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Single-crystal growth experiments in the system CsF-Er 2 O 3 -SiO 2  resulted in the simultaneous crystallization of two chemically related compounds within the same run: Cs 2 Er[Si 6 O 14 ]F (phase I) and Cs 2 Er[Si 4 O 10 ]F (phase II). They represent the first examples for cesium erbium silicates containing fluorine. Basic crystallographic data are – phase I: space group  Cmca ,  a =17.2556(6) Å,  b =24.6565(7) Å,  c =14.4735(5) Å,  V =6157.9(3) Å 3 ,  Z =16; phase II: space group  Pnma ,  a =22.3748(7) Å,  b =8.8390(2) Å,  c =11.9710(4) Å,  V =2367.5(1) Å 3 ,  Z =8. The structures were determined by direct methods and refined to residuals of  R (| F |)=0.0229 for 2920 (phase I) and 0.0231 for 2314 (phase II) independent observed reflections with  I &gt;2σ( I ). The structure of phase I represents a previously unknown structure type with a three dimensional tetrahedral framework consisting of Q 3  and Q 4  groups in the ratio 2:1. Basic building units of the network are unbranched  sechser  single-chains running parallel to [001]. The network can be conveniently built up from the condensation of tetrahedral layers parallel to (010) or (100), respectively. The crystal structure of phase II can be classified as a  tubular  or  columnar  chain silicate indicating that the backbones of the structure are multiple chains of silicate tetrahedra. This structure is isotypic to a Cs 2 Y[Si 4 O 10 ]F, a compound that has been characterized previously. Alternatively, both compounds can be described as mixed octahedral-tetrahedral frameworks, which can be classified according to their  polyhedral microensembles . A topological analysis of both nets is presented.

Single-crystal X-ray diffraction study of Cs 2 Er[Si 6 O 14 ]F and Cs 2 Er[Si 4 O 10 ]F