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A New 5,5′‐Bitetrazole Thorium(IV) Compound: Synthesis, Crystal Structure and Quantum Chemical Investigation
Author(s) -
Pohl Roland W. H.,
Wiebke Jonas,
Klein Axel,
Dolg Michael,
Maggiarosa Nicola
Publication year - 2009
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.200900152
Subject(s) - chemistry , triclinic crystal system , thorium , valence (chemistry) , crystal structure , crystallography , hydrate , quantum chemical , double salt , density functional theory , stereochemistry , molecule , inorganic chemistry , computational chemistry , uranium , organic chemistry , materials science , metallurgy
Thorium(IV) 5,5′‐bitetrazolate hydrate C 4 H 26 N 16 O 13 Th has been prepared and structurally analysed by single crystal XRD. The compound crystallises in the triclinic space group P $\bar {1}$ with the cell constants a = 1058.2(2), b = 1081.6(2), c = 1136.7(2) pm, α = 73.46(2), β = 83.98(2), γ = 66.01(2)°. The observed structure is similar to the salt‐like structures of the corresponding Tb III and Er III systems with respect to the non‐coordinating behaviour of the 5,5′‐bitetrazolate dianions. The Th IV cations form discrete hydroxo‐bridged binuclear thorium‐aqua complexes with Th–Th distances of 399(7) pm. Comparison with structural data of known hydrolysis products of the hydrated Th IV cation, and density functional calculations on gas phase molecular clusters, employing relativistic large‐core pseudopotentials and large valence‐only (7s7p5d2f1g)/[6s5p4d2f1g] basis sets for Th IV , confirm the identification of the cation in C 4 H 26 N 16 O 13 Th as [(μ‐OH) 2 Th 2 (H 2 O) 14 ] 6+ .(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)