Na2ZnSi2O6 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. Zn(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra. Si(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra and corners with two equivalent Si(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Si(1) atoms. In the third O site, O(3) is bonded to two equivalent Na(1), one Zn(1), and one Si(1) atom to form distorted corner-sharing ONa2ZnSi trigonal pyramids.
Na2ZnSi2O6 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. The Na(1)-O(1) bond length is 2.24 Å. There is one shorter (2.45 Å) and one longer (2.50 Å) Na(1)-O(2) bond length. Both Na(1)-O(3) bond lengths are 2.33 Å. Zn(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra. Both Zn(1)-O(1) bond lengths are 1.93 Å. Both Zn(1)-O(3) bond lengths are 1.95 Å. Si(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with two equivalent Zn(1)O4 tetrahedra and corners with two equivalent Si(1)O4 tetrahedra. The Si(1)-O(1) bond length is 1.60 Å. The Si(1)-O(3) bond length is 1.60 Å. Both Si(1)-O(2) bond lengths are 1.66 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Si(1) atoms. In the third O site, O(3) is bonded to two equivalent Na(1), one Zn(1), and one Si(1) atom to form distorted corner-sharing ONa2ZnSi trigonal pyramids.