CaNa3B5O10 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(6), and two equivalent O(10) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. Ca(1) is bonded to one O(1), one O(3), one O(4), one O(7), and two equivalent O(8) atoms to form distorted CaO6 octahedra that share  an edgeedge with one Ca(1)O6 octahedra and  an edgeedge with one B(1)O4 tetrahedra. There are five inequivalent B sites. In the first B site, B(1) is bonded to one O(10), one O(2), one O(4), and one O(7) atom to form BO4 tetrahedra that share  an edgeedge with one Ca(1)O6 octahedra. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(6), one O(7), and one O(9) atom. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(8) atom. In the fifth B site, B(5) is bonded in a trigonal planar geometry to one O(10), one O(3), and one O(9) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(2), two equivalent Na(3), one Ca(1), and one B(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Na(2), one B(1), and one B(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ca(1), and one B(5) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Ca(1), one B(1), and one B(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(3), one B(2), and one B(4) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one B(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Na(3), one Ca(1), one B(1), and one B(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Ca(1), and one B(4) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Na(2), one B(3), and one B(5) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Na(1), one B(1), and one B(5) atom.
CaNa3B5O10 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(6), and two equivalent O(10) atoms. The Na(1)-O(2) bond length is 2.37 Å. The Na(1)-O(3) bond length is 2.55 Å. The Na(1)-O(6) bond length is 2.21 Å. There is one shorter (2.31 Å) and one longer (2.43 Å) Na(1)-O(10) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.60 Å. The Na(2)-O(2) bond length is 2.79 Å. The Na(2)-O(4) bond length is 2.53 Å. The Na(2)-O(6) bond length is 2.25 Å. The Na(2)-O(8) bond length is 2.37 Å. The Na(2)-O(9) bond length is 2.48 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. The Na(3)-O(3) bond length is 2.44 Å. The Na(3)-O(5) bond length is 2.36 Å. The Na(3)-O(6) bond length is 2.49 Å. The Na(3)-O(7) bond length is 2.46 Å. There is one shorter (2.55 Å) and one longer (2.70 Å) Na(3)-O(1) bond length. Ca(1) is bonded to one O(1), one O(3), one O(4), one O(7), and two equivalent O(8) atoms to form distorted CaO6 octahedra that share  an edgeedge with one Ca(1)O6 octahedra and  an edgeedge with one B(1)O4 tetrahedra. The Ca(1)-O(1) bond length is 2.24 Å. The Ca(1)-O(3) bond length is 2.26 Å. The Ca(1)-O(4) bond length is 2.40 Å. The Ca(1)-O(7) bond length is 2.47 Å. There is one shorter (2.31 Å) and one longer (2.35 Å) Ca(1)-O(8) bond length. There are five inequivalent B sites. In the first B site, B(1) is bonded to one O(10), one O(2), one O(4), and one O(7) atom to form BO4 tetrahedra that share  an edgeedge with one Ca(1)O6 octahedra. The B(1)-O(10) bond length is 1.46 Å. The B(1)-O(2) bond length is 1.47 Å. The B(1)-O(4) bond length is 1.49 Å. The B(1)-O(7) bond length is 1.46 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(2)-O(1) bond length is 1.32 Å. The B(2)-O(4) bond length is 1.39 Å. The B(2)-O(5) bond length is 1.40 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(6), one O(7), and one O(9) atom. The B(3)-O(6) bond length is 1.31 Å. The B(3)-O(7) bond length is 1.41 Å. The B(3)-O(9) bond length is 1.42 Å. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(8) atom. The B(4)-O(2) bond length is 1.37 Å. The B(4)-O(5) bond length is 1.40 Å. The B(4)-O(8) bond length is 1.33 Å. In the fifth B site, B(5) is bonded in a trigonal planar geometry to one O(10), one O(3), and one O(9) atom. The B(5)-O(10) bond length is 1.39 Å. The B(5)-O(3) bond length is 1.33 Å. The B(5)-O(9) bond length is 1.41 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(2), two equivalent Na(3), one Ca(1), and one B(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Na(2), one B(1), and one B(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ca(1), and one B(5) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Ca(1), one B(1), and one B(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(3), one B(2), and one B(4) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one B(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Na(3), one Ca(1), one B(1), and one B(3) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Ca(1), and one B(4) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Na(2), one B(3), and one B(5) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Na(1), one B(1), and one B(5) atom.