Na2CdSnS4 is Stannite-like structured and crystallizes in the tetragonal I-4 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent S(1) atoms to form NaS4 tetrahedra that share corners with four equivalent Na(2)S4 tetrahedra, corners with four equivalent Cd(1)S4 tetrahedra, and corners with four equivalent Sn(1)S4 tetrahedra. In the second Na site, Na(2) is bonded to four equivalent S(1) atoms to form NaS4 tetrahedra that share corners with four equivalent Na(1)S4 tetrahedra, corners with four equivalent Cd(1)S4 tetrahedra, and corners with four equivalent Sn(1)S4 tetrahedra. Cd(1) is bonded to four equivalent S(1) atoms to form CdS4 tetrahedra that share corners with four equivalent Na(1)S4 tetrahedra, corners with four equivalent Na(2)S4 tetrahedra, and corners with four equivalent Sn(1)S4 tetrahedra. Sn(1) is bonded to four equivalent S(1) atoms to form SnS4 tetrahedra that share corners with four equivalent Na(1)S4 tetrahedra, corners with four equivalent Na(2)S4 tetrahedra, and corners with four equivalent Cd(1)S4 tetrahedra. S(1) is bonded to one Na(1), one Na(2), one Cd(1), and one Sn(1) atom to form corner-sharing SNa2CdSn tetrahedra.
Na2CdSnS4 is Stannite-like structured and crystallizes in the tetragonal I-4 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to four equivalent S(1) atoms to form NaS4 tetrahedra that share corners with four equivalent Na(2)S4 tetrahedra, corners with four equivalent Cd(1)S4 tetrahedra, and corners with four equivalent Sn(1)S4 tetrahedra. All Na(1)-S(1) bond lengths are 2.76 Å. In the second Na site, Na(2) is bonded to four equivalent S(1) atoms to form NaS4 tetrahedra that share corners with four equivalent Na(1)S4 tetrahedra, corners with four equivalent Cd(1)S4 tetrahedra, and corners with four equivalent Sn(1)S4 tetrahedra. All Na(2)-S(1) bond lengths are 2.84 Å. Cd(1) is bonded to four equivalent S(1) atoms to form CdS4 tetrahedra that share corners with four equivalent Na(1)S4 tetrahedra, corners with four equivalent Na(2)S4 tetrahedra, and corners with four equivalent Sn(1)S4 tetrahedra. All Cd(1)-S(1) bond lengths are 2.57 Å. Sn(1) is bonded to four equivalent S(1) atoms to form SnS4 tetrahedra that share corners with four equivalent Na(1)S4 tetrahedra, corners with four equivalent Na(2)S4 tetrahedra, and corners with four equivalent Cd(1)S4 tetrahedra. All Sn(1)-S(1) bond lengths are 2.43 Å. S(1) is bonded to one Na(1), one Na(2), one Cd(1), and one Sn(1) atom to form corner-sharing SNa2CdSn tetrahedra.