Na2Al2Si3O14 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaO6 pentagonal pyramids that share corners with two equivalent Al(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(1)O6 pentagonal pyramids,  an edgeedge with one Al(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. Al(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AlO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form SiO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra and corners with two equivalent Si(2)O4 tetrahedra. In the second Si site, Si(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Si(1)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. There are seven inequivalent O sites. In the first O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one Si(2) atom. In the second O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one Si(2) atom. In the third O site, O(5) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the fourth O site, O(6) is bonded in a distorted L-shaped geometry to two equivalent Na(1) and one O(7) atom. In the fifth O site, O(7) is bonded in a single-bond geometry to one O(6) atom. In the sixth O site, O(1) is bonded in a bent 150 degrees geometry to one Al(1) and one Si(1) atom. In the seventh O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one Si(2) atom.
Na2Al2Si3O14 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to one O(3), one O(4), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaO6 pentagonal pyramids that share corners with two equivalent Al(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Na(1)O6 pentagonal pyramids,  an edgeedge with one Al(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The Na(1)-O(3) bond length is 2.38 Å. The Na(1)-O(4) bond length is 2.40 Å. There is one shorter (2.49 Å) and one longer (2.56 Å) Na(1)-O(2) bond length. There is one shorter (2.67 Å) and one longer (2.68 Å) Na(1)-O(6) bond length. Al(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form AlO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. The Al(1)-O(1) bond length is 1.76 Å. The Al(1)-O(2) bond length is 1.77 Å. The Al(1)-O(3) bond length is 1.76 Å. The Al(1)-O(4) bond length is 1.76 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form SiO4 tetrahedra that share corners with two equivalent Al(1)O4 tetrahedra and corners with two equivalent Si(2)O4 tetrahedra. Both Si(1)-O(1) bond lengths are 1.64 Å. Both Si(1)-O(5) bond lengths are 1.63 Å. In the second Si site, Si(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids,  a cornercorner with one Si(1)O4 tetrahedra, corners with three equivalent Al(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. The Si(2)-O(2) bond length is 1.64 Å. The Si(2)-O(3) bond length is 1.63 Å. The Si(2)-O(4) bond length is 1.63 Å. The Si(2)-O(5) bond length is 1.65 Å. There are seven inequivalent O sites. In the first O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one Si(2) atom. In the second O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one Si(2) atom. In the third O site, O(5) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the fourth O site, O(6) is bonded in a distorted L-shaped geometry to two equivalent Na(1) and one O(7) atom. The O(6)-O(7) bond length is 1.93 Å. In the fifth O site, O(7) is bonded in a single-bond geometry to one O(6) atom. In the sixth O site, O(1) is bonded in a bent 150 degrees geometry to one Al(1) and one Si(1) atom. In the seventh O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Al(1), and one Si(2) atom.