Co3W9C4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent W sites. In the first W site, W(1) is bonded in a distorted T-shaped geometry to three equivalent W(2), one C(1), and two equivalent C(2) atoms. In the second W site, W(2) is bonded in a 10-coordinate geometry to two equivalent W(2), six equivalent W(1), and two equivalent Co(1) atoms. Co(1) is bonded in a 2-coordinate geometry to two equivalent W(2) and two equivalent C(2) atoms. There are two inequivalent C sites. In the first C site, C(1) is bonded to six equivalent W(1) atoms to form distorted edge-sharing CW6 pentagonal pyramids. In the second C site, C(2) is bonded to four equivalent W(1) and two equivalent Co(1) atoms to form CCo2W4 octahedra that share corners with six equivalent C(2)Co2W4 octahedra and edges with two equivalent C(1)W6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 42-43°.
Co3W9C4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent W sites. In the first W site, W(1) is bonded in a distorted T-shaped geometry to three equivalent W(2), one C(1), and two equivalent C(2) atoms. There is one shorter (2.78 Å) and two longer (2.82 Å) W(1)-W(2) bond lengths. The W(1)-C(1) bond length is 2.21 Å. Both W(1)-C(2) bond lengths are 2.12 Å. In the second W site, W(2) is bonded in a 10-coordinate geometry to two equivalent W(2), six equivalent W(1), and two equivalent Co(1) atoms. Both W(2)-W(2) bond lengths are 2.57 Å. Both W(2)-Co(1) bond lengths are 2.65 Å. Co(1) is bonded in a 2-coordinate geometry to two equivalent W(2) and two equivalent C(2) atoms. Both Co(1)-C(2) bond lengths are 2.05 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded to six equivalent W(1) atoms to form distorted edge-sharing CW6 pentagonal pyramids. In the second C site, C(2) is bonded to four equivalent W(1) and two equivalent Co(1) atoms to form CCo2W4 octahedra that share corners with six equivalent C(2)Co2W4 octahedra and edges with two equivalent C(1)W6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 42-43°.