Bis(diisopropyl­ammonium) tetra­chloridocuprate(II)

Xu, J.

doi:10.1107/S1600536812004928

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m285

doi:10.1107/S1600536812004928

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Bis(diisopropylammonium) tetrachloridocuprate(II)

Jie Xu ^a ^*

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wangyc33@yahoo.com.cn

(Received 3 February 2012; accepted 4 February 2012; online 10 February 2012)

In the title molecular salt, (C₆H₁₆N)₂[CuCl₄], the Cu^II ion adopts an extremely distorted tetrahedral coordination geometry. All the ammonium H atoms are involved in N—H⋯Cl hydrogen bonds, which serve to link the cations and anions into chains propagating along the c-axis direction.

Related literature

For background to molecular ferroelectric crystals, see: Fu et al. (2011 ).

Experimental

Crystal data

(C₆H₁₆N)₂[CuCl₄]
M_r = 409.74
Monoclinic, P 2₁ /c
a = 10.541 (2) Å
b = 14.402 (3) Å
c = 14.641 (6) Å
β = 114.38 (2)°
V = 2024.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 298 K
0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.910, T_max = 1.000
20644 measured reflections
4637 independent reflections
3904 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.081
S = 1.10
4637 reflections
180 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—Cl1	2.2419 (9)
Cu1—Cl3	2.2439 (11)
Cu1—Cl2	2.2495 (8)
Cu1—Cl4	2.2714 (8)

Cl1—Cu1—Cl3	139.39 (3)
Cl1—Cu1—Cl2	99.91 (3)
Cl3—Cu1—Cl2	95.93 (3)
Cl1—Cu1—Cl4	96.75 (3)
Cl3—Cu1—Cl4	98.18 (3)
Cl2—Cu1—Cl4	134.61 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯Cl4ⁱ	0.90	2.40	3.281 (2)	168
N1—H1D⋯Cl1ⁱ	0.90	2.43	3.282 (2)	157
N2—H2B⋯Cl3	0.90	2.37	3.2434 (19)	164
N1—H1E⋯Cl2	0.90	2.44	3.321 (2)	167
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004928/hb6624sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004928/hb6624Isup2.hkl

checkCIF report

Comment top

Simple organic salts containig amino cations have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (e.g. Fu et al., 2011). As part of our ongonig studies in this area, we now present the crystal structure of the title compound.

The asymmetric unit of the title compound contains two di-isopropylammonium cations and one CuCl₄^2- anion (Table 1 and Fig. 1). Both the amine N atoms are protonated.

In the crystal structure, all the amino H atoms are involved in N—H···Cl H-bonding interactions with the Cl atoms of the CuCl₄^2- anion with N···Cl distances between the range of 3.243 (2)Å to 3.321 (2)Å. These hydrogen bonds link the ionic units into a one-dimentional chain along the c-axis (Table 2 and Fig. 2).

Related literature top

For background to molecular ferroelectric crystals, see: Fu et al. (2011).

Experimental top

A mixture of di-isopropylamine (0.8 mmol) and CuCl₂ (0.4 mmol) were dissolved in HCl/EtOH/distilled water (1:1:1 v/v) solvent. The solution was slowly evaporated in air affording blue block-shaped crystals of the title compound.

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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with displacement ellipsoids drawn at the 30% probability level. C-bound H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of the title compound viewed along the a axis showing the one-dimensionnal hydrogen bondings chain (dashed line). H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Bis(diisopropylammonium) tetrachloridocuprate(II) top

Crystal data top

(C₆H₁₆N)₂[CuCl₄]	F(000) = 860
M_r = 409.74	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3479 reflections
a = 10.541 (2) Å	θ = 3.0–27.5°
b = 14.402 (3) Å	µ = 1.60 mm⁻¹
c = 14.641 (6) Å	T = 298 K
β = 114.38 (2)°	Block, blue
V = 2024.5 (10) Å³	0.10 × 0.03 × 0.03 mm
Z = 4

Data collection top

Rigaku Mercury2 CCD diffractometer	4637 independent reflections
Radiation source: fine-focus sealed tube	3904 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD profile fitting scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.910, T_max = 1.000	l = −18→19
20644 measured reflections

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.029P)² + 0.869P] where P = (F_o² + 2F_c²)/3
4637 reflections	(Δ/σ)_max = 0.001
180 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

(C₆H₁₆N)₂[CuCl₄]	V = 2024.5 (10) Å³
M_r = 409.74	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.541 (2) Å	µ = 1.60 mm⁻¹
b = 14.402 (3) Å	T = 298 K
c = 14.641 (6) Å	0.10 × 0.03 × 0.03 mm
β = 114.38 (2)°

Data collection top

Rigaku Mercury2 CCD diffractometer	4637 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	3904 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.036
20644 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.10	Δρ_max = 0.50 e Å⁻³
4637 reflections	Δρ_min = −0.41 e Å⁻³
180 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
N2	0.48865 (18)	0.84283 (12)	0.29600 (13)	0.0392 (4)
H2B	0.4207	0.8195	0.3114	0.047*
H2C	0.4804	0.8158	0.2384	0.047*
C8	0.4613 (2)	0.94547 (15)	0.27605 (18)	0.0452 (5)
H8A	0.5328	0.9714	0.2569	0.054*
C11	0.6264 (2)	0.81319 (18)	0.37713 (17)	0.0487 (5)
H11A	0.6318	0.8358	0.4417	0.058*
C9	0.3211 (3)	0.95517 (19)	0.1884 (2)	0.0620 (7)
H9A	0.3002	1.0198	0.1737	0.093*
H9B	0.2506	0.9273	0.2051	0.093*
H9C	0.3233	0.9246	0.1308	0.093*
C12	0.7457 (3)	0.8551 (2)	0.3585 (2)	0.0673 (8)
H12A	0.7451	0.9213	0.3656	0.101*
H12B	0.7350	0.8399	0.2919	0.101*
H12C	0.8324	0.8306	0.4062	0.101*
C10	0.6302 (3)	0.7088 (2)	0.3796 (2)	0.0698 (8)
H10A	0.5538	0.6858	0.3927	0.105*
H10B	0.7164	0.6883	0.4317	0.105*
H10C	0.6229	0.6856	0.3162	0.105*
C7	0.4685 (3)	0.99487 (19)	0.3691 (2)	0.0634 (7)
H7A	0.5602	0.9880	0.4216	0.095*
H7B	0.4014	0.9684	0.3901	0.095*
H7C	0.4485	1.0596	0.3546	0.095*
N1	0.09163 (18)	0.59594 (13)	0.28500 (13)	0.0411 (4)
H1D	0.1413	0.6268	0.2574	0.049*
H1E	0.0943	0.6299	0.3374	0.049*
C2	−0.0577 (2)	0.5925 (2)	0.20865 (19)	0.0576 (7)
H2A	−0.1146	0.5644	0.2400	0.069*
C6	0.0892 (3)	0.4518 (2)	0.3773 (3)	0.0843 (10)
H6A	−0.0008	0.4332	0.3287	0.126*
H6B	0.0785	0.4906	0.4269	0.126*
H6C	0.1423	0.3977	0.4091	0.126*
C5	0.1649 (3)	0.50524 (16)	0.32533 (18)	0.0487 (6)
H5A	0.1638	0.4680	0.2690	0.058*
C4	0.3141 (3)	0.5256 (2)	0.3944 (2)	0.0600 (7)
H4A	0.3572	0.5601	0.3588	0.090*
H4B	0.3633	0.4683	0.4180	0.090*
H4C	0.3169	0.5614	0.4505	0.090*
C3	−0.1049 (3)	0.6917 (2)	0.1807 (2)	0.0803 (9)
H3A	−0.0877	0.7268	0.2405	0.120*
H3B	−0.2027	0.6926	0.1381	0.120*
H3C	−0.0542	0.7187	0.1459	0.120*
C1	−0.0719 (3)	0.5348 (2)	0.1193 (2)	0.0827 (10)
H1A	−0.0459	0.4718	0.1401	0.124*
H1B	−0.0120	0.5593	0.0904	0.124*
H1C	−0.1667	0.5365	0.0704	0.124*
Cu1	0.26640 (3)	0.773295 (18)	0.52212 (2)	0.03879 (9)
Cl4	0.49483 (6)	0.73243 (4)	0.58638 (4)	0.05000 (15)
Cl3	0.23772 (7)	0.80136 (4)	0.36402 (4)	0.05210 (15)
Cl2	0.06532 (6)	0.69540 (5)	0.48106 (5)	0.05519 (16)
Cl1	0.27415 (8)	0.85100 (5)	0.65701 (5)	0.06438 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0416 (10)	0.0417 (10)	0.0380 (9)	−0.0027 (8)	0.0200 (8)	−0.0017 (8)
C8	0.0522 (13)	0.0385 (11)	0.0523 (13)	−0.0042 (10)	0.0289 (11)	−0.0003 (10)
C11	0.0464 (13)	0.0602 (15)	0.0355 (12)	0.0030 (11)	0.0128 (10)	0.0007 (11)
C9	0.0689 (18)	0.0498 (15)	0.0628 (16)	0.0123 (13)	0.0226 (14)	0.0078 (12)
C12	0.0449 (14)	0.082 (2)	0.0716 (19)	−0.0011 (14)	0.0208 (14)	−0.0004 (15)
C10	0.0741 (19)	0.0608 (17)	0.0659 (18)	0.0115 (14)	0.0201 (16)	0.0158 (14)
C7	0.0783 (19)	0.0520 (15)	0.0686 (18)	−0.0088 (13)	0.0390 (16)	−0.0174 (13)
N1	0.0389 (10)	0.0450 (10)	0.0401 (10)	−0.0018 (8)	0.0171 (8)	0.0045 (8)
C2	0.0355 (12)	0.0780 (19)	0.0547 (15)	−0.0065 (12)	0.0140 (11)	0.0168 (13)
C6	0.082 (2)	0.0666 (19)	0.096 (2)	−0.0093 (16)	0.0291 (19)	0.0345 (18)
C5	0.0543 (14)	0.0417 (12)	0.0470 (13)	0.0021 (10)	0.0179 (11)	0.0009 (10)
C4	0.0502 (15)	0.0638 (16)	0.0601 (16)	0.0099 (12)	0.0169 (13)	0.0094 (13)
C3	0.0601 (18)	0.096 (2)	0.071 (2)	0.0284 (17)	0.0131 (15)	0.0132 (18)
C1	0.073 (2)	0.085 (2)	0.0594 (18)	−0.0175 (17)	−0.0040 (15)	−0.0042 (16)
Cu1	0.04210 (16)	0.04234 (16)	0.03866 (15)	−0.00002 (11)	0.02342 (12)	−0.00011 (11)
Cl4	0.0416 (3)	0.0643 (4)	0.0472 (3)	0.0021 (3)	0.0214 (3)	−0.0004 (3)
Cl3	0.0613 (4)	0.0590 (3)	0.0436 (3)	−0.0059 (3)	0.0292 (3)	0.0079 (3)
Cl2	0.0426 (3)	0.0740 (4)	0.0546 (3)	−0.0075 (3)	0.0258 (3)	0.0014 (3)
Cl1	0.0727 (4)	0.0751 (4)	0.0618 (4)	−0.0067 (3)	0.0443 (4)	−0.0227 (3)

Geometric parameters (Å, º) top

N2—C11	1.509 (3)	N1—H1D	0.9000
N2—C8	1.511 (3)	N1—H1E	0.9000
N2—H2B	0.9000	C2—C1	1.504 (4)
N2—H2C	0.9000	C2—C3	1.513 (4)
C8—C7	1.510 (3)	C2—H2A	0.9800
C8—C9	1.511 (4)	C6—C5	1.519 (4)
C8—H8A	0.9800	C6—H6A	0.9600
C11—C10	1.505 (4)	C6—H6B	0.9600
C11—C12	1.517 (4)	C6—H6C	0.9600
C11—H11A	0.9800	C5—C4	1.507 (3)
C9—H9A	0.9600	C5—H5A	0.9800
C9—H9B	0.9600	C4—H4A	0.9600
C9—H9C	0.9600	C4—H4B	0.9600
C12—H12A	0.9600	C4—H4C	0.9600
C12—H12B	0.9600	C3—H3A	0.9600
C12—H12C	0.9600	C3—H3B	0.9600
C10—H10A	0.9600	C3—H3C	0.9600
C10—H10B	0.9600	C1—H1A	0.9600
C10—H10C	0.9600	C1—H1B	0.9600
C7—H7A	0.9600	C1—H1C	0.9600
C7—H7B	0.9600	Cu1—Cl1	2.2419 (9)
C7—H7C	0.9600	Cu1—Cl3	2.2439 (11)
N1—C5	1.508 (3)	Cu1—Cl2	2.2495 (8)
N1—C2	1.509 (3)	Cu1—Cl4	2.2714 (8)

C11—N2—C8	118.27 (18)	C5—N1—H1E	107.8
C11—N2—H2B	107.7	C2—N1—H1E	107.8
C8—N2—H2B	107.7	H1D—N1—H1E	107.1
C11—N2—H2C	107.7	C1—C2—N1	111.2 (2)
C8—N2—H2C	107.7	C1—C2—C3	112.5 (2)
H2B—N2—H2C	107.1	N1—C2—C3	107.1 (2)
C7—C8—C9	112.9 (2)	C1—C2—H2A	108.6
C7—C8—N2	110.6 (2)	N1—C2—H2A	108.6
C9—C8—N2	107.23 (19)	C3—C2—H2A	108.6
C7—C8—H8A	108.7	C5—C6—H6A	109.5
C9—C8—H8A	108.7	C5—C6—H6B	109.5
N2—C8—H8A	108.7	H6A—C6—H6B	109.5
C10—C11—N2	108.0 (2)	C5—C6—H6C	109.5
C10—C11—C12	112.7 (2)	H6A—C6—H6C	109.5
N2—C11—C12	110.2 (2)	H6B—C6—H6C	109.5
C10—C11—H11A	108.6	C4—C5—N1	108.54 (19)
N2—C11—H11A	108.6	C4—C5—C6	112.4 (2)
C12—C11—H11A	108.6	N1—C5—C6	110.2 (2)
C8—C9—H9A	109.5	C4—C5—H5A	108.5
C8—C9—H9B	109.5	N1—C5—H5A	108.5
H9A—C9—H9B	109.5	C6—C5—H5A	108.5
C8—C9—H9C	109.5	C5—C4—H4A	109.5
H9A—C9—H9C	109.5	C5—C4—H4B	109.5
H9B—C9—H9C	109.5	H4A—C4—H4B	109.5
C11—C12—H12A	109.5	C5—C4—H4C	109.5
C11—C12—H12B	109.5	H4A—C4—H4C	109.5
H12A—C12—H12B	109.5	H4B—C4—H4C	109.5
C11—C12—H12C	109.5	C2—C3—H3A	109.5
H12A—C12—H12C	109.5	C2—C3—H3B	109.5
H12B—C12—H12C	109.5	H3A—C3—H3B	109.5
C11—C10—H10A	109.5	C2—C3—H3C	109.5
C11—C10—H10B	109.5	H3A—C3—H3C	109.5
H10A—C10—H10B	109.5	H3B—C3—H3C	109.5
C11—C10—H10C	109.5	C2—C1—H1A	109.5
H10A—C10—H10C	109.5	C2—C1—H1B	109.5
H10B—C10—H10C	109.5	H1A—C1—H1B	109.5
C8—C7—H7A	109.5	C2—C1—H1C	109.5
C8—C7—H7B	109.5	H1A—C1—H1C	109.5
H7A—C7—H7B	109.5	H1B—C1—H1C	109.5
C8—C7—H7C	109.5	Cl1—Cu1—Cl3	139.39 (3)
H7A—C7—H7C	109.5	Cl1—Cu1—Cl2	99.91 (3)
H7B—C7—H7C	109.5	Cl3—Cu1—Cl2	95.93 (3)
C5—N1—C2	118.04 (19)	Cl1—Cu1—Cl4	96.75 (3)
C5—N1—H1D	107.8	Cl3—Cu1—Cl4	98.18 (3)
C2—N1—H1D	107.8	Cl2—Cu1—Cl4	134.61 (3)

C11—N2—C8—C7	−59.6 (3)	C5—N1—C2—C1	−56.3 (3)
C11—N2—C8—C9	176.88 (19)	C5—N1—C2—C3	−179.6 (2)
C8—N2—C11—C10	−177.9 (2)	C2—N1—C5—C4	176.3 (2)
C8—N2—C11—C12	−54.4 (3)	C2—N1—C5—C6	−60.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl4ⁱ	0.90	2.40	3.281 (2)	168
N1—H1D···Cl1ⁱ	0.90	2.43	3.282 (2)	157
N2—H2B···Cl3	0.90	2.37	3.2434 (19)	164
N1—H1E···Cl2	0.90	2.44	3.321 (2)	167

Symmetry code: (i) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	(C₆H₁₆N)₂[CuCl₄]
M_r	409.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.541 (2), 14.402 (3), 14.641 (6)
β (°)	114.38 (2)
V (Å³)	2024.5 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.60
Crystal size (mm)	0.10 × 0.03 × 0.03

Data collection
Diffractometer	Rigaku Mercury2 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.910, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20644, 4637, 3904
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.10
No. of reflections	4637
No. of parameters	180
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.41

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

Selected geometric parameters (Å, º) top

Cu1—Cl1	2.2419 (9)	Cu1—Cl2	2.2495 (8)
Cu1—Cl3	2.2439 (11)	Cu1—Cl4	2.2714 (8)

Cl1—Cu1—Cl3	139.39 (3)	Cl1—Cu1—Cl4	96.75 (3)
Cl1—Cu1—Cl2	99.91 (3)	Cl3—Cu1—Cl4	98.18 (3)
Cl3—Cu1—Cl2	95.93 (3)	Cl2—Cu1—Cl4	134.61 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl4ⁱ	0.90	2.40	3.281 (2)	168
N1—H1D···Cl1ⁱ	0.90	2.43	3.282 (2)	157
N2—H2B···Cl3	0.90	2.37	3.2434 (19)	164
N1—H1E···Cl2	0.90	2.44	3.321 (2)	167

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

This work was supported by the Doctoral Foundation of Southeast University, China.

References

Fu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011). Adv. Mater. 23, 5658–5662. Web of Science CSD CrossRef CAS PubMed Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar