Rb3C31H3(N8O)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a pentagonal pyramidal geometry to one N(10), one N(14), one N(15), one N(3), one N(5), and one N(7) atom. The Rb(1)-N(10) bond length is 2.98 Å. The Rb(1)-N(14) bond length is 2.98 Å. The Rb(1)-N(15) bond length is 3.04 Å. The Rb(1)-N(3) bond length is 3.01 Å. The Rb(1)-N(5) bond length is 3.07 Å. The Rb(1)-N(7) bond length is 3.07 Å. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one N(1), one N(16), one N(4), one N(6), one O(2), and two equivalent O(1) atoms. The Rb(2)-N(1) bond length is 3.18 Å. The Rb(2)-N(16) bond length is 3.05 Å. The Rb(2)-N(4) bond length is 3.03 Å. The Rb(2)-N(6) bond length is 2.95 Å. The Rb(2)-O(2) bond length is 3.10 Å. There is one shorter (3.02 Å) and one longer (3.03 Å) Rb(2)-O(1) bond length. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to one N(12), one N(15), one N(2), one N(5), one N(7), and one N(8) atom. The Rb(3)-N(12) bond length is 3.09 Å. The Rb(3)-N(15) bond length is 3.10 Å. The Rb(3)-N(2) bond length is 3.00 Å. The Rb(3)-N(5) bond length is 3.10 Å. The Rb(3)-N(7) bond length is 3.22 Å. The Rb(3)-N(8) bond length is 2.97 Å. There are thirty-one inequivalent C sites. In the first C site, C(1) is bonded in a linear geometry to one C(6) and one N(1) atom. The C(1)-C(6) bond length is 1.43 Å. The C(1)-N(1) bond length is 1.14 Å. In the second C site, C(2) is bonded in a linear geometry to one C(7) and one N(2) atom. The C(2)-C(7) bond length is 1.42 Å. The C(2)-N(2) bond length is 1.13 Å. In the third C site, C(3) is bonded in a linear geometry to one C(8) and one N(3) atom. The C(3)-C(8) bond length is 1.43 Å. The C(3)-N(3) bond length is 1.14 Å. In the fourth C site, C(4) is bonded in a linear geometry to one C(9) and one N(4) atom. The C(4)-C(9) bond length is 1.42 Å. The C(4)-N(4) bond length is 1.15 Å. In the fifth C site, C(5) is bonded in a linear geometry to one C(10) and one N(5) atom. The C(5)-C(10) bond length is 1.44 Å. The C(5)-N(5) bond length is 1.13 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one C(1), one C(10), and one C(7) atom. The C(6)-C(10) bond length is 1.41 Å. The C(6)-C(7) bond length is 1.42 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(2), one C(6), and one C(8) atom. The C(7)-C(8) bond length is 1.40 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 1.40 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(4), and one C(8) atom. The C(9)-C(10) bond length is 1.40 Å. In the tenth C site, C(10) is bonded in a trigonal planar geometry to one C(5), one C(6), and one C(9) atom. In the eleventh C site, C(11) is bonded in a linear geometry to one C(16) and one N(6) atom. The C(11)-C(16) bond length is 1.43 Å. The C(11)-N(6) bond length is 1.14 Å. In the twelfth C site, C(12) is bonded in a linear geometry to one C(17) and one N(7) atom. The C(12)-C(17) bond length is 1.42 Å. The C(12)-N(7) bond length is 1.14 Å. In the thirteenth C site, C(13) is bonded in a linear geometry to one C(18) and one N(8) atom. The C(13)-C(18) bond length is 1.42 Å. The C(13)-N(8) bond length is 1.14 Å. In the fourteenth C site, C(14) is bonded in a linear geometry to one C(19) and one N(9) atom. The C(14)-C(19) bond length is 1.43 Å. The C(14)-N(9) bond length is 1.14 Å. In the fifteenth C site, C(15) is bonded in a linear geometry to one C(20) and one N(10) atom. The C(15)-C(20) bond length is 1.43 Å. The C(15)-N(10) bond length is 1.14 Å. In the sixteenth C site, C(16) is bonded in a trigonal planar geometry to one C(11), one C(17), and one C(20) atom. The C(16)-C(17) bond length is 1.42 Å. The C(16)-C(20) bond length is 1.40 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(12), one C(16), and one C(18) atom. The C(17)-C(18) bond length is 1.40 Å. In the eighteenth C site, C(18) is bonded in a trigonal planar geometry to one C(13), one C(17), and one C(19) atom. The C(18)-C(19) bond length is 1.41 Å. In the nineteenth C site, C(19) is bonded in a trigonal planar geometry to one C(14), one C(18), and one C(20) atom. The C(19)-C(20) bond length is 1.42 Å. In the twentieth C site, C(20) is bonded in a trigonal planar geometry to one C(15), one C(16), and one C(19) atom. In the twenty-first C site, C(21) is bonded in a tetrahedral geometry to one N(11); one H(3); and two equivalent H(1,2) atoms. The C(21)-N(11) bond length is 1.48 Å. The C(21)-H(3) bond length is 0.96 Å. Both C(21)-H(1,2) bond lengths are 0.96 Å. In the twenty-second C site, C(22) is bonded in a linear geometry to one C(27) and one N(12) atom. The C(22)-C(27) bond length is 1.42 Å. The C(22)-N(12) bond length is 1.14 Å. In the twenty-third C site, C(23) is bonded in a linear geometry to one C(28) and one N(13) atom. The C(23)-C(28) bond length is 1.43 Å. The C(23)-N(13) bond length is 1.13 Å. In the twenty-fourth C site, C(24) is bonded in a distorted linear geometry to one C(29) and one N(14) atom. The C(24)-C(29) bond length is 1.42 Å. The C(24)-N(14) bond length is 1.13 Å. In the twenty-fifth C site, C(25) is bonded in a linear geometry to one C(30) and one N(15) atom. The C(25)-C(30) bond length is 1.43 Å. The C(25)-N(15) bond length is 1.14 Å. In the twenty-sixth C site, C(26) is bonded in a linear geometry to one C(31) and one N(16) atom. The C(26)-C(31) bond length is 1.42 Å. The C(26)-N(16) bond length is 1.14 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one C(22), one C(28), and one C(31) atom. The C(27)-C(28) bond length is 1.41 Å. The C(27)-C(31) bond length is 1.41 Å. In the twenty-eighth C site, C(28) is bonded in a trigonal planar geometry to one C(23), one C(27), and one C(29) atom. The C(28)-C(29) bond length is 1.41 Å. In the twenty-ninth C site, C(29) is bonded in a trigonal planar geometry to one C(24), one C(28), and one C(30) atom. The C(29)-C(30) bond length is 1.41 Å. In the thirtieth C site, C(30) is bonded in a trigonal planar geometry to one C(25), one C(29), and one C(31) atom. The C(30)-C(31) bond length is 1.40 Å. In the thirty-first C site, C(31) is bonded in a trigonal planar geometry to one C(26), one C(27), and one C(30) atom. There are sixteen inequivalent N sites. In the first N site, N(6) is bonded in a distorted bent 150 degrees geometry to one Rb(2) and one C(11) atom. In the second N site, N(7) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), and one C(12) atom. In the third N site, N(11) is bonded in a trigonal planar geometry to one C(21), one O(1), and one O(2) atom. The N(11)-O(1) bond length is 1.22 Å. The N(11)-O(2) bond length is 1.22 Å. In the fourth N site, N(8) is bonded in a distorted bent 150 degrees geometry to one Rb(3) and one C(13) atom. In the fifth N site, N(9) is bonded in a single-bond geometry to one C(14) atom. In the sixth N site, N(1) is bonded in a distorted single-bond geometry to one Rb(2) and one C(1) atom. In the seventh N site, N(2) is bonded in a distorted single-bond geometry to one Rb(3) and one C(2) atom. In the eighth N site, N(3) is bonded in a distorted bent 150 degrees geometry to one Rb(1) and one C(3) atom. In the ninth N site, N(4) is bonded in a distorted bent 150 degrees geometry to one Rb(2) and one C(4) atom. In the tenth N site, N(15) is bonded in a distorted trigonal planar geometry to one Rb(1), one Rb(3), and one C(25) atom. In the eleventh N site, N(16) is bonded in a distorted bent 150 degrees geometry to one Rb(2) and one C(26) atom. In the twelfth N site, N(12) is bonded in a distorted single-bond geometry to one Rb(3) and one C(22) atom. In the thirteenth N site, N(13) is bonded in a single-bond geometry to one C(23) atom. In the fourteenth N site, N(14) is bonded in a distorted single-bond geometry to one Rb(1) and one C(24) atom. In the fifteenth N site, N(10) is bonded in a distorted linear geometry to one Rb(1) and one C(15) atom. In the sixteenth N site, N(5) is bonded in a distorted trigonal planar geometry to one Rb(1), one Rb(3), and one C(5) atom. There are two inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(21) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(21) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Rb(2) and one N(11) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Rb(2) and one N(11) atom. Linkers: 12 N#C[C]1C(C#N)=C(C#N)C(C#N)=C1C#N ,4 C[N+](=O)[O-]. Metal clusters: 12 [Rb]. The MOF has largest included sphere 4.70 A, density 1.30 g/cm3, surface area 4672.86 m2/g, accessible volume 0.31 cm3/g