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Linear Trimeric Hafnium Clusters in Hf0.86(1)I3
Department für Chemie, Universität zu Köln, Greinstraße 6, D-50939 Köln, Germany
Fakultät für Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany
* Author to whom correspondence should be addressed.
Received: 21 March 2011; in revised form: 4 May 2011 / Accepted: 9 May 2011 / Published: 10 May 2011
Abstract: The reduction of hafnium tetraiodide, HfI4, with aluminum at 600 °C or 850 °C in the presence of a NaI flux resulted in black single crystals of Hf0.86(1)I3. This composition corresponds well to the upper end of the non-stoichiometry range 0.89 ≤ x ≤ 1.00 previously reported for HfxI3. The crystal structure (a = 1250.3(2), c = 1999.6(3) pm, R-3m, Z = 18) is made up of hexagonal closest packed layers of iodide ions. One third of the octahedral holes would be filled as in TiI3 or ZrI3 if it were Hf1.00I3. In Hf0.86(1)I3, one out of six octahedral holes along  are, however, only occupied by 16%. In contrast to TiI3-I and ZrI3, one striking structural feature is in the formation of linear hafnium trimers with identical Hf―Hf distances of 318.3(2) pm rather than the formation of dimers. These may be associated with Hf―Hf bonding although only 2.64 electrons are available for one Hf5.16I18 column.
Keywords: hafnium; Iodide; cluster; crystal structure
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MDPI and ACS Style
Beekhuizen, J.; Mudring, A.-V.; Meyer, G. Linear Trimeric Hafnium Clusters in Hf0.86(1)I3. Crystals 2011, 1, 40-46.
Beekhuizen J, Mudring A-V, Meyer G. Linear Trimeric Hafnium Clusters in Hf0.86(1)I3. Crystals. 2011; 1(2):40-46.
Beekhuizen, Jan; Mudring, Anja-Verena; Meyer, Gerd. 2011. "Linear Trimeric Hafnium Clusters in Hf0.86(1)I3." Crystals 1, no. 2: 40-46.