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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): m682.
Published online 2010 May 22. doi:  10.1107/S1600536810017459
PMCID: PMC2979359

Tetra­imidazole­bis(trichloro­acetato)copper(II)

Abstract

The title compound, [Cu(C2Cl3O2)2(C3H4N2)4], was prepared by the reaction of imidazole and trichloro­acetatocopper(II). The CuII atom adopts a distorted octa­hedral coordination geometry, binding the N atoms of four imidazole ligands and the carboxyl­ate O atoms of two trichloro­acetate anions. The mol­ecular structure and packing are stabilized by N—H(...)O hydrogen-bonding inter­actions. Close inter­molecular Cl(...)Cl contacts [3.498 (3) Å] are also found in the structure.

Related literature

For background to work on metal-organic frameworks, see: Chen et al. (2001 [triangle]); Fang et al. (2005 [triangle]). For a related structure, see: Moncol et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m682-scheme1.jpg

Experimental

Crystal data

  • [Cu(C2Cl3O2)2(C3H4N2)4]
  • M r = 660.61
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m682-efi1.jpg
  • a = 10.054 (2) Å
  • b = 10.539 (2) Å
  • c = 12.959 (3) Å
  • α = 108.12 (3)°
  • β = 92.93 (3)°
  • γ = 95.18 (3)°
  • V = 1295.2 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.50 mm−1
  • T = 293 K
  • 0.22 × 0.20 × 0.18 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • 12377 measured reflections
  • 5823 independent reflections
  • 5048 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.168
  • S = 1.05
  • 5823 reflections
  • 316 parameters
  • H-atom parameters constrained
  • Δρmax = 1.43 e Å−3
  • Δρmin = −0.86 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017459/sj2779sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017459/sj2779Isup2.hkl

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

Acknowledgments

The authors would like to thank the Natural Science Foundation of Shandong Province for financial support (No. Y2008B30).

supplementary crystallographic information

Comment

Metal-organic framework coordination polymers have attracted tremendous attention because of their molecular topologies and their potentially useful ion exchange, adsorption, catalytic and magnetic properties (Chen et al., 2001; Fang et al., 2005 ). In order to search for new complexes of this type, we synthesized the title compound and report its crystal structure here.

The title structure contains one copper(II) cation, four imidazole ligands and two trichloroacetate anions. The coordination sphere of the copper(II) ion is best described as a slightly distorted octahedron. The Cu—N bond lengths are in agreement with those reported recently (Moncol et al., 2007). The crystal packing is stabilized by C—H···O and N—H···O hydrogen interaction (Table 1).

Experimental

The title compound was obtained by adding imidazole(4 mmol) dropwise to a solution of copper(II) trichloroacetate acid (1 mmol) in ethanol (30 ml) with stirring for 1 hour at room temperature. A blue solution formed and after a few days rod-like crystals precipitated.

Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.93Å, Uiso=1.2Ueq (C) for aromatic H atoms and 0.86Å, Uiso = 1.2Ueq (N) for the NH groups.

Figures

Fig. 1.
The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Crystal packing of the title compound viewed down the c axis.

Crystal data

[Cu(C2Cl3O2)2(C3H4N2)4]Z = 2
Mr = 660.61F(000) = 662
Triclinic, P1Dx = 1.694 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.054 (2) ÅCell parameters from 2238 reflections
b = 10.539 (2) Åθ = 2.1–26.3°
c = 12.959 (3) ŵ = 1.50 mm1
α = 108.12 (3)°T = 293 K
β = 92.93 (3)°Rod, blue
γ = 95.18 (3)°0.22 × 0.20 × 0.18 mm
V = 1295.2 (4) Å3

Data collection

Bruker SMART CCD area-detector diffractometer5048 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.053
graphiteθmax = 27.5°, θmin = 3.0°
[var phi] and ω scansh = −13→10
12377 measured reflectionsk = −13→13
5823 independent reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.1013P)2 + 0.8989P] where P = (Fo2 + 2Fc2)/3
5823 reflections(Δ/σ)max < 0.001
316 parametersΔρmax = 1.43 e Å3
0 restraintsΔρmin = −0.85 e Å3

Special details

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 > 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)

xyzUiso*/Ueq
Cu10.26177 (3)0.25376 (3)0.24476 (3)0.02655 (14)
Cl10.41741 (11)−0.13876 (10)0.38566 (9)0.0542 (3)
Cl4−0.12008 (10)0.61045 (11)0.09196 (10)0.0593 (3)
Cl60.14287 (9)0.67968 (9)0.19926 (13)0.0687 (4)
Cl20.44972 (12)−0.16467 (11)0.16082 (9)0.0619 (3)
Cl30.67814 (10)−0.15040 (9)0.30617 (13)0.0744 (4)
Cl5−0.08098 (15)0.63279 (11)0.31833 (10)0.0716 (4)
N70.2999 (2)0.3951 (2)0.3900 (2)0.0290 (5)
N30.2209 (2)0.1099 (2)0.1006 (2)0.0296 (5)
N10.1157 (2)0.1667 (2)0.3089 (2)0.0294 (5)
O10.6441 (2)0.1316 (2)0.3576 (2)0.0412 (6)
O30.1177 (2)0.4023 (2)0.1870 (2)0.0390 (5)
C160.0052 (3)0.4292 (3)0.1668 (2)0.0271 (6)
N50.4180 (2)0.3358 (2)0.1859 (2)0.0269 (5)
C140.5229 (3)−0.0894 (3)0.2966 (3)0.0349 (7)
N80.3302 (3)0.5850 (3)0.5243 (2)0.0424 (7)
H8A0.33490.66950.55910.051*
C15−0.0107 (3)0.5819 (3)0.1915 (3)0.0357 (7)
C40.1621 (3)−0.0146 (3)0.0788 (3)0.0377 (7)
H4A0.1307−0.05070.13110.045*
C3−0.0074 (3)0.1991 (3)0.3191 (3)0.0335 (6)
H3A−0.03900.27080.30180.040*
N60.6185 (2)0.3773 (3)0.1383 (2)0.0337 (6)
H6A0.70060.36860.12450.040*
O20.4247 (2)0.1096 (2)0.3115 (2)0.0460 (6)
C120.2979 (4)0.5269 (3)0.4173 (3)0.0394 (7)
H12A0.27690.57270.36890.047*
N2−0.0805 (3)0.1150 (3)0.3579 (2)0.0376 (6)
H2A−0.16330.11840.37130.045*
C130.5316 (3)0.0686 (3)0.3258 (3)0.0294 (6)
C90.5368 (3)0.2938 (3)0.1716 (3)0.0313 (6)
H9A0.56080.21590.18330.038*
C10.1205 (3)0.0559 (3)0.3430 (3)0.0399 (7)
H1A0.19570.01120.34540.048*
N40.1536 (3)−0.0808 (3)−0.0272 (3)0.0433 (7)
H4B0.1195−0.1626−0.05810.052*
C80.5480 (3)0.4792 (3)0.1302 (3)0.0424 (8)
H8B0.57890.55220.10860.051*
C2−0.0014 (3)0.0224 (4)0.3726 (3)0.0438 (8)
H2B−0.0262−0.04910.39780.053*
C70.4245 (3)0.4526 (3)0.1596 (3)0.0381 (7)
H7A0.35460.50520.16180.046*
C110.3542 (4)0.4870 (4)0.5681 (3)0.0456 (8)
H11A0.37850.49800.64090.055*
C60.2081 (5)0.0029 (5)−0.0779 (3)0.0653 (13)
H6B0.2160−0.0161−0.15230.078*
C50.2490 (5)0.1207 (4)0.0017 (3)0.0543 (10)
H5A0.29020.1974−0.00950.065*
C100.3354 (4)0.3696 (3)0.4845 (3)0.0405 (7)
H10A0.34520.28520.49040.049*
O4−0.1012 (2)0.3534 (2)0.1345 (2)0.0390 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0222 (2)0.0225 (2)0.0301 (2)−0.00600 (13)0.00312 (13)0.00353 (15)
Cl10.0542 (6)0.0461 (5)0.0682 (6)−0.0106 (4)0.0040 (4)0.0314 (4)
Cl40.0390 (5)0.0648 (6)0.0921 (8)0.0136 (4)−0.0025 (5)0.0498 (6)
Cl60.0311 (5)0.0322 (5)0.1425 (12)−0.0079 (3)−0.0069 (5)0.0329 (5)
Cl20.0673 (7)0.0517 (6)0.0537 (6)−0.0014 (5)0.0007 (5)0.0010 (4)
Cl30.0299 (5)0.0347 (5)0.1577 (13)0.0097 (4)−0.0054 (6)0.0295 (6)
Cl50.0955 (9)0.0523 (6)0.0649 (7)0.0291 (6)0.0273 (6)0.0068 (5)
N70.0274 (12)0.0239 (12)0.0307 (12)−0.0021 (9)0.0016 (9)0.0032 (9)
N30.0265 (12)0.0227 (12)0.0352 (13)−0.0011 (9)0.0000 (9)0.0045 (9)
N10.0220 (12)0.0265 (12)0.0366 (13)−0.0031 (9)0.0016 (9)0.0072 (10)
O10.0255 (11)0.0243 (11)0.0680 (16)−0.0004 (8)0.0045 (10)0.0072 (10)
O30.0243 (11)0.0312 (11)0.0648 (16)0.0079 (9)−0.0020 (10)0.0193 (10)
C160.0235 (13)0.0207 (13)0.0377 (15)0.0043 (10)0.0042 (10)0.0096 (10)
N50.0215 (11)0.0241 (11)0.0319 (12)−0.0026 (9)0.0001 (9)0.0059 (9)
C140.0225 (14)0.0250 (14)0.056 (2)0.0005 (11)−0.0017 (12)0.0128 (13)
N80.0403 (16)0.0304 (14)0.0435 (16)−0.0018 (11)0.0021 (12)−0.0050 (12)
C150.0238 (14)0.0259 (14)0.058 (2)0.0039 (11)0.0032 (13)0.0142 (13)
C40.0408 (18)0.0237 (14)0.0433 (18)−0.0025 (12)0.0015 (13)0.0049 (12)
C30.0240 (14)0.0353 (16)0.0424 (17)0.0007 (11)0.0042 (11)0.0144 (13)
N60.0193 (12)0.0384 (14)0.0436 (15)0.0014 (10)0.0066 (10)0.0132 (11)
O20.0285 (12)0.0370 (13)0.0778 (19)0.0111 (10)0.0030 (11)0.0239 (12)
C120.0413 (18)0.0271 (15)0.0458 (19)0.0002 (13)−0.0012 (14)0.0075 (13)
N20.0210 (12)0.0474 (16)0.0459 (15)−0.0026 (11)0.0043 (10)0.0184 (12)
C130.0260 (14)0.0209 (13)0.0437 (16)0.0048 (10)0.0085 (11)0.0121 (11)
C90.0257 (14)0.0303 (14)0.0398 (16)0.0050 (11)0.0042 (11)0.0132 (12)
C10.0252 (15)0.0426 (18)0.059 (2)0.0046 (13)0.0035 (13)0.0259 (15)
N40.0420 (16)0.0270 (14)0.0465 (17)−0.0031 (11)−0.0039 (12)−0.0062 (12)
C80.0301 (16)0.0394 (18)0.067 (2)0.0030 (13)0.0102 (15)0.0290 (16)
C20.0341 (18)0.049 (2)0.056 (2)−0.0062 (14)0.0003 (14)0.0309 (17)
C70.0255 (15)0.0341 (16)0.062 (2)0.0053 (12)0.0068 (13)0.0243 (15)
C110.049 (2)0.048 (2)0.0307 (16)−0.0056 (16)0.0007 (13)0.0033 (14)
C60.087 (3)0.059 (3)0.0338 (19)−0.020 (2)0.0015 (19)−0.0010 (18)
C50.073 (3)0.047 (2)0.0355 (18)−0.0206 (19)−0.0033 (17)0.0105 (15)
C100.048 (2)0.0372 (17)0.0346 (16)0.0008 (14)0.0011 (13)0.0101 (13)
O40.0229 (10)0.0261 (11)0.0637 (16)−0.0024 (8)−0.0011 (9)0.0102 (10)

Geometric parameters (Å, °)

Cu1—N71.997 (2)N8—H8A0.8600
Cu1—N32.001 (2)C4—N41.327 (4)
Cu1—N12.011 (3)C4—H4A0.9300
Cu1—N52.022 (3)C3—N21.333 (4)
Cu1—O32.479 (2)C3—H3A0.9300
Cu1—O22.618 (2)N6—C91.333 (4)
Cl1—C141.768 (4)N6—C81.367 (4)
Cl4—C151.767 (4)N6—H6A0.8600
Cl6—C151.757 (3)O2—C131.220 (4)
Cl2—C141.778 (4)C12—H12A0.9300
Cl3—C141.754 (3)N2—C21.364 (5)
Cl5—C151.768 (4)N2—H2A0.8600
N7—C121.325 (4)C9—H9A0.9300
N7—C101.370 (4)C1—C21.353 (5)
N3—C41.328 (4)C1—H1A0.9300
N3—C51.362 (5)N4—C61.350 (6)
N1—C31.316 (4)N4—H4B0.8600
N1—C11.375 (4)C8—C71.348 (5)
O1—C131.240 (4)C8—H8B0.9300
O3—C161.226 (4)C2—H2B0.9300
C16—O41.245 (4)C7—H7A0.9300
C16—C151.565 (4)C11—C101.358 (5)
N5—C91.312 (4)C11—H11A0.9300
N5—C71.372 (4)C6—C51.357 (5)
C14—C131.582 (4)C6—H6B0.9300
N8—C121.339 (5)C5—H5A0.9300
N8—C111.358 (5)C10—H10A0.9300
N7—Cu1—N3178.78 (10)N3—C4—H4A124.3
N7—Cu1—N187.99 (10)N1—C3—N2110.6 (3)
N3—Cu1—N190.80 (11)N1—C3—H3A124.7
N7—Cu1—N591.08 (10)N2—C3—H3A124.7
N3—Cu1—N590.11 (10)C9—N6—C8107.4 (3)
N1—Cu1—N5175.95 (10)C9—N6—H6A126.3
N7—Cu1—O388.90 (10)C8—N6—H6A126.3
N3—Cu1—O391.37 (9)N7—C12—N8110.6 (3)
N1—Cu1—O395.17 (9)N7—C12—H12A124.7
N5—Cu1—O388.70 (9)N8—C12—H12A124.7
N7—Cu1—O288.42 (10)C3—N2—C2108.2 (3)
N3—Cu1—O291.36 (10)C3—N2—H2A125.9
N1—Cu1—O287.03 (9)C2—N2—H2A125.9
N5—Cu1—O289.06 (9)O2—C13—O1129.8 (3)
O3—Cu1—O2176.47 (7)O2—C13—C14113.8 (3)
C12—N7—C10105.8 (3)O1—C13—C14116.3 (2)
C12—N7—Cu1130.0 (2)N5—C9—N6111.3 (3)
C10—N7—Cu1124.2 (2)N5—C9—H9A124.4
C4—N3—C5104.8 (3)N6—C9—H9A124.4
C4—N3—Cu1129.0 (2)C2—C1—N1109.2 (3)
C5—N3—Cu1126.2 (2)C2—C1—H1A125.4
C3—N1—C1106.1 (3)N1—C1—H1A125.4
C3—N1—Cu1126.4 (2)C4—N4—C6107.9 (3)
C1—N1—Cu1127.3 (2)C4—N4—H4B126.0
O3—C16—O4129.6 (3)C6—N4—H4B126.0
O3—C16—C15116.0 (3)C7—C8—N6106.1 (3)
O4—C16—C15114.3 (2)C7—C8—H8B126.9
C9—N5—C7105.8 (3)N6—C8—H8B126.9
C9—N5—Cu1127.4 (2)C1—C2—N2105.9 (3)
C7—N5—Cu1126.8 (2)C1—C2—H2B127.0
C13—C14—Cl3114.2 (2)N2—C2—H2B127.0
C13—C14—Cl1108.4 (2)C8—C7—N5109.4 (3)
Cl3—C14—Cl1108.81 (19)C8—C7—H7A125.3
C13—C14—Cl2108.8 (2)N5—C7—H7A125.3
Cl3—C14—Cl2107.99 (19)C10—C11—N8106.2 (3)
Cl1—C14—Cl2108.56 (17)C10—C11—H11A126.9
C12—N8—C11108.0 (3)N8—C11—H11A126.9
C12—N8—H8A126.0N4—C6—C5105.9 (4)
C11—N8—H8A126.0N4—C6—H6B127.0
C16—C15—Cl6112.6 (2)C5—C6—H6B127.0
C16—C15—Cl4111.9 (2)C6—C5—N3110.0 (4)
Cl6—C15—Cl4107.7 (2)C6—C5—H5A125.0
C16—C15—Cl5106.0 (2)N3—C5—H5A125.0
Cl6—C15—Cl5109.80 (19)C11—C10—N7109.4 (3)
Cl4—C15—Cl5108.70 (17)C11—C10—H10A125.3
N4—C4—N3111.3 (3)N7—C10—H10A125.3
N4—C4—H4A124.3

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N8—H8A···O1i0.862.032.885 (3)177
N6—H6A···O4ii0.862.022.854 (3)164
N2—H2A···O1iii0.861.962.790 (3)162
N4—H4B···O4iv0.861.932.764 (3)162

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2779).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, B., Eddaoudi, M., Hyde, S. T., OKeeffe, M. & Yaghi, O. M. (2001). Science, 291, 1021–1023. [PubMed]
  • Fang, Q. R., Zhu, G. S., Xue, M., Sun, J. Y., Wei, Y., Qiu, S. & Xu, R. R. (2005). Angew. Chem. Int. Ed.44, 3845–3848. [PubMed]
  • Moncol, J., Maroszova, J., Peter, L., Mark, H., Marian, V., Morris, H., Svorec, J., Melnik, M., Mazur, M. & Koman, M. (2007). Inorg. Chim. Acta, 360, 3213–3225.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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