NaBSiO4 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 9-coordinate geometry to three equivalent O(2) and six equivalent O(3) atoms. In the second Na site, Na(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form distorted NaO6 pentagonal pyramids that share corners with six equivalent Si(1)O4 tetrahedra, edges with three equivalent B(1)O4 tetrahedra, and  a faceface with one Na(3)O6 octahedra. In the third Na site, Na(3) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form NaO6 octahedra that share corners with six equivalent B(1)O4 tetrahedra, corners with six equivalent Si(1)O4 tetrahedra, and  a faceface with one Na(2)O6 pentagonal pyramid. B(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form BO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Na(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 62-71°. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(2)O6 pentagonal pyramids, and corners with four equivalent B(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-84°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(3), one B(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one B(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to two equivalent Na(1), one B(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one B(1), and one Si(1) atom.
NaBSiO4 crystallizes in the hexagonal P6_3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 9-coordinate geometry to three equivalent O(2) and six equivalent O(3) atoms. All Na(1)-O(2) bond lengths are 2.70 Å. There are three shorter (2.60 Å) and three longer (2.69 Å) Na(1)-O(3) bond lengths. In the second Na site, Na(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form distorted NaO6 pentagonal pyramids that share corners with six equivalent Si(1)O4 tetrahedra, edges with three equivalent B(1)O4 tetrahedra, and  a faceface with one Na(3)O6 octahedra. All Na(2)-O(2) bond lengths are 2.28 Å. All Na(2)-O(4) bond lengths are 2.41 Å. In the third Na site, Na(3) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form NaO6 octahedra that share corners with six equivalent B(1)O4 tetrahedra, corners with six equivalent Si(1)O4 tetrahedra, and  a faceface with one Na(2)O6 pentagonal pyramid. All Na(3)-O(1) bond lengths are 2.41 Å. All Na(3)-O(4) bond lengths are 2.60 Å. B(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form BO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Na(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 62-71°. The B(1)-O(1) bond length is 1.48 Å. The B(1)-O(2) bond length is 1.49 Å. The B(1)-O(3) bond length is 1.48 Å. The B(1)-O(4) bond length is 1.50 Å. Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra, corners with two equivalent Na(2)O6 pentagonal pyramids, and corners with four equivalent B(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-84°. The Si(1)-O(1) bond length is 1.64 Å. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.64 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(3), one B(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one B(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to two equivalent Na(1), one B(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one B(1), and one Si(1) atom.