(S)-1,2,4-Trimethyl­piperazine-1,4-diium tetra­chloridozincate(II)

Ru, Z.

doi:10.1107/S1600536810028631

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m1013

https://doi.org/10.1107/S1600536810028631

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(S)-1,2,4-Trimethylpiperazine-1,4-diium tetrachloridozincate(II)

Zong-ling Ru ^a ^*

^aDepartment of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayrzl@yahoo.com.cn

(Received 3 July 2010; accepted 17 July 2010; online 24 July 2010)

In the title compound, (C₇H₁₈N₂)[ZnCl₄], the Zn atom adopts a slightly distorted tetrahedral geometry. The diprotonated piperazine ring adopts a chair conformation. In the crystal structure, the cations and anions are linked by intermolecular N—H⋯Cl hydrogen bonds into a chain along [001].

Related literature

For the ferroelectric behavior of chiral coordination compounds, see: Fu et al. (2007 ). For non-linear optical second harmonic generation of chiral coordination compounds, see: Qu et al. (2003 ). For transition-metal complexes of (S)-2-methylpiperazine, see: Ye et al. (2009 ). For puckering parameters, see: Cremer & Pople (1975 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

(C₇H₁₈N₂)[ZnCl₄]
M_r = 337.40
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.5197 (17) Å
b = 9.7036 (19) Å
c = 17.013 (3) Å
V = 1406.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.48 mm⁻¹
T = 293 K
0.30 × 0.28 × 0.26 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.80, T_max = 0.90
14785 measured reflections
3217 independent reflections
2802 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.067
S = 1.08
3217 reflections
138 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 1355 Friedel pairs
Flack parameter: 0.046 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.93 (3)	2.16 (3)	3.092 (2)	177 (3)
N2—H2C⋯Cl2ⁱⁱ	0.91 (3)	2.24 (3)	3.140 (3)	171 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 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: https://doi.org/10.1107/S1600536810028631/bx2289sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028631/bx2289Isup2.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 (S)-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, (C₇H₁₈N₂)[ZnCl₄] (Fig.1), consists of one 1,2,4-trimethylpiperazinium cation and one ZnCl₄^2-anion. The Zn atom adopts a slightly distorted tetrahedral geometry. The diprotonated piperazine ring adopts a chair conformation with Cremer & Pople (1975) puckering parameters : Q_T =0.5673 (3)Å, θ = 1.8 (3)° , φ= 67 (10)°. In the crystal structure, cations and anions are linked by intermolecular N—H···Cl hydrogen bonds into a one-dimensional chain viewed along the c-axis with set graph-motif C₂²(9) (Bernstein, et al., 1995) (Fig.2).

Related literature top

For the ferroelectric behavior, see: Fu et al. (2007). For non-linear optical second harmonic generation, see: Qu et al. (2003). For transition-metal complexes of (S)-2-methylpiperazine, see: Ye et al. (2009). For puckering parameters, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of (S)-1,2,4-trimethylpiperazine quinine (1 mmol, 0.128 g), ZnCl₂(1 mmol, 0.136 g) and 10% aqueous HCl (6 ml) were mixed and dissolved in 20 ml water by heating to 363 K (15 min) forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed after 8 days.

Structure description top

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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. The packing viewed along the b-axis. Hydrogen bonds are drawn as dashed lines

(S)-1,2,4-Trimethylpiperazine-1,4-diium tetrachloridozincate(II) top

Crystal data top

(C₇H₁₈N₂)[ZnCl₄]	F(000) = 688
M_r = 337.40	D_x = 1.593 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2802 reflections
a = 8.5197 (17) Å	θ = 3.2–27.5°
b = 9.7036 (19) Å	µ = 2.48 mm⁻¹
c = 17.013 (3) Å	T = 293 K
V = 1406.5 (5) Å³	Block, colourless
Z = 4	0.30 × 0.28 × 0.26 mm

Data collection top

Rigaku SCXmini diffractometer	3217 independent reflections
Radiation source: fine-focus sealed tube	2802 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −11→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −12→12
T_min = 0.80, T_max = 0.90	l = −22→22
14785 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0257P)² + 0.2767P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
3217 reflections	Δρ_max = 0.36 e Å⁻³
138 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1355 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.046 (14)

Crystal data top

(C₇H₁₈N₂)[ZnCl₄]	V = 1406.5 (5) Å³
M_r = 337.40	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.5197 (17) Å	µ = 2.48 mm⁻¹
b = 9.7036 (19) Å	T = 293 K
c = 17.013 (3) Å	0.30 × 0.28 × 0.26 mm

Data collection top

Rigaku SCXmini diffractometer	3217 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2802 reflections with I > 2σ(I)
T_min = 0.80, T_max = 0.90	R_int = 0.038
14785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	Δρ_max = 0.36 e Å⁻³
S = 1.08	Δρ_min = −0.36 e Å⁻³
3217 reflections	Absolute structure: Flack (1983), 1355 Friedel pairs
138 parameters	Absolute structure parameter: 0.046 (14)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
Zn1	0.59768 (3)	0.49854 (3)	0.125016 (17)	0.03377 (9)
C1	0.2131 (4)	0.8709 (3)	0.14589 (17)	0.0359 (7)
H1	0.2576	0.8595	0.1986	0.043*
C2	0.3442 (3)	0.8994 (3)	0.08782 (17)	0.0368 (7)
H2A	0.4167	0.8223	0.0882	0.044*
H2B	0.3000	0.9060	0.0354	0.044*
C3	0.3220 (4)	1.1457 (3)	0.10626 (19)	0.0481 (9)
H3A	0.2799	1.1599	0.0539	0.058*
H3B	0.3791	1.2281	0.1212	0.058*
C4	0.1875 (4)	1.1231 (3)	0.16346 (19)	0.0449 (8)
H4A	0.2283	1.1194	0.2166	0.054*
H4B	0.1151	1.2000	0.1602	0.054*
C5	−0.0354 (4)	0.9767 (4)	0.19972 (18)	0.0491 (8)
H5A	0.0010	0.9678	0.2529	0.074*
H5B	−0.0935	0.8958	0.1853	0.074*
H5C	−0.1019	1.0562	0.1955	0.074*
C6	0.5641 (4)	1.0490 (4)	0.0483 (2)	0.0628 (11)
H6A	0.6305	0.9691	0.0477	0.094*
H6B	0.6241	1.1279	0.0643	0.094*
H6C	0.5224	1.0643	−0.0034	0.094*
C7	0.1282 (4)	0.7396 (3)	0.1223 (2)	0.0580 (9)
H7A	0.0840	0.7508	0.0708	0.087*
H7B	0.0458	0.7209	0.1593	0.087*
H7C	0.2011	0.6642	0.1219	0.087*
Cl1	0.44725 (9)	0.46036 (8)	0.01637 (4)	0.0479 (2)
Cl2	0.42671 (10)	0.48120 (12)	0.22655 (4)	0.0642 (3)
Cl3	0.70714 (11)	0.70748 (9)	0.11735 (6)	0.0600 (2)
Cl4	0.79167 (12)	0.34029 (10)	0.13266 (5)	0.0606 (2)
N1	0.1024 (2)	0.9929 (3)	0.14575 (12)	0.0334 (5)
N2	0.4314 (3)	1.0266 (3)	0.10512 (14)	0.0390 (6)
H1A	0.054 (3)	1.003 (3)	0.0967 (16)	0.033 (7)*
H2C	0.477 (4)	1.023 (3)	0.1532 (18)	0.046 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03299 (15)	0.04154 (17)	0.02676 (15)	−0.00188 (15)	−0.00155 (14)	−0.00045 (16)
C1	0.0323 (14)	0.0395 (17)	0.0359 (16)	0.0029 (14)	−0.0043 (14)	0.0082 (12)
C2	0.0345 (16)	0.0368 (17)	0.0390 (15)	0.0024 (13)	0.0001 (13)	−0.0014 (13)
C3	0.055 (2)	0.0371 (18)	0.052 (2)	−0.0065 (15)	0.0007 (17)	0.0019 (14)
C4	0.048 (2)	0.0392 (19)	0.0472 (17)	−0.0059 (15)	−0.0009 (17)	−0.0108 (14)
C5	0.0387 (16)	0.064 (2)	0.0445 (17)	0.0051 (17)	0.0090 (14)	0.0016 (15)
C6	0.045 (2)	0.084 (3)	0.059 (2)	−0.0144 (19)	0.0148 (18)	0.0118 (19)
C7	0.0445 (18)	0.0365 (17)	0.093 (3)	−0.0038 (13)	0.009 (2)	0.008 (2)
Cl1	0.0417 (4)	0.0762 (6)	0.0259 (3)	−0.0185 (4)	−0.0051 (3)	0.0063 (3)
Cl2	0.0424 (4)	0.1219 (9)	0.0283 (4)	−0.0064 (6)	0.0046 (3)	0.0013 (4)
Cl3	0.0541 (4)	0.0453 (5)	0.0806 (6)	−0.0143 (4)	−0.0084 (6)	−0.0038 (5)
Cl4	0.0641 (5)	0.0642 (6)	0.0536 (5)	0.0256 (5)	−0.0113 (5)	−0.0086 (4)
N1	0.0325 (11)	0.0402 (13)	0.0274 (11)	0.0026 (14)	−0.0013 (9)	0.0007 (10)
N2	0.0331 (13)	0.0481 (17)	0.0357 (13)	−0.0095 (11)	−0.0032 (10)	0.0030 (10)

Geometric parameters (Å, º) top

Zn1—Cl3	2.2355 (9)	C4—H4A	0.9700
Zn1—Cl4	2.2597 (9)	C4—H4B	0.9700
Zn1—Cl2	2.2658 (8)	C5—N1	1.499 (3)
Zn1—Cl1	2.2795 (8)	C5—H5A	0.9600
C1—N1	1.513 (4)	C5—H5B	0.9600
C1—C2	1.517 (4)	C5—H5C	0.9600
C1—C7	1.519 (4)	C6—N2	1.504 (4)
C1—H1	0.9800	C6—H6A	0.9600
C2—N2	1.470 (4)	C6—H6B	0.9600
C2—H2A	0.9700	C6—H6C	0.9600
C2—H2B	0.9700	C7—H7A	0.9600
C3—N2	1.485 (4)	C7—H7B	0.9600
C3—C4	1.519 (5)	C7—H7C	0.9600
C3—H3A	0.9700	N1—H1A	0.93 (3)
C3—H3B	0.9700	N2—H2C	0.91 (3)
C4—N1	1.487 (4)

Cl3—Zn1—Cl4	108.34 (5)	N1—C5—H5A	109.5
Cl3—Zn1—Cl2	112.33 (4)	N1—C5—H5B	109.5
Cl4—Zn1—Cl2	112.08 (4)	H5A—C5—H5B	109.5
Cl3—Zn1—Cl1	109.55 (3)	N1—C5—H5C	109.5
Cl4—Zn1—Cl1	110.33 (4)	H5A—C5—H5C	109.5
Cl2—Zn1—Cl1	104.16 (3)	H5B—C5—H5C	109.5
N1—C1—C2	108.4 (2)	N2—C6—H6A	109.5
N1—C1—C7	111.1 (3)	N2—C6—H6B	109.5
C2—C1—C7	109.3 (3)	H6A—C6—H6B	109.5
N1—C1—H1	109.3	N2—C6—H6C	109.5
C2—C1—H1	109.3	H6A—C6—H6C	109.5
C7—C1—H1	109.3	H6B—C6—H6C	109.5
N2—C2—C1	113.2 (2)	C1—C7—H7A	109.5
N2—C2—H2A	108.9	C1—C7—H7B	109.5
C1—C2—H2A	108.9	H7A—C7—H7B	109.5
N2—C2—H2B	108.9	C1—C7—H7C	109.5
C1—C2—H2B	108.9	H7A—C7—H7C	109.5
H2A—C2—H2B	107.7	H7B—C7—H7C	109.5
N2—C3—C4	111.7 (3)	C4—N1—C5	110.3 (2)
N2—C3—H3A	109.3	C4—N1—C1	111.1 (2)
C4—C3—H3A	109.3	C5—N1—C1	113.9 (2)
N2—C3—H3B	109.3	C4—N1—H1A	107.7 (19)
C4—C3—H3B	109.3	C5—N1—H1A	102.4 (16)
H3A—C3—H3B	107.9	C1—N1—H1A	111.0 (18)
N1—C4—C3	111.1 (2)	C2—N2—C3	109.8 (2)
N1—C4—H4A	109.4	C2—N2—C6	111.9 (2)
C3—C4—H4A	109.4	C3—N2—C6	111.6 (3)
N1—C4—H4B	109.4	C2—N2—H2C	111 (2)
C3—C4—H4B	109.4	C3—N2—H2C	107 (2)
H4A—C4—H4B	108.0	C6—N2—H2C	105.5 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.93 (3)	2.16 (3)	3.092 (2)	177 (3)
N2—H2C···Cl2ⁱⁱ	0.91 (3)	2.24 (3)	3.140 (3)	171 (3)

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₇H₁₈N₂)[ZnCl₄]
M_r	337.40
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.5197 (17), 9.7036 (19), 17.013 (3)
V (Å³)	1406.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.48
Crystal size (mm)	0.30 × 0.28 × 0.26

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.80, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	14785, 3217, 2802
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.067, 1.08
No. of reflections	3217
No. of parameters	138
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.36
Absolute structure	Flack (1983), 1355 Friedel pairs
Absolute structure parameter	0.046 (14)

Computer programs: CrystalClear (Rigaku/MSC, 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	0.93 (3)	2.16 (3)	3.092 (2)	177 (3)
N2—H2C···Cl2ⁱⁱ	0.91 (3)	2.24 (3)	3.140 (3)	171 (3)

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

This work was supported by a start-up grant from Anyang Institute of Technology.

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