NaCaBe2B2O6F crystallizes in the monoclinic Cc space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and two equivalent F(1) atoms. Ca(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CaO6 octahedra that share corners with three equivalent Be(1)O3F tetrahedra and corners with three equivalent Be(2)O3F tetrahedra. There are two inequivalent Be sites. In the first Be site, Be(1) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form BeO3F tetrahedra that share corners with three equivalent Ca(1)O6 octahedra and  a cornercorner with one Be(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 62-74°. In the second Be site, Be(2) is bonded to one O(4), one O(5), one O(6), and one F(1) atom to form BeO3F tetrahedra that share corners with three equivalent Ca(1)O6 octahedra and  a cornercorner with one Be(1)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 63-77°. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. There are six inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Be(2), and one B(1) atom. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one Be(2), and one B(1) atom. In the third O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ca(1), one Be(1), and one B(2) atom. In the fourth O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Be(1), and one B(2) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Be(1), and one B(2) atom. In the sixth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Be(2), and one B(1) atom. F(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Be(1), and one Be(2) atom.
NaCaBe2B2O6F crystallizes in the monoclinic Cc space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and two equivalent F(1) atoms. The Na(1)-O(1) bond length is 2.56 Å. The Na(1)-O(3) bond length is 2.49 Å. The Na(1)-O(4) bond length is 2.63 Å. The Na(1)-O(5) bond length is 2.52 Å. There is one shorter (2.43 Å) and one longer (2.56 Å) Na(1)-F(1) bond length. Ca(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted CaO6 octahedra that share corners with three equivalent Be(1)O3F tetrahedra and corners with three equivalent Be(2)O3F tetrahedra. The Ca(1)-O(1) bond length is 2.42 Å. The Ca(1)-O(2) bond length is 2.37 Å. The Ca(1)-O(3) bond length is 2.43 Å. The Ca(1)-O(4) bond length is 2.38 Å. The Ca(1)-O(5) bond length is 2.43 Å. The Ca(1)-O(6) bond length is 2.38 Å. There are two inequivalent Be sites. In the first Be site, Be(1) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form BeO3F tetrahedra that share corners with three equivalent Ca(1)O6 octahedra and  a cornercorner with one Be(2)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 62-74°. The Be(1)-O(1) bond length is 1.61 Å. The Be(1)-O(2) bond length is 1.62 Å. The Be(1)-O(3) bond length is 1.60 Å. The Be(1)-F(1) bond length is 1.68 Å. In the second Be site, Be(2) is bonded to one O(4), one O(5), one O(6), and one F(1) atom to form BeO3F tetrahedra that share corners with three equivalent Ca(1)O6 octahedra and  a cornercorner with one Be(1)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 63-77°. The Be(2)-O(4) bond length is 1.60 Å. The Be(2)-O(5) bond length is 1.61 Å. The Be(2)-O(6) bond length is 1.63 Å. The Be(2)-F(1) bond length is 1.66 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. The B(1)-O(4) bond length is 1.39 Å. The B(1)-O(5) bond length is 1.38 Å. The B(1)-O(6) bond length is 1.39 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(2)-O(1) bond length is 1.38 Å. The B(2)-O(2) bond length is 1.38 Å. The B(2)-O(3) bond length is 1.39 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Be(2), and one B(1) atom. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one Be(2), and one B(1) atom. In the third O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Ca(1), one Be(1), and one B(2) atom. In the fourth O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Be(1), and one B(2) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Be(1), and one B(2) atom. In the sixth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Be(2), and one B(1) atom. F(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Be(1), and one Be(2) atom.