Polyamines. III. Spectroscopic properties of N,N-bis-(phthalimidopropyl)-N-octylamine and supramolecular interactions in its crystals

Article abstract of DOI:10.1016/j.molstruc.2009.12.034

A new derivative of polyamine, N,N-bis-(phthalimidopropyl)-N-octylamine has been synthesized and its structure studied by X-ray diffraction, FTIR, ¹H and ¹³C NMR spectroscopy. The B3LYP and DFT calculations have been carried out. The molecular conformation of N,N-bis-(phthalimidopropyl)-N-octylamine is folded and stabilized by an intramolecular C{single bond}H?O hydrogen bond. A close similarity to the conformation of N,N-bis-(phthalimidopropyl)-N-propylamine has been found. The both molecules differ by the length of the saturated chains on the N-amine atom. The long N-octyl chain substituent gives rise to the supramolecular structure which is different to that one formed by the N-propyl derivative. The supramolecular structure is driven by weak C{single bond}H?O and π?π interactions. The optimized bond lengths as well as bond angles for N,N-bis-(phthalimidopropyl)-N-octylamine calculated by B3LYP/6-31G(d,p) approach are compared with the X-ray data. The screening constants for ¹³C and ¹H atoms have been calculated by the GIAO/B3LYP/6-31G(d,p) approach and analyzed. Linear correlations between the experimental ¹H and ¹³C chemical shifts and the computed screening constants have been obtained.

Full text of DOI:10.1016/j.molstruc.2009.12.034

Journal of Molecular Structure 967 (2010) 34–41
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Polyamines. III. Spectroscopic properties of N,N-bis-(phthalimidopropyl)-
N-octylamine and supramolecular interactions in its crystals
a
a
b
b
Bogumił Brycki a, , Justyna Werner , Iwona Kowalczyk , Teresa Borowiak , Irena Wolska
*
a Laboratory of Microbiocides Chemistry, Faculty of Chemistry, Adam Mickiewicz University, 60-780 Poznan´, Poland
b Department of Crystallography, 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:
A new derivative of polyamine, N,N-bis-(phthalimidopropyl)-N-octylamine has been synthesized and its
structure studied by X-ray diffraction, FTIR, 1H and 13C NMR spectroscopy. The B3LYP and DFT calcula-
tions have been carried out. The molecular conformation of N,N-bis-(phthalimidopropyl)-N-octylamine
is folded and stabilized by an intramolecular CAHꢀ ꢀ ꢀO hydrogen bond. A close similarity to the conforma-
tion of N,N-bis-(phthalimidopropyl)-N-propylamine has been found. The both molecules differ by the
length of the saturated chains on the N-amine atom. The long N-octyl chain substituent gives rise to
the supramolecular structure which is different to that one formed by the N-propyl derivative. The supra-
Received 5 November 2009
Accepted 16 December 2009
Available online 29 December 2009
Keywords:
N,N-bis-(phthalimidopropyl)-N-octylamine
X-ray diffraction
B3LYP calculations
FTIR and NMR spectra
Supramolecular structure
molecular structure is driven by weak CAHꢀ ꢀ ꢀO and
pꢀ ꢀ ꢀp interactions. The optimized bond lengths as
well as bond angles for N,N-bis-(phthalimidopropyl)-N-octylamine calculated by B3LYP/6-31G(d,p)
approach are compared with the X-ray data. The screening constants for 13C and 1H atoms have been cal-
culated by the GIAO/B3LYP/6-31G(d,p) approach and analyzed. Linear correlations between the experi-
mental 1H and 13C chemical shifts and the computed screening constants have been obtained.
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
taining molecules have been synthesized and screened in a variety
of animal models of disorders of the central nervous system [8].
Polyamines are ubiquitous and essential compounds in pro-
karyotic and eukaryotic cells. Their cations have been reported to
possess a wide range of activities both within and external to the
central nervous system [1,2].
Many of these compounds have been based on toxins extracted
from spiders such as Agenelopsis aperta and Argiope lobata, and
the wasp Philantus triangulum [9]. These compounds comprise a
long poly(aminoalkane) chain linked to an aromatic or heterocyclic
group through a carbonyl group.
Recently, we have intensively investigated norspermidine
derivatives as antimicrobial agents. Some of these compounds
comprise aminoalkane chain linked to an aromatic or heterocyclic
group through a carbonyl group. N,N-bis-(phthalimidopropyl)-N-
octylamine [hereafter (1)] is a new compound in this series, which
display an antimicrobial activity and can also be used as an inter-
calator in DNA.
Polyamines usually adopt extended conformations whereas
some alkylamine–phthalimides, the polyamines with two terminal
amine groups blocked by phthalimide moieties, can feature folded
molecular geometries provided that steric conditions in a molecule
allow intramolecular interactions to operate. So, the folded confor-
The structural roles of polyamines are being determined at
molecular levels, contributing to the understanding of polynucleo-
tide and protein organization and interaction, as well as to the
solution of problem of genome transfer. Simple polyamines like
spermidine and spermine, can cause DNA to condense and aggre-
gate and induce B- to Z transition in certain DNA sequences. This
led the researchers to focus their attention on the potential use
of polyamines as antitumor drugs [3]. The metabolism of poly-
amines in prokaryotes has also been extensively studied [4]. The
inhibition of enzymes involved in the metabolism of parasitic pro-
tozoa has been recognized as a promising strategy for the chemo-
therapy of tropical diseases [5].
However, disadvantages associated with using the simple poly-
amines related to transport through biological membranes and
various toxic side effects can hinder these compounds from pro-
ceeding to clinical use [6,7]. Therefore various new polyamine con-
mations can be attributed to CAHꢀ ꢀ ꢀ
, C@Oꢀ ꢀ ꢀC@O or CAHꢀ ꢀ ꢀO
p
intramolecular interactions [10–12] and are characterized by
N(amine)-CACAN(phthalimide) torsion angle of about 60°. Those
alkylamine–phthalimides that have no possibility for such interac-
tions feature fully extended phthalimide functionalities with the
N+(amine)ACACAN(phthalimide) torsion angle of about 170°, e.g.
[10,11].
* Corresponding author. Tel.: +48 61 829 1314; fax: +48 61 865 8008.
E-mail address: brycki@amu.edu.pl (B. Brycki).
0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.12.034

B. Brycki et al. / Journal of Molecular Structure 967 (2010) 34–41
35
In the current paper we present the X-ray structure as well as
2. Experimental
results on B3LYP calculations, FTIR, Raman and NMR spectroscopy
of N,N-bis (phthalimidopropyl)-N-octylamine. We have been aim-
ing in recognizing the conformational preference of (1) whose ter-
2.1. Synthesis
tiary amine function is located across
a long octyl chain.
N,N-bis-(phthalimidopropyl)-N-octylamine (1) was prepared
according to the method reported previously [13]. A mixture
N,N-bis-(3-aminopropyl)amine (0.14 M) with phthalic anhydride
(0.31 M) were added to ice acetic acid (300 cm3) and stirred at
room temperature for 2 h. At the next stage N,N-bis-(phthalimido-
propyl)-amine was refluxed with octylbromide (0.15 M) and so-
dium carbonate in ethanol for 24 h. The crude product was
recrystallized from anhydrous ethanol; M.p. 89–91 °C, Yield 70%.
Elemental analysis: exp. and (calc): %C 71.43 (71.55); %H 7.52
(7.41); %N 8.29 (8.34).
Potentially, all the conditions exist to stabilize the same kind of
folded conformation as in the case of compounds quoted above.
The other aspect consisted in determination of the nature of supra-
molecular interactions in the crystal of (1).
Table 1
Crystal data, data collection and structure refinement for N,N-bis-(phthalimidopro-
pyl)-N-octylamine (1).
Compound
(1)
Empirical formula
Formula weight
T (K)
C30H37N3O4
503.63
120(2)
2.2. Instrumentation
Wavelength (Å)
Crystal system, space group
Unit cell dimensions
a (Å)
b (Å)
c (Å)
0.71073
Triclinic, P ꢁ 1
Crystals suitable for X-ray analysis were grown by slow evapora-
tion from ethanol solution. All details of the measurements, crystal
data and structure refinement are given in Table 1. The data were
collected on an Oxford Diffraction KM4CCD diffractometer [14] at
8.4035(4)
15.6219(6)
21.2487(11)
85.340(4)
85.403(4)
82.531(4)
2749.9(2)
4, 1.217
0.081
1080
4.11–26.37
ꢁ10 6 h 6 10
ꢁ19 6 k 6 19
ꢁ26 6 l 6 26
120 K, using graphite-monochromated MoKa radiation. The unit
a
(°)
b (°)
cell parameters were determined by least-squares treatment of set-
ting angles of highest-intensity reflections chosen from the whole
experiment. Intensity data were corrected for the Lorentz and
polarization effects [15]. The structure was solved by direct meth-
ods by use the SHELXS97 program [16] and refined by the full-ma-
trix least-squares method with the SHELXL97 program [17]. Seven
reflections were excluded from the reflection file due to their large
(|Fo|2 ꢁ |Fc|2) differences. The function w(|Fo|2 ꢁ |Fc|2)2 was mini-
c
(°)
Volume (Å3)
Z, Dx (Mg/m3)
l
(mmꢁ1
)
F (0 0 0)
h range for data collection (°)
hkl range
mized with wꢁ1 = [ 2(Fo)2 + (0.0714P)2], where P = (Fo2 + 2Fc2)/3.
r
Reflections:
Collected
32399
11208 (0.057)
4688
11208/0/667
Multi-scan
0.987
0.0496
0.1620
0.272/ꢁ0.218
All non-hydrogen atoms were refined with anisotropic thermal
parameters. The coordinates of the hydrogen atoms were calcu-
lated in idealized positions and refined as a riding model with their
thermal parameters calculated as 1.2 (1.5 for methyl group) times
Ueq of the respective carrier carbon atom.
The NMR spectra were recorded in CDCl3 on a Varian Gemini
300VT spectrometer, operating at 300.07 and 75.46 MHz for 1H
and 13C, respectively.
Unique (Rint
)
Observed (I > 2
r
(I))
Data/restraints/parameters
Absorption correction
Goodness-of-fit on F2
R(F) (I > 2
wR(F2) (all data)
Max/min.
(e/Å3)
r
(I))
D
q
Fig. 1. A perspective view of the N,N-bis-(phthalimidopropyl)-N-octylamine molecule together with the atom numbering scheme. Only molecule A is presented.

36
B. Brycki et al. / Journal of Molecular Structure 967 (2010) 34–41
The FTIR spectra in Nujol and Florolube mulls at 2 cmꢁ1 resolu-
bond angles and for this reason only molecule A is depicted in
Fig. 1 which shows also the atom numbering scheme. The both
molecules adopt folded conformations which are stabilized by
weak intramolecular CAHꢀ ꢀ ꢀO hydrogen bonds (Table 2, Fig. 1)
with the angles between their phthalimide residues of 67.9(1)°
and 67.4(1)° for molecules A and B, respectively. The same type
of conformation with similar parameters was found in N,N-bis-
(phthalimidopropyl)-N-propylamine [hereafter (2)] [12]. Such
close similarity follows from the same length of the N-propylamine
parts in both, (1) and (2). For the N-propylamine chains, from C(6A)
to C(6B) and from C(6C) to C(6D) in molecules A and B, respec-
tively, torsion angles exhibit the same pattern (Table 3), so the con-
formation of this part of molecules can be defined as follows: sc,
ap, sc, sc, ap, sc, ap, ac (sc stands for a synclinal conformation, ap
for an antiperiplanar one and ac for an anticlinal one [22]. The
ranges for the synclinal torsion angles are from about ꢁ55° to
ꢁ88° and from about 57° to 79°, whereas those for antiperiplanar
are from about ꢁ161° to 178°; the anticlinal torsion angle adopts
the value of about ꢁ118° and 109° in molecules A and B, respec-
tively. However, surprisingly, all these torsion angles are of oppo-
site signs in both molecules and this phenomenon might be
interpreted by the close packing requirements. On the other hand,
the conformations of the octyl chains are diverse in both molecules
(Table 3) and the pattern is as follows: ap, sc, sc, ap, sc, ap, ap, ap
and ap, sc, ap, ap, ap, sc, ap, ap for molecules A and B, and chains
from C(3A) to C(21A) and C(3C) and C(21C), respectively. Also in
this case the close packing requirements influence the conforma-
tion of the eight-membered octyl chain.
tion and Raman spectrum were recorded on a Bruker IFS 66v/S
instrument, evacuated to avoid water and CO2 absorption. The cal-
culations were performed using the Gaussian 98 package [18] at
the B3LYP [19,20] levels of the theory with the 6-31G(d,p) basis
set [21]. The molecular parameters were optimized in ab initio cal-
culations at density-functional (DFT) levels of the theory using the
split-valence polarized 6-31G(d,p) basis set.
CCDC 752433 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cam-
bridge Crystallographic Data Centre, 12, Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033).
3. Results and discussion
3.1. The crystal structure of (1)
The asymmetric unit of (1) contains two independent molecules
A and B which do not differ significantly in their bond lengths or
Table 2
Hydrogen-bonding geometry (Å and deg) for N,N-bis-(phthalimidopropyl)-N-octyl-
amine (1).
DAHꢀ ꢀ ꢀA
d(DAH)
d(Hꢀ ꢀ ꢀA)
d(Dꢀ ꢀ ꢀA)
<(DHA)
Intramolecular interactions
C4BAH4BAꢀ ꢀ ꢀO6A
0.97
0.97
2.75
2.65
3.592(3)
3.389(3)
146
133
Due to a lack of strong hydrogen bond donors the molecules are
organized into three-dimensional network only by weak intermo-
C4DAH4DBꢀ ꢀ ꢀO6C
Intermolecular interactions in the segment of molecules A
lecular interactions, the CAHꢀ ꢀ ꢀO hydrogen bonds and
pꢀ ꢀ ꢀp
C3AAH3AAꢀ ꢀ ꢀO6Bi
C9BAH9Bꢀ ꢀ ꢀO13Bii
C8BAH8Bꢀ ꢀ ꢀO6Aii
0.97
0.93
0.93
2.64
2.60
2.56
3.510(3)
3.421(3)
3.385(3)
150
147
148
stacking.
Thus, the supramolecular structure consists of separate seg-
ments, each formed by only one kind of molecules, A or B
(Fig. 2). The segments in turn consist of molecular columns whose
Intermolecular interactions in the segment of molecules B
C9DAH9Dꢀ ꢀ ꢀO13Di
C8DAH8Dꢀ ꢀ ꢀO6Ci
C3CAH3CAꢀ ꢀ ꢀO6Dii
C11CAH11Cꢀ ꢀ ꢀO6Diii
0.93
0.93
0.97
0.93
2.61
2.44
2.73
2.59
3.432(3)
3.305(3)
3.524(3)
3.434(3)
148
155
140
151
Interactions between segments
C8AAH8Aꢀ ꢀ ꢀO13D
0.93
2.59
2.62
2.54
2.62
2.65
2.53
3.460(3)
3.470(4)
3.288(3)
3.329(3)
3.228(3)
3.304(3)
157
153
138
134
121
141
C8CAH8Cꢀ ꢀ ꢀO13B
0.93
0.93
0.93
0.93
0.93
C10DAH10Dꢀ ꢀ ꢀO6Ai
C10BAH10Bꢀ ꢀ ꢀO6Cii
C10DAH10Dꢀ ꢀ ꢀO13Aiv
C10BAH10Bꢀ ꢀ ꢀO13Cv
Symmetry codes: (i) 1 + x, y, z; (ii) ꢁ1 + x, y, z; (iii) 1 ꢁ x, 2 ꢁ y, ꢁz ; (iv) 2 ꢁ x, 1 ꢁ y,
1 ꢁ z; (v) ꢁx, 2 ꢁ y, ꢁz.
Table 3
The mutual twist of phthalimide planes in (1) and (2).
Molecule A (1)
C3AAC4AAN5AAC13A
C3AAC4AAN5AAC6A
C3BAC4BAN5BAC13B
C3BAC4BAN5BAC6B
87.3(3)°
ꢁ88.8(3)°
61.8(3)°
ꢁ118.0(3)°
Molecule B (1)
C3CAC4CAN5CAC13C
C3CAC4CAN5CAC6C
C3DAC4DAN5DAC13D
C3DAC4DAN5DAC6D
ꢁ92.3(3)°
79.6(3)°
ꢁ65.2(3)°
109.5(3)°
Molecule (2) [14]
C3AC4AN5AC13
C3AC4AN5AC6
C30AC40AN50AC130
C30AC40AN50AC60
ꢁ83.0(1)°
93.2(1)°
84.3(2)°
ꢁ103.4(1)°
Fig. 2. The supramolecular structure of (1). Segments built of molecules A alternate
with segments built of molecules B, a projection along the [1 0 0] axis.

B. Brycki et al. / Journal of Molecular Structure 967 (2010) 34–41
37
central parts are formed from phthalimide stacks, and it is worthy
of note that only one phthalimide unit of each molecule of the col-
umn participates in the stack. The stacks of mutually parallel and
interlocked phthalimide units related by inversion centers extend
Fig. 3. A supramolecular column formed by molecules A: (a) A projection along the [1 0 0] axis. Stacking of phthalimide residues is shown in the center of the column. In the
peripheral parts of the column the octyl chains and the second phthalimide residue of each molecule are located. Hydrogen bonds CAHꢀ ꢀ ꢀO are indicated by broken lines. (b) A
projection of the column along the [0 0 1] axis.
Table 4
Torsion angles (deg) for N,N-bis-(phthalimidopropyl)-N-octylamine (1).
Molecule A
Molecule B
The N-propylamine chains:
C6AAN5AAC4AAC3A
N5AAC4AAC3AAC2A
C4AAC3AAC2AAN1A
C3AAC2AAN1AAC2B
C2AAN1AAC2BAC3B
N1AAC2BAC3BAC4B
C2BAC3BAC4BAN5B
C3BAC4BAN5BAC6B
ꢁ88.8(3)
173.7(2)
ꢁ55.4(3)
ꢁ65.3(3)
163.8(2)
ꢁ66.1(3)
175.9(2)
ꢁ118.0(3)
C6CAN5CAC4CAC3C
N5CAC4CAC3CAC2C
C4CAC3CAC2CAN1C
C3CAC2CAN1CAC2D
C2CAN1CAC2DAC3D
N1CAC2DAC3DAC4D
C2DAC3DAC4DAN5D
C3DAC4DAN5DAC6D
79.6(3)
ꢁ171.5(2)
57.2(3)
77.3(3)
ꢁ161.5(2)
62.9(3)
A175.1(2)
109.5(3)
The octyl chains:
C3BAC2BAN1AAC14A
C2BAN1AAC14AAC15A
N1AAC14AAC15AAC16A
C14AAC15AAC16AAC17A
C15AAC16AAC17AAC18A
C16AAC17AAC18AAC19A
C17AAC18AAC19AAC20A
C18AAC19AAC20AAC21A
C3AAC2AAN1AAC14A
C2AAN1AAC14AAC15A
ꢁ73.9(3)
164.2(2)
ꢁ53.8(3)
ꢁ176.4(2)
66.2(3)
165.5(3)
ꢁ176.6(3)
172.2(3)
172.0(2)
ꢁ72.4(3)
C3DAC2DAN1CAC14C
C2DAN1CAC14CAC15C
N1CAC14CAC15CAC16C
C14CAC15CAC16CAC17C
C15CAC16CAC17CAC18C
C16CAC17CAC18CAC19C
C17CAC18CAC19CAC20C
C18CAC19CAC20CAC21C
C3CAC2CAN1CAC14C
72.5(3)
ꢁ154.9(2)
ꢁ179.8(2)
166.7(3)
ꢁ178.8(3)
ꢁ74.2(4)
ꢁ175.4(3)
177.5(3)
ꢁ156.1(2)
C2CAN1CAC14CAC15C
79.1(3)

38
B. Brycki et al. / Journal of Molecular Structure 967 (2010) 34–41
along the [1 0 0] direction. Within the A stack an overlap takes
place between the C@O bond and the phenyl ring of two consecu-
tive phthalimide units.
(N(1A)AC(2A)AC(3A)AC(4A)) has an antiperiplanar conformation
but in the crystal this is a synclinal conformation (Table 5). The
conformation of the octyl chain (C(2B)AN(1A)AC(14A)AC(15A))
in the gas phase is synclinal while in crystal this conformation is
antiperiplanar.
The conformation differences are probably caused by intermo-
lecular interactions in the crystals. It is well known that intermo-
lecular interactions may cause the molecular geometry in the
crystals to be different from that of the free molecules [23,24].
The column is stabilized by the stacking interactions just men-
tioned and by intermolecular weak hydrogen bonds CAHꢀ ꢀ ꢀO indi-
cated in Table 2 and in Fig 3. The remaining parts of the molecules
that do not participate in the stacks, form layers which are built out
of the octyl chains and the phthalimidopropyl fragments and are
located out of the stacks The octyl chains make a steric hindrance
which prevents the stacking interactions of the phthalimide units
situated in these peripheral parts of the columns. The layers extend
also in the [1 0 0] direction. The structure of a segment formed
from molecules A is shown in Fig. 3(a) and (b). The segments made
of molecules B are similar and for this reason haven’t been pre-
sented in a separate figure. Molecules B form also stacks of parallel
phthalimidopropyl units but with almost no overlap.
3.3. 1H NMR and 13C NMR spectra
The proton chemical shift assignments are based on the 2D
COSY experiments, in which the proton–proton connectivity is ob-
served through the off-diagonal peaks in the counter plot. The 2D
heteronuclear shifts correlated counter map (HETCOR) has been
used to identify resonance signals in the 13C NMR spectra.
The A and B segments interact by CAHꢀ ꢀ ꢀO hydrogen bonds be-
tween the both kinds of molecules (Table 3).
The experimental chemical shifts in CDCl3 and the GIAO shield-
ing constants calculated for (1) are listed in Table 6. The correlations
between the experimental 1H and 13C chemical shifts (dexp) and the
3.2. B3LYP calculations
computed screening constants (
r
calc) are shown in Fig. 4. For 1H and
13C the correlation is linear and described by the following equation:
The optimized geometry parameters computed by using of the
B3LYP are compared with the X-ray diffraction data in Table 5.
The experimental and calculated bond lengths and bond angles
are comparable in most cases. In crystal structure the length of
hydrogen bond (C(4B)AH(4BA)ꢀ ꢀ ꢀO(6A) is 3.592(3) Å while in the
gas phase this distance is over 6 Å. It means that no hydrogen bond
in gas phase is present.
According to the torsion angles presented in Table 4, the mole-
cules in the gas phase are more folded in comparison to those in
the crystal. The torsion angle in the gas phase of the N-propyl chain
dexp ¼ A ꢀ rcalc þ B ð1Þ
Values of the slope (AC = ꢁ1.0891, AH = ꢁ0.9834) and intercept
(BC = 201.1927, BH = 31.4254) were determined through a fit of the
computed shielding constants to the experimental chemical shifts.
The very good correlation coefficients (r2 = 0.9876) for 1H and
(r2 = 0,9966) for 13C correlations confirm the optimized geometry
of (1).
The aromatic protons of phthalimide ring at 293 K show multi-
plets of AA0XX0 type according to Pople’s notation (Fig 5) [25]. This
type of splitting is characteristic for ortho-disubstituted benzene
ring, like in ortho-dichlorobenzene [26]. However, in N,N0,N00–
(nitrilotriethylene)trisphthalimide aromatic protons of phthali-
mide ring show unusual NMR characteristic, which is strongly
dependent on temperature [11]. Initially multiplets at 213 K go
through a singlet at 283 K to become again multiplet at 323 K. It re-
flects dynamic behavior of molecule in solution and molecular
interactions between phthalimide rings [11].
Table 5
Selected X-ray and B3LYP parameters of N,N-bis-(phthalimidopropyl)-N-octylamine
(1).
Parameters
X-ray
B3LYP 6-31G(d,p)
Bond lengths (Å)
N(1A)AC(2A)
N(1A)AC(14A)
C(4A)AN(5A)
N(5A)AC(6A)
N(5B)AC(6B)
N(5A)AC(13A)
N(5B)AC(13B)
C(6A)AO(6A)
C(13A)AO(13A)
1.464(3)
1.463
1.466
1.457
1.404
1.404
1.404
1.404
1.215
1.215
1.479(3)
1.454(3)
1.390(3)
1.398(3)
1.392(3)
1.401(3)
1.217(3)
1.210(3)
3.4. FTIR and Raman spectra
The FTIR spectra of (1) in the solid state and calculated
spectrum are presented in Fig. 6 and the assignments proposed
Bond angles (°)
Table 6
C(2A)AN(1A)AC(2B)
C(2A)AN(1A)AC(14A)
C(13A)AN(5A)AC(4A)
C(6A)AN(5A)AC(4A)
N(5A)AC(6A)AC(7A)
O(13A)AC(13A)AN(5A)
111.6(2)
113.3
112.7
124.0
123.6
105.6
125.3
Chemical shifts (d, ppm) in CDCl3 and calculated GIAO nuclear magnetic shielding
tensors (rcal) for N,N-bis-(phthalimidopropyl)-N-octylamine (1).
109.7(2)
124.0(2)
123.6(2)
106.2(2)
125.8(3)
dexp.
dcalc
rcalc
dexp. dcalc rcalc
C (2)
C (3)
C (4)
51.4
26.2
36.5
53.4
29.3
33.5
135.71
157.87
153.95
H (2)
H (3)
H (4)
H (8,11)
H (9,10)
H (14)
2.48 2.55 29.36
1.80 1.86 30.06
3.73 3.51 28.39
7.82 7.91 23.91
7.71 7.70 24.13
2.48 2.55 29.36
Torsion angles (°)
C(2B)AN(1A)AC(14A)AC(15A)
C(14A)AN(1A)AC(2A)AC(3A)
C(2A)AC(3A)AC(4A)AN(5A)
C(3A)AC(4A)AN(5A)AC(13A)
C(3A)AC(4A)AN(5A)AC(6A)
C(13A)AN(5A)AC(6A)AO(6A)
O(6A)AC(6A)AC(7A)AC(8A)
N(5A)AC(6A)AC(7A)AC(8A)
C(13A)AN(5A)AC(6A)AC(7A)
C(14A)AC(15A)AC(16A)AC(17A)
N(1A)AC(2B)AC(3B)AC(4B)
N(1A)AC(2A)AC(3A)AC(4A)
164.2(2)
172.0(2)
173.7(2)
87.3(3)
ꢁ88.8(3)
ꢁ179.5(2)
2.3(5)
ꢁ67.9
ꢁ160.1
178.0
92.1
ꢁ86.6
179.8
ꢁ0.19
179.9
0.17
C (6,13) 168.4 168.7 29.87
C (7,12) 133.8 132.6 63.00
C (8,11) 132.2 131.1 64.33
C (9,10) 123.1 121.6 73.12
C (14)
C (15)
C (16)
C (17)
C (18)
C (19)
C (20)
C (21)
a
H (15–19) 2.37 1.72 30.21
53.7
31.9
29.6
29.3
27.5
26.9
22.7
14.1
60.3
29.4
26.6
29.1
29.6
30.8
21.6
9.9
129.41
157.72
160.35
158.00
157.59
156.46
164.87
175.62
201.1927
ꢁ1.0891
0.9966
H (20)
H (21)
1.24 1.56 30.37
0.87 1.14 30.79
ꢁ178.0(3)
0.8(3)
ꢁ176.4(2)
ꢁ66.1(3)
ꢁ55.4(3)
179.1
179.6
177.1
31.4254
Hydrogen bond (Å)
C(4B)AH(4BA)ꢀ ꢀ ꢀO(6A)
b
ꢁ0.9834
3.592(3)
6.41
r2
0.9876

B. Brycki et al. / Journal of Molecular Structure 967 (2010) 34–41
39
8
(b)
(a)
150
120
90
6
4
2
0
60
30
0
-30
0
30
60
90 120 150 180
22
24
26
28
30
σ
calc [ppm]
σcalc [ppm]
Fig. 4. The relationship for (1): (a) between the experimental 13C chemical shifts (d) and the GIAO computed 13C screening constants (
r H
) and (b) between the experimental 1
chemical shifts (d) and the GIAO computed 1H screening constants (
r).
7.850
7.800
7.750
7.700
7.650
ppm (t1)
Fig. 5. The 1N,N-bis-(phthalimidopropyl)-N-octylamine (1) in CD3Cl.
1.2
(a)
1.0
0.8
0.6
0.4
0.2
0.0
0.8
(b)
0.6
0.4
0.2
0.0
3500 3000 2500 2000
1500
1000
500
Wavenumbers/cm-1
Fig. 6. The spectra of N,N-bis-(phthalimidopropyl)-N-octylamine: (a) FTIR spectrum in Nujol and Fluorolube emulsion; and (b) Raman spectrum.

40
B. Brycki et al. / Journal of Molecular Structure 967 (2010) 34–41
are given in Table 7. These assignments are partly based on the cal-
culated spectrum of N-aminophthalimide [27].
1710 cmꢁ1. In the Raman spectrum this absorption is very small
and lies at 1707 cmꢁ1 [30]. The difference between intensities of
symmetric and asymmetric stretching vibrations of carbonyl
groups is connected to with the symmetry of the molecule. When
In general, the bands around 1650–1350 cmꢁ1 in FTIR spectra
are assigned to skeletal CAC stretching modes of benzene ring.
The CAN stretching vibrations of (1) are observed at 1187 and
two C@O bonds are not coplanar the intensity of
lower than that of the sC@O [27]. The split of
m
asC@O should be
1178 cmꢁ1
.
m
m
asC@O and sC@O
m
The FTIR spectrum of (1) shows characteristic bands at 1771
bands suggests the nonequivalence of carbonyl groups in pthali-
mide moiety which is confirmed by X-ray data.
and 1764 cmꢁ1 which are due to asymmetric stretching vibrations
of carbonyl group
Raman spectrum this absorption is very strong and lies at 1770
and 1765 cmꢁ1. The symmetric stretching vibration
sC@O appears
masC@O in a phthalimide moiety [28,29]. In the
4. Conclusions
m
in the FTIR spectrum as broad and intensive bands at 1721 and
The molecular structure of N,N-bis-(phthalimidopropyl)-N-
octylamine (1) has been determined by X-ray diffraction and by
the B3LYP calculations. In the crystal the molecule adopts a folded
conformation which is stabilized by an intramolecular CAHꢀ ꢀ ꢀO
hydrogen bond.
Table 7
FTIR and Raman frequencies of N,N-bis-(phthalimidopropyl)-N-octylamine (1).
The supramolecular structure is also stabilized by weak
FTIR
Raman
Proposed assignment
CAHꢀ ꢀ ꢀO and
p
ꢀ ꢀ ꢀ interactions. No C@Oꢀ ꢀ ꢀC@O interactions have
p
2974w
2952w
2924w
2871w
2854vw
2822vw
1771w
1764w
1721s
3093w
3061m
2943m
2849m
2802w
2732w
1777vs
1765s
m
m
m
m
m
m
m
m
m
m
m
m
CH
been found. The supramolecular structure of (1) differs from that
of (2) and the difference is caused by a diverse length of the ali-
phatic chains on the N-amine atom.
CH2
CH2
CH2
CH2
CH2
asCO
asCO
sCO
sCO
CC
Both FTIR and Raman spectra are consistent with the observed
structure in the crystal.
Good correlations between the experimental 13C and 1H chem-
ical shifts in CDCl3 solution of (1) and GIAO/B3LYP/6-31G(d,p) cal-
1710s
1707vw
1611w
1467vw
1453w
culated isotropic shielding tensors (dexp = Aꢀ
rcalc + B) have
1610w
1465w
1447w
1430w
1396m
1374w
1366w
1329w
1311w
1294vw
1286vw
1279vw
1250vw
1212vw
1187w
1178w
1113vw
1099vw
1087vw
1065vw
1050vw
1038w
1021vw
984vw
976vw
950vw
911vw
897vw
883vw
869vw
857vw
819vw
795vw
759vw
723m
confirmed the optimized geometry of (1).
CC
dasCH3
m
m
dasCH3
m
dCH2
dCH2
m
m
m
1437vw
1399vw
1384vw
1368vw
1326vw
1315vw
1298vw
1282vw
1264vw
1253vw
CC
CC
Acknowledgments
This work was supported by the funds from Adam Mickiewicz
University, Faculty of Chemistry.
CC, dCH2
CC
CC
CC
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dCH2
m
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bCH
bCH
c
c
m
dCH2
bCC
c
c
dCH2
dCO
c
CC
CN
CN
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CH
CH
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1049vw
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975vw
CH
CH
CH
879vw
870vw
bCC
c
m
m
c
sring
dCO
bCC
bring
CH
CC
CC
CH
816vw
802vw
758vw
713vw
691vw
628vw
531w
716m
694vw
630w
571w
531vw
c
c
CH
CC
483vw
472
sring
sring
464vw
355vw
278vw
241vw
193w
159w
87m
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