NaYb3Ti2(SbO7)2 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent O(2), two equivalent O(5), and four equivalent O(4) atoms to form distorted NaO8 hexagonal bipyramids that share edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with four equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Sb(1)O6 octahedra. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with four equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four 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(5) 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(1)O6 octahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, edges with two equivalent Yb(1)O8 hexagonal bipyramids, and edges with four equivalent Yb(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-47°. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, and edges with four equivalent Yb(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-45°. 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(1)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 45-48°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Yb(2), one Ti(1), and one Ti(2) atom. In the second O site, O(2) is bonded to one Na(1), one Yb(1), and two equivalent Sb(1) atoms to form distorted ONaYbSb2 tetrahedra that share corners with two equivalent O(5)NaYb3 tetrahedra, corners with four equivalent O(2)NaYbSb2 tetrahedra, and  an edgeedge with one O(5)NaYb3 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Yb(1), one Yb(2), one Ti(1), and one Sb(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Yb(2), one Ti(2), and one Sb(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Yb(1), and two equivalent Yb(2) atoms to form ONaYb3 tetrahedra that share corners with two equivalent O(2)NaYbSb2 tetrahedra, corners with four equivalent O(5)NaYb3 tetrahedra, and  an edgeedge with one O(2)NaYbSb2 tetrahedra.
NaYb3Ti2(SbO7)2 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent O(2), two equivalent O(5), and four equivalent O(4) atoms to form distorted NaO8 hexagonal bipyramids that share edges with two equivalent Yb(1)O8 hexagonal bipyramids, edges with four equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Sb(1)O6 octahedra. Both Na(1)-O(2) bond lengths are 2.57 Å. Both Na(1)-O(5) bond lengths are 2.32 Å. All Na(1)-O(4) bond lengths are 2.64 Å. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with four equivalent Yb(2)O8 hexagonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Sb(1)O6 octahedra. Both Yb(1)-O(2) bond lengths are 2.48 Å. Both Yb(1)-O(5) bond lengths are 2.21 Å. All Yb(1)-O(3) bond lengths are 2.57 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(5) 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(1)O6 octahedra. Both Yb(2)-O(1) bond lengths are 2.62 Å. Both Yb(2)-O(3) bond lengths are 2.56 Å. Both Yb(2)-O(4) bond lengths are 2.51 Å. Both Yb(2)-O(5) bond lengths are 2.20 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, edges with two equivalent Yb(1)O8 hexagonal bipyramids, and edges with four equivalent Yb(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-47°. Both Ti(1)-O(1) bond lengths are 1.95 Å. All Ti(1)-O(3) bond lengths are 1.97 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, and edges with four equivalent Yb(2)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-45°. Both Ti(2)-O(1) bond lengths are 1.94 Å. All Ti(2)-O(4) bond lengths are 1.97 Å. 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(1)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 45-48°. Both Sb(1)-O(2) bond lengths are 2.01 Å. Both Sb(1)-O(3) bond lengths are 1.99 Å. Both Sb(1)-O(4) bond lengths are 1.99 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Yb(2), one Ti(1), and one Ti(2) atom. In the second O site, O(2) is bonded to one Na(1), one Yb(1), and two equivalent Sb(1) atoms to form distorted ONaYbSb2 tetrahedra that share corners with two equivalent O(5)NaYb3 tetrahedra, corners with four equivalent O(2)NaYbSb2 tetrahedra, and  an edgeedge with one O(5)NaYb3 tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Yb(1), one Yb(2), one Ti(1), and one Sb(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Yb(2), one Ti(2), and one Sb(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Yb(1), and two equivalent Yb(2) atoms to form ONaYb3 tetrahedra that share corners with two equivalent O(2)NaYbSb2 tetrahedra, corners with four equivalent O(5)NaYb3 tetrahedra, and  an edgeedge with one O(2)NaYbSb2 tetrahedra.