NaCa2Al2As2O11F4 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), one O(8), and two equivalent F(1) atoms. Ca(1) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), one F(1), and two equivalent F(2) atoms. Al(1) is bonded to one O(1), one O(2), one O(4), one O(7), one F(1), and one F(2) atom to form AlO4F2 octahedra that share  a cornercorner with one Al(1)O4F2 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 42°. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(3), one O(8), and two equivalent O(4) atoms to form AsO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 52°. In the second As site, As(2) is bonded to one O(5), one O(6), and two equivalent O(7) atoms to form AsO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 59°. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a water-like geometry to one Na(1) and one As(1) atom. In the second O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the third O site, O(2) is bonded in a distorted single-bond geometry to one Ca(1) and one Al(1) atom. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Ca(1), and one As(1) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one Al(1) and one As(1) atom. In the sixth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Ca(1), and one As(2) atom. In the seventh O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one As(2) atom. In the eighth O site, O(7) is bonded in a distorted trigonal planar geometry to one Ca(1), one Al(1), and one As(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Na(1), one Ca(1), and one Al(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one Al(1) atom.
NaCa2Al2As2O11F4 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 4-coordinate geometry to one O(3), one O(5), one O(8), and two equivalent F(1) atoms. The Na(1)-O(3) bond length is 2.53 Å. The Na(1)-O(5) bond length is 2.72 Å. The Na(1)-O(8) bond length is 2.46 Å. Both Na(1)-F(1) bond lengths are 2.19 Å. Ca(1) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), one F(1), and two equivalent F(2) atoms. The Ca(1)-O(2) bond length is 2.83 Å. The Ca(1)-O(3) bond length is 2.49 Å. The Ca(1)-O(5) bond length is 2.36 Å. The Ca(1)-O(6) bond length is 2.44 Å. The Ca(1)-O(7) bond length is 2.50 Å. The Ca(1)-F(1) bond length is 2.41 Å. There is one shorter (2.38 Å) and one longer (2.39 Å) Ca(1)-F(2) bond length. Al(1) is bonded to one O(1), one O(2), one O(4), one O(7), one F(1), and one F(2) atom to form AlO4F2 octahedra that share  a cornercorner with one Al(1)O4F2 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 42°. The Al(1)-O(1) bond length is 1.87 Å. The Al(1)-O(2) bond length is 1.96 Å. The Al(1)-O(4) bond length is 1.87 Å. The Al(1)-O(7) bond length is 1.90 Å. The Al(1)-F(1) bond length is 1.80 Å. The Al(1)-F(2) bond length is 1.92 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(3), one O(8), and two equivalent O(4) atoms to form AsO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 52°. The As(1)-O(3) bond length is 1.71 Å. The As(1)-O(8) bond length is 1.76 Å. Both As(1)-O(4) bond lengths are 1.71 Å. In the second As site, As(2) is bonded to one O(5), one O(6), and two equivalent O(7) atoms to form AsO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 59°. The As(2)-O(5) bond length is 1.71 Å. The As(2)-O(6) bond length is 1.69 Å. Both As(2)-O(7) bond lengths are 1.74 Å. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a water-like geometry to one Na(1) and one As(1) atom. In the second O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the third O site, O(2) is bonded in a distorted single-bond geometry to one Ca(1) and one Al(1) atom. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Ca(1), and one As(1) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one Al(1) and one As(1) atom. In the sixth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Ca(1), and one As(2) atom. In the seventh O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one As(2) atom. In the eighth O site, O(7) is bonded in a distorted trigonal planar geometry to one Ca(1), one Al(1), and one As(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Na(1), one Ca(1), and one Al(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Ca(1) and one Al(1) atom.