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A few black, rectangular thin plates of Ca 21 SrSi 24 O 2  were obtained by serendipity in a solid-state reaction of calcium metal, strontium chloride and silicon powder at 1200 K for 2 days designed to produce ‘Ca 2 SrCl 2 [Si 3 ]’. The title compound forms next to some CaSi and some remaining educts. Ca 21 SrSi 24 O 2  crystallizes in the monoclinic space group  C 2/ m  (no. 12) with unit cell parameters of  a =1895.2(2),  b =450.63(5) and  c =1397.33(18) pm and  β =112.008(7)° ( Z =1). The title compound shows planar, eight-membered, kinked Si 8  chains with Si–Si distances between 241.4 and 245.0 pm indicating bonding interactions and kinked ‘rope ladders’ connecting the chains with interatomic Si–Si distances in the range 268.1–274.7 pm. Embedded in between these silicon substructures are columns of oxygen centered, apex sharing [(Ca 1− x   Sr  x  ) 6/2 O] octahedra and calcium ions.

Oxide meets silicide – synthesis and single-crystal structure of Ca 21 SrSi 24 O 2