LiIn4(Ge2O7)2 crystallizes in the trigonal R3m space group. Li(1) is bonded in a 4-coordinate geometry to three equivalent In(1), one O(2), three equivalent O(3), and three equivalent O(6) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded in a 9-coordinate geometry to one Li(1), one O(1), one O(2), one O(4), one O(6), two equivalent O(3), and two equivalent O(5) atoms. In the second In site, In(2) is bonded to one O(1), one O(2), three equivalent O(4), and three equivalent O(6) atoms to form distorted InO8 hexagonal bipyramids that share edges with six equivalent Ge(1)O6 octahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form GeO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra, and edges with two equivalent In(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-49°. In the second Ge site, Ge(2) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form corner-sharing GeO6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. There are six inequivalent O sites. In the first O site, O(5) is bonded to two equivalent In(1), one Ge(1), and one Ge(2) atom to form distorted OIn2Ge2 tetrahedra that share corners with four equivalent O(5)In2Ge2 tetrahedra, corners with two equivalent O(2)LiIn4 trigonal bipyramids,  an edgeedge with one O(1)In4 tetrahedra, and edges with two equivalent O(4)In2Ge2 tetrahedra. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one In(1), one In(2), and two equivalent Ge(1) atoms. In the third O site, O(1) is bonded to one In(2) and three equivalent In(1) atoms to form OIn4 tetrahedra that share corners with six equivalent O(4)In2Ge2 tetrahedra, corners with four equivalent O(2)LiIn4 trigonal bipyramids, and edges with three equivalent O(5)In2Ge2 tetrahedra. In the fourth O site, O(2) is bonded to one Li(1), one In(2), and three equivalent In(1) atoms to form distorted OLiIn4 trigonal bipyramids that share corners with four equivalent O(1)In4 tetrahedra, corners with six equivalent O(5)In2Ge2 tetrahedra, and edges with three equivalent O(4)In2Ge2 tetrahedra. In the fifth O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), two equivalent In(1), one Ge(1), and one Ge(2) atom. In the sixth O site, O(4) is bonded to one In(1), one In(2), and two equivalent Ge(1) atoms to form distorted OIn2Ge2 tetrahedra that share corners with two equivalent O(1)In4 tetrahedra, corners with four equivalent O(4)In2Ge2 tetrahedra, edges with two equivalent O(5)In2Ge2 tetrahedra, and  an edgeedge with one O(2)LiIn4 trigonal bipyramid.
LiIn4(Ge2O7)2 crystallizes in the trigonal R3m space group. Li(1) is bonded in a 4-coordinate geometry to three equivalent In(1), one O(2), three equivalent O(3), and three equivalent O(6) atoms. All Li(1)-In(1) bond lengths are 2.66 Å. The Li(1)-O(2) bond length is 2.07 Å. All Li(1)-O(3) bond lengths are 2.45 Å. All Li(1)-O(6) bond lengths are 1.94 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded in a 9-coordinate geometry to one Li(1), one O(1), one O(2), one O(4), one O(6), two equivalent O(3), and two equivalent O(5) atoms. The In(1)-O(1) bond length is 2.15 Å. The In(1)-O(2) bond length is 2.19 Å. The In(1)-O(4) bond length is 2.30 Å. The In(1)-O(6) bond length is 2.72 Å. Both In(1)-O(3) bond lengths are 2.59 Å. Both In(1)-O(5) bond lengths are 2.36 Å. In the second In site, In(2) is bonded to one O(1), one O(2), three equivalent O(4), and three equivalent O(6) atoms to form distorted InO8 hexagonal bipyramids that share edges with six equivalent Ge(1)O6 octahedra. The In(2)-O(1) bond length is 2.16 Å. The In(2)-O(2) bond length is 2.28 Å. All In(2)-O(4) bond lengths are 2.47 Å. All In(2)-O(6) bond lengths are 2.50 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form GeO6 octahedra that share corners with two equivalent Ge(2)O6 octahedra, corners with four equivalent Ge(1)O6 octahedra, and edges with two equivalent In(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-49°. The Ge(1)-O(3) bond length is 1.93 Å. The Ge(1)-O(5) bond length is 1.95 Å. Both Ge(1)-O(4) bond lengths are 1.92 Å. Both Ge(1)-O(6) bond lengths are 1.93 Å. In the second Ge site, Ge(2) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form corner-sharing GeO6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. All Ge(2)-O(3) bond lengths are 1.93 Å. All Ge(2)-O(5) bond lengths are 1.98 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded to two equivalent In(1), one Ge(1), and one Ge(2) atom to form distorted OIn2Ge2 tetrahedra that share corners with four equivalent O(5)In2Ge2 tetrahedra, corners with two equivalent O(2)LiIn4 trigonal bipyramids,  an edgeedge with one O(1)In4 tetrahedra, and edges with two equivalent O(4)In2Ge2 tetrahedra. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one In(1), one In(2), and two equivalent Ge(1) atoms. In the third O site, O(1) is bonded to one In(2) and three equivalent In(1) atoms to form OIn4 tetrahedra that share corners with six equivalent O(4)In2Ge2 tetrahedra, corners with four equivalent O(2)LiIn4 trigonal bipyramids, and edges with three equivalent O(5)In2Ge2 tetrahedra. In the fourth O site, O(2) is bonded to one Li(1), one In(2), and three equivalent In(1) atoms to form distorted OLiIn4 trigonal bipyramids that share corners with four equivalent O(1)In4 tetrahedra, corners with six equivalent O(5)In2Ge2 tetrahedra, and edges with three equivalent O(4)In2Ge2 tetrahedra. In the fifth O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), two equivalent In(1), one Ge(1), and one Ge(2) atom. In the sixth O site, O(4) is bonded to one In(1), one In(2), and two equivalent Ge(1) atoms to form distorted OIn2Ge2 tetrahedra that share corners with two equivalent O(1)In4 tetrahedra, corners with four equivalent O(4)In2Ge2 tetrahedra, edges with two equivalent O(5)In2Ge2 tetrahedra, and  an edgeedge with one O(2)LiIn4 trigonal bipyramid.