New discrete and polymeric supramolecular architectures derived from dinuclear Co(II), Ni(II) and Cu(II) complexes of aryl-linked bis-beta-diketonato ligands and nitrogen bases: synthetic, structural and high pressure studies.
New examples of nitrogen base adducts of dinuclear Co(II), Ni(II) and Cu(II) complexes of the doubly deprotonated forms of 1,3-aryl linked bis-beta-diketones of type [RC(=O)CH(2)C(=O)C(6)H(4)C(=O)CH(2)C(=O)R] (L(1)H(2)) incorporating the mono- and difunctional amine bases pyridine (Py), 4-ethylpyridine (EtPy), piperidine (pipi), 1,4-piperazine (pip), N-methylmorpholine (mmorph), 1,4-dimethylpiperazine (dmpip) and N,N,N',N'-tetramethylethylenediamine (tmen) have been synthesised by reaction of the previously reported [Cu(2)(L(1))(2)].2.5THF (R = Me), [Cu(2)(L(1))(2)(THF)(2)] (R = t-Bu), [Ni(2)(L(1))(2)(Py)(4)] (R = t-Bu) and [Co(2)(L(1))(2)(Py)(4)] (R = t-Bu) complexes with individual bases of the above type. Comparative X-ray structural studies involving all ten base adduct derivatives have been obtained and reveal a range of interesting discrete and polymeric molecular architectures. The respective products have the following stoichiometries: [Cu(2)(L(1))(2)(Py)(2)].Py (R = Me), [Cu(2)(L(1))(2)(EtPy)(2)].2EtPy (R = t-Bu), [Cu(2)(L(1))(2)(pipi)(2)].2pipi (R = t-Bu), [Cu(2)(L(1))(2)(mmorph)(2)] (R = t-Bu), [Cu(2)(L(1))(2)(tmen)(2)] (R = t-Bu) and {[Cu(2)(L(1))(2)(pip)].pip.2THF}(n), [Co(2)(L(1))(2)(tmen)(2)] (R = t-Bu), [Ni(2)(L(1))(2)(Py)(4)].dmpip (R = t-Bu), [Ni(2)(L(1))(2)(pipi)(4)].pipi (R = t-Bu) and [Ni(2)(L(1))(2)(tmen)(2)] (R = t-Bu). The effect of pressure on the X-ray structure of [Cu(2)(L(1))(2)(mmorph)(2)] has been investigated. An increase in pressure from ambient to 9.1 kbar resulted in modest changes to the unit cell parameters as well as a corresponding decrease of 6.7 percent in the unit cell volume. While a small 'shearing' motion occurs between adjacent molecular units throughout the lattice, no existing bonds are broken or new bonds formed.
Clegg
Jack K
JK
School of Chemistry, University of Sydney, NSW, 2006, Australia.
Hayter
Michael J
MJ
Jolliffe
Katrina A
KA
Lindoy
Leonard F
LF
McMurtrie
John C
JC
Meehan
George V
GV
Neville
Suzanne M
SM
Parsons
Simon
S
Tasker
Peter A
PA
Turner
Peter
P
White
Fraser J
FJ
D003035:Cobalt / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005029:Ethylenediamines / Q000737:chemistry; D007659:Ketones / Q000737:chemistry; D008024:Ligands; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D000077489:Piperazine; D010879:Piperazines / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry; D011312:Pressure; D011725:Pyridines / Q000737:chemistry
D056831:Coordination Complexes; D005029:Ethylenediamines; D007659:Ketones; D008024:Ligands; D010879:Piperazines; D011108:Polymers; D011725:Pyridines; C005798:N,N,N',N'-tetramethylethylenediamine; D000077489:Piperazine; D003035:Cobalt; D003300:Copper; D009532:Nickel; D009584:Nitrogen; C522350:1,4-dimethylpiperazine