The triethyl ammonium salt of O,O′-bis(o-tolyl) dithiophosphate [Et3NH]+[(2-MeC6H4O) 2PS2]-

Article abstract of DOI:10.1007/s10870-005-2218-4

The X-ray structure of the triethyl ammonium salt of O,O′-bis(o- tolyl)dithiophosphate, [Et₃NH]⁺[(2-MeC₆H ₄O)₂PS₂]^-, has been determined. Crystal data: Monoclinic, P2₁

Full text of DOI:10.1007/s10870-005-2218-4

Journal of Chemical Crystallography, Vol. 35, No. 6, June 2005 (ꢀC 2005)
DOI: 10.1007/s10870-005-2218-4
ꢀ
The triethyl ammonium salt of O,O -bis(o-tolyl)
+
−
2
dithiophosphate [Et NH] [(2-MeC H O) PS ]
3
6 4
2
(1)
(1)
(2)
(2)
(3)∗
J. E. Drake, C. L. B. MacDonald, A. Kumar, S. K. Pandey, and R. Ratnani
Received September 2, 2004; accepted December 21, 2004
ꢁ
The X-ray structure of the triethyl ammonium salt of O,O -bis(o-tolyl)dithiophosphate,
+ −
[
Et3NH] [(2-MeC6H4O)2PS2] , has been determined. Crystal data: Monoclinic,
˚
˚
˚
◦
P21/c, a = 15.4342(6) A, b = 10.1913(4) A, c = 14.0729(6) A, β = 100.855(1) , V =
˚
−3
2
174.0(2) A , Z = 4. The immediate environment around phosphorous is distorted tetra-
hedral with two sulfur and two oxygen atoms in the coordination sphere, with N--- H--- S
bonding involving only one of the sulfur atoms.
KEY WORDS: Synthesis; structure; cresol; tolyl; dithiophosphate.
Introduction
The chemistry of dithio ligands has been
tal structure of the triethyl ammonium salt of
O,O -bis(o-tolyl)dithiophosphate.
ꢁ
1,2
Experimental
All synthesis work was done under strictly
shown to be quite versatile not only because
of various bonding modes with several met-
3
als and metalloids but also because of their
4
anhydrous conditions in a nitrogen atomosphere.
wide range of applications in agricultural and
◦
5
Triethylamine (b.p. 88.8 C) and o-cresol (b.p.
industrial fields. A literature survey reveals a
◦
191 C) were freshly distilled prior to use. P S
2 5
ꢁ
variety of work carried out on O,O -dialkyl and
ꢁ
was procured commercially and it was used
as such. Toluene was dried by refluxing over
sodium metal. Micro elemental analysis (C and
H) was carried out on a Vario EL III elemental
O,O -alkylene dithiophosphate chemistry includ-
ing a report on the crystal and molecular struc-
6
tures of two triethyl ammonium salts and our
7
report of two cyclic dithiophosphoric acids.
ꢁ
analyzer while sulfur was estimated as BaSO4
However, no report is available on O,O -bis(o-
by Messenger’s method. The IR spectrum
tolyl)dithiophosphates and their metal complexes,
ꢁ
was recorded on a FTIR Perkin Elmer-377
with the exception of a patent report on O,O -
1
8
spectrophotometer. H NMR spectra were
bis(p-tolyl)dithiophosphate. We report the crys-
recorded on a Jeol FX 90Q 90 MHz using TMS
31
as external reference. The P NMR spectrum
was recorded on a Bruker DRX 300 (120 MHz)
using 85% H PO as external reference.
(1)
(2)
(3)
∗
Department of Chemistry and Biochemistry, University of
Windsor, Windsor, Ontario, N9B 3P4, Canada.
Department of Chemistry, Jammu University, Jammu 180 006,
India.
Department of Pure & Applied Chemistry, M.D.S. University,
Ajmer, 305 009 India.
To whom correspondence should be addressed at Department of
Pure & Applied Chemistry, M.D.S. University, Ajmer, 305 009
India; e-mail: meena ratnani@hotmail.com.
3
4
+
−
2
Synthesis of [Et NH] [(2-MeC H O) PS ]
3
6
4
2
A toluene solution (40 mL) of freshly dis-
tilled o-hydroxy toluene (9.37 g, 8.99 mmol) was
4
47
1
074-1542/05/0600-0447/0 ꢀC 2005 Springer Science+Business Media, Inc.

448
Drake, MacDonald, Kumar, Pandey, and Ratnani
+
added dropwise to a toluene (80 mL) suspension
of P S (5.0 g, 2.24 mmol). After stirring the con-
Table 1. Crystal Data and Structure Refinement for [Et3NH]
−
[(2-MeC6H4O)2PS2]
2
5
◦
tents for 5–7 minutes at ∼40 C, a toluene so-
Empirical formula
Formula weight
Temperature (K)
C20H30NO2PS2
411.54
173(2)
lution (40 mL of Et N (4.55 g, 4.59 mmol) was
3
added dropwise. All the P S dissolved within
2
5
˚
Wavelength (A)
0.71073
Monoclinic
15–20 min giving a clear solution. Evaporation of
Crystal system
Space group
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-
P2 /c
1
˚
a (A)
15.4342(6)
˚
b (A)
10.1913(4)
14.0729(6)
100.855(1)
2174.0(2)
4
˚
c (A)
◦
β ( )
◦
Volume ( A˚ )
3
ture. Yield: (18.1 g, 97.8%); m.p.: 56–58 C; Anal:
Z
Calcd. for C H O PS N (M.W. 411.54): C,
20
30
2
2
3
Density (calculated) (g/cm )
Absorption coefficient (mm 1) 0.333
1.257
5
8.31%; H, 7.28%; S, 15.55% Found: C, 58.29%;
−
1
H, 7.30%; S, 15.54%; H NMR (CDCl , δ ppm):
3
F (000)
Crystal size (mm )
θ range for data collection ( )
880
3
1
.25 (t, 9H, ---CH of Et N, J = 7.2 Hz), 2.23
0.50 × 0.40 × 0.30
3
3
◦
2.41–27.51
(
s, 6H, ---CH of cresol), 3.09 (m, 6H, ---CH
3
2
Index ranges
−20 ≤ h ≤ 20, −13 ≤ k ≤ 13,
−18 ≤ l ≤ 18
of Et N), 7.0–7.2 (m, 8H, ---C H ), 9.24 (s,1H,
3
6
4
31
-
--NH); P (CDCl , δ ppm): 105.6 (s); IR (KBr):
Reflections collected
20706
3
Independent reflections
Max. and min. transmission
Refinement method
4988 [Rint = 0.0473]
3
6
381b, 2950b, 1615m, 1502s, 1488s, 1108s, 909s,
80s, 596s, 540w and 468m cm .
0.9068 and 0.8514
−
1
2
Full-matrix least-squares on F
4988/0/306
1.011
R1 = 0.0492, wR2 = 0.1093
R1 = 0.0811, wR2 = 0.1253
0.354 and −0.511
CCDC 248927
Data/restraints/parameters
2
Goodness-of-fit on F
2
2
Final R indices [F > 4σ(F )]
R indices (all data)
Crystal structure determination
Largest diff. peak and hole
Deposition number
+
A colorless block crystal of [Et NH] [(2-
3
−
MeC H O) PS ] was mounted on a glass fiber,
6
4
2
2
covered in Paratone-N and placed rapidly into the
cold N stream of the Kryo-Flex low temperature
2
device. A hemisphere of data was collected on a
Bruker APEX CCD diffractometer using a count-
ing time of 20 s per frame. Data reduction was
in idealized positions with isotropic thermal
parameters set at 1.2 times that of the carbon or
nitrogen atom to which they were attached. The
final cycle of full-matrix least-squares refinement
was based on 4988 observed reflections (3041
for F > 4σ(F )) and 306 variable parameters
and converged (largest parameter shift was 0.001
times its esd).
9
performed using the SAINT software and the
data was corrected for Lorentz, polarization and
absorption effects using the SAINT and SADABS
programs. Cell refinement gave cell constants cor-
responding to a monoclinic cell whose dimensions
are given in Table 1 along with other experimental
parameters.
2
2
Selected distances and bond angles are given
+
−
in Table 2 and [Et NH] [(2-MeC H O) PS ] is
3
6
4
2
2
1
0
The structure was solved by direct methods
displayed in the ORTEP diagram in Fig. 1 in
which one set of the disordered cation is omitted
for clarity. Additional material available from the
Cambridge Crystallographic Data Centre com-
prises the final atomic coordinates and thermal
parameters for all atoms and all distances and
bond angles.
11
and was refined using the WinGX version of
12
SHELX-97. All of the non-hydrogen atoms
+
were treated anisotropically. The [Et NH]
3
cation was badly disordered but could be
modelled satisfactorily with two orientations of
equal occupancy. Hydrogen atoms were included

ꢀ
Triethyl ammonium salt of O,O -bis(o-tolyl)dithiophosphate
449
˚
◦
+
−
Table 2. Selected Bond Distances (A) and angles ( ) for [Et3NH] [(2-MeC6H4O)2PS2]
˚
Bond distances (A)
S(1) ---- P(1)
P(1) ---- O(1)
O(1) ---- C(1)
N(a) ---- H(1a)
H(1a) ---- S(2)
N(1a) ---- S(2)
1.954(1)
1.632(2)
1.403(2)
0.93
2.42
3.286(6)
S(2) ---- P(1)
1.966(1)
1.613(2)
1.399(3)
0.93
2.33
3.211(7)
P(1) ---- O(2)
O(2) ---- C(8)
N(1b) ---- H(1b)
H(1b) ---- S(2)
N(1b) ---- S(2)
◦
Bond angles ( )
O(1) ---- P(1) ---- O(2)
O(1) ---- P(1) ---- S(1)
O(1) ---- P(1) ---- S(2)
N(1a) ---- H(1a) ---- S(2)
97.07(8)
111.44(7)
109.66(7)
154.93
S(1) ---- P(1) ---- S(2)
O(2) ---- P(1) ---- S(1)
O(2) ---- P(1) ---- S(2)
N(1b) ---- H(1b) ---- S(2)
118.62(4)
106.09(8)
111.81(8)
158.23
Results and discussion
Reaction of o-cresol with P S in the pres-
The IR spectrum shows all characteristic
bands in their expected region. The H NMR
spectrum of the compound shows the chemi-
1
2
5
ence of triethyl amine in 4:1:2 molar ratio in
cal shift for the ---NH proton at δ, 9.2 ppm
toluene is quite facile at room temperature af-
in addition to the characteristic chemical shifts
+
−
2
31
fording [Et NH] [(2-MeC H O) PS ] in quan-
for all other protons. The P NMR spec-
3
6
4
2
titative yield, initially as a colorless viscous pasty
mass which turns crystalline on standing 3–4 days
at room temperature.
trum shows a singlet at δ, 105.6 ppm, indicat-
ing the equivalent nature of the phosphorus nu-
clei as well as the symmetric nature of the
species.
Toluene
(2-MeC H OH) + P S + 2Et N —–−→
+ −
[Et NH] [(2-MeC H O) PS ] crystallizes
3 6 4 2 2
4
6
4
2
5
3
∼
15 min.
+
−
as monoclinic in the space group P2 /c. In the
1
[
Et NH] [(2-MeC H O) PS ] + H S
3
6
4
2
2
2
ORTEP diagram in Fig. 1, the expected distorted
tetrahedral environment around phosphorous in
−
the anion[(2-MeC H O) PS ] can be clearly
6
4
2
2
seen with two sulfur and two oxygen atoms mak-
ing up the coordination sphere. The formation of
an N(1b)---H(1b)---S(2) hydrogen bond is also
evident. The N(1a)---H(1a) and N(1b)---H(1b)
˚
bond lengths are fixed at 0.93 A, while the
N(1a)---S(2) and N(1b)---S(2) distances refine to
˚ ˚
erage N(1)---S(2) distance of 3.25(5) A compares
3
.286(6) A and 3.211(6) A, respectively. The av-
˚
6
˚
well with the value of 3.248(6) A reported for
+ −
Et NH] [(OCH CMe CH O)PS ] . The aver-
3 2 2 2 2
[
age values for the remaining hydrogen bonding
+
−
parameters in [Et NH] [(2-MeC H O) PS ] of
3
6
4
2
2
H(1)---S(2) and N(1)---H(1)---S(2) are 2.37 A
˚
◦
6
˚
and 156 , respectively, compared to 2.44 A and
◦ +
160 in [Et NH] [(OCH CMe CH O)PS ] .
3 2 2 2
−
+
−
Fig. 1. ORTEP plot of [Et
3
NH] [(2-MeC
6
H
4
O)
2
PS
2
] . The
2
The average N(1)---S(1) distance of 3.60(10) A
˚
atoms are drawn with 50% probability ellipsoids with one
set of the disordered cation removed for clarity.
+
−
in [Et NH] [(2-MeC H O) PS ] suggests very
3
6
4
2
2

450
Drake, MacDonald, Kumar, Pandey, and Ratnani
◦
7
+
2
little, if any, hydrogen bonding involving the
second sulfur atom.
(
97.6(2) ) but smaller than those in K [(MeO)
−
◦ 13
OPS ] ·H O (100.93(7) ) or the six-membered
2
2
The S(1)---P(1) bond length of 1.954(1) A
˚
ring systems in HS POCH CMe CH O,
2
2
2
2
˚
---
◦ 7 +
105.1(1) ) and [Et NH] [(OCH CMe CH O)
3 2 2 2
compared with 1.966(1) A for S(2) P(1) is con-
sistent with the former not being involved in hy-
drogen bonding. Both bonds are close to the range
(
−
◦ 6
(101.4(2) ) or the eight-membered
PS2]
+
−
ring in [Et NH] [CH 6-t-Bu-4-C H OPS ]
3
2
6
4
2
6
+
˚
1.945(1) to 1.962(2) A) reported for [Et NH]
3
◦
6
(
[
(103.5(4) ). Thus, despite some interesting
variations, in general, the basic structural features
around phosphorus remain much the same.
−
+
(OCH CMe CH O)PS ] and [Et NH] [CH 6-
2
2
2
2
3
2
−
t-Bu-4-C H OPS ] , longer than the terminal
P -- -- -- S bond, 1.923(2) and 1.908(2) A in HS2
POCMe CMe O and HS POCH CMe CH O,
6
4
2
˚
2
2
2
2
2
2
Supplementary material Additional material available from the
Cambridge Crystallographic Data Centre (CCDC no. 248927) com-
prises the final atomic coordinates for all atoms, thermal parame-
ters, and a complete listing of bond distances and angles. Copies
of this information may be obtained free of charge on appli-
cation to The Director, 12 Union Road, Cambridge CB2 2EZ,
UK (fax: +44-1223-336033; e-mail:deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk).
7
respectively, but shorter than the values of
+
˚ ˚
.007(6) A and 2.011(5) A obtained in K
2
2
[
−
13
(MeO)OPS ] ·H O, reflecting the partial dou-
2
2
ble bond character of the S---P bond. The
P---O bond lengths of 1.632(2) A and 1.613(2) A,
are similar to those in [Et NH] [(OCH CMe
CH O)PS ] and [Et NH] [CH 6-t-Bu-4-C H
OPS ] , which range from 1.636(3) A to
˚
.611(2) A, slightly longer than those in HS
POCMe CMe O (1.594(3) and 1.589(3) A)
and HS POCH CMe CH O (1.583(3) A and
˚
˚
+
3
+
2
2
−
2
2
3
2
6
4
Acknowledgments
−
˚
2
6
1
2
7
J. E. Drake and C. L. B. MacDonald thank
the Natural Sciences and Engineering Research
Council of Canada for financial support.
˚
2
2
˚
2
˚
˚
2
2
2
7
1
1
.582(3) A), but similar to the value of
+
−
13
.635(1) A found in K [(MeO)OPS ] ·H O.
2
2
2
◦
References
The S---P---S bond angle of 118.62(4)
+
−
in [Et NH] [(2-MeC H O) PS ] is slightly
3
6
4
2
2
1
2
. Chauhan, H.P.S. Coord. Chem. Rev. 1998, 173 , 1.
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2003, 28, 405.
3. Haiduc, I. Rev. Inorg. Chem. 1981, 3, 353.
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5. Nicholls, M.A.; Bancroft, G.M.; Nortan, P.R.; Kasrai, M.;
Stasio, G.D.; Frazer, B.H. Tribiol. Lett. 2004, 17, 245.
. Kumara Syamy, K.C.; Kumarasyamy, S.; Raja, S.; Kumar, K.S.
J. Chem. Cryst. 2001, 31, 51.
7. Drake, J.E.; Khasrou, L.N.; Mislankar, A.G.; Ratnani, R. Poly-
hedron. 2000, 19, 407.
8. Markova, E.I.; Akhnedzade, D.A.; Dzhanikbekov, N.F. Azerb.
Khim. 1984, 1, 135–138; Chem. Abstr. 1984, 101, 221365.
. SAINT. (2001). Bruker AXS, Inc. Madison, WI.
10. Sheldrick, G.M. Acta Cryst. 1990, A46, 467.
11. Farrugia, L.J. J. Appl. Cryst. 1999, 32, 837.
12. Sheldrick, G.M. SHELXL97, Structure Determination Soft-
ware; University of Gottingen, Germany, 1997.
13. Gupta, M.C. Ph.D. Thesis, University of Rajasthan, India, 2004.
smaller than those of the other two triethylammo-
+
−
nium salts, [Et NH] [(OCH CMe CH O)PS ]
3
2
2
2
2
◦
6
+
(
119.27(8) )
and [Et NH] [CH 6-t-Bu-4-
C H OPS ] (120.49(8) ). All three triethyl-
3 2
6
4
−
◦
6
4
2
ammonium salts have larger S---P---S angles
6
than those in the monodentate ligand in Ph Te
2
◦
7
7
[
S POCMe CMe O] (114.3(1) and 115.2(1) ),
2
2
2
2
◦
the free acids HS POCMe CMe O (112.78(8) ),
2
2
2
◦
7
+
HS POCH CMe CH O (115.64(8) ), or K
2
2
2
2
13
2
9
−
◦
[
(MeO)OPS ] ·H O (113.67(3) ). The O---P---O
2
2
◦
+
bond angle of 97.07(8) in [Et NH] [(2-
3
−
MeC H O) PS ] is similar to that in the five-
6
4
2
2
membered ring system, HS POCMe CMe O
2
2
2