V5W5Si6 is Khatyrkite-derived structured and crystallizes in the monoclinic Cm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one W(3), two equivalent W(4), one Si(3), one Si(5), two equivalent Si(1), and two equivalent Si(4) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to two equivalent V(3), one W(2), two equivalent W(4), one Si(2), one Si(4), two equivalent Si(1), and two equivalent Si(5) atoms. In the third V site, V(3) is bonded in a 15-coordinate geometry to one V(5), two equivalent V(2), one W(2), one W(3), two equivalent W(1), two equivalent W(4), one Si(3), one Si(5), two equivalent Si(1), and two equivalent Si(2) atoms. In the fourth V site, V(4) is bonded in a 9-coordinate geometry to one W(1), two equivalent W(4), one Si(2), one Si(4), two equivalent Si(1), and two equivalent Si(3) atoms. In the fifth V site, V(5) is bonded in a 11-coordinate geometry to one V(3), two equivalent W(3), two equivalent W(4), one Si(3), one Si(4), two equivalent Si(1), and two equivalent Si(2) atoms. There are four inequivalent W sites. In the first W site, W(1) is bonded in a 7-coordinate geometry to one V(4), two equivalent V(3), one Si(2), one Si(5), two equivalent Si(1), and two equivalent Si(3) atoms. In the second W site, W(2) is bonded in a 7-coordinate geometry to one V(2), one V(3), one Si(3), one Si(4), two equivalent Si(1), and two equivalent Si(5) atoms. In the third W site, W(3) is bonded in a 9-coordinate geometry to one V(1), one V(3), two equivalent V(5), one Si(2), one Si(5), two equivalent Si(1), and two equivalent Si(4) atoms. In the fourth W site, W(4) is bonded in a 11-coordinate geometry to one V(1), one V(2), one V(3), one V(4), one V(5), two equivalent W(4), one Si(2), one Si(3), one Si(4), and one Si(5) atom. There are five inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to one V(1), one V(2), one V(3), one V(4), one V(5), one W(1), one W(2), one W(3), and two equivalent Si(1) atoms. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to one V(2), one V(4), two equivalent V(3), two equivalent V(5), one W(1), one W(3), and two equivalent W(4) atoms. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one V(1), one V(3), one V(5), two equivalent V(4), one W(2), two equivalent W(1), and two equivalent W(4) atoms. In the fourth Si site, Si(4) is bonded in a 10-coordinate geometry to one V(2), one V(4), one V(5), two equivalent V(1), one W(2), two equivalent W(3), and two equivalent W(4) atoms. In the fifth Si site, Si(5) is bonded in a 10-coordinate geometry to one V(1), one V(3), two equivalent V(2), one W(1), one W(3), two equivalent W(2), and two equivalent W(4) atoms.
V5W5Si6 is Khatyrkite-derived structured and crystallizes in the monoclinic Cm space group. There are five inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one W(3), two equivalent W(4), one Si(3), one Si(5), two equivalent Si(1), and two equivalent Si(4) atoms. The V(1)-W(3) bond length is 2.73 Å. Both V(1)-W(4) bond lengths are 2.99 Å. The V(1)-Si(3) bond length is 2.47 Å. The V(1)-Si(5) bond length is 2.50 Å. Both V(1)-Si(1) bond lengths are 2.55 Å. Both V(1)-Si(4) bond lengths are 2.84 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to two equivalent V(3), one W(2), two equivalent W(4), one Si(2), one Si(4), two equivalent Si(1), and two equivalent Si(5) atoms. Both V(2)-V(3) bond lengths are 2.84 Å. The V(2)-W(2) bond length is 2.72 Å. Both V(2)-W(4) bond lengths are 2.99 Å. The V(2)-Si(2) bond length is 2.50 Å. The V(2)-Si(4) bond length is 2.48 Å. Both V(2)-Si(1) bond lengths are 2.55 Å. Both V(2)-Si(5) bond lengths are 2.82 Å. In the third V site, V(3) is bonded in a 15-coordinate geometry to one V(5), two equivalent V(2), one W(2), one W(3), two equivalent W(1), two equivalent W(4), one Si(3), one Si(5), two equivalent Si(1), and two equivalent Si(2) atoms. The V(3)-V(5) bond length is 2.70 Å. The V(3)-W(2) bond length is 3.18 Å. The V(3)-W(3) bond length is 3.17 Å. Both V(3)-W(1) bond lengths are 3.20 Å. Both V(3)-W(4) bond lengths are 2.98 Å. The V(3)-Si(3) bond length is 2.49 Å. The V(3)-Si(5) bond length is 2.49 Å. Both V(3)-Si(1) bond lengths are 2.59 Å. Both V(3)-Si(2) bond lengths are 2.82 Å. In the fourth V site, V(4) is bonded in a 9-coordinate geometry to one W(1), two equivalent W(4), one Si(2), one Si(4), two equivalent Si(1), and two equivalent Si(3) atoms. The V(4)-W(1) bond length is 2.72 Å. Both V(4)-W(4) bond lengths are 2.98 Å. The V(4)-Si(2) bond length is 2.52 Å. The V(4)-Si(4) bond length is 2.50 Å. Both V(4)-Si(1) bond lengths are 2.55 Å. Both V(4)-Si(3) bond lengths are 2.81 Å. In the fifth V site, V(5) is bonded in a 11-coordinate geometry to one V(3), two equivalent W(3), two equivalent W(4), one Si(3), one Si(4), two equivalent Si(1), and two equivalent Si(2) atoms. Both V(5)-W(3) bond lengths are 2.85 Å. Both V(5)-W(4) bond lengths are 2.96 Å. The V(5)-Si(3) bond length is 2.45 Å. The V(5)-Si(4) bond length is 2.50 Å. Both V(5)-Si(1) bond lengths are 2.53 Å. Both V(5)-Si(2) bond lengths are 2.83 Å. There are four inequivalent W sites. In the first W site, W(1) is bonded in a 7-coordinate geometry to one V(4), two equivalent V(3), one Si(2), one Si(5), two equivalent Si(1), and two equivalent Si(3) atoms. The W(1)-Si(2) bond length is 2.48 Å. The W(1)-Si(5) bond length is 2.56 Å. Both W(1)-Si(1) bond lengths are 2.58 Å. Both W(1)-Si(3) bond lengths are 2.85 Å. In the second W site, W(2) is bonded in a 7-coordinate geometry to one V(2), one V(3), one Si(3), one Si(4), two equivalent Si(1), and two equivalent Si(5) atoms. The W(2)-Si(3) bond length is 2.59 Å. The W(2)-Si(4) bond length is 2.50 Å. Both W(2)-Si(1) bond lengths are 2.58 Å. Both W(2)-Si(5) bond lengths are 2.84 Å. In the third W site, W(3) is bonded in a 9-coordinate geometry to one V(1), one V(3), two equivalent V(5), one Si(2), one Si(5), two equivalent Si(1), and two equivalent Si(4) atoms. The W(3)-Si(2) bond length is 2.54 Å. The W(3)-Si(5) bond length is 2.48 Å. Both W(3)-Si(1) bond lengths are 2.55 Å. Both W(3)-Si(4) bond lengths are 2.82 Å. In the fourth W site, W(4) is bonded in a 11-coordinate geometry to one V(1), one V(2), one V(3), one V(4), one V(5), two equivalent W(4), one Si(2), one Si(3), one Si(4), and one Si(5) atom. Both W(4)-W(4) bond lengths are 2.48 Å. The W(4)-Si(2) bond length is 2.59 Å. The W(4)-Si(3) bond length is 2.62 Å. The W(4)-Si(4) bond length is 2.59 Å. The W(4)-Si(5) bond length is 2.60 Å. There are five inequivalent Si sites. In the first Si site, Si(1) is bonded in a 10-coordinate geometry to one V(1), one V(2), one V(3), one V(4), one V(5), one W(1), one W(2), one W(3), and two equivalent Si(1) atoms. There is one shorter (2.46 Å) and one longer (2.50 Å) Si(1)-Si(1) bond length. In the second Si site, Si(2) is bonded in a 10-coordinate geometry to one V(2), one V(4), two equivalent V(3), two equivalent V(5), one W(1), one W(3), and two equivalent W(4) atoms. In the third Si site, Si(3) is bonded in a 10-coordinate geometry to one V(1), one V(3), one V(5), two equivalent V(4), one W(2), two equivalent W(1), and two equivalent W(4) atoms. In the fourth Si site, Si(4) is bonded in a 10-coordinate geometry to one V(2), one V(4), one V(5), two equivalent V(1), one W(2), two equivalent W(3), and two equivalent W(4) atoms. In the fifth Si site, Si(5) is bonded in a 10-coordinate geometry to one V(1), one V(3), two equivalent V(2), one W(1), one W(3), two equivalent W(2), and two equivalent W(4) atoms.