2-Methyl­piperazinediium tetra­chlorido­zincate(II)

Yin, M.; Wu, S.-T.

doi:10.1107/S1600536810012547

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m515

https://doi.org/10.1107/S1600536810012547

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2-Methylpiperazinediium tetrachloridozincate(II)

Ming Yin ^a ^* and Shao-Tong Wu ^a

^aSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: yinming1978@yahoo.cn

(Received 23 March 2010; accepted 3 April 2010; online 10 April 2010)

The asymmetric unit of the title compound, (C₅H₁₄N₂)[ZnCl₄], consists of a diprotonated 2-methylpiperazine cation and a tetrachloridozincate anion. The Zn^II 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 ). For nonlinear optical second harmonic generation induced by coordination polymers, see: Qu et al. (2003 ). For transition-metal complexes of (R)-2-methylpiperazine, see: Ye et al. (2009 ).

Experimental

Crystal data

(C₅H₁₄N₂)[ZnCl₄]
M_r = 309.35
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.088
S = 1.11
2423 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2ⁱ	0.90	2.48	3.346 (3)	161
N1—H1B⋯Cl3ⁱⁱ	0.90	2.55	3.284 (3)	140
N1—H1B⋯Cl1ⁱⁱ	0.90	2.72	3.322 (3)	125
N2—H2A⋯Cl4	0.90	2.25	3.150 (3)	174
N2—H2B⋯Cl2ⁱⁱⁱ	0.90	2.48	3.199 (3)	137
N2—H2B⋯Cl3ⁱⁱⁱ	0.90	2.77	3.444 (3)	133
Symmetry codes: (i) x, y, z+1; (ii) -x, -y, -z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012547/hy2296Isup2.hkl

checkCIF report

Comment top

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 Zn^II 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).

Related literature top

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

Experimental top

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.

Structure description top

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) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	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.

2-Methylpiperazinediium tetrachloridozinc(II) top

Crystal data top

(C₅H₁₄N₂)[ZnCl₄]	F(000) = 624
M_r = 309.35	D_x = 1.662 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2112 reflections
a = 8.4183 (17) Å	θ = 3.2–26.0°
b = 14.939 (3) Å	µ = 2.81 mm⁻¹
c = 9.830 (2) Å	T = 291 K
β = 90.35 (3)°	Block, colorless
V = 1236.3 (4) Å³	0.35 × 0.25 × 0.15 mm
Z = 4

Data collection top

Rigaku SCXmini CCD diffractometer	2423 independent reflections
Radiation source: fine-focus sealed tube	2112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.440, T_max = 0.678	l = −12→12
11203 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0275P)² + 1.3805P] where P = (F_o² + 2F_c²)/3
2423 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

(C₅H₁₄N₂)[ZnCl₄]	V = 1236.3 (4) Å³
M_r = 309.35	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.4183 (17) Å	µ = 2.81 mm⁻¹
b = 14.939 (3) Å	T = 291 K
c = 9.830 (2) Å	0.35 × 0.25 × 0.15 mm
β = 90.35 (3)°

Data collection top

Rigaku SCXmini CCD diffractometer	2423 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2112 reflections with I > 2σ(I)
T_min = 0.440, T_max = 0.678	R_int = 0.045
11203 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.11	Δρ_max = 0.67 e Å⁻³
2423 reflections	Δρ_min = −0.45 e Å⁻³
110 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.3285 (4)	0.0505 (2)	0.7709 (4)	0.0525 (9)
H1C	0.3682	0.0101	0.8405	0.063*
H1D	0.3282	0.0188	0.6848	0.063*
C2	0.4331 (4)	0.1290 (3)	0.7618 (4)	0.0518 (9)
H2C	0.5384	0.1101	0.7346	0.062*
H2D	0.4419	0.1571	0.8505	0.062*
C3	0.2019 (3)	0.2241 (2)	0.6920 (3)	0.0373 (7)
H3	0.2013	0.2560	0.7791	0.045*
C4	0.0994 (4)	0.1433 (2)	0.7029 (4)	0.0429 (8)
H4A	0.0917	0.1145	0.6147	0.051*
H4B	−0.0066	0.1613	0.7297	0.051*
C5	0.1468 (4)	0.2868 (2)	0.5815 (4)	0.0521 (9)
H5A	0.1518	0.2569	0.4952	0.078*
H5B	0.2141	0.3386	0.5801	0.078*
H5C	0.0393	0.3047	0.5988	0.078*
Cl1	0.20460 (10)	−0.02794 (6)	0.10506 (9)	0.0464 (2)
Cl2	0.19838 (10)	0.21504 (6)	0.07287 (9)	0.0490 (2)
Cl3	−0.04089 (10)	0.10987 (6)	0.33241 (9)	0.0470 (2)
Cl4	0.40648 (12)	0.10940 (8)	0.37036 (10)	0.0670 (3)
N1	0.1644 (3)	0.07835 (19)	0.8046 (3)	0.0428 (7)
H1A	0.1639	0.1037	0.8877	0.051*
H1B	0.1013	0.0297	0.8072	0.051*
N2	0.3697 (3)	0.19527 (18)	0.6611 (3)	0.0379 (6)
H2A	0.3721	0.1708	0.5775	0.046*
H2B	0.4330	0.2438	0.6607	0.046*
Zn1	0.19783 (4)	0.10028 (3)	0.22722 (4)	0.03895 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.056 (2)	0.043 (2)	0.059 (2)	0.0128 (17)	0.0036 (19)	0.0120 (17)
C2	0.0327 (18)	0.066 (2)	0.057 (2)	0.0041 (16)	−0.0075 (16)	0.0141 (19)
C3	0.0335 (16)	0.0407 (18)	0.0376 (17)	0.0001 (13)	0.0016 (14)	0.0058 (14)
C4	0.0302 (16)	0.050 (2)	0.049 (2)	−0.0042 (14)	0.0006 (14)	0.0125 (16)
C5	0.048 (2)	0.050 (2)	0.058 (2)	0.0058 (16)	−0.0006 (18)	0.0196 (18)
Cl1	0.0528 (5)	0.0424 (5)	0.0441 (5)	0.0075 (4)	0.0048 (4)	−0.0056 (4)
Cl2	0.0456 (5)	0.0490 (5)	0.0527 (5)	0.0104 (4)	0.0109 (4)	0.0079 (4)
Cl3	0.0396 (4)	0.0540 (5)	0.0474 (5)	0.0026 (4)	0.0088 (4)	−0.0057 (4)
Cl4	0.0453 (5)	0.1063 (9)	0.0493 (6)	0.0189 (5)	−0.0136 (4)	−0.0232 (5)
N1	0.0417 (15)	0.0416 (16)	0.0451 (16)	−0.0079 (12)	0.0057 (13)	0.0112 (13)
N2	0.0265 (13)	0.0475 (16)	0.0398 (15)	−0.0088 (11)	0.0010 (11)	0.0074 (12)
Zn1	0.0354 (2)	0.0457 (2)	0.0357 (2)	0.00775 (16)	−0.00171 (16)	−0.00409 (16)

Geometric parameters (Å, º) top

C1—C2	1.470 (5)	C4—H4B	0.9700
C1—N1	1.482 (4)	C5—H5A	0.9600
C1—H1C	0.9700	C5—H5B	0.9600
C1—H1D	0.9700	C5—H5C	0.9600
C2—N2	1.496 (4)	Cl1—Zn1	2.2616 (10)
C2—H2C	0.9700	Cl2—Zn1	2.2895 (10)
C2—H2D	0.9700	Cl3—Zn1	2.2702 (11)
C3—C4	1.487 (4)	Cl4—Zn1	2.2480 (12)
C3—C5	1.505 (4)	N1—H1A	0.9000
C3—N2	1.509 (4)	N1—H1B	0.9000
C3—H3	0.9800	N2—H2A	0.9000
C4—N1	1.495 (4)	N2—H2B	0.9000
C4—H4A	0.9700

C2—C1—N1	110.4 (3)	C3—C5—H5A	109.5
C2—C1—H1C	109.6	C3—C5—H5B	109.5
N1—C1—H1C	109.6	H5A—C5—H5B	109.5
C2—C1—H1D	109.6	C3—C5—H5C	109.5
N1—C1—H1D	109.6	H5A—C5—H5C	109.5
H1C—C1—H1D	108.1	H5B—C5—H5C	109.5
C1—C2—N2	110.9 (3)	C1—N1—C4	111.8 (3)
C1—C2—H2C	109.5	C1—N1—H1A	109.3
N2—C2—H2C	109.5	C4—N1—H1A	109.3
C1—C2—H2D	109.5	C1—N1—H1B	109.3
N2—C2—H2D	109.5	C4—N1—H1B	109.3
H2C—C2—H2D	108.0	H1A—N1—H1B	107.9
C4—C3—C5	112.3 (3)	C2—N2—C3	112.7 (2)
C4—C3—N2	109.1 (3)	C2—N2—H2A	109.0
C5—C3—N2	108.5 (3)	C3—N2—H2A	109.0
C4—C3—H3	109.0	C2—N2—H2B	109.0
C5—C3—H3	109.0	C3—N2—H2B	109.0
N2—C3—H3	109.0	H2A—N2—H2B	107.8
C3—C4—N1	111.4 (3)	Cl4—Zn1—Cl1	111.20 (4)
C3—C4—H4A	109.3	Cl4—Zn1—Cl3	113.67 (4)
N1—C4—H4A	109.3	Cl1—Zn1—Cl3	108.70 (4)
C3—C4—H4B	109.3	Cl4—Zn1—Cl2	111.39 (5)
N1—C4—H4B	109.3	Cl1—Zn1—Cl2	106.39 (4)
H4A—C4—H4B	108.0	Cl3—Zn1—Cl2	105.07 (4)

N1—C1—C2—N2	−55.8 (4)	C3—C4—N1—C1	−57.4 (4)
C5—C3—C4—N1	175.0 (3)	C1—C2—N2—C3	55.8 (4)
N2—C3—C4—N1	54.6 (4)	C4—C3—N2—C2	−54.5 (4)
C2—C1—N1—C4	57.2 (4)	C5—C3—N2—C2	−177.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱ	0.90	2.48	3.346 (3)	161
N1—H1B···Cl3ⁱⁱ	0.90	2.55	3.284 (3)	140
N1—H1B···Cl1ⁱⁱ	0.90	2.72	3.322 (3)	125
N2—H2A···Cl4	0.90	2.25	3.150 (3)	174
N2—H2B···Cl2ⁱⁱⁱ	0.90	2.48	3.199 (3)	137
N2—H2B···Cl3ⁱⁱⁱ	0.90	2.77	3.444 (3)	133

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

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[ZnCl₄]
M_r	309.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	8.4183 (17), 14.939 (3), 9.830 (2)
β (°)	90.35 (3)
V (Å³)	1236.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.81
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku SCXmini CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.440, 0.678
No. of measured, independent and observed [I > 2σ(I)] reflections	11203, 2423, 2112
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.088, 1.11
No. of reflections	2423
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.45

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱ	0.90	2.48	3.346 (3)	161
N1—H1B···Cl3ⁱⁱ	0.90	2.55	3.284 (3)	140
N1—H1B···Cl1ⁱⁱ	0.90	2.72	3.322 (3)	125
N2—H2A···Cl4	0.90	2.25	3.150 (3)	174
N2—H2B···Cl2ⁱⁱⁱ	0.90	2.48	3.199 (3)	137
N2—H2B···Cl3ⁱⁱⁱ	0.90	2.77	3.444 (3)	133

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

Acknowledgements

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

References

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