Coordination mode of the zinc(II) and cadmium(II) cations with N-(diisopropoxyphosphoryl)thiobenzamide

Article abstract of DOI:10.1002/ejic.200501005

Reaction of the potassium salt of N-(diisopropoxyphosphoryl)thiobenzamide (iPrO)₂P(O)NHC(S)C₆H₅ (HL) with Zn^II and Cd^II cations in aqueous EtOH leads to three different complexes: [Zn(L-O,S)₂] (1), [Cd₂(L-O,S)₄] (2) and [Cd(HL-O)₂(L-O,S)₂] (3). The structures of these compounds were investigated by single-crystal X-ray diffraction analysis, EI-MS and ES-MS, IR, ¹H, ¹³C and ³¹P NMR spectroscopy and microanalysis. The zinc(II) atom in complex 1 is in a distorted tetrahedral ZnO₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. The cadmium(II) complex 2 is centrosymmetric and consists of dimeric species. Two [Cd(L-O,S)₂] moieties are connected by two bridging [S-Cd-S] units through the sulfur atoms of the ligand C=S groups. Complex 2 has a distorted trigonal-bipyramidal Cd(O^ax)₂(S^eq)₃ core. Complex 3 has a tetragonal-bipyramidal environment, Cd(O^ax)₂(O ^eq)₂(S^eq)₂, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in a typical 1,5-O,S coordination mode. The ligands are in a trans configuration. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200501005

FULL PAPER
DOI: 10.1002/ejic.200501005
Coordination Mode of the Zinc(II) and Cadmium(II) Cations with
N-(Diisopropoxyphosphoryl)thiobenzamide
Felix D. Sokolov,[a] Damir A. Safin,*[a] Nail G. Zabirov,[a] Vasiliy V. Brusko,[a]
Bulat I. Khairutdinov,[a] Dmitry B. Krivolapov,[b] and Igor A. Litvinov[b]
Keywords: Chelates / Coordination modes / Crystal structures / (Thioacylamido)phosphates / Zinc() / Cadmium() com-
plexes
Reaction of the potassium salt of N-(diisopropoxyphosphor- connected by two bridging [S–Cd–S] units through the sulfur
yl)thiobenzamide (iPrO)2P(O)NHC(S)C6H5 (HL) with ZnII atoms of the ligand C=S groups. Complex 2 has a distorted
and CdII cations in aqueous EtOH leads to three different trigonal-bipyramidal Cd(Oax)2(Seq
) core. Complex 3 has a
3
complexes: [Zn(L-O,S)2] (1), [Cd2(L-O,S)4] (2) and [Cd(HL- tetragonal-bipyramidal environment, Cd(Oax)2(Oeq)2(Seq)2,
O)2(L-O,S)2] (3). The structures of these compounds were in- and two neutral ligand molecules are coordinated in the axial
vestigated by single-crystal X-ray diffraction analysis, EI-MS positions through the oxygen atoms of the P=O groups. The
and ES-MS, IR, 1H, 13C and 31P NMR spectroscopy and mi- base of the bipyramid is formed by two anionic ligands in a
croanalysis. The zinc(II) atom in complex 1 is in a distorted typical 1,5-O,S coordination mode. The ligands are in a trans
tetrahedral ZnO2S2 environment formed by the C=S sulfur configuration.
atoms and the P=O oxygen atoms of two deprotonated li-
gands. The cadmium(II) complex 2 is centrosymmetric and (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
consists of dimeric species. Two [Cd(L-O,S)2] moieties are Germany, 2006)
taining two CdII cations in a distorted tetrahedral CdS4 en-
vironment.
Introduction
Amidophosphates of the type RC(X)NHP(Y)RЈ2 (X, Y
The structure of ZnII and CdII complexes with the gene-
= O or S; R = Alk, Ar, ArNH, AlkNH, Alk2N; RЈ = OAlk,
ral formula M[L-S,SЈ]2 {L = [H2NC(S)NP(S)(C6H5)2]–, M
OAr, Ar) are attractive because of their ability to form
= ZnII;[16] L = [C6H5NHC(S)NP(S)(OiPr)2]–, M = ZnII or
stable chelates with d- and f-metal cations. These complexes
CdII;[17] L = [C6H5C(S)NP(S)(OiPr)2]–, M = ZnII[17] and
possess antivirus[1] and anticancer activity,[2] and show non-
CdII[18]} has been investigated by IR and NMR spec-
linear optical properties.[3] They can be used as components
troscopy[16–18] and X-ray analysis.[16] It was established that,
of ion-selective electrodes,[4–7] or as extragents and masking
in all cases, there is chelate formation in which the metal
reagents in analytical chemistry.[8,9]
cation has a distorted tetrahedral MS4 environment.
An application as structural blocks for the synthesis of
In contrast to dithio derivatives, the ZnII and CdII com-
supramolecular coordination compounds has excited a new
plexes with N-acylamidophosphates RC(X)NHP(Y)RЈ2,
wave of interest in the coordination chemistry of amido-
containing both donor atoms of sulfur and oxygen (X ϶
phosphates[10,11] and their nearest analogues such as 1,3-
Y), were not studied earlier. The substitution of two sulfur
[12]
dichalcogenimidodiphosphinates R2P(X)NHP(Y)RЈ2
or
atoms in the central ion coordination sphere by oxygen
atoms lowers the degree of stabilisation of π interactions.
This leads to an increase in the coordination numbers of
the ZnII and CdII cation from 4 to 5 and 6, respectively. For
example, it is known that CdII complexes with R2P(X)-
NHP(Y)RЈ2 (X = S, Y = O or X = Y = O) exhibit dinuclear
structures in which the imidodiphosphinate anions act
simultaneously as didentate ligands and as bridging units
through the oxygen atoms of the P=O groups.[12]
carbamoylphosphane oxide R2P(O)CH2C(X)RЈ.[13] Polynu-
clear complexes of the type MnLn (M = CoII, NiII, PdII,
AgI, ZnII, CdII, HgII) of bis(bipodal) amidothiophosphates
with the general formula [(iPrO)2P(S)NHC(S)NH]2Z [Z =
(CH2)2O(CH2)2, (CH2)2O(CH2)2O(CH2)2, (CH2)2, (CH2)7]
have been investigated.[14,15] It was established that the cad-
mium() complex with bipodal amidophosphate, where Z
= (CH2)2,[15] represents a macrocyclic dimer (n = 2) con-
The present work was carried out with the aim of ap-
praising the influence of the cation (MII = ZnII and CdII)
on the formation of either mono- or dinuclear complexes
with the amidophosphate ligand (iPrO)2P(O)NHC(S)C6H5
(HL).
[a] Department of Chemistry, Kazan State University,
Kremlevskaya St. 18, 420008 Kazan, Russia
Fax: +7-843-254-3734
E-mail: damir.safin@ksu.ru
[b] A. E. Arbuzov Institute of Organic and Physical Chemistry,
Arbuzov St. 8, 420088 Kazan, Russia
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D. A. Safin et al.
FULL PAPER
The main difference involves the absorption bands of the
SCN group.[19,20] In the spectrum of a suspension of 1 in
Nujol there is an intense absorption band at 1528 cm–1,
whereas in 2 the participation of sulfur atoms in dimer for-
mation results in the occurrence of three intense absorption
bands in the given area: 1536, 1576 and 1584 cm–1. In a
CCl4 solution of complex 2 the bands merge into one with
a maximum of 1536 cm–1, which suggests the dissociation
of the dimeric molecules.
Results and Discussion
Synthesis
The ligand HL was prepared by reaction of thiobenz-
amide C6H5C(S)NH2 with diisopropyl chlorophosphate
(iPrO)2P(O)Cl.
Complexes of HL with ZnII and CdII cations (1–3) were
prepared by the following procedure: the ligand was con-
verted into the potassium salt KL, followed by reaction
with salts of the corresponding metals. The compounds ob-
tained are crystalline solids that are soluble in most polar
solvents. Reaction of the salt KL with ZnCl2 in aqueous
EtOH leads only to the formation of the complex [ZnL2]
(1). Reaction with Cd(CH3COO)2 leads to the formation
of two complexes: [Cd2L4] (2) and [Cd(HL)2L2] (3)
(Scheme 1). Complex 3 was separated from the mixture by
extraction with n-hexane.
The IR spectrum of 3 contains two bands for different
phosphorus groups. Along with the above band corre-
sponding to the L form, a strong P=O band is observed at
1240 cm–1 because of the bound neutral molecules of HL.
Its frequency also decreases relative to that of the band of
the free ligand; however, the shift is 12 cm–1. The absorp-
tion band for the NH group at 3176 cm–1 also indicates the
presence of HL molecules in complex 3.
The 31P{1H} NMR signals of complexes 1 and 2 appear
at δ = 5.7 and 3.0 ppm, respectively, and a down-field shift,
relative to that of the free ligand HL (δ = –5.6 ppm), is
observed. Full width at half peak maximum is in the range
1.0–5.0 Hz.
1
The H NMR spectra contain a single set of signals for
the (iPrO)2P(O) and C6H5 protons. The o-phenyl proton
signals in complexes 1 and 2 are shifted down-field. The
1
signal for the NHP(O) group proton is absent in H NMR
spectra. This confirms the presence of the HL anionic form
in the structures of complexes 1 and 2.
The formation of dimeric structures in solution would
lead to doubling or to exchange broadening of the signals
in the NMR spectra. Distinction between the trailer and
bridging ligand forms should be shown in the NMR spectra
for 13C and 31P nuclei. Experimental evidence has shown
that in both complexes 1 and 2 the 13C and 31P NMR spec-
tra indicate that there is no doubling or exchange broaden-
ing of the signals for carbon and phosphorus atoms. Thus,
the NMR spectroscopic data confirm that in CDCl3 solu-
tion complexes 1 and 2 are exclusively in the monomeric
form.
Scheme 1.
There are two singlet signals at δ = –6.0 and 3.7 ppm,
which have identical integrated intensities, in the 31P{1H}
NMR spectrum of complex 3. The signal at δ = –6.0 ppm
is in the region that is characteristic for neutral N-phos-
phorylated thioamides and thioureas, whereas the second
signal corresponds to the amidophosphate environment in
complexes of N-acylamidophosphate anions.
It has been shown that in the crystal form all listed com-
plexes have various coordination environments at the metal
atoms. The IR and NMR spectroscopic data confirm that
in CDCl3 and CCl4 solutions and in all three cases the dom-
inating forms are [ML2] chelates with a tetrahedral MO2S2
core.
1
The H NMR spectrum contains a double set of equal-
intensity signals for the (iPrO)2P(O) and C6H5 protons. The
spectrum of complex 3 basically represents the sum of the
spectra of ligand HL and complex 2 (Figure 1). The assign-
IR and NMR Spectroscopy
1
ment of the H NMR spectrum of compound 3 is executed
The IR spectrum of 1 in Nujol is similar to the spectrum by comparing the spectrum of 3 with those of HL and com-
of 2. The absorption bands of the P=O group of the anionic plex 2. For a more exact reference of OCH proton signals
forms L in complexes 1 and 2 are shifted by approximately of complex 3, the spectrum of a mixture of 3 and HL was
70 cm–1 to low frequencies relative to the band of the parent run at a molar ratio of 3:1. The increase in intensities of
ligand HL. This confirms their participation in chelate for- the low-field OCH group signal and the signal for the high-
mation. The signal for the NH proton is absent in the IR field o-C6H5 protons, concerning the neutral HL form, con-
spectra of complexes 1 and 2.
firms the reference made by comparison of the spectra.
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Coordination Mode of ZnII and CdII with N-(Diisopropoxyphosphoryl)thiobenzamide
FULL PAPER
ular ions of 2 [Cd2L4]+ and 3 [Cd(HL)2L2]+ are unstable
under the measurement conditions, and the heaviest molec-
ular ion observed in the spectra of 2 and 3 corresponds to
the neutral [CdL2]+ complex core.
ES-MS experiments (electrospray method) on complexes
1 and 2 show peaks for the molecular ions [ML2 + Na]+
and [ML2 + K]+. The cations [ML2 + H]+, on the contrary,
are unstable. This is, apparently, connected to the separat-
ing of the HL molecule.
The ES-MS data of 2 (Figure 2) shows propensity to di-
mer formation. The intensity of the [Cd2L3]+ peak in the
electrospray spectrum of complex 2 is 38% and is maximal
in a number of the investigated compounds. The [Cd2L4 +
Na]+ peak has an intensity of 0.8%.
The molecular ion peak of 3 is absent. Its electrospray
spectrum contains all ions characteristic of the [CdL2] com-
plex core: [CdL2 + H]+ (low intensity), [CdL2 + Na]+,
[CdL2 + K]+, [Cd2L3]+.
1
Figure 1. H NMR spectra of complexes 3 (A), 2 (C) and HL (B).
Signals of HL (free and in the structure of 3) are marked * and a
signal for the solvent #.
EI and ES Mass Spectrometry
Crystal Structure of 1
The electron impact mass spectrum (EI-MS) of 1 con-
According to the X-ray data, complex 1 is a spirocyclic
chelate with a distorted tetrahedral ZnO2S2 core (Figure 3).
tains the [ZnL2]+ structure molecular ion peak. The molec-
Figure 3. Molecular structure of complex 1.
Table 1. Selected bond lengths [Å], and bond and torsion angles [°]
for complex 1.[a]
Bond lengths
Zn1–S2
Zn1–O1
S2–C1
2.288(1)
1.962(2)
1.735(3)
P1–O1
P1–N1
N1–C1
1.492(2)
1.614(2)
1.285(3)
Bond angles
S2–Zn1–O1
102.83(8)
118.82(8)
104.52(14) P1–N1–C1
113.64(80) S2–C1–N1
O1–P1–N1
Zn1–O1–P1
118.9(1)
125.1(1)
133.4(1)
129.1(2)
114.7(2)
S2–Zn1–S2_a
S2–Zn1–O1_a
O1–Zn1–O1_a
Zn1–S2–C1
107.7(1)
S2–C1–C2
Torsion angles
O1–Zn1–S2–C1
S2–Zn1–O1–P1
Zn1–S2–C1–N1
1.4(1)
11.4(2)
–4.9(3)
N1–P1–O1–Zn1
O1–P1–N1–C1
P1–N1–C1–S2
–21.2(2)
–108.6(3)
–4.6(4)
Figure 2. ES-MS spectra of complex 2. Peak A is observed for the
[CdL2 + Na]+ cation, pattern B is calculated for C26H38CdN2Na-
O6P2S2, peak C is observed for the [Cd2L3]+ cation and pattern D
is calculated for C39H57Cd2N3O9P3S3.
[a] Symmetry transformations used to generate equivalent atoms:
_a (–x, y, –z + 1/2).
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D. A. Safin et al.
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Similarly to those of the [CoIIL2] complex with the same
ligand, investigated by us earlier,[21] the six-membered che-
late rings are practically flat. The phosphorus atoms usually
have a tetrahedral configuration in such compounds. Se-
lected values of bond lengths, bond and torsion angles are
given in Table 1.
Crystal Structure of 2
The X-ray data show that in a crystal form complex 2 is
a centrosymmetric dimer. In contrast to the imidodiphos-
phinate complexes, the bond does not occur through the
oxygen atoms of the P=O[12] groups, but through the sulfur
atoms of the C=S groups of the deprotonated ligand HL.
Complex 2 contains two types of ligand anions – tridentate
bridging and didentate terminal (Figure 4).
Figure 4. Molecular structure of complex 2.
The CdII cations are in a distorted trigonal-bipyramidal
environment (CdO2S3). The axial positions are occupied by Cd01–O1B 155°), while the Cd01–O1A bond is practically
the oxygen atoms of the P=O groups, and the sulfur atoms perpendicular to the Cd2S4 plane. The S2B–Cd01–S2B_a
lie in its base. The Cd2S4 moiety is flat in the molecule of 2 angle in the Cd2S4 plane is more than 50° sharper than
(Table 2). Predictably, coordination bonds with the sulfur S2A–Cd01–S2B.
atoms of terminal ligands Cd01–S2A are, essentially, more
The lengths of the bonds in the S–C–N–P–O backbone
than 0.16 Å shorter than with the bridging sulfur atoms confirm the distinction in negative charge delocalisation
Cd01–S2B. The lengths of the Cd–O bonds in the CdII cat- mechanisms in bridging and terminal ligands. It is known
ion’s coordination sphere are practically equivalent, but the that three tautomeric forms, A, B and C, contribute to the
bond with the oxygen atom of the bridging ligand, Cd01– distribution of electronic density in six-membered chelates
O1B, deviates from the normal to the Cd2S4 plane (O1A– of (thioacylamido)phosphates (Scheme 2).
Table 2. Selected bond lengths [Å], and bond and torsion angles [°] for complex 2.[a]
Bond lengths
Cd01–S2A
Cd01–S2B
Cd01–O1A
Cd01–O1B
Cd01–S2B_a
S2A–C1A
S2B–C1B
2.5015(2)
2.6620(1)
2.313(3)
2.300(3)
2.5957(1)
1.744(5)
1.761(5)
P1A–O1A
P1A–N1A
P1B–O1B
P1B–N1B
N1A–C1A
N1B–C1B
1.444(2)
1.616(5)
1.468(4)
1.625(5)
1.283(7)
1.278(7)
Bond angles
S2A–Cd01–S2B
S2A–Cd01–S2B_a
S2B–Cd01–S2B_a
O1B–Cd01–S2B_a
S2A–Cd01–O1A
S2A–Cd01–O1B
S2B–Cd01–O1A
S2B–Cd01–O1B
O1A–Cd01–O1B
O1A–Cd01–S2B_a
Cd01–S2A–C1A
143.94(5)
123.91(5)
92.14(4)
105.9(1)
91.3(1)
Cd01–S2B–C1B
Cd01–S2B–Cd01_a
C1B–S2B–Cd01_a
O1A–P1A–N1A
O1B–P1B–N1B
Cd01–O1A–P1A
Cd01–O1B–P1B
P1A–N1A–C1A
P1B–N1B–C1B
S2A–C1A–N1A
S2B–C1B–N1B
114.2(2)
87.86(4)
96.4(2)
119.7(2)
120.6(2)
125.2(2)
128.8(2)
132.8(4)
130.4(4)
128.6(4)
127.6(4)
85.0(1)
83.46(9)
85.33(9)
155.3(1)
96.4(1)
110.6(2)
Torsion angles
C1A–S2A–Cd01–O1A
P1A–O1A–Cd01–S2A
Cd01–O1A–P1A–N1A
C1A–N1A–P1A–O1A
N1A–C1A–S2A–Cd01
S2A–C1A–N1A–P1A
–18.2(2)
–6.8(2)
–34.5(6)
–34.5(6)
25.8(5)
–0.1(8)
C1B–S2B–Cd01–O1B
P1B–O1B–Cd01–S2B
Cd01–O1B–P1B–N1B
C1B–N1B–P1B–O1B
N1B–C1B–S2B–Cd01
S2B–C1B–N1B–P1B
–167.73(19)
–19.3(3)
43.7(4)
–35.5(6)
20.5(5)
–0.3(7)
[a] Symmetry transformations used to generate equivalent atoms: _a (1–x, 1 –y, 1 –z).
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Coordination Mode of ZnII and CdII with N-(Diisopropoxyphosphoryl)thiobenzamide
FULL PAPER
Scheme 2.
Displacement of electronic density on the sulfur atom in
bridging ligands leads to the shortening of the C–N and
P=O bonds and also to the lengthening of the P–N and
C=S bonds because of the prevalence of the tautomeric
form A. The P=O bond in these ligands is even shorter than
in the free ligand molecule.[19] In the cases with terminal
ligands, the contribution of forms B and C which leads to
average bonds lengths in the cycle, is shown to a greater
degree.
The dimer formation leads to a significant lengthening
Figure 5. Molecular structure of complex 3.
of the Cd–S bonds in six-membered chelate cycles of the
bridging ligands. Therefore, these bonds are the longest in
a number of compounds investigated by us, their lengths
exceeding even those of the bridging Cd–S bonds connect-
ing [CdL2] moieties in the structure of the dimer.
Table 3. Selected bond lengths [Å], and bond and torsion angles [°]
for complex 3.[a]
Bond lengths
Cd1–S2
Cd1–O1
Cd1–O1A
S2–C1
S2A–C1A
P1–O1
2.546(2) P1–N1
1.611(3)
1.467(2)
1.677(3)
1.289(3)
1.363(4)
0.81(3)
2.273(2) P1A–O1A
2.372(2) P1A–N1A
1.687(3) N1–C1
1.637(3) N1A–C1A
1.444(2) N1A–H1A
Crystal Structure of 3
According to the Cambridge Crystallographic Database,
there are no structural analogues of complex 3 that involve
N-acylamidophosphates or related chelators such as imido-
diphosphinates and β-dicarbonyl compounds and Group
IIB cations. The nearest analogue of complex 3 is described
for iBu2NC(S)NHC(O)C6H5 (HQ). The complex has the
structure [Cd(HQ-S)(Q-O,S)2] (4).[22] As in complex 2, the
Bond angles
S2–Cd1–O1
89.74(8) O1A–P1A–N1A
88.76(7) Cd1–O1–P1
106.4(1)
120.6(1)
137.0(1)
134.6(2)
131.1(2)
116.7(2)
128.6(2)
114.6(2)
123.4(2)
S2–Cd1–O1A
S2–Cd1–S2_a
O1–Cd1–O1A
180.00
Cd1–O1A–P1A
89.25(8) P1–N1–C1
CdII cation in complex 4 is in a distorted trigonal-bipyrami- O1–Cd1–O1_a
180.00
180.00
P1A–N1A–C1A
N1–C1–C2
dal Cd(Oax)2(Seq)3 environment.
O1A–Cd1–O1A_a
Cd1–S2–C1
The molecule of complex 3 in a crystal is located in a
O1–P1–N1
105.1(1) S2–C1–N1
122.3(1) S2–C1–C2
114.9(2) S2A–C1A–N1A
121.8(2)
special position at the symmetry centre. The coordination
N1A–C1A–C2A
geometry of the CdII atom is tetragonal bipyramidal (D2h)
S2A–C1A–C2A
(Figure 5). Isostructural complexes of CoII and NiII with
Torsion angles
HL exist and have been synthesised by us previously.[21]
O1–Cd1–S2–C1
The equatorial positions of the bipyramid are occupied
O1A–Cd1–S2–C1
–39.8(1) O1–P1–N1–C1
–15.6(3)
177.2(2)
–30.1(2)
–174.5(2)
5.9(4)
49.5(1)
39.2(1)
O1A–P1A–N1A–C1A
N1A–P1A–O1A–Cd1
by two N-phosphorylthiobenzamide anions, bonded
S2–Cd1–O1–P1
through sulfur atoms and oxygen atoms of the phosphoryl O1A–Cd1–O1–P1
–49.5(1) P1–N1–C1–C2
S2–Cd1–O1A–P1A
68.8(2)
27.8(3)
P1–N1–C1–S2
P1A–N1A–C1A–S2A
groups. The six-membered Cd–O–P–N–C–S cycle has a
Cd1–S2–C1–N1
half-chair conformation; the O–P–N–C–S backbone is flat
N1–P1–O1–Cd1
0.1(4)
179.1(2)
–18.9(2) P1A–N1A–C1A–C2A
(Table 3). The ligands are in a trans configuration. A nega-
[a] Symmetry transformations used to generate equivalent atoms:
_a (2 – x, –y, 2 – z).
tive charge delocalisation in the S–C–N–P–O moiety also
takes place in this case. This leads to the contraction of the
C–N and P–N bonds and also to the lengthening of the
C=S bonds, but the P=O bond lengths decrease by 0.013 Å
relative to that of the free ligand HL. As in complex 2, this of C–N and P–N bonds in a crystal are practically identical
observation results from a significant preference of the form to those of free N-phosphorylthiobenzamide HL. Some
A (Scheme 2).
lengthening of the P=O and C=S bonds is observed, which
Neutral ligand molecules are coordinated in the axial po- results from the displacement of electronic density in the S–
sitions through the oxygen atoms of the phosphoryl groups. C–N–P–O moiety on the oxygen atom of the phosphoryl
The conformation of the neutral molecules and the lengths group.
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D. A. Safin et al.
FULL PAPER
H, C6H5), 7.85–7.88 (m, 2 H, o-H, C6H5), 8.49 (s, 1 H, NH) ppm.
There are two intramolecular NH···S bonds between the
neutral and anionic ligands in the crystal of complex 3. The
hydrogen bond parameters are as follows: N(1A)–H(1A)···
S(2) (–x, –y, –z), d(N–H) 0.81(3) Å, d(H···S) 2.72(3) Å,
d(N···S) 3.499(3) Å, Є(N–H···S) 164(2)°.
31P{1H} NMR (CDCl ): δ = –5.6 ppm. IR: ν = 3104 (NH), 1500
˜
3
(S=C–N), 1012 (POC), 1252 (P=O) cm–1.
Synthesis of [ZnL2] (1): A suspension of HL (1.505 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) solu-
tion of ZnCl2 (0.381 g, 2.8 mmol) was added dropwise under vigor-
ous stirring to the resulting potassium salt. The mixture was stirred
at room temperature for a further 3 h and left overnight. The re-
sulting complex was extracted with dichloromethane, washed with
water and dried with anhydrous MgSO4. The solvent was then re-
moved in vacuo. A colourless precipitate was isolated from dichlo-
romethane by n-hexane. Yield (based on the metal salt): 0.865 g
(52%). M.p. 92 °C. 1H NMR (CDCl3): δ = 1.34 (d, 3JH,H = 5.9 Hz,
Conclusion
Comparison of the data of complex compounds of cad-
mium(), known from the literature, with acylureas and im-
idodiphosphinates shows that the cadmium() cation in the
structure of the complex CdO2S2 core exhibits properties of
a “universal” Lewis acid. Its coordination environment can
be expanded because of interaction with both “soft” and
“hard” bases. Differences in modes of interaction are ap-
parently related to the distribution of electronic density in
the ligand molecules.
These features of complexes with a CdO2S2 core can be
used in the future for the creation of new types of building
blocks for polynuclear metal-containing macrocyclic com-
pounds. We have recently reported the synthesis of close
structural analogues of the ligand HL that contain crown
ether moieties and their complexes with NiII and
CuI.[11,23–25] The cavities of the macrocycles in the given
structures remain free and are capable of participating in
secondary coordination. We suppose that the combination
of the CdO2S2 core and crown ether in the molecule will
allow one to synthesise compounds that are able to bind
cations, by the crown ether moiety, and anions and neutral
molecules, by the electrophilic CdO2S2 core. Such kinds of
compounds are of interest as agents for molecular recogni-
tion and membrane transport.
3
12 H, CH3), 1.35 (d, JH,H = 5.8 Hz, 12 H, CH3), 4.72 (d. sept,
3
3JPOCH = 7.6 Hz, JH,H = 6.2 Hz, 4 H, OCH), 7.35–7.40 (m, 4 H,
m-H, C6H5), 7.45–7.50 (m, 2 H, p-H, C6H5), 8.26–8.29 (m, 4 H, o-
H, C6H5) ppm. 13C{1H} NMR (CDCl3): 24.5 (CH3), 73.5 (OCH),
128.4 (o-C, C6H5), 129.3 (m-C, C6H5), 132.6 (p-C, C6H5), 143.8
(ipso-C, C6H5), 195.2 (C=S) ppm. 31P{1H} NMR (CDCl3):
5.7 ppm. IR: ν = 1528 (SCN), 996 (POC), 1152 (P=O) cm–1. EI-
˜
MS: m/z (%) = 664 (8) [M]+, 301 (8) [HL]+. ES-MS (positive ion):
m/z (%) = 687 (100) [M + Na]+, 703 (10) [M + K]+, 1032 (1)
[M2L3]+, 1353 [M2L4 + Na]+. C26H38N2O6P2S2Zn (666.05): calcd.
C 46.87, H 5.77, N 4.18; found C 46.88, H 5.75, N 4.19.
Synthesis of [Cd2L4] (2) and [Cd(HL)2L2] (3): A suspension of HL
(1.806 g, 6 mmol) in aqueous ethanol (20 mL) was mixed with an
ethanol solution of potassium hydroxide (0.336 g, 6 mmol). An
aqueous (20 mL) solution of Cd(CH3COO)2·2H2O (0.798 g,
3 mmol) was added dropwise to the resulting potassium salt under
vigorous stirring. The mixture was stirred at room temperature for
a further 3 h and left overnight. The resulting complex was ex-
tracted with dichloromethane, washed with water and dried with
anhydrous MgSO4. The solvent was then removed in vacuo. The
residue was extracted by n-hexane. A hexane insoluble deposit was
recrystallised from a dichloromethane/n-hexane mixture, and com-
plex 2 was isolated. Complex 2 was obtained as colourless crystals.
Yield (based on the metal salt): 0.918 g (43%). M.p. 102 °C. 1H
Experimental Section
3
NMR (CDCl3): 1.40 (d, JH,H = 6.4 Hz, 24 H, CH3), 4.82 (d. sept,
3
3JPOCH = 7.5 Hz, JH,H = 6.4 Hz, 4 H, OCH), 7.34–7.39 (m, 4 H,
Physical Measurements: Infrared spectra (Nujol) were recorded
with a Specord M-80 spectrometer in the range 400–3600 cm–1.
NMR spectra were obtained on a Varian Unity-300 NMR spec-
trometer at 25 °C. 1H, 31P{1H} and 13C{1H} NMR spectra were
recorded at 299.948, 121.420 and 75.429 MHz, respectively. Chemi-
cal shifts are reported with reference to SiMe4 (1H and 13C{1H})
and H3PO4 (31P{1H}). Electron ionisation mass spectra were mea-
sured on a TRACE MS Finnigan MAT instrument. The ionisation
energy was 70 eV. The substance was injected directly into the ion
source at 150 °C. Heating was carried out in a programmed mode
from 35–200 °C at a rate of 35 °C/min. Electrospray ionisation
mass spectra were measured with a Thermo Finnigan LCQ mass
spectrometer on a 10–6  solution in a CHCl3/CH3OH mixture (1:1
v/v). The speed of a sample submission was 3 µL/min. The ioni-
sation energy was 4.1 kV. The capillary temperature was 210 °C.
Elemental analyses were performed on a Perkin–Elmer 2400 CHN
microanalyser.
m-H, C6H5), 7.44–7.49 (m, 2 H, p-H, C6H5), 8.23–8.26 (m, 4 H, o-
H, C6H5) ppm. 13C{1H} NMR (CDCl3): 24.5 (CH3), 73.2 (OCH),
128.4 (o-C, C6H5), 129.5 (m-C, C6H5), 132.4 (p-C, C6H5), 144.3
(ipso-C, C6H5), 193.9 (C=S) ppm. 31P{1H} NMR (CDCl3):
3.0 ppm. IR: ν = 1536, 1576, 1584 (SCN), 1015 (POC), 1184 (P=O)
˜
cm–1. EI-MS: m/z (%) = 714 (34) [ML2]+, 301 (15) [HL]+. ES-MS
(positive ion): m/z (%) = 715 (2) [ML2 + H]+, 737 (100) [ML2
+
Na]+, 753 (2) [ML2 + K]+, 1126 (38) [M2L3]+, 1449 (0.8) [M2L4 +
Na]+. C52H76Cd2N4O12P4S4 (1424.12): calcd. C 43.80, H 5.34, N
3.97; found C 43.81, H 5.33, N 3.98.
At the solvent-removal stage (hexane soluble), product 3 was iso-
lated. Complex 3 was obtained as yellow crystals. Yield (based on
the metal salt): 0.355 g (18%). M.p. 94 °C. 1H NMR (CDCl3): 1.29
3
3
(d, JH,H = 6.1 Hz, 36 H, CH3, L + HL), 1.35 (d, JH,H = 6.1 Hz,
12 H, CH3, L), 4.67 (d. sept, JPOCH = 3JH,H = 6.2 Hz, 4 H, OCH,
L), 4.82 (d. sept, JPOCH = JH,H = 6.4 Hz, 4 H, OCH, HL), 7.47–
Synthesis of (iPrO)2P(O)NHC(S)C6H5 (HL): N-Diisopropoxy- 7.74 (m, 12 H, m-H + p-H, C6H5, L + HL), 7.95–7.98 (m, 4 H, o-
3
3
3
phosphorylthiobenzamide was prepared according to previously
H, C6H5, HL), 8.26–8.28 (m, 4 H, o-H, C6H5, L), 9.15 [s, 2 H,
described methods.[26] M.p. 134 °C. 1H NMR (CDCl3): δ = 1.34 (d,
NHP(O)] ppm. 31P{1H} NMR (CDCl3): –6.0 (HL), 3.7 (L) ppm.
3
3JH,H = 5.9 Hz, 6 H, CH3), 1.38 (d, JH,H = 6.2 Hz, 6 H, CH3),
IR: ν = 1536 (SCN), 1013 (POC), 1168 (L, P=O), 1240 (HL, P=O)
˜
3
3
4.83 (d. sept, JPOCH = JH,H = 6.1 Hz, 2 H, OCH), 8.49 [s, 1 H,
cm–1. EI-MS: m/z (%) = 714 (29) [M – 2HL]+, 301 (73) [HL]+. ES-
NHP(O)], 7.37–7.42 (m, 2 H, m-H, C6H5), 7.49–7.54 (m, 1 H, p- MS (positive ion): m/z (%) = 715 (2) [ML2 + H]+, 737 (100) [ML2 +
2032
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Eur. J. Inorg. Chem. 2006, 2027–2034

Coordination Mode of ZnII and CdII with N-(Diisopropoxyphosphoryl)thiobenzamide
Table 4. Crystal data, data collection and refinement details for complexes 1–3.
FULL PAPER
1
2
3
Empirical formula
Formula mass
Space group
C26H38N2O6P2S2Zn
666.05
C2/c (molecule in special P1 (molecule in special
C52H78Cd2N6O10P4S4
1424.12
C52H78CdN4O12P4S4
1315.70
P21/n (molecule in special
¯
position on the axis 2)
position)
10.569(3)
10.941(2)
15.560(4)
74.11(2)
72.92(3)
79.93(3)
1645.5(8)
1
position)
13.375(9)
12.858(7)
18.594(7)
90
90.71(6)
90
3197(3)
2
1.37
a [Å]
b [Å]
c [Å]
α [°]
18.324(9)
9.730(9)
18.24(2)
90
93.35(7)
90
3247(5)
4
1.36
β [°]
γ [°]
V [Å3]
Z
Dcalcd. (mg/m3)
1.44
F(000)
Crystal colour
Crystal form
Crystal size [mm]
Radiation [Å]
Temperature [K]
1392
732
1372
colourless
prismatic
0.3×0.3×0.3
colourless
prismatic
0.4×0.3×0.2
1.54184
293
colourless
prismatic
0.2×0.3×0.2
0.71073
293
293
Scan mode
Recording range θmax [°]
ω
70.07
ω
57.19
ω
6.29
Absorption correction
ψ-scan
35.14
ψ-scan
77.46
ψ-scan
28.11
µ [cm–1]
Scan speed (°/min)
No. of recorded reflections
variable, 1–16.4
3373
variable, 1–16.4
3726
variable, 1–16.4
7205
No. of independent reflections with I Ն 3σ(I)
3016
2999
3695
3239
5022
6606
No. of independent reflections with F2 Ն 2σ(F2)
R (%)
Rw (%)
S
0.0449
0.1236
1.061
0.0557
0.1362
1.047
0.033
0.083
1.011
Na]+, 753 (2) [ML2 + K]+, 1126 (7) [M2L3]+. C52H78CdN4O12P4S4
(1315.70): calcd. C 47.44, H 6.01, N 4.29; found C 47.42, H 6.03,
N 4.28.
Acknowledgments
This work was supported by the Russian Foundation for Basic Re-
search (grant nos. 03-03-32372-a, 03-03-96225-r2003tatarstan_a),
the joint program of CRDF and the Russian Ministry of Education
(BHRE 2004 Y2-C-07-02, grants REC-007). D.A.S. thanks the Fa-
culty of Chemistry of the University of Wroclaw for a scholarship.
Crystal Structure Determination and Refinement: The X-ray diffrac-
tion data for the crystals of 1–3 were collected on a CAD4 Enraf–
Nonius automatic diffractometer using graphite-monochromated
Mo-Kα (0.71073 Å) and Cu-Kα (1.54184 Å) radiation. The crystal
data, data collection and the refinement are given in Table 4. The
stability of the crystals and the experimental conditions were
checked every 2 h using three control reflections, while the orienta-
tion was monitored every 200 reflections by centring two standards.
No significant decay was observed. An empirical absorption cor-
rection based on ψ-scans was applied. The structure was solved by
direct methods using the SIR[27] program and refined by the full-
matrix least-squares using the SHELXS-97[28] program. All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms for
compounds 1 and 3 were located from a subsequent difference map
and refined isotropically in the final cycles. The hydrogen atoms
for compound 2 were included in calculated positions with thermal
parameters 30% larger than the atom to which they were attached.
All calculations were performed on a PC using the WinGX[29] pro-
gram. Cell parameters, data collection and data reduction were per-
formed on an Alpha Station 200 computer using the MolEN[30]
program. All figures were made using the program PLATON.[31]
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Received: November 11, 2005
Published Online: March 23, 2006
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Eur. J. Inorg. Chem. 2006, 2027–2034