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Systematic Counterion Tuning of the Solid‐State Structure of [Pt(thiourea) 4 ] 2+
Author(s) -
Schiessl Wolfgang,
Puchta Ralph,
Bugarčić Živadin D.,
Heinemann Frank W.,
van Eldik Rudi
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200601028
Subject(s) - chemistry , thiourea , crystallography , homoleptic , platinum , hydrogen bond , crystal structure , counterion , molecule , stereochemistry , ion , metal , catalysis , organic chemistry
Four different limiting molecular conformations are possible for the homoleptic square‐planar complex tetrakis(thiourea)platinum(II) depending on the up‐down orientation of the four thiourea (TU) ligands with respect to the PtS 4 plane. The realization of all four possible conformers can be achieved by a systematic variation of the counter anion making use of their individual hydrogen bonding ability. In total, the molecular and crystal structures of seven tetrakis(thiourea)platinum(II) complexes were determined by X‐ray diffraction. These are: [Pt(TU) 4 ]Cl 2 , [Pt(TU) 4 ]I 2 , [Pt(TU) 4 ](CF 3 SO 3 ) 2 , [Pt(TU) 4 ](BPh 4 ) 2 , [Pt(TU) 4 ](ClO 4 ) 2 , [Pt(TU) 4 ]SiF 6 · 0.25H 2 O and [Pt(TU) 4 ]S 2 O 6 . In all cases thiourea is coordinated by the sulfur atom and the two amino groups are not involved in the complex formation. The four independent Pt–S distances do not differ significantly from each other with an average value of 2.324(3) Å. The coordination geometry around the platinum center is distorted square‐planar. The orientation of the four TU groups in [Pt(TU) 4 ] 2+ depends on the molecular packing forces and hydrogen bonding ability of the counter anion. Hydrogen bonds of the type N–H ··· X (X = Cl – , I – , F – , O and S) are observed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)