Na11TiNb2Si4P2O25F is Esseneite-derived structured and crystallizes in the triclinic P1 space group. There are eleven inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(17), one O(18), one O(23), one O(25), one O(3), and one F(1) atom to form NaO5F octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, edges with two equivalent Na(2)O5F octahedra, edges with two equivalent Na(11)O6 octahedra, and edges with two equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 54-62°. In the second Na site, Na(2) is bonded to one O(17), one O(18), one O(24), one O(25), one O(4), and one F(1) atom to form distorted NaO5F octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, edges with two equivalent Na(1)O5F octahedra, edges with two equivalent Na(11)O6 octahedra, and edges with two equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 56-61°. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(14), one O(5), and one O(8) atom. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(12), one O(13), one O(2), one O(6), and one O(7) atom. In the fifth Na site, Na(5) is bonded to one O(1), one O(13), one O(15), and one O(6) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. In the sixth Na site, Na(6) is bonded to one O(14), one O(16), one O(2), and one O(5) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the seventh Na site, Na(7) is bonded in a 8-coordinate geometry to one O(12), one O(13), one O(20), one O(21), one O(9), two equivalent O(15), and one F(1) atom. In the eighth Na site, Na(8) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(14), one O(19), one O(22), one O(25), and two equivalent O(16) atoms. In the ninth Na site, Na(9) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(20), one O(21), one O(6), and one O(7) atom. In the tenth Na site, Na(10) is bonded in a 6-coordinate geometry to one O(11), one O(19), one O(2), one O(22), one O(5), and one O(8) atom. In the eleventh Na site, Na(11) is bonded to one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom to form distorted NaO6 octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, edges with two equivalent Na(1)O5F octahedra, edges with two equivalent Na(2)O5F octahedra, and edges with two equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 53-55°. Ti(1) is bonded to one O(23), one O(24), one O(25), one O(3), one O(4), and one F(1) atom to form TiO5F octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, edges with two equivalent Na(1)O5F octahedra, edges with two equivalent Na(2)O5F octahedra, and edges with two equivalent Na(11)O6 octahedra. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(12), one O(18), one O(20), one O(21), one O(7), and one O(9) atom to form distorted NbO6 octahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and corners with two equivalent Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-62°. In the second Nb site, Nb(2) is bonded to one O(10), one O(11), one O(17), one O(19), one O(22), and one O(8) atom to form distorted NbO6 octahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-61°. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(15), one O(21), one O(3), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(5)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-67°. In the second Si site, Si(2) is bonded to one O(10), one O(16), one O(22), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(2)O6 octahedra,  a cornercorner with one Na(6)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-69°. In the third Si site, Si(3) is bonded to one O(11), one O(16), one O(19), and one O(23) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(2)O6 octahedra,  a cornercorner with one Na(6)O4 tetrahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-62°. In the fourth Si site, Si(4) is bonded to one O(12), one O(15), one O(20), and one O(24) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(5)O4 tetrahedra, and  a cornercorner with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-62°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Na(6)O4 tetrahedra, and corners with two equivalent Na(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. In the second P site, P(2) is bonded to one O(14), one O(2), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Na(5)O4 tetrahedra, and corners with two equivalent Na(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. There are twenty-five inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), one Na(5), one Na(9), and one P(1) atom to form distorted corner-sharing ONa3P tetrahedra. In the second O site, O(2) is bonded to one Na(10), one Na(4), one Na(6), and one P(2) atom to form distorted corner-sharing ONa3P tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(11), one Ti(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted tetrahedral geometry to one Na(11), one Na(2), one Ti(1), and one Si(2) atom. In the fifth O site, O(5) is bonded to one Na(10), one Na(3), one Na(6), and one P(1) atom to form distorted corner-sharing ONa3P trigonal pyramids. In the sixth O site, O(6) is bonded to one Na(4), one Na(5), one Na(9), and one P(2) atom to form distorted corner-sharing ONa3P trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(4), one Na(9), one Nb(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(10), one Na(3), one Nb(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(7), one Nb(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(8), one Nb(2), and one Si(2) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(10), one Na(3), one Na(8), one Nb(2), and one Si(3) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(4), one Na(7), one Na(9), one Nb(1), and one Si(4) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), one Na(5), one Na(7), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(6), one Na(8), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(7), one Si(1), and one Si(4) atom. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to one Na(6), two equivalent Na(8), one Si(2), and one Si(3) atom. In the seventeenth O site, O(17) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(11), one Na(2), and one Nb(2) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(11), one Na(2), and one Nb(1) atom. In the nineteenth O site, O(19) is bonded in a 2-coordinate geometry to one Na(10), one Na(8), one Nb(2), and one Si(3) atom. In the twentieth O site, O(20) is bonded in a 2-coordinate geometry to one Na(7), one Na(9), one Nb(1), and one Si(4) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one Na(7), one Na(9), one Nb(1), and one Si(1) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Na(10), one Na(8), one Nb(2), and one Si(2) atom. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one Na(1), one Na(11), one Ti(1), and one Si(3) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(11), one Na(2), one Ti(1), and one Si(4) atom. In the twenty-fifth O site, O(25) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(8), and one Ti(1) atom. F(1) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(7), and one Ti(1) atom.
Na11TiNb2Si4P2O25F is Esseneite-derived structured and crystallizes in the triclinic P1 space group. There are eleven inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(17), one O(18), one O(23), one O(25), one O(3), and one F(1) atom to form NaO5F octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, edges with two equivalent Na(2)O5F octahedra, edges with two equivalent Na(11)O6 octahedra, and edges with two equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Na(1)-O(17) bond length is 2.33 Å. The Na(1)-O(18) bond length is 2.54 Å. The Na(1)-O(23) bond length is 2.30 Å. The Na(1)-O(25) bond length is 2.46 Å. The Na(1)-O(3) bond length is 2.31 Å. The Na(1)-F(1) bond length is 2.26 Å. In the second Na site, Na(2) is bonded to one O(17), one O(18), one O(24), one O(25), one O(4), and one F(1) atom to form distorted NaO5F octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, edges with two equivalent Na(1)O5F octahedra, edges with two equivalent Na(11)O6 octahedra, and edges with two equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 56-61°. The Na(2)-O(17) bond length is 2.61 Å. The Na(2)-O(18) bond length is 2.30 Å. The Na(2)-O(24) bond length is 2.33 Å. The Na(2)-O(25) bond length is 2.32 Å. The Na(2)-O(4) bond length is 2.26 Å. The Na(2)-F(1) bond length is 2.38 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(14), one O(5), and one O(8) atom. The Na(3)-O(1) bond length is 2.25 Å. The Na(3)-O(11) bond length is 2.80 Å. The Na(3)-O(14) bond length is 2.42 Å. The Na(3)-O(5) bond length is 2.33 Å. The Na(3)-O(8) bond length is 2.33 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(12), one O(13), one O(2), one O(6), and one O(7) atom. The Na(4)-O(12) bond length is 2.81 Å. The Na(4)-O(13) bond length is 2.42 Å. The Na(4)-O(2) bond length is 2.25 Å. The Na(4)-O(6) bond length is 2.33 Å. The Na(4)-O(7) bond length is 2.34 Å. In the fifth Na site, Na(5) is bonded to one O(1), one O(13), one O(15), and one O(6) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Na(5)-O(1) bond length is 2.22 Å. The Na(5)-O(13) bond length is 2.31 Å. The Na(5)-O(15) bond length is 2.38 Å. The Na(5)-O(6) bond length is 2.28 Å. In the sixth Na site, Na(6) is bonded to one O(14), one O(16), one O(2), and one O(5) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Na(6)-O(14) bond length is 2.31 Å. The Na(6)-O(16) bond length is 2.37 Å. The Na(6)-O(2) bond length is 2.22 Å. The Na(6)-O(5) bond length is 2.28 Å. In the seventh Na site, Na(7) is bonded in a 8-coordinate geometry to one O(12), one O(13), one O(20), one O(21), one O(9), two equivalent O(15), and one F(1) atom. The Na(7)-O(12) bond length is 2.51 Å. The Na(7)-O(13) bond length is 2.31 Å. The Na(7)-O(20) bond length is 2.90 Å. The Na(7)-O(21) bond length is 2.75 Å. The Na(7)-O(9) bond length is 2.35 Å. There is one shorter (2.71 Å) and one longer (2.81 Å) Na(7)-O(15) bond length. The Na(7)-F(1) bond length is 2.25 Å. In the eighth Na site, Na(8) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(14), one O(19), one O(22), one O(25), and two equivalent O(16) atoms. The Na(8)-O(10) bond length is 2.36 Å. The Na(8)-O(11) bond length is 2.53 Å. The Na(8)-O(14) bond length is 2.31 Å. The Na(8)-O(19) bond length is 2.89 Å. The Na(8)-O(22) bond length is 2.74 Å. The Na(8)-O(25) bond length is 2.31 Å. There is one shorter (2.74 Å) and one longer (2.78 Å) Na(8)-O(16) bond length. In the ninth Na site, Na(9) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(20), one O(21), one O(6), and one O(7) atom. The Na(9)-O(1) bond length is 2.25 Å. The Na(9)-O(12) bond length is 2.54 Å. The Na(9)-O(20) bond length is 2.58 Å. The Na(9)-O(21) bond length is 2.51 Å. The Na(9)-O(6) bond length is 2.28 Å. The Na(9)-O(7) bond length is 2.52 Å. In the tenth Na site, Na(10) is bonded in a 6-coordinate geometry to one O(11), one O(19), one O(2), one O(22), one O(5), and one O(8) atom. The Na(10)-O(11) bond length is 2.52 Å. The Na(10)-O(19) bond length is 2.58 Å. The Na(10)-O(2) bond length is 2.25 Å. The Na(10)-O(22) bond length is 2.53 Å. The Na(10)-O(5) bond length is 2.29 Å. The Na(10)-O(8) bond length is 2.51 Å. In the eleventh Na site, Na(11) is bonded to one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom to form distorted NaO6 octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, edges with two equivalent Na(1)O5F octahedra, edges with two equivalent Na(2)O5F octahedra, and edges with two equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 53-55°. The Na(11)-O(17) bond length is 2.31 Å. The Na(11)-O(18) bond length is 2.31 Å. The Na(11)-O(23) bond length is 2.59 Å. The Na(11)-O(24) bond length is 2.59 Å. The Na(11)-O(3) bond length is 2.48 Å. The Na(11)-O(4) bond length is 2.49 Å. Ti(1) is bonded to one O(23), one O(24), one O(25), one O(3), one O(4), and one F(1) atom to form TiO5F octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, edges with two equivalent Na(1)O5F octahedra, edges with two equivalent Na(2)O5F octahedra, and edges with two equivalent Na(11)O6 octahedra. The Ti(1)-O(23) bond length is 2.04 Å. The Ti(1)-O(24) bond length is 2.05 Å. The Ti(1)-O(25) bond length is 1.72 Å. The Ti(1)-O(3) bond length is 1.99 Å. The Ti(1)-O(4) bond length is 2.00 Å. The Ti(1)-F(1) bond length is 2.17 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(12), one O(18), one O(20), one O(21), one O(7), and one O(9) atom to form distorted NbO6 octahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and corners with two equivalent Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-62°. The Nb(1)-O(12) bond length is 2.06 Å. The Nb(1)-O(18) bond length is 1.80 Å. The Nb(1)-O(20) bond length is 2.04 Å. The Nb(1)-O(21) bond length is 2.01 Å. The Nb(1)-O(7) bond length is 2.24 Å. The Nb(1)-O(9) bond length is 1.99 Å. In the second Nb site, Nb(2) is bonded to one O(10), one O(11), one O(17), one O(19), one O(22), and one O(8) atom to form distorted NbO6 octahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-61°. The Nb(2)-O(10) bond length is 1.98 Å. The Nb(2)-O(11) bond length is 2.07 Å. The Nb(2)-O(17) bond length is 1.79 Å. The Nb(2)-O(19) bond length is 2.04 Å. The Nb(2)-O(22) bond length is 2.01 Å. The Nb(2)-O(8) bond length is 2.26 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(15), one O(21), one O(3), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(5)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-67°. The Si(1)-O(15) bond length is 1.65 Å. The Si(1)-O(21) bond length is 1.61 Å. The Si(1)-O(3) bond length is 1.60 Å. The Si(1)-O(9) bond length is 1.61 Å. In the second Si site, Si(2) is bonded to one O(10), one O(16), one O(22), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(2)O6 octahedra,  a cornercorner with one Na(6)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-69°. The Si(2)-O(10) bond length is 1.61 Å. The Si(2)-O(16) bond length is 1.65 Å. The Si(2)-O(22) bond length is 1.61 Å. The Si(2)-O(4) bond length is 1.60 Å. In the third Si site, Si(3) is bonded to one O(11), one O(16), one O(19), and one O(23) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(1)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(2)O6 octahedra,  a cornercorner with one Na(6)O4 tetrahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-62°. The Si(3)-O(11) bond length is 1.64 Å. The Si(3)-O(16) bond length is 1.65 Å. The Si(3)-O(19) bond length is 1.63 Å. The Si(3)-O(23) bond length is 1.61 Å. In the fourth Si site, Si(4) is bonded to one O(12), one O(15), one O(20), and one O(24) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(2)O5F octahedra,  a cornercorner with one Na(11)O6 octahedra,  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(5)O4 tetrahedra, and  a cornercorner with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-62°. The Si(4)-O(12) bond length is 1.64 Å. The Si(4)-O(15) bond length is 1.65 Å. The Si(4)-O(20) bond length is 1.64 Å. The Si(4)-O(24) bond length is 1.60 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Na(6)O4 tetrahedra, and corners with two equivalent Na(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(13) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(14), one O(2), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one Na(5)O4 tetrahedra, and corners with two equivalent Na(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. The P(2)-O(14) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.57 Å. There are twenty-five inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), one Na(5), one Na(9), and one P(1) atom to form distorted corner-sharing ONa3P tetrahedra. In the second O site, O(2) is bonded to one Na(10), one Na(4), one Na(6), and one P(2) atom to form distorted corner-sharing ONa3P tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(11), one Ti(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted tetrahedral geometry to one Na(11), one Na(2), one Ti(1), and one Si(2) atom. In the fifth O site, O(5) is bonded to one Na(10), one Na(3), one Na(6), and one P(1) atom to form distorted corner-sharing ONa3P trigonal pyramids. In the sixth O site, O(6) is bonded to one Na(4), one Na(5), one Na(9), and one P(2) atom to form distorted corner-sharing ONa3P trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(4), one Na(9), one Nb(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(10), one Na(3), one Nb(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(7), one Nb(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(8), one Nb(2), and one Si(2) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(10), one Na(3), one Na(8), one Nb(2), and one Si(3) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(4), one Na(7), one Na(9), one Nb(1), and one Si(4) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), one Na(5), one Na(7), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(6), one Na(8), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(7), one Si(1), and one Si(4) atom. In the sixteenth O site, O(16) is bonded in a 5-coordinate geometry to one Na(6), two equivalent Na(8), one Si(2), and one Si(3) atom. In the seventeenth O site, O(17) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(11), one Na(2), and one Nb(2) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(11), one Na(2), and one Nb(1) atom. In the nineteenth O site, O(19) is bonded in a 2-coordinate geometry to one Na(10), one Na(8), one Nb(2), and one Si(3) atom. In the twentieth O site, O(20) is bonded in a 2-coordinate geometry to one Na(7), one Na(9), one Nb(1), and one Si(4) atom. In the twenty-first O site, O(21) is bonded in a 4-coordinate geometry to one Na(7), one Na(9), one Nb(1), and one Si(1) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Na(10), one Na(8), one Nb(2), and one Si(2) atom. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one Na(1), one Na(11), one Ti(1), and one Si(3) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(11), one Na(2), one Ti(1), and one Si(4) atom. In the twenty-fifth O site, O(25) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(8), and one Ti(1) atom. F(1) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(7), and one Ti(1) atom.