Synthesis and crystal structures of two novel niobium oxo-selenides:: K4Nb2Se11O consisting of infinite anionic chains and Cs4Nb2Se11O being the first example for the coexistence of molecular and infinite chainlike transition metal polychalcogenide anions in one compound

被引:12
作者
Durichen, P [1 ]
Krause, O [1 ]
Bensch, W [1 ]
机构
[1] Univ Kiel, Inst Anorgan Chem, D-24098 Kiel, Germany
关键词
D O I
10.1021/cm970829l
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The new compounds K4Nb2Se11O and Cs4Nb2Se11O have been synthesized from a K2Sen and Cs2Sen flux, respectively. K4Nb2Se11O crsytallizes in the orthorhombic space group Pbca with lattice parameters a = 15.946(4) Angstrom, b = 13.872(3) Angstrom, c = 18.622(3) Angstrom, V= 4119(2) Angstrom(3), Z = 8. The structure has been refined to a wR(2)(F-2) of 0.1547 for 163 parameters and 4714 reflections. The R-1(F) amounts to 0.0410. Cs4Nb2Se11O crsytallizes in the triclinic space group P-1 with unit cell dimensions a = 12.023(4) Angstrom, b = 14.367(4) Angstrom, c = 14.571(4) Angstrom, alpha = 76.90(2)degrees, beta = 78.43(2)degrees, gamma = 71.89(2)degrees, V = 2307(1) Angstrom(3), ((Z) over bar= 4). Refinement against F resulted in a wR(2) of 0.1075 for 326 parameters and 10542 unique reflections. The R1(F) amounts to 0.0411. The structures of both compounds consist of expanded and interconnected Nb(2)Q(11) units (Q = Se, O) which are built up of two face-sharing pentagonal NbSe6O and NbSe7 bipyramids. In K4Nb2Se11O the Nb2Q11 units are interconnected by Se-3(2-) anions giving rise to infinite anionic (1)(infinity)[Nb2Se11O](4-) chains which are separated by the K+ cations. Cs4Nb2Se11O resembles a mixture of molecular [Nb2Se11O](4-) anions and,(1)(infinity)[Nb2Se11O](4-) infinite anionic chains coexisting in one structure. Both compounds exhibit Se-n(n-) anions with unusual bonding properties. In K4Nb2Se11O, a nearly linear Se-3(4-) anion is found, whereas Cs4Nb2Se11O contains a See fragment which carries six negative charges.
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页码:2127 / 2134
页数:8
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