DOE OSTI2020
Ti4V3Mn5 crystallizes in the orthorhombic Amm2 space group. The structure is three-dimensional. there are five inequivalent Ti sites. In the first Ti site, Ti is bonded in a 12-coordinate geometry to four Ti, five V, and seven Mn atoms. There are three shorter (2.98 Å) and one longer (2.99 Å) Ti–Ti bond lengths. There are a spread of Ti–V bond distances ranging from 2.83–2.87 Å. There are a spread of Ti–Mn bond distances ranging from 2.79–2.87 Å. In the second Ti site, Ti is bonded in a 4-coordinate geometry to four Ti, four V, and eight Mn atoms. The Ti–Ti bond length is 2.90 Å. There are a spread of Ti–V bond distances ranging from 2.83–2.88 Å. There are six shorter (2.83 Å) and two longer (2.85 Å) Ti–Mn bond lengths. In the third Ti site, Ti is bonded in a 4-coordinate geometry to four Ti, four V, and eight Mn atoms. All Ti–Ti bond lengths are 2.98 Å. There are a spread of Ti–V bond distances ranging from 2.83–2.88 Å. There are six shorter (2.83 Å) and two longer (2.85 Å) Ti–Mn bond lengths. In the fourth Ti site, Ti is bonded in a 12-coordinate geometry to four Ti, five V, and seven Mn atoms. The Ti–Ti bond length is 2.98 Å. There are a spread of Ti–V bond distances ranging from 2.83–2.87 Å. There are a spread of Ti–Mn bond distances ranging from 2.79–2.87 Å. In the fifth Ti site, Ti is bonded in a 4-coordinate geometry to four Ti, four V, and eight Mn atoms. The Ti–Ti bond length is 2.90 Å. There are a spread of Ti–V bond distances ranging from 2.83–2.88 Å. There are six shorter (2.83 Å) and two longer (2.85 Å) Ti–Mn bond lengths. There are two inequivalent V sites. In the first V site, V is bonded to six Ti, one V, and five Mn atoms to form distorted VTi6Mn5V cuboctahedra that share corners with two equivalent VTi6Mn4V2 cuboctahedra, corners with ten MnTi6Mn2V4 cuboctahedra, edges with six equivalent VTi6Mn5V cuboctahedra, faces with five VTi6Mn5V cuboctahedra, and faces with fifteen MnTi6Mn2V4 cuboctahedra. The V–V bond length is 2.51 Å. There are a spread of V–Mn bond distances ranging from 2.39–2.47 Å. In the second V site, V is bonded to six Ti, two equivalent V, and four equivalent Mn atoms to form distorted VTi6Mn4V2 cuboctahedra that share corners with eight VTi6Mn5V cuboctahedra, corners with ten MnTi6Mn4V2 cuboctahedra, edges with two equivalent VTi6Mn4V2 cuboctahedra, edges with four equivalent MnTi6Mn4V2 cuboctahedra, faces with six equivalent VTi6Mn5V cuboctahedra, and faces with twelve MnTi6Mn2V4 cuboctahedra. There are two shorter (2.37 Å) and two longer (2.49 Å) V–Mn bond lengths. There are three inequivalent Mn sites. In the first Mn site, Mn is bonded to six Ti, four V, and two equivalent Mn atoms to form distorted MnTi6Mn2V4 cuboctahedra that share corners with four equivalent VTi6Mn5V cuboctahedra, corners with fourteen MnTi6Mn2V4 cuboctahedra, edges with six MnTi6Mn2V4 cuboctahedra, faces with eight MnTi6Mn2V4 cuboctahedra, and faces with ten VTi6Mn5V cuboctahedra. There are one shorter (2.36 Å) and one longer (2.50 Å) Mn–Mn bond lengths. In the second Mn site, Mn is bonded to six Ti, two equivalent V, and four equivalent Mn atoms to form distorted MnTi6Mn4V2 cuboctahedra that share corners with six VTi6Mn5V cuboctahedra, corners with twelve MnTi6Mn2V4 cuboctahedra, edges with two equivalent MnTi6Mn4V2 cuboctahedra, edges with four equivalent VTi6Mn4V2 cuboctahedra, faces with six equivalent VTi6Mn5V cuboctahedra, and faces with twelve MnTi6Mn2V4 cuboctahedra. There are two shorter (2.34 Å) and two longer (2.52 Å) Mn–Mn bond lengths. In the third Mn site, Mn is bonded to six Ti, two equivalent V, and four Mn atoms to form distorted MnTi6Mn4V2 cuboctahedra that share corners with eight VTi6Mn5V cuboctahedra, corners with ten MnTi6Mn2V4 cuboctahedra, edges with six MnTi6Mn2V4 cuboctahedra, faces with eight VTi6Mn5V cuboctahedra, and faces with ten MnTi6Mn2V4 cuboctahedra. There are one shorter (2.33 Å) and one longer (2.53 Å) Mn–Mn bond lengths.