Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 6| June 2010| Page m656
https://doi.org/10.1107/S1600536810017289

Bis(4-fluoro­anilinium) tetra­chloridocuprate(II)

Min Min Zhaoa* and Ping Ping Shia

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: zmmzyahfdzg@126.com

(Received 5 May 2010; accepted 11 May 2010; online 15 May 2010)

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[Yuan, B.-L., Lan, H.-C., Chen, Y.-P. & Li, Y.-B. (2004). Acta Cryst. E60, m617-m619.]); Bhattacharya et al. (2004[Bhattacharya, R., Chanda, S., Bocelli, G., Cantoni, A. & Ghosh, A. (2004). J. Chem. Crystallogr. 34, 393-400.]). For the ferroelectric properties of a related ammonium metal(II) salt, see: Zhang et al. (2009[Zhang, W., Cheng, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 12544-12545.]); Ye et al. (2009[Ye, H. Y., Fu, D. W., Zhang, Y., Zhang, W., Xiong, R. G. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 42-43.]).

[Scheme 1]

Experimental

Crystal data

  • (C6H7FN)2[CuCl4]

  • Mr = 429.59

  • Monoclinic, P 21 /c

  • 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.667, Tmax = 0.674

  • 8010 measured reflections

  • 1863 independent reflections

  • 1555 reflections with I > 2σ(I)

  • Rint = 0.050
Refinement

  • R[F2 > 2σ(F2)] = 0.058

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1B⋯Cl2 0.89 2.37 3.248 (6) 168
N1—H1A⋯Cl3i 0.89 2.37 3.196 (5) 154
N1—H1C⋯Cl3ii 0.89 2.55 3.353 (6) 151
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017289/im2199Isup2.hkl

checkCIF report


Comment top

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.

Related literature top

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

Experimental top

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 top

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).

Structure description top

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.

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

Computing details top

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

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.
Bis(4-fluoroanilinium) tetrachloridocuprate(II) top
Crystal data top
(C6H7FN)2[CuCl4]F(000) = 430
Mr = 429.59Dx = 1.763 Mg m−3
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 mm−1
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 top
Rigaku SCXmini
diffractometer		1863 independent reflections
Radiation source: fine-focus sealed tube1555 reflections with I > 2σ(I)
Graphite monochromatorRint = 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 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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.059P)2 + 3.9072P]
where P = (Fo2 + 2Fc2)/3
1863 reflections(Δ/σ)max = 0.001
98 parametersΔρmax = 1.03 e Å−3
0 restraintsΔρmin = −0.88 e Å−3
Crystal data top
(C6H7FN)2[CuCl4]V = 809.0 (3) Å3
Mr = 429.59Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.603 (3) ŵ = 2.02 mm−1
b = 7.3893 (15) ÅT = 293 K
c = 7.1238 (14) Å0.20 × 0.20 × 0.20 mm
β = 99.92 (3)°
Data collection top
Rigaku SCXmini
diffractometer		1863 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1555 reflections with I > 2σ(I)
Tmin = 0.667, Tmax = 0.674Rint = 0.050
8010 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.166H-atom parameters constrained
S = 1.16Δρmax = 1.03 e Å−3
1863 reflectionsΔρmin = −0.88 e Å−3
98 parameters
Special details top

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) top
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) top
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, º) top
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 code: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, º) top
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.

Experimental details

Crystal data
Chemical formula(C6H7FN)2[CuCl4]
Mr429.59
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)15.603 (3), 7.3893 (15), 7.1238 (14)
β (°) 99.92 (3)
V (Å3)809.0 (3)
Z2
Radiation typeMo Kα
µ (mm−1)2.02
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku SCXmini
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.667, 0.674
No. of measured, independent and
observed [I > 2σ(I)] reflections		8010, 1863, 1555
Rint0.050
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.166, 1.16
No. of reflections1863
No. of parameters98
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.03, −0.88

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl20.892.373.248 (6)168.2
N1—H1A···Cl3i0.892.373.196 (5)154.4
N1—H1C···Cl3ii0.892.553.353 (6)150.8
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1.
 

Acknowledgements

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

References

First citationBhattacharya, R., Chanda, S., Bocelli, G., Cantoni, A. & Ghosh, A. (2004). J. Chem. Crystallogr. 34, 393–400.  Web of Science CSD CrossRef CAS Google Scholar
 First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
 First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationYe, H. Y., Fu, D. W., Zhang, Y., Zhang, W., Xiong, R. G. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 42–43.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationYuan, B.-L., Lan, H.-C., Chen, Y.-P. & Li, Y.-B. (2004). Acta Cryst. E60, m617–m619.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationZhang, W., Cheng, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. P. (2009). J. Am. Chem. Soc. 131, 12544–12545.  Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 6| June 2010| Page m656
https://doi.org/10.1107/S1600536810017289
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS