TlP3 crystallizes in the trigonal R3m space group. Tl(1) is bonded to one P(2) and three equivalent P(3) atoms to form TlP4 tetrahedra that share corners with six equivalent Tl(1)P4 tetrahedra and corners with six equivalent P(1)P4 trigonal pyramids. There are three inequivalent P sites. In the first P site, P(1) is bonded to one P(3) and three equivalent P(2) atoms to form PP4 trigonal pyramids that share corners with six equivalent Tl(1)P4 tetrahedra and corners with six equivalent P(1)P4 trigonal pyramids. In the second P site, P(2) is bonded to one Tl(1) and three equivalent P(1) atoms to form distorted PTlP3 trigonal pyramids that share corners with six equivalent P(3)Tl3P tetrahedra and corners with six equivalent P(2)TlP3 trigonal pyramids. In the third P site, P(3) is bonded to three equivalent Tl(1) and one P(1) atom to form PTl3P tetrahedra that share corners with six equivalent P(3)Tl3P tetrahedra and corners with six equivalent P(2)TlP3 trigonal pyramids.
TlP3 crystallizes in the trigonal R3m space group. Tl(1) is bonded to one P(2) and three equivalent P(3) atoms to form TlP4 tetrahedra that share corners with six equivalent Tl(1)P4 tetrahedra and corners with six equivalent P(1)P4 trigonal pyramids. The Tl(1)-P(2) bond length is 2.65 Å. All Tl(1)-P(3) bond lengths are 2.65 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one P(3) and three equivalent P(2) atoms to form PP4 trigonal pyramids that share corners with six equivalent Tl(1)P4 tetrahedra and corners with six equivalent P(1)P4 trigonal pyramids. The P(1)-P(3) bond length is 2.19 Å. All P(1)-P(2) bond lengths are 2.50 Å. In the second P site, P(2) is bonded to one Tl(1) and three equivalent P(1) atoms to form distorted PTlP3 trigonal pyramids that share corners with six equivalent P(3)Tl3P tetrahedra and corners with six equivalent P(2)TlP3 trigonal pyramids. In the third P site, P(3) is bonded to three equivalent Tl(1) and one P(1) atom to form PTl3P tetrahedra that share corners with six equivalent P(3)Tl3P tetrahedra and corners with six equivalent P(2)TlP3 trigonal pyramids.