Synthesis and crystal structure of complexes of bipodal thiophosphorylated thioureas with divalent transition metals

Article abstract of DOI:10.1016/j.poly.2004.07.005

According to X-ray crystallography, the title compounds exist as metallomacrocycles in the crystal.

Full text of DOI:10.1016/j.poly.2004.07.005

Polyhedron 23 (2004) 2243–2252
www.elsevier.com/locate/poly
Synthesis and crystal structure of complexes of bipodal
thiophosphorylated thioureas with divalent transition metals
a,
a
b
Nail G. Zabirov *, Vasiliy V. Brusko , Alexander Y. Verat a,1, Dmitry B. Krivolapov ,
b
Igor A. Litvinov , Rafael A. Cherkasov
a
a
Department of Chemistry, Kazan State University, Kremlevskaya Street 18, 420008, Kazan, Russia
b
Arbusov Institute of Organic and Physical Chemistry, Arbuzov St. 8, 420088, Kazan, Russia
Received 7 November 2003; accepted 1 July 2004
Available online 28 August 2004
Abstract
New complexes of bipodal thiophosphorylated thioureas {[(iPrO)2P(S)NC(S)NH]2Z}M, where Z = m-C6H4, p-C6H4, M = Co,
Ni, Zn, Cd have been prepared and characterized. The crystal and molecular structures of Cd(II), Z = CH2CH2 and Pd(II),
Z = (CH2CH2)2O complexes have been determined by single crystal X-ray diffraction analyses. Both complexes are binuclear in
the solid state with a M2L2 stoichiometry. The cadmium and palladium atoms are four-coordinated and have the configuration
of a slightly distorted tetrahedron for cadmium and a distorted square plane for palladium. Metal-containing macrocycles are
formed as well as two spirocycles.
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: P,S-metallocycles; Supramolecular chemistry; Bipodal ligands; Crystal structures; Macrocycles; Phosphorylated urea complexes
1. Introduction
2. Experimental
We have recently reported the syntheses and com-
plexing properties of bipodal thiophosphorylated thiou-
reas [(iPrO)2P(S)NHC(S)NH]2Z, where Z = (CH2)2,
(CH2)7, (CH2)2O(CH2)2, (CH2)2O(CH2)2O(CH2)2, and
some properties of the chelate complexes formed by
these ligands with a series of metal ions [1,2].
In this paper, we report on the synthesis of the bis-
urea [(iPrO)2P(S)NHC(S)NH]2Z complexes with Co(II),
Ni(II), Zn(II) and Cd(II) (Z = m-C6H4, p-C6H4), to-
gether with the X-ray study of the bis-urea
[(iPrO)2P(S)NHC(S)NHCH2]2 and the complexes with
the cadmium(II) ion (1) (Z = CH2CH2) and the palla-
dium(II) ion (2) (Z = (CH2CH2)2O).
2.1. Synthesis of [(iPrO)2P(S)NHC(S)NH]2-m-C6H4
(3)
A solution of m-phenylenediamine (2.163 g, 0.02 mol)
in anhydrous benzene (50 ml) was added dropwise under
stirring to a benzene solution (25 ml) of diisopropylthio-
phosphoryl isothiocyanate (9.572 g, 0.04 mol). The mix-
ture was heated to 60 ꢁC and stirred for 2 h. The solvent
was removed in vacuum. A colourless precipitate was
crystallized from benzene. Yield: 8.33 g (ꢀ71%), m.p.
122 ꢁC. Anal. Calc. for C20H36N4O4P2S4: C, 40.95; H,
6.14; P, 10.58. Found: C, 41.58; H, 6.25; P, 10.30%.
3
1H NMR (C6D6) 1.33 (d, 24H, CH3, JHH 6.1 Hz),
3
4.78 (d, sept, 4H, OCH, JHH 6.3 Hz, JPOCH 10.7
3
2
Hz), 6.86 (d, 2H, NHP(S), JPH 9.8 Hz), 7.24 (t, 1H,
*
Corresponding author. Tel./fax: +7 8432 543734.
E-mail addresses: zabirov@mi.ru (N.G. Zabirov), averat@mail.ru
3
3
m-C6H4, JHH 8.2 Hz), 7.46 (d. d, 2H, m-C6H4, JHH
4
7.8 Hz, JHH 1.9 Hz), 8.14 (m, 1H, m-C6H4), 9.68 (s,
(A.Y. Verat).
1
Tel.: +7 8432 607654; fax: +7 8432 543734.
2H, C6H4NH). 31P{1H} NMR (ppm), 53.5. IR (cmꢁ1):
0277-5387/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2004.07.005

2244
N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
3430(s) (NH), 3190(br, s) (NH), 1550(s) (S@CAN),
1315(m) (C@S), 1000(vs) (POC), 980(vs) (POC),
655(m) (P@S).
was precipitated from methylene chloride by n-hexane.
Yield: ꢀ41%, m.p. 156 ꢁC. Anal. Calc. for C20H34Co-
N4O4P2S4: C, 37.29; H, 5.28; P, 9.63; Co, 9.15. Found:
C, 37.67; H, 5.72; P, 9.32; Co, 8.86%. 31P{1H} NMR
(acetone; ppm; width at half height, Hz; integral inten-
sity, %), 56.46 (58 Hz, 64.6%), 58.632 (79 Hz, 35.4%).
IR (cmꢁ1): 3350(s) (NH), 1550(s) (SCN), 970(br, vs)
(POC), 560, 580 (m) (P@S).
2.2. Synthesis of [(iPrO)2P(S)NHC(S)NH]2-p-C6H4
(4)
A solution of diisopropylthiophosphoryl isothiocya-
nate (9.572 g, 0.04 mol) in anhydrous benzene (25 ml)
was added dropwise under stirring to a solution of p-
phenylenediamine (2.163 g, 0.02 mol) in 50 ml of benzene
heated to 60 ꢁC. The mixture was refluxed with stirring for
3 h. n-Hexane (30 ml) was added, the mixture cooled down
to 0 ꢁC and then a white solid precipitated. The precipitate
was crystallized twice from benzene. Yield: 8.8 g (ꢀ75%),
m.p. 139 ꢁC. Anal. Calc. for C20H36N4O4P2S4: C, 40.95;
H, 6.14; P, 10.58. Found: C, 41.09; H, 6.25; P, 10.18%.
2.5. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-m-C6H4
Ni} (7)
This was prepared similarly to compound 6 by using
Ni(NO3)2 Æ 6H2O. Yield: ꢀ45%, m.p. 140 ꢁC. Anal. Calc.
for C20H34N4NiO4P2S4: C, 37.30; H, 5.28; P, 9.63; Ni,
9.12. Found: C, 37.22; H, 5.68; P, 9.98; Ni, 9.95%.
31P{1H} NMR (CH2Cl2; ppm; width at half height,
Hz; integral intensity, %), 51.20 (187 Hz, 51.3%), 53.05
(58 Hz, 36.6%), 54.40 (90 Hz, 12.1%). IR (cmꢁ1):
3345(s) (NH), 1545(s) (SCN), 975(br, vs) (POC), 573,
589(m) (P@S).
3
1H NMR (C6D6) 1.22 (d, 12H, CH3, JHH 6.0 Hz), 1.25
3
(d, 12H, CH3, JHH 6.4 Hz), 4.90 (d, sept, 4H, OCH,
3
3JHH 6.2 Hz, JPOCH 10.6 Hz), 6.50 (d, 2H, NHP(S),
2JPH 8.4 Hz), 7.83 (s, 4H, C6H4), 10.19 (s, 2H,
C6H4NH). 31P{1H} NMR (ppm), 53.28. IR (cmꢁ1):
3360(s) (NH), 3110(s) (NH), 1565(s) (S@CAN),
1335(m) (C@S), 980(vs) (POC), 655(m) (P@S).
2.6. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-m-C6H4
Zn} (8)
2.3. Synthesis of [(iPrO)2P(S)NHC(S)NHCH2]2 (5)
This was prepared similarly to compound 6 by using
ZnCl2. Yield: ꢀ84%, m.p. 150 ꢁC. Anal. Calc. for
C20H34N4O4P2S4Zn: C, 36.94; H, 5.23; P, 9.53; Zn,
10.06. Found: C, 37.16; H, 5.17; P, 9.24; Zn, 9.76%.
31P{1H} NMR ((CD3)2CO; ppm), 56.24. 1H NMR
The compound was prepared as described above for 3
from ethylenediamine (1.202 g, 0.02 mol, as an acetonit-
rile solution, 15 ml) and diisopropylthiophosphoryl
isothiocyanate (9.572 g, 0.04 mol) in benzene (25 ml)
to give 7.54 g (ꢀ70%, after crystallization from benzene)
of 5 as colourless crystals. M.p. 111 ꢁC. Anal. Calc. for
C16H36N4O4P2S4: C, 35.67; H, 6.74; P, 11.50. Found: C,
3
((CD3)2CO; ppm): 1.478 (d, 12H, JHH 5.5 Hz); 1.482
(d, 12H, 3JHH 6.0 Hz), 4.92 (d. sept, 4H, 3JPOCH 9.9 Hz;
3JHH 6.1 Hz), 7.44 (m, 3H, Ph); 8.15 (m, 1H), 9.59 (br.
4
d, 2H, JPNCNH 7.8 Hz). IR (cmꢁ1): 3340(br, s) (NH),
1
35.64; H, 6.67; P, 11.09%. H NMR (C6D6) 1.404 (d,
1520(s) (SCN), 1000(b, vs) (POC), 569, 595(m) (P@S).
3
12H, CH3, JHH 6.2 Hz), 1.409 (d, 12H, CH3, JHH 6.3
3
Hz), 3.97 (m, 4H, CH2CH2), 4.88 (d. sept, 4H, OCH,
3
2.7. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-m-
C6H4Cd} (9)
3JHH 6.3 Hz, JPOCH 10.4 Hz), 7.53 (d, 2H, NHP(S),
2JPH 8.3 Hz), 8.35 (br. s, 2H, CH2NH). 31P{1H} NMR
(ppm), 51.46. IR (cmꢁ1): 3440(s) (NH), 1560(s)
(S@CAN), 1315(m) (C@S), 1010(vs) (POC), 640(m)
(P@S).
This was prepared similarly to compound 6 by using
Cd(CH3COO)2 Æ H2O. Yield: ꢀ69%, m.p. 146–147 ꢁC.
Anal. Calc. for C20H34CdN4O4P2S4: H, 4.88; P, 8.88.
Found: H, 5.59; P, 8.20%. 31P{1H} NMR ((CD3)2CO;
ppm), 55.54. 1H NMR ((CD3)2CO; ppm): 1.496 (d.
2.4. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-m-C6H4
Co} (6)
3
3
12H, JHH 6.5 Hz); 1.471 (d, 12H, JHH 6.5 Hz), 4.92
3
3
(d. sept, 4H, JPOCH 10.2 Hz; JHH 6.1 Hz), 7.39 (m,
3H, Ph), 8.30 (m, 1H, Ph), 9.64 (br. d, 2H, NH, 4JPNCNH
8.2 Hz). IR (cmꢁ1): 3200(br, s) (NH), 1490(s) (SCN),
1005(br, vs) (POC), 573, 594(m) (P@S).
A suspension of 3 (1.173 g, 2 mmol) in anhydrous
ethanol (20 ml) was mixed with an ethanol solution of
potassium hydroxide (0.224 g, 4 mmol). To the resulting
potassium salt, a water (20 ml) solution of Co(NO3)2 Æ 6-
H2O (0.579 g, 2.2 mmol) was added dropwise with vig-
orous stirring. The mixture was stirred at room
temperature for a further 3 h and left overnight. The
resulting complex was extracted with methylene chlo-
ride, washed with water and dried over MgSO4. Then
the solvent was removed in vacuum. A green precipitate
2.8. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-p-
C6H4Co} (10)
A
[(iPrO)2P(S)NHC(S)NH]2-p-C6H4 in anhydrous ethanol
suspension of 1.173
g
(2 mmol) of
(20 ml) was mixed with an ethanol solution of potassium

N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
2245
hydroxide (0.224 g, 4 mmol). To the resulting potassium
salt, a water (20 ml) solution of Co(NO3)2 Æ 6H2O (0.579
g, 2.2 mmol) was added dropwise with vigorous stirring.
The resulting complex was extracted with methylene
chloride as a suspension and then the organic phase
was washed with water (20 ml). The solvent was re-
moved in vacuum. The residue was dried over MgSO4
as an acetone solution and the solvent was removed in
vacuum. A green solid was precipitated from acetone
by n-hexane and dried in vacuum at 50 ꢁC. Yield:
66%, m.p. 190–200 ꢁC, decomposes. Anal. Calc. for
C20H34CoN4O4P2S4: C, 37.29; H, 5.28; P, 9.63; Co,
9.15. Found: C, 36.60; H, 5.38; P, 11.94; Co, 11.37%.
31P{1H} NMR (CH2Cl2; ppm; width at half height,
Hz); 169.54 (341 Hz). IR (cmꢁ1): 3360(br, s) (NH),
1504(s) (SCN), 1000(br, vs) (POC), 568(m) (P@S).
10.04%. 31P{1H} NMR ((CD3)2CO; ppm), 56.39. 1H
3
NMR ((CD3)2CO; ppm): 1.475 (d, 24H, JHH 6.2 Hz),
3
4.90 (d. sept, 4H, JPOCH 10.2 Hz; JHH 6.1 Hz), 7.79
3
4
(s, 4H, Ph), 9.577 (d, 2H, NH, JPNCNH 8.2 Hz). IR
(cmꢁ1): 3280(br, s) (NH), 1500(s) (SCN), 980(br, vs)
(POC), 575(m) (P@S).
2.10. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-p-
C6H4Cd} (12)
This was prepared similarly to compound 10 by using
Cd(CH3COO)2 Æ H2O. Yield: ꢀ20%, m.p. 175 ꢁC. Anal.
Calc. for C20H34CdN4O4P2S4: C, 34.46; H, 4.88; P,
8.88; Cd, 16.12. Found: C, 34.71; H, 4.56; P, 9.06; Cd,
16.71%. 31P{1H} NMR ((CH3)2CO; ppm), 55.29. IR
(cmꢁ1): 3220(br, s) (NH), 1510(s) (SCN), 980–1000
(POC), 568(m) (P@S).
2.9. Synthesis of {[(iPrO)2P(S)NC(S)NH]2-p-
C6H4Zn} (11)
2.11. Physical measurements
This was prepared similarly to compound 10 by using
ZnCl2. Yield: ꢀ65%, m.p. 305 ꢁC, decomposes. Anal.
Calc. for C20H34N4O4P2S4Zn: C, 36.94; H, 5.23; P,
9.53; Zn, 10.06. Found: C, 36.60; H, 5.22; P, 9.89; Zn,
Infrared spectra (Nujol) were recorded on a Specord
M-80 spectrometer in the range 400–3600 cmꢁ1. NMR
spectra were obtained on a Varian Unity-300 NMR
spectrometer at 25 ꢁC. 1H and 31P spectra were recorded
Table 1
Crystal data, data collection and refinement parameters for 1, 2 and 5
1
2
5
Empirical formula
C
32H68N8O8P4S8Cd2
C36H76N8O10P4S8Pd2 Æ 2CH2Cl2
C16H36N4O4P2S4
Formula weight
Space group
Unit cell dimensions
1298.1
P21/n
772.03
ꢀ
538.69
P21/n
P1
˚
a (A)
15.297(2)
12.938(5)
9.883(4)
12.368(2)
10.556(2)
12.521(1)
˚
b (A)
˚
c (A)
30.089(5)
90
14.481(4)
73.75(2)
10.723(2)
90
a (ꢁ)
b (ꢁ)
c (ꢁ)
103.55(1)
90
5787(2)
82.74(3)
72.12(2)
1616(1)
103.41(1)
90
1378.5(4)
3
˚
V (A )
Z
4
1.49
1
1.59
2
1.30
Dcalc (g cmꢁ3
F(000)
)
664
792
orange
prismatic
572
colourless
prismatic
Crystal colour
Crystal form
Crystal size (mm)
colourless
prismatic
0.4 · 0.3 · 0.2
0.71073
294
0.4 · 0.3 · 0.4
0.71073
143
0.4 · 0.3 · 0.4
0.71073
294
˚
Radiation (A)
Temperature (K)
Scan mode
x/2h
33.76
x/2h
26.28
x
32.28
Recording range hmax (ꢁ)
Absorption correction
w-scans
11.81
none
11.3
none
4.9
l (cmꢁ1
)
Scan speed (ꢁ minꢁ1
Index ranges
)
Variable, 1-16.4
0 6 h 6 16, ꢁ16 6 k 6 0,
ꢁ36 6 l 6 37
11091
Variable, 1-16.4
ꢁ11 6 h 6 0, ꢁ15 6 k 6 13,
Variable, 1-16.4
0 6 h 6 12, 0 6 k 6 12,
ꢁ16 6 l 6 16
5944
3693
ꢁ13 6 l 6 13
No. of recorded reflections
Observed reflections F2 P 4r(Fo)
R (%)
Rw (%)
S
1895
784
6704
0.038
0.058
0.138
0.997
0.057
0.149
0.991
0.087
1.000

2246
N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
at 299.948 and 121.420 MHz, respectively. Chemical
shifts are reported with reference to SiMe4 (1H) and
H3PO4 (31P).
3.2. IR and NMR spectroscopy
The IR spectra of 1, 2, 6–12 exhibit absorptions at
450–300 cmꢁ1, which correspond to the stretching vibra-
tion of M–S bonds. The absorption band of the P@S
group is shifted from 630–655 cmꢁ1 in the parent ligands
to 560–595 cmꢁ1 in the complexes. The strong infrared
absorption observed for all complexes in the region
1490–1570 cmꢁ1 was assigned to the group vibrations
of the SCN fragment. The signal of the C(S)NHP(S)
2.12. Crystal structure determination and refinement
The crystals of 1 were obtained from the mixture of
dichloromethane and n-hexane (1:13) and the crystals
of 2 via the slow evaporation of solvent from a dichloro-
methane solution. At room temperature the crystals of
2, taken from the saturated solution, lose solvents mol-
ecules and destroy themselves.
1
group proton is absent in NMR H spectra. The signal
of the ZNH proton is shifted upfield with respect to
4
the same signal of free ligands. High JPNCNH coupling
The X-Ray diffraction data for the crystals of 1 and 2
were collected on a CAD4 Enraf-Nonius automatic dif-
fractometer using graphite monochromated Mo Ka
constants, about 8 Hz, were noted previously for the
complexes of N-diisopropoxyphosphoryl-N0-phenyl
thiourea [6]. Such a high constant can be explained by
the almost planar bond arrangement in the PNCNH
backbone and by the accordance of this fragment con-
figuration to the so-called W-criterion [7]. 31P NMR
spectra of complexes 1, 2, 6–9, 11 and 12 each show a
resonance in the region 51–59 ppm. As a rule the signals
are shifted downfield with respect to the parent ligands.
Obtained IR and NMR spectral data are evidence of the
chelate knot formation with participation of C@S and
P@S groups and the metal cation. Due to the presence
of the paramagnetic centres, the signals for the 1H
NMR spectrum of cobalt and nickel complexes 6, 7
and 10 are broadened and their number increased, this
makes assignment of the signals much more
complicated.
˚
(0.71073 A) radiation. Molecules of 2 and 5 in the crys-
tals are in special positions. The details of crystal data,
data collection and the refinement are given in Table 1.
The stability of the crystals and the experimental con-
ditions were checked every 2 h using three control reflec-
tions, while the orientation was monitored every 200
reflections by centreing two standards. No significant
decay was observed. An empirical absorption correction
based on w-scans was applied. The structures were
solved by direct methods using the SIR 92 [3] program
and refined using the SHELXL-97 program [4]. For the
crystals (1, 2, 5) all non-hydrogen atoms were refined
anisotropically. The positions of the hydrogen atoms
were idealised. All figures were made using the program
PLATON [5].
Divalent metals can form complexes of 1:1 ML A and
2:2 M2L2 B compositions with such a kind of bipodal
ligands. Formation of oligomeric or polymeric composi-
tions MnLn (C) is also possible.
3. Results and discussion
3.1. Synthesis
Ligands were prepared by the addition reaction of
bis-amines H2N–Z–NH2 to diisopropoxythiopho-
sphoryisothiocyanate (iPrO)2P(S)NCS.
M
M
M
M
M
n
A
B
C
H
N
H
N
NH
NH
Z
(i-PrO)2P
S
P(OPr-i)2
S
Thus, there is the possibility of an equilibrium in
solution between all described types of complexes. We
suppose that the equilibrium state depends first of all
on the bridging chain Z length and secondly on the nat-
ure of the metal.
The 31P NMR spectra of cobalt and nickel complexes
6, 7 and 10 show several (up to three) signals of different
intensities and widths at half height, which correspond
to the different metal cation environments in the com-
plexes. Such behaviour is common of the other com-
plexes of bipodal thiophosphorylated thiourea [1]. The
nickel cation has a cis-square-planar coordination envi-
ronment in a dimer B and a trans-square-planar in an
oligomer C. Nickel can also stay tetrahedral. Moreover,
Ni(II) cations can be coordinated by lone pair donors,
S
S
3–5
Complexes of [(iPrO)2P(S)NHC(S)NH]2(m-C6H4) and
[(iPrO)2P(S)NHC(S)NH]2(p-C6H4) with Co(II), Ni(II),
Zn(II) and Cd(II) 6–12 were prepared by the following
procedure: the ligands were converted to their potassium
salts, followed by interaction with inorganic salts of the
corresponding metals. The obtained compounds are crys-
talline solids, soluble in most polar solvents. According to
elemental analyses, they have a ratio M/L = 1:1. Com-
plexes of bis-urea [(iPrO)2P(S)NHC(S)NH]2(p-C6H4)
are unstable in solution, in the presence of moisture,
alcohols and air oxygen.

N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
2247
such as nitrogen or oxygen, which are present in the lig-
and molecules. Different signals in the phosphorus spec-
trum of 7 can be due to any of proposed forms.
Cobalt(II) cations are usually tetrahedral, but they can
also form adducts with donor molecules.
The crystal structure of 5 is shown in Fig. 1, selected val-
ues of bond lengths, bond and torsion angles are given
in Table 2. The NC(S)N fragment is almost planar,
which is evidence of the resonance between the nitrogen
lone pair and the double C@S bond. The conformation
of the P–N–C–N fragment is almost shielded, torsion
\P(1)–N(1)–C(1)–N(2) = 8.5(1)ꢁ. The NH group pro-
tons stay in an anti-disposition. The molecule has an
inversion centre (see Table 3).
In the crystals of bisthiourea intra- and inter-molecu-
lar H-bonds of the NHꢂ ꢂ ꢂS type were found. Their
parameters are presented in Table 3. Intermolecular
H-bonds form endless chains. In the crystal these chains
are oriented parallel to each other, along the OY axis.
31P NMR spectra of complexes 1, 8, 9, 11 and 12 ex-
hibit only one signal. Cd(II) and Zn(II) cations are dia-
magnetic and their signals in 31P NMR spectra are less
sensitive to the environment of the metal cation. That
is why both forms can have the same chemical shift.
In contrast to nickel, palladium(II) does not give a
tetrahedral form or adducts and cis- and trans-isomers
have different signals in spectra, as shown for the com-
plex of N-diisopropoxythiophosphoryl-N0-phenylthio-
urea with Pd(II) [6]. Nonetheless, the 31P spectrum of
compound 2 shows a single resonance, which could cor-
respond to the binuclear complex as the only form pre-
sent in solution.
3.4. Crystal structures of 1 and 2
Figs. 2 and 3 show the structures of 1 and 2, respec-
tively, selected values of bond lengths, bond and torsion
angles are given in Tables 4 and 5. For compound 1 only
the data concerning one chelate knot are presented. The
second one has a very similar geometry. According to
the X-ray data these complexes are of M2L2 structure.
3.3. Crystal structure of 5
Ligand 5 has been studied by X-ray analysis in order
to compare its structure with the structures of 1 and 2.
Fig. 1. Molecular structure of 5.
Table 2
˚
Selected bond distances (A), bond and torsion angles (ꢁ) for the ligand 5
Bond distances
P(1)–S(1)
S(2)–C(1)
P(1)–O(2)
P(1)–O(3)
N(1)–H(1)
1.921(4)
1.683(6)
1.546(5)
1.522(6)
0.8597
P(1)–N(1)
N(1)–C(1)
N(2)–C(1)
N(2)–H(2)
1.684(5)
1.382(7)
1.306(8)
0.8597
Bond angles
S(1)–P(1)–N(1)
P(1)–N(1)–C(1)
S(2)–C(1)–N(1)
P(1)–N(1)–H(1)
117.0(2)
N(1)–C(1)–N(2)
S(2)–C(1)–N(2)
C(1)–N(2)–C(2)
C(1)–N(1)–H(1)
117.5(5)
124.0(5)
125.3(5)
116.23
127.5(4)
118.5(5)
116.22
Torsion angles
P(1)–N(1)–C(1)–N(2)
P(1)–N(1)–C(1)–S(2)
8.5(1)
–170.9(4)
S(1)–P(1)–N(1)–C(1)
–52.7(7)

2248
N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
Table 3
Parameters of H-bonds in the bisthiourea 5
Bond
Symmetry operation
d(D–H)
d(Hꢂ ꢂ ꢂA)
2.62
2.59
d(Dꢂ ꢂ ꢂA)
3.467(4)
3.332(6)
\(DHA)
N1–H1ꢂ ꢂ ꢂS2
N2–H2ꢂ ꢂ ꢂS1
Bond lengths in A and bond angles in degrees.
ꢁx, 1 ꢁ y, 1 ꢁ z
0.86
0.86
170.0
145.0
intramolecular
˚
Each ligand ‘‘tail’’ covers only its own metal atom. The
coordination sphere of the metal includes a second lig-
and molecule. The structures of the described complexes
are similar to the structures of the complexes of para-
phenylene bis(imines) and para-phenylene methylpyri-
dines [8,9]. In the crystal of compound 1 there is only
the independent molecule in the asymmetric part of
the lattice. In compound 2 the molecule is in a special
position respective to the centre of symmetry. The cad-
mium and palladium atoms are four-coordinated and
have the configuration of a slightly distorted tetrahe-
dron for cadmium and a distorted square plane for pal-
ladium. The tetrahedral configuration of the cadmium
atoms in compound 1 resembles those previously found
in imidobis-seleno-[Ph2P(Se)NP(Se)Ph2]2Cd [10] and -
thiophosphinyl [iPr2P(S)NP(S)iPr2]2Cd [11] cadmium
complexes. They have a bis-chelate structure with a tet-
rahedral configuration of the central atom.
In compound 1 the Cd–S(C) bond lengths range from
˚
2.527(1) to 2.536(1) A, and Cd–S(P) bond lengths range
˚
from 2.503(2) to 2.523(1) A. This reveals the equaliza-
tion of the metal bond lengths with either the thiophos-
phoryl or the thiocarbonyl sulfur atoms. The values of
˚
the P–S (1.990 A mean) and C–S (1.760 A mean) bond
˚
Fig. 2. Molecular structure of complex 1.
Fig. 3. Molecular structure of complex 2.

N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
2249
Table 4
lengths also correspond to the values intermediate be-
˚
˚
thioureas) and the single (P–S 2.05–2.11 A, C–S 1.751
˚
Selected bond distances (A), bond and torsion angles (ꢁ) for complex 1
˚
tween double (P@S 1.91–1.92 A, C@S 1.68 A in the
Bond distances
Cd(1)–S(1)
Cd(1)–S(3)
S(1)–P(1)
S(2)–C(1)
P(1)–N(1)
N(1)–C(1)
2.522(1) Cd(1)–S(2)
2.522(1) Cd(1)–S(4)
1.989(2) S(3)–P(2)
1.764(4) S(4)–C(2)
1.603(4) P(2)–N(3)
1.310(5) N(3)–C(2)
2.536(1)
2.532(1)
1.986(2)
1.758(4)
1.595(4)
1.317(6)
˚
A) bonds [12]. The P@S bonds order stays in agreement
with IR spectroscopy observations. Meanwhile, the C–
N and P–N bonds are shorter on comparison with those
˚
in the free ligand 5 (C–N 1.382(7), P–N 1.684(5) A). This
picture is characteristic for the complexes discussed.
The metal-containing heterocycles CdSPNCS have
the conformation of a non-symmetric boat, with the
most deviation of P and S(C) atoms from the mean
square planes of these fragments (Table 6).
In complex 2 the palladium atom has a distorted
square-planar configuration. The deviations of the S(1)
and S(4a) atoms from the plane S(1)S(2)S(3a)S(4a) are
Bond angles
S(1)–Cd(1)–S(2)
S(3)–Cd(1)–S(4)
S(1)–Cd(1)–S(3)
Cd(1)–S(1)–P(1)
Cd(1)–S(3)–P(2)
P(1)–N(1)–C(1)
S(1)–P(1)–N(1)
S(2)–C(1)–N(1)
100.62(4)
S(2)–Cd(1)–S(4)
S(1)–Cd(1)–S(4)
S(2)–Cd(1)–S(3)
Cd(1)–S(2)–(1)
Cd(1)–S(4)–(2)
P(2)–N(3)–C(2)
S(3)–P(2)–N(3)
S(4)–C(2)–N(3)
105.68(4)
118.96(4)
117.22(4)
92.9(1)
103.49(4)
111.47(5)
97.84(5)
96.49(7)
127.9(3)
116.4(1)
126.4(3)
92.2(1)
128.7(3)
115.7(1)
127.0(3)
˚
ꢁ0.147(2) and ꢁ0.154(2) A, respectively, S(2) and
˚
S(3a) atoms are 0.158(2) and 0.154(2) A, respectively.
The palladium atom deviates from the plane
Torsion angles
˚
S(1)S(2)S(3a)S(4a) by 0.0305(6) A. The Pd–S(C) and
Pd–S(P) bond lengths are within the usual limits for
bonds of these kinds. For example, in the complex
P(1)–N(1)–C(1)–S(2)
S(1)–P(1)–N(1)–C(1) ꢁ68.9(4)
ꢁ1.1(5)
P(2)–N(3)–C(2)–S(4)
S(3)–P(2)–N(3)–C(2) ꢁ67.3(4)
ꢁ8.5(6)
˚
[PhC(S)NP(S)(OiPr)2]2Pd (13) Pd–S(C) is 2.310 A and
˚
Pd–S(P) is 2.341 A [13]. The Pd–S(P) bond lengths in
the compounds Pd[(EtO)2P(S)NP(S)Ph2]2 (14) [14],
Pd[{(PhO)2P(S)}2N]2 [15], Pd[{iPr2P(S)}2N]2 [16] are in
˚
the range 2.325–2.351 A. The Pd–S(C) bond lengths in
the complex Pd[Et2NC(S)NC(O)Ph]2 (15) are 2.310–
Table 5
˚
Selected bond distances (A), bond and torsion angles (ꢁ) for complex 2
Bond distances
Pd(1)–S(1)
Pd(1)–S(2)
S(1)–P(1)
S(2)–(1)
2.342(2) Pd(1)–S(3)
2.289(2) Pd(1)–S(4)
2.004(3) S(3)–P(2)
1.733(8) S(4)–(2)
1.580(6) P(2)–N(3)
1.333(9) N(3)–C(2)
2.354(2)
2.296(2)
1.993(3)
1.739(8)
1.579(6)
1.319(9)
˚
2.315 A [17]. The values of the bond lengths also show
the equalization of the bond lengths, but in contrast to
complex 1, there is an evident difference between the
bonds M–S(P) and M–S(C) in complex 2.
P(1)–N(1)
N(1)–C(1)
The metal-containing six-membered heterocycle
Pd(1)S(1)P(1)N(1)C(1)S(2) is in a ‘‘sofa’’ conformation.
The conformation of the second metal-containing heter-
ocycle Pd(1)(ꢁx, ꢁy, 1 ꢁ z)S(3)P(2)N(3)C(2)S(4) is a
non-symmetric boat, see Table 7. The conformation of
the SCNPS backbone in 1 and 2 is similar: the NC(S)NP
fragment is almost planar and the phosphoryl sulfur is
deviated from its least-square plane. Torsion S–P–N–C
angles range from 67.3(4)ꢁ to 72.3(5)ꢁ for 1 and
23.2(8)ꢁ to 48.4(7)ꢁ for 2. The values of torsion angles
in compounds 1 and 2 show that these deviations are
higher in the cadmium complex 1.
Bond angles
S(1)–Pd(1)–S(2)
S(1)–Pd(1)–S(3)
Pd(1)–S(1)–P(1)
Pd(1)–S(2)–C(1)
P(1)–N(1)–C(1)
S(1)–P(1)–N(1)
S(2)–C(1)–N(1)
96.05(7)
85.26(7)
99.48(9)
115.0(2)
128.9(5)
119.0(2)
129.9(6)
S(2)–Pd(1)–S(4)
80.31(7)
99.32(7)
97.57(9)
115.4(3)
126.5(5)
117.1(2)
129.7(6)
S(3)–Pd(1)–S(4)
Pd(1)–S(3)–P(2)
Pd(1)–S(4)–C(2)
P(2)–N(3)–C(2)
S(3)–P(2)–N(3)
S(4)–C(2)–N(3)
Torsion angles
P(1)–N(1)–C(1)–S(2)
S(1)–P(1)–N(1)–C(1)
15(1)
23.2(8)
P(2)–N(3)–C(2)–S(4)
S(3)–P(2)–N(3)–C(2) ꢁ48.4(7)
ꢁ2(1)
Table 6
˚
Deviations (A) from the mean-square planes CdSPNCS in 1
Atoms in plane
Deviation
Atoms in plane
Deviation
Atoms in plane
Deviation
Atoms in plane
Deviation
Cd(1)
S(1)
ꢁ0.4825
0.0958
0.4879
Cd(1)
S(3)
ꢁ0.3911
ꢁ0.1801
0.5063
Cd(2)
S(5)
ꢁ0.4419
ꢁ0.1369
0.5083
Cd(2)
S(7)
ꢁ0.3636
ꢁ0.2061
0.5205
P(1)
N(1)
C(1)
S(2)
P(2)
N(3)
C(2)
S(4)
P(3)
N(5)
C(3)
S(6)
P(4)
N(7)
C(4)
S(8)
ꢁ0.3018
ꢁ0.2765
0.6687
ꢁ0.2614
ꢁ0.3098
0.6360
ꢁ0.3009
ꢁ0.2779
0.6493
ꢁ0.2652
ꢁ0.3045
0.6189

2250
N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
Table 7
Deviations (A) from the mean-square planes PdSPNCS in 2
Table 8
Parameters of intramolecular H-bonds of the complex 1
˚
Atoms in plane
Deviation
Atoms in plane
Deviation
Bond
d(D–H)
d(Hꢂ ꢂ ꢂA)
d(Dꢂ ꢂ ꢂA)
\(DHA)
Pd(1)
S(1)
ꢁ0.4537
0.5521
Pd(1)
0.2818
0.5275
N2–H2ꢂ ꢂ ꢂS8
N4–H4ꢂ ꢂ ꢂS6
N6–H6ꢂ ꢂ ꢂS4
N8–H8ꢂ ꢂ ꢂS2
0.86
0.86
0.86
0.86
2.66
2.69
2.82
2.63
3.504(3)
3.529(4)
3.662(4)
3.477(3)
168.0
167.0
167.0
170.0
S(3) (ꢁx, ꢁy, 1 ꢁ z)
P(2) (ꢁx, ꢁy, 1 ꢁ z)
N(3) (ꢁx, ꢁy, 1 ꢁ z)
C(2) (ꢁx, ꢁy, 1 ꢁ z)
S(4) (ꢁx, ꢁy, 1 ꢁ z)
P(1)
N(1)
C(1)
S(2)
ꢁ0.2806
ꢁ0.0894
0.1879
ꢁ0.4083
0.0435
0.2021
˚
Bond lengths in A and bond angles in degrees.
0.0837
ꢁ0.0829
intramolecular H-bonds take place (Fig. 5). The H-
bonds parameters of complexes 1 and 2 are presented
in Tables 8 and 9. As a result of hydrogen bonding in
2 centrosymmetric dimers are formed. Since the first
molecule of the dimer lies in the local symmetry centre,
the second molecule is linked to another dimerꢀs mole-
cule. Finally, due to this interaction the dimers are
linked into endless chains.
In the crystal of complex 1 intramolecular H-bonds
of the NHꢂ ꢂ ꢂS type were found (Fig. 4). In contrast to
complex 1, in the crystal of complex 2 both inter- and
The nature of the close chemical environment of the
central atom imposes a major impact on the chelate
knot structure. If these atoms are the same then the
square-planar complexes of ‘‘soft’’ metals with anionic
ligands of the [A(X)NB(Y)] type have, as a rule, a
trans-structure: 13 [13], 14 [14], [PhNHC(S)-
NP(S)(OiPr)2]2Ni [18], [Pr2NC(S)NP(S)(OPh)2]2Ni [19],
[MeNHC(S)NP(S)Ph2]2Ni
[20],
[(EtO)2P(S)NP(S)-
Ph2]2Pt [14], [Me2P(S)NP(S)Ph2]2Ni [21], [Et2NC(S)-
NC(S)Ph]2Ni [22]. The only exception is the complex
{[H2NC(S)NP(S)Ph2]2Pt}(Et2O) [23]. If X ¼ Y the cis-
structure is preferable due to the trans-influence: 15
[17], [Et2NC(S)NC(O)Ph]2Cu [24], [Ph2P(Se)NP(O)-
Ph2]2Pd [25], [(iPrO)2P(O)NC(S)Ph]2Cu [26], [(iPrO)2-
P(O)NC(S)NEt2]2Cu [27]. The central atomꢀs surround-
ings affects in turn the structure of the macrocyclic
complexes with bipodal ligands. For example the dimer
Fig. 4. H-bonds in complex 1.
Fig. 5. H-bonds in complex 2.

N.G. Zabirov et al. / Polyhedron 23 (2004) 2243–2252
2251
Table 9
Parameters of H-bonds of the complex 2
Bond
Symmetry operation
d(D–H)
d(Hꢂ ꢂ ꢂA)
2.34
1.99
d(Dꢂ ꢂ ꢂA)
3.177(7)
2.823(8)
\(DHA)
N2–H2ꢂ ꢂ ꢂO3
N4–H4ꢂ ꢂ ꢂO5
Bond lengths in A and bond angles in degrees.
Intramolecular
1.00
0.86
141.0
164.0
ꢁx, 1 ꢁ y, ꢁz
˚
and trimer complexes with bipodal O,S-acylthioureas
have the cis-structure only [28,29].
[2] V.V. Brusꢀko, F.D. Sokolov, N.G. Zabirov, R.A. Cherkasov, A.I.
Rakhmatullin, A.Yu. Verat, Russ. J. Gen. Chem. 69 (1999) 664.
[3] A. Altomare, G. Cascarano, C. Giacovazzo, D. Viterbo, Acta
Crystallogr. A 47 (1991) 744.
Ligands having coordinating atoms with similar do-
nor abilities can form both cis- and trans-isomers
depending on slight peculiarities like the entropy of an
isomer, steric preferences, polarity of media. Hence, it
is evident, why the complexes with S,S-bipodal ligands
form both polymers [1,2] and dimers as in this case.
When there is a tendency to form chelate molecules with
a trans-structure, the minimal accepted size for the cyclic
molecule (ML)n should be n = 4.
The results of the presented work are in a good agree-
ment with the data published by Kluiber and Lewis [30],
Kobuke and Satoh [31], – both the dimeric complexes 1
and 2 are formed with ligands that contain less than 7
atoms in the bridging chain Z.
[4] G.M. Sheldrick, SHELX-97 Program for Crystal Structure Anal-
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[8] B.J. McNelis, L.C. Nathan, C.J. Clark, J. Chem. Soc., Dalton
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[10] V. Garcia-Montalvo, J. Novosad, P. Kilian, J.D. Woollins,
A.M.Z. Slawin, P. Garcia y Garcia, M. Lopez-Cardozo, G.
Espinosa-Perez, R. Cea-Olivares, J. Chem. Soc., Dalton Trans.
(1997) 1025.
[11] D. Cupertino, R. Keyte, A.M.Z. Slawin, D.J. Williams, J.D.
Woollins, Inorg. Chem. 35 (1996) 2695.
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Acknowledgements
[14] D.C. Cupertino, R.W. Keyte, A.M.Z. Slawin, J.D. Woollins,
Polyhedron 18 (1998) 311.
Financial support from the Russian Foundation for
Basic Research (Grants #00-03-32742 and 03-03-
32372-a) and joint program of CRDF and Russian Min-
istry of Education ‘‘Basic Research & High Education’’
(Grant REC-007) is gratefully acknowledged.
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Chem. 619 (1993) 1147.
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Appendix A. Supplementary material
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Chem. 586 (1990) 136.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre CCDC Nos. 189278, 189279 and 218902.
Copies of the data can be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: +44-(1223)-336033; e-mail: depos-
it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.a-
c.uk). Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.poly.2004.07.005.
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