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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): m515.
Published online 2010 April 10. doi:  10.1107/S1600536810012547
PMCID: PMC2979142

2-Methyl­piperazinediium tetra­chlorido­zincate(II)

Abstract

The asymmetric unit of the title compound, (C5H14N2)[ZnCl4], consists of a diprotonated 2-methyl­piperazine cation and a tetra­chloridozincate anion. The ZnII ion is in a slightly distorted tetra­hedral coordination environment. The six-membered piperazine ring adopts a chair conformation. The crystal structure is stabilized by inter­molecular N—H(...)Cl hydrogen bonds.

Related literature

For ferroelectricity in coordination polymers, see: Fu et al. (2007 [triangle]). For nonlinear optical second harmonic generation induced by coordination polymers, see: Qu et al. (2003 [triangle]). For transition-metal complexes of (R)-2-methyl­piperazine, see: Ye et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m515-scheme1.jpg

Experimental

Crystal data

  • (C5H14N2)[ZnCl4]
  • M r = 309.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m515-efi1.jpg
  • a = 8.4183 (17) Å
  • b = 14.939 (3) Å
  • c = 9.830 (2) Å
  • β = 90.35 (3)°
  • V = 1236.3 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.81 mm−1
  • T = 291 K
  • 0.35 × 0.25 × 0.15 mm

Data collection

  • Rigaku SCXmini CCD diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.440, T max = 0.678
  • 11203 measured reflections
  • 2423 independent reflections
  • 2112 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.088
  • S = 1.11
  • 2423 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 0.67 e Å−3
  • Δρmin = −0.45 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810012547/hy2296sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012547/hy2296Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

The existence of a chiral center 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 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 (±)-2-methylpiperazine cation and a tetrachloridozinc anion with the ZnII ion in a slightly distorted tetrahedral coordination environment (Fig. 1). The 6-membered ring of piperazine adopts a chair conformation. The crystal structure is stabilized by intermolecular N—H···Cl hydrogen bonds (Table 1). The hydrogen bonds form a three-dimensional network (Fig. 2).

Experimental

A mixture of (±)-2-methylpiperazine (1 mmol, 0.100 g), ZnCl2 (1 mmol, 0.136 g) and 10% aqueous HCl (6 ml) was dissolved in 30 ml water by heating to 353 K (10 min), forming a clear solution. The reaction mixture was cooled slowly to room temperature and crystals of the title compound formed after 6 d.

Refinement

H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.98 (CH), 0.97 (CH2) and 0.96 (CH3) Å, N—H = 0.90 Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C, N).

Figures

Fig. 1.
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The crystal packing viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

Crystal data

(C5H14N2)[ZnCl4]F(000) = 624
Mr = 309.35Dx = 1.662 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2112 reflections
a = 8.4183 (17) Åθ = 3.2–26.0°
b = 14.939 (3) ŵ = 2.81 mm1
c = 9.830 (2) ÅT = 291 K
β = 90.35 (3)°Block, colorless
V = 1236.3 (4) Å30.35 × 0.25 × 0.15 mm
Z = 4

Data collection

Rigaku SCXmini CCD diffractometer2423 independent reflections
Radiation source: fine-focus sealed tube2112 reflections with I > 2σ(I)
graphiteRint = 0.045
Detector resolution: 13.6612 pixels mm-1θmax = 26.0°, θmin = 3.2°
ω scansh = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −18→18
Tmin = 0.440, Tmax = 0.678l = −12→12
11203 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.0275P)2 + 1.3805P] where P = (Fo2 + 2Fc2)/3
2423 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.67 e Å3
0 restraintsΔρmin = −0.45 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.3285 (4)0.0505 (2)0.7709 (4)0.0525 (9)
H1C0.36820.01010.84050.063*
H1D0.32820.01880.68480.063*
C20.4331 (4)0.1290 (3)0.7618 (4)0.0518 (9)
H2C0.53840.11010.73460.062*
H2D0.44190.15710.85050.062*
C30.2019 (3)0.2241 (2)0.6920 (3)0.0373 (7)
H30.20130.25600.77910.045*
C40.0994 (4)0.1433 (2)0.7029 (4)0.0429 (8)
H4A0.09170.11450.61470.051*
H4B−0.00660.16130.72970.051*
C50.1468 (4)0.2868 (2)0.5815 (4)0.0521 (9)
H5A0.15180.25690.49520.078*
H5B0.21410.33860.58010.078*
H5C0.03930.30470.59880.078*
Cl10.20460 (10)−0.02794 (6)0.10506 (9)0.0464 (2)
Cl20.19838 (10)0.21504 (6)0.07287 (9)0.0490 (2)
Cl3−0.04089 (10)0.10987 (6)0.33241 (9)0.0470 (2)
Cl40.40648 (12)0.10940 (8)0.37036 (10)0.0670 (3)
N10.1644 (3)0.07835 (19)0.8046 (3)0.0428 (7)
H1A0.16390.10370.88770.051*
H1B0.10130.02970.80720.051*
N20.3697 (3)0.19527 (18)0.6611 (3)0.0379 (6)
H2A0.37210.17080.57750.046*
H2B0.43300.24380.66070.046*
Zn10.19783 (4)0.10028 (3)0.22722 (4)0.03895 (14)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.056 (2)0.043 (2)0.059 (2)0.0128 (17)0.0036 (19)0.0120 (17)
C20.0327 (18)0.066 (2)0.057 (2)0.0041 (16)−0.0075 (16)0.0141 (19)
C30.0335 (16)0.0407 (18)0.0376 (17)0.0001 (13)0.0016 (14)0.0058 (14)
C40.0302 (16)0.050 (2)0.049 (2)−0.0042 (14)0.0006 (14)0.0125 (16)
C50.048 (2)0.050 (2)0.058 (2)0.0058 (16)−0.0006 (18)0.0196 (18)
Cl10.0528 (5)0.0424 (5)0.0441 (5)0.0075 (4)0.0048 (4)−0.0056 (4)
Cl20.0456 (5)0.0490 (5)0.0527 (5)0.0104 (4)0.0109 (4)0.0079 (4)
Cl30.0396 (4)0.0540 (5)0.0474 (5)0.0026 (4)0.0088 (4)−0.0057 (4)
Cl40.0453 (5)0.1063 (9)0.0493 (6)0.0189 (5)−0.0136 (4)−0.0232 (5)
N10.0417 (15)0.0416 (16)0.0451 (16)−0.0079 (12)0.0057 (13)0.0112 (13)
N20.0265 (13)0.0475 (16)0.0398 (15)−0.0088 (11)0.0010 (11)0.0074 (12)
Zn10.0354 (2)0.0457 (2)0.0357 (2)0.00775 (16)−0.00171 (16)−0.00409 (16)

Geometric parameters (Å, °)

C1—C21.470 (5)C4—H4B0.9700
C1—N11.482 (4)C5—H5A0.9600
C1—H1C0.9700C5—H5B0.9600
C1—H1D0.9700C5—H5C0.9600
C2—N21.496 (4)Cl1—Zn12.2616 (10)
C2—H2C0.9700Cl2—Zn12.2895 (10)
C2—H2D0.9700Cl3—Zn12.2702 (11)
C3—C41.487 (4)Cl4—Zn12.2480 (12)
C3—C51.505 (4)N1—H1A0.9000
C3—N21.509 (4)N1—H1B0.9000
C3—H30.9800N2—H2A0.9000
C4—N11.495 (4)N2—H2B0.9000
C4—H4A0.9700
C2—C1—N1110.4 (3)C3—C5—H5A109.5
C2—C1—H1C109.6C3—C5—H5B109.5
N1—C1—H1C109.6H5A—C5—H5B109.5
C2—C1—H1D109.6C3—C5—H5C109.5
N1—C1—H1D109.6H5A—C5—H5C109.5
H1C—C1—H1D108.1H5B—C5—H5C109.5
C1—C2—N2110.9 (3)C1—N1—C4111.8 (3)
C1—C2—H2C109.5C1—N1—H1A109.3
N2—C2—H2C109.5C4—N1—H1A109.3
C1—C2—H2D109.5C1—N1—H1B109.3
N2—C2—H2D109.5C4—N1—H1B109.3
H2C—C2—H2D108.0H1A—N1—H1B107.9
C4—C3—C5112.3 (3)C2—N2—C3112.7 (2)
C4—C3—N2109.1 (3)C2—N2—H2A109.0
C5—C3—N2108.5 (3)C3—N2—H2A109.0
C4—C3—H3109.0C2—N2—H2B109.0
C5—C3—H3109.0C3—N2—H2B109.0
N2—C3—H3109.0H2A—N2—H2B107.8
C3—C4—N1111.4 (3)Cl4—Zn1—Cl1111.20 (4)
C3—C4—H4A109.3Cl4—Zn1—Cl3113.67 (4)
N1—C4—H4A109.3Cl1—Zn1—Cl3108.70 (4)
C3—C4—H4B109.3Cl4—Zn1—Cl2111.39 (5)
N1—C4—H4B109.3Cl1—Zn1—Cl2106.39 (4)
H4A—C4—H4B108.0Cl3—Zn1—Cl2105.07 (4)
N1—C1—C2—N2−55.8 (4)C3—C4—N1—C1−57.4 (4)
C5—C3—C4—N1175.0 (3)C1—C2—N2—C355.8 (4)
N2—C3—C4—N154.6 (4)C4—C3—N2—C2−54.5 (4)
C2—C1—N1—C457.2 (4)C5—C3—N2—C2−177.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl2i0.902.483.346 (3)161
N1—H1B···Cl3ii0.902.553.284 (3)140
N1—H1B···Cl1ii0.902.723.322 (3)125
N2—H2A···Cl40.902.253.150 (3)174
N2—H2B···Cl2iii0.902.483.199 (3)137
N2—H2B···Cl3iii0.902.773.444 (3)133

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2296).

References

  • Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. D. (2007). J. Am. Chem. Soc.129, 5346–5347. [PubMed]
  • Qu, Z.-R., Zhao, H., Wang, X.-S., Li, Y.-H., Song, Y.-M., Liu, Y.-J., Ye, Q., Xiong, R.-G., Abrahams, B. F., Xue, Z.-L. & You, X.-Z. (2003). Inorg. Chem.42, 7710–7712. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Ye, H.-Y., Fu, D.-W., Zhang, Y., Zhang, W., Xiong, R.-G. & Huang, S. D. (2009). J. Am. Chem. Soc.131, 42–43. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography