π
ꢀCOMPLEXES OF COPPER(I) HALIDES WITH 3ꢀ(ALLYLAMINO)ꢀ(C3H5NHC2H4CN, Apn)
87
lation in a vacuum of a waterꢀjet pump. The yield of Selected bond lengths and bonds angles are given in
Apn was 88% (15 mL).
the captions for figures.
The coordinates of atoms and other parameters for
Synthesis of 3ꢀ(diallylamino)propanenitrile. A mixꢀ
ture of acrylonitrile (7 mL, 0.11 mol) and diallylamine
(16 mL, 0.13 mol) was heated with a reflux condenser
compounds
Crystallographic Data Centre (nos. 811967, 811968,
811969, and 811970 for compounds II III, and IV
I–IV were deposited with the Cambridge
I,
,
,
in a water bath at 50–60°C for 8 h followed by storing
ccdc.cam.ac.uk).
at room temperature for 24 h [13]. After a small
amount of unreacted starting substances was distilled
off in a vacuum of a waterꢀjet pump, the redꢀorange
liquid was distilled at 130
Dapn was 75% (13 mL).
°C (20 mmHg). The yield of
RESULTS AND DISCUSSION
The inorganic fragment Cu2Cl2 in structure
I
Synthesis of I–VI. Colorless crystals of
compound were obtained by the ac electrochemical
synthesis ( = 0.45 V, init = 0.58 mA) [14] on copper
wire electrodes from CuCl2 2Н2О (0.8 g, 4.5 mmol),
(Fig. 1) is identical to that in structure [4]. The trigꢀ
V
I
U
onal pyramidal coordination environment of Cu(I) is
formed by the C=C bond, the amine nitrogen atom,
the chlorine atom in the base of the pyramid, and the
second Cl atom in the apical position. The C=C coorꢀ
dination bond length is 1.373(2) Å. The bridging funcꢀ
tion of the Apn molecule joins particular units Cu2Cl2
into a threeꢀdimensional framework. It is surprisingly
that the N atom of the cyano group of the Apn ligand
is not coordinated by the metal atom.
I
⋅
Apn (0.6 mL, 5 mmol), and 95% С2Н5ОН (4.5 mL)
for 4 days. Colorless crystals of complex II were
obtained for 24 h under similar conditions using
approximately the same amounts of reactants (an ethꢀ
anolic solution of Apn was pretitrated with a concenꢀ
trated aqueous solution of HCl to pH 4.5). Colorless
crystals of compound III were obtained by the ac elecꢀ
The protonation of the amine N atom changes the
coordination behavior of the Apn molecule: in the
trochemical synthesis [14] from CuCl2 · 2Н2О (0.70 g,
4 mmol), Dapn (0.7 mL, 4.3 mmol), and 95%
С2Н5ОН (4 mL) without HCl for 8 days. The crystals
of compound III are also formed using an ethanolic
solution of Dapn pretitrated with a concentrated
aqueous solution of HCl to pH 4.5. Yellowish crystals
of complex IV were grown for 5 days on copper elecꢀ
trodes under the conditions of ac electrochemical synꢀ
thesis from CuBr2 (0.67 g, 4 mmol), Dapn (0.7 mL,
4.3 mmol, was not titrated with HBr), and ethanol
structure of
π
complex II, the N atom of the cyano
group enters into the coordination environment of
Cu(I). The structure of this compound consists of infiꢀ
n−
3
n
nite ribbons
similar to those described in
,
Cu Cl
(
)
2
the structures of [H+(diallylamine)Cu2Br3] [19] and
complex VI [5]. The inorganic fragments are
joined into the threeꢀdimensional framework by the
bridging cations Н+Аpn (Fig. 2). Unlike structure
π σ
,
I,
(4 mL). The density of crystals of I–IV was deterꢀ
mined by the flotation method in a chloroform–broꢀ
moform mixture (Table 1).
the trigonal pyramidal environment of one of the
independent metal atoms in structure II contains the
C=C bond and the Cl atoms, whereas the second
Cu(I) atom is inside the slightly deformed tetrahedron
with the nitrile N atom and three Cl atoms in the verꢀ
tices. The structure of complex II is close to that of
complex VI [5].
Xꢀray diffraction analysis. After preliminary studies
by the photomethod, diffraction sets obtained on
KUMAꢀKM4/CCD and Rigaku AFC7 singleꢀcrystal
π σ
,
diffractometers (CCD detector, Мо
К
radiation,
α
graphite monochromator,
ature attachment) were used for structure determinaꢀ
tion of compounds IV. Corrections to the Lorentz
ω
scan mode, lowꢀtemperꢀ
Isostructural
differ in structure from compounds
π
complexes III and IV substantially
and II. They
I
I–
were formed during the synthesis in a medium of proꢀ
tonogenic ethanol, and the acidic medium appeared
and polarization factors were applied to reflection
intensities. The Xꢀray experimental data were proꢀ
cessed using the CrysAlisRED program [15] for comꢀ
due to the solvolysis of CuCl2 2H2O or CuBr2. The
⋅
pronation of the amine nitrogen atom of Dapn imparts
the cationic state Н+Dapn to the ligand molecule and,
hence, in structures III and IV it is coordinated to the
Cu(I) atom by the C=C bond only (unlike II, where
both the cyano group and the C=C bond are coordiꢀ
nated by the copper(I) atom). Owing to the bridging
function of the halogen atoms, the polymeric anion
n−
pounds
gram was used for processing the Xꢀray data for comꢀ
plex II [16]. Structures IV were solved by direct
I, III, and IV. The Rigaku Crystal Clear proꢀ
I–
methods, and light atoms were revealed from the difꢀ
ference Fourier syntheses. An absorption correction
was applied by the analytical method [17]. The strucꢀ
tures of compounds
SHELX program package [18]. The hydrogen atoms
in structures IV were found from the difference
I–IV were solved using the
appears in which the Cu(I) atom coordiꢀ
,
nates the C=C bond and three X atoms (X = Cl, Br)
(Fig. 3).
CuX
(
)
2
n
I–
Fourier syntheses and refined in the riding model
along with the nonꢀhydrogen atoms. The crystalloꢀ
The C=C bond coordinated by copper(I) is elonꢀ
graphic data for compounds
I–IV and conditions of gated to 1.374(3) Å in III and to 1.365(5) Å in IV.
the diffraction experiment are collected in Table 1. Another double bond in the Н+Dаpn cation, which
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
No. 2
2012
Luk'yanov
