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The complexes formed between the "gallium dihalides" (Ga2X4) and 1,4-dioxane (diox), Ga2X4-2(diox) (X = Cl, Br, I), have been reinvestigated. Ga2Cl4'2C4H802 forms triclinic crystals, space group Rl, with a -8.829 (5) Á, b = 9.101 (5)A, c = 10.82 (1) A, a = 107.27°, ß = 91.73 (2)°, y = 72.34 (2)°, Z = 2, Dcalcd = 1,943 g cm*3, and £>measd = 1.95 g cm"3.The structure has been solved from 3034 diffractometer-measured intensities with Mo Ka radiation ( 0.7107 A) and refined by full-matrix least squares to R = 0.085. The crystal structure shows that the complex is a discrete molecule containing a gallium-gallium bond of length 2.406 (1) A with dioxane acting as a monodentate ligand. Spectroscopic and other evidence is presented which shows that the bromide and iodide complexes have a similar structure.

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