Ce-4 Si4O4N6 O - A hyperbolically layered oxonitridosilicate oxide with an ordered distribution of oxygen and nitrogen

Irran, E., Kollisch, K., Leoni, S., Nesper, R., Henry, P. F., Weller, M. T. and Schnick, W. (2000) Ce-4 Si4O4N6 O - A hyperbolically layered oxonitridosilicate oxide with an ordered distribution of oxygen and nitrogen. Chemistry - A European Journal, 6 (15), 2714-2720. (doi:10.1002/1521-3765(20000804)6:15<2714::AID-CHEM2714>3.0.CO;2-J).

Abstract

The yellow-orange oxonitridosilicate oxide Ce-4[Si4O4N6]O was obtained by the reaction of cerium metal with Si(NH)(2) and SiO2 in a radiofrequency furnace at 1560 degrees C, The crystal structure was determined by single-crystal X-ray diffraction (a = 1033.67(6) pm, P2(1)3, Z = 4. R1 = 0.0412, wR2 = 0.0678) and powder neutron diffraction, In the solid there are complex cations [Ce4O](10+) that are enveloped by a hyperbolical layer structure [Si4O4N6](10-). The layer is built up by corner-sharing SiON3 tetrahedra of Q(3) type The oxygen atoms of the SiON3 tetrahedra are terminally bound to Si, while all nitrogen atoms bridge two neighboring Si centres, The crystallographic differentiation of O and N was unequivocally possible by a careful evaluation of the single-crystal X-ray diffraction data combined with lattice-energy calculations by using the MAPLE concept (Madelung part of lattice energy). Furthermore the results were confirmed by the chemical analyses. Subsequently, the determined N/O distribution and their crystallographic ordering was proved by neutron powder diffraction, In accordance with the molar ratio Si:(O,N) = 2:5 the [Si4O4N6](10-) network may be classified as a layer silicate. In this specific case a hyperbolically corrugated topology of the layers is observed; this is correlated to periodic nodal surface (PNS) representatives.

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