Mendeleev Commun., 2010, 20, 47–49
Supramolecular organization in the crystal of 10·DMSO is
References
governed by rather strong H-bond with the solvate molecule
[N(3)···O(1S) 2.834(3) Å, Figure 1] and a number of weak
contacts, such as C–H···O, C–H···N, C–H···S, C–H···π, and H···H
ones, completing the formation of the 3D framework. In the case
of the 10·Bz crystallosolvate, despite the presence of the con-
venient donors and acceptors of proton, there are no H-bonds
between the species and the strongest intermolecular interac-
tion is C(2)–O(1)···S(1) binding [S···O 3.163(2) Å]. The latter
leads to the formation of the centrosymmetric dimers, which
are further held together by means of weaker contacts of the
same types as those in the crystal of 10·DMSO. The solvate
benzene species are bound to the molecules of the product via
the H···H contacts.
1 R. C. Elderfield and R. N. Prasad, J. Org. Chem., 1959, 24, 1410.
2 K. S. Dhaka, H. S. Chaudhary, K. S. Sharma and H. K. Pujari, Indian J.
Chem., 1976, 14B (7), 541.
3 M. Gordon, J. Am. Chem. Soc., 1951, 73, 984.
4 S. Bala, M. L. Sachdeva, R. N. Handa and H. K. Pujari, Heterocycles,
1980, 14 (2), 149.
5 A. Singh, K. S. Dhaka, H. S. Chaudhary and H. K. Pujari, Indian J. Chem.,
1977, 15B (1), 46.
6 S. V. Vasilevsky, Yu. V. Nelyubina and A. N. Kravchenko, Mendeleev
Commun., 2009, 19, 279.
7 A. S. Sigachev, A. N. Kravchenko, K. A. Lyssenko, P. A. Belyakov, O. V.
Lebedev and N. N. Makhova, Mendeleev Commun., 2003, 190.
8 G. M. Sheldrick, SHELXTL v. 5.10, Structure Determination Software
Suite, Bruker AXS, Madison, Wisconsin, USA.
Thus, as a result of the detailed study of the condensation of
HalCH2COOH with imidazotriazinone 7, we have established
that the reaction occurs regiospecifically depending on reaction
conditions. Carboxyethylation at the sulfur atom of compound
7 occurs by carrying out the reaction in EtOH, while tricycle 10
is formed in AcOH. Compound 10 was obtained from acid 8
regiospecifically. Structures of compounds 8 and 10 were proved
1
using NMR spectroscopy (1H-{13C} HSQC, H-{15N} HSQC,
TOCSY, NOESY and HMBC, HSQCED).† X-ray analysis of
10 was also carried out.‡
†
The 1H and 13C NMR spectra were recorded on a Bruker AM-300
spectrometer (300.13 MHz for 1H and 75.47 MHz for 13C NMR spectra).
Chemical shifts were measured with reference to the residual protons of
a [2H6]DMSO solvent (d 2.50 ppm). Mass spectra were measured on an
MS 30 spectrometer. Melting points were determined in a GALLENKAMP
instrument (Sanyo).
Commercially available compounds (thiosemicarbazide, EtOH, AcONa,
BrCH2COOH, ClCH2COOH, AcOH, Ac2O, Py) supplied by ACROS
were used in the syntheses. The solvents were used without preliminary
purification.
Received: 2nd July 2009; Com. 09/3361
‡
Crystallographic data. Crystals of 10·DMSO (C22H25N5O3S2, M = 471.59)
are monoclinic, space group P21/n, at 120 K: a = 8.8821(7), b = 15.4896(13)
and c = 16.4553(13) Å, b = 90.588(5)°, V = 2263.8(3) Å3, Z = 4 (Z' = 1),
dcalc = 1.384 g cm–3, m(MoKα) = 2.70 cm–1, F(000) = 992. Intensities of
23005 reflections were measured with a Bruker SMART 1000 CCD
diffractometer [l(MoKα) = 0.71072 Å, w-scans, 2q < 56°] and 5458
independent reflections (Rint = 0.0430) were used in further refinement.
Crystals of 10·Bz (C23H22N5O2S, M = 432.52) are monoclinic, space
group P21/n, at 120 K: a = 15.8295(13), b = 8.3843(7) and c = 16.6669(13) Å,
b = 112.721(5)°, V = 2040.4(3) Å3, Z = 4 (Z' = 1/2), dcalc = 1.408 g cm–3,
m(MoKα) = 1.91 cm–1, F(000) = 908. Intensities of 18316 reflections were
measured with a Bruker SMART 1000 CCD diffractometer [l(MoKα) =
The crystals for XRD study were prepared by crystallizing compound
10 from [2H6]DMSO and benzene.
{(5,7-Dimethyl-6-oxo-4a,7a-diphenyl-4,4a,5,6,7,7a-hexahydro-1H-imidazo-
[4,5-e]-1,2,4-triazin-3-yl)thio}acetic acid 8: yield: 85% (using BrCH2COOH)
1
or 90% (using ClCH2COOH), mp 243–245 °C. H NMR ([2H6]DMSO)
d: 2.52 [s, 3H, Me–N(5)], 2.53 [s, 3H, Me–N(2)], 3.75 (m, 2H, CH2),
6.83 [d, 2H, o-Ph–C(15) and o-Ph–C(19), J 8.1 Hz], 7.05 [m, 8H,
Ph–C(9–13, 16–18)], 7.15 [s, 1H, N(1)H], 7.93 [s, 1H, N(4)H], 12.85
(br. s, 1H, COOH). 13C {1H} NMR ([2H6]DMSO) d: 25.4 (Me), 25.7
(Me), 32.6 (SCH2), 82.4 [C(7a)], 83.6 [C(4a)], 127.1 [C(Ph)], 127.6
[C(Ph)], 127.8 [C(Ph)], 127.9 [C(Ph)], 128.2 [C(Ph)], 135.9 [C(14)],
136.9 [C(8)], 145.1 (CS), 158.2 [C(6)], 170.2 (COOH). MS, m/z (%):
411 (M+, 3), 316 (15), 278 (35), 264 (100), 249 (12), 234 (10), 207 (21),
118 (35), 104 (15), 101 (24), 59 (45).
1,3-Dimethyl-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e]-1,3-
thiazolo[3,2-b]-1,2,4-triazine-2,7(1H,6H)-dione 10: yield: 75% (using
BrCH2COOH) or 63% (using ClCH2COOH) or 83% (by boiling of
compound 8 in Ac2O), mp 280–282 °C. 1H NMR ([2H6]DMSO) d: 2.56
[s, 3H, Me–N(3)], 2.58 [s, 3H, Me–N(1)], 4.18 (m, 2H, CH2), 6.70 [d,
2H, o-Ph–C(17, 21), J 6.9 Hz], 6.78 [d, 2H, o-Ph–C(11, 15), J 7.3 Hz],
7.02–7.15 (m, 6H, Ph), 7.37 (s, 1H, NH). 13C {1H} NMR ([2H6]DMSO)
d: 25.1 (Me), 25.8 (Me), 30.0 [C(6)], 79.3 [C(9a)], 81.2 [C(3a)], 126.1
[C(Ph)], 127.1 [C(Ph)], 127.6 [C(Ph)], 127.7 [C(Ph)], 127.8 [C(Ph)],
128.0 [C(Ph)], 134.2 [C(Ph)], 135.4 [C(Ph)], 151.0 [C(4a)], 159.1 [C(2)],
165.8 [C(7)]. MS, m/z (%): 392 [(M+ – 1), 2], 316 (6), 278 (24), 265
(21), 264 (100), 249 (11), 207 (31), 118 (52), 104 (17), 77 (30), 51 (38).
= 0.71072 Å, w-scans, 2q < 56°] and 4916 independent reflections (Rint =
= 0.0389) were used in further refinement.
The structures were solved by a direct method and refined by the full-
matrix least-squares technique against F2 in the anisotropic–isotropic
approximation. The hydrogen atom of NH group was located from the
Fourier density synthesis. The H(C) atom positions were calculated. All
hydrogen atoms were refined in the isotropic approximation in riding
model with the Uiso(H) parameters equal to 1.2Ueq(Ci), for methyl groups
equal to 1.5Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent
thermal parameters of the carbon atoms to which corresponding H atoms
are bonded. For 10·DMSO the refinement converged to wR2 = 0.1329 and
GOF = 1.001 for all independent reflections [R1 = 0.0532 was calculated
against F for 3638 observed reflections with I > 2s(I)]. For 10·Bz the
refinement converged to wR2 = 0.1224 and GOF = 1.002 for all independent
reflections [R1 = 0.0478 was calculated against F for 3251 observed reflec-
tions with I > 2s(I)]. All calculations were performed using SHELXTL
PLUS 5.0.8
CCDC 758605 and 758606 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cambridge
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2010.
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