Molecular and crystal structure of 5-amino-3-(N-p-methylbenzoyl-N-p- toluenesulfonyl)amino-1-phenyl-1,2,4-triazole

Article abstract of DOI:10.1007/s10593-007-0125-7

It has been established by X-ray structural analysis that the initial product of the interaction of 5-amino-1-phenyl-3-p-toluenesulfonylamino-1,2,4- triazole with p-methylbenzoyl chloride is 5-amino-3-(N-pmethylbenzoyl-N-p- toluenesulfonyl)amino-1-phenyl-

Full text of DOI:10.1007/s10593-007-0125-7

Chemistry of Heterocyclic Compounds, Vol. 43, No. 6, 2007
MOLECULAR AND CRYSTAL STRUCTURE
OF 5-AMINO-3-(N-p-METHYLBENZOYL-
N-p-TOLUENESULFONYL)AMINO-
1-PHENYL-1,2,4-TRIAZOLE
V. M. Chernyshev1, V. A. Rakitov1, V. A. Taranushich1, and Z. A. Starikova2
It has been established by X-ray structural analysis that the initial product of the interaction of 5-amino-
1-phenyl-3-p-toluenesulfonylamino-1,2,4-triazole with p-methylbenzoyl chloride is 5-amino-3-(N-p-
methylbenzoyl-N-p-toluenesulfonyl)amino-1-phenyl-1,2,4-triazole.
Keywords: amino- and 3,5-diamino-1,2,4-triazole, 5-amino-3-(N-p-methylbenzoyl-N-p-toluenesulfonyl)-
amino-1-phenyl-1,2,4-triazole, 1,2,4-triazole, acylation, X-ray structural analysis.
3,5-Diamino-1-R-1,2,4-triazoles enter into the composition of medicinal preparations [1] and are used
for obtaining substances possessing a wide spectrum of biological activity [2, 3]. On acylating 5-amino-
1-phenyl-3-p-toluenesulfonylamino-1,2,4-triazole (1) with p-methylbenzoyl chloride in acetonitrile in the
presence of pyridine a compound is obtained which, on the basis of data of elemental analysis, IR and NMR
spectroscopy, was assigned the structure of 5-amino-3-(N-p-methylbenzoyl-N-p-toluenesulfonyl)amino-
1-phenyl-1,2,4-triazole (2) [4]. However the spectral data presented in [4] were not able completely to exclude
the possibility of isomeric structures of this compound, such as structures 3 and 4.
O
R
N
N
R
Ph
N
Ts
N
N
H
N
NH2
N
Ph
N
RCOCl
2
Ts
N
O
–
N
+
NH2
N
Ph
N
1
N
Ph
Ts
N
N
Ts
O
NH2
N
NH2
R
4
3
R = p-MeC6H4
__________________________________________________________________________________________
1South-Russian State Technical University, Novocherkassk 346428; e-mail: tnw@novoch.ru.
2A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow 117813;
e-mail: star@xray.ineos.ac.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 917-921,
June, 2007. Original article submitted February 26, 2006.
776
0009-3122/07/4306-776©2007 Springer Science+Business Media, Inc.

Since the structure of the obtained compound enables the special features of the acylation reactions of
3-acylamino-5-amino- and 5-amino-3-sulfonylamino-1-R-1,2,4-triazoles to be understood [4], we have carried
out an X-ray structural analysis of it.
Fig. 1. Structure of the compound 2 molecule.
Fig. 2. System of intermolecular hydrogen bonds in the crystal of compound 2.
777

According to the data of X-ray structural analysis (Figs. 1, 2, Tables 1, 2) the compound 2 molecule has
a non-planar structure. The phenyl group makes a dihedral angle of 29.4° with the plane of the triazole ring, and
the benzene rings of the p-methylbenzoyl and p-toluenesulfonyl groups are inclined to the triazole ring at 50.1
and 28.6° respectively.
The bond lengths in the triazole ring are in agreement with the corresponding values of substituted
triazoles studied previously [3, 5-11]. The N(4) and N(5) atoms have a trigonal pyramidal configuration (sum of
valence angles 336.2 and 350.5° respectively). The deviation of the N(4) atom from the plane of the triazole ring
is 0.014(3) Å, while the N(5) atom deviates by 0.091(3) Å, probably as a result of the reduced intramolecular
contact C(2)···C(9) of 3.05 Å and the shortened contacts at N(1)···C(9) of 3.18 and N(3)···C(4) 3.19 Å.
The C(1)–N(4) bond length (1.360(2) Å) is in agreement with corresponding values in other 5-amino-
1,2,4-triazoles (1.347-1.371 Å [5-7]). The C(2)–N(5) bond (1.423(2) Å) is lengthened in comparison with
3-amino-1,2,4-triazoles, in which it is 1.370-1.376 Å [3, 9-11], and is closest to the analogous bond in
1-(1-methyl-5-morpholino-1,2,4-triazol-3-yl)-3-phenyl-2-thioxoimidazolidine-4,5-dione (1.429 Å) [8], in which
the 3-amino group of the 1,2,4-triazole is included in an imidazolidine ring.
The system of atoms formed by the carbonyl group, the N(5) atom, and the sulfonyl group (O(3)–C(3)–
N(5)–S(1)–O(1)–O(2)) is close in geometric parameters to the corresponding segment in N-tolyl-N-tosyl-
p-chlorobenzamide [12]. The bond length of C(3)–N(5) is 1.429(2), S(1)–N(5) 1.706(1) Å (1.418 and 1.704 Å
respectively [12]), the angles O(3)C(3)N(5) 121.2(2), C(3)N(5)S(1) 119.1(1), O(1)S(1)N(5) 106.16(7), O(1)S(1)O(2)
120.77(8)° (121.3, 118.4, 107.1, 119.5° [12]), the carbonyl group is almost coplanar with the S(1)–O(2) bond, the
TABLE 1. Some Bond Lengths (d) in Compound 2
Bond
d, Å
Bond
N(5)–C(3)
O(3)–C(3)
S(1)–N(5)
S(1)–O(1)
S(1)–O(2)
S(1)–C(11)
C(3)–C(4)
d, Å
N(1)–C(2)
N(1)–N(2)
N(2)–C(1)
N(3)–C(1)
N(3)–C(2)
N(4)–C(1)
N(5)–C(2)
N(2)–C(18)
1.301(2)
1.388(2)
1.366(2)
1.328(2)
1.357(2)
1.360(2)
1.423(2)
1.424(2)
1.429(2)
1.208(2)
1.706(1)
1.426(1)
1.428(1)
1.757(2)
1.490(2)
TABLE 2. Some Valence Angles (ω) in Compound 2.
Angle
ω,deg
Angle
ω, deg
C
(2)N(1)N(2)
101.1(1)
109.3(1)
102.2(1)
117.7(1)
109.8(1)
130.4(1)
119.9(1)
122.9(1)
119.3(1)
124.0(2)
126.2(1)
108.9
H(1N4)N(4)H(2N4)
C(2)N(5)C(3)
C(2)N(5)S(1)
C(3)N(5)S(1)
O(3)C(3)N(5)
O(3)C(3)C(4)
N(5)C(3)C(4)
O(1)S(1)O(2)
O(1)S(1)N(5)
O(2)S(1)N(5)
O(1)S(1)C(11)
O(2)S(1)C(11)
N(5)S(1)C(11)
115.6
C(1)N(2)N(1)
C(1)N(3)C(2)
N(1)C(2)N(3)
N(3)C(1)N(2)
C(1)N(2)C(18)
N(1)N(2)C(18)
N(1)C(2)N(5)
N(3)C(2)N(5)
N(3)C(1)N(4)
N(4)C(1)N(2)
C(1)N(4)H(1N4)
C(1)N(4)H(2N4)
115.7(1)
115.7(1)
119.1(1)
121.2(2)
123.9(2)
115.0(1)
120.77(8)
106.16(7)
103.92(7)
109.73(8)
108.09(8)
107.30(7)
111.6
778

fragment O(3)C(3)N(5)S(1)O(2) is planar within the limits ±0.02 Å, and the pseudotorsion angle O(3)C(3)S(1)O(2) is
174.9° (178.4° [12]). It should be noted that in compound 2 the N(5)–S(1) bond length is greater than the length
characteristic of N-acyl-N-tosylamino fragments (1.60-1.64 Å) [13]. The same S–N bond length is found only in
two more molecules containing the fragment under consideration [14, 15].
In the crystal, molecules are combined in centrosymmetric H-dimers (Fig. 2) as a result of a hydrogen
bond N(3)···H(1NA)–N(4A) [parameters of the hydrogen bond are length N(3)···N(4A) 3.016(2), N(3)···H(1NA) 2.14 Å,
angle N(3)···H(1NA)–N(4A) 171°). In addition, in the dimer a second interaction was observed of the unshared pair
of the N(4) atom and the π-system of the ring C(11A)–C(16A) and correspondingly of the N(4A) atom and the
π-system of the ring C(11)–C(16). The distance N(4)···centroid (C(11A)–C(16A)) is equal to 3.284 Å.
The X-ray structural analysis data therefore confirmed the proposed direction of the acylation reaction of
3-acylamino-5-amino- and 5-amino-3-sulfonylamino-1-R-1,2,4-triazoles [4]. Acylation of the substituted
3-amino group initially is confirmed by the formation of 5-amino-3-(N,N-diacyl)amino- or 5-amino-3-(N-acyl-
N-sulfonyl)amino-1-R-1,2,4-triazoles, which are then rearranged to the thermodynamically more stable
3,5-diacylamino- or 5-acylamino-3-sulfonylamino-1-R-1,2,4-triazoles.
EXPERIMENTAL
X-ray Structural Investigation. Colorless prismatic crystals of compound 2, obtained from a DMF–EtOH,
1 : 1 mixture, were monoclinic, C23H21N5O3S. At 120 K a = 8.1186(6), b = 18.204(1), c = 14.666(1) Å,
β = 94.203(2)°, V = 2161.7(3) Å3, Mr = 447.51, Z = 4, space group P21/c, dcalc = 1.375 g/cm3. The experimental
collection of 13461 reflections was obtained on a Bruker SMART CCD area detector diffractometer at 120 K
(λMoKα radiation, 2θmax = 54.00°) with a monocrystal of size 0.50×0.40×0.35 mm. After averaging equivalent
reflections 5814 independent reflections were obtained (Rint = 0.0448), which were used to decipher and refine
the structure. Absorption (µ = 0.186 mm-1) was not taken into consideration.
The structure was solved by the direct method, all the non-hydrogen atoms were localized in electron
density difference syntheses and refined on F2 in an anisotropic approach. The hydrogen atoms of the NH2
hkl
group were localized in electron density difference syntheses and refined by the riding model isotropic approach;
H(C) hydrogen atoms were placed in geometrically calculated positions and moved on refining in the rider
model with U(H) = nU(C), where n = 1.2 and 1.5 for CH and CH3 groups respectively, U(C) is the equivalent
temperature factor of the carbon atom to which the corresponding H atom is linked.
Final values of the uncertainty factors: R1 = 0.0436 (calculated on Fhkl for 3766 reflections with
I >2σ(I)), wR2 = 0.1016 (calculated on F2hkl for all 4534 reflections), GOOF = 1.004, 289 refined parameters.
All calculations were carried out with the SHELXTL PLUS 5 set of programs [16].
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