TiCo3(PO4)4 crystallizes in the monoclinic Pm space group. Ti(1) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form distorted TiO6 pentagonal pyramids that share corners with four equivalent Co(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted CoO6 octahedra that share corners with four equivalent Co(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. In the second Co site, Co(2) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form distorted CoO6 octahedra that share corners with four equivalent Ti(1)O6 pentagonal pyramids,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. In the third Co site, Co(3) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form distorted CoO6 octahedra that share corners with four equivalent Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one Ti(1)O6 pentagonal pyramid, and  an edgeedge with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Ti(1)O6 pentagonal pyramid, and  an edgeedge with one Ti(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 35-60°. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-56°. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Ti(1)O6 pentagonal pyramids, and  an edgeedge with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-47°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Co(2) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Co(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ti(1), one Co(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Co(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Co(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Co(3) and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Ti(1), one Co(2), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Co(1) and one P(4) atom.
TiCo3(PO4)4 crystallizes in the monoclinic Pm space group. Ti(1) is bonded to one O(1), one O(9), two equivalent O(11), and two equivalent O(5) atoms to form distorted TiO6 pentagonal pyramids that share corners with four equivalent Co(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-50°. The Ti(1)-O(1) bond length is 1.90 Å. The Ti(1)-O(9) bond length is 1.90 Å. Both Ti(1)-O(11) bond lengths are 2.02 Å. Both Ti(1)-O(5) bond lengths are 2.06 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(12), one O(4), two equivalent O(2), and two equivalent O(8) atoms to form distorted CoO6 octahedra that share corners with four equivalent Co(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. The Co(1)-O(12) bond length is 1.91 Å. The Co(1)-O(4) bond length is 1.86 Å. Both Co(1)-O(2) bond lengths are 2.14 Å. Both Co(1)-O(8) bond lengths are 2.12 Å. In the second Co site, Co(2) is bonded to one O(3), one O(7), two equivalent O(11), and two equivalent O(5) atoms to form distorted CoO6 octahedra that share corners with four equivalent Ti(1)O6 pentagonal pyramids,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The Co(2)-O(3) bond length is 1.94 Å. The Co(2)-O(7) bond length is 1.94 Å. Both Co(2)-O(11) bond lengths are 2.24 Å. Both Co(2)-O(5) bond lengths are 2.20 Å. In the third Co site, Co(3) is bonded to one O(10), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form distorted CoO6 octahedra that share corners with four equivalent Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. The Co(3)-O(10) bond length is 1.88 Å. The Co(3)-O(6) bond length is 1.92 Å. Both Co(3)-O(2) bond lengths are 2.13 Å. Both Co(3)-O(8) bond lengths are 2.10 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one Ti(1)O6 pentagonal pyramid, and  an edgeedge with one Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(10) bond length is 1.54 Å. Both P(1)-O(2) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(6), one O(9), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Ti(1)O6 pentagonal pyramid, and  an edgeedge with one Ti(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 35-60°. The P(2)-O(6) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.54 Å. Both P(2)-O(5) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, and  an edgeedge with one Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-56°. The P(3)-O(4) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.51 Å. Both P(3)-O(8) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(12), one O(3), and two equivalent O(11) atoms to form PO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Ti(1)O6 pentagonal pyramids, and  an edgeedge with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-47°. The P(4)-O(12) bond length is 1.54 Å. The P(4)-O(3) bond length is 1.51 Å. Both P(4)-O(11) bond lengths are 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Co(2) and one P(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Co(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ti(1), one Co(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Co(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Co(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Co(3) and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Ti(1), one Co(2), and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Co(1) and one P(4) atom.