untitled European Journal of Chemistry 6 (3) (2015) 237‐241 European Journal of Chemistry ISSN 2153‐2249 (Print) / ISSN 2153‐2257 (Online)  2015 Atlanta Publishing House LLC ‐ All rights reserved ‐ Printed in the USA http://dx.doi.org/10.5155/eurjchem.6.3.237‐241.1265 European Journal of Chemistry Journal webpage: www.eurjchem.com Synthesis, characterization and crystal structure of cis‐bis[4‐fluoro‐N‐(diethylcarbamothioyl)benzamido‐κ2O,S]platinum(II) Ilkay Gumus 1,*, Ummuhan Solmaz 1, Omer Celik 2, Gun Binzet 1,3, Gulten Kavak Balcı 4 and Hakan Arslan 1 1 Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, 33343, Turkey 2 Science and Technology Application and Research Center, Dicle University, Diyarbakır, 21280, Turkey 3 Department of Chemistry, Faculty of Education, Mersin University, Mersin, 33343, Turkey 4 Department of Physics, Faculty of Sciences, Dicle University, 21280 Diyarbakır, Turkey * Corresponding author at: Department of Chemistry, Faculty of Arts and Science, Mersin University, Mersin, 33343, Turkey. Tel.: +90.538.5589656. Fax: +90.324.3610047. E‐mail address: gumus.ilkay84@gmail.com (I. Gumus). ARTICLE INFORMATION ABSTRACT DOI: 10.5155/eurjchem.6.3.237‐241.1265 Received: 08 April 2015 Received in revised form: 20 May 2015 Accepted: 28 May 2015 Published online: 30 September 2015 Printed: 30 September 2015 cis‐Bis[4‐fluoro‐N‐(diethylcarbamothioyl)benzamido‐κ2O,S]platinum(II), cis‐[Pt(L‐O,S)2], was synthesized and characterized by elemental analyses, FT‐IR and NMR techniques. The obtained metal complex was also characterized by a single crystal X‐ray diffraction study. Molecule formula of the title compound is C24H28F2N4O2PtS2: tetragonal, space group I41/a, a = 19.7530(4) Å, b = 19.7530(4) Å, c = 13.7137(3) Å, V = 5350.83(19) Å3, Z = 8, Dcalc = 1.742 g/mm3, 22890 reflections measured (3.62 ≤ 2Θ ≤ 52.72), 2733 (Rint = 0.0272), which were used in all calculations. A square‐planar coordination geometry is formed around the Pt atom by two S atoms and two O atoms of the N‐(diethylcarbamothioyl)‐4‐fluorobenzamide ligand which are a cis configuration. KEYWORDS Thiourea Synthesis Cis‐configuration Benzoyl thiourea Platinum complex X‐ray single crystal diffraction Cite this: Eur. J. Chem. 2015, 6(3), 237‐241 1. Introduction Thioureas are important organic compounds possessing significant biological activities, act as corrosion inhibitors, catalyst and antioxidant, and are polymer components [1‐13]. Moreover, the hydrogen‐bonding ability of the thiourea moiety has been extensively used in the construction of anion receptors. Thiourea derivatives have attracted considerable attention due to their potential applications [14‐22]. Thiourea‐ based compounds are good candidates for coordination to transition metals as they have sulfur and oxygen donor atoms [13,23‐30]. They are also able to bind through multiple bonding modes with one metal ion: chelation through both S and O, just through S, or just through O atoms [31]. Thioureas are selective ligands for the platinum group metals such as rhodium, platinum and palladium [32]. Platinum‐thiourea complexes have attracted interest because of their luminescence properties [33] that find applications in optoelectronic devices [34‐36], luminescent probes for biomolecules [37,38] and chemical sensors [38‐41]. In the present study, we combined thiourea group with fluorine‐containing organic compound was report the preparation and characterization of new N‐(diethylcarbamo thioyl)‐4‐fluoro benzamide (HL) thiourea compound and its Pt(II) complex (Scheme 1). The crystal and molecular struc‐ tures of Pt (II) complex were characterized by single crystal X‐ ray diffraction study. 2. Experimental 2.1. Instrumentation C, H, and N analyses were carried out on a Carlo Erba MOD 1106 elemental analyzer. Infrared measurement was recorded in the range 400‐4000 cm−1 on FT‐IR/FIR/NIR Spectrometer Frontier, ATR Instrument. The 1H NMR spectrums were recorded in CDCl3 solvent on Bruker 400 MHz spectrophoto‐ meter using tetramethylsilane as an internal reference. Crystallographic measurements of the compound were carried out at 296(2) K using a Bruker APEX‐II CCD area‐detector diffractometer. 238 Gumus et al. / European Journal of Chemistry 6 (3) (2015) 237‐241 Scheme 1 The intensity data were collected using graphite monochromated Mo‐Kα radiation (λ = 0.71073 Å). Absorption corrections were applied with the program SADABS [42]. The structure was solved by direct methods SHELXS‐97 [43], and refined by full‐matrix least‐squares techniques on F2 using SHELXL‐97 [43] with refinement of F2 against all reflections. Hydrogen atoms were constrained by difference maps and were refined isotropically, and all non‐H atoms were refined anisotropically. Crystallographic data and details of data collections and structure refinements of compound cis‐[Pt(L‐ O,S)2] are listed in Table 1. The molecular structure plots were prepared using PLATON [44] and ORTEPIII [44]. The anisot‐ ropic thermal parameters and structure factors (observed and calculated), full list of bond distances, bond angles and torsional angles are given in supplementary materials. The geometric special details: all esds (except the esd in the dihedral angle between two planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving planes. Table 1. Crystal data and structure refinement for cis‐[Pt(L‐O,S)2]. Empirical formula C24H28F2N4O2PtS2 Formula weight 701.74 Temperature (K) 296.15 Crystal system Tetragonal Space group I41/a a (Å) 19.7530(4) b (Å) 19.7530(4) c (Å) 13.7137(3) Volume (Å3) 5350.83(19) Z 8 ρcalc (g/cm3) 1.742 Μ (mm‐1) 5.443 F (000) 2752.0 Crystal size (mm3) 0.45 × 0.15 × 0.15 Radiation Mo Kα (λ = 0.71073 Å) 2Θ range for data collection (°) 3.616 to 52.724 Index ranges ‐27 ≤ h ≤ 29 ‐26 ≤ k ≤ 31 ‐21 ≤ l ≤ 20 Reflections collected 22890 Independent reflections 2733 [Rint = 0.0272, Rsigma = 0.0268] Data/restraints/parameters 2733/44/158 Goodness‐of‐fit on F2 1.058 Final R indexes [I ≥ 2σ (I)] R1 = 0.0303, wR2 = 0.0787 Final R indexes [all data] R1 = 0.0405, wR2 = 0.0847 Largest diff. peak/hole (eÅ‐3) 0.61/‐0.72 2.2. Reagents 4‐Fluorobenzoyl chloride, potassium thiocyanate, diethylamine were purchased from Merck and used as received. Acetone and dichloromethane used without further purification. Ethanol was dried and distilled before the using. All the other chemicals used for the preparation of the ligand and platinum complex were of reagent grade quality. 2.3. Synthesis of ligand HL was prepared according to previously published method [45‐47]. A solution of 4‐fluoro benzoyl chloride (5.10‐2 mol) in acetone (50 mL) was added dropwise to a suspension of potassium thiocyanate (5.10‐2 mol) in acetone (30 mL). The reaction mixture was heated under reflux for 30 min, and then cooled to room temperature. A solution of diethylamine (5.10‐2 mol) in acetone (10 mL) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 mL) was added and the solution filtered. The solid product was washed with water and purified by recrystallization from an ethanol:dichloromethane mixture (1:1, v:v) (Scheme 1). N‐(diethylcarbamothioyl)‐4‐fluorobenzamide, (HL): Color: White. Yield: 88 %. FT‐IR (ATR, ν, cm‐1): 3293 (w) (NH), 2998, 2977, 2933 (vw) (CH), 1647 (s) (C=O), 1275 (m) (C=S), 761 (w) (C‐F). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.41 (s, 1H, NH), 7.88 (d, 2H, Ar‐H), 7.16 (d, 2H, Ar‐H), 4.04 (q, 2H, N‐CH2), 3.70 (q, 2H, N‐CH2), 1.38 (t, 3H, CH3), 1.32 (t, 3H, CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 179.39 (C=S), 166.76 (C=O), 130.61 (C‐Ar), 130.52 (C‐Ar), 116.01 (C‐Ar), 115.78 (C‐Ar), 47.94 (C‐ N), 47.63 (C‐N), 13.28 (CH3), 11.47 (CH3). Anal. calcd. for C12H15FN2OS: C, 56.67; H, 5.94; N, 11.01; Found: C, 56.50; H, 5.90; N, 11.01%. 2.4. Synthesis of the complex The solution of N‐(diethylcarbamothioyl)‐4‐fluoro benzamide in ethanol (50 mL) at 70 °C was added dropwise a solution of potassium tetrachloroplatinate(II) (10.0 mmol) in water (50 mL). The reaction mixture was stirred for 30 min, and then cooled to room temperature. A brown precipitate was formed which was filtered off and recrystallized from ethanol:dichloromethane mixture (2:1, v:v) (Scheme 2). Cis‐bis[4‐fluoro‐N‐(diethylcarbamothioyl)benzamido‐κ2O, S] platinum(II), (cis‐[Pt(L‐O,S)2]): Color: Yellow. Yield: 83 %. FT‐ IR (ATR, ν, cm‐1): 2989, 2939, 2871 (w) (C‐H), 1597 (w) ν(C‐ N), 1489 (vs) ν(C‐O), 759 (w) ν(C‐F). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.22 (d, 4H, Ar‐Ha), 7.10 (d, 4H, Ar‐Hb), 3.80 (dd, 8H, N‐CH2), 1.28 (t, 12H, CH2‐CH3). 13C NMR (100 MHz, CDCl3, δ, ppm): 167.50 (2C, C‐S), 167.07 (2C, C‐O), 131.60 (2C, C‐Ar), 131.68 (2C, C‐Ar), 115.19 (4C, C‐Ar), 114.97 (4C, C‐Ar), 47.07 (2C‐N), 45.97 (2C‐N), 13.12 (2CH3), 12.44 (2CH3). Anal. calcd. for C24H28F2N4O2PtS2: C, 41.08; H, 4.02; N, 7.98; Found: C, 40.20; H, 4.00; N, 7.9 %. 3. Results and discussion 3.1. Synthesis and characterization 4‐Fluoro benzoyl isothiocyanate was synthesized by reaction of 4‐flouro benzoyl chloride with an equimolar amount of potassium thiocyanate in dry acetone. HL was synthesized from 4‐flourobenzoyl isothiocyanate and diethyl amine in dry acetone. Both HL and cis‐[Pt(L‐O,S)2] compounds were characterized by elemental analysis, FT‐IR, 1H NMR and 13C NMR techniques. Data of the synthesized compounds confirmed the proposed structures given in Scheme 1 and 2. The FT‐IR spectra of HL was showed characteristic bands at 3293 and 1647 cm−1 corresponding to ν(NH) and (C=O), respectively. Moreover synthesized free ligand showed weak intensity C=S stretching vibration in the 1275 cm−1. The FT‐IR spectra of the platin complex displayed important differences when compared with the FT‐IR spectra of the corresponding ligand. Gumus et al. / European Journal of Chemistry 6 (3) (2015) 237‐241 239 Table 2. Selected bond lengths (Å) and bond angles (°) for cis‐[Pt(L‐O,S)2]. Atom Atom Length, Å Atom Atom Atom Angle, ° Pt1 S11 2.2232(13) S11 Pt1 S1 86.08(7) Pt1 S1 2.2232(12) O1 Pt1 S1 94.49(9) Pt1 O1 2.033(3) O11 Pt1 S11 94.49(9) Pt1 O11 2.033(3) O11 Pt1 S1 178.19(10) S1 C8 1.710(5) O1 Pt1 S11 178.19(10) F1 C5 1.362(5) O1 Pt1 O11 84.98(15) O1 C1 1.262(5) C8 S1 Pt1 108.42(15) N1 C1 1.313(5) C1 O1 Pt1 128.8(2) N1 C8 1.346(5) C1 N1 C8 127.1(4) N2 C8 1.340(6) C8 N2 C9 120.9(4) N2 C9 1.460(7) C8 N2 C11 122.0(5) N2 C11 1.500(8) C9 N2 C11 116.5(5) C1 C2 1.504(5) O1 C1 N1 131.1(4) C2 C3 1.386(6) O1 C1 C2 114.6(3) C2 C7 1.370(6) N1 C1 C2 114.3(4) C9 C10 1.489(9) F1 C5 C6 118.3(5) C11 C12 1.127(16) C4 C5 F1 118.7(5) N1 C8 S1 129.7(3) N2 C8 S1 116.0(3) N2 C8 N1 114.3(4) N2 C9 C10 110.7(6) C12 C11 N2 124.6(15) 1 1‐x, 1/2‐y, +z Scheme 2 Figure 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The most important differences are the ν(N‐H) band of free ligand disappeared completely in the spectra of the Pt(II) complex indicating that the deprotanation of the NH group and coordination via the thiolate S‐atom and carbonyl O‐atom. These results agree with the data in the literature [45,46]. The 1H NMR spectra of the HL ligand and its platin complex were recorded in CDCl3. The 1H NMR data of the obtained compounds were given in the experimental section and consistent with the structural results. The N‐H signal in the 1H NMR spectrum for the ligand at 8.41 ppm disappeared upon the complexation reaction. All other proton signals were appeared in appropriate place (Section 2.3 and 2.4). The molecular structures and packing diagrams of cis‐ [Pt(L‐O,S)2] are depicted in Figures 1 and 2, respectively. Crystallographic information was briefly given in Table 1 for the title compound. Selected bond lengths and angles of the compounds are presented in Table 2. The structure of the platin complex shows that the platin atom with 4‐fold coordination set up by two oxygen and two sulfur atoms [S(1)‐Pt(1)‐O(1): 178.19(10) and O(1)‐Pt(1)‐ S(1): 94.49(9)°] in a cis geometry. The bond distances of the C‐ S [S(1)‐C(8): 1.710(5)] and C‐O [C1‐O1: 1.262(5) Å] in the chelate ring are longer than average C=S and C=O double bond distances of thiourea derivatives [47]. 240 Gumus et al. / European Journal of Chemistry 6 (3) (2015) 237‐241 Figure 2. Packing diagram for the title compound. The bond lengths of all C‐N bonds in the chelate rings (C1‐ N1 1.313(5), N1‐C8 1.346(5), C8‐N2 1.340(6) Å) are shorter than the normal C‐N single bond (1.48 Å) and longer than normal C=N double bond (1.25 Å) due to the strong delocalization in the chelate rings. As expected, the Pt‐O bond distance [2.033(3) Å] is shorter than Pt‐S bond distance [2.2232(13) Å]. These parameters indicate that shift from the square planar structure to tetrahedral structure. These results are confirmed by C1‐N1‐C8‐N2 showing sp2 hybridization in N1 atoms [48‐51]. All the other bond lengths and bond angles fall within the expected range. 4. Conclusions In this work, N‐(diethylcarbamothioyl)‐4‐fluorobenzamide ligand and its Pt(II) complex has been synthesized and characterized by elemental analysis, FT‐IR spectroscopy, 1H NMR and 13C NMR techniques. Crystal and molecular structures of metal complex was analyzed by X‐ray single crystal diffraction method. Cis‐bis[4‐fluoro‐N‐(diethylcarbamo thioyl)benzamido‐κ2O,S]platinum(II) has been reported to crystallize in the tetragonal space group I41/a. The crystal structure of cis‐[Pt(L‐O,S)2] confirms that the N‐(diethyl carbamothioyl)‐4‐fluoro benzamide ligand is a bidentate chelating ligand, coordinating to the platin through thio‐ carbonyl and carbonyl groups. The comparative analysis was performed with literature data. The structure of this compound is consistent with the structure of other thiourea derivatives. 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