ZnC8H6S(NO)4 crystallizes in the monoclinic P2_1/c space group. Zn(1) is bonded to one N(1), one N(2), one N(3), one N(4), one O(1), and one O(2) atom to form distorted ZnN4O2 octahedra that share corners with two equivalent S(1)O4 tetrahedra. The Zn(1)-N(1) bond length is 2.30 Å. The Zn(1)-N(2) bond length is 2.11 Å. The Zn(1)-N(3) bond length is 2.13 Å. The Zn(1)-N(4) bond length is 2.32 Å. The Zn(1)-O(1) bond length is 2.04 Å. The Zn(1)-O(2) bond length is 2.05 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(1), one N(1), and one N(2) atom. The C(1)-C(1) bond length is 1.48 Å. The C(1)-N(1) bond length is 1.33 Å. The C(1)-N(2) bond length is 1.34 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(3), one N(2), and one H(1) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-N(2) 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 single-bond 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(1), and one H(3) atom. The C(4)-N(1) bond length is 1.34 Å. The C(4)-H(3) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(5), one N(3), and one N(4) atom. The C(5)-C(5) bond length is 1.49 Å. The C(5)-N(3) bond length is 1.34 Å. The C(5)-N(4) bond length is 1.34 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(7), one N(4), and one H(4) atom. The C(6)-C(7) bond length is 1.40 Å. The C(6)-N(4) bond length is 1.34 Å. The C(6)-H(4) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(6) and one H(5) atom. The C(7)-H(5) bond length is 1.09 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one N(3) and one H(6) atom. The C(8)-N(3) bond length is 1.34 Å. The C(8)-H(6) bond length is 1.09 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Zn(1), one C(1), and one C(4) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Zn(1), one C(1), and one C(2) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Zn(1), one C(5), and one C(8) atom. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Zn(1), one C(5), and one C(6) atom. There are six 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. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(6) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(7) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(8) atom. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with two equivalent Zn(1)N4O2 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. The S(1)-O(1) bond length is 1.52 Å. The S(1)-O(2) bond length is 1.51 Å. The S(1)-O(3) bond length is 1.47 Å. The S(1)-O(4) bond length is 1.49 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Zn(1) and one S(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Zn(1) and one S(1) atom. In the third O site, O(3) is bonded in a single-bond geometry to one S(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one S(1) atom. Linkers: 3 c1cnc(-c2ncccn2)nc1. Metal clusters: 4 [Zn]. The MOF has largest included sphere 2.44 A, density 1.98 g/cm3, surface area 3411.50 m2/g, accessible volume 0.12 cm3/g