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Bis(1,3,5-trimethylbenzene)gallium(I) tetra­chloridoaluminate(III), [(1,3,5-(CH 3 ) 3 C 6 H 3 ) 2 Ga][AlCl 4 ] ( 1 ), bis(1,3,5-trimethylbenzene)gallium(I) tetrabromido­aluminate(III), [(1,3,5-(CH 3 ) 3 C 6 H 3 ) 2 Ga][AlBr 4 ] ( 2 ) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III), [1,3,5-(CH 3 ) 3 C 6 H 3 Ga][AlI 4 ] ( 3 ) were synthesized from the corresponding subvalent Ga I /Al III  mixed metal halides and characterized  via  C,H analysis, Raman spectroscopy, X-ray powder diffraction and X-ray single crystal diffraction. Compound  1  crystallizes in the noncentrosymmetric monoclinic space group  Cc  isotypic to [(1,3,5-(CH 3 ) 3 C 6 H 3 ) 2 Ga][GaCl 4 ]. For  2  and  3  the monoclinic space group  P 2 1 / n  is found, however, they are neither isotypic nor homotypic. While  2  is isotypic to [(1,3,5-(CH 3 ) 3 C 6 H 3 ) 2 In][InBr 4 ],  3  establishes a new structure type. In the solids of all three title compounds coordination polymeric chains are found, in  1  and  2  built up from bis(arene)-coordinated, in  3  from mono(arene)-coordinated Ga +  ions and the corresponding Al X  4  −  anions in a 1κCl:2κCl′ ( 1 ), 1κCl,Cl′:2κCl″ ( 2 ) or 1κCl,Cl′:2κCl″:3κCl‴ ( 3 ) bridging mode. Taking into account the weaker coordinating character of the AlCl 4  −  as compared to the AlBr 4  −  anion, in line with expectations the number of gallium halogen contacts is increased and the strength of the  π -arene bonding is reduced in the bromide  2  as compared to the chloride  1 . Finally, with the even more strongly coordinating AlI 4  −  anion the arene coordination is limited to one molecule. Considering mesitylene complexes of gallium, the formation of a mono(arene) complex is unprecedented and even considering group 13 elements in general, the formation of a mono(mesitylene) complex like  3  is unusual. Furthermore, compound  3  is the first structurally characterized arene solvate of a main group metal tetraiodidometallate.

zeitschrift für naturforschung b

Investigation of mesitylene-solvated group 13 mixed-metal halides: syntheses and crystal structures of bis(1,3,5-trimethylbenzene)gallium(I) tetrachlorido- and tetrabromidoaluminate(III) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III). Variation of the gallium- π -arene bond strength