NaCuC16H10(NS)6 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in an octahedral geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. Both Na(1)-N(1) bond lengths are 2.44 Å. Both Na(1)-N(2) bond lengths are 2.50 Å. Both Na(1)-N(3) bond lengths are 2.53 Å. Cu(1) is bonded in a square co-planar geometry to two equivalent S(2) and two equivalent S(3) atoms. Both Cu(1)-S(2) bond lengths are 2.18 Å. Both Cu(1)-S(3) bond lengths are 2.18 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(4), one C(8), and one H(1) atom. The C(1)-C(4) bond length is 1.41 Å. The C(1)-C(8) bond length is 1.39 Å. The C(1)-H(1) bond length is 1.09 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one H(2) atom. The C(2)-C(3) bond length is 1.41 Å. The C(2)-C(5) bond length is 1.38 Å. The C(2)-H(2) 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 N(1) atom. The C(3)-C(4) bond length is 1.45 Å. The C(3)-N(1) bond length is 1.35 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one N(3) atom. The C(4)-N(3) bond length is 1.36 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(2), one C(8), and one S(2) atom. The C(5)-C(8) bond length is 1.44 Å. The C(5)-S(2) bond length is 1.74 Å. In the sixth C site, C(6) is bonded in a linear geometry to one C(7) and one N(2) atom. The C(6)-C(7) bond length is 1.44 Å. The C(6)-N(2) bond length is 1.17 Å. In the seventh C site, C(7) is bonded in a distorted trigonal non-coplanar geometry to one C(6), one H(3), one H(4), and one H(5) atom. The C(7)-H(3) bond length is 1.10 Å. The C(7)-H(4) bond length is 1.10 Å. The C(7)-H(5) bond length is 1.10 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one C(1), one C(5), and one S(3) atom. The C(8)-S(3) bond length is 1.74 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Na(1), one C(3), and one S(1) atom. The N(1)-S(1) bond length is 1.62 Å. In the second N site, N(2) is bonded in a bent 150 degrees geometry to one Na(1) and one C(6) atom. In the third N site, N(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one C(4), and one S(1) atom. The N(3)-S(1) bond length is 1.63 Å. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(7) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(7) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one N(1) and one N(3) atom. In the second S site, S(2) is bonded in a water-like geometry to one Cu(1) and one C(5) atom. In the third S site, S(3) is bonded in a water-like geometry to one Cu(1) and one C(8) atom. Linkers: 4 [S]c1cc2nsnc2cc1[S]. Metal clusters: 2 [Na] ,2 [Cu]. The MOF has largest included sphere 1.87 A, density 1.79 g/cm3, surface area 3983.38 m2/g, accessible volume 0.13 cm3/g