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[Sb 7 Se 8 Br 2 ] 3+ and [Sb 13 Se 16 Br 2 ] 5+ – Double and Quadruple Spiro Cubanes from Ionic Liquids
Author(s) -
Ahmed Ejaz,
Breternitz Joachim,
Groh Matthias F.,
Isaeva Anna,
Ruck Michael
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201301155
Subject(s) - antimony , chemistry , crystallography , bromine , isostructural , triclinic crystal system , crystal structure , atom (system on chip) , selenium , x ray crystallography , inorganic chemistry , organic chemistry , computer science , diffraction , optics , embedded system , physics
The reaction of antimony and selenium in the bromine‐rich Lewis acidic ionic liquid [BMIm]Br · 4.7AlBr 3 (BMIm: 1‐butyl‐3‐methylimidazolium) in the presence of a small amount of NbCl 5 at 160 °C yielded dark‐red crystals of [Sb 7 Se 8 Br 2 ][AlX 4 ] 3 . For X = Cl 0.15(1) Br 0.85(1) , the compound is isostructural to [Sb 7 S 8 Br 2 ][AlCl 4 ] 3 [ P 2 1 2 1 2 1 , a = 12.5132(5) Å, b = 17.7394(6) Å, c = 18.3013(6) Å]. For a higher chlorine content, X = Cl 0.58(1) Br 0.42(1) , a slightly disordered variant with a bisected unit cell is found [ P 2 1 2 1 2, a = 12.3757(3) Å, b = 17.4116(5) Å, c = 9.0420(2) Å]. The [Sb 7 Se 8 Br 2 ] 3+ heteropolycation ( C 2 symmetry) is a spiro double‐cubane with an antimony atom on the shared corner. From this distorted octahedrally coordinated central atom, tricoordinate selenium and antimony atoms alternate in the bonding sequence. The terminal antimony atoms each bind to a bromine atom. Quantum chemical calculations confirm polar covalent Sb–Se bonding within the cubes and indicate three‐center, four‐electron bonds for the six‐coordinate spiro atoms. The calculated charge distribution reflects the electron‐donor role of the antimony atoms. The use of a chlorine‐rich ionic liquid resulted in the formation of triclinic [Sb 13 Se 16 Br 2 ][AlX 4 ] 5 with X = Cl 0.80(1) Br 0.20(1) [ P $\bar {1}$ , a = 9.0842(5) Å, b = 19.607(1) Å, c = 21.511(1) Å, α = 64.116(6)°, β = 79.768(7)°, γ = 88.499(7)°]. The cationic cluster [Sb 13 Se 16 Br 2 ] 5+ is a bromine‐terminated spiro quadruple‐cubane. This 31 atom concatenation of four cubes is assumed to be the largest known discrete main group polycation. A similar reaction in a chloride‐free system yielded [Sb 7 Se 8 Br 2 ][Sb 13 Se 16 Br 2 ][AlBr 4 ] 8 . In its monoclinic structure [ P 2/ c , a = 27.214(5) Å, b = 9.383(2) Å, c = 22.917(4) Å, β = 101.68(1)°], the two types of polycations alternate in layers along the a axis. In the series [Sb 4+3 n Se 4+4 n Br 2 ] (2+ n )+ , these cations are the members with n = 1 and 3.