Premium
Compounds with Cluster Cations together with Cluster Anions [(M 6 X 12 )(EtOH) 6 ] 2+ besides [(Mo 6 Cl 8 )Cl 4 X 2 ] 2– (M = Nb, Ta; X = Cl, Br) – Synthesis and Crystal Structures
Author(s) -
Bašic I.,
Brničević N.,
Beck U.,
Simon A.,
McCarley R. E.
Publication year - 1998
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(199804)624:4<725::aid-zaac725>3.0.co;2-x
Subject(s) - triclinic crystal system , chemistry , crystallography , crystal structure , cluster (spacecraft) , octahedron , hydrogen bond , molecule , bond length , ion , stereochemistry , organic chemistry , computer science , programming language
Compounds consisting of both cluster cations and cluster anions of the composition [(M 6 X 12 )(EtOH) 6 ][(Mo 6 Cl 8 )Cl 4 X 2 ] · n EtOH · m Et 2 O (M = Nb, Ta; X = Cl, Br) have been prepared by the reaction of (M 6 X 12 )X 2 · 6 EtOH with (Mo 6 Cl 8 )Cl 4 . IR data are given for three compounds. The structures of [(Nb 6 Cl 12 )(EtOH) 6 ][(Mo 6 Cl 8 )Cl 6 ] · 3 EtOH · 3 Et 2 O 1 and [(Ta 6 Cl 12 )(EtOH) 6 ][(Mo 6 Cl 8 )Cl 6 ] · 6 EtOH 2 have been solved in the triclinic space group P 1 (No. 2). Crystal data: 1 , a = 10.641(2) Å, b = 13.947(2) Å, c = 15.460(3) Å, α = 65.71(2)°, β = 73.61(2)°, γ = 85.11(2)°, V = 2005.1(8) Å 3 and Z = 1; 2 , a = 11.218(2) Å, b = 12.723(3) Å, c = 14.134(3) Å, α = 108.06(2)°, β = 101.13(2)°, γ = 91.18(2)°, V = 1874.8(7) Å 3 and Z = 1. Both structures are built of octahedral [(M 6 Cl 12 )(EtOH) 6 ] 2+ cluster cations and [(Mo 6 Cl 8 )Cl 6 ] 2– cluster anions, forming distorted CsCl structure types. The Nb–Nb and Ta–Ta bond lengths of 2.904 Å and 2.872 Å (mean values), respectively, are rather short, indicating weak M–O bonds. All O atoms of coordinated EtOH molecules are involved in H bridges. The Mo–Mo distances of 2.603 Å and 2.609 Å (on average) are characteristic for the [(Mo 6 Cl 8 )Cl 6 ] 2– anion, but there is a clear correlation between the number of hydrogen bridges to the terminal Cl and the corresponding Mo–Cl distances.