AIP Conf

Synthesis, structure and spectroscopic
investigations of a metal-organic crystal:

Thiourea silver nitrate for optical devices
Cite as: AIP Conference Proceedings 2265, 030410 (2020); https://doi.org/10.1063/5.0017262
Published Online: 05 November 2020
J. Venkatamuthukumar, N. Sivakumar, R. Jayavel, and G. Anbalagan
AIP Conference Proceedings 2265, 030410 (2020); https://doi.org/10.1063/5.0017262 2265, 030410
© 2020 Author(s).
Synthesis, structure and spectroscopic investigations of a
metal-organic crystal: Thiourea silver nitrate for optical
devices
J. Venkatamuthukumar1, N. Sivakumar1,2*, R. Jayavel2 and G. Anbalagan3
1
Saveetha School of Engineering, Saveetha University, Chennai 602 105, India
2
Crystal Growth Centre, Anna University, Chennai 600 025, India
3
Department of Nuclear Physics, University of Madras, Chennai 600 025, India
*Corresponding author: nsivakumar1986@gmail.com
Abstract.A metal-organic crystal, thiourea silver nitrate (TUAgN) was synthesized by conventional chemical route at
room temperature. Powder X-ray diffraction showed the crystalline property of the material. The estimated cell
parameters from the prominent planes results in tetragonal crystal system of the titled material. Various vibrational and
polarizational modes were completely discussed by FT-Infrared and Confocal Raman analysis. Chemical components
present in the crystal were further confirmed with NMR spectral studies.
INTRODUCTION
Metal organic single crystals have the advantages of both organic and metallic properties. In the recent decades,
search is going on to the growth of metal organic single crystals due to their wide optical transparency in the visible
region, many applications in laser technology, communication technology and for optical data storage devices (1-3).
Inorganic materials may possess high thermal stability, wide optical transparent window and significant mechanical
properties. However, these materials cannot be opted for nonlinear optical devices due to its lack of extended π-
electron dislocations (4). Thiourea is aorgano-sulfur material with a unique dipole moment property and having a
natural tendency to form a hydrogen bond network with the other suitable compound (5). A material to exhibit NLO,
it must satisfy the condition of non-centrosymmetric space group, large conjugated π-electrons cloud and more
hydrogen bonds (6). We have been reported some of the titled derivatives and checked their optical nonlinearity.
Actually the titled compound is a polymorphic material which will results in different structure at different
temperatures (7-9). Present research work deals with the effect of molar ratio on thriourea and silver nitrate
materials. In this paper we have discussed the synthesis part, crystalline nature and various spectroscopic
investigations of the titled material.
EXPERIMENTAL SECTION
Thiourea and silver nitrate were taken in 1:4 molar ratio. The weighed thiourea was taken in a beaker with 100ml
of distilled water and stirred well with a magnetic stirrer. The calculated amount of silver nitrate was added gently
into the thriourea solution. The mixture was allowed to stirrer for 5 hours to get a homogenous solution. The final
solution was filtered with a Whatman filter paper and kept in the dust free place for the slow evaporation. The
obtained polycrystalline materials were subjected to various characterizational studies.
DAE Solid State Physics Symposium 2019

AIP Conf. Proc. 2265, 030410-1–030410-4; https://doi.org/10.1063/5.0017262
Published by AIP Publishing. 978-0-7354-2025-0/$30.00
030410-1
Powder X-ray diffraction study
The obtained polycrystalline material were crushed into a fine powder and is tested with Rich Seifert X-ray
powderdiffractometer with Cu-Kα radiation of wavelength 1.5406 Å. The recorded powder X-ray diffraction
spectrum of TUAgN in the 2theta range from 5 to 50 at the rate of 1 /min is shown in Fig. 1. All the peaks were
completely indexed and reveal the good crystalline behavior. The prominent planes were selected and the lattice
parameter values were estimated with the help of XRDA software. The unit cell values of TUAgN crystal were
found to be a=14.7801Å, b=14.1078Å, c=23.9831Å and V=5060Å3.
FIGURE 1.Powder X-Ray spectrum of TUAgN
FTIR and Confocal Raman spectral studies

FTIR spectrum provides all the vibrational details of the investigated material. The sample was tested at room
temperature with Perkin Elmer Spectrum one FT-IR spectrometer in the range 400 – 4000 cm-1 by a KBr pellet
technique with a resolution of 2 cm-1. Raman spectroscopy will provide all the molecular details about the materials
along with their metal vibrations. Raman spectra can be studied for the sample in two different modes either fourier
transform or Confocal methods. In confocal Raman technique, laser source of wavelength 532nm is used. Therefore
the peaks which are not appeared in the FT-Raman can also be identified. The recorded FTIR spectrum of TUAgN
is presented in Fig. 2. Shift in peak position of the spectra provides the conformation about the complex formation.
In general there are two ways by which one can confirm the metal co-ordination with thiourea. The Ag metal may
co-ordinate with the thiourea with through N or S in thiourea. Therefore the CS and CN stretching vibrations must
be present in the recorded spectrum.
The prepared TUAgN material was studied by Confocal Raman Spectra using WITEC alpha 300 Confocal
Raman system in the range 0-3800 cm-1 with Nd:YAG laser of wavelength 532 nm. The obtained Confocal Raman
spectrum of TUAgN is shown in Fig. 3. In pure thiourea molecule, CS will be bonded with NH group. But in
TUAgN crystal CS is bonded with Ag ion. The force of interaction present between CS and NH pair of thiourea
shifts its Raman NCN vibration at 495 cm-1 to 483 cm-1 (8). The IR band of pure thiourea at 3371, 3272, 1472, 1414,
1083, 728, 501 cm-1 are shifted to 3375, 3284, 1467, 1385, 1092, 716, 493 cm-1 in TUAgN crystal. These bands are
corresponds to asymmetric stretching of NH2, symmetric stretching of NH2, asymmetric stretching of CN,
asymmetric stretching of CS, symmetric stretching of CN, symmetric stretching of CS and bending vibration of
NCN respectively. The similar bands were appeared at 3318, 3225, 1490, 1425, 1063, 740, 483 cm-1 in the confocal
Raman spectrum. The confocal Raman spectrum at 177 cm-1 confirms the stretching vibration of AgS.
030410-2
FIGURE 2.FTIR spectrum of TUAgN FIGURE 3. Confocal Raman spectrum of TUAgN
NMR spectral studies
The chemical structure of the compound can be completely identified by NMR spectral studies. The 1H NMR
and 13C NMR studies were carried out on the TUAgN material with the help of BrukerAdvance III 500 MHz
spectrometer at 22 °C with D2O as a solvent and their respective spectrums are shown in Figs. 4 and 5 respectively.
It is noticed that a strong peak at 4.702 ppm exhibits the presence of amide group in TUAgN material. This single
peak is slightly downfield which reveals the presence of sulphur in the amide group. The materials with C=O of
COOH groups generally show their signals in between 150 to 185 ppm. In the titled material, signal at 179.49 ppm
reveals the presence of sulphur in TUAgN crystal.
FIGURE 4.1H NMR spectraof TUAgN FIGURE 5.13C spectra of TUAgN
030410-3
ACKNOWLEDGMENTS
One of the author express his since thanks to UGC-Dr.D.S. Kothari Fellowship scheme for providing financial
support (Grant No. F.4-2/2006(BSR)/PH/16-17/0109) and Crystal Growth Centre, Anna University for providing
excellent lab facilities.
REFERENCES
1. Z. Zhi-Gang, Appl. Opt. 52, 5701-5706 (2013).
2. Z. Zhi-Gang and Y. Wen-Xuan, J. Appl. Phys. 109, 103-106 (2011).
3. Z. Zhi-Gang and Z. Yujun. Appl. Opt. 51, 3424-3430 (2012).
4. J. Ramajothi. S. Dhanuskodi and K. Nagarajan, Cryst. Res. Technol. 39, 414-420 (2004).
5. M.M. Kumari, P.I. Ramachandra, C. Ravikumar, I.H. Joe and I. Nemec, J. Raman Spectros. 42, 1462-1469,
(2011).
6. V. Krishnakumar, and R. Nagalakshmi, SpectrochimicaActa A. 6, 499-507( 2005).
7. N. Sivakumar, N. Kanagathara, K. Gayathri, P.Krishnan and G. Anbalagan, J. Therm. Anal. Calorim. 115,
1295-1301 (2014).
8. N. Sivakumar, N. Kanagathara, B. Varghese, G.Bhagavannarayana, S. Gunasekaran and G.Anbalagan,
9. SpectrochimicaActa A. 118, 603-613, (2014).
10. N. Sivakumar. V. Jaisankar, G. Chakkaravarthi and G. Anbalagan, Mater. Letter. 132, 298-301 (2014).
030410-4

AIP Conf

Uploaded by

Copyright:

Available Formats

AIP Conf

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

AIP Conf

Uploaded by

Copyright:

Available Formats

Synthesis, structure and spectroscopic

investigations of a metal-organic crystal:

J. Venkatamuthukumar, N. Sivakumar, R. Jayavel, and G. Anbalagan

AIP Conference Proceedings 2265, 030410 (2020); https://doi.org/10.1063/5.0017262 2265, 030410

DAE Solid State Physics Symposium 2019

FIGURE 1.Powder X-Ray spectrum of TUAgN

FTIR and Confocal Raman spectral studies

NMR spectral studies

FIGURE 4.1H NMR spectraof TUAgN FIGURE 5.13C spectra of TUAgN

You might also like