Modulation of Crystal Packing via the Tuning of Peripheral Functionality for a Family of Dinuclear Mesocates

Article abstract of DOI:10.1002/asia.202000686

A family of four novel pyrazinyl-hydrazone based ligands have been synthesized with differing functionality at the 5-position of the central aromatic ring. Previous work has shown such ligands to form dinuclear triple mesocates which pack to form hexagonal channels capable of gas sorption. The effect of the peripheral functionality of the ligand on the crystal packing was investigated by synthesizing complexes 1 to 4 which feature amino, bromo, iodo and methoxy substituents respectively. Complexes 1 to 3 crystallized in the same hexagonal space group P6₃/m and featured 1D channels. However, on closer inspection while the packing of 1 is mediated by hydrogen bonding interactions, the packing of complexes 2 and 3 are not, due to a subtlety different π–π stacking interaction enforced by the halogen substituent. The more bulky nature of the methoxy substituent of 4 results in the complex crystallizing in the triclinic space group P-1, featuring an entirely different crystal packing.

Full text of DOI:10.1002/asia.202000686

CHEMISTRY
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Accepted Article
Title: Modulation of Crystal Packing via the Tuning of Peripheral
Functionality for a Family of Dinuclear Mesocates
Authors: Ben H Wilson and Paul E Kruger
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10.1002/asia.202000686
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Modulation of Crystal Packing via the Tuning of Peripheral
Functionality for a Family of Dinuclear Mesocates
Benjamin H. Wilson*[a,b] and Paul E. Kruger [a]
Abstract: A family of four novel pyrazinyl-hydrazone based ligands
have been synthesized with differing functionality at the 5-position of
the central aromatic ring. Previous work has shown such ligands to
form dinuclear triple mesocates which pack to form hexagonal
channels capable of gas sorption. The effect of the peripheral
functionality of the ligand on the crystal packing was investigated by
synthesizing complexes 1 to 4 which feature amino, bromo, iodo and
methoxy substituents respectively. Complexes 1 to 3 crystallized in
the same hexagonal space group P63/m and featured 1D channels.
However, on closer inspection while the packing of 1 is mediated by
hydrogen bonding interactions, the packing of complexes 2 and 3 are
not, due to a subtlety different π-π stacking interaction enforced by
the halogen substituent. The more bulky nature of the methoxy
substituent of 4 results in the complex crystallizing in the triclinic space
group P-1, featuring an entirely different crystal packing.
bonds,9 systematically altering peripheral functional groups while
retaining an isostructural framework is challenging unlike in
MOFs.10 Therefore, a system in which peripheral functionality of
the ligand can be modulated without significantly altering the
crystal packing is highly desirable. We recently reported a
dinuclear triple mesocate incorporating a bispyrazinyl-hydrazone
ligand.5b The mesocate complex featured strong hydrogen
bonding and π-π stacking interactions between the hydrazide and
pyrazine moieties on neighboring complexes. This resulted in the
mesocates packing such that microporous hexagonal channels
were formed. Removal of the solvent molecules from these
channels resulted in a porous material which exhibited selective
carbon dioxide sorption over nitrogen rationalised by the
presence of fluorinated anions in the pores.11 In this work, the
peripheral functionality of the ligand is modified to investigate the
effect on the crystal packing to assess the reliability of this
mesocate tecton.The 5-position of the central aromatic ring of this
family of ligands can be readily functionalized via a number of
commercially available or readily synthesized isophthalic acid
precursors. We report the synthesis of four novel bispyrazinyl-
hydrazone ligands with amino, bromo, iodo and methoxy and their
resulting Fe(II) complexes and seek to rationalize the differences
in the crystal packing.
Introduction
Crystal engineering describes the use of supramolecular
interactions to design materials with desirable properties.1 One
strategy it to utilise molecular tectons designed to form specific,
spatially oriented intermolecular interactions and therefore
assemble in a controlled manner.2 This approach can be utilised
to engineer molecular materials containing extrinsic porosity,3
exemplified by the growing number of Hydrogen Bonded Organic
frameworks (HOFs)4 and other Molecular Porous Materials
(MPMs)3,5. Discrete metallo-supramolecular assemblies are an
attractive supramolecular tecton for building framework materials
as they provide a scaffold for the controlled orientation of
hydrogen bonding moieties.6 Framework materials based on
molecular species often suffer from instability unlike Metal
Organic Frameworks (MOFs)7 due to the weaker nature of the
network forming interactions. However, molecular species have
enhanced solubility making them solution processable.8 Due to
the weaker nature of hydrogen bonds compared to coordinate
[a]
[b]
B. H. Wilson, Prof. P. E. Kruger
MacDiarmid Institute for Advanced Materials and Nanotechnology,
School of Physical and Chemical Sciences
University of Canterbury
Christchurch 8041, New Zealand
B. H. Wilson
Department of Chemistry and Biochemistry
University of Windsor
Windsor, Ontario, N9B 3P4, Canada
E-mail: bwilson@uwindsor.ca
Figure 1. (top) The bispyrazinyl-hydrazone ligands for which the 5 position of
the central aromatic ring (R) has been functionalised with amino, bromo, iodo
and methoxy substituents. (bottom) A schematic representation of the dinuclear
triple mesocate formed with the family of ligands described above.
Supporting information for this article is given via a link at the end of
the document
Results and Discussion
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Ligands L1 to L4 formed complexes 1 to 4 with the molecular
formula [Fe2(L)3](BF4)4. Complexes 1 and 2 were synthesized by
stirring the appropriate ligand and Fe(BF4)2·6H2O in nitromethane
in a stoichiometry of 3:2. The poor solubility of ligands L3 and L4
in nitromethane required complexes 3 and 4 to first be
synthesized in acetonitrile, followed by subsequent crystallization
from nitromethane. The effect on the crystal packing by
modulating the peripheral functionality was then investigated
(figure 1).
results in the formation of intramolecular hydrogen bonding
interactions between the carbonyl oxygen atom and a hydrazide
group on an adjacent (inter-strand) ligand, O13···H11(N11),
2.328(3) Å, 127.7(3)° (figure 2, table S3). These hydrogen
bonding interactions are reinforced by three crystallographically
identical reciprocal edge-to-face C-H ···π interactions, C15-
H15···π(center-of-ring) 2.928(4) Å, 152.7(5)° (figure S2, table S4).
The mesocate structure is predominantly favored by the 1,3-
substitution pattern on the central phenyl spacer which induced
the bidentate coordination sites to be orientated in the same
direction.12 The intra-strand hydrogen bonding interactions further
support the formation of the mesocates structure. The C-H···π
interactions occur as a result of the strained ligand conformation
adopted upon the mesocate formation enforced by the 1,2-
substitution pattern on the central phenyl spacer. The
supramolecular interactions occurring between the mesocates in
1 are analogous to that of our previously reported complex, the
most prominent being a hydrogen bonding interaction between
the N6 atom of the pyrazine ring and the hydrazide moieties on
neighboring mesocates N11-H11···N6, 2.240(5) Å (figure S4,
table S5). An off-set π-π stacking interaction between the
pyrazine rings of neighboring mesocates is also evident with a
centroid-centroid separation of 3.719(4)Å (figure S4, table S6)
which extends down the crystallographic c-axis. This gives rise to
the formation of large hexagonal channels parallel to the
crystallographic c-axis (figure 2, figure S4-5). The Fe1-Fe1ˈ
spacing of adjacent mesocates forming a channel is 8.3172(6) Å
the channel diameter at the closest contact is ca. 6.09 Å. The
tetrafluoroborate anions line the sides of the 1-D channels,
disordered over two positions. Due to the high symmetry of the
space group and the disordered exhibited by the solvent
molecules, they were unable to be modelled satisfactorily and
therefore the SQUEEZE13 function of PLATON14 was applied. The
solvent accessible void was calculated to be 1031 Å3 and
contained 330 electrons, corresponding to 145 electrons per
mesocate. Therefore, the contents of the channel can be
approximated as three toluene molecules (150 electrons). TGA
analysis showed a 4.97% weight loss between 20 and 152 °C,
which is approximates one molecule of toluene which constitutes
5.1% of the mass of 1·C6H7, in agreement with the elemental
analysis. Thermogravimetric analysis also reveals that 1 is stable
until 200 °C after which there is a rapid decrease in the mass due
to decomposition. The addition of the amino substituent has had
a negligible effect on the crystal packing of 1 compared to our
previously reported complex,5b indicating the inherent stability of
the complementary hydrogen bonding and π-π stacking
interactions.
Complex 1
Vapor diffusion of toluene into a dark red nitromethane solution of
complex 1 gave red rod-shaped crystals. Single crystal X-ray
diffraction was conducted at 120 K and the data was solved and
refined in the same hexagonal space group as our previously
reported complex; P63/m.5b Much like the original complex, the
asymmetric unit contained one half of a ligand fragment
coordinated to one third of an Fe(II) center in a bidentate fashion.
The two crystallographically unique Fe-N bonds are 1.946(4) Å
(Fe1-N2) and 1.962(4) Å (Fe1-N3) and indicate that the Fe(II)
center is in the low spin state at 120 K (figure S1). The pitch of the
mesocate runs parallel to the crystallographic c-axis and
measures 11.625(2) Å and is congruent with a 3-fold roto-
inversion axis. The action of the aforementioned roto-inversion
axis followed by reflection about a mirror plane perpendicular to
the crystallographic c-axis generates the complete dinuclear triple
mesocate structure. The carbonyl functionality is not coplanar
with the central phenyl ring and exhibits an out of plane twist of
26.4(7)° (measured as the C13-C12-C14-C15 torsion). This
Complex 2
Vapor diffusion diisopropyl ether into a dark red nitromethane
solution of complex 2 gave red rod-shaped crystals. Single crystal
X-ray diffraction was conducted at 120 K and the data was solved
and refined in the same hexagonal space group as 1, P63/m,
however with a longer crystallographic c-axis dimension. The
asymmetric unit contained one half of a ligand fragment
coordinated to one third of an Fe(II) center in a bidentate fashion.
The two crystallographically unique Fe-N bonds are 1.95(1) Å
(Fe1-N2) and 1.953(9) Å (Fe1-N3) and indicate that the Fe(II)
Figure 2. (top) The dinuclear triple mesocate structure of 1 showing the
hydrazide hydrogen bonding interactions with the carbonyl oxygen atoms in
blue. (left) View of the crystal packing of 1 down the crystallographic c-axis
showing the hexagonal 1-D channel with the amine substituents highlighted in
space filling representation with the tetrafluoroborate anions. (right) The crystal
packing viewed down the crystallographic c-axis showing the tetrafluoroborate
anions lining the channel in space filling representation.
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twist of 23(2)° (measured as the C13-C12-C14-C15 torsion). This
results in the formation of intramolecular hydrogen bonding
interactions between the carbonyl oxygen atom and a hydrazide
group on an adjacent (inter-strand) ligand, O13···H11(N11),
2.370(8) Å, 123.4(7)° (table S3). These hydrogen bonding
interactions are reinforced by three crystallographically identical
reciprocal
edge-to-face
C-H···π
interactions,
C15-
H15···π(center-of-ring) 2.882(7) Å, 148.8(1)°(figure S7, table S4).
The combination of the hydrogen bonding and C-H···π
interactions result from the mesocate structure enforced by the
1,3-substitution pattern on the central phenyl spacer as discussed
for 1.
On first appearance, the packing of 2 seems analogous to 1.
When viewed down the crystallographic c-axis
a similar
hexagonal packing occurs (figure 3, figure S8), however with a
more compact 1-D channel. On closer inspection, the pyrazine
rings π-π stack upon one another with a noticeably larger centroid
separation of 4.16(1) Å (table S6). This is due to the stacking
interaction occurring between the opposite faces of the pyrazine
rings in comparison to 1. A direct consequence of this change in
π-π stacking is that the pyrazine-hydrazide hydrogen bond,
observed in 1, does not form. Instead a weak C-H···N interaction
between C4 and N6 of neighboring pyrazine rings occurs while
the hydrazide moieties form a hydrogen bonding interaction with
the tetrafluoroborate anions (figure 3, figure S6, table S5). The
Fe1···Fe1ˈ spacing of the Fe(II) centers coordinated to these
pyrazine rings also increases to 9.410(3) Å. The more expanded
packing along the crystallographic c-axis can be attributed to the
incorporation of the bromine functionality on C17. These bromine
atoms are orientated into the hexagonal channel towards one
another with a Br18···Br18 separation of 3.837(4) Å, 144.1(7)°
resulting in the formation of a trimeric type II halogen bond (figure
3).15 This more expanded packing of the mesocates propagates
along the c-axis resulting in a significantly long c-axis dimension
for 2 of 34.658(6) Å) in comparison to 1, 24.854(2) Å. There is
also a small decrease in the crystallographic a and b-axis from
14.340(1) Å for 1 to 12.928(3) Å for 2. This compression in the
crystallographic a and b-axis manifests itself as a more compact
1-D channel with a diameter at the closest contact of ca. 4.77 Å.
The tetrafluoroborate anions line the sides of the noticeably
thinner channel. As with 1, disordered solvent molecules occupy
the middle of the channel which, due to the high symmetry of the
space group, are unable to be modelled satisfactorily and
therefore the SQUEEZE13 function of PLATON14 was applied. The
solvent accessible void was calculated to be 1157 Å3 and
calculated to contain 362 electrons, corresponding to 181
electrons per mesocate. Therefore, the contents of the channel
can be approximated as two nitromethane molecule and two
diisopropyl ether molecules (148 electrons). Thermogravimetric
analysis reveals a weight loss of 5.91% between 26 and 133 °C
which corresponds to the loss of one diisopropyl ether molecule
which constitutes 5.1% of the mass of 2·C6H14O and is also
observed in the elemental analysis. Thermogravimetric analysis
also reveals that 2 is stable until 200 °C after which there is a rapid
decrease in the mass due to decomposition. While a similar
hexagonal type packing to 1 is observed, the incorporation of the
bromo substituent results in a halogen bonding interaction which
Figure 3. (top) The N6···H4(C4) interactions and the offset π···π interaction are
shown in green. The π···π interaction is measured via the centroid ···centroid
(red) separations. (middle) The crystal packing of
2 viewed down the
crystallographic c-axis. The trimeric Br···Br halogen bonding interactions are
shown in green. The three mesocates in pale green sit above the three
mesocates shown in pale blue. Hydrogen atoms and tetrafluoroborate anions
omitted for clarity. (bottom) Crystal packing of 2 in space filling representation
highlighting the apparent lack of 1D channels down the crystallographic c-axis.
center is in the low spin state at 120 K (figure S6). The pitch of the
mesocate runs parallel to the crystallographic c-axis and
measures 11.599(5) Å and is congruent with a 3-fold roto-
inversion axis. The action of the roto-inversion axis followed by
reflection about
a
mirror plane perpendicular to the
crystallographic c-axis generates the complete dinuclear triple
mesocate structure (figure S7). The carbonyl functionality is not
coplanar with the central phenyl ring and exhibits an out of plane
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prevents the hydrogen bonding interaction of 1 occurring. This
results expansion and contraction along the crystallographic c-
axis and crystallographic a and b-axis respectively giving rise to a
more compact 1-D channel.
S14-15). The π-π stacking of the pyrazine rings of neighboring
complexes upon
Complex 3
Vapour diffusion of diisopropyl ether into a dark red nitromethane
solution of complex 3 gave red prismatic crystals. Single crystal
X-ray diffraction was conducted at 120 K and the data was solved
and refined in the same hexagonal space group as 1, P63/m,
however with a longer crystallographic c-axis dimension. The
asymmetric unit contained one half of a ligand fragment
coordinated to one third of an Fe(II) centre in a bidentate fashion.
The two crystallographically unique Fe-N bonds are 1.958(7) Å
(Fe1-N2) and 1.955(7) Å (Fe1-N3) and indicate that the Fe(II)
centre is in the low spin state at 120 K (figure S10). The pitch of
the mesocate runs parallel to the crystallographic c-axis and
measures 11.622(4) Å and is congruent with a 3-fold roto-
inversion axis (figure S11). The action of the aforementioned roto-
inversion axis followed by reflection about a mirror plane
perpendicular to the crystallographic c-axis generates the
complete dinuclear triple mesocate structure. The carbonyl
functionality is not coplanar with the central phenyl ring and
exhibits an out of plane twist of 22.9(9)° (measured as the C13-
C12-C14-C15 torsion). This results in the formation of
intramolecular hydrogen bonding interactions between the
carbonyl oxygen atom and a hydrazide group on an adjacent
(inter-strand) ligand, O13···H11(N11), 2.942(9) Å, 125.0(6)°
(figure 4, table S3). These hydrogen bonding interactions are
reinforced by three crystallographically identical reciprocal edge-
to-face C-H ···π interactions, C15-H15···π(centre-of-ring)
2.850(5) Å, 147.3(7)° (figure S11, table S4).
Figure 5. (top) The dinuclear triple mesocate structure of 3 showing the
hydrazide hydrogen bonding interactions with the carbonyl oxygen atoms in
blue. Hydrogen atoms not participating in hydrogen bonding interactions and
tetrafluoroborate anions are omitted for clarity. (bottom) The crystal packing
viewed down the crystallographic c-axis. The complexes shown in green
interact with the neighbouring complexes shown in orange via non-conventional
O···H(C) interactions.
one another with a centroid···centroid separation of 4.182(7) Å, is
noticeably longer than that of 1 and similar to that of 2 (figure S10).
Much like 2, the opposite faces of the pyrazine rings are involved
in this stacking interaction, resulting in the absence of the
pyrazine-hydrazide hydrogen bonding interaction. Analogous to 2,
a weak C-H···N interaction between C4 and N6 of neighboring
pyrazine rings occurs, while the hydrazide moieties form a
hydrogen bonding interaction with the tetrafluoroborate anions
(figure S13, table S5-S6). The Fe1···Fe1 spacing of the Fe(II)
centers coordinated to these pyrazine rings is 9.424(2) Å similar
to that of 2. The iodo substituents are orientated into the
hexagonal channel towards one another with an I18···I18
separation of 3.985(2) Å resulting in a trimeric type II halogen
bond analogous to 2 (figure S13).15 Unlike the bromo substituents
of 2, the iodine atoms are modeled as disordered over two
positions with an occupancy ratio of 9:1.
Figure 4. The dinuclear triple mesocate structure of 3 showing the hydrazide
hydrogen bonding interactions with the carbonyl oxygen atoms in blue.
Hydrogen atoms not participating in hydrogen bonding interactions and
tetrafluoroborate anions are omitted for clarity.
The combination of the hydrogen bonding and C-H···π
interactions result from the mesocate structure enforced by the
1,3-substitution pattern on the central phenyl spacer as discussed
for 1 and 2. The similar nature of the ligand substituent to 2 results
in the complex adopting an isomorphous crystal packing (figure
This more expanded packing of the mesocates propagates along
the c-axis resulting in a significantly long c-axis dimension for 3 of
34.658(6) Å) in comparison to 1, 24.854(2) Å and similar to the
values for 2. Likewise, as for 2, there is also a small decrease in
the crystallographic a and b-axis from 14.340(1) Å for 1 to
12.928(3) Å for 3. The more compact 1D channel of 3 possesses
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a
diameter at the closest contact of ca. 3.99 Å. The
contain 345 electrons, corresponding to 173 electrons per
helicate. The solvent content can therefore be approximated as
tow diisopropyl ether and tow nitromethane molecules (180
electrons). Thermogravimetric analysis reveals a weight loss of
6.12% between 41 and 177 °C which corresponds to the loss of
one diisopropyl ether and one water molecule which constitutes
6.4% of the mass of 4·C6H14O·H2O and is also observed in the
elemental analysis. Thermogravimetric analysis also reveals that
the complex is stable until 200 °C after which there is a rapid
decrease in the mass due to decomposition. The incorporation of
the sterically encumbered methoxy substituent prohibits the
hexagonal type packing observed for 1 to 3 to occur, resulting in
a less symmetrical packing arrangement adopted instead.
Comparison of complexes 1 to 4
Structures 1-3 all crystallize in the same hexagonal space group
P63/m resulting in hexagonal channels parallel to the
crystallographic c-axis. However, only 1 has identical crystal
packing to that of our previously reported structure, as the amino
substituent plays no significant structure direction role. For 2 and
3. The propensity of the halogen functionalities to form halogen
bonds alters the crystal packing subtly. Looser packing of the
mesocates in 2 and 3 results in a significantly longer c-axis while
the a and b axis are slightly smaller than those of 1 and our
previously reported complex. When a more bulky substituent, that
cannot form stabilizing interactions with substituents on
neighboring mesocates, is employed the complexes pack in an
entirely different manner. The complex now crystallizes in the
triclinic space group P-1 and the hexagonal channels present in
complexes 1 to 3 no longer occur. This change in the packing is
proposed to be due to a steric effect, in contrast to 2 and 3 where
it is proposed to be due to an electronic effect (halogen bonding).
Computational chemistry is a complementary technique to single
crystal X-ray diffraction which can provide further insight into how
differing supramolecular interactions influence the 3D structure,23
however, it is beyond the scope of this work.
tetrafluoroborate anions line the sides of the noticeably thinner
channel in a manner analogous to 2. As with 1 and 2, disordered
solvent molecules occupy the middle of the channel which, due to
the high symmetry of the space group, are unable to be modelled
satisfactorily and therefore the SQUEEZE13 function of PLATON14
was applied. The solvent accessible void was calculated to be
1129 Å3 and calculated to contain 312 electrons, corresponding
to 156 electrons per mesocate. Therefore, the contents of the
channel can be approximated as two diisopropyl ether and one
water molecule (158 electrons). Thermogravimetric analysis
reveals a weight loss of 4.81% between 41 and 177 °C which
corresponds to the loss of one diisopropyl ether molecule which
constitutes 4.8% of the mass of 3·C6H14O and is also observed in
the elemental analysis. Thermogravimetric analysis also reveals
that the complex is stable until 200 °C after which there is a rapid
decrease in the mass due to decomposition.
Complex 4
Vapor diffusion of diisopropyl ether into a dark red nitromethane
solution of 4 gave red plate crystals. Single crystal X-ray
diffraction was conducted at 120 K and the data was solved and
refined in the triclinic space group P-1. The asymmetric unit
contained three ligands and two crystallograpically unique Fe(II)
centers (figure S16). The ligands coordinated to the Fe(II) centers
in a bidentate manner, forming a dinuclear triple mesocate. The
Fe-N bond lengths indicate that both Fe(II) centers exist in the low
spin state at 120 K (table S2). The pitch of the mesocate
measures 11.624(1) Å and the axis is no longer coincident with
the crystallographic c-axis. Like the previous complexes, the
carbonyl functionality is not coplanar with the central aromatic
rings of the ligands and with torsion angles ranging from 19.5(5)
to 23.0(6)°. As with the previously discussed complexes,
intramolecular hydrogen bonding interactions between the
carbonyl oxygen atom and a hydrazide group on an adjacent
(inter-strand) ligand, O···H(N), with values ranging from 2.856(5)
to 3.098(4) Å (figure 5, table S3). These hydrogen bonding
interactions are reinforced by three reciprocal edge-to-face C-
H···π interactions, C15-H15···π(center-of-ring) with values
ranging from 2.834(2) Å to 2.900(2) Å as observed in 1 to 3 (figure
S18, table S4). The inclusion of the methoxy functionality make
the complex sufficiently sterically encumbered such that the
packing observed for 1 or 2 and 3 cannot occur. Instead the
hydrazide moieties participate in hydrogen bonding interactions
with the tetrafluoroborate anions and a nitromethane solvent
molecule (figure S18, table S5). There are only weak
supramolecular interactions between neighboring mesocates in
the form of non-conventional hydrogen bonds. There are two
types of C-H···O interactions between the acetyl group of the
ligand on one mesocate and the carbonyl oxygen and the
methoxy oxygen atoms on a neighboring mesocate (figure S20).
This interaction leads to the formation of supramolecular dimers,
which pack end-on-end down the crystallographic c-axis (figure 5,
figures S20-22). While some of the nitromethane solvent
molecules were able to be modelled in the crystal structure, there
remained a large amount of disordered solvent and therefore the
SQUEEZE13 function of PLATON14 was applied. The solvent
accessible void was calculated to be 1126 Å3 and calculated to
Conclusions
A family of four novel pyrazinyl-hydrazone ligands have been
synthesized with a variety of functionality at the 5-position of the
central aromatic ring. When complexed with Fe(II), these ligands
coordinate in an unusual bidentate manner resulting in the
formation of dinuclear triple mesocates. While the variation of the
substituents in the 5-position of the central aromatic ring, R, have
no effect on the structure of the discrete complex formed, they
have a significant influence on the crystal packing of the complex
This is observed for 4, where the methoxy substituent has a major
structure directing role. When R = NH2, for 1, the complexes form
strong pyrazine-pyrazine π-π and pyrazine-hydrazone hydrogen
bonds, resulting in the formation of hexagonal channels parallel
to the c-axis. When R = Br or I for 2 and 3 respectively, the packing
is subtly different. The π-π interactions of the pyrazine rings occur
between the opposite faces and there are no pyrazine-hydrazone
hydrogen bonds. It is proposed that the occurrence of halogen
bonds between the Br or I substituents are responsible for the
altered crystal packing. When R = OMe for 4 the complex adopts
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catalytic amount of glacial acetic acid and the resulting white suspension
stirred at reflux overnight. After cooling to room temperature, the
precipitate was filtered and washed with ethanol (2x5 mL) the diethyl ether
(2x5 mL) to give a white powder (1.2 g, 2.9 mmol, 100% yield) MP: >300 °C
νmax (cm-1): 3396 (w), 3165 (br., w), 2961 (br. w), 1645 (s), 1615 (s), 1518
(s), 1471 (w), 1424 (m), 1346 (m), 1330 (m), 1258 (s), 1172 (m), 1156 (m),
1141 (m), 1118 (w), 1085 (m), 1052 (w), 1013 (m), 986 (w), 899 (w), 880
(w), 855 (s), 802 (w), 716 (w), 731 (w), 687 (m), 662 (br., m), 573 (w), 481
(w), 464 (w) ESI-MS: [C20H20N9O2]+ calc. 418.1735, meas. 418.1743
an entirely different crystal packing and the hexagonal channels
observed in the previous structures do not occur. As no prominent
intermolecular interactions can be ascertained from the structure
we postulate that the steric bulk of the methoxy substituent is
responsible for the drastic change in the crystal packing. The
variation of the peripheral functionality has provided insight into
how different types of supramolecular interactions modulate the
crystal packing whether it be a subtle or significant change.
Synthesis of 5-bromo isophatholyl hydrazide
Experimental Section
5-Bromo dimethyl isophthalate (0.8 g, 2.9 mmol) was dissolved in ethanol
(3 mL) heated at reflux to give a yellow solution. Hydrazine monohydrate
was added (0.71 mL, 15 mmol) and the resulting yellow solution which
formed a white precipitate after several hours. A further 3 mL of ethanol
was added and the white suspension was heated at reflux overnight. The
suspension was then cooled to room temperature and the white solid was
separated by filtration and washed with ethanol (3x5 mL) then diethyl ether
(2x10 mL) to give a white powder (0.78 g, 2.9 mmol, 100% yield). MP:
280 °C 1H-NMR (D6-DMSO): 4.55 (br. s., 4 H) 8.08 (d, J = 1.17 Hz, 2 H)
8.24 (d, J = 1.56 Hz, 2 H) 9.93 (br. s., 2 H) 13C-NMR (D6-DMSO): 122, 126,
132, 136, 164 νmax (cm-1): 3290 (s), 3176 (w), 3071 (w), 1638 (s), 1618 (s),
1571 (m), 1512 (s), 1430 (w), 1340 (m), 1313 (m), 1267(w), 1117 (m),
1005 (m), 914 (w), 888 (m), 788 (w), 769 (w), 741 (m), 731 (m), 675 (s),
624 (s) ESI-MS: [C8H10BrN4O2]+ meas. 272.9983, calc. 272.9982
Materials and methods
All reagents were used as received without further purification from BDH
1
and Sigma Aldrich. H and 13C-NMR measurements were carried out on
an Agilent 400 MR spectrometer operating at 400 MHz for 1H and 101 MHz
for 13C. Mass spectrometry analysis was obtained on a Bruker maXis 4G
time of flight spectrometer. Infrared spectra were recorded on a Bruker
ALPHA Platinum ATR FT-IR spectrometer in the range 400–4000 cm−1
.
Elemental analysis for C, H and N were carried out at Campbell Micro
Analytical Laboratories, Otago University, Dunedin. Difficulties were
encountered in synthesizing the complexes in bulk quantities and the
presence of impurities is reflected in the elemental analysis. However, as
it is solely the crystal structure of interest, the elemental analyses obtained
were deemed sufficient. Thermo gravimetric analysis was carried out on
an Alphatech SDT Q600 TGA/DSC apparatus. The sample holder was
alumina crucible and it was heated at 1° min-1 under a nitrogen flow of 100
mL min-1. Single crystal X-ray diffraction was carried out on an Agilent
Supernova with an Atlas CCD area detector using graphite-
monochromatized Cu-Kα (λ = 1.54178 Å) radiation. The structures were
solved using intrinsic phasing with SHELXT16 and refined on Olex217 using
all data by full matrix least-squares procedures with SHELXT-97.18 Non-
hydrogen atoms were refined with anisotropic displacement parameters.
Hydrogen atoms were included in calculated positions with isotropic
displacement parameters 1.2 times the isotropic equivalent of their carrier
atoms. The functions minimized were Σw(Fo2 − Fc2), with w = [σ2(Fo2) + aP2
Synthesis of L3
5-Bromo isophthaloyl hydrazide (0.703g, 2.57 mmol) was stirred in ethanol
(50 mL) at room temperature. 2-Pyridinecarboxaldehyde (564 μL, 5.92
mmol) was added followed by two drops of glacial acetic acid. The
resulting white suspension was heated overnight at reflux. Upon cooling to
room temperature, the white precipitate was filtered and washed with
ethanol (2x10 mL) and then diethyl ether (2x10 mL) to give a white powder
(0.854 mg, 1.8 mmol, 74% yield). MP: 256-258 °C νmax (cm-1):3220 (w, br.),
3053 (w, br.), 1649 (s), 1587 (w), 1544 (s), 1470 (m), 1430 (m), 1368 (m),
1341 (w), 1295 (s), 1274 (s), 1249 (s), 1167 (m), 1148 (m), 1064 (m), 994
(m), 951 (m), 890 (m), 785 (s), 753 (w), 729 (s) ESI-MS: [C20H18BrN8O2]+
meas.451.0523, calc. 451.0513, [C20H19BrN8O2]2+ meas. 227.0282 calc.
227.0283
+ bP]−1, where P = [max(Fo)2 + 2Fc ]/3. CCDC 2008563 to 2008566 contain
2
the supplementary crystallographic data for this paper. These data are
provided free of charge by the Cambridge Crystallographic Data Centre.
5-Bromo isophthalic acid,19 dimethyl 5-bromo isophthalate,19 dimethyl 5-
iodoisophthalate,20 5-Iodo isophthaloyl hydrazide21 and dimethyl 5-
methoxy isophthalate22 were synthesised following literature procedures.
Synthesis of L4
5-Iodo isophthaloyl hydrazide (400 mg, 1.2 mmol) was stirred in 25 mL
ethanol at room temperature. 2-Acetyl pyrazine (351 mg, 2.9 mmol) was
added followed by a catalytic amount of glacial acetic acid. The resulting
white suspension was heated at reflux overnight. The suspension was
filtered and washed with ethanol (2x5 mL) the diethyl ether (2x5 mL) to
give an off-white powder (561 mg, 1.1 mmol, 92% yield). MP: >300 °C νmax
(cm-1): 3171 (br., w), 3019 (br., w), 1665 (m), 1646 (s), 1615 (w), 1537 (s),
1468 (m), 1422 (m), 1369 (m), 1304 (w) 1252 (m), 1171 (s) 1155 (m) 1118
(s) 1073 (m), 1047 (m), 1012 (w), 986 (m), 928 (w), 866 (w), 855 (m), 821
(m), 789 (w), 761 (w), 728 (w), 713 (m), 682 (m), 652 (br., m), 564 (w), 459
(m)
Synthesis of 5-Amino isophthaloyl hydrazide
Dimethyl 5-amino isophthalate (1 g, 4.8 mmol) was dissolved in ethanol (5
mL) at reflux. Hydrazine mono hydrate (1.9 mL, 38 mmol) was added and
the resulting white suspension stirred at reflux overnight. After cooling to
room temperature, the white precipitate was filtered and washed with
ethanol (3x5 mL) and then diethyl ether (10 mL) to give a white powder
1
(968 mg, 4.6 mmol, 96% yield). MP: >300 °C H-NMR (D6-DMSO): 9.44
(2H, br., s), 7.29 (1H, s), 7.05 (2H, s), 5.39 (2H, s), 4.41 (4H, br., s) 13C-
NMR (D6-DMSO): 167, 149, 135, 115, νmax (cm-1): 3416(w), 3303 (br., m),
3219 (br., w), 1667 (m), 1589 (s), 1516 (s), 1309 (m), 1076 (w), 1001 (w),
946 (m), 869 (m), 818 (w), 750 (w), 729 (m), 679 (m), 598 (w), 443 (m)
ESI-MS: [C8H12N5O2]+ calc. 210.0986, meas. 210.0988
Synthesis of L4 5-methoxy isophthaloyl hydrazide
Dimethyl 5-hydroxy isophthalate (1.5 g, 6.7 mmol) was dissolved in ethanol
(10 mL) at reflux. Hydrazine mono hydrate (1.95 mL, 40 mmol) was added
and the resulting yellow solution heated at reflux overnight. During this time
a white suspension form which was subsequently cooled to room
temperature and then in the fridge for 15 minutes. The white precipitate
Synthesis of L1
5-Amino isophthaloyl hydrazide (600 mg, 2.9 mmol) was stirred in ethanol
(50 mL) at room temperature. 2-Acetyl pyrazine was added followed by a
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was filtered and washed with ethanol (2 mL) and diethyl ether (10 mL) to
give a white powder (1.36 g, 91 % yield). MP: 230-233 °C H-NMR (D6-
1468 (m), 1422 (m), 1369 (w), 1304 (m), 1252 (m), 1171 (s), 1155 (m),
1118 (m), 1073 (m)1047 (m), 1012 (w), 986 (w), 928 (m), 896 (m), 855 (w),
821 (w), 789 (w), 761 (w), 728 (w), 713 (m), 682 (m), 652 (m), 564 (w), 459
(m)
1
DMSO): 9.78 (2H, s), 7.84 (1H, s), 7.45 (2H, s), 4.49 (4H, br. s), 3.81 (3H,
s) 13C-NMR (D6-DMSO): 166, 159, 135, 119, 115, 56 νmax (cm-1):3323 (br.,
w), 3301 (br., w), 1643 (m), 1622 (m), 1592 (s), 1535 (m), 1511 (s), 1468
(w), 1452 (w), 1358 (w), 1314 (s), 1285 (m), 1251 (w), 1164 (m), 1131 (w),
1059 (m), 1006 (m), 978 (m), 907 (m), 870 (m), 821 (w), 728 (w), 687 (s),
621 (m), 594 (s), 543 (s), 437 (w) ESI-MS: [C9H13N4O3]+ calc. 225.0983,
meas. 225.0973
Synthesis of [Fe2(L4)3](BF4)2, 4
L4 (16.1 mg, 37.3 μmol) and Fe(BF4)2·6H2O (8.4 mg, 24.9 μmol) were
stirred in acetonitrile (10 mL) for 1 hour to give a dark red-purple solution.
The solvent was removed under reduced pressure to give a purple solid.
The purple solid was dissolved in nitromethane and stirred at room
temperature for 1 hour with a pinch of ascorbic acid. After standing at room
temperature for 1 hour the solution was filtered and vapor diffusion of
diisopropyl ether gave dark red block crystals suitable for single crystal X-
ray diffraction [Fe2(C21H20N8O3)3](BF4)4·3C6H14O·25H2O Found: C, 38.76
H, 3.86 N, 13.15 requires: C, 38.71 H, 6.10 N, 13.38% νmax (cm-1): 3432
(br., w), 3523 (br., w), 1791 (w), 1663 (s), 1593 (s), 1524 (w), 1499 (w),
1471 (m), 1409 (w), 1375 (m), 1344 (m), 1312 (w), 1284 (w), 1237 (br., m),
1194 (w), 1152 (w), 1054 (br., s), 890 (w), 847 (w), 794 (m), 761 (m), 746
(m), 693 (w), 675 (w), 650 (m), 602 (m), 520 (m), 469 (m)
Synthesis of L4
5-Methoxy isophthaloyl hydrazide (500 mg, 2.2 mmol) was stirred in
ethanol (40 mL) at room temperature. 2-Acetyl pyrazine (626 mg, 5.1
mmol) was added followed by a catalytic amount of glacial acetic acid. The
resulting white suspension was stirred at reflux overnight. After cooling the
room temperature, the precipitate was filtered and washed with ethanol
(3x5 mL) and diethyl ether (10 mL) to give a white powder (876 mg, 2.0
mmol, 91% yield). MP: >300 °C νmax (cm-1): 3166 (br., w), 3014 (br., w),
2960 (br. w), 1664 (m), 1643 (s), 1596 (w), 1539 (s), 1516 (m), 1496 (m),
1426 (m) 1369 (w), 1338 (s), 1317 (s), 1291 (w), 1254 (s), 1171 (m), 1155
(m), 1141 (m), 1121 (m), 1081 (m), 1047 (m), 1012 (m), 988 w), 903 (w),
877 (w), 853 (m), 840 (s), 762 (w), 730 (w), 687 (m), 662 (br. m), 572 (w),
478 (w) ESI-MS: [C21H21N8O3]+ calc., 433.1732 meas. 433.1738
Acknowledgements
The authors gratefully acknowledge the MacDiarmid Institute for
financial support. BHW gratefully acknowledges the receipt of the
Roper Scholarship (UC) and the New Zealand-France Friendship
Fund for financial support.
Synthesis of [Fe2(L1)3](BF4)2, 1
L1 (15.6 mg, 37.3 μmol) and Fe(BF4)2·6H2O (8.4 mg, 24.9 μmol) were
stirred in nitromethane (15 mL) overnight at ambient temperature. The
resulting red solution was filtered and vapour diffusion of toluene resulted
in red prism crystals suitable for single crystal X-ray diffraction.
[Fe2(C20H19N9O2)3](BF4)4·3C7H8·29H2O Found: C, 38.94 H, 3.70 N,
14.72% requires: C, 38.75 H, 5.58 N, 15.07% νmax (cm-1): 3207 (br., w),
1673 (m), 1632 (m), 1598 (s), 1571 (w), 1515 (w), 1492 (s), 1469 (s), 1374
(m), 1343 (w), 1288 (m), 1230 (m), 1190 (m), 1154 (w), 1035 (br., s) 881
(w), 849 (w), 798 (m), 761 (m), 693 (w), 669 (w), 650 (m), 602 (w), 580 (w),
490 (m)
Keywords: molecular porous materials • mesocate • Iron(II) •
crystal engineering • hydrazone
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A series of dinuclear double
Benjamin H. Wilson* and Paul E.
mesocates have been prepared with
different peripheral functionality on the
ligand. In certain cases this pendant
functionality - via either the formation
of additional supramolecular
interactions or an increase in steric
Kruger*
Page No. – Page No.
Modulation of Crystal Packing via the
Tuning of Peripheral Functionality for
a Family of Dinuclear Mesocates
Modulation of
Crystal Packing
bulk – has significant implications for
the crystal packing
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Author(s), Corresponding Author(s)*
((Insert TOC Graphic here; max. width: 11.5 cm; max. height: 2.5 cm))
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Title
Text for Table of Contents
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