Bis(triphenyl­phosphanyl­idene)iminium dichloridotriphenyl­stannate(IV)

Lucio De Lorentiis; Claudia Graiff; Giovanni Predieri

doi:10.1107/S1600536811035422

. 2011 Sep 14;67(Pt 10):m1356. doi: 10.1107/S1600536811035422

Bis(triphenylphosphanylidene)iminium dichloridotriphenylstannate(IV)

Lucio De Lorentiis ^a, Claudia Graiff ^a,^*, Giovanni Predieri ^a

PMCID: PMC3201402 PMID: 22065826

Abstract

The structure of the title compound, [Ph₃P=N=PPh₃]⁺[Ph₃SnCl₂]⁻ or (C₃₆H₃₀NP₂)[Sn(C₆H₅)₃Cl₂], obtained as a by product of the reaction between Ph₃SnCl and [Ph₃P=N=PPh₃]⁺·HSeO₃ ⁻, consists of discrete essentially isolated ions. Both the cation and the anion lie on twofold axes which pass through the central N atom in the cation and through the Sn^IV atom in the anion. In the crystal, the ions interact only through a weak interaction between the Cl atom of the anion and an H atom of a phenyl ring of the cation.

Related literature

For general background to selenite compounds, see: Delferro et al. (2010 ▶, 2011 ▶). For related structures, see: Harrison et al. (1978 ▶); Nayek et al. (2010 ▶); Ng (1995 ▶, 1999 ▶). For details of the Cambridge Crystal Structure Database, see: Allen (2002 ▶).

Experimental

Crystal data

(C₃₆H₃₀NP₂)[Sn(C₆H₅)₃Cl₂]
M _r = 959.44
Orthorhombic,
a = 17.9119 (6) Å
b = 9.7744 (3) Å
c = 13.3835 (4) Å
V = 2343.16 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 296 K
0.42 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.629, T _max = 0.746
36432 measured reflections
7179 independent reflections
6352 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.065
S = 1.04
7179 reflections
273 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 3430 Friedel pairs
Flack parameter: −0.022 (13)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035422/su2296sup1.cif

e-67-m1356-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035422/su2296Isup2.hkl

e-67-m1356-Isup2.hkl^{(351.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035422/su2296Isup3.mol

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Cl1ⁱ	0.93	2.79	3.718 (2)	173

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the PRIN 2008-Molecular Clusters in Nanoscience and the University of Parma, Italy, is gratefully acknowledged.

supplementary crystallographic information

Comment

The title compound was isolated from a dichloromethane solution as a by product of the reaction between of Ph₃SnCl with [Ph₃P=N=PPh₃]⁺ HSeO₃^- in dichloromethane solvent. The hydrogen selenite salt, prepared in the framework of our research activity on selenite compounds (Delferro et al., 2010, Delferro et al., 2011), contained a significant amount of [Ph₃P=N=PPh₃]⁺ Cl^-, which is responsible of the formation of the title compound.

The structure of the title compound consists of discrete [Ph₃P=N=PPh₃]⁺ and [Ph₃SnCl₂]^- ions (Fig. 1). The [Ph₃P=N=PPh₃]⁺, (or PPN⁺ for simplicity), cation is rather typical, lieing on a two fold axis that passes through the central N atom, N1. The P1—N1 bond distance of 1.5763 (9) Å and the P1—N1—P1ⁱ [symmetry code (i) = -x + 2, -y + 1, z] bond angle of 141.9 (2)° are in good agreement with the average values of 1.577 (6) Å and 143 (9)° found in 1409 PPN⁺ cations reported in the Cambridge Crystal Structure Database (CSD, V5.32, last update May 2011; Allen, 2002), see Fig. 3. In particular, examining the 1409 PPN⁺ cations it is evident that less than 40 examples present a linear geometry at the nitrogen atom. On excluding these cases the mean value of the P—N—P bond angle is reduced to 142 (7)°, even more in agreement with the angle in the title compound. The P atom is tetrahedral, with the C—P—C and C—P—N angles averaging 109 (3)°.

The [Ph₃SnCl₂]^- anion exhibits trigonal bipyramidal geometry at the tin atom, with the usual equatorial arrangement of organic groups and the chlorine atoms occupying axial positions. The anion is lying on a two-fold axis passing through the tin atom and atom C25 and C28 of one phenyl ring. The Cl1—Sn1 bond distance is 2.5858 (4) Å and the Cl—Sn—Clⁱⁱ [symmetry code: (ii) = -x + 2, -y + 2, z] bond angle is 177.83 (4)°, both in agreement with the values found in four examples (Ng, 1995,1999; Harrison et al., 1978; Nayek et al., 2010) reported in the CSD: The mean values are 2.590 (2) Å and 176.6 (7)°, respectively. The mean planes of the phenyl rings form dihedral angles of 59.70 (2)° and 38.78 (2)° with the SnC₃ mean plane.

In the crystal there is a weak interaction between the chlorine atom of the dichlorotriphenylstannate anion and a hydrogen atom of a phenyl ring of the bis(triphenylphosphine)iminium cation (Table 1).

Experimental

A dichloromethane solution of equimolar amounts of triphenyl-tin chloride and bis(triphenylphosphine)iminium hydrogenselenite was stirred at room temperature for 1 h. The solution was then cooled slowly to 278 K. Crystals suitable for X-ray analysis were obtained from the solution in two days.