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Synthesis, physicochemical, XRD/HSA-interactions, heteromeric [CH···Cl/CH···πPh] synthon, DFT, thermal and 1BNA-DNA molecular coupling of cis-Ni(S, N)2 complex using hydrazine carbodithioate schiff base

BMC Chemistry volume 19, Article number: 108 (2025) Cite this article

Abstract

The reaction of bidentate-S, N-thione Schiff base ligand, Phenyl (E)-2-(1-phenylethylidene)-hydrazine-1-carbodithioate (PPEHCDT) with NiCl2.3H2O produced a neutral NiII(S, N)2 complex with cis form as kinetic favor isomer. Various physicochemical techniques, including EDX, FAB-MS, UV-Vis, IR, CHN, and XRD-crystal analysis, were employed to characterize the desired complex. These techniques provided evidence supporting the coordination of the ligand with the Ni-center, as indicated by the neutral cis-Ni(L)2 formula. The XRD-results revealed a cis-isomer as anionic S-thiol and bis-bidentate-N-azomethine, as well as a slightly distorted square planar neutral cis-Ni(PPEHCDT)2 complex. In contrast, the DFT simulation supported a distorted tetrahedral as favor geometry, despite the fact that the XRD/DFT structural parameters results agreed. Moreover, the Molecular Electrostatic Potential (MEP) together with the Hirshfeld Surface Analysis (HSA) confirmed the XRD seen in appearance of the Heteromeric sub-synthons via C-H….πPh and C-H···S interactions. Moreover, the TG/DTG technique exhibited a high level of stability (∼ 250 °C) and a two-step thermal degradation process for the prepared cis-Ni(PPEHCDT)2 complex. Furthermore, it has been observed that the molecular docking of 1BNA-DNA with the free ligand is superior to that of the cis-Ni(PPEHCDT)2 complex due to the presence of two H-bonds with a larger binding energy as opposed to a single H-bond with a lower binding energy.

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Introduction

The transition metal ion nitrogen-sulfur bi-chelated ligand complexes that were accomplished from dithiocarbazic acid and S-alkyl thioesters were recently studied for their structural uniqueness and applications [1,2,3,4]. The mode of coordination of such ligands together with their thiol/thione isomerization pronounced their biological activities against cancer cells, viruses, microbes, fungal, and bacterial [2,3,4]. Moreover, the multifaceted industrial chemistry of ligand-complexes results in the participation of such new materials in non-biological and biological catalysis approaches [5]. Furthermore, the coordination of several types of hydrazonedithioate (as S and N ligands) is an essential piece of research to develop new complexes with industrial molecular magnetism, semiconducting behavior, electrochemical, and optoelectronic properties [6].

The transition metal ions [M(S, N)2]n complexes using hydrazone dithioate ligands established several metal centers with different oxidation numbers of Fe(II&III), Mn(II, IV & VI), Co(III&II), Cu(I&II) and Ni(II), engage in the electrochemical oxidation of water [7,8,9,10]. Ni(S, N)2 complexes were found to be the best catalysts among the others for the oxidation of water [11,12,13,14,15,16]. Therefore, the oxidation catalytic properties of such complexes, especially Ni(II) have been developed industrially for oxidation of enantioselective sulfides, alcohols, and alkenes [17,18,19,20]. In the natural biological system, Ni(II) with N, S containing bi-, tri-, or multi-chelated ligand complexes were used as a model for Ni(II)-enzymes like Ni-containing superoxide dismutase and bi-functional acetyl–CoA/carbon monoxide dehydrogenase synthase [21, 22].

In light of the growing interest in dithiocarbazic acid ligands and their metal complexes [1, 23,24,25], the primary objective of this study was to ascertain the molecular structure of the cis-Ni(PPEHCDT)2 complex during its interaction with the S-PPEHDC ligands. This study aimed to investigate the thiol-thione coordination mode behavior of the desired tridentate hydrazinecarbodithioate Schiff base via various physicochemical measurements, with particular emphasis on crystallographic XRD-one. The DFT, XRD, thermal behavior, HSA, MEP, MAC/NPA, DOS, HOMO/LUMO, and physicochemical properties together with their 1BNA-DNA docking behaviors were investigated.

Experimental

Chemicals and measurements

Chemicals and solvents fine are available from Fluka. In order to measure the infrared vibrations in the 4000–200 cm− 1 wavenumber range, the PerkinElmer Spectrum 1000 FT-IR Spectrometer was used. The UV–Vis. data was achieved via TU-1901 double-beam spectrophotometer. Using a 711 A (8 kV) Finnigan, FAB-MS data were gathered. An Elementar Analyzer Varrio EL was used to get the CHN analysis.

Synthesis of Ni(II) complex

The PPEHCDT ligand and its Ni-complex were designed and synthesized in quantitative yield using a recent synthesis approach [1], based on our knowledge of hydrazinecarbodithioate polychelate ligands, which can act as tridentate or bidentate ligands, and insights from relevant literature reviews. It is noteworthy to notice that past publications have documented the utilization of distinct nickel transition components in the synthesis of analogous complexes [1, 23,24,25]. The desired complex was prepared by adding a hot solution of BPEHCDT ligand (0.31 g, 1.0 mmol) in 20 mL of ethanol to a solution of NiCl2.3H2O (0.24 g, 1 mmol) in ethanol (30 mL). The mixture was stirred for an hour. The solution’s volume was then reduced to half and refrigerated in a refrigerator for eight hours. The green precipitate was filtered and thoroughly washed with methanol and n-hexane, respectively. M.p 223 °C, yield in 76%. Anal. Calcd for C30H26N4NiS4: C, 57.24; H, 4.16; and N, 8.90. Found C, 57.21; H, 4.27; N, 8.73. FAB-MS: [M+] = 629.3 m/z. Selected IR data (cm− 1): v(C-H, Ph) 3080–3020 cm− 1, v(C-H, alkyl) 2920–2890 cm− 1, v(2 C = N) 1570 b, v(N-N) 1118 s, v(CSS) 825 cm− 1, v(Ni-N) 622 cm-1, cm− 1, v(Ni-S) 502 cm-1, cm− 1. UV–vis. Ligand bands like π→π* at 238 nm, π →n, at 302, n→π* at 360, 397,238, 290, and d→d (Ni2+) band at 420 nm.

Computation and XRD-crystal

HSA was achieved via CrystalExplorer platform, version 17 [26]. Gaussian W09 software was utilized for all the DFT stimulations [27]. The LANL2DZ was used as a basis set for Ni(II) the heavy atoms, while DFT 6-311G(d, p) was used for the other atoms. The docking studies were performed via Autodock 4.2 software, 2016 [28]. The 3D structure of the used DNA was obtained from the Protein Data Bank (PDB) via the 1bna code; the structure is readily accessible free on the PDB website [29]. The resolution of the 1BNA DNA structure, determined by SC-XRD, is 1.90 Å; the structure was obtained by crystallizing the protein under a precise method. The 1BNA-DNA structure is a distinguished B-form DNA dodecamer and was one of the first high-resolution DNA structures revealed using X-ray crystallography [30].

Single-crystal XRD data was collected on a Bruker AXS Smart Apex CCD diffractometer with graphite monochromatic Mo-Kα radiation of λ = 0.071073 Å at a temperature of 130 ± 2 K, using the scanning technique to a maximum of 137 ± 2 K. The structure was solved by direct method employing SIR-92 and full-matrix least squares refinement [31]. All nonhydrogen atoms were anisotropically refined through SHELXL [32]. Hydrogen atoms were located geometrically and were refined isotropically. Table 1 reports the crystal data.

Table 1 cis-Ni(PPEHCDT)2 complex structure refinement data
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Results and discussion

Preparation, CHN-EA, MS, EDX and IR of cis-Ni(PPEHDC)2 complex

To obtain the required cis-Ni(PPEHDC)2 complex, the PPEHDC ligand was treated with NiCl2.3H2O in a hot EtOH solution at room temperature, as shown in Scheme 1. The cis-Ni(PPEHDC)2 complex was collected as a brownish powder with a good yield of 78%. The complex is slightly soluble in methanol, chlorinated solvents, and hot water but never in n-hexane. The cis-Ni(PPEHDC)2 molecular structure was examined using various spectral techniques, including IR, FAB-MS, CHN-EA, UV-vis, EDX, TG/DTG, and XRD-crystal. The XRD result showed the PPEHDC ligand as S (thiol) and N (azometh) and not with thione form ligand mode of coordination.

Furthermore, it was observed that the cis-isomer of the neutral Ni(PPEHDC)2 complex was exclusively obtained as the kinetically favored isomer. Conversely, there was no indication of the formation of the trans-Ni(PPEHDC)2 complex isomer, which is thermodynamically favored. This observation has been substantiated through XRD-crystal analysis.

Scheme 1
figure 1

Cis-Ni(PPEHDC)2 complex synthesis

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Cis-Ni(PPEHDC)2 complex formula weight was confirmed by FAB-MS, [M + 1+] = 629.3 m/z (628.2 m/z theoretical). The CHN-elemental analysis aligns with the molecular formula of the complex C30H26N4NiS4. Moreover, EDX-analysis confirmed the purity and the atomic continent, as only energy peaks belong to C, N, S and Ni were detected, as shown in Fig. 1a.

Fig. 1
figure 1

(a) EDX spectra, (b) IR, (c) DFT and (d) DFT/Exp.-IR correlation diagram

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The solid-state FT-IR of cis-Ni(PPEHDC)2 complex was recorded, as seen in Fig. 1b. Several IR stretching vibration bands were observed; the main groups CPh-H, Calkyl-H, C = N◊Ni, C = N, N-N, CS2, N◊Ni and S◊Ni stretching vibrations were sited to 3080 − 3020, 2920 − 2890, 1575, 1570, 1118, 825, 622, 502 cm− 1, respectively. The same functional group stretching vibrations were observed by DFT-IR with slight shifts in their wavenumber values, as seen in Fig. 1c. Furthermore, the DFT and experimental IR wavenumber values exhibit a high level of agreement, as evidenced by a graphical correlation of 0.997, as seen in Fig. 1d.

X-Ray and DFT computations

The DFT-optimized and ORTEP diagrams of cis-Ni(PPEHDC)2 complex structures and their parameters have been illustrated in Fig. 2; Table 2. C32H30N4NiS4 is Monoclinic in crystal system, C2/c with Z = 4 per cell. The two PPEHDC ligands bonded to Ni(II) center via S and N provided by 2 anionic via S- and 2 neutral N-groups to form the neutral cis-Ni(PPEHDC)2 complex with two five-hetero-metal-membered center cis-Ni(N, S)2 rings (Fig. 2b). The bond and angle values of the Ni(II)-complex are in high agreement with previously similar structures [1, 23, 24]. The Ni(II) center geometry was solved as a distorted square planar with τ = 30.2o (Fig. 2b). The DFT optimization result of the cis-Ni(PPEHDC)2 complex revealed that the square planar geometry is more favourable than the tetrahedron geometry. This observation was not surprising since the DFT theory neglected any internal interactions (gaseous state). Hence, it is possible through DFT to observe that the tetrahedral structure around metal center is a preferred isomer over the square planar geometry because it has a lower steric hindrance that minimizes the internal repulsion. As the distorted square planar around the Ni(II) center has been confirmed experimentally by XRD-crystal, it can be said in this manuscript that the DFT-theory contradicted the results of XRD in judging the final geometry around the metal central atom, but it agreed in judging the other structural parameters.

Fig. 2
figure 2

(a) ORTEP diagram, (b) distorted square planar, (c) DFT optimization, and (d) DFT-tetrahedral structure of cis-Ni(PPEHDC)2 complex

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Table 2 Designated DFT/XRD bonds and angles lengths
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The DFT-optimized angles and bond lengths were consistent with experimental XRD data, as shown in Fig. 3. Figure 3a shows acceptable levels of DFT and XRD in terms of angles and bond lengths. Bond lengths were in great agreement, as shown in Fig. 3a, with a graphical correlation R2 = 0.972 (Fig. 3b). Even two distinct geometries were proposed: the tetrahedral structure was seen by DFT and the square planar structure was validated by XRD; their angles also exhibited excellent agreement, as shown in Fig. 3c, with graphical correlation R2 = 0.9798 (Fig. 3d).

Fig. 3
figure 3

(a) XRD/DFT-bond lengths histogram, (b) XRD/DFT-bond lengths graphical correlation, (c) XRD/DFT-angles histogram, and (d) DFT/Exp. angles correlation diagram

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Heteromeric [CH···Cl/CH···πPh] synthon and HSA investigation

Typically, the occurrence of two primary large synthons of 2D-S24-type cyclic bonding is uncommon (Fig. 4a). This is because each synthon is composed of a triple-side sub-synthon, specifically 2S11 and 1S10, which bind through two short contacts: Calkyl-H…S with a radius of 2.902 µ and Cph-H…Ph with a radius of 2.974 γ (Fig. 4b). The non-classical shorter hydrogen bonds, specifically H…S and H…Ph, exhibit a two-dimensional chain formation, as depicted in Fig. 4b. Furthermore, the cis-Ni(PPEHDC)2 lattice exhibited a notable increase in crystalline matrix stability as well as enhanced optical and electrical characteristics due to the presence of eight interactions per two synthons [33].

Fig. 4
figure 4

(a) 2D-S24 triple sub-synthon, and (b) 2S11 + S10 sub-synthons including H….S and H···πPh interactions

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To confirm the packing result, the HSA of cis-Ni(PPEHDC)2 was performed in between − 0.632 and 1.876 a.u. using the CIF crystallographic data [34,35,36,37,38,39,40,41,42]. The HSA and 2D-FP collected results are illustrated in Fig. 5. The existence of S and N heteroatoms together with π of the aromatic rings, in addition to several polar hydrogens, enhanced the formation of eight red-dots, including the presence of short interactions like H….S and H···πPh as seen in dorm (Fig. 5a). Moreover, 2D-FP intermolecular H-to-atom ratios are displayed in Fig. 5b. It was found that the H···H (51.5%) interaction has the highest ratio among all interactions, while the H···Ni reflected a 0.1% ratio (Fig. 5c). The 2D-FP ratio analysis is illustrated in the following order: H….H > C….H > S…H> (N….H, Ni….H, 0%).

Fig. 5
figure 5

(a) dnorm, (b) shape index, and (c) 2D-FP over the cis-Ni(PPEHDC)2 complex surface

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MEP, and MAC/NPA

MEP map of cis-Ni(PPEHDC)2 complex is computed to explore the binding properties of the complex. The potential increased, ranging from blue, green, yellow, orange, and red, reflecting the degree of the electronic density of each atom. The MEP results indicated that the etheric S and coordinated S atoms display the highest e-rich/nucleophilic sites (red color). Meanwhile, the e-poor/electrophilic spots (blue) are highly seated on the phenyl and methyl protons. Usually, aromatic rings are rich with \(\:\pi\:\) electrons; they are distinguished as yellow areas (Fig. 6). Non-classical C-H···πPh and C-H….S H-bond interactions can be computed using MEP theory that is consistent with the HSA and XRD outcome. The atomic charge of our molecule surface behavior MAC and NPA charge distribution in cis-Ni(PPEHDC)2 complex were calculated and displayed as seen in Fig. 6. In general, the NPA reflected the Ph charges with higher values compared to MAC results. All atomic charges of each atom on the surface of the core of the molecule were collected in Table 3. The comparative study of both the models, MAC and NPA, is accepted since a high graphical correlation is detected at 0.8921, as seen in Fig. 6d.

Fig. 6
figure 6

(a) MEP, (b) MAC/NPA, (c) MAC vs. NPA, and (d) MAC/NPA correlation of cis-Ni(PPEHDC)2 complex

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Table 3 NPA/MAC charge population
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HOMO/LUMO and DOS

The HOMO and LUMO shapes and energy levels provide input about stability, the relationship orbitals, and the general chemical and structural properties of the prepared new compounds. In the HOMO, the main electron density focused around the Ni(II) and the core atoms of cis-Ni(PPEHDC)2; meanwhile, in LUMO focus only around the core atoms and not on Ni(II) center. Both HOMO and LUMO defocused the terminal phenyls. Moreover, the ELUMO, EHOMO, and ΔE were calculated to be -0.0833, -0.1921, and 0.1088 a.u (2.9598 eV), respectively, as shown in Fig. 7a. In order to verify the HOMO and LUMO energy values, they were calculated using another model, like the Density of State (DOS). The net energy resulted in by DOS ΔEDOS was found to be consistent with ΔEHOMO/LUMO with very close 2.988 eV, as seen in Fig. 7b.

Fig. 7
figure 7

(a) HOMO and LUMO shapes and energy and (b) DOS diagrams of cis-Ni(PPEHDC)2 complex

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TG/DTG analysis

The thermal behavior of the desired cis-Ni(PPEHDC)2 complex has been performed in an ambient conditions using a heat rate of 10 °C/min via TG/DTG, as shown in Fig. 8. Figure 8 shows the complex exhibitin high thermal stability. The stability of the complex up to 250 °C can be attributed to the absence of uncoordinated or coordinated water molecules on the nickel atom. This is evidenced by the absence of any weight loss in the complex between 50 and 160 °C, as depicted in Fig. 8a. This finding is consistent with both the IR and XRD results. The desired complex underwent two primary decay processes. The initial step exhibited the most pronounced mass decay within the temperature range of 250–300 °C, with TDTG = 280 °C (Fig. 8) and mass of 39.6%. This loss can be mainly attributed to the de-structured of one piece of the PPEHDC ligand to form cis-Ni(PPEHDC)2 complex. Meanwhile, the second step involved a wide range of temperatures from 420 to 510 °C, with TDTG = 480 °C and mass loss of 40.5%.This loss can be attributed to the de-structuring of the second ligand component, which occurred simultaneously with the reaction with atmospheric O2 to produce nickel oxide as a final product with ∼ 19.3% yield [44].

Fig. 8
figure 8

TGA of the cis-Ni(PPEHDC)2 complex

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Molecular docking studies

In the field of structural drug design (SDD), understanding the binding of medications to DNA or enzymes can be accomplished by the most successful theoretical molecular coupling method, which distinguished as an outstanding methodology [43,44,45]. The methodology in this section focuses on the interaction between the free PPEHCDT ligand and its cis-Ni(PPEHCDT)2 complex with 1BNA-DNA helices. This algorithm will analyze different positions, orientations, and types of interaction between PPEHCDT or cis-Ni(PPEHCDT)2 and DNA using Autodock 4.2 [28] output virtualized via PyMOL [46] software. Its goal is to identify the configuration that offers the greatest fit to assess the experimental better future chemotherapy. Table 4; Fig. 9 show the final docked pictures and the binding energy estimates for the ligand and its complexes. The PPEHCDT docked with 1BNA resulted like the cisplatin binding mode; mimic a good docking by cross-linking of the 1BNA both double helix [42] with a minor grove site interaction (Fig. 9a) via two short hydrogen bonds. The first was via NH of hydrazine carbodithioate and cytosine (DC23:O4) bases of DNA with 1.985 Å length, and the second hydrogen bond was through sulfur of dithioate and guanine (DG4:H22) bases of DNA with 2.323 Å length (Fig. 9b). These two H-bond result the binding energy with a very good value of -8.84 kcal/mol. Other weak binding interactions as Ph π: π, S-π and VdW, were also recorded, as seen in Fig. 9b. A dramatical change in the bonding mode was obtained when the cis-Ni(PPEHCDT)2 was introduced instead of the free ligand. The complex binds the 1BNA to the major grove instead of the minor grove position (Fig. 9c) [44, 45]. Only one hydrogen bond via sulfur of dithioate and adenine (DA18:H62) with 2.234 Å length has been detected (Fig. 9d); moreover, a lower binding energy of -6.34 kcal/mol has been recorded as seen in Table 4. Additionally, inhibition constant (IC) value of cis-Ni(PPEHCDT)2 complex is lower than that of the free ligand which reflects the complex as better 1BNA binder (Table 4). However, they usually used the binding energy values in the final judgment on the ability of compounds to bind with DNA better, since it is a more reliable parameter. Conversely, the ligand efficiency values aligned with the bonding energy values, indicating that the free PPEHCDT ligand is a more effective DNA-binder compared to its cis-Ni(PPEHCDT)2 complex, as PPEHCDT exhibited a higher negative B.E value (Table 4).

Table 4 Docking data of both the PPEHCDT and its cis-Ni(PPEHCDT)2
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Fig. 9
figure 9

Docking result of both the PPEHCDT and its cis-Ni(PPEHCT)2 with 1BNA: (a) PPEHCDT ‘s connection site, (b) 2D-interactions of PPEHCDT, (c) cis-Ni(PPEHCDT)2’s connection site, and (d) Nucleotides medium with their H-bond interacted to cis-Ni(PPEHCDT)2

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Conclusions

A novel neutral Nickel(II) complex with two Ni(PPEHDC)2 bidentate N, S-type ligands has been prepared in a good yield. The structural formula of cis-Ni(PPEHDC)2 isomer was evidenced by XRD and further supported via EDX, IR, UV-Vis, CHN-EA, and FAB-MS analysis. X-ray diffraction reflected the cis-Ni(PPEHDC)2 complex with distorted square planar as opposed to the tetrahedral geometry revealed by the DFT theoretical analysis. The cis-Ni(PPEHDC)2 was chelated to the Ni(II) center via S-thiol and N-azomethine atoms to form a unique cis-conformation square planar. Additionally, the DFT/XRD angles and bond length values were of good consistency. The MEP, MAC/NPA, and HSA calculation results proved the XRD-experimental result in the 2D-S24 synthons formation via C-H···πPh and C-H···S interactions. The cis-Ni(PPEHDC)2 is thermally stable up to 250 oC; it decomposed to nickel oxide final product in a two-step decomposition mechanism. Moreover, investigations of 1BNA docking with the free ligand and its Ni-complex showed a dramatical shift in binding locations, H-bond quantity and type, and binding energy values.

Data availability

The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.

References

  1. Boshaala A, Salih KSM, Bader N, Almughery AA, Zarrouk A, Warad I. XRD/HSA, noncovalent interactions and influence of solvent Polarity on spectral properties of dithiocarbazate schiff base and its cis-Cu(II) complex: experimental and theoretical studies. J Mol Liq. 2021;330:115551.

    Article  CAS  Google Scholar 

  2. Singh NK, Bharty MK, Kushawaha SK, Singh UP. Pooja Tyagi, synthesis, spectral and structural studies of a Mn(II) complex of [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid Ethyl ester and Mn(II) and Ni(II) complexes of [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid Methyl ester. Polyhedron. 2010;29:1902.

    Article  CAS  Google Scholar 

  3. Otero L, Vieites M, Boiani L, Denicola A, Rigol C, Opazo L, Olea-Azar C, Maya JD, Morello A, Krauth-Siegel RL, Piro OE, Castellano E, Gonzalez M, Gambino D, Cerecetto H. Novel antitrypanosomal agents based on palladium nitrofurylthiosemicarbazone complexes: DNA and redox metabolism as potential therapeutic targets. J Med Chem. 2006;49:3322.

    Article  CAS  PubMed  Google Scholar 

  4. Tarafder MTH, Ali MA, Wee DJ, Azahari K, Silong S, Crouse DA. Coordination chemistry and biological activity of nickel (II) and copper(II) ion complexes with nitrogen–sulphur donor ligands derived from S-benzyldithiocarbazate (SBDTC). Trans Met Chem. 2000;25:456.

    Article  CAS  Google Scholar 

  5. Beckett R, Hoskins BF. Square-planar complexes of pentane-2, 4-dithione (dithioacetylacetone): crystal structures of the Cobalt (II) and nickel (II) derivatives. J Chem Soc Dalton Trans (1974) 622.

  6. Singh V, Chauhan R, Kumar A, Bahadur L, Singh N. Efficient phenylmercury (II) Methylferrocenyldithiocarbamate functionalized dye-sensitized solar cells. Dalton Trans. 2010;39:9779.

    Article  CAS  PubMed  Google Scholar 

  7. eizi HF, Shiri F, Bagheri R, Singh J, Chae KH, Song Z, Najafpour MM. The application of a nickel(ii) schiff base complex in water oxidation: the importance of nanosized materials. Catal Sci Technol. 2018;8:3954.

    Article  Google Scholar 

  8. Najafpour MM, Renger G, Hołyn´ ska M, Moghaddam AN, Aro E-M, Carpentier R, Nishihara H, Eaton-Rye JJ, Shen J-R, Allakhverdiev SI. Nanosized manganese oxide/holmium oxide: A new composite for water oxidation. Chem Rev. 2016;116:2886.

    Article  CAS  PubMed  Google Scholar 

  9. Rüttinger W, Dismukes GC. Synthetic water-oxidation catalysts for artificial photosynthetic water oxidation. Chem Rev. 1997;97:1.

    Article  PubMed  Google Scholar 

  10. McEvoy JP, Brudvig GW. Water-splitting chemistry of photosystem II. Chem Rev. 2006;106:4455.

    Article  CAS  PubMed  Google Scholar 

  11. Sarkar S, Nag SK, Chattopadhyay AP, Dey K, Islam SM, Sarkar A, Sarkar S. Synthesis, structure and catalytic activities of nickel(II) complexes bearing N4 tetradentate schiff base ligand. J Mol Struct. 2018;1160:9.

    Article  CAS  Google Scholar 

  12. Cao Y, Lu M, Fang J, Shi L, Zhang D. Hexagonal Boron nitride supported mesosio 2-confined Ni catalysts for dry reforming of methane. Chem Commun. 2017;53:7549.

    Article  CAS  Google Scholar 

  13. Han Y, Wu Y, Lai W, Cao R. Electrocatalytic water oxidation by a water-Soluble nickel porphyrin complex at neutral pH with low overpotential. Inorg Chem. 2015;54:5604.

    Article  CAS  PubMed  Google Scholar 

  14. Najafpour MM, Feizi H. Nano-sized manganese oxide: a proposed catalyst for water oxidation in the reaction of some manganese complexes and cerium (IV) ammonium nitrate. Dalton Trans. 2012;41:10292.

    Article  CAS  PubMed  Google Scholar 

  15. Schley ND, Blakemore JD, Subbaiyan NK, Incarvito CD, D’Souza F, Crabtree RH, Brudvig GW. Elucidating molecular iridium water oxidation catalysts using Metal–Organic frameworks: A comprehensive structural, catalytic, spectroscopic, and kinetic study. J Am Chem Soc. 2011;133:10473.

    Article  CAS  PubMed  Google Scholar 

  16. Zhang M, Zhang MT, Hou C, Ke ZF, Lu TB. Angew. Homogeneous electrocatalytic water oxidation at neutral pH by a robust macrocyclic nickel (II) complex chem. Int Ed. 2014;53:13042.

    Article  CAS  Google Scholar 

  17. Grivani G, Khalaji AD, Tahmasebi V, Gotoh K, Ishida H. Synthesis, characterization and crystal structures of new bidentate schiff base ligand and its vanadium(IV) complex: the catalytic activity of Vanadyl complex in epoxidation of alkenes. Polyhedron. 2012;31:265.

    Article  CAS  Google Scholar 

  18. Lippard SJ, Berg JM. Principles of bioinorganic chemistry. California: University Science Books; 1994.

    Google Scholar 

  19. Amini M, Arab A, Soleyman R, Ellern A, Woo LK. Synthesis, characterization and crystal structures of oxovanadium(V) complexes derived from similar aroylhydrazone ligands. J Coord Chem. 2013;66:3770.

    Article  CAS  Google Scholar 

  20. Khadir N, Amini M, Assoud A, Bagherzadeh M, Boghaei DM. Synthesis and characterization of two binuclear nickel(II) complexes of thiophenol-based end-off compartmental ligands and their application as catalysts for selective oxidation of sulfides. J Coord Chem. 2016;69:103.

    Article  CAS  Google Scholar 

  21. Doukov TI, Iverson TM, Seravalli J, Ragsdale SW, Drennan CL. A Ni-Fe-Cu center in a bifunctional carbon monoxide dehydrogenase/ Acetyl-CoA synthase. Science. 2002;298:567.

    Article  CAS  PubMed  Google Scholar 

  22. Wuerges J, Lee JW, Yim YI, Yim HS, Kang SO, Carugo KD. Crystal structure of nickel-containing superoxide dismutase reveals another type of active site. Proc Natl Acad Sci USA. 2004;101:8569.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  23. Boshaala A, Yamin BM, Ben Amer YO, Ghaith GSH, Almughery AA, Zarrouk A, Warad I. Crystal interaction, Hirshfeld surface analysis, and spectral analysis of new dithiocarbazate schiff bases derivative (LH) and its neutral cis-Cu (L) 2 complex. J Mol Struct. 2021;1224:129207.

    Article  CAS  Google Scholar 

  24. Boshaala AM, AlFarha KA, Sheppaek H, Algezzeri WO, Zarrouk A, Warad I. Crystal interaction, XRD powder, and Hirshfeld surface analysis of S-benzyl-β-N-(1-(4-chlorophenyl) ethylidene) dithiocarbazate schiff base. Mor J Chem. 2020;8:1048.

    CAS  Google Scholar 

  25. Lindner E, Warad I, Eichele K, Mayer HA. Supported organometallic complexes part 34: synthesis and structures of an array of diamine(ether-phosphine)ruthenium(II) complexes and their application in the catalytic hydrogenation of trans-4-phenyl-3-butene-2-one. Inorg Chim Acta. 2003;350:49.

    Article  CAS  Google Scholar 

  26. Wolff SK, Grimwood DJ, McKinnon JJ, Turner MJ, Jayatilaka D, Spackman MA. Crystal explorer 3.0. Perth, Australia: University of Western; 2012.

    Google Scholar 

  27. Frisch GWTMJ, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR. Gaussian 09, Revision E.01, Gaussian, Inc., Wallingford CT, 2009.

  28. Forli S, Huey R, Pique ME, Sanner MF, Goodsell DS, Olson AJ. Computational protein-ligand Docking and virtual drug screening with the AutoDock suite. Nat Protoc. 2016;11:905.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. https://www.rcsb.org/structure/1BNA

  30. Drew R, Wing M, Takano T, Broka C, Tanaka S, Itakura K, Dickerson E. Proc Natl Acad Sci. 1981;78:2179.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  31. Burla M, Caliandro R, Camalli M, Carrozzini B, Cascarano GL, DeCaro L, Giacovazzo C, Polidori G. Spagna SIR2004: an improved tool for crystal structure determination and refinement. J Appl Crystallogr. 2005;38:381.

    Article  CAS  Google Scholar 

  32. Sheldrich GM. SHELX-97, release 97‐2. Germany: University of Goettingen; 1998.

    Google Scholar 

  33. Srijana PJ, Narayana B, Sarojini BK, Ai Wong Q, K.Quah C, Likhitha U. Synthesis and structural studies on the supramolecular architecture of two novel proton transfer molecular salts of 2– aminopyridine. J Mol Struct. 2023;1274:134426.

    Article  CAS  Google Scholar 

  34. Guerraoui A, Djedouani A, Jeanneau E, Boumaza A, Alsalme A, Zarrouk A, Salih KSM, Warad I. Crystal structure and spectral of new hydrazine-pyran-dione derivative: DFT enol↔hydrazone tautomerization via zwitterionic intermediate, Hirshfeld analysis and optical activity studies. J Mol Struct. 2020;1220:1890.

    Article  Google Scholar 

  35. Tabti S, Djedouani A, Aggoun D, Warad I, Rahmouni S, Romdhane S, Fouzi H. New Cu(II), Co(II) and Ni(II) complexes of chalcone derivatives: synthesis, X-ray crystal structure, electrochemical properties and DFT computational studies. J Mol Struct. 2018;1155:11.

    Article  CAS  Google Scholar 

  36. Hema MK, Karthik CS, Warad I, Lokanath NK, Zarrouk A, Kumara K, Pampa KJ, Mallu P. Regular square Planer bis-(4,4,4-trifluoro-1-(thiophen-2-yl)butane1,3-dione)/copper(II) complex: Trans/cis-DFT isomerization, crystal structure, thermal, solvatochromism, Hirshfeld surface and DNA binding analysis. J Mol Struct. 2018;1157:69.

    Article  CAS  Google Scholar 

  37. Spackman MA, Jayatilaka D. Hirshfeld Surf Anal CrystEngComm. 2009;11:19.

    CAS  Google Scholar 

  38. Warad I, Awwadi FF, Abd Al-Ghani B, Sawafta A, Shivalingegowda N, Lokanath NK, Mubarak MS, Ben Hadda T, Zarrouk A, Al-Rimawi F, Odeh AB, Barghouthi SA. Ultrasound-assisted synthesis of two novel [CuBr(diamine)2H2O]Br complexes: solvatochromism, crystal structure, physicochemical, Hirshfeld surface thermal, DNA/binding, antitumor and antibacterial activities. Ultrason Sonochem. 2018;48:1.

    Article  CAS  PubMed  Google Scholar 

  39. Hema MK, Karthik CS, Lokanath NK, Mallu P, Zarrouk A, Salih KSM, Warad I. Synthesis of novel Cubane [Ni4(O∩O)4(OCH3)4(OOH)4] cluster: XRD/HSA-interactions, spectral, DNA-binding, Docking and subsequent thermolysis to NiO nanocrystals. J Mol Liq. 2020;315:113756.

    Article  CAS  Google Scholar 

  40. Aouad MR, Messali M, Rezki N, Said MA, Lentz D, Zubaydi L, Warad I. Hydrophobic pocket docking, double-proton prototropic tautomerism in contradiction to single-proton transfer in thione⇔ thiol schiff base with triazole-thione moiety: green synthesis, XRD and DFT-analysis. J Mol Struct. 2019;1180:455.

    Article  CAS  Google Scholar 

  41. Aouad MR, Messali M, Rezki N, Al-Zaqri N, Warad I. Single proton intramigration in novel 4-phenyl-3-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)-1H-1,2,4-triazole-5(4H)-thione: XRD-crystal interactions, physicochemical, thermal, Hirshfeld surface, DFT realization of Thiol/thione tautomerism. J Mol Liq. 2018;264:621.

    Article  CAS  Google Scholar 

  42. Faydy ME, About H, Warad I, Kerroum Y, Berisha A, Podvorica F, Bentiss F, Kaichouh G, Lakhrissi B, Zarrouk A. Insight into the corrosion Inhibition of new bis-quinolin-8-ols derivatives as highly efficient inhibitors for C35E steel in 0.5 M H2SO4. J Mol Liq. 2021;342:117333.

    Article  Google Scholar 

  43. Ray B, Mehrotra R. Nucleic acid binding mechanism of flavone derivative: structural analysis to unveil anticancer potential. J Photochem Photobiol B: Biol. 2020;211:111990.

    Article  CAS  Google Scholar 

  44. Haleel AK, Mahendiran D, Rafi UM, Veena V, Shobana S. Rahiman Tetrazolo[1,5-a]pyrimidine-based metal(II) complexes as therapeutic agents: DNA interaction, targeting topoisomerase I and cyclin-dependent kinase studies. Inorg Nano-Met Chem. 2018;48:12.

    Google Scholar 

  45. Baronea G, Terenzi A, Lauria A, Maria Almerico A, Leal JM, Bustoc N, García B. DNA-binding of nickel(II), copper(II) and zinc(II) complexes: Structure–affinity relationships. Coor Chem Revi. 2013;257:2848.

    Article  Google Scholar 

  46. BIOVIA DS. Discover Studio Visualiser v19.10.18287. 2018 (San Diego, USA).

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Acknowledgements

The authors extend their sincere thanks to Dr. Ulrich Florke, Department Chemie, Universität Paderborn, Warbuger Strasse 100, 33098 Paderborn, Germany for free solving of the crystal structure. Similar thanks go to Prof. Faisal Abdul Azim Al-Abdali, the General Manger of the Libyan Authority for Scientific Research for his unlimited support; special thanks go to staff members at the Libyan Authority for Scientific Research and Manchester Salt and Catalysis Ltd, UK. Other thank go to Dr. Aysha Mezoughi Tripoli University chemistry department for providing chemicals and lab facilitates.

Funding

This study did not receive any external support.

Author information

Authors and Affiliations

  1. Libyan Authority for Scientific Research, Tripoli, Libya

    Ahmed Boshaala, Abrahem F. Abrahem, Iman Muhmoud & Nagi Greesh

  2. School of Chemistry, Biomedical Sciences Research Complex, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK

    Nawaf Al-Maharik

  3. Department of Applied Chemistry, Arab American University (AAUP), Jenin, P.O Box 240, Palestine

    Hisham Qrareya

  4. Biochemistry Department, Benghazi University, Benghazi, Libya

    Ibtisam Kaziri

  5. Department of Applied Medical Science, Libyan International Medical University, Benghazi, Libya

    Ibtisam Kaziri

  6. Department of Chemistry Faculty of Science, University of Tripoli, Tripoli, Libya

    Rabia Alghazeer

  7. Libyan Advanced Centre for Chemical analysis, Tajour, Libya

    Nagi Greesh

  8. Laboratory of Materials, Nanotechnology and Environment, Faculty of Sciences, Mohammed V University in Rabat, P.O. Box. 1014, Rabat, Morocco

    Abdelkader Zarrouk

  9. Department of Dentistry and Dental Surgery, Faculty of Medicine and Health Sciences, An-Najah National University, P.O. Box 7, Nablus, Palestine

    Khalil Shalalin

  10. Department of Chemistry, Science College, An-Najah National University, P.O. Box 7, Nablus, Palestine

    Ismail Warad

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  1. Ahmed Boshaala
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Contributions

Author Contributions: Study concept and design (A.B., I.W.); data acquisition (A.F.A., I.M.); methodology (R.A., I.K., N.G.), software (I.W., A.Z.); analysis and interpretation of data (I.W., A.B., N.A.M.); drafting of the manuscript (A.B., I.W., K.S.); critical revision of the manuscript (I.W., N.A.M., H.Q.), supervision (A.B., I.W.).

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Correspondence to Ahmed Boshaala or Ismail Warad.

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Boshaala, A., Al-Maharik, N., Qrareya, H. et al. Synthesis, physicochemical, XRD/HSA-interactions, heteromeric [CH···Cl/CH···πPh] synthon, DFT, thermal and 1BNA-DNA molecular coupling of cis-Ni(S, N)2 complex using hydrazine carbodithioate schiff base. BMC Chemistry 19, 108 (2025). https://doiorg.publicaciones.saludcastillayleon.es/10.1186/s13065-025-01471-9

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BMC Chemistry

ISSN: 2661-801X

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