Synthesis and characterization of copper(I) halide complexes with N-(2, 6-diisopropylphenyl)-N′-benzoylthiourea: Monomeric, dimeric, and cage structures

Article abstract of DOI:10.1002/zaac.201400079

The N-(2, 6-diisopropylphenyl)-N′-benzoylthiourea ligand (shown as L) (1) was synthesized and characterized. Reactions of 1 with CuCl₂ and CuBr₂ afforded the monomeric L₂CuCl (2) and dimeric [LBrCu(μ-L)]₂ (3), r

Full text of DOI:10.1002/zaac.201400079

ARTICLE
DOI: 10.1002/zaac.201400079
Synthesis and Characterization of Copper(I) Halide Complexes with
N-(2,6-Diisopropylphenyl)-NЈ-benzoylthiourea: Monomeric, Dimeric, and
Cage Structures
[a]
[a]
[a]
[a]
Xiao-Ya Zhao, Cheng-Ben Zhu, Hai-Pu Li, Ying Yang,* and
Herbert W. Roesky*[
b]
Dedicated to Professor Helmut Werner on the Occasion of His 80th Birthday
Keywords: Acylthiourea; Copper(I) halides; S ligands; Cage compounds
Abstract. The N-(2,6-diisopropylphenyl)-NЈ-benzoylthiourea ligand
shown as L) (1) was synthesized and characterized. Reactions of 1 meric couple. The product of 1 and CuI was found to be dimeric
with CuCl and CuBr afforded the monomeric L CuCl (2) and di- [LICu(μ-L)] (5), which is isomorphous to 3. All compounds obtained
meric [LBrCu(μ-L)] (3), respectively, due to the reduction of Cu .
The reaction of 1 and CuCl gave the same product L
2 2 2 4
of adamantanoid cage (LCu) (μ-L) Cu (μ-Br) (4) containing enantio-
(
2
2
2
2
II
1
13
2
were fully characterized by elemental analysis, IR, H NMR and
C
2
CuCl (2), while NMR spectroscopy, and single-crystal X-ray diffraction.
the treatment of 1 with CuBr led to the formation of a rare example
Introduction
their complexes with “elusive” properties of binding modes,
beneficial in the presence of O, N, NЈ, and S donor atoms.
On the one hand, the N,N-dialkyl-NЈ-acylthiourea is able to
[
7]
Copper complexes with sulfur donors have attracted re-
newed interest for their pharmaceutical activity and potential
applicability as metal-based drugs, especially in the explora-
tion of the role of Cu system as antioxidant for preventing
oxidative DNA damage.[ Among these sulfur containing li-
coordinate only through sulfur as the neutral, monodentate li-
[
1]
[8]
gand, while it is also possible to act as a chelating bidentate
I
O,S-monoanionic ligand to form a six-membered ring with the
2]
[9]
metal ion in cis/trans arrangement. On the other hand, N-
gands, thiourea and its derivatives have been frequently re-
alkyl/aryl-NЈ-acylthiourea mostly behaves as a soft ligand with
I
[3]
ported to support Cu complexes. The acylthiourea deriva-
tives represent one of the popular members in the family of
thiourea and are attracting much research attention due to their
the sulfur donor in unidentate or diverse bridging modes in
I
[10]
its complexes with Cu salts,
favored by the formation of
intramolecular hydrogen bond (N–H···O). In a few cases, an
easy availability,[ facile reactivity and widespread application
4]
[11]
O,N-mode was observed.
Moreover, acylthiourea ligands
in analytical and heterocyclic chemistry.[
5]
The basic
have developed a wide variety of supramolecular synthons by
the intermolecular hydrogen bonds to generate 1D or 2D coor-
C(O)N(H)C(S)N unit that is shared by acylthiourea ligands is
also regarded as the core segment of special drugs with high
scores according to visual and structural criteria.[ Another
appealing feature of acylthioureas is the structural diversity of
[12]
dination polymers.
6]
The crystallization of acylthiourea complexes may be rel-
evant to the solvents, the strong hydrogen-bonding characteris-
[
13]
tics, modification by substitution,
tion between reactants.
or the relative concentra-
*
*
Dr. Y. Yang
[14]
Starting from the basic molecule of
Fax: +86-731-88879616
E-Mail: yangy@csu.edu.cn
Prof. Dr. H. W. Roesky
Fax: +49-551-39-33373
E-Mail: hroesky@gwdg.de
N-aryl-NЈ-benzoylthiourea, a number of derivatives have been
synthesized and structurally characterized with varying aryl
[
15]
[16]
[17]
rings typically modified by methyl,
carboxyl,
phenyl,
[18]
[19]
[10,20]
[
[
a] School of Chemistry and Chemical Engineering, Centre for hydroxyl,
trifluoromethyl,
ferrocenoyl,
and hal-
Environment and Water Resource
Central South University
Lushannan Road 932
[21]
ide
substituents. However, the isopropyl group, which has
been used as a bulky group in a number of ligand systems,
was not so common in acylthiourea derivatives.[ Previous
[
22]
12]
4
10083 Changsha, P. R. China
b] Institut für Anorganische Chemie
Universität Göttingen
work with β-diketiminato ligands has shown that the substitu-
Tammannstrasse 4
ent effect on the synthesis of dialuminoxanes is of principal
37077 Göttingen, Germany
[23]
importance.
In this study the synthesis of a new ligand
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201400079 or from the au-
thor.
N-(2,6-diisopropylphenyl)-NЈ-benzoylthiourea, as well as its
reactions with copper halides and the spectroscopic characteri-
1
614
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 640, (8-9), 1614–1621

Copper(I) Halide Complexes with N-(2,6-Diisopropylphenyl)-NЈ-benzoylthiourea
zation and structural determination of new copper(I) halide
acylthiourea complexes are reported.
The treatment of 1 in CH Cl with the ethanol solution of
2 2
CuCl and CuBr lead to the formation of L CuCl (2) and
2
2
2
[
LBrCu(μ-L)] (3), respectively, as shown in Scheme 1. The
H NMR spectrum of 2 exhibits that the NH protons resonate
2
1
at δ = 12.45 and 11.37 ppm, presenting a downfield shift when
compared to those of the free acylthiourea ligand (11.87,
Results and Discussion
9.25 ppm).
The N-(2,6-diisopropylphenyl)-NЈ-benzoylthiourea ligand
(1, shown as L) was readily prepared in moderate yield based
on the general procedure described in the literature for its
methyl analogue N-(2,6-dimethylphenyl)-NЈ-benzoylthiourea
[15]
1
(1Ј, donated as LЈ).
In the H NMR spectrum of 1, the
presence of one characteristic septet (δ =3.11 ppm) and two
doublet signal (1.32, 1.20 ppm) indicate the isopropyl group,
appearing relatively rotation-free of aryl flank in solution. Two
singlet signals were found at low field (11.87, 9.25 ppm),
which are assignable to the proton signals for thioamide aryl–
Scheme 1. Preparation of compounds 2 and 3.
Similarly, signals of the NH protons of 3 are observed at
NH and amide acyl–NH groups, respectively. This is consistent comparable positions (12.41 and 11.07 ppm). The single septet
with the observation of two distinctive absorption bands at siganl is upfield shifted in both cases (2.99–3.00 ppm). These
211 and 3232 cm– in the FT-IR spectra due to the N–H changes are indicative for the complex formation.
1
[10]
The com-
3
stretching vibrations. X-ray quality single crystals were ob- position of 2 and 3 was further confirmed by elemental analy-
tained from a saturated THF solution. Room-temperature X- sis and single-crystal X-ray diffraction.
ray diffraction data of 1·THF indicate that the structure belongs
Compound L CuCl (2) crystallizes in the triclinic space
to the monoclinic space group P2 /c with two symmetry inde- group P1 with one severely disordered molecule of n-hexane
2
¯
1
pendent molecules in a centrosymmetric unit. One of them is in the unit cell. No acceptable connectivity could be estab-
depicted in Figure S1 (Supporting Information) with selected lished for the embedded solvent molecule. The disordered
bond lengths and angles, and crystal data and structure refine- electron density was excluded using the SQUEEZE function
ments are listed in Table S1 (Supporting Information). The of the PLATON program.[ The X-ray structure reveals 2 as
C(2)–O(1) bond length [1.219(2) Å] of 1·THF is found to be a mono nuclear copper(I) chloride complex coordinated by two
exactly the same as that of its methyl analogue,[ whereas the sulfur atoms of each acylthiourea ligand and one chlorine atom
C(1)–S(1) separation [1.676(2) Å] is slightly longer than that (Figure 1).
25]
15]
of 1Ј [1.6599(19) Å]. As expected, an intramolecular hydrogen
bonding interaction N(1)–H(1A)···O(1) [D···A, 2.664(2) Å;
D–H···A, 134.2°] is present and helps to form a pseudo-six-
membered ring. Closer examination reveals that the two inde-
pendent molecules in the crystal structure of 1·THF form a
twelve-membered cyclic dimer[
12,24]
mediated by intramolecu-
lar N–H···O hydrogen bonds (Figure S2) and thus construct
molecular chains by intramolecular N–H···S contacts along the
a axis.
Furthermore, the single crystals of the ligand L without sol-
vent molecules present in the structure were obtained from n-
¯
hexane solution. 1 crystallizes in the triclinic space group P1
3
with a small cell volume [927.50(18) Å ]. In contrast to its
THF solvate, 1 contains a single ligand molecule in the centro-
symmetric unit. Yet similarly, ligand molecules are connected
by intermolecular hydrogen bonds to produce the molecular
chain along the diagonal of a and b crystallographic axes (Fig-
ure S3, Supporting Information). Instead, its methyl analogue
Figure 1. Molecular structure of 2, showing intramolecular hydrogen
bonds as dotted lines. Thermal ellipsoids are drawn at 30% level.
Other hydrogen atoms are omitted for clarity. Selected bond lengths
/Å and angles /°: Cu(1)–S(1) 2.2026(6), Cu(1)–S(2) 2.2114(7), Cu(1)–
1
Ј showed a weak intermolecular C–H···S interaction in the
[15]
solid state.
It is well known that the preparation of complexes of CuI Cl(1) 2.2236(7); S(1)–Cu(1)–S(2) 115.71(2). Hydrogen bonds D···A
distances /Å and D–H···A angles /°: N(2)–H(1A)···O(1) [2.621(3),
with thiourea derivatives can be simply achieved by mixing
137], N(3)–H(1B)···Cl(1) [3.277(2), 166], N(4)–H(2A)···O(2)
II
[13]
the solution of ligand and the corresponding Cu salt,
[
2.618(3), 141], N(1)–H(2B)···Cl(1) [3.454(2), 157].
II
I
where Cu is reduced to Cu with concomitant oxidation of a
portion of the thiourea ligand. In some cases, the chemical
The two ligands of 2 adopt a cis arrangement relative to the
composition or structures of final products depend on the thio- chlorine atom. This butterfly-like structure with a less confor-
urea ligand involved and also on the reaction conditions.[
13,14]
mational flexibility is common in literature.
[10,26]
One of the
1615
Z. Anorg. Allg. Chem. 2014, 1614–1621
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de

X.-Y. Zhao, C.-B. Zhu, H.-P. Li, Y. Yang, H. W. Roesky
ARTICLE
main driving factors for the structural feature are the intra- formed by combining L CuCl molecules with the single intra-
2
molecular hydrogen bonds between Cl(1) and N(1)/N(3) atoms molecular hydrogen bonding interaction of N(3)–H(3)···O(1A)
to form pseudo-six-membered rings. The Cu–Cl and Cu–S [D···A, 3.273(4) Å, D–H···A, 132.5°, [–x+3/2, –y+2,
[10,26]
bond lengths are each found in the reasonable range,
and z+1/2]] (Figure S7). Interestingly, 2·tol crystallizes in a chiral
the sum of the bond angles around the copper is exactly 360° space group. The possible axial chirality could be induced by
to exhibit a trigonal planar arrangement. Aromatic rings funda- restricted rotation of the ligand framework along the molecule
mentally occupy the opposite sides of the CuS Cl plane when axis in the case of using an achiral ligand.[
28]
2
compared to their counterparts. There are no intermolecular
The structure of 3 (Figure 3) of composition [LBrCu(μ-L)]2
hydrogen bonds evident in the structure. Instead, the crystal cocrystallizes with two toluene solvent molecules in the tri-
¯
packing structure of 2 (Figure 2) shows the significant stabili- clinic space group P1. The dimer is located in a crystallo-
zation by intermolecular π–π stacking interactions between graphic center of symmetry, comprising a [Cu(μ-S)]2 four-
two neighboring phenyl rings (I)···(I) in the cell, centroid– membered ring. One striking feature is that the Cu···Cu
centroid distance 3.8041(14) Å, face-to-face, with a dihedral separation [2.6121(6) Å] is obviously the shortest thus far ob-
angle of 0°. Additionally, similar but much weaker intermo- served in the analogous systems bearing the [SBrCu(μ-S)]
2
[13,29]
lecular π–π stacking interactions are found between their sib- core involving heterocyclic thiones
or acyclic thiourea
ling phenyl rings (II)···(II) [centroid–centroid distance derivative,[30] and similar to but still slightly shorter than
4.2553(16) Å].
that of a related compound containing a [PBrCu(μ-S)]
2
[31]
core [2.6906(1) Å].
Comparable Cu···Cu separations
32a]
2.6316(13)[32b]] were previously reported on
[
2.619(2) Å,[
copper(II) compounds containing the [SClCu(μ-S)] core.
2
Figure 2. Structure diagram of 2, showing the intermolecular π–π
stacking interactions between phenyl rings: (I)···(I), centroid–centroid
distance 3.8041(14) Å, dihedral angle 0°, slip angle 22°, perpendicular
distance between the rings 3.5274(9) Å, slippage 1.424 Å; (II)···(II),
centroid–centroid distance 4.2553(16) Å, dihedral angle 0°, slip angle
3
2
6.8°, perpendicular distance between the rings 3.4069(11) Å, slippage
.55 Å.
Figure 3. Molecular structure of 3, showing intramolecular hydrogen
bonds as dotted lines. Other hydrogen atoms are omitted for clarity.
Selected bond lengths /Å and angles /°: Cu(1)–S(1) 2.3863(7), Cu(1)–
S(2) 2.2829(7), Cu(1)–Br(1) 2.4207(4), Cu(1)–Cu(1A) 2.6121(6);
Cu(1)–S(1)–Cu(1A) 66.29(2). Hydrogen bonds D···A distances /Å and
D–H···A angles /°: N(2)–H(2A)···O(1) [2.605(3), 133], N(4)–H(4A)
The two short contacts in zigzag arrangement form the teeth
of adjacent molecular arrays and interlock them into a coordi-
nation chain in the c axis direction (Figure S4).
In contrast, from the concentrated toluene solution, 2·tol was
obtained, which crystallizes with a toluene molecule in the or-
thorhombic space group P2 2 2 . The observation that the
·
··O(2) [2.658(3), 130], N(3)–H(3A)–Br(1) [3.527(2); 172.0], N(1)–
H(1A)–Br(1A) [3.399(2), 149.9; (–x+2, –y+1, –z+1)].
1
1 1
crystal contains solvent molecules and gives rise to a different
space group is commonly seen in practice.[
The closed-shell interactions between the central d10 metal
27]
The crystal atoms are generally designated as metallophilic interactions.
structures of 2 and 2·tol (Figure S5) are essentially similar with For example, aurophilicity has long been recognized and plays
respect to the cis arrangement of two ligands and bond angles a dominant role in gold chemistry, while cuprophilic interac-
around the copper atom (360°). However, the torsion angles of tions are still controversial.[ Metallophilic Cu –Cu interac-
33]
I
I
Cl(1)–Cu(1)–S(1)–C(1) [–29.90(19)°] and Cl(1)–Cu(1)–S(2)– tions are frequently evidenced between 2.60 and 3.50 Å in li-
[
33f]
C(21) [19.42(19)°] of 2·tol are significantly different from, and gand-unsupported systems.
In an alternative view, the van
I
I
wider than, those of 2 [11.85(9), 8.93(9)°]. The aromatic rings der Waals radius (Cu –Cu 2.80 Å) is often used as reference
of 2·tol are almost located on the same sides of the CuS Cl data to draw a comparison to the cuprophilicity before exten-
2
plane. The packing diagram of 2·tol gives a plausible explana- sive calculations or spectroscopic characterizations are carried
tion that the molecular skeleton bends slightly to embrace the out.[ However, metallophilic effects concerning bridging li-
cocrystallized molecule of toluene (Figure S6). Consequently, gands should be treated with caution, because the effects are
an interesting wave-shape molecular chain along the c axis is easily blurred by the architecture of the ligand. The short
34]
1
616
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© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 1614–1621

Copper(I) Halide Complexes with N-(2,6-Diisopropylphenyl)-NЈ-benzoylthiourea
Cu···Cu contact [2.6121(6) Å] in 3, together with the com-
pressed Cu–S–Cu angle [66.29(2)°], might suggest the pres-
ence of weak attractive metallophilic interactions between the
central copper atoms. However, the close proximity of copper
atoms could be caused by the ring constraint and ligand ef-
fect.[
34g]
Another feature in 3 is that a 2D molecular sheet is as-
sembled by intermolecular hydrogen bonding interaction
of N(4)–H(4A)···O(2A) [D···A, 3.104(3) Å, D–H···A, 142°,
[
–x+2, –y+1, –z]] along the c axis and by intermolecular π–π
stacking interactions between two neighboring phenyl rings
I)···(I) along the axis [centroid–centroid distance
(
b
Figure 4. Core structure of 4. Thermal ellipsoids are drawn at 30%
3
.7630(19) Å, face-to-face, with a dihedral angle of 0°, slip level. Other atoms are omitted for clarity. Selected bond lengths /Å
and angles /°: for 4a: S(1)–Cu(1) 2.2687(18), S(4)–Cu(4) 2.3208(18),
angle 25°, perpendicular distance between the rings
.4110(12) Å, slippage 1.589 Å] (Figure S8, Supporting Infor-
mation).
Br(4)–Cu(1) 2.3273(11), Br(4)–Cu(4) 2.5392(9), Cu(1)–Cu(3)
3
2
2
.6223(10); Cu(1)–Br(1)–Cu(3) 67.60(3); for 4b: S(7)–Cu(7)
.2792(16), S(7)–Cu(8) 2.3208(17), Br(7)–Cu(7) 2.3314(11), Br(7)–
At the same time, reactions of the acylthiourea ligand 1 and Cu(6) 2.5267(10), Cu(5)–Cu(7) 2.6140(12); Cu(5)–Br(5)–Cu(7)
67.39(3).
copper(I) halides were conducted for comparison (Scheme 2).
The product of 1 and CuCl was found to be identical to
L CuCl (2) according to spectroscopic and structural charac-
2
I
4 exhibits Cu ions both in tricoordinate [Cu(1) and Cu(3)] and
tetracoordinate [Cu(2) and Cu(4)] mode with distorted trigonal
planar and tetrahedral coordination, respectively. As expected,
the Cu–S and Cu–Br bond lengths of the tricoordinate copper
terization. However, treatment of 1 with CuBr gave product 4
with slightly different chemical shifts of NH protons (12.47,
10.95 ppm) compared to those of 3 (12.41, 11.07 ppm). Ele-
mental analysis of 4 suggests a 1:1 stoichiometry copper(I)
bromide of acylthiourea ligand.
ions are distinctly shorter than those of the tetracoordinate
[36]
ones.
For instance in 4a, the bond lengths of Cu(1) and
Cu(3) with respective bridging atoms S(1), S(3), Br(2), or
Br(4) (if available) are shorter than those involving Cu(2) and
Cu(4) atoms.
It has been shown that reactions between copper(I) halides
and thiourea or its derivatives frequently generate a variety of
complexes, which have unpredictable stoichiometry and
stereochemistry.[
37]
This structural diversity originates from
the propensity of the halide to act as terminal or bridging li-
gand and of the thiourea ligand to coordinate in a monodentate
Scheme 2. Reaction of 1 with copper(I) halides.
X-ray structural analysis confirmed the 1:1 composition of or a bridging mode.[ In the known tetranuclear Cu systems
36]
I
4
and further indicated the formation of a cage-like compound with sulfur donor, the adamantanoid cages often contain the
[38]
(LCu) (μ-L) Cu (μ-Br) . Complex 4 crystallizes in the tri- Cu S core,
in which simply the soft anions like halides
2
2
2
4
4 6
¯
clinic space group P1. There are two inequivalent molecules have the chance to bind with the copper site in a terminal
in the asymmetric unit. They have the same overall structure, fashion (Cl,[
39] [13,37]
I
). Only one comparable example involv-
but their conformations are distinctly different by forming an ing edge-bridging bromine atoms in the P Cu Br core with
4
4
4
enantiomeric couple. The different core structures are illus- adamantane-like topology was established by treatment of
trated in Figure 4.
Each molecule contains an unprecedented central S Cu Br
4
framework of an adamantane-like structure that comprises four dergo a similar “windshield-wiper” sliding movement of the
1,1Ј-diphosphaferrocene with CuBr, but with single conforma-
tion.[ In solution, the core structures of 4a to 4b might un-
36]
2
4
[36]
annealed six-membered SCu Br rings in a chair conformation. ligands along each Cu···Cu pair vector (Cu1,2 and Cu3,4) by
3
2
In each molecule, four CuBr units form a puckered Cu (μ- simultaneously changing the role of terminal and bridging
4
Br) eight-membered ring, which is rarely reported in litera- mode, so as to refold the Cu Br ring and then interconverse
4
4
4
ture.[ Taking 4a for example, the four bromide anions almost to each other. Compound 4 is relatively stable under ambient
35]
II
lie in a common plane, as indicated by the tiny deviation of condition. In contrast to some cases, Cu compound was poss-
the Br(1) atom from the Br(2)Br(3)Br(4) plane (0.086 Å). The ibly formed in air to introduce a μ -O into the cage.
[40]
4
four copper atoms create a highly distorted tetrahedron with
A detailed investigation of the molecular structure of 4 leads
Cu···Cu distances ranging from 2.622 to 3.739 Å, and they can to the finding that the terminal sulfur donors nearly lie on the
be divided into two special Cu···Cu pairs (Cu1,2 and Cu3,4) by plane defined by two tetracoordinate copper atoms and their
the Br quasi-plane, each bridged by one sulfur donor of the bridging bromide atom. This plane could describe the charac-
4
acylthiourea ligand. The sulfur atoms of the other two ligands teristic position of each molecule. Such two planes of 4a and
additionally coordinate to one copper atom of the pairs above 4b are roughly perpendicular (86.09°) to each other. In ad-
[Cu(2) in Cu1,2 and Cu(4) in Cu3,4] in a terminal fashion. Thus dition, exemplified by 4a (Figure 5), the top apex bromide
Z. Anorg. Allg. Chem. 2014, 1614–1621
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de 1617

X.-Y. Zhao, C.-B. Zhu, H.-P. Li, Y. Yang, H. W. Roesky
ARTICLE
atom Br(3), which connects two tetracoordinate copper atoms, lecular hydrogen bonding interaction is detected in 2Ј. The
exhibits potentially weak intramolecular hydrogen bonding molecules are connected by intermolecular π–π stacking inter-
with two nitrogen atoms from the bridging ligands, while the actions between two neighboring 2,6-dimethylphenyl rings,
shoulder bromide atoms Br(2) and Br(4) form weak intramo- face-to-face, in a direction parallel to each other, resulting in
lecular hydrogen interaction each with the nitrogen donor from one type of 1D strand along the c axis (Figure S11).
the terminal ligand. Restrictions imposed by those interactions
together with steric strain of the ligand render short [LICu(μ-L)] (5) of 1:2 stoichiometry (Scheme 2). In the H
The reaction of 1 with CuI afforded the dimeric adduct
1
2
Cu(1)···Cu(3) distance of 2.6223(10) Å. Also the inward bend- NMR spectrum of 5, there are two singlet signals found at low
ing of the copper atoms Cu(1) and Cu(3) in 4a results in a field (12.17, 10.34 ppm) responsible for NH proton reso-
somewhat acute Cu(1)–Br(1)–Cu(3) angle of 67.60(3)°, which nances, which are shifted slightly upfield relative to those of
[36]
is very close to that in the P Cu Br complex [66.61(5)°].
2–4. The iodide (5) and bromide (3) complexes are isomorph-
4
4
4
The root tip bromide atom Br(1) is found to be innocent in ous, therefore, the molecular conformation of them is very
any hydrogen bonding interaction. According to the vector similar. The dimer 5 is located around a crystallographic center
moving from the top Br(3) to the Br(1), both 4a and 4b show of symmetry, one half comprising the asymmetric unit of the
the same direction in the cell. The ligands residing on the op-
structure (Figure S12). The Cu···Cu distance [2.7378(8) Å]
falls in the expected range. As in the form of 3 and the parent
ligand, it appears that hydrogen bonding is an important con-
tributor to the stability of 5, and each iodide is involved in
intramolecular hydrogen bonds with nitrogen donors from
two adjacent terminal and bridging ligands. Molecules of 5
are connected by intermolecular N(2)–H(2A)···O(1A) [D···A,
posite sides of the S Cu Br core adopt the cis arrangement
2
4
4
relative to each other, while each ligand is in the trans arrange-
ment with respect to its nearest neighbors. It is interesting to
note that all ligand planes (defined by N O) tilt relative to the
2
top bromide vector by 11–23° in anti-clock wise in 4a and in
clock wise in 4b, when looking inwards the molecule.
3.260(3) Å, D–H···A, 132.9°, [–x, 1–y, 1–z]] hydrogen bonds
forming chains running along the b axis (Figure S13, Support-
ing Information).
Conclusions
The new acylthiourea ligand N-(2,6-diisopropylphenyl)-NЈ-
benzoylthiourea (1, shown as L) and its derivatives with cop-
per(I) halides (2–5) were synthesized and characterized. In the
solid state of 1·THF, molecular dimeric chains are formed by
intermolecular hydrogen bonding along the a axis, which is
totally different with its methyl analogue by a weak intermo-
lecular C–H···S interaction. The reaction of 1 with CuCl and
2
CuBr afforded mononuclear L CuCl (2) and dimeric dinu-
2
2
Figure 5. Molecular structure of 4a with intramolecular hydrogen
bonds as dotted lines. Other hydrogen atoms are omitted for clarity.
Hydrogen bonds D···A distances /Å and D–H···A angles /°: N(2)–
H(2A)···Br(3) [3.631(4), 172.5], N(6)–H(6A)···Br(3) [3.717(4), 167.5],
clear [LBrCu(μ-L)] (3), respectively. Complex 3 exhibits the
2
shortest Cu···Cu separation [2.6121(6) Å] so far known of this
type. A molecular chain is also formed in 3 by intermolecular
N(4)–H(4A)···Br(2) [3.556(5), 145.2], N(8)–H(8A)···Br(4) [3.509(4), N–H···O hydrogen bonding along the c axis. Treatment of 1
151.6].
with CuCl gave the same complex L CuCl (2), while the prod-
2
uct of 1 and CuI turned out to be the dimeric adduct [LICu(μ-
Intermolecular N–H···O hydrogen bonding interactions of 4
L)] (5) with a structure resembling to that of [LBrCu(μ-L)]2
give rise to an infinite 2D grid in the ac plane of the unit cell.
Each molecule is interconnected to its four enantiomers (Fig-
ure S9), so as to define 4 a racemic compound.
In a comparative manner, the complexation reaction of the
methyl derivative N-(2,6-dimethylphenyl)-NЈ-benzoylthiourea
2
(3). Instead, the direct reaction of 1 with CuBr led to the for-
mation of the adamantanoid cage (LCu) (μ-L) Cu (μ-Br) (4)
2
2
2
4
with two inequivalent molecules as enantiomeric couple. Inter-
molecular N–H···O hydrogen bonding of cages 4 give rise to
(
1Ј) with CuBr in a 1:1 ratio (Scheme S1) was carried out. an infinite 2D grid in the ac plane of the unit. In sharp contrast,
Instead of cage structure, the product turned out to be the di- treatment of its methyl analogue with CuBr resulted in the
mer [LЈBrCu(μ-LЈ)] (2Ј), which crystallizes also with two tol- formation of dimeric [LЈBrCu(μ-LЈ)] (2Ј). These results sug-
gest that the ligand effect plays an important role in thiourea
2
2
¯
uene molecules in the triclinic space group P1 (Figure S10,
Supporting Information) and is isostructural with 3 and con- derivatives. The isopropyl-substituted ligand L provided
tains the [SBrCu(μ-S)] core. The Cu···Cu separation of 2Ј unique examples of copper(I) halide complexes with structural
2
[
2.6235(6) Å] is slightly longer than that of 3 but still shorter diversity feature of monomeric, dimeric, and cage conforma-
[13,29,30]
than those of other analogues.
No evident intermo- tions.
1
618
www.zaac.wiley-vch.de
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2014, 1614–1621

Copper(I) Halide Complexes with N-(2,6-Diisopropylphenyl)-NЈ-benzoylthiourea
Ar/Ph), 2.99 [sept, 3JHH = 6.5 Hz, 2 H, CH(CH
)
2
], 1.26 [d, 3JHH
], 1.16 [d, JHH = 6.9 Hz, 6 H, CH(CH ] ppm.
C NMR (101 MHz, CDCl ): δ = 182.58 (C = S), 169.77 (C=O),
145.13, 134.12, 130.88, 129.99, 129.55, 128.73, 124.00, 123.54 (Ar/
=
3
3
6
.8 Hz, 6 H, CH(CH
3
)
2
3 2
)
Experimental Section
1
3
3
All chemicals commercially available used in the synthesis were of
analytical grade and used as received. Melting points were measured in Ph), 28.89 [CH(CH ) ], 24.43, 23.06 [CH(CH ) ] ppm. IR (KBr): ν˜ =
3
2
3 2
sealed glass tubes using a Büchi B-540 instrument without correction.
3518 (w), 3424 (w), 3187 (m), 2963 (m), 2868 (w), 1675 (s), 1599
Elemental analyses for carbon, hydrogen, and nitrogen were performed (w), 1510 (vs), 1384 (w), 1362 (w), 1317 (m), 1260 (s), 1205 (m),
1
13
with a Thermo Quest Italia SPA EA1110 instrument. The H and
C
1158 (s), 1104 (w), 1084 (w), 1024 (w), 852 (w), 799 (m), 752 (m), 732
–
1
NMR spectra were recorded with 5 mm tubes in CDCl solution using (m), 712 (m), 687 (m), 661 (m) cm . C H Br Cu N O S (1648.83):
3
8
0
96
2
2 8 4 4
AVANCE III 400 and AVANCE III HD 500 spectrometers. Infrared calcd. C 58.28, H 5.87, N 6.80%; found C 58.40, H 5.53, N 6.58%.
spectra were recorded by using KBr pellets with a NEXUS670 X-ray quality single crystals of 3·2tol were obtained from a concen-
(Thermo Fisher Scientific) FT-IR spectrometer.
trated toluene solution.
N-(2,6-diisopropylphenyl)-NЈ-benzoylthiourea (L) (1): Ligand (L)
(LCu) (µ-L) Cu (µ-Br) (4): The procedure for the preparation of 4
2
2
2
4
was prepared using a similar procedure to that described for was similar to that described for compound 2 using 1 (1.70 g, 5 mmol)
[
15]
N-(2,6-dimethylphenyl)-NЈ-benzoylthiourea
by the reaction of in THF (30 mL) and CuBr (0.72 g, 5 mmol) in ethanol (30 mL) to
benzoyl chloride with KSCN in acetone to produce benzoyl isothiocya-
nate, followed by the condensation with 2,6-diisopropylaniline. The
afford a yellow solid, which was recrystallized from ethanol (1.06 g,
1
0.55 mmol, 44%). M.p. 238–240 °C. H NMR (400 MHz, CDCl ): δ
3
product in 50 mmol scale synthesis was recrystallized from acetone to = 12.47 (s, 1 H, NH), 10.95 (s, 1 H, NH), 8.28, 7.62, 7.51, 7.38, 7.21
3
give a moderate yield (13.79 g, 40.50 mmol, 81%). M.p. 195–197 °C.
(m, 8 H, Ar/Ph), 2.98 [sept, J = 6.5 Hz, 2 H, CH(CH ) ], 1.27 [d,
HH
3 2
1
3
3
H NMR (500 MHz, CDCl
3
): δ = 11.87 (s, 1 H, NH), 9.25 (s, 1 H,
3 2
JHH = 6.7 Hz, 6 H, CH(CH ) ], 1.16 [d, JHH = 6.7 Hz, 6 H,
NH), 7.94, 7.68, 7.57 (m, 5 H, Ph), 7.40, 7.25 (m, 3 H, Ar), 3.11 [sept, CH(CH ) ] ppm. C NMR (101 MHz, CDCl ): δ = 179.77 (C = S),
1
3
3
2
3
3
], 1.32 [d, 3
], 1.20 [d, JHH = 6.9 Hz, 6 H, CH(CH
101 MHz, CDCl ): δ = 181.39 (C = S), 167.04 (C=O), 145.59, 133.81,
29.25, 129.12, 127.67, 123.86 (Ar/Ph), 28.92 [CH(CH ], 24.41, (vw), 1508.32 (s), 1489.02 (m), 1383.85 (vw), 1362.48 (w), 1311.86
3.13 [CH(CH ] ppm. IR (KBr): ν˜ = 3232 (m), 3122 (m), 2962 (s),
(w), 1257.56 (m), 1204.29 (w), 1154.31 (m), 1102.71 (vw), 1067.16
868 (m), 1667 (s), 1600 (w), 1527 (vs), 1383 (m), 1362 (m), 1326 (w), 1023.98 (vw), 799.39 (w), 750.99 (w), 704.57 (w), 685.29 (w),
J
HH = 7.0 Hz, 2 H, CH(CH
3
)
2
JHH = 6.8 Hz, 6 H, 169.84 (C=O), 145.12, 134.13, 131.56, 130.69, 129.59, 128.74, 124.02
3
13
CH(CH
3
)
2
3 2
3 2 3 2
) ] ppm. C NMR (Ar/Ph), 28.91 [CH(CH ) ), 24.45, 23.08 (CH(CH ) ] ppm. IR (KBr):
(
3
ν˜ = 3150.96 (w), 2962.96 (m), 2867.51 (w), 1672.45 (m), 1596.04
1
2
2
3 2
)
3 2
)
–
1
(m), 1259 (s), 1204 (m), 1156 (s), 1058 (w), 1025 (w), 999 (w), 931
80 96 4 4 8 4 4
661.86 (w) cm . C H Br Cu N O S (1935.73): calcd. C 49.64, H
(
w), 802 (m), 752 (w), 701 (m), 686 (m), 665 (m), 621 (w), 531 (w) 5.00, N 5.79%; found C 49.34, H 5.15, N 5.63%. X-ray quality single
–
1
cm . C20
H
24
N
2
OS (340.5): calcd. C 70.55, H 7.10, N 8.23%; found
crystals of 4 were obtained from a concentrated THF solution.
C 70.63, H 7.38, N 8.40%. X-ray quality single crystals of 1·THF
were obtained from a concentrated THF solution.
[
LICu(μ-L)]
to that described for compound 2 using 1 (0.85g, 2.5 mmol) in THF
20 mL) and CuI (0.25 g, 1.3 mmol) in ethanol (20 mL) to afford a
yellow precipitate. The solid was separated by filtration and washed
2
(5): The procedure for the preparation of 5 was similar
L
2
CuCl (2): To a solution of 1 (3.40 g, 10 mmol) in dichloromethane
30 mL) at room temperature was added drop by drop a solution of
CuCl ·2H O (0.85 g, 5 mmol) in ethanol (30 mL) in 15 min under in-
(
(
1
2
2
with n-hexane (0.4 g, 0.23 mmol, 37%). H NMR (400 MHz, CDCl
δ = 12.17 (s, 1 H, NH), 10.34 (s, 1 H, NH), 8.17, 7.64, 7.53, 7.37,
7
):
3
tense stirring. An additional 6 h was allowed to insure completion of
complexation. The precipitate was separated by filtration, washed with
distilled water repeatedly, and dried at 80 °C to obtain a white solid
3
.22 (m, 8 H, Ar/Ph), 3.01 [sept, JHH = 6.5 Hz, 2 H, CH(CH
3
)
2
], 1.26
HH = 6.7 Hz, 6 H,
): δ = 180.49 (C = S),
68.96 (C=O), 145.34, 133.96, 131.91, 130.70, 129.34, 129.24,
28.86, 123.91 (Ar/Ph), 28.85 [CH(CH ], 24.38, 23.08 [CH(CH
3
3
[
d,
J
HH = 6.7 Hz, 6 H, CH(CH
3
)
2
], 1.17 [d,
J
(1.60 g, 2.05 mmol, 41%). Complex 2 was alternatively accomplished
13
CH(CH
1
1
3
)
2
] ppm. C NMR (126 MHz, CDCl
3
by using 1 (1.70 g, 5 mmol) in THF and CuCl (0.25 g, 2.5 mmol) in
ethanol (30 mL) in moderately higher yield (1.35 g, 1.73 mmol, 69%).
3
)
2
3 2
) ]
1
M.p. 239–241 °C. H NMR (500 MHz, CDCl
3
): δ = 12.45 (br., 1 H,
ppm. IR (KBr): ν˜ = 3210 (w), 2961 (w), 2926 (vw), 2866 (vw), 1672
w), 1528 (m), 1507 (m), 1488 (w), 1363 (vw), 1317 (vw), 1257 (w),
200 (vw), 1152 (w), 800 (vw), 752 (vw), 702 (vw), 685 (vw), 664
NH), 11.37 (s, 1 H, NH), 8.31, 7.64, 7.52, 7.36, 7.21 (m, 8 H, Ar/Ph),
(
1
(
6
3
3
3
.00 [sept, JHH = 6.5 Hz, 2 H, CH(CH
H, CH(CH
], 1.16 [d, 3
NMR (101 MHz, CDCl
33.96, 131.78, 131.07, 129.52, 129.42, 128.64, 123.96 (Ar/Ph), 28.85
CH(CH ], 24.43, 23.04 [CH(CH ] ppm. IR (KBr): ν˜ = 3440 (w),
357 (w), 3187 (w), 2963 (w), 2868 (vw), 1672 (m), 1514 (s), 1465
3
)
2
], 1.27 [d, JHH = 6.4 Hz, 6
13
)
2
J
HH = 6.4 Hz, 6 H, CH(CH
): δ = 181.36 (C = S), 169.80 (C=O), 145.22,
3
)
2
] ppm.
C
–1
3
2 2 8 4 4
w) cm . C80H96Cu I N O S
(1742.83): calcd. C 55.13, H 5.55, N
3
.43%; found C 55.25, H 5.42, N 6.35%. X-ray quality single crystals
1
[
3
of 5 were obtained from a concentrated toluene solution.
3
)
2
3 2
)
X-ray Crystallography: Data were collected with a Bruker SMART
(
1
w), 1396 (vw), 1363 (vw), 1315 (w), 1261 (m), 1205 (w), 1157 (m), APEX II CCD diffractometer for 1·THF, 2–5, and 2Ј·2tol and an Ox-
103 (vw), 1084 (vw), 1025 (vw), 936 (vw), 852 (vw), 800 (w), 732 ford Gemini S Ultra system for 1. The diffraction data were obtained
–1
(w), 711 (w), 687 (w), 662 (w) cm . C40
H48ClCuN
4
O
2
S
2
(779.96):
α
by using graphite monochromated Mo-K radiation with a ω-2θ scan
calcd. C 61.60, H 6.20, N 7.18%; found C 61.85, H 5.93, N 6.97%.
X-ray quality single crystals of 2 were obtained from a mixture of n-
hexane and diethyl ether (1:1). From a concentrated toluene solution
of 2, X-ray quality single crystals of 2·tol were obtained.
technique at room temperature. The structure was solved by direct
[
41]
methods with SHELX-97. A full-matrix least-squares refinement on
2
[41]
F was carried out by using SHELXL-97.
Crystallographic data (excluding structure factors) for the structures in
2
(3): The procedure for the preparation of 3 was similar this paper have been deposited with the Cambridge Crystallographic
[LBrCu(μ-L)]
to that described for compound 2 using 1 (3.40 g, 10 mmol) and CuBr
2
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-968855 (1·THF), CCDC-979429 (1), CCDC-968856
(2), CCDC-974673 (2·tol), CCDC-968857 (3·2tol), CCDC-968858 (4),
(
2
1.12 g, 5 mmol) to afford a yellow green solid (0.99 g, 0.60 mmol,
1
4%). M.p. 241–243 °C. H NMR (500 MHz, CDCl
3
): δ = 12.41 (s,
1
H, NH), 11.07 (s, 1 H, NH), 8.28, 7.63, 7.51, 7.37, 7.22 (m, 8 H,
Z. Anorg. Allg. Chem. 2014, 1614–1621
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1619

X.-Y. Zhao, C.-B. Zhu, H.-P. Li, Y. Yang, H. W. Roesky
ARTICLE
CCDC-968859 (5), and CCDC-968860 (2Ј·2tol) (Fax: +44-1223-336-
Mathers, S. J. Holland, M. J. R. Stark, G. Pass, J. Woods, D. P.
Lane, N. J. Westwood, Cancer Cell 2008, 13, 454–463.
7] N. Gunasekaran, P. Ramesh, M. N. G. Ponnuswamy, R. Karv-
embu, Dalton Trans. 2011, 40, 12519–12526.
8] a) N. Gunasekaran, S. W. Ng, E. R. T. Tiekink, R. Karvembu,
Polyhedron 2012, 34, 41–45; b) U. Braun, R. Richter, J. Sieler,
A. I. Yanovsky, Y. T. Struchkov, Z. Anorg. Allg. Chem. 1985, 529,
033; E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
[
[
Supporting Information (see footnote on the first page of this article):
Figures S1–S13: Molecular structures and packing diagrams. Tables
S1a and S1b: Structural data for 1–5 and 2Ј·2tol. Spectroscopic data
for 1Ј and 2Ј.
201–208.
[
9] a) N. Hung Huy, T. Pham Chien, A. Rodenstein, R. Kirmse, U.
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Acknowledgements
This work was supported by the Research Fund for Teachers of Central
South University (2013JSJJ007), and the Science and Technology
Planning Project of Hunan Province of China (2013FJ2003). Support
of the Deutsche Forschungsgemeinschaft is gratefully acknowledged.
1
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Received: February 20, 2014
Published Online: May 2, 2014
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