Ba4Na2W2O11 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with four equivalent W(2)O6 octahedra and corners with two equivalent W(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-3°. In the second Na site, Na(2) is bonded to one O(6), two equivalent O(4), and two equivalent O(7) atoms to form distorted NaO5 square pyramids that share corners with two equivalent W(2)O6 octahedra and corners with three equivalent W(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. Ba(1) is bonded in a 10-coordinate geometry to one O(1), one O(2), one O(6), one O(7), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(6), two equivalent O(5), and two equivalent O(7) atoms to form WO5 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra and corners with three equivalent Na(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the second W site, W(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form WO6 octahedra that share corners with four equivalent Na(1)O6 octahedra and corners with two equivalent Na(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-3°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(2)Ba4NaW octahedra, corners with four equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(2)Ba4NaW octahedra, faces with two equivalent O(4)Ba4NaW octahedra, and faces with four equivalent O(3)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 0-54°. In the second O site, O(2) is bonded to one Na(1), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(1)Ba4NaW octahedra, corners with four equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(1)Ba4NaW octahedra, faces with two equivalent O(4)Ba4NaW octahedra, and faces with four equivalent O(3)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 0-56°. In the third O site, O(3) is bonded to one Na(1), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(3)Ba4NaW octahedra, corners with four equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(3)Ba4NaW octahedra, faces with two equivalent O(1)Ba4NaW octahedra, faces with two equivalent O(2)Ba4NaW octahedra, and faces with two equivalent O(4)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 1-55°. In the fourth O site, O(4) is bonded to one Na(2), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(1)Ba4NaW octahedra, corners with two equivalent O(2)Ba4NaW octahedra, corners with four equivalent O(3)Ba4NaW octahedra, corners with six equivalent O(4)Ba4NaW octahedra, corners with two equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(7)Ba2NaW trigonal pyramids,  a faceface with one O(1)Ba4NaW octahedra,  a faceface with one O(2)Ba4NaW octahedra, and faces with two equivalent O(3)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 2-56°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Ba(1), and one W(1) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Na(2), four equivalent Ba(1), and one W(1) atom. In the seventh O site, O(7) is bonded to one Na(2), two equivalent Ba(1), and one W(1) atom to form distorted OBa2NaW trigonal pyramids that share corners with two equivalent O(1)Ba4NaW octahedra, corners with two equivalent O(2)Ba4NaW octahedra, corners with two equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(3)Ba4NaW octahedra, corners with two equivalent O(7)Ba2NaW trigonal pyramids, and edges with two equivalent O(4)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 28-81°.
Ba4Na2W2O11 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with four equivalent W(2)O6 octahedra and corners with two equivalent W(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-3°. The Na(1)-O(1) bond length is 2.32 Å. The Na(1)-O(2) bond length is 2.34 Å. Both Na(1)-O(3) bond lengths are 2.26 Å. Both Na(1)-O(5) bond lengths are 2.42 Å. In the second Na site, Na(2) is bonded to one O(6), two equivalent O(4), and two equivalent O(7) atoms to form distorted NaO5 square pyramids that share corners with two equivalent W(2)O6 octahedra and corners with three equivalent W(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. The Na(2)-O(6) bond length is 2.25 Å. Both Na(2)-O(4) bond lengths are 2.39 Å. Both Na(2)-O(7) bond lengths are 2.62 Å. Ba(1) is bonded in a 10-coordinate geometry to one O(1), one O(2), one O(6), one O(7), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. The Ba(1)-O(1) bond length is 2.87 Å. The Ba(1)-O(2) bond length is 2.85 Å. The Ba(1)-O(6) bond length is 3.24 Å. The Ba(1)-O(7) bond length is 2.69 Å. There is one shorter (2.82 Å) and one longer (2.95 Å) Ba(1)-O(3) bond length. There is one shorter (3.00 Å) and one longer (3.01 Å) Ba(1)-O(4) bond length. There is one shorter (2.88 Å) and one longer (3.22 Å) Ba(1)-O(5) bond length. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(6), two equivalent O(5), and two equivalent O(7) atoms to form WO5 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra and corners with three equivalent Na(2)O5 square pyramids. The corner-sharing octahedral tilt angles are 7°. The W(1)-O(6) bond length is 1.85 Å. Both W(1)-O(5) bond lengths are 1.94 Å. Both W(1)-O(7) bond lengths are 1.90 Å. In the second W site, W(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form WO6 octahedra that share corners with four equivalent Na(1)O6 octahedra and corners with two equivalent Na(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-3°. The W(2)-O(1) bond length is 1.94 Å. The W(2)-O(2) bond length is 1.98 Å. Both W(2)-O(3) bond lengths are 1.95 Å. Both W(2)-O(4) bond lengths are 1.99 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(2)Ba4NaW octahedra, corners with four equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(2)Ba4NaW octahedra, faces with two equivalent O(4)Ba4NaW octahedra, and faces with four equivalent O(3)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 0-54°. In the second O site, O(2) is bonded to one Na(1), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(1)Ba4NaW octahedra, corners with four equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(1)Ba4NaW octahedra, faces with two equivalent O(4)Ba4NaW octahedra, and faces with four equivalent O(3)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 0-56°. In the third O site, O(3) is bonded to one Na(1), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(3)Ba4NaW octahedra, corners with four equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(3)Ba4NaW octahedra, faces with two equivalent O(1)Ba4NaW octahedra, faces with two equivalent O(2)Ba4NaW octahedra, and faces with two equivalent O(4)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 1-55°. In the fourth O site, O(4) is bonded to one Na(2), four equivalent Ba(1), and one W(2) atom to form distorted OBa4NaW octahedra that share corners with two equivalent O(1)Ba4NaW octahedra, corners with two equivalent O(2)Ba4NaW octahedra, corners with four equivalent O(3)Ba4NaW octahedra, corners with six equivalent O(4)Ba4NaW octahedra, corners with two equivalent O(7)Ba2NaW trigonal pyramids, edges with two equivalent O(7)Ba2NaW trigonal pyramids,  a faceface with one O(1)Ba4NaW octahedra,  a faceface with one O(2)Ba4NaW octahedra, and faces with two equivalent O(3)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 2-56°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Ba(1), and one W(1) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Na(2), four equivalent Ba(1), and one W(1) atom. In the seventh O site, O(7) is bonded to one Na(2), two equivalent Ba(1), and one W(1) atom to form distorted OBa2NaW trigonal pyramids that share corners with two equivalent O(1)Ba4NaW octahedra, corners with two equivalent O(2)Ba4NaW octahedra, corners with two equivalent O(4)Ba4NaW octahedra, corners with four equivalent O(3)Ba4NaW octahedra, corners with two equivalent O(7)Ba2NaW trigonal pyramids, and edges with two equivalent O(4)Ba4NaW octahedra. The corner-sharing octahedral tilt angles range from 28-81°.