Cf. Martens et al., X-RAY STRUCTURES OF MONONUCLEAR AND DINUCLEAR CU(II) COMPLEXES OF NOVEL PYRIDINE CROWN-ETHER LIGANDS, Inorganic chemistry, 33(24), 1994, pp. 5541-5546
Two novel pyridine-crown ether ligands, 1 and 2, have been synthesized
by high-pressure additions of monoaza-15-crown-5 and diaza-18-crown-6
, respectively, to 2-vinylpyridine. Treatment of ligand 1 with 1 equiv
of Cu(ClO4)(2).6H(2)O results in the formation of a mononuclear coppe
r(II) complex 3, which crystallizes, as revealed by single-crystal X-r
ay diffraction, in the monoclinic space group P2(1)/c (No. 14) with a
= 8.4636(10) Angstrom, b = 15.912(5) Angstrom, c = 19.373(4) Angstrom,
beta = 110.341(16)degrees, V = 2446.3(1.0) Angstrom(3), and Z = 4. Th
e structure refinement converged to R = 0.040 and R(w) = 0.050. The co
pper(II) ion in 3 is surrounded by two crown ether oxygen atoms and tw
o nitrogen atoms as well as by an oxygen atom of a methanol molecule w
hich is bound in the crown ether ring. The geometry around the metal c
enter is that of a distorted trigonal bipyramid. Addition of 1 equiv o
f Cu(ClO4)(2).6H(2)O to ligand 2 yields a dinuclear Cu(II) complex (4)
, which coprecipitates with the bisprotonated ligand 2. The X-ray stru
cture of 4.2.2HClO(4) reveals a monoclinic space group C2/c (No. 15) w
ith a = 26.4295(12) Angstrom b = 9.8275(4) Angstrom, c = 26.8414(15) A
ngstrom, beta = 104.272(4)degrees, V = 6756.5(6) Angstrom(3), and Z =
4. The structure refinement converged to R = 0.078 and R(w) = 0.071. C
omplex 4 consists of a dinuclear [Cu-2(OH).2](3+) cation, With a perch
lorate anion bound to it through a bifurcated hydrogen bond to the bri
dging hydroxo group. Each copper ion is 5-fold coordinated, viz. by tw
o nitrogen and two oxygen atoms from the crown ether moiety and a brid
ging hydroxo group. Both copper ions have a trigonal bipyramidal envir
onment. Ligand 2 is protonated on the amine functions present in the c
rown ether ring. Each proton forms a trifurcated II-bond with two crow
n ether oxygen atoms and a pyridine nitrogen. Complex formation in sol
ution proceeds stepwise both for 3 and 4. At low Cu(II) to 1 ratios, t
wo ligands molecules 1 coordinate to one Cu(II) ion. This intermediate
reacts further at higher copper(II) concentrations to yield complex 3
. Complex 4 is formed via a mononuclear copper(II) complex which is th
ought to have a structure simular to that of complex 3. Both 3 and 4 u
ndergo irreversible oxidations in acetonitrile solution, at +0.04 and
-0.36 V vs Fc/Fc(+), respectively.