Li2In2SiSe6 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one Se(1), one Se(2), one Se(4), and one Se(5) atom to form LiSe4 trigonal pyramids that share corners with two equivalent Li(2)Se4 tetrahedra, corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent In(1)Se4 tetrahedra, and corners with three equivalent In(2)Se4 tetrahedra. In the second Li site, Li(2) is bonded to one Se(1), one Se(2), one Se(3), and one Se(6) atom to form LiSe4 tetrahedra that share corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent In(1)Se4 tetrahedra, corners with three equivalent In(2)Se4 tetrahedra, and corners with two equivalent Li(1)Se4 trigonal pyramids. There are two inequivalent In sites. In the first In site, In(1) is bonded to one Se(1), one Se(2), one Se(3), and one Se(5) atom to form InSe4 tetrahedra that share corners with two equivalent In(2)Se4 tetrahedra, corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent Li(2)Se4 tetrahedra, and corners with three equivalent Li(1)Se4 trigonal pyramids. In the second In site, In(2) is bonded to one Se(1), one Se(2), one Se(4), and one Se(6) atom to form InSe4 tetrahedra that share corners with two equivalent In(1)Se4 tetrahedra, corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent Li(2)Se4 tetrahedra, and corners with three equivalent Li(1)Se4 trigonal pyramids. Si(1) is bonded to one Se(3), one Se(4), one Se(5), and one Se(6) atom to form SiSe4 tetrahedra that share corners with two equivalent Li(2)Se4 tetrahedra, corners with two equivalent In(1)Se4 tetrahedra, corners with two equivalent In(2)Se4 tetrahedra, and corners with two equivalent Li(1)Se4 trigonal pyramids. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SeLi2In2 tetrahedra. In the second Se site, Se(2) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SeLi2In2 trigonal pyramids. In the third Se site, Se(3) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(1), and one Si(1) atom. In the fourth Se site, Se(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one In(2), and one Si(1) atom. In the fifth Se site, Se(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one In(1), and one Si(1) atom. In the sixth Se site, Se(6) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(2), and one Si(1) atom.
Li2In2SiSe6 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one Se(1), one Se(2), one Se(4), and one Se(5) atom to form LiSe4 trigonal pyramids that share corners with two equivalent Li(2)Se4 tetrahedra, corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent In(1)Se4 tetrahedra, and corners with three equivalent In(2)Se4 tetrahedra. The Li(1)-Se(1) bond length is 2.69 Å. The Li(1)-Se(2) bond length is 2.67 Å. The Li(1)-Se(4) bond length is 2.90 Å. The Li(1)-Se(5) bond length is 2.68 Å. In the second Li site, Li(2) is bonded to one Se(1), one Se(2), one Se(3), and one Se(6) atom to form LiSe4 tetrahedra that share corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent In(1)Se4 tetrahedra, corners with three equivalent In(2)Se4 tetrahedra, and corners with two equivalent Li(1)Se4 trigonal pyramids. The Li(2)-Se(1) bond length is 2.69 Å. The Li(2)-Se(2) bond length is 2.68 Å. The Li(2)-Se(3) bond length is 2.66 Å. The Li(2)-Se(6) bond length is 2.71 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one Se(1), one Se(2), one Se(3), and one Se(5) atom to form InSe4 tetrahedra that share corners with two equivalent In(2)Se4 tetrahedra, corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent Li(2)Se4 tetrahedra, and corners with three equivalent Li(1)Se4 trigonal pyramids. The In(1)-Se(1) bond length is 2.63 Å. The In(1)-Se(2) bond length is 2.63 Å. The In(1)-Se(3) bond length is 2.67 Å. The In(1)-Se(5) bond length is 2.66 Å. In the second In site, In(2) is bonded to one Se(1), one Se(2), one Se(4), and one Se(6) atom to form InSe4 tetrahedra that share corners with two equivalent In(1)Se4 tetrahedra, corners with two equivalent Si(1)Se4 tetrahedra, corners with three equivalent Li(2)Se4 tetrahedra, and corners with three equivalent Li(1)Se4 trigonal pyramids. The In(2)-Se(1) bond length is 2.65 Å. The In(2)-Se(2) bond length is 2.64 Å. The In(2)-Se(4) bond length is 2.66 Å. The In(2)-Se(6) bond length is 2.65 Å. Si(1) is bonded to one Se(3), one Se(4), one Se(5), and one Se(6) atom to form SiSe4 tetrahedra that share corners with two equivalent Li(2)Se4 tetrahedra, corners with two equivalent In(1)Se4 tetrahedra, corners with two equivalent In(2)Se4 tetrahedra, and corners with two equivalent Li(1)Se4 trigonal pyramids. The Si(1)-Se(3) bond length is 2.28 Å. The Si(1)-Se(4) bond length is 2.27 Å. The Si(1)-Se(5) bond length is 2.30 Å. The Si(1)-Se(6) bond length is 2.29 Å. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SeLi2In2 tetrahedra. In the second Se site, Se(2) is bonded to one Li(1), one Li(2), one In(1), and one In(2) atom to form corner-sharing SeLi2In2 trigonal pyramids. In the third Se site, Se(3) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(1), and one Si(1) atom. In the fourth Se site, Se(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one In(2), and one Si(1) atom. In the fifth Se site, Se(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one In(1), and one Si(1) atom. In the sixth Se site, Se(6) is bonded in a trigonal non-coplanar geometry to one Li(2), one In(2), and one Si(1) atom.