X-ray, optical, vibrational, electrical, and DFT study of the polymorphic structure of ethylenediammonium bis iodate α-C2H10N2(IO3)2 and β-C2H10N2(IO3)2
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The interaction of ethylenediamine with iodic acid by the slow evaporation method at room temperature gives rise to the crystals of α-C2H10N2(IO3)2 and β-C2H10N2(IO3)2 denoted as α-EBI and β-EBI, respectively. The acentric crystal structures of both polymorphs that consist of [C2H10N2]2+ cations and [IO3]− anions connected together by N–H…O hydrogen bonds are discussed and compared. The optical properties of both polymorphs were determined using UV-vis diffuse reflectance spectroscopy (DRS) showing a wide transparency windows. The DFT calculations using the mixed B3PW91/[6–31 + (d, p), LanL2Dz] basis set of optimized geometries, dipole moment (μ), polarizability (α), first static hyperpolarizability (β), and population analysis were also reported. The experimental and theoretical IR and Raman spectra were compared, and the careful and complete assignment of the vibrational motions of both compounds was undertaken with the aid of potential energy distribution (PED) analysis. DSC and AC conductivity analysis revealed that α-C2H10N2(IO3)2 and β-C2H10N2(IO3)2 undergo a first-order phase transition around 360 K. The electrical σtot (ω, T) conductivity obeyed to Jonscher’s power law and the temperature dependence of the S(T) parameter showed that the electrical conductivity of both polymorph phases might be treated using the correlated barrier hopping (CBH) model.
KeywordsIodate salt Acentric structure Vibrational spectra Electrical Optical properties DFT
The authors are grateful to Mr. Giovani Predieri, Mr. Pier Paolo Lottici, and Mr. Danilo Bersani for their help with the vibrational measurement. Moreover, authors wish to thank Mr. Salvatore Vantaggio and Dr. Silvio Scaravonati of the Department of Mathematical, Physical and Computer Sciences of the University of Parma for their contribution in carrying out the impedance spectroscopy measurements. In addition, the authors would like to express their deepest appreciation to Mr. Paolo Pelagatti for his warm hospitality and technical help. Last but not least, the authors would like to extend their sincere thanks especially to Mr. Davide Balestri and to all the members of the Units of Analytical Chemistry Cultural Heritage, Inorganic and Crystallography (SCVSA department, university of Parma, Italy), for their technical help and warm hospitality. Finally, the authors acknowledge also the support of the Tunisian Ministry of Higher Education and Scientific Research (LR11ES46).
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Conflict of interest
The authors declare that they have no conflicts of interest.
- 5.Petrosyan AM et al (1998) Investigation of some new nonlinear optical crystals by means of NQR, IR and X-ray diffraction methods. Zeitschrift fur Naturforschung - Section A J Phys Sci 53a:528–536Google Scholar
- 11.Bruker AXS Inc. (2014) APEX2 suite for crystallographic software—single crystal X-ray diffractionGoogle Scholar
- 14.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin J, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) GAUSSIAN09 Rev B01. Gaussian Inc, WallingfordGoogle Scholar
- 15.Frisch A, Nielson AB, Holder AJ (2000) GAUSSVIEW user manual. Gaussian Inc., PittsburghGoogle Scholar
- 16.Jamróz M H (2004) Vibrational energy distribution analysis (VEDA). Technical report, WarsawGoogle Scholar
- 18.Petrosyan AM, Shishkin VA (1996) Correlation between structural, infrared and nuclear quadrupole resonance data of iodates. Z Naturforsch Sect A J Phys Sci 51:667–671Google Scholar
- 20.Gholizadeh M et al (2011) 1,1′-(Ethane-1,2-di-yl)dipyridinium bis-(iodate). Acta Crystallogr Sect E: Struct Rep Online 67:o1614–o1615Google Scholar
- 31.Gardner K (2005) Cellref version 1.00Google Scholar
- 39.Kurtz HA, Dudis DS (1998) Quantum mechanical methods for predicting nonlinear optical properties. Rev Comput Chem 12:241–279Google Scholar
- 40.Poulsen TD, Ogilby PR, Mikkelsen KV (2001) A quantum mechanical method for calculating nonlinear optical properties of condensed phase molecules coupled to a molecular mechanics field: a quadratic multiconfigurational self-consistent-field/molecular mechanics response method. J Chem Phys 115:7843–7851CrossRefGoogle Scholar