Cr3Co2 crystallizes in the orthorhombic Cmm2 space group. There are seven inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 15-coordinate geometry to one Cr(1), one Cr(6), two equivalent Cr(3), two equivalent Cr(5), two equivalent Cr(7), one Co(5), two equivalent Co(4), and four equivalent Co(2) atoms. In the second Cr site, Cr(2) is bonded in a 15-coordinate geometry to one Cr(2), one Cr(5), one Cr(7), two equivalent Cr(4), two equivalent Cr(6), two equivalent Co(3), two equivalent Co(5), and four equivalent Co(1) atoms. In the third Cr site, Cr(3) is bonded in a 7-coordinate geometry to one Cr(1), one Cr(3), four equivalent Cr(4), one Co(5), two equivalent Co(1), and two equivalent Co(2) atoms. In the fourth Cr site, Cr(4) is bonded in a 14-coordinate geometry to one Cr(2), one Cr(4), one Cr(5), one Cr(6), one Cr(7), four equivalent Cr(3), one Co(5), two equivalent Co(1), and two equivalent Co(2) atoms. In the fifth Cr site, Cr(5) is bonded in a 7-coordinate geometry to one Cr(2), two equivalent Cr(1), two equivalent Cr(4), two equivalent Cr(7), one Co(4), two equivalent Co(1), and two equivalent Co(2) atoms. In the sixth Cr site, Cr(6) is bonded in a 7-coordinate geometry to one Cr(1), two equivalent Cr(2), two equivalent Cr(4), one Co(3), two equivalent Co(1), two equivalent Co(2), and two equivalent Co(5) atoms. In the seventh Cr site, Cr(7) is bonded in a 7-coordinate geometry to one Cr(2), two equivalent Cr(1), two equivalent Cr(4), two equivalent Cr(5), one Co(4), two equivalent Co(1), and two equivalent Co(2) atoms. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to one Cr(5), one Cr(6), one Cr(7), two equivalent Cr(2), two equivalent Cr(3), two equivalent Cr(4), one Co(1), one Co(3), and one Co(5) atom to form distorted CoCr9Co3 cuboctahedra that share corners with two equivalent Co(3)Cr6Co6 cuboctahedra, corners with two equivalent Co(4)Cr8Co4 cuboctahedra, corners with three equivalent Co(1)Cr9Co3 cuboctahedra, corners with four equivalent Co(2)Cr9Co3 cuboctahedra, edges with three equivalent Co(1)Cr9Co3 cuboctahedra,  a faceface with one Co(3)Cr6Co6 cuboctahedra, faces with two equivalent Co(1)Cr9Co3 cuboctahedra, and faces with four equivalent Co(2)Cr9Co3 cuboctahedra. In the second Co site, Co(2) is bonded to one Cr(5), one Cr(6), one Cr(7), two equivalent Cr(1), two equivalent Cr(3), two equivalent Cr(4), one Co(2), one Co(4), and one Co(5) atom to form distorted CoCr9Co3 cuboctahedra that share corners with two equivalent Co(3)Cr6Co6 cuboctahedra, corners with two equivalent Co(4)Cr8Co4 cuboctahedra, corners with three equivalent Co(2)Cr9Co3 cuboctahedra, corners with four equivalent Co(1)Cr9Co3 cuboctahedra, edges with three equivalent Co(2)Cr9Co3 cuboctahedra,  a faceface with one Co(4)Cr8Co4 cuboctahedra, faces with two equivalent Co(2)Cr9Co3 cuboctahedra, and faces with four equivalent Co(1)Cr9Co3 cuboctahedra. In the third Co site, Co(3) is bonded to two equivalent Cr(6), four equivalent Cr(2), two equivalent Co(5), and four equivalent Co(1) atoms to form distorted CoCr6Co6 cuboctahedra that share corners with eight equivalent Co(1)Cr9Co3 cuboctahedra, corners with eight equivalent Co(2)Cr9Co3 cuboctahedra, edges with two equivalent Co(3)Cr6Co6 cuboctahedra, and faces with four equivalent Co(1)Cr9Co3 cuboctahedra. In the fourth Co site, Co(4) is bonded to two equivalent Cr(5), two equivalent Cr(7), four equivalent Cr(1), and four equivalent Co(2) atoms to form CoCr8Co4 cuboctahedra that share corners with eight equivalent Co(1)Cr9Co3 cuboctahedra, corners with eight equivalent Co(2)Cr9Co3 cuboctahedra, edges with two equivalent Co(4)Cr8Co4 cuboctahedra, and faces with four equivalent Co(2)Cr9Co3 cuboctahedra. In the fifth Co site, Co(5) is bonded in a distorted linear geometry to one Cr(1), two equivalent Cr(2), two equivalent Cr(3), two equivalent Cr(4), two equivalent Cr(6), one Co(3), two equivalent Co(1), and two equivalent Co(2) atoms.
Cr3Co2 crystallizes in the orthorhombic Cmm2 space group. There are seven inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 15-coordinate geometry to one Cr(1), one Cr(6), two equivalent Cr(3), two equivalent Cr(5), two equivalent Cr(7), one Co(5), two equivalent Co(4), and four equivalent Co(2) atoms. The Cr(1)-Cr(1) bond length is 2.54 Å. The Cr(1)-Cr(6) bond length is 2.89 Å. Both Cr(1)-Cr(3) bond lengths are 2.39 Å. Both Cr(1)-Cr(5) bond lengths are 2.80 Å. Both Cr(1)-Cr(7) bond lengths are 2.78 Å. The Cr(1)-Co(5) bond length is 2.84 Å. There is one shorter (2.57 Å) and one longer (2.59 Å) Cr(1)-Co(4) bond length. All Cr(1)-Co(2) bond lengths are 2.65 Å. In the second Cr site, Cr(2) is bonded in a 15-coordinate geometry to one Cr(2), one Cr(5), one Cr(7), two equivalent Cr(4), two equivalent Cr(6), two equivalent Co(3), two equivalent Co(5), and four equivalent Co(1) atoms. The Cr(2)-Cr(2) bond length is 2.60 Å. The Cr(2)-Cr(5) bond length is 2.79 Å. The Cr(2)-Cr(7) bond length is 2.80 Å. Both Cr(2)-Cr(4) bond lengths are 2.37 Å. Both Cr(2)-Cr(6) bond lengths are 2.81 Å. There is one shorter (2.56 Å) and one longer (2.63 Å) Cr(2)-Co(3) bond length. Both Cr(2)-Co(5) bond lengths are 2.84 Å. There are two shorter (2.61 Å) and two longer (2.67 Å) Cr(2)-Co(1) bond lengths. In the third Cr site, Cr(3) is bonded in a 7-coordinate geometry to one Cr(1), one Cr(3), four equivalent Cr(4), one Co(5), two equivalent Co(1), and two equivalent Co(2) atoms. The Cr(3)-Cr(3) bond length is 2.29 Å. There are a spread of Cr(3)-Cr(4) bond distances ranging from 2.75-2.81 Å. The Cr(3)-Co(5) bond length is 2.67 Å. There is one shorter (2.41 Å) and one longer (2.46 Å) Cr(3)-Co(1) bond length. There is one shorter (2.44 Å) and one longer (2.46 Å) Cr(3)-Co(2) bond length. In the fourth Cr site, Cr(4) is bonded in a 14-coordinate geometry to one Cr(2), one Cr(4), one Cr(5), one Cr(6), one Cr(7), four equivalent Cr(3), one Co(5), two equivalent Co(1), and two equivalent Co(2) atoms. The Cr(4)-Cr(4) bond length is 2.33 Å. The Cr(4)-Cr(5) bond length is 2.74 Å. The Cr(4)-Cr(6) bond length is 2.70 Å. The Cr(4)-Cr(7) bond length is 2.74 Å. The Cr(4)-Co(5) bond length is 2.70 Å. There is one shorter (2.43 Å) and one longer (2.47 Å) Cr(4)-Co(1) bond length. There is one shorter (2.42 Å) and one longer (2.43 Å) Cr(4)-Co(2) bond length. In the fifth Cr site, Cr(5) is bonded in a 7-coordinate geometry to one Cr(2), two equivalent Cr(1), two equivalent Cr(4), two equivalent Cr(7), one Co(4), two equivalent Co(1), and two equivalent Co(2) atoms. Both Cr(5)-Cr(7) bond lengths are 2.25 Å. The Cr(5)-Co(4) bond length is 2.49 Å. Both Cr(5)-Co(1) bond lengths are 2.50 Å. Both Cr(5)-Co(2) bond lengths are 2.53 Å. In the sixth Cr site, Cr(6) is bonded in a 7-coordinate geometry to one Cr(1), two equivalent Cr(2), two equivalent Cr(4), one Co(3), two equivalent Co(1), two equivalent Co(2), and two equivalent Co(5) atoms. The Cr(6)-Co(3) bond length is 2.47 Å. Both Cr(6)-Co(1) bond lengths are 2.51 Å. Both Cr(6)-Co(2) bond lengths are 2.51 Å. There is one shorter (2.24 Å) and one longer (2.25 Å) Cr(6)-Co(5) bond length. In the seventh Cr site, Cr(7) is bonded in a 7-coordinate geometry to one Cr(2), two equivalent Cr(1), two equivalent Cr(4), two equivalent Cr(5), one Co(4), two equivalent Co(1), and two equivalent Co(2) atoms. The Cr(7)-Co(4) bond length is 2.48 Å. Both Cr(7)-Co(1) bond lengths are 2.49 Å. Both Cr(7)-Co(2) bond lengths are 2.53 Å. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to one Cr(5), one Cr(6), one Cr(7), two equivalent Cr(2), two equivalent Cr(3), two equivalent Cr(4), one Co(1), one Co(3), and one Co(5) atom to form distorted CoCr9Co3 cuboctahedra that share corners with two equivalent Co(3)Cr6Co6 cuboctahedra, corners with two equivalent Co(4)Cr8Co4 cuboctahedra, corners with three equivalent Co(1)Cr9Co3 cuboctahedra, corners with four equivalent Co(2)Cr9Co3 cuboctahedra, edges with three equivalent Co(1)Cr9Co3 cuboctahedra,  a faceface with one Co(3)Cr6Co6 cuboctahedra, faces with two equivalent Co(1)Cr9Co3 cuboctahedra, and faces with four equivalent Co(2)Cr9Co3 cuboctahedra. The Co(1)-Co(1) bond length is 2.41 Å. The Co(1)-Co(3) bond length is 2.32 Å. The Co(1)-Co(5) bond length is 2.51 Å. In the second Co site, Co(2) is bonded to one Cr(5), one Cr(6), one Cr(7), two equivalent Cr(1), two equivalent Cr(3), two equivalent Cr(4), one Co(2), one Co(4), and one Co(5) atom to form distorted CoCr9Co3 cuboctahedra that share corners with two equivalent Co(3)Cr6Co6 cuboctahedra, corners with two equivalent Co(4)Cr8Co4 cuboctahedra, corners with three equivalent Co(2)Cr9Co3 cuboctahedra, corners with four equivalent Co(1)Cr9Co3 cuboctahedra, edges with three equivalent Co(2)Cr9Co3 cuboctahedra,  a faceface with one Co(4)Cr8Co4 cuboctahedra, faces with two equivalent Co(2)Cr9Co3 cuboctahedra, and faces with four equivalent Co(1)Cr9Co3 cuboctahedra. The Co(2)-Co(2) bond length is 2.38 Å. The Co(2)-Co(4) bond length is 2.34 Å. The Co(2)-Co(5) bond length is 2.48 Å. In the third Co site, Co(3) is bonded to two equivalent Cr(6), four equivalent Cr(2), two equivalent Co(5), and four equivalent Co(1) atoms to form distorted CoCr6Co6 cuboctahedra that share corners with eight equivalent Co(1)Cr9Co3 cuboctahedra, corners with eight equivalent Co(2)Cr9Co3 cuboctahedra, edges with two equivalent Co(3)Cr6Co6 cuboctahedra, and faces with four equivalent Co(1)Cr9Co3 cuboctahedra. Both Co(3)-Co(5) bond lengths are 2.55 Å. In the fourth Co site, Co(4) is bonded to two equivalent Cr(5), two equivalent Cr(7), four equivalent Cr(1), and four equivalent Co(2) atoms to form CoCr8Co4 cuboctahedra that share corners with eight equivalent Co(1)Cr9Co3 cuboctahedra, corners with eight equivalent Co(2)Cr9Co3 cuboctahedra, edges with two equivalent Co(4)Cr8Co4 cuboctahedra, and faces with four equivalent Co(2)Cr9Co3 cuboctahedra. In the fifth Co site, Co(5) is bonded in a distorted linear geometry to one Cr(1), two equivalent Cr(2), two equivalent Cr(3), two equivalent Cr(4), two equivalent Cr(6), one Co(3), two equivalent Co(1), and two equivalent Co(2) atoms.