Ce10[Si10O9N17]Br, Nd10[Si10O9N17]Br and Nd10[Si10O9N17]Cl oxonitridosilicate halides with a new layered structure type

The isotypic oxonitridosilicate halides Ce10[Si10O9N17]Br, Nd10[Si10O9N17]Br and Nd10[Si10O9N17]Cl were obtained by the reaction of the respective lanthanide metals, their oxides and halides with “Si(NH)2” in a radiofrequency furnace at temperatures around 1800 °C, using CsBr, resp. CsCl, as a flux. The crystal structures were determined by single-crystal X-ray diffraction (Pbam, no. 55, Z=2; Ce/Br: a=10.6117(9) Å, b=11.2319(10) Å, c=11.688(8) Å, R1=0.0356; Nd/Br: a=10.523(2) Å, b=11.101(2) Å, c=11.546(2) Å, R1=0.0239; Nd/Cl: a=10.534(2) Å, b=11.109(2) Å, c=11.543(2) Å, R1=0.0253) and represent a new layered structure type. The structure refinements were performed utilizing an O/N-distribution model according to Paulings rules, i.e. nitrogen was positioned on all bridging sites and mixed O/N-occupation was assumed on the terminal sites resulting in charge neutrality of the compounds. The layers consist of condensed [SiN2(O/N)2] and [SiN3(O/N)] tetrahedra of Q2 and Q3 type. The chemical composition of the compounds was derived from chemical analyses for Nd10[Si10O9N17]Br and electron probe micro analyses (EPMA) for all three compounds. The results of IR spectroscopic investigations are reported.