Indian Journal of Chemistry

 

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical
 

Total visitors: 1,426      since 30-06-06

 

VOLUME 45A

NUMBER 6

JUNE 2006

CONTENTS

Papers

 

1339

 

Some boric acid esters of glycerol – An ab initio treatment

 

 

 

 

 

 

 

 

Lemi Türker*

 

 

 

 

Some neutral acyclic and cyclic boric acid-glycerol esters and the corresponding alkoxide complex form of these cyclic esters are treated quantum chemically at the level of 6-311G* (RHF, with and without MP2 correlation).

 

 

 

1345

 

Investigations on UV and IR spectra for C80On (n=1, 2)

 

 

 

 

 

 

 

 

 

 

 

 

 

H Sun, Q Teng*, S Wu & Z Wang

 

 

 

 

Equilibrium geometries and relative stability of possible isomers for C80O and C80O2 have been studied using the AM1 method. The most stable geometry for C80O has been found to be 1,2-C80O when the oxygen atom is added to the 6/5 bond. The most stable geometry for C80O2 is 1,2,14,15-C80O2 with an epoxide structure at the C(1)-C(2) bond.

 

           

 


1351

 

Structural diversity in supramolecular architectures of Mn(II) through non-covalent interactions

 

 

 

 

 

 

 

 

 

Ananta Kumar Ghosh, Debajyoti Ghoshal*, Michael G B Drew &
Nirmalendu Ray Chaudhuri*


 

 

 

Two supramolecular networks of manganese(II) have been  synthesized and characterized by single crystal X-ray analysis. Both the structures are monomeric but extended to higher dimension in the solid state by strong π-π and
C–H…π in
teractions.

 

 

1356

 

Unusual coordination preferences of flexible tetradentate ligands and thiocyanate anions
leads to trans nickel(II) and cis manganese(II) compounds

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Tapan K Karmakar, Barindra K Ghosh,A Usman, Hoong–Kun Fun &Swapan K Chandra*

 

 

 

 

Synthesis, characterisation and properties of two trans-nickel(II) complexes with thiocyanate coordination, [Ni(L1)(NCS)2] and [Ni(L2)(NCS)2]  and comparison
of the results with cis-[Mn(L1)(NCS)2] and
cis-[Mn(L2)(NCS)2] are described. Study reveals that the nickel atom always produces trans isomer and manganese atom gives the cis isomer. Both metals are hexacoordinated with an unusual preferential binding of tetradentate ligands and thiocyanate anions.

 

 

 

1362

 

Synthesis and characterisation of aroylhydrazone complexes derived from some piperidin-4-ones

 

 

 

 

 

 

A Manimekalai* & B Senthil Sivakumar

 

 

 

 

Aroylhydrazone complexes of Ni(II) and Cu(II) of the types [M(L1)2](NO3)2.nH2O, [M(HL2)2](NO3)2 and [M2(HL3)(NO3)4].nH2O [L1= cis-2,6-diphenylpiperidin-4-one benzoylhydrazone, HL2= cis-2,6-diphenylpiperidin-4-one salicyloylhydrazone and HL3= trans-3-methyl-cis-2,6-diphenylpiperidin-4-one salicyloylhydrazone have been synthesized and characterized. The coordination of the ligands is through >C=O and >C=N groups. In bimetallic MDPSH complexes, coordination occurs through phenolic oxygen and amide nitrogen atoms.

 

1368

 

Synthesis and characterization of trivalent chromium, manganese, iron and cobalt complexes with Schiff bases derived from
4-amino-5-mercapto-1,2,4-triazoles

 

 

 

 

Vinod K Sharma* & Shipra Srivastava

 

 

 

 

Cr(III), Mn(III), Fe(III) and Co(III) complexes with Schiff bases derived from 3-substituted phenyl-4-amino-5-mercapto-1,2,4-triazoles and anisaldehyde, veratraldehyde, salicylaldehyde and 2-hydroxyacetophenone have been prepared and characterized. Data suggest a six-coordinated octahedral geometry for all the complexes.

 

1375

 

Synthesis and spectroscopic structural elucidation of five-coordinate homo- and heterometallic complexes of aluminium(III)

 

 

 

 

 

Nandu Bala Sharma, Seema Bansal,
Yash Pal Singh & Anirudh Singh*

 

 

 

 

 

 

1381

 

Studies on excess molar volumes and viscosity deviations of binary mixtures of butylamine and N, N- dimethylformamide with some alkyl acetates at 298.15 K

 

 

 

 

 

 

 

 

 

Vikas Kumar Dakua, Biswajit Sinha & Mahendra Nath Roy*

 

 

 

 

Densities and viscosities have been measured for the binary mixtures of butylamine and N, N- dimethylformamide with methyl acetate, ethyl acetate, butyl acetate and iso-amyl acetate at 298.15 K over the entire composition range and from these data, excess molar volume and viscosity deviation have been determined. The excess properties are found to be either negative or positive depending on the molecular interactions and the nature of liquid mixtures.

Notes

 

1390

 

Derivatisation and transition metal chemistry of a new monophosphinite ligand:                               2-(diphenylphosphinoxy)naphthyl

 

 

 

 

 

 

 

 

Benudhar Punji & Maravanji S Balakrishna*

 

 

 

 

The synthesis, derivatisation and transition metal chemistry of monophosphophinite is described.

 

 

1395

 

Synthesis and characterization of a new Schiff base ligand derived from benzo-15-crown-5 and its complexes with cobalt(II), nickel(II) and copper(II)

 

 

 

 

 

 

 

İbrahim Erden*, Nebahat Demirhan &Ulvi Avcıata

 

 

 

 

 

1400

 

Studies on the crystallographic changes in an analogue of aluminosilicate mineral Muscovite on sorption of UO22+, Th4+ & Ru3+

 

 

 

 

 

 

 

 

 

Radha Tomar*, Pankaj Sharma,Pratibha Sharma & Renu Tomar

 

 

 

 

An analogue of aluminosilicate mica mineral Muscovite has been synthesized hydrothermally at 200°C and sorption studies performed for UO22+, Th4+ and Ru3+ at room temperature in acidic medium. Energy dispersive spectrometry mapping indicates that metal ions are sorbed on the synthesized material by ion-exchange mechanism. Also, structure of the mineral is retained upon UO22+, Th4+ and Ru3+ sorption implying that surface and end sites are affected by the sorption while the interlayer positions of the mineral are not engaged in metal ion sorption.

 

1405

 

Surface and thermodynamic properties of linear alkyl benzene sulphonate and sodium lauryl sulphate in water

 

 

 

 

 

 

N D Kandpal* & H K Sanwal

 

 

 

 

The surface parameters, maximum surface excess, minimum area per molecule and surface pressure for linear alkyl benzene sulphonate and sodium lauryl sulphate in water have been calculated along with thermodynamic parameters from surface tension measurements. Micellization is favored both by energy effects as well as by entropy gain. The increase in critical micelle concentration with increase in temperature corresponds to the high symmetry of the system.

 

 

1408

 

Determination of cadmium(II) with 5-Br-PADAP in the presence of CPC and HDPBA

 

 

 

 

 

 

 

 

 

Ravi Kumar Banjare & Manas Kanti Deb*

 

 

 

 

2 - ( 5 – Bromo – 2 - pyridylazo) – 5 - diethylaminophenol

in presence of a cationic surfactant has been used for the spectrophotometric determination of Cd(II). The red coloured Cd(II) complex with lmax at 560 nm has been extracted with N-hydroxy-N,N′-diphenylbenzamidine in dichloromethane in the pH range 8.6-10.6 and has a detection limit of 0.01 mmg ml-1. The system obeys Beer’s law in the range 0.05-1.0 mg ml-1.

 

Authors for correspondence are indicated by (*)

  

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1339-1344

Some boric acid esters of glycerol- An ab initio treatment

Lemi Türker

Received 30 November 2005; revised 24 April 2006

Some neutral acyclic and cyclic boric acid-glycerol esters and the corresponding alkoxide complexes of these cyclic esters have been treated quantum chemically at the level of 6-311G* (RHF, with and without MP2 correlation). Possible routes for the acyclic monoesters to the cyclic diesters are discussed. The terminal acyclic monoester is found to be more stable than the isomer with the internal ester group. Among the cyclic diesters, it is found that a six-membered ring is favoured energetically over the ester possessing a five-membered ring.

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1345-1350

Investigations on UV and IR spectra for C80On (n=1,2)

 

H Sun, Q Teng *, S Wu & Z Wang

Received 8 November 2005; revised 17 February 2006

Equilibrium geometries and relative stability of possible isomers for C80O and C80O2 have been studied using the AM1 method. The most stable geometry for C80O has been found to be 1,2-C80O when the oxygen atom is added to the 6/5 bond. The most stable geometry for C80O2 is 1,2,14,15-C80O2 with an epoxide structure at the C(1)-C(2) bond. UV-vis and IR spectra for the isomers of C80On (n=1,2) have been investigated using the INDO/CIS and AM1 methods. First absorptions in the electronic spectra and strongest absorptions in the IR spectra are blue-shifted in the order C80(Ih), 1,2-C80O and 1,2,14,15-C80O2 as the LUMO-HOMO energy gap increases and the conjugated system gets stabilized. Also, the C-C bonds are strengthened owing to the addition of the oxygen atoms.

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1351-1355

 

Structural diversity in supramolecular architectures of Mn(II) through
non-covalent interactions

Ananta Kumar Ghosh, Debajyoti Ghoshal *, Michael G B Drew  & Nirmalendu Ray Chaudhuri *

Received 13 September 2005; accepted 24 February 2006

Two mononuclear complexes of manganese(II), [Mn(OCN)2(phen)2] 1 and [Mn(NCO)2(bpy)2] 2 [1,10-phenanthroline (phen); 2,2¢-bipyridine (bpy)], have been synthesized and characterized by single crystal X-ray analysis, infra-red spectroscopy and magnetic studies. The coordination structure of complex 2 is already reported. The cyanate anions are pendent in both the complexes. In 1, cyanate anion links manganese(II) through O-atom, whereas in 2 it coordinates through N-atom. The mononuclear fragments of 1 are built up to a supramolecular lamellar 3D architecture by π-π interactions only. On the other hand, mononuclear fragments of 2 are assembled to a 2D supramolecular brick-wall architecture by C-H˙˙˙π interactions.

IPC Code: Int. Cl.8 C07F13/00

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1356-1361



Unusual coordination preferences of flexible tetradentate ligands and thiocyanate anions leads to trans nickel(II) and cis manganese(II) compounds

Tapan K Karmakar, Barindra K Ghosh, A Usman, Hoong–Kun Fun & Swapan K Chandra*

Received 30 November 2005; revised 24 February 2006

The synthesis, characterisation and properties of two trans nickel(II) complexes with thiocyanate coordination, [Ni(L1)(NCS)2] (1) and [Ni(L2)(NCS)2] (2) and comparison of the results with cis-[Mn(L1)(NCS)2](3)and cis-[Mn(L2)(NCS)2] (4) (L1 and L2 = tetradentate ligands, derived from bis condensation between pyridine-2-carboxaldehyde and 1,3-diaminopropane and 2-benzoyl pyridine and 1,3-diaminopropane respectively) are described. The structures have been determined by single crystal X-ray diffraction studies. Study reveals that the nickel atom always produces trans isomer and manganese atom gives the cis isomer. Both metals are hexacoordinated with an unusual preferential binding of tetradentate ligands and thiocyanate anions.

IPC Code: Int. Cl.8  C07F13/00; C07F15/04

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1362-1367

Synthesis and characterisation of aroylhydrazone complexes
derived from some piperidin-4-ones

A  Manimekalai*  &  B Senthil Sivakumar

Received 5 August 2005; revised 27 March 2006

Ni(II) and Cu(II) complexes of the types [M(L1)2](NO3)2·nH2O, [M(HL2)2](NO3)2 and [M2(HL3)(NO3)4]·nH2O [L1= cis-2,6-diphenylpiperidin-4-one benzoylhydrazone (DPBH), HL2= cis-2,6-diphenylpiperidin-4-one salicyloylhydrazone (DPSH) and HL3= trans-3-methyl-cis-2,6-diphenylpiperidin-4-one salicyloylhydrazone (MDPSH)] have been synthesized and characterized on the basis of elemental, electronic, IR and ESR spectral analyses and also by conductivity measurements, magnetic moment measurements and thermogravimetric analyses (TGA/DTA). The results reflect coordination of the ligands through >C=O and >C=N groups. In bimetallic MDPSH complexes coordination occurs through phenolic oxygen and amide nitrogen atoms. The powder X-ray diffraction analysis reveals that DPBH and DPSH complexes of Ni(II) crystallize in simple cubic unit lattice.

IPC Code: Int. Cl.8 C07F1/08; C07F15/04

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1368-1374

 

Synthesis and characterization of trivalent chromium, manganese, iron and cobalt complexes with Schiff bases derived from 4-amino-5-mercapto-1,2,4-triazoles

 

Vinod K Sharma* & Shipra Srivastava

Received 21 July 2005; revised 10 April 2006

Coordination complexes of Cr(III), Mn(III), Fe(III) and Co(III) with Schiff bases derived from
3-substituted phenyl-4-amino-5-mercapto-1,2,4-triazoles and anisaldehyde, veratraldehyde, salicylaldehyde, 2-hydroxyacetophenone have been prepared and characterized by elemental analyses, electrical conductance, magnetic moments and spectral (electronic, IR, 1H NMR, FAB mass) data. On the basis of spectroscopic studies Schiff bases L1H and L2H are monobasic bidentate towards Cr(III), Mn(III), Fe(III) and Co(III) having composition [M(L1or2)3] and Schiff bases L3H2 and L4H2 are dibasic tridentate towards all the metals with composition [ML3(H2O)2X] and [ML4(H2O)2X] where M = Cr(III), Mn(III), Fe(III) and Co(III) and X = Cl and OAc. Various physicochemical data suggest a six-coordinated octahedral geometry for all the complexes. Ligands and their complexes have been screened for their antibacterial activity against gram-positive and gram-negative bacteria.

IPC Code: Int. Cl.8 C07F11/00; C07F13/00; C07F15/02; C07F15/06; C07F251/02

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp.1375-1380

Synthesis and spectroscopic structural elucidation of five-coordinate homo- and heterometallic complexes of aluminium(III)

Nandu Bala Sharma, Seema Bansal, Yash Pal Singh & Anirudh Singh*

Received 30 November 2005; revised 27 February 2006

Equimolar reactions of Schiff bases (HL) and b-ketoamines(HL*) with Al(OPri)3 in benzene afford mixed-ligand cyclic five-coordinate aluminium complexes of the type [Al(h2-L) (h2-L*)(OPri)] (where L = L1, L* = L3  (1) and L = L2, L* = L4 (2)), in which the deprotonated forms of Schiff base OC6H4CH=NCH(CH3)Et (L = L1) and OC10H6CH=NC6H3(CH3) 2-2,6 (L = L2) as well as b-ketoamines OC(CH3)=CHC(CH3)=NR(R=Et(L* = L3), R=C6H3(CH3)2-2,6 (L* = L4)) are bonded to aluminium in a bidentate (h2) fashion through O, N donor atoms. The complexes (1) and (2) on reaction with hexylene glycol (abbreviated as HOGOH) afford complexes of the type [Al(h2-L)(h2-L*)(OGOH)] (3) (L = L1, L* = L3) and (4) (L = L2, L* = L4) containing three entirely different organic moieties. The latter two complexes on reaction in 1:1 molar ratio in benzene with B(OPri)3, Ti(OPri)4, and Nb(OPri)5 afford novel heterobimetallic complexes of the type [Al(h2-L)(h2-L*) {OGOM(OPri)n-1}] (5, M = B, n = 3, L = L1, L* = L3; 6, M = B, n = 3, L = L2, L* = L4; 7, M = Ti, n = 4, L = L1, L* = L3; 8, M = Ti, n = 4, L = L2, L* = L4; 9, M = Nb, n = 5, L = L1, L* = L3; 10, M = Nb, n = 5, L = L2, L* = L4). All these homo- and heterometallic derivatives have been characterized by elemental analysis, molecular weight measurements, IR and NMR (1H, 27Al, and 13C) spectral studies and plausible structures have been suggested.

IPC Code: Int. Cl.8 C07F5/00; C07F251/00

Indian Journal of Chemistry
Vol. 45A, June 2006, pp 1381-1389

 

Studies on excess molar volumes and viscosity deviations of binary mixtures of butylamine and N, N-dimethylformamide with some alkyl acetates at 298.15 K

 

Vikas Kumar Dakua, Biswajit Sinha & Mahendra Nath Roy *

Received 26 December 2005; revised 21 April 2006

Densities and viscosities have been measured for the binary mixtures of butylamine (BA) and N, N-dimethyl­formamide (DMF) with methyl acetate (MA), ethyl acetate (EA), butyl acetate (BUA) and iso-amyl acetate (AA) at 298.15 K over the entire composition range. From density and viscosity data, the values of excess molar volume (VE) and viscosity deviation (Dh) have been determined. These results have been fitted to Redlich–Kister type polynomial equations to estimate the binary coefficients and standard errors between the experimental and computed values. The density and viscosity data have been analyzed in terms of semiempirical viscosity models and the results have been discussed in terms of molecular interactions and structural effects. The excess properties are found to be either negative or positive depending on the molecular interactions and the nature of liquid mixtures.

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1390-1394

 

Derivatisation and transition metal chemistry of a new monophosphinite ligand:2-(diphenylphosphinoxy)naphthyl

Benudhar Punji & Maravanji S Balakrishna*

Received 30 November 2005; revised 4 April 2006

Reaction of monophosphinite ligand, 2-(diphenylphosphi­noxy)naphthyl, C10H7OPPh2 (1) with elemental sulphur or selenium gives the corresponding sulphide C10H7OP(S)Ph2 (2) or selenide C10H7OP(Se)Ph2 (3) derivatives. Reaction of 1 with [CpRu(PPh3)2Cl] gives monosubstituted complex, [CpRu(C10H7OPPh2)(PPh3)Cl] (4) as well as the disubstituted complex, [CpRu(C10H7OPPh2)2Cl] (5) depending upon the reaction conditions. Treatment of 1 with [Rh(CO)2Cl]2 affords a trans-complex, [Rh(CO)(C10H7OPPh2)2Cl] (6). Reaction of 1 with [Pd(COD)Cl2] results in the formation of an unexpected chloro-bridged dipalladium complex; [Pd(PPh2O)(PPh2OH)(μ-Cl)]2 (7), whereas similar reaction with [Pt(COD)Cl2] gives cis-[Pt(C10H7OPPh2)2Cl2] (8) in good yield.

IPC Code: Int. Cl.8 C07F15/00

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1395-1399

Synthesis and characterization of a new Schiff base ligand derived from benzo-15-crown-5 and its complexes with cobalt(II), nickel(II) and copper(II)

İbrahim Erden*, Nebahat Demirhan & Ulvi Avcıata

Received 5 September 2005; revised 30 March 2006

A new Schiff base ligand, N-quino[8,7-b]azin-5-yl-2,3,5,6,8, 9,11,12-octahydrobenzo [b][1,4,7,10,13]pentaoxacyclopentade­cin-15-ylmethanimine (1) has been synthesized from the reaction of 5-amino-1,10-phenanthroline with 4'-formylbenzo-15-crown-5. The ligand reacts with Co(II), Ni(II) and Cu(II)  salts to form complexes. The ligand and the complexes have been characterized by FTIR, 1H NMR (DMSO-d6), UV-vis, elemental analysis, mass spectra (LC-MS) and magnetic measurements. The metal to the ligand ratio of the Co(II), Ni(II) and Cu(II) complexes have been found to be 1:2. Protonation constants of the ligand and overall formation constants of the complexes have been calculated from potentiometric data using the computer program TITFIT.

IPC Code: Int. Cl.8  C07F1/08; C07F15/04; C0715/06; C07C251/02

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1400-1404

 

Studies on the crystallographic changes in an analogue of aluminosilicate mineral Muscovite on sorption of UO22+, Th4+ & Ru3+

Radha Tomar*, Pankaj Sharma, Pratibha Sharma &

Renu Tomar

Received 13 February 2006; revised 10 April 2006

An analogue of aluminosilicate mica mineral Muscovite has been synthesized hydrothermally at 200°C and sorption studies performed for UO22+, Th4+ and Ru3+ at room temperature in acidic medium (0.1 M). The X-ray diffractograms and scanning electron micrographs have been used to verify changes in crystallinity and crystal morphology on sorption. The synthesized gel has been characterized by X-ray powder diffraction, energy dispersive spectrometry, thermogravimetric analysis, FT-IR spectroscopy and scanning electron microscopy. The chemical composition of the gel is found to be K1.4Al4.2 (Si6Al2O20) (OH)42H2O. Energy dispersive spectrometry (EDS) mapping indicates that metal ions are sorbed on the synthesized material by ion-exchange mechanism. Also, the structure of aluminosilicate mineral Muscovite is retained upon UO22+, Th4+ and Ru3+ sorption implying that surface and end sites are more affected upon sorption while the interlayer positions of the mineral are not engaged in metal ion sorption.

IPC Code: Int. Cl.8 C01B33/42

 

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1405-1407

 

Surface and thermodynamic properties of linear alkyl benzene sulphonate and sodium lauryl sulphate in water

N D Kandpal*, & H K Sanwal

Received 19 April 2005; revised 7 April 2006

The surface parameters, maximum surface excess, minimum area per molecule, surface pressure for linear alkyl benzene sulphonate and sodium lauryl sulphate in water have been calculated along with thermodynamic parameters from surface tension measurements. Micellization is favored both by energy effects as well as by entropy gain. The increase in critical micelle concentration with increase in temperature corresponds to the high symmetry of the system.

IPC Code: G01N13/00; G01N13/02

 

Indian Journal of Chemistry
Vol. 45A, June 2006, pp. 1408-1412

 

Determination of cadmium(II) with 5-Br-PADAP in the presence of CPC and HDPBA

Ravi Kumar Banjare & Manas Kanti Deb*

Received 17 November 2005; revised 8 February 2006

2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP), a trihydroxy phenyl dye and N-hydroxy-N,N’-diphenylbenzamidine (HDPBA), a reported extractant, in presence of a cationic surfactant (CPC) have been used for the spectrophotometric determination of cadmium(II). The Cd(II)-CPC-(5-Br-PADAP) red coloured complex formed in aqueous medium has been extracted with N-hydroxy-N,N’-diphenylbenzamidine in dichloromethane in the pH range 8.6-10.6. This extracted complex shows maximum absorbance at lmax = 560 nm against reagent blank with molar absorptivity of 9.5×104 dm3 mol-1 cm-1. The detection limit of the method is 0.01 mg ml-1. The relative standard deviation (RSD, n=10) for solutions containing 0.40 mg ml-1 Cd(II) is 1.6%. The system obeys Beer’s law in the range 0.05-1.0 mg ml-1. The effect of foreign ions and other experimental variables have been studied. Cd(II) has been successfully determined in standard, environmental and biological samples using the present method.

IPC Code: Int. Cl.8 G01N21/00