Hydrothermal syntheses, architectures and magnetic properties of six novel MnII coordination polymers with mixed ligands

Article abstract of DOI:10.1002/ejic.200501155

Six novel manganese(II) coordination polymers, namely [Mn(oba)(4,4′- bpy)]_n·n(4,4′-bpy) (1), [Mn(oba)(phen)(H ₂O)]_n (2), [Mn₂(oba)₂(2,2′- bpy)₂(H₂O)₂]_n·nH ₂oba (3), [Mn₂(cca)₂-(4,4′-bpy) ₂]_n·2n(4,4′-bpy) (4), [Mn(cca)(phen)] _n (5) and [Mn(cca)(2,2′-bpy)]_n·0.25nH ₂O (6) [H₂oba = 4,4′-oxybis(benzoic acid); 4,4′-bpy = 4,4′-bipyridine; phen = 1,10-phenanthroline; 2,2′-bpy = 2,2′-bipyridine; H₂cca = p-carboxycinnamic acid] have been synthesised under hydrothermal conditions. Complexes 1 and 4 possess 3D microporous metal-organic frameworks with free 4,4′-bpy ligands in the channels. The Mn^II ions in complex 2 are bridged into 1D infinite double-chain structures, and those in complex 3 are bridged into 1D zigzag chains. Hydrogen bonds cause the formation of 3D supramolecular networks for complexes 2 and 3. Complex 5 is a complicated 3D metal-organic framework, and the Mn^II ions in complex 6 are linked into 2D layers with cavities; interpenetration of these 2D layers results in the formation of a 3D supramolecular network. Magnetic susceptibility measurements indicate that complex 2 displays a weak ferromagnetic interaction between the Mn^II ions with the following parameters: J = 0.462(3) cm^-1, g = 2.0387(6), zJ′ = -0.0062(3) cm^-1 and R = 8.0 × 10^-6. Complex 4 shows antiferromagnetic coupling between the Mn^II ions with J = -0.718(4) cm^-1, g = 1.986(4) and R = 2.3 × 10 ^-4. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200501155

FULL PAPER
DOI: 10.1002/ejic.200501155
Hydrothermal Syntheses, Architectures and Magnetic Properties of Six Novel
MnII Coordination Polymers with Mixed Ligands
Chang-Yan Sun,[a] Song Gao,*[b] and Lin-Pei Jin*[a]
Keywords: Coordination polymers / Magnetic properties / Manganese / Microporous materials / Organic–inorganic hybrid
composites
Six novel manganese(II
)
coordination polymers, namely
of 3D supramolecular networks for complexes 2 and 3. Com-
plex 5 is a complicated 3D metal-organic framework, and the
MnII ions in complex 6 are linked into 2D layers with cavities;
interpenetration of these 2D layers results in the formation of
a 3D supramolecular network. Magnetic susceptibility mea-
[Mn(oba)(4,4Ј-bpy)]n·n(4,4Ј-bpy) (1), [Mn(oba)(phen)(H2O)]n
(2), [Mn2(oba)2(2,2Ј-bpy)2(H2O)2]n·nH2oba (3), [Mn2(cca)2-
(4,4Ј-bpy)2]n·2n(4,4Ј-bpy) (4), [Mn(cca)(phen)]n (5) and
[Mn(cca)(2,2Ј-bpy)]n·0.25nH2O (6) [H2oba = 4,4Ј-oxybis(ben-
zoic acid); 4,4Ј-bpy = 4,4Ј-bipyridine; phen = 1,10-phenan- surements indicate that complex 2 displays a weak ferromag-
throline; 2,2Ј-bpy = 2,2Ј-bipyridine; H2cca = p-carboxycin- netic interaction between the MnII ions with the following
namic acid] have been synthesised under hydrothermal con-
ditions. Complexes 1 and 4 possess 3D microporous metal-
organic frameworks with free 4,4Ј-bpy ligands in the chan-
nels. The MnII ions in complex 2 are bridged into 1D infinite
double-chain structures, and those in complex 3 are bridged
into 1D zigzag chains. Hydrogen bonds cause the formation
parameters:
–0.0062(3) cm–1 and R = 8.0×10–6. Complex 4 shows antifer-
romagnetic coupling between the MnII ions with
–0.718(4) cm–1, g = 1.986(4) and R = 2.3×10–4
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
J = , g = 2.0387(6), zJЈ =
0.462(3) cm–1
J
=
.
metal centres and on the coordination behaviour of the or-
ganic ligands. When long bridging ligands are used to con-
nect metal ions, their versatile coordination modes may lead
to new architectures with novel topologies and interesting
properties.
4,4Ј-Oxybis(benzoic acid) (H2oba) is a typical example
of long V-shaped ligands. Its coordination chemistry has
been studied and some coordination polymers have been
obtained.[7] Because of its two oxo carboxylate groups,
H2oba can coordinate to metal ions in didentate, tridentate,
tetradentate, pentadentate and hexadentate modes. p-Car-
boxycinnamic acid (H2cca) also has two oxo carboxylate
groups. There is only one cobalt() complex known with
H2cca,[8] and we are interested in the architecture of metal
complexes with this asymmetrical functional carboxylate li-
gand.
The choice of a suitable co-ligand often has a significant
effect on the formation and structure of metal complexes.
4,4Ј-Bipyridine (4,4Ј-bpy) has been demonstrated to be one
of the most important rigid linear co-ligands and has been
extensively used to connect metal ions.[9] Chelating N-con-
taining aromatic ligands, such as 2,2Ј-bipyridine (2,2Ј-bpy)
and 1,10-phenanthroline (phen), can not only affect the co-
ordination geometry of metal ions but also bring about π-
π stacking interactions, which are important for the con-
struction of supramolecular networks.[10]
Introduction
Manganese-based coordination compounds have re-
ceived considerable interest in the fields of supramolecular
chemistry, crystal engineering and materials chemistry. This
interest arises not only from their remarkable magne-
tochemical properties,[1] but also from their rich biochemis-
try.[2] Furthermore, due to their low cost and toxicity, man-
ganese coordination compounds are growing in importance
as homogeneous catalysts.[3] As far as we know, the current
focus is on the construction of molecule-based magnetic
materials. The main approach is to employ short bridging
ligands to connect manganese ions. These short ligands,
such as azide,[4] cyanide[5] and oxalate,[6] efficiently mediate
the magnetic coupling. Long bridging ligands, because of
their large separation and thus their inefficiency in trans-
mitting magnetic interactions, have seldom been used to
construct manganese coordination compounds.
It is well-known that the topology of coordination com-
pounds depends both on the coordination geometry of the
[a] School of Chemistry, Beijing Normal University,
Beijing 100875, P. R. China
Fax: +86-105-880-2075
E-mail: lpjin@bnu.edu.cn
[b] State Key Laboratory of Rare Earth Materials Chemistry and
Applications, College of Chemistry and molecular Engineering,
Peking University,
Beijing 100871, P. R. China
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Taking into account the above-mentioned aspects, we re-
port here the syntheses, structures and magnetic properties
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of six novel MnII coordination compounds, namely
[Mn(oba)(4,4Ј-bpy)]n·n(4,4Ј-bpy) (1), [Mn(oba)(phen)-
(H2O)]n (2), [Mn2(oba)2(2,2Ј-bpy)2(H2O)2]n·nH2oba (3),
[Mn2(cca)2 (4,4Ј-bpy)2]n·2n(4,4Ј-bpy) (4), [Mn(cca)(phen)]n
(5) and [Mn(cca)(2,2Ј-bpy)]n·0.25nH2O (6). All six coordi-
nation polymers contain long spacers (oba/cca) and co-li-
gands (4,4Ј-bpy/phen/2,2Ј-bpy), and possess very different
structures, ranging from 1D chains to 2D layers and 3D
metal-organic frameworks.
Results and Discussion
Scheme 1. The coordination modes of the oba ligands in complexes
1–3.
Description of the Structures
[Mn(oba)(4,4Ј-bpy)]n·n(4,4Ј-bpy) (1)
Complex 1 is a 3D porous coordination polymer contain-
ing channels with guest 4,4Ј-bpy molecules. There is only
one metal environment in complex 1, as shown in Figure 1.
Each MnII ion is coordinated to four oxygen atoms of four
oba ligands and two nitrogen atoms of two 4,4Ј-bpy ligands,
and is located in a slightly distorted octahedral geometry.
The average Mn–N bond length is 2.322 Å and the Mn–O
bond lengths are in the range 2.147–2.162 Å. Each oba li-
gand in complex 1 is severely bent at the ether-oxygen site
(C–O–C = 118.6°) and adopts a bis(bridging didentate)
mode, linking four MnII ions (see Scheme 1a). All MnII ions
are connected by oba ligands into 2D pillar-like layers. The
nearest Mn···Mn distance in these layers is 4.835 Å. The
4,4Ј-bpy ligands bridge these layers into a 3D porous frame-
work with channels of about 11×14 Å (based on the dis-
tance between metal ions), as shown in Figure 2. The chan-
nels are big enough to accommodate free 4,4Ј-bpy mole-
cules.
Figure 2. The 3D porous framework of complex 1 viewed along
the c axis, with space-filling models representing the free 4,4Ј-bpy
molecules.
Figure 1. The coordination environment of the MnII ion in complex 1 with 30% thermal ellipsoids. All hydrogen atoms have been omitted
for clarity.
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MnII Coordination Polymers with Mixed Ligands
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[Mn(oba)(phen)(H2O)]n (2)
channels of about 3×13 Å. This is small and means that it
is unable to incorporate any guest molecules.
Figure 3 shows the coordination environment of the
MnII ions in complex 2. The coordination geometry around
each MnII ion is N2O4, with three oxygens from three oba
ligands, one oxygen from a coordinated water molecule and
two nitrogens from one phen ligand, and can be described
[Mn2(oba)2(2,2Ј-bpy)2(H2O)2]n·nH2oba (3)
There are two kinds of crystallographically different
as a distorted octahedron. The average Mn–N bond length MnII ions in complex 3, as shown in Figure 4. Both Mn(1)
is 2.271 Å and the Mn–O bond lengths are in the range and Mn(2) are coordinated to three oxygen atoms of two
2.107–2.158 Å. The oba ligands are also bent (C–O–C: oba ligands, one from a coordinated water molecule and
118.6°), as in complex 1. The coordination modes in com- two nitrogen atoms of a 2,2Ј-bpy ligand, but their bond
plexes 1 and 2, however, are different as each oba ligand in lengths and bond angles are different. The average Mn(1)–
complex 2 adopts a tridentate mode, linking three MnII N bond length is 2.261 Å and the Mn(1)–O bond lengths
ions, as shown in Scheme 1b. This coordination mode has are in the range 2.085–2.408 Å, while the average Mn(2)–N
not been reported before. The bridging carboxylate oxygen bond length is 2.242 Å and the Mn(2)–O bond lengths are
atoms cause the formation of the building blocks of Mn2O2 in the range 2.095–2.363 Å. Mn(1) and Mn(2) are bridged
cores, in which the Mn···Mn distance is 3.387 Å (Mn–O– by an oba ligand with a distance of 14.365 Å. There are
Mn angle: 101.81°). These cores are interconnected by oba three kinds of oba ligands in complex 3, two of which coor-
ligands into 1D double-chain structures. A similar structure dinate in a tridentate mode linking two MnII ions (see
has been reported for [Zn(bpndc)(phen)(H2O)]n.[11] There Scheme 1c). They are bent at the ether-oxygen sites (C–O–
are hydrogen bonds between the coordinated water mole- C = 118.4° and 119.9°), and connect the MnII ions into 1D
cules and the uncoordinated carboxylate oxygen atoms infinite zigzag chains (the Mn···Mn distance within a chain
(O···O distances of 2.697 and 2.740 Å). In addition, weak is 14.365 Å). The third kind of oba ligand is protonated and
π-π stacking interactions exist between phen molecules of does not coordinate to MnII. It is also bent at the ether-
neighbouring chains, with an average distance of 3.53 Å. oxygen sites, with a C–O–C angle of 120.2°. There are hy-
Both the hydrogen bonds and π-π stacking interactions re- drogen bonds between the coordinated water molecules and
sult in the formation of a 3D supramolecular network with the coordinated oba/free H2oba ligands (O···O distances of
Figure 3. The coordination environment of the MnII ion in complex 2 with 30% thermal ellipsoids. All hydrogen atoms have been omitted
for clarity.
Figure 4. The coordination environments of the MnII ions in complex 3 with 30% thermal ellipsoids. Free H2oba ligands and all hydrogen
atoms have been omitted for clarity.
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2.896, 2.753 and 2.855 Å), forming a 3D supramolecular Mn(1) and Mn(2) are bridged by two carboxylate groups
network, as shown in Figure 5.
of two cca ligands with a distance of 5.112 Å. Each cca
ligand in complex 4 adopts a tetradentate mode, linking
four MnII ions (see Scheme 2a). All MnII ions are connected
by cca ligands into 2D pillar-like layers. These layers are
interconnected by 4,4Ј-bpy ligands, resulting in the forma-
tion of a 3D porous framework with channels of about
11×11 Å, similar to those in complex 1. These channels
contain free 4,4Ј-bpy molecules.
Scheme 2. The coordination modes of the cca ligands in complexes
4–6.
Figure 5. The 3D supramolecular network of complex 3 viewed
along the a axis, with space-filling models representing the free
H2oba ligands.
[Mn(cca)(phen)]n (5)
[Mn2(cca)2(4,4Ј-bpy)2]n·2n(4,4Ј-bpy) (4)
There is only one metal environment in complex 5, as
Complex 4 possesses a 3D porous metal-organic frame- shown in Figure 7. Each MnII ion is placed in a distorted
work whose channels contain free 4,4Ј-bpy molecules. Sim- octahedron, which is completed by four oxygen atoms of
ilar to complex 3, there are two types of MnII environments four cca ligands and two nitrogen atoms of one phen mole-
(see Figure 6). Both Mn(1) and Mn(2) are coordinated to cule with the same Mn–N distance. The Mn–N bond length
four oxygen atoms of four cca ligands and two nitrogen is 2.317 Å and the Mn–O bond lengths are in the range
atoms of two 4,4Ј-bpy molecules, and are located in slightly 2.094–2.203 Å. Each cca ligand adopts a tetradentate mode,
distorted octahedra. However, their bond lengths and linking four MnII ions (see Scheme 2a). The nearest
angles are different. The Mn(1)–N bond length is 2.275 Å Mn···Mn distance is 4.587 Å. All MnII ions are linked by
and the Mn(1)–O bond lengths are in the range 2.152– cca ligands into a 3D metal-organic framework with 1D
2.173 Å, while the Mn(2)–N bond length is 2.299 Å and channels. However, chelating phen ligands occupy the diag-
the Mn(2)–O bond lengths are in the range 2.166–2.197 Å. onal position, which greatly decreases the dimension of the
Figure 6. The coordination environments of the MnII ions in complex 4 with 30% thermal ellipsoids. All hydrogen atoms have been
omitted for clarity.
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MnII Coordination Polymers with Mixed Ligands
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Figure 7. The coordination environment of the MnII ion in complex 5 with 30% thermal ellipsoids. All hydrogen atoms have been omitted
for clarity.
channels. All phen rings are parallel to each other, and the ing interactions between 2,2Ј-bpy molecules (the nearest
nearest face-to-face distance is 3.29 Å, indicating the pres- distance is 3.29 Å) further stabilize the supramolecular
ence of π-π stacking interactions.
structure.
It is obvious from the above descriptions that the carbox-
ylate ligands and the co-ligands have significant effects on
[Mn(cca)(2,2Ј-bpy)]n·0.25nH2O (6)
Because of the disorder of the cca ligands, there are four the formation and architecture of the resulting complexes.
types of MnII environment. Figure 8 shows one of them, The structures of these six complexes can be simplified as
and the others can be found in the Supporting Information shown in Scheme 3. Although complexes 1, 2 and 3 contain
(Figures S1–S3). Each MnII ion is coordinated to four oxy- the same carboxylate ligand oba, they possess different
gen atoms of three cca ligands and two nitrogen atoms of structures. In complex 1, both V-shaped oba and linear 4,4Ј-
one 2,2Ј-bpy molecule. The cca ligands in complex 6 adopt bpy ligands work as bridging ligands, resulting in the for-
two kinds of coordination modes, namely bis(bridging di- mation of a 3D porous structure. The free 4,4Ј-bpy ligands
dentate) and bis(chelating didentate) (see Scheme 2). The may be one of the important factors for the construction of
dinuclear species [Mn2(cca)2(2,2Ј-bpy)2], which has a metal– the porous structure as they might function as templates
metal distance of 4.462 Å, can be regarded as a secondary and occupy the pores, thus preventing further interpen-
building block. These moieties are linked by cca ligands etration. Complexes 2 and 3 possess infinite 1D chains,
into 2D grid-like layers with cavities of about 12×13 Å, and which may be attributed to the existence of the terminal
the 2D layers are interpenetrated, resulting in the formation ligands phen/2,2Ј-bpy/H2O. These terminal ligands occupy
of a 3D supramolecular network in which weak π-π stack- the coordination sites of the metal ions and prevent the
Figure 8. The coordination environment of the MnII ion in complex 6 with 30% thermal ellipsoids. All hydrogen atoms have been omitted
for clarity.
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structures from extending into higher dimensions. Complex while complex 5 possesses a complicated 3D structure and
2 has a double-chain structure while complex 3 has a single- complex 6 is made up of 2D grid-like layers when only co-
chain structure because the oba ligands adopt different co- ordination bonds are considered. The existence of coordi-
ordination modes in the two complexes (see Scheme 1 i and nated water molecules in complexes 2 and 3 is one impor-
b). When the oba ligand is replaced by cca, we obtain the tant factor for the formation of the chain structures. The
box-like structure of complex 4. Both cca and 4,4Ј-bpy are V-shaped oxo carboxylate ligand oba is also fundamental
bridging ligands that link metal ions into a 3D porous for the construction of chains in the presence of terminal
structure. The presence of free 4,4Ј-bpy works as template, ligands such as phen and 2,2Ј-bpy,[7a,7b,7e] while the linear
promoting the formation of the 3D porous structure. How- ligand cca contributes to higher dimensionalities in com-
ever, with the terminal ligand phen, complex 5 possesses a plexes 5 and 6, thus showing that the shape of the ligands
3D metal-organic framework due to the tetradentate bridg- plays an important role in the architecture of coordination
ing ligand cca, and in complex 6 the introduction of 2,2Ј- polymers.
bpy as a ligand leads to 2D grid-like layers, where hydrogen
bond and π-π stacking interactions result in a 3D supramo-
lecular network.
Magnetic Properties
Magnetic Properties of Complex 2
The χm–1 and χmT vs. T plots (2–300 K) of complex 2 are
shown in Figure 9. The magnetic susceptibility data (10 to
300 K) of complex 2 obey the Curie–Weiss law very well,
with a Weiss constant, θ, of +3.2 K and a Curie constant,
C, of 4.554(1) cm3 Kmol–1. The value of C is consistent
with one spin-only MnII ion with S = 5/2 and g = 2.040.
The positive Weiss constant and the increase of χmT upon
cooling are typical of a ferromagnetic coupling between the
MnII ions. Based on the structural data, the magnetic
susceptibility data of complex 2 can be analysed by using
a Mn2 dimer model with an intradimer interaction J and
including the contribution of the intermolecular interaction
zJЈ. Assuming an isotropic exchange, the exchange Hamil-
tonian H = –2JS1S2, with S1 = S2 = 5/2, and the expression
for magnetic susceptibility may be used to fit the data.[12]
The least-squares fit of the experimental data in the whole
temperature range gives the following parameters: J =
0.462(3) cm–1, g = 2.0387(6), zJЈ = –0.0062(3) cm–1, and R
= 8.0×10–6.
Scheme 3. A simplified representation of the structures of com-
plexes 1–6.
Both oba and cca have two exo carboxylate groups, but
there are some differences in their complexes. Comparing
complexes 1 and 4, although they are both 3D porous struc-
tures they are quite different: complex 1 possesses dumb-
bell-like channels while complex 4 possesses regular rhom-
bus channels. This is because oba is V-shaped whereas cca
is nearly linear. The introduction of phen and 2,2Ј-bpy as
Figure 9. Temperature dependence of χm–1 and χmT for complex 2.
Line I is the fit of the Curie–Weiss law and line II is the fit using
ligands in the MnII/oba and MnII/cca systems results in dif-
ferent structures. Complexes 2 and 3 are infinite 1D chains, a dimer model (see text).
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MnII Coordination Polymers with Mixed Ligands
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Clearly, a weak ferromagnetic interaction is observed in g = 2.0098. The negative Weiss constant and the peak in the
the doubly (µ-O)-carboxylate bridged MnII dimer, while χm curve for the complex are typical of antiferromagnetic
some structurally similar MnII dimers show weak antiferro- coupling between the MnII ions. Based on the structural
magnetic coupling between the MnII ions (Table 1).[13] The data, complex 4 can be viewed as a 1D uniform chain along
ferromagnetic coupling in complex 2 may be mainly due to the a axis. Consequently, the magnetic susceptibility data of
the smaller Mn–O–Mn angle, which facilitates ferromag- complex 4 can be analysed by using a 1D Fisher model with
netic coupling as in some azido- or chloro-bridged MnII an intradimer interaction J. Assuming isotropic exchange,
dimers.[14]
the exchange Hamiltonian is H = –2JSiSj with Si = Sj =
5/2 and the expression of magnetic susceptibility may be
used to fit the data.[16] The least-squares fit of the experi-
mental data in the whole temperature range gives the fol-
lowing parameters: J = –0.718(4) cm–1, g = 1.986(4), and R
= 2.3×10–4. The J value falls in the range for other carbox-
ylato-bridged MnII compounds.[17]
Table 1. Comparison of the magnetic coupling constant J and
structural parameters for MnII2(µ-O)2 complexes.
Compd. J [cm–1] Mn···Mn [Å] Mn–O–Mn [°]
Ref.
[13a]
A
B
–0.631
–0.655
3.712(2)
3.726(4)
109.1(3), 109.8(3)
108.9(3)
[13a]
105.04(7),
102.77(7)
101.81(7)
[13b]
C
–0.785
3.460(1)
D
+0.462
3.387(12)
this work
Magnetic Properties of Complex 3
The χm–1 and χmT vs. T plots (2–300 K) of complex 3 are
shown in Figure 10. The magnetic susceptibility data (2 to
300 K) of complex 3 obey the Curie–Weiss law very well
with a very small Weiss constant of 0.09 K and a Curie
constant of 9.004(1) cm3 Kmol–1. The value of C is consis-
tent with two non-interacting spin-only MnII ions with S =
5/2 and g = 2.029. The very small Weiss constant suggests
essentially no magnetic coupling between the MnII ions,
which is consistent with the long separation between the
MnII ions in this complex. The peak around 50 K might
arise from the effect of oxygen.[15]
–1
Figure 11. Temperature dependence of χm and χm for complex 4.
Line I is the fit of the Curie–Weiss law and line II is the fit using
a 1D Fisher model.
Conclusions
In summary, microporous MnII coordination polymers
(complexes 1 and 4) are formed by using the V-shaped li-
gand oba or the linear ligand cca with the rigid ligand 4,4Ј-
bpy. The free 4,4Ј-bpy ligand acts as a template and also
occupies the pore, thus preventing interpenetration. The in-
troduction of terminal ligands such as 2,2Ј-bpy and phen
leads to the formation of 1D chains for complexes 2 and 3;
hydrogen bonds mould these chains into 3D supramolec-
ular networks. In complex 6, the MnII ions are coordinated
by cca and 2,2Ј-bpy into 2D layers that interpenetrate to
form a 3D supramolecular network. A weak ferromagnetic
interaction is observed in the doubly (µ-O)-carboxylate-
bridged MnII dimer in complex 2, which may be mainly due
to the smaller Mn–O–Mn angle.
–1
Figure 10. Temperature dependence of χm and χmT for complex
3. The line is the fit of the Curie–Weiss law.
Magnetic Properties of Complex 4
–1
Experimental Section
The χm and χm vs. T plots (2–300 K) of complex 4 are
shown in Figure 11. The magnetic susceptibility data (20 to
300 K) of complex 4 obey the Curie–Weiss law very well
with a Weiss constant of –15.8 K and a Curie constant of
8.8355(7) cm3 Kmol–1. The value of C is consistent with
General Remarks: All reagents were used as received without fur-
ther purification. The C, H, N microanalyses were carried out with
a Vario EL elemental analyzer. The IR spectra were recorded with
a Nicolet Avatar 360 FT-IR spectrometer using the KBr pellet tech-
two non-interacting spin-only MnII ions with S = 5/2 and nique. The magnetic susceptibilities were obtained for crystalline
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Table 2. Crystal data and structure refinement parameters for complexes 1–6.
1
2
3
4
5
6
Chemical formula
Crystal system
Space group
Formula weight
a [Å]
C34H24MnN4O5 C26H18MnN2O6 C62H46Mn2N4O17 C60H44Mn2N8O8 C24H14N2O4Mn C20H14.50MnN2O4.25
monoclinic
P2/c
triclinic
triclinic
triclinic
monoclinic
C2/c
monoclinic
C2/c
¯
¯
¯
P1
P1
P1
623.51
13.251(4)
11.742(4)
9.317(3)
90
509.36
1228.91
11.317(4)
16.036(5)
17.986(6)
64.910(6)
87.609(6)
76.789(6)
2872.3(16)
2
1114.91
10.224(2)
11.723(2)
12.227(2)
65.980(3)
71.305(3)
84.622(4)
1266.7(4)
1
449.31
405.78
7.699(2)
11.671(4)
13.477(4)
82.295(5)
83.799(5)
73.086(5)
1145.1(6)
2
21.897(7)
11.677(4)
7.396(2)
90
15.009(2)
19.383(2)
13.926(2)
90
b [Å]
c [Å]
α [°]
β [°]
90.195(7)
90
100.311(6)
90
114.709(2)
90
γ [°]
V [Å3]
1449.6(8)
2
1860.6(10)
4
3680.8(8)
8
Z
F(000)
642
522
1264
574
916
1660
Dc [gcm–3]
T [K]
1.428
1.477
1.421
1.462
1.604
1.464
293(2)
293(2)
293(2)
293(2)
293(2)
293(2)
θ range [°]
µ [mm–1]
GOF
Final R indices
[I Ͼ 2σ(I)]
1.73–26.39
0.506
2.26–26.43
0.623
1.25–25.01
0.516
1.90–25.01
0.566
1.89–26.49
0.747
1.83–26.35
0.747
1.025
1.042
1.003
1.013
1.127
1.046
R1 = 0.0544
wR2 = 0.1118
R1 = 0.0408
wR2 = 0.0934
R1 = 0.0593
wR2 = 0.1392
R1 = 0.0509
wR2 = 0.1140
R1 = 0.0573
wR2 = 0.1600
R1 = 0.0360
wR2 = 0.0838
Table 3. Selected bond lengths [Å] and angles [°] for complexes 1–3.
1[a]
Mn(1)–O(1)
2.162(2)
2.147(2)
89.08(6)
90.92(6)
178.16(13)
93.66(9)
171.18(12)
Mn(1)–N(1)
2.333(4)
Mn(1)–O(2)#1
Mn(1)–N(2)#4
2.311(4)
86.48(9)
94.41(6)
85.59(6)
180.0
O(1)–Mn(1)–N(1)
O(1)–Mn(1)–N(2)#4
O(1)#3–Mn(1)–O(1)
O(2)#1–Mn(1)–O(1)
O(2)#1–Mn(1)–O(2)#2
O(2)#2–Mn(1)–O(1)
O(2)#1–Mn(1)–N(1)
O(2)#1–Mn(1)–N(2)#4
N(2)#4–Mn(1)–N(1)
2[b]
Mn(1)–O(1)
2.156(2)
2.208(2)
2.107(2)
78.19(7)
91.32(7)
95.32(7)
164.77(7)
91.55(7)
92.05(7)
103.36(7)
92.39(7)
Mn(1)–O(6)
2.159(2)
2.251(2)
2.290(2)
87.36(7)
88.55(7)
161.31(7)
169.16(7)
92.13(7)
98.78(7)
73.06(7)
Mn(1)–O(1)#2
Mn(1)–N(1)
Mn(1)–O(4)#1
Mn(1)–N(2)
O(1)–Mn(1)–O(1)#2
O(1)–Mn(1)–O(6)
O(1)–Mn(1)–N(1)
O(1)–Mn(1)–N(2)
O(1)#2–Mn(1)–N(1)
O(1)#2–Mn(1)–N(2)
O(4)#1–Mn(1)–O(1)
O(4)#1–Mn(1)–O(1)#2
O(4)#1–Mn(1)–O(6)
O(4)#1–Mn(1)–N(2)
O(4)#1–Mn(1)–N(1)
O(6)–Mn(1)–O(1)#2
O(6)–Mn(1)–N(1)
O(6)–Mn(1)–N(2)
N(1)–Mn(1)–N(2)
3[c]
Mn(1)–O(1)
2.157(3)
Mn(2)–O(5)#1
2.095(4)
Mn(1)–O(2)
2.407(3)
Mn(2)–O(10)
2.179(4)
Mn(1)–O(6)
2.176(4)
Mn(2)–O(11)
2.363(4)
Mn(1)–O(8)
2.085(4)
Mn(2)–O(12)
2.176(4)
Mn(1)–N(1)
2.274(4)
Mn(2)–N(3)
2.248(5)
Mn(1)–N(2)
2.249(4)
Mn(2)–N(4)
2.236(4)
O(1)–Mn(1)–O(2)
O(1)–Mn(1)–O(6)
O(1)–Mn(1)–N(1)
O(1)–Mn(1)–N(2)
O(6)–Mn(1)–O(2)
O(6)–Mn(1)–N(1)
O(6)–Mn(1)–N(2)
O(8)–Mn(1)–O(1)
O(8)–Mn(1)–O(2)
O(8)–Mn(1)–O(6)
O(8)–Mn(1)–N(1)
O(8)–Mn(1)–N(2)
N(1)–Mn(1)–O(2)
N(2)–Mn(1)–O(2)
N(2)–Mn(1)–N(1)
56.98(12)
101.89(15)
91.62(15)
151.88(16)
84.01(14)
161.44(14)
90.36(16)
100.70(14)
156.97(14)
96.62(15)
93.25(15)
102.93(16)
92.99(14)
100.09(15)
72.09(16)
O(5)#1–Mn(2)–O(10)
O(5)#1–Mn(2)–O(11)
O(5)#1–Mn(2)–O(12)
O(5)#1–Mn(2)–N(3)
O(5)#1–Mn(2)–N(4)
O(10)–Mn(2)–O(11)
O(10)–Mn(2)–N(3)
O(10)–Mn(2)–N(4)
O(12)–Mn(2)–O(10)
O(12)–Mn(2)–O(11)
O(12)–Mn(2)–N(3)
O(12)–Mn(2)–N(4)
N(3)–Mn(2)–O(11)
N(4)–Mn(2)–N(3)
N(4)–Mn(2)–O(11)
96.02(15)
151.78(14)
87.94(16)
99.51(16)
110.32(16)
57.73(13)
92.40(16)
151.33(17)
98.30(18)
86.20(16)
166.28(16)
93.89(18)
92.34(15)
72.76(17)
97.61(16)
[a] Symmetry transformations used to generate equivalent atoms: #1 –x, –y, –z + 1; #2 x, –y, z + 1/2; #3 –x, y, –z + 3/2; #4 x, y – 1, z.
[b] Symmetry transformations used to generate equivalent atoms: #1 –x + 1, –y, –z + 2; #2 –x + 1, –y, –z + 1. [c] Symmetry transforma-
tions used to generate equivalent atoms: #1 x – 1, y + 1, z + 1; #2 x + 1, y – 1, z – 1.
2418
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 2411–2421

MnII Coordination Polymers with Mixed Ligands
FULL PAPER
samples using a Quantum Design MPMS SQUID magnetometer.
The experimental susceptibilities were corrected for the sample
holder and the diamagnetism contributions estimated from Pascal’s
constants.
3049 (w), 1602 (s), 1553 (m), 1519 (m), 1496 (m), 1429 (m), 1384
(s), 1335 (s), 1238 (s), 1160 (m), 1137 (w), 1102 (w), 1047 (w), 1011
(w), 876 (w), 849 (m), 786 (m), 698 (w).
Synthesis of [Mn2(oba)2(2,2Ј-bpy)2(H2O)2]n·nH2oba (3): The synthe-
sis of complex 3 followed a similar procedure as for complex 1 but
with 2,2Ј-bpy (0.016 g, 0.1 mmol) instead of 4,4Ј-bpy·2H2O. Yield:
0.032 g (52.1%). C62H46Mn2N4O17 (1228.9): calcd. C 60.59, H
Synthesis of [Mn(oba)(4,4Ј-bpy)]n·n(4,4Ј-bpy) (1): A mixture of
H2oba (0.026 g, 0.1 mmol), Mn(OAc)2·4H2O (0.024 g, 0.1 mmol),
4,4Ј-bpy·2H2O (0.019 g, 0.1 mmol), NaOH solution (0.3 mL,
0.65 ) and deionized water(5 mL) was sealed in a Teflon-lined
stainless-steel vessel (25 mL) and heated at 180 °C for 72 h. The
vessel was then cooled slowly to room temperature. Yellow crystals
were isolated by filtration, and washed with water and ethanol.
Yield: 0.011 g (17.6%). C34H24MnN4O5 (623.51): calcd. C 65.44, H
3.74, N 4.56; found C 60.38, H 3.84, N 4.81. IR (KBr pellet): ν =
˜
3462 cm–1 (m), 3044 (w), 1596 (s), 1565 (m), 1499 (w), 1401 (s),
1316 (w), 1229 (s), 1165 (m), 1100 (w), 1061 (w), 1016 (w), 877 (m),
783 (m), 764 (m), 644 (w).
Synthesis of [Mn2(cca)2(4,4Ј-bpy)2]n·2n(4,4Ј-bpy) (4): A mixture of
H2cca (0.02 g, 0.1 mmol), Mn(OAc)2·4H2O (0.024 g, 0.1 mmol),
4,4Ј-bpy·2H2O (0.038 g, 0.2 mmol), NaOH solution (0.3 mL,
0.65 ) and deionized water (5 mL) was sealed in a Teflon-lined
stainless-steel vessel (25 mL) and heated at 140 °C for 72 h. The
vessel was then cooled slowly to room temperature. Yellow crystals
were isolated by filtration, and washed with water and ethanol.
Yield: 0.020 g (35.9%). C60H44Mn2N8O8 (1114.9): calcd. C 64.58,
H 3.95, N 10.05; found C 64.20, H 4.12, N 9.97. IR (KBr pellet):
3.85, N 8.98; found C 65.82, H 3.93, N 8.80. IR (KBr pellet): ν =
˜
3439 cm–1 (s), 3072 (w), 1648 (m), 1602 (s), 1560 (m), 1532 (m),
1496 (w), 1413 (m), 1386 (s), 1240 (s), 1159 (m), 1097 (w), 1071
(w), 1011 (w), 879 (w), 803 (m), 785 (m), 695 (w).
Synthesis of [Mn(oba)(phen)(H2O)]n (2): The synthesis of complex
2 followed a similar procedure as for complex 1 but with phen·H2O
(0.020 g, 0.1 mmol) instead of 4,4Ј-bpy·2H2O. Yield: 0.040 g
(78.5%). C26H18MnN2O6 (509.36): calcd. C 61.25, H 3.53, N 5.50;
found C 60.88, H 3.67, N 5.53. IR (KBr pellet): ν = 3317 cm–1 (m), ν = 3442 cm–1 (s), 1638 (m), 1588 (s), 1550 (s), 1492 (m), 1417 (m),
˜
˜
Table 4. Selected bond lengths [Å] and angles [°] for complexes 4–6.
4[a]
Mn(1)–O(1)
Mn(1)–O(3)#1
Mn(1)–N(1)
2.173(3)
2.152(2)
2.278(3)
87.10(10)
92.90(10)
180.0
91.57(10)
88.43(10)
180.0
Mn(2)–O(2)
Mn(2)–O(4)#2
Mn(2)–N(2)#6
2.166(2)
2.197(3)
2.299(3)
180.0
89.43(10)
90.57(9)
88.95(11)
91.05(11)
179.998(1)
86.45(10)
93.55(11)
180.0
O(1)–Mn(1)–N(1)
O(1)–Mn(1)–N(1)#3
O(1)#3–Mn(1)–O(1)
O(3)#1–Mn(1)–O(1)
O(3)#1–Mn(1)–O(1)#3
O(3)#1–Mn(1)–O(3)#2
O(3)#1–Mn(1)–N(1)
O(3)#1–Mn(1)–N(1)#3
N(1)#3–Mn(1)–N(1)
O(2)–Mn(2)–O(2)#4
O(2)–Mn(2)–O(4)#2
O(2)–Mn(2)–O(4)#5
O(2)–Mn(2)–N(2)#6
O(2)–Mn(2)–N(2)#7
O(4)#2–Mn(2)–O(4)#5
O(4)#2–Mn(2)–N(2)#6
O(4)#2–Mn(2)–N(2)#7
N(2)#6–Mn(2)–N(2)#7
91.76(10)
88.24(10)
180.0
5[b]
Mn(1)–O(1)
Mn(1)–O(2)#2
2.094(3)
2.203(3)
113.4(2)
86.1(1)
100.3(1)
87.9(1)
158.1(1)
100.3(1)
86.1(1)
Mn(1)–N(1)
2.317(4)
O(1)–Mn(1)–O(1)#1
O(1)–Mn(1)–O(2)#2
O(1)–Mn(1)–O(2)#3
O(1)–Mn(1)–N(1)
O(1)–Mn(1)–N(1)#1
O(1)#1–Mn(1)–O(2)#2
O(1)#1–Mn(1)–O(2)#3
O(2)#2–Mn(1)–O(2)#3
O(2)#2–Mn(1)–N(1)
O(2)#3–Mn(1)–N(1)
O(2)#2–Mn(1)–N(1)#1
O(2)#3–Mn(1)–N(1)#1
N(1)–Mn(1)–N(1)#1
168.3(2)
85.6(1)
84.9(1)
84.9(1)
85.6(1)
71.4(2)
6[c]
Mn(1)–O(1)
Mn(1)–O(2)#3
Mn(1)–O(5)
2.12(4)
2.08(2)
2.15(2)
94.4(1)
87.3(1)
95.0(8)
164.4(8)
101.9(1)
116.6(5)
168.6(8)
94.2(5)
Mn(1)–O(6)
Mn(1)–N(1)
Mn(1)–N(2)
O(2)#3–Mn(1)–N(2)
O(5)–Mn(1)–O(6)
O(5)–Mn(1)–N(1)
O(5)–Mn(1)–N(2)
N(1)–Mn(1)–O(6)
N(2)–Mn(1)–O(6)
N(1)–Mn(1)–N(2)
2.51(2)
2.245(2)
2.290(2)
87.8(7)
55.2(3)
145.1(3)
92.1(5)
91.7(4)
84.8(7)
71.86(7)
O(1)–Mn(1)–O(5)
O(1)–Mn(1)–O(6)
O(1)–Mn(1)–N(1)
O(1)–Mn(1)–N(2)
O(2)#3–Mn(1)–O(1)
O(2)#3–Mn(1)–O(5)
O(2)#3–Mn(1)–O(6)
O(2)#3–Mn(1)–N(1)
[a] Symmetry transformations used to generate equivalent atoms: #1 –x, –y, –z + 1; #2 x, y + 1, z; #3 –x, –y + 1, –z + 1; #4 –x + 1,
–y + 1, –z + 1; #5 –x + 1, –y, –z + 1; #6 x + 1, y, z – 1; #7 –x, –y + 1, –z + 2; #8 x, y – 1, z. [b] Symmetry transformations used to
generate equivalent atoms: #1 –x, y, –z + 3/2; #2 x, –y, z – 1/2; #3 –x, –y, –z + 2; #4 –x + 1/2, –y – 1/2, –z + 2. [c] Symmetry
transformations used to generate equivalent atoms: #1 x + 1/2, y + 1/2, z; #2 –x + 1/2, –y + 1/2, –z + 1; #3 –x + 1, –y + 1, –z + 1; #4
–x, –y + 1, –z; #5 x – 1/2, y – 1/2, z.
Eur. J. Inorg. Chem. 2006, 2411–2421
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2419

C.-Y. Sun, S. Gao, L.-P. Jin
FULL PAPER
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Synthesis of [Mn(cca)(phen)]n (5): The synthesis of complex 5 fol-
lowed a similar procedure as for complex 4 except that phen·H2O
(0.020 g, 0.1 mmol) was used instead of 4,4Ј-bpy·2H2O and the
temperature was 160 °C. Yield: 0.022 g (48.9%). C24H14MnN2O4
(449.31): calcd. C 62.07, H 3.29, N 6.58; found C 61.75, H 3.43, N
6.86. IR (KBr pellet): ν = 3439 cm–1 (s), 1649 (s), 1606 (m), 1509
˜
(m), 1425 (m), 1381 (s), 1099 (w), 987 (w), 851 (m), 789 (m), 730
(m), 636 (w).
Synthesis of [Mn(cca)(2,2Ј-bpy)]n·0.25nH2O (6): The synthesis of
complex 6 followed a similar procedure as for complex 4 except
that 2,2Ј-bpy (0.016 g, 0.1 mmol) was used instead of 4,4Ј-
bpy·2H2O and the temperature was 120 °C. Yield: 0.017 g (41.9%).
C20H14.50MnN2O4.25 (405.78): calcd. C 59.15, H 3.57, N 6.90;
found C 58.91, H 3.81, N 6.82. IR (KBr pellet): ν = 3431 cm–1 (m),
˜
3025 (m), 1646 (s), 1616 (s), 1536 (s), 1473 (m), 1439 (s), 1390 (s),
1312 (m), 1245 (m), 1171 (m), 1098 (w), 1016 (m), 984 (m), 862
(m), 763 (m), 737 (m), 647 (m), 625 (w).
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direct methods and refined by full-matrix least-squares on F2 using
the SHELXS-97 and SHELXL-97 programs, respectively.[18] Non-
hydrogen atoms were refined anisotropically. Hydrogen atoms were
placed in geometrically calculated positions. The crystallographic
data for complexes 1 to 6 are listed in Table 2, and selected bond
lengths and angles in Tables 3 and 4.
¯
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CCDC-293769 to -293774 (for 1–6, respectively) contain the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): The other three kinds of coordination environments of the
MnII ion in complex 6.
Acknowledgments
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This work was supported by the National Natural Science Founda-
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Received: December 30, 2005
Published Online: April 18, 2006
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