Li2Yb5O4(BO3)3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one O(8) and two equivalent O(1) atoms. In the second Li site, Li(2) is bonded to one O(10), one O(7), and three equivalent O(13) atoms to form a mixture of corner and edge-sharing LiO5 trigonal bipyramids. There are five inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one O(4), one O(6), one O(9), two equivalent O(3), and two equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share corners with two equivalent Yb(3)O6 octahedra,  an edgeedge with one Yb(5)O7 pentagonal bipyramid, and edges with two equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 57°. In the second Yb site, Yb(2) is bonded in a 7-coordinate geometry to one O(13), one O(3), two equivalent O(10), and three equivalent O(9) atoms. In the third Yb site, Yb(3) is bonded to one O(1), one O(12), two equivalent O(2), and two equivalent O(6) atoms to form distorted YbO6 octahedra that share corners with two equivalent Yb(1)O7 pentagonal bipyramids, edges with two equivalent Yb(3)O6 octahedra, and edges with two equivalent Yb(5)O7 pentagonal bipyramids. In the fourth Yb site, Yb(4) is bonded in a 7-coordinate geometry to one O(11), one O(3), one O(7), two equivalent O(4), and two equivalent O(8) atoms. In the fifth Yb site, Yb(5) is bonded to one O(4), one O(6), two equivalent O(12), and three equivalent O(11) atoms to form distorted YbO7 pentagonal bipyramids that share edges with two equivalent Yb(3)O6 octahedra,  an edgeedge with one Yb(1)O7 pentagonal bipyramid, and edges with four equivalent Yb(5)O7 pentagonal bipyramids. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(13), one O(3), and one O(7) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(5) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(12), one O(2), and one O(8) atom. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Yb(3), and one B(2) atom to form distorted OLi2YbB tetrahedra that share corners with two equivalent O(1)Li2YbB tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, and corners with two equivalent O(6)Yb4 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Yb(3) and one B(3) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Yb(2), one Yb(4), two equivalent Yb(1), and one B(1) atom. In the fourth O site, O(4) is bonded to one Yb(1), one Yb(5), and two equivalent Yb(4) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(11)Yb4 tetrahedra,  a cornercorner with one O(9)Yb4 tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra,  an edgeedge with one O(8)LiYb2B tetrahedra,  an edgeedge with one O(6)Yb4 tetrahedra, and edges with two equivalent O(11)Yb4 tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Yb(1) and one B(2) atom. In the sixth O site, O(6) is bonded to one Yb(1), one Yb(5), and two equivalent Yb(3) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(9)Yb4 tetrahedra, corners with two equivalent O(1)Li2YbB tetrahedra, corners with two equivalent O(6)Yb4 tetrahedra, corners with three equivalent O(11)Yb4 tetrahedra, and  an edgeedge with one O(4)Yb4 tetrahedra. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(2), one Yb(4), and one B(1) atom. In the eighth O site, O(8) is bonded to one Li(1), two equivalent Yb(4), and one B(3) atom to form distorted OLiYb2B tetrahedra that share corners with two equivalent O(1)Li2YbB tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, corners with two equivalent O(11)Yb4 tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra, and  an edgeedge with one O(4)Yb4 tetrahedra. In the ninth O site, O(9) is bonded to one Yb(1) and three equivalent Yb(2) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(4)Yb4 tetrahedra,  a cornercorner with one O(6)Yb4 tetrahedra, corners with two equivalent O(9)Yb4 tetrahedra, corners with three equivalent O(13)Li3YbB trigonal bipyramids, and edges with two equivalent O(9)Yb4 tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Yb(2), and one B(2) atom. In the eleventh O site, O(11) is bonded to one Yb(4) and three equivalent Yb(5) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(4)Yb4 tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, corners with two equivalent O(11)Yb4 tetrahedra, corners with three equivalent O(6)Yb4 tetrahedra, edges with two equivalent O(11)Yb4 tetrahedra, and edges with two equivalent O(4)Yb4 tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Yb(3), two equivalent Yb(5), and one B(3) atom. In the thirteenth O site, O(13) is bonded to three equivalent Li(2), one Yb(2), and one B(1) atom to form distorted OLi3YbB trigonal bipyramids that share corners with three equivalent O(9)Yb4 tetrahedra, corners with two equivalent O(13)Li3YbB trigonal bipyramids, and edges with two equivalent O(13)Li3YbB trigonal bipyramids.
Li2Yb5O4(BO3)3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one O(8) and two equivalent O(1) atoms. The Li(1)-O(8) bond length is 1.94 Å. Both Li(1)-O(1) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded to one O(10), one O(7), and three equivalent O(13) atoms to form a mixture of corner and edge-sharing LiO5 trigonal bipyramids. The Li(2)-O(10) bond length is 2.10 Å. The Li(2)-O(7) bond length is 2.09 Å. There are two shorter (2.10 Å) and one longer (2.22 Å) Li(2)-O(13) bond length. There are five inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one O(4), one O(6), one O(9), two equivalent O(3), and two equivalent O(5) atoms to form distorted YbO7 pentagonal bipyramids that share corners with two equivalent Yb(3)O6 octahedra,  an edgeedge with one Yb(5)O7 pentagonal bipyramid, and edges with two equivalent Yb(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 57°. The Yb(1)-O(4) bond length is 2.31 Å. The Yb(1)-O(6) bond length is 2.34 Å. The Yb(1)-O(9) bond length is 2.37 Å. Both Yb(1)-O(3) bond lengths are 2.49 Å. Both Yb(1)-O(5) bond lengths are 2.34 Å. In the second Yb site, Yb(2) is bonded in a 7-coordinate geometry to one O(13), one O(3), two equivalent O(10), and three equivalent O(9) atoms. The Yb(2)-O(13) bond length is 2.34 Å. The Yb(2)-O(3) bond length is 2.50 Å. Both Yb(2)-O(10) bond lengths are 2.33 Å. There is one shorter (2.28 Å) and two longer (2.32 Å) Yb(2)-O(9) bond lengths. In the third Yb site, Yb(3) is bonded to one O(1), one O(12), two equivalent O(2), and two equivalent O(6) atoms to form distorted YbO6 octahedra that share corners with two equivalent Yb(1)O7 pentagonal bipyramids, edges with two equivalent Yb(3)O6 octahedra, and edges with two equivalent Yb(5)O7 pentagonal bipyramids. The Yb(3)-O(1) bond length is 2.32 Å. The Yb(3)-O(12) bond length is 2.39 Å. Both Yb(3)-O(2) bond lengths are 2.35 Å. Both Yb(3)-O(6) bond lengths are 2.32 Å. In the fourth Yb site, Yb(4) is bonded in a 7-coordinate geometry to one O(11), one O(3), one O(7), two equivalent O(4), and two equivalent O(8) atoms. The Yb(4)-O(11) bond length is 2.28 Å. The Yb(4)-O(3) bond length is 2.73 Å. The Yb(4)-O(7) bond length is 2.27 Å. Both Yb(4)-O(4) bond lengths are 2.29 Å. Both Yb(4)-O(8) bond lengths are 2.36 Å. In the fifth Yb site, Yb(5) is bonded to one O(4), one O(6), two equivalent O(12), and three equivalent O(11) atoms to form distorted YbO7 pentagonal bipyramids that share edges with two equivalent Yb(3)O6 octahedra,  an edgeedge with one Yb(1)O7 pentagonal bipyramid, and edges with four equivalent Yb(5)O7 pentagonal bipyramids. The Yb(5)-O(4) bond length is 2.29 Å. The Yb(5)-O(6) bond length is 2.25 Å. Both Yb(5)-O(12) bond lengths are 2.35 Å. All Yb(5)-O(11) bond lengths are 2.33 Å. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(13), one O(3), and one O(7) atom. The B(1)-O(13) bond length is 1.39 Å. The B(1)-O(3) bond length is 1.41 Å. The B(1)-O(7) bond length is 1.37 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(5) atom. The B(2)-O(1) bond length is 1.37 Å. The B(2)-O(10) bond length is 1.37 Å. The B(2)-O(5) bond length is 1.39 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(12), one O(2), and one O(8) atom. The B(3)-O(12) bond length is 1.38 Å. The B(3)-O(2) bond length is 1.38 Å. The B(3)-O(8) bond length is 1.38 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Yb(3), and one B(2) atom to form distorted OLi2YbB tetrahedra that share corners with two equivalent O(1)Li2YbB tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, and corners with two equivalent O(6)Yb4 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Yb(3) and one B(3) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Yb(2), one Yb(4), two equivalent Yb(1), and one B(1) atom. In the fourth O site, O(4) is bonded to one Yb(1), one Yb(5), and two equivalent Yb(4) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(11)Yb4 tetrahedra,  a cornercorner with one O(9)Yb4 tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra,  an edgeedge with one O(8)LiYb2B tetrahedra,  an edgeedge with one O(6)Yb4 tetrahedra, and edges with two equivalent O(11)Yb4 tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Yb(1) and one B(2) atom. In the sixth O site, O(6) is bonded to one Yb(1), one Yb(5), and two equivalent Yb(3) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(9)Yb4 tetrahedra, corners with two equivalent O(1)Li2YbB tetrahedra, corners with two equivalent O(6)Yb4 tetrahedra, corners with three equivalent O(11)Yb4 tetrahedra, and  an edgeedge with one O(4)Yb4 tetrahedra. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(2), one Yb(4), and one B(1) atom. In the eighth O site, O(8) is bonded to one Li(1), two equivalent Yb(4), and one B(3) atom to form distorted OLiYb2B tetrahedra that share corners with two equivalent O(1)Li2YbB tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, corners with two equivalent O(11)Yb4 tetrahedra, corners with two equivalent O(4)Yb4 tetrahedra, and  an edgeedge with one O(4)Yb4 tetrahedra. In the ninth O site, O(9) is bonded to one Yb(1) and three equivalent Yb(2) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(4)Yb4 tetrahedra,  a cornercorner with one O(6)Yb4 tetrahedra, corners with two equivalent O(9)Yb4 tetrahedra, corners with three equivalent O(13)Li3YbB trigonal bipyramids, and edges with two equivalent O(9)Yb4 tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Yb(2), and one B(2) atom. In the eleventh O site, O(11) is bonded to one Yb(4) and three equivalent Yb(5) atoms to form OYb4 tetrahedra that share  a cornercorner with one O(4)Yb4 tetrahedra, corners with two equivalent O(8)LiYb2B tetrahedra, corners with two equivalent O(11)Yb4 tetrahedra, corners with three equivalent O(6)Yb4 tetrahedra, edges with two equivalent O(11)Yb4 tetrahedra, and edges with two equivalent O(4)Yb4 tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Yb(3), two equivalent Yb(5), and one B(3) atom. In the thirteenth O site, O(13) is bonded to three equivalent Li(2), one Yb(2), and one B(1) atom to form distorted OLi3YbB trigonal bipyramids that share corners with three equivalent O(9)Yb4 tetrahedra, corners with two equivalent O(13)Li3YbB trigonal bipyramids, and edges with two equivalent O(13)Li3YbB trigonal bipyramids.