Ag2C2N4H3S crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a distorted bent 120 degrees geometry to one N(1) and one S(2) atom. The Ag(1)-N(1) bond length is 2.28 Å. The Ag(1)-S(2) bond length is 2.56 Å. In the second Ag site, Ag(2) is bonded in a distorted bent 150 degrees geometry to one S(1) and one S(2) atom. The Ag(2)-S(1) bond length is 2.42 Å. The Ag(2)-S(2) bond length is 2.51 Å. In the third Ag site, Ag(3) is bonded in a distorted T-shaped geometry to one N(5), one S(1), and one S(2) atom. The Ag(3)-N(5) bond length is 2.27 Å. The Ag(3)-S(1) bond length is 2.72 Å. The Ag(3)-S(2) bond length is 2.48 Å. In the fourth Ag site, Ag(4) is bonded in a distorted trigonal planar geometry to one N(2), one N(6), and one S(1) atom. The Ag(4)-N(2) bond length is 2.26 Å. The Ag(4)-N(6) bond length is 2.35 Å. The Ag(4)-S(1) bond length is 2.65 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one N(1), one N(4), and one S(1) atom. The C(1)-N(1) bond length is 1.31 Å. The C(1)-N(4) bond length is 1.31 Å. The C(1)-S(1) bond length is 1.74 Å. In the second C site, C(2) is bonded in a tetrahedral geometry to one N(4), one H(1), one H(2), and one H(3) atom. The C(2)-N(4) bond length is 1.43 Å. The C(2)-H(1) bond length is 0.96 Å. The C(2)-H(2) bond length is 0.96 Å. The C(2)-H(3) bond length is 0.96 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one N(5), one N(8), and one S(2) atom. The C(3)-N(5) bond length is 1.31 Å. The C(3)-N(8) bond length is 1.35 Å. The C(3)-S(2) bond length is 1.74 Å. In the fourth C site, C(4) is bonded in a tetrahedral geometry to one N(8); one H(5); and two equivalent H(4,6) atoms. The C(4)-N(8) bond length is 1.46 Å. The C(4)-H(5) bond length is 0.95 Å. Both C(4)-H(4,6) bond lengths are 0.96 Å. There are eight inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Ag(1), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.34 Å. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Ag(4), one N(1), and one N(3) atom. The N(2)-N(3) bond length is 1.32 Å. In the third N site, N(3) is bonded in a water-like geometry to one N(2) and one N(4) atom. The N(3)-N(4) bond length is 1.35 Å. In the fourth N site, N(4) is bonded in a 2-coordinate geometry to one C(1), one C(2), and one N(3) atom. In the fifth N site, N(5) is bonded in a 3-coordinate geometry to one Ag(3), one C(3), and one N(6) atom. The N(5)-N(6) bond length is 1.36 Å. In the sixth N site, N(6) is bonded in a distorted trigonal planar geometry to one Ag(4), one N(5), and one N(7) atom. The N(6)-N(7) bond length is 1.25 Å. In the seventh N site, N(7) is bonded in a water-like geometry to one N(6) and one N(8) atom. The N(7)-N(8) bond length is 1.33 Å. In the eighth N site, N(8) is bonded in a 3-coordinate geometry to one C(3), one C(4), and one N(7) atom. There are five 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(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(2) atom. In the fourth H site, H(4,6) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(4) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Ag(2), one Ag(3), one Ag(4), and one C(1) atom to form corner-sharing SAg3C tetrahedra. In the second S site, S(2) is bonded to one Ag(1), one Ag(2), one Ag(3), and one C(3) atom to form corner-sharing SAg3C tetrahedra. Linkers: 4 CN1[N]N=NC1=S ,4 CN1N=N[N]C1=S. Metal clusters: 16 [Ag]. The MOF has largest included sphere 9.11 A, density 1.61 g/cm3, surface area 2266.38 m2/g, accessible volume 0.40 cm3/g