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Tetramethylformamidinium trichlorogermanite, [CH(NMe 2 ) 2 ][GeCl 3 ], tetramethylformamidinium trichlorostannite, [CH(NMe 2 ) 2 ][SnCl3], bis-(tetramethylformamidinium hexaiododigallate, [CH(NMe 2 ) 2 ] 2 [Ga 2 I 6 ] and bis-(tetramethylformamidinium hexachlorodiindate, [CH(NMe 2 ) 2 ] 2 [In 2 Cl 6 ] have been prepared by the reactions between tetramethylformamidinium chloride, [CH(NMe 2 ) 2 ]Cl, and the corresponding low valent halides GeCl 2  (as dioxane adduct), SnCl 2 , “GaI” and InCl. Their crystal structures have been determined by single crystal X-ray diffraction. [CH(NMe 2 ) 2 ][GeCl 3 ] aggregates in a centrosymmetric dimeric structure, in which two trigonal pyramidal GeCl 3  units are connected together by two weak Ge···Cl bonds and each Ge atom is bonded to one cation by a weak Ge···N contact. Two sets of weak hydrogen bonds C-H···Cl are observed with bond lengths of 2.87(2) Å and 2.85(2) Å . In [CH(NMe 2 ) 2 ][SnCl 3 ], the SnCl 3  − units adopts a (3+3) coordination with three normal Sn-Cl bonds and three weak Sn···Cl contacts. [CH(NMe 2 ) 2 ] 2 [Ga 2 I 6 ] and [CH(NMe 2 ) 2 ] 2 [In 2 Cl 6 ] contain metal-metal bonded anions with distorted staggered ethane-like conformations. The metal-metal bond lengths are 2.423(1) Å (Ga-Ga) and 2.719(1) Å (In-In). Their Raman spectra contain intense bands at 118.7 cm −1 (Ga-Ga) and 174.7 cm −1 (In-In) associated with metal-metal stretching modes.

Formamidinium Salts of Low Valent Metal Halide Anions MX 3 – (M = Ge, Sn) and M 2 X 6 2– (M = Ga, In)