Zr4WC5 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(3) atoms to form ZrC6 octahedra that share corners with three equivalent Zr(2)C6 octahedra, corners with three equivalent W(1)C6 octahedra, edges with three equivalent Zr(2)C6 octahedra, edges with three equivalent W(1)C6 octahedra, and edges with six equivalent Zr(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the second Zr site, Zr(2) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form a mixture of corner and edge-sharing ZrC6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. W(1) is bonded to six equivalent C(3) atoms to form WC6 octahedra that share corners with six equivalent Zr(1)C6 octahedra, edges with six equivalent Zr(1)C6 octahedra, and edges with six equivalent W(1)C6 octahedra. The corner-sharing octahedral tilt angles are 5°. There are three 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(3)Zr3W3 octahedra, corners with three equivalent C(2)Zr6 octahedra, edges with three equivalent C(3)Zr3W3 octahedra, edges with three equivalent C(2)Zr6 octahedra, and edges with six equivalent C(1)Zr6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second C site, C(2) is bonded to six equivalent Zr(2) atoms to form a mixture of corner and edge-sharing CZr6 octahedra. The corner-sharing octahedra are not tilted. In the third C site, C(3) is bonded to three equivalent Zr(1) and three equivalent W(1) atoms to form CZr3W3 octahedra that share corners with three equivalent C(3)Zr3W3 octahedra, corners with three equivalent C(1)Zr6 octahedra, edges with three equivalent C(1)Zr6 octahedra, and edges with nine equivalent C(3)Zr3W3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
Zr4WC5 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(3) atoms to form ZrC6 octahedra that share corners with three equivalent Zr(2)C6 octahedra, corners with three equivalent W(1)C6 octahedra, edges with three equivalent Zr(2)C6 octahedra, edges with three equivalent W(1)C6 octahedra, and edges with six equivalent Zr(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. All Zr(1)-C(1) bond lengths are 2.33 Å. All Zr(1)-C(3) bond lengths are 2.37 Å. In the second Zr site, Zr(2) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form a mixture of corner and edge-sharing ZrC6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. All Zr(2)-C(1) bond lengths are 2.35 Å. All Zr(2)-C(2) bond lengths are 2.34 Å. W(1) is bonded to six equivalent C(3) atoms to form WC6 octahedra that share corners with six equivalent Zr(1)C6 octahedra, edges with six equivalent Zr(1)C6 octahedra, and edges with six equivalent W(1)C6 octahedra. The corner-sharing octahedral tilt angles are 5°. All W(1)-C(3) bond lengths are 2.23 Å. There are three 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(3)Zr3W3 octahedra, corners with three equivalent C(2)Zr6 octahedra, edges with three equivalent C(3)Zr3W3 octahedra, edges with three equivalent C(2)Zr6 octahedra, and edges with six equivalent C(1)Zr6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second C site, C(2) is bonded to six equivalent Zr(2) atoms to form a mixture of corner and edge-sharing CZr6 octahedra. The corner-sharing octahedra are not tilted. In the third C site, C(3) is bonded to three equivalent Zr(1) and three equivalent W(1) atoms to form CZr3W3 octahedra that share corners with three equivalent C(3)Zr3W3 octahedra, corners with three equivalent C(1)Zr6 octahedra, edges with three equivalent C(1)Zr6 octahedra, and edges with nine equivalent C(3)Zr3W3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.