The crystal structures of Hg2P3Br(I) and Hg2P3Cl(II) have been refined by least-squares full-matrix procedures to R = 0.037 (I) and R = 0.035 (II). I is orthorhombic, space group Pbcn, a = 8.014(1) Å, b = 8.902(1) Å, c = 7.823(1) Å, Z = 4. II is monoclinic, space group C2/c, a = 7.834(2) Å, b = 8.844(1) Å, c = 7.591(1) Å, β = 98.68(1), Z = 4. Both structures consist of [unk](P1−) helical chains running along the c-direction. The conformation of the chains is the same in I and II but the arrangement of the chains within the unit cells is different. The structures are also compared with those of Cd2Z3X (X = Cl, Br, I; Z = P, As).
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