Bis(4-fluoro-anilinium) tetra-chloridocuprate(II).

The crystal structure of the title compound, (C(6)H(7)FN)(2)[CuCl(4)], consists of parallel two-dimensional perovskite-type layers of corner-sharing CuCl(6) octa-hedra. These are bonded together via N-H⋯Cl hydrogen bonds from the 4-fluoro-anilinium chains, which are almost perpendicular to the layers. The CuCl(4) 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 CuCl(6) octa-hedra. The Cu atoms are situated on crystallographic centers of inversion.

Related literature

For similar 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

Crystal data

(C6H7FN)2[CuCl4]

M = 429.59

Monoclinic,

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 ▶) 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 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ▶).

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

(C6H7FN)2[CuCl4]	F(000) = 430
Mr = 429.59	Dx = 1.763 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7279 reflections
a = 15.603 (3) Å	θ = 3.1–27.5°
b = 7.3893 (15) Å	µ = 2.02 mm−1
c = 7.1238 (14) Å	T = 293 K
β = 99.92 (3)°	Prism, green
V = 809.0 (3) Å3	0.20 × 0.20 × 0.20 mm
Z = 2

Rigaku SCXmini diffractometer	1863 independent reflections
Radiation source: fine-focus sealed tube	1555 reflections with I > 2σ(I)
graphite	Rint = 0.050
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.667, Tmax = 0.674	l = −9→9
8010 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166	H-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 parameters	Δρmax = 1.02 e Å−3
0 restraints	Δρmin = −0.88 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.1209 (5)	0.6057 (12)	0.4232 (12)	0.0590 (19)
H1	0.0831	0.6781	0.4781	0.071*
C2	0.0896 (5)	0.4848 (12)	0.2821 (12)	0.061 (2)
C3	0.1426 (5)	0.3721 (12)	0.2064 (12)	0.066 (2)
H3	0.1195	0.2860	0.1166	0.079*
C4	0.2304 (4)	0.3856 (10)	0.2627 (10)	0.0487 (16)
H4	0.2677	0.3125	0.2076	0.058*
C5	0.2632 (4)	0.5085 (8)	0.4019 (8)	0.0333 (12)
C6	0.2098 (4)	0.6174 (10)	0.4819 (10)	0.0486 (16)
H6	0.2328	0.6998	0.5759	0.058*
N1	0.3577 (3)	0.5283 (7)	0.4557 (8)	0.0392 (12)
H1A	0.3728	0.6415	0.4337	0.059*
H1B	0.3841	0.4524	0.3872	0.059*
H1C	0.3735	0.5032	0.5790	0.059*
F1	0.0021 (3)	0.4721 (10)	0.2268 (10)	0.100 (2)
Cu1	0.5000	0.5000	0.0000	0.0265 (3)
Cl2	0.47957 (10)	0.28942 (18)	0.22368 (19)	0.0370 (4)
Cl3	0.64585 (9)	0.4598 (2)	0.0752 (2)	0.0403 (4)

	U11	U22	U33	U12	U13	U23
C1	0.042 (4)	0.066 (5)	0.071 (5)	0.009 (3)	0.015 (4)	−0.003 (4)
C2	0.033 (3)	0.087 (6)	0.058 (5)	−0.012 (4)	−0.003 (3)	0.009 (4)
C3	0.055 (5)	0.074 (6)	0.067 (5)	−0.018 (4)	0.003 (4)	−0.024 (4)
C4	0.044 (4)	0.049 (4)	0.053 (4)	−0.008 (3)	0.010 (3)	−0.015 (3)
C5	0.034 (3)	0.034 (3)	0.029 (3)	0.003 (2)	−0.001 (2)	0.003 (2)
C6	0.045 (4)	0.046 (4)	0.054 (4)	−0.001 (3)	0.006 (3)	−0.006 (3)
N1	0.043 (3)	0.033 (3)	0.041 (3)	−0.001 (2)	0.008 (2)	0.003 (2)
F1	0.037 (3)	0.143 (6)	0.114 (5)	−0.019 (3)	−0.007 (3)	−0.020 (4)
Cu1	0.0304 (5)	0.0262 (5)	0.0233 (5)	0.0012 (4)	0.0060 (3)	0.0062 (3)
Cl2	0.0525 (9)	0.0308 (7)	0.0289 (7)	−0.0017 (6)	0.0101 (6)	0.0064 (5)
Cl3	0.0301 (7)	0.0449 (8)	0.0455 (8)	0.0038 (6)	0.0050 (6)	0.0011 (6)

C1—C2	1.370 (12)	C5—N1	1.465 (8)
C1—C6	1.381 (10)	C6—H6	0.9300
C1—H1	0.9300	N1—H1A	0.8900
C2—C3	1.350 (12)	N1—H1B	0.8900
C2—F1	1.359 (9)	N1—H1C	0.8900
C3—C4	1.362 (10)	Cu1—Cl3	2.2657 (15)
C3—H3	0.9300	Cu1—Cl3i	2.2657 (15)
C4—C5	1.376 (8)	Cu1—Cl2	2.2884 (13)
C4—H4	0.9300	Cu1—Cl2i	2.2884 (13)
C5—C6	1.353 (9)
C2—C1—C6	118.3 (7)	C5—C6—C1	119.7 (7)
C2—C1—H1	120.8	C5—C6—H6	120.2
C6—C1—H1	120.8	C1—C6—H6	120.2
C3—C2—F1	119.7 (8)	C5—N1—H1A	109.5
C3—C2—C1	122.0 (7)	C5—N1—H1B	109.5
F1—C2—C1	118.1 (8)	H1A—N1—H1B	109.5
C2—C3—C4	119.4 (7)	C5—N1—H1C	109.5
C2—C3—H3	120.3	H1A—N1—H1C	109.5
C4—C3—H3	120.3	H1B—N1—H1C	109.5
C3—C4—C5	119.4 (7)	Cl3—Cu1—Cl3i	180.00 (2)
C3—C4—H4	120.3	Cl3—Cu1—Cl2	90.06 (6)
C5—C4—H4	120.3	Cl3i—Cu1—Cl2	89.94 (6)
C6—C5—C4	121.1 (6)	Cl3—Cu1—Cl2i	89.94 (6)
C6—C5—N1	119.7 (5)	Cl3i—Cu1—Cl2i	90.06 (6)
C4—C5—N1	119.2 (6)	Cl2—Cu1—Cl2i	180.00 (5)

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···Cl3ii	0.89	2.37	3.196 (5)	154
N1—H1C···Cl3iii	0.89	2.55	3.353 (6)	151

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) ; (ii) .