An unusual diverse coordination of silver(I) with N-allylthiohydantoin ligand in the presence of benzene- and p-toluenesulfonate anions

Article abstract of DOI:10.1016/j.ica.2018.09.029

Crystalline silver(I) coordination compounds [Ag₂(HL)₄(C₆H₅SO₃)₂]·0.5C₃H₇OH (1) and [Ag₂(HL)(L)(CH₃C₆H₄SO₃)] (2) (HL = 3-(prop-2-en-1-yl)-2-thioxoimidazolidin-4-one) have been obtained using silver(I) salts and the organic ligand HL. Three independent Ag(I) atoms in crystal 1 adopt exclusively different coordination environment: tetragonal pyramidal, seesaw and distorted tetrahedral. In crystal 2 metal ions coordination polyhedra are characterized by seesaw and distorted tetrahedral arrangements. Thiohydantoin molecules in both structures are attached to Ag(I) only through thiohydantoin S-atom, while its anionic form in 2 plays a role of N,S-linker. C₆H₅SO₃^? anions in 1 are bound to the Ag(I) ions in a bridging mode, connecting silver ions into serpentine-like {Ag₄(C₆H₅SO₃)₄}_n chains, within which silver ions are additionally bind with μ₂-S atoms of HL. Simultaneous coordination of HL and L^? moieties in polymeric chains of 2 allow the formation of Ag….Ag metallophilic interactions with the distance range of 2.99–3.13 ?.

Full text of DOI:10.1016/j.ica.2018.09.029

Accepted Manuscript
Research paper
An unusual diverse coordination of silver(I) with N-allylthiohydantoin ligand
in the presence of benzene- and p-toluenesulfonate anions
A.A. Fedorchuk, Yu.I. Slyvka, V. Kinzhybalo, T. Lis, M.G. Mys'kiv
PII:
S0020-1693(18)30730-8
https://doi.org/10.1016/j.ica.2018.09.029
ICA 18487
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
10 May 2018
3 August 2018
9 September 2018
Please cite this article as: A.A. Fedorchuk, Yu.I. Slyvka, V. Kinzhybalo, T. Lis, M.G. Mys'kiv, An unusual diverse
coordination of silver(I) with N-allylthiohydantoin ligand in the presence of benzene- and p-toluenesulfonate anions,
Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.09.029
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An unusual diverse coordination of silver(I) with N-allylthiohydantoin ligand in
the presence of benzene- and p-toluenesulfonate anions
a
a,*
b
c
a
A. А. Fedorchuk , Yu. I. Slyvka , V. Kinzhybalo , T. Lis , M. G. Mys’kiv
a
Faсulty of Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya 6, 79005 Lviv,
Ukraine
b
Institute of Low Temperature and Structure Research, Okólna 2, 50-422 Wrocław, Poland
c
Faсulty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383 Wrocław, Poland
*Corresponding author. Tel.: +380322394506; e-mail: yurii.slyvka@lnu.edu.ua (Yu. I. Slyvka)
Highlights:
-
-
-
Two novel complexes with unusual diverse coordination of Ag(I) with N-
allylthiohydantoin were studied
Different Ag(I) arrangements are determined by variable thiohydantoin
coordination modes
Simulations presence of molecular ligand and its ionic form were observed
Abstract:
Crystalline
SO ]·0.5C
silver(I)
coordination
(HL)(L)(CH
compounds
[
(
Ag
2
(HL)
4
(С
6
H
5
3
)
2
3
H
7
OH (1) and [Ag
2
3
С
6
H
4
SO
3
)] (2) (HL = 3-
prop-2-en-1-yl)-2-thioxoimidazolidin-4-one) have been obtained using silver(I) salts
and the organic ligand HL. Three independent Ag(I) atoms in crystal 1 adopt
exclusively different coordination environment: tetragonal pyramidal, seesaw and
distorted tetrahedral. In crystal 2 metal ions coordination polyhedra are characterized
by seesaw and distorted tetrahedral arrangements. Thiohydantoin molecules in both
structures are attached to Ag(I) only through thiohydantoin S-atom, while its anionic
-
form in 2 plays a role of N,S-linker. C
6
H
5
SO
3
anions in 1 are bound to the Ag(I) ions
(C SO
-S atoms of HL.
in a bridging mode, connecting silver ions into serpentine-like {Ag
4
6
H
5
3
) }
4 n
chains, within which silver ions are additionally bind with µ
2
–
Simultaneous coordination of HL and L moieties in polymeric chains of 2 allow the
formation of Ag….Ag metallophilic interactions with the distance range of 2.99 -
3
.13 Å.
Keywords: silver(I); benzenesulfonate anion; toluenesulfonate anion; thiohydantoin;
crystal structure.

1
. Introduction
Heterocyclic compounds containing 2-thioxoimidazolidin-4-ones (namely 2-
thiohydantoin) fragment possess valuable pharmaceutical properties such as
anticarcinogenic, antimutagenic, antimicrobial, anticonvulsant, etc [1-7]. They also
exhibit fluorescence sensing properties towards Cu2+ and Cu [8] and may by
successfully used in crystal engineering of organometallics. Due to simultaneous
presence of thiocarbamide and carbonyl as well as N–H donor groups,
+
2
-thiohydantoins take part in the controlled formation of hydrogen bonded arrays
determining a special condition of target supramolecular assemblies formation [9].
Despite the huge advances in synthesis and possible application of 2-thiohydantoin
derivatives, the data concerning its use as ligands in coordination compounds still
remains quite limited, only 28 corresponding entries have been found in Cambridge
Crystallographic Database [10]. Among these some of copper containing complexes
were found to be cytotoxic for a variety of cancer cell lines. The presence of N-allyl
radical at imidazolin-4-one core significantly reduces the toxicity of copper (mixed
valence) chloride complexes in comparison with the well-known drug cisplatin [11].
In contrast to copper, coordination chemistry of 3,5-dihydroimidazol-4-ones
regarding to silver(I) salts is represented by only one AgNO
3
derivative, containing 2-
(methylthio)-3-phenyl-5-(pyridine-3-ylmethylene)-3,5-dihydro-4H-imidazol-4-one as
a ligand [12]. The ligand molecule is connected to silver ion in a bridging mode by
means of pyridine nitrogen atom and S-methyl sulfur one, while N atom of imidazol-
4
-one ring remains unbound to the metal centre. In this aspect coordination activity of
imidazol-4-one fragment in regard to copper and silver is significantly different, since
+
Cu ions in all the cases are attached to heterocyclic N atom of 2-S-alkyl-imidazol-4-
ones, leaving sulfur atom uncoordinated [13]. Contrary to the above,
2
-thioxoimidazolidin-4-ones (non S-substituted 2-thiohydantoin) tend to be bound to
+
“
soft” Cu ions by means of the only exocyclic sulfur atom [14].
Taking into account that according to HSAB theory [15] olefinic C=C bond acts
as a “soft” base, a comprehensive investigation of thiohydantoin allyl derivatives
coordination with Ag(I) becomes very attractive. Allylic C=C bond may successfully

compete with exocyclic sulfur in metal coordination, causing an exclusive inorganic
fragment formation, like it was observed for copper(I) π-complexes with allyl
derivatives of heterocycles [16]. To study coordination behaviour of N-allyl-2-
thiohydantoin in regard to silver(I) herein we present synthesis and structural
characterization of [Ag
2
(HL)
4
(С
6
H
5
SO
3
)
2
]·0.5C
3
H
7
OH (1) complex with an unusually
(HL)(L)(CH SO )] (2)
diverse Ag(C SO ) coordination mode and [Ag
6
H
5
3
2
3
С
6
H
4
3
coordination compound, emphasizing the influence of thiohydantoin ligand on
exclusively different environments of Ag+.
2
. Experimental section
2
.1. Materials and instrumentation
Unless mentioned otherwise, all chemicals were obtained from commercial
1
sources and used without further purification. The NMR experiments: H NMR (500
1
3
1
MHz), C{ H} NMR (125 MHz) were recorded on a Bruker Avance 500 MHz NMR
spectrometer. The chemical shifts are reported in ppm relative to the residual peak of
1
13
1
the deuterated CD OD for the H and C{ H} NMR spectra. The infrared (IR)
3
spectra were recorded on the Bruker IFS-88 spectrometer for 1 and on FT-IR
Spectrum BX-II (Perkin Elmer) for 2 as nujol mulls. Diffraction data for 1 and 2
crystals were collected on an Agilent Xcalibur four-circle diffractometer with Mo K
a
radiation (λ = 0.71073 Å) and a Ruby and Atlas CCD detectors, respectively [17].
Hirshfeld surfaces of the molecules in complex 1 and fingerprint plots were produced
by CrystalExplorer software [18, 19]. Ligand HL was synthesized from
allylisothiocyanate and glycine in the presence of triethylamine and pyridine, in
1
accordance with the reported method [20]. H NMR (500 MHz, CD
3
OD) δ, 5.84
p.p.m. (ddt, J = 17.1, 10.4, 5.6 1H, =CH), 5.18 p.p.m. (ddd, J = 17.1, 2.9, 1.5 Hz, 1H,
CH =), 5.14 p.p.m. (ddd, J = 10.5, 2.5, 1.0 Hz, 1H, -CH =), 4.38 p.p.m. (dt, J = 5.6
Hz, 1.5 2H, CH ). C{ H} NMR (125 MHz, CD OD) δ, p.p.m.
85.74 p.p.m. (-C=S), 174.17 p.p.m. (-C=O), 132.62 p.p.m. (=CH), 117.94 p.p.m.
2
2
1
3
1
2
), 4.14 (s, 2H, CH
2
3
1
-1
(CH
2
=), 49.48 p.p.m. (CH
2
), 43.80 p.p.m. (CH ). IR (nujol, cm ): 3488 (w), 3225 (s),
2
3
1
091 (w), 3011 (vw), 1864 (vw), 1751 (vs), 1650 (m), 1524 (vs), 1431 (vs), 1367 (w),
344 (vs), 1306 (s), 1289 (w), 1260 (s), 1176 (vs), 1106 (m), 1048 (m), 1029 (m),

9
5
94 (m), 977 (w), 930 (s), 893 (m), 755 (vw), 719 (w), 700 (vs), 610 (m), 581 (m),
63 (m), 541 (m), 515 (m), 474 (m), 440 (vw).
2
.2. Synthesis of the [Ag
To the mixture of HL (50 mg, 0.32 mmol) and Ag
mL of n-propanol was added. After careful stirring of the obtained suspension,
2
(HL)
4
(С
6
H
5
SO
3
)
2
]·0.5C
3
H
7
OH (1)
2
CO (45 mg, 0.16 mmol)
3
1
followed by upholding it for one minute, a yellow clear solution (with furry gray-
brown precipitate) was obtained. The mixture acidity was adjusted by 0.25 ml of 40%
aqueous benzenesulfonic acid solution. After the evolution of gas stopped, reddish-
brown solution containing some amount of gray-brown precipitate was obtained.
Keeping the reactor at room temperature in a dark place during 48 h led to yellowish
crystals of [Ag
2
(HL)
4
(С
6
H
5
SO
3
)
2
]·0.5C
3
H
7
OH, which have appeared on the
1
precipitate surface. Yield about 55%. H NMR (500 MHz, CD
3
OD) δ, 7.86 p.p.m. (d,
J = 7.6 8H, HPh-2,6), 7.46 p.p.m. (d, J = 6.3 12H, HPh-3-5), 5.93 p.p.m. (ddd, J
22.3, 10.5, 5.4 8H, =CH), 5.42-5.17 p.p.m. (m, 16H, CH =), 4.46 p.p.m. (d, J = 5.3
Hz, 16H, -CH ), 4.28 p.p.m. (s, 8H, CH ), 3.50 p.p.m. (t, J = 6.6 Hz, 2H, CH ), 1.51-
.56 p.p.m. (m, 2H, CH ), 0.93 p.p.m. (t, J = 7.4 Hz, 3H, CH ). C{ H} NMR (125
OD) δ, p.p.m. 185.00 p.p.m. (-C=S), 173.15 p.p.m. (-C=O), 132.08 p.p.m.
=
2
2
2
2
1
3
1
1
2
3
MHz, CD
3
(=CH), 131.37 p.p.m. (CPh-4), 129.35 p.p.m. (CPh-3,5), 126.97 p.p.m. (CPh-2,6),
-
1
1
3
1
1
17.85 p.p.m. (CH
2
=), 50.18 p.p.m. (CH
2
), 44.26 p.p.m. (CH ). IR (nujol, cm ):
2
561 (w), 3509 (w), 3127 (m), 3084 (m), 3046 (m), 1758 (vs), 1658 (vw), 1644 (w),
536 (vs), 1447 (vs), 1423 (m), 1409 (m), 1365 (v), 1334 (vs), 1262 (m), 1224 (s),
176 (vs), 1152 (vs), 1120 (vs), 1068 (m), 1058 (m),1030 (m), 1012 (s), 995 (m), 986
(
w), 923 (m), 910 (m), 878 (m), 758 (m), 694 (s), 652 (m), 611 (s), 580 (m), 565 (m),
44 (m), 521 (w), 484 (v), 437 (vw).
5
2
0
.3. Synthesis of the [Ag
To the mixture of p-CH
.36 mmol) 1 mL of n-propanol and 1 mL of water was added. After the evolution of
2
(HL)(L)(CH
3
6
С H
4
SO
3
)] (2)
3
6
С H
4
SO
3
H (125 mg, 0.73 mmol) and Ag
2
CO (100 mg,
3
gas stopped, 125 mg of HL (0.80 mmol) was added and orange-brown suspension
with yellow-grey precipitate was obtained. Keeping the reactor at room temperature

in
Ag
was about 36%.
a
dark place during 100
h
led to colourless crystals of
[
2
(HL)(L)(CH SO )], which have appeared on the precipitate surface. Yield
3
С
6
H
4
3
-
1
IR (nujol, cm ): 2724 (w), 2682 (vw), 2361 (w), 2340 (w), 1760 (m), 1739 (m),
1
1
9
5
647(vw), 1623 (m), 1539 (w), 1516 (s), 1456 (s), 1410 (vw), 1339 (w), 1328 (w),
299 (w), 1248 (w), 1194 (m), 1171 (v), 1159 (vw), 1130 (m), 1045 (w), 1014 (vw),
26 (w), 919 (w), 882 (w), 816 (v), 776 (vw), 772 (m), 694 (m), 660 (w), 598 (vw),
65 (w).
2
.4. Single crystal X-ray diffraction studies.
The collected diffraction data for 1 and 2 were processed with the CrysAlis PRO
program [21]. The structures were solved by direct methods and refined by least
2
squares method on F by SHELXL-2014 with the following graphical user interfaces
of OLEX2 [22, 23]. Atomic displacements for non-hydrogen atoms in both structures
were refined using an anisotropic model. Solvent n-propanol carbon atoms in 1 were
refined with fixed at 0.5 atom site occupancy factors, the molecule is disordered
around the center of inversion. One of metal atoms (Ag2) in 1 is splitted into two
equivalent positions (s.o.f. 50%). All hydrogen atoms in 1 and 2 were placed in ideal
positions and refined as riding atoms with relative isotropic displacement parameters.
The crystal parameters, data collection and the refinement are summarized in Table 1.
Table 1. Selected crystal data and structure refinement parameters of 1 and 2.[a]
Crystal data
CCDC number [a]
1
2
1842308
1842309
Empirical formula
C
·
36
H
42Ag
2
N
8
O
10
S
6
C
19
H
22Ag
2
N
4
O
S
5 3
0.5C
1184.92
Crystal system, space group Triclinic, P1
3
H OH
7
-1
Formula weight (g·mol )
698.32
Triclinic, P1
a (Å)
b (Å)
c (Å)
α (º)
12.301(3)
14.334(4)
14.377(4)
106.77(5)
92.90(5)
7.255 (2)
12.532 (3)
14.211 (4)
67.41 (5)
84.69 (5)
β (º)

γ (º)
V (Å3)
Z
102.81(5)
89.70 (5)
2348.9(13)
1187.2 (7)
2
2
-1
µ (mm )
1.16
1.95
F(000)
1202
692
Crystal size (mm)
Crystal color
0.40× 0.12 × 0.07
yellow
0.48× 0.20 × 0.13
clear colourless
Calculated density, g/cm3
Data collection
1.675
1.176
Radiation type, wavelength, Mo Ka, 0.71073
λ(Å)
Mo Ka, 0.71073
Temperature, K
80(2)
100(2)
θ range for data collection
2.0 – 30.8
2.8 – 29.3
(
º)
Index ranges
–17 ≤ h ≤ 17, –16 ≤ k ≤ 20, –9 ≤ h ≤ 9, –16 ≤ k ≤ 17,
–
18 ≤ l ≤ 20
–18 ≤ l ≤ 19
Measured reflections
22124
13183
7031
25660
5919
Independent reflections
Observed refl. (I > 2σ(I))
5206
R
int
0.052
0.029
99.94%
Completeness to θ = 25.49 99.86 %
2
2
Refinement on
F
F
Data/restraints/parameters 13183/3/602
5919/0/299
2
2
R[F > 2σ(F )]
wR(F2 )
0.062
0.029
0.120
0.071
GooF = S
1.00
1.05
∆
ρ
max/∆ρmin (e Å3 )
0.74 and -1.27
1.09 and -1.32
[
a] CCDC number contain the supplementary crystallographic data for this paper. Copies of
the data can be obtained free of charge on applications to the Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Fax: int.code +(1223)336–033; e-mail for inquiry:
fileserv@ccdc.cam.ac.uk).
3
. Results and discussion
3
.1 Crystal structure descriptions.
Asymmetric part of [Ag
2
4
(HL) (С
6
H
5
SO
)
3 2
3
]·0.5C H
7
OH (1) crystal is represented
by three independent silver(I) atoms, each of which possess different coordination
(
Fig. 1). A closest Ag1 environment includes three bridging exocyclic sulfur atoms
S1, S2 and S3) of the three neighbouring thiohydantoin molecules (correspondingly
(

1
2
3
named HL , HL and HL ) and one oxygen (O25) atom of benzenesulfonate anion
-
(Fig. 1). Due to some steric hindrance (caused by C
6
H
5
SO
3
anion) Ag1—S3 bond
distance is significantly longer (2.808(2) Å) in comparison with the other two Ag1—
S1 (2.443(2) Å) and Ag1—S2 (2.450(2) Å). The nearest to Ag1 atom – O36 of the
adjacent C
although this distance is shorter than the sum of corresponding VdW radii (3.24 Å)
24, 25]. Therefore, according to geometric index, proposed by Addison [26]
geometrical environment of Ag1 metal center can be treated as tetragonal pyramid
=0.23).
6
H
5
SO -
3
anion is placed at quite long distance from Ag1 of 3.067(3) Å,
[
(τ
5
Figure 1. Asymmetric part of crystal 1 along with the numbering scheme.
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1.
Table 2
Selected interatomic distances and angles for crystal 1.
Distance
(Å)
Distance
(Å)
Ag1—S1
Ag1—S2
Ag1—S3
Ag1—O25
2.443(2)
2.450(2)
2.809(2)
2.675(3)
Ag2—S3
Ag2 —S3i a
Ag2—S2
Ag2—O26
2.394(4)
2.456(4)
3.191(3)
2.728(4)

i
Ag1—O36
Ag3—S4
Ag3—O15
Ag3—S1
3.067(3)
2.475(2)
2.634(4)
3.085(2)
Ag2—O26
S1...S2
S3...S3
3.197(4)
4.659(4)
4.817(4)
i
Angle
(º)
Angle
(º)
S1—Ag1—O25
S2—Ag1—O25
S3—Ag1—O25
S1—Ag1—S2
S1—Ag1—S3
S2—Ag1—S3
O25—Ag1—O36
S4—Ag3—O15
98.83(8)
102.67(9)
85.46(8)
144.43(6)
111.06(6)
98.67(6)
158.21(10)
94.78(9)
85.22(9)
79.86(9)
85.22(9)
S3—Ag2—O26
79.40(11)
166.61(6)
111.23(13)
83.73(9)
90.18(10)
111.23(13)
173.35(8)
89.71(9)
80.30(8)
119.48(6)
i
S3—Ag2—S3
i
S3 —Ag2—O26
O26—Ag2—S2
S3—Ag2—S2
i
S3 —Ag2—S2
i
S2—Ag2—S2
Ag1—S3—Ag2
Ag1—S2—Ag2
Ag1—S1—Ag3
ii
S4—Ag3—O15
S1—Ag3—O15
S1—Ag3—O15
ii
[a] Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1.
The Ag3 atom lies on the center of symmetry and is surrounded by four S atoms
1
4
(
two terminal and two bridging) of four symmetry related HL and HL molecules
-
and by two O atoms of the two bridging C
6
H
5
SO
3
anions (Fig. 2). Two terminal
sulfur atoms of two centrosymmetrically related HL moieties are closer to the metal
center (Ag3—S4 2.475(2) Å) than the other bridging two (Ag3—S1 3.085(2) Å) and
together with two O15 form square surrounding of the metal ion. Both Ag3—S4 and
Ag3—O15 bond distance values are comparable with Ag1—S1, Ag1—S2 and Ag1—
O25 (Table 2) ones. It is worth to note, that Ag3—S1 bond distance value is
significantly shorter than its corresponding VdW radii sum (3.52 Å). Therefore
symmetry related S1 atoms complete Ag3 surrounding to distorted octahedral with
three different atom pairs.

Figure 2. Coordination environment of Ag3 in 1.
Symmetry codes: (ii) −x+1, −y+1, −z+1.
Somewhat similar coordination environment may be attributed to Ag2 atom: two
2
3
O atoms and four thiohydantoin S atoms (of HL and HL ) form distorted tetrahedron.
i
But significant removal of centrosymmetrically related S2 and S2 atoms from the
octahedron middle point by 3.391(4) Å allows Ag2 atom to be split with two
centrosymmetrically related sites (Fig. 3), enabling seesaw arrangement of the metal.
i
The distance from Ag2 to opposite thiohydantoin S3 of 3.602(4) Å somewhat
exceeds the sum of corresponding VdW radii (3.52 Å) and also confirms the seesaw
i
geometry of Ag2 arrangement. S3—Ag2—S3 bond angle of 166.61(6)º indicates
closer to linear atoms arrangement, while the remaining atoms pair forms O26—
Ag2—S2 angle of 83.73(9)º. Ag2—S2 bond value of 3.191(3) Å is comparable with
i
Ag3—S1 of 3.085(2) Å. The nearest to silver(I) S3 and S3 atoms are separated from
i
each other at the distance of 4.817(5) Å, that is closer than analogous S4…S4
4
.950(5) Å and S1…S2 4.659(4) Å distances. In contrast, due to significant
-
packaging hindrance of C
6
H
5
SO
3
anion Ag2—O26 distance is somewhat longer
(
Ag2—O26 2.728(4) Å) in comparison with the other observed.

Figure 3. Coordination environment of disordered Ag2 in 1. Symmetry codes: (i) −x,
−
y, −z+1. Hydrogen atoms are omitted for clarity.
Figure 4. Different types of Ag(I) coordination arrangement in crystal 1.
1
4
All four HL - HL moieties have similar geometrical parameters except for the
conformation of non-coordinated allyl groups, which are involved into C–H…O and
1
4
C–H…π types of intermolecular interactions (Fig. 5). HL – HL moieties according
to Klyne-Prelog system are characterized by synclinal conformation (+96.19(5)º
1
2
3
4
(
HL ), -64.69(5)º (HL ), -64.86(6)º (HL ), -66.38(6)º (HL )) relative N1–C4 bond and
1
2
3
synperiplanar (-5.8(7)º (HL ), -2.8(7)º (HL )) and anticlinal (+119.8(6)º(HL ), -

4
1
21.4(6)º (HL )) conformation relative to C4—C5 bond. The distance value changes
in the range of 1.451 - 1.459(6) Å for C3—N2 between methylene carbon atom and
1
4
unsubstituted nitrogen of HL - HL thiohydantoin rings, what indicates the presence
of dominant σ-component of the bond. Due to the effect of conjugation between
heterocyclic nitrogen atoms and S=C and C=O bonds in thiohydantoin the bond
lengths of C1—N1 and C2—N1 are al most identical and range from 1.375 to
1
.396(6) Å correspondingly for all four molecules. The C1—N2 bond value is
4
1
significantly shorter and decreases in the order: 1.324(5) Å (HL ), 1.314(6) Å (HL ),
2
3
1
.311(6) Å (HL ) and 1.308(6) Å (HL ).
Figure 5. (a) Overlay of N-allylthiohydantoin molecules in (a) 1 and (b) 2. Molecule
A in 1 is inverted. Atoms used for overlay fit are labeled.
-
Two independent C
6
H
5
SO
3
anions are bound to the Ag(I) atoms in a bridging
(C SO chain (Fig. 6).
mode, connecting silver ions into serpentine-like {Ag
4
6
H
5
3
) }
4 n
+
Additionally S atoms of thiohydantoin molecules bind neighboring Ag ions. Organic
HL molecules are additionally fixed to the organometallic chain with N–H…O
hydrogen bonds (Table 3) and both anions are involved in hydrogen bonding
simultaneously with two thiohydantoin molecules.

Figure 6. Organometallic chains with {Ag
4
(C
6
H
5
SO
3
)
4
n
} fragments in 1. Symmetry
codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1.
Table 3. Geometry of N–H..O hydrogen bonds in the crystals of 1 and 2.
Atoms involved
D−H···A
Symmetry
Angle
D−H···A
Distances, Å
H···A
D···H
1
D···A
N2A−H2A···O36
N2B−H2B···O25
N2C−H2C···O26
N2D−H2D···O15
0.88
0.88
0.88
0.88
2
1.93
1.95
2.13
2.05
2.778(6)
2.827(5)
2.962(6)
2.821(5)
161.6
172.5
157.4
145.7
−x, −y, −z+1
N2B−H2B···O33 −x+2, −y+2, −z+1
0.88
1.86
2.712(3)
162.1
In contrast to other coordination compounds of ionic silver(I) salts with N-allyl
derivatives of heterocycles [27-29], in which allylic C=C bond is involved in metal
coordination, N-allyl residue of thiohydantoin in 1 prefers to be unattached to the
metal. The planes of neighboring independent thiohydantoin rings are wrapped
relative to each other by 49.1(3)º, so that the O atom of one HL is oriented very close
(~3.1 Å) to the center of the second thiohydantoin ring.
It should be noted, that 1 may be considered as a new example of coordination
+
SO
-, since only one entry (corresponding to silver(I)
mode of Ag and C
6
H
5
3
benzenesulfonate) in Cambridge Structural Database was deposited up-to-date and
shows a tridentate coordination of the anion [30]. In the last structure nine-
-
coordinated Ag(I) is occupied by six O atoms of the tridentate-bridging C
6
H
5
SO
3
anions and by three neighboring Ag atoms (Ag – Ag 2.915(1) Å), forming a two-

dimensional infinite array incorporating a first known six-fold metal-bridging mode
for the sulfonate ion.
1
The comparison of H NMR-spectra of HL and 1 in deuterated CD
3
OD solvent
indicates the inactivity of the allyl group with respect to Ag(I)-(C=C) π-interaction.
This fact agrees with HSAB rule as well as with a large affinity of Ag(I) to O and S
atoms. In contrast to 1, there are a number of earlier studied crystalline coordination
compounds of Ag(I) with allyl derivatives of heterocycles, in which metal ion is π,σ-
2
bonded to the organic ligand through η -coordination of the allylic C=C bond [31-35].
During a formation of [Ag
2
(HL)(L)(CH
3
С
6
H
4
SO )] (2) complex HL ligands
3
undergo partial deprotonation, resulting in coordination to the metal of
–
simultaneously neutral HL and anionic L forms of the N-allylthiohydantoin ligand.
Independent part of crystal 2 is represented by two different four-coordinated silver(I)
atoms (Fig. 7). Ag1 surrounding in structure 2 is close to seesaw arrangement (τ =
4
–
0
.63) and includes one heterocyclic N atom of the L anion, one O atom of the
–
CH
3
C
6
H
4
SO
3
anion and two bridging exocyclic sulfur atoms (S1 and S2) from two
–
different HL and L ligand moieties (Fig. 8). Ag2 atoms have distorted tetrahedral
–
surrounding (τ
4
= 0.82) formed by O atom of the bridging CH
3
C
6
H
4
SO
3
anion and
three bridging S atoms of allylthiohydantoin ligands, one of which is from HL (S2)
–
i
ii
molecule and two – from L anions (S1 and S1 ). As the result, Ag(I) atoms in 2
–
stitch allylthiohydantoin ligands together with CH
3
6
C H
4
SO
3
anions into polymer
i
chain. Ag2—S2 and Ag2—S1 distances are comparable and equal to 2.5650(13) Å
ii
and 2.5611(11) Å, respectively, but they are significantly shorter than Ag2—S1
–
(
2.7199(12) Å). Each L fragment is involved in coordination with four different Ag
ions: one Ag ion is attached through Ag1—N2A bond (2.208(3) Å) and the other
three Ag ions through Ag—S1 interactions. Due to geometrical reasons all three
–
Ag—S1 bonds are not equal in this structure (Table 4). Unlike L , HL is bonded only
i
with two Ag ions through bridging S2 atom (Ag1—S2 , 2.6192(13) Å, Ag2—S2
2
.5650(13) Å). Neutral HL ligands are additionally involved in N–H…O hydrogen
bonds with neighbouring toluenesulfonate anions (Table 3).

Figure 7. Part of crystal 2 along with the numbering scheme. Symmetry codes: (i)
x+1, −y+2, −z+1; (ii) x+1, y, z.
−
Figure 8. Coordination environments of Ag1 (a) and Ag2 (b) in crystal 2.
Table 4
Selected interatomic distances and angles for crystal 2.
Distance
(Å)
Distance
(Å)
Ag1—N2A
Ag1—O13
2.208(3)
2.568(3)
2.6192(13)
2.6437(16)
3.1295(14)
3.0126(17)
(º)
Ag2—S2
Ag2—O23
2.5650(13)
2.489(3)
2.7199(12)
2.5611(11)
2.9899(15)
3.0497(15)
(º)
i a
ii
Ag1—S2
Ag1— S1
Ag2— S1
Ag2— S1
i
i
iii
ii
Ag2 — Ag2
Ag2 — Ag1
Angle
Ag2 — Ag1
Ag1 — Ag1
Angle
ii
N2A—Ag1—O13
94.80(9)
S2—Ag2—O23
101.57(6)

i
i
i
N2A—Ag1—S1
N2A—Ag1—S2
142.14(7)
128.46(7)
86.84(4)
77.43(7)
116.23(6)
S2—Ag2—S1
136.93(4)
102.90(4)
96.35(8)
104.67(6)
107.39(5)
ii
S2—Ag2— S1
O23—Ag2—S1
O23—Ag2—S1
i
i
ii
i
S1 —Ag1—S2
i
S1 —Ag1—O13
i
ii
i
S2 —Ag1—O13
S1 —Ag2—S1
[
a] Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1, y, z.; (iii) −x+2, −y+2,
−
z+1
It should be noted, that dehydrogenation of thiohydantoin molecule during
transition metal ion complexation is not a unique phenomenon and recently was
encountered in the reaction of 5-(pyridine-2-yl-methyl)-2-thioxo-4-imidazolidinones
–
and copper(II) chloride [36]. Simultaneous coordination of HL and L moieties in
polymeric chain of 2 makes possible Ag … Ag metallophilic interactions (Fig. 9)
with the distance range of 2.99 - 3.13 Å. All marked Ag(I)….Ag(I) distances are
significantly shorter than the sum of corresponding metal VdW radii (3.44 Å). Taking
into account general geometry of the {[Ag
2
(HL)(L)(CH
3
С
6
H
4
SO
3
)]}
n
chain, two
} fragment
types of fragments ({Ag } and {Ag }) may be marked. In {Ag
4
S
4
2
S
2
4
S
4
Ag….Ag distances are relatively close (2.99 - 3.01 Å) and are somewhat shorter than
Ag2….Ag2 distance (3.13 Å) in {Ag } (Fig. 9).
S
2 2
Figure 9. Ag—S bonded chain with metallophilic interactions in 2.
3
.2 Vibrational spectra of compounds 1 and 2.
Although the spectra of coordination compounds 1 and 2 are complex, their
comparison with IR-spectrum of respective ligands leads to certain conclusions. The
-1
bands at 1152, 1120, 1012, 652 cm in IR-spectrum of complex 1 and 1159, 1130,
-
1
1
014, 660 cm in 2 are not present in the spectrum of free HL, and in accordance
with literature data [37] can be assigned to benzenesulfonate and toluenesulfonate

anions as νas(SO
3
), ν(SO
3
), ν
s
(SO
3
) and δ
s
(SO
3
) modes, respectively. The bands at
-
1
-1
1
068 and 878 cm in 1 as well as at 1045 and 882 cm in 2 also can be assigned to
C
6
H
5
SO -
The bands at 1751, 1650 and 1524 cm in spectrum of free ligand and 1758, 1658
3
and CH
3
C
6
H
4
SO -
anions as ν(C–C)ring+ ν(C–S) and γ(CH) + δ(CS) modes.
3
-
1
-
1
and 1524 cm in spectrum of complex 1 and 1760, 1647, 1516 of complex 2 arise
from HL thiohydantoin C=O vibration, allyl C=C stretching and ring motions [38,
3
9].
3
.3 Hirshfeld surfaces of the ligand in 1.
The Hirshfeld surfaces were built for all independent thiohidantoin moieties to
analyze interactions between the ligands. The most prominent interactions between
hydantoin N-H and anion O atoms as well as between hydantoin O and other H atoms
can be seen in the Hirshfeld surface plots as the middle and poorly red areas (Fig.
1
0A). Fingerprint plots were produced to show the intermolecular surface bond
distances with the regions highlighted for (N)H···O and (HL)O···H interactions. From
Fig. 10 one can derive the most significant (HL)O···H interaction of HL in
comparison with the other three ligands, that may be explained by participation of HL
in hydrogen bonding with hydroxyl group of the solvent propanol molecule. C–
H…π-interactions between hydrogen atoms of allyl group or thiohydantoin methyl
groups and benzensulfonate phenyl rings make up 2.4 - 12.6% of the surface area.
The contribution to the surface area for S…H contacts is in the range of 3.7 to 8.4%.

1
4
Figure 10. Hirshfeld surface analysis of thiohydantoin HL – HL molecules (corresponding to S1 –
S4 atoms) in complex 1. (A) Hirshfeld surfaces mapped with dnorm which highlights both donor and
1
4
acceptor ability. (B) Fingerprint plots for HL – HL molecules resolved into (HL)O···H contacts.
The full fingerprint appears beneath each decomposed plot in grey. (C) Fingerprint plots for four
1
4
HL – HL resolved into (N)H···O contacts. The full fingerprint appears beneath each decomposed
plot in grey.
4
. Conclusions
By the reaction of N-allylthiohydantoin with Ag(C
Ag(CH SO ) the two new σ-complexes (1 and 2) with an interestingly diverse
6
H
5
SO
3
)
and
3
C
6
H
4
3
Ag(I) coordination environments were synthesized. The structure 1 represents the
second known (and completely different from earlier studied) example of
AgC
6
H
5
SO coordination mode. Different silver(I) arrangements are determined by
3
variable thiohydantoin coordination modes due to steric hindrances, caused in 1 by
both an efficient (N)H…O (1.93 - 2.13 Å) bonding with the anions and allyl group
mobility and partial deprotonation of HL in complex 2. Ag(I) environments in 1
appear to be tetragonal pyramidal, seesaw and distorted octahedral, while in 2 metal
atoms are characterized by seesaw and distorted tetrahedral arrangements.

Independent C
6
H
5
SO -
3
anions in 1 are bound to the Ag(I) ions in a bridging mode,
(C SO fragment. The last ones
connecting silver ions into serpentine-like {Ag
4
6
H
5
3
) }
4 n
are sewn by bridging S atoms of thiohydantoin into infinite chains. Simultaneous
coordination of HL and L– moieties in polymeric chains in 2 makes possible
Ag….Ag metallophilic interactions with the distance range of 2.99 - 3.13 Å. Due to
HSAB theory rule as well as a large affinity of Ag(I) to O atoms Ag(I)-(C=C) π-
bonding does not occur in the studied compounds.
5
References
1
. C. Carmi, A. Cavazzoni, V. Zuliani, A. Lodola, F. Bordi, P. V lazzi, R. R. Alfieri,
P. Petronini, M. Mor, Bioorg. Med. Chem. Lett. 16 (2006) 4021-4025.
https://doi.org/10.1016/j.bmcl.2006.05.010.
2
. A. Cavazzoni, R. R. Alfieri, C. Carmi, V. Zuliani, M. Galetti, C. Fumarola, R.
Frazzi, M. Bonelli, F. Bordi, A. Lodola, M. Mor, P. G. Petronini, Mol. Cancer
Ther. 7 (2008) 361-370. https://doi.org/10.1158/1535-7163.MCT-07-0477
. C. Harrison, Nat. Rev. Drug. Disc. 8 (2009) 452-453. https:// doi:10.1038/nrd2903
. M. Mudit, M. Khanfar, A. Muralidharan, S. Thomas, G. V. Shah, R. W. M. van
Soest, K. A. Sayed, Bioorg. Med. Chem. 17 (2009) 1731-1738.
https://doi.org/10.1016/j.bmc.2008.12.053
3
4
5
6
7
. H. C.
Shen,
S. P. Balk,
Cancer
Cell
15
(2009)
461-463.
https://doi.org/10.1016/j.ccr.2009.05.005
. Q. Zhu, Y. Pan, Z. Xu, R. Li, G. Qiu, W. Xu, X. Ke, L. Wu, X. Hu Eur. J. Med.
Chem. 44 (2009) 296-302. https://doi.org/10.1016/j.ejmech.2008.02.024
. R. Raj, V. Mehra, J. Gut, P. J. Rosenthal, K. J. Wicht, T. J. Egan, M. Hopper,
L. A. Wrischnik, K.M. Land, V. Kumar, Eur. J. Med. Chem. 84 (2014) 425-432.
https://doi.org/10.1016/j.ejmech.2014.07.048
8
. Weifeng Zeng, Xiaodong Yang, Xiuli Chen, Yichen Yan, Xinwei Lu, Jinqing Qu,
Ruiyuan
https://doi.org/10.1016/j.eurpolymj.2014.10.015
. S. Jha, J. D. Silversides, R. W. Boyle, S. J. Archibald, Cryst. Eng. Comm. 12
2010) 1730-1739. https://doi.org/10.1039/B924683E
0.C. R. Groom, I. J. Bruno, M. P. Lightfoot, S. C. Ward, Acta Cryst. B72 (2016)
71-179 https://doi.org/doi:10.1107/S2052520616003954
1.A.G. Majouga, M. I. Zvereva, M. P. Rubtsova, D. A. Skvortsov, A. V. Mironov,
D. M. Azhibek, O. O. Krasnovskaya, V. M. Gerasimov, A. V. Udina,
Liu,
Eur.
Polym.
J.
61
(2014)
309-315.
9
1
1
(
1
N. I. Vorozhtsov, E. K. Beloglazkina, L. Agron, L. V. Mikhina, A. V. Tretyakova,
N. V. Zyk, N. S. Zefirov, A. V. Kabanov, O. A. Dontsova, J. Med. Chem. 57
(
2014) 6252-6258. https://doi.org/doi:10.1021/jm500154f
2.S. Z. Vatsadze, A. G. Majouga, E. K. Beloglazkina, A. V. Mironov, N. V. Zyk,
Mendeleev Commun. 17 (2007) 77–79.
https://doi.org/10.1016/j.mencom.2007.03.007
1

1
3.E. K. Beloglazkina,
R. B. Romashkina, N. V. Zyk, A. A. Moiseeva, K. P. Butin, Izv. Akad. Nauk
SSSR, Ser. Khim.(Russ.) (Russ.Chem.Bull.) (2005), 2771–2782.
https://doi.org/10.1007/s11172-006-0190-6
S. Z. Vatsadze,
A. G. Mazhuga,
N. A. Frolova,
1
1
1
4.P. Aslanidisa, S. Kyritsisa, M. Lalia-Kantouria, B. Wicherb, M. Gdaniec,
Polyhedron 48 (2012) 140-145. https://doi.org/10.1016/j.poly.2012.08.065
5.R.G.
https://doi.org/10.1021/ja00905a001
6.Y. Slyvka, E. Goreshnik, O. Pavlyuk, M. Mys’kiv, Centr. Eur. J. Chem. 11 (12)
2013) 1875-1901. https://doi.org/10.2478/s11532-013-0323-3
Pearson,
J.
Am.
Chem.
Soc.
85
(1963)
3533-3539.
(
1
1
7.Agilent, CrysAlis PRO, Agilent Technologies, Yarnton, England, 2011
8.S.K. Wolff, D.J. Grimwood, J.J. McKinnon, M.J. Turner, D. Jayatilaka, M.A.
Spackman, University of Western Australia, 2012.
1
2
9.M.A. Spackman, D. Jayatilaka, Cryst. Eng. Comm., 11 (2009) 19-32.
https://doi.org/10.1039/B818330A
0.Michael E. Garst, Lloyd J. Dolby, Shervin Esfandiari, Alfred A. Avey, Jr., Vivian
Rose MacKenzie, Charles David Muchmore, Unite States, Patent 2007. U.S.
Patent 7.919.630 B2, April 5, 2011.
2
2
1.Agilent, CrysAlis PRO, Agilent Technologies, Yarnton, England, 2011.
2.G.M.
Sheldrick.
Acta
Cryst.
C71
(2015)
3-8.
https://doi.org/10.1107/S2053273314026370
2
2
2
2
2
2
3.O.V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J.
Appl. Cryst. 42, (2009) 339-341. https://doi.org/10.1107/S0021889808042726
4.A.
https://doi.org/10.1021/j100785a001
5.Santiago Alvarez, Dalton
https://doi.org/10.1039/c3dt50599e
Bondi,
J.
Phys.
Chem.,
68
(1964)
441-451.
Trans.
42
(2013)
8617-8736.
6.A. W. Addison, N. T. Rao, J. Reedijk, J. van Rijn, G. C. Verschoor, J. Chem. Soc.
Dalton Trans. (1984) 1349-1356. https://doi.org/10.1039/DT9840001349
7.A. V. Noshchenko, Yu. I. Slyvka, A. V. Pavlyuk, M. G. Mys’kiv, Russ. J. Coord.
Chem. 36, 8 (2010) 585-594. https://doi.org/10.1134/S1070328410080051
8.Solomon W. Kelemu, Christopher M. Fitchett, Matthew I.J. Polson, Jan L.
Wikaira, Peter J. Steel, J. Organomet. Chem. 749 (2014) 129-133.
https://doi.org/10.1016/j.jorganchem.2013.09.029
2
3
9.S.W.
Kelemu,
P.J.
Steel,
Polyhedron
71
(2014)
99-103.
https://doi.org/10.1016/j.poly.2014.01.011
0.G.K. H. Shimizu,
J.A. Ripmeester,
G.D. Enright,
Chem.
C.I. Ratcliffe,
Commun.
K.F. Preston,
(1999)
J.L. Reid,
1485-1486.
https://doi.org/10.1039/A904445K
3
3
3
3
1.S.W. Kelemu, P.J. Steel, Cryst. Eng. Comm.15 (2013) 9072-9079.
https://doi.org/10.1039/C3CE41708E
2.Yu. I. Slyvka, J. Struct. Chem. 56, 1 (2015) 179-180.
https://doi.org/10.1134/S0022476615010242
3.Yu. I. Slyvka, N. T. Pokhodylo, E. A. Goreshnik, M. G. Mys’kiv, J. Struct. Chem.
5, 2 (2014) 368-369. https://doi.org/10.1134/S0022476614020279
5
4.Yu. Slyvka, O. Pavlyuk, N. Pokhodylo, B. Ardan, Z. Mazej, E. Goreshnik, Acta.
Chim. Slov. 58 (2011) 134-138. http://acta-arhiv.chem-soc.si/58/58-1-134.pdf

3
3
3
3
3
5.Yu. I. Slyvka, J. Struct. Chem. 58, 2 (2017) 356-357.
https://doi.org/10.1134/S0022476617020184
6.A.G. Majouga, E.K. Beloglazkina, A.V. Yudina, A.V. Mironov , N.V. Zyk, Inorg.
Chem. Commun. 51 (2015) 114-117. https://doi.org/10.1016/j.inoche.2014.11.021
7.M. Ristovaa, L. Pejova, M. Zugicb, B. Soptrajanov, J. Mol. Struct. 482–483
(1999) 647-651. https://doi.org/10.1016/S0022-2860(98)00890-4
8.R.S. Lebedev, R. P. Chumakova, V. N. Yukhimets, V. I. Yakimenko, Soviet.
Phys. J. 13 (1970) 18-23. https://doi.org/10.1007/BF00817216
9.A. Sharma, V. Gupta, R. Mishra, P. Tandon, Sh. Maeda, K.-K. Kunimoto, J. Mol.
Struct. 1004 (2011) 237-247. https://doi.org/10.1016/j.molstruc.2011.08.011

Highlights:
-
-
-
Two novel complexes with unusual diverse coordination of Ag(I) with N-
allylthiohydantoin were studied
Different Ag(I) arrangements are determined by variable thiohydantoin
coordination modes
Simultaneous presence of molecular ligand and its ionic form was observed