Na6NbIn3Si2(PO6)4 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(21), one O(23), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(12), one O(2), one O(22), one O(24), and one O(4) atom. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(13), one O(14), one O(19), one O(2), one O(20), one O(21), and one O(22) atom. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(13), one O(24), one O(3), one O(6), and one O(7) atom. In the sixth Na site, Na(6) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(15), one O(22), one O(5), and one O(9) atom. Nb(1) is bonded to one O(10), one O(16), one O(19), one O(2), one O(22), and one O(8) atom to form NbO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are three inequivalent In sites. In the first In site, In(1) is bonded to one O(1), one O(15), one O(20), one O(21), one O(7), and one O(9) atom to form InO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the second In site, In(2) is bonded to one O(11), one O(13), one O(18), one O(23), one O(3), and one O(5) atom to form InO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the third In site, In(3) is bonded to one O(12), one O(14), one O(17), one O(24), one O(4), and one O(6) atom to form InO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-40°. In the second Si site, Si(2) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-49°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(21), one O(22), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-39°. In the second P site, P(2) is bonded to one O(23), one O(24), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-44°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-39°. In the fourth P site, P(4) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-49°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one Na(6), one In(1), and one P(3) atom to form distorted corner-sharing ONa3InP trigonal bipyramids. In the second O site, O(2) is bonded to one Na(2), one Na(3), one Nb(1), and one Si(1) atom to form distorted corner-sharing ONa2NbSi trigonal pyramids. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one Na(5), one In(2), and one P(4) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(4), one In(3), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(6), one In(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(5), one In(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(5), one In(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Nb(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(6), one In(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(6), one Nb(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(5), one In(2), and one Si(2) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(5), one In(3), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one In(2), and one Si(1) atom. In the fourteenth O site, O(14) is bonded in a 2-coordinate geometry to one Na(3), one In(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Na(6), one In(1), and one Si(2) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one Nb(1) and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one In(3), and one Si(1) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Na(4), one In(2), and one P(3) atom. In the nineteenth O site, O(19) is bonded in a distorted linear geometry to one Na(3), one Nb(1), and one Si(2) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Na(3), one In(1), and one P(4) atom. In the twenty-first O site, O(21) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one In(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(6), one Nb(1), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one In(2), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one In(3), and one P(2) atom.
Na6NbIn3Si2(PO6)4 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(21), one O(23), one O(3), and one O(9) atom. The Na(1)-O(1) bond length is 2.56 Å. The Na(1)-O(11) bond length is 2.43 Å. The Na(1)-O(21) bond length is 2.58 Å. The Na(1)-O(23) bond length is 2.47 Å. The Na(1)-O(3) bond length is 2.48 Å. The Na(1)-O(9) bond length is 2.44 Å. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(12), one O(2), one O(22), one O(24), and one O(4) atom. The Na(2)-O(10) bond length is 2.60 Å. The Na(2)-O(12) bond length is 2.49 Å. The Na(2)-O(2) bond length is 2.66 Å. The Na(2)-O(22) bond length is 2.63 Å. The Na(2)-O(24) bond length is 2.48 Å. The Na(2)-O(4) bond length is 2.38 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(13), one O(14), one O(19), one O(2), one O(20), one O(21), and one O(22) atom. The Na(3)-O(1) bond length is 2.47 Å. The Na(3)-O(13) bond length is 2.65 Å. The Na(3)-O(14) bond length is 2.87 Å. The Na(3)-O(19) bond length is 2.96 Å. The Na(3)-O(2) bond length is 2.63 Å. The Na(3)-O(20) bond length is 2.46 Å. The Na(3)-O(21) bond length is 2.44 Å. The Na(3)-O(22) bond length is 2.83 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom. The Na(4)-O(17) bond length is 2.56 Å. The Na(4)-O(18) bond length is 2.51 Å. The Na(4)-O(23) bond length is 2.49 Å. The Na(4)-O(24) bond length is 2.55 Å. The Na(4)-O(3) bond length is 2.40 Å. The Na(4)-O(4) bond length is 2.43 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(13), one O(24), one O(3), one O(6), and one O(7) atom. The Na(5)-O(11) bond length is 2.40 Å. The Na(5)-O(12) bond length is 2.46 Å. The Na(5)-O(13) bond length is 2.44 Å. The Na(5)-O(24) bond length is 2.43 Å. The Na(5)-O(3) bond length is 2.88 Å. The Na(5)-O(6) bond length is 2.82 Å. The Na(5)-O(7) bond length is 2.93 Å. In the sixth Na site, Na(6) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(15), one O(22), one O(5), and one O(9) atom. The Na(6)-O(1) bond length is 2.60 Å. The Na(6)-O(10) bond length is 2.57 Å. The Na(6)-O(15) bond length is 2.37 Å. The Na(6)-O(22) bond length is 2.52 Å. The Na(6)-O(5) bond length is 2.72 Å. The Na(6)-O(9) bond length is 2.47 Å. Nb(1) is bonded to one O(10), one O(16), one O(19), one O(2), one O(22), and one O(8) atom to form NbO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The Nb(1)-O(10) bond length is 2.11 Å. The Nb(1)-O(16) bond length is 1.98 Å. The Nb(1)-O(19) bond length is 1.92 Å. The Nb(1)-O(2) bond length is 1.96 Å. The Nb(1)-O(22) bond length is 2.08 Å. The Nb(1)-O(8) bond length is 2.07 Å. There are three inequivalent In sites. In the first In site, In(1) is bonded to one O(1), one O(15), one O(20), one O(21), one O(7), and one O(9) atom to form InO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The In(1)-O(1) bond length is 2.23 Å. The In(1)-O(15) bond length is 2.10 Å. The In(1)-O(20) bond length is 2.17 Å. The In(1)-O(21) bond length is 2.20 Å. The In(1)-O(7) bond length is 2.09 Å. The In(1)-O(9) bond length is 2.13 Å. In the second In site, In(2) is bonded to one O(11), one O(13), one O(18), one O(23), one O(3), and one O(5) atom to form InO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The In(2)-O(11) bond length is 2.17 Å. The In(2)-O(13) bond length is 2.16 Å. The In(2)-O(18) bond length is 2.21 Å. The In(2)-O(23) bond length is 2.21 Å. The In(2)-O(3) bond length is 2.34 Å. The In(2)-O(5) bond length is 2.16 Å. In the third In site, In(3) is bonded to one O(12), one O(14), one O(17), one O(24), one O(4), and one O(6) atom to form InO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The In(3)-O(12) bond length is 2.22 Å. The In(3)-O(14) bond length is 2.09 Å. The In(3)-O(17) bond length is 2.09 Å. The In(3)-O(24) bond length is 2.26 Å. The In(3)-O(4) bond length is 2.15 Å. The In(3)-O(6) bond length is 2.17 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-40°. The Si(1)-O(13) bond length is 1.65 Å. The Si(1)-O(17) bond length is 1.62 Å. The Si(1)-O(2) bond length is 1.70 Å. The Si(1)-O(9) bond length is 1.62 Å. In the second Si site, Si(2) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-49°. The Si(2)-O(11) bond length is 1.63 Å. The Si(2)-O(15) bond length is 1.62 Å. The Si(2)-O(19) bond length is 1.73 Å. The Si(2)-O(4) bond length is 1.62 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(21), one O(22), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-39°. The P(1)-O(21) bond length is 1.54 Å. The P(1)-O(22) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(23), one O(24), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-44°. The P(2)-O(23) bond length is 1.55 Å. The P(2)-O(24) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-39°. The P(3)-O(1) bond length is 1.55 Å. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(14) bond length is 1.53 Å. The P(3)-O(18) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(2)O6 octahedra, and  a cornercorner with one In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-49°. The P(4)-O(12) bond length is 1.54 Å. The P(4)-O(16) bond length is 1.59 Å. The P(4)-O(20) bond length is 1.54 Å. The P(4)-O(3) bond length is 1.55 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one Na(6), one In(1), and one P(3) atom to form distorted corner-sharing ONa3InP trigonal bipyramids. In the second O site, O(2) is bonded to one Na(2), one Na(3), one Nb(1), and one Si(1) atom to form distorted corner-sharing ONa2NbSi trigonal pyramids. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one Na(5), one In(2), and one P(4) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(4), one In(3), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(6), one In(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(5), one In(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(5), one In(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Nb(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(6), one In(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(6), one Nb(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(5), one In(2), and one Si(2) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(5), one In(3), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one In(2), and one Si(1) atom. In the fourteenth O site, O(14) is bonded in a 2-coordinate geometry to one Na(3), one In(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Na(6), one In(1), and one Si(2) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one Nb(1) and one P(4) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one In(3), and one Si(1) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Na(4), one In(2), and one P(3) atom. In the nineteenth O site, O(19) is bonded in a distorted linear geometry to one Na(3), one Nb(1), and one Si(2) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Na(3), one In(1), and one P(4) atom. In the twenty-first O site, O(21) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one In(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(6), one Nb(1), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one In(2), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one In(3), and one P(2) atom.