Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et 3NH]+[(4-MeC6H4O)2PS 2]-

Article abstract of DOI:10.1007/s10870-006-9107-3

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, I

Full text of DOI:10.1007/s10870-006-9107-3

ꢀ
C
Journal of Chemical Crystallography, Vol. 36, No. 10, October 2006 ( 2006)
DOI: 10.1007/s10870-006-9107-3
Triethyl ammonium salt of
O,Oꢀ-bis(p-tolyl)dithiophosphate,
[Et3NH]+[(4-MeC6H4O)2PS2]−
A. L. Bingham,(1) J. E. Drake,(2) C. Gurnani,(3) M. B. Hursthouse,(1)
M. E. Light,(1) M. Nirwan,(3) and R. Ratnani(3)∗
Received March 11, 2006; accepted May 5, 2006
Published Online June 27, 2006
Triethyl ammonium Salt of O,Oꢁ-bis(p-tolyl)dithiophosphate and O,Oꢁ-bis(m-
tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively
1
with P2S5 in toluene and have been characterized by elemental analysis, IR, H and
31P NMR spectroscopy. The molecular structure of O,Oꢁ-bis(p-tolyl)dithiophosphate
has been determined. Crystal data: [Et3NH]+[(4-MeC6H4O)2PS2]−◦: Monoclinic, P21/c,
−3
˚
˚
˚
˚
a = 15.2441(9) A, b = 10.415(2) A, c = 3.9726(9) A, β = 91.709(7) , V = 2217.5(1) A
,
Z = 4.
KEY WORDS: Synthesis; p-cresol; o-cresol; tolyl; dithiophosphate; NMR; X-ray analysis.
Introduction
Among sulfur donor ligands, O,Oꢁ-dialkyl
MeC6H4O)2PS2]−,8 HS2POCH2CMe2CH2O and
HS2POCMe2CMe2O,9 we report the synthesis
and characterization of triethyl ammonium salts
of O,Oꢁ-bis(p-tolyl)dithiophosphate and O,Oꢁ-
bis(m-tolyl)dithiophosphate and crystal struc-
ture of triethyl ammonium salt of O,Oꢁ-bis(p-
tolyl)dithiophosphate.
as well as alkylene dithiophosphate ligands have
been used for producing potential coordination
compounds with most of the metals of the periodic
table.1–4 The importance of dithiophosphates and
their complexes in oil and agriculture industries
is well known.5–7 The synthesis and characteriza-
tion of diaryl dithiophosphates adds a new devel-
opment in this field. In continuation of our earlier
reports on the crystal structures of [Et3NH]+[(o-
Experimental
Triethylamine (b.p. 88◦C), p-cresol (b.p.
202◦C) and m-cresol (b.p. 203◦C) were purchased
from E. Merck and were freshly distilled prior to
use and P2S5 (E.Merck) was used as such. Toluene
and benzene were dried over sodium metal. These
salts were synthesized under anhydrous condi-
tions by the method previously described.8 Micro
elemental analysis (C and H) was carried out on
a Vario EL III Elemental analyzer while sulfur
(1) Department of Chemistry, University of Southampton, Highfield
Southampton SO17 1BJ, UK.
(2) Department of Chemistry and Biochemistry, University of
Windsor, Windsor, Ontario, Canada N9B 3P4.
(3) Department of Pure & Applied Chemistry, M.D.S. University,
Ajmer 305 009, India.
∗
To whom correspondence should be addressed; e-mail:
ratnaniraju@yahoo.co.uk.
627
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1074-1542/06/1000-0627/0 2006 Springer Science+Business Media, Inc.

628
Bingham, Drake, Gurnani, Hursthouse, Light, Nirwan, and Ratnani
Table 1. Crystal Data and Structure Refinement for [Et3NH]+[(4-
was estimated as BaSO4 by Messenger’s method.
The IR Spectrum was recorded on a Perkin Elmer
MeC6H4O)2PS2]−
1
PE 983G spectrophotometer. H and 31P NMR
[ Et3NH]+[(4-MeC6H4O)2PS2]−
spectra were recorded on a Bruker AV300 using
TMS and 85% H3PO4, respectively, as external
references.
Empirical formula
Formula weight
Temperature (K)
C20H30NO2PS2
411.54
120(2)
˚
Wavelength (A)
0.71073
Crystal system
Space group
Monoclinic
P21/c
15.2441(9)
10.415(1)
13.9726(9)
91.709(7)
2217.5(4)
Synthesis of [Et3NH]+[(4-MeC6H4O)2PS2]− (1)
and [Et3NH]+[(3-MeC6H4O)2PS2]− (2)
˚
a (A)
˚
b (A)
˚
c (A)
β (◦)
Volume (A
P2S5 (5.0 g, 2.24 mmol) was added slowly
in ∼ 60 min with the help of spatula to a stir-
ring toluene solution (40 mL) of freshly distilled
p-cresol (9.37 g, 8.99 mmol). After stirring the
contents for 5–7 min at ∼ 40◦C, a toluene solu-
tion (40 mL) of Et3N (4.55 g, 4.59 mmol) was
added dropwise. All the P2S5 dissolved within
15–20 min giving a clear solution. Pumping off
excess of toluene under reduced pressure afforded
the desired compound in quantitative yield as a
colorless thick mass, which became a crystalline
solid on standing for 3–4 days at room tempera-
ture. [Et3NH]+[(4-MeC6H4O)2PS2]− (1). Yield:
(18.1 g, 97.8%); m.p.: 57◦C; Anal: Calcd. for
C20H30O2PS2N (M.W. 411.54): C, 58.31%; H,
7.28%; S, 15.55% Found: C, 58.46%; H, 7.48%;
S, 15.65%; 1H NMR (CDCl3, δ ppm): 1.31 (t, 9H,
−3
˚
)
Z
4
Density (calculated, g/cm3)
Absorption coefficient (mm−1
F (0 0 0)
1.233
0.326
880
)
Crystal size (mm3)
θ range for data collection (◦)
Index ranges
0.16 × 0.10 × 0.04
3.17 to 27.58
− 19 ≤ h ≤ 19, − 12 ≤ k ≤ 13,
− 18 ≤ l ≤ 17
22,295
5093 [Rint = 0.0612]
0.9871 and 0.9497
Full-matrix least-squares on F2
5093/0/241
1.035
Reflections collected
Independent reflections
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [F2 > 4σ(F 2)] R1 = 0.0427, wR2 = 0.0892
R indices (all data)
R1 = 0.0629, wR2 = 0.0970
0.0028(6)
0.307 and − 0.282
Extinction Coefficient
Largest diff. peak and hole
−3
˚
(e A
)
–
–
CH3 of Et3N, J = 7.3 Hz), 2.19 (s, 6H, CH3
–
of cresol), 3.05(q, 6H, CH2 of Et3N), 7.16–7.23
Crystal structure determination
(m, 8H, C6H4), 9.28 (s,1H, NH); 31P (CDCl3,
δ ppm): 106.8 (s); IR (Nujol): 3350b, 2965b,
1600m, 1500s, 1474s, 1102s, 938s, 687s, 596s,
541w and 467m cm−1.
–
–
A colourless lath crystal of [Et3NH]+[(4-
MeC6H4O)2PS2]− (1) was mounted on glass fi-
bres and immediately frozen under liquid nitro-
gen. Data were collected on a Bruker–Nonius
Kappa CCD area detector diffractometer, with ϕ
and ω scans chosen to give a complete asymmetric
unit. Cell refinement10 gave cell constants corre-
sponding to monoclinic for 1 whose dimensions
are given in Table 1 along with other experimen-
tal parameters. Absorption corrections were ap-
plied.11
Similarly was prepared [Et3NH]+[(3-
MeC6H4O)2PS2]− (2). Colorless crystalline
solid. Yield: 96%; m. p.: 60◦C; Anal: Calcd. for
C20H30O2PS2N (M.W. 411.54): C, 58.31%; H,
7.28%; S, 15.55% Found: C, 58.51%; H, 7.43%;
S, 15.75%; 1H NMR (CDCl3, δ ppm): 1.27 (t, 9H,
–
–
CH3 of Et3N, J = 7.3 Hz), 2.29 (s, 6H, CH3 of
–
cresol), 3.12(q, 6H, CH2 of Et3N), 7.08–7.20
(m, 8H, C6H4), 9.22 (s,1H, NH); 31P (CDCl3,
δ ppm): 106.4 (s); IR (Nujol): 3350b, 2940b,
1581m, 1502s, 1480s, 1110s, 928s, 690s, 598s,
543w and 443m cm−1.
The structure was solved by direct method12
and was refined using the WinGX version13 of
SHELX-97.14 All of the non-hydrogen atoms
were treated anisotropically. Hydrogen atoms
–
–

Triethyl ammonium salts of O,Oꢀ-bis(p- and m-tolyl)dithiophosphate
629
◦
˚
Table 2.
Selected Bond Distances [A] and Angles [ ] for
[Et3NH]+[(4-MeC6H4O)2PS2]−
–
–
S(1) P(1)
1.9514(7)
1.9653(7)
1.623(1)
1.609(1)
1.396(2)
1.407(2)
0.93
N(1) S(1)
3.732(2)
97.00(7)
118.26(3)
110.98(5)
110.79(5)
112.96(5)
104.65(5)
162.85
–
– –
O(1) P(1) O(2)
– –
S(1) P(1) S(2)
– –
O(1) P(1) S(1)
– –
O(1) P(1) S(2)
– –
O(2) P(1) S(1)
– –
O(2) P(1) S(2)
– –
N(1) H(1) S(2)
S(2) P(1)
–
P(1) O(1)
–
P(1) O(2)
–
O(1) C(1)
–
O(2) C(8)
–
N(1) H(1)
–
H(1) S(2)
2.40
–
–
–
N(1) S(2)
3.302(2)
3.15
N(1) H(1) S(1)
122.24
–
H(1) S(1)
were included in idealized positions with isotropic
thermal parameters set at 1.2 times that of the
carbon atom to which they were attached. The fi-
nal cycles of full-matrix least-squares refinement
were based on 5093 (1) observed reflections (3988
(1) for F2>4σ(F2)) and 241 (1) variable param-
eters and converged (largest parameter shift was
0.001 times its esd).
Fig. 1. ORTEP plot of [Et3NH]+[(4-MeC6H4O)2PS2]− (1).
The non-hydrogen atoms are drawn with 50% probability
ellipsoids
106.4 ppm for 1 and 2, respectively, indicating
the equivalent nature of the phosphorus nuclei as
well as the symmetric nature of the species in
solution.
Selected distances and bond angles are given
in Table 2 and the molecule is displayed as ORTEP
diagram in Fig. 1.
[Et3NH]+[(4-MeC6H4O)2PS2]−(1) crystal-
lizes as monoclinic, in the space group P21/c.
The expected distorted tetrahedral environment
around the phosphorus atom of the anion is ev-
ident from the ORTEP diagram in Fig. 1 with
two oxygen and two sulfur atoms in the coor-
dination sphere, as was found for the analogous
ortho salt, [Et3NH]+[(2-MeC6H4O)2PS2]−.8 The
Results and discussion
The synthesis of O,Oꢁ-bis(p-tolyl) dithio-
phosphate or O,Oꢁ-bis(m-toly)dithiophosphate by
reaction of p- or m-cresol with P2S5 and Et3N in
toluene in ratio of 4:1:2 gives quantitative yields
for both compounds.
– –
anion and cations are linked by N H S hydrogen
˚
–
4(p/m − MeC6H4OH) + P2S5 + 2Et3N
bonds. The N(1) S(2) distance in 1 of 3.302(2) A
is well within the acceptable distances for hy-
→[Et3NH]+[(p/m − MeC6H4O)2PS2]− + H2S
–
drogen bonding. With the N H bond fixed at
˚
˚
–
Thewhitesolidsobtained were recrystallized
from refluxing benzene solution, at room temper-
ature.
The IR spectra show all characteristic bands
in their expected regions. The H NMR spectra
0.93 A, the H(1) S(2) bond is 2.40 A in 1, with
N(1) H(1) S(2) angle of 162.8 , similar to the
values of 2.33 and 2.42 A for the two disordered
cations in the ortho salt , with N H S angles of
◦
–
–
˚
8
– –
1
154.9 and 158.2. As with the ortho salt, in the para
–
of both compounds show the chemical shift for
salt (1) the other NH(1) S(1) distance is too long
˚
–
the NH proton at δ, 9.28 and 9.22 ppm for 1
(3.15 A) to be considered a hydrogen bond of any
and 2, respectively, in addition to the character-
istic chemical shifts for all other protons. The
31P NMR spectra show a singlet at δ, 106.8 and
significance (Fig. 1).
It is clear that the sulfur atom involved in
forming strong hydrogen bond, S(2)has the longer

630
Bingham, Drake, Gurnani, Hursthouse, Light, Nirwan, and Ratnani
Supplementary materials Additional material available from the
˚
–
–
P S bonds, with S(2) P(1) 1.9653(7) A in 1.
Cambridge Crystallographic Data Centre (CCDC no. 600927 for
[Et3NH]+[(4-MeC6H4O)2PS2]− comprises the final atomic coor-
dinates for all atoms, thermal parameters, and a complete listing
of bond distances and angles. Copies of this information may be
obtained free of charge on application to The Director, 12 Union
Road, Cambridge CB2 2EZ, UK (fax: + 44-1223-336033; email:
deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).
Whereas, S(1) is not involved in hydrogen bond-
ing, the S(1) P(1) bond is the shortest of the S P
–
–
˚
bonds at 1.9514(7) A.
–
All of the S P bonds in 1, along with those
of their ortho analogue,8 cover a relatively narrow
˚
range of bond lengths (1.9514(7) to 1.968(3) A).
=
These are longer than the terminal P S bonds,
1.923(2) and 1.908(2) A in HS2POCMe2CMe2O
˚
Acknowledgment
and HS2POCH2CMe2CH2O,9 respectively, but
˚
M.N. thanks the CSIR, New Delhi for finan-
cial support. M.B.H. thanks the UK Engineering
and Physical Sciences Council for support of the
X-ray facilities at Southampton University. J.E.D.
thankstheUniversityofWindsorforfinancialsup-
port.
shorter than those of 2.007(6) and 2.011(5) A
in K2+[(MeO)OPS2]− H2O,15 reflecting their
–
partial double bond character. The P O bond
˚
˚
lengths of 1.623(1) A and 1.609(1) A in 1
are similar to those of the ortho analogue,
[Et3NH]+[(2-MeC6H4O)2PS2]− where the val-
8
˚
ues are 1.632(2) and 1.613(2) A. How-
ever, these bonds are slightly longer than in
the free acids HS2POCMe2CMe2O (1.594(3)
References
˚
and (1.589(3) A), and HS2POCH2CMe2CH2O
9
˚
(1.583(3) and (1.582(3) A).
1. Cotero-Villegas, A.M.; Toscano, R.A.; Munoz-Hernandez, M.;
Lopez-Cardoso, M., Garcia, Y.; Garcia, P.; Ceaolivares, R. J.
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thouse, M.B.; Light, M.E. Inorg. Chim. Acta 2004, 357(4), 939.
3. Jain, P.U.; Paul, H.; Munshi, P.; Walawalkar, M.G.; Lahiri, G.K.
Polyhedron 2001, 20(3–4), 245.
– –
The average S P S bond angle of
118.26(3)◦ in 1 is similar to those in [Et3
NH]+[(2-MeC6H4O)2PS2]− (118.62(4)◦) but
smaller than in [Et3NH]+[CH2{6-t-Bu-4-C6H4
O}2PS2]− (120.49(8)◦)16 and larger than in the
free acids HS2POCMe2CMe2O (112.78(8)◦)
and HS2POCH2CMe2CH2O (115.64(8)◦) and
4. Szucova, L.; Travneck, Z.; Marek, J. Polyhedron 2003, 22(10),
1341.
5. Nicholls, M.A.; Stasio, G.D.; Frazer, B.H.; Norton, P.R.; Kasrai,
M.; Bancroft, G.M. Tribolo. Lett. 2005, 38(1), 15.
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Zhiming, Z. Wear, 2005.
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Ratnani, R. J. Chem. Crystallog. 2005, 35, 447.
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13. Farrugia, L.J. J. Appl. Cryst. 1999, 32, 837.
14. Sheldrick, G.M. SHELXL97 Structure Determination Software,
University of Gottingen, Germany, 1997.
15. Gupta, M.C., Ph.D. Thesis, University of Rajasthan, India, 2004.
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J. Chem. Cryst. 2001, 31, 51.
also in K2+[(MeO)OPS2]−.H2O (113.67(3)◦).
◦
– –
The O P O bond angle of 97.00(7) in 1,
is similar to the ortho analogue, [Et3NH]+[(2-
MeC6H4O)2PS2]−, (97.07(8)◦). This angle broa-
dens slightly in [Et3NH]+[CH2{6tBu-4-C6H4
O}2PS2]− (103.5(4)◦), in HS2POCMe2CMe2O
(105.1(1)◦), in K2+[(MeO)OPS2]−.H2O (100.93
(7)◦)andin[Et3NH]+[(OCH2CMe2CH2O)2PS2]−
(101.4(2)◦).16 The above comparisons, in general
reflect that the different alkylene or aryl groups
do not greatly influence the basic structural
feature around phosphorus.