Monatsh Chem

DOI 10.1007/s00706-015-1413-z

ORIGINAL PAPER

Quantum chemical investigations of a co-crystal of 1,3,5-tris(4-

hydroxyphenyl)benzene and 2,4,6-trimethoxy-1,3,5-triazine
Ömer Dereli • Semiha Bahçeli • Asghar Abbas •

Muhammad Moazzam Naseer

Received: 23 December 2014 / Accepted: 2 January 2015

Ó Springer-Verlag Wien 2015

Abstract In the present study, quantum chemical inves- Graphical abstract

tigations were carried out on our previously reported co-
crystal based on 1,3,5-tris(4-hydroxyphenyl)benzene and
2,4,6-trimethoxy-1,3,5-triazine, which showed CHp and
pp interactions driven layer-by-layer self-assembly of
hydrogen-bonded hexagonal blocks in the solid state.
Using the DFT/B3LYP calculation method with
6-311??G(d,p) basis set in the ground state, the optimized
molecular geometric parameters, conformational analysis,
vibrational wavenumbers and their assignments, the
HOMO–LUMO analysis, molecular electrostatic potential,
thermodynamic properties, and atomic charges were cal- Keywords Co-crystal  Supramolecular chemistry 
culated to understand various structural features that are Self-assembly  Quantum chemical calculations 
playing an important role in its packing. Furthermore, the Density functional theory
simulated infrared and Raman spectra of the co-crystal are
plotted using the calculated results. The calculated results
are in a good agreement with experimental data. The study
with constructive propositions may be helpful in under- Introduction
standing complex self-assembled systems and in the
construction of similar molecular self-assemblies. Molecular self-assembly, where molecules adopt a defined
arrangement without any guidance from an external
source, is an important aspect of bottom-up approaches to
Electronic supplementary material The online version of this nanotechnology. By virtue of this process, the desired
article (doi:10.1007/s00706-015-1413-z) contains supplementary functional materials may be achieved depending on the
material, which is available to authorized users. shape, symmetry, and functionality of the individual
A. Abbas  M. M. Naseer (&)
building components [1–13]. However, to reach at per-
Department of Chemistry, Quaid-i-Azam University, Islamabad fection level observed in materials created by nature
45320, Pakistan through this process, a complete understanding and con-
e-mail: moazzam@qau.edu.pk trol of non-covalent interactions is required [14–20]. This
Ö. Dereli
is the main driving force, leading supramolecular chem-
Department of Physics, Education Faculty, Necmettin Erbakan ists towards the development of novel molecular
University, 42090 Meram Konya, Turkey assemblies of distinct shapes for their application in many
fields such as microelectronics [21], medicine and bio-
S. Bahçeli
Department of Physics, Faculty of Arts and Science, Süleyman
technology [22], catalysis [23], sensors [24], and solar
Demirel University, East Campus, 32260 Isparta, Turkey fuel cells [25].

123

It is now well established that the faces of two aromatic
rings with opposite quadrupole moments have attractive
face-to-face stacked interactions. The benzene–perfluoro-
benzene p–p interaction is a representative example of this
phenomenon [26–29]. The F atoms due to their electron-
withdrawing nature reduce the electron density in the
center of perfluorobenzene making it favorable for inter-
actions with an electron-rich benzene ring. Inspired by this,
we recently used 2,4,6-trimethoxy-1,3,5-triazine (2) (hav-
ing the sign of the permanent quadrupole opposite [30–32]
to that of benzene) and cultivated its co-crystal with 1,3,5-
tris(4-hydroxyphenyl)benzene (1) [33]. The crystal struc-
ture revealed layer-by-layer assembly driven mainly by
CHp and pp interactions. Each layer of this assembly
was composed of [3 ? 3] type hexagonal blocks of 1 and 2
stabilized by intermolecular hydrogen bonds.
Herein, as continuation of our study [33], we report the
results of a quantum chemical investigation of the co-
crystal constructed from 1 and 2. The present study aims to
give a complete description and molecular vibrations at the
DFT/B3LYP level of theory using the 6-311??G(d,p)
basis set. From the results of the present study, it is
anticipated that quantum chemical calculation is an
important approach which can be used to predict and
construct similar molecular self-assemblies.
Results and discussion
Molecular geometry
The molecular structure along with the atom numbering
scheme of a co-crystal based on 1,3,5-tris(4-hydroxy-
phenyl)benzene (1) and 2,4,6-trimethoxy-1,3,5-triazine (2)
is given in Fig. 1. Figure 2 shows the comparison between
Fig. 1 Structure and atom numbering scheme of a co-crystal of 1,3,5-
tris(4-hydroxyphenyl)benzene (1) and 2,4,6-trimethoxy-1,3,5-triazine
(2)
123
Ö. Dereli et al.
calculated (shown by tube model) and experimental
(shown by ball-bond model) geometry of the co-crystal
(Fig. 2a), 1 alone (Fig. 2b), and 2 alone (Fig. 2c). Fur-
thermore, the optimized molecular geometry parameters
(bond lengths and angles) using the DFT/B3LYP method
with 6-311G(d,p) basis set in comparison to the experi-
mental results are given in Table 1 [33]. The results of the
conformational analysis carried out by considering the
orientations of the H2–N7 bond axis (a hydrogen bond
formed between OH groups of 1 and nitrogen of 2) are
presented in Fig. 3. The conformer with a torsion angle of
174.94° around the H2–N7 bond axis and a DFT energy of
-1775.536 Hartrees was found to be the most stable one
having good correlation with the unit cell given in the
crystallographic structure (Fig. 2a) [33]. Therefore, all
other calculations were performed using this conformation.
As shown in Fig. 2 and Table 1, there is no significant
difference between experimental and calculated results,
except some small deviations that were observed in the
connection regions. For example, calculated and experi-
mental distances observed between H2N7 hydrogen
bonds are 1.973 and 2.275 Å, and H10O4 hydrogen
bonds are 2.844 and 2.459 Å. Similarly, the calculated
values for C11–H2–N7–C24 and C12–O4–H10–C50
dihedral angles are 179.47° and 93.07° while the experi-
mental counterparts are 174.94° and 115.24°. These small
deviations between calculated and experimental results can
be attributed to the difference in structural environments as
experimental results were obtained from the solid phase,
while the theoretical calculations belong to gaseous phase.
According to the classification of hydrogen bonds by Jef-
frey [34] based on donor–acceptor distances, a hydrogen
bond is considered to be strong and resemble covalent
bonds in most of their properties when the distance is
2.2–2.5 Å. However, the nature of these hydrogen bond
interactions is electrostatic when the donor–acceptor dis-
tances are 2.5–3.2 Å (moderate in strength) and 3.2–4.0 Å
(weak in strength) regardless of significant charge transfer
in the hydrogen bond. Based on the above classifications,
the calculated and experimental values of hydrogen bonds
present in this self-assembled structure are either strong
and covalent (between H2N7) or moderate and electro-
static (H10O4). The detailed experimental and
theoretical geometry parameters are provided in the Table
S1 (Supplementary Information).
Vibrational analysis
According to the normal-mode analysis, the co-crystal
consists of 66 atoms and it has 192 fundamental vibrations.
All of the calculated modes are numbered from the smallest
to the largest frequency, and the calculated IR intensities,
Raman scattering activities, and all vibrational frequency
Quantum chemical investigations of a co-crystal
Fig. 2 Comparison of calculated (tube model) and experimental (ball-bond model) geometries of a whole co-crystal, b 1,3,5-tris(4-
hydroxyphenyl)benzene (1) alone, and c 2,4,6-trimethoxy-1,3,5-triazine (2) alone
assignments of the co-crystal are listed in Table 2. The
simulated IR and Raman spectra of the co-crystal using the
B3LYP/6–311??G(d,p) level of the theory are given in
Figs. 4, 5.
As shown in Table 2, the calculated bands at the interval
3705–3439 cm-1 can be assigned to the free OH stretching
vibrations of 1, while the computed wavenumbers at the
region 3088–3025 cm-1 can be attributed to the CH
stretching modes of aromatic rings [35, 36]. Meanwhile,
the asymmetric CH stretching modes of aromatic rings (or
methylene groups in 2) are calculated at 2955 and
2953 cm-1 [37]. Similarly, the calculated bands at the
regions 1602–1570, 1565, 1494, and 1436 cm-1 can be
attributed to the CC stretching modes of the rings [36, 38–
41]. The HCC and HCH bending modes of aromatic rings
are calculated at the interval 1499 and 1495 cm-1 and at
the interval 1462–1443 cm-1, respectively. Furthermore,
the calculated values for the NC stretching vibrational
modes of 2 are observed at 1566 and 1562 cm-1 with ring
CC stretching mode at 1543, 1362, 1353, and 1257 cm-1
[39, 42]. The calculated wavenumber values as 1353, 1249,
and 1024 cm-1 can be attributed to the CO stretching mode
of 2 [37, 43].
The most indicative vibrational bands for the NH
stretching mode (a hydrogen bond formed between 1 and
2) are calculated as 105 and 77 cm-1 (Table 2). This
confirms that the calculated IR bands corresponding to the
atoms not included in the hydrogen bonding appear at
higher wavenumbers as compared with those involved in
the intermolecular hydrogen bonding [44].
HOMO–LUMO analysis
The energy gap between HOMO and LUMO is a critical
parameter to determine molecular electrical transport
properties [45, 46]. By analyzing HOMO and LUMO
energy values, molecular properties, such as the chemical
reactivity, kinetic stability, optical polarizability, chemical
hardness and softness, and electronegativity can be
accessed.
HOMO–LUMO energies of the co-crystal were calculated,
and from the shape of the orbitals shown in Fig. 6, it is quite
clear that the HOMO is localized over 2, while the LUMO is
localized over 1, indicating the charge transfer from 2 to 1.
Furthermore, the calculated HOMO–LUMO energies are
used to determine the electronegativity, chemical hardness
and softness, and electrophilicity index (Table 3). The values
of hardness and softness of the system clearly indicate that the
system is relatively hard and stable [47].
Molecular electrostatic potential
The molecular electrostatic potential (MEP) is not only a
useful tool to understand the molecular interactions in any
structure, but also a valuable method for the prediction of
(1) sites for the electrophilic and nucleophilic attack; (2)
investigations of biological recognition; (3) hydrogen
bonding interactions; (4) molecular cluster and crystal
behavior, etc. [48, 49]. Furthermore, it provides correla-
tions between chemical reactivity and the partial charges,
dipole moments, and electronegativity of a molecule.
The 3D plot of the MEP of the co-crystal based on 1 and
2 is obtained from the optimized molecular structure
(Fig. 7). It is clear from the figure that areas related to
oxygen atoms show slightly positive electrostatic potential
(yellow color) and hydrogens connected to the oxygen
represent the regions of sharply positive electrostatic
potential (blue color), indicating H of OH groups as site of
hydrogen bonding in the co-crystal.
Atomic charges and thermodynamic properties
Mulliken atomic charges and thermodynamic properties,
such as thermal energy, heat capacity, entropy and dipole
moment were also studied. (Table 4 and Table S2, Sup-
plementary information).
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 Ö. Dereli et al.

Table 1 Experimental and optimized geometry parameters of the co-crystal

1,3,5-Tris(4-hydroxyphenyl)benzene (1) part 2,4,6-Trimethoxy-1,3,5-triazine (2) part
a a
Parameters Calculated X-ray Parameters Calculated X-ray Parameters Calculated X-Raya
Bond length/Å Bond angle/° Bond length/Å

O1–H2 0.977 0.840 C9–C29–C35 120.2 119.7 O3–C11 1.441 1.449

O1–C9 1.358 1.370 C36–C30–C65 119.9 119.7 O3–C23 1.324 1.323
C9–C29 1.399 1.390 C28–C31–C37 119.9 119.7 O4–C12 1.44 1.449
C9–C50 1.399 1.381 C29–C35–C41 121.6 121.6 O4–C24 1.329 1.323
O26–H27 0.963 0.840 C30–C36–C42 121.7 121.6 O5–C13 1.44 1.449
O26–C28 1.367 1.370 C31–C37–C43 121.7 121.6 O5–C25 1.327 1.323
C28-C31 1.396 1.390 C35–C41–C44 117.4 117.5 N6–C23 1.339 1.344
C28–C52 1.396 1.381 C35–C41–C54 121.3 122.2 N6–C25 1.325 1.322
C29–C35 1.388 1.384 C44–C41–C54 121.3 120.3 N7–C23 1.333 1.322
C30–H33 1.083 0.950 C36–C42–C45 117.5 117.5 N7–C24 1.346 1.344
C30–C36 1.388 1.384 C36–C42–C55 121.2 122.2 N8–C24 1.32 1.322
C30–C65 1.396 1.390 C45–C42–C55 121.3 120.3 N8–C25 1.342 1.344
C31–C37 1.388 1.384 C37–C43–C46 117.5 117.5 R2 = 0.99452
C35–C41 1.404 1.391 C37–C43–C56 121.2 122.2
C36–C42 1.404 1.391 C46–C43–C56 121.3 120.3 Bond angle/°
C37–C43 1.404 1.391 C41–C44–C50 121.7 121.4 C11–O3–C23 119 118.4
C41–C44 1.402 1.398 C42–C45–C51 121.4 121.4 C12–O4–C24 118 118.4
C41–C54 1.485 1.484 C43–C46–C52 121.4 121.4 C13–O5–C25 117.7 118.4
C42–C45 1.401 1.398 C9–C50–C44 120 120.1 C23–N6–C25 114.2 112.8
C42–C55 1.486 1.484 C45–C51–C65 120.1 120.1 C23–N7–C24 113.8 112.8
C43–C46 1.401 1.398 C28–C52–C46 120.1 120.1 C24–N8–C25 113.5 112.8
C43–C56 1.486 1.484 C41–C54–C57 120.9 120.4 O3–C23–N6 114.1 112.5
C44–C50 1.391 1.382 C41–C54–C59 120.8 121 O3–C23–N7 120.3 120.3
C45–C51 1.391 1.382 C57–C54–C59 118.3 118.4 N6–C23–N7 125.6 127.2
C46–C52 1.391 1.382 C42–C55–C57 120.7 121 O4–C24–N7 113.5 112.5
C51–C65 1.396 1.381 C42–C55–C58 120.7 120.4 O4–C24–N8 120 120.3
C54–C57 1.400 1.392 C57–C55–C58 118.6 118.4 N7–C24–N8 126.6 127.2
C54–C59 1.400 1.399 C43–C56–C58 120.8 121 O5–C25–N6 119.5 120.3
C55–C57 1.400 1.399 C43–C56–C59 120.7 120.4 O5–C25–N8 114.1 112.5
C55–C58 1.400 1.392 C58–C56–C59 118.6 118.4 N6–C25–N8 126.4 127.2
C56–C58 1.400 1.399 C54–C57–C55 121.6 121.5 R2 = 0.98980
C56–C59 1.400 1.392 C55–C58–C56 121.4 121.5 Selected dihedral angle/°
O63–H64 0.963 0.840 C54–C59–C56 121.6 121.5 C13–O5–C25–N8 179.83 174.86
O63–C65 1.367 1.370 H64–O63–C65 109.2 109.5 C12–O4–C24–N7 178.92 174.86
R2 = 0.99518 C30–C65–C51 119.5 119.7 C11–O3–C23–N6 177.7 174.86
C30–C65–O63 117.6 117.1
Bond angle/° C51–C65–O63 122.9 123.2
H2–O1–C9 111.2 109.5 R2 = 0,97487
O1–C9–C29 117.8 117.1 Selected dihedral angle/°
O1–C9–C50 123.1 123.2 H2–O1–C9–C29 178.95 179.9
C29–C9–C50 119.1 119.7 H27–O26–C28–C31 179.42 179.9
H27–O26–C28 109.2 109.5 H64–O63–C65–C30 179.49 179.9
O26–C28–C31 117.6 117.1 C44–C41–C54–C57 141.12 145.4
O26–C28–C52 122.9 123.2 C46–C43–C56-C59 139.82 145.4
C31–C28–C52 119.5 119.7 C45–C42–C55–C58 139.54 145.4

123
Quantum chemical investigations of a co-crystal

Table 1 continued
1,3,5-Tris(4-hydroxyphenyl)benzene (1) part 2,4,6-Trimethoxy-1,3,5-triazine (2) part
a a
Parameters Calculated X-ray Parameters Calculated X-ray Parameters Calculated X-Raya
Bond length/Å Bond angle/° Bond length/Å

Selected bond length/Å and dihedral angle of connection region/°

H2–N7 1.973 2.275 O4–H10 2.844 2.459
C11–H2–N7–C24 179.47 174.94 C12–O4–H10–C50 93,07 115,24
a
Taken from Ref. [33]

Conclusions

In conclusion, we have verified the molecular structure

Fig. 3 Conformational analysis/scanned potential energy surface
around the H2N7 bond axis
and packing of a co-crystal using DFT/B3LYP computa-
tional method with 6-311??G(d,p) basis set. It is found
that self-assembled hexagonal blocks, which represent the
basic supramolecular entity of the crystal structure, are
formed by strong and mostly covalent hydrogen bonding
interactions between OH of 1,3,5-tris(4-hydroxy-
phenyl)benzene (1) and N of 2,4,6-trimethoxy-1,3,5-
triazine (2). Furthermore, one stable conformer was
identified for the co-crystal. The HOMO–LUMO analysis
shows that the charge transfer occurred from 2 to 1
indicating the favorable face-to-face p–p stacking. Fur-
thermore, the calculated HOMO–LUMO energies were
used to determine the electronegativity, chemical hardness

Table 2 Calculated vibrational spectra of the co-crystal

Mode Theoretical wavenumber/cm-1 TED/%
a b
Unscaled freq Scaled freq IcIR IdRAMAN

1 3831 3705 5 2 99tOH

2 3831 3704 6 2 99tOH
3 3556 3439 100 12 98tOH
4 3194 3088 1 3 97tCH
5 3193 3088 1 3 89tCH
6 3190 3085 1 4 82tCH
7 3187 3082 1 2 80tCH
8 3183 3078 0 1 80tCH
9 3182 3077 0 1 88tCH
10 3181 3076 0 0 71tCH
11 3178 3073 0 0 77tCH
12 3177 3072 1 0 82tCH
13 3174 3069 1 0 87tCH
14 3173 3068 0 1 78tCH
15 3170 3065 1 1 82tCH
16 3168 3063 1 1 85tCH
17 3165 3060 1 1 100tCH
18 3163 3059 1 2 96tCH
19 3159 3055 1 2 100tCH
20 3147 3043 2 2 91tCH

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 Ö. Dereli et al.

Table 2 continued
Mode Theoretical wavenumber/cm-1 TED/%
a b
Unscaled freq Scaled freq IcIR IdRAMAN

21 3146 3042 2 2 91tCH

22 3137 3034 1 1 91tCH
23 3132 3029 1 1 100tCH
24 3128 3025 1 1 100tCH
25 3056 2955 1 3 97tCH
26 3056 2955 2 2 92tCH
27 3054 2953 3 3 99tCH
28 1657 1602 5 35 46tCC ? 15dHCC
29 1657 1602 3 35 51tCC
30 1656 1602 3 38 51tCC
31 1632 1578 3 21 34tCC
32 1631 1577 5 19 19tCC ? 10dCCC
33 1624 1570 6 3 10tCC
34 1620 1566 17 13 26tNC ?16tCC
35 1618 1565 6 27 29tCC ? 12dHCC
36 1615 1562 49 13 28tNC ?12tCC
37 1596 1543 49 0 64tNC
38 1562 1511 2 1 42tOC ? 13dCNC
39 1550 1499 2 22 27dHCC
40 1546 1495 18 5 20dHCC
41 1545 1494 15 4
42 1512 1462 6 1 31dHCH ? 18tNC ?15CHCHO
43 1507 1457 3 1 42dHCH ? 10tOC
44 1500 1451 2 2 75dHCH
45 1497 1447 2 1 71dHCH
46 1495 1446 8 1 44dHCH ? 12CHCHO
47 1492 1443 7 0 42dHCH ? 15CHCOC ? 13CHCHO
48 1485 1436 2 2 19tCC
49 1484 1435 1 1 74dHCH ? 17CHCOC
50 1483 1434 1 1 75dHCH ? 17CHCOC
51 1483 1434 5 3 10dHCH
52 1465 1416 0 1
53 1446 1398 0 0 21dHCH ? 19CHCHO ? 13tOC
54 1434 1387 4 1 11dHCC ? 23tOC
55 1433 1386 2 1
56 1409 1362 34 0 40tNC ?14CHCHO
57 1399 1353 48 0 12tNC ? 40tOC ? 11dNCN
58 1385 1339 2 1 25dCOH ? 18dHCC ? 13tCC
59 1369 1324 2 100 34tCC
60 1366 1321 1 27 22dHCC ? 16dHOC ? 17tCC
61 1364 1319 5 1 23dHCC ? 23dHOC ? 22tCC
62 1335 1291 0 0 53dHCC ? 23tCC
63 1327 1283 0 0 15dHCC ? 21tCC
64 1313 1270 1 0 27tCC ? 26dHCC
65 1312 1269 1 0 38tCC
66 1302 1259 10 1 52tOC ? 16dHCC ? 10tCC
67 1300 1257 1 1 83tNC

123
Quantum chemical investigations of a co-crystal

Table 2 continued
Mode Theoretical wavenumber/cm-1 TED/%
a b
Unscaled freq Scaled freq IcIR IdRAMAN

68 1292 1249 6 1 48tOC

69 1292 1249 13 1 49tOC
70 1277 1235 1 0 34tCC ? 28dHCC
71 1260 1218 0 24 31tCC ? 25dHCC
72 1258 1217 0 27 27tCC ? 24dHCC
73 1248 1207 11 5 21tCC ? 18dCOH ?11dHCC
74 1234 1193 12 2 32CHCHO ? 13tOC
75 1232 1192 13 1 44CHCOC ? 11tOC
76 1210 1170 0 0 53CHCOC
77 1198 1158 1 1 25dHOC ? 18dHCC
78 1198 1158 4 0 31dHOC ? 16dHCC
79 1196 1157 0 7 43dHCC
80 1194 1155 12 3 34dHCC ? 11dHOC
81 1193 1154 21 3 36dHCC ? 17dHOC
82 1176 1137 0 0 67CHCOC ? 31dHCH
83 1174 1135 0 0 67CHCOC ? 31dHCH
84 1170 1132 0 0 72dHCO
85 1147 1109 9 0 47tOC ? 16CHCHO
86 1144 1106 13 0 38tOC ? 24CHCOC
87 1129 1092 0 0 50dHCC ? 26tCC
88 1127 1090 1 0 11dHCC ? 11tCC
89 1127 1089 1 0 12dHCC ? 10tCC
90 1113 1076 1 1 24tCC ? 21dHCC ? 14dCCC
91 1112 1075 1 1 28dHCC ? 11tCC
92 1059 1024 0 1 74tOC
93 1047 1012 0 8 34dCCC
94 1028 994 0 0 67dCCC
95 1028 994 0 0 56dCCC
96 1021 987 0 3 36dCCC
97 1011 978 0 31 65tCC ? 22dCCC
98 1000 967 0 5 59tNC ? 30dNCN
99 969 937 0 1 67CHCCC
100 969 937 0 0 66CHCCC ? 14CCCCC
101 968 937 0 1 64CHCCC ? 15CCCCO
102 965 933 1 0 69tOC
103 959 927 2 0 73tOC
104 952 921 0 0 51CHCCC ? 20CCCCC
105 947 915 0 0 51CHCCC
106 945 914 0 0 47CHCCC ? 11CCCCC
107 918 887 0 1 73CHCCC
108 915 885 0 1 76CHCCC
109 905 875 1 0 72CHCCC
110 863 834 1 2 26tCC
111 862 834 1 1 13tCC
112 847 819 3 1 61CHCCC ? 16CCOCC
113 844 817 2 1 55CHCCC ? 11COCCC ? 10CCCCC
114 843 815 5 0 54CHCCC ? 13COCCC

123
 Ö. Dereli et al.

Table 2 continued
Mode Theoretical wavenumber/cm-1 TED/%
a b c d
Unscaled freq Scaled freq IIR IRAMAN

115 841 813 3 1 75CCNCN

116 840 812 1 24 15tOC ? 10tCC
117 826 798 1 4 90CHCCC
118 812 786 1 2 70CHCCC
119 812 785 1 2 82CHCCC
120 797 771 0 3 18dCCC
121 795 769 0 3 16tOC
122 769 744 1 1 43dCOC
123 764 739 0 0 77CONNC
124 760 735 0 0 73CONNC
125 741 717 0 0 40CCCCC ? 16CHCCC
126 738 714 0 1 52CCCCC ? 10CHCCC
127 737 712 0 0 48CCCCC ? 10CHCCC
128 731 707 1 0 70CCCCC ? 11CHCCC
129 721 697 3 1 39CCNHO ? 10dHNC
130 663 641 0 3 37dCCC
131 663 641 0 2 40dCCC ? 12dCCO
132 655 633 0 0 51dCCC
133 623 602 0 1 40CCCCC
134 622 601 0 1 49CCCCC
135 615 595 0 1 54dCOC ? 10tNC
136 606 586 0 0 69dCNC
137 603 583 0 0 45dCCC ? 10tOC
138 579 560 1 0 36dCCC
139 573 554 2 0 48dCCC
140 572 553 2 0 43dCCC ? 11tOC
141 570 551 0 7 34tOC ? 19dCNC ? 12tNC
142 532 515 1 0 35CCOCC ? 14CHCCC
143 530 513 1 0 35COCCC ? 20CHCCC ? 11CCCCC
144 507 490 1 0 26COCCC ? 12CCOCC
145 454 439 1 2 36dCOC ? 14dCCO
146 450 436 1 1 28dCCO ? 18dCOC
147 448 433 2 1 57dCOC ? 12tOC
148 434 420 1 0 51dCCO ? 10COCCC
149 427 413 0 5 66CCCCO ? 12CHCCC
150 425 411 0 4 75CCCCC
151 424 410 0 3 75CCCCC ? 10CHCCC
152 423 409 0 1 42dCCO
153 390 377 0 1 10dCCO
154 385 372 0 1 12COCCC ? 10dCCO ? 10dCCC
155 347 335 1 0 19CCCCC ? 13CCCCC ? 12CCCCO
156 340 329 4 3 95CHOCC
157 340 329 9 2 92CHOCC
158 321 310 0 2 18CCCCO
159 318 308 0 2 32CCCCC
160 287 278 0 2 66dCOC
161 272 263 0 3 12dCCC

123
Quantum chemical investigations of a co-crystal

Table 2 continued
Mode Theoretical wavenumber/cm-1 TED/%
a b c d
Unscaled freq Scaled freq IIR IRAMAN

162 270 261 0 3 23dCCC ? 15CCCCC

163 263 254 0 0 41CCNCN
164 244 236 0 0 46CCNCN ? 11CCOCN
165 239 231 0 0 60 CCOCN ?11CHCOC
166 224 217 0 0 20 CCCCC ?15CCCCO ? 13dCCC
167 215 208 1 3 25CHCOC ? 24dNCO
168 207 200 0 5 33tCC
169 187 181 0 1 77dCOC
170 187 181 0 2 30CHCOC ? 27dNCO
171 182 176 0 6 28 CCCCO ? 10CCCCC
172 179 173 0 9 43CCCCC
173 164 159 0 1 68CHCOC
174 154 149 0 0 63CHCOC ? 13CCNCN
175 126 122 0 1 40CCOCN
176 115 112 0 1 32CCOCN ? 11CCCCC
177 113 110 0 1 44CCOCN
178 109 105 0 5 12tNH ? 10CCOCN
179 98 95 1 1 54CCOCN ? 19CCNCN
180 97 94 0 10 39CCCCC ? 16dCCC
181 80 77 0 21 24tNH ? 15dHNC
182 71 68 0 9 24dHNC ? 20tNH
183 55 53 0 88 57CCCCC
184 47 46 0 73 58CCCCC
185 42 40 0 37 47CCCCC ? 10dCCC
186 38 37 0 19 57CCCCC
187 34 33 0 14 32CCCCC ? 14dCCC ? 10tNH
188 31 30 0 11 27CCCCC ? 13dCCC ? 11dHNC
189 26 25 0 19 25CHNCN ? 11CCCCC
190 11 11 0 36 44CHNCN ? 24dOHN
191 9 9 0 61 77CCOHN
192 8 8 0 36 65CHOCC ? 10CCNHO
t stretching, d in-plane bending, C out-of-plane bending
a
IR and Raman calculated spectra
b
Obtained from the wave numbers calculated at B3LYP/6-311G(d,p) using scaling factors 0.967
c
Relative intensities of IR normalized with highest peak absorption equal to 100
d
Relative intensities of Raman normalized with highest peak absorption equal to 100
e
Total energy distribution calculated B3LYP/6-311G(d,p) level of theory. Only contributions C10 % are listed

and softness, and electrophilicity index. Vibrational band Computational details

assignments, simulated infrared and Raman spectra,
atomic charges and thermodynamic properties of the co-
crystal were also computed. The method used in this
study may prove to be a useful tool not only to support
the experimental results but also help to predict the
intermolecular interactions and construct designed
molecular self-assembled structures.
In this study, all calculations were performed with the
GaussView 5 molecular visualization program and
Gaussian 09 program package [50, 51]. The molecular
structure and vibrational calculations of the co-crystal were
computed by the Becke-3-Lee–Yang–Parr (B3LYP) [52,
53] method of theory with the 6–311??G(d,p) basis set in

123
 Ö. Dereli et al.

Fig. 4 Theoretical FT-IR

spectrum of the co-crystal

Fig. 5 Theoretical Raman

spectrum of the co-crystal

Fig. 6 3D plots of HOMO and LUMO

123
Quantum chemical investigations of a co-crystal

Table 3 The calculated HOMO–LUMO energies/eV of the co-crystal and the other parameters derived from these energies
EHOMO ELUMO ELUMO - EHOMO Electronegativity Hardness Softness Electrophilicity index

-5.525 -0.880 4.645 -3.203 -2.322 -0.215 -2.208

f ðt0  ti Þ4 Si
Ii ¼
ti ½1  expðhcti =kTÞ
where t0 cm-1 is the exciting frequency, ti is the vibra-
tional wavenumber of the ith normal mode, h, c, and k are
well-known universal constants and f is the suitably chosen
common scaling factor for all the peak intensities [57, 58].

Acknowledgments MMN is highly grateful to the Department of

Chemistry, Quaid-i-Azam University for providing necessary
research facilities.

References
Fig. 7 The MEP surface of co-crystal calculated at B3LYP/6-
311??G(d,p) level 1. Quesada-Moreno MM, Aviles-Moreno JR, Lopez-Gonzalez JJ,
Claramunt RM, Lopez C, Alkorta I, Elguero J (2014) Tetrahedron
Asymmetry 25:507
Table 4 Thermodynamic parameters of the co-crystal
2. Cross JM, Fennessy RV, Harding LP, Rice CR, Hardie MJ, Slater
Thermal Entropy S/J K C (2013) Chem Commun 49:11290
energy E/kJ mol-1 3. Stevenson KA, Melan CFC, Fleischel O, Wang RY, Petitjean A
(2012) Cryst Growth Des 12:5169
Electronic 0.000 Electronic 0.000 4. Goel M, Jayakannan M (2012) Chem Eur J 18:11987
Translational 3.719 Translational 186.866 5. Reviriego F, Navarro P, Aran VJ, Jimeno ML, Garcia-Espana E,
Latorre J, Yunta MJR (2011) J Org Chem 76:8223
Rotational 3.719 Rotational 165.050 6. Onet CI, Zhang L, Clerac R, Jean-Denis JB, Feeney M, McCabe
Vibrational 1,448.856 Vibrational 626.353 T, Schmitt W (2011) Inorg Chem 50:604
Total 1,456.294 Total 978.269 7. Guarrera D, Taylor LD, Warner JC (1994) Chem Mater 6:1293
8. Hagrman D, Hagrman PJ, Zubieta J (1999) Angew Chem Int Ed
Heat capacity
38:3165
Cv/J mol-1K-1
9. Abbas A, Nazir H, Naseer MM, Bolte M, Hussain S, Hafeez N,
Electronic 0.000 Dipol moment D/D 3.8435 Hasan A (2014) Spectrochim Acta A 120:176
Translational 12.472 Zero-point vibrational 1362.499 10. Chang YF, Lu ZY, An LJ, Zhang JP (2012) J Phys Chem C
energy/kJ mol-1 116:1195
Rotational 12.472 Sum of electronic and -1,775.016565 11. Tahir MN, Eberhardt M, Therese HA, Kolb U, Theato P, Muller
zero-point energies/ WE, Schroder HC, Tremel W (2006) Angew Chem Int Ed
hartree particle-1 45:4803
12. Hoger S (2004) Chemistry 10:1320
Vibrational 540.882 Sum of electronic and -1,775.090988
13. Granick S, Lin Z, Bae SC (2003) Nature 425:467
thermal free energies/
14. Vallavoju N, Sivaguru J (2014) Chem Soc Rev 43:4084
hartree particle-1
15. Weissman H, Rybtchinski B (2012) Curr Opin Colloid Interface
Total 565.826 Sci 17:330
16. Lehn JM (2011) C R Chim 14:348
17. Chopra D, Row TNG (2011) Cryst Eng Comm 13:2175
the ground state. As this type of calculation has the well- 18. Rotello VM (2001) Curr Org Chem 5:1079
known systematic errors, the calculated vibrational wave- 19. Claessens CG, Stoddart JF (1997) J Phys Org Chem 10:254
20. Lindsey JS (1991) New J Chem 15:153
numbers were scaled by 0.967 for the used level of DFT
21. Black CT, Ruiz R, Breyta G, Cheng JY, Colburn ME, Guarini
[54, 55]. The assignments of fundamental vibrational KW, Kim HC, Zhang Y (2007) IBM J Res Dev 51:605
modes of the co-crystal were performed on the basis of 22. Zhang S, Marini DM, Hwang W, Santoso S (2002) Curr Opin
total energy distribution (TED) analysis using the VEDA 4 Chem Biol 6:865
23. Weis M, Waloch C, Seiche W, Breit B (2006) J Am Chem Soc
program [56].
128:4188
The Raman activities (Si) calculated using Gaussian 09 24. Stojanovic MN, de Prada P, Landry DW (2000) J Am Chem Soc
program have been converted to relative Raman intensities 122:11547
(Ii) using the following relationship: 25. Jiang SP, Liu Z, Tian ZQ (2006) Adv Mater 18:1068

123

26. Williams JH (1993) Acc Chem Res 26:593
27. West J, Mecozzi S, Dougherty DA (1997) J Phys Org Chem
10:347
28. Luhmer M, Bartik K, Dejaegere A, Bovy P, Reisse J (1994) Bull
Soc Chim France 131:603
29. Dennis GR, Ritchie GLD (1991) J Phys Chem 95:656
30. Mooibroek TJ, Gamez P (2007) Inorg Chim Acta 360:381
31. Mascal M, Armstrong A, Bartberger MD (2002) J Am Chem Soc
124:6274
32. Wang DX, Zheng QY, Wang QQ, Wang MX (2008) Angew
Chem 120:7595
33. Naseer MM, Hameed S (2012) Cryst Eng Comm 14:4247
34. Jeffrey GA (1997) An introduction to hydrogen bonding. Oxford
University Press, New York
35. Khosa MA, Wu J, Ullah A (2013) RSC Adv 3:20800
36. Lambert JB, Shurvell HF, Cooks RG (1987) Introduction to
organic spectroscopy. Macmillan Publish, NewYork
37. Ullah A, Alongi J, Russo S (2011) Polym Bull 67:1169
38. Bellamy LJ (1975) The infrared spectra of complex molecules,
3rd edn. Wiley, New York
39. Colthup NB, Daly LH, Wiberley E (1964) Introduction to infra-
red and raman spectroscopy. Academic Press, New York
40. Stuart BH (2004) Infrared spectroscopy: fundamentals and
applications. Wiley, New York
41. Silverstein RM, Webster FX (1998) Spectroscopic identification
of organic compounds, 6th edn. Wiley, New York
42. Lefrada L, Bouchemma A, Bouhenguel M, Ferhati A, Chebbah M
(2012) Eur J Chem 3:404
43. Shaw RA, Ward P (1967) 1,3,5-Triazines. Part VII. The ultra-
violet, infrared, and 1H nuclear magnetic resonance spectra of
some chloro-1,3,5-triazine derivatives. J Chem Soc B 123–126.
doi:10.1039/J29670000123
44. Lehn JM (1995) Supramolecular chemistry: concepts and per-
spectives. Wiley-VCH, Weinheim
45. Gökce H, Bahçeli S (2013) Spectrochim Acta A 114:61
46. Fukui K (1982) Science 218:747
123
Ö. Dereli et al.
47. Mary YS, Jojo PJ, Panicker CY, Van Alsenoy C, Ataei S, Yildiz I
(2014) Spectrochim Acta A 122:499
48. Pirnau A, Chis V, Oniga O, Leopold N, Szabo L, Baias M, Cozar
O (2008) Vib Spectrosc 48:289
49. Murray JS, Sen K (1996) Molecular Electrostatic Potentials
Concepts and Applications. Elsevier Science BV, Amsterdam
50. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA,
Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson
GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF,
Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K,
Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao
O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F,
Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN,
Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC,
Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M,
Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts
R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C,
Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth
GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas
Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian
09, revision C.01. Gaussian, Inc., Wallingford
51. Dennington R, Keith T, Millam J (2009) GaussView, version 5.
Semichem Inc, Shawnee Mission
52. Becke AD (1993) J Chem Phys 98:5648
53. Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785
54. Foresman JB, Frisch E (1993) Exploring Chemistry with Elec-
tronic Structure Methods. Gaussian Inc, Pittsburgh
55. http://cccbdb.nist.gov/vibscalejust.asp
56. Jamr’oz MH (2004) Vibrational energy distribution Analysis.
VEDA4, Warsaw
57. Keresztury G, Holly S, Varga J, Besenyei G, Wang AY, Durig JR
(1993) Spectrochim Acta A 49:2007
58. Keresztury G (2002) In: Chalmers JM, Griffith PR (eds) Raman
spectroscopy: theory in hand book of vibrational spectroscopy,
vol 1. Wiley, New York