NaYbN4 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(4) atoms to form NaN6 octahedra that share corners with two equivalent Yb(2)N6 pentagonal pyramids, corners with four equivalent Na(2)N6 pentagonal pyramids, edges with two equivalent Yb(1)N6 octahedra,  an edgeedge with one Na(2)N6 pentagonal pyramid, and  an edgeedge with one Yb(2)N6 pentagonal pyramid. In the second Na site, Na(2) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(4) atoms to form NaN6 pentagonal pyramids that share corners with four equivalent Na(1)N6 octahedra,  an edgeedge with one Na(1)N6 octahedra, edges with two equivalent Yb(1)N6 octahedra, and edges with two equivalent Yb(2)N6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-30°. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to two equivalent N(1), two equivalent N(3), and two equivalent N(4) atoms to form YbN6 octahedra that share edges with two equivalent Na(1)N6 octahedra, edges with two equivalent Na(2)N6 pentagonal pyramids, and edges with two equivalent Yb(2)N6 pentagonal pyramids. In the second Yb site, Yb(2) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted YbN6 pentagonal pyramids that share corners with two equivalent Na(1)N6 octahedra,  an edgeedge with one Na(1)N6 octahedra, edges with two equivalent Yb(1)N6 octahedra, and edges with two equivalent Na(2)N6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 31°. There are four inequivalent N sites. In the first N site, N(3) is bonded to one Na(1), one Na(2), one Yb(1), and one Yb(2) atom to form a mixture of distorted corner and edge-sharing NNa2Yb2 tetrahedra. In the second N site, N(4) is bonded in a T-shaped geometry to one Na(1), one Na(2), and one Yb(1) atom. In the third N site, N(1) is bonded in an L-shaped geometry to one Yb(1) and one Yb(2) atom. In the fourth N site, N(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one Yb(2) atom.
NaYbN4 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(4) atoms to form NaN6 octahedra that share corners with two equivalent Yb(2)N6 pentagonal pyramids, corners with four equivalent Na(2)N6 pentagonal pyramids, edges with two equivalent Yb(1)N6 octahedra,  an edgeedge with one Na(2)N6 pentagonal pyramid, and  an edgeedge with one Yb(2)N6 pentagonal pyramid. Both Na(1)-N(2) bond lengths are 2.44 Å. Both Na(1)-N(3) bond lengths are 2.47 Å. Both Na(1)-N(4) bond lengths are 2.64 Å. In the second Na site, Na(2) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(4) atoms to form NaN6 pentagonal pyramids that share corners with four equivalent Na(1)N6 octahedra,  an edgeedge with one Na(1)N6 octahedra, edges with two equivalent Yb(1)N6 octahedra, and edges with two equivalent Yb(2)N6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-30°. Both Na(2)-N(2) bond lengths are 2.48 Å. Both Na(2)-N(3) bond lengths are 2.49 Å. Both Na(2)-N(4) bond lengths are 2.66 Å. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to two equivalent N(1), two equivalent N(3), and two equivalent N(4) atoms to form YbN6 octahedra that share edges with two equivalent Na(1)N6 octahedra, edges with two equivalent Na(2)N6 pentagonal pyramids, and edges with two equivalent Yb(2)N6 pentagonal pyramids. Both Yb(1)-N(1) bond lengths are 2.43 Å. Both Yb(1)-N(3) bond lengths are 2.31 Å. Both Yb(1)-N(4) bond lengths are 2.42 Å. In the second Yb site, Yb(2) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted YbN6 pentagonal pyramids that share corners with two equivalent Na(1)N6 octahedra,  an edgeedge with one Na(1)N6 octahedra, edges with two equivalent Yb(1)N6 octahedra, and edges with two equivalent Na(2)N6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 31°. Both Yb(2)-N(1) bond lengths are 2.43 Å. Both Yb(2)-N(2) bond lengths are 2.43 Å. Both Yb(2)-N(3) bond lengths are 2.36 Å. There are four inequivalent N sites. In the first N site, N(3) is bonded to one Na(1), one Na(2), one Yb(1), and one Yb(2) atom to form a mixture of distorted corner and edge-sharing NNa2Yb2 tetrahedra. In the second N site, N(4) is bonded in a T-shaped geometry to one Na(1), one Na(2), and one Yb(1) atom. In the third N site, N(1) is bonded in an L-shaped geometry to one Yb(1) and one Yb(2) atom. In the fourth N site, N(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one Yb(2) atom.