H-bond mediated self-assembly 1-dimensional array of 3,6-Bis(3′- Pyridyl)-1,2,4,5-tetrazine with trimesic acid

Article abstract of DOI:10.1080/15421400590958214

3,6-Bis(3'-pyridyl)-l,2,4,5-tetrazine was prepared by reaction of 3-cyanopyridine with hydrazine. Slow evaporation of 3,6-bis(3′-pyridyl)-l, 2,4,5-tetrazine with trimesic acid, in a 2:1 molar ratio in methanol afforded single crystals of 1 C₃₃H₂₂N₁₂O₆, suitable for X-ray analysis. The product was characterized by spectroscopic and single-crystal X-ray diffraction studies. The hydrogen bond mediated self-assembly of 3,6-bis(3'-pyridyl)-l,2,4,5-tetrazine with trimesic acid molecules generates 1-dimensional multi-compartmental arrays in the solid state as revealed by X-ray crystallographic analysis. The crystal structure of 1 is monoclinic with a = 28.445(3), b = 6.7088(10), c = 33.846(4) A, a = 90°, β= 108.112(7°, γ -90°, Z = 8, and space group C2/c. The directional intermodular hydrogen bonding between 3,6-bis(3′-pyridyl)- 1,2,4,5-tetrazine and trimesic acid molecules uses O-H...N and C-H...O interactions, together with intramolecular C-H...N hydrogen bonding, to build up the one-dimensional network structure.

Full text of DOI:10.1080/15421400590958214

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H-Bond Mediated Self-Assembly
1-Dimensional Array of 3,6-
Bis(3′-Pyridyl)-1,2,4,5-
Tetrazine with Trimesic Acid
Wen-Jwu Wang a & Jau-Shuenn Wang a
a Department of Chemistry , Tamkang University ,
Tamsui, Taipei, Taiwan (ROC)
Published online: 31 Aug 2006.
To cite this article: Wen-Jwu Wang & Jau-Shuenn Wang (2005) H-Bond Mediated
Self-Assembly 1-Dimensional Array of 3,6-Bis(3′-Pyridyl)-1,2,4,5-Tetrazine with
Trimesic Acid, Molecular Crystals and Liquid Crystals, 440:1, 147-152, DOI:
10.1080/15421400590958214
To link to this article: http://dx.doi.org/10.1080/15421400590958214
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Mol. Cryst. Liq. Cryst., Vol. 440, pp. 147–152, 2005
Copyright # Taylor & Francis Inc.
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400590958214
H-Bond Mediated Self-Assembly 1-Dimensional Array of
3,6-Bis(30-Pyridyl)-1,2,4,5-Tetrazine with Trimesic Acid
Wen-Jwu Wang
Jau-Shuenn Wang
Department of Chemistry, Tamkang University, Tamsui, Taipei,
Taiwan (ROC)
3,6-Bis(30-pyridyl)-1,2,4,5-tetrazine was prepared by reaction of 3-cyanopyridine
with hydrazine. Slow evaporation of 3,6-bis(30-pyridyl)-1,2,4,5-tetrazine with tri-
mesic acid, in a 2:1 molar ratio in methanol afforded single crystals of 1
C33H22N12O6, suitable for X-ray analysis. The product was characterized by spec-
troscopic and single-crystal X-ray diffraction studies. The hydrogen bond
mediated self-assembly of 3,6-bis(30-pyridyl)-1,2,4,5-tetrazine with trimesic acid
molecules generates 1-dimensional multi-compartmental arrays in the solid state
as revealed by X-ray crystallographic analysis. The crystal structure of 1 is mono-
ꢀ
ꢀ
˚
clinic with a ¼ 28.445(3), b ¼ 6.7088(10), c ¼ 33.846(4) A, a ¼ 90 , b ¼ 108.112(7 ,
c ¼ 90ꢀ, Z ¼ 8, and space group C2=c. The directional intermolecular hydrogen
bonding between 3,6-bis(30-pyridyl)-1,2,4,5-tetrazine and trimesic acid molecules
uses OꢁH ꢂ ꢂ ꢂ N and CꢁH ꢂ ꢂ ꢂ O interactions, together with intramolecular
CꢁH ꢂ ꢂ ꢂ N hydrogen bonding, to build up the one-dimensional network structure.
Keywords: hydrogen-bond; monoclinic; multi-compartmental arrays; one-dimensional
network; self-assembly; solid state; trimesic acid
INTRODUCTION
The design of new molecular architectures has generated great inter-
est in crystal engineering over recent years. Especially, much investi-
gation into organic compounds has been carried out using the presence
of functional groups that can form strong and stable intermolecular
interactions [1]. Therefore, recognizing geometry and functionality
at the molecular level has relevant implications in the design of
This work was supported by the National Science Council, Taiwan (ROC), and
Tamkang University.
Address correspondence to Wen-Jwu Wang, Department of Chemistry, Tamkang
University, Tamsui 251, Taipei, Taiwan (ROC). E-mail: wjw@mail.tku.edu.tw
147

148
W.-J. Wang and J.-S. Wang
supramolecular patterns. These patterns in turn can be translated
into physical or chemical properties in a solid. Non-covalent interac-
tions have been extensively used in crystal engineering, since they
are the fundamental cause of the formation of crystals [2]. Hydrogen
bonding, p-p interactions, and p-hydrogen interactions have been used
in particular for this purpose. Hydrogen bonding is the most studied
intermolecular interaction, presumably due to its frequent presence
in organic solid molecules. The selectivity and directional nature of
hydrogen bonding has led to its extensive use in the construction
and stabilization of large non-covalently bonded molecular and supra-
molecular structures. Hydrogen bonds are formed when a donor
(DꢁH), with an available acidic hydrogen atom, is brought into inti-
mate contact with an acceptor (A) [3].
Hydrogen-bonded supramolecular structures represent a primary
tool for crystal engineering [4–6]. In such a context, trimesic acid
(benzene-1,3,5-tricarboxylic acid, TMA) is a molecule which predictably
forms networks with interesting supramolecular properties as a result
of its molecular symmetry and complementary hydrogen-bonding
capabilities. Carboxylic acids can form homo- or hetero-dimers
with a variety of complementary functional groups (e.g. pyridines,
2-aminopyridines and pyrimidines), This has allowed functionalized
TMA [7], its deprotonated forms [8], or its metal complexes [9, 10] to
be exploited as templates in crystal engineering studies. In this contri-
bution we report a one-dimensional network in the co-crystal of TMA,
2[3,6-bis(30-pyridyl)-1,2,4,5-tetrazine]ꢂ TMA, 1, the supramolecular
structure of which is effectively an enlargement of TMA.
EXPERIMENTAL
3,6-Bis(30-pyridyl)-1,2-dihydro-1,2,4,5-tetrazine [11]
A mixture of 3-cyanopyridine (10.4 g, 0.1 mol, Aldrich, 98%, b.p. 201ꢀC)
and an excess of hydrazine hydrate (10 ml, 0.32 mol, Aldrich) were
warmed on a water bath for 6 hr. The solid was collected and crystal-
lized from ethanol as yellow needles, m.p. 233–235ꢀC. The yield was
8.6 g (72%).
3,6-Bis(30-pyridyl)-1,2,4,5-tetrazine [11]
3,6-Bis(30-pyridyl)-1,2-dihydro-1,2,4,5-tetrazine (7.0 g) was dissolved
in a mixture of glacial acetic acid (300 ml) and water (200 ml) and
cooled to 0ꢀC. Sodium nitrite (9.2 g) in cold water (25 ml) was added
to this solution slowly with vigorous stirring. The color of the solution

H-Bond Mediated Self-Assembly
149
turned red-purple. The mixture was neutralized with ammonia
solution and the product was collected by filtration. It was crystallized
from ethanol to afford purplish red plates, m.p. 201–202ꢀC. The yield
was 4.2 g (61%).
2[3,6-Bis(30-pyridyl)-1,2,4,5-tetrazine] ? TMA
Crystals of the compound suitable for single-crystal X-ray analysis
were grown by slow evaporation of a methanol solution containing a
mixture of 3,6-bis(30-pyridyl)-1,2,4,5-tetrazine and trimesic acid in a
2:1 molar ratio.
RESULTS AND DISCUSSION
The title compound, 2[3,6-bis(30-pyridyl)-1,2,4,5-tetrazine] ꢂ TMA, 1,
consists of 3,6-bis(30-pyridyl)-1,2,4,5-tetrazine (3-pta) and trimesic
acid (TMA) in a 2:1 ratio as shown in Figure 1. Molecules of the title
compound are linked by OꢁHꢂ ꢂ ꢂN and CꢁHꢂ ꢂ ꢂO intermolecular hydro-
gen-bonding. Within the asymmetric unit of the crystal 1, both 3-pta
FIGURE 1 The structure and atom-numbering scheme of 1.

150
W.-J. Wang and J.-S. Wang
ꢀ
˚
TABLE 1 Hydrogen-Bonding Geometry Close Contacts (A, )
D–Hꢂ ꢂ ꢂA
D–H
Hꢂ ꢂ ꢂA
D–Hꢂ ꢂ ꢂA
O1ꢁH43ꢂ ꢂ ꢂN2i
0.93(7)
0.95(6)
0.71(6)
0.93(1)
0.93(1)
1.73(7)
1.67(6)
1.95(6)
2.56(6)
2.39(5)
2.649(9)
2.605(1)
2.652(1)
3.246(1)
3.182(1)
169(6)
171(5)
171(7)
130(3)
142(4)
O3ꢁH44ꢂ ꢂ ꢂN35ii
iii
O6ꢁH45ꢂ ꢂ ꢂN150
C1ꢁH1ꢂ ꢂ ꢂO2iv
v
C16ꢁH16ꢂ ꢂ ꢂO50
Symmetry codes: (i) 1=2 ꢁ x, 1=2 ꢁ y, ꢁ z; (ii) x, 1 þ y, z; (iii) 1 ꢁ x, y, 1=2 ꢁ z; (iv)
1=2 ꢁ x, 1=2 ꢁ y, ꢁ z; (v) 1 ꢁ x, ꢁ 1 þ y, 1=2 ꢁ z.
molecules are interconnected with a trimesic acid molecule by means
of intermolecular OlꢁH43ꢂ ꢂ ꢂN2, C1ꢁH1ꢂ ꢂ ꢂO2 and O3ꢁH44ꢂ ꢂ ꢂN35
hydrogen-bonding, with angles of 169(6)ꢀ, 130(5)ꢀ and 171(5)ꢀ respect-
ively. The carboxylate group of the trimesic acid exhibits further
hydrogen-bonding O6ꢁH45ꢂ ꢂ ꢂN150 and C16ꢁH16ꢂ ꢂ ꢂO50 with a 3-pta
of the adjacent asymmetric unit, with angles of 171(7)ꢀ and 142(6)ꢀ
respectively, to build up the expanded one-dimensional network struc-
ture. The hydrogen bond parameters are listed in Table 1. For two
neighboring chains, the molecules extend the one-dimensional net-
work in the reverse direction through anti-parallel packing as shown
in Figure 2. In the asymmetric unit, only one of the 3-pta molecules
generates an intermolecular hydrogen-bond with the adjacent asym-
metric unit to create molecular ribbons. The other 3-pta does not
intereact with the adjacent asymmetric unit, therefore the one-dimen-
sional chains form branches of 3-pta molecules, that mutually inter-
digitate. In the packing as shown in Figure 3., TMA is connected to
FIGURE 2 The expanded structure of 1, showing the molecular ribbons pro-
jected onto the ac plane.

H-Bond Mediated Self-Assembly
151
FIGURE 3 The unit cell packing diagram of 1.
TABLE 2 Crystal Data of 1 [12]
C33H22N12O6
Mr ¼ 682.63
Dx ¼ 1.477 Mg=m3
h ¼ 2.25–25.00ꢀ
m ¼ 0.107 mmꢁ1
T ¼ 293(2) K
Monoclinic, C2=c
˚
a ¼ 28.445(3) A
˚
b ¼ 6.7088(10) A
0.55 ꢃ 0.13 ꢃ 0.05 mm
˚
˚
c ¼ 33.846(4) A
Wavelength ¼ 0.71073 A
F(000) ¼ 2816
h ¼ 0 < 33
a ¼ 90ꢀ
b ¼ 108.112(7)ꢀ
c ¼ 90ꢀ
k ¼ 0 < 7
˚
V ¼ 6138.91(3) A
l ¼ ꢁ40 < 38
Z ¼ 8
5508 Reflections collected
5395 Independent reflections Rint ¼ 0.0937
Absorption correction: empirical
Tmin ¼ 0.3539, Tmax ¼ 0.3366
Refinement method: Full-matrix least-squares on F2
Data=restraints=parameters: 5395=0=472
Goodness-of-fit on F2: 0.957
Final R indices [I > 2r(I)]: R1 ¼ 0.0975, wR2 ¼ 0.0595
R indices (all data): R1 ¼ 0.3511, wR2 ¼ 0.0951
Largest diff. Peak and hole: 235 and –233 e nm ꢁ3

152
W.-J. Wang and J.-S. Wang
three 3-pta molecules by OꢁHꢂ ꢂ ꢂN and CꢁHꢂ ꢂ ꢂO interactions, in
which only two of the 3-pta extend to generate intermolecular
hydrogen-bonds with the adjacent trimesic acid molecules through
O6ꢁH45ꢂ ꢂ ꢂN150 and C16ꢁH16ꢂ ꢂ ꢂO50 interactions, that consequently
maintain the one-dimensional structure.
Within the asymmetric unit of 1, the 3-pta and trimesic acid mole-
cules are nearly planar. The dihedral angles between 3-pta and TMA
are 7.3ꢀ and 5.1ꢀ respectively. For the trimesic acid, the two O atoms of
the carboxylate groups are slightly displaced from the plane of the
aromatic ring. The dihedral angles of the carboxylate groups
O1=O2=C43=C37, O3=O4=C44=C39 and O5=O6=C45=C41 with respect
to the attached aromatic rings are 4.0ꢀ, 4.9ꢀ and 3.6ꢀ, respectively.
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