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Acta Cryst. (2007). E63, m1966    [ doi:10.1107/S1600536807029674 ]

Tetrakis([mu]-chloroacetato-[kappa]2O:O')bis[(N,N-dimethylformamide-[kappa]O)copper(II)]

L. Sieron

Abstract top

In the title dimeric complex, [Cu2(C2H2ClO2)4(C3H7NO)2], the CuII atom has a five-coordinate square-pyramidal environment, with the carbonyl O atom of the dimethylformamide ligand at the apical position. The complex molecule is located on a crystallographic inversion centre, with a Cu...Cu separation of 2.6614 (4) Å. Intermolecular C-H...O hydrogen bonds are present in the crystal structure.

Comment top

The structure determination of the title compound, (I), was undertaken as a continuation of earlier studies of copper(II) complexes with monochloroacetic acid (Sieroń, 2007).

The title compound (I) contains a dimeric copper(II) complex, [Cu2(CH2ClCOO)4(DMF)2], composed of two CuII centres, four chloroacetate and two DMF ligands (Fig. 1).

The CuII atom has a regular five-coordinate square-pyramidal environment, with the basal plane defined by the O atoms of four bridging bidentate carboxylate groups of monochloroacetate ligands. The CuII atom deviates out of the mean plane formed by the four basal O atoms towards the apical O5 atom of the DMF ligand by 0.2104 (7) Å. The O–C distances in the chloroacetate groups are approximately equal and range from 1.247 (2) to 1.262 (2) Å, indicating the distinct delocalization of their π electrons (Borthwick, 1980). The planes of the two independent bridging chloroacetate groups are perpendicular within experimental error. The apical DMF ligand is twisted by a dihedral angle of 33.8 (1)° with respect to the C1/O1/O3i mean plane. Selected bond distances and bond angles are listed in Table 1. Complex molecules are linked by two Csp3–H···O hydrogen bonds (Table 2), forming eight-membered rings described by the R22(8) graph-set motif (Etter et al., 1990) as shown in Fig. 2. The Cu···Cu distance of 2.6614 (4) Å is comparable to those found in other dimeric copper(II) monochloroacetates (Shi et al., 1999, 2001; Calderazzo et al., 2003).

Related literature top

For related literature, see: Borthwick (1980); Calderazzo et al. (2003); Etter et al. (1990); Shi et al. (1999, 2001), Sieroń (2007).

Experimental top

A mixture of chloroacetic acid (1 mmol) and CuCO3·Cu(OH)2·H2O (0.5 mmol) in a mixture of water (50 ml) and DMF (25 ml) was heated to boiling. The solution was filtered and allowed to cool to room temperature. Turquoise prismatic crystals of (I) were obtained after a few days.

Refinement top

All H atoms were initially located in a difference Fourier synthesis, but were positioned with idealized geometry, with C–H = 0.93, 0.96 and 0.97 Å, and refined using a riding model. The methyl H atoms were allowed to rotate to best fit the experimental electron density (AFIX 137). The isotropic displacement parameters of all H atoms were refined freely.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 40% probability level. Unlabelled atoms are related to labelled atoms by the symmetry code (−x, −y + 1, −z).
[Figure 2] Fig. 2. The packing of (I), showing a hydrogen-bonded chain (dashed lines) running along the a axis.
Tetrakis(µ-chloroacetato-κ2O:O')bis[(N,N-\ dimethylformamide-κO)copper(II)] top
Crystal data top
[Cu2(C2H2ClO2)4(C3H7NO)2]Z = 1
Mr = 647.24F000 = 326
Triclinic, P1Dx = 1.745 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.9969 (6) ÅCell parameters from 3751 reflections
b = 8.0326 (5) Åθ = 2.6–31.2º
c = 10.2420 (7) ŵ = 2.21 mm−1
α = 87.824 (5)ºT = 294 K
β = 71.974 (6)ºPrism, blue-green
γ = 80.015 (6)º0.45 × 0.25 × 0.20 mm
V = 616.05 (8) Å3
Data collection top
Kuma KM-4 CCD diffractometer2814 independent reflections
Monochromator: graphite2660 reflections with I > 2σ(I)
Detector resolution: 8.2356 pixels mm-1Rint = 0.009
T = 294 Kθmax = 27.5º
ω scansθmin = 2.6º
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		h = −10→10
Tmin = 0.511, Tmax = 0.639k = −10→8
6079 measured reflectionsl = −11→13
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullOnly H-atom displacement parameters refined
R[F2 > 2σ(F2)] = 0.023  w = 1/[σ2(Fo2) + (0.0379P)2 + 0.2335P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.60 e Å−3
2814 reflectionsΔρmin = −0.35 e Å−3
159 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0116 (18)
Crystal data top
[Cu2(C2H2ClO2)4(C3H7NO)2]γ = 80.015 (6)º
Mr = 647.24V = 616.05 (8) Å3
Triclinic, P1Z = 1
a = 7.9969 (6) ÅMo Kα
b = 8.0326 (5) ŵ = 2.21 mm−1
c = 10.2420 (7) ÅT = 294 K
α = 87.824 (5)º0.45 × 0.25 × 0.20 mm
β = 71.974 (6)º
Data collection top
Kuma KM-4 CCD diffractometer2814 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		2660 reflections with I > 2σ(I)
Tmin = 0.511, Tmax = 0.639Rint = 0.009
6079 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023159 parameters
wR(F2) = 0.067Only H-atom displacement parameters refined
S = 1.07Δρmax = 0.60 e Å−3
2814 reflectionsΔρmin = −0.35 e Å−3
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Cu10.10233 (3)0.56685 (2)−0.11043 (2)0.0311 (1)
Cl10.09850 (10)0.09076 (8)−0.39180 (6)0.0685 (2)
Cl20.41733 (10)0.10139 (9)0.20517 (8)0.0734 (3)
O10.0899 (2)0.35412 (17)−0.19692 (14)0.0464 (4)
O20.30126 (17)0.44111 (18)−0.05042 (14)0.0444 (4)
O3−0.08262 (19)0.24157 (16)−0.01133 (13)0.0440 (4)
O40.12946 (18)0.32648 (19)0.13481 (15)0.0469 (4)
O50.26071 (19)0.66002 (18)−0.29703 (13)0.0454 (4)
N10.3366 (2)0.6631 (2)−0.52957 (16)0.0482 (5)
C10.0121 (2)0.2386 (2)−0.13520 (17)0.0348 (5)
C20.0355 (3)0.0721 (3)−0.2111 (2)0.0499 (6)
C30.2762 (2)0.3470 (2)0.05293 (18)0.0348 (5)
C40.4480 (3)0.2523 (3)0.0732 (2)0.0496 (6)
C50.2393 (3)0.6247 (3)−0.4080 (2)0.0485 (6)
C60.3121 (5)0.6134 (6)−0.6568 (3)0.0921 (13)
C70.4803 (4)0.7616 (3)−0.5441 (3)0.0669 (8)
H10.12560−0.00930−0.187200.100 (11)*
H2−0.075800.02850−0.180200.080 (9)*
H30.521200.19530−0.012300.068 (8)*
H40.513000.333800.093900.084 (9)*
H50.146800.56640−0.403600.069 (8)*
H610.221900.54310−0.636300.18 (2)*
H620.422400.55170−0.714600.138 (16)*
H630.275800.71250−0.703300.16 (2)*
H710.583800.71390−0.617300.099 (11)*
H720.509700.75850−0.459900.114 (13)*
H730.441100.87660−0.564600.160 (19)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0345 (1)0.0302 (1)0.0256 (1)−0.0117 (1)−0.0016 (1)0.0007 (1)
Cl10.0935 (5)0.0635 (4)0.0471 (3)−0.0030 (3)−0.0226 (3)−0.0226 (3)
Cl20.0839 (4)0.0667 (4)0.0857 (5)−0.0212 (3)−0.0482 (4)0.0314 (3)
O10.0620 (8)0.0387 (7)0.0344 (7)−0.0211 (6)−0.0014 (6)−0.0072 (5)
O20.0375 (6)0.0468 (7)0.0452 (7)−0.0104 (5)−0.0067 (5)0.0106 (6)
O30.0575 (8)0.0348 (6)0.0368 (7)−0.0173 (6)−0.0046 (6)−0.0034 (5)
O40.0394 (7)0.0560 (8)0.0429 (7)−0.0116 (6)−0.0090 (6)0.0136 (6)
O50.0524 (8)0.0470 (7)0.0303 (6)−0.0182 (6)0.0015 (5)0.0043 (5)
N10.0490 (9)0.0533 (10)0.0316 (8)0.0045 (7)−0.0043 (7)0.0022 (7)
C10.0404 (8)0.0298 (8)0.0351 (9)−0.0075 (6)−0.0114 (7)−0.0042 (6)
C20.0699 (13)0.0351 (9)0.0458 (11)−0.0136 (9)−0.0158 (10)−0.0088 (8)
C30.0381 (8)0.0302 (8)0.0370 (9)−0.0099 (6)−0.0101 (7)−0.0026 (6)
C40.0436 (10)0.0430 (10)0.0626 (13)−0.0090 (8)−0.0171 (9)0.0097 (9)
C50.0437 (10)0.0527 (11)0.0426 (10)−0.0095 (8)−0.0036 (8)0.0021 (9)
C60.080 (2)0.143 (3)0.0394 (13)0.012 (2)−0.0140 (13)−0.0079 (16)
C70.0647 (14)0.0596 (14)0.0565 (14)−0.0130 (11)0.0101 (12)0.0130 (11)
Geometric parameters (Å, °) top
Cu1—O11.9856 (14)N1—C71.473 (4)
Cu1—O21.9823 (15)C1—C21.527 (3)
Cu1—O3i1.9719 (13)C3—C41.520 (3)
Cu1—O4i1.9879 (16)C2—H10.97
Cu1—O52.1304 (14)C2—H20.97
Cl1—C21.769 (2)C4—H30.97
Cl2—C41.769 (2)C4—H40.97
O1—C11.249 (2)C5—H50.93
O2—C31.262 (2)C6—H610.96
O3—C11.259 (2)C6—H620.96
O4—C31.247 (2)C6—H630.96
O5—C51.250 (2)C7—H710.96
N1—C51.306 (3)C7—H720.96
N1—C61.456 (4)C7—H730.96
Cu1···Cu1i2.6614 (4)
O1—Cu1—O288.42 (6)O5—C5—N1125.1 (2)
O1—Cu1—O593.93 (6)Cl1—C2—H1109
O1—Cu1—O3i167.75 (6)Cl1—C2—H2109
O1—Cu1—O4i90.31 (6)C1—C2—H1109
O2—Cu1—O597.35 (6)C1—C2—H2109
O2—Cu1—O3i90.21 (6)H1—C2—H2108
O2—Cu1—O4i167.87 (6)Cl2—C4—H3109
O3i—Cu1—O598.32 (5)Cl2—C4—H4109
O4i—Cu1—O594.78 (6)C3—C4—H3109
O3i—Cu1—O4i88.48 (6)C3—C4—H4109
Cu1—O1—C1125.19 (12)H3—C4—H4108
Cu1—O2—C3122.57 (12)O5—C5—H5117
Cu1i—O3—C1120.41 (12)N1—C5—H5117
Cu1i—O4—C3122.77 (13)N1—C6—H61109
Cu1—O5—C5119.27 (15)N1—C6—H62109
C5—N1—C6123.4 (2)N1—C6—H63109
C5—N1—C7120.42 (19)H61—C6—H62109
C6—N1—C7116.1 (2)H61—C6—H63109
O1—C1—O3126.43 (16)H62—C6—H63110
O1—C1—C2119.16 (16)N1—C7—H71109
O3—C1—C2114.37 (15)N1—C7—H72109
Cl1—C2—C1113.61 (15)N1—C7—H73109
O2—C3—O4126.68 (17)H71—C7—H72109
O2—C3—C4113.55 (16)H71—C7—H73109
O4—C3—C4119.78 (16)H72—C7—H73109
Cl2—C4—C3114.60 (15)
Symmetry codes: (i) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O2ii0.972.483.394 (3)158
Symmetry codes: (ii) −x+1, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.9856 (14)O1—C11.249 (2)
Cu1—O21.9823 (15)O2—C31.262 (2)
Cu1—O3i1.9719 (13)O3—C11.259 (2)
Cu1—O4i1.9879 (16)O4—C31.247 (2)
Cu1—O52.1304 (14)O5—C51.250 (2)
Cu1···Cu1i2.6614 (4)
O1—Cu1—O288.42 (6)O2—Cu1—O3i90.21 (6)
O1—Cu1—O593.93 (6)O2—Cu1—O4i167.87 (6)
O1—Cu1—O3i167.75 (6)O3i—Cu1—O598.32 (5)
O1—Cu1—O4i90.31 (6)O4i—Cu1—O594.78 (6)
O2—Cu1—O597.35 (6)O3i—Cu1—O4i88.48 (6)
Symmetry codes: (i) −x, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O2ii0.972.483.394 (3)158
Symmetry codes: (ii) −x+1, −y+1, −z.
Acknowledgements top

(there are no acknowledgements)

references
References top

Borthwick, P. W. (1980). Acta Cryst. B36, 628–632.

Calderazzo, F., Donati, N., Englert, U., Marchetti, F., Pampaloni, G. & Passarelli, V. (2003). Inorg. Chim. Acta, 346, 100–110.

Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.

Shi, Q., Cao, R., Hong, M. C., Wang, Y. Yu. & Shi, Q. Z. (2001). Transition Met. Chem. 26, 657–661.

Shi, Q., Wang, Y. Y., Tang, Z. X. & Shi, Q. Z. (1999). Jiegou Huaxue (Chin. J. Struct. Chem.), 18, 94–97.

Sieroń, L. (2007). Acta Cryst. E63, m1659–m1661.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.