Li2SiS3 is Enargite-like structured and crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded to one S(2) and three equivalent S(1) atoms to form LiS4 tetrahedra that share corners with five equivalent Si(1)S4 tetrahedra and corners with seven equivalent Li(1)S4 tetrahedra. Si(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form SiS4 tetrahedra that share corners with two equivalent Si(1)S4 tetrahedra and corners with ten equivalent Li(1)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1) and one Si(1) atom to form SLi3Si tetrahedra that share corners with five equivalent S(2)Li2Si2 tetrahedra and corners with seven equivalent S(1)Li3Si tetrahedra. In the second S site, S(2) is bonded to two equivalent Li(1) and two equivalent Si(1) atoms to form SLi2Si2 tetrahedra that share corners with two equivalent S(2)Li2Si2 tetrahedra and corners with ten equivalent S(1)Li3Si tetrahedra.
Li2SiS3 is Enargite-like structured and crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded to one S(2) and three equivalent S(1) atoms to form LiS4 tetrahedra that share corners with five equivalent Si(1)S4 tetrahedra and corners with seven equivalent Li(1)S4 tetrahedra. The Li(1)-S(2) bond length is 2.52 Å. There is one shorter (2.41 Å) and two longer (2.43 Å) Li(1)-S(1) bond lengths. Si(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form SiS4 tetrahedra that share corners with two equivalent Si(1)S4 tetrahedra and corners with ten equivalent Li(1)S4 tetrahedra. Both Si(1)-S(1) bond lengths are 2.07 Å. There is one shorter (2.19 Å) and one longer (2.23 Å) Si(1)-S(2) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1) and one Si(1) atom to form SLi3Si tetrahedra that share corners with five equivalent S(2)Li2Si2 tetrahedra and corners with seven equivalent S(1)Li3Si tetrahedra. In the second S site, S(2) is bonded to two equivalent Li(1) and two equivalent Si(1) atoms to form SLi2Si2 tetrahedra that share corners with two equivalent S(2)Li2Si2 tetrahedra and corners with ten equivalent S(1)Li3Si tetrahedra.