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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): m656.
Published online 2010 May 15. doi:  10.1107/S1600536810017289
PMCID: PMC2979418

Bis(4-fluoro­anilinium) tetra­chloridocuprate(II)

Abstract

The crystal structure of the title compound, (C6H7FN)2[CuCl4], consists of parallel two-dimensional perovskite-type layers of corner-sharing CuCl6 octa­hedra. These are bonded together via N—H(...)Cl hydrogen bonds from the 4-fluoro­anilinium chains, which are almost perpendicular to the layers. The CuCl4 dianions have two short Cu—Cl bonds [2.2657 (15) and 2.2884 (13) Å] and two longer bonds [2.8868 (15) Å], giving highly Jahn–Teller-distorted CuCl6 octa­hedra. The Cu atoms are situated on crystallographic centers of inversion.

Related literature

For similar ammonium salts, see: Yuan et al. (2004 [triangle]); Bhattacharya et al. (2004 [triangle]). For the ferroelectric properties of a related ammonium metal(II) salt, see: Zhang et al. (2009 [triangle]); Ye et al. (2009 [triangle]).

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Object name is e-66-0m656-scheme1.jpg

Experimental

Crystal data

  • (C6H7FN)2[CuCl4]
  • M r = 429.59
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m656-efi1.jpg
  • a = 15.603 (3) Å
  • b = 7.3893 (15) Å
  • c = 7.1238 (14) Å
  • β = 99.92 (3)°
  • V = 809.0 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.02 mm−1
  • T = 293 K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.667, T max = 0.674
  • 8010 measured reflections
  • 1863 independent reflections
  • 1555 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.166
  • S = 1.16
  • 1863 reflections
  • 98 parameters
  • H-atom parameters constrained
  • Δρmax = 1.03 e Å−3
  • Δρmin = −0.88 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017289/im2199sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017289/im2199Isup2.hkl

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

Acknowledgments

The authors are grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.

supplementary crystallographic information

Comment

Copper(II) halides occur in a variety of geometrical conformations including tetrahedral, square-pyramidal, square-bipyramidal, square-planar and trigonal–bipyramidal (Bhattacharya et al., 2004; Yuan et al., 2004). The perovskite-layer copper chlorides have attracted a great deal of attention due to their magnetic properties and interesting structural phase transitions. This study is a part of our systematic investigation of dielectric ferroelectric, phase transitions materials (Ye et al., 2009; Zhang et al., 2009), including organic ligands, metal-organic coordination compounds and organic inorganic hybrid compounds. Below the melting point (m.p. 440 K) of the 4-fluoroanilinium tetrachlorocuprate, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 6 to 11).

The asymmetric unit of the title compound is composed of a (C6H7FN+) cation and one half of the anionic (CuCl42-) moiety (Fig 1). Tetrachlorocuprate(II) salt of 4-fluoroanilinium ion typically crystallizes in a two-dimensional perovskite-type (CuCl42-) layer structure with layers separated by the organic cations. The CuCl42- ion is almost square, with an out-of-plane Cu1—Cl3 bond length of 2.266 (2) Å , an in-plane Cu1—Cl2 bond length of 2.288 (1) Å and a Cl3—Cu1—Cl2 angle of 90.06 (6)°. The perovskite-type layer consists of cornersharing octahedra in the bc plane. The distance of Cu to the in-plane Cl2 atom of the next CuCl42- ion is approximately 2.9 Å and is significantly longer than the distances in the CuCl42- square due to the Jahn-Teller effect. The Cu atom is situated on a crystallographic center of inversion. In the bc plane, Cu atoms and Cl2 atoms form a puckered plane and the Cu—Cl3 bond is nearly perpendicular to this plane. The organic chains are arranged between the layers. NH3+ groups fit into cavities of the CuCl42- layer and N—H···Cl hydrogen bonds bind the organic chains (Fig. 2). Details of the hydrogen-bonding geometry are given in Table 1.

Experimental

An excess of hydrogen chloride was slowly added to 20 ml of an ethanolic solution of 4-fluoroaniline (222 mg, 0.002 mol). Then copper dichloride dihydrate (170 mg, 0.001 mol) was added to the mixture. After several days, the title salt, (C6H7FN+)2(CuCl42-), was formed and recrystallized from an ethanolic solution at room temperature to afford green prismatic crystals suitable for X-ray analysis.

Dielectric studies (capacitance and dielectric loss measurements) were performed on powder samples which have been pressed into tablets on the surfaces of which a conducting carbon glue was deposited. The automatic impedance TongHui2828 Analyzer has been used. In the measured temperature ranges (80 K to 430 K), the title structure showed no dielectric anomaly.

Refinement

All C—H hydrogen atoms were calculated geometrically and were refined using a riding model with C—H distances ranging from 0.93 to 0.97 Å and Uiso(H) = 1.2 Ueq(C). Hydrogen positions at nitrogen were also calculated geometrically and included into the refinement with N—H = 0.89 Å and Uiso(H) = 1.5 Ueq(N).

Figures

Fig. 1.
The molecular structure of one cation and one anion of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

Crystal data

(C6H7FN)2[CuCl4]F(000) = 430
Mr = 429.59Dx = 1.763 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7279 reflections
a = 15.603 (3) Åθ = 3.1–27.5°
b = 7.3893 (15) ŵ = 2.02 mm1
c = 7.1238 (14) ÅT = 293 K
β = 99.92 (3)°Prism, green
V = 809.0 (3) Å30.20 × 0.20 × 0.20 mm
Z = 2

Data collection

Rigaku SCXmini diffractometer1863 independent reflections
Radiation source: fine-focus sealed tube1555 reflections with I > 2σ(I)
graphiteRint = 0.050
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scansh = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.667, Tmax = 0.674l = −9→9
8010 measured reflections

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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166H-atom parameters constrained
S = 1.16w = 1/[σ2(Fo2) + (0.059P)2 + 3.9072P] where P = (Fo2 + 2Fc2)/3
1863 reflections(Δ/σ)max = 0.001
98 parametersΔρmax = 1.02 e Å3
0 restraintsΔρmin = −0.88 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
C10.1209 (5)0.6057 (12)0.4232 (12)0.0590 (19)
H10.08310.67810.47810.071*
C20.0896 (5)0.4848 (12)0.2821 (12)0.061 (2)
C30.1426 (5)0.3721 (12)0.2064 (12)0.066 (2)
H30.11950.28600.11660.079*
C40.2304 (4)0.3856 (10)0.2627 (10)0.0487 (16)
H40.26770.31250.20760.058*
C50.2632 (4)0.5085 (8)0.4019 (8)0.0333 (12)
C60.2098 (4)0.6174 (10)0.4819 (10)0.0486 (16)
H60.23280.69980.57590.058*
N10.3577 (3)0.5283 (7)0.4557 (8)0.0392 (12)
H1A0.37280.64150.43370.059*
H1B0.38410.45240.38720.059*
H1C0.37350.50320.57900.059*
F10.0021 (3)0.4721 (10)0.2268 (10)0.100 (2)
Cu10.50000.50000.00000.0265 (3)
Cl20.47957 (10)0.28942 (18)0.22368 (19)0.0370 (4)
Cl30.64585 (9)0.4598 (2)0.0752 (2)0.0403 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.042 (4)0.066 (5)0.071 (5)0.009 (3)0.015 (4)−0.003 (4)
C20.033 (3)0.087 (6)0.058 (5)−0.012 (4)−0.003 (3)0.009 (4)
C30.055 (5)0.074 (6)0.067 (5)−0.018 (4)0.003 (4)−0.024 (4)
C40.044 (4)0.049 (4)0.053 (4)−0.008 (3)0.010 (3)−0.015 (3)
C50.034 (3)0.034 (3)0.029 (3)0.003 (2)−0.001 (2)0.003 (2)
C60.045 (4)0.046 (4)0.054 (4)−0.001 (3)0.006 (3)−0.006 (3)
N10.043 (3)0.033 (3)0.041 (3)−0.001 (2)0.008 (2)0.003 (2)
F10.037 (3)0.143 (6)0.114 (5)−0.019 (3)−0.007 (3)−0.020 (4)
Cu10.0304 (5)0.0262 (5)0.0233 (5)0.0012 (4)0.0060 (3)0.0062 (3)
Cl20.0525 (9)0.0308 (7)0.0289 (7)−0.0017 (6)0.0101 (6)0.0064 (5)
Cl30.0301 (7)0.0449 (8)0.0455 (8)0.0038 (6)0.0050 (6)0.0011 (6)

Geometric parameters (Å, °)

C1—C21.370 (12)C5—N11.465 (8)
C1—C61.381 (10)C6—H60.9300
C1—H10.9300N1—H1A0.8900
C2—C31.350 (12)N1—H1B0.8900
C2—F11.359 (9)N1—H1C0.8900
C3—C41.362 (10)Cu1—Cl32.2657 (15)
C3—H30.9300Cu1—Cl3i2.2657 (15)
C4—C51.376 (8)Cu1—Cl22.2884 (13)
C4—H40.9300Cu1—Cl2i2.2884 (13)
C5—C61.353 (9)
C2—C1—C6118.3 (7)C5—C6—C1119.7 (7)
C2—C1—H1120.8C5—C6—H6120.2
C6—C1—H1120.8C1—C6—H6120.2
C3—C2—F1119.7 (8)C5—N1—H1A109.5
C3—C2—C1122.0 (7)C5—N1—H1B109.5
F1—C2—C1118.1 (8)H1A—N1—H1B109.5
C2—C3—C4119.4 (7)C5—N1—H1C109.5
C2—C3—H3120.3H1A—N1—H1C109.5
C4—C3—H3120.3H1B—N1—H1C109.5
C3—C4—C5119.4 (7)Cl3—Cu1—Cl3i180.00 (2)
C3—C4—H4120.3Cl3—Cu1—Cl290.06 (6)
C5—C4—H4120.3Cl3i—Cu1—Cl289.94 (6)
C6—C5—C4121.1 (6)Cl3—Cu1—Cl2i89.94 (6)
C6—C5—N1119.7 (5)Cl3i—Cu1—Cl2i90.06 (6)
C4—C5—N1119.2 (6)Cl2—Cu1—Cl2i180.00 (5)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl20.892.373.248 (6)168
N1—H1A···Cl3ii0.892.373.196 (5)154
N1—H1C···Cl3iii0.892.553.353 (6)151

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2199).

References

  • Bhattacharya, R., Chanda, S., Bocelli, G., Cantoni, A. & Ghosh, A. (2004). J. Chem. Crystallogr.34, 393–400.
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Ye, H. Y., Fu, D. W., Zhang, Y., Zhang, W., Xiong, R. G. & Huang, S. P. (2009). J. Am. Chem. Soc.131, 42–43. [PubMed]
  • Yuan, B.-L., Lan, H.-C., Chen, Y.-P. & Li, Y.-B. (2004). Acta Cryst. E60, m617–m619.
  • Zhang, W., Cheng, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. P. (2009). J. Am. Chem. Soc.131, 12544–12545. [PubMed]

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