Study of N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium chloride dihydrate by DFT calculations, NMR and FTIR spectroscopy

Article abstract of DOI:10.1016/j.molstruc.2009.03.005

N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium chloride dihydrate (1) and N,N-dimethyl(carboxymethyl)-3-phthalimidopropylammonium hydrochloride (3) have been obtained in reaction of N,N-dimethyl-3-phthalimidopropylamine with ethyl chloroacetate and chloroacetic acid, respectively. N,N-dimethyl(carboethoxymethyl)-3-phthalimido-propylammonium chloride dihydrate (1) has been characterized by FTIR and NMR spectroscopy. Moreover, for (1) and (3) B3LYP calculations have been carried out. The optimized bond lengths, bond angles and torsion angles calculated by B3LYP/6-31G(d,p) approach have been presented. Both FTIR and Raman spectra of (1) are consistent with the calculated structures in the gas phase. Correlations between the experimental ¹H and ¹³C NMR chemical shifts (δ_exp) of investigated compound in D₂O, and the GIAO/B3LYP/6-31G(d,p) calculated magnetic isotropic shielding tensors (σ_calc), δ_exp = a + b σ_calc, are reported. The assignments of the anharmonic experimental solid state vibrational frequencies of (1) based on the calculated B3LYP/6-31G(d,p) harmonic frequencies have been made. Linear correlations between the experimental ¹H and ¹³C chemical shifts and the computed screening constants confirm the optimized geometry.

Full text of DOI:10.1016/j.molstruc.2009.03.005

Journal of Molecular Structure 928 (2009) 12–17
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Study of N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium
chloride dihydrate by DFT calculations, NMR and FTIR spectroscopy
*
Iwona Kowalczyk
´
Laboratory of Microbiocides Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium chloride dihydrate (1) and N,N-
dimethyl(carboxymethyl)-3-phthalimidopropylammonium hydrochloride (3) have been obtained in
reaction of N,N-dimethyl-3-phthalimidopropylamine with ethyl chloroacetate and chloroacetic acid,
respectively. N,N-dimethyl(carboethoxymethyl)-3-phthalimido-propylammonium chloride dihydrate
(1) has been characterized by FTIR and NMR spectroscopy. Moreover, for (1) and (3) B3LYP calculations
have been carried out. The optimized bond lengths, bond angles and torsion angles calculated by B3LYP/
6-31G(d,p) approach have been presented. Both FTIR and Raman spectra of (1) are consistent with the
calculated structures in the gas phase. Correlations between the experimental 1H and 13C NMR chemical
shifts (dexp) of investigated compound in D2O, and the GIAO/B3LYP/6-31G(d,p) calculated magnetic iso-
Received 23 February 2009
Accepted 1 March 2009
Available online 13 March 2009
Keywords:
N,N-dimethyl(carboethoxymethyl)-3-
phthalimidopropylammonium chloride
N,N-dimethyl(carboxymethyl)-3-
phthalimidopropylammonium
hydrochloride
tropic shielding tensors (rcalc), dexp = a + b rcalc, are reported. The assignments of the anharmonic exper-
imental solid state vibrational frequencies of (1) based on the calculated B3LYP/6-31G(d,p) harmonic
frequencies have been made. Linear correlations between the experimental 1H and 13C chemical shifts
and the computed screening constants confirm the optimized geometry.
Intermolecular hydrogen bonds
DFT calculations
FTIR and NMR spectra
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium
chloride dihydrate analyzed by FTIR and NMR spectroscopy and
Quaternaryalkylammonium saltsplayan important roleinthe liv-
ing organisms and many functions of prokaryotic and eukaryotic cells
have been shown to be alkylammonium salts dependent [1,2]. These
compounds also exhibit an excellent antimicrobial activity, therefore
they are used as antiseptics, bactericides and fungicides, and as ther-
apeuticagents, as well. In general, ammonium salts with good antimi-
crobial activities contain one or two alkyl chains with the lengths in
the range of C8–C14. For the applications as softeners and hair condi-
tioning agents chain lengths between C16 and C18 are used [3–5].
Phthalimides, and N-substituted phthalimides are an important
class of compounds because of their biological activities as antimi-
crobial agents [6,7]. It has recently been shown that tetrachloroph-
B3LYP calculations has been presented in this paper. The above com-
pounds belong to N,N-dimethyl-3-phthalimidopropylammonium
derivatives investigated in our laboratory in order to better under-
stand the mechanism of their biological activity. The another aspect
of my interest in quaternary derivatives of N,N-dimethyl-3-phtha-
limidopropylamine is the role of counterions and molecules of water
in their formation in the solid state and in isolated entities.
2. Experimental
2.1. Synthesis
N,N-dimethyl-3-phthalimidopropylamine was obtained by the
reaction of a commercially available N,N-dimethylpropyl-1,3-dia-
mine with phthalic anhydride in acetic acid. The reaction mixture
was heated under reflux for 4 h. The product was purified by meth-
od given in our previous paper [13]. N,N-dimethyl(carboethoxym-
ethyl)-3-phthalimidopropylammonium chloride dihydrate (1) was
prepared by reaction of equimolar amounts of N,N-dimethyl-3-
phthalimidopropylamine and ethyl chloroacetate acid in anhy-
drous ethanol. The product was purified by crystallization from
ethanol (Yield 62%, m.p. 74–77 °C. Elemental analysis: found (calc)
%C 53.11 (53.26); %H 7.29 (7.45); %N 6.86 (6.90). ES+MS m/z
319(C17H23N2O4). N,N-dimethyl(carboxymethyl)-3-phthalimido-
propylammonium hydrochloride (3) was prepared by reaction of
thalimides derivatives are good a-glucosidase inhibitors [8].
The use of microbiocides of the same type for a long time may
cause an increase of resistance of microorganisms what is a very
serious problem. Antimicrobial resistance of bacteria comprises a
wide variety of biochemical mechanisms and processes that allow
microorganisms to grow in the presence of microbiocides [9–11].
To avoid this problem structures and types of microbiocides must
to be continuously changed [12,13].
One of the quaternary ammonium derivatives are betaines, their
hydrochlorides and esters. The molecular structure of N,N-
* Tel.: +48 61 829 1306; fax: +48 61 865 8008.
E-mail address: iwkow@amu.edu.pl
0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.03.005

I. Kowalczyk / Journal of Molecular Structure 928 (2009) 12–17
13
equimolar amounts of N,N-dimethyl-3-phthalimidopropylamine
and chloroacetic acid in anhydrous ethanol. The product was puri-
fied by crystallization from ethanol (Yield 65%, m.p. 170–175 °C.
Elemental analysis: found (calc) %C 54.36 (54.38); %H 8.54
(8.46); %N 6.13 (6.04). ES+MS m/z 291(C15H19N2O4).
32°, acquisition time 5 s, FT size 32 K and digital resolution 0.3 Hz
per point, and for the carbon spectra pulse width 60°, FT size 60 K
and digital resolution 0.6 Hz per point, the number of scans varied
from 1200 to 10,000 per spectrum. The 13C and 1H chemical shifts
were measured in D2O relative to TSP in d (ppm). All proton and car-
bon-13 resonances were assigned by 1H (COSY) and 13C (HETCOR).
The FTIR spectra in Nujol and Florolube mulls at 2 cmÀ1 resolu-
tion and Raman spectrum were recorded on a Bruker IFS 66 v/S
instrument, evacuated to avoid water and CO2 absorption. Each
spectrum consists of 250 scans at 31 °C.
2.2. Instrumentation
NMR spectra were measured with a Varian Gemini 300 VT spec-
trometer, operating at 300.07 and 75.4614 Hz for 1H and 13C, respec-
tively. Typical conditions for the proton spectra were: pulse width
MS spectra were measured in water solution on Waters Micro-
mass ZQ spectrometer.
O
The calculations were performed using the GAUSSIAN 03 pro-
gram package [14] at the B3LYP [15–17] levels of theory with the
6-31G(d,p) basis set [18]. The NMR isotropic shielding constants
were calculated using the standard GIAO (Gauge-Independent
Atomic Orbital) approach [19,20] of Gaussian 03.
7
15
8
CH3
6
5
9
2
2H2O
Cl
10
CH2
11
CH2
12
CH2
13
1 N
N
14
CH3
3
16 CH2
4
3. Results and discussion
O
COOCH2CH3
3.1. B3LYP calculations
17 18 19
Fig. 1. The structures and numbering of carbons for (1).
The structure and numbering of carbons for (1) is given in Fig. 1.
The optimized geometry parameters were computed by using the
Table 1
Calculated structural parameters (B3LYP/6-31G(d,p)) for N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium chloride dihydrate (1), N,N-dimethyl(carboeth-
oxymethyl)-3-phthalimidopropylammonium chloride monohydrate (1a), N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium chloride (1b), N,N-dimethyl-3-
phthalimidopropylammonium hydrochloride monohydrate (2), N,N-dimethyl-3-phthalimidopropylammonium hydrochloride (2a), N,N-dimethyl(carboxymethyl)-3-phthalim-
idopropylammonium hydrochloride (3).
Parameters
1
1a
1b
2
2a
3
Energy (a.u.)
À1685.19979
À1608.76331
À1532.32021
À1302.25627
À1225.81479
À1453.68555
Bond lengths [Å]
N(1)AC(9)
N(1)AC(2)
N(1)AC(10)
C(2)AO(2)
C(9)AO(9)
C(16)AH
1.402
1.411
1.454
1.212
1.217
1.090
1.402
1.410
1.454
1.212
1.217
1.091
1.405
1.408
1.455
1.215
1.215
1.090
1.401
1.413
1.455
1.211
1.218
1.406
1.407
1.454
1.215
1.215
1.405
1.408
1.453
1.213
1.216
1.088
Bond angles [°]
C(9)AN(1)AC(10)
N(1)AC(10)AC(11)
O(9)AC(9)AN(1)
C(3)AC(4)AC(5)
C(5)AC(6)AC(7)
C(6)AC(7)AC(8)
123.5
112.0
125.3
117.3
121.1
117.4
123.5
112.0
124.9
117.4
121.1
117.4
123.7
112.2
125.2
117.4
121.1
117.4
123.8
112.1
125.1
117.3
121.1
117.4
123.7
112.4
125.1
117.4
121.1
117.4
124.2
112.2
125.1
117.4
121.1
117.4
Torsion angles [°]
C(2)AN(1)AC(10)AC(11)
C(9)AN(1)AC(10)AC(11)
C(8)AC(9)AN(1)AC(10)
N(1)AC(10)AC(11)AC(12)
O(2)AC(2)AN(1)AC(9)
C(16)AC(17)AOAC(18)
C(17)AOAC(18)AC(19)
C(12)AN(13)AC(16)AC(17)
C(11)AC(12)AN(13)AC(14)
C(11)AC(12)AN(13)AC(15)
109.8
À72.9
À177.9
172.0
À179.5
173.9
À100.8
179.5
55.2
107.1
70.0
116.5
116.5
À177.8
173.8
À177.8
–
75.3
À105.6
À178.5
174.2
178.7
–
88.6
À74.5
À178.5
174.1
À179.8
À169.4
173.0
À111.2
À178.2
173.4
178.5
À175.6
À87.8
178.7
53.7
À91.1
À179.0
173.2
À178.4
–
–
–
–
–
–
À175.7
171.9
52.8
172.0
58.1
À61.2
À67.9
174.0
177.2
173.2
173.4
168.6
Hydrogen bonds and short contacts lengths
Distances [Å]
HOAHÁÁÁCl
3.079
2.824
3.455
3.719
3.444
3.775
3.131
–
3.435
3.511
3.389
3.676
–
–
3.085
–
3.324
3.398
–
–
–
–
–
OÁÁÁHAO
C(12)AHÁÁÁCl
C(14)AHÁÁÁCl
C(16)AHÁÁÁCl
N(13) ÁÁCl
3.354
3.431
3.245
3.570
3.322
3.341
–
3.362
3.378
3.228
3.541
3.757
3.473
Angles [deg]
HOAHÁÁÁCl
161.3
158.6
157.2
141.1
156.3
162.2
–
153.4
146.8
154.0
–
–
164.8
–
148.4
152.5
–
–
–
–
–
HOAHÁÁÁO
C(12)AHÁÁÁCl
C(14)AHÁÁÁCl
C(16)AHÁÁÁCl
152.3
145.0
155.5
147.6
145.2
–
150.4
145.9
154.1

14
I. Kowalczyk / Journal of Molecular Structure 928 (2009) 12–17
B3LYP/6-31G(d,p) and presented in Table 1. The calculated bond
lengths and bond angles for N,N-dimethyl(carboethoxymethyl)-3-
phthalimidopropylammonium chloride dihydrate (1), monohy-
drate (1a) and their anhydrous analogue (1b) are compared
with N,N-dimethyl-3-phthalimidopropylammonium hydrochlo-
ride monohydrate (2) [21], its anhydrous analogue (2a) and with
N,N-dimethyl(carboxymethyl)-3-phthalimidopropylammonium
hydrochloride (3). The structures optimized at the B3LYP/6-
31G(d,p) level of theory for (1), (1a), (1b), (2) and (2a) are shown
in Fig. 2. The calculated bond lengths and bond angles for
N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammom-
nium chloride dihydrate, monohydrate and its anhydrous analogue
are very similar, however the torsion angles are substantially dif-
ferent what shows a crucial role of water molecule in the structure
of cation (Table 1). The high tendency to form hydrates by ammo-
nium cations arises from much lower energy of hydrates in com-
parison to anhydrous analogues. The calculated energy for N,N-
dimethyl(carboethoxymethyl)-3-phthalimidopropylammoni-
um chloride dihydrate (1) is about 5% lower than for monohydrate
(1a) and 10% lower in comparison to anhydrous form (1b) (Table
1). The similar effect is observed for N,N-dimethyl-3-phthalimido-
propylammonium hydrochloride monohydrate (2) where the cal-
culated energy for monohydrate is about 7% lower than for
anhydrous form (2a) [21] (Table 1). The chloride anion in (1) is en-
gaged in four non-linear hydrogen bonds. Three hydrogen bonds
are formed between chloride anion and hydrogen at C(12), C(14),
and C(16). The fourth hydrogen bond is between chloride anion
and one molecule of water (Table 1). Additionally the chloride an-
ion interacts via Coulombic attractions with positively charged
nitrogen atom. The N+(13)Á Á ÁClÀ distances are 3.775, 3.676 and
3.570 Å, for (1), (1a) and for (1b), respectively. The structure of
(1) has the lowest energy among the compounds (1), (1a), (1b).
The one molecule of water is engaged in two different hydrogen
bonds, OAHÁ Á ÁCl of 3.079 Å and OÁ Á ÁHAO of 2.824 Å. These data
prove that the water play an important role in the molecular struc-
ture of compound (1).
3.2. FTIR and Raman spectra
Room-temperature solid-state FTIR and Raman spectra as well
as the calculated spectra of (1) are shown in Fig. 3. The observed
and calculated harmonic frequencies and their tentative assign-
ments are listed in Table 2. These assignments are partly based
on the calculated spectrum of N-aminophthalimide [22]. In the
FTIR spectrum of (1) there are five stretching vibrations assigned
to the water molecules. The frequencies of these bands are 3565,
3513, 3435, 3359 and 3200 cmÀ1. The band in the vicinity about
3600 cmÀ1 is typical for OAH group that does not establish an H-
bond; it allows us to unambiguously characterize such an OAH
group [23]. The broad band that extend from 3400 to 2200 cmÀ1
suggest that water molecules in (1) form hydrogen bonds. A similar
situation is observed for N,N-dimethyl-3-phthalimidopropylam-
monium hydrochloride monohydrate [21]. This absorption is typi-
cal for hydrogen bond longer than 3 Å. In this case the calculated
length of hydrogen bond OAHÁ Á ÁCl is 3.079 Å. In the Raman spec-
trum (Fig. 3b) this absorption is absent. There is no theoretical
counterpart of the vibration observed in the FTIR spectrum for
(1) in the solid state in 2805–2471 cmÀ1 region because the theo-
retical data concern isolated molecule in the gas phase where no
intermolecular hydrogen bonds exist; these intermolecular inter-
actions are responsible for the absorption in the above region in
the solid state.
The FTIR spectrum of (1) shows characteristic bands at
1772 cmÀ1 which is due to asymmetric stretching vibrations of
carbonyl group
man spectrum this absorption is very strong and lies at 1770 cmÀ1
The symmetric stretching vibration sC@O appears in the FTIR
masC@O in a phthalimide moiety [24,25]. In the Ra-
.
m
spectrum as an intensive and broad nonsymmetrical band at
1703 cmÀ1 what can suggest the small nonequivalence of carbonyl
groups in the phtalimide moiety. The FTIR spectrum of N,N-
dimethyl(carboxymethyl)-3-phthalimidopropylammonium hydro-
chloride (3) (Fig. 3a, dotted line) shows characteristic vibration
Fig. 2. Structures of (a) N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropy-
lammonium chloride dihydrate (1), (b) N,N-dimethyl(carboethoxymethyl)-3-
phthalimidopropylammonium chloride monohydrate (1a), (c) N,N-dimethyl
(carboethoxymethyl)-3-phthalimido-propylammonium chloride (1b); (d) N,N-
dimethyl-3-phthalimidopropylammonium hydrochloride monohydrate (2); (e)
N,N-dimethyl-3-phthalimidopropylammonium hydrochloride (2a) calculated by
the B3LYP/6-31G(d,p) method.
bands of
1769 cmÀ1 and at 1709 cmÀ1, respectively. In this case the
and sC@O bands are more symmetrical in comparison to carbonyl
bands of (1). In the Raman spectrum of (1) this absorption is very
masC@O and
msC@O in
a
phthalimide moiety at
masC@O
m

I. Kowalczyk / Journal of Molecular Structure 928 (2009) 12–17
15
2.0
1.5
1.0
0.5
a
0.0
150
b
100
50
0
c
0.6
0.4
0.2
0.0
90
d
60
30
0
3500 3000 2500 2000
1500
1000
500
Wavenumbers [cm-1]
Fig. 3. FTIR spectra in Nujol and Fluorolube mulls of N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium chloride dihydrate (1) solid line, of
N,N-dimethyl(carboxymethyl)-3-phthalimidopropylammonium hydrochloride (3) dotted line (a); calculated FTIR spectrum (b); Raman spectrum (c); calculated Raman
spectrum (d).
weak and lies at 1706 cmÀ1 [26]. The nonequivalence of
m
asC@O in
The relations between the experimental 1H and 13C chemical shifts
FTIR spectrum is observed for N,N-bis-(phthalimidopropyl)-N-pro-
pylamine [27]. In contrast to above examples, in N,N-dimethyl-3-
phthalimidopropylammonium hydrochloride monohydrate and
N-n-butyltetrachlorophthalimide no split of the carbonyl bands
in FTIR spectra were observed in spite of different interactions of
each carbonyl group in the supramolecular structure [21,28]. The
(dexp) and the GIAO (Gauge-Independent Atomic Orbitals) isotropic
magnetic shielding tensors (rcalc) for (1) is shown in Fig. 4. Both
correlations are linear, described by the relationship: dexp = a + b
r
calc. The a and b parameters are given in Table 3. The very good
correlation coefficients (r2 = 0.9379) for 1H and (r2 = 0.9984) for
13C correlations of N,N-dimethyl(carboethoxymethyl)-3-phthalim-
idopropylammonium chloride dihydrate confirm the optimized
geometry of (1).
stretching vibration m(COO) of carboxy group for (1) is observed
at 1742 cmÀ1 and the stretching vibration
m(COOH) of carboxyl
group in FTIR spectrum for (3) is observed at 1721 cmÀ1. The
OH-bending d(HOH) of water molecule for (1) gives a fairly sharp
strong band at 1611 cmÀ1 in the FTIR spectra whereas in the Ra-
The correlation between the experimental chemical shifts and
calculated isotropic screening constants are better for carbon-13
atoms than for protons. The protons are located on the periphery
of the molecule and thus are supposed to be more efficient in inter-
molecular (solute–solvent) effects than carbons. The differences
between the exact values of the calculated and experimental shifts
for protons are probably due to the fact that the shifts are calcu-
lated for single molecules in gas phase. For this reason the agree-
ment between the experimental and the calculated data for
proton is worse than for carbon-13.
man spectrum this vibration gives a weak band at 1612 cmÀ1
.
In general, the calculated frequency values with 6-31G(d,p) ba-
sis set are close to experimental values of vibrational frequency.
The spectroscopic results and calculated data confirm the presence
of two molecules of water which interact via hydrogen bond be-
tween themselves and one of them additionally interact with chlo-
ride anion.
3.3. 1H NMR and 13C NMR spectra
4. Conclusions
The proton chemical shift assignments (Table 3) are based on
2D COSY experiments, in which the proton–proton connectivity
is observed through the off-diagonal peaks in the counter plot.
N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylamm-
onium chloride dihydrate (1) has been obtained by reaction of N,N-
dimethyl-3-propylamine with ethyl chloroacetate. The structure of

16
I. Kowalczyk / Journal of Molecular Structure 928 (2009) 12–17
Table 2 (continued)
Table 2
Observed and calculated B3LYP/6-31G(d,p) vibrational frequencies and infrared
intensities for N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium
chloride dihydrate (1).
Raman
IR
IR (calc.)
INT
Proposed assignment
321 w
251 w
203 w
169 w
167 w
102 s
355
259
216
182
169
114
98
21.3
15.3
5.78
22.6
14.8
6.58
6.34
5.77
6.20
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Raman
IR
3565 m
3513 m
3436 m
3359 m
3200 w
3059 w
IR (calc.)
INT
Proposed assignment
3653
3581
3484
3381
3221
3103
3097
3073
3061
3049
3011
2986
41.0
78.1
365
598
10.2
17.5
44.1
16.2
8.59
25.1
243
146
m
m
m
OH
OH
OH
vOH
m
m
m
m
m
m
m
OH
CH
CH
67
53
3063 w
The abbreviations are: s, strong; m, medium, w, weak; vw, very weak;
b, in plane bending; d, deformation; c, out of plane bending; and s, twisting.
m, stretching;
3023 w
2955 m
3012 w
2958 m
2943 w
2927 m
2911 m
2805 w
2784 vw
2697 vw
2574 w
2471 w
CH
CH2
CH2
CH2
vCH2
2825 vw
m
m
m
m
m
CH2
OH
OH
OH
OH
Table 3
Chemical shifts (d ppm) in D2O and calculating GIAO nuclear magnetic shielding
tensors ( cal) for N,N-dimethyl(carboethoxymethyl)-3-phthalimidopropylammonium
chloride dihydrate (1). The predicted GIAO chemical shifts were computed from the
linear equation dexp. = a + b rcalc with
experimental data.
r
1851
1795
1764
1721
1662
1649
1540
1528
1518
1510
1501
1497
1489
1466
1435
1398
1386
1369
1333
1314
1308
1291
1251
1221
1196
1158
1144
1127
1085
1060
1038
1034
1010
984
975
948
931
906
882
849
812
810
771
747
721
704
623
570
540
496
18.4
230
469
a and b determined from the fit the
1770 s
1743 w
1706 w
1772 s
1742 s
1703 s
1652 m
1611 m
m
m
m
m
asCO
COO
sCO
CC
93.7
12.3
3.91
36.2
7.38
11.9
3.81
7.70
20.0
19.1
6.16
57.5
79.3
15.6
65.4
40.8
2.76
3.49
289
60.9
20.9
22.0
19.7
8.71
26.9
11.8
45.2
16.1
124
dexp.
dcalc
rcalc
dexp.
dcalc
7.21
rcalc
C (4,7)
C (3,8)
C (5,6)
C (2,9)
C (10)
C (11)
C(12)
C(14,15)
C(16)
C(17)
C(18)
C(19)
a
126.1
133.6
137.6
172.7
37.2
24.6
63.8
55.2
65.1
126.65
136.38
136.65
172.27
38.12
25.99
67.63
51.71
62.30
165.82
67.63
14.47
72.71
63.61
63.36
H(4–7)
H(10)
H(11)
H(12)
H(14,15)
H(16)
H(18)
H(19)
7.82
3.71
2.21
3.77
3.31
4.21
4.19
1.26
23.94
28.17
29.91
27.16
28.29
26.35
27.35
30.47
1612 w
d(HOH)
3.39
1.82
4.30
3.28
5.03
4.13
1.31
m
m
m
m
m
m
m
CC
CC
CC
CC
CC
CC
CC, bCH2
30.04
155.51
166.85
127.91
142.80
132.89
36.07
127.91
177.63
204.3909
À1.0692
0.9984
1469 w
1453 w
1485 m
1470 m
1449 m
1399 s
1373 m
1350 m
1340 m
1313 m
1299 w
1282 w
1236 m
1221 m
1201 s
1171 w
1145 w
1125 vw
1104 w
1085 w
1079 vw
1048 m
1030 m
1012 m
985 w
basCH3
bOH
bsCH3
m
m
m
m
m
bCH2
bCH2
m
vCC
m
m
m
m
c
c
c
bCH2
bCCC
bCO
c
c
bCCC
bCCC
sring
bCCC
bCCC
bCCC
bCCC
bCNC
bring
bNCC
bCCC
167.6
66.2
15.9
1400 w
1374 w
1349 w
1322 w
CO
CC
CN
CC
28.8577
À0.9041
0.9379
b
r2
1276 w
CC, bCH2
1222 vw
1189 s
1169 w
CC
200
8
6
4
2
0
CC
CN
CN
CN
CH2
CH2
CH2
a
b
1128 vw
1106 vw
160
120
80
1079 vw
1035 vw
1008 m
986 vw
975 vw
928 vw
904 vw
890 w
0.03
26.6
0.75
38.7
33.7
10.2
22.3
8.96
145
40
969 w
923 m
0
0
40
120 160 200
80
calc [ppm]
22 24 26 28 30 32
CH2
CH2
904 vw
890 w
870 vw
840 vw
805 w
798 w
759 w
725 s
705 w
694 vw
607 w
550 w
530 w
486 w
σ
σcalc [ppm]
872 w
841 vw
Fig. 4. Plots of the experimental chemical shifts (dexp) vs the magnetic isotropic
shielding tensors ( calc) from the GIAO/B3LYP/6-31G(d,p) for N,N-dimethyl(carbo-
ethoxymethyl)-3-phthalimidopropylammonium chloride dihydrate (1); dpred = a + b
calc. (a) carbon-13; (b) proton.
r
800 vw
761 w
708 m
28.6
20.8
235
r
35.9
1.46
13.8
1.94
6.63
25.8
0.05
1.77
41.7
5.32
4.55
9.91
671 vw
605
the investigated compound has been analyzed by FTIR and NMR
spectroscopy and B3LYP calculations and compared with N,N-
dimethyl(carboxymethyl)-3-phthalimidopropylammonium hydro-
chloride (3). Both FTIR and Raman spectra of (1) are consistent
with the calculated structures in the gas phase and prove a crucial
role of water molecules in structure of the investigated compound.
The good correlations between the experimental 13C and 1H chem-
ical shifts in D2O solution and GIAO/B3LYP/6-31G(d,p) calculated
571 vw
525 vw
511 vw
464 vw
435 vw
421 w
406 vw
374 vw
354 w
s
s
c
ring
ring
CCC
462 vw
444 vw
468
440
428
419
397
369
Lattice mode
Lattice mode
Lattice mode
Lattice mode
Lattice mode
isotropic shielding tensors (dexp = a + b
optimized geometry of (1).
rcalc) has confirmed the

I. Kowalczyk / Journal of Molecular Structure 928 (2009) 12–17
17
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 C.01, Gaussian,
Inc., Wallingford CT, 2004.
Acknowedgment
This work was supported by the funds from Adam Mickiewicz
University, Faculty of Chemistry.
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