Na6CaGe3Si2(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 7-coordinate geometry to one O(16), 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(14), one O(23), one O(4), one O(5), and one O(8) atom. In the sixth Na site, Na(6) is bonded in a 8-coordinate geometry to one O(10), one O(16), one O(18), one O(2), one O(21), one O(6), one O(7), and one O(9) atom. Ca(1) 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 CaO6 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 Ge sites. In the first Ge site, Ge(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 GeO6 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 Ge site, Ge(2) 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 GeO6 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 Ge site, Ge(3) 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 GeO6 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(1), one O(10), one O(14), and one O(18) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-39°. In the second Si site, Si(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. 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 Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-37°. 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 Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-44°. In the third P site, P(3) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-44°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-39°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ge(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(6), one Ge(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(4), one Ge(3), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Ca(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(5), one Ge(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(6), one Ca(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(6), one Ge(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Na(5), one Ge(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Ge(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(6), one Ge(2), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(5), one Ge(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(5), one Ca(1), and one Si(2) atom. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to one Na(3), one Ge(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Ca(1), and one Si(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Ge(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Ge(2), and one Si(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Ca(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Na(4), one Na(6), one Ge(3), and one Si(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Ge(2), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Ge(1), and one Si(2) atom. In the twenty-first O site, O(21) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(6), one Ge(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Ge(2), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 5-coordinate geometry to one Na(1), one Na(4), one Na(5), one Ge(3), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Ca(1), and one P(2) atom.
Na6CaGe3Si2(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 2.46 Å. The Na(1)-O(11) bond length is 2.45 Å. The Na(1)-O(21) bond length is 2.55 Å. The Na(1)-O(23) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.47 Å. The Na(1)-O(9) bond length is 2.57 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 2.45 Å. The Na(2)-O(12) bond length is 2.35 Å. The Na(2)-O(2) bond length is 2.41 Å. The Na(2)-O(22) bond length is 2.44 Å. The Na(2)-O(24) bond length is 2.43 Å. The Na(2)-O(4) bond length is 2.51 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 2.57 Å. The Na(3)-O(13) bond length is 2.77 Å. The Na(3)-O(14) bond length is 2.57 Å. The Na(3)-O(19) bond length is 2.57 Å. The Na(3)-O(2) bond length is 2.39 Å. The Na(3)-O(20) bond length is 2.67 Å. The Na(3)-O(21) bond length is 2.46 Å. The Na(3)-O(22) bond length is 2.54 Å. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(16), one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom. The Na(4)-O(16) bond length is 2.80 Å. The Na(4)-O(17) bond length is 2.35 Å. The Na(4)-O(18) bond length is 2.70 Å. The Na(4)-O(23) bond length is 2.76 Å. The Na(4)-O(24) bond length is 2.34 Å. The Na(4)-O(3) bond length is 2.31 Å. The Na(4)-O(4) bond length is 2.35 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(14), one O(23), one O(4), one O(5), and one O(8) atom. The Na(5)-O(11) bond length is 2.65 Å. The Na(5)-O(12) bond length is 2.28 Å. The Na(5)-O(14) bond length is 2.32 Å. The Na(5)-O(23) bond length is 2.28 Å. The Na(5)-O(4) bond length is 2.48 Å. The Na(5)-O(5) bond length is 2.72 Å. The Na(5)-O(8) bond length is 2.86 Å. In the sixth Na site, Na(6) is bonded in a 8-coordinate geometry to one O(10), one O(16), one O(18), one O(2), one O(21), one O(6), one O(7), and one O(9) atom. The Na(6)-O(10) bond length is 2.41 Å. The Na(6)-O(16) bond length is 2.47 Å. The Na(6)-O(18) bond length is 2.78 Å. The Na(6)-O(2) bond length is 2.74 Å. The Na(6)-O(21) bond length is 2.55 Å. The Na(6)-O(6) bond length is 2.50 Å. The Na(6)-O(7) bond length is 2.85 Å. The Na(6)-O(9) bond length is 2.42 Å. Ca(1) 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 CaO6 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 Ca(1)-O(12) bond length is 2.23 Å. The Ca(1)-O(14) bond length is 2.21 Å. The Ca(1)-O(17) bond length is 2.24 Å. The Ca(1)-O(24) bond length is 2.26 Å. The Ca(1)-O(4) bond length is 2.37 Å. The Ca(1)-O(6) bond length is 2.15 Å. There are three inequivalent Ge sites. In the first Ge site, Ge(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 GeO6 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 Ge(1)-O(1) bond length is 1.85 Å. The Ge(1)-O(15) bond length is 1.84 Å. The Ge(1)-O(20) bond length is 1.80 Å. The Ge(1)-O(21) bond length is 1.99 Å. The Ge(1)-O(7) bond length is 1.89 Å. The Ge(1)-O(9) bond length is 1.95 Å. In the second Ge site, Ge(2) 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 GeO6 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 Ge(2)-O(10) bond length is 1.88 Å. The Ge(2)-O(16) bond length is 1.87 Å. The Ge(2)-O(19) bond length is 1.98 Å. The Ge(2)-O(2) bond length is 2.09 Å. The Ge(2)-O(22) bond length is 2.00 Å. The Ge(2)-O(8) bond length is 1.92 Å. In the third Ge site, Ge(3) 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 GeO6 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 Ge(3)-O(11) bond length is 2.01 Å. The Ge(3)-O(13) bond length is 1.96 Å. The Ge(3)-O(18) bond length is 1.89 Å. The Ge(3)-O(23) bond length is 2.05 Å. The Ge(3)-O(3) bond length is 1.88 Å. The Ge(3)-O(5) bond length is 2.02 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(14), and one O(18) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-39°. The Si(1)-O(1) bond length is 1.65 Å. The Si(1)-O(10) bond length is 1.66 Å. The Si(1)-O(14) bond length is 1.60 Å. The Si(1)-O(18) bond length is 1.70 Å. In the second Si site, Si(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. The Si(2)-O(12) bond length is 1.59 Å. The Si(2)-O(16) bond length is 1.69 Å. The Si(2)-O(20) bond length is 1.62 Å. The Si(2)-O(3) bond length is 1.67 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 Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-37°. The P(1)-O(21) bond length is 1.58 Å. The P(1)-O(22) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.50 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 Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-44°. The P(2)-O(23) bond length is 1.58 Å. The P(2)-O(24) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.53 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-44°. The P(3)-O(13) bond length is 1.57 Å. The P(3)-O(17) bond length is 1.51 Å. The P(3)-O(2) bond length is 1.58 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ge(1)O6 octahedra,  a cornercorner with one Ge(2)O6 octahedra, and  a cornercorner with one Ge(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-39°. The P(4)-O(11) bond length is 1.56 Å. The P(4)-O(15) bond length is 1.52 Å. The P(4)-O(19) bond length is 1.58 Å. The P(4)-O(4) bond length is 1.53 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ge(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(6), one Ge(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(4), one Ge(3), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Ca(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(5), one Ge(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(6), one Ca(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(6), one Ge(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Na(5), one Ge(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Ge(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(6), one Ge(2), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(5), one Ge(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(5), one Ca(1), and one Si(2) atom. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to one Na(3), one Ge(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Ca(1), and one Si(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Ge(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Ge(2), and one Si(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Ca(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Na(4), one Na(6), one Ge(3), and one Si(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Ge(2), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Ge(1), and one Si(2) atom. In the twenty-first O site, O(21) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(6), one Ge(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Ge(2), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 5-coordinate geometry to one Na(1), one Na(4), one Na(5), one Ge(3), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Ca(1), and one P(2) atom.