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C22H24N4, triclinic, P 1 ‾ $P‾{1}$ (no. 2), a = 9.217(4) Å, b = 9.774(4) Å, c = 10.843(4) Å, α = 96.770(2)°, β = 101.791(5)°, γ = 105.873(3)°, V = 903.9(6) Å3, Z = 2, R gt (F) = 0.0391, wR ref (F 2) = 0.1069, T = 93(2) K.

An octamethyl substituted tetraazacylotetradecadiene ligand salt Me8[14]diene.2HClO4 (L.2HClO4) on reduction produced three isomeric C-chiral ligands LA, LB & LC. Interaction of LB with excess acrylonitrile resulted in a N-pendent cyanoethyl derivative ligand, LBX. Reaction of LBX with nickel(II) salt, Ni(CH3COO)2.4H2O followed by the addition of NaClO4 afforded the complex, [NiLB](ClO4)2, as resulted by the interaction with LB instead of LBX with the same nickel(II) salt which on twelve hours reflux with acrylonitrile yielded square planar nickel(II) diperchlorate complex, [NiLBX](ClO4)2, This complex underwent axial addition reactions with KX (X = SCN, Br or I) and NaNO2 to form octahedral diisothiocyanatonickel(II) complex, [NiLBX(NCS)2]; dibromidonickel(II) complex, [NiLBXBr2]; diiodidonickel(II) complex, [NiLBXI2] and monoaquamononitronickel(II) perchlorate complex, [NiLBX(NO2)(H2O)](ClO4) respectively. The ligand, LBX with copper(II) chloride yielded purple dichloridocopper(II) complex, [CuLBXCl2] of octahedral geometry which underwent axial substitution reactions with KX and NaNO2 to form octahedral diisothiocyanatocopper(II) complex [CuLBX(NCS)2]; dibromidocopper(II) complex [CuLBXBr2]; diiodidocopper(II) complex, [CuLBXI2] and dinitrocopper(II) complex [CuLBX(NO2)2] respectively. These complexes were characterized on the basis of elemental, spectroscopic, magnetochemical and conductrometric analysis. The antibacterial activities of the ligand and complexes have been investigated against different human pathogenic gram positive and gram negative bacteria.

Interaction of CH3I with L (3,10-C-meso-Me8[14]diene) in the ratio of 4:1 in ethanolic solution at room temperature yielded N-pendent dimethyl derivative [(L-2H)(–CH3)2] denoted by LZ. Interaction of nickel(II) acetate tetrahydrate with LZ and subsequent addition of NaClO4·6H2O produced square planar orange-yellow product, [NiLZ](ClO4)2. The reaction of copper(II) perchlorate hexahydrate with LZ afforded four coordinated square planar red [CuLZ](ClO4)2. However, on the reaction of zinc(II) nitrate hexahydrate with LZ furnished white six coordinated two distereoisomeric complexes [ZnLZα(NO3)2] and [ZnLZβ(NO3)2]. Axial addition reactions on four coordinated square planar [NiLZ](ClO4)2 with KX (X= SCN, NO3, Cl, Br or I) and NaNO2 resulted in six coordinated octahedral and square pyramidal axial addition products, such as [NiLZ(NCS)2], [NiLZ(NO3)(ClO4)], [NiLZCl(ClO4)], [NiLZBr2], [NiLZI2] and [NiLZ(NO2)](ClO4), respectively. However axial substitution reactions on [ZnLZα(NO3)2] with KY (Y= SCN, Cl or Br) and NaNO2 produced six coordinated octahedral axial substitution products [ZnLZα(NCS)2], [ZnLZαCl2], [ZnLZαBr2] and [ZnLZα(NO2)2]. Similarly, the axial substitution reactions on [ZnLZβ(NO3)2] with KI and NaClO4.6H2O resulted in six coordinated octahedral axial substitution products [ZnLZβI2] and [ZnLZβ(H2O)2](ClO4)2, respectively. The compounds have been characterized by analytical, spectroscopic, magnetochemical and conductivity data. The antimicrobial activities of the new ligand and its complexes have been tested against different micro pathogens. Nickel(II), copper(II) and zinc(II) complexes with an N-pendent dimethyl derivative ligand LZ of an octamethyl tetraazmacrocyclic ligand were prepared. The compounds were characterized by different analytical and spectroscopic methods. Antibacterial and antifungal activities of these compounds against some bacteria and fungi were also investigated.

Biologically important tetraaza-macrocyclic ligand 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene dihydroperchlorate, Me8[14]diene·2HClO4 (L1·2HClO4) was synthesized by the condensation of 1,2-diaminopropane with acetone in presence of quantitative amount of HClO4 and three isomeric ligands designated as LA, LB and LC were separated by the reduction of L1·2HClO4 with NaBH4 and fractional crystallization from xylene. The nitrato, nitro, bromido, and iodido complexes of palladium with diene ligand L1 were prepared by the interaction of L1·2HClO4 with K2[Pd(NO3)4], K2[Pd(NO2)4], K2[PdBr4], and K2[PdI4] (prepared by the reactions with PdCl2 with KNO3, KNO2, KBr, and KI, respectively), respectively. The bromide and iodido complexes of LA were prepared by the axial substitution reactions with [PdLACl2]Cl2. By contrast, similar complexes of other isomeric ligands LB and LC were prepared by axial addition reactions of [PdLʹ][PdCl4] (L′ = LB or LC) with KBr and KI, respectively. The complexes were characterized on the basis of elemental analysis: IR, 1H-NMR, UV–Vis spectroscopic analysis, and magnetic and molar conductivity data. The antifungal and antibacterial activities of these compounds have been studied against some phyto-pathogenic fungi and bacteria.

Condensation of 1,2-diamino propane with acetone in the presence of perchloric acid furnished a 14-membered octamethyl tetraazamacrocycle, Me8[14]diene⋅2HClO4, which further produced a mixture of isomeric ligands, Me8[14]anes (LA, LB, and LC), on reduction with NaBH4 and subsequent extraction with CHCl3 (pH > 12). The isomers were separated by fractional crystallization from xylene. Interaction of LC with excess acrylonitrile afforded an N-pendant derivative, LCX, in which two cyanoethyl groups were attached to less crowded nitrogen atoms (N4 and N11). Upon the interaction of LCX with Ni(CH3COO)2⋅4H2O, Cu(ClO4)₂⋅6H2O, and Co(CH3COO)₂⋅4H₂O, square planar [Ni(LCX)](ClO4)2 and [Cu(LCX)](ClO4)2 and octahedral trans-[Co(LCX)Cl2](ClO4), respectively, were produced. Axial substitution reactions of trans-[Co(LCX)Cl2](ClO4) with KCNS, KM (M = NO3, Br, or I), and NaNO2 afforded substituted trans-[Co(LCX)(NCS)2](SCN), trans-[CoLCX(X)2](ClO4), and trans-[Co(LCX)(NO2)2](ClO4), respectively. The ligand and corresponding metal complexes were characterized based on the analytical, spectroscopic, magnetic moment, and molar conductivity data. Gram-positive and gram-negative bacteria and different fungi were used to evaluate the antibacterial and antifungal activities of the ligand and its metal complexes.

The ligand salt, Me6[14]diene·2HClO4 (L·2HClO4) was prepared by condensation of acetone and ethylene diamine in the presence of perchloric acid. On reduction of this diene ligand salt, L·2HClO4 with sodium borohydride, the two isomeric ligands, ‘tet-a’ and ‘tet-b’ were produced. The ligands, on reaction with ZnX2 (X=Cl, ClO4, NO3 or CH3COO) and ZnSO4 produced the corresponding complexes. These complexes have been characterized on the basis of elemental analyses; IR, UV–Vis and 1H-NMR spectroscopies; magnetic and conductance data. Based on these data, all of the complexes of the diene ligand L, as well as the perchlorate complexes of all of the ligands attained a square-pyramidal arrangement, whereas the complexes of ‘tet-a’ and ‘tet-b’, with X=NO3, Cl or CH3COO and with ZnSO4 salt, were octahedral. Moreover, all complexes were monometallic except the nitrato complex, [(ZnL)2(µ-NO3)](ClO4)3 which is bimetallic. The structure of [(ZnL)2(µ-NO3)](ClO4)3 has been confirmed by X-ray crystallography. In this complex the zinc centres lie within a N4O donor set, with the four nitrogen donors from L and one of the oxygen atom stemming from the bridging NO3. The complexes show different electrolytic behavior in different solvents. The antibacterial activities of the ligands and complexes towards different phytopathogenic bacteria have been investigated.

Hexamethyl derivative salt of the fourteen membered tetraazamacrocycle, Me6[14]diene.2HClO4 (L.2HClO4) has been synthesized by the condensation of ethylenediamine with acetone in presence of quantitative amount of perchloric acid. This diene ligand salt on reduction with NaBH4 followed by extraction with CHCl3 at pH above 12 resulted in a mixture of isomeric ligands, Me6[14]anes which were separated by fractional crystallization from xylene and designated by ‘tet-a’ and ‘tet-b’. Interaction of ‘tet-b’ with excess of acrylonitrile yielded an N-pendent derivative ‘tet-bx’ in which two cyanoethyl groups were attached on less crowded two trans-N atoms. Interactions of nickel(II) acetate tetrahydrate and copper(II) perchlorate hexahydrate with ‘tet-bx’ followed by subsequent addition of NaClO4·6H2O and HClO4 in case of nickel(II) produced square planar orange [Ni(‘tet-bx’)](ClO4)2 and six coordinated octahedral reddish purple [Cu(‘tet-bx’)(ClO4)2] complex respectively. The axial addition reactions on [Ni(‘tet-bx’)](ClO4)2 with NCS, NO3, NO2, Cl, Br and I afforded different colored six coordinated octahedral axial addition products: violet [Ni(‘tet-bx’)(NCS)2]; violet [Ni(‘tet-bx’)(NO3)(ClO4)]; green [Ni(‘tet-bx’)(NO2)(H2O)](ClO4); brown [Ni(‘tet-bx’)(ClO4)Cl]; brown [Ni(‘tet-bx’)(H2O)Br](ClO4) and pink [Ni(‘tet-bx’)(ClO4)I] respectively. All compounds have been characterized by different analytical and spectroscopic parameters. The antimicrobial activities of the concerned ligand and its complexes have been investigated against different bacteria and fungi.

The molybdenum complexes of different Schiff base ligands have drawn remarkable attention due to their different biological and analytical activities. Several molybdenum complexes of different Schiff base ligands, L1 to L11 derived from dithiocarbazate, have been synthesized by the reaction of the ligands with molybdenum(VI)acetylacetonate. The complexes were characterized on the basis of IR, 1H NMR and electronic spectral analyses, along with elemental, magnetochemical and conductometric data. All the complexes are diamagnetic and non-electrolytes in DMF solution. The molecular structures of two complexes were confirmed by X-ray crystallographic studies. Antibacterial and antifungal characteristics of the concerned compounds were investigated against different gram-positive and Gram negative bacteria, and against fungi, respectively. Most of the complexes show good activity against fungi and bacteria; in some cases, the complexes were more active than the standard medications Nystatin and Ampicillin respectively.

The hexamethyl tetraazacyclotetradecadiene dihydroperchlorate Me6[14]diene. 2HClO4 (L·2HClO4) on reduction produced two isomeric C- chiral ligands ‘tet-a’ and ‘tet-b’. Reactions of these isomeric ligands with PdCl2 produced square planar tetrachlorodipalladium(II) complexes, [PdL′][PdCl4] (L′ = ‘tet-a’ or ‘tet-b’). Similar reactions of L·2HClO4 with different palladium(II) salts, K2Pd(SCN)4, K2PdBr4 and K2PdI4 produced octahedral palladium(IV) thiocyanato, bromido and iodido complexes. Tetrachlorodipalladium(II) complex of isomeric ligands [PdL′][PdCl4] underwent substitution reactions with KCNS and KNO2 to form tetrathiocyanato dipalladium(II) and tetranitrodipalladium(II) complexes, [PdL′][Pd(NCS)4] and [PdL′][Pd(NO2)4] respectively. However the same tetrachloro complexes underwent axial addition reactions with KBr and KI to form dibromidopalladium(IV) dibromide and diiodidopalladium(IV) diiodide complexes, [PdL′][PdBr2]Br2 and [PdL′][PdI2]I2 respectively. The complexes were characterized on the basis of elemental, spectroscopic, magnetochemical and conductometric analysis. The antibacterial and antifungal activities of the ligands and their complexes have been investigated towards different gram positive and gram negative bacteria and fungi.

An isomeric ligand, $$\hbox {L}_{\mathrm{B}}$$ of 3,10-C-meso- $$\hbox {Me}_{8}$$ [14]ane on alkylation reaction with excess acrylonitrile resulted in a stereoselective product trans-(3S,5S,10R,12R)-N1,N8-bis(2-cyanoethyl)-C-meso-derivative, $$\hbox {L}_{\mathrm{BX}}$$ . Reaction of $$\hbox {L}_{\mathrm{B}}$$ with Cd( $$\hbox {ClO}_{4})_{2}\cdot 4\hbox {H}_{2}\hbox {O}$$ in methanol gave the octahedral complex, [Cd( $$\hbox {L}_{\mathrm{B}})$$ ( $$\hbox {ClO}_{4})_{2}$$ ] whereas interaction of the ligand $$\hbox {L}_{\mathrm{BX}}$$ with Cd( $$\hbox {NO}_{3})_{2}\cdot 4\hbox {H}_{2}\hbox {O}$$ in methanol yielded a square pyramidal mononitratocadmium(II) nitrate complex, [Cd( $$\hbox {L}_{\mathrm{BX}})$$ ( $$\hbox {NO}_{3})$$ ]( $$\hbox {NO}_{3})$$ and an octahedral dinitratocadmium(II) complex, [Cd( $$\hbox {L}_{\mathrm{BX}})$$ ( $$\hbox {NO}_{3})_{2}$$ ]. The complexes, [Cd( $$\hbox {L}_{\mathrm{B}})$$ ( $$\hbox {ClO}_{4})_{2}$$ ] and [Cd( $$\hbox {L}_{\mathrm{BX}})$$ ( $$\hbox {NO}_{3})_{2}$$ ] underwent axial substitution reactions with KCNS and KBr to produce octahedral diisothiocyanatocadmium(II) complexes, [Cd( $$\hbox {L}_{\mathrm{B}})$$ (NCS) $$_{2}$$ ] and [Cd( $$\hbox {L}_{\mathrm{BX}})$$ (NCS) $$_{2}$$ ] and octahedral dibromidocadmium(II) complexes, [Cd( $$\hbox {L}_{\mathrm{B}})\hbox {(Br)}_{2}$$ ] and [Cd( $$\hbox {L}_{\mathrm{BX}})\hbox {(Br)}_{2}$$ ], respectively; whereas, [Cd( $$\hbox {L}_{\mathrm{BX}})$$ ( $$\hbox {NO}_{3})$$ ]( $$\hbox {NO}_{3})$$ underwent axial addition with KCl, simultaneous axial substitution and anion exchange with KCNS and simultaneous axial addition, substitution and anion exchange with $$\hbox {NaClO}_{4}\cdot 6\hbox {H}_{2}\hbox {O}$$ to produce octahedral [Cd( $$\hbox {L}_{\mathrm{BX}})$$ ( $$\hbox {NO}_{3})$$ Cl], square planar octahedral [Cd( $$\hbox {L}_{\mathrm{BX}})$$ ( $$\hbox {H}_{2}\hbox {O}$$ ) $$_{2}$$ ]( $$\hbox {ClO}_{4})_{2}$$ , respectively. The newly prepared compounds have been characterized by different analytical and spectroscopic methods. The antibacterial activities of the ligands, metal salts and complexes have been tested against two selected gram positive bacteria and two gram negative bacteria.

One isomeric ligand, LB among three isomers (LA, LB and LC) of 2,9- C-meso-2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecanes, differing in the orientation of methyl groups on the chiral carbon atoms) on interaction with vinyl acetate produces 2,9-C-meso-2,5,5,7,9,12,12,14- octamethyl-1,8-diaza-4,11-diazoniacyclotetradecane as its bis(acetate) trihydrate, [LBH2][OOCCH3]2.3H2O. This ligand salt trihydrate reacts with Zn(CH3COO)2.2H2O to produce square pyramidal monoacetatozinc(II) acetate complex [ZnLB(CH3COO)](CH3COO), which undergoes anion exchange reaction with NaClO4.6H2O to produce monoacetatozinc(II) perchlorate complex, [ZnLB(CH3COO)](ClO4). The complex, [ZnLB(CH3COO)](ClO4) undergoes axial substitution reactions with KSCN, NaNO2 and KNO3 to form the substitution products, [ZnLB(NCS)](NCS), [ZnLB(NO2)](ClO4) and [ZnLB(NO3)](ClO4) respectively where CH3COOis replaced by NCS- , NO3 - and NO2 - . All these complexes have been characterized on the basis of analytical, spectroscopic, conductometric and magnetochemical data. The antifungal and antibacterial activities of these compounds have been studied against some phytopathogenic fungi and bacteria.

Condensation of ethylendiamine with acetone in the presence of quantitative amount of perchloric acid, yielded the ligand 5,7,7,12,14,14- hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene dihydroperchlorate (denoted by L.2HClO4). The ligand L.2HClO4 on reduction with NaBH4, yielded an isomeric mixture of saturated macrocycles, the Me6[14]anes, which were resolved into two distinct C-chiral isomers (denoted by ‘tet-a’ and ‘tet-b’). Interaction of ligands L.2HClO4, ‘tet-a’ and ‘tet-b’ with salts CdI2, Cd(NO3)2.4H2O, CdCl2.2H2O and Cd(ClO4)2.6H2O produced different five coordinated square pyramidal and six coordinated octahedral cdmium(II) complexes. Among them the complexes, cis-[Cd(teta)( NO3)](NO3) and cis-[Cd(tet-b)(NO3)](NO3) underwent axial ligand substitution reaction with KCNS; whereas complex [Cd(tet-a)I2] underwent axial ligand substitution reaction and complex [CdLI](ClO4) underwent simultaneous ligand substitution and addition reaction with NaNO2. Characterization of all the complexes were carried out on the basis of elemental analysis; FT-IR, UV-Vis. and 1H-NMR spectroscopy; melting point determination as well as by magnetic moment and conductivity measurements. Molar conductivity measurment of the complexes reavealed that they show different electrolytic behavior in different solvents.