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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1028.
Published online 2008 July 16. doi:  10.1107/S1600536808021521
PMCID: PMC2961950

3,3′-Bis(4-fluoro­benz­yl)-1,1′-ethyl­enediimidazolium tribromidocuprate(I)

Abstract

The title compound, (C22H22F2N4)[CuBr3], crystallizes with the cation situated on an inversion center and the anion on a twofold rotation axis along one Cu—Br bond. The two imidazole rings are in an anti configuration. The anion has a trigonal planar coordination geometry.

Related literature

For general background, see: Liao et al. (2007 [triangle]). For the structure of another salt of this cation, see: Lee et al. (2007 [triangle]).

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Object name is e-64-m1028-scheme1.jpg

Experimental

Crystal data

  • (C22H22F2N4)[CuBr3]
  • M r = 683.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1028-efi1.jpg
  • a = 15.4994 (11) Å
  • b = 11.0825 (8) Å
  • c = 15.4464 (12) Å
  • β = 117.582 (4)°
  • V = 2351.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.06 mm−1
  • T = 150 (2) K
  • 0.30 × 0.21 × 0.19 mm

Data collection

  • Bruker SMART 1000 diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001 [triangle]) T min = 0.213, T max = 0.318
  • 11647 measured reflections
  • 2686 independent reflections
  • 2242 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.091
  • S = 1.03
  • 2686 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 1.51 e Å−3
  • Δρmin = −0.73 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021521/cf2209sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021521/cf2209Isup2.hkl

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

Acknowledgments

The authors are grateful to the National Science Council of Taiwan for financial support of this work.

supplementary crystallographic information

Comment

Our group is interested in the preparation of imidazolium salts, which can be employed as ligand precursors for N-heterocyclic carbenes (Liao et al., 2007). In an unsuccessful attempt to prepare a copper carbene complex using 1,1'-bis(4-fluorobenzyl)-3,3'-ethylenediimidazolium dibromide, we isolated the title compound (I). Here we present its structure (Fig. 1). In our previous work (Lee et al., 2007), we reported the structure of 1,1'-bis(4-fluorobenzyl)-3,3'-ethylenediimidazolium dichloride monohydrate (II), which features the same imidazolium cation with chloride anions.

Compound (I) crystallizes in the monoclinic space group C2/c with the imidazolium cation situated on a center of inversion. An notable feature is the anti configuration of the two imdazole rings, which is in contrast to the structure of (II). Also, there is no guest water incorporation as in the structure of (II). The anion lies on a twofold rotation axis and has trigonal-planar geometry.

Experimental

The compound was prepared by heating a mixture of 1,1'-bis(4-fluorobenzyl)-3,3'-ethylenediimidazolium dibromide (0.10 g, 18.5 mmol), copper dibromide (0.0496 g, 22.2 mmol), and sodium acetate (0.0304 g, 37.0 mmol) in DMSO (5 ml) at 353 K for 4 h. After cooling, the solvent was removed completely under vacuum. The residual solid was washed with water and dichloromethane. Crystals were obtained by vapor diffusion of diethyl ether into a DMF solution of the compound.

Refinement

All H atoms were positioned geometrically and refined with a riding model, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all other H atoms.

Figures

Fig. 1.
The structure of (I), showing 50% probability displacement ellipsoids for non-H atoms. H atoms are of arbitrary size. Unlabeled atoms of the imidazolium cation are related to labeled atoms by 3/2-x, 3/2-y, -z; for the anion, the symmetry operation for ...

Crystal data

(C22H22F2N4)[CuBr3]F000 = 1336
Mr = 683.71Dx = 1.931 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3837 reflections
a = 15.4994 (11) Åθ = 2.4–27.1º
b = 11.0825 (8) ŵ = 6.06 mm1
c = 15.4464 (12) ÅT = 150 (2) K
β = 117.582 (4)ºPrism, colorless
V = 2351.7 (3) Å30.30 × 0.21 × 0.19 mm
Z = 4

Data collection

Bruker SMART 1000 diffractometer2686 independent reflections
Monochromator: graphite2242 reflections with I > 2σ(I)
Detector resolution: 8.3 pixels mm-1Rint = 0.023
T = 150(2) Kθmax = 27.5º
ω scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 2001)h = −20→20
Tmin = 0.214, Tmax = 0.318k = −14→14
11647 measured reflectionsl = −20→20

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.091  w = 1/[σ2(Fo2) + (0.0522P)2 + 7.4402P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2686 reflectionsΔρmax = 1.51 e Å3
146 parametersΔρmin = −0.73 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Cu10.50000.18316 (6)0.25000.03387 (17)
Br10.48562 (2)0.06476 (3)0.11487 (2)0.02810 (12)
Br20.50000.39352 (5)0.25000.03037 (14)
F10.8176 (2)0.0493 (2)0.03890 (16)0.0474 (6)
N10.71155 (19)0.6850 (2)0.08805 (18)0.0213 (6)
N20.7085 (2)0.5320 (2)0.17325 (18)0.0213 (5)
C10.7483 (2)0.7770 (3)0.0448 (2)0.0224 (6)
H1A0.81430.80300.09330.027*
H1B0.70500.84840.02540.027*
C20.7660 (2)0.6007 (3)0.1510 (2)0.0241 (7)
H2A0.83430.59110.17590.029*
C30.6162 (2)0.6686 (3)0.0690 (3)0.0286 (7)
H3A0.56180.71580.02640.034*
C40.6148 (3)0.5730 (3)0.1223 (3)0.0287 (7)
H4A0.55910.54010.12410.034*
C50.7439 (3)0.4259 (3)0.2389 (2)0.0254 (7)
H5A0.69410.40140.25860.030*
H5B0.80390.44780.29860.030*
C60.7651 (2)0.3216 (3)0.1889 (2)0.0229 (7)
C70.6915 (3)0.2417 (3)0.1315 (2)0.0290 (7)
H7A0.62860.25090.12680.035*
C80.7084 (3)0.1489 (3)0.0809 (3)0.0355 (9)
H8A0.65810.09450.04160.043*
C90.8001 (3)0.1388 (3)0.0898 (2)0.0325 (8)
C100.8756 (3)0.2142 (3)0.1463 (3)0.0324 (8)
H10A0.93860.20330.15130.039*
C110.8573 (2)0.3071 (3)0.1961 (2)0.0268 (7)
H11A0.90820.36100.23520.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0247 (3)0.0338 (4)0.0381 (3)0.0000.0102 (3)0.000
Br10.02629 (19)0.0309 (2)0.02709 (18)−0.00222 (13)0.01230 (14)−0.00081 (13)
Br20.0272 (2)0.0304 (3)0.0374 (3)0.0000.0182 (2)0.000
F10.0816 (19)0.0265 (12)0.0329 (11)0.0060 (11)0.0254 (12)−0.0055 (9)
N10.0236 (13)0.0230 (14)0.0183 (12)−0.0005 (11)0.0107 (10)0.0001 (10)
N20.0242 (13)0.0216 (13)0.0204 (12)0.0010 (11)0.0123 (10)0.0022 (10)
C10.0282 (16)0.0202 (16)0.0216 (14)−0.0029 (13)0.0138 (12)0.0006 (12)
C20.0242 (16)0.0266 (17)0.0220 (15)0.0003 (13)0.0112 (12)0.0039 (12)
C30.0228 (16)0.0292 (18)0.0350 (18)0.0036 (14)0.0144 (14)0.0086 (14)
C40.0233 (16)0.0311 (18)0.0371 (18)0.0013 (14)0.0185 (14)0.0046 (15)
C50.0322 (18)0.0232 (17)0.0238 (15)0.0011 (14)0.0156 (14)0.0059 (13)
C60.0271 (16)0.0210 (16)0.0208 (14)−0.0014 (13)0.0112 (12)0.0042 (12)
C70.0268 (17)0.0274 (18)0.0300 (17)−0.0066 (14)0.0107 (13)0.0044 (14)
C80.044 (2)0.0245 (18)0.0269 (17)−0.0103 (16)0.0068 (15)0.0037 (14)
C90.055 (2)0.0176 (16)0.0223 (15)0.0036 (16)0.0151 (15)0.0021 (13)
C100.0349 (19)0.031 (2)0.0313 (17)0.0040 (15)0.0155 (15)−0.0002 (15)
C110.0260 (17)0.0248 (17)0.0259 (15)−0.0017 (13)0.0089 (13)−0.0024 (13)

Geometric parameters (Å, °)

Cu1—Br22.3314 (9)C3—H3A0.950
Cu1—Br12.3869 (5)C4—H4A0.950
Cu1—Br1i2.3869 (5)C5—C61.508 (5)
F1—C91.368 (4)C5—H5A0.990
N1—C21.331 (4)C5—H5B0.990
N1—C31.379 (4)C6—C71.390 (5)
N1—C11.470 (4)C6—C111.391 (5)
N2—C21.333 (4)C7—C81.388 (6)
N2—C41.370 (4)C7—H7A0.950
N2—C51.482 (4)C8—C91.369 (6)
C1—C1ii1.532 (6)C8—H8A0.950
C1—H1A0.990C9—C101.373 (5)
C1—H1B0.990C10—C111.390 (5)
C2—H2A0.950C10—H10A0.950
C3—C41.349 (5)C11—H11A0.950
Br2—Cu1—Br1123.349 (16)N2—C5—C6110.9 (3)
Br2—Cu1—Br1i123.349 (16)N2—C5—H5A109.5
Br1—Cu1—Br1i113.30 (3)C6—C5—H5A109.5
C2—N1—C3108.6 (3)N2—C5—H5B109.5
C2—N1—C1124.8 (3)C6—C5—H5B109.5
C3—N1—C1126.6 (3)H5A—C5—H5B108.0
C2—N2—C4108.7 (3)C7—C6—C11119.1 (3)
C2—N2—C5123.3 (3)C7—C6—C5120.4 (3)
C4—N2—C5127.9 (3)C11—C6—C5120.5 (3)
N1—C1—C1ii108.8 (3)C8—C7—C6121.2 (3)
N1—C1—H1A109.9C8—C7—H7A119.4
C1ii—C1—H1A109.9C6—C7—H7A119.4
N1—C1—H1B109.9C9—C8—C7117.5 (3)
C1ii—C1—H1B109.9C9—C8—H8A121.2
H1A—C1—H1B108.3C7—C8—H8A121.2
N1—C2—N2108.4 (3)F1—C9—C8118.3 (3)
N1—C2—H2A125.8F1—C9—C10118.0 (4)
N2—C2—H2A125.8C8—C9—C10123.6 (4)
C4—C3—N1107.0 (3)C9—C10—C11118.0 (4)
C4—C3—H3A126.5C9—C10—H10A121.0
N1—C3—H3A126.5C11—C10—H10A121.0
C3—C4—N2107.4 (3)C10—C11—C6120.5 (3)
C3—C4—H4A126.3C10—C11—H11A119.8
N2—C4—H4A126.3C6—C11—H11A119.8

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y+3/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CF2209).

References

  • Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lee, H. M., Chen, C.-Y., Chen, W.-L. & Lin, H.-C. (2007). Acta Cryst. E63, o315–o316.
  • Liao, C.-Y., Chan, K.-T., Zeng, J.-Y., Hu, C.-H., Tu, C.-Y. & Lee, H. M. (2007). Organometallics, 26, 1692–1702.
  • Sheldrick, G. M. (2001). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography