Journal of the Indian Chemical Society 100 (2023) 101020

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Journal of the Indian Chemical Society

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Computational, structural, spectral, optical and Hirshfeld surface analysis

of (E)-2-(3,4,5-trimethoxybenzylidene) hydrazinecarbothioamide
(ETMBHC): Third order NLO single crystal
S. Sathiya a, *, R.R. Saravanan b, M. Shaik Abdul Khader c, V. Porkalai d
a
Department of Physics, Arasu Engineering College, Kumbakonam, Tamil Nadu, 612 501, India
b
Department of Physics, Meenakshi Chandrasekaran College of Arts and Science, (Affiliated to Bharathidasan University, Tiruchirapalli), Karambayam, Pattukkottai,
Thanjavur, Tamil Nadu, 614 626, India
c
Department of Mechanical Engineering, Annai College of Engineering and Technology, Kovilacheri, Kumbakonam, Thanjavur, Tamil Nadu, 612 503, India
d
Department of Physics, Nethaji Subash Chandra Bose Arts and Science College, Mahatma Gandhi Nagar, Senthamangalam, Thiruvarur, Tamil Nadu, 610001, India

A R T I C L E I N F O A B S T R A C T

Keywords: By using a slow evaporation solution growth technique, single crystals of (E)-2-(3,4,5-trimethoxybenzylidene)
XRD hydrazine carbothioamide (ETMBHC) have been produced. The crystalline compound has the following prop­
FTIR erties: a = 7.471 (3), b = 9.705 (4), c = 11.168 (4), = 73.200(11)◦ , = 70.633 (10)◦ , = 70.334 (10)◦ ; it belongs to
FT-Raman
the triclinic system with space group P. The ETMBHC chemical is a member of the P-1 triclinic system. Fourier
NLO
transformations and Fourier transform infrared (FT-IR) The functional groups have been identified by Raman
Z-Scan
TGA spectrum research. To understand how charge transfer occurs inside molecules and to establish that the title
DFT crystal is appropriate for NLO applications, the HOMO and LUMO energies for the grown crystal were computed.
TGA-DTG analysis was used to study the melting point and thermal stability. Z-scan analyses were used to
determine the grown crystal’s nonlinear absorption coefficient and third-order nonlinear refractive index.

1. Introduction Because thiosemicarbazones react with a wide variety of metals, they

can exhibit both hard (N) and soft (A) donor ligands [7]. These sub­
The design and synthesis of effective nonlinear optically NLO active stances have also been used in the production of pharmaceutical and
materials have received a lot of attention from researchers in the current bioactive materials [8,9]. Most areas of chemistry, including medicinal
technological era due to their multimodal practical applications in chemistry, make substantial use of thiosemicarbazones. These kinds of
telecommunication, optical limiting, optical switching, optical data substances also function as multi-dentate chelating agents with high
storage, and photoelectronic devices [1]. Typically, organic materials affinity for a range of transition metals [10].
are better NLO materials than inorganic ones because they are less In this study, the crystal structures of (E)-2-(3,4,5-trimethox­
expensive, have larger optical nonlinearities, are structurally extensible, ybenzylidene) hydrazinecarbothioamide (ETMBHC) are synthesized,
have ultra-fast optical response times, and are simpler to fabricate [2,3]. crystallized, and determined. The crystal structures are then compre­
The most potential third-order NLO material candidates are often hensively described using the FT-IR, FT-Raman, DFT, TG/DTA, UV–Vi­
thought to be organic materials since they are inexpensive, relatively sible, and Z-scan methods. The outcomes that were seen are thoroughly
cheap to synthesize, adaptable, and tailorable [4]. As a result of described and explained.
increased electronic delocalization in metal complexes, the materials
may be coupled with metal ions to create complexes, further enhancing 2. Experimental
and altering third-order NLO performance [5]. When external physical
light variables change, organic third-order NLO materials containing Thiosemicarbazide and 3,4,5-trimethoxybenzaldehyde were com­
photosensitive groups may undergo structural changes that might bined in a 1:1 M ratio. 40 mL of ethanol and 0.7 g of thiosemicarbazide
modify their third-order NLO capabilities [6]. (0.0076 mol) were introduced to a flask with a flat bottom. 10 mL of an

* Corresponding author.
E-mail address: [email protected] (S. Sathiya).

https://doi.org/10.1016/j.jics.2023.101020
Received 11 October 2022; Received in revised form 16 February 2023; Accepted 4 May 2023
Available online 21 May 2023
0019-4522/© 2023 Indian Chemical Society. Published by Elsevier B.V. All rights reserved.
S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Table 1
Crystal Data and Refinement details of ETMBHC.
Formula weight 287.33

Temperature 296(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 7.471(3) Å, b = 9.705(4) Å, c = 11.168(4) Å
α = 73.200(11)◦ . β = 70.633(10)◦ . γ = 70.334
(10)◦ .
Volume 704.8(5) Å3
Z 2
Density (calculated) 1.354 Mg/m3
Absorption coefficient 0.243 mm− 1
F(000) 304
Crystal size 0.200 × 0.150 × 0.150 mm3
Theta range for data collection 2.274–24.997◦ .
Index ranges − 8 ≤ h<=8, − 11 ≤ k<=11, − 13 ≤ l<=13
Reflections collected 13725
Independent reflections 2464 [R(int) = 0.0622]
Completeness to theta = 99.50%
24.997◦
Max. and min. transmission 0.7437 and 0.5437
Data/restraints/parameters 2464/7/195
Goodness-of-fit on F2 1.186
Final R indices [I > 2sigma(I)] R1 = 0.1024, wR2 = 0.3116
R indices (all data) R1 = 0.1143, wR2 = 0.3258
Largest diff. peak and hole 1.439 and − 0.400 e.Å− 3

Fig. 1. Schematic diagram of ETMBHC. Table 2

Hydrogen bonds for ETMBHC [Å and ◦ ].
ethanolic solution containing 1.5 g of 3,4,5-trimethoxybenzaldehyde D-H … A d(D-H) d(H … A) d(D … A) <(DHA)
(0.0076 mol) was added to this solution, and the mixture was well
C(9)-H(9A) … S(1)#1 0.96 3.02 3.903(7) 153.8
agitated for an hour while being kept on a magnetic stirrer. One hour C(10)-H(10C)⋯O(3) 0.96 2.54 3.076(9) 115.6
later, a rough solid was produced (Fig. 1). This undeveloped solid was N(2)-H(2A) … O(4) 0.85(2) 2.06(2) 2.902(7) 171(6)
washed with water two to three times, dried, and then washed with N(3)-H(3A) … O(2) #2
0.84(2) 2.30(4) 3.049(7) 149(6)
#3
diethyl ether before being stored for two days under vacuum. Thin Layer N(3)-H(3B)⋯S(1) 0.85(2) 2.59(3) 3.407(6) 162(7)
#4
O(4)-H(4A) … S(1) 0.85(2) 2.51(3) 3.352(6) 169(8)
Chromatography was used to determine the composition’s purity (TLC). O(4)-H(4B)⋯O(1)#5 0.85(2) 2.27(6) 2.988(6) 142(8)
Using the slow evaporation solution growth method, the crude sample Symmetry transformations used to generate equivalent atoms:
was recrystallized from ethanol. #1 x-1,y,z+1 #2 -x,-y+1,-z+1 #3 -x+1,-y+2,-z #4 -x+2,-y+1,-z #5 x+1,y,z-1

3. Characterization details

Utilizing the NETZSCH STA 449 F3 Jupiter, Thermogravimatric -

Differential Thermal Analysis measurements were performed. Using a
PerkinElmer FT-IR spectrometer and the KBr pellet technique, an FT-IR
spectrum was captured in the 4000-400 cm− 1 region to identify the
different functional groups contained in the ETMBHC crystal. FT-Raman
measurements were conducted using an Nd-YAG laser source with a
wavelength of 1064 nm and an InGaAs detector, with the results being
recorded using a Thermo electron company USA Nexus 670 spectrom­
eter. Using a SHIMADZU 1800 UV–Vis spectrometer, the ETMBHC
crystal’s UV–Visible spectrum was captured between 190 and 800 nm.
The third-order nonlinearity of the ETMBHC crystal, using the Nd: YAG
laser utilized as the laser source at a wavelength of 532 nm was deter­
mined using the Z-scan method. On an Enraf Nonius CAD4-MV31 single-
crystal X-ray diffractometer outfitted with CuK radiation (= 1.5418), the
diffraction data from a chosen single crystal of ETMBHC were obtained
at ambient temperature.
Fig. 2. ORTEP diagram of ETMBHC.
4. Computational details

was used for data reduction and cell refinement [14]. With the aid of
The optimized geometry was obtained using quantum chemical
SHELXS-97 [15] and SHELXL-97 [16], the crystal structure was directly
calculations, the HOMO-LUMO performed with the Gaussian-09W [11]
solved, and the refinement was carried out using complete matrix least
software, taking the Becke3-Lee-Yang-Parr (B3LYP) functional together
square data fitting. There were no gaps in the crystal lattice that might
with the B3LYP/6–31++G(d,p) basis set [12]. To create visual pre­
have been accessed by solvents, as shown by PLATON’s [17,18] analysis
sentations and confirm the normal mode assignments, the GaussView05
of the structure. The Crystal Explorer tool was used to analyze Hirshfeld
application [13] was used. Respective the crystal composition SAINT
surfaces [19].

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S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Fig. 3. Hydrogen bonding diagram of ETMBHC.

Fig. 4a. b,c dnorm, Curvedness and Shapeindex of ETMBHC.

5. Result & discussion [20] to see intermolecular interactions and determine the function of the
organic base in structure propagation.
5.1. Single crystal X-ray diffraction studies The following equation represents the normalized contact distance
dnorm based on di (nearest nucleus internal to the surface) and de
The crystalline nature and lattice characteristics of the generated (nearest nucleus external to the surface).
ETMBHC crystal were confirmed by single-crystal X-ray diffraction
analysis. C11H17N3O4S is the empirical formula for ETMBHC. ETMBHC dnorm = di – rivdW/ rivdW + de – revdW/ revdW
has a molecular weight of 287.33. Tables 1 and 2 provide an overview of where the van der Waals radii of two atoms that are internal and exterior
crystal data, data collecting settings, reliability factor, and hydrogen to the molecular surface are rivdW and revdW, respectively. Hirshfeld
bonding tables. The grown ETMBHC crystals’ molecular structure surface analysis combined with 2D fingerprint plots allows for the
(ORTEP) is shown in Fig. 2. Fig. 3 depicts the hydrogen bonding diagram quantification of the intermolecular interactions in the ETMBHC crys­
for the ETMBHC. tals. The molecular Hirshfeld surfaces over dnorm, curvedness and
The ETMBHC crystallises under the Triclinic system, with lattice shapeindex are shown in Fig. 4a,b,c. The bright red regions on the
parameters a = 7.471(3), b = 9.705(4), c = 11.168(4), α = 73.200(11)◦ , Hirshfeld surface are the hydrogen bond acceptors. About 44.8% of in­
β = 70.633(10)◦ , γ = 70.334(10)◦ , and volume of the unit cell V = 704.8 teractions are between H and H. Fig. 5 shows the two-dimensional
(5)3 with the space group P-1, according to single-crystal X-ray fingerprint plots for the ETMBHC crystal, individually emphasizing the
diffraction examinations. The ETMBHC has a density of 1.354 Mg/m3, H⋯S, C⋯H, and H⋯H intermolecular interactions, which are respec­
and Z = 2. The ETMBHC’s Goodness of Fit (S) value is 1.186. For tively around 15.4%, 9.2% and 44.8%.
structural solution and refinement, a total of 13725 reflections (2464
distinct reflections, Rint = 0.0622) were combined. 0.7437 and 0.5437
are the greatest and lowest transmission factors, respectively. 99.5% of 5.3. Molecular geometrical analysis
the data is complete.
Table 3 lists the ETMBHC crystal’s optimal structural characteristics.
For comparison, the equivalent results from SCXRD (Single Crystal X-
5.2. Hirshfeld surface analysis Ray Diffraction) investigations are also provided. The intermolecular
electrostatic interactions in the crystalline state are most likely the cause
The Crystal Explorer tool [21] was used to analyze Hirshfeld surfaces of some variation in the estimated geometric parameters from the

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S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Fig. 5. 2D fingerprint plot of ETMBHC.

Table 3
Comparison of experimental and theoretical geometry.
Bond Length XRD Ref [27] DFT Bond Length Ref [27] XRD DFT

C(1)–C(6) 1.394(8) – 1.394 C(4)–C(5) 1.383(3) 1.406(8) 1.413

C(1)–C(2) 1.408(8) 1.389(2) 1.405 C(5)–O(3) – 1.367(7) 1.369
C(1)–C(7) 1.468(7) – 1.461 C(5)–C(6) – 1.387(8) 1.401
C(2)–C(3) 1.378(8) 1.391(3) 1.390 C(7)–N(1) – 1.276(7) 1.285
C(3)–O(1) 1.377(7) 1.363(19) 1.372 C(8)–N(3) – 1.313(8) 1.367
C(3)–C(4) 1.398(8) 1.400(3) 1.424 C(8)–N(2) – 1.352(7) 1.375
C(4)–O(2) 1.372(6) 1.372(2) 1.368 C(8)–S(1) – 1.694(6) 1.669
C(11)–O(3) 1.424(8) – 1.431 C(9)–O(1) 1.424(2) 1.422(8) 1.425
N(1)–N(2) 1.377(6) – 1.357 C(10)–O(2) 1.425(3) 1.442(8) 1.437
Bond Angle XRD DFT Bond Angle XRD DFT
C(6)-C(1)-C(2) 119.9(5) – 119.229 C(6)-C(5)-C(4) – 119.4(5) 120.049
C(6)-C(1)-C(7) 119.2(5) – 119.425 C(5)-C(6)-C(1) – 120.6(5) 121.328
C(2)-C(1)-C(7) 121.0(5) – 121.340 N(1)-C(7)-C(1) – 120.1(5) 121.928
C(3)-C(2)-C(1) 119.6(5) – 120.183 N(3)-C(8)-N(2) – 117.2(5) 114.625
O(1)-C(3)-C(2) 124.2(5) – 122.521 N(3)-C(8)-S(1) – 122.8(5) 121.959
O(1)-C(3)-C(4) 115.1(5) – 116.346 N(2)-C(8)-S(1) – 120.0(4) 121.416
C(2)-C(3)-C(4) 120.7(5) – 121.133 C(3)-O(1)-C(9) – 117.0(5) 118.562
O(2)-C(4)-C(3) 119.0(5) – 126.086 C(4)-O(2)-C(10) – 115.6(5) 115.789
O(2)-C(4)-C(5) 121.1(5) – 115.836 C(5)-O(3)-C(11) – 117.1(4) 118.230
C(3)-C(4)-C(5) 119.9(5) – 118.078 C(7)-N(1)-N(2) – 116.1(5) 117.140
O(3)-C(5)-C(6) 124.9(5) – 123.976 C(8)-N(2)-N(1) – 119.2(5) 120.429

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S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

the calculated and experimental values of C–C bonds.

The estimated value for the bond length of N1–N2 is 1.357 Å whereas
the experimental value is 1.377 Å. The found deviation is 0.01 9. The
bond angles of C6–C1–C2, C6–C1–C7, C2–C1–C7, C3–C2–C1,
C2–C3–C4, C3–C4–C5, C6–C5–C4, and C5–C6–C1 are estimated as
119.9, 119.2, 121.0, 119.6, 120.7, 119.9, 119.4, and 120.6◦ , respec­
tively, while the bond angles of O1–C3–C2, O1–C3–C4, O2–C4–C3, and
O2–C4–C5 are 122.5◦ , 116.3◦ , 126.0◦ , and 115.8◦ , respectively.
Compared to the experimental value, e,g., we see reveals a 2.26◦ dif­
ference in O2–C4– C5.

5.4. Vibrational assignments

Aliphatic compounds exhibit C–H stretching bands between 3000

and 2850 cm− 1. O–H stretching vibrations are responsible for the
wavelength that is generated between 3700 and 3600 cm− 1. In general,
N–H stretching is seen between 3400 and 3300 cm− 1. O–H, C–H, and
N–H stretching are often responsible for the basic vibrations from the
4000–2500 cm− 1. Figs. 6 and 7 depict the predicted and experimental
FT-IR and FT-Raman spectra, respectively. Table 4 lists the theoretical
Fig. 6. Experimental and Theoretical spectrum of FT-IR. and experimental vibrational wavenumbers (cm− 1) of the ETMBHC
crystal as determined by B3LYP/6–31++G(d,p). The Scaling factor is
experimental SCXRD data. The ETMBHC molecule’s C7–N1, C8–N3, and 0.952.
C8–N2 bond lengths are determined at 1.276, 1.1313, and 1.352 Å,
respectively. the computed bond lengths are 1.285, 1.367, and 1.375 Å. 5.4.1. C–H stretching vibration
The standard variation of the C–N bond length is 0.0285 on average. The heteroaromatic organic compounds and their derivatives have a
The average C–O bond length of the ETMBHC molecule as deter­ structure that is very similar to that of benzene and typically exhibit
mined by experimental data and B3LYP calculations using the 6–31++G multiple weak bands in the range of 3100 to 3000 cm− 1, which is the
(d,p) basis set is 1.4006 Å, 1.4002 Å, respectively. Similar to C1–C6, region that is characteristic of the complete identification of C–H
C1–C2, C1–C7, C2–C3, C3–C4, C4–C5, and C5–C6 of the ETMBHC stretching vibrations. These vibrations are not found to be impacted by
molecule, the experimental bond length values are 1.394, 1.408, 1.468, the type and position of the substituent [22,23].
1.378, 1.398, 1.406, and 1.38 7. C–C bonds have an average experi­ The C–H stretching vibrations of the ETMBHC were attributed to the
mental value of 1.4055 Å. A 0.006 Å difference was discovered between wavenumbers determined by B3LYP/6–31++G(d,p) at 2998 and 2947
cm− 1. C–H stretching vibrations were assigned to the two detected bands

Fig. 7. Experimental and Theoretical spectrum of FT-Raman.

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S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Table 4
Theoretical and Experimental vibrational wavenumbers (cm− 1) of ETMBHC crystal calculated by B3LYP/6–31++G(d,p).
S. Exp. IR (cm− 1) Exp. Raman (cm− 1) Theo. Freq. (Scaled) (cm− 1) Reduced Mass Force const. IR Intensity Raman Intensity Depolar (P) Depolar (U)
No

1 – – 23.11113 7.2741 0.0025 5.027 1.5965 0.75 0.8571

2 – – 39.96039 5.0737 0.0053 4.3742 0.7099 0.7478 0.8557
3 – – 41.35402 6.8538 0.0076 7.1141 1.4022 0.3524 0.5212
4 – – 58.39482 3.4453 0.0076 3.5328 0.0207 0.75 0.8571
5 – – 83.04068 2.9332 0.0131 0.3871 0.0095 0.75 0.8571
6 – – 92.42102 5.9293 0.0329 0.059 0.3108 0.75 0.8571
7 – 116 114.8274 3.4277 0.0294 10.2277 0.4902 0.75 0.8571
8 – – 126.8985 5.1208 0.0536 9.4603 0.3412 0.75 0.8571
9 – – 136.0538 7.7793 0.0936 0.9315 7.0381 0.5807 0.7347
10 – – 173.9304 2.3785 0.0468 28.8354 4.3196 0.75 0.8571
11 – 190 185.0953 4.0253 0.0897 3.0585 1.614 0.3737 0.544
12 – 199 200.9267 1.9312 0.0507 13.4092 0.3479 0.75 0.8571
13 – 222 218.8017 3.6316 0.113 0.3548 0.4703 0.7431 0.8526
14 – – 228.8974 1.1475 0.0391 0.0065 1.7817 0.75 0.8571
15 – 234 235.3965 5.0253 0.181 3.2669 0.7587 0.2232 0.3649
16 – – 239.0218 1.1102 0.0412 0.0181 0.2745 0.75 0.8571
17 – 255 259.4051 1.982 0.0867 0.0416 0.1242 0.75 0.8571
18 – – 273.419 2.6642 0.1295 2.8188 0.102 0.75 0.8571
19 – 274 274.2504 1.2074 0.059 136.547 0.3386 0.75 0.8571
20 – 290 287.4608 4.2861 0.2302 0.2762 5.8406 0.1768 0.3004
21 – 326 324.578 4.3795 0.2999 0.7449 1.6111 0.5061 0.6721
22 – 365 362.1733 4.6646 0.3978 10.5268 12.1162 0.2547 0.4061
23 – – 370.0414 3.5461 0.3157 4.154 3.8925 0.75 0.8571
24 – – 386.3095 1.3812 0.134 77.8188 0.54 0.75 0.8571
25 – – 401.9235 4.5275 0.4755 8.0532 2.7666 0.1601 0.2761
26 – 426 421.1707 3.8053 0.4388 25.4093 1.0472 0.4789 0.6477
27 464 465 467.1305 5.8254 0.8264 2.79 14.232 0.1244 0.2212
28 492 494 491.4606 1.0559 0.1658 19.3015 0.8637 0.75 0.8571
29 – 516 513.9914 6.4123 1.1013 2.4138 3.4988 0.5442 0.7048
30 551 – 554.0811 4.608 0.9197 0.0077 0.7589 0.75 0.8571
31 – 577 575.6387 9.0087 1.9406 2.1538 2.0514 0.75 0.8571
32 – – 579.5757 6.5517 1.4307 0.847 9.4207 0.6209 0.7661
33 – – 583.113 4.5133 0.9976 5.1688 0.7359 0.7499 0.8571
34 634 631 634.6458 6.6595 1.7437 31.5783 5.7662 0.4832 0.6516
35 – – 665.3491 4.913 1.4139 1.1965 17.8014 0.174 0.2964
36 – – 666.4982 7.4462 2.1504 0.0856 0.7785 0.7499 0.8571
37 716 714 718.7677 5.2217 1.7537 12.2345 37.8466 0.0698 0.1304
38 771 769 772.7711 4.5068 1.7496 49.6685 11.1941 0.0996 0.1811
39 – – 807.3466 1.3199 0.5593 32.8925 0.4763 0.7499 0.8571
40 – – 818.4949 1.4256 0.6209 0.9237 0.0998 0.75 0.8571
41 – – 884.6386 6.7288 3.4233 17.6915 0.828 0.1212 0.2161
42 914 907 909.1718 1.5232 0.8185 17.446 6.5914 0.75 0.8571
43 – 943 949.6214 3.1391 1.8403 17.0701 15.9511 0.0342 0.0661
44 – – 980.0855 2.5231 1.5756 36.5557 42.6082 0.4892 0.657
45 994 995 991.5317 5.615 3.5887 30.1086 41.9972 0.2397 0.3867
46 – – 1029.783 3.5223 2.4282 54.9964 9.4497 0.7425 0.8522
47 1095 1100 1091.509 4.2004 3.2533 340.8225 31.758 0.32 0.4849
48 – – 1107.474 1.2511 0.9976 2.5008 3.1247 0.75 0.8571
49 – – 1110.016 1.2537 1.0042 0.0084 2.9733 0.75 0.8571
50 – – 1111.474 1.2659 1.0167 0.5916 0.6149 0.75 0.8571
51 – – 1113.237 2.5983 2.0934 21.6042 696.778 0.3039 0.4662
52 – – 1140.548 2.0614 1.7433 87.29 66.0069 0.3716 0.5419
53 – – 1146.699 1.4015 1.198 56.1769 14.1138 0.6749 0.8059
54 1157 1155 1157.72 1.7615 1.5348 28.9423 22.2891 0.6459 0.7849
55 – – 1164.664 1.678 1.4797 105.7046 13.1093 0.2578 0.4099
56 – 1196 1200.138 2.0531 1.9224 84.9998 5.1551 0.4841 0.6524
57 – – 1212.626 2.1543 2.0593 73.8042 19.0034 0.394 0.5653
58 1238 1236 1241.699 2.5222 2.5281 247.2068 10.3219 0.2967 0.4577
59 – – 1280.638 5.8373 6.2236 234.0197 252.271 0.2304 0.3745
60 1287 1285 1288.71 2.5289 2.7304 558.6605 145.984 0.2057 0.3412
61 1326 1323 1324.643 4.2616 4.8612 202.8483 29.5408 0.4236 0.5951
62 – – 1345.631 2.3526 2.7693 375.801 72.6553 0.2201 0.3608
63 1377 – 1381.337 2.2753 2.8223 126.5269 250.124 0.3616 0.5312
64 – – 1406.378 1.3074 1.6811 47.5898 9.3034 0.6605 0.7955
65 1418 1414 1416.154 1.3232 1.7251 31.0514 158.129 0.3417 0.5094
66 – – 1420.779 1.0498 1.3776 15.2453 22.2361 0.75 0.8571
67 – – 1423.147 1.0465 1.3778 2.3663 15.1104 0.7499 0.8571
68 – – 1423.207 1.3954 1.8374 7.0811 4.6194 0.1622 0.2791
69 – – 1424.005 1.0502 1.3844 4.7536 7.9563 0.75 0.8571
70 – – 1431.008 1.0655 1.4185 6.8585 11.2027 0.2724 0.4281
71 – – 1433.056 1.0484 1.3997 40.1167 6.0918 0.6432 0.7828
72 – – 1437.173 1.072 1.4395 72.935 4.8443 0.2967 0.4576
73 1455 – 1458.429 2.9955 4.1421 317.5128 12.342 0.3287 0.4948
(continued on next page)

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S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Table 4 (continued )
S. Exp. IR (cm− 1) Exp. Raman (cm− 1) Theo. Freq. (Scaled) (cm− 1) Reduced Mass Force const. IR Intensity Raman Intensity Depolar (P) Depolar (U)
No

74 – – 1501.236 1.887 2.7647 259.6721 40.1597 0.4084 0.58

75 1535 1537 1537.873 7.2742 11.184 157.5054 578.274 0.351 0.5196
76 – – 1552.848 1.2142 1.9034 200.9029 3.4699 0.6266 0.7704
77 1569 – 1564.307 5.5956 8.9016 5.8811 1539.96 0.3948 0.5661
78 – 1603 1604.11 7.69 12.863 5.2066 3265.43 0.317 0.4814
79 – – 2878.524 1.0858 5.8489 70.3315 78.872 0.3999 0.5714
80 – – 2882.207 1.0327 5.577 42.0475 130.665 0.0355 0.0685
81 – – 2907.672 1.0282 5.6512 100.7695 259.838 0.0294 0.0571
82 – – 2908.934 1.0278 5.6542 93.352 205.114 0.0525 0.0997
83 2945 2947 2947.446 1.1069 6.2513 27.0052 37.591 0.75 0.8571
84 – – 2986.041 1.1075 6.4197 30.8166 58.9762 0.75 0.8571
85 – – 2990.117 1.1072 6.4357 21.7259 116.532 0.6874 0.8148
86 – – 2990.196 1.1068 6.4337 24.6725 133.395 0.6785 0.8085
87 – – 2990.57 1.1077 6.4401 29.9589 64.8588 0.7499 0.8571
88 3006 3008 2998.943 1.1018 6.4421 23.4528 119.012 0.4737 0.6428
89 – – 3048.592 1.0905 6.5889 4.2194 78.655 0.3714 0.5416
90 – – 3091.676 1.0904 6.7759 3.6678 18.0323 0.1518 0.2636
91 – – 3300.225 1.075 7.6114 23.1797 426.653 0.1506 0.2618
92 3398 3393 3411.418 1.0476 7.926 60.2774 397.796 0.2281 0.3715
93 3555 3549 3557.704 1.1029 9.075 73.0993 95.1222 0.7451 0.8539

Table 5
HOMO-LUMO parameters of ETMBHC.
HOMO energy − 0.17398

LUMO energy − 0.26566

Frontier molecular orbital energy gap 0.09168
Ionization energy(I) − 0.17398
Global hardness(η) − 0.04584
Chemical potential(μ) − 0.21982
global Electrophilicity powerω − 0.52706

1
experimental findings from both FTIR spectra at 634, 716, and 771 cm−
and FT-Raman spectra at 631, 714, and 769 cm− 1.

5.4.4. C–O vibrations

Typically, the C–O stretching manifests as a significant absorption in
the range of 1260 to 1000 cm− 1 [25]. The band was detected in the
FT-IR spectra at 1095 and 1157 cm− 1 and in the FT Raman spectrum at
1100 and 1155 cm− 1. C–O vibration is attributed to the estimated values
at 1091 and 1157 cm− 1 in the B3LYP/6–31++G (d,p) technique.

5.5. Frontier molecular orbital (FMO) and ultra Violet‒Visible (UV–Vis)

spectral analysis
Fig. 8. HOMO LUMO diagram of ETMBHC.
The highest occupied molecular orbital (HOMO) and the lowest
in the FT-IR spectrum at 3006 and 2945 cm− 1 and one detected band in unoccupied molecular orbital (LUMO) are both referred to as Frontier
the FT-Raman spectrum at 3008 and 2947 cm− 1. Molecular Orbitals (FMOs). According to B3LYP/6–31++G(d,p) calcu­
lations for the gas phase, the HOMO-LUMO energies for the ETMBHC
5.4.2. N–H stretching vibration molecule are shown in Fig. 8.
At 3500-3300 cm− 1, the N–H stretching vibration generates a faint The electron-donating nature of a molecule is determined by the
band. The NH2 stretching vibration is attributed to the band that can be energy of the HOMO, and the electron-accepting nature is determined
seen at 3414 cm− 1 in the FTIR spectra of the 2-amino-4,6-dimethoxy by the energy of the LUMO. The final charge transfer contact inside the
pyrimidine molecule [24]. Huey reported in 2007 that the FT-Raman molecule is explained by the energy gap of HOMO = − 0.17398 a.u. and
band was seen at 3418 cm− 1 for the same vibration. The N–H stretch­ LUMO = − 0.26566 a.u. The frontier orbital energy gap of the investi­
ing vibrations in our ETMBHC molecule may be seen in the FTIR at 3398, gated molecule is discovered to be 0.09168. The ETMBC’s HOMO-LUMO
and 3555 cm− 1, and in the FT-Raman spectrum at 3393 and 3549 cm− 1. parameters are shown in Table 5.
By using the B3LYP/6–31++G (d, p) level, the stretching mode was The ETMBHC molecule’s calculated and observed UV–Vis spectra are
estimated at the higher wavenumbers 3411 and 3557 cm− 1. shown in Fig. 9. It should be noted that the experimental result and
computed absorption peak are situated at 320.42, 358, and 340 nm,
5.4.3. C–S vibrations respectively. As a consequence, the predicted result and the experi­
In the region of 670–930 cm− 1, C–S stretching bands are often seen mental results correspond rather well.
with moderate intensity. The computed bands at the B3LYP level in the
same location indicate band positions at 634, 718, and 772 cm− 1 for the
C–S stretching vibrations, and they are in very good agreement with

7
S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Fig. 9. Experimental and Calculated UV–Vis spectrum of ETMBHC.

Fig. 10. TG and DTG of ETMBHC

5.6. Thermal studies takes place in the temperature range of 290 to 410 ◦ C. With a weight
reduction of roughly 17.30%, the third stage of weight loss takes place
ETMBHC crystalline samples were subjected to TG-DTG analyses at between 240 and 290 ◦ C.
heating rates of 10 ◦ C/min in nitrogen atmospheres from room tem­
perature to 710 ◦ C. Thermogravimetric analysis (TGA) and differential 5.7. Z-scan measurement
thermal analysis were used to examine the thermal stability variations of
the ETMBHC crystalline sample (DTG). Fig. 10 depicts the ETMBHC’s A minimal proportion of third-order nonlinear effect may also be
TG-DTG curves. produced by a non-centrosymmetric crystal that produces second har­
It is evident from the TG curve that the material is stable up to monics. The spatial and temporal pulse propagation of second har­
100 ◦ C, followed by a single-step substantial weight loss that corre­ monics will be significantly disrupted by the third-order nonlinear
sponds to the DTA curve and is about 32.58% between 410 and 655 ◦ C. effect, which also results in pulse broadening [26]. Therefore, under­
With a weight loss of around 29.52%, the second stage of weight loss standing the third harmonic impact is crucial and must be defined to

8
S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

Fig. 11. a and bOpen & Closed aperture and ratio of ETMBHC crystal.

effectively produce second harmonics. The nonlinear refractive index 6. Conclusion

may be used to assess the spectrum and temporal pulse broadening
brought on by third-order effects and the optical damage brought on by The Slow Evaporation Solution growth Technique was used to create
self-focusing (n2). Fig. 11a and b depict the open and closed apertures as ETMBHC single crystals from ethanol. X-ray investigations on a single
well as the ETMBHC crystal’s ratio. crystal verified the ETMBHC crystal’s cell characteristics. The crystal is a
The non-linear phase shift’s sign determines how to calculate the member of the P-1 space group’s triclinic system. It is a desirable choice
peak and valley’s locations with the z-axis. The difference in normalized for second and third harmonics generation and device applications
transmittance between the peak and valley may be used to estimate the because it has optical transmittance over the whole visible range. FTIR
size of the phase shift. and FT-Raman analyses were used to validate the existence of functional
groups. Using the DFT approach at the B3LYP/6–31++G(d,p) level of
ΔTp –v = 0.406 (1 − S)0.25 |φ| (1) theory, the molecular structure, FMOs, and electronic absorption spectra
for the ETMBHC have been computed.
where S is the aperture linear transmittance and is calculated using the
following equation
( / ) Declaration of competing interest
S = 1 – exp − 2 ra 2 ωa 2 (2)
The authors whose names are included in this research paper. It is
where ra is the radius of the aperture and ωa is the beam radius at the
certify that they have NO affiliations with or involvement in any orga­
aperture, the non-linear refractive index is given by the relation
nization or entity with any financial interest (such as honoraria;
/
n2 = φ KI0 Leff (3) educational grants; participation in speakers’ bureaus; membership,
employment, consultancies, stock ownership, or other equity interest;
where K = 2π/ λ (where λ is the laser wavelength). and expert testimony or patent-licensing arrangements), or non-
I0 is the input intensity, (Z = 0, Leff = [1-exp(-α L)]/ α is the effective financial interest (such as personal or professional relationships, affili­
thickness of the sample and α is the linear absorption coefficient of the ations, knowledge or beliefs) inthe subject matter or materials discussed
ETMBHC crystal. From the open aperture Z – scan data, the non-linear in this manuscript.
absorption coefficient is estimated as
√̅̅̅ / References
β = 2 2ΔT I0Leff (4)
[1] T.C. Lin, J.M. Cole, A.P. Higginbotham, A.J. Edwards, R.O. Piltz, J. Perez-Moreno,
J.-Y. Seo, S.-C. Lee, K. Clays, O.-P. Kwon, Molecular origins of the high-
Where Δ T is the one valley at the open aperture Z-scan curve. performance nonlinear optical susceptibility in a phenolic polyene chromophore:
For saturable absorption and two-photon absorption, the values will electron density distributions, hydrogen bonding, and ab initio calculations,
be negative and positive, respectively. Equation (1) defines the real and J. Phys. Chem. C 117 (2013) 9416–9430.
[2] M. Hasmuddin, M.M. Abdullah, P. Singh, M. Shkir, N. Vijayan, M.A. Wahab, Ab-
imaginary components of the third-order non-linear optical suscepti­
initio study of L-tartaric acid (LTA) single crystal for NLO application, Opt Laser.
bility χ3. Technol. 74 (2015) 53–59.
( )/ ( / ) [3] X. Wang, Y. Du, S. Ding, Q. Wang, G. Xiong, M. Xie, X. Shen, D. Pang, Preparation
Re χ 3 (esu) = 10− 4 ε0 C2 n0 2 n2 π Cm2 W (5) and third-order optical nonlinearity of self-assembled chitosan/CdSe- ZnS core-
shell quantum dots multilayer films, J. Phys. Chem. B 110 (2006) 1566–1570.
( )/ [4] L. Wen, Y. Fang, J. Yang, Y. Han, Y. Song, Third-order nonlinear optical properties
Im χ 3 (esu) = 10− 2
ε0 C2 n0 2 λβ 4π2 (Cm / W) (6) and ultrafast excited-state dynamics of benzothiazolium salts: transition in
absorption and refraction under different time regimes, Dyes Pigments 156 (2018)
where ε0 is the vacuum permittivity, n0 is the linear refractive index of 26–32.
[5] A. Fihey, A. Perrier, W.R. Browne, D. Jacquemin, Multiphotochromic molecular
the sample & C is the velocity of the light in a vacuum. In our experiment
systems, Chem. Soc. Rev. 44 (11) (2015) 3719–3759.
for ETMBHC crystal non linear refractive index n2 = 2.17 × 10− 10(Cm2/ [6] N.Y. Li, D. Liu, Z.G. Ren, C. Lollar, J.P. Lang, H.C. Zhou, Controllable fluorescence
W). The absorption coefficient β calculated from open aperture switching of a coordination chain based on the photoinduced single-crystal-
normalized transmittance was obtained to β = 2.28 × 10− 4(Cm/W). tosingle-crystal reversible transformation of a syn-[2.2]metacyclophane, Inorg.
Chem. 57 (2) (2018) 849–856.
According to the equation by (5) & (6), this value of n2 & β can be used to [7] J.S. Casas, M.S. Garcia-Tasende, J. Sordo, Coord. Chem. Rev. 209 (2000) 197–261.
calculate χ3. The Third-order nonlinear optical susceptibility χ3=3.131 [8] E. Manoj, M.R.P. Kurup, Polyhedron 27 (2008) 275.
× 10− 8esu. [9] E. Maccioni, M.C. Cardia, S. Distinto, L. Bonsignore, A. De Logu, Farmaco 58
(2003) 951–959.

9
S. Sathiya et al. Journal of the Indian Chemical Society 100 (2023) 101020

[10] A.J.M. Al-Karawi, W. Clegg, R.S. Harrington, R.A. Henderson, Dalton Trans. (2009) [20] G. Kaur, P. Panini, D. Chhopra, A. Roy Choudhury, Structural investigation of weak
564. intermolecular interactions in fluorine substituted isomeric N-benzylideneanilines
[11] M.J. Frisch, et al., Gaussian-09, Revision A.01, Gaussian, Inc., Wallingford, CT, cryst, Growth Des 12 (10) (2012) 5096–5110.
2009. [21] M.A. Spackman, J.J. McKinnon, Fingerprinting intermolecular interactions in
[12] H.B. Schlegel, Optimization of equilibrium geometries and transition structures, molecular crystals, CrystEngComm 4 (2002) 378–392.
J. Comput. Chem. 3 (1982) 214–218. [22] A. Eşme, S.G. Sağdınç, Theoretical studies of molecular structures, infrared spectra,
[13] R. Dennington, T. Keith, J. Millam, GaussView, Version 5, Semichem Inc., Shawnee NBO and NLO properties of some novel 5-arylazo-6-hydroxy-4-phenyl-3-cyano-2-
Mission, KS, 2009. pyridone dyes, Acta Phys. Pol. 130 (2016) 1273–1287.
[14] SAINT Plus (V 6.14), Bruker AXS Inc., Madison, WI, 2008. [23] G. Varsanyi, Assignment for Vibrational Spectra of Seven Hundred Benzene
[15] G.M. Sheldrick, A short history of SHELX, Acta Crystallogr. E 64 (2008) 112–122. Derivatives, Academic Kiaclo, Budapest, 1973.
[16] G.M. Sheldrick, Crystal structure refinement with SHELXL, Acta Crystallogr. C 71 [24] R. Huey, G.M. Morris, A.J. Olson, D.S. Goodsell, J. Comput. Chem. 28 (2007)
(2015) 3–8. 1145–1152.
[17] A.L. Spek, PLATON, A Multipurpose Crystallographic Tool, Utrecht University, [25] M. Snehalatha, C. Ravikumar, I. Hubert Joe, V.S. Jayakumar, J. Raman Spectrosc.
Utrecht, Netherland, 2002. 40 (2009) 1121.
[18] A.L. Spek, Single-crystal structure validation with the program PLATON, J. Appl. [26] J.J. Rodrigues Jr., L. Misoguti, F.D. Nunes, C.R. Mendonca, S.C. Zilio, Optical
Crystallogr. 36 (2003) 7–13. properties of L-threonine crystals, Opt. Mater. 22 (2003) 235–240.
[19] S.K. Wolff, D.J. Grimwood, J.J. McKinnon, D. Jayatilaka, M.A. Spackman, [27] M.A.A.A.A. Islam, M.C. Sheikh, A.A. Mahmud, R. Miyatake, E. Zangrandod Benzyl,
CrystalExplorer1.5, University of Western Australia, 2005. http://www.Theochem. 3-(3,4,5-trimethoxybenzylidene)dithiocarbazate IUCrData vol. 1, 2016,
uwa.edu.au/crystal_explorer/. p. x160190.

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