Ba 32 [Li 15 Si 9 W 16 N 67 O 5 ]: A Barium‐Containing Oxonitridolithotungstosilicate with a Highly Condensed Network Structure

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 [ P 2 1 / n (no. 14), a = 8.3402(3), b = 8.5465(3), c = 16.6736(6) Å, β = 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 vertex‐ (WN 4 ) and edge‐sharing (LiN 3 O, Li/SiN 3 O, and SiN 3 O) tetrahedra with Ba 2+ ions that fill the voids of the structure. The network is characterized by channels of fünfer rings running along [100] as well as channels of sechser and achter rings along [010]. Magnetic measurements verified an oxidation state of +VI for W. X‐ray spectroscopy, lattice energy calculations with MAPLE, and X‐ray diffraction confirmed the chemical composition and the structural model of Ba 32 [Li 15 Si 9 W 16 N 67 O 5 ]. IR spectra corroborated the absence of N–H bonds. The optical band gap of Ba 32 [Li 15 Si 9 W 16 N 67 O 5 ] has been determined by UV/Vis spectroscopy.