(R)-2-Methyl­piperazine-1,4-diium tetra­chloridoanti­monate(III) chloride

Li, L.; Wang, G.-X.

doi:10.1107/S1600536810047689

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1629

https://doi.org/10.1107/S1600536810047689

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(R)-2-Methylpiperazine-1,4-diium tetrachloridoantimonate(III) chloride

Lu Li ^a and Guo-Xi Wang ^a ^*

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

(Received 22 October 2010; accepted 17 November 2010; online 24 November 2010)

In the complex anion of the title compound, (C₅H₁₄N₂)[SbCl₄]Cl, the Sb atom is tetracoordinate within a saw-horse configuration. The cation adopts a chair conformation. The crystal structure is stabilized by intermolecular N—H⋯Cl hydrogen bonds.

Related literature

For related structures, see: Bujak & Zaleski (1999 ); Feng et al. (2007 ); Chen (2009 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

(C₅H₁₄N₂)[SbCl₄]Cl
M_r = 401.18
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.745 (5) Å
b = 10.773 (7) Å
c = 16.318 (9) Å
V = 1361.6 (14) Å³
Z = 4
Mo Kα radiation
μ = 2.97 mm⁻¹
T = 293 K
0.28 × 0.26 × 0.22 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.8, T_max = 0.9
13665 measured reflections
3086 independent reflections
3003 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.042
S = 1.08
3086 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 1299 Friedel pairs
Flack parameter: −0.037 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1E⋯Cl5ⁱ	0.90	2.29	3.190 (3)	179
N2—H2B⋯Cl5ⁱⁱ	0.90	2.27	3.150 (3)	166
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: https://doi.org/10.1107/S1600536810047689/bx2322sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047689/bx2322Isup2.hkl

checkCIF report

Comment top

Rencently, the crystal structure of some halogenoantimonate salts has been reported (Feng et al., 2007; Bujak & Zaleski, 1999; Chen, 2009).The construction of new members of this family is important in the development of modern coordination chemistry. We report here the crystal structure of the title compound. In the complex anion of the title compound, C₅H₁₄N₂. SbCl₄.Cl, the Sb atom is tetracoordinate and has a saw-horse geometry.The cation complex adopt chair conformation with Cremer & Pople (1975) puckering parameters: Q_T = 0.556 (3) Å,

θ = 1.8 (3) ° , φ = 97 (14)°. The crystal structure is stabilized by two intermolecular N—H···Cl hydrogen bonds, Table 1.

Related literature top

For related structures, see: Bujak & Zaleski (1999); Feng et al. (2007); Chen (2009). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A mixture of (R)-2-Methylpiperazine (2 mmol, 0.2 g), SbCl₃(2 mmol, 0.46 g) and 10% aqueous HCl (20 ml) were mixed and dissolved in 10 ml water by heating to 353 K (0.5 h) forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed after 13 days.

Structure description top

θ = 1.8 (3) ° , φ = 97 (14)°. The crystal structure is stabilized by two intermolecular N—H···Cl hydrogen bonds, Table 1.

For related structures, see: Bujak & Zaleski (1999); Feng et al. (2007); Chen (2009). For puckering parameters, see: Cremer & Pople (1975).

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. A view of (I) with atom labels. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. Packing diagram.

(R)-2-Methylpiperazine-1,4-diium tetrachloridoantimonate(III) chloride top

Crystal data top

(C₅H₁₄N₂)[SbCl₄]Cl	F(000) = 776
M_r = 401.18	D_x = 1.957 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3003 reflections
a = 7.745 (5) Å	θ = 2.9–27.5°
b = 10.773 (7) Å	µ = 2.97 mm⁻¹
c = 16.318 (9) Å	T = 293 K
V = 1361.6 (14) Å³	Block, colorless
Z = 4	0.28 × 0.26 × 0.22 mm

Data collection top

Rigaku SCXmini diffractometer	3086 independent reflections
Radiation source: fine-focus sealed tube	3003 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.9°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→14
T_min = 0.8, T_max = 0.9	l = −21→21
13665 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)] = 0.019	H-atom parameters constrained
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.0207P)²] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.003
3086 reflections	Δρ_max = 0.90 e Å⁻³
119 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1283 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.037 (17)

Crystal data top

(C₅H₁₄N₂)[SbCl₄]Cl	V = 1361.6 (14) Å³
M_r = 401.18	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.745 (5) Å	µ = 2.97 mm⁻¹
b = 10.773 (7) Å	T = 293 K
c = 16.318 (9) Å	0.28 × 0.26 × 0.22 mm

Data collection top

Rigaku SCXmini diffractometer	3086 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	3003 reflections with I > 2σ(I)
T_min = 0.8, T_max = 0.9	R_int = 0.026
13665 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.042	Δρ_max = 0.90 e Å⁻³
S = 1.08	Δρ_min = −0.33 e Å⁻³
3086 reflections	Absolute structure: Flack (1983), 1283 Friedel pairs
119 parameters	Absolute structure parameter: −0.037 (17)
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
Sb1	0.83387 (2)	0.572289 (14)	0.552350 (9)	0.02499 (5)
C1	0.3416 (5)	0.7218 (3)	0.70580 (19)	0.0533 (8)
H1A	0.2382	0.7109	0.6742	0.080*
H1B	0.4391	0.6931	0.6748	0.080*
H1C	0.3562	0.8082	0.7185	0.080*
C2	0.3278 (4)	0.6485 (2)	0.78422 (15)	0.0306 (5)
H2	0.4326	0.6617	0.8167	0.037*
C3	0.3079 (4)	0.5122 (3)	0.76750 (17)	0.0380 (7)
H3A	0.2117	0.4997	0.7304	0.046*
H3B	0.4114	0.4817	0.7407	0.046*
C4	0.1252 (4)	0.4866 (3)	0.8900 (2)	0.0479 (8)
H4A	0.1130	0.4402	0.9406	0.058*
H4B	0.0214	0.4743	0.8577	0.058*
C5	0.1455 (5)	0.6213 (3)	0.90911 (17)	0.0428 (7)
H5A	0.2425	0.6329	0.9459	0.051*
H5B	0.0424	0.6515	0.9363	0.051*
Cl1	0.59794 (9)	0.41872 (8)	0.59619 (5)	0.03962 (16)
Cl2	1.05446 (8)	0.42321 (8)	0.59260 (5)	0.03824 (16)
Cl3	0.82868 (11)	0.47961 (7)	0.41391 (4)	0.04005 (15)
Cl4	1.08779 (11)	0.72263 (7)	0.49885 (5)	0.04645 (19)
Cl5	0.84080 (12)	0.67609 (6)	0.71841 (4)	0.04331 (16)
N1	0.1748 (3)	0.69351 (19)	0.83223 (13)	0.0326 (5)
H1D	0.1906	0.7739	0.8451	0.039*
H1E	0.0799	0.6883	0.8006	0.039*
N2	0.2777 (3)	0.4395 (2)	0.84360 (15)	0.0375 (5)
H2A	0.3721	0.4439	0.8757	0.045*
H2B	0.2606	0.3593	0.8305	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.02595 (8)	0.02336 (8)	0.02566 (7)	0.00076 (7)	0.00008 (7)	0.00201 (6)
C1	0.0526 (18)	0.063 (2)	0.0443 (16)	−0.003 (2)	0.0064 (18)	0.0194 (15)
C2	0.0271 (12)	0.0357 (14)	0.0289 (12)	−0.0029 (13)	−0.0017 (13)	0.0037 (10)
C3	0.0417 (18)	0.0405 (16)	0.0317 (14)	0.0067 (14)	0.0011 (14)	−0.0054 (11)
C4	0.046 (2)	0.0357 (17)	0.062 (2)	0.0015 (13)	0.0161 (16)	0.0157 (14)
C5	0.054 (2)	0.0423 (16)	0.0323 (14)	0.0061 (15)	0.0106 (15)	0.0039 (12)
Cl1	0.0315 (3)	0.0423 (4)	0.0450 (4)	−0.0033 (3)	0.0028 (3)	0.0054 (3)
Cl2	0.0314 (3)	0.0346 (4)	0.0488 (4)	0.0052 (3)	−0.0072 (3)	0.0052 (4)
Cl3	0.0360 (3)	0.0527 (4)	0.0314 (3)	−0.0035 (4)	0.0012 (4)	−0.0102 (3)
Cl4	0.0452 (4)	0.0438 (5)	0.0504 (4)	−0.0103 (4)	0.0059 (3)	−0.0038 (4)
Cl5	0.0481 (4)	0.0430 (4)	0.0389 (3)	0.0054 (4)	−0.0081 (4)	−0.0019 (3)
N1	0.0381 (12)	0.0246 (11)	0.0350 (11)	0.0031 (11)	−0.0027 (12)	0.0009 (8)
N2	0.0374 (12)	0.0264 (12)	0.0486 (13)	0.0024 (10)	−0.0033 (11)	−0.0007 (11)

Geometric parameters (Å, º) top

Sb1—Cl2	2.4351 (12)	C3—H3B	0.9700
Sb1—Cl3	2.4702 (14)	C4—N2	1.492 (4)
Sb1—Cl1	2.5667 (13)	C4—C5	1.493 (4)
Sb1—Cl4	2.6932 (13)	C4—H4A	0.9700
C1—C2	1.507 (4)	C4—H4B	0.9700
C1—H1A	0.9600	C5—N1	1.493 (3)
C1—H1B	0.9600	C5—H5A	0.9700
C1—H1C	0.9600	C5—H5B	0.9700
C2—N1	1.501 (4)	N1—H1D	0.9000
C2—C3	1.502 (4)	N1—H1E	0.9000
C2—H2	0.9800	N2—H2A	0.9000
C3—N2	1.486 (4)	N2—H2B	0.9000
C3—H3A	0.9700

Cl2—Sb1—Cl3	89.51 (4)	N2—C4—C5	110.7 (3)
Cl2—Sb1—Cl1	89.95 (5)	N2—C4—H4A	109.5
Cl3—Sb1—Cl1	89.02 (4)	C5—C4—H4A	109.5
Cl2—Sb1—Cl4	88.38 (5)	N2—C4—H4B	109.5
Cl3—Sb1—Cl4	87.62 (4)	C5—C4—H4B	109.5
Cl1—Sb1—Cl4	176.26 (3)	H4A—C4—H4B	108.1
C2—C1—H1A	109.5	C4—C5—N1	110.3 (2)
C2—C1—H1B	109.5	C4—C5—H5A	109.6
H1A—C1—H1B	109.5	N1—C5—H5A	109.6
C2—C1—H1C	109.5	C4—C5—H5B	109.6
H1A—C1—H1C	109.5	N1—C5—H5B	109.6
H1B—C1—H1C	109.5	H5A—C5—H5B	108.1
N1—C2—C3	109.2 (3)	C5—N1—C2	113.0 (2)
N1—C2—C1	109.3 (3)	C5—N1—H1D	109.0
C3—C2—C1	111.4 (2)	C2—N1—H1D	109.0
N1—C2—H2	109.0	C5—N1—H1E	109.0
C3—C2—H2	109.0	C2—N1—H1E	109.0
C1—C2—H2	109.0	H1D—N1—H1E	107.8
N2—C3—C2	112.3 (2)	C3—N2—C4	111.7 (2)
N2—C3—H3A	109.1	C3—N2—H2A	109.3
C2—C3—H3A	109.1	C4—N2—H2A	109.3
N2—C3—H3B	109.1	C3—N2—H2B	109.3
C2—C3—H3B	109.1	C4—N2—H2B	109.3
H3A—C3—H3B	107.9	H2A—N2—H2B	107.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···Cl5ⁱ	0.90	2.29	3.190 (3)	179
N2—H2B···Cl5ⁱⁱ	0.90	2.27	3.150 (3)	166

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

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[SbCl₄]Cl
M_r	401.18
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.745 (5), 10.773 (7), 16.318 (9)
V (Å³)	1361.6 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.97
Crystal size (mm)	0.28 × 0.26 × 0.22

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.8, 0.9
No. of measured, independent and observed [I > 2σ(I)] reflections	13665, 3086, 3003
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.042, 1.08
No. of reflections	3086
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.33
Absolute structure	Flack (1983), 1283 Friedel pairs
Absolute structure parameter	−0.037 (17)

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—H1E···Cl5ⁱ	0.90	2.29	3.190 (3)	179.1
N2—H2B···Cl5ⁱⁱ	0.90	2.27	3.150 (3)	165.9

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

Acknowledgements

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

References

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