1—O3i2.5052 (19)
C13—C151.362 (4)O3—H3B0.9018
C13—H130.9300O3—H3A0.9200
C3—C1—C5117.9 (3)C14—C16—C12120.9 (3)
C3—C1—C7121.0 (3)C14—C16—H16119.6
C5—C1—C7121.1 (3)C12—C16—H16119.6
C6—C2—C3119.5 (3)N1—C17—H17A109.5
C6—C2—H2120.2N1—C17—H17B109.5
C3—C2—H2120.2H17A—C17—H17B109.5
C2—C3—C1121.3 (3)N1—C17—H17C109.5
C2—C3—H3119.4H17A—C17—H17C109.5
C1—C3—H3119.4H17B—C17—H17C109.5
C6—C4—C5119.2 (3)N1—C19—H19A109.5
C6—C4—H4120.4N1—C19—H19B109.5
C5—C4—H4120.4H19A—C19—H19B109.5
C4—C5—C1120.9 (3)N1—C19—H19C109.5
C4—C5—H5119.5H19A—C19—H19C109.5
C1—C5—H5119.5H19B—C19—H19C109.5
C2—C6—C4121.1 (3)O2i—Cu1—O2180.00 (6)
C2—C6—Br1120.3 (3)O2i—Cu1—N290.81 (8)
C4—C6—Br1118.6 (3)O2—Cu1—N289.19 (8)
C1—C7—C10111.0 (2)O2i—Cu1—N2i89.19 (8)
C1—C7—H7A109.4O2—Cu1—N2i90.81 (8)
C10—C7—H7A109.4N2—Cu1—N2i180.00 (11)
C1—C7—H7B109.4O2—Cu1—O396.11 (7)
C10—C7—H7B109.4O2—Cu1—O3i83.89 (7)
H7A—C7—H7B108.0O3—Cu1—N292.98 (7)
O1—C10—O2125.9 (2)O3—Cu1—O2i83.89 (7)
O1—C10—C7118.6 (2)O3—Cu1—O3i180.00 (7)
O2—C10—C7115.5 (2)O3—Cu1—N2i87.02 (7)
N1—C12—C13122.9 (3)N2—Cu1—O3i87.02 (7)
N1—C12—C16122.8 (3)O2i—Cu1—O3i96.11 (7)
C13—C12—C16114.2 (2)O3i—Cu1—N2i92.98 (7)
C15—C13—C12120.6 (3)C12—N1—C17121.5 (3)
C15—C13—H13119.7C12—N1—C19121.4 (3)
C12—C13—H13119.7C17—N1—C19117.1 (3)
N2—C14—C16124.2 (3)C15—N2—C14115.4 (2)
N2—C14—H14117.9C15—N2—Cu1123.04 (18)
C16—C14—H14117.9C14—N2—Cu1121.40 (18)
N2—C15—C13124.6 (2)C10—O2—Cu1125.44 (18)
N2—C15—H15117.7H3B—O3—H3A105.6
C13—C15—H15117.7
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O2ii0.902.032.901 (3)161
O3—H3A···O10.921.792.688 (3)163
Symmetry codes: (ii) x, y−1, z.
Table 1
Selected geometric parameters (Å) top
Cu1—O22.0006 (17)Cu1—O32.5052 (19)
Cu1—N22.004 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O2i0.902.032.901 (3)161
O3—H3A···O10.921.792.688 (3)163
Symmetry codes: (i) x, y−1, z.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.

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

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

Liu, Z.-D. & Zhu, H.-L. (2004). Acta Cryst. E60, m1866–m1868.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yang, H.-L., You, Z.-L. & Zhu, H.-L. (2004). Acta Cryst. E60, m1213–m1214.

You, Z.-L., Zhu, H.-L. & Liu, W.-S. (2004). Acta Cryst. E60, m1863–m1865.