synthesis, characterizations, crystal structure, density functional theory and td dft studies of one...

7/25/2019 Synthesis, Characterizations, Crystal Structure, Density Functional theory and TD DFT Studies of one new dichloro

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Imperial Journal of Interdisciplinary Research (IJIR)

Vol-2, Issue-3 , 2016

ISSN : 2454-1362 , http://www.onlinejournal.in

Imperial Journal of Interdisciplinary Research (IJIR) Page 28

Synthesis, Characterizations, CrystalStructure, Density Functional theory and TD

DFT Studies of one new dichloro-bis(pyridine-N)-CuII, C20H20Cl4Cu2N4 complex.

Dhrubajyoti MajumdarAssistant Professor

Department of Chemistry, Tamralipta mahavidyalaya, Tamluk,Purbamedinipur, W.B., India, 721636.

Abstract : A new novel tetracoordinatedmononuclear copper (II) complex [CuII(py)2Cl2] (1)with pyridine as coligand has been synthesized andcharacterized by elemental analysis (carbon,hydrogen and nitrogen),1H NMR, FT-IR and UV-Vis spectroscopic techniques. The copper (II)complex structure was unambiguously confirmedby single crystal XRD. The complex crystallizes inmonoclinic system, space group P 21 /n, with thevalues a = 3.8742(7), b = 8.6325(17), and c =17.096(3) ; = 90.00, = 91.974, and =90.00 ; V = 571.42(18) 3 and Z = 1. The titledCopper(II) complex is purely mononuclear in

nature where Cu(II) ion is coordinated with two Natoms of two pyridine ligands and two chlorideions(Cl-) and displays completely square planargeometry. The crystal packing is stabilized byintermolecular hydrogen bonding. The geometry ofCu(II) complex was optimized in the singlet groundstates by DFT calculation ( using B3LYPfunctional). Electronic spectra of respectivecomplex(1) was explained in a lucid manner usingTDDFT calculation.

Key words:Cu(II) complex, DFT and TDDFT.

1. INTRODUCTION

Aromatic nitrogen heterocycles are important classof ligands in the field of synthetic coordinationchemistry. Pyridine, Pyrazine, Bipyridine or itsanalogous ligands like phenantroline, methyl orethyl substituted phenantroline are widely used insynthetic coordination chemistry to prepare vastnumber of metal complexes for their potentialapplications in photochromic compounds [1],catalytic role like hydrogenation of olefins [2],analytical chemistry, biological application[3-8]]and also in the mimic chemistry after substitutionof suitable side chain in the nitrogen heterocycles.

All heterocyle ligands have extended cloud thattakes part interaction with suitable metal ions like

Cu(II) which mimic various biological system andhence their study have gained emergingimportance. These ligands due to their chelatingnature in coordinated complexes effectively controlthe aggregation behavior by chelating aroundcentral metal ion. In this regard pyridine or itssubstituted analogous nitrogen donor ligands havebeen extensively used in the field of coordinationchemistry. The coordination chemistry ofcopper(II) has been connected to diverse fields likeindustry and medicinal biochemistry. Aromaticnitrogen heterocycles form very well known lewisacid base adducts with copper(II) ion via molecular

chelating association [9-10]] and thus copper(II)complexes increase their coordination number andthis sometimes puzzling variation in complexesstructural formats [11]. Coordination geometry ofCu(II) depends on ligand used, coligands and alsothe counterions nature [12]. Hence we made anattempt to study the structural variation ofreference Cu(II) complex. In the present researchwork, we report complex(1) synthetic details,spectroscopic analysis, crystal structuredetermination by using single crystal XRD. Theexperimental structure of complex (1) wascompared with the theoretical calculation results at

different levels of DFT and basis sets.2. EXPERIMENTAL2.1 Materials

All the reagents are analytical grade and wereprocured from commercial sources and wereused without further purification. CuCl2.2H2Owas purchased from S.D. fine chemicals,Mumbai (India), and pyridine from (E. Marck,India). Methanol solvent purified and driedaccording to standard procedures.

2.2 Physical measurement

Elemental analysis (carbon, hydrogen andnitrogen) of Cu(II) complex was determined
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Copper(II) complex was characterized by FT-IRand UV-VIS spectroscopy and elementalanalysis(CHN). In addition 1H NMR spectroscopywas used to further characterization of complex(1)(Supporting information 1). The 1H NMRspectrum finely confirmed the complexstructure(1).The FT-IR spectra of the Cu(II)complex shows C=N stretching frequency ofpyridine appears near to 1652 cm-1. The Cu-Nlinkage of Cu(II) complex confirmed by weakbands at 548cm-1 (Supporting information 2).

6. DFT and TD DFT analysis

DFT and TDDFT computations of optimizedstructure of complex (1)was performed in order toestablish its electronics structure and spectraltransitions. The geometric structures of the isolatedcomplexes were fully optimized at the Beckesthree- parameter hybrid exchange functional andthe Lee-Yang-Parr non-local correlation functional(B3LYP) level in the ground state. The optimizedstructures are depicted in fig. 2a. The energy andcomposition of selected MOS (Fig.2band 2c )ofcomplex(1) are summarized in Table 6. TheHOMO of and spin as well as LUMO of spinare concentrated on coordinated ligand forcomplex(1). For comparison ,the geometricalparameters of complex(1) was investigated bymeans of density functional theory (DFT)

calculations at the B3LYP level using 6-31G(d-p),LanL2DZ basis sets and results were comparedwith the experimental data Table 4. According tothis Table, the agreement between the mostgeometrical parameters calculated at the differentDFT levels and the experimental data are goodagreement, suggesting that the DFT/B3LYPmethod and the basis sets used in the calculationare reasonable. The calculated Mullikan charges onthe copper atom in complex(1) (Cu1=0.254) isconsiderably lower than the formal charges of +2,confirming a significant charge donation from theligands. The calculated Mullikan charges for N1

and N2 of Pyridine effective donor center -0.254are less than -1. All these results indicate electrontransfer occurs from the donor atoms to the centralcopper atom. TDDFT calculations have beenperformed to get deep insight into the electronictransitions of complex(1).The calculated verticalelectronic transitions are summarized in Table 5.For complex(1) transitions at 257.5 nm and 287 nmcorresponds to L1LCT and LMCT. Transitions at259.54 nm, 264.35 nm due to both L1LCT and288.74 nm corresponds to LMCT.

7.

Conclusion

We have successfully synthesized the titledcomplex(1) and characterized by IR, UV-Vis ,1HNMR spectroscopic study .The molecular andcrystal structure were determined by single crystalX-ray diffraction and calculated at the DFT levels.The best agreement between theoretical andexperimental results were obtained by usingB3LYP level with 6-31G(d-p) and LanL2DZ basissets.

8. Acknowledgement

DJM thanks Department of chemistry, TamraliptaMahavidyalaya, Tamluk, Purba Medinipur, forgiving the laboratory facilities.

9. Supplementary data

CCDC 1429679 contain the supplementarycrystallographic data for title complex(1). The datacan be obtained free of charge viahttp://www.ccdc.cam.ac.uk/ conts/retrieving.html,or from the Cambridge Crystallographic DataCentre, 12 Union Road, Cambridge CB2 1EZ, UK;fax: (+44) 1223-336-033; or e-mail:[email protected].

10. References[1] Liu W. L., Zou Y., Li. Y., Yao G.Y., and MengQ.J., 2004. Polyhedron 23: 849-855.

[2] Zhao J., Zhao B., LIU J., Xu W., and Wang Z.,2001. Spectrochem. Acta Part A 57: 149-154.[3] Rajasekar M., Sreedaran S., Prabu R.,Narayanan V., Jegadeesh R., Raman N., andRahiman A. K., 2010. J. Coord. Chem. 63:136-146.[4] Abdallah S. M., Mohamed G.G., Zayed M.A.,Abou M.S., and EI-Ela., 2009. Spectrochem . ActaPart A 73: 833-840.[5] Dhanaraj C.J., and Nair M.S., 2009.J.Coord.Chem. 62: 4018-4028.[6] Karthikeyan M.S., Parsad D.J., Poojary B., BhatK.S., Holla B.S., and Kumari N.S.,2006.Bioorg.Med.Chem. 14: 7482-7489.

[7] Panneerselvam P., Nair R.R., Vijayalakshmi G.,Subhramanian E.H., and Sridhar S.K., 2005.Eur.J.Med.Chem. 40: 225-229.[8] Wang C., Wu X., Tu S., and Jiang B., 2009.Synth. React.Iorg.Met-Org. Chem 39:78-82.[9] Mestrovic E., Bucar D.-K., Halasz I., andStilinovic., 2004. Acta Crystallographica SectionE 60: 1920-1922.[10] Ainscough E.W., Brodie A.M., Denny W.A.,and Finlay G.J., 1998. Journal of InorganicBiochemistry 70: 175-185.[11] Cotton F.A., and Wilkinson G., 1988.Angew.Chem. Int. Ed. Engl.27:436.

[12] Karlin K.D., and Zubieta J., CopperCoordination chemistry Biochemical and Inorganic
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Perspectives,Adenine Press, New YORK, 1983and refs. Therein.[13] Sheldrick,G.M., 1990. Acta Crystallogr.,Sect., A 46: 467-473.

[14] Gaussian 09, Revision C.01, Frisch,M.J.,Trucks,G.W., Schlegel,H.B., Scuseria,G.E.,Robb,M.A., Cheeseman,J.R., Scalmani, G.,Barone,V., Mennucci, B., Petersson,G.A.,Nakatsuji,H., Caricato,M., Li,X., Hratchian,H.P.,Izmaylov,A.F., Bloino,J., Zheng,G., Sonnenberg,J.L., Hada, M., Ehara,M., Toyota,K., Fukuda,R.,Hasegawa, J., Ishida, M., Nakajima,T., Honda, Y.,Kitao, O., Nakai, H., Vreven,T., Montgomery,J.A.,Peralta. Jr., J. E. Ogliaro,f., Bearpark,M., Heyd,J.J., Brothers, E., Kudin,K.N.,Staroverov,V.N.,Keith, T., Kobayashi, R.,

Normand, J., Raghavachari, K., Rendell,A.,Burant, J.C., Iyengar, S.S., Tomasi,J., Cossi,M.,Rega,N., Millam, J.M., Klene,M., Knox,J.E.,Cross,J.B., Bakken,V., Adamo,C.,Jaramillo,J., Gomperts, R. Stratmann, R.E.,Yazyev, O., Austin, A.J., Cammi, R., Pomelli,C.,Ochterski, J.W., Martin, R.L. Morokuma,K.,Zakrzewski, V.J., Voth, G.A., Salvador,P.,Dannenberg, J.J., Dapprich,S., Daniels,A.D.,Farkas,O., . Foresman,J.B., Ortiz,J.V.,Cioslowski,J., and Fox,D.J., Gaussian, Inc.,Wallingford CT, 2010.

[15] . Lee, C., Yang, W., and Parr,R.G., 1988.Phys. Rev., B 37:785-789.

Table 1

Crystal data and Refinement details for Complex(1)Empirical formula C20H20Cl4Cu2N4

Formula weight 609.59

Temperature ( K ) 293(2)

Wavelength ( ) 0.71073

Crystal system Monoclinic

Space group P21 / n

Unit cell dimensions

a ( ) 3.8742(7)

b ( ) 8.6325(17)

c ( ) 17.096(3) ( ) 90.00

( ) 91.974(10)

( ) 90.00

Volume ( A3) 571.42(18)

Z 1

Density cal( Mg m-3) 1.771

Absorption coefficient ( mm-1) 2.373

F ( 000 ) 306

Range ( ) for data collection 25.50

Index ranges -4h4

-10k9

-19l20

Goodness-of-fit on F2 1.230

Completeness to theta 0.994

Independent reflections ( Rint ) 0.0544(835)

Refinement method Full-matrix least squares on F2

Reflections collected 1067

Final R indices [I 2( I )] R1=0.0840, R2=0.2175

Largest difference peak and hole ( eA-3) 1.771

Table 2Selected some bond distances ( ) and angles ( ) for complex (1)


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Selected some Bond distances Bond distances value ( )

Cu1-N1 2.037

Cu1-Cl1 2.318

N1-C1 1.35(1)

N1-C5 1.34(1)Cu1-Cl1 2.318

Selected angles Bond angles value ( )

N1-Cu1-Cl1 90.1

N1-Cu1-N1 180.00

N1-Cu1-Cl1 89.9

Cl1-Cu1-N1 89.9

Cl1-Cu1-Cl1 180.00

Cu1-N1-C1 120.1

Cu1-N1-C5 121.5

Table 3Selected some Copper square planar complexes (Cu-N) Bond distances ( ) andBond angle() values.

Complexes Cu-N() 0-Cu-N() N-Cu-N ( ) Ref

C28H28CuN6O4 2.014 91.4 16

2( C30H26CuN2O2 ),

C2H3N

1.956

1.942

93.42

171.48

171.23

93.11

86.40 17

C14H18ClCuN3O5 1.903

1.935

2.020

97.6

176.8

97.5

83.8

164.8

81.1

18

C9H9CuN5O5 1.920

1.956

1.925

173.43 176.92 19

C36H32CdCu2N6O4S2 1.953

1.952

1.962

1.978

92.01

164.80

163.20

92.4992.03

170.96

91.67

96.71

97.24

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C34H32Cu2N6O10Sr 1.9739

1.98871.9740

1.9760

92.11

167.31169.26

92.61

91.83165.

96.62

96.63

21

Table 4Experimental and calculated bond distances () for complex

Experimental Calculated

Cu1 -Cl1 2.318(2) 2.39298

Cu1 -N1 2.037(7) 1.99960

Cu1-Cl1_d 2.318(2) 2.39303Cu1-N1_d 2.037(7) 1.99960

Experimental and calculated bond angles () for complex

Experimental Calculated

Cl1-Cu1-N1 90.1(2) 90.00447

Cl1-Cu1-Cl1_d 180.00 179.93717

Cl1-Cu1-N1_d 89.9(2) 90.00595

Cl1_d-Cu1-N1 89.9(2) 89.99571

N1-Cu1-N1_d 180.00 179.97255Cl1_d-Cu1-N1_d 90.1(2) 89.99390

Table 5Selected list of excitation energies of complex(1)in Methanol using CPCM model.

Excitation Wavelength

(nm)

Oscillatory

strength (f)

Major Contribution Assignment

4 534.54 0.0087 HOMO-1()LUMO() (99%) L1MCT

6 487.66 0.0008 HOMO-3() LUMO() (97%) L1MCT

8 395.51 0.0007 HOMO-13() LUMO() (68%) IMCT

9 393.89 0.173 HOMO-4() LUMO() (94%) L1MCT

12 325.68 0.0015 HOMO-5() LUMO +3() (10%),HOMO-5() LUMO +4() (10%)

ILCTILCT

14 302.07 0.0189 HOMO() LUMO() (84%) L1LCT

16 290.50 0.0134 HOMO-9() LUMO() (94%) LMCT

18 290.12 0.0028 HOMO-5() LUMO() (19%),

HOMO-2() LUMO +1() (10%),

HOMO-6() LUMO +2() (13%),

HOMO-5() LUMO +1() (18%)

ILCT

L1LCT

ILCT

ILCT

19 288.74 0.2786 HOMO-10() LUMO() (95%) LMCT

22 272.65 0.0002 HOMO() LUMO +1() (52%) L1LCT

24 267.53 0.0002 HOMO-1() LUMO() (64%), HOMO()

LUMO +1() (30%)

L1LCTL1LCT

26 264.35 0.0054 HOMO-2() LUMO +1() (94%) L1LCT


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28 261.91 0.0075 HOMO-3() LUMO() (11%),

HOMO-2() LUMO +1() (15%),HOMO-1() LUMO +2() (69%)

L1LCTL1LCT

L1LCT

30 259.54 0.0041 HOMO-3() LUMO() (84%) L1LCT

LMCT= Pyridine ring to copper charge transfer, L1MCT= Chlorine to copper charge transfer,ILCT= Intra pyridine charge transfer, L1LCT= Chlorine to pyridine charge trans

Table 6Selected MOs along with their energies and compositions of complex(1)

MOs Energy (eV) % of CompositionRing Cu Cl

-MOsLUMO+15 4.17 100 0 0

LUMO+14 3.99 98 2 0

LUMO+13 3.98 92 7 1

LUMO+12 3.70 98 2 0LUMO+11 3.47 96 4 0

LUMO+10 2.73 97 3 0

LUMO+9 2.73 100 0 0

LUMO+8 2.11 13 86 1

LUMO+7 0.92 0 100 0

LUMO+6 0.74 0 100 0

LUMO+5 0.49 0 100 0

LUMO+4 0.48 0 97 3

LUMO+3 -1.07 99 1 0

LUMO+2 -1.13 98 2 0

LUMO+1 -1.76 99 1 0

-1.82 98 1 1

-6.85 27 16 57

HOMO -1 -7.18 6 1 92

HOMO -2 -7.26 16 2 82

HOMO -3 -7.30 3 4 93

HOMO -4 -7.52 1 4 94

HOMO -5 -7.96 98 0 2

HOMO -6 -8.04 88 0 11

HOMO -7 -8.09 20 7 73

HOMO -8 -8.62 90 7 3HOMO -9 -8.88 79 3 18

HOMO -10 -9.28 97 2 2

HOMO -11 -9.33 35 49 16

HOMO -12 -10.37 13 87 0

HOMO -13 -10.44 4 93 3

HOMO -14 -10.61 31 61 7

HOMO -15 -10.63 61 38 1

-MOsLUMO+15 4.01 98 2 0

LUMO+14 3.99 92 8 0

LUMO+13 3.70 98 2 0LUMO+12 3.50 96 3 1


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LUMO+11 2.75 100 0 0

LUMO+10 2.75 97 2 0

LUMO+9 2.09 13 87 1

LUMO+8 0.92 -5 105 1

LUMO+7 0.75 0 100 0LUMO+6 0.59 -1 100 0

LUMO+5 0.48 0 97 3

LUMO+4 -1.08 99 0 0

LUMO+3 -1.13 98 1 1

LUMO+2 -1.73 99 1 0

LUMO+1 -1.79 98 1 1

3.68 18 53 30

7.09 6 2 92

HOMO -1 -7.17 15 2 83

HOMO -2 -7.19 2 5 93

HOMO -3 -7.43 2 4 93

HOMO -4 -7.68 9 10 81

HOMO -5 -7.96 98 0 1

HOMO -6 -8.03 91 0 9

HOMO -7 -8.56 87 10 3

HOMO -8 -8.69 5 53 41

HOMO -9 -8.80 89 2 8

HOMO -10 -9.05 95 2 3

HOMO -11 -9.55 26 61 14

HOMO -12 -9.95 9 91 0

HOMO -13 -9.97 1 93 5HOMO -14 -10.31 55 39 5

HOMO -15 -10.49 27 71 1

ALL FIGURESFig.2a. DFT complex(1) optimized structure (Selected and MOS( Fig. 2b & 2c).)

Alpha MOsFig.2b

HOMO-5, 54HOMO-4, 55 HOMO-3, 56

HOMO-2,57 HOMO-1,58 HOMO,59


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LUMO, 60 LUMO+1, 61LUMO+2, 62

LUMO+3, 63LUMO+4, 64

LUMO+5, 65

Beta MOs Fig.2c

HOMO-5, 53HOMO-4, 54

HOMO-3, 55

HOMO-2, 56 HOMO-1, 57 HOMO, 58

LUMO, 59

LUMO+1, 60 LUMO+2, 61

LUMO+3, 62LUMO+4, 63 LUMO+5, 64

Additional Supporting Files can be downloaded from main issue of journalhttp://www.onlinejournal.in/v2i32016/

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