Re6P13 crystallizes in the trigonal R-3 space group. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded to one P(2), one P(4), one P(5), and three equivalent P(3) atoms to form distorted ReP6 octahedra that share corners with four equivalent Re(1)P6 octahedra,  a cornercorner with one P(4)Re3P tetrahedra, corners with two equivalent P(2)Re2P2 tetrahedra, corners with two equivalent P(5)Re2P2 tetrahedra, and  an edgeedge with one Re(1)P6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second Re site, Re(2) is bonded in a 6-coordinate geometry to one P(1), one P(2), one P(3), one P(5), and two equivalent P(4) atoms. There are five inequivalent P sites. In the first P site, P(1) is bonded to three equivalent Re(2) and one P(1) atom to form PRe3P trigonal pyramids that share corners with three equivalent P(2)Re2P2 tetrahedra, corners with three equivalent P(5)Re2P2 tetrahedra, and corners with six equivalent P(4)Re3P tetrahedra. In the second P site, P(2) is bonded to one Re(1), one Re(2), and two equivalent P(2) atoms to form distorted PRe2P2 tetrahedra that share corners with two equivalent Re(1)P6 octahedra, corners with two equivalent P(2)Re2P2 tetrahedra, corners with two equivalent P(5)Re2P2 tetrahedra, corners with three equivalent P(4)Re3P tetrahedra, and  a cornercorner with one P(1)Re3P trigonal pyramid. The corner-sharing octahedral tilt angles range from 66-67°. In the third P site, P(3) is bonded in a 4-coordinate geometry to one Re(2) and three equivalent Re(1) atoms. In the fourth P site, P(4) is bonded to one Re(1), two equivalent Re(2), and one P(5) atom to form distorted PRe3P tetrahedra that share  a cornercorner with one Re(1)P6 octahedra, corners with two equivalent P(4)Re3P tetrahedra, corners with three equivalent P(2)Re2P2 tetrahedra, corners with four equivalent P(5)Re2P2 tetrahedra, and corners with two equivalent P(1)Re3P trigonal pyramids. The corner-sharing octahedral tilt angles are 62°. In the fifth P site, P(5) is bonded to one Re(1), one Re(2), one P(4), and one P(5) atom to form distorted PRe2P2 tetrahedra that share corners with two equivalent Re(1)P6 octahedra, corners with two equivalent P(2)Re2P2 tetrahedra, corners with four equivalent P(4)Re3P tetrahedra, and  a cornercorner with one P(1)Re3P trigonal pyramid. The corner-sharing octahedral tilt angles range from 69-74°.
Re6P13 crystallizes in the trigonal R-3 space group. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded to one P(2), one P(4), one P(5), and three equivalent P(3) atoms to form distorted ReP6 octahedra that share corners with four equivalent Re(1)P6 octahedra,  a cornercorner with one P(4)Re3P tetrahedra, corners with two equivalent P(2)Re2P2 tetrahedra, corners with two equivalent P(5)Re2P2 tetrahedra, and  an edgeedge with one Re(1)P6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The Re(1)-P(2) bond length is 2.35 Å. The Re(1)-P(4) bond length is 2.42 Å. The Re(1)-P(5) bond length is 2.54 Å. There are a spread of Re(1)-P(3) bond distances ranging from 2.38-2.41 Å. In the second Re site, Re(2) is bonded in a 6-coordinate geometry to one P(1), one P(2), one P(3), one P(5), and two equivalent P(4) atoms. The Re(2)-P(1) bond length is 2.72 Å. The Re(2)-P(2) bond length is 2.29 Å. The Re(2)-P(3) bond length is 2.39 Å. The Re(2)-P(5) bond length is 2.48 Å. There is one shorter (2.38 Å) and one longer (2.45 Å) Re(2)-P(4) bond length. There are five inequivalent P sites. In the first P site, P(1) is bonded to three equivalent Re(2) and one P(1) atom to form PRe3P trigonal pyramids that share corners with three equivalent P(2)Re2P2 tetrahedra, corners with three equivalent P(5)Re2P2 tetrahedra, and corners with six equivalent P(4)Re3P tetrahedra. The P(1)-P(1) bond length is 2.20 Å. In the second P site, P(2) is bonded to one Re(1), one Re(2), and two equivalent P(2) atoms to form distorted PRe2P2 tetrahedra that share corners with two equivalent Re(1)P6 octahedra, corners with two equivalent P(2)Re2P2 tetrahedra, corners with two equivalent P(5)Re2P2 tetrahedra, corners with three equivalent P(4)Re3P tetrahedra, and  a cornercorner with one P(1)Re3P trigonal pyramid. The corner-sharing octahedral tilt angles range from 66-67°. Both P(2)-P(2) bond lengths are 2.16 Å. In the third P site, P(3) is bonded in a 4-coordinate geometry to one Re(2) and three equivalent Re(1) atoms. In the fourth P site, P(4) is bonded to one Re(1), two equivalent Re(2), and one P(5) atom to form distorted PRe3P tetrahedra that share  a cornercorner with one Re(1)P6 octahedra, corners with two equivalent P(4)Re3P tetrahedra, corners with three equivalent P(2)Re2P2 tetrahedra, corners with four equivalent P(5)Re2P2 tetrahedra, and corners with two equivalent P(1)Re3P trigonal pyramids. The corner-sharing octahedral tilt angles are 62°. The P(4)-P(5) bond length is 2.27 Å. In the fifth P site, P(5) is bonded to one Re(1), one Re(2), one P(4), and one P(5) atom to form distorted PRe2P2 tetrahedra that share corners with two equivalent Re(1)P6 octahedra, corners with two equivalent P(2)Re2P2 tetrahedra, corners with four equivalent P(4)Re3P tetrahedra, and  a cornercorner with one P(1)Re3P trigonal pyramid. The corner-sharing octahedral tilt angles range from 69-74°. The P(5)-P(5) bond length is 2.30 Å.