Ag3C8P2H12S6(OF)4 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 3-coordinate geometry to one S(4), one O(1), and one O(4) atom. The Ag(1)-S(4) bond length is 2.56 Å. The Ag(1)-O(1) bond length is 2.28 Å. The Ag(1)-O(4) bond length is 2.41 Å. In the second Ag site, Ag(2) is bonded in a 3-coordinate geometry to one S(5), one O(2), and one O(4) atom. The Ag(2)-S(5) bond length is 2.52 Å. The Ag(2)-O(2) bond length is 2.34 Å. The Ag(2)-O(4) bond length is 2.35 Å. In the third Ag site, Ag(3) is bonded in a 2-coordinate geometry to one S(2), one O(1), and one O(3) atom. The Ag(3)-S(2) bond length is 2.73 Å. The Ag(3)-O(1) bond length is 2.42 Å. The Ag(3)-O(3) bond length is 2.28 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a trigonal non-coplanar geometry to one C(2) and three equivalent H(1,2,3) atoms. The C(1)-C(2) bond length is 1.53 Å. All C(1)-H(1,2,3) bond lengths are 0.98 Å. In the second C site, C(2) is bonded to one C(1), one S(1), one S(2), and one S(4) atom to form corner-sharing CCS3 tetrahedra. The C(2)-S(1) bond length is 1.81 Å. The C(2)-S(2) bond length is 1.82 Å. The C(2)-S(4) bond length is 1.82 Å. In the third C site, C(3) is bonded in a trigonal non-coplanar geometry to one C(4); one H(6); and two equivalent H(4,5) atoms. The C(3)-C(4) bond length is 1.53 Å. The C(3)-H(6) bond length is 0.98 Å. Both C(3)-H(4,5) bond lengths are 0.98 Å. In the fourth C site, C(4) is bonded to one C(3), one S(4), one S(5), and one S(6) atom to form corner-sharing CCS3 tetrahedra. The C(4)-S(4) bond length is 1.83 Å. The C(4)-S(5) bond length is 1.82 Å. The C(4)-S(6) bond length is 1.81 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(6); one H(9); and two equivalent H(7,8) atoms. The C(5)-C(6) bond length is 1.53 Å. The C(5)-H(9) bond length is 0.98 Å. Both C(5)-H(7,8) bond lengths are 0.98 Å. In the sixth C site, C(6) is bonded to one C(5), one S(1), one S(3), and one S(5) atom to form corner-sharing CCS3 tetrahedra. The C(6)-S(1) bond length is 1.81 Å. The C(6)-S(3) bond length is 1.82 Å. The C(6)-S(5) bond length is 1.82 Å. In the seventh C site, C(7) is bonded in a trigonal non-coplanar geometry to one C(8) and three equivalent H(10,11,12) atoms. The C(7)-C(8) bond length is 1.53 Å. All C(7)-H(10,11,12) bond lengths are 0.98 Å. In the eighth C site, C(8) is bonded to one C(7), one S(2), one S(3), and one S(6) atom to form corner-sharing CCS3 tetrahedra. The C(8)-S(2) bond length is 1.83 Å. The C(8)-S(3) bond length is 1.82 Å. The C(8)-S(6) bond length is 1.81 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one O(1), one O(2), one F(1), and one F(2) atom. The P(1)-O(1) bond length is 1.47 Å. The P(1)-O(2) bond length is 1.47 Å. The P(1)-F(1) bond length is 1.54 Å. The P(1)-F(2) bond length is 1.54 Å. In the second P site, P(2) is bonded in a tetrahedral geometry to one O(3), one O(4), one F(3), and one F(4) atom. The P(2)-O(3) bond length is 1.44 Å. The P(2)-O(4) bond length is 1.47 Å. The P(2)-F(3) bond length is 1.55 Å. The P(2)-F(4) bond length is 1.54 Å. There are six inequivalent H sites. In the first H site, H(1,2,3) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(4,5) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(6) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(7,8) is bonded in a single-bond geometry to one C(5) atom. In the fifth H site, H(9) is bonded in a single-bond geometry to one C(5) atom. In the sixth H site, H(10,11,12) is bonded in a single-bond geometry to one C(7) atom. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one C(2) and one C(6) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Ag(3), one C(2), and one C(8) atom. In the third S site, S(3) is bonded in a distorted water-like geometry to one C(6) and one C(8) atom. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one Ag(1), one C(2), and one C(4) atom. In the fifth S site, S(5) is bonded in a distorted trigonal non-coplanar geometry to one Ag(2), one C(4), and one C(6) atom. In the sixth S site, S(6) is bonded in a water-like geometry to one C(4) and one C(8) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ag(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ag(3) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ag(1), one Ag(2), and one P(2) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one P(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one P(1) atom. In the third F site, F(3) is bonded in a single-bond geometry to one P(2) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to one P(2) atom. Linkers: 4 C[C@]12S[C@]3(C)S[C@](C)(S1)S[C@](C)(S2)S3. Metal clusters: 2 F[P](F)(O[Ag])O[Ag]O[P](F)(F)O[Ag].F[P](F)(O[Ag])O[Ag]O[P](F)(F)O[Ag]. The MOF has largest included sphere 4.22 A, density 2.34 g/cm3, surface area 2814.80 m2/g, accessible volume 0.17 cm3/g