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Ionothermal Synthesis, Crystal Structure, and Chemical Bonding of the Niobium(IV) Complex Nb 2 (Se 2 ) 2 (AlCl 4 ) 4
Author(s) -
Müller Ulrike,
Isaeva Anna,
Ruck Michael
Publication year - 2014
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/zaac.201400095
Subject(s) - niobium , monoclinic crystal system , chemistry , crystallography , crystal structure , selenium , adduct , lewis acids and bases , ionic bonding , molecule , crystal (programming language) , arsenic , bond length , inorganic chemistry , ion , catalysis , organic chemistry , computer science , programming language
The reaction of selenium and NbCl 5 with arsenic in the Lewis‐acidic ionic liquid BMImCl · 4.8AlCl 3 at 100 °C yielded dark‐red block‐shaped crystals of Nb 2 Se 4 (AlCl 4 ) 4 , which immediately decompose when exposed to humid air. Arsenic takes the part of the reducing agent for niobium as well as selenium. The crystal structure was described in the monoclinic space group P 2 1 / n (no. 14) with a = 898.0(1) pm, b = 991.3(1) pm, c = 1629.1(2) pm, and β = 92.43(1)° at 296(1) K. The unit cell contains two C 2h symmetric Nb 2 (Se 2 ) 2 (AlCl 4 ) 4 molecules. The latter consist of a central rectangular bipyramid [Nb 2 (Se 2 ) 2 ] 4+ and four η 2 ‐coordinating AlCl 4 – tetrahedra. Diamagentism of the compound and DFT‐based real‐space bonding analysis imply a chemical bond between the niobium(IV) cations, which are 292.2(2) pm apart. Nb 2 Se 4 (AlCl 4 ) 4 can be interpreted as the AlCl 3 adduct of NbSe 2 Cl 2 .