AgH21(C5N2)3 crystallizes in the tetragonal I4_1/acd space group. Ag(1) is bonded in a 4-coordinate geometry to one N(4), one N(5), and two equivalent N(1) atoms. The Ag(1)-N(4) bond length is 2.39 Å. The Ag(1)-N(5) bond length is 2.25 Å. There is one shorter (2.27 Å) and one longer (2.74 Å) Ag(1)-N(1) bond length. There are fifteen inequivalent C sites. In the first C site, C(1) is bonded in a trigonal non-coplanar geometry to one C(2); one H(3); and two equivalent H(1,2) atoms. The C(1)-C(2) bond length is 1.48 Å. The C(1)-H(3) bond length is 0.96 Å. Both C(1)-H(1,2) bond lengths are 0.96 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one N(2) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-N(2) bond length is 1.34 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(8) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-C(8) bond length is 1.47 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one N(1) atom. The C(4)-C(5) bond length is 1.49 Å. The C(4)-N(1) bond length is 1.34 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(4); one H(6); and two equivalent H(4,5) atoms. The C(5)-H(6) bond length is 0.96 Å. Both C(5)-H(4,5) bond lengths are 0.96 Å. In the sixth C site, C(6) is bonded in a trigonal non-coplanar geometry to one C(7); one H(8); and two equivalent H(7,9) atoms. The C(6)-C(7) bond length is 1.48 Å. The C(6)-H(8) bond length is 0.96 Å. Both C(6)-H(7,9) bond lengths are 0.96 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(6), one C(8), and one N(4) atom. The C(7)-C(8) bond length is 1.41 Å. The C(7)-N(4) bond length is 1.34 Å. In the eighth C site, C(8) is bonded in a trigonal planar geometry to one C(3), one C(7), and one C(9) atom. The C(8)-C(9) bond length is 1.38 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(10), one C(8), and one N(3) atom. The C(9)-C(10) bond length is 1.49 Å. The C(9)-N(3) bond length is 1.35 Å. In the tenth C site, C(10) is bonded in a trigonal non-coplanar geometry to one C(9), one H(10), one H(11), and one H(12) atom. The C(10)-H(10) bond length is 0.96 Å. The C(10)-H(11) bond length is 0.96 Å. The C(10)-H(12) bond length is 0.96 Å. In the eleventh C site, C(11) is bonded in a trigonal non-coplanar geometry to one C(12), one H(13), one H(14), and one H(15) atom. The C(11)-C(12) bond length is 1.49 Å. The C(11)-H(13) bond length is 0.96 Å. The C(11)-H(14) bond length is 0.96 Å. The C(11)-H(15) bond length is 0.96 Å. In the twelfth C site, C(12) is bonded in a distorted trigonal planar geometry to one C(11), one C(13), and one N(6) atom. The C(12)-C(13) bond length is 1.39 Å. The C(12)-N(6) bond length is 1.34 Å. In the thirteenth C site, C(13) is bonded in a trigonal planar geometry to one C(12), one C(13), and one C(14) atom. The C(13)-C(13) bond length is 1.49 Å. The C(13)-C(14) bond length is 1.40 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(13), one C(15), and one N(5) atom. The C(14)-C(15) bond length is 1.49 Å. The C(14)-N(5) bond length is 1.33 Å. In the fifteenth C site, C(15) is bonded in a trigonal non-coplanar geometry to one C(14); one H(17); and two equivalent H(16,18) atoms. The C(15)-H(17) bond length is 0.96 Å. Both C(15)-H(16,18) bond lengths are 0.96 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 4-coordinate geometry to two equivalent Ag(1), one C(4), and one N(2) atom. The N(1)-N(2) bond length is 1.35 Å. In the second N site, N(2) is bonded in a 2-coordinate geometry to one C(2), one N(1), and one H(19) atom. The N(2)-H(19) bond length is 0.86 Å. In the third N site, N(3) is bonded in a 1-coordinate geometry to one C(9), one N(4), and one H(20) atom. The N(3)-N(4) bond length is 1.35 Å. The N(3)-H(20) bond length is 0.86 Å. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Ag(1), one C(7), and one N(3) atom. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Ag(1), one C(14), 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 3-coordinate geometry to one C(12), one N(5), and one H(21) atom. The N(6)-H(21) bond length is 0.86 Å. There are seventeen inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(1) atom. In the third H site, H(4,5) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(6) is bonded in a single-bond geometry to one C(5) atom. In the fifth H site, H(7,9) is bonded in a single-bond geometry to one C(6) atom. In the sixth H site, H(8) is bonded in a single-bond geometry to one C(6) atom. In the seventh H site, H(10) is bonded in a single-bond geometry to one C(10) atom. In the eighth H site, H(11) is bonded in a single-bond geometry to one C(10) atom. In the ninth H site, H(12) is bonded in a single-bond geometry to one C(10) atom. In the tenth H site, H(13) is bonded in a single-bond geometry to one C(11) atom. In the eleventh H site, H(14) is bonded in a single-bond geometry to one C(11) atom. In the twelfth H site, H(15) is bonded in a single-bond geometry to one C(11) atom. In the thirteenth H site, H(16,18) is bonded in a single-bond geometry to one C(15) atom. In the fourteenth H site, H(17) is bonded in a single-bond geometry to one C(15) atom. In the fifteenth H site, H(19) is bonded in a single-bond geometry to one N(2) atom. In the sixteenth H site, H(20) is bonded in a single-bond geometry to one N(3) atom. In the seventeenth H site, H(21) is bonded in a single-bond geometry to one N(6) atom. Linkers: 48 Cc1n[nH]c(C)c1-c1c(C)n[nH]c1C. Metal clusters: 16 [N][Ag][Ag][N]. The MOF has largest included sphere 6.44 A, density 1.36 g/cm3, surface area 4943.55 m2/g, accessible volume 0.30 cm3/g