NaYb3Ti2(SbO7)2 crystallizes in the monoclinic P2/c space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form distorted NaO8 hexagonal bipyramids that share edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Yb(3)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Yb(3)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Sb(1)O6 octahedra. In the second Yb site, Yb(2) is bonded to two equivalent O(1), two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(3)O8 hexagonal bipyramids, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. In the third Yb site, Yb(3) is bonded to two equivalent O(1), two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 42-45°. In the second Ti site, Ti(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 42-48°. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form SbO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, and edges with two equivalent Yb(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-49°. In the second Sb site, Sb(2) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form SbO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-49°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Yb(1), one Yb(2), and one Yb(3) atom to form ONaYb3 tetrahedra that share corners with two equivalent O(4)NaYbSb2 tetrahedra, corners with two equivalent O(7)Yb2TiSb tetrahedra, corners with four equivalent O(1)NaYb3 tetrahedra,  an edgeedge with one O(4)NaYbSb2 tetrahedra, and  an edgeedge with one O(7)Yb2TiSb tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Yb(1), one Ti(1), and one Sb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Yb(1), one Yb(2), one Ti(2), and one Sb(1) atom. In the fourth O site, O(4) is bonded to one Na(1), one Yb(2), one Sb(1), and one Sb(2) atom to form distorted ONaYbSb2 tetrahedra that share corners with two equivalent O(1)NaYb3 tetrahedra, corners with two equivalent O(4)NaYbSb2 tetrahedra, corners with four equivalent O(7)Yb2TiSb tetrahedra,  an edgeedge with one O(1)NaYb3 tetrahedra, and  an edgeedge with one O(4)NaYbSb2 tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Yb(1), one Yb(3), one Ti(1), and one Ti(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Yb(3), one Ti(1), and one Sb(2) atom. In the seventh O site, O(7) is bonded to one Yb(2), one Yb(3), one Ti(2), and one Sb(2) atom to form distorted OYb2TiSb tetrahedra that share corners with two equivalent O(1)NaYb3 tetrahedra, corners with two equivalent O(7)Yb2TiSb tetrahedra, corners with four equivalent O(4)NaYbSb2 tetrahedra,  an edgeedge with one O(1)NaYb3 tetrahedra, and  an edgeedge with one O(7)Yb2TiSb tetrahedra.
NaYb3Ti2(SbO7)2 crystallizes in the monoclinic P2/c space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form distorted NaO8 hexagonal bipyramids that share edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Yb(3)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. Both Na(1)-O(1) bond lengths are 2.34 Å. Both Na(1)-O(2) bond lengths are 2.67 Å. Both Na(1)-O(4) bond lengths are 2.56 Å. Both Na(1)-O(6) bond lengths are 2.63 Å. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Yb(3)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Sb(1)O6 octahedra. Both Yb(1)-O(1) bond lengths are 2.23 Å. Both Yb(1)-O(2) bond lengths are 2.53 Å. Both Yb(1)-O(3) bond lengths are 2.54 Å. Both Yb(1)-O(5) bond lengths are 2.62 Å. In the second Yb site, Yb(2) is bonded to two equivalent O(1), two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(3)O8 hexagonal bipyramids, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Sb(1)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. Both Yb(2)-O(1) bond lengths are 2.20 Å. Both Yb(2)-O(3) bond lengths are 2.60 Å. Both Yb(2)-O(4) bond lengths are 2.50 Å. Both Yb(2)-O(7) bond lengths are 2.54 Å. In the third Yb site, Yb(3) is bonded to two equivalent O(1), two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. Both Yb(3)-O(1) bond lengths are 2.18 Å. Both Yb(3)-O(5) bond lengths are 2.63 Å. Both Yb(3)-O(6) bond lengths are 2.52 Å. Both Yb(3)-O(7) bond lengths are 2.54 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 42-45°. Both Ti(1)-O(2) bond lengths are 2.01 Å. Both Ti(1)-O(5) bond lengths are 1.93 Å. Both Ti(1)-O(6) bond lengths are 1.96 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 42-48°. Both Ti(2)-O(3) bond lengths are 1.97 Å. Both Ti(2)-O(5) bond lengths are 1.93 Å. Both Ti(2)-O(7) bond lengths are 2.00 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form SbO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(1)O8 hexagonal bipyramids, and edges with two equivalent Yb(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-49°. Both Sb(1)-O(2) bond lengths are 1.97 Å. Both Sb(1)-O(3) bond lengths are 1.99 Å. Both Sb(1)-O(4) bond lengths are 2.03 Å. In the second Sb site, Sb(2) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form SbO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Yb(2)O8 hexagonal bipyramids, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 45-49°. Both Sb(2)-O(4) bond lengths are 2.00 Å. Both Sb(2)-O(6) bond lengths are 2.01 Å. Both Sb(2)-O(7) bond lengths are 1.99 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Yb(1), one Yb(2), and one Yb(3) atom to form ONaYb3 tetrahedra that share corners with two equivalent O(4)NaYbSb2 tetrahedra, corners with two equivalent O(7)Yb2TiSb tetrahedra, corners with four equivalent O(1)NaYb3 tetrahedra,  an edgeedge with one O(4)NaYbSb2 tetrahedra, and  an edgeedge with one O(7)Yb2TiSb tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Yb(1), one Ti(1), and one Sb(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Yb(1), one Yb(2), one Ti(2), and one Sb(1) atom. In the fourth O site, O(4) is bonded to one Na(1), one Yb(2), one Sb(1), and one Sb(2) atom to form distorted ONaYbSb2 tetrahedra that share corners with two equivalent O(1)NaYb3 tetrahedra, corners with two equivalent O(4)NaYbSb2 tetrahedra, corners with four equivalent O(7)Yb2TiSb tetrahedra,  an edgeedge with one O(1)NaYb3 tetrahedra, and  an edgeedge with one O(4)NaYbSb2 tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Yb(1), one Yb(3), one Ti(1), and one Ti(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Yb(3), one Ti(1), and one Sb(2) atom. In the seventh O site, O(7) is bonded to one Yb(2), one Yb(3), one Ti(2), and one Sb(2) atom to form distorted OYb2TiSb tetrahedra that share corners with two equivalent O(1)NaYb3 tetrahedra, corners with two equivalent O(7)Yb2TiSb tetrahedra, corners with four equivalent O(4)NaYbSb2 tetrahedra,  an edgeedge with one O(1)NaYb3 tetrahedra, and  an edgeedge with one O(7)Yb2TiSb tetrahedra.