Fe2As3(CO6)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in an octahedral geometry to one O(17), one O(18), one O(3), one O(4), one O(6), and one O(7) atom. The Fe(1)-O(17) bond length is 2.08 Å. The Fe(1)-O(18) bond length is 2.13 Å. The Fe(1)-O(3) bond length is 2.05 Å. The Fe(1)-O(4) bond length is 1.95 Å. The Fe(1)-O(6) bond length is 1.92 Å. The Fe(1)-O(7) bond length is 1.96 Å. In the second Fe site, Fe(2) is bonded in an octahedral geometry to one O(10), one O(11), one O(12), one O(14), one O(19), and one O(20) atom. The Fe(2)-O(10) bond length is 1.95 Å. The Fe(2)-O(11) bond length is 1.94 Å. The Fe(2)-O(12) bond length is 2.01 Å. The Fe(2)-O(14) bond length is 1.99 Å. The Fe(2)-O(19) bond length is 2.08 Å. The Fe(2)-O(20) bond length is 2.09 Å. In the third Fe site, Fe(3) is bonded in an octahedral geometry to one O(1), one O(2), one O(21), one O(22), one O(8), and one O(9) atom. The Fe(3)-O(1) bond length is 1.93 Å. The Fe(3)-O(2) bond length is 1.93 Å. The Fe(3)-O(21) bond length is 2.09 Å. The Fe(3)-O(22) bond length is 2.17 Å. The Fe(3)-O(8) bond length is 1.98 Å. The Fe(3)-O(9) bond length is 1.95 Å. In the fourth Fe site, Fe(4) is bonded in an octahedral geometry to one O(13), one O(15), one O(16), one O(23), one O(24), and one O(5) atom. The Fe(4)-O(13) bond length is 2.00 Å. The Fe(4)-O(15) bond length is 2.03 Å. The Fe(4)-O(16) bond length is 1.93 Å. The Fe(4)-O(23) bond length is 2.07 Å. The Fe(4)-O(24) bond length is 2.14 Å. The Fe(4)-O(5) bond length is 1.94 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(19) and one O(21) atom. The C(1)-O(19) bond length is 1.28 Å. The C(1)-O(21) bond length is 1.24 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one O(20) and one O(22) atom. The C(2)-O(20) bond length is 1.27 Å. The C(2)-O(22) bond length is 1.25 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one O(17) and one O(23) atom. The C(3)-O(17) bond length is 1.24 Å. The C(3)-O(23) bond length is 1.27 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(18) and one O(24) atom. The C(4)-O(18) bond length is 1.26 Å. The C(4)-O(24) bond length is 1.26 Å. There are six inequivalent As sites. In the first As site, As(1) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. The As(1)-O(1) bond length is 1.67 Å. The As(1)-O(2) bond length is 1.68 Å. The As(1)-O(3) bond length is 1.68 Å. In the second As site, As(2) is bonded in a water-like geometry to one O(4) and one O(5) atom. The As(2)-O(4) bond length is 1.68 Å. The As(2)-O(5) bond length is 1.69 Å. In the third As site, As(3) is bonded in a trigonal non-coplanar geometry to one O(6), one O(7), and one O(8) atom. The As(3)-O(6) bond length is 1.65 Å. The As(3)-O(7) bond length is 1.66 Å. The As(3)-O(8) bond length is 1.68 Å. In the fourth As site, As(4) is bonded in a water-like geometry to one O(10) and one O(9) atom. The As(4)-O(10) bond length is 1.69 Å. The As(4)-O(9) bond length is 1.68 Å. In the fifth As site, As(5) is bonded in a trigonal non-coplanar geometry to one O(11), one O(12), and one O(13) atom. The As(5)-O(11) bond length is 1.66 Å. The As(5)-O(12) bond length is 1.67 Å. The As(5)-O(13) bond length is 1.68 Å. In the sixth As site, As(6) is bonded in a trigonal non-coplanar geometry to one O(14), one O(15), and one O(16) atom. The As(6)-O(14) bond length is 1.65 Å. The As(6)-O(15) bond length is 1.66 Å. The As(6)-O(16) bond length is 1.66 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(3) and one As(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(3) and one As(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Fe(1) and one As(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Fe(1) and one As(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Fe(4) and one As(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Fe(1) and one As(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(1) and one As(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Fe(3) and one As(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Fe(3) and one As(4) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Fe(2) and one As(4) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one As(5) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one Fe(2) and one As(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Fe(4) and one As(5) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Fe(2) and one As(6) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Fe(4) and one As(6) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Fe(4) and one As(6) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Fe(1) and one C(3) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Fe(1) and one C(4) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one Fe(2) and one C(1) atom. In the twentieth O site, O(20) is bonded in a bent 120 degrees geometry to one Fe(2) and one C(2) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Fe(3) and one C(1) atom. In the twenty-second O site, O(22) is bonded in a bent 120 degrees geometry to one Fe(3) and one C(2) atom. In the twenty-third O site, O(23) is bonded in a bent 120 degrees geometry to one Fe(4) and one C(3) atom. In the twenty-fourth O site, O(24) is bonded in a water-like geometry to one Fe(4) and one C(4) atom. Linkers: 4 [O]C(=O)C([O])=O. Metal clusters: 8 [Fe]. The MOF has largest included sphere 4.04 A, density 2.15 g/cm3, surface area 2347.19 m2/g, accessible volume 0.20 cm3/g