Na11TiNb2Si4P2(O12F)2 is Esseneite-derived structured and crystallizes in the triclinic P-1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(3), one O(8), and one O(9) atom. In the second Na site, Na(2) is bonded to one O(1), one O(11), one O(6), one O(7), one O(9), two equivalent O(4), and one F(1) atom to form distorted NaO7F hexagonal bipyramids that share corners with two equivalent Na(2)O7F hexagonal bipyramids,  a cornercorner with one Ti(1)O4F2 octahedra, corners with two equivalent Na(6)O4F2 octahedra,  a cornercorner with one Na(3)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra,  an edgeedge with one Na(3)O4 tetrahedra, edges with two equivalent Si(1)O4 tetrahedra, and edges with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-69°. In the third Na site, Na(3) is bonded to one O(10), one O(4), one O(8), and one O(9) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Na(2)O7F hexagonal bipyramid,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Na(2)O7F hexagonal bipyramid. In the fourth Na site, Na(4) is bonded to two equivalent O(12), two equivalent O(2), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Ti(1)O4F2 octahedra, and edges with four equivalent Na(6)O4F2 octahedra. The corner-sharing octahedral tilt angles are 53°. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), and one O(8) atom. In the sixth Na site, Na(6) is bonded to one O(12), one O(2), two equivalent O(5), and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with two equivalent Na(2)O7F hexagonal bipyramids, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(6)O4F2 octahedra, edges with two equivalent Na(4)O6 octahedra, and edges with two equivalent Ti(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 54-61°. Ti(1) is bonded to two equivalent O(12), two equivalent O(2), and two equivalent F(1) atoms to form TiO4F2 octahedra that share corners with two equivalent Na(2)O7F hexagonal bipyramids, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(4)O6 octahedra, and edges with four equivalent Na(6)O4F2 octahedra. Nb(1) is bonded to one O(1), one O(11), one O(3), one O(5), one O(6), and one O(7) atom to form distorted NbO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra, corners with two equivalent Na(6)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and edges with two equivalent Na(2)O7F hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 53-61°. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(11), one O(12), one O(4), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(6)O4F2 octahedra,  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Ti(1)O4F2 octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(3)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and edges with two equivalent Na(2)O7F hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 36-62°. In the second Si site, Si(2) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(6)O4F2 octahedra,  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Ti(1)O4F2 octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(3)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, and edges with two equivalent Na(2)O7F hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 28-69°. P(1) is bonded to one O(10), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O7F hexagonal bipyramid,  a cornercorner with one Nb(1)O6 octahedra, and corners with three equivalent Na(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Nb(1), and one Si(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Ti(1), and one Si(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(5), one Nb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), two equivalent Na(6), and one Nb(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Nb(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(2), one Na(5), one Nb(1), and one Si(1) atom. In the eighth O site, O(8) is bonded in a distorted tetrahedral geometry to one Na(1), one Na(3), one Na(5), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(5), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(5), one Nb(1), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Ti(1), and one Si(1) atom. F(1) is bonded to one Na(2), two equivalent Na(6), and one Ti(1) atom to form a mixture of distorted corner and edge-sharing FNa3Ti tetrahedra.
Na11TiNb2Si4P2(O12F)2 is Esseneite-derived structured and crystallizes in the triclinic P-1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(3), one O(8), and one O(9) atom. The Na(1)-O(10) bond length is 2.37 Å. The Na(1)-O(11) bond length is 2.96 Å. The Na(1)-O(3) bond length is 2.38 Å. The Na(1)-O(8) bond length is 2.29 Å. The Na(1)-O(9) bond length is 2.49 Å. In the second Na site, Na(2) is bonded to one O(1), one O(11), one O(6), one O(7), one O(9), two equivalent O(4), and one F(1) atom to form distorted NaO7F hexagonal bipyramids that share corners with two equivalent Na(2)O7F hexagonal bipyramids,  a cornercorner with one Ti(1)O4F2 octahedra, corners with two equivalent Na(6)O4F2 octahedra,  a cornercorner with one Na(3)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra,  an edgeedge with one Na(3)O4 tetrahedra, edges with two equivalent Si(1)O4 tetrahedra, and edges with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-69°. The Na(2)-O(1) bond length is 2.71 Å. The Na(2)-O(11) bond length is 2.65 Å. The Na(2)-O(6) bond length is 2.42 Å. The Na(2)-O(7) bond length is 2.90 Å. The Na(2)-O(9) bond length is 2.35 Å. There is one shorter (2.78 Å) and one longer (2.85 Å) Na(2)-O(4) bond length. The Na(2)-F(1) bond length is 2.37 Å. In the third Na site, Na(3) is bonded to one O(10), one O(4), one O(8), and one O(9) atom to form distorted NaO4 tetrahedra that share  a cornercorner with one Na(2)O7F hexagonal bipyramid,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Na(2)O7F hexagonal bipyramid. The Na(3)-O(10) bond length is 2.34 Å. The Na(3)-O(4) bond length is 2.45 Å. The Na(3)-O(8) bond length is 2.26 Å. The Na(3)-O(9) bond length is 2.37 Å. In the fourth Na site, Na(4) is bonded to two equivalent O(12), two equivalent O(2), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Ti(1)O4F2 octahedra, and edges with four equivalent Na(6)O4F2 octahedra. The corner-sharing octahedral tilt angles are 53°. Both Na(4)-O(12) bond lengths are 2.65 Å. Both Na(4)-O(2) bond lengths are 2.53 Å. Both Na(4)-O(5) bond lengths are 2.36 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), and one O(8) atom. The Na(5)-O(1) bond length is 2.67 Å. The Na(5)-O(10) bond length is 2.36 Å. The Na(5)-O(11) bond length is 2.55 Å. The Na(5)-O(3) bond length is 2.60 Å. The Na(5)-O(7) bond length is 2.69 Å. The Na(5)-O(8) bond length is 2.29 Å. In the sixth Na site, Na(6) is bonded to one O(12), one O(2), two equivalent O(5), and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with two equivalent Na(2)O7F hexagonal bipyramids, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, edges with two equivalent Na(6)O4F2 octahedra, edges with two equivalent Na(4)O6 octahedra, and edges with two equivalent Ti(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 54-61°. The Na(6)-O(12) bond length is 2.38 Å. The Na(6)-O(2) bond length is 2.34 Å. There is one shorter (2.33 Å) and one longer (2.63 Å) Na(6)-O(5) bond length. There is one shorter (2.32 Å) and one longer (2.45 Å) Na(6)-F(1) bond length. Ti(1) is bonded to two equivalent O(12), two equivalent O(2), and two equivalent F(1) atoms to form TiO4F2 octahedra that share corners with two equivalent Na(2)O7F hexagonal bipyramids, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(4)O6 octahedra, and edges with four equivalent Na(6)O4F2 octahedra. Both Ti(1)-O(12) bond lengths are 2.06 Å. Both Ti(1)-O(2) bond lengths are 2.00 Å. Both Ti(1)-F(1) bond lengths are 2.00 Å. Nb(1) is bonded to one O(1), one O(11), one O(3), one O(5), one O(6), and one O(7) atom to form distorted NbO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra, corners with two equivalent Na(6)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and edges with two equivalent Na(2)O7F hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 53-61°. The Nb(1)-O(1) bond length is 2.04 Å. The Nb(1)-O(11) bond length is 2.09 Å. The Nb(1)-O(3) bond length is 2.27 Å. The Nb(1)-O(5) bond length is 1.81 Å. The Nb(1)-O(6) bond length is 2.03 Å. The Nb(1)-O(7) bond length is 2.07 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(11), one O(12), one O(4), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(6)O4F2 octahedra,  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Ti(1)O4F2 octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(3)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and edges with two equivalent Na(2)O7F hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 36-62°. The Si(1)-O(11) bond length is 1.65 Å. The Si(1)-O(12) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.68 Å. The Si(1)-O(7) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(6)O4F2 octahedra,  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Ti(1)O4F2 octahedra, corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Na(3)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, and edges with two equivalent Na(2)O7F hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 28-69°. The Si(2)-O(1) bond length is 1.62 Å. The Si(2)-O(2) bond length is 1.63 Å. The Si(2)-O(4) bond length is 1.67 Å. The Si(2)-O(6) bond length is 1.62 Å. P(1) is bonded to one O(10), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(2)O7F hexagonal bipyramid,  a cornercorner with one Nb(1)O6 octahedra, and corners with three equivalent Na(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. The P(1)-O(10) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(8) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Nb(1), and one Si(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Ti(1), and one Si(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(5), one Nb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), two equivalent Na(6), and one Nb(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Nb(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(2), one Na(5), one Nb(1), and one Si(1) atom. In the eighth O site, O(8) is bonded in a distorted tetrahedral geometry to one Na(1), one Na(3), one Na(5), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(5), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(5), one Nb(1), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Ti(1), and one Si(1) atom. F(1) is bonded to one Na(2), two equivalent Na(6), and one Ti(1) atom to form a mixture of distorted corner and edge-sharing FNa3Ti tetrahedra.