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The reactions of the group 15 trihalides, MX3 (M = As, Sb, Bi; X = Cl, Br), with the phosphine selenide SeP(p-FC6H4)3 result in the formation of co-crystals of formula MX3·SeP(p-FC6H4)3. No reaction was observed with MI3 (M = As, Sb, Bi). The structures of MX3·SeP(p-FC6H4)3 (M = As, X = Br 2; M = Sb, X = Cl 3; M = Bi, X = Cl 5; M = Bi, X = Br 6) have been established, and are isomorphous, crystallising in the cubic I23 space group. All the structures feature a primary MX3 unit, which has three weak secondary MSe interactions to SeP(p-FC6H4)3 molecules. However, each of these SeP(p-FC6H4)3 molecules bridges three MX3 molecules, resulting in the generation of an M4Se4 (M = As, Sb, Bi) distorted cuboid linked by the pnictogen–chalcogen interactions. Four opposing corners of the cuboid are occupied by the M atom (M = As, Sb, Bi) of an MX3 pyramid, and the other four by the selenium atom of the phosphine selenide.
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