Halide anions driven self-assembly of haloperfluoroarenes: Formation of one-dimensional non-covalent copolymers

Article abstract of DOI:10.1016/j.jfluchem.2009.07.005

The supramolecular organization in six solid assemblies involving iodo- and bromoperfluoroarene derivatives is described. Single crystal X-ray analyses show that the formation of the supramolecular architectures is controlled by I^-?Br-Ar_F, I^-?I-Ar_F, Br^-?I-Ar_F, and Cl^-?I-Ar_F halogen bondings thus proving the X^-?X′-Ar_F supramolecular synthon, where X can be the same as or different from X′, is particularly robust. In five of the described architectures halide anions form two halogen bondings and form infinite chains wherein dihaloperfluoroarenes, which function as bidentate electron acceptors, and halide anions, which function as bidentate electron donors, alternate. This behaviour shows halide anions have a fair tendency to work as bidentate halogen bonding acceptors.

Full text of DOI:10.1016/j.jfluchem.2009.07.005

Journal of Fluorine Chemistry 130 (2009) 1171–1177
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Halide anions driven self-assembly of haloperfluoroarenes: Formation
of one-dimensional non-covalent copolymers
Antonio Abate a, Serena Biella a, Gabriella Cavallo a, Franck Meyer a, Hannes Neukirch a,
Pierangelo Metrangolo a, Tullio Pilati b, Giuseppe Resnati a, , Giancarlo Terraneo
*
a,**
a NFMLab-Department of Chemistry, Materials and Chemical Engineering ‘‘Giulio Natta’’, Politecnico di Milano, Via L. Mancinelli 7, 20131 Milan, Italy
b C.N.R.-I.S.T.M., University of Milan, Via C. Golgi 19, 20133 Milan, Italy
A R T I C L E I N F O
A B S T R A C T
Article history:
The supramolecular organization in six solid assemblies involving iodo- and bromoperfluoroarene
derivatives is described. Single crystal X-ray analyses show that the formation of the supramolecular
architectures is controlled by Iꢁꢀ ꢀ ꢀBr–ArF, Iꢁꢀ ꢀ ꢀI–ArF, Brꢁꢀ ꢀ ꢀI–ArF, and Clꢁꢀ ꢀ ꢀI–ArF halogen bondings thus
proving the Xꢁꢀ ꢀ ꢀX0–ArF supramolecular synthon, where X can be the same as or different from X0, is
particularly robust. In five of the described architectures halide anions form two halogen bondings and
form infinite chains wherein dihaloperfluoroarenes, which function as bidentate electron acceptors, and
halide anions, which function as bidentate electron donors, alternate. This behaviour shows halide
anions have a fair tendency to work as bidentate halogen bonding acceptors.
Received 14 May 2009
Received in revised form 7 July 2009
Accepted 8 July 2009
Available online 16 July 2009
Keywords:
Fluorine
Iodine
ß 2009 Elsevier B.V. All rights reserved.
Halogen bonding
Self-assembly
Crystal engineering
Supramolecular chemistry
1. Introduction
being 0.009 in CH3I and 0.165 in CF3I [3]. In general, iodo-
perfluorocarbons, and iodine substituted heteroaromatic cations,
The electron density around halogen atom in organic halides is
anisotropically distributed. A region of positive electrostatic
potential is present along the extension of the C–X bond axis
typically present particularly remarkable
atom.
The term halogen bonding (XB) has been introduced to
designate any non-covalent interaction DꢀꢀꢀX–Y in which X is an
electrophilic halogen atom (Lewis acid, XB-donor), D is a donor of
electron density (Lewis base, XB-acceptor), and Y is carbon,
s-holes on the iodine
(X = Cl, Br, I) and this electropositive crown, also named
s-hole, is
surrounded by an electroneutral ring and, further out, an
electronegative belt [1]. Halogen atoms can thus work as electron
donors in directions perpendicular to the C–X bond (at the
electronegative belt) and as electron acceptors on the extension of
the C–X bond (at the electropositive crown). The extent of this
electropositive crown increases with the polarizability of the
halogen and its magnitude also depend on the electron with-
drawing power of the neighbouring groups on the carbon skeleton
[2]. For instance, chlorine in CH3Cl does not present any positive
electrostatic potential, but it appears in CH2FCl, and becomes even
greater in CF3Cl; similarly, in iodomethane derivatives the positive
charge on iodine atom increases with the fluorination degree,
nitrogen, halogen, etc. [4] The presence of a s-hole accounts for the
formation of XBs, as this electropositive region can interact
attractively with any electron rich sites. In the last decade a
renewed interest in XB proved the effectiveness of the interaction
in driving self-assembly processes and the XB rapidly became a
new paradigm in supramolecular chemistry [5]. The use of neutral
electron donors (most frequently pyridine, amine, carbonyl, and
ether moieties) is now well established. It allows for the self-
assembly of a variety of supramolecular architectures in the solid
and the obtainment of useful functional properties [6]. The use of
anionic electron donors in XB directed processes has received far
less attention [7] and in this paper we will describe the formation
of halogen bonded (X-bonded) supramolecular structures when
iodo- and bromoperfluorocarbon derivatives interact with iodide,
bromide, or chloride anions.
* Corresponding author. Tel.: +39 02 2399 3032; fax: +39 02 2399 3180.
** Corresponding author. Tel.: +39 02 2399 3063; fax: +39 02 2399 3180.
E-mail addresses: giuseppe.resnati@polimi.it (G. Resnati),
giancarlo.terraneo@polimi.it (G. Terraneo).
In general, the number of XBs formed by a given anion can vary
from one aggregate to another as a function of the composition of
URL: http://nfmlab.chem.polimi.it/
0022-1139/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2009.07.005

1172
A. Abate et al. / Journal of Fluorine Chemistry 130 (2009) 1171–1177
Scheme 1. XB donors and acceptors.
the system, the molecular structure of the interacting partners, and
the overall geometric and electronic requirements in the crystal
packing. For instance, bromide and iodide anions most frequently
give rise to two or three XBs [8], but the formation of one [9], four
[10], or even five [11], six or eight [10a,11,12] XBs has been
reported. Here we describe how on evaporation of solutions of
2,3,5,6-tetrafluoro-1,4-diiodobenzene (1) and tetra-n-butylammo-
nium chloride or bromide, (2 and 3, respectively, Scheme 1), the
1:1 crystalline adducts 7 and 8 are formed wherein 1 and chloride
or bromide anions work as bidentate XB donors and acceptors,
respectively, and alternate along the formed supramolecular
anionic infinite chains (Scheme 2).
In order to check if also iodide anions have a possible tendency
to form two XBs, we studied the interactions’ pattern in tris-
(2,3,5,6-tetrafluoro-4-iodophenyl)ammonium iodides 4 and 6 and
the structurally related tris-(2,3,5,6-tetrafluoro-4-bromopheny-
l)ammonium iodide 5 (Scheme 1). The chemical structure of
modules 4–6 makes three XB donor sites available to any iodide
anions so that iodide anions could work as mono-, bi-, or tridentate
XB acceptors and afford, for instance, discrete dimeric adducts,
infinite chains, or honeycomb nets, respectively. Actually, in
crystalline 4–6 too, the presence of X-bonded infinite chains is
observed, wherein iodide anions are bidentate XB acceptors and
bridge the iodo- or bromotetrafluorobenzene rings of two different
Scheme 2. X-bonded infinite chains wherein iodide anions are bidentate XB acceptors.

A. Abate et al. / Journal of Fluorine Chemistry 130 (2009) 1171–1177
1173
Table 1
Selected crystallographic and data collection parameters for X-bonded adducts 4–8.
7
8
4a
4b
5
6
Formula
C
22H36 ClF4I2N
C24H16 Br3F4I2N
724.23
C24H16F12I4N4
1096.01
Colourless
0.04 ꢂ 0.05 ꢂ 0.24
Monoclinic
P21/n
C24H16F12I4N4
1096.01
Colourless
0.04 ꢂ 0.08 ꢂ 0.32
Monoclinic
P21/n
C24H16 Br3F12IN4
955.04
C30H25F12I4NO6
1231.11
Colourless
0.10 ꢂ 0.12 ꢂ 0.27
Monoclinic
P21/c
M
679.77
Colourless
0.17 ꢂ 0.28 ꢂ 0.30
Monoclinic
P21/c
Crystal color
Dimension [mm3]
Crystal system
Space group
Colourless
0.28 ꢂ 0.32 ꢂ 0.36
Monoclinic
C2/c
Colourless
0.11 ꢂ 0.19 ꢂ 0.32
Monoclinic
P21/n
˚
a [A]
9.1025(12)
13.951(2)
21.671(3)
94.89(2)
2742.0(7)
4
49.295(6)
8.6878(10)
13.944(2)
102.86(2)
5821.9(13)
8
7.9773(12)
13.853(2)
26.390(3)
93.33(2)
2911.4(7)
4
7.775(2)
21.702(6)
18.075(5)
94.94(2)
3038.5(14)
4
8.1986(12)
13.793(2)
26.977(3)
94.06(2)
3043.0(7)
4
7.8994(12)
27.005(4)
17.766(3)
94.99(2)
3775.5(10)
4
˚
b [A]
˚
c [A]
b
[8]
3
˚
V [A ]
Z
T [K]
90
297
297
297
297
90
rcalc [g cmꢁ1
]
1.647
1.653
2.500
2.396
2.085
2.166
m(Mo-K
a
) [mmꢁ1
]
2.427
3.567
4.383
4.200
5.089
3.402
2umax [8]
31.56
25.36
27.50
27.54
27.52
25.00
Data collected
Unique data
Rint
54256
28887
58392
56837
60426
75872
0.0259
8776
0.0344
6594
6942
6996
11885
5328
0.0510
0.0506
0.0346
0.0298
No. of obs. data Io > 2
No. of parameters
No. of restraints
Rall
s(Io)]
8048
3675
3035
4815
5648
9785
415
344
400
406
461
526
0
226
547
22
85
366
0.0200
0.0171
0.0405
0.0394
1.034
0.0586
0.1491
0.1109
0.0819
0.2410
0.2187
1.055
0.0494
0.0502
Robs
0.0324
0.0844
0.0383
0.0377
wRall
0.0781
0.2539
0.1105
0.0994
wRobs
0.0690
0.2299
0.1044
0.0994
Goodness-of-fit
1.018
0.898
1.053
1.074
ꢁ3
˚
Drmin,max [e A
]
ꢁ0.35, 0.69
731756
ꢁ0.46, 0.44
731757
ꢁ1.30, 1.88
731752
ꢁ1.51, 2.90
731753
ꢁ1.14, 0.96
731754
ꢁ2.16, 1.61
731755
CCDC
ammonium cations, the third halotetrafluorobenzene remaining
uninvolved in any XB formation (Scheme 2).
bromides 2 and 3, in our case). The anion is the XB acceptor, the
cation plays no active role, as far as XB formation is concerned, and
the XB donor is a third neutral halogenated component present in
the co-crystal.
2. Results and discussion
Melting point analysis, beside the usual advantages of simple
and fast measurements, gives a reliable proof that 7 and 8 are well-
defined chemical species rather than a mechanical mixture of
starting modules. When a solid is a mixture of two non-interacting
compounds, it commonly has a melting point broad and lower than
the pure components. Indeed, melting points of both 7 and 8 are
sharp (474–477 K and 453–457 K, respectively,) and much higher
than those of pure starting modules (1, 381–383 K; 2, 356–359 K;
3, 374–478 K). Although the numerous parameters affecting the
crystal packing prevents from quantitatively predicting the
strength of the intermolecular interactions moving from the
observed melting points, the dramatic melting points’ increase in 7
and 8, compared to starting materials, indicates the interactions
driving the assembly of starting modules are quite strong in both
adducts. The FT-IR, 1H, and 19F NMR spectra of 7 and 8 correspond
approximately to the sum of the spectra of the starting modules,
It is common that the number of ligands which surround
anions, and form their coordination sphere, largely exceeds the
requirements of the neutrality principle both in the solid and in
solution [13]. In most cases these ligands are hydrogen bonding
(HB) donors, as in organic materials strong (e.g. –OH, –NH2, etc.)
and weak (e.g. –CH) hydrogen bonding donor sites are ubiquitous.
An iodoperfluorocarbon forming a X-bonded anionic adduct can
thus be interpreted as the iodoperfluorocarbon substituting for a
HB donor in the coordination sphere of the anion. Such a
substitution may occur at one, or some, or all of the sites in the
coordination sphere of the anion. This accounts for the variability
in the number of XBs formed by a given anion.
The X-bonded architectures formed by anions can be divided
into two groups, the heteromeric three component systems and the
heteromeric two component systems [14]. These two groups can be
identified as they present some specific features in relation to the
effect that the composition of the system and the molecular
structure of the interacting partners have on the number of XBs
formed by a given anion. The identification of these two groups
thus helps in identifying the key factors determining the number of
XBs formed by an anion.
the minor changes being consistent with XBs presence. 1H and 19
F
NMR spectra in the presence of 2,2,2-trifluoroethyl ether as
Table 2
˚
XB distances (A), angles (8), and Ri ratios for X-bonded adducts 4–8. Ri = XBi/
(rvdW1 + rvdW2) were the rwdW1 is the van der Waals radius of the halogen (1.98
˚
and 1.85 A for I and Br, resꢁpectively) and rvdW2 is the radius of the halide anion
ꢁ
(2.16, 195, 1.81 A for I , Br , and Clꢁ, respectively, Ref. [16]).
˚
2.1. Co-crystals 7 and 8
Structure XB
X
ꢁꢀ ꢀ ꢀX1 (A) R1
X
ꢁꢀ ꢀ ꢀX2
R2
Xꢀ ꢀ ꢀXꢁꢀ ꢀ ꢀX (8)
˚
The X-bonded co-crystals 7 and 8 have been obtained by mixing
equimolar amounts of 1,4-diiodotetrafluorobenzene (1) and tetra-
n-butylammonium chloride (2) or bromide (3) and by using the
slow evaporation technique. Adducts 7 and 8 are two cases of
heteromeric three component systems which, in general, are
formed when an XB-donor (diiodotetrafluorobenzene 1 in our
cases) self-assembles with a salt (the ammonium chloride and
7a
8
Clꢁꢀ ꢀ ꢀI
2.9758(7)
0.79 3.0906(6) 0.82 108.03(1)
0.81 3.2216(7) 0.82 138.38(2)
Brꢁꢀ ꢀ ꢀI 3.1721(7)
4a
4b
5
6a
Iꢁꢀ ꢀ ꢀI
Iꢁꢀ ꢀ ꢀI
3.548(2)
3.720(2)
0.87 3.652(2)
0.91
0.88
64.77(3)
Iꢁꢀ ꢀ ꢀBr 3.6206(7)
0.99 3.7600(7) 0.94
63.38(2)
Iꢁꢀ ꢀ ꢀI
3.4920(5)
0.84 3.5010(5) 0.85 128.88(1)
a
Data at 90 K.

1174
A. Abate et al. / Journal of Fluorine Chemistry 130 (2009) 1171–1177
internal standard for signal integration [15], revealed the 1:2 and
1:3 ratio were 1:1.
Single crystal X-ray diffraction analysis of 7 and 8 (Table 1) has
given details about the supramolecular organisation of these co-
crystals, confirming that the Clꢁꢀ ꢀ ꢀI and Brꢁꢀ ꢀ ꢀI XBs are responsible
for the self-assembly of the iodofluorocarbon
1 with the
ammonium salts 2 and 3. From the compositional point of view,
the two co-crystals differ only for the halide anion (Clꢁ in 7 and Brꢁ
in 8), but despite this apparently minor difference, the two crystals
are not isostructural; the space groups of 7 and 8 are P21/c and C2/c,
respectively, and non-minor packing differences exist between the
two co-crystals. All the geometric parameters (Table 2) are
completely consistent with X-bonded systems, Xꢁꢀ ꢀ ꢀI XBs being
as short as 0.80 times the sum of van der Waals radius of iodine and
the corresponding halide ionic radius [16].
Both the heteromeric three component systems are charac-
terised by the presence of infinite, one-dimensional, and X-bonded
chains where the diiodotetrafluorobenzene and the halide anions
alternate and behave as ditopic XB donors and acceptors,
respectively (Fig. 1). The coordination spheres of two halides are
completed by one HB with an acidic N-CH2 hydrogen atom. Both
infinite chains adopt a zig-zag arrangement and the Iꢀ ꢀ ꢀXꢁꢀ ꢀ ꢀI angle
is much larger in 7 than in 8. Moreover, in 7 all the benzene rings
are almost perpendicular to the plane containing halide anions,
while in 8 they are alternatively parallel and perpendicular to the
same plane (the perpendicular ring is rotationally disordered and
both the refined models are nearly perpendicular to the halide
plane).
Q1
Fig. 1. Mercury ball and stick plots of supramolecular anions of cocrystals 7 and 8. Colour
code: C, gray; F, green; I, violet; Cl, green; Br, brown. (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of the article.)
Fig. 2. Mercury projections of 4a, 5 and 6 infinite chains in ball and stick style. Colour code: C, gray; F, green; I, violet; N, blue; O, red; H not shown for clarity. (For interpretation
of the references to color in this figure legend, the reader is referred to the web version of the article.)

A. Abate et al. / Journal of Fluorine Chemistry 130 (2009) 1171–1177
1175
2.2. Crystals 4–6
are quite close to the corresponding sum of the van der Waals
radius of bromine and the iodide anion radius. When neutral
electron donors are used, bromoperfluorocarbons are weaker XB
donors than iodoperfluorocarbon analogues and the above-
discussed differences between 4, 6 and 5 shows this is also the
case when anionic electron donors are used.
Ammonium iodides 4–6 are heteromeric two-component
systems, namely they are salts wherein the halogen substituted
cation functions as the XB donor and the anion functions as the XB
acceptor. In heteromeric two-component systems the require-
ments of charge balance heavily affects the number of XBs formed
by the anion as the number of C–X groups in the halocarbon cation
determines the maximum number of XBs the anion can form. This
is the case, among others, in monohalopyridinium halides and
monohaloanilinium halides where the monodentate cation forces
the potentially polydentate anion to form a single XB and gives rise
to discrete adducts [17]. When in the same systems the cation
bears two or three halogen atoms, its ability to function as a di- or
tridentate XB donor frequently can elicits the di- or tridentate
potential of halide anions and infinite chains [18] or (6,3) nets [19]
can be formed, respectively.
As discussed in the Introduction, halide anions frequently have
a complex coordination sphere where XB and HB may coexist. This
is the case for 4a where several short Iꢁꢀ ꢀ ꢀH contacts are present. As
expected, Iꢁꢀ ꢀ ꢀH–N distances are shorter than Iꢁꢀ ꢀ ꢀH–C distances
and the shortest HB involves the inner (NꢁH)+ group (Iꢁꢀ ꢀ ꢀN
˚
distance 3.316 A). Also in 5 and 6, the shortest HB involves the
ꢁ
inner (NꢁH)+ group (I ꢀ ꢀ ꢀN distances are 3.492 and 3.570 A in 5
˚
and 6, respectively) while in 4b the only of Iꢁꢀ ꢀ ꢀN contacts is as long
˚
as 3.709 A.
3. Conclusions
Crystals of ammonium iodides 4–6 suitable for X-ray structure
determination were obtained on crystallization from acetone and
by using the isotherm diffusion technique with chloroform as the
external solvent. The iodotetrafluorophenyl salt 4 afforded two
polymorphs 4a and 4b while the bromotetrafluorophenyl salt 5
and the iodotetrafluorophenyl salt 6 both gave a single polymorph
(Table 1). In the last two compounds and in 4a, iodide anions
function as bidentate XB acceptors and interact with two
halotetrafluorophenyl groups of two different ammonium cations.
One of the two remaining halotetrafluorophenyl groups of
ammonium cations also works as XB donors towards iodide
anions and X-bonded infinite chains are formed where cations and
anions alternate (Fig. 2).
Differently, in 4b both cations and anions are monodentate and
X-bonded discrete ion pairs are formed (Fig. 3). In all these
structures, the overall crystal packing requirements clearly
prevent the XB donor potential of the cation, and of the anion,
from being saturated. In fact, one or two halotetrafluorophenyl
groups (in 4a, 5, and 6 or 4b, respectively) form no XB. It is
interesting to observe that all Iꢁꢀ ꢀ ꢀI interactions in 4a, b and 6 are
much shorter than the sum of the van der Waals radius of iodine
and the iodide anion radius (Table 2) while Iꢁꢀ ꢀ ꢀBr distances in 5
A quite large number of solid supramolecular assemblies have
been obtained on interaction of iodo- and bromoperfluoroarenes
with neutral XB acceptors [20] while few examples are reported
where anionic XB acceptors are used [21]. In this paper we have
described six solid assemblies where the supramolecular archi-
tectures formation is controlled by Iꢁꢀ ꢀ ꢀBr–ArF, Iꢁꢀ ꢀ ꢀI–ArF, Brꢁꢀ ꢀ ꢀI–
ArF, and Clꢁꢀ ꢀ ꢀI–ArF halogen bondings. Clearly, the supramolecular
organization of haloperfluoroarene derivatives can be effectively
driven by halide anions and the Xꢁꢀ ꢀ ꢀX0–ArF supramolecular
synthon (X being the same as or different from X0) seems to be
particularly robust.
In five of the described assemblies halide anions form two XBs
and this behaviour is consistent with generalizations from the
Cambridge Structure Database according to which halide anions
seem to have a bias towards the formation of two or three XBs [14].
In heteromeric three component systems, anions can, in principle,
give any number of XBs, if the stoichiometry in the formed adducts
varies conveniently. In our cases, when ammonium chloride 2 and
bromide 3 self-assemble with diiodotetrafluorobenzene 1, three,
four, or even more XBs can be formed if the halide anion:diiodote-
trafluorobenzene ratio in the resulting co-crystal is not 1:1 (as in 7
and 8) but becomes 1:1.5 or 1:2 etc. The number of XBs given by
the anion is not pre-established also in heteromeric three
component systems, the chemical nature of these systems simply
fixing the maximum number of XBs the anion can give rise too.
Indeed, iodide anions in 4–6 can form one, two, or three XBs if two,
one, or zero halotetrafluorobenzene residues remain uninvolved in
XB formation. The preferential dicoordinate behaviour of halide
anions observed in the structure here described probably derives
from a balance between the inherent coordination profile of halide
anions, the molecular structure of the interacting partners, and
general entropic reasons. If working as tri- or tetra-coordinating
sites, halide anions would probably form two- or three-dimen-
sional networks [8–12], but these processes are much less likely to
occur than the observed formation of infinite chains (one-
dimensional nets).
4. Experimental
4.1. General
Commercial HPLC-grade solvents were used without further
purification. Starting materials were purchased from Sigma–
Aldrich, Acros Organics, and Apollo Scientific. Reactions were
carried out in oven-dried glassware under a nitrogen atmosphere.
Melting points were determined with a Reichert instrument by
observing the melting and crystallising process through an optical
microscope. Thermal analyses were recorded with a Linkam
Fig. 3. Mercury ball and stick structures of 4a and 4b showing the different XB
patterns and cation conformations. Colour code: C, gray; F, yellow; I, violet; N, blue.
(For interpretation of the references to color in this figure legend, the reader is
referred to the web version of the article.)

1176
A. Abate et al. / Journal of Fluorine Chemistry 130 (2009) 1171–1177
DSC600 Stage (temperature range: ꢁ196–600 8C) coupled with the
LN94 cooling system. 1H NMR and 19F NMR spectra were recorded
at ambient temperature with a Bruker AV 500 spectrometer.
Unless otherwise stated, CDCl3 or CD3CN were used as both solvent
l)amine and pentafluorobromobenzene through
strictly similar to that described above for the iodo analogue. 1H
NMR (250 MHz, CDCl3): 4.3 (3H, br, NH), 3.5 (6H, t, J = 6 Hz, NH-
CH2), 2.8 (6H, t, J = 6 Hz, N-CH2), 19F NMR (235 MHz, CDCl3):
ꢁ159.2 (2F, d, J = 18.3 Hz, CF-CN), ꢁ136.3 (2F, d, J = 18.3 Hz, CF-
CBr). IR: max (selected bands) 3396, 2841, 1641, 1493, 1260, 1155,
1076, 956, 827 cmꢁ1
1.0 mL of 57% aqueous HI solution is mixed with 2.0 mL of
MeOH and anhydrous Na2SO4 is added in sufficient amount to
remove water. The solution is filtered and added to a solution of
tris-(2-(2,3,5,6-tetrafluoro-4-bromophenyl)-aminoethyl)amine in
toluene under vigorous stirring. After 30 min at room temperature
the formed precipitate is filtered. m.p. 465–467 K; 1H NMR
a procedure
d
d
and internal standard in 1H NMR spectra
CHD2CN = 1.94). For 19F NMR spectra, CDCl3 or CD3CN were used
(dCHCl3 = 7.26,
d
n
as solvent and CFCl3 as internal standard. All chemical shift values
were given in ppm. IR spectra were obtained in KBr pellets in a
PerkinElmer 2000 FT-IR spectrometer. The values were given in
wave numbers and were rounded to 1 cmꢁ1 upon automatic
assignment. The mass spectra were recorded with a Finnigan Mod
TSQ-70 instrument in FAB mode from a m-NBA matrix. The X-ray
crystal structures were determined using a Bruker Smart Apex
diffractometer.
.
(250 MHz, CD3CN):
t, N-CH2); 19F NMR (235 MHz, CD3CN):
ꢁ139.4 (2F, d, CF-CBr). IR: max (selected bands) 3277, 2955, 1642,
1492, 1162, 957, 829 cmꢁ1
d
5.1 (br, NH), 3.8 (6H, q, NH-CH2), 3.6 (6H,
d
ꢁ159.2 (2F, d, CF-CN),
4.1.1. Co-crystal 7 and 8
n
.
The slow evaporation technique was used. Equimolar amounts
1,4-diiodotetrafluorobenzene (1) and of the tetra-n-butylammo-
nium chloride (2) or bromide (3) are separately dissolved in
acetonitrile at room temperature, only as much solvent as
necessary is used for complete dissolution. The saturated solutions
are mixed in an open clear borosilicate glass vial and placed in a
closed cylindrical wide-mouth bottle containing vaseline oil.
Solvents are allowed to slowly evaporate at room temperature
and to be absorbed by vaseline oil until the white crystals of 7 and 8
are formed. The crystals are filtered off the mother liquor (from
which one to two further crystal fractions could be obtained in the
same manner), washed with n-pentane and rapidly dried in air at
room temperature. 7: mp 474–477 K; IR. nmax (selected bands)
2959, 2873, 1452, 937, 755 cmꢁ1. 8: mp 453–457 K; IR. nmax
4.4. Tris((2-(2,3,5,6-tetrefluoro-4-iodophenoxy)ethoxy)-
ethyl)ammonium iodide (6)
In the first reaction step tris(2-hydroxyethoxyethyl)amine was
synthesized. Na2CO3 (3.0 equiv., 5.46 mmol, 579 mg) is added to a
solution of 2-(2-aminoethoxy)ethanol (1.0 equiv., 1.82 mmol,
192 mg) in 1.5 mL of p-xylene. The resulting heterogeneous
mixture is heated to 120 8C and 2-(2-chloroethoxy)ethanol is
added (2.2 equiv., 4.02 mmol, 500 mg). After stirring overnight the
reaction mixture is filtered, the yellowish solid taken up with EtOH,
filtered again, and the solvent removed. The residue is subjected to
column chromatography (SiO2, MeOH/EtOAc 1:1) to give a pale
(selected bands) 2957, 2875, 1453, 937, 756 cmꢁ1
.
yellow oil (412 mg, 81%). 1H NMR (250 MHz, CDCl3):
d 4.35 (brs,
6H), 3.60–3.55 (m, 12H), 2.65 (t, 6H, J = 5.0 Hz). ESI-MS, positive-
ion mode: m/z 282 [M++H], 304 [M+Na+]. IR: nmax 3282, 2918,
2860, 2820, 1481, 1447, 1360, 1353, 1312, 1286, 1253, 1120, 1105,
1078, 1063, 1044, 1025, 927, 914, 887, 827 cmꢁ1. In the second
step tris(2-hydroxyethoxyethyl)amine (1.0 equiv., 0.370 mmol,
104 mg), iodopentafluorobenzene (9 equiv., 3.33 mmol, 980 mg)
and Cs2CO3 (3 equiv., 1.11 mmol, 384 mg) are heated to 80 8C
under vigorous stirring for 18 h. The product is purified by flash
chromatography (230–400 mesh), increasing the solvent polarity
from pure n-hexane to n-hexane: EtOAc 1:1. Tris((2-(2,3,5,6-
tetrefluoro-4-iodophenoxy)ethoxy)-ethyl)amine is obtained as
slightly yellowish oil (229 mg, 50% yield). 1H NMR (250 MHz,
4.2. Tris-(2-(2,3,5,6-tetrafluoro-4-iodophenyl)-
aminoethyl)ammonium iodide (4)
A mixture of tris(2-aminoethyl)amine (1.0 mmol, 150 mg),
pentafluoroiodobenzene (5.0 mmol, 0.67 mL) and K2CO3 (3.5 mmol,
483 mg) are stirred in 1 mL of refluxing THF for 48 h. The reaction is
monitored by TLC on silica gel plates with CH2Cl2 as eluent. The
solution is filtered and the solvent is evaporated. Flash chromato-
graphy (230–400 mesh) of the dry crude mixture with petroleum
ether: CH2Cl2 3:2 (Rf = 0.56) affords a clean product, which is further
purified by crystallisation from dichloromethane to yield a yellow
solid (0.48 g, 50%). m.p. 351 K; 1H NMR (250 MHz, CDCl3):
br, NH), 3.5 (6H, q, J = 6 Hz, NH-CH2), 2.8 (6H, t, J = 6 Hz, N-CH2); 19
NMR (235 MHz, CDCl3):
ꢁ158.1 (2F, d, J = 19.4 Hz, CF-CN), ꢁ123.5
(2F, d, J = 19.4 Hz, CF-CI). IR: max (selected bands) 3345, 2846, 1638,
1484, 1459, 1153, 1073, 958, 803 cmꢁ1
d
4.3 (3H,
CDCl3):
J = 5.8 Hz), 2.74 (t, 6H, J = 5.8 Hz). 19F NMR (235.3 MHz, CDCl3):
ꢁ121.99 (d, 6F), ꢁ154.58 (d, 6F); ESI-MS, positive-ion mode: m/z
1103 [M+H+], 1126 [M+Na+]. IR:
max (selected bands) 2929, 2869,
d 4.35 (t, 6H, J = 4.5 Hz), 3.76 (t, 6H, J = 4.5 Hz), 3.56 (t, 6H,
F
d
d
n
n
.
1630, 1477, 1357, 1271, 1092, 970, 865, 797 cmꢁ1. 1.0 mL of 57%
aqueous HI solution is mixed with 2.0 mL of MeOH and anhydrous
Na2SO4 is added in sufficient amount to remove water. The
solution is filtered and added to a solution of tris((2-(2,3,5,6-
tetrefluoro-4-iodophenoxy)ethoxy)-ethyl)amine in toluene under
vigorous stirring. After 30 min at room temperature the precipitate
is filtered.
1.0 mL of 57% aqueous HI solution is mixed with 2.0 mL of
MeOH and water is removed by adding sufficient amount of
anhydrous Na2SO4. The solution is filtered and added to a solution
of tris-(2-(2,3,5,6-tetrafluoro-4-iodophenyl)-aminoethyl)amine in
toluene under vigorous stirring. The precipitate 4 is filtered after
30 min at room temperature. Two different thermal events can be
detected (by visual inspection and by DSC analyses) at 327 K
(minor) and 468 K (major); 1H NMR (250 MHz, CD3CN):
NH), 3.8 (6H, brq, NH-CH2), 3.6 (6H, brt, N-CH2); 19F NMR
(235 MHz, CD3CN):
ꢁ158.1 (2F, d, CF-CN), ꢁ126.4 (2F, d, CF-CI).
IR: max (selected bands) 3247, 2889, 1638, 1460, 1364, 1115, 969,
956 cmꢁ1
d
5.1 (br,
4.4.1. Crystal 4a, b, 5 and 6
Crystals suitable for X-ray analyses of 4a,b, 5 and 6 have been
obtained adopting the diffusion technique. The compounds are
dissolved in acetone in an opened vial which is placed in a
closed cylindrical wide-mouth bottle containing chloroform.
Solvents are allowed to mix by slow diffusion in gas and liquid
phase at room temperature until crystals were formed. The
crystals are filtered off the mother liquor (from which one to
two further crystal fractions could be obtained in the same
manner), washed with n-pentane and rapidly dried in air at
room temperature.
d
n
.
4.3. Tris-(2-(2,3,5,6-tetrafluoro-4-bromophenyl)-
aminoethyl)ammonium iodide (5)
Tris-(2-(2,3,5,6-tetrafluoro-4-bromophenyl)-aminoethyl)a-
mine was prepared in 65% isolated yield from tris(2-aminoethy-

A. Abate et al. / Journal of Fluorine Chemistry 130 (2009) 1171–1177
1177
(d) P. Metrangolo, C. Pra¨sang, G. Resnati, R. Liantonio, A.C. Whitwood, D.W. Bruce,
Chem. Commun. (2006) 3290–3292;
(e) G. Marras, P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, New J. Chem. 30 (2006)
1397–1402;
(f) T. Imakubo, N. Tajima, M. Tamura, R. Kato, Y. Nishio, K. Kajita, Synth. Met. 133–
134 (2003) 181–183;
4.4.2. X-ray structures determination
Table 1 reports the crystallographic data. All crystal data were
obtained using a Bruker diffractometer with CCD area-detector and
˚
Mo-Ka radiation (l = 0.71073 A). Structures were solved by SIR2002
[22] and refined by SHELX-97 [23]. A first data collection of 6 was
carried on at room temperature; data were very poor due to the high
librational disorder involving all the three iodotetrafluorobenzenes;
wereport dataof a seconddatacollection atlowtemperate. Alsodata
of 7 were collected at low temperature; data of this structure were
verygood, incontrast ofall the otherthat aremoreorless disordered.
Crystals of4a and 4b werealwaysmixed together, grownepitaxially;
they were always very small and any attempt to grow separately the
twopolymorphsfailed;dataofboththetwostructuresarethenquite
poor. With exclusion of 7, all the structures were refined using
restraints and constraints on the disordered parts.
Copies of the 4a, 4b, 5, 6, 7, and 8 data can be obtained, free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
Cambridge Crystallographic Data Centre, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033; or e-mail:
deposit@ccdc.cam.ac.uk).
(g) T. Imakubo, T. Maruyama, H. Sawa, K. Kobayashi, Chem. Commun. (1998)
2021–2022.
[7] (a) D.W. Bruce, P. Metrangolo, F. Meyer, C. Pra¨sang, G. Resnati, G. Terraneo, A.C.
Whitwood, New J. Chem. 32 (2008) 477–482;
(b) R. Liantonio, P. Metrangolo, F. Meyer, T. Pilati, W. Navarrini, G. Resnati, Chem.
Commun. (2006) 1819–1821;
(c) G. Gattuso, R. Liantonio, P. Metrangolo, F. Meyer, G. Resnati, A. Pappalardo,
M.F. Parisi, T. Pilati, I. Pisagatti, G. Resnati, Supramol. Chem. 18 (2006) 235–246;
(d) A. Farina, S.V. Meille, M.T. Messina, P. Metrangolo, G. Resnati, Angew. Chem.
Int. Ed. 38 (1999) 2433–2436.
[8] (b) H. Bock, S. Holl, Z. Naturforsch. B: Chem. Sci. 56 (2001) 152–163;
(b) A. Casnati, R. Liantonio, P. Metrangolo, G. Resnati, R. Ungaro, F. Ugozzoli,
Angew. Chem. Int. Ed. 45 (2006) 1915–1918;
(c) A. Mele, P. Metrangolo, H. Neukirch, T. Pilati, G. Resnati, J. Am. Chem. Soc. 127
(2005) 14972–14973.
[9] G. Gattuso, A. Pappalardo, M.F. Parisi, I. Pisagatti, F. Crea, R. Liantonio, P. Metran-
golo, W. Navarrini, G. Resnati, T. Pilati, S. Pappalardo, Tetrahedron 63 (2007)
4951–4958.
[10] (a) S.V. Lindeman, J. Hecht, J.K. Kochi, J. Am. Chem. Soc. 125 (2003) 11597–11606;
(b) M. Ghassemzadeh, K. Harms, K. Dehnicke, Chem. Ber. 129 (1996) 115–120.
[11] H. Bock, S. Holl, Z. Naturforsch. B: Chem. Sci. 57 (2002) 843–858.
[12] (a) H.M. Yamamoto, J.I. Yamaura, R. Kato, J. Am. Chem. Soc. 120 (1998) 5905–
5913;
Acknowledgments
(b) S.V. Rosokha, I.S. Neretin, T.Y. Rosokha, J. Hecht, J.K. Kochi, Heteroat. Chem. 17
(2006) 449–459;
(c) T. Nakamoto, Q. Wang, Y. Miyazaki, M. Sorai, Polyhedron 21 (2002) 1299–
1304.
The financial support by Fondazione Cariplo (Project ‘‘Self-
Assembled Nanostructured Materials: A Strategy for the Control of
Electrooptic Properties’’) and Istituto Italiano di Tecnologia
(Politecnico di Milano Unit, Research Line 1) are gratefully
acknowledged.
[13] K. Bowman-James, Acc. Chem. Res. 38 (2005) 671–678.
[14] P. Metrangolo, T. Pilati, G. Terraneo, S. Biella, G. Resnati, CrystEngComm, 2009.
doi:10.1039/b821300c.
[15] M.T. Messina, P. Metrangolo, S. Pappalardo, M.F. Parisi, T. Pilati, G. Resnati, Chem.
Eur. J. 6 (2000) 3495–3500.
[16] L. Pauling, The Nature of the Chemical Bond, 3rd ed, Cornell University Press,
Ithaca, NY, 1960.
References
[17] (a) Z. Dega-Szafran, A. Katrusiak, M. Szafran, J. Mol. Struct. 570 (2001) 165–174;
(b) M. Freytag, P.G. Jones, B. Ahrens, A.K. Fischer, New J. Chem. 23 (1999) 1137–
1139;
(c) Z. Fu, T. Chivers, Can. J. Chem. 84 (2006) 140–145;
(d) L. Gray, P.G. Jones, Z. Naturforsch. B: Chem . Sci. 57 (2002) 61–72.
[18] (a) E. Lopez-Dupla, P.G. Jones, F. Vancea, Z. Naturforsch. B: Chem. Sci. 58 (2003)
191–200;
[1] (a) F.F. Awwadi, R.D. Willet, K.A. Peterson, B. Twamley, Chem. Eur. J. 12 (2006)
8952–8960;
(b) P. Politzer, P. Lane, M.C. Concha, Y. Ma, J.S. Murray, J. Mol. Model. 13 (2007)
305–311;
(c) P. Auffinger, F.A. Hays, E. Westhof, P.S. Ho, Proc. Natl. Acad. Sci. USA 101 (2004)
16789–16794;
(d) J.S. Murray, M.C. Concha, P. Lane, P. Hobza, P. Politzer, J. Mol. Model. 14 (2008)
699–704;
(e) P. Politzer, J.S. Murray, M.C. Concha, J. Mol. Model. 14 (2008) 659–665;
(f) T. Brinck, J.S. Murray, P. Politzer, Int. J. Quant. Chem.: Quant. Biol. Symp. 19
(1992) 57–64.
(b) L. Gray, P.G. Jones, Z. Naturforsch. B: Chem. Sci. 57 (2002) 73–82;
(c) T.A. Logothetis, F. Meyer, P. Metrangolo, T. Pilati, G. Resnati, New. J. Chem. 28
(2004) 760–763.
[19] J. Beck, A. Hormel, M. Koch, Eur. J. Inorg. Chem. (2002) 2271–2275.
[20] (a) P. Metrangolo, F. Meyer, T. Pilati, D.M. Proserpio, G. Resnati, Cryst. Growth
Des. 8 (2008) 654–659;
[2] T. Clark, M. Hennemann, J.S. Murray, P. Politzer, J. Mol. Model. 13 (2007) 291–296.
[3] (a) G. Valerio, G. Raos, S.V. Meille, P. Metrangolo, G. Resnati, J. Phys. Chem. A 104
(2000) 1617–1620;
(b) R. Bianchi, A. Forni, T. Pilati, Chem. Eur. J. 9 (2003) 1631–1638.
[4] (a) P. Metrangolo, T. Pilati, G. Resnati, CrystEngComm 8 (2006) 946–947;
(b) K. Rissanen, CrystEngComm 10 (2008) 1107–1113;
(c) P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem. Int. Ed.
47 (2008) 6114–6127;
(b) C.B. Aakero¨y, J. Desper, B.A. Helfrich, P. Metrangolo, T. Pilati, G. Resnati, A.
Stevenazzi, Chem. Commun. (2007) 4236–4238;
(c) R. Bertani, F. Chaux, M. Gloria, P. Metrangolo, R. Milani, T. Pilati, G. Resnati, M.
Sansotera, A. Venzo, Inorg. Chim. Acta 360 (2007) 1191–1199;
(d) R. Bertani, E. Ghedini, M. Gleria, R. Liantonio, G. Marras, P. Metrangolo, F.
Meyer, T. Pilati, G. Resnati, CrystEngComm 7 (2005) 511–513;
(e) E. Guido, P. Metrangolo, W. Panzeri, T. Pilati, G. Resnati, M. Ursini, T.A.
Logothtis, J. Fluorine Chem. 126 (2005) 197–207;
(f) A. De Santis, A. Forni, R. Liantonio, P. Metrangolo, T. Pilati, G. Resnati, Chem.
Eur. J. 9 (2003) 3974–3983;
(g) R. Liantonio, S. Luzzati, P. Metrangolo, T. Pilati, G. Resnati, Tetrahedron 58
(2002) 4023–4029;
(d) P. Metrangolo, G. Resnati, T. Pilati, R. Liantonio, F. Meyer, J. Polym. Chem. A 45
(2007) 1–15;
(e) P. Metrangolo, H. Neukirch,T. Pilati, G. Resnati, Acc. Chem. Res. 38(2005) 386–395;
(f) P. Metrangolo, G. Resnati, T. Pilati, S. Biella, in: P. Metrangolo, G. Resnati
(Eds.), Halogen Bonding Fundamentals and Applications, 30, Springer, Berlin,
2008, pp.105–136;
(g) P. Metrangolo, T. Pilati, G. Resnati, A. Stevenazzi, Curr. Opin. Coll. Interface
Sci. 8 (2003) 215–222;
(h) A.C. Legon, Angew. Chem. Int. Ed. 38 (1999) 2686–2714;
(i) B.D. Fox, R. Liantonio, P. Metrangolo, T. Pilati, G. Resnati, J. Fluorine Chem. 125
(2004) 271–281.
(h) M.T. Messina, P. Metrangolo, W. Panzeri, T. Pilati, G. Resnati, Tetrahedron 57
(2001) 8543–8550.
[21] (a) T. Caronna, R. Liantonio, T.A. Logothetis, P. Metrangolo, T. Pilati, G. Resnati, J.
Am. Chem. Soc. 126 (2004) 4500–4501;
(b) J. Grebe, G. Geiseler, K. Harms, K. Dehnicke, Z. Naturforsch. B 54 (1999) 77–86;
(c) P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Chem. Commun.
(2008) 1635–1637.
[5] P. Metrangolo, G. Resnati, Chem. Eur. J. 7 (2001) 2511–2519.
[6] (a) P. Metrangolo, G. Resnati, Science 321 (2008) 918;
(b) P. Metrangolo, Y. Carcenac, M. Lahtinen, T. Pilati, K. Rissanen, A. Vij, G. Resnati,
Science 323 (2009) 1461–1464;
[22] M.C. Burla, M. Camalli, B. Carrozzini, G.L. Cascarano, C. Giacovazzo, G. Polidori, R.R.
Spagna, J. Appl. Cryst. 36 (2003) 1103–1112.
[23] G.M. Sheldrick, SHELXL-97. Program for the Refinement of Crystal Structures,
Univ. of Go¨ttingen, German, 1997.
(c) E. Cariati, A. Forni, S. Biella, P. Metrangolo, F. Meyer, G. Resnati, S. Righetto, E.
Tordin, R. Ugo, Chem. Commun. (2007) 2590–2592;