Tetra­chlorido­(1,10-phenanthroline-κ2 N,N′)tin(IV) 1,2-dichloro­ethane hemisolvate

Badri Z Momeni; Frank Rominger; Simin S Hosseini

doi:10.1107/S1600536809017346

. 2009 May 29;65(Pt 6):m690. doi: 10.1107/S1600536809017346

Tetrachlorido(1,10-phenanthroline-κ² N,N′)tin(IV) 1,2-dichloroethane hemisolvate

Badri Z Momeni ^a,^*, Frank Rominger ^b, Simin S Hosseini ^a

PMCID: PMC2969692 PMID: 21583047

Abstract

The asymmetric unit of the title compound, [SnCl₄(C₁₂H₈N₂)]·0.5C₂H₄Cl₂, contains a tin complex and one disordered half-molecule of the solvent dichloroethane [occupancies 0.71 (2):0.29 (2)]. The six coordinate Sn(IV) atom adopts a distorted octahedral geometry. π–π interactions between adjacent aromatic rings [interplanar distance 3.483 (5) Å] seem to be effective in the stabilization of the crystal packing.

Related literature

For tin(IV) halide complexes with a variety of Lewis bases, see: Harrison et al. (1972 ▶). For 1:1 complexes of the type [SnX ₄(NN)] (X = halide; NN = 1,10-phenanthroline or 2,2′-bipyridyl ligand), see: Matsubayashi & Iyoda (1977 ▶). For the structure of the title complex without the co-crystallized solvent, see: Su et al. (2007 ▶) and with co-crystallized benzene, see: Hall & Tiekink (1996 ▶). For the preparation of trans-[PtClMe₂(CH₂Cl)(phen)] used in the synthesis, see: Monaghan & Puddephatt (1985 ▶).

Experimental

Crystal data

[SnCl₄(C₁₂H₈N₂)]·0.5C₂H₄Cl₂
M _r = 490.17
Orthorhombic,
a = 14.4478 (2) Å
b = 12.3681 (1) Å
c = 18.3551 (2) Å
V = 3279.91 (6) Å³
Z = 8
Mo Kα radiation
μ = 2.37 mm⁻¹
T = 200 K
0.20 × 0.18 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T _min = 0.649, T _max = 0.765
31457 measured reflections
3747 independent reflections
2954 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.085
S = 1.05
3747 reflections
195 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Data collection: SMART (Bruker, 1995 ▶); cell refinement: SAINT (Bruker, 1995 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017346/hg2511sup1.cif

e-65-0m690-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017346/hg2511Isup2.hkl

e-65-0m690-Isup2.hkl^{(183.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Sn1—N21	2.224 (3)
Sn1—N11	2.238 (3)
Sn1—Cl2	2.3333 (12)
Sn1—Cl1	2.3708 (10)
Sn1—Cl4	2.4095 (10)
Sn1—Cl3	2.4480 (10)

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Acknowledgments

We thank the Science Research Council of K. N. Toosi University of Technology for financial support. We also thank Johnson Matthey for the generous loan of platinum salt.

supplementary crystallographic information

Comment

It has long been known that tin(IV) halides form complexes with a variety of Lewis bases (Harrison et al., 1972). Bidentate diimine ligandes are one of the strongest bases towards tin(IV) halides and more often form 1:1 complexes of the type [SnX₄(NN)] (X = halide; NN = diimine ligand). Among them, the 1,10-phenanthroline and 2,2'-bipyridyl ligands are of particular interest (Matsubayashi & Iyoda, 1977). The title compound reported here, an adventitious result of our work on organoplatinum complexes, has a distorted octahedral geometry including different Sn—Cl and Sn—N bond lengths (see Fig. 1). The Cl3—Sn—Cl4 geometry shows remarkable deviation from linearity with a bond angle of 170.32 (4)°. The contraction of N11—Sn1—N21 to 74.7 (1) from the ideal 90° is typical for a chelating phenanthroline ligand. Figure 2 depicts the π-π interaction between adjacent aromatic rings, which seems, among Cl···Cl van der Waals contacts, to be significant in the stabilization of the crystal packing, as both preliminary structure determinations of the same complex, either without cocrystallized solvent (Su et al., 2007) or with co-crystallized benzene (Hall & Tiekink, 1996) show the same intermolecular contact features.

Experimental

A solution of SnCl₂*2H₂O (40 mg, 0.18 mmol) in THF (1 ml) and a solution of PPh₃ (26 mg, 0.10 mmol) in dichloromethane (1 ml) were added to a dichloromethane solution (10 ml) of cis- and trans-[PtClMe₂{CH₂Cl}(phen)] (50 mg, 0.10 mmol) (Monaghan & Puddephatt, 1985) under Argon atmosphere. The reaction mixture was stirred for 3 h whereupon the yellow solution turned colourless. The solvent was removed under vacuum and the resulting white oily residue was solidified from CH₂Cl₂-diethylether solution to afford trans-[PtMe₂(CH₂Cl)(phen)(PPh₃)][SnCl₃]* C₂Cl₂H₄. Yield: 85%; m.p. 429 K. Anal. Calc. for C₃₅H₃₅Cl₆N₂PPtSn: C, 40.4; H, 3.4; N, 2.7. Found: C, 39.7; H, 3.0; N, 2.5. NMR data in 1,2-dichloroethane/CDCl₃: δ (³¹P) 1.50 [¹J(¹⁹⁵Pt-³¹P) = 1036 Hz]. The title complex crystallized during the slow decomposition of the organoplatinum(IV) species from a 1,2-dichloroethane solution yielding yellow polyhedral crystals.