Synthesis, growth, structural and optical studies of a novel organic Piperazine (bis) p-toluenesulfonate single crystal

Article abstract of DOI:10.1016/j.saa.2014.12.069

A novel organic single crystal of Piperazinium (bis) p-toluenesulfonate (PPTS) was grown by a slow evaporation solution growth technique. The structure of the grown crystal was determined using single crystal X-ray diffraction analysis. The PPTS crystal b

Full text of DOI:10.1016/j.saa.2014.12.069

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Accepted Manuscript
Synthesis, growth, structural and optical studies of a novel organic Pipera-
zine(bis) p-toluenesulfonate single crystal
P. Rekha, G. Peramaiyan, M. NizamMohideen, R. Mohan Kumar, R.
Kanagadurai
PII:
S1386-1425(14)01849-6
http://dx.doi.org/10.1016/j.saa.2014.12.069
SAA 13119
DOI:
Reference:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
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Received Date:
Revised Date:
Accepted Date:
20 September 2014
26 November 2014
17 December 2014
Please cite this article as: P. Rekha, G. Peramaiyan, M. NizamMohideen, R. Mohan Kumar, R. Kanagadurai,
Synthesis, growth, structural and optical studies of a novel organic Piperazine(bis) p-toluenesulfonate single crystal,
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.
2014.12.069
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Synthesis, growth, structural and optical studies of a novel organic Piperazine
(bis) p-toluenesulfonate single crystal
P. Rekhaa, G. Peramaiyanb, M. NizamMohideenc, R. Mohan Kumara, R. Kanagaduraia*
aDepartment of Physics, Presidency College, Chennai - 600005, India
bDepartment of Physics, Vel Tech University, Chennai-600062, India
cDepartment of Physics, The New College (Autonomous), Chennai-600014, India
Abstract
A novel organic single crystal of Piperazinium (bis) p-toluenesulfonate (PPTS) was
grown by a slow evaporation solution growth technique. The structure of the grown crystal was
determined using single crystal X-ray diffraction analysis. The PPTS crystal belongs to the
triclinic crystal system with space group of P1 The presence of functional groups was confirmed
.
by FTIR spectral analysis. The optical transmittance range and cut-off wavelength were
identified by UV-vis-NIR spectral studies. The luminescent properties of PPTS crystal were
investigated. The thermal behavior of PPTS crystal was studied by TG-DT analyses.
Keywords : Crystal structure; Growth from solutions; Organic compounds; optical properties;
FTIR spectroscopy
Corresponding author :
Dr. Ramajayam Kanagadurai
Department of Physics
Presidency College
Chennai-600 005, India. Tel : +91 9443887130,
Email : srkanagadurai@yahoo.co.in
1

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1.
Introduction
In recent years, organic materials are of considerable interest due to their potential
applications such as frequency conversion, optical signal processing, light modulation, optical
switching, etc. Organic molecules are especially interesting, because they can offer a highly
aligned and stable orientation of chromophores in the crystal lattice [1-5]. Organic materials
contain donor and acceptor groups positioned at either end of a suitable conjugation path.
Generally, benzene derivatives have permitted an increase in the number of π- electron clouds as
well as their delocalization length, so as to lead to a remarkable enhancement in the molecular
hyperpolarizability. The chromophores present in the organic molecules with delocalized
electrons exhibit various photo responses such as photoluminescence, photoconductive,
photovoltaic, photo catalytic behaviors, and so on [6]. The rational control over the molecular
self-assembly process is critical and unpredictable in intelligent crystal engineering.
Crystal engineering is achieved by bottom-up construction of functional materials from
molecular building blocks [7]. These building blocks are influenced by relatively strong
interactions that often display considerable consistency which are known as supramolecular
synthons. In a supramolecular structure, the control of molecular orientation is difficult and
identified as major barrier in materials design. To control the structure of solids, many attempts
have been focused on crystal engineering via charge transfer, electrostatic, hydrogen bond and
π-π interactions. Efforts have been made in forming noncentrosymmetric crystal structures by
hydrogen bonding with π-π interactions for quadratic nonlinear optical applications. However,
crystal structures with inversion centre are preferred, because of more favourable intermolecular
dipole-dipole interactions with close packing for the third order nonlinear optical, optical
limiting and three dimensional fluorescence microscopy applications [8]. p-toluenesulfonic acid
2

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has a methyl group as an electron donor and a sulfonate group as an electron acceptor to induce
high NLO character. Piperazine is a symmentric diamine in six membered saturated ring and has
cycloaliphatic secondary amine with two NH groups [9]. In the present investigation, we report
the growth, structural, spectroscopical, optical and thermal properties of a novel organic crystal
of Piperazinium (bis) p-toluenesulphonate (PPTS) for the first time.
2.
Experimental
2.1
Material Synthesis and growth
The PPTS compound was synthesised by dissolving Piperazine (8.614 g) and
p-toluenesulfonic acid monohydrate (38.044 g) of 1:2 ratio in methanol solvent at room
temperature. The protonated piperazine and deprotonated p-toluenesulfonic acid form
piperazinium (bis) p-toluenesulfonate compound. The reaction scheme is depicted in Fig.1.
The synthesized salt was purified by the successive recrystallization process.
The required solution was stirred continuously for 4 hr to achieve the homogeneous mixing.
Then, the solution was filtered and placed in a dust free atmosphere. The PPTS single crystals
were grown by slow evaporation solution technique. After the growth period of 28 days, good
quality crystals with the dimension up to 12×7×7 mm3 were harvested as shown in Fig.2.
3.
Results and discussion
3.1
Single crystal X- ray diffraction study
The crystal structure was determined from single-crystal X-ray diffraction data.
The intensity data were collected on a Bruker kappa APEXII single crystal X-ray diffractometer
with graphite monochromated MoKα radiation (λ= 0.71073 Å) at 293 K [10]. The structure was
3