Unexpected complexation of allylpseudothiohydantoin hydrochlorides towards CuX (X?=?Cl, NO3, ClO4, BF4, 1/2SiF6). The first known examples of joint CuI(Cl,ClO4) and CuI(Cl,BF4) π-complexes

Article abstract of DOI:10.1080/00958972.2017.1286012

By means of alternating current-electrochemical synthesis starting from a mixture of 2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-one (3-allylpseudothiohydantoin, napt) and 2-allylamino-1,3-thiazol-4(5H)-one (allylaminopseudothiohydantoin, aapt) hydrochlorides and corresponding copper(II) salts five new π-complexes, [Cu(napt)Cl] (1), [Cu₂(aapt)₂Cl]NO₃ (2), [Cu₂(aapt)₂Cl]BF₄ (3), [Cu₂(aapt)₂Cl]ClO₄ (4) and [Cu₂(aapt)₂Cl]₂SiF₆·2H₂O (5), were obtained and studied by X-ray single crystal diffraction and IR-spectroscopy. Napt and aapt molecules are selectively coordinated to Cu⁺ depending on the anion type. In crystals of 1 and 5, the organic ligands are attached to the metal in a chelating N,(C=C)-bidentate mode. The aapt molecule in 2-4 acts as a tridentate chelating ligand, being coordinated to the copper(I) ion through the heterocyclic N atom, carbonyl O atom, and C=C?bond of allyl group, forming an original cationic [Cu₂(aapt)₂Cl]⁺ fragment with both a bridging Cl^– ion and O atom of the C=O group. In the presence of the doubly charged SiF₆ ^2– anion, Cu(I) in 5 prefers to be bonded with two bridging Cl^– ions, rather than the C=O group, causing [Cu₂(aapt)₂Cl]⁺ units to associate into the infinite cationic chains. Crystals of 3 and 4 are the first known examples of the simultaneous BF₄ ^–/Cl^– or ClO₄ ^–/Cl^– participation in copper(I) π-complex formation.

Full text of DOI:10.1080/00958972.2017.1286012

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Unexpected complexation of
allylpseudothiohydantoin hydrochlorides towards
CuX (X = Cl, NO , ClO , BF , 1/2SiF ). The first known
3
4
I
4
6
I
examples of joint Cu (Cl,ClO ) and Cu (Cl,BF ) π-
4
4
complexes
A. A. Fedorchuk, V. V. Kinzhybalo, Yu. I. Slyvka, E. A. Goreshnik, T. J.
Bednarchuk, T. Lis & M. G. Mys’kiv
To cite this article: A. A. Fedorchuk, V. V. Kinzhybalo, Yu. I. Slyvka, E. A. Goreshnik,
T. J. Bednarchuk, T. Lis & M. G. Mys’kiv (2017): Unexpected complexation of
allylpseudothiohydantoin hydrochlorides towards CuX (X = Cl, NO , ClO , BF , 1/2SiF ). The
3
4
4
6
I
I
first known examples of joint Cu (Cl,ClO ) and Cu (Cl,BF ) π-complexes, Journal of Coordination
4
4
Chemistry, DOI: 10.1080/00958972.2017.1286012
To link to this article: http://dx.doi.org/10.1080/00958972.2017.1286012
Accepted author version posted online: 24
Jan 2017.
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Date: 27 January 2017, At: 03:35

Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://dx.doi.org/10.1080/00958972.2017.1286012
Unexpected complexation of allylpseudothiohydantoin hydrochlorides
towards CuX (X = Cl, NO , ClO , BF , 1/2SiF ). The first known examples of
3
4
4
6
I
I
joint Cu (Cl,ClO ) and Cu (Cl,BF ) π-complexes
4
4
A. А. FEDORCHUK†, V. V. KINZHYBALO‡, YU. I. SLYVKA†, E. A.GORESHNIK§, T. J. BEDNARCHUK‡,
T. LIS¶ and M. G. MYS’KIV*†
†
‡
§
Department of Inorganic Chemistry, Kyryla i Mefodiya 6, 79005 Lviv, Ukraine
Institute of Low Temperature and Structure Research, Okólna 2, 50-422 Wrocław, Poland
Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39,
SI-1000 Ljubljana, Slovenia
Faсulty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383 Wrocław, Poland
¶
By means of alternating current-electrochemical synthesis starting from a mixture of 2-imino-3-
prop-2-en-1-yl)-1,3-thiazolidin-4-one (3-allylpseudothiohydantoin, napt) and 2-allylamino-1,3-
thiazol-4(5H)-one (allylaminopseudothiohydantoin, aapt) hydrochlorides and corresponding
copper(II) salts five new π-complexes, [Cu(napt)Cl] (1), [Cu (aapt) Cl]NO (2),
Cu (aapt) Cl]BF (3), [Cu (aapt) Cl]ClO (4) and [Cu (aapt) Cl] SiF ·2H O (5), were obtained
(
2
2
3
[
2
2
4
2
2
4
2
2
2
6
2
and studied by X-ray single crystal diffraction and IR-spectroscopy. Napt and aapt molecules are
+
selectively coordinated to Cu depending on the anion type. In crystals of 1 and 5, the organic
ligands are attached to the metal in a chelating N,(C=C)-bidentate mode. The aapt molecule in
2
-4 acts as a tridentate chelating ligand, being coordinated to the copper(I) ion through the
heterocyclic N atom, carbonyl O atom and C=C-bond of allyl group, forming an original cationic
+
–
[
2 2
Cu (aapt) Cl] fragment with both a bridging Cl ion and O atom of the C=O group. In the
2
–
presence of the doubly charged SiF6 anion, Cu(I) in 5 prefers to be bonded with two bridging
+
Cl ions, rather than the C=O group, causing [Cu (aapt) Cl] units to associate into the infinite
2
2
–
–
4
cationic chains. Crystals of 3 and 4 are the first known examples of the simultaneous BF /Cl or
–
4
–
ClO /Cl participation in copper(I) π-complex formation.
*Corresponding author. Email: myskiv@lnu.edu.ua
1

Keywords: Copper(I); π-Complex; Pseudothiohydantoin; Heteroanionic; Crystal structure
. Introduction
1
Pseudothiohydantoin (2-amino-1,3-thiazol-4(5H)-one) based compounds are known in medicine
as anticancer, antibacterial, anti-inflammatory or antifungal drugs [1-5]. They also could be used
as inhibitors of exonuclease activity [6]. The presence of several potential coordination centers in
these molecules can make them an important tool in crystal engineering. A modification of the
pseudothiohydantoin ring (possessing, according to HSAB theory [7], borderline basicity) by an
allyl group would also significantly extend its unusual coordination behavior regarding Cu(I) (as
“soft acid”). The ability of allyl derivatives of some heterocyclic compounds to promote
formation of copper(I) compounds with earlier unknown or unusual inorganic fragments was
previously discovered [8, 9]. Only two metal-olefin π-compounds with pseudothiohydantoin
derivatives were known in literature, in which the allyl group of the ligand is attached to the
metal center, not directly to the pseudothiohydantoin ring, but through the oxygen in the
p-phenolic substituents [7, 10]. Despite the huge advances in synthesis and possible application
of pseudothiohydantoin derivatives, the data concerning their use as ligands in organometallic
chemistry is still quite limited; only 11 (2 of them are π-compounds) corresponding entries have
been found in the Cambridge Crystallographic Database [11]. In order to examine the
coordinating behavior of N-allyl derivatives of pseudothiohydantoin regarding to Cu(I) from
viewpoint of crystal engineering, we report here the results of synthesis and structure
characterization of the five π-complexes, [Cu(napt)Cl] (1), [Cu (aapt) Cl]NO (2),
2
2
3
[
Cu (aapt) Cl]BF (3), [Cu (aapt) Cl]ClO (4) and [Cu (aapt) Cl] SiF ·2H O (5), with 2-imino-
2
2
4
2
2
4
2
2
2
6
2
3
1
-(prop-2-en-1-yl)-1,3-thiazolidin-4-one (3-allylpseudothiohydantoin, napt) and 2-allylamino-
,3-thiazol-4(5H)-one (allylaminopseudothiohydantoin, aapt), emphasizing the role of inorganic
anion in complexation of the metal center with organic ligands, enabling up-to-date unknown
I
I
mixed-anion Cu (Cl,ClO ) and Cu (Cl,BF ) π-complex compounds formation.
4
4
2
2
. Experimental
.1. Materials and instrumentation
Unless otherwise mentioned, all chemicals were obtained from a commercial source (Sigma
Aldrich) and used without purification. The infrared (IR) spectrum of 5 was recorded between
2

KBr plates on the Bruker IFS-88 spectrometer and IR spectra of the
allylaminopseudothiohydantoin hydrochlorides mixture was recorded in KBr pellets on a FT-IR
-1
Spectrum BX-II (Perkin Elmer) from 4000-400 cm . The Hirshfeld surface of the molecules in 1
and Fingerprint plots were produced by CrystalExplorer software [12, 13].
2
.2. Preparation of N-allylthiourea
A solution of 20.0 mL (0.206 mol) allylisothiocyanate in 20 mL of ethanol was slowly added
through a backflow condenser to an efficiently cooled by running water 23.10 mL solution of
concentrated aqueous ammonia (0.309 mol) in 10 mL of ethanol [14]. After the end of the
exothermal reaction, the solution was stirred for 1.5 h. After that ethanol was evaporated from
the solution to give 22.50 g (0.194 mol) of N-allylthiourea (yield 94.2%), m.p. 71 °C.
2
.3. Preparation of N-allylpseudothiohydantoin hydrochloride
N-allylpseudothiohydantoin hydrochloride was obtained by refluxing, on a glycerin bath, a
mixture of ethyl chloroacetate 5.85 g (0.048 mol) [15] and allylthiourea 4.87 g (0.042 mol) in
5
0 mL of benzene for 2 h. After that, the reaction mixture was cooled to room temperature and
the white precipitate was removed by filtration to give 7.01 g (0.036 mol, yield 96.7%). The final
product consists of the mixture of two isomers – 2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-
one and 2-(prop-2-en-1-ylamino)-1,3-thiazol-4(5H)-one hydrochlorides with molar ratio about
6
5 to 35 percent of a product with mp 145 °C (scheme 1). This mixture was further used for
complex preparation without additional isomer separation.
1
NMR Н (400 MHz, DMSO-d ), δ, ppm: 2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-
6
one (napt), 10.07 (s, 1H), 9.39 (s, 1H), 5.81-5.71 (m, 1H), 5.34 (d, J = 16.4, 1H), 5.19 (d, J =
1
0.0, 1H), 4.47 (d, J = 3.8, 2H), 4.25 (s, 2H); 2-(Prop-2-en-1-ylamino)-1,3-thiazol-4(5H)-one
(aapt), 9.66 (s, 1H), 7.53-7.27 (m, 1H), 5.89-5.79 (m, 1H), 5.21 (d, J = 18.6, 1H), 5.13 (d, J =
1
0.0, 1H), 4.05 (d, J = 4.3, 2H), 3.86 (s, 2H).
-1
IR (KBr, cm ) for napt and aapt mixture: 3492 (w), 2992 (w), 2958 (w), 2794 (vs),
700 (vw), 2362 (w), 2338 (vw), 1884 (vw), 1752 (vs), 1662 (s), 1578 (s), 1550 (m), 1504 (w),
430 (s), 1384 (w), 1354 (w), 1362 (s), 1290 (m), 1260 (vw), 1224 (s), 1184 (s), 1156 (s),
122 (vw), 1096 (vw), 1032 (w), 994 (m), 964 (m), 942 (s), 904 (w), 892 (m), 844 (m), 830 (m),
2
1
1
3

7
4
92 (m), 764 (s), 698 (w), 668 (vw), 602 (m), 574 (s), 546 (m), 520 (m), 480 (s), 456 (m),
08 (vw).
Scheme 1. Preparation of allylpseudothiohydantoin hydrochlorides.
2
.4. Preparation of complexes
Crystals of π-complexes 1-5 were obtained by alternating current-electrochemical synthesis [16]
starting from the mixture of 2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-one (napt) and 2-(prop-
2
-en-1-ylamino)-1,3-thiazol-4(5H)-one hydrochlorides (aapt) and corresponding Cu(II) salt in an
appropriate solvent.
2
.4.1. Preparation of [Cu(napt)Cl] (1). In 3 mL of acetonitrile solution of
N-allylpseudothiohydantoin hydrochloride mixture (0.45 mmol, 0.087 g) CuCl ·2H O (0.086 g,
2
2
0
3
.50 mmol) was dissolved with stirring. The prepared green solution was placed into a small
.5 mL test-tube and then copper-wire electrodes in cork were inserted. Few good quality yellow
crystals of (μ -(2-imino-3-(prop-2-en-1-yl)-1,3-thiazolidin-4-one))-chloro-copper(I) (1)
2
acceptable for X-ray crystal structure analysis were obtained on copper wire electrodes after
applying alternating current tension (0.45 V) for 75 h and cooling of reactor to -3 °C during
1
2 days.
2
.4.2. Preparation of [Cu (aapt) Cl]NO (2). In 3 mL of propylene carbonate solution of
2
2
3
N-allylpseudothiohydantoin hydrochloride (0.45 mmol, 0.087 g) Cu(NO
3
)
2
2
·3H O (0.35 mmol,
0
3
.085 g,) was dissolved with stirring. The prepared green solution was placed into a small
.5 mL test-tube and then copper-wire electrodes in cork were inserted. A miserable amount of
4

good quality yellow crystals of (μ-chloro)-bis(μ-(2-(prop-2-en-1-ylamino)-1,3-thiazol-4(5H)-
one))-dicopper(I) nitrate (2) acceptable for X-ray crystal structure analysis were obtained on
copper wire electrodes after applying alternating current tension (0.7 V) for 120 h and cooling of
reactor to -3 °C during 8 days.
2
.4.3. Preparation of [Cu (aapt) Cl]BF (3). In 3 mL of ethanol solution of
2 2 4
N-allylpseudothiohydantoin hydrochloride (0.45 mmol, 0.087 g) Cu(BF ) ·6H O (0.25 mmol,
4
2
2
0
.087 g) was dissolved with stirring. The prepared green solution was placed into a small 3.5 mL
test-tube and then copper-wire electrodes in cork were inserted. A small amount of good quality
yellow crystals of (μ-chloro)-bis(μ-(2-(prop-2-en-1-ylamino)-1,3-thiazol-4(5H)-one))-
dicopper(I) tetrafluoroborate (3) acceptable for X-ray crystal structure analysis were obtained on
copper wires after applying alternating current tension (0.6 V) for 100 h.
2
.4.4. Preparation of [Cu (aapt) Cl]ClO (4). In 3 mL of ethanol – propylene carbonate (1 : 1)
2 2 4
solution of N-allylpseudothiohydantoin hydrochloride (0.45 mmol, 0.087 g) Cu(ClO
4 2 2
) ·6H O
(0.25 mmol, 0.093 g) was dissolved with stirring. The prepared green solution was placed into a
small 3.5 mL test-tube and then copper-wire electrodes in cork were inserted. Few good quality
yellow crystals of (μ-chloro)-bis(μ-(2-(prop-2-en-1-ylamino)-1,3-thiazol-4(5H)-one))-
dicopper(I) perchlorate (4) acceptable for X-ray crystal structure analysis were obtained on
copper wires after applying alternating current tension (0.6 V) for 100 h.
2
.4.5. Preparation of [Cu (aapt) Cl] SiF ·2H O (5). In 3 mL of propylene carbonate solution
2 2 2 6 2
6 2
of N-allylpseudothiohydantoin hydrochloride (0.45 mmol, 0.087 g) CuSiF ·4H O (0.35 mmol,
0
.097 g) was added. Alternating current electrochemical reduction (0.8 V, 50 Hz) was acting on
received mixture for 3 weeks. Suitable for X-ray study crystals of (μ-dichloro)-bis(μ-(2-(prop-2-
en-1-ylamino)-1,3-thiazol-4(5H)-one))-dicopper(I) hexafluorosilicate–water (1/2) (5), formed on
the copper wires after holding of the reactor for additional 3 weeks without applying of ac at
-1
-
3 °C. Yield: about 35%. IR (KBr, cm ): 3467 (vs), 3226 (s), 2974 (s), 2924 (s), 2851 (m),
2
1
9
362 (w), 2337 (w), 1781 (m), 1705 (m), 1588 (s), 1512 (m), 1457 (m), 1431 (m), 1360 (m),
326 (m), 1286 (m), 1253 (m), 1205 (m), 1122 (w), 1071 (w), 1053 (w), 991 (w), 966 (vw),
20 (w), 898 (w), 839 (w), 742 (vs), 539 (m), 482 (vs), 399 (vw).
5

2
.5. X–ray crystal structure determination
Diffraction data for 1 were collected on an Agilent Gemini A four-circle diffractometer with
Atlas CCD detector. Diffraction data for 2-4 were collected on an Agilent Xcalibur four-circle
diffractometer with Atlas CCD detector. Diffraction data for 5 were collected on Kuma
KM4CCD diffractometer. The collected data for 1-5 were processed with CrysAlis Pro program
[17]. The structures were solved by direct methods using SHELXT and refined by least squares
2
2
method on F by SHELXL with the following graphical user interfaces of OLEX [18, 19].
Atomic displacements for non-hydrogen atoms were refined using an anisotropic model.
Positions of non-disordered imine and water hydrogens, involved in hydrogen bonding, were
refined with fixed N–H (0.88 Å) or O–H (0.85 Å) (using DFIX instruction) and with U (H) =
iso
1
.2 U (N) and U (H) = 1.5 U (O). The other hydrogens were placed in ideal positions and
eq
iso
eq
refined as riding atoms with relative isotropic displacement parameters.
The figures were prepared using DIAMOND 3.1 software [20]. Crystal parameters, data
collection and the refinement are summarized in table 1.
3
. Results and discussion
A suitable technique to obtain N-allylpseudothiohydantoins is a reaction between ethyl
chloroacetate and N-allylthiourea. Resulting product is the mixture of two isomers – 2-imino-3-
(prop-2-en-1-yl)-1,3-thiazolidin-4-one (napt) and 2-(prop-2-en-1-ylamino)-1,3-thiazol-4(5H)-one
(aapt) hydrochlorides with molar ratio about 65 : 35 percent from NMR data. This mixture was
used for further synthesis of coordination compounds of copper(I) starting from Cu(II) salts such
as CuCl ·2H O, Cu(NO ·3H O, Cu(BF ·6H O, Cu(ClO ·6H O and CuSiF ·4H
O. Under ac
electrochemical conditions, due to the Cu + Cu ↔ 2Cu reaction, [Cu(napt)Cl] (1),
2
2
)
3 2
2
4
)
2
2
4
)
2
2
6
2
2
+
0
+
[Cu
2
(aapt)
2
Cl]NO
3
(2), [Cu
2
(aapt)
2
Cl]BF
4
2 2 4
(3), [Cu (aapt) Cl]ClO (4) and
[
Cu (aapt) Cl] SiF ·2H O (5) were obtained; high quality crystals of 1-4, suitable for single-
2
2
2
6
2
crystal X-ray analysis, were isolated, however, in small quantities.
In π-complex 1, the Cu(I) ion has a distorted trigonal planar environment which includes
the imino N atom, C=C bond of the allyl group (considering C=C bond as one coordination
center) and one terminal Cl ion (figure 1, table 2). Thus, the napt molecule plays the role of a
bidentate chelating ligand, forming a seven-membered {C N Cu} ring. Because of high ability of
4
2
6

Cu(I) and Cl ions to form a polymeric structure through covalent bonding, the formation of
isolated CuCl units in the structure of Cu(I) π-complexes with allyl derivatives of heterocycles is
rather rare and was previously found only in a few π-compounds ([Cu(N-allyl-2-
iminobenzothiazole)Cl] π-complex – for example) [21, 22]. The nearest Cl ion of the
+
neighboring [Cu(napt)Cl] unit is displaced from the Cu by 4.651(2) Å; thus, the above
fragments are packed in the structure in such a way that endocyclic S atom of nearest napt
molecule forms a weak contact with Cu(I), enabling dimerization of [Cu(napt)Cl] units into a
ii
{[Cu(napt)Cl]}
2
fragment (figure 2). The Cu1-S1 distance of 3.034(2) Å is shorter than the sum
of van der Waals radii of Cu and S (3.20 Å reported by Bondi [23, 24] and significantly shorter
than the corresponding sum, according to Batsanov and Alvarez [25, 26]. Thus, taking into
account a weakly coordinated S atom (at the apical position), the environment of Cu(I) in 1 may
be considered as trigonal pyramidal (the displacement of the Cu ion from the average plane of
2
equatorial ligands is equal to 0.134(1) Å). {[Cu(napt)Cl]} dimers are connected by N-H…O and
C-H…Cl hydrogen bonds into a double H-bonded chain (figure 2, table 3).
The N-allyl group of napt in 1 adopts an anticlinal conformation (-144.8(3)º) relative to
the C6–C7 bond. Both C2–N3 (1.389(3) Å) and C4–N3 (1.381(4)) distance values in the
pseudothiohydantoin ring are practically the same and indicate the noticeable contribution of the
π-component of the bonds due to the electron density delocalization between the C=O and NH
groups and the endocyclic N atom.
To analyze intermolecular interactions, the Hirshfeld surface was built for [Cu(napt)Cl]
fragment in 1. The most prominent N-H…O and C-H…Cl interactions between the moieties in 1
can be seen in the Hirshfeld surface plot as the red areas (figure 3). Fingerprint plots were
produced to show the intermolecular surface bond distances with the regions highlighted for
H….O, H….Cl and Cu….S interactions. The contribution to the surface area from H…H
contacts is 32.5%.
In contrast to napt in 1, isomeric pseudothiohydantoin aapt molecule in the crystals of 2-4
acts as a tridentate ligand. The aapt moiety is attached to the same metal center in a chelating
mode by the olefinic C=C bond of the allylamino group and heterocyclic N atom, forming a
seven-membered {C N Cu} metallocycle (figure 4, table 4). One bridging Cl ion completes the
4
2
coordination environment of both crystallographically independent Cu(I) ions, forming an
+
original cationic [Cu (aapt) Cl] unit with {Cu(L)Cl} fragments topologically related to 1.
2
2
7

+
Formation of the [Cu (aapt) Cl] cation with the copper(I) ion attached to the aapt endocyclic N
2
2
atom allows the ligand carbonyl O atom to act as a weakly coordinated bridging center. This O
atom completes the neighboring metal surroundings to trigonal-pyramidal (chloride ion, ring
nitrogen atom and C=C bond of allyl group are at the basal positions). The geometrically forced
significant difference in Cu2A-O11 (2.899(3) Å) and Cu1-O21 (2.523(2) Å) bond lengths in 2
causes the disordering of Cu2 position over two sites with an occupancy ratio of 0.642(4) :
0
.358(4), which allows the O11 atom to be displaced from Cu2B only by 2.285(3) Å. In contrast
-
-
to 2, isotypic 3 and 4 structures with pseudospherical BF
disordering character: the Cu2 position is split over two sites with occupancy ratios of 0.957(4) :
.043(4) for 3 and 0.952(4) : 0.048(4) for 4; Cu2A-O11 and Cu1-O21 distance values are
4 4
and ClO anions show reverse
0
comparable: 2.344(2) Å and 2.387(2) in 3 and 2.356(2) Å and 2.392(2) in 4. Thus, the Cu2A part
with the lower s.o.f. (in 3 and 4) possesses a trigonal planar environment (as well as the Cu2B
part with higher s.o.f. in 2) being coordinated through the olefinic C=C bond of allyl group, ring
N atom and chloride ion. The corresponding Cu–O distance (2.899(3) in 2, 2.962(12) in 3 and
2
.938(10) Å in 4) borders with the sum of van der Waals radii of Cu and O (2.92 Å) as reported
by Bondi. These Cu–O distances significantly exceed the nominal limit of Cu–O bond distances
2.45 Å), calculated for apically bonded O donors in the structures of copper(I) π-complexes with
(
allyl derivatives of heterocycles [8]. The disordering of allylamino groups in the structures 2-4
seems to be caused by a significant flexibility of this part of the ligand moiety.
Despite some differences in the anion’s geometry in structures 2, 3 and 4, a similar
pattern of hydrogen bonds is observed (table 3, figure 5). A hydrogen atom of the aapt amino
group is involved in N–H…X (X = O or F) bonding with anions forming the infinite H-connected
chains, which in turn are bound into a supramolecular framework by weak C–H…X contacts.
n+
2-
The structure of 5 is built of cationic {Cu (aapt) Cl} chains and SiF6 anions,
2
2
n
interconnected through water molecules. The above cation may be treated as polymerized
+
[
Cu (aapt) Cl] tectons, in which pseudothiohydantoin molecules tend to be coplanar, preventing
2
2
carbonyl O atom coordination to the Cu(I) (figure 6, table 5). Thus, in contrast to 2-4, the aapt
molecule in π-complex 5 acts as only a bidentate chelating ligand, being attached to the Cu(I)
through the olefinic C=C bond of allyl group and the N13 atom. The coordination environment
of the metal includes two ligand donor centers and two bridging Cl ions, which form a cationic
n+
{
Cu (aapt) Cl} chain fragment with four-coordinated Cl ions (figure 7). The N-allyl group of
2
2
n
8

aapt in 5 possesses an anticlinal conformation (142.7(4)º) with respect to the C16-C17 bond.
Distances C12–N12 (1.313(5) Å) and C14–N13 (1.387(5) Å) in the pseudothiohydantoin ring
indicate a significant contribution of the π-component of the bonds due to the electron density
delocalization between the C=O and NH groups and the endocyclic N atom.
2
-
Water molecules in 5 play a role of the specific H-bonded connectors between SiF
6
2
n-
anions, involving them into O–H…F hydrogen bonding and producing {(H O) SiF } chains
2
2
6 n
(figure 6). The last ones are bonded through N–H…F and C–H…F into framework with four
n+
cationic {Cu
2
(aapt)
2
Cl}
n
chains.
2
-
Due to the O−H···F and N−H···F hydrogen bonds (2.10-2.32 Å) of the SiF6 anion, the
cationic chains are connected in a 3D - hydrogen bound framework (table 3).
+
Since similar [Cu (aapt) Cl] fragments were observed in 2-4, it can be assumed that the
2
2
-
-
-
anion (BF , ClO , NO ) does not cause a significant influence over the formation of this unit. A
4
4
3
+
possible mechanism of 2-4 formation is shown in scheme 2. Formation of Cu (which according
to HSAB theory acts as “soft” acid) under the ac electrochemical conditions causes the
deprotonation of the initial allylpseudothiohydantoin hydrochloride to the neutral molecule due
to the Cu–N bond formation. This is confirmed by the fact that the five-membered heterocyclic
ring allows a good π-electron conjugation with the nitrogen atom of the amino group, enabling
the proton transfer and charge transfer process during heavy-metal complex formation [27, 28].
Therefore, the neutral aapt molecule may easily by coordinated to the metal in a chelating mode,
–
using the available endocyclic N atom and allylic C=C bond. The presence of Cl ion in the
solution is a crucial factor for coordination Cu–Cl bonding, which produces a {Cu(aapt)Cl}
tectone – a basic building unit for structure construction. So, in the structures of 2-4, the
{
Cu(aapt)Cl} unit is interconnected (through bridging Cl and O donor centers) with another
+
+
organometallic {Cu(aapt)} fragment into the [Cu (aapt) Cl] cation. However, in the presence
2
2
2
-
of the doubly charged SiF
6
anion, the ligand O atoms prefer to participate in H-bond formation,
+
allowing a polymerization of the above [Cu (aapt) Cl] fragments into infinite chains.
2
2
9

+
Scheme 2. Probable mechanism of [Cu
2
(aapt)
2
Cl] fragment formation.
n+
Scheme 3. Probable mechanism of [Cu (aapt) Cl] fragment formation.
2
2
n
4
. Conclusion
The synthesis and structure characterization of the five new π-compounds, [Cu(napt)Cl] (1),
[
Cu (aapt) Cl]NO (2), [Cu (aapt) Cl]BF (3), [Cu (aapt) Cl]ClO (4) and
2
2
3
2
2
4
2
2
4
[
Cu (aapt) Cl] SiF ·2H O (5), with 3-allylpseudothiohydantoin (napt) and
2
2
2
6
2
allylaminopseudothiohydantoin (aapt) have been performed. Observed complexation of Cu(I)
+
towards napt and aapt depends largely on the anion type. The formation of Cu (which according
to HSAB theory acts as “soft” acid) under the ac-electrochemical conditions causes a
deprotonation of the initial allylpseudothiohydantoin hydrohlorides to the neutral molecule,
+
which in turn, due to the Cu–N bond formation, produces [Cu (aapt) Cl] units. Due to the
2
2
–
–
4
unusual structure of the last fragment, the first known examples of the simultaneous BF /Cl or
10

–
4
–
ClO /Cl participation in copper(I) π-complex construction were observed. In the case of doubly
2
-
+
n+
charged SiF6 anion, [Cu (aapt) Cl] cations are combined into infinite {Cu (aapt) Cl} chains.
2
2
2
2
n
Supplementary material
CCDC 1514805, 1514795, 1514922, 1514923 and 1514797 contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033).
References
[1]
[2]
[3]
[4]
[5]
[6]
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Filimonov, V.V. Poroikov, I. Alam, A.K. Saxena. J. Med. Chem., 51, 1601 (2008).
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van Rossum-Fikkert, A. Kertokalio, F. Romoli, A. Ismail, E. Ismalaj, E. Petricci, M.J.
Neale, R.G. Bristow, J.-Y. Masson, C. Wyman, P.A. Jeggo, J.A. Tainer. Mol. Cell, 53, 7
(2014).
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[8]
[9]
R.G. Pearson. J. Am. Chem. Soc., 85, 3533 (1963).
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Organomet. Chem., 810, 1 (2016).
[
10] E. Goreshnik, V. Karpyak, M. Mys'kiv. Acta Crystallogr., Sect. C: Cryst. Struct.
Commun., 61, 390 (2005).
[11] F.H. Allen. Acta Cryst., B58, 380 (2002).
11

[12] CrystalExplorer Software, S.K. Wolff, D.J. Grimwood, J.J. McKinnon, M.J. Turner, D.
Jayatilaka, M.A. Spackman, University of Western Australia (2012).
[13] M.A. Spackman, D. Jayatilaka. CrystEngComm, 11, 19 (2009).
[14] Ya. E. Filinchuk, V.V. Oliinik, T. Glovyak, M.G. Mys'kiv. Russ. J. Coord. Chem., 27,
1
26 (2001).
[
[
[
[
[
15] C.F.H. Allen, J.A. VanAllan. Org. Synth., 27, 71 (1947).
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17] Agilent, CrysAlis PRO, Agilent Technologies, Yarnton, England (2011).
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Cryst., 42, 339 (2009).
[
[
[
[
[
[
[
[
20] Crystal Impact GbR, Bonn, Germany, DIAMOND v3.1 (2004–2005).
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22] J. Pang, G.-X. Wang, R.-G. Xiong. Chin. J. Inorg. Chem., 7, 1227 (2007).
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Struct., 1086, 125 (2015).
12

Table 1. Selected crystal data and structure refinement parameters of 1-5.
№
1
2
3
4
5
CCDC
1514805
1514795
1514922
1514923
1514797
number
Molecular [Cu(C H N
[Cu (C H N OS)
[Cu (C H N OS) [Cu (C H N OS)
[Cu (C H N OS) Cl] S
6
8
2
2
6
8
2
2
2
6
8
2
2
2
6
8
2
2
2
6
8
2
2
2
formula
OS)Cl]
Cl]NO
3
Cl]BF
4
Cl]ClO
4
iF ·2H O
6 2
Formula
weight
255.19
536.95
561.75
574.39
1128.00
-1
(
g·mol )
Crystal
system
Triclinic
Monoclinic
P2 /n
Monoclinic
P2 /n
Monoclinic
P2 /n
Orthorhombic
Space
group
P-1
1
1
1
Ccce
a (Å)
b (Å)
c (Å)
α (º)
7.102(3)
7.279(3)
9.374(3)
70.38(3)
71.54(3)
89.81(3)
430.1(3)
2
11.232(4)
11.895(4)
13.836(4)
90
11.679(4)
11.612(4)
14.498(4)
90
11.597(4)
11.704(4)
14.675(4)
90
28.745(7)
17.444(5)
7.370(3)
90
β (º)
99.61(3)
90
103.27(3)
90
103.69(3)
90
90
γ (º) 3
90
V (Å )
1822.6(10)
4
1913.7(11)
4
1935.3(11)
4
3696(2)
4
Z
-1
μ (mm )
F(000)
3.04
2.75
2.64
2.73
2.76
256
1080
1120
1152
2264
Crystal
0.47 × 0.37 × 0.27 × 0.24 ×
0.47 × 0.17 ×
0.05
0.31 × 0.17 × 0.08 0.44 × 0.10 × 0.10
size (mm) 0.17
0.13
Crystal
color and
shape
Yellow
blocks
Yellow blocks
Yellow plates
Yellow plates
Colorless blocks
Kuma KM4CCD
Diffracto
Agilent
Agilent Xcalibur, Agilent Xcalibur, Agilent Xcalibur,
meter and Gemini A,
Atlas
Atlas
Atlas
Atlas
detector
type
Radiation Mo Kα,
Mo Kα, 0.71073
Mo Kα, 0.71073
Mo Kα, 0.71073
Mo Kα, 0.71073
type,
0.71073
wavelengt
h, λ (Å)
Temperat
150(1)
100(1)
100(1)
100(1)
150(1)
ure, K
θ range
4.5 – 29.4
2.5 – 29.7
2.5 – 29.6
2.5 – 29.4
3.1 – 36.8
for data
collection
(
º)
Index
ranges
–9 ≤ h ≤ 9,
–15 ≤ h ≤ 15,
–16 ≤ k ≤ 16,
–18 ≤ l ≤ 18
–15 ≤ h ≤ 15,
–14 ≤ k ≤ 14,
–19 ≤ l ≤ 18
–16 ≤ h ≤ 14,
–15 ≤ k ≤ 10,
–19 ≤ l ≤ 19
–38 ≤ h ≤ 36,
–26 ≤ k ≤ 22,
–9 ≤ l ≤ 9
–7 ≤ k ≤ 10,
–
11 ≤ l ≤ 12
13

Measured 2910
reflections
46193
4844
21854
4809
9930
4547
13006
2532
Independe 1987
nt
reflections
Observed
1751
112
4045
337
3624
289
3656
289
1905
133
reflns. (I >
2
σ(I))
Refined
parameter
s
R
0.024
0.033
0.029
0.024
0.038
0.038
0.024
0.032
0.074
0.055
int
2
R[F >
2
2
σ(F )]
2
wR(F )
0.081
0.059
1.04
0.082
1.05
0.069
1.02
0.146
1.04
Goodness 1.08
of fit
Δρ /Δρ
1.52
0.35
0.88
0.59
0.80
max
mi
3
n
(e Å )
-0.88
-0.34
-0.51
-0.42
-0.83
14

Table 2. Selected bond distances (Å) and angles (°) in 1.
Cu1–Cl1
Cu1–N2
Cu1–m
2.202(1)
1.991(3)
1.931(3)
1.370(4)
N2–Cu1–Cl1
N2–Cu1–m
Cl1–Cu1–m
C6–C7–C8
113.03(8)
112.8(1)
132.8(1)
122.7(3)
C7–C8
m is a mid-point of C7–C8 double bond.
15

Table 3. Geometry of selected hydrogen bonds in 1 and 3-5.
Atoms involved
D−H···A
Symmetry
Distances (Å)
Angle (°)
D−H···A
D···H
H···A
D···A
1
N2—H2···O1
x, 1+y, z
0.85(2)
0.87(2)
0.86(2)
2.23(2)
2.25(3)
2.28(2)
3.078(3)
2.990(4)
3.031(3)
171(3)
143(3)
145(3)
3
N22—H22···F2
x+1/2, −y+1/2, z+1/2
x−1/2, −y+1/2, z−1/2
4
N22—H22···O2
5
N12—H12···F1
N12—H12···F2
O21—H21···F2
0.86(2)
0.86(2)
0.90(2)
2.10(3)
2.27(3)
2.32(3)
2.821(4)
3.082(6)
3.190(9)
141(4)
156(4)
161(7)
−x+1, −y+1/2, z
−x+1, −y+1/2, z
16

Table 4. Selected bond distances (in Å) in 2-4.
2
3
4
Cu1–Cl1
Cu1–O21
Cu1–N13
2.2459(7)
2.523(2)
1.9765(14)
1.952(2)
1.958(5)
2.1981(8)
2.900(2)
2.0177(15)
1.949(5)
2.3336(14)
2.285(3)
1.9883(16)
1.953(5)
1.370(14)
1.36(3)
Cu1–Cl1
Cu1–O21
Cu1–N13
2.2569(10)
2.387(2)
1.987(2)
1.943(2)
1.938(5)
2.2468(9)
2.344(2)
2.015(2)
1.940(3)
2.226(12)
2.961(12)
1.987(12)
2.001(13)
1.379(7)
1.393(10)
1.361(4)
Cu1–Cl1
Cu1–O21
Cu1–N13
2.2566(9)
2.392(2)
1.989(2)
1.944(4)
1.936(11)
2.2412(9)
2.356(2)
2.012(2)
1.941(3)
2.249(10)
2.938(10)
1.940(10)
2.012(11)
1.368(5)
1.431(14)
1.364(4)
Cu1–m1A
Cu1–m11A
Cu1–m11B
Cu2A–Cl1
Cu2A–O11
Cu2A–N23
Cu2A–m12
Cu2B–Cl1
Cu2B–O11
Cu2B–N23
Cu2B–m12
C17A–C18
C17B–C18
C27–C28
Cu1–m11A
Cu1–m11B
Cu2A–Cl1
Cu2A–O11
Cu2A–N23
Cu2A–m12
Cu2B–Cl1
Cu2B–O11
Cu2B–N23
Cu2B–m12
C17A–C18
C17B–C18
C27–C28
Cu1–m1B
Cu2A– Cl1
Cu2A–O11
Cu2A–N23
Cu2A–m2A
Cu2B–Cl1
Cu2B–O11
Cu2B–N23
Cu2B–m2B
C17A–C18A
C17B–C18B
C27A–C28A
C27B–C28B
1.360(5)
1.382(10)
m1A, m1B, m2A, m2B, m1A, m1B and m2 are mid-points of C17A–C18A, C17B–C18B, C27A–C28A and
C27B–C28B bonds correspondingly in 2; m11A, m11B and m12 are mid-points of C17A–C18, C17B–C18 and
C27–C28 bonds correspondingly in 3 and 4.
17

Table 5. Selected bond lengths (Å) and angles (deg) in 5.
ii
i
Cu1–Cl1
Cu1–Cl1
2.7454(14)
2.2770(11)
1.989(3)
Cl1–Cu1–Cl1
93.93(3)
i
N13—Cu1—Cl1
N13—Cu1—Cl1
N13—Cu1—m
C18–C17–C16
99.46(10)
121.27(10)
112.87(15)
122.3(4)
Cu1–N13
Cu1–m
1.954(4)
C17–C18
1.368(6)
Symmetry codes: (i) 1.5−x, 1−y, z; (ii) 1.5−x, y, 0.5+z; m is a mid-point of
C17–C18 bond.
18

Figure captions
Figure 1. Independent part in 1. Thermal ellipsoids are drawn at 70% probability level.
Figure 2. {[Cu(napt)Cl]}
–y, 1–z; (iii) x, –1+y, z.
2
dimers and H-bonded array in 1. Symmetry codes: (i) x, 1+y, z; (ii) –x,
2
Figure 3. Hirshfeld surface analysis of [Cu(napt)Cl] fragment in 1. Hirshfeld surface is mapped
which highlights both donor and acceptor ability. Fingerprint plots of crystal fragment
with d
norm
resolved into H…O, H…Cl and Cu…S. The full fingerprint appears beneath each decomposed
plot in grey.
Figure 4. Coordination environment of Cu(I) in 2 (a) and 3 (b). Disordered part B of ligand
molecule is omitted for clarity. Thermal ellipsoids are drawn at 70% probability level.
cF li ag r ui tr ye .5. H-bonded chains in 2 (a) and 3 (b). Disordered part with lower s.o.f. is omitted for
Figure 6. Cationic and anionic chains in 5. Symmetry codes: (i) −x+1, −y+1/2, z; (ii) x, 1−y,
0
.5+z; (iii) x, 0.5−y, 1.5−z.
Figure 7. Structural fragment of 5. Symmetry codes: (i) 1.5−x, 1−y, z; (ii) 1.5−x, y, 0.5+z.
19

2
0

2
1

2
2

23

24

2
5

2
6

27