LiZr4Ge crystallizes in the monoclinic Pm space group. Li(1) is bonded to two equivalent Zr(2), two equivalent Zr(3), two equivalent Zr(4), four equivalent Zr(1), and two equivalent Ge(1) atoms to form LiZr10Ge2 cuboctahedra that share corners with four equivalent Li(1)Zr10Ge2 cuboctahedra, corners with six equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with three equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with eight equivalent Ge(1)Li2Zr10 cuboctahedra, faces with two equivalent Ge(1)Li2Zr10 cuboctahedra, and faces with four equivalent Li(1)Zr10Ge2 cuboctahedra. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to four equivalent Li(1), two equivalent Zr(4), and two equivalent Ge(1) atoms. In the second Zr site, Zr(2) is bonded to two equivalent Li(1), two equivalent Zr(4), and four equivalent Ge(1) atoms to form distorted ZrLi2Zr2Ge4 cuboctahedra that share corners with four equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, corners with six equivalent Li(1)Zr10Ge2 cuboctahedra, edges with two equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with three equivalent Li(1)Zr10Ge2 cuboctahedra, edges with four equivalent Ge(1)Li2Zr10 cuboctahedra, and faces with two equivalent Zr(2)Li2Zr2Ge4 cuboctahedra. In the third Zr site, Zr(3) is bonded in a distorted L-shaped geometry to two equivalent Li(1), four equivalent Zr(4), and two equivalent Ge(1) atoms. In the fourth Zr site, Zr(4) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Zr(1), two equivalent Zr(2), four equivalent Zr(3), and two equivalent Ge(1) atoms. Ge(1) is bonded to two equivalent Li(1), two equivalent Zr(1), two equivalent Zr(3), two equivalent Zr(4), and four equivalent Zr(2) atoms to form distorted GeLi2Zr10 cuboctahedra that share corners with four equivalent Ge(1)Li2Zr10 cuboctahedra, edges with four equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with eight equivalent Li(1)Zr10Ge2 cuboctahedra, faces with two equivalent Li(1)Zr10Ge2 cuboctahedra, and faces with four equivalent Ge(1)Li2Zr10 cuboctahedra.
LiZr4Ge crystallizes in the monoclinic Pm space group. Li(1) is bonded to two equivalent Zr(2), two equivalent Zr(3), two equivalent Zr(4), four equivalent Zr(1), and two equivalent Ge(1) atoms to form LiZr10Ge2 cuboctahedra that share corners with four equivalent Li(1)Zr10Ge2 cuboctahedra, corners with six equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with three equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with eight equivalent Ge(1)Li2Zr10 cuboctahedra, faces with two equivalent Ge(1)Li2Zr10 cuboctahedra, and faces with four equivalent Li(1)Zr10Ge2 cuboctahedra. Both Li(1)-Zr(2) bond lengths are 3.00 Å. Both Li(1)-Zr(3) bond lengths are 3.35 Å. Both Li(1)-Zr(4) bond lengths are 2.97 Å. There are two shorter (3.00 Å) and two longer (3.01 Å) Li(1)-Zr(1) bond lengths. Both Li(1)-Ge(1) bond lengths are 3.13 Å. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to four equivalent Li(1), two equivalent Zr(4), and two equivalent Ge(1) atoms. Both Zr(1)-Zr(4) bond lengths are 3.18 Å. There is one shorter (2.91 Å) and one longer (2.92 Å) Zr(1)-Ge(1) bond length. In the second Zr site, Zr(2) is bonded to two equivalent Li(1), two equivalent Zr(4), and four equivalent Ge(1) atoms to form distorted ZrLi2Zr2Ge4 cuboctahedra that share corners with four equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, corners with six equivalent Li(1)Zr10Ge2 cuboctahedra, edges with two equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with three equivalent Li(1)Zr10Ge2 cuboctahedra, edges with four equivalent Ge(1)Li2Zr10 cuboctahedra, and faces with two equivalent Zr(2)Li2Zr2Ge4 cuboctahedra. Both Zr(2)-Zr(4) bond lengths are 3.16 Å. All Zr(2)-Ge(1) bond lengths are 3.00 Å. In the third Zr site, Zr(3) is bonded in a distorted L-shaped geometry to two equivalent Li(1), four equivalent Zr(4), and two equivalent Ge(1) atoms. All Zr(3)-Zr(4) bond lengths are 3.02 Å. There is one shorter (2.93 Å) and one longer (2.94 Å) Zr(3)-Ge(1) bond length. In the fourth Zr site, Zr(4) is bonded in a 12-coordinate geometry to two equivalent Li(1), two equivalent Zr(1), two equivalent Zr(2), four equivalent Zr(3), and two equivalent Ge(1) atoms. Both Zr(4)-Ge(1) bond lengths are 3.31 Å. Ge(1) is bonded to two equivalent Li(1), two equivalent Zr(1), two equivalent Zr(3), two equivalent Zr(4), and four equivalent Zr(2) atoms to form distorted GeLi2Zr10 cuboctahedra that share corners with four equivalent Ge(1)Li2Zr10 cuboctahedra, edges with four equivalent Zr(2)Li2Zr2Ge4 cuboctahedra, edges with eight equivalent Li(1)Zr10Ge2 cuboctahedra, faces with two equivalent Li(1)Zr10Ge2 cuboctahedra, and faces with four equivalent Ge(1)Li2Zr10 cuboctahedra.