Na3InSnSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(7), one O(9), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. In(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form InO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. Sn(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form SnO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-43°. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. S(1) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-36°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one In(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Sn(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one S(1) atom. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one In(1), and one Si(2) atom to form distorted ONa2InSi trigonal pyramids that share corners with two equivalent O(11)Na2SiSn trigonal pyramids and  an edgeedge with one O(9)Na2InSi trigonal pyramid. In the ninth O site, O(9) is bonded to one Na(1), one Na(3), one In(1), and one Si(1) atom to form distorted ONa2InSi trigonal pyramids that share corners with two equivalent O(11)Na2SiSn trigonal pyramids and  an edgeedge with one O(8)Na2InSi trigonal pyramid. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Sn(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(3), one Sn(1), and one Si(2) atom to form distorted corner-sharing ONa2SiSn trigonal pyramids. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Sn(1), and one S(1) atom.
Na3InSnSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(7), one O(9), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.36 Å. The Na(1)-O(10) bond length is 2.71 Å. The Na(1)-O(11) bond length is 2.43 Å. The Na(1)-O(7) bond length is 2.63 Å. The Na(1)-O(9) bond length is 2.38 Å. There is one shorter (2.78 Å) and one longer (2.90 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.40 Å. The Na(2)-O(12) bond length is 2.67 Å. The Na(2)-O(2) bond length is 2.52 Å. The Na(2)-O(4) bond length is 2.88 Å. The Na(2)-O(6) bond length is 2.78 Å. The Na(2)-O(7) bond length is 2.56 Å. The Na(2)-O(8) bond length is 2.41 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. The Na(3)-O(10) bond length is 2.48 Å. The Na(3)-O(11) bond length is 2.61 Å. The Na(3)-O(12) bond length is 2.80 Å. The Na(3)-O(7) bond length is 2.80 Å. The Na(3)-O(8) bond length is 2.45 Å. The Na(3)-O(9) bond length is 2.37 Å. In(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form InO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The In(1)-O(1) bond length is 2.08 Å. The In(1)-O(2) bond length is 2.12 Å. The In(1)-O(3) bond length is 2.16 Å. The In(1)-O(7) bond length is 2.33 Å. The In(1)-O(8) bond length is 2.14 Å. The In(1)-O(9) bond length is 2.15 Å. Sn(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form SnO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Sn(1)-O(10) bond length is 2.09 Å. The Sn(1)-O(11) bond length is 2.03 Å. The Sn(1)-O(12) bond length is 2.25 Å. The Sn(1)-O(4) bond length is 2.33 Å. The Sn(1)-O(5) bond length is 2.01 Å. The Sn(1)-O(6) bond length is 2.00 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-43°. The Si(1)-O(1) bond length is 1.62 Å. The Si(1)-O(10) bond length is 1.70 Å. The Si(1)-O(6) bond length is 1.66 Å. The Si(1)-O(9) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-44°. The Si(2)-O(11) bond length is 1.66 Å. The Si(2)-O(2) bond length is 1.63 Å. The Si(2)-O(5) bond length is 1.67 Å. The Si(2)-O(8) bond length is 1.63 Å. S(1) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-36°. The S(1)-O(12) bond length is 1.50 Å. The S(1)-O(3) bond length is 1.46 Å. The S(1)-O(4) bond length is 1.49 Å. The S(1)-O(7) bond length is 1.49 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one In(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Sn(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one S(1) atom. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one In(1), and one Si(2) atom to form distorted ONa2InSi trigonal pyramids that share corners with two equivalent O(11)Na2SiSn trigonal pyramids and  an edgeedge with one O(9)Na2InSi trigonal pyramid. In the ninth O site, O(9) is bonded to one Na(1), one Na(3), one In(1), and one Si(1) atom to form distorted ONa2InSi trigonal pyramids that share corners with two equivalent O(11)Na2SiSn trigonal pyramids and  an edgeedge with one O(8)Na2InSi trigonal pyramid. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Sn(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(3), one Sn(1), and one Si(2) atom to form distorted corner-sharing ONa2SiSn trigonal pyramids. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Sn(1), and one S(1) atom.