Optik 127 (2016) 24952499

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Optik
journal homepage: www.elsevier.de/ijleo

Studies on the growth, spectral, thermal, and optical properties of

l-arginine adipate crystal
K. Ramya a , N.T. Saraswathi b , C. Ramachandra Raja c,
a
b
c

Department of Physics, T.U.K. Arts College, Thanjavur, 613 002, Tamilnadu, India
Molecular Biophysics Lab, School of Chemical and Biotechnology, SASTRA University, Thanjavur 613 401, Tamilnadu, India
Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 001, Tamilnadu, India

a r t i c l e

i n f o

Article history:
Received 28 April 2015
Accepted 16 November 2015
Keywords:
Optical materials
Crystal growth
Infrared spectroscopy
X-ray diffraction
Nuclear magnetic resonance

a b s t r a c t
Single crystals of l-arginine adipate were grown by liquid diffusion technique. The unit cell parameters were characterized by single crystal X-ray diffraction analysis. The structure of grown crystals was
determined from Nuclear Magnetic Resonance spectral analysis. The UVvisNIR spectrum and Second
Harmonic Generation were used to nd its optical characteristics feature. The fundamental functional
groups were identied from Fourier Transform Infra Red spectral analysis. The thermal behavior of the
crystal has been found out by Thermal Gravimetric Analysis and Differential Thermal Analysis.
2015 Elsevier GmbH. All rights reserved.

1. Introduction
Organic crystals exhibit unique properties due to its high chemical purity, which founds a lot of interest in the eld of solid-state
lasers. In the case of optical gain materials, the stimulated emission
of cross-section is high and has a broad tunable emission of wavelength. Organic crystals shows excellent optical nonlinear activity
than inorganic crystals [1,2]. Being highly pure it possess properties
like high thermal stability and high polarized emission of radiation
and low scattering densities [3]. The centrosymmetric nature of the
crystal possesses the properties of third order non-linearity and
the third order non-linear susceptibilities are useful for all optical
switching, modulating and computing devices [4]. The third order
non-linear optical materials have weak non-linear absorption and
have considerable attention of their potential use in the optical signal processing devices [5]. Arginine is the most common amino
acid with a proton acceptor carbonyl ( COO) group and the proton
donor ( NH2 ) group. -Amino acid compounds have some special features such as molecular chirality, high transparency in UV

Corresponding author. Tel.: +91 9976696277.

E-mail address: crraja phy@yahoo.com (C.R. Raja).

http://dx.doi.org/10.1016/j.ijleo.2015.11.152
0030-4026/ 2015 Elsevier GmbH. All rights reserved.

and visible regions, and the zwitterionic nature of the molecule,

which hardens the crystal [6]. l-Arginine found advantages with
different salts, and a number of different acids on reaction with
arginine were synthesized and grown. The crystal structure of
l-arginine adipate was rst reported by Roy et al. [7]. It crystallizes in the monoclinic crystal system, having P21 space group,
b = 5.9510(7) A,
c = 16.719(5) A,

with the values of a = 12.494(4)A,

3
= 105.977(5) , Z = 2, and V = 1195.1(6) A . In the present work,
the studies on the growth of l-arginine adipate crystal are carried out by liquid diffusion method. And the grown crystals were
characterized by X-ray Diffraction analysis (XRD), Fourier Transform Infra Red Spectroscopy (FTIR), Nuclear Magnetic Resonance
Spectroscopy (NMR), Thermal studies, optical characterization like
UVvisNIR Spectroscopy, and Second Harmonic Generation (SHG)
property.

2. Experimental
Crystals of l-arginine adipate were obtained from liquid diffusion method by making aqueous solution of l-arginine and adipic
acid in equimolar ratio with the addition of ethanol or acetonitrile
as the precipitant. Transparent crystals of l-arginine adipate were

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K. Ramya et al. / Optik 127 (2016) 24952499

grown in a period of one week. The formation of the complex

l-arginine adipate is given below.

2.1. Characterisation
Single crystal XRD study was carried out using Nonius
CAD4/MACH 3 single crystal X-ray diffractometer with MoK
radiation. The 1 H NMR and 13 C NMR spectra were
( = 0.71069 A)
recorded for the crystals by dissolving in heavy water (D2 O) using
Bruker 300 MHz (ultrasheild)TM instrument at room temperature
(300 MHz for 1 H NMR (Nuclear Magnetic Resonance) and 75 MHz
for 13 C NMR) for the conrmation of molecular structure. The
transparency range was investigated by 35 model PerkinElmer
double beam UVvisNIR spectrometer in the range from 190 nm
to 1100 nm. FTIR (Fourier Transform Infra Red) spectrum was
recorded by the KBr pellet technique using a SPECTROMRX1 FTIR
spectrometer to conrm the functional groups. TGA (Thermal
Gravimetric Analysis)/DTA (Differential Thermal Analysis) were
carried out using the instrument SDT Q600 V20.9 Build 20 at a heating rate of 20 C/min in nitrogen atmosphere in temperature range
301100 C. The measurement of the SHG efciency was determined using powder technique developed by Kurtz and Perry. The
SHG measurement was carried out using Q-switched mode locked
Nd:YAG laser with rst harmonic output at 1064 nm, with an input
energy of 1.9 m J/pulse and a pulse width of 10 ns at a repetition
rate of 10 Hz.

are shown in Figs. 1 and 2. The chemical shifts are tabulated in

Tables 2 and 3.
In the 1 H NMR spectrum the appearance of an intense peak at
= 4.676 ppm due to the presence of D2 O solvent. The spectrum
shows two triplet peaks at = 3.601 ppm and = 3.075 ppm corresponds to the proton of CH and CH2 groups of l-arginine.
Two multiplets at = 1.764 ppm and = 1.382 ppm corresponds to
the two CH2 groups of l-arginine. Similarly the two CH2 protons of adipate appeared at = 2.028 ppm and = 1.565 ppm. There
is no peaks appeared for NH2 and COOH groups in 1 H NMR,
indicates that they are ionic in nature and are involved in secondary
forces.
The 13 C NMR spectrum of l-arginine adipate crystals showed
nine different peaks corresponds to nine carbon atoms. The signal
at = 183.57 ppm and = 174.34 ppm conrms the presence of carbonyl groups of l-arginine and adipic acid respectively. The carbon
attached to NH C NH2 group shows the signal at = 156.70 ppm.
The signal at = 54.19 ppm is due to the carbon atom attached
to amino group. The signals at = 40.41 ppm, = 27.77 ppm and
= 25.03 ppm owes to three CH2 groups of l-arginine moiety.
Similarly the signals for two CH2 groups in adipic acid appeared
at = 37.32 ppm and = 23.84 ppm.
3.3. UVvisNIR spectral analysis

3. Result and discussion

3.1. Single crystal XRD
Single crystal X-ray diffraction analysis was carried out to nd
the lattice parameters. This study reveals that the grown crystals
of l-arginine adipate belong to the monoclinic system. The determined unit cell parameters are listed in Table 1. The observed values
of l-arginine adipate crystal is found to be in good agreement with
the reported values [7].

The UV Visible spectrum of the crystal in Fig. 3 shows an excellent transparency in the entire UVvisNIR region. All amino acids
possess the property, that the absorption of radiation is absent in
the entire visible region [8,9]. From the spectrum it is clear that

3.2. NMR studies

In order to analyse carbon-hydrogen bonded network of the
crystal, 1 H NMR and 13 C NMR spectra were recorded using D2 O
solvent in Bruker 300 Hz(Ultrasheid) instrument at room temperature. The 1 H NMR and 13 C NMR spectrum of l-arginine adipate
H NMR spectrum of l-arginine adipate.

Fig. 1.

Fig. 2.

13

Table 1
Unit cell parameters of l-arginine adipate.
Cell parameters

Values

a (A)

b (A)

c (A)

12.47
5.99

16.65
90
105.88
90

V (A 3 )
Crystal system

1197
Monoclinic

C NMR spectrum of l-arginine adipate.

K. Ramya et al. / Optik 127 (2016) 24952499

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Table 2
The chemical shifts in 1 H NMR spectrum of l-arginine adipate crystal.
Chemical shift (ppm)
l-Arginine adipate

l-Arginine

Adipic acid

Group identication

Assignment

4.676
3.601
3.075
2.028
1.764
1.565
1.382

3.27
3.21

1.63

2.21

1.51

D2 O
CH
CH2
CH2
CH2
CH2
CH2

Singlet
Triplet
Triplet
Triplet
Multiplet
Triplet
Multiplet

Table 3
The chemical shifts in 13 C NMR spectrum of l-arginine adipate crystal.
Chemical shift (ppm)
l-Arginine adipate

l-Arginine

Adipic acid

183.57
174.34
156.70
54.19
40.41
37.32
27.48
25.76
23.84

175.38

157.85
55.45
41.64

28.77
25.03

174.28

33.35

24.00

Group identication
COOH
COOH
NH C NH2
C NH2
CH2
CH2
CH2
CH2
CH2

l-arginine adipate crystal have a lower cut off wavelength at

206 nm. Due to high transmission in the entire UVvisNIR region
this can be used as a suitable material for optoelectronic application.
3.4. FTIR spectral analysis
The identication of functional groups was performed by
infrared spectroscopy. The FTIR spectrum of l-arginine adipate
was recorded by Perkin Elmer Spectrometer in the frequency
4004000 cm1 using KBr pellet technique and is shown in Fig. 4.

Table 4
FTIR spectral assignments for l-Arginine adipate single crystal.
l-Arginine adipate

l-Arginine

Assignment

3390.77
2938.71
1640.85
1533.96
1488.22
1392.54
1329.46
1166.15
1084.13
917.28
854.45
535.77

3382
2928
1680
1536
1464
1410
1325
1174
1086
918
848
522

O H stretching
CH3 asymmetric stretching
NH2 out of plane bending
O H bending
CH3 asymmetric bending
CH3 symmetric plain bending
O H bending vibration
C C C symmetric stretching
C H in plane deformation
C C stretching
C C stretching
C O bending vibration

The identied groups are stocked in Table 4. A strong broad absorption band is observed between 3500 cm1 and 2000 cm1 , is due to
the superimposed OH and NH3 + stretching bands [10]. The presence of OH stretching is assigned at 3390.77 cm1 . The peak at
854.45 cm1 is assigned to stretching of C C group. The symmetric
plain bending of CH3 groups are slightly shifted to 1392.54 cm1
in the grown crystal. The asymmetric stretching of CH3 group
is observed at 2938.71 cm1 [11]. The peak at 1084.13 cm1 is
assigned to the C H in plane deformation mode [12]. Two bands
are observed at 1533.96 cm1 and 1329.46 cm1 are attributed

Fig. 3. UVvisNIR spectrum of l-arginine adipate.

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K. Ramya et al. / Optik 127 (2016) 24952499

Fig. 4. FTIR spectrum of l-arginine adipate crystal.

Fig. 5. TGA and DTA spectrum of l-arginine adipate.

to bending mode of OH group. The symmetric stretching of

C C C bond is observed at 1166.15 cm1 . The C O bending and
C C stretching of absorption bands appear at 535.77 cm1 and
854.45 cm1 are due to the vibrations of functional groups and
carbon chain of l-arginine [13].
3.5. Thermal studies
The thermal properties of l-arginine adipate crystal was analysed from TG-DTA studies and the thermograms are shown in
Fig. 5. The weight loss of about (2%) is observed initially near
the temperature 89 C corresponds to the evaporation of adsorbed
water molecule present in the crystal, which is indicated in the
DTA curve by an endothermic peak at 89 C. It is observed that
the decomposition of l-arginine adipate starts at 266 C. This is
supported by the DTA analysis where an endothermic reaction is
observed at 266.67 C. And the peak at 266 C represents the melting point. It can see from the thermal analysis that when l-arginine
adipate is subjected to continuous heating, does not remain stable
for a long temperature change. It decomposes with the remaining
residue of about 0.0899% of its initial mass at 600 C.

3.6. Second harmonic generation studies

Second Harmonic Generation (SHG) test for the powder samples
of l-arginine adipate have been studied by Kurtz powder technique
[14]. The powdered sample were illuminated using Nd:YAG laser
emitting a fundamental wavelength of 1064 nm. Due to its centrosymmetric nature l-arginine adipate crystal is inactive in the
generation of second harmonic wavelength [7].
4. Conclusion
Crystals of l-arginine adipate have been successfully grown
from liquid diffusion method. The lattice parameters have been calculated from single crystal X-ray studies. The molecular structure
of the l-arginine adipate was conrmed by NMR analysis. Optical
transmission studies showed that the crystal was optically transparent through the UVvisNIR region. The FTIR spectrum reveals
various functional groups present in the grown crystal. The thermal properties have been reported by TGA and DTA analyses. The
l-arginine adipate crystal does not exhibit second harmonic generation property.

K. Ramya et al. / Optik 127 (2016) 24952499

Acknowledgements
The authors wish to thank SASTRA university for the NMR
and TG/DTA characterization facilities. One of the author (N.T.S.)
acknowledges the Department of Science and Technology, Govt. of
India fast track scheme for young scientist (SR/FT/LS-156/2009).
The authors thank St. Joseph College, Tiruchirappalli for FTIR
and UV spectra. The authors are also grateful to Dr. P. K. Das,
Indian Institute of Science, Bangalore for the measurement of SHG
efciency.
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