Halogen and chalcogen-bonding interactions in sulphur-rich π-electron acceptors

Article abstract of DOI:10.1039/c8ce02046a

In order to explore the feasibility of generating halogen bonding interactions between sulphur-rich π-electron acceptors, we prepared three bithiazolidinylidene derivatives substituted by iodine atoms, namely 3,3′-bis(iodophenyl)bithiazolidinylidene-2,4,2′,4′-tetrathione (BIP-BTTT). Sulphur and iodine heteroatoms were introduced to the skeleton of the acceptor molecule to induce chalcogen...chalcogen and halogen bonding interactions. Both interactions can be evidenced by X-ray diffraction studies in the synthetic precursors as well as in the acceptors themselves.

Full text of DOI:10.1039/c8ce02046a

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DOI: 10.1039/C8CE02046A
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Halogen and chalcogen-bonding interactions in sulphur-rich -
electron acceptor
Yann Le Gal, Adrien Colas, Frédéric Barrière, Vincent Dorcet, Thierry Roisnel and Dominique
Lorcy*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
In order to explore the feasibility of generating halogen bonding interactions between sulphur-rich -electron acceptors, we
prepared three bithiazolidinylidene derivatives substituted by iodine atoms, namely the 3,3’-bis(iodophenyl)
bithiazolidinylidene-2,4,2′,4′-tetrathione (BIP-BTTT). Sulphur and iodine heteroatoms were introduced on the skeleton of
the acceptor molecule to induce chalcogen···chalcogen and halogen bonding interactions. Both interactions can be
evidenced by X-ray diffraction studies in the synthetic precursors as well as in the acceptors themselves.
www.rsc.org/
n-channel OFET,12 we focused our interest on other interactions
than the chalcogen···chalcogen contacts. For that purpose, we
investigated the synthesis of similar acceptors substituted with
Introduction
The design of molecules for the elaboration of semi-conducting
molecular materials relies essentially on the intrinsic properties
of the molecular precursors. However, the properties of the
materials are also based on the solid state organization and on
the intermolecular interactions between molecules within the
material.1-2 Indeed, weak interactions between molecules will
result into an insulating material with no charge carrier
delocalization. Various types of intermolecular interactions
have been explored such as chalcogen···chalcogen contacts,3
hydrogen bonding,4-5  stacking,6 halogen bonding,7 either
separately or cooperatively.8 In this context, we recently
developed the synthesis of sulphur-rich electron acceptors with
a bithiazolidinylidene-2,4,2′,4′-tetrathione (BTTT) backbone
(Chart 1).9
halogen atoms such as iodine, potentially able to form halogen
bonds (XB) with the chalcogen atoms of the neighbouring
molecules, acting as XB acceptors. Indeed, we recently reported
for example that the exocyclic sulphur atom in thiazoline-2-
thiones can act as an efficient XB acceptor toward organic
iodinated molecules.13 Therefore we investigated the synthesis
of 3,3’-bis(iodophenyl)-BTTT, BIP-BTTT (Chart 1) where the
nitrogen atom of the heterocyles, the thiazoline-2-thione
moieties, are substituted by an ortho, meta or para iodophenyl
moiety. These different substitution patterns led to the analysis
of the influence of the localization of the halogen atom on the
intermolecular interactions. In this study, we report the
syntheses and X-ray structure investigations of the precursors
and the novel electron acceptors BIP-BTTT. Electrostatic surface
potential (ESP) calculations carried out on four of the
Chart 1
I
S
crystallographically characterized compounds provide
a
S
S
S
S
R
R
S
complementary understanding of the organization of the
molecules in the solid state.
S
N
2-iodo
3-iodo
4-iodo
N
N
N
S
S
S
S
I
S
BIP-BTTT
BTTT
Results and Discussion
The strategy we used to synthetize the acceptors BIP-BTTT 4a-c
starting from the 2-, 3- and 4-iodoaniline is outlined in Scheme
1. Addition of triethylamine to a solution of the iodoaniline in
carbon disulphide led to the dithiocarbamate salts 1a-c in good
yields. Alkylation of 1a-c with chloroethanal followed by
cyclization and dehydration in the presence of sulphuric acid
allowed us to isolate the thiazoline-2-thione 2a-c. The next step
consists in the construction of the fused dithiole-2-one rings on
the thiazoline-2-thione 2a-c. Successive addition of LDA and
Several members of this family led to air-stable n-channel
organic field effect transistors (OFET) exhibiting good
performances.10,11 The air stability and the enhanced charge
mobility were ascribed to the presence of S···S intermolecular
interactions.10 As the intermolecular interactions are of high
importance for the charge mobility as well as for the stability of
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226, sulphur to thiazoline-2-thione 2a-c followed by the addition of
F-35000 Rennes, France. Email : Dominique.lorcy@univ-rennes1.fr
† Electronic Supplementary Information (ESI) available: crystallographic data in CIF
format. CCDC 1872721-1872724. See DOI: 10.1039/x0xx00000x
triphosgene afforded the dithiol-2-one 3a-c. We previously
demonstrated that a thermal treatment of such protected
dithiolene ligands within a dithiol-2-one cycle is an efficient
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strategy for the synthesis of the acceptor skeleton.9 The Crystals of sufficient quality for an X-ray diffractioVnieswtAurdticylewOnelirnee
acceptors BIP-BTTT 4a-c were therefore synthetized by simply obtained by slow concentration of a CHD2COl2I: 1s0o.1lu0t3i9o/nC8oCfE022b0,436Aa
heating the bicyclic structures 3a-c into refluxing toluene. These and 3c as well as from a CHCl3 solution of the acceptor 4c. The
acceptors 4a-c were obtained as deep purple compounds molecular structure of 2b is reported in Figure 1. The thiazole
poorly soluble in common organic solvents, the less soluble one core is planar, while the phenyl ring is located in a plane forming
being para-substituted 4a.
a dihedral angle of 63.4(5)° with the thiazoline-2-thione core.
The sulphur atoms can behave as a Lewis base and form
intermolecular halogen bonding with the iodine atom of a
neighbouring molecule.13,15 However in 2b, only a short
distance between the hydrogen atom of the thiazoline ring and
the sulphur atom of the thione (2.788 (4) Å), assigned to an
hydrogen bond (HB), was observed.
I
S
I
i
N
ii
NH2
N
H
S
S
S
I
a
b
c
4-IC6H4
3-IC6H4
2-IC6H4
HNEt3
2a-c
1a-c
I
I
S
S
S
N
S
S
S
N
iii
iv
S
O
N
S
S
S
I
3a-c
4a-c
BIP-BTTT
Scheme 1. Synthetic path to BIP-BTTT derivatives 4a-c, 26-36% yield
from 2a-c. Reactants and conditions: i) CS2, NEt3; ii) ClCH2CHO, H2SO4;
iii) LDA, S8, (Cl3CO)2CO; iv) toluene, .
Fig. 1 View of the C-H···S= and C-I···S= interactions on the bc
plane for 2b.
Table 2 Revelant interatomic distances (Å) and angles (°) for the
halogen bonding, hydrogen bonding and chalcogen
interactions. The van der Waals contact distances amount to
S···I: 3.78 Å, S···S: 3.60 Å, S···O: 3.32 Å, O···I: 3.50 Å, H···S: 3.00
Å.
Electrochemical investigations carried out by cyclic
voltammetry allowed us to determine the redox potentials of
these derivatives. They were performed in DMSO for the three
acceptors 4a-c and in CH2Cl2 for 4b-c ; 4a being not soluble
enough in dichloromethane. The redox potentials are collected
in Table 1 together with those of DEBTTT (R = Et, Chart 1) for
comparison. Two reversible monoelectronic reduction waves
are observed for these three acceptors, either in DMSO or in
CH2Cl2, attributed to the successive reduction of the acceptor
into the radical anion and the dianion. Compared to DEBTTT, in
both solvents the redox potentials of the acceptors 4a-c are
slightly shifted towards more anodic potentials indicating a
weak effect of the iodophenyl substituent on the overall
accepting ability of these molecules. 4a-c and DEBTTT exhibit
slightly lower electron accepting ability than TCNQ (E1 = 0.18 V
and E2 = -0.37 V vs SCE).14
Distances (Å)
Angles (°)
2b S2···H 2.788(4)
C9-H9···S2 175.9(3) H9··· S2=C10 98.4(2)
3a O1···I1 3.271(12) C8-I1···O1 161.4 (4) I1···O1=C4 109.2(8)
S1···S3 3.329(4)
3c O12···I1 3.252 (5) C1-I1···O12 154.6 (9) I1···O12=C11 111.1(2)
S2···S4 3.416(1)
4c S15···I2 3.763(7)
C21-I2···S15 155.5(5) I2 ··S15=C64 118.7(6)
S16···I1 3.390(11) C1-I1···S16 158.2(3) I1··· S16=C62 119.4(6)
Table 1 Redox potentials E1/2 V vs SCE, in CH2Cl2 and DMSO for
DEBTTT and 4a-c
S5···I11 3.533(4)
S3···S6 3.177(7)
C51-I11···S5 156.3(3) C12=S5···I11 124.9(5)
CH2Cl2
DMSO
1
2
1
2
Acceptors E1/2
E1/2
E1/2
E1/2
The molecular structures of dithiol-2-ones 3a and 3c are
reported in Figure 2. For both derivatives the dithiol-2-one and
the fused thiazoline core are coplanar and form with the plane
of the aromatic substituent a dihedral angle of 50.5(2)° for 3a
and 100.2(3)° for 3c. Short I···O contacts are observed between
two neighbouring molecules of 3.271 Å for 3a and 3.252 Å for
DEBTTT
4a
-0.05 -0.44
0.06 -0.41
0.09 -0.33
0.1 -0.34
0.05 -0.37
4b
4c
-0.01 -0.43
-0.04 -0.48
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3c, corresponding to a reduction ratio of 93.4% and 92.9% pointing in the same direction above the plane of Vthiewe Aarcticclee pOtnolinre.
respectively, relative to the van der Waals contact distance The plane of the phenyl rings is almostDpOeI:r1p0e.1n0d39ic/Cu8laCrE0to204th6Ae
(3.50 Å), indicating
a sizeable XB interaction between plane of the acceptor. The molecules are associated through
neighbouring molecules (Figure 2a and 2b).16 The C-I···O angles, I···S=C XB interaction networks between I1···S16 3.390(11) Å and
at 161.4° and 154.6°, are here closer to linearity and consistent I11···S5 3.533(11) Å for the most significant short distances
with an XB interaction. In addition, for both structures, corresponding respectively to 89.7% and 93.4% of the van der
chalcogen···chalcogen contacts are also observed between Waals distances. Besides these intramolecular contacts, short
neigboring molecules, at a distance shorter than the sum of the S···S intermolecular contacts are also observed between
van der Waals radii, either of the two sulphur centers (3.60 Å) neighbouring molecules, S3···S6 3.177(7) Å lower than the van
or the sulphur and the oxygen atoms (3.32 Å). The shortest der Waals radius of sulphur, corresponding to a reduction ratio
sulphur···sulphur contacts measured for 3a and 3c are reported of 88.2%. Nevertheless, due to steric hindrance generated by
in Figures 2c and 2d. The crystal structure of 3a reveals S···O and the iodophenyl rings, these S···S contacts within these acceptors
S···S distances of 3.274(12) Å and 3.329(5) Å respectively, the are less numerous than those observed with DEBTTT where
latter corresponds to 93% of the van der Waals distance and is extensive three-dimensional S···S interactions were noticed.9
due to strong non covalent bonding between two molecules.
Comparatively the S···S distances within 3c (the shortest being
3.416(1) Å) are longer than in 3a. This is ascribed to a steric
effect in the solid state of the ortho position of the iodine atom
on the phenyl ring.
Fig. 3 Molecular structure of the acceptor 4c showing the
intramolecular S···S contacts (top), the shortest intermolecular
contacts (bottom left) and the XB bonds between two
Fig. 2 View of the XB interactions, O···I contacts shorter than the
sum of the van der Waals radii in dark grey dotted lines in 3a (a)
and 3c (b). View of the chalcogen interactions, S···S contacts
neighbouring molecules (bottom right).
shorter than the sum of the van der Waals radii in dark grey
dotted lines in 3a (c) and 3c (d).
Electrostatic surface potential calculations have been
performed on the optimized geometry of the four molecules
that have been crystallographically characterized, namely 2b,
3a, 3c and 4c. These calculations were carried out in order to
estimate the halogen bond donor abilities of the iodophenyl
Among the three electron acceptors, only the ortho substituted
derivative 4c could be analysed by X-ray diffraction study. The
substituent within these different structures and to rationalize
molecular structure of this derivative is presented in Figure 3. It
crystallizes in the triclinic system, space group P-1, with two
crystallographically independent molecules in the unit cell in
general position. This acceptor exhibits a planar skeleton and a
trans configuration of the two thiazoline-2-thione rings with
short intramolecular S···S contacts between the S atom of a
thiocarbonyl group and the S atom of the thiazole ring (2.94
Å/2.91 Å). These short S···S contacts are in the same range as
those observed for different acceptors belonging to the same
family.9
the interactions taking place in the crystal.9 As shown in Figure
4, for 2b the maximum calculated positive electrostatic surface
potential (ESP) is found at the hydrogen atoms located on the
thiazole ring (+31.74 kcal.mol-1) compared to only +23.89
kcal.mol-1 at the iodine atom. The most negative calculated ESP
is -29.09 kcal.mol-1 and located on the thione’s sulphur atom
(C=S). This calculated charge repartition is in good agreement
with the organization of the molecule 2b in the solid state
where predominant hydrogen bonding interactions were
observed between the hydogen atom on the thiazoline ring and
the sulphur atom of the thione, while no specific halogen
bonding interaction involving the iodine atom was detected.
Interestingly, the ortho-iodophenyl substituents on the
nitrogen atoms have a similar orientation with the iodine
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Fig. 5 Molecular electrostatic potential surface mVaiepwpAerdticlae tOntlhinee
0.001 e-.au-3 isodensity surface for 4a and 4b. The colour scales
DOI: 10.1039/C8CE02046A
range from -29 kcal.mol-1 (red) to +35 kcal.mol-1 (blue).
We also performed some ESP calculations for the two other
acceptors that have not been crystallographically characterized
in order to analyse the influence of the localization of the
halogen atom. For both acceptors, 4a and 4b, the most negative
calculated ESP is located on the thione’s sulphur atom (C=S) as
for the acceptor 4c. On the other hand, the highest ESP value
over the whole molecules 4a and 4b is not found at the -hole
like for 4c (Figure 5) but located para to the iodine atom on the
aromatic ring, potentially a less favorable charge distribution for
the growing of crytals in these cases.
Conclusions
In this study we investigated the synthesis of sulphur-rich electron -
acceptors, the bithiazolidinylidenes, substituted by iodophenyl
substituents, which can act as halogen bond donor toward thione
(C=S) or ketone (C=O) groups acting as XB acceptors. Single crystals
of the synthetic intermediates as well as one of the acceptors have
been obtained. For the precursors, when the thione (C=S) and ketone
(C=O) groups are present on the molecule, a halogen bond is formed
between the iodine atom of one molecule and the C=S/C=O moieties
of the neighbouring ones. For the acceptor 4c, in accordance with the
calculated ESP maxima, I···S=C halogen bonds are observed between
neighbouring molecules as well as S···S interactions. Thus we
managed to generate from these BIPBTTT acceptors the coexistence
of two types of intermolecular interactions in the solid state. The
next step will be the design of sulphur-rich electron acceptor
substituted by groups bearing an iodine atom but less bulky than
phenyl in order to increase the strength of the intermolecular
interactions.
Fig. 4 Molecular electrostatic potential surface mapped at the
0.001 e-.au-3 isodensity surface for 2b, 3a, 3c and 4c. The
common colour scale ranges from -29 kcal.mol-1 (red) to +35
kcal.mol-1 (blue).
For the dithiol-2-one 3a and 3c, the most negative calculated
ESP is now located on the oxygen atom of the dithiole rings
(C=O, -19.92 and -25.14 kcal.mol-1 respectively) while the most
positive ESP is on the bicyclic structure (+24.88 and +34.83
kcal.mol-1). The electrostatic surface potential value on the -
hole of the halogen is lower (blue dot on the iodine atom in
Figure 5, +17.67 and +26.89 kcal.mol-1). Despite these slighltly
lower values, the organization of both molecules in the solid
state shows XB interactions (C=O···I) between their iodine atom
and the oxygen atom of a vicinal molecule.
The acceptor 4c is the only example where the highest ESP value
over the whole molecule is found at the -hole of the iodine
atom (+24.48 kcal.mol-1, Figure 5) while for the three other
derivatives, it was either found on an hydrogen atom for 2b or
on the bicycle structure for 3. The most negative calculated ESP
for 4c is found on the sulphur atoms of the thione (-19.96
kcal.mol-1). In accordance with these calculations, the iodine
atom of this acceptor is indeed involved in short XB interactions
with the thione’s sulphur atom in the solid state (Table 2).
Experimental section
All commercial chemicals were used without further purification. The
solvents were purified and dried by standard methods. All the NMR
spectra were obtained in CDCl3 unless indicated otherwise. Chemical
1
shifts are reported in ppm and H NMR spectra were referenced to
residual CHCl3 (7.26 ppm) and 13C NMR spectra were referenced to
CHCl3 (77.2 ppm). The 13C NMR spectra of the acceptors 4a-c could
not be obtained due to their low solubility. Melting points were
measured on a Kofler hot-stage apparatus and are uncorrected. Mass
spectra and Elemental analyses were performed at the Centre
Régional de Mesures Physiques de l'Ouest, Rennes. Cyclic
voltammetry were carried out on a 10-3 M solution in CH2Cl2,
containing 0.1
M
nBu4NPF6 as supporting electrolyte.
Voltammograms were recorded at 0.1 Vs-1 on a platinum electrode
and the potentials were measured versus the Saturated Calomel
Electrode (SCE).
N-iodophenyl-1,3-thiazoline-2-thione 2a-c : To a solution of 4-
iodoaniline, 3-iodoaniline or 2-iodoaniline (12 g, 54.8 mmol) was
added 100 mL of triethylamine and 100 mL of carbon disulphide. The
solution was stirred under argon 24h. The solution was filtered and
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the yellow solid was washed with diethylether. The dithiocarbamate mL) was added and the solution was washed with water (3 x 20 mL)
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salts 1a-c were used without further purification; 1a: yield: 95%, Mp and dried over MgSO4. The concentrated sDoOluI:ti1o0n.10w3a9s/Cp8uCrEif0i2e0d46bAy
1
: 92°C. H NMR (300 MHz) δ 1.30 (t, 9H, 3J=7.3Hz, CH3), 3.17 (q, 6H, chromatography on silica gel using CH2Cl2-petroleum ether as the
3J=7.3Hz, CH2), 7.43 (m, 2H, Ar), 7.53 (m, 2H, Ar), 9.45 (s, 1H, NH); 13
C
eluent. Brown powders were obtained for 3a and 3c. 3b was not
NMR (75 MHz) δ 8.8 (CH3), 46.0 (CH2), 88.2 (Ar), 125.2 (Ar), 137.7 (Ar), isolated, the crude oil was used without further purification.
1
140.8 (Ar), 214.3 (C=S); 1b: yield: 97%; Mp: 100°C; H NMR (300 3a : yield : 36%; Mp = 174°C; 1H NMR (300 MHz) δ 7.20 (m, 2H, Ar) ;
MHz) δ 1.36 (t, 9H, 3J=7.3Hz, CH3), 3.23 (q, 6H, 3J=7.3Hz, CH2), 6.99 (t, 7.92 (m, 2H, Ar). 13C NMR (CDCl3, 75 MHz) δ = 96.8 (Ar), 102.1 (C=C),
1H, 3J=8.1Hz, Ar), 7.39 (d, 1H, 3J=8.1Hz, Ar), 7.62 (d, 1H, 3J=8.1Hz, Ar), 127.1 (C=C), 128.3 (2Ar), 137.2 (Ar), 139.6 (2Ar), 186.1 (C=S), 188.1
8.10 (s, 1H, Ar), 9.40 (s, 1H, NH); 13C NMR (75 MHz) δ 8.8 (CH3), 46.0 (C=O); IR (C=S): 1261 cm-1, (C=O): 1695 cm-1; HRMS (ESI) calcd for
(CH2), 93.3 (Ar), 122.8 (Ar), 129.7 (Ar), 131.8(Ar), 133.3 (Ar), 142.1 C10H4INOS4 [M+H]+: 409.82933. Found: 409.8296; Anal. calcd for
(Ar), 214.7 (C=S); 1c: yield : 92%; Mp: 95 °C; 1H NMR (300 MHz) δ 1.36 C10H4INOS4: C, 29.34; H, 0.99; N, 3.42. Found: C, 29.68; H, 1.06; N,
3
(t, 9H, J=7.3Hz, CH3), 3.22 (q, 6H, 3J=7.3Hz, CH2), 6.85 (m, 1H, Ar), 3.50.
7.31 (m, 1H, Ar), 7.78 (d, 1H, 3J=8.1Hz, Ar), 8.08 (d, 1H, 3J=8.1Hz , Ar), 3c : yield : 60% ; Mp = 200°C ; 1H NMR (300 MHz) δ 7.29 (m, 1H,
9.02 (s, 1H, NH); 13C NMR (75 MHz) δ 9.2 (CH3) ; 46.0 (CH2) ; 95.0 (Ar) ; Ar), 7.44 (m, 1H, Ar), 7.58 (m, 1H, Ar), 8.02 (m, 1H, Ar); 13C NMR
114.8 (Ar) ; 127.7 (Ar) ; 128.8 (Ar) ; 138.8 (Ar) ; 142.2 (Ar) ; 215.5 (75 MHz) δ 94.2 (Ar), 108.1 (C=C), 112.6 (C=C), 131.1 (Ar), 131.7
(C=S); To a solution of the dithiocarmate salt (1a-c) (20.6 g, 52.0 (Ar), 138.8 (Ar), 139.4 (Ar), 143.7 (Ar), 191.6 (C=S), 192.1 (C=0);
mmol) was added 1 equivalent of chloroacetaldehyde (0.96 mL, 52.0 IR (C=S): 1289 nm , IR (C=O): 1660 nm; HRMS (ESI) calcd for
mmol). The solution was stirred for 12h at rt and 9/10 of the solvent C10H4INOS4 [M+H]+: 431.81127. Found: 431.8110; Anal. calcd
was evaporated in vacuo. The mixture was added to 15 mL of H2SO4 for C10H4INOS4: C, 29.34; H, 0.99; N, 3.42 .Found: C, 29.65; H,
at 0°C and stirred for further 10 minutes. The solution was extracted 0.92; N, 3.21.
with CH2Cl2 (3 x 50 mL), washed with water (3 x 20 mL) and dried over
MgSO4. The precipitate was washed with ethanol. Brown powders
Synthesis of BIP-BTTT 4a-c. A solution of thiazoline-thione 3a-c
(243mg, 0.59 mmol), (crude compound for 3b) in 30 mL of toluene
were obtained.
1
2a: yield: 71%; Mp = 211°C; H NMR (300 MHz) δ 6.67 (d, 1H, was refluxed for 16h. 80% of the solvent was removed in vacuo and
3J=4,7Hz, SCH), 7.08 (d, 1H, 3J=4,7Hz, NCH), 7.27 (d, 2H, 3J=4,7Hz, Ar), the concentrated solution was filtrated and the precipitate was
7.85 (d, 2H, 3J=4,7Hz, Ar); 13C NMR (75 MHz) 95.0 (Ar), 111.6 (C=C), washed with ethanol. Dark purple powders were obtained. Crystals
128.4 (2Ar), 132.1 (C=C), 138.3 (Ar), 138.9 (2Ar), 214.5 (C=S); HRMS of 4c of sufficient quality for X-ray diffraction were obtained by slow
+
(ESI) calcd for C9H6INNaS2 [M+Na] : 341.88786. Found: 341.8882; evaporation of CHCl3 solution.
1
Anal calcd for C9H6INS2: C, 33.87; H, 1.89; N, 4.39. Found: C, 33.68; H, 4a: yield: 72%, Mp>250°C; . H NMR (CS2, 300 MHz) δ 7.08 (d, 4H,
1.82; N, 4.38.
Ar), 7.89 (d, 4H, Ar); HRMS (ESI) calcd for C18H9N2IS6 [M]+: 697.70958.
2b: yield 87%; Mp : 119°C; 1H NMR (300 MHz) δ 6.68 (d, 1H, 3J=4.7Hz, Found 697.7101; UV-vis (CHCl2) λmax(nm) (ε[L.mol-1.cm-1])= 242
SCH), 7.10 (d, 1H, 3J=4.7Hz, NCH), 7.24 (m, 1H, Ar), 7.51 (m, 1H, Ar), (24640), 358 (11500), 520 (2550); Anal. calcd for [C18H8I2N2S6 +
7.80 (m, 2H, Ar), 7.83; 13C NMR (75 MHz) δ 93.9 (Ar), 111.6 (C=C), Toluene (8/1)]: C, 31.93 ; H, 1.28 ; N, 3.95. Found: C, 32.08 ; H, 1.27 ;
126.1 (C=C), 130.8 (Ar), 132.1 (Ar), 135.3 (Ar), 138.3 (Ar), 139.3 (Ar), N, 3.95.
1
188.7 (C=S); HRMS (ESI) calcd for C9H6INNaS2 [M+Na] +: 341.88786. 4b: yield : 30% (calculated from 2b), mp>250°C; H NMR (CS2, 300
Found: 341.8881. Anal calcd for C9H6INS2: C, 33.87; H, 1.89; N, 4.39. MHz) δ 7.18 (m, 2H, Ar), 7.32(m, 2H, Ar), 7.52 (m, 2H, Ar), 7.83 (m,
Found C, 33.51; H, 1.69; N, 4.42.
2H, Ar); UV-vis (CHCl2) λmax(nm) (ε[L.mol-1.cm-1])= 232(36060), 359
2c: yield 72%; Mp :180°C; 1H NMR (300 MHz) δ 6.71 (d, 1H, 3J=4,7Hz, (18370), 512(3420); HRMS (ESI) calcd for C18H9N2IS6 [M+Na]+:
SCH), 6.98 (d, 1H, 3J=4,7Hz, NCH), 7.22 (m, 1H, Ar), 7.40 (m, 1H, Ar), 720.69935. Found 720.6993. Analysis calcd for [C18H8I2N2S6 + Toluene
7.52 (m, 1H, Ar), 7.99 (m, 1H, Ar); 13C NMR (75 MHz) δ 96.7 (Ar), 111.7 (8/1)]: C, 31.93 ; H, 1.28 ; N, 3.95. Found: C, 32.04 ; H, 1.32 ; N, 4.18.
(C=C), 129.2 (C=C), 129.8 (Ar), 131.4 (2Ar), 140.4 (Ar), 141.5 (Ar), 4c: yield : 60%, mp = 200°C. 1H NMR (300 MHz) δ 7.27 (m, 2H,
189.0 (C=S); HRMS (ESI) calcd for C9H6INNaS2 [M+Na]+: 341.88786. Ar), 7.41 (m, 2H, Ar), 7.54 (m, 2H, Ar), 8.02 (m, 2H, Ar); UV-vis
Found 341.8877. Anal calcd for C9H6INS2: C, 33.87; H, 1.89; N, 4.39. (CHCl2) λmax(nm) (ε[L.mol-1.cm-1]):226(28670), 358(14928),
Found: C, 33.76; H, 1.69; N, 4.44.
511(2270); HRMS (ESI) calcd for C18H9N2IS6 [M]- : 697.71068.
Found: 697.7107; Analysis calcd for [C18H8I2N2S6 + Toluene
Synthesis of bicycle 3a-c: To a -10°C cooled solution of thiazoline (2a- (8/1)]: C, 31.93 ; H, 1.28 ; N, 3.95. Found: C, 31.77 ; H, 1.25 ; N,
c) (1 g, 3.12 mmol) in 80 mL of dry THF under nitrogen was added a 3.96.
solution of LDA prepared from diisopropylamine (0.66 ml, 4.8 mmol)
and n-BuLi 1.6M (2.93 mL, 4.8 mmol) in 10mL of dry THF. After Crystallography
Data were collected on a D8 VENTURE Bruker AXS diffractometer
stirring for 30 min at -10°C, sulphur S8 (150 mg, 4.8 mmol) was added
and the solution was stirred for an additional 30 min. A solution of with graphite-monochromated Mo-K radiation ( = 0.71073 Å) for
LDA diisopropylamine (0.88mL, 6.24 mmol) and n-BuLi (3.9 mL, 6.24
mmol) in 15mL of dry THF was added. The mixture was stirred for 3
hours and S8 (200 mg, 6.24 mmol) was added. After 30 min,
triphosgene (1.11 g, 3.7 mmol) was added to the reaction mixture.
The reaction was stirred overnight and water (15 mL) was slowly
added. The solvent was evaporated in vacuo. Dichloromethane (50
2b, 3a, 3c and 4c The structures were solved by dual-space algorithm
using the SHELXT program,17 and then refined with full-matrix least-
square methods based on F2 (SHELXL).18 All non-hydrogen atoms
were refined with anisotropic atomic displacement parameters. H
atoms were finally included in their calculated positions. Concerning
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ARTICLE
3a, the use of Platon/TwinRotMat19 routine allowed to detect the
presence of a twinning in the measured crystal. Satisfactory final
structural refinement has been performed considering the presence
of such a twinning and on the hklf5 file format, leading to a refined
twin ratio of 0.19. Crystallographic data on X-ray data collection and
structure refinements are given in Table 3
5
6
7
E. D. Głowacki, M. Irimia-Vladu, S. Bauer and N.VSie.wSaArrtiicclieftOcnil,inJe.
Mater. Chem. B, 2013, 1, 3742-3753.
K. S. Kim, P. Tarakeshwar and J. Y. Lee,DCOhIe: m10..1R0e3v9./,C280C0E002, 014060A,
4145-4185.
(a) G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimagi,
G. Resnati and G. Terraneo, Chem. Rev., 2016, 116, 2478–
2601. (b) L. C. Gilday, S. W. Robinson, T. A. Barendt, M. J.
Langton, B. R. Mullaney and P. D. Beer, Chem. Rev., 2015, 115,
7118–7195(a) G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A.
Priimagi, G. Resnati and G. Terraneo, Chem. Rev., 2016, 116,
2478–2601. (b) L. C. Gilday, S. W. Robinson, T. A. Barendt, M.
J. Langton, B. R. Mullaney and P. D. Beer, Chem. Rev., 2015,
115, 7118–7195.
Table 3 Crystallographic data
Compound
Formula
2b
3a
3c
4c
C9H6INS2 C10H4INOS4 C10H4INOS
C18H8I2N2S6
8
9
A. S. Mahadevi and G. N. Sastry, Chem. Rev., 2016, 116, 2775-
2825
4
(a) Y. Le Gal, N. Bellec, F. Barrière, R. Clérac, M. Fourmigué, V.
Dorcet, T. Roisnel, and D. Lorcy, Dalton Trans., 2013, 42,
16672-16679. (b) Y. Le Gal, D. Ameline, N. Bellec, A. Vacher, T.
Roisnel, V. Dorcet, O. Jeannin and D. Lorcy, Org. Biomol.
Chem., 2015, 13, 8479–8486. (c) Y. Le Gal, M. Rajkumar, A.
Vacher, V. Dorcet, T. Roisnel, M. Fourmigué, F. Barrière, T.
Guizouarn and D. Lorcy, CrysEngComm. 2016, 18, 3925–3933.
FW
(g·mol–1)
Crystal
system
Space group
a (Å)
319.17
monoclinic monoclinic monoclinic
C 2/c P21/n P21/c
409.28
409.28
698.42
triclinic
P-1
8.7777(10) 4.1078(7)
11.1568(15) 24.675(5)
8.1394(7) 12.5260(18)
10 A. Filatre-Furcate, T. Higashino, D. Lorcy and T. Mori, J. Mater.
Chem. C, 2015, 3, 3569-3573.
11 (a) K. Iijima, Y. Le Gal, T. Higashino, D. Lorcy, T. Mori, J. Mater.
Chem. C, 2017, 5, 9121–9127. (b) K. Iijima, Y. Le Gal, D. Lorcy
and T. Mori, RSC Adv., 2018, 8, 18400–18405.
12 C. Wang, H. Dong, W. Hu, Y. Liu and D. Zhu, Chem. Rev., 2012,
112, 2208–2267.
13 Y. Le Gal, D. Lorcy, O. Jeannin, F. Barrière, V. Dorcet, J. Lieffrig
and M. Fourmigué, CrystEngComm., 2016, 18, 5474–5481.
14 M. L. Kaplan, R. C. Haddon, F. B. Bramwell, F. Wudl, J. H.
Marshall, D. O. Cowan and S. Gronowitz, J. Phys. Chem., 1980,
84, 427–431.
15 M. Arca, M. C. Aragoni, F. A. Devillanova, A. Garau, F. Isaia, V.
Lippolis, A. Mancini and G. Verani, Bioinorg. Chem. Appl.,
2006, 58937.
b (Å)
c (Å)
 
 
 
V (Å3)
T (K)
Z
6.9798(7)
22.487(2)
90
14.352(2)
14.522(2)
117.141(4)
95.478(5)
100.638(5)
2234.7(6)
150(2)
21.241(3)
90
13.943(3)
90
96.632(4) 118.785(7)
94.788(3)
90
1273.1(2)
150(2)
4
90
2066.3(5)
150(2)
8
90
1238.6(4)
150(2)
4
4
Dcalc (g·cm–3)
 (mm–1)
Total refls.
2.052
3.454
8223
2.195
3.238
11687
2.135
3.151
14751
2.076
3.384
51086
Abs. Corr. multi-scan
multi-scan multi-scan
multi-scan
10225
(0.1050)
6098
Uniq. refls.
(Rint)
2344
(0.0274)
2188
-
2904
(0.0404)
2675
16 P. Auffinger, F. A. Hays, E. Westhof and P. S. Ho, Proc. Natl.
Acad. Sci. USA, 2004, 101,16789–16794.
17 G. M. Sheldrick, Acta Cryst., 2015, A71, 3–8.
18 G. M. Sheldrick, Acta Cryst., 2015, C71, 3–8.
19 A. L. Spek, Acta Cryst., 1990, A46, C34.
Uniq. refls.
8472
(I > 2σ(I))
0.0307,
0.0974
0.0336,
0.1095
1.101
0.0758,
0.1622
0.1094,
0.1758
1.042
0.0306,
0.0814
0.0337,
0.0834
1.054
0.1160,
0.3164
0.1793,
0.3626
1.079
R1, wR2
R1, wR2
(all data)
GoF
Theoretical Modeling
Electrostatic Surface Potential calculations were carried out on the
optimized geometry of the molecules (with Density Functional
Theory using the Gaussian 09 Revision D.01 software, the B3LYP
functional and the 6-31+G** basis set for all atoms and the LANLdp
basis set for iodine). GaussView 5.0.9 was used to generate the
figures.
Notes and references
1
S. Sutton, C. Risko and J. L. Brédas, Chem. Mater., 2016, 28, 3-
16.
2
3
G. R. Desiraju, J. Am. Chem. Soc., 2013, 135, 9952-9967.
R. Gleiter, G. Haberhauer, D. B. Werz, F. Rominger and C.
Bleiholder, Chem. Rev., 2018, 118, 2010-2041.
G. R. Desiraju, Cryst. Growth Des., 2011, 11, 896-898.
4
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View Article Online
DOI: 10.1039/C8CE02046A
Graphical abstract
Sulphur and iodine heteroatoms on the acceptor skeleton induce chalcogen∙∙∙ chalcogen and
halogen-bonding interactions.