bis (diethyldithiocarbamato)antimony(iii) derivatives with oxygen- and sulfur-donor...

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BIS(DIETHYLDITHIOCARBAMATO)ANTIMONY(III)DERIVATIVES WITH OXYGEN AND SULFUR DONORLIGANDS: SYNTHESIS, ESI–MASS AND SPECTRALCHARACTERIZATIONH. P.S. Chauhan a , Jaswant Carpenter a , Sumit Bhatiya a & Abhilasha Bakshi aa School of Chemical Sciences, Devi Ahilya University, Takshashila Campus, Khandwa Road,Indore, 452001, IndiaAccepted author version posted online: 05 Apr 2013.

To cite this article: Phosphorus, Sulfur, and Silicon and the Related Elements (2013):BIS(DIETHYLDITHIOCARBAMATO)ANTIMONY(III) DERIVATIVES WITH OXYGEN AND SULFUR DONOR LIGANDS: SYNTHESIS,ESI–MASS AND SPECTRAL CHARACTERIZATION, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:10.1080/10426507.2013.777729

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ACCEPTED MANUSCRIPT 1

BIS(DIETHYLDITHIOCARBAMATO)ANTIMONY(III) DERIVATIVES WITH

OXYGEN AND SULFUR DONOR LIGANDS: SYNTHESIS, ESI–MASS AND

SPECTRAL CHARACTERIZATION

H.P.S. Chauhan*, Jaswant Carpenter§, Sumit Bhatiya

† and Abhilasha Bakshi

‡ School of Chemical Sciences, Devi Ahilya University, Takshashila Campus, Khandwa Road,

Indore–452001, India

*Corresponding author; E-mail: [email protected],

Tel.: 0731-2460208 (O), Mob.: +91-9826219748

Fax: 0731-2365782

§E-mail: [email protected],

†Email: [email protected],

‡ Email: [email protected]

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Abstract

Replacement reactions of bis(diethyldithiocarbamato)antimony(III) chloride have been carried

out with oxygen and sulfur donor ligands such as disodium oxalate, sodium acetate, sodium

salicylate, benzoic acid, thioglycolic acid, acetylacetone, thiphenol, ethane-1,2-dithiol and 2,2-

dimethylpropane-1,3-diol to give mixed bis(diethyldithiocarbamato)antimony(III) derivatives of

the corresponding ligands. These derivatives have been characterized by the physicochemical

[melting point & molecular weight determination, elemental analysis (C, H, N, S and Sb)],

spectral [FT–IR, far IR, NMR (1H and

13C)], ESI–mass, powder XRD and SEM studies.

Abstract Graphical

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Keywords

antimony(III); dithiocarbamates; 1H and 13C NMR; ESI-mass; powder XRD; SEM.

[Supplementary materials are available for this article. Go to the publisher’s online

edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following

free supplemental files: Additional figures and tables.]

<AQ> Editorial work on your manuscript has created a file of supplemental materials

that will be available on-line only.</AQ>

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INTRODUCTION

Carboxylic and phenolic ligands are versatile in nature and exhibit various types of coordination

patterns with transition, as well as main group metals. Dithiocarbamate complexes of various

metals are used in analytical chemistry1, medicines2, as antioxidants3, polymer photo stabilizers4,

precursor for creating sulfide film semiconductor5 and exhibit anti–alkylation6 and anti–HIV

properties7. These ligands and their antimony derivatives have been investigated as antiwear

agents or multifunctional additives to lubricants8. The compounds of antimony containing Sb–S

bonds have been widely used in industrial processes9; Takahashi et al. have reported some

antimony compounds can affect the repair of a DNA double strand breaks10. Trivalent antimony

compound have also been used as drugs for the treatments of laishmaniasis span more than 50

years11, 12. It has been reported that compounds of organoantimony possess potent in vitro

activity against certain cancer cells13, and find extensive applications in chemotherapy14–16,

antimicrobial14, antiparasitic15, and antitumor16–18 activities. A large number of antimony

compounds have been tested as bactericides17, fungicides12, and antifertility agents19.

In view of the interesting results obtained earlier on some dithiolate As(III), Sb(III), and

Bi(III) derivatives with sulfur and oxygen donor ligands20–23 in our laboratory, we report herein

synthesis, spectroscopic characterization and ESI-mass studies of some mixed

bis(diethyldithiocarbamato)antimony(III) oxo and thio carboxylic and phenolic compounds of

the general formula [(C2H5)2NCS2]2SbL where L = ½ OOCCOO (1), OOCCH3 (2),

OOCC6H4(OH) (3), OOCC6H5 (4), SCH2COOH (5), SOCCH3 (6), CH3C(O)CHC(O)CH3 (7),

SC6H5 (8), ½ SCH2CH2S (9) and ½ OCH2C(CH3)2CH2O (10).

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RESULTS AND DISCUSSION

Synthesis

Bis(diethyldithiocarbamato)antimony(III) derivatives have been synthesized by the reactions of

bis(diethyldithiocarbamato)antimony(III) chloride with oxygen and sulfur donor ligands in 1:1

and 2:1 molar ratios in refluxing anhydrous benzene* for ~5h.

Scheme 1

Scheme 2

*Benzene is a carcinogenic solvent! This was used as the most suitable solvent for the

reactions. Benzene was collected and all precautions were taken to prevent discharge/release of

benzene. In future we will not use benzene as a solvent and will use some other alternative safer

solvents.

IR and far–IR

The bands of medium to strong intensity 1600–1700 cm–1 and 1200–1350 cm–1 are attributed to

asymmetric υ(COO–) and symmetric υ(COO–) respectively20–24. The bands present due to υ(C–

N) at 1450–1476 cm–1 in the free ligands are shifted to higher frequencies in the complexes and

present in the region 1490–1510 cm–1 and another band at 1050–1070 cm–1 due to υ(C–S)

indicating anisobidentade behavior of the dithiocarbamate group in the complexes25–27. In

addition to these, the bands appearing between 500–600 cm–1 and 300–350 cm–1 may be

assigned to υ(Sb–O) and υ(Sb–S) respectively.

1H NMR

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All the spectra of these complexes exhibit the expected pattern without any appreciable shift

from the reported data21–24. The spectra of the dithiocarbamate exhibit CH3 protons signal at δ

1.25–1.35 which split into a triplet and CH2 protons at δ 3.70–3.80 which splits into a quartet. A

singlet at δ 10.35 is observed for the complex containing phenyl –OH (compound 3). In addition

to these, complexes also show expected protons resonance due to corresponding carboxylic and

phenolic proton of ligand moieties.

13C

NMR

The 13C NMR spectra of diethyldithiocarbamate (dtc) moieties show signals in the range δ 12.0–

12.4 and δ 48.6–49.1 due to β–C and α–C, respectively. All these complexes also show a weak

signal at δ 195.7–196.7 due to NCS2 carbon resonance as well as compound 1-6 exhibit an

expected weak signal between δ 169.8–172.6 due to COO carbon.

ESI–mass spectral studies

ESI–mass spectral data of the two of the synthesized complexes were obtained over a

temperature range (100–300oC), as these complexes might undergo a thermolytic decomposition

at elevated temperature. It is common with such type of complexes that molecular ion peak is not

observed; these may be attributed to the pyrolytic decomposition of the complexes in the direct

inlet chamber at the high temperature of the experiment or due to the electron impact28, 29. The

base peak [{(C2H5)NCS2}Sb]+ in both complexes is found to be the most abundance exhibit

strong chelating properties of the dithiocarbamate group. These ions are probably formed by the

cleavage of one of the Sb–S bond of bridging 1,2–dithiolate ligand in the complex 9. It is

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supported by the [{(C2H5)2NCS2}Sb–S–CH2–CH2–S]+ fragment obtain at m/z 509 with 11%

abundance. ESI–mass spectral data of 9 and 10 are shown in Table S 1 and S 2.

Powder X–ray diffraction data

Powder X–ray diffraction pattern for four of the complexes 1, 4, 7 and 10 have been studied

which are showed in Figure 1, S 1, S 2 and S 3.

Figure 1

Complexes have monoclinic crystal lattice with unit cell volume V = 504.63 Å (1), V = 1252.05

Å (4), V = 604.88 Å (7), and V = 770.94 Å (10), and are crystalline in the nature. Average

particles size of the synthesized complexes were determined with the help of the Scherrer

formula26, In which particle size D is defined as 0.9λ /B cosθ, where 0.9 = constant, λ =

wavelength, B = angular width and θ = diffraction angle. The powder X–ray diffraction data of

all four complexes are shown in Table S 3, S 4, S 5 and S 6. In some deviation between the

distances (d) may exceed up to 1.65 as observed in Table S 5, which shows that synthesized

complexes are in multiphase complexes, as we synthesized mixed ligand complexes which

characteristic of both ligands as observed in X–ray diffraction pattern of complexes. Interplanar

d spacing and unit cell volume of the synthesized complexes were calculated by the formulae30:

V = abc sin β

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We have obtained interplanar distances matched with complexes of

bis(diethyldithiocarbamato)antimony(III) with of oxalate, benzoate, acetylacetonate and 2,2-

dimethylpropane-1,3-diol ligands, which are equal and in some cases nearly matches to standard

diffraction card JCPDS 72–0022, 43–1978, 46–1954, 14–0882, 41–1634, and 38–1792.

Monoclinic crystal lattice shows that complexes have lower symmetry which is due to the

complex nature and lone pair of electron present on antimony which does not take part in

bonding and results in distorted geometry of complexes. Along with these formulae, other

informations related to our synthesized complexes are collected from the standard book30.

SEM studies

Scanning electron microscopic studies of four of the synthesized complexes, 1, 4, 7, and 10 have

been carried out at a magnification of ×500–50 µm and ×7500–2 µm. The particles of complex 1

(Figure S 4) and 7 (Figure S 5) possess highly irregular surface morphology and rough texture

appears with grooves and ridges on the surface which reveals that the complexes are crystalline

in nature.

Complex 4 (Figure S 6) and 10 (Figure S 7) have large aggregates or exist as

agglomerated particles. It is noteworthy that the agglomerates consist of a large number of tiny

particles. This implies that the agglomerates could result from the flocculation of primary

particles. The average particle size found from SEM shows that the complexes are nano range

(3.19 to 3.64 nm) crystalline solids.

Structure elucidation

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In the IR spectra of all these synthesized complexes, the presence of strong band in the region

1490–1510 cm–1 due to υ(C–N) and another at 1050–1070 cm–1 due to υ(C–S) indicate the

anisobidentate nature of the dithiocarbamate ligands. In addition, the band appearing between

500–600 cm–1 and 300–350 cm–1 is due to of υ(Sb–O) and υ(Sb–S) for oxygen and sulfur donor

ligands respectively, which clearly indicates the bonding between antimony metal and oxygen

and sulfur atoms of the ligands.

Figure 2

Figure 3

On the basis of above studies tentative structures have been proposed as distorted

octahedral geometry with a stereochemically active lone pair of electron occupying one of the

vertex of the octahedra. Distorted octahedral geometry has also been supported by monoclinic

crystal system which also indicates lower symmetry of the complexes. Thus on the basis of

above studies and earlier reported data, it is tentatively concluded that complexes are crystalline

in nature, rough surface, exist as agglomerates, nano range particle size and having distorted

octahedral geometry with monoclinic crystal system.

EXPERIMENTAL

Material and methods

All the experimental manipulations have been carried out under moisture free condition.

Antimony trichloride (E.Merck) was distilled before use. Solvents (benzene, dichloromethane,

chloroform etc.) were purified by standard methods31. Anhydrous benzene was handled very

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carefully as it is carcinogenic. Sodium diethyldithiocarbamate (BDH) and ligands [benzoic acid,

thiobenzoic acid, thioacetic acid, thiophenol, sodium salicylate, thioglycolic acid and disodium

oxalate (all Fluka and Merck Germany)] were used as received without further purification.

Antimony(III)tris(diethyldithiocarbamate) and bis(diethyldithiocarbamato)–antimony(III)

chloride were prepared by the method reported in the literature20, 21.

Synthesis of compound 2–8 in 1:1 molar ratios

Synthesis of [(C2H5)2NCS2]2SbOOCCH3

Bis(diethyldithiocarbamato)antimony(III)chloride (1.5g; 0.33 mmol) dissolved in benzene (~40

mL) was added to sodium acetate (0.27g; 0.33 mmol) drop by drop in a round bottom flask. The

reaction mixture was refluxed for ~5h. It was cooled and precipitated sodium chloride was

filtered off. The solvent was removed under reduced pressure to get the product. Finally the

compound was crystallized in dichloromethane.

All other compounds (3–8) were synthesized by adopting the similar procedure.

Synthesis of compound 1, 9 and 10 in 2:1 molar ratios

Synthesis of [{(C2H5)2NCS2}2Sb(µ2-OOCCOO)]

The benzene solution (~40 mL) of bis(diethyldithiocarbamato)antimony(III) chloride (1.49g;

3.30 mmol) was added drop by drop to disodium oxalate (0.22g; 1.64 mmol). The reaction

mixture was refluxed for ~5h and filtered. The solvent from the filtrate was removed under

vacuum to obtain the product. The compound 9 and 10 also prepared by similar procedure.

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Analytical methods and physical measurements

Antimony was estimated iodometrically and sulfur was estimated gravimetrically as barium

sulphate32. Melting points were determined on a B10 Tech India melting point apparatus and are

uncorrected. Molecular weights were determined cryoscopically in benzene. 1H (at 500 MHz)

and 13C (at 125.8 MHz) NMR spectra were obtained on a Brucker FT NMR spectrometer in

CDCl3 solution using TMS as an internal standard, Infrared spectra (KBr) were recorded at BX

series in the range 4000–400 cm–1 and far–IR spectra were recorded as a Nujol mull over CsI

disks using a Megna–IR Spectrophotometer–550 instrument in the range 600–50 cm–1. Powder

X–ray diffraction studies performed on diffractometer system XPERT–PRO using CuK,

radiation at a wavelength of 1.54 and SEM studies were carried out on and JSM–5600

scanning electron microscope at accelerating voltage of 0.5–30 kV.

Analytical and spectral data

Analytical and spectral data (state, colour, yield, melting point, IR, NMR and elemental analysis)

of individual compound are as follows:

(1) White solid; yield: 90 %, m.p.: 98oC, M.W. found (calcd.): 913 (925) g/mol; 1H NMR: δ 1.27

(t, J = 7.0 Hz, 24H, CH3 dtc), 3.74 (q, J = 7.0 Hz, 16H, CH2 dtc). 13C NMR: δ 12.1 (CH3), 49.1

(CH2), 171.6 (COO), 195.7 (NCS2); IR (vmax cm–1): 2960, 1698, 1510, 1265, 1070, 570, 304;

Analysis (%): for C22H40N4O4S8Sb2, found: Sb 26.21, S 27.54, C 27.89, H 4.24, N 5.81, calcd.:

Sb 26.34, S 27.74, C 28.58, H 4.36, N 6.06.

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(2) Light green sticky solid; yield: 72 %, M.W. found (calcd.): 468 (477) g/mol; 1H NMR: δ 1.24

(t, J = 7.0 Hz, 24H, CH3 dtc), 2.15 (s, 3H, CH3 acetate), 3.71 (q, J = 7.0 Hz, 16H, CH2 dtc). 13C

NMR: δ 12.2 (CH3 dtc), 22.7 (CH3 acetate), 48.7 (CH2 dtc), 170.1 (COO), 196.6 (NCS2); IR (vmax

cm–1): 2990, 1685, 1510, 1265, 1050, 570, 310; Analysis (%): for C12H23N2O2S4Sb, found: Sb

25.01, S 26.72, C 29.92, H 4.72, N 5.68, calcd.: Sb 25.51, S 26.87, C 30.19, H 4.86, N 5.87.

(3) Yellow semi–solid; yield: 79 %, M.W. found (calcd.): 541 (555) g/mol; 1H NMR: δ 1.25 (t, J

= 7.0 Hz, 24H, CH3 dtc), 3.71 (q, J = 7.0 Hz, 16H, CH2 dtc), 7.30 (m, 4H, C6H4), 10.35 (s, 1H

C2–OH). 13C NMR: δ 12.2 (CH3), 48.8 (CH2), 117.1 (Ring C–3), 118.7 (Ring C–4), 125.4 (Ring

C–6), 129.3, (Ring C–5), 129.8 (Ring C–1), 161.8 (Ring C–2), 172.6 (COO), 196.6 (NCS2). IR

(vmax cm–1): 2985, 1655, 1500, 1270, 1070, 560, 310; Analysis (%): for C17H25N2O3S4Sb, found:

Sb 21.75, S 22.89, C 36.32, H 4.42, N 4.89, calcd.: Sb 21.92, S 23.09, C 36.76, H 4.54, N 5.04.

(4) Light yellow solid; yield: 95 %, m.p.: 57oC, M.W. found (calcd.): 524 (539) g/mol; 1H

NMR: δ 1.23 (t, J = 7.0 Hz, 24H, CH3 dtc), 3.72 (q, J = 7.0 Hz, 16H, CH2 dtc), 7.39 (t, J = 7.5

Hz, 1H, Ring C–4), 7.52 (s, J = 7.5 Hz, 1H, Ring C–3), 8.02 (d, J = 7.0 Hz, 1H, ring C–2). 13C

NMR: 12.4 (CH3), 48.9 (CH2), 128.5 (Ring C–3, C–4), 129.8 (Ring C–2, C–6), 130.3 (Ring C–

1), 133.6 (Ring C–4), 171.8 (COO), 196.7 (NCS2); IR (vmax cm–1): 2995, 1670, 1504, 1290,

1076, 565, 315; Analysis (%): for C17H25N2O2S4Sb, found: Sb 22.50, S 23.66, C 37.72, H 4.55,

N 4.96, calcd.: Sb 22.57, S 23.78, C 37.85, H 4.67, N 5.19.

(5) Light yellow solid; yield: 88 %, m.p.: 96oC, M.W. found (calcd.): 497 (509) g/mol; 1H NMR:

δ 1.35 (t, J = 7.0 Hz, 24H, CH3 dtc), 2.97 (s, 2H, CH2 acetate), 3.73 (q, J = 7.5 Hz, 16H, CH2

dtc), 9.10 (s, 1H, COOH). 13C NMR: 12.2 (CH3 dtc), 42.5 (CH2 acetate), 48.6 (CH2 dtc), 181.7

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(COO), 196.3 (NCS2); IR (vmax cm–1): 2970, 1640, 1510, 1265, 1050, 304; Analysis (%): for

C12H23N2O2S5Sb, found: Sb 23.74, S 31.40, C 27.88, H 4.36, N 5.33, calcd.: Sb 23.90, S 31.47,

C 28.29, H 4.55, N 5.50.

(6): Orange solid; yield: 92 %, m.p.: 79oC, M.W. found (calcd.): 481 (493) g/mol; 1H NMR: δ

1.24 (t, J = 7.5 Hz, 24H, CH3 dtc), 2.21 (s, 3H, CH3 acetate), 3.71 (q, J = 7.0 Hz, 16H, CH2 dtc).

13C NMR: 12.2 (CH3 dtc), 22.8 (CH3 acetate), 48.7 (CH2), 169.8 (COO), 196.6 (NCS2); IR (vmax

cm–1): 2950, 1660, 1497, 1075, 320; Analysis (%): for C12H23N2OS5Sb, found: Sb 23.54, S

32.11, C 28.93, H 4.58, N 5.49, calcd.: Sb 24.68, S 32.49, C 29.21, H 4.70, N 5.68.

(7) Brown solid; yield: 94 %, m.p.: 88oC, M.W. found (calcd.): 509 (517) g/mol; 1H NMR: δ

1.34 (t, J = 7.0 Hz, 24H, CH3 dtc), 2.05 (s, 3H, CH3 enolic), 2.22 (s, 3H, CH3 ketonic), 2.34 (s,

1H, CH acac), 3.80 (q, J = 7.0 Hz, 16H, CH2 dtc). 13C NMR: 12.2 (CH3 dtc), 24.8 (CH3 enolic),

30.9 (CH3 ketonic), 48.9 (CH2 dtc), 101.5 (CH enolic), 192.4 (C enolic), 196.1 (NCS2). IR (vmax

cm–1): 2910, 1700, 1510, 1070, 570, 310; Analysis (%): for C15H27N2O2S4Sb, found: Sb 23.41, S

24.65, C 34.63, H 5.01, N 5.29, calcd.: Sb 23.58, S 24.79, C 34.82, H 5.26, N 5.41.

(8) Yellow semi–solid; yield: 81%, M.W. found (calcd.): 518 (527) g/mol; 1H NMR: δ 1.23 (t, J

= 7.0 Hz, 24H, CH3 dtc), 3.62 (q, J = 7.0 Hz, 2H, CH2 dtc), 7.41 (m, 16H, C6H5). 13C NMR: 12.2

(CH3), 48.8 (CH2), 126.7 {C6H5(C–4)}, 128.5 {C6H4 (C–2, 3, 5 and 6)}, 129.5 {C6H4 (C–1)},

196.6 (NCS2); IR (vmax cm–1): 2985, 1505, 1055, 315; Analysis (%): for C16H25N2S5Sb, found:

Sb 22.83, S 30.24, C 36.32, H 4.60, N 5.26, calcd.: Sb 23.08, S 30.40, C 36.43, H 4.78, N 5.31.

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(9) Yellow solid; yield: 90 %; m.p.: 72oC, M.W. found (calcd.): 920 (929) g/mol; 1H NMR: δ

1.25 (t, J = 7.5 Hz, 24H, CH3 dtc), 3.55 (s, 2H, SCH2 dithiol), 3.74 (q, J = 7.5 Hz, 16H, CH2 dtc).

13C NMR: 12.4 (CH3), 42.3 (SCH2 dithiol), 49.0 (CH2 dtc), 196.5 (NCS2); IR (vmax cm–1): 2990,

1495, 1070, 305; Analysis (%): for C22H44N4S10Sb2, found: Sb 25.90, S 33.98, C 28.28, H 4.65,

N 5.99, calcd.: Sb 26.22, S 34.52, C 28.45, H 4.78, N 6.03.

(10) Light yellow solid; yield: 85 %, m.p.: 83oC, M.W. found (calcd.): 933 (939) g/mol; 1H

NMR: δ 0.82 (s, 6H, CH3 ligand), 1.26 (t, J = 7.0 Hz, 24H, CH3 dtc), 3.41 (s, 2H, OCH2), 3.74 (q,

J = 7.0 Hz, 16H, CH2 dtc). 13C NMR: 12.3 (CH3 dtc), 21.4 (CH3 ligand), 36.5 (C quaternary),

42.4 (OCH2), 49.0 (CH2 dtc), 196.5 (NCS2); IR (vmaxcm–1): 2990, 1490, 1060, 560, 310; Analysis

(%): for C25H50N4O2S8Sb2, found: Sb 25.81, S 27.15, C 31.87, H 5.31, N 5.89, calcd.: Sb

25.94, S 27.33, C 31.99, H 5.37, N 5.97.

CONCLUSION

The synthesis of bis(diethyldithiocarbamato)antimony(III) derivatives with oxygen and sulfur

donor ligands was accomplished and their structures characterized tentatively to be crystalline in

nature, rough surface, exist as agglomerates, nano range particle size (3.19 to 3.64 nm) and

having distorted octahedral geometry with monoclinic crystal system by elemental analysis,

spectral data (IR, 1H, 13C NMR, ESI–mass) SEM, and powder XRD.

Acknowledgements

Financial Assistance from University grant commission [F.39-801/2010(SR)], New Delhi is

gratefully acknowledged. We are also thankful to School of Studies in Chemistry, Vikram

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University, Ujjain; SAIF, IIT Bombay and UGC–DAE–CSR, Indore for FT–IR, far–IR spectra,

and Powder XRD and SEM studies respectively.

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10 20 30 40 50

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Figure 1: Powder XRD pattern of bis(diethyldithiocarbamato)antimony(III) benzoate 4

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Figure 2: Proposed structure of bis(diethyldithiocarbamato)antimony(III) thiophenolate 8

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Figure 3: Proposed structure of di-µ-ethane-1,2-dithiolato

bis(diethyldithiocarbamato)antimony(III) 9

Scheme 1: Synthesis of bis(diethyldithiocarbamato)antimony(III) acetate.

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Scheme 2: Synthesis of di-µ-oxolatobis(diethyldithiocarbamato)antimony(III).

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