Versatile coordination of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide towards Zn(II) and Cd(II)

Article abstract of DOI:10.1016/j.poly.2009.03.007

Reaction of the potassium salt of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide p-BrC₆H₄C(S)NHP(O)(OiPr)₂ (HL) with Zn(II) and Cd(II) cations in aqueous EtOH leads to the three different complexes: [Zn(L-O,S)₂

Full text of DOI:10.1016/j.poly.2009.03.007

Polyhedron 28 (2009) 1504–1510
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Versatile coordination of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide
towards Zn(II) and Cd(II)
a
a
b
c
Damir A. Safin a, , Axel Klein , Maria G. Babashkina , Heinrich Nöth , Dmitriy B. Krivolapov ,
*
Igor A. Litvinov c, Henryk Kozlowski d
a Institut für Anorganische Chemie, Universität zu Köln, Greinstrasse 6, D-50939 Köln, Germany
b A.E. Arbuzov Institute of Organic and Physical Chemistry, Arbuzov Street 8, 420088, Kazan, Russian Federation
c Department Chemie und Biochemie der Universität München, Butenandtstrasse 5-13 (Haus D), D-81377 München, Germany
d Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie Street 14, 50383, Wroclaw, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of the potassium salt of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide p-
BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Zn(II) and Cd(II) cations in aqueous EtOH leads to the three different
complexes: [Zn(L-O,S)2] (1), [Cd(p-BrC6H4C(S)NH2-S)(L-O,S)2] (2) and [Cd(HL-O)2(L-O,S)2] (3). The struc-
tures of these compounds were investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P
NMR spectroscopy, MALDI TOF spectrometry, and microanalysis. The Zn(II) atom in complex 1 is in a dis-
torted tetrahedral O2S2 environment formed by the C@S sulfur atoms and the P@O oxygen atoms of two
deprotonated ligands. Complex 2 has a trigonal-bipyramidal coordination core, Cd(Oax)2(Seq)3, and two
deprotonated ligand molecules L are coordinated in the axial positions through the oxygen atoms of
the P@O groups. The trigonal plane is formed by the sulfur atoms of two anionic ligands and one p-bro-
mothiobenzamide. The Cd(II) cation in complex 3 has an octahedral environment, (Oax)2(Oeq)2(Seq)2, with
two neutral ligand molecules coordinated in the axial positions through the oxygen atoms of the P@O
groups. The equatorial plane is formed by two anionic ligands in a typical 1,5-O,S-coordination mode.
The corresponding neutral and deprotonated ligands are in a trans disposition.
Received 19 January 2009
Accepted 2 March 2009
Available online 18 March 2009
Keywords:
Cadmium
Zinc
Crystal structure
Luminescence
Thiobenzamide ligands
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
diethyl-N’-benzoylthio(seleno)urea as SSPs was published by Koch
et al. [18].
Complexes of late transition metal cations are of great interest
as precursors for novel materials with nanosized structures [1–
22]. During the last years symmetric or asymmetric organic and
organoelement compounds with the A and B fragments (acetates,
carbamates, imides, phosphites, phosphinates, phosphonates,
phosphates, imidodiphosphites, imidodiphosphinates, imi-
dodiphosphonates, and imidodiphosphates) (Chart 1) have found
application as single-source precursors (SSPs) for the synthesis of
thin films, nanocrystals, and semiconductors [13–18]. In this con-
nection the syntheses of new potential SSPs remains actual to this
day.
In the literature there are many examples of SSPs, representing
Group 12 metal complexes with ligands of common formulas
R0R00P(X)–N(H)–P(Y)R0R00 and RC(X)–N(H)–C(Y)R0 [16–18]. Com-
pounds with X, Y = S and/or Se have been extensively studied,
whereas the corresponding oxygen derivatives are still poorly
investigated. Recently, utilization of Cd(II) complexes with N,N-
Our scientific groups have been investigating complexes of N-
(thio)phosphorylated (thio)amides and (thio)ureas RC(X)NHP(Y)R2
(HZ), containing various functional substituents [23–45]. HZ con-
tain X, Y donor atoms and an amido nitrogen atom which can be
involved in complexation. In terms of reactivity HZ compounds
are quite different from each other depending on the nature and
combination of atoms X and Y in the molecule, as well as the nat-
ure of substituents of (thio)carbonyl and (thio)phosphoryl moie-
ties. We possess ample knowledge on the complexation
properties of dithioderivatives HZ (X = Y = S). These compounds
usually form stable chelate complexes with d-metal cations, con-
taining a tetrahedral [M(II) = Co(II), Zn(II), Cd(II)] [24–34] or planar
[M(II) = Ni(II), Pd(II), Pt(II)] [34–38] MS4 core. The anionic form Z
behaves as a bidentate ligand.
Substitution of one sulfur atom in the central coordination
sphere by an oxygen atom lowers the degree of stabilization of
p-interactions. As a result, the MO2S2 core is less stable than the
MS4 fragment. Because of this, HZ with X = S and Y = O can show
significant changes in complexation properties as compared with
dithiophosphoryl analogs.
* Corresponding author.
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.2009.03.007

D.A. Safin et al. / Polyhedron 28 (2009) 1504–1510
1505
R''
P
turns out to be considerably less stable than that of CdS4 or ZnO2S2.
As a result, the complexes are hydrolytically unstable and tend to
increase the coordination number of the central atom even in dry
solvents [24,25].
C
X
A
R
R'
Y
B
We assume that the reason for the propensity of Cd(II) com-
plexes to hydrolysis is the formation of dimeric molecules
[Cd2L4] in the aqueous ethanol medium:
X, Y = O, S, Se
R, R', R'' = alkyl, aryl, O-alkyl, O-aryl, N-alkyl2, N-aryl2
Chart 1.
2CdðCH3COOÞ2 þ 4KL ! ½Cd2L4ꢀ þ 4CH3COOK
½Cd2L4ꢀ ¡ 2CdL2
ð1Þ
In this contribution we report the synthesis, structures, and
chemical properties of complexes of N-(diisopropoxyphosphoryl)-
p-bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) [45] with
Zn(II) ([Zn(L-O,S)2], 1) and Cd(II) ([Cd(p-BrC6H4C(S)NH2-S)(L-O,S)2],
2; [Cd(HL-O)2(L-O,S)2], 3) cations. In the ligand HL both –C(X)R and
–P(Y)R0R00 functional groups are combined (X = S, Y = O, R = p-C6H4,
R0 = R00 = OiPr), and bonded by the NH fragment. The phosphory-
lated thiobenzamide HL is easily deprotonated in alkaline medium,
leading to a thioamide with the negative charge delocalized in the
O–P–N–C–S backbone [23].
The structure of a similar dimeric complex 5 was reported earlier
[24]. In the dimeric molecule of composition [Cd2Q4] the complex
units [CdQ2] are connected by bridging Cd–S–Cd bonds (Scheme 2).
X-ray data have shown that the cyclic bonds in the bridging tri-
dentate ligands Q are significantly elongated in comparison with
terminal bidentate ones. Decrease of the electron density, intro-
duced by the electron-withdrawing effect of the two Cd(II) cations
might result in the facilitation of the nucleophilic attack of H2O
molecules and, thus, promote hydrolysis. An assumed reaction of
that type is shown in the following equation:
The luminescence properties of the novel compounds and pre-
viously described [24] complexes of thiobenzamide C6H5C(S)-
NHP(O)(OiPr)2 (HQ) with Zn(II) and Cd(II) cations: [Zn(Q-O,S)2]
(4), [Cd2(Q-O,S)4] (5), [Cd(HQ-O)2(Q-O,S)2] (6), were also measured.
½Cd2L4ꢀ þ 3H2O ! ½CdL2ꢀ þ p-BrC6H4CðSÞNH2
þ ðiPrOÞ2PðOÞOH þ CdðOHÞ2 þ HL
ð2Þ
Recently, we have established [24] that the complex 5 is unsta-
ble in solution and dissociates to the mononuclear complexes.
However, even if the equilibrium is almost quantitatively shifted
to the right (Eq. (1)), the small amount of easily hydrolyzing dimer
molecules could provide the accumulation of the hydrolysis prod-
uct in the reaction mixture. Interestingly, Zn(II) complexes exhibit
no dimer formation under the same reaction conditions.
2. Results and discussion
The ligand HL was prepared by the reaction of p-bromothioben-
zamide p-BrC6H4C(S)NH2 with diisopropyl chlorophosphate
(iPrO)2P(O)Cl [45]. The product was carefully purified by extraction
and recrystallization, and it definitely contains no traces of starting
thioamide according to the spectral and microanalysis data.
Complexes 1–3 were prepared by the following procedure: the
ligand was deprotonated in situ using KOH, followed by reaction
with salts of the corresponding metals. The compounds obtained
are crystalline solids, which are soluble in most polar solvents.
The corresponding reaction using ZnCl2 in aqueous EtOH leads
exclusively to the formation of the complex [ZnL2] (1), while the
same reaction with Cd(CH3COO)2 leads to the formation of two
complexes: [Cd(p-BrC6H4C(S)NH2)L2] (2) and [Cd(HL)2L2] (3)
(Scheme 1). Complex 3 was separated from the mixture by extrac-
tion with n-hexane.
N-Phosphoryl-p-bromothiobenzamide
HL
and
p-
BrC6H4C(S)NH2, which are formed as a result of hydrolysis (Eq.
(2)), can serve as neutral ligands in the coordination sphere of
[CdL2] as in complexes 2 and 3. In the 31P{1H} spectrum of the reac-
tion mixture there is also a signal at ꢁ1.7 ppm, which might corre-
spond to (iPrO)2P(O)OH (dP 2.98 ppm in THF-d8 [46]).
The molecular structures of these compounds were investigated
by MALDI, IR, 1H, 31P{1H} NMR spectroscopy and by microanalysis.
In the IR spectrum of HL there are bands of all characteristic
groups. The P@O group is observed as an intense band at
1256 cmꢁ1. The band at 1504 cmꢁ1 corresponds to the S@C–N frag-
ment. The NH group shows a band at 3080 cmꢁ1
.
The properties of complexes of the ‘‘soft”, easily polarizable
Cd(II) cation differ considerably from those of Zn(II) derivatives
with the same ligands. The coordination environment of CdO2S2
The IR spectrum of 1 in Nujol is similar to the spectrum of 2. The
resonances of the P@O group of the anionic forms of L in complexes
1 and 2 are shifted by approximately 100 cmꢁ1 to low frequencies
relative to the band of the parent ligand HL. This confirms their
participation in chelate formation. The spectra contain very intense
bands corresponding to the conjugated SCN group at 1512–
1544 cmꢁ1. This fact also confirms the formation of the anionic
forms of L [23–25].
OiPr
R
N
H
N
OiPr
1) +KOH
2) + 1/2 ZnCl2
P
R
OiPr
P
S
O
OiPr
S
O
Zn
O
P
S
HL
iPrO
The main difference between the two complexes 1 and 2 in-
volves the absorption bands of the NH2 group in the IR spectrum
of complex 2 while for complex 1 no signals are observed in the
R
N
iPrO
1) +KOH
2) +1/2 Cd(CH3COO)2
1
OiPr
OiPr
S
iPrO
iPrO
iPrO
P
P
Ph
iPrO
N
OiPr
N
R
O
Ph
S
N
H
O
N
O
OiPr
N
P
S
iPrO
iPrO
P
R
O
S
S
R
P
S
O
Cd
O
S
NH2
S
Cd
O
R
R
Cd
Cd
S
S
O
H
P
N
R
O
P
N
R
N
OiPr
OiPr
N
OiPr
P
O
P
iPrO
P
OiPr
OiPr
OiPr
S
OiPr
iPrO
iPrO
N
Ph
3
2
Ph
Scheme 1. Preparation of complexes 1–3 (R = p-BrC6H4).
Scheme 2. Structure of 5 [24].

1506
D.A. Safin et al. / Polyhedron 28 (2009) 1504–1510
Table 1
characteristic area of the NH group. There is an intense band at
1664 cmꢁ1 and two bands of low intensity at 3104 and 3280 cmꢁ1
Photophysical data for complexes 1–6a.
.
The IR spectrum of 3 shows two bands for different phosphorus
groups. Along with the above band corresponding to the L form at
1156 cmꢁ1, a strong P@O band is observed at 1248 cmꢁ1 due to the
bound neutral molecules of HL. Its frequency also decreases rela-
tive to that of the band of the free ligand; however, the shift is only
8 cmꢁ1. The band for the NH group at 3160 cmꢁ1 also indicates the
presence of HL molecules in complex 3. The SCN group shows an
intense band at 1528 cmꢁ1 and indicates the presence of the anio-
nic form of L.
Complex
Emission max, nm
Complex
Emission max, nm
1
2
3
395
331, 397
394
4
5
6
392
322, 394
397
a
Excitation at 249 nm.
The IR spectra of HL and complexes 1–3 exhibit a very intense
band at 1000–1008 cmꢁ1 corresponding to the POC group.
The 31P{1H} NMR signals of complexes 1 and 2 appear at d = 6.9
and 4.3 ppm, respectively, and a down-field shift, relative to that of
the free ligand HL (d = ꢁ5.9 ppm), is observed.
The 1H NMR spectra of complexes 1 and 2 contain a single set of
signals for the (iPrO)2P(O) and C6H4 protons of the anionic form L.
The o-phenylene proton signals in 1 and 2 are shifted down-field
relative to that of the free ligand (
C6H4 proton signals are practically not shifted
D
d = 0.36 ppm), while the m-
d = 0.01–
(
D
0.04 ppm). The signal for the NHP(O) group proton is absent in
the 1H NMR spectra. This confirms the presence of the HL anionic
form in the structures of complexes 1 and 2.
The main difference involves the proton signals of the p-
BrC6H4C(S)NH2 group in the 1H NMR spectrum of complex 2. The
signals for the C6H4 protons of the p-bromothiobenzamide are ob-
served at d = 7.55 and 7.68 ppm. There are two singlets at d = 7.35
and 9.61 ppm corresponding to the NH2 group protons due to the
constrained rotation around the CN bond, typical for the thioamide
group.
Fig. 1. Emission spectra of complexes 1–6 (the excitation wavelength was 249 nm).
There are two singlets at d = ꢁ5.3 and 4.4 ppm, which have
identical integrated intensities, in the 31P{1H} NMR spectrum of
complex 3. The signal at d = ꢁ5.3 ppm is in the region characteristic
for neutral N-phosphorylated thioamides and thioureas, whereas
the second signal corresponds to the amidophosphate environ-
ment in complexes of N-acylamidophosphate anions.
parent ligands HL and HQ nor p-BrC6H4C(S)NH2 show any emission
under the same conditions). On first view, all compounds 1–6 ex-
hibit practically the same fluorescence properties, respectively.
Complexes 1, 3, 4 and 6 show a blue emission band with the
maximum intensity at 392–397 nm upon excitation at 249 nm (Ta-
ble 1, Fig. 1). Complexes 2 and 5 give a blue emission band at 394–
397 nm and additionally exhibit bands of low intensity at 322–
331 nm (Table 1, Fig. 1). The emissions of 1–6 are proposed to be
the result of the coordination of L, Q and p-BrC6H4C(S)NH2 to Zn(II)
or Cd(II), and according to previous data [32,33], these emission
bands can be assigned to the emission from a an excited ligand-
to-metal charge transfer (LMCT) state.
In the solid state, the emission bands of complexes 1 and 6 have
equal intensities. Replacing the p-bromosubstituted ligand to the
nonsubstituted analog in the complexes with the same environ-
ment of the metal cation (compare complexes 1 to 4 and, 3 to 6
respectively), leads to an increase in intensity, which may be due
The 1H NMR spectrum contains a double set of equal intensity
signals for the (iPrO)2P(O) and C6H4 protons. The assignment of
the 1H NMR spectrum of compound 3 is executed by comparing
the spectrum of 3 with those of HL and complex 2. For more exact
reference of OCH and C6H4 proton signals of complex 3, the spec-
trum of a mixture of 3 and HL was recorded at a molar ratio of
2:1. The increase in intensities of the low-field OCH group signal
and the signals for the m- and o-C6H4 protons at d = 7.47 and
7.81 ppm, respectively, concerning the neutral HL form, confirms
the reference made by comparison of the spectra. The 1H NMR
spectrum of complex 3 shows a signal for the NH group of the
phosphorylamide fragment as a doublet (2JP,H = 10.1 Hz).
MALDI experiments on complexes 1 and 2 show peaks for the
molecular ions [M+H]+, [M+Na]+ and [M+K]+. These peaks are very
intense in the mass spectrum of 1 but have low intensities (less
than 8%) in the spectrum of complex 2. In the MALDI mass spec-
trum of 2 there are molecular ion peaks corresponding to the addi-
tional p-bromothiobenzamide ligand.
The molecular ion peak of 3 is not observed under the same
measurement conditions, only ions characteristic for the [CdL2]
complex core, [CdL2 + H]+, [CdL2 + Na]+ and [CdL2 + K]+, are found
in the MALDI spectrum.
The MALDI data of 1–3 show propensity to dimer formation.
The intensity of the [M2L3]+ peak in the spectra of complexes 1–3
is in the range of 12–19%. The peaks corresponding to the dimer
formation were also observed in the ES (electrospray) mass spectra
of complexes 4–6 [24].
to stronger
r-donation from Q and HQ than L and HL.
Emission spectra of 2 and 5 are practically isomorphic and the
intensities of both bands in 2 are smaller than in 5. The Cd(II) cat-
ion in complexes 2 and 5 is pentacoordinated with trigonal-bipyra-
midal O2S3 environment, which may lead to the appearance of the
low-intensive band at 322–331 nm. There are two metal atoms in a
molecule of 5 and only one central cation in 2. Thus, this fact to-
gether with more electron donation from Q leads to an increase
in intensity of both emission bands in complex 5 compared with 2.
Crystals of 1–3 were obtained by slow evaporation of the sol-
vent from dichloromethane/n-hexane solutions of the complexes.
The crystals were measured and the structures were solved under
the conditions and with the results outlined in Table 2.
According to the X-ray data, complex 1 in a crystal is a spirocy-
clic chelate with a distorted tetrahedral ZnO2S2 core (Fig. 2). S(1)–
Zn–O(1) and O(1)–Zn–O(1)a (1 ꢁ x, 1 ꢁ y, ꢁz) angles are reduced
whereas S(1)–Zn–O(1)a (1 ꢁ x, 1 ꢁ y, ꢁz) and S(1)–Zn–S(1)a (1ꢁx,
+1, ꢁy, ꢁz) are increased in comparison with an ideal tetrahedral
The data of the emission spectra for complexes 1–6 in the solid
state at room temperature are listed in Table 1 (note that neither

D.A. Safin et al. / Polyhedron 28 (2009) 1504–1510
1507
Table 2
Crystal data, data collection and refinement details for 1–3.
1
2
3
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C26H36Br2N2O6P2S2Zn
823.82
monoclinic
C2/c
13.184(1)
21.878(2)
13.648(2)
90
C33H42Br3CdN3O6P2S3
1086.97
monoclinic
P2(1)
15.144(3)
11.918(2)
23.868(5)
90
C52H74Br4Cd1N4O12P4S4
1634.32
triclinic
P–1
12.352(14)
12.763(15)
12.89(3)
101.36(2)
95.89(2)
114.90(1)
1767(5)
b (Å)
c (Å)
a
(°)
b (°)
117.356(1)
90
3496.2(7)
96.41(3)
90
4281(2)
c
(°)
V (Å3)
Z
4
4
1
Dcalc (Mg mꢁ3
)
1.565
3.238
1664
1.686
3.574
2160
1.533
2.833
822
Absorption coefficient,
F(000)
l
(mmꢁ1
)
Recording range, h (°)
Number of recorded reflections
2.0–28.0
9753
3.2–25.0
14922
2.8–22.2
8306
Number of recorded independent reflections (Rint
R indices (all data)
S
)
4014 (0.028)
R1 = 0.0337, wR2 = 0.0809
1.03
14922 (0.0000)
R1 = 0.0579, wR2 = 0.1521
1.01
4006 (0.151)
R1 = 0.0711, wR2 = 0.1381
0.90
Table 3
Selected bond lengths (Å), and bond angles (°) for complex 1.
Bond lengths
Zn(1)–O(1)
P(3)–O(1)
P(3)–O(2)
P(3)–O(3)
P(3)–N(2)
1.960(2)
1.490(2)
1.568(2)
1.551(2)
1.607(2)
Zn(1)–S(1)
N(2)–C(1)
O(2)–C(8)
O(3)–C(11)
S(1)–C(1)
2.2980(7)
1.286(3)
1.466(3)
1.481(3)
1.734(2)
Bond angles
O(1)–Zn(1)–O(1)a
O(1)–Zn(1)–S(1)
O(1)–Zn(1)–S(1)a
S(1)–Zn(1)–S(1)a
C(1)–S(1)–Zn(1)
P(3)–O(1)–Zn(1)
O(1)–P(3)–O(3)
O(1)–P(3)–O(2)
O(3)–P(3)–O(2)
O(1)–P(3)–N(2)
107.6(1)
103.31(5)
111.70(6)
118.98(4)
107.45(9)
124.8(1)
113.2(1)
104.7(1)
108.8(1)
120.9(1)
O(3)–P(3)–N(2)
O(2)–P(3)–N(2)
N(2)–C(1)–C(2)
N(2)–C(1)–S(1)
C(2)–C(1)–S(1)
C(1)–N(2)–P(3)
C(8)–O(2)–P(3)
C(11)–O(3)–P(3)
O(3)–C(11)–C(12)
O(3)–C(11)–C(13)
101.8(1)
107.1(2)
115.7(2)
129.0(2)
115.3(2)
133.6(2)
122.8(2)
121.9(2)
106.7(3)
106.7(3)
Fig. 2. Thermal ellipsoid representation of complex 1 (hydrogen atoms are omitted
for clarity). Ellipsoids are drawn at the 30% probability level.
Torsion angles
O(1)–Zn(1)–S(1)–C(1)
S(1)a–Zn(1)–S(1)–C(1)
O(1)a–Zn(1)–S(1)–C(1)
S(1)–Zn(1)–O(1)–P(3)
S(1)a–Zn(1)–O(1)–P(3)
O(1)a–Zn(1)–O(1)–P(3)
Zn(1)–S(1)–C(1)–N(2)
Zn(1)–S(1)–C(1)–C(2)
(1 ꢁ x,1 ꢁ y, ꢁz)
110.0(1)
ꢁ129.75(9)
ꢁ5.3(1)
O(2)–P(3)–O(1)–Zn(1)
O(3)–P(3)–O(1)–Zn(1)
N(2)a–P(3)–O(1)–Zn(1)
O(2)–P(3)–N(2)a–C(1)a
O(3)–P(3)–N(2)a–C(1)a
S(1)–C(1)–N(2)–P(3)a
C(1)–C(1)–N(2)–P(3)a
129.5(1)
ꢁ112.2(1)
8.8(2)
ꢁ130.2(3)
115.8(3)
1.5(4)
angle of 109.5° (Table 3). Similarly to those of the [Co(II)Q2] [28,29]
and complex 4 [24], investigated by us earlier, the six-membered
chelate rings are practically planar in the molecule of 1. The max-
imum deviation from the best plane Zn–O–P–N–C–S is observed
for P(1) phosphorus and O(1) oxygen atoms. The phenylene ring
is rotated relative to the plane of the conjugated SCN moiety [tor-
sion angles are N(2)–C(1)–C(2)–C(3) 16.1(3)° and S(1)–C(1)–C(2)–
C(7) 17.8(3)°].
127.6(1)
ꢁ1.4(1)
ꢁ119.7(1)
6.2(3)
ꢁ174.4(2)
ꢁ177.9(2)
Complex 2 (Fig. 3) crystallizes in the chiral space group P2(1).
The asymmetric unit contains two independent molecules.
There are intra- and intermolecular hydrogen bonds of the type
N–HꢂꢂꢂO in the crystal of complex 2. The intramolecular H-bond is
formed between the oxygen atom of the P@O group of the anionic
ligand L and one of the hydrogen atom of the NH2 fragment of p-
bromothiobenzamide. The intramolecular hydrogen bond parame-
ters in Molecule 1 are as follows: N(3)–H(3 M)ꢂꢂꢂO(4), d(HꢂꢂꢂO)
2.2(1) Å, d(NꢂꢂꢂO) 2.93(1) Å, —(N–HꢂꢂꢂO) 158(1)°. The hydrogen bond
parameters in Molecule 2 are as follows: N(6)–H(6 M)ꢂꢂꢂO(10),
d(HꢂꢂꢂO) 2.1(1) Å, d(NꢂꢂꢂO) 2.86(1) Å, —(N–HꢂꢂꢂO) 157(1)°.
As a result of the intermolecular H-bonds chains along the b
axis are formed. The intermolecular H-bonds are as follows:
N(3)–H(3 N)ꢂꢂꢂO(1) (ꢁ1 ꢁ x, 1/2 + y, 2 ꢁ z), d(HꢂꢂꢂO) 1.91(9) Å,
d(NꢂꢂꢂO) 2.93(1) Å, —(N–HꢂꢂꢂO) 172.1(8)° N(6)–H(6 N)ꢂꢂꢂO(7)
(ꢁ1 ꢁ x, 1/2–y, 3–z), d(HꢂꢂꢂO) 2.3(1) Å, d(NꢂꢂꢂO) 3.0(1) Å, —(N–HꢂꢂꢂO)
169(1)°.
The Cd(II) cations are present in a distorted trigonal-bipyrami-
dal environment (O2S3). The axial positions are occupied by the
oxygen atoms of the phosphoryl groups. Three sulfur atoms, corre-
sponding to the two anionic forms L and one p-bromothiobenza-
mide, lie in its base. The six-membered Cd–O–P–N–C–S cycles
have a distorted boat conformation with the C@S sulfur atom
and the P@O oxygen atom in apical positions (Table 4). The lengths
of the Cd–S bonds in the chelate rings of the Molecule 1 are prac-
tically equivalent, but in the Molecule 2 the difference is about
0.014(1) Å. The third Cd–S bonds in both molecules are almost
equal to each other (
D
ꢃ 0.003 Å). The bonds with the oxygen
atoms in the chelate rings of the Molecule 1 differ on 0.08 Å, but
the Cd–O bonds difference in the Molecule 2 is only 0.03 Å. The
Cd(1)–O(1) and Cd(2)–O(7) bonds in the Molecules 1 and 2, respec-
tively, deviate from the normal to the CdS3 plane [O(1)–Cd(1)–O(4)
169.3(2)° and O(7)–Cd(2)–O(10) 171.1(2)°], while the Cd(1)–O(4)

1508
D.A. Safin et al. / Polyhedron 28 (2009) 1504–1510
Fig. 4. Thermal ellipsoid representation of complex 3 (hydrogen atoms are omitted
for clarity). Ellipsoids are drawn at the 30% probability level.
Fig. 3. Thermal ellipsoid representation of one of the two independent molecules of
complex 2 (hydrogen atoms are omitted for clarity). Ellipsoids are drawn at the 30%
probability level.
and Cd(2)–O(10) bonds stay practically perpendicular to the CdS3
plane.
The molecule of complex 3 in the crystal is located in a special
position at the symmetry centre. The coordination geometry of the
Cd(II) atom is tetragonal bipyramidal (D2 h) (Fig. 4). Isostructural
complexes of Co(II) [28,29], Ni(II) [35] with HQ, and Cd(II), Ni(II)
with HL [24,45] have been synthesized and structurally character-
ized by us previously.
The equatorial positions of the bipyramid are occupied by two
N-phosphoryl-p-bromothiobenzamide anions L, bonded through
sulfur atoms and oxygen atoms of thiocarbonyl and phosphoryl
groups, respectively. The six-membered Cd–O–P–N–C–S cycle lies
between a boat and a chair conformations since the O–P–N–C–S
backbone is flat (Table 5). The ligands show trans configuration.
Neutral ligand molecules are coordinated in the axial positions
through the oxygen atoms of the phosphoryl groups. The lengths
of the Cd–O bonds in the chelate rings are 2.300(9) Å while the
bonds with the axial oxygen atoms are 2.419(9) Å.
Table 4
Selected bond lengths (Å), and bond angles (°) for complex 2.
Molecule 1
Molecule 2
Bond lengths
Cd(1)–O(1)
Cd(1)–O(4)
Cd(1)–S(1)
Cd(1)–S(2)
Cd(1)–S(3)
P(1)–O(1)
P(1)–O(2)
P(1)–O(3)
P(1)–N(1)
P(2)–O(4)
P(2)–O(5)
P(2)–O(6)
P(2)–N(2)
2.418(6)
2.339(6)
2.514(3)
2.519(2)
2.570(3)
1.493(6)
1.565(7)
1.556(7)
1.637(8)
1.491(6)
1.567(7)
1.563(7)
1.613(8)
Cd(2)–O(7)
Cd(2)–O(10)
Cd(2)–S(4)
Cd(2)–S(5)
Cd(2)–S(6)
P(3)–O(7)
P(3)–O(8)
P(3)–O(9)
P(3)–N(4)
P(4)–O(10)
P(4)–O(11)
P(4)–O(12)
P(4)–N(5)
2.355(6)
2.323(6)
2.516(3)
2.530(2)
2.567(2)
1.467(6)
1.587(9)
1.524(8)
1.620(8)
1.494(6)
1.579(7)
1.558(7)
1.623(8)
There are two intramolecular NHꢂꢂꢂO bonds between the oxygen
atom of the P@O group of the anionic ligand L and the hydrogen
atom of the NH fragment of the neutral ligand HL in the crystal
of complex 3. The hydrogen bond parameters are as follows:
N(1B)–H(1B)ꢂꢂꢂO(1A) (1 ꢁ x, ꢁy, ꢁz), d(HꢂꢂꢂO) 2.11 Å, d(NꢂꢂꢂO)
2.92(1) Å, —(N–HꢂꢂꢂO) 157°.
Bond angles
O(4)–Cd(1)–O(1)
O(1)–Cd(1)–S(1)
O(1)–Cd(1)–S(2)
O(4)–Cd(1)–S(3)
S(1)–Cd(1)–S(3)
O(10)–Cd(2)–O(7)
O(7)–Cd(2)–S(4)
O(7)–Cd(2)–S(5)
O(10)–Cd(2)–S(6)
S(4)–Cd(2)–S(6)
C(1)–S(1)–Cd(1)
C(8)–S(2)–Cd(1)
C(15)–S(3)–Cd(1)
P(1)–O(1)–Cd(1)
P(2)–O(4)–Cd(1)
169.3(2)
91.1(2)
94.2(2)
O(4)–Cd(1)–S(1)
O(4)–Cd(1)–S(2)
S(1)–Cd(1)–S(2)
O(1)–Cd(1)–S(3)
S(2)–Cd(1)–S(3)
O(10)–Cd(2)–S(4)
O(10)–Cd(2)–S(5)
S(4)–Cd(2)–S(5)
O(7)–Cd(2)–S(6)
S(5)–Cd(2)–S(6)
C(51)–S(4)–Cd(2)
C(58)–S(5)–Cd(2)
C(65)–S(6)–Cd(2)
P(3)–O(7)–Cd(2)
P(4)–O(10)–Cd(2)
88.9(2)
94.5(2)
126.4(1)
76.7(2)
114.86(9)
96.5(2)
92.3(2)
120.70(9)
78.8(2)
117.42(9)
108.9(3)
110.0(3)
112.8(3)
119.2(4)
114.7(3)
93.9(2)
118.2(1)
171.1(2)
91.6(2)
86.8(2)
93.8(2)
120.27(9)
111.6(3)
107.5(3)
114.6(3)
110.6(3)
113.3(3)
3. Experimental
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} NMR spectra (CDCl3) were recorded at 299.948 and
121.420 MHz, respectively. Chemical shifts are reported with refer-
ence to SiMe4 (1H) and H3PO4 (31P{1H}). MALDI mass spectra of 1–3
were obtained using a Bruker Reflex IV spectrometer. Fluorescence
measurements were made on a SLM Aminco 500 spectrofluorome-
ter at room temperature. Elemental analyses were performed on a
Perkin–Elmer 2400 CHN microanalyser.
Torsion angles
S(2)–Cd(1)–S(1)–C(1)
S(3)–Cd(1)–S(1)–C(1)
O(1)–Cd(1)–S(1)–C(1)
O(4)–Cd(1)–S(1)–C(1)
S(1)–Cd(1)–O(1)–P(1)
S(2)–Cd(1)–O(1)–P(1)
S(3)–Cd(1)–O(1)–P(1)
S(1)–Cd(1)–O(4)–P(2)
S(2)–Cd(1)–O(4)–P(2)
S(3)–Cd(1)–O(4)–P(2)
Cd(1)–S(1)–C(1)–N(1)
105.6(4)
ꢁ65.8(4)
9.7(4)
O(2)–P(1)–O(1)–Cd(1)
O(3)–P(1)–O(1)–Cd(1)
N(1)–P(1)–O(1)–Cd(1)
O(1)–P(1)–N(1)–C(1)
O(2)–P(1)–N(1)–C(1)
O(3)–P(1)–N(1)–C(1)
O(5)–P(2)–O(4)–Cd(1)
O(6)–P(2)–O(4)–Cd(1)
N(2)–P(2)–O(4)–Cd(1)
P(1)–N(1)–C(1)–S(1)
171.6(3)
58.5(4)
ꢁ68.5(5)
ꢁ159.6(4)
61.3(9)
31.6(4)
ꢁ174.7(8)
ꢁ64.4(9)
68.4(4)
ꢁ173.3(3)
ꢁ56.6(5)
ꢁ1.6(1)
ꢁ95.0(4)
150.4(4)
ꢁ108.7(3)
17.7(3)
133.1(3)
ꢁ27.0(1)
3.1. Syntheses
p-BrC6H4C(S)NHP(O)(OiPr)2 (HL). N-(diisopropoxyphosphoryl)-
p-bromothiobenzamide was prepared according to previously de-
scribed methods [45].

D.A. Safin et al. / Polyhedron 28 (2009) 1504–1510
1509
Table 5
Selected bond lengths (Å), and bond angles (°) for complex 3.
Bond lengths
Cd(1)–O(1A)
Cd(1)–O(1B)
Cd(1)–S(1A)
N(1A)–C(1A)
N(1B)–C(1B)
P(1A)–O(1A)
P(1A)–O(2A)
P(1A)–O(3A)
2.300(9)
2.419(9)
2.570(7)
1.28(2)
1.42(2)
1.509(9)
1.54(1)
1.59(2)
P(1B)–O(1B)
1.475(8)
P(1B)–O(2B)
P(1B)–O(3B)
P(1A)–N(1A)
P(1B)–N(1B)
S(1A)–C(1A)
S(2B)–C(1B)
1.557(9)
1.57(1)
1.61(1)
1.66(1)
1.74(1)
1.61(1)
Bond angles
O(1A)–Cd(1)–O(1B)
O(1A)–Cd(1)–O(1A_a)
O(1A)–Cd(1)–O(1B_a)
S(1)–Cd(1)–O(1ª)
S(1)–Cd(1)–O(1ª_a)
S(1A)–Cd(1)–O(1B)
S(1A)–Cd(1)–O(1B_a)
S(1A)–Cd(1)–S(1ª_a)
Cd(1)–S(1A)–C(1ª)
Cd(1)–O(1A)–P(1ª)
Cd(1)–O(1B)–P(1B)
O(1A)–P(1A)–O(2A)
89.7(2)
180.00
O(1A)–P(1A)–O(3A)
O(1A)–P(1A)–N(1A)
O(1B)–P(1B)–O(2B)
O(1B)–P(1B)–O(3B)
O(1B)–P(1B)–N(1B)
O(2A)–P(1A)–O(3A)
O(2A)–P(1A)–N(1A)
O(3A)–P(1A)–N(1A)
O(2B)–P(1B)–O(3B)
O(2B)–P(1B)–N(1B)
O(3B)–P(1B)–N(1B)
103.8(6)
122.2(5)
114.9(5)
116.0(5)
108.0(4)
110.2(7)
101.8(5)
104.7(6)
101.2(5)
108.7(4)
107.6(5)
90.3(2)
89.6(2)
90.4(2)
90.2(2)
89.8(2)
180.00
108.5(4)
124.6(4)
136.1(4)
113.7(5)
Torsion angles
O(1A)–Cd(1)–S(1ª)–C(1A)
O(1B)–Cd(1)–S(1ª)–C(1A)
O(1A_a)–Cd(1)–S(1A)–C(1A)
O(1B_a)–Cd(1)–S(1A)–C(1A)
S(1A)–Cd(1)–O(1A)–P(1A)
O(1B)–Cd(1)–O(1A)–P(1A)
S(1ª_a)–Cd(1)–O(1A)–P(1A)
O(1B_a)–Cd(1)–O(1A)–P(1A)
S(1A)–Cd(1)–O(1B)–P(1B)
O(1A)–Cd(1)–O(1B)–P(1B)
S(1A_a)–Cd(1)–O(1B)–P(1B)
O(1A_a)–Cd(1)–O(1B)–P(1B)
Cd(1)–O(1A)–P(1A)–O(2A)
ꢁ30.8(5)
58.9(5)
149.2(5)
ꢁ121.1(5)
27.7(5)
ꢁ62.5(5)
ꢁ152.3(5)
117.5(5)
80.3(6)
169.9(7)
ꢁ99.7(6)
ꢁ10.1(7)
114.1(5)
Cd(1)–O(1A)–P(1A)–O(3A)
Cd(1)–O(1A)–P(1A)–N(1A)
Cd(1)–O(1B)–P(1B)–O(2B)
Cd(1)–O(1B)–P(1B)–O(3B)
Cd(1)–O(1B)–P(1B)–N(1B)
C(1A)–N(1A)–P(1A)–O(1A)
C(1A)–N(1A)–P(1A)–O(2A)
C(1A)–N(1A)–P(1A)–O(3A)
C(1B)–N(1B)–P(1B)–O(1B)
C(1B)–N(1B)–P(1B)–O(2B)
C(1B)–N(1B)–P(1B)–O(3B)
N(1A)–C(1A)–S(1A)–Cd(1)
S(2B)–C(1B)–N(1B)–P(1B)
ꢁ126.2(6)
ꢁ8.7(8)
ꢁ136.2(6)
106.2(6)
ꢁ14.7(8)
ꢁ19.9(2)
ꢁ148.0(1)
97.3(2)
ꢁ168.6(1)
ꢁ43.4(1)
65.5(1)
21.6(1)
ꢁ11.9(2)
[ZnL2] (1). A suspension of HL (1.9 g, 5 mmol) in aqueous etha-
nol (20 mL) was mixed with an ethanol solution of potassium
hydroxide (0.28 g, 5 mmol). An aqueous (20 mL) solution of ZnCl2
(0.82 g, 2.8 mmol) was added dropwise under vigorous stirring to
the resulting potassium salt. The mixture was stirred at room tem-
perature for further 3 h and left overnight. The complex was ob-
tained by extraction of the reaction mixture by dichloromethane,
washed with water and dried using anhydrous MgSO4. The solvent
was then removed in vacuo. A colorless precipitate was recrystal-
requires C, 36.46; H, 3.89; N, 3.87%.).
m
max/cmꢁ1 3280, 3104, 1664
(NH2), 1512 (SCN), 1157 (P@O), 1000 (POC). dH 9.61 (1H, br. s,
NH2), 8.14 (4H, m, 3J 8.5, o-H, C6H4, L), 7.68 (2H, m, 3J 8.4, o-H,
C6H4), 7.55 (2H, m, 3J 8.4, m-H, C6H4), 7.47 (4H, m, 3J 8.5, m-H,
C6H4, L), 7.35 (1H, s, NH2), 4.72 (4H, d sept, 3J 6.3 Hz, OCH), 1.34
(24H, d, 3J 6.1, CH3). dP 4.3. m/z (MALDI) 217 (100) [p-
BrC6H4C(S)NH2 + H]+, 240 (13) [p-BrC6H4C(S)NH2 + Na]+, 217 (5)
[p-BrC6H4C(S)NH2 + K]+, 873 (34) [CdL2 + H]+, 896 (48)
[CdL2 + Na]+, 1089 (6) [M + H]+, 1112 (3) [M + Na]+, 1128 (7)
[M + K]+, 1364 (19) [Cd2L3]+. At the solvent-removal stage (hexane
soluble), product 3 was isolated. Complex 3 was obtained as orange
crystals. Yield 0.21 g, m.p. 114 °C. (Found: C, 38.37; H, 4.46; N,
3.50%. C52H74Br4CdN4O12P4S4 requires C, 38.28; H, 4.57; N,
ized from
a dichloromethane/n-hexane mixture. Yield 1.73 g
(84%), m.p. 143 °C. (Found: C, 37.82; H, 4.47; N, 3.31%.
C26H36Br2N2O6P2S2Zn requires C, 37.90; H, 4.40; N, 3.40%.). mmax
/
cmꢁ1 1544 (SCN), 1152 (P@O), 1000 (POC). dH 8.14 (4H, m, 3J 8.4,
o-H, C6H4), 7.50 (4H, m, 3J 8.4, m-H, C6H4), 4.71 (4H, d sept, 3J
6.2, OCH), 1.36 (12H, d, 3J 5.6, CH3), 1.35 (12H, d, 3J 5.6, CH3). dP
6.9. m/z (MALDI) 826 (81) [M+H]+, 849 (100) [M+Na]+, 864 (52)
[M+K]+, 1271 (12) [Zn2L3]+.
3.43%.). m
max/cmꢁ1 3160 (NH), 1528 (SCN), 1248 (P@O, HL), 1156
(P@O, L), 1004 (POC). dH 9.00 (2H, d, 3J 10.1, NH), 8.13 (4H, m, 3J
7.9, o-H, C6H4, L), 7.81 (4H, m, 3J 8.3, o-H, C6H4, HL), 7.53 (4H, m,
3J 7.9, m-H, C6H4, L), 7.47 (4H, m, 3J 7.9, m-H, C6H4, HL), 4.83 (4H,
d sept, 3J 6.3, OCH, HL), 4.65 (4H, d sept, 3J 6.2, OCH, L), 1.36
(12H, d, 3J 6.3, CH3, L), 1.30 (36H, br s, CH3, L + HL). dP 4.4 (2P, L),
ꢁ5.3 (2P, HL). m/z (MALDI) 873 (67) [CdL2 + H]+, 896 (100)
[CdL2 + Na]+, 912 (17) [CdL2 + K]+, 1364 (15) [Cd2L3]+.
[Cd(p-BrC6H4C(S)NH2)L2] (2) and [Cd(HL)2L2] (3). A suspension of
HL (1.91 g, 5 mmol) in aqueous ethanol (20 mL) was mixed with an
ethanol solution of potassium hydroxide (0.28 g, 5 mmol). An
aqueous (20 mL) solution of Cd(CH3COO)2 ꢂ 2H2O (0.82 g,
2.8 mmol) was added dropwise under vigorous stirring to the
resulting potassium salt. The mixture was stirred at room temper-
ature for a further 3 h and left overnight. The complex was ob-
tained by extraction of the reaction mixture by dichloromethane,
washed with water and dried with anhydrous MgSO4. The solvent
was then removed in vacuo. The residue was extracted using n-
hexane. The hexane insoluble residue was recrystallized from a
dichloromethane/n-hexane mixture, and complex 2 was isolated.
Complex 2 was obtained as colorless crystals. Yield 0.44 g, mp
129 °C. (Found: C, 36.35; H, 3.96; N, 3.81%. C33H42Br3CdN3O6P2S3
3.2. Structure determination
The data for 1 and 3 were collected at 20 °C using a Bruker
Smart Apex2 diffractometer and graphite-monochromated Mo K
a
radiation generated from Diffraction X-ray tube operated at
50 kV and 30 mA. The images were indexed, integrated and scaled
using the APEX2 data reduction package [47]. All raw data were
corrected for absorption using SADABS [48] The structure was solved
by heavy atom and direct method using SIR [49] program and the

1510
D.A. Safin et al. / Polyhedron 28 (2009) 1504–1510
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4. Conclusions
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The data obtained testify that the structure of the chelate com-
plexes of 12 Group metal cations with N-phosphorylated thioam-
ides of general formula RC(S)NHP(O)R0R00 depends on the nature of
the central ion, and unlike dithioanaloges RC(S)NHP(S)R0R00 which
form only complexes with a MS4 core. For the ligands containing dif-
ferent donor atoms, sulfur and oxygen simultaneously, the increase
in the coordination number of the central atom by dimerization or
interaction with nucleophilic species is observed for complexes of
Cd(II), while only tetracoordinated [M{RC(S)NP(O)R0R00}-O,S)2] com-
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We assume, that dimerization of the Cd(II) compounds in aque-
ous ethanol media can promote their hydrolysis, while the mono-
nuclear Zn(II) compounds are obtained in good yield and show no
tendency to hydrolytic destruction.
The luminescent properties of the new complexes has shown
that the observed emission bands can be assigned ligand-to-metal
charge transfer (LMCT).
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This work was supported by the Russian Science Support Foun-
dation and partly by University of Wroclaw. M.G.B. and D.A.S.
thank DAAD for the scholarships (Forschungsstipendien 2008/
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the crystal structure determination.
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Appendix A. Supplementary data
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crystallographic data for (1), (2) and (3). These data can be ob-
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