Synthesis and characterization of N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr)2 (p-(4-imidazol-1-yl)-C6H4NH, p-N{triple bond, long}C-C6H4NH, (CH2{double bond, long}CH-CH2)<su

Article abstract of DOI:10.1016/j.poly.2009.10.010

Reaction of p-(4-imidazol-1-yl)-C₆H₄NH₂, p-N(triple bond, long)C-C₆H₄NH₂ or (CH₂(double bond, long)CH-CH₂)₂NH with O,O′-diisopropylthiophosphoric acid isoth

Full text of DOI:10.1016/j.poly.2009.10.010

Polyhedron 29 (2010) 715–718
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Polyhedron
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Synthesis and characterization of N-thiophosphorylated thioureas
RC(S)NHP(S)(OiPr)2 (p-(4-imidazol-1-yl)–C6H4NH, p-N„C–C6H4NH,
(CH2@CH–CH2)2N): Unexpected formation of o-HO–C6H4NHC(S)NHP(S)(OiPr)2
from p-N„C–C6H4NHC(S)NHP(S)(OiPr)2
a
b
a
Damir A. Safin a, , Maria G. Babashkina , Michael Bolte , Axel Klein
*
a Institut für Anorganische Chemie, Universität zu Köln, Greinstrasse 6, D-50939 Köln, Germany
b Institut für Anorganische Chemie J.-W.-Goethe-Universität, Frankfurt/Main, Germany
a r t i c l e i n f o
a b s t r a c t
Reaction of p-(4-imidazol-1-yl)–C6H4NH2, p-N„C–C6H4NH2 or (CH2@CH–CH2)2NH with O,O0-diisopro-
pylthiophosphoric acid isothiocyanate (iPrO)2P(S)NCS leads to p-(4-imidazol-1-yl)–C6H4NHC(S)
NHP(S)(OiPr)2 (HLI), p-N„C–C6H4NHC(S)NHP(S)(OiPr)2 (HLII) and (CH2@CH–CH2)2NC(S)NHP(S)(OiPr)2
(HLIII). Recrystallization of HLII from 96% aqueous EtOH solution leads to the formation of o-HO–
C6H4NHC(S)NHP(S)(OiPr)2 (HLIV). The structures of HLI–IV were investigated by 1H and 31P{1H} NMR spec-
troscopy, and microanalysis. The molecular structures of HLI,IV were elucidated by single crystal X-ray
diffraction analysis. Single crystal X-ray diffraction studies showed that HLI,IV form both intra- and inter-
molecular hydrogen bonds, the latter leading to the formation of polymeric chains.
Article history:
Received 15 September 2009
Accepted 12 October 2009
Available online 15 October 2009
Keywords:
Thiophosphorylthiourea
Crystal structure
NMR spectroscopy
Hydrogen bond
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
2. Experimental
Phosphorylated thioamides and thioureas RCðSÞNHPðXÞR02 have
long attracted attention of researchers due to their ability to form
stable chelate complexes with IB, IIB, and VIIIB group transition
metal cations. These compounds and their complexes exhibit anti-
viral activity [1]. They can be used as stationary phases for GLC [2],
as well as components of ion-selective electrodes [3–6], extract-
ants [7–9] and masking reagents in analytical chemistry [10].
This contribution is a continuation of our previously started
investigations on the synthesis and characterization of N-
(thio)phosphorylated (thio)amides and (thio)ureas [8,9,11]. Herein,
we report the synthesis and characterization of N-thiophosphorylat-
ed thioureas p-(4-Imidazol-1-yl)–C6H4NHC(S)NHP(S)(OiPr)2 (HLI),
p-N„C–C6H4NHC(S)NHP(S)(OiPr)2 (HLII), (CH2@CH–CH2)2NC(S)
NHP(S)(OiPr)2 (HLIII) and o-HO–C6H4NHC(S)NHP(S)(OiPr)2 (HLIV).
These compounds are of interest due to the presence of additional
functional groups as the imidazole nitrogen atom in HLI, the cyano
group in HLII, alkenyl fragments in HLIII and the hydroxyl group in
HLIV. Thus, HLI–IV might be used as complexing agents towards var-
ious metal cations both by the chelate C(S)NHP(S) backbone and a
substituent at the thiocarbonyl group.
2.1. Synthesis of HLI–III
A solution of p-(4-imidazol-1-yl)–C6H4NH2, p-N„C–C6H4NH2
or (CH2@CH–CH2)2NH (0.795, 0.590 or 0.485 g, respectively;
5 mmol) in anhydrous CH2Cl2 (15 mL) was treated under vigorous
stirring with a solution of (iPrO)2P(S)NCS (1.434 g, 6 mmol) in the
same solvent (15 mL). The mixture was stirred for 1 h. The solvent
was removed in a vacuum, and the product was purified by recrys-
tallization from a 1:5 (v/v) mixture of dichloromethane and n-
hexane.
HLI: Yield 1.672 g (84%), mp 84 °C. 1H NMR d (ppm): 1.40 (d,
3JH,H = 6.2 Hz, 12H, CH3, iPr), 4.88 (d. sept, JPOCH = 10.6 Hz,
3
3JH,H = 6.1 Hz, 2H, OCH), 7.17–7.91 (m, overlapped with the solvent
signal, aryl + PNH), 9.96 (s, 1H, NH); 31P{1H} NMR d (ppm): 51.8.
31P NMR d (ppm): 51.6–52.0 (m). Anal. Calc. for C16H23N4O2PS2: C
48.23, H 5.82, N 14.06. Found: C 48.29, H 5.73, N 14.16%.
HLII: Yield 1.66 g (93%), oil. 1H NMR
d (ppm): 1.24 (d,
3JH,H = 6.2 Hz, 12H, CH3, iPr), 4.73 (d. sept, JPOCH = 9.8 Hz,
3JH,H = 6.0 Hz, 2H, OCH), 7.06–7.84 (m, overlapped with the solvent
signal, C6H4 + PNH), 9.12 (s, 1H, NH); 31P{1H} NMR d (ppm): 53.7.
3
31P NMR d (ppm): 53.7 (d. t, JPOCH = 9.9 Hz, JPNH = 4.2 Hz). Anal.
Calc. for C14H20N3O2PS2: C 47.05, H 5.64, N 11.76. Found: C
46.97, H 5.69, N 11.82%.
3
2
HLIII: Yield 1.142 g (68%), mp 47 °C. 1H NMR d (ppm): 1.36 (d,
3JH,H = 6.2 Hz, 12H, CH3, iPr), 4.27 (br. s, 4H, CH2@CH–CH2), 4.91
* Corresponding author. Tel.: +49 78432315397.
E-mail address: damir.safin@ksu.ru (D.A. Safin).
0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.10.010

716
D.A. Safin et al. / Polyhedron 29 (2010) 715–718
(d. sept, 3JPOCH = 10.5 Hz, 3JH,H = 6.1 Hz, 2H, OCH), 5.16–5.42 (m, 4H,
CH2@CH–CH2), 5.72–5.96 (m, 2H, CH2@CH–CH2), 6.56 (s, 1H, NH);
2.4. Crystal structure determination and refinement
31P{1H} NMR
d
(ppm): 58.3; 31P NMR
d
(ppm): 58.3 (t,
The X-ray data for HLI,IV were collected on a STOE IPDS-II dif-
fractometer with graphite-monochromatized Mo Ka radiation
3JPOCH = 2JPNH = 10.5 Hz). Anal. Calc. for C13H25N2O2PS2: C 46.41, H
7.49, N 8.33. Found: C 46.30, H 7.44, N 8.39%.
generated by fine-focus X-ray tube operated at 50 kV and 40 mA.
The images were indexed, integrated and scaled using the X-Area
data reduction package [12]. Data were corrected for absorption
using the PLATON program [13]. The structures were solved by direct
method using the SHELXS-97 program [14] and refined on F2 with
full-matrix least-squares using SHELXL-97 [15].
2.2. Synthesis of HLIV
N-Thiophosphorylated thiourea HLIV was prepared by the
recrystallization of HLII (0.714 g, 2 mmol) from a 96% aqueous
EtOH solution (20 mL). Yield 0.682 g (98%), mp 128 °C. 1H NMR d
3
3
3. Results and discussion
(ppm): 1.39 (d, JH,H = 6.0 Hz, 6H, CH3, iPr), 1.40 (d, JH,H = 6.0 Hz,
3
3
6H, CH3, iPr), 4.87 (d. sept, JPOCH = 10.5 Hz, JH,H = 6.1 Hz, 2H,
OCH), 6.64–6.82 (m, 1H, OH), 6.92–7.42 (m, overlapped with the
solvent signal, C6H4 + PNH), 9.70 (s, 1H, NH); 31P{1H} NMR d
The compounds HLI–III were synthesized by the treatment of the
corresponding amine with the isothiocyanate (iPrO)2P(S)NCS
(Scheme 1). N-Thiophosphorylated thiourea HLIV was prepared
by recrystallization of HLII from a 96% aqueous EtOH solution
(Scheme 2). It should be noted that the recrystallization of HLII
from other solvents (dried or aqueous CH2Cl2, CH3CN, C6H6, DMSO,
or dried EtOH) did not lead to crystals, and only fine crystalline
material of HLII was isolated. Thus, the synthesis of HLIV by recrys-
tallization from 96% EtOH is evidently the result of the water pres-
ent in the solvent and we also can state that the influence of EtOH
is obvious and important. The substitution of the H-atom by an HO
group in the benzene group in HLII occurs in the meta-position to
the N„C substituent (ꢀM, ꢀI effects) and in the ortho-position
relative to the NHC(S)NHP(S)(OiPr)2-group (+M, ꢀI). The reaction
occurs at very high yields at very mild conditions, but at present
3
(ppm): 52.5. 31P NMR d (ppm): 52.5 (t, JPOCH = 2JPNH = 10.4 Hz).
Anal. Calc. for C13H21N2O3PS2: C 44.82, H 6.08, N 8.04. Found: C
44.94, H 5.98, N 8.09%.
2.3. Physical measurements
NMR spectra in CDCl3 solution were obtained on a Bruker
Avance 300 MHz spectrometer at 25 °C. 1H and 31P{1H} NMR spec-
tra were recorded at 299.948 and 121.420 MHz, respectively.
Chemical shifts are reported with reference to SiMe4 (1H) and
85% H3PO4 (
31P{1H} and 31P). Elemental analyses were performed
on a CHNS HEKAtech EuroEA 3000 analyzer.
H
H
N
NH2
N
N
O
O
N
N
P
S
N
N
S
HLI
H
H
N
N
C
NH2
O
N
O
O
S
C
N
P
S
C
P
S
O
S
HLII
H
N
NH
O
O
N
P
S
S
HLIII
Scheme 1. Preparation of HLI–III
.
OH
H
N
H
N
H
N
H
O
96% aq. EtOH
O
O
N
C
P
N
P
O
S
S
S
S
HLII
HLIV
Scheme 2. Preparation of HLIV
.

D.A. Safin et al. / Polyhedron 29 (2010) 715–718
717
Table 1
Table 2
Crystal data, data collection and refinement details for HLI,IV
.
Selected bond lengths (Å), and bond and torsion angles (°) for HLI.
HLI
HLIV
Bond lengths
P(1)–O(1)
P(1)–O(2)
P(1)–N(1)
P(1)–S(1)
1.5782(11)
1.5795(11)
1.6651(14)
1.9139(6)
S(2)–C(1)
N(1)–C(1)
N(2)–C(1)
1.6608(15)
1.3827(19)
1.351(2)
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C16H23N4O2PS2
398.47
C13H21N2O3PS2
348.41
monoclinic
P21/c
12.4913(8)
11.3434(9)
13.9608(9)
90
114.775(4)
90
1796.1(2)
4
1.288
173(2)
736
triclinic
ꢀ
P1
Bond angles
9.5103(6)
9.5970(6)
12.3632(7)
70.576(5)
79.302(5)
71.337(5)
1004.24(11)
2
O(1)–P(1)–O(2)
O(1)–P(1)–N(1)
O(2)–P(1)–N(1)
O(1)–P(1)–S(1)
O(2)–P(1)–S(1)
99.71(6)
N(2)–C(1)–S(2)
N(1)–C(1)–S(2)
N(1)–P(1)–S(1)
C(1)–N(1)–P(1)
N(2)–C(1)–N(1)
124.49(11)
120.53(11)
112.86(5)
129.75(11)
114.96(13)
b (Å)
c (Å)
102.04(6)
106.91(7)
117.40(5)
116.13(5)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Torsion angles
O(1)–P(1)–N(1)–C(1)
O(2)–P(1)–N(1)–C(1)
S(1)–P(1)–N(1)–C(1)
49.87(15)
P(1)–N(1)–C(1)–N(2)
P(1)–N(1)–C(1)–S(2)
ꢀ3.6(2)
Dcalc (g cmꢀ3
T (K)
)
1.318
173(2)
420
ꢀ54.33(15)
178.03(9)
176.78(12)
F(0 0 0)
l
(mmꢀ1
)
0.362
0.395
Reflections collected 19226
Unique reflections 3760
Observed reflections 3309 (Rint = 0.054)
R indices (all data)
9283
3355
2909 (Rint = 0.039)
Table 3
Selected bond lengths (Å), and bond and torsion angles (°) for HLIV
.
R1 = 0.0366, wR2 = 0.0850 R1 = 0.0456, wR2 = 0.0911
Bond lengths
P(1)–O(1)
P(1)–O(2)
P(1)–N(1)
P(1)–S(1)
1.5742(14)
1.5690(15)
1.6847(16)
1.9105(7)
S(2)–C(1)
N(1)–C(1)
N(2)–C(1)
1.6894(17)
1.374(2)
1.332(2)
Bond angles
O(2)–P(1)–O(1)
O(1)–P(1)–N(1)
O(2)–P(1)–N(1)
O(1)–P(1)–S(1)
O(2)–P(1)–S(1)
96.54(8)
N(2)–C(1)–S(2)
N(1)–C(1)–S(2)
N(1)–P(1)–S(1)
C(1)–N(1)–P(1)
N(2)–C(1)–N(1)
123.36(13)
120.01(12)
108.81(6)
130.11(13)
116.62(15)
106.20(8)
105.25(8)
119.57(6)
118.86(6)
Torsion angles
O(1)–P(1)–N(1)–C(1)
O(2)–P(1)–N(1)–C(1)
S(1)–P(1)–N(1)–C(1)
ꢀ53.29(17)
48.37(17)
176.78(14)
P(1)–N(1)–C(1)–N(2)
P(1)–N(1)–C(1)–S(2)
14.3(2)
ꢀ166.41(10)
thioureas contain a set of signals for the iPr protons: a doublet or
two doublets for the CH3 protons at 1.24–1.40 ppm and a doublet
of septets for the CH protons at 4.73–4.91 ppm. The spectra of
HLI,II,IV exhibit signals for the aryl and PNH protons at 6.92–
7.91 ppm. The signal for the arylNH proton in the spectra of HLI,II,IV
is at 9.12–9.96 ppm, which is in the low-field area due to hydrogen
bond formation of the aryl N–HꢁꢁꢁO@P type. The signal for the OH
proton in the spectrum of HLIV was observed as a multiplet at
6.64–6.82 ppm. The signals for the CH2@CH–CH2 protons were
found at 4.27–5.96 ppm, while the PNH proton signal was ob-
Fig. 1. Thermal ellipsoid representation of HLI. Ellipsoids are drawn at the 30%
probability level.
served at 6.56 ppm in the spectrum of HLIII
.
Crystals of HLI were obtained by slow evaporation of its satu-
rated solution in CH2Cl2–n-hexane (1:3 v/v), while crystals of HLIV
were obtained by recrystallization of HLII from a 96% aqueous EtOH
solution. Results of the structure solution and refinements are col-
lected in Table 1. The representative structures are shown in Figs. 1
and 2, bonding parameters are collected in Tables 2 and 3.
The compounds HLI and HLIV crystallize in the space groups P1
ꢀ
and P21/c, respectively. The parameters of the C@S, C–N, P–N and
P@S bonds observed in the molecular structures of HLI and HLIV (Ta-
bles 2 and 3) are in the typical range for N-thiophosphorylated thio-
urea derivatives [11]. The S–C–N–P backbone in the crystal phase
has an E-conformation. The phenylene ring in HLI is considerably ro-
tatedrelativeto theflattenedNC(S)NPbackbone(torsionangleC(1)–
N(2)–C(11)–C(12) is ꢀ51.0(2)°) and the imidazolring (torsionangles
C(13)–C(14)–N(21)–C(25) and C(15)–C(14)–N(21)–C(22) are
43.3(2)° and 45.2(2)°, respectively). The phenylen ring in HLIV is also
considerably rotated relative to the flattened NC(S)NP backbone
(torsion angle C(1)–N(2)–C(11)–C(16) is 59.2(3)°). The crystal struc-
tures of HLI (Fig. 3, Table 4) and HLIV (Fig. 4, Table 4) are stabilized by
intramolecular hydrogen bonds of the type N(2)–H(2)ꢁꢁꢁO(1).
Fig. 2. Thermal ellipsoid representation of HLIV. Ellipsoids are drawn at the 30%
probability level.
we have no clue about the reaction mechanism. A nucleophilic aro-
matic substitution of the CN group (by OHꢀ) should not be largely
favored by an amino group in p-position. Secondly it should be
combined with a highly preferred anionic H shift in the transition
state.
The 31P{1H} NMR spectra of HLI–IV each contain a singlet signal
at 51.8, 53.7, 58.3 and 52.5 ppm, respectively, which is typical for
N-thiophosphorylated thioureas [11]. The 1H NMR spectra of the

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D.A. Safin et al. / Polyhedron 29 (2010) 715–718
Fig. 3. Hydrogen bonding in the crystal of HLI. H-atoms, not involved in hydrogen bonding, are omitted.
orylisothiocyanate to the corresponding amine. Recrystallization of
HLII from a 96% aqueous EtOH solution leads to the formation of
HLIV
Single crystal X-ray diffraction studies showed that the thio-
ureas HLI,IV form both intra- and intermolecular hydrogen bonds
with the latter leading to polymeric chains in the crystal structure.
Table 4
Hydrogen bond lengths (Å) and angles (°) for HLI,IV
.
.
D–HꢁꢁꢁA
d(D–H)
d(HꢁꢁꢁA)
d(DꢁꢁꢁA)
\ðDHAÞ
HLIa
N(1)–H(1)ꢁꢁꢁN(23)#1
N(2)–H(2)ꢁꢁꢁO(1)
0.80(2)
0.81(2)
0.82(2)
0.79(2)
0.84(3)
2.10(2)
2.18(2)
2.55(2)
2.32(2)
2.39(3)
2.8939(19)
2.8599(18)
3.3562(15)
2.994(2)
179(2)
140.9(19)
169(2)
145(2)
168(3)
HLIIb
N(1)–H(1)ꢁꢁꢁS(2)#1
N(2)–H(2)ꢁꢁꢁO(1)
O(3)–H(3)ꢁꢁꢁS(2)#2
3.2178(17)
Supplementary data
a
Symmetry transformations used to generate equivalent atoms: #1 x, y, z ꢀ 1.
Symmetry transformations used to generate equivalent atoms: #1 ꢀx, ꢀy + 1,
b
CCDC 745307 and 745308 contain the supplementary crystallo-
graphic data for HLI,IV. 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, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
ꢀz; #2 x, ꢀy + 1/2, z + 1/2.
References
[1] N.G. Zabirov, O.K. Pozdeev, F.M. Shamsevaleev, R.A. Cherkasov, G.Kh.
Gilmanova, Pharm. Chem. J. 23 (1989) 423 (Engl.Transl.).
[2] Z.P. Vetrova, N.G. Zabirov, T.N. Shuvalova, L.S. Smerkovich, L.A. Ivanova, A.K.
Golberg, N.T. Karabanov, Russ. J. Gen. Chem. 62 (1992) 883.
[3] L.G. Shaidarova, A.V. Gedmina, V.V. Brusko, N.G. Zabirov, N.A. Ulakhovich, G.K.
Budnikov, Anal. Sci. 17 (2001) i957.
[4] M.P. Kutyreva, N.G. Zabirov, V.V. Brusko, N.A. Ulakhovich, Anal. Sci. 17 (2001)
i1049.
[5] L.G. Shaidarova, A.V. Gedmina, V.V. Brusko, N.G. Zabirov, N.A. Ulakhovich, G.K.
Budnikov, Russ. J. Appl. Chem. 75 (2002) 919.
[6] L.G. Shaidarova, A.V. Gedmina, N.A. Ulakhovich, G.K. Budnikov, N.G. Zabirov,
Russ. J. Gen. Chem. 72 (2002) 1565.
Fig. 4. Hydrogen bonding in the crystal of HLIV. H-atoms, not involved in hydrogen
bonding, are omitted.
[7] O. Navratil, E. Herrmann, N.T.T. Chau, Ch. Tea, J. Smola, Collect. Czech. Chem.
Commun. 58 (1993) 798.
[8] R.C. Luckay, X. Sheng, C.E. Strasser, H.G. Raubenheimer, D.A. Safin, M.G.
Babashkina, A. Klein, Dalton Trans. (2009) 4646.
[9] R.C. Luckay, X. Sheng, C.E. Strasser, H.G. Raubenheimer, D.A. Safin, M.G.
Babashkina, A. Klein, Dalton Trans. (2009) 8227.
[10] M.G. Zimin, G.A. Lazareva, N.I. Saveleva, R.G. Islamov, N.G. Zabirov, V.F.
Toropova, A.N. Pudovik, Zh. Obshch. Khim. (USSR) 52 (1982) 1776.
[11] F.D. Sokolov, V.V. Brusko, N.G. Zabirov, R.A. Cherkasov, Curr. Org. Chem. 10
(2006) 27.
Furthermore, the molecules of HLI form polymeric chains due to the
intermolecular hydrogen bonds of the type N(1)–H(1)ꢁꢁꢁN(23)#1
(Fig. 3, Table 4), while molecules of HLIV form polymeric chains
due to the intermolecular hydrogen bonds of the type O(3)–
H(3)ꢁꢁꢁS(2)#2. Finally, these chains were interconnected by intermo-
lecular hydrogen bonds of the type N(1)–H(1)ꢁꢁꢁS(2)#1 (Fig. 4,
Table 4).
[12] Stoe & Cie, X-Area, Area-Detector Control and Integration Software, Stoe & Cie,
Darmstadt, Germany, 2001.
[13] A.L. Spek, J. Appl. Crystallogr. A 36 (2003) 7.
4. Conclusions
[14] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
[15] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (2008) 112.
In summary, we have demonstrated the syntheses of three new
N-thiophosphorylated thioureas HLI–III by addition of thiophosph-