Design of zigzag-like supramolecular 1D assemblies of polyfluorinated meta-arylenediamines and 18-crown-6

Article abstract of DOI:10.1016/j.molstruc.2011.03.067

According to the X-ray crystal data, 1D assemblies formed by alternate arylenediamine and crown ether molecules are the motif of the supramolecular architecture of crystal associates of 18-crown-6 and polyfluorinated meta-arylenediamines, i.e. 2,4,5-trifl

Full text of DOI:10.1016/j.molstruc.2011.03.067

Journal of Molecular Structure 995 (2011) 109–115
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Design of zigzag-like supramolecular 1D assemblies of polyfluorinated
meta-arylenediamines and 18-crown-6
⇑
Tamara A. Vaganova, Soltan Z. Kusov, Inna K. Shundrina, Yurij V. Gatilov, Evgenij V. Malykhin
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentiev Avenue 9, 630090 Novosibirsk, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
According to the X-ray crystal data, 1D assemblies formed by alternate arylenediamine and crown ether
molecules are the motif of the supramolecular architecture of crystal associates of 18-crown-6 and
polyfluorinated meta-arylenediamines, i.e. 2,4,5-trifluoro-, tetrafluoro-, 2,5,6-trifluoro-4-trifluoro-
methyl-, 2,5-difluoro-4,6-bis(trifluoromethyl)-1,3-phenylenediamines, and hexafluoro-2,7-naphthylen-
ediamine. Molecules in the assemblies are coordinated by means of the hydrogen bond between the
oxygen atoms of the crown ether and the hydrogen atoms of the polyfluoroarene amino groups. Due
to the mutual meta-location of amino groups in a rigid aromatic framework, the molecules of the each
component are arranged in a zigzag line along the rod axis. The zigzag arrangement of components in
the 1D assemblies and the supramolecular architecture of co-crystals persist when the aromatic frame-
work size increases and when one or two bulky CF3 groups are incorporated into ortho-positions to the
amino groups. Using differential scanning calorimetry (DSC), specific melting heats of co-crystals have
been determined, which trend towards a decrease with an increase of the 1D assembly unit lengths.
Ó 2011 Elsevier B.V. All rights reserved.
Received 8 February 2011
Received in revised form 29 March 2011
Accepted 31 March 2011
Available online 6 April 2011
Keywords:
Molecular crystals
Supramolecular architecture
X-ray diffraction analysis
Polyfluorinated arylenediamines
Crown ether
Melting heats
1. Introduction
atom (associate of thiourea [6]). Of course, the two last associates
have the stoichiometry of amine:crown = 2:1.
Molecular associates of organic mono- or diamines and 18-
crown-6 provide great scope for crystal engineering based on using
the hydrogen bond as a design element [1]. The supramolecular
architecture of these co-crystals often has a 1D motif À rods (chains,
lines) consisting of alternate molecules of components [2–6]. There
are several supramolecular synthones, which provide the 1D
Configuration of 1D assemblies depends on the chemical struc-
ture of the components and on the stoichiometry of the associates.
In most of the known associates, the planes of 18-crown-6 mole-
cules are parallel [2–6]. In the rods formed by para-arylenediamines
(tetrafluoro-para-phenylenediamine (CCDC 800765 [7]), and hexa-
fluoro-pseudopara-naphthylenediamine (CCDC 800767 [7]), the
planes of aromatic ring are also parallel to each other; therefore this
type of configuration was entitled ‘‘pairwise parallel’’ (Fig. 1a) [2].
Along with this, there are rare examples of 1D assemblies, in which
both components are arranged in a zigzag line along the rod axis
(Fig. 1b): crown ether molecules are oriented under an angle to
each other and amine molecules are shifted to the periphery of
the rod. Such a configuration is realized in 1D assemblies of 18-
crown-6 and 4-amine-1,2,5-oxadiazole-3-carbonic acid [8] or tetra-
fluoro-meta-phenylenediamine (CCDC 800766 [7]) [2]. In the latter
case, the zigzag arrangement of the rod components is caused, most
likely, by the meta-location of amino groups in an aromatic ring.
However, hexafluoro-pseudometa-naphthylenediamine, the struc-
tural analog of this molecule, and 18-crown-6 are able to form
the associate of stoichiometry 2:1, respectively, composed of the
pairwise parallel components (CCDC 800768 [7]) (Fig. 1c). The rod
structure. First of all, it is
a
hydrogen-bonded synthon
C(N)ANAHÁ Á ÁOACcrown on either side of a crown ether plane. The
second synthon, which is responsible for the binding the (di)ami-
neÁ Á ÁcrownÁ Á Á(di)amine fragment into a polymolecular associate,
has a variable nature depending on the amine structure. As a rule,
both amino groups of diamines participate uniformly in the forma-
tion of alternate 1D assemblies. This structural type was realized in
co-crystals of 18-crown-6 with polyfluorinated phenylene- and
naphthylenediamines [2], bis-thiourea (H2NC(S)NHNHC(S)NH2),
and dithiooxamide (H2NC(S)C(S)NH2) [3]. Associates formed by
monoamines have various types of bonding: synthon
NACH2AHÁ Á ÁOACcrown involving ‘‘acidic’’ hydrogen of the methyl
group (associate of methylthiourea [4]);
p-stacking of aromatic
rings (associate of 2,4-dinitrophenylhydrazine [5]); synthon
NAHÁ Á ÁS@C formed by the amino group and sp2-hybridic sulfur
is formed by means of the
p-stacking of hexafluoronaphthylene
rings and the interaction CareneANAHÁ Á ÁOACcrown, in which amino
groups from the different naphthylenediamine molecules take
part [2].
⇑
Corresponding author. Fax: +7 (383) 330 9752.
E-mail address: malykhin@nioch.nsc.ru (E.V. Malykhin).
0022-2860/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2011.03.067

110
T.A. Vaganova et al. / Journal of Molecular Structure 995 (2011) 109–115
Fig. 1. Graphs of the supramolecular 1D motifs: pairwise parallel (a and c); zigzag-like (b).
Fig. 2. Structures of the polyfluorinated arylenediamines I–V.
The investigation of the associates structure and its relationship
at the rate 10 °C minÀ1 to the temperature below the onset of the
mass loss. Melting points were determined on a Apotec RS
instrument.
with thermodynamic characteristics of co-crystals has some prac-
tical aspects. The selectivity of the formation of crystal associates
from isomeric polyfluorinated para- and meta-arylenediamines
and 18-crown-6 was found [2] to depend on their melting heats.
When the amount of crown ether is insufficient, associates of
para-arylenediamines, possessing greater melting heats, crystallize
selectively from solutions of the isomer mixtures, whereas meta-
isomers, possessing smaller melting heats, remain in a solution.
The empirically revealed effect of molecular recognition was ap-
plied for the preparation of the highly purified polyfluoroarylen-
ediamines [9,10], which are widely used as building blocks in the
synthesis of polymers for optical communications [11–13], and
as bioactive substance precursors [14]. In addition, the 1D supra-
molecular architecture suggests anisotropy of physical properties,
which is the higher the less 1D structures interact with each other.
Such an effect can be used in creating high performance materials.
The aim of the present work is to synthesize the zigzag-like 1D
assemblies of 18-crown-6 with polyfluoro-meta-arylenediamines,
namely, 2,4,5-trifluoro-1,3-phenylenediamine (I), 2,5,6-trifluoro-
4-trifluoromethyl-1,3-phenylenediamine (II), 2,5-difluoro-4,6-bis-
(trifluoromethyl)-1,3-phenylenediamine (III) and hexafluoro-2,
7-naphthylenediamine (IV) (Fig. 2). The use of such a set of
meta-arylenediamines, including tetrafluoro-1,3-phenylenedi-
amine (V) [2], makes it possible to study the dependence of the
1D assemblies geometric parameters and of the co-crystal melting
heats on the size of an aromatic ring and substituents in the
ortho-positions relative to the amino groups. In the work (i) crys-
tal associates of the 18-crown-6 and polyfluoroarylenediamines
with the stoichiometry of 1:1 were obtained; (ii) structures of
co-crystals were characterized by the X-ray analysis; (iii) melting
heats of crystal associates were determined by the differential
scanning calorimetry (DSC) and a relationship between the melt-
ing heat and the 1D assembly unit length was revealed.
2.2. Reagents
2,4,5-Trifluoro-1,3-phenylenediamine (I), mp 71–72 °C [9],
2,5,6-trifluoro-4-trifluoromethyl-1,3-phenylenediamine (II), mp
31.5–32.5 °C [9], 2,5-difluoro-4,6-bis(trifluoromethyl)-1,3-phenyl-
enediamine (III), mp 67–68 °C [9], 1,3,4,5,6,8-hexafluoro-2,7-
naphthylenediamine (IV), mp 235–238 °C (decomp.) [10] were
synthesized using the procedures described in the mentioned
Refs.
2.3. Preparation of associates of 18-crown-6 and arylenediamines
A solution of 18-crown-6 (1.9 mmol) in a low polar solvent
(5 mL) was added to a solution of polyfluoroarylenediamine
(1.85 mmol) in the same solvent (5 mL). The mixture was kept
for 1–2 h at room temperature (ꢀ22 °C) upon stirring. The precip-
itate formed was filtered off, washed with the cold solvent, and
dried in air to a constant weight.
Associate
18-crown-6, 1:1 (A-I), was precipitated from a solution in tert-
butyl methyl ether, yield 76%, mp 96–97 °C (CCl4). IR,
/cmÀ1
of
2,4,5-trifluoro-1,3-phenylenediamine
and
m
:
3458, 3357, 3298, 1659 (NH2); 2881, 2822, 1524, 1499, 1351
(Caliph.AH); 1636 (Carom.ACarom.); 1111 (Caliph.AO). 1H NMR
(DMSO-d6), d: 3.51 (br.s, 24H, CH2); 4.94, 5.24 (both br.s, 2H each,
NH2); 5.88 (ddd, 1H, H(6), JHF = 13, JHF = 8, JHF = 8). 19F NMR (DMSO-
d6), d: À172.9 (ddd, 1F, F(4), JFF = 23, JHF = 8, JFF = 2); À158.9 (ddd,
1F, F(2), JFF = 11, JHF = 8, JFF = 2); À146.2 (ddd, 1F, F(5), JFF = 23,
JHF = 12, JFF = 11).
Associate of 2,5,6-trifluoro-4-trifluoromethyl-1,3-phenylenedi-
amine and 18-crown-6, 1:1 (A-II), was precipitated from a solution
in pentane, yield 96%, mp 95–96 °C (CCl4). IR, m
/cmÀ1: 3445, 3362,
2. Experimental
3332, 1659 (NH2); 2889, 2826, 1528, 1503, 1475, 1350 (Caliph.AH);
1640 (Carom.ACarom.); 1109 (Caliph.AO). 1H NMR (DMSO-d6), d: 3.51
(br.s, 24H, CH2), 5.32 (br.s, 2H, NH2), 6.07 (br.s, 2H, NH2). 19F NMR
(DMSO-d6), d: À173.0 (dd, 1F, F(6), JFF = 4, JFF = 32), À157.8 (dd, 1F,
F(2), JFF = 4, JFF = 9), À149.1 (m, F(5)), À53.0 (d, 3F, (CF3), JFF = 23.0).
Associate of 2,5-difluoro-4,6-bis(trifluoromethyl)-1,3-phenyl-
enediamine and 18-crown-6, 1:1 (A-III), was precipitated from a
2.1. Measurements
1H and 19F NMR spectra were recorded on a Bruker AV-300
spectrometer using the residual protons in the deuterated
solvent and C6F6 (d = À163 ppm from CCl3F) as internal standards,
J are given in Hz. IR spectra were recorded on a Bruker Vector-22
spectrometer for KBr disks. Thermal analysis was performed on
solution in pentane, yield 90%, mp 90–91 °C (CCl4). IR,
m :
/cmÀ1
3486, 3382, 3307, 3245, 3211, 1649 (NH2); 2892, 2831, 1520,
1356 (Caliph.AH); 1108 (Caliph.AO). 1H NMR (DMSO-d6) d: 3.51
(br.s, 24H, CH2), 6.12 (br.s, 4H, C(1)NH2, C(3)NH2). 19F NMR
a
STA 409 PC Luxx Netzch synchronous thermal analyzer.
Heating of the samples was performed under argon atmosphere

T.A. Vaganova et al. / Journal of Molecular Structure 995 (2011) 109–115
111
(DMSO-d6), d: À158.5 (d, 1F, F(2), JFF = 10.0), À121.2 (m, 1F, F(5)),
À53.3 (d, 6F, C(4)CF3, C(6)CF3, JFF = 25.0).
associate A-III the difference electron density peaks located around
crown ether ring O4O5O6 were interpreted as the minor part of the
disordered (0.763:0.237) crown ether ring. Atoms O6 and C20 of the
major part are also disordered over two positions in 0.8:0.2 ratio.
The minor parts of the disordered atoms in A-I—A-III were refined
in isotropic approximation. The intermolecular interactions were
analyzed using PLATON [16] and MERCURY programs [17].
Associate of 1,3,4,5,6,8-hexafluoro-2,7-naphthylenediamine
and 18-crown-6, 1:1 (A-IV), was precipitated from a solution in
tert-butyl methyl ether, yield 98%, mp 130.6–132 °C (CCl4). IR, m/
cmÀ1: 3461, 3437, 3353, 3296, 3229, 3194, 1664 (NH2); 2891,
1538, 1467, 1353 (Caliph.AH); 1621 (Carom.ACarom.); 1112
(Caliph.AO). 1H NMR (acetone-d6), d: 3.58 (br.s, 24H, CH2); 5.35
(br.s, 4H, C(2)NH2, C(7)NH2). 19F NMR (acetone-d6), d: À157.9 (m,
2F, F(3), F(6)); À152.8 (m, 2F, F(4), F(5)); À149.0 (m, 2F, F(1),
F(8)).
3. Results and discussion
Monocrystals of A-I—A-III for the X-ray diffraction were ob-
tained from the solutions in CCl4; monocrystal of A-IV À from
the solution in acetone, because the crystallization from a less po-
lar solvent results in co-crystals of variable stoichiometry (for
example, from chloroform solution the co-crystal of stoichiometry
2:1 in favor of IV was obtained [2]).
3.1. Analysis of associates structure
The crystal associates A-I—A-IV of 18-crown-6 and polyfluoro-
arylenediamines I—IV respectively precipitate upon mixing the
solutions of equimolar amounts of the components in a low-polar
aprotic solvents. According to the 1H NMR data the stoichiometry
of components in A-I—A-IV is 1:1. The melting points of co-crystals
differ from those of individual components that testifies to the for-
mation of so-called ‘‘guest–host molecular complexes’’ [18].
The crystallographic data on the associates A-I—A-IV and the
parameters of their structure refinements are given in Table 1.
The crown ether molecules in the co-crystals are in the two
different conformations. The conformation of 18-crown-6 in
associates A-I and A-IV is close to the classic crown 3(TGT,T-GT)
2.4. X-ray diffraction study of associates A-I—A-IV
Single crystal X-ray diffraction was performed on a Bruker Kap-
pa Apex II diffractometer equipped with a two-dimensional CCD-
detector using
x, / scanning. Absorption correction was applied
using the SADABS program. The crystallographic data and parame-
ters of refinement of the structures are given in Table 1. The struc-
tures were solved by the direct method and refined by full-matrix
least-squares method in an anisotropic approximation (except H
atoms) using the SHELXL-97 program [15]. Positions of hydrogen
atoms of amino groups were found from difference map and refined
isotropically, the rest hydrogen atoms were located geometrically
and refined in the riding model. In associate A-I phenylenediamine
molecule is disordered; the major and minor parts (0.853:0.147)
are disposed in the different planes with closely located nitrogen
atoms. The major parts of hydrogen and fluorine atoms at C4 and
C6 atoms are also disordered in 0.5:0.5 ratio. Trifluoromethyl
groups (C7) in associates A-II and A-III are disordered over two
positions in 0.765:0.235 and 0.883:0.117 ratios, accordingly. In
(T stand for twist,
G stand for gauche); in A-V – close to
2(TGT,TGT,GGT); and the crown ether molecules in associates
A-II and A-III have the above alternate conformations.
In the phenylenediamine associates the distance between the
amino group nitrogen atoms (NarÁ Á ÁNar) depends on the volume
of ortho-located substituents. Thus, in the case of small substitu-
ents (hydrogen and fluorine atoms) the distance NarÁ Á ÁNar is
4.84 Å and 4.86 Å [2] in I and V, respectively; replacing one or
two fluorine atoms with bulky CF3 groups in II and III results in
diminishing NarÁ Á ÁNar down to 4.76 Å and 4.71 Å, respectively.
Thereby, the bulky substituents in the ortho-positions ‘‘prop up’’
the amino groups, thus decreasing the distance NarÁ Á ÁNar.
Table 1
Crystallographic data and structure refinement parameters of associates A-I—A-IV.
Parameter
Associate
A-I
A-II
A-III
A-IV
Chemical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
C6H5F3N2, C12H24O6
426.43
150
Orthorhombic
Pbca
15.675(2)
14.437(2)
18.811(3)
90
90
90
4257(1)
8
1.331
C7H4F6N2, 2/2(C12H24O6)
494.43
150
Triclinic
P-1
8.260(3)
9.332(4)
15.498(6)
79.68(2)
77.08(2)
77.51(2)
1125.9(7)
2
C8H4F8N2, 2/2(C12H24O6)
544.44
173
Triclinic
P-1
8.601(1)
9.685(1)
16.200(2)
95.469(7)
103.723(6)
105.439(6)
1245.5(3)
2
C10H4F6N2, C12H24O6
530.46
150
Monoclinic
C2/c
27.110(4)
8.8378(15)
20.605(3)
90
93.468(6)
90
4928(1)
8
1.430
0.132
b (Å)
c (Å)
a
(deg)
b (deg)
c
(deg)
Cell volume (Å3)
Z
dcalc (gÁcmÀ3
)
1.458
0.138
1.452
0.144
l
(mmÀ1
)
0.115
Crystal dimensions (mm)
h range (deg)
0.14 Â 0.26 Â 0.58
0.18 Â 0.19 Â 0.25
0.48 Â 0.38 Â 0.10
0.60 Â 0.15 Â 0.07
27.04
27.72
26.08
28.14
Reflections collected/unique
R (int)
62875/4665
0.0568
3813
16759/5193
0.0554
3921
16198/4891
0.0306
4150
40579/5975
0.0672
4648
Reflections with I > 2
r(I)
Parameters
299
327
373
341
Final R1 (I > 2
r
(I))
0.0540
0.1804
1.073
0.0582
0.1679
1.079
0.0574
0.1710
1.005
0.0376
0.1105
1.018
Final wR2 (all data)
Goodness-of-fit on F2
CCDC number
785019
785020
785021
785022

112
T.A. Vaganova et al. / Journal of Molecular Structure 995 (2011) 109–115
Table 2
Supramolecular parameters of the rods of associates A-I—A-V.
Associate
Direction
of the
rod axis
Length of the
rod unit/ module
of the cell axis (Å)
Slope of the
18-crown-6 plane
to the rod axis (deg)
Slope of the
arylenediamine plane
to the rod axis (deg)
Dihedral angle
between the
18-crown-6
planes (deg)
Dihedral angle
between the
arylenediamine
planes (deg)
Sequence of the
molecules
in the roda
A-I
a
c
a + c
c
15.68
15.50
16.44
20.61
16.10
65; 115
49; 135
44; 132b
60; 120
37; 143
17b
12
16
10
0
40
4b
0
0
95
0
.1.1(i).1(ii)
.1.2.1(iii)
.1.2.1(iv)
.1.1(v).1(iii)
.1.2.1(vi)
A-II
A-III
A-IV
A-Vc
86
93b
60
b
107
a
b
c
1 and 2 denote symmetry unrelated crown ether molecules; i = 1/2 + x, y, 1/2 À z; ii = 1 + x, y, z; iii = x, y, 1 + z; iv = 1 + x, y, 1 + z; v = x, 1 À y, 1/2 + z; vi = x, 1 + y, z.
Data for the major part of disordered arylenediamine or crown ether molecules.
Ref. [2].
Fig. 3. View of the associate fragments with the numbering scheme (the minor components of the disordered molecules and H atoms of crown ether are omitted): A-I, F2A
and F2B denote disordered F atom (a); A-II (b); A-III (c); A-IV (d).
The supramolecular architecture of crystal associates A-IÀA-IV
has a general 1D motif similar to that of associate A-V [2]: the rods
composed of alternating molecules of arylenediamine and 18-
crown-6. Co-crystals of A-II and A-III present two crystallographic
unrelated crown ether molecules, which have different orientation
relative to the cell axes and lie on two different centers of
symmetry (here designed as 1 and 2). The sequence of the mole-
cules along the rod for the structures A-I—A-IV is presented in
Table 2. Fig. 3a–d reveal the view of the four rod fragments.
Fig. 4a and b reveal the side view of the rods (a) and rods cross-sec-
tion (b). The rods are parallel to specific crystallographic axes, as
reported in Table 2. Along the rods, the six oxygen atoms centroids
of crown ether molecules lie on a straight line in the first three
structures, which, in fact, is the rod axis. In A-IV crown ether
centroids slightly deviate from the axis: the angle among three
consecutive centroids is 170°.

T.A. Vaganova et al. / Journal of Molecular Structure 995 (2011) 109–115
113
Fig. 4. Rods of the associates A-I—A-V: side (a) and cross-section (b) views.
Molecules of components are disposed in the rods as follows.
The mean planes of the six oxygen atoms of the crown ether macro
cycle are oriented at the slopes of 37–65° to the rod axis. In the
rods containing two different conformations of crown ether mole-
cules there are two slightly differing slope angles (Table 2). The
mutual arrangement of the adjacent crown ether molecules is
characterized by dihedral angles 42–107°. The amino groups in
the arylenediamines are arranged near the rod axes, while the
mass centers of the molecules are positioned at the periphery of
the rods; some fluorine atoms and CF3 groups go beyond the
perimeter of the rod cross-section and weakly interact with
crown-ether hydrogen atoms of the closest rods. The neighboring
arylenediamine molecules in associates A-I—A-III and A-V are dis-
posed diametrically opposite to each other; their antiphase dispo-
sition is somewhat disturbed only in associate A-IV (Fig. 4). The
aromatic ring planes in A-I—A-IV are nearly parallel to the rod
axes, the angle being <17° in all four cases (Table 2). Thus, the both
components in the co-crystals are arranged in a zigzag line along
the rod axes, according to Fig. 4a.
substituents in the ortho-positions relative to the amino groups
influence the lU to a lesser extent. The incorporation of the two
CF3 groups in going from A-V to A-III increases the unit length. Sur-
prisingly, the replacement of one fluorine atom in symmetrical
phenylenediamine V with both the bulky CF3 group and small
hydrogen atom (asymmetrical phenylenediamines II and I, respec-
tively) results in a decrease of the rod unit length lU.
In co-crystals A-I—A-IV, as well as in A-V, all the rods are par-
allel and realize a ‘‘ledge-to-cavity’’ packing (Fig. 5). Mutual shift
of the units in the neighboring rods reaches quarter of the unit
length. According to the minimal distance between the rod axes,
which is smaller than the rod diameter, layers can be selected in
the co-crystals. Table 3 reports the directions of the layers prop-
agation, the distance between the closest rods, and the relative
shift.
Alternating molecules of components are assembled into rods by
means of hydrogen bonds CcrownAOÁ Á ÁHANarylene. Geometrical
parameters of these bonds are given in Table 4. In co-crystals there
are some contacts CaryleneAFÁ Á ÁHACaliph at the distances slightly
shorter than the sum of Van der Waals radii, both within and be-
tween the rods. However, this type of hydrogen bond is known
[19] to have a considerably smaller energy as compared with the
The rod unit is composed of four sequentially located mole-
cules. The length of the rod unit (lU) is equal to the module of cell
axis being parallel to the rod axis (in A-III – |a + c|) (Table 2).
Replacement of the phenylene framework in diamine with the
naphthylene one results in a substantial increase of the rod unit
length lU. Such an effect was observed in the rods with the pairwise
parallel arrangement of components [2]. Varying the volume of
interaction
FÁ Á ÁHACaliph cannot perform the rod-supporting function. As
whole, the supramolecular architecture of the co-crystals
A-I—A-IV, as well as A-V, has the motif no higher than 1D.
C
areneANAHÁ Á ÁOACcrown
,
hence contact
CaryleneA
a

114
T.A. Vaganova et al. / Journal of Molecular Structure 995 (2011) 109–115
meta-arylenediamines increase. Together with the data [2] for
para-arylenediamine associates having the pairwise parallel com-
ponents arrangement, the results obtained point to the possibility
of designing co-crystal structure on the basis of the arylenediam-
ines structure, specifically, of the mutual arrangement of the amino
groups in a rigid framework.
3.2. Thermal analysis of associates A-I—A-IV
The thermal characteristics of co-crystals A-I—A-IV were stud-
ied by using the differential scanning calorimetry (DSC). In spite
of a pronounced structural anisotropy, DSC curves of all associates
exhibit a single endothermic peak of the crystal-to-liquid phase
transition. The temperatures of the phase transition and values of
the specific weight melting heats (
the values of the melting heats per unit of the rod (
culated (Table 5). The HW values and melting points are repro-
D
HW) were determined and
D
HU) were cal-
D
ducible in a cyclic melting-crystallization regime, which testifies
to the uniformity of associate structures crystallizing from melts
or solutions.
Owing to the absence of strong interactions between the rods,
melting heats of co-crystals appear to be predominately deter-
mined by breaking of H-bonds within the 1D assembly. Besides,
changing the crown ether conformation during the co-crystals
melting make some contribution into the phase transition heat.
The previous calculation made by the DFT PBE/3Z method [2]
showed the energy of the 3(TGT,T-GT) conformation of crown
ether in a gas phase to be lower by 13.4 kJ molÀ1 than that of the
2(TGT,TGT,GGT) conformation. However, the melting heats of co-
crystals A-II and A-III, in which the high-energy conformation of
crown ether molecules alternates with the low-energy conforma-
tion, represent the two extreme values of the range and differ by
37 kJ g-unitÀ1. On the other hand, the melting heats of co-crystal
A-I, whose crown ether molecules are in the low-energy conforma-
tion 3(TGT,T-GT), and of co-crystal A-V, whose crown ether
molecules are in the high-energy conformation 2(TGT,TGT,GGT),
differ from each other insignificantly. These facts point that the dif-
ference of the energies of crown ether conformations is not a factor
governing the difference of the co-crystal melting heats.
Comparison of the
DHU values of co-crystals with the configura-
tion and geometric parameters of 1D assemblies leads to the
following conclusions. The specific melting heat of hexafluoro-
pseudometa-naphthylenediamine associate A-IV is lower then that
of hexafluoro-pseudopara-naphthylenediamine associate, whose
rod has a pairwise parallel configuration (2Á57 kJ g-molÀ1, the unit
of a pairwise parallel rod consists of 2 molecules [2]). These data
agree with the conclusion made for the associates of tetrafluoro-
para- vs. -meta-phenylenediamines [2] that supramolecular 1D
assemblies with the pairwise parallel arrangement of components
Fig. 5. Packing of rods in the co-crystal A-I: ledge-to-cavity arrangement (a) and
cross-section (b).
have larger values of
assemblies.
DHU as compared with the zigzag-like
Table 3
Supramolecular parameters of the layers formed by the rods in associates A-I – A-V.
The tendency to a decrease of the co-crystal melting heat with
an increase of the rod unit length, revealed for pairwise parallel
1D assemblies [2], also exists in a series of the zigzag-like rods.
Thus, in going from phenylene to naphthylene associate (from A-
V to A-IV) the rod unit length increases appreciably followed by
a decrease of the melting heat. The replacement of one fluorine
atom in A-V with hydrogen atom or CF3 group (A-I and A-II,
respectively) results in a decrease of the rod unit length and an in-
Associate
Direction of
the layer
Distance between
the rod axes (Å)
Shift of the rods
(Å/% of the unit length)
A-I
a, b
a, c
a + c, a À c
c, a À b
a, b
7.19
8.05
8.23
7.43
7.56
3.98/25
1.85/12
2.48/15
5.47/27
0
A-II
A-III
A-IV
A-Va
a
Ref. [2].
crease of the
III) causes an increase of the rod unit length and a decrease of
the HU value. The revealed tendency is one of rare examples
DHU value. The incorporation of two CF3 groups (A-
Thus, the 1D assemblies structure (the zigzag arrangement of
D
the components) and the supramolecular architecture of co-crys-
tals (parallel packing of the rods) persist when both the volume
of substituents and the size of the aromatic framework in the
(see [20] and Refs. therein) of a relationship between parameters
of supramolecular unit and thermodynamic characteristics of
crystal phase.

T.A. Vaganova et al. / Journal of Molecular Structure 995 (2011) 109–115
115
Table 4
Hydrogen bonding NAHÁ Á ÁO in the rods of associates A-I – A-IV (data for the main part of disordered molecules of arylenediamine in A-I and crown ether in A-III).
Associate
Interaction XAHÁ Á ÁY
lX–H (Å)
lXÁ Á ÁY (Å)
lHÁ Á ÁY (Å)
Angle XAHÁ Á ÁY (deg)
Symmetry code for acceptor
A-I
N1AH1Á Á ÁO2
N2AH4Á Á ÁO5
0.80(3)
0.81(3)
3.261(3)
3.129(3)
2.47(3)
2.33(3)
174(2)
174(2)
À1/2 + x, y, 1/2 À z
À1 + x, y, z
A-II
N1AH1Á Á ÁO5
N1AH1Á Á ÁO6
N1AH2Á Á ÁO4
N1AH2Á Á ÁO5
N2AH3Á Á ÁO2
0.89(3)
0.89(3)
0.83(3)
0.83(3)
0.87(3)
3.149(3)
3.078(3)
3.178(3)
3.165(3)
3.266(3)
2.40(3)
2.41(3)
2.57(3)
2.38(3)
2.42(3)
142(2)
132(3)
131(2)
158(2)
165(3)
1 À x, 1 À y, 1 À z
1 À x, 1 À y, 1 À z
À1 + x, y, z
À1 + x, y, z
Àx, 1 À y, 1 À z
A-III
A-IV
N1AH2Á Á ÁO2
N2AH3Á Á ÁO4
N2AH3Á Á ÁO5
N2AH4Á Á ÁO5
N2AH4Á Á ÁO6
N1AH1Á Á ÁO1
N1AH2Á Á ÁO5
N2AH3Á Á ÁO6
N2AH4Á Á ÁO2
0.83(3)
0.88(4)
0.88(4)
0.77(4)
0.77(4)
3.073(3)
3.049(5)
3.222(3)
3.235(3)
3.014(5)
2.26(4)
2.40(4)
2.41(4)
2.58(5)
2.44(4)
169(3)
131(3)
153(3)
144(3)
133(3)
1 À x, 1 À y, 1 À z
x, y, z
x, y, z
1 À x, 1 À y, 1 À z
1 À x, 1 À y, 1 À z
0.87(2)
0.81(2)
0.88(2)
0.82(2)
3.100(2)
3.206(2)
3.056(2)
3.206(2)
2.25(2)
2.49(2)
2.26(2)
2.49(2)
166(2)
148(2)
152(2)
146(2)
x, y, À1 + z
x, y, À1 + z
x, 2 À y, À1/2 + z
x, 2Ày, À1/2 + z
Table 5
Melting points and melting heats of associates A-I–A-V according to the DSC.
References
Associate
TOM (°C)
TMAX (°C)
D
HW (J gÀ1
)
D )
HU (kJ g-unitÀ1
a
a
b
[1] B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629;
T. Steiner, Angew. Chem. Int. Ed. 41 (2002) 48;
A-I
95.5
93
98.6
97
92.2
131
92.5
134
121
76
95
123
114
120
83
101
109
A. Norman, A.A. Rahman, R. Bishop, D.C. Craig, M.L. Scudder, Eur. J. Org. Chem.
(2003) 72;
G.R. Desiraju, Angew. Chem. Int. Ed. 46 (2007) 8342.
A-II
A-III
A-IV
A-Vc
87
[2] S.Z. Kusov, Yu.V. Gatilov, I.Yu. Bagryanskaya, G.V. Romanenko, T.A. Vaganova,
I.K. Shundrina, E.V. Malykhin, Russ. Chem. Bull. Int. Ed. 59 (2010) 382.
[3] Yu. Simonov, M. Fonari, M. Zaworotko, H. Abourahma, J. Lipkowski, E. Ganin, A.
Yavolovskii, Org. Biomol. Chem. 1 (2003) 2922.
[4] W.H. Watson, J. Galloy, D.A. Grossie, F. Vogtle, W. Muller, J. Org. Chem. 49
(1984) 347.
127
89.5
a
b
c
TOM is the onset of melting; TMAX is the melting peak temperature.
HU is the melting heat calculated on the weight of unit.
Ref. [2].
D
[5] R. Hilgenfeld, W. Saenger, Z. Naturforsch., B: Chem. Sci. 36 (1981) 242.
[6] M.G. Drew, D.G. Nicholson, Acta Crystallogr. C 41 (1985) 1358.
[7] Cambridge Structural Database System, Version 5.31, 2009 (May 2010 update).
[8] M.S. Fonari, Yu.A. Simonov, V.Ch. Kravtsov, J. Lipkowski, E.V. Ganin, A.A.
Yavolovskii, J. Mol. Struct. 647 (2003) 129.
4. Conclusions
[9] T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, I.K. Shundrina, E.V. Malykhin, Russ.
Chem. Bull. Int. Ed. 56 (2007) 2239.
Thus, in this work supramolecular zigzag-like 1D assemblies of
18-crown-6 and polyfluorinated meta-arylenediamines were de-
signed. Alternating molecules of the components are assembled
into rods by means of hydrogen bonds between the amino group
hydrogen atoms and the crown ether oxygen atoms (synthon
[10] T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, I.K. Shundrina, G.E. Sal’nikov, V.I.
Mamatyuk, E.V. Malykhin, J. Fluorine. Chem. 129 (2008) 253.
[11] S. Ando, T. Matsuura, S. Sasaki, Macromolecules 25 (1992) 5858.
[12] I.K. Shundrina, T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, E.V. Karpova, V.V.
Koval, Yu.V. Gerasimova, E.V. Malykhin, J. Fluorine. Chem. 130 (2009) 733.
[13] EP Pat. 1275679, Chem. Abstrs. 138 (2003) 90676.
[14] L. Revesz, F.E. Di Padova, T. Buhl, R. Feifel, H. Gram, P. Hiestand, U. Manning, R.
Wolf, A.G. Zimmerlin, Bioorg. Med. Chem. Lett. 12 (2002) 2109;
D.J. McNamara, P.D. Cook, J. Med. Chem. 30 (1987) 340;
C
areneANAHÁ Á ÁOcrown). In co-crystals, rods are parallel, shifted one
along the other, hence realizing the ‘‘ledge-to-cavity’’ packing.
Geometrical parameters of the rods and melting heats of the crys-
tal associates were determined.
M.-C. Liu, M.-Z. Luo, D.E. Mozdziesz, T.-S. Lin, G.E. Dutschman, E.A. Gullen,
Y.-C. Cheng, A.C. Sartorelli, Nucleosides, Nucleotides, Nucleic Acids 20
(2001) 1975.
The influence of the isomerism, symmetry and size of polyflu-
oroarylenediamines on the features of the supramolecular
architecture and melting heat of the co-crystals can be briefly
described as follows:
[15] G.M. Sheldrick, SHELXL-97–Programs for Crystal Structure Analysis, Release
97-2, University of Gottingen, Gottingen, Germany, 1998.
[16] A.L. Spek, PLATON,
A Multipurpose Crystallographic Tool, Version 10M,
Utrecht University, Utrecht, The Netherlands, 2003;
A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7.
[17] C.F. Macrae, P.R. Edgington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M.
Towler, J. van de Streek, J. Appl. Crystallogr. 39 (2006) 453.
[18] F.F. Vogtle, W. Muller, Chem. Ber. 114 (1981) 3179.
[19] D. Dunitz, A. Gavezzotti, W.B. Schweizer, Helv. Chem. Acta 86 (2003) 4073;
D. Dunitz, R. Taylor, Chem. Eur. J. 3 (1997) 89.
(i) The pairwise parallel arrangement of components in the
rods is replaced by the zigzag arrangement in going from
perfluorinated para- to meta-arylenediamines.
(ii) The length of the rod unit increases and the melting heat
decreases in going from perfluorinated meta-phenylene- to
pseudometa-naphthylenediamines as well as in the case of
perfluorinated para-arylenediamines.
(iii) The length of the rod unit decreases and the melting heat
increases in going from the symmetrical phenylenediamines
III and V to the asymmetrical I and II.
[20] C. Ouvrard, J.B.O. Mitchell, Acta Crystallogr., Sect. B: Struct. Sci. 859 (2003)
676;
V.M. Egorov, V.A. Marikhin, L.P. Myasnikova, N.N. Nakamura, Phys. Solid State
(Engl. Trans.) 51 (2009) 2129;
A.O. Surov, G.L. Perlovich, Russ. J. Struct. Chem. (Engl. Trans.) 51 (2010)
308.