Synthesis and structural characterization of silver(I) and gold(I) complexes of N,N′-diisobutyloxycarbonyl-N″,N?-(1,3-propylene)-bisthiourea

Article abstract of DOI:10.1016/j.poly.2017.08.014

N,N′-diisobutyloxycarbonyl-N″,N?-(1,3-propylene)-bisthiourea (L) and its silver(I) and gold(I) complexes were designed and synthesized. Treatment of 1,3-propanediamine with the isothiocyanate ⁱPrCH₂OC(O)NCS yielded bisthiourea L with

Full text of DOI:10.1016/j.poly.2017.08.014

Accepted Manuscript
Synthesis and Structural Characterization of Silver(I) and Gold(I) Complexes
of N,N’-diisobutyloxycarbonyl-N”,N’ ”-(1,3-propylene)-bisthiourea
Jing-Jing Wei, Jing-Jing Xiao, Jia-Wen Yu, Xiao-Yi Yi, Sheng Liu, Guang-Yi
Liu
PII:
S0277-5387(17)30545-4
DOI:
http://dx.doi.org/10.1016/j.poly.2017.08.014
POLY 12778
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
5 June 2017
15 August 2017
Please cite this article as: J-J. Wei, J-J. Xiao, J-W. Yu, X-Y. Yi, S. Liu, G-Y. Liu, Synthesis and Structural
Characterization of Silver(I) and Gold(I) Complexes of N,N’-diisobutyloxycarbonyl-N”,N’ ”-(1,3-propylene)-
bisthiourea, Polyhedron (2017), doi: http://dx.doi.org/10.1016/j.poly.2017.08.014
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Synthesis and Structural Characterization of Silver(I) and Gold(I)
Complexes of
N,N’-diisobutyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea
Jing-Jing Wei†1, Jing-Jing Xiao†1, Jia-Wen Yu1, Xiao-Yi Yi*1, Sheng Liu1, Guang-Yi
Liu*1
1. College of Chemistry and Chemical Engineering, Central South University, Changsha,
Hunan 410083, P. R. China
Fax: 86 731 88879616; Tel: 86 731 88879616;
*To whom correspondence should be addressed. E-mail: xyyi@csu.edu.cn;
guangyiliu@csu.edu.cn
† To whom make equal contribution to this research

Abstract
N,N’-diisobutyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea (L) and its silver(I) and
gold(I) complexes were designed and synthesized. Treatment of 1,3-propanediamine with
i
the isothiocyanate PrCH2OC(O)NCS yielded bisthiourea L with over 90% yield.
Treatment of L with AgNO3 in CH3CN afforded coordination polymer
{[Ag(L)(NO3)·CH3CN]}n (1) with layer structure, while with HAuCl4 in CH3CN resulted
in reduction of Au3+ to Au+ to yield molecular [Au(L)Cl] (2). Ligand L and complexes 1
and 2 were fully characterized by IR, 1H NMR, UV-vis，cyclic voltammetry and element
analysis. The X-ray diffraction analysis displays that the bisthiourea L behaves as sulfur
donor to coordinate to Ag and Au atom with µ3-(S, µ2-S’,S’) and µ2-S, S’ coordination
mode in 1 and 2, respectively.
Keywords
Bisthiourea; Sulfur donor; Silver complex; Gold complex

1. Introduction
N,N’-disubstiuted thiourea, as valuable industrial material and organic intermediate,
has expanded significantly due to its potential applications in metallurgical industry and
medical field [1-4]. With the simultaneous presence of S, N and O donors, thiourea ligand
is featured with strong coordination ability, varieties of coordination modes and easy
modification. It becomes a topic of an increasing interest in the last few years. As shown
in Scheme 1, N,N’-disubstiuted thiourea might act as neutral or anionic ligand. i) to be
neutral ligand, thiourea performance as S donor [5,6]; ii) to be anionic ligand, thiourea
behaves as N donor, bidentated N, S donor, O, S donor, N, O donor or tridentated N, O, S
donor [7-10]. To date, numerous transition metal complexes with thiourea derivatives
have been reported [11-15]. We specially concerned the steiric and/or electronic
modification of thiourea derivatives in hydrometallurgy for separation and concentration
of
noble
metals.
In
our
previous
work,
N,N’
N,N’
-diisopropoxypropyl-N’’,N’’’-oxydiethylenedicarbonyl
and
-diethyl-N’’ ,N’’’-oxydiethylenedicarbonyl bisthioureas were successfully used in
flotation separation of copper sulfide minerals [16], however, how the bisthioureas
interact with silver or gold is still unknown. Thus, as continuous work to investigate the
coordination chemistry of N,N’-disubstiuted bisthiourea, we herein will describe the
synthesis, solid structure of silver(I) and gold(I) complexes by the
N,N’-diisobutyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea (L) ligand in this paper.
2. Experimental Section
2.1 General
1
Solvents were purified, distilled and degassed prior to use. H NMR spectra were
recorded on a Bruker AVANCE spectrometer operating at 400 MHz, and chemical
shifts (δ, ppm) were reported with reference to SiMe4. Infrared spectra (KBr) were
recorded on Nicolet 6700 spectrometer FT-IR spectrophotometer. ESI-MS was
performed in a Bruker Daltonik GmbH, Bremen mass spectrometer equipped with an

electrospray ionization (ESI) source, and the experimental parameters were as follows:
capillary temperature, 200 oC; capillary voltage, 4500 V; flow rate, 4 L/min; hexapole,
127 V. Potential measured in CH3CN with 0.1 M [n-Bu4N]PF6 as supporting
electrolyte; scan rate = 100 mVs-1; Glassy carbon working electrode, Pt counter
electrode, reference electrode: AgNO3/Ag (0.1 M acetonitrile). UV–Vis spectra were
recorded on a UV759S machine. Elemental analyses for C, H, N and S were
performed on a Perkin Elmer 240C elemental analyzer. All of chemicals were
obtained from J&K Scientific Ltd.
2.2 Preparation of L
A mixture of NaSCN (0.11 mol) and phase transfer catalyst N,N-dimethylaniline
(DMA) (0.006 mol) in water (50 mL) was dropwise added isobutyl chlorocarbonate (0.1
mol) within 1 h at 0 °C. After the reaction mixture was continued to stir for 2.5 h at 0 °C,
orange-red intermediate of isobutyloxycarbonyl isothiocyanate was observed.
1,3-propanediamine aqueous solution (0.06 mol) was added slowly within 30 min at 0°C,
and the reaction mixture was continued to stir for 2 h at low temperature, and for 1 h at
room temperature. The white solid was filtered, washed with water (3×20 mL).
Recrystallization from ethanol-water gave colorless block crystals that were suitable for
X-ray diffraction analysis. Yield: 18.06 g (76 %). Melting point: 150～152°C. IR (KBr,
cm-1): 3229 (m), 3181 (m), 2959 (m), 2877 (w), 1714 (s), 1547 (vs), 1465 (m), 1245 (m),
1
1206 (s), 1027 (s). H NMR (d6-DMSO, ppm): δ 0.902 (s, 12H), 1.880 (s, 4H), 3.607 (s,
4H), 3.873 (s, 4H), 9.916 (s, 2H), 10.924 (s, 2H). 13C NMR (d6-DMSO, ppm): δ 180.040,
153.843, 71.582, 42.672, 27.799, 19.121. ESI-MS+: m / z+ = 393.2242 (M + H+), Calc.
393.1625. Anal. Calc. for C15H28S2O4N4: C, 45.90; H, 7.19; N, 14.27; S, 16.34. Found: C,
45.98; H, 7.72; N, 14.22; S, 16.38.
2.3 Preparation of Complex {[Ag(L)(NO3)·CH3CN]}n (1)
Ligand L (39 mg, 0.1 mmol) in MeCN (10 mL) was dropwise added into AgNO3 (17
mg, 0.1 mmol) in MeCN (10 mL). The mixture was stirred overnight at room temperature.

The white precipitate was collected after filtrating, and washing with cooled CH3CN.
Yield: 33.0 mg (59%). Slow evaporation of solution of white solid in CH3CN afforded
colorless needle crystals which were suitable for X-ray diffraction analysis. IR (KBr,
cm-1): 3225 (m), 2962 (m), 2871 (w), 1718 (s), 1536 (vs), 1381 (s), 1290 (m), 1225 (m),
1
1030 (m). H NMR (d6-DMSO, ppm): δ 0.907-0.924 (d, J=6.8, 12H), 1.888-1.955 (m,
2H), 2.015-2.048 (t, 2H), 3.688-3.733 (m, 4H), 3.932-3.949 (d, J=6.8, 4H),
10.270-10.299 (t, 2H), 11.179 (s, 2H). ESI-MS+: m / z+ = 501.1292 (M - NO3), Calc.
501.059. Anal. Calc. for C15H28AgS2O7N5: C, 32.03; H, 5.02; N, 12.45; S, 11.40. Found:
C, 32.10; H, 5.12; N, 12.46; S, 11.58.
2.4 Preparation of Complex [Au(L)Cl] (2)
Ligand L (15 mg, 0.038 mmol) in CH3CN (5 mL) was dropwise added into
HAuCl4·4H2O (16 mg, 0.038 mmol) in CH3CN (5 mL). The reaction mixture was stirred
overnight at room temperature, and the filtrated, during which color of solution was
changed from pale yellow to colorless. Slow evaporation of filtrate at room temperature
afforded colorless needle cystals that were suitable for X-ray diffraction analysis. Yield:
15.1 mg (46 %). IR (KBr, cm-1): 3217 (m), 2957 (m), 2871 (w), 1722 (vs), 1623 (m), 1514 (vs),
1
1268 (s), 1223 (s), 1028 (m)., H NMR (d6-DMSO, ppm): δ 0.920-0.937 (d, J=6.8, 12H),
1.916-1.983 (m, 2H), 2.014-2.072 (m, 2H), 3.747-3.762 (d, J=6, 4H), 3.963-3.980 (d,
J=6.8, 4H), 10.580 (s, 2H), 11.542 (s, 2H). ESI-MS+: m / z+ = 589.1653 (M - AuCl2),
Calc. 589.1212; m / z+ = 1177.3168 ([M - AuCl2]2 - H+), Calc. 1177.2352; m / z+ =
1373.2900 ([M - AuCl2]2 + Au - 2H+), Calc.1373.1939. Anal. Calc. for
C15H28Au2Cl2S2O4N4: C, 21.01; H, 3.29; N, 6.53; S, 7.48. Found: C, 20.03; H, 3.51; N,
6.57; S, 8.57. Anal. Calc. for C15H28Au2Cl2S2O4N4: C, 21.01; H, 3.29; N, 6.53; S, 7.48.
Found: C, 19.93; H, 3.51; N, 6.51; S, 8.25.
2.5 X-ray crystallography

Diffraction data of L, 1 and 2 were recorded on a Bruker CCD diffractometer with
monochromatized Mo-Kα radiation (λ = 0.71073 Å). The collected frames were
processed with the software SAINT. The absorption correction was treated with
SADABS [17]. Structures were solved by direct methods and refined by full-matrix
least-squares on F2 using the SHELXTL software package [18]. Atomic positions of
non-hydrogen atoms were refined with anisotropic parameters. All hydrogen atoms were
introduced at their geometric positions and refined as riding atoms. In complex 2, due to
the serious disorder, we employed PLATON/SQUEEZE to calculate the diffraction
contribution of co-crystallized solvent molecules.
3. Results and Discussions
3.1 Synthesis and characterization
N,N’-diisobutyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea (L), as shown in
Scheme 2, was synthesized by treatment of 1,3-propanediamine with the isothiocyanate
iPrCH2OC(O)NCS with high yield. It is noteworthy that reaction of isothiocyanate with
amine leading to the corresponding thiourea is frequently observed, while with diamine
resulting in the bisthiourea is less common in the literature. Bisthiourea L is ready to
react with transition metal salt, AgNO3 and HAuCl4 , to afford corresponding metal
complexes {[Ag(L)(NO3)·CH3CN]}n (1) and [Au(L)Cl] (2), respectively. During the
synthesis, dilute solutions of L and metal salt (< 0.015 molL-1) is critical to obtain the
final product of 1 and 2, or L would be precipitated and not reacted with the metal salt
completely. Similar reaction of L with other transition metal salt, such as [Cu(CH3CN)4]+,
Mn2+, Fe2+, Fe3+, Co2+ and Ni2+, were tried. Unfortunately, no products based on L are
isolated. Complex 1, 2 and L, as colorless crystalline solid, are air stable and soluble in
common organic solvent such as CH2Cl2, CH3CN and THF, but insoluble in H2O, ether
and hexane.
1
These compounds were characterized by IR, H NMR, UV-vis, cyclic voltammetry
and elemental analyses and X-ray diffraction analysis. The IR spectrum of L shows weak
bands at around 3229 cm-1 for ν(N-H), 2959 cm−1 for ν(C-H) and intense bands 1714 and

1547 cm-1 assigned to ν(C=O) and ν(C=S), respectively. In complexes 1 and 2,
persistence of bands at around 3225 and 1718-1722 cm-1 due to ν(N-H), ν(C=O),
respectively, suggests the presence of an N-H, C=O groups which does not participate in
bonding with the metal ion. However, the C=S bonds suffer negative shift of 11 and 33
cm-1 for 1 and 2, respectively, indicating of coordination of the ligand via thioamide
sulfur atom. In addition, a distinctive signal at 1381 cm-1 in 1 are due to N=O stretching
1
frequencies of the coordinated nitrate ligand. The H NMR spectra of L, 1 and 2 in
d6-DMSO reveal a single set of signals for iPr protons, containing a doublet for the –CH3
group at ca. 0.91 ppm and a quartet for the –CH- group at ca. 1.92 ppm. The signals for
the C–CH2-C, CH2O, CH2N groups in 1 and 2 in these compounds were observed at
about 2.03, 3.73 and 3.95 ppm, respectively. It is worth noting that the signals for the
NHCS and NHCO protons in 1 and 2 at 10.3 and 11.4 ppm, respectively, are similar with
that found in L (9.92 and 10.9 ppm), indicating thioamide nitrogen does not coordinate to
metal ion. The L, 1 and 2 have similar UV-vis spectra (S3). The L has a single intense
absorption band at 270 nm. A slight blue-shift of 5 nm and 6 nm are observed in
complexes 1 and 2, respectively. The ligand and the complexes 1 and 2 are not
luminescent in solution and in the solid state. The formal potential for L, 1 and 2 have
been determined by cyclic voltammetry (S4). The cyclic voltammograms for these
compounds display irreversible redox couples in range of -0.5~1.0 V vs Ag/AgNO3
electrode and an anodic peak at 1.50 V vs Ag/AgNO3 electrode assignable to the ligand.
Addition anodic peaks at 1.62 V vs Ag/AgNO3 electrode for complex 2 could be
attributed to the AuI/AuIII oxidation couple.
3.2 Structure description
Crystals of L were obtained by slow evaporation of its ethanol-water solution, and
crystal of 1 and 2 were from evaporation of its acetonitrile solution. A summary of
crystallographic data and experimental details for L, 1 and 2 are listed in Table 1. The
selected bond distances and bond angles are shown in Table 2. Their ORTEP diagrams
are displayed in Figure 1-3, respectively.
Ligand L crystallizes in the space groups P-1. As shown in Fig. 1, backbone in L

bends in the same direction. The C-C, C-N, C=O bonds are in the typical range of
hydrocarbon compounds. The C-S bond distance are 1.672(5) Å and1.675(3) Å, which
are well similar with those observed in other thiourea derivatives. The O2 and O4 atoms
form two set of intramolecular hydrogen bonds with the each neighboring amide. The
O2···N2 and O4···N4 distances are 2.664(4) and 2.670(6) Å, respectively. Intermolecular
N-H···S hydrogen bonds are present between the thioamide sulfur and NH hydrogen of
nearby molecule of the ligand. The N1···Si and N3···Sii distance are 3.329(3), 3.374(4) Å,
respectively (symmetry code: i: 2-x, 1-y, -z; ii: 1-x, 2-y, 1-z).
Complex 1 crystallizes in monoclinic space group P2(1)/c with one co-crystallized
acetonitrile molecule. Fig. 2a shows the asymmetric building unit of 1, which consists of
one silver atom, one nitrate anion and one bisthiourea L ligand. The bisthiourea L
behaves as sulfur donor ligand to coordinate to silver atoms. Two sulfur donors have
different coordination mode. One is κ-S, and another one is µ2-S’,S’. It means one sulfur
donor links one silver atom, and another sulfur atom bridges two silver atoms. Each silver
atom is coordinated by one O atom from nitrate anion, three S atoms from three
equivalent bisthiourea ligand, generating a distorted {AgOS3} tetrahedron geometry. The
Ag-O bond distance is 2.423(6) Å. The bond distances of Ag-S1 (2.402(2) Å) is slightly
shorter than that of Ag-S3 (2.4492(19) Å and 2.835(2) Å). The bond angles of S-Ag-O
and S-Ag-S are 95.33(17)-107.28(16)o, and 94.57(7)-133.10(7)o, respectively. Fig. 2b
displays that {AgOS3} tetrahedron is side-shared by each other to form a Ag2S2
four-membered rings. The Ag···Ag distance is 3.596 Å. Each Ag2S2 ring crosslinks four
bisthiourea L to generate a two-dimensional layer structure. To our knowledge, this is the
first report of layer structure based on the bisthiourea ligand. Within the layer, hydrogen
bonds are found between amide NH and the ketone oxygen and nitrate oxygen atoms.
The co-crystallized CH3CN solvent molecules are occupied between the layers (Fig. 2c).
Complex 2 crystallizes in triclinic space group P-1. Unlike the coordination polymer
1, complex 2 is molecular compound. As shown in Fig. 3, L as a neutral bidentated
ligand binds to two Au atom in µ-(κ-S, κ-S’) bonding mode. The bond situation in 2 is
analogous to those in chloro(N,N-diethyl-N’-benzoylthiourea)gold(I) [19] or
chloro(N,N-diethyl-N’-camphanylthiourea)gold(I) [20], where the neutral thiourea
derivatives are S-bonded to gold, but unlike to [{Au(PPh3)}2(L’-κ-S)] (H2L’ =

3,3,3,3-tetraethyl-1,1-isophthaloylbisthiourea) [21], where the aroylthiourea unit is
deprotonnated. The reduction reaction of Au3+ to Au1+ in 2 takes place by the addition of
bisthiourea. The analogous reduction reaction of Cu2+/Cu+ in presence of thiourea had
been chemically and electrochemically proved in solution [6, 15]. Each Au atom in 2 is
almost linearly coordinated to S and Cl atom. The bond angle of S-Au-Cl are 176.71(11)o
o
and 177.11(9) . The average bond distances of Au-S and Au-Cl are 2.256 and 2.266 Å,
respectively. Intramolecular hydrogen bonds in 2 are observed between N-H and the
neighboring ketone oxygen.
4. Conclusion
N,N’-diisobutyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea and its silver(I) and
gold(I) complexes are prepared and fully characterized. This bisthiourea was readily
synthesized by treatment of isothiocyanate with the diamine. Treatment of bisthiourea
with AgNO3 and HAuCl4 in CH3CN afforded coordination polymer 1 and molecular 2,
respectively. In complex 1, each silver atom is four-fold coordination, and Ag2S2 unit
crosslinks four bisthiourea ligands to form a two-dimensional layer structure. In complex
2, reduction reaction of Au3+ to Au+ took place in presence of bisthiourea, and each gold
atoms is two-fold coordination. In these two complexes, bisthiourea only acts as sulfur
donor to coordinate to silver and gold atom. We also investigated the reaction of
bisthiourea with relative harder metal cations, such as Mn2+, Fe2+, Fe3+, Co2+ and Ni2+, to
understand the coordination capability of nitrogen and oxygen donor in bisthiourea,
however, no products was detected. According to the above information, we believe
N,N’-diisobutyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea have a remarkable high
affinity with soft acid-type heavy metal ions but not the hard acid-type metal ions based
on the theory of hard soft acid base. This bisthiourea is featured with high selective
coordination capability, and has potential application in the area of metallurgical industry.
Acknowledgements

This work was supported by the National Natural Science Foundation of China (project
21571190 and 51474253), the National Basic Research Pro-gram of China (973 program)
(2014CB643403), the National High Technology Research and Development Program of
China (863program) (2013AA064101), Hunan Provincial Science and Technology Plan
Project, China (No. 2016TP1007), and Grants from the Project of Innovation-driven Plan
in Central South University (2015CXS004).
Notes and references
† Electronic Supplementary Information (ESI) available. CCDC reference numbers
1553269, 1553265 and 1553270 for L, 1 and 2, respectively.
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Scheme 1 Bonding mode of thiourea
M
M
M
S
S
S
S
M
M
N
NHR2
N
NHR2
HN
R1O
NHR2
HN
NHR2
R1O
O
R1O
O
O
R1O
O
bidentated N,S donor
N donor
S donor
S donor
S
M
M
O
O
S
HN
R1O
NR2
M
S
R1O
N
NR2
M
R1O
N
NHR2
O
bidentated O,S donor
tridentated N,O,S donor
bidentated N,O donor

Scheme
2
The
Synthesis
of
ligand
N,
N’-diisobutyryl
butyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea (L)
S
S
O
O
HN
N
H
N
H
NH
NaSCN, DMA
at 0oC in H2O
H2N(CH2)3NH2
at 0oC in H2O
O
NCS
O
Cl
O
O
O
O
L

Fig. 1 ORTEP diagram of L. All hydrogen atoms except for amine hydrogen are omitted
for clarity.

Fig. 2a ORTEP diagram of 1. All hydrogen atoms except for amine hydrogen,
co-crystallized CH3CN molecule are omitted for clarity.

Fig. 2b The layer structure of 1. The hydrogen atoms, nitrate anion and iPrOC(O)N
groups of bisthiourea L are omitted for clarity.

Fig. 2c The packing diagram of 1.

Fig. 3 ORTEP diagram of 2. All hydrogen atoms except for amine hydrogen are omitted
for clarity.

Table 1 Crystallographic data and experimental details for L, 1 and 2.
Compound
Empirical formula
Formula weight
Crystal system
a (Å )
L
C15H28N4O4S2
392.53
1
2
C17H31AgN6O7S2 C15H28Au2Cl2N4O4S2
603.47
Monoclinic
15.191(6)
9.491(4)
19.178(7)
90
857.37
Triclinic
5.3870(2)
10.0364(5)
19.9721(9)
100.539(3)
95.523(4)
104.613(3)
1015.68(8)
P-1
Triclinic
9.5694(4)
11.0116(5)
12.8381(6)
77.836(3)
83.740(3)
68.267(3)
1227.72(10)
P-1
b (Å )
c (Å )
α (o)
β (o)
γ (o)
111.578(15)
90
V (Å3)
2571.3(18)
P2(1)/c
4
Space group
Z
2
2
Dcalc (g cm-3)
T (K)
1.284
1.559
2.319
296(2)
293(2)
1240
296(2)
F(000)
420
804
Μ (mm-1)
Total reflections
Independent
reflections
Rint
0.288
0.993
12.351
11445
17154
9143
4497
5858
4728
0.0496
0.1027
0.0275
R1,b wR2 c (I > 2σ(I))
R1, wR2 (all data)
Goodness-of-fit a
0.0756, 0.1912
0.1235, 0.2288
0.0759, 0.1749
0.1776, 0.2175
1.032
0.0657, 0.1603
0.0807, 0.1666
1.175
1.050
½
a GoF = [Σw(|Fo| − |Fc|)2/(Nobs − Nparam)] . b R1 = Σ||Fo| − |Fc||/Σ|Fo|. c wR2 [(Σw|Fo| − |Fc|)2/Σw2|Fo|2]½.

Table 2 Selected bond lengths (Å) and bond angles (°) for L, 1 and 2
Bond lengths (Å) Bond angles (°)
N, N’-diisobutyryl butyloxycarbonyl-N”,N’”-(1,3-propylene)-bisthiourea (L)
S(1)-C(6)
S(2)-C(10)
O(2)-C(5)
O(4)-C(11)
1.675(3)
1.672(5)
1.205(4)
1.217(5)
Complex 1
Ag(1)-S(1)
Ag(1)-S(3A)
Ag(1)-S(3B)
Ag(1)-O(5)
S(1)-C(6)
2.402(2)
2.4492(19)
2.835(2)
2.423(6)
1.683(7)
1.702(7)
1.203(7)
1.313(8)
S(1)-Ag(1)-O(5)
S(1)-Ag(1)-S(3A)
S(1)-Ag(1)-S(3B)
104.02(16)
133.10(7)
116.40(7)
O(5)-Ag(1)-S(3A) 107.28(16)
O(5)-Ag(1)-S(3B) 95.33(17)
S(3A)-Ag(1)-S(3B) 94.57(7)
S(3)-C(10)
O(2)-C(5)
O(3)-C(11)
Symmetry transformations used to generate equivalent atoms:
-x+1,y+1/2,-z+1/2.
A x,-y+3/2,z+1/2; B
Complex 2
Au(1)-S(1)
Au(2)-S(2)
Au(1)-Cl(2)
Au(2)-Cl(1)
S(1)-C(10)
S(2)-C(6)
2.256(3)
2.257(3)
2.268(2)
2.264(3)
1.739(8)
1.705(7)
1.221(10)
1.203(12)
S(1)-Au(1)-Cl(2)
S(2)-Au(2)-Cl(1)
177.11(9)
176.71(11)
O(1)-C(5)
O(3)-C(11)

Graphic abstract (Pictogram)
The designed bisthiourea ligand acts as neutral sulfur donor, while interestingly its silver
complex displays a layer structure and gold complex is a molecular compound.
[Ag(L)NO3⋅CH3CN]
n
3
1
3
S
S
Layer structure of 1
HN
N
H
N
H
NH
O
O
O
O
L
[Au(L)Cl]
2
Molecular 2