Materials Data on Na11TiNb2Si4P2(O12F)2 by Materials Project

Na11TiNb2Si4P2(O12F)2 is Esseneite-derived structured and crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are six inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 4-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.29–2.96 Å. In the second Na1+ site, Na1+ is bonded to seven O2- and one F1- atom to form distorted NaO7F hexagonal bipyramids that share corners with two equivalent NaO7F hexagonal bipyramids, a cornercorner with one TiO4F2 octahedra, corners with two equivalent NaO4F2 octahedra, a cornercorner with one NaO4 tetrahedra, a cornercorner with one PO4 tetrahedra, edges with two equivalent NbO6 octahedra, an edgeedge with one NaO4 tetrahedra, and edges with four SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 49–69°. There are a spread of Na–O bond distances ranging from 2.35–2.90 Å. The Na–F bond length is 2.37 Å. In the third Na1+ site, Na1+ is bonded to four O2- atoms to form distorted NaO4 tetrahedra that share a cornercorner with one NaO7F hexagonal bipyramid, corners with two SiO4 tetrahedra, corners with three equivalent PO4 tetrahedra, and an edgeedge with one NaO7F hexagonal bipyramid. There are a spread of Na–O bond distances ranging from 2.26–2.45 Å. In the fourth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with two equivalent NbO6 octahedra, corners with four SiO4 tetrahedra, edges with two equivalent TiO4F2 octahedra, and edges with four equivalent NaO4F2 octahedra. The corner-sharing octahedral tilt angles are 53°. There are a spread of Na–O bond distances ranging from 2.36–2.65 Å. In the fifth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.29–2.69 Å. In the sixth Na1+ site, Na1+ is bonded to four O2- and two equivalent F1- atoms to form NaO4F2 octahedra that share corners with two equivalent NaO7F hexagonal bipyramids, corners with two equivalent NbO6 octahedra, corners with two SiO4 tetrahedra, edges with two equivalent TiO4F2 octahedra, and edges with four NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 54–61°. There are a spread of Na–O bond distances ranging from 2.33–2.63 Å. There are one shorter (2.32 Å) and one longer (2.45 Å) Na–F bond lengths. Ti4+ is bonded to four O2- and two equivalent F1- atoms to form TiO4F2 octahedra that share corners with two equivalent NaO7F hexagonal bipyramids, corners with four SiO4 tetrahedra, and edges with six NaO4F2 octahedra. There are two shorter (2.00 Å) and two longer (2.06 Å) Ti–O bond lengths. Both Ti–F bond lengths are 2.00 Å. Nb+4.50+ is bonded to six O2- atoms to form distorted NbO6 octahedra that share corners with three NaO6 octahedra, a cornercorner with one PO4 tetrahedra, corners with four SiO4 tetrahedra, and edges with two equivalent NaO7F hexagonal bipyramids. The corner-sharing octahedra tilt angles range from 53–61°. There are a spread of Nb–O bond distances ranging from 1.81–2.27 Å. There are two inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one TiO4F2 octahedra, corners with two NaO6 octahedra, corners with two equivalent NbO6 octahedra, a cornercorner with one NaO4 tetrahedra, a cornercorner with one SiO4 tetrahedra, and edges with two equivalent NaO7F hexagonal bipyramids. The corner-sharing octahedra tilt angles range from 36–62°. There are a spread of Si–O bond distances ranging from 1.63–1.68 Å. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one TiO4F2 octahedra, corners with two NaO6 octahedra, corners with two equivalent NbO6 octahedra, a cornercorner with one NaO4 tetrahedra, a cornercorner with one SiO4 tetrahedra, and edges with two equivalent NaO7F hexagonal bipyramids. The corner-sharing octahedra tilt angles range from 28–69°. There are a spread of Si–O bond distances ranging from 1.62–1.67 Å. P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one NaO7F hexagonal bipyramid, a cornercorner with one NbO6 octahedra, and corners with three equivalent NaO4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. There are a spread of P–O bond distances ranging from 1.55–1.59 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to two Na1+, one Nb+4.50+, and one Si4+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Ti4+, and one Si4+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+, one Nb+4.50+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to three Na1+ and two Si4+ atoms. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one Nb+4.50+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Nb+4.50+, and one Si4+ atom. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to two Na1+, one Nb+4.50+, and one Si4+ atom. In the eighth O2- site, O2- is bonded in a distorted tetrahedral geometry to three Na1+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+, one Nb+4.50+, and one Si4+ atom. In the twelfth O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Ti4+, and one Si4+ atom. F1- is bonded in a 4-coordinate geometry to three Na1+ and one Ti4+ atom.

Na₁₁TiNb₂Si₄P₂(O₁₂F)₂为源自埃森石（Esseneite）的衍生结构，结晶于三斜晶系P-1空间群，整体为三维骨架结构。该结构中存在6个不等价的Na⁺位点：
1. 第一个Na⁺位点中，Na⁺采取四配位几何构型，与5个O²⁻原子成键，Na-O键长分布范围为2.29~2.96 Å。
2. 第二个Na⁺位点中，Na⁺与7个O²⁻和1个F¹⁻原子配位，形成畸变的NaO₇F六方双锥多面体；该多面体与2个等价的NaO₇F六方双锥共角，与1个TiO₄F₂八面体共角、与2个等价的NaO₄F₂八面体共角、与1个NaO₄四面体共角、与1个PO₄四面体共角，与2个等价的NbO₆八面体共边、与1个NaO₄四面体共边、与4个SiO₄四面体共边。共角八面体的倾斜角范围为49~69°；Na-O键长分布为2.35~2.90 Å，Na-F键长为2.37 Å。
3. 第三个Na⁺位点中，Na⁺与4个O²⁻原子配位形成畸变的NaO₄四面体多面体，该多面体与1个NaO₇F六方双锥共角、与2个SiO₄四面体共角、与3个等价的PO₄四面体共角，且与1个NaO₇F六方双锥共边；Na-O键长分布为2.26~2.45 Å。
4. 第四个Na⁺位点中，Na⁺与6个O²⁻原子配位形成畸变的NaO₆八面体多面体，该多面体与2个等价的NbO₆八面体共角、与4个SiO₄四面体共角、与2个等价的TiO₄F₂八面体共边、与4个等价的NaO₄F₂八面体共边；共角八面体倾斜角为53°；Na-O键长分布为2.36~2.65 Å。
5. 第五个Na⁺位点中，Na⁺采取六配位几何构型，与6个O²⁻原子成键，Na-O键长分布为2.29~2.69 Å。
6. 第六个Na⁺位点中，Na⁺与4个O²⁻和2个等价的F¹⁻原子配位形成NaO₄F₂八面体多面体，该多面体与2个等价的NaO₇F六方双锥共角、与2个等价的NbO₆八面体共角、与2个SiO₄四面体共角、与2个等价的TiO₄F₂八面体共边、与4个NaO₄F₂八面体共边；共角八面体倾斜角范围为54~61°；Na-O键长分布为2.33~2.63 Å，Na-F键长分别为2.32 Å（较短）和2.45 Å（较长）。

Ti⁴+与4个O²⁻和2个等价的F¹⁻原子配位形成TiO₄F₂八面体多面体，该多面体与2个等价的NaO₇F六方双锥共角、与4个SiO₄四面体共角，且与6个NaO₄F₂八面体共边；Ti-O键长分为两组，较短键长为2.00 Å，较长键长为2.06 Å，Ti-F键长均为2.00 Å。

Nb⁴.⁵⁺与6个O²⁻原子配位形成畸变的NbO₆八面体多面体，该多面体与3个NaO₆八面体共角、与1个PO₄四面体共角、与4个SiO₄四面体共角，且与2个等价的NaO₇F六方双锥共边；共角八面体倾斜角范围为53~61°；Nb-O键长分布为1.81~2.27 Å。

该结构中存在2个不等价的Si⁴+位点：
1. 第一个Si⁴+位点中，Si⁴+与4个O²⁻原子配位形成SiO₄四面体多面体，该多面体与1个TiO₄F₂八面体共角、与2个NaO₆八面体共角、与2个等价的NbO₆八面体共角、与1个NaO₄四面体共角、与1个SiO₄四面体共角，且与2个等价的NaO₇F六方双锥共边；共角八面体倾斜角范围为36~62°；Si-O键长分布为1.63~1.68 Å。
2. 第二个Si⁴+位点中，Si⁴+与4个O²⁻原子配位形成SiO₄四面体多面体，该多面体与1个TiO₄F₂八面体共角、与2个NaO₆八面体共角、与2个等价的NbO₆八面体共角、与1个NaO₄四面体共角、与1个SiO₄四面体共角，且与2个等价的NaO₇F六方双锥共边；共角八面体倾斜角范围为28~69°；Si-O键长分布为1.62~1.67 Å。

P⁵+与4个O²⁻原子配位形成PO₄四面体多面体，该多面体与1个NaO₇F六方双锥共角、与1个NbO₆八面体共角，且与3个等价的NaO₄四面体共角；共角八面体倾斜角为46°；P-O键长分布为1.55~1.59 Å。

该结构中存在12个不等价的O²⁻位点：
1. 第一个O²⁻位点中，O²⁻采取二配位几何构型，与2个Na⁺、1个Nb⁴.⁵⁺和1个Si⁴+原子成键。
2. 第二个O²⁻位点中，O²⁻采取四配位几何构型，与2个Na⁺、1个Ti⁴+和1个Si⁴+原子成键。
3. 第三个O²⁻位点中，O²⁻采取单配位几何构型，与2个Na⁺、1个Nb⁴.⁵⁺和1个P⁵+原子成键。
4. 第四个O²⁻位点中，O²⁻采取五配位几何构型，与3个Na⁺和2个Si⁴+原子成键。
5. 第五个O²⁻位点中，O²⁻采取畸变矩形跷跷板型几何构型，与3个Na⁺和1个Nb⁴.⁵⁺原子成键。
6. 第六个O²⁻位点中，O²⁻采取三配位几何构型，与1个Na⁺、1个Nb⁴.⁵⁺和1个Si⁴+原子成键。
7. 第七个O²⁻位点中，O²⁻采取二配位几何构型，与2个Na⁺、1个Nb⁴.⁵⁺和1个Si⁴+原子成键。
8. 第八个O²⁻位点中，O²⁻采取畸变四面体几何构型，与3个Na⁺和1个P⁵+原子成键。
9. 第九个O²⁻位点中，O²⁻采取畸变矩形跷跷板型几何构型，与3个Na⁺和1个P⁵+原子成键。
10. 第十个O²⁻位点中，O²⁻采取畸变矩形跷跷板型几何构型，与3个Na⁺和1个P⁵+原子成键。
11. 第十一个O²⁻位点中，O²⁻采取单配位几何构型，与3个Na⁺、1个Nb⁴.⁵⁺和1个Si⁴+原子成键。
12. 第十二个O²⁻位点中，O²⁻采取四配位几何构型，与2个Na⁺、1个Ti⁴+和1个Si⁴+原子成键。

F¹⁻采取四配位几何构型，与3个Na⁺和1个Ti⁴+原子成键。