Synthesis, Structural Characterization and Thermal Stability of [Mn(3-bpd)2(NCS)2(H2O)2]·2H2O (1) and {[Mn(bpe)(NCS)2(H2O)2]·(3-bpd)·(bpe)·H2O}n (2) from One-Pot Crystallization

• Published in: Journal of the Chinese Chemical Society (Taipei) 2009-08, Vol.56 (4), p.709-717
• Main Authors: Liu, Chuan-Yien, Lee, Gene-Hsiang, Wang, Hsin-Ta
• Format: Article
• Language: English
• Subjects: 3-bpd; bpe; Coordination polymer; Metal-organic framework
• ISSN: 0009-4536; 2192-6549
• DOI: 10.1002/jccs.200900106

Two supramolecular architectures, [Mn(3‐bpd)2(NCS)2(H2O)2]·2H2O (1) and {[Mn(bpe)(NCS)2(H2O)2]·(3‐bpd)·(bpe)·H2O}n (2) [bpe = 1,2‐bis(4‐pyridyl)ethylene and 3‐bpd = 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene] have been synthesized and characterized by spectroscopic, elemental and single crystal X‐ray diffraction analyses. Compound 1 crystallizes in the monoclinic system, space group P21/c, with chemical formula C26H28Mn N10O4S2, a = 9.1360(6), b = 9.7490(6), c = 17.776(1) Å, β = 93.212(1)°, and Z = 2 while compound 2 crystallizes in the orthorhombic system, space group P212121, with chemical formula C38H36Mn1N10O3S2, a = 14.1902(6), b = 15.4569(7), c = 18.2838(8) Å, α = β = γ = 90°, and Z = 4. Structural determination reveals that the coordination geometry at Mn(II) in compound 1 or 2 is a distorted octahedral which consists of two nitrogen donors of two NCS−ligands, two oxygen donors of two water molecules, and two nitrogen donors of two 3‐bpd ligands for 1 and two dpe ligands for 2, respectively. The two 3‐bpd ligands in 1 adopt a monodentate binding mode and the dpe in 2 adopts a bismonodentate bridging mode to connect the Mn(II) ions forming a 1D chain‐like coordination polymer. Both the π‐π stacking interactions between the coordinated and the free pyridyl‐based ligands and intermolecular hydrogen bonds among the coordinated and the crystallized water molecules and the free pyridyl‐based ligands play an important role in construction of these 3D supramolecular architectures. Two supramolecular architectures, [Mn(3‐bpd)2(NCS)2(H2O)2].2H2O (1) and {[Mn(bpe)(NCS)2(H2O)2].(3‐bpd).(bpe).H2O}n (2) [bpe = 1,2‐bis(4‐pyridyl)ethylene and 3‐bpd = 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene] have been synthesized and characterized. Both the p‐p stacking interactions and intermolecular hydrogen bonds play important roles in construction of their 3D supramolecular architectures.