Cu3H8(CN2)8(CH3CHO)2 crystallizes in the monoclinic C2/m space group. The structure consists of four dimethyl ether molecules inside a Cu3H8(CN2)8 framework. In the Cu3H8(CN2)8 framework, there are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted square co-planar geometry to four equivalent N(1) atoms. All Cu(1)-N(1) bond lengths are 2.03 Å. In the second Cu site, Cu(2) is bonded in a tetrahedral geometry to two equivalent N(3) and two equivalent N(4) atoms. Both Cu(2)-N(3) bond lengths are 1.99 Å. Both Cu(2)-N(4) bond lengths are 2.05 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one N(1), and one N(4) atom. The C(1)-C(2) bond length is 1.49 Å. The C(1)-N(1) bond length is 1.35 Å. The C(1)-N(4) bond length is 1.34 Å. In the second C site, C(2) is bonded in a distorted water-like geometry to one C(1), one H(1), and one H(2) atom. The C(2)-H(1) bond length is 1.10 Å. The C(2)-H(2) bond length is 1.10 Å. There are four inequivalent N sites. In the first N site, N(2) is bonded in a water-like geometry to one N(1) and one N(3) atom. The N(2)-N(1) bond length is 1.34 Å. The N(2)-N(3) bond length is 1.32 Å. In the second N site, N(3) is bonded in a trigonal planar geometry to one Cu(2), one N(2), and one N(4) atom. The N(3)-N(4) bond length is 1.36 Å. In the third N site, N(4) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(1), and one N(3) atom. In the fourth N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(1), and one N(2) atom. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. Linkers: 1 C1Cc2nnnn2[Cu]2(n3nnnc3CCO1)n1nnnc1CCOCCc1nnnn12. Metal clusters: 2 [Cu]. The MOF has largest included sphere 2.45 A, density 2.11 g/cm3, surface area 3207.56 m2/g, accessible volume 0.11 cm3/g