New tetraaza[14]annulene receptors derived from 2,3-diaminonaphthalene: Synthesis and crystal structures

Article abstract of DOI:10.1080/10610278.2013.766736

The first synthesis of the bis(2-hydroxybenzoyl)dinaphthotetraaza[14] annulene ligand and its O,O-bis-alkylated derivatives containing a decanedioxy bridging moiety, pendant bis-alkoxy groups as well as dicationic butoxypyridinium substituents is reported. The synthetic procedures, full analytical and spectroscopic characterisation (NMR, MS and IR) and crystal structures of the new products are described. The crystal structures show that naphthylene moieties incorporated into the investigated derivatives provide additional opportunities for non-covalent interactions between the molecules.

Full text of DOI:10.1080/10610278.2013.766736

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Supramolecular Chemistry
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New tetraaza[14]annulene receptors derived from 2,3-
diaminonaphthalene: synthesis and crystal structures
Alicja Kaźmierska a , Marlena Gryl a , Katarzyna Stadnicka a & Julita Eilmes a
a Department of Chemistry , Jagiellonian University , Ingardena 3, Kraków , 30-060 , Poland
Published online: 11 Feb 2013.
To cite this article: Alicja Kaźmierska , Marlena Gryl , Katarzyna Stadnicka & Julita Eilmes (2013) New tetraaza[14]annulene
receptors derived from 2,3-diaminonaphthalene: synthesis and crystal structures, Supramolecular Chemistry, 25:5, 276-285,
DOI: 10.1080/10610278.2013.766736
To link to this article: http://dx.doi.org/10.1080/10610278.2013.766736
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Supramolecular Chemistry, 2013
Vol. 25, No. 5, 276–285, http://dx.doi.org/10.1080/10610278.2013.766736
New tetraaza[14]annulene receptors derived from 2,3-diaminonaphthalene:
synthesis and crystal structures
´
Alicja Kazmierska, Marlena Gryl, Katarzyna Stadnicka and Julita Eilmes*
´
Department of Chemistry, Jagiellonian University, Ingardena 3, Krakow 30-060, Poland
(Received 21 November 2012; final version received 9 January 2013)
The first synthesis of the bis(2-hydroxybenzoyl)dinaphthotetraaza[14]annulene ligand and its O,O-bis-alkylated derivatives
containing a decanedioxy bridging moiety, pendant bis-alkoxy groups as well as dicationic butoxypyridinium substituents is
reported. The synthetic procedures, full analytical and spectroscopic characterisation (NMR, MS and IR) and crystal
structures of the new products are described. The crystal structures show that naphthylene moieties incorporated into the
investigated derivatives provide additional opportunities for non-covalent interactions between the molecules.
Keywords: dinaphthotetraaza[14]annulene; synthesis; receptors; crystal structure; non-covalent interactions
1. Introduction
macrocycle, will differ remarkably from those correspond-
ing to the o-phenylene-based analogues. Similarly, the
acid–base behaviour of the free ligands is expected to be
modified significantly. In addition, the new receptors are
potential fluorescent probes based on the well-known
fluorescence characteristics of o-diaminonaphthalene
derivatives and their use for the detection and bioimaging
of nitric oxide (7).
Dibenzotetraaza[14]annulenes (DBTAAs) are interesting
macrocycles for both theoretical and practical reasons. The
publication of studies of their chemistry has been growing
in recent years (1–5). Our laboratory has shown that
DBTAAs exhibited remarkable peripheral reactivity,
allowing the preparation of various derivatives with
modified structures and properties (2). Thus, among other
results, new DBTAA-based liquid crystals have been
developed, as well as water-soluble derivatives with
promising DNA/RNA-binding properties (3, 4). The latest
progress made in this field concerns acid–base behaviour
and tautomerism involving superstructured molecules
produced by the peripheral derivatisation of simple
DBTAA substrates (5).
In this study, we report on the preparation of the
previously unknown DNTAA ligand 1 and its derivatives,
among which a bridged product 3 and water-soluble bis-
pyridinium derivative 5 are of particular interest as a
lacunar-type receptor and a potential DNA-binding agent,
respectively. The crystal structures of 3, 4 and 5 have been
determined and analysed, paying special attention to non-
covalent interactions. Scheme 1 outlines the reactions
carried out.
In line with our previous results and the above-
mentioned purposes, our present study focuses on a
structurally related system containing 2,3-diamino-
naphthalene moieties. The few previously published
studies concerning the dinaphthotetraaza[14]annulene
(DNTAA) system were mainly limited to the unsubstituted
macrocycle and its transition metal complexes (6).
2. Results and discussion
2.1 Synthesis
9,20-Bis(2-hydroxybenzoyl)-7,18-dihydrodinaphtho[-
b,i][1,4,8,11]tetraazacyclotetradecine (DNTAA) 1 was
synthesised from 2,3-diaminonaphthalene and 3-formyl-
chromone in 70% yield using a procedure analogous to that
used earlier for the corresponding DBTAA ligand (8).
To synthesise products 2–5 shown in Scheme 1, we
used reactivity of OH groups at the meso benzoyl
substituents of 1.
Compounds 2–4 were synthesised via the alkylation of
1 with corresponding aliphatic bromides, carried out in
anhydrous dimethylformamide (DMF) in the presence of
anhydrous potassium carbonate. The lacunar product 3
Compared with the DBTAA derivatives studied earlier
in our group, the target molecule contains more extended
aromatic moieties due to the incorporation of
o-naphthylene units in the place of o-phenylene units. It
is reasonable to presume that such a change in structure
will influence the overall electronic system of the
macrocyclic core, thus modifying properties that are
crucial for potential applications. It is therefore expected
that the features depending on p–p aromatic interactions,
such as DNA-binding behaviour and the mesomorphic
properties of materials derived from the DNTAA
*Corresponding author. Email: jeilmes@chemia.uj.edu.pl
q 2013 Taylor & Francis

Supramolecular Chemistry
277
28
29 OH
27
24
O
26
23
25
9
10
8
5
2
6
1
12
17
13
16
7N N11
14
15
4
3
a
H
O
c
H
Ob
22N N18
Br
d
19
21
20
NH2
NH2
Br(CH2)4Br
O
N
N
N
N
H
H
HO
1
O
O
O
Br
O
O
CH3(CH2)7Br
4
Br(CH2)10Br
py
a
Br
a
O
O
O
O
c
c
e
f
Ob
e
O b
g
N
a
d
d
b
g
f
c
h
d
N
f
N
N
N
N
N
N
N
N
N
H
H
g
H
H
e
H
H
N
N
h
i
j
O
N
O
O
O
O
O
Br
2
3
5
Scheme 1. Syntheses of DNTAA 1 and its O,O-bis-alkylated derivatives 2–5.
was prepared by the bis-alkylation of 1 using 1,10-
dibromodecane. To synthesise the dicationic derivative 5,
substrate 1 was transformed to dibromide 4, which was
subjected to the reaction with anhydrous pyridine.
of 4.3(2)8 and 14.0(1)8, respectively (Figure 1(a)). The
dihedral angle between naphthalene rings themselves is
11.4(2)8. The benzoyl rings, C24-C29 and C42-C47, are at
53.5(1)8 and 53.8(1)8 dihedral angles against the
tetraaza[14]annulene ring and at 73.4(2)8 between
themselves.
All new products have been characterised by elemental
analysis, HR-MS, ESI-MS, 1H and 13C NMR and IR
1
spectroscopies. H and 13C NMR signals, their assign-
Crucial bond lengths and angles within the 14-
membered ring are given in Table 2. The values of the
appropriate valence angles at nitrogen atoms N7 and N18:
C6aZN7ZC8 ¼ 124.0(5) and C17aZN18ZC19 ¼
124.1(5)8 confirmed H-atom localisations at the nitrogen
atoms. On the contrary, the angles at N11 and N22:
C10ZN11ZC11a ¼ 120.3(5) and C21ZN22ZC22a ¼
121.5(5)8 indicate the sp2 hybridisation of the nitrogen
atoms. The intramolecular H-bonds, N7ZH7· · ·N11 and
N18ZH18· · ·N22, are described by the following geo-
ments and other spectroscopic and analytical data are
collected in Section 3.
2.2 Crystallography
The structures of compounds 3, 4 and 5 with the atom-
numbering scheme are shown in Figures 1–3, respectively.
Crystal data, data collection and structural refinement
details are given in Table 1.
˚
metrical parameters: 0.89(1), 2.07(4), 2.746(7) A and
˚
131(5)8 and 0.89(1), 2.15(5), 2.764(8) A and 126(5)8,
respectively.
Compound 3 (C50H46N4O4) crystallises in space group
P21/c (Z ¼ 4) with 0.90 CHCl3 per lacunar molecule in the
asymmetric part of the unit cell. Molecules of 3 occupy the
general position of the space group. The chlorine atoms of
the solvent molecules are disordered.
Packing of the molecules (Figure 1(b)) in the structure
is governed by weak intermolecular CZH· · ·O interactions
(9) between benzoyl CZH and carbonyl groups:
The conformation of the DNTAA moiety of 3 is not
˚
planar with the distortion from planarity of 0.1798(6) A
1
2
1
2
2x þ 1,
C43ZH43· · ·O23x,2y þ ,z 2 and C44ZH44· · ·O48
1
1
y þ , 2 z 2
2
2
, the geometrical parameters of which are
given in Table 3. Relatively short distances between H-
(rms deviation of the fitted atoms). The planes of two
naphthalene rings: C6a-C22a and C11a-C17a, with the
mean plane of the 14-membered ring form dihedral angles
˚
atoms and O-acceptors, 2.47 and 2.38 A, respectively, and

´
A. Kazmierska et al.
278
Figure 1. (a) Side view of 3 with the atom-numbering scheme. Atomic displacement ellipsoids are drawn at 30% probability level. The
DNTAA ring is not planar, and the positions of H-atoms are localised at N7 and N18 nitrogen atoms. (b) Packing of 3 viewed in [0 1 0]
direction. H-atoms were omitted for the clarity. The displacement ellipsoids are drawn at 30% probability level. The disordered molecules
of chloroform are shown. (c) The pair of 3 related by the centre of symmetry at (1/2, 0, 0) due to p–p (dashed lines in magenta) and
CZH· · ·p (dashed lines in black) interactions (compare Table 3). The displacement ellipsoids are drawn at 50% probability level.
Symmetry code i: 1 2 x, 2y, 2z.
˚
CZH· · ·O angles close to 1638 (almost linear H-bonds)
seem to be significant for the crystal structure stability.
Apart from mentioned H-bonds, the assembly is controlled
by p–p interactions between naphthalene rings
Cg2· · ·Cg32x þ 1, 2 y, 2 z and between the naphthalene
ring and pentanediimine system Cg1· · ·Cg62x þ 1, 2 y, 2 z
(Table 3), with the centroid–centroid distance of 3.709 and
of 3.12 and 3.13 A and nearly linear CHCg angles of 1758
and 1578, respectively.
Compound 4 crystallises in space group P21/n with
two centrosymmetric molecules of C48H42Br2N4O4 in the
unit cell (the asymmetric part contains one-half of the
molecule). Conformation of 4 with the atom-numbering
scheme is shown in Figure 2(a).
˚
3.742 A, respectively. It is worth noting that CgZCg
˚
distances are considered to be in the range of 3.4–4.0 A
Essential bond lengths are given in Table 2. H-atoms at
N2 and N9 are found to be disordered with the site
occupancy factor of 0.5. The conformation of the
DNTAA ring is chair like. The naphthalene moieties are
parallel to each other and form the angles of 4.3(1)8
with the inner fragment of the 14-membered ring,
i.e. N2ZC2aZC8aZN9ZN2iZC2aiZC8aiZN9i {(i)
2x þ 1, 2 y þ 1, 2 z þ 1}, whereas the pentanediimine
moiety forms the angle of 14.7(1)8 against the naphthalene
best planes.
(9), whereas the distance of one ring centroid to the plane
˚
of another ring interacting via p–p should be ca. 3.40 A.
In the case of the dimer of 3, the appropriate distances
are as follows: Cg62x þ 1, 2 y, 2 z to (C1 ^ C6a) ring
plane ¼ 3.407(3) and Cg32x þ 1, 2 y, 2 z to (C2 ^ C5a)
˚
ring plane ¼ 3.464 A.
Packing of the molecules, shown in Figure 1(b),(c),
also revealed intramolecular CZH· · ·p interactions
between alkyl CH2 groups and pentanediimine system,
the most significant of which are C33ZH33a· · ·Cg5 and
C37ZH37b· · ·Cg6, with relatively short H· · ·Cg distances
Side chains in meso positions are antiperiplanar with
dihedral angle of 88.47(5)8 between 14-membered ring
and the benzoyl best plane.

Supramolecular Chemistry
279
Figure 2. (a) View of 4 showing the conformation of DNTAA ring and antiperiplanar side chains with their atom-numbering scheme.
1 1 1
ꢀ
Atomic displacement ellipsoids are drawn at 50% probability level. The molecule is centrosymmetric: 1 (2,2,2). H-atoms at nitrogen N2
and N9 are disordered with the side occupancy factor of 0.5. The H-atom at N9 is not shown. (b) Packing of 4 viewed in [010] direction.
Note that H-atoms at nitrogen N2 and N9 are disordered with the side occupancy factor of 0.5. CZH· · ·p interactions are marked by
dashed lines (compare Table 3).
Packing of the molecules, shown in Figure 2(b), revealed
weak interactions of CZH·· ·O, CZH·· ·p and p–p types,
the geometrical parameters of which are given in Table 3.
The structure is stabilised by intermolecular interactions
between the aromatic CZH group and the oxygen atom
anions and two methanol molecules in the unit cell (the
asymmetric part contains half of the contents).
Conformation of 5 with the atom-numbering scheme is
shown in Figure 3(a),(b). Compound 5 is centrosymmetric:
21 (12,0,0). The values of bond lengths and angles for
pentanediimine system in 14-membered ring are given in
1
1
1
of carbonyl group, with H7· · ·O122x þ 1 ,y 2 , 2 z þ 1
˚
2
2
2
distance of 2.50 A, between methine C1ZH1 and benzoyl
ring, with H1· · ·Cg32x þ 1, 2 y þ 1, 2 z þ 1 distance of
Table 2. H-atom at N9 and also that at N92x þ 1, 2 y, 2 z
,
are localised. The value of valence angle C10ZN9ZC8a ¼
˚
2.92 A and between the adjacent naphthalene rings
125.7(1) in contrary to C1ZN9ZC2a ¼ 118.2(1) confirms
H-atom assignment. The geometrical parameters of
intramolecular H-bond N9ZH9·· ·N22x þ 1, 2 y, 2 z within
14-membered ring are as follows: 0.86(1), 2.09(2),
Cg2· · ·Cg22x þ 1, 2 y, 2 z þ 1, with the centroid–centroid
˚
distance of 3.542 A.
In conclusion, the pseudo-hexagonal packing of the
molecules in both 3 and 4 crystal structures is governed by
weak interactions between C-H from benzoyl group (in 3)
or from naphthalene part (in 4) and carbonyl CvO as well
as by p–p interactions (in the mode face-to-face) between
both naphthalene rings from one side and, either
pentanediimine or naphthalene moieties. The behaviour
of benzoyl fragment, together with edge-to-face inter-
action between the methine C1ZH1 and the gravity centre
of benzoyl ring as (Table 3), seems to play a significant
role in intermolecular interactions of the molecules.
˚
2.766(2) A and 136(2)8. An intermolecular H-bond,
O37ZH37·· ·Br1x22,y,z þ 1, is observed between the bro-
mide anion and the methanol molecule, and has the
˚
following parameters: 0.82(1), 2.44(1), 3.253(1) A and
169(2)8.
The conformation of the DNTAA ring is chair like and
is similar to that found for compound 4. Two naphthalene
rings are parallel to each other. The dihedral angle between
the inner fragment, N2ZC2aZC8aZN9ZN2iiZC2aiiZ
C8aiiZN9ii {(ii) 2x þ 1, 2 y, 2 z}, of 14-membered ring
and the naphthalene ring is 5.2(1)8 and the pentanediimine
system is inclined at 18.3(1) to the naphthalene ring best
ꢀ
Compound 5 crystallises in space group P1 (Z ¼ 1)
with one tetraaza cation C58H52N6O24þ, two bromide

´
A. Kazmierska et al.
280
Figure 3. (a) View of 5 onto DNTAA ring with the atom-numbering scheme. Atomic displacement ellipsoids are drawn at 50%
probability level. (b) View of 5 showing the conformation of tetraaza[14]annulene ring and antiperiplanar side chains with their atom-
numbering scheme. Atomic displacement ellipsoids are drawn at 50% probability level. (c) Packing of 5 viewed in [010] direction.
Methanol molecules and Br2 anions are omitted for clarity. p–p interactions between the benzoyl and pyridine rings are marked by
dashed lines (compare Table 3).
plane. The side chains (related by the centre of symmetry)
are bent above and below the 14-membered ring with the
angle of 69.34(3)8 between the macro ring and the benzoyl
ring.
In comparison to 3 and 4, 5 has additionally the
pyridine moiety which also interacts with the benzoyl
group in face-to-face mode despite being involved in
CZH· · ·Cg edge-to-face interaction (Table 3).
Packing of the molecules, shown in Figure 3(c),
revealed CZH· · ·p and p–p interactions. The most
significant were those between pyridine and benzoyl
3. Experimental
rings, with the Cg3·· ·Cg42x þ 1,y,z distance of 3.518 A,
˚
3.1 General
and between naphthalene rings with the distances
of Cg1· · ·Cg22x þ 1, 2 y þ 1, 2 z and Cg2· · ·Cg22x þ 1,
2,3-Diaminonaphthalene, 3-formylchromone, 1-bromo-
octane and 1,10-dibromodecane were purchased from
commercial sources (Sigma-Aldrich), and were used as
received. Solvents were dried using standard methods, and
were freshly distilled before use.
2 y þ 1, 2 z
˚
equal to 3.863 and 3.721 A, respectively. The
geometrical parameters characterising the intermolecular
interactions are given in Table 3.

Supramolecular Chemistry
281
a
b
g
b
b
s
u
r
s
r
m
u

´
A. Kazmierska et al.
282
˚
Table 2. Bond lengths (A) and angles (8) characteristic for pentanediimine system in 14-membered ring.
3
4
5
N7ZC8
C6aZN7
C10ZN11
N11ZC11a
C19ZN18
N18ZC17a
C8ZN7(C6a
C10ZN11ZC11a
C19ZN18ZC17a
C21ZN22ZC22a
1.333(6)
1.409(7)
1.311(6)
1.401(8)
1.317(6)
1.400(8)
124.0(5)
120.3(5)
124.1(5)
121.5(5)
N9ZC10
C8aZN9
C1ZN2
1.298(3)
1.407(3)
1.308(3)
1.418(2)
1.298(3)
1.407(3)
122.6(2)
122.2(2)
122.6(2)
122.2(2)
C1ZN2
N2ZC2a
N9ZC10
1.297(2)
1.416(2)
1.336(2)
1.412(2)
1.297(2)
1.416(2)
118.2(1)
125.7(1)
118.2(1)
125.7(1)
N2ZC2a
C8aZN9
N9iZC10i
C8aiZN9i
C8aZN9(C10
C1ZN2ZC2a
C1iiZN2ii
N2iiZC2aii
C1ZN2ZC2a
C8aZN9ZC10
C8ai ZN9i ZC10i
C1iZN2iZC2ai
C1iiZN2iiZC2aii
C8aii ZN9 ZC10ii
ii
Symmetry codes: (i) 2x þ 1, 2y þ 1, 2z þ 1; (ii) 2x þ 1, 2y, 2z.
Elemental analyses were carried out on an Elementar
vario MICRO cube analyser. 1H and 13C NMR
spectroscopy was carried out using a Bruker AVANCE
II 300 spectrometer. Chemical shifts (d) are expressed in
parts per million and J values in Hz. Signal multiplicities
are denoted as s (singlet), d (doublet), t (triplet), q (quartet)
and m (multiplet). ESI mass spectra were taken on a
Bruker Daltonics Esquire 3000 spectrometer. HR-MS
spectra were taken on a Waters Micromass Quattro LC
apparatus. The IR spectra were recorded with a Thermo
˚
Table 3. The geometrical parameters (A, 8) for weak interactions.
D-H· · ·A
D-H
H· · ·A
D· · ·A
D-H· · ·A
3
^0.01
3.36
3.18
3.65
3.52
2.66
3.12
3.13
3.32
3.38
3.18
3.22
2.47
2.38
^0.005
4.197
4.010
4.325
4.189
3.617
4.108
4.061
4.051
4.002
3.908
4.154
3.388
3.295
3.742
3.709
^0.002
3.644
4.480
3.961
3.852
6.126
3.435
3.632
3.542
^0.002
3.672
3.706
4.075
3.863
3.721
3.518
^1
147
147
128
127
164
175
157
132
125
135
169
163
163
1
2
12, z þ
12, z þ
C26ZH26· · ·Cg1x, 2y 2
C25ZH25· · ·Cg2x, 2y 2
C31ZH31a· · ·Cg3
0.95
1
2
0.95
0.99
0.99
0.99
0.99
0.99
0.99
0.95
0.95
0.95
0.95
0.95
C32ZH32b· · ·Cg32x, 2y, 2z
C31ZH31b· · ·Cl52x, 2y, 2z
C33ZH33a· · ·Cg5
C37ZH37b· · ·Cg6
C38ZH38a· · ·Cg72x, 2y, 2z
C45ZH45· · ·Cg72x þ 1, 2y, 2z
C46ZH46· · ·Cg72x þ 1, 2y, 2z
12, 2z 2
1
2
C2ZH2· · ·Cg82x þ 1, y 2
1
2
12, z 2
C43ZH43· · ·O23x, 2y þ
12, 2z 2
1
2
C44ZH44· · ·O482x þ 1, y þ
Cg1· · ·Cg62x þ 1, 2y, 2z
Cg2· · ·Cg32x þ 1, 2y, 2z
4
^0.01
2.92
3.60
3.29
3.08
4.35
2.50
^2
134
155
127
136
155
169
C1ZH1· · ·Cg32x þ 1, 2 y þ 1, 2z þ 1
0.95
0.95
0.99
0.99
1.954(3)
0.95
1
2
1
2
1
2
C6ZH6· · ·Cg32x þ 1 , y 2 1 , 2z þ 1
12, z þ
12, z þ
1
2
1
2
C21ZH21a· · ·Cg5x2 , 2y þ
1
2
1
2
C22ZH22a· · ·Cg1x2 , 2y þ
C23ZBr1· · ·Cg3x, y21, z
12, 2z þ 112
1
2
C7ZH7· · ·O122x þ 1 , y 2
Cg1· · ·Cg42x þ 1, 2y, 2z þ 1
Cg2· · ·Cg22x þ 1, 2y, 2z þ 1
5
^0.01
2.78
3.06
^2
156
127
136
C14ZH14· · ·Cg2
C15ZH15· · ·Cg1
0.95
0.95
0.91
C37ZH37b· · ·Cg32x þ 1, 2y þ 1, 2z
Cg1· · ·Cg22x þ 1, 2y þ 1, 2z
Cg2· · ·Cg22x þ 1, 2y þ 1, 2z
Cg3· · ·Cg42x þ 1, y, z
3.37
O37ZH37· · ·Br1x22,y,z þ 1
0.82(1)
2.44
3.253(1)
169
Notes: The appropriate ring gravity centres are defined as follows: for compound 3 Cg1, (C1 ^ C6a); Cg2, (C2 ^ C5a); Cg3, (C17 ^ C12a); Cg4, (C16a ^ C13); Cg5, (N7-C8-
C9-C10-N11); Cg6, (N18-C19-C20-C21-N22); Cg7, (C29 ^ C25); Cg8, (C46 ^ C44); for compound 4 Cg1, (C3a ^ C7a); Cg2, (C2a ^ C8a); Cg3, (C13 ^ C18); Cg4,
(N2ZC1ZC11iZC10iZN9i) with (i) ¼ (2x þ 1, 2y þ 1, 2z þ 1); Cg5, (C2aZC3ZC3aZC4ZC5ZC6ZC7ZC7aZC8ZC8a) and for compound 5 Cg1, (C3a ^ C7a); Cg2,
(C2a ^ C8a); Cg3, (C13 ^ C18); Cg4, (N24 ^ C29).

Supramolecular Chemistry
Fisher Scientific Nicolet IR200. Melting points were 3.2.3 Lacunar compound (3)
283
measured using a Boethius apparatus, and were not
corrected.
A reaction mixture consisting of 1 (0.15 g, 0.24 mmol),
1,10-dibromodecane (0.08 g, 0.26 mmol), potassium car-
bonate (0.5 g) and DMF (75 mL) was stirred for 48 h at
room temperature and then transferred to a separatory
funnel and partitioned between chloroform (50 mL) and
water (50 mL). The organic layer was separated, washed
with water (5 £ 50 mL) and then dried over anhydrous
MgSO4. The solvent was evaporated under vacuum, and
the oily residue was chromatographed on a silica gel
column using toluene–acetone (20:1) as eluent. The main
yellow fraction was collected and evaporated to dryness. A
solid residue was recrystallised from chloroform–hexane
(1:3). Yellow crystals were filtered off and washed with n-
hexane. Yellow prisms, yield 0.047 g (26%), mp . 3008C.
Crystals suitable for X-ray measurements were grown
from CDCl3. 1H NMR (300 MHz, CDCl3, d ppm): 0.78 (m,
4H, CH2), 0.93 (m, 4H, CH2), 1.12 (m, 4H, CH2), 1.53 (m,
4H, CH2), 3.93 (t, J ¼ 5.2 Hz, 4H, OCH2), 6.98–7.65 (m,
20H, ArH), 8.81 (d, J ¼ 6.6, 4H, vCHN), 13.74 (t,
J ¼ 6.6, 2H, NH); 13C NMR (75 MHz, CDCl3, d ppm):
27.2, 30.3, 30.4, 30.8, 69.4, 111.9, 112.4, 112.7, 121.9,
126.6, 128.1, 130.1, 130.6, 132.4, 136.9, 153.4, 156.7,
194.0; IR (ATR) nmax(cm21): 3052, 2925, 2851, 1650,
1610, 1592, 1560, 1290, 1249; ESI-HR-MS (m/z)
789.3423 (M þ Naþ).
3.2 Syntheses
3.2.1 9,20-Bis(2-hydroxybenzoyl)-7,18-
dihydrodinaphtho[b,i][1,4,8,11]tetraazacyclotetradecine
(1)
A reaction mixture consisting of 2,3-diaminonaphthalene
(0.12 g, 0.75 mmol) and 3-formylchromone (0.125 g,
0.75 mmol) in chloroform (20 mL) was refluxed with
stirring for 1 h. A yellow-orange, fairly insoluble
precipitate was collected and washed thoroughly with
hot butanol and chloroform. Yellow-orange powder, yield
0.175 g (70%), mp 233–2348C. 1H NMR (300 MHz,
0
DMSO-d6, d ppm): 7.00 (t, J ¼ 7.4, 2H, H26,26 ), 7.04 (d,
0
J ¼ 8.4,
2H,
H28,28 ),
7.42–7.47
(m,
8H,
0
0
H3,4,14,15,25,25 ,27,27 ), 7.84 (m, 4H, H2,5,13,16), 7.88 (s, 4H,
H1,6,12,17), 8.85 (d, 4H, J ¼ 6.4,vNCH), 10.32 (s, 2H,
OH), 13.87 (t, J ¼ 6.4, 2H, NH); IR (ATR) nmax(cm21):
3046, 1636, 1619, 1562, 1478, 1314, 1292, 1222. Anal.
Calcd for C40H28N4O4: C, 76.42; H, 4.49; N, 8.91. Found:
C, 76.30; H, 4.56; N, 8.99%.
3.2.2 9,20-Bis[2-(octoxy)benzoyl]-7,18-
dihydrodinaphtho[b,i][1,4,8,11]tetraazacyclotetradecine
(2)
3.2.4 9,20-Bis[2-(4-bromobutoxy)benzoyl]-7,18-
dihydrodinaphtho[b,i][1,4,8,11]tetraazacyclotetradecine
(4)
A reaction mixture consisting of 1 (0.126 g, 0.2 mmol),
anhydrous potassium carbonate (0.5 g) and n-octyl
bromide (0.11 mL, 0.6 mmol) in anhydrous DMF
(75 mL) was heated with stirring for 5 h at 808C. During
this time, the colour of the solution changed slowly from
orange to brown. The reaction mixture was cooled to room
temperature and then transferred to a separatory funnel and
partitioned between chloroform (50 mL) and water
(50 mL). The organic layer was separated, washed with
water (5 £ 50 mL) and dried over anhydrous MgSO4. The
solvent was removed under reduced pressure, and the oily
residue was chromatographed on a silica gel column using
toluene–acetone (10:1) as eluent. The main yellow
fraction was collected and concentrated into a small
volume. The product was precipitated with n-hexane
(5 mL). Yellow powder, yield 0.077 g (44%), mp 1438C.
1H NMR (300 MHz, CDCl3, d ppm): 0.62 (t, J ¼ 6.9 Hz,
6H, CH3), 0.96–1.09 (m, 16H, CH2), 1.23 (m, 4H, CH2),
1.62 (m, 4H, CH2), 3.98 (t, J ¼ 6.6 Hz, 4H, CH2O), 6.99–
7.69 (m, 20H, Ar-H), 8.84 (br s, 4H, vCHN), 13.92 (br s,
2H, NH); 13C NMR (75 MHz, CDCl3, d ppm): 14.54,
22.98, 26.57, 29.74, 29.75, 29.85, 69.37, 111.68, 112.99,
113.25, 121.63; 126.71, 128.05, 130.27, 132.13, 132.53,
137.39, 154.11, 193.90; IR (ATR) nmax(cm21): 3165,
3095, 2954, 2888, 1607, 1580, 1487, 1252, 1156; ESI-HR-
MS (m/z) 875.4503 (M þ Naþ).
A reaction mixture consisting of 1 (0.14 g, 0.22 mmol),
1,4-dibromobutane (0.26 mL, 2.2 mmol), potassium car-
bonate (0.12 g) and DMF (35 mL) was stirred for 48 h at
room temperature and then transferred to a separatory
funnel and partitioned between chloroform (50 mL) and
water (50 mL). The organic layer was separated, washed
with water (5 £ 50 mL) and then dried over anhydrous
MgSO4. The solvent was evaporated under vacuum, and
the oily residue was chromatographed on a silica gel
column using toluene–acetone (40:1) as eluent. The main
yellow fraction was collected, concentrated to a small
volume and left to crystallise in air. Deep-orange crystals
were collected and washed with n-hexane. Yield 0.044 g
(22%), mp 2638C. Crystals suitable for X-ray measure-
ments were grown from toluene. 1H NMR (300 MHz,
CDCl3, d ppm): 1.83 (m, 8H, ZCH2CH2Z), 3.23 (t,
J ¼ 6.3 Hz, 4H, CH2Br), 4.02 (t, J ¼ 6.3 Hz, 4H, CH2O),
6.99–7.69 (m, 20H, ArH), 8.82 (d, J ¼ 7.1 Hz, 4H,
vCHN), 13.94 (t, J ¼ 7.1 Hz, 2H, NH); 13C NMR
(75 MHz, CDCl3, d ppm): 28.35, 29.95, 33.97, 68.37,
111.74, 113.10, 113.39, 121.96, 126.81, 128.13, 130.23,
132.13, 132.57, 137.36, 154.00, 156.39, 193.68; IR (ATR)
n
max(cm21): 3053, 2954, 2930, 2870, 1657, 1609, 1562,
1286, 1254; ESI-MS (m/z) 897.20 (Mþ). Anal. Calcd for

´
A. Kazmierska et al.
284
C48H42Br2N4O4: C, 64.15; H, 4.71; N, 6.23. Found: C,
64.31; H, 4.64; N, 6.15%.
Crystal data: 3 C50H46N4O4·0.90 CHCl3: T ¼ 110(2) K,
monoclinic, space group P21/c, a ¼ 13.8790(8),
˚
b ¼ 15.7021(10), c ¼ 20.6126(12)A, b ¼ 105.886(6),
3
V ¼ 4320.5(4)A , Z ¼ 4, Dx ¼ 1.344 Mgm23. Intensity
˚
3.2.5 9,20-Bis{2-[4-(N-pyridinium-1-
yl)butoxy]benzoyl}-7,18-dihydrodinaphtho[b,i][1,4,8,
11]tetraazacyclotetradecine dibromide pentahydrate (5)
data: umax ¼ 25.008, completeness 0.998, R ¼ 0.1001 for
5056 reflections with I . s(I), wR 2 ¼ 0.2603 for all 7597
unique reflections; relatively high R-factors are due to
disordered solvent molecules (site occupancy factors for
chlorine atoms of chloroform molecules with different
orientations are as follows: 0.30 at positions Cl1ZCl2ZCl4,
0.30 at positions Cl3ZCl5ZCl6, 0.20 at positions
Cl5ZCl6ZCl7 and 0.10 at positions Cl2ZCl4ZCl8), good-
ness-of-fit parameters S ¼ 1.024. CCDC N. 898799.
Pyridine (20 mL) was added to 4-bromobutoxy derivative
4 (0.08 g, 0.09 mmol), and the mixture was heated with
stirring for 8 h at 458C. The solution was then cooled to
room temperature, and the precipitate was collected by
filtration and washed with n-hexane. Yellow powder, yield
0.082 g (86%), mp 256–2588C. Crystals suitable for X-ray
measurements were grown from methanol–pyridine (1:1).
1H NMR (300 MHz, CDCl3, d ppm): 1.60 (m, 4H, CH2),
1.85 (m, 4H, CH2), 4.12 (t, J ¼ 6.3 Hz, 4H, CH2O), 4.43
(t, J ¼ 7.5 Hz, 4H, CH2Nþ), 7.10 (t, J ¼ 7.5 Hz, 2H,
Crystal data: 4 C48H42Br2N4O4: T ¼ 110(2) K, mono-
clinic, space group P21/n, a ¼ 15.8211(3), b ¼ 7.9364(1),
3
˚
˚
c ¼ 16.0007(3) A, b ¼ 90.832(2)8, V ¼ 2008.88(6) A ,
Z ¼ 2 (Z0 ¼ 0.5), Dx ¼ 1.486 Mg m23. Intensity data:
umax ¼ 30.008, completeness 0.997, R ¼ 0.0403 for 3859
reflections with I . s(I), wR 2 ¼ 0.1124 for all 5835
unique reflections, goodness-of-fit parameters S ¼ 0.954.
CCDC N. 898800.
0
0
H27,27 ), 7.21 (d, J ¼ 8.4 Hz, 2H, H29,29 ), 7.40 (m, 6H,
0
0
H3,4,26,26 ,14,15), 7.53 (dt, J ¼ 1.6, 7.5 Hz, 2H, H28,28 ),
0
7.72 (m, 4H, Hf,f ), 7.73 (m, 4H, H1,6,12,17), 7.82
0
(m, 4H, H2,5,13,16), 8.26 (tt, J ¼ 1.2, 7.9 Hz, 2H, Hg,g ),
8.73 (d, J ¼ 6.5 Hz, 4H, vCHN), 8.79 (dd, J ¼ 1.2,
Crystal data: 5 C58H52N6O24þ2Br2 2 CH3OH:
0
6.9 Hz, 4H, He,e ), 13.51 (t, J ¼ 6.5 Hz, 2H, NH);
13C NMR (75 MHz, CDCl3, d ppm): 26.26, 29.08, 61.22,
68.49, 111. 60, 113.87, 114.14, 127.41, 128.66, 128.80,
129.82, 130.51, 132.59, 132.82, 136.89, 145.35, 146.18,
154.51, 156.40, 170.31, 192.83; IR (ATR) nmax(cm21):
3470, 3407, 3126, 3052, 2940, 2868, 1649, 1588, 1562,
1483, 1416, 1289, 1256; ESI-MS (m/z) 448.40 (M2þ/2).
Anal. Calcd for C58H52Br2N6O4·5 H2O: C, 60.74; H, 5.45;
N, 7.33. Found: C, 61.12; H, 5.18; N, 7.34%.
T ¼ 113(2) K, triclinic, space group P1, a ¼ 9.0889(2),
ꢀ
˚
b ¼ 9.3100(2), c ¼ 15.4082(4) A, a ¼ 82.966(2),
3
˚
b ¼ 79.175(2), g ¼ 87.680(2)8, V ¼ 1270.76(5) A ,
Z ¼ 1 (Z0 ¼ 0.5), Dx ¼ 1.465 Mg m23. Intensity data:
umax ¼ 30.008, completeness 0.999, R ¼ 0.0331 for 6565
reflections with I . s(I), wR 2 ¼ 0.0874 for all 7398
unique reflections, goodness-of-fit parameters S ¼ 1.060.
CCDC N. 898801.
3.3 Crystallography
4. Conclusions
X-ray measurements for crystals 3, 4 and 5 were taken on
SuperNova diffractometer (Oxford Diffraction) (10),
equipped with Dual Cu at zero Atlas diffractometer and
CryoJet low temperature device using MoKa radiation
A new bis(2-hydroxybenzoyl) derivative of the DNTAA
macrocycle 1 was obtained as a fairly insoluble product of
a reaction between 2,3-diaminonaphthalene and 3-
formylchromone. The alkylation of both phenolic OH
groups of 1 successfully led to new derivatives with open-
chain pendant substituents and an O,O-bis-alkylated
bridging superstructure. Crystallographic studies of the
products 3–5 were carried out, revealing numerous non-
covalent interactions. Among the interactions, those
involving naphthylene moieties, in both p–p and CH–p
modes, seem to have a crucial role in stabilising the crystal
structures. Thus, the presence of naphthylene fragments in
the structures of DNTAA derivatives provides additional
opportunities for non-covalent interactions of the
molecules.
˚
(l ¼ 0.71073 A); data collection, CrysAlisPRO (10); cell
refinement, CrysAlisPRO (10); data reduction, CrysAlis-
PRO (10); absorption correction, multi-scan (10); program
used to solve structure, SIR92 (11); program used to refine
structure, SHELXL97 (12); molecular graphics, ORTEP-3
(13); software used to prepare material for publication,
SHELXL97 (12) and WinGX (14).
The structures were solved by direct methods and
refined by full matrix least squares using anisotropic
displacement parameters for non-H-atoms. The H-atoms
of aromatic CZH, methyl and methylene groups were
found on Fourier difference maps and included in the
refinement in the positions calculated from geometrical
conditions. The H-atoms at N and O-atoms were localised
on Fourier difference maps and refined with restrained
NZH and OZH distances (DFIX procedure in SHELX97)
in riding model with Uizo ¼ UEquation (parent atom).
In summary, the new macrocyclic ligand 1, incorpor-
ating naphthylene moieties crucial for generating non-
covalent interactions and carrying reactive phenolic OH
substituents, represents a valuable building block that is
suitable for use in the preparation of various supramole-
cular receptors.

Supramolecular Chemistry
285
´
Eilmes, A.; Gorecki, M.; Frelek, J.; Heinrich, B.; Donnio,
B. Tetrahedron 2012, 68, 3875–3884; (c) Grolik, J.; Dudek,
Ł.; Eilmes, J. Tetrahedron Lett. 2012, 53, 5127–5130.
Acknowledgements
This research was carried out using the equipment that was
purchased, thanks to the financial support of the European
Regional Development Fund in the framework of the Polish
Innovation Economy Operational Program (contract No.
POIG.02.01.00-12-023/08).
´
(4) (a) Pawlica, D.; Radic-Stojkovic, M.; Sieron, L.; Piantani-
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