Ti3(PO4)4N2 crystallizes in the monoclinic P2_1 space group. The structure consists of four ammonia atoms inside a Ti3(PO4)4 framework. In the Ti3(PO4)4 framework, there are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a rectangular see-saw-like geometry to one O(13), one O(2), one O(5), and one O(9) atom. In the second Ti site, Ti(2) is bonded to one O(1), one O(10), one O(11), one O(14), and one O(4) atom to form distorted TiO5 trigonal bipyramids that share  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the third Ti site, Ti(3) is bonded to one O(15), one O(16), one O(3), one O(6), and one O(7) atom to form TiO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(3)O5 trigonal bipyramid and corners with two equivalent Ti(2)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ti(3)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ti(2)O5 trigonal bipyramids. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(16) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(2)O5 trigonal bipyramid and corners with two equivalent Ti(3)O5 trigonal bipyramids. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(2) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one Ti(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Ti(3) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(4) atom.
Ti3(PO4)4N2 crystallizes in the monoclinic P2_1 space group. The structure consists of four ammonia atoms inside a Ti3(PO4)4 framework. In the Ti3(PO4)4 framework, there are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a rectangular see-saw-like geometry to one O(13), one O(2), one O(5), and one O(9) atom. The Ti(1)-O(13) bond length is 1.92 Å. The Ti(1)-O(2) bond length is 1.90 Å. The Ti(1)-O(5) bond length is 1.85 Å. The Ti(1)-O(9) bond length is 1.85 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(10), one O(11), one O(14), and one O(4) atom to form distorted TiO5 trigonal bipyramids that share  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Ti(2)-O(1) bond length is 1.98 Å. The Ti(2)-O(10) bond length is 1.86 Å. The Ti(2)-O(11) bond length is 1.86 Å. The Ti(2)-O(14) bond length is 1.85 Å. The Ti(2)-O(4) bond length is 1.97 Å. In the third Ti site, Ti(3) is bonded to one O(15), one O(16), one O(3), one O(6), and one O(7) atom to form TiO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Ti(3)-O(15) bond length is 1.97 Å. The Ti(3)-O(16) bond length is 1.96 Å. The Ti(3)-O(3) bond length is 1.85 Å. The Ti(3)-O(6) bond length is 1.87 Å. The Ti(3)-O(7) bond length is 1.87 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(3)O5 trigonal bipyramid and corners with two equivalent Ti(2)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ti(3)O5 trigonal bipyramids. The P(2)-O(5) bond length is 1.61 Å. The P(2)-O(6) bond length is 1.58 Å. The P(2)-O(7) bond length is 1.59 Å. The P(2)-O(8) bond length is 1.47 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ti(2)O5 trigonal bipyramids. The P(3)-O(10) bond length is 1.58 Å. The P(3)-O(11) bond length is 1.58 Å. The P(3)-O(12) bond length is 1.47 Å. The P(3)-O(9) bond length is 1.62 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(16) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(2)O5 trigonal bipyramid and corners with two equivalent Ti(3)O5 trigonal bipyramids. The P(4)-O(13) bond length is 1.57 Å. The P(4)-O(14) bond length is 1.56 Å. The P(4)-O(15) bond length is 1.54 Å. The P(4)-O(16) bond length is 1.52 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(2) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one Ti(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Ti(3) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(4) atom.