(2R)-2-Methyl­piperazinediium tetra­chloridocuprate(II)

Chen, L.Z.; Wan, S.

doi:10.1107/S1600536810007877

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m376

doi:10.1107/S1600536810007877

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(2R)-2-Methylpiperazinediium tetrachloridocuprate(II)

Li Zhaung Chen ^a ^* and Sheng Wan ^a

^aSchool of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

(Received 21 January 2010; accepted 2 March 2010; online 6 March 2010)

In the title compound, (C₅H₁₄N₂)[CuCl₄], the copper(II) ion has a slightly tetrahedrally distorted square-planar coordination geometry and the diprotonated piperazine ring adopts a chair conformation. In the crystal structure, cations and anions are linked by intermolecular N—H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For the ferroelectric and non-linear optical properties of chiral organic ligands, see: Fu et al. (2007 ); Qu et al. (2003 ). For transition metal complexes of 2-methylpiperazine, see: Ye et al. (2009 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

(C₅H₁₄N₂)[CuCl₄]
M_r = 307.53
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0169 (12) Å
b = 12.985 (3) Å
c = 14.644 (3) Å
V = 1144.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.80 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.22 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.87, T_max = 0.90
11992 measured reflections
2627 independent reflections
2469 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.060
S = 1.10
2627 reflections
111 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Absolute structure: Flack (1983 ), 1091 Friedel pairs
Flack parameter: 0.00 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.90	2.36	3.149 (6)	147
N1—H1B⋯Cl1ⁱⁱ	0.90	2.31	3.182 (6)	163
N2—H2A⋯Cl4ⁱⁱⁱ	0.90	2.33	3.218 (6)	168
N2—H2B⋯Cl4^iv	0.90	2.39	3.192 (6)	148
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007877/rz2412sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007877/rz2412Isup2.hkl

checkCIF report

Comment top

The existence of a chiral centre in an organic ligand is very important for the construction noncentrosymmetric or chiral coordination polymers that exhibit desirable physical properties such as ferroelectricity (Fu et al., 2007) and nonlinear optical second harmonic generation (Qu et al., 2003). Chiral (R)-2-methylpiperazine has a chiral centre which have shown tremendous scope in the synthesis of transition metal complexes (Ye et al., 2009). The construction of new members of this family of ligands is an important direction in the development of modern coordination chemistry. We report here the crystal structure of the title compound

The asymmetric unit of the title compound consists of a diprotonated (R)-2-methylpiperazine cation and a tetrachlorocuprate anion (Fig. 1). The copper(II) metal centre is in a slightly tetrahedrally distorted square-planar coordination geometry (maximum displacement 0.0252 (18) Å for atom Cl1). The 6-membered piperazine ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.570 (6) Å, θ = 178.6 (6)° and ϕ = -127.3 (3)°. The crystal structure is stabilized by inter-ion N—H···Cl hydrogen interactions (Table 1) forming a three-dimensional network (Fig. 2).

Related literature top

For the ferroelectric and non-linear optical properties of chiral organic ligands, see: Fu et al. (2007); Qu et al. (2003). For transition metal complexes of 2-methylpiperazine, see: Ye et al. (2009). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of (R)-2-methylpiperazine (1 mmol, 0.1 g ), CuCl₂ (1 mmol, 0.136 g) and 10% aqueous HCl (6 ml) were mixed and dissolved in 30 ml water by heating to 353 K (10 minute) forming a clear solution. The reaction mixture was then cooled slowly to room temperature. Single crystals of the title compound suitable for X-ray analysis were formed after 12 days on slow evaporation of the solvent.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. Packing diagram viewed approximately along the a axis. Hydrogen bonds are drawn as dashed lines.

(2R)-2-Methylpiperazinediium tetrachloridocuprate(II) top

Crystal data top

(C₅H₁₄N₂)[CuCl₄]	F(000) = 620
M_r = 307.53	D_x = 1.785 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2469 reflections
a = 6.0169 (12) Å	θ = 3.1–27.5°
b = 12.985 (3) Å	µ = 2.80 mm⁻¹
c = 14.644 (3) Å	T = 293 K
V = 1144.1 (4) Å³	Block, yellow
Z = 4	0.30 × 0.25 × 0.22 mm

Data collection top

Rigaku SCXmini diffractometer	2627 independent reflections
Radiation source: fine-focus sealed tube	2469 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.87, T_max = 0.90	l = −18→18
11992 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0239P)² + 0.0175P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.060	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.30 e Å⁻³
2627 reflections	Δρ_min = −0.53 e Å⁻³
111 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.193 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1091 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (3)

Crystal data top

(C₅H₁₄N₂)[CuCl₄]	V = 1144.1 (4) Å³
M_r = 307.53	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0169 (12) Å	µ = 2.80 mm⁻¹
b = 12.985 (3) Å	T = 293 K
c = 14.644 (3) Å	0.30 × 0.25 × 0.22 mm

Data collection top

Rigaku SCXmini diffractometer	2627 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2469 reflections with I > 2σ(I)
T_min = 0.87, T_max = 0.90	R_int = 0.051
11992 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.060	Δρ_max = 0.30 e Å⁻³
S = 1.10	Δρ_min = −0.53 e Å⁻³
2627 reflections	Absolute structure: Flack (1983), 1091 Friedel pairs
111 parameters	Absolute structure parameter: 0.00 (3)
1 restraint

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

	x	y	z	U_iso*/U_eq
Cu1	0.82482 (13)	1.34903 (5)	0.01022 (5)	0.0237 (3)
Cl4	0.8203 (3)	1.32659 (11)	0.17172 (9)	0.0251 (4)
Cl3	0.8247 (3)	1.17476 (11)	−0.00811 (9)	0.0256 (4)
Cl2	0.8317 (3)	1.52141 (11)	0.02454 (12)	0.0365 (4)
Cl1	0.8196 (3)	1.36387 (11)	−0.14937 (10)	0.0250 (4)
N1	0.8224 (9)	1.0679 (4)	0.1788 (3)	0.0289 (11)
H1A	0.9338	1.1063	0.1559	0.035*
H1B	0.6932	1.0976	0.1626	0.035*
N2	0.6773 (9)	0.8919 (4)	0.2799 (3)	0.0263 (11)
H2A	0.8089	0.8638	0.2951	0.032*
H2B	0.5692	0.8523	0.3038	0.032*
C5	0.6696 (17)	0.7855 (5)	0.1398 (5)	0.055 (2)
H5C	0.5702	0.7410	0.1725	0.083*
H5B	0.8190	0.7603	0.1458	0.083*
H5A	0.6288	0.7867	0.0764	0.083*
C2	0.6553 (12)	0.8933 (5)	0.1786 (4)	0.0300 (14)
H2C	0.5097	0.9221	0.1630	0.036*
C4	0.8395 (11)	1.0661 (5)	0.2797 (4)	0.0309 (14)
H4B	0.8227	1.1354	0.3035	0.037*
H4A	0.9850	1.0408	0.2975	0.037*
C3	0.6623 (12)	0.9975 (5)	0.3195 (4)	0.0304 (13)
H3B	0.6801	0.9939	0.3853	0.036*
H3A	0.5170	1.0264	0.3067	0.036*
C1	0.8335 (12)	0.9624 (5)	0.1390 (4)	0.0323 (14)
H1D	0.9786	0.9329	0.1512	0.039*
H1C	0.8150	0.9666	0.0733	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0339 (4)	0.0198 (4)	0.0174 (4)	−0.0001 (3)	−0.0003 (3)	0.0000 (3)
Cl4	0.0236 (7)	0.0309 (8)	0.0209 (7)	−0.0006 (7)	−0.0001 (7)	−0.0035 (6)
Cl3	0.0392 (8)	0.0197 (7)	0.0178 (7)	−0.0004 (7)	0.0001 (7)	0.0001 (5)
Cl2	0.0540 (10)	0.0222 (8)	0.0333 (9)	−0.0006 (8)	−0.0017 (10)	−0.0016 (6)
Cl1	0.0238 (7)	0.0308 (8)	0.0205 (7)	−0.0010 (7)	−0.0001 (7)	0.0047 (6)
N1	0.025 (2)	0.034 (3)	0.028 (3)	−0.004 (3)	0.000 (3)	0.013 (2)
N2	0.026 (2)	0.028 (3)	0.024 (3)	−0.004 (3)	0.002 (3)	0.011 (2)
C5	0.090 (6)	0.035 (4)	0.041 (5)	−0.005 (5)	−0.005 (6)	0.000 (3)
C2	0.033 (3)	0.031 (3)	0.026 (3)	−0.001 (3)	−0.003 (3)	0.007 (3)
C4	0.037 (3)	0.031 (3)	0.025 (3)	−0.004 (3)	−0.003 (3)	0.009 (3)
C3	0.037 (3)	0.032 (3)	0.023 (3)	0.001 (3)	0.005 (3)	0.006 (3)
C1	0.037 (3)	0.039 (4)	0.022 (3)	0.000 (3)	0.005 (3)	0.007 (3)

Geometric parameters (Å, º) top

Cu1—Cl2	2.2485 (16)	C5—H5C	0.9600
Cu1—Cl3	2.2788 (16)	C5—H5B	0.9600
Cu1—Cl1	2.3451 (15)	C5—H5A	0.9600
Cu1—Cl4	2.3831 (15)	C2—C1	1.514 (9)
N1—C4	1.482 (8)	C2—H2C	0.9800
N1—C1	1.490 (8)	C4—C3	1.506 (9)
N1—H1A	0.9000	C4—H4B	0.9700
N1—H1B	0.9000	C4—H4A	0.9700
N2—C2	1.489 (8)	C3—H3B	0.9700
N2—C3	1.492 (7)	C3—H3A	0.9700
N2—H2A	0.9000	C1—H1D	0.9700
N2—H2B	0.9000	C1—H1C	0.9700
C5—C2	1.513 (9)

Cl2—Cu1—Cl3	178.25 (7)	N2—C2—C5	111.0 (5)
Cl2—Cu1—Cl1	90.66 (6)	N2—C2—C1	109.0 (5)
Cl3—Cu1—Cl1	87.95 (5)	C5—C2—C1	111.4 (6)
Cl2—Cu1—Cl4	91.68 (6)	N2—C2—H2C	108.5
Cl3—Cu1—Cl4	89.74 (5)	C5—C2—H2C	108.5
Cl1—Cu1—Cl4	177.28 (6)	C1—C2—H2C	108.5
C4—N1—C1	111.9 (4)	N1—C4—C3	110.3 (6)
C4—N1—H1A	109.2	N1—C4—H4B	109.6
C1—N1—H1A	109.2	C3—C4—H4B	109.6
C4—N1—H1B	109.2	N1—C4—H4A	109.6
C1—N1—H1B	109.2	C3—C4—H4A	109.6
H1A—N1—H1B	107.9	H4B—C4—H4A	108.1
C2—N2—C3	111.8 (4)	N2—C3—C4	110.5 (5)
C2—N2—H2A	109.3	N2—C3—H3B	109.6
C3—N2—H2A	109.3	C4—C3—H3B	109.6
C2—N2—H2B	109.3	N2—C3—H3A	109.6
C3—N2—H2B	109.3	C4—C3—H3A	109.6
H2A—N2—H2B	107.9	H3B—C3—H3A	108.1
C2—C5—H5C	109.5	N1—C1—C2	111.3 (5)
C2—C5—H5B	109.5	N1—C1—H1D	109.4
H5C—C5—H5B	109.5	C2—C1—H1D	109.4
C2—C5—H5A	109.5	N1—C1—H1C	109.4
H5C—C5—H5A	109.5	C2—C1—H1C	109.4
H5B—C5—H5A	109.5	H1D—C1—H1C	108.0

C3—N2—C2—C5	−179.7 (7)	N1—C4—C3—N2	56.1 (7)
C3—N2—C2—C1	57.3 (7)	C4—N1—C1—C2	56.4 (7)
C1—N1—C4—C3	−55.8 (7)	N2—C2—C1—N1	−56.0 (7)
C2—N2—C3—C4	−58.1 (7)	C5—C2—C1—N1	−178.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.36	3.149 (6)	147
N1—H1B···Cl1ⁱⁱ	0.90	2.31	3.182 (6)	163
N2—H2A···Cl4ⁱⁱⁱ	0.90	2.33	3.218 (6)	168
N2—H2B···Cl4^iv	0.90	2.39	3.192 (6)	148

Symmetry codes: (i) x+1/2, −y+5/2, −z; (ii) x−1/2, −y+5/2, −z; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[CuCl₄]
M_r	307.53
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.0169 (12), 12.985 (3), 14.644 (3)
V (Å³)	1144.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.80
Crystal size (mm)	0.30 × 0.25 × 0.22

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.87, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	11992, 2627, 2469
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.060, 1.10
No. of reflections	2627
No. of parameters	111
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.53
Absolute structure	Flack (1983), 1091 Friedel pairs
Absolute structure parameter	0.00 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90	2.36	3.149 (6)	147.1
N1—H1B···Cl1ⁱⁱ	0.90	2.31	3.182 (6)	162.9
N2—H2A···Cl4ⁱⁱⁱ	0.90	2.33	3.218 (6)	167.6
N2—H2B···Cl4^iv	0.90	2.39	3.192 (6)	147.7

Symmetry codes: (i) x+1/2, −y+5/2, −z; (ii) x−1/2, −y+5/2, −z; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2.

Acknowledgements

This work was supported by a start-up grant from Jiangsu University of Science and Technology

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