V16Co3Ge4C10H40(NO3)10 crystallizes in the tetragonal I4_1cd space group. There are sixteen inequivalent V sites. In the first V site, V(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The V(1)-O(1) bond length is 1.98 Å. The V(1)-O(2) bond length is 1.92 Å. The V(1)-O(3) bond length is 2.03 Å. The V(1)-O(4) bond length is 1.92 Å. In the second V site, V(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(2), one O(5), and one O(6) atom. The V(2)-O(1) bond length is 1.98 Å. The V(2)-O(2) bond length is 1.94 Å. The V(2)-O(5) bond length is 1.93 Å. The V(2)-O(6) bond length is 1.92 Å. In the third V site, V(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. The V(3)-O(5) bond length is 1.97 Å. The V(3)-O(6) bond length is 1.92 Å. The V(3)-O(7) bond length is 1.95 Å. The V(3)-O(8) bond length is 1.89 Å. In the fourth V site, V(4) is bonded in a 4-coordinate geometry to one O(10), one O(7), one O(8), and one O(9) atom. The V(4)-O(10) bond length is 1.95 Å. The V(4)-O(7) bond length is 1.93 Å. The V(4)-O(8) bond length is 1.97 Å. The V(4)-O(9) bond length is 1.94 Å. In the fifth V site, V(5) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(12), and one O(9) atom. The V(5)-O(10) bond length is 1.90 Å. The V(5)-O(11) bond length is 1.94 Å. The V(5)-O(12) bond length is 1.97 Å. The V(5)-O(9) bond length is 1.92 Å. In the sixth V site, V(6) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(12), one O(13), and one O(14) atom. The V(6)-O(11) bond length is 1.95 Å. The V(6)-O(12) bond length is 1.97 Å. The V(6)-O(13) bond length is 1.93 Å. The V(6)-O(14) bond length is 2.04 Å. In the seventh V site, V(7) is bonded in a 4-coordinate geometry to one O(13), one O(14), one O(15), and one O(16) atom. The V(7)-O(13) bond length is 1.92 Å. The V(7)-O(14) bond length is 2.01 Å. The V(7)-O(15) bond length is 1.94 Å. The V(7)-O(16) bond length is 1.95 Å. In the eighth V site, V(8) is bonded in a distorted trigonal pyramidal geometry to one O(15), one O(16), one O(3), and one O(4) atom. The V(8)-O(15) bond length is 1.92 Å. The V(8)-O(16) bond length is 1.93 Å. The V(8)-O(3) bond length is 2.00 Å. The V(8)-O(4) bond length is 1.96 Å. In the ninth V site, V(9) is bonded in a 5-coordinate geometry to one O(17), one O(18), one O(19), one O(2), and one O(6) atom. The V(9)-O(17) bond length is 1.98 Å. The V(9)-O(18) bond length is 1.95 Å. The V(9)-O(19) bond length is 1.62 Å. The V(9)-O(2) bond length is 1.95 Å. The V(9)-O(6) bond length is 1.95 Å. In the tenth V site, V(10) is bonded in a distorted see-saw-like geometry to one O(17), one O(18), one O(20), and one O(21) atom. The V(10)-O(17) bond length is 1.93 Å. The V(10)-O(18) bond length is 1.92 Å. The V(10)-O(20) bond length is 1.98 Å. The V(10)-O(21) bond length is 2.00 Å. In the eleventh V site, V(11) is bonded in a distorted see-saw-like geometry to one O(10), one O(18), one O(21), and one O(8) atom. The V(11)-O(10) bond length is 1.97 Å. The V(11)-O(18) bond length is 1.95 Å. The V(11)-O(21) bond length is 2.01 Å. The V(11)-O(8) bond length is 1.93 Å. In the twelfth V site, V(12) is bonded in a distorted L-shaped geometry to one O(16), one O(17), one O(20), and one O(4) atom. The V(12)-O(16) bond length is 1.93 Å. The V(12)-O(17) bond length is 1.90 Å. The V(12)-O(20) bond length is 2.02 Å. The V(12)-O(4) bond length is 1.93 Å. In the thirteenth V site, V(13) is bonded in a 4-coordinate geometry to one O(22), one O(23), one O(5), and one O(7) atom. The V(13)-O(22) bond length is 2.05 Å. The V(13)-O(23) bond length is 1.93 Å. The V(13)-O(5) bond length is 1.95 Å. The V(13)-O(7) bond length is 1.94 Å. In the fourteenth V site, V(14) is bonded in a distorted see-saw-like geometry to one O(22), one O(23), one O(24), and one O(25) atom. The V(14)-O(22) bond length is 2.00 Å. The V(14)-O(23) bond length is 1.92 Å. The V(14)-O(24) bond length is 2.00 Å. The V(14)-O(25) bond length is 1.93 Å. In the fifteenth V site, V(15) is bonded in a 5-coordinate geometry to one O(13), one O(15), one O(24), one O(25), and one O(26) atom. The V(15)-O(13) bond length is 1.91 Å. The V(15)-O(15) bond length is 1.96 Å. The V(15)-O(24) bond length is 2.03 Å. The V(15)-O(25) bond length is 1.91 Å. The V(15)-O(26) bond length is 1.61 Å. In the sixteenth V site, V(16) is bonded in a 4-coordinate geometry to one O(11), one O(23), one O(25), and one O(9) atom. The V(16)-O(11) bond length is 1.96 Å. The V(16)-O(23) bond length is 1.95 Å. The V(16)-O(25) bond length is 1.95 Å. The V(16)-O(9) bond length is 1.94 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one N(1), one N(2), one N(3), one O(28), and one O(30) atom to form distorted CoN3O2 square pyramids that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, and  an edgeedge with one Co(2)N3O2 square pyramid. The Co(1)-N(1) bond length is 2.11 Å. The Co(1)-N(2) bond length is 2.15 Å. The Co(1)-N(3) bond length is 2.09 Å. The Co(1)-O(28) bond length is 2.16 Å. The Co(1)-O(30) bond length is 2.09 Å. In the second Co site, Co(2) is bonded to one N(4), one N(5), one N(6), one O(28), and one O(30) atom to form distorted CoN3O2 square pyramids that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(3)O4 tetrahedra, and  an edgeedge with one Co(1)N3O2 square pyramid. The Co(2)-N(4) bond length is 2.13 Å. The Co(2)-N(5) bond length is 2.19 Å. The Co(2)-N(6) bond length is 2.16 Å. The Co(2)-O(28) bond length is 2.05 Å. The Co(2)-O(30) bond length is 2.23 Å. In the third Co site, Co(3) is bonded in an octahedral geometry to one N(10), one N(7), one N(8), one N(9), one O(19), and one O(26) atom. The Co(3)-N(10) bond length is 2.11 Å. The Co(3)-N(7) bond length is 2.08 Å. The Co(3)-N(8) bond length is 2.11 Å. The Co(3)-N(9) bond length is 2.15 Å. The Co(3)-O(19) bond length is 2.20 Å. The Co(3)-O(26) bond length is 2.16 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(22), one O(27), and one O(28) atom to form GeO4 tetrahedra that share  a cornercorner with one Co(1)N3O2 square pyramid and  a cornercorner with one Co(2)N3O2 square pyramid. The Ge(1)-O(1) bond length is 1.74 Å. The Ge(1)-O(22) bond length is 1.76 Å. The Ge(1)-O(27) bond length is 1.80 Å. The Ge(1)-O(28) bond length is 1.70 Å. In the second Ge site, Ge(2) is bonded in a trigonal non-coplanar geometry to one O(24), one O(27), and one O(3) atom. The Ge(2)-O(24) bond length is 1.73 Å. The Ge(2)-O(27) bond length is 1.77 Å. The Ge(2)-O(3) bond length is 1.75 Å. In the third Ge site, Ge(3) is bonded to one O(12), one O(21), one O(29), and one O(30) atom to form GeO4 tetrahedra that share  a cornercorner with one Co(1)N3O2 square pyramid and  a cornercorner with one Co(2)N3O2 square pyramid. The Ge(3)-O(12) bond length is 1.77 Å. The Ge(3)-O(21) bond length is 1.75 Å. The Ge(3)-O(29) bond length is 1.79 Å. The Ge(3)-O(30) bond length is 1.70 Å. In the fourth Ge site, Ge(4) is bonded in a trigonal non-coplanar geometry to one O(14), one O(20), and one O(29) atom. The Ge(4)-O(14) bond length is 1.74 Å. The Ge(4)-O(20) bond length is 1.76 Å. The Ge(4)-O(29) bond length is 1.77 Å. There are ten inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal non-coplanar geometry to one N(1), one H(21), and one H(22) atom. The C(1)-N(1) bond length is 1.38 Å. The C(1)-H(21) bond length is 0.97 Å. The C(1)-H(22) bond length is 0.97 Å. In the second C site, C(2) is bonded in a distorted trigonal non-coplanar geometry to one N(2) and two equivalent H(23,24) atoms. The C(2)-N(2) bond length is 1.42 Å. Both C(2)-H(23,24) bond lengths are 0.97 Å. In the third C site, C(3) is bonded in a distorted trigonal non-coplanar geometry to one N(3), one H(25), and one H(26) atom. The C(3)-N(3) bond length is 1.34 Å. The C(3)-H(25) bond length is 0.97 Å. The C(3)-H(26) bond length is 0.97 Å. In the fourth C site, C(4) is bonded in a 3-coordinate geometry to one C(5), one N(4), one H(27), and one H(28) atom. The C(4)-C(5) bond length is 1.47 Å. The C(4)-N(4) bond length is 1.46 Å. The C(4)-H(27) bond length is 0.97 Å. The C(4)-H(28) bond length is 0.97 Å. In the fifth C site, C(5) is bonded in a 4-coordinate geometry to one C(4), one N(5), one H(29), and one H(30) atom. The C(5)-N(5) bond length is 1.49 Å. The C(5)-H(29) bond length is 0.97 Å. The C(5)-H(30) bond length is 0.97 Å. In the sixth C site, C(6) is bonded in a 3-coordinate geometry to one N(6), one H(31), and one H(32) atom. The C(6)-N(6) bond length is 1.45 Å. The C(6)-H(31) bond length is 0.97 Å. The C(6)-H(32) bond length is 0.97 Å. In the seventh C site, C(7) is bonded in a 3-coordinate geometry to one N(7) and two equivalent H(33,34) atoms. The C(7)-N(7) bond length is 1.47 Å. Both C(7)-H(33,34) bond lengths are 0.97 Å. In the eighth C site, C(8) is bonded in a 3-coordinate geometry to one N(8), one H(35), and one H(36) atom. The C(8)-N(8) bond length is 1.47 Å. The C(8)-H(35) bond length is 0.97 Å. The C(8)-H(36) bond length is 0.97 Å. In the ninth C site, C(9) is bonded in a 3-coordinate geometry to one N(9), one H(37), and one H(38) atom. The C(9)-N(9) bond length is 1.46 Å. The C(9)-H(37) bond length is 0.97 Å. The C(9)-H(38) bond length is 0.97 Å. In the tenth C site, C(10) is bonded in a 3-coordinate geometry to one N(10) and two equivalent H(39,40) atoms. The C(10)-N(10) bond length is 1.46 Å. Both C(10)-H(39,40) bond lengths are 0.97 Å. There are ten inequivalent N sites. In the first N site, N(1) is bonded in a 4-coordinate geometry to one Co(1); one C(1); and two equivalent H(1,2) atoms. Both N(1)-H(1,2) bond lengths are 0.90 Å. In the second N site, N(2) is bonded in a 2-coordinate geometry to one Co(1), one C(2), one H(3), and one H(4) atom. The N(2)-H(3) bond length is 0.90 Å. The N(2)-H(4) bond length is 0.90 Å. In the third N site, N(3) is bonded in a 4-coordinate geometry to one Co(1), one C(3), one H(5), and one H(6) atom. The N(3)-H(5) bond length is 0.90 Å. The N(3)-H(6) bond length is 0.90 Å. In the fourth N site, N(4) is bonded in a 2-coordinate geometry to one Co(2); one C(4); and two equivalent H(7,8) atoms. Both N(4)-H(7,8) bond lengths are 0.90 Å. In the fifth N site, N(5) is bonded in a 2-coordinate geometry to one Co(2), one C(5), one H(10), and one H(9) atom. The N(5)-H(10) bond length is 0.90 Å. The N(5)-H(9) bond length is 0.90 Å. In the sixth N site, N(6) is bonded in a 2-coordinate geometry to one Co(2); one C(6); and two equivalent H(11,12) atoms. Both N(6)-H(11,12) bond lengths are 0.90 Å. In the seventh N site, N(7) is bonded in a distorted water-like geometry to one Co(3), one C(7), one H(13), and one H(14) atom. The N(7)-H(13) bond length is 0.90 Å. The N(7)-H(14) bond length is 0.90 Å. In the eighth N site, N(8) is bonded in a 2-coordinate geometry to one Co(3), one C(8), one H(15), and one H(16) atom. The N(8)-H(15) bond length is 0.90 Å. The N(8)-H(16) bond length is 0.90 Å. In the ninth N site, N(9) is bonded in a 2-coordinate geometry to one Co(3), one C(9), one H(17), and one H(18) atom. The N(9)-H(17) bond length is 0.90 Å. The N(9)-H(18) bond length is 0.90 Å. In the tenth N site, N(10) is bonded in a 2-coordinate geometry to one Co(3), one C(10), one H(19), and one H(20) atom. The N(10)-H(19) bond length is 0.90 Å. The N(10)-H(20) bond length is 0.90 Å. There are thirty-four inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one N(1) atom. In the second H site, H(3) is bonded in a single-bond geometry to one N(2) atom. In the third H site, H(4) is bonded in a single-bond geometry to one N(2) atom. In the fourth H site, H(5) is bonded in a single-bond geometry to one N(3) atom. In the fifth H site, H(6) is bonded in a single-bond geometry to one N(3) atom. In the sixth H site, H(7,8) is bonded in a single-bond geometry to one N(4) atom. In the seventh H site, H(9) is bonded in a single-bond geometry to one N(5) atom. In the eighth H site, H(10) is bonded in a single-bond geometry to one N(5) atom. In the ninth H site, H(11,12) is bonded in a single-bond geometry to one N(6) atom. In the tenth H site, H(13) is bonded in a single-bond geometry to one N(7) atom. In the eleventh H site, H(14) is bonded in a single-bond geometry to one N(7) atom. In the twelfth H site, H(15) is bonded in a single-bond geometry to one N(8) atom. In the thirteenth H site, H(16) is bonded in a single-bond geometry to one N(8) atom. In the fourteenth H site, H(17) is bonded in a single-bond geometry to one N(9) atom. In the fifteenth H site, H(18) is bonded in a single-bond geometry to one N(9) atom. In the sixteenth H site, H(19) is bonded in a single-bond geometry to one N(10) atom. In the seventeenth H site, H(20) is bonded in a single-bond geometry to one N(10) atom. In the eighteenth H site, H(21) is bonded in a single-bond geometry to one C(1) atom. In the nineteenth H site, H(22) is bonded in a single-bond geometry to one C(1) atom. In the twentieth H site, H(23,24) is bonded in a single-bond geometry to one C(2) atom. In the twenty-first H site, H(25) is bonded in a single-bond geometry to one C(3) atom. In the twenty-second H site, H(26) is bonded in a single-bond geometry to one C(3) atom. In the twenty-third H site, H(27) is bonded in a single-bond geometry to one C(4) atom. In the twenty-fourth H site, H(28) is bonded in a single-bond geometry to one C(4) atom. In the twenty-fifth H site, H(29) is bonded in a single-bond geometry to one C(5) atom. In the twenty-sixth H site, H(30) is bonded in a single-bond geometry to one C(5) atom. In the twenty-seventh H site, H(31) is bonded in a single-bond geometry to one C(6) atom. In the twenty-eighth H site, H(32) is bonded in a single-bond geometry to one C(6) atom. In the twenty-ninth H site, H(33,34) is bonded in a single-bond geometry to one C(7) atom. In the thirtieth H site, H(35) is bonded in a single-bond geometry to one C(8) atom. In the thirty-first H site, H(36) is bonded in a single-bond geometry to one C(8) atom. In the thirty-second H site, H(37) is bonded in a single-bond geometry to one C(9) atom. In the thirty-third H site, H(38) is bonded in a single-bond geometry to one C(9) atom. In the thirty-fourth H site, H(39,40) is bonded in a single-bond geometry to one C(10) atom. There are thirty inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(9) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(8), and one Ge(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(12), and one V(8) atom. In the fifth O site, O(5) is bonded in a T-shaped geometry to one V(13), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(9) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(13), one V(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(11), one V(3), and one V(4) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(16), one V(4), and one V(5) atom. In the tenth O site, O(10) is bonded in a T-shaped geometry to one V(11), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(16), one V(5), and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(5), one V(6), and one Ge(3) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one V(15), one V(6), and one V(7) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(6), one V(7), and one Ge(4) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one V(15), one V(7), and one V(8) atom. In the sixteenth O site, O(16) is bonded in a T-shaped geometry to one V(12), one V(7), and one V(8) atom. In the seventeenth O site, O(17) is bonded in a distorted T-shaped geometry to one V(10), one V(12), and one V(9) atom. In the eighteenth O site, O(18) is bonded in a distorted T-shaped geometry to one V(10), one V(11), and one V(9) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 120 degrees geometry to one V(9) and one Co(3) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one V(10), one V(12), and one Ge(4) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal planar geometry to one V(10), one V(11), and one Ge(3) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one V(13), one V(14), and one Ge(1) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one V(13), one V(14), and one V(16) atom. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one V(14), one V(15), and one Ge(2) atom. In the twenty-fifth O site, O(25) is bonded in a distorted T-shaped geometry to one V(14), one V(15), and one V(16) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one V(15) and one Co(3) atom. In the twenty-seventh O site, O(27) is bonded in a bent 120 degrees geometry to one Ge(1) and one Ge(2) atom. In the twenty-eighth O site, O(28) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one Ge(1) atom. In the twenty-ninth O site, O(29) is bonded in a bent 120 degrees geometry to one Ge(3) and one Ge(4) atom. In the thirtieth O site, O(30) is bonded in a distorted trigonal planar geometry to one Co(1), one Co(2), and one Ge(3) atom. Linkers: 13 NCCN ,16 [O][Ge]([O])O[Ge]([O])([O])[O]. Metal clusters: 128 [V] ,24 [Co]. The MOF has largest included sphere 6.57 A, density 1.65 g/cm3, surface area 2328.83 m2/g, accessible volume 0.28 cm3/g