Na2BaSr6Al6(OF16)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), two equivalent F(7), and two equivalent F(8) atoms to form NaO2F4 octahedra that share corners with two equivalent Na(2)O2F4 octahedra, corners with two equivalent Al(3)F6 octahedra, and corners with two equivalent Al(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-75°. In the second Na site, Na(2) is bonded to one O(1), one O(2), two equivalent F(11), and two equivalent F(12) atoms to form distorted NaO2F4 octahedra that share corners with two equivalent Na(1)O2F4 octahedra, corners with two equivalent Al(3)F6 octahedra, and corners with two equivalent Al(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-75°. Ba(1) is bonded in a 9-coordinate geometry to one F(10), two equivalent F(11), two equivalent F(13), two equivalent F(18), and two equivalent F(2) atoms. There are four inequivalent Sr sites. In the first Sr site, Sr(1) is bonded in a 9-coordinate geometry to one O(1), one F(12), one F(13), one F(16), one F(17), one F(18), one F(2), one F(8), and one F(9) atom. In the second Sr site, Sr(2) is bonded in a 9-coordinate geometry to one O(2), one F(1), one F(10), one F(11), one F(14), one F(15), one F(17), one F(18), and one F(7) atom. In the third Sr site, Sr(3) is bonded in a 10-coordinate geometry to one F(3), one F(4), two equivalent F(1), two equivalent F(15), two equivalent F(16), and two equivalent F(2) atoms. In the fourth Sr site, Sr(4) is bonded in a 9-coordinate geometry to one F(9), two equivalent F(1), two equivalent F(12), two equivalent F(14), and two equivalent F(17) atoms. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(3), one F(9), two equivalent F(17), and two equivalent F(5) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 36°. In the second Al site, Al(2) is bonded to one F(10), one F(4), two equivalent F(18), and two equivalent F(6) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 36°. In the third Al site, Al(3) is bonded to one F(1), one F(11), one F(13), one F(16), one F(5), and one F(7) atom to form AlF6 octahedra that share  a cornercorner with one Na(1)O2F4 octahedra,  a cornercorner with one Na(2)O2F4 octahedra, and  a cornercorner with one Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-54°. In the fourth Al site, Al(4) is bonded to one F(12), one F(14), one F(15), one F(2), one F(6), and one F(8) atom to form AlF6 octahedra that share  a cornercorner with one Na(1)O2F4 octahedra,  a cornercorner with one Na(2)O2F4 octahedra, and  a cornercorner with one Al(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-57°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), and two equivalent Sr(1) atoms to form ONa2Sr2 tetrahedra that share corners with two equivalent O(2)Na2Sr2 tetrahedra and edges with two equivalent F(12)NaSr2Al tetrahedra. In the second O site, O(2) is bonded to one Na(1), one Na(2), and two equivalent Sr(2) atoms to form ONa2Sr2 tetrahedra that share corners with two equivalent O(1)Na2Sr2 tetrahedra and corners with two equivalent F(12)NaSr2Al tetrahedra. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a 1-coordinate geometry to one Sr(2), one Sr(3), one Sr(4), and one Al(3) atom. In the second F site, F(2) is bonded in a 1-coordinate geometry to one Ba(1), one Sr(1), one Sr(3), and one Al(4) atom. In the third F site, F(3) is bonded in a distorted linear geometry to one Sr(3) and one Al(1) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to one Sr(3) and one Al(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Al(1) and one Al(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Al(2) and one Al(4) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Na(1), one Sr(2), and one Al(3) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Na(1), one Sr(1), and one Al(4) atom. In the ninth F site, F(9) is bonded in a 1-coordinate geometry to one Sr(4), two equivalent Sr(1), and one Al(1) atom. In the tenth F site, F(10) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Sr(2), and one Al(2) atom. In the eleventh F site, F(11) is bonded in a 4-coordinate geometry to one Na(2), one Ba(1), one Sr(2), and one Al(3) atom. In the twelfth F site, F(12) is bonded to one Na(2), one Sr(1), one Sr(4), and one Al(4) atom to form distorted FNaSr2Al tetrahedra that share  a cornercorner with one O(2)Na2Sr2 tetrahedra,  an edgeedge with one O(1)Na2Sr2 tetrahedra, and  an edgeedge with one F(12)NaSr2Al tetrahedra. In the thirteenth F site, F(13) is bonded in a distorted single-bond geometry to one Ba(1), one Sr(1), and one Al(3) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one Sr(2), one Sr(4), and one Al(4) atom. In the fifteenth F site, F(15) is bonded in a 2-coordinate geometry to one Sr(2), one Sr(3), and one Al(4) atom. In the sixteenth F site, F(16) is bonded in a 1-coordinate geometry to one Sr(1), one Sr(3), and one Al(3) atom. In the seventeenth F site, F(17) is bonded in a 1-coordinate geometry to one Sr(1), one Sr(2), one Sr(4), and one Al(1) atom. In the eighteenth F site, F(18) is bonded in a 4-coordinate geometry to one Ba(1), one Sr(1), one Sr(2), and one Al(2) atom.
Na2BaSr6Al6(OF16)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), two equivalent F(7), and two equivalent F(8) atoms to form NaO2F4 octahedra that share corners with two equivalent Na(2)O2F4 octahedra, corners with two equivalent Al(3)F6 octahedra, and corners with two equivalent Al(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 44-75°. The Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(2) bond length is 2.32 Å. Both Na(1)-F(7) bond lengths are 2.32 Å. Both Na(1)-F(8) bond lengths are 2.30 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), two equivalent F(11), and two equivalent F(12) atoms to form distorted NaO2F4 octahedra that share corners with two equivalent Na(1)O2F4 octahedra, corners with two equivalent Al(3)F6 octahedra, and corners with two equivalent Al(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 54-75°. The Na(2)-O(1) bond length is 2.27 Å. The Na(2)-O(2) bond length is 2.27 Å. Both Na(2)-F(11) bond lengths are 2.47 Å. Both Na(2)-F(12) bond lengths are 2.46 Å. Ba(1) is bonded in a 9-coordinate geometry to one F(10), two equivalent F(11), two equivalent F(13), two equivalent F(18), and two equivalent F(2) atoms. The Ba(1)-F(10) bond length is 2.70 Å. Both Ba(1)-F(11) bond lengths are 2.76 Å. Both Ba(1)-F(13) bond lengths are 2.79 Å. Both Ba(1)-F(18) bond lengths are 2.87 Å. Both Ba(1)-F(2) bond lengths are 2.75 Å. There are four inequivalent Sr sites. In the first Sr site, Sr(1) is bonded in a 9-coordinate geometry to one O(1), one F(12), one F(13), one F(16), one F(17), one F(18), one F(2), one F(8), and one F(9) atom. The Sr(1)-O(1) bond length is 2.45 Å. The Sr(1)-F(12) bond length is 2.57 Å. The Sr(1)-F(13) bond length is 2.55 Å. The Sr(1)-F(16) bond length is 2.52 Å. The Sr(1)-F(17) bond length is 2.61 Å. The Sr(1)-F(18) bond length is 2.55 Å. The Sr(1)-F(2) bond length is 2.90 Å. The Sr(1)-F(8) bond length is 2.61 Å. The Sr(1)-F(9) bond length is 2.99 Å. In the second Sr site, Sr(2) is bonded in a 9-coordinate geometry to one O(2), one F(1), one F(10), one F(11), one F(14), one F(15), one F(17), one F(18), and one F(7) atom. The Sr(2)-O(2) bond length is 2.47 Å. The Sr(2)-F(1) bond length is 2.93 Å. The Sr(2)-F(10) bond length is 2.99 Å. The Sr(2)-F(11) bond length is 2.53 Å. The Sr(2)-F(14) bond length is 2.56 Å. The Sr(2)-F(15) bond length is 2.50 Å. The Sr(2)-F(17) bond length is 2.55 Å. The Sr(2)-F(18) bond length is 2.61 Å. The Sr(2)-F(7) bond length is 2.63 Å. In the third Sr site, Sr(3) is bonded in a 10-coordinate geometry to one F(3), one F(4), two equivalent F(1), two equivalent F(15), two equivalent F(16), and two equivalent F(2) atoms. The Sr(3)-F(3) bond length is 2.53 Å. The Sr(3)-F(4) bond length is 2.56 Å. Both Sr(3)-F(1) bond lengths are 2.57 Å. Both Sr(3)-F(15) bond lengths are 2.98 Å. Both Sr(3)-F(16) bond lengths are 2.93 Å. Both Sr(3)-F(2) bond lengths are 2.57 Å. In the fourth Sr site, Sr(4) is bonded in a 9-coordinate geometry to one F(9), two equivalent F(1), two equivalent F(12), two equivalent F(14), and two equivalent F(17) atoms. The Sr(4)-F(9) bond length is 2.54 Å. Both Sr(4)-F(1) bond lengths are 2.61 Å. Both Sr(4)-F(12) bond lengths are 2.64 Å. Both Sr(4)-F(14) bond lengths are 2.75 Å. Both Sr(4)-F(17) bond lengths are 2.94 Å. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one F(3), one F(9), two equivalent F(17), and two equivalent F(5) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 36°. The Al(1)-F(3) bond length is 1.81 Å. The Al(1)-F(9) bond length is 1.83 Å. Both Al(1)-F(17) bond lengths are 1.83 Å. Both Al(1)-F(5) bond lengths are 1.83 Å. In the second Al site, Al(2) is bonded to one F(10), one F(4), two equivalent F(18), and two equivalent F(6) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 36°. The Al(2)-F(10) bond length is 1.81 Å. The Al(2)-F(4) bond length is 1.81 Å. Both Al(2)-F(18) bond lengths are 1.85 Å. Both Al(2)-F(6) bond lengths are 1.83 Å. In the third Al site, Al(3) is bonded to one F(1), one F(11), one F(13), one F(16), one F(5), and one F(7) atom to form AlF6 octahedra that share  a cornercorner with one Na(1)O2F4 octahedra,  a cornercorner with one Na(2)O2F4 octahedra, and  a cornercorner with one Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-54°. The Al(3)-F(1) bond length is 1.87 Å. The Al(3)-F(11) bond length is 1.85 Å. The Al(3)-F(13) bond length is 1.81 Å. The Al(3)-F(16) bond length is 1.80 Å. The Al(3)-F(5) bond length is 1.86 Å. The Al(3)-F(7) bond length is 1.82 Å. In the fourth Al site, Al(4) is bonded to one F(12), one F(14), one F(15), one F(2), one F(6), and one F(8) atom to form AlF6 octahedra that share  a cornercorner with one Na(1)O2F4 octahedra,  a cornercorner with one Na(2)O2F4 octahedra, and  a cornercorner with one Al(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-57°. The Al(4)-F(12) bond length is 1.86 Å. The Al(4)-F(14) bond length is 1.82 Å. The Al(4)-F(15) bond length is 1.80 Å. The Al(4)-F(2) bond length is 1.86 Å. The Al(4)-F(6) bond length is 1.87 Å. The Al(4)-F(8) bond length is 1.82 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), and two equivalent Sr(1) atoms to form ONa2Sr2 tetrahedra that share corners with two equivalent O(2)Na2Sr2 tetrahedra and edges with two equivalent F(12)NaSr2Al tetrahedra. In the second O site, O(2) is bonded to one Na(1), one Na(2), and two equivalent Sr(2) atoms to form ONa2Sr2 tetrahedra that share corners with two equivalent O(1)Na2Sr2 tetrahedra and corners with two equivalent F(12)NaSr2Al tetrahedra. There are eighteen inequivalent F sites. In the first F site, F(1) is bonded in a 1-coordinate geometry to one Sr(2), one Sr(3), one Sr(4), and one Al(3) atom. In the second F site, F(2) is bonded in a 1-coordinate geometry to one Ba(1), one Sr(1), one Sr(3), and one Al(4) atom. In the third F site, F(3) is bonded in a distorted linear geometry to one Sr(3) and one Al(1) atom. In the fourth F site, F(4) is bonded in a distorted linear geometry to one Sr(3) and one Al(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Al(1) and one Al(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Al(2) and one Al(4) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Na(1), one Sr(2), and one Al(3) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Na(1), one Sr(1), and one Al(4) atom. In the ninth F site, F(9) is bonded in a 1-coordinate geometry to one Sr(4), two equivalent Sr(1), and one Al(1) atom. In the tenth F site, F(10) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Sr(2), and one Al(2) atom. In the eleventh F site, F(11) is bonded in a 4-coordinate geometry to one Na(2), one Ba(1), one Sr(2), and one Al(3) atom. In the twelfth F site, F(12) is bonded to one Na(2), one Sr(1), one Sr(4), and one Al(4) atom to form distorted FNaSr2Al tetrahedra that share  a cornercorner with one O(2)Na2Sr2 tetrahedra,  an edgeedge with one O(1)Na2Sr2 tetrahedra, and  an edgeedge with one F(12)NaSr2Al tetrahedra. In the thirteenth F site, F(13) is bonded in a distorted single-bond geometry to one Ba(1), one Sr(1), and one Al(3) atom. In the fourteenth F site, F(14) is bonded in a distorted single-bond geometry to one Sr(2), one Sr(4), and one Al(4) atom. In the fifteenth F site, F(15) is bonded in a 2-coordinate geometry to one Sr(2), one Sr(3), and one Al(4) atom. In the sixteenth F site, F(16) is bonded in a 1-coordinate geometry to one Sr(1), one Sr(3), and one Al(3) atom. In the seventeenth F site, F(17) is bonded in a 1-coordinate geometry to one Sr(1), one Sr(2), one Sr(4), and one Al(1) atom. In the eighteenth F site, F(18) is bonded in a 4-coordinate geometry to one Ba(1), one Sr(1), one Sr(2), and one Al(2) atom.