Boron site preference in ternary Ta and Nb boron silicides

X-ray single crystal (XSC) and neutron powder diffraction data (NPD) were used to elucidate boron site preference for five ternary phases. Ta3Si1−xBx (x=0.112(4)) crystallizes with the Ti3P-type (space group P42/n) with B-atoms sharing the 8g site with Si atoms. Ta5Si3−x (x=0.03(1); Cr5B3- type) crystallizes with space group I4/mcm, exhibiting a small amount of vacancies on the 4a site. Both, Ta5(Si1−xBx)3, x=0.568(3), and Nb5(Si1−xBx)3, x=0.59(2), are part of solid solutions of M5Si3 with Cr5B3-type into the ternary M–Si–B systems (M=Nb or Ta) with B replacing Si on the 8h site. The D88-phase in the Nb–Si–B system crystallizes with the Ti5Ga4-type revealing the formula Nb5Si3B1−x (x=0.292(3)) with B partially filling the voids in the 2b site of the Mn5Si3 parent type. The crystal structures of a series of compounds have been solved from X-ray single crystal diffractometry revealing details on the boron incorporation. [Display omitted] ► Structure of a series of compounds have been solved by X-ray single crystal diffractometry. ► Ta3(Si1−xBx) (x=0.112) crystallizes with the Ti3P-type, B and Si atoms randomly share the 8g site. ► Structure of Nb5Si3B1−x (x=0.292; Ti5Ga4-type) was solved from NPD.