Self-Assembly of Discrete Copper(I)-Halide Complexes with Diacylthioureas

Article abstract of DOI:10.1002/zaac.201700430

Three diacylthioureas 1,4-C₆H₄[C(O)NHC(S)NHAr]₂ (Ar = 2,6-iPr₂C₆H₃) (L¹, 1), 1,3-C₆H₄[C(O)NHC(S)NHAr]₂ (L², 2), and 1,3-C₆H

Full text of DOI:10.1002/zaac.201700430

Title: Self-Assembly of Discrete Copper(I)-Halide Complexes with
Diacylthioureas
Authors: Herbert W. Roesky, Xianhui Hou, Fanfan Wang, Li Han, Xia
Pan, Haipu Li, and Ying Yang
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To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.201700430
Link to VoR: http://dx.doi.org/10.1002/zaac.201700430

10.1002/zaac.201700430
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ARTICLE
Self-Assembly of Discrete Copper(I)-Halide Complexes with
Diacylthioureas
Xianhui Hou,[a] Fanfan Wang,[a] Li Han,[a] Xia Pan,[a] Haipu Li,[a] Ying Yang,*[a] and Herbert W. Roesky*[b]
Abstract: Three diacylthioureas 1,4-C6H4[C(O)NHC(S)NHAr]2 (Ar =
2,6-iPr2C6H3) (L1, 1), 1,3-C6H4[C(O)NHC(S)NHAr]2 (L2, 2) and 1,3-
group) or diacyl chlorides[10] (Y spacer and Z end group). In the
complexation reactions, the bipodal HHL tends to be
deprotonated into the dianionic ligand and generates the 2:2 or
C6H4[C(O)NHC(S)NHArꞌ]2 (Arꞌ
=
2,6-Me2C6H3) (L3, 3) were
synthesized and characterized. The CuI complexes from the
reactions of bipodal ligands Ln with CuX (X = Cl, Br, I) were
structurally investigated by single crystal X-ray diffraction methods.
Treatment of L1 with CuX gave the metallamacrocyclic complexes
(L1CuX)2 (X = Cl, 4; Br, 5; I, 6) with the ligand to metal in a ratio of
2:2, where both sulfur and halide anions function as terminal
substituents. In contrast, when L2 or L3 was reacted with CuBr, the
two Ln ligands coordinate to four copper atoms each in a bridging
and terminal fashion to yield [Ln(CuBr)2]2 (n = 2, 7; 3, 8). The
obtained S4Cu4Br4 core contains all four bromide anions in bridging
positions. The reaction of L3 with CuX (X = Cl, I) gave the 3:3
trinuclear complexes (L3CuX)3 (X = Cl, 9; I, 10), interconnected by
halide bridges. The obtained diacylthioureas (1-3) and their CuI
complexes (4-10) were also characterized by elemental analysis,
FT-IR, 1H- and 13C NMR spectroscopy.
3:3 metallamacrocycles, using the κ-O,S mode to chelate metal
13]
centers like CoII,[11] NiII,[12] CuII,[12a,
ZnII, CdII,[13b, 14], HgII,[15]
PtII,[16] PtIV,[17] PdII,[18] RuII,[19] and ReV.[20] In rare cases, HHL was
also found to support polymeric compounds of PbII[13a] or AgI[21]
with or without deprotonation, respectively.
Scheme 1. Monoacylthioureas (HL and H2L) and diacylthioureas (HHL and
H4L). Among the Y and Z substituents, one of them represents the spacer
group and the other is the end group.
Introduction
Acylthiourea derivatives containing the C(O)NHC(S)N core
fragment have been well recognized due to their biological,[1]
optical,[2] analytical,[3] and catalytic properties.[4] Their CuI
complexes are also attractive in view of the metal-based drugs.[5]
As addressed before,[6] the acyclic mono-acylthioureas can be
generally divided into two main classes (Scheme 1): N,N-
disubstituted acylthiourea (HL) and N-alkyl/aryl-N’-acylthiourea
(H2L). When treated with metal reagents, HL is readily
deprotonated into the monoanionic ligand to give O,S-
bis(chelate)-MII complexes in most of the cases.[7] In contrast
H2L behaves always as a neutral sulfur donor in terminal or
bridging mode to support a variety of coordination complexes[6, 8]
due to the ligand specificity.
Under similar conditions, the bipodal diacylthioureas that
contain two C(O)NHC(S)N fragments in each molecule also can
be classified into 3,3ꞌ-disubstituted diacylthiourea (HHL, Scheme
1) and 3,3ꞌ-monosubstituted diacylthiourea (H4L). The role of Y
and Z substituents acting as either spacer or end group depends
on the properties of the used diamines[9] (Z spacer and Y end
In contrast, the investigation of coordination complexes with
the diacylthiourea H4L is largely unexplored. When considering
the performance of the mono-acylthiourea H2L,[6, 8] the bipodal
H4L can be expected to bring abundant structural variety in the
complexation with CuX (X = Cl, Br, I). The two sulfur and the
involved halides could play an alternative role in terminal or
bridging positions. The only previous related report revealed that
H4L can form a coordination polymer with CuCl (H4L
=
Fe[C5H4C(O)NHC(S)NHiPr]2),[22]
where the isopropyl
substituents were less bulky and the relative position of the
sulfur pair was disordered. Based on this finding, we propose
the synthesis of new H4L diacylthioureas: 1,4-C6H4[C(O)NHC(S)
NHAr]2 (Ar
=
2,6-iPr2C6H3) (denoted as L1, 1), 1,3-
C6H4[C(O)NHC(S)NHAr]2 (L2, 2) and 1,3-C6H4[C(O)NHC(S)
NHArꞌ]2 (Arꞌ = 2,6-Me2C6H3) (L3, 3), starting from isophthaloyl
dichloride or terephthaloyl dichloride. Each of Ln is armed with
bulky aryl flanks and shows a large separation between two
sulfur atoms to support the self-assembly with CuI halides.
Complexation reactions of Ln with CuX were carried out in a
comparative manner to investigate the possible formation of
discrete or infinite supramolecular species by coordination-
driven self-assembly.[23]
[a] School of Chemistry and Chemical Engineering
Centre for Environment and Water Resource
Central South University
Lushannan Road 932, 410083 Changsha, P. R. China
Fax: +86-731-88879616
E-mail: yangy@csu.edu.cn
[b] Institut für Anorganische Chemie
Universität Göttingen
Results and Discussion
Tammannstrasse 4, 37077 Göttingen, Germany
Fax: +49-551-39-33373
E-mail: hroesky@gwdg.de
Supporting information for this article is given via a link at the end of
the document.
The diacylthiourea 1,4-C6H4[C(O)NHC(S)NHAr]2 (Ar = 2,6-
iPr2C6H3) (L1, 1) (Scheme 2) was isolated as a yellow solid in
moderate yield (74%) from the successive reaction of
terephthaloyl dichloride with potassium thiocyanate and then
2,6-diisopropyl aniline, by following the previous procedure.[10d,
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24]
The melting point of L1 (259-260°C) is much higher than its
further confirmed as a dimeric binuclear CuI complex (L1CuCl)2
(4) by single crystal X-ray diffraction. 4·2CH2Cl2 crystallizes in
the triclinic space group P-1, and its molecular structure is
shown in Figure 1. The two L1 ligands are each adopting a cis
configuration and they act like a pair of tweezers to the CuCl
molecules. The two CuCl moieties are arranged opposite to
each other with a Cl(1)···Cl(1A) distance of 4.563 Å. It is
interesting to note that the L1 ligands represent a ring system
with two CuCl molecules, instead of forming a zipper-like
polymeric chain in interlace mode. It was suggested that under
given conditions the self-assembly of discrete supramolecules
are more thermodynamically favored than oligomeric or
phenyl analogue 1,4-C6H4[C(O)NHC(S)NHPh]2 (215-220°C).[10d]
In the FT-IR spectrum, the NH absorption bands were observed
at 3432 and 3248 cm–1, and the H NMR spectrum recorded in
1
CDCl3 confirmed the presence of NH groups (δ 11.76 and 9.43
ppm) as well as the characteristic isopropyl groups (δ 3.13 ppm
for the tertiary H atoms and δ 1.24-1.35 ppm for the Me groups).
Furthermore, the 13C NMR spectrum showed the featured
resonances of C=S (δ 179.84 ppm) and C=O (δ 164.52 ppm).
The structure of L1 was elucidated by single crystal X-ray
diffraction. As shown in Figure S1 (see Supporting Information),
there are two independent molecules of L1 in one unit cell, with
totally different S-C-C-S torsions (4.35° for 1a and -76.29° for 1b, polymeric products.[26]
Figure S2). The packing diagram of L1 (Figure S3) and the
topological analysis (Figure S4) by TOPOS[25] indicated that the
neighboring 1b molecules are connected by each other through
N–H···O intermolecular hydrogen bonds to form the zigzag
chains along the b axis. These chains are weaved into an infinite
network through N–H···S intermolecular hydrogen bonds by
molecular pairs of 1a.
Scheme 3. Preparation of (L1CuCl)2 (4), (L1CuBr)2 (5) and (L1CuI)2 (6)
Scheme 2. Diacylthioureas Ln (1-3) in study
Figure 1. Molecular structure of complex (L1CuCl)2 (4). Solvent molecules and
all hydrogen atoms except for NH groups were omitted for clarity. Selected
bond lengths /Å and angles /°: Cu(1)–S(1) 2.2176(2), Cu(1)–S(2) 2.132(9),
Cu(1)–Cl(1) 2.1865(12), Cl(1)···Cl(1A) 4.563; S(1)–Cu(1)–S(2) 102.4(3),
Cl(1)–Cu(1)–S(1) 129.88(4), Cl(1)–Cu(1)–S(2) 125.2(3).
Likewise, 1,3-C6H4[C(O)NHC(S)NHAr]2 (L2, 2) and 1,3-
C6H4[C(O)NHC(S)NHArꞌ]2 (Arꞌ = 2,6-Me2C6H3) (L3, 3) were
synthesized (Scheme 2) and characterized by spectroscopic
techniques. The molecular structure of L3 is shown in Figure S5,
and the simplified topological network (Figure S6) and packing
diagram (Figure S7) suggest that the L3 molecules are
connected into double chains through N–H···O intermolecular
hydrogen bonds in three alternate directions. These chains are
further cross-linked through N–H···S intermolecular hydrogen
bonds.
Treatment of L1 (1) in ethanol with an equivalent of CuCl in
acetonitrile afforded a yellow solid 4 (Scheme 3). Its melting
point (304-305°C) was found considerably higher than that of its
parent ligand L1 (259-260°C). The NH adsorption bands are red-
shifted to 3213 and 3151 cm-1, suggesting a general effect
In (L1CuCl)2 (4) the chlorides function as terminal ligands.
No comparable example of 4 was found in the literature, where
neutral diacylthiourea ligands operate as building block for an
empty metallamacrocycle. Previously we have reported on a CuI
chloride complex (H2L)2CuCl supported by the bulky mono-
acylthiourea (H2L = PhC(O)NHC(S)NHAr),[8] whose molecule
exhibited a butterfly-like structure (Figure S8). In comparison,
the S-Cu-S bond angle of 4 (102.4(3)°) is much more acute than
that in (H2L)2CuCl (115.71(2)°),[8] indicating the structural
constrain imposed by the formed macrocycle. In the crystal
structure the neighboring molecules of 4 are connected through
a pair of N–H···O intermolecular hydrogen bonds resulting in a
chain-of-rings (Figure S9).
during coordination of the acylthiourea ligand to the metal atom
22]
of the ν(NH) frequencies.[5a,
The elemental analysis of 4
indicated a composition of 1:1 stoichiometric ratio of the ligand
L1 to copper chloride, and its structure and composition were
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The reaction of L1 (1) with CuBr afforded an analogous
metallamacrocyclic complex (L1CuBr)2 (5), as revealed by
spectroscopic characterizations and single crystal X-ray
structural analysis (Figure S10). The Br(1)···Br(1A) separation is
4.313 Å, indicating a large cavity within the macrocycle. The
packing style of 5 (Figure S11) is almost the same to that of 4.
Furthermore, the unit cell parameters[27] indicate that complex
(L1CuI)2 (6) is isostructural to (L1CuX)2 (X = Cl 4, Br, 5).
It turned out that the diacylthiourea L1 (1) resulted in the
formation of discrete supramolecular CuI complex (L1CuX)2,
although the halide has been changed. Therefore it is of interest
to examine whether moving the acylthiourea substituents from
the para to the meta position on the benzene ring (as from L1 to
L2 in Scheme 2) or decreasing the steric hindrance of the aryl
groups (as from L2 to L3) would show different complexation
mode in the products.
The reaction of the 1:1 molar ratio of L2 (2) with CuBr
resulted in the formation of 7 (Scheme 4) as the direct
(separable) product in relatively low yield, which could be
improved by doubling the amount of CuBr. The elemental
analysis suggested a 1:2 composition of ligand to metal. Due to
the low quality of single crystals, the molecular structure of 7
could not been solved with a high level of accuracy.[28] However,
the data obtained allowed unambiguously to determine the
structure as the discrete tetranuclear complex [L2(CuBr)2]2
(Figure S12) with the characteristic S4Cu4Br4 cores as
enantiomeric pairs.
molecules of
intermolecular N–H···O hydrogen bonds (Figure S14).
8
stage-like nets are formed by three
Figure 2. Molecular structure of [L3(CuBr)2]2 (8). All hydrogen atoms except for
NH groups were omitted for clarity. Selected bond lengths /Å and angles /°:
Cu(1)–Br(1) 2.3378(19), Cu(1)–Br(3) 2.3651(18), Cu(1)···Cu(3) 2.6482(18),
Cu(2)–Br(1) 2.4617(16), Cu(2)–Br(2) 2.5681(16), Cu(3)–Br(4) 2.3343(18),
Cu(3)–Br(3) 2.3665(17), Cu(4)–Br(4) 2.4688(16), Cu(4)–Br(2) 2.5380(15);
Cu(1)–Br(3)–Cu(3) 68.07(5), Cu(2)–Br(2)–Cu(4) 102.67(5).
The resulting powders from reaction of L2 with CuCl or CuI
could not be obtained in a crystalline form, while the products of
L3 with the copper salts (Scheme 5) were easily recrystallized in
good shaped crystals. However, the single crystals of 9 became
fragile and quickly decayed after being removed from the solvent.
Therefore they could only be used for the determination of the
unit cell parameters,[29] which were found to be totally different
from those of [L3(CuBr)2]2 (8) but almost the same to those of 10.
Crystals of the latter were stable during X-ray data collection.
Scheme 4. Preparation of [L2(CuBr)2]2 (7) and [L3(CuBr)2]2 (8)
Similarly, the 1:2 reaction of L3 (3) with CuBr led to the
production of [L3(CuBr)2]2 (8, Scheme 4) in moderate yield (60%).
The single crystal X-ray diffraction analysis revealed that 8
(Figure 2) is isostructural to 7 in view of the tetranuclear
composition and the resulting S4Cu4Br4 core. The four bromide
atoms function as bridging species while each L3 ligand provides
one bridging and one terminal sulfur atom. Previously, under the
Scheme 5. Preparation of (L3CuCl)3 (9) and (L3CuI)3 (10)
The molecular structure of 10 is depicted in Figure 3 with
selected bond lengths and angles. (L3CuI)3 (10) crystallized in
the orthorhombic space group P212121, with a puckered six-
membered Cu3I3 ring centered in the molecular domain, where
all iodine atoms act as the bridging ligands and sulfur atoms are
arranged in terminal positions. The copper atoms in 10 are all
located in the tetragonal environment completed by two sulfur
and two iodine atoms. In addition, each ligand plane of L3
(represented by the C6H4 ring plane) intersects with the Cu3
plane by about 28.5° and thus provides three blades of a chiral
propeller-like structure (Figure S15).
support of mono-acylthioureas (H2L), we reported on the
8]
formation of the adamantanoid cage (H2LCuBr)4,[6,
which
shares the same S4Cu4Br4 core with that of 7 and of 8. In this
respect, each diacylthiourea ligand in 7 or 8 simply mimics a pair
of mono-acylthioureas. The S···S separation (6.980-7.035 Å) of
each diacylthiourea ligand in 8 was found much larger than that
in the free L3 ligand (6.579 Å) or those in the counterparts of
(H2LCuBr)4 (6.593-6.655 Å).[6, 8] This observation suggests that
both the diacylthiourea ligand and the S4Cu4Br4 core can adjust
the constraint by more or less transformation in the geometry.
In the packing diagram, the molecule of 7 was arranged in a
tetrahedral center and connected with four neighbors by four
intermolecular N–H···O hydrogen bonds (Figure S13). In the
A similar Cu3I3 ring was furnished by triazacyclohexane
(R3TAC) bearing three thioether functionalities (R),[30] where
each copper atom is bound to two bromide bridges, one nitrogen
and one sulfur atom. In the current case, benefiting from the
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large S···S separation in L3, the Cu3I3 ring in 10 is more Conclusions
stretched and spread, as indicated by the wider Cu–I–Cu angles
Three diacylthioureas (Ln) were synthesized, each supported
by bulky aryl flanks, which are showing a large S···S separation.
Their self-assemblies with CuI halides were investigated and
examined in view of the ligand effect. The single crystal
structural analysis revealed that the complexation products of Ln
with CuX (X = Cl, Br, I) turned out to be the discrete
supramolecular CuI complexes, instead of an infinite
coordination polymer. Reactions of L1 (1) with CuX gave the
binuclear metallamacrocyclic complexes (L1CuX)2 (X=Cl, 4; Br, 5;
I, 6), while the complexation of L2 (2) or L3 (3) with CuBr
produced the tetranuclear copper clusters [Ln(CuBr)2]2 (n = 2, 7;
3, 8). Interestingly, L3 (3) supported the formation of trinuclear
complexes (L2CuX)3 (X= Cl, 9; I, 10) with a three-blade propeller
structure. The reported results show that the mono-acylthiourea
H2L ligands are less competent in self-assembly with CuI halide
in a 2:1 stoichiometry, in a monomeric or dimeric configuration
or in a 3:1 composition, respectively to give mononuclear or
binuclear complexes.[6] In contrast the bipodal diacylthioureas Ln
proved to be the ligand of choice to design and synthesize the
discrete supramolecular complexes by self-assembly.
(about 102°) and longer Cu···Cu distances (about 4.1 Å), when
compared to those counterparts in R3TAC(CuI)3 (about 68° and
2.9 Å).[30] In the packing diagram, each molecule of 10 has four
direct neighbors to construct the three-dimensional grids by four
intermolecular N–H···O hydrogen bonds (Figure S16).
Experimental Section
Figure 3. Molecular structure of (L3CuI)3 (10). Solvent molecules and all
hydrogen atoms except for NH groups were omitted for clarity. Selected bond
lengths /Å and angles /°: Cu(1)-S(1) 2.3118(13), Cu(1)-S(6) 2.3429(13),
Cu(1)–I(1) 2.5944(6), Cu(1)–I(2) 2.6537(7), Cu(2)–S(2) 2.3435(13), Cu(2)–I(2)
2.6164(6), Cu(3)–S(4) 2.3394(13), Cu(3)–I(1) 2.6388(7); Cu(1)–I(1)–Cu(3)
101.99(2), Cu(2)–I(2)–Cu(1) 102.14(2), Cu(3)–I(3)–Cu(2) 102.72(2).
All reagents and solvents used in the synthesis were purchased from
commercial sources and used as received. Melting points were
determined with a sealed capillary tube using an X-4B apparatus.
Elemental analyses for carbon, hydrogen, nitrogen, and sulfur were
carried out with a Thermo Quest Italia SPA EA1110 instrument. The 1H
and 13C NMR spectra were recorded in 5 mm tubes in a DMSO-d6 or
CDCl3 solution using AVANCE III 400 or AVANCE III HD 500
spectrometers. Infrared spectra were recorded by using KBr pellets with
a Nicolet iS 50 (Thermo Nicolet Corporation) FT-IR spectrometer.
Complex (L3CuI)3 (10) was found be sensitive to moisture
and then tended to slowly transform into a binuclear complex
[L3′Cu(µ-I)]2 (11, Scheme S1) by partially hydrolyzing one of the
acylthiourea groups of L3 into the acylurea functionality. This
hydrolysis undergoing desulfurization has been known for
monoacylthioureas.[1d, 31] In this way, L3′ can be considered as a
bulky monoacylthiourea. CuI complexes of Cu2X2 with halide
bridges and terminal acylthioureas are so far rare, and the first
one of this type that was isolated and characterized as the 4:2
binuclear [(H2L)2Cu(μ-I)]2.[6] In compound 11, the more bulky L3′
has caused a 2:2 dimeric complex formation (Figure S17). A
related [LCu(µ-I)]2 complex was previously prepared using
thioamidoguanidine (L),[32] where the copper atoms were
additionally coordinated by morpholine-O atoms to give a 1D
coordination polymer. In contrast, the copper atoms in 11 are
three-coordinate and the adjacent molecules are connected
through two intermolecular N–H···O hydrogen bonds (Figure
S18).
1,4-C6H4[C(O)NHC(S)NHAr]2 (Ar = 2,6-iPr2C6H3) (L1, 1): To an acetone
solution (300 mL) of potassium thiocyanate (4.85 g, 50.0 mmol) was
added terephthaloyl dichloride (5.08 g, 25 mmol) at ambient temperature
under rigorous stirring. Then the reaction mixture was further stirred for 1
h under 50°C, forming the terephthaloyl diisothiocyanate. Finally to this
mixture was added 2,6-diisopropyl aniline (9.4 mL, 50 mmol) drop by
drop, followed by another 2 h stirring to complete the reaction. Then the
obtained mixture was poured into a beaker containing water (500 mL).
The colored precipitates were filtered off, washed thoroughly with ethanol
(100 mL), and dried in air at 80°C to give a yellow solid. Yield: 10.87 g,
18.1 mmol, 72.4%. M.p.: 259.1-260.3°C. 1H NMR (500 MHz, CDCl3, ppm)
δ 11.76 (s, 2H, NH), 9.43 (s, 2H, NH), 8.14 (s, 4H, Ph-H), 7.43 (t, J = 7.7
Hz, 2H, Ar-H), 7.29 (d, J = 7.2 Hz, 4H, Ar-H), 3.13 (sept, J = 6.8 Hz, 4H,
CH(CH3)2), 1.35 (d, J = 6.8 Hz, 12H, CH(CH3)2), 1.24 (d, J = 6.9 Hz, 12H,
CH(CH3)2). 1H NMR (500 MHz, DMSO-d6, ppm): δ 11.87 (s, 4H, NH),
8.16 (s, 4H, Ph-H), 7.32-7.36 (m, 2H, Ar-H), 7.22-7.24 (m, 4H, Ar-H),
3.06 (sept, J = 6.9 Hz, 4H, CH(CH3)2), 1.23 (d, J = 6.8 Hz, 12H,
CH(CH3)2), 1.15 (d, J = 6.8 Hz, 24H, CH(CH3)2). 13C NMR (101 MHz,
CDCl3, ppm) δ 179.84 (C=S), 164.52 (C=O), 144.47, 135.15, 131.55,
128.26, 127.46, 122.92 (Ar/Ph-C), 27.92, (CH(CH3)2), 23.38, 22.12
(CH(CH3)2). FT-IR (KBr, cm-1): ṽ 3432.16 (vs, NH), 3248.29 (w, NH),
2960.73 (m), 2866.88 (m), 1674.05 (w, C=O), 1529.69 (s), 1484.12 (s),
1380.99 (vs), 1321.81 (w), 1257.49 (m), 1152.06 (w, C=S), 1122.77 (m),
804.38 (w), 726.75 (w), 610.06 (w). Anal. Calcd. for C34H42N4O2S2
(602.86): C, 67.74; H, 7.02; N, 9.29; S, 10.64%. Found: C, 67.83; H, 7.30;
For further comparison the assembly of CuI complexes with
a less bulky 1,4-C6H4[C(O)NHC(S)NHArꞌ]2 (L4, Figure S19) was
also investigated. However L4 was sparingly soluble in common
organic solvents and was also found to be easily hydrolyzed to
give the diacylurea (Figure S20). The latter prevented the
separation of the resulting products.
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N, 9.54; S, 10.61%. X-ray quality single crystals of 1 were obtained from
a concentrated dichloromethane solution.
Hz, 12H, CH(CH3)2). 13C NMR (126 MHz, CDCl3, ppm): δ 179.76 (C=S),
167.34 (C=O), 144.10, 134.27, 130.67, 128.80, 128.47, 122.99 (Ar/Ph-C),
27.86 (CH(CH3)2), 23.40, 22.04 (CH(CH3)2). FT-IR (KBr, cm-1): ṽ 3213.65
(vs, NH), 3151.58 (vs, NH), 2964.23 (vw), 2363.2 (vw), 1676.26 (vw,
C=O), 1518.82 (vw), 1319.89 (w), 1261.47 (vw), 1203.79 (vw), 1152.6
(vw, C=S), 1087.56 (vw), 1016.13 (vw), 862.04 (vw), 800.34 (vw), 749.46
(vw), 684.39 (vw), 621.89 (vw), 454.17 (vw). Anal. Calcd. for
C68H84Br2Cu2N8O4S4 (1492.61): C, 54.72; H, 5.67; N, 7.51; S, 8.59%.
Found: C, 54.81; H, 5.97; N, 7.77; S, 8.80%. Yellow X-ray quality single
crystals of 5 were obtained from a concentrated dichloromethane solution.
1,3-C6H4[C(O)NHC(S)NHAr]2 (L2, 2): The procedure was similar to that
for L1(1) using isophthaloyl dichloride (5.08 g, 25 mmol), potassium
thiocyanate (4.85 g, 50.0 mmol) and 2,6-diisopropyl aniline (9.4 mL, 50
mmol) to obtain a white solid. Yield: 13.6 g, 22.6 mmol, 90.4%. M.p.:
1
235.0°C. H NMR (400 MHz, CDCl3, ppm): δ 11.80 (s, 2H, NH), 9.65 (s,
2H, NH), 8.67 (s, 1H, Ph-H), 8.26 (dd, J = 7.8, 1.7 Hz, 2H, Ph-H), 7.79 (t,
J = 7.8 Hz, 1H, Ph-H), 7.41-7.45 (m, 2H, Ar-H), 7.28-7.30 (m, 4H, Ar-H),
3.13 (sept, J = 6.8 Hz, 4H, CH(CH3)2), 1.34 (d, J = 6.8 Hz, 12H,
CH(CH3)2), 1.24 (d, J = 6.9 Hz, 12H, CH(CH3)2). 13C NMR (126 MHz,
CDCl3, ppm) δ 181.11 (C=S), 165.73 (C=O), 145.31, 132.91-132.48,
129.26, 123.93 (Ar/Ph-C), 28.95 (CH(CH3)2), 24.41, 23.13 (CH(CH3)2).
FT-IR (KBr, cm-1): ṽ 3225.38 (vw, NH), 2963.67 (w), 1676.19 (w, C=O),
1513.97 (m), 1324.59 (vw), 1229.6 (vw), 1155.59 (w, C=S), 803.53 (vw),
736.86 (vw), 690.99 (vw). Anal. Calcd. for C34H42N4O2S2 (602.86): C,
67.74; H, 7.02; N, 9.29; S, 10.64%. Found: C, 67.92; H, 6.96; N, 9.44; S,
10.59%.
(L1CuI)2 (6): The procedure was similar to that for 4 using L1 (1) (0.602 g,
1 mmol), and CuI (0.19 g, 1 mmol) to obtain a yellow solid. Yield: 0.435 g,
0.27 mmol, 54.9%. M.p. 282.7-283.9°C. 1H NMR (400 MHz, DMSO-d6,
ppm): δ 11.91 (s, 2H, NH), 11.64 (s, 2H, NH), 8.25 (s, 4H, Ph-H), 7.34-
7.37 (m, 2H, Ar-H), 7.24-7.25 (m, 4H, Ar-H), 3.04 (sept, J = 6.9Hz, 4H,
CH(CH3)2), 1.22 (d, J = 6.5 Hz, 12H, CH(CH3)2), 1.15 (d, J = 6.6 Hz, 12H,
CH(CH3)2). 13C NMR (126 MHz, CDCl3, ppm): δ 180.35 (C=S), 168.37
(C=O), 145.14, 135.18, 131.55, 129.95, 129.56, 124.02 (Ar/Ph-C), 28.91
(CH(CH3)2), 24.42, 23.07 (CH(CH3)2). FT-IR (KBr, cm-1): ṽ 3215.40 (vs,
NH), 3163.69 (vs, NH), 2963.49 (w), 2869.01 (m), 1676.41 (w, C=O),
1516.27 (s), 1321.19 (vs), 1259.5 (m), 1202.35 (m), 1153.48 (w, C=S),
1120.32 (m), 1086.46 (w), 801.18 (w), 747.5 (w), 683.83 (w), 608.6 (w).
Anal. Calcd. for C68H84I2Cu2N8O4S4 (1586.61): C, 51.48; H, 5.34; N, 7.06;
S, 8.08%. Found: C, 51.67; H, 5.45; N, 6.75; S, 7.72%.
1,3-C6H4[C(O)NHC(S)NHArꞌ]2 (Arꞌ
=
2,6-Me2C6H3) (L3, 3): The
procedure was similar to that for L1 (1) using isophthaloyl dichloride (5.08
g, 25 mmol), potassium thiocyanate (4.85 g, 50.0 mmol) and 2,6-dimethyl
aniline (6.16 mL, 50 mmol) to obtain a yellow solid. Yield: 11.4 g, 23.3
1
mmol, 93.2%. M.p.: 217°C. H NMR (500 MHz, DMSO-d6, ppm) δ 11.88
(s, 2H, NH), 11.67 (s, 2H, NH), 8.68 (s, 1H, Ph-H), 8.22 (d, J = 7.8 Hz,
2H, Ph-H), 7.73 (t, J = 7.8 Hz, 1H, Ph-H), 7.14-7.19 (m, 6H, Ar-H), 2.24
(s, 12H, CH3). 13C NMR (126 MHz, DMSO-d6, ppm) δ 180.56 (C=S),
167.49 (C=O), 136.74, 135.55, 133.77, 132.33, 129.57, 129.38, 128.40,
127.99 (Ar/Ph-C), 18.35 (CH3). FT-IR (KBr, cm-1): ṽ 3336.68 (s, NH),
3186.12 (s, NH), 3070.05 (m), 3038.07 (m), 2981.54 (m, CH3), 2918.66
(m), 2855 (w), 1676.55 (vs, C=O), 1601.57 (w), 1529.82 (vs), 1512.54
(vs), 1442.43 (m), 1376.48 (w), 1325.8 (m), 1275.31 (m), 1235.49 (m),
1215.79 (m), 1159.35 (s, C=S), 1108.8 (w), 1091.75 (w), 764.18 (w),
731.58 (w), 682.76 (w). Anal. Calcd. for C26H26N4O2S2 (490.64): C, 63.65;
H, 5.34; N, 11.42; S, 13.07%. Found: C, 63.45; H, 5.25; N, 10.91; S,
13.24%. Yellow X-ray quality single crystals of 3 were obtained from a
concentrated acetone solution.
[L2(CuBr)2]2 (7): The procedure was similar to that for 4 using L2 (2)
(0.605 g, 1 mmol), and CuBr (0.29 g, 2 mmol) to obtain a yellow solid.
Yield: 0.605 g, 0.34 mmol, 67.6%. M.p. 320°C. 1H NMR (400 MHz, CDCl3,
ppm) δ 12.07 (s, 2H, NH), 11.05 (s, 2H, NH), 8.85 (s, 1H, Ph-H), 8.46 (d,
J = 7.5 Hz, 2H, Ph-H), 7.69 (t, J = 7.8 Hz, 1H, Ph-H), 7.38 (t, J = 7.7 Hz,
2H, Ar-H), 7.22 (d, J = 7.8 Hz, 4H, Ar-H), 2.99 (sept, J = 6.8 Hz, 4H,
CH(CH3)2), 1.20 (d, J = 6.8 Hz, 12H, CH(CH3)2), 1.15 (d, J = 6.8 Hz, 15H,
CH(CH3)2). 13C NMR (126 MHz, CDCl3, ppm) δ 180.82 (C=S), 167.67
(C=O), 145.31, 134.10, 131.91, 129.34, 123.92 (Ar/Ph-C), 28.86
(CH(CH3)2), 24.36, 23.08 (CH(CH3)2). FT-IR (KBr, cm-1): ṽ 3226.57 (w,
NH), 2963.65 (w), 1679.15 (w, C=O), 1533.13 (m), 1322.06 (w), 1231.36
(w), 1207.05 (w), 1158.43 (w, C=S), 801.48 (w), 742.85 (w), 679.66 (w).
Anal. Calcd. for C68H84Br8Cu8N8O4S4 (1779.51): C, 45.90; H, 4.76; N,
6.30; S, 7.21%. Found: C, 45.97; H, 4.74; N, 6.44; S, 7.50%. Yellow X-
ray quality single crystals of 7 were obtained from a concentrated filtered
reaction solution.
(L1CuCl)2 (4): To a solution of L1 (0.602 g, 1 mmol) in ethyl alcohol (40
mL) at ambient temperature was added a suspension of CuCl (0.105 g, 1
mmol) in acetonitrile (10 mL) drop by drop under rigorous stirring. Then
stirring was continued for 4 h to insure the completion of complexation.
The resultant precipitate was filtered, washed with ethanol repeatedly,
and dried at 80°C to obtain a yellow powder. Yield: 0.365 g, 0.26 mmol,
51.6%. M.p. 303.5-304.8°C.1H NMR (400 MHz, DMSO-d6, ppm) δ 11.87
(s, 4H, NH), 8.17 (s, 4H, PhH), 7.32-7.37 (m, 2H, Ar-H), 7.23-7.25 (m, 4H,
Ar-H), 3.06 (sept, J = 6.7 Hz, 4H, CH(CH3)2), 1.23 (d, J = 6.8 Hz, 12H,
CH(CH3)2), 1.15 (d, J = 6.8 Hz, 12H, CH(CH3)2). 13C NMR (126 MHz,
CDCl3, ppm) δ 181.19 (C=S), 168.34 (C=O), 145.13, 135.24, 131.73,
129.77, 129.51, 124.02 (Ar/Ph-C), 28.90 (CH(CH3)2), 24.43, 23.07
(CH(CH3)2). FT-IR (KBr, cm-1): ṽ 3211.76 (w, NH), 3146.94 (m, NH),
2963.96 (s), 2930.38 (m), 1675.17 (s, C=O), 1520.09 (vs), 1363.21 (w),
1319.33 (m), 1262.58 (s), 1202.61 (m), 1151.29 (s, C=S), 1120.55 (m),
1088.97 (w), 800.08 (m), 745.61 (m), 682.42 (m). Anal. Calcd. for
C68H84Cl2Cu2N8O4S4 (1403.70): C, 58.19; H, 6.03; N, 7.98; S, 9.14%.
Found: C, 57.99; H, 6.16; N, 7.80; S, 8.85%. Yellow X-ray quality single
crystals of 4 were obtained from a concentrated dichloromethane solution.
[L3(CuBr)2]2 (8)：The procedure was similar to that for 4 using L3 (3)
(0.49 g, 1 mmol), and CuBr (0.29 g, 2 mmol) to obtain a yellow solid.
1
Yield: 0.467 g, 0.3 mmol, 60%. M.p. 224°C. H NMR (500 MHz, DMSO-
d6, ppm) δ 11.90 (s, 2H, NH), 11.47 (s, 2H, NH), 8.89 (s, 1H, Ph-H), 8.28
(d, J = 7.6 Hz, 2H, Ph-H), 7.76 (t, J = 7.8 Hz, 1H, Ph-H), 7.14-7.21 (m,
6H, Ar-H), 2.21 (s, 12H, CH3). 13C NMR (126 MHz, DMSO-d6, ppm) δ
179.70 (C=S), 168.25 (C=O), 136.48, 135.40, 134.08, 132.07, 128.47,
128.30, 127.20 (Ar/Ph-C), 18.27 (CH3). FT-IR (KBr, cm-1): ṽ 3219.08 (m,
NH), 3163.06 (m, NH), 3066.03 (w), 3032.7 (w), 2981.35 (w), 2919.22
(w), 2872.2 (vw), 2854.34 (vw), 1678.62 (m, C=O), 1602.53 (w), 1582.93
(vw), 1525.07 (s), 1518.21 (s), 1443.27 (w), 1397.45 (vw), 1376.32 (vw),
1335.07 (w), 1283.56 (vw), 1263.04 (vw), 1230.33 (w), 1157.32 (m, C=S),
1114.22 (vw), 1090.4 (vw), 1068.1 (vw), 1033.36 (vw), 771.01 (vw),
751.11 (vw), 738.27 (vw), 728.73 (vw), 687.87 (vw), 677.23 (vw). Anal.
Calcd. for C52H52Br4Cu4N8O4S4 (1555.08): C, 40.16; H, 3.37; N, 7.21; S,
8.25%. Found: C, 40.33; H, 3.53; N, 6.85; S, 8.25%. Yellow X-ray quality
(L1CuBr)2 (5): The procedure was similar to that for 4 using L1 (1) (0.602
g, 1 mmol), and CuBr (0.145 g, 1 mmol) to obtain a yellow solid. Yield:
0.45 g, 0.30 mmol, 60.2%. M.p. 289.7-290.9°C. 1H NMR (400 MHz,
DMSO-d6, ppm) δ 11.88 (s, 2H, NH), 11.82 (s, 2H, NH), 8.19 (s, 4H, Ph-
H), 7.32-7.37 (m, 2H, Ar-H), 7.23-7.25 (m, 4H, Ar-H), 3.05 (sept, J = 6.7
Hz, 4H, CH(CH3)2), 1.23 (d, J = 6.8 Hz, 12H, CH(CH3)2), 1.15 (d, J = 6.8
single crystals of
dichloromethane solution.
8 were obtained from a concentrated acetone-
(L3CuCl)3 (9): The procedure was similar to that for 4 using L3 (3) (0.49 g,
1 mmol) and CuCl (0.105 g, 1 mmol) to obtain a yellow powder. Yield:
0.465 g, 0.263 mmol, 78.2%. M.p.: 217°C. 1H NMR (500 MHz, DMSO-d6,
This article is protected by copyright. All rights reserved.

10.1002/zaac.201700430
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
ppm) δ 11.89 (s, 2H, NH), 11.59 (s, 2H, NH), 8.78 (s, 1H, Ph-H), 8.26 (d,
J = 7.2 Hz, 2H, Ph-H), 7.76 (t, J = 7.2 Hz, 1H, Ph-H), 7.14-7.20 (m, 6H,
Ar-H), 2.21 (s, 12H, CH3). 13C NMR (126 MHz, DMSO-d6, ppm) δ 180.37
(C=S), 167.40 (C=O), 136.67, 135.51, 133.82, 132.32, 129.43, 128.41,
128.03 (Ar/Ph-C), 18.31 (CH3). FT-IR (KBr, cm-1): ṽ 3212.61 (m, NH),
3156.78 (m, NH), 3027.39 (w), 2980.76 (w), 2919.34 (w), 2855.54 (vw),
1677.33 (m, C=O), 1601.19 (vw), 1528.65 (s), 1442.64 (w), 1376.99 (vw),
1332.38 (w), 1285.21 (vw), 1231.41 (w), 1157.61 (w, C=S), 1114.3 (vw),
1089.41 (vw), 1033.64 (vw), 752.85 (vw), 732.91 (vw), 678.51 (vw). Anal.
Calcd. for C78H78Cl3Cu3N12O6S6 (1768.91): C, 52.96; H, 4.44; N, 9.50; S,
10.87%. Found: C, 52.99; H, 4.21; N, 9.22; S, 10.40%. Yellow X-ray
quality single crystals of 9 were obtained from a concentrated acetone
solution.
N. Tahir, S. Ullah, F. Huq, Aust. J. Chem. 2013, 66, 1352-1360; d)
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(L3CuI)3 (10): The procedure was similar to that for 4 using L3 (3) (0. 49g,
1 mmol) and CuI (0.19 g, 1 mmol) to obtain a yellow solid. Yield: 0.51 g,
0.25 mmol, 75%. M.p. 281°C. 1H NMR (500 MHz, DMSO-d6, ppm) δ
11.98 (s, 2H, NH), 11.19-11.28 (br, 2H, NH), 9.12-21 (br, 1H, Ph-H), 8.32
(m, 2H, Ph-H), 7.84 (m, 1H, Ph-H), 7.14-7.27 (m, 6H, Ar-H), 2.24 (s, 12H,
CH3). 13C NMR (126 MHz, DMSO-d6, ppm) δ 179.14 (C=S), 166.21
(C=O), 136.36, 135.21, 134.69, 131.37, 130.47, 129.71, 128.56 (Ar/Ph-
C), 18.33 (CH3). IR (KBr, cm-1): ṽ 3247.78 (s, NH), 3167.19 (m), 3027.16
(w), 2974.53 (w), 2917.84 (w), 2854.56 (vw), 1680.59 (s, C=O), 1600.3
(w), 1527.6 (vs), 1508.75 (vs), 1442.11 (w), 1376.13 (w), 1335.69 (w),
1281.26 (w), 1215.51 (m), 1157.83 (m, C=S), 1117.83 (vw), 1083.8 (vw),
1034.37 (vw), 755.75 (vw), 743.2 (vw), 676.08 (vw). Anal. Calcd. For
C78H78I3Cu3N12O6S6 (2043.27): C, 45.85; H, 3.85; N, 8.23; S, 9.41%.
Found: C, 45.85; H, 4.04; N, 7.82; S, 9.76%. Yellow X-ray quality single
crystals of 10 were obtained from a concentrated acetone solution.
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X-ray Crystallography: Data were collected with a Bruker SMART
APEX II CCD diffractometer. The diffraction data were obtained using
graphite monochromated Mo-Kα radiation with a ω-2θ scan technique at
room temperature. The structure was solved by direct methods with
SHELX-97.[33] A full-matrix least-squares refinement on F2 was carried
out by using SHELXL-97.[33] Crystallographic data with structure factors
for the structures in this paper have been deposited with the Cambridge
Crystallographic 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-1576583 ((1·CH2Cl2)2·H2O),
CCDC-1576584 (2), CCDC-1576585 (4·2CH2Cl2), CCDC-1576586
(5·2CH2Cl2), CCDC-1576588 (8), CCDC-1576587 (10), CCDC-1576590
(11), CCDC-1576589 (12·2THF), and CCDC-1576591 (13·2DMSO) (Fax:
+44-1223-336-033;E-Mail:deposit@ccdc.cam.ac.uk,
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http://www.ccdc.cam.ac.uk)
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21771194), and the Special Fund for Agro-
scientific Research in the Public Interest (201503108). Support
of the Deutsche Forschungsgemeinschaft (RO 224/68-1) is
gratefully acknowledged.
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Keywords: Diacylthiourea • Copper(I) complex • Self-assembly •
Bipodal ligand
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10.1002/zaac.201700430
Zeitschrift für anorganische und allgemeine Chemie
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[27]Unit cell parameters for (L1CuI)2 2CH2Cl2 (6). Triclinic, P-1. a =
8.543(2), b = 14.920(4), c = 18.450(5) Å; α = 74.226(12), β =
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=37.032(10), b = 13.568(3), c = 25.418(7) Å; β = 132.220(14)º; V
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[29]Unit cell parameters for (L3CuCl)3 (9). Orthorhombic. a =19.45, b
= 19.72, c = 28.07 Å; V = 10766 Å3.
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10.1002/zaac.201700430
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
Entry for the Table of Contents
Layout 2: (11.5cm*2.5cm)
FULL PAPER
X. H. Hou, F. F. Wang, L. Han, X. Pan,
H. P. Li, Y. Yang,* and H. W. Roesky*
Page No. – Page No.
Self-Assembly of Discrete Copper(I)-
Halide Complexes with
Diacylthioureas
The self-assemblies of three different diacylthioureas (L) with CuX (X = Cl, Br, I) led
to the formation of discrete copper(I) complexes, including the binuclear (LCuX)2,
tetranuclear [L(CuX)2]2, and trinuclear (LCuX)3 species.
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