Unlike typical hexa-hydrates, the title compound, [Mg(C2H6O)2(H2O)4]Br2·2C2H6O or [Mg(H2O)4(DME)2]Br2·DME2 (DME = dimethyl ether, C2H6O), is a water-poor magnesium(II) complex. The central magnesium cation (site symmetry 1) is coordinated by four water mol-ecules and two mol-ecules of dimethyl ether and adopts a slightly elongated trans-octa-hedral coordination geometry. The water mol-ecules are linked to outer-sphere bromide anions and additional dimethyl ether mol-ecules via O-H⋯Br and O-H⋯O hydrogen bonds. Due to the volatility of dimethyl ether, the presence of coordinating and non-coordinating mol-ecules of this ether makes this solid state structure presented here particularly inter-esting. To investigate the inter-molecular inter-actions leading to this special coordination, a Hirshfeld surface analysis was performed. It showed that the H⋯H inter-actions (70.4%) make the largest contribution to the crystal packing, followed by H⋯Br inter-actions (19.4%), H⋯O inter-actions (10.1%) and Br⋯O inter-actions (0.1%).
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