Bis(4-methyl­piperidinium) hexa­chlorido­stannate(IV)

Shahzadi, S.; Khan, H.N.; Ali, S.; Helliwell, M.

doi:10.1107/S1600536808007368

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m573

doi:10.1107/S1600536808007368

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Bis(4-methylpiperidinium) hexachloridostannate(IV)

Saira Shahzadi,^a Hamid Nawaz Khan,^b Saqib Ali ^b ^* and Madeleine Helliwell ^c

^aDepartment of Chemistry, GC University, Faisalabad, Pakistan, ^bDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^cSchool of Chemistry, The University of Manchester, Manchester M13 9PL, England
^*Correspondence e-mail: drsa54@yahoo.com

(Received 15 February 2008; accepted 17 March 2008; online 29 March 2008)

The crystal structure of the title compound, (C₆H₁₄N)₂[SnCl₆], is built of 4-methylpiperidinium cations, occupying special positions on the mirror plane, and hexachloridostannate(IV) anions on a special position of 2/m symmetry. The ions are linked via N—H⋯Cl hydrogen bonds into chains running along the b axis.

Related literature

For related literature, see: Shahzadi, Ali & Fettouhi (2006 ); Shahzadi, Ali, Bhatti et al. (2006 ).

Experimental

Crystal data

(C₆H₁₄N)₂[SnCl₆]
M_r = 531.75
Orthorhombic, P n n m
a = 13.123 (5) Å
b = 7.722 (5) Å
c = 10.500 (5) Å
V = 1064.0 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.95 mm⁻¹
T = 100 (2) K
0.25 × 0.25 × 0.25 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: none
7975 measured reflections
1153 independent reflections
1055 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.040
S = 1.04
1153 reflections
65 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1	0.88 (3)	2.63 (3)	3.258 (3)	129 (2)
N1—H2N⋯Cl2ⁱ	0.84 (3)	2.72 (2)	3.413 (2)	141.6 (5)
N1—H2N⋯Cl2ⁱⁱ	0.84 (3)	2.72 (2)	3.413 (2)	141.6 (5)
Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y+1, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007368/ya2069sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007368/ya2069Isup2.hkl

checkCIF report

Comment top

We report here the crystal structure of the title compound (I) as shown in Fig. 1. The Sn1—Cl distances span the range of 2.417 (1)–2.431 (1) Å; the N1—C1 bond is 1.500 (2) Å. The N—H···Cl bonds link the ions into chains along the b axis (Table 1, Fig. 2).

Related literature top

For related literature, see: Shahzadi, Ali & Fettouhi (2006); Shahzadi, Ali, Bhatti et al. (2006).

Experimental top

The 4-methyl-1-piperidine carbodithioic acid (3.0 g, 17.1 mmol) and tin tetrachloride pentahydrate (5.99 g, 17.1 mmol) were added to 100 ml of dry methanol in round bottom flask and stirred for 6 h. The resulting clear solution was evaporated at room temperature. Colourless crystals of the title compound were obtained after recrystallization in chlorofom and n-hexane (1:1). Yield: 64%. m.p. 228°C.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structure of (I) with displacement ellipsoids drawn at the 50% probability level. The unlabelled atoms of the 4-methylpiperidinium cation are symmetry related (symmetry code x, y, -z). The unlabelled Cl atoms are symmetry related to Cl1 (symmetry code -x, 2 - y, -z) and Cl2 (symmetry codes -x, 2 - y, -z; -x, 2 - y, z; x, y, -z).
	Fig. 2. Fragment of the crystal packing of (I) showing chain along the b axis, viewed approximately along the diagonal of the bc-plane; H-bonds are shown as dashed lines.

Bis(4-methylpiperidinium) hexachloridostannate top

Crystal data top

(C₆H₁₄N)₂[SnCl₆]	F(000) = 532
M_r = 531.75	D_x = 1.660 Mg m⁻³
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P22n	Cell parameters from 3718 reflections
a = 13.123 (5) Å	θ = 2.5–26.3°
b = 7.722 (5) Å	µ = 1.95 mm⁻¹
c = 10.500 (5) Å	T = 100 K
V = 1064.0 (9) Å³	Pyramidal, colourless
Z = 2	0.25 × 0.25 × 0.25 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	1055 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 26.3°, θ_min = 2.5°
ϕ and ω scans	h = −16→16
7975 measured reflections	k = −9→9
1153 independent reflections	l = −13→13

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)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.040	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0164P)²] where P = (F_o² + 2F_c²)/3
1153 reflections	(Δ/σ)_max < 0.001
65 parameters	Δρ_max = 0.78 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

(C₆H₁₄N)₂[SnCl₆]	V = 1064.0 (9) Å³
M_r = 531.75	Z = 2
Orthorhombic, Pnnm	Mo Kα radiation
a = 13.123 (5) Å	µ = 1.95 mm⁻¹
b = 7.722 (5) Å	T = 100 K
c = 10.500 (5) Å	0.25 × 0.25 × 0.25 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	1055 reflections with I > 2σ(I)
7975 measured reflections	R_int = 0.050
1153 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.040	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.78 e Å⁻³
1153 reflections	Δρ_min = −0.29 e Å⁻³
65 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
Sn1	0.0000	1.0000	0.0000	0.01428 (9)
Cl1	0.18119 (5)	0.94377 (8)	0.0000	0.02127 (15)
Cl2	−0.02412 (3)	0.77582 (6)	0.15973 (4)	0.02279 (12)
N1	0.16716 (17)	0.5226 (3)	0.0000	0.0187 (5)
H1N	0.128 (2)	0.615 (4)	0.0000	0.022*
H2N	0.130 (2)	0.434 (4)	0.0000	0.022*
C1	0.23016 (14)	0.5228 (2)	0.11919 (17)	0.0202 (4)
H1C	0.1850	0.5171	0.1946	0.024*
H1D	0.2701	0.6313	0.1242	0.024*
C2	0.30167 (13)	0.3686 (2)	0.11902 (17)	0.0194 (4)
H2A	0.2611	0.2607	0.1235	0.023*
H2B	0.3456	0.3736	0.1956	0.023*
C3	0.36885 (19)	0.3640 (3)	0.0000	0.0194 (6)
H3	0.4130	0.4696	0.0000	0.023*
C4	0.4374 (2)	0.2055 (4)	0.0000	0.0271 (7)
H4A	0.4780 (15)	0.200 (3)	−0.0726 (19)	0.032*
H4B	0.399 (2)	0.102 (4)	0.0000	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01250 (13)	0.01126 (13)	0.01907 (14)	−0.00031 (9)	0.000	0.000
Cl1	0.0136 (3)	0.0153 (3)	0.0349 (4)	0.0005 (2)	0.000	0.000
Cl2	0.0214 (2)	0.0228 (2)	0.0242 (3)	−0.00568 (18)	−0.00453 (18)	0.00756 (19)
N1	0.0165 (11)	0.0122 (12)	0.0274 (13)	0.0012 (9)	0.000	0.000
C1	0.0205 (10)	0.0199 (10)	0.0203 (10)	−0.0007 (8)	−0.0011 (7)	−0.0040 (8)
C2	0.0189 (10)	0.0200 (10)	0.0192 (10)	0.0010 (8)	−0.0028 (8)	−0.0011 (8)
C3	0.0151 (13)	0.0189 (14)	0.0241 (15)	0.0003 (10)	0.000	0.000
C4	0.0239 (16)	0.0321 (18)	0.0252 (17)	0.0102 (13)	0.000	0.000

Geometric parameters (Å, º) top

Sn1—Cl1	2.4170 (11)	C1—H1C	0.9900
Sn1—Cl1ⁱ	2.4170 (11)	C1—H1D	0.9900
Sn1—Cl2ⁱⁱ	2.4310 (11)	C2—C3	1.530 (2)
Sn1—Cl2ⁱⁱⁱ	2.4310 (11)	C2—H2A	0.9900
Sn1—Cl2ⁱ	2.4310 (11)	C2—H2B	0.9900
Sn1—Cl2	2.4310 (11)	C3—C4	1.519 (4)
N1—C1ⁱⁱⁱ	1.500 (2)	C3—C2ⁱⁱⁱ	1.530 (2)
N1—C1	1.500 (2)	C3—H3	1.0000
N1—H1N	0.88 (3)	C4—H4A	0.931 (19)
N1—H2N	0.84 (3)	C4—H4B	0.95 (3)
C1—C2	1.516 (2)

Cl1—Sn1—Cl1ⁱ	180.000 (5)	N1—C1—C2	109.83 (15)
Cl1—Sn1—Cl2ⁱⁱ	89.990 (19)	N1—C1—H1C	109.7
Cl1ⁱ—Sn1—Cl2ⁱⁱ	90.010 (19)	C2—C1—H1C	109.7
Cl1—Sn1—Cl2ⁱⁱⁱ	90.010 (19)	N1—C1—H1D	109.7
Cl1ⁱ—Sn1—Cl2ⁱⁱⁱ	89.990 (19)	C2—C1—H1D	109.7
Cl2ⁱⁱ—Sn1—Cl2ⁱⁱⁱ	180.0	H1C—C1—H1D	108.2
Cl1—Sn1—Cl2ⁱ	89.990 (19)	C1—C2—C3	112.08 (16)
Cl1ⁱ—Sn1—Cl2ⁱ	90.010 (19)	C1—C2—H2A	109.2
Cl2ⁱⁱ—Sn1—Cl2ⁱ	87.24 (5)	C3—C2—H2A	109.2
Cl2ⁱⁱⁱ—Sn1—Cl2ⁱ	92.76 (5)	C1—C2—H2B	109.2
Cl1—Sn1—Cl2	90.010 (19)	C3—C2—H2B	109.2
Cl1ⁱ—Sn1—Cl2	89.990 (19)	H2A—C2—H2B	107.9
Cl2ⁱⁱ—Sn1—Cl2	92.76 (5)	C4—C3—C2ⁱⁱⁱ	111.10 (15)
Cl2ⁱⁱⁱ—Sn1—Cl2	87.24 (5)	C4—C3—C2	111.10 (15)
Cl2ⁱ—Sn1—Cl2	180.0	C2ⁱⁱⁱ—C3—C2	109.6 (2)
C1ⁱⁱⁱ—N1—C1	113.1 (2)	C4—C3—H3	108.3
C1ⁱⁱⁱ—N1—H1N	108.7 (8)	C2ⁱⁱⁱ—C3—H3	108.3
C1—N1—H1N	108.7 (8)	C2—C3—H3	108.3
C1ⁱⁱⁱ—N1—H2N	108.6 (10)	C3—C4—H4A	112.1 (14)
C1—N1—H2N	108.6 (10)	C3—C4—H4B	111.2 (18)
H1N—N1—H2N	109 (3)	H4A—C4—H4B	105.6 (17)

C1ⁱⁱⁱ—N1—C1—C2	−56.8 (2)	C1—C2—C3—C4	−178.20 (18)
N1—C1—C2—C3	55.7 (2)	C1—C2—C3—C2ⁱⁱⁱ	−55.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.88 (3)	2.63 (3)	3.258 (3)	129 (2)
N1—H2N···Cl2^iv	0.84 (3)	2.72 (2)	3.413 (2)	142 (1)
N1—H2N···Cl2^v	0.84 (3)	2.72 (2)	3.413 (2)	142 (1)

Symmetry codes: (iv) −x, −y+1, −z; (v) −x, −y+1, z.

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N)₂[SnCl₆]
M_r	531.75
Crystal system, space group	Orthorhombic, Pnnm
Temperature (K)	100
a, b, c (Å)	13.123 (5), 7.722 (5), 10.500 (5)
V (Å³)	1064.0 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.25 × 0.25 × 0.25

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7975, 1153, 1055
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.040, 1.04
No. of reflections	1153
No. of parameters	65
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.88 (3)	2.63 (3)	3.258 (3)	129 (2)
N1—H2N···Cl2ⁱ	0.84 (3)	2.72 (2)	3.413 (2)	141.6 (5)
N1—H2N···Cl2ⁱⁱ	0.84 (3)	2.72 (2)	3.413 (2)	141.6 (5)

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

Acknowledgements

SA is thankful to Quaid-i-Azam University, Islamabad, Pakistan, for financial support.

References

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