Journal of Molecular and Engineering Materials

Vol. 2, Nos. 3 & 4 (2014) 1450006 (9 pages)

© World Scienti¯c Publishing Company
DOI: 10.1142/S2251237314500063

SYNTHESIS, GROWTH AND

CHARACTERIZATION STUDIES
OF p-HYDROXYBENZOIC ACID ADDITION
WITH THE GUANIDINIUM CARBONATE
SINGLE-CRYSTALS

M. DHAVAMURTHY*,§, G. PERAMAIYAN†,
S. SYED SURESH BABU‡ and R. MOHAN*
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com

*Department of Physics, Presidency College, Chennai 600 005, India

by Mr M Dhavamurthy on 07/24/15. For personal use only.

†Department
of Physics, Vel Tech Dr. RR &
Dr. SR Technical University, Avadi, Chennai 600 062, India
‡Department of Physics, The New College
Royapettah, Chennai 600 014, India
§
mdhavam@gmail.com

Received 8 October 2014

Accepted 24 February 2015
Published 27 March 2015

An organic nonlinear optical (NLO) crystal of Guanidinium carbonate (GUCT) was synthesized
by the slow evaporation solution growth method using water as solvent. The GUCT crystalized in
the tetragonal crystal system with non-centrosymmetric space group P 43 21 2, which has been
con¯rmed by single-crystal X-ray di®raction. The crystalline perfection of the grown crystals has
been analyzed by high-resolution X-ray di®raction (HRXRD) rocking curve measurements. The
UV-Vis-NIR spectrum studies have been carried out to identify the optical transmittance, lower
cut o® wavelength and optical band gap energy of GUCT crystal. The luminescence spectrum of
crystal contains a green emission band with
max , 545 nm. From thermo-gravimetric analysis
(TGA), the thermal stability of the grown crystal is found to be 117
C. The dielectric tensor
components "11 and "22 of the grown crystal were evaluated as a function of frequency at 40
C.
The mechanical strength and its parameters of the grown crystals have been determined by
Vickers' microhardness test. The Kurtz-powder technique reveals that the second harmonic
generation (SHG) e±ciency of the grown crystal is 5.2 times greater than that of KDP.

Keywords: Crystal structure; growth from solutions; organic compounds; dielectric materials;
nonlinear optical material.

1. Introduction a great impact on information technology and in-

Nonlinear optical (NLO) materials play a vital dustrial applications. The aromatic acid molecules
role in nonlinear optics and in particular, they have attract great interest because of their importance in
§
Corresponding author.

1450006-1
 M. Dhavamurthy et al.
crystal engineering, due to their ability to form
strong and directional hydrogen bond,1 whereby
the number of carboxylic groups and the di®erent
placement of the carboxylic group on the aromatic
ring may lead to variable hydrogen bonding fash-
ions and supramolecular architectures. An organic
molecule with signi¯cant NLO activity generally
consists of -electron conjugated moiety substitut-
ed by an electron donor on one end of the conju-
gated structure and an electron acceptor group on
the other end.2,3 The delocalized conjugated
-electrons provide asymmetrical nature for the
entire length of conjugation under the perturbation
of an external electric ¯eld. The guanidine molecule
is characterized by a Y-shaped CN3 moiety, with an
unusually high basicity attributed to the delocali-
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com
zation of the positive charge over the entire CN3
framework, which resonance stabilizes the cation.
by Mr M Dhavamurthy on 07/24/15. For personal use only.
The guanidinium ion can form a broad family of
hydrogen-bonded crystals like guanidinium sulfo-
nates [C(NH2)3] þ [RS03]  , which forms unique two-
dimensional (2D) hydrogen bonded networks in the
solid state,4 if R was a simple alkane or arene
rnoiety's. Similarly the reported structure of gua-
nidinium carbonate (GUCT) ions is e®ectively
planer with bond distance C–O 1.294(4), 1.287(5)
and C–N 1.358(6), 1.335(6), 1.355(6)
A. It belongs
to tetragonal crystal system and the crystal struc-
ture can be either non-centrosymmetric or centro-
symmetric.5 However, the grown crystal is non-
centrosymmetric with the space group P43212.
Thus aforementioned information suggest that the
highly directing hydrogen-bonding and ionic char-
acter of the guanidinium sulfonate and carbonate
networks provide a wide-range for materials design,
particularly for low dimensional electronic proper-
ties and second harmonic generation (SHG).6 Thus
our work is focused on the growth, thermal, di-
electric tensor, linear and NLO behavior of the
GUCT single-crystal.
OH
NH
HO O +
H2N NH2
OH
O OH
Fig. 1.
2. Experimental
2.1. Material synthesis and crystal
growth
The GUCT was prepared by dissolving an equimo-
lar ratio of pure GUCT and p-hydroxybenzoic acid
(p-HOBA) in deionized water. The prepared solu-
tion was continually stirred for 4 h at 30
C to attain
homogeneity. The measured pH value of this solu-
tion is 11 and the solution was turned into a high
viscous, dense and brownish solution after 2 h. Then
the saturated solution was transferred to a crystal-
lizer and covered by a perforated polyethylene sheet
for controlled evaporation at room temperature.
After a period of 35 days, the grown optically clear
crystal with the maximum size 22  21  9 mm3 was
obtained from the mixture solution.
4-HOBA, possess the para substituted hydroxyl
group and carboxylic group on the benzene, which
form intermolecular hydrogen bonds. In early
reports, p-HOBA was always deprotonated as the p-
hydroxybenzoate anion (p-HOBAA–) and the cor-
responding organic bases were always protonated,9,10
which means an increase of the hydrogen bond ac-
ceptor sites in p-HOBA and the increase of the hy-
drogen bond donor sites in the organic bases. The
determining factor appears to be the greater acidity
of the phenolic hydroxyl group, which means that the
O–H bond is more strongly polarized as O–H than for
alcohols and the large electron density of the car-
boxylic hydroxyl group, due to the resonance mech-
anism. The carboxylic group and phenolic group of p-
HOBAA– therefore possess stronger hydrogen bonds
than alcohols, thereby resulting in higher boiling
points, higher water solubility, and increased ability
to act as solvents for reasonably polar organic mole-
cules. Hence that the reaction mechanism and crystal
structure analyses suggest that the proton transfer
does not take place from the carboxyl hydrogen to the
nitrogen atom of guanidinium cation (Fig. 1), which
O
+
HN NH3+ H3N NH2
-
O O-
NH2 NH
Reaction scheme of GUCT.
1450006-2
 Synthesis, Growth and Characterization Studies of p-HOBA

is also due to the de¯ciency of lone pair electron in Table 1. Crystal data and structure re¯nement for GUCT
guanidinium cation. crystal.
The reason for the color changes with corre- Empirical formula C2 H6 N3 O2
sponding pH value of solutions is due to halo- Formula weight 104.10
chromic e®ect, which means the addition of Temperature 293(2) K
p-HOBA into the GUCT solution. It is seen that, Wavelength 0.71073 A
Crystal system, space group Tetragonal, P43 21 2
during this chemical reaction the formation of am- Unit cell dimensions a ¼ 6:9621ð3Þ
A,  ¼ 90

monium ion (NH þ 3 ), when an amino group of gua- b ¼ 6:9621ð3Þ
A,  ¼ 90

nidinium is transformed into an ammonium group, c ¼ 19:5828ð9Þ
A,  ¼ 90

its in°uence upon to the solution color.11 The high Volume

949.19(7) A 3
viscosity of the solution is due to numerous inter- Z, Calculated density 8, 1.457 Mg/m 3
mediate hydrogen bonds in GUCT crystals, which Absorption coe±cient 0.127 mm 1
also gives stability to the grown crystal. F(000) 440
Crystal size 0:30  0:30  0:25 mm
Theta range for data collection 3.11 to 27.49 deg.
Limiting indices 9 <¼ h <¼ 8,
3. Results and Discussion 4 <¼ k <¼ 9, 25 <¼
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com

l <¼ 25
3.1. Single-crystal X-ray di®raction Re°ections collected/unique 7359/1085
by Mr M Dhavamurthy on 07/24/15. For personal use only.

study [RðintÞ ¼ 0:0224]

Completeness to theta ¼ 27:49 99.7%
The crystal structure was determined from single-
Max. and min. transmission 0.9690 and 0.9629
crystal X-ray di®raction data. The intensity data Re¯nement method Full-matrix least-squares on
were collected on a Bruker kappa APEXII single- F^ 2
crystal X-ray di®ractometer with graphite mono- Data/restraints/parameters 1085/0/57
chromated MoK radiation (
¼ 0:71073
A) at Goodness-of-¯t on F 2 1.121
293 K.7 The structure was solved by the direct Final R indices [I > 2sigma(I)] R1 ¼ 0:0327, wR2 ¼ 0:0951
R indices (all data) R1 ¼ 0:0369, wR2 ¼ 0:0982
method and re¯ned by the full matrix least squares
Absolute structure parameter 0(2)
technique on F2 employing the SHELXL 97 pro- Extinction coe±cient 0.172(13)
gram package.8 The crystallographic data for Largest di®. peak and hole 0.117 and 0.105 e
A 3
structure analysis of the title compound are listed
in Table 1. The crystal structure of GUCT along
the crystallographic y-axes is depicted in the Fig. 2.
The asymmetric unit of the title compound com-
prises of a guanidine cation and a carbonate anion
Table 2. Hydrogen bonds for GUCT [

A and deg.].
(Fig. 3). The chemical composition of the crystal
is 2(C H6 N3), CO3 (GUCT). The GUCT compound D–H    A d (D–H) d(H    A) d(D    A) < (DHA)
crystallizes in a tetragonal crystal system with space
N(1)–Hð1AÞ 0.86 2.12 2.9100(13) 153.2
group P43212. The cell parameters are a ¼ b ¼    O(2)
6:9621ð3Þ
A, c ¼ 19:5828ð9Þ
A and volume V ¼ N(1)–Hð1BÞ 0.86 1.96 2.7805(16) 159.2


949:20ð7Þ A .3
   O(1)#2
The dihedral angle between the mean plane of N(2)–Hð2AÞ 0.86 2.09 2.9432(15) 171.2
the C1/N1/N2/N3 (guanidine molecule) and the    O(2)#3
C2/O1/O2/O1A (carbonate molecule) is 72.31(9)

N(2)–Hð2BÞ 0.86 2.29 3.144(2) 171.9
A.    O(1)#4
The C–N bond distances of the NH2 groups (C1–N1, N(3)–Hð3AÞ 0.86 2.39 3.1842(19) 154.7
C1–N2 and C1–N3) are 1.307(2), 1.323(2) and 1.315    O(1)
(2)

A, respectively, which is short for a C–N single N(3)–Hð3BÞ 0.86 1.94 2.7687(17) 162.4
bond, but still not quite as contracted as one would    O(1)#5
expect for a fully established C–N. These bond Symmetry transformations used to generate equivalent
length features are consistent with an imino reso- atoms:
nance form as is commonly found for C–N single #1 y,x,z #2 x1/2,yþ3/2,zþ1/4 #3 y1/2,
bonds involving sp 2 hybridized C and N atoms. The xþ3/2,zþ1/4
bond distances C2–O2 and C2–O1 [1.282(2) and #4 y1/2,xþ5/2,zþ1/4 #5 x1/2,yþ5/2,zþ1/4.

1450006-3
 M. Dhavamurthy et al.

Fig. 5. Packing diagram of GUCT crystal viewed down the

b-axis. Dashed lines indicate intermolecular N–H    O hydrogen
bonds.
Fig. 2. As-grown crystal of GUCT.

N–H    O hydrogen bonds, forming an R 22 (8) ring

J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com

motif. These motifs are connected via N–H    O

by Mr M Dhavamurthy on 07/24/15. For personal use only.

hydrogen bonds, forming zig-zag chains. The atoms

Fig. 3. ORTEP diagram of GUCT crystal.
1.268(2)

A, respectively], clearly indicate the pres-
ence of C¼O double bonds, including those also
generated through resonance. In the crystal struc-
ture, all hydrogen atoms participate in the inter-
molecular interaction in the form of N–H    O
hydrogen bonds. In the crystal, C1/N1/N2/N3
(guanidine molecule) interact with the C2/O1/O2/
O1

A (carbonate molecule) via two pair of
N1, N2 and N3 in the molecule at (x, y, z) act as
hydrogen donor to O1 in the molecule at (1=2 þ x,
3=2  y, 1=4  z), (1=2 þ y, 5=2  x, 1=4 þ z) and
(1=2 þ x, 5=2  y, 1=4  z) and O2 with molecule
at (1=2 þ y, 3=2  x, 1=4 þ z), respectively. The
zig-zag chain is formed between symmetry related
molecules through N1–H1A    O2, N1–H1B    O1,
N2–H2A    O2, N2–H2B    O1, N3–H3A    O1
and N3–H3B    O1 hydrogen bonds, which form a
three-dimensional (3D) network (Fig. 2). The mor-
phology of GUCT crystal is triangle in shape with
eight symmetrical faces as shown in Fig. 6. The
crystallographic planes (0 1 2), (1 0 2), (0 1 2),

Fig. 4. Molecular con¯guration and atom numbering for

GUCT crystal. Displacement ellipsoids are drawn at the 40%
probability level. Fig. 6. Morphology of GUCT crystal.

1450006-4
 Synthesis, Growth and Characterization Studies of p-HOBA

(0 1 2), (1 0 2), (0 1 2), (1 0 2) and (1 0 2) 0 2 4 6 8 10

10
are clearly identi¯ed. It is observed that the grown 8x10
5
GUCT
GUCT crystal has two prominent °at faces such as (1 0 2) plane
8
(1 0 2) and (1 0 2) having large area compared to

Diffracted X-ray intensity [c/s]

MoKa
5 1
6x10
the other crystallography axial faces. (+, -, - +)
6
13.3"
5
4x10

3.2. HRXRD analysis 4

The crystalline perfection of the grown single-crys- 2x10

5

tals was characterized by high-resolution X-ray 2

di®raction (HRXRD) studies using a multi-crystal 0

X-ray di®ractometer.12 Figure 3 shows the high- 0

-1000 -500 0 500 1000
resolution rocking/di®raction curves (DCs) of Glancing angle (arc s)
GUCT crystals using (1 0 2) di®racting planes in
symmetrical Bragg geometry. The dispersion phe- Fig. 7. HRXRD spectrum of GUCT crystal.
nomenon is well described by comparing the
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com

DCs recorded in dispersive (þ, , , þ) and such unavoidable defects is of great importance,
non-dispersive (þ, , , þ) con¯gurations.13 particularly in case of phase matching application.
by Mr M Dhavamurthy on 07/24/15. For personal use only.

This arrangement improves the spectral purity

(
=
<< 10 5 ) of the MoK1 beam. The diver-
gence of the exploring beam in the horizontal plane
(plane of di®raction) was estimated to be << 3 arc s.
The specimen occupies the fourth crystal stage in
symmetrical Bragg geometry for di®raction in (þ,
, , þ) con¯guration. The rocking or DCs were
recorded by changing the glancing angle (angle be-
tween the incident X-ray beam and the surface of
the specimen) around the Bragg di®raction peak
position B (taken as zero for the sake of conve-
nience) starting from a suitable arbitrary glancing
angle. The detector was kept at the same angular
position 2B with wide opening for its slit, the so-
called ! scan. Before recording the DC, to remove
the non-crystallized solute atoms which remained
on the surface of the crystal and also to ensure the
surface planarity, the specimen was ¯rst lapped and
3.3. Thermal properties
Thermo gravimetric analysis (TGA) and Di®eren-
tial thermal analysis measure the change in weight
loss and the melting point of a material respectively
as a function of temperature in a controlled atmo-
sphere. The thermal properties of GUCT crystal
have been analyzed using a STA 409 PC/PG ther-
mal analyzer at a heating rate of 10
C min 1 from
32
C to 500
C. The initial mass taken was 5.24 mg.
As shown in the Fig. 8, the TG-DTA curve of
GUCT crystal is thermally stable up to 117
C. The
decomposition process of the GUCT could be di-
vided into two steps. The 53% weight loss was
10

chemically etched in a non-preferential etchent of 100

Endothermic
8

water and acetone mixture in 1:2 volume ratio. As 6

seen in the Fig. 7, the DC contains a single peak and 80

4
indicates that the specimen is free from structural 2
Weight loss %

DTA ( C/mg)

60
grain boundaries. The curve is extremely sharp 0
having full width at half maximum (FWHM) of 13.3
40 -2
arc s as expected for an ideally perfect crystal from
-4
the plane wave dynamical theory of X-ray di®rac-
tion.14 Though the specimen contains very low angle 20 -6

boundaries, the grown crystal has high perfection as -8

0
the angle spread of the DC is 3 arc min which is -10

relatively low.15 This is due the solvent molecules or 0 100 200 300 400 500
thermal °uctuations during the growth process and
Temperature (oC)
such defects may not in°uence the NLO properties
of the crystals. However, a quantitative analysis of Fig. 8. TG-DTA diagram of GUCT crystal.

1450006-5
 M. Dhavamurthy et al.

0 2 4 6 8 10 0 2 4 6 8 10
10 10
8
3.0x10
50

2.5x10
8 8
8
40
8
2.0x10
% Transmittance

−1 2
α hν) (eV m )
6
6
30 1.5x10
8

2
4
8
4 1.0x10

(α
20

7
5.0x10 2
10 2

0.0

0
220 nm
0 0 1 2 3 4 5 6
100 200 300 400 500 600 700 800 900 Photon Energy (eV)
Wavelength (nm)
Fig. 10. Plot of (hÞ 2 versus photon energy of GUCT
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com

Fig. 9. UV-Vis-NIR transmission spectrum of GUCT crystal. crystal.

by Mr M Dhavamurthy on 07/24/15. For personal use only.

occurred between 120
C and 207
C due to the loss
of 2(NH3) and CO3 (experimental 95.4 gm, calcu-
lated 94.0 gm). The small endothermic peak at
147
C is found to be matching with the ¯rst weight
loss in TGA curve which is ascribed to the energy
required for the release of the above gaseous mole-
cules. This is followed by another weight loss (36%)
occurring between 248
C and 324
C. There is no
residue weight loss observed after 500
C, which
eventually indicates that the sample is totally
decomposed before this temperature.
3.4. UV-Vis-NIR spectrum
The UV–Vis transmission spectrum of GUCT has
been recorded using a T90þPG spectrophotometer
in the range between 190 and 900 nm. The optical
transmittance spectrum provides the information
of optically induced electronic transitions, band
structure and energy gap in crystalline materials.
The linear transmission spectrum was recorded on
the grown crystal of thickness 2.5 mm with the xy-
polarization focused on the polished surface (1 0
2). The sample exhibits a large transparency win-
dow over the entire visible range with a lower cuto®
wavelength of 220 nm (Fig. 9). It is due to then n–*
transition of C¼O present in the molecular struc-
ture of the crystal. The absorption coe±cient \" of
a crystalline solid obeys the following relationship16:
ðhÞ / ðEg  hÞ n
where Eg is the optical energy gap, and `n' is the
exponent that characterizes the optical absorption
process; n ¼ 1=2 for direct allowed transition, 3/2
for direct forbidden transition, 2 for indirect allowed
transition and 3 for indirect forbidden transition.17
The graph representing ðhÞ 1=2 against h
(Fig. 10), may be resolved into two straight line
fragments. The straight line obtained at lower
photon energies corresponds to the photon absorp-
tion process and cuts the energy axis at a value
equal to Eg  Ep. The other line, which represents
the dependence in the high energy range, corre-
sponds to the photon emission process and cuts the
energy axis at a value of Eg þ Ep: This behavior is
just what one would expect if the absorption in this
range is due to an indirect transition (n ¼ 2). From
the intercept of the two straight lines, the observed
optical band gap of the GUCT crystal is found to be
5.5 eV.
3.5. Photoluminescence study
Fluorimeter characterizes the relationship between
absorbed and emitted photons at a speci¯ed wave-
length. These properties of GUCT powder sample
were analyzed using a FP-6500 spectra°uorometer
with high pressure Xenon lamp as excitation source
at room temperature. Generally, the °uorescent
compounds interact with the excitation light to
decompose or otherwise change their structure.
Thus, the excitation energy of the longest wave-
length that results in detectable °uorescent emission
intensity may be used to minimize this possibility.18
In our work, a ¯xed wavelength of 270 nm is used to

1450006-6
 Synthesis, Growth and Characterization Studies of p-HOBA

7 0 2 4 6 8 10 0 2 4 6 8 10
2.5x10 10 450 10
Excitation = 260 nm
(0 1 0)
2.0x10
7 400 (0 0 1)
8
8
o
Temp = 50 C
Emission indensity (a.u.)

350
7
1.5x10
6

Dielectric tensor
6
300
7
1.0x10
4 250
4
6
5.0x10
200
2
2
0.0 150

0
200 300 400 500 600 700 800 100 0
wavelength (nm) 2 3 4 5 6

Log f (Hz)
Fig. 11. Photoluminescence spectrum of GUCT crystal.
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com

Fig. 12. Plot of log f versus dielectric tensor for GUCT crystal.
by Mr M Dhavamurthy on 07/24/15. For personal use only.

excite the sample and the emitted light of wave-

function of frequency along the b and c axes as
length range between 522 and 563 nm is detected.
shown in the Fig. 13.
When excited at 270 nm, the maximum emission
Dielectric loss is the absorption of energy by
intensity occurs at green region with a sharp edge at
the movement of charges in an alternating ¯eld,
545 nm (Fig. 11) corresponding to 2.2 eV.
and is particularly high around the relaxation and
resonance frequencies occurring in polarization
mechanisms. The large dielectric loss in the power
3.6. Dielectric studies frequency region (50–60 s 1 ) is due to the rotation
Dielectric constant is one of the basic electro optical of dipoles as there is a small degree of DC conduc-
properties of solids. The dielectric permittivity ("r ) tivity in the material. The low value of dielectric
and dielectric loss (tan ) of GUCT were measured loss suggests that the samples possess enhanced
using an Agilent 4284A LCR meter with the fre- optical quality with a fewer defects and this pa-
quency range between 100 Hz and 5 MHz at 50
C. rameter is of vital importance for NLO materials in
The dielectric permittivity ("r ) of a crystal is their application.21
expressed by a second-order tensor.19 For tetragonal
crystal system, there are two independent tensor
components "11 and "22 corresponding to the crys- 2.5
0 2 4 6 8 10
10
tallography planes < 010 > and < 001 > respective-
(0 1 0)
ly. The anisotropy in the dielectric behavior is (0 0 1)
evident as the dielectric permittivity "11 and "22
2.0 8
Temp = 50oC
values vary with di®erently cut and polished sur-
faces in the ranges 409.42–153.34 and 376.40–140.98 1.5
6
Dielectric loss

respectively. The dielectric permittivity values de-

crease with increasing frequency as shown in the 1.0
Fig. 12. The large dielectric permittivity at lower 4

frequency region is due to that the space charge and 0.5

orientational polarizations are active.20 At su±- 2
ciently high frequencies (above  10 15 Hz), none of
0.0
the polarization mechanisms is able to switch rap-
idly enough to remain in step with the ¯eld. The 0
2 3 4 5 6
material no longer possesses the ability to polarize,
Log f (Hz)
and the dielectric constant drops to saturation as
that of vacuum. The dielectric loss is studied as a Fig. 13. Plot of log f versus dielectric loss for GUCT crystal.

1450006-7
 M. Dhavamurthy et al.
0 2 4 6
100
80
Hardness no (kg/mm )
2
60
40
20
0 0
0 200 400 600
Load (kg)
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com
Fig. 14. Plot of load (P Þ versus hardness number (Hv) for
various planes of GUCT crystal.
by Mr M Dhavamurthy on 07/24/15. For personal use only.
3.7. Mechanical studies
Hardness is a measure of the resistance of solid
matter to various kinds of permanent shape change
when a force is applied. The Vickers hardness (Hv)
number, the hardness of the material, is determined
by the load (g) over the surface area ( m2) of the
indentation and not the area normal to the force and
it depends on di®erent parameters such as inter-
atomic spacing, Debye temperature and lattice en-
ergy. The indentation was made on the smooth
surface (
1 0 2) of GUCT crystal with the applied load
ranging from 1 g to 2000 g. By varying the loads over
a ¯xed interval of time 15 s, the values of Hv at dif-
ferent loads were calculated using the expression22,23
1:8544  P
Hv ¼ kg mm 2
d2
where, `p' is the applied load and `d' is the average
diagonal length of the indentation mark. The load
versus hardness value of GUCT single-crystal is
shown in the Fig. 15. It is observed that the micro-
hardness value increases with increasing applied load
and this outcome is known as reverse indentation
e®ect. By plotting of log P versus log d using Mayer's
relation (P ¼ k1d n Þ, the work hardening coe±cient
`n' is calculated as 2.71, which con¯rms that the
crystal belongs to soft material.24
3.8. NLO studies
Kurtz powder test with Nd:YAG laser radiation
on the GUCT sample con¯rms SHG. The proton
8 10 0 2 4 6 8 10
10 10
3.0
8 8
2.5
6 6
2.0
Log p
4 1.5 4
1.0
2 2
0.5
0
800 1000 1.2 1.4 1.6 1.8 2.0 2.2
Log d
Fig. 15. Plot of log d versus log P for various planes of GUCT
crystal.
acceptor amine (–NH) group and the proton donor
(–OH) group of GUCT25 provide infrastructure to
introduce the charge asymmetry formed which is
essential for second-order nonlinearity. A funda-
mental laser beam of 1064 nm wavelength with the
beam energy 3.8 mJ/pulse was used for this tech-
nique. The observed SHG signal energy outputs are
3 mV and 15.6 mV for KDP and GUCT respec-
tively. It is revealed that the SHG e±ciency of
GUCT is 5.2 times greater than that of KDP crys-
tal. Thus GUCT is more e±cient than the reported
Guanidium 4-aminobenzoate26 and Guanidium
4-nitrobenzoate27 crystals.
4. Conclusions
The organic nonlinear single-crystals of GUCT were
grown successfully in aqueous by slow evaporation
method. Single-crystal X-ray di®raction data
reveals that the GUCT belongs to tetragonal crystal
system with non-centrosymmetric space group.
FWHM value of grown crystal is 13.3 arc s, which
shows that the crystalline perfection is good. The
thermal gravimetric analysis reveals that the sample
is thermally stable up to 117
C without decompo-
sition. UV-vis-NIR spectral study revealed that
the GUCT crystal is transparent in the visible re-
gion with lower cut-o® wavelength 220 nm. The
luminescent study showed that the GUNP crystal
exhibits green emission 542 nm. The dielectric ten-
sor components were measured and found to
"11 ¼ 409:42–153.34; "22 ¼ 376:40–140.98 and low
1450006-8

value of dielectric loss suggests that the GUCT
crystal possesses enhanced optical quality with low
density of defects. Micro hardness studies revealed
that the GTCA crystal belongs to hard material
category. The SHG e±ciency of GUCT is found to
be 5.2 times more than that of KDP. These e±cient
and high quality organic NLO crystals can be di-
rectly utilized for electro-optic and photonic device
applications.
Acknowledgments
The authors are thankful to SAIF, IIT Madras, for
characterization studies, Prof. R. Baskaran, Crystal
growth center, Anna University for providing
HRXRD studies and Dr. N. Nizam Mohaideen,
J. Mol. Eng. Mater. 2014.02. Downloaded from www.worldscientific.com
Department of Physics, The New College (Auton-
omous) for XRD structure determination regarding
by Mr M Dhavamurthy on 07/24/15. For personal use only.
this paper.
References
1. B. R. Bhogala and A. Nangia, Cryst. Growth Des. 3,
547 (2003).
2. D. S. Chemla and J. Zyss, Non-linear Optical
Properties of Organic Molecules and Crystals (New
York, 1991).
3. B. F. Levine and C. G. Bethea, Appl. Phys. Lett. 24,
445 (1974).
4. V. A. Russell, M. C. Etter and M. D. Ward, J. Am.
Chem. Soc. 116, 1941 (1994).
5. J. M. Adams and R. W. H. Small, Acta Cryst. B30,
2191 (1974).
6. A. Victoria and R. Margaret, Chem. Mater. 6, 1206
(1994).
7. BrukerAPEX2, SAINT, XPREP and SADABS.
Bruker AXS Inc., Madison, Wisconsin, USA (2004).
8. G. M. Sheldrick, Acta Cryst. A 64, 112 (2008).
9. Y. Moritani, N. Sasahara, S. Kashino and M. Haisa,
Acta Crystallogr. C 43, 151 (1987).
1450006-9
Synthesis, Growth and Characterization Studies of p-HOBA
10. H. Parshad, K. Frydenvang, T. Liljefors, H. O. Sor-
ensen and C. Larsen, Int. J. Pharm. 269, 157 (2004).
11. W. Madelung, Zeitschr. Fur € Elektrochemie, 37, 197
(1931).
12. K. Lal and G. Bhagavannarayana, J. Appl. Crys-
tallogr. 22, 209 (1989).
13. N. Renukaa, N. Vijayanb, B. Rathi, R. Ramesh
Babud, K. Nagarajane, D. Haranath and G. Bha-
gavannarayana, Optik 123, 189 (2012)
14. B. W. Batterman and H. Cole, Rev. Mod. Phys. 36
681 (1964).
15. G. Bhagavannarayana, R. V. Ananthamurthy, G.
C. Budakoti, B. Kumar and K. S. Bartwal, J. Appl.
Cryst. 38, 768 (2005).
16. I. Watanbe and T. Okumura, Jpn. J. Appl. Phys.
25, 1851 (1986).
17. M. A. Ga®ar, Physica B 327 43 (2003).
18. G. Guilbault, Practical Fluorescence. Modern.
Monographs in Analytical Chemistry (1990).
19. D. Berlincourt and W. R. Cook Jr. and M. E. Ran-
der, Acta Crystallographica 16, 163 (1963).
20. C. P. Smyth, Dielectric Behavior and Structure
(McGrew-Hill, New York, 1965).
21. C. Balarew and R. Duhlew, J. Solid State Chem. 55,
1 (1984).
22. H. Paredes, D. G. Mintik, O. H. Negrete, H. E.
Ponce, M. E. Alvarez, R. R. R. Mijangos and A. D.
Moller, J. Phys. Chem. Solids 69, 1974 (2008).
23. A. Joseph Arul Pragasam, J. Mhadavan, M. G.
Mohamed, S. Selvakumar, K. Ambujan and P.
Sagayaraj, Optical Materials 29, 173 (2009).
24. J. Madhavan, S. Aruna, K. Prabha, J. Packium
Julius, P. Ginson Joseph, S. Selvakumar and P.
Sagayaraj, J. Cryst. Growth, 293, 409 (2006).
25. J. M. Adams and R. W. H. Small, Acta Cryst. B30,
2191 (1974).
26. T. Arumanayagam and P. Murugakoothan, Mater.
Lett. 65, 2748 (2011).
27. T. Arumanayagam and P. Murugakoothan, J.
Cryst. Growth 362, 304 (2011).