Mn3(W5C2)2 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent W sites. In the first W site, W(1) is bonded in a 2-coordinate geometry to two equivalent W(3) and two equivalent Mn(1) atoms. In the second W site, W(2) is bonded in a distorted bent 150 degrees geometry to one W(3) and two equivalent C(1) atoms. In the third W site, W(3) is bonded to six equivalent W(1) and six equivalent W(2) atoms to form WW12 cuboctahedra that share edges with six equivalent C(1)Mn2W4 octahedra and faces with two equivalent W(3)W12 cuboctahedra. Mn(1) is bonded in a 3-coordinate geometry to two equivalent W(1), one C(2), and two equivalent C(1) atoms. There are two inequivalent C sites. In the first C site, C(2) is bonded in a trigonal planar geometry to three equivalent Mn(1) atoms. In the second C site, C(1) is bonded to four equivalent W(2) and two equivalent Mn(1) atoms to form CMn2W4 octahedra that share corners with six equivalent C(1)Mn2W4 octahedra and edges with two equivalent W(3)W12 cuboctahedra. The corner-sharing octahedral tilt angles range from 26-41°.
Mn3(W5C2)2 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent W sites. In the first W site, W(1) is bonded in a 2-coordinate geometry to two equivalent W(3) and two equivalent Mn(1) atoms. Both W(1)-W(3) bond lengths are 2.59 Å. Both W(1)-Mn(1) bond lengths are 2.61 Å. In the second W site, W(2) is bonded in a distorted bent 150 degrees geometry to one W(3) and two equivalent C(1) atoms. The W(2)-W(3) bond length is 2.94 Å. Both W(2)-C(1) bond lengths are 2.13 Å. In the third W site, W(3) is bonded to six equivalent W(1) and six equivalent W(2) atoms to form WW12 cuboctahedra that share edges with six equivalent C(1)Mn2W4 octahedra and faces with two equivalent W(3)W12 cuboctahedra. Mn(1) is bonded in a 3-coordinate geometry to two equivalent W(1), one C(2), and two equivalent C(1) atoms. The Mn(1)-C(2) bond length is 1.85 Å. Both Mn(1)-C(1) bond lengths are 2.06 Å. There are two inequivalent C sites. In the first C site, C(2) is bonded in a trigonal planar geometry to three equivalent Mn(1) atoms. In the second C site, C(1) is bonded to four equivalent W(2) and two equivalent Mn(1) atoms to form CMn2W4 octahedra that share corners with six equivalent C(1)Mn2W4 octahedra and edges with two equivalent W(3)W12 cuboctahedra. The corner-sharing octahedral tilt angles range from 26-41°.