1148 Acta Chim. Slov. 2020, 67, 1148–1154
Fedorchuk et al.:   Cu(I) Arylsulfonate π-Complexes   ...
DOI: 10.17344/acsi.2020.6045
Scientific paper
Cu(I) Arylsulfonate π-Complexes  
with 3-Allyl-2-thiohydantoin: The Role of the Weak 
Interactions in Structural Organization
Andrii Fedorchuk,1 Evgeny Goreshnik,2,* Yurii Slyvka3  
and Marian Mys’kiv3
1 Institute of Nuclear Physics, Polish Academy of Sciences,  
Radzikowskiego 152, PL-31342 Krakow, Poland
2 Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39,  
SI-1000 Ljubljana, Slovenia
3 Department of Inorganic Chemistry, Ivan Franko National University of Lviv,  
Kyryla i Mefodiya 6, 79005 Lviv, Ukraine 
* Corresponding author: E-mail: evgeny.goreshnik@ijs.si  
Phone: +386 1 477 36 45
Received: 04-12-2020
Abstract
The present work is directed toward preparation and structural characterization of two novel Cu(I) arylsulfonate π-com-
plexes with 3-allyl-2-thiohydantoin, namely [Cu2(Hath)4](C6H5SO3)2 (1) and [Cu2(Hath)4](p-CH3C6H4SO3)2 · 2H2O (2) 
(Hath = 3-allyl-2-thiohydantoin), obtained by the means of alternating current electrochemical synthesis and studied 
with X-ray diffraction method. In both structures, the inner coordination sphere is represented by the cationic dimer 
[Cu2(Hath)4]2+ with one crystallographically independent copper(I) atom which has a trigonal pyramidal coordination 
environment formed by three Hath thiogroup S atoms and double C=C bond of its allyl group. [Cu2(Hath)4]2+ fragments 
in both coordination compounds are very similar, despite some divergences such as a big difference in Cu−S distance to 
the apical S atom (3.0374(8) Å in 1 and 2.7205(9) Å in 2). This difference was explained by the impact of the system of 
weak interactions, which are quite different. 
Keywords: Copper(I) arylsulfonate; π-complex; thiohydantoin; weak interaction; crystal structure.
1. Introduction
In the last years both 2-thiohydantoin (2-thioxoim-
idazolidin-4-ones) and hydantoin core fragments were 
studied as useful scaffolds in medicinal chemistry due to 
their synthetic feasibility and versatility of substituents. 1–5 
Moreover, their derivatives are already used in commer-
cially available drugs such as Phenytoin, Dantrolene and 
Allantoin. The presence of several active chemical groups, 
as well as simple synthetic route advantages, could make 
them interesting not only as biologically active compounds 
but also as compounds of great interest in the chemistry of 
coordination compounds too. Although, due to the pres-
ence of capable for  complex compound formation  func-
tional groups, 2-thiohydantoin based compounds were 
found to have an application in the analytical chemistry as 
reagents for the determination of several d-metals (includ-
ing Cu and Ag).6, 7 Despite the small number of such rep-
resentatives (according to the Cambridge Crystallographic 
Database only 12 copper coordination compounds with 
2-thiohydantoin still known),8 it was already investigated 
that they could have a potential interest as optical materi-
als due to their fluorescence sensing properties and lumi-
nescence towards Cu+ and Cu2+ as well as the possibility of 
successful usage in crystal engineering of organometal-
lics.9,10 Moreover, previously, we have shown, that Cu(I) 
π-complexes with allyl derivatives of heterocycles can pos-
sess noticeable non-linear optical properties.11–15 
This work is the continuation of our previous stud-
ies, in which we have studied the coordination behavior of 
1149Acta Chim. Slov. 2020, 67, 1148–1154
Fedorchuk et al.:   Cu(I) Arylsulfonate π-Complexes   ...
3-allyl-2-thiohydantoin (Hath) regarding Ag(I), where ob-
tained coordination compounds have already shown inter-
esting structural peculiarities, confirming the status of 
2-thiohydantoin-based molecules as the potential ligands 
in the structural engineering.16,17 
2. Experimental
2. 1. General Consideration
Unless otherwise mentioned, all chemicals were ob-
tained from a commercial source (Sigma Aldrich) and 
used without further purification. The NMR experiments: 
1H NMR (500 MHz), 13C{1H} NMR (125 MHz) spectra for 
Hath were recorded on a Bruker Avance 500 MHz NMR 
spectrometer. The chemical shifts are reported in ppm rel-
ative to the residual peak of the deuterated CD3OD for the 
1H and 13C{1H} NMR spectra. Carbon, hydrogen, nitrogen 
and sulfur contents for Hath, 1 and 2 compounds were de-
termined using a CHNS elemental analyzer vario EL cube 
(Elementar) operating in the CHNS mode. The infrared 
(IR) spectrum for Hath was recorded on the Bruker IFS-88 
spectrometer as nujol mulls. Diffraction data for 1 and 2 
were collected on a Gemini+ diffractometer with Mo Ka 
radiation (λ = 0.71073 Å) and Atlas CCD detector. 
2. 2.  Preparation of 3-allyl-2-
thioxoimidazolidin-4-one (Hath)
Ligand Hath was synthesized from allylisothiocya-
nate and glycine at the presence of triethylamine and pyri-
dine, in accordance with the reported method. 16 Yield 
57%. M.p. 91–92 °C. Anal. calcd. for C6H8N2OS: C, 46.13; 
H, 5.16; N, 17.93; S, 20.53; found: C, 45.93; H, 5.44; N, 
17.92; S, 20.65.
1H NMR (500 MHz, CD3OD) 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, CH2=), 5.14 p.p.m. (ddd, J = 10.5, 2.5, 1.0 Hz, 
1H, -CH2=), 4.38 p.p.m. (dt, J = 5.6 Hz, 1.5 2H, CH2), 4.14 
(s, 2H, CH2). 
13C{1H} NMR (125 MHz, CD3OD) δ, p.p.m. 185.74 
p.p.m. (-C=S), 174.17 p.p.m. (-C=O), 132.62 p.p.m. (=CH), 
117.94 p.p.m. (CH2=), 49.48 p.p.m. (CH2), 43.80 p.p.m. 
(CH2). 
IR (nujol, cm–1): 3488 (w), 3225 (s), 3091 (w), 3011 
(vw), 1864 (vw), 1751 (vs), 1650 (m), 1524 (vs), 1431 (vs), 
1367 (w), 1344 (vs), 1306 (s), 1289 (w), 1260 (s), 1176 (vs), 
1106 (m), 1048 (m), 1029 (m), 994 (m), 977 (w), 930 (s), 
893 (m), 755 (vw), 719 (w), 700 (vs), 610 (m), 581 (m), 563 
(m), 541 (m), 515 (m), 474 (m), 440 (vw).
2. 3. Preparation of Complexes 
2. 3. 1. Preparation of [Cu2(Hath)4](C6H5SO3)2 (1) 
To the solution of Cu(C6H5SO3)2·6H2O (0.157 g, 0.4 
mmol) in 4.5 ml of n-propanol 0.156 g (1 mmol) of 3-al-
lyl-2-thiohydanthoine (Hath) was added and obtained 
mixture was stirred. The resulting orange-brown solution 
was placed into a 5 mL test tube and then copper-wire 
electrodes in cork were inserted. The inner mixture in the 
obtained cell was subjected to alternating-current elec-
trochemical recovery (0.6 V, 50 Hz) for 5 days.18 Crystals 
1, suitable for X-ray diffraction studies, were formed on 
copper wires while maintaining this reactor for 2 weeks at 
–3 °C. Yield 35%. M.p. 128 °C. Anal. calcd. for C18H21 
CuN4O5S3: C, 40.55; H, 3.97; N, 10.51; S, 18.04; found: C, 
40.08; H, 3.72; N, 10.67; S, 17.86.
2. 3. 2.  Preparation of [Cu2(Hath)4]
(p-CH3C6H4SO3)2  · 2H2O (2) 
To 5 ml of a solution of 0.198 g (0.4 mmol) of 
Cu(p-CH3C6H4SO3)2 · 6H2O in n-propanol was added 
0.156 g (1 mmol) of 3-allyl-2-thiohydanthine (Hath) and 
stirred. The resulting orange-brown solution was placed 
into a 5 mL test tube and then copper-wire electrodes in 
cork were inserted. The inner mixture in the obtained cell 
was subjected to alternating-current electrochemical re-
covery (0.6 V, 50 Hz) during 2 days. Crystals 2, suitable for 
X-ray diffraction studies, were formed on copper wires. 
Yield 43%. M.p. 113 °C. Anal. calcd. for C19H25CuN4O6S3: 
C, 40.38; H, 4.46; N, 9.91; S, 17.02; found: C, 40.17; H, 4.34; 
N, 9.86; S, 17.21.
2. 4. X–Ray Crystal Structure Determination
The collected data for 1 & 2 were processed with 
CrysAlis Pro program.19 The structures were solved by du-
al-space algorithm using SHELXT and refined by least 
squares method on F2 by SHELXL-2014 with the following 
graphical user interfaces of OLEX2.20–22 Atomic displace-
ments for non-hydrogen atoms were refined using an 
anisotropic model. Hydrogen atoms were placed in ideal 
positions and refined as riding atoms with relative isotro-
pic displacement parameters. The figures were prepared 
using DIAMOND 3.1 software. Crystal parameters, data 
collection and the refinement parameters are summarized 
in Table 1.
3. Results and Discussion 
π-Complex [Cu2(Hath)4](C6H5SO3)2 (1) forms tri-
clinic crystals in the centrosymmetric space group P -1. This 
compound is composed of the centrosymmetric cationic 
[Cu2(Hath)4]2+ dimers (Fig. 1) with one crystallographi-
cally independent Cu atom and outer coordination sphere 
represented by benzenesulfonate anions. Cu(I) atom in 1 
has a trigonal pyramidal coordination environment (geo-
metric index τ4 = 0.80).23 Sulfur atom and C5A=C6A ole-
fine group from one Hath moiety and S centre from anoth-
er ligand unit form basal plane of the metal ion coordination 
1150 Acta Chim. Slov. 2020, 67, 1148–1154
Fedorchuk et al.:   Cu(I) Arylsulfonate π-Complexes   ...
sphere, and sulfur atom from one more Hath molecule is 
located at the apical position. The distance to the apical 
sulfur atom Cu1–S1i is equal to 3.0374(8) Å and is signifi-
cantly greater than Cu–S distances to the equatorial S1 and 
S2 atoms (Table 2).
In the mentioned cationic fragment [Cu2(Hath)4]2+ 
there are two crystallographically independent molecules 
of organic ligand Hath. One of them is coordinated to the 
Cu atom by the thiogroup S1 atom and double C=C bond 
of the allyl group. Thus, the first ligand molecule possesses 
a bidentate chelate function, forming a seven-membered 
{C4NSCu} cycle. The aforementioned S1 atom of the first 
ligand is also coordinated to the Cu1i atom, and, due to the 
cetrosymmetricity of the structure, a flat four-membered 
{Cu2S2} cycle with a S1–Cu1–S1i angle of 97.04(3)° is 
formed. Second ligand molecule is coordinated to the Cu1 
atom only through its S2 atom, complementing copper’s 
coordination number to four. Accordingly – allyl group of 
the second ligand molecule doesn’t participate in the metal 
bonding and is freely located in the crystal structure with 
anticlinal conformation (119.8(3)°) relative to the C4B–
C5B bond.
The structure of the complex [Cu2(Hath)4]
(p-CH3C6H4SO3)2 · 2H2O (2) is quite similar to the struc-
ture 1. It has similar cationic [Cu2(Hath)4]2+ fragments, 
but the outer coordination sphere is filled with p-toluene-
sulfonate anions and water molecules (Fig. 3). Regarding 
the cationic fragment, the main differences are in the no-
ticeable shortening of the Cu−S distance to the apical atom 
Table 1. Selected crystal data and structure refinement parameters of 1 and 2.
 [Cu2(Hath)4] [Cu2(Hath)4]
 (С6H5SO3)2 (1) (CH3C6H4SO3)2 × 2H2O (2)
Formula weight (g·mol–1) 533.11 565.15
Crystal system and space group Triclinic, P -1. Triclinic, P -1.
a(Å) 9.1664(6) 9.4494(3)
b(Å) 10.7387(6) 10.3035(4)
c(Å) 12.4008(6) 14.4419(6)
α(º) 93.096(4) 94.228(3)
β(º) 95.581(5) 94.821(3)
γ(º) 114.254(6) 116.983(4)
V(Å3) 1101.71(12) 1238.64(9)
Z 2 2
D (g/cm3) 1.607 1.515
µ (mm–1) 1.31 1.18
F(000) 548 584
Crystal size (mm) 0.53 × 0.42 × 0.34 0.60 × 0.36 × 0.25
Crystal colour colourless colourless
Temperature of the data collections (K) 150(2) 150(2)
θ range for data collection (°) 3.7 – 28.9 3.5–28.8
 −12≤ h ≤9 −11≤ h ≤ 11
Index ranges −14 ≤ k ≤ 13 −13 ≤ k ≤ 13
 −16≤ l ≤ 16 −19≤ l ≤ 18
Measured reflections 7786 8562
Independent reflections 4534 5143
Reflections with I > 2σ(I) 3954 4274
Refined parameters 288 302
Rint 0.022 0.024
R[F2 > 2σ(F2 )] 0.038 0.047
wR(F2 ) 0.091 0.132
Δρmax/Δρmin(e/Å3 ) 1.11, −0.65 1.04, −0.78
Table 2. Selected bond lengths (Å) and angle values (°) in 1 and 2.
  1 2
 Bond d, Å
 Cu1–S1 2.2573(8) 2.2785(8)
 Cu1–S2 2.2556(7) 2.2644(9)
 Cu1–S1X 3.0374(8) 2.7205(9)
 Cu1–m* 1.978(3) 1.994(3)
 C5A–C6A 1.361(4) 1.363(5)
 Angles ω, °
 S2–Cu1–S1 112.97(3) 112.06(3)
 S1–Cu1–S1X** 97.04(3) 97.21(3)
 m–Cu1–S1 117.03(8) 116.37(3)
 m–Cu1–S2 129.53(8) 128.32(3)
*m – middle point of C5A–C6A bond; **S1X – S1i atom for 1 and S1ii 
atom for 2 Symmetry codes: (i) 1−x, 2−y, 1−z; (ii) 2−x, 1−y, 1−z.
1151Acta Chim. Slov. 2020, 67, 1148–1154
Fedorchuk et al.:   Cu(I) Arylsulfonate π-Complexes   ...
(2.7205(9) Å in 2 compared to 3.0374(8) Å in 1) (Table 2) 
and a slightly different conformation of the uncoordinated 
ligand molecule, in particular, the torsion angle N23−
C4B−C5B−C6B is equal to 142.6(7)° (in contrast to 
119.8(3)° in 1). These differences can be explained, taking 
into account some features of the differences in the outer 
coordination sphere (Fig 2). 
Benzenesulfonate anions are located in the outer co-
ordination sphere and take part in the formation of weak 
bonding in the structure 1. Two out of three oxygen atoms 
of the same anion (O13 and O33) participate in N–H···O 
bonding (Table 3, Fig. 2) with N–H groups of different cat-
ionic fragments, connecting them into infinite H-bonded 
chain (Fig 3). Also, one of the oxygen atoms of C6H5SO3– 
anion (O13) forms a weak Cu–O contact with a bond 
length of 3.409(5) Å. Nevertheless, this distance is notice-
ably longer than the sum of van der Waals radii of Cu and 
O by Bondi (2.92 Å),24,25  it is still less than the correspond-
ing value according to both Batsanov and Alvarez studies 
– namely 3.55 Å and 3.88 Å respectively.26,27
The system of hydrogen bonding in 2 is much more 
complicated than in 1 due to the presence of the water 
Figure. 1. Cationic fragment [Cu2(hath)4]2+ in the structures 1 (a) and 2 (b). Symmetry codes: (i) 1−x, 2−y, 1−z; (ii) 2−x, 1−y, 1−z.
Figure. 2. Systems of weak bonding in the structure 1 (a) and 2 (b). Symmetry codes: (i) 1−x, 2−y, 1−z; (ii) 2−x, 1−y, 1−z; (iii) x−1, y, z; (iv) 1− x, −y, −z.
Table 3. Geometry of selected hydrogen bonds in 1.
Atoms involved  Distances, Å  Angle, deg
D−H···A D···H D···H D···H D−H···A
N2A–H2A···O33iii 0.86 1.99 2.743(3) 146
N2B–H2B···O13 0.86 2.01 2.774(3) 148
Symmetry code: (iii) x−1, y, z.
1152 Acta Chim. Slov. 2020, 67, 1148–1154
Fedorchuk et al.:   Cu(I) Arylsulfonate π-Complexes   ...
molecule (Table 4, Fig 3). As one of the results of its pre-
sentence in 2 all three anion’s O atoms participate in a for-
mation of hydrogen bonding – two of them (O23 and 
O33) form N–H···O bonding, like in 1, and the third one 
(O13) is connected with water molecule HwB atom. Sec-
ond water hydrogen HwA atom is involved in Ow–
HwA···O1Biv H-bonding with carbonyl C=O Hath group. 
As a result of all bonding, 2D H-bonded net is formed (Fig 
3). Also, like in 1, there is a weak Cu–O bonding but in 
structure 2, the corresponding distance is noticeably great-
er and is equal to 3.610(3) Å, which is still less than the 
sum of van der Waals radii by Alvarez (3.88 Å). 
As it was shown before, Cu1–S1X distance to the api-
cal S1X atom (X = i in 1 and ii in 2) is noticeably different 
in these two structures. Moreover, since all other distances 
and angles within the coordination environment of Cu 
atom are almost the same (Table 2) as well as a composi-
tion of the cationic fragment, it can be concluded that the 
cause of these differences should be found in the outer co-
ordination sphere. As a possible reason, we would like to 
introduce the confrontation of Cu–S bonding and Cu–O 
weak interaction. One can notice that in 1 structure Cu–S 
interaction is weaker (3.0374(8) Å) in comparison with 2 
(2.7205(9) Å) and vise versa – Cu–O interaction in 1 is 
Table 4. Geometry of selected hydrogen bonds in 2.
Atoms involved  Distances, Å  Angle, deg
D−H···A D···H H···A D···A D−H···A
N21–H21···O23iii 0.88 1.93 2.761(4) 156
N2A–H2A···O33ii 0.88 1.91 2.764(3) 164
Ow–HwA···O1Biv 0.85 2.00 2.841(6) 173
Ow–HwB···O13iii 0.85 2.08 2.914(5) 168
Symmetry codes: (ii) 2−x, 1−y, 1−z; (iii) x−1, y, z; (iv) 1−x, −y, −z. 
Figure. 3. 1D H-bonded chain in 1 (a) and 2D H-bonded net in 2 (b).
1153Acta Chim. Slov. 2020, 67, 1148–1154
Fedorchuk et al.:   Cu(I) Arylsulfonate π-Complexes   ...
stronger (3.409(3) Å) than  in 2 (3.610(3) Å) (Fig 2). In our 
previous works we have shown an impact of a weak inter-
actions, including hydrogen bonding, on the structural 
organization in π-complex compounds.28–30 The weaken-
ing of the Cu–O interaction in 2 (and the strengthening of 
Cu–S as a result) can be explained by the fact, that the an-
ion in 2 is involved in a larger number of the H-bonding, 
due to the presence of the water molecule, all of which 
competes with the Cu–O interaction. Finally, since the wa-
ter was presented in both reaction mixtures, but co-crys-
tallized only in 2, its presence in its crystal structure should 
be explained by the different character of benzene- and 
p-toluenesulfonate anions.
In our previous works we have synthesized a series 
of Ag(I) arylsulfonates coordination compounds with 
Hath possessing a completely different geometry and 
more complicated geometry, namely [Ag2(Hath)4(С6H5 
SO3)2] · 0.5C3H7OH, [Ag2(Hath)4(CH3C6H4SO3)2] and 
[Ag2(Hath)(ath)(CH3С6H4SO3)].16,17 In the first two co-
ordination compounds, a complex coordination chain is 
formed, within which there are three crystallographically 
independent Ag(I) atoms with different coordination en-
vironments (tetragonal pyramidal, seesaw and distorted 
octahedral), four crystallographically independent mole-
cules of Hath ligand and two anions of benzene- or tolue-
nesulfonate. The Hath molecule is coordinated exclusive-
ly through the S atom of the thiogroup, which is bonded 
to several metal centers simultaneously. In complex 
[Ag2(Hath)(ath)(CH3С6H4SO3)], part of the molecules of 
3-allyl-2-thiohydantoin is in the deprotonated form (ath). 
In all these three compounds double bonds of allyl groups 
have stayed unbounded. The lack of coordination of the 
2-thiohydantoin ligand C=C by the double bond of the 
allyl group in the case of Ag(I) complexes in contrast to 
Cu(I) ones, can be explained by the greater philicity of 
the Ag(I) atom to the exocyclic Sulfur atom, which in 
case of Ag(I) complexes tend to be bonded with a maxi-
mal amount of Ag(I) atoms.
4. Conclusions
Two novel copper(I) π-complexes [Cu2(Hath)4]
(C6H5 SO3)2 (1) and [Cu2(Hath)4] · 2CH3C6H4SO3 · 2H2O 
(2) (Hath = 3-allyl-2-thiohydantoine) were synthesized and 
characterized by the X-ray diffraction method. Both struc-
tures contain centrosymmetric cationic dimer 
[Cu2(Hath)4]2+ in which Cu(I) atom has a trigonal pyrami-
dal coordination environment. In contrast to Ag(C6H5SO3) 
& Ag(CH3C6H4SO3) complexes, in which Ag(I) prefers to 
be bound with ligand by S-atom only, copper(I) coordi-
nation environment in 1 & 2 includes both ligand`s exo-
cyclic sulfur atom and allylic C=C bond. Nevertheless, 
both [Cu2(Hath)4]2+ are very similar, there are some dif-
ferences, including the difference in the Cu1−S1X dis-
tance (3.0374(8) Å in 1 and 2.7205(9) Å in 2). As a possi-
ble explanation, the confrontation of Cu–S and Cu–O 
weak interaction was proposed. Due to this model this 
difference is explained by the fact, that the anion in 2 is 
involved in a larger number of the H-bonding, due to the 
presence of the water molecule in it, and acts on Cu(I) 
atom weaker than in 1. 
Supplementary material
CCDC numbers 1997084 (1) and 1997085 (2) con-
tains the supplementary crystallographic data for this pa-
per. Copies of the data can be obtained free of charge on 
applications to the Director, CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK (Fax: int. code +(1223)336–033; 
e-mail for inquiry: fileserv@ccdc.cam.ac.uk).
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Povzetek
V tem delu je predstavljena sinteza in strukturna karakterizacija dveh novih Cu(I) arilsulfonatnih π-kompleksov z 
3-alil-2-tiohidantoinom, in sicer [Cu2(Hath)4](C6H5SO3)2 (1) in [Cu2(Hath)4](p-CH3C6H4SO3)2·2H2O (2) (Hath = 
3-alil-2-tiohidantoin). Spojini smo pridobili z elektrokemijsko sintezo s spremenljivim tokom in preučevali z rentgensko 
difrakcijo. V obeh spojinah je notranja koordinacijska sfera sestavljena iz kationskega dimera [Cu2(Hath)4]2+ z enim kris-
talografsko neodvisnim Cu(I) atomom ki ima trigonalno piramidalno okolje ki ga tvorijo trije S atomi iz Hath tioskupin 
in dvojna C=C vez iz alilne skupine. Fragmenti [Cu2(Hath)4]2+ so zelo podobni v obeh koordinacijskih spojinah kljub 
nekaterim odstopanjem, npr. Veliki razliko v razdalji Cu-S do apikalnega S atoma (3.0374(8) Å v 1 in 2.7205(9) Å v 2). 
To razliko lahko razložimo z vplivom sistema šibkih interakcij, ki so bistveno različne.