Na3WN3 crystallizes in the monoclinic Cc space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one N(2), one N(6), and two equivalent N(4) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one N(4), two equivalent N(1), and two equivalent N(3) atoms. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(3), and two equivalent N(5) atoms. In the fourth Na site, Na(4) is bonded to two equivalent N(5) and two equivalent N(6) atoms to form distorted NaN4 tetrahedra that share corners with two equivalent W(1)N4 tetrahedra, corners with two equivalent W(2)N4 tetrahedra, and edges with two equivalent Na(4)N4 tetrahedra. In the fifth Na site, Na(5) is bonded in a 4-coordinate geometry to one N(2), one N(4), one N(5), and one N(6) atom. In the sixth Na site, Na(6) is bonded in a 4-coordinate geometry to one N(1), one N(3), one N(4), and one N(6) atom. There are two inequivalent W sites. In the first W site, W(1) is bonded to one N(1), one N(2), one N(3), and one N(6) atom to form WN4 tetrahedra that share corners with two equivalent Na(4)N4 tetrahedra and corners with two equivalent W(2)N4 tetrahedra. In the second W site, W(2) is bonded to one N(1), one N(2), one N(4), and one N(5) atom to form WN4 tetrahedra that share corners with two equivalent Na(4)N4 tetrahedra and corners with two equivalent W(1)N4 tetrahedra. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Na(6), two equivalent Na(2), one W(1), and one W(2) atom. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one W(1), and one W(2) atom. In the third N site, N(3) is bonded in a 6-coordinate geometry to one Na(6), two equivalent Na(2), two equivalent Na(3), and one W(1) atom. In the fourth N site, N(4) is bonded to one Na(2), one Na(5), one Na(6), two equivalent Na(1), and one W(2) atom to form a mixture of edge and corner-sharing NNa5W octahedra. The corner-sharing octahedral tilt angles range from 49-56°. In the fifth N site, N(5) is bonded in a 6-coordinate geometry to one Na(5), two equivalent Na(3), two equivalent Na(4), and one W(2) atom. In the sixth N site, N(6) is bonded to one Na(1), one Na(5), one Na(6), two equivalent Na(4), and one W(1) atom to form a mixture of edge and corner-sharing NNa5W octahedra. The corner-sharing octahedral tilt angles range from 49-56°.
Na3WN3 crystallizes in the monoclinic Cc space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one N(2), one N(6), and two equivalent N(4) atoms. The Na(1)-N(2) bond length is 2.63 Å. The Na(1)-N(6) bond length is 2.47 Å. There is one shorter (2.41 Å) and one longer (2.42 Å) Na(1)-N(4) bond length. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one N(4), two equivalent N(1), and two equivalent N(3) atoms. The Na(2)-N(4) bond length is 2.45 Å. There is one shorter (2.67 Å) and one longer (2.85 Å) Na(2)-N(1) bond length. There is one shorter (2.46 Å) and one longer (2.51 Å) Na(2)-N(3) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(3), and two equivalent N(5) atoms. The Na(3)-N(2) bond length is 2.89 Å. There is one shorter (2.34 Å) and one longer (2.68 Å) Na(3)-N(3) bond length. There is one shorter (2.42 Å) and one longer (2.50 Å) Na(3)-N(5) bond length. In the fourth Na site, Na(4) is bonded to two equivalent N(5) and two equivalent N(6) atoms to form distorted NaN4 tetrahedra that share corners with two equivalent W(1)N4 tetrahedra, corners with two equivalent W(2)N4 tetrahedra, and edges with two equivalent Na(4)N4 tetrahedra. There is one shorter (2.43 Å) and one longer (2.57 Å) Na(4)-N(5) bond length. There is one shorter (2.33 Å) and one longer (2.40 Å) Na(4)-N(6) bond length. In the fifth Na site, Na(5) is bonded in a 4-coordinate geometry to one N(2), one N(4), one N(5), and one N(6) atom. The Na(5)-N(2) bond length is 2.48 Å. The Na(5)-N(4) bond length is 2.42 Å. The Na(5)-N(5) bond length is 2.61 Å. The Na(5)-N(6) bond length is 2.56 Å. In the sixth Na site, Na(6) is bonded in a 4-coordinate geometry to one N(1), one N(3), one N(4), and one N(6) atom. The Na(6)-N(1) bond length is 2.48 Å. The Na(6)-N(3) bond length is 2.54 Å. The Na(6)-N(4) bond length is 2.64 Å. The Na(6)-N(6) bond length is 2.50 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one N(1), one N(2), one N(3), and one N(6) atom to form WN4 tetrahedra that share corners with two equivalent Na(4)N4 tetrahedra and corners with two equivalent W(2)N4 tetrahedra. The W(1)-N(1) bond length is 1.93 Å. The W(1)-N(2) bond length is 1.94 Å. The W(1)-N(3) bond length is 1.82 Å. The W(1)-N(6) bond length is 1.82 Å. In the second W site, W(2) is bonded to one N(1), one N(2), one N(4), and one N(5) atom to form WN4 tetrahedra that share corners with two equivalent Na(4)N4 tetrahedra and corners with two equivalent W(1)N4 tetrahedra. The W(2)-N(1) bond length is 1.95 Å. The W(2)-N(2) bond length is 1.93 Å. The W(2)-N(4) bond length is 1.83 Å. The W(2)-N(5) bond length is 1.83 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Na(6), two equivalent Na(2), one W(1), and one W(2) atom. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one W(1), and one W(2) atom. In the third N site, N(3) is bonded in a 6-coordinate geometry to one Na(6), two equivalent Na(2), two equivalent Na(3), and one W(1) atom. In the fourth N site, N(4) is bonded to one Na(2), one Na(5), one Na(6), two equivalent Na(1), and one W(2) atom to form a mixture of edge and corner-sharing NNa5W octahedra. The corner-sharing octahedral tilt angles range from 49-56°. In the fifth N site, N(5) is bonded in a 6-coordinate geometry to one Na(5), two equivalent Na(3), two equivalent Na(4), and one W(2) atom. In the sixth N site, N(6) is bonded to one Na(1), one Na(5), one Na(6), two equivalent Na(4), and one W(1) atom to form a mixture of edge and corner-sharing NNa5W octahedra. The corner-sharing octahedral tilt angles range from 49-56°.