Synthesis of pyrido[1,2-a][1,3,5]triazine derivatives by aminomethylation of 6-amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles

Article abstract of DOI:10.1007/s10593-014-1447-x

The aminomethylation of 6-amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5- dicarbonitriles by treatment with primary amines and an excess of formaldehyde resulted in the formation of 3-R-8-aryl-6-oxo-1,3,4,6-tetrahydro-2H-pyrido[1,2- a][1,3,5]triazine-7,9-dica

Full text of DOI:10.1007/s10593-014-1447-x

Chemistry of Heterocyclic Compounds, Vol. 50, No. 1, April, 2014 (Russian Original Vol. 50, No. 1, January, 2014)
SYNTHESIS OF PYRIDO[1,2-a][1,3,5]TRIAZINE
DERIVATIVES BY AMINOMETHYLATION OF
6-AMINO-4-ARYL-2-OXO-1,2-DIHYDROPYRIDINE-
3,5-DICARBONITRILES
1
1
1
*
A. N. Khrustaleva , K. A. Frolov , V. V. Dotsenko ,
A. O. Dmitrienko2, I. S. Bushmarinov2, and S. G. Krivokolysko1
The aminomethylation of 6-amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles by treatment
with primary amines and an excess of formaldehyde resulted in the formation of 3-R-8-aryl-6-oxo-
1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitriles. The structure of 6-oxo-3,8-di-
phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitrile was investigated by X-ray
structural analysis.
Keywords: 6-amino-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles, pyrido[1,2-a][1,3,5]triazines, multi-
component cyclocondensation, Mannich reaction, X-ray structural analysis.
3-Cyanopyridine-2(1Н)-chalcogenones are important starting reagents for the preparation of various
heterocyclic systems, many of which exhibit biological activity [1-7]. Our research group is currently engaged
in the study of aminomethylation reactions of 3-cyanopyridine-2(1Н)-thione and -selenone [8-29]. At the same
time, the literature contains only isolated reports of reactions involving their oxygen-containing analogs [1, 3].
We decided to continue our research program in this direction by studying the reactivity of the 6-amino-4-aryl-
2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles 1a,b under the conditions of the Mannich reaction.
It was established that the starting pyridones 1a,b readily reacted with primary amines and an excess of
formaldehyde, forming the 3-R-8-aryl-6-oxo-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbo-
nitriles 2a-h in 23-77% yields (Scheme 1).
The substantial difference in the yields was likely due to the different solubility of the reaction products.
The reaction presumably involved the non-isolating intermediate 3, which underwent an intramolecular
cyclocondensation upon interacting with a second molecule of formaldehyde, resulting in compounds 2a-h.
Remarkably, the direction of Mannich reaction with analogous sulfur-containing pyridines
_______
*To whom correspondence should be addressed, e-mail: khrustaleva.anastasia@yandex.ru.
1"ChemEx" Laboratory, Vladimir Dal' East Ukrainian National University, 20-A/7 Molodyozhnyi Kv.,
Lugansk.
2A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St.,
Moscow 117813, Russia; e-mail: dmitrienka@gmail.com.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 52-58, 2014. Original article
submitted December 18, 2013.
46
0009-3122/14/5001-0046©2014 Springer Science+Business Media New York

Scheme 1
Ar
N
Ar
Ar
NC
HN
CN
O
RNH2
HCHO
NC
CN
O
NC
CN
O
HCHO
EtOH

EtOH

HN
N
H
H2N
N
H
1a,b
N
R
NHR
3
2a–h
CN
O
N
NC
O
1,4-(NH2)2C6H4,
HCHO, DMF
Ph
Ph
N
1a
N
N
CN
N
H
N
H
NC
5
1a, 2a–e Ar = Ph; 1b, 2f–h Ar = 4-MeOC6H4;
2 a,f R = Me, b,g R = CH2Ph, c R = Ph, d,h R = 4-MeC6H4, e R = 4-FC6H4
depended on the nature of the amine. Thus, using highly nucleophilic aliphatic amines led to pyrido[1,2-а]-
[1,3,5]triazine derivatives, while in the case of aromatic amines only the dipyridotetrazocines 4 were formed or
mixtures of the latter with pyrido[1,2-а][1,3,5]triazines [28] (Scheme 2).
Scheme 2
Ar
CN
Ar
N
NC
HN
S
CN
S
NC
HN
Ar
ArNH2,
HCHO
RCH2NH2,
HCHO
N
NC
CN
S
NH
CN
N
H2N
N
H
N
S
CH2R
NC
Ar
4
It was established that aminomethylation of the oxygen-containing substrates 1a,b led to the formation of
pyrido[1,2-a][1,3,5]triazines regardless of the nature of the amine component. The attempts under similar conditions
to perform a reaction of compounds 1a,b with secondary amines (morpholine) and НСНО were not successful,
and the starting pyridones were isolated in 51 and 70% yields, respectively. The reaction of the pyridone 1а with
p-phenylenediamine in a 2:1 stoichiometry in the presence of excess НСНО gave 3,3'-(1,4-phenylene)bis(6-oxo-
8-phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitrile) (5) in 65% yield (Scheme 1).
The obtained compounds 2a-h were fine crystalline powders, poorly soluble in EtOH and ether, and
moderately soluble in acetone and DMSO. Compound 5 was insoluble in EtOH and acetone, poorly soluble in
DMF and DMSO. The structures of compounds 2a-h and 5 were confirmed by spectral data. The IR spectra
contained stretching bands of С=О groups at 1710-1725 cm-1, conjugated nitrile groups at 2200-2232 cm-1, and
1
N–H bonds at 3167-3480 cm-1. The Н NMR spectra of these compounds exhibited signals due to the two
methylene groups 2-СН2 and 4-СН2 (resolved as broadened singlets at 4.33-5.07 ppm and 4.89-5.63 ppm,
respectively) and NH proton signals as broadened singlets at 8.91-9.31 ppm.
The structure of 6-oxo-3,8-diphenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbo-
nitrile (2с) was confirmed by X-ray structural analysis (Fig. 1). The central fused ring system in the molecule 2с
was essentially planar (the mean least square deviation of atoms from the plane was 0.05 Å), except for the
N(3) atom, which deviated from the plane by 0.726(2) Å. This atom had a pronounced pyramidal configuration
(with the substituents deviating from the plane by 0.353(2) Å) and its lone electron pair was not conjugated to
the phenyl ring, as evidenced by the pseudo torsion angle (lone pair)–N(3)–C(10)–C(11) equal to 60°.
47

Fig. 1. The molecular structure of compound 2с with atoms represented by thermal vibration ellipsoids of 50%
probability.
At the same time, the pseudo torsion angles (lone pair)–N(3)–C(2)–N(1) and (lone pair)–N(3)–C(4)–N(5)
were optimal for the stereoelectronic interactions nN → σ*C–N, with the values of 167.7 and 171.9°, respectively.
Indeed, the bond N(5)–C(4) (1.493(2) Å) was lengthened by 0.059(4) Å, compared to the bond C(4)–N(3)
(1.434(2) Å), while the bond N(1)–C(2) (1.478(2) Å) was longer by 0.035(4) Å than the bond N(3)–C(2) (1.443(2)
Å). This meant that there were both (lone pair)–N(3)–C(2)–N(1) and (lone pair)–N(3)–C(4)–N(5) stereoelectronic
interactions observed in the crystal, and the N(5) atom of the amide was a stronger electron acceptor than the N(1)
atom of the enamine, as it was expected.
The phenyl ring С(18)–С(23) was rotated by 61.78(5)° relative to the central fused ring system, and was
not involved in conjugation with the double bond system. The diene fragment С(7)–С(8)–С(9)–С(9а) was
strongly conjugated: the formal single bond C(8)–C(9) (1.405(2) Å) was shorter than the formal double bond
C(9)–C(9a) (1.415(2) Å). This could be explained by the significant resonance contribution of canonical
structures with charge transfer from the N(1) and N(5) atoms to the C(7) or С(9) atoms, where the negative
charge may be stabilized by the cyano groups.
Compound 2с in crystalline state formed chains of intramolecular N(1)–H(1)···O(11) hydrogen bonds along
the axis a (N···O 2.931(3) Å, N–H···O 155(2)°). The links between these chains consisted of weak C–H···π
interactions.
Thus, the aminomethylation of 6-amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles could be
successfully used for the synthesis of new pyrido[1,2-a][1,3,5]triazine derivatives.
EXPERIMENTAL
1
IR spectra were recorded in Nujol on an IKS-29 spectrometer. Н NMR spectra were acquired on
Bruker DRX-500 (500 MHz) and Varian Unity Plus (400 MHz) instruments in DMSO-d6, 13С NMR spectra
were recorded on a Bruker DRX-500 (125 MHz) instrument in DMSO-d6, with TMS as internal standard.
HPLC/MS analysis was performed on an Agilent 1100 liquid chromatograph with DAD and ELSD Sedex 75
detectors, fitted with an Agilent LC/MSD VL mass spectrometer, using electrospray ionization at the ambient
pressure. Elemental analysis was performed on a Carlo-Erba 1106 Elemental Analyzer. Melting points were
determined on a Kofler bench and were not corrected. The purity of the obtained compounds was controlled by
TLC on Silufol UV-254 plates, the eluent was 1:1 acetone–hexane, visualization by iodine vapor or under UV
light.
48

Preparation of 6-Amino-4-aryl-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles 1a,b (General
Method). Compounds 1a,b were obtained by a modification of the literature method [30]. Sodium metal
(0.69 g, 0.03 mol) was dissolved in absolute EtOH (30 ml), and a mixture of the corresponding aryl-
methylidenemalononitrile (0.02 mol) and cyanoacetamide (1.68 g, 0.02 mol) was added. The reaction mixture
was refluxed for 2 h (precipitation was observed) and left overnight at 20°С, then acidified with conc. HCl to
рН 4-5. The mixture was maintained at 4°С for 48 h. The precipitate was filtered off and washed with cold
EtOH. An additional crop of the product was obtained from the mother liquors after keeping for 72 h in a
refrigerator. Compounds 1a,b were used for further transformations without additional purification.
6-Amino-2-oxo-4-phenyl-1,2-dihydropyridine-3,5-dicarbonitrile (1a). Yield 2.2 g (46%), yellow
fine crystalline powder, mp 267-269°С (mp 270°С [30], 315-320°C [31]). IR spectrum, , cm-1: 3320 (N–Н),
1
2220 (С≡N), 1695 (С=О). H NMR spectrum (500 MHz), , ppm: 7.42-7.52 (5H, m, H Ph); 8.36 (2H, br. s,
NH2); 12.52 (1H, br. s, NH). Mass spectrum, m/z: 237 [М+H]+. Mass spectrum, m/z: 235 [M-H]-, 471 [2М-H]-.
6-Amino-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (1b). Yield 2.5 g (46%),
greenish-yellow fine crystalline powder, mp >250°С (mp 205-207°С [32], 290°C (decomp.) [33]). IR spectrum,
1
, cm-1: 3330, 3180 (N–Н), 2235, 2220 (С≡N), 1665 (С=О). H NMR spectrum (400 MHz), , ppm (J, Hz):
3.82 (3Н, s, OСН3); 7.07 (2H, d, 3J = 8.1, H Ar); 7.43 (2H, d, 3J = 8.1, H Ar); 8.27 (2H, br. s, NH2); 12.32 (1H,
br. s, NH). Mass spectrum, m/z: 267 [М+H]+. Mass spectrum, m/z: 265 [M-H]-, 531 [2М-H]-.
Preparation of 3-R-8-Aryl-6-oxo-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitri-
les 2a-h (General Method). A mixture of the pyridone 1a,b (1.7 mmol) and the corresponding primary amine
(3.7 mmol) was stirred in EtOH (30 ml) at 60°C until the dissolution of the starting reagents. Then 37%
formalin (2.0 ml, 26.6 mmol, free of paraform impurity) was added. The obtained solution was refluxed for
2-3 min and quickly filtered through a folded paper filter. The reaction mixture was left at 20°С for 48-72 h.
The precipitate formed was filtered off and washed with EtOH. Compounds 2c,d,e,g were additionally purified
by recrystallization from a 1:1 mixture of EtOH–acetone.
3-Methyl-6-oxo-8-phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitrile
(2a). Yield 150 mg (30%), light-yellow fine crystals, mp 236-238°С (decomp.). IR spectrum, ν, cm-1: 3390,
1
3300 (N–H), 2220, 2200 (С≡N), 1723 (С=О). H NMR spectrum (400 MHz), δ, ppm: 2.48 (3H, s, СН3); 4.34
(2H, br. s, 2-CH2); 4.90 (2H, br. s, 4-CH2); 7.45-7.56 (5H, m, H Ph); 8.98 (1H, br. s, NH). Mass spectrum, m/z:
292 [M+H]+. Mass spectrum, m/z: 290 [M-H]-. Found, %: C 65.81; Н 4.60; N 24.13. C16H13N5O. Calculated, %:
C 65.97; Н 4.50; N 24.04.
3-Benzyl-6-oxo-8-phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitrile
(2b).
Yield 480 mg (77%), yellow fine crystals, mp 232-234°С (decomp.). IR spectrum, ν, cm-1: 3480, 3302 (N–H),
1
2220 (С≡N), 1710 (С=О). H NMR spectrum (500 MHz), δ, ppm: 3.88 (2H, br. s, CH2Ph); 4.40 (2H, br. s,
2-CH2); 4.97 (2H, br. s, 4-CH2); 7.30-7.39 (5Н, m, H Ph); 7.46-7.51 (2H, m, H Ph); 7.53-7.59 (3H, m, H Ph); 8.98
(1H, br. s, NH). 13С NMR spectrum, δ, ppm: 54.3 (CH2Ph); 59.5, 61.5 (С-2,4); 75.1 (С-9); 86.8 (С-7); 115.2
(C≡N); 116.3 (C≡N); 127.6 (C Ar); 127.9 (C Ar); 128.3 (C Ar); 128.6 (C Ar); 128.9 (C Ar); 130.2 (C Ar);
134.5 (C Ar); 136.9 (C Ar); 153.7 (С-8); 158.8 (С-9а); 160.2 (С-6). Mass spectrum, m/z: 368 [M+H]+. Mass
spectrum, m/z: 366 [M-H]-. Found, %: C 71.83; H 4.78; N 18.88. C22H17N5O. Calculated, %: C 71.92; H 4.66;
N 19.06.
6-Oxo-3,8-diphenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbonitrile
(2с).
Yield 140 mg (23%), light-yellow fine crystals, mp 202-204°С (decomp.). IR spectrum, ν, cm-1: 3292 (N–H),
1
2222 (С≡N), 1720 (С=О). H NMR spectrum (500 MHz), δ, ppm: 5.07 (2H, br. s, 2-CH2); 5.63 (2H, br. s,
4-CH2); 7.00-7.05 (1Н, m, H Ph); 7.12-7.18 (2H, m, H Ph); 7.32-7.39 (2H, m, H Ph); 7.44-7.55 (5H, m, H Ph);
9.31 (1Н, br. s, NH). 13С NMR spectrum, δ, ppm: 58.9, 59.9 (С-2,4); 75.2 (С-9); 87.0 (С-7); 114.9 (C≡N);
116.0 (C≡N); 117.8 (C Ar); 122.6 (C Ar); 127.9 (C Ar); 128.6 (C Ar); 129.7 (C Ar); 130.3 (C Ar); 134.2
(C Ar); 145.6 (C Ar); 153.8 (С-8); 158.5 (С-9а); 160.4 (С-6). Mass spectrum, m/z: 352.0 [M-H]-. Found, %:
C 71.41; H 4.39; N 19.77. C21H15N5O. Calculated, %: C 71.38; H 4.28; N 19.82.
49

3-(4-Methylphenyl)-6-oxo-8-phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbo-
nitrile (2d). Yield 450 mg (72%), yellow fine crystals, mp 183-185°С (decomp.). IR spectrum, ν, cm-1: 3342
1
(N–H), 2232, 2210 (С≡N), 1712 (С=О). H NMR spectrum (500 MHz), δ, ppm (J, Hz): 2.22 (3H, s, 4-СН3);
3
3
5.02 (2H, br. s, 2-CH2); 5.59 (2H, br. s, 4-CH2); 7.03 (2Н, d, J = 8.2, Н Ar); 7.14 (2Н, d, J = 8.2, Н Ar);
7.45-7.55 (5H, m, H Ph); 9.29 (1H, br. s, NH). 13С NMR spectrum, δ, ppm: 20.1 (СН3); 59.1, 60.2 (С-2,4); 75.1
(С-9); 87.0 (С-7); 114.9 (C≡N); 116.0 (C≡N); 117.8 (C Ar); 127.9 (C Ar); 128.6 (C Ar); 130.1 (C Ar); 130.3
(C Ar); 131.6 (C Ar); 134.2 (C Ar); 143.2 (C Ar); 153.8 (С-8); 158.5 (С-9а); 160.4 (С-6). Mass spectrum, m/z:
366.1 [M-H]-. Found, %: C 71.84; Н 4.75; N 18.97. C22H17N5O. Calculated, %: C 71.92; Н 4.66; N 19.06.
3-(4-Fluorophenyl)-6-oxo-8-phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbo-
nitrile (2e). Yield 190 mg (30%), light-yellow fine crystals, mp 172-174°С (decomp.). IR spectrum, ν, cm-1:
1
3241 (N–H), 2222, 2200 (С≡N), 1711 (С=О). H NMR spectrum (500 MHz), δ, ppm: 5.01 (2H, br. s, 2-CH2);
5.58 (2H, br. s, 4-CH2); 7.18-7.22 (4Н, m, H Ar); 7.47-7.58 (5H, m, H Ar); 9.27 (1H, br. s, NH). Mass
spectrum, m/z: 370.0 [M-H]-. Found, %: C 67.88; Н 3.88; N 18.79. C21H14FN5O. Calculated, %: C 67.92;
Н 3.80; N 18.86.
8-(4-Methoxyphenyl)-3-methyl-6-oxo-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbo-
nitrile (2f). Yield 169 mg (31%), mustard yellow fine crystals, mp 252-254°С (decomp.). IR spectrum, ν, cm-1:
3308 (N–H), 2206 (С≡N), 1710 (С=О). 1H NMR spectrum (500 MHz), δ, ppm (J, Hz): 2.47 (3H, s, CH3); 3.83
3
(3H, s, ОСН3); 4.33 (2H, br. s, 2-CH2); 4.89 (2H, br. s, 4-CH2); 7.08 (2Н, d, J = 8.3, Н Ar); 7.45 (2Н, d,
3J = 8.3, Н Ar); 8.91 (1H, br. s, NH). Mass spectrum, m/z: 322.0 [M+H]+. Mass spectrum, m/z: 320.1 [M-H]-.
Found, %: C 63.49; Н 4.79; N 21.69. C17H15N5O2. Calculated, %: C 63.54; Н 4.71; N 21.79.
3-Benzyl-8-(4-methoxyphenyl)-6-oxo-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-dicarbo-
nitrile (2g). Yield 189 mg (28%), yellow-green fine crystals, mp 204-206°С (decomp.). IR spectrum, ν, cm-1:
3451, 3272 (N–H), 2219, 2205 (С≡N), 1725 (С=О). 1H NMR spectrum (400 MHz), δ, ppm (J, Hz): 3.83 (3H, s,
3
ОСН3); 3.87 (2H, br. s, СН2Ph); 4.39 (2H, br. s, 2-CH2); 4.95 (2H, br. s, 4-CH2); 7.10 (2Н, d, J = 8.3, Н Ar);
7.28-7.37 (5H, m, H Ph); 7.45 (2Н, d, 3J = 8.3, Н Ar); 8.92 (1H, br. s, NH). Mass spectrum, m/z: 398.1 [M+H]+.
Mass spectrum, m/z: 396.1 [M-H]-. Found, %: C 69.39; Н 4.90; N 17.58. Calculated, %: C 69.51; Н 4.82;
N 17.62.
8-(4-Methoxyphenyl)-3-(4-methylphenyl)-6-oxo-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-
1
7,9-dicarbonitrile (2h). Yield 182 mg (27%), yellow-green fine crystals, mp 158-160°С (decomp.). H NMR
spectrum (500 MHz), δ, ppm (J, Hz): 2.22 (3H, s, СН3); 3.81 (3H, s, ОСН3); 5.01 (2H, br. s, 2-CH2); 5.57 (2H,
br. s, 4-CH2); 7.01 (2Н, d, 3J = 8.3, Н Ar); 7.06 (2Н, d, 3J = 8.3, Н Ar); 7.14 (2Н, d, 3J = 8.8, Н Ar); 7.43 (2Н, d,
3J = 8.8, Н Ar); 9.20 (1H, br. s, NH). Mass spectrum, m/z: 396.1 [M-H]-. Found, %: C 69.37; Н 4.84; N 17.55.
C23H19N5O2. Calculated, %: C 69.51; Н 4.82; N 17.62.
3,3'-(1,4-Phenylene)bis(6-oxo-8-phenyl-1,3,4,6-tetrahydro-2Н-pyrido[1,2-а][1,3,5]triazine-7,9-
dicarbonit-rile (5). A mixture of the pyridone 1а (600 mg, 2.5 mmol) and p-phenylenediamine (140 mg,
1.3 mmol) in DMF (10 ml) was stirred at 60°C until the dissolution of the starting reagents, then 37% formalin
(2.5 ml, 33.3 mmol, free of paraform impurity) was added. The obtained solution was refluxed for 5 min and
quickly filtered through a folded paper filter. The reaction mixture was left for 24 h at 20°С. The precipitate
formed was filtered off and washed with EtOH. Yield 510 mg (65%), light-yellow fine crystals, mp 237-239°С.
IR spectrum, ν, cm-1: 3342, 3167 (N–H), 2220 (С≡N), 1710 (С=О). 1H NMR spectrum (500 MHz), δ, ppm: 5.01
(4H, br. s, 2,2'-CH2); 5.57 (4H, br. s, 4,4'-CH2); 7.14 (4Н, br. s, H Ar); 7.40-7.57 (10H, m, H Ph); 9.01 (2H,
br. s, 2NH). Compound 5 could not be characterized by HPLC/MS due to its low solubility. Found, %: C 68.69;
Н 3.97; N 22.22. Calculated, %: C 68.78; Н 3.85; N 22.28.
X-ray Structural Investigation of Compound 2с. Monocrystals of compound 2с (C21H15N5O,
M 353.38) were grown from a 1:1 mixture of EtOH and acetone and were rhombic, space group Pbca (No. 61).
The unit cell parameters at 100 K: a 14.496(10), b 10.013(7), c 23.526(16) Å; V 3415(4) Å3; Z 8;
μ(MoKα) 0.089 mm-1; dcalc 1.375 g/cm3. In the range of 3.462 ≤ 2θ ≤ 66.454° there were 32742 reflections
measured, of which 6343 were independent (Rint 0.1490, Rsigma 0.1255). The final probability factors: R1 0.0610
50

(reflections with I > 2σ(I)), wR2 0.1344 (all reflections). A suitable quality crystal was selected and positioned
on a glass needle in a Bruker APEX II DUO instrument. The measurements were performed with the Olex2
software package [34], the structure was solved with the olex2.solve software by the "charge flipping" method
and was refined by the method of least squares, using the ShelXLMP-2012 software [35]. The complete set of
X-ray structural data for compound 2с was deposited at the Cambridge Crystallographic Data Center (deposit
CCDC 976616).
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