Na4InGeSi2PO12 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. 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 P(1)O4 tetrahedra. Ge(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 GeO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent P(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 In(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-40°. 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 In(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-38°. P(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-37°. 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 In(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(3), one In(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), one In(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(2), one Na(3), one Ge(1), 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 Ge(1), 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 Ge(1), and one P(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(3), one Na(4), one In(1), and one Si(2) atom to form distorted ONa3InSi trigonal bipyramids that share  a cornercorner with one O(12)Na3SiGe trigonal bipyramid, corners with two equivalent O(11)Na3SiGe trigonal bipyramids,  an edgeedge with one O(12)Na3SiGe trigonal bipyramid, and  a faceface with one O(8)Na3InSi trigonal bipyramid. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one Na(4), one In(1), and one Si(1) atom to form distorted ONa3InSi trigonal bipyramids that share  a cornercorner with one O(11)Na3SiGe trigonal bipyramid, corners with three equivalent O(12)Na3SiGe trigonal bipyramids,  an edgeedge with one O(11)Na3SiGe trigonal bipyramid, and  a faceface with one O(7)Na3InSi trigonal bipyramid. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(4), one In(1), and one P(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 Ge(1), and one P(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(2), one Na(4), one Ge(1), and one Si(1) atom to form distorted ONa3SiGe trigonal bipyramids that share  a cornercorner with one O(8)Na3InSi trigonal bipyramid, corners with two equivalent O(7)Na3InSi trigonal bipyramids,  an edgeedge with one O(8)Na3InSi trigonal bipyramid, and  a faceface with one O(12)Na3SiGe trigonal bipyramid. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Na(4), one Ge(1), and one Si(2) atom to form distorted ONa3SiGe trigonal bipyramids that share  a cornercorner with one O(7)Na3InSi trigonal bipyramid, corners with three equivalent O(8)Na3InSi trigonal bipyramids,  an edgeedge with one O(7)Na3InSi trigonal bipyramid, and  a faceface with one O(11)Na3SiGe trigonal bipyramid.
Na4InGeSi2PO12 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 2.65 Å. The Na(1)-O(10) bond length is 2.66 Å. The Na(1)-O(11) bond length is 2.41 Å. The Na(1)-O(3) bond length is 2.93 Å. The Na(1)-O(7) bond length is 2.46 Å. The Na(1)-O(9) bond length is 2.45 Å. There is one shorter (2.66 Å) and one longer (2.85 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 2.96 Å. The Na(2)-O(11) bond length is 2.61 Å. The Na(2)-O(12) bond length is 2.42 Å. The Na(2)-O(3) bond length is 2.46 Å. The Na(2)-O(4) bond length is 2.87 Å. The Na(2)-O(6) bond length is 2.71 Å. The Na(2)-O(8) bond length is 2.35 Å. The Na(2)-O(9) bond length is 2.58 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 2.44 Å. The Na(3)-O(12) bond length is 2.63 Å. The Na(3)-O(4) bond length is 2.70 Å. The Na(3)-O(6) bond length is 2.93 Å. The Na(3)-O(7) bond length is 2.44 Å. The Na(3)-O(8) bond length is 2.56 Å. There is one shorter (2.54 Å) and one longer (2.85 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 2.51 Å. The Na(4)-O(11) bond length is 2.54 Å. The Na(4)-O(12) bond length is 2.46 Å. The Na(4)-O(7) bond length is 2.47 Å. The Na(4)-O(8) bond length is 2.52 Å. The Na(4)-O(9) bond length is 2.64 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 P(1)O4 tetrahedra. The In(1)-O(1) bond length is 2.11 Å. The In(1)-O(2) bond length is 2.03 Å. The In(1)-O(3) bond length is 2.06 Å. The In(1)-O(7) bond length is 2.16 Å. The In(1)-O(8) bond length is 2.12 Å. The In(1)-O(9) bond length is 2.20 Å. Ge(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 GeO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Ge(1)-O(10) bond length is 2.17 Å. The Ge(1)-O(11) bond length is 1.95 Å. The Ge(1)-O(12) bond length is 1.97 Å. The Ge(1)-O(4) bond length is 1.89 Å. The Ge(1)-O(5) bond length is 1.93 Å. The Ge(1)-O(6) bond length is 2.01 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 In(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-40°. The Si(1)-O(11) bond length is 1.69 Å. The Si(1)-O(2) bond length is 1.60 Å. The Si(1)-O(5) bond length is 1.69 Å. The Si(1)-O(8) bond length is 1.62 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 In(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-38°. The Si(2)-O(12) bond length is 1.69 Å. The Si(2)-O(3) bond length is 1.60 Å. The Si(2)-O(4) bond length is 1.69 Å. The Si(2)-O(7) bond length is 1.63 Å. P(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-37°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(10) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.58 Å. The P(1)-O(9) bond length is 1.53 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 In(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(3), one In(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), one In(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(2), one Na(3), one Ge(1), 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 Ge(1), 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 Ge(1), and one P(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(3), one Na(4), one In(1), and one Si(2) atom to form distorted ONa3InSi trigonal bipyramids that share  a cornercorner with one O(12)Na3SiGe trigonal bipyramid, corners with two equivalent O(11)Na3SiGe trigonal bipyramids,  an edgeedge with one O(12)Na3SiGe trigonal bipyramid, and  a faceface with one O(8)Na3InSi trigonal bipyramid. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one Na(4), one In(1), and one Si(1) atom to form distorted ONa3InSi trigonal bipyramids that share  a cornercorner with one O(11)Na3SiGe trigonal bipyramid, corners with three equivalent O(12)Na3SiGe trigonal bipyramids,  an edgeedge with one O(11)Na3SiGe trigonal bipyramid, and  a faceface with one O(7)Na3InSi trigonal bipyramid. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(4), one In(1), and one P(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 Ge(1), and one P(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(2), one Na(4), one Ge(1), and one Si(1) atom to form distorted ONa3SiGe trigonal bipyramids that share  a cornercorner with one O(8)Na3InSi trigonal bipyramid, corners with two equivalent O(7)Na3InSi trigonal bipyramids,  an edgeedge with one O(8)Na3InSi trigonal bipyramid, and  a faceface with one O(12)Na3SiGe trigonal bipyramid. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Na(4), one Ge(1), and one Si(2) atom to form distorted ONa3SiGe trigonal bipyramids that share  a cornercorner with one O(7)Na3InSi trigonal bipyramid, corners with three equivalent O(8)Na3InSi trigonal bipyramids,  an edgeedge with one O(7)Na3InSi trigonal bipyramid, and  a faceface with one O(11)Na3SiGe trigonal bipyramid.