LiInSe2 is Lavarevi\'{c}ite-like structured and crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form LiSe4 tetrahedra that share corners with four equivalent Li(1)Se4 tetrahedra and corners with eight equivalent In(1)Se4 tetrahedra. In(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form InSe4 tetrahedra that share corners with four equivalent In(1)Se4 tetrahedra and corners with eight equivalent Li(1)Se4 tetrahedra. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Li(1) and two equivalent In(1) atoms to form corner-sharing SeLi2In2 tetrahedra. In the second Se site, Se(2) is bonded to two equivalent Li(1) and two equivalent In(1) atoms to form corner-sharing SeLi2In2 tetrahedra.
LiInSe2 is Lavarevi\'{c}ite-like structured and crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form LiSe4 tetrahedra that share corners with four equivalent Li(1)Se4 tetrahedra and corners with eight equivalent In(1)Se4 tetrahedra. There is one shorter (2.55 Å) and one longer (2.56 Å) Li(1)-Se(1) bond length. There is one shorter (2.56 Å) and one longer (2.57 Å) Li(1)-Se(2) bond length. In(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form InSe4 tetrahedra that share corners with four equivalent In(1)Se4 tetrahedra and corners with eight equivalent Li(1)Se4 tetrahedra. There is one shorter (2.59 Å) and one longer (2.60 Å) In(1)-Se(1) bond length. Both In(1)-Se(2) bond lengths are 2.60 Å. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Li(1) and two equivalent In(1) atoms to form corner-sharing SeLi2In2 tetrahedra. In the second Se site, Se(2) is bonded to two equivalent Li(1) and two equivalent In(1) atoms to form corner-sharing SeLi2In2 tetrahedra.