Zr4C3N is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form ZrC6 octahedra that share corners with three equivalent Zr(2)C3N3 octahedra, corners with three equivalent Zr(1)C6 octahedra, edges with three equivalent Zr(2)C3N3 octahedra, and edges with nine equivalent Zr(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second Zr site, Zr(2) is bonded to three equivalent C(1) and three equivalent N(1) atoms to form ZrC3N3 octahedra that share corners with three equivalent Zr(2)C3N3 octahedra, corners with three equivalent Zr(1)C6 octahedra, edges with three equivalent Zr(1)C6 octahedra, and edges with nine equivalent Zr(2)C3N3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. There are two inequivalent C sites. In the first C site, C(1) is bonded to three equivalent Zr(1) and three equivalent Zr(2) atoms to form CZr6 octahedra that share corners with three equivalent C(2)Zr6 octahedra, corners with three equivalent N(1)Zr6 octahedra, edges with three equivalent C(2)Zr6 octahedra, edges with three equivalent N(1)Zr6 octahedra, and edges with six equivalent C(1)Zr6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second C site, C(2) is bonded to six equivalent Zr(1) atoms to form a mixture of corner and edge-sharing CZr6 octahedra. The corner-sharing octahedral tilt angles are 2°. N(1) is bonded to six equivalent Zr(2) atoms to form NZr6 octahedra that share corners with six equivalent C(1)Zr6 octahedra, edges with six equivalent C(1)Zr6 octahedra, and edges with six equivalent N(1)Zr6 octahedra. The corner-sharing octahedral tilt angles are 3°.
Zr4C3N is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form ZrC6 octahedra that share corners with three equivalent Zr(2)C3N3 octahedra, corners with three equivalent Zr(1)C6 octahedra, edges with three equivalent Zr(2)C3N3 octahedra, and edges with nine equivalent Zr(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All Zr(1)-C(1) bond lengths are 2.39 Å. All Zr(1)-C(2) bond lengths are 2.33 Å. In the second Zr site, Zr(2) is bonded to three equivalent C(1) and three equivalent N(1) atoms to form ZrC3N3 octahedra that share corners with three equivalent Zr(2)C3N3 octahedra, corners with three equivalent Zr(1)C6 octahedra, edges with three equivalent Zr(1)C6 octahedra, and edges with nine equivalent Zr(2)C3N3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All Zr(2)-C(1) bond lengths are 2.29 Å. All Zr(2)-N(1) bond lengths are 2.36 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded to three equivalent Zr(1) and three equivalent Zr(2) atoms to form CZr6 octahedra that share corners with three equivalent C(2)Zr6 octahedra, corners with three equivalent N(1)Zr6 octahedra, edges with three equivalent C(2)Zr6 octahedra, edges with three equivalent N(1)Zr6 octahedra, and edges with six equivalent C(1)Zr6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second C site, C(2) is bonded to six equivalent Zr(1) atoms to form a mixture of corner and edge-sharing CZr6 octahedra. The corner-sharing octahedral tilt angles are 2°. N(1) is bonded to six equivalent Zr(2) atoms to form NZr6 octahedra that share corners with six equivalent C(1)Zr6 octahedra, edges with six equivalent C(1)Zr6 octahedra, and edges with six equivalent N(1)Zr6 octahedra. The corner-sharing octahedral tilt angles are 3°.