Structure of methyl 4-(trimethylammonium)benzoate iodide studied by X-ray diffraction, DFT calculations, NMR and FTIR spectra

Article abstract of DOI:10.1016/j.molstruc.2011.09.028

The structure of methyl 4-(trimethylammonium)benzoate iodide, 4-(Me) ₃N⁺C₆H₄CO₂MeI ^-, (1a) has been determined by X-ray diffraction, DFT calculations and characterized by FTIR and NMR spect

Full text of DOI:10.1016/j.molstruc.2011.09.028

Journal of Molecular Structure 1006 (2011) 330–336
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Structure of methyl 4-(trimethylammonium)benzoate iodide studied by X-ray
diffraction, DFT calculations, NMR and FTIR spectra
⇑
M. Szafran , A. Katrusiak, Z. Dega-Szafran, A. Komasa, I. Kowalczyk
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60780 Poznan´, Poland
a r t i c l e i n f o
a b s t r a c t
The structure of methyl 4-(trimethylammonium)benzoate iodide, 4-(Me)3N+C6H4CO2MeIÀ, (1a) has been
determined by X-ray diffraction, DFT calculations and characterized by FTÀIR and NMR spectroscopy. The
Article history:
Received 5 July 2011
Received in revised form 6 September 2011
Accepted 6 September 2011
Available online 1 October 2011
+
ꢀ
crystals are triclinic, space group P1. The electrostatic distances N Á Á ÁI vary between 4.423(3) and
5.152(2) Å. The interpretation of 1H and 13C NMR spectra has been based on 2D experiments and calcu-
lated 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 experimen-
tal solid state vibrational frequencies of the investigated ester (1a) based on the calculated harmonic fre-
quencies are proposed.
Keywords:
Methyl 4-(trimethylammonium)benzoate
iodide
X-ray diffraction
Ó 2011 Elsevier B.V. All rights reserved.
B3LYP calculations
FTIR and NMR spectra
Electrostatic interactions
1. Introduction
Recently, we have described the structures of 4-(trimethylam-
monium)benzoic acid chloride [7]. In this paper, we report the
Both (dimethylamino)-benzoic acids and their esters upon
treatment with methyl iodide in methyl alcohol gave quaternary
iodides [1–4]. Quaternization of 4-(dimethylamino)benzoic acid
by excess of methyl iodide in methyl alcohol depends on temper-
ature and time of refluxing [1]. 4-(Trimethylammonium)benzoic
acid iodide (4-carboxyphenyltrimethylammonium iodide) was ob-
tained after refluxing the mixture for 6–16 h [1,5] but on prolonged
refluxing for 32–40 h methyl 4-(trimethylammonium)benzoate io-
dide, 4-(Me)3N+C6H4CO2MeIÀ, is formed [1].
crystal structure of methyl 4-(trimethylammonium)benzoate io-
dide (p-carbomethoxyphenyltrimethylammonium iodide) (Fig. 1),
and results of its FTIR, NMR and B3LYP investigations. In 4-(trime-
thylammonium)benzoic acid chloride the ClÀ anion is engaged both
in the hydrogen bond with the carboxylic group (COOHÁ Á ÁClÀ) and
electrostatic interactionswiththe positively charged nitrogen atoms
(N+ÁÁÁClÀ). In the ester investigated the anion is engaged mainly in
electrostatic interactions (N+Á Á ÁIÀ). Thus the differences in electro-
static interactions between these compounds can be estimated.
Wood et al. [6], in the pyrolysis electron impact (EI) mass spec-
trometry experiment of N-(trimethylammonium)carboxylates
(Me3N+–(CH2)nCOOÀ) and their hydrochlorides, observed the
reaction of isomerization to more volatile methyl esters (Me2N–
(CH2)nCOOMe). It is probable that 4-(trimethylammonium)benzoic
acid iodide on heating also isomerised to methyl 4-(dimethyl-
amino)benzoate, which further reacts with methyl iodide to form
methyl 4-(trimethylammonium)benzoate iodide (1).
2. Experimental and calculations
2.1. Synthesis
A solution of 4-(dimethylamino)benzoic acid (15 g) in methanol
(70 cm3) and methyl iodide (30 g) was heated at 70° in a sealed
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 63%, m.p. 182 °C, Ref. [2] 170 °C.
Basicity of trimethylammoniobenzoates (Me3N+C6H4COOÀ)
have been measured by kinetic methods. Their gas-phase basicities
are in the range 248.4–267.5 kcal/mol and are classified as organic
superbases [4].
2.2. Measurements
⇑
The X-ray diffraction measurements were carried out on a KUMA
KM4-CCD diffractometer [8,9]. The structure was solved by direct
Corresponding author. Tel.: +48 61 8291320; fax: +48 61 8291505.
E-mail address: szafran@amu.edu.pl (M. Szafran).
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.09.028

M. Szafran et al. / Journal of Molecular Structure 1006 (2011) 330–336
331
Table 2
Atomic coordinates (Â104) and equivalent isotropic displacement parameters
(Å2 Â 103) for methyl 4-(trimethylammonium)benzoate iodide. Ueq (Uiso for H-atoms)
is defined as one third of the trace of the orthogonalized Uij tensor.
x
y
z
Ueq/Uiso
I(1)
O(1)
O(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
N(1)
C(8)
1778(1)
À4728(4)
À4419(4)
À2068(5)
À1018(6)
575(6)
1109(5)
121(5)
À1458(5)
À3824(6)
2830(4)
2609(6)
3209(6)
4527(6)
À6477(6)
À1401
1285
6892(1)
9818(3)
10,980(3)
9073(4)
8585(4)
7611(4)
7085(4)
7570(4)
8586(4)
10,087(4)
5985(3)
4662(4)
5410(5)
6732(5)
10,734(5)
8926
7172(1)
3207(3)
828(3)
2035(4)
3221(4)
3337(4)
2251(3)
1040(4)
934(4)
1925(4)
2444(3)
3820(4)
1241(4)
2478(4)
3264(5)
3959
51(1)
50(1)
57(1)
33(1)
44(1)
43(1)
33(1)
39(1)
40(1)
40(1)
34(1)
46(1)
47(1)
50(1)
71(2)
53
Fig. 1. The asymmetric unit of the crystal structure of methyl 4-(trimethylammo-
nium)benzoate iodide (1a). Thermal ellipsoids have been drawn at the 50%
probability level.
C(9)
C(10)
C(11)
H(2)
methods with the SHELXS-97 program and refined on F2 full-matrix
least-squares with SHELXL-97 [10]. All hydrogen atoms were
located from the molecular geometry and their isotropic displace-
ment parameters were based on Ueq of their carriers. The crystal
data, together with the details concerning the data collection and
structure refinement are given in Table 1 and the atomic coordinates
are in Table 2. The parameters in the CIF form are available as Elec-
tronic Supplementary Information from the Cambridge Crystallo-
graphic Database Centre (CCDC 832438). Molecular illustrations
were prepared using ORTEPII [11] and the XP [12] packages.
FTIR spectra were recorded in Nujol and Fluorolube mulls on a
Bruker IFS 66 v/S spectrometer, evacuated to avoid water and CO2
absorptions, at 2 cmÀ1 resolution. Each FTIR spectrum consisted of
64 scans.
H(3)
7309
4132
52
H(5)
H(6)
505
7223
8945
4996
3994
4152
6235
4892
4739
7586
6040
7046
10,439
10,608
11,764
307
108
4606
3955
3779
346
1221
1392
1605
2573
3277
4236
2679
2914
46
48
69
69
69
71
71
71
75
75
75
106
106
106
À2116
H(8A)
H(8B)
H(8C)
H(9A)
H(9B)
H(9C)
H(10A)
H(10B)
H(10C)
H(11A)
H(11B)
H(11C)
2366
3746
1575
3353
2173
4344
4662
5637
4362
À6998
À7353
À6239
NMR spectra were recorded on a Bruker Advance DRX spec-
trometer operating at 599.93 and 150.85 MHz for 1H and 13C,
respectively. The spectra were measured in DMSO-d6 solution rel-
ative to TMS. The 2D 1H–1H (COSY), 1H–13C (HETCOR) and Hetero-
nuclear Multiple-Bond Connectivity (HMBC) spectra were obtained
with the standard Bruker software.
2.3. Calculations
Optimization of geometrical parameters was performed using
the Gaussian 03 program package [13]. The X-ray geometry of 1a
was used as a starting point of calculations. The calculations em-
ployed the hybrid B3LYP exchange–correlation functional, which
combined the exchange functional of Becke [14,15] with the gradi-
ent-correlation functional of Lee et al. [16] approach in conjunction
with the 6–311G(d,p) basis set [17]. 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 [18,19], where the 6–311G(d,p) basis set created
by Glukhovtsev et al. [20] is made available. Glukhovtsev et al.
tested their basis on a set of iodine-containing species assessing
theoretical results by comparison with experimental data.
Table 1
Crystal data and structure refinement for methyl 4-(trimethylammonium)benzoate
iodide.
Empirical formula
Formula weight
C11H16INO2
321.15
Temperature
Wavelength
293(2) K
0.71073 Å
ꢀ
Crystal system, space group
Triclinic, P1
Unit cell dimensions
a = 7.1767(6) Å
b = 9.7452(7) Å
c = 10.1282(8) Å
The magnetic isotropic shielding constants for isolated mole-
cule and in DMSO were calculated with the standard GIAO/
B3LYP/6-311G(d,p) (Gauge-Independent Atomic Orbital) approach
with the Gaussian 03 program package using the conductor-like
screening solvation model (COSMO) [21–23].
a
= 67.455(7) °
b = 83.613(7) °
c
= 82.257(7) °
Volume
646.88(9) Å3
Z, calculated density
Absorption coefficient
F(000)
2, 1.649 g/cm3
2.458 mmÀ1
316
3. Results and discussion
Crystal size
0.13 Â 0.08 Â 0.06 mm
h range for data collection
Max/min indices h, k, l
Reflections collected/unique
hMax(°)/completeness (%)
Absorption correction
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R1/wR2 indices [I > 2rI
R1/R2 indices (all data)
Largest diff. peak and hole
2.87–29.20
3.1. Molecular parameters
À8/9, À13/13, À8/13
4877/2936 [R(int) = 0.0271]
29.20/84.0
The molecular structure and atom numbering of 4-
(Me)3N+C6H4CO2MeIÀ are shown in Fig. 1, and the projection of
the crystal structure viewed along the layers formed by the ions
is given in Fig. 2. An autostereogram of one sheet of ions is pre-
sented in Fig. 3. The crystal structure of 1a can be described as built
of layers of cations with IÀ anions located on both sides of the lay-
ers, as shown in Fig. 2. Within the layers the cation dimers can be
None
Full-matrix least-squares on F2
2936/0/136
1.079
]
0.0401/0.0635
0.0561/0.0722
0.304 and À0.426 e ÅÀ3

332
M. Szafran et al. / Journal of Molecular Structure 1006 (2011) 330–336
Table 3
Experimental (X-ray) and calculated by the B3LYP/6-311G(d,p) method bond lengths
(Å), bond and torsion angles (deg) for methyl 4-(trimethylammonium)benzoate
iodide.
X-ray
1a
B3LYP
1b (vacuum)
1c (DMSO)
Bonds
O(1)–C(7)
O(1)–C(11)
O(2)–C(7)
C(1)–C(2)
C(1)–C(6)
C(1)–C(7)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(4)–N(1)
C(5)–C(6)
N(1)–C(8)
N(1)–C(9)
N(1)–C(10)
1.332(4)
1.448(5)
1.199(4)
1.380(5)
1.379(4)
1.479(5)
1.369(5)
1.379(4)
1.374(5)
1.500(5)
1.385(5)
1.503(4)
1.510(4)
1.511(5)
1.3424
1.4410
1.2082
1.3968
1.3943
1.4963
1.3905
1.3924
1.3940
1.5103
1.3909
1.5211
1.4998
1.5212
1.3388
1.4444
1.2125
1.3981
1.3939
1.4948
1.3890
1.3945
1.3912
1.5073
1.3925
1.5166
1.5070
1.5166
Fig. 2. The crystal structure of methyl 4-(trimethylammonium)benzoate iodide
(1a) viewed along the layers formed by the ions.
Angles
O(1)–C(7)–C(1)
O(2)–C(7)–C(1)
O(2)–C(7)–O(1)
C(1)–C(2)–C(3)
C(1)–C(6)–C(5)
C(2)–C(3)–C(4)
C(2)–C(1)–C(6)
C(2)–C(1)–C(7)
C(3)–C(4)–N(1)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(4)–N(1)–C(8)
C(4)–N(1)–C(9)
C(4)–N(1)–C(10)
C(5)–C(4)–N(1)
C(6)–C(1)–C(7)
C(7)–O(1)–C(11)
C(8)–N(1)–C(9)
C(8)–N(1)–C(10)
C(9)–N(1)–C(10)
110.8(3)
125.1(4)
123.9(4)
121.5(3)
121.0(3)
118.8(3)
118.6(3)
121.8(3)
117.0(3)
121.3(3)
118.7(3)
110.4(3)
112.4(3)
109.2(3)
121.7(3)
119.7(3)
116.9(3)
107.7(3)
109.3(3)
107.7(3)
112.14
132.87
123.99
120.63
120.56
119.02
119.50
122.81
117.70
121.21
119.09
109.44
112.60
109.44
121.10
117.69
115.90
108.11
109.09
108.10
112.39
129.93
123.68
120.33
120.75
119.52
119.42
122.38
117.89
120.87
119.11
109.58
112.76
109.59
121.24
118.20
116.26
107.74
109.38
107.73
Selected torsion angles
C(2)–C(1)–C(7)–O(1)
C(6)–C(1)–C(7)–O(1)
C(2)–C(1)–C(7)–O(2)
C(6)–C(1)–C(7)–O(2)
C(11)–O(1)–C(7)–O(2)
C(1)–C(2)–C(3)–C(4)
C(2)–C(3)–C(4)–C(5)
C(2)–C(3)–C(4)–N(1)
C(2)–C(1)–C(6)–C(5)
C(3)–C(4)–C(5)–C(6)
C(3)–C(4)–N(1)–C(8)
C(3)–C(4)–N(1)–C(9)
C(3)–C(4)–N(1)–C(10)
C(4)–C(5)–C(6)–C(1)
C(5)–C(4)–N(1)–C(10)
C(5)–C(4)–N(1)–C(8)
C(5)–C(4)–N(1)–C(9)
C(6)–C(1)–C(2)–C(3)
C(7)–C(1)–C(2)–C(3)
C(7)–C(1)–C(6)–C(5)
N(1)–C(4)–C(5)–C(6)
C(11)–O(1)–C(7)–C(1)
À33.3(5)
146.2(4)
150.4(4)
À30.1(6)
À3.8(6)
À1.5(6)
2.8(6)
0.04
À179.96
À179.96
0.04
0.01
0.00
0.00
180.00
0.00
0.11
À179.91
À179.96
0.02
0.03
0.02
À0.01
180.00
À0.01
0.00
À178.2(4)
3.2(6)
À1.2(6)
56.0(4)
0.00
59.76
60.07
176.3(3)
À64.2(4)
À1.9(6)
114.8(4)
À125.0(4)
À4.8(5)
À1.5(6)
178.0(4)
À176.3(4)
179.9(3)
179.9(3)
À179.99
À59.74
0.00
120.61
À120.24
0.01
À179.94
À59.96
0.00
120.05
À119.93
0.61
À0.02
179.96
À179.97
180.00
179.96
Fig. 3. An autostereogram [39] of one sheet of ions (cf. Fig. 2).
0.00
180.00
180.00
180.00
À180.00
easily distinguished (Fig. 3); they are formed of antiparallel cations
with partly stacked benzene rings and two pairs of C(10)HÁ Á ÁO(2)
and C(9)HÁ Á ÁO(2) contacts (2.333 and 2.692 Å, symmetry code:
(Àx, 2 À y, Àz). These contacts involve ammonium methyl
hydrogens and an oxygen atom. The most immediate surrounding
of the iodide anions includes hydrogen atoms of ammonium, ester
methyl and phenyls.
Fig. 4. Comparison of X-ray (1a) and B3LYP (1b–1c) structures of methyl 4-
(trimethylammonium) benzoate iodide.

M. Szafran et al. / Journal of Molecular Structure 1006 (2011) 330–336
333
Table 4
Energies (Hartree, a.u.), dipole moments (
iodide.
l, Debye) and the shortest intermolecular contacts for methyl 4-(trimethylammonium)benzoate
Compounds
Energy
l
N+Á Á ÁIÀ
O(1)Á Á ÁIÀ
O(2)Á Á ÁIÀ
X-ray
1a
4.423(2)a
4.508(2)b
5.152(3)c
3.951(2)d
4.139(2)e
4.632(2)f
6.153(3)c
7.674(3)c
B3LYP/6-311G(d,p)
1b (vacuum)
1c (DMSO)
À7553.68963489
À7553.73970129
13.1864
19.5895
5.3082
4.7299
7.1056c
7.2373c
8.4166c
6.4363c
Symmetry codes:
a
1 À x, 1 À y, 1 À z.
b
Àx, 1 À y, 1 À z.
c
x, y, z.
d
Àx, 2 À y, 1 À z.
e
Àx, 2 À y, 1 À z.
f
x + 1, y, z.
180
160
140
120
100
80
9
8
7
6
5
4
3
a
b
60
40
0
20 40 60 80 100 120 140
22
24
26
28
Magnetic isotropic shielding constants
Fig. 5. Plots of the experimental chemical shifts (dexp) in DMSO-d6 vs. the magnetic isotropic shielding constants (rcalc) from the GIAO/B3LYP/6-311G(d,p) calculated for
methyl 4-(trimethylammonium)benzoate iodide in DMSO; dexp = a + b calc; (a) carbon-13, and (b) proton.
r
The optimized structures (1b and 1c) are compared to that deter-
mined by X-ray analysis in Fig. 4. The calculated bond lengths, bond
angles, and selected torsion angles are summarized in Table 3. In
crystals the COOMe group is twisted relative to the benzene ring
by ca. 33° (C(2)–C(1)–C(7)–O(1) = À33.3(5)°), while in the opti-
mized structure the planar conformation of the cation was observed
(Table 3). In 4-(trimethylammonium)benzoic acid chloride the con-
formations are reverse; in crystal the structure is planar, while in the
optimized structure it is twisted by 82° [7]. As shown in Figs. 2 and 3,
in the crystal IÀ anion is engaged in electrostatic contacts with the
positively charged nitrogen atoms; the N+Á Á ÁIÀ distances are
4.423(2), 4.508(2) and 5.152(3) (Table 4) Å. In 4-(trimethylammoni-
um)benzoic acid chloride [7] the N+Á Á ÁClÀ distances are 3.977, 4.214,
5.199 and 9.337 (x, y, z) Å (5.388 Å average value).The other contacts
in 1a are between IÀ anion and oxygen atoms (Table 4).
and the Gauge Including Atomic Orbitals (GIAO) magnetic isotropic
shielding constants ( calc), which are widely used [25–28], are usu-
ally linear and described by the following 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 (Fig. 5). As in Table 5,
r
r
r
the agreements between the experimental and calculated data
are satisfactory, both for carbon-13 and proton.
3.3. FTIR spectra
The experimental solid-state and the calculated spectra of 4-
(Me)3N+C6H4CO2MeIÀ are shown in Fig. 6. The intense band at
1724 cmÀ1 arises from the
mC@O vibration. Table 6 lists the
experimental and calculated frequencies, and intensities for
normal modes in the optimized molecule 1b. A comparison of
the calculated and experimental frequencies shows typical differ-
ences. The calculated bands are shifted to higher wavenumbers
relative to the experimental data. Two facts may be responsible
for the differences between the experimental and computed
spectra of the molecule investigated. The first is that the
experimental spectrum was recorded for the complex 1a in the
3.2. 1H and 13C NMR spectra
The assignments of proton and carbon-13 chemical shifts for
4-(Me)3N+C6H4CO2MeIÀ, listed in Table 5, are based on two
dimensional 1H–1H, 1H–13C and HMBC experiments [24]. The rela-
tion between the experimental 13C and 1H chemical shifts (dexp
)

334
M. Szafran et al. / Journal of Molecular Structure 1006 (2011) 330–336
Table 5
Experimental in DMSO-d6, predicted (dpred = a + b
6-311G(d,p) isotropic magnetic shielding constants (
r
calc) carbon-13 and proton chemical shifts (ppm) and calculated GIAO/B3LYP/
r
calc) for methyl 4-(trimethylammonium)benzoate iodide.
Atoma
dexp (DMSO-d6)
dpred (DMSO)
rcalc (DMSO)
Carbon
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)OO
C(8)
C(9)
131.00
130.73
121.41
150.48
121.41
130.73
164.89
56.36
56.36
56.36
56.36
52.71
131.45
131.64
123.09
150.20
117.98
132.47
163.88
45.9184
45.7203
54.6680
26.2866
60.0170
44.8466
11.9602
128.4451
122.8355
122.8294
124.7034
128.2826
175.3017
À0.9550
0.9992
C(10)
C(8)–C(10) av
C(11)
ab
56.21
52.81
bc
rd
Av. dif.e
R.m.s.f
À1.11
1.57
Proton
H(2)
H(6)
H(3)
H(5)
8.163
8.163
8.159
8.159
8.176
8.231
8.534
7.585
23.2906
23.2254
22.8632
23.9966
28.3662
28.3628
28.7313
27.2079
28.7653
28.9457
28.9481
28.7654
27.2009
28.3660
27.9316
27.8748
27.8759
28.5606
27.6824
À0.8375
0.9888
NCH3
NCH3 av
OCH3
3.66
3.91
3.926
3.763
OCH3 av
ab
bc
rd
Av. dif.e
R.m.s.f
À1.67
0.34
a
b
c
d
e
f
Numbering of atoms is in Fig. 1.
Intercept.
Slope.
Correlation coefficient.
Average (signed) differences between experimental and predicted chemical shifts.
Root-mean-square errors.
1.5
1.2
0.9
0.6
0.3
a
solid state, while the computed spectrum refers to the isolated
molecule 1b in the gas phase. The second is the fact that the
experimental results are anharmonic vibrations, while the calcu-
lated values are harmonic ones. Similar discrepancies between
the calculated and experimental frequencies have been noted
for 4-(trimethylammonium)benzoic acid chloride [7]. The overes-
timation of the computed wavenumbers is quite systematic and
can be corrected by applying appropriate scaling factors or
scaling equations [29–37]. In Fig. 7, a linear relation between
the experimental and calculated frequencies characterized by a
good correlation coefficient is shown. This scaling procedure, as
recommended by Alcolea Palafox [32] was used. The scaled IR
spectrum is shown in Fig. 6b and the predicted frequencies are
0.0
400
3500
3000
2500
2000
1500
1000
500
b
300
200
100
0
3500
3000
2500
2000
1500
1000
500
listed in Table 6 as
mscaleq. Scaling of the harmonic vibrational
Wavenumbers (cm-1)
frequencies reproduced the experimental solid-state FTIR
frequencies with the r.m.s. error of 38.1 cmÀ1. The vibrational
band assignments of 4-(Me)3N+C6H4CO2MeIÀ was made using
Gauss-View molecular visualization program [38].
Fig. 6. Vibrational spectra of methyl 4-(trimethylammonium)benzoate iodide: (a)
solid-state FTIR spectrum of 1a; (b) calculated and scaled IR spectrum by the B3LYP/
6-311G(d,p) approach for 1b.

M. Szafran et al. / Journal of Molecular Structure 1006 (2011) 330–336
335
Table 6
3500
Experimental (solid state) and calculated vibrational data for methyl 4-(trimethy-
lammonium)benzoate iodide.
3000
2500
2000
1500
1000
500
a
mexp
mcal
Acal
mscaleq
Assignments
3104
3070
3225
3219
3204
3168
3167.8
3165
3159.3
3159.1
3126
3118
3111
3074
3053
3043
2993
2982
1787
1647
1626
1543
1525
1515
1511
1498
1495
1490
1488
1484
1475
1469
1456
1450
1445
1355
1343
1306
1293
1259
1253
1227
1215
1174
1163
1145
1142
1132
1123
1086
1057
1031
989
4.09
1.45
0.32
3.92
15.72
11.59
1.45
3058
3052
3038
3004
3004
3002
2996
2996
2965
2958
2951
2917
2897
2888
2841
2831
1715
1584
1565
1487
1470
1461
1457
1445
1442
1437
1436
1432
1424
1418
1406
1400
1395
1311
1300
1266
1254
1219
1216
1192
1181
1142
1132
1115
1113
1103
1095
1060
1033
1009
970
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
m
CH
CH
CH
3057
3046
3033
3008
2997
2947
2913
asCH3
asCH3
asCH3
asCH3
asCH3
asOCH3
asCH3
asCH3
sCH3
sOCH3
CH +
sCH3
sCH3
C@O
CC
1.73
18.43
105.73
0.002
16.27
29.62
527.13
199.08
44.92
254.13
24.33
3.03
0
0
500 1000 1500 2000 2500 3000 3500
2874
2846
2820
2812
Calculated frequencies by B3LYP/6-311G (d,p), cm-1
msCH3
Fig. 7. Correlation between the experimental and calculated wavenumbers (cmÀ1
for methyl 4-(trimethylammonium)benzoate iodide; scaled = 46.2639 + 0.9337
calc., r = 0.9989.
)
m
1724
1689
1607
1516
1488
1482
1474
1456
1451
m
CC
8.65
dCH
4. Conclusions
47.52
24.37
16.63
9.26
40.67
0.27
dCH3
dCH3
dCH3
dOCH3
dOCH3
dCH3
The molecular and crystal structures of methyl 4-(trimethylam-
monium)benzoate iodide were determined by X-ray diffraction
and B3LYP/6–311G(d,p) level of theory. In the crystals (1a) the IÀ
ion is involved in three short N+Á Á ÁIÀ electrostatic interactions
(average value is 4.694 Å). In the isolated molecules (1b and 1c),
according to the B3LYP calculations the N+Á Á ÁIÀ distance is slightly
different. In 4-(trimethylammonium)benzoic acid chloride [6] the
N+Á Á ÁClÀ average value is longer (5.388 Å) and it is caused by the
hydrogen bond. The correlations between the experimental car-
bon-13 and hydrogen chemical shifts in DMSO-d6 and the mag-
1428
1417
1411
2.52
dCH3
10.24
28.67
0.62
5.19
7.02
dCH3 + dCH
dCH3 + dCH
dCH
dCH
1384
m
m
COO +
CN + dCH3
mCN + dCH3
1.85
1328
1308
1291
1281
11.85
13.87
354.29
115.18
4.02
dCH3
dCH3
netic isotropic shielding constants,
rcalc, calculated by the GIAO/
c
c
c
c
c
c
c
OCH3
OCH3
B3LYP/6-311G(d,p) approach are linear with good correlation coef-
ficients. The B3LYP computed wavenumbers, scaled by the scaling
equation, reproduced the FTIR solid-state experimental spectrum
CH +
CH3
cCH3
1244
1201
1154
8.49
74.34
23.25
0.78
2.76
0.05
97.60
19.12
4.07
0.38
0.01
29.22
0.27
19.06
13.89
25.71
0.04
23.92
2.22
7.66
20.09
8.46
22.09
3.49
0.76
10.73
3.16
CH
OCH3
OCH3
with r.m.s. of 38.1 cmÀ1
.
+
m
CAO
Acknowledgment
1124
dCH +
c
CH3
c
CH3
1109
1014
972
Ring
Ring
´
Calculations were performed at the Poznan Supercomputing
and Networking Centre.
c
c
c
CH3
CH3
CH
+
c
CN
References
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944
862
852
Ring
c
c
c
c
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