NaAuC8H6(N2S)2 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded in a 7-coordinate geometry to one Au(1), two equivalent N(1), two equivalent N(2), and two equivalent S(1) atoms. The Na(1)-Au(1) bond length is 3.14 Å. Both Na(1)-N(1) bond lengths are 2.48 Å. Both Na(1)-N(2) bond lengths are 2.54 Å. Both Na(1)-S(1) bond lengths are 3.15 Å. Au(1) is bonded in a T-shaped geometry to one Na(1) and two equivalent S(1) atoms. Both Au(1)-S(1) bond lengths are 2.29 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one N(1), one N(2), and one S(1) atom. The C(1)-N(1) bond length is 1.35 Å. The C(1)-N(2) bond length is 1.35 Å. The C(1)-S(1) bond length is 1.74 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(3), one N(1), and one H(1) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-N(1) bond length is 1.34 Å. The C(2)-H(1) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(2), one C(4), and one H(2) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-H(2) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one N(2), and one H(3) atom. The C(4)-N(2) bond length is 1.35 Å. The C(4)-H(3) bond length is 1.10 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Na(1), one C(1), and one C(2) atom. In the second N site, N(2) is bonded in a trigonal non-coplanar geometry to one Na(1), one C(1), and one C(4) atom. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. S(1) is bonded in a 3-coordinate geometry to one Na(1), one Au(1), and one C(1) atom. Linkers: 4 S=C1N=C[CH]C=N1. Metal clusters: 2 [Na] ,2 [Au]. The MOF has largest included sphere 2.03 A, density 2.53 g/cm3, surface area 2726.37 m2/g, accessible volume 0.08 cm3/g