untitled ISSN 215 Synthes N'1,N'4‐b Ahmed Ab Department of C * Corresponding Tel.: +965.66734 ARTICLE IN DOI: 10.5155/e Received: 03 No Received in rev Accepted: 29 No Published onlin Printed: 31 Mar KEYWORDS Bis(hydrazones Metal complexe Thermal analys Magnetic mome X‐ray crystallog Tetrametallic co 1. Introduct Hydrazo due to their and cleave conditions [ activity as w hydrazone pharmacolog used agains tuberculosis and pyridine than INH [4 aminobenzoy aminobenzoy of Cu(II) com benzylidene‐ active. The bactericidal acetylmonox tetrahedral complexes [ nicotinylhyd groups (NH (N2O2). The r 53‐2249 (Print) sis and ch bis((E)‐3, bd‐Elhamied Chemistry, Faculty g author at: Depart 4989. Fax: +965.24 FORMATION eurjchem.7.1.81‐90 ovember 2015 vised form: 25 Nov ovember 2015 ne: 31 March 2016 rch 2016 S s) es sis ent graphy omplexes tion nes and their m antimicrobial the DNA stra [2]. They have well as pharm complexes act gical useful. Iso st a wide spe . Hydrazones d e aldehydes sho 4]. The antibac ylhydrazone ylhydrazone co mplexes is more ‐hydrazoquinol chelation pu agent [5]. Bin ximehydrazone) for the Zn(II) [6]. Metal com drazone) release CO) and beha results provide / ISSN 2153‐225 ht Europ aracteriz 4‐dihydro d El‐Asmy *, of Science, Kuwait tment of Chemistry, 4816482. E‐mail ad 0.1359 ember 2015 metal complexe activities [1]. nds under dif e applications macological app t as enzyme onicotinic acid ectrum of bact derived from c owed better an cterial activity and 4‐hydro omplexes show e than Zn(II) com line was prove ushed the lig nuclear complex ) have oct ) and square‐p plexes of 2,5‐h ed two protons aves as a bine d a square‐plan European Journ Europ 57 (Online)  20 ttp://dx.doi.org pean Jo Journal web ation of tr oxybenzy , Bakir Jerag University, Safat, 1 y, Faculty of Science ddress: aelasmy@ya ABSTRACT Single crysta grown by slow and Cu(II)/Zn Vis, IR, NMR formation of behaves as hexadentate complexes. A [Ni3Zn(SHBH‐ [Ni4(SHBH‐H) (H2O)6Cl2]⋅2H confirm hydra their molecul homometallic energies for indicating tha Cite this: Eur. s have much in The complexes fferent physiol to hold therap plications [3]. inhibitors and d hydrazide (IN terial ailments condensation o ntitubercular ac of acetopheno oxy‐acetopheno wed that the ac mplexes. 7‐Chlo ed to be biolog gand to be p xes of oxalyl b tahedral geom planar for the hexanedione b s from the two a egative tetrade nar for [Cu(L)]⋅ al of Chemistry 7 pean Journal of C 016 Atlanta Pub /10.5155/eurjch ournal bpage: www. ri‐ and te ylidene)‐s gh and Maya 13060, Kuwait e, Kuwait University ahoo.com (A.A. El‐A al of N'1,N'4‐bis w evaporation m n(II) complexes h R, MS spectra, tri‐ and tetra a tetranegativ in the Co(II) A square‐planar ‐6H)(H2O)6Cl2]⋅H )(H2O)4(OAc)2]⋅6 H2O were sugges ated and coordin lar ion peaks a c complexes are [Co2Zn(SHBH‐ at the three Co st . J. Chem. 2016, nterest s bind logical peutic Aroyl d are NH) is s, e.g., of INH ctivity one‐4‐ one‐4‐ ctivity oro‐4‐ gically potent bis(di‐ metry, e rest is(iso‐ amide entate ⋅2H2O, squ The [VO dihy solv tetr was squ and M30 aur trin the The oxy bon sub rize carb alco hyd acti bis( com 7 (1) (2016) 81‐ Chemistry lishing House LL hem.7.1.81‐90.1 of Che .eurjchem.co tra‐metal uccinohy ada Samir Al y, Safat, 13060, Kuw Asmy). s((E)‐3,4‐dihydr method. Its, Co(II have been prepa thermal and m ‐metallic compl ve hexadentate complex and r for [Co3(SHBH H2O and [Cu3 6H2O, [Zn3(SHB sted based on nated water as w and the isotopic highly stable th 4H)(H2O)4Cl2].2 tabilized the com 7(1), 81‐90 uare‐pyramidal e ESR spectra O(L)]⋅H2O and [ ydroxy‐benzyli ved. The ligan radentate and t s proposed for uare‐pyramid fo d Cd(II). Some c 010, Candida reus and Salmo nuclear comple metal centers e IR spectra re ygen, enolate o nded as a mono bstituted terpht ed. The comple bons including ohol using H2O drazone compl ivity as catalyst On continuat (hydrazones) a mplexes contain ‐90 LC ‐ All rights re 1356 emistry m llic compl ydrazide li wait. roxybenzylidene I), Ni(II), Cu(II), ared and charact magnetic measu lexes (homo‐ a in the Co(II) hexanegative o H‐6H)(H2O)6], [C 3Zn(SHBH‐6H)(H BH‐4H)‐(H2O)4Cl the magnetic a well as the final c species of eac han the heterom H2O are highe mplex. for [VO(L)]⋅H2 supported the [Cu(L)(H2O)2]⋅2 idene isonicotin nd acts as a tribasic tetrade r the Co(II), C or the VO(II) a complexes have albicans, Esch onella sp. PA39 exes of substitu have distorted evealed the coo oxygen and az dentate ligand thalo and oxalo exes were evalu g cycloalkenes, O2 as terminal lexes, 4 show t [10]. tion to our and up to date ning Co(II), Ni served ‐ Printed y lexes of )succinohydrazi Zn(II), Co(II)/Zn terized by eleme rements. The d and hetero‐nucl )/Zn(II) comple octadentate in Cu4(SHBH‐H)(H2 H2O)6Cl2] and l2]⋅2H2O and [ nd spectral dat product. The ma ch complex. It i metallic complexe er than [Co3(S O and octahedr e mononuclear 2H2O [7]. Single nyl‐hydrazone w a neutral bide ntate. A tetrahe Cu(II) and Hg( and octahedral e activities agai herichia coli, 93 [8]. In the uted succinoyl d octahedral st ordination thro zomethine nitr [9]. Bis(hydrox o hydrazides w uated for oxida , cyclic alkane oxidant. Of the ed the best s earlier work e, no research (II), Cu(II), Zn d in the USA ide (SHBH) wa n(II), Ni(II)/Zn(I ental analysis, UV data confirm th lear). The ligan ex; hexanegativ the tetrametall 2O)4(OAc)2]⋅3H2 tetrahedral fo [Co2Zn(SHBH‐6H ta. The TGA da ass spectra depi is found that th es. The calculate SHBH‐6H)‐(H2O) ral for the rest. r geometry for e crystal of 3,4‐ was grown and entate; dibasic edral geometry (II) complexes; l for the Ni(II) inst Bacillus sp. Staphylococcus three hetero‐ dihydrazones, tereochemistry. ough phenolate rogen. NO3‐ is xylbenzylidene) were character‐ ation of hydro‐ es and benzyl‐ e studied aroyl selectivity and k [11‐14] on was done on (II) and Cd(II) as II) V‐ he nd ve lic O, or H) ata ict he ed )6] . r ‐ d c y ; ) . s ‐ , . e s ) ‐ ‐ ‐ l d n n ) 82 El‐Asmy et al. / European Journal of Chemistry 7 (1) (2016) 81‐90 ions (homo‐ or hetero‐complexes) of N'1,N'4‐bis((E)‐3,4‐ dihydroxybenzylidene)succinohydrazide. The complexes reported herein are investigated to the first time. 2. Experimental 2.1. Materials Cobalt(II) chloride hexahydrate, nickel(II) chloride hexahydrate, nickel(II) acetate trihydrate, copper(II) chloride dihydrate, copper(II) acetate monohydrate, zinc(II) chloride dihydrate, diethyl succinate, hydrazine hydrate, 3,4‐di‐ hydroxy‐benzaldehyde, ethanol, diethyl ether and DMSO were obtained from the BDH Chemicals. 2.2. Physical measurements The IR spectra were recorded on a FT/IR‐6300 type A (400‐4000 cm‐1) as KBr discs. The 1H NMR spectra of the ligand and its diamagnetic complexes were recorded in DMSO‐ d6, on a Bruker WP 200 SY spectrometer (300 MHz) at room temperature using tetramethylsilane (TMS) as an external standard. Varian Micro V1.5.8, CHNS Mode 15073036 was used for elemental analysis of SHBH and its complexes at the Microanalytical Unit of Kuwait University, Kuwait. The metal content was determined using ICP‐OES GBC Quantium Sequential at Kuwait University, Kuwait. Electronic spectra of the complexes were recorded on Cary 5 UV‐Vis Spectro‐ photometer, Varian (200‐900 nm). Mass spectra were recorded on a GC‐MS Thermo‐DFS (BG‐FAB) mass spectro‐ meter. Magnetic susceptibility was measured for powered samples using a Johnson‐Matthey magnetic balance, UK. Hg[Co(SCN)4] was used as a calibrant and corrections for diamagnetism were calculated from Pascal’s constants. Thermogravimetric analysis (TGA) was carried out (10‐850 °C) using a Shimadzu TGA‐60; the nitrogen flow and heating rate were 50 mL/min and 10 °C/min, respectively. The X‐ray single crystal diffraction data were collected on a Rigaku R‐ AXIS RAPID diffractometer using filtered MoKα radiation. The structure was solved by the direct methods and expanded using Fourier techniques at Kuwait University, Kuwait. The molecular geometry of the Co(II) and Ni(II) complexes are first optimized at molecular mechanics (MM+) level. Semi empirical method PM3 is then used for optimizing the full geometry of the system using Polak‐Ribiere (conjugate gradient) algorithm and Unrestricted Hartee‐Fock (UHF) is employed keeping RMS gradient of 0.01 kcal/Å.mol. Quantum chemical calculations for the ligand and some of its metal complexes were used to optimize the geometry and spectral calculation by Gaussian 03W suite program [15] using the Becke3‐Lee‐Yang‐Parr (B3LYP) exchange‐correlation functional with standard 6‐ 311++G (d, p) basis set. 2.3. Synthesis 2.2.1. Synthesis of N'1,N'4‐bis((E)‐3,4‐dihydroxy benzylidene)succinohydrazide The ligand was prepared by adding 7.3 g (0.05 mol) of succinic acid dihydrazide, dissolved in 30 mL ethanol, with 13.8 g (0.1 mol) of 3,4‐dihydroxybenzaldehyde, in 30 mL ethanol, and heating the mixture on a water bath for 2 h. The off‐white precipitate thus formed was filtered off, recrystallized from ethanol and allow to dry in a desiccator over silica gel. Single crystals were grown by slow evaporation and analyzed by X‐ray spectroscopy. It was characterized by elemental analysis and spectral studies. Color: Off‐white. Yield: 88%. M.p.: 206‐208 °C. FT‐IR (KBr, ν, cm‐1): 3282 (OH), 3163 (NH), 1644 (C=O), 1589 (C=N). 1H NMR (300 MHz, DMSO‐ d6, δ, ppm): 11.2 (s, 1H, NH), 11.0 (s, 1H, NH), 9.29 (s, 4H, OH), 7.97‐7.82 (d, 2H, Ar‐H), 7.17 (s, 2H, Ar‐H), 6.90‐6.86 (d, 4H, Ar‐ H+CH=N), 2.92 (s, 2H, CH2), 3.45 (s, 2H, CH2). 13C NMR (300 MHz, DMSO‐d6, δ, ppm): 173.39, 167.92, 147.88, 146.42, 125.95, 29.03. MS (EI, m/z (%)): 386.12 (100), 387.13 (19.9), 388.13 (3.1), 387.12 (1.5). UV/Vis (Nujol, νmax, cm‐1): 33330, 26040, 21830. 2.2.2. Synthesis of the complexes In general, the solid complexes were prepared by reacting the calculated amounts for 4:1 ratio [M:L] of the metal salt and SHBH in EtOH and the mixture was heated under reflux on a water bath with continuous stirring for 3‐6 h. In the preparation of the metal acetate complexes, the medium solution is H2O:EtOH (1:1, v:v). The precipitate thus formed was filtered off, washed with hot water, hot ethanol and diethyl ether and finally dried. The mixed Co/Zn complex was prepared by adding 0.387 g (0.01 mol) of the ligand, in 30 mL EtOH, to a mixture of 0.75 g (0.02 mol) CoCl2.6H2O and 0.33 g (0.02 mol) of ZnCl2.2H2O, in 30 mL EtOH, and heating the mixture on a water bath for 5 h. The color of the mixture was changed instantly followed by the formation of colored precipitate which is filtered, washed and allowed to dry. [Ni3Zn(SHBH‐6H)(H2O)6Cl2]⋅H2O was prepared by adding 0.387 g (0.01 mol) of SHBH, in 30 mL EtOH, to a mixture of 0.1 g (0.03 mol) NiCl2⋅6H2O and 0.17 g (0.01 mol) of ZnCl2⋅2H2O, in 30 mL EtOH, and heating the mixture on a water bath for 3 h. The formed precipitate is filtered, washed with water, ethanol and finally with ether and allowed to dry. Similar procedure was carried out for the preparation of [Cu3Zn(SHBH‐6H)(H2O)6Cl2]. The purity of the compounds as formulated was established by microanalysis. 3. Results and discussion 3.1. General information The CHN analysis of the ligand coincides with SHBH⋅3H2O; its single crystal has 4H2O. The color, melting points and elemental analyses of SHBH and its complexes are presented in Table 1. The data confirm: [Co3(SHBH‐6H)(H2O)6], [Co2Zn(SHBH‐4H)(H2O)4Cl2]⋅2H2O: [Ni4(SHBH‐6H)(H2O)4 (OAc)2]⋅6H2O, [Cu4(SHBH‐6H)(H2O)4(OAc)2]⋅3H2O, [Zn3(SHBH‐ 4H)(H2O)4Cl2]⋅2H2O, [Ni3Zn(SHBH‐6H)(H2O)4Cl2]⋅H2O, and [Cu3Zn(SHBH‐6H)(H2O)6Cl2]. The TGA data indicate a high stability for tetrametallic complexes. Unfortunately, the complexes are insoluble in all organic solvents, so, their molar conductance and NMR were not measured. Although single crystals are not grown, the suggested structures are consistent with all other evidence. 3.2. Analysis of SHBH single crystal SHBH crystals (colorless, platelet) with the formula C18H26N4O16 have molecular weight of 458.42 g/mol. It belongs to monoclinic system with no centrosymmetric P21/c(#14) space group (Table 2) having four water molecules; its half molecule has two water molecules (Figure 1). The estimated cell parameters are a = 6.027(2) Å, b = 6.256(2) Å, c = 27.977(7) Å, β = 94.216 °. The distance of O1‐C3 (1.378 Å) is more than that of O2‐C4 (1.356 Å) because the O1‐C3‐C2 angle (123.7 °) is less than that of O2‐C4‐C5 (124.8 °). The O3‐C8 (1.245 Å) is relavent to double bond character. The N1‐C7 is less than N2‐C8. The distance of N1‐N2 is 1.415 Å. The higher distance is for C1‐C7 due to the attraction of more electronegative N atom. The N1‐C7 is shorter than N2‐C8 related to its double bond nature confirming the condensation process (Table 3‐6). Table 1. Eleme Compound, Empirical form SHBH⋅2H2O C18H22N4O8 SHBH C18H18N4O6 [Co3(SHBH‐6H) C18H24N4O12Co3 [Ni4(SHBH‐6H) C22H38N4O20Ni4 [Cu4(SHBH‐6H) C22H32N4O17Cu4 [Zn3(SHBH‐4H( C18H26N4O12Zn3 [Co2Zn(SHBH‐4 C18H30N4O14Co2 [Ni3Zn(SHBH‐6 C18H26N4O13Ni3 [Cu3Zn(SHBH‐6 C18H24N4O12Cu3 * a Anhydrous li Table 2. Crysta Empirical form Formula weigh Temperature/K Crystal system Space group a/Å b/Å c/Å β/° Volume/Å3 Z ρcalcg/cm3 μ/mm‐1 F(000) Crystal size/mm Radiation Index ranges Reflections coll Independent re Data/restraints Goodness‐of‐fit Final R indexes Final R indexes Largest diff. pea ental analysis and s mula )(H2O)6] 3 )(H2O)4(OAc)2]⋅6H2 )(H2O)4(OAc)2]⋅3H 4 (H2O)4)Cl2]⋅2H2O 3 4H)(H2O)6Cl2]⋅2H2O 2ZnCl2 6H)(H2O)6Cl2]⋅H2O ZnCl2 6H)(H2O)6Cl2] 3Zn Cl2 igand, b for [Co3(SH al data and structur mula ht K m3 lected eflections s/parameters t on F2 s [I≥2σ (I)] s [all data] ak/hole / e Å‐3 El‐Asmy et some properties of M.w; C (Found 440.42 386.37 (387.50 665.20 (577.00 2O 913.55 (603.50 H2O 878.70 (602.00 757.41 (603.00 O 780.62 (781.90 818.93 (693.00 815.27 (804.00 HBH‐6H)], c for [Ni re refinement for S Figure 1. X‐ra al. / European Jo f SHBH and its com alcd. d) Color 2 4 0) a Off‐wh 6 0) b Brown 2 0) c Brown 4 0) d Light b 6 0) e Orange 8 0) Brown 6 0) f Pale br 2 0) Brown 3(SHBH‐6H)]⋅3H2O SHBH. ay single crystal str ournal of Chemis mplexes *. M.p., hite 206‐ n > 325 n >325 brown >325 e >325 n >325 rown >325 n >325 O, d for [Cu2(SHBH‐ C18H 458.4 293 Mono P21/ 6.026 6.256 27.97 94.21 1052 2 1.447 0.119 484.0 0.200 Mo K ‐7 ≤ h 7835 1854 1854 1.080 R1 = wR2 0.42/ ructure of a) half m stry 7 (1) (2016) , oC C Calcd. (Found) 208 49.08 (49.18) 5 32.50 (32.26) 5 28.92 (28.67) 5 30.07 (29.86) 5 28.54 (28.74) 5 27.69 (27.76) 5 26.40 (26.69) 5 27.52 (27.66) ‐6H)(OAc)(H2O)2], 26N4O10 42 oclinic c 68(14) 60(14) 77(7) 16(7) 2.0(5) 7 9 0 0 × 0.080 × 0.030 Kα (λ = 0.71075) h ≤ 7, ‐7 ≤ k ≤ 6, ‐3 5 4 [Rint = 0.0758] 4/5/163 0 0.0615 = 0.2064 /‐0.46 molecule and b) com 81‐90 H Calcd. (Found) 5.49 (5.26) 3.64 (3.88) 4.19 (3.96) 3.67 (3.53) 3.46 (3.33) 3.87 (3.33) 3.20 (3.17) 2.97 (2.40) e for [Zn3(SHBH‐6 2 ≤ l ≤ 32 (a) mplete molecule. N Calcd. (Found) M Calc (Fo 12.77 (13.06) ‐ 8.42 (8.12) 26.5 (26 6.13 (6.25) 25.7 (26 6.38 (6.67) 28.9 (28 7.40 (7.38) 25.8 (26 7.17 (7.80) Co= Zn= 6.84 (6.71) Ni= Zn= 6.87 (7.07) 6H)], f [Ni3Zn(SHBH (b) 83 cd. ound) 58 6.86) 72 6.17) 92 8.61) 88 6.04) =15.10 14.03) =8.37 (9.50) =23.51 (23.78) =7.98 (7.46) H‐6H)(H2O)4]. 84 El‐Asmy et al. / European Journal of Chemistry 7 (1) (2016) 81‐90 Table 3. Bond lengths for SHBH. Atom Atom Length/Å Atom Atom Length/Å O1 C3 1.378(5) C1 C7 1.439(6) O2 C4 1.356(5) C2 C3 1.375(5) O3 C8 1.245(5) C3 C4 1.409(6) N1 N2 1.415(5) C4 C5 1.377(6) N1 C7 1.285(5) C5 C6 1.389(6) N2 C8 1.308(5) C8 C9 1.451(7) C1 C2 1.407(6) C9 C9 1 1.415(8) C1 C6 1.392(6) 1 ‐1‐x, 2‐y, 1‐z. Table 4. Bond angles for SHBH. Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚ N2 N1 C7 113.6(4) O2 C4 C5 124.8(4) N1 N2 C8 121.6(4) C3 C4 C5 119.4(4) C2 C1 C6 118.8(4) C4 C5 C6 120.3(4) C2 C1 C7 122.5(4) C1 C6 C5 120.9(4) C6 C1 C7 118.7(4) N1 C7 C1 123.7(4) C1 C2 C3 120.2(4) O3 C8 N2 123.3(4) O1 C3 C2 123.7(4) O3 C8 C9 124.7(4) O1 C3 C4 115.9(3) N2 C8 C9 111.9(4) C2 C3 C4 120.4(4) C8 C9 C91 121.8(5) O2 C4 C3 115.8(4) 1 ‐1‐x, 2‐y, 1‐z. Table 5. Hydrogen bonds for SHBH. D H A d(D‐A)/Å d(D‐H)/Å d(H‐A)/Å D‐H‐A/° O1 H1 O5 2.800(5) 0.820 2.016 159.7 O2 H2 O11 2.858(4) 0.820 2.166 142.2 O4 H4A O32 2.903(5) 0.824 2.08(4) 177(5) O5 H5A O4 2.783(6) 0.821 1.966(19) 173(6) O5 H5B O33 2.874(5) 0.820 2.07(6) 168(5) N2 H2A O54 2.920(5) 0.860 2.064 173.1 1 2‐x, 1/2+y, 3/2‐z; 2 ‐x, 1‐y,1‐z; 3 1+x, +y, +z; 4‐1+x ,1+y, +z. Table 6. Torsion angles for SHBH. A B C D Angle/˚ A B C D Angle/˚ N2 N1 C7 C1 ‐176.8(3) C1 C2 C3 C4 1.6(6) C7 N1 N2 C8 ‐180.0(3) O1 C3 C4 O2 ‐0.1(5) N1 N2 C8 O3 3.8(6) O1 C3 C4 C5 ‐179.3(3) N1 N2 C8 C9 ‐177.0(3) C2 C3 C4 O2 178.3(4) C2 C1 C6 C5 ‐0.1(6) C2 C3 C4 C5 ‐0.8(6) C6 C1 C2 C3 ‐1.1(6) O2 C4 C5 C6 ‐179.5(4) C2 C1 C7 N1 ‐5.6(6) C3 C4 C5 C6 ‐0.4(6) C7 C1 C2 C3 178.5(4) C4 C5 C6 C1 0.9(6) C6 C1 C7 N1 173.9(4) O3 C8 C9 C91 15.7(8) C7 C1 C6 C5 ‐179.7(4) N2 C8 C9 C91 ‐163.5(5) C1 C2 C3 O1 179.9(4) C8 C9 C91 C81 ‐180(4) 1 ‐1‐x, 2‐y, 1‐z. Figure 2. Structure of [Cu4(SHBH‐6H)(H2O)4(OAc)2]⋅3H2O. 3.3. IR and NMR spectra of SHBH and complexes The positions of the important bands in the IR spectra of SHBH and its complexes are shown in Table 7. SHBH has good coordination ability for the studied metal ions. Its spectrum showed bands at 3282, 3163, 1644 and 1589 cm‐1 due to (OH), (NH), (C=O) and (C=N), respectively [16]. Its 1H NMR spectrum has signals at δ 11.2 (s, 1H, NH), 11.0 (s, 1H, NH), 9.29 (s, 4H, OH), 7.97‐7.82 (d, 2H, Ar‐H), 7.17 (s, 2H, Ar‐ H), 6.90‐6.86 (d, 4H, Ar‐H+CH=N), 2.92 (s, 2H, CH2), 3.45 (s, 2H, CH2). 13C NMR spectrum showed peaks at δ 173.39, 167.92 (C=O); δ 147.88, 146.42 (C=N); δ 125.95 (C‐O) and 29.03 ppm (CH). The ligand has multi donor groups, so different modes of chelation are proposed. Tentative assignments of the observed bands for the compounds were made by complete comparison of the spectra of complexes with that of SHBH. In [Cu4(SHBH‐6H)(H2O)4(OAc)2]⋅3H2O (Figure 2), [Ni4(SHBH‐6H)(H2O)4(OAc)2]⋅6H2O, [Ni3Zn(SHBH‐6H)(H2O)6 Cl2]⋅H2O, [Cu3Zn(SHBH‐6H)(H2O)6Cl2]⋅H2O, the ligand acts as a hexanegative octadentate with the four metal ions coordi‐ nating through the deprotonated OH’s, the two enolic carbonyl and the two C=N groups. Complete disappearance of the OH band confirmed their involvement in coordination after deprotonation. New observed band at 3350‐3550 cm‐1 is due to the hydrated or coordinated water. The absence of (NH) and (C=O) bands indicates enolization of the amidic group. Table 7. IR spe Compound SHBH [Co3(SHBH‐6H) [Ni4(SHBH‐6H) [Cu4(SHBH‐6H) [Zn3(SHBH‐6H) [Co2Zn(SHBH‐4 [Ni3Zn(SHBH‐6 [Cu3Zn(SHBH‐6 * Hydrated or c ** New azometh Table 8. Molecu Parameters Total Energy (K Total Energy (a Binding Energy Isolated Atomic Electronic Ener Core‐Core Inter Heat of Format Gradient (Kcal/ Dipole (Debyes The (C indicating its new bands a (M‐N) [17] wavenumber duo to δ(OH 6H)‐(H2O)4(O cm‐1 are att difference (1 Density in Table 8 fo The data of formation of of Cu(31)‐O Cu(31) bond vely, suggest same observ around Cu(3 ectral data of SHBH )(H2O)6] )(H2O)4(OAc)2]⋅6H )(H2O)4(OAc)2]⋅3H )(H2O)4Cl2]⋅2H2O 4H)(H2O)4Cl2]⋅2H2O 6H)(H2O)6Cl2]⋅H2O 6H)(H2O)6Cl2] coordinated water. hine group due to ular parameters of Kcal/mol) a.u) y (Kcal/mol) c Energy (Kcal/mo rgy (Kcal/mol) raction (Kcal/mol) tion (Kcal/mol) /mol) s) C=N) band is s coordination. at 520‐543 and ]. The (M‐O) r than (M‐N). H) of the coord OAc)2] ⋅3H2O, t tributed to νa 150 cm‐1) indica functional theo for [Cu4(SHBH‐ f binding and f metal complex O(39), Cu(31)‐ ds are 1.953, 1 ting small disto vation was ded 30). However, El‐Asmy et H and its metal com ν(OH) (H 3423* (vbr) 2O 3431* (vbr) H2O 3425* (br) 3425* (br) O 3398* (br) 3418* (br) 3418* (vbr) enolization of NHC f some complexes. [Co3(SHBH 265680.17 423.388 467492.52 ol) ‐201812.3 ‐1037819. ) 1303499.9 201812.34 1037819.7 46.889 Figure shifted to l . The spectra o d 425‐458 cm‐1 vibration is Also, the new b dinated water two new band as and νs of th ates a bidentate ory (DFT) calcu 6H)(H2O)4(OAc total energy c x process is end O(38), O(27)‐ 1.942, 1.930 an ortion than the duced for the Cu(29) and C al. / European Jo mplexes. H2O) ν(OH) 3282 (br) ‐ ‐ ‐ ‐ ‐ 3226 (br C=O. H‐6H)(H2O)6 75 21 46 .785 961 46 785 e 3. Molecular mod lower wavenu of complexes sh 1 due to (M‐O observed at h band at 1338 c [18]. In [Cu4(S s at 1560 and he acetate ion e coordination. ulations were s c)2]⋅3H2O (Figu clearly out tha doergic. The len Cu(31) and O nd 1.965 Å, res e square‐planar coordination a Cu(28) in whic ournal of Chemis ν(N‐H) ν 3163 (w) 1 ( ‐ ‐ ‐ 1 ( 3246 (br) 1 ( ‐ 1 ( r) ‐ ‐ [Cu4(SHBH‐ ‐288280.953 ‐459.405 ‐7224.877 ‐281056.076 ‐2480853.10 2102572.15 ‐502.019 66.394 11.269 deling of [Cu4(SHB umber howed O) and higher cm‐1 is SHBH‐ 1410 n; the shown ure 3). at the ngthes O(26)‐ specti‐ r. The atoms ch the Cu( and 9). 1.85 are the hyb hex 4). the and corr new evid app coo due stry 7 (1) (2016) ν(C=O) ν(C=N 1644 (s) 1589 (s) ‐ 1574 (m) 1642 (m) 1584 (m) 1574 (m) 1644 (vw) 1583 (m) 1650 (w) 1578 (m) ‐‐ 1583 (m) ‐ 1551 (m) ‐6H)(H2O)4(OAc)2 3 6 05 52 BH‐6H)(H2O)4(OAc (II) is surround d enolic carbony The N(18)‐Cu( 54 Å. The bond approximately range 70‐104 bridization. In [Co3(SHB xanegative hexa The deprotona donor groups d (C=O); appea responding to  w band at 3423 dence for the O pearance of δ( ordinated water e to (M‐O) [17] 81‐90 N) ν(C=N)** ‐ 1490 (m) 1488 (s) 1487 (s) 1491 (s) 1488 (s) 1488 (s) 1457 (s) 2].3H2O [Co2 1290 463. 4756 ‐185 ‐893 1184 4812 2216 24.9 c)2]⋅3H2O. ded by acetate yl oxygen have (29) and N(4)‐C d lengths of the y similar. The b 4 and 120‐12 H‐6H)(H2O)6], adentate with t ated OH’s and t according to di arance of new b (C=N)* and ( 3 cm‐1 due to t OH coordinatio (OH) at 1366 r. The spectrum ]. ν(C‐O) υ(M‐ ‐ ‐ 1174 (m) 523 (w) 1164 (w) 534 (vw) 520 (vw) 1176 (w) 521 (br) 1170 (m) 510 (br) 1163 530 (w) 1199 (m) 543 (w) 2Zn(SHBH‐4H)(H2 0573.824 .059 675.039 5101.215 3961.753 4535.577 238.843 6.843 87 oxygen, azome different bond Cu(28) have th e acetate oxygen bond angles (T 8 ° confirmin the ligand the three coba the two enolic C isappearance o bands at 1490 (C‐O) [19], and he coordinated on after deprot cm‐1 which i m showed a ne 85 ‐O) υ(M‐N) ‐ ‐ ) 434 (w) ) 460 (vw) 425 (vw) 458 (w) 2O)4Cl2].2H2O ethine nitrogen d lengths (Table he same length, ns with copper Table 9) are in g sp3 and sp2 acts as a alt ions (Figure C‐O groups are of (OH), (NH) and 1174 cm‐1, d appearance of d water. Strong tonation is the is due to the w band at 523 n e , r n 2 a e e ) , f g e e 3 86 El‐Asmy et al. / European Journal of Chemistry 7 (1) (2016) 81‐90 Table 9. Bond length and bond angles of [Cu4(SHBH‐6H)(H2O)4(OAc)2].3H2O. Atom‐Atom Length/Å Atom‐Atom‐Atom Length/Å Cu(31)‐O(39) 1.953 O(39)‐Cu(31)‐O(38) 102.963 Cu(31)‐O(38) 1.942 O(39)‐Cu(31)‐O(27) 104.388 Cu(30)‐O(37) 1.936 O(39)‐Cu(31)‐O(26) 101.106 Cu(30)‐O(36) 1.954 O(38)‐Cu(31)‐O(27) 120.97 Cu(29)‐O(43) 1.872 O(38)‐Cu(31)‐O(26) 128.653 Cu(29)‐O(42) 1.87 O(27)‐Cu(31)‐O(26) 95.347 Cu(28)‐O(35) 1.871 O(37)‐Cu(30)‐O(36) 101.571 Cu(28)‐O(34) 1.873 O(37)‐Cu(30)‐O(13) 128.64 O(27)‐Cu(31) 1.93 O(37)‐Cu(30)‐O(12) 124.103 O(26)‐Cu(31) 1.965 O(36)‐Cu(30)‐O(13) 101.071 N(18)‐Cu(29) 1.854 O(36)‐Cu(30)‐O(12) 102.83 O(17)‐Cu(29) 1.82 O(13)‐Cu(30)‐O(12) 94.33 O(13)‐Cu(30) 1.97 O(43)‐Cu(29)‐O(42) 70.514 O(12)‐Cu(30) 1.93 O(43)‐Cu(29)‐N(18) 170.149 N(4)‐Cu(28) 1.854 O(43)‐Cu(29)‐O(17) 97.062 O(1)‐Cu(28) 1.821 O(42)‐Cu(29)‐N(18) 101.573 C(41)‐O(43)‐Cu(29) 89.677 O(42)‐Cu(29)‐O(17) 166.662 C(41)‐O(42)‐Cu(29) 89.518 N(18)‐Cu(29)‐O(17) 91.269 H(69)‐O(39)‐Cu(31) 95.891 O(35)‐Cu(28)‐O(34) 70.456 H(61)‐O(39)‐Cu(31) 96.387 O(35)‐Cu(28)‐N(4) 101.629 H(70)‐O(38)‐Cu(31) 99.53 O(35)‐Cu(28)‐O(1) 166.568 H(60)‐O(38)‐Cu(31) 96.948 O(34)‐Cu(28)‐N(4) 169.927 H(67)‐O(37)‐Cu(30) 100.547 O(34)‐Cu(28)‐O(1) 97.174 H(59)‐O(37)‐Cu(30) 98.975 N(4)‐Cu(28)‐O(1) 91.221 H(68)‐O(36)‐Cu(30) 95.91 Cu(31)‐O(27)‐C(22) 89.36 H(58)‐O(36)‐Cu(30) 96.702 Cu(31)‐O(26)‐C(23) 81.769 C(33)‐O(35)‐Cu(28) 89.544 Cu(29)‐N(18)‐C(19) 121.628 C(33)‐O(34)‐Cu(28) 89.643 Cu(29)‐N(18)‐N(16) 105.238 Cu(30)‐O(13)‐C(9) 81.681 Cu(28)‐N(4)‐N(3) 105.226 Cu(30)‐O(12)‐C(8) 88.907 Cu(28)‐O(1)‐C(2) 106.054 Cu(28)‐N(4)‐C(5) 121.623 C(15)‐C(14)‐C(44)‐C(2) 86.748 Table 10. Bond length and bond angles of [Co3(SHBH‐6H)(H2O)6]. Atom‐Atom Length/Å Atom‐Atom‐Atom Length/Å Co(35)‐O(37) 2.025 H(61)‐O(32)‐H(50) 107.729 Co(35)‐O(36) 1.961 H(61)‐O(32)‐Co(29) 104.161 Co(29)‐O(33) 2.021 H(50)‐O(32)‐Co(29) 106.879 Co(29)‐O(32) 1.975 H(56)‐O(31)‐H(49) 107.77 Co(28)‐O(31) 1.975 H(56)‐O(31)‐Co(28) 104.104 Co(28)‐O(30) 2.021 H(49)‐O(31)‐Co(28) 106.855 O(27)‐Co(29) 1.909 H(57)‐O(30)‐H(48) 108.279 O(26)‐Co(29) 1.861 H(57)‐O(30)‐Co(28) 109.543 O(13)‐Co(28) 1.913 H(48)‐O(30)‐Co(28) 105.901 O(12)‐Co(28) 1.862 O(33)‐Co(29)‐O(32) 87.176 O(1)‐Co(35) 1.9 O(33)‐Co(29)‐O(27) 96.637 H(59)‐O(37)‐Co(35) 105.558 O(33)‐Co(29)‐O(26) 92.96 H(55)‐O(37)‐Co(35) 104.434 O(32)‐Co(29)‐O(27) 89.072 H(58)‐O(36)‐Co(35) 107.937 O(32)‐Co(29)‐O(26) 178.956 H(54)‐O(36)‐Co(35) 102.559 O(27)‐Co(29)‐O(26) 89.884 O(37)‐Co(35)‐O(36) 90.429 O(31)‐Co(28)‐O(30) 87.221 O(37)‐Co(35)‐O(17) 90.677 O(31)‐Co(28)‐O(13) 89.427 O(37)‐Co(35)‐O(1) 88.106 O(31)‐Co(28)‐O(12) 178.878 O(36)‐Co(35)‐O(17) 178.044 O(30)‐Co(28)‐O(13) 97.948 O(36)‐Co(35)‐O(1) 71.645 O(30)‐Co(28)‐O(12) 92.726 O(17)‐Co(35)‐O(1) 106.781 O(13)‐Co(28)‐O(12) 89.47 H(60)‐O(33)‐Co(29) 108.862 O(1)‐Co(35)‐O(37)‐H(55) 38.995 H(51)‐O(33)‐Co(29) 105.751 O(1)‐Co(35)‐O(37)‐H(59) 152.668 Figure 4. Structure of [Co3(SHBH‐6H)(H2O)6]. The calculated energetic parameters shown in Table 8 for [Co3(SHBH‐6H)(H2O)6] (Figure 5) indicate exoergic process for the complex formation. Bond lengthes and angles are shown in Table 10. The last mode of chelation in which SHBH acts as a tetrabasic hexadentate through the four deprotonated OH and two C=O was depicted in [Zn3(SHBH‐4H)(H2O)4Cl2]⋅2H2O and [Co2Zn(SHBH‐4H)(H2O)4Cl2]⋅2H2O (Figure 6). The (C=O) appeared at 1650 (1644 cm‐1) indicating chelation through this group (keto form). Also, the disappearance of OH band confirmed its deprotonation through coordination. The complexes showed new band at 521 (510) cm‐1 due to (M‐O). Table 11. Bond Atom‐Atom‐At Cl(37)‐Zn(35)‐ Cl(37)‐Zn(35)‐ H(53)‐O(33)‐Co H(58)‐O(32)‐H H(58)‐O(32)‐Co H(52)‐O(32)‐Co H(56)‐O(31)‐H H(56)‐O(31)‐Co H(51)‐O(31)‐Co H(57)‐O(30)‐H H(57)‐O(30)‐Co H(50)‐O(30)‐Co O(33)‐Co(29)‐O O(33)‐Co(29)‐O O(33)‐Co(29)‐O O(32)‐Co(29)‐O O(32)‐Co(29)‐O O(27)‐Co(29)‐O O(31)‐Co(28)‐O O(31)‐Co(28)‐O O(31)‐Co(28)‐O O(30)‐Co(28)‐O The broa 6H)(H2O)6], 6H)‐(H2O)4(O [Zn3(SHBH‐4 H2O and [Cu of the hydr observed in (H2O)6Cl2] at and wagging The calc 4H)(H2O)4Cl indicating th the complex 11. The geo (Figure 6). d length and bond tom Cl(36) O(17) o(29) H(52) o(29) o(29) H(51) o(28) o(28) H(50) o(28) o(28) O(32) O(27) O(26) O(27) O(26) O(26) O(30) O(13) O(12) O(13) ad band in the [Co2Zn(SHBH OAc)2]⋅6H2O, [ 4H)(H2O)4Cl2]⋅2 u3Zn(SHBH‐6H) rated or coord n [Co3(SHBH‐6 t 1660 and 131 g [ρw(OH2)] vibr culated energi 2]⋅2H2O are h hat the three Co . Bond lengths metry around El‐Asmy et angles of [Co2Zn(S Figur e range 3398‐3 H‐4H)(H2O)4Cl2] [Cu4(SHBH‐6H) 2H2O, [Ni3Zn(S )(H2O)6Cl2] are dinated water 6H)(H2O)6] and 17 cm‐1 are due rations of the co ies (Table 8) igher than [C o lowered the e and angles are the Zn atom i al. / European Jo SHBH‐6H)(H2O)4Cl Length/Å 108.871 110.257 104.457 104.595 104.018 104.361 104.605 104.023 104.363 104.766 104.362 104.435 113.033 112.354 112.292 112.368 112.245 93.019 113.028 112.395 112.22 112.337 Figure 5.Molecul re 6. Molecular mo 3431 for [Co3(S ]⋅2H2O, [Ni4(S )(H2O)4(OAc)2]⋅ HBH‐6H)(H2O) attributed to  [20]. Other d [Cu3Zn(SHBH to bending [δ( oordinated wat for [Co2Zn(S o3(SHBH‐6H)(H energy and stab e presented in s purely tetrah ournal of Chemis 2].2H2O. Atom‐A O(30)‐C O(13)‐C Zn(35)‐ Co(28)‐ Co(28)‐ O(31)‐C O(30)‐C O(30)‐C O(13)‐C Zn(35)‐ Co(28)‐ Co(28)‐ Zn(35)‐ Zn(35)‐ Co(29)‐ Co(29)‐ Co(28)‐ Co(28)‐ O(27)‐C O(26)‐C O(17)‐Z O(1)‐Zn lar modeling of [Co odeling of [Co2Zn(S SHBH‐ SHBH‐ ⋅3H2O, 6Cl2]⋅‐ (OH) bands H‐6H) (OH2)] er. SHBH‐ H2O)6] bilized Table hedral 3.4. sho at m liga with mol sho to C m/z mol inte a p [Co one stry 7 (1) (2016) Atom‐Atom Co(28)‐O(12) Co(28)‐O(12) ‐O(17)‐C(15) ‐O(13)‐C(9) ‐O(12)‐C(8) Co(28)‐O(12) Co(28)‐O(13) Co(28)‐O(12) Co(28)‐O(12) ‐O(17)‐C(15) ‐O(13)‐C(9) ‐O(12)‐C(8) ‐Cl(37) ‐Cl(36) ‐O(33) ‐O(32) ‐O(31) ‐O(30) Co(29) Co(29) Zn(35) n(35) o3(SHBH‐6H)(H2O) SHBH‐4H)(H2O)6Cl . Mass spectra The data of F own in Table 1. m/z = 387.5 co and, C18H18N4O6 h 5% intensity lecules with hy owed a peak at C11H9O4N2. Othe z due to C6H5O2 The spectrum lecular ion pe ensity 6% may peak at 551.4 3(SHBH‐6H)]. N e at 69. 81‐90 )6]. l2]⋅2H2O. AB‐MS of the The MS of SHB orresponding t 6 (386.374). Th y may be due t ydrogen bond in 235.3 with int er peaks are obs 2, C6H3O and 6 C m of [Co3(SH eak at 577.5 be due to [Co3( 4 m/z (intens Numerous peak Length 112.31 93.02 122.11 106.77 106.94 112.22 112.33 112.31 93.02 122.11 106.77 106.94 2.24 2.239 1.82 1.82 1.82 1.82 1.776 1.776 1.87 1.871 ligand and its H showed mole to the anhydro he peak shown to combination nteraction. Also tensity of 88% served at 110.9 C. HBH‐6H)(H2O)6] m/z (Calcd. 6 (SHBH‐6H)(H2O ity 13%) cor ks are observed 87 h/Å 12 12 75 46 2 37 12 12 75 46 complexes are ecular ion peak us form of the n at 772.7 m/z n of two ligand o, the spectrum corresponding 9, 99.8 and 70.9 ] exhibit the 665.205) with O)] followed by responding to d with the final e k e z d m g 9 e h y o l 88 Table 12. Magn Compound SHBH [Co3(SHBH‐6H) [Ni4(SHBH‐6H) [Cu4(SHBH‐H)( [Zn3(SHBH‐6H) [Co2Zn(SHBH‐4 [Ni3Zn(SHBH‐6 [Cu3Zn(SHBH‐6 * Value for each However (OAc)2]⋅6H2O The value co acetate and e ending with correspond t The mol ⋅3H2O is 60 [Cu2(SHBH‐6 to the remov intensity) fol [Zn3(SHB [Zn3(SHBH‐6 peak at 368 intensity foll 69 m/z whic same mechan The m/z with intensit This peak h observed con final intense The m/z with no isoto formula acco the differenc [Cu3(SHBH‐6 final at 78.9 m Very sm (SHBH‐6H)(H 6H)(H2O)4] f was observe isotope. The peaks. The fi with three is 3.5. Electron The mag of the comp temperature The abso → π* and n → 26040 and 2 spectra of [Co3(SHBH‐6 for [Co2Zn(S and 21930 c 238190 and 31850, 2512 6H)Cl2].2H2O [Cu4(SHBH‐H In the el 6H2O, a stro tetrahedral steric hindr difference b compared to netic moments and )(H2O)6] )(H2O)4(OAc)2]⋅6H2 (H2O)4(OAc)2]⋅3H2O )(H2O)4Cl2]⋅2H2O 4H)(H2O)4Cl2]⋅2H2O 6H)(H2O)6Cl2]⋅H2O 6H)(H2O)6Cl2] h metal ion. r, the mass s O showed m/z orresponds to eight water mo h a peak at to 6 C. lecular ion pea 02 m/z with i 6H)(H2O)2(OAc) val of OAc + H2O llowed by peak BH‐4H)(H2O)4C 6H)] with inten 8.3 m/z is obs lowed by peaks ch proved that nism after this z value 781.9 o ty of 3% is due has no isotopi ntaining the ba peak at 78.9 m/ z value of [Cu opic species and ording to the e ce is large. Ano 6H)]. The base m/z. mall peak was H2O)6Cl2]⋅H2O followed by nu ed at 419.9 m/ e base peak at inal peak at 57 sotopes. nic and magnet gnetic moments lexes measured e are presented orption spectru → π* bands of C 21830 cm‐1. Di its complexes 6H)(H2O)6]; 337 SHBH‐6H)(H2O) cm‐1 for [Ni4(SH 22120 cm‐1 fo 25, 21275, 183 O and 34010, 2 H)(H2O)4(OAc)2 lectronic spectr ng band at 156 geometry. The rance produce between size a o acetates. Add E d electronic spectra μeff (BM) I ( 3 2.84* 2 2O 2.13* 3 O 1.19* 3 3 O 3.66* 3 0.00 2 0.76* 3 spectrum of [N value of 603.5 [Ni3(SHBH‐6H) olecules. Multi‐p 69.0 m/z (7 ak of [Cu4(SHBH intensity of 3% )] followed by o O. The base pea ks at 99, 73 and l2]⋅2H2O has nsity of 7%. It served in all c s at 313.2, 236.2 t the complexe step. f [Co2Zn(SHBH to its formula C ic species. Num ase peak at 133 /z having more u3Zn(SHBH‐6H) d low intensity elemental analy other peak at peak is observ observed at 6 corresponding umerous small /z with intensi t 115.0 m/z ha .0 m/z is due t tic studies s and the elect d in Nujol (200 in Table 12. m of SHBH (Fig C=C, C=O and C ifferent bands at: 27320 an 780, 29240, 26 )4Cl2].2H2O; 33 HBH‐H)(H2O)4( or [Ni3Zn(SHBH 15 and 16600 29410, 25125 2].3H2O. rum of [Ni4(SH 625 cm‐1 is assi e distortion m d by the bul and space occ ditional bands El‐Asmy et al. / Eu al bands of the com ntra ligand and c (cm‐1) 33330; 26040; 218 27320; 23255 33780; 30120; 251 34010; 29410; 251 31850; 25125; 212 33780; 29240; 268 27320; 238190; 22 33110; 28410; 238 Ni4(SHBH‐6H)( 5 with 3% inte )(OAc)] withou peaks were obs 8% intensity) H‐6H)(H2O)4 (O % correspondi one at 523.4 m/ ak at 135 m/z ( 69 m/z. 603.5 m/z du t is noticed tha omplexes with 2, 111.1, 97.1, 8 s degraded wit ‐4H)(H2O)6Cl2] C18H30N4O14Co2 merous peaks 3.0 m/z (100% e isotopes. )(H2O)6Cl2] is (2%). The sugg ysis is 815.336 566.7 m/z is d ved at 176.3 an 693.0 m/z in [ g to [Ni3Zn (S peaks. The hig ity of 16% an aving multi iso to the presence ronic spectral 0‐1000 nm) at gure 7) showed =N groups at 3 are observed i nd 23255 cm 6880 and 23360 3780, 30120, 2 (OAc)2].6H2O, 2 H‐6H)(H2O)6Cl2 cm‐1 for [Zn4(S and 22730 cm BH‐H)(H2O)4(O igned to 3T1 → ay be attribut lky ligand and cupied by SHB centered at 1 uropean Journal mpounds. charge transfer 830 125; 21930 125; 22730 275; 18315; 16600 880; 23360 2120 810 (H2O)4 ensity. ut one served may OAc)2] ing to /z due 100% ue to at the h high 83 and th the ⋅2H2O 2ZnCl2. were %) and 804.0 gested 6 m/z; duo to nd the [Ni3Zn SHBH‐ gh one d one otopic of 5C bands room d the π 33330; in the m‐1 for 0 cm‐1 25125 27320, ].H2O; SHBH‐ m‐1 for OAc)2]. 3A2 of ted to d the BH as 9610; 183 mom spin and atom (H2 168 is ty [21 stru Fig and tetr to C squ with 6H) spin 9b) of Chemistry 7 ( d‐d trans (cm‐1) 20830; 17 19610; 18 20580; 17 20830; 20 20160; 18 19920; 16 315 and 16720 ment is 2.13 B n only value fo d may be due ms. On the oth O)4Cl2].3H2O (F 835, 14580 and ypical of a squa ]. The diamag ucture. Figure 7 gure 8. Electronic s [Co3(SHBH‐6H d 16080 (Figure rahedral geome Co‐SHBH CT. Th uare‐planar geo h a tetrahedral The room tem )(H2O)4Cl2].2H2 n‐only value (3 showed bands (1) (2016) 81‐90 sition 7670; 16080 8315; 16720; 1562 7480; 15200 0160; 18115; 1683 8380; 16835; 1458 6555; 14750 cm‐1 may be d BM for each Ni or the presence to strong inte her hand, the sp Figure 8) show d 13620 cm‐1. T are‐planar struc gnetic nature s 7. Absorption spect spectrum of [Ni3Zn H)(H2O)6] show e 9a) in agreem etry [22]. The ba he magnetic mo ometry. Its mol structure. perature magn O (3.66 BM) is 3.87 BM). The s at 20160, 1811 25 35; 15015 80; 13620 ue to O → MCT atom which is e of two electr eraction betwee pectrum of [Ni3 wed bands at he strong band cture and is due supports the a trum of SHBH in N n(SHBH‐6H)(H2O)6 wed bands at ment with those and at 20830 cm oment (2.83 BM ecular modelin etic moment of s expected to b electronic spe 15, 16835 and 1 Probable Structure Square‐planar Tetrahedral Square‐planar Tetrahedral Tetrahedral Square‐planar Square‐planar T. The magnetic s less than the rons (2.87 BM) en the four Ni 3Zn(SHBH‐6H)‐ 20160, 18380, d at 20160 cm‐1 e to 1A1g → 1A2g aforementioned Nujol. 6Cl2]⋅H2O in Nujol. 20830, 17670 e reported for a m‐1 may be due M) supports the ng is consistent f [Co2Zn(SHBH‐ e less than the ectrum (Figure 15015 cm‐1. c e ) i ‐ , 1 g d 0 a e e t ‐ e e Table 13. Deco Complex SHBH.2H2O [Co3(SHBH‐6H) [Ni4(SHBH‐6H) [Cu4(SHBH‐6H) [Zn3(SHBH‐4H) [Co2Zn(SHBH‐6 [Ni3Zn(SHBH‐6 The band structure [23 Three b H)(H2O)4(OA (20580, 174 cm‐1) are as respectively and 0.76 BM between the copper in the Figure 9. El [Co2Zn(SHBH‐6 omposition steps o )(H2O)6] )(H2O)4(OAc)2]⋅6H )(H2O)4(OAc)2]⋅3H )(H2O)4Cl2]⋅2H2O 6H)(H2O)4Cl2]⋅2H2O 6H)(H2O)6Cl2]⋅H2O d at 16835 cm‐ 3]. bands observed Ac)2].3H2O and 480 and 15200 signed to dxz → [24‐26]. The s M, respectively, e four copper at e second compl ectronic spectra 6H)(H2O)4Cl2]⋅2H2O El‐Asmy et f the compounds b Mid 119 226 450 >50 79 352 522 >60 2O 77 416 600 >60 H2O 75 269 433 >50 71 400 575 >60 O 84 234 79 236 ‐1 is due to 4A2 d in the spe d [Cu3Zn(SHB 0) and (19920 → dxy in a squa ubnormal mag , may be due t toms in the firs lex. of a) [Co3(SH O. al. / European Jo based on the therm d‐Point Temp. (°C) 6 0 0 6 0 0 0 4 6  4T1 of tetrah ctra of [Cu4(S BH‐6H)(H2O)6Cl 0, 16555 and 1 are‐planar geom gnetic moments to strong intera st complex and BH‐6H)(H2O)6] a ournal of Chemis mogravimetric data ) Removed ‐ 2H2O ‐ C6H5O2 ‐ C3H5N2 C9H7N2O3 ‐ 6H2O ‐ C9H7N2O ‐ C9H7N2O Co3O2 ‐ 6H2O+2 ‐ 2H2O + ‐ 2OAc 2NiO + 2N ‐ 3H2O+2 ‐ 2H2O+ C ‐ C9H7N2O 4 CuO ‐ 6H2O ‐ZnCl2 + O ‐ C6H3ZnO C12H11N4O ‐ 2H2O ‐ 4H2O ‐H2O+4H ‐ 2H2O + hedral SHBH‐ l2] at 14750 metry, s, 1.19 action three (a) (b) and b) 3.6. com stab Tab The stab [Zn com coo the the resi step 5H2 resi sho of 6 is C ⋅6H obs step ther deg the [26 rem ind 4. C It w Co2 Cu2 hex hex octa geo stry 7 (1) (2016) a. d species 3 O2 O2 H2O (coordinated) C18H18N4O6 Ni H2O (coordinated) C9H7N2O3 O3 O2 O2 O2Zn 2O (coordinated) Cl2 . Thermal anal The thermog mplexes were r bility of the stu ble 13, the com ey have stability ble one is [Ni4 3(SDHBH‐6H)(H mplex is found ordinated water temperature b The thermogra removal of 2H idue at > 500 °C In [Cu4(SHBH‐ ps at mid‐point 2O, (2H2O + C idue is 4 CuO w The thermo owed three step 6H2O, (ZnCl2 + C12H11N4O2Zn. The TGA the H2O showed the served at 416 °C p at 600 °C is du The TG curve rmal steps aft gradation steps removal of 6 .45 (calcd. 26 moval of the c icate the weak Conclusion A new ligand w was introduced +, Ni2+, Cu2+, Z +/Zn2+ or Ni xadentate in xadentate in the adentate in th ometry was 81‐90 Weigh 8.53 ( 25.55 24.80 (50.35 16.98 26.45 27.63 30.67 ) 15.44 42.77 12.57 29.22 ) 11.44 23.68 19.59 37.96 11.20 23.96 23.96 40.86 5.91 ( 9.82 ( 11.18 13.44 lysis gravimetric cu recorded to giv udied complexe mplexes were f y temperature 4(SHBH‐6H)(H2 H2O)4Cl2]⋅2H2O d more than h rs were evolved elow 100 °C ind am of the ligan H2O, C6H5O2, C C. ‐6H)(H2O)4(OA ts of 75, 269 an C9H7N2O3) and with weight loss gram of [Z ps at 71, 400 an O2) and C6H3Zn ermogram of e evolution of C the loss of 4H ue to the evolut e of [Co3(SHBH ter which it le were observe H2O with 16.9 6.33)] and C9H coordinated w bond with the c was prepared a d for chelation Zn2+ and comb i2+/Zn2+. It ch the Co2+/Zn e trimetallic Co( he tetrametalli proposed ht loss %, Found (9.32) (28.24) (21.76) 5 (50.00) (16.25) (26.33) (26.33) (31.39) (14.02) (42.29) (12.92) (29.22) (10.25) (24.04) (21.75) (37.03) (14.28) (22.21) (22.76) (40.74) (4.92) (9.84) (11.00) (13.06) urves (25‐800 ve an insight in es. Investigation found stable th in the range 2 O)4(OAc)2]⋅6H2 O. The stabil hetero complex d with the hydr dicating weak b nd showed thre C3H5N2 leaving c)2]⋅3H2O, the d 433 °C are du C9H7N2O3, res of calc. 37.96 ( Zn3(SHBH‐4H)(H nd 575 °C, due t nO2, respective [Ni4(SHBH‐6H 6H2O and in th H2O with C18H18N tion of 2 OAc. H‐6H)(H2O)6] d eft Co3O2 at > ed at 79, 352 a 98 (calcd. 16.25 H7N2O2 [27.63 water at this m cobalt ions. and structurally n with individu bined metal io helated as a n2+ complex; (II) complex an ic complexes. for [Co3(SHB 89 (Calcd.) 0 °C) of all nto the thermal n of the data in han the ligand. 20‐418 °C. The 2O followed by ity of homo x. Some of the rated waters in bonds. ee steps due to C9H7N2O3 as a decomposition ue to the loss of spectively. The (Found: 37.03). H2O)4Cl2]⋅2H2O to the evolution ly. The residue )(H2O)4(OAc)2] he second step N4O6. The third displayed three > 600 °C. The and 522 due to 5%), C9H7N2O2 (26.33)]. The mid‐point may y characterized. ual metal ions: ons: Co2+/Zn2+, tetranegative hexanegative d hexanegative Square‐planar BH‐6H)(H2O)6], l l n . e y o e n o a n f e O n e ] p d e e o 2 e y . : , e e e r , 90 El‐Asmy et al. / European Journal of Chemistry 7 (1) (2016) 81‐90 [Cu4(SHBH‐H)(H2O)4(OAc)2].3H2O, [Ni3Zn(SHBH‐6H)(H2O)6 Cl2].H2O and [Cu3Zn(SHBH‐6H)(H2O)6Cl2] and tetrahedral for [Ni4(SHBH‐H)(H2O)4(OAc)2].6H2O, [Zn3(SHBH‐4H)‐(H2O)4Cl2]. 2H2O and [Co2Zn(SHBH‐6H)(H2O)4‐Cl2].2H2O. Supplementary material Crystallographic data for the structure reported in this paper have been deposited with Cambridge Crystallographic Data Center as supplementary publication CCDC‐1053722. 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