The oxonitridosilicate fluoride phosphor Li24Sr12[Si24N47O]­F:Eu2+ was synthesized from Si3N4, SrH2, LiNH2, LiF, and EuF3 as dopant in a radio frequency furnace. The crystal structure (space group Pa3̅ (no. 205), a = 10.72830(10) Å, R 1 = 0.0401, wR 2 = 0.0885, Z = 1) of the host compound Li24Sr12[Si24N47O]F was solved and refined on the basis of single-crystal X-ray diffraction data. Li24Sr12[Si24N47O]F is homeotypic with the nitridosilicate Li2SrSi2N4 as both compounds are characterized by the same tetrahedra network topology, but Li24Sr12[Si24N47O]F is an oxonitridosilicate and contains an additional F site. The implemented F is verified by EDX measurements as well as through calculations with PLATON. Besides, the electrostatic consistency of the refined crystal structure is proven by lattice energy calculations. The Eu2+-doped compound Li24Sr12[Si24N47O]­F:Eu2+ shows an orange to red luminescence (λmax = 598 nm; fwhm = 81 nm) under excitation with blue light, which differs from that of Li2SrSi2N4:Eu2+ (λem = 613 nm; fwhm = 86 nm) due to the additional F site. According to the blue-shifted emission, application in LEDs for sectors with low CRI is conceivable.

LiCa 4 Si 4 N 8 F and LiSr 4 Si 4 N 8 F were synthesized from Si 3 N 4 , LiNH 2 , CaH 2 /SrH 2 , and LiF through a metathesis reaction in a radiofrequency furnace. The crystal structures of both compounds were solved and refined on the basis of single-crystal X-ray diffraction data [LiCa 4 Si 4 N 8 F: P2 1 /c (no. 14), a = 10.5108 (3), b = 9.0217(3), c = 10.3574(3) Å, = 117.0152(10)°, R 1 = 0.0422, wR 2 = 0.0724, Z = 4; LiSr 4 Si 4 N 8 F: P4nc (no. 104), a = 9.3118(4), b = 9.3118(4), c = 5.5216(2) Å, R 1 = 0.0160, wR 2 = 0.0388, Z = 2]. The silicate substructure of both compounds is built up of vertex-sharing SiN 4 tetrahedra, thereby forming a structure analogous to the BCT zeolite with Ca 2+ /Sr 2+ , Li + , and Fions filling the voids. The crystal structure of LiSr 4 Si 4 N 8 F is homeo- [a] Chemistry of LMU Munich) for performing the EDX measurements. Financial support by the Fonds der Chemischen Industrie (FCI) is gratefully acknowledged.

The oxonitridolithotungstosilicate Ba 32 [Li 15 Si 9 W 16 -N 67 O 5 ] was synthesized by metathesis reaction of the reactive starting compounds Si(NH) 2 , LiNH 2 , LiF, and BaH 2 in a radiofrequency furnace at 1000°C by using tungsten crucibles. Single crystals of Ba 32 [Li 15 Si 9 W 16 N 67 O 5 ] were obtained as a byproduct from reaction of the starting materials with the crucible. The crystal structure was solved and refined on the basis of single-crystal X-ray diffraction data [P2 1 /n (no. 14), a = 8.3402 (3), b = 8.5465(3), c = 16.6736(6) Å, = 99.1950(10)°, Z = 1, R 1 (all) = 0.0302]. Ba 32 [Li 15 Si 9 W 16 N 67 O 5 ] is the first oxonitridolithotungstosilicate containing a three-dimensional network of [a]