Systematic Construction of Ternary Cocrystals by Orthogonal and Robust Hydrogen and Halogen Bonds

Article abstract of DOI:10.1021/jacs.6b02854

A carefully designed strategy is presented for the construction of ternary cocrystals, based on the orthogonality of two supramolecular interaction modes: hydrogen bonding between crown ethers and thioureas and the halogen bonding between thioureas and perfluorohalocarbons. Tested on a set comprising two crown ethers, two thioureas and five halogen bond donors, the strategy resulted in a high, 75% success rate, with 15/20 component combinations yielding at least one cocrystal. Crystal structure analysis revealed the interplay between the hydrogen and halogen bonding motifs, also shedding light on the variables affecting their formation.

Full text of DOI:10.1021/jacs.6b02854

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Article
Systematic Construction of Ternary Co-crystals by
Orthog-onal and Robust Hydrogen and Halogen Bonds
Filip Topi#, and Kari Rissanen
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b02854 • Publication Date (Web): 04 May 2016
Downloaded from http://pubs.acs.org on May 4, 2016
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Systematic Construction of Ternary Coꢀcrystals by Orthogoꢀ
nal and Robust Hydrogen and Halogen Bonds
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Filip Topić and Kari Rissanen*
University of Jyvaskyla, Department of Chemistry, Nanoscience Center, P.O. Box 35, FIꢀ40014 University of
Jyvaskyla, Finland.
Supporting Information Placeholder
ABSTRACT: A carefully designed strategy is presented for construction of ternary coꢀcrystals, based on the orthogoꢀ
nality of two supramolecular interaction modes: hydrogen bonding between crown ethers and thioureas and the haloꢀ
gen bonding between thioureas and perfluorohalocarbons. Tested on a set comprising two crown ethers, two thioureas
and five halogen bond donors, the strategy resulted in a high, 75% success rate, with 15/20 component combinations
yielding at least one coꢀcrystal. Crystal structure analysis revealed the interplay between the hydrogen and halogen
bonding motifs, also shedding light on the variables affecting their formation.
what could be considered as an extension of this apꢀ
proach, robust synthons were identified in a series of
1. INTRODUCTION
In the last two decades, one of the intensively pursued
research topics in crystal engineering has been that of
coꢀcrystals,1,2 although they have been known for much
longer.3 However, this comes as no surprise, given their
great potential as e.g. pharmaceutical,4ꢀ6 luminescent,7
photoꢀmechanical,8 ferroelectric9 or energetic10,11 (exploꢀ
sive!) materials. From the very beginning, one of the
challenges has been the rational design of strategies
enabling deliberate and systematic construction of coꢀ
crystals. While this has largely been overcome in case of
binary coꢀcrystals (i.e. comprising two components),
much fever strategies have been developed for successꢀ
ful construction of ternary and more complex coꢀcrystals.
The seminal paper, not only posing this challenge, but
also offering the first examples of designꢀbased hydroꢀ
genꢀbonded ternary molecular solids (coꢀcrystal), was
that of Aakeröy et al.,12 wherein two different carboxylic
acid molecules were coꢀcrystallized with isonicotinamide.
More specifically, the stronger of the two acids was posꢀ
tulated to bind to the pyridine moiety of isonicotinamide
while the weaker acid binds to the amide moiety, yielding
a discrete 1:1:1 ternary supermolecule, by exploiting the
hierarchy13 of supramolecular synthons.14 The strategy
was later shown to be a general one, using different
components selected based on the same principles.15ꢀ17
A great body of work on the preparation of ternary18ꢀ22
and even quaternary23,24 coꢀcrystals has been recently
reported by Desiraju and coꢀworkers. First, a shapeꢀ
based approach was devised, where one component in
a binary coꢀcrystal can be partially replaced by a third
component,25 in such a way that the molecules particiꢀ
pating in (stronger) hydrogen bonding are left in place,
while the weakly interacting molecules of the same kind
are substituted by similarly shapes ones. This was
demonstrated through successful substitution of loosely
bound 4,4’ꢀbipyridine molecules in its coꢀcrystals with 2ꢀ
or 5ꢀmethylresorcinol by similarly shaped molecules.18 In
crystal forms based on binary coꢀcrystals comprising
heterocyclic bases and polyhydroxyphenols. Upon the
introduction of a third component, the more robust
synthons persisted while the presumably less reliable
ones incorporated the newly introduced third component
instead, yielding ternary coꢀcrystals.19,20 Remarkably, the
same reasoning could be applied sequentially to afford
quaternary23,24 and even quinternary23 coꢀcrystals. Finalꢀ
ly, Desiraju and colleagues also reported the so far only
strategy utilizing a combination of halogen (C−X···O2N; X
= I, Br) and hydrogen bonding (carboxylic acidꢀamide
heterosynthon) to construct binary or ternary coꢀ
crystals,21 depending on the exact nature of the compoꢀ
nents bearing these functional groups.22
We have recently been interested in using concerted
hydrogen and halogen bonding to construct sophisticatꢀ
ed supramolecular assemblies both in solution and the
solid state. A particularly efficient approach was adopted
where
Nꢀalkylammonium
resorcinarene
halide
(NARX),26,27 supramolecular species consisting of differꢀ
ent cationic resorcinarene derivatives and hydrogen
bonded halide anions, were used as halogen bond acꢀ
ceptors with a number of donors. All three components
(Nꢀalkylammonium resorcinarene cations, halide anions
and halogen bond donors) could be varied in an orthogꢀ
onal manner to yield deep cavity cavitands28,29 and capꢀ
sules,30 as well as various dumbbellꢀlike and polymeric
pseudocapsular architectures.31 Inspired by this, we set
out to devise a strategy for assembling ternary coꢀ
crystals with distinct supramolecular role for each comꢀ
ponent which would, by virtue of the orthogonality of
hydrogen and halogen bonds, also allow for tuning of the
structure by changing one, two or all of the components
while still successfully producing the ternary coꢀcrystal.
One of the first questions one faces when designing
such a strategy is evaluating its outcomes. When can a
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strategy be deemed successful? We propose the followꢀ
reas (C and D) and five different perfluorinated halogen
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ing criteria: First, as an obvious conditio sine qua non, it
has to yield ternary coꢀcrystals. Second, it should do so
with a high supramolecular yield,32 and finally, the preꢀ
cise control of the stoichiometry and structure should be
achieved.
bond donors, encompassing monoꢀ and ditopic, aromatic
and nonꢀaromatic, linear and nonꢀlinear and iodineꢀ and
bromineꢀbased ones (1 ꢀ 5). The coꢀcrystallization
screening was initially conducted by simple solution
crystallization, which was subsequently modulated
where necessary to yield better diffraction quality crysꢀ
tals or a pure bulk phase (see SI).
In order to achieve all these goals, we adopted an enꢀ
tirely new approach. Arman et al. reported that the
N−H———S type hydrogen bonding between thioureaꢀtype
molecules is preserved in the structures of their C−I———S
halogen bonded coꢀcrystals.33 Moreover, the set of coꢀ
crystals described consisted of three different thioureas
and three different halogen bond donors, suggesting that
the orthogonality of hydrogen and halogen bonding
could be a general property of such systems. Later,
Robertson et al. showed the halogen bonds between
diiodine as the donor and tetramethylthiourea as the
acceptor to be particularly robust in solution, which was
ascribed to their pronounced chargeꢀtransfer character.34
Inspired by the former and encouraged by the latter, we
decided to combine these approaches by introducing a
third component which would engage in hydrogen bondꢀ
ing with thiourea without competing for the halogen bond
donor, yielding ternary coꢀcrystals by two parallel but
orthogonal selfꢀassembly processes. Here, crown ethers
emerged as an unorthodox but promising choice
(Scheme 1).
Scheme 2. Components used
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The results are summarized in Table 1.; Out of 20 posꢀ
sible (2 × 2 × 5) combinations, 15 yielded at least one
ternary coꢀcrystal, thus giving a high supramolecular
yield of 15/20 = 75%. Taking into account the stoichioꢀ
metric variations (A—D—22/A—D2—22), polymorphism (αꢀ
B—C—12/βꢀB—C—12) and the fact that some structures were
determined at different temperatures, this resulted in a
total of 21 different crystal structures (Tables S1aꢀS1e).
Scheme 1. Motif combination
Table 1. The obtained ternary coꢀcrystals
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2
3
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5
C
D
A—C—12 A—C2—22 A—C2—32 A—C2—42 A—C—5
A—D—22
A
B
A—D—12.2
A—D2—32 A—D—42
A—D—5
A—D2—22
αꢀB—C—12
βꢀB—C—12
a
a
C
D
−
B—C—3
−
−
B—C—5
B—D—5
a
a
a
−
−
B—D2—32
a No ternary phases were observed.
Possessing only ether oxygen atoms as possible accepꢀ
tors, they were expected to reliably interact with thiourea
NHR (R = H, alkyl) groups through multiple hydrogen
bonds, thanks to the macrocyclic effect.35ꢀ37 At the same
time, due to the high directionality of halogen bonds with
respect to the donor,38 hypothetical formation of halogen
bonds with crown ether would not benefit from such
enhancement, thus being restricted to C−X———O(ether)
interactions, which we expected to be easily outcompetꢀ
ed by C−X———S(thiourea) interactions with their more
pronounced covalent character.34,39 Finally, as our deꢀ
sign proved successful, these components will allow for
easy expansion of the component set – a large number
of thioureas, crown ethers of various sizes and perfluoriꢀ
nated halogen bond donors are commercially available,
not to mention the easy synthetic accessibility of many
more.
Given the expected orthogonality of hydrogen and
halogen bonds in the ternary coꢀcrystal structures, it
should be possible to analyze the hydrogen and halogen
bonding motifs independently. Focusing on the hydrogen
bonding between A/B and C/D, two binding stoichiꢀ
ometries can be observed, respectively 1:1 and 1:2,
originating in three different binding motifs between them
(Scheme 3). Whereas the motif III only appears in two
polymorphs of B—C—12 and can thus be considered
somewhat exotic, the rest of the structures exhibit either
motif I or II, which makes it worthwhile to explore the
possible factors that steer the formation of one or the
other. Fortunately, our component set was tailored to
enable the comparative analysis of the behavior of each
crown ether/thiourea combination in ternary coꢀcrystals
with up to 5 different halogen bond donors.
2. RESULTS AND DISCUSSION
Our starting component set (Scheme 2) thus comꢀ
prised two crown ethers (A and B), two different thiouꢀ
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Scheme 3. Hydrogen bondꢀmediated binding motifs A—D2—22, witnesses the delicate interplay of interactions
1
2
between crown ethers and thioureas.
dictating the exact supramolecular outcome.
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Individual hydrogen bonds are not marked as they vary
between different occurrences of the same motif.
Thus, for the coꢀcrystal subset with A and C, motif II
occurs in 3/5 coꢀcrystals (A—C2—22, A—C2—32, A—C2—42), with
the remaining two exhibiting motif I (Table 1; also vide
infra). This might be correlated with the structure of preꢀ
viously described binary coꢀcrystal A—C2,35 which also
shows motif II, indicating a slight preference for this bindꢀ
ing motif, i.e. stoichiometry, with the combination of A
and C. Moreover, in the systems where II is present, with
only one NH2 group fully engaged in hydrogen bonding
with A, the other NH2 group is able to facilitate aggregaꢀ
tion of A—C2 moieties by forming further hydrogen bonds.
This is indeed the case for A—C2—32 and A—C2—42, where
2D sheets are formed through N−H———S hydrogen bonds
between A—C2 moieties (Figure 1a). It thus comes as no
surprise that the two coꢀcrystals are in fact isomorphous,
with the sheets interlinked through halogen bonding with
3 or 4, respectively, which also form stacks between the
sheets (Figure 1b,1c). Contrasting that is A—C2—22,
where the A—C2 moieties are instead linked into chains
by C−I———S halogen bonding with 2 (Figure 2). This reꢀ
veals a clear hydrogen bonding hierarchy in these sysꢀ
tems, where the recognition of C by A through multiple
N−H———O hydrogen bonds is much more reliable than the
N−H———S hydrogen bonding, which can be overruled
even by C−I———S halogen bonding.
Still, judging from the relevant ternary coꢀcrystal strucꢀ
tures described here as well as the structure of their
binary coꢀcrystal, motif II is clearly preferred with A and
C. The combination of A and D shows significantly difꢀ
ferent trends, with the preference for motif I starting from
the previously described binary coꢀcrystal A—D36 and also
observed in 4/6 ternary coꢀcrystals reported here. With
the potential of halogen bond (XB) donors 1 and 5 for
facilitating the formation of motif I already established, its
reappearance in A—D—12.2 and A—D—5 is of little surprise
(Table 1; also vide infra). However, it might be much
more interesting to contrast the behavior of XB donors 2ꢀ
4 with A and D to that with A and C. Especially with 2,
the isolation of two stoichiometric variations, A—D—22 and
Figure 1. a) Hydrogen bonded A—C2 2D sheets in A—C2—32
(and A—C2—42) with hydrogen atoms of A omitted for clarity;
b) Packing of A—C2—32 , with columns of 3 between the A—C2
sheets; c) Packing of A—C2—42 , with columns of 4 between
the A—C2 sheets.
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Figure 2. Chains of A—C2 motif II moieties, formed through
C−I———S halogen bonding with 2 as a ditopic donor.
Initially, A—D—22 is formed as the kinetic product, with A
and D assembling into motif I and 2 only serving as a
monotopic halogen bond donor, not utilizing its full poꢀ
tential (Figure 3a).33 The system evolves, however,
resulting in the formation of A—D2—22 with the reꢀemerging
motif II, and the formation of chains through N−H———S
hydrogen bonds supported by C−I———S and C−I———O haloꢀ
gen bonding with 2 again acting as a ditopic donor (Figꢀ
ure 3b).
Figure 4. Halogen bonded ribbons in the isomorphous
structures of a) A—D2—32 and b) B—D2—32 , comprising motif II
type A—D2/B—D2 moieties linked by C−I———S halogen bonds
with 3. Disorder of A is not shown in a).
Figure 5. Hydrogen bonded columns (motif I) connected by
C−Br———S and C−Br———O halogen bonds with 4 in A—D—42.
Remarkably, coꢀcrystallization experiments on the
component subset comprising crown ether A, thioureas
C and D, and XB donors 1ꢀ5 resulted in a 100% success
rate, with each of the combinations yielding at least one
ternary coꢀcrystal. Repeating all these experiments with
benzoꢀcrown ether B instead of A, however, halved the
success rate, showing B to be a much more selective
coꢀformer than A. Still, the structures of the ternary coꢀ
crystals obtained with such a selective coꢀformer might
reveal particularly robust supramolecular motifs, sugꢀ
gesting possible improvements to our synthetic strategy.
Figure 3. a) Hydrogen bonded motif I formed in A—D—22,
decorated by 2 acting as a monotopic halogen bond donor;
b) Motif II in A—D2—22, with A—D2 moieties connected by
N−H———S hydrogen bonds and C−I———S halogen bonds with 2,
now as a ditopic donor. Disorder of 2 is omitted in a).
Next, the structure of A—D2—32, featuring thiourea D in the
more stable cis conformation40 still exhibits motif II, with
A—D2 moieties connected into chains through C−I———S
halogen bonds with XB donor 3 (Figure 4a). Based on
previous observations with A and C, formation of an
isomorphous structure might be expected with 4. Yet,
with the C−I———S halogen bonds playing a pivotal role in
the structure of A—D2—32, it seems that the presumably
weaker XB donor 4 cannot support the formation of an
isomorphous structure through C−Br———S halogen bonds.
Instead, the balance of interactions is once again tipped
in favor of motif I, resulting in A—D—42. While the stoichiꢀ
ometry might be surprising at first, given that 4 is a ditopꢀ
ic XB donor, it is a result of each molecule of 4 forming
one C−Br———S and one C−Br———O halogen bond respecꢀ
tively with D and A (Figure 5).
A unique example among all the ternary coꢀcrystals
presented here, the combination of benzoꢀcrown ether
B, thiourea C and XB donor 1 yielded a polymorphic pair
of coꢀcrystals αꢀB—C—12 (Figure 6a) and βꢀB—C—12 (Figꢀ
ure 6b), both of which feature the motif III, not observed
in any of the other structures.
Figure 6. Discrete B—C—12 assemblies in the two polyꢀ
morphs a) αꢀB—C—12 and b) βꢀB—C—12.
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The two polymorphs arise from different packing of the
discrete B—C—12 moieties: in both structures, they can be
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3
4
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seen as forming layers through stacking of the aromatic
rings of B and 1. These layers then pack in a parallel [βꢀ
B—C—12] or antiꢀparallel fashion [αꢀB—C—12], giving rise to
two polymorphs (Figures S21ꢀS24). To the best of our
knowledge, this is the first example of polymorphism in
ternary coꢀcrystals. Both of the other two structures with
the combination of B and C, namely B—C—3 and B—C—5,
show the B and C forming motif I, with the hydrogen
bonded columns B—C interlinked by C−I———S halogen
bonds, respectively through 3 (Figures S25, S26b) or 5
(Figure 8c). Surprisingly, the stacking of the phenyl rings
of B and 3 does not seem to interfere with the formation
of motif I between B and C (Figure S26a) or the infinite
halogenꢀbonded chains between C and 3, with all three
seemingly acting in concert (Figure S26b).
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Finally, only two ternary coꢀcrystals were observed
when the combination of B and D was employed. One of
the two is B—D2—32, reminiscent of A—D2—32 not only in its
stoichiometry but actually forming an isomorphous strucꢀ
ture consisting of B—D2—motif IIꢀtype moieties forming
ribbons through C−I———S halogen bonds with 3 (Figure
4b). This might be a unique example of quite a drastic
perturbation (replacement of the plain 18ꢀcrownꢀ6 A with
benzoꢀsubstituted B) which does not radically influence
the overall structure. No less remarkably, like all the coꢀ
crystals involving XB donor 5 so far, the B—D—5 once
again sports the motif I columns of B and D interlinked
by halogen bonding with 5 (vide infra).
Figure 7. Different metrics of the motif I columns in a)
A—C—12 and b) A—D—12.2. Hydrogen and halogen bonds are
shown as dashed green and black lines, respectively, while
the hydrogen atoms of A are omitted for clarity.
of motif I (or motif III, still with the same stoichiometry),
unlike the motif II formed with 2, 3 and 4 as halogen
bond donors. In fact, it seems that XB donors 1 and 5
having little in common with 2ꢀ4 might just be at the root
of their different behavior: While all of 2ꢀ4 are aromatic
and ditopic donors, 1 is aromatic but monotopic, and 5 is
ditopic but aliphatic. Both the monotopic 1 and the conꢀ
formationally flexible 5 are expected to eliminate or reꢀ
duce the communication between the halogen bond
acceptors, with any significant packing preferences also
being absent in the case of 5. This in turn seems to allow
for the almost perfect orthogonality of hydrogen and
halogen bonding in these systems, reliably yielding terꢀ
nary coꢀcrystals with expected stoichiometries and suꢀ
pramolecular motifs.
Clearly, two intriguing aspects of the mentioned strucꢀ
tures deserve particular highlighting. First, the curious
stoichiometry of A—D—12.2 compared to similar A—C—12
merits further explanation. This seems to be a conseꢀ
quence of the elongation of motif Iꢀtype columns upon
changing from C to D, which is best quantified through
the distance between the centroids of neighboring moleꢀ
cules of A in the same column (Figure 7). This expanꢀ
sion of the structure is also reflected in the increased
distance between molecules of XB donor 1 in A—D—12.2
(Figure 7b), allowing for inclusion of an excess of 1
(Figure S10).
On the other hand, focusing the analysis on the haloꢀ
gen bonding reveals very few surprises and only a few
general structural features are worth commenting. Both
thioureas C and D seem to act almost exclusively as
bifurcated acceptors,41 with the only exception being
A—D2—22 (Figure 3b). The relative geometries manifest a
notable degree of variation, judged especially by the
X———S———X and X———S−C angles (Tables S3, S5, ꢁ, S35).
While the former can be explained by a relatively weak
interaction energy dependence on the X———S distance
and the N−C−S———X torsional angle on the relevant interꢀ
vals, as established by Pennington and coꢀworkers,33 the
latter can be explained by a partial C−X———π character
due to the π(C=S) electron participation. Moreover, the
quadrupolar stacking of the aromatic rings also influꢀ
ences the orientation of the aromatic halogen bond doꢀ
nor with respect to the thiourea acceptor, such as in α/βꢀ
B—C—12 (Figure 6). Nevertheless, the halogen bonding
seems to operate rather predictably especially with 1, 3
and 5 as donors, forming discrete 1———C/D———1 assemblies
or infinite ———C/D———3/5———C/D———3/5——— chains.
Another striking observation is that of the identical
1:1:1 stoichiometry in all ternary coꢀcrystals involving 5,
with motif I also appearing in all four crystal structures,
despite their differences (Figure 8). Specifically, it is
interesting to note how the difference in halogen bonding
connectivity e.g. between A—C—5 (Figure 8a) and A—D—5
(Figure 8b) does not affect the above mentioned stoiꢀ
chiometry and the appearance of motif I columns. Moreꢀ
over, the effect of the motif I column elongation upon
change from C to D again becomes evident when comꢀ
paring B—C—5 (Figure 8c) and B—D—5 (Figure 8d), with
increased distance allowing for the pairing of B—D colꢀ
umns through phenyl ring stacking in B—D—5.
Looking at the coꢀcrystal series with XB donors 1 and
5 raises the question: What are the different (possibly
shared) characteristics of 1 and 5 driving the formation
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peculiarity in its behavior, causing it to act as a monotopꢀ
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3
4
5
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ic donor in A—D—22 (Figure 3a), to form one C−I———S and
one C−I———O halogen bond in A—D2—22, reinforcing the
hydrogen bonded chains (Figure 3b), only to emerge as
the seemingly key interaction in linking individual A—C2
moieties into chains in A—C2—22 (Figure 2). Similarly, the
expectedly weaker C−Br———S halogen bonding seems to
fall victim to aromatic ring stacking of 4 in A—C2—42, with
one of the two symmetrically independent C−Br———S halꢀ
ogen bonds assuming exclusively C−Br———π character
(Figure S6), or to the realization of the robust hydrogen
bonding motif I and stacking of 4 in A—D—42, forming one
C−Br———S and one C−Br———O halogen bond instead (Figꢀ
ure 5), reminiscent of 2 in A—D2—22.
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3. SUMMARY AND CONCLUSIONS
Our work outlines a designꢀbased strategy for conꢀ
struction of ternary coꢀcrystals based on the ability of
thioureas to simultaneously engage in hydrogen and
halogen bonding in an orthogonal manner, with the
crown ethers and the perfluorocarbon halides as the
other coꢀformers. This ability is presumed to arise from
the fundamentally different nature of the two interactions,
the predominantly electrostatic hydrogen bonding and
the halogen bonding with a significant chargeꢀtransfer
character. The strategy was tested on a compact but
diverse set of commercially available components, yieldꢀ
ing ternary coꢀcrystals for 15/20 different component
combinations. Detailed structural analysis was undertakꢀ
en in order to identify and critically examine the variables
influencing its efficacy.
The hydrogen bonding in the obtained ternary coꢀ
crystal structures is classified as belonging to one of
three different motifs (I, II and III), whose formation can
be correlated with the particular structural features of the
components. Namely, the stacking of the aromatic rings
(present in benzoꢀcrown ether B and XB donors 1ꢀ4),
sterical crowding of halogen bond donor atoms (as in
e.g. 2) or the Brꢀbased donor (4) all seem to be imꢀ
portant variables which can influence the coꢀcrystal forꢀ
mation. On the other hand, crown ethers A and B as well
as thioureas C and D are shown to be structurally equivꢀ
alent to a great degree, with the structural features often
preserved on changing between A and B (e.g. for
A—D2—32/B—D2—32) or C and D (e.g. for A—C—12/A—D—12.2).
Remarkably, all of these observations are validated by
coꢀcrystals with the nonꢀaromatic, linear, flexible and
iodineꢀbased XB donor 5, which all exhibit the same
hydrogen bonding motif I and the same halogen bonded
infinite chains.
Finally, the presented results show how the orthogoꢀ
nality of hydrogen and halogen bonding can be achieved
and employed to prepare complex molecular solids –
ternary coꢀcrystals. The principles outlined here hold
great potential for the effective design of highly complex,
functional molecular solids from simple building blocks.
This research direction, as well as a detailed study of the
particular interactions and their interplay in these sysꢀ
tems, is currently being pursued in our laboratory.
Figure 8. Linking of the hydrogen bonded motif I columns
by halogen bonds with 5 in the structures of a) A—C—5, b)
A—D—5, c) B—C—5 and d) B—D—5. Hydrogen atoms of A and B
and minor disorder components are omitted for clarity.
ASSOCIATED CONTENT
In contrast, the sterical crowding of the donor iodine
atoms in orthoꢀpositions of 2 seems to induce some
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22. Tothadi, S.; Sanphui, P.; Desiraju, G. R. Cryst. Growth
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107.
Supporting Information. Experimental details, powder
1
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5
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7
8
diffraction studies, single crystal Xꢀray structure analysis
with additional figures and tables of selected hydrogen and
halogen bonds. This material is available free of charge via
the Internet at http://pubs.acs.org. CCDC 1469004ꢀ1469024
contain the supplementary crystallographic data for this
paper. The data can be obtained free of charge from The
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AUTHOR INFORMATION
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Corresponding Author
28. Beyeh, N. K.; Cetina, M.; Rissanen, K. Chem. Commun.
2014, 50, 1959ꢀ1961.
*kari.t.rissanen@jyu.fi
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sanen, K. Org. Chem. Front. 2015, 2, 340ꢀ345.
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
F.T. and K.R. gratefully acknowledge the Academy of Finꢀ
land (K.R. grant nos. 263256 and 265328) and the Universiꢀ
ty of Jyväskylä for financial support. F.T. acknowledges the
PhD scholarship from NGSꢀNANO and the 2015 Ludo
Frevel Crystallography Scholarship from ICDD.
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