Substituent dependent dimensionalities in cobalt isophthalate supramolecular complexes and coordination polymers containing dipyridylamine ligands

Article abstract of DOI:10.1016/j.ica.2011.09.016

Hydrothermal synthesis has afforded cobalt 5-substituted isophthalate complexes with 4,4′-dipyridylamine (dpa) ligands, showing different dimensionalities depending on the steric bulk and hydrogen-bonding facility of the substituent. [Co(tBuip)(dpa)(H

Full text of DOI:10.1016/j.ica.2011.09.016

Inorganica Chimica Acta 378 (2011) 269–279
Contents lists available at SciVerse ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Substituent dependent dimensionalities in cobalt isophthalate supramolecular
complexes and coordination polymers containing dipyridylamine ligands
⇑
Jacqueline S. Lucas, Lestella D. Bell, Chaun M. Gandolfo, Robert L. LaDuca
Lyman Briggs College and Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
a r t i c l e i n f o
a b s t r a c t
Hydrothermal synthesis has afforded cobalt 5-substituted isophthalate complexes with 4,40-dipyridyl-
amine (dpa) ligands, showing different dimensionalities depending on the steric bulk and hydrogen-
bonding facility of the substituent. [Co(tBuip)(dpa)(H2O)]n (1, tBuip = 5-tert-butylisophthalate) is a
(4,4) grid two-dimensional coordination polymer featuring 2-fold parallel interpenetration. [Co(MeO-
ip)2(Hdpa)2] (2, MeOip = 5-methoxyisophthalate) is organized into 3-fold parallel interpenetrated (4,4)
grids through strong N–H+ꢀ ꢀ ꢀOꢁ hydrogen bonding. {([Co(OHip)(dpa)(H2O)3])3ꢀ2H2O}n (3, OHip = 5-
hydroxyisophthalate) possesses 1-D chain motifs. The 5-methyl derivative {[Co(mip)(dpa)]ꢀ3H2O}n (4,
mip = 5-methylisophthalate) has a 3-D 658 cds topology. {[Co(H2O)4(Hdpa)2](nip)2ꢀ2H2O} (5, nip = 5-
nitroisophthalate) and {[Co(sip)(Hdpa)(H2O)4]ꢀ2H2O} (6, sip = 5-sulfoisophthalate) are coordination com-
plexes. Antiferromagnetic superexchange is observed in 1 and 4, with concomitant zero-field splitting.
Thermal decomposition behavior of the higher dimensionality complexes is also discussed.
Ó 2011 Elsevier B.V. All rights reserved.
Article history:
Received 18 March 2011
Received in revised form 25 August 2011
Accepted 2 September 2011
Available online 21 September 2011
Keywords:
Hydrothermal synthesis
Cobalt
Isophthalate
Coordination polymer
Dipyridylamine
Thermogravimetric analysis
1. Introduction
[26] have been seeing more recent use in coordination polymer
chemistry, in order to evaluate the effect of the substituent on
Coordination polymer crystalline solids, constructed from the
linkage of metal ions through anionic and neutral organic ligands,
may have important industrial applications [1] including gas stor-
age [2], absorption and separation [3], cation or anion exchange
[4], catalysis [5], guest-dependent luminescence [6], and in non-
linear optical devices [7]. Anionic aromatic dicarboxylates such
as terephthalate [8] or isophthalate (ip) [9] have been frequently
used as linking ligands towards the construction of divalent metal
coordination polymers, through their ability to stabilize a neutral
crystalline framework. A synergism between divalent metal ion
coordination environment, carboxylate group position, carboxylate
binding or bridging modes and the presence of any dipyridyl coli-
gands [10] is responsible for the supramolecular arrangement dur-
ing self-assembly. Therefore any a priori prediction of coordination
polymer structure can remain elusive. In coordination polymer sol-
ids containing divalent cobalt ions, the presence of multinuclear
clusters can cause temperature-dependent or field-dependent
magnetic behavior such as spin-canting and single-chain magne-
tism [11].
structural topology and the resulting influence on physical proper-
ties. For instance, {[Co(OHip)(dpp)]ꢀH2O}n (dpp = 1,3-di(4-pyridyl)
propane) shows a 4-fold interpenetrated diamondoid topology,
while its nickel derivative [Ni(OHip)(dpp)1.5(H2O)]n displays inter-
digitated sets of 1-D ribbon motifs [12]. The 3-D network material
[Zn(tBuip)]n (tBuip = 5-tert-butylisophthalate) synthesized by Li
et al. contains 1-D solvent-free channels that permit the separation
of methanol from water [23]. A recent unique example of 2-fold
interpenetration of self-penetrated mab 446108 topology networks
was seen in a zinc mip coordination polymer with a very long
dipyridylbenzamide ligand [24]. [Cu4(OH)2(sip)2(2,20-bipyridine)2
(H2O)2]n and {[Cu4(OH)2(sip)2(H2O)2]ꢀ4H2O}n adopt uncommon
3-D (4.62)2(4261083) rutile and (456)2(41161483) fluorite variant net-
works, respectively [26a].
Solid solutions of substituted isophthalate coordination poly-
mers can also perform useful separations, as discovered Kitagawa
et al. in a recent study [27]. Crystalline solid solutions of the lay-
ered phase {[Zn(nip)(4,40-bpy)](0.5DMFꢀ0.5MeOH)}n with its iso-
structural MeOip analog can be tailored in order to change the
gate-opening pressure for water adsorption. Additionally, CO2
absorption selectivity can be increased by adjusting the number
of MeOip ligands in the solid solution.
Substituted isophthalate ligands such as 5-hydroxyisophthalate
(OHip) [12–15], 5-methoxyisophthalate (OMeip) [16,17], 5-nitro-
isophthalate (nip) [18–22], 5-tert-butylisophthalate (tBuip) [23],
5-methylisophthalate (mip) [24,25], or 5-sulfoisophthalate (sip)
Although there has been some recent exploratory synthesis of
substituted isophthalate coordination polymer phases, studies that
systematically investigate size-dependent steric effects imposed
by these substituents have been less common. Yang et al. showed
⇑
Corresponding author.
E-mail address: laduca@msu.edu (R.L. LaDuca).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.09.016

270
J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
that increasing steric hindrance caused a decrease in coordination
polymer dimensionality in a system with monodentate pyridine
coligands [28]. [Zn4(H2O)(ip)4(py)6]n (py = pyridine), {[Zn2(OHip)2
(py)4]2ꢀ(py)}n, and [Zn(tBuip)(py)2]n show 2-D grid-like layers, 1-
56.01; H, 4.72; N, 8.86%. IR (cmꢁ1): 3400 (w, br), 2949 (w), 1598
(s), 1562 (w), 1523 (s), 1438 (m), 1355 (s), 1214 (s), 1016 (s),
910 (m), 847 (w), 806 (s), 777 (m), 726 (s), 692 (w).
D
single-stranded chains, and 1-D double-stranded ribbons,
2.3. Preparation of [Co(MeOip)2(Hdpa)2]n (2)
respectively. We were recently able to corroborate this apparent
trend in a system with the long-spanning tethering ligand bis(4-
pyridylformyl)piperazine (bpfp) [29]. {[Cu(ip)(4-bpfp)]ꢀ2H2O}n
Cobalt nitrate hexahydrate (108 mg, 0.37 mmol), dpa (63 mg,
0.37 mmol), 5-methoxyisophthalic acid (72 mg, 0.37 mmol) and
10 mL deionized water were placed into a 23 mL Teflon-lined acid
digestion bomb. The bomb was sealed and heated in an oven at
120 °C for 48 h, and then cooled slowly to 25 °C. Purple needles
of 2 (16 mg, 5% yield based on Co) were isolated after manual sep-
aration from unreacted organics, washing with distilled water, hot
ethanol, and acetone and drying in air. Anal. Calc. for C38H32Co-
N6O10 (2): C, 57.65; H, 4.07; N, 10.62. Found: C, 57.28; H, 3.83;
N, 10.40%. IR (cmꢁ1): 3380 (w), 3108 (w), 1692 (w), 1643 (w),
1595 (w), 1568 (m), 1525 (s), 1445 (m), 1363 (s), 1288 (w), 1247
(w), 1208 (m), 1122 (w), 1056 (s), 1013 (s), 910 (w), 972 (w),
835 (w), 814 (m), 763 (s), 703 (s), 680 (w).
has
a (4,4) rectangular grid structure, while [Cu2(tBu ip)2
(4-bpfp)(H2O)2]n and {[Cu(MeOip)(HMeOip)2(4-bpfp) ]ꢀ3H2O}n dis-
play 1-D ladder and chain motifs, respectively.
The angular disposition of the pyridyl nitrogen donor atoms
and central hydrogen bonding point of contact within 4,40-dipyr-
idylamine (dpa) has provided access to many new coordination
polymer topologies in aliphatic or aromatic dicarboxylate sys-
tems [30–32]. For example, {[Ni(dpa)2(succinate)0.5]Cl}n pos-
sesses a unique self-penetrated regular (6,5) 3-D network with
610 rld-z topology [30]. {[Cd(phthalate)(dpa)(H2O)]ꢀ4H2O}n has
an unprecedented 4-connected uninodal self-penetrated three-
dimensional 7482 topology (yyz net), constructed from the inter-
locking of [Cd(dpa)]n double helices with [Cd(pht)]n single heli-
ces [31]. To date, however, there have been no reports of
coordination polymers containing both dpa and substituted iso-
phthalate ligands. In this study we report the preparation and
structural characterization of [Co(tBuip)(dpa)(H2O)]n (1),
[Co(MeOip)2(Hdpa)2]n (2), {[Co(OHip)(dpa)(H2O)3]3ꢀ2H2O}n (3),
{[Co(mip)(dpa)]ꢀ2H2O}n (4), {[Co(H2O)4(Hdpa)2](nip)2ꢀ2H2O} (5,
nip = 5-nitroisophthalate) and {[Co(sip)(Hdpa)(H2O)4]ꢀ2H2O} (6,
sip = 5-sulfoisophthalate) whose dimensionalities and topologies
differ greatly from each other, depending on the nature of the
5-position substituent. Thermal decomposition behavior of the
higher dimensionality complexes is also presented, along with
the variable temperature magnetic susceptibility of 1 and 4 be-
cause of their closely spaced cobalt ions.
2.4. Preparation of {([Co(OHip)(dpa)(H2O)3])3ꢀ2H2O}n (3)
Cobalt nitrate hexahydrate (110 mg, 0.377 mmol), dpa (62 mg,
0.37 mmol), 5-hydroxyisophthalic acid (62 mg, 0.34 mmol), 2 mL
of 1.0 M NaOH solution, and 10 mL deionized water were placed
into a 23 mL Teflon-lined acid digestion bomb. The bomb was
sealed and heated in an oven at 120 °C for 48 h, and then cooled
slowly to 25 °C. Pink blocks of 3 (33 mg, 20% yield based on 5-
hydroxyisophthalic acid) were isolated after manual separation
from unreacted organics, washing with distilled water, hot ethanol,
and acetone and drying in air. Anal. Calc. for C54H61Co3N9O26 (3): C,
45.39; H, 4.30; N, 8.82. Found: C, 46.10; H, 3.91; N, 9.10%. IR
(cmꢁ1): 2961 (w), 1595 (vs), 1556 (vs), 1514 (vs), 1400 (vs), 1367
(vs), 1351 (vs), 1299 (m), 1269 (m), 1213 (m), 1132 (w), 1094
(w), 1064 (w), 1017 (m), 973 (w), 844 (m), 818 (vs), 784 (vs),
718 (s).
2. Experimental
2.5. Preparation of {[Co(mip)(dpa)]ꢀ3H2O}n (4)
2.1. General considerations
Cobalt nitrate hexahydrate (103 mg, 0.35 mmol), dpa (59 mg,
0.35 mmol), 5-methylisophthalic acid (62 mg, 0.34 mmol), 2 mL
of 1.0 M NaOH solution, and 10 mL deionized water were placed
into a 23 mL Teflon-lined acid digestion bomb. The bomb was
sealed and heated in an oven at 150 °C for 48 h, and then cooled
slowly to 25 °C. Magenta blocks of 4 (69 mg, 44% yield based on
5-methylisophthalic acid) were isolated after manual separation
from unreacted organics, washing with distilled water, hot ethanol,
and acetone and drying in air. Anal. Calc. for C19H21CoN3O7 (4): C,
49.36; H, 4.58; N, 9.09. Found: C, 49.90; H, 3.73; N, 9.12%. IR
(cmꢁ1): 3651 (w), 3281 (w), 3175 (w), 3067 (w), 1615 (w), 1580
(m), 1547 (w), 1523 (s), 1442 (w), 1424 (m), 1383 (s), 1349 (m),
1252 (w), 1214 (m), 1115 (w), 1060 (w), 1017 (s), 951 (w), 926
(w), 905 (w), 838 (w), 811 (m), 797 (m), 774 (s), 723 (s), 665 (w).
Cobalt salts and substituted isophthalic acids were commer-
cially obtained. 4,40-Dipyridylamine was synthesized using a pub-
lished procedure [33]. Water was deionized above 3 MX-cm
in-house. Elemental analysis was carried out using a Perkin–Elmer
2400 Series II CHNS/O Analyzer. IR spectra were recorded on pow-
dered samples using a Perkin–Elmer Spectrum One instrument.
Thermogravimetric analysis was performed on a TA Instruments
high-resolution Q500 thermal analyzer under flowing N2. Variable
temperature magnetic susceptibility data (2–300 K) for 1 was col-
lected on a Quantum Design MPMS SQUID magnetometer at an ap-
plied field of 0.1 T. After each temperature change the sample was
kept at the new temperature for 5 min before magnetization mea-
surement to ensure thermal equilibrium. The susceptibility data
was corrected for diamagnetism using Pascal’s constants [34] and
for the diamagnetism of the sample holder.
2.6. Preparation of {[Co(H2O)4(Hdpa)2](nip)2ꢀ2H2O}n (5)
2.2. Preparation of [Co(tBuip)(dpa)(H2O)]n (1)
Cobalt nitrate hexahydrate (102 mg, 0.35 mmol), dpa (61 mg,
0.35 mmol), 5-nitroisophthalic acid (77 mg, 0.36 mmol), 2 mL of
1.0 M NaOH solution, and 10 mL deionized water were placed into
a 23 mL Teflon-lined acid digestion bomb. The bomb was sealed
and heated in an oven at 120 °C for 48 h, and then cooled slowly
to 25 °C. Pink needles of 5 (63 mg, 39% yield based on dpa) were
isolated after manual separation from unreacted organics, washing
with distilled water, hot ethanol, and acetone and drying in air.
Anal. Calc. for C36H38CoN8O18 (5): C, 46.51; H, 4.12; N, 12.05.
Found: C, 46.58; H, 3.86; N, 11.80%. IR (cmꢁ1): 3098 (w), 1646
Cobalt nitrate hexahydrate (108 mg, 0.37 mmol), dpa (63 mg,
0.37 mmol), 5-tert-butylisophthalic acid (72 mg, 0.37 mmol) and
10 mL deionized water were placed into a 23 mL Teflon-lined acid
digestion bomb. The bomb was sealed and heated in an oven at
120 °C for 48 h, and then cooled slowly to 25 °C. Pink blocks of 1
(66 mg, 38% yield based on Co) were isolated after washing with
distilled water, ethanol, and acetone and drying in air. Anal. Calc.
for C44H46Co2N6O10 (1): C, 56.42; H, 4.95; N, 8.97. Found: C,

J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
271
(w), 1599 (m), 1560 (m), 1532 (m), 1518 (m), 1426 (w), 1337 (vs),
1204 (m), 1094 (w), 1079 (w), 1062 (w), 1014 (w), 973 (w), 921
(w), 847 (w), 825 (m), 788 (m), 723 (s).
within the sip ligands give rise to an intense feature at
1199 cmꢁ1 in the spectrum of 6.
4.2. Structural description of [Co(tBuip)(dpa)(H2O)]n (1)
2.7. Preparation of {[Co(sip)(Hdpa)(H2O)4]ꢀ2H2O}n (6)
The asymmetric unit of compound 1 contains two crystallo-
graphically distinct cobalt atoms, two tBuip ligands, two dpa li-
gands, and two aqua ligands. The coordination environment at
each cobalt atom is a distorted {CoO4N2} octahedron, with a chelat-
ing tBuip carboxylate group, a monodentate tBuip carboxylate
group (Fig. 1), and a dpa pyridyl nitrogen donor occupying equato-
rial sites. A dpa pyridyl nitrogen donor atom and an aqua ligand
take up the axial positions. Thus at each cobalt atom, dpa pyridyl
donors are oriented in a cis disposition. Bond lengths and angles
within the coordination sphere are given in Table S2.
Cobalt atoms in 1 are connected into [Co(tBuip)(H2O)]n chains
that are oriented parallel to the b crystal direction. Crystallograph-
ically distinction between the chains is enforced by differences in
the torsion of the carboxylate groups relative to the tBuip aromatic
ring planes. In one type of tBuip ligand, these torsion angles are
5.4° and 19.2°, while in the other they are less twisted, measuring
3.2° and 17.1°. Adjacent [Co(tBuip)(H2O)]n chains are connected by
dpa ligands into (4,4) grid [Co(tBuip)(dpa)(H2O)]n coordination
polymer layers (Fig. 2). The dpa ligands bridge Coꢀ ꢀ ꢀCo distances
of 11.833 or 11.868 Å, with slightly difference inter-ring torsions
(13.2° or 12.1°, respectively).
Cobalt sulfate hexahydrate (83 mg, 0.32 mmol), dpa (34 mg,
0.20 mmol), sodium 5-sulfoisophthalate (53 mg, 0.20 mmol),
1.0 mL of 1.0 M NaOH, and 10 mL deionized water were placed into
a 23 mL Teflon-lined acid digestion bomb. The bomb was sealed
and heated in an oven at 120 °C for 48 h, and then cooled slowly
to 25 °C. Magenta blocks of 6 (74 mg, 64% yield based on Co) were
isolated after manual separation from unreacted organics, washing
with distilled water, hot ethanol, and acetone and drying in air.
Anal. Calc. for C18H25CoN3O13S (6): C, 37.12; H, 4.33; N, 7.21.
Found: C, 36.91; H, 4.12; N, 7.19%. IR (cmꢁ1): 3302 (w, br), 2516
(w, br, 2091 (w), 1643 (w), 1601 (s), 1545 (m), 1505 (s), 1474
(w), 1428 (s), 1361 (s), 1338 (s), 1199 (s), 1105 (s), 1043 (s),
1019 (m), 991 (w), 953 (w), 903 (w), 842 (w), 822 (s), 777 (s),
713 (s), 670 (w).
3. X-ray crystallography
Reflection data for 1–6 were collected on a Bruker-AXS SMART-
CCD X-ray diffractometer using graphite-monochromated MoK
a
radiation (k = 0.71073 Å). The data were processed via SAINT [35],
and subjected to Lorentz and polarization effect and absorption
corrections using SADABS [36]. The structures were solved using di-
rect methods with SHELXTL [37]. The crystal of 5 was non-merohed-
rally twinned. Its twin law was found using CELLNOW [38], and only
reflections from the major twin component was used. All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms
bound to carbon were placed in calculated positions and refined
isotropically with a riding model. Hydrogen atoms bound to the
dpa central amine and protonated pyridyl groups and ligated water
molecules were found by Fourier difference map where possible.
Water molecule disorder in 3, 5, and 6 was modeled using partial
occupancies. Crystallographic details for 1–6 are given in Table 1.
Large windows within an undulating (4,4) [Co(tBuip)(dpa)
(H2O)]n layer, as defined by through-space Coꢀ ꢀ ꢀCo contact dis-
tances of ꢂ14.8 and 16.2 Å, permit parallel 2d + 2d ? 2D interpen-
etration of an identical layer. Hydrogen bonding donation
(Table S2) from the dpa amine functional groups in one layer to
unligated carboxylate oxygen atoms in the other serves to stabilize
the interpenetrated structure. The sterically bulky tert-butyl sub-
stituents project above and below each individual layer, fitting into
pockets bracketed by tert-butyl groups belonging to the other
layer.
Interpenetrated layer pairs stack along the a direction (Fig. 3),
anchored by hydrogen bonding donation (Table S1) from the aqua
ligands in one layer to ligated oxygen atoms within monodentate
tBuip carboxylate groups and also oxygen atoms within chelating
tBuip carboxylate groups in the other layer. The Coꢀ ꢀ ꢀCo distances
across the pairwise Co–O–Hꢀ ꢀ ꢀO–Co supramolecular contacts mea-
sure 4.936 Å (Fig. 4). Aromatic rings of the tBuip ligands in adjacent
4. Results and discussion
4.1. Synthesis and Infrared Spectroscopy
layer pairs engage in p–p stacking interactions (3.67 Å centroid-to-
Compounds 1–6 were prepared as crystalline solids by hydro-
thermal reaction of a cobalt salt with dpa and the appropriate 5-
substituted isophthalic acid. An examination of each sample under
a microscope showed only pink blocks for 1, magenta rhombs for 2,
pink blocks for 3, magenta blocks for 4, pink needles for 5, and ma-
genta blocks for 6. The infrared spectra of 1–6 were consistent with
the components seen in their crystal structures. Features corre-
sponding to pyridyl or phenyl ring flexing and puckering modes
were observed in the region between 600 and 820 cmꢁ1. Medium
intensity bands in the range of ꢂ1600 to ꢂ1200 cmꢁ1 arise from
stretching modes of the aromatic rings of the dicarboxylate ligands
and pyridyl rings within the dpa ligands [39]. Asymmetric and
symmetric C–O stretching modes of the benzenedicarboxylate
moieties were evidenced by very strong, slightly broadened bands
at 1523 and 1355 cmꢁ1 for 1, 1525 and 1363 cmꢁ1 for 2, 1514 and
1351 cmꢁ1 for 3, 1523 and 1383 cmꢁ1 for 4, 1518 and 1337 cmꢁ1
for 5, and 1505 and 1361 cmꢁ1 for 6. Weak, broad spectral features
in the region of ꢂ3400 cmꢁ1 represent O–H stretching modes with-
in the aqua ligands in 1 and 3–6, and the N–H stretching mode for
dpa central amine in 1–6. An intense band at 1204 cmꢁ1 in the
spectrum of 5 is attributed to the N–O stretching modes of the ni-
tro substituents in the nip ligands. The sulfonate substituents
centroid distance), serving a supporting structure stabilizing role.
The interpenetrated layer structure of 1 contrasts greatly with its
3-D unsubstituted isophthalate (ip) analog {[Co(ip)(dpa)]ꢀ3H2O}n
[40]. This material possesses orthogonally arranged sets of parallel
1-D [Co(ip)]n chains bearing anti–syn bridged {Co(OCO)2} dinuclear
units, pillared by dpa ligands into a 3-D 4-connected 658 cds topol-
ogy network (Fig. 5). It is likely that the steric hindrance imparted
by the 5-position tert-butyl groups in the tBuip ligands of 1 prevents
aggregation into a 3-D coordination polymer lattice. This result cor-
roborates the dimensionality-reducing trend caused by bulkier 5-
position substituents seen previously by Wang and co-workers
[28] and our group [29].
4.3. Structural description of [Co(MeOip)2(Hdpa)2]n (2)
The asymmetric unit of compound 2 contains a cobalt atom on a
crystallographic 2-fold axis, one MeOip ligand, and a dpa molecule
protonated at one of its pyridyl rings. Operation of the crystallo-
graphic 2-fold axis results in a complete neutral [Co(MeOip)2
(Hdpa)2] coordination complex, in which a distorted {CoO2N2} tet-
rahedral geometry is present (Fig. 6). Bond lengths and angles
within the coordination sphere are listed in Table S3.

272
J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
Table 1
Crystal and Structure refinement data for 1–6.
Data
1
2
3
4
5
6
Formula
C
44H46Co2N6O10
C38H32CoN6O10
791.63
monoclinic
C2/c
25.790(9)
9.139(3)
17.161(5)
90
122.83(2)
90
C54H61Co3N9O26
1428.91
monoclinic
P21/c
18.176(2)
14.0057(18)
24.547(3)
90
111.181(1)
90
C19H21CoN3O7
462.32
monoclinic
C2/c
15.7443(9)
12.7077(7)
21.1794(12)
90
103.919(1)
90
C36H38CoN8O18
929.67
C18H25CoN3O13
582.40
monoclinic
P21
8.2251(17)
17.033(4)
8.4919(18)
90
91.731(2)
90
1189.1(4)
2
S
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
936.73
monoclinic
P21/c
23.7681(15)
18.6018(12)
9.9930(6)
90
93.781(1)
90
triclinic
ꢀ
P1
7.9028(11)
13.8666(19)
18.278(3)
90.689(2)
91.289(2)
97.937(2)
1983.1(5)
2
a
(°)
b (°)
c
(°)
V (Å3)
Z
4408.6(5)
4
1.411
3399(2)
4
1.547
5826.8(13)
4
1.629
4113.0(4)
8
1.493
D (g cmꢁ3
l
)
1.557
0.523
1.627
0.882
(mmꢁ1
)
0.816
0.578
0.941
0.881
Crystal size (mm)
Minimum/
0.28 ꢃ 0.20 ꢃ 0.18
0.40 ꢃ 0.10 ꢃ 0.10
0.41 ꢃ 0.18 ꢃ 0.16
0.45 ꢃ 0.22 ꢃ 0.20
0.58 ꢃ 0.10 ꢃ 0.04
0.36 ꢃ 0.19 ꢃ 0.16
0.8061/0.8697
0.8014/0.9466
0.6995/0.8671
0.6921/0.8456
0.7525/0.9773
0.7407/0.8688
maximum
transmission
hkl Ranges
ꢁ28 6 h 6 28,
ꢁ22 6 k 6 22,
ꢁ12 6 l 6 12
32022
8057
0.0680
ꢁ30 6 h 6 30,
ꢁ10 6 k 6 10,
ꢁ20 6 l 6 20
13588
3088
0.0797
ꢁ21 6 h 6 21,
ꢁ16 6 k 6 16,
ꢁ29 6 l 6 29
42146
10674
0.0462
ꢁ18 6 h 6 19,
ꢁ15 6 k 6 15,
ꢁ25 6 l 6 25
14864
3812
0.0277
ꢁ9 6 h 6 9,
ꢁ16 6 k 6 16,
0 6 l 6 21
30694
7175
0.0871
ꢁ9 6 h 6 9,
ꢁ20 6 k 6 20,
ꢁ9 6 l 6 10
7063
3886
0.0209
Total reflections
Unique reflections
Rint
Parameters/
restraints
583/6
257/1
911/39
285/3
619/22
370/18
a
R1 (all data)
0.0854
0.0610
0.1739
0.1534
0.1104
0.0828
0.2279
0.2090
0.0675
0.0430
0.1197
0.1052
0.0490
0.0419
0.1223
0.1169
0.1354
0.0607
0.1314
0.1120
0.0308
0.0299
0.0812
0.0802
a
R1 [I > 2
r
(I)]
b
wR2 (all data)
wR2 [I > 2
b
r(I)]
Maximum/
0.905/ꢁ0.952
0.877/ꢁ0.612
0.875/ꢁ0.743
0.852/ꢁ0.579
0.361/ꢁ0.638
0.755/ꢁ0.253
minimum
residual (e Åꢁ3
Goodness-of-fit
(GOF) on F2
)
1.071
1.058
1.038
1.061
0.981
1.046
a
R1
wR2 = {
=
R
||Fo| ꢁ |Fc||/
R|Fo|.
b
2
R
[w(Fo ꢁ Fc2)2]/
R .
[wFo2]2}1/2
Fig. 1. Coordination environment of 1, shown with 50% thermal ellipsoids and atom numbering scheme. Hydrogen atoms have been omitted.
Individual [Co(MeOip)2(Hdpa)2] coordination complexes are
The very large 27.4 ꢃ 29.1 Å apertures in a single supramolecu-
lar layer, as measured by Coꢀ ꢀ ꢀCo through-space distances, allow
interpenetration of two other identical [Co(MeOip)2(Hdpa)2]n
supramolecular nets (Fig. 7). The interpenetration of the individual
rhomboid grid layers is fostered by C–Hꢀ ꢀ ꢀO non-classical hydro-
gen bonding (Cꢀ ꢀ ꢀO distance = 3.338(4) Å) between Hdpa pyridyl
rings and the unligated oxygen atoms of the MeOip monodentate
carboxylate groups. The pyridyl rings of the Hdpa ligands undergo
a slight twist in order to optimize these interactions, with a dihe-
dral angle of 11.9° between the ring planes.
linked into a supramolecular (4,4) grid structure by charge-sepa-
rated ionic-character N+–Hꢀ ꢀ ꢀOꢁ hydrogen bonding (Nꢀ ꢀ ꢀO3 dis-
tance = 2.609(6) Å) distance between the protonated pendant
pyridyl groups of the dpa ligands and unligated MeOip carboxylate
termini (Table S2). The long N–H bond distance (1.32(6) Å) is as-
cribed to the electrostatic attraction on the part of the negatively
charged MeOip carboxylate oxygen. While this strong intermolec-
ular interaction in 2 is best considered to be a N+–Hꢀ ꢀ ꢀOꢁ electro-
static-type attraction, some quasi-covalent N–Hꢀ ꢀ ꢀO character can
be invoked [41]. Hydrogen bonding has been referred to as
‘‘incipient proton transfer’’ [42], with these interactions in 2 being
an example.
The resulting 3-fold parallel interpenetrated network in 2 con-
trasts with the topology of another coordination complex showing
polycatenation of hydrogen-bonded (4,4) supramolecular grids,

J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
273
Fig. 2. A single [Co(tBuip)(dpa)(H2O)]n layer in 1.
Fig. 3. Interpenetration and stacking of [Co(tBuip)(dpa)(H2O)]n layers in 1. Hydrogen bonding is indicated as dashed lines.
{[Pt(Hinic)2(inic)2]ꢀ2H2O} (inic = isonicotinate) [43]. This species
possess three orthogonal sets of parallel non-interpenetrated
(4,4) grids, forming a 2d + 2d + 2d ? 3D supramolecular arrange-
ment. The 3-fold parallel interpenetration of 2 falls short of the re-
cord level of parallel interpenetration of hydrogen bonded
coordination complexes, seen in the 5-fold supramolecular (4,4)
grid layers in [Co (BPDC)2(Hdpa)2] (BPDC = biphenyldicarboxylate)
[44]. In this previously reported material, the greater length of the
BPDC ligands in comparison to MeOip promotes the generation of
larger grid apertures, allowing for a higher level of interpenetra-
tion. It is clear that judicious adjustment of the length of the mono-
dentate dicarboxylate ligand in [Co(dicarboxylate)2(Hdpa)2] type
coordination complexes can allow a modicum of design of inter-
penetrated hydrogen bonded networks. Three-fold interpenetrated
[Co(MeOip)2(Hdpa)2]n supramolecular layers in 2 aggregate via
hydrogen bonding pathways between central N–H amine

274
J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
Fig. 4. Close-up view of supramolecular hydrogen-bonding bridged dimeric units in 1. Hydrogen bonding is indicated as dashed lines.
Fig. 5. Three-dimensional 658 topology cds network in [Co(ip)(dpa)]n.
Fig. 6. [Co(MeOip)2(Hdpa)2] coordination complex in 2.

J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
275
coordination environment at each cobalt atom is a distorted
{CoO4N2} octahedron, with cis disposed dpa pyridyl nitrogen do-
nors, three aqua ligands arranged in a meridional orientation,
and an oxygen donor atom from an OHip ligand. Bond lengths
and angles within the slightly crystallographically distinct coordi-
nation environments are listed in Table S4.
The Co1 atoms are joined by dipodal dpa ligands into [Co
(OHip)(dpa)(H2O)3]n coordination polymer chains (Fig. 8). As the
OHip ligands are monodentate, they serve as pendant groups and
do not participate in coordination polymer linkages. The Co1ꢀ ꢀ ꢀCo1
distance through the dpa tethers is 11.410 Å; the pyridyl rings of
the dpa ligands are twisted by 44.5° relative to each other. Simi-
larly, the Co2 and Co3 atoms alternate and are bridged by dpa li-
gands within crystallographically distinct [Co(OHip)(dpa)(H2O)3]n
chains, but with Coꢀ ꢀ ꢀCo distances of 11.477 and 11.506 Å, respec-
tively. The different metal–metal contact distances are enforced by
the variances in the dihedral angles between dpa pyridyl rings
(42.9° and 46.4°, respectively). All [Co(OHip)(dpa)(H2O)3]n chains
within 3 are oriented parallel to the b crystal direction.
Neighboring chains are aggregated by supramolecular hydrogen
bonding between OHip hydroxyl groups and aqua ligands, and also
between aqua ligands and unligated OHip carboxylate groups
(Fig. 9). Water molecules of crystallization occupy 2.1% of the unit
cell volume, and are anchored to the coordination polymer chains
by hydrogen bonding acceptance from the dpa central amine func-
tional groups. Some data regarding the extensive hydrogen bond-
ing interactions in 3 is listed in Table S2.
Fig. 7. Three-fold parallel interpenetration of [Co(MeOip)2(Hdpa)2]n hydrogen-
bonded supramolecular layers in 2.
functional groups of the dpa ligands, and unligated MeOip
carboxylate oxygen atoms.
4.4. Structural description of {([Co(OHip)(dpa)(H2O)3])3ꢀ2H2O}n (3)
The large asymmetric unit of compound 3 contains three diva-
lent cobalt atoms (Co1, Co2, Co3) with three aqua ligands on each,
three dpa ligands, three OHip ligands, and two water molecules of
crystallization. One of the water molecules in 3 (O3/O3A) was dis-
ordered over bound and unbound positions in a 84/16 ratio. The
4.5. Structural description of {[Co(mip)(dpa)]ꢀ3H2O}n (4)
The asymmetric unit of compound 4 contains a divalent cobalt
atom, a fully deprotonated mip ligand, a dpa ligand, and three
Fig. 8. A single [Co(OHip)(dpa)(H2O)3]n coordination polymer chain in 3.
Fig. 9. Supramolecular hydrogen bonding between neighboring chains in 3 (dashed lines).

276
J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
water molecules of crystallization, one of which is disordered. A
distorted {CoO4N2} octahedral coordination environment exists at
cobalt, with dpa pyridyl nitrogen donors in the axial positions.
Within the equatorial plane lie a chelating mip carboxylate group
and two cis oxygen donors from two other mip ligands. Bond
lengths and angles within the coordination sphere are listed in
Table S5.
functional groups of the Hdpa ligands, aqua ligands, nip carboxyl-
ate groups, and water molecules of crystallization. Detailed infor-
mation regarding the myriad hydrogen bonding pathways within
the coordination complex salt 5 can be found in Table S2 in the
Supplementary information. Protonation of one of the pyridyl rings
of the dpa precursors results in monodentate pendant Hdpa li-
gands, preventing aggregation into a higher dimensionality coordi-
nation polymer.
Exotridentate mip ligands with a l3-
j4-O,O0:O00:O000 binding
mode connect cobalt ions in 4 into [Co(mip)]n chains with embed-
ded anti–syn bridged {Co2(OCO)2} dinuclear kernels (Fig. 10). These
dinuclear units alternate with {Co2(OC5O)2} 16-membered circuits
along the chain motifs. The Coꢀ ꢀ ꢀCo through-space distances across
the dinuclear kernels and larger circuits are 4.020 and 7.558 Å,
respectively. Orthogonally disposed sets of parallel [Co(mip)]n
4.7. Structural description of {[Co(sip)(Hdpa)(H2O)4]ꢀ2H2O}n (6)
According to single crystal X-ray diffraction, compound 6 is a
simple neutral [Co(sip)(Hdpa)(H2O)4] coordination complex with
a slightly distorted octahedral coordination at cobalt. The sip and
singly protonated Hdpa ligands are disposed in a cis orientation,
while the remaining four coordination sites are filled by aqua li-
gands. The sip ligand is bound to cobalt through one of its carbox-
ylate groups, in a monodentate fashion. Relevant bond lengths and
angles within the coordination sphere are given in Table S7.
Charge balance is provided by the protonated pyridyl rings of
the Hdpa ligands, which also connect neighboring coordination
complexes into supramolecular chains via N–H+ꢀ ꢀ ꢀOꢁ hydrogen
bonding donation to unligated sip carboxylate groups. These same
unligated sip carboxylate oxygen atoms accept hydrogen bonding
from aqua ligands in neighboring chains, thereby forming supra-
molecular layers arranged in the ac crystal planes (Fig. 13). Central
amine groups of the Hdpa ligands promote aggregation into the
full supramolecular 3-D crystal structure. Hydrogen bonding infor-
mation is listed in Table S2. It appears that coordination polymer
generation is curtailed during the self-assembly of 6 by proton-
ation of one of the dpa pyridyl rings, as well as the poor ligating
ability of the diffusely charged sip sulfonate group. The ability of
one of the sip carboxylate groups to bind to cobalt is also likely re-
duced by its dual hydrogen bonding acceptance.
ꢀ
chains are arranged along the ½110ꢄ and [110] crystal directions,
linked by pairs of dpa ligands into a 3-D [Co(mip)(dpa)]n coordina-
tion polymer network (Fig. 11a). The Coꢀ ꢀ ꢀCo contact distance
through the dpa ligands, which have an inter-ring dihedral angle
of 34.9°, is 11.577 Å. If the {Co2(OCO)2} dinuclear units are consid-
ered 4-connected nodes, the topology of 4 is that of a 658 cds net-
work (Fig. 11b). This relatively uncommon 3-D topology was
encountered in the previously reported unsubstituted isophthalate
analog of 4, {[Co(ip)(dpa)]ꢀ3H2O}n [40]. Apparently the small steric
bulk and the lack of hydrogen-bonding facility of the methyl group
in the mip ligand result in an inability to alter coordination poly-
mer topology from that of the unsubstituted isophthalate deriva-
tive. Water molecules of crystallization occupy incipient 1-D
channels, totaling 22.7% of the unit cell volume, situated between
the dpa ligand pairs.
4.6. Structural description of {[Co(H2O)4(Hdpa)2](nip)2ꢀ2H2O}n (5)
The asymmetric unit of compound 5 contains two divalent co-
balt atoms on crystallographic inversion centers, four aqua ligands,
two singly protonated Hdpa ligands, two unligated nip dianions,
and two water molecules of crystallization. At each crystallograph-
ically distinct cobalt atom, there is a {CoO4N2} octahedral coordina-
tion environment, with trans Hdpa pyridyl nitrogen donor atoms in
axial positions and four aqua ligands in the equatorial planes. Bond
lengths and angles within the coordination spheres are listed in
Table S6.
In contrast to the tBuip, OHip, and mip coordination polymers
discussed earlier, compound 5 is a simple coordination cation/an-
ion salt-like complex. Here, isolated [Co(H2O)4(Hdpa)2]4+ cations
and nip anions form chain motifs (Fig. 12) through strong
N–H+ꢀ ꢀ ꢀOꢁ charge-separated hydrogen-bonding between the pro-
tonated pyridyl groups of the Hdpa ligands and nip carboxylate
oxygen atoms. Other nip anions are anchored to the coordination
complex cations by hydrogen bonding acceptance from aqua li-
gands at carboxylate oxygen atom lone pairs. In turn these chains
construct the supramolecular 3-D crystal structure through addi-
tional hydrogen bonding patterns involving the central amine
4.8. Thermogravimetric analysis
According to thermogravimetric analysis (TGA), the aqua li-
gands of 1 were ejected between ꢂ105 and ꢂ210 °C, as evidenced
by a 3.6% observed mass loss (3.8% calc). The mass then remained
stable until ꢂ325 °C, where ligand pyrolysis ensued. The 17.0%
remnant at ꢂ400 °C corresponded well with a deposition of CoO
(16.0% calc). For compound 2, the mass remained stable until
ꢂ305 °C, where all ligands were combusted in a two-step process.
The 10.6% remnant at ꢂ450 °C matched roughly with a deposition
of CoO (9.5% calc) with some remaining carbon-containing compo-
nents. Dehydration of 4 occurred from 25 to ꢂ100 °C, with a mass
loss of 9.7% (11.8% calc); it is likely that some water loss occurred
on standing. The mass of 4 then remained nearly constant to
ꢂ370 °C. Although phase transformations cannot be ruled out
completely, it is plausible that the 3-D coordination polymer
framework of the cds network results in enhanced thermal
Fig. 10. [Co(mip)]n chain in 4.

J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
277
Fig. 11. (a) [Co(mip)(dpa)]n network in 4. [Co(mip)]n chains and water molecules of crystallization are shown in red and orange in the online version of this article,
respectively. (b) Schematic representation of the 658 cds network topology of 4. The spheres represent the 4-connected {Co2(OCO)2} dinuclear units, with mip and dpa
connections rendered in red and blue, respectively. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this paper.)
Fig. 12. Supramolecular chain of [Co(H2O)4(Hdpa)2]4+ complex cations and nip anions in 5. Hydrogen bonding is indicated as dashed lines.
Fig. 13. Supramolecular layer of [Co(sip)(Hdpa)(H2O)4] neutral coordination complexes in 6.

278
J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
Fig. 14. Variable temperature magnetic data for 1. The best fit to Eq. (1) in the text
Fig. 15. Variable temperature magnetic data for 4. The best fit to Eq. (1) in the text
is drawn as a thin black line.
is drawn as a thin black line.
finally reaching 0.49 cm3-K mol Coꢁ1 at 2 K. The inverse suscepti-
bility data were fit to the Curie-Weiss law (Fig. S5), giving
stability. Ligand ejection occurred above 370 °C, which was incom-
plete by the end of the experiment at 480 °C. The 39.6% mass rem-
nant is consistent with a deposition of CoCO3 (25.7% calc) and
uncombusted organics. Thermograms for 1, 2, and 4 are shown
in Figs. S1–S3, respectively.
C = 3.29 cm3-K mol Coꢁ1 and
H
= ꢁ8.0 K. The
vmT behavior and lar-
ger Weiss constant possibly indicates stronger antiferromagnetic
coupling than that seen in 1. The Rueff model was once again ap-
plied, giving best-fit values (Fig. 14) of A = 0.76(3) cm3-K mol
Coꢁ1 and B = 2.57(3) cm3-K mol Coꢁ1 giving g = 2.72(3),
D = 21(1) cmꢁ1, and J = ꢁ2.27(4) cmꢁ1 with R = 1.01 ꢃ 10ꢁ3. It is
apparent that the dual carboxylate bridges between S = 3/2 ions
in 4 promotes stronger antiferromagnetic coupling than that affor-
ded by the hydrogen-bonding mediated exchange pathway in 1. In
both cases the magnitude of the zero-field splitting is largely the
same, given similar coordination environments.
4.9. Variable temperature magnetic properties of 1 and 4
The magnetic susceptibility of 1 and 4 as a function of tempera-
ture was measured in order to investigate the possibility of hydro-
gen-bonding
or
carboxylate-bridge
mediated
magnetic
superexchange. As mentioned previously, pairwise Co–O–Hꢀ ꢀ ꢀ
O–Co supramolecular contacts are present in 1, whose metal atoms
are slightly less than 5 Å apart. The
v
mT product value for 1 at 300 K
mT value decreased
was 2.72 cm3-K mol Coꢁ1. Upon cooling the
v
5. Conclusions
very slowly, dropping to 2.65 cm3-K mol Coꢁ1 at 70 K, 2.33 cm3-
K mol Coꢁ1 at 30 K, and 2.00 cm3-K mol Coꢁ1 at 2 K. The inverse sus-
ceptibilitydatawere fitover theentiretemperaturerange totheCur-
ie-Weiss law (Fig. S4), yielding C = 2.75 cm3-K mol Coꢁ1 and
The dimensionality of cobalt isophthalate coordination poly-
mers containing 4,40-dipyridylamine depends critically upon the
steric hindrance or hydrogen-bonding facility of any 5-position iso-
phthalate substituents. Substituents with a small degree of steric
bulk (hydrogen, methyl) permits generation of uncommon 3-D
4-connected 658 cds networks, based on antiferromagnetically
coupled anti–syn bridged {Co2(OCO)2} dinuclear units. Bulkier sub-
stituents (tert-butyl, methoxy) tend to reduce coordination poly-
mer dimensionality, consistent with some recent literature
precedent. Substituents that can participate in hydrogen bonding,
such as nitro, hydroxy, and sulfonate groups, can promote forma-
tion of simple coordination complexes via ample hydrogen bond-
ing pathways. It is clear that deliberate alteration of 5-position
substituents within isophthalate-type ligands can provide a modi-
cum of crystal design in this system.
H
= ꢁ3.2 K. Although the negative value for
H portends antiferro-
magnetic coupling, care must be taken in this interpretation because
of the likelihood of zero-field splitting in distorted octahedral S = 3/2
coordination environments [45]. The phenomenological expression
of Rueff (Eq. (1)) [46] was used to model the variable temperature
magnetic data for 1 to estimate the competing effects of antiferro-
magnetic superexchange (J) and zero-field splitting (D). Best-fit val-
ues (Fig. 13) were A = 0.71(4) cm3-K mol Coꢁ1 and B = 2.16(3) cm3-K
mol Coꢁ1 giving g = 2.47(4), D = 24(3) cmꢁ1, and J = ꢁ0.19(2) cmꢁ1
with R = {
R
[(
v
mT)obs ꢁ (
v
mT)calc]2/
R
[(
v
mT)obs]2} = 3.71 ꢃ 10ꢁ3. The
small, negativeJ value indicates veryweak antiferromagnetichydro-
gen-bonding mediated coupling between cobalt ions in different
coordination polymer layers, consistent with literature precedent
[47].
Acknowledgments
v
mT ¼ A expðꢁD=kTÞ þ B expðJ=kTÞ
Financial support for this work was provided by the donors of
the American Chemical Society Petroleum Research Fund (Type B
Grant for undergraduate research). C.M.G. thanks the Michigan
State University Honors College for his Professorial Assistantship.
where
A þ B ¼ C ¼ ð5Ng2b2=4kÞ
ð1Þ
For 4, which possesses anti–syn bridged {Co2(OCO)2} dinuclear
kernels, the
mT product value for 1 at 300 K was 3.19 cm3-K mol
Coꢁ1. The
mT value decreased slowly upon cooling (Fig. 15), reach-
ing 3.13 cm3-K mol Coꢁ1 at 100 K and 2.84 cm3-K mol Coꢁ1 at 50 K.
Below this temperature the mT product decayed more rapidly,
v
Appendix A. Supplementary material
v
CCDC 809642, 809641, 813224, 815145, 815423, and 815840
contain the supplementary crystallographic data for 1–6. These
v

J.S. Lucas et al. / Inorganica Chimica Acta 378 (2011) 269–279
279
(b) X.-N. Cheng, W.-X. Zhang, Y.-Y. Lin, Y.-Z. Zheng, X.-M. Chen, Adv. Mater. 19
(2007) 1494.
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Metrical parameters for bond lengths, bond angles, and hydro-
gen-bonding are given in Tables S1–S7. Additional thermogravi-
metric analysis and magnetic data figures are also given in
Figures S1–S5. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.ica.2011.09.016.
[9] (a) J. Tao, M.L. Tong, X.M. Chen, J. Chem. Soc., Dalton Trans. (2000) 3669;
(b) S.A. Bourne, J. Lu, B. Moulton, M.J. Zaworotko, Chem. Commun. (2001) 861;
(c) J. Tao, X.M. Chen, R.B. Huang, L.S. Zhen, J. Solid State Chem. 170 (2003) 130.
[10] (a) B. Chen, C. Liang, J. Yang, D.S. Contreras, Y.L. Clancy, E.B. Lobkovsky, O.M.
Yaghi, S. Dai, Angew. Chem., Int. Ed. 45 (2006) 1390;
(b) S.W. Lee, H.J. Kim, Y.K. Lee, K. Park, J.H. Son, Y. Kwon, Inorg. Chim. Acta 353
(2003) 151.
[11] M. Kurmoo, Chem. Soc. Rev. 38 (2009) 1353 (and references therein).
[12] X.J. Li, R. Cao, W.H. Bi, Y.Q. Wang, Y.L. Wang, X. Li, Polyhedron 24 (2005) 2955.
[13] H.Y. He, Y.L. Zhou, Y. Hong, L.G. Zhu, J. Mol. Struct. 737 (2005) 97.
[14] X.J. Li, X.Y. Wang, S. Gao, R. Cao, Inorg. Chem. 45 (2006) 1508.
[15] R.K. Feller, A.K. Cheetham, Dalton Trans. (2008) 2034.
[16] L.F. Ma, B. Li, X.Y. Sun, L.Y. Wang, Y.T. Fan, Z. Anorg. Allg. Chem. 636 (2010)
1606.
[17] Z.M. Wilseck, C.M. Gandolfo, R.L. LaDuca, Inorg. Chim. Acta 363 (2010) 3865.
[18] M. Du, Z.H. Zhang, Y.P. You, X.J. Zhao, CrystEngComm 10 (2008) 306.
[19] J. Luo, M. Hong, R. Wang, R. Cao, L. Han, D. Yuan, Z. Lin, Y. Zhou, Inorg. Chem. 42
(2003) 4486.
[20] Y. Liu, Q. He, X. Zhang, Z. Xue, C. Lv, Acta Crystallogr., Sect. E 64 (2008) m1605.
[21] F. Wang, K.J. Deng, G.Y. Lai, L. Cao, L.L. Wen, D.F. Li, J. Inorg. Organomet. Polym.
19 (2009) 494.
[22] L.K. Sposato, R.L. LaDuca, Acta Crystallogr., Sect. E 65 (2009) m1082.
[23] L. Pan, B. Parker, X. Huang, D.H. Olson, J. Lee, J. Li, J. Am. Chem. Soc. 128 (2006)
4180.
[24] Z. Zhang, S. Chen, J. Mi, M. He, Q. Chen, M. Du, Chem. Commun. 46 (2010) 8427.
[25] B. Xu, G. Li, H. Yang, S. Gao, R. Cao, Inorg. Chem. Commun. 14 (2011) 493.
[26] (a) Q.Y. Liu, D.Q. Yuan, L. Xu, Cryst. Growth Des. 7 (2007) 1832;
(b) C. Gandolfo, R.L. LaDuca, Cryst. Growth Des. 11 (2011) 1328.
[27] T. Fukushima, S. Horike, Y. Inubushi, K. Nakagawa, Y. Kubota, M. Takata, S.
Kitagawa, Angew. Chem., Int. Ed. 49 (2010) 4820.
[28] D.S. Zhou, F.K. Wang, S.Y. Yang, Z.X. Xie, R.B. Huang, CrystEngComm 11 (2009)
2548.
[29] Z.M. Wilseck, C.M. Gandolfo, R.L. LaDuca, Inorg. Chim. Acta 363 (2010) 3865.
[30] M.R. Montney, S. Mallika Krishnan, N.M. Patel, R.M. Supkowski, R.L. LaDuca,
Cryst. Growth Des. 7 (2007) 1145.
[31] E. Shyu, R.M. Supkowski, R.L. LaDuca, Inorg. Chem. 48 (2009) 2723.
[32] R.L. LaDuca, Coord. Chem. Rev. 253 (2009) 1759.
[33] P.J. Zapf, R.L. LaDuca, R.S. Rarig, K.M. Johnson, J. Zubieta, Inorg. Chem. 37 (1998)
3411.
[34] O. Kahn, Molecular Magnetism, VCH Publishers, New York, 1993.
[35] SAINT, Software for Data Extraction and Reduction, Version 6.02 Bruker AXS,
Inc., Madison, WI, 2002.
[36] SADABS, Software for Empirical Absorption Correction, Version 2.03 Bruker AXS,
Inc., Madison, WI, 2002.
[37] G.M. Sheldrick, SHELXTL, Program for Crystal Structure Refinement, University of
Göttingen, Göttingen, Germany, 1997.
[38] G.M. Sheldrick, CELLNOW, University of Göttingen, Göttingen, Germany, 2003.
[39] M. Kurmoo, C. Estournes, Y. Oka, H. Kumagai, K. Inoue, Inorg. Chem. 44 (2005)
217.
[40] K.M. Blake, M.A. Braverman, J.H. Nettleman, L.K. Sposato, R.L. LaDuca, Inorg.
Chim. Acta 363 (2010) 3966.
References
[1] (a) C. Janiak, Dalton Trans. (2003) 2781 (and references therein);
(b) U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastré, J.
Mater. Chem. 16 (2006) 626;
(c) A.U. Czaja, N. Trukhan, U. Müller, Chem. Soc. Rev. 38 (2009) 1284 (and
references therein);
(d) C. Janiak, J.K. Vieth, New J. Chem. 34 (2010) 2366.
[2] (a) L. Pan, D.H. Olson, L.R. Ciemnolonski, R. Heddy, J. Li, Angew. Chem., Int. Ed.
45 (2006) 616;
(b) M. Dinca, A.F. Yu, J.R. Long, J. Am. Chem. Soc. 128 (2006) 8904;
(c) J.L.C. Roswell, O.M. Yaghi, Angew. Chem., Int. Ed. 44 (2005) 4670;
(d) R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R.V. Belosludov, T.C.
Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita, Nature 436
(2005) 238;
(e) A.C. Sudik, A.R. Millward, N.W. Ockwig, A.P. Côté, J. Kim, O.M. Yaghi, J. Am.
Chem. Soc. 127 (2005) 7110;
(f) X. Zhao, B. Xiao, A.J. Fletcher, K.M. Thomas, D. Bradshaw, M.J. Rosseinsky,
Science 306 (2004) 1012;
(g) N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O’Keeffe, O.M. Yaghi,
Science 300 (2003) 1127;
(h) G. Férey, M. Latroche, C. Serre, F. Millange, T. Loiseau, A. Percheron-Guegan,
Chem. Commun. (2003) 2976;
(i) H. Li, M. Eddaoudi, M. O’Keeffe, O.M. Yaghi, Nature 402 (1999) 276.
[3] (a) J.-R. Li, R.J. Kuppler, H.-C. Zhou, Chem. Soc. Rev. 38 (2009) 1477 (and
references therein);
(b) A. Cingolani, S. Galli, N. Masciocchi, L. Pandolfo, C. Pettinari, A. Sironi, Chem.
Eur. J. 14 (2008) 9890;
(c) J.S. Seo, D. Whang, H. Lee, S.I. Jun, J. Oh, Y.J. Jeon, K. Kim, Nature 404 (2000)
982;
(d) A. Mallick, S. Saha, P. Pachfule, S. Roy, R. Banerjee, J. Mater. Chem. 20 (2010)
9073.
[4] (a) Q.-R. Fang, G.-S. Zhu, M. Xue, J.-Y. Sun, S.-L. Qiu, Dalton Trans. (2006) 2399;
(b) X.-M. Zhang, M.-L. Tong, H.K. Lee, X.-M. Chen, J. Solid State Chem. 160
(2001) 118;
(c) O.M. Yaghi, H. Li, T.L. Groy, Inorg. Chem. 36 (1997) 4292.
[5] (a) J.Y. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Chem.
Soc. Rev. 38 (2009) 1450 (and references therein);
(b) L. Ma, C. Abney, W. Lin, Chem. Soc. Rev. 38 (2009) 1248;
(c) S.G. Baca, M.T. Reetz, R. Goddard, I.G. Filippova, Y.A. Simonov, M. Gdaniec,
N. Gerbeleu, Polyhedron 25 (2006) 1215;
[41] T. Steiner, Angew. Chem., Int. Ed. 41 (2002) 48.
(d) H. Han, S. Zhang, H. Hou, Y. Fan, Y. Zhu, Eur. J. Inorg. Chem. 8 (2006) 1594;
(e) C.-D. Wu, A. Hu, L. Zhang, W. Lin, J. Am. Chem. Soc. 127 (2005) 8940;
(f) W. Mori, S. Takamizawa, C.N. Kato, T. Ohmura, T. Sato, Micropor. Mesopor.
Mater. 73 (2004) 31;
[42] H.B. Burgi, J.D. Dunitz, Acc. Chem. Res. 16 (1983) 153.
[43] C.B. Aakeröy, A.M. Beatty, D.S. Leinen, Angew. Chem., Int. Ed. 38 (1999) 1815.
[44] M.R. Montney, R.M. Supkowski, R.L. LaDuca, CrystEngComm 10 (2008) 111.
[45] R.L. Carlin, Magnetochemistry, Springer-Verlag, Berlin, 1986.
[46] J.M. Rueff, N. Masciocchi, P. Rabu, A. Sironi, A. Skoulios, Eur. J. Inorg. Chem.
(2001) 2843.
(g) N. Guillou, Q. Gao, P.M. Forster, J.S. Chang, M. Noguès, S.-E. Park, G. Férey,
A.K. Cheetham, Angew. Chem., Int. Ed. 40 (2001) 2831.
[6] (a) H.A. Habib, A. Hoffmann, H.A. Höppe, G. Steinfeld, C. Janiak, Inorg. Chem. 48
(2009) 2166;
[47] (a) C. Desplanches, E. Ruiz, A. Rodríguez-Fortea, S. Alvarez, J. Am. Chem. Soc.
124 (2002) 5197;
(b) W. Chen, J.Y. Wang, C. Chen, Q. Yue, H.M. Yuan, J.S. Chen, S.N. Wang, Inorg.
Chem. 42 (2003) 944;
(c) N. Hao, E. Shen, Y.B. Li, E.B. Wang, C.W. Hu, L. Xu, Eur. J. Inorg. Chem. (2004)
4102.
(b) M. Ardon, A. Bino, K. Michelsen, E. Pedersen, J. Am. Chem. Soc. 109 (1987)
5585;
(c) U. Bosek, K. Wieghardt, B. Nuber, J. Weiss, Angew. Chem., Int. Ed. 29 (1990)
1055;
(d) P.A. Goodson, J. Glerup, D.J. Hodgson, K. Michelsen, U. Rychlewska, Inorg.
Chem. 33 (1994) 359.
[7] (a) S. Zang, Y. Su, Y. Li, Z. Ni, Q. Meng, Inorg. Chem. 45 (2006) 174;
(b) L. Wang, M. Yang, G. Li, Z. Shi, S. Feng, Inorg. Chem. 45 (2006) 2474.
[8] (a) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keefee, O.M. Yaghi,
Science 295 (2002) 469;