Growth and characterization of a new organic single crystal: 1-(4-Nitrophenyl) pyrrolidine (4NPY)

Article abstract of DOI:10.1016/j.saa.2014.11.086

A new 1-(4-Nitrophenyl) pyrrolidine single crystal has grown by slow evaporation solution growth technique. The grown crystal have characterized by single crystal X-ray analysis, and it shows that 1-(4-Nitrophenyl) pyrrolidine crystallizes in the orthorhombic space group Pbca, with cell parameters a = 10.3270 (5) A?, b = 9.9458 (6) A?, c = 18.6934 (12) A?, and Z = 8. Powder XRD pattern confirmed that grown crystal posses highly crystalline nature. The functional groups have identified by using FTIR spectral analysis. The absorbance and the luminescence spectra of the title compound have analyzed using UV-Visible and PL spectra. The thermo analytical properties of the crystal have studied using TG/DTA spectrum. The mechanical property of the grown crystal has determined using Vickers micro hardness measurement. The grown features of the crystal have analyzed using etching technique.

Full text of DOI:10.1016/j.saa.2014.11.086

Accepted Manuscript
Growth and characterization of a new organic single crystal: 1-(4-Nitrophenyl)
pyrrolidine (4NPY)
M. Nirosha, S. Kalainathan, P.G. Aravindan
PII:
S1386-1425(14)01750-8
http://dx.doi.org/10.1016/j.saa.2014.11.086
SAA 13022
DOI:
Reference:
To appear in:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
Received Date:
Revised Date:
Accepted Date:
8 January 2014
4 August 2014
20 November 2014
Please cite this article as: M. Nirosha, S. Kalainathan, P.G. Aravindan, Growth and characterization of a new organic
single crystal: 1-(4-Nitrophenyl) pyrrolidine (4NPY), Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.11.086
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Growth and characterization of a new organic single crystal: 1-(4-Nitrophenyl) pyrrolidine
4NPY)
(
a
a
b
M. Nirosha , S. Kalainathan , P. G. Aravindan
a
Center for Crystal Growth, VIT University, Vellore – 632014, Tamilnadu, India.
b
Crystal Growth and Crystallography Division, VIT University, Vellore 632 014, India
Abstract
A new 1-(4-Nitrophenyl) pyrrolidine single crystal has grown by slow evaporation solution
growth technique. The grown crystal have characterized by single crystal x-ray analysis, and it
shows that 1-(4-Nitrophenyl) pyrrolidine crystallizes in the orthorhombic space group Pbca, with
cell parameters a = 10.3270 (5) Å, b = 9.9458 (6) Å, c = 18.6934 (12) Å, and Z = 8. Powder
XRD pattern confirmed that grown crystal posses highly crystalline nature. The functional
groups have identified by using FTIR spectral analysis. The absorbance and the luminescence
spectra of the title compound have analyzed using UV–Visible and PL spectra. The thermo
analytical properties of the crystal have studied using TG/DTA spectrum. The mechanical
property of the grown crystal has determined using Vickers micro hardness measurement. The
grown features of the crystal have analyzed using etching technique.
Keywords: Crystal structure, Growth from solution, characterizations
*
corresponding author
Prof.S.Kalainathan
VIT University, Vellore – 632014, Tamilnadu, India.
Phone: +91-416-2202350 Fax: 0416-2243092
Email Address: kalainathan@yahoo.com
1

1
. Introduction
In recent years, the interest of organic materials having aromatic rings has increased
considerably. Organic materials offer flexibility to molecular design, large nonlinear response
over a broad frequency range and high damage resistance to optical radiation. Hence these
materials make it desirable to replace electronic switching circuits in computing and
telecommunication systems [1-4]. The presences of heterocyclic in all kinds of organic
compounds are of interest in electronics, optics, biology, and materials science. Heterocycles
have used as additives and modifiers in industrial applications including reprography,
information storage, plastics, solvents, antioxidants and vulcanization accelerators. Optically
active pyrrolidine rings remain an area of intense research due to their natural occurrence found
in natural alkaloid products and as bio-molecules [5]. The various N - substituted pyrrolidine
compounds such as N - (substituted phenyl) pyrrolidine – 2 - carboxamide, N - substituted 2, 5-
dimethyl pyrrole, N - (2 - Napthyloxy methyl carbonyl) pyrrolidine in anticonvulsant activities
has also well known [6-8]. The title compound 1 - (4 - Nitrophenyl) pyrrolidine (4NPY) is an
intermediate compound in the synthesis of 1 - (4 - aminophenyl) pyrrolidine sulfate, and it has
synthesized from 1 – chloro – 4 - nitrobenzene. The chlorinated nitro aromatic compounds are
good precursors to introduce nitrogen substituent, hence acts as a starting materials for the
preparation of various N-heterocycles and a number of industrial chemicals [9-10]. Nitrobenzene
compounds possess high contribution of anharmonic electron-phonon interaction and can be
used as a material for the fast-response, degenerate four-wave mixing. Optical-grade organic
single crystals of substituted pyrrolidine derivatives with high optical nonlinearities and low
melting temperatures are promising materials for optoelectronics, and nonlinear optical (NLO)
applications [11]. The discoveries of new materials exhibiting nonlinear optical properties in
2

combination with other desirable physical properties (optical transparency, thermal, optical and
mechanical stability) continue to be an important research goal in nonlinear optics [12-13]. The
present work deals with the synthesis, growth, crystal structure and characterizations of novel
organic single crystal, of 1-(4-Nitrophenyl) pyrrolidine.
2
.
Experimental
2
.1. Synthesis and Growth
4
NPY have prepared by following the procedure in ref [9]. The calculated amounts of
pyrrolidine, Na
2
CO , 2-propanol have combined with 4 -chloronitrobenzene with water. The
3
mixture has refluxed for 1 hour. The resultant mixture has filtered washed with cold water and
◦
dried in vacuo at 50 C. The final product has purified by recrystallization process using ethanol
as solvent. In order to grow the single crystals of 4NPY, a saturated solution have prepared at
◦
room temperature (30 C) using ethanol as solvent and placed in a constant temperature bath.
When solution evaporates, the saturation gradually attains supersaturated level leading to
nucleation and the growth of the crystals. Within two weeks of time, the crystals of appreciable
size 4mm x 3mm x 3mm have harvested. The as grown 4NPY crystals have shown in Fig.S1.
3
3
.
Results and discussion
.1. Single crystal and Powder XRD
The single crystal X-ray diffraction (XRD) analysis of 4NPY crystal have carried out using
ENRAF NONIUS X-ray diffractometer with MoK radiation of wavelength λ=0.71073Å at room
α
temperature and the unit cell parameters, and morphology of the grown crystal has identified.
The morphology of the grown crystal has shown in Fig S2. The structure of the grown crystal has
solved by the direct method and computerized by the full matrix least square technique using the
SHELXL program. The compound crystallized in orthorhombic system and Pbca space group
3

(
[
Table 1). The related reported structures have compared with the present crystal structures
14-15]. The bond distances and angles have agreed with standard reported structures [16]. The
selected bond distances and angles have listed in Tables 2. The torsion angles represent the
◦
orientation of nitro group with benzene plane by -3.4 . The conformation of pyrrolidine ring
system has an envelope on C8 atom which has evidenced from the lowest mirror symmetry of
0
.7.3(10) ˚ (D. Cremer & J.A. Pople) [17]. The twisted nitro group results short contact between
O2 and H2 by distance 2.44 Å. The mean plane calculation shows C8 atom having highest
deviation in respect of other atoms in pyrrolidine ring. The observed site occupation factors of
pyrrolidine ring system shows disorder by 0.705(10):0.295(10) and with their sum constrained
unity. The hydrogen atoms have fixed by geometrically on their parent atoms, with C-H distance
in the range 0.93-0.97 Å. Fig. S3 shows the molecular structure with the numbering scheme of
4
NPY molecule. Apart from the van der Waals interactions, crystal packing has stabilized by C-
H...π and π…π interactions. One of the hydrogen atom (H10D) at X, Y, Z interact with the
centroid of a benzene ring at 3/2-X, 1/2+Y, Z with distance of 2.88 Å, angle D-H...A= 124˚;
D...A= 3.52 Å and zigzag chain ride in the b axis [Fig.1]. The aromatic π…π interaction exists
with another benzene ring at 2-X, 2-Y, and 2-Z by 4.00Å. The purity and crystalline nature of
4
NPY compound has confirmed by recording powder X-ray diffraction pattern using a RICHER
◦
SEIFERT X-ray diffractometer employing CuK
α
(1.54058 Å) in the range of 10-70 in the steps
◦
of 0.02 . The well defined Bragg’s peaks at particular 2 theta angles in the powder XRD
spectrum has shown in Fig.2. It reflects good crystalline nature of the grown crystal. The peaks
have indexed using APPLEMAN program from the 2 theta values. The lattice parameters
calculated from powder xrd analysis are in good agreement with the data obtained from single
crystal XRD analysis.
4

3
.2 FTIR spectrum
-1
The FTIR spectrum of the grown crystal has recorded in the middle IR between 400-4000 cm .
It has carried out using FT-IR 4100 type-A spectrophotometer employing KBr pellet technique at
room temperature. FTIR spectroscopy has widely used for the detection of functional groups of
the synthesized compound [18]. The recorded spectrum of 4NPY has shown in Fig.3. The peak
-1
observed at 1109.07 cm is due to the presence of C-N asymmetric stretching of the heterocyclic
-1
ring present in the compound. The peak observed at 3388.93 cm has assigned to the presence of
-1
four asymmetric CH
NO vibration. The presence of symmetric C-N bond has confirmed by the peak observed at
193.94 cm . The peaks observed at 2858.51 cm , and 2976.16 cm are due to the presence of
four C-H bonds present in the compound.
2
of the heterocyclic ring. The peak at 1523.76 cm confirms the presence
2
-1
-1
-1
1
3
.3 UV-visible studies
The UV-Vis-NIR spectrum gives information about the structure of the molecule. The absorption
of UV and visible light involves promotion of the electron in the σ and π orbital from the ground
state to higher states [19]. The UV-vis spectrum has carried out using ELICO SL 218 double
beam UV–vis spectrophotometer in the range 190-1100 nm. The spectrum has recorded for 2mm
thickness crystal and as shown in Fig.4. From the spectrum, it has seen that the crystal has a
lower cut-off wavelength of 529nm. The crystal shows its transparency from 530-1100nm. The
crystal shows its transparency from 530-1100nm. Optical band gap value has calculated from the
1
/2
Tauc’s plot between the absorption coefficient (αhυ) and photon energy (hυ). The band gap
obtained from the graph for 4NPY has shown in Fig.S4. The optical band gap value of 4NPY is
5

2
.21 eV. The lower band gap of the title material suggests that it may be utilized in visible light-
responsive devices and ambipolar organic thin film transistors [20-21].
3
.4 Photoluminescence studies
The Photoluminescence spectrum provides information of different energy states available
between the valence band and conduction band responsible for radiative recombination [22].
The PL spectrum have recorded using Jobin Yvon-Spex spectrofluorometer (Fluorolog version
3
: Model FL3-11) at room temperature for a spectral resolution of 0.2nm; 450W high pressure
xenon lamp acts as an excitation source. The PL intensity is most probably dependent on the
crystalline nature and structural perfection of the grown crystal. Fig. 5 represents the PL
spectrum of 4NPY single crystal. The sample has excited at 529 nm. The emission spectrum has
recorded between 540-720 nm. The broad emission band appeared in the region 552-567 nm
owing to the emission of green radiation. The luminescence in the green spectral regime, which
is of the high importance for display and solid-state lighting applications [23].
3
.5 Thermal analysis
Thermo gravimetric methods have mainly limited to decomposition and oxidation reactions and
to physical processes such as vaporization, sublimation and desorption. Thermo grams provide
information about decomposition patterns and weight loss of the materials [24]. Thermo
gravimetric analysis and differential thermal analysis (TG/DTA) for 4NPY have recorded using a
SDT Q600 V8 instrument. The analyses have carried out in an atmosphere of nitrogen at a
◦
◦
◦
heating rate of 10 C/min for the temperature range 30 C -1000 C. The Thermogravimetric
spectrum of 4NPY has shown in Fig.6. The title compound exhibited good resistance to thermal
6

◦
decomposition up to 163 C. The compound undergoes decomposition in a single stage which
◦
◦
starts at 163 C and completes at 227 C.
3
.6 Micro hardness studies
Micro hardness studies have carried out with Mututoyo MH-112 micro hardness tester using
Vickers diamond pyramidal indenter attached to a metallurgical microscope. The hardness of the
material plays a significant role in device fabrication. Micro hardness studies have applied to
understand with plasticity of the substance [25]. Experiment has carried out with Mututoyo MH-
1
12 micro hardness tester using Vickers diamond pyramidal indenter attached to a metallurgical
microscope. Crystal with flat and smooth faces free from any defects has chosen for the static
indentation tests. The indentations have made at room temperature with a constant indentation
time of 10s. Vickers microhardness test has carried out on (001) face of the grown crystal. The
surface has gently polished with water. Then the polished crystal has correctly mounted on the
base of the microscope and indented gently by applying loads 10-100g with a dwell time of 10s.
At least five indentations have made on sample for each load. The indented surface has
examined under the microscope. The lengths of the two diagonals of the indentations have
measured by a calibrated micrometer attached to the eyepiece of the microscope after unloading.
The average diagonal lengths measured at each time. The Vickers microhardness number of the
crystal H
v
has calculated using the formula.
P
H =1.8544
(1)
v
2
d
7

Where P is the load applied, and d is the mean diagonal length of the indentation. The plot
between load (P) and (H ) of 4NPY single crystal is shown in Fig.S5. It is evident from the plot
that the microhardness value decreases with the increasing load.
v
3
.7 Etching studies
The microstructure has revealed by a surface treatment using an appropriate chemical reagent in
a procedure termed etching [26]. To investigate the perfection of crystalline sample, etching
studies has done using deionized water as an etchant at room temperature for etching times of
3
0s, 45s, and 60s. Etch patterns have analyzed using a Carl Zeiss metallurgical micro-scope
(
Axios kop 40 MAT) in the reflection mode. Etching technique helps to develop some features
such as growth striations, etch spirals; rectangular etch pits etc., on the crystal surface. The
etching studies have carried out on the fresh cleavage surface (001) plane of the single crystal.
During etching reaction at the perfect lattice, the energy barrier E (activation energy) is
a
substantially higher than at the defect. Hence etch rates at defect sites are higher than etch rates
of the perfect lattice giving rise to the formation of etch pits at defect sites. The specimen surface
must first be ground and polished to a smooth and mirror like finish. This can be accomplished
by using successively finer abrasive papers and powders. Surface layer has removed by means of
etching a fresh surface appeared gave clear etch pits. Fig.S6 (a) shows the surface of the crystal
before etching. It is clear from the image that the grown crystal has a smooth surface.
Fig.S6 (b & c) shows the formation of triangular pits on the surface of the crystal for etch time of
3
0 and 45 sec. When the etching time increased for 60s, the pattern remains the same, but the
size of the etch pits has slightly increased which as shown in Fig.S6 (d). This may due to the
presence of dislocation caused by thermal stresses which has imposed on the growth surface
[
27].
8

4
.
Conclusions
A new organic 1-(4-Nitrophenyl) pyrrolidine single crystal have synthesized by slow evaporation
technique. Crystal of size 4mm x 3mm x 3mm have obtained at room temperature. The single
crystal X-ray diffraction confirms that the grown crystal belongs to the orthorhombic crystal
system with the space group Pbca. From the FTIR spectrum, the presence of functional groups of
the material has confirmed. The lower cut off wavelength through UV-Vis spectrum is 529 nm.
The PL spectrum shows green emission in the crystal. The micro hardness studies revealed that
the crystal develops cracks for load above 100g. The thermal analyses reveal that the crystal has
◦
good stability up to 163 C. Hardness study indicates that the hardness decreases with increasing
load. The chemical etching study shows the triangular etch patterns. The shape of the etch pit
increases on increasing the etching time.
Acknowledgements
The author acknowledges Dr. U. Madhusudhanan, IGCAR for PL studies and SAIF, IIT madras
for proving the S-XRD facility. The authors are also thankful to VIT University for providing
excellent research facilities.
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Figure captions
Fig.1 packing diagram of 4NPY
Fig.2 powder xrd spectrum of 4NPY
Fig.3 FTIR spectrum of 4NPY
Fig.4 absorbance spectrum of 4NPY
Fig.5 Luminescence spectrum of 4NPY
Fig.6 TG/DTA spectrum of 4NPY
Fig.1 packing diagram of 4NPY
11

Fig.2 Powder xrd spectrum of 4NPY
Fig.3 FTIR spectrum of 4NPY
12

Fig. 4 Absorbance spectrum of 4NPY
Fig. 5 Luminescence spectrum of 4NPY
13

Fig.6 TG/DTA spectrum of 4NPY
14

Table 1
Crystal data and structure refinement of 4NPY
Empirical formula
Formula weight
Wavelength
C
10
H
12
N
2
O
2
192.22
0.71073Å
Orthorhombic
Crystal system
◦
Unit cell dimensions
a = 10.3270 (5) Å, α = 90
b = 9.9458 (6) Å, β = 90
◦
◦
c = 18.6934 (12) Å, γ = 90
3
Volume
1920.00(19) Å
3
Z, Density (calculated)
Absorption coefficient
F(000)
8, 1.330 Mg/m
-1
0.094mm
816
0.30 x 0.30 x 0.25 mm
.94 to 24.87°.
3
Crystal size
Theta range for data collection
2
Index ranges
-11≤h≤12, -8≤k≤11, -22≤l≤19
Reflections collected
8501
Independent reflections
Completeness to theta = 24.87
1663 [R(int) = 0.0236]
99.8%
◦
2
Refinement method
Full-matrix least-squares on F
Data/ restraints/ parameters
1
663 / 157 / 174
2
Goodness-of-fit on F
1.072
Final R indices [I>2σ]
R indices (all data)
R1 = 0.0348, wR2 = 0.0932
R1 = 0.0582, wR2 = 0.1091
-
3
Largest diff. peak and hole
0.140 and -0.146 e.Å
15

Table 2
Bond lengths (Å) and angles (deg) for 4NPY
Bonds
Bond lengths (Å)
C(1)-N(1)
C(4)-N(2)
N(1)-O(1)
N(1)-O(2)
N(2)-C(7)
N(2)-C(10)
N(2’)-C(7’)
N(2’)-C(10’)
Bond angles (deg.)
C(4)-N(2)-N(7)
C(4)-N(2)-C(10)
C(4)-N(2’)-C(7’)
C(4)-N(2’)-C(10’)
O(1)-N(1)-C(1)
O(2)-N(1)-C(1)
C(6)-C(1)-N(1)
C(2)-C(1)-N(1)
1.433(2)
1.299(8)
1.2280(2)
1.2265(2)
1.462(9)
1.455(9)
1.468(2)
1.472(2)
124.5(7)
125.5(8)
123.8(2)
120.3(2)
118.91(2)
119.36(2)
120.06(2)
120.14(2)
16

Graphical abstract
17

Highlights
ꢀ
1-(4-Nitrophenyl) pyrrolidine, a new organic single crystal has grown by slow
evaporation technique.
ꢀ
ꢀ
ꢀ
ꢀ
The absorbance spectrum shows the lower cut off wavelength at 529 nm.
◦
The Thermogravimetric analysis shows that the crystal has stable upto 163 C.
The Photoluminescence spectrum shows the green emission in the crystal.
Micro hardness and etching studies have carried out for the grown crystal.
18