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In this contribution, we briefly review the results of collaborative research between crystallography groups in St. Petersburg and Kiel, and report on the synthesis and crystal structure of Tl 16 (SiO 4 ) 2 (SO 4 )(OH) 6  ( 1 ), a new and unusual compound obtained from highly-alkaline TlOH solution. Its structure [monoclinic,  C 2/ m ,  a  = 28.7140(18),  b  = 7.3686(5),  c  = 7.4426(5) Å, β = 104.653(2)°,  V  = 1523.50(17) Å 3 ,  R  1  = 0.066 for 1528 independent observed reflections] can be described as an alternation of electroneutral [Tl 5 (SiO 4 )(OH)] and [Tl 3 (SO 4 ) 0.5 (OH) 2 ] layers. The [Tl 5 (SiO 4 )(OH)] layer consists of Tl(1)O 4  tetragonal pyramids sharing common corners with the SiO 4  tetrahedra to form pseudotetragonal [Tl(SiO 4 )] 3-  layers capped by OH(1)-centered [(OH)Tl 4 ] square pyramids with the Tl(2) and Tl(3) atoms in their apices. The [Tl 3 (SO 4 ) 0.5 (OH) 2 ] layers contain OH(2)- and OH(3)-centered [(OH)Tl 4 ] square pyramids sharing common edges to form large (∼ 7.4 × 7.4 Å) cavities occupied by disordered (SO 4 ) tetrahedra. The electroneutral character of the [Tl 5 (SiO 4 )(OH)] and [Tl 6 (SO 4 )(OH) 4 ] layers allows us to suggest that the phases with these chemical compositions may form as independent compounds in highly alkaline Tl-bearing systems.

Crystallography between Kiel and St. Petersburg: review of collaboration and the crystal structure of [Tl 5 (SiO 4 )(OH)] 2 [Tl 6 (SO 4 )(OH) 4 ]