VMn4Se5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. V(1) is bonded to six equivalent Se(1) atoms to form VSe6 octahedra that share corners with six equivalent Mn(1)Se6 octahedra, edges with six equivalent V(1)Se6 octahedra, and edges with six equivalent Mn(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent Se(1) and three equivalent Se(2) atoms to form MnSe6 octahedra that share corners with three equivalent V(1)Se6 octahedra, corners with three equivalent Mn(2)Se6 octahedra, edges with three equivalent V(1)Se6 octahedra, edges with three equivalent Mn(2)Se6 octahedra, and edges with six equivalent Mn(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second Mn site, Mn(2) is bonded to three equivalent Se(2) and three equivalent Se(3) atoms to form a mixture of corner and edge-sharing MnSe6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent V(1) and three equivalent Mn(1) atoms to form SeMn3V3 octahedra that share corners with three equivalent Se(1)Mn3V3 octahedra, corners with three equivalent Se(2)Mn6 octahedra, edges with three equivalent Se(2)Mn6 octahedra, and edges with nine equivalent Se(1)Mn3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Se site, Se(2) is bonded to three equivalent Mn(1) and three equivalent Mn(2) atoms to form SeMn6 octahedra that share corners with three equivalent Se(1)Mn3V3 octahedra, corners with three equivalent Se(3)Mn6 octahedra, edges with three equivalent Se(1)Mn3V3 octahedra, edges with three equivalent Se(3)Mn6 octahedra, and edges with six equivalent Se(2)Mn6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the third Se site, Se(3) is bonded to six equivalent Mn(2) atoms to form a mixture of corner and edge-sharing SeMn6 octahedra. The corner-sharing octahedral tilt angles are 1°.
VMn4Se5 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. V(1) is bonded to six equivalent Se(1) atoms to form VSe6 octahedra that share corners with six equivalent Mn(1)Se6 octahedra, edges with six equivalent V(1)Se6 octahedra, and edges with six equivalent Mn(1)Se6 octahedra. The corner-sharing octahedral tilt angles are 2°. All V(1)-Se(1) bond lengths are 2.66 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent Se(1) and three equivalent Se(2) atoms to form MnSe6 octahedra that share corners with three equivalent V(1)Se6 octahedra, corners with three equivalent Mn(2)Se6 octahedra, edges with three equivalent V(1)Se6 octahedra, edges with three equivalent Mn(2)Se6 octahedra, and edges with six equivalent Mn(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. All Mn(1)-Se(1) bond lengths are 2.74 Å. All Mn(1)-Se(2) bond lengths are 2.68 Å. In the second Mn site, Mn(2) is bonded to three equivalent Se(2) and three equivalent Se(3) atoms to form a mixture of corner and edge-sharing MnSe6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. All Mn(2)-Se(2) bond lengths are 2.72 Å. All Mn(2)-Se(3) bond lengths are 2.70 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent V(1) and three equivalent Mn(1) atoms to form SeMn3V3 octahedra that share corners with three equivalent Se(1)Mn3V3 octahedra, corners with three equivalent Se(2)Mn6 octahedra, edges with three equivalent Se(2)Mn6 octahedra, and edges with nine equivalent Se(1)Mn3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Se site, Se(2) is bonded to three equivalent Mn(1) and three equivalent Mn(2) atoms to form SeMn6 octahedra that share corners with three equivalent Se(1)Mn3V3 octahedra, corners with three equivalent Se(3)Mn6 octahedra, edges with three equivalent Se(1)Mn3V3 octahedra, edges with three equivalent Se(3)Mn6 octahedra, and edges with six equivalent Se(2)Mn6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the third Se site, Se(3) is bonded to six equivalent Mn(2) atoms to form a mixture of corner and edge-sharing SeMn6 octahedra. The corner-sharing octahedral tilt angles are 1°.