Na4ReN3 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one N(1), one N(2), and two equivalent N(3) atoms. In the second Na site, Na(2) is bonded in a trigonal non-coplanar geometry to one N(1), one N(2), and one N(3) atom. In the third Na site, Na(3) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form a mixture of distorted corner and edge-sharing NaN4 trigonal pyramids. In the fourth Na site, Na(4) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form a mixture of distorted corner and edge-sharing NaN4 trigonal pyramids. Re(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one N(3) atom. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(4), two equivalent Na(3), and one Re(1) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Re(1) atom. In the third N site, N(3) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Re(1) atom to form distorted corner-sharing NNa5Re octahedra. The corner-sharing octahedral tilt angles are 56°.
Na4ReN3 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one N(1), one N(2), and two equivalent N(3) atoms. The Na(1)-N(1) bond length is 2.99 Å. The Na(1)-N(2) bond length is 2.45 Å. There is one shorter (2.42 Å) and one longer (2.55 Å) Na(1)-N(3) bond length. In the second Na site, Na(2) is bonded in a trigonal non-coplanar geometry to one N(1), one N(2), and one N(3) atom. The Na(2)-N(1) bond length is 2.32 Å. The Na(2)-N(2) bond length is 2.39 Å. The Na(2)-N(3) bond length is 2.45 Å. In the third Na site, Na(3) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form a mixture of distorted corner and edge-sharing NaN4 trigonal pyramids. The Na(3)-N(2) bond length is 2.61 Å. The Na(3)-N(3) bond length is 2.41 Å. There is one shorter (2.45 Å) and one longer (2.52 Å) Na(3)-N(1) bond length. In the fourth Na site, Na(4) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form a mixture of distorted corner and edge-sharing NaN4 trigonal pyramids. The Na(4)-N(1) bond length is 2.59 Å. The Na(4)-N(3) bond length is 2.56 Å. There is one shorter (2.44 Å) and one longer (2.49 Å) Na(4)-N(2) bond length. Re(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one N(3) atom. The Re(1)-N(1) bond length is 1.80 Å. The Re(1)-N(2) bond length is 1.82 Å. The Re(1)-N(3) bond length is 1.81 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(4), two equivalent Na(3), and one Re(1) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Re(1) atom. In the third N site, N(3) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one Re(1) atom to form distorted corner-sharing NNa5Re octahedra. The corner-sharing octahedral tilt angles are 56°.