Yb5(SiO4)3S crystallizes in the hexagonal P6_3/m space group. The structure consists of two hydrogen sulfide atoms inside a Yb5(SiO4)3 framework. In the Yb5(SiO4)3 framework, there are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form distorted YbO6 pentagonal pyramids that share corners with four equivalent Yb(1)O6 pentagonal pyramids, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. In the second Yb site, Yb(2) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with four equivalent Yb(1)O6 pentagonal pyramids and  an edgeedge with one Yb(1)O6 pentagonal pyramid. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Yb(1), two equivalent Yb(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OYb3Si tetrahedra. In the second O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Yb(1) and one Si(1) atom. In the third O site, O(2) is bonded to one Yb(1), two equivalent Yb(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OYb3Si tetrahedra.
Yb5(SiO4)3S crystallizes in the hexagonal P6_3/m space group. The structure consists of two hydrogen sulfide atoms inside a Yb5(SiO4)3 framework. In the Yb5(SiO4)3 framework, there are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form distorted YbO6 pentagonal pyramids that share corners with four equivalent Yb(1)O6 pentagonal pyramids, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The Yb(1)-O(2) bond length is 2.25 Å. The Yb(1)-O(3) bond length is 2.40 Å. There are two shorter (2.31 Å) and two longer (2.39 Å) Yb(1)-O(1) bond lengths. In the second Yb site, Yb(2) is bonded in a 6-coordinate geometry to three equivalent O(2) and three equivalent O(3) atoms. All Yb(2)-O(2) bond lengths are 2.44 Å. All Yb(2)-O(3) bond lengths are 2.38 Å. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with four equivalent Yb(1)O6 pentagonal pyramids and  an edgeedge with one Yb(1)O6 pentagonal pyramid. The Si(1)-O(2) bond length is 1.64 Å. The Si(1)-O(3) bond length is 1.62 Å. Both Si(1)-O(1) bond lengths are 1.66 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Yb(1), two equivalent Yb(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OYb3Si tetrahedra. In the second O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Yb(1) and one Si(1) atom. In the third O site, O(2) is bonded to one Yb(1), two equivalent Yb(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OYb3Si tetrahedra.