Na2Yb2B2TeO10 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 8-coordinate geometry to one O(2), one O(4), two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms. Yb(1) is bonded to one O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share corners with two equivalent Te(1)O6 octahedra,  an edgeedge with one Te(1)O6 octahedra, and edges with three equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 47-49°. B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. Te(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form TeO6 octahedra that share corners with four equivalent Yb(1)O7 pentagonal bipyramids and edges with two equivalent Yb(1)O7 pentagonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to two equivalent Na(1), one Yb(1), and one B(1) atom. In the second O site, O(2) is bonded to one Na(1), two equivalent Yb(1), and one Te(1) atom to form distorted ONaYb2Te tetrahedra that share corners with three equivalent O(4)NaYb2B tetrahedra, corners with three equivalent O(2)NaYb2Te tetrahedra, and  an edgeedge with one O(4)NaYb2B tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one B(1), and one Te(1) atom. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Yb(1), and one B(1) atom to form distorted ONaYb2B tetrahedra that share corners with three equivalent O(2)NaYb2Te tetrahedra,  an edgeedge with one O(4)NaYb2B tetrahedra, and  an edgeedge with one O(2)NaYb2Te tetrahedra. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Yb(1), and one Te(1) atom.
Na2Yb2B2TeO10 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 8-coordinate geometry to one O(2), one O(4), two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms. The Na(1)-O(2) bond length is 2.62 Å. The Na(1)-O(4) bond length is 2.46 Å. There is one shorter (2.36 Å) and one longer (2.92 Å) Na(1)-O(1) bond length. There is one shorter (2.56 Å) and one longer (2.58 Å) Na(1)-O(3) bond length. There is one shorter (2.80 Å) and one longer (2.99 Å) Na(1)-O(5) bond length. Yb(1) is bonded to one O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share corners with two equivalent Te(1)O6 octahedra,  an edgeedge with one Te(1)O6 octahedra, and edges with three equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 47-49°. The Yb(1)-O(1) bond length is 2.32 Å. There is one shorter (2.32 Å) and one longer (2.41 Å) Yb(1)-O(2) bond length. There is one shorter (2.33 Å) and one longer (2.43 Å) Yb(1)-O(4) bond length. There is one shorter (2.36 Å) and one longer (2.53 Å) Yb(1)-O(5) bond length. B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. The B(1)-O(1) bond length is 1.36 Å. The B(1)-O(3) bond length is 1.40 Å. The B(1)-O(4) bond length is 1.37 Å. Te(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form TeO6 octahedra that share corners with four equivalent Yb(1)O7 pentagonal bipyramids and edges with two equivalent Yb(1)O7 pentagonal bipyramids. Both Te(1)-O(2) bond lengths are 1.92 Å. Both Te(1)-O(3) bond lengths are 2.05 Å. Both Te(1)-O(5) bond lengths are 1.91 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to two equivalent Na(1), one Yb(1), and one B(1) atom. In the second O site, O(2) is bonded to one Na(1), two equivalent Yb(1), and one Te(1) atom to form distorted ONaYb2Te tetrahedra that share corners with three equivalent O(4)NaYb2B tetrahedra, corners with three equivalent O(2)NaYb2Te tetrahedra, and  an edgeedge with one O(4)NaYb2B tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one B(1), and one Te(1) atom. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Yb(1), and one B(1) atom to form distorted ONaYb2B tetrahedra that share corners with three equivalent O(2)NaYb2Te tetrahedra,  an edgeedge with one O(4)NaYb2B tetrahedra, and  an edgeedge with one O(2)NaYb2Te tetrahedra. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Yb(1), and one Te(1) atom.