Tetrachloro-(acetylacetonato)stannate(IV) and tri-iodocadmate(II) stabilized by a heptacyclic cation: Synthesis, characterization, and crystal structure European Journal of Chemistry 15 (4) (2024) 338-344 European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2024 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. https://dx.doi.org/10.5155/eurjchem.15.4.338-344.2593 European Journal of Chemistry View Journal Online View Article Online Tetrachloro-(acetylacetonato)stannate(IV) and tri-iodocadmate(II) stabilized by a heptacyclic cation: Synthesis, characterization, and crystal structure Adrienne Ndiolene 1, Tidiane Diop 1,*, Mouhamadou Sembene Boye 2, and Aminata Diasse-Sarr 1 1 Département de Chimie, Université Cheikh Anta Diop de Dakar, BP 5005 Fan-Dakar, Sénégal 2 Département de Physique Chimie, Faculté des Sciences et Technologies de l’Education et de la Formation, Université Cheikh Anta Diop, Boulevard Habib, Bourguiba, BP 5036 Fann-Dakar, Sénégal * Corresponding author at: Département de Chimie, Université Cheikh Anta Diop de Dakar, BP 5005 Fan-Dakar, Sénégal. e-mail: tidiane3.diop@ucad.edu.sn (T. Diop). 10.5155/eurjchem.15.4.338-344.2593 Received: 31 August 2024 Received in revised form: 21 November 2024 Accepted: 30 November 2024 Published online: 31 December 2024 Printed: 31 December 2024 The tin (IV) and cadmium (II) complexes were synthesized in mixture, the ligand 4,4'- (ethane-1,2-diylbis(azanylylidene))bis(pent-2-en-2-ol), and the halide metal (SnCl2 or CdI2). Complex synthesis involves partial hydrolysis of the ligand followed by condensation cyclization. The new tin complex obtained crystallizes in the monoclinic space group P21/n with a = 8.5468(5) Å, b = 17.9907(9) Å, c = 12.7227(7) Å, β = 94.220(5) °, V = 1950.98(18) Å3 and Z = 4. The asymmetric unit consists of an anion tetrachloro-(acetylacetonato) stannate(IV) and a heptacyclic cation. The geometry of the complex is octahedral with cis coordination of the two oxygens of the acetylacetone. The cadmium complex crystallizes in the orthorhombic space group Pbca with a = 14.7395(9) Å, b = 8.5914(5) Å, c = 23.2825(13) Å, V = 2948.3(3) Å3, Z = 8. The geometry around cadmium is a deformed tetrahedron. The heptacyclic cation and the anionic complex are interconnected through hydrogen bonding interactions, specifically N–H···Cl or N–H···I, forming a network. Crystal structure Tin (IV) complex Heptacyclic cation Hydrogen bonding Tri-iodocadmate (II) Hybrid organic-inorganic Cite this: Eur. J. Chem. 2024, 15(4), 338-344 Journal website: www.eurjchem.com 1. Introduction In recent years, the attention to organic/inorganic compounds has increased, and tin (IV) complexes containing mono- and bidentate O-donor ligands are becoming increasingly important because of a number of compounds [1]. Hybrid organic-inorganic compounds are an emerging class of new materials that hold significant promise [2]. These complex structures, based on a molecular-scale composite of organic and inorganic components, allow the combination of the properties of organic and inorganic elements in a unique material [3]. Organic and inorganic compounds are embedded, and only weak bonds (hydrogen, van der Waals, or ionic bonds) give the cohesion to the whole structure. Inorganic compounds, typically characterized by covalent and ionic interactions, exhibit a wide range of electronic properties, including high electrical mobility and a broad spectrum of band gaps (e.g., insulators, semiconductors, and metals). They also possess notable magnetic and dielectric properties, thermal stability, and mechanical hardness [4]. Organic compounds, which typically interact through weaker interactions, with van der Waals or hydrogen bonding, offer the potential of high luminescence efficiency, large polarizability, plastic mechanical properties, and in some cases exhibit conducting properties [3,5]. Hybrid organic/inorganic compounds are considered innovative advanced materials. Promising applications are expected in many fields including optics, electronics, mechanics, protective coatings, catalysis, sensors, biology, and others [6-16]. Recently, organic/inorganic hybrid semi- conductor materials with a perovskite structure have attracted attention as light sensitizers for solar cells due to their superb photovoltaic characteristics [17]. In this present study, we report the synthesis of a tetradentate ligand (4,4'-(ethane-1,2- diylbis(azanylylidene))bis(pent-2-en-2-ol)) and two new complexes tetrachloro-(acetylacetonato)stannate(IV) and tri- iodocadmate(II)) stabilized by a heptacyclic cation. These new complexes will be characterized by infrared spectroscopy (IR) and single-crystal X-ray diffraction (SCXRD). 2. Experimental 2.1. Materials and physical measurements ABSTRACT RESEARCH ARTICLE KEYWORDS https://dx.doi.org/10.5155/eurjchem.15.4.338-344.2593 https://www.eurjchem.com/ https://dx.doi.org/10.5155/eurjchem.15.4.338-344.2593 mailto:tidiane3.diop@ucad.edu.sn http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.15.4.338-344.2593&domain=pdf&date_stamp=2024-12-31 Ndiolene et al. / European Journal of Chemistry 15 (4) (2024) 338-344 339 2024 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.15.4.338-344.2593 Table 1. Crystallographic data of the prepared complexes. Compound Tin complex Cadmium complex Empirical formula C12H20Cl4N2O2Sn C7H13CdI3N2 Formula weight (g/mol) 484.79 618.29 Temperature (K) 297(2) 120.01 Crystal system Monoclinic Orthorhombic Space group P21/n Pbca a, (Å) 8.5468(5) 14.7395(9) b, (Å) 17.9907(9) 8.5914(5) c, (Å) 12.7227(7) 23.2825(13) β (°) 94.220(5) 90 Volume (Å3) 1950.98(18) 2948.3(3) Z 4 8 ρcalc (g/cm3) 1.65 2.786 μ (mm-1) 1.861 7.733 F(000) 960.0 2208.0 Crystal size (mm3) 0.41 × 0.17 × 0.13 0.18 × 0.18 × 0.04 Radiation MoKα (λ = 0.71073) MoKα (λ = 0.71073) 2Θ range for data collection (°) 3.92 to 52.74 5.528 to 54.96 Index ranges -10 ≤ h ≤ 9, -22 ≤ k ≤ 22, -15 ≤ l ≤ 15 -19 ≤ h ≤ 19, -11 ≤ k ≤ 11, -30 ≤ l ≤ 30 Reflections collected 21391 72979 Independent reflections 3984 [Rint = 0.0537, Rsigma = 0.0324] 3377 [Rint = 0.0278, Rsigma = 0.0083] Data/restraints/parameters 3984/6/202 3377/0/120 Goodness-of-fit on F2 1.059 1.183 Final R indexes [I≥2σ (I)] R1 = 0.0347, wR2 = 0.0847 R1 = 0.0196, wR2 = 0.0476 Final R indexes [all data] R1 = 0.0456, wR2 = 0.0932 R1 = 0.0205, wR2 = 0.0481 Largest diff. peak/hole (e.Å-3) 0.69/-0.43 0.72/-0.57 HO N N OH OO H2N NH22 2H2OEtOH Scheme 1. Synthesis of ligand (4,4'-(ethane-1,2-diylbis(azanylylidene))bis(pent-2-en-2-ol)). Scheme 2. Oxidation of tin: Sn2+ to Sn4+. Chemicals (acetylacetone, ethylenediamine, SnCl2, CdI2) were purchased from Sigma-Aldrich and used without further purification. The solvent used for the synthesis is absolute ethanol. Infrared spectra were recorded on a FT-IR Bruker Tensor 27 spectrometer in the range of 4000-200 cm-1. 1H and 13C NMR spectra were recorded on a Bruker AV2 (400 MHz) spectrometer in DMSO-d6. X-ray crystallographic data were collected using a Crys Alis PRO 1.171.41.93a diffractometer operating at T = 297 K for the tin complex and 120 K for the cadmium complex. Data were measured using φ and ω scans with MoKα radiation (λ = 0.71073 Å). The structure was solved by direct methods using SIR92 [18] and was refined by least squares minimization with SHELXL [19]. The program used for the representation of molecular and crystal structures: OLEX2 [20]. Crystal data, data collection, and structure refinement details for the complexes are summarized in Table 1. 2.2. Synthesis 2.2.1. Synthesis of the ligand The ligand was synthesized by mixing in a round bottom flask containing ethanol, 6 g (60 mmol) of pentane-2,4-dione and 1.8 g (30 mmol) of ethylenediamine. This mixture is refluxed for 5 h at a temperature of 80 °C; the yellow coloration of the mixture is obtained. After 5 hours of stirring and heating, the mixture is filtered and slowly evaporated for a few days, and the yield obtained is 82% (Scheme 1). 4, 4'-(Ethane-1, 2-diylbis(azanylylidene))bis(pent-2-en-2- ol): Color: White. Yield: 82%. FT-IR (ν, cm-1): 3261 (OH), 2980 (CH), 1602 (C=N). 1H NMR (400 MHz, DMSO-d6, δ, ppm): 1.86 (s, 6H, CH3-C-OH), 1.89 (s, 6H, CH3-C=N), 3.39 (s, 4H, CH2-CH2), 4.94 (s, 2H, CH=C), 14.00 (s, 2H, -OH). 13C NMR (100 MHz, DMSO-d6, 340 Ndiolene et al. / European Journal of Chemistry 15 (4) (2024) 338-344 2024 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.15.4.338-344.2593 Scheme 3. Synthesis of the tin complex. δ, ppm): 193.67 (C2, C2’), 163.40 (C4, C4’), 95.57 (C3, C3’), 43.33 (C6, C6’), 29.07 (C5, C5’), 18.71 (C1, C1’). Solubility: Ethanol, methanol, dimethylsulfoxide, DMF, acetonitrile, acetone, and chloroform. 2.2.2. Synthesis of complexes 2.2.2.1. Synthesis of tin (IV) complex The complex was synthesized by mixing 0.222 g (1 mmol) of the ligand and 0.379 g (2 mmol) of tin(II) chloride in absolute ethanol in a 1:1 ratio. The precipitate mixture obtained is then refluxed for 14 h at a temperature of 80 °C. The yellow solution was then slowly cooled to room temperature and then filtered. After a few days of evaporation of the filtrate, a small yellow crystal was obtained for X-ray diffraction. The crystallographic and IR spectra study of the complex showed a hydrolysis of the ligand as well as an oxidation of tin (II) to tin (IV) (Scheme 2), the hydrolysis of the ligand giving two molecules of acetylacetone and ethylene diamine. Acetylacetone reacts with ethylenediamine by dehydration followed by condensation to give a heptacyclic cation and the acetylacetonate ion. These react with SnCl4 from the Jorgensen symbiosis (Scheme 3), to give the anionic tetrachloro-(acetylacetonato)stannate (IV) complex and a heptacyclic cation (5,7-dimethyl-2,3-dihydro- 1H-1,4-diazepin-4-ium). 5, 7-Dimethyl-2, 3-dihydro-1H-1, 4-diazepin-4-ium tetra chloro-(acetylacetonato)stannate(IV): Color: Yellow. Yield: 32%. FT-IR (ν, cm-1): 3289 (NH) (amine), 3000 (CH), 1659 (C=O) (ketone), 1595 (C=N) (imine). 2.2.2.2. Synthesis of cadmium (II) complex The complex was synthesized by mixing 0.222 g (1 mmol) of the ligand and 2 mmol of CdI2 in absolute ethanol in a 1:1 ratio. This precipitate mixture obtained is then refluxed for a minimum of 5 h at 80 °C. The solutions were then slowly cooled to room temperature and then filtered. After a few days of evaporation of the filtrate, small yellow crystals were obtained for SCXRD. The crystallographic study of the complexes showed that the ligand was partially hydrolyzed. The crystallographic study of the complex showed the hydrolysis of the ligand. The latter reacts with the ketone group of the imine to give a heptacyclic cation (Scheme 4). 5,7-Dimethyl-2,3-dihydro-1H-1,4-diazepin-4-ium tri-iodo cadmate(II): Color: Yellow. Yield: 26%. FT-IR (ν, cm-1): 3271 (NH) (amine), 3097 (CH), 1620 (C=N) (imine). 3. Results and discussion 3.1. IR spectra of complexes The infrared spectrum of the tin complex shows an absorption band at 3289 cm-1 attributed to ν(NH) of a secondary amine, we also observe the presence of small bands around 3000 cm-1 corresponding to the ν(CH). The band at 1659 cm-1 is attributed to ν(C=O) of a ketone, the reduction of this band compared to that of a free ketone expected around 1720 cm-1 shows that C=O participates in the coordination of tin [21]. The vibration band ν(C=N) of the cation appears at 1595 cm-1. For the cadmium complex, the infrared spectrum of the complex shows a band at 1620 cm-1 attributed to the vibration band of the azomethine group ν(C=N) contained in the cation. We also note the presence of aliphatic ν(CH) bands at 2929 and 3097 cm-1 and an absorption band relative to ν(NH) at 3271 cm-1 [22]. 3.2. Crystallographic study of tin complex Crystal structure analysis reveals that the tin complex crystallizes in a monoclinic system with P21/n space group. The parameters of unit cell are: a = 8.5468(5) Å, b = 17.9907(9) Å, c = 12.7227(7) Å, and β = 94.220(5)° (Table 1). The asymmetric unit consists of an anion tetrachloro-(acetylacetonate)stannate (IV) and a heptacyclic cation (Figure 1). The anion contains an ion acetylacetonate and a fraction of SnCl4. The CO bond lengths in the ion acetylacetonate (O1-C2 = 1.281 Å and O2-C4 = 1.282 Å) indicate that these are double bonds (C=O the ketone group) (Table 2) [23]. The geometry around the tin complex is octahedral with cis coordination of the C=O groups of the acetylacetonate ion. The equatorial positions of the octahedron are occupied by two oxygen atoms of the acetylacetonate ion (O1 and O2) and two chlorine atoms (Cl1 and Cl2). The values of the angles around the tin are: Cl2-Sn1-O1 = 89.05(8)°, O1- Sn1-O2 = 86.044(10)°, O2-Sn1-Cl1 = 87.95(7)° and Cl2-Sn1-Cl1 = 96.57(4)° (Table 2). The deformation of the bond angles around the tin compared to the ideal angle shows that the geometry is a deformed octahedron [24], the axial positions are occupied by the chlorine atoms Cl3 and Cl4. Thus, the distances Sn1-O (Sn1-O1 = 2.095 Å and Sn1-O2 = 2.093 Å) and Sn1-Cl (Sn1-Cl1 = 2.3763 Å, Sn1-Cl2 = 2.3749 Å, Sn1-Cl3 = 2.4129 Å, Sn1-Cl4 = 2.4097 Å) are in good agreement with that reported in the literature [25-29]. Ndiolene et al. / European Journal of Chemistry 15 (4) (2024) 338-344 341 2024 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.15.4.338-344.2593 Table 2. Bond lengths and angles for the tin complex. Atom Atom Length (Å) Atom Atom Length (Å) C1 C2 1.500(6) Cl4 Sn1 2.4097(11) C2 C3 1.368(6) C6 C7 1.505(6) C2 O1 1.281(5) C7 C8 1.386(6) C3 C4 1.382(6) C7 N1 1.306(6) C4 C5 1.494(5) C8 C9 1.391(6) C4 O2 1.282(4) C9 C10 1.482(6) O1 Sn1 2.095(2) C9 N2 1.305(5) O2 Sn1 2.093(2) C11 C12 1.478(6) Cl1 Sn1 2.3763(10) C11 N1 1.456(6) Cl2 Sn1 2.3749(10) C12 N2 1.445(6) Cl3 Sn1 2.4129(11) Atom Atom Atom Angle (°) Atom Atom Atom Angle (°) C3 C2 C1 120.3(4) Cl1 Sn1 Cl3 92.93(4) O1 C2 C1 114.2(4) Cl1 Sn1 Cl4 92.01(4) O1 C2 C3 125.5(4) Cl2 Sn1 Cl1 96.57(4) C2 C3 C4 127.4(4) Cl2 Sn1 Cl3 90.90(4) C3 C4 C5 121.0(4) Cl2 Sn1 Cl4 91.64(4) O2 C4 C3 125.0(4) Cl4 Sn1 Cl3 174.15(4) O2 C4 C5 114.0(4) C8 C7 C6 118.3(4) C2 O1 Sn1 127.1(3) N1 C7 C6 115.4(4) C4 O2 Sn1 127.1(2) N1 C7 C8 126.2(4) O1 Sn1 Cl1 174.36(8) C7 C8 C9 131.8(4) O1 Sn1 Cl2 89.05(8) C8 C9 C10 119.1(4) O1 Sn1 Cl3 86.45(8) N2 C9 C8 125.4(4) O1 Sn1 Cl4 88.32(8) N2 C9 C10 115.4(4) O2 Sn1 O1 86.44(10) N1 C11 C12 114.4(5) O2 Sn1 Cl1 87.95(7) N2 C12 C11 111.9(4) O2 Sn1 Cl2 175.48(7) C7 N1 C11 125.7(4) O2 Sn1 Cl3 88.87(8) C9 N2 C12 126.0(4) O2 Sn1 Cl4 88.18(8) Table 3. Geometric parameters of hydrogen bonds of the tin complex. D-H···A * d(D-H), Å d(H-A), Å d(D-A), Å ∠ D-H-A, ° N1-H1··· Cl31 0.859(19) 2.69(2) 3.502(4) 159(3) N2-H2··· Cl42 0.851(19) 2.52(2) 3.350(4) 164(3) * Symmetry codes: (1) x+1 /2, -y+1/2, z-1/2; (2) –x+1/2, y+1/2, -z+1/2. Scheme 4. Synthesis of the cadmium complex. Figure 1. Crystal structure of the tin complex. 342 Ndiolene et al. / European Journal of Chemistry 15 (4) (2024) 338-344 2024 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.15.4.338-344.2593 Table 4. Bond lengths and angles for the cadmium complex *. Atom Atom Length (Å) Atom Atom Length (Å) I1 Cd 2.7231(4) N2 C4 1.449(5) I2 Cd1 2.8789(4) C1 C2 1.398(6) I2 Cd 2.8256(4) C1 C6 1.504(6) I3 Cd 2.7275(4) C2 C3 1.392(6) N1 C1 1.314(5) C3 C7 1.505(6) N1 C5 1.451(5) C4 C5 1.524(6) N2 C3 1.323(5) Atom Atom Atom Angle (°) Atom Atom Atom Angle (°) Cd I2 Cd1 102.608(12) N1 C1 C2 126.0(4) I1 Cd I2 111.910(13) N1 C1 C6 115.5(4) I1 Cd I22 109.756(12) C2 C1 C6 118.5(4) I1 Cd I3 121.276(13) C3 C2 C1 131.2(4) I2 Cd I22 101.225(12) N2 C3 C2 126.8(4) I3 Cd I2 108.178(13) N2 C3 C7 114.9(4) I3 Cd I22 102.255(12) C2 C3 C7 118.2(4) C1 N1 C5 125.0(3) N2 C4 C5 111.8(3) C3 N2 C4 126.6(4) N1 C5 C4 113.0(3) * Symmetry codes: 1 1/2-x, 1/2+y, +z; 2 1/2-x, -1/2+y, +z. Table 5. Geometric parameters of hydrogen bonds of the cadmium complex. D-H···A d(D-H), Å d(H-A), Å d(D-A), Å ∠ D-H-A, ° N1-H1···I1 0.879(5) 2.977(3) 3.742(3) 1146.6(3) N2-H2···I3 0.881(5) 2.735(3) 3.528(3) 150.4(3) Figure 2. The N-H···Cl hydrogen bonds of the tin complex. Symmetry codes: i x+1 /2, -y+1/2, z-1/2; ii –x+1/2, y+1/2, -z+1/2. Figure 3. Infinite chain of the tin complex. The anionic complex is linked to the heptacyclic cation by hydrogen bonds of type Cl31···H1-N1 and Cl42···H2-N2 (Table 3) that form an infinite chain (Figures 2 and 3). 3.3. Crystallographic study of cadmium complex The complex of cadmium crystallizes in the orthorhombic system with the Pbca space group. The parameters of unit cell are a = 14.7395(9) Å, b = 8.5914(5) Å, c = 23.2825(13) Å, V = 2948.3(3) Å3, Z = 8. This structure reveals that cadmium is tetracoordinated with four iodine atoms (Figure 4). Ndiolene et al. / European Journal of Chemistry 15 (4) (2024) 338-344 343 2024 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.15.4.338-344.2593 Figure 4. Crystal structure of the cadmium complex, Symmetry codes: i 1/2-x, 1/2+y, +z; ii 1/2-x, -1/2+y, +z. Figure 5. Infinite three-dimensional structure of the cadmium complex stabilized by hydrogen bonds (dotted line). Three non-equivalent iodine atoms are noted in the crystal structure, the terminal atoms I1 and I3, and one atom I2 serve as a bridge between two cadmium atoms. The geometry around cadmium is a distorted tetrahedron with the following bond lengths and angles: Cd-I1 = 2.7231(4); Cd1-I2 = 2.8789(4); Cd- I2 = 2.8256(4); Cd-I3 = 2.7275(4); I1-Cd-I22 = 109.756(12)°, I1- Cd-I2 = 111.910(13)°; I3-Cd-I22 = 102.255(12)° and I3-Cd-I1 = 121.276(13)° (Table 4). These values obtained are similar to those reported by Gesing et al. [30]. The CdI3- ion is linked to the heptacyclic cation by interatomic hydrogen bonds between the terminal iodine and the hydrogens of the imine groups forming an infinite three-dimensional structure; N1–H1···I1 = 2.976 Å, N2–H2···I3 = 2.735 Å (Table 5) and C5–H1···I3 = 3.144 Å (Figure 5). 4. Conclusion In summary, two new coordination complexes C12H20N2O2·SnCl4 and CdI3·C7H13N2 were obtained, and their structures were characterized by IR spectra and X-ray diffraction. In the tin complex, the atom Sn(IV) was coordinated by two O atoms of the acetylacetonate anion acting as bidentate ligands and four ion chlorides. The geometry of the tin complex is octahedral and that of the cadmium complex is tetrahedral. The heptacyclic cation and the complex anionic are interlinked by hydrogen bonding interactions, namely N–H···Cl and N–H···I, forming a chain network. Acknowledgements The authors are thankful to the Service Commun De’analyse par Diffraction des Rayons X, Université de Bretagne Occidentale, 6 Avenue Victor Le Gorgeu, CS 93837, F-29238 BREST Cedex 3, France. Supporting information CCDC-2112975 (C12H20N2O2·SnCl4) and CCDC-2115928 (CdI3·C7H13N2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interest: The authors declare that they have no conflict of interest. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. CRediT authorship contribution statement Conceptualization: Tidiane Diop, Aminata Diasse-Sarr; Methodology: Adrienne Ndiolene, Tidiane Diop; Software: Mouhamadou Sembene Boye; Validation: Adrienne Ndiolene, Tidiane Diop; Formal Analysis: Adrienne Ndiolene; Investigation: Adrienne Ndiolene, Tidiane Diop; Resources: Tidiane Diop, Aminata Diasse-Sarr; Data Curation: Adrienne Ndiolene; Writing - Original Draft: Adrienne Ndiolene, Tidiane Diop; Writing - Review and Editing: Mouhamadou Sembene Boye, Aminata Diasse-Sarr; Visualization: Adrienne Ndiolene; Supervision: Tidiane Diop, Aminata Diasse-Sarr; Project Administration: Aminata Diasse-Sarr. http://www.ccdc.cam.ac.uk/data_request/cif mailto:data_request@ccdc.cam.ac.uk 344 Ndiolene et al. / European Journal of Chemistry 15 (4) (2024) 338-344 2024 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.15.4.338-344.2593 ORCID and Email Adrienne Ndiolene adrienne.ndiolene@ucad.edu.sn https://orcid.org/0009-0004-2411-8836 Tidiane Diop tidiane3.diop@ucad.edu.sn https://orcid.org/0000-0003-1098-451X Mouhamadou Sembene Boye mouhasboye@hotmail.com https://orcid.org/0009-0000-8447-6409 Aminata Diasse-Sarr aminatadiasse.sarr@ucad.edu.sn https://orcid.org/0000-0002-4143-4281 References [1]. BelhajSalah, S.; Abdelbaky, M.; García-Granda, S.; Essalah, K.; Ben Nasr, C.; Mrad, M. Synthesis, crystal structure, vibrational, optical properties, thermal analysis and theoretical study of a new Sn(IV) complex (C5H14N2)2[SnCl6]2·5H2O. Solid State Sci. 2018, 86, 77–85. [2]. Sanchez, C.; Julián, B.; Belleville, P.; Popall, M. Applications of hybrid organic–inorganic nanocomposites. J. Mater. Chem. 2005, 15 (35-36), 3559. [3]. Borriello, I.; Cantele, G.; Ninno, D. Ab initioinvestigation of hybrid organic-inorganic perovskites based on tin halides. Phys. Rev. B. 2008, 77 (23), 235214 https://doi.org/10.1103/PhysRevB.77.235214. [4]. Ding, X.; Wang, S.; Li, Y.; Huang, W. Inorganic anion-assisted supramolecular assemblies of bent dipyridines: effects of anionic geometries on hydrogen-bonding networks. Inorg. Chem. Front. 2015, 2 (3), 263–272. [5]. Ndiaye, M.; Pouye, S. F.; Diop, M. B.; Diop, L.; Samb, A.; Oliver, A. G. Tin(IV) Halides Zero-dimensional based Inorganic-Organic Hybrid Materials: Crystal Structures and Hirshfeld Surface Analysis. Earthline J. Chem. Sci. 2023, 57–76. [6]. Liu, Y.; Summers, M.; Edder, C.; Fréchet, J.; McGehee, M. Using Resonance Energy Transfer to Improve Exciton Harvesting in Organic–Inorganic Hybrid Photovoltaic Cells. Adv. Mater. 2005, 17 (24), 2960–2964. [7]. Man, X.; Li, S.; Xu, G.; Li, W.; Zhu, M.; Zhang, Z.; Liang, H.; Yang, F. Developing a Copper(II) Isopropyl 2-Pyridyl Ketone Thio semicarbazone Compound Based on the IB Subdomain of Human Serum Albumin–Indomethacin Complex: Inhibiting Tumor Growth by Remodeling the Tumor Microenvironment. J. Med. Chem. 2024, 67 (7), 5744–5757. [8]. Man, X.; Li, W.; Zhu, M.; Li, S.; Xu, G.; Zhang, Z.; Liang, H.; Yang, F. Anticancer Tetranuclear Cu(I) Complex Catalyzes a Click Reaction to Synthesize a Chemotherapeutic Agent in situ to Achieve Targeted Dual-Agent Combination Therapy for Cancer. Angew. Chem. Int. Ed. 2024, https://doi.org/10.1002/anie.202411846. [9]. Li, W.; Li, T.; Pan, Y.; Li, S.; Xu, G.; Zhang, Z.; Liang, H.; Yang, F. Designing a Mitochondria-Targeted Theranostic Cyclometalated Iridium(III) Complex: Overcoming Cisplatin Resistance and Inhibiting Tumor Metastasis through Necroptosis and Immune Response. J. Med. Chem. 2024, 67 (5), 3843–3859. [10]. Hermi, S.; Alotaibi, A. A.; Lefebvre, F.; Ben Nasr, C.; Mrad, M. H. Elaboration, crystal structure, physico-chemical characterization and theoretical investigation of a new non-centrosymmetric Sn(IV) complex (C4H12N2)[SnCl6]·3H2O. J. Mol. Struct. 2020, 1216, 128296. [11]. Shaheen, S. E.; Brabec, C. J.; Sariciftci, N. S.; Padinger, F.; Fromherz, T.; Hummelen, J. C. 2.5% Efficient organic plastic solar cells. Appl. Phys. Lett. 2001, 78 (6), 841–843. [12]. Ilayabarathi, P.; Chandrasekaran, J.; Maadeswaran, P. Synthesis, growth and characterization of l-tyrosine hydrochloride a semi- organic nonlinear optical crystal. Optik 2013, 124 (12), 1125–1127. [13]. Chandran, S. K.; Paulraj, R.; Ramasamy, P. Crystal growth, spectral, optical, laser damage, photoconductivity and dielectric properties of semiorganic l-cystine hydrochloride single crystal. Spectrochim. Acta A: Mol. Biomol. Spectrosc. 2015, 151, 432–437. [14]. Liu, X.; Ji, C.; Wu, Z.; Li, L.; Han, S.; Wang, Y.; Sun, Z.; Luo, J. [C5H12N]SnCl3: A Tin Halide Organic–Inorganic Hybrid as an Above- Room-Temperature Solid-State Nonlinear Optical Switch. Chemistry A. European J. 2019, 25 (10), 2610–2615. [15]. Zhou, C.; Lin, H.; Tian, Y.; Yuan, Z.; Clark, R.; Chen, B.; van de Burgt, L. J.; Wang, J. C.; Zhou, Y.; Hanson, K.; Meisner, Q. J.; Neu, J.; Besara, T.; Siegrist, T.; Lambers, E.; Djurovich, P.; Ma, B. Luminescent zero- dimensional organic metal halide hybrids with near-unity quantum efficiency. Chem. Sci. 2018, 9 (3), 586–593. [16]. Ndiolene, A.; Diop, T.; Boye, M. S.; Diasse-Sarr, A.; Englert, U. A new organic–inorganic compound, ethylenediammonium hexachlorido stannate(IV) p-anisaldehyde disolvate. Acta Crystallogr E. Cryst Commun 2021, 77 (7), 696–699. [17]. Guo, X.; McCleese, C.; Kolodziej, C.; Samia, A. C.; Zhao, Y.; Burda, C. Identification and characterization of the intermediate phase in hybrid organic–inorganic MAPbI3perovskite. Dalton Trans. 2016, 45 (9), 3806–3813. [18]. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. Completion and refinement of crystal structures withSIR92. J. Appl Crystallogr 1993, 26 (3), 343–350. [19]. Sheldrick, G. M. Crystal structure refinement withSHELXL. Acta Crystallogr C. Struct Chem 2015, 71 (1), 3–8. [20]. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, 339–341. [21]. El-Ansary, A. L.; Abdel-Kader, N. S. Synthesis, Characterization of La(III), Nd(III), and Er(III) Complexes with Schiff Bases Derived from Benzopyran-4-one and Thier Fluorescence Study. Int. J. Inorg. Chem. 2012, 2012, 1–13. [22]. El-Boraey, H. A. Structural and thermal studies of some aroylhydrazone Schiff’s bases-transition metal complexes. J. Therm Anal Calorim 2005, 81 (2), 339–346. [23]. Ramadan, R. M.; Abdel-Rahman, L. H.; Ismael, M.; Youssef, T. A.; Ali, S. A. Synthesis and spectroscopic studies of some chromium and molybdenum derivatives of bis-(acetylacetone)ethylenediimine ligand. J. Mol. Struct. 2013, 1049, 7–12. [24]. Elinburg, J. K.; Hyre, A. S.; McNeely, J.; Alam, T. M.; Klenner, S.; Pöttgen, R.; Rheingold, A. L.; Doerrer, L. H. Formation of monomeric Sn(ii) and Sn(iv) perfluoropinacolate complexes and their characterization by 119Sn Mössbauer and 119Sn NMR spectroscopies. Dalton Trans. 2020, 49 (39), 13773–13785. [25]. Pettinari, C.; Marchetti, F.; Cingolani, A.; Lorenzotti, A.; Mundorff, E.; Rossi, M.; Caruso, F. Tin(IV) and organotin(IV) derivatives of novel β- diketones. Inorg. Chim. Acta 1997, 262 (1), 33–46. [26]. Zhou, Y.; Richeson, D. S. Bulky Amidinate Complexes of Tin(IV). Synthesis and Structure of Sn(RNC(R‘)NR)2Cl2 (R = Cyclohexyl, R‘ = H, Me; R = SiMe3, R‘ = tBu). Inorg. Chem. 1997, 36 (4), 501–504. [27]. Diop, T.; Lee, A. v.; Diop, L. Tetrabutylammonium butyltetra chloridostannate(IV). Acta Crystallogr E. Struct Rep Online 2013, 69 (10), m562–m563. [28]. Pettinari, C.; Marchetti, F.; Gregori, A.; Cingolani, A.; Tanski, J.; Rossi, M.; Caruso, F. Tin(IV) and organotin(IV) derivatives of novel β- diketones I. Dialkyltin(IV) complexes of 1-phenyl-3-methyl-4-R′(CO)- pyrazol-5-one (R′ = CCl3, OCH3, OC2H5, OiC3H7, OC7H7). Crystal and molecular structure of trans-dimethylbis]1-phenyl-3-methyl- 4-i- propoxycarbonyl-pyrazolon-5-ato]tin(IV). Inorg. Chim. Acta 1997, 257 (1), 37–48. [29]. Hajlaoui, S.; Chaabane, I.; Oueslati, A.; Guidara, K.; Bulou, A. A theoretical study on the molecular structure and vibrational (FT-IR and Raman) spectra of new organic–inorganic compound [N(C3H7)4]2SnCl6. Spectrochim. Acta A: Mol. Biomol. Spectrosc. 2014, 117, 225–233. [30]. Gesing, T. M.; Lork, E.; Terao, H.; Ishihara, H. NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH2)3]CdI3 and [4- ClC6H5NH3]3CdBr5. Z. fur Naturforsch. B 2016, 71 (3), 241–248. Copyright © 2024 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at https://www.eurjchem.com/index.php/eurjchem/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution, or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (https://www.eurjchem.com/index.php/eurjchem/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). mailto:adrienne.ndiolene@ucad.edu.sn https://orcid.org/0009-0004-2411-8836 mailto:tidiane3.diop@ucad.edu.sn https://orcid.org/0000-0003-1098-451X mailto:mouhasboye@hotmail.com https://orcid.org/0009-0000-8447-6409 mailto:aminatadiasse.sarr@ucad.edu.sn https://orcid.org/0000-0002-4143-4281 https://doi.org/10.1103/PhysRevB.77.235214 https://doi.org/10.1002/anie.202411846 https://www.eurjchem.com/index.php/eurjchem/terms http://creativecommons.org/licenses/by-nc/4.0 https://www.eurjchem.com/index.php/eurjchem/terms 1. Introduction 2. Experimental 2.1. Materials and physical measurements 2.2. Synthesis 2.2.1. Synthesis of the ligand 2.2.2. Synthesis of complexes 2.2.2.1. Synthesis of tin (IV) complex 2.2.2.2. Synthesis of cadmium (II) complex 3. Results and discussion 3.1. IR spectra of complexes 3.2. Crystallographic study of tin complex 3.3. Crystallographic study of cadmium complex 4. Conclusion Acknowledgements Supporting information Disclosure statement CRediT authorship contribution statement ORCID and Email References PrintField10: PrintField11: PrintField12: PrintField13: PrintField14: PrintField15: PrintField16: PrintField20: PrintField21: PrintField22: PrintField23: PrintField24: PrintField25: PrintField26: