Stable σh-adducts in reactions of ferrocenyllithium with azines

Article abstract of DOI:10.1007/s11172-008-0292-4

Stable σ^H-adducts as intermediates of the nucleophilic substitution of hydrogen in 3-(2-pyridyl)-1,2,4-triazines were obtained for the first time using ferrocenyllithium as a nucleophilic reagent. The three-dimensional structures of the reaction products were established based on the X-ray diffraction study of 1-[4-ethyl-6-phenyl-3-(2-pyridyl)-5(H)-1,2,4- triazin-5-yl]ferrocene.

Full text of DOI:10.1007/s11172-008-0292-4

Russian Chemical Bulletin, International Edition, Vol. 57, No. 10, pp. 2156—2161, October, 2008
2156
H
Stable σ ꢀadducts in reactions of ferrocenyllithium with azines*
I. A. Utepova,a A. E. Lakhina,a M. V. Varaksin,a I. S. Kovalev,a V. L. Rusinov,a P. A. Slepukhin,b
M. I. Kodess,b and O. N. Chupakhina,b
aUrals State Technical University,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 0458. Eꢀmail: rusinov@mail.ustu.ru
bI. Ya. Postovsky Institute of Organic Synthesis, Urals Branch of the Russian Academy of Sciences,
22 ul. S. Kovalevskoi, 620041 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 1189. Еꢀmail: chupakhin@ios.uran.ru
H
Stable σ ꢀadducts as intermediates of the nucleophilic substitution of hydrogen in 3ꢀ(2ꢀpyridyl)ꢀ
1,2,4ꢀtriazines were obtained for the first time using ferrocenyllithium as a nucleophilic reꢀ
agent. The threeꢀdimensional structures of the reaction products were established based on the
Xꢀray diffraction study of 1ꢀ[4ꢀethylꢀ6ꢀphenylꢀ3ꢀ(2ꢀpyridyl)ꢀ5(H)ꢀ1,2,4ꢀtriazinꢀ5ꢀyl]ferrocene.
H
Key words: ferrocene, 1,2,4ꢀtriazines, σ ꢀadducts, nucleophilic substitution of hydrogen
(SNH), C—C coupling.
Heterocyclic derivatives of ferrocene have a wide range
of useful properties. For example, certain compounds posꢀ
sess redox sensitivity,1—6 photophysical properties,7,8 or
magnetic properties,9—12 and can serve as ligands for the
synthesis of transition metal complexes.13—18 Some of these
compounds are planar chiral derivatives used as catalytic
reagents for various asymmetric reactions19—21 or belong
to physiologically active substances.22—27
Scheme 1
Earlier,28 we have developed an efficient method for
the synthesis of heterocyclic derivatives of ferrocene by
the direct noncatalyzed C—Cꢀcrossꢀcoupling of ferroꢀ
cenyllithium with various azines using the nucleophilic
substitution of hydrogen (SNH). It is commonly accepted
that the oxidative nucleophilic substitution of hydrogen
SNH(AO) involves two steps (Scheme 1).29,30 The first step
involves the addition of a nucleophilic fragment to comꢀ
pounds 1 containing electronꢀwithdrawing substituents
giving rise to σHꢀadducts 2. In the second step, these
intermediates undergo aromatization under the action of
oxidizing agents to form the corresponding SNH products 3.
W — acceptor
when exposed to atmospheric oxygen to give products
of substitution of hydrogen in azine.28 The first step of the
nucleophilic substitution of hydrogen is reversible; the
oxidation by atmospheric oxygen can be accompanied by
protolytic decomposition of adducts 2. The use of DDQ
as the oxidizing agent allowed us to prepare products in
substantially higher yields (60—80%) compared to the
yields obtained in earlier studies (2—40%).31 As a result,
we synthesized various monoazinylꢀ and 1,1´ꢀdiazinylꢀ
ferrocenes (derivatives of monoꢀ, diꢀ, and triazines).
So far, the formation of intermediate dihydro comꢀ
pounds in the reactions of ferrocenyllithium with azines
has been postulated.31—33 In the present study, we experiꢀ
mentally detected these σHꢀadducts.
Results and Discussion
The earlier studies of the reactions of ferrocenyllithium
with monoꢀ and diazines have shown that the characterisꢀ
tic features of the SNH reactions are that the intermediate
σHꢀadducts (heteroanalogs of intermediates 2) are unꢀ
stable and undergo immediate spontaneous oxidation
The mechanism of this transformation was confirmed
by NMR data. We chose the reaction of ferrocenyllithium
(4) with pyrazine (5) (Scheme 2) as a model reaction.
The formation of σHꢀadduct 6 was spectroscopically
1
detected. The H NMR spectrum was recorded immediꢀ
ately after the preparation of ferrocenyllithium directly
in an NMR tube followed by the addition of pyrazine in
* Dedicated to Academician B. A. Trofimov on the occasion of
his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2116—2120, October, 2008.
1066ꢀ5285/08/5710ꢀ2156 © 2008 Springer Science+Business Media, Inc.

Stable σHꢀadducts of ferrocenyllithium with azines
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 10, October, 2008
2157
Scheme 2
Scheme 4
THFꢀd8. This spectrum shows a signal for the proton at
the sp3ꢀhybridized carbon atom with a chemical shift
(5.59 ppm) characteristic of these compounds.34 When
exposed to atmospheric oxygen for 1 h, intermediate 6 is
transformed into pyrazinylferrocene characterized earlier.28
We succeeded, for the first time, in isolating stable
σHꢀadducts of azines with ferrocenyllithium by performꢀ
ing the reaction with 3ꢀ(2ꢀpyridyl)ꢀ1,2,4ꢀtriazines. Pyridylꢀ
triazines 7a,b react with ferrocenyllithium 4 (in a ratio of
1 : 1) at room temperature to give salts of σHꢀadducts
8a,b. The latter are readily hydrolyzed in air to form
dihydro compounds 9a,b. σHꢀAdducts 9a,b were prepared
in 75—76% yields (Scheme 3) and were isolated by aluꢀ
mina column chromatography.
The aromatization of compounds 9a,b giving rise to
the corresponding triazinylferrocenes 10a,b can be perꢀ
formed with the use of DDQ.28 Thus, the reactions of σHꢀ
adducts 9a,b with DDQ in THF at room temperature
afford arylpyridyltriazinylferrocenes 10a,b in virtually
quantitative yields.
The IR spectra of compounds 9a,b contain NH
stretching bands at 3300—3500 cm–1. The mass spectra
have molecular ion peaks. The 1H NMR spectra of
adducts 9a,b show signals for the protons at the sp3ꢀhyꢀ
bridized C(5) atom at δ 5.72—5.76 and signals for the
proton of the NH group of the triazine ring at δ 11.00,
which confirm the formation of the dihydro compounds.
The 13C NMR spectra of compounds 9a,b have a signal at
δ 50 typical of sp3ꢀhybridized carbon atoms.34 In the
1H NMR spectra of aromatic compounds 10a,b, signals
for protons at the C(5) atom and the NH groups are
absent, and the signals for protons of the substituted ferꢀ
rocene fragment are shifted downfield compared to those
of the σHꢀadduct (δ 4.00—4.20 and 4.07—4.60, respecꢀ
tively). In the 13C NMR spectra, the characteristic signal
for sp3ꢀhybridized carbon atoms is absent.
Compounds 9a,b were synthesized as racemic mixꢀ
tures. The resolution of these compounds on a analytical
chiral Chiralcel ODꢀH column showed that the ratio of
stereoisomers was 1 : 1 in both cases.
Derivatives 9a,b can exist as two tautomers (A and B)
due to prototropic tautomerism (Scheme 4).
Scheme 3
(7a,b), R = H (a), OMe (b)

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 10, October, 2008
Utepova et al.
Scheme 5
The NMR data show that in DMSOꢀd6, heterocyclic
compounds 9a,b exist, apparently, predominantly as the
tautomer A. This is confirmed by the crossꢀpeak between
the proton at the N(2) atom and the signals for the C(3)
and C(2') atoms in the 2D HMBC spectra, as well as by
the singlet structure of the signal for H(5) in the 1H NMR
spectra of compounds 9a,b. However, the alkylation of
σHꢀadduct 11 in alkaline conditions proceeds at the N(4)
atom, which confirms the existence of the tautomer B.
Derivative 12 was synthesized by the reaction of comꢀ
pound 9a with ethyl iodide in dry THF in the presence of
sodium hydride under alkaline conditions at room temꢀ
perature (Scheme 5).
The threeꢀdimensional structures of the σHꢀadducts
were established based on Xꢀray diffraction data for comꢀ
pound 12 (Fig. 1).
According to the Xꢀray diffraction data, derivative 12
crystallizes in the monoclinic space group P21/c. The aroꢀ
maticity of the triazine ring is disturbed, no equalization
Table 2. Principal crystallographic data and the Xꢀray diffracꢀ
tion data collection and refinement statistics for compound 12
Parameter
Characteristics
Molecular formula
Molecular weight
C26H24FeN4
448.34
T/K
295(2)
λ/Å
Crystal system
Space group
a/Å
b/Å
c/Å
0.71073
Monoclinic
P21/c
9.3471(8)
20.7674(13)
10.7865(10)
96.248(7)
2081.4(3)
4
C(18)
C(26)
C(19)
C(16)
C(17)
C(25)
C(15)
N(1)
F(1)
C(14)
β/deg
C(24)
V/Å3
N(4)
C(2)
C(3)
C(13)
C(8)
C(9)
C(4)
Z
C(23)
dcalc/g cm–3
1.431
0.746
936
C(10)
C(20)
C(1)
N(2)
μ/mm–1
C(22)
C(21)
C(12)
F(000)
C(7)
C(11)
Crystal dimensions/mm
2θꢀScan range/deg
Completeness based on 2θ
hkl ranges
0.24×0.18×0.13
2.82—30.51
96.9
–13 < h < 6
–29 < k < 29
–15 < l < 15
13945
N(3)
C(5)
C(6)
(%)
max
Fig. 1. Molecular structure of 12.
Total number of reflections
Number of independent reflections
Rint
6171
0.0273
Table 1. Selected bond lengths (d) and bond angles (ω) in comꢀ
pound 12
Number of reflections with I>2σ(I)
Number of refined parameters
Absorption correction
Transmission
(maximum/minimum)
GOOF (based on F2)
3436
280
Analytical
Bond
d/Å
Angle
ω/deg
C(1)—N(1) 1.354(19)
C(1)—N(1)—C(2) 115.79(14)
C(1)—N(2)—N(3) 116.56(12)
C(3)—N(3)—N(2) 120.30(12)
N(3)—C(3)—C(2) 120.71(14)
C(15)—C(2)—C(3) 114.98(12)
N(1)—C(2)—C(15) 112.87(12)
C(1)—N(1)—C(25) 124.40(13)
C(2)—N(1)—C(25) 119.24(11)
N(1)—C(2)—C(3) 106.23(11)
N(1)—C(26)—C(26) 113.83(13)
C(1)—N(2)
N(2)—N(3)
N(3)—C(3)
C(3)—C(2)
C(2)—C(15) 1.516(2)
C(2)—N(1) 1.464(19)
1.306(18)
1.397(17)
1.284(18)
1.524(19)
0.849/0.775
1.003
R factors (based on reflections with I>2σ(I))
R1
wR2
0.0340
0.0670
R factors (based on all reflections)
N(1)—C(25) 1.465(18)
C(25)—C(26) 1.512(2)
R1
wR2
0.0841
0.0720
0.481/–0.298
Δρmax/Δρmin/eÅ–3

Stable σHꢀadducts of ferrocenyllithium with azines
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 10, October, 2008
2159
(75%), m.p. 195 °C. Found (%): C, 68.24; H, 4.84; N, 13.69.
C24H20FeN4. Calculated (%): C, 68.59; H, 4.80; N, 13.33.
IR, ν/cm–1: 3335 (NH), 2956, 1467, 1334, 1147. MS, m/z
of the bond lengths in the diene system of dihydrotriazine
being observed (C(3)=N(3), 1.284(2) Å; N(3)—N(2),
1.397(2) Å; N(2)=C(1), 1.306(2) Å). The bond lengths
and bond angles have typical values (Table 1). The charꢀ
acter of displacement ellipsoids for the unsubstituted
cyclopentadienyl ring of the ferrocenyl substituent is
indicative of the probable unresolved disorder of the
carbon atoms.
Hence, we spectroscopically detected and isolated for
the first time individual intermediate σHꢀadducts that are
formed in the reactions of ferrocenyllithium with azines,
thus confirming the mechanism of these transformations.
The newly synthesized σHꢀadducts have pronounced comꢀ
plexing properties and are of interest by themselves for
coordination chemistry as chiral ligands for metal cations.
1
(Irel(%)): 420 [M]+ (100). H NMR, δ: 4.01 (m, 1 H, Cp—H);
4.04 (m, 2 H, Cp—H); 4.06 (s, 5 H, Cp—H); 4.16 (m, 1 H,
Cp—H); 5.76 (s, 1 H, H(5)); 7.41—7.57 (m, 3 H, Hm, Hp); 7.59
(ddd, 1 H, H(5´), J = 7.7, 4.9, and 1.0 Hz); 7.93 (dd, 2 H, Ho,
J = 8.4 and 1.4 Hz); 8.01 (td, 1 H, H(4´), J = 7.7 and 1.8 Hz);
8.27 (dt, 1 H, H(3´), J = 7.8 and 1.0 Hz); 8.68 (ddd, 1 H, H(6´),
J = 4.9, 1.8, and 1.0 Hz); 11.16 (s, 1 H, NH). 13C NMR, δ:
50.08 (C(5)); 66.52, 66.90, 67.43, 67.48 (CH—Cp); 68.55
(5 CH—Cp); 88.52 (C—Cp); 120.99 (C(3´)); 125.75 (C(5´));
126.01 (Co); 128.58 (Cm); 129.03 (Cp); 135.27 (Ci); 137.58
(C(4´)); 142.83 (C(6)); 148.47 (C(6´)); 149.69 (C(2´));
150.04 (C(3)).
(R,S)ꢀ[6ꢀ(4ꢀMethoxyphenyl)ꢀ3ꢀ(2ꢀpyridyl)ꢀ2,5ꢀdihydroꢀ2(H)ꢀ
1,2,4ꢀtriazinꢀ5ꢀyl]ferrocene (9b). Compound 9b was obtained in
a yield of 1.3 g (76%) , m.p. 170 °C. Found (%): C, 66.68; H,
4.81; N, 12.17. C25H22FeN4O. Calculated (%): C, 66.68; H,
4.92; N, 12.44. IR, ν/cm–1: 3333 (NH), 2929, 1615, 1525, 1465,
1337, 1145, 1109. MS, m/z (Irel(%)): 450 [M]+ (100). 1H NMR,
δ: 3.80 (s, 3 H, OMe); 3.98—4.04 (m, 3 H, Cp—H); 4.10 (s, 5 H,
Cp—H); 4.19 (m, 1 H, Cp—H); 5.72 (s, 1 H, H(5)); 7.02 (d,
2 H, Hm, J = 8.9 Hz); 7.58 (ddd, 1 H, H(5´), J = 7.7, 4.8, and
1.0 Hz); 7.88 (d, 2 H, Ho, J = 8.9 Hz); 8.01 (td, 1 H, H(4´),
J = 7.7 and 1.7 Hz); 8.28 (dt, 1 H, H(3´), J = 7.7 and 1.0 Hz);
8.67 (ddd, 1 H, H(6´), J = 4.8, 1.7, and 1.0 Hz); 11.01 (s, 1 H,
NH). 13C NMR, δ: 49.98 (C(5)); 55.18 (OMe); 66.51, 66.83,
67.31, 67.56 (CH—Cp); 68.55 (5 CH—Cp); 88.85 (C—Cp);
113.95 (Cm); 120.91 (C(3´)); 125.67 (C(5´)); 127.41 (Ci); 127.51
(Co); 137.53 (C(4´)); 142.56 (C(6)); 148.43 (C(6´)); 149.77
(C(2´)); 150.09 (C(3)); 159.97 (Cp).
Synthesis of compounds 10a,b (general procedure). A soluꢀ
tion of DDQ (3.8 mmol) in THF (10 mL) was added to a
solution of adduct 8 (3.8 mmol) in a minimum amount of THF
at room temperature. The reaction mixture was immediately
filtered through an Al2O3 layer, the Al2O3 layer was repeatedly
washed with THF, the solvent was evaporated, and the residue
was chromatographed on Al2O3. The reaction product was eluted
with ethyl acetate (Rf 0.3—0.4). The solvent was evaporated,
and the precipitate was recrystallized from hexane if required.
[6ꢀPhenylꢀ3ꢀ(2ꢀpyridyl)ꢀ1,2,4ꢀtriazinꢀ5ꢀyl]ferrocene (10a).
Compound 10a was obtained in a yield of 1.1 g (90%) as darkꢀ
red crystals, m.p. 185 °C. Found (%): C, 68.91; H, 4.36; N,
13.07. C24H18FeN4. Calculated (%): C, 68.92; H, 4.34; N, 13.39.
IR, ν/cm–1: 2958, 1487, 1384, 1140, 1111. MS, m/z (Irel(%)):
418 [M]+ (100). 1H NMR, δ: 4.09 (s, 5 H, Cp—H); 4.53 (m,
2 H, Cp—H); 4.59 (m, 2 H, Cp—H); 7.62—7.69 (m, 6 H, Ph,
H(5´)); 8.10 (td, 1 H, H(4´), J = 7.8 and 1.8 Hz); 8.55 (dt, 1 H,
H(3´), J = 7.8 and 1.0 Hz); 8.88 (ddd, 1 H, H(6´), J = 4.7, 1.8,
and 1.0 Hz). 13C NMR, δ: 70.18 (5 CH—Cp); 70.61, 72.19
(CH—Cp); 77.09 (C—Cp); 123.82 (C(3´)); 125.53 (C(5´));
128.57, 129.03 (Co, Cm); 129.56 (Cp); 136.36 (Ci); 137.34
(C(4´)); 150.02 (C(6´)); 153.00 (C(2)); 155.51 (C(6)); 158.56
(C(5)); 160.32(C(3)).
Experimental
1
The H and 13C NMR spectra were measured on a Brukerꢀ
DRXꢀ400 spectrometer (400 and 100 MHz, respectively)
in DMSOꢀd6/CCl4; the chemical shifts are expressed on the
δ scale relative to SiMe4 as the internal standard. The assignꢀ
ment of the 1H and 13C signals was made based on combined
2D heteronuclear 1Hꢀ13C HSQC and 1Hꢀ13C HMBC experiꢀ
ments. The IR spectra were recorded on a Perkin Elmer
Spectrum One B spectrometer in KBr pellets. The mass spectra
were obtained on a Varian MATꢀ311A spectrometer using a
direct inlet system; the ionizing electron energy was 70 eV; the
ionization chamber temperature was 100—300 °C. The elemenꢀ
tal analysis (C, H, N) was carried out on a Perkin Elmer 2400ꢀII
analyzer. The HPLC analysis was performed on a Merck Hitachi
system (DIACEL Chiralcel ODꢀH column). The melting points
were determined on a Boetius apparatus. The Rf values were
measured on Polygram Alox N/UVꢀ254 plates with a stationary
Al2O3 phase. The column chromatography was performed using
Aluminum oxide (Fluka, Germany).
The solvents were purified and dried according to standard
procedures. Ferrocene, sodium hydride, ethyl iodide, and THF
were purchased from Aldrich. All other reagents and solvents
were of Russian production.
Bromoferrocene,35 6ꢀphenylꢀ3ꢀ(2ꢀpyridyl)ꢀ1,2,4ꢀtriazine
(7a),36 and 6ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀ(2ꢀpyridyl)ꢀ1,2,4ꢀtriazine
(7b)36 were synthesized according to known procedures.
Synthesis of compounds 9a,b (general procedure). A solution
of heterocyclic compound 7a or 7b (3.8 mmol) in anhydrous
THF (30 mL) was added to a solution of ferrocenyllithium 4 in
anhydrous diethyl ether (which was prepared by the addition of
a 2.5 M nꢀbutyllithium solution (1.6 mL, 4 mmol) in hexane
(20 mL) to a solution of bromoferrocene (3.8 mmol) in anhyꢀ
drous diethyl ether) under argon at room temperature. The
reaction mixture was stirred for 15 min. The suspension was
concentrated under reduced pressure. The residue was subjected
to preparative column chromatography on Al2O3. Ferrocene
was eluted with hexane, and then the reaction product was eluted
with ethyl acetate (Rf 0.5—0.6). The solvent was concentrated,
and the residue was recrystallized from a 1 : 1 benzene—methaꢀ
nol mixture if required.
[6ꢀ(4ꢀMethoxyphenyl)ꢀ3ꢀ(2ꢀpyridyl)ꢀ1,2,4ꢀtriazinꢀ5ꢀyl]ꢀ
ferrocene (10b). Compound 10b was obtained in a yield of 1.2 g
(92%) as darkꢀviolet crystals, m.p. 160 °C. Found (%): C, 67.47;
H, 4.48; N, 12.15. C25H20FeN4O. Calculated (%): C, 66.98; H,
4.50; N, 12,15. IR, ν/cm–1: 2925, 1609, 1520, 1487, 1384, 1346,
1180, 1111. MS, m/z (Irel(%)): 448 [M]+ (100). 1H NMR, δ:
(R,S)ꢀ[6ꢀPhenylꢀ3ꢀ(2ꢀpyridyl)ꢀ2,5ꢀdihydroꢀ2(H)ꢀ1,2,4ꢀtriazinꢀ
5ꢀyl]ferrocene (9a). Compound 9a was obtained in a yield of 1.2 g

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Utepova et al.
3.89 (s, 3 H, OMe); 4.07 (s, 5 H, Cp—H); 4.60 (s, 4 H, Cp—H);
7.18 (s, 2 H, Hm, J = 6.7 Hz); 7.62 (d, 2 H, Ho, J = 6.7 Hz); 7.64
(ddd, 1 H, H(5´), J = 7.8, 4.7, and 1.0 Hz); 8.09 (td, 1 H, H(4´),
J = 7.8 and 1.8 Hz); 8.54 (dt, 1 H, H(3´), J = 7.8 and 1.0 Hz);
8.88 (ddd, 1 H, H(6´), J = 4.7, 1.8, and 1.0 Hz). 13C NMR, δ:
55.30 (OMe); 70.15 (5 CH—Cp); 70.70, 72.08 (CH—Cp); 77.41
(C—Cp); 113.98 (Cm); 123.75 (C(3´)); 125.46 (C(5´)); 128.34
(Ci); 130.51 (Co); 137.31 (C(4´)); 150.00 (C(6´)); 153.05 (C(2´));
155.20 (C(6)); 158.38 (C(5)); 159.96 (C(3)); 160.24 (Cp).
(R,S)ꢀ[4ꢀEthylꢀ6ꢀphenylꢀ3ꢀ(2ꢀpyridyl)ꢀ5(H)ꢀ1,2,4ꢀtriazinꢀ
5ꢀyl]ferrocene (12). Sodium hydride (3.4 mg, 0.143 mmol) was
added to a solution of ligand 9a (50 mg, 0.119 mmol) in dry
THF (15 mL), and the reaction mixture was stirred until comꢀ
plete dissolution. Then EtI (0.011 mL, 0.143 mmol) was added
to the reaction mixture, and the mixture was stirred at room
temperature for 5 h. The solution was concentrated in vacuo,
and the residue was chromatographed on Al2O3 using ethyl
acetate as the eluent (Rf 0.7). Compound 12 was obtained in a
yield of 25 mg (39%), m.p. 132 °C. Found (%): C, 67.64; H,
5.41; N, 12.50. C26H24FeN4. Calculated (%): C, 69.65; H, 5.40;
N, 12.50. 1H NMR, δ: 1.21 (t, 3 H, J = 7 Hz, N—CH2—Me);
3.50 (m, 1 H, N—CH2—Me); 3.94 (m, 1 H, N—CH2—Me);
3.96 (s, 5 H, Cp—H); 4.05 (m, 1 H, Cp—H); 4.08 (m, 1 H,
Cp—H); 4.21 (m, 1 H, Cp—H); 4.23 (m, 1 H, Cp—H); 5.41 (s,
1 H, H(5)); 7.35 (m, 1 H, Py); 7.45 (m, 1 H, Py); 7.52 (m, 2 H,
Ph); 7.78 (m, 1 H, Py); 8.13 (m, 3 H, Ph); 8.67 (m, 1 H, Py).
Xꢀray diffraction study. Brown prismatic single crystals suitꢀ
able for Xꢀray diffraction were grown by slow evaporation from
diethyl ether. The Xꢀray diffraction data were collected on an
automated Xcalibur 3 diffractometer (λMo, graphite monochroꢀ
mator, 295(2) K, ωꢀscanning technique, the scanning step was
1°). The structure was solved by direct methods with the use of
the SHELXS97 program package37 and refined by the fullꢀ
matrix leastꢀsquares method with anisotropic displacement
parameters for all nonhydrogen atoms (with isotropic displaceꢀ
ment parameters for H atoms) using the SHELXL97 program
package.38 The hydrogen atoms were located in difference elecꢀ
tron density maps and refined using a riding model with fixed
thermal parameters.
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This study was financially supported by the Russian Foundaꢀ
tion for Basic Research (Project Nos 07ꢀ03ꢀ96104r_Ural_a
and 06ꢀ03ꢀ32764) and the Council on Grants of the Presiꢀ
dent of the Russian Federation (Program for State Support
of Leading Scientific Schools of the Russian Federation,
Grant NShꢀ3758.2008.3).
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and N. N. Meleshonkova, Izv. Akad. Nauk, Ser. Khim., 1996,
2743 [Russ. Chem. Bull., 1996, 45, 2602 (Engl. Transl.)].
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Received December 18, 2007;
in revised form July 25, 2008