Na2In2SiS6 is Chalcostibite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form NaS4 trigonal pyramids that share corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent Si(1)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, and corners with three equivalent In(2)S4 tetrahedra. In the second Na site, Na(2) is bonded to one S(1), one S(2), one S(3), one S(5), and one S(6) atom to form distorted NaS5 square pyramids that share  a cornercorner with one Si(1)S4 tetrahedra, corners with three equivalent In(2)S4 tetrahedra, corners with four equivalent In(1)S4 tetrahedra, corners with three equivalent Na(1)S4 trigonal pyramids, and  an edgeedge with one Si(1)S4 tetrahedra. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form InS4 tetrahedra that share corners with four equivalent Na(2)S5 square pyramids, corners with two equivalent In(2)S4 tetrahedra, corners with two equivalent Si(1)S4 tetrahedra, and corners with three equivalent Na(1)S4 trigonal pyramids. In the second In site, In(2) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form InS4 tetrahedra that share corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent Si(1)S4 tetrahedra, and corners with three equivalent Na(1)S4 trigonal pyramids. Si(1) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form SiS4 tetrahedra that share  a cornercorner with one Na(2)S5 square pyramid, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent In(2)S4 tetrahedra, corners with two equivalent Na(1)S4 trigonal pyramids, and  an edgeedge with one Na(2)S5 square pyramid. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Na(2), one In(1), and one In(2) atom to form SNa2In2 tetrahedra that share corners with four equivalent S(2)Na2In2 tetrahedra and corners with three equivalent S(5)Na2InSi trigonal pyramids. In the second S site, S(2) is bonded to one Na(1), one Na(2), one In(1), and one In(2) atom to form SNa2In2 tetrahedra that share corners with four equivalent S(1)Na2In2 tetrahedra and corners with three equivalent S(5)Na2InSi trigonal pyramids. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one In(1), and one Si(1) atom. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Na(1), one In(2), and one Si(1) atom. In the fifth S site, S(5) is bonded to one Na(1), one Na(2), one In(1), and one Si(1) atom to form distorted corner-sharing SNa2InSi trigonal pyramids. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Na(2), one In(2), and one Si(1) atom.
Na2In2SiS6 is Chalcostibite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form NaS4 trigonal pyramids that share corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent Si(1)S4 tetrahedra, corners with three equivalent In(1)S4 tetrahedra, and corners with three equivalent In(2)S4 tetrahedra. The Na(1)-S(1) bond length is 2.75 Å. The Na(1)-S(2) bond length is 2.73 Å. The Na(1)-S(4) bond length is 2.96 Å. The Na(1)-S(5) bond length is 2.77 Å. In the second Na site, Na(2) is bonded to one S(1), one S(2), one S(3), one S(5), and one S(6) atom to form distorted NaS5 square pyramids that share  a cornercorner with one Si(1)S4 tetrahedra, corners with three equivalent In(2)S4 tetrahedra, corners with four equivalent In(1)S4 tetrahedra, corners with three equivalent Na(1)S4 trigonal pyramids, and  an edgeedge with one Si(1)S4 tetrahedra. The Na(2)-S(1) bond length is 2.76 Å. The Na(2)-S(2) bond length is 2.75 Å. The Na(2)-S(3) bond length is 2.81 Å. The Na(2)-S(5) bond length is 3.06 Å. The Na(2)-S(6) bond length is 2.87 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form InS4 tetrahedra that share corners with four equivalent Na(2)S5 square pyramids, corners with two equivalent In(2)S4 tetrahedra, corners with two equivalent Si(1)S4 tetrahedra, and corners with three equivalent Na(1)S4 trigonal pyramids. The In(1)-S(1) bond length is 2.45 Å. The In(1)-S(2) bond length is 2.46 Å. The In(1)-S(3) bond length is 2.51 Å. The In(1)-S(5) bond length is 2.51 Å. In the second In site, In(2) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form InS4 tetrahedra that share corners with three equivalent Na(2)S5 square pyramids, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent Si(1)S4 tetrahedra, and corners with three equivalent Na(1)S4 trigonal pyramids. The In(2)-S(1) bond length is 2.47 Å. The In(2)-S(2) bond length is 2.47 Å. The In(2)-S(4) bond length is 2.51 Å. The In(2)-S(6) bond length is 2.49 Å. Si(1) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form SiS4 tetrahedra that share  a cornercorner with one Na(2)S5 square pyramid, corners with two equivalent In(1)S4 tetrahedra, corners with two equivalent In(2)S4 tetrahedra, corners with two equivalent Na(1)S4 trigonal pyramids, and  an edgeedge with one Na(2)S5 square pyramid. The Si(1)-S(3) bond length is 2.13 Å. The Si(1)-S(4) bond length is 2.12 Å. The Si(1)-S(5) bond length is 2.15 Å. The Si(1)-S(6) bond length is 2.12 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Na(2), one In(1), and one In(2) atom to form SNa2In2 tetrahedra that share corners with four equivalent S(2)Na2In2 tetrahedra and corners with three equivalent S(5)Na2InSi trigonal pyramids. In the second S site, S(2) is bonded to one Na(1), one Na(2), one In(1), and one In(2) atom to form SNa2In2 tetrahedra that share corners with four equivalent S(1)Na2In2 tetrahedra and corners with three equivalent S(5)Na2InSi trigonal pyramids. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one In(1), and one Si(1) atom. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Na(1), one In(2), and one Si(1) atom. In the fifth S site, S(5) is bonded to one Na(1), one Na(2), one In(1), and one Si(1) atom to form distorted corner-sharing SNa2InSi trigonal pyramids. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Na(2), one In(2), and one Si(1) atom.