Ti7P4 crystallizes in the monoclinic C2/m space group. There are eight inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a distorted square co-planar geometry to two equivalent P(1) and two equivalent P(4) atoms. In the second Ti site, Ti(2) is bonded in a distorted square co-planar geometry to two equivalent P(2) and two equivalent P(3) atoms. In the third Ti site, Ti(3) is bonded in a 4-coordinate geometry to one P(2), two equivalent P(1), and two equivalent P(4) atoms. In the fourth Ti site, Ti(4) is bonded in a 4-coordinate geometry to one P(1), one P(3), and two equivalent P(2) atoms. In the fifth Ti site, Ti(5) is bonded to one P(4), two equivalent P(1), and two equivalent P(3) atoms to form a mixture of distorted corner, face, and edge-sharing TiP5 trigonal bipyramids. In the sixth Ti site, Ti(6) is bonded in a 5-coordinate geometry to two equivalent P(4) and three equivalent P(1) atoms. In the seventh Ti site, Ti(7) is bonded to one P(4), two equivalent P(2), and two equivalent P(3) atoms to form a mixture of distorted corner, face, and edge-sharing TiP5 trigonal bipyramids. In the eighth Ti site, Ti(8) is bonded in a 5-coordinate geometry to two equivalent P(3) and three equivalent P(2) atoms. There are four inequivalent P sites. In the first P site, P(3) is bonded in a 8-coordinate geometry to one Ti(2), one Ti(4), two equivalent Ti(5), two equivalent Ti(7), and two equivalent Ti(8) atoms. In the second P site, P(4) is bonded to one Ti(1), one Ti(5), one Ti(7), two equivalent Ti(3), and two equivalent Ti(6) atoms to form a mixture of distorted corner and edge-sharing PTi7 pentagonal bipyramids. In the third P site, P(1) is bonded in a 9-coordinate geometry to one Ti(1), one Ti(4), two equivalent Ti(3), two equivalent Ti(5), and three equivalent Ti(6) atoms. In the fourth P site, P(2) is bonded in a 9-coordinate geometry to one Ti(2), one Ti(3), two equivalent Ti(4), two equivalent Ti(7), and three equivalent Ti(8) atoms.
Ti7P4 crystallizes in the monoclinic C2/m space group. There are eight inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a distorted square co-planar geometry to two equivalent P(1) and two equivalent P(4) atoms. Both Ti(1)-P(1) bond lengths are 2.65 Å. Both Ti(1)-P(4) bond lengths are 2.44 Å. In the second Ti site, Ti(2) is bonded in a distorted square co-planar geometry to two equivalent P(2) and two equivalent P(3) atoms. Both Ti(2)-P(2) bond lengths are 2.61 Å. Both Ti(2)-P(3) bond lengths are 2.48 Å. In the third Ti site, Ti(3) is bonded in a 4-coordinate geometry to one P(2), two equivalent P(1), and two equivalent P(4) atoms. The Ti(3)-P(2) bond length is 2.98 Å. Both Ti(3)-P(1) bond lengths are 2.59 Å. Both Ti(3)-P(4) bond lengths are 2.54 Å. In the fourth Ti site, Ti(4) is bonded in a 4-coordinate geometry to one P(1), one P(3), and two equivalent P(2) atoms. The Ti(4)-P(1) bond length is 2.64 Å. The Ti(4)-P(3) bond length is 2.45 Å. Both Ti(4)-P(2) bond lengths are 2.45 Å. In the fifth Ti site, Ti(5) is bonded to one P(4), two equivalent P(1), and two equivalent P(3) atoms to form a mixture of distorted corner, face, and edge-sharing TiP5 trigonal bipyramids. The Ti(5)-P(4) bond length is 2.41 Å. Both Ti(5)-P(1) bond lengths are 2.52 Å. Both Ti(5)-P(3) bond lengths are 2.55 Å. In the sixth Ti site, Ti(6) is bonded in a 5-coordinate geometry to two equivalent P(4) and three equivalent P(1) atoms. Both Ti(6)-P(4) bond lengths are 2.53 Å. There are two shorter (2.53 Å) and one longer (2.82 Å) Ti(6)-P(1) bond length. In the seventh Ti site, Ti(7) is bonded to one P(4), two equivalent P(2), and two equivalent P(3) atoms to form a mixture of distorted corner, face, and edge-sharing TiP5 trigonal bipyramids. The Ti(7)-P(4) bond length is 2.47 Å. Both Ti(7)-P(2) bond lengths are 2.53 Å. Both Ti(7)-P(3) bond lengths are 2.53 Å. In the eighth Ti site, Ti(8) is bonded in a 5-coordinate geometry to two equivalent P(3) and three equivalent P(2) atoms. Both Ti(8)-P(3) bond lengths are 2.54 Å. There are two shorter (2.58 Å) and one longer (2.74 Å) Ti(8)-P(2) bond length. There are four inequivalent P sites. In the first P site, P(3) is bonded in a 8-coordinate geometry to one Ti(2), one Ti(4), two equivalent Ti(5), two equivalent Ti(7), and two equivalent Ti(8) atoms. In the second P site, P(4) is bonded to one Ti(1), one Ti(5), one Ti(7), two equivalent Ti(3), and two equivalent Ti(6) atoms to form a mixture of distorted corner and edge-sharing PTi7 pentagonal bipyramids. In the third P site, P(1) is bonded in a 9-coordinate geometry to one Ti(1), one Ti(4), two equivalent Ti(3), two equivalent Ti(5), and three equivalent Ti(6) atoms. In the fourth P site, P(2) is bonded in a 9-coordinate geometry to one Ti(2), one Ti(3), two equivalent Ti(4), two equivalent Ti(7), and three equivalent Ti(8) atoms.