VC8H4O5C4H4S crystallizes in the triclinic P1 space group. The structure consists of four thiophene molecules inside a VC8H4O5 framework. In the VC8H4O5 framework, there are three inequivalent V sites. In the first V site, V(1,4) is bonded to one O(1), one O(10), one O(15), one O(20), one O(4), and one O(5) atom to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 49°. The V(1,4)-O(1) bond length is 2.09 Å. The V(1,4)-O(10) bond length is 1.97 Å. The V(1,4)-O(15) bond length is 1.97 Å. The V(1,4)-O(20) bond length is 1.98 Å. The V(1,4)-O(4) bond length is 1.65 Å. The V(1,4)-O(5) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(16), one O(19), one O(2), one O(3), one O(6), and one O(9) atom to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(2)-O(16) bond length is 1.99 Å. The V(2)-O(19) bond length is 1.99 Å. The V(2)-O(2) bond length is 2.08 Å. The V(2)-O(3) bond length is 1.65 Å. The V(2)-O(6) bond length is 1.98 Å. The V(2)-O(9) bond length is 1.98 Å. In the third V site, V(3) is bonded to one O(12), one O(13), one O(18), one O(2), one O(3), and one O(7) atom to form distorted corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 48°. The V(3)-O(12) bond length is 1.98 Å. The V(3)-O(13) bond length is 1.99 Å. The V(3)-O(18) bond length is 1.99 Å. The V(3)-O(2) bond length is 1.65 Å. The V(3)-O(3) bond length is 2.08 Å. The V(3)-O(7) bond length is 1.98 Å. There are thirty inequivalent C sites. In the first C site, C(17) is bonded in a trigonal planar geometry to one C(21), one C(25), and one C(33) atom. The C(17)-C(21) bond length is 1.40 Å. The C(17)-C(25) bond length is 1.48 Å. The C(17)-C(33) bond length is 1.41 Å. In the second C site, C(18) is bonded in a trigonal planar geometry to one C(22), one C(26), and one C(34) atom. The C(18)-C(22) bond length is 1.40 Å. The C(18)-C(26) bond length is 1.48 Å. The C(18)-C(34) bond length is 1.40 Å. In the third C site, C(19) is bonded in a trigonal planar geometry to one C(23), one C(27), and one C(35) atom. The C(19)-C(23) bond length is 1.40 Å. The C(19)-C(27) bond length is 1.48 Å. The C(19)-C(35) bond length is 1.40 Å. In the fourth C site, C(20) is bonded in a trigonal planar geometry to one C(24), one C(28), and one C(36) atom. The C(20)-C(24) bond length is 1.40 Å. The C(20)-C(28) bond length is 1.48 Å. The C(20)-C(36) bond length is 1.41 Å. In the fifth C site, C(21) is bonded in a distorted trigonal planar geometry to one C(17); one C(41,44); and one H(17,20) atom. The C(21)-C(41,44) bond length is 1.39 Å. The C(21)-H(17,20) bond length is 1.09 Å. In the sixth C site, C(22) is bonded in a distorted trigonal planar geometry to one C(18), one C(42), and one H(18) atom. The C(22)-C(42) bond length is 1.39 Å. The C(22)-H(18) bond length is 1.09 Å. In the seventh C site, C(23) is bonded in a distorted trigonal planar geometry to one C(19), one C(43), and one H(19) atom. The C(23)-C(43) bond length is 1.39 Å. The C(23)-H(19) bond length is 1.09 Å. In the eighth C site, C(24) is bonded in a distorted trigonal planar geometry to one C(20); one C(41,44); and one H(17,20) atom. The C(24)-C(41,44) bond length is 1.39 Å. The C(24)-H(17,20) bond length is 1.09 Å. In the ninth C site, C(25) is bonded in a distorted bent 120 degrees geometry to one C(17), one O(17), and one O(5) atom. The C(25)-O(17) bond length is 1.28 Å. The C(25)-O(5) bond length is 1.28 Å. In the tenth C site, C(26) is bonded in a distorted bent 120 degrees geometry to one C(18), one O(18), and one O(6) atom. The C(26)-O(18) bond length is 1.28 Å. The C(26)-O(6) bond length is 1.28 Å. In the eleventh C site, C(27) is bonded in a distorted bent 120 degrees geometry to one C(19), one O(19), and one O(7) atom. The C(27)-O(19) bond length is 1.28 Å. The C(27)-O(7) bond length is 1.28 Å. In the twelfth C site, C(28) is bonded in a distorted bent 120 degrees geometry to one C(20), one O(20), and one O(8) atom. The C(28)-O(20) bond length is 1.28 Å. The C(28)-O(8) bond length is 1.28 Å. In the thirteenth C site, C(29,32) is bonded in a distorted trigonal planar geometry to one C(33); one C(37); and one H(21,22,23,24) atom. The C(29,32)-C(33) bond length is 1.39 Å. The C(29,32)-C(37) bond length is 1.40 Å. The C(29,32)-H(21,22,23,24) bond length is 1.09 Å. In the fourteenth C site, C(30) is bonded in a distorted trigonal planar geometry to one C(34); one C(38); and one H(21,22,23,24) atom. The C(30)-C(34) bond length is 1.39 Å. The C(30)-C(38) bond length is 1.40 Å. The C(30)-H(21,22,23,24) bond length is 1.09 Å. In the fifteenth C site, C(31) is bonded in a distorted trigonal planar geometry to one C(35); one C(39); and one H(21,22,23,24) atom. The C(31)-C(35) bond length is 1.39 Å. The C(31)-C(39) bond length is 1.40 Å. The C(31)-H(21,22,23,24) bond length is 1.09 Å. In the sixteenth C site, C(33) is bonded in a distorted trigonal planar geometry to one C(17); one C(29,32); and one H(25,28) atom. The C(33)-H(25,28) bond length is 1.09 Å. In the seventeenth C site, C(34) is bonded in a distorted trigonal planar geometry to one C(18); one C(30); and one H(26,27) atom. The C(34)-H(26,27) bond length is 1.09 Å. In the eighteenth C site, C(35) is bonded in a distorted trigonal planar geometry to one C(19); one C(31); and one H(26,27) atom. The C(35)-H(26,27) bond length is 1.09 Å. In the nineteenth C site, C(36) is bonded in a distorted trigonal planar geometry to one C(20); one C(29,32); and one H(25,28) atom. The C(36)-C(29,32) bond length is 1.39 Å. The C(36)-H(25,28) bond length is 1.09 Å. In the twentieth C site, C(37) is bonded in a trigonal planar geometry to one C(29,32); one C(41,44); and one C(45) atom. The C(37)-C(41,44) bond length is 1.40 Å. The C(37)-C(45) bond length is 1.48 Å. In the twenty-first C site, C(38) is bonded in a trigonal planar geometry to one C(30), one C(42), and one C(46) atom. The C(38)-C(42) bond length is 1.40 Å. The C(38)-C(46) bond length is 1.48 Å. In the twenty-second C site, C(39) is bonded in a trigonal planar geometry to one C(31), one C(43), and one C(47) atom. The C(39)-C(43) bond length is 1.40 Å. The C(39)-C(47) bond length is 1.48 Å. In the twenty-third C site, C(40) is bonded in a trigonal planar geometry to one C(29,32); one C(41,44); and one C(48) atom. The C(40)-C(29,32) bond length is 1.40 Å. The C(40)-C(41,44) bond length is 1.40 Å. The C(40)-C(48) bond length is 1.48 Å. In the twenty-fourth C site, C(41,44) is bonded in a distorted trigonal planar geometry to one C(21); one C(37); and one H(29,30,31) atom. The C(41,44)-H(29,30,31) bond length is 1.09 Å. In the twenty-fifth C site, C(42) is bonded in a distorted trigonal planar geometry to one C(22); one C(38); and one H(29,30,31) atom. The C(42)-H(29,30,31) bond length is 1.09 Å. In the twenty-sixth C site, C(43) is bonded in a distorted trigonal planar geometry to one C(23); one C(39); and one H(29,30,31) atom. The C(43)-H(29,30,31) bond length is 1.09 Å. In the twenty-seventh C site, C(45) is bonded in a distorted bent 120 degrees geometry to one C(37), one O(13), and one O(9) atom. The C(45)-O(13) bond length is 1.28 Å. The C(45)-O(9) bond length is 1.28 Å. In the twenty-eighth C site, C(46) is bonded in a distorted bent 120 degrees geometry to one C(38), one O(10), and one O(14) atom. The C(46)-O(10) bond length is 1.28 Å. The C(46)-O(14) bond length is 1.28 Å. In the twenty-ninth C site, C(47) is bonded in a distorted bent 120 degrees geometry to one C(39), one O(11), and one O(15) atom. The C(47)-O(11) bond length is 1.28 Å. The C(47)-O(15) bond length is 1.28 Å. In the thirtieth C site, C(48) is bonded in a distorted bent 120 degrees geometry to one C(40), one O(12), and one O(16) atom. The C(48)-O(12) bond length is 1.28 Å. The C(48)-O(16) bond length is 1.28 Å. There are eight inequivalent H sites. In the first H site, H(17,20) is bonded in a single-bond geometry to one C(21) atom. In the second H site, H(18) is bonded in a single-bond geometry to one C(22) atom. In the third H site, H(19) is bonded in a single-bond geometry to one C(23) atom. In the fourth H site, H(21,22,23,24) is bonded in a single-bond geometry to one C(29,32) atom. In the fifth H site, H(25,28) is bonded in a single-bond geometry to one C(33) atom. In the sixth H site, H(26,27) is bonded in a single-bond geometry to one C(34) atom. In the seventh H site, H(29,30,31) is bonded in a single-bond geometry to one C(41,44) atom. In the eighth H site, H(32) is bonded in a single-bond geometry to one C(41,44) atom. The H(32)-C(41,44) bond length is 1.09 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to two equivalent V(1,4) atoms. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one V(2) and one V(3) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one V(2) and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to two equivalent V(1,4) atoms. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1,4) and one C(25) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one C(26) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one C(27) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1,4) and one C(28) atom. The O(8)-V(1,4) bond length is 1.97 Å. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one V(2) and one C(45) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one V(1,4) and one C(46) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(1,4) and one C(47) atom. The O(11)-V(1,4) bond length is 1.97 Å. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(3) and one C(48) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one V(3) and one C(45) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one V(1,4) and one C(46) atom. The O(14)-V(1,4) bond length is 1.98 Å. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one V(1,4) and one C(47) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one V(2) and one C(48) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one V(1,4) and one C(25) atom. The O(17)-V(1,4) bond length is 1.98 Å. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one V(3) and one C(26) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one V(2) and one C(27) atom. In the twentieth O site, O(20) is bonded in a bent 120 degrees geometry to one V(1,4) and one C(28) atom. Linkers: 4 [O]C(=O)c1ccc(C([O])=O)cc1. Metal clusters: 4 [V]. The MOF has largest included sphere 2.95 A, density 1.45 g/cm3, surface area 4316.70 m2/g, accessible volume 0.24 cm3/g