ZrNb2VC4 is alpha Po-derived structured and crystallizes in the trigonal R3m space group. Zr(1) is bonded to three equivalent C(1) and three equivalent C(4) atoms to form ZrC6 octahedra that share corners with three equivalent Nb(1)C6 octahedra, corners with three equivalent V(1)C6 octahedra, edges with three equivalent Nb(1)C6 octahedra, edges with three equivalent V(1)C6 octahedra, and edges with six equivalent Zr(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form NbC6 octahedra that share corners with three equivalent Zr(1)C6 octahedra, corners with three equivalent Nb(2)C6 octahedra, edges with three equivalent Zr(1)C6 octahedra, edges with three equivalent Nb(2)C6 octahedra, and edges with six equivalent Nb(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second Nb site, Nb(2) is bonded to three equivalent C(2) and three equivalent C(3) atoms to form NbC6 octahedra that share corners with three equivalent Nb(1)C6 octahedra, corners with three equivalent V(1)C6 octahedra, edges with three equivalent Nb(1)C6 octahedra, edges with three equivalent V(1)C6 octahedra, and edges with six equivalent Nb(2)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. V(1) is bonded to three equivalent C(3) and three equivalent C(4) atoms to form VC6 octahedra that share corners with three equivalent Zr(1)C6 octahedra, corners with three equivalent Nb(2)C6 octahedra, edges with three equivalent Zr(1)C6 octahedra, edges with three equivalent Nb(2)C6 octahedra, and edges with six equivalent V(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are four inequivalent C sites. In the first C site, C(1) is bonded to three equivalent Zr(1) and three equivalent Nb(1) atoms to form CZr3Nb3 octahedra that share corners with three equivalent C(2)Nb6 octahedra, corners with three equivalent C(4)Zr3V3 octahedra, edges with three equivalent C(2)Nb6 octahedra, edges with three equivalent C(4)Zr3V3 octahedra, and edges with six equivalent C(1)Zr3Nb3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second C site, C(2) 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)Nb3V3 octahedra, corners with three equivalent C(1)Zr3Nb3 octahedra, edges with three equivalent C(3)Nb3V3 octahedra, edges with three equivalent C(1)Zr3Nb3 octahedra, and edges with six equivalent C(2)Nb6 octahedra. The corner-sharing octahedra are not tilted. In the third C site, C(3) is bonded to three equivalent Nb(2) and three equivalent V(1) atoms to form CNb3V3 octahedra that share corners with three equivalent C(2)Nb6 octahedra, corners with three equivalent C(4)Zr3V3 octahedra, edges with three equivalent C(2)Nb6 octahedra, edges with three equivalent C(4)Zr3V3 octahedra, and edges with six equivalent C(3)Nb3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth C site, C(4) is bonded to three equivalent Zr(1) and three equivalent V(1) atoms to form CZr3V3 octahedra that share corners with three equivalent C(3)Nb3V3 octahedra, corners with three equivalent C(1)Zr3Nb3 octahedra, edges with three equivalent C(3)Nb3V3 octahedra, edges with three equivalent C(1)Zr3Nb3 octahedra, and edges with six equivalent C(4)Zr3V3 octahedra. The corner-sharing octahedral tilt angles are 1°.
ZrNb2VC4 is alpha Po-derived structured and crystallizes in the trigonal R3m space group. Zr(1) is bonded to three equivalent C(1) and three equivalent C(4) atoms to form ZrC6 octahedra that share corners with three equivalent Nb(1)C6 octahedra, corners with three equivalent V(1)C6 octahedra, edges with three equivalent Nb(1)C6 octahedra, edges with three equivalent V(1)C6 octahedra, and edges with six equivalent Zr(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. All Zr(1)-C(1) bond lengths are 2.32 Å. All Zr(1)-C(4) bond lengths are 2.31 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to three equivalent C(1) and three equivalent C(2) atoms to form NbC6 octahedra that share corners with three equivalent Zr(1)C6 octahedra, corners with three equivalent Nb(2)C6 octahedra, edges with three equivalent Zr(1)C6 octahedra, edges with three equivalent Nb(2)C6 octahedra, and edges with six equivalent Nb(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. All Nb(1)-C(1) bond lengths are 2.24 Å. All Nb(1)-C(2) bond lengths are 2.25 Å. In the second Nb site, Nb(2) is bonded to three equivalent C(2) and three equivalent C(3) atoms to form NbC6 octahedra that share corners with three equivalent Nb(1)C6 octahedra, corners with three equivalent V(1)C6 octahedra, edges with three equivalent Nb(1)C6 octahedra, edges with three equivalent V(1)C6 octahedra, and edges with six equivalent Nb(2)C6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. All Nb(2)-C(2) bond lengths are 2.25 Å. All Nb(2)-C(3) bond lengths are 2.24 Å. V(1) is bonded to three equivalent C(3) and three equivalent C(4) atoms to form VC6 octahedra that share corners with three equivalent Zr(1)C6 octahedra, corners with three equivalent Nb(2)C6 octahedra, edges with three equivalent Zr(1)C6 octahedra, edges with three equivalent Nb(2)C6 octahedra, and edges with six equivalent V(1)C6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. All V(1)-C(3) bond lengths are 2.15 Å. All V(1)-C(4) bond lengths are 2.16 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded to three equivalent Zr(1) and three equivalent Nb(1) atoms to form CZr3Nb3 octahedra that share corners with three equivalent C(2)Nb6 octahedra, corners with three equivalent C(4)Zr3V3 octahedra, edges with three equivalent C(2)Nb6 octahedra, edges with three equivalent C(4)Zr3V3 octahedra, and edges with six equivalent C(1)Zr3Nb3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second C site, C(2) 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)Nb3V3 octahedra, corners with three equivalent C(1)Zr3Nb3 octahedra, edges with three equivalent C(3)Nb3V3 octahedra, edges with three equivalent C(1)Zr3Nb3 octahedra, and edges with six equivalent C(2)Nb6 octahedra. The corner-sharing octahedra are not tilted. In the third C site, C(3) is bonded to three equivalent Nb(2) and three equivalent V(1) atoms to form CNb3V3 octahedra that share corners with three equivalent C(2)Nb6 octahedra, corners with three equivalent C(4)Zr3V3 octahedra, edges with three equivalent C(2)Nb6 octahedra, edges with three equivalent C(4)Zr3V3 octahedra, and edges with six equivalent C(3)Nb3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth C site, C(4) is bonded to three equivalent Zr(1) and three equivalent V(1) atoms to form CZr3V3 octahedra that share corners with three equivalent C(3)Nb3V3 octahedra, corners with three equivalent C(1)Zr3Nb3 octahedra, edges with three equivalent C(3)Nb3V3 octahedra, edges with three equivalent C(1)Zr3Nb3 octahedra, and edges with six equivalent C(4)Zr3V3 octahedra. The corner-sharing octahedral tilt angles are 1°.