Cu2C14N5H9S crystallizes in the monoclinic Pc space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 4-coordinate geometry to one N(1), one N(3), one N(5), and one S(1) atom. The Cu(1)-N(1) bond length is 1.98 Å. The Cu(1)-N(3) bond length is 2.05 Å. The Cu(1)-N(5) bond length is 1.88 Å. The Cu(1)-S(1) bond length is 2.51 Å. In the second Cu site, Cu(2) is bonded in a 3-coordinate geometry to one N(2), one N(4), and one S(1) atom. The Cu(2)-N(2) bond length is 1.92 Å. The Cu(2)-N(4) bond length is 1.91 Å. The Cu(2)-S(1) bond length is 2.39 Å. There are fourteen inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(5) and one H(1) atom. The C(1)-C(5) bond length is 1.41 Å. The C(1)-H(1) bond length is 1.09 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one N(3) and one H(2) atom. The C(2)-N(3) bond length is 1.35 Å. The C(2)-H(2) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(4), one N(3), and one H(3) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-N(3) bond length is 1.35 Å. The C(3)-H(3) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one H(4) atom. The C(4)-C(5) bond length is 1.41 Å. The C(4)-H(4) bond length is 1.09 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(1), one C(4), and one C(6) atom. The C(5)-C(6) bond length is 1.45 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(5), one C(7), and one N(1) atom. The C(6)-C(7) bond length is 1.40 Å. The C(6)-N(1) bond length is 1.37 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(6), one C(8), and one H(5) atom. The C(7)-C(8) bond length is 1.40 Å. The C(7)-H(5) bond length is 1.08 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(7), one C(9), and one N(2) atom. The C(8)-C(9) bond length is 1.45 Å. The C(8)-N(2) bond length is 1.37 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(13), and one C(8) atom. The C(9)-C(10) bond length is 1.41 Å. The C(9)-C(13) bond length is 1.41 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(11), one C(9), and one H(6) atom. The C(10)-C(11) bond length is 1.38 Å. The C(10)-H(6) bond length is 1.09 Å. In the eleventh C site, C(11) is bonded in a distorted trigonal planar geometry to one C(10), one N(4), and one H(7) atom. The C(11)-N(4) bond length is 1.36 Å. The C(11)-H(7) bond length is 1.09 Å. In the twelfth C site, C(12) is bonded in a distorted trigonal planar geometry to one C(13), one N(4), and one H(8) atom. The C(12)-C(13) bond length is 1.39 Å. The C(12)-N(4) bond length is 1.36 Å. The C(12)-H(8) bond length is 1.09 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(12), one C(9), and one H(9) atom. The C(13)-H(9) bond length is 1.09 Å. In the fourteenth C site, C(14) is bonded in a distorted linear geometry to one N(5) and one S(1) atom. The C(14)-N(5) bond length is 1.18 Å. The C(14)-S(1) bond length is 1.64 Å. There are five inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Cu(1), one C(6), 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 3-coordinate geometry to one Cu(2), one C(8), and one N(1) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(1), one C(2), and one C(3) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Cu(2), one C(11), and one C(12) atom. In the fifth N site, N(5) is bonded in a linear geometry to one Cu(1) and one C(14) atom. There are nine inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) 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(3) atom. In the fourth H site, H(4) 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(7) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(10) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(11) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(12) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(13) atom. S(1) is bonded in a distorted T-shaped geometry to one Cu(1), one Cu(2), and one C(14) atom. Linkers: 1 [CH]1C(c2ccncc2)=NN=C1c1ccncc1 ,1 [C][C](/C=C\[N])C1=NN=C(c2ccncc2)[CH]1 ,1 C1=C(c2ccncc2)[N]N=C1c1ccncc1 ,1 [C][C](/C=C\[N])C1=CC(c2ccncc2)=N[N]1 ,1 [CH]=C(/C=C\[N])C1=CC(c2ccncc2)=N[N]1 ,1 [CH]=C(/C=C\[N])C1=N[N]C(c2ccncc2)=C1. Metal clusters: 4 [Cu]. The MOF has largest included sphere 2.08 A, density 2.00 g/cm3, surface area 3636.23 m2/g, accessible volume 0.11 cm3/g