Spectroscopic properties of N-n-butyltetrachlorophthalimide and supramolecular interactions in its crystals

Article abstract of DOI:10.1016/j.molstruc.2006.10.002

A number of N-n-alkyltetrachlorophthalimides has been synthesized and N-n-butyltetrachlorophthalimide has been characterized by X-ray diffraction, FT-IR and NMR spectroscopy. Also B3LYP and DFT calculations have been carried out. The optimized bond lengths, bond angles and torsion angles calculated by B3LYP/6-31G(d,p) approach have been 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 which confirm the optimized geometry. In the supramolecular structure halogen bonds and intermolecular Cl?Cl interactions have been found as the main driving force which connects molecules into centrosymmetric tapes and planar sheets.

Full text of DOI:10.1016/j.molstruc.2006.10.002

Journal of Molecular Structure 833 (2007) 197–202
www.elsevier.com/locate/molstruc
Spectroscopic properties of N-n-butyltetrachlorophthalimide
and supramolecular interactions in its crystals
a
a
b,
b
*
´
Teresa Borowiak , Irena Wolska , Bogumił Brycki , Andrzej Zielinski ,
b,
*
Iwona Kowalczyk
a
Department of Crystallography, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan´, Poland
Laboratory of Microbiocides Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan´, Poland
b
Received 27 July 2006; accepted 2 October 2006
Available online 28 November 2006
Abstract
A number of N-n-alkyltetrachlorophthalimides has been synthesized and N-n-butyltetrachlorophthalimide has been characterized by
X-ray diffraction, FT-IR and NMR spectroscopy. Also B3LYP and DFT calculations have been carried out. The optimized bond
lengths, bond angles and torsion angles calculated by B3LYP/6-31G(d,p) approach have been compared with the X-ray data. The screen-
ing 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 which confirm the opti-
mized geometry. In the supramolecular structure halogen bonds and intermolecular Clꢀ ꢀ ꢀCl interactions have been found as the main
driving force which connects molecules into centrosymmetric tapes and planar sheets.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: N-n-Butyltetrachlorophthalimide; X-ray diffraction; Supramolecular crystal structure; Intermolecular halogen bond; B3LYP calculations;
FT-IR and NMR spectra
1. Introduction
In order to better understand the mechanism of biolog-
ical activity, we have synthesized a series of N-n-alkyltetra-
chlorophthalimides and in this paper the X-ray structure as
well as results on B3LYP calculations, FT-IR and NMR
spectroscopy of N-n-butyltetrachlorophthalimide [hereaf-
ter (1)] are presented.
There is also another aspect of our interest in tetrachlor-
ophthalimides, namely their supramolecular crystal struc-
tures which in the absence of strong hydrogen bond
donors and/or acceptors may be stabilized by the other
weak intermolecular forces. In (1) the two carbonyl groups
can potentially be involved in intermolecular carbonyl-car-
bonyl interactions that are able to compete successfully with
hydrogen bonds [5]. On the other hand, the carbon bonded
chlorine atoms C–Cl and electronegative oxygen atoms of
the carbonyl groups may form halogen bonds C–Clꢀ ꢀ ꢀO,
moreover, weak C–Hꢀ ꢀ ꢀO or C–Hꢀ ꢀ ꢀp bonds can be formed,
also Clꢀ ꢀ ꢀCl intermolecular interactions and pꢀ ꢀ ꢀp stacking
can influence the supramolecular packing motif [6–15].
Phthalimides, tetrachlorophthalimides, and N-substitut-
ed phthalimides are an important class of compounds
because of their biological activity. It has recently been
shown that tetrachlorophthalimide derivatives are good
a-glucosidase inhibitors. Inhibition of this enzyme decreas-
es glucose level in blood by delaying digestion of poly- and
oligosaccharides to absorbable monosaccharides, and due
to that tetrachlorophthalimides can be potentially valuable
for various diseases treatment as diabetes, certain forms of
hyperlipoteinemia, and obesity [1,2]. Structure-activity
relationship studies on N-n-alkyltetrachlorophthalimide
derivatives indicated that the hydrophobic groups at the
N atom are of crucial meaning [3,4].
*
Corresponding authors. Tel.: +48 61 829 1314/1306; fax: +48 61 865
8008.
E-mail address: iwkow@amu.edu.pl (I. Kowalczyk).
0022-2860/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2006.10.002

198
T. Borowiak et al. / Journal of Molecular Structure 833 (2007) 197–202
Table 2
The Cambridge Structural Database search (Version
Crystal data, data collection and structure refinement for (1)
5.27, 2006) [16] revealed 14 structures of tetrachlorophthal-
imides substituted at its N atom either with aromatic resi-
dues or with more complex groups but no one structure
with aliphatic substituents was found.
Compound
(1)
Empirical formula
Formula weight
T (K)
C12H9Cl4NO2
341.00
120(2)
˚
Wavelength (A)
0.71073
2. Experimental
Crystal system, space group
Triclinic, P ꢁ 1
Unit cell dimensions
˚
2.1. Synthesis
a (A)
5.2054(4)
11.3155(7)
12.1036(7)
103.678(5)
98.793(6)
101.459(6)
663.78(8)
2, 1.706
˚
b (A)
A mixture of equimolar amounts of tetrachlorophthalic
anhydride and amine in toluene was heated under reflux for
12 h. After this time the solution was removed under
reduced pressure. The residue was crystallized from hexane
and isopropanol (9:1) and dried under reduced pressure.
The melting points, yields and elemental analyses are given
in Table 1.
˚
c (A)
a (°)
b (°)
c (°)
3
˚
Volume (A )
Z, Dx (Mg/m3)
l (mmꢁ1
F(000)
)
0.886
344
h range for data collection (°)
hkl range
3.53–29.54
ꢁ4 6 h 6 7
ꢁ14 6 k 6 15
ꢁ16 6 l 6 16
2.2. Instrumentation
Crystals suitable for X-ray analysis were grown by slow
evaporation from hexane solution. All details of the X-ray
measurements, crystal data and structure refinement details
are given in Table 2. The data were collected on an Oxford
Diffraction KM4CCD diffractometer [17] at 120 K, using
graphite-monochromated Mo Ka radiation. A total of
782 frames were measured in six separate runs. The x-scan
was used with a step of 0.75°, two reference frames were
measured after every 50 frames, they did not show any
systematic changes either in peak positions or in their
intensities. The unit cell parameters were determined by
least-squares treatment of setting angles of 5199 highest-
intensity reflections chosen from the whole experiment.
Intensity data were corrected for the Lorentz and polariza-
tion effects [18]. The structure was solved by direct methods
with the SHELXS97 program [19] and refined by the
Reflections
Collected
Unique (Rint
6132
3265 (0.026)
3028
3265/0/172
1.077
0.0286
0.0764
0.475/ꢁ0.342
)
Observed (I > 2r(I))
Data/restraints/parameters
Goodness-of-fit on F2
R(F) (I > 2r(I))
wR(F2) (all data)
Max./min. Dq (e/A )
3
˚
For all obtained N-n-alkyltetrachlorophthalimides
NMR spectra in CDCl3 were measured with a Varian
Gemini 300VT spectrometer, operating at 300,07 and
75,46 Hz H and 13C, respectively. Infrared spectra were
1
recorded in the KBr pellets using a FT-IR Bruker IFS
113v spectrometer.
full-matrix least-squares method with the SHELXL97
The calculations were performed using the Gaussian 98
package [21] at the B3LYP [22,23] levels of theory with the
6-31G(d,p) basis set [24]. The molecular parameters were
optimized in ab initio calculations at density-functional
(DFT) levels of the theory using the split-valence polarized
6-31G(d,p) basis set.
CCDC 616256 for (1) contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/
P
2
2 2
program [20]. The function
w(jFoj ꢁ jFcj ) was mini-
mized with wꢁ1 = [r2(Fo)2 + (0.0422P)2 + 0.3079P], where
P ¼ ðF 2o þ 2F 2cÞ=3. All non-hydrogen atoms were refined
with anisotropic thermal parameters. The coordinates of
the hydrogen atoms were calculated 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.
Table 1
Preparation of N-n-alkyltetrachlorophthalimides
R
Formula
Elemental analysis (calc)/found (%)
Yield (%)
M.p. (°C)
C
H
N
C2H5
C4H9
C6H13
C8H17
C10H21
C12H25
C10H5Cl4NO2
C12H9Cl4NO2
C14H13Cl4NO2
C16H17Cl4NO2
C18H21Cl4NO2
C20H25Cl4NO2
C22H29Cl4NO2
(38.4) 38.3
(42.3) 42.3
(45.6) 45.5
(48.4) 48.7
(50.8) 50.6
(53.0) 52.8
(54.6) 54.7
(1.6) 1.9
(2.7) 2.5
(3.6) 4.0
(4.3) 4.3
(5.0) 4.9
(5.5) 5.5
(6.1) 6.1
(4.5) 4.4
(4.1) 4.1
(3.8) 3.8
(3.6) 3.7
(3.3) 3.2
(3.1) 3.2
(2.9) 2.9
75
98
90
90
95
90
93
190–191
150–151
145–146
142–143
135–136
135–136
130–131
C
14H29

T. Borowiak et al. / Journal of Molecular Structure 833 (2007) 197–202
199
Table 3
data_request/cif, or by emailing data_request@ccdc.cam.
Weak intermolecular interactions in crystals of (1)
ac.uk, or by contacting The Cambridge Crystallographic
Data Centre, 12, Union Road, Cambridge CB2 1EZ,
UK; fax: +44 1223 336033.
Cl(4)ꢀ ꢀ ꢀO(2)(i)
3.020(1) A
˚
Cl(7)ꢀ ꢀ ꢀO(9)(ii)
2.963(1) A
˚
C(4)–Cl(4)ꢀ ꢀ ꢀO(2)(i)
C(7)–Cl(7)ꢀ ꢀ ꢀO(9)(ii)
Cl(5)ꢀ ꢀ ꢀCl(6)(iii)
178.22(5)°
175.34(5)°
˚
3. Results and discussion
3.549(1) A
Symmetry codes: (i) ꢁx, 1 ꢁ y, 1 ꢁ z; (ii) 2 ꢁ x, ꢁy, 1 ꢁ z; (iii) 2 ꢁ x,
3.1. The crystal structure of (1)
1 ꢁ y, 2 ꢁ z.
A perspective view of the molecular structure together
with the atom numbering scheme is shown in Fig. 1. The
isoindole moiety is approximately planar, as in the other
structures [25–28] with maximum deviations between
˚
ꢁ0.032(1) and 0.029(1) A for C(5) and C(7), respectively.
The bond lengths and angles in the phthalimide moiety
are also comparable to those reported in the literature
[28]. The C–Cl bond lengths are in the range of 1.713(2)–
˚
1.716(2) A and are in agreement with the values reported
in the literature [25,26].
The main driving force for the supramolecular structure
formation are C–Clꢀ ꢀ ꢀO and C–Clꢀ ꢀ ꢀCl–C intermolecular
interactions. The Clꢀ ꢀ ꢀO distances are shorter than the
sum of oxygen and chlorine van der Waals radii (Table
3, Fig. 2). The attractive nature of this interaction has been
recognized by Lommerse et al. [6] as mainly due to electro-
static effects, but polarization, charge-transfer, and disper-
sion contributions all play an important role in causing
interpenetration of van der Waals volumes. The linearity
of the C–Clꢀ ꢀ ꢀO contacts [C(4)–Cl(4)ꢀ ꢀ ꢀO(2) and C(7)–
Cl(7)ꢀ ꢀ ꢀO(9)] is also observed (Table 3, Fig. 2) and is
explained by the anisotropic electron distribution of elec-
tron density around the halogen nucleus [6]. In (1), the
Clꢀ ꢀ ꢀO interactions connect molecules related by subse-
quent centers of inversion into infinite tapes, Fig. 2. The
n-butyl substituents of the neighboring molecules which
form one tape are oriented in opposite directions, accord-
ing to the inversion centers and resemble antennas, almost
perpendicular to the flat tetrachlorophthalimide moieties
[the torsion angle C(9)–N(1)–C(10)–C(11) is ꢁ73.3.(2)°].
The Clꢀ ꢀ ꢀCl intermolecular interactions between the
tapes give rise in turn to flat molecular sheets (Fig. 2) with
Fig. 2. The structure of one sheet formed from molecular tapes stabilized
by halogen bonds Clꢀ ꢀ ꢀO. The tapes are connected by Clꢀ ꢀ ꢀCl interactions.
Fig. 3. Stacking of the parallel sheets.
˚
the Cl(5)ꢀ ꢀ ꢀCl(6) distance of 3.549(1) A. This kind of inter-
actions has been recognized earlier as the one which is able
to steer the crystal packing towards a layered arrangement
[11]. However, no consensus exists in the outlook on the
nature of Clꢀ ꢀ ꢀCl interactions. One explanation [11,29] is
that there is a specific attractive force which produces short
contacts in certain directions. The other explanation is that
the atomic charge density of chlorine atoms has a non-
Fig. 1. A view of the molecule of (1). Displacement ellipsoids are drawn at
the 50% probability level and H atoms are depicted as spheres of arbitrary
radii.

200
T. Borowiak et al. / Journal of Molecular Structure 833 (2007) 197–202
Fig. 4. Details of the stacking between two parallel molecular tapes.
Fig. 5. Electrostatic interactions between molecules of two neighboring sheets. Symmetry codes: (i) 2 + x, y, 1 + z; (ii) 1 + x, y, 1 + z; (iii) 2 ꢁ x, 1 ꢁ y,
2 ꢁ z; (iv) 1 ꢁ x, 1 ꢁ y, 2 ꢁ z; (v) x, 1 + y, 1 + z; (vi) ꢁ1 + x, 1 + y, 1 + z.
spherical shape, producing a decreased repulsion and thus
closer Clꢀ ꢀ ꢀCl contacts in certain directions [8]. The
C–Clꢀ ꢀ ꢀCl angles, h1 and h2 are 150.44(5)° and 148.01(5)°
for the C(5)–Cl(5)ꢀ ꢀ ꢀCl(6) (2ꢁx, 1ꢁy, 2ꢁz) and
C(6)–Cl(6)ꢀ ꢀ ꢀCl(5) (2ꢁx, 1ꢁy, 2ꢁz), respectively, and the
interacting chlorine atoms are related by inversion centers.
The third level of the supramolecular structure organiza-
tion concerns interactions between the two-dimensional
sheets. They are stacked in a parallel mode and separated
data in Table 4. The experimental and calculated bond
lengths and bond angles are comparable in the most
cases.
Table 4
Selected X-ray and B3LYP parameters for N-n-butyltetrachlorophthali-
mide (1)
Parameters
X-ray
B3LYP 6-31G(d,p)
Bond lengths
N(1)–C(2)
N(1)–C(10)
C(7)–C(8)
C(8)–C(9)
C(10)–C(11)
C(2)–O(2)
˚
by 3.281(1) A (Fig. 3), the distance determined by the
1.398(2)
1.466(2)
1.381(2)
1.501(2)
1.523(2)
1.205(2)
1.390
1.460
1.380
1.500
1.530
1.212
length of the aliphatic chains [the distance C(10)ꢀ ꢀ ꢀC(13)
˚
is 3.891(2) A] on one side and by weak electrostatic interac-
tions between parallel tapes of two stacked sheets on the
other one. Molecules of two parallel tapes are stacked with
no overlap, the molecules of one tape are positioned over
gaps of the other tape (Fig. 4) in consequence of electro-
Bond angles
C(9)–N(1)–C(10)
N(1)–C(10)–C(11)
N(1)–C(2)–C(3)
C(9)–C(8)–C(7)
C(11)–C(12)–C(13)
O(9)–C(9)–N(1)
123.6(1)
111.6(1)
105.1(1)
130.4(1)
112.3(1)
125.2(1)
123.9
113.7
105.6
130.4
112.5
125.4
static
interactions
C(2)d+ꢀ ꢀ ꢀCl(4)dꢁ
,
C6d+ꢀ ꢀ ꢀCl4dꢁ
,
C3d+ꢀ ꢀ ꢀCl7dꢁ, and C9d+ꢀ ꢀ ꢀCl7d+. All these distances are
shorter than the sum of the respective van der Waals radii
and are equal to 3.311(1), 3.370(1), 3.389(1), and
˚
3.437(1) A, respectively (Fig. 5).
Torsion angles
No other types of intermolecular interactions have been
found in the supramolecular structure of (1).
C(2)–N(1)–C(10)–C(11)
C(9)–N(1)–C(10)–C(11)
C(8)–C(9)–N(1)–C(10)
N(1)–C(10)–C(11)–C(12)
C(10)–C(11)–C(12)–C(13)
O(2)–C(2)-N(1)–C(9)
O(2)–C(2)-N(1)–C(10)
O(9)–C(9)–N(1)–C(10)
101.0(1)
ꢁ73.3(2)
174.4(1)
ꢁ169.0(1)
177.6(1)
ꢁ178.2(1)
7.0(2)
78.9
ꢁ103.3
ꢁ178.8
63.6
177.8
ꢁ178.8
1.0
3.2. B3LYP calculations
The optimized geometry parameters were computed by
using the B3LYP and compared with the X-ray diffraction
ꢁ5.1(2)
ꢁ0.8

T. Borowiak et al. / Journal of Molecular Structure 833 (2007) 197–202
201
Fig. 6. FT-IR spectra of N-n-butyltetrachlorophthalimide (KBr pellet).
imides the stretching vibrations mCH2 and mCH3 groups are
observed in the region 2962–2853 cmꢁ1 and the deforma-
tion vibrations dCH2 and dCH3 in the region 1465–1385
cmꢁ1. The intense deformation band, c(C–H), of methy-
lene and methyl groups, lie in the range of 721–727 cmꢁ1
and depend on the alkyl substituent.
The characteristic vibration bands of mas C@O and ms
C@O are observed at 1773 and 1702 cmꢁ1, respectively
(Fig. 6) [4]. These bands, both asymmetric and symmetric,
of N-n-alkyl tetrachlorophthalimides slightly shift to lower
frequencies as the length of alkyl chain increases. No split
of the carbonyl bands was observed and that confirms the
equivalence of the both carbonyl groups in the phthalimide
moiety.
Table 5
Chemical shifts (d, ppm) in CD3Cl and calculated GIAO nuclear magnetic
shielding tensors (rcal) for N-n-butyltetrachlorophthalimide
dexp.
dcalc
rcalc
C (2,9)
C (3,8)
C (4,7)
C (5,6)
C (10)
C (11)
C (12)
C (13)
163.4
129.4
127.5
139.8
38.7
30.3
20.8
13.6
158.3
134.0
124.2
143.9
39.1
30.1
20.5
13.3
155.4
131.9
122.5
141.5
40.4
31.7
22.4
15.5
H (10)
H (11)
H (12)
H (13)
3.70
3.64
3.62
1.66
1.34
0.95
1.80
1.37
0.84
1.83
1.41
0.90
The predicted GIAO chemical shifts were computed from the linear
equation dexp. = A Æ rcalc + B with A and B determined from the fit of the
experimental data.
1
3.4. H NMR and 13C NMR spectra
1
In the H NMR spectra of N-n-alkyltetrachlorophthali-
Some discrepancies in the values of torsion angles
between the X-ray and theoretical data concern mainly the
n-butyl substituent and are caused by the packing forces [30].
mides the protons of methylene and methyl groups are
observed as triplets and multiplets in the range of 0.8–
4.0 ppm.
13C NMR spectra of N-n-alkyltetrachlorophthalimides
show signals about 163 ppm for carbon atoms of carbonyl
groups, and signals in the range of 127–140 ppm for carbon
atoms of aromatic ring. The signal of aliphatic carbon
atom attached to nitrogen atom is about 39 ppm. The res-
3.3. FT-IR spectra
The IR spectra of (1) in the solid state are presented in
Fig. 6. In the FT-IR spectra of N-n-alkyltetrachlorophthal-
a
b
4
3
2
1
0
150
120
90
60
30
0
0
1
2
3
4
0
30
60
90 120 150
σ (calc)
σ
(calc)
Fig. 7. The relationship (a) between the experimental 13C chemical shifts (d) and the GIAO computed 13C screening constants (r) and (b) between the
experimental 1H chemical shifts (d) and the GIAO computed 1H screening constants (r).

202
T. Borowiak et al. / Journal of Molecular Structure 833 (2007) 197–202
[2] S. Adisakwattana, K. Sookkongware, S. Roengsumran, A. Petsom,
N. Ngamrojnavanich, W. Chavasiri, S. Deesamer, S. Yibchok-anun,
Bioorg. Med. Chem. Lett. 14 (2004) 2893.
[3] H. Takahashi, S. Sou, R. Yamasaki, M. Sodeoka, Y. Hashimoto,
Chem. Pharm. Bull. 48 (2000) 1494.
[4] N. Puviarasan, V. Arjunan, S. Mohan, Turk. J. Chem. 26 (2002)
323.
[5] F.H. Allen, C.A. Baalham, J.P.M. Lommerse, P.R. Raithby, Acta
Crystallogr. B 54 (1998) 320.
[6] J.P.M. Lommerse, A.J. Stone, R. Taylor, F.H. Allen, J. Am. Chem.
Soc. 118 (1996) 3108.
[7] F. Zordan, L. Brammer, P. Sherwood, J. Am. Chem. Soc. 127 (2005)
5979.
[8] S.L. Price, A.J. Stone, J. Lucas, R.S. Rowland, A.E. Thornley, J. Am.
Chem. Soc. 116 (1994) 4910.
[9] G.R. Desiraju, R. Parthasarathy, J. Am. Chem. Soc. 111 (1989) 8725.
[10] O.V. Grineva, P.M. Zorky, Cryst. Rep. 45 (2000) 633.
[11] V.R. Pedireddi, D.S. Reddy, B.S. Goud, D.C. Craig, A.D. Rae, G.R.
Desiraju, J. Chem. Soc. Perkin Trans. 2 (1994) 2353.
[12] D.M.Y. Barrett, I.A. Kahwa, J.T. Mague, G.I. McOherson, J. Org.
Chem. 60 (1995) 5946.
[13] D.M.Y. Barrett, I.A. Kahwa, D.J. Williams, Acta Crystallogr. C 52
(1996) 2069.
[14] D.M.Y. Barrett, I.A. Kahwa, B. Raduchel, A.J.P. White, D.J.
¨
Williams, J. Chem. Soc. Perkin Trans. 2 (1998) 1851.
[15] R.C. Howell, S.H. Edwards, A.S. Gajadhar-Plummer, I.A. Kahwa,
G.L. McPherson, J.T. Mague, A.J.P. White, D.J. Williams, Molecules
8 (2003) 565, G4.
onance lines for other aliphatic carbon atoms are observed
between 20 and 40 ppm.
The proton chemical shift assignments are based on the
2D COSY experiments, in which the proton–proton con-
nectivity is observed through the off-diagonal peaks in
the counter plot. The 2D heteronuclear shifts correlated
counter map (HETCOR) has been used to identify reso-
nance signals in the 13C NMR spectra.
The experimental chemical shifts in CDCl3 and the
GIAO shielding constants calculated for N-n-butyltetra-
chlorophthalimide are listed in Table 5. The correlations
between the experimental 1H and 13C chemical shifts (dexp
)
and the computed screening constants (rcalc) are shown in
Fig. 7. For 1H and 13C the correlation is linear and
described by the following equation:
dexp ¼ A ꢀ rcalc þ B
Values of the slope (AC = 1.0366, AH = 1.0329) and inter-
cept (BC = ꢁ2.7491, BH = ꢁ0.09138) were determined
through a fit of the computed shielding constants to the
experimental chemical shifts.
The very good correlation coefficients (r2 = 0.99221) for
1H and (r2 = 0.99726) for 13C correlations confirm the opti-
mized geometry of (1).
[16] F.H. Allen, Acta Crystallogr. B 58 (2002) 380.
[17] Oxford Diffraction Poland, CrysAlisCCD, CCD data collection GUI,
version 1.171, 2003.
4. Conclusions
[18] Oxford Diffraction Poland, CrysAlisRED, CCD data reduction GUI,
version 1.171, 2003.
The molecular and crystal structures of N-n-butyltetra-
chlorophthalimide (1) have been determined by X-ray dif-
fraction and by the B3LYP calculations.
[19] G.M. Sheldrick, Acta Crystallogr. A 46 (1990) 467.
[20] G.M. Sheldrick, SHELXL97, Program for the Refinement of Crystal
Structures, University of Go¨ttingen, Germany, 1997.
[21] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb,
J.R. Cheeseman, V.G. Zakrzewski, A.J. Jr. Montgomery, R.E.
Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels,
K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi,
R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J.
Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K.
Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslow-
ski, J.V. Ortiz, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I.
Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-
Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe,
P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, J.L. Andres, C.
Gonzalez, M. Head-Gordon, E.S. Replogle, J.A. Pople, GAUSSIAN
98, Revision A 6 Gaussian, Inc., Pittsburg, PA, 1998.
[22] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
The main driving force for the supramolecular structure
are halogen bonds C–Clꢀ ꢀ ꢀO and intermolecular Clꢀ ꢀ ꢀCl
interactions. The first type of interactions generates centro-
symmetric molecular tapes and the Clꢀ ꢀ ꢀCl interactions
connect the tapes into planar sheets. The sheets in turn,
are positioned one over another and connected via weak
electrostatic interactions of the Cd+ꢀ ꢀ ꢀCldꢁ type.
FT-IR spectra are consistent with the observed structure
in the crystal. The good correlations between the experi-
1
mental 13C and H chemical shifts in CDCl3 solution of
(1) and GIAO/B3LYP/6–31G(d,p) calculated isotropic
shielding tensors (dexp = A Æ rcalc + B) have confirmed the
optimized geometry of (1).
[23] P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, J. Phys.
Chem. 98 (1994) 11623.
[24] W.J. Hehre, L. Random, P.V.R. Schleyer, J.A. Pople, Ab Initio
Molecular Orbital Theory, Wiley, New York, 1986.
Acknowledgement
[25] L.-S. Zhou, Y.-Q. Feng, B. Gao, D.-X. Shi, X.-F. Li, Acta
Crystallogr. E 59 (2003) o1066.
[26] X.-G. Liu, Y.-Q. Feng, W. Wang, Z.-P. Liang, G. Yang, Acta
Crystallogr. E 61 (2005) o1316.
This work was supported by the funds from Adam
Mickiewicz University, Faculty of Chemistry.
[27] X.-G. Liu, Y.-Q. Feng, P. Wu, X. Chen, F. Li, Acta Crystallogr. E 60
(2004) o2293.
References
[28] S.W. Ng, Acta Crystallogr. C 48 (1992) 1694.
[1] S. Sou, S. Mayumi, H. Takahashi, R. Yamasaki, S. Kadoya, M.
Sodeoka, Y. Hashimoto, Bioorg. Med. Chem. Lett. 10 (2000)
1081.
[29] N. Ramasubbu, R. Parthasarathy, P. Murray-Rust, J. Am. Chem.
Soc. 108 (1986) 4308.
[30] I. Hargittai, Pure Appl. Chem. 61 (1989) 651.