Bis(dimethyl­ammonium) tetra­chlorido­dimethyl­stannate(IV)

Diop, T.; Diop, L.; Michaud, F.

doi:10.1107/S1600536811013584

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m696

doi:10.1107/S1600536811013584

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Bis(dimethylammonium) tetrachloridodimethylstannate(IV)

Tidiane Diop,^a ^* Libasse Diop ^a and Francois Michaud ^b

^aLaboratoire de Chimie, Universite Chekh Anta Diop, Dakar, Senegal, and ^bService commun d'analyse par diffraction des rayons X, Universite de Bretagne Occidentale, 6 avenue Victor Le Gorgeu, CS 93837, F-29238 BREST Cedex 3, France
^*Correspondence e-mail: cakdiop@ucad.sn

(Received 1 March 2011; accepted 11 April 2011; online 7 May 2011)

Regular crystals of the title compound, (C₂H₈N)₂[Sn(CH₃)₂Cl₄], were obtained by reacting SnMe₂Cl₂ with (CH₃)₂NH·HCl in ethanol in a 1:1 ratio. The Sn atom lies on a center of symmetry and is six-coordinated. It has a distorted octahedral SnC₂Cl₄ environment with the Cl atoms in cis positions. The Cl atoms are connected to dimethylammonium cations through N—H⋯Cl hydrogen bonds, forming an infinite chain extending parallel to [010].

Related literature

For background to organotin(IV) chemistry, see: Gielen et al. (1996 ); Evans & Karpel (1985 ); Crowe et al. (1994 ); Diasse-Sarr et al. (1997); Diop et al. (2002, 2003). For related compounds, see: Valle et al. (1985 ); Casas et al. (1996 ); Diop et al. (2011 ).

Experimental

Crystal data

(C₂H₈N)₂[SnCH₃)₂Cl₄]
M_r = 382.75
Triclinic, $[P \overline 1]$
a = 6.6162 (9) Å
b = 7.3703 (11) Å
c = 8.4555 (12) Å
α = 109.625 (14)°
β = 98.345 (12)°
γ = 92.812 (12)°
V = 382.13 (9) Å³
Z = 1
Mo Kα radiation
μ = 2.34 mm⁻¹
T = 297 K
0.5 × 0.3 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.352, T_max = 0.652
3329 measured reflections
1871 independent reflections
1839 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.060
S = 1.06
1871 reflections
64 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1E⋯Cl1	0.9	2.31	3.201 (2)	169
N1—H1D⋯Cl2ⁱ	0.9	2.37	3.229 (2)	160
Symmetry code: (i) x, y+1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013584/br2163sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013584/br2163Isup2.hkl

checkCIF report

Comment top

As some compounds belonging to organotin family have been screened and found to be very more active than cis platin towards some kinds of cancer, many groups have been involved in the seek of new organotin compounds (Gielen, 1996; Crowe, 1994). In another hand the various applications of compounds of this family have been outlined (Evans & Karpel, 1985). In our group we have yet published some papers in this field (Diop et al. 2002; Diop et al. 2003; Diasse-Sarr et al. 1997). In this paper we have initiated the study of the interactions between (CH₃)₃NH.Cl and SnMe₂Cl₂ which has yielded [(CH₃)₂NH₂⁺]₂[SnMe₂Cl₄^2-], X-ray structure determination of which has been carried out.

In the [SnMe₂Cl₄]^2- anion the tin atom, which lies on a center of symmetry, is coordinated to the two methyl groups and four Cl atoms (Fig 1) in an octahedral geometry with trans methyl groups.

The Sn—C bond distances (2.116Å) are practically equal to those found in other octahedral dimethyltin(IV) diaquo-dichloro complexes SnMe₂(H₂O)₂Cl₂ (2.112 Å) reported by Valle et al. (1985) and longer than those in [Hthiamine][SnMe₂(H₂O)₂Cl₂]Cl (2.092 Å and 2.084 Å) reported by Casas et al. (1996).

The Cl—Sn—Cl and Cl—Sn—CH3 angles being very near to 90° indicates an almost perfect octahedron. The interactions between [(CH₃)NH₂⁺] and anion are hydrogen bonds type. The C—N—C angles of the cation is close to 109°, in agreement with the expected sp³ hybridation. The interactions between [(CH₃)NH₂⁺] and anion imply hydrogen bonds.

Related literature top

For background to organotin(IV) chemistry, see: Gielen et al. (1996); Evans & Karpel (1985); Crowe et al. (1994); Diasse-Sarr et al. (1997); Diop et al. (2002, 2003). For related compounds, see: Valle et al. (1985); Casas et al. (1996); Diop et al. (2011).

Experimental top

The title compound has been obtained as white crystalline solid by reacting dimethylammonium chloride (Merck) with dimethyltin dichloride (Aldrich) in ethanol (1/1 ratio, mp: 190°). After a slow solvent evaporation colourless crystals suitable for X-ray work were obtained. All the chemicals were used without any further purification.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. Molecular packing around one anion implying hydrogen bonds (dashed lines) with the atom numbering used and 50% probability displacement elipsoids. Symmetry operations : ['] -x, -y, -z; [''] x, y+1,z, ['''] -x, -y, -z.

Bis(dimethylammonium) tetrachloridodimethylstannate(IV) top

Crystal data top

(C₂H₈N)₂[SnCH₃)₂Cl₄]	Z = 1
M_r = 382.75	F(000) = 190
Triclinic, P1	D_x = 1.663 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6162 (9) Å	Cell parameters from 3675 reflections
b = 7.3703 (11) Å	θ = 2.9–31.3°
c = 8.4555 (12) Å	µ = 2.34 mm⁻¹
α = 109.625 (14)°	T = 297 K
β = 98.345 (12)°	Fragment of rounded block, colourless
γ = 92.812 (12)°	0.5 × 0.3 × 0.2 mm
V = 382.13 (9) Å³

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	1871 independent reflections
Radiation source: sealed X-ray tube	1839 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 8.3622 pixels mm^-1	θ_max = 28.3°, θ_min = 4.1°
4 stepped ω–scans over 115 deg. with kappa –79 deg. (chi –58.3 deg.), phi 0, 90, 180, 270 deg. step 1 deg., exposure time 45 s detector distance 50 mm detector angle 30 deg.	h = −8→7
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2009)	k = −9→9
T_min = 0.352, T_max = 0.652	l = −11→11
3329 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0362P)² + 0.2233P] where P = (F_o² + 2F_c²)/3
1871 reflections	(Δ/σ)_max < 0.001
64 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

(C₂H₈N)₂[SnCH₃)₂Cl₄]	γ = 92.812 (12)°
M_r = 382.75	V = 382.13 (9) Å³
Triclinic, P1	Z = 1
a = 6.6162 (9) Å	Mo Kα radiation
b = 7.3703 (11) Å	µ = 2.34 mm⁻¹
c = 8.4555 (12) Å	T = 297 K
α = 109.625 (14)°	0.5 × 0.3 × 0.2 mm
β = 98.345 (12)°

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	1871 independent reflections
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2009)	1839 reflections with I > 2σ(I)
T_min = 0.352, T_max = 0.652	R_int = 0.018
3329 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.06	Δρ_max = 0.56 e Å⁻³
1871 reflections	Δρ_min = −0.43 e Å⁻³
64 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	0.2689 (4)	0.3818 (4)	0.5967 (3)	0.0404 (5)
H1A	0.2902	0.2502	0.5847	0.061*
H1B	0.1366	0.3849	0.5343	0.061*
H1C	0.275	0.4566	0.715	0.061*
Cl1	0.25609 (10)	0.40746 (9)	0.20155 (7)	0.04289 (14)
Cl2	0.64584 (8)	0.16207 (8)	0.39707 (7)	0.03603 (12)
Sn1	0.5	0.5	0.5	0.02900 (8)
C2	0.2993 (5)	0.8184 (6)	0.0309 (4)	0.0621 (8)
H2A	0.4272	0.764	0.0166	0.093*
H2B	0.3073	0.9423	0.0167	0.093*
H2C	0.1905	0.7333	−0.0527	0.093*
C3	0.0570 (4)	0.9131 (4)	0.2302 (4)	0.0479 (6)
H3A	0.0331	0.9174	0.3406	0.072*
H3B	−0.0493	0.8274	0.1442	0.072*
H3C	0.0563	1.0407	0.2239	0.072*
N1	0.2581 (3)	0.8422 (3)	0.2023 (3)	0.0381 (4)
H1D	0.3576	0.9263	0.28	0.046*
H1E	0.2622	0.7276	0.2183	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0393 (11)	0.0380 (11)	0.0450 (12)	−0.0035 (9)	0.0167 (10)	0.0128 (10)
Cl1	0.0486 (3)	0.0369 (3)	0.0360 (3)	−0.0001 (2)	−0.0059 (2)	0.0094 (2)
Cl2	0.0387 (3)	0.0282 (2)	0.0402 (3)	0.00715 (19)	0.0087 (2)	0.0093 (2)
Sn1	0.03107 (11)	0.02496 (11)	0.03074 (11)	−0.00012 (7)	0.00626 (7)	0.00940 (8)
C2	0.0604 (18)	0.078 (2)	0.0417 (14)	−0.0007 (16)	0.0195 (13)	0.0098 (14)
C3	0.0387 (12)	0.0550 (15)	0.0478 (14)	0.0036 (11)	0.0083 (10)	0.0151 (12)
N1	0.0382 (10)	0.0390 (10)	0.0351 (9)	0.0007 (8)	0.0029 (7)	0.0120 (8)

Geometric parameters (Å, º) top

C1—Sn1	2.116 (2)	C2—H2A	0.96
C1—H1A	0.96	C2—H2B	0.96
C1—H1B	0.96	C2—H2C	0.96
C1—H1C	0.96	C3—N1	1.475 (3)
Cl1—Sn1	2.6441 (7)	C3—H3A	0.96
Cl2—Sn1	2.6297 (7)	C3—H3B	0.96
Sn1—C1ⁱ	2.116 (2)	C3—H3C	0.96
Sn1—Cl2ⁱ	2.6297 (7)	N1—H1D	0.9
Sn1—Cl1ⁱ	2.6441 (7)	N1—H1E	0.9
C2—N1	1.468 (4)

Sn1—C1—H1A	109.5	Cl1ⁱ—Sn1—Cl1	180
Sn1—C1—H1B	109.5	N1—C2—H2A	109.5
H1A—C1—H1B	109.5	N1—C2—H2B	109.5
Sn1—C1—H1C	109.5	H2A—C2—H2B	109.5
H1A—C1—H1C	109.5	N1—C2—H2C	109.5
H1B—C1—H1C	109.5	H2A—C2—H2C	109.5
C1ⁱ—Sn1—C1	180.00 (13)	H2B—C2—H2C	109.5
C1ⁱ—Sn1—Cl2ⁱ	90.42 (7)	N1—C3—H3A	109.5
C1—Sn1—Cl2ⁱ	89.58 (7)	N1—C3—H3B	109.5
C1ⁱ—Sn1—Cl2	89.58 (7)	H3A—C3—H3B	109.5
C1—Sn1—Cl2	90.42 (7)	N1—C3—H3C	109.5
Cl2ⁱ—Sn1—Cl2	180	H3A—C3—H3C	109.5
C1ⁱ—Sn1—Cl1ⁱ	90.43 (8)	H3B—C3—H3C	109.5
C1—Sn1—Cl1ⁱ	89.57 (8)	C2—N1—C3	112.7 (2)
Cl2ⁱ—Sn1—Cl1ⁱ	89.90 (2)	C2—N1—H1D	109.1
Cl2—Sn1—Cl1ⁱ	90.10 (2)	C3—N1—H1D	109.1
C1ⁱ—Sn1—Cl1	89.57 (8)	C2—N1—H1E	109.1
C1—Sn1—Cl1	90.43 (8)	C3—N1—H1E	109.1
Cl2ⁱ—Sn1—Cl1	90.10 (2)	H1D—N1—H1E	107.8
Cl2—Sn1—Cl1	89.90 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···Cl1	0.9	2.31	3.201 (2)	169
N1—H1D···Cl2ⁱⁱ	0.9	2.37	3.229 (2)	160

Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	(C₂H₈N)₂[SnCH₃)₂Cl₄]
M_r	382.75
Crystal system, space group	Triclinic, P1
Temperature (K)	297
a, b, c (Å)	6.6162 (9), 7.3703 (11), 8.4555 (12)
α, β, γ (°)	109.625 (14), 98.345 (12), 92.812 (12)
V (Å³)	382.13 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.34
Crystal size (mm)	0.5 × 0.3 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction	Multi-scan (CrysAlis CCD; Oxford Diffraction, 2009)
T_min, T_max	0.352, 0.652
No. of measured, independent and observed [I > 2σ(I)] reflections	3329, 1871, 1839
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 1.06
No. of reflections	1871
No. of parameters	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.43

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···Cl1	0.9	2.31	3.201 (2)	169
N1—H1D···Cl2ⁱ	0.9	2.37	3.229 (2)	160

Symmetry code: (i) x, y+1, z.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m696

doi:10.1107/S1600536811013584

Open

access