catena-Poly[[[diaqua(tetramethylethylenediamine-κ²N,N′)nickel(II)]-μ-sulfato-κ²O:O′] monohydrate]

Abstract

The title compound, {[Ni(SO4)(C6H16N2)(H2O)2]·H2O}n, contains a NiII atom that is coordinated nearly octa­hedrally by a chelating tetra­ethyl­enediamine (tmeda) ligand, two water mol­ecules in a cis arrangement and two O atoms of two sulfate anions in a trans arrangement. The sulfate anions act as μ2-bridging ligands leading to a chain structure of alternating NiO4N2 octa­hedra and SO4 tetra­hedra parallel to [001]. The polymeric chains are linked by O—H⋯O hydrogen bonds between coordinating water mol­ecules and sulfate anions to give double strands. There is a lattice water mol­ecule which is also involved in O—H⋯O hydrogen bonding between adjacent [Ni(SO4)(tmeda)(H2O)2] chains.

A Practical Synthesis of [(tmeda)Ni(CH3)2], Isotopically Labeled [(tmeda)Ni(13CH3)2], and Neutral Chelated-Nickel Methyl Complexes

“…Promising results, however, were obtained when [(tmeda)­NiSO 4 ] ( 3 ) obtained by azeotropic dehydration of [(tmeda)­(H 2 O) 2 NiSO 4 (H 2 O)] was reacted with methyllithium at 243–263 K: Though the reaction failed in mixtures of toluene and thf probably due to complete insolubility of 3 , a slow formation of 5 was evident in thf. The crude product obtained after 2 h at 253 K and filtration, however, contains huge amounts of unreacted methyllithium which at 253 K already causes the decomposition of 5 to nickel black and, notably, methane (not ethane as observed in the presence of, e.g.…”

“…Ni­(acac) 2 , Ni­(OAc) 2 ·4H 2 O, and 13 CH 3 I were purchased from Aldrich, and methyllithium (1.6 M in diethyl ether) and n -butyllithium were purchased from Acros Organics and Aldrich. [(tmeda)­Ni­(acac) 2 ], [(tmeda) 2 Ni 2 (OAc) 4 (H 2 O)], [(tmeda)­(H 2 O) 2 NiSO 4 ], and [(tmeda)­NiF 2 ] n were synthesized by known procedures. 1 H NMR spectra are referenced to the residual protio signal of the deuterated solvent, 13 C NMR spectra are referenced to the deuterated solvent signal, and 31 P NMR spectra are referenced indirectly by using the deuterium on-resonance signal of the lock channel.…”

“…Therefore, a synthesis protocol involving more easily removable lithium salts was envisaged: in a first set of experiments a combination of anhydrous nickel sulfate, tmeda, and methyllithium failed to generate 5 (and insoluble lithium sulfate) in diethyl ether, toluene, thf, or mixtures thereof. 15 Promising results, however, were obtained when [(tmeda)-NiSO 4 ] (3) obtained by azeotropic dehydration of [(tmeda)-(H 2 O) 2 NiSO 4 (H 2 O)] 16 was reacted with methyllithium at 243−263 K: Though the reaction failed in mixtures of toluene and thf probably due to complete insolubility of 3, a slow formation of 5 was evident in thf. The crude product obtained after 2 h at 253 K and filtration, however, contains huge Scheme 2.…”