The evaluation of the role of C-H?F hydrogen bonds in crystal altering the packing modes in the presence of strong hydrogen bond

Article abstract of DOI:10.1016/j.molstruc.2015.10.105

Interactions involving fluorine is an area of contemporary research. To unravel the importance of weak C-H?F hydrogen bonds and C-H?π interactions in organic compounds in the presence of strong hydrogen bond, a series of N-benzylideneanilines with simultaneously hydroxyl (-OH) and fluorine substitutions were synthesized for structural analysis. These compounds have been studied through experimental single crystal X-ray diffraction analysis and computational methods (Gaussian09 and AIM2000). The hydroxyl group present in all the molecules were found to form strong O-H?N hydrogen bond, but the spatial arrangement of the molecules connected by this hydrogen bond have been found to be controlled by the weak C-H?F and C-H?O hydrogen bonds, weak C-H?π and π?π interactions. This manuscript illustrates the importance of several weaker interactions in altering the packing modes in the presence of strong hydrogen bonds.

Full text of DOI:10.1016/j.molstruc.2015.10.105

Journal of Molecular Structure 1106 (2016) 154e169
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
The evaluation of the role of CeH/F hydrogen bonds in crystal
altering the packing modes in the presence of strong hydrogen bond
Gurpreet Kaur 1, Sandhya Singh 1, Amritha Sreekumar, Angshuman Roy Choudhury*
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Sector 81, Knowledge City, S. A. S. Nagar, Manauli PO,
Mohali, 140306, Punjab, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Interactions involving fluorine is an area of contemporary research. To unravel the importance of weak C
Received 13 August 2015
Received in revised form
29 October 2015
Accepted 30 October 2015
Available online 6 November 2015
eH/F hydrogen bonds and CeH/
p interactions in organic compounds in the presence of strong
hydrogen bond, a series of N-benzylideneanilines with simultaneously hydroxyl (eOH) and fluorine
substitutions were synthesized for structural analysis. These compounds have been studied through
experimental single crystal X-ray diffraction analysis and computational methods (Gaussian09 and
AIM2000). The hydroxyl group present in all the molecules were found to form strong OeH/N hydrogen
bond, but the spatial arrangement of the molecules connected by this hydrogen bond have been found to
Keywords:
be controlled by the weak CeH/F and CeH/O hydrogen bonds, weak CeH/
p and p/p interactions.
N-benzylideneanilines
CeH/F hydrogen bond
Gaussian09
This manuscript illustrates the importance of several weaker interactions in altering the packing modes
in the presence of strong hydrogen bonds.
© 2015 Elsevier B.V. All rights reserved.
AIM2000
Weak interactions
Organic fluorine
Benzylideneanilines
CLP
1. Introduction
known to yield highly stable crystal structures thereby making it
difficult to alter the packing features through small alteration in the
Crystal engineering deals with the understanding of both strong
and weak intermolecular forces to build a desired three dimen-
sional architecture to achieve robust molecular framework for
advanced applications [1]. A clear understanding of strong and
weak interactions is needed for appropriate applications of crystal
engineering to design different functional materials. Crystallization
of molecules from different solvents and solvent mixtures or by
using different crystallization techniques are known to result into
different crystal structures (polymorphs) of the same compound
[2]. The connection between molecular structure and its crystal
structure can only be achieved through an understanding of
intermolecular interactions in the solid state [3]. Various strong and
weak intermolecular forces include strong and weak hydrogen
parent molecule [7]. On the other hand, the crystal structures
governed by only weak hydrogen bonds or by a combination of
strong and a number of weak hydrogen bonds are altered easily by
minor changes in the parent molecule [8]. Weaker hydrogen bonds
result into lower stabilization energies while forming molecular
assemblies by the formation of dimers, trimers, tetramers, chains,
ladders, ribbons etc. [9] Therefore, crystal structures governed by
these interactions can easily be altered by the incorporation of
other functional groups. Among the weak hydrogen bonds, the
interactions offered by “organic fluorine” [10] are of specific inter-
est because of its ambiguous behaviour [11] in the solid state. In
spite of the highest electronegativity of fluorine, it was considered
to be weaker electron acceptor than oxygen or nitrogen and was
refuted to have true hydrogen bonds by Howard et al. [11c] Thalladi
et al. [12] for the first time glorified the role of CeH/F interactions
in their structural investigations on fluoro-benzenes using newly
developed techniques of in-situ crystallization [12,13]. In the last
decade, a number of research groups have illustrated that organic
fluorine offers various intermolecular interactions such as
bonds [3], interaction involving halogens [4], XeH/
p
(X ¼ C, N, O)
interactions [5], interactions [6] etc. The molecules, which
p/p
pack in the crystal lattice through strong hydrogen bonds are
* Corresponding author.
CeH/FeC, CeF/XeC (X ¼ F, Cl, Br) and CeF/p [14]. The signif-
E-mail address: angshurc@iisermohali.ac.in (A.R. Choudhury).
These two authors have contributed equally towards this manuscript.
1
icance of these interactions in crystal engineering have been
http://dx.doi.org/10.1016/j.molstruc.2015.10.105
0022-2860/© 2015 Elsevier B.V. All rights reserved.

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
155
highlighted in the review by Berger et al. [15], by Chopra and Guru
Row [16] in their recent highlight and further by Chopra in his
perspective [17]. The polarizability of organic fluorine was earlier
refuted based on the high electronegativity of F. A recent experi-
mental charge density study first revealed the formation of sigma
hole on fluorine thereby indicating that organic fluorine is also
partially polarizable [18].
Ultra detector at 40 kV of tube voltage and 40 mA of the current.
The data sets were collected over 2q
ranging from 5 to 50ꢀ with a
scanning speed of 5ꢀ per minute with 0.02ꢀ step for all the
compounds.
The PXRD patterns have been simulated from the crystal co-
ordinates using Mercury [20] and compared with the observed
PXRD patterns using WINPLOTR210 (ESI, Fig. S4: 1 to 24). The
simulated PXRD patterns were found to match with the experi-
mentally observed PXRD recorded on the bulk sample. This in-
dicates that the bulk phase is represented by the structure
determined by the single crystal X-ray diffraction technique.
Melting points and the melting enthalpies of all the compounds
(Table S1) were determined from the DSC (Perkin Elmer DSC 8000)
traces recorded at 5ꢀ per minute heating rate under Nitrogen at-
mosphere (ESI, Fig. S5: 1 to 24).
Since, the interactions offered by organic fluorine are generally
weak in nature, their application in crystal engineering has mostly
been studied in the absence of any strong hydrogen bond donor and
acceptors group(s) [9a-d,14a-d]. Our recent structural in-
vestigations in a series of N-benzylideneaniline and azobenzene
indicate that the weak interactions offered by organic fluorine are
capable of offering various repetitive supramolecular synthons
through CeH/FeC hydrogen bonds [9a-d]. In this manuscript, we
intend to evaluate the structure directing/controlling ability of
organic fluorine in the presence of a hydroxyl group in fluorinated
N-benzylideneanilines. These molecules containing simultaneously
eOH and CeF groups offer an opportunity for a systematic analysis
of weak hydrogen bonds offered by the CeF group in the presence
of strong hydrogen bonds involving the eOH group. We have
structurally analysed and computationally studied these molecules
to achieve an understanding of the individual roles played by
organic fluorine and the hydroxyl group in crystal packing. Our
earlier structural studies on N-benzylideneanilines contained
structures of 87 compounds (1 to 87) [9a,c,d]. Therefore, the new
compounds studied in this manuscript have been numbered from
88 to 111 so that direct comparison can be made with the previ-
ously reported structures.
3. Diffraction data collection and structure solution
Single crystal X-ray diffraction data for the crystals were
recorded using Mo e Ka radiation at 100.0(1) K using Oxford
cryosystem either on Bruker AXS KAPPA APEX-II CCD diffractom-
eter or on a Rigaku XtaLAB mini diffractometer using Mercury375/
M CCD detector using graphite monochromator. The data sets,
which collected on Bruker diffractometer were recorded using a
detector distance of 6.0 cm with varying 2q position of the de-
tector using the APEX-II suit [22], data reduction and integration
were performed SAINT V7.685A12 [22] (Bruker AXS, 2009) and
absorption corrections and scaling were done using SADABS
V2008/112 [22] (Bruker AXS). The remaining data sets collected on
XtaLAB mini diffractometer were recorded using a fixed detector
distance of 5.0 cm and the detector kept at 2
q
¼ 29.85ꢀ and were
2. Experimental section
processed with Rigaku Crystal Clear suite 2.0 [23]. All the crystal
structures were solved using SHELXS [24] and were refined using
the SHELXL [24] available within Olex2 [25]. All the hydrogen
atoms have been geometrically fixed and refined using the riding
model except the hydrogen of the eOH group, which has been
located from the difference Fourier map and was refined iso-
tropically. Complete crystal data collection and refinement details
for all the compounds are available in the Tables S1aed (ESI). The
thermal ellipsoid plots of all the molecules have been drawn at
50% probability for the non-H atoms using Mercury and are shown
with the atom labels in the ESI (Fig. S6: 1 to 20). All the packing
and interaction diagrams have been generated using Mercury 3.5
[20]. Geometric calculations have been done using PARST [26] and
PLATON [27].
2.1. Procedure for synthesis
All the starting materials were purchased from Sigma Aldrich
and were used without further purification. All the compounds
were synthesized using the mechano-chemical approach [19].
Corresponding benzaldehyde (0.5 mmol) and aniline (0.5 mmol)
were ground using mortar and pestle with approximately 100 ml
methanol. The resulting mixture slowly solidified upon grinding for
10e15 min to yield the desired product. The solid crude products
were then dissolved in various solvents (methanol, ethanol, hex-
ane, ethyl acetate, chloroform and dichloromethane) and the so-
lutions were allowed to evaporate slowly in refrigerator (4 ꢀC) for
recrystallization and subsequent growth of single crystals suitable
for structure determination.
Scheme 1 describes all the molecules studied and the method of
nomenclature used in this manuscript. Based on the nature and
position of the substitutions, the compounds have been sub divided
into 6 groups as indicated in the Scheme 1. Out of 24 synthesized
compounds, 20 compounds yielded single crystals of good quality
for structural analysis. Remaining four compounds (C.N. 100, 101,
102 and 103), although crystalline (PXRD pattern in ESI), have al-
ways resulted into the glassy material during the recrystallization
process.
3.1. Crystallographic modelling of disorder
Among the 20 compounds reported in this manuscript, the
compound 90 was found to have positional disorder due to rota-
tion of the aniline ring around C8eN1 bond and the compounds
104 and 108 were found to exhibit positional disorder due to in-
plane flipping of the molecule around C]N bond. PART com-
mand was used to analyse these positional disorders. These dis-
orders were refined for two independent positions, namely A and
B (‘A’ for higher occupancy). For the purpose of refinement, the
position of the carbon atoms in part A and B of the phenyl rings
were fixed at the same position using EXYZ command in
SHELXL2013. Thermal parameters were also constrained to be
equal for the atoms at the same position using EADP command in
SHELXL2013. All hydrogen atoms were then positioned geomet-
rically and refined using a riding model with Uiso (H) ¼ 1.2 Ueq (C,
N). The occupancy ratio for the two parts in 90, 104 and 108 were
All the synthesized compounds were characterized by 1H
NMR (400 MHz, Bruker Biospin Advance-III NMR spectrometer)
(ESI, Fig. S2: 1 to 20) and FTIR (Perkin Elmer Spectrum2) (ESI,
Fig. S3: 1 to 20) spectroscopy. Powder X-ray Diffraction (PXRD)
data were recorded on a Rigaku Ultima IV diffractometer using
parallel beam geometry, Cu e K
a
radiation, 2.5ꢀ primary and
secondary solar slits, 0.5ꢀ divergence slit with 10 mm height
limit slit, sample rotation stage (120 rpm) attachment and DTex

156
G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Scheme 1. Numbering scheme and systematic identification numbers of the compounds studied.
found to be 0.882(3): 0.118(3), 0.506(7): 0.494(7) and 0.896(3):
0.104(3) respectively.
the stabilization energies of the molecular dimers formed through
OeH/N or CeH/O or CeH/F hydrogen bonds have been calcu-
lated using the MP2 [28] level of theory with 6-31 þ G(d) basis set
using the Gaussian09 [29] as has been described in detail in our
earlier publication [9c]. The pairs of molecules, which are found to
be connected with each other by OeH/N/CeH/O/CeH/F
hydrogen bonds, were selected for the calculation of single point
energy of the dimer (Edimer) and the single point energy of the
corresponding monomers were also calculated using Gaussian09 in
the same method and same basis set. The stabilization energies
(SEG09 ¼ Edimer ꢁ 2 ꢂ Emonomer) of these dimers were corrected for
the basis set superposition error (BSSE) using the counterpoise
method [30]. GaussView [31] was used to visualize the molecular
4. Theoretical calculations
4.1. Stabilization energy calculations by Gaussian09
The crystal structures reported in this manuscript are found to
be controlled by combined effects of strong (OeH/N) and weak
(CeH/O, CeH/F) hydrogen bonds and much weaker interactions
involving the aromatic
p systems (CeH/p and p/p). As we are
interested to evaluate the ability of organic fluorine in altering the
crystal packing in the presence of other stronger hydrogen bonds,

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
157
dimers while the Gaussian calculation were carried out.
The compounds 89, 90 and 91 contain fluorine at para-, meta-
and ortho-position of the A ring respectively. In case of 89, the
CeH/F hydrogen bond involving F1 and H13 connects two R22ð7Þ
dimers formed by OeH/N and CeH/O hydrogen bonds (Fig. 2a).
In the case of 90, a pair of CeH/F hydrogen bonds involving F1 and
H11 connects two R22ð7Þ dimers (Fig. 2b) utilizing the synthon II
[9d], identified by us recently. A CeH/F hydrogen bond involving
F2 and H16 similarly connects two R22ð7Þ dimers (Fig. 2c) in 91.
Although the R22ð7Þ dimers are common in all the structures
belonging to this group, the way these dimers are connected to
each other in the crystal lattice through weak CeH/F hydrogen
bond(s) is different in 89, 90 and 91. One of the two molecules
present in the asymmetric unit of 91 did not have any interaction
involving the fluorine atom.
4.2. CoulombeLondonePauli (CLP) energy calculations
The lattice energies of these crystal structures were calculated
using the semi-classical density sums (SCDS) PIXEL method [32],
which was implemented within the 2011 version of the CLP model
of intermolecular interaction package. This calculation further
partitioned the lattice energy into columbic (ECOUL), polarization
(EPOL), dispersion (EDISP) and repulsion (EREP) components.
4.3. Analysis of topological properties
The wave function files for the interacting dimers were gener-
ated using the Gaussian09. These wave function files were then
used as inputs for AIM2000 package [33] for the analysis of topo-
In addition to the resemblance in the formation of strong
hydrogen bonded chains of dimers, similarity in the weak CeH/
p
logical parameters like electron densities (rc) and Laplacian (V2rc
)
interactions (involving H7 with Cg1 and H9 with Cg2) have also
been identified in the structures of 88, 89 and 90 (Fig. 3, Table 3a).
at the bond critical points (BCP). These topological properties
provide the information about the nature of the concerned inter-
In the case of 91, weak p/p interactions have also been observed
between two R22ð7Þ dimers (Fig. 3d, Table 3b).
action. The topological properties like electron density (r) and
Laplacian (V2r), local potential (V(rCP)), kinetic (G(rCP)) and total
energy densities (E(rCP)) at the BCPs of CeH/F hydrogen bonds
have been plotted against bond path (Rij) using sigma plot [34].
5.2. Structural comparison of the compounds belonging to group 1b
All the four compounds belonging to this group (92, 93, 94 and
95) crystallize in the monoclinic centrosymmetric P21/c space
group (Table 4). The compounds 92 and 94 are isostructural, but 93
and 95 adopt different unit cell parameters. All the four compounds
have the same R22ð7Þ dimers formed by strong OeH/N and
CeH/O hydrogen bonds as were seen in all four compounds
belonging to group 1a (Fig. 4, Table 5). The stabilization energies for
these dimers are in the range between ꢁ7.3 and ꢁ12.5 kcal/mol.
The dimer in 95 has the highest stabilization energy as it has one
OeH/N hydrogen bond and two CeH/O hydrogen bonds forming
the dimer (Fig. 4d).
5. Structural description of the compounds studied
Here, we intend to discuss the effect of the position of fluorine
on the crystal structures of our model system by keeping the po-
sition of the eOH substitution constant in one ring, while the po-
sition of the fluorine atom is varied on the other ring. Following this
method, 24 compounds have been subdivided into six classes
namely group 1a, group 1b, group 2a, group 2b, group 3a and group
3b (Scheme 1). The phenyl ring originating from aniline is desig-
nated as the “A” ring, while the same originating from the benz-
aldehyde will be designated as the “B” ring.
In the structures of 92, 93, 94 and 95, the R22ð7Þ dimers are
connected to each other by CeH/F and/or CeH/O hydrogen
bonds (Fig. 5, Table 5). Both 92 and 94 have additional CeH/O
hydrogen bonds involving H1A with O1 and H9 with O1 (Fig. 5,
Table 5). The fluorine atom present at the meta-position of the A
ring in 94 is involved in a short contact with H6 (Fig. 5, Table 5).
Interestingly, the ortho-fluorinated compound (95) forms a dimer
(Fig. 5, Table 5) adopting the robust synthon IV involving two
different CeH/F hydrogen bonds reported by us recently [9d].
In addition to these interactions, there are different weak
5.1. Structural comparison of the compounds belonging to group 1a
Among the compounds belonging to this group (88, 89, 90 and
91), 88 and 90 are iso-structural (Pbca), while 89 and 91 are
different from the other two (space groups Pca21 and P2/c respec-
tively) (Table 1). All the four compounds have been found to form
dimers involving OeH/N and CeH/O hydrogen bonds together
forming a seven membered ring (Fig. 1), which can be designated
with the graph set notation R22ð7Þ as described by Etter [35]. These
dimers have been found to have stabilization energies
between ꢁ6.4 and ꢁ9.3 kcal/mol (Table 2).
CeH/p interactions in the structure of 92, 93 and 94 (Table 6). The
R22ð7Þ dimers in 92, 93 and 94 are connected to each other by uti-
lizing two CeH/p interactions between a pair of dimers (Fig. 6a, b
Table 1
Unit cell parameters of the compounds belonging to group 1a (88, 89, 90, 91) compounds.
Identification code
88
89
90
91
CCDC No.
Crystal system
Space group
a/Å
b/Å
c/Å
1040698
Orthorhombic
Pbca
10.8047(6)
9.4127(5)
19.9210(11)
90
90
1040699
Orthorhombic
Pca21
10.9585(12)
9.7492(10)
9.4677(9)
90
90
1040700
Orthorhombic
Pbca
10.879(2)
9.323(2)
19.888(4)
90
90
90
2017.1(8)
8
1
1040701
Monoclinic
P2/c
19.737(4)
6.1175(14)
18.701(4)
90
118.201(4)
90
1989.9(8)
8
ꢀ
ꢀ
a
b
g
/
/
ꢀ
/
90
90
Volume/Å3
2025.99(19)
8
1
1011.50(18)
4
1
Z
Z0
2

158
G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Fig. 1. OeH/N and CeH/O hydrogen bonded dimers in 88 (a), 89 (b), 90 (c) and 91 (d).
Table 2
Intermolecular hydrogen bonds of the compounds belonging to group 1a (88, 89, 90, 91) compounds.
Code
88
DeH/A (D ¼ C, O; A ¼ O, N, F)
d H/A/Å
:DeH/A/ꢀ
Symmetry code
SEG09 kcal/mol
r
eÅꢁ3
V
2r eÅꢁ5
O1eH1/N1
C7eH7/O1
C11eH11/O1
O1eH1/N1
C7eH7/O1
C13eH13/F1
O1eH1/N1
C7eH7/O1
C11AeH11A/O1
C11AeH11A/F1
O1eH1/N2
C20eH20/O1
O2eH2/N1
C7eH7/O2
1.78
2.73
2.75
1.78
2.72
2.54
1.87
2.70
2.68
2.69
1.92
2.63
1.86
2.60
2.61
171
140
124
176
143
127
174
140
124
148
169
156
166
156
149
1 ꢁ x, y þ ½, ½ ꢁ z
ꢁ7.7
0.22
0.03
0.04
0.29
0.04
0.04
0.23
0.04
0.02
0.03
0.29
0.04
0.24
0.04
0.03
0.82
0.16
0.17
0.92
0.18
0.23
0.85
0.18
0.18
0.15
0.91
0.19
0.89
0.21
0.18
1 ꢁ x, y ꢁ ½, ½ ꢁ z
2
ꢁ x, 1 ꢁ y, zꢀꢁ ½
ꢁ1.6
ꢁ9.3
3
89
90
2 ꢁ x, 2 ꢁ y, z þ ½
2 ꢁ x, 2 ꢁ y, z ꢁ ½
x þ ½, 1 ꢁ y, z
ꢁ1.4
ꢁ7.2
1 ꢁ x, y ꢁ ½, ½ ꢁ z
1 ꢁ x, y þ ½, ½ ꢁ z
3
2
ꢁ x, 1 ꢁ y, z ꢁ ½
ꢁ1.3
ꢁ1.9
ꢁ6.4
2 ꢁ x, 2 ꢁ y, - z
x, y þ 1, z
91
x, y ꢁ 1, z
x, 2 ꢁ y, z ꢁ ½
x, 2 ꢁ y, z þ ½
ꢁx, y þ 1, ½ ꢁ z
ꢁ8.9
ꢁ1.6
C16eH16/F2
and c, Table 6). 95 does not have any CeH/
p
interaction.
CeH/F hydrogen bonds were identified (Fig. 8, Table 8). Once
again, it was found that the compound (99) with fluorine at the
ortho-position, forms a dimer (Fig. 8, Table 8) adopting the robust
synthon I(A) involving CeH/F hydrogen bonds reported by us
recently with the similar stabilization energy [9d]. Compounds 97
5.3. Structural comparison of the compounds belonging to group 2a
The compounds 96 and 97 were found to crystallize in the non-
centrosymmetric P212121 and Pna21 space groups respectively,
while 98 and 99 were crystallized in the centrosymmetric P21/c
space group (Table 7). The compounds 96, 97 and 98 were found to
have the same R22ð7Þ dimer as was seen in the compounds
belonging to group 1a and 1b (Fig. 7). The compound 98 has an
additional CeH/O hydrogen bond in this dimer (Fig. 7c).
and 98 also found to have a few weak CeH∙∙∙
p interactions to
stabilize the crystals structures (Table 9).
5.4. Structural comparison of the compounds belonging to group 2b
Interestingly, the compound 99 does not have the same R22ð7Þ
dimer. This has a centrosymmetric dimer through two OeH/N
hydrogen bonds between the two molecules (Fig. 7d). These dimers
have stabilization energies between ꢁ6.9 and ꢁ10.4 kcal/mol. In
addition to these strong hydrogen bonds in 97, 98 and 99, various
The compounds 100, 101, 102 and 103 belonging to group 2b
were crystalline in nature (ESI, Fig. S4:13e16), but suitable single
crystals for these compounds could not be grown by standard
methods. Therefore, structures of these compounds could not be
determined.

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
159
Fig. 2. (a) CeH/F hydrogen bonds in the structure 89 interlinking strong hydrogen bonded dimers (b) Centrosymmetric dimer in 90 formed through weak CeH/F hydrogen
bonds, which interlinks strong hydrogen bonded dimers; (c) Weak CeH/F hydrogen bond in the structure of 91 joining the strong hydrogen bonded dimers.
Fig. 3. CeH/
p interactions in the crystal lattices of 88, 89, 90 and p/p interactions in 91 in figures a, b, c and d respectively.
Table 3a
Intermolecular CeH/
89, 90) compounds.
p interactions of the compounds belonging to group 1a (88,
Table 3b
Intermolecular
compounds.
p/p interactions of the compounds belonging to group 1a (91)
Code CeH/
p
C/
p
(Å) H/
p
(Å) :CeH/
p
(ꢀ) Symmetry code
88
89
90
C7eH7/Cg2 3.49
C9eH9/Cg1 3.70
C7eH7/Cg2 3.35
C9eH9/Cg1 3.62
C7eH7/Cg2 3.46
C9eH9/Cg1 3.67
2.93
2.83
2.83
2.73
2.89
2.78
120
156
117
157
120
157
½ ꢁ x, ½ þ y, z
x ꢁ ½, y, ½ ꢁ z
½ ꢁ x, y, ½ þ z
½ þ x, ꢁy, z
Code
91
CgA/CgB
D (Å)
D1 (Å)
D2 (Å)
Symmetry code
Cg1/Cg2
Cg3/Cg4
Cg2/Cg2
Cg4/Cg4
3.76
3.75
3.82
4.18
3.25
3.37
3.53
3.34
3.43
3.39
3.53
3.34
1 ꢁ x, y, ½ ꢁ z
ꢁx, y, ½ ꢁ z
½ ꢁ x, ½ þ y, z
x ꢁ ½, y, ½ ꢁ z
1 ꢁ x, ꢁy, 1 ꢁ z
ꢁx, 1 ꢁ y, 1 ꢁ z

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G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Table 4
Unit cell parameters of the compounds belonging to group 1b (92, 93, 94, 95) compounds.
Identification code
92
93
94
95
CCDC No.
Crystal system
Space group
a/Å
b/Å
c/Å
1040702
Monoclinic
P21/c
6.4504(5)
14.4278(11)
12.7143(10)
90
121.331(5)
90
1010.71(14)
4
1040703
Monoclinic
P21/c
9.2568(8)
12.2098(10)
14.5949(11)
90
141.693(5)
90
1022.53(16)
4
1040704
Monoclinic
P21/c
6.598(2)
14.197(5)
12.582(4)
90
120.439(18)
90
1016.2(6)
4
1040705
Monoclinic
P21/c
5.9223(6)
16.9858(18)
11.7847(11)
90
122.080(6)
90
1004.47(18)
4
ꢀ
ꢀ
ꢀ
/
a
b
g
/
/
Volume/Å3
Z
Z0
1
1
1
1
5.5. Structural comparison of the compounds belonging to group 3a
5.6. Structural comparison of the compounds belonging to group 3b
Compounds 104 and 106 were crystallized in the non-
centrosymmetric Cc and Pca21 space groups respectively, while
105 and 107 were crystallized in the centrosymmetric P21/c space
group (Table 10). All the compounds belonging to group 3a have
intramolecular OeH/N hydrogen bond involving the ortho-hy-
droxyl group and the imine nitrogen (ESI (Fig. S6:13e16), Table 11).
Since the eOH group is locked within the molecule in these com-
pounds, they were packed in the lattice through various different
weak CeH/O and CeH/F hydrogen bonds (Table 12, Fig. 9) and
The compounds 108 (disordered) and 111 were crystallized in
non-centrosymmetric orthorhombic space groups Pca21 and
P212121 respectively, while the other two compounds (109 and 110)
were found to adopt centrosymmetric monoclinic P21/c space
group (Table 14). Once again the ortho hydroxyl group on the A ring
was found to be locked through intramolecular OeH/N hydrogen
bond (ESI (Fig. S6:17e20), Table 15). All the four compounds
belonging to this group were found to have various different
CeH/O, CeH/F and OeH/F (in 111) hydrogen bonds (Fig. 10,
CeH/
p
interactions (Table 13, Fig. 9).
Table 16) and weak CeH/p interaction in their crystal lattice
(Fig. 10, Table 17).
Fig. 4. Formation of strong hydrogen bonded dimers in 92, 93, 94 and 95 in figures a, b, c and d respectively.

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
161
Table 5
Intermolecular hydrogen bonds of the compounds belonging to group 1b (92, 93, 94, 95) compounds.
Code
92
DeH/A (D ¼ C, O; A ¼ O, N, F)
d H/A/Å
:DeH/A/ꢀ
Symmetry code
SEG09 kcal/mol
r
eÅꢁ3
V
2r eÅꢁ5
O1eH1/N1
C7eH7/O1
C1eH1A/O1
C9eH9/O1
O1eH1/N1
C7eH7/O1
C4eH4/O1
C9eH9/F1
O1eH1/N1
C7eH7/O1
C1eH1A/O1
C9eH9/O1
C6eH6/F1
O1eH1/N1
C7eH7/O1
C13eH13/O1
C1eH1A/F1
C9eH9/F1
1.81
2.64
2.64
2.50
1.98
2.54
2.68
2.66
1.95
2.64
2.65
2.57
2.42
1.85
2.42
2.65
2.72
2.55
170
147
130
172
167
137
136
156
167
144
136
173
176
174
160
135
174
151
x þ 1, ½ ꢁ y, z þ ½
x ꢁ 1, ½ ꢁ y, z ꢁꢀ½
x, ½ ꢁ y, z þ ½
ꢁ7.3
0.21
0.04
0.05
0.06
0.19
0.05
0.03
0.03
0.23
0.04
0.04
0.05
0.05
0.25
0.07
0.04
0.02
0.80
0.20
0.2
ꢁ3.6
ꢁ8.1
0.23
0.64
0.22
0.16
0.16
0.79
0.21
0.19
0.20
0.26
0.83
0.28
0.22
0.13
0.04
93
94
x ꢁ 1, ꢁ½ ꢁ y, z ꢁ ½
x þ 1, ꢁ½ ꢁ y, z þ ½
x, y þ 1, z
ꢁ1.5
ꢁ2.3
ꢁ8.1
x ꢁ 1, ½ ꢁ y, z ꢁ ½
x, ½ ꢁ y, z þ ½
x, ½ ꢁ y, z ꢁ ½
x ꢁ 1, ½ ꢁ y, z ꢁ ½
x ꢁ 1, ½ ꢁ y, z ꢁ ½
ꢁ4.0
x þ 1, y, z
ꢁ2.5
3
95
x,
x,
x,
2
2
2
ꢁ y, z ꢁ ½
ꢁ y, z ꢁ ½
ꢁ y, z ꢁ ½
ꢁ12.5
3
3
1 ꢁ x, 2 ꢁ y, 2 ꢁ z
1 ꢁ x, 2 ꢁ y, 2 ꢁ z
ꢁ2.3
Fig. 5. CeH/O or (and) CeH/F hydrogen bonds in a, b, c and d in the compounds 92, 93, 94 and 95 respectively.
6. Discussion
studied in this manuscript, it is evident that the hydroxyl group
generally preferred to form only one type of dimer (R22ð7Þ), when it
is at para- or at meta-positions except for the compound 99. But the
spatial dispositions of the two molecules connected by this R22ð7Þ
From the above crystallographic data, structural descriptions
and the various packing characteristics observed in the compounds
Table 6
Intermolecular CeH/
p
interactions of the compounds belonging to group 1b (92, 93, 94) compounds.
CeH/ C/ (Å) H/ (Å)
Code
p
p
p
:CeH/
p
(ꢀ)
Symmetry code
92
93
C5eH5/Cg2
C3eH3/Cg2
C10eH10/Cg1
C13eH13/Cg1
C5eH5/Cg2
3.47
3.46
3.48
3.46
3.42
2.57
2.79
2.76
2.77
2.52
158
129
133
130
158
1 ꢁ x, y ꢁ ½, ½ ꢁ z
ꢁx, ꢁy, ꢁz
x, y þ ½, ½ ꢁ z
ꢁx, y þ ½, ½ ꢁ z
ꢁx, y þ ½, ½ ꢁ z
94

162
G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Fig. 6. CeH/
p
interactions unifying the strong hydrogen bonded dimers in the crystal lattice of 92 in (a), 94 in (b) and 93 in (c) and (d).
Table 7
Unit cells parameters of the compounds belonging to group 2a (96, 97, 98, 99) compounds.
Identification code
96
97
98
99
CCDC No.
Crystal system
Space group
a/Å
b/Å
c/Å
1040706
Orthorhombic
P212121
5.463(8)
10.613(15)
17.22(3)
90
90
90
999(3)
4
1
1040707
Orthorhombic
Pna21
16.779(2)
5.4254(7)
23.148(3)
90
90
90
2107.3(5)
8
2
1040708
Monoclinic
P21/c
11.2365(6)
6.0355(3)
20.7780(10)
90
133.006(3)
90
1030.46(10)
4
1040709
Monoclinic
P21/c
12.086(6)
14.403(6)
5.855(3)
90
95.76(3)
90
1014.2(8)
4
ꢀ
ꢀ
a
b
g
/
/
ꢀ
/
Volume/Å3
Z
Z0
1
1
dimer were found to be different in all the compounds. Further, the
angle between the two phenyl rings (Table 18) have been noted to
vary significantly making the molecule planar for the cases where
eOH group forms intramolecular hydrogen bond (105e110) and
non-planar in all other cases except in 104 and 111. These packing
and conformational differences should be attributed to the fact that
the fluorine atoms present in the molecules at different positions
preferred to form different weak, but significantly stabilizing
CeH/F hydrogen bonds. Our general observation in cases of
compounds 1, 10 and 13 [9a] suggests that the fluorine atom at the
para-position of the phenyl ring prefers to either form one CeH/F
hydrogen bond or a bifurcated CeH/F hydrogen bond as have been
seen in our earlier cases reported recently [9d]. Further, the fluorine
substitution at the meta-position have been found to form a
centrosymmetric dimer in general as was also observed in our
earlier reports [9c,d]. The fluorine at the ortho-position has been
seen mostly to form dimers involving the imine hydrogen, when
the same is not involved in any strong hydrogen bond. In the cases
of compounds 104e111, where the hydroxyl group is locked by
intramolecular OeH/N hydrogen bonding, the calculated lattice
energies of these structures have been found to be at least 20 kJ/
mol lower (102e111 kJ/mol for 104e111, compared to 132e142 kJ/
mol for 88e99) than those packed by intermolecular OeH/N
hydrogen bonds. This indicates that the stability of these crystal
structures are significantly controlled by the strong hydrogen
bonds while the relative packing features are controlled by the
weaker CeH/F hydrogen bonds, CeH/p and p/p interactions.
From the AIM analyses, we noted that the higher values of
electron density (between 0.2 and 0.3 eÅꢁ3) and Laplacian (be-
tween 0.65 and 0.95 eÅꢁ5) at the bond critical points indicate
strong hydrogen bonds (OeH/N). The weaker hydrogen bonds,
like CeH/F and CeH/O, are identified from the lower values of
electron density (
(V2r) (between 0.1 and 0.3 eÅꢁ5) at the bond critical points. The
topological parameters [
, V2r, V(rCP), G(rCP) and E(rCP)] at the
r
) (between 0.02 and 0.03 eÅꢁ3) and Laplacian
r
(3, ꢁ1) bond critical point for CeH/F and CeH/O hydrogen bonds
have been found to vary exponentially with the bond path, as was
seen by us earlier [9a,c,d]. These plots along with the fitted equa-
tion and the corresponding values of R2 are given in figure ST1 and
ST2 in ESI; the values of these parameters are given in the table ST1

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
163
Fig. 7. (a) CeH/O and OeH/N hydrogen bonds in 96; (b) CeH/O and OeH/N hydrogen bonded dimer between the two molecules of the asymmetric unit of 97 (c) Molecules of
98 interacting through OeH/N and CeH/O hydrogen bonds in its crystal lattice. (d) Centrosymmetric dimers formed via strong OeH/N hydrogen bonds in 99.
Fig. 8. (a) CeH/F intermolecular hydrogen bonds in 97 (b) CeH/O hydrogen bonds interconnecting dimers formed by CeH/F hydrogen bonds in 98; (c) Molecular chain
formation via CeH/F intermolecular hydrogen bonds involving imine hydrogen in 99.

164
G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Table 8
Intermolecular hydrogen bonds of the compounds belonging to group 2a (96, 97, 98, 99) compounds.
Code
96
DeH/A (D ¼ C, O; A ¼ O, N, F)
d H/A/Å
:DeH/A/ꢀ
Symmetry code
3
SEG09 kcal/mol
r
eÅꢁ3
V
2r eÅꢁ5
O1eH1/N1
C7eH7/O1
C12eH12/O1
O1eH1/N2
C20eH20/O1
O2eH2/N1
C7eH7/O2
C13eH13/O2
C3eH3/F1
1.98
2.73
2.60
1.90
2.72
1.78
2.73
2.54
2.63
2.47
2.63
1.85
2.64
2.69
2.57
2.45
2.14
158
140
123
167
147
160
147
120
136
170
152
169
146
127
136
162
146
x ꢁ ½,
2
ꢁ y, 1 ꢁ z
ꢁ6.9
0.19
0.03
0.05
0.21
0.03
0.28
0.04
0.06
0.03
0.04
0.03
0.04
0.04
0.04
0.05
0.05
0.13
0.7
2 ꢁ x, 2 ꢁ y, z ꢁ ½
0.14
0.21
0.76
0.16
0.86
0.18
0.25
0.19
0.22
0.18
0.19
0.2
3
3
2
2
þ x,
ꢁ y, 1 ꢁ z
ꢁ1.2
ꢁ8.2
97
x, y, z
x, y ꢁ 1, z
x, yþ1, z
ꢁ10.1
x, y ꢁ 1, z
x, y ꢁ 2, z
ꢁ1.2
ꢁ2.0
ꢁ2.7
ꢁ2.3
ꢁ8.9
x ꢁ ½, ꢁy ꢁ ½, z
C9eH9/F2
½ ꢁ x, y þ ½, z þ ½
C22eH22/F1
O1eH1/N1
C7eH7/O1
C13eH13/O1
C12eH12/O1
C1eH1A/F1
O1eH1/N1
(dimer)
1 ꢁ x, ꢁy, z ꢁ ½
3
98
99
ꢁx, y þ ½, ꢁz þ
2
3
ꢁx, y ꢁ ½,
2
2
ꢁ z
ꢁ z
3
ꢁx, y ꢁ ½,
0.19
0.22
0.24
0.5
5
1 þ x,
2
ꢁ y, ½ þ z
ꢁ1.9
ꢁ4.2
ꢁx, 1 ꢁ y, 2 ꢁ z
1 ꢁ x, 1 ꢁ y, 1 ꢁ z
ꢁ10.4
C11eH11/O1
C1eH1A/F1
2.74
2.37
123
159
x þ 1, y, z
x, y, z þ 1
ꢁ1.5
ꢁ5.2
0.04
0.06
0.17
0.28
Table 9
Intermolecular CeH/
p
interactions of the compounds belonging to group 2a (97 and 98) compounds.
CeH/ C/ (Å) H/ (Å)
Code
97
p
p
p
:CeH/
p
(ꢀ)
Symmetry code
3
C4eH4/Cg2
C17eH17/Cg4
C9eH9/Cg2
C11eH11/Cg1
3.61
3.74
3.39
3.67
2.70
2.84
2.66
2.81
161
160
134
152
½ þ x,
½ þ x,
2
2
ꢁ y, z
ꢁ y, z
3
98
x, 1 þ y, z
3
1 þ x,
2
ꢁ y, ½ þ z
Table 10
Unit cells parameters of the compounds belonging to group 3a (104, 105, 106, 107) compounds.
Identification code
104
105
106
107
CCDC No.
Crystal system
Space group
a/Å
b/Å
c/Å
1040690
Monoclinic
Cc
5.8088(12)
12.891(3)
14.025(3)
90
101.972(3)
90
1027.3(4)
4
1040691
Monoclinic
P21/c
12.6969(7)
5.7190(3)
14.5222(8)
90
107.1660(10)
90
1007.53(9)
4
1040692
Orthorhombic
Pca21
24.8208(11)
3.8115(2)
10.6318(5)
90
90
1040693
Monoclinic
P21/c
4.6762(8)
18.667(3)
12.957(2)
90
116.201(11)
90
1014.8(3)
4
ꢀ
ꢀ
a
b
g
/
/
ꢀ
/
90
Volume/Å3
1005.82(8)
4
1
Z
Z0
1
1
1
and ST2 in the ESI.
compounds (99e111) with intramolecular OeH/N hydrogen bond
were approximately 5e7 kcal/mol lower than those having inter-
molecular OeH/N hydrogen bond. This feature is also observed in
the melting characteristic of these compounds. The compounds 88
The lattice energies were calculated using PIXEL and various
components of lattice energies are given in the Table ST0 in the ESI.
It is evident from this table that the lattice energies of the
Table 11
Geometrical parameters for intramolecular OeH/N hydrogen bonds of the compounds belonging to group 3a (104, 105, 106, 107) compounds.
Code
OeH/N
d H/N/Å
:OeH/N/ꢀ
Symmetry code
104
105
106
107
O1eH1/N1
O1eH1/N1
O1eH1/N1
O1eH1/N2
1.92
1.78
1.79
1.86
137
154
151
146
x, y, z
x, y, z
x, y, z
x, y, z

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
165
Table 12
Intermolecular hydrogen bonds of the compounds belonging to group 3a (105 and 107) compounds.
Code
105
CeH/A (A ¼ O, F)
d H/A/Å
:CeH/A/ꢀ
Symmetry code
SEG09 kcal/mol
r
eÅꢁ3
V
2r eÅꢁ5
C13eH13/O1
C12eH12/F1
C1eH1A/O1
C3eH3/O1
C3eH3/F1
2.70
2.62
2.56
2.67
2.62
160
148
154
150
126
ꢁx, ꢁy, ꢁz
ꢁ3.1
ꢁ1.1
ꢁ4.3
0.03
0.03
0.05
0.04
0.03
0.16
0.17
0.21
0.17
0.19
1 ꢁ x, y ꢁ ½, ½ ꢁ z
3
107
x þ 1,
2
2
ꢁ y, z þ ½
ꢁ y, z þ ½
3
x þ 1,
3
x,
2
ꢁ y, ½ þ z
ꢁ2.0
Fig. 9. (a) CeH/
molecular hydrogen bonds in 105; (d) CeH/
p
interactions in 104 by which molecules propagate in the lattice; (b) Formation of antiparallel dimer via CeH/O hydrogen bonds in 105; (c) CeH/F inter-
interactions in 105; (e) OeH/N (intramolecular), CeH/O and CeH/F hydrogen bond in 107.
p
to 98 have higher melting point (86e186 ꢀC) and higher melting
enthalpy (19.5e44.8 kJ/mol) in general, while the same for 99 to 111
are found to be much lower. Further, the dispersion components of
the lattice energy have been found to be the highest in all the
compounds, especially for those compounds (99e111), which had
intramolecular hydrogen bonds. This observation indicates that the
weak CeH/F and CeH/O hydrogen bonds mostly offer
stabilization through dispersion forces.
All the compounds reported in this manuscript also have various
weak CeH/p interactions. The contribution of these interactions
cannot be ignored as they also show favourable geometrical pa-
rameters indicating a sense of directionality (d (H/
p
) ¼ 2.5e2.9 Å,
:CeH/
p
¼ 130e160ꢀ). Therefore, it can be inferred that the
combined influence of a number of weak interactions (CeH/F,

166
G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Table 13
Intermolecular CeH/
p
interactions of the compounds belonging to group 3a (104 and 105) compounds.
Code
104
CeH/
p
C/
p
(Å)
H/
p
(Å)
:CeH/
p
(ꢀ)
Symmetry code
C3BeH3B/Cg2
C5BeH5B/Cg2
C9BeH9B/Cg1
C11BeH11B/Cg1
C3eH3/Cg2
3.54
3.57
3.53
3.57
3.47
3.41
2.84
2.74
2.83
2.74
2.76
2.71
131
146
131
146
132
131
x ꢁ ½, y ꢁ ½, z
x, ꢁy, z ꢁ ½
x ꢁ ½, ½ þ y, z
½ þ x, ½ ꢁ y, ½ þ z
ꢁx, ½ þ y, ½ ꢁ z
ꢁx, ½ þ y, ½ ꢁ z
105
C10eH10/Cg1
Table 14
Unit cells parameters of the compounds belonging to group 3b (108, 109, 110, 111) compounds.
Identification code
108
109
110
111
CCDC No.
Crystal system
Space group
a/Å
b/Å
c/Å
1040694
Orthorhombic
Pca21
12.1651(11)
6.0020(6)
13.8111(13)
90
90
1040695
Monoclinic
P21/c
21.6018(15)
5.9384(4)
17.2691(12)
90
113.142(4)
90
2037.0(2)
8
1040696
Monoclinic
P21/c
12.330(4)
5.8464(15)
21.381(6)
90
138.261(1)
90
1040690
Orthorhombic
P212121
6.5279(6)
10.9920(9)
14.3681(12)
90
ꢀ
ꢀ
a
b
g
/
/
90
90
ꢀ
/
90
Volume/Å3
1008.42(17)
4
1
1026.1(5)
4
1
1030.98(15)
4
1
Z
Z0
2
CeH/O and CeH/
p
) have enforced these molecules to adopt
mechanism. The other weaker interactions have been shown to
be highly influential in altering the overall packing character-
istics of these molecules without significant hindrance to the
strong OeH/N hydrogen bond. Although, the compounds
with the eOH group at the meta-position of A ring were crys-
talline when synthesized, they did not yield suitable single
crystal for structural analysis. Further, these compounds have
been found to be highly unstable in solution. That is why the
NMR spectra of these compounds could not be recorded.
Moreover, it should be noted that the presence of F at the meta-
position of A or B ring does not alter the packing of molecules in
the crystal lattice of the compounds belonging to group 1a and
1b (eOH group at para-position; compounds 88e95). Therefore,
the compounds 88 and 90; 92 and 94; are found to be iso-
structural with similar unit cell parameters and the packing
characteristics. Intramolecular OeH/N hydrogen bond in the
compounds 104e111 have been found to be responsible for
different 3D arrangements with both centrosymmetric (Pbca, P2/c
and P21/c) and non-centrosymmetric (Cc, Pca21, P212121 and Pna21)
space groups. In addition, it is observed that even though the
compounds belonging to one group are crystallized in the same
space group (group 1b) had widely different structures mostly due
to differences in CeH/F, CeH/O and CeH/p interactions.
It is worth mentioning that the structures of the compounds 92
[36], 93 [37], 105 [38] and 108 [39] were reported earlier at room
temperature, just as a structural report and in-depth structural
analyses of these compounds were not done. Further, three poly-
morphs of the compound 104 [40] were reported earlier using a
single crystal data recorded at 120 K. As we intended to analyse all
the structures at 100 K, we made all the compounds, crystallized
them and conducted the entire study at the same temperature. The
polymorph of 104, reported by us in this manuscript is different
from those reported earlier.
locking the compounds in
a near planar conformation,
thereby allowing the weaker hydrogen bonds to completely
control the structural features. As a result, a wide variation in
the unit cell parameters and space groups have been seen in
these compounds. Based on the results described above, it
may be concluded that the supramolecular recognition patterns
of various organic molecules can be altered by a number of
much weaker interactions even in the presence of strong
hydrogen bonds as shown here.
7. Conclusions
This manuscript highlights the importance of a number of
weak interactions in the presence of a strong hydrogen bond in
the packing of a series of small organic molecules. Because of
the strong directionality and high stabilization energy associ-
ated with the strong OeH/N hydrogen bond, these molecules
generally had the R22ð7Þ dimer as the primary recognition
Table 15
Intramolecular OeH/N hydrogen bond of the compounds belonging to group 3b compounds.
Code
OeH/N
d H/N/Å
:OeH/N/ꢀ
Symmetry code
108
109
O1eH1/N1
O1eH1/N1
O2eH2/N2
O1eH1/N1
O1eH1/N1
2.10
2.01
1.88
2.01
2.14
118
114
127
117
120
x, y, z
x, y, z
x, y, z
x, y, z
x, y, z
110
111

G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
167
Fig. 10. (a) CeH/O intermolecular hydrogen in 108; (b) CeH/
CeH/F intermolecular hydrogen bonds in 109; (e) Tetrameric unit formation by CeH/F hydrogen bonds in 109; (f) CeH/
of molecular layers through CeH/O and CeH/F hydrogen bonds in 110; (h) Formation of molecular chain via CeH/O, CeH/F and OeH/F hydrogen bonds in the structure of
compound 111; (i) CeH/ interactions interconnecting the above formed chains in the lattice of 111.
p
interactions in the crystal lattice of 108; (c) CeH/O intermolecular hydrogen bonds in 109; (d) CeH/O and
p
interactions in the crystal lattice of 109; (g) Formation
p

168
G. Kaur et al. / Journal of Molecular Structure 1106 (2016) 154e169
Table 16
Intermolecular hydrogen bonds of the compounds belonging to group 3b (108, 109, 110, 111) compounds.
Code
DeH/A (D ¼ C, O; A ¼ O, F)
d H/A/Å
:DeH/A/ꢀ
Symmetry code
SEG09 kcal/mol
r
eÅꢁ3
V
2r eÅꢁ5
108
109
C4AeH4A/O1
C1eH1A/O1
C14eH14/O2
C3eH3/F2
C16eH16/F1
C23eH23/F1
C1eH1A/O1
C11eH11/F1
C1eH1A/O1
C7eH7/F1
2.54
2.57
2.61
2.69
2.67
2.65
2.70
2.65
2.53
2.66
2.26
141
124
126
129
131
145
125
145
169
143
134
½ ꢁ x, y ꢁ 1, z ꢁ ½
x, y ꢁ 1, z
ꢁ1.4
ꢁ4.2
ꢁ4.3
ꢁ1.0
ꢁ2.7
ꢁ2.1
ꢁ4.5
ꢁ0.7
ꢁ3.7
0.06
0.05
0.05
0.03
0.03
0.03
0.04
0.03
0.05
0.03
0.06
0.24
0.23
0.2
x, y ꢁ 1, z
x, ½ ꢁ y, z ꢁ ½
x, y ꢁ 1, z
0.15
0.16
0.17
0.18
0.17
0.21
0.16
0.34
1 ꢁ x, y ꢁ ½, ½ ꢁ z
x, y ꢁ 1, z
110
111
x þ 1, y, z
x ꢁ 1, y, z
x þ 1, y, z
O1eH1/F1
x þ 1, y, z
Table 17
Intermolecular CeH/
p
interactions of the compounds belonging to group 3b (108, 109, 110, 111) compounds.
CeH/ C/ (Å) H/ (Å)
Code
108
p
p
p
:CeH/
p
(ꢀ)
Symmetry code
C5AeH5A/Cg2
C7AeH7A/Cg2
C9AeH9A/Cg1
C9eH9/Cg2
3.57
3.43
3.68
3.50
3.48
3.57
3.44
3.36
2.84
2.79
2.94
2.78
2.77
2.88
2.72
2.59
135
125
136
134
132
130
133
138
½ ꢁ x, y, z ꢁ ½
½ þ x, 2 ꢁ y, z
x ꢁ ½, 1 ꢁ y, z
109
110
111
ꢁx, ½ þ y, ½ ꢁ z
1 ꢁ x, y ꢁ ½, ½ ꢁ z
1 ꢁ x, y ꢁ ½, ½ ꢁ z
ꢁx, y ꢁ ½, ½ ꢁ z
2 ꢁ x, y ꢁ ½, ½ ꢁ z
C22eH22/Cg4
C4eH4/Cg1
C9eH9/Cg2
C5eH5/Cg2
Table 18
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List of the angle between the two phenyl rings in 88e111.
Compound no
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Compound no
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