Intramolecular hydrogen bonds in the sulfonamide derivatives of oxamide, dithiooxamide, and biuret. FT-IR and DFT study, AIM and NBO analysis

Article abstract of DOI:10.1016/j.tet.2010.08.076

The hydrogen bonding in [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]biuret 1, [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]oxamide 2, and [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]dithiooxamide 3, the sulfonamide derivatives of biuret 4, oxamide 5, and d

Full text of DOI:10.1016/j.tet.2010.08.076

Tetrahedron 66 (2010) 8551e8556
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Intramolecular hydrogen bonds in the sulfonamide derivatives of oxamide,
dithiooxamide, and biuret. FT-IR and DFT study, AIM and NBO analysis
*
B.A. Shainyan , N.N. Chipanina, T.N. Aksamentova, L.P. Oznobikhina, G.N. Rosentsveig, I.B. Rosentsveig
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Science, 1 Favorsky Street, 664033 Irkutsk, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 June 2010
Received in revised form 13 August 2010
Accepted 31 August 2010
Available online 9 September 2010
The hydrogen bonding in [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]biuret 1, [(1-arylsulfonylamino-
2,2,2-trichloro)ethyl]oxamide 2, and [(1-arylsulfonylamino-2,2,2-trichloro)ethyl]dithiooxamide 3, the
sulfonamide derivatives of biuret 4, oxamide 5, and dithiooxamide 6, has been studied by molecular
spectroscopy and DFT theoretical calculations including frequency calculations, at the B3LYP/6-311þG
(d,p) level of theory. The analysis of the C]O/HN and C]S/HN intramolecular hydrogen bonds closing
the five- and six-membered rings employing the atoms-in-molecules (AIM) method using the MP2(full)/
6-311þþG(d,p) wave functions has shown that their stability is increased in comparison to the original
molecules and is much higher in the thiocarbonyl compounds. The results of the AIM and the NBO
analysis of donoreacceptor interactions are in good agreement with each other and with the experi-
mental FT-IR spectroscopy data.
Keywords:
Amides and thioamides
Hydrogen bonding
FT-IR spectroscopy
AIM analysis
Ó 2010 Elsevier Ltd. All rights reserved.
NBO analysis
Quantum chemical calculations
1. Introduction
theoretical calculations including the AIM and NBO analysis of
[(1-arylsulfonylamino-2,2,2-trichloro)ethyl]biuret (1), [(1-arylsul-
Compounds containing the amide or thioamide group are of
great interest due to their biological activity.1 Hydrogen bonding in
these systems is the dominant interaction determining the con-
formation of the molecules and investigation of this may be helpful
for peptide and protein structural characterization. Biuret and its
derivatives are used as ligands in the synthesis of complex
compounds.2,3
Recent quantum chemical studies of biuret and its thio-analogs
have shown that the minima on the potential energy surface cor-
respond exclusively to the trans-isomers, whereas the cis-isomers
represent transition states.4 The molecules exist predominantly
in the diketo-form, although they are capable of tautomeric
transformation to give the corresponding enols.5 The presence of
intramolecular hydrogen bonds plays an important role in
these systems.6 The sulfonamide group in unsaturated nitrogen-
fonylamino-2,2,2-trichloro)ethyl]oxamide (2), and [(1-arylsulfony-
lamino-2,2,2-trichloro)ethyl]dithiooxamide (3). highly acidic
A
SO2NH group in these compounds is capable of forming strong
hydrogen bonds.8 All experimental measurements were performed
for compounds 1be3b, whereas, without loss of generality, the
unsubstituted analogs 1ae3a were used for the theoretical analysis.
The spectra of compounds 1be3b were compared to the spectra of
the model compounds: biuret (4), oxamide (5), dithiooxamide (6)
(rubeanic acid). We have also measured the NH-acidity of com-
pounds 1be3b by potentiometric titration in methanol. Polyamide
systems similar to 1e6 are used as strong NH acids,9 reagents for
asymmetric synthesis, and supramolecular chemistry,10 in the syn-
thesis of macrocyclic nitrogen-containing compounds.11
The structure and composition of compounds 1be3b was
proved by FT-IR and 1H, 13C NMR spectroscopy, and elemental
analysis.12 The experimental frequencies nNH and nCO were assigned
by comparing them with those derived from theoretical calcula-
tions of the vibrational spectra. The theory of atoms in molecules
(AIM) was employed to indicate the existence and the relative
strength of the intramolecular hydrogen bonds NH/O]C and
NH/S]C closing the five- and six-membered rings in the studied
molecules. The natural bond orbital (NBO) analysis was used to
determine the importance of delocalization interactions in the
conjugated fragments of the molecules.
containing ligands results in a decrease of the
s
-donating ability of
-acceptor
the nitrogen atom lone pair and an increase of the
p
properties of the chelating bidentate fragment.7 In order to
investigate the presence and the nature of hydrogen bonds in the
sulfonamide derivatives of polyamide molecules, in the present
work we have performed the FT-IR spectroscopic study and DFT
* Corresponding author. E-mail address: bagrat@irioch.irk.ru (B.A. Shainyan).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.08.076

8552
B.A. Shainyan et al. / Tetrahedron 66 (2010) 8551e8556
CCl3
O
C
O
C
HN
C
CH
H
NHSO2C6H4X-p
N
CH
CCl3
C
O
NHSO2C6H4X-p
H2N
N
H2N
O
H
1a (X = H); 1b (X = Cl).
2a (X = H); 2b (X = Cl).
S
O
C
NH2
C
O
S
H
NHSO2C6H4X-p
C
N
CH
CCl3
C
S
H2N
C
NH2
C
NH2
N
C
O
C
S
O
H2N
H2N
H2N
H
4
5
6
3a (X = H); 3b (X = Cl).
2. Results and discussion
2.1. Potentiometric acidity
only by the electronegativity of substituent R but also by nonvalent
interactions in the molecule, including intramolecular hydrogen
bonding.14
The sulfonamide derivatives 1e3, as well as their model com-
pounds 4e6 have two electron donating groups (C]O or C]S) and
from two to four proton donor groups NH. Therefore, in the solid
state they can exist as self-associates due to intermolecular hy-
drogen bonds and are also capable of formation of different intra-
molecular hydrogen bonds depending on the relative orientation of
the donor and acceptor groups.
The values of pKa of compounds 1be3b demonstrate rather high
acidity of the SO2NH group and are equal to 11.77, 11.18, and 11.69,
respectively. They are more acidic than 4-chloro-N-[2,2,2-trichloro-
1-(p-tolyl)-ethyl]benzenesulfonamide 4-ClC6H4SO2NHCH(Tol-p)CCl3
(pKa 13.04) or N-methyltrifluoromethanesulfonamide (12.70),13
although less acidic than trifluoromethanesulfonamide itself (pKa
11.06) in the same solvent.14 It is pertinent to mention that the
potentiometric acidity of sulfonamides RSO2NHR0 is determined not
2.2. Geometry and FT-IR spectroscopy
In the early studies, a detailed analysis of the IR spectra of crys-
talline biuret and its thio-analogs in the region of the NH stretching
vibrations was shown to be difficult.15,16 Complete assignment was
successfully made by the use of quantum chemical calculations of
the vibrational spectra of these molecules and their deuterated an-
alogs, and by invoking the experimental and theoretical spectra of
formamide and thioformamide, whose FT-IR spectra were obtained
in the gas phase and in the matrix-isolated state.17
We have analyzed the FT-IR spectra of compounds 1be3b,
4e6 in the solid state and in acetonitrile solution and compared
them to the results of calculations (B3LYP/6-311þG(d,p)) of the
vibrational frequencies of the isolated model molecules 1ae3a,
4e6 (Table 1). All vibrational calculations were performed in the
Table 1
Experimental (FT-IR) and B3LYP/6-311þG(d,p) calculated frequencies of nNH and nCO vibrations of compounds 1e6 (for numbering of atoms see Fig. 1)
1b
1a
4
nexp, cmꢀ1
nacalcd, cmꢀ1
Mode assignment
nexp, cmꢀ1
nacalcd, cmꢀ1
Mode assignment
Solid
MeCN
Solid
MeCN
3446m
3472w
3710
n
as(N1H2)
3402bvs
3486m
3710
3709
3620
3591
3519
n
n
n
n
n
as(N1H2)
as(N2H2)
(N3H3)
s(N1H2)
s(N2H2)
3337w
3366m
3616
3591
3494
3442
n(N3H3)
n
s(N1H2)
n(N4H4)
n(N2H2)
3385m
3333w
3270w
3205m
3140w
1695s
(1701)c
2b
3310w
3200m
3250bs
1713s
1766
1756
2a
3712
3576
3548
3506
1778
1744
3a
n
n
asC]Oþ
d
NH2
1725bvs
(1690)
5
3378m
3177m
1712s
1792
1764
n
n
as(C]O)
s(C]O)
sC]Oþ
d
N3H
3379m
3320m
3461w
3347m
n
n
n
n
n
n
as(NH2)
s(NH2)
dd
3713
3573
n
n
as(NH2)
s(NH2)
(N2H2)
(N4H4)
sC]Oþ
3198m
(1713)
1661s
3b
3293m
1706s
d
NH2
(1703)
1652s
6
3286s
3204m
3126s
1786
1761
n
n
s(C]O)
asC]Oþ
d
NH2
as(C]O)
3378m
3375w
3261m
3200w
3675
n
as(NH2)
3375m
3263m
3677
3472
n
as(NH2)
2
n
d(NH2)
3230m
3478
3468
3328
n(N4H4)
n
s(NH2)
n(N2H2)
s(NH2)
3140w
a
Unscaled harmonic wavenumbers.
Data for biuret-anhydrate from Ref. 17.
The numbers in parentheses refer to the Raman frequencies.
Compound is insoluble in MeCN.
b
c
d

B.A. Shainyan et al. / Tetrahedron 66 (2010) 8551e8556
8553
harmonic approximation. The structures with the trans orienta-
tion of the carbonyl or thiocarbonyl groups were used for the
geometry optimization, since, for example, the cis-form of biuret
4 is 12.3 kcal/mol less stable than its trans-form, and the cis-
forms of oxamide 5 and dithiooxamide 6 do not correspond to
minima on the potential energy surface (PES), and during the
geometry optimization are transformed into the trans-forms.
In the IR spectrum of the solid compound 1b, five stretching
vibrational bands nNH are observed (Table 1). In solution, the lowest
frequency band at 3140 cmꢀ1 disappears, clearly pointing to its
belonging to vibrations of the NH groups participating in the for-
mation of an intermolecular hydrogen bond. Other nNH bands
correspond to the free NH groups and to those involved in the
intramolecular hydrogen bonds NH/O]C.
The global minimum on the PES of the model molecule 1a cor-
responds to the structure with free NH2 and NH groups, and with the
amide and sulfonamide NH groups closing the two six-membered
rings by formation of the NH/O]C intramolecular hydrogen bonds
(Fig. 1). This form has the largest dipole moment (m 10.06 D) and,
hence, should be stabilized inpolar media. Following the orderof the
calculated frequencies of molecule 1a and comparing them to the
experimental and calculated vibrational frequencies of biuret 4
(Table 1) we have made the assignment of the nNH and nC]O bands in
the FT-IR spectrum of compound 1b in solution. The highest fre-
quency band at 3472 cmꢀ1 belongs to the asymmetric stretch of the
free NH2 group in 1b. In the spectrum of a solution of formamide, the
similar band is located at 3480 cmꢀ1 and in the spectrum of biuret
4 d at 3486 cmꢀ1. The next band in the FT-IR spectrum of 1b at
Fig. 1. B3LYP/6-311þG(d,p) calculated structures of molecules 1e6.

8554
B.A. Shainyan et al. / Tetrahedron 66 (2010) 8551e8556
3366 cmꢀ1 corresponds to the stretching vibrations of the free NH
group and symmetric stretch of the NH2 group, as does the band at
3385 cmꢀ1 in the FT-IR spectrum of biuret 4. Their position corre-
sponds to the values of nNH 3350e3360 cmꢀ1 in the spectra of ace-
tonitrile solutions of a wide series of acetanilides containing both
electron donor and acceptor substituents in the benzene ring.18 The
bands relating to the vibrations of the sulfonamide and amide
groups of 1b, which according to calculations are involved in the
formation of intramolecular hydrogen bonds appear at 3310 and
3200 cmꢀ1, respectively. Their relative positions correlate with the
calculated H-bond lengths (lHO) of the amide (lHO 1.876 Å) and sul-
fonamide (lHO 2.067 Å) groups NH in 1a (Fig.1). The single nC]O band
at 1713 cmꢀ1 in the spectrum of the solution of 1b and at 1695 cmꢀ1
in the spectrum of the solid sample corresponds to the stretching
vibrations of the carbonyl groups involved in the formation of
intramolecular hydrogen bonds. In the Raman spectrum of solid 1b
the bands of the carbonyl group stretching vibrations appear at
similarly substituted amides (D
pKa reaches 7e8 units19) the H-
bond formed by the amide NH group in the studied molecules is
shorter than (in 1a, 3a) or comparable with (in 2a) that formed by
the sulfonamide NH group. This reflects the principal difference
between the thermodynamic acidity determined by the stability of
the corresponding anion, and the spectroscopic acidity, which is
determined as the value of DnNH and is a measure of a hydrogen
bond donating ability. Moreover, for molecular systems containing
intramolecular hydrogen bonds the value of DnNH is determined not
only by the proton donating ability of the NH acid itself but also by
steric restrictions imposed by the arrangement of the acidic and
basic centers in the molecule.
2.3. Atoms in molecules analysis
The AIM analysis was used to determine the presence of bond
critical points (BCPs) of the intramolecular bonds NH/X (X¼O, S)
and to evaluate their energies. The most often used criteria of the
existence of hydrogen bonding interactions are the electron density
1701 cmꢀ1
.
The relative stability of the intramolecular hydrogen bonds
formed with participation of the amide and sulfonamide NH groups
in compound 2 is different from that in 1. In the most stable
r
(rc) and the Laplacian of the electron density V2r(rc) at the BCPs.
These parameters for the intramolecular NH/X along with the
lengths and angles of the corresponding hydrogen bonds in the
studied molecules are given in Table 2.
structure of the model compound 2a, (m 6.72 D) two five-mem-
bered rings are closed by the amide hydrogen bonds NH/O]C,
whereas the sulfonamide NH group is involved in closing the six-
membered ring (Fig. 1). The length of the H/O bond (lHO 2.290 Å)
formed by the NH2 group is comparable with the length of the
similar bond in oxamide 5 (lHO 2.286 Å), both being 0.3 Å longer
(and, hence, weaker) than the H-bond of the similar type in the six-
membered ring of biuret 4. The H-bond in the five-membered ring
in molecule 2a formed by the secondary amino group (lHO 2.176 Å),
although shorter than that with the primary amino group NH2 by
0.1 Å, is still longer than the H-bond in the six-membered ring
formed by the sulfonamide group (lHO 2.117 Å). In the FT-IR spec-
trum of the acetonitrile solution of compound 2b, the high fre-
Table 2
Bond lengths (lH/X, Å), bond angles (:(NHX), deg), electron densities (r
(rc), e/Å3),
Laplacians (V2r(rc), e/Å5) at BCPs, and bond energies for hydrogen bonds (EH/X, kcal/
mol) in molecules 1e4, 6
Molecule, H-bond
lH/X
:(NHX)
r
(rc)
V
2r(rc)
EH/X
ꢀGc/Vc
1a, N2H2/O1
N4H4/O2
2a, N4H4/O2
3a, N1H1/S2
N2H2/S1
N4H4/S2
4, N2H2/O1
6, NH/S
1.876
2.067
2.117
2.385
2.264
2.441
1.960
2.418
135.6
125.0
124.1
113.1
121.7
126.7
129.4
112.9
0.217
0.154
0.140
0.149
0.187
0.132
0.182
0.129
2.805
2.009
1.800
1.592
1.676
1.273
2.466
1.530
8.6
5.4
4.8
4.6
6.0
3.8
6.8
4.3
1.033
1.104
1.108
1.058
0.954
1.042
1.093
1.080
quency band nas
appears at 3461 cmꢀ1 (Table 1), as in the
NH2
spectrum of compound 1b, where this group is H-nonbonded. This
also points to a weak intramolecular H-bond formed by the primary
amino group in 2. According to calculations and in analogy with the
spectrum of solution of 1b, a wide intense band at 3347 cmꢀ1 is due
to the stretching vibrations nsNH2 and nNH of the amide groups, and
the lowest frequency band at 3293 cmꢀ1 corresponds to the nNH
vibrations of the sulfonamide group, which forms the shortest H-
bond. In the calculated spectra of molecule 2a and its molecular
ancestor oxamide 5, the inversion of asymmetric and symmetric
stretching vibrations of the carbonyl groups occurs, and it is
reflected in the IR and Raman spectra of the solid samples. The high
frequency band appears in the Raman spectrum at 1713 (for 2b) and
No BCP corresponding to the NH/O hydrogen bond was found
for oxamide 5, as distinct from its thio analog 6, which has two
identical BCPs the two NH/S hydrogen bonds. There is good cor-
relation between the r
(rc) and V2r(rc) values and the NH/X dis-
tances, which, in turn, correlate well with the corresponding nNH
frequencies. Positive values of Laplacian V2r(rc) in Table 2 are in-
dicative of depletion of electronic charge along the bond path,
which is characteristic of closed shell interactions such as hydrogen
bonds. The penultimate column in Table 2 shows the hydrogen
1703 cmꢀ1 (for 5) and belongs to the ns
vibrations. The nas
C]O
C]O
bond energies calculated similar to20
:
vibration band in the IR spectra of solid compounds 2b and 5 ap-
pear at 1661 and 1652 cmꢀ1, respectively, whereas in the solution of
EH/X ¼ 1=2Vc; Vc ¼ 1=4V2rðrcÞ ꢀ 2Gc
2b the frequency of nas
is equal to 1706 cmꢀ1
.
C]O
The molecular structure of [(1-phenylsulfonylamino-2,2,2-tri-
chloro)ethyl]dithiooxamide 3a is similar to that of its oxamide
analog 2a (Fig. 1) with the two five-membered rings closed by the
NH/S]C hydrogen bonds and one six-membered ring closed by
the NH/S]C hydrogen bond. The difference between compound
2a and its dithio analog 3a is that, while for 2a the N4H4/O2 is the
shortest hydrogen bond in the molecule, for 3a the H-bond
N4H4/S2 is the longest one (Fig. 1). Moreover, introduction of the
CH(CCl3)NHSO2Ar moiety into the molecule of oxamide 5 leads to
elongation of the N1H1/O2 H-bond and contraction of the
N2H2/O1 H-bond, while for dithiooxamide 6 it results in con-
traction of both the N1H1/S2 and N2H2/S1 H-bonds. This is
reflected in the order of the experimental nNH frequencies (Table 1).
To conclude this section, a general remark should be made, that
in spite of much lower pKa values for sulfonamides relative to the
where Vc is the local potential electron energy density and Gc is the
local kinetic electron energy density. Finally, the last column gives
the ratio ꢀGc/Vc, which was used as a criterion of the nature of H-
bond:20,21 for ꢀGc/Vc>1 the H-bond is noncovalent, while for
0.5<ꢀGc/Vc<1 it is partly covalent.
As can be seen, in practically all cases the H-bonds in the sys-
tems under consideration are noncovalent, their values being very
close to those obtained for NeH/O]C H-bonds.20 The only ex-
ception is the N2H2/S1 H-bond in 3a, which has a small covalent
contribution. This is consistent with the largest value of EH/X for
this H-bond in 3a, as well as with the strongest interaction
nS1
/s
*
found by the NBO analysis (vide infra).
N2eH2
The abovementioned absence of BCP in 5 and its presence in 6 is
presumably caused by two factors. First, the thiocarbonyl group is
much more basic than the carbonyl group due to the lower

B.A. Shainyan et al. / Tetrahedron 66 (2010) 8551e8556
8555
electronegativity and higher polarizability of sulfur versus oxy-
gen.22 Second, although the H/O distance in 5 is 0.13 Å shorter
than the H/S distance in 6, it is only 0.34 Å less than the sum of the
vdW radii of H and O atoms, whereas the latter distance is 0.64 Å
less than the sum of the vdW radii of H and S atoms.
In 2a, the values of E(2) for the nO1
/s N2eH2 and nO2/s
* *
N1eH1
interactions are 7 and 15 times, respectively, less than in biuret 1a
(Table 3). The only more or less significant interaction is the one
with the sulfonamide NH group (3.74 kcal/mol). This is consistent
with the results of the AIM analysis, which finds only one BCP in 2a
belonging to the N4H4/O2 H-bond. Nonvalent interactions in the
model compound 5 are practically negligible, which is also in line
with the absence of the corresponding BCPs (vide supra).
2.4. NBO analysis
On the example of formamides, ureas, biuret, isocyanates, and
their thio analogs, the electron delocalization through covalent
bonds in thioamides was shown to be more efficient than in am-
The NBO method was used for quantitative analysis of the elec-
tron delocalization from the lone pairs of the nitrogen and oxygen
atoms to the adjacent antibonding
p
*
and
*
s -orbitals (Table 3).
ides, which was assigned to lower values of DEij and larger matrix
As an independent characteristic of the NH/X hydrogen bond
energy we have analyzed the second-order interaction energies E(2)
between the donor orbitals (lone pairs on X) and acceptor orbitals
elements of the Fockian Fij determining E(2) by equation E(2)¼ꢀ2Fij/
D
Eij.5,23 As follows from the AIM and NBO analysis of compounds
1e6, the same is true for the noncovalent hydrogen bonding in-
teractions. The NBO analysis clearly shows (Table 3) that all three
(
s
NeH) forming the hydrogen bond. In 1a, the value of E(2) for the
*
nO1
/s
*
orbital interaction (10.84 kcal/mol) is notably larger
N2eH2
such interactions in 3a, nS1
/s
*
,
nS2
/s
*
,
and
N2eH2
N1eH1
than that in biuret 4 (6.82 kcal/mol). This is presumably due to the
electroneacceptor effect of the CH(CCl3)NHSO2Ph substituent since
the positive NBO charge on H2 increases on going from biuret 4 to
molecule 1a by 0.021ꢁ0.001 e, thus favoring the N2H2/O1 H-bond
formation. The N4H4/O2 H-bond in 1a is characterized by much
lower value of E(2) (4.70 kcal/mol) than the N2H2/O1 Hebond. The
NBO charge on H4 is 0.008 e more positive than that on H2.
Therefore, the main reason for the weaker N4H4/O2 relative to the
N2H2/O1 H-bond lies in different geometry of the two H-bonded
rings. The ring that includes the amide NH group is planar since all
the constituting atoms are sp2 hybridized. The presence of the sp3
hybridized CH atom in the ring formed with participation of the
sulfonamide NH group leads, first, to the lengthening of the cor-
responding NeCH bonds and, second, to nonplanarity of the ring
and deviation of the NH group from the plane of the remaining four
atoms. As a result, the N4H4/O2 H-bond becomes 0.192 Å longer
(and, hence, weaker) than the N2H2/O1 H-bond.
nS2 N4eH4, are much more efficient than the corresponding
orbital interactions in 2a, and the AIM analysis finds three BCPs
corresponding to H-bonds in 3a and only one in 2a.
/
*
s
3. Conclusions
The experimental and theoretical study of hydrogen bonding in
compounds 1e3 has shown them to be strong NH acids due to the
presence of the sulfonamide group with the pKa values in meth-
anol of 11e12 units. They are also capable of forming intra-
molecular hydrogen bonds due to both the amide and the
sulfonamide NH group with the carbonyl or thiocarbonyl group.
The relative stability of these H-bonds depends on the structure of
the centers of basicity in the molecule. For example, in compound
2a, the sulfonamide group forms the shortest (and strongest) H-
bond, whereas in compounds 1a and 3a it is the longest (and
weakest) one. The AIM analysis showed that all H-bonds in mol-
ecules 1ae3a are noncovalent, except the N2H2/S1 H-bond in 3a,
which has a small covalent contribution. No BCP corresponding to
the NH/O H-bond was found for oxamide 5, whereas for more
basic dithiooxamide 6 each of the two NH/S H-bonds has BCP.
The NBO analysis method showed that the second-order C]
X/HN (X¼O, S) interaction energy E(2), which is an independent
characteristic of the NH/X H-bond energy, vary from 0.7 to
11.6 kcal/mol and correlate well with the hydrogen bond energies
predicted by the AIM analysis and with the experimental FT-IR
spectroscopy data.
Table 3
Second order perturbation energies E(2) (kcal molꢀ1) for orbital interactions related
to hydrogen bond formation in molecules 1e6
Molecule
Interaction
E(2)
1a
nN1
nN2
nN3
nN3
nO1
nO2
/
/
/
/
/
/
p
p
p
p
s
s
*
*
*
*
26.01
65.82
44.50
34.15
10.84
4.70
C1eO1
C2eO2
C2eO2
C1eO1
N2eH2
N4eH4
*
*
2a
3a
4
nN1
nN2
nO1
nO2
nO2
/
/
/
/
/
p
p
s
s
s
*
69.15
70.71
1.63
0.69
3.74
C1eO1
C2eO2
N2eH2
N1eH1
N4eH4
4. Experimental section
*
*
*
*
4.1. General
Compounds 1be3b were synthesized by addition of biuret,
nN1
nN2
/
p
p
*
88.76
91.98
11.63
4.74
C1eO1
C2eO2
/
*
oxamide,
and
dithiooxamide
to
4-chloro-N-(2,2,2-tri-
chloroethylidene)benzenesulfonamide p-ClC6H4SO2N]CHCCl3.12
nS1
nS2
nS2
/
/
/
s
s
s
*
N2eH2
N1eH1
N4eH4
*
*
5.78
4.2. IR experiments
nN1
nN2
nN3
nN3
nO1
/
/
/
/
/
p
p
p
p
*
8.08
62.62
42.32
28.40
6.82
C1eO1
C2eO2
C2eO2
C1eO1
N2eH2
*
*
*
The FT-IR spectra were recorded on a portable diamond ATR/FT-
IR (RAM II) Spectrometer Varian 3100. The potentiometric acidity of
compounds 1be3b was measured by titration with 0.1 M NaOH
solution in methanol.
s
*
5
6
nN1
nN2
nO1
nO2
/
/
/
/
p
p
s
s
*
68.53
68.53
0.80
C1eO1
C2eO2
N2eH2
N1eH1
*
*
*
4.3. Computational details
0.80
All calculations were performed by the DFT method using the
B3LYP exchange correlationpotential and the 6-311þG(d,p) basis set
as implemented in the Gaussian03 program package.24 All calcu-
lated structures correspond to minima on the potential energy
nN1
nN2
/
p
p
*
87.80
87.80
5.11
C1eO1
C2eO2
/
*
nS1
nS2
/
s
s
*
N2eH2
N1eH1
/
*
5.11

8556
B.A. Shainyan et al. / Tetrahedron 66 (2010) 8551e8556
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Hessian matrices. All energies were calculated with the ZPE cor-
rection. The AIM analysis25 was performed by the use of the
AIM2000 program (version 2.0)26 with the wave function taken
from the MP2/6-311þþG** single point calculations. The NBO
analysis27 as implemented into the Gaussian03 package was per-
formed using the 6-311þG** basis set on the previously DFT opti-
mized structures. The van der Waals radii of H¼1.20 Å, O¼1.40 Å,
and S¼1.85 Å are used in the discussion.
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Levkovskaya, G. G. Russ. J. Org. Chem. Engl. Transl. 2008, 44, 1486 Compounds 2b
and 3b were prepared similarly; for synthetic details, see Supplementary data.
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14. Sterkhova, I. V.; Meshcheryakov, V. I.; Chipanina, N. N.; Kukhareva, V. A.;
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Acknowledgements
ꢀ
We thank V.A. Kukhareva (Irkutsk Institute of Chemistry) for
potentiometric titration of compounds 1be3b.
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Supplementary data
21. Zió1kowski, M.; Grabowski, S. J.; Leszczynski, J. J. Phys. Chem. A 2006, 110, 6514.
22. Abboud, J.-L. M.; Mó, O.; de Paz, J. L. G.; Yáñez, M.; Esseffar, M.; Bouab, W.;
El-Mouhtadi, M.; Mokhlisse, R.; Ballesteros, E.; Herreros, M.; Homan, H.;
Lopez-Mardomingo, C.; Notario, R. J. Am. Chem. Soc. 1993, 115, 12468.
23. Bharatam, P. V.; Moudgil, R.; Kaur, D. J. Phys. Chem. A 2003, 107, 1627.
24. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Montgomery, J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.;
Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.;
Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.;
Toyota, K.; Fukuda, R.; Nasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
Farkas, O.; Malik, D. K.; Rabuk, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J.
V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.;
Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.;
Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.;
Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 2003;
Gaussian: Pittsburg, 2003.
Supplementary data includes synthetic details, NMR and IR
spectra of the products, total energies, and optimized geometries of
compounds 1e6. Supplementary data associated with this article
can be found in online version at doi:10.1016/j.tet.2010.08.076.
These data include MOL files and InChIKeys of the most important
compounds described in this article.
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