Eu5V3S6O7 crystallizes in the orthorhombic Pmmn space group. There are three inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 4-coordinate geometry to two equivalent S(1), three equivalent S(2), one O(1), one O(4), and two equivalent O(2) atoms. In the second Eu site, Eu(2) is bonded in a 4-coordinate geometry to one S(3), four equivalent S(4), two equivalent O(1), and two equivalent O(2) atoms. In the third Eu site, Eu(3) is bonded in a 9-coordinate geometry to one S(2), one S(3), two equivalent S(4), two equivalent O(4), and three equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted linear geometry to two equivalent S(2), two equivalent S(4), one O(2), and one O(3) atom. In the second V site, V(2) is bonded in a 2-coordinate geometry to two equivalent S(1), two equivalent S(3), and two equivalent O(4) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to four equivalent Eu(1) and two equivalent V(2) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Eu(3), three equivalent Eu(1), and two equivalent V(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Eu(2), two equivalent Eu(3), and two equivalent V(2) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Eu(2), two equivalent Eu(3), and two equivalent V(1) atoms. There are four inequivalent O sites. In the first O site, O(3) is bonded to three equivalent Eu(3) and one V(1) atom to form a mixture of distorted corner and edge-sharing OEu3V tetrahedra. In the second O site, O(4) is bonded to one Eu(1), two equivalent Eu(3), and one V(2) atom to form distorted OEu3V tetrahedra that share  a cornercorner with one O(1)Eu4 tetrahedra, corners with two equivalent O(2)Eu3V tetrahedra, corners with three equivalent O(4)Eu3V tetrahedra, corners with four equivalent O(3)Eu3V tetrahedra, and  an edgeedge with one O(3)Eu3V tetrahedra. In the third O site, O(1) is bonded to two equivalent Eu(1) and two equivalent Eu(2) atoms to form OEu4 tetrahedra that share corners with two equivalent O(4)Eu3V tetrahedra, corners with two equivalent O(1)Eu4 tetrahedra, and edges with four equivalent O(2)Eu3V tetrahedra. In the fourth O site, O(2) is bonded to one Eu(2), two equivalent Eu(1), and one V(1) atom to form distorted OEu3V tetrahedra that share  a cornercorner with one O(3)Eu3V tetrahedra, corners with two equivalent O(4)Eu3V tetrahedra, corners with three equivalent O(2)Eu3V tetrahedra, and edges with two equivalent O(1)Eu4 tetrahedra.
Eu5V3S6O7 crystallizes in the orthorhombic Pmmn space group. There are three inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 4-coordinate geometry to two equivalent S(1), three equivalent S(2), one O(1), one O(4), and two equivalent O(2) atoms. Both Eu(1)-S(1) bond lengths are 2.98 Å. There are two shorter (3.14 Å) and one longer (3.29 Å) Eu(1)-S(2) bond length. The Eu(1)-O(1) bond length is 2.38 Å. The Eu(1)-O(4) bond length is 2.70 Å. Both Eu(1)-O(2) bond lengths are 2.38 Å. In the second Eu site, Eu(2) is bonded in a 4-coordinate geometry to one S(3), four equivalent S(4), two equivalent O(1), and two equivalent O(2) atoms. The Eu(2)-S(3) bond length is 3.16 Å. All Eu(2)-S(4) bond lengths are 3.12 Å. Both Eu(2)-O(1) bond lengths are 2.29 Å. Both Eu(2)-O(2) bond lengths are 2.51 Å. In the third Eu site, Eu(3) is bonded in a 9-coordinate geometry to one S(2), one S(3), two equivalent S(4), two equivalent O(4), and three equivalent O(3) atoms. The Eu(3)-S(2) bond length is 2.99 Å. The Eu(3)-S(3) bond length is 2.99 Å. Both Eu(3)-S(4) bond lengths are 3.15 Å. Both Eu(3)-O(4) bond lengths are 2.49 Å. There are two shorter (2.44 Å) and one longer (2.53 Å) Eu(3)-O(3) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted linear geometry to two equivalent S(2), two equivalent S(4), one O(2), and one O(3) atom. Both V(1)-S(2) bond lengths are 2.48 Å. Both V(1)-S(4) bond lengths are 2.56 Å. The V(1)-O(2) bond length is 1.85 Å. The V(1)-O(3) bond length is 1.82 Å. In the second V site, V(2) is bonded in a 2-coordinate geometry to two equivalent S(1), two equivalent S(3), and two equivalent O(4) atoms. Both V(2)-S(1) bond lengths are 2.57 Å. Both V(2)-S(3) bond lengths are 2.43 Å. Both V(2)-O(4) bond lengths are 1.83 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to four equivalent Eu(1) and two equivalent V(2) atoms. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Eu(3), three equivalent Eu(1), and two equivalent V(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Eu(2), two equivalent Eu(3), and two equivalent V(2) atoms. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to two equivalent Eu(2), two equivalent Eu(3), and two equivalent V(1) atoms. There are four inequivalent O sites. In the first O site, O(3) is bonded to three equivalent Eu(3) and one V(1) atom to form a mixture of distorted corner and edge-sharing OEu3V tetrahedra. In the second O site, O(4) is bonded to one Eu(1), two equivalent Eu(3), and one V(2) atom to form distorted OEu3V tetrahedra that share  a cornercorner with one O(1)Eu4 tetrahedra, corners with two equivalent O(2)Eu3V tetrahedra, corners with three equivalent O(4)Eu3V tetrahedra, corners with four equivalent O(3)Eu3V tetrahedra, and  an edgeedge with one O(3)Eu3V tetrahedra. In the third O site, O(1) is bonded to two equivalent Eu(1) and two equivalent Eu(2) atoms to form OEu4 tetrahedra that share corners with two equivalent O(4)Eu3V tetrahedra, corners with two equivalent O(1)Eu4 tetrahedra, and edges with four equivalent O(2)Eu3V tetrahedra. In the fourth O site, O(2) is bonded to one Eu(2), two equivalent Eu(1), and one V(1) atom to form distorted OEu3V tetrahedra that share  a cornercorner with one O(3)Eu3V tetrahedra, corners with two equivalent O(4)Eu3V tetrahedra, corners with three equivalent O(2)Eu3V tetrahedra, and edges with two equivalent O(1)Eu4 tetrahedra.