Sm6Fe6As6O5F crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 4-coordinate geometry to one As(1), one As(2), one As(3), one As(4), one O(1), one O(3), and two equivalent O(2) atoms. In the second Sm site, Sm(2) is bonded in a 4-coordinate geometry to two equivalent As(2), two equivalent As(4), one O(1), two equivalent O(2), and one F(1) atom. In the third Sm site, Sm(3) is bonded in a 4-coordinate geometry to one As(1), one As(2), one As(3), one As(4), one O(2), two equivalent O(3), and one F(1) atom. In the fourth Sm site, Sm(4) is bonded in a 4-coordinate geometry to two equivalent As(2), two equivalent As(4), one O(1), two equivalent O(3), and one F(1) atom. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one As(1), one As(4), and two equivalent As(2) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. In the second Fe site, Fe(2) is bonded to one As(1), one As(3), and two equivalent As(2) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. In the third Fe site, Fe(3) is bonded to one As(2), one As(3), and two equivalent As(4) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. In the fourth Fe site, Fe(4) is bonded to one As(1), one As(3), and two equivalent As(4) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to two equivalent Sm(1), two equivalent Sm(3), one Fe(2), one Fe(4), and two equivalent Fe(1) atoms. In the second As site, As(2) is bonded in a 8-coordinate geometry to one Sm(1), one Sm(2), one Sm(3), one Sm(4), one Fe(2), one Fe(3), and two equivalent Fe(1) atoms. In the third As site, As(3) is bonded in a 8-coordinate geometry to two equivalent Sm(1), two equivalent Sm(3), one Fe(2), one Fe(4), and two equivalent Fe(3) atoms. In the fourth As site, As(4) is bonded in a 8-coordinate geometry to one Sm(1), one Sm(2), one Sm(3), one Sm(4), one Fe(1), one Fe(4), and two equivalent Fe(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Sm(2), one Sm(4), and two equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with two equivalent O(2)Sm4 tetrahedra, corners with two equivalent F(1)Sm4 tetrahedra, edges with two equivalent O(2)Sm4 tetrahedra, and edges with two equivalent O(3)Sm4 tetrahedra. In the second O site, O(2) is bonded to one Sm(2), one Sm(3), and two equivalent Sm(1) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(1)Sm4 tetrahedra,  a cornercorner with one O(2)Sm4 tetrahedra, corners with two equivalent O(3)Sm4 tetrahedra,  an edgeedge with one O(1)Sm4 tetrahedra,  an edgeedge with one O(2)Sm4 tetrahedra,  an edgeedge with one O(3)Sm4 tetrahedra, and  an edgeedge with one F(1)Sm4 tetrahedra. In the third O site, O(3) is bonded to one Sm(1), one Sm(4), and two equivalent Sm(3) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one F(1)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra,  an edgeedge with one O(1)Sm4 tetrahedra,  an edgeedge with one O(2)Sm4 tetrahedra,  an edgeedge with one O(3)Sm4 tetrahedra, and  an edgeedge with one F(1)Sm4 tetrahedra. F(1) is bonded to one Sm(2), one Sm(4), and two equivalent Sm(3) atoms to form FSm4 tetrahedra that share corners with two equivalent O(1)Sm4 tetrahedra, corners with two equivalent O(3)Sm4 tetrahedra, edges with two equivalent O(2)Sm4 tetrahedra, and edges with two equivalent O(3)Sm4 tetrahedra.
Sm6Fe6As6O5F crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 4-coordinate geometry to one As(1), one As(2), one As(3), one As(4), one O(1), one O(3), and two equivalent O(2) atoms. The Sm(1)-As(1) bond length is 3.31 Å. The Sm(1)-As(2) bond length is 3.32 Å. The Sm(1)-As(3) bond length is 3.31 Å. The Sm(1)-As(4) bond length is 3.30 Å. The Sm(1)-O(1) bond length is 2.33 Å. The Sm(1)-O(3) bond length is 2.36 Å. There is one shorter (2.33 Å) and one longer (2.35 Å) Sm(1)-O(2) bond length. In the second Sm site, Sm(2) is bonded in a 4-coordinate geometry to two equivalent As(2), two equivalent As(4), one O(1), two equivalent O(2), and one F(1) atom. Both Sm(2)-As(2) bond lengths are 3.23 Å. Both Sm(2)-As(4) bond lengths are 3.32 Å. The Sm(2)-O(1) bond length is 2.26 Å. Both Sm(2)-O(2) bond lengths are 2.33 Å. The Sm(2)-F(1) bond length is 2.42 Å. In the third Sm site, Sm(3) is bonded in a 4-coordinate geometry to one As(1), one As(2), one As(3), one As(4), one O(2), two equivalent O(3), and one F(1) atom. The Sm(3)-As(1) bond length is 3.34 Å. The Sm(3)-As(2) bond length is 3.23 Å. The Sm(3)-As(3) bond length is 3.33 Å. The Sm(3)-As(4) bond length is 3.22 Å. The Sm(3)-O(2) bond length is 2.32 Å. There is one shorter (2.28 Å) and one longer (2.34 Å) Sm(3)-O(3) bond length. The Sm(3)-F(1) bond length is 2.44 Å. In the fourth Sm site, Sm(4) is bonded in a 4-coordinate geometry to two equivalent As(2), two equivalent As(4), one O(1), two equivalent O(3), and one F(1) atom. Both Sm(4)-As(2) bond lengths are 3.22 Å. Both Sm(4)-As(4) bond lengths are 3.31 Å. The Sm(4)-O(1) bond length is 2.27 Å. Both Sm(4)-O(3) bond lengths are 2.31 Å. The Sm(4)-F(1) bond length is 2.45 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one As(1), one As(4), and two equivalent As(2) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. The Fe(1)-As(1) bond length is 2.62 Å. The Fe(1)-As(4) bond length is 2.61 Å. There is one shorter (2.61 Å) and one longer (2.63 Å) Fe(1)-As(2) bond length. In the second Fe site, Fe(2) is bonded to one As(1), one As(3), and two equivalent As(2) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. The Fe(2)-As(1) bond length is 2.59 Å. The Fe(2)-As(3) bond length is 2.61 Å. Both Fe(2)-As(2) bond lengths are 2.61 Å. In the third Fe site, Fe(3) is bonded to one As(2), one As(3), and two equivalent As(4) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. The Fe(3)-As(2) bond length is 2.63 Å. The Fe(3)-As(3) bond length is 2.62 Å. There is one shorter (2.61 Å) and one longer (2.63 Å) Fe(3)-As(4) bond length. In the fourth Fe site, Fe(4) is bonded to one As(1), one As(3), and two equivalent As(4) atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. The Fe(4)-As(1) bond length is 2.62 Å. The Fe(4)-As(3) bond length is 2.62 Å. Both Fe(4)-As(4) bond lengths are 2.62 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to two equivalent Sm(1), two equivalent Sm(3), one Fe(2), one Fe(4), and two equivalent Fe(1) atoms. In the second As site, As(2) is bonded in a 8-coordinate geometry to one Sm(1), one Sm(2), one Sm(3), one Sm(4), one Fe(2), one Fe(3), and two equivalent Fe(1) atoms. In the third As site, As(3) is bonded in a 8-coordinate geometry to two equivalent Sm(1), two equivalent Sm(3), one Fe(2), one Fe(4), and two equivalent Fe(3) atoms. In the fourth As site, As(4) is bonded in a 8-coordinate geometry to one Sm(1), one Sm(2), one Sm(3), one Sm(4), one Fe(1), one Fe(4), and two equivalent Fe(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Sm(2), one Sm(4), and two equivalent Sm(1) atoms to form OSm4 tetrahedra that share corners with two equivalent O(2)Sm4 tetrahedra, corners with two equivalent F(1)Sm4 tetrahedra, edges with two equivalent O(2)Sm4 tetrahedra, and edges with two equivalent O(3)Sm4 tetrahedra. In the second O site, O(2) is bonded to one Sm(2), one Sm(3), and two equivalent Sm(1) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(1)Sm4 tetrahedra,  a cornercorner with one O(2)Sm4 tetrahedra, corners with two equivalent O(3)Sm4 tetrahedra,  an edgeedge with one O(1)Sm4 tetrahedra,  an edgeedge with one O(2)Sm4 tetrahedra,  an edgeedge with one O(3)Sm4 tetrahedra, and  an edgeedge with one F(1)Sm4 tetrahedra. In the third O site, O(3) is bonded to one Sm(1), one Sm(4), and two equivalent Sm(3) atoms to form OSm4 tetrahedra that share  a cornercorner with one O(3)Sm4 tetrahedra,  a cornercorner with one F(1)Sm4 tetrahedra, corners with two equivalent O(2)Sm4 tetrahedra,  an edgeedge with one O(1)Sm4 tetrahedra,  an edgeedge with one O(2)Sm4 tetrahedra,  an edgeedge with one O(3)Sm4 tetrahedra, and  an edgeedge with one F(1)Sm4 tetrahedra. F(1) is bonded to one Sm(2), one Sm(4), and two equivalent Sm(3) atoms to form FSm4 tetrahedra that share corners with two equivalent O(1)Sm4 tetrahedra, corners with two equivalent O(3)Sm4 tetrahedra, edges with two equivalent O(2)Sm4 tetrahedra, and edges with two equivalent O(3)Sm4 tetrahedra.