Zr3V9Ge10 crystallizes in the monoclinic Cm space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one Ge(2), one Ge(7), one Ge(8), two equivalent Ge(5), and two equivalent Ge(6) atoms. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to one Ge(3), one Ge(7), one Ge(8), two equivalent Ge(5), and two equivalent Ge(9) atoms. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one Ge(4), one Ge(6), one Ge(9), two equivalent Ge(5), and two equivalent Ge(8) atoms. There are seven inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one Ge(1), one Ge(3), one Ge(6), one Ge(7), one Ge(8), and one Ge(9) atom. In the second V site, V(2) is bonded in a 6-coordinate geometry to one Ge(2), one Ge(4), one Ge(6), one Ge(7), one Ge(8), and one Ge(9) atom. In the third V site, V(3) is bonded in a 7-coordinate geometry to one Ge(3), one Ge(4), one Ge(6), two equivalent Ge(2), and two equivalent Ge(5) atoms. In the fourth V site, V(4) is bonded in a 7-coordinate geometry to one Ge(3), one Ge(4), one Ge(7), two equivalent Ge(1), and two equivalent Ge(5) atoms. In the fifth V site, V(5) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(2), one Ge(8), two equivalent Ge(4), and two equivalent Ge(5) atoms. In the sixth V site, V(6) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(2), one Ge(9), two equivalent Ge(3), and two equivalent Ge(5) atoms. In the seventh V site, V(7) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(6), one Ge(9), two equivalent Ge(5), and two equivalent Ge(7) atoms. There are nine inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 7-coordinate geometry to one V(5), one V(6), one V(7), two equivalent V(1), two equivalent V(4), one Ge(2), and two equivalent Ge(3) atoms. In the second Ge site, Ge(2) is bonded in a 10-coordinate geometry to one Zr(1), one V(5), one V(6), two equivalent V(2), two equivalent V(3), one Ge(1), and two equivalent Ge(4) atoms. In the third Ge site, Ge(3) is bonded in a 10-coordinate geometry to one Zr(2), one V(3), one V(4), two equivalent V(1), two equivalent V(6), one Ge(4), and two equivalent Ge(1) atoms. In the fourth Ge site, Ge(4) is bonded in a 10-coordinate geometry to one Zr(3), one V(3), one V(4), two equivalent V(2), two equivalent V(5), one Ge(3), and two equivalent Ge(2) atoms. In the fifth Ge site, Ge(5) is bonded in a 10-coordinate geometry to one Zr(1), one Zr(2), one Zr(3), one V(3), one V(4), one V(5), one V(6), one V(7), and two equivalent Ge(5) atoms. In the sixth Ge site, Ge(6) is bonded in a 9-coordinate geometry to one Zr(3), two equivalent Zr(1), one V(3), one V(7), two equivalent V(1), and two equivalent V(2) atoms. In the seventh Ge site, Ge(7) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(2), one V(4), two equivalent V(1), two equivalent V(2), and two equivalent V(7) atoms. In the eighth Ge site, Ge(8) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(2), two equivalent Zr(3), one V(5), two equivalent V(1), and two equivalent V(2) atoms. In the ninth Ge site, Ge(9) is bonded in a 9-coordinate geometry to one Zr(3), two equivalent Zr(2), one V(6), one V(7), two equivalent V(1), and two equivalent V(2) atoms.
Zr3V9Ge10 crystallizes in the monoclinic Cm space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one Ge(2), one Ge(7), one Ge(8), two equivalent Ge(5), and two equivalent Ge(6) atoms. The Zr(1)-Ge(2) bond length is 2.67 Å. The Zr(1)-Ge(7) bond length is 2.81 Å. The Zr(1)-Ge(8) bond length is 2.78 Å. Both Zr(1)-Ge(5) bond lengths are 2.88 Å. Both Zr(1)-Ge(6) bond lengths are 2.93 Å. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to one Ge(3), one Ge(7), one Ge(8), two equivalent Ge(5), and two equivalent Ge(9) atoms. The Zr(2)-Ge(3) bond length is 2.70 Å. The Zr(2)-Ge(7) bond length is 2.74 Å. The Zr(2)-Ge(8) bond length is 2.83 Å. Both Zr(2)-Ge(5) bond lengths are 2.82 Å. Both Zr(2)-Ge(9) bond lengths are 2.89 Å. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one Ge(4), one Ge(6), one Ge(9), two equivalent Ge(5), and two equivalent Ge(8) atoms. The Zr(3)-Ge(4) bond length is 2.68 Å. The Zr(3)-Ge(6) bond length is 2.83 Å. The Zr(3)-Ge(9) bond length is 2.85 Å. Both Zr(3)-Ge(5) bond lengths are 2.88 Å. Both Zr(3)-Ge(8) bond lengths are 2.90 Å. There are seven inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one Ge(1), one Ge(3), one Ge(6), one Ge(7), one Ge(8), and one Ge(9) atom. The V(1)-Ge(1) bond length is 2.52 Å. The V(1)-Ge(3) bond length is 2.53 Å. The V(1)-Ge(6) bond length is 2.62 Å. The V(1)-Ge(7) bond length is 2.68 Å. The V(1)-Ge(8) bond length is 2.63 Å. The V(1)-Ge(9) bond length is 2.71 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one Ge(2), one Ge(4), one Ge(6), one Ge(7), one Ge(8), and one Ge(9) atom. The V(2)-Ge(2) bond length is 2.55 Å. The V(2)-Ge(4) bond length is 2.55 Å. The V(2)-Ge(6) bond length is 2.65 Å. The V(2)-Ge(7) bond length is 2.62 Å. The V(2)-Ge(8) bond length is 2.68 Å. The V(2)-Ge(9) bond length is 2.61 Å. In the third V site, V(3) is bonded in a 7-coordinate geometry to one Ge(3), one Ge(4), one Ge(6), two equivalent Ge(2), and two equivalent Ge(5) atoms. The V(3)-Ge(3) bond length is 2.49 Å. The V(3)-Ge(4) bond length is 2.58 Å. The V(3)-Ge(6) bond length is 2.55 Å. Both V(3)-Ge(2) bond lengths are 2.86 Å. Both V(3)-Ge(5) bond lengths are 2.65 Å. In the fourth V site, V(4) is bonded in a 7-coordinate geometry to one Ge(3), one Ge(4), one Ge(7), two equivalent Ge(1), and two equivalent Ge(5) atoms. The V(4)-Ge(3) bond length is 2.60 Å. The V(4)-Ge(4) bond length is 2.51 Å. The V(4)-Ge(7) bond length is 2.47 Å. Both V(4)-Ge(1) bond lengths are 2.82 Å. Both V(4)-Ge(5) bond lengths are 2.59 Å. In the fifth V site, V(5) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(2), one Ge(8), two equivalent Ge(4), and two equivalent Ge(5) atoms. The V(5)-Ge(1) bond length is 2.48 Å. The V(5)-Ge(2) bond length is 2.57 Å. The V(5)-Ge(8) bond length is 2.51 Å. Both V(5)-Ge(4) bond lengths are 2.85 Å. Both V(5)-Ge(5) bond lengths are 2.61 Å. In the sixth V site, V(6) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(2), one Ge(9), two equivalent Ge(3), and two equivalent Ge(5) atoms. The V(6)-Ge(1) bond length is 2.67 Å. The V(6)-Ge(2) bond length is 2.47 Å. The V(6)-Ge(9) bond length is 2.50 Å. Both V(6)-Ge(3) bond lengths are 2.85 Å. Both V(6)-Ge(5) bond lengths are 2.60 Å. In the seventh V site, V(7) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(6), one Ge(9), two equivalent Ge(5), and two equivalent Ge(7) atoms. The V(7)-Ge(1) bond length is 2.59 Å. The V(7)-Ge(6) bond length is 2.73 Å. The V(7)-Ge(9) bond length is 2.71 Å. Both V(7)-Ge(5) bond lengths are 2.83 Å. Both V(7)-Ge(7) bond lengths are 2.89 Å. There are nine inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 7-coordinate geometry to one V(5), one V(6), one V(7), two equivalent V(1), two equivalent V(4), one Ge(2), and two equivalent Ge(3) atoms. The Ge(1)-Ge(2) bond length is 2.62 Å. Both Ge(1)-Ge(3) bond lengths are 2.93 Å. In the second Ge site, Ge(2) is bonded in a 10-coordinate geometry to one Zr(1), one V(5), one V(6), two equivalent V(2), two equivalent V(3), one Ge(1), and two equivalent Ge(4) atoms. Both Ge(2)-Ge(4) bond lengths are 2.89 Å. In the third Ge site, Ge(3) is bonded in a 10-coordinate geometry to one Zr(2), one V(3), one V(4), two equivalent V(1), two equivalent V(6), one Ge(4), and two equivalent Ge(1) atoms. The Ge(3)-Ge(4) bond length is 2.55 Å. In the fourth Ge site, Ge(4) is bonded in a 10-coordinate geometry to one Zr(3), one V(3), one V(4), two equivalent V(2), two equivalent V(5), one Ge(3), and two equivalent Ge(2) atoms. In the fifth Ge site, Ge(5) is bonded in a 10-coordinate geometry to one Zr(1), one Zr(2), one Zr(3), one V(3), one V(4), one V(5), one V(6), one V(7), and two equivalent Ge(5) atoms. There is one shorter (2.53 Å) and one longer (2.60 Å) Ge(5)-Ge(5) bond length. In the sixth Ge site, Ge(6) is bonded in a 9-coordinate geometry to one Zr(3), two equivalent Zr(1), one V(3), one V(7), two equivalent V(1), and two equivalent V(2) atoms. In the seventh Ge site, Ge(7) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(2), one V(4), two equivalent V(1), two equivalent V(2), and two equivalent V(7) atoms. In the eighth Ge site, Ge(8) is bonded in a 9-coordinate geometry to one Zr(1), one Zr(2), two equivalent Zr(3), one V(5), two equivalent V(1), and two equivalent V(2) atoms. In the ninth Ge site, Ge(9) is bonded in a 9-coordinate geometry to one Zr(3), two equivalent Zr(2), one V(6), one V(7), two equivalent V(1), and two equivalent V(2) atoms.