Directed assembly of dinuclear and mononuclear copper(II)-carboxylates into infinite 1-D motifs using isonicotinamide as a high-yielding supramolecular reagent

Article abstract of DOI:10.1039/B308446A

Isonicotinamide has been employed as a supramolecular reagent in the synthesis of five Cu(II) complexes, tetrakis(μ-acetato-O,O′)-bis(isonicotinamide-N)dicopper(II) acetonitrile; trans-diaquabis(2-fluorobenzoato-O)-bis(isonicotinamide-N)copper(II), bis{bis(μ₂-acetato-O)-acetic acid-O-bis(isonicotinamide-N)copper(II)} bis(methanol), bis(acetato-O)-acetic acid-O-bis(isonicotinamide-N)copper(II) acetic acid, bis(2-fluorobenzoato-O)-2-fluorobenzoic acid-O-bis(isonicotinamide-N)copper(II). The crystal structure determination of these compounds demonstrate that an effective supramolecular reagent can be combined with very different (chemically and structurally) inorganic building blocks and still create a family of inorganic-organic hybrid materials that all display the same principal supramolecular motifs; infinite 1-D chains. This consistency (which can be equated with a high supramolecular synthetic 'yield') has been achieved in the presence of several potentially disruptive (in a structural sense) molecules, e.g. water, methanol, and acetic acid. This illustrates that flexible or unpredictable coordination chemistry does not, in itself, necessarily prevent supramolecular synthesis using a reliable supramolecular reagent, in this case the structurally bifunctional isonicotinamide ligand.

Full text of DOI:10.1039/B308446A

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Directed assembly of dinuclear and mononuclear copper(II)-
carboxylates into infinite 1-D motifs using isonicotinamide as a
high-yielding supramolecular reagent
Christer B. Aakeröy,a Alicia M. Beatty,b John Desper,a Mick OЈSheac and
Jesús Valdés-Martínezd
a Department of Chemistry, Kansas State University, Manhattan, KS, 66506, USA.
E-mail: aakeroy@ksu.edu; Fax: 1 785 532 6666; Tel: 1 785 532 6665
b Department of Chemistry, Mississippi State University, Box 9573, Mississippi State, MS,
39762, USA
c Department of Physics, Kansas State University, Manhattan, KS, 66506, USA
d Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior,
Ciudad Universitaria, Coyoacán 04510, D.F., México. E-mail: jvaldes@servidor.unam.mx
Received 22nd July 2003, Accepted 27th August 2003
First published as an Advance Article on the web 8th September 2003
Isonicotinamide has been employed as a supramolecular reagent in the synthesis of five Cu() complexes,
tetrakis(µ-acetato-O,OЈ)-bis(isonicotinamide-N)dicopper() acetonitrile; trans-diaquabis(2-fluorobenzoato-O)-
bis(isonicotinamide-N)copper(), bis{bis(µ2-acetato-O)-acetic acid-O-bis(isonicotinamide-N)copper()}
bis(methanol), bis(acetato-O)-acetic acid-O-bis(isonicotinamide-N)copper() acetic acid, bis(2-fluorobenzoato-O)-
2-fluorobenzoic acid-O-bis(isonicotinamide-N)copper(). The crystal structure determination of these compounds
demonstrate that an effective supramolecular reagent can be combined with very different (chemically and
structurally) inorganic building blocks and still create a family of inorganic–organic hybrid materials that all display
the same principal supramolecular motifs; infinite 1-D chains. This consistency (which can be equated with a high
supramolecular synthetic ‘yield’) has been achieved in the presence of several potentially disruptive (in a structural
sense) molecules, e.g. water, methanol, and acetic acid. This illustrates that flexible or unpredictable coordination
chemistry does not, in itself, necessarily prevent supramolecular synthesis using a reliable supramolecular reagent,
in this case the structurally bifunctional isonicotinamide ligand.
pyrazine and Cu() ions to produce a 2-D network with
Introduction
rectangular channels,15 and similar 2-D square networks with
open channels have been constructed from Zn()12 or Cd()16
and 4,4Ј-bpy. Other examples include Ag() helicates,17 circular
double helicates,18 supramolecular macrocycles,19 zinc()
porphyrins assembled into cages,20 and a large number of
interpenetrating diamondoid structures.21
Crystal engineering1,2 has focused primarily on the syntheses
of (i) extended organic networks (notably using hydrogen
bonds),3–,5 and (ii) transition-metal based coordination poly-
mers (relying on coordinate covalent bonds).6,7 Much less work
has been done on the construction of inorganic–organic hybrid
materials with intermolecular forces.8 The synthetic tools avail-
able for the construction of such assemblies are non-covalent
interactions, many of which are poorly understood and difficult
to calculate and measure. Consequently, controlling the proper-
ties of a solid through precise control over its crystal structure
or principal structural motifs is a formidable task. The good
news is that many assemblies and structural patterns have been
constructed through intermolecular interactions, and the use of
molecules or ions (instead of atoms) as building blocks of func-
tional solids and ordered networks has become an important
synthetic strategy in chemistry and materials science.
Only recently have non-covalent interactions (notably hydro-
gen bonds) been used in a deliberate strategy for connecting
metal complexes into extended networks.22–26 The inherent co-
ordination geometry of the metal ion can be propagated
through ligand-based hydrogen-bond interactions into
a
specific supramolecular architecture which demonstrates that
hydrogen bonds working in concert are capable of ‘mano-
euvring’ substantial complex ions into desirable motifs, even in
the presence of competing cation–anion, solvent–metal, and
solvent–solvent interactions.
Effective supramolecular synthesis requires non-covalent
intermolecular forces that consistently form reliable and specific
motifs even in the presence of potentially disrupting counter-
ions, solvent molecules, and other chemical or geometric
variables. This is particularly important in the design on new
functional materials where a desirable physical property is
crucially dependent upon an optimum three-dimensional
structure. In the context of molecular-based magnet materials,
Cu() has played a prominent role, both in experimental and
theoretical studies.27 Unfortunately (from the point of view of
structural consistency) Cu() displays a very varied and
unpredictable coordination chemistry, which makes it all the
more difficult to incorporate such ions into extended assemblies
with predetermined topology and connectivity.
Composite hybrid materials are of crucial importance in
natural systems9 but the combination of organic ligands and
transition-metal ions also brings together synthetic flexibility
(from the principles of organic chemistry) and properties and
reactivities inherent in metal ions. The reasons for incorporat-
ing metal ions into supramolecular networks are numerous;
metal ions give access to physical properties that are less com-
mon in organic solids e.g. magnetic properties, conductivity,
and catalytic activity (metal complexes with hydrogen-bonding
capabilities may also be used as chemotherapeutic com-
pounds).10 Metal ions also display a range of coordination
geometries allowing for greater flexibility in constructing
materials with specific dimensions and topologies. Supra-
molecular synthesis of metal-containing materials has prim-
arily been achieved by coordinating bifunctional ligands such
as 4,4Ј-bipyridine to metal ions.11–14 Some examples include
In this paper we demonstrate how isonicotinamide can be
employed as a practical ‘supramolecular reagent’, an effective
tool for consistently assembling coordination complexes of
D a l t o n T r a n s . , 2 0 0 3 , 3 9 5 6 – 3 9 6 2
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
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Cu(), with widely differing geometries and ligands, into
infinite 1-D chains. The supramolecular synthetic strategy
employed here combines the metal-coordinating ability of
pyridine and the robust self-complementary hydrogen-
bonding ability of the amide functionality.28 This approach
allows for the repeated construction of infinite 1-D motifs
containing either mononuclear or dinuclear copper() co-
ordination complexes as illustrated by the crystal structures of
tetrakis(µ-acetato-O,OЈ)-bis(isonicotinamide-N)-dicopper()
acetonitrile 1, trans-diaqua-bis(2-fluorobenzoato-O)-bis(iso-
SHELXL-97.29 Non-hydrogen atoms were found by successive
full matrix least squares refinement on F 2 and refined with
anisotropic thermal parameters. Hydrogen atom positions
were located from difference Fourier maps and a riding model
with fixed thermal parameters [uij = 1.2Uij(eq) for the atom to
which they are bonded] was used for subsequent refinements.
Table 1 provides crystallographic details for 1–5, and the
molecular geometries and numbering scheme are shown in
Figs. 1a–e.
CCDC reference numbers 215919–215923.
See http://www.rsc.org/suppdata/dt/b3/b308446a/ for crystal-
lographic data in CIF or other electronic format.
nicotinamide-N)copper()
2,
bis{bis(µ2-acetato-O)-acetic
acid-O-bis(isonicotinamide-N)copper()} bis(methanol) 3,
bis(acetato-O)-acetic acid-O-bis(isonicotinamide-N)copper()
acetic acid 4, and bis(2-fluorobenzoato-O)-2-fluorobenzoic acid-
O-bis(isonicotinamide-N), 5.
Magnetic measurements
Magnetic measurements were carried out using a Quantum
Design MPMS5 SQUID magnetometer with maximum applied
field of 55 kOe. Samples in powder form were packed in plastic
capsules and the measurements were performed under flowing
He gas.
Experimental
Preparation of 1
A solution of isonicotinamide (0.40 g, 3.2 mmol) in acetonitrile
was added to a solution of copper() acetate in acetonitrile
(0.050 g, 0.25 mmol) with a few drops of glacial acetic acid (to
obtain a clear solution). The mixture was heated for fifteen
minutes and left to stand at ambient temperature, blue-green
crystals of 1 appeared overnight. Repeated recrystallization
from acetonitrile with a few drops of acetic acid produced
crystals suitable for single-crystal X-ray diffraction.
Results
The crystal structure of 1 contains the commonly occurring
dinuclear (‘paddlewheel’)copper() unit constructed by four
bridging acetate ligands, Table 2. The ‘peripheral’ coordination
site on each ion is occupied by an isonicotinamide ligand (co-
ordination through the pyridine nitrogen atom). This arrange-
ment means that the two amide functionalities are oriented in a
linear fashion but pointing in opposite directions. Each amide
moiety forms two symmetry related N–H ؒ ؒ ؒ O hydrogen
bonds, Table 3, with an adjacent metal complex, resulting in
infinite linear chains of ions, Fig. 2. Neighbouring chains are
arranged in a parallel manner although there are no strong
hydrogen bonds between chains.
Preparation of 2
Blue crystals of 2 were obtained either from the same solution
as 5 or by recrystallisation of 5 in water.
Preparation of 3
The remaining N–H proton on each amide functionality
forms an N–H. ؒ ؒ ؒ N hydrogen bond (r(N ؒ ؒ ؒ N) 3.07 Å) to
the included acetonitrile. The Cu ؒ ؒ ؒ Cu separation within the
dinuclear core is 2.61 Å, and the Cu ؒ ؒ ؒ Cu distance between
adjacent metal-complexes within each hydrogen-bonded chain
is 17.0 Å. The shortest through-space inter-chain distance
between Cu() ions is 6.2 Å.
The crystal structure of 2 contains copper() ions in an elon-
gated tetragonal octahedral (4 ϩ 2) coordination geometry,
with two molecules of water and isonicotinamide and two
2-fluorobenzoate ions, all coordinated in a trans fashion, Table
2. There are no bridging or chelating ligands; this is a mono-
nuclear species. As in the crystal structure of 1, the two
isonicotinamide ligands act as conventional ligands (through
the pyridine nitrogen atom) and as supramolecular reagents
through self-complementary N–H ؒ ؒ ؒ O hydrogen-bond
interactions, Fig. 3, Table 3.
As well as being weakly coordinated to the metal-ion
(r(O ؒ ؒ ؒ Cu) 2.65 Å) the water molecule also acts as a
hydrogen-bond acceptor for an anti-amide proton and as an
intramolecular hydrogen-bond donor to a non-coordinated
carboxylate oxygen atom. The water molecules effectively
act as bridges between parallel hydrogen-bonded chains,
Fig. 4.
The Cu ؒ ؒ ؒ Cu distance between adjacent metal-ions within
each hydrogen-bonded chain is 16.8 Å. The shortest through-
space inter-chain Cu ؒ ؒ ؒ Cu distance is 7.5 Å.
A solution of isonicotinamide (0.40 g, 3.2 mmol) in methanol
was added to a solution of copper() acetate in methanol
(0.050 g, 0.25 mmol) with a few drops of glacial acetic acid (to
obtain a clear solution). The mixture was heated for fifteen
minutes and left to stand at ambient temperature, blue crystals
of 3 suitable for single-crystal X-ray diffraction appeared
overnight.
Preparation of 4
A 5 mL aliquot of the mother liquor of 1 was added to a vial.
The vial was tightly capped and left undisturbed at Ϫ20 C.
After several days, blue crystals of 4 appeared.
Preparation of 5
Copper() nitrate trihydrate (Cu(NO3)2ؒ3H2O (0.24 mg, 1.0
mmol) was dissolved in 3.5 mL of methanol with stirring.
2-Fluorobenzoic acid (0.28 g 2.0 mmol) was dissolved in
methanol (30 ml) and added to the methanolic copper solution
resulting in a light-green color. Isonicotinamide (0.49 g
4.0 mmol) dissolved in methanol (10 mL) was added to the
solution, whereupon the color changed to blue. The mixture
was then heated for fifteen minutes. The solution obtained was
left to stand at room temperature. Clear blue crystals of 5 pre-
cipitated first followed by the appearance of blue crystals of 2.
The copper() ions in 3 are coordinated to two iso-
nicotinamide ligands and two acetate ions in a plane in a trans-
geometry, with a third acetate ion completing a near-perfect
(4 ϩ 1) square pyramidal arrangement (τ = 0.00),30 Table 2. Two
of the acetate ions coordinate to neighbouring copper ions in a
µ2-manner which creates a dinuclear species with a Cu ؒ ؒ ؒ Cu
separation of 3.5 Å.. These dinuclear building blocks are sub-
sequently extended into two infinite parallel chains via the self-
X-Ray crystallography
Crystalline samples of 1–5 were placed in inert oil, mounted on
a glass pin, and transferred to the cold gas stream of the dif-
fractometer. Crystal data were collected and integrated using a
Bruker SMART 1000 system, with graphite monochromated
Mo-Kα (λ = 0.71073 Å) radiation at 223 K. The structures were
solved by direct methods using SHELXS-97 and refined using
D a l t o n T r a n s . , 2 0 0 3 , 3 9 5 6 – 3 9 6 2
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Table 2 Selected bond distances for 1–5
1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
Cu1
O3
O4
O2
O1
1.9605(14)
1.9609(15)
1.9749(15)
1.9758(16)
2.1783(16)
2.6111(5)
1.9312(16)
2.0445(19)
2.6525(21)
1.9591(17)
1.9895(16)
2.0227(18)
2.0270(18)
1.9765(16)
1.9824(14)
2.5113(17)
1.9944(17)
2.0121(18)
1.936(2)
N1
Cu1
O17
N1
O1S
O41
O31
N1
N21
O31
O41
O52
N11
N21
O37
O58
N11
N21
O48
2
3
4
5
2.007(2)
2.011(2)
2.022(2)
2.235(2)
complementary, symmetry related, N–H ؒ ؒ ؒ O interactions
between adjacent amide moieties, Fig. 5, Table 3.
The crystal lattice also contains two non-coordinated meth-
anol molecules. Parallel chains are bridged by one methanol
molecule that accepts a hydrogen bond from the anti-amide
proton and donates a hydrogen bond to an uncoordinated
carboxylate oxygen atom. The second molecule of methanol is
not engaged in any significant intermolecular interactions. The
Cu ؒ ؒ ؒ Cu distance between adjacent metal-ions within each
hydrogen-bonded chain is 16.7 Å.
The magnetization in this dinuclear complex was measured
as a function of temperature in an applied field of 200 Oe from
which the mass susceptibility χ(T) was determined. The Néel
temperature, Tn in the antiferromagnetic susceptibility χ(T) =
C/(T ϩ Tn),31 and the effective moment per formula unit, µ,
were determined from a Curie–Weiss analysis of magnetic
susceptibility data.32 We find Tn of 0.7 ( 0.1) K and µ of 1.66
(
0.05) µB (ground state is a singlet). This type of magnetic
behavior is expected for a Cu–O–Cu moiety with a bridging
angle of 103.3Њ (the µ-oxo being part of a carboxylate unit),
Fig. 6.33
The crystal structure of 4 has an unexpected chemical com-
position with two isonicotinamide ligands and two acetate ions
in a plane in a trans-geometry, with a molecule of acetic acid
completing a (4 ϩ 1) square pyramidal arrangement (τ = 0.06)
around the metal ion, Table 2. The coordinated acetic acid also
forms an intramolecular hydrogen bond to a coordinated
acetate ion. A second molecule of acetic acid (which is not
coordinated to the metal ion), forms a hydrogen bond to a
coordinated acetate ligand. Despite the complexity of these
intermolecular interactions, the desired amide–amide hydrogen
bonds prevail, and the result is infinite chains of linearly
organized copper() complexes. Neighbouring chains are
bridged via an N–H ؒ ؒ ؒ O hydrogen bond involving the anti-
amide proton and an acetate ligand. Fig. 7, Table 3.
The Cu ؒ ؒ ؒ Cu distance between adjacent metal-ions within
each hydrogen-bonded chain is 16.7 Å. The shortest through-
space inter-chain Cu ؒ ؒ ؒ Cu distance is 8.1 Å.
The copper() ions in 5 are five coordinated in a heavily dis-
torted square pyramidal geometry (τ = 0.35) generated by two
isonicotinamide molecules, two benzoate ions, and one neutral
molecule of 2-fluorobenzoic acid, Table 2. The expected amide–
amide interaction is observed leading to infinite hydrogen-
bonded infinite chains, Fig. 8, Table 3.
The Cu ؒ ؒ ؒ Cu distance between adjacent metal-ions within
each hydrogen-bonded chain is 16.7 Å. The shortest through-
space inter-chain Cu ؒ ؒ ؒ Cu distance is 8.1 Å.
D a l t o n T r a n s . , 2 0 0 3 , 3 9 5 6 – 3 9 6 2
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Fig. 1 Molecular geometries, thermal ellipsoids, and numbering schemes for 1–5.
Fig. 2 Infinite chain of dinuclear Cu()-complexes in 1 held together by self-complementary amide ؒ ؒ ؒ amide hydrogen-bond interactions.
description, R22(8) for all five structures. More importantly, this
Discussion
consistency (which can be equated with a high supramolecular
synthetic ‘yield’) has been achieved in the presence of several
potentially disruptive (in a structural sense) molecules, e.g.
water, methanol, and acetic acid. For this set of compounds, the
most consistent structural element is the self-complementary
amide ؒ ؒ ؒ amide interaction, which acts as a reliable linker
between neighboring Cu() complexes even though they display
dramatically different coordination geometries. A consequence
The crystal structures of 1–5 demonstrate that a specific inter-
molecular connector can be combined with very different
(chemically and structurally) building blocks and still create a
family of inorganic–organic hybrid materials that all display the
same principal supramolecular connectivity. This observation
is also reflected by the fact that the principal amide ؒ ؒ ؒ
amide hydrogen-bond interaction carries the same graph-set
D a l t o n T r a n s . , 2 0 0 3 , 3 9 5 6 – 3 9 6 2
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Table 3 Hydrogen-bond geometries for 1–5a
D–H
H ؒ ؒ ؒ A
D ؒ ؒ ؒ A
Є (DHA)
1
2
0.79(3)
0.84(3)
2.29(3)
2.05(3)
3.069(3)
2.881(2)
166(3)
173(3)
N7–H7A ؒ ؒ ؒ N1S
N7–H7B ؒ ؒ ؒ O7
Ϫ x, Ϫy ϩ 1, Ϫz
0.83(3)
0.92(3)
0.83(3)
0.71(3)
1.97(3)
1.85(3)
2.33(3)
2.19(3)
2.794(3)
2.757(3)
3.145(3)
2.905(3)
171(3)
167(3)
170(3)
175(3)
O1S–H1S ؒ ؒ ؒ O18
O1S–H2S ؒ ؒ ؒ O18
N7–H7A ؒ ؒ ؒ O1S
N7–H7B ؒ ؒ ؒ O7
Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 1
Ϫx ϩ 1, Ϫy ϩ 2, Ϫz ϩ 1
3 Ϫ x ϩ 1, Ϫy ϩ 3, Ϫz
3
4
0.86(3)
0.86(3)
0.79(3)
0.83(3)
0.83
2.08(3)
2.04(3)
2.11(3)
2.11(3)
1.95
2.930(3)
2.879(3)
2.901(3)
2.881(3)
2.754(3)
172(3)
165(3)
174(3)
154(3)
162.2
N7–H7A ؒ ؒ ؒ O27
N7–H7B ؒ ؒ ؒ O32
N27–H27A ؒ ؒ ؒ O7
N27–H27B ؒ ؒ ؒ O1S
O1S–H1S ؒ ؒ ؒ O42
x ϩ 1, y ϩ 1, z Ϫ 1
Ϫx ϩ 1, Ϫy ϩ 2, Ϫz ϩ 1
x Ϫ 1, y Ϫ 1, z ϩ 1
x, y Ϫ 1, z
0.87(3)
0.89(3)
0.74(3)
0.84(3)
0.83
1.99(3)
2.00(3)
2.20(3)
2.14(3)
1.82
2.860(3)
2.875(2)
2.940(3)
2.920(2)
2.649(2)
2.634(3)
176(2)
169(3)
173(3)
154(2)
173.0
N17–H17A ؒ ؒ ؒ O27
N17–H17B ؒ ؒ ؒ O42
N27–H27A ؒ ؒ ؒ O17
N27–H27B ؒ ؒ ؒ O41
O61–H61 ؒ ؒ ؒ O32
O51–H51 ؒ ؒ ؒ O31
x Ϫ 1, y, z Ϫ 1
x, Ϫy ϩ 3/2, z Ϫ 1/2
x ϩ 1, y, z ϩ 1
x, Ϫy ϩ 3/2, z ϩ 1/2
0.83
1.81
170.4
5
0.76
0.65
0.76
0.69
2.16
2.25
2.16
2.30
2.891(3)
2.889(3)
2.912(3)
2.968(3)
162.9
165.4
170.3
164.5
N17–H17A ؒ ؒ ؒ O27
N17–H17B ؒ ؒ ؒ O57
N27–H27A ؒ ؒ ؒ O17
N27–H27B ؒ ؒ ؒ O58
x ϩ 1, y, z ϩ 1
x, Ϫy ϩ 1/2, z ϩ 1/2
x Ϫ 1, y, z Ϫ 1
x, Ϫy ϩ 1/2, z Ϫ 1/2
a No suitable H-bond found for O38 ؒ ؒ ؒ O47 = 2.568(3) Å.
Fig. 3 Infinite chain of octahedrally coordinated Cu()-complexes in 2 held together by self-complementary amide ؒ ؒ ؒ amide hydrogen-bond
interactions.
Fig. 4 Adjacent chains in 2 are bridged through hydrogen bonds involving coordinated water molecules.
of this supramolecular robustness is that the intra-chain separ-
ation of Cu() ions shows very little variation, 16.7–17.0 Å,
despite large changes in the local environment around each
Cu() ion. This illustrates the fact that the very flexible
and often unpredictable coordination chemistry of copper()
does not, in itself, necessarily prevent subsequent successful
D a l t o n T r a n s . , 2 0 0 3 , 3 9 5 6 – 3 9 6 2
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Fig. 5 Infinite chains of Cu()-complexes in 3 held together by self-complementary amide ؒ ؒ ؒ amide hydrogen-bond interactions.
supramolecular synthesis. Isonicotinamide appears to be a very
effective supramolecular reagent for the construction of infinite
1-D metal-containing motifs.
The next phase in our investigation will employ a combin-
ation of reliable supramolecular reagents with coordination
complexes where the coordination geometry is under stricter
control with the aid of suitable chelating ligands.
Acknowledgements
We are grateful for generous financial support from the
National Science Foundation (CHE-0078996), Consejo
Nacional de Ciencia y Technologia (40332) and Universidad
Nacional Autónoma de México, (DGAPA).
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