XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
49
T1: O–7
New salts and molecular adducts of dimethylglycine
Aram M. Petrosyan
1
, Vahram V. Ghazaryan
1
, Gerald Giester
2
,
Michel Fleck
2
, Zbigniew Tylczyński
3
, and Maciej Wiesner
3
1
Crystal growth lab, Institute of Applied Problems of Physics, NAS of Armenia, 25 Nersessyan Str.,
0014 Yerevan, Armenia, e-mail: aram.m.petrosyan@gmail.com
2
Institute of Mineralogy and Crystallography, University of Vienna, Althanstr. 14, A-1090 Vienna,
Austria
3
Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland
Among salts of glycine and its N-methyl derivatives salts of N,N-dimethylglycine (DMG)
were less studied [1]. Crystal structures of dimethylglycinium chloride [2], dimethylglycinium
trifluoroacetate [3], molecular adduct DMGellagic acid [4] and of a compound of
dimethylglycine with squaric acid [5] were determined. All these crystals have centrosymmetric
structures. We undertook a systematic work on obtaining and investigation of crystalline salts
and molecular adducts of dimethylglycine. In results of investigation of reaction of
dimethylglycine in water media with various acids (HCl, HBr, HI, HNO
3
, HBF
4
, HClO
4
, H
3
PO
3
,
H
2
SiF
6
, CH
3
SO
3
H, NH
2
SO
3
H, CCl
3
COOH, oxalic, picric, maleic, fumaric, malonic, succinic,
tartaric) we obtained more than 30 crystalline salts and molecular adducts. Particularly, we
obtained for the first time 11 salts with dimethylglycine dimethylglycinium dimeric cation
(DMG···DMGH):
(DMG· ··DMGH)Cl,
(DMG···DMGH)Br,
(DMG···DMGH)I,
(DMG···DMGH)NO
3
,
(DMG···DMGH)BF
4
,
(DMG···DMGH)ClO
4
·H
2
O,
(DMG···DMGH)CH
3
SO
3
,
(DMG···DMGH)NH
2
SO
3
·H
2
O,
(DMG···DMGH)
2
SiF
6
·2H
2
O,
(DMG···DMGH) picrate, (DMG···DMGH) maleate. The majority of obtained salts has
centrosymmetric structure, however, some of them crystallize with polar symmetry:
(DMG···DMGH)Cl (s.g. P2
1
), (DMG···DMGH)Br (P2
1
), (DMG···DMGH) maleate (P2
1
),
(DMGH) maleate (Pna2
1
), (DMGH) (maleic acid···maleate) (Pca2
1
), DMG·L-tartaric acid
(P2
1
), DMG·D-tartaric acid (P2
1
). Two of them, (DMG···DMGH)Cl and (DMG···DMGH)Br,
are new ferroelectrics [6]. We compared obtained data with respective data of salts of glycine,
sarcosine (N-monomethylglycine) and betaine (N,N,N-trimethylglycine). In some cases,
respective salts of glycine, sarcosine and betaine were not known previously. Structures and
vibrational spectra of these salts also will be reported.
Keywords: salts of dimethylglycine; vibrational spectroscopy; crystal structure
Acknowledgment
This work was made possible in part by a research grant condmatex-4423 from the Armenian National
Science and Education Fund (ANSEF) based in New York, USA.
References
[1] M. Fleck, A.M. Petrosyan, Salts of amino acids: crystallization, structure and properties. Springer,
Dordrecht, 2014.
[2] B.D. Santarsiero, R.E. Marsh, J. Crystallogr. Spectrosc. Res. 13(1983) 245.
[3] V.H. Rodrigues, J.A. Paixão, M.M.R.R. Costa, A. Matos Beja, Acta Crystallogr. C57(2001) 417.
[4] Padmini Kavuru, Dalia Aboarayes, Kapildev K. Arora, et al., Crystal Growth Design 10(2010) 3568.
[5] M. Anioła, Z. Dega-Szafran, A. Katrusiak, M. Szafran, New J. Chem. 38(2014) 3556.
[6] A.M. Petrosyan, V.V. Ghazaryan, G. Giester, M. Fleck, Z. Tylczyński, M. Wiesner, Armenian patent
application AM20170042 (priority: 20 March 2017, positive decision: 18 April 2017).
XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
50
T1: O–8
Vibrational spectroscopic aspects of thermal effects observed
in the family of aminopyrimidium salts
Irena Matulková
1
, Ivan Němec
1
, Ivana Císařová
1
, and Přemysl Vaněk
2
1
Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030/8, 128
40 Prague 2, Czech Republic, e-mail: ivan.nemec@natur.cuni.cz
2
Department of Dielectric, Institute of Physics ASCR, v.v.i., Na Slovance 2, 182 21 Prague 8, Czech
Republic
The most of physical properties (including the optical properties) of crystalline materials are
intimately related to the symmetry of their crystal structures, and the eventual phase transitions
are frequently accompanied by the changes of their physical properties. In addition to the
“classical” phase transitions (i.e., first order transitions, second order and/or lambda transitions),
other rarely observed effects, such as glass transitions and isostructural phase transitions [1], can
occur in the family of molecular crystals based on aminopyrimidimium salts. Very interesting
phenomenon of isostructural phase transitions is generally characterized by the discontinuity of
the changes of the unit cell parameters and atomic coordinates connected with a temperature
decrease or increase [2, 3].
This contribution deals with the detailed explanation of the thermal effects observed for
several compounds belonging to the family of aminopyrimidinium salts (studied as a prospective
molecular materials for nonlinear optics) by the combination of the vibrational spectroscopic (IR
and Raman – see Fig. 1.), X-ray diffraction and calorimetric methods. Particular attention will
be focused on the explanation of the temperature behaviour of diamino- and
triaminopyrimidinium phosphates and dicarboxylates.
Fig. 1. Temperature dependent Raman spectra of triaminopyrimidinium hydrogen malonate.
Keywords: Vibrational Spectroscopy; Crystal Structure; Phase Transition
Acknowledgment
Financial support from the CUCAM project (project No. CZ.02.1.01/0.0/0.0/15_003/0000417) is gratefully
acknowledged.
References
[1] D. Chernyshov,M. Hostettler, K.W. Tornroos, H.-B. Burgi, Angew. Chem. Int. Ed. Engl. 42 (2003)
3825.
[2] M. Barma, T.A. Kaplan, S.D. Mahanti, Phys. Lett. A 57 (1976) 168.
[3] V.E. Schneider, E.E. Tornau, Phys. Status Solidi B 111 (1982) 565.
Dostları ilə paylaş: |