Synthesis and steric structure of N′′-(arylmethylidene)- N′′′-(1-methyl-3-phenylprop-2-yn-1-ylidene) thiocarbonohydrazides

Article abstract of DOI:10.1134/s1070428008010144

Thiocarbonohydrazones derived from aromatic aldehydes reacted with 4-phenylbut-3-yn-2-one in aqueous acetic acid (20°C, 2 h) to produce previously unknown N′′-[(E-s-cis)-arylmethylidene]- N′′′-[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-ylidene] thiocarbono

Full text of DOI:10.1134/s1070428008010144

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 1, pp. 114–119. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © T.E. Glotova, M.Yu. Dvorko, N.N. Chipanina, A.I. Albanov, L.V. Sherstyannikova, O.N. Kazheva, A.N. Chekhlov, O.A. D’yachenko,
2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 1, pp. 117–121.
Dedicated to Full Member of the Russian Academy of Sciences
G.A. Tolstikov on his 75th anniversary
Synthesis and Steric Structure
of N″-(Arylmethylidene)-N″′-(1-methyl-3-phenylprop-
2-yn-1-ylidene)thiocarbonohydrazides
T. E. Glotovaa, M. Yu. Dvorkoa, N. N. Chipaninaa, A. I. Albanova, L. V. Sherstyannikovaa,
O. N. Kazhevab, A. N. Chekhlovb, and O. A. D’yachenkob
a Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: glotova@irioch.irk.ru
b Institute of Chemical Physics Problems, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, Russia
Received May 30, 2007
Abstract—Thiocarbonohydrazones derived from aromatic aldehydes reacted with 4-phenylbut-3-yn-2-one in
aqueous acetic acid (20°C, 2 h) to produce previously unknown N″-[(E-s-cis)-arylmethylidene]-N″′-[(Z-s-
trans)-1-methyl-3-phenylprop-2-yn-1-ylidene]thiocarbonohydrazides with high chemo-, regio-, and stereo-
selectivity. The steric structure of N″-[(E-s-cis)-benzylidene]-N″′-[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-
ylidene]thiocarbonohydrazide in crystal and in solution was studied by X-ray analysis and IR and NMR
spectroscopy.
DOI: 10.1134/S1070428008010144
Thiocarbonohydrazones and their complexes with
transition complexes exhibit a broad spectrum of bio-
logical activity (antituberculostatic, antitumor, anti-
viral, fungicidal) [1–5]. Hydrazones having unsaturat-
ed fragments, including acetylenic, attract interest as
highly reactive building blocks for organic synthesis.
Such N,S-multident conjugated systems are promising
as ligands for the preparation of polynuclear com-
plexes [3–8] possessing specific properties (such as
redox and magnetic) [3, 7, 9–11]. A convenient ap-
proach to such compounds may be based on reactions
of accessible α-acetylenic ketones with thiocarbono-
hydrazide (thiocarbonic acid dihydrazide) and its
derivatives [2, 12].
the carbonyl group to produce functionally substituted
dihydropyrazoles [14].
In continuation of our studies on reactions of bi-
electrophilic α-acetylenic ketones with thiocarbonohy-
drazones and their synthetic potential, we examined
the reactions of 4-phenylbut-3-yn-2-one (I) with thio-
carbonohydrazones IIa–IId derived from aromatic
Scheme 1.
S
O
+
Ph
H2N
N
R
N
N
Me
H
H
I
IIa–IId
S
We previously reported that terminal α-acetylenic
ketones react with aromatic aldehyde thiocarbonohy-
drazones to give, depending on the reactant ratio,
2-(2-acylvinyl)- or 2,2-bis(2-acylvinyl)thiocarbonohy-
drazones [13] and that the reactions of benzaldehyde
thiocarbonohydrazone with 1-benzoyl- and 1-thenoyl-
2-phenylacetylenes involve the triple C≡C bond and
Me
N
N
H
NH
AcOH, H2O
–H2O
N
R
Ph
IIIa–IIId
R = Ph (a), 4-Me2NC6H4 (b), 4-ClC6H4 (c), 4-O2NC6H4 (d).
114

SYNTHESIS AND STERIC STRUCTURE OF N″-(ARYLMETHYLIDENE)-...
aldehydes. The reactions were carried out in aqueous
115
acetic acid at room temperature (reaction time 2 h),
and they involved exclusively the carbonyl group in
molecule I to give the corresponding N″-[(E-s-cis)-
arylmethylidene]-N′′′-[(Z-s-trans)-1-methyl-3-phenyl-
prop-2-yn-1-ylidene]thiocarbonohydrazides IIIa–IIId
in 78–82% yield (Scheme 1).
S
C18
N2
C1
N1
C2
N3
N4
C3
C4
H1
The molecular and crystalline structure of com-
pound IIIa was determined by X-ray analysis of its
single crystal. Conformational behavior of compounds
IIIa–IIId in solution was studied by IR spectroscopy
C11
C12
i
1
and H, 13C, and 15N NMR using two-dimensional
C5
C17
C6
homo- and heteronuclear correlation techniques. We
also performed quantum-chemical calculations of nor-
mal vibration frequencies for molecule IIIa with the
geometric parameters determined by X-ray analysis.
C13
C14
iii
ii
C10
C7
C16
The crystalline structure of IIIa is represented by
one crystallographically independent C18H16N4S mole-
cule (Fig. 1) located in the general position. The mole-
cule has almost planar structure: the maximal deviation
of non-hydrogen atoms from the mean-square plane
does not exceed 0.44 Å (C14). The maximal deviation
from the plane formed by all non-hydrogen atoms
(except for carbon atoms in the benzene rings; plane i
in Fig. 1) is observed for the N3 atom (0.06 Å). The
distance between the N3 and N1 atoms is equal to
2.23(2) Å; it suggests formation of intramolecular hy-
drogen bond N···H (the sum of the van der Waals radii
of the nitrogen and hydrogen atoms is 2.75 Å [15]).
Also, formation of a weak hydrogen bond like
N1–H1 ···C3 is possible, as was reported in [16, 17].
The H1 ···C3 distance is 2.37(2) Å; the sum of the
corresponding van der Waals radii (C and H) is 2.9 Å
[15]. The dihedral angle between the benzene ring
planes (ii and iii) is 163.0°, and the dihedral angles
between the i and ii and i and iii planes are 176.3° and
166.6°, respectively. The torsion angles N1N2C2C18,
C1N1N2C2, N2N1C1S, N2N1C1N4, SC1N4N3, N1C1N4N3,
C1N4N3C11, C18C2C3C4, and C2C3C4C5 are 179.7(2),
177.4(2), 0.4(2), 178.7(1), 177.2(1), 3.6(2), 177.4(1),
3(2), and 3(4)°, respectively.
C15
C9
C8
Fig. 1. Structure of the molecule of N″-[(E-s-cis)-benzyli-
dene]-N″′-[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-
ylidene]thiocarbonohydrazide (IIIa) with atom numbering
according to the X-ray diffraction data.
(a)
a
c
0
b
(b)
a
c
Molecules IIIa in crystals are arranged in layers
parallel to the ac plane (Figs. 2a, 3), and the layers are
stacked along the b axis (Fig. 2b). No shortened inter-
molecular contacts were revealed in the stacks thus
formed. Molecules in neighboring stacks are linked in
pairs through shortened intermolecular interactions
S···H4 2.53(2) Å [the N4–H4 bond length is 0.91(2) Å,
and the angle SH4N4 is 168(2)°] and S···H11 2.88(2) Å
[C11–H11 1.03(2) Å, ∠SH11C11 147(1)°] (the sum of the
van der Waals radii of S and H is 3.00 Å [15]).
0
b
Fig. 2. Packing of molecules of N″-[(E-s-cis)-benzylidene]-
N″′-[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-ylidene]thio-
carbonohydrazide (IIIa) in crystal.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

GLOTOVA et al.
bonding. On the other hand, the observed frequency is
116
considerably lower than that typical of free NH groups
in the IR spectra of aromatic thiourea derivatives
(3390 cm–1) [18].
The above assignment of νNH bands in the IR spec-
tra of IIIa was compared with the results of quantum-
chemical calculations of the corresponding normal
vibration frequencies of molecule IIIa, which were
performed using the geometric parameters determined
by X-ray analysis. The non-valence N···H distance
(2.209 Å) in the optimized structure was similar to that
found for the crystalline state. The calculated νNH
values (with a scaling factor of 0.945) for the free NH
group (3328 cm–1) and NH group involved in intra-
molecular hydrogen bond (3283 cm–1) agree well with
the experimental frequencies measured for compound
IIIa in solution (3335 and 3265 cm–1, respectively).
The calculated frequencies for the free NH groups in
aromatic derivatives of thiourea (3390–3400 cm–1)
were also consistent with the experimental values.
Therefore, molecules IIIa in crystal and in solution
have the same structure, and the low stretching vibra-
tion frequency of the free NH group in the IR spectra
of IIIa in solution is determined by stereoelectronic
factors.
C11
H11
N4
H4
S
H11′
H4′
N4′
C11′
S′
Fig. 3. Associates in the crystalline structure of N″-[(E-s-
cis)-benzylidene]-N″′-[(Z-s-trans)-1-methyl-3-phenylprop-2-
yn-1-ylidene]thiocarbonohydrazide (IIIa). Intermolecular
interactions are shown with dashed lines.
Rupture of =S ···H–N intermolecular hydrogen
bonds in going to solution is also confirmed by the
1H NMR data. Dilution of a solution of IIIa in CDCl3
is accompanied by upfield shift of the NH signal
The IR spectrum of a crystalline sample of IIIa
contains two bands in the region corresponding to N–H
stretching vibrations, at 3265 and 3130 cm–1. Among
these, the high-frequency band (3265 cm–1) does not
change its position in going to CHCl3 solution and is
concentration-independent in the range from 10–2 to
10–4 M. These data indicate that this band belongs to
stretching vibrations of the N1H1 group involved in
intramolecular hydrogen bonding NH···N (in agree-
ment with the X-ray diffraction data). The peak intens-
ity of the low-frequency band (3130 cm–1) in solution
decreases in parallel with the concentration. Simul-
taneously, a new absorption band appears at 3335 cm–1
whose intensity increases synchronously. We can con-
clude that dissolution of compound IIIa is accompa-
nied by dissociation of associates linked through inter-
molecular hydrogen bonds =S···H–N (νNH 3130 cm–1),
and the band appearing at 3335 cm–1 in the IR spec-
trum of solution should be assigned to stretching vibra-
tions of the free N4H group. The higher frequency of
N4H stretching vibrations (3335 cm–1) as compared to
the N1H1 group (3265 cm–1) may be rationalized by
participation of the latter in intramolecular hydrogen
(NHN=CHPh) from δ 11.01 to 10.12 ppm (1JNH
=
98.3 Hz). On the other hand, the NOESY spectrum of
a dilute solution contained a cross peaks resulting from
dipole–dipole interactions between the =CH and HNN3
protons, indicating E configuration of the benzylidene
fragment in IIIa, as in crystal. The chemical shift of
the NH proton that does not participate in intermolec-
ular hydrogen bonding (NHN2=C fragment) does not
1
depend on the concentration (δ 11.20 ppm, JNH
=
93.58 Hz).
The 13C NMR spectrum of IIIa is characterized by
a large difference in the chemical shifts of the α- and
β-acetylenic carbon atoms, ∆δ(Csp) = 22.83 ppm. This
difference may be rationalized in terms of anti orienta-
tion of the acetylenic fragment with respect to the lone
electron pair on the N2 atom and, correspondingly, cis
orientation of the acetylenic fragment and NH group
with respect to the C=N2 bond. An analogous ∆δ(Csp)
value (20.29 ppm) was reported in [19] for (Z)-4-phen-
ylbut-3-yn-2-one phenylhydrazone, while the ∆δ(Csp)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

SYNTHESIS AND STERIC STRUCTURE OF N″-(ARYLMETHYLIDENE)-...
117
value for the E isomer was 1.98 ppm. According to
[19], signal from the methyl carbon atom oriented syn
with respect to the lone electron pair on the hydrazone
nitrogen atom (Z isomer) appears in a weaker field
(δC 21.78 ppm) than the corresponding signal of the
E isomer (δC 16.33 ppm). A similar patter was also
observed for the methyl carbon signals in the 13C NMR
spectra of Z and E isomers of ketone oximes [20]. In
the 13C NMR spectrum of IIIa, the methyl carbon
nuclei resonated at δC 22.99 ppm. Taking into account
that this value approaches that reported for the
HNN=C(CH3)C≡CPh fragment in the spectrum of
(Z)-4-phenylbut-3-yn-2-one phenylhydrazone [19], the
corresponding fragment in molecule IIIa was assigned
Z configuration.
calculations of isolated molecule IIIa were performed
at the B3LYP/6-311G* level using Gaussian-98 soft-
ware package [21].
N″-[(E-c-cis)-Arylmethylidene]-N″′-[(Z-s-trans)-
1-methyl-3-phenylprop-2-yn-1-ylidene]thiocarbono-
hydrazides IIIa–IIId (general procedure). Thiocar-
bonohydrazone IIa–IId, 5 mmol, was added under
stirring to a solution of 0.72 g (5 mmol) of 4-phenyl-
but-3-yn-2-one (I) in 20 ml of acetic acid, the mixture
was stirred for 1 h at 20°C, 20 ml of water was added,
and the mixture was stirred for 1 h more. The precip-
itate was filtered off, washed with 20 ml of water,
dried in a vacuum desiccator over CaCl2, and recrystal-
lized from acetonitrile.
N″-[(E-s-cis)-Benzylidene]-N″′-[(Z-s-trans)-1-
methyl-3-phenylprop-2-yn-1-ylidene]thiocarbono-
hydrazide (IIIa). Yield 1.31 g (82%), mp 154–156°C.
IR spectrum (KBr), ν, cm–1: 2179 w (C≡C); 3130,
Thus the above data demonstrate that the Z-s-trans
and E-s-cis configurations of the hydrazone fragments
in molecule IIIa, determined by X-ray analysis, are
conserved for monomeric molecules in dilute solution.
This conclusion may be important, e.g., while planning
syntheses of complexes on the basis of functionalized
N,S-electron-donor ligands capable of coordinating
metal cations in different modes.
1
3265 (NH). H NMR spectrum, δ, ppm: 2.41 s (3H,
Me), 7.07–7.59 m (10H, Ph), 8.07 s (1H, CH=N),
1
10.12 s (1H, HNN=CH, JNH = 98.3 Hz), 11.20 s (1H,
HNN=CMe, 1JNH = 93.58 Hz). 13C NMR spectrum, δC,
ppm: 22.99 (Me); 80.05 (MeCC≡); 102.88 (PhC≡);
120.33, 127.41, 128.65, 128.74, 130.21, 130.51,
132.06, 132.86 (Carom); 137.10 (C=N); 144.11 (CH=N);
173.89 (C=S). 15N NMR spectrum, δN, ppm: –208.30
The spectral parameters of compounds IIIb–IIId
both in crystal (IR) and in solution (IR, NMR) were
similar to those found for compound IIIa, indicating
their analogous structure. The nature of substituent in
the aromatic ring of initial thiocarbonohydrazones IIa–
IId almost did not affect the yield of target products
IIIa–IIId.
1
(HNN=CH, JNH = 98.3 Hz), –207.04 (HNN=CMe,
1JNH = 93.58 Hz), –70.3 (N=CH), –55.3 (N=CMe).
Found, %: C 67.23; H 5.21; N 17.38; S 10.34.
C18H16N4S. Calculated, %: C 67.48; H 5.03; N 17.49;
S 10.01.
Thus we have developed a simple procedure for the
synthesis of previously unknown highly functionalized
dihydrazones having an acetylenic bond as potential
precursors of drugs, practically important materials,
and intermediate products for organic synthesis.
N″-[(E-s-cis)-4-Dimethylaminobenzylidene]-N″′-
[(Z-s-trans)-1-methyl-3-phenylprop-2-yn-1-ylidene]-
thiocarbonohydrazide (IIIb). Yield 1.44 g (79%),
mp 170–173°C. IR spectrum (KBr), ν, cm–1: 2179 w
1
(C≡C); 3117, 3256 (NH). H NMR spectrum, δ, ppm:
EXPERIMENTAL
2.39 s (3H, Me), 2.95 s (6H, Me2N), 6.28–7.61 m (9H,
H
arom), 7.90 s (1H, CH=N), 10.67 (1H, HNN=CH,
1
1JNH = 98.3 Hz), 11.21 s (1H, HNN=CMe, JNH
=
The IR spectra were recorded on a Specord 75-IR
spectrophotometer from samples prepared as KBr
pellets or solutions in CHCl3. The NMR spectra were
measured from solutions in CDCl3 on Bruker DPX-
94.02 Hz). 13C NMR spectrum, δC, ppm: 22.97 (Me);
40.06 (NMe2); 80.36 (MeCC≡); 102.36 (PhC≡);
111.59, 120.44, 120.74, 128.72, 128.92, 129.81,
132.26, 151.78 (Carom); 136.02 (C=N); 144.73 (CH=N);
173.12 (C=S). 15N NMR spectrum, δN, ppm: –210.6
1
400 and AV-400 spectrometers (400.13 MHz for H,
100.61 MHz for 13C, and 40.53 MHz for 15N) using
hexamethyldisiloxane (1H, 13C) and nitromethane (15N)
as internal references. The X-ray diffraction data were
obtained on an Enraf Nonius CAD-4 diffractometer
(ω/2θ scanning, MoKα irradiation, graphite mono-
chromator) at room temperature. Quantum-chemical
1
(HNN=CH, JNH = 98.3 Hz), –207.6 (HNN=CMe,
1JNH = 94.02 Hz), –87.6 (N=CH), –59.81 (N=CMe).
Found, %: C 66.19; H 5.83; N 19.02; S 8.80.
C20H21N5S. Calculated, %: C 66.09; H 5.82; N 19.27;
S 8.82.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008

GLOTOVA et al.
118
REFERENCES
N″-[(E-s-cis)-4-Chlorobenzylidene]-N″′-[(Z-s-
trans)-1-methyl-3-phenylprop-2-yn-1-ylidene]thio-
carbonohydrazide (IIIc). Yield 1.43 g (81%),
mp 169–171°C. IR spectrum (KBr), ν, cm–1: 2180 w
1. Blumenkopf, T.A., Harrington, J.A., Koble, C.S.,
Bankston, D.D., Morrison, R.W., Jr., Bigham, E.C.,
Styles, V.L., and Spector, T., J. Med. Chem., 1992,
vol. 35, p. 2306.
2. Dimmock, J.R., Kumar, P., Allen, T.M., Kao, G.Y.,
Halleran, S., Balzarini, J., and De Clercq, E., Phar-
mazie, 1997, vol. 52, p. 182.
1
(C≡C); 3119, 3276 (NH). H NMR spectrum, δ, ppm:
2.40 s (3H, Me), 6.98–7.56 m (9H, Harom), 7.98 s (1H,
1
CH=N), 10.76 s (1H, HNN=CH, JNH = 98.1 Hz),
1
11.17 s (1H, HNN=CMe, JNH = 93.9 Hz). 13C NMR
spectrum, δC, ppm: 22.96 (Me); 80.03 (MeCC≡);
102.93 (PhC≡); 120.28, 128.47, 128.85, 129.00,
130.38, 131.36, 131.99, 136.46 (Carom); 137.42 (C=N);
142.49 (CH=N); 173.91 (C=S). 15N NMR spectrum,
3. Naik, A.D., Annigeri, S.M., Gangadharmath, U.B.,
Revankar, V.K., and Mahale, V.B., J. Inclusion Phenom.
Macrocyclic Chem., 2002, vol. 43, p. 291.
4. Azza Abu-Hussen, A.A. and Adel Emara, A.A.,
1
J. Coord. Chem., 2004, vol. 57, p. 973.
δN, ppm: –210.8 (HNN=CH, JNH = 98.1 Hz), –207.2
1
5. Bacchi, A., Carcelli, M., Pelagatti, P., Pelizzi, G.,
Rodriguez-Arguelles, M.C., Rogolino, D., Solinas, C.,
and Zani, F., J. Inorg. Biochem., 2005, vol. 99, p. 397.
6. Bacchi, A., Bonini, A., Carcelli, M., Ferraro, F.,
Leporati, E., Pelizzi, C., and Pelizzi, G., J. Chem. Soc.,
Dalton Trans., 1996, p. 2699.
(HNN=CMe, JNH = 93.9 Hz), –74.0 (N=CH), –61.8
(N=CMe). Found, %: C 60.68; H 4.04; Cl 10.12;
N 15.98; S 9.13. C18H15ClN4S. Calculated, %: C 60.92;
H 4.26; Cl 9.99; N 15.79; S 9.04.
N″-[(Z-s-trans)-1-Methyl-3-phenylprop-2-yn-1-
ylidene]-N″′-[(E-s-cis)-4-nitrobenzylidene]thiocar-
bonohydrazide (IIId). Yield 1.43 g (78%), mp 174–
176°C. IR spectrum (KBr), ν, cm–1: 2177 w (C≡C);
7. Moubaraki, B., Murray, K.S., Ranford, J.D., Wang, X.,
and Xu, Y., Chem. Commun., 1998, p. 353 .
8. Cheng, H., Chun-ying, D., Chen-jie, F., Yong-jiang, L.,
and Meng Qing-jin, J. Chem. Soc., Dalton Trans. 2000,
p. 1207.
1
3100, 3275 (NH). H NMR spectrum, δ, ppm: 2.40 s
(3H, Me), 7.42–7.78 (9H, Harom), 8.09 s (1H, CH=N),
10.71 s (1H, HNN=CH), 11.23 s (1H, HNN=CMe).
13C NMR spectrum, δC, ppm: 22.94 (Me); 79.82
(MeCC≡); 103.20 (PhC≡); 120.08, 123.95, 127.72,
129.03, 130.72, 131.88, 138.82, 148.42 (Carom); 138.21
(C=N); 140.66 (CH=N); 174.02 (C=S). 15N NMR
spectrum, δN, ppm: –208.7 (HNN=CH), –205.7
(HNN=CMe), –74.6 (N=CH), –61.9 (N=CMe). Found,
%: C 59.31; H 4.07; N 19.38; S 8.60. C18H15N5O2S.
Calculated, %: C 59.16; H 4.14; N 19.17; S 8.78.
9. Lahav, M., Gabai, R., Shipway, A.N., and Willner, I.,
Chem. Commun., 1999, p. 1937.
10. Matthews, C.J., Xu, Z., Mandal, S.K., Thompson, L.K.,
Biradha, K., Poirier, K., and Zaworotko, M.J., Chem.
Commun., 1999, p. 347.
11. Colacio, E., Lopez-Magana, C., McKee, V., and Rome-
rosa, A., J. Chem. Soc., Dalton Trans., 1999, p. 2923.
12. Popat, K.H., Purohit, D.H., Chovatia, P.T., and
Joshi, H.S., J. Indian Chem. Soc., 2005, vol. 82, p. 940.
13. Komarova, T.N., Nakhmanovich, A.S., Glotova, T.E.,
and Lopyrev, V.A., Izv. Ross. Akad. Nauk, Ser. Khim.,
1998, p. 2083.
14. Dvorko, M.Yu., Albanov, A.I., Chipanina, N.N., Sher-
styannikova, L.V., Samoilov, V.G., Komarova, T.N., and
Glotova, T.E., Khim. Geterotsikl. Soedin., 2006, p. 1655.
X-Ray analysis of compound IIIa. Single crystals
suitable for X-ray analysis were obtained by slow
evaporation of a solution of compound IIIa in aceto-
nitrile at a constant temperature. Rhombic crystals with
the following unit cell parameters: a = 20.911(4), b =
6.841(1), c = 24.241(5) Å; V = 3467.7(1) Å3; space
group Pbcn; Z = 8; dcalc = 1.23 g/cm3. The structure
was solved by the direct methods with subsequent
Fourier syntheses using SHELXS-97 program [22] and
was refined by the least-squares procedure in full-
matrix anisotropic approximation for all non-hydrogen
atoms using SHELXL-97 program [23]. The coordi-
nates of hydrogen atoms were determined experimen-
tally and were refined in isotropic approximation. The
complete set of crystallographic data was deposited to
the Cambridge Crystallographic Data Center (entry
no. CCDC 648092).
15. Bondi, A., J. Phys. Chem., 1964, vol. 68, p. 441.
16. Viswamitra, M.A., Radhakrishnan, R., Bandekar, J., and
Desiraju, G.R., J. Am. Chem. Soc., 1993, vol. 115,
p. 4868.
17. Nishio, M. Cryst. Eng. Commun., 2004, vol. 6, no. 27,
p. 130.
18. Sudha, L.V. and Sathyanarayana, D.N., Spectrochim.
Acta, Part A, 1984, vol. 40, p. 751.
19. Ananchenko, G.S., Petrov, A.A., and Ershov, B.A., Russ.
J. Org. Chem., 1999, vol. 35, p. 153.
20. Afonin, A.V., Ushakov, I.A., Tarasova, O.A.,
Shmidt, E.Yu., Mikhaleva, A.I., and Voronov, V.K.,
Russ. J. Org. Chem., 2000, vol. 36, p. 1777.
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SYNTHESIS AND STERIC STRUCTURE OF N″-(ARYLMETHYLIDENE)-...
119
21. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuse-
ria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzew-
ski, V.G., Montgomery, J.A., Stratmann, R.E., Bur-
ant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D.,
Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J.,
Barone, V., Cossi, M., Cammi, R., Mennucci, B.,
Pomelli, C., Adamo, C., Clifford, S., Ochterski, J.,
Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K.,
Malick, D.K., Rabuck, A.D., Raghavachari, K., Fores-
man, J.B., Cioslowski, J., Ortiz, J.V., Stefanov, B.B.,
Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gom-
perts, R., Martin, R.L., Fox, D.J., Keith, T., Al-La-
ham, M.A., Peng, C.Y., Nanayakkara, A., Gonzalez, C.,
Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W.,
Wong, M.W., Andres, J.L., Gonzalez, C., Head-Gor-
don, M., Replogle, E.S., and Pople, J.A., Gaussian 98,
Revision A.6, Pittsburgh PA: Gaussian, 1998.
22. Sheldrick, G.M., SHELXS-97. A Program for Crystal
Structure Determination, Gottingen: Univ. of Gottingen,
1997.
23. Sheldrick, G.M., SHELXL-97. A Program for the Refine-
ment of Crystal Structures. Gottingen: Univ. of Gottin-
gen, 1997.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 1 2008