Crystal structure of afghanite, the eight-layer member of the cancrinite-group: evidence for long-range Si,Al ordering

Afghanite, ideally [(Na,K)(22)Ca-10][Si24Al24O96](SO4)(6)Cl-6, is the eight-layer member of the cancrinite-group (ABABACAC stacking sequence). Its structure was refined in the P31c space group to R = 4.5% by means of single-crystal X-ray diffraction data. The cell parameters are a = 12.8013(7) Angstrom, c = 21.4119(18) Angstrom. The P6(3)mc space group proposed in a previous structure refinement is not consistent with the ordered Si,AI pattern suggested by an Si/Al ratio equal to 1 shown by afghanite and other members of the cancrinite-group. The Si-O and Al-O bond distances, 1.61(2) Angstrom and 1.72(2) Angstrom respectively, found in the structure refinement, are in accordance with an ordered Si,AI distribution which is allowed by the P31c space group, a maximal non isomorphic subgroup of P6(3)mc. Afghanite contains six 11-hedra (cancrinite) cages and two 23-hedra (liottite) cages. Four cancrinite cages are stacked along [0 0 z]. They contain a regular....Ca-Cl-Ca-Cl.... chain similar to that observed in davyne and related phases: in particular Ca is located near the center of the bases whereas Cl is near the center of the cage. A liottite cage with a base-sharing cancrinite cage is stacked along [2/3 1/3 z] and [1/3 2/3 z]. The liottite cage hosts a maximum of three sulphate groups which alternate regularly with cation-containing planes. The cancrinite cage, that shares the bases with the liottite cages, presents a disordered distribution of Cl and F reading to two possible configurations similar to those observed in liottite