New Suberato‐bridged Supramolecular Layers: Crystal Structure of [Cu 2 (phen) 2 (C 8 H 12 O 4 ) 2 ] · 3 H 2 O with phen = 1,10‐phenanthroline

The reaction of CuCl 2  · 2 H 2 O, 1,10‐phenanthroline (phen), suberic acid and Na 2 CO 3 in a CH 3 CN–H 2 O solution yielded blue needle‐like crystals of [Cu 2 (phen) 2 (C 8 H 12 O 4 ) 2 ] · 3 H 2 O. The crystal structure (monoclinic, P 2 1 / n , a  = 10.756(2) Å, b  = 9.790(2) Å, c  = 18.593(4) Å, β = 91.15(3)°, Z  = 2, R  = 0.043, w R 2  = 0.1238) consists of suberato‐bridged $^2_\infty$ [Cu 2 (phen) 2 (C 8 H 12 O 4 ) 4/2 ] layers and hydrogen bonded H 2 O molecules. The Cu atoms are coordinated by two N atoms from one bidentate chelating phen ligand and three carboxyl O atoms from different suberato ligands to form distorted [CuN 2 O 3 ] square‐pyramids with one carboxyl O atom at the apical position (d(Cu–N) = 2.017(2), 2.043(3) Å, basal d(Cu–O) = 1.936(2), 1.951(2) Å and axial d(Cu–O) = 2.389(2) Å). Two [CuN 2 O 3 ] square‐pyramids are condensed via a common O–O edge to a centrosymmetric [Cu 2 N 4 O 4 ] dimer with the Cu…Cu distance of 3.406(1) Å indicating no interaction between Cu atoms. The resultant [Cu 2 N 4 O 4 ] dimers are interlinked by the tridentate suberato ligands to form $^2_\infty$ [Cu 2 (phen) 2 (C 8 H 12 O 4 ) 4/2 ] layers parallel to (101). These are assembled via π‐π stacking interactions into 3D network with H 2 O molecules in the tunnels extending in the [010] direction.