Naslov
Compounds with cluster cations together with cluster anions [(M_6X_12)(EtOH)_6]^2+ besides [(Mo_6Cl_8)Cl_4X_2]^2- (M = Nb, Ta; X = Cl, Br) - Synthesis and crystal structures

Autori
Bašic, Ivan ; Brničević, Nevenka ; Beck, Ulrich ; Simon, Arndt ; McCarley, Robert E.

Izvornik
Zeitschrift für anorganische und allgemeine Chemie (0044-2313) 624 (1998); 725-732

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
hexanuclear metal halide cluster; cluster cation-cluster anion salts; H-bridges; crystal structure

Sažetak
Compounds consisting of both cluster cations and cluster anions of the composition [(M_6X_12)(EtOH)_6][(Mo_6Cl_8)Cl_4X_2]xnEtOHxmEt_2O (M = Nb, Ta; X = Cl, Br) have been prepared by the reaction of (M_6X_12)X_2x6EtOH with (Mo_6Cl_8)Cl_4. IR data are given for three compounds. The structures of [(Nb_6Cl_12)(EtOH)_6][(Mo_6Cl_8)Cl_6]x3EtOHx3Et_2O (1) and [(Ta_6Cl_12)(EtOH)_6][(Mo_6Cl_8)Cl_6]x6EtOH (2) have been solved in the triclinic space group P-1 (No. 2). Crystal data: 1, a = 10.641(2) A, b = 13.947(2) A, c = 15.460(3) A, alpha = 65.71(2)^o, beta = 73.61(2)^o, gamma = 85,11(2)^o, V = 2005.1(8) A^3 and Z = 1; 2, a = 11.218(2) A, b = 12.723(3) A, c = 14,134(3) A, alpha = 108,06(2)^o, beta = 101.12(3)^o, gamma = 91,18(2)^o, V = 1874.8(7) A^3 and Z = 1. Both structures are built of octahedral [(M_6Cl_12)(EtOH)_6]^2+ cluster cations and [(Mo6_Cl_8)Cl_6]^2- cluster anions, forming distorted CsCl structure types. The Nb-Nb and Ta-Ta bond lengths of 2.904 A and 2.872 A (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 and 2.609 A (on average) are characteristic for the [(Mo_6Cl_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.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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