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[Be(ND 3 ) 4 ]Cl 2 : Synthesis, Characterisation and Space‐Group Determination Guided by Solid‐State Quantum Chemical Calculations
Author(s) -
Kraus Florian,
Baer Sebastian A.,
Hoelzel Markus,
Karttunen Antti J.
Publication year - 2013
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.201300356
Subject(s) - chemistry , orthorhombic crystal system , crystallography , quantum chemical , group (periodic table) , microcrystalline , space group , solid state , chemical stability , crystal structure , thermogravimetric analysis , x ray crystallography , stereochemistry , molecule , diffraction , organic chemistry , physics , optics
Abstract Treatment of BeCl 2 with dry liquid ND 3 and subsequent removal of the solvent leads to the colourless microcrystalline powder of [Be(ND 3 ) 4 ]Cl 2 . It crystallises in the orthorhombic space group Pna 2 1 with a = 9.395(4), b = 11.901(6), c = 6.761(3) Å, V = 755.9(6) and Z = 4 at 27 °C, and a = 9.3736(8), b = 11.8162(12), c = 6.6596(6) Å, V = 737.62(12) and Z = 4 at –269.6 °C. The structure contains the tetrahedral tetraammineberyllium(II) cation which follows the octet rule. It was shown to be stable under ambient conditions and temperatures up to approximately 175 °C. We additionally discuss the aid of solid‐state quantum chemical calculations for the assignment of proper crystallographic space groups in cases where the choice between centrosymmetry and noncentrosymmetry is not completely obvious, e.g. here between Pna 2 1 and Pnma . Thermogravimetric measurements show that [Be(ND 3 ) 4 ]Cl 2 decomposes only above approximately 175 °C, giving off two equivalents of ND 3 to form [Be(ND 3 ) 2 Cl 2 ]. The latter seems to be stable up to approximately 300 °C after which it sublimes. These results show unambiguous evidence for the stability of the tetraammineberyllium(II) cations of the title compounds from –269.6 °C to 175 °C.