Syntheses and Crystal Structures of [M 2 (H 2 O) 2 (phen) 2 (C 7 H 10 O 4 ) 2 ] · 4 H 2 O with M = Mn II , Cu II and phen = 1,10‐phenanthroline

Two mixed ligand complexes of [M 2 (H 2 O) 2 (phen) 2 (C 7 H 10 O 4 ) 2 ] · 4 H 2 O(M = Mn ( 1 ), Cu ( 2 )) were synthesized and the crystal structures were established using the single crystal X‐ray diffraction methods. In 1 ( P 1 (no. 2), a  = 10.169(1) Å, b = 10.194(1) Å, c  = 11.921(2) Å, α = 65.55(1)°, β = 65.54(1)°, γ = 88.96(1)°, V  = 1006.3(3) Å 3 , Z  = 1), the Mn atoms are octahedrally coordinated by two N atoms of one phen ligands and four O atoms of one H 2 O molecule and three tridentate pimelato ligands (d(Mn–N) = 2.284, 2.303 Å; d(Mn–O) = 2.152–2.200 Å). Two adjacent [MnN 2 O 4 ] octahedra are condensed via two bidentate bridging carboxyl O atoms into [Mn 2 N 4 O 6 ] subunits, which are interlinked through pimelato ligands to form 1D $^1_\infty$ [Mn 2 (H 2 O) 2 (phen) 2 (C 7 H 10 O 4 ) 4/2 ] bands with phen ligands on both sides. The 1D bands extending in [010] direction are assembled into 2D layers parallel to (100) by π‐π stacking interactions between two adjacent phen rings from different bands. The hydrogen bonded H 2 O molecules are sandwiched between layers. Complex 2 ( P 2 1 / n (no. 14), a = 9.908(1) Å, b  = 11.620(1) Å, c  = 17.890(2) Å, β = 103.15(1)°, V = 2005.7(3) Å 3 , Z = 2) consists of the centrosymmetric dinuclear [Cu 2 (H 2 O) 2 ‐ (phen) 2 (C 7 H 10 O 4 ) 2 ] complex molecules and hydrogen bonded H 2 O molecules. Each Cu atom coordinates to two N atoms of one phen ligand and three O atoms of one H 2 O molecule and two bis‐monodentate pimelato ligands to give a distorted square‐pyramidal coordination with the H 2 O molecule at the apical site (d(Cu–N) = 2.023, 2.030 Å, basal d(Cu–O) = 1.941, 1.967 Å, axial d(Cu–O) = 2.268 Å). The π‐π stacking interactions and hydrogen bonding are responsible for the supramolecular assemblies.