KBi2(C6O7)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(11), and one O(6) atom. The K(1)-O(1) bond length is 2.88 Å. The K(1)-O(10) bond length is 2.88 Å. The K(1)-O(11) bond length is 2.84 Å. The K(1)-O(6) bond length is 2.81 Å. There are twelve inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.52 Å. The C(1)-O(1) bond length is 1.22 Å. The C(1)-O(2) bond length is 1.27 Å. In the second C site, C(2) is bonded in a water-like geometry to one C(1) and one C(3) atom. The C(2)-C(3) bond length is 1.53 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one O(7) atom. The C(3)-C(4) bond length is 1.57 Å. The C(3)-O(7) bond length is 1.41 Å. In the fourth C site, C(4) is bonded in a bent 120 degrees geometry to one C(3) and one C(5) atom. The C(4)-C(5) bond length is 1.49 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(3), and one O(4) atom. The C(5)-O(3) bond length is 1.26 Å. The C(5)-O(4) bond length is 1.26 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(6)-O(5) bond length is 1.31 Å. The C(6)-O(6) bond length is 1.28 Å. In the seventh C site, C(7) is bonded in a distorted bent 120 degrees geometry to one C(8), one O(8), and one O(9) atom. The C(7)-C(8) bond length is 1.52 Å. The C(7)-O(8) bond length is 1.24 Å. The C(7)-O(9) bond length is 1.29 Å. In the eighth C site, C(8) is bonded in a water-like geometry to one C(7) and one C(9) atom. The C(8)-C(9) bond length is 1.53 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(10), one C(8), and one O(14) atom. The C(9)-C(10) bond length is 1.52 Å. The C(9)-O(14) bond length is 1.43 Å. In the tenth C site, C(10) is bonded in a bent 120 degrees geometry to one C(11) and one C(9) atom. The C(10)-C(11) bond length is 1.51 Å. In the eleventh C site, C(11) is bonded in a distorted bent 120 degrees geometry to one C(10), one O(10), and one O(11) atom. The C(11)-O(10) bond length is 1.25 Å. The C(11)-O(11) bond length is 1.26 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one O(12) and one O(13) atom. The C(12)-O(12) bond length is 1.28 Å. The C(12)-O(13) bond length is 1.25 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted pentagonal pyramidal geometry to one O(10), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. The Bi(1)-O(10) bond length is 2.44 Å. The Bi(1)-O(3) bond length is 2.46 Å. The Bi(1)-O(5) bond length is 2.33 Å. The Bi(1)-O(7) bond length is 2.12 Å. The Bi(1)-O(8) bond length is 2.51 Å. The Bi(1)-O(9) bond length is 2.43 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(12), one O(14), and one O(2) atom. The Bi(2)-O(1) bond length is 2.46 Å. The Bi(2)-O(11) bond length is 2.44 Å. The Bi(2)-O(12) bond length is 2.28 Å. The Bi(2)-O(14) bond length is 2.12 Å. The Bi(2)-O(2) bond length is 2.50 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(1), one C(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one C(1) and one Bi(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one C(5) and one Bi(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one C(5) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to one C(6) and one Bi(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one K(1) and one C(6) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one C(3) and one Bi(1) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one C(7) and one Bi(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one C(7) and one Bi(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one K(1), one C(11), and one Bi(1) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one K(1), one C(11), and one Bi(2) atom. In the twelfth O site, O(12) is bonded in a distorted water-like geometry to one C(12) and one Bi(2) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one C(12) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one C(9) and one Bi(2) atom. Linkers: 8 [O]C(=O)[C]C([O])([C]C([O])=O)C([O])=O. Metal clusters: 4 [K] ,8 [Bi]. The MOF has largest included sphere 4.74 A, density 2.25 g/cm3, surface area 2200.81 m2/g, accessible volume 0.17 cm3/g