Na2CdSnS4 is Stannite-like structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent S(1) and two equivalent S(2) 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 two equivalent S(1) and two equivalent S(2) 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 two equivalent S(1) and two equivalent S(2) 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 two equivalent S(1) and two equivalent S(2) 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. There are two inequivalent S sites. In the first S site, 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. In the second S site, S(2) 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 monoclinic C2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent S(1) and two equivalent S(2) 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. Both Na(1)-S(1) bond lengths are 2.74 Å. Both Na(1)-S(2) bond lengths are 2.77 Å. In the second Na site, Na(2) is bonded to two equivalent S(1) and two equivalent S(2) 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. Both Na(2)-S(1) bond lengths are 2.89 Å. Both Na(2)-S(2) bond lengths are 2.84 Å. Cd(1) is bonded to two equivalent S(1) and two equivalent S(2) 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. Both Cd(1)-S(1) bond lengths are 2.57 Å. Both Cd(1)-S(2) bond lengths are 2.56 Å. Sn(1) is bonded to two equivalent S(1) and two equivalent S(2) 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. Both Sn(1)-S(1) bond lengths are 2.42 Å. Both Sn(1)-S(2) bond lengths are 2.43 Å. There are two inequivalent S sites. In the first S site, 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. In the second S site, S(2) is bonded to one Na(1), one Na(2), one Cd(1), and one Sn(1) atom to form corner-sharing SNa2CdSn tetrahedra.