Novel mono- and bimetallic organotin(iv) compounds as potential linkers for coordination polymers.

The reaction of [2-(O[double bond, length as m-dash]CH)C6H4]Me2SnCl (2), obtained by the hydrolysis of [2-{(CH2O)2CH}C6H4]Me2SnCl (1), with the appropriate diamine, in a 2 : 1 molar ratio, in the absence of a solvent or catalyst, resulted in the bimetallic species ClSnMe2[2-C6H4(4-CH[double bond, length as m-dash]N-1,1'-C6H4C6H4-4'-N[double bond, length as m-dash]CH)-2'-C6H4]Me2SnCl (4) and ClSnMe2[2-C6H4(CH[double bond, length as m-dash]NCH2CH2N[double bond, length as m-dash]CH)-2'-C6H4]Me2SnCl (5). The reaction of 2 and 5 with KSCN gave the corresponding isothiocyanates [2-(O[double bond, length as m-dash]CH)C6H4]Me2Sn(NCS) (3) and (SCN)SnMe2[2-C6H4(CH[double bond, length as m-dash]NCH2CH2N[double bond, length as m-dash]CH)-2'-C6H4]Me2Sn(NCS) (6). Treating 3 with H2NCH2CH2NH2 also resulted in the corresponding bimetallic compound 6. The reaction of 2 with sodium isonicotinate gave [2-(O[double bond, length as m-dash]CH)C6H4]Me2SnO(O)CC5H4N-4 (7) and the subsequent treatment with ZnTPP (TPP = tetraphenylporphyrinate) led to the isolation of the heterobimetallic complex [{2-(O[double bond, length as m-dash]CH)C6H4}Me2SnO(O)CC5H4N-4]ZnTPP (8). The compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry in solution and IR spectroscopy in the solid state. The molecular structures for compounds 1-6 and 8 were established by single-crystal X-ray diffraction. For all compounds intramolecular O→Sn or Nimine→Sn coordination results in hypercoordinated species with a distorted trigonal bipyramidal (C,E)C2SnX core (E = O, Nimine; X = Cl, Nisothiocyanato, Oisonicotinato). In the heterobimetallic complex 8 the zinc atom has a distorted square pyramidal geometry with the Npyridyl atom at the apical position.

Di(imino)aryltin(IV) dichlorides as tectons for heterometallic coordination compounds.

Hydrolysis of [2-{(CH2O)2CH}C6H4]2SnCl2 (1) [prepared from 2-[(CH2O)2CH]C6H4MgBr and SnCl4, in 2 : 1 molar ratio] gave [2-(O=CH)C6H4]2SnCl2 (2). Treatment of with the appropriate amine, in the absence of a solvent or catalyst, resulted in the isolation in high yields of [2-(RN[double bond, length as m-dash]CH)C6H4]2SnCl2 [R = 2'-C10H7 (3), 2',4',6'-Me3C6H2 (4), PhCH2 (5), Me2NCH2CH2 (6), 2'-PyCH2 (7)]. The reaction of with [Pd(COD)Cl2] provided the heterometallic species [Cl2Pd{2-(2'-PyCH2N[double bond, length as m-dash]CH)C6H4}2SnCl2] (8). The compounds were characterised by multinuclear NMR spectroscopy in solution, and mass spectrometry and IR spectroscopy in the solid state. The molecular structures of 1, 2, 4-7 and 8·CH3CN were established by single-crystal X-ray diffraction. For all diorganotin(IV) dichlorides intramolecular O→Sn or Nimine→Sn coordination results in hypercoordinated species with a distorted octahedral (C,E)2SnCl2 core (E = O, N). The presence of intramolecular N→Sn interactions in solution, responsible for the restriction of free rotation of mesityl groups around the C-N(=C) single bonds, is suggested by (1)H and (13)C NMR data. In the heterometallic dinuclear complex 8 the octahedral coordination around tin is preserved as in 7 and the nitrogen atoms from the pyridyl groups in the pendant arms are coordinated to palladium, leading to a trans-square planar PdCl2N2 core.

The Reaction and Materials Chemistry of [Sn6 (O)4 (OSiMe3 )4 ]: Chemical Vapour Deposition of Tin Oxide.

[Sn6 (O)4 (OSiMe3 )4 ] and [{Sn(OSiMe3 )2 }2 ] have been used to deposit SnO thin films by chemical vapour deposition. Films derived from [Sn6 (O)4 (OSiMe3 )4 ] comprise uniform cubes and are highly oriented, whereas those deposited from [{Sn(OSiMe3 )2 }2 ] are made up of a continuous non-oriented layer with oriented cubes on the surface. The structure of a co-crystal, 2 Sn6 (O)4 (OSiMe3 )4 ⋅[Sn(OSiMe3 )2 ]2 ⋅4 THF, shows that [{Sn(OSiMe3 )2 }2 ], a liquid at room temperature, adopts a µ-OSiMe3 -bridged dimeric structure. [Sn6 (O)4 (OSiMe3 )4 ] reacts with O2 in a controlled manner to afford the novel oxo-cluster [Sn4( O)(OSiMe3 )8 ], the structure of which is reported. In addition, a crystal of {[Sn4 (O)(OSiMe3 )5 ]+ 2 [Sn(O)(OSiMe3 )4 Cl]+ 2 }[Cl]- 4 has been fortuitously isolated from the presence of SnCl2 in the starting material for the preparation of [Sn6 (O)4 (OSiMe3 )4 ], and has been shown to incorporate two novel cationic oxo-tin clusters.

Di-µ-chlorido-bis[chloridobis(dimethyl sulfoxide-κO)tin(II)].

The structure of the title compound, [Sn(2)Cl(4)(C(2)H(6)OS)(4)], contains dimers formed through weak Sn⋯Cl [3.691 (2) Å] inter-actions, resulting in a planar Sn(2)Cl(2) core with an inversion center at the centre of the four-membered ring. The Sn(II) atoms are penta-coordinated and have a distorted octa-hedral Ψ-SnCl(3)O(2) coordination geometry. The O atoms from the dimethyl sulfoxide mol-ecules occupy trans positions, while the Cl atoms exhibit a meridional arrangement.

Hydrogen bonding in substitutionally disordered di-µ-hydroxido-bis-{aqua-tri[bromido/chlorido(1/2)]tin(IV)} acetone disolvate.

The structure of the title compound, [Sn(2)Br(1.97)Cl(4.03)(OH)(2)(H(2)O)(2)]·2C(3)H(6)O, contains two hexa-coordinated Sn atoms bridged symmetrically by two hydroxide groups, with an inversion center in the middle of the planar Sn(2)O(2) ring, half of the mol-ecule being generated by inversion symmetry. The other sites of the distorted octa-hedral coordination geometry are occupied by halide atoms and water mol-ecules. The structure exhibits substitutional disorder of the halide atoms bonded to the Sn atom, with 0.672 (4) occupancy for Cl and 0.328 (4) for Br for each halide position. The compound crystallizes with two acetone mol-ecules, which are involved in intra- and inter-molecular O-H⋯O contacts. The water mol-ecules coordinated to the Sn atoms are also involved in O-H⋯O and O-H⋯X contacts, leading to a polymeric array along the a axis.