DOE OSTI2020
Na9ZrP4O16Cl crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are nine inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a distorted rectangular see-saw-like geometry to four O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.28–2.38 Å. The Na–Cl bond length is 3.14 Å. In the second Na1+ site, Na1+ is bonded to five O2- atoms to form distorted NaO5 square pyramids that share a cornercorner with one ZrO6 octahedra, corners with three PO4 tetrahedra, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Na–O bond distances ranging from 2.28–2.54 Å. In the third Na1+ site, Na1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Na–O bond distances ranging from 2.33–2.37 Å. In the fourth Na1+ site, Na1+ is bonded in a 7-coordinate geometry to six O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.45–2.97 Å. The Na–Cl bond length is 2.85 Å. In the fifth Na1+ site, Na1+ is bonded in a 4-coordinate geometry to four O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.26–2.44 Å. The Na–Cl bond length is 3.02 Å. In the sixth Na1+ site, Na1+ is bonded in a 7-coordinate geometry to six O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.36–2.98 Å. The Na–Cl bond length is 2.80 Å. In the seventh Na1+ site, Na1+ is bonded in a 4-coordinate geometry to four O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.41–2.45 Å. The Na–Cl bond length is 2.92 Å. In the eighth Na1+ site, Na1+ is bonded in a 4-coordinate geometry to five O2- and one Cl1- atom. There are a spread of Na–O bond distances ranging from 2.40–2.77 Å. The Na–Cl bond length is 2.99 Å. In the ninth Na1+ site, Na1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Na–O bond distances ranging from 2.36–3.08 Å. Zr4+ is bonded to six O2- atoms to form ZrO6 octahedra that share a cornercorner with one NaO5 square pyramid and corners with six PO4 tetrahedra. There are a spread of Zr–O bond distances ranging from 2.08–2.13 Å. There are four inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent ZrO6 octahedra and a cornercorner with one NaO5 square pyramid. The corner-sharing octahedra tilt angles range from 27–38°. There are a spread of P–O bond distances ranging from 1.53–1.59 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one ZrO6 octahedra, a cornercorner with one NaO5 square pyramid, and an edgeedge with one NaO5 square pyramid. The corner-sharing octahedral tilt angles are 41°. There are a spread of P–O bond distances ranging from 1.54–1.61 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent ZrO6 octahedra. The corner-sharing octahedra tilt angles range from 18–38°. There are a spread of P–O bond distances ranging from 1.52–1.58 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one ZrO6 octahedra and a cornercorner with one NaO5 square pyramid. The corner-sharing octahedral tilt angles are 35°. There are a spread of P–O bond distances ranging from 1.54–1.60 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to four Na1+ and one P5+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Zr4+, and one P5+ atom. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Na1+ and one P5+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Zr4+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+, one Zr4+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one Na1+, one Zr4+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a 5-coordinate geometry to four Na1+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to three Na1+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to three Na1+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one P5+ atom. In the twelfth O2- site, O2- is bonded in a 1-coordinate geometry to five Na1+ and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a 4-coordinate geometry to four Na1+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Na1+, one Zr4+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+, one Zr4+, and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one P5+ atom. Cl1- is bonded in a 6-coordinate geometry to six Na1+ atoms.