Anhydrous Methane Sulfonates of Group 13 Metals: Synthesis and Characterization of Ga(CH₃SO₃)₃, In(CH₃SO₃)₃, and Tl(CH₃SO₃)₃

The anhydrous group 13 methanesulfonates M[CH 3 SO 3 ] 3 (M = Ga, In, Tl) are obtained from reactions of Ga 2 [SO 4 ] 3 , In 2 O 3 , and Tl[NO 3 ], respectively, with CH 3 SO 3 H in sealed glass ampoules at a temperature of 140 °C. The crystal structure of Ga[CH 3 SO 3 ] 3 is trigonal rhombohedral (R, Z = 6, a = 14.8795(3), c = 8.6780(3) Å) and shows the octahedrally coordinated Ga 3+ ions linked into chains. The methanesulfonates of In and Tl are isotypic and crystallize with monoclinic symmetry ( P 2 1 / c , Z = 4, In: a = 8.907(1), b = 13.280(1), c = 9.762(1) Å, β = 109.25(1)°; Tl: a = 8.9441(9), b = 13.2831(8), c = 9.8316(8) Å, β = 109.40(1)°). In the crystal structure of both compounds, the cations are in octahedral coordination and connected to layers. The thermal decomposition of the compounds leads to the oxides M 2 O 3 (M = Ga, In), and to the sulfide Tl 2 S.