Crystal structure, spectroscopic investigation and thermal properties of l -lysine p-toluenesulfonate

Accepted Manuscript Crystal structure, spectroscopic investigation and thermal properties of L-lysine p-toluenesulfonate L. Wang, D.H. Wang, G.H. Zhang, D. Xu, W.X. Deng PII:

S0022-2860(15)30424-5

DOI:

10.1016/j.molstruc.2015.11.019

Reference:

MOLSTR 21969

To appear in:

Journal of Molecular Structure

Received Date: 20 August 2015 Revised Date:

8 November 2015

Accepted Date: 11 November 2015

Please cite this article as: L. Wang, D.H. Wang, G.H. Zhang, D. Xu, W.X. Deng, Crystal structure, spectroscopic investigation and thermal properties of L-lysine p-toluenesulfonate, Journal of Molecular Structure (2015), doi: 10.1016/j.molstruc.2015.11.019. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Crystal structure, spectroscopic investigation and thermal properties

L. Wanga,b,∗, D.H. Wanga, G.H. Zhangb, D. Xub, W.X. Denga a

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of L-lysine p-toluenesulfonate

School of Materials Science and Engineering, Xi’an Shiyou University, Xi’an 710065, P.R. China b

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State Key Laboratory of Crystal Materials and Institute of Crystal Materials, Shandong University, Jinan 250100, P.R. China

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Keywords Crystal structure, X-ray diffraction, Molecule spectroscopy, Thermal analysis, Optical properties

Abstract

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A novel organic crystal was prepared from L-lysine (Lly) and p-toluenesulfonic acid (pTS), which was grown from an aqueous solution by slow cooling method. The crystal system and the lattice parameters have been confirmed by single crystal X-ray diffraction studies. The FT-IR, FT-Raman, 1 H-NMR and 13C-NMR spectral of the crystal have been recorded and analyzed. The spectral analyses confirmed the presence of various functional groups and the molecular configurations in LLTS crystal. The UV-Vis-NIR transmittance spectrum has been carried out which shows the cutoff wavelength around 280 nm. The thermal properties of crystal have been evaluated from thermo gravimetric (TG) and differential thermal analysis (DTA). The melting point of grown crystal is fairly high, at around 259 °C. The nonlinear optical (NLO) properties of LLTS crystal were demonstrated by powder SHG experiment and also by quantum chemical calculations. The powder SHG efficiency of LLTS crystal is relatively low and very different from theoretical calculation results.

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1. Introduction

The importance of amino acids in nonlinear optical (NLO) applications is due to the fact that all the amino acids have chiral symmetry and crystallize in noncentrosymmetric space groups [1]. Since 1983, L-arginine phosphate monohydrate (LAP) crystal composed of chiral L-arginine with phosphate has been found as a NLO crystal [2], more and more chiral amino salt crystals have been discovered and displayed NLO properties [3-7]. LAP crystal is an excellent NLO material, which has high NLO coefficient (>1pm·V-1) and high laser damage threshold (63 GW·cm-2 with wavelength of 1053 nm and pulse-width at 1 ns), etc. [8, 9]. In L-arginine series crystals, varied conformations of L-arginine molecular have been observed [10-13]. The different conformations of L-arginine molecular may have tremendous effects on the crystal properties. As one of the three ∗

Corresponding author. E-mail: [email protected]

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diamino carboxylic acids for body growth [14], L-lysine (Llys) has a carboxyl group and an α-amino group which same as L-arginine molecular, while the only difference between them is that the terminal amino group of Llys replaced the guanidine group of L-arginine. As a comparative work, some novel Llys salts has been synthesized and studied [15, 16]. The benzenesulfonic acids (BSA) are strong anionic connectors. Hideko Koshima and co-workers have reported a series of organic crystals of various BSA and amino-nitropyridine (ANP), which were designed for NLO materials and had fairly high melting points such as around 200 °C [17]. Among them, the crystal of p-toluenesulfonic acid (pTS) with ANP has the relatively high second harmonic generation (SHG) efficiency. Thus, in this paper, a novel organic crystal was prepared from Llys and pTS. Single crystal structure and spectral studies for L-lysine p-toluenesulfonate (LLTS) crystal are reported for the first time. The Llys molecular configuration in LLTS crystal is analyzed by 1H-NMR and 13C-NMR spectral. UV-Vis-NIR transmittance spectrum, thermal properties and NLO properties of the grown crystal are also presented and discussed.

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2. Experimental procedure 2.1 Synthesis

2.2 Solubility

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The title compound was synthesized by dissolving equimolar ratio of commercially available AR grade Llys and pTS in deionized water. The required amount of starting materials for the synthesis of LLTS according to the following chemical reaction:

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The synthesized salt was purified by repeated recrystallization process and the recrystallized materials were used for solubility study and single crystal growth. The solubility of LLTS was estimated for various temperatures from 25 to 45 ºC in steps of 5 ºC. The variation of solubility (g LLTS/100 ml water) with temperature is shown in Fig.S1 (Supplementary material). The solubility increases linearly with the temperature. Hence, slow cooling technique was adopted to grow good quality LLTS single crystals. The solubility of LLTS was found to be 65.20 g/100ml at 40 ºC.

2.3 Crystal growth The synthesized salt was formed based on spontaneous crystallization by slowing evaporation method at 40 °C. The impurity content of the synthesized salt was minimized by purifying the growth solution by repeated recrystallization processes. Saturated aqueous solution of LLTS at 40 °C was prepared using recrystallized material in accordance with the solubility data. Before 2

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starting the crystal growth process, the solution was overheated at 45 °C for 24 hours in order to have high homogeneity. The bulk single crystal was grown by slow cooling technique, in a constant temperature bath controlled to an accuracy of ±0.1 °C. The temperature was lowered at rate of 0.1 °C per day as the growth progressed. After 20 days, optically transparent yellow crystals were harvested and the photograph is shown in Fig. 1.

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2.4 Characterization

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The crystal structure and cell parameters were measured on a Bruker AXS SMART APEX II CCD single X-ray diffractometer with Mo Kα radiation, λ=0.71073 Å. A yellow single crystal (0.25 mm × 0.23 mm × 0.08 mm) was selected and X-ray diffraction intensity data were collected at 296(2) K. Powder X-ray diffraction analysis was done using a Bruker AXS D8 advance X-ray diffractometer. The IR spectrum was recorded in the range 400-4000 cm-1 employing a NEXUS 670 FT-IR spectrometer. The Raman spectrum was performed at room temperature using NXR FT-Raman spectrometer with InGaAs as a detector and CaF2 as the beam splitter. The 1H-NMR and 13C-NMR spectra were recorded using Broker advance 300M spectrometer with D2O as a solvent. The transmittance spectrum from 190 to 2500 nm of the grown crystal was recorded using Hitachi model U-3500 recording spectrophotometer at room temperature. The test crystal was polished to make it totally transparent beforehand and the thickness of the sample was 1 mm. Thermo gravimetric (TG) and differential thermal analysis (DTA) for LLTS crystal were carried out at nitrogen atmosphere on a Diamond TG/DTA Perkin Elmer instrument to study the thermal properties. The second harmonic generation (SHG) measurements were performed using an Nd:YAG laser with fundamental radiation of 1064 nm as the optical source. Theoretical calculation of hyperpolarizability provides another method to investigate SHG properties of materials. The nonlinear response of an isolated molecule in an electric field Ei (ω) can be represented as a Taylor expansion of the total dipole moment µt induced by the field [18]:

µt = µ0 + αi j E + βi j k Ei Ej + L

(1)

1 ∑ (βijj + β jij + β jji ) 3 i≠ j

(2)

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βi = βiii +

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Where αij is linear polarizability, µ0 is the permanent dipole moment, and βijk are the first-order hyperpolarizability tensor components. The components of first-order hyperpolarizibility can be determined using the relation [18]

Using the x, y and z components, permanent dipole moment µ0 can be calculated by the following equation [18]: 1

µ0 = ( µ x 2 + µ y 2 + µ z 2 ) 2

(3)

The complete equation for calculating the first-order hyperpolarizability from GAUSSIAN 03 output is given as follows [19].

βtotal = ( β x + β y + β z )

1 2 1 2 2

= [( β xxx + β xyy + β xzz ) + ( β yyy + β yzz + β yxx ) + ( β zzz + β zxx + β zyy ) ] 2

2

3

(4)

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As the components of GAUSSIAN 03 output are reported in atomic units, the calculated values have to be converted into electrostatic units (1 a.u. = 8.3693 × 10-33 esu). The electric dipole moment and first-order hyperpolarizability were calculated using the finite field method, which offers a straightforward approach for the calculation of hyperpolarizabilities[20]. All the calculations were carried out by the density functional triply parameter hybrid model DFT/B3LYP using GAUSSIAN 03W program on an Intel Pentium(R) 4 CPU 3.00 GHz with 1 GB RAM and Microsoft Windows XP as the operating system. The 6-31G (d, p) basis set has been employed.

3. Results and discussion 3.1 Crystal structure

3.2 IR and Raman spectra

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The crystal data and details of the data collection for the crystal structure determination are listed in Table 1. The crystal system is orthorhombic with four formula units in unit cell (Z = 4). The unit cell parameters are: a = 5.3464(4), b = 15.3387(13), c = 18.5276(15) Å and V = 1519.4(2) Å3 and the space group is P212121. The molecular structure and perspective viewed along a-axis are shown in Fig. 2. Fig.S2 (Supplementary material) gives the experimental and calculated XRPD patterns derived from the single crystal data by the mercury program [21]. The results show that the structure of grown crystal is consistent with the results determined using X-ray single-crystal diffraction at room temperature.

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Vibrational spectroscopy is an important tool in understanding the chemical bonding and provides useful information in studying the microscopic mechanism of the NLO properties of new materials. The molecular structure of the synthesized compound can also be confirmed by the spectral analysis. The FT-IR and Raman spectra of LLTS are presented in Fig. 3a and b, respectively. The vibrational band assignment was based on the results of a previous study on interpretation of the vibrational spectra of Llys, pTS and their complexes [7, 22-25]. The observed bands and assignments are given in Table 2. The bands of intermolecular hydrogen bonding generally appear at 3550-3200cm-1 [26]. In our study, the very strong broad band at 3451 cm-1 in the IR spectrum has been assigned to H-bonding stretching vibrations. The stretching vibration of detached N-H bond customarily located at 3500-3300 cm-1 [27], while there is a distinct strong and broad absorption band at 3068-3262 cm-1. The corresponding bands of NH2 shift to lower wavenumber, which may be attributed to the influence of protonation and hydrogen bond [28]. The strong peak at 3262 cm-1 in the IR spectrum shows the presence of NH3+ asymmetric stretching vibration. The symmetric stretching of NH3+ produces peak at 3068 cm-1 in the Raman spectrum as a strong line. The very strong absorption band due to NH3+ asymmetric scissoring occurs at 1642 cm-1, while the symmetric scissoring of NH3+ appears at 1506 cm-1 in the IR spectrum. The twisting, rocking and wagging vibrations of NH3+ are observed in the IR spectrum at 1332, 1175 and 848 cm-1, respectively. In aromatic compounds, the CH3 asymmetric stretching vibrations are expected in the range 2925-3000 cm-1 and symmetric CH3 vibrations in the range 2905-2940 cm-1 [29, 30]. Therefore, 4

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3.3 NMR spectrum

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the bands at 2948 and 2912 cm-1 in the Raman spectrum are assigned to CH3 asymmetric and symmetric stretching, respectively. The other bands such as 3028, 2984, 2875, 2931 and 2865 cm-1 are assigned to the CH and CH2 asymmetric and symmetric stretching, which include the CH stretching of aromatic ring [31]. The CH3 and CH2 scissoring vibrations is observed at 1468 and 1443 cm-1 in the IR spectrum respectively [30], while the CH scissoring vibration is located at 1384 cm-1 as a weak line in the Raman spectrum. The Raman band occurs at 956 cm and the IR band at 951cm are assigned to the CH3 rocking modes. The CH rocking and twisting vibration modes appear as weak peaks in IR spectrum at 1312 and 734 cm-1, respectively. The bands at 1312 and 813 cm-1 in IR spectrum are assigned to CH2 twisting and rocking vibrational modes, respectively. The aromatic CH rocking vibrational is identified at 1357 cm-1 in IR spectrum and 1359 cm-1 in Raman spectrum, respectively. It is well known that the carboxyl group has characteristic infrared bands: O-H stretching around 3500 cm-1, C=O stretching at 1700-1780 cm-1, COO- asymmetric stretching at 1550-1610 cm-1 and symmetric stretching at 1300-1420 cm-1 [32]. For the title complex, the IR bands of COO- asymmetric and symmetric stretching are observed at 1582 and 1400 cm-1 as strong and medium lines respectively. The C-O asymmetric and symmetric stretching produce peaks at 1220 and 1213 cm-1, respectively. The strong peaks at 1124 and 1006 cm-1 in the IR spectrum are due to the SO3 asymmetric and symmetric stretching vibration modes, respectively [24]. The corresponding bands in the Raman spectrum respectively occur at 1124 and 1012 cm-1. The strong bands at 682 and 565 cm-1 in the IR spectrum are due to the SO3 scissoring vibration. The C-C, C-N, and C-C-N stretching vibration bands are observed at 1058 cm-1 in Raman, 917 and 888 cm-1 in IR, respectively. The C-N wagging vibration band is located at 427 cm-1 in the IR spectrum and at 430 cm-1 in the Raman spectrum, respectively.

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The 1H-NMR and 13C-NMR spectral analyses are the two important analytical techniques used to the study the structure of organic compounds. The chemical shift scale can be roughly divided into regions that correspond to specific chemical environments. The 1H-NMR and 13 C-NMR spectra of LLTS in D2O are shown in Figs. 4 and 5 respectively, the atom numbering see Fig. 2a. In the 1H-NMR of LLTS (Fig. 4), the signals at 2.918-2.968 and 3.665-3.706 ppm are assigned to the protons of C13 and C9 from Llys, respectively. The proton signals of C10, C11 and C12 are split into a multiplet due to the influence of the adjacent CH group, which were confirmed centered at 1.645, 1.413 and 1.820 ppm, respectively. The proton signals of two amino from Llys cation are disappear in the spectrum, due to fast deuterium exchange which took place in two groups. The solvent H2O in D2O produces an intense signal at 4.700 ppm. The proton signals at 7.290 and 7.620 ppm are split into doublet of doublet owing to the splitting of neighboring protons, which are attributed to the aromatic ring. The signal at 2.327 ppm is assigned to the three protons of methyl group from the pTS. In the 13C-NMR of LLTS (Fig. 5), the signal at 174.491 ppm in the down field region is assigned to the carboxylic carbon (C8). The chemical shifts of C9, C10, C11, C12 and C13 from Llys are confirmed at 54.507, 26.384, 21.434, 29.866 and 39.083 ppm, respectively. The six signals observed for six types of carbons clearly confirm Llys purity. The presence of the signals at 125.369-142.507 ppm is attributed to the six carbons of the aromatic ring. Since the C2 and C6 are chemically equivalent atoms, as well as C3 and C5, which give their signals at 125.369 and 129.471 ppm, respectively. The signal at 20.499 ppm is 5

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3.4 Transmittance and absorption spectra

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attributed to the Para methyl carbon to sulfo aromatic ring (C7). The 1H-NMR and 13C-NMR chemical shifts of Llys molecular in different Llys salts are tabulated with the assignments in Tables 3. The 13C-NMR chemical shifts of Llys in three crystals have no significant difference, which indicate that the conformations of Llys in three crystals are similar. Relative to L-lysine monohydrochloride dehydrate (LLMHCl) crystal [33], the proton chemical shifts of L-lysine in LLNP and LLTS crystals are both shift to downfield [16]. L-arginine has the same carboxyl, α-amino and carbon chain as L-lysine, the only difference is that the guanidine group replaced the terminal amino group of L-lysine. In L-arginine salt crystals[12, 34], the main proton chemical shifts of L-arginine are shift to downfield, while the chemical shifts of hydrogen atoms nearly the guanidine are shift to upfield. Therefore, in L-arginine salt crystals, due to the guanidine, the protons chemical shifts of L-arginine at both ends had the different change trends, which should be the main reason for L-arginine with multiple conformations.

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To determine the optical transmission range and hence to know the suitability of LLTS single crystals for optical applications, the transmittance spectrum of the LLTS crystal was recorded from UV to NIR in the wavelength range of 250-2500 nm at room temperature. Fig. 6 gives the recorded optical transmittance spectrum of grown crystal in which characteristic UV cut-off wavelength of LLTS crystal occurs at around 280 nm. The wide optical transmission window is an encouraging optical property seen in LLTS crystal and is of vital importance for optical materials. The optical absorbance was recorded in the wavelength range of 200-1100 nm using a Unico UV-2102-PC spectrophotometer at room temperature. Fig. 7 shows the absorption spectrum of LLTS single crystal along with Tauc’s plot. The thickness of the sample used for measurement was 1 mm. The absorbance was reduced drastically from 280 to 1100 nm due to its good optical behavior. Using Tauc’s relation [35], the energy (hν) vs. (αhν)2 plot has been drawn (where α is the absorption coefficient) and the energy band gap is found to be 4.12 eV. This energy band gap is quite high for a transparent single crystal, shows that LLTS crystal has excellent transparency.

3.5 Thermal properties

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Thermo gravimetric (TG) and differential thermal analyses (DTA) give information regarding phase transition, and different stages of decomposition of the crystal. The thermal analysis of LLTS crystal was carried out from 30 to 650 °C at a heating rate 10 °C·min-1 in nitrogen ambient. The simultaneous TG/DTA thermograms of LLNP are presented in Fig. 8. From the TG thermogram, it is observed that, the compound starts to melt around 240 °C. Thus, it is quite interesting and important point that the good thermal stability of the LLTS crystal up to 240 °C. The mass loss from 240 to 293 °C is equal to 12.8 % which corresponds to the loss of CO2. In the DTA thermogram, the first endothermic peak at 259 °C corresponds to melting point of the substance, which may be attributed to utilization of energy to break the three-dimensional steric structure of the crystal. Below the melting point there is no endothermic or exothermic peak, which illustrates the absence of isothermic transition in LLTS crystal. The followed sharply mass loss about 61.0% appears between 293 and 383 °C. During the stage, the second endothermic peak occurred at 332 °C corresponds to the full decomposition of the compound, which is assigned to the release of gas molecules like CO, SO2 etc. After 383 °C, there is decomposition, illustrated by the loss of mass, where much more volatile substance like NH3 and CO might be liberated. 6

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3.6 NLO propertiesexperimental and computational

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Remaining 10 % charred as carbon and hydrogen molecules and may be treated as residue. Based on the results of TG and DTA, LLTS crystal is thermally stable up to 240 °C, which is much higher than other Llys salt crystals such as L-lysine trifluoroacetate (LLTF) (215.7 °C) [15] and L-lysine hydrochloride dehydrate (LLHCD) at 77.1 °C [36]. The excellent thermal stability should be attributed to the pTS is a strong anionic connector and water molecular absence in crystal structure [17].

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The SHG experiment was carried out using powder technique. The LLTS crystal powder samples were irradiated at 1064 nm by a Nd:YAG laser, and the green light (at 532 nm) was observed. From these measurements it is observed that the SHG efficiency of LLTS crystal is relatively poor, that is about 0.2 times that of KDP crystal. LLTS crystal contains Llys cation and pTS anion, and whose single crystal structure and molecule spectroscopy results have shown that there are strong hydrogen bonds located between the two charged groups. For investigating the different contributions of the two groups on hyperpolarizibility of the crystal, the three geometry models were established: Llys cation, pTS anion and LLTS. Before calculating the hyperpolarizabilities of three geometry models, those were treated as isolated molecules (gas). In the hyperpolarizability calculations, as for the widely existing ionic interactions, the geometric optimizations have not been performed in the case of any possible structural deviations from model to model [37]. In the presence of an applied electric field, the first order hyperpolarizibility is a third rank tensor that can be described by a 3 × 3 × 3 matrix. The 27 components of 3D matrix can be reduced to 10 components due to Kleinman symmetry [38]. The calculated values of first-order hyperpolarizibility are tabulated in Table 4. The calculated first-order hyperpolarizability value of LLTS is 4.44 × 10-28 esu, while for Llys cation and pTS anion, the first-order hyperpolarizabilities are 7.03× 10-30 and 4.87 × 10-30 esu, respectively. The interaction between the positive and negative ions is strong enough to make a contribution to first-order hyperpolarizability values of LLTS. The first-order hyperpolarizability value of LLTS is nearly 1660 times that of urea [39]. However, the actual powder SHG efficiency of LLTS crystal is relatively low. This phenomenon should be attributed to the opposite orientation of adjacent LLTS molecule in crystal structure, which makes the polarity of LLTS molecule offset in crystal. Thus, the NLO properties of crystal not only depend on first-order hyperpolarizability value of molecule, but the arrangement of molecules in crystal structure also plays an important role.

4. Conclusions

A novel amino salt, LLTS crystal has been grown by slow cool technique from an aqueous solution. Single crystal XRD technique confirmed that it belongs to orthorhombic system with the space group P212121. The FT-IR and Raman spectra studies have analyzed the vibrational frequencies corresponding to various functional groups in the crystal. The 280 nm cutoff wavelength and good transmittance have been determined from the UV-Vis-NIR transmittance spectrum. The TG/DTA studies have indicated that the crystal is fairly thermally stable up to 240 °C. The second-order NLO properties of LLTS crystal were demonstrated by powder SHG experiment and also by quantum chemical calculations. The first-order hyperpolarizability value 7

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of LLTS molecule were found to be 4.44 × 10-28 esu employing the GAUSSIAN 03W program at the B3LYP/6-31g(d, p) basis set. Due to the reverse arrangement of adjacent LLTS molecules in crystal structure, the powder SHG efficiency of LLTS crystal is relatively low and very different from theoretical calculation results.

Acknowledgements

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This work was supported by National Natural Science Foundation of China (No. 50872067), the SRF for ROCS, SEM and the Youth Scientist Fund of Shandong Province (BS2011CL025), Natural Science Foundation of Shaanxi Province (No.2015JM6327) and Provincial College Students’ Training Programs for Innovation and Entrepreneurship of Shaanxi province (1322).

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Figure captions

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Fig. 1. Photograph of grown LLTS crystals. Fig. 2. (a) Molecular structure with atom numbering and (b) perspective viewed along the a-axis. Fig. 3. (a) FT-IR and (b) Raman spectra of LLNP crystal. Fig. 4. 1H- NMR spectrum of LLTS. Fig. 5. 13C-NMR spectrum of LLTS. Fig. 6. UV-Vis-NIR transmittance spectrum of LLTS crystal. Fig. 7. Optical absorption spectrum of LLTS single crystal along with Tauc’s plot. Fig. 8. TG and DTA thermograms for LLTS crystal.

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Photograph of grown LLTS crystals

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Fig. 2. (a) Molecular configuration with atom numbering and (b) perspective viewed along the a-axis.

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Fig.3 (a) FT-IR and (b) Raman spectra of LLNP crystal.

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H- NMR spectrum of LLTS.

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Fig.4

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13

C-NMR spectrum of LLTS.

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Fig. 5

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UV-Vis-NIR transmittance spectrum of LLTS crystal.

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Fig. 6

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Optical absorption spectrum of LLTS single crystal along with Tauc’s plot.

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Fig. 7

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TG and DTA thermograms for LLTS crystal.

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Fig. 8

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Table captions Table 1 Crystal data and structure refinement for LLTS. Table 2 FT-IR and Raman vibrational spectral data and their assignments for LLTS crystal.

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Table 3 Chemical shifts (1H, 13C) of L-lysine molecular in several L-lysine salts. Table 4 First-order hyperpolarizabilities (β) of LLTS, Llys cation and pTS anion.

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Table 1 Crystal data and structure refinement for LLTS. LLTS

Empirical formula

C13H22N2O5S

Formula weight

318.39

Temperature

293(2) K

Wavelength

0.71073 Å

Crystal system, Space group

Orthorhombic, P212121

Unit cell dimensions

a = 5.3464(4) Å

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b = 15.3387(13) Å

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Identification code

c = 18.5276(15) Å 1519.4(2) Å3

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M AN U

Volume

4

1.392 Mg/m3

Density (calculated)

0.236 mm-1

Absorption coefficient F(000)

680

0.25 × 0.23 × 0.08 mm3

Crystal size

Index ranges Reflections collected Independent reflections Completeness to q= 27.38°

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Refinement method

1.72 - 27.38°

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Theta range for data collection

-6 ≤ h ≤ 6, -16 ≤ k ≤ 19, -23 ≤ l ≤ 23

9299 3401 [R(int) = 0.0215] 99.70 % Full-matrix least-squares on F2 3401/0/216

Goodness-of-fit on F2

1.033

Final R indices [I>2s(I)]

R1 = 0.0332, wR2 = 0.0874

R indices (all data)

R1 = 0.0391, wR2 = 0.0915

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Data / restraints / parameters

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Table 2 FT-IR and Raman vibrational spectral data and their assignments for LLTS crystal. FT-Raman (cm-1)

Mode assignments

3451vsb 3262s

2945w 1642vs 1582ssh 1506m 1468wsh 1443w 1400m

1384w 1359w

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1478w, 1464w 1443m

1308w 1228wsh 1213m 1186w, 1171w 1124vs 1058w 1037m 1012m 956w

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1357w 1332w 1312w 1220s

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1175s 1124s 1035m 1006m 951w 917vw 888w 848w 813m 796wsh 734w 682s 639w 565s 501m 427w

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3068s 2984m, 2865m 2948m 2912s 1646vw 1581wsh

ν(H-bonding) νas(NH3+) νs(NH3+) ν(CH) + ν(CH2) νas(CH3) νs(CH3) δas(NH3+) νas(COO-) δs(NH3+) δ(CH3) δ(CH2) νs(COO-) δ(CH) ρ(CH)ring τ(NH3+) ρ(CH) νas(C-O) νs(C-O) ρ(NH3+) νas(SO3) ν(C-C) ν(C-S) νs(SO3) δ(C-H)

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FT-IR (cm-1)

803vs

ν(C-N) ν(C-C-N) ω(NH3+) ρ(CH2) δ(CO)

684w 637s 576w,555w 503w 430w

τ(CH) δas(SO3) + ν(C-S) ρ(C-O) δs(SO3) +δ(C-C-C) ρ(C-C-C) ω(C-N)

853m

s - strong, w - weak, v - very, sh - shoulder, b - broad, m - medium, ν- stretching, s - symmetric, as - antisymmetric,

δ-

scissoring (symmetric in-plane), ρ - rocking (antisymmetric in-plane), ω - wagging (symmetric out-of-plane), τ - twisting (antisymmetric out-of-plane).

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Table 3 Chemical shifts (1H, 13C) of L-lysine molecular in several L-lysine salts. C10-H

C11-H

C12-H

C13-H

C8

C9

C10

C11

C12

C13

LLMHCl[30]

3.6

1.7

1.3

1.5

2.9

174.7

54.5

26.8

21.8

29.8

39.0

LLNP[16]

3.64

1.78

1.40

1.63

2.93

175.12

54.60

26.43

21.46

30.14

39.08

LLTS

3.68

1.82

1.41

1.64

2.94

174.49

54.50

26.38

21.43

29.86

39.08

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C9-H

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Table 4 First-order hyperpolarizabilities (β) of LLTS, Llys cation and pTS anion.

Llys cation

pTS anion

βxxx

25.17

-0.85

-0.59

βxxy

-93.49

-0.75

0.53

βxyy

12.41

-0.22

-0.41

βyyy

-100.83

-3.37

2.61

βxxz

-133.00

-0.12

-0.44

βxyz

-7.14

-0.31

0.18

βyyz

-35.48

-0.57

-1.00

βxzz

-43.39

-0.45

0.00

βyzz

-30.76

-2.34

βzzz

-214.25

-1.63

βtot

444.05

7.03

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LLTS

0.86

-1.15 4.87

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Hyperpolarizability β (−2ω, ω,ω) in 10

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−30

esu.

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Highlights 1. A novel amino salt crystal has been grown by slow cool technique from an aqueous solution. 2. Good transparency and optical band gap of LLTS crystal has been found from transmittance and absorption spectrum. 3. The melting point of LLTS crystal is fairly high, at around 259 °C.