Investigation of Charge Transfer

Co-crystals from Electron Rich

and Electron Deficient Compounds
A THESIS
submitted in partial fulfillment of the requirements
for the award of the dual degree of

Bachelor of Science – Master of Science

in

CHEMISTRY

by

AKSHAJ PREM

(13003)

DEPARTMENT OF CHEMISTRY
INDIAN INSTITUTE OF SCIENCE EDUCATION AND
RESEARCH BHOPAL
BHOPAL – 462 066

APRIL 2018

i
i
 Indian Institute of Science Education and Research,
Bhopal
DEPARTMENT OF CHEMISTRY

CERTIFICATE
This is to certify that AKSHAJ PREM, BS-MS (Dual Degree) student in the Department of

Chemistry, has completed bonafide work on the dissertation entitled INVESTIGATION OF

CHARGE TRANSFER CO-CRYSTALS FROM ELECTRON RICH AND

ELECTRON DEFICIENT COMPOUNDS under my supervision and guidance.

April 2018

IISER Bhopal Dr. Deepak Chopra

Committee Member Signature Date

Dr. Deepak Chopra

Prof. Sangit Kumar

Prof. Alakesh Bisai

i
 ACADEMIC INTEGRITY AND
COPYRIGHT DISCLAIMER
I hereby declare that this MS-Thesis is my own work and, to the best of my

knowledge, that it contains no material previously published or written by another person,

and no substantial proportions of material which have been accepted for the award of any

other degree or diploma at IISER Bhopal or any other educational institution, except where

due acknowledgement is made in the document.

I certify that all copyrighted material incorporated into this document is in compliance

with the Indian Copyright (Amendment) Act (2012) and that I have received written

permission from the copyright owners for my use of their work, which is beyond the scope of

that law. I agree to indemnify and saveguard IISER Bhopal from any claims that may arise

from any copyright violation.

April 2018
IISER Bhopal Akshaj Prem

ii
 ACKNOWLEDGEMENT
First of all I like to express my sincere gratitude to my MS project supervisor Dr.

Deepak Chopra for giving me an opportunity to work in Crystallography and Crystal

Chemistry Laboratory (CCCL) and for the support, encouragement and enthusiasm he has

shown. I would like to thank Mr. Rohit Bhowal for guiding me throughout my project and

also other lab mates Dr. Manjeet Singh, Ms. Peuli Ghosh, Mr.Subhrajyoti Bhandari, Mr.

Rahul Shukla, Mr. Pradip Kumar Mondal, Ms. Avantika Hasija, Ms. Gulshan Rani, Mr. Devi

Prasad A S, Mr. Athul Babu T, Mr. Ajay Kharbade and Ms. Shraddha Gedam for supporting

me. I would like to acknowledge IISER Bhopal and convey my regards to Department of

Chemistry and Central Instrumentation Facility (CIF). I would like to acknowledge

Suprakash Biswas and Dr. Apurba Lal Koner for the support in photophysical measurements.

I really appreciate their support. I am thankful to all my friends at IISER Bhopal for

supporting me and being with me throughout the journey five years at IISER Bhopal.

Finally, I would like to thank my family and friends for being with me always and supporting

me.

Akshaj Prem

iii
 ABSTRACT
Co-crystals are gaining the extensive interest of researchers from various fields of chemical

sciences. In the current study, the co-crystallization of 4-Nitro-1,8-naphthalic anhydride and

3,5-Dinitrobenzonitrile with 1,3,5-Tris(4-aminophenyl) benzene and 3,3’,5,5’-

Tetramethylbenzidine resulted in the formation of four two component co-crystals. Solvent

drop grinding method with components in 1:1 stoichiometric ratio was used for co-

crystallization. Co-crystals were isolated as single crystals by slow evaporation method and

characterized by X-ray diffraction methods. Further differential scanning calorimetry (DSC)

and infrared spectroscopy have been done to characterize the co-crystals .Charge transfer

interactions in the co-crystal are studied by UV-Vis spectroscopy (UV-Vis).The main

stabilizing factors in the crystal packing are π···π stacking and hydrogen bonding interactions.

iv
LIST OF SYMBOLS OR
ABBREVIATIONS
SCXRD Single Crystal X-ray Diffraction

PXRD Powder X-ray Diffraction

DSC Differential Scanning Calorimetry

NNA 4-Nitro-1,8-naphthalic anhydride

DNB 3,5-Dinitrobenzonitrile

TAPB 1,3,5-Tris(4-aminophenyl) benzene

TMB 3,3ʹ,5,5ʹ-Tetramethylbenzidine

FT-IR Fourier transform Infrared Spectroscopy

UV-Vis Ultraviolet-Visible spectroscopy

a Unit cell dimension

b Unit cell dimension

c Unit cell dimension

α Interfacial angle between unit cell dimension b &c

β Interfacial angle between unit cell dimension a & c

γ Interfacial angle between unit cell dimension a & b

λ Wavelength

v
 LIST OF FIGURES AND TABLES
Title Page

Figure 1: Co-crystal formation. 1

Figure 2: Flowchart for co-crystal design strategies based on synthon competition. 3

Figure 3: Donor–acceptor interactions between the molecules. 4

Figure 4: Images of Co-crystal preparation depicting colour changes during 8

grinding.

Figure 5: Differential Scanning Calorimetry (DSC) traces overlay of all co- 11

crystals.

Figure 6: Experimental PXRD pattern of co-crystal 1 with simulated PXRD 12

pattern.

Figure 7: Experimental PXRD pattern of co-crystal 2 with simulated PXRD 12

pattern.

Figure 8: Experimental PXRD pattern of co-crystal 3 with simulated PXRD 13

pattern.

Figure 9: Experimental PXRD pattern of co-crystal 4 with simulated PXRD 13

pattern.

Figure 10: Solid state absorption spectra of all co-crystals. 14

Figure 11: FT-IR (Fourier transform Infrared Spectroscopy) of co-crystals. 15

Figure 12: ORTEP of co-crystal 1 with 50% ellipsoidal probability. 16

Figure 13: Packing diagram of co-crystal 1 showing interactions. 17

Figure 14: Packing view of co-crystal 1 via N–H···O, N–H···N and C–H···O 17

interactions along the b axis.

Figure 15: ORTEP view of co-crystal 2 with 50% ellipsoidal probability. 19

vi
Figure 16: Packing diagram of co-crystal 2 showing interactions. 19

Figure 17: Packing diagram of co-crystal 2 showing N–H···O and C–H···O 21

interactions.

Figure 18: ORTEP view of co-crystal 3 with 50% ellipsoidal probability. 22

Figure 19: Packing diagram of co-crystal 3 showing interactions. 22

Figure 20: Packing diagram of co-crystal 3 showing C–H···O and N–H···O 24

interactions.

Figure 21: ORTEP of co-crystal 4 with 50% ellipsoidal probability. 24

Figure 22: Packing diagram of co-crystal 4 showing interactions and N··· 24

interactions.

Figure 23: Packing diagram of co-crystal 4 via C–H···O and N–H···O interactions. 25

Figure 24: Packing view of the crystal structure highlighting the zigzag molecular 25

chain.

Figure 25: Packing diagram of co-crystal 4 via C–H···N interactions. 26

Table 1: Scheme for the experiments for obtaining co-crystals 5-6

Table 2: Crystallographic table and refinement data of co-crystal 1, 2, 3 and 4. 9-10

Table 3: Interaction table of co-crystal 1. 18

Table 4: Interaction table of co-crystal 2. 21

Table 5: Interaction table of co-crystal 3. 23-24

Table 6: Interaction table of co-crystal 4. 26-27

Table 7: Melting points of co-crystals and starting materials. 27-28

vii
TABLE OF CONTENTS
i. Certificate

ii. Academic Integrity and Copyright Disclaimer

iii. Acknowledgement

iv. Abstract

v. List of Symbols

vi. List of Figures and Tables

1. Introduction … 1-4

2. Material and methods … 5-15

2.1. Chemicals and materials

2.2. Co-crystal preparation

2.3. Characterization Methods

2.3.1. Single X ray Diffraction

2.3.2. Differential Scanning Calorimetry

2.3.3. Powder X ray Diffraction

2.3.4. Spectroscopic studies

a) UV-Vis Spectroscopy

b) IR Spectroscopy

3. Results and discussion … 16-28

4. Conclusions … 28

5. References … 29-33

viii
ix
 1. INTRODUCTION
Co-crystals

Co-crystals are crystalline single phase materials composed of two or more different

molecular or ionic compounds, generally in a stoichiometric amount.1The definition of co-

crystals,1,2,3,4,5 has been a topic of debate in the literature. As co-crystals have the opportunity

to access new solid forms and therefore modified physical properties they have high

relevance in both academic research and industrial applications. Co-crystallisation has shown

promise in the tuning of a range of physical properties including dissolution rate,7

compressibility8 and physical stability.9 There are many different methods in which

crystallization can be done for a single component system including cooling, solvent

evaporation, dry grinding, liquid-assisted grinding (LAG),10 sublimation, crystallization from

the melt, crystallization from gels,11 use of supercritical fluids,12 pressurisation13 and many

more.

Figure 1: Co-crystal formation.

1
The launch pad for systematic consideration of co-crystal design and prediction was Etter's

1990 publication14 investigating the predictability of hydrogen bonds which, based on the

evidence of known crystal structures, also set forth a list of empirical hydrogen-bonding rules

for neutral, organic compounds. In this study, Etter proposed three general rules for organic

compounds:

1. All good proton donors and acceptors are used in hydrogen bonding.

2. Six-membered ring intramolecular hydrogen bonds form in preference to intermolecular

hydrogen bonds.

3. The best proton donors and acceptors remaining after intramolecular hydrogen bond

formation form intermolecular hydrogen bonds.

Inherent to these rules is the principle that one can determine not only which donors and

acceptors are ‘good’ (for rule 1), but also those that are the ‘best’ (for rule 3). Building on

these empirical hydrogen-bonding rules, Desiraju introduced another concept in 199515 that is

central to co-crystal design – that of the supramolecular synthon:

“Supramolecular synthons are structural units within supermolecules which can be formed

and/or assembled by known or conceivable synthetic operations involving intermolecular

interactions.”

The principle put forth in this study is that a supramolecular synthon must be “robust enough

to be exchanged from one network structure to another”.15 Essentially, there must be

evidence that the structural unit is reproducible across multiple solid state environments. An

intermolecular structural unit in general may be referred to as an interaction motif; if the

motif in question is then shown to be robust and reproducible then it could be referred to as a

synthon. If these supramolecular synthons are genuinely reproducible, then they could be

used in the rational design of a co-crystal.

2
Subsequent researchers in the field of crystal engineering such as Aakeröy3,16 and

Zaworotko2,17,18developed the concepts presented by Etter and Desiraju into a transferable

knowledge-based workflow through which the relative quality of particular donors, acceptors

and synthons can be assessed quantitatively. This can then be used to predict how robust a

given synthon will be.

Figure 2: Flowchart for co-crystal design strategies based on synthon competition.1

A co-crystal strategy can realize the introduction of diverse neutral molecules19,20 and

is likely to obtain superior properties because of synergistic effects of the individual

components.21 Supramolecular organic co-crystal chemistry which focuses on the

study of various non covalent interactions, such as hydrogen bonds, C−H···π, π···π,

and charge-transfer (CT) interactions induced by molecular recognition, has been of

significance in recent years because of their remarkable structural topologies and

potential applications.22 Co-crystal engineering may facilitate further design and

development of novel materials for nonlinear optical and optoelectronic applications.

3
During the structural optimization process23, parameters such as 1) strength of the

electron- donor and -acceptor groups, 2) the coplanarity of conjugated systems, and 3)

the length and path of conjugated chains should be considered.24 Intermolecular

strategies circumvent the challenges associated with single molecular systems.25

Organic charge-transfer complexes that assemble into intermolecular architectures

through noncovalent interactions offer numerous advantages, including 1) a plentiful

supply of materials obtained from simple molecular units without complicated

synthetic procedures, 2) modulated properties through selecting suitable conformers,

and 3) tunable morphologies and size by control of the interactions in multiple

components.26

 Donor–acceptor interactions between the molecular

components are the main driving force

Figure 3: Donor–acceptor interactions between the molecules.

Method called “Solvent drop grinding”27 is used for co-crystallization of selected starting

materials. Electron rich and electron deficient aromatic rings are taken as starting materials to

design Strong interactions and charge transfer phenomena .The outcome of co-crystals

was confirmed by powder X-ray diffraction analysis (PXRD), and structurally characterized

by single crystal X-ray diffraction analysis (SCXRD).

4
 2. MATERIALS AND METHODS
2.1. Chemicals and materials: 4-Nitro-1,8-naphthalic anhydride was obtained from Sigma-

Aldrich Co. and 3,5-Dinitrobenzonitrile which obtained from TCI Chemicals (India) Pvt. Ltd.

were used acceptors for co-crystal synthesis. 1,3,5-Tris(4-aminophenyl) benzene and

3,3’,5,5’-Tetramethylbenzidine were purchased from TCI Chemicals (India) Pvt. Ltd. and

were used as donors for co-crystal synthesis. All these chemicals have been used as received

without further purification. Various HPLC grade solvents of different polarity were used for

crystallization process like dichloromethane, acetone, ethyl acetate, methanol, ethanol,

isopropyl alcohol, diethyl ether, diisopropyl ether, Isooctane, toluene, trifluorotoluene

without further purification. The crystals obtained were then characterized structurally using

SCXRD.

Table 1: Chemical Scheme for obtaining co-crystals

Sl Sample Code Starting Materials

No.

4-Nitro-1,8-naphthalic 1,3,5-Tris(4-aminophenyl)benzene

Co-crystal 1 anhydride (NNA) (TPB)

5
 2

Co-crystal 2 4-Nitro-1,8-naphthalic 3,3ʹ,5,5ʹ-Tetramethylbenzidine

Anhydride (NNA) (TMB)

Co-crystal 3 3,5-Dinitrobenzonitrile 1,3,5-Tris(4-aminophenyl) benzene

(DNB) (TPB)

3,5-Dinitrobenzonitrile 3,3ʹ,5,5ʹ-Tetramethylbenzidine
Co-crystal 4
(DNB) (TMB)

2.2. Co-crystal Preparation:

A method known as solvent-drop grinding (SDG) was used for co-crystal synthesis by

mechanical grinding of components using mortar and pestle. The two components of co-

crystals were taken in a 1:1 stoichiometric ratio for grinding. Methanol was used as a solvent

for grinding. Grinding was usually carried out for 75 minutes with dropwise addition of

solvent at an interval of 15 minutes each. The resulting powder was air dried and crystallized

6
using various solvents in 5ml beakers and 5ml vials and then kept for crystallization at low

temperature (4˚C).28 These crystals obtained were then characterized structurally using

SCXRD. Following these experiments, the observed stoichiometric ratio, as obtained via

SCXRD, was used to reproduce the formation of all of the as-synthesized (bulk) co-crystals

and was used for all of the further experiments. Furthermore, the PXRD patterns obtained for

all of the powdered samples along with the PXRD patterns collected on the obtained single

crystals are in complete agreement with each other.

I. Co-crystal 1: A mixture of 4-nitro-1,8-naphthalic anhydride and 1,3,5-tris(4-

aminophenyl) benzene taken in 1:1 molar ratio was mechanically grounded using

mortar and pestle with drop-wise addition of methanol. The resulting mixture was

dissolved in dichloromethane in a 5 ml vial and kept for crystallization at low

temperature (4˚C).

II. Co-crystal 2: A mixture of 4-nitro-1,8-naphthalic anhydride and 3,3ʹ,5,5ʹ-

tetramethylbenzidine taken in 1:1 molar ratio was mechanically ground using mortar

and pestle with drop-wise addition of methanol. The resulting mixture was dissolved

in dichloromethane in a 5 ml vial and kept for crystallization at low temperature

(4˚C).

III. Co-crystal 3: A mixture of 3,5-dinitrobenzonitrile and 1,3,5-tris(4-aminophenyl)

benzene taken in 1:1 molar ratio was mechanically ground using mortar and pestle

with drop-wise addition of methanol. The resulting mixture was dissolved in

dichloromethane in a 5 ml vial and kept for crystallization at low temperature (4˚C).

IV. Co-crystal 4: A mixture of 3,5-dinitrobenzonitrile and 3,3ʹ,5,5ʹ-tetramethylbenzidine

taken in 1:1 molar ratio was mechanically ground using mortar and pestle with drop-

wise addition of methanol. The resulting mixture was dissolved in dichloromethane in

a 5 ml vial and kept for crystallization at low temperature (4˚C).

7
 TAPB+NNA

Initial mixture After 15mins After 30mins Final Product

TMB+NNA

Initial mixture Within 15mins After 30mins Final Product

TAPB+DNB

Initial mixture Within 15mins Final Product

TMB+DNB

Initial mixture After mixing(within in 5 mins) After 75 mins

Figure 4: Images of Co-crystal preparation depicting colour changes during grinding.

8
2.3. Characterization Studies

2.3.1. Crystal data collection and structure solution

Single crystals of co-crystal 1, co-crystal 2, co-crystal 3 and co-crystal 4 suitable for X-Ray

single crystal analysis were obtained by slow evaporation method at low temperature, by

using solvent dichloromethane. Single Crystal X-ray Diffraction data were collected on

Bruker AXS Kappa APEXII diffractometer using MoKα radiation (λ= 0.71073 Å) and

APEX2 software.29 Data integration and reduction were carried out with SAINT.30 Both

datasets were collected at –173˚C using an Oxford Cryostream low-temperature device.

Absorption correction were performed by multi-scan method implemented in SADABS.31

Both the crystal structures were solved by direct methods using SIR 2014.32 The crystal

structure refinement was done in the program package WinGX33 and all non-hydrogen atoms

were refined anisotropically by full matrix least squares calculations based on F2 with

SHELXL–2016.34All of the hydrogen atoms have been located from the difference Fourier

map. Details of crystal data, data collection and refinement details are provided in the

following Table. The PLATON35 and MERCURY36 programs were used for structure

analysis and molecular and crystal structure drawings preparation.

Table 2: Crystallographic table and refinement data of co-crystal 1, 2 , 3 and 4.

Sample Code Co-crystal 1 Co-crystal 2 Co-crystal 3 Co-crystal 4

Formula C36 H25 N4 O5 C28 H25 N3 O5 C31 H22 N6 O5 C23 H23 N5 O4
Solvent DCM DCM DCM DCM
Formula Weight 593.60 483.51 558.54 433.46
Temperature 100(1) 100(1) 100(1) 100(1)
Wavelength ( Å ) 0.71073 0.71073 0.71073 0.71073
Crystal System Monoclinic Monoclinic Monoclinic Monoclinic
Space Group P21/c P21/c C 2/c C 2/c

9
 Z´, Z 2, 8 2, 8 3, 8 2, 8
a( Å ) 15.0020(5) 10.9617(5) 28.799(6) 31.2029(11)
b( Å ) 7.5587(2) 15.6825(8) 7.2045(13) 6.8944(3)
c( Å ) 25.1734(8) 13.4532(7) 28.780(5) 19.5728(8)
α ) 90 90 90 90
β ) 101.094(2) 99.498(2) 119.657(5) 99.506(2)
γ ) 90 90 90 90
Volume (Å-3) 2801.21(15) 2281.0(2) 5189.1(17) 4152.8(3)
Density (g cm-3) 1.408 1.408 1.430 1.387
F 000), μ mm-1) 1236, 0.096 1016, 0.098 2320, 0.100 1824, 0.098
θ min, max) 1.938, 25.087 1.884, 27.877 3.561, 28.926 2.110, 30.344
hmin,max, kmin,max, (-17,17), (-9,9), (-14,13), (-18,20), (-22,37), (-9,9), (-44,44), (-9,9),
lmin,max (-29,30) (-17,17) (-38,32) (-27,27)
Treatment of Located Located Located Located
Hydrogen
No. unique 4933, 3424 5437, 2409 6436, 2819 6174, 4369
ref/obs. Ref.
No of Parameter 489 400 439 358
R_all, R_obs 0.0903, 0.0605 0.1966, 0.0838 0.2112,0.0970 0.0866, 0.0564
wR2_all, 0.1723, 0.1540 0.2289, 0.1755 0.2635,0.2031 0.1582, 0.1400
wR2_obs
Δρmin,max(eÅ-3) -0.367, 0.606 -0.390, 0.285 -0.414 , 0.331 -0.354, 0.445
G.o.F 1.054 0.978 0.985 1.030

2.3.2. Differential Scanning Calorimetry (DSC)

Perkin-Elmer DSC 6000 Instrument under nitrogen gas atmosphere was used for the DSC

experiment. Precisely weighed sample of each co-crystal were placed in non-hermetic sealed

aluminum pans and then allowed to scan with respect to an aluminum pan containing

vacuum.

10
All of the samples were scanned at a rate of 5˚C/min in different ranges of temperature under

a dry nitrogen atmosphere at a flow rate of 20 ml/min.

Figure 5: Differential Scanning Calorimetry (DSC) traces overlay of all co-crystals.

2.3.3. Powder X-ray Diffraction (PXRD)

The experimental powder X-ray diffraction patterns of co-crystals were recorded on

PANalytical Empyrean X-ray Diffractometer with a Cu Kα radiation (1.54060 Å). Bulk

powder of each sample was placed on a silica sample holder and measured by a continuous

scan between 5 to 55º in 2θ with a step size of 0.013103º. Simulated powder X-ray

diffraction patterns of all co-crystals were obtained by Mercury 3.6 software package [10].

11
Figure 6:Experimental PXRD pattern of co-crystal 1 with simulated PXRD pattern.

Figure 7:Experimental PXRD pattern of co-crystal 2 with simulated PXRD pattern.

12
Figure 8:Experimental PXRD pattern of co-crystal 3 with simulated PXRD pattern.

Figure 9:Experimental PXRD pattern of co-crystal 4 with simulated PXRD pattern.

13
2.3.4. Spectroscopic Studies

(a) Diffuse reflectance UV-Vis NIR spectroscopy

The spectra of solid powdered samples were collected under ambient conditions on a
Cary 5000 UV-Vis-NIR (Agilent) equipped with diffuse reflectance accessory
sampling kit. The Spectralon reflectance standard disk was used as a reference material
for background correction.

Figure 10: Solid state absorption spectra of all co-crystals

14
 (b) Infrared Spectroscopy (IR)

The dry powder was mixed and pelletized with KBr for recording IR. The IR spectra
were obtained on PerkinElmer Spectrum BX FT-IR spectrometer operated via Spectrum
v5.3.1 software.

Figure 11: FT-IR (Fourier transform Infrared Spectroscopy) of co-crystals.

15
 3. RESULTS AND DISCUSSION
All co-crystals were synthesized using potential electron rich and electron acceptor molecules

as components. Solvent drop grinding (SDG) method in which each of the constituents were

taken in a 1:1 ratio and crystallized using various solvents of different polarity to obtain novel

co-crystals. Four co-crystals were synthesized and characterized by single crystal X-ray

diffraction studies.

Co-crystal 1

Figure 12: ORTEP of co-crystal 1 with 50% ellipsoidal probability.

TAPB : NNA crystallizes in the monoclinic crystal system with the centrosymmetric space

group P21/c. The asymmetric unit consists of one of TAPB and one NNA molecule and the

unit cell contains a total of 8 molecules.

16
Figure 13: Packing diagram of co-crystal 1 showing interactions.

NNA is an electron deficient (acceptor) and TAPB is an electron rich (donor) molecule and

the crystal packing of this co-crystal is principally guided by stacking interactions

between the donor and acceptor molecules.

Figure 14: Packing view of co-crystal 1 via N–H···N, N–H···O and C–H···O interactions
along the b axis.

17
TAPB is a propeller shaped molecule with dihedral angles of 14˚, 34˚ and 38˚ between the

central and peripheral aryl rings. The two adjacent donor molecules in the crystal lattice are

connected via N–H···N interactions while the donor and acceptor molecules are connected

via strong N–H···O and weak C(sp2)–H···O interactions when the crystal packing is viewed

down the ac plane.

Table 3: Interaction table of co-crystal 1.

Cocrystal Interactions Symmetry D•••A Å) H•••A Å) D-

H...A(°)
C1(π)···C31(π) x,y,z 3.265

C22(π)···C28(π) x,-1+y,z 3.277

C22(π)···C27(π) x,-1+y,z 3.349

C19(π)···C34(π) x,-1+y,z 3.356

Co-crystal 1
C24(π)···C29(π) x,-1+y,z 3.315

C19(π)···C25(π) x,y,z 3.398

C21(π)···C36(π) x,-1+y,z 3.211

C36(π)···C36(π) 1-x,y,1-z 3.073

N1–H1NA··· O3 -x,-1/2+y,1/2-z 3.378 2.521 146

N2–H2NB··· O3 1-x,-1/2+y,1/2-z 2.976 2.203 142
C18–H18··· O2 1-x.-y,1-z 3.378 2.474 153
C20–H20···O2 1-x.-y,1-z 3.979 2.555 170
C12–H12···O4A -x.-y,1-z 3.412 2.669 136
N3–H3NB··· N1 -x,1-y,1-z 3.186 2.406 139
N3–H3NA··· N2 x,1/2-y,-1/2+z 3.221 2.296 162

18
Co-crystal 2

Figure 15: ORTEP of co-crystal 2 with 50% ellipsoidal probability

TMB : NNA crystallizes in the monoclinic crystal system with centrosymmetric space group

P21/c. The asymmetric unit consists of one TMB and one NNA molecule and there are a total

of 8 molecules in the unit cell.

Figure 16: Molecular motif of co-crystal 2 showing interactions

19
In this co-crystal TMB is electron rich molecule (donor) while NNA is electron deficient

molecule (acceptor) and the principal driving force for packing the two molecules in the

crystal lattice is stacking interactions.

Figure 17: Packing diagram of co-crystal 2 showing N–H···O and C–H···O interactions.

Along with stacking interactions additional non-covalent intermolecular contacts are

also present in the crystal lattice. The donor and acceptor molecules in adjacent stacking

columns are connected via strong and directional N–H···O interactions when viewed down

the ab plane while weak C(sp3)–H···O interactions connects the donor and acceptor

molecules from adjacent stacked columns as well as between molecules of the same column

when viewed down the ac plane.

20
Table 4: Interaction table of co-crystal 2

Cocrystal Interactions Symmetry D•••A Å) H•••A Å) D-

H...A(°)
C4(π)···C18(π) x,1/2-y,-1/2+z 3.327

C3(π)···C17(π) x,1/2-y,-1/2+z 3.315

C6(π)···C21(π) x,1/2-y,-1/2+z 3.319

Co-crystal 2
C10(π)···C27(π) x,1/2-y,-1/2+z 3.329

C10(π)···C28(π) x,1/2-y,-1/2+z 3.329

C14(π)···C26(π) x,1/2-y,-1/2+z 3.349

C16– H16A··· O5 x,1/2-y,-1/2+z 3.203 2.591 117

C7–H7C···O2 x,1/2-y,-1/2+z 3.471 2.717 128
N1–H1A···O3 1-x,1/2+y,1.5-z 3.304 2.664 128

Co-crystal 3

Figure 18: ORTEP view of co-crystal 3 with 50% ellipsoidal probability

21
TAPB:DNB crystallizes in the monoclinic crystal system with centrosymmetric space group

C2/c. There is one TAPB, one DNB and one water molecule in the asymmetric unit and there

are a total of 24 molecules in the unit cell.

Figure 19: Molecular trimer of co-crystal 3 showing interactions.

In this co-crystal TAPB is an electron rich molecule (donor) while DNB is an electron

deficient molecule (acceptor). The principal driving force for packing the two molecules in

the crystal lattice is π···π stacking interactions between the donor and acceptor molecules.

Figure 20: Packing diagram of co-crystal 3 showing C–H···O and N–H···O interactions.

22
TAPB is a propeller shaped molecule with dihedral angles of 5˚, 14˚ and 24˚ between the

central and peripheral aryl rings. Apart from the π···π stacking interactions, there are exists

additional non-covalent contacts between the two components and guest water molecules

present in the crystal lattice. The two adjacent donor molecules are connected through the

guest water molecule via strong N–H···O interactions, while the neighbouring donor and

acceptor molecules are connected via strong N–H···O and weak C(sp2)–H···O interactions

when the crystal packing is viewed down the ac plane.

Table 5: Interaction table of co-crystal 3.

Cocrystal Interactions Symmetry D•••A Å) H•••A Å) D-

H...A(°)
C28(π)···C11(π) x,y,z 3.365

C28(π)···C19(π) x,y,z 3.324

C28(π)···C20(π) x,y,z 3.209

C28(π)···C9(π) x,1+y,z 3.380

Co-crystal 3 C30(π)···C4(π) x,1+y,z 3.377

C30(π)···C5(π) x,1+y,z 3.281

C30(π)···C7(π) x,1+y,z 3.385

N3–H3A···O1 1-x,y.1.5-z 3.165 2.319 160

N1–H1B···O4 1-x,1-y,1-z 3.202 2.482 137
C2–H2···O4 1-x,1-y,1-z 3.295 2.479 139
C18–H18···O3 1/2-x,1.5-y,1-z 3.425 2.614 147
C20–H20···O3 1/2-x,1.5-y,1-z 3.583 2.708 133

23
 N2–H2A···O5 1/2-x,1/2+y,1/2-z 3.048 2.245 152
N1–H1A···O5 1-x,1-y,1-z 2.959 2.597 103
N3–H3B···O5 1/2-x,1.5-y,1-z 3.111 2.299 153

Co-crystal 4

Figure 21: ORTEP of co-crystal 4 with 50% ellipsoidal probability.

TMB:DNB crystallizes in the monoclinic crystal system with centrosymmetric space group

C2/c. There is one TMB and one DNB molecule in the asymmetric unit and there are a total

of 16 molecules in the unit cell.

Figure 22: Packing diagram of co-crystal 4 highlighting interactions and N···

interactions.

24
Here DNB is electron deficient (acceptor) due to the presence of two nitro groups and one

cyano group and TMB is electron rich (donor) due to the presence of amine and methyl

groups. The two molecular components are stacked over each other through π···π stacking

and N···π interactions which are perpendicular to the molecular planes of both the molecules

in the crystal lattice.

Figure 23: Packing diagram of co-crystal 4 via C–H···O and N–H···O interactions down the
ac plane.

The adjacent donor and acceptor molecules of this co-crystal are connected to each other via

strong N–H···O and weak C(sp2/sp3)–H···O interactions in the crystal lattice. Here the donor

and acceptor molecules together are layered over alternate molecules along the b axis in a

zigzag like pattern forming an infinite molecular chain. TMB and DNB molecules along the

chain are connected to each other via strong N–H···O and weaker C(sp2)–H···O interactions

while the adjacent molecular chains are held together via weak C(sp3)–H···O interactions.

Figure 24: Packing view of the crystal structure highlighting the zigzag molecular chain

down the b axis.

25
Figure 25: Packing motifs of co-crystal 4 via C–H···N interactions involving the amino

group and the cyano group.

There also exists the presence of weak C(sp2)–H···N(sp3) interactions between the amine

group of the donor and the aromatic proton of the acceptor molecules while there are weak

C(sp2)–H···N(sp) between the cyano group and aromatic proton of acceptor molecules.

Table 6: Interaction table of co-crystal 4.

Cocrystal Interactions Symmetry D•••A Å) H•••A Å) D-

H...A(°)
C18(π)···C3(π) x,y,z 3.161

C18(π)···C4(π) x,y,z 3.395

C20(π)···C9(π) x,y,z 3.310

C20(π)···C14(π) x,y,z 3.300

Co-crystal 4
C22(π)···C5(π) x,y,z 3.328

C18(π)···C9(π) x,1+y,z 3.187

C20(π)···C13(π) x,1+y,z 3.330

26
 N3···C1(π) x,y,z 3.089

N3···C5(π) x,1+y,z 3.127

N4···C11(π) x,1+y,z 3.175

C8–H8A···O1 x,y,z 3.405 2.660 130

C8–H8B···O3 1-x,1-y,1-z 3.655 2.684 172
C3–H3···O4 1-x,1-y,1-z 3.639 2.655 174
C10–H10···O4 1-x,1-y,1-z 3.411 2.501 156
N1–H23···O1 x,1-y,1/2+z 2.984 2.348 129
C8–H8C···O3 x,1-y,1/2+z 3.495 2.589 155
C22–H22···N5 1/2-x,1.5-y,1-z 3.283 2.750 114
C20–H20···N2 x,1-y,1/2+z 3.485 2.639 157

Furthermore, the PXRD patterns obtained for all of the powdered samples along with the

PXRD patterns collected on the obtained single crystals are in complete agreement with

each other. Homogeneity and phase purity of samples can be established by PXRD patterns.

Thermal stabilities of the bulk materials have been investigated by DSC. These are based on

principle of change in heat (either in terms of endothermic or exothermic process) with the

change in the physical state of the compound.

Table 7: Melting point of co-crystals and starting materials.

Starting Melting point Co-crystals Melting point

Materials ( oC ) ( oC )
NNA 226-229

TAPB 165
Co-crystal 1 173.00

27
 NNA 226-229

TMB 168-171
Co-crystal 2 148.93
DNB 126-130

TABP 165
Co-crystal 3 191.43

DNB 126-130

TMB 168-171
Co-crystal 4 188.71

The thermal stability of the co-crystals were assessed by differential scanning calorimetry

(DSC) and then compared with the starting materials. It was observed that although the

thermal stability of co-crystal 1 is slightly greater than TAPB but it is considerably much

lesser than NNA, while co-crystal 2 is thermally much less stable than either of the starting

materials. But co-crystal 3 and co-crystal 4 shows sharp endothermic peaks at higher

temperature than both the starting materials indicating greater thermal stability than both the

components.

In the UV-Visible specta there is a significant red shift observed in co-crystals as compared

to the starting materials. The absorption maxima of co-crystals occur in a range of 500-

700nm except for co-crystal 2. In the case of co-crystal 1 an absorption peak is observed at

657 nm, which is significantly red shifted from the absorption peaks of both the starting

materials (408 nm-TAPB, 396-NNA). Whereas in co-crystal 2, the absorption peak (460nm),

is slightly shifted in comparison to the starting materials, which shows absorption maxima at

412 nm (TMB) and 396nm (NNA) respectively. Co-crystal 3 has an absorption peak at 535

nm which shows a major shift as compared to its starting materials (407 nm-TAPB, 382 nm-

DNB). Co-crystal 4 has a very large shift in the absorption maxima as compared to both the

28
starting materials. Co-crystal 4 shows absorption peak at 638nm and starting materials have

absorption maxima at 412 nm (TMB) and 382nm (DNB). This suggests the existence of

charge transfer, the mechanism for this process forms the future course of study.

In infrared spectroscopy characteristic peaks of C=O and N-O of NNA was observed at 1750

cm-1 and 1530 cm-1 respectively and for TAPB a characteristic peak of N-H was observed at

3347 cm-1. In the case of the co-crystal 1, a red shifted peak for N-O (1516 cm-1) was found

as compared to the starting material (NNA). For co-crystal 2, it showed a red shifted peak for

N-H at 3358 cm-1 as compared to TMB which has a characteristic peak at 3379 cm-1. DNB

which is one of the staring materials of co-crystal 3, shows characteristic peaks of C≡N and

N-O at 2249 cm-1 and 1555 cm-1 respectively. As compared with the stretching frequencies of

DNB, co-crystal 3 shows a red shift for C≡N (2240 cm-1). In the case of co-crystal 4, it shows

red shifts for C≡N (2234 cm-1) and N-O (1542 cm-1). These shifts can be due to the presence

of hydrogen bonds in the co-crystals.

29
 4. CONCLUSIONS
In summary we have developed several mixed Charge Transfer solid state materials each

based on two components system and displays mechanochromism upon mechanical grinding

of the starting components. Crystal structural investigation establishes that molecular

recognition between donor and acceptor molecules results in adjusting the stacking modes of

the donor molecules upon introduction of the acceptor. Because of the unique mixed stacking

of D··A··D··A··D in the crystalline state, the charge transfer state has been achieved;

therefore such a packing arrangement is beneficial for the development of efficient solid state

materials for next-generation luminescent materials. The future work will be focussed on

quantitatively understanding the role of different intermolecular interaction by calculating the

interaction energies of interactions such as π- π stacking, N-H···O, O-H···O hydrogen bonds

present in the reported co-crystals. Beside this, we will also check these co-crystals for

possible solid-state fluorescent properties.

Author Contributions

Akshaj Prem performed the co-crystal synthesis, IR measurements and crystal structure

refinement by himself. Mr. Rohit Bhowal (PhD Research scholar, CCCL) did the single

crystal data collection, and gave initial guidance to Akshaj Prem about crystallization

procedures. Akshaj Prem carried out solid state UV-visible spectra measurements under the

guidance of Suprakash Biswas (PhD Research Scholar, Dr. Apurba Lal Koner Lab). Mr.

Manoj Kumar Tripathi (operator, CIF, IISER Bhopal) recorded the PXRD measurements.

Mr. Manoj Kumar Rout (operator, CIF, IISER Bhopal) recorded the DSC data. All the

ORTEPs, packing diagrams and graphs were drawn by Akshaj Prem using Mercury 3.10 and

Origin 8 softwares respectively. Akshaj Prem wrote the report with inputs from Dr. Deepak

Chopra.

30
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