Zn4C9H6(N3S)4 crystallizes in the trigonal R3m space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(2), two equivalent N(3), and one S(2) atom to form corner-sharing ZnSN3 tetrahedra. The Zn(1)-N(2) bond length is 2.00 Å. Both Zn(1)-N(3) bond lengths are 2.03 Å. The Zn(1)-S(2) bond length is 2.30 Å. In the second Zn site, Zn(2) is bonded to three equivalent N(1) and one S(2) atom to form corner-sharing ZnSN3 tetrahedra. All Zn(2)-N(1) bond lengths are 1.94 Å. The Zn(2)-S(2) bond length is 2.37 Å. There are two inequivalent C sites. In the first C site, C(2) is bonded in a trigonal planar geometry to one N(2), one N(3), and one H(1) atom. The C(2)-N(2) bond length is 1.36 Å. The C(2)-N(3) bond length is 1.33 Å. The C(2)-H(1) bond length is 1.08 Å. In the second C site, C(1) is bonded in a linear geometry to one N(1) and one S(1) atom. The C(1)-N(1) bond length is 1.19 Å. The C(1)-S(1) bond length is 1.62 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a linear geometry to one Zn(2) and one C(1) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Zn(1) and two equivalent C(2) atoms. In the third N site, N(3) is bonded in a 3-coordinate geometry to one Zn(1), one C(2), and one N(3) atom. The N(3)-N(3) bond length is 1.37 Å. H(1) is bonded in a single-bond geometry to one C(2) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a single-bond geometry to one C(1) atom. In the second S site, S(2) is bonded in a distorted trigonal pyramidal geometry to one Zn(2) and three equivalent Zn(1) atoms. Linkers: 1 [N]1=CN=NC=1. Metal clusters: 4 [Zn]. The MOF has largest included sphere 2.38 A, density 2.37 g/cm3, surface area 3431.98 m2/g, accessible volume 0.07 cm3/g