Molecular and electronic structure of triethylammonium salt of N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-sulfanylidene] ethanesulfonamide

Article abstract of DOI:10.1080/17415993.2012.747091

Molecular and electronic structure of triethylammonium salt of formally conjugated N-[(1-acetyl- 2-oxopropyl)(phenyl)-λ⁴- sulfanylidene]ethanesulfonamide anion, synthesized by reaction of N-(ethylsulfonyl)benzenesulfinimidoyl chloride with acet

Full text of DOI:10.1080/17415993.2012.747091

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Molecular and electronic structure
of triethylammonium salt of N-[(1-
acetyl-2-oxopropyl)(phenyl)-λ4-
sulfanylidene]ethanesulfonamide
Vadim M. Timoshenko a , Elena I. Kaminska a , Alexander B.
Rozhenko a b , Yuriy G. Vlasenko a , Alexandr N. Chernega a & Yuriy
G. Shermolovich a
a Institute of Organic Chemistry of NAS of Ukraine, Murmans'ka 5,
Kyiv, 02094, Ukraine
b Fakultät für Chemie der Universität Bielefeld, Postfach 100131,
33501, Bielefeld, Germany
Version of record first published: 03 Dec 2012.
To cite this article: Vadim M. Timoshenko , Elena I. Kaminska , Alexander B. Rozhenko ,
Yuriy G. Vlasenko , Alexandr N. Chernega & Yuriy G. Shermolovich (2012): Molecular and
electronic structure of triethylammonium salt of N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-
sulfanylidene]ethanesulfonamide, Journal of Sulfur Chemistry, DOI:10.1080/17415993.2012.747091
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Journal of Sulfur Chemistry, 2012
http://dx.doi.org/10.1080/17415993.2012.747091
Molecular and electronic structure of triethylammonium
salt of N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-
sulfanylidene]ethanesulfonamide
Vadim M. Timoshenkoa*, Elena I. Kaminskaa, Alexander B. Rozhenkoa,b, Yuriy G. Vlasenkoa,
Alexandr N. Chernegaa and Yuriy G. Shermolovicha
aInstitute of Organic Chemistry of NAS of Ukraine, Murmans’ka 5, Kyiv 02094, Ukraine; bFakultät für
Chemie der Universität Bielefeld, Postfach 100131, 33501 Bielefeld, Germany
(Received 8 October 2012; final version received 2 November 2012)
Molecular and electronic structure of triethylammonium salt of formally conjugated N-[(1-acetyl-
2-oxopropyl)(phenyl)-λ4-sulfanylidene]ethanesulfonamide anion, synthesized by reaction of N-
(ethylsulfonyl)benzenesulfinimidoyl chloride with acetylacetone in the presence of triethylamine, has been
studied theoretically and by X-ray diffraction.
O
O
S
Et
N
S
HNEt3
O
O
Keywords: sulfilimine;β-diketone;X-rayinvestigation;densityfunctionaltheory;RI-SCS-MP2;Mayer’s
bond orders; NBO charges
1. Introduction
Sulfilimines belong to a class of organosulfur compounds with a sulfur to nitrogen formal double
bond which have found widespread applications in organic syntheses and shown a variety of useful
properties (1–3). The growing interest in this type of compound is attributed to their application
in asymmetric syntheses. A new convenient routine for the synthesis of differently substituted
sulfilimines has been reported recently by Magnier and coworkers (4–6). But the definition of
bonding character in sulfilimines and its dependence on a type of substituents still remains a
=
challengefortheorists. Previously, itwasshownthatiminophosphinesincludingP Ndoublebond
are able to transfer the effects of substituents within the push–pull phosphabutadiene molecules,
*Corresponding author. Email: vadim@ioch.kiev.ua
© 2012 Taylor & Francis

2
V.M. Timoshenko et al.
R
S
R
S
O O
S
O O
S
R'
N
R"
R'
N
R"
A
B
Figure 1. Mesomeric forms of sulfonylsulfinilimines.
and the resulted structural and spectral effects can be referred to some sort of conjugation (7).
=
=
In contrast to phosphorus(III) in the P N fragment, the sulfur atom environment in the >S(:) N
ꢀ
=
−
= −
moiety is not planar. The nature of the S(IV) N and S(VI) N bonds in R2S N SO2R was
investigated theoretically (8) and by IR and UV spectroscopic methods (9). But the question still
remains open if the SIV N π-system can be involved in the interaction of the push–pull character
=
with attached substituents (Figure 1).We report here the first molecular structure of a sulfilimine, in
whichanacetylacetonideanionicmoietyisbondedtothesulfuratom:thetriethylammoniumsaltof
N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-sulfanylidene]ethanesulfonamide (1). In the current study,
we also estimate the extent of delocalization of anionic negative charge on the electronegative
imino-nitrogen and oxygen atoms of the SO2 group.
2. Results and discussion
2.1. N-Aryl(alkyl)sulfonylsulfinilimines
The analysis of the data from the X-ray diffraction study on the molecular structures of
N-aryl(alkyl)sulfonylsulfinilimines, reported in the literature (10–13), demonstrates a common
feature inherent to these compounds: the formally double SIV N bond is always noticeably longer
=
than the SVI N single bond. The corresponding bonds lengths for compounds 2 and 3 (Figure 2),
−
for which crystallography data are available from the Cambridge Structural Database, are given
in Table 1 (the complete set of data is collected and presented in the Supplementary Information).
The effect might be referred to as delocalization of electron density on the oxygen atoms, as
described by mesomeric form B. In this case, the SIV N π-system participates in conjugation
=
behaving similar to other classical π-bonds.
We have first undertaken a thorough theoretical study on the structures of sulfonylsulfinilimines
2, 3. Geometry optimization for 2 and 3 was carried out using two different DFT approaches:
RI-BP86/TZVP (14, 15) and TPSSh/TZVP (16). The equilibrium structures predicted by calcu-
lations for 2, 3 differ significantly from those found in the crystal (Table 1). The SVI–N bonds
are longer than the SIV N bonds (2) or possess practically the same length (3). Modeling the
=
crystal environment as a strongly polar solution (water) using the Conductor like Screening Model
N
H
O S
O
N
S
O
O
O S
O
O S
O
O S
O
N
N
N
Me
R
S
S
S
Me
4
1
2
3
Figure 2. Chemical structures of sulfonylsulfinilimines calculated in this work.

−
Table 1. Experimental (X-Ray diffraction) and calculated S N bond lengths (Å) and Mayer’s bond orders (23) for 1–4.
1
1a
2
3
4
SIV
N
SVI
N
SIV
N
SVI
N
SIV
N
SVI
N
SIV
N
SVI
N
SIV
N
SVI
N
=
−
=
−
=
−
=
−
=
−
Data
Experiment
1.652
1.599
–
–
1.641
1.597
1.650 (24)
1.632, 1.638
(25)a
1.672
1.688
1.592 (22)
1.608, 1.611
(23)a
1.672
1.649
–
–
TPSSh calc.
1.705
–
1.033
–
1.666
–
1.001
–
1.684
1.693
1.078
1.051
1.658
1.652
1.117
1.119
1.649
1.688
1.024
1.000
1.681
1.654
1.107
1.157
1.667 (1.660)b
1.684 (1.678)b
1.083
1.676 (1.662)b
1.654 (1.640)b
1.027
TPSSh-COSMO calc.
Mayer bond orders (TPSSh)
Mayer bond orders (TPSSh-
COSMO)
1.014
0.964
1.103
1.183
1.036
1.098
Notes: aTwo different molecules were found in the crystallographic cell; bCalculated at the RI-MP2-SCS/TZVP level of theory.

4
V.M. Timoshenko et al.
Me
R
S
Me
R
S
O O
S
Me
R
S
O O
S
O O
S
O
N
R"
O
N
R"
O
N
R"
Me
O
Me
O
Me
O
C
D
E
Figure 3. Mesomeric forms of sulfonylsulfinilimines with acetylacetonide substituent.
IV
(COSMO) procedure (17–19) yields a shorter SVI N bonds in comparison to the S
N dis-
−
=
tances, but in fact all the bonds seem to be slightly elongated compared with the experimental
ones. It is more pronounced for the BP86 “pure functional” and the corresponding data (see the
Supplementary Information) will not be considered here. The TPSSh functional belongs to the
family of hybrid meta-GGA DFT methods and is considered to provide quite reliable geome-
tries (20). In support of this suggestion, the model structure 4 calculated using the more superior
RI-SCS-MP2 approach (21, 22) indicates the bond lengths similar to those derived at the DFT
(TPSSh) level of theory (Table 1).
As the SVI N bonds become shorter by using the COSMO procedure, the corresponding
−
Mayer’s bond orders (23) calculated for 2 and 3 (Table 1) become close to 1.2. Thus, the polar
environment causes some electron density polarization within the SIV N π-system towards the
=
electron acceptor RSO2 group (mesomeric form B), as predicted by calculations.
2.2. Synthesis, molecular structure and quantum chemical investigations of 1
We expected an enforced effect by attaching a negatively charged acetylacetonide substituent to
the SIV atom and forming an ylidic conjugated form of the anion (Figure 3). In this case, negative
charge would be partially delocalized at nitrogen (mesomeric form D) and on the sulfonyl oxygens
(E). This should be indicated by a shortening of the C–SIV bond and probably, more pronounced
VI
changes in the SIV N and S –N bond lengths.
=
Compound 1 was synthesized by reaction of N-(ethylsulfonyl)benzenesulfinimidoyl chloride
(5) with acetylacetone in presence of triethylamine (Scheme 1). A crystal of 1 suitable for X-ray
investigation was grown from etheral solution.
, C6H6
S
2EtSO2NCl2
+
S
EtSO N
2
O
O
O
NSO2Et
S
, 2 Et3N
S
+
HNEt
3
Cl
CCl4
O
5
1
Scheme 1. Synthesis of sulfilimine 1.
The molecular structure of compound 1 was determined by single-crystal X-ray diffraction.
The perspective view of molecule 1 and selected structure parameters are given in Figure 4 and
in Tables 2 and 3.

Journal of Sulfur Chemistry
5
Table 2. Crystal data and structure refinement for the compound 1.
Molecular formula
C13H16NO4S2 · C6H16
416.61
N
Formula weight
Space group
P21/n
Monoclinic
173(1)
Crystal system
Temperature (K)
Wavelength (Å)
0.71078
9.0475(3)
15.0508(6)
16.7121(8)
90
a (Å)
b (Å)
c (Å)
α (◦)
β (◦)
95.269(2)
90
γ (◦)
V (Å3)
2266.1(2)
4
Z
Calculated density (g · cm−3
)
1.22
Absorption coefficient (mm−1
)
0.260
F(000)
896
Crystal size (mm)
Theta range for data collection (◦)
0.35 × 0.43 × 0.57
1.82–26.78
Index ranges, hkl
−10 to 11, −16 to 19, −15 to 20
No. of reflections collected
No. of independent reflections (Rint
15575
)
4714
99.9
Completeness to theta = 26.78◦ (%)
Absorption correction
None
Refinement method
Full-matrix least-squares on F
3297, 0, 248
Data, restraints, parameters
Goodness-of-fit on F
1.074
Final R-indices [I > 3σ(I)]
R-indices (all data)
Largest diff. peak and hole (e Å−3
R1 = 0.0416, wR2 = 0.0453
R1 = 0.0674, wR2 = 0.0673
0.28 and −0.21
)
Table 3. Selected bond lengths (Å) and
valence angles (◦) for the compound 1.
Bond length
Å
S(1)–N(1)
S(1)–C(1)
S(1)–C(7)
C(7)–C(8)
O(3)–C(8)
S(2)–O(1)
S(2)–O(2)
S(2)–N(1)
S(2)–C(12)
1.652(2)
1.795(2)
1.725(2)
1.437(3)
1.227(3)
1.443(2)
1.440(2)
1.599(2)
1.778(2)
Valence angles
(◦)
N(1)S(1)C(7)
S(1)C(7)C(8)
C(7)C(8)O(3)
111.1(1)
116.1(2)
121.6(2)

6
V.M. Timoshenko et al.
Figure 4. ORTEP plot of 1 from X-ray crystal structure.
In the solid state, the HN+Et3 cation and anion 1a are connected by weak (24) inter-
−
molecular hydrogen bonds N(2) H(1) · · · N(1) [N(2)–N(3) 2.995(4) Å, N(2)–H 0.75(3) Å,
◦
−
N(1)–H 2.34(3) Å, N(2)HN(1) 146(3) ] and N(2) H · · · O(3) [N(2)–O(3) 3.002(4) Å, N(2)–
H 0.75(3) Å, O(3)–H 2.42(3) Å, N(2)HO(3) 135(3)◦] forming the six-membered ring
N(1)S(1)C(7)C(8)O(3)H(1). The S(1)C(7)C(8)C(10)O(3)O(4) delocalized acetylacetonide sub-
unit is nearly planar. The two C–C bond distances [C(7)–C(8) and C(7)–C(10)] and two C–O
bond distances [C(8)–O(3) and C(10)–O(4)] are slightly different, which is probably determined
−
by the weak N(2) H · · · O(3) hydrogen bonding. The S(1) atom has a pyramidal configuration
(the sum of corresponding bond angles 318.0(3)◦). The S(2) atom has a distorted tetrahedral
coordination. But it is worthy to note that the S(1)–C(7) bond (1.725 Å) is distinctly shorter
than the S(1)–C(1) bond (1.795 Å). This agrees well with some contribution of the mesomeric
form E. On the other hand, the S(1)–N(1) (1.652 Å) and S(2)–N(1) (1.599 Å) are almost
identical to those found in the neutral sulfilimine 2 (1.641 and 1.597 Å, respectively). There-
fore, there is no visible sign of strengthening the conjugation effect in 1 compared with 2
and 3.
Structure 1 has been calculated using the TPSSh/TZVP level of approximation, both in the
anionic form (1a) and as an ion pair with tetraethyl ammonium cation (1). The optimized structures
are shown in Figure 5.
VI
While in the calculated structure 1a, the SIV N bond is longer than the S
N bond, they
=
−
are again elongated compared with the experimental values (1.684 vs. 1.652 Å and 1.658 vs.
1.599 Å, respectively). Additionally, in this case, modeling the crystal environment as the solvent
effect in water does not significantly change the bond lengths: 1.693 Å (SIV N) and 1.652 Å
=

Journal of Sulfur Chemistry
7
Figure 5. Equilibrium (TPSSh/TZVP) structures of 1 (a) and 1a (b).
(SVI N). The corresponding bonds are even longer in the optimized structure of the ion pair
−
1 involving triethyl ammonium cation (1.705 and 1.666 Å, respectively). In the equilibrium
structure, the hydrogen bonding is clearly formed with participation of the imino-nitrogen atom
1
=
(S N · · · H 1.857 Å).
The S–C bond length toward the acetyl acetonide moiety (1.755 Å) is still shorter than the
S–CPh distance (1.814 Å), which is in accord with the partially ylidic character of the former
bond. The Mayer bond orders calculated for these two C–S bonds in 1a also differ significantly
VI
(1.043 and 0.745). On the contrary, the bond indices for the formally different SIV N and S
bonds (1.078 and 1.117) are close.
N
=
−
To estimate the net charge transfer toward the N-SO2Et moiety, we have calculated the NBO
total charges (25–28) on the atoms for 1a (Figure 6). All the bonds in the C–S–N–S–(O)2 moiety
are strongly polarized, as evident from the total NBO charge values.
A summation of the NBO charges within the acetyl acetonide moiety provides the value of
−0.884 instead of −1.000. The remaining −0.116e is delocalized on the electronegative imino-
nitrogen and oxygen atoms of the sulfonyl group. Thus, the charge delocalization within 1a really
takes place but it is insignificant.

8
V.M. Timoshenko et al.
–0.610
O
C
–0.965 O
O
+0.489
S
S
H
+0.200
+0.224
–1.080
–0.573
-0.672
N
C
C
C
H
+0.496
H
H
H
+0.229
+0.246
+0.210
C
H
O
–0.635
-
0
.
7
0
0
+0.212
Figure 6. Total NBO charge values calculated for some atoms in 1a.
3. Conclusions
The molecular structure of N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-sulfanylidene]ethanesulfon-
amide (1) has been determined by X-ray investigations. This species can be formally considered
as a push–pull sulfilimine. Such consideration agrees well with the bond alternation found
VI
in the single-crystal structure: the elongated SIV N and shortened S
N bonds. Similar
=
−
structural features have also been found for the other known sulfilimines. Quantum chem-
istry calculations carried out at the DFT (TPSSh) and RI-SCS-MP2 levels of approximation
in the gas phase predict such effect for 1, whereas for the sulfilimines 2 and 3 it comes
to the fore only by modeling the polar environment in the crystal. It has also been demon-
strated that in 1 the negative charge is partially delocalized at the electronegative imino-nitrogen
and oxygen atoms, which is in line with some contribution of push–pull conjugation in
N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-sulfanylidene]ethanesulfonamide.
4. Experimental
4.1. General experimental information
1H and 13C NMR spectra were recorded with a Bruker AVANCE 400 spectrometer (400.13 MHz
for 1H and 100.62 MHz for 13C) using CDCl3 as solvent at room temperature and chemical shifts
are referred to the solvent signal at δH = 7.26 ppm (residual CHCl3) and δC = 77.16 ppm (CDCl3).
MS data were obtained on ADSI MS, Agilent 1100\DAD\MSD VL G1965 instrument.
4.2. Synthesis of N-(ethylsulfonyl)benzenesulfinimidoyl chloride (5)
A mixture of diphenyldisulfide (0.44 g, 2 mmol) and N,N-dicloroethanesulfamide (0.7 g, 4 mmol)
in dry benzene (15 ml) was refluxed for 2 h. Solvent was removed in vacuum to give in residue
chloride 5 (1.1 g) as an orange oil, which was pure enough to use in the next step without additional
1
3
purification. H NMR (CDCl3, 400 MHz): δ = 1.51 (t, 3H, JHH = 7.5 Hz, CH3), 3.30 (q, 2H,

Journal of Sulfur Chemistry
9
3JHH = 7.5 Hz, CH2), 7.69 (m, 3H, CHAr), 8.06 (m, 2H, CHAr). MS (Irel, %) m/z: 253 (10%) and
251 (25%) (M+), 77 (Ph+).
4.3. Synthesis of triethylammonium salt of
N-[(1-acetyl-2-oxopropyl)(phenyl)-λ4-sulfanylidene]ethanesulfonamide (1)
A solution of chloride 5 (0.5 g, 2 mmol) in CCl4 (60 ml) was added for 20 min to a mixture of
acetylacetone (0.8 g, 8 mmol) and Et3N (0.8 g, 8 mmol) in CCl4 (15 ml) at 0oC. The mixture was
additionally stirred for 2 h without cooling, precipitate of Et3N · HCl was filtered off and solvent
was removed in vacuum. The residue was washed with hexane (50 ml) and treated with cold
diethyl ether to give 1 as orange oil which slowly solidified at standing. The crystal for X-ray
investigation has grown at slow evaporation of etheral solution. Yield 0.4 g (48%), mp 78–80oC.
1H NMR (CDCl3, 400 MHz): δ = 1.15 (t, 9H, 3JHH = 7.0 Hz, 3CH3), 1.36 (t, 3H, 3JHH = 7.5 Hz,
CH3), 2.42 (s, 6H, 2CH3), 3.15 (m, 8H, 4CH2), 7.42 (m, 3H, CHAr), 7.66 (m, 2H, CHAr), 15.5 (br,
1H, NH). 13C NMR (CDCl3, 100 MHz): δ = 8.27 (CH3, CH3CH2N), 8.93 (CH3, CH3CH2SO2),
45.65 (CH2, CH3CH2N), 48.29 (CH2, CH3CH2SO2), 102.48 (OC–C–CO), 125.34 (CHPh), 128.74
−
(CHPh), 129.10 (CHPh), 138.55 (CPh), 191.48 (C O). Anal. Calcd. for C19H32N2O4S2: S, 15.39;
N, 6.72%. Found: S, 15.18; N, 6.54%.
4.4. X-ray structure determination of 1
The crystallographic measurements were performed at 173(1) K on a Bruker Smart Apex
II diffractometer operating in the ω and ϕ scans mode (only cell measurements were per-
formed at 293(1) K). The intensity data were collected using Mo-Kα radiation (λ = 0.71078Å).
The SADABS procedure absorption correction (29) was applied. The structure was solved by
direct methods and refined by the full-matrix least-squares technique in the anisotropic approxi-
mation for the non-hydrogen atoms using the SHELXS97 and SHELXL97 programs (30, 31) and
CRYSTALS program package (32). All hydrogen atoms were located in the difference Fourier
maps and refined with fixed positional and thermal parameters (only H(1) atom participating
in the hydrogen bonds was refined isotropically). In the refinement, 4714 independent reflec-
tions (3297 reflections with I ≥ 3σ(I)) were used. Convergence was obtained at R1 = 0.0674
and wR2 = 0.0673 for all reflections, and R1 = 0.0416 and wR2 = 0.0453 for observed ones,
GOF = 1.074 (248 parameters; observed/variable ratio 13.3; the largest and minimal peaks in the
final difference map 0.28 and –0.21 e/Å3). Chebyshev weighting scheme (33) with parameters
0.741, 0.359 and 0.410 was used. CCDC-881430 contains the supplementary crystallographic data
for this article. These data can be obtained free of charge at www.ccdc.cam.ac.uk/data_request/cif;
www.ccdc.cam.ac.uk/conts/retrieving.html.
4.5. Details of calculations
All structures were optimized using the ORCA program packet (34, 35) without any symme-
try restriction. The complete data set is listed in the Supplementary Information to this paper.
The X-ray determined structures were used as starting geometries. Initially, the structures were
optimized using the RI-BP86 approach (14, 15) and then re-optimized at the TPSSh (16, 20)
level of theory. In the both cases, the TZVP basis sets (the TZV basis sets of triple-zeta quality
(36) plus one p-function set for hydrogen and one d-function set for all other atoms). In order to
increase the efficiency of the calculations, the parallel RIJCOSX algorithm (37, 38) was used with
accurate grid parameters (Grid5, GridX6). For all optimized geometries, the vibrational analyses
were carried out numerically and no imaginary frequencies were found. The Mayer bond orders

10 V.M. Timoshenko et al.
(23) were derived for the equilibrium structures. The crystal environment was mimicked as an
effect of strongly polar solvent (water) using the COSMO procedure (17–19). The structure 4
was additionally optimized at the RI-SCS-MP2/TZVP level of theory (21, 22). The NBO analy-
sis (27–30) was carried out at the B3LYP/TZVP (39, 40) level of theory using the Gaussian-03
program set (41). The structures were presented graphically using the JMol program.2
Acknowledgements
The authors thank to Dr V.V. Trachevsky, the Joint Use Center of NMR Spectroscopy at the G.V. Kurdyumov Institute for
Metal Physics of NAS of Ukraine for recording the NMR spectra. We greatly acknowledge Prof. Dr Uwe Manthe for the
access to the computer cluster at the Chemistry Department of the University of Bielefeld and to the Gaussian-03 set of
program. We also thank to the team of the Supercomputer at the Institute of Cybernetic, NAS of Ukraine, providing an
access to the SKIT-3 computer cluster for A.B.R. for the ORCA calculations.
Notes
1. Two different structures 1 and 1ꢀ with very close total energies are localized by geometry optimization (see the
Supplementary Information). Structure 1 with the conformation of the triethylammonium cation similar to that
found in the experiment was discussed in the paper.
2. Jmol: an open-source Java viewer for chemical structures in 3D. See also http://www.jmol.org/.
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