research article synthesis and use of [cd(detu) 2(oocch 3 2]·h … · 2019. 7. 31. · group...

Hindawi Publishing CorporationThe Scientific World JournalVolume 2013 Article ID 907562 6 pageshttpdxdoiorg1011552013907562

Research ArticleSynthesis and Use of [Cd(Detu)

2(OOCCH

3)2]middotH2O as Single

Molecule Precursor for Cds Nanoparticles

Peter A Ajibade

Department of Chemistry University of Fort Hare Private Bag X1314 Alice 5700 South Africa

Correspondence should be addressed to Peter A Ajibade pajibadeufhacza

Received 17 June 2013 Accepted 15 July 2013

Academic Editors A I Matesanz A Souldozi and W-Y Wong

Copyright copy 2013 Peter A Ajibade This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Substituted thiourea ligands are of interest because they possess various donor sites for metal ions and their application inseparation of metal ions and as antimicrobial agentsThe coordination of the sulfur donor atom led to interest in them as precursorfor semiconductor nanoparticles In this study cadmium(II) complex of diethylthiourea was synthesized and characterized byelemental analysis FTIR and X-ray crystallography Single crystal X-ray structure of the complex showed that the octahedralgeometry around the Cd ion consists of two molecules of diethylthiourea acting as monodentate ligands and two chelating acetateions The thermal decomposition of the compound showed that it decomposed to give CdS The compound was thermolysed inhexadecylamine (HDA) to prepare HDA-capped CdS nanoparticles The absorption spectrum showed blue shifts in its absorptionband edges which clearly indicated quantum confinement effect and the emission spectrum showed characteristic band edgeluminescence The broad diffraction peaks of the XRD pattern showed the materials to be of the nanometric size

1 Introduction

Substituted thiourea showsmore diverse coordination chem-istry because of its conformational isomerism steric effectand the presence of donor sites on the substituted groupsand intramolecular interactions [1ndash9] Their chemistry hasattracted attention due to various applications in separationof metal ions and as antimicrobial agents [2ndash8] Coordi-nation abilities of these ligands showed that the N-alkylthiourea with the coplanar N

2CS skeletal atoms can exist

in two possible conformational forms whereas three differ-ent conformations are possible for NN1015840-dialkyl substitutedthiourea [8] Several studies have been done to understandthe coordination chemistry of this type of ligand and itsbiological activities [7ndash10] and recently the use of the d10metal complexes as precursors formetal sulfide nanoparticles[11ndash14] Group 12 coordination compounds of thiourea havereceived attention in recent years for their nonlinear opticalproperties [9 10] and their use as single source precursorsfor the preparation of semiconducting materials based onmetal sulfide (MS) through thermal decomposition of thecorresponding complexes [2 11ndash15] In this study the syn-thesis characterization and thermal and single crystal X-ray

studies of Cd(II) complex of diethylthiourea are presentedThe complex was used to prepare hexadecylamine- (HDA-)capped CdxSy nanoparticles and the optical and structuralproperties of the nanoparticles determined

2 Experimental Section

21 Materials and Instrumentation All the reagents andsolvents used were of analytical grades and used withoutfurther purification IR spectrum was obtained as KBr discson a Perkin-Elmer Paragon 1000 FTIR spectrophotometerequipped with CsI window (4000ndash250 cmminus1) Thermogravi-metric analysis was performed on a Perkin Elmer thermo-gravimetric analyzer (TGA 7) fitted with a thermal analysiscontroller (TAC 7DX) A flow of N

2was maintained with a

heating rate of 10∘Cmin between ambient temperature and800∘C 10ndash12mg of the sample was loaded into an aluminacup and weight changes were recorded as a function oftemperature

22 Synthesis of the [Cd(detu)2(OOCCH

3)2]sdotH2O The com-

plex was prepared by addition of 2mmol (0533 g) of Cd

2 The Scientific World Journal

C1

C2

C3

C4

C5

C6

C7C8

C9

C10

C11

C12

C13

C14

S1

S2

01S

02

03

04

N1

N2

N3

N4 Cd1

01

Figure 1 The molecular structure of [Cd(detu)2(CH3COO)

2]sdotH2O

showing the atom-labeling scheme Displacement ellipsoids aredrawn at 50 probability level H atoms are represented by circlesof arbitrary radius

(CH3COO)

2sdot2H2O dissolved in 50mL of absolute ethanol

to a stirring 4mmol of diethylthiourea (0529 g) in 50mLabsolute ethanolThemixturewas refluxed for 6 h and filteredand left to evaporate slowly at room temperature Whitecrystals suitable for X-ray analysis were obtained after fewdays Anal Calc For C

14H32CdN4O5S2 C 3278 N 1092 H

629 S 1250 Found C 3301 N 1064 H 603 S 1279

23 Single Crystal X-Ray Crystallography Single crystalssuitable for X-ray analysis for [Cd(detu)

2(OOCCH

3)2]sdotH2O

were obtained after few days by slow evaporation of ethanolicsolution of the complex The data sets for the single crystalX-ray studies were collected with Mo K120572 radiation (k =071073) at 100(2) K on a Bruker SMART APEX [16 17] CCDdiffractometer equipped with an Oxford Cryosystems lowtemperature device Unit cell dimensions were obtained byleast-squares refinement based on the setting angles of 925reflections with theta (ℎ) angles ranging from 250 to 2650The structure was solved by direct methods and refined byfull-matrix least square on1198652 (SHELX97) [18 19] and there isa water molecule in the asymmetric unit All hydrogen atomsbonded to carbon were included in calculated positionsThose bonded to nitrogen and oxygen were found by thedifference Fourier techniques and refined isotropically

24 Synthesis of CdS Nanoparticles About 05 g of[Cd(detu)

2(CH3COO)

2]sdotH2O was dissolved in 10mL of

trinoctylphosphine and injected into 6 g of hot hexadecylam-ine (HDA) at 150∘C A subsequent decrease in temperature of20ndash30∘C was observedThe solution was heated to 150∘C and

stabilized at this temperature for 1 h The solution was thenallowed to cool to 70∘C an excess of methanol was addedand a flocculants precipitate was formed The solid wasseparated by centrifugation and redispersed in toluene Thetoluene was removed under vacuum to give HDA-cappedCdS nanoparticles

25 Characterization of Nanoparticles XRD patterns wererecorded by a Bruker D8 Advance X-ray diffractometerequipped with a proportional counter using Ni-filteredCu K120572 radiation (120582 = 15405A) Transmission electronmicroscopy (TEM) imageswere obtained on aPhilipsCM200compustage transmission electron microscope with an accel-erating voltage of 200 kV The electronic spectra of thecomplexes were taken on a Perkin Elmer Lambda 250UV-vis spectrometer A Perkin Elmer LS 45 Fluorimeter was usedto measure the photoluminescence of the nanoparticles TheSEM image was obtained in a Jeol JSM-6390 LV apparatususing an accelerating voltage between 15ndash20 kV at differentmagnifications Composition and energy dispersive spec-trum was processed using energy dispersive X-ray analysis(EDX) attached to the SEM with Noran System six software

3 Results and Discussion

31 Molecular Structure of [Cd(detu)2(OOCCH

3)2]sdotH2O The

molecular structure of the complex with atom numberingscheme is shown in Figure 1 The crystal data and structurerefinement are presented inTable 1 and selected bond lengthsand angles are given in Table 2 The cadmium in the molec-ular structure is a six-coordinate CdS

2O4form in which the

Cd ion is coordinated to two monodentate diethylthioureasand two chelating acetate ions The coordination polyhedralaround Cd(II) is a distorted octahedron which might be dueto the small bite angles of the acetate ions O(2)ndashCd(1)ndashO(1)[5451(6)∘] and O(4)ndashCd(1)ndashO(3) [5420(6)] This also ledto deviation of trans O(4)ndashCd(1)ndashO(1) O(2)ndashCd(1)ndashS(1) andO(3)ndashCd(1)ndashS(2) bond angles significantly from 180∘ (rangesfrom 14121(6)∘ to 15148(4)∘) The diethylthiourea ligandsare cis to each other and SndashCd(1)ndashS bond angle around thecadmium ion is 10283(3)∘ which deviates considerably from90∘ This may be ascribed to the steric interaction betweenthe substituents on the diethylthiourea The CndashSndashCd bondangles of 10882(8)∘ and 11159(8)∘ are slightly greater than thetetrahedral value

The SndashCndashN and NndashCndashN bond angles ranges from11851(17)∘ to 12162(17)∘ and are within the expected rangeof tetrahedral The CndashN bonds (1327(3) A to 1458(3) A) andCndashS bonds 1727(2) A to 1730(2) A are intermediate betweensingle and double bonds This may be attributed to thedelocalization of electron in the thioamide bonds [20 21]Thehydrogen bonding network within the molecule is betweenthe acetate oxygen atom and NH and acetate oxygen atomand the hydrogen atoms of water within the crystal lattice(Table 3) Each water molecule within the crystal lattice islinked to three cadmium complex units via intermolecularhydrogen bondsTheother intermolecular hydrogen bondingis between the acetate oxygen atom and the NH of the

The Scientific World Journal 3

Table 1 Summary of crystal data and structure refinement for[Cd(detu)2(CH3COO)2]sdotH2O

Compound [Cd(detu)2(CH3COO)2]sdotH2OEmpirical formula C14H32CdN4O5S2Formula weight 51296Temperature 100(2) KWavelength 071073Crystal system MonoclinicSpace group P2(1)cUnit cell dimensions119886 (A) 11755(4)119887 (A) 12262(4)119888 (A) 16609(5)120573 (∘) 108071(5)120574 (∘) 90

Volume (A3) 22759(12)119885 4119863calc Mgm3 1487Absorption coefficient (mmminus1) 1172119865(000) 1056Crystal size (mm) 025 times 020 times 020

Theta range (∘) 182 to 2643

Limiting indices minus14 le ℎ le 14 minus15 le 119896 le 15minus20 le 1 le 20

Reflections collected 17814Independent reflection 4672 [119877(int) = 00300]Refinement method Full-matrix least squares on 1198652

Completeness to 120579 = 2640 997Datarestraintsparameters 46720265Goodness of fit on 1198652 1110Final 119877 indices [119868 gt 2sigma(119868)] 1198771 = 00273 1199081198772 = 00607119877 indices (all data) 1198771 = 00324 1199081198772 = 00625Largest diff peak and hole esdotAminus3 0441 and minus0321

diethylthiourea of neighbouring cadmium complex unitThecrystal packing (Figure 2) contained four cadmium complexunits in two parallel chains Each adjacent molecule is linkedby intermolecular hydrogen bonds through a water moleculevia the acetate oxygen atoms

32 Infrared Spectra Studies The IR spectra of the ligand andcomplexwere compared and assigned on careful comparisonThe absorption band in the 3430ndash3200 cmminus1 experiencedonly very slight changes in the complex The NndashH bandoccurs at 3275 cmminus1 with a shoulder at 3430 cmminus1 in thespectrum of the complex The bands overlap with the CndashH band to form a generally broad band This is due to thepresence of H-bonds networks in the molecular structureof the complex as confirmed by the single crystal X-raystructure of the compound (Figure 3) The ](C=S) stretchingvibrations occur at 747 cmminus1 and the thioamide bond isobserved as multiple band in the region 1554ndash1562 cmminus1This

Table 2 Selected bond length and angles for [Cd(detu)2sdot(CH3COO)2]sdotH2O

Bond length (A) Bond angles (∘)Cd(1)ndashO(4) 23077(18) S(1)ndashCd(1)ndashS(2) 10283(3)Cd(1)ndashO(2) 23714(18) O(2)ndashCd(1)ndashO(1) 5451(6)Cd(1)ndashO(1) 24200(18) O(4)ndashCd(1)ndashO(3) 5420(6)Cd(1)ndashO(3) 24753(17) O(2)ndashCd(1)ndashO(3) 7928(6)Cd(1)ndashS(1) 25587(8) C(2)ndashS(1)ndashCd(1) 10882(8)Cd(1)ndashS(2) 25656(9) C(6)ndashS(2)ndashCd(1) 11559(8)Cd(1)ndashC(13) 2745(2) O(4)ndashCd(1)ndashS(1) 11464Cd(1)ndashC(11) 2748(2) O(2)ndashCd(1)ndashS(1) 14557(4)O(1)ndashC(11) 1271(3) O(1)ndashCd(1)ndashS(1) 9520(4)O(1)ndashC(13) 1249(3) O(3)ndashCd(1)ndashS(1) 9372(5)O(1)ndashC(13) 1252(3) O(4)ndashCd(1)ndashS(2) 9749(4)O(1)ndashC(13) 1259(3) O(2)ndashCd(1)ndashS(2) 9855(5)S(1)ndashC(1) 1727(2) O(1)ndashCd(1)ndashS(2) 9943(4)S(2)ndashC(6) 1730(2) O(3)ndashCd(1)ndashS(2) 15148(4)N(1)ndashC(1) 1327(3) N(2)ndashC(1)ndashN(1) 1191(2)N(1)ndashC(2) 1459(3) N(4)ndashC(6)ndashN(3) 1198(2)N(2)ndashC(1) 1324(3) N(2)ndashC(1)ndashS(1) 12010(17)N(2)ndashC(4) 1458(3) N(1)ndashC(1)ndashS(1) 12081(17)

N(4)ndashC(6)ndashS(2) 12162(17)N(3)ndashC(6)ndashS(2) 11851(17)

Table 3 Hydrogen bond details for [Cd(detu)2(CH3COO)2]sdotH2O

DndashHsdot sdot sdotA 119889 (DndashH) 119889

(Hsdot sdot sdotA)119889

(Dsdot sdot sdotA) lt(DHA)

N(2)ndashH(2N)sdot sdot sdotO(1S)1 077(2) 214(2) 2886(3) 162 (2)N(1)ndashH(1N)sdot sdot sdotO(1) 078(3) 209(3) 2886(3) 174 (3)O(1S)ndashH(1O)sdot sdot sdotO(2) 075(3) 210(3) 2843(3) 170(3)N(3)ndashH(3N)sdot sdot sdotO(3)2 079(3) 205(3) 2821(3) 166(3)O(1S)ndashH(2O)sdot sdot sdotO(1)3 078(3) 210(3) 2882(3) 173N(4)ndashH(4N)sdot sdot sdotO(4) 074(2) 205(3) 2780(3) 170(3)Symmetry transformations used to generate equivalent atoms 1119909minus119910 = 32119911 minus 12 2119909 minus119910 + 32 119911 + 12 3 minus 119909 + 1 119910 minus 12 minus119911 + 12

might be due to the overlap of the acetate ions with CndashNbond stretching vibrations The presence of multiple bandsin the region 552ndash672 cmminus1 can be attributed to the SndashCdndashOinteractions

33 Thermogravimetric Studies Thermogravimetric analysisof the compound [Cd(detu)

2(OOCCH

3)2]sdotH2O has been

carried out to study the pyrolysis pattern in the temperaturerange 20ndash800∘C From the thermogram (TGADTG) inFigure 3 the complex undergoes two decomposition stagesThe first decomposition occurs between 24∘C and 78∘C witha mass loss of 35 and the second decomposition startsat 114∘C and ends at 233∘C with a 71 mass loss Thishuge mass loss corresponds to the loss of the ligands andformation of CdS The DTG peak temperature for each ofthe decomposition stages are 61∘C and 186∘C respectively


Figure 2 Crystal packing diagram of [Cd(detu)2(CH3COO)

2]sdot

H2O Hydrogen bonds are indicated by dashed lines

minus00018

minus00016

minus00014

minus00012

minus0001

minus00008

minus00006

minus00004

minus00002

0

00002

0

20

40

60

80

100

120

20 220 420 620 820 1020

Dr w

eigh

t (

min

)

TGA

wei

ght (

)

Cd(etu)2(OOCCH3)2

TGADTG

Temperature (∘C)

Figure 3 Superimposed TGDTG curves of [Cd(detu)2sdot

(OOCCH3)2]sdotH2O

Considering the DTG peak temperatures the first decom-position stage is due to entrapped solvent molecule Thermaldecomposition of related thiourea complexes reported in theliterature has indicated that the residue formed correspondsto the formation of CdS [22] Here the weight of the residuecalculated for CdS (368mg) agrees favourably with theexpected (365mg) The DTA curve shows two pronouncedendothermic peaks The first and sharp peak is due to themelting of the complex at a temperature of 145∘C Thesecond broad endothermic minimum which occurs at 182∘Crepresents the decomposition of the complex Comparing theTG curve with the DTA it could be inferred that the seconddecomposition which gave CdS commenced in the liquidphase after the melting of the sample

800

900

700

600

500

400

300

200

100

0360 410 460 510 560 610

025

02

015

01

005

0

Inte

nsity

(au

)

Wavelength (nm)

Abso

rban

ce (a

u)

PLUV

Figure 4 Absorption and photoluminescence spectra of the HDA-capped nanoparticles

111

200 lowast

220

lowast311

331

0

2000

4000

6000

8000

10000

12000

25 35 45 55 65 75 85

Figure 5 X-ray diffraction pattern of the CdS nanoparticles

Figure 6 TEM image of the CdS nanoparticles

34 Synthesis and Characterization of Nanoparticles HDA-capped CdS nanoparticles were synthesized at 150∘C usingthe cadmium complex Optical properties of the nanopar-ticles were investigated by UV-vis and photoluminescencespectroscopy at room temperature (Figure 4) and show CdSnanoparticles with excitonic features at 420 nm and emissionat 559 nmTheCdS nanoparticles showed quantum size effect


A B

15KV 15KVtimes180 100120583m UFH-SEM UFH-SEM10120583mtimes1100

Figure 7 SEM Image of the nanoparticles

which is manifested as a blue shift in their absorption bandedges in comparison to that of the bulk

The cadmium complex produced particles in the hexag-onal phase with XRD patterns (Figure 5) indexed to 111 200220 311 and 331 for peaks with 2120579 values of 264 358 439516 and 705 respectively The peaks are generally broadindicative of nanoscale particles The TEM image of the CdSnanoparticles is presented in Figure 6 The nanoparticles arealmost spherical in shape A little aggregation is observedwhich could be ascribed to the effect of the small dimensionsand high surface energy associated with nanodimensionalparticlesThe sizes of the nanoparticles ranged between 5 and19 nm The SEM image of the prepared CdS nanoparticlesis shown in Figure 7 The CdS nanoparticles have sphericalmorphology and show an average agglomerate size Theagglomeration of the nanoparticlesmay arise from their smalldimension and high surface energy

4 Conclusions

Thereaction of cadmium acetate with diethylthiourea yieldedthe coordination complexes [Cd(detu)

2(OOCH

3)2]sdotH2O

Recrystallization of the complex yielded well-defined crys-tals characterized by FTIR elemental analysis and single-crystal X-ray diffraction Single crystal X-ray structure of thecompound revealed that the coordination geometry aroundthe Cd(II) is octahedron comprising of two diethylthiourealigands and two acetate ions acting as bidentate chelatingligands The single-source precursor route has been usedfor the preparation of CdS nanoparticles by thermolysis ofthe complex in hexadecylamine (HDA) to prepared HDA-capped nanoparticles The absorption spectrum showed blueshifts in their absorption band edges which clearly indicatedquantum confinement effect and the emission spectrumshowed characteristic band edge luminescence The broaddiffraction peaks of the XRD pattern showed the materialsto be of the nanometric size with predominantly hexagonalphaseTheTEMmicrographs showed theCdSmorphology to

be almost spherical shape with particle sizes ranging between5 and 19 nm

Conflict of Interests

The authors declare no conflict of interest

Acknowledgments

The author gratefully acknowledged the financial support ofGMRDC University of Fort Hare and NRF South Africafor KIC grant Professor Paul OrsquoBrien and Dr MadeleineHelliwell contributions are gratefully acknowledged

References

[1] J Duque O Estevez-Hernandez E Reguera J Ellena and RS Correa ldquoSynthesis characterization and single crystal X-raystructure of the 1-furoyl-3-cyclohexylthiourea cadmium chlo-ride complex Cd[C

4H3OC(O)NHC(S)NHC

6H11]4Cl2rdquo Jour-

nal of Coordination Chemistry vol 62 no 17 pp 2804ndash28132009

[2] R Del Campo J J Criado E Garcıa et al ldquoThiourea derivativesand their nickel(II) and platinum(II) complexes antifungalactivityrdquo Journal of Inorganic Biochemistry vol 89 no 1-2 pp74ndash82 2002

[3] P A Ajibade and N H Zulu ldquoSynthesis characterization andantibacterial activity of metal complexes of phenylthioureathe X-ray single crystal structure of [Zn(SC(NH

2)NHC

6H5)2sdot

(OOCCH3)2]sdotC2H5OHrdquo Journal of Coordination Chemistry

vol 63 no 18 pp 3229ndash3239 2010[4] K S Kumar S K Singh and S N Pandeya ldquoSynthesis and

antibacterial activity of pyridyl thioureas and arylthiosemicar-bazonesrdquo Bollettino Chimico Farmaceutico vol 140 no 4 pp238ndash242 2001

[5] I Kucukguzel S G Kucukguzel S Rollas andM Kiraz ldquoSome3-thioxoalkylthio-124-triazoles with a substituted thioureamoiety as possible antimycobacterialsrdquo Bioorganic and Medic-inal Chemistry Letters vol 11 no 13 pp 1703ndash1707 2001

[6] T K Venkatachalam E A Sudbeck and F M UckunldquoRegiospecific synthesis X-ray crystal structure and biological


activities of 5-bromothiophenethyl thioureasrdquo Tetrahedron Let-ters vol 42 no 38 pp 6629ndash6632 2001

[7] M J Moloto M A Malik P OrsquoBrien M Motevalli andG A Kolawole ldquoSynthesis and characterisation of some N-alkylaryl and NN1015840-dialkylaryl thiourea cadmium (II) com-plexes the single crystal X-ray structures of [CdCl

2(CS(NH

2)sdot

NHCH3)2]2n and [CdCl

2(CS(NH

2)sdot NHCH

2CH3)2]rdquo Polyhe-

dron vol 22 no 4 pp 595ndash603 2003[8] V Venkataramanan M R Srivivasan and H L Bhat ldquoVibra-

tional spectroscopic study of zinc tris(thiourea) sulfate a neworganometallic nonlinear-optical crystalrdquo Journal of RamanSpectroscopy vol 25 pp 805ndash811 1994

[9] V Venkataramanan H L Bhat M R Srinivasao P Ayyuband M S Multani ldquoVibrational spectroscopic study of thesemiorganic nonlinear optical crystal bis(thiourea)cadmiumchloriderdquo Journal of Raman Spectroscopy vol 28 no 10 pp779ndash784 1997

[10] M Stoev S Ruseva and B Keremidchieva ldquoPreparation ofCdS by thermal decomposition of double salts and saturatedsolutions of the systems Cd(HCOO)

2-CS(NH

2)2-CH3OH and

Cd(CH3COO)

2-CS(NH

2)2-CH3OHrdquo Monatshefte fur Chemie

Chemical Monthly vol 125 no 11 pp 1215ndash1221 1994[11] M Stoev and S Ruseva ldquoPreparation of cadmium sulfide from

CdCl2(CdBr

2 CdI2)-CS(NH

2)2-CH3OH systemsrdquoMonatshefte

fur Chemie vol 125 no 6-7 pp 599ndash606 1994[12] M A Martınez C Guillen and J Herrero ldquoMorphological and

structural studies of CBD-CdS thin films by microscopy anddiffraction techniquesrdquoApplied Surface Science vol 136 no 1-2pp 8ndash16 1998

[13] M J Moloto N Revaprasadu P OrsquoBrien and M A Malik ldquoN-alkylthioureacadmium (II) complexes as novel precursors forthe synthesis of CdS nanoparticlesrdquo Journal ofMaterials Sciencevol 15 no 5 pp 313ndash316 2004

[14] P S Nair N Revaprasadu T Radhakrishnan and G AKolawole ldquoPreparation of CdS nanoparticles using the cad-mium(II) complex of NN1015840-bis(thiocarbamoyl)hydrazine as asimple single-source precursorrdquo Journal of Materials Chemistryvol 11 no 6 pp 1555ndash1556 2001

[15] P S Nair M M Chili T Radhakrishnan N RevaprasaduP Christian and P OrsquoBrien ldquoSome effects of the nature ofthe ligands and temperature of decomposition on the forma-tion of CdS nanoparticles from cadmium complexes of alkyl-substituted thioureasrdquo South African Journal of Science vol 101no 9-10 pp 466ndash470 2005

[16] Bruker ldquoSAINT Version 6 36ardquo Bruker AXS Madison WisUSA 2002

[17] Bruker ldquoSMART (Version 5 625) SADABS (Version 2 03a) andSHELXTL (Version 6 12)rdquo Bruker AXS Madison Wis USA2001

[18] GM Sheldrick TWINABS University of Gottingen Germany2007

[19] M C Burla R Caliandro M Camalli et al ldquoSIR2004 animproved tool for crystal structure determination and refine-mentrdquo Journal of Applied Crystallography vol 38 no 2 pp 381ndash388 2005

[20] A A Aly E K Ahmed K M El-Mokadem and M E-A FHegazy ldquoUpdate survey on aroyl substituted thioureas and theirapplicationsrdquo Journal of Sulfur Chemistry vol 28 no 1 pp 73ndash93 2007

[21] M Merdivan F Karipcin N Kulcu and R S AygunldquoStudy of the thermal decompositions on N N-dialkyl-N1015840-benzoylthiourea complexes of Cu(II) Ni(II) Pd(II) Pt(II)

Cd(II) Ru(III) and Fe(III)rdquo Journal of Thermal Analysis andCalorimetry vol 58 pp 551ndash557 1999

[22] T Mandal V Stavila I Rusakova S Ghosh and K H Whit-mire ldquoMolecular precursors for cds nanoparticles synthesisand characterization of carboxylate-Thiourea or -Tcadmiumcomplexes and their decompositionrdquo Chemistry of Materialsvol 21 no 23 pp 5617ndash5626 2009

Submit your manuscripts athttpwwwhindawicom

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Applied ChemistryJournal of



Theoretical ChemistryJournal of


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Spectroscopy

Analytical ChemistryInternational Journal of


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Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


C1

C2

C3

C4

C5

C6

C7C8

C9

C10

C11

C12

C13

C14

S1

S2

01S

02

03

04

N1

N2

N3

N4 Cd1

01

Figure 1 The molecular structure of [Cd(detu)2(CH3COO)

2]sdotH2O

showing the atom-labeling scheme Displacement ellipsoids aredrawn at 50 probability level H atoms are represented by circlesof arbitrary radius

(CH3COO)

2sdot2H2O dissolved in 50mL of absolute ethanol

to a stirring 4mmol of diethylthiourea (0529 g) in 50mLabsolute ethanolThemixturewas refluxed for 6 h and filteredand left to evaporate slowly at room temperature Whitecrystals suitable for X-ray analysis were obtained after fewdays Anal Calc For C

14H32CdN4O5S2 C 3278 N 1092 H

629 S 1250 Found C 3301 N 1064 H 603 S 1279

23 Single Crystal X-Ray Crystallography Single crystalssuitable for X-ray analysis for [Cd(detu)

2(OOCCH

3)2]sdotH2O

were obtained after few days by slow evaporation of ethanolicsolution of the complex The data sets for the single crystalX-ray studies were collected with Mo K120572 radiation (k =071073) at 100(2) K on a Bruker SMART APEX [16 17] CCDdiffractometer equipped with an Oxford Cryosystems lowtemperature device Unit cell dimensions were obtained byleast-squares refinement based on the setting angles of 925reflections with theta (ℎ) angles ranging from 250 to 2650The structure was solved by direct methods and refined byfull-matrix least square on1198652 (SHELX97) [18 19] and there isa water molecule in the asymmetric unit All hydrogen atomsbonded to carbon were included in calculated positionsThose bonded to nitrogen and oxygen were found by thedifference Fourier techniques and refined isotropically

24 Synthesis of CdS Nanoparticles About 05 g of[Cd(detu)

2(CH3COO)

2]sdotH2O was dissolved in 10mL of

trinoctylphosphine and injected into 6 g of hot hexadecylam-ine (HDA) at 150∘C A subsequent decrease in temperature of20ndash30∘C was observedThe solution was heated to 150∘C and

stabilized at this temperature for 1 h The solution was thenallowed to cool to 70∘C an excess of methanol was addedand a flocculants precipitate was formed The solid wasseparated by centrifugation and redispersed in toluene Thetoluene was removed under vacuum to give HDA-cappedCdS nanoparticles

25 Characterization of Nanoparticles XRD patterns wererecorded by a Bruker D8 Advance X-ray diffractometerequipped with a proportional counter using Ni-filteredCu K120572 radiation (120582 = 15405A) Transmission electronmicroscopy (TEM) imageswere obtained on aPhilipsCM200compustage transmission electron microscope with an accel-erating voltage of 200 kV The electronic spectra of thecomplexes were taken on a Perkin Elmer Lambda 250UV-vis spectrometer A Perkin Elmer LS 45 Fluorimeter was usedto measure the photoluminescence of the nanoparticles TheSEM image was obtained in a Jeol JSM-6390 LV apparatususing an accelerating voltage between 15ndash20 kV at differentmagnifications Composition and energy dispersive spec-trum was processed using energy dispersive X-ray analysis(EDX) attached to the SEM with Noran System six software

3 Results and Discussion

31 Molecular Structure of [Cd(detu)2(OOCCH

3)2]sdotH2O The

molecular structure of the complex with atom numberingscheme is shown in Figure 1 The crystal data and structurerefinement are presented inTable 1 and selected bond lengthsand angles are given in Table 2 The cadmium in the molec-ular structure is a six-coordinate CdS

2O4form in which the

Cd ion is coordinated to two monodentate diethylthioureasand two chelating acetate ions The coordination polyhedralaround Cd(II) is a distorted octahedron which might be dueto the small bite angles of the acetate ions O(2)ndashCd(1)ndashO(1)[5451(6)∘] and O(4)ndashCd(1)ndashO(3) [5420(6)] This also ledto deviation of trans O(4)ndashCd(1)ndashO(1) O(2)ndashCd(1)ndashS(1) andO(3)ndashCd(1)ndashS(2) bond angles significantly from 180∘ (rangesfrom 14121(6)∘ to 15148(4)∘) The diethylthiourea ligandsare cis to each other and SndashCd(1)ndashS bond angle around thecadmium ion is 10283(3)∘ which deviates considerably from90∘ This may be ascribed to the steric interaction betweenthe substituents on the diethylthiourea The CndashSndashCd bondangles of 10882(8)∘ and 11159(8)∘ are slightly greater than thetetrahedral value

The SndashCndashN and NndashCndashN bond angles ranges from11851(17)∘ to 12162(17)∘ and are within the expected rangeof tetrahedral The CndashN bonds (1327(3) A to 1458(3) A) andCndashS bonds 1727(2) A to 1730(2) A are intermediate betweensingle and double bonds This may be attributed to thedelocalization of electron in the thioamide bonds [20 21]Thehydrogen bonding network within the molecule is betweenthe acetate oxygen atom and NH and acetate oxygen atomand the hydrogen atoms of water within the crystal lattice(Table 3) Each water molecule within the crystal lattice islinked to three cadmium complex units via intermolecularhydrogen bondsTheother intermolecular hydrogen bondingis between the acetate oxygen atom and the NH of the





















2(OOCCH





2]sdot


minus00018

minus00016

minus00014

minus00012

minus0001

minus00008

minus00006

minus00004

minus00002

0

00002

0

20

40

60

80

100

120

20 220 420 620 820 1020

Dr w

eigh

t (

min

)

TGA

wei

ght (

)

Cd(etu)2(OOCCH3)2

TGADTG

Temperature (∘C)


(OOCCH3)2]sdotH2O


800

900

700

600

500

400

300

200

100

0360 410 460 510 560 610

025

02

015

01

005

0

Inte

nsity

(au

)

Wavelength (nm)

Abso

rban

ce (a

u)

PLUV


111

200 lowast

220

lowast311

331

0

2000

4000

6000

8000

10000

12000

25 35 45 55 65 75 85





A B





4 Conclusions


2(OOCH

3)2]sdotH2O





Acknowledgments


References


4H3OC(O)NHC(S)NHC





2)NHC

6H5)2sdot









2(CS(NH

2)sdot


2(CS(NH

2)sdot NHCH






2-CS(NH

2)2-CH3OH and

Cd(CH3COO)

2-CS(NH



CdCl2(CdBr

2 CdI2)-CS(NH
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





















2(OOCCH





2]sdot


minus00018

minus00016

minus00014

minus00012

minus0001

minus00008

minus00006

minus00004

minus00002

0

00002

0

20

40

60

80

100

120

20 220 420 620 820 1020

Dr w

eigh

t (

min

)

TGA

wei

ght (

)

Cd(etu)2(OOCCH3)2

TGADTG

Temperature (∘C)


(OOCCH3)2]sdotH2O


800

900

700

600

500

400

300

200

100

0360 410 460 510 560 610

025

02

015

01

005

0

Inte

nsity

(au

)

Wavelength (nm)

Abso

rban

ce (a

u)

PLUV


111

200 lowast

220

lowast311

331

0

2000

4000

6000

8000

10000

12000

25 35 45 55 65 75 85





A B





4 Conclusions


2(OOCH

3)2]sdotH2O





Acknowledgments


References


4H3OC(O)NHC(S)NHC





2)NHC

6H5)2sdot









2(CS(NH

2)sdot


2(CS(NH

2)sdot NHCH






2-CS(NH

2)2-CH3OH and

Cd(CH3COO)

2-CS(NH



CdCl2(CdBr

2 CdI2)-CS(NH
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



2]sdot


minus00018

minus00016

minus00014

minus00012

minus0001

minus00008

minus00006

minus00004

minus00002

0

00002

0

20

40

60

80

100

120

20 220 420 620 820 1020

Dr w

eigh

t (

min

)

TGA

wei

ght (

)

Cd(etu)2(OOCCH3)2

TGADTG

Temperature (∘C)


(OOCCH3)2]sdotH2O


800

900

700

600

500

400

300

200

100

0360 410 460 510 560 610

025

02

015

01

005

0

Inte

nsity

(au

)

Wavelength (nm)

Abso

rban

ce (a

u)

PLUV


111

200 lowast

220

lowast311

331

0

2000

4000

6000

8000

10000

12000

25 35 45 55 65 75 85





A B





4 Conclusions


2(OOCH

3)2]sdotH2O





Acknowledgments


References


4H3OC(O)NHC(S)NHC





2)NHC

6H5)2sdot









2(CS(NH

2)sdot


2(CS(NH

2)sdot NHCH






2-CS(NH

2)2-CH3OH and

Cd(CH3COO)

2-CS(NH



CdCl2(CdBr

2 CdI2)-CS(NH
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


A B





4 Conclusions


2(OOCH

3)2]sdotH2O





Acknowledgments


References


4H3OC(O)NHC(S)NHC





2)NHC

6H5)2sdot









2(CS(NH

2)sdot


2(CS(NH

2)sdot NHCH






2-CS(NH

2)2-CH3OH and

Cd(CH3COO)

2-CS(NH



CdCl2(CdBr

2 CdI2)-CS(NH
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




2(CS(NH

2)sdot


2(CS(NH

2)sdot NHCH






2-CS(NH

2)2-CH3OH and

Cd(CH3COO)

2-CS(NH



CdCl2(CdBr

2 CdI2)-CS(NH
























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

research article synthesis and use of [cd(detu) 2(oocch 3 2]·h … · 2019. 7. 31. · group...

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