Novel material for second harmonic generation: 3-Amino-1,2,4-triazolinium(1+) hydrogen l -tartrate

Journal of Molecular Structure 834–836 (2007) 328–335 www.elsevier.com/locate/molstruc

Novel material for second harmonic generation: 3-Amino-1,2,4-triazolinium(1+) hydrogen L-tartrate Irena Matulkova´ a

a,*

, Ivan Neˇmec a, Ivana Cı´sarˇova´ a, Petr Neˇmec b, Zdeneˇk Micˇka

a

Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry, Hlavova 8, 128 40 Prague 2, Czech Republic b Charles University in Prague, Faculty of Mathematics and Physics, Department of Chemical Physics and Optics, Ke Karlovu 3, 121 16 Prague 2, Czech Republic Received 6 October 2006; received in revised form 3 November 2006; accepted 6 November 2006 Available online 4 January 2007

Abstract The X-ray structural analysis of 3-amino-1,2,4-triazolinium(1+) hydrogen L-tartrate has been carried out. This organic salt crystallises ˚ , b = 6.7690(2) A ˚ , c = 9.2170(3) A ˚ , b = 95.726(2), V = 478.81(2) A ˚ 3, Z = 2, in the monoclinic space group P21, a = 7.7130(2) A R = 0.0255 for 5922 observed reflections. The crystal structure is formed by a 3D network of hydrogen L-tartrate anions (interconnected by O–H  O hydrogen bonds) with 3-amino-1,2,4-triazolinium(1+) cations located in the cavities of this network and connected with anions via N–H  O and O–H  N hydrogen bonds. The FTIR and FT Raman spectra were recorded, calculated and discussed. Quantitative measurements of second harmonic generation of powdered 3-amino-1,2,4-triazol-4-ium hydrogen L-tartrate at 800 nm were performed and a relative efficiency of 50% (compared to KDP) was observed.  2006 Elsevier B.V. All rights reserved. Keywords: 3-Amino-1,2,4-triazolinium(1+) hydrogen L-tartrate; Crystal structure; Vibrational spectra; HF; B3LYP; MP2; Second harmonic generation

1. Introduction 3-Amino-1,2,4-triazole has been widely studied for its variety of uses [1–5]. One of the most interesting studies is related to its use as an agent to treat Alzheimer’s disease, based on reduction of cytotoxic peptides in myeloma cells [1]. 3-Amino-1,2,4-triazole (Amitrole) was also patented as a herbicide in 1954. It is still used for control of annual grasses and perennial and annual broadleaved weeds [2]. Other applications of 3-amino-1,2,4-triazole lie in the fields of corrosion inhibition [3,4] and modification of the surface of silica gel in chromatography [5]. Several molecular complexes of 3-amino-1,2,4-triazole with substituted aromatic and heterocyclic carboxylic acids have been discussed [6] in relation to their solid-state packing and interactive modes of 3-aminotriazole. The nature of phosphate

*

Corresponding author. Tel.: +420 221 951 245; fax: +420 221 951 253. E-mail address: [email protected] (I. Matulkova´).

0022-2860/$ - see front matter  2006 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2006.11.019

anion-organic cation interaction was studied in the paper [7] concerning 3-amino-1,2,4-triazolinium(1+) hydrogen phosphate. Triazoles have been studied sporadically by the methods of vibrational spectroscopy [8–10]. Recently, a paper [9] comparing the theoretical calculations of the vibrational modes of triazole and tetrazole with the measured spectra was published. The motivation for preparation of 3-amino-1,2,4-triazolinium(1+) hydrogen L-tartrate (3-atHT) lay in the fact that organic non-linear optical (NLO) materials frequently exhibit more versatile properties compared to inorganic materials. They can have larger second-order molecular hyperpolarizabilities (b), higher resistance to optical damage, more favourable physical properties and easier synthetic modification [11]. The feasibility of utilization of the 3-amino-1,2,4-triazolinium(1+) cation (i.e. a nitrogencontaining ion with a delocalized p-electron system, which serves as the main carrier of NLO properties) in material design is also based on the observation of second harmonic

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generation in the chiral Cd(II) coordination polymer with 3-amino-1,2,4-triazole ligands [12]. As was mentioned in a review [13], several groups were interested in the preparation of NLO materials for second harmonic generation (SHG) by combining organic polarizable cations and dicarboxylic acids, especially chiral tartaric acid. These salts, based on a non-centrosymmetric tartrate anionic framework with incorporated organic cations, exhibit thermal and structural stability, which is provided by the selectivity and directionality of hydrogen bonds. Hydrogen bonding in this class of materials strongly influences not only the lattice energy, but also the NLO properties [14–16]. In this paper, which is part of our project focused on preparation and study of novel NLO materials, the crystal structure, vibrational spectra and determination of SHG efficiency of 3-amino-1,2,4-triazolinium(1+) hydrogen Ltartrate are reported and discussed. 2. Experimental Crystals of 3-atHT were prepared by spontaneous crystallisation of an equimolar mixture of 3-amino-1,2,4-triazole (purum, Fluka) and L-tartaric acid (purum, Lachema) in a desiccator over KOH at room temperature. The prepared colourless crystals were filtered off, washed with methanol and dried in a desiccator over KOH. The crystals of 3-atHT are stable in the air up to the melting point at 443 K. Collection of X-ray data was performed on a Nonius Kappa CCD diffractometer (MoKa radiation, graphite monochromator). The phase problem was solved by direct methods (SIR-92 [17]) and the non-hydrogen atoms were refined anisotropically, using the full-matrix least-squares procedure (SHELXL-97 [18]). The positions of hydrogen atoms were localised on difference Fourier maps and were fixed during refinement using rigid body approximation with assigned displacement parameters equal to 1.2 Uiso (pivot atom). The basic crystallographic data, measurement and refinement details are summarised in Table 1. Crystallographic data for 3-atHT have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication CCDC 622634. A copy of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CG21, EZ, UK (fax: +44 1223 336 033; e-mail: deposit@ ccdc.cam.ac.uk). The infrared spectra were recorded on a Nicolet Magna 760 FTIR spectrometer (2 cm1 resolution, Happ-Genzel apodization) by the nujol mull and DRIFTS techniques in the 100–4000 cm1 region. The Raman spectra of polycrystalline samples were recorded on a Nicolet Magna 760 FTIR spectrometer equipped with the Nicolet Nexus FT Raman module (2 cm1 resolution, Happ-Genzel apodization, 1064 nm Nd:YVO4 laser excitation, 200 mW power at the sample) in the 100–3700 cm1 region.

329

Table 1 Crystal data and structure refinement for 3-atHT Identification code Empirical formula Formula weight Temperature a b c b Volume Z Calculated density Crystal system Space group Absorption coefficient F(0 0 0) Crystal size Diffractometer and radiation used Scan technique Completeness to h Range of h, k and 1 h range for data collection Reflection collected/unique (Rint) No. of observed reflection Absorption correction Function minimized Parameters refined R, wR [I > 2r(I)] R, wR (all data) Value of S Max and min in final Dq map Weight scheme Sources of atom. scatt. fact. Program used

3-atHT C6H10N4O6 234.18 293(2) K ˚ 7.7130(2) A ˚ 6.7690(2) A ˚ 9.2170(3) A 95.726(2) ˚3 478.81(2) A 2 1.624 Mg/m3 Monoclinic P21 0.146 mm1 244 0.60 · 0.35 · 0.30 mm Nonius Kappa CCD, ˚ k = 0.71073 A x and W scans to fill the Ewald sphere 98.0% 9 fi 10, 8 fi 8, 11 fi 11 3.29–27.51 5922/2151 (0.0150) 2121 None RwðF 2o  F 2c Þ2 145 0.0255, 0.0700 0.0259, 0.0707 1.096 ˚ 3 0.179 and 0.140 eA w ¼ ½r2 ðF 2o Þ þ ð0:0404P Þ2 þ 0:0512P 1 SHELXL97 [18] SHELXL97 [18], PLATON [22], SIR97 [17]

The quantum chemical calculations were performed by applying the closed-shell restricted Hartree-Fock (HF), Density Functional Theory (B3LYP) and Møller Plesset perturbation (MP2) methods with the 6-31G and 6-311G basis sets. The calculations and visualisations of the results were carried out with the Gaussian 98W [19] and GaussViewW 2.1 [20] program packages. The geometry optimisations, also providing the molecular energies, were followed by frequency calculations together with IR and Raman intensities using the same basis set. The calculated geometry and frequencies scaled with precomputed vibrational scaling factors [21] were compared to the experimental values. The UV–Vis-NIR spectrum of a 3-atHT aqueous solution (quartz cell) was recorded in the 190–1100 nm range using a Unicam UV 300 spectrometer. The measurements of SHG at 800 nm were performed with 90 fs laser pulses generated at an 82 MHz repetition rate by a Ti:sapphire laser (Tsunami, Spectra Physics). For quantitative determination of the SHG efficiency, the intensity of the back-scattered laser light at 400 nm generated in the sample was measured by a grating spectrograph

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with diode array (InstaSpec II, Oriel) and the signal was compared with that generated in KDP (i.e. KH2PO4). The experiment was performed using a powdered sample (75–150 lm particle size) loaded into 5 mm glass cells with the aid of a vibrator and the measurements were repeated on different areas of the same sample (the results were averaged). This experimental procedure minimises the signal fluctuations induced by sample packing.

3. Results and discussion 3.1. The crystal structure of 3-atHT The crystals of 3-atHT belong in the monoclinic space group P21. The atom numbering is depicted in Fig. 1 (PLATON software [22]). The selected bond lengths and angles, including those of hydrogen bonds, are presented in Table 2. The crystal structure is based on a 3D network of hydrogen L-tartrate anions interconnected by two types of O–H  O hydrogen bonds (see Fig. 2) with lengths of ˚ . The first type (O1–H1  O5v) con2.515(1) and 2.632(1) A nects the protonised carboxylic group with the carboxylate group of another anion. The second type (O4–H4  O5vi) links the hydroxyl group with the carboxylate group of another anion. Participation of the O5 oxygen atom in the two strongest inter-molecular H-bonds is reflected in ˚ ) compared the elongation of the C9–O5 bond (1.270(1) A ˚ ). to the similar C9–O6 bond (1.237(2) A Planar 3-amino-1,2,4-triazolinium(1+) cations are located in the cavities of the hydrogen L-tartrate network and connected with anions via the N–H  O and O–H  N hydrogen bonds (see Fig. 3), with lengths of ˚ and 3.155(1) A ˚ , respectively. There 2.732(1)–3.016(2) A is no hydrogen bonding between the cations and,

Table 2 ˚ ) and angles () for 3-atHT Selected bond lengths (A Bond/angle

Value

Angle

Value

N1–C5 N1–N2 N2–C3 N4–C5 C3–N6 C3–N4 C6–O2 C6–O1 C6–C7 C7–O3 C7–C8 C8–O4 C8–C9 C9–O6 C9–O5 N1–C5–N4 N2–C3–N4

1.289(2) 1.380(2) 1.330(2) 1.365(2) 1.325(2) 1.347(2) 1.202(2) 1.305(1) 1.531(1) 1.415(1) 1.535(2) 1.411(1) 1.532(1) 1.237(2) 1.270(1) 112.3(1) 105.7(1)

N6–C3–N2 N6–C3–N4 C3–N2–N1 C3–N4–C5 C5–N1–N2 C6–C7–C8 C9–C8–C7 O1–C6–C7 O2–C6–O1 O2–C6–C7 O3–C7–C6 O3–C7–C8 O4–C8–C9 O4–C8–C7 O5–C9–C8 O6–C9–O5 O6–C9–C8

127.1(1) 127.2(1) 111.6(1) 106.7(1) 103.7(1) 107.8(1) 108.0(1) 111.8(1) 126.4(1) 121.8(1) 113.3(1) 110.6(1) 111.6(1) 108.5(1) 115.1(1) 125.2(1) 119.6(1)

Hydrogen bonds D–H  A

d(D–H)

d(H  A)

d(D  A)

<(DHA)

N2–H2A  O6i N4–H4A  O2ii N4–H4A  O4iii N6–H6A  O3i N6–H6B  O4iii N6–H6B  O6iii O3–H3  N1iv O1–H1  O5v O3–H3  O1 O4–H4  O5vi

0.88 0.95 0.95 0.96 0.92 0.92 0.88 0.99 0.88 0.89

1.88 2.34 1.99 2.08 2.30 2.15 2.34 1.53 2.07 1.77

2.732(1) 2.914(2) 2.800(1) 3.016(2) 2.998(2) 3.003(1) 3.155(1) 2.515(1) 2.579(1) 2.631(1)

160.6 118.2 141.5 164.6 132.4 152.7 154.5 170.8 115.7 162.1

Note. Equivalent positions: (i) x + l, y  l/2, z + 2; (ii) x, y  l/2, z + l; (iii) x, y  l, z; (iv) x, y + l/2, z + 2; (v) x  l, y, z; (vi) x + l, y + l/2, z + l. Abbreviations: A, acceptor; D, donor.

according to the arrangement of 3-aminotriazole rings, no p–p interaction can be considered for crystal structure stabilisation. 3.2. Cation geometry optimisation and calculation of vibrational frequencies

Fig. 1. Atom numbering of 3-atHT. Dashed lines indicate hydrogen bonds.

The geometry of the isolated 3-amino-1,2,4-triazolinium(1+) cation was optimised using the HF, B3LYP and MP2 methods for the 6-31G and 6-311G basis sets. The comparison of the experimental (3-atHT crystal structure) and the calculated values of the geometry-optimised structures for more sophisticated 6-311G basis set is presented in Table 3. It is apparent that the best match with the Xray diffraction data was obtained for the HF method. This method very slightly underestimates the bond lengths with the exception of the N4–C5 bond, which is slightly overestimated. The B3LYP and MP2 methods systematically overestimate all the bond lengths (the biggest difference ˚ was found in the case of the MP2 method for of 0.41 A the N1–C5 bond). The values of the optimised inter-atomic angles fluctuate slightly around the values from the crystal structure. The biggest difference (1.71) was observed for the N1–C5–N4 angle obtained by the HF method.

I. Matulkova´ et al. / Journal of Molecular Structure 834–836 (2007) 328–335

331

Fig. 2. 3D network of hydrogen L-tartrate anions (projection to xy plane). Dashed lines indicate hydrogen bonds.

Fig. 3. The arrangement of 3-amino-1,2,4-triazolinium(1+) cations in the 3D network of hydrogen L-tartrate anions (projection to yz plane). Dashed lines indicate hydrogen bonds.

According to successful geometry optimisation, the fundamental vibrational frequencies of 3-amino-1,2,4-triazolinium(1+) cation were calculated using the HF, B3LYP and MP2 methods for the 6-31G and 6-311G basis sets. The results of these calculations, together with the experimental data for 3-amino-1,2,4-triazolinium(1+) chloride, are presented in Table 4. The best match with the recorded spectra was obtained for the scaled HF/6-311G method. The largest differences were observed for the stretching N–H vibrations due to the fact that the formation of hydrogen bonds, which strongly affects the positions and intensities of the bands, was not considered in the calculation.

3.3. Vibrational spectra of 3-atHT The FTIR and FT Raman spectra of 3-atHT recorded at room temperature are depicted in Fig. 4. The wavenumbers of the observed maxima and their intensities are presented in Table 5. The assignment of the bands of the 3-amino-1,2,4-triazolinium(1+) cation is based on the HF/6-311G calculations (see Table 4). The vibrational bands of the hydrogen tartrate anions were assigned according to earlier spectroscopic studies of the compounds of L-tartaric acid [23–26]. The structured, strong to weak-intensity bands in the 3550–2200 cm1 region in the IR spectrum and weak bands

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332

Table 3 Determined and calculated bond lengths and angles for 3-amino-1,2,4-triazolinium(l+) cation X-ray data (3-atHT)

Geometry optimisation

Bond

˚) (A

Angle

()

N(1)–C(5) N(1)–N(2) N(2)–C(3) N(2)–H(2A) C(3)–N(6) C(3)–N(4) N(4)–C(5) N(4)–H(4A) N(6)–H(6A) N(6)–H(6B)

1.289(2) 1.380(2) 1.330(2) 0.8821 1.325(2) 1.347(2) 1.365(2) 0.9524 0.9601 0.9240

C(5)–N(1)–N(2) C(3)–N(2)–N(1) C(3)–N(2)–H(2) N(l)–N(2)–H(2) N(2)–C(3)–N(6) N(2)–C(3)–N(4) N(6)–C(3)–N(4) C(3)–N(4)–C(5) N(l)–C(5)–N(4) C(3)–N(6)–H(6A) C(3)–N(6)–H(6B) H(6A)–N(6)–H(6B) C(3)–N(4)–H(4A) C(5)–N(4)–H(4A)

103.7(1) 111.6(1) 125.5 122.5 127.1(1) 105.7(1) 127.2(1) 106.7(1) 112.3(1) 121.7 121.9 112.3 122.1 130.6

B3LYP/6-311G ˚) Bond (A Angle ()

HF/6-311G ˚) Bond (A

1.307 1.400 1.350 1.000 1.330 1.360 1.390 1.000 1.000 1.000

1.270 1.380 1.320 0.980 1.320 1.340 1.390 0.990 0.990 0.990

located in the Raman spectrum in the 3450–3000 cm1 region can be assigned to the stretching vibrations of the NH and OH groups participating in the hydrogen bonds of the N–H  O, O–H  N or O–H  O types. Manifestations of m OH vibrations of the strongest O–H  O hydro˚ ) are somewhat complicated by gen bond (2.515 A overlapping with the m C@O, d NH2, d ring and d NH mixed vibrations in the 1720–1650 cm1 region in the IR spectrum. The vibrational bands of the out-of-plane O–H(  O) and N–H(  O) bending modes were observed in the 890–850 cm1 region. The positions of the bands of these stretching and out-of-plane bending modes are in agreement with the correlation curves [27,28] for the O–H  O and N–H  O hydrogen bonds found in the 3-atHT crystal structure. The sharp bands recorded at 2921 and 2906 cm1 in the Raman spectrum (2921 and 2905 cm1 in the IR spectrum) correspond to the C–H stretching vibrations of the hydrogen tartrate anion. The strong mixed bands of the stretching C@O vibration located in the IR spectrum at 1694 and 1676 cm1 (1697 cm1 Raman) are associated with the presence of a protonised carboxylic group in the structure. Medium to weak-intensity bands corresponding to the antisymmetric stretching vibration of the carboxylate group (mixed with cation vibrations) were recorded at 1630, 1573 and 1539 cm1 in the IR spectrum (1606 and 1572 cm1 in the Raman spectrum), while those of the symmetric stretching vibration were observed at 1438 and 1445 cm1 in the IR and the Raman spectra, respectively. The assignment of the rest of the hydrogen tartrate vibrational bands is presented in Table 5. The bands corresponding to the stretching CH vibrations of the aromatic triazole ring were recorded at 3171 and 3122 cm1 in the Raman spectrum and 3168 cm1 in the IR spectrum. The presence of the –NH2 group in the cation skeleton is reflected in several bands of deformation,

103.86 112.30 129.21 118.48 128.05 104.63 127.31 108.08 111.07 121.51 121.91 116.57 126.23 125.67

Angle () 104.78 111.75 126.50 119.14 127.76 105.25 126.98 107.52 110.59 121.43 121.68 116.88 126.50 125.96

MP2/6-311G ˚) Bond (A Angle () 1.330 1.410 1.350 1.000 1.340 1.370 1.400 1.010 1.000 1.000

103.30 112.88 129.00 118.09 128.10 104.78 127.11 108.13 110.86 121.41 121.67 116.91 126.23 125.64

rocking and wagging vibrations (see Table 5). Vibrational manifestations of the 3-amino-1,2,4-triazolinium(1+) cation with the main contribution of the stretching and deformation motions of triazole ring are located in the 1630–990 cm1 region in both the spectra. The pair of dominant Raman bands at 1047 and 726 cm1 is associated with the mixed vibrational motions of the m ring, c CH, d NH and c NH, m ring, respectively. Several bands located below 165 cm1 can be assigned to external modes of the 3-atHT crystals. 3.4. Second harmonic generation Crystals of 3-atHT are non-centrosymmetric (space group P21) and optically transparent down to 245 nm (see Fig. 5). The relative SHG efficiency of a powdered sample at 800 nm was observed as equal to 50% compared to KDP. 4. Conclusions The novel organic salt 3-amino-1,2,4-triazolinium(1+) hydrogen L-tartrate was prepared and its crystal structure was solved by the method of X-ray structural analysis. The crystal structure is formed by a 3D network of hydrogen L-tartrate anions (interconnected by O–H  O hydrogen bonds) with 3-amino-1,2,4-triazolinium(1+) cations located in the cavities of this network and connected with anions via N–H  O and O–H  N hydrogen bonds. The FTIR and FT Raman spectra were recorded, calculated and discussed. The results of quantitative measurements of SHG of powdered samples (50% efficiency compared to KDP) together with optical transparency down to 245 nm and thermal stability (melting at 443 K) leads to the conclusion that 3-amino-1,2,4-triazolinium(1+) hydrogen L-tartrate is a promising novel NLO material.

Table 4 Calculated and experimental fundamental frequencies of 3-amino-l,2,4-triazolinium(l+) cation B3LYP

MP2

HF

Measured

283 319 394 615 619 663 673 710 727 852 903 979 1018 1044 1076 1231 1328 1384 1453

0/0 0/2 0/3 20/1 1/0 15/1 24/2 1/20 96/0 1/2 3/5 0/1 0/15 1/7 2/0 2/12 3/7 3/11 1/2

280 313 394 616 621 659 679 712 725 844 911 985 1020 1044 1076 1233 1326 1387 1448

0/0 0/1 0/3 23/0 1/0 20/1 17/1 1/20 93/0 2/1 4/5 1/1 0/14 1/7 2/1 2/12 2/8 4/10 1/3

236 258 389 495 572 606 621 658 699 770 885 957 1001 1043 1067 1203 1308 1388 1427

0/2 0/0 0/3 75/1 9/1 9/0 12/1 99/1 1/22 8/2 2/6 0/2 1/21 0/5 2/1 2/9 2/6 6/11 1/5

123 200 324 379 500 527 595 601 696 713 892 968 1001 1039 1067 1190 1301 1382 1416

11/1 22/0 73/0 0/3 4/1 44/1 0/0 85/1 2/22 21/1 4/5 1/2 2/20 0/5 3/1 3/9 2/6 10/11 1/6

293 360 400 625 673 690 721 735 809 926 934 1003 1034 1073 1079 1253 1357 1426 1492

0/0 0/2 0/3 1/1 16/0 26/0 1/16 1/2 0/0 4/5 0/3 1/1 0/16 1/3 2/3 1/14 1/1 2/12 2/2

289 348 398 624 633 671 699 720 772 911 935 1015 1037 1069 1083 1254 1348 1418 1484

0/0 0/1 0/3 3/1 14/0 44/1 11/1 1/15 82/0 0/3 5/5 3/1 0/17 1/2 2/3 1/13 0/2 3/13 2/2

cN–C–NH2 sNH2, dNH dN–C–NH2 crg, cCH xNH, cNH crg, cCH cNH, crg mrg crg, cNH, cCH cCH mrg, drg, dNH, dCH mrg, dCH, dNH2 mrg, dCH, dNH mrg, dNH2 mrg, drg, dNH mrg, drg, dCH mrg, drg, dNH mrg, drg, dNH mrg, drg, dNH2, dNH

1531 1648 1690 3222 3466 3517 3543 3574

6/13 0/4 100/10 5/95 39/100 34/67 26/89 22/53

1528 1651 1678 3197 3468 3522 3549 3578

5/15 13/1 100/12 4/87 39/100 34/63 24/86 21/48

1478 1654 1682 3199 3440 3478 3499 3559

7/4 28/2 100/16 6/89 53/100 51/54 34/83 29/49

1468 1634 1672 3133 3400 3443 3466 3522

8/5 100/7 86/12 6/80 70/100 66/48 40/79 35/43

1618 1673 1704 3181 3444 3509 3532 3554

8/23 0/3 95/16 4/95 29/100 32/49 21/86 22/51

1607 1668 1686 3149 3445 3516 3538 3558

8/26 20/0 100/19 3/86 33/100 36/48 22/85 23/46

mrg, drg, dCH drg, dNH2 dNH2, drg, dNH mCH 9 mNH2 > > = mNH mNH > > ; mNH2

Raman 297 w

628 m

624 w 633 w

706 755 789 875 949

700 w 732 s 791 w

m m m w m

1052 1092 1264 1351 1420 1482

m m w m m m

1618 1657 1691 2906

m s vs s

952 m 1039 s 1059 s 1263 1349 1431 1478 1572 1617

s m m m s m

1689 m 2937 w

2992–3304 3107–3304

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6-31G IR/Raman 6-311G IR/Raman 6-31G IR/Raman 6-311G IR/Raman 6-31G IR/Raman 6-311G IR/Raman 3-amino-1,2,4-triazolinium chloride S.F.a intensities S.F.a 0.966 intensities S.F.a 0.957 intensities S.F.a 0.950 intensities S.F.a 0.903 intensities S.F.a 0.904 intensities Assignment IR 0.962

Note. Calculated IR and Raman intensities are presented in relative scale (from 0 to 100). Abbreviation and Greek symbols used for vibrational modes: rg, ring; m, stretching; d, deformation or in-plane bending; c, out-of-plane bending; x, wagging. a Precomputed vibrational scaling factor [21].

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Fig. 5. UV–vis-NIR spectrum of 3-atHT aqueous solution. Fig. 4. FTIR (nujol mull) and FT Raman spectra of 3-atHT. Nujol bands are indicated by asterisks.

Table 5 FTIR and FT Raman spectra of 3-atHT IR (cm1)

Raman (cm1)

Assignment

IR (cm1)

Raman (cm1)

Assignment

3452 3360 3307 3260 3168

3451 w 3361 w

mN–H(  O), mO–H(  N)

1043 w 985 vw 952 w 894 w 887 w 860 m 843 vw 830 vw 788 vw 775 w 753 w 721 w 706 w 626 w

1047 vs 989 m 966 m 889 s

mrg, cCH, dNH mrg, drg, dNH, dCH mCC

2973 2921 2905 2870 2795 2723 2425 2346 2297 1694 1676 1630

m s s sb s s s s s s m wb w wb s s m

1573 m 1539 mb 1438 m 1413 m 1389 m 1338 1324 1293 1265 1221 1126 1102 1076

sh s w m sb s vw s

3260 wb 3171 m 3122 w 2921 m 2906 m

mCH mN–H(  O), mO–H(  O) mCHa mN–H(  O), mO–H(  O)

mO–H(  O)

cCH, cO–H(  O), cN–H(  O) 865 w 841 w

779 m 726 s 712 sh 619 w

1697 m

mC@O, dNH2, drg, dNH, mO–H(  O)

603 vw 577 vw

masCOO, mrg, drg, dCH 1606 w 1572 w 1471 1445 1404 1390 1376 1345 1322 1289 1252 1222 1125 1100 1065

w w m m m m w w s m w w m

mrg, drg, dNH2, dNH msCOO dNH, mrg, drg msCOO dNH, mrg, drg mrg, drg, dNH mC–O mC–O, mrg, drg, dCH qNH2, dCHa mC–NH2 dCHa mrg, dNH2, mC–O

488 463 431 393 352 313 261 227 189 165 154 142

w vw vw m vw vw vw vw m vw vw vw

121 vw 109 vw

589 w 530 m 488 m 431 388 352 309 260 209 187

s w w w w w m

dCOO cCH, dCOO cNH, dCOO, crg, cCH crg cNH, mrg cNH, crg xNH2, cNH crg, cCH, qCOO dCOO ? dN–C–NH2 xCOO, sNH2, dNH xCOO, sCC xCOO, sCC, cN–C–NH2 ? sCOO External modes

156 vs 130 s 117 w

Note. Abbreviations: rg, ring; vs, very strong; s, strong; m, medium; w, weak; vw, very weak; b, broad; sh, shoulder; m, stretching; d, deformation or inplane bending; c, out-of-plane bending; q, rocking; x, wagging; s, torsion; s, symmetric; as, antisymmetric. a Vibrations associated wilh hydrogen tartrate anion.

I. Matulkova´ et al. / Journal of Molecular Structure 834–836 (2007) 328–335

Acknowledgement This study was financially supported by the Grant Agency of Charles University in Prague (Grant No. 337/2005/BCH). References [1] N.G.N. Milton, Neurotoxicology 22 (2001) 767. [2] M. Chicharro, A. Zapardiel, E. Bermejo, M. Moreno, Talanta 59 (2003) 37. [3] W. Qafsaoui, C. Blanc, N. Pe´bere, H. Takenouti, A. Srhiri, G. Mankowski, Electrochim. Acta 47 (2002) 4339. [4] M. Sahin, S. Bilgic, H. Yilmaz, Appl. Surf. Sci. 195 (2002) 1. [5] N.L.D. Filho, Colloids Surf. A Physicochem. Engin. Aspects 144 (1998) 219. [6] W. Li, H.-P. Jia, Z.-F. Ju, J. Zhang, Cryst. Growth Des. 6 (9) (2006) 2136. [7] L. Baouab, T. Guerfel, M. Soussi, A. Jouini, J. Chem. Crystallogra. 30 (12) (2000) 805. [8] V.P. Sinditskii, V.I. Sokol, A.E. Fogel’zang, M.D. Dutov, V.V. Serushkin, M.A. Porai-Koshits, B.S. Svetlov, Zh. Neorg. Khim. 32 (1987) 1459. [9] F. Billes, H. Endre´di, G. Keresztury, J. Mol. Struct. (Teochem) 530 (2000) 183. [10] M.H. Palmer, D. Christen, J. Mol. Struct. 705 (2004) 177. [11] P. Dastidar, T.N.G. Row, B.R. Prasad, C.K. Subramanian, S. Bhattacharya, J. Chem. Soc. Perkin Trans. 2 (1993) 2419. [12] D.E. Lynch, T. Dougall, G. Smith, K.A. Byriel, C.H.L. Kennard, J. Chem. Crystallogr. 29 (1) (1999) 67. [13] T.N. Guru Row, Coord. Chem. Rev. 183 (1999) 81. [14] C.B. Aakero¨y, K.R. Seddon, Chem. Soc. Rev. 22 (6) (1993) 397. [15] D. Xue, S. Zhang, J. Phys. Solids 57 (1996) 1321. [16] D. Xue, S. Zhang, J. Phys. Chem. A 101 (1997) 5547.

335

[17] A. Altomare, M.C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A. Guagliardi, G. Polidori, J. Appl. Crystallogr. 27 (1994) 435. [18] G.M. Sheldrick, SHELXL 97, Program for Refinement from Diffraction Data, University of Go¨ttingen Germany, Go¨ttingen, 1997. [19] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery, Jr., R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, P. Salvador, J.J. Dannenberg, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, A.G. Baboul, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, J.L. Andres, C. Gonzalez, M. Head-Gordon, E.S. Replogle, J.A. Pople, Gaussian 98, Revision A.11, Gaussian, Inc., Pittsburgh PA, 2001. [20] GaussViewW, version 2.1, Gaussian, Inc., Pittsburgh PA, 2001. [21] Russell D. Johnson III (Ed.), NIST Computational Chemistry Comparison and Benchmark DataBase, NIST Standard Reference Database Number 101 Release 10, May 2004, http://srdata.nist.gov/ cccbdb/vibscalejust.asp. [22] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7. [23] S. Debrus, M.K. Marchewka, J. Baran, M. Drozd, R. Czopik, A. Pietraszko, H. Ratajczak, J. Solid. State Chem. 178 (2005) 2880. [24] M.B. Salah, K. Mouaı¨ne, P. Becker, C. Carabatos-Ne´delec, Phys. State Sol. (b) 220 (2000) 1025. [25] P. Kolandaivel, S. Selvasekarapandian, Cryst. Res. Technol. 28 (5) (1993) 665. [26] M.K. Marchewka, H. Ratajczak, S. Debrus, J. Nonlinear Opt. Phys. Mater. 12 (1) (2003) 113. [27] A. Lautie´, F. Froment, A. Novak, Spectrosc. Lett. 9 (1976) 289. [28] A. Novak, Struct. Bond. 18 (1973) 177.