Zr3PO2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent P(1) and three equivalent O(1) atoms to form ZrP3O3 octahedra that share corners with three equivalent Zr(2)O6 octahedra, corners with three equivalent Zr(1)P3O3 octahedra, edges with three equivalent Zr(2)O6 octahedra, and edges with nine equivalent Zr(1)P3O3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second Zr site, Zr(2) is bonded to six equivalent O(1) atoms to form ZrO6 octahedra that share corners with six equivalent Zr(1)P3O3 octahedra, edges with six equivalent Zr(2)O6 octahedra, and edges with six equivalent Zr(1)P3O3 octahedra. The corner-sharing octahedral tilt angles are 3°. P(1) is bonded to six equivalent Zr(1) atoms to form PZr6 octahedra that share corners with six equivalent O(1)Zr6 octahedra, edges with six equivalent P(1)Zr6 octahedra, and edges with six equivalent O(1)Zr6 octahedra. The corner-sharing octahedral tilt angles are 6°. O(1) is bonded to three equivalent Zr(1) and three equivalent Zr(2) atoms to form OZr6 octahedra that share corners with three equivalent P(1)Zr6 octahedra, corners with three equivalent O(1)Zr6 octahedra, edges with three equivalent P(1)Zr6 octahedra, and edges with nine equivalent O(1)Zr6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Zr3PO2 is Caswellsilverite-like structured and crystallizes in the trigonal P-3m1 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent P(1) and three equivalent O(1) atoms to form ZrP3O3 octahedra that share corners with three equivalent Zr(2)O6 octahedra, corners with three equivalent Zr(1)P3O3 octahedra, edges with three equivalent Zr(2)O6 octahedra, and edges with nine equivalent Zr(1)P3O3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All Zr(1)-P(1) bond lengths are 2.60 Å. All Zr(1)-O(1) bond lengths are 2.40 Å. In the second Zr site, Zr(2) is bonded to six equivalent O(1) atoms to form ZrO6 octahedra that share corners with six equivalent Zr(1)P3O3 octahedra, edges with six equivalent Zr(2)O6 octahedra, and edges with six equivalent Zr(1)P3O3 octahedra. The corner-sharing octahedral tilt angles are 3°. All Zr(2)-O(1) bond lengths are 2.32 Å. P(1) is bonded to six equivalent Zr(1) atoms to form PZr6 octahedra that share corners with six equivalent O(1)Zr6 octahedra, edges with six equivalent P(1)Zr6 octahedra, and edges with six equivalent O(1)Zr6 octahedra. The corner-sharing octahedral tilt angles are 6°. O(1) is bonded to three equivalent Zr(1) and three equivalent Zr(2) atoms to form OZr6 octahedra that share corners with three equivalent P(1)Zr6 octahedra, corners with three equivalent O(1)Zr6 octahedra, edges with three equivalent P(1)Zr6 octahedra, and edges with nine equivalent O(1)Zr6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.