Zr5V5Si6 crystallizes in the monoclinic Cm space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 5-coordinate geometry to one Si(1), two equivalent Si(2), and two equivalent Si(4) atoms. In the second Zr site, Zr(2) is bonded in a 5-coordinate geometry to one Si(3), two equivalent Si(1), and two equivalent Si(4) atoms. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to one Si(3), two equivalent Si(2), and two equivalent Si(4) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one Si(1), one Si(3), two equivalent Si(2), and two equivalent Si(4) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one Si(1), one Si(3), two equivalent Si(2), and two equivalent Si(4) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one Si(1), two equivalent Si(2), and two equivalent Si(3) atoms. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), one V(3), two equivalent V(1), and two equivalent V(2) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Zr(3), one V(3), two equivalent V(1), and two equivalent V(2) atoms. In the third Si site, Si(3) is bonded in a 9-coordinate geometry to one Zr(2), two equivalent Zr(3), two equivalent V(1), two equivalent V(2), and two equivalent V(3) atoms. In the fourth Si site, Si(4) is bonded in a 9-coordinate geometry to one Zr(2), two equivalent Zr(1), two equivalent Zr(3), two equivalent V(1), and two equivalent V(2) atoms.
Zr5V5Si6 crystallizes in the monoclinic Cm space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 5-coordinate geometry to one Si(1), two equivalent Si(2), and two equivalent Si(4) atoms. The Zr(1)-Si(1) bond length is 2.74 Å. There is one shorter (2.70 Å) and one longer (2.72 Å) Zr(1)-Si(2) bond length. There is one shorter (2.83 Å) and one longer (2.84 Å) Zr(1)-Si(4) bond length. In the second Zr site, Zr(2) is bonded in a 5-coordinate geometry to one Si(3), two equivalent Si(1), and two equivalent Si(4) atoms. The Zr(2)-Si(3) bond length is 2.63 Å. There is one shorter (2.82 Å) and one longer (2.83 Å) Zr(2)-Si(1) bond length. Both Zr(2)-Si(4) bond lengths are 2.67 Å. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to one Si(3), two equivalent Si(2), and two equivalent Si(4) atoms. The Zr(3)-Si(3) bond length is 2.66 Å. Both Zr(3)-Si(2) bond lengths are 2.82 Å. There is one shorter (2.69 Å) and one longer (2.71 Å) Zr(3)-Si(4) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one Si(1), one Si(3), two equivalent Si(2), and two equivalent Si(4) atoms. The V(1)-Si(1) bond length is 2.62 Å. The V(1)-Si(3) bond length is 2.64 Å. There is one shorter (2.65 Å) and one longer (2.70 Å) V(1)-Si(2) bond length. There is one shorter (2.63 Å) and one longer (2.68 Å) V(1)-Si(4) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to one Si(1), one Si(3), two equivalent Si(2), and two equivalent Si(4) atoms. The V(2)-Si(1) bond length is 2.62 Å. The V(2)-Si(3) bond length is 2.64 Å. There is one shorter (2.64 Å) and one longer (2.71 Å) V(2)-Si(2) bond length. There is one shorter (2.63 Å) and one longer (2.68 Å) V(2)-Si(4) bond length. In the third V site, V(3) is bonded in a 5-coordinate geometry to one Si(1), two equivalent Si(2), and two equivalent Si(3) atoms. The V(3)-Si(1) bond length is 2.48 Å. Both V(3)-Si(2) bond lengths are 2.58 Å. There is one shorter (2.76 Å) and one longer (2.77 Å) V(3)-Si(3) bond length. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), one V(3), two equivalent V(1), and two equivalent V(2) atoms. In the second Si site, Si(2) is bonded in a 9-coordinate geometry to two equivalent Zr(1), two equivalent Zr(3), one V(3), two equivalent V(1), and two equivalent V(2) atoms. In the third Si site, Si(3) is bonded in a 9-coordinate geometry to one Zr(2), two equivalent Zr(3), two equivalent V(1), two equivalent V(2), and two equivalent V(3) atoms. In the fourth Si site, Si(4) is bonded in a 9-coordinate geometry to one Zr(2), two equivalent Zr(1), two equivalent Zr(3), two equivalent V(1), and two equivalent V(2) atoms.