Formation of M4Se4 cuboids (M = As, Sb, Bi) via secondary pnictogen-chalcogen interactions in the co-crystals MX3·Se=P(p-FC6)H4)3 (M = As, X = Br; M = Sb, X = Cl; M = Bi, X = Cl, Br).

The reactions of the group 15 trihalides, MX(3) (M = As, Sb, Bi; X = Cl, Br), with the phosphine selenide SeP(p-FC(6)H(4))(3) result in the formation of co-crystals of formula MX(3)·SeP(p-FC(6)H(4))(3). No reaction was observed with MI(3) (M = As, Sb, Bi). The structures of MX(3)·SeP(p-FC(6)H(4))(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.

Structural isomerism in tris-tolyl halo-phosphonium and halo-arsonium tri-halides, [(CH3C6H4)3EX][X3], (E = P, As; X = Br, I).

The group 15 ligands (o-CH(3)C(6)H(4))(3)P, (m-CH(3)C(6)H(4))(3)P, (p-CH(3)C(6)H(4))(3)P, Ph(3)As, (o-CH(3)C(6)H(4))(3)As and (p-CH(3)C(6)H(4))(3)As have been reacted with two equivalents of di-iodine or di-bromine to yield complexes of formula R(3)EX(4) (E = P, As; X = I, Br). These halogenated group 15 compounds are ionic, [R(3)EX][X(3)] consisting of halo-phosphonium or halo-arsonium cations and trihalide anions. These adducts exhibit structural isomerism and may exist either as simple 1:1 ion pairs, [R(3)EX][X(3)], isomer (A), which display a weak XX interaction between cation and anion, or as a 2:1 complex, which consists of a [{R(3)EX}(2)X(3)](+) cationic species made up of two [R(3)EX](+) cations interacting with one [X(3)](-) anion.