Synthesis and crystal
structure of N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium
(dalltmen2+) compounds: {dalltmen}(ClO4)2
and the copper(I) nitrate π-complex [{dalltmen}0.5Cu(NO3)2]
Chem.
Met. Alloys 5 (2012) 90-97
https://doi.org/10.30970/cma5.0212
Mykhaylo MONCHAK, Evgeny GORESHNIK, Maryan MYS’KIV
N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium dichloride ({dalltmen}Cl2) was
synthesized from N,N,N',N'-tetramethylethylenediamine
(obtained by the Eschweiler-Clarke reaction of ethylenediamine, formaldehyde and formic acid) and allyl chloride. Then an ethanol solution of KOH was added to replace the Cl–
anions by OH– ones and N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium
dihydroxide ({dalltmen}(OH)2) was obtained. Single crystals of
{dalltmen}(ClO4)2 (I) and the π-complex [{dalltmen}0.5Cu(NO3)2]
(II) were obtained from alcohol solutions containing the hydroxide of the tetramethylethylenediamine diallyl
derivative, previously titrated by HClO4 (or HNO3), and
Cu(ClO4)2∙6H2O (or Cu(NO3)2·3H2O)
by ac-electrochemical synthesis on
copper wire electrodes. The structures of compounds I and II were
determined by X-ray diffraction. Crystals I are orthorhombic: space group Pbca, Z =
4,
a = 11.4125(6), b = 10.4604(5), c = 15.2884(8)
Å, V = 1825.1(2) Å3.
The structure consists of N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium
cations and ClO4– anions, which
are held together by electrostatic interactions and hydrogen bonds. Crystals II
are monoclinic: space group P21/c, Z = 4, a =
7.9620(4), b = 8.2823(4), c = 15.6224(8) Å, β = 96.793(2)°,
V = 1022.97(9) Å3. The
structure contains infinite anionic chains (Cu(NO3)2–)n
with only one independent metal atom. The C=C bonds of the centrosymmetric
N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium
cation are π-coordinated by Cu(I) atoms from
parallel inorganic fragments, so that the dalltmen2+
moities play a bridging role, connecting separate (Cu(NO3)2–)n
polymeric chains into layers (coordination nets). A branched system of hydrogen
bonds connects the nets into a framework.
Fragment of crystal structure II
Keywords
N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium cation /
Anionic chains / Copper(I) nitrate π‑complex / Hydrogen bonds