NaPrTiNbO6F crystallizes in the tetragonal P4_122 space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form distorted NaO6F2 hexagonal bipyramids that share edges with two equivalent Na(1)O6F2 hexagonal bipyramids, edges with four equivalent Pr(1)O6F2 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. Pr(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form distorted PrO6F2 hexagonal bipyramids that share edges with two equivalent Pr(1)O6F2 hexagonal bipyramids, edges with four equivalent Na(1)O6F2 hexagonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, edges with two equivalent Na(1)O6F2 hexagonal bipyramids, and edges with four equivalent Pr(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 44-48°. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, edges with two equivalent Pr(1)O6F2 hexagonal bipyramids, and edges with four equivalent Na(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-44°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Pr(1), one Ti(1), and one Nb(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Pr(1), one Ti(1), and one Nb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Pr(1) and two equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Na(1) and two equivalent Nb(1) atoms to form distorted ONa2Nb2 trigonal pyramids that share corners with two equivalent F(1)Na2Pr2 tetrahedra,  an edgeedge with one F(1)Na2Pr2 tetrahedra, and edges with two equivalent O(4)Na2Nb2 trigonal pyramids. F(1) is bonded to two equivalent Na(1) and two equivalent Pr(1) atoms to form FNa2Pr2 tetrahedra that share corners with four equivalent F(1)Na2Pr2 tetrahedra, corners with two equivalent O(4)Na2Nb2 trigonal pyramids, and  an edgeedge with one O(4)Na2Nb2 trigonal pyramid.
NaPrTiNbO6F crystallizes in the tetragonal P4_122 space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form distorted NaO6F2 hexagonal bipyramids that share edges with two equivalent Na(1)O6F2 hexagonal bipyramids, edges with four equivalent Pr(1)O6F2 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. Both Na(1)-O(1) bond lengths are 2.82 Å. Both Na(1)-O(2) bond lengths are 2.76 Å. Both Na(1)-O(4) bond lengths are 2.54 Å. Both Na(1)-F(1) bond lengths are 2.20 Å. Pr(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form distorted PrO6F2 hexagonal bipyramids that share edges with two equivalent Pr(1)O6F2 hexagonal bipyramids, edges with four equivalent Na(1)O6F2 hexagonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Pr(1)-O(1) bond lengths are 2.47 Å. Both Pr(1)-O(2) bond lengths are 2.53 Å. Both Pr(1)-O(3) bond lengths are 2.69 Å. Both Pr(1)-F(1) bond lengths are 2.34 Å. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, edges with two equivalent Na(1)O6F2 hexagonal bipyramids, and edges with four equivalent Pr(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 44-48°. Both Ti(1)-O(1) bond lengths are 2.01 Å. Both Ti(1)-O(2) bond lengths are 1.98 Å. Both Ti(1)-O(3) bond lengths are 1.97 Å. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, edges with two equivalent Pr(1)O6F2 hexagonal bipyramids, and edges with four equivalent Na(1)O6F2 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-44°. Both Nb(1)-O(1) bond lengths are 2.02 Å. Both Nb(1)-O(2) bond lengths are 2.01 Å. Both Nb(1)-O(4) bond lengths are 2.00 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Pr(1), one Ti(1), and one Nb(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Pr(1), one Ti(1), and one Nb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Pr(1) and two equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Na(1) and two equivalent Nb(1) atoms to form distorted ONa2Nb2 trigonal pyramids that share corners with two equivalent F(1)Na2Pr2 tetrahedra,  an edgeedge with one F(1)Na2Pr2 tetrahedra, and edges with two equivalent O(4)Na2Nb2 trigonal pyramids. F(1) is bonded to two equivalent Na(1) and two equivalent Pr(1) atoms to form FNa2Pr2 tetrahedra that share corners with four equivalent F(1)Na2Pr2 tetrahedra, corners with two equivalent O(4)Na2Nb2 trigonal pyramids, and  an edgeedge with one O(4)Na2Nb2 trigonal pyramid.