Bis(2-methyl­piperidinium) penta­chlorido­anti­monate(III)

Xu, Q.

doi:10.1107/S1600536812017163

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m671

doi:10.1107/S1600536812017163

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Bis(2-methylpiperidinium) pentachloridoantimonate(III)

Qian Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xqchem@yahoo.com.cn

(Received 31 March 2012; accepted 18 April 2012; online 25 April 2012)

The asymmetric unit of the title compound, (C₆H₁₄N)₂[SbCl₅], contains one cation and half of the anion on a special position (specifically, the Sb^III ion and three chloride anions are situated on a mirror plane). In the [SbCl₅]²⁻ unit, the Sb^III ion is coordinated by five chloride anions [Sb—Cl = 2.3721 (11)–2.6656 (12) Å] in a distorted square-pyramidal geometry. However, one chloride anion from a neighbouring [SbCl₅]²⁻ unit provides a short Sb⋯Cl contact of 3.3600 (12) Å and completes the Sb coordination environment up to an elongated octahedron. In the crystal, N—H⋯Cl hydrogen bonds link cations and anions into columns propagating along [100].

Related literature

For the crystal structure of bis(4-benzylpiperidinium) pentachloridoantimonate(III), see: Marsh (1995 ). For background to ferroelectric metal-organic frameworks, see: Fu et al. (2009 ); Ye et al. (2006 ); Zhang et al. (2008 , 2010 ).

Experimental

Crystal data

(C₆H₁₄N)₂[SbCl₅]
M_r = 499.36
Orthorhombic, P n m a
a = 7.5995 (15) Å
b = 23.165 (5) Å
c = 11.453 (2) Å
V = 2016.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 293 K
0.28 × 0.25 × 0.21 mm

Data collection

Rigaku Mercury70 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.421, T_max = 0.558
19754 measured reflections
2361 independent reflections
1938 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.065
S = 1.08
2361 reflections
98 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Cl3ⁱ	0.90	2.40	3.226 (3)	153
N1—H1E⋯Cl1ⁱⁱ	0.90	2.48	3.373 (3)	173
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006 ); cell refinement: SCXmini Benchtop Crystallography System Software; data reduction: SCXmini Benchtop Crystallography System Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017163/cv5279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017163/cv5279Isup2.hkl

checkCIF report

Comment top

As a contribution to a search for new ferroelectric materials (Fu et al., 2009; Ye et al., 2006; Zhang et al., 2008; Zhang et al., 2010), we have synthesized the title compound, (I). Herewith we present its crystal structure.

The asymmetric unit of (I), 2(C₆H₁₄N)⁺[SbCl₅]^2-, contains one cation and one-half of the anion in a special position (Fig. 1). The Sb1 atoms coordinated in a slightly distorted square-pyramidal geometry by five Cl atoms and distance of the top Cl2 and Sb1 is 2.3721 (11) Å much shorter than the mean values of other Sb—Cl[2.636 (11) Å]. The bond angles around the Sb1 are in the range 84.93 (2)–91.454 (19)° and correspond to those observed in the related compound 2(C₁₂H₁₈N)⁺[SbCl₅]^2- (Marsh, 1995).

In the crystal structure, intermolecular N—H···Cl hydrogen bonds (Table 1) link cations and anions into columns propagated in [100] (Fig. 2). In the title compound, no dielectric anomalies were observed in the range from 190 K to its melting point, which is more than 357 K.

Related literature top

For the crystal structure of bis(4-benzylpiperidinium) pentachloridoantimonate(III), see: Marsh (1995). For background to ferroelectric metal-organic frameworks, see: Fu et al. (2009); Ye et al. (2006); Zhang et al. (2008, 2010).

Experimental top

The mixture of SbCl₃(1.1 g, 5 mmol) and 2-methypiperidine (1.05 g, 10 mmol) in hydrochloric acid solution was stirred for several minutes at room temperature. Colourless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the solution at room temperature over 2 weeks.

Computing details top

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); cell refinement: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); data reduction: SCXmini Benchtop Crystallography System Software (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the (I), with the displacement ellipsoids drawn at the 30% probability level [symmetry code: (A) x, 0.5 - y, z].
	Fig. 2. A portion of the packing diagram with hydrogen bonds shown as dashed lines.

Bis(2-methylpiperidinium) pentachloridoantimonate(III) top

Crystal data top

(C₆H₁₄N)₂[SbCl₅]	F(000) = 1000
M_r = 499.36	D_x = 1.645 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2361 reflections
a = 7.5995 (15) Å	θ = 2.2–27.5°
b = 23.165 (5) Å	µ = 2.03 mm⁻¹
c = 11.453 (2) Å	T = 293 K
V = 2016.2 (7) Å³	Block, colourless
Z = 4	0.28 × 0.25 × 0.21 mm

Data collection top

Rigaku Mercury70 CCD diffractometer	2361 independent reflections
Radiation source: fine-focus sealed tube	1938 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −9→9
T_min = 0.421, T_max = 0.558	k = −30→30
19754 measured reflections	l = −14→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0181P)² + 1.8699P] where P = (F_o² + 2F_c²)/3
2361 reflections	(Δ/σ)_max = 0.001
98 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

(C₆H₁₄N)₂[SbCl₅]	V = 2016.2 (7) Å³
M_r = 499.36	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.5995 (15) Å	µ = 2.03 mm⁻¹
b = 23.165 (5) Å	T = 293 K
c = 11.453 (2) Å	0.28 × 0.25 × 0.21 mm

Data collection top

Rigaku Mercury70 CCD diffractometer	2361 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1938 reflections with I > 2σ(I)
T_min = 0.421, T_max = 0.558	R_int = 0.061
19754 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.08	Δρ_max = 0.58 e Å⁻³
2361 reflections	Δρ_min = −0.52 e Å⁻³
98 parameters

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
C1	0.8199 (5)	0.1245 (2)	−0.1957 (3)	0.0703 (12)
H1A	0.7817	0.1631	−0.2129	0.105*
H1B	0.7841	0.0991	−0.2575	0.105*
H1C	0.9457	0.1238	−0.1887	0.105*
C2	0.7387 (5)	0.10494 (17)	−0.0830 (3)	0.0554 (10)
H2	0.6106	0.1081	−0.0900	0.066*
C3	0.7834 (6)	0.04338 (18)	−0.0511 (4)	0.0750 (13)
H3A	0.7347	0.0177	−0.1098	0.090*
H3B	0.9103	0.0388	−0.0519	0.090*
C4	0.7143 (7)	0.0260 (2)	0.0672 (4)	0.0866 (15)
H4A	0.7536	−0.0128	0.0855	0.104*
H4B	0.5866	0.0259	0.0659	0.104*
C5	0.7785 (6)	0.06724 (18)	0.1599 (4)	0.0707 (12)
H5A	0.7284	0.0566	0.2348	0.085*
H5B	0.9055	0.0647	0.1661	0.085*
C6	0.7275 (5)	0.12723 (16)	0.1310 (3)	0.0552 (10)
H6A	0.7741	0.1534	0.1895	0.066*
H6B	0.6002	0.1306	0.1314	0.066*
N1	0.7977 (4)	0.14369 (12)	0.0122 (3)	0.0499 (7)
H1D	0.7632	0.1799	−0.0044	0.060*
H1E	0.9160	0.1435	0.0147	0.060*
Cl1	0.73805 (11)	0.13613 (4)	0.45405 (8)	0.0508 (2)
Cl2	0.58634 (15)	0.2500	0.61136 (10)	0.0463 (3)
Cl3	1.05345 (15)	0.2500	0.57047 (11)	0.0489 (3)
Cl4	0.48085 (16)	0.2500	0.31467 (11)	0.0529 (3)
Sb1	0.76256 (3)	0.2500	0.44041 (2)	0.03097 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.070 (3)	0.095 (3)	0.046 (2)	−0.005 (2)	−0.001 (2)	−0.007 (2)
C2	0.047 (2)	0.065 (2)	0.054 (2)	0.0012 (18)	−0.0107 (18)	−0.0133 (18)
C3	0.090 (3)	0.048 (2)	0.088 (3)	−0.004 (2)	0.006 (3)	−0.017 (2)
C4	0.111 (4)	0.051 (3)	0.098 (4)	−0.014 (3)	0.008 (3)	−0.005 (3)
C5	0.077 (3)	0.071 (3)	0.064 (3)	−0.007 (2)	−0.003 (2)	0.012 (2)
C6	0.065 (2)	0.051 (2)	0.050 (2)	−0.0070 (19)	0.0054 (19)	−0.0070 (17)
N1	0.0522 (17)	0.0429 (17)	0.0547 (18)	0.0026 (14)	−0.0054 (15)	−0.0050 (14)
Cl1	0.0496 (5)	0.0453 (5)	0.0576 (5)	0.0051 (4)	0.0006 (4)	−0.0039 (4)
Cl2	0.0521 (7)	0.0532 (7)	0.0336 (6)	0.000	0.0144 (5)	0.000
Cl3	0.0438 (6)	0.0535 (7)	0.0493 (7)	0.000	−0.0117 (6)	0.000
Cl4	0.0481 (7)	0.0584 (8)	0.0523 (7)	0.000	−0.0189 (6)	0.000
Sb1	0.02942 (15)	0.03721 (16)	0.02627 (14)	0.000	0.00072 (12)	0.000

Geometric parameters (Å, º) top

C1—C2	1.500 (5)	C5—C6	1.480 (5)
C1—H1A	0.9600	C5—H5A	0.9700
C1—H1B	0.9600	C5—H5B	0.9700
C1—H1C	0.9600	C6—N1	1.511 (5)
C2—N1	1.481 (4)	C6—H6A	0.9700
C2—C3	1.511 (6)	C6—H6B	0.9700
C2—H2	0.9800	N1—H1D	0.9000
C3—C4	1.509 (6)	N1—H1E	0.9000
C3—H3A	0.9700	Cl1—Sb1	2.6491 (10)
C3—H3B	0.9700	Cl2—Sb1	2.3721 (11)
C4—C5	1.510 (6)	Cl3—Sb1	2.6656 (12)
C4—H4A	0.9700	Cl4—Sb1	2.5802 (12)
C4—H4B	0.9700	Sb1—Cl1ⁱ	2.6491 (10)

C2—C1—H1A	109.5	C4—C5—H5A	109.5
C2—C1—H1B	109.5	C6—C5—H5B	109.5
H1A—C1—H1B	109.5	C4—C5—H5B	109.5
C2—C1—H1C	109.5	H5A—C5—H5B	108.1
H1A—C1—H1C	109.5	C5—C6—N1	110.3 (3)
H1B—C1—H1C	109.5	C5—C6—H6A	109.6
N1—C2—C1	109.0 (3)	N1—C6—H6A	109.6
N1—C2—C3	109.0 (3)	C5—C6—H6B	109.6
C1—C2—C3	113.6 (3)	N1—C6—H6B	109.6
N1—C2—H2	108.4	H6A—C6—H6B	108.1
C1—C2—H2	108.4	C2—N1—C6	113.8 (3)
C3—C2—H2	108.4	C2—N1—H1D	108.8
C4—C3—C2	113.0 (4)	C6—N1—H1D	108.8
C4—C3—H3A	109.0	C2—N1—H1E	108.8
C2—C3—H3A	109.0	C6—N1—H1E	108.8
C4—C3—H3B	109.0	H1D—N1—H1E	107.7
C2—C3—H3B	109.0	Cl2—Sb1—Cl4	89.56 (5)
H3A—C3—H3B	107.8	Cl2—Sb1—Cl1	84.93 (2)
C3—C4—C5	110.5 (4)	Cl4—Sb1—Cl1	88.54 (2)
C3—C4—H4A	109.6	Cl2—Sb1—Cl1ⁱ	84.93 (2)
C5—C4—H4A	109.6	Cl4—Sb1—Cl1ⁱ	88.542 (19)
C3—C4—H4B	109.6	Cl1—Sb1—Cl1ⁱ	169.47 (4)
C5—C4—H4B	109.6	Cl2—Sb1—Cl3	90.40 (4)
H4A—C4—H4B	108.1	Cl4—Sb1—Cl3	179.96 (4)
C6—C5—C4	110.6 (4)	Cl1—Sb1—Cl3	91.454 (19)
C6—C5—H5A	109.5	Cl1ⁱ—Sb1—Cl3	91.454 (19)

N1—C2—C3—C4	53.2 (5)	C4—C5—C6—N1	−56.7 (5)
C1—C2—C3—C4	175.0 (4)	C1—C2—N1—C6	−178.6 (3)
C2—C3—C4—C5	−55.2 (6)	C3—C2—N1—C6	−54.0 (4)
C3—C4—C5—C6	56.5 (5)	C5—C6—N1—C2	57.2 (4)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl3ⁱⁱ	0.90	2.40	3.226 (3)	153
N1—H1E···Cl1ⁱⁱⁱ	0.90	2.48	3.373 (3)	173

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

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N)₂[SbCl₅]
M_r	499.36
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	7.5995 (15), 23.165 (5), 11.453 (2)
V (Å³)	2016.2 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.03
Crystal size (mm)	0.28 × 0.25 × 0.21

Data collection
Diffractometer	Rigaku Mercury70 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.421, 0.558
No. of measured, independent and observed [I > 2σ(I)] reflections	19754, 2361, 1938
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.065, 1.08
No. of reflections	2361
No. of parameters	98
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.52

Computer programs: SCXmini Benchtop Crystallography System Software (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl3ⁱ	0.90	2.40	3.226 (3)	153.1
N1—H1E···Cl1ⁱⁱ	0.90	2.48	3.373 (3)	172.6

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

Acknowledgements

This work was supported by Southeast University.

References

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