Ga 2 Cl 4 reacts with hexamethylbenzene in benzene to give (hexamethylbenzene)gallium (I)- tetrachlorogallate(III), (CH 3 ) 6 C 6 G a + GaCl 4 - , in high yield. The complex crystallizes in the rhombohedral space group R 3 m with four formula units per cell. Cell constants are a = 12.449(3) Å and α = 91.01(2)°. In the structure tetrameric clusters can be identified containing two crystallographically independent formula units, one having 3 m and the other three having m symmetry. In both types of (arene)Ga + cations the Ga atoms are symmetrically positioned over the arene ring, 2.43(3) and 2.51(3) Å , respectively, away from the ring plane. Four (arene)Ga + cations and four GaCl 4 - anions are aggregated in such a way that the Ga 1 atoms are surrounded by six or seven chlorine atoms, respectively, at distances in the range 3.16(1) to 3.67(1) Å . The four hexamethylbenzene molecules form an efficient cover around the inorganic [Ga + GaCl 4 - ] 4 framework. Between the tetrameric clusters there are no contacts of the Ga 1 ···Cl Type.
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Thewalt et al. (1984) studied this question.