Synthesis and spectroscopic characterization of toluene-3,4- dithiolatoarsenic(III)- O, O -ditolyl/alkylene dithiophosphate compounds: Crystal structure of [CH 3C 6H 3S 2As{S 2P(OC 6H

Article abstract of DOI:10.1080/00958972.2014.899356

Toluene-3,4-dithiolate complexes, [CH₃C₆H ₃S₂As{S₂P(OR)₂}] and [CH ₃C₆H₃S₂AsS₂POGO] (R = o-, m-, p-C₆H₄Me; G = -

Full text of DOI:10.1080/00958972.2014.899356

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Synthesis and spectroscopic
characterization of toluene-3,4-
dithiolatoarsenic(III)-O,O’-
ditolyl/alkylene dithiophosphate
compounds: crystal structure of
[CH3C6H3S2As{S2P(OC6H4Me-m)2}]
Seema Maheshwaria, Kavita Bundelab & Krishan Gopal Ojhaa
a Department of Pure & Applied Chemistry, M.D.S. University,
Ajmer, India
b Department of Chemistry, Govt. P.G. College, Mandsour, India
Accepted author version posted online: 10 Mar 2014.Published
online: 01 Apr 2014.
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To cite this article: Seema Maheshwari, Kavita Bundela & Krishan Gopal Ojha (2014) Synthesis
and spectroscopic characterization of toluene-3,4-dithiolatoarsenic(III)-O,O’-ditolyl/alkylene
dithiophosphate compounds: crystal structure of [CH3C6H3S2As{S2P(OC6H4Me-m)2}], Journal of
Coordination Chemistry, 67:6, 1088-1096, DOI: 10.1080/00958972.2014.899356
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Journal of Coordination Chemistry, 2014
Vol. 67, No. 6, 1088–1096, http://dx.doi.org/10.1080/00958972.2014.899356
Synthesis and spectroscopic characterization of
toluene-3,4-dithiolatoarsenic(III)-O,O’-ditolyl/alkylene
dithiophosphate compounds: crystal structure of
[CH3C6H3S2As{S2P(OC6H4Me-m)2}]
SEEMA MAHESHWARI*†, KAVITA BUNDELA‡ and KRISHAN GOPAL OJHA†
†Department of Pure & Applied Chemistry, M.D.S. University, Ajmer, India
‡Department of Chemistry, Govt. P.G. College, Mandsour, India
(Received 8 November 2013; accepted 31 January 2014)
Toluene-3,4-dithiolate complexes, [CH3C6H3S2As{S2P(OR)2}] and [CH3C6H3S2AsS2POGO]
(R = o-, m-, p-C6H4Me; G = –CH2C(CH3)2CH2–, –CHCH3CH2(CH3)2C–), have been synthesized by
reaction of toluene-3,4-dithiolatoarsenic(III) chloride [C6H3(CH3)S2AsCl] with ammonium salts of
the corresponding O,O’-ditolyl/alkylene dithiophosphate by refluxing in benzene followed by stir-
ring. These complexes have been characterized by elemental analysis and IR, 1H, and 31P NMR
spectroscopy. Single-crystal X-ray diffraction analysis of [CH3C6H3S2As{S2P(OC6H4Me-m)2}]
revealed distorted trigonal-bipyramidal geometry with an anisobidentate chelating mode of the
ditolyl moiety in these complexes.
Keywords: Toluene-3,4-dithiolatoarsenic(III) derivatives; Dithiophosphates; Crystal structure;
1H NMR; 31P NMR
*Corresponding author. Email: seemamaheshwari2008@gmail.com
© 2014 Taylor & Francis

Dithiophosphate arsenic(III) compounds
1089
1. Introduction
Arsenic, antimony, and bismuth halides function as very weak Lewis acids towards thio-
ethers [1] and have great affinity for anionic dithiolato [2–14] ligands. These complexes
exhibit remarkable diversity in their coordination patterns because these complexes imitate
unpredictable structural behavior due to the presence of a lone pair of electrons on the
arsenic, small ligand bite, and molecular associations. The dithiolato ligands can behave as
monodentate [8, 9], bidentate [6–10], and bridging [14]. A number of arsenic(III) com-
plexes with these ligands have been set forth and some have also been characterized by sin-
gle-crystal X-ray structural analysis [4–7]. In the last few decades, a range of dithiolato
ligands with group 15 metal complexes have been studied with O,O’-dialkyl/ditolyl [4–13],
alkylene [15, 16], and mixed ligand [17–19] dithiophosphates. Arsenic thiolates such as
British anti-lewisite have been used in chelation therapy for heavy metal poisoning which
rely on the high affinity of arsenic for sulfur ligands [20]. Toluene-3,4-dithiol (H2tdt) is an
attractive choice as a potential S,Sʹ-bidentate metal scavenger [21]. Although some of the
chemistry of toluene-3,4-dithiolatoarsenic(III) compounds have been already explored,
chemistry of heteroleptic toluene-3,4-dithiolatoarsenic(III) compounds with bulky dithiolato
ligands are still in their infancy. The lack of single-crystal X-ray structural analysis of
arsenic thiolates and their interesting structural behavior prompted us to explore the chemis-
try of toluene-3,4-dithiolatoarsenic(III) ditolyl/alkylene dithiophosphates.
2. Experimental
2.1. Materials and methods
Stringent precautions were taken to exclude atmospheric moisture throughout the experi-
mental manipulations owing to hydrolyzation of the starting materials as well as the newly
synthesized compounds. CH3C6H3(SH)2, P2S5, and As2O3 were purchased from E. Merck
and used as received. SOCl2, o-, m-, p-cresols, and solvents (benzene, n-hexane) (E. Merck)
were distilled prior to use. Literature methods were used for the preparation of O,O’-ditolyl
[22–24] and alkylene dithiophosphoric acids [25]. Ammonium salts of the dithiophosphoric
acids were prepared by reaction of the parent acid with an equimolar amount of ammonia
in benzene. Arsenic trichloride was prepared by reaction of arsenic trioxide and thionyl
chloride [26]. Toluene-3,4-dithiolatoarsenic(III) chloride [27] was prepared by reaction of
arsenic(III) chloride and toluene-3,4-dithiol in equimolar ratio (1 : 1) in anhydrous benzene.
2.2. Analytical methods of physical measurements
Sulfur was estimated gravimetrically as barium sulfate (Messenger’s method) [28] and
arsenic(III) was estimated iodometrically [28]. IR spectra were recorded on a Perkin-Elmer
577 spectrophotometer in KBr pellets from 350 to 4000 cm−1. 1H NMR and 31P NMR spec-
tra were recorded on a Bruker DRX-300 spectrometer in CDCl3 solutions using TMS and
H3PO4 as an internal and external standard, respectively.
X-ray diffraction analysis: a yellow thin plate of [CH3C6H3S2As{S2P(OC6H4Me-m)2}]
was mounted on a glass fiber. Data were collected on a Bruker-Nonius Kappa CCD area
detector diffractometer. Cell refinement gave cell constants corresponding to a monoclinic

1090
S. Maheshwari et al.
cell whose dimensions are given in table 1 along with other experimental parameters. An
absorption correction was also applied [29]. The structure was solved by direct methods
[30] and was refined using the WinGX version [31] of SHELX-97 [32]. All non-hydrogen
atoms were treated anisotropically.
2.3. Synthesis of [CH3C6H3S2As{S2P(OC6H4Me-m)2}] (1)
Benzene solution of (10 mL) toluene-3,4-dithiolatoarsenic(III) chloride (0.27 g, 1.02 mM)
was added dropwise with constant stirring to benzene suspension of the ammonium salt
of di-(m-tolyl)dithiophosphoric acid (0.33 g, 1.02 mM). The color of the reaction mixture
was changed to yellow and then refluxed for ~5 h. Then the contents were brought to
room temperature and ammonium chloride was separated by filtration under anhydrous
conditions, and excess solvent was removed from the filtrate in vacuum yielding a pale
yellow viscous oily liquid of [CH3C6H3S2As{S2P(OC6H4Me-m)2}] yellow crystals of
which were obtained after several weeks by layering of hexane to the viscous liquid.
Yield: 0.45 g, 82%. Anal. Calcd for C21H20AsO2PS4: As – 13.9%; S – 23.7%. Found:
As – 13.5%; S – 22.9%, 31P NMR (CDCl3): 84.97 δ.
2.4. Synthesis of [CH3C6H3S2As{S2P(OC6H4Me-o)2}] (2)
The aforesaid method gave yellow oily viscous liquid. Yield: 0.29 g, 79%, Anal. Calcd for
C21H20AsO2PS4: As – 13.9%; S – 23.7% Found: As – 13.4%; S – 23.3%, 31P NMR
(CDCl3): 83.29 δ.
Table 1. Crystal data and structure refinement for [CH3C6H3S2As{S2P(OC6H4Me-m)2}].
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C21H20AsO2PS4
538.50
120(2)
0.71073
Monoclinic
P2(1)/n
12.437(2)
b (Å)
9.719(2)
c (Å)
19.447(3)
β (°)
106.016(2)
2259.5(7)
4
1.583
1.961
1096
0.10 × 0.08 × 0.02
3.02–27.51
Volume (Å3)
Z
Density (Calcd), g/cm3
Absorption coefficient (mm−1
F (0 0 0)
)
Crystal size (mm3)
θ Range for data collection (°)
Index ranges
Reflections collected
−16 ≤ h ≤ 16, −12 ≤ k ≤ 12, −25 ≤ l ≤ 25
28,223
Independent reflections
Max. and min. transmission
Refinement method
5164 [R(int) = 0.0925]
0.9618 and 0.8280
Full-matrix least-squares on F2
5164/0/262
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [F2>4σ (F2)]
R indices (all data)
1.148
R1 = 0.0705, wR2 = 0.1204
R1 = 0.1110, wR2 = 0.1380
0.613 and −0.618
Largest diff. peak and hole (e·Å−3
)

Dithiophosphate arsenic(III) compounds
1091
2.5. Synthesis of [CH3C6H3S2As{S2P(OC6H4Me-p)2}] (3)
The aforesaid method gave yellow oily viscous liquid. Yield: 0.35 g, 88%, Anal. Calcd for
C21H20AsO2PS4: As – 13.9%; S – 23.7%. Found: As – 13.5%; S – 22.9%, 31P NMR
(CDCl3): 83.95 δ.
2.6. Synthesis of [CH3C6H3S2As{S2POCH2C(CH3)2CH2O}] (4)
The aforesaid method gave yellow oily viscous liquid. Yield: 0.28 g, 85%, Anal. Calcd for
C12H16AsO2PS4: As – 17.5%; S – 30.0%. Found: As – 16.9%; S – 29.2%, 31P NMR
(CDCl3): 84.59 δ.
2.7. Synthesis of [CH3C6H3S2AsS2POCHCH3CH2(CH3O] (5)
The aforesaid method gave yellow oily viscous liquid. Yield: 0.91 g, 85%. Anal. Calcd for
C13H18AsO2PS4: As – 17.0%; S – 29.0%. Found: As – 16.5%; S – 28.7%, 31P NMR
(CDCl3): 84.22 δ.
3. Results and discussion
3.1. Synthesis and characterization
Toluene-3,4-dithiolatoarsenic(III) ditolyl/alkylene dithiophosphate complexes have been
synthesized by reactions of toluene-3,4-dithiolatoarsenic(III) chloride with ammonium ditol-
yl/alkylene dithiophosphates in equimolar ratio in anhydrous benzene by refluxing the con-
tents for ~5 h.
Refluxing
CH3C6H3S2AsCl þ NH4S2PðORÞ2 ꢀ!
½CH3C6H3S2AsfS2PðORÞ2gꢁ þ NH4Cl #
ðR ¼ o-; m-; p-C6H4MeÞ
CH3C6H3S2AsCl þ NH4S2POGO Reꢀfl!uxing
½CH3C6H3S2AsS2POGOꢁ þ NH4Cl #
ðR ¼ o-; m-; p-C6H4MeÞ; G ¼ ꢀCH2CðCH3Þ2CH2ꢀ; ꢀCHCH3CH2ðCH3Þ2CꢀÞ
These derivatives are non-volatile yellow viscous liquids except [CH3C6H3S2As{S2P
(OC6H4Me-m)2}], yellow crystals of which were obtained after several weeks by layering
of hexane to the viscous liquid, and all are soluble in common organic solvents like

1092
S. Maheshwari et al.
benzene, chloroform, and dichloromethane. The products were characterized by elemental
1
analysis, IR, H, 31P NMR spectroscopy, and single-crystal X-ray diffraction analysis. Ele-
mental analyses are consistent to the molecular formula of the complexes.
3.2. Infrared spectra
IR spectra (table 2) of the toluene-3,4-dithiolatoarsenic(III) ditolyl/alkylene dithiophosphate
complexes have been measured from 350 to 4000 cm−1 and the important bands have been
assigned on the basis of comparison with spectra of salts of O,O’-di(o-, m- or p-tolyl) [23,
24] and alkylene dithiophosphoric acids [25] and analogous compounds [33].
Two strong bands at 1040–1160 cm−1 and 808–851 cm−1 are assigned to [(P)–O–C] and
[P–O–(C)] stretches of dithiophosphate, respectively, in 1–5. A strong band due to (P=S)
stretch present in the spectra of ammonium salts of ditolyldithiophosphoric acids is shifted
to lower frequencies (625–668 cm−1) in all these toluene-3,4-dithiolatoarsenic(III)ditolyl/
alkylene dithiophosphate derivatives. This shift probably indicates bidentate chelation of
ditolyldithiophosphate with arsenic(III). Bands of medium intensities present at
505–546 cm−1 may be ascribed to (P–S). Bands of medium to strong intensities at
681–740 cm−1 may be attributed to an asymmetrically trisubstituted benzene ring.
3.3. 1H NMR spectra
1H NMR spectra of these compounds have been recorded in CDCl3 solution at room tem-
1
perature using TMS as an internal standard. H NMR data (table 3) of these derivatives are
similar to those of the corresponding salt of dithiophosphates, probably due to the large sep-
aration between arsenic and the hydrogens. In all these compounds ring methyl protons
[CH3 (7)] appear in the region 2.16–2.22 δ as a very sharp three proton singlet. A multiplet
due to trisubstituted tolyl ring is at 6.75–7.49 δ. In the ditolyl dithiophosphate derivatives
(1–3) (table 3), a very sharp six proton singlet at 2.25–2.32 δ is due to ditolyl methyl pro-
tons on various positions (-o, -m, -p). An eight proton multiplet at 7.11–7.28 δ is due to
tolyl rings A and B.
In both the alkylene dithiophosphate derivatives (4 and 5) (table 3), a six proton singlet
at 2.36 δ is due to two similar methyls [CH3 (11 and 12)] of the ligand. Another four proton
singlet at 3.82 δ and two proton singlet at 4.02 δ due to [OCH2 (8 and 9)] and [OCH2 (9)]
in 4 and 5 (table 3), respectively, are observed. In addition, derivative 5 (table 3) and one
proton singlet at 3.82 δ due to [(CH (8)] and a three proton doublet at 3.92–3.94 δ are
Table 2. IR spectroscopic data of toluene-3,4-dithiolatoarsenic(III) ditolyl/alkylenedithiophosphates.
Trisubstitution
aromatic ring
ν(As–S) ν[(P)–O–C] ν[P–O–(C)] ν(P=S) ν(P–S)
S.No. Compounds
1
2
3
4
[CH3C6H3S2As{S2P(OC6H4Me-o)2}]
315
312
325
310
1114
1142
1160
1054
808
851
819
811
665
667
625
668
531
546
511
505
712
731
740
681
[CH3C6H3S2As{S2P(OC6H4Me-m)2}]
[CH3C6H3S2As{S2P(OC6H4Me-p)2}]
[CH3C6H3S2As{S2POCH2C
(CH3)2CH2O}]
5
[CH3C6H3S2AsS2P{CH3CHOCH2C
(CH3)2O}]
309
1040
812
630
531
698

Dithiophosphate arsenic(III) compounds
1093
Table 3. 1H and 31P NMR spectroscopic data of toluene-3,4-dithiolatoarsenic(III) ditolyl/alkylenedithiophosphates.
S.No. Compounds
1H Chemical shift (δ)
31P Chemical shift (δ)
10
B
1
2.16 [(3H,s, ring CH3 (7)]
2.32 [(6H,s, ring CH3 (14) & CH3 (21)]
6.92–7.10 [(3H,m, ring A]
83.29
H3C
14
11
12
9
6
H C
37
5
4
O
8
S
S
S
13
20
1
A
3
As
P
7.11–7.23 [(8H,m, ring B & C]
2
15
16
S
O
19
18
C
H C
3 21
17
H3C
14
10
2
3
2.18 [(3H,s, ring CH3 (7)]
2.26 [(6H,s, ring CH3 (14) & CH3 (21)]
6.85–6.98 [(3H,m, ring A]
84.97
83.95
9
11
12
B
6
H C
3 7
8
O
O
1
5
4
S
S
S
As
S
7.14–7.27 [(8H,m, ring B & C]
13
20
A
P
2
15
19
18
3
C
16
17
CH3
21
10
B
2.22 [(3H,s, ring CH3 (7)]
2.25 [(6H,s, ring CH3 (14) & CH3 (21)]
6.85–6.96 [(3H,m, ring A]
11
CH3
14
9
8
2
12
H3C
7
O
1
3
4
S
S
S
As
13
20
7.12–7.28 [(8H,m, ring B & C]
P
A
5
6
15
S
O
19
C
16
18
CH3
21
17
6
8
4
5
2.17 [(3H,s, ring CH3 (7)]
84.59
84.22
H C
3 7
5
4
S
As
S
O
P
S
S
CH3
11
1
1
2.36 [(6H,s, ring CH3 (11) & CH3 (12)]
3.82 [4H,s,OCH2 (8) & OCH2 (9)]
6.93–7.36 [(3H,m, ring A]
2.17 [(3H,s, ring CH3 (7)]
2.36 [(6H,s, ring CH3 (11) & CH3 (12)]
3.82 [1H,s,CH (8)]
10
9
A
3
CH3
2
2
O
12
CH3
13
6
A
3
H C
3 7
5
O
8
S
S
CH3
11
As
10
P
CH3
12
4
S
S
O
9
3.92–3.94 [(3H,d, CH3 (13) J = 8.0 Hz]
4.02 [(2H,s, OCH2 (9)]
6.75–7.46 [(3H,m, ring A]
Note: s = singlet, d = doublet, m = multiplet.
observed due to methyl proton (13). Although NMR spectra confirm the compounds
investigated, they provide no information about the details of the coordinated ligands.
Therefore, single-crystal X-ray diffraction was performed to establish the structural details.
3.4. 31P NMR spectra
On the basis of the analysis of proton decoupled 31P NMR spectra of a number of the com-
plexes, Glidewell concluded that complexes showing their NMR signal at 82–101 δ and less
than 82 δ exhibit bidentate and monodentate coordination of ligands, respectively [34]. A
sharp singlet at 83.29–84.97 δ of 31P NMR spectra of all these toluene-3,4-dithiolatoarsenic
ditolyl/alkylenedithiophosphate complexes suggests bidentate coordination of the dithio-
phosphate to arsenic (table 3). Occurrence of a singlet for 1–5 indicates equivalent phospho-
rous nuclei and purity of the compound.

1094
S. Maheshwari et al.
3.5. Crystal and molecular structure of [CH3C6H3S2As{S2P(OC6H4Me-m)2}]
The single-crystal X-ray structure in the ORTEP diagram in figure 1 demonstrates anisobid-
entate coordination of the dithiophosphate.
The arsenic is attached with two sulfurs of toluene-3,4-dithiolate with the As(1)–S1
2.2425 Å and As(1)–S2 2.2311 Å bond lengths and one sulfur of dithiophosphate with As
(1)–S3 2.3374 Å bond length (table 4). S4 is in close proximity to the arsenic, having As
(1)–S4 3.2335 Å. This distance is still within the sum of the van der Waals radii of arsenic
and sulfur of 3.74 Å, but this reflects the presence of the weak covalent bond. Hence, the
geometry of the molecule is believed to be distorted trigonal bipyramidal where As(1)–S2
and As(1)–S3 are present as equatorial bonds and the stereochemically active lone pair of
the electron is present on the remaining equatorial position of the trigonal-bipyramidal
plane. S1 and S4 occupy axial positions making a trans basal angle of 161.89(54)° with
Figure 1. Structure of monomer unit of [CH3C6H3S2As{S2P(OC6H4Me-m)2}]. Hydrogens are omitted for clarity
(teal = As; yellow = S; red = O; pink = P; black = C, see http://dx.doi.org/10.1080/00958972.2014.899356 for color
version).
Table 4. Selected bond lengths [Å] and angles [°] for [CH3C6H3S2As{S2P(OC6H4Me-m)2}].
Bond lengths
Angles
Bond lengths
Angles
As(1)–S(1)
As(1)–S(2)
As(1)–S(3)
S(3)–P(1)
S(4)–P(1)
S(1)–C(1)
S(2)–C(7)
O(2)–C(15)
C(1)–C(2)
C(2)–H(2)
P(1)–O(2)
P(1)–O(1)
O(1)–C(8)
C(1)–C(7)
C(2)–C(3)
C(3)–C(5)
2.2425(16)
2.2311(16)
2.3374(15)
2.055(2)
1.929(2)
1.778(6)
1.764(6)
1.407(6)
1.400(8)
0.9500
1.596(4)
1.599(4)
1.417(7)
1.385(8)
1.380(9)
1.406(10)
S(2)–As(1)–S(1)
S(2)–As(1)–S(3)
S(1)–As(1)–S(3)
S(3)–As(1)–S(4)
C(1)–S(1)–As(1)
C(7)–S(2)–As(1)
P(1)–S(3)–As(1)
O(2)–P(1)–O(1)
O(2)–P(1)–S(4)
O(1)–P(1)–S(4)
O(2)–P(1)–S(3)
O(1)–P(1)–S(3)
S(4)–P(1)–S(3)
C(8)–O(1)–P(1)
C(15)–O(2)–P(1)
C(7)–C(1)–S(1)
91.91(6)
99.58(6)
93.35(6)
72.93(44)
99.8(2)
100.0(2)
96.41(7)
100.2(2)
116.70(17)
115.35(16)
100.29(16)
105.49(16)
116.50(9)
124.2(3)
122.6(3)
120.6(4)

Dithiophosphate arsenic(III) compounds
1095
Figure 2. View of the chain polymer showing the long As–S contacts (teal = As; yellow = S; red = O; pink = P;
black = C, see http://dx.doi.org/10.1080/00958972.2014.899356 for color version).
each other. S1 is 2.2366 Å above and S4 is 2.9922 Å below the plane defined by S2, S3,
and arsenic.
In dithiophosphates, the P–S bond associated with strong As–S bonds is significantly
longer (2.055(2) Å) than that associated with weaker As⋯S bonds (1.929(2) Å), as is plau-
sible to maintain bond order conservation around sulfur. These monomeric units are very
loosely assembled into chain polymer via bridging through sulfur of the neighboring unit
(As⋯S = 3.762(3) and 3.873(3) Å) (figure 2). The value of the bite angle (72.937(44)°)
between sulfurs of the ligand is similar to the other dithiophosphate complexes. Thus, the
1
crystal structure provides confirmation about the structural conclusion based on IR, H, and
31P NMR spectroscopy.
4. Concluding comments
We have prepared and characterized [CH3C6H3S2As{S2P(OR)2}] and [CH3C6H3S2As-
1
S2POGO] (R = o-, m-, p-C6H4Me; G = –CH2C(CH3)2CH2–, –CHCH3CH2(CH3)2C–) IR, H,
and 31P NMR spectral data and elemental analyses of these compounds are consistent with
complexes containing bidentate ligands; single-crystal structure confirms distorted trigonal-
bipyramidal geometry with an anisobidentate chelating mode of the ligand in these
complexes.
Supplementary material
Supplementary data CCDC 905095 contain the supplementary crystallographic data for
[CH3C6H3S2As{S2P(OC6H4Me-m)2}]. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (+44) 1223-336-033; or Email:
deposit@ccdc.cam.ac.uk

1096
S. Maheshwari et al.
Acknowledgments
We are thankful to SAIF, Panjab University, Panjab and CDRI, Lucknow for the 1H and
31P NMR spectral analyses. We also thank Dr W. Zhang, University of Southampton,
Southampton, UK for assisting with the crystallographic data collection.
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