Structure of methyl 3-(trimethylammonium)benzoate iodide studied by X-ray diffraction, DFT calculations, NMR and FTIR spectra

Article abstract of DOI:10.1016/j.molstruc.2012.02.051

The structure of methyl 3-(trimethylammonium)benzoate iodide, 3-(Me) ₃N⁺C₆H₄CO₂MeI ^-, (1a) has been determined by X-ray diffraction, DFT calculations and characterized by FTIR and NMR spectroscopy. The crystals are orthorhombic, space group Pnma and the structure is stabilized by interaction of I anion with the N, O(1) and O(2) atoms. The N?I distances vary between 4.541(3) and 7.752(3) ?. The correlation between the atomic distances and the Mulliken atomic charges is linear. Charge on the quaternary nitrogen atom depends on options used for generating electrostatic potential-derived charges. The interpretation of ¹H and ¹³C NMR spectra in DMSO-d ₆ has been based on 2D experiments and calculated GIAO/B3LYP/6-311G(d,p) magnetic isotropic shielding constants. The FTIR spectrum of the solid compound is consistent with the X-ray results. The probable assignments of the anharmonic experimental vibrational frequencies of the investigated ester (1a) based on the calculated harmonic frequencies are proposed.

Full text of DOI:10.1016/j.molstruc.2012.02.051

Journal of Molecular Structure 1017 (2012) 115–122
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Structure of methyl 3-(trimethylammonium)benzoate iodide studied by X-ray
diffraction, DFT calculations, NMR and FTIR spectra
⇑
M. Szafran, A. Katrusiak, I. Kowalczyk , A. Komasa, Z. Dega-Szafran
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60780 Pozna n´ , Poland
a r t i c l e i n f o
a b s t r a c t
+
À
Article history:
3 6 4 2
The structure of methyl 3-(trimethylammonium)benzoate iodide, 3-(Me) N C H CO MeI , (1a) has been
Received 28 December 2011
Received in revised form 21 February 2012
Accepted 21 February 2012
Available online 14 March 2012
determined by X-ray diffraction, DFT calculations and characterized by FTIR and NMR spectroscopy. The
crystals are orthorhombic, space group Pnma and the structure is stabilized by interaction of I anion with
the N, O(1) and O(2) atoms. The NÁ Á ÁI distances vary between 4.541(3) and 7.752(3) Å. The correlation
between the atomic distances and the Mulliken atomic charges is linear. Charge on the quaternary nitro-
gen atom depends on options used for generating electrostatic potential-derived charges. The interpreta-
Keywords:
1
13
6
tion of H and C NMR spectra in DMSO-d has been based on 2D experiments and calculated GIAO/
Methyl 3-(trimethylammonium)benzoate
iodide
X-ray diffraction
B3LYP calculations
FTIR and NMR spectra
B3LYP/6-311G(d,p) magnetic isotropic shielding constants. The FTIR spectrum of the solid compound is
consistent with the X-ray results. The probable assignments of the anharmonic experimental vibrational
frequencies of the investigated ester (1a) based on the calculated harmonic frequencies are proposed.
Ó 2012 Elsevier B.V. All rights reserved.
1
. Introduction
Zwitterions are compounds with oppositely charged centers
2. Experimental and calculations
2.1. Synthesis
and are often referred to as betaines, dipolar ions, salt-bridged-
containing molecules, and inner salts. This diverse nomenclature
reflects the extraordinary importance of these species in biological
transformations, organic synthesis, the preparation of novel mate-
rials, and as chromatographic supports [1–3].
A solution of 3-(dimethylamino)benzoic acid (15 g) in methanol
(70 cm ) and methyl iodide (30 g) was heated at 70 °C in a sealed
3
tube for 40 h. Yellow crystals were filtered off and washed with
small amount of acetone. The filtrate was evaporated to dryness
under reduced pressure and the solid residue was washed with
acetone. Both fractions of the crystals were combined and recrys-
tallized from methanol, total yield 65 %, m.p. 210 °C, 220–221 °C
Ref. [6].
An interesting group of compounds of this type are ortho- meta-
and para-N,N,N-trimethylammoniumbenzoates (benz-betaines),
+
À
(
CH
In the pyrolysis electron impact (EI) mass spectrometry
experiment on N,N,N-trimethylammoniumalkanocarboxylates
3 3 6 4
) N AC H ACOO , their salts and esters [4–6].
+
À
(
Me
cott [7] have observed the methyl transfer to more volatile methyl
esters (Me NA(CH COOMe). Quaternization of N,N-dimethyla-
3 2 n
N A(CH ) COO ) and their hydrochlorides, Wood and Colla-
2
.2. Measurements
2
2 n
)
The X-ray diffraction measurements were carried out on a
minobenzoic acids by an excess of methyl iodide in methyl alcohol
depends on temperature and time of refluxing [6]. In N,N,N-trime-
thylammoniumbenzoic acid hydroiodide, heating triggers methyl
transfer and methyl N,N-dimethylaminobenzoate hydroiodide is
KUMA KM4-CCD diffractometer [11,12]. The structure of 1a was
solved by direct methods with the SHELXS-97 and refined on F2
full-matrix least-squares with SHELXL-97 [13]. All hydrogen atoms
were calculated from the molecular geometry and their isotropic
displacement parameters were based on Ueq of their carriers. The
crystal data, together with the details concerning data collection
and structure refinement are given in Table 1 and the atomic coor-
dinates in Table A in Supplementary material. The experimental
and the calculated bond lengths, bond angles, and selected torsion
angles are summarized in Table 2. The crystal data and atomic
parameters in the CIF form are available as Electronic Supplemen-
tary Information from the Cambridge Crystallographic Database
Center (CCDC 859169). Molecular illustrations were prepared
using ORTEPII [14] and XP [15] programs.
formed (Me NAC H
2 6 4
ACOOMeÁHI).
Recently, we have described the structures of methyl 4-(trime-
thylammonium)benzoate iodide [8], 4-(trimethylammonium)ben-
zoic acid chloride [9] and 4-(trimethylammonium)benzoate [10].
In this paper, we report the crystal structure and spectroscopic
properties of methyl 3-(trimethylammonium)benzoate iodide
(
m-carboxymethoxyphenyltrimethylammonium iodide) (1a).
⇑
Corresponding author. Tel.: +48 61 8291306; fax: +48 61 8291505.
E-mail address: iwkow@amu.edu.pl (I. Kowalczyk).
0
022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.02.051

1
16
M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
Table 1
Table 2
Crystal data and structure refinement for methyl 3-(trimethylammonium)benzoate
iodide (1a).
Experimental (X-ray) and calculated by the B3LYP/6-311G(d,p) method bond lengths
(Å), bond and torsion angles (deg.) for methyl 3-(trimethylammonium)benzoate
iodide.
Empirical formula
Formula weight
Temperature
11 2
C H16INO
290.07
293(2) K
0.71073 Å
X-ray
B3LYP
1a
1b (vacuum)
1c (DMSO)
Wavelength
Crystal system
Space group
Orthorhombic
Pnma
Bonds
O(1)AC(7)
O(1)AC(11)
O(2)AC(7)
C(1)AC(2)
C(1)AC(6)
C(1)AC(7)
C(2)AC(3)
C(3)AC(4)
C(4)AC(5)
C(5)AC(6)
N(1)AC(3)
N(1)AC(8)
N(1)AC(9)
N(1)AC(9A)
1.334(16)
1.447(18)
1.197(17)
1.405(17)
1.345(18)
1.490(20)
1.352(18)
1.370(19)
1.410(20)
1.441(19)
1.508(15)
1.508(18)
1.525(14)
1.525(14)
1.3336
1.4400
1.2128
1.4032
1.3923
1.4959
1.3820
1.3999
1.3872
1.3962
1.5180
1.5049
1.5117
1.5117
1.3365
1.4448
1.2128
1.3998
1.3941
1.4949
1.3854
1.3963
1.3902
1.3916
1.5080
1.5080
1.5148
1.5151
Unit cell dimensions
a = 12.2502(5) Å
b = 7.0998(4) Å
c = 14.8763(7) Å
3
Volume
Z
Calculated density
Absorption coefficient
F(000)
1293.85(11) Å
4
3
1.489 g/cm
2.450 mm
À1
556
Crystal size
0.09 Â 0.06 Â 0.05 mm
h range for data collection (°)
Max/min. indices h, k, l
Reflections collected/unique
2.15–26.51
À11/15, À8/8, À18/18
8260/1440 [R(int) = 0.0989]
26.51/99.1
h
Max(°)/Completeness (%)
Absorption correction
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
None
Angles
Full-matrix least-squares on F2
1440/0/85
O(1)AC(7)AC(1)
O(2)AC(7)AC(1)
O(1)AC(7)AO(2)
C(1)AC(2)AC(3)
C(1)AC(6)AC(5)
C(2)AC(3)AC(4)
C(2)AC(1)AC(7)
C(2)AC(1)AC(6)
C(2)AC(3)AN(1)
C(6)AC(1)AC(7)
C(3)AC(4)AC(5)
C(4)AC(3)AN(1)
C(4)AC(5)AC(6)
C(3)AN(1)AC(8)
C(3)AN(1)AC(9)
C(8)AN(1)AC(9)
C(9)AN(1)AC(9A)
C(7)AO(1)AC(11)
112.3(12)
124.4(13)
123.2(14)
118.8(11)
120.5(13)
122.8(12)
117.7(12)
120.9(13)
120.5(11)
121.4(12)
119.6(13)
116.8(12)
117.3(12)
112.4(10)
109.8(7)
112.12
123.42
124.46
118.89
119.70
121.23
116.14
120.50
120.81
123.36
119.31
117.93
120.33
112.62
109.50
107.74
109.68
102.02
112.34
123.74
123.92
119.38
119.53
120.75
116.98
120.35
121.08
122.67
119.41
118.17
120.59
112.80
109.60
107.59
109.59
116.38
1.085
Final R indices [I > 2
R1/R2 indices (all data)
Largest diff. peak and hole
r
I
]
R1 = 0.0376, wR2 = 0.0836
0.0490/0.0902
3.804 and À1.210 e Å
À3
FTIR spectra were recorded in Nujol and Fluorolube mulls on a
Bruker IFS 66v/S spectrometer, evacuated to avoid water and CO
absorptions, at 2 cm resolution. Each FTIR spectrum was mea-
sured by acquisition of 64 scans.
2
À1
NMR spectra were recorded on a Bruker Avance DRX spectrom-
eter operating at 599.93 and 150.85 MHz for 1H and 13C, respec-
6
tively. The spectra were measured in DMSO-d solution relative
107.4(7)
109.8(13)
116.8(12)
1
1
1
13
a
to TMS. The 2D H– H (COSY), H– C (HETCOR) and Heteronuclear
Multiple-Bond Connectivity (HMBC) spectra were obtained with
the standard Bruker software.
Selected torsion angles
C(1)AC(7)A O(1)AC(11)
C(2)AC(1)AC(7)AO(1)
C(6)AC(1)AC(7)AO(1)
C(2)AC(1)AC(7)AO(2)
C(6)AC(1)AC(7)AO(2)
C(2)AC(1)AC(6)AC(5)
C(3)AC(4)AC(5)AC(6)
C(2)AC(3)AN(1)AC(8)
C(4)AC(3)AN(1)AC(8)
C(2)AC(3)AN(1)AC(9)
C(4)AC(3)AN(1)AC(9)
C(2)AC(3)AN(1)AC(9A)
C(4)AC(3)AN(1)AC(9A)
C(1)AC(2)AC(3)AC(4)
C(1)AC(6)AC(5)AC(4)
180
180
0
0
180
0
0
0
180
À119.6(2)
60.4(2)
119.6(7)
À60.4(7)
0
À179.99
180.00
0.01
179.77
À179.64
0.37
2
.3. Calculations
0.00
0.11
The optimization of geometrical parameters was performed
À179.99
À179.89
using the Gaussian 03 program package [16]. The X-ray geometry
of 1a was used as a starting point of calculations. The calculations
employed the hybrid B3LYP exchange–correlation functional,
which combined the exchange functional of Becke [17,18] with
the gradient-correlation functional of Lee et al. [19] approach in
conjunction with the 6-311G(d,p) basis set [20]. The basis set for
iodine is not available in the standard set of basis functions offered
by the Gaussian 03 program. Therefore it has been fetched from the
EMSL Basis Set Library [21,22], where the 6-311G(d,p) basis set
created by Glukhovtsev et al. [23] is provided.
0.00
0.22
À0.004
0.02
À0.15
À1.07
178.88
118.77
178.88
À120.93
59.02
179.98
119.99
À60.13
À119.83
60.16
0.01
0.003
À0.01
0
À0.05
a
Symmetry code: x, Ày + 0.5, z.
The conductor like-screening solvation model, COSMO [24–26]
+
À
3 6 4 2
was applied to calculate the structure of 3-(Me) N C H CO MeI
of isolated molecule and in DMSO. The magnetic isotropic shielding
constants were calculated using the standard GIAO/B3LYP/6-
3
11G(d,p) (Gauge-Independent Atomic Orbital) approach with
the Gaussian 03 program package using COSMO model [24–26].
3
. Results and discussion
3.1. Molecular parameters
The molecular structure and atom numbering of 3-
N+C
MeI are shown in Fig. 1, while a projection of
À
(
Me)
3
6 4
H CO
2
the crystal structure viewed in perpendicular to the layers formed
of the ions is in Fig. 2. A view of the structure along the sheets of
ions is presented in Fig. 3. The crystal structure of 1a can be
Fig. 1. The asymmetric unit of the crystal structure of methyl 3-(trimethylammo-
nium)benzoate iodide (1a). Thermal ellipsoids have been drawn at the 50%
probability level.

M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
117
described as built of layers of cations and I anions lying in mirror
planes perpendicular to the y-axis (Fig. 2). Additionally it is appar-
ent that the cohesion forces in this crystal are controlled in nature
by relatively short NÁ Á ÁI and NÁ Á ÁO distances (Table 3). Within the
layers each cation forms three CHÁ Á ÁI contacts to three I anions,
and two contacts CHÁ Á ÁI to the anions in neighboring layers (Ta-
ble 4). Of these five CHÁ Á ÁI contacts, two are formed by the ring
hydrogen, C(4)H and C(6)H, and the remaining three by methyl
The optimized structures (1b in vacuum and 1c in DMSO) are
compared to that determined by X-ray analysis in Fig. 4. The
calculated bond lengths, bond angles, and selected torsion angles
are summarized in Table 2. In the crystals the COOMe group is
in plane of the benzene ring (C(2)AC(1)AC(7)AO(1) = 180°,
C(2)AC(1)AC(7)AO(2) = 0°). In the optimized structure the confor-
mation of the cation is also planar (Table 2). In crystal (1a) the an-
ion I is engaged in contacts with the nitrogen atoms; the NÁ Á ÁI
distances are 4.451(3), 4.599(3), 4.795(3) and 7.752(3) Å. The other
contacts in 1a are between I anion and oxygen atoms (Table 3). The
relation between NÁ Á ÁI and OÁ Á ÁI distances and the Mulliken atomic
charges is linear (Fig. 5).
3
hydrogen atoms, all of methyl C(8)H . Thus I anion is fivefold coor-
dinated in the form of pseudo-trigonal bipiramid. Another type of
short contacts is C(11)AH(11A)Á Á ÁO(2), involving methoxy atoms
(Table 4).
Fig. 2. Autostereographic projection [45] of the crystal structure of methyl 3-(trimethylammonium)benzoate iodide (1a) viewed perpendicular to the layers formed of the
ions.
Fig. 3. An autostereogram along the sheets of ions (cf. Fig. 2).

1
18
M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
Table 3
Energies (Hartree, a.u.), dipole moments (
l
, Debye), the shortest intermolecular contacts and atomic charges for methyl 3-(trimethylammonium)benzoate iodide.
Compounds
Energy
l
NÁ Á ÁI
O(1)Á Á ÁI
O(2)Á Á ÁI
Atomic charge
I
N
O(1)
O(2)
X-ray
a
4.794(2)d
5.038(2)
4.971(2)e
6.953(2)
1
a
4.541)(3)
b
c
4
.599(3)
.795(3)
4
B3LYP/6-311G(d,p)
b (vacuum)
Mulliken atomic charge
NPA
MK
7.752(3)
7.400
1
À7553.65520995
À7553.73668195
25.8758
35.4759
5.312
5.849
7.087
7.728
À0.8524
À0.9167
À0.8346
À0.7810
À0.3892
À0.3069
0.1174
À0.3074
À0.5157
À0.2225
À0.3385
À0.3659
À0.6187
À0.5525
À0.5393
CHELPG
0.1193
1
c (DMSO)
8.162
Mulliken atomic charge
À0.988
À0.3948
À0.3134
0.0712
À0.3301
À0.5333
À0.3048
À0.4291
À0.3894
À0.6353
À0.5999
À0.5793
NPA
MK
CHELPG
À0.9964
À1.0013
À0.9418
0.0960
Symmetry codes:
a
x À 1, y, z;
b
1
À x, Ày, 1 À z;
c
d
e
x À 0.5, y, 0.5 À z;
0
1
.5 À x, Ày, z À 0.5;
À x, Ày, 1 À z;
Table 4
The closest CHÁ Á ÁI contacts in methyl 3-(trimethylammonium)benzoate iodide (Å and deg.).
DAHÁ Á ÁA
d(DAH)
d(HÁ Á ÁA)
d(DÁ Á ÁA)
<(DAHÁ Á ÁA)
a
C(4)AH(4)Á Á ÁI(1)
C(5)AH(5)Á Á ÁI(1)
C(6)AH(6)Á Á ÁI(1)
0.93
0.93
0.93
0.96
0.96
0.96
0.96
3.04
3.39
3.25
3.29
3.08
3.02
2.63
3.958(12)
3.992(12)
3.932(13)
4.090(14)
4.029(14)
4.029(14)
3.582(5)
170.9
124.7
132.2
142.6
168.8
170.3
170.4
b
C(11)AH(11BÁ)ÁÁI(1)
c
C(8)AH(8A)Á Á ÁI(1)
d
C(8)AH(8B)Á Á ÁI(1)
e
C(11)AH(11A)Á Á ÁO(2)
Symmetry codes:
a
0
1
2
1
0
.5 + x, 0.5 À y, z;
.5 À x, 0.5 + y, Àz;
À x, 1 À y, Àz;
+ x, y, z;
b
c
d
e
.5 + x, 1.5 À y, z.
The Natural Population Analysis (NPA) and Mulliken charges
molar properties such as dipole moments, shows that the
charge of the nitrogen atom is positive (Table 3). A similar
charge distribution on the nitrogen atom was observed in
betaine [27].
on the nitrogen atom are negative. On the other hand, fitting
the electrostatic potential according to MK (MertzKollman) and
CHELPG schemes, which are directed to accurately produce
Fig. 4. Comparison of X-ray (1a) and B3LYP (1b–1c) structures of methyl 3-(trimethylammonium)benzoate iodide.

M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
119
8
8
7
7
6
6
5
.5
.0
.5
.0
.5
.0
.5
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
-
0.40
-0.38
-0.36
-0.34
-0.32
-0.30
Mulliken atomic charges
Fig. 5. Correlation between NÁ Á ÁI, O(1)Á Á ÁI and O(2)Á Á ÁI distances (Å) with the
Mulliken atomic charges; d(NÁI, O(1)ÁI, O(2)ÁI) = À4.0291 À 30.1876 M(e), r = 0.9843
in vacuum and DMSO solution.
8.4
8.5
8.6
8
.5
8.3
8.1
ppm
7.9
7.7
Table 5
Experimental (dexp in DMSO-d
6
) and predicted (dpred = a + b rcalc, in DMSO) carbon-13
and proton chemical shifts, and calculated GIAO/B3LYP/6-311G(d,p) isotropic mag-
Fig. 6. 1H– H COSY spectrum of methyl 3-(trimethylammonium)benzoate iodide
1
netic shielding constants (rcalc) for methyl 3-(trimethylammonium)benzoate iodide.
(
1a) in DMSO-d
6
.
Atom
d
exp
d
pred
r
calc
1
a
1c
1c
Carbon-13
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
Orbitals (GIAO) magnetic isotropic shielding constants (
which are widely used [29–32], are usually linear and described
by the equation dexp = a + b calc. The slope and intercept of the
least-square correlation lines are used to scale the GIAO isotropic
absolute shielding constants , and to predict chemical shifts in
DMSO for 1c (Fig. 8, Table 5). As shown in Table 5, the agreement
between the experimental and calculation data is satisfactory, both
for 13-carbon and hydrogen atoms.
rcalc),
131.26
121.06
147.43
130.54
130.77
125.47
165.0
130.80
118.53
145.72
125.27
132.70
132.63
163.90
55.29
46.4878
59.2775
30.9508
52.2495
44.5101
44.5866
12.0097
125.1609
128.0769
175.4223
À0.9598
0.9960
r
r
C(8)AC(10)
C(11)
56.38
52.74
52.49
a
a
b
b
c
r
3.3. FTIR spectra
d
Av. dif.
0.37
3.42
R.m.se
Proton
H(2)
The solid-state and calculated IR spectra of 3-
N+C
H
MeI are shown in Fig. 9. The intense band at
À
8.43
8.31
7.82
8.14
3.93
3.67
8.15
7.99
8.14
8.37
4.12
3.53
23.5046
23.6694
23.5114
23.2598
27.8579
28.4952
29.9009
À0.9255
0.9923
(Me)
1
4
CO
3
6
2
H(4)
H(5)
H(6)
À1
714 cm arises from the mC@O vibration. Table 6 lists the exper-
imental and calculated frequencies, and intensities for normal
modes in the optimized molecule 1b. The comparison of calculated
and experimental frequencies shows typical differences. Two rea-
sons may be responsible for the differences between the experi-
mental and computed spectra of the molecule investigated. The
first is that the experimental spectrum was recorded for complex
1a in the solid state, while the computed spectrum refers to the
isolated molecule 1b in the gas phase. The second reason is that
the experimental results are anharmonic vibrations, while the cal-
culated values are harmonic ones. Similar discrepancies between
the calculated and experimental frequencies have been noted for
OCH
3
av
av
NCH
3
a
a
b
b
c
r
d
Av. dif.
0.04
0.30
R.m.sf
a
b
c
Intercept.
Slope.
Correlation coefficient.
d
Average (signed) differences between experimental and predicted chemical
shifts.
4
-(trimethylammonium)benzoate iodide [8]. The overestimation
f
Root-mean-square errors.
of the computed wavenumbers is quite systematic and can be cor-
rected by applying appropriate scaling factors or scaling equations
[
33–41]. Fig. 10 shows a linear relation between the experimental
1
13
3
.2. H and C NMR spectra
and calculated frequencies, characterized by a good correlation
coefficient. The scaling procedure, recommended by Alcolea Pala-
fox [36] was used. The scaled IR spectrum is shown in Fig. 9b
and the predicted frequencies are listed in Table 6 as mscaleq. Scaling
of the harmonic vibrational frequencies reproduced the
The assignments of proton and carbon-13 chemical shifts for 3-
+
À
(
Me)
3
N C
6
H
4
CO
2
MeI , listed in Table 5, were based on two dimen-
1
1
1
13
sional H– H, H– C experiments (Figs. 6 and 7). Additionally, the
1
13
H– C HMBC spectrum (Fig. 7) shows a three bond correlation
between the C@O carbon atoms and C(2)H, C(6)H, C(11)H protons
in compound 1a [28]. The relation between the experimental
and 1H chemical shifts (dexp) and the Gauge Including Atomic
experimental solid-state FTIR frequencies with the r.m.s.
À1
3
error of 57.8 cm
3-(Me) CO
N+C
visualization program [42] and data [43,44].
. The vibrational band assignments of
1
3
À
C
3
H
6 4
2
MeI were made using Gauss-View molecular

1
20
M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
Fig. 7. 1H–13C HMBC spectrum of methyl 3-(trimethylammonium)benzoate iodide (1a) in DMSO-d
6
.
180
160
140
120
100
10
9
a
b
8
7
6
8
6
4
0
0
0
5
4
3
0
20 40 60 80 100 120 140
23
24
25
26
27
28
29
Magnetic isotropic shielding constants
Fig. 8. Plots of the experimental chemical shifts (dexp) in DMSO-d
6
vs. the magnetic isotropic shielding constants (rcalc) from the GIAO/B3LYP/6-311G(d,p) calculated for
methyl 3-(trimethylammonium)benzoate iodide in DMSO-d
6
; dexp = a + brcalc; (a) carbon-13, (b) proton.
a
1
1
0
0
.5
.0
.5
.0
b
8
0
0
0
0
0
6
4
2
3
000
2500
2000
1800
1600
1400
1200
1000
800
600
400
Wavenumbers/cm-1
Fig. 9. Vibrational spectra of methyl 3-(trimethylammonium)benzoate iodide: (a) solid-state FTIR spectrum; (b) calculated and scaled IR spectrum by the B3LYP/6-311G(d,p)
approach for 1b.

M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
121
Table 6 (continued)
a
b
Assignmentsc
CH
bRing
3
2
1
000
000
000
0
m
exp
m
cal
A
cal
m
scaleq
9
9
9
85w
58w
41w
998
975
963
949
912
873
829
8
776
745
692
668
573
563
519
470
444
424
38.08
0.34
14.76
20.23
1.71
38.72
44.11
3.75
31.73
9.07
11.03
3.51
12.77
1.16
7.12
1.19
1003
982
971
958
924
888
847
844
798
770
721
699
611
602
561
516
492
474
c
3
c
c
c
c
c
c
s
s
s
s
CH +
OCH
swCOO
3
+
c
CH
3
8
8
8
85vw
74m
22w
CH
CH
CH
CH
3
26
3
+ cOCH
3
7
7
7
6
55m
Ring
Ring +
Ring
42vw
39vw
83w
635vw
72vw
561vw
18vw
cCH
Ring + c
CH
bRing
0
1000
2000
3000
5
bRing +
bRing +
c
c
CH
CN
-1
Calculated frequencies by B3LYP/6-311G(d,p), cm
5
s
s
s
Ring +
Ring +
Ring +
cCN
cCN
cCN
À1
Fig. 10. Correlation between the experimental and calculated wavenumbers (cm
for methyl 3-(trimethylammonium)benzoate iodide; scaled = 82.5544 + 0.9223
calc., r = 0.9976.
)
469vw
420vw
0.09
0.10
m
d
m
Av.
À39.11
À0.018
e
R.m.s.
91.05
57.81
a
b
c
Intensity: s – strong, m – medium, w – weak, vw – very weak.
Scaling equation: scaleq = 82.5544 + 0.9223 cal; r = 0.9976.
as – asymmetric, s – symmetric, – stretching, d – deformation,
– out-of-plane bending or wagging, w – twisting, bRing –
Ring – ring torsion.
Table 6
m
m
Experimental (solid state) and calculated vibrational data for methyl 3-(trimethy-
lammonium)benzoate iodide.
m
q or b – rocking
or in plane bending,
ring deformation,
c
s
a
b
Assignmentsc
s
m
exp
m
cal
A
cal
m
scaleq
d
Average (signed) differences between experimental and computed frequencies.
Root-mean-square errors.
3125vw
3093vw
3082w
3073w
3051w
3025m
3222
3192
3187
3182
3174
3172
3
3170
3163
5.55
1.51
0.18
0.40
10.46
28.74
2.18
26.20
2.15
3054
3027
3022
3017
3010
3008
3007
3006
3000
2999
2964
2932
2925
2919
2916
2898
1712
1592
1558
1494
1475
1474
1467
1463
1459
1458
1453
1452
1443
1432
1414
1413
1342
1296
1283
1270
1243
1243
1206
1186
1165
1149
1132
1131
1113
1095
1071
1068
1017
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
CH
CH
CH
CH +
CH +
asCH
asCH
asCH
asOCH
asCH
asCH
e
m
m
asCH
asCH
3
3
3
171
3
4. Conclusions
2
2
998w
951w
3
3
In crystals of methyl 3-(trimethylammonium)benzoate iodide,
3
162
0.02
3
1
a, I ion is involved in four short NÁ Á ÁI interactions of the average
2
2
2
897w
844vw
822vw
3124
3089
3082
3
3
20.48
111.43
16.81
6.15
3
distance 5.422 Å. The cohesion forces are complemented by short
CHÁ Á ÁI and CHÁ Á ÁO contacts. In the isolated molecule 1b and in
DMSO solution 1c, according to the B3LYP/6-311G(d,p) calcula-
tions, the NÁ Á ÁI distance is somewhat longer. The correlation
between NÁ Á ÁI and OÁ Á ÁI atomic distances with the Mulliken atomic
charges is linear. Charge on the quaternary nitrogen atom depends
on options used for generating electrostatic potential-derived
s
CH
OCH
3
s
3
075
072
s 3
CH + m CH
2.15
s
CH
3
2
1
1
1
1
1
1
1
1
1
1
1
1
696vw
714s
3052
1767
1636
1600
1530
1510
1509
1501
1497
1492
1491
1486
1485
32.89
351.39
31.22
32.33
58.37
24.98
37.78
14.23
4.96
0.30
19.30
0.65
10.43
0.02
24.37
5.31
s
CH
3
C@O
CC
CC
CC
CC
674vw
654wv
638wv
611wv
591w
517vw
487w
468w
454m
440w
418w
charges. The magnetic isotropic shielding constants,
culated by the GIAO/B3LYP/6-311G(d,p) approach and linear corre-
lations with H and C chemical shifts were obtained. The B3LYP
computed wavenumbers, scaled by the scaling equation, repro-
duced the FTIR solid-state experimental spectrum with r.m.s. of
rcalc, were cal-
bCH
1
13
dCH
3
dOCH
dOCH
3
3
dCH
dCH
dCH
dCH
dCH
dCH
3
3
3
3
À1
5
7.8 cm
.
+ dCH
+ dCH
1
475
1463
444
1442
366
Acknowledgement
1
408vw
392vw
1
Calculations were performed at the Pozna n´ Supercomputing
and Networking Centre.
1
8.54
6.45
m
m
COO +
CN + dCH
mCN + dCH
3
1
3
1
1
1
1
1
1
1
1
1
1
340vw
317w
1316
1301
1287
1258
1258
1218
1196
1174
1156
1138
1
1117
1098
1
1
64.28
420.58
47.74
1.32
35.51
14.94
62.41
0.77
33.78
18.13
0.61
3.10
8.59
dCH
CH
OCH
CH +
3
q
Appendix A. Supplementary material
291m
274m
238w
189vw
176wv
139w
c
c
c
c
c
c
3
c
CH
3
CH
CH
3
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.molstruc.2012.
2.051.
OCH
OCH
3
+
m
CAO
0
3
121vw
111vw
dCH + wagCH
3
c
CH
3
References
137
bRing
bRing
Ring
bRing
bRing
1
1
091vw
049vw
[
1] X. Domingo, Betaines, Amphoteric Surfactans, second ed., E.G.M. Lomax,
Marcel Dekker Inc., New York, 1996. pp. 76–190.
072
069
0.02
0.09
36.28
[
[
[
2] A. Schmidt, Adv. Heterocyl. Chem. 85 (2003) 68.
3] E. Alcalde, Adv. Heterocyl. Chem. 60 (1994) 197.
4] E.F. Strittmatter, R.L. Wong, E.R. Williams, J. Am. Chem. Soc. 122 (2000) 1247.
1
003w
1013
3
cCH + cCN

1
22
M. Szafran et al. / Journal of Molecular Structure 1017 (2012) 115–122
[
5] J. Picha, R. Cibulka, F. Liseka, P. Parik, O. Pytela, Collect. Czech. Chem. Commun.
9 (2004) 2239.
6] W. Tadras, A.B. Sakla, J. Chem. Soc. (1954) 1116;
R. Willstätter, W. Kahn, Ber. 37 (1904) 401.
7] G.W. Wood, R.J. Collacott, Org. Mass Spectrom. 18 (1983) 42. and references
cited therein.
8] M. Szafran, A. Katrusiak, Z. Dega-Szafran, A. Komasa, I. Kowalczyk, J. Mol.
Struct. 1006 (2011) 330.
[21] D. Feller, J. Comp. Chem. 17 (13) (1996) 1571.
[22] K.L. Schuchardt, B.T. Didier, T. Elsethagen, L. Sun, V. Gurumoorthi, J. Chase, J. Li,
T.L. Windus, J. Chem. Inf. Model. 47 (2007) 1045.
[23] M.N. Glukhovtsev, A. Pross, M.P. McGrath, L. Radom, J. Chem. Phys. 103 (1995)
1878.
[24] V. Barone, M. Cossi, J. Phys. Chem. A 102 (1998) 1995.
[25] G. Brancoto, N. Rega, V. Barone, J. Chem. Phys. 125 (2006) 164515.
[26] K. Wolinski, J.F. Hilton, P. Pulay, J. Am. Chem. Soc. 112 (1990) 8251. and
references cited therein.
6
[
[
[
[
9] M. Szafran, A. Katrusiak, Z. Dega-Szafran, I. Kowalczyk, J. Mol. Struct. 996
(
2011) 75.
10] M. Szafran, A. Katrusiak, Z. Dega-Szafran, I. Kowalczyk, J. Mol. Struct. 1005
2011) 144.
11] KUMA KM4 CCD Software, Version 161, Kuma Diffraction, Wrocław, Poland,
999.
[27] T.H. Nyrönem, R. Suontamo, H. Pitkänen, Theor. Chem. Acc. 101 (1999) 209.
[28] H. Simpson, Organic Structure Determination Using 2-D NMR Spectroscopy,
Academic Press Elsevier, Amsterdam, 2008.
[
[
(
[29] R. Ditchfield, Mol. Phys. 27 (1994) 789.
1
[30] A. Forsyth, A.B. Sebag, J. Am. Chem. Soc. 119 (1997) 9483.
[31] B. O s´ miałowski, E. Kolehmainen, R. Gawinecki, Magn. Res. Chem. 39 (2001)
334. and references cited therein.
[
[
[
12] CrysAlis, 162, Kuma Diffraction, Wrocław, Poland, 1999.
13] G.M. Sheldrick, Acta Crystallogr. A 64 (2008) 112.
14] C.K. Johnson, ORTEPII, Report ORNL-5138, Oak Ridge National Laboratory,
Tennessee, USA, 1976.
15] Stereochemical Workstation Operation Manual, Release 3.4, Siemens
Analytical X-ray Instruments INC., Madison, 1989.
[32] A.R. Katritzky, N.G. Akhmedov, A. G u} ven, E.F.V. Scriven, S. Majumder, R.G.
Akhmedova, C.D. Hall, J. Mol. Struct. 783 (2006) 191.
[33] A.P. Scott, L. Radom, J. Phys. Chem. 100 (1996) 16502.
[34] P. Pulay, X. Zhou, G. Fogarasi, in: R. Fausto (Ed.), In Recent Experimental and
Computational Advances in Molecular Spectroscopy, Kluver Academic,
Netherlands, 1993, pp. 88–111.
[35] M. Alcolea Palafox, Recent Res. Dev. Phys. Chem. Transworld Research
Network, vol. 2, Trivandrum, India, 1998, 213.
[36] M. Alcolea Palafox, Int. J. Quant. Chem. 77 (2000) 661.
[37] M. Alcolea Palafox, V.K. Rastogi, Spectrochim. Acta A 58 (2002) 411.
[38] K. Szczepaniak, M.M. Szczesniak, W.B. Person, J. Phys. Chem. A 104 (2000)
3852.
[39] K. Szczepaniak, W.B. Person, D. Had zˇ i, J. Phys. Chem. A 109 (2005) 6710.
[40] M. Alcolea Palafox, M. Gill, N.J. Nunez, V.K. Rastogi, L. Mittal, R. Sharma, Int. J.
Quant. Chem. 103 (2005) 394.
[41] Y.I. Binev, M.K. Georgieva, L.I. Daskalowa, Spectrochim. Acta A 60 (2004) 2601.
[42] R. Dennington II, T. Keith, J. Millam, Gauss View, Version 4.1.2, Semichem. Inc.,
Shawnee Mission, KS, 2007.
[
[
16] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann,
O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K.
Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, GAUSSIAN 03, Revision B.05, Gaussian, Inc., Pittsburgh PA, 2003.
17] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[
[
[
[
[43] S.A. Brandán, F. Márquez Lopez, M. Montejo, J.J. Lopez Gonzalez, A. Ben Altebef,
Spectrochim. Acta A 75 (2010) 1422.
18] A.D. Becke, J. Chem. Phys. 107 (1997) 8554.
19] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785.
20] W.J. Hehre, L. Random, P.v.R. Schleyer, J.A. Pople, Ab Initio Molecular Orbital
Theory, Wiley, New York, 1986.
[44] E. Romano, A.B. Raschi, A. Benarente, S.A. Brandán, Spectrochim. Acta A 84
(2011) 111.
[45] A. Katrusiak, J. Mol. Graph. Model 19 (2001) 363.