Complexes of N-thiophosphorylthiourea (EtO)2P(O)CH2C6H4-4-[NHC(S)NHP(S)(OiPr)2] with Zn(II), Cd(II), Co(II) and Cu(PPh3)(I)

Article abstract of DOI:10.1016/j.poly.2008.06.005

Reaction of O,O'-diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with diethyl 4-aminobenzylphosphonate (EtO)₂P(O)CH₂C₆H₄-4-NH₂ leads to the new N-thiophosphorylated thiourea (E

Full text of DOI:10.1016/j.poly.2008.06.005

Polyhedron 27 (2008) 2978–2982
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Complexes of N-thiophosphorylthiourea
(EtO)2P(O)CH2C6H4-4-[NHC(S)NHP(S)(OiPr)2] with Zn(II), Cd(II),
Co(II) and Cu(PPh3)(I)
a
a
b
a
Damir A. Safin a, , Maria G. Babashkina , Timur R. Gimadiev , Michael Bolte , Marina V. Pinus ,
*
Dmitriy B. Krivolapov c, Igor A. Litvinov c
a A.M. Butlerov Chemistry Institute, Kazan State University, Kremlevskaya Street 18, 420008 Kazan, Russia
b Institut für Anorganische Chemie J.-W.-Goethe-Universität, Frankfurt/Main, Germany
c A.E. Arbuzov Institute of Organic and Physical Chemistry, Arbuzov Street 8, 420088, Kazan, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of O,O’-diisopropylthiophosphoric acid isothiocyanate (iPrO)2P(S)NCS with diethyl 4-amin-
obenzylphosphonate (EtO)2P(O)CH2C6H4-4-NH2 leads to the new N-thiophosphorylated thiourea (EtO)2-
P(O)CH2C6H4-4-[NHC(S)NHP(S)(OiPr)2] (HL). Reaction of the potassium salt of HL with Zn(II), Cd(II) and
Co(II) in aqueous EtOH leads to complexes of formula M(L-S,S’)2 (ML2). Heteroligand copper(I) complex of
HL and triphenylphosphine was prepared by the reaction of the potassium salt KL and Cu(PPh3)3I. Copper
in complex Cu(PPh3)L is bound by one PPh3 and one SCNPS fragment of the chelating ligand. Compounds
obtained were investigated by IR, UV–Vis, 1H and 31P{1H} NMR spectroscopy, and microanalysis. The
structures of HL and Cu(PPh3)L were investigated by single crystal X-ray diffraction analysis.
Ó 2008 Elsevier Ltd. All rights reserved.
Received 26 March 2008
Accepted 8 June 2008
Available online 14 July 2008
Keywords:
Chelate
Copper
Zinc
Cadmium
Cobalt
Crystal structures
N-Thiophosphorylthiourea
1. Introduction
Published data reveal that structure and properties of triphenyl-
phosphine containing complexes of XCNPY or XPNPX are strongly
Imidodiphosphinates R2P(X)NHP(X)R’2 (X = S, Se) [1–5] and
their complexes with divalent d-metal cations have been exten-
sively investigated. Formation of chelate complexes of the ML2
structure is characteristic for them. Ligands are coordinated biden-
tately in these compounds, through the atoms of X of the
thio(seleno)carbonic and thio(seleno)phosphoric groups. Cobalt(II)
chelates with oxygen-containing ligands RC(O)NHP(O)R’2 show the
expressed propensity to oligomerization in the solid phase and to
the formation of complexes with the solvent molecules [6–8].
Heteroligand copper(I) complexes of triphenylphosphine and
XCNPY or XPNPX (X, Y = O, S, Se) backbone ligands [8–11] have
been earlier reported. It was established that PPh3 was used as
an additional donor ligand to prepare the non-cluster complex of
Cu(I), where the copper atom is bound only to one molecule of che-
lating SPNPS ligand [10]. In this case, the filling of coordination
sites of copper(I) is necessary to prevent cluster formation.
dependent on the nature of chelating ligand. To the best of our
knowledge, there are no data explaining reasons of one or two
PPh3 molecules binding with Cu(I) metal centre. For this purpose
we conceived to use thiophosphorylated thiourea, containing steri-
cally demanding substituent capable to the hydrogen bonds
formation.
Amidophosphates RC(S)NHP(X)R2 have long attracted attention
of researchers due to their ability to form stable chelates with IB,
IIB, and VIIIB group transition metal cations. These compounds
and their complexes exhibit antiviral activity [12]. They can be
used as stationary phases for GLC [13], as well as components of
ion-selective electrodes [14–17], extractants [18], and masking re-
agents in analytical chemistry [19].
These investigations are caused by the further utilizing of ob-
tained Zn(II), Cd(II), Co(II) and Cu(I) compounds with dithiocon-
taining ligand as single source molecular precursors for the
preparation of metal sulfide thin films and nanocrystals by chem-
ical vapor deposition [20,21].
We report here the structure of the thiourea (EtO)2P(O)CH2C6H4-
4-[NHC(S)NHP(S)(OiPr)2] (HL) and complex Cu(PPh3-P){(EtO)2-
P(O)CH2C6H4-4-[NHC(S)NP(S)(OiPr)2]-S,S0} (Cu(PPh3)L) deter-
mined by X-ray single crystal diffraction.
* Corresponding author. Tel.: +7 843 231 53 97; fax: +7 843 231 54 16.
E-mail address: damir.safin@ksu.ru (D.A. Safin).
0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.06.005

D.A. Safin et al. / Polyhedron 27 (2008) 2978–2982
2979
(0.489 g, 0.5 mmol) was added dropwise under vigorous stirring
to the resulting potassium salt. The mixture was stirred at room
temperature for a further hour and a precipitate was filtered off.
The filtrate was concentrated until the crystallization began. The
residue was recrystallized from a dichloromethane–n-hexane mix-
ture 1:5 (v/v). Complex was obtained as colorless crystals. Yield:
0.295 g (73%). M.p. 127 °C. 1H NMR (CDCl3): d = 1.12–1.44 (m,
2. Experimental
2.1. Synthesis of HL
A
solution of diethyl 4-aminobenzylphosphonate (0.243 g,
1 mmol) in CH2Cl2 (15 mL) was added dropwise to a solution of
SCNP(S)(OiPr)2 (0.263 g, 1.1 mmol) in the same solvent (15 mL).
The mixture was stirred at room temperature for 3 h. The solvent
was then removed in vacuum. The residue was recrystallized from
a dichloromethane–n-hexane mixture 1:5 (v/v). The product was
obtained as colorless crystals. Yield: 0.429 g (89%). M.p. 73 °C. 1H
2
18H, CH3, EtO + iPrO), 3.10 (d, JP,H = 21.3 Hz, 2H, CH2, P(O)CH2),
3
3.89–4.08 (m, 4H, OCH, EtO), 4.73 (d. sept, JH,H = 6.1 Hz,
3JPOCH = 10.4 Hz, 2H, OCH, iPrO), 7.13–7.23, 7.28–7.77 (m, 19H,
C6H4 + C6H5), 8.47 (s, 1H, NH). 31P{1H} NMR (CDCl3): d = –0.9 (1P,
3
PPh3), 27.1 (1P, P@O), 55.3 (1P, P@S). IR:
m = 606 (P@S), 962, 974,
NMR (CDCl3): d = 1.26 (t, JH,H = 7.1 Hz, 6H, CH3, EtO), 1.38 (d,
998, 1017 (POC), 1252 (P@O), 1530 (S@C–N), 3263 (NH) cm–1. Anal.
Calc. for C36H46CuN2O5P3S2 (807.36): C, 53.56; H, 5.74; N, 3.47.
Found: C, 53.43; H, 5.85; N, 3.34.
3JH,H = 6.2 Hz, 12H, CH3, iPrO), 3.14 (d, JP,H = 21.5 Hz, 2H, CH2,
2
3
3
P(O)CH2), 4.04 (d. quart, JH,H = 7.1 Hz, JPOCH = 8.8 Hz, 4H, OCH2,
3
3
EtO), 4.86 (d. sept, JH,H = 6.2 Hz, JPOCH = 10.5 Hz, 2H, OCH, iPrO),
2
7.19 (d, JPNH = 10.4 Hz, 1H, NH, P(S)NH), 7.27–7.53 (m, 4H, C6H4),
9.66 (s, 1H, NH). 31P{1H} NMR (CDCl3): d = 26.7 (1P, P@O), 53.4
2.4. Physical measurements
(1P, P@S). IR:
1559 (S@C–N), 3126, 3272 (NH) cm–1
18H32N2O5P2S2 (482.53): C, 44.80; H, 6.68; N, 5.81. Found: C,
m
= 622 (P@S), 968, 992, 1026 (POC), 1207 (P@O),
Infrared spectra (Nujol) were recorded with a Specord M-80
spectrometer in the range 400–3600 cmꢁ1. NMR spectra were ob-
tained on a Varian Unity-300 NMR spectrometer at 25 °C. 1H and
31P{1H} spectra were recorded at 299.948 and 75.429 MHz, respec-
tively. Chemical shifts are reported with reference to SiMe4 (1H)
.
Anal. Calc. for
C
44.68; H, 6.79; N, 5.74.
2.2. Synthesis of ML2
and H3PO4 (
31P{1H}). Electronic spectra of absorption in 0.001 M
solution of CH2Cl2 were measured on a Perkin–Elmer Lambda-35
spectrometer in the range 200–1000 nm. Elemental analyses were
performed on a Perkin–Elmer 2400 CHN microanalyser.
A suspension of HL (0.241 g, 0.5 mmol) in aqueous ethanol
(20 mL) was mixed with an ethanol solution of potassium hydrox-
ide (0.031 g 0.55 mmol). An aqueous (20 mL) solution of ZnCl2,
Cd(CH3COO)2ꢀ2H2O, Co(NO3)2 ꢀ 6H2O (0.041, 0.080 or 0.087 g,
respectively; 0.3 mmol) was added dropwise under vigorous stir-
ring to the resulting potassium salt. The mixture was stirred at
room temperature for a further 3 h and left overnight. The result-
ing complex was extracted with dichloromethane, washed with
water and dried with anhydrous MgSO4. The solvent was then re-
moved in vacuo. The residue was recrystallized from a dichloro-
methane/n-hexane mixture.
2.5. Crystal structure determination and refinement
Crystals of HL were obtained by slow evaporation of the solvent
from dichloromethane/n-hexane solution.
Mr = 482.54 g mol–1
crystal system: monoclinic, space group:
P21/c, a = 7.6294(1), b = 9.3135(2), c = 35.2519(6) Å, b = 94.964
(1)°, V = 2495.48(8) Å3, = 1.284 g cm–3
Cell parameters and
intensities of 5931 independent reflections, from which 3689 with
I P 2 , were measured ( -scan, h 6 27.00°) at 296 K on a Bruker
Smart Apex II diffractometer and graphite-monochromatied Mo
radiation generated by fine-focus X-ray tube operated at
C18H32N2O5P2S2,
,
q
.
ZnL2. Complex was obtained as colorless crystals. Yield: 0.157 g
r
x
(61%). M.p. 163 °C. 1H NMR (CDCl3): d = 1.08–1.47 (m, 36H, CH3,
2
EtO + iPrO), 3.13 (d, JP,H = 21.1 Hz, 4H, CH2, P(O)CH2), 3.93–4.10
Ka
3
3
(m, 8H, OCH2, EtO), 4.79 (d. sept, JH,H = 6.2 Hz, JPOCH = 10.1 Hz,
50 kV and 30 mA. The images were indexed, integrated and scaled
4H, OCH, iPrO), 7.25–7.79 (m, 8H, C6H4), 6.53 (s, 2H, NH). 31P{1H}
using the Apex2 data reduction package [22]. Data were corrected
NMR (CDCl3): d = 24.9 (2P, P@O), 56.0 (2P, P@S). IR:
m = 603
for absorption using SADABS [23] program (l
Mo 3.71 cm–1). The
(P@S), 1008, 1012 (POC), 1263 (P@O), 1547 (S@C–N), 3305 (NH)
cm–1. Anal. Calc. for C36H62N4O10P4S4Zn (1028.44): C, 42.04; H,
6.08; N, 5.45. Found: C, 42.13; H, 5.91; N, 5.52.
structure was solved by direct method using SIR-97 [24] program
and refined first isotropically and then anisotropically using SHEL-
XL97 [25] and WINGX programs [26]. Hydrogen atoms were revealed
CdL2. Complex was obtained as colorless crystals. Yield: 0.231 g
from
Dq maps and refined isotropically. The final residuals were
(86%). M.p. 109 °C. 1H NMR (CDCl3): d = 1.17–1.51 (m, 36H, CH3,
R
ob = 0.0492, Rwob = 0.0903 based on 3689 independent reflec-
2
EtO + iPrO), 3.03 (d, JP,H = 21.8 Hz, 4H, CH2, P(O)CH2), 3.85–4.02
tions with F2 P 2
r. All figures were made using the program PLA-
3
3
(m, 8H, OCH2, EtO), 4.82 (d. sept, JH,H = 6.2 Hz, JPOCH = 10.3 Hz,
TON [27].
4H, OCH, iPrO), 7.27–7.72 (m, 8H, C6H4), 6.71 (s, 2H, NH). 31P{1H}
Crystals of Cu(PPh3)L were obtained by slow evaporation of the
NMR (CDCl3): d = 25.2 (2P, P@O), 56.2 (2P, P@S). IR:
m = 607
solvent from dichloromethane/n-hexane solution.
C36H46Cu-
(P@S), 1007 (POC), 1259 (P@O), 1539 (S@C–N), 3296 (NH) cm–1
.
N2O5P3S2, Mr = 807.32 g mol–1, crystal system: triclinic, space
Anal. Calc. for C36H62CdN4O10P4S4 (1075.46): C, 40.20; H, 5.81; N,
5.21. Found: C, 40.39; H, 5.73; N, 5.30.
ꢀ
group: P1, a = 8.9510(8), b = 11.5966(9), c = 20.0844(16) Å,
a =
77.572(6)°,
= 1.363 g cm–3. Cell parameters and intensities of 18274 reflec-
tions (7710 unique, Rint = 0.0822), from which 4594 had I P 2
were measured ( -scan, h 6 25.12°) at 173 K on a STOE IPDS-II dif-
fractometer and graphite-monochromatied Mo K radiation gener-
b = 77.538(6)°,
c
= 79.331(7)°,
V = 1966.8(3) Å3,
CoL2. Complex was obtained as green crystals. Yield: 0.233 g
q
(91%). M.p. 94 °C. IR:
m = 600 (P@S), 1012 (POC), 1260 (P@O),
r,
1551 (S@C–N), 3311 (NH) cm–1. UV–Vis spectra, [kmax, nm (
e,
x
1 mol–1 dm3cm–1)]: 558 (263), 607 (286), 668 (157). Anal. Calc.
for C36H62CoN4O10P4S4 (1021.99): C, 42.31; H, 6.11; N, 5.48. Found:
C, 42.47; H, 6.25; N, 5.41.
a
ated by fine-focus X-ray tube operated at 50 kV and 40 mA. The
images were indexed, integrated and scaled using the X-Area pack-
age [28]. Data were corrected for absorption using PLATON [27] pro-
gram (l
Mo 0.826 mm–1). The structure was solved by direct
2.3. Synthesis of Cu(PPh3)L
method using SHELXS [29] program and refined first isotropically
and then anisotropically using SHELXL97 [25]. Hydrogen atoms
A suspension of HL (0.241 g, 0.5 mmol) in aqueous ethanol
(15 mL) was mixed with an ethanol solution of KOH (0.031 g
0.55 mmol). A dichloromethane (15 mL) solution of Cu(PPh3)3I
were revealed from
Dq maps and refined using a riding model.
The final residuals were Rob = 0.0466, Rwob = 0.0801 based on

2980
D.A. Safin et al. / Polyhedron 27 (2008) 2978–2982
4594 independent reflections with F2 P 2
r. All figures were made
3.2. IR, UV–Vis and NMR spectroscopic data
using the program PLATON [27].
The IR spectrum of HL contains a weak band at 622 cmꢁ1 as-
signed to the P@S group. It is shifted to low frequencies
(600ꢁ607 cmꢁ1) in the spectra of complexes ML2 and Cu(PPh3)L
due to the coordination with the cation. Occurrence of the new
broad and strong absorption peak at 1530ꢁ1551 cmꢁ1, related to
the conjugated SCN group [30], also proves the formation of 1,5-
S,S0-chelate. Presence of the substituted POC groups in HL and its
complexes are seen in the IR spectra by their absorption bands at
3. Results and discussion
3.1. Synthesis
N-Thiophosphorylated thiourea HL was prepared by the addi-
tion of diethyl 4-aminobenzylphosphonate (EtO)2P(O)CH2C6H4-4-
NH2 to O,O’-diisopropylthiophosphoric acid isothiocyanate
(iPrO)2P(S)NCS (Scheme 1).
962ꢁ1026 cmꢁ1
.
There are two bands for the ArNH and P(S)NH groups at 3126
and 3272 cmꢁ1 in the IR spectrum of HL, whereas a unique band
at 3296ꢁ3311 and 3263 cmꢁ1 related to the ArNH group was ob-
served in the spectra of complexes ML2 and Cu(PPh3)L, respec-
tively. It should be noted that the band for the ArNH group in
the IR spectra of ML2 is shifted to high frequencies whereas in
Cu(PPh3)L this band is practically at the same frequencies relative
to the band of the parent ligand HL. The similar is observed for the
P@O absorption band in the IR spectra. The band at
1259ꢁ1263 cmꢁ1 in the spectra of ML2 corresponds to the P@O
group and shifted to high frequencies relative to that in HL. The
P@O band at 1257 cmꢁ1 in the IR spectrum of complex Cu(PPh3)L
is practically at the same area as it was observed in the parent thio-
urea (1252 cmꢁ1) due to the intermolecular NꢁHꢀꢀꢀO@P hydrogen
bonds in a crystal (Figs. 1 and 2). This confirms the preservation
of the hydrogen bonding in the structure of Cu(PPh3)L and absence
of it in complexes ML2.
Complexes of HL with the Zn(II) (ZnL2), Cd(II) (CdL2) and Co(II)
(CoL2) cations were prepared by the following procedure: ligand
was converted into potassium salt KL and followed by reaction
with ZnCl2, Cd(CH3COO)2 ꢀ 2H2O or Co(NO3)2 ꢀ 6H2O in aqueous
EtOH (Scheme 2).
Reaction of the potassium salt of HL with Cu(PPh3)3I in aqueous
EtOH/CH2Cl2 leads to mononuclear Cu(PPh3)L complex (Scheme
2).
The compounds obtained are colorless (HL, ZnL2 and CdL2) or
green (CoL2) crystalline powders, soluble in acetone, benzene,
dichloromethane and insoluble in water and n-hexane. UV–Vis,
1H, 31P{1H} NMR in solution and IR data indicated that the thiourea
HL is a 1,5-S,S0-ligand.
The 31P{1H} NMR spectrum of HL in a CDCl3 solution shows two
single resonances at 26.7 and 53.4 ppm, corresponding to the
phosphorus atoms of the P@O and P@S groups, respectively. In
the 31P{1H} NMR spectra of complexes ZnL2, CdL2 and Cu(PPh3)L,
the resonance for the phosphoryl and thiophosphoryl groups are
shown at 24.9ꢁ27.1 and 55.3ꢁ56.2 ppm, respectively. The signal
corresponding to the P@S group is low-field shifted, whereas the
singlet for the P@O group is practically at the same region relative
to those in the parent ligand for Cu(PPh3)L and low-field shifted in
the 31P{1H} NMR spectra of complexes ZnL2 and CdL2. The signal of
the triphenylphosphine group in copper(I) complex is shifted
downfield relative to the free PPh3 and exhibit 31P{1H} NMR
(EtO)2P CH2
O
NH2
S
C N P(OiPr)2
S
H
H
N
(EtO)2P CH2
N C
S
P(OiPr)2
O
S
HL
Scheme 1. Preparation of HL.
N
H
(EtO)2P CH2
O
N C
P(OiPr)2
S
S
M/2
M = Zn(II) (ZnL2); Cd(II) (CdL2); Co(II) (CoL2)
1. KOH
2. 1/2 M(II)
HL
1. KOH
2. Cu(PPh3)3I
Fig. 1. Molecular structure and hydrogen bonding dimer in crystal of HL. Selected
bond distances (Å) and angles (°): S(1)–P(1) 1.9166(11), S(2)–C(1) 1.657(3), P(1)–
O(1) 1.583(2), P(1)–O(2) 1.561(2), P(1)–N(1) 1.666(2), P(2)–O(3) 1.556(2), P(2)–
O(4) 1.570(2), P(2)–O(5) 1.469(2), N(1)–C(1) 1.376(3), N(2)–C(1) 1.346(3); S(1)–
P(1)–O(1) 115.73(8), S(1)–P(1)–O(2) 115.57(8), S(1)–P(1)–N(1) 118.90(8), O(1)–
P(1)–O(2) 102.92(9), O(1)–P(1)–N(1) 94.11(10), O(2)–P(1)–N(1) 106.58(11), O(3)–
P(2)–O(4) 105.24(10), O(3)–P(2)–O(5) 113.44(10), O(4)–P(2)–O(5) 113.67(11),
P(1)–N(1)–C(1) 126.8(2), S(2)–C(1)–N(1) 120.3(2), S(2)–C(1)–N(2) 127.1(2), N(1)–
C(1)–N(2) 112.6(2). The intermolecular hydrogen bond parameters in the molecule
are as follows: N(1)ꢁH(1)ꢀꢀꢀO(5)0(1–x, 1–y, –z): d(NꢁH) 0.81(3), d(HꢀꢀꢀO0) 2.26(3),
d(NꢀꢀꢀO0) 2.997(3), \(NHO0) 153(3); N(2)ꢁH(2)ꢀꢀꢀO(5)0 (1–x, 1–y, –z): d(NꢁH)
0.79(3), d(HꢀꢀꢀO0) 2.11(3), d(NꢀꢀꢀO0) 2881(3), \(NHO0) 167(3).
N
H
(EtO)2P CH2
O
N C
P(OiPr)2
S
S
Cu
PPh3
Cu(PPh3)L
Scheme 2. Preparation of ZnL2, CdL2, CoL2 and Cu(PPh3)L.

D.A. Safin et al. / Polyhedron 27 (2008) 2978–2982
2981
X-ray analysis of the product HL showed that the NC(S)N fragm-
net is almost planar, which is evidence of the resonance between
the nitrogen lone pair and the double C@S bond. The phosphorus
atoms have a distorted tetrahedral configuration typical of phos-
phates. The conformation of the N–C–N–P fragmnet is almost
shielded, torsion angle N(2)–C(1)–N(1)–P(1) is ꢁ173.8(2)°. The
bonds C(1)–S(2) and P(1)–S(1) are in anti-orientation. The mole-
cule of HL in the crystal has a syn-orientation of the bonds N(1)–
H(1) and N(2)–H(2) and an anti-orientation of the P(1)–N(1) and
N(2)–C(1) bonds. Such arrangement, apparently, is caused by the
formation of the intermolecular hydrogen bonds N(1)ꢁH(1)ꢀꢀꢀO(5)0
(1 ꢁ x, 1 ꢁ y, ꢁz), N(2)ꢁH(2)ꢀꢀꢀO(5)0 (1 ꢁ x, 1 ꢁ y, ꢁz) and
N(1)0ꢁH(1)0ꢀꢀꢀO(5), N(2)0ꢁH0ꢀꢀꢀO(5) (Fig. 1). As a result of the inter-
molecular interactions, a centosymmetric dimer is formed.
The molecular structure of complex Cu(PPh3)L is shown in Fig.
2. The geometry around the Cu atom is trigonal formed by two sul-
furs and one PPh3. S–P and S–C bonds are longer while P–N and N–
C are shorter in comparison to those for the free ligand HL and
have intermediate bond order values between the double and sin-
gle. The six-membered CuSPNCS metallocyle has the conformation
of a distorted boat with the P(1) an S(1) atoms showing the great-
est deviation from the least square plane of the CuSPNCS cycle,
0.4260(13) and ꢁ0.3256(13) Å, respectively. The fragment NC(S)NP
is almost planar, the sulfur of the thiophosphoryl group is signifi-
cantly deviated from the average plane of this fragment, torsion
angle S(1)ꢁP(1)ꢁN(1)ꢁ(1) is ꢁ57.5(4)°. The phosphorus atoms
have a distorted tetrahedral configuration.
Fig. 2. Molecular structure and hydrogen bonding dimer in crystal of Cu(PPh3)L.
Selected bond distances (Å) and angles (°): Cu(1)–S(1) 2.2485(11), Cu(1)–S(2)
2.2163(11), Cu(1)–P(3) 2.2142(11), S(1)–P(1) 1.9950(13), S(2)–C(1) 1.754(4), P(1)–
O(1) 1.583(3), P(1)–O(2) 1.588(3), P(1)–N(1) 1.600(3), P(2)–O(3) 1.579(4), P(2)–
O(4) 1.579(3), P(2)–O(5) 1.474(3), N(1)–C(1) 1.326(5), N(2)–C(1) 1.353(5); S(1)–
Cu(1)–S(2) 115.77(4), S(1)–Cu(1)–P(3) 118.63(4), S(2)–Cu(1)–P(3) 124.78(4),
Cu(1)–S(1)–P(1) 94.83(5), Cu(1)–S(2)–C(1) 104.63(13), S(1)–P(1)–O(1) 113.38(10),
S(1)–P(1)–O(2) 109.24(11), S(1)–P(1)–N(1) 118.28(13), O(1)–P(1)–O(2) 102.08(14),
O(1)–P(1)–N(1)
106.69(15),
O(2)–P(1)–N(1)
105.71(15),
O(3)–P(2)–O(4)
104.27(18), O(3)–P(2)–O(5) 115.38(19), O(4)–P(2)–O(5) 113.47(17), P(1)–N(1)–
C(1) 129.1(3), S(2)–C(1)–N(1) 128.4(3), S(2)–C(1)–N(2) 113.9(3), N(1)–C(1)–N(2)
117.6(3). The intermolecular hydrogen bond parameters in the molecule are as
follows: N(2)ꢁH(2)ꢀꢀꢀO(5)0 (1–x, 2–y, 1–z): d(NꢁH) 0.84(4), d(HꢀꢀꢀO0) 2.10(4),
d(NꢀꢀꢀO0) 2.922(4), \(NHO0) 164(4).
chemical shift at ꢁ0.9 ppm. In solution, the exchange between free
and bound triphenylphosphine group of complex Cu(PPh3)L re-
sults in a signal broadening of the 31P{1H} NMR spectrum, as it
was previously observed for the Cu(I) complexes with N-thi-
ophosphorylated thioureas and thioamides [31,32].
In a crystal two molecules of complex Cu(PPh3)L also form a
centrosymmetric dimer, which is caused by the formation of the
intermolecular hydrogen bonds N(2)ꢁH(2)ꢀꢀꢀO(5)0 (1 ꢁ x, 2 ꢁ y,
1 ꢁ z) (Fig. 2). As a result of the intermolecular interactions and
steric demanding, only one molecule of PPh3 is coordinated with
the Cu atom. Complex Cu(PPh3)L is the first example of copper(I)
complexes of N-thiophosphorylated thioureas and thioamides of
common formula RC(S)NHP(S)R02 and one molecule of PPh3.
The 1H NMR spectra of HL, ZnL2, CdL2 and Cu(PPh3)L contain a
set of signals, corresponding to the resulting products. The signals
for the CH3 protons of the (iPrO)2P(S) and (EtO)2P(O) groups are ob-
served as a doublet, triplet or multiplet at 1.08–1.51 ppm and a
doublet of septets, doublet of quartets or multiplet at 3.85–
4.86 ppm, corresponding to the OCH and OCH2 protons. The signals
for the C6H4 protons in the spectra of HL, ZnL2, CdL2 and Cu(PPh3)L
are shown as a multiplet at 7.25–7.79 ppm. The signals for the C6H5
protons in the 1H NMR spectrum of Cu(PPh3)L are observed as a
multiplet at 7.13–7.23 ppm. The CH2 protons doublet signals are
at 3.03–3.14 ppm. There is a doublet and singlet for the P(S)NH
and ArNH protons at 7.19 and 9.66 ppm, respectively, in the spec-
trum of HL, whereas only one singlet signal for the ArNH proton at
6.53–6.71 (ZnL2 and CdL2) and 8.47 [Cu(PPh3)L] ppm is observed
in the 1H NMR spectra of complexes. This confirms the anionic
forms L in the structure of complex.
4. Conclusions
In summary, novel Zn(II), Cd(II), Co(II) and Cu(PPh3)(I) com-
plexes with N-thiophosphorylated thiourea HL have been success-
fully synthesized. Copper(I) complex dissociates in a solution of
CDCl3, splitting off a molecule of triphenylphosphine. This process
has reversible character.
NMR and UV–Vis experiments in solution and IR have shown
that HL is a 1,5-S,S0-ligand in all complexes obtained.
Crystal structures of HL and Cu(PPh3)L were determined by sin-
gle crystal X-ray diffraction. According to the X-ray data, both li-
Investigation of complex CoL2 by NMR spectroscopy was not
successful, because of the paramagnetic Co(II) cation presence.
In the UV-spectrum of complex CoL2 there is an absorption
gand and complex in
a crystal form dimer structures by
intermolecular hydrogen bonds.
band with peaks at 558 (
e ,
max, 263 mol–1 dm3 cm–1), 607 (emax
286 mol–1 dm3 cm–1) and 668 (emax
,
157 mol–1 dm3 cm–1) nm.
5. Appendix A. Supplementary data
The specified absorption band corresponds to a transition from
the basic state 4A2 to a 4T1(P) state. The thin structure is caused
by spin–orbital interaction as a result of which, first, there is a
splitting of the state 4T1(P) and, secondly, there are resolved
transitions in the next doublet states with the same intensity.
Other possible transitions: 4A2 ? 4T2 and 4A2 ? 4T1(F) are outside
of the visible area. Data of UV-spectroscopy unequivocally con-
firm the tetrahedral environment of the Co(II) cation in complex
CoL2.
CCDC 680113 and 682359 contain the supplementary crystallo-
graphic data for (HL) and [Cu(PPh3)L]. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033;
or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgment
3.3. Crystal structures
This work was supported by the joint program of CRDF and the
Russian Ministry of Education and Science (BRHE 2008 Y5-C-07-
09); Russian Science Support Foundation.
According to the X-ray data, the molecule of HL in a crystal is
located in a special position at the symmetry centre (Fig. 1).

2982
D.A. Safin et al. / Polyhedron 27 (2008) 2978–2982
[16] L.G. Shaidarova, A.V. Gedmina, V.V. Brusko, N.G. Zabirov, N.A. Ulakhovich, G.K.
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