Supramolecular 1D assemblies of polyfluorinated arylenediamines and 18-crown-6

Article abstract of DOI:10.1007/s11172-010-0090-7

Rods (1D assemblies) formed by alternate crown ether and arylenediamine molecules are the motif of the supramolecular architecture of crystals of molecular associates of 18-crown-6 with tetrafluoro-1,4- and -1,3-phenylenediamines, hexafluoro-2,6- and -2,

Full text of DOI:10.1007/s11172-010-0090-7

Russian Chemical Bulletin, International Edition, Vol. 59, No. 2, pp. 382—390, February, 2010
382
Supramolecular 1D assemblies
of polyfluorinated arylenediamines and 18ꢀcrownꢀ6
S. Z. Kusov,a Yu. V. Gatilov,a I. Yu. Bagryanskaya,a G. V. Romanenko,b
T. A. Vaganova,a I. K. Shundrina,a and E. V. Malykhina
aN. N. Vorozhtsov Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences,
9 prosp. Akad. Lavrent´eva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 9752. Eꢀmail: malykhin@nioch.nsc.ru
bInstitute «International Tomography Center»,
Siberian Branch of the Russian Academy of Sciences,
3a ul. Institutskaya, 630090 Novosibirsk, Russian Federation
Rods (1D assemblies) formed by alternate crown ether and arylenediamine molecules are
the motif of the supramolecular architecture of crystals of molecular associates of 18ꢀcrownꢀ6
with tetrafluoroꢀ1,4ꢀ and ꢀ1,3ꢀphenylenediamines, hexafluoroꢀ2,6ꢀ and ꢀ2,7ꢀnaphthylenediꢀ
amines. Molecules in the assemblies are arranged via Hꢀbond predominantly between the
crown ether oxygen atoms and the polyfluoroarene amino group hydrogen atoms. Influence of
the amino groups mutual arrangement and the aromatic framework size on the crystal suꢀ
pramolecular architecture is characterized. Specific melting heats of the crystalline 1D assemꢀ
blies of paraꢀ and pseudoꢀparaꢀarylenediamines are higher than those of metaꢀ and pseudoꢀ
metaꢀanalogs; the associates having higher melting heats selectively crystallize from solutions
of isomeric phenyleneꢀ or naphthylenediamine mixtures.
Key words: molecular crystals, supramolecular architecture, Xꢀray diffraction analysis,
polyfluorinated compounds, arylenediamines, crown ether, melting heat, highꢀperforꢀ
mance materials.
Crown ethers, in particular, 18ꢀcrownꢀ6, and comꢀ
assemblies are formed at least by two different synthons.
pounds containing an amino group form molecular crysꢀ
tals, which is confirmed by reproducible stoichiometry of
the components and melting points differing from characꢀ
teristics of the individual compounds.1 The Cambridge
Structural Database2 contains information on structures
of 70 associates of 18ꢀcrownꢀ6 with different amines. In
them, the amino group is bonded by the hydrogen bond
with one or two oxygen atoms of the crown ether.3 And in
the crystals, there are represented the amine—crown or
amine—crown—amine groups isolated in space (the stoꢀ
ichiometry of the components is 1 : 1 and 1 : 2, respectively).
In the latter case, two molecules of the amino compound
flank the plane of the crown ether.4 The presence of two
amino groups in one molecule gives an opportunity to
form polymolecular associates, i.e., oneꢀdimensional suꢀ
pramolecular 1D assemblies, which motif is the rod (chain,
line) from alternating units ...—crown—diamine—... Among
the known associates involving 18ꢀcrownꢀ6, examples of
1D assemblies based exclusively on the supramolecular
synthon5 Ccrown—O...H—N are not numerous: these are
associates of bisꢀthiourea (H2NC(S)NHNHC(S)NH2)
and dithiooxamide (H2NC(S)C(S)NH2).6 Most of the 1D
For example, in the associate of 18ꢀcrownꢀ6 with thioꢀ
urea7 of stoichiometry 1 : 2, the synthon C=S...H—N
formed by two thiourea molecules is also involved into the
construction of the elemental unit of the rod. The authors
in work8 consider the fragment Ccrown—O...H—CH2—N
as the second synthon forming the rod in the methylthioꢀ
urea associate, i.e., they suggest involvement of the "acidꢀ
ic" hydrogen of the methyl group into the formation of
a hydrogen bond. In the associate of 18ꢀcrownꢀ6 with
2,4ꢀdinitrophenylhydrazine9 of stoichiometry 1 : 2, the
synthon Ccrown—O...H—N is combined with the πꢀstacꢀ
king interaction of the phenyl rings. Considerable amount
of associates of 18ꢀcrownꢀ6 and amines are twoꢀ and threeꢀ
dimensional constructions.
From the point of view of crystal engineering, supramoꢀ
lecular architecture based on 1D assemblies is promising
since it suggests anisotropy of physical properties of the
crystals, which is the higher the less is the interaction of
the 1D assemblies between each other. This circumstance
can be used in the development of highꢀtech functional
materials and suggests the urgency of design of organic
crystals based on 1D assemblies, first of all those, which,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 375—372, February, 2010.
1066ꢀ5285/10/5902ꢀ0382 © 2010 Springer Science+Business Media, Inc.

Supramolecular 1D assemblies
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
383
due to the specificity of the chemical structure of moleꢀ
culeꢀcomponents, possess additional possibilities for transꢀ
mission of effects along the rod. Such a possibility is proꢀ
vided, for example, by the conjugation chain involving the
aromatic ring and synthons forming the rod, due to which
it is able to transmit a signal (for example, disturbance of
electron density) to the other end of the supramolecular
assembly with insignificant loss of its intensity.
Earlier,10,11 we have reported on the formation of twoꢀ
component crystalline associates of 18ꢀcrownꢀ6 and polyꢀ
fluorinated paraꢀ and metaꢀphenylenediamines or pseuꢀ
doꢀparaꢀ and pseudoꢀmetaꢀnaphthylenediamines from soꢀ
lutions in tertꢀbutyl methyl ether. When amount of the
crown ether is insufficient, crystallization of the mixture
of isomeric arylenediamines occurs selectively with reꢀ
spect to paraꢀ and pseudoꢀparaꢀisomers. The effect of "moꢀ
lecular recognition" found empirically was used during
preparation of polyfluoroarylenediamines in the highly
pure state with subsequent use in the synthesis of polyimꢀ
ides,12 analogs of known material for optical applicaꢀ
tions13. In addition, these pairs of compounds a priori
meet requirements for the construction of crystalline 1D
assemblies.
The purpose of the present work consists in the revealꢀ
ing specificities of supramolecular architecture of crysꢀ
tals of twoꢀcomponent associates of 18ꢀcrownꢀ6 and polyꢀ
fluorinated arylenediamines, as well as possible reasons of
isomeric selectivity during formation of crystal phase.
In this work, we used tetrafluoroꢀ1,4ꢀ and ꢀ1,3ꢀpheꢀ
nylenediamines, hexafluoroꢀ2,6ꢀ and ꢀ2,7ꢀnaphthyleneꢀ
diamines (paraꢀ, metaꢀ, pseudoꢀparaꢀ, and pseudoꢀmetaꢀ
isomers 1—4, respectively) and 18ꢀcrownꢀ6. Such a set of
aromatic substrates allows us to characterize the influence
of the aromatic framework size and mutual arrangement
of the amino groups on the supramolecular architecture
and properties of the crystalline associates.
Results and Discussion
Xꢀray diffraction analysis of associates. Crystal asꢀ
sociates of 18ꢀcrownꢀ6 and tetrafluoroꢀparaꢀphenylꢀ
enediamine (C12H24O6•C6H4N2F4 (Kꢀ1)), tetrafluoroꢀ
metaꢀphenylenediamine (C12H24O6•C6H4N2F4 (Кꢀ2)),
hexafluoropseudoꢀparaꢀnaphthylenediamine (C12H24O6•
•C10H4N2F6 (Кꢀ3)) and hexafluoropseudoꢀmetaꢀnaphthꢀ
ylenediamine (C12H24O6•2C10H4N2F6 (Кꢀ4)) are formed
upon mixing solutions of equimolar amounts of the comꢀ
ponents in lowꢀpolar aprotic solvents. Associates Кꢀ1—Кꢀ3
have stoichiometry of 1 : 1, in associate Кꢀ4, the proporꢀ
tion 18ꢀcrownꢀ6 : 4 is 1 : 2. The crystallographic data and
parameters of the structure refinements are given in Table 1.
Singleꢀcrystal Xꢀray diffraction analysis of the strucꢀ
ture of compound 1 was reported in Ref. 14, the data on
the structures of compounds 2—4 are absent. The bond
distances Carom—Carom, Carom—F and Carom—N in the
free diamine 1 and that included into associate Кꢀ1 are
approximately the same. Therefore, it can be suggested
that the inclusion of molecules of polyfluoroarylenediꢀ
amines 2—4 into the molecular associates with the crown
ether will not considerably affect the interatomic distancꢀ
es in the molecules. In the naphthylenediamines 3 and 4
associated with 18ꢀcrownꢀ6, there is realized the alternaꢀ
tion of the bond distances Carom—Carom of the naphthaꢀ
lene framework (see, for example, Ref. 15). Note that in
all the arylenediamines under consideration in the associꢀ
ates Кꢀ1—Кꢀ4 and in the free diamine 1,14 the amino
groups have a pyramidal structure, as well as in the crysꢀ
talline adduct of 3,5ꢀdinitroꢀ1ꢀcyanobenzene and 1,3ꢀpheꢀ
nylenediamine.16 The amino groups in associate Кꢀ3 have
the most planar structure. This is also indicated by the
calculations by the DFT PBE/3Z method for compounds
1—4 (in the gas phase).
Supramolecular architecture of associates Кꢀ1—Кꢀ4
has a general motif, the rods from the alternating moleꢀ
cules of arylenediamine and crown ether (Figs 1—4), the
geometric characteristics of which are given in Table 2.
The mutual coordination of the molecules in the rods is preꢀ
dominantly determined by the synthon Ccrown—O...H—N
(the geometrical parameters are given in Table 3). The
contact Carom—F...H—Caliph with the distances less than
the sum of the Van der Waals radii is found only in the rods
of associates Кꢀ1 and Кꢀ4 (see Table 3).
The units and rods in the crystals of associates of paraꢀ
phenylenediamine Кꢀ1 and pseudoꢀparaꢀnaphthyleneꢀ
diamine Кꢀ3 have virtually identical spatial structure
(cf. Figs 1 and 3). The molecules of diamine and 18ꢀcrownꢀ
6 in associate Кꢀ1 are arranged in special positions with
the symmetry C2h, whereas in associate Кꢀ3, with the symꢀ

384
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Kusov et al.
Table 1. Crystallographic data and parameters of refinement of the structure of associates Кꢀ1—Кꢀ4
Parameter
Кꢀ1
Кꢀ2
Кꢀ3
Кꢀ4
Chemical formula
Molecular weight
Crystal system
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
C18H28F4N2O6
444.42
Monoclinic
C2/m
8.243(4)
16.916(8)
8.857(4)
90
115.997(7)
90
C18H28F4N2O6
444.42
Monoclinic
P21/n
C22H28F6N2O6
530.46
Monoclinic
C2/c
20.617(2)
9.845(1)
15.854(2)
90
129.840(6)
90
C32H32F12N4O6
796.62
Triclinic
P–1
7.565(7)
16.10(1)
18.31(2)
90
100.33(2)
90
2194(3)
4
1.346
9.322(1)
9.330(1)
11.037(1)
95.191(7)
108.697(8)
107.583(8)
848.0(2)
1
γ/deg
V/Å3
1110.1(9)
2
1.330
2470.9(5)
4
1.426
Z
dcalc/g cm–3
1.560
1.51
μ/cm–1
1.20
1.21
1.32
Number of measured/indeꢀ
pendent reflections
Number of reflections
with I > 2σ(I)
Number of refining
parameters
R1 for I > 2σ(I)
wR2 for all the reflections
GOOF
4298/833
16362/3192
2494/2425
3512/3297
742
102
1996
271
1334
188
1962
273
0.0432
0.1038
1.125
0.0916
0.2236
1.089
0.0919
0.3109
1.114
0.0613
0.2200
1.028
metry Ci. The conformation of the crown ether in associꢀ
is shifted to the periphery, approximately half of the moleꢀ
cule goes beyond the perimeter of the rod crossꢀsection
(see Fig. 2, c), but the amino groups are arranged close
enough to its axis. The length of the rod elemental unit in
Кꢀ2 is less than in Кꢀ1. It is obvious that such a structure
of 1D assembly is due to the mutual metaꢀarrangement of
the amino groups in phenylenediamine 2.
Associate Кꢀ4 differs in the stoichiometry of the comꢀ
ponents from those considered above (see Fig. 4, a), howꢀ
ever, a supramolecular 1Dꢀmotif with the inꢀpairs parallel
arrangement of the components similar to that in associꢀ
∨
ate Кꢀ1 is close to the classic crown D3d: 3(TGT,TGT).17
There is a disorder of positions of some atoms of 18ꢀcrownꢀ
6 in associate Кꢀ3, but the conformation of the main part
∨
of the molecule is also close to D3d: 3(TGT,TGT). The
centers of masses of the molecules of the rods Кꢀ1 and Кꢀ3
components are on the rod axis, the slopes of the planes of
18ꢀcrownꢀ6 and arylenediamines to the axis are different
(see Table 2; Fig. 5, a). It cannot be excluded that the
angle formed by the planes of the crown ether and aryleneꢀ
diamine molecules is affected by the degree of pyramidalꢀ
ity of the amino groups and is optimum from the point of
view of the hydrogen bonding efficiency. The arylenediꢀ
amine molecules do not virtually go beyond the perimeter
of the rod crossꢀsection (see Figs 1, c and 3, c). The length
of the elemental unit in the assemblies (see Table 2) is
determined by the size of the aromatic framework of the
diamine: the distance between molecules of the crown
ether in the rod increases from Кꢀ1 to Кꢀ3.
Table 2. Supramolecular parameters of rods of associates
Кꢀ1—Кꢀ4
Parameter
Кꢀ1
Кꢀ2
Кꢀ3
Кꢀ4
Direction
of the rod axis
a + c
b
a + b, a + b + c
a – b
The structure of the 1D assembly of associate Кꢀ2 is
given in Fig. 2. The molecule of 18ꢀcrownꢀ6 is in the
conformation Ci: 2(TGT,TGT,GGT)17 and is placed in
the center of symmetry, whereas the molecule of diamine
2 is in general position. The mutual arrangement of the
components in the rod considerably differs from that in
Кꢀ1 and Кꢀ3: the planes of the neighboring crown ether
molecules in Кꢀ2 are arranged the zigzag (see Figs 2, b and
5, b and Table 2). The plane of the molecule of phenyleneꢀ
diamine 2 is parallel to the rod axis, the center of its mass
Length of the rod
unit/Å
9.08
77
8.05
11.4
12.6
Slope of the plane of
18ꢀcrownꢀ6 to the rod
axis/deg
37,
143
71
82
Slope of the plane of
diamine to the rod
axis/deg
20
0
0
77
0
21
0
Angle between the
18ꢀcrownꢀ6 planes/deg
107

Supramolecular 1D assemblies
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
385
ates Кꢀ1 and Кꢀ3 is present in the structure of its crystals
as well (see Figs 4, b and 5, c). Two molecules of diamine
4 bound by the πꢀstacking interaction are present between
the molecules of crown ether in the rod: the centers of
masses of the molecules are displaced from the rod axis to
the periphery, the planes of the molecules are arranged by
the type «faceꢀtoꢀface» with the shift (the interplane and
intercentroid distances are 3.33 and 3.59 Å, respectively)
and turn by 180°. Such distances are characteristic of the
πꢀstacking, in which the pairs arene—polyfluoroarene are
involved (the stabilization energy is ~18—29 kJ mol–1 18
)
a
or, considerably more seldom, polyfluoroarene—polyfluꢀ
oroarene (the stabilization energy ~16—23 kJ mol–1).19
C(3A)
O(3A)
C(2A)
F(2)
C(2)
a
N(1)
C(1)
C(1A)
O(1A)
C(1B)
O(2B)
N(2)
C(2B)
C(3B)
F(3)
C(3)
O(6B)
C(6B)
F(4)
C(4B)
O(4B)
C(2)
C(5B)
C(4)
C(1)
b
F(1)
C(4A)
O(4A)
C(5)
C(3A)
C(6)
N(6)
F(5)
C(5A)
C(2A)
C(1A)
a
O(6A)
C(6A)
b
O(2A)
0
b
a
c
c
b
0
c
c
Fig. 1. Structure of associate Кꢀ1: the fragment of the rod (here
and in Figs 2—4 the numeration is given for atoms in the indeꢀ
pendent part of the unit cell) (a); plane of the rods, the view
from above (b); planes of the rods, the view along the rod axis (c).
Fig. 2. Structure of associate Кꢀ2: fragment of the rod (a); plane
of the rods, the view from above (b); planes of the rods, the view
along the rod axis (c).

386
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
Kusov et al.
It cannot be excluded that the πꢀstacking in a certain
degree is due to the dipoleꢀdipole interaction18,20 of two
molecules of diamine 4. Static polarization of the electron
density, when the amino groups in the naphthalene frameꢀ
work have the pseudoꢀmetaꢀarrangement, develops a diꢀ
pole along the bond C(9)—C(10); different directions of
the dipoles in the molecules turned by 180° provides their
mutual πꢀcoordination. Two amino groups from different
molecules of the diamine, imitating pseudoꢀparaꢀarranged
substituents, are involved into the formation of the hydroꢀ
gen bonds with molecules of 18ꢀcrownꢀ6 (see Fig. 5, c).
This is the reason that the supramolecular structure of 1D
assembly Кꢀ4 based on the pseudoꢀmetaꢀnaphthylenediꢀ
amine is similar to the structure of associates Кꢀ1 and Кꢀ3
based on the paraꢀ and pseudoꢀparaꢀarylenediamines (the
inꢀpairs parallel arrangement of the molecules), rather than
to the structure of associate Кꢀ2 based on the metaꢀpheꢀ
nylenediamine (the zigzag arrangement of the molecules).
The configuration of the "dimer" formed by the molecules
of diamine 4 and its slope to the rod axis are so that the
length of the elemental unit of the rod Кꢀ4 is somewhat
larger than the length of the unit of the rod Кꢀ3.
C(14A)
C(13A)
C(13)
a
a
C(12)
O(1)
C(14)
F(1)
C(6A)
C(6B)
F(3)
O(2)
N(1)
C(1)
C(2)
F(2)
C(3)
C(11)
C(5)
C(4)
O(2A)
C(15)
O(3)
C(7)
C(8)
C(16)
O(1)
F(6)
C(1)
N(2)
F(1)
N(1)
C(7)
C(5)
F(5)
C(2)
C(8) C(9)
C(3)
F(2)
C(9)
C(4)
C(11A)
C(10B)
F(4)
C(10)
O(2)
F(3)
F(2A)
C(10A)
O(3B)
C(11)
O(3A)
a
b
b
0
c
0
b
a
b
c
c
c
Fig. 3. Structure of associate Кꢀ3: fragment of the rod (a); plane
of the rods, the view from above (b); planes of the rods, the view
along the rod axis (c).
Fig. 4. Structure of associate Кꢀ4: fragment of the rod (a); plane
of the rods, the view from above (b); planes of the rods, the view
along the rod axis (c).

Supramolecular 1D assemblies
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
387
Table 3. Parameters of interactions Ccrown—O...H—N and
Carom—F...H—Caliph in the rods of associates Кꢀ1—Кꢀ4
the fluorine atom of the molecule of arylenediamine from
the neighboring rod (N(1)—H(1A)...F(4)ꢀCarom), which
is not comparable in its strength21 with the interactions
supporting the structure of the rod. To sum up, the suꢀ
pramolecular architecture of associates Кꢀ1—Кꢀ4 have the
motif not higher than 1D supplemented by a weak interꢀ
rod interaction in associate Кꢀ4.
Assoꢀ
ciate
Interꢀ
action
lX...Y
lH...Y
Angle
X—H...Y/deg
Å
Кꢀ1 N(1)—H(11)...O(3A) 3.242(3) 2.45(2)
C(3A)—H(3AB)...F(2) 3.354(4) 2.44(3)
Кꢀ2 N(2)—H(2B)...O(6B) 3.182(6) 2.45
N(2)—H(2A)...O(6B) 3.353(7) 2.55
N(6)—H(6A)...O(2A) 3.213(6) 2.40
N(6)—H(6B)...O(2A) 3.162(6) 2.42
160(2)
152(2)
144
156
157
Mutual arrangement of the 1D assemblies in crystals is
different. In the crystals Кꢀ3, alternating layers of the parꢀ
allel rods are clearly observed; rods are placed in the neighꢀ
boring layers in the directions a + b and a – b at an angle
51° (see Fig. 3, c and Tables 2 and 4). Units in the neighꢀ
boring rods are displaced with respect to each other both
inside the layer and between the layers and are arranged by
the type "ledgeꢀtoꢀcavity" (ledge is the crown ether moleꢀ
cule). This decreases the distance between the rod axes,
which, as a result, becomes smaller than the rod diameter.
In associates Кꢀ1, Кꢀ2, and Кꢀ4, the rods have a parallel
placement in all the volume of crystals. Mutual displaceꢀ
ment of the units in the neighboring rods of associates Кꢀ1
and Кꢀ4 reaches half of the unit length. In associate Кꢀ2,
the molecules of metaꢀphenylenediamine play the part of
ledges (see Fig. 2, c), the zigzag placement of the rods in
crystal Кꢀ2 is realized without displacement of the units
with respect to each other.
In accordance with principle of close packing,22 a criꢀ
terion of layers in crystals Кꢀ1, Кꢀ2, and Кꢀ4 is the maxiꢀ
mum density of the supramolecular elements in the plane
and/or the maximum rarefaction between the elements
belonging to the neighboring layers. Using this criterion,
it is possible to separate layers in Кꢀ1 — plane a + c, a – c,
in Кꢀ2 — plane b, a, in Кꢀ4 — plane a + b + c, a – b + c
(see Table 4). This is the plane in Кꢀ4, in which the interꢀ
rod contact is realized. It should be noted, however, that
in associate Кꢀ3, in which arrangement of layers is obviꢀ
ous and defined by other criterion, i.e., by parallelity of the
rods (see above), the distance between the rods in the layer
is larger than the distance between the rods in the neighꢀ
boring layers (6.49 Å).
145
Кꢀ3 N(1)—H(1B)...O(1)
N(1)—H(1A)...O(1)
Кꢀ4 N(2)—H(2A)...O(3)
N(2)—H(2B)...O(3)
3.14(1)
2.31(7)
163(5)
170(6)
171(5)
161
3.408(8) 2.57(5)
3.211(5) 2.36(5)
3.559(6) 2.69(4)
C(16)—H(16A)...F(5) 3.272(5) 2.49
C(12)—H(12A)...F(2) 3.386(6) 2.50
138
151
C(11)—H(11B)...F(2) 3.42
2.57
146
The rods of associates Кꢀ1—Кꢀ3 are based on the
synthon of the same type, i.e., Ccrown—O...H—N. The
πꢀstacking interaction of two molecules of naphthyleneꢀ
diamines are additionally involved into the formation of
the rod Кꢀ4. Shortened contacts between the atoms of the
neighboring rods in the crystals of associates Кꢀ1—Кꢀ3
are absent. In the crystal Кꢀ4, there is present a shortened
contact between the hydrogen atom of the amino group,
which is not involved into the formation of the rod, and
a
b
Table 4. Supramolecular parameters of the planes formed by the
rods in the crystals of associates Кꢀ1—Кꢀ4
Parameter
Кꢀ1
Кꢀ2
Кꢀ3
Кꢀ4
Directions
of the planes
a + c,
a – c
b, a
a + b, a + b + c,
a – b
8.83
a – b + c
8.38
c
Distances between
the rod axes/Å
7.22
7.56
~0
Shift of the rods
with respect to each
other/Å
3.96
4.24
51.3
4.09
0
Angles between rods
in the neighboring
planes/deg
0
0
Fig. 5. Graphical picturing of the supramolecular 1Dꢀmotifs:
associates Кꢀ1 and Кꢀ3 (a); Кꢀ3 (b) and Кꢀ4 (c).

388
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Kusov et al.
Thermal analysis of associates Кꢀ1—Кꢀ4. The study of
going from Кꢀ1 to Кꢀ3, due to the increase in the linear
sizes of the units. Associates Кꢀ3 and Кꢀ4, characterized
by the inꢀpairs parallel structure of the rod and comparaꢀ
ble linear sizes of the unit, have close values of ΔHL. Howꢀ
ever, in this case it is necessary to take into account the
different stoichiometry of the unit of associate Кꢀ4, as well
as additional involvement of the synthon of another type
(πꢀstacking) and half as large than in Кꢀ1—Кꢀ3 amount of
hydrogen bonds per one molecule of diamine. For examꢀ
ple, allowance for the difference in stoichiometry of the
components can be made by calculation of the melting
heat of associate Кꢀ4 per one molecule of diamine (ΔHL*)
(see Table 5). The value of ΔHL* of associate Кꢀ4 is less
than ΔHL of associate Кꢀ3, which is symbatic to the selecꢀ
tivity of crystallization of these associates from solution
when shortage of the crown ether is present.
It should be note that the ratio of values ΔHW found for
the pairs of isomers (Кꢀ1 vs Кꢀ2 and Кꢀ3 vs Кꢀ4) does not
agree with the common concept on the influence of mutuꢀ
al arrangement of amino groups in the aromatic frameꢀ
work on the N—H bond polarization degree, as well as on
the strength of the hydrogen bond formed by this fragꢀ
ment.23 Obviously, the dependence of the crystals decomꢀ
position heat on this factor is mediated by the effects of
the crystal lattice.
thermal characteristics of associates Кꢀ1—Кꢀ4 was perꢀ
formed in order to find a dependence between the melting
(decomposition) heats of crystals and the supramolecular
architecture and possible reasons of the isomeric selectiviꢀ
ty during crystallization from solutions. Method of differꢀ
ential scanning calorimetry (DSC) was used to determine
characteristic temperatures of the phase transition crysꢀ
talꢀtoꢀliquid and the value ΔHW (specific melting weight
heat), which is used to calculate the value ΔHL (melting
heat per unit) (Table 5). It was established that the value
ΔHW and melting points of crystals are reproducible in
cyclic heating—cooling regime.
The value ΔHW for associate Кꢀ1 is higher than for
associate Кꢀ2 (paraꢀ and metaꢀphenylenediamines, respecꢀ
tively), whereas for associate Кꢀ3 it is higher than for assoꢀ
ciate Кꢀ4 (pseudoꢀparaꢀ and pseudoꢀmetaꢀnaphthyleneꢀ
diamines, respectively). Comparison of these results with
the data on the selectivity of formation of crystals of assoꢀ
ciates from solutions of arylenediamine mixtures if shortꢀ
age of the crown ether is present (associate Кꢀ1 predomiꢀ
nantly crystallizes from the mixture 1 + 2,10 whereas assoꢀ
ciate Кꢀ3 from the mixture 3 + 4 (see Ref. 11)) indicates
that crystallization from the solution takes place selecꢀ
tively in favor of the structure with higher heat of decomꢀ
position of the crystal lattice. Consequently, for the lowꢀ
polar solvents the difference in contribution of isomers
desolvation to the values of crystal formation heat can be
neglected and the value ΔHW can be considered as a meaꢀ
sure of selectivity of crystallization of isomeric diamine
associates.
In conclusion, in this work we suggested a new group
of objects for the crystals engineering — the associates of
polyfluoroarylenediamines with 18ꢀcrownꢀ6, which are
supramolecular 1D assemblies based on the synthon
C
crown—O...H—N; the πꢀstacking of two aromatic moleꢀ
cules is also involved into the formation of assembly Кꢀ4.
We characterized the influence of mutual arrangement of
the amino groups in the aromatic framework and its size
on the architecture of crystals. In the associates of pheꢀ
nylenediamines going from paraꢀ (Кꢀ1) to metaꢀisomer
(Кꢀ2), the inꢀpairs parallel arrangement of the molecules
in the rod is changed to the zigzag one; contrary to this, in
the associates of naphthylenediamines going from pseuꢀ
doꢀparaꢀ (Кꢀ3) to pseudoꢀmetaꢀisomer (Кꢀ4) the inꢀpairs
parallel arrangement of the component planes in the rod
remains the same due to the πꢀstacking of two molecules
of arylenediamine and involvement of two amino groups
from different molecules, imitating the pseudoꢀparaꢀarranꢀ
ged substituents, into the formation of the rod. With inꢀ
crease of the linear sizes of the aromatic framework going
from paraꢀ (Кꢀ1) to pseudoꢀparaꢀarylenediamine (Кꢀ3),
the structure of the rod is retained, but disparalleling of the
rods in the neighboring layers occurs; in contrast to this,
the stoichiometry and structure of the rod change going
from metaꢀ (Кꢀ2) to pseudoꢀmetaꢀarylenediamine (Кꢀ4).
On comparison of melting heats values for all the set of
associates Кꢀ1—Кꢀ4, it is correct to operate with the valꢀ
ues ΔHL (see Table 5). Analysis of the ΔHL dependence on
the supramolecular architecture of 1D assemblies shows
that the decrease of this value from Кꢀ1 to Кꢀ2 is apparꢀ
ently due to the change in the mutual arrangement of the
molecules in the rod from the inꢀpairs parallel to the zigꢀ
zag; whereas in the case of rods of the same structure
Table 5. Melting points and melting heats of associates
Кꢀ1—Кꢀ4 according to the DSC
Assoꢀ
ciate
Tonset
Tmax
ΔHW
ΔHL (ΔHL*)
/J g–1
/kJ mol–1
°C
Кꢀ1
Кꢀ2
Кꢀ3
Кꢀ4
129.7
89.5
160.9
124.9
132.9
92.5
165.6
131.7
170
123
108
78
75.5
54.7
57.3
62.1 (41.4)
Note. Tonset is the temperature of the extrapolated onset of meltꢀ
ing, Tmax is the melting peak temperature, ΔHW is the specific
weighting melting heat, ΔHL is the melting heat calculated on
the weight of unit, ΔHL* is the melting heat calculation on the
weight of unit of Кꢀ4 lacking one diamine molecule.
Experimental
1
H and 19F NMR spectra were recorded on a Bruker AVꢀ300
spectrometer, signals for the residual protons in the deuterated

Supramolecular 1D assemblies
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
389
solvent and C6F6, respectively, were used as references. IR specꢀ
tra were recorded on a Bruker Vectorꢀ22 spectrometer in the
diffuse reflection mode. Thermal analysis was performed on a
STA 409 PC Luxx Netzch synchronous thermal analyzer. Heatꢀ
ing of the samples was performed under argon atmosphere at the
rate 10 К min–1 to the temperature below the onset of the mass
loss. Melting points for the samples were determined according
to GOST 18995.4ꢀ73 on a Tempꢀ2 apparatus in automatic mode.
Quantum chemical calculations for the gas phase was performed
by the PBE density functional method with the 3z basis using the
PRIRODA program.24
Synthesis of crystalline associates of polyfluoroarylenediamines
1—4 with 18ꢀcrownꢀ6 (general procedure). A solution of
18ꢀcrownꢀ6 (2.8 g, 10.6 mmol) in tertꢀbutyl methyl ether
(10 mL) was added to a solution of polyfluorophenylenediamine
(10 mmol, 1.7 g of diamines 1 and 2, 2.7 g of diamines 3 and 4)
in tertꢀbutyl methyl ether (10 mL) at room temperature
with stirring. The mixture was kept for 1 h under these conꢀ
ditions. A precipitate formed was filtered off, washed with
tertꢀbutyl methyl ether, and dried. Monocrystals for Xꢀray difꢀ
fraction were grown from the solutions of the associates in
chloroform.
P4 diffractometer (MoꢀKα radiation, θ/2θꢀscanning, θ < 26°) at
room temperature. The crystallographic data and parameꢀ
ters of refinement of the structures are given in Table 1.
The structures were solved by the direct method and refined in
the anisotropicꢀisotropic approximation using the SHELXLꢀ97
program.25 Positions of the hydrogen atoms of 18ꢀcrownꢀ6
in crystals Кꢀ2—Кꢀ4 were specified geometrically and reꢀ
fined using the riding model. In crystal Кꢀ3, a disorder of
a number of crown ether atoms in proportion 0.37 : 0.63 was
observed, which was the reason to set geometrical limitations in
the refinement. In crystal Кꢀ4, a number of crown ether atoms
are disordered in proportion 0.23 : 0.77. The minor part of the
disordered atoms in Кꢀ3 and Кꢀ4 was refined in isotropic apꢀ
proximation. Geometrical analysis was performed using the
PLATON program.26
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1635 (Carom—Carom); 1109 (Caliph—O). Found (%): C, 48.70;
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1H NMR (DMSOꢀd6), δ: 3.50 (s, 24 H, CH2); 5.74 (br.s,
4 H, NH2). 19F NMR (DMSOꢀd6), δ: 8.1 (m, 2 F, F(4), F(8));
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3435, 3342, 3228 (NH2); 2884, 1532, 1469 (Caliph—H); 1616,
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Associate of hexafluoroꢀ2,7ꢀnaphthylenediamine (4) with
18ꢀcrownꢀ6, 2 : 1 (Кꢀ4). The yield was 58%, m.p. 126—127 °C.
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NH2). 19F NMR (DMSOꢀd6), δ: 5.3 (m, 4 F, F(3), F(6)); 9.2
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Received January 20, 2009;
in revised form April 30, 2009