Synthesis, crystal and molecular-electronic structure, and kinetic investigation of two new sterically hindered isomeric forms of the dimethyl[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride

Article abstract of DOI:10.1016/j.molstruc.2017.02.016

Two new structural isomers – 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesu

Full text of DOI:10.1016/j.molstruc.2017.02.016

Journal of Molecular Structure 1137 (2017) 1e8
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, crystal and molecular-electronic structure, and kinetic
investigation of two new sterically hindered isomeric forms of the
dimethyl[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride
,
*
L. Rublova a, B. Zarychta b, V. Olijnyk b, B. Mykhalichko c
a Department of General Chemistry, Donetsk National Technical University, Donetsk 83001, Ukraine
b Faculty of Chemistry, Opole University, Opole 45-052, Poland
c Department of Burning Processes and General Chemistry, L'viv State University of Life Safety, L'viv 79007, Ukraine
a r t i c l e i n f o
a b s t r a c t
Article history:
Two new structural isomers e 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride
(1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by
interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesulfonamide or N-(2,6-dimethylphenyl)-N-
methylbenzenesulfonamide with chlorosulfonic acid. Both compounds have been structurally charac-
terized by X-ray single crystal diffraction at 100 K. The crystals of 1 are triclinic: space group P1,
Received 15 November 2016
Received in revised form
3 February 2017
Accepted 4 February 2017
a ¼ 8.1542(2), b ¼ 11.0728(3), c ¼ 11.2680(3) Å,
a
¼ 116.557(3),
b
¼ 95.155(2),
g
¼ 108.258(2)ꢀ,
V ¼ 831.97(4) Å3, Z ¼ 2, R ¼ 0.0251 for 2429 reflections; the crystals of 2 are monoclinic: space group P21/
Keywords:
c, a ¼ 11.7428(2), b ¼ 11.3518(2), c ¼ 12.5886(2) Å,
b
¼ 93.659(2)ꢀ, V ¼ 1674.66(5) Å3, Z ¼ 4, R ¼ 0.0269 for
Sterically hindered derivatives of aromatic
sulfonic acids
X-ray crystal structure determination
Kinetics of substitution reactions in aqueous
solution
2622 reflections. The structure of both isomers is organized as molecular crystals. These sterically hin-
dered organic molecules are cross-linked into framework by means of hydrogen bonds of CeH/O type
(H/O distances are in range 2.27(2)e2.76(2) Å). The ab initio quantum-chemical calculations of an
electronic structure of the isomeric molecules of 1 and 2 have been performed using the restricted
Hartree-Fock method with a 6-31G* basis set. The calculated values of charge density concentrated on
the electronegative atoms of the sterically hindered molecules are in good agreement with parameters of
the intramolecular hydrogen bonds. The obtained data of the kinetic investigations of the substitution
reactions in aqueous solution well correlate with stereo-chemical characteristics of the both molecules of
the dimethyl[methyl(phenylsulfonyl)amino]-benzenesulfonyl chloride.
Quantum-chemical analysis
Ortho-effect
© 2017 Published by Elsevier B.V.
1. Introduction
parameters of the solvolysis processes [9e13]. That is why high
reactivity of bulky organic molecules of this family makes their
Dimethyl[methyl(phenylsulfonyl)amino]benzenesulfonyl chlo-
ride belongs to the family of aromatic sulfonic acids derivatives,
which are very attractive objects due to their wide applications, in
particular, in industry [1], medicine [2], agriculture [3], high poly-
mers production [4], as extraction agents [5], dyestuffs [6], de-
tergents [7], or as heat-sensitive recording materials [8] etc.
Throughout the long time, a specific attention of researchers has
been paid to the synthesis and study of the reactivity of the steri-
cally hindered derivatives of aromatic sulfonic acids, which ste-
reospecific features are believed to play an important role in crucial
change of some physical and chemical properties, e.g. of kinetic
structures more preferable agents in the organic synthesis. For
instance, the bulky molecules of benzenesulfonyl chlorides de-
rivatives show a biological activity and consequently they can be
used as potential new broad-spectrum antibacterial drugs [14e17].
Currently, ascertainment of relationships between structure and
reactivity of sterically hindered derivatives of aromatic sulfonic
acids, in particular, the benzenesulfonyl chlorides, is one of the
principal problems of organic chemistry. These bulky organic
molecules can show hyperreactivity in solvolysis reactions. A
dominant role in such processes belongs to the ortho-effect or,
more broadly, proximity effect which nevertheless is a little-
studied phenomenon. It can be explained by the lack of
reliable structural data needed for an adequate interpretation of
solvent molecules behavior in the conditions of nucleophilic attack
* Corresponding author.
E-mail address: mykhalitchko@email.ua (B. Mykhalichko).
on a crowded reaction center. Unfortunately, a quantitative
http://dx.doi.org/10.1016/j.molstruc.2017.02.016
0022-2860/© 2017 Published by Elsevier B.V.

2
L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
interpretation of this effect is also absent in the literature.
Kinetic investigations of the hydrolysis of ortho-alkyl-
substituted analogues of benzenesulfonyl chloride reveal that
values of rate constants obtained experimentally and calculated on
the basis of formalistic approach may significantly differ [18,19].
Though on the other hand, ortho-alkyl derivatives of benzene-
sulfonyl chlorides show increased reactivity in all cases of hydro-
lysis [20e23]. In such substitution reactions, the ortho-effect is
defined not only by the nature of substituents, but also the stereo-
chemical features of substrate initial state and transition state of a
nucleophilic substitution process [24e26]. Therefore a combined
experimental and theoretical study of the correlations between
structure and reactivity of the sterically hindered organic mole-
cules e ortho-alkyl derivatives of benzenesulfonyl chloride must be
an investigation priority.
Scheme 2b). Both compounds were twice recrystallized out of
isopropanol.
Single crystals suitable for an X-ray crystal structure analysis
grew on the liquid-liquid interface of a two-phase system consist-
ing out of dry dichloromethane and octane. First the crystals of 1
(1.5 g) or 2 (1.7 g) have been dissolved in 15 mL of dichloromethane.
Next the solution was filtered and octane (20 mL) was dropwise
added to the filtrate. At this stage it is important to prevent a mixing
of two layers of dichloromethane and octane. The single crystals of
1 or 2 have crystallized out at once after evaporation of dichloro-
methane at room temperature.
2.2. X-ray crystal structure determination
Single crystals of the compounds 1 and 2 were mounted on the
The synthesis, X-ray crystal structure determination of
Xcalibur diffractometer (Mo Ka-radiation,
monochromator) equipped with a CCD detector. 180
l
¼ 0.71073 Å, graphite
two sterically hindered isomers
e 2,4-dimethyl-5-[methyl(-
u
oscillation
phenylsulfonyl)amino]-benzenesulfonyl chloride (1) and 2,4-
dimethyl-3-[methyl(phenylsulfonyl)amino]-benzenesulfonyl chlo-
ride (2) (see Scheme 1), the quantum-chemical calculations of their
molecular electronic structures as well as the kinetics of the neutral
hydrolysis studied for both isomeric forms are reported in this
article.
images with an increment of 0.5 frame width and 20 s (1), 25 s (2)
exposure per image were collected at 100.0(1) K using 60 mm
crystal-to-detector distance. After integration the data set was
corrected for Lorentz and polarization effects [27]. Cell parameters
were obtained by a least-squares refinement based on reflection
angles in the range 6.5 < 2q
< 59.1ꢀ. Structures were solved by
direct methods applying SHELX software package [28]. All atoms
were located from difference Fourier synthesis and refined by
least-squares method in the full-matrix anisotropic (non-hydrogen
atoms) and isotropic (hydrogen atoms) approximation. Finally,
Uiso(H) values were in the range of 1.5e2.5Ueq(C). The crystallo-
graphic data for the compounds 1 and 2 as well as details of X-ray
experiment are listed in Table 1. The bond lengths and bond angles
for both compounds are given in Tables S1 and S2, Supp. Info,
respectively. Structures image was prepared by using the DIA-
MOND program [29]. The molecular structures and crystal pack-
ings of both isomers are presented on Fig. 1 and Fig. 2,
respectively.
2. Experimental
2.1. Synthesis
The isomer 1 has been synthesized by three stages (Scheme 2a).
At first the N-sulfonyl-substituted amide (С6Н5eSO2N(H)
eС6Н3(СН3)2) has been prepared in an aqueous solution at tem-
perature of 70 ꢀC. The 2,4-xylidine (0.04 mol, 4.8 g) has been placed
in the flask containing benzenesulfonyl chloride (0.045 mol, 7.9 g)
and vigorously stirred. The resulting HCl was neutralized by
NaHCO3. After reprecipitation out of alkaline solution, the N-phe-
nylsulfonyl-2,4-xylidine yield has amounted to 7.4 g (72%). Then
solution of the N-phenylsulfonyl-2,4-xylidine (0.0285 mol, 7.4 g) in
5% aqueous sodium hydroxide was prepared and methyl iodide
(0.056 mol, 3.5 mL) was added at temperature of 80ꢀС. As a result
the white solid phase of С6Н5eSO2N(CH3)eС6Н3(СН3)2 has been
crystallized out; the product yield has amounted to 5.9 g (80%).
Finally, С6Н5eSO2N(CH3)eС6Н3(СН3)2 (0.02 mol, 5.5 g) was
mixed with chlorosulfonic acid at temperature of ꢁ5 ꢀC. The reac-
tion mixture was left for two days, and next 20 mL of chloroform
was added. Contents of the reactor was poured out onto ice, washed
out with water four times and dried by means of an anhydrous
calcium chloride. The white solid phase of 1 was obtained after
chloroform evaporation. The final product yield has amounted to
3.4 g (42%).
2.3. Kinetic measurements
Kinetic experiments have been performed under conditions of a
pseudo-first order with respect to the nucleophilic reactant in 70%
aqueous dioxane at temperature range 303e323 K on a Helios
Gamma ultravioletevisible spectrophotometer (298 nm for 1 and
305 nm for 2). Thermodynamic parameters of a transition state, Ea
and lgA, have been determined out of the Arrhenius equation by
means of graphical method. The following correlations were used
for calculating D DS
Hs and s [30]:
D
Hs ¼ Ea ꢁ RT;
The isomer 2 has been synthesized by the same way, as 1 (see
D
Ss ¼ 2,303R(lgA ꢁ lgT ꢁ 10,75).
Scheme 1. Graphical formulas of 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]-benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]-benzene-
sulfonyl chloride (2).

L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
3
Scheme 2. Synthesis stages of 1 (a) and 2 (b).
mechanical calculations (the restricted Hartree-Fock (RHF) method
with a 6e31G* basis set) were performed using the HyperChem
program version 8.0.6 [31]. The structures of two isomers deter-
mined by X-ray crystallography were used as starting points for
2.4. Quantum-chemical analysis
Computer simulation of the electronic structure of two molec-
ular isomers (1 and 2) has been carried out. The ab initio quantum-
Table 1
Crystal data and experimental details for the single crystal samples of 1 and 2.
Compound
1
2
Empirical formula
Formula weight
Color, shape
C15H16S2O4NCl
418.5
colorless, prism
0.70 ꢂ 0.30 ꢂ 0.30
P1
C15H16S2O4NCl
418.5
colorless, plate
0.50 ꢂ 0.40 ꢂ 0.15
P 21/c
Crystal size [mm3]
Space group
a [Å]
b [Å]
c [Å]
8.1542(2)
11.0728(3)
11.2680(3)
116.557(3)
95.155(2)
108.258(2)
831.97(4)
2, 1.492
11.7428(2)
11.3518(2)
12.5886(2)
a
b
g
[ꢀ]
[ꢀ]
[ꢀ]
93.659(2)
V [Å3]
1674.66(5)
4, 1.483
776
Z, dc [g cm¡3
F(000)
]
388
49.99
2
qmax [o]
49.99
Refl. collected/unique
Data/restraints/parameters
Rint, Rs
5296/2906
2906/0/272
0.0131, 0.0247
10089/2934
2934/0/272
0.0138, 0.0126
Final R indices [I > 2
R indices (all data)
Weighing scheme
s
(I)]
R1 ¼ 0.0251, wR2 ¼ 0.0673
R1 ¼ 0.0269, wR2 ¼ 0.0725
R1 ¼ 0.0319
R1 ¼ 0.0304
w ¼ [
s
2(F2o)þ(0.0441P)2 þ0.00P]ꢁ1
w ¼ [
s
2(F2o)þ(0.0414P)2 þ1.07P]ꢁ1
where P ¼ (F2oþ2Fc2)/3
where P ¼ (F2oþ2Fc2)/3
Goodness of fit on F2
Largest diff. peak and hole [e Å¡3
1.042
1.047
]
0.33(5) and e0.40(5)
0.38(5) and e0.35(5)

4
L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
Fig. 1. The numbered atoms of two isomers: (a) for 1 and (b) for 2. Thermal ellipsoids with 50% probability are indicated for non-hydrogen atoms.
designing molecules models. Calculations of charge density on
atoms were carried out without optimization of molecules.
Molecular-electronic simulations have been carried out under the
hypothesis that the isomeric molecules are in the vacuum as iso-
lated particles. Charges density distribution on atoms of isomers is
represented in Fig. S1, Supp. Info. The calculated total energy and
binding energy for 1 or 2 molecules in vacuum were ꢁ577535
and ꢁ41400 kJ/mol or ꢁ577121 and ꢁ40986 kJ/mol, respectively.
sulfonyl-amidic fragments, whose the O atoms participate in
hydrogen bonding of (S)O/H type, takes place [32,33].
On the other hand, the (С)Н/O(S) hydrogen bonds with
participating the eSO2Cl groups also arise in the structures of both
isomers. However, these hydrogen bonds in 2 are stronger than in 1
(the O3/H(Me) and O4/H(Ar) distances in 1 are 2.56(2) and
2.41(2) Å, in 2 are 2.27(3) and 2.36(2) Å, respectively). It is partic-
ularly remarkable that the shortening of (C)H/O(SOCl) hydrogen
bridges correlates with the weakening of S2eCl1 bond instead of
S2eO bonds which are involved into H-bonding (Table 2). It is not
difficult to see that the above-said structural parameters of
isomeric forms can exercise influence onto reactivity of the
appropriate molecules. For instance, the neutral hydrolysis of iso-
mer 2 occurs more readily than 1.
3. Results and discussion
3.1. Crystal structures description
Data obtained from X-ray diffraction analysis reveals some
remarkable features of the molecular structures of isomers 1 and 2.
Although the preferred molecular conformation in a solid phase
can differ from the one that can be in a solution, the obtained
structural information can be useful for interpretation of the kinetic
behavior of two structural isomeric derivatives of ortho-substituted
benzenesulfonyl chloride in the hydrolysis.
The presence in the molecules of both isomers of the eSO2e and
eSO2Cl polar groups provides the formation of intermolecular (S)
O/H hydrogen bonds having length 2.37(2)e2.76(2) Å. Owing to
cross-linking, the molecules
1 and 2 self-assemble, forming
framework of the crystal structures (see Fig. 2). It should be
emphasized that the Cl1 atom in 2 is also involved into the for-
mation of (S)Cl/H intermolecular hydrogen bridge (Table 3, Fig. 2)
resulting in the weakening of SeCl bond.
Three-dimensional structures of 1 and 2 are presented in Fig. 1;
selected crystallographic parameters for two isomers are summa-
rized in Table 2. Noticeable differences in bond lengths and bond
angles are observed in the CeSO2eN fragments of isomeric mole-
cules 1 and 2. So, in 2, in contrast to 1, the C11eS1eN1 bond angle
extremely differs from the ideal tetrahedral value of 109.28ꢀ; one of
two SeO bonds in 2 is significantly lengthened (S1eO1 distances in
1 and 2 are 1.431(1) and 1.529(1) Å, respectively). This fact can be
explained by the participation of the O1 atom of both isomeric
molecules in the intramolecular hydrogen bridges but with
different H-bond strength (Table 3). It also influences onto the
conformational parameters of the isomers (torsion angles of
C11eS1eN1eC25 and C11eS1eN1eC01 in 1 or 2 are 92.2(1)
and ꢁ60.6(1)ꢀ or 106.6(1) and ꢁ81.3(1)ꢀ, respectively). There is a
need to emphasize once again that the greater lengthening of
S1eO1 bond in 2 compared to 1 is apparently caused by the for-
mation of the intramolecular hydrogen bonds that have different
strength. Apparently the relevant redistribution of electron density
between two SeO bonds within the sulfonate groups of the
3.2. Stereo-chemical aspect of the neutral hydrolysis process
The crystal chemical analysis of 1 and 2 has revealed that crystal
packing of both isomers is provided by non-valent cross-linking
(SeO/H hydrogen bridges) of the appropriate molecules with each
other. It specifies the mutual orientation of the separate fragments
in the appropriate molecules. As can be seen from Fig.1 and Table 3,
the certain orientation of the separate fragments of the bulky
molecules also results in formation of intramolecular hydrogen
bonds. These intramolecular hydrogen bonds in 2 more strongly
fasten the eSO2Cl group and, thus, prevent its free rotation around
the S2eC21 bond. Therefore the molecule 2 is more rigid than of 1.
It facilitates a frontal nucleophilic attack and generates a non-
classical transition state of SN2 type. That is why the molecules of
isomer 2 react more readily with water than isomer 1. The stepwise
conversion of isomer 2 during the neutral hydrolysis as well as the

L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
5
Fig. 2. Crystal packing of the molecules 1 (a) and 2 (b). Hydrogen bonds are depicted by dot lines.

6
L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
Table 2
C21eS2eCl1 bond angle is larger than those in 1. Within a distorted
Selected bond lengths (Å) and bond angles (ꢀ) in 1 and 2.
eSO2Cl group of molecule 2 (O3eS2eO4 bond angle is 122.93(8)ꢀ
instead of 109.28ꢀ), a further lengthening of the S2eCl1 bond is
followed by decrease of the absolute value of activation entropy,
Bonds
1
2
Angles
1
2
S1eO1
S1eO2
S1eN1
S1eC11
S2eO4
S2eO3
S2eC21
S2eCl1
1.431(1)
1.435(1)
1.638(1)
1.766(2)
1.422(1)
1.423(1)
1.759(2)
2.0392(6)
1.529(1)
1.445(1)
1.603(1)
1.685(2)
1.409(1)
1.420(1)
1.712(2)
2.1468(6)
O1eS1eO2
O1eS1eN1
O2eS1eN1
O1eS1eC11
O2eS1eC11
N1eS1eC11
O4eS2eO3
O4eS2eC21
O3eS2eC21
O4eS2eCl1
O3eS2eCl1
C21eS2eCl1
120.19(7)
106.03(7)
107.46(7)
108.25(7)
107.00(8)
107.30(7)
119.56(8)
109.49(8)
111.71(7)
105.87(7)
105.56(6)
103.09(6)
121.05(7)
110.92(7)
105.73(7)
109.31(8)
106.02(8)
102.09(8)
122.93(8)
108.54(8)
106.70(8)
102.37(6)
107.53(6)
108.03(6)
j
D
Ssj. It facilitates frontal nucleophilic attack and makes the hy-
drolysis process by more favorable.
Thus, a shortening of the intramolecular (S)O/H bonds, pa-
rameters of which in many respects are specified by stereochem-
istry of the isomers, causes a certain deficiency of electron density
on donor atoms of oxygen. It can be explained by “partial overlap”
of atomic orbital, occupied by lone electron pair, of the more
electronegative atom (oxygen) with unoccupied atomic orbital of
the more electropositive atom (hydrogen). The structural parame-
ters of the intramolecular (S)O/H bonds in 1 and 2 are in good
agreement with the calculated energies of the frontier MOs (Fig. 4).
In particular, the HOMO level in 2 (ꢁ8.368 eV) is more stabilized
compared to that in 1 (ꢁ8.089 eV).
stereochemistry of the transition state is represented in
Scheme 3 [34].
On the other hand, the H/H contacts springing up between
methyl groups and phenyl moieties are also very important for the
additional stabilization of molecular conformations upon crystal-
lizing of isomers [35,36]. So, in 1 (Fig. 3a) the H022/H231 and
H033/H231 distances are 2.39(4) and 2.25(5) Å, respectively,
while in 2 (Fig. 3b) the similar H022/H231 contact is 2.32(3) Å.
Nevertheless these intramolecular contacts in both isomers are
more lengthened than averaged values of analogous H/H dis-
tances (~2.12e2.15 Å) used in R. Bader's theory “Atoms in Mole-
cules” [37] as criterion of influence on conformations stabilization.
Thus, the correlation between charge density values (obtained
from quantum-chemical calculations) and length of H/O distances
of the intramolecular hydrogen bond (obtained from X-ray crystal
structures analyses) is the most objective evaluation parameter.
It should be interesting to consider the influence of strength of
the intramolecular hydrogen bonds onto the reactivity of two
structural isomers 1 and 2. So, the quantum-chemical calculations
performed for both isomers have revealed that the value of a charge
density (d) on oxygen atoms of the sulfonylchloride group depends
on rigidity of the eSO2Cl group fastening by intramolecular
hydrogen bonds (Table 3). As can be seen from Fig. 3, in 2 the
d
values on the oxygen atoms participating in formation of the
more strong H-bonds (distances O3/H033 and O4/H221 are
2.27(3) and 2.36(2) Å, respectively) are equal ꢁ0,514 (on the O3)
and ꢁ0.518 (on the O4) e. On the other hand, in 1 the
d values on
the same O atoms involved into formation of the less strong H-
bonds (distances O3/H032 and O4/H261 are 2.56(2) and 2.41(2)
Å, respectively) increase to ꢁ0,529 (on the O3) and ꢁ0.524 (on the
O4) e.
The values of dH/O and
d have an inversely proportional depen-
dence: a shortening of dH/O is accompanied by an increase in
Such redistribution of electronic density among atoms of the
isomers entails specific changes of the geometrical parameters in
the molecules 1 and 2. So, the S2eCl1 bond in 2 compared to 1 is
weaker (Table 2). In 2 the S2eC21 bond length (1.712(2) Å) is
shorter than in 1. The bonds lengths of S2eO3 (1.420(1) Å) and
S2eO4 (1.409(1) Å) in 2 somewhat differ between themselves. In 2
the bond angles of C21eS2eO3 and O4eS2eCl1 are lesser and
d
(Fig. 5).
The reactivity differences observed between two structural
isomers,1 and 2, in aqueous solution cannot be explained only from
the activation enthalpy values, though the increase in reactivity of
2, as opposed to 1, is accompanied by the increase in
D
Hs value
(Table 4). However, such behavior is an untypical for the majority of
organic reactions [18,19]. In contrast to it, the absolute value of
Table 3
Hydrogen bonds parameters (Å and ꢀ) in 1 and 2.
H-bondsa
DeH
H/A
D/A
DeH/A
1
C01eH011/O2
C12eH121/O2
C03eH032/O2i
C02eH021/O1
C23eH231/O4ii
C26eH261/O4
C03eH032/O3
C12eH121/O3iii
2
1.02(7)
0.91(5)
0.93(3)
1.00(3)
0.97(3)
0.97(3)
0.93(3)
0.91(5)
2.53(2)
2.55(2)
2.76(2)
2.64(2)
2.34(2)
2.41(2)
2.56(2)
2.67(2)
3.008(9)
2.903(3)
3.388(3)
3.191(7)
3.338(3)
2.843(4)
3.091(4)
3.403(4)
106(3)
104(3)
125(1)
116(3)
171(3)
106(2)
116(4)
141(4)
C03eH032/O1
C16eH161/O1
C01eH011/O1iv
C16eH161/O2v
C12eH121/O2
C12eH121/O2vi
C03eH033/O3
C23eH231/O3vii
C22eH221/O4
C13eH131/O4viii
C14eH141/Cl1viii
0.98(2)
0.94(2)
0.93(2)
0.94(2)
0.94(2)
0.94(2)
0.85(4)
0.95(2)
0.92(2)
0.98(2)
0.87(2)
2.68(2)
2.50(2)
2.63(2)
2.48(2)
2.63(2)
2.51(2)
2.27(3)
2.75(2)
2.36(2)
2.75(2)
2.83(2)
3.076(2)
2.826(3)
3.246(3)
3.126(2)
2.878(3)
3.359(2)
2.895(2)
3.300(2)
2.750(2)
3.395(3)
3.460(2)
104(2)
100(2)
124(2)
126(2)
96(2)
151(2)
131(3)
117(2)
106(2)
124(2)
130(2)
a
Symmetry codes: (i) x, y, ꢁ1þz; (ii) 1 þ x, y, z; (iii) x, y, 1 þ z; (iv) x, 0.5ey, 0.5 þ z;
(v) ex, 0.5 þ y, 0.5ez; (vi) ex, ey, ez; (vii) 1ex, 0.5 þ y, 0.5ez; (viii) e1 þ x, 0.5ey,
0.5 þ z.
Scheme 3. Stereochemistry of the neutral hydrolysis reaction of the 2,4-dimethyl-3-
[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2).

L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
7
Fig. 3. Charge density (
d
, e) distribution on the atoms of the eSO2Cl and eSO2e groups in the molecule 1 (a) and 2 (b).
activation entropy, j
D
Ssj, is lower for 2 than for 1. Thus, there are
molecular isomers 1 and 2 has provided by reliable information on
the stereochemistry of the initial and transitional states of these
molecules in aqueous solution. For the reasons given above, these
two structural isomers show the different reactivity in the hydro-
lysis process.
losses of activation enthalpy for 2 in comparison with 1, since after
formation of the activated complex, steric parameters of the tran-
sition state any more cannot be a rate-determining factor of the
hydrolysis reaction. Greater rate of the neutral hydrolysis observed
for 2 can be explained by the elimination of steric hindrances for
the potential nucleophilic attack in the initial state of 2 and by the
formation of the less ordered transition state [38].
4. Conclusions
Thus, the study of the crystal and electronic structure of two
Thus, two new structural isomers of ortho-alkyl derivatives of
benzenesulfonyl chloride have been synthesized. Both obtained
isomeric forms e 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]-
Fig. 5. Plot of dH/O versus
d
for both isomeric forms (r ¼ 0.97).
Table 4
The effective rate constants and thermodynamic data for reactions of the neutral
hydrolysis of 1 and 2.
Isomer
keff 104, sꢁ1
D
Hs
,
e
D
Ss, J
molꢁ1 Kꢁ1
D
Gs313
kJ molꢁ1
,
kJ molꢁ1
303 K
313 K
323 K
1
2
0.603
0.686
1.16
1.49
2.17
3.79
49.5 0.5
66.8 4.9
186
131 15
2
108
108
1
8
Fig. 4. Calculated frontier MO energies of 1 (a) and 2 (b).

8
L. Rublova et al. / Journal of Molecular Structure 1137 (2017) 1e8
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benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenyl-
sulfonyl)amino]-benzenesulfonyl chloride (2) e are organized as
molecular crystals. The crystal chemical analysis of isomers 1 and 2
has revealed that polar groups (eSO2Cl and eSO2e) in the sterically
hindered molecules generate the intramolecular hydrogen bonds of
a (C)H/O(S) type. Both structures are stabilized by the branched
system of intermolecular hydrogen bridges of the (C)H/O and (C)
H/Cl types.
The crystal structure data and quantum-chemical calculations
have been used for interpretation of behavior of the bulky mole-
cules 1 and 2 in aqueous solution. Unlike 1, the molecule 2 has a
more rigid structure and a more “labile” SeCl bond. It creates
favorable conditions for reaction of nucleophilic substitution on
substrate in 2 and stabilizes a bimolecular transition state. The
particular molecular structure promotes the certain reallocation of
charge density on atoms in molecule 2 and leads to a possible
frontal attack of nucleophilic agent and formation of non-classical
transition state of SN2 type. It is reverberated on values of ther-
modynamic parameters of the transition state and the hyperreac-
tivity of the isomer 2.
Appendix A. Supplementary data
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