Identification of a Near-Linear Supramolecular Water Dimer, (H₂O)₂, in the Channel of an Inorganic Framework Material

Abstract

Supramolecular water dimer, (H(2)O)(2), is fundamentally important. During the course of our work on polyoxometalates, we have been able to identify the existence of hydrogen-bonded, near-linear water dimers in the "sinuous" channels of an inorganic framework material, Na(3)(n)(H(2)O)(6)(n)[Al(OH)(6)Mo(6)O(18)](n)() x 2nH(2)O, 1. The three-dimensional network structure of 1 in the solid state is assembled by the Anderson type of heteropolyanions as building blocks sharing sodium cations. Vibrational spectroscopy, X-ray powder diffraction technique, TG-DSC analyses, and single-crystal X-ray structure analysis have characterized this host-guest system, 1. Crystal data for 1: triclinic space group Ponemacr;, a = 12.0618 (3) A, b = 13.1570 (4) A, c = 14.1563 (4) A, alpha = 80.7850 (10) degrees, beta = 75.2660 (10) degrees, gamma = 68.9210 (10) degrees, and Z = 3.

Structural Diversity in Zinc Phosphates and Phosphinates: Observation of a Lattice Water Dimer Sandwiched Between Phosphoryl Oxygen Atoms

“…Similarly, the H6B atom on O6 forms a hydrogen bond with O4 of the phosphinate ligand on one side. This is a slightly different situation compared to the earlier examples of water dimer found in inorganic frameworks, [24,25] where the dimer is normally held by the metal-coordinated water molecule rather than an M=O or an E=O acceptor.…”

“…[20,21] Although the structure of the water dimer was characterized by molecular beam experiments as early as 1977, [22] the existence of such dimeric units in organic [23] and inorganic [24,25] host lattices has been studied only recently. The formation of the water dimer in 3 represents a case of capture of the water dimer between free P=O groups in the lattice.…”

“…These two water molecules have only one hydrogen bond between them (O6-H6A···05), as has also been determined for the water dimer by both gas-phase studies [22] and solid-state crystal diffraction in organic and inorganic lattices. [23][24][25] In addition to the solitary hydrogen bond between the two water molecules, the water dimer is involved in three additional hydrogen bonds to the P=O oxygen atoms in the neighborhood. For example, both the hydrogen atoms of O5 are involved in P=O···H-O interaction with two different phosphinate moieties on either Figure 10.…”

From Molecular to Two‐Dimensional Anderson Polyoxomolybdate: Synthesis, Crystal Structure, and Thermal Behavior of [{Ni(H2O)4}2{Ni(OH)6Mo6O18}]·4H2O and [Ni(H2O)6][Ag2{Ni(OH)6Mo6O18}]·8H2O

“…[11][12][13][14][15][16][17] Recently, the formation of molecular, spiralshaped, and two-dimensional Anderson inorganic-organic hybrids have been reported. [18][19][20] With chromonium, [(H 2 O) 4 Ag 3 ][Cr(OH) 6 Mo 6 O 18 ]·3H 2 O was characterized as an open 3D framework by An et al, [20] whereas with nickel, the structure of (NH 4 ) 4 [Ni(OH) 6 Mo 6 O 18 ]·4H 2 O revealed [21] the Anderson units are interlinked by ammonium cations and water molecules.…”

μ‐η1:η1‐N,N'‐Imidazolidine‐Bridged Dicopper(II/III) Complexes of a New Dinucleating μ‐Bis(tetradentate) Schiff Base Ligand: Synthesis, Structural Characterization, 1H NMR Spectroscopy, and Magnetic Coupling

“…The complex also binds a water dimer showing a novel example of simple near-linear selfassembled water cluster (H 2 O) 2 in a crystalline dimetal complex. [16] Recently, it has been discovered that certain imidazole compounds can stabilize similar infinite 1D water chains [17] as potential models of biologically relevant proton wires. Similar tetrameric water structure has also been identified recently in an organic macrocyclic ligand crystal host.…”