NaCaBO3 crystallizes in the monoclinic Pc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one B(2), one O(6), one O(8), two equivalent O(10), and two equivalent O(12) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one B(1), one O(5), one O(7), two equivalent O(11), and two equivalent O(9) atoms. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. In the fourth Na site, Na(4) is bonded to one O(1), one O(3), one O(9), two equivalent O(12), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ca(2)O7 pentagonal bipyramid,  a cornercorner with one Ca(3)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Na(4)O7 pentagonal bipyramids, and edges with two equivalent Ca(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 73°. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form CaO6 octahedra that share  a cornercorner with one Na(4)O7 pentagonal bipyramid,  a cornercorner with one Ca(2)O7 pentagonal bipyramid,  a cornercorner with one Ca(3)O7 pentagonal bipyramid,  a cornercorner with one Ca(4)O7 pentagonal bipyramid, edges with two equivalent Ca(1)O6 octahedra,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one Ca(2)O7 pentagonal bipyramid,  an edgeedge with one Ca(3)O7 pentagonal bipyramid, and  an edgeedge with one Ca(4)O7 pentagonal bipyramid. In the second Ca site, Ca(2) is bonded to one O(1), one O(10), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Na(4)O7 pentagonal bipyramid,  a cornercorner with one Ca(4)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Ca(2)O7 pentagonal bipyramids, and edges with two equivalent Ca(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 64°. In the third Ca site, Ca(3) is bonded to one O(11), one O(2), one O(3), two equivalent O(10), and two equivalent O(7) atoms to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Na(4)O7 pentagonal bipyramid,  a cornercorner with one Ca(4)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Ca(2)O7 pentagonal bipyramids, and edges with two equivalent Ca(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 71°. In the fourth Ca site, Ca(4) is bonded to one O(12), one O(2), one O(4), two equivalent O(8), and two equivalent O(9) atoms to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ca(2)O7 pentagonal bipyramid,  a cornercorner with one Ca(3)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Na(4)O7 pentagonal bipyramids, and edges with two equivalent Ca(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 69°. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one Na(2), one O(11), one O(4), and one O(9) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one Na(1), one O(10), one O(12), and one O(3) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(1), one O(5), and one O(6) atom. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(2), one O(7), and one O(8) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(4), one Ca(2), two equivalent Ca(1), and one B(3) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ca(3), one Ca(4), two equivalent Ca(1), and one B(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(4), one Ca(1), one Ca(3), and one B(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), and one B(1) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Na(2), one Na(3), two equivalent Na(4), and one B(3) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), two equivalent Ca(2), and one B(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), two equivalent Ca(3), and one B(4) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), two equivalent Ca(4), and one B(4) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Na(4), two equivalent Na(2), two equivalent Ca(4), and one B(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Na(1), one Ca(2), two equivalent Ca(3), and one B(2) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to two equivalent Na(2), one Ca(3), two equivalent Ca(2), and one B(1) atom. In the twelfth O site, O(12) is bonded in a 1-coordinate geometry to two equivalent Na(1), two equivalent Na(4), one Ca(4), and one B(2) atom.
NaCaBO3 crystallizes in the monoclinic Pc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one B(2), one O(6), one O(8), two equivalent O(10), and two equivalent O(12) atoms. The Na(1)-B(2) bond length is 2.55 Å. The Na(1)-O(6) bond length is 2.28 Å. The Na(1)-O(8) bond length is 2.32 Å. There is one shorter (2.46 Å) and one longer (2.75 Å) Na(1)-O(10) bond length. There is one shorter (2.33 Å) and one longer (2.52 Å) Na(1)-O(12) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one B(1), one O(5), one O(7), two equivalent O(11), and two equivalent O(9) atoms. The Na(2)-B(1) bond length is 2.65 Å. The Na(2)-O(5) bond length is 2.22 Å. The Na(2)-O(7) bond length is 2.38 Å. There is one shorter (2.49 Å) and one longer (2.78 Å) Na(2)-O(11) bond length. There is one shorter (2.39 Å) and one longer (2.74 Å) Na(2)-O(9) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. The Na(3)-O(5) bond length is 2.37 Å. The Na(3)-O(6) bond length is 2.49 Å. The Na(3)-O(7) bond length is 2.53 Å. The Na(3)-O(8) bond length is 2.54 Å. In the fourth Na site, Na(4) is bonded to one O(1), one O(3), one O(9), two equivalent O(12), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ca(2)O7 pentagonal bipyramid,  a cornercorner with one Ca(3)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Na(4)O7 pentagonal bipyramids, and edges with two equivalent Ca(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 73°. The Na(4)-O(1) bond length is 2.73 Å. The Na(4)-O(3) bond length is 2.45 Å. The Na(4)-O(9) bond length is 2.44 Å. There is one shorter (2.66 Å) and one longer (2.73 Å) Na(4)-O(12) bond length. There is one shorter (2.47 Å) and one longer (2.60 Å) Na(4)-O(5) bond length. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form CaO6 octahedra that share  a cornercorner with one Na(4)O7 pentagonal bipyramid,  a cornercorner with one Ca(2)O7 pentagonal bipyramid,  a cornercorner with one Ca(3)O7 pentagonal bipyramid,  a cornercorner with one Ca(4)O7 pentagonal bipyramid, edges with two equivalent Ca(1)O6 octahedra,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one Ca(2)O7 pentagonal bipyramid,  an edgeedge with one Ca(3)O7 pentagonal bipyramid, and  an edgeedge with one Ca(4)O7 pentagonal bipyramid. The Ca(1)-O(3) bond length is 2.23 Å. The Ca(1)-O(4) bond length is 2.28 Å. There is one shorter (2.36 Å) and one longer (2.38 Å) Ca(1)-O(1) bond length. There is one shorter (2.40 Å) and one longer (2.48 Å) Ca(1)-O(2) bond length. In the second Ca site, Ca(2) is bonded to one O(1), one O(10), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Na(4)O7 pentagonal bipyramid,  a cornercorner with one Ca(4)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Ca(2)O7 pentagonal bipyramids, and edges with two equivalent Ca(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 64°. The Ca(2)-O(1) bond length is 2.50 Å. The Ca(2)-O(10) bond length is 2.35 Å. The Ca(2)-O(4) bond length is 2.36 Å. There is one shorter (2.49 Å) and one longer (2.65 Å) Ca(2)-O(11) bond length. There is one shorter (2.40 Å) and one longer (2.41 Å) Ca(2)-O(6) bond length. In the third Ca site, Ca(3) is bonded to one O(11), one O(2), one O(3), two equivalent O(10), and two equivalent O(7) atoms to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Na(4)O7 pentagonal bipyramid,  a cornercorner with one Ca(4)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Ca(2)O7 pentagonal bipyramids, and edges with two equivalent Ca(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 71°. The Ca(3)-O(11) bond length is 2.38 Å. The Ca(3)-O(2) bond length is 2.61 Å. The Ca(3)-O(3) bond length is 2.35 Å. There is one shorter (2.42 Å) and one longer (2.62 Å) Ca(3)-O(10) bond length. There is one shorter (2.44 Å) and one longer (2.46 Å) Ca(3)-O(7) bond length. In the fourth Ca site, Ca(4) is bonded to one O(12), one O(2), one O(4), two equivalent O(8), and two equivalent O(9) atoms to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Ca(2)O7 pentagonal bipyramid,  a cornercorner with one Ca(3)O7 pentagonal bipyramid,  an edgeedge with one Ca(1)O6 octahedra, edges with two equivalent Na(4)O7 pentagonal bipyramids, and edges with two equivalent Ca(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 69°. The Ca(4)-O(12) bond length is 2.29 Å. The Ca(4)-O(2) bond length is 2.70 Å. The Ca(4)-O(4) bond length is 2.42 Å. There is one shorter (2.47 Å) and one longer (2.49 Å) Ca(4)-O(8) bond length. There is one shorter (2.40 Å) and one longer (2.57 Å) Ca(4)-O(9) bond length. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one Na(2), one O(11), one O(4), and one O(9) atom. The B(1)-O(11) bond length is 1.40 Å. The B(1)-O(4) bond length is 1.38 Å. The B(1)-O(9) bond length is 1.38 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one Na(1), one O(10), one O(12), and one O(3) atom. The B(2)-O(10) bond length is 1.42 Å. The B(2)-O(12) bond length is 1.38 Å. The B(2)-O(3) bond length is 1.37 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(1), one O(5), and one O(6) atom. The B(3)-O(1) bond length is 1.40 Å. The B(3)-O(5) bond length is 1.37 Å. The B(3)-O(6) 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(7), and one O(8) atom. The B(4)-O(2) bond length is 1.40 Å. The B(4)-O(7) bond length is 1.40 Å. The B(4)-O(8) bond length is 1.39 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(4), one Ca(2), two equivalent Ca(1), and one B(3) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ca(3), one Ca(4), two equivalent Ca(1), and one B(4) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(4), one Ca(1), one Ca(3), and one B(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), and one B(1) atom. In the fifth O site, O(5) is bonded in a 1-coordinate geometry to one Na(2), one Na(3), two equivalent Na(4), and one B(3) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), two equivalent Ca(2), and one B(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), two equivalent Ca(3), and one B(4) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), two equivalent Ca(4), and one B(4) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Na(4), two equivalent Na(2), two equivalent Ca(4), and one B(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Na(1), one Ca(2), two equivalent Ca(3), and one B(2) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to two equivalent Na(2), one Ca(3), two equivalent Ca(2), and one B(1) atom. In the twelfth O site, O(12) is bonded in a 1-coordinate geometry to two equivalent Na(1), two equivalent Na(4), one Ca(4), and one B(2) atom.