Eu7(ClF6)2 crystallizes in the hexagonal P-6 space group. There are three inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 9-coordinate geometry to three equivalent F(1) and six equivalent F(4) atoms. In the second Eu site, Eu(2) is bonded in a 9-coordinate geometry to two equivalent Cl(2), one F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. In the third Eu site, Eu(3) is bonded in a 9-coordinate geometry to two equivalent Cl(1), one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to six equivalent Eu(3) atoms to form distorted ClEu6 pentagonal pyramids that share corners with six equivalent F(4)Eu5 square pyramids, corners with six equivalent F(1)Eu4 tetrahedra, corners with six equivalent F(2)Eu4 tetrahedra, edges with three equivalent F(1)Eu4 tetrahedra, edges with three equivalent F(2)Eu4 tetrahedra, edges with six equivalent F(3)Eu4 tetrahedra, and faces with two equivalent Cl(1)Eu6 pentagonal pyramids. In the second Cl site, Cl(2) is bonded to six equivalent Eu(2) atoms to form distorted ClEu6 pentagonal pyramids that share corners with six equivalent F(4)Eu5 square pyramids, corners with six equivalent F(1)Eu4 tetrahedra, corners with six equivalent F(3)Eu4 tetrahedra, edges with three equivalent F(4)Eu5 square pyramids, edges with three equivalent F(3)Eu4 tetrahedra, edges with six equivalent F(2)Eu4 tetrahedra, and faces with two equivalent Cl(2)Eu6 pentagonal pyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Eu(1), one Eu(2), and two equivalent Eu(3) atoms to form FEu4 tetrahedra that share corners with two equivalent Cl(1)Eu6 pentagonal pyramids, corners with two equivalent Cl(2)Eu6 pentagonal pyramids, corners with two equivalent F(4)Eu5 square pyramids, corners with two equivalent F(3)Eu4 tetrahedra, corners with four equivalent F(1)Eu4 tetrahedra, corners with four equivalent F(2)Eu4 tetrahedra,  an edgeedge with one Cl(1)Eu6 pentagonal pyramid, edges with four equivalent F(4)Eu5 square pyramids,  an edgeedge with one F(2)Eu4 tetrahedra, and edges with two equivalent F(3)Eu4 tetrahedra. In the second F site, F(2) is bonded to two equivalent Eu(2) and two equivalent Eu(3) atoms to form FEu4 tetrahedra that share corners with two equivalent Cl(1)Eu6 pentagonal pyramids, corners with two equivalent F(4)Eu5 square pyramids, corners with four equivalent F(1)Eu4 tetrahedra, corners with four equivalent F(2)Eu4 tetrahedra, corners with four equivalent F(3)Eu4 tetrahedra,  an edgeedge with one Cl(1)Eu6 pentagonal pyramid, edges with two equivalent Cl(2)Eu6 pentagonal pyramids, edges with two equivalent F(4)Eu5 square pyramids,  an edgeedge with one F(1)Eu4 tetrahedra, and edges with two equivalent F(3)Eu4 tetrahedra. In the third F site, F(3) is bonded to two equivalent Eu(2) and two equivalent Eu(3) atoms to form FEu4 tetrahedra that share corners with two equivalent Cl(2)Eu6 pentagonal pyramids, corners with four equivalent F(4)Eu5 square pyramids, corners with two equivalent F(1)Eu4 tetrahedra, corners with four equivalent F(2)Eu4 tetrahedra, corners with four equivalent F(3)Eu4 tetrahedra,  an edgeedge with one Cl(2)Eu6 pentagonal pyramid, edges with two equivalent Cl(1)Eu6 pentagonal pyramids,  an edgeedge with one F(4)Eu5 square pyramid, edges with two equivalent F(1)Eu4 tetrahedra, and edges with two equivalent F(2)Eu4 tetrahedra. In the fourth F site, F(4) is bonded to one Eu(3), two equivalent Eu(1), and two equivalent Eu(2) atoms to form distorted FEu5 square pyramids that share corners with two equivalent Cl(1)Eu6 pentagonal pyramids, corners with two equivalent Cl(2)Eu6 pentagonal pyramids, corners with four equivalent F(4)Eu5 square pyramids, corners with two equivalent F(1)Eu4 tetrahedra, corners with two equivalent F(2)Eu4 tetrahedra, corners with four equivalent F(3)Eu4 tetrahedra,  an edgeedge with one Cl(2)Eu6 pentagonal pyramid, edges with four equivalent F(4)Eu5 square pyramids,  an edgeedge with one F(3)Eu4 tetrahedra, edges with two equivalent F(2)Eu4 tetrahedra, and edges with four equivalent F(1)Eu4 tetrahedra.
Eu7(ClF6)2 crystallizes in the hexagonal P-6 space group. There are three inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 9-coordinate geometry to three equivalent F(1) and six equivalent F(4) atoms. All Eu(1)-F(1) bond lengths are 2.40 Å. All Eu(1)-F(4) bond lengths are 2.70 Å. In the second Eu site, Eu(2) is bonded in a 9-coordinate geometry to two equivalent Cl(2), one F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Both Eu(2)-Cl(2) bond lengths are 3.09 Å. The Eu(2)-F(1) bond length is 2.42 Å. There is one shorter (2.47 Å) and one longer (2.49 Å) Eu(2)-F(2) bond length. Both Eu(2)-F(3) bond lengths are 2.45 Å. Both Eu(2)-F(4) bond lengths are 2.78 Å. In the third Eu site, Eu(3) is bonded in a 9-coordinate geometry to two equivalent Cl(1), one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Eu(3)-Cl(1) bond lengths are 3.12 Å. The Eu(3)-F(4) bond length is 2.54 Å. Both Eu(3)-F(1) bond lengths are 2.47 Å. Both Eu(3)-F(2) bond lengths are 2.53 Å. There is one shorter (2.49 Å) and one longer (2.57 Å) Eu(3)-F(3) bond length. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to six equivalent Eu(3) atoms to form distorted ClEu6 pentagonal pyramids that share corners with six equivalent F(4)Eu5 square pyramids, corners with six equivalent F(1)Eu4 tetrahedra, corners with six equivalent F(2)Eu4 tetrahedra, edges with three equivalent F(1)Eu4 tetrahedra, edges with three equivalent F(2)Eu4 tetrahedra, edges with six equivalent F(3)Eu4 tetrahedra, and faces with two equivalent Cl(1)Eu6 pentagonal pyramids. In the second Cl site, Cl(2) is bonded to six equivalent Eu(2) atoms to form distorted ClEu6 pentagonal pyramids that share corners with six equivalent F(4)Eu5 square pyramids, corners with six equivalent F(1)Eu4 tetrahedra, corners with six equivalent F(3)Eu4 tetrahedra, edges with three equivalent F(4)Eu5 square pyramids, edges with three equivalent F(3)Eu4 tetrahedra, edges with six equivalent F(2)Eu4 tetrahedra, and faces with two equivalent Cl(2)Eu6 pentagonal pyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded to one Eu(1), one Eu(2), and two equivalent Eu(3) atoms to form FEu4 tetrahedra that share corners with two equivalent Cl(1)Eu6 pentagonal pyramids, corners with two equivalent Cl(2)Eu6 pentagonal pyramids, corners with two equivalent F(4)Eu5 square pyramids, corners with two equivalent F(3)Eu4 tetrahedra, corners with four equivalent F(1)Eu4 tetrahedra, corners with four equivalent F(2)Eu4 tetrahedra,  an edgeedge with one Cl(1)Eu6 pentagonal pyramid, edges with four equivalent F(4)Eu5 square pyramids,  an edgeedge with one F(2)Eu4 tetrahedra, and edges with two equivalent F(3)Eu4 tetrahedra. In the second F site, F(2) is bonded to two equivalent Eu(2) and two equivalent Eu(3) atoms to form FEu4 tetrahedra that share corners with two equivalent Cl(1)Eu6 pentagonal pyramids, corners with two equivalent F(4)Eu5 square pyramids, corners with four equivalent F(1)Eu4 tetrahedra, corners with four equivalent F(2)Eu4 tetrahedra, corners with four equivalent F(3)Eu4 tetrahedra,  an edgeedge with one Cl(1)Eu6 pentagonal pyramid, edges with two equivalent Cl(2)Eu6 pentagonal pyramids, edges with two equivalent F(4)Eu5 square pyramids,  an edgeedge with one F(1)Eu4 tetrahedra, and edges with two equivalent F(3)Eu4 tetrahedra. In the third F site, F(3) is bonded to two equivalent Eu(2) and two equivalent Eu(3) atoms to form FEu4 tetrahedra that share corners with two equivalent Cl(2)Eu6 pentagonal pyramids, corners with four equivalent F(4)Eu5 square pyramids, corners with two equivalent F(1)Eu4 tetrahedra, corners with four equivalent F(2)Eu4 tetrahedra, corners with four equivalent F(3)Eu4 tetrahedra,  an edgeedge with one Cl(2)Eu6 pentagonal pyramid, edges with two equivalent Cl(1)Eu6 pentagonal pyramids,  an edgeedge with one F(4)Eu5 square pyramid, edges with two equivalent F(1)Eu4 tetrahedra, and edges with two equivalent F(2)Eu4 tetrahedra. In the fourth F site, F(4) is bonded to one Eu(3), two equivalent Eu(1), and two equivalent Eu(2) atoms to form distorted FEu5 square pyramids that share corners with two equivalent Cl(1)Eu6 pentagonal pyramids, corners with two equivalent Cl(2)Eu6 pentagonal pyramids, corners with four equivalent F(4)Eu5 square pyramids, corners with two equivalent F(1)Eu4 tetrahedra, corners with two equivalent F(2)Eu4 tetrahedra, corners with four equivalent F(3)Eu4 tetrahedra,  an edgeedge with one Cl(2)Eu6 pentagonal pyramid, edges with four equivalent F(4)Eu5 square pyramids,  an edgeedge with one F(3)Eu4 tetrahedra, edges with two equivalent F(2)Eu4 tetrahedra, and edges with four equivalent F(1)Eu4 tetrahedra.