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The crystal chemistry of binary and ternary intermetallic compounds with orthorhombic Re 3 B or MgCuAl 2  type structure is reviewed. Besides the preparation techniques and crystal chemistry we focus on the structure–property relations and chemical bonding peculiarities. So far about 100 compounds with this structural arrangement have been reported. The large family of intermetallics comprises borides, aluminides, gallides, indides, thallides, and stannides, but also some magnesium and cadmium compounds.

Re 3 B type intermetallics — crystal chemistry, bonding and properties