Molecule 1,5-C10H6(SO2Cl)2 as prototype of conformational properties of naphthalene sulfonyl derivatives

Article abstract of DOI:10.1016/j.molstruc.2016.07.083

Conformational composition of the vapor (T?=?413(5)?K) and the conformer structures of 1,5-naphthalenedisulfonylchloride (1,5-NaphDSC) have been studied by a combined gas-phase electron diffraction and mass spectrometry (GED/MS) method complemented by quantum chemical calculations. According to quantum chemical calculations at DFT/B3LYP/cc-pVTZ and MP2/cc-pVTZ theory levels, the molecule 1,5-NaphDSC possesses four conformers differing mutual orientation of the two SO₂Cl groups. GED data clearly indicate that only two conformers, whose structures are characterized by deviation of two S[sbnd]Cl bonds from perpendicular position relative to the plane of the naphthalene skeleton (syn-symmetry C₂ and anti-symmetry C_i), are present in vapor at 413?K. The following geometrical parameters of these conformers were obtained from the experiment (? and degrees; uncertainties are in parentheses): r_h1(C[sbnd]H)?=?1.098(9), r_h1(C[sbnd]C)?=?1.405(3), r_h1(C[sbnd]S)?=?1.781(4), r_h1(S[sbnd]O)?=?1.426(3), r_h1(S[sbnd]Cl)?=?2.056(4), ∠C[sbnd]C_S[sbnd]C?=?122.9(1), ∠C_S[sbnd]S[sbnd]Cl?=?101.8(6); C9[sbnd]C1[sbnd]S[sbnd]Cl?=?71.2(12), C10[sbnd]C5[sbnd]S[sbnd]Cl?=?71.2(12)-syn conformer; C9[sbnd]C1[sbnd]S[sbnd]Cl?=?71.2(12), C10[sbnd]C5[sbnd]S[sbnd]Cl?=??71.2(12) -anti-conformer. The presence of C₉H_n⁺ ions in the mass spectra of naphthalenesulfonyl chlorides, which are absent in the mass spectrum of naphthalene, may be attributed to the weakening of two C[sbnd]C bonds adjacent to the substituent of the naphthalene skeleton. This reflects in the geometric parameters of 1,5-NaphDSC. The barriers to internal rotation of sulfonyl chloride groups were calculated. It is shown that the low-energy syn- and anti-conformers are structurally rigid, in contrast to high-energy conformers with one or two S[sbnd]Cl bonds, lying in the plane of the naphthalene skeleton. The dependence of C1[sbnd]C2, C[sbnd]S, S[sbnd]Cl bond lengths from SO₂Cl groups orientation relative to naphthalene skeleton is discussed in terms of NBO-analysis of electron density distribution. The relationship between conformational properties of molecule and some physicochemical characteristics of the 1,5-NaphDSC compound is discussed.

Full text of DOI:10.1016/j.molstruc.2016.07.083

Accepted Manuscript
Molecule 1,5-C H (SO Cl) as prototype of conformational properties of
0 6
1
2
2
naphthalene sulfonyl derivatives
Vjacheslav M. Petrov, Nina I. Giricheva, Sergey N. Ivanov, Valentina N. Petrova,
Georgiy V. Girichev
PII:
S0022-2860(16)30767-0
10.1016/j.molstruc.2016.07.083
MOLSTR 22786
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 3 June 2016
Revised Date: 15 July 2016
Accepted Date: 18 July 2016
Please cite this article as: V.M. Petrov, N.I. Giricheva, S.N. Ivanov, V.N. Petrova, G.V. Girichev,
Molecule 1,5-C H (SO Cl) as prototype of conformational properties of naphthalene sulfonyl
0 6
1
2
2
derivatives, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.07.083.
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ACCEPTED MANUSCRIPT
Molecule 1,5-C H (SO Cl) as Prototype of Conformational Properties
1
0
6
2
2
of Naphthalene Sulfonyl Derivatives
#
#*
#
§
Vjacheslav M. Petrov, Nina I. Giricheva, Sergey N. Ivanov , Valentina N. Petrova ,
Georgiy V. Girichev
§
#
Ivanovo State University, Ivanovo 153460, Russia; e-mail: n.i.giricheva@mail.ru
Ivanovo State University of Chemistry and Technology, Ivanovo 153460, Russia;
§
e-mail: girichev@isuct.ru
Conformational composition of the vapor (T=413(5) K) and the conformer
structures of 1,5-naphthalenedisulfonylchloride (1,5-NaphDSC) have been studied
by a combined gas-phase electron diffraction and mass spectrometry (GED/MS)
method complemented by quantum chemical calculations. According to quantum
chemical calculations at DFT/B3LYP/cc-pVTZ and MP2/cc-pVTZ theory levels,
the molecule 1,5-NaphDSC possesses four conformers differing mutual orientation
of the two SO Cl groups.
2
GED data clearly indicate that only two conformers, whose structures are
characterized by deviation of two S-Cl bonds from perpendicular position relative
to the plane of the naphthalene skeleton (syn-symmetry C and anti-symmetry C ),
2
i
are present in vapor at 413 K.
The following geometrical parameters of these conformers were obtained
from the experiment (Å and degrees; uncertainties are in parentheses): r (C-H) =
h1
1
.098(9), rh1(C-C)=1.405(3), rh1(C-S)=1.781(4), rh1(S-O)=1.426(3), r (S-
h1
Cl)=2.056(4), ∠ C-C -C = 122.9(1), ∠ C -S-Cl = 101.8(6); C9-C1-S-Cl =71.2(12),
S
S
C10-C5-S-Cl =71.2(12)-syn conformer; C9-C1-S-Cl =71.2(12), C10-C5-S-Cl=-
1.2(12) -anti-conformer.
7
+
The presence of C H ions in the mass spectra of naphthalenesulfonyl chlo-
9
n
rides, which are absent in the mass spectrum of naphthalene, may be attributed to
the weakening of two C–C bonds adjacent to the substituent of the naphthalene
skeleton. This reflects in the geometric parameters of 1,5-NaphDSC.
The barriers to internal rotation of sulfonyl chloride groups were calculated. It
is shown that the low-energy syn- and anti-conformers are structurally rigid, in con-
trast to high-energy conformers with one or two S-Cl bonds, lying in the plane of
the naphthalene skeleton.
The dependence of C1-C2, C-S, S-Cl bond lengths from SO Cl groups orien-
2
tation relative to naphthalene skeleton is discussed in terms of NBO-analysis of
electron density distribution.
The relationship between conformational properties of molecule and some
physicochemical characteristics of the 1,5-NaphDSC compound is discussed.
1

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Keywords: 1,5-naphthalenedisulfonylchloride, molecular structure, gas-phase electron
diffraction, mass spectrometry, quantum chemical calculations, conformational properties,
transition barriers
Introduction
The conformational properties of monosubstituted naphthalene molecules such as: 1-
naphthalenesulfonyl chloride (1-NaphSCl), 2-naphthalenesulfonyl chloride (2-NaphSCl) [2],
1- and 2-naphthalene sulfonyl amides [3] and 2-naphthalenesulfonyl fluoride [2] were
determined by GED and quantum chemical methods. It was shown that 1- and 2-
monosubstituted naphthalenes (1-NaphSO X and 2-NaphSO X (X=F, Cl, NH )) demonstrate
2
2
2
the different conformational properties and have a different number of conformers. The
molecule 1-NaphSCl has two conformers, and 2-NaphSCl - only one. It should be pointed out
that the S–X bond deviation from orthogonal position relative to the naphthalene frame by
about 20° is characteristic for the most stable conformer in 1- and 2-monosubstituted
naphthalenes. In contrast, SO X substituent in benzene moiety is characterized by the exactly
2
orthogonal position of the S−X bond with respect to the ring [4-6].
The correlation between nonequivalence of the C–C bonds in the naphthalene frame
and spatial orientation of the SO NH substituents in 1-NaphSO NH and 2-NaphSO NH was
2
2
2
2
2
2
discussed in Ref. 3. It was shown that the S–N bond deviates in different directions from the
short C1–C2 bond of the naphthalene frame depending on 1- or 2-position of the substituent in
these molecules.
The structure of 1,5-disubstituted naphthalene 1,5-Naph(SO X) in a gas phase has
2
2
not been studied yet, although such investigations can not only disclose the conformational
properties of the gaseous compound, but predict conformations that may be implemented in
crystals [e.g., 7-12]. In crystals of different compounds the SO X group can possess a different
2
spatial location relative to the plane of the naphthalene frame, as well as the different relative
orientation with respect to other substituents.
Detailed knowledge about the conformation properties of 1,5-naphthalenedisulfonyl
derivatives is important because these compounds are used as crosslinking agents in the syn-
thesis of macromolecular compounds - polysulfones, polysulfonamides and are the base for a
2

ACCEPTED MANUSCRIPT
synthesis of highly thermostable polymers and adhesives [13,14], polymer membranes [15,16]
,
fluorescent probes [17] etc.
The 1,5-naphthalenedisulfonylchloride (1,5-NaphDSC) is used for synthesis of many
other 1,5-naphthalenedisulfonyl derivatives, and the knowledge of conformational properties
of this compound seems to be important for understanding the reaction mechanisms. In this
connection it is interesting to see the relationship between conformational properties of mole-
cule and some physicochemical characteristics. So the conformational features of the 1,5-
NaphDSC can be related to the kinetics of hydrolysis of this compound in aqueous i-PrOH
mixtures [18] manifested by sharply nonmonotonic dependence of the activation parameters
on solvent composition. Two sharp minima of activation enthalpy are detected at 0.014 and
0
.018 m.f. i-PrOH, what the authors [18] attribute to the selective hydration of two 1,5-
NaphDSC conformers.
The 1.5-NaphDSC is a suitable object for electron diffraction study. The scattering
ability of chlorine atoms of this compound is high compared with that of the nitrogen or oxy-
gen atoms in 1,5-Naph (SO X) (X = NH , OH), and this makes the reliability to determine the
2
2
2
spatial locations of two SO X groups relative to the naphthalene frame in the case of 1,5-
2
NaphDSC also significantly higher.
The present work reports the structural and electronic characteristics of the 1,5-
NaphDSC conformers and its correlation with molecular structures of monosubstituted 1-
NaphSC studied previously [1].
Experimental
1,5-NaphDSC was synthesized by reaction of 1.5-naphthalenedisulfonic acid (1,5-
NaphDSAc) with a threefold molar excess of PCl . The product was recrystallized from a hex-
5
ane/propan-2-ol mixture (80/20 vol.%) to obtain a sample melting point 183 °C (mp. = 183 ° C
[
19,20]).
The diffraction patterns were recorded using a combined EMR-100/APDM-1 appa-
ratus, which allows carrying out synchronous gas electron diffraction and mass spectrometric
GED/MS) experiments [21]. The sample was evaporated from a stainless steel (X18H10T)
(
effusion cell with the ratio of the cross sectional area of the internal cylindrical part to the area
of the effusion hole equals to 150. A temperature of the effusion cell was measured by a
3

ACCEPTED MANUSCRIPT
W/Re-5/20 tungsten-rhenium thermocouple. Accurate wavelengths of electrons were deter-
mined from the diffraction patterns of the polycrystalline ZnO recorded before and after pat-
terns of the sample. Main conditions of the GED/MS experiment are listed in the Table 1.
Table 1.
Conditions of the synchronous GED/MS experiments.
nozzle-to-plate distance, mm
electron beam current, ꢀA
temperature of effusion cell, K
accelerating voltage, kV
ionization voltage, V
338
1.4
598
1.0
413(5)
88.3
50
412(5)
89.0
50
exposure time, s
100
45
-
6
-6
residual gas pressure, Torr
scattering angles, Å-1
1.4⋅10
2.0·10
2.5-30.0
1.3-17.1
The optical densities of the diffraction patterns were measured by a computer-
controlled MD-100 (Carl Zeiss, Jena) microdensitometer [22]. Molecular scattering intensity
I(s) −G(s)
were calculated as sM (s) =
⋅s , where I(s) is a total experimental scattering intensi-
G(s)
ty function and G(s) is a background function.
Table 2 lists mass-spectra of 1,5-NaphDSC recorded simultaneously with electron
diffraction patterns. All of the observed ions originate from a single molecular form (C H -
1
0
6
(
SO
spectra.
Table 2.
2
Cl)
2
). Neither thermal destruction nor volatile admixtures were detected in the mass-
Ions relative abundance in mass spectrum of saturated vapor over 1,5-NaphDSC (Uioniz=50V)
recorded simultaneously with the diffraction pattern, and mass spectra of 1-NaphSC and naph-
thalene С Н for comparison.
1
0
8
ion
m/e,
а.е.м.
1,5-NaphDSC
1-NaphSC
[1] [23]
С Н
10 8
our data
14
[23]
3
7
+
C H (SO Cl)
328
326
1
0
6
2
2
3
5
37
C H S O Cl Cl
58
1
0
6
2
4
4

ACCEPTED MANUSCRIPT
3
5
+
C H (SO Cl)
2
324
291
289
228
226
191
175
164
162
149
146
143
134
128
127
126
115
72
37
92
1
0
6
2
3
7
+
C H S O Cl
1
0
6
2
4
3
5
+
C H S O Cl
1
0
6
2
4
3
7
+
a
C H SO Cl
41
98
24
48
29
-
11.0
29.2
16.7
3.9
1
0
7
2
3
5
+
a
C H SO Cl
1
0
7
2
+
C H SO
C H SO
1
0
7
2
+
1
0
7
3
7
+
a
a
C H Cl
31
76
18
42
10.4
32.1
1
0
7
3
5
+
C H Cl
1
0
7
3
5
+
C H Cl
30
18
9
6
+
C H S
9
6
+
C H O
8.8
3.9
1
0
7
+
C H S
32
8
3
6
1
12
+
a
b
C C H
19
11
100
30
10
12
-
25.0
100
13.6
6.3
6.3
2.1
11
1
9
7
+
a
b
C H ,
100
100
1
0
7
+
a
b
C H
20
20
10.8
-
8.2
-
1
0
6
+
+
+
+
+
a
C H
9
7
n
3
n
n
c
C H
100-103
87 c
74-77 c
63-65
23
15
32
25
8
C H
7
C H
22
15
10.2
10.8
3.4
6.8
6
C H
5
a
Ion contains the number of hydrogen atoms smaller by one (and one a.m.u.) than that written
in the formula.
Ion contains the number of hydrogen atoms bigger by one (and one a.m.u.) than that written
b
in the formula.
c
Group of ions with different number of hydrogen atoms; intensity of ion involved in group is
given.
Quantum chemical calculations
Quantum chemical (QC) calculations were performed using Gaussian 03 program
package [24]. DFT/B3LYP [25] and MP2 [26,27] methods with cc-pVTZ [28-29] basis sets
were chosen. Geometry optimization and calculation of the frequencies were performed for all
the stationary points on the PES of 1,5-NaphDSC.
By analogy with the 1-NaphSC, which has two conformers, ‘skewed’ (C9-C1-S-Cl) =
71.4(21)° ) and ‘planar’, in which the S–Cl bond lies in the plane of the naphthalene frame[1],
we supposed the molecule 1,5-NaphDSC has four conformers differing mutual orientation of
two groups SO Cl: 'skewed-skewed-syn' – conformer I, 'skewed-skewed-anti' - conformer II,
2
'skewed-planar' - conformer III, and 'planar- planar' - conformer IV (Fig. 1). QC calculations at
MP2/cc-pVTZ and DFT/B3LYP/cc-pVTZ theory levels show that all of these conformers cor-
5

ACCEPTED MANUSCRIPT
respond to a minima on the PES.
Fig. 1 The 1,5-NaphDSC conformers: 'skewed-skewed-syn' – conformer I, 'skewed-skewed-
anti' - conformer II, 'skewed-planar' - conformer III and 'planar-planar' - conformer IV.
Relative total energies ∆E, relative Gibbs free energies ∆G° for conformers of 1,5-
T
NaphDSC along with the relative conformer ratios χ in a gas phase at the temperature of GED
experiment are summarized in Table 3.
Table 3.
Calculated (B3LYP/cc-pVTZ) relative total energies ∆E, relative Gibbs free energies ∆G° of
T
conformers of 1,5-NaphDSC molecule and the conformer ratio χ in gas phase at T=413 K.
conformer I
skewed-
skewed-syn'
conformer II
'skewed-skewed- 'skewed-planar'
anti'
conformer III
conformer IV
'planar-planar'
'
a
∆
E , kcal/mol
0.02
0
32.4
49.8
0.0
3.73
3.22
25.4
1.0
7.44
6.57
25.2
0.02
°
4
∆G
, kcal/mol
13
0.01
33.5
49.2
b
-1
ν , cm
χ, mol %
1
a
relative total energies ∆E calculated by MP2/cc-pVTZ are 0, 0.01, 4.09 and 8.17 kcal/mol
for I, II, III and IV conformers, correspondently
b
lowest frequency
The nature of stabilization of the certain geometry configurations of 1,5-NaphDSC was
interpreted in terms of the NBO-analysis [30]. Chemcraft program [31] was used for the visu-
alization of the molecular structures and orbitals.
6

ACCEPTED MANUSCRIPT
Structural analysis
According to mass-spectra, the saturated vapor of 1,5-NaphDSC at the temperature of
GED/MS experiment contains the single molecular form C H (SO Cl) .
1
0
6
2
2
Geometry configuration of this molecule was described by 12 independent parameters
accounting for the nonequivalence of the bond lengths C-C in the naphthalene skeleton, the
deviation of bonds C1-S from bisection of corresponding bond angles C9-C1-C2, the out-of-
plane movement of S atom and the internal rotation of the sulfonyl chloride groups around the
bonds C1-S (Fig. 1). The set of independent parameters included: five bond lengths C2-H, C1-
C2, C1-S, S-O1, S-Cl, five bond angles C9-C1-C2, C9-C1-S, C1-S-Cl, C1-S-O1, O1-S-Cl,
dihedral angle C10-C9-C1-S describing the movement of the sulfur atom out of the naphtha-
lene plane and two φ1(C9-C1-S-Cl) and φ2(C10-C5-S-Cl) torsion angles taking into account
the rotation of the two SO Cl groups whose initial values depend on the conformers symmetry.
2
All bond lengths C-H in the naphthalene fragment were assumed to be equal and to bisect cor-
responding bond angles C-C-C. The differences ∆r(C-C) arising due to nonequivalence of the
bond lengths C-C were taken from the QC calculations at B3LYP/cc-pVTZ level of theory and
were not included in variation during the least-squares procedure. The same adoption was
made for the C-C-C bond angles.
The geometry of the molecule was investigated in terms of r -structure. Vibrational
h1
corrections (∆r = r – r ) were calculated using program Shrink [32] assuming curvilinear rela-
a
h1
tions between Cartesian and internal coordinates. The force field used in this calculation was
obtained from B3LYP/cc-pVTZ calculations. The vibrational amplitudes for the terms pos-
sessing the close internuclear distances were refined in groups corresponding to the peaks on
the radial distribution curve f(r) (Fig. 2). Structural analysis was performed utilizing modified
KCED-35 program which is similar to the algorithm described in [33].
Two correlation coefficients happened to possess magnitude larger than 0.7: p /p = -0.80,
2
5
p /p = -0.73 (p in Table 4).
6
7
i
Experimental structural parameters of 1,5-NaphDSC corresponding to the theoretical
sM(s) curve which is in the best agreement with experimental data are listed in Table 4. Exper-
imental and theoretical scattering intensity curves are given in the Fig. 3.
7

ACCEPTED MANUSCRIPT
Table 4.
Experimental (GED) and calculated (B3LYP/cc-pVTZ)/(MP2/cc-pVTZ) structural parameters of 1,5-NaphDSC conformers
distances in Å, angles in deg.) in comparison with parameters of monosubstituted 1−NaphSC.
(
1
,5-NaphDSC
conformer II
1−NaphSC
conformer
'skewed'
conformer I
conformer III
'skewed-planar'
QC
'skewed- skewed-syn'
'skewed-skewed-anti'
a
QC
re structure
[1]
a
a
GED ,
GED
QC
GED
rh1 structure
QC
re structure
Parameters
rh1 structure
rh1 structure
re structure
re structure
skewed
SO Cl group
planar
2
[
1]
SO Cl group
2
b
а
b
а
b
1
C-H
1.098(9) p
1.079/1.080
1.371/1.379
1.404/1.403
1.368/1.377
1.417/1.415
1.426/1.422
1.435/1.439
1.401/1.403
1.797/1.772
2.114/2.072
1.444/1.441
122.5/122.7
122.6/122.0
101.2/99.8
110.2/110.1
106.2/106.5
72.7/70.3
1.098(9) p
1.081/1.080
1.371/1.379
1.404/1.403
1.368/1.377
1.417/1.415
1.427/1.422
1.435/1.438
1.401/1.403
1.797/1.772
2.114/2.072
1.444/1.441
122.5/122.7
122.6/122.0
101.2/ 99.8
110.2/110.1
106.2/106.5
72.7/70.3
1.079/1.080
1.371/1.378
1.404/1.403
1.368/1.376
1.418/1.416
1.427/1.422
1.079/1.080
1.366/1.378
1.406/1.403
1.367/1.376
1.417/1.416
1.429/1.422
1.082(6) p1
1.380(3)p2
1.081/1.081
1.373/1.380
1.406/1.406
1.368/1.376
1.415/1.414
1.427/1.422
1.432/1.434
1.400/1.402
1.791/1.769
2.121/2.077
1.444/1.441
122.6/122.9
122.3/121.8
101.4/99.8
110.5/110.3
105.9/106.2
73.0/70.4
1
c
C1-C2, (C5-C6)
C2-C3, (C6-C7)
C3-C4, (C7-C8)
1.376(3) p2
1.376(3) p2
c
c
1.408(3) (p2)
1.373(3) (p2)
1.422(3) (p2)
1.431(3) (p2)
1.440(3) (p2)
1.405(3)
1.408(3) (p2)
1.373(3) (p2)
1.422(3) (p2)
1.431(3) (p2)
1.440(3) (p2)
1.405(3)
1.413(3) (p2)
1.375(3) (p2)
1.422(3) (p2)
1.434(3) ( p2)
1.439(3) (p2)
1.407(3)
c
c
C4-C10, (C8-C9)
C1-C9, (C5-C10)
C9-C10
1.435/1.438
1.401/1.403
1.797/1.772
b
(
C-C)
C-S
1.781(4) p3
2.056(4) p4
1.426(3) p5
122.9(1) p6
122.7(3) p7
101.8(6) p8
109.3(4) p9
106.2(2) p10
71.2(12) p11
71.2(12)
1.781(4) p3
2.056(4) p4
1.426(3) p5
122.9(1) p6
122.7(3) p7
101.8(6) p8
109.3(4) p9
106.2(2) p10
71.2(12) p11
288.8(12)
1.810/1.782
2.111/2.068
1.444/1.442
122.2/122.2
116.6/115.8
104.2/103.1
109.3/109.1
106.2/106.4
1.764(5) p3
2.051(5) p4
1.425(3) p5
S-Cl
S=O
2.114/2.072
1.444/1.441
122.6/122.7
122.5/122.8
101.2/99.8
110.2/110.1
106.2/106.5
72.9/70.3
b
c
а
C9-C1-C2, (C10-C5-C6)
122.5(1) p6
c
C9-C1-S, (C10-C5-S)
122.1(5) p7
101.5(10) p8
110.2(7) p9
106.4(3) p10
71.4(21) p11
C1-S-Cl, (C5-S-Cl)
b
C-S-O
b
O-S-Cl
φ1(C9-C1-S-Cl)
φ2(C10-C5-S-Cl)
72.7/ 70.3
287.3/289.7
179.3/179.4
180/180
φ(C10-C9-C1-S),
178.0(32) p12
179.1/179.1
178.0(32) p12
179.0/179.3
179.6/180
179.3(55) p12
179.2/179.2
8
c
(
φ(C9-C10-C5-S))

ACCEPTED MANUSCRIPT
5
1.4(49) p13
50.3
48.6(49) p13
3.34
49.7
0
0
100
-
conformer ratio χ,
mol %
R , %, GED
f
3.68
a
2
2 1/2
Total error limit in interatomic distances was estimated as σ=[(2.5σ ) + (0.002r) ] ; total error in angles and in mole fraction was
LS
taken to be equal 3σ (all in the units of last significant digit).
LS
b
Average values.
c
Parameter in 'skewed-planar' conformer III.
9

ACCEPTED MANUSCRIPT
Results and discussion
Fragmentation of 1,5-NaphDSC by electron ionization
In Table 2 the mass spectra of disubstituted 1,5-NaphDSC, monosubstituted 1-
NaphSC and naphthalene molecules are compared. The distinctive feature of the mass-
spectrum of 1,5-NaphDSC containing two sulfonyl chloride groups as compared to the mass-
spectrum of 1-NaphSC appears in the increasing of the relative intensities of the ions occurring
due to elimination of the atoms (groups of atoms) of substituents. The ions with a lack of chlo-
rine atom of one sulfonyl chloride group as well as ions with a lack of whole sulfonyl chloride
group are the most probable to form. One more feature of the mass spectrum of 1,5-NaphDSC
+
+
+
is the presence of C H Cl , C H S , and C H S ions. The formation of the first of them is
9
6
9
6
8
6
+
+
similar to the appearance of C H and C H Cl ions in the mass spectrum of monosubstituted
9
7
10
7
sulfonyl chloride and related to the detachment of the C–SO Cl moiety belonging to one of
2
+
substituents and the elimination of the SO group of the second substituent. Possibly C H Cl
2
9
6
ion consists of two cyclic fragments: five- and six-membered (with the Cl atom as a substitu-
+
ent). The C H S ion seems to consist of two cyclic six-membered fragments, one of which
9
6
+
involves a sulfur atom, and the C H S ion consists of the same six-membered fragment and
8
6
the five-membered one remaining after the loss of the C–SO Cl group by the second substitu-
2
ent
.
The common feature of the mass-spectra of mono- and disubstituted naphthalene sul-
fonyl chlorides is the predominance of the ions forming by loss or destruction of the substitu-
ents over those, which are formed by destruction of the naphthalene fragment. Besides, one
+
can find signals corresponding to the ions C H in the spectra of naphthalenesulfonylhalides
9
n
while they are absent or have very low intensity in the spectrum of naphthalene. It may be
connected with weakening of the bonds C-C adjacent to a substituent that appears in the elon-
gation of these bonds and decreasing of the Wiberg bond indexes [34] (Table 5) as compared
with unsubstituted naphthalene.
Table 5.
The bond lengths r(C–C) and Wiberg bond indexes Q(C–C) by scheme [34] for naphthalene,
1- NaphSC and 1,5-NaphDSC.
Molecule
r(C1-C2), Q(C1-C2) r(C1-C9), Q(C1-C9)
1
0

ACCEPTED MANUSCRIPT
Å
Å
C H
8
1.370
1.561
1.512
1.515
1.416
1.280
1.239
1.243
1
0
1
1
-C H SO Cl
1.380(3)
1.376(3)
1.434(3)
1.431(3)
1
0
7
2
.5-C H -(SO Cl)
2
1
0
6
2
Conformational composition of the 1,5-NaphDSC vapor according to GED data and QC
calculations.
According to Table 3 the calculated relative conformer ratios χ indicate that only two
conformers I and II can be present in the 1,5-NaphDSC vapor at the temperature of the GED
experiment.
This is confirmed by Figure 2 which shows the experimental function f(r) and the dif-
ference curves between the experimental and theoretical functions ꢁf (r), corresponding to
each of the conformers.
f(r)
0
0
∆
f(r)
a)
b)
c)
d)
e)
0
0
1
2
3
4
5
6
7
8
9
10
Å
Fig. 2. Experimental (dots) and theoretical (lines) radial distribution curves f(r) and their dif-
ferences ꢁf(r) for the separate conformers of 1,5-NaphDSC (b-e) and for the optimal conform-
ers ratio (a):
a) conformer I:conformer II (51.4(49)%:48.6(49)%, R =3.34%);
f
1
1

ACCEPTED MANUSCRIPT
b) 'skewed- skewed-syn' – conformer I, R =3.85%;
f
c) 'skewed- skewed-anti' - conformer II, R =3.64%;
f
d) 'skewed-planar' - conformer III, R =7.15%;
f
e) 'planar- planar' - conformer IV, R =9.47%
f
100
sM(s)
a)
0
b)
100
∆
sM(s)
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32
Fig. 3. Experimental (dots) and calculated (for the optimal I/II conformers ratio - lines)
molecular intensities sM(s) and their differences ꢁsM(s) for the long (a) and short (b) nozzle-
to-plate distances.
According to Figure 2 it can be argued that the structure of conformers III and IV do
not satisfy GED data, while the theoretical functions f(r) of both conformers I and II are very
close to the experimental function and with each other despite the difference in the distances
between Cl atoms of the two SO Cl groups, which equal 7.34 and 8.36 Å in the I(syn) and
2
II(anti) conformers, respectively. The proximity of the O…O distances between these groups
(7.73 (2), 7.97, 7.99 and 8.94 Å in conformer I and 7.54 (2), 7.89, 8.08 and 8.99 Å in conform-
er II) results in the similarity of theoretical functions f(r) of conformers I and II as well.
The scanning of conformer ratio with relaxation of the geometric parameters of con-
formers I and II was undertaken (Fig.4).
1
2

ACCEPTED MANUSCRIPT
For the individual conformer II, disagreement factor R between experimental and the-
f
oretical functions sM(s) is 3.64%, for conformer I R is 3.85%. The lowest R = 3.34% corre-
f
f
sponds to the conformers mixture with mole fractions (χ 43%(25) χ 57(25)%). According to
I=
, II=
Hamilton criterion [35] at the significance level of 0.05 the models of individual conformers
may be excluded from consideration. The result of simultaneous refinement of structural pa-
rameters and conformer ratio is in agreement with this conclusion (Fig.2).
Thus, the GED data as well as QC calculations indicate that saturated vapor of 1,5-
NaphDSC at 413(5) K consists of the conformers I and II mixture with approximately equal
mole fractions.
3,90
3,85
3,80
3,75
3,70
3,65
3,60
3,55
3,50
3,45
3,40
3,35
3,30
3,90
3,85
3,80
3,75
3,70
3,65
3,60
3,55
3,50
3,45
3,40
3,35
3,30
R , %
R , %
f
f
0.05 significance level
0
10
20
30
40
50
60
70
80
90
100
Mole fraction of syn-conformer (I), %.
Fig. 4. The dependence of R value on the mole fraction of conformer I of 1,5-NaphDSC.
f
Conformational properties and features of conformers geometric structure
Molecule 1,5-NaphDSC has two coordinates associated with internal rotation SO Cl
2
groups about C1-S and C5-S bonds (numbering of atoms is shown in Fig. 1). The conforma-
tional properties of 1,5-NaphDSC were determined from the torsional potential functions
U(φ1,φ2) of the SO Cl group obtained by scanning φ1(C9–C1–S–Cl) angle with a step 10 de-
2
grees and an relaxation of other parameters including the φ2(C10–C5–S–Cl) torsion angle.
Two different starting positions of the other SO Cl group (φ2 equals 72.7° or 180°) were
2
1
3

ACCEPTED MANUSCRIPT
used.
In Figure 5 the U(φ1/72.7°) is the potential function of the first SO Cl group internal ro-
2
tation when the starting value of φ2(C10–C5–S–Cl) angle is equal to 72.7°. The U(φ1/180°)
potential function corresponds to scanning the angle φ1 when the starting value of φ2 angle is
180°. It should be noted that at scanning of the PES along the coordinate φ1, the geometrical
parameters and spatial position of the second sulfonyl chloride group remain practically un-
changed, indicating the independent rotation of the two substitutes.
The calculations predict the existence of three minima of the U(φ1/72.7°) potential
function. The minimum at φ1/φ2=72.7°/72.7° corresponds to conformer I ('skewed-skewed-
syn'), the minimum at φ1/φ2=287.3/72.7° is connected with existence of conformer II
('skewed-skewed-anti'), at last the minimum at φ1/φ2=180/72.7° corresponds to conformer III
('planar- skewed'). In turn, the minima of the U(φ1/180°) function correspond to conformers III
('skewed-planar', φ1/φ2=72.7/180°), IV ('planar-planar', φ1/φ2=180/180°) and enantiomer III*
('skewed-planar', φ1/φ2=287.3/180°).
As seen from the U(φ1/72.7°) plot, conformers I and II are the most stable structures in
comparison with conformers III and IV. The barriers to internal rotation of the sulfonyl chlo-
ride group for these conformers exceed considerably the thermal energy (0.8 kcal/mol) corre-
sponding to the temperature of the GED experiment. Therefore, the conformers I and II can be
considered as rigid molecular systems and the harmonic vibration approximation can be used
to describe their nuclear dynamics. In contrast, the conformers III and IV have to be regarded
as a non-rigid molecular systems due to the shallow potential well at φ1=180°, which is not
deeper than 0.4 kcal/mol. Note that the lowest vibrational mode for both conformers III and IV
corresponds to the torsional motion of the “planar” SO Cl group, and only five levels of this
2
vibration mode fit in the potential wells of conformers III and IV. However, both III and IV
conformers were excluded from consideration during structural analysis of experimental data
because they possess the high total energies.
1
4

ACCEPTED MANUSCRIPT
18
16
14
12
10
8
6
4
2
0
E, kcal/mol
18
16
14
12
10
8
ο
U(ϕ1/180
)
ο
U(ϕ1/72.7
)
IV
III
6
III
I
III*
II
4
2
0
0
30
60
90
120 150 180 210 240 270 300 330 360
ϕ1(C9-C1-S-Cl), deg.
Fig. 5. Potential functions of internal rotation U(φ1/72.7°) and U(φ1/180°) of the sulfonyl
chloride group of 1.5-NaphDSC as calculated by B3LYP/cc-pVTZ method. Minima corre-
spond to conformers I, II, III, IV and enantiomer III*.
The statistical analysis of X-ray data [36] showed that in crystal the naphthalene sulfonic
derivatives exist in the conformations with the bond S-X of SO X group in skewed or in pla-
2
nar positions with respect to the naphthalene skeleton, and skewed conformation meets about 9
times frequently than planar conformation. On a qualitative level, there is a correspondence
between the relative energies of skewed and planar conformers of free molecules, calculated
by B3LYP/cc-pVTZ method, and the probability of their structures realization in crystals.
Table 4 shows the experimental and calculated geometrical parameters of the most stable
conformers I and II as well as the calculated parameters of conformer III having the sulfonyl
chloride groups in skewed and in planar positions. Comparing the geometric characteristics of
conformers shows that the parameters of the naphthalene skeleton and SO Cl group parame-
2
ters in conformers I and II are close, while there is a difference in C1-C2, C-S, S-Cl bond
lengths (Tabl. 4) and Wiberg bond indexes as well as in atomic charges (Tabl. 6) for sulfonyl
chloride groups in skewed and in planar positions of conformer III.
These features can be explained in terms of NBO-analysis of the electron density dis-
tribution. Due to donor-acceptor interaction of the π(C1-C2) and σ*(S-Cl) orbitals in skewed
conformers the electron density transfer from the bonding to the antibonding NBOs takes
place. As a result, both bonds become weaker, and the bond C-S, in contrast, a more strong
1
5

ACCEPTED MANUSCRIPT
(Fig. 6, Table 6), leading to a corresponding change in the lengths and Wiberg bond indexes
compared to similar ones for sulfonyl chloride groups in planar positions in which this interac-
tion is absent.
Fig. 6 The donor-acceptor interaction of the π (C1-C2) and σ*(S-Cl) orbitals for sulfonyl chlo-
ride group in skewed position
It is noted that the planar structure of naphthalene skeleton is kept in all conformers,
and the Siamese C9-C10 bond is longer than the other C-C bonds in the skeleton. The data
presented in Table 5 indicate that the introduction of the SO Cl substituent in the naphthalene
2
framework lowers the Wiberg bond indexes of the two C–C bonds adjacent to the substituent.
The relationship between conformational properties and some physicochemical character-
istics of 1,5-NaphDSC.
Table 6 shows the some characteristics of 1,5-NaphDSC conformers and skewed
conformer of 1-NaphSC.
Table 6. The dipole moment values (ꢀ), the energies of frontier orbitals, NBO atomic charges
(q), Wiberg bond indexes (Q) and wave numbers of stretching S-Cl vibrations for 1,5-
NaphDSC conformers and skewed conformer of 1-NaphSC (B3LYP/cc-pVTZ).
a
1
-NaphSC
skewed
1,5-NaphDSC
Parameters
conformer III
skewed “planer”
conformer
conformer conformer
II
I
SO Cl group SO Cl group
2
2
1
6

ACCEPTED MANUSCRIPT
ꢀ
, D
5.426
0.949
-7.676
-3.308
-0.266
2.086
0.0
1.252
-7.615
-3.150
EHOMO, eV
ELUMO, eV
q(Cl)
-6.920
-2.588
-0.279
2.088
-0.874
-0.269
-0.161
-0.048
0.8529
0.6843
338.5
-
-7.674
-3.296
-0.266
2.086
-0.266
2.086
-0.251
2.068
q(S)
q(O)
-0.870
-0.261
-0.156
-0.045
0.8441
0.6943
341.9(16)
343.1(9)
-0.870
-0.261
-0.156
-0.045
0.8441
0.6947
341.2(0)
343.3(27)
-0.870
-0.261
-0.154
-0.042
0.8434
0.6952
-0.863
-0.337
-0.174
-0.046
0.8267
0.7036
q(C1)
q(C2)
q(C9)
Q(C-S)
Q(S-Cl)
νs(S-Cl), cm
-
1
b
341.4(12)
342.5(8)
-
1
νas(S-Cl), cm
a
For 'planar-planar' conformer IV the dipole moment value is 0, ν (S-Cl)=343(0), ν (S-
s
as
-1
Cl)=340.7(22) cm , EHOMO=-7.56 eV. ELUMO =-2.92 eV.
b
Intensity in brackets, km/mole.
In conformers I and II of 1,5-NaphDSC the NPA charges are practically identical, as
well as the energies of the frontier orbitals. Other orientation of SO Cl groups leads to chang-
2
ing NPA charges in the groups as well as to increasing the energies of frontier orbitals of con-
formers III and IV. However, the energies of HOMO and LUMO orbitals of any 1,5-NaphDSC
conformer are significantly lower the energies of frontier orbitals of 1-NaphSC (Table 6) and,
especially, of the frontier orbitals (Ehomo =-6.09, Elumo=-1.30 eV) of the naphthalene molecule.
Thus, the introduction of the second SO Cl group in monosubstituted naphthalene greatly in-
2
creases electron acceptor ability.
At the same time, the values and directions of the dipole moments of 1,5-NaphDSC
conformers are different (Table 6). Thus, the conformer ratio may affect the physicochemical
properties of the compound. For example, the vibrational spectra of the conformers will be
different. Since conformers II and IV have a center of symmetry, the symmetric vibrations ac-
tivity in IR spectrum will be absent, and the spectra will contain smaller number of bands than
the spectrum of conformers I and III which do not have a center of symmetry.
1
7

ACCEPTED MANUSCRIPT
Due to that the 1,5-NaphDSC conformers have the different dipole moments, they will
interact with the solvent differently, and their relative energy and the conformer ratio in the
solvent may change in comparison with the gas phase. Thus, in an aqueous medium the Gibbs
0
free energy difference ꢁG 2 of conformers I and II is 0.53 kcal/mol (calculation by PCM
98
method) in comparison with 0.02 kcal/mol in gas phase. Besides, the dipole moment of the
conformer I increases from 0.95 to 1.35 D at the transition from the gas phase to the aqueous
medium.
Obviously, the different conformers ability to hydration is the reason for appearance of
two sharp minima of activation enthalpy of 1,5-NaphDSC hydrolysis on the concentration de-
pendence of the aqueous i-PrOH mixtures [18]. At specific compositions of the aqueous i-
PrOH mixture some hydrate V-structures are formed in bulky water which possess maximal
complementarity to the structures of hydration shells for each of the 1,5-NaphDSC conform-
ers.
Conclusion
By GED and quantum chemical methods it was established that gas phase of 1,5-
NaphDSC at T = 413 (5) K contains two conformers with syn and anti S-Cl bonds orientations
of two sulfonyl chloride groups. The S-Cl bonds have skewed towards the longer C-C bonds
of naphthalene skeleton, i.e., position of the sulfonyl chloride groups is the same as in a stable
conformer of monosubstituted 1- NaphSC [1].
The introduction of two electron withdrawing SO Cl substituents in the naphthalene
2
framework significantly lowers the energy of frontier orbitals and increases the lengths of the
two C–C bonds adjacent to the substituent. The weakening of these C-C bonds is confirmed by
+
the presence of C Hn ions in the mass spectra of naphthalene sulfonyl halides which are ab-
9
sent or have very low abundence in the mass spectrum of naphthalene.
Though four conformers of 1,5-NaphDSC have close NPA-charges on the atoms and
energy frontier orbitals, they differ by a magnitude and direction of the dipole moment, by the
number of bands in the IR spectra and by the interaction with the solvent. The different con-
formers abilities to hydration may be the reason for appearance of two sharp minima of activa-
tion enthalpy of 1,5-NaphDSCh hydrolysis [18] on the concentration dependence of the aque-
ous i-PrOH mixtures.
For conformer III of 1,5-NaphDSC it is shown that the bond lengths C1-C2, C-S, S-Cl
1
8

ACCEPTED MANUSCRIPT
depend on SO Cl groups orientation with respect to the naphthalene skeleton. Within the
2
NBO-analysis the explanation for this fact is given.
Detected structural features of the 1,5-NaphDSC conformers allow to predict the con-
formational properties of unstudied mono- and disubstituted naphthalenes.
Acknowledgement
This work was supported by Russian Ministry of Education and Science (Project No
4.1385.2014K).
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[
[
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[
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Highlitght
1. Gas-phase electron diffraction and mass spectrometry (GED/MS) investigation of 1,5-
naphthalenedisulfonylchloride (1,5-NaphDSC).
2
3
4
5
. Fragmentation of 1,5-NaphDSC by electron ionization.
. Conformational composition of the vapor according to GED data and QC calculations.
. Conformational properties and features of conformer structures.
. The relationship between conformational properties and some physicochemical character-
2
1

ACCEPTED MANUSCRIPT
istics of 1,5-NaphDSC.
Graphical abstract
8
9 keV
+
+
C H (SO Cl)
2
10
6
2
C H S O Cl
10
6
2
4
+
C H SO Cl
10
6
2
+
C H Cl
10
6
+
C H
1
0
6
+
C H
9
6
5
0 eV
2
2