Na2BaFe4F12 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one F(6), one F(8), two equivalent F(1), and two equivalent F(2) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Ba(1) is bonded to one F(5), one F(6), one F(7), one F(8), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form BaF12 cuboctahedra that share faces with four equivalent Fe(1)F6 octahedra and faces with four equivalent Fe(2)F6 octahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with four equivalent Fe(2)F6 octahedra, and faces with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 23-34°. In the second Fe site, Fe(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(7), and one F(8) atom to form FeF6 octahedra that share corners with two equivalent Fe(2)F6 octahedra, corners with four equivalent Fe(1)F6 octahedra, and faces with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 22-34°. There are eight inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), one Ba(1), one Fe(1), and one Fe(2) atom to form distorted FBaNaFe2 trigonal pyramids that share corners with four equivalent F(2)BaNa2Fe2 trigonal bipyramids, corners with two equivalent F(1)BaNaFe2 trigonal pyramids, and  an edgeedge with one F(2)BaNa2Fe2 trigonal bipyramid. In the second F site, F(2) is bonded to one Na(1), one Na(2), one Ba(1), one Fe(1), and one Fe(2) atom to form distorted FBaNa2Fe2 trigonal bipyramids that share  a cornercorner with one F(2)BaNa2Fe2 trigonal bipyramid, corners with four equivalent F(1)BaNaFe2 trigonal pyramids,  an edgeedge with one F(2)BaNa2Fe2 trigonal bipyramid, and  an edgeedge with one F(1)BaNaFe2 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(2), one Ba(1), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Na(2), one Ba(1), one Fe(1), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Ba(1) and two equivalent Fe(1) atoms. In the sixth F site, F(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ba(1), and two equivalent Fe(1) atoms. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Ba(1) and two equivalent Fe(2) atoms. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ba(1), and two equivalent Fe(2) atoms.
Na2BaFe4F12 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one F(6), one F(8), two equivalent F(1), and two equivalent F(2) atoms. The Na(1)-F(6) bond length is 2.61 Å. The Na(1)-F(8) bond length is 2.61 Å. Both Na(1)-F(1) bond lengths are 2.32 Å. Both Na(1)-F(2) bond lengths are 2.33 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Both Na(2)-F(2) bond lengths are 2.70 Å. Both Na(2)-F(3) bond lengths are 2.36 Å. Both Na(2)-F(4) bond lengths are 2.35 Å. Ba(1) is bonded to one F(5), one F(6), one F(7), one F(8), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form BaF12 cuboctahedra that share faces with four equivalent Fe(1)F6 octahedra and faces with four equivalent Fe(2)F6 octahedra. The Ba(1)-F(5) bond length is 2.83 Å. The Ba(1)-F(6) bond length is 2.90 Å. The Ba(1)-F(7) bond length is 2.82 Å. The Ba(1)-F(8) bond length is 2.91 Å. Both Ba(1)-F(1) bond lengths are 2.82 Å. Both Ba(1)-F(2) bond lengths are 2.88 Å. Both Ba(1)-F(3) bond lengths are 2.84 Å. Both Ba(1)-F(4) bond lengths are 2.84 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form FeF6 octahedra that share corners with two equivalent Fe(1)F6 octahedra, corners with four equivalent Fe(2)F6 octahedra, and faces with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 23-34°. The Fe(1)-F(1) bond length is 2.13 Å. The Fe(1)-F(2) bond length is 2.15 Å. The Fe(1)-F(3) bond length is 2.12 Å. The Fe(1)-F(4) bond length is 2.09 Å. The Fe(1)-F(5) bond length is 2.07 Å. The Fe(1)-F(6) bond length is 2.09 Å. In the second Fe site, Fe(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(7), and one F(8) atom to form FeF6 octahedra that share corners with two equivalent Fe(2)F6 octahedra, corners with four equivalent Fe(1)F6 octahedra, and faces with two equivalent Ba(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles range from 22-34°. The Fe(2)-F(1) bond length is 2.12 Å. The Fe(2)-F(2) bond length is 2.16 Å. The Fe(2)-F(3) bond length is 2.11 Å. The Fe(2)-F(4) bond length is 2.10 Å. The Fe(2)-F(7) bond length is 2.06 Å. The Fe(2)-F(8) bond length is 2.10 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded to one Na(1), one Ba(1), one Fe(1), and one Fe(2) atom to form distorted FBaNaFe2 trigonal pyramids that share corners with four equivalent F(2)BaNa2Fe2 trigonal bipyramids, corners with two equivalent F(1)BaNaFe2 trigonal pyramids, and  an edgeedge with one F(2)BaNa2Fe2 trigonal bipyramid. In the second F site, F(2) is bonded to one Na(1), one Na(2), one Ba(1), one Fe(1), and one Fe(2) atom to form distorted FBaNa2Fe2 trigonal bipyramids that share  a cornercorner with one F(2)BaNa2Fe2 trigonal bipyramid, corners with four equivalent F(1)BaNaFe2 trigonal pyramids,  an edgeedge with one F(2)BaNa2Fe2 trigonal bipyramid, and  an edgeedge with one F(1)BaNaFe2 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(2), one Ba(1), one Fe(1), and one Fe(2) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Na(2), one Ba(1), one Fe(1), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Ba(1) and two equivalent Fe(1) atoms. In the sixth F site, F(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ba(1), and two equivalent Fe(1) atoms. In the seventh F site, F(7) is bonded in a distorted T-shaped geometry to one Ba(1) and two equivalent Fe(2) atoms. In the eighth F site, F(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ba(1), and two equivalent Fe(2) atoms.