Formation of M4Se4 cuboids (M = As, Sb, Bi) via secondary pnictogen–chalcogen interactions in the co-crystals MX3·SeP(p-FC6H4)3 (M = As, X = Br; M = Sb, X = Cl; M = Bi, X = Cl, Br)

Abstract

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. All the structures feature a primary MX(3) unit, which has three weak secondary MSe interactions to SeP(p-FC(6)H(4))(3) molecules. However, each of these SeP(p-FC(6)H(4))(3) molecules bridges three MX(3) molecules, resulting in the generation of an M(4)Se(4) (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 MX(3) pyramid, and the other four by the selenium atom of the phosphine selenide.

A Survey of Supramolecular Aggregation Based on Main Group Element⋯Selenium Secondary Bonding Interactions—A Survey of the Crystallographic Literature

“…Each of the molecules is located on a crystallographic 3-fold axis of symmetry and associate with a crystallographic site of symmetry 23. It can be noted from the Figure 7a The first selenide included in this survey is noted in the crystal of 21 [46], where two distinct molecules associate via As … Se interactions, with the participating atoms being arsenic(III) and selenide-selenium atoms, indicative of a pnictogen interaction. Each of the molecules is located on a crystallographic 3-fold axis of symmetry and associate with a crystallographic site of symmetry 23.…”

“…A relatively small number of compounds featuring As … Se interactions in their crystals are known and the chemical structures for the interacting species are shown in Figure 6, that is for 21-27, and, as demonstrated above, even though there is only a small number of examples, there is a great diversity in supramolecular architectures. The first selenide included in this survey is noted in the crystal of 21 [46], where two distinct molecules associate via As … Se interactions, with the participating atoms being arsenic(III) and selenide-selenium atoms, indicative of a pnictogen interaction. Each of the molecules is located on a crystallographic 3-fold axis of symmetry and associate with a crystallographic site of symmetry 23.…”

“…by two Sb … Se interactions; 29 [54] was employed as a precursor for CVD of Sb2Se3 and aerosolassisted chemical vapor deposition (AACVD) of Sb2Se3 thin films. The last zero-dimensional aggregate is found in the crystal of 32 [46;GEXSIN;3.36 Å ]. This is centered about a distorted Sb4Se4 cube, sustained by eight Sb … Se interactions, as described above for isostructural 21 [46], Figure 7b.…”

Phosphine chalcogenide complexes of antimony(III) halides

“…2,3 Transition metal-like coordination chemistry of SbX 3 acceptors has been recognized with comprehensive characterization of neutral complexes with nitrogen, 2,4-6 phosphorus, 7 oxygen, and sulfur donors. 3,[8][9][10][11][12][13][14][15] In comparison, complexes of pnictogen chalcogenide, R 3 PnCh (Pn = P, As, Sb, or Bi; Ch = O, S, Se, or Te), ligands on antimony halides have been identified in a nonsystematic fashion, on the basis of the isolation and characterization of rare examples. In this manner, examples of complexes involving two phosphine oxide or arsine oxide ligands with antimony trihalides, (R 3 PnO) 2 SbX 3 (X = halide), have been reported, while only 1:1 complexes have been reported with phosphine sulfide and phosphine selenide ligands, (R 3 PCh)SbX 3 (Ch = S or Se; X = halide).…”

“…In this manner, examples of complexes involving two phosphine oxide or arsine oxide ligands with antimony trihalides, (R 3 PnO) 2 SbX 3 (X = halide), have been reported, while only 1:1 complexes have been reported with phosphine sulfide and phosphine selenide ligands, (R 3 PCh)SbX 3 (Ch = S or Se; X = halide). 3,[9][10][11][12][13] As part of our systematic assessment of the coordination chemistry of Sb(III), we report here spectroscopic and solid-state data for derivatives of (Cy 3 PCh) n SbX 3 (Ch = O or S; X = F, Cl, Br, or I; n = 1 or 2), representing prototypical examples of phosphine chalcogenide complexes of SbX 3 .…”