Na4Ga2Si2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), one O(9), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(11), one O(12), one O(3), one O(4), one O(6), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(4), one O(6), one O(7), one O(8), and two equivalent O(2) atoms. In the fourth Na site, Na(4) is bonded in a distorted hexagonal planar geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. There are two inequivalent Ga sites. In the first Ga site, Ga(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 distorted GaO6 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. In the second Ga site, Ga(2) 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 GaO6 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(11), one O(2), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-44°. In the second Si site, Si(2) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-38°. S(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-36°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), one Ga(1), and one S(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Na(3), one Ga(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ga(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ga(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ga(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Na(2), one Na(3), one Ga(2), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(3), one Na(4), one Ga(1), and one Si(2) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one Na(4), one Ga(1), and one Si(1) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(4), one Ga(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Ga(2), and one S(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(2), one Na(4), one Ga(2), and one Si(1) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Na(4), one Ga(2), and one Si(2) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids.
Na4Ga2Si2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), one O(9), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.73 Å. The Na(1)-O(10) bond length is 2.58 Å. The Na(1)-O(11) bond length is 2.40 Å. The Na(1)-O(3) bond length is 2.85 Å. The Na(1)-O(7) bond length is 2.35 Å. The Na(1)-O(9) bond length is 2.54 Å. There is one shorter (2.56 Å) and one longer (2.80 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(11), one O(12), one O(3), one O(4), one O(6), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.94 Å. The Na(2)-O(11) bond length is 2.47 Å. The Na(2)-O(12) bond length is 2.40 Å. The Na(2)-O(3) bond length is 2.52 Å. The Na(2)-O(4) bond length is 2.81 Å. The Na(2)-O(6) bond length is 2.72 Å. The Na(2)-O(8) bond length is 2.44 Å. The Na(2)-O(9) bond length is 2.51 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(4), one O(6), one O(7), one O(8), and two equivalent O(2) atoms. The Na(3)-O(10) bond length is 2.49 Å. The Na(3)-O(12) bond length is 2.45 Å. The Na(3)-O(4) bond length is 2.57 Å. The Na(3)-O(6) bond length is 2.94 Å. The Na(3)-O(7) bond length is 2.52 Å. The Na(3)-O(8) bond length is 2.45 Å. There is one shorter (2.63 Å) and one longer (2.76 Å) Na(3)-O(2) bond length. In the fourth Na site, Na(4) is bonded in a distorted hexagonal planar geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. The Na(4)-O(10) bond length is 2.61 Å. The Na(4)-O(11) bond length is 2.48 Å. The Na(4)-O(12) bond length is 2.44 Å. The Na(4)-O(7) bond length is 2.43 Å. The Na(4)-O(8) bond length is 2.45 Å. The Na(4)-O(9) bond length is 2.65 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(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 distorted GaO6 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 Ga(1)-O(1) bond length is 2.23 Å. The Ga(1)-O(2) bond length is 1.84 Å. The Ga(1)-O(3) bond length is 1.91 Å. The Ga(1)-O(7) bond length is 2.02 Å. The Ga(1)-O(8) bond length is 1.91 Å. The Ga(1)-O(9) bond length is 2.32 Å. In the second Ga site, Ga(2) 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 GaO6 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 Ga(2)-O(10) bond length is 2.17 Å. The Ga(2)-O(11) bond length is 2.00 Å. The Ga(2)-O(12) bond length is 2.02 Å. The Ga(2)-O(4) bond length is 1.89 Å. The Ga(2)-O(5) bond length is 1.95 Å. The Ga(2)-O(6) bond length is 2.05 Å. There are two inequivalent Si sites. In the first Si site, Si(1) 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 Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-44°. The Si(1)-O(11) bond length is 1.65 Å. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(5) bond length is 1.64 Å. The Si(1)-O(8) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-38°. The Si(2)-O(12) bond length is 1.66 Å. The Si(2)-O(3) bond length is 1.64 Å. The Si(2)-O(4) bond length is 1.64 Å. The Si(2)-O(7) bond length is 1.66 Å. S(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-36°. The S(1)-O(1) bond length is 1.47 Å. The S(1)-O(10) bond length is 1.50 Å. The S(1)-O(6) bond length is 1.49 Å. The S(1)-O(9) bond length is 1.48 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), one Ga(1), and one S(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Na(3), one Ga(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ga(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ga(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ga(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Na(2), one Na(3), one Ga(2), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(3), one Na(4), one Ga(1), and one Si(2) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one Na(4), one Ga(1), and one Si(1) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(4), one Ga(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Ga(2), and one S(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(2), one Na(4), one Ga(2), and one Si(1) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Na(4), one Ga(2), and one Si(2) atom to form a mixture of distorted corner, edge, and face-sharing ONa3GaSi trigonal bipyramids.