Nb4WC5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to three equivalent C(1) and three equivalent C(3) atoms to form NbC6 octahedra that share corners with three equivalent Nb(2)C6 octahedra, corners with three equivalent W(1)C6 octahedra, edges with three equivalent Nb(2)C6 octahedra, edges with three equivalent W(1)C6 octahedra, and edges with six equivalent Nb(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Nb site, Nb(2) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form a mixture of corner and edge-sharing NbC6 octahedra. The corner-sharing octahedra are not tilted. W(1) is bonded to six equivalent C(3) atoms to form WC6 octahedra that share corners with six equivalent Nb(1)C6 octahedra, edges with six equivalent Nb(1)C6 octahedra, and edges with six equivalent W(1)C6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are three inequivalent C sites. In the first C site, C(1) is bonded to three equivalent Nb(1) and three equivalent Nb(2) atoms to form CNb6 octahedra that share corners with three equivalent C(3)Nb3W3 octahedra, corners with three equivalent C(2)Nb6 octahedra, edges with three equivalent C(3)Nb3W3 octahedra, edges with three equivalent C(2)Nb6 octahedra, and edges with six equivalent C(1)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second C site, C(2) is bonded to six equivalent Nb(2) atoms to form a mixture of corner and edge-sharing CNb6 octahedra. The corner-sharing octahedra are not tilted. In the third C site, C(3) is bonded to three equivalent Nb(1) and three equivalent W(1) atoms to form CNb3W3 octahedra that share corners with three equivalent C(3)Nb3W3 octahedra, corners with three equivalent C(1)Nb6 octahedra, edges with three equivalent C(1)Nb6 octahedra, and edges with nine equivalent C(3)Nb3W3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Nb4WC5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to three equivalent C(1) and three equivalent C(3) atoms to form NbC6 octahedra that share corners with three equivalent Nb(2)C6 octahedra, corners with three equivalent W(1)C6 octahedra, edges with three equivalent Nb(2)C6 octahedra, edges with three equivalent W(1)C6 octahedra, and edges with six equivalent Nb(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. All Nb(1)-C(1) bond lengths are 2.24 Å. All Nb(1)-C(3) bond lengths are 2.26 Å. In the second Nb site, Nb(2) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form a mixture of corner and edge-sharing NbC6 octahedra. The corner-sharing octahedra are not tilted. All Nb(2)-C(1) bond lengths are 2.25 Å. All Nb(2)-C(2) bond lengths are 2.24 Å. W(1) is bonded to six equivalent C(3) atoms to form WC6 octahedra that share corners with six equivalent Nb(1)C6 octahedra, edges with six equivalent Nb(1)C6 octahedra, and edges with six equivalent W(1)C6 octahedra. The corner-sharing octahedral tilt angles are 2°. All W(1)-C(3) bond lengths are 2.20 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded to three equivalent Nb(1) and three equivalent Nb(2) atoms to form CNb6 octahedra that share corners with three equivalent C(3)Nb3W3 octahedra, corners with three equivalent C(2)Nb6 octahedra, edges with three equivalent C(3)Nb3W3 octahedra, edges with three equivalent C(2)Nb6 octahedra, and edges with six equivalent C(1)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second C site, C(2) is bonded to six equivalent Nb(2) atoms to form a mixture of corner and edge-sharing CNb6 octahedra. The corner-sharing octahedra are not tilted. In the third C site, C(3) is bonded to three equivalent Nb(1) and three equivalent W(1) atoms to form CNb3W3 octahedra that share corners with three equivalent C(3)Nb3W3 octahedra, corners with three equivalent C(1)Nb6 octahedra, edges with three equivalent C(1)Nb6 octahedra, and edges with nine equivalent C(3)Nb3W3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.