AgC3H3S(NO)3CF3 crystallizes in the orthorhombic Pna2_1 space group. The structure consists of four trifluoromethane molecules inside a AgC3H3S(NO)3 framework. In the AgC3H3S(NO)3 framework, Ag(1) is bonded in a 5-coordinate geometry to one N(1), one N(2), one N(3), one O(2), and one O(3) atom. The Ag(1)-N(1) bond length is 2.26 Å. The Ag(1)-N(2) bond length is 2.41 Å. The Ag(1)-N(3) bond length is 2.32 Å. The Ag(1)-O(2) bond length is 2.68 Å. The Ag(1)-O(3) bond length is 2.62 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(3), and one H(2) atom. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(3) bond length is 1.34 Å. The C(1)-H(2) bond length is 1.09 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(1) atom. The C(2)-N(1) bond length is 1.34 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 trigonal planar geometry to one N(2), one N(3), and one H(3) atom. The C(3)-N(2) bond length is 1.34 Å. The C(3)-N(3) bond length is 1.34 Å. The C(3)-H(3) bond length is 1.09 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Ag(1), one C(1), and one C(2) atom. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Ag(1), one C(2), and one C(3) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Ag(1), one C(1), and one C(3) 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(1) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. S(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.46 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(3) bond length is 1.46 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1) and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ag(1) and one S(1) atom. Linkers: 4 C1=NC=[N]=C[N]1. Metal clusters: 4 [Ag]. The MOF has largest included sphere 2.53 A, density 2.50 g/cm3, surface area 3064.26 m2/g, accessible volume 0.08 cm3/g