Crystal and molecular structure of methyl-(4-chlorophenyl)sulfone

Article abstract of DOI:10.1134/S0022476617070307

Sulfones are known to be biologically active compounds. X-ray diffraction is used to determine the crystal and molecular structure of methyl-(4-chlorophenyl)sulfone. The closest molecules are in pairs oriented to each other by their chlorine atoms. The cr

Full text of DOI:10.1134/S0022476617070307

Journal of Structural Chemistry. Vol. 58, No. 7, pp. 1468-1471, 2017.
Original Russian Text © 2017 S. N. Adamovich, A. N. Mirskova, E. A. Zel’bst, V. S. Fundamensky.
CRYSTAL AND MOLECULAR STRUCTURE
OF METHYL-(4-CHLOROPHENYL)SULFONE
1,2 1,2
S. N. Adamovich , A. N. Mirskova ,
UDC 541.272:548.737
3
E. A. Zel′bst , and V. S. Fundamensky
4
Sulfones are known to be biologically active compounds. X-ray diffraction is used to determine the crystal
and molecular structure of methyl-(4-chlorophenyl)sulfone. The closest molecules are in pairs oriented to
each other by their chlorine atoms. The crystal architecture is formed by endless ribbons of paired
associates of the molecules under study.
DOI: 10.1134/S0022476617070307
Keywords: methyl(4-chlorophenyl)sulfone, crystal and molecular structure, arylsulfonylacetic acids,
protatranes, biologically active derivatives.
We have previously synthesized a series of ethanol-ammonium salts and ionic liquids (protatranes,
hydrometalatranes, metalprotatranes and their analogs) [1-6] based on biologically active arylchalcogenylacetic acids
RYСН СООН (R = aryl, indolyl, pyridinyl; Y = O, S, SO , Se), biogenic ethanolamines (mono-, di- and triethanolamines)
2
2
and essential metals (Ca, Mg, Zn). Compounds exhibiting immunotropic, anticancer, antimetastatic, and other activities were
1
revealed among them. The structure of atranes was proved by IR, H, C, and N NMR spectroscopy, quantum chemical
13
15
–
+
calculations, and XRD [7-12]. Developing these studies, we have obtained 4-ClC H SО CH COO ⋅НN (CH CH OH)
6 4 2 2 2 3
2
– +
protatrane (I) and 4-ClC H SО CH COО ⋅НN (Ме)(CH СН ОН) quasiprotatrane (II). Their crystal and molecular
6
4
2
2
2
2
2
structures were determined [7, 10]. For the comparative study of the pharmacological action of these compounds, we have
– +
synthesized their simplest analog 4-ClC H SO СН CОО ⋅НN (Ме )CH CH OH hypoprotatrane (III). All the previously
6
4
2
2
2
2
2
obtained compounds, including I and II, are stable on storage and heating (200 °C and higher). However, during
recrystallization (isopropyl alcohol, 45 °C) III unexpectedly undergoes soft decarboxylation with the formation of methyl-(4-
chlorophenyl)sulfone (IV) according to the following scheme:
−
+
4-ClC H SO СН CОО ⋅ НN (Ме )CH CH OH → 4-ClC H SO CH +Ме NCH CH OH +CO
6
4
2
2
2
2
2
6
4
2
3
2
2
2
2
(III)
(IV)
Sulfones actively suppress agents of a series of diseases and are used for the treatment of tuberculosis, lepra, lupus
erythematosus [13].
Here we report the results of the X-ray diffraction study of the crystal and molecular structure of methyl(4-
chlorophenyl)sulfone (IV). The three-dimensional set of intensities was measured on an automated Bruker Kappa APEX-II
diffractometer; the experimental data are listed in Table 1.
1
2
Favorsky Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia. Irkutsk Research
3
Center, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia. Pedagogical Institute of the Irkutsk State
4
University, Russia; zelbst@rambler.ru. St. Petersburg State Technological Institute, Russia. Translated from Zhurnal
Strukturnoi Khimii, Vol. 58, No. 7, pp. 1506-1509, September-October, 2017. Original article submitted November15, 2016;
revised December 19, 2016..
1468
0022-4766/17/5807-1468 © 2017 by Pleiades Publishing, Ltd.

TABLE 1. Experimental Data and Refinement Parameters of the Molecular Structure of Methyl-(4-Chlorophenyl)Sulfone
Compound
IV
Chemical formula
Crystal size, mm
Temperature, K
Wavelength λ, Å
Space group; Z
C7 H7 Cl O2 S
0.14×0.18×0.30
293
0.71073
P-1; 2
62
2θ , deg
max
a, b, c, Å
5.429(1), 6.995(1), 10.952(2)
95.27(1), 94.31(1), 90.64(1)
α, β, γ, deg
3
V, Å
412.9(1)
1.533
2493
3
d, g/cm
Total number of reflections
Number of reflections with I > 2σ(I)
Limiting indices, h, k, l
1201
0 ≤ h ≤ 7, –10 ≤ k ≤ 10, –14 ≤ l ≤ 14
Number of parameters refined
μ, 1/mm
110
0.659
The refinement of the unit cell parameters and the primary processing of the experimental reflections was performed
using the Bruker SAINT programs; the structure solution was carried out using the SIR-2011 software package [14]. The
structure was refined by the full-matrix least-squares techniques in the anisotropic approximation for non-hydrogen atoms.
All the hydrogen atoms were found in the difference Fourier maps and refined as a rigid body to R = 0.052, R = 0.054. The
w
СIF-files containing the complete information on the structure of IV (Fig. 1) have been deposited with the Cambridge
Crystallographic Data Centre (CCDC 904358) (www.ccdc.cam.ac.uk/data_request/cif).
The crystal structure of IV consists of dimers formed by weak intermolecular contacts Cl…Cl = 3.324(4) Å. The
molecular packing in the crystal looks like a staircase in which the opposite sulfone groups are in the same plane and form
an endless ribbon of these stairs (Fig. 2). Thus, the crystal architecture consists of ribbons of paired associates of these
molecules.
Table 2 lists some interatomic distances in methyl-(4-chlorophenyl)sulfone molecules and related 4-chlorine-3-
nitraphenyl methyl sulfone (VERZUO); 5-chlorine-2-(methylsulfonyl)phenyl-imidazolidine-2,4-dione (VARBAR); cis-4-(4-
chlorophenyl)sulfonyl-4-(2-5-difluorophenyl)cyclohexanol (IDANIL), and 4-fluoro-3-nitrophenyl methylsulfone (VERZOI)
[15]. The С–С bond lengths are averaged in the phenyl rings (Table 2); in IV the planes of their rings are parallel to each
other. The chlorine (fluorine in VERZOI) and sulfur atoms, which occupy para positions, lie in the plane of these rings. All
the interatomic distances of the corresponding atoms are comparable (with regard to their errors) with those of the title
Fig. 1. The molecule of methyl-
(4-chlorophenyl)sulfone IV.
1469

Fig. 2. Fragment of the molecular packing of IV in the crystal.
TABLE 2. Interatomic Distances in the Structures of IV and the Related Molecules
Interatomic distance, Å
Ref. code
Cl–C
(C–C) av. Ph.
S–C
S–Me
S–O
S–O
Space group
1
2
904358, IV
VERZUO
VARBAR
IDANIL
1.743(5)
1.719(2)
1.380 (7)
1.383(4)
1.385(8)
1.369(3)
1.378(3)
1.774(5)
1.774(2)
1.783(6)
1.761(2)
1.774(2)
1.752(5)
1.751(3)
1.766(6)
1.836(2)
1.745(3)
1.438(5)
1.434(1)
1.440(4)
1.436(1)
1.424(2)
1.442(3)
1.436(2)
1.444(4)
1.448(1)
1.429(2)
P-1
P-1
1.739(6)
P2 /c
1
1.734(2)
P2 /c
1
VERZOI
F-C 1.333(3)
P2 /c
1
molecule, despite the type of substituents (complex and less complex) in the ortho position of the benzene ring or at the sulfur
atom in the latter (Table 2).
The coordination polyhedron of sulfur is a slightly distorted tetrahedron. Two out of four its vertices are occupied by
oxygen atoms, the other two are occupied by carbon atoms of the methyl and 4-chlorophenyl groups. In the latter two cases,
the bond lengths (S–C, S–Me) correspond to the electronic effects of substituents, and both S–O bonds differ only by
0.004 Å, and they are close to the bond lengths in the related sulfone molecules [16, 17].
In the polyhedron of the sulfur atom the bond angles are the same as in related sulfones (Table 2). In the molecule of
IV, the OSO angle is 118.3(2)°, nearly 120°; both OSC angles (108.3(2)°) are closer to tetrahedral, and the CSC angle
(104.5(2)°) is far from the tetrahedral one. The torsion angles between sulfur and the benzene ring, on the one hand, and those
between chlorine and the benzene ring, on the other hand, are nearly 180°, thus proving the planar structure of the Cl–Ph–S
moiety. The bond lengths and angles in the phenyl ring of the molecule of IV are typical.
The research was carried out in the framework of the Integration Program of the Irkutsk Research Center of the
Siberian Branch of the Russian Academy of Sciences “Basic Researches and Cross-Cutting Technologies as a Basis of the
Leading Development of the Baikal Region and Its Interregional Communications”.
REFERENCES
1. S. N. Adamovich, A. N. Mirskova, R. G. Mirskov, and U. Schilde, Chem. Central J., 5, 23 (2011).
2. A. N. Mirskova, S. N. Adamovich, R. G. Mirskov, and U. Schilde, Chem. Central J., 7, 4 (2013).
3. A. N. Mirskova, S. N. Adamovich, R. G. Mirskov, and M. G. Voronkov, Russ. Chem. Bull. (Int. Ed.), 63, 1869 (2014).
4. A. N. Mirskova, S. N. Adamovich, R. G. Mirskov, et. al., Open Chem., 13, 149 (2015).
5. S. N. Adamovich, R. G. Mirskov, and A. N. Mirskova, Russ. Chem. Bull. (Int. Ed.), 64 (2015).
6. S. N. Adamovich, G. A. Kuznetsova, I. A. Ushakov, et. al., Russ. Chem. Bull. (Int. Ed.), 65 (2016).
1470

7. V. E. Shklover, G. V. Gridunova, Yu. T. Struchkov, et. al., Dokl. Chem., 269 (1983).
8. M. G. Voronkov, V. S. Fundamenskii, E. A. Zelbst, and S. N. Adamovich, J. Struct. Chem., 51, 790 (2010).
9. N. N .Chipanina, T. N. Aksamentova, S. N. Adamovich, et. al., Comput. Theor. Chem., 985, 36 (2012).
10. M. G. Voronkov, V. S. Fundamenskii, S. N. Adamovich, et. al., J. Struct. Chem., 54, 182 (2013).
11. I. A. Ushakov, V. K. Voronov, S. N. Adamovich, et. al., Russ. Chem. Bull. (Int. Ed.), 64, 58 (2015).
12. I. A. Ushakov, V. K. Voronov, S. N. Adamovich, et. al., J. Mol. Struct., 1103, 125 (2016).
13. M. D. Mashkovsky, Medicine Remedies. 15 ed. [in Russian], Novaya Volna, Moscow (2005).
14. M. C. Burla, M. Caliandro, M. Camalli, et. al., J. Appl. Crystallogr., 45, 357 (2012).
15. Cambridge Structural Database.Version 5.32, University of Cambridge, UK.
16. W. Adam, N. Carballeira, E.-M. Peters, et. al., J. Am. Chem. Soc., 105, 1532 (1983).
17. J. P. Scott, P. R. Mullens, S. E. Brewer, et. al., J. Org. Biomol. Chem., 4, 1806 (2006).
1471