Co2Re5P12 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Re sites. In the first Re site, Re(1) is bonded to one P(4), one P(6), two equivalent P(2), and two equivalent P(5) atoms to form distorted ReP6 octahedra that share corners with two equivalent Re(3)P6 octahedra, corners with five equivalent Co(1)P6 octahedra,  a cornercorner with one P(3)Re3P tetrahedra, edges with two equivalent Re(1)P6 octahedra, and edges with two equivalent Re(2)P6 octahedra. The corner-sharing octahedral tilt angles range from 40-58°. In the second Re site, Re(2) is bonded to one P(3), one P(5), two equivalent P(1), and two equivalent P(4) atoms to form distorted ReP6 octahedra that share corners with two equivalent Re(3)P6 octahedra, corners with four equivalent Co(1)P6 octahedra,  a cornercorner with one P(6)Co2ReP tetrahedra, corners with two equivalent P(2)Re3P tetrahedra, edges with two equivalent Re(1)P6 octahedra, edges with two equivalent Re(2)P6 octahedra, and  a faceface with one Co(1)P6 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. In the third Re site, Re(3) is bonded to two equivalent P(2) and four equivalent P(3) atoms to form ReP6 octahedra that share corners with four equivalent Re(1)P6 octahedra, corners with four equivalent Re(2)P6 octahedra, corners with four equivalent P(6)Co2ReP tetrahedra, and edges with two equivalent Re(3)P6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. Co(1) is bonded to one P(4), one P(5), two equivalent P(1), and two equivalent P(6) atoms to form CoP6 octahedra that share corners with four equivalent Re(2)P6 octahedra, corners with five equivalent Re(1)P6 octahedra, corners with two equivalent P(2)Re3P tetrahedra, corners with two equivalent P(3)Re3P tetrahedra, edges with two equivalent Co(1)P6 octahedra, and  a faceface with one Re(2)P6 octahedra. The corner-sharing octahedral tilt angles range from 40-58°. There are six inequivalent P sites. In the first P site, P(6) is bonded to one Re(1), two equivalent Co(1), and one P(3) atom to form distorted PCo2ReP tetrahedra that share  a cornercorner with one Re(2)P6 octahedra, corners with two equivalent Re(3)P6 octahedra, corners with two equivalent P(6)Co2ReP tetrahedra, and corners with two equivalent P(2)Re3P tetrahedra. The corner-sharing octahedral tilt angles range from 69-71°. In the second P site, P(1) is bonded in a 5-coordinate geometry to two equivalent Re(2), two equivalent Co(1), and one P(2) atom. In the third P site, P(2) is bonded to one Re(3), two equivalent Re(1), and one P(1) atom to form distorted PRe3P tetrahedra that share corners with two equivalent Re(2)P6 octahedra, corners with two equivalent Co(1)P6 octahedra, corners with two equivalent P(6)Co2ReP tetrahedra, corners with three equivalent P(2)Re3P tetrahedra, and corners with four equivalent P(3)Re3P tetrahedra. The corner-sharing octahedral tilt angles range from 59-65°. In the fourth P site, P(3) is bonded to one Re(2), two equivalent Re(3), and one P(6) atom to form PRe3P tetrahedra that share  a cornercorner with one Re(1)P6 octahedra, corners with two equivalent Co(1)P6 octahedra, corners with four equivalent P(2)Re3P tetrahedra, corners with four equivalent P(3)Re3P tetrahedra, and  an edgeedge with one P(3)Re3P tetrahedra. The corner-sharing octahedral tilt angles range from 70-73°. In the fifth P site, P(4) is bonded in a 4-coordinate geometry to one Re(1), two equivalent Re(2), and one Co(1) atom. In the sixth P site, P(5) is bonded in a 5-coordinate geometry to one Re(2), two equivalent Re(1), one Co(1), and one P(5) atom.
Co2Re5P12 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Re sites. In the first Re site, Re(1) is bonded to one P(4), one P(6), two equivalent P(2), and two equivalent P(5) atoms to form distorted ReP6 octahedra that share corners with two equivalent Re(3)P6 octahedra, corners with five equivalent Co(1)P6 octahedra,  a cornercorner with one P(3)Re3P tetrahedra, edges with two equivalent Re(1)P6 octahedra, and edges with two equivalent Re(2)P6 octahedra. The corner-sharing octahedral tilt angles range from 40-58°. The Re(1)-P(4) bond length is 2.40 Å. The Re(1)-P(6) bond length is 2.47 Å. Both Re(1)-P(2) bond lengths are 2.48 Å. Both Re(1)-P(5) bond lengths are 2.43 Å. In the second Re site, Re(2) is bonded to one P(3), one P(5), two equivalent P(1), and two equivalent P(4) atoms to form distorted ReP6 octahedra that share corners with two equivalent Re(3)P6 octahedra, corners with four equivalent Co(1)P6 octahedra,  a cornercorner with one P(6)Co2ReP tetrahedra, corners with two equivalent P(2)Re3P tetrahedra, edges with two equivalent Re(1)P6 octahedra, edges with two equivalent Re(2)P6 octahedra, and  a faceface with one Co(1)P6 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. The Re(2)-P(3) bond length is 2.44 Å. The Re(2)-P(5) bond length is 2.58 Å. Both Re(2)-P(1) bond lengths are 2.41 Å. Both Re(2)-P(4) bond lengths are 2.35 Å. In the third Re site, Re(3) is bonded to two equivalent P(2) and four equivalent P(3) atoms to form ReP6 octahedra that share corners with four equivalent Re(1)P6 octahedra, corners with four equivalent Re(2)P6 octahedra, corners with four equivalent P(6)Co2ReP tetrahedra, and edges with two equivalent Re(3)P6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. Both Re(3)-P(2) bond lengths are 2.36 Å. All Re(3)-P(3) bond lengths are 2.41 Å. Co(1) is bonded to one P(4), one P(5), two equivalent P(1), and two equivalent P(6) atoms to form CoP6 octahedra that share corners with four equivalent Re(2)P6 octahedra, corners with five equivalent Re(1)P6 octahedra, corners with two equivalent P(2)Re3P tetrahedra, corners with two equivalent P(3)Re3P tetrahedra, edges with two equivalent Co(1)P6 octahedra, and  a faceface with one Re(2)P6 octahedra. The corner-sharing octahedral tilt angles range from 40-58°. The Co(1)-P(4) bond length is 2.15 Å. The Co(1)-P(5) bond length is 2.25 Å. Both Co(1)-P(1) bond lengths are 2.31 Å. Both Co(1)-P(6) bond lengths are 2.27 Å. There are six inequivalent P sites. In the first P site, P(6) is bonded to one Re(1), two equivalent Co(1), and one P(3) atom to form distorted PCo2ReP tetrahedra that share  a cornercorner with one Re(2)P6 octahedra, corners with two equivalent Re(3)P6 octahedra, corners with two equivalent P(6)Co2ReP tetrahedra, and corners with two equivalent P(2)Re3P tetrahedra. The corner-sharing octahedral tilt angles range from 69-71°. The P(6)-P(3) bond length is 2.30 Å. In the second P site, P(1) is bonded in a 5-coordinate geometry to two equivalent Re(2), two equivalent Co(1), and one P(2) atom. The P(1)-P(2) bond length is 2.26 Å. In the third P site, P(2) is bonded to one Re(3), two equivalent Re(1), and one P(1) atom to form distorted PRe3P tetrahedra that share corners with two equivalent Re(2)P6 octahedra, corners with two equivalent Co(1)P6 octahedra, corners with two equivalent P(6)Co2ReP tetrahedra, corners with three equivalent P(2)Re3P tetrahedra, and corners with four equivalent P(3)Re3P tetrahedra. The corner-sharing octahedral tilt angles range from 59-65°. In the fourth P site, P(3) is bonded to one Re(2), two equivalent Re(3), and one P(6) atom to form PRe3P tetrahedra that share  a cornercorner with one Re(1)P6 octahedra, corners with two equivalent Co(1)P6 octahedra, corners with four equivalent P(2)Re3P tetrahedra, corners with four equivalent P(3)Re3P tetrahedra, and  an edgeedge with one P(3)Re3P tetrahedra. The corner-sharing octahedral tilt angles range from 70-73°. In the fifth P site, P(4) is bonded in a 4-coordinate geometry to one Re(1), two equivalent Re(2), and one Co(1) atom. In the sixth P site, P(5) is bonded in a 5-coordinate geometry to one Re(2), two equivalent Re(1), one Co(1), and one P(5) atom. The P(5)-P(5) bond length is 2.30 Å.