Substituent effects on hydrogen bonding of aromatic amide-carboxylate

Article abstract of DOI:10.1016/j.saa.2016.05.008

N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different substituents (X: Br, Cl, OCH₃, CH₃), and their crystal structures have been analyzed in order to understand the variations in their molecular geome

Full text of DOI:10.1016/j.saa.2016.05.008

Substituent effects on hydrogen bonding of aromatic amide-carboxylate
Ibrahim Sen, Hulya Kara, Akın Azizoglu
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doi: 10.1016/j.saa.2016.05.008
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11 December 2015
27 April 2016
9 May 2016
Please cite this article as: Ibrahim Sen, Hulya Kara, Akın Azizoglu, Sub-
stituent effects on hydrogen bonding of aromatic amide-carboxylate, (2016), doi:
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ACCEPTED MANUSCRIPT
Substituent Effects on Hydrogen Bonding of Aromatic Amide-
Carboxylate
Ibrahim Sen,a Hulya Kara,b and Akın Azizoglu a,c,*
a Department of Chemistry, Faculty of Arts and Sciences, University of Balikesir,TR 10145, Balikesir, Turkey
b Department of Physics, Faculty of Arts and Sciences, University of Balikesir, TR 10145, Balikesir, Turkey
c Havran Vocational School, University of Balikesir, TR 10560, Havran, Balikesir, Turkey
ABSTRACT
N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different
substituents (X: Br, Cl, OCH3, CH3), and their crystal structures have been analyzed in order
to understand the variations in their molecular geometries with respect to the substituents by
using 1H-NMR, 13C-NMR, IR and X-ray single-crystal diffraction. The carboxylic acid group
2
forms classic O–H···O hydrogen bonded dimers in a centrosymmetric R2 (8) ring motifs
for BAA-Br and BAA-Cl. However, no carboxylic acid group forms classic O–H···O
hydrogen bonded dimers in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two
crystallographically independent molecules in BAA-OCH3. DFT computations show that the
interaction energies between monomer and dimer are in the range of 0.5 – 3.8 kcal/mol with
the B3LYP/6-31+G*, B3LYP/6-31++G*, B3LYP/6-31++G**, and B3LYP/AUG-cc-pVDZ
levels of theory. The presence of different hydrogen bond patterns is also governed by the
substrate. For monomeric compounds studied herein, theoretical calculations lead to two low-
energy conformers; trans (a) and cis (b). Former one is more stable than latter by about 4
kcal/mol.
Keywords: Hydrogen bonding, Crystal structure, Computational methods, DFT
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1. Introduction
The basis of crystal engineering is to understand the relationship between the
crystal structure and molecular structure. This can be achieved by studying the most
prominent intermolecular interactions in the crystals, mainly the hydrogen bonds [1].
Hydrogen bonding has considerable interest in many fields within chemistry and
material science because of its fundamental role in the vital biological, chemical
processes and crystal engineering [2]. Among the most widely investigated ones are the
strong O-H···O, O-H···N, N-H···N, and N-H···O non-covalent interactions in various
organic compounds, which have already found extensive applications in molecular
recognition and self-assembly [3].
Amides tends to form modestly intermolecular and intramolecular N-H···O
hydrogen bonding. To exploit weak intramolecular N-H···O-H hydrogen bonding in
amide derivatives, the more competitive intermolecular N-H···O=C interaction needs
to suppressed. Several techniques have been developed to investigate weak inter- or
intramolecular hydrogen bonding in solution and/or in the solid phase. The NMR
spectroscopy is promising for studies in solution [4], the IR spectroscopy can be used
to detect samples in both the solution and solid state [5]. The computational studies can
provide useful information about the effects of discrete factors on the stability of the
H-bonds, [6, 7b] which are particularly valuable when experimental evidences are not
available.
Controlling the crystal structure provides to understand the strength and
directional preferences of hydrogen bonds and intermolecular interactions. The
energies for the strongest O-H···O hydrogen bonds are within 8-11 kcal/mol ranges
and weaker than covalent bonds, the former can be easily deformed by packing forces
and exhibit variable geometry in crystals [8].
Comparing the energies of different conformers of a compound helps us to
understand inter and intramolecular influences on a particular crystal form.
Computational techniques are used for studying intermolecular interactions between
different molecules of co-crystalline materials and help to determine the influence of
nearest neighbor molecules in a crystal on the molecular polarization [9].
In this report, X-ray crystallographic, NMR studies, and theoretical calculations
at DFT levels were used to probe the effects of substituent groups on the stabilization
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of amide N-H···O hydrogen bonds. The importance of substituents in amide hydrogen
bonding has been demonstrated using a series of small-organic molecule models
derived from 2-benzamidobenzoic acids (Scheme 1).
Scheme 1
2. Materials and Methods
2.1. General Procedure for the preparation of target compounds
The procedure to synthesize the target compounds is known in the literature [7].
To a solution of anthranilic acid (1.1 mmol) in anhydrous THF (5 ml) was added 1.0
mmol of the appropriate benzoyl chloride at room temperature. After cooling the
solution with ice bath, 1.2 mmol of triethylamine was added dropwise and reaction was
stirred at room temperature for additional 3-10 h. The mixture was poured into a 25
mL cold solution of 1.0 M HCl, and precipitates were collected by filtration.
Recrystallization from acetonitrile afforded the desired compound in quantitative
1
yields. Data for H NMR spectra are reported as follows: chemical shift (multiplicity,
coupling constants, and number of hydrogens). Abbreviations are as follows: s
1
(singlet), d (doublet), t (triplet), m (multiplet). H-NMR spectra were recorded on a
Bruker Model Avance DMX 400 Spectrometer at 400 MHz. It is also recommended to
1
acquire H NMR spectra in DMSO-d6, where otherwise exchangable protons such as
those of COOH, NH, and NH2 are usually visible [10]. All chemical reagents and
solvents were purchased from Merck or Aldrich Co. and used without further
purification. Analytical grade solvents were used for the crystallization experiments.
FT–IR spectra were measured with a Perkin–Elmer Model Bx 1600 instrument with
the samples as KBr pellets in the 4000–400 cm−1 range.
2-(4-Bromobenzamido)benzoic acid (BAA-Br): IR : ν 3317 (N-H), 3102 (Ar-H),
3024 (Ar-H), 2643 (OH-C=O), 1689 (C=O), 1661 (C=O, first amide band), 1585
1
(C=O, secondary amide band), 1485-1468 (C=C) cm-1; H-NMR (400 MHz, DMSO
d6): δ=13.2 (s, 1H), 12.1 (s, 2H), 8.7 (dd, J=8.2, 1.1 Hz, 2H), 8.1 (dd, J=7.9, 1.5 Hz,
2H), 7.9 (d, J=8.4 Hz), 7.4-7.3 (m), 7.2 (td, J=8.0, 1.0 Hz).
2-(4-Chlorobenzamido)benzoic acid (BAA-Cl): IR: ν 3311 (N-H), 3102 (Ar-H),
3024 (Ar-H), 2650 (OH-C=O), 1692 (C=O), 1659 (C=O, first amide band), 1587
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1
(C=O, secondary amide band), 1488-1468 (C=C), cm-1; H-NMR (400 MHz, DMSO
d6): δ=13.4 (s, 1H), 12.1 (s, 2H), 8.7 (dd, J=8.3, 1.1 Hz, 2H), 8.0 (dd, J=8.0, 1.5 Hz,
2H), 7.9 (d, J=8.7 Hz), 7.7-7.6 (m), 7.2 (td, J=8.0, 1.2 Hz).
2-(4-Methoxybenzamido)benzoic acid (BAA-OCH3): IR: ν 3317 (N-H), 3127 (Ar-
H), 2368 (OH-C=O), 1685 (C=O), 1647 (C=O), first amide band), 1585 (C=O,
1
secondary amide band), 1508-1458 (C=C), cm-1; H-NMR (400 MHz, DMSO d6):
δ=13.4 (s, 1H), 12.1 (s, 2H), 8.7 (d, J=8.2 Hz, 2H), 8.1 (dd, J=8.1, 1.5 Hz, 1H), 7.7 (d,
J=8.3 Hz), 7.6-7.5 (m), 7.3-7.2 (m), 6.9 (d, J=8.5 Hz), 3.7 (s, 3H).
2-(4-Methylbenzamido)benzoic acid (BAA-CH3): IR: ν 3317 (N-H), 3124 (Ar-H),
2345 (OH-C=O), 1654 (C=O, first amide band), 1542 (C=O, secondary amide band),
1508-1449 (C=C), cm-1; 1H-NMR (400 MHz, DMSO d6): δ=12.2 (s, 1H), 8.7 (d, J=8.1
Hz, 1H), 8.1 (d, J=8.0 Hz, 1H), 7.9 (d, J=8.1 Hz, 2H), 7.7 (t, J=8.0 Hz, 1H), 7.4 (d,
J=8.0 Hz, 2H), 7.2 (t, J=7.7 Hz, 1H), 2.4 (s, 4H).
2.2. Crystal structure determination
Diffraction measurements were made on a Bruker ApexII kappa CCD
diffractometer using graphite monochromated Mo–K radiation (λ = 0.71073 Å) at 100
K for BAA-Br, BAA-Cl, BAA-OCH3, and BAA-CH3. The intensity data were
integrated using the APEXII program [11]. Absorption corrections were applied based
on equivalent reflections using SADABS [12]. The structures were solved by direct
methods and refined using full–matrix least–squares against F2 using SHELXL [13].
All non–hydrogen atoms were assigned anisotropic displacement parameters and
refined without positional constraints. Hydrogen atoms were included in idealized
positions with isotropic displacement parameters constrained to 1.5 times the Uequiv of
their attached carbon atoms for methyl hydrogens, and 1.2 times the Uequiv of their
attached carbon atoms for all others. All of the crystallographic computations were
carried out using Shelxtl, Mercury 3.3 [14] and Ortep-3 [15] programs. Details of the
data collection parameters and crystallographic information for the complexes are
summarized in Table 1. Ortep diagrams of BAAs are depicted in Figure 1, and packing
diagrams are displayed Figure 2, Figure 3, Figure 4, and Figure 5.
2.3. Computational Details
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The initial geometries of BAAs have been calculated with density functional theory
(DFT) [16] using the combined Becke’s three-parameter exchange functional and the
gradient-corrected functional of Lee, Yang and Parr (B3LYP functional) [17] at the 6-31+G*
level. This functional has been demonstrated to predict reliable geometries for hydrogen
bonded systems [18]. Single point calculations at the B3LYP/6-31+G*, B3LYP/6-31++G**
and B3LYP/AUG-cc-pVDZ [19] level were performed on the fully optimized geometries
using the B3LYP/6-31+G* method. All calculations in the gas phase are achieved using the
Gaussian03 program [20].
3. Results and discussion
3.1. Description of the crystal structure of BAAs
Crystals of BAA-Br, BAA-Cl, BAA-OCH3, and BAA-CH3 have analogous
structures with different substituents. Intramolecular N–H···O hydrogen bonds are
observed in BAAs. The carboxylic acid group forms classic O–H···O hydrogen
2
bonded dimers in a centrosymmetric R2 (8) ring motifs which link the molecules into
pairs around inversion centers in a supramolecular assembly in the unit cell of BAA-
Br and BAA-Cl
.
Fig. 1
Table.1
In the crystalline architecture of BAA-Br, the dimers are involved in N1–
H1···O3 interactions generating an open ended chain structure along the b axis (Fig.
2a). These chains form zig-zag packing structure in the bc plane (Fig. 2b). The parallel
arrangement of the almost planar dimeric units in columns is indicated by the
projection in Fig. 2c.
Fig. 2
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In the crystalline architecture of BAA-Cl, intermolecular C5–H5···O3 weak
2
hydrogen bonds link the dimers generating R2 (14) motifs (Figure 3a). The dimers
linked by C–H···Cl [21] and C–H···O [22] weak intermolecular interactions to form
infinite 3D structure of BAA-Cl (Figure 3b and Figure 3c). This hydrogen bonded
polymeric networks lie in the ab-plane and stacks along to the c-axis (Figure 3b). The
parallel arrangement of the almost planar dimeric units in columns is indicated by the
projection in the bc-plane and stacks along to the a-axis (Fig. 3c). Besides that there is
an intermolecular C11-H11···
H··· = 127 , Cg2 = C9-C10-C11-C12-C13-C14, xiii = 1-x,-1/2+y,1/2-z] in 2. π ··· π
stacking is not discernible due to the large distances between adjacent arene moieties
(d > 4 Å) for BAA-Br and BAA-Cl
 contact [H···Cg2 = 2.88 Å, C11··· = 3.5303 Å, C11-


.
Fig. 3
The atomic size, polarization, and radial anisotropy increase in the order Cl < Br < I,
whereas electronegativity changes are in the reverse order [23]. While Cl···H interaction is
seen for BAA-Cl, Br···H interaction not appears for BAA-Br (Table 2).
Table 2
The carboxylic acid group don’t form classic O–H···O hydrogen bonded dimers
in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two
crystallographically independent molecules in BAA-OCH3 (Figure 1c). In the
crystalline architecture of BAA-OCH3, intermolecular O2−H2···O7/O6−H6···O3 and
2
C21−H21···O1/C6−H6···O5 hydrogen bonds link the molecules, generating R2 (10)
motifs and also the O2/O6 atom of carboxylate group form bifurcated weak hydrogen
2
bond with methyl group of aromatic ring which produce R2 (8) motifs via
C3−H3···O4/C18−H18···O8 and C15−H15B···O2/C30−H30B···O6 weak interactions
which leads to form 2D sheet in bc plane. C30−H30A···O1 weak intermolecular
interaction connect the molecules in the structure of BAA-OCH3 which form to
channels in 3D network of hydrogen bonds. This polymeric networks lie in the ac-
plane and stacks along to the b-axis (Figure 4b). Besides that π ··· π interactions
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between the aromatic rings (Cg2···Cg2xiii =3.8525 Å, Cg3···Cg3xiv =3.6702 Å,
Cg4···Cg4iii =3.7778 Å, [Cg2=C9-C10-C11-C12-C13-C14, Cg3=C16-C17-C18-C19-
C20-C21, Cg4=C24-C25-C26-C27-C28-C29, iii = 2-x,1-y,-z, xiii = -x,-y,1-z, xiv = 2-
x,-y,-z] are also observed in the hydrogen bonded assembly of BAA-OCH3
.
Fig. 4
The geometrical parameters show that N-H···O interactions should be stronger
than C-H···O interactions if we assume that the proton···acceptor distance is an
approximation of hydrogen bonding strength. Additionally, the N-H···O bond for
crystal structure BAA-OCH3 should be the strongest of all of the interactions of this
type. The geometrical parameters for the O-H···N intramolecular H bond also show
that this is the strongest interaction for all H bonds existing within the crystal structures
investigated here [24].
In the crystalline architecture of BAA-CH3, intermolecular O2−H2···O3 and
2
C6−H6···O1 hydrogen bonds link the molecules generating R2 (10) motifs which leads
to form hydrogen bonded one-dimensional chain structure of BAA-CH3 along a axis.
Also the O1 atom of carboxylate group form bifurcated C10−H10···O1 weak
intermolecular hydrogen bond which leads to form 2D sheet in bc plane (Figure 5b).
This polymeric 2D networks lie in the ac-plane and stacks along to the b-axis (Figure
5c). π ···π stacking is not discernible due to the large distances between adjacent arene
moieties (d > 4 Å) for BAA-CH3
.
Fig. 5
3.2 DFT Calculations
The energetic of hydrogen bonds in the solid state cannot be directly measured,
and this type of bonding leaves upon questions in many structural works.
Computational chemistry, on the other hand, generates theoretical results on hydrogen
bond energies at an inflationary rate, many obtained at high levels [25] and even more
in rather routine computations using black-box methods. Density functional theory
(DFT) is very appealing due to its excellent performance to cost ratio, and DFT
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methods, very successful in modeling hydrogen bonded systems, are widely used in the
computational chemistry community [26]. Hence, we wish to determine the strength of
hydrogen-bonding in BAA-Br, BAA-Cl, BAA-OCH3, and BAA-CH3 with the help of
DFT calculations using various diffuse functions. The geometries of monomers and
dimers of title compounds were initially optimized at the B3LYP/6-31G* level of
theory. Then, single point calculations were achieved at B3LYP/6-31+G*, B3LYP/6-
31++G*, B3LYP/6-31++G**, and B3LYP/AUG-cc-pVDZ levels. The interaction
energy of
and that of isolated monomers (in the geometry of the complex), was calculated using
the formula; Eint = Edimer - 2Emonomer (Table 3). The trends in interaction energy are
E of dimers, defined as the difference between the energy of the complex

similar at all levels of theory except for B3LYP/AUG-cc-pVDZ level. Moreover, the
geometrical parameters in the crystalline architecture of BAA-OCH3 show that N-
H···O interactions should be stronger than C-H···O interactions if we assume that the
proton···acceptor distance is an approximation of hydrogen bonding strength. This
experimental finding is only proved by diffuse double-ζ basis function AUG-cc-pVDZ,
which shows the highest interaction energy for dimer BAA-OCH3. Baruah et al. stated
that the importance of such small interaction energies in crystal lattice is well
documented with the help of AUG-cc-pVDZ basis set [25b]. The dimeric structure in
BAA-OCH3 should help reduce the torsion of the amide unit from the attached phenyl
ring. It is also reasonable to indicate that the inter- and intramolecular interactions
actually stabilized each other to result in the final crystal structures.
Table 3
Understanding the relationship between molecular structure and crystal structure
is the basis aspect in crystal engineering. Carboxylic acids play important roles in
many processes in chemistry and biology [27]. There should be two forms for the
monomer of studied carboxylic acids; trans (
carboxylic -OH group pointing toward the amide group, while the latter has the two
pointing away from each other. A 180 rotation about the C-O single bond would
a) and cis (b). The former has the

transform one isomer into the other. To understand the structural geometry of the
N−H···O hydrogen bond, conformational search calculations were performed at the
B3LYP/6-31+G* level. The theoretical calculations resulted in two low-energy
8

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conformers for compounds BAA-Br
In conformer and , N-H bond lengths of BAA-Br
remained unchanged. However, it is only shorter by 0.01 Ǻ in the trans conformer of
BAA-Cl. In conformer , O···H distances are found to be 1.85 Ǻ for BAA-Br BAA-
Cl BAA-OCH3, and BAA-CH3, whereas in conformer , these values are determined
to be 1.82, 1.81, 1.83, 1.83 Ǻ respectively. The relative energies realized through
calculations predicted trans conformers of BAA-Br BAA-Cl BAA-OCH3, and BAA-
,
BAA-Cl
,
BAA-OCH3, and BAA-CH3 (Fig. 6).
a
b
,
BAA-OCH3, and BAA-CH3
b
,
,
a
,
,
CH3, to be more stable by 4.18, 4.44, 4.04, and 4.01 kcal/mol, respectively.
Fig. 6
4. Conclusions
In this study, the roles of intermolecular interactions of a series of four amide
derivatives (BAAs) have been analyzed through single crystal studies and DFT
computations. These compounds demonstrate the formation N−H···O=C as a primary
structural motif, which constitute the key supramolecular synthon essential for the
formation of the crystal packing. The analysis of the interaction energy of the
molecular pairs via quantum chemical calculations suggests the presence of significant
stabilization from strong as well as weak interactions in the crystal packing, where it
has been observed for BAA-Br and BAA-Cl that the centrosymmetric N−H···O
supramolecular synthon has a significant contribution toward the overall stabilization.
DFT calculations about monomer and dimer of BAAs to determine the strength
of intermolecular hydrogen bonds show that the lowest interaction energy with
B3LYP/6-31+G*, B3LYP/6-31++G*, and B3LYP/6-31++G** basis sets is determined
in the compound BAA-CH3, whereas that with the AUG-cc-pVDZ basis set is found in
the compound BAA-Br. We have also demonstrated with the help of quantum
chemical calculations that intramolecular N-H···O=C hydrogen bonds exist in title
compounds when the competing intramolecular N-H···O-H hydrogen bond is inhibited
with the energy barriers of 4 kcal/mol.
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Acknowledgments
The authors are indebted to the Scientific and Technical Research Council of
Turkey (TUBITAK) and Balikesir Uinversity for their financial support. Prof. Kara
would like to thank TUBITAK for NATO-B1 and the Royal Society short visit
fellowship for financial support and Prof. Guy Orpen (School of Chemistry, University
of Bristol, UK) for his hospitality. The authors are also very grateful to Dr. Mairi F.
Haddow (The School of Chemistry, University of Bristol) for the X-ray measurements.
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FIGURE CAPTIONS
Fig. 1. The ORTEP illustrations of BAA-Br, BAA-Cl, BAA-OCH3, and BAA-CH3.
Fig. 2. (a) Hydrogen bonded dimers are involved in N–H···O intermolecular interactions
generating an open ended chain structure of BAA-Br. (b) The zig-zag chain structure of
BAA-Br in the bc-plane. (c) View of the same dimers in 1 BAA-Br as in Figure 2b after a
90 rotation, showing the planar sheet (view down crystallographic axis b direction). (d)
Space filling representation of BAA-Br as in Figure 1c.
Fig. 3. (a) Hydrogen bonded dimers are involved in C–H···Cl weak interactions generating a
2D sheet in the structure of BAA-Cl. (b) The packing structure of BAA-Cl in the ab-plane
(view down crystallographic axis c direction). (c) View of the same dimers in BAA-Cl as in
Figure 3b after a 90 rotation, showing the planar sheet in the bc-plane (view down
crystallographic axis a direction). (d) Space filling representation of BAA-Cl as in Figure 3c.
Fig. 4. (a) Hydrogen bonded 2D sheet in the structure of BAA-OCH3 in bc plane. (b)
C−H···O weak intermolecular interaction connect the molecules in the structure of BAA-
OCH3 which form to channels in 3D network of hydrogen bonds (view down crystallographic
axis b direction). (c) Space filling representation of BAA-OCH3 as in Figure 3c.
Fig. 5. (a) Hydrogen bonded one-dimensional chain structure of BAA-CH3. (b) C−H···O
weak intermolecular hydrogen bond form 2D sheet in bc plane. (c) View of the same 2D
sheets in BAA-Cl as in Figure 5b after a 90 rotation, the polymeric 2D networks lie in the
ac-plane and stacks along to the b-axis. (d) Space filling representation of BAA-CH3 as in
Figure 5c.
Fig. 6. Low-energy conformers and the relative energy for the title compounds BAA-Br,
BAA-Cl, BAA-OCH3, and BAA-CH3 at B3LYP/6-31+G* level. The selected O ... H and N-H
distances are given in Å.
Scheme 1 Synthesis of title compounds; BAA-Br, BAA-Cl, BAA-OCH3, and BAA-CH3.
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BAA-Br
BAA-Cl
BAA-OCH3
Fig. 1
BAA-CH3
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(a)
(b)
(c)
(d)
Fig. 2
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(a)
(b)
(c)
(d)
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Fig. 3
(a)
(b)
(c)
Fig. 4
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(a)
(b)
(c)
(d)
Fig. 5
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1.85
1.01
H
N
1.81-1.83
1.01
H
O
O
HO
X
O
X
=180o
H

N
O
O
Relative energies
X=Br,
X=Cl,
(0.00 kcal/mol)
(0.00 kcal/mol)
(4.18 kcal/mol)
(4.44 kcal/mol)
(4.04 kcal/mol)
(4.01 kcal/mol)
X=OCH3, (0.00 kcal/mol)
X=CH3, (0.00 kcal/mol)
Fig. 6
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O
O
COH
X
N(C2H5)3
N
+
H
-NH(C2H5)3Cl
COOH
NH2
CCl
O
X
X= Br= BAA-Br
Cl= BAA-Cl
OCH3= BAA-OCH3
CH3= BAA-CH3
Scheme 1
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TABLE CAPTIONS
Table 1 Crystal data and structure refinement of compounds BAA-Br, BAA-Cl, BAA-OCH3,
and BAA-CH3.
Table 2 Intramolecular and intermolecular hydrogen bond geometry (bond length in Å, bond
angle and in ) of compounds BAA-Br, BAA-Cl, BAA-OCH3, and BAA-CH3.
Table 3 Interaction Energies (Eint = Edimer - 2Emonomer) of BAA-Br, BAA-Cl, BAA-OCH3,
and BAA-CH3 (in kcal/mol).
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Table 1
Compound No
BAA-Br
C14H10BrNO3
320.13
BAA-Cl
C14H10ClNO3
275.68
BAA-OCH3
C15H13NO4
283.26
BAA-CH3
C15H13NO3
255.26
Chemical Formula
Mw
Crystal system
Space group
monoclinic
C2/c
monoclinic
P21/c
triclinic
P-1
monoclinic
P21/c
Unit cell dimensions
a= 27.3559(12) Ǻ a= 6.6989(5) Ǻ
b= 4.9265(2) Ǻ b= 7.2140(6) Ǻ
c= 20.8382(10) Ǻ c= 25.1489(18) Ǻ c= 13.828(3) Ǻ
a= 7.1716(11) Ǻ a= 11.7376(6) Ǻ
b= 12.971(2) Ǻ
b= 14.7540(9) Ǻ
c= 7.3524(4) Ǻ
α= 90 
α= 90 
β= 117.954(2) 
γ= 90 
2480.7(2)
100(2)
α= 90 
β= 92.624(4) 
γ=90 
1214.07(16)
100(2)
α= 83.900(9) 
β= 81.801(9) 
γ= 78.948(9) 
1245.3(4)
β= 100.234(3) 
γ= 90 
1253.01(12)
100(2)
V / Å3
T / K
100(2)
Z

8
4
4
4
calc / g cm-3
1.714
1.508
1.511
1.353
μ/mm-1
3.317
0.317
0.106
0.095
Reflections collected
30344
11505
2669
12983
4699
10665
2148
Independent reflections 2849
R1 [I > 2σ(I)]
0.0210
0.0558
0.0316
0.0722
0.0405
WR2 (all data)
0.0867
0.2608
0.1055
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Table 2
BAA-Br
D−H···A*
N1−H1···O1
N1−H1···O3i
O2−H2···O1ii
N1−H1A···O1
O2−H2···O1iii
C5−H5···O3iv
C3−H3···Cl1v
N1−H1…O1
D-H
0.80
0.80
0.84
0.81
0.84
0.95
0.95
0.80
H···A D···A D-H···A
2.06
2.54
1.81
1.99
1.83
2.45
2.84
1.94
2.676
3.128
2.646
2.671
2.670
3.357
3.737
2.645
133
132
177
141
176
160
157
145
BAA-Cl
BAA-OCH3
O2−H2···O7vi
N2−H2A···O5
O6−H6A···O3
C3−H3···O4i
0.82
0.80
0.82
0.93
0.93
0.93
0.93
0.93
0.96
0.96
0.82
0.82
0.95
0.95
1.82
1.95
1.86
2.56
2.60
2.54
2.52
2.69
2.66
2.72
1.92
1.82
2.60
2.67
2.638
2.649
2.645
3.421
3.439
3.390
3.367
3.575
3.550
3.568
2.638
2.639
3.491
3.397
180
146
160
153
150
151
152
154
154
148
145
178
155
134
C6−H6···O5
C18−H18···O8vii
C21−H21···Oviii
C15−H15B···O2vii
C30−H30B···O6i
C30−H30A···O1ix
N1−H1A···O1
O2−H2···O3x
BAA-CH3
C6−H6···O1xi
C10−H10···O1xii
*D: Donor, A: Acceptor; Symmetry codes: (i) [x,1+y,z], (ii) [1/2-x,3/2-y,-z], (iii) [2-x,1-y,-z],
(iv) [-x,-y,-z], (v) [x,1/2-y,1/2+z], (vi) [-1+x,y,1+z], (vii) [x,-1+y,z], (viii) [1+x,y,-1+z],
(ix) [1-x,1-y,1-z], (x) [-x,1/2+y,1/2-z], (xi) [-x,-1/2+y,1/2-z], (xii) [x,1/2-y,-1/2+z]
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Table 3
(Eint)
Basis sets
6-31+G*
BAA-Br
-3.58
BAA-Cl
BAA-OCH3
BAA-CH3
-1.97
-2.54
-2.99
6-31++G*
6-31++G**
AUG-cc-pVDZ
-3.76
-3.76
-0.51
-2.64
-2.47
-1.78
-3.17
-3.03
-2.71
-2.23
-1.99
-1.68
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GRAPHICAL ABSTRACT
H
O
O
HO
X
O
X
=180o
H
N
H
N

O
O
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HIGHLIGHTS
► N-(p-benzoyl)-anthranilic acid derivatives have been analyzed and characterized.
►
N-H···O=C hydrogen bonds are more stable than N-H···O-H hydrogen bonds.
► The interaction energy values of monomers are more stable than dimers.
►
The research shows intra and inter-molecular interactions in the title compound.
27