Na4LaGeSi2PO12 crystallizes in the monoclinic Cc space group. There are four 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 3-coordinate geometry to one O(12), one O(3), one O(6), and one O(8) atom. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(10), one O(2), and one O(7) atom. In the fourth Na site, Na(4) 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. La(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 LaO6 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-52°. 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-48°. 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 La(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(3), one La(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Ge(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a 2-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 3-coordinate geometry to one Na(2), one Ge(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one La(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a 1-coordinate geometry to one Na(2), one Na(4), one La(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one La(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a 4-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 in a 4-coordinate geometry to one Na(1), one Na(4), one Ge(1), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ge(1), and one Si(2) atom.
Na4LaGeSi2PO12 crystallizes in the monoclinic Cc space group. There are four 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 2.46 Å. The Na(1)-O(10) bond length is 2.93 Å. The Na(1)-O(11) bond length is 2.39 Å. The Na(1)-O(7) bond length is 2.79 Å. The Na(1)-O(9) bond length is 2.34 Å. There is one shorter (2.81 Å) and one longer (2.85 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 3-coordinate geometry to one O(12), one O(3), one O(6), and one O(8) atom. The Na(2)-O(12) bond length is 2.35 Å. The Na(2)-O(3) bond length is 2.29 Å. The Na(2)-O(6) bond length is 2.74 Å. The Na(2)-O(8) bond length is 2.33 Å. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(10), one O(2), and one O(7) atom. The Na(3)-O(10) bond length is 2.34 Å. The Na(3)-O(2) bond length is 2.31 Å. The Na(3)-O(7) bond length is 2.36 Å. In the fourth Na site, Na(4) 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(4)-O(10) bond length is 2.34 Å. The Na(4)-O(11) bond length is 2.49 Å. The Na(4)-O(12) bond length is 2.37 Å. The Na(4)-O(7) bond length is 2.62 Å. The Na(4)-O(8) bond length is 2.83 Å. The Na(4)-O(9) bond length is 2.90 Å. La(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 LaO6 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 La(1)-O(1) bond length is 2.32 Å. The La(1)-O(2) bond length is 2.22 Å. The La(1)-O(3) bond length is 2.25 Å. The La(1)-O(7) bond length is 2.42 Å. The La(1)-O(8) bond length is 2.33 Å. The La(1)-O(9) bond length is 2.44 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 2.24 Å. The Ge(1)-O(11) bond length is 1.94 Å. The Ge(1)-O(12) bond length is 1.98 Å. The Ge(1)-O(4) bond length is 1.92 Å. The Ge(1)-O(5) bond length is 1.99 Å. The Ge(1)-O(6) bond length is 2.11 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-52°. The Si(1)-O(11) bond length is 1.70 Å. The Si(1)-O(2) bond length is 1.60 Å. The Si(1)-O(5) bond length is 1.72 Å. The Si(1)-O(8) bond length is 1.61 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. The Si(2)-O(12) bond length is 1.70 Å. The Si(2)-O(3) bond length is 1.59 Å. The Si(2)-O(4) bond length is 1.73 Å. The Si(2)-O(7) bond length is 1.62 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-48°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(10) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.59 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 3-coordinate geometry to one Na(1), one La(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(3), one La(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Ge(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a 2-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 3-coordinate geometry to one Na(2), one Ge(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one La(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a 1-coordinate geometry to one Na(2), one Na(4), one La(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one La(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a 4-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 in a 4-coordinate geometry to one Na(1), one Na(4), one Ge(1), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ge(1), and one Si(2) atom.