Ni6Si2B crystallizes in the hexagonal P-62m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted L-shaped geometry to two equivalent B(1) and two equivalent Si(1) atoms. In the second Ni site, Ni(2) is bonded in a 5-coordinate geometry to one B(1) and four equivalent Si(1) atoms. B(1) is bonded in a 9-coordinate geometry to three equivalent Ni(2) and six equivalent Ni(1) atoms. Si(1) is bonded in a 9-coordinate geometry to three equivalent Ni(1) and six equivalent Ni(2) atoms.
Ni6Si2B crystallizes in the hexagonal P-62m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted L-shaped geometry to two equivalent B(1) and two equivalent Si(1) atoms. Both Ni(1)-B(1) bond lengths are 2.05 Å. Both Ni(1)-Si(1) bond lengths are 2.34 Å. In the second Ni site, Ni(2) is bonded in a 5-coordinate geometry to one B(1) and four equivalent Si(1) atoms. The Ni(2)-B(1) bond length is 2.37 Å. All Ni(2)-Si(1) bond lengths are 2.35 Å. B(1) is bonded in a 9-coordinate geometry to three equivalent Ni(2) and six equivalent Ni(1) atoms. Si(1) is bonded in a 9-coordinate geometry to three equivalent Ni(1) and six equivalent Ni(2) atoms.