Syntheses, crystal structures, and magnetic properties of copper(II) and manganese(II) compounds constructed from 5-sulfoisophthalic acid (H 3SIP) and 2,2′-bipyridine (bpy) ligands

Article abstract of DOI:10.1002/ejic.200701147

The compounds [Cu₂(SIP-O)(bpy)₂(H₂O) ₂]·7H₂O (1) and [Mn(HSIP)(bpy)]_n (2) were synthesized by the hydrothermal reactions of Cu(OH)₂ or MnCl₂, 5-sulfoisophthalic acid monosodium salt (NaH₂SIP), and 2,2′-bipyridine (bpy). Single-crystal X-ray diffraction reveals that the unprecedented hydroxylation of SIP^3- catalyzed by Cu²⁺ occurs and produces the discrete SIP-O^4--bridged dicopper(II) compound 1. The hydrogen-bonding association of the seven lattice water molecules of 1 leads to the formation of an unusual 2D-layered water consisting of fused four- and sixteen-membered water rings and a discrete water octamer consisting of a cyclic tetramer and four dangling water molecules. Compound 2 is a 3D coordination polymer and has two kinds of topologically equivalent 4-connected nodes based on Mn²⁺ and HSIP^2- with a rare (4.6⁵) topology. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200701147

FULL PAPER
DOI: 10.1002/ejic.200701147
Syntheses, Crystal Structures, and Magnetic Properties of Copper(II) and
Manganese(II) Compounds Constructed from 5-Sulfoisophthalic Acid (H3SIP)
and 2,2Ј-Bipyridine (bpy) Ligands
Qing-Yan Liu,[a] Yu-Ling Wang,[b] Jun Zhao,[a] and Li Xu*[a]
Keywords: Dinuclear copper / Manganese / Hydrothermal synthesis / Crystal structures / Magnetic properties
The compounds [Cu2(SIP-O)(bpy)2(H2O)2]·7H2O (1) and
[Mn(HSIP)(bpy)]n (2) were synthesized by the hydrothermal
reactions of Cu(OH)2 or MnCl2, 5-sulfoisophthalic acid mono-
sodium salt (NaH2SIP), and 2,2Ј-bipyridine (bpy). Single-
crystal X-ray diffraction reveals that the unprecedented hy-
droxylation of SIP3– catalyzed by Cu2+ occurs and produces
the discrete SIP-O4–-bridged dicopper(II) compound 1. The
hydrogen-bonding association of the seven lattice water
molecules of 1 leads to the formation of an unusual 2D-lay-
ered water consisting of fused four- and sixteen-membered
water rings and a discrete water octamer consisting of a cy-
clic tetramer and four dangling water molecules. Compound
2 is a 3D coordination polymer and has two kinds of topologi-
cally equivalent 4-connected nodes based on Mn2+ and
HSIP2– with a rare (4.65) topology.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
while, the seven crystal lattice water molecules in 1 form an
unprecedented 2D-layered water with 4.82 topology con-
sisting of a 16-membered ring fused to a four-membered
ring, and a discrete water octamer consisting of a cyclic
tetramer and four dangling water molecules. MnII com-
pound 2 has an interesting 3D structure pillared by sulfo-
nate groups, and it has a unique (4.65) topology based on
two equivalent 4-connected nodes.
Introduction
The design and construction of metal–organic frame-
works (MOFs) is one of the most active areas of materials
research in recent years. The intense interest in these materi-
als is driven by their potential applications as functional
materials (catalysis, magnetism, electric conductivity, and
nonlinear optics) and intriguing structural diversities.[1–3]
Many efforts have thus far been devoted to the study of
carboxylate-based compounds.[4] However, relatively little
attention has been paid to the sulfonate-based assemblies,
despite the fact that the sulfonate group bears diversified
coordinating modes and ligating sensitivity to the nature
(hardness) of the metal ions.[5] Recently, 5-sulfoisophthalic
acid (H3SIP) was successfully used to investigate the lantha-
nide contraction effect[6] and the coordination polymer
chemistry of the main group metal lead(II),[7] because of
its multiple coordinating modes and the sensitivity of the
sulfonate group to the surrounding chemical environment.
The present work deals with the hydrothermal reaction of
Cu(OH)2 (or MnCl2), NaH2SIP, and bpy at 160 °C, which
produces the dimeric [Cu2(SIP-O)(bpy)2(H2O)2]·7H2O (1)
{or 3D [Mn(HSIP)(bpy)]n (2)}. Unprecedented in situ hy-
droxylation of SIP occurs in the case of Cu(OH)2. Mean-
Results and Discussion
Hydrothermal Synthesis
Hydrothermal synthesis is widely employed to produce
new materials with diverse structural architectures, but it
remains a black box. This method can minimize the prob-
lems associated with ligand solubility and enhance the reac-
tivity of reactants in favor of efficient molecular building
during the crystallization process. In the preparation of
compounds 1 and 2 (Scheme 1), the reaction conditions are
[a] State Key Laboratory of Structural Chemistry, Fujian Institute
of Research on the Structure of Matter, Chinese Academy of
Sciences,
Fuzhou, Fujian, 350002, P. R. China
Fax: +86-591-83705045
E-mail: xli@fjirsm.ac.cn
[b] College of Chemistry and Chemical Engineering, Jiangxi Nor-
mal University,
Scheme 1. Coordination modes of the SIP-O and HSIP ligands ob-
served in compounds 1 and 2.
Nanchang, Jiangxi 330022, P. R. China
Eur. J. Inorg. Chem. 2008, 1157–1163
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1157

Q.-Y. Liu, Y.-L. Wang, J. Zhao, L. Xu
FULL PAPER
almost the same but the outcomes are quite different. The Table 1. Selected bond lengths [Å] and bond angles [°] for 1 and
2.[a]
solution reactions between CuII and SIP were reported pre-
viously to produce CuII–SIP coordination polymers.[5] Un-
der the present hydrothermal conditions, however, the un-
usual hydroxylation of SIP occurs in situ to yield the or-
Compound 1
Cu1–O1
Cu1–O5
1.902(3)
1.998(3)
1.990(3)
1.978(3)
2.172(3)
1.905(3)
1.958(3)
1.982(3)
2.007(3)
2.197(4)
94.13(14)
101.59(13)
117.57(14)
O10–Cu1–N2
O5–Cu1–O1
O5–Cu1–N2
N1–Cu1–N2
N1–Cu1–O1
O9–Cu2–O3
O9–Cu2–O5
O9–Cu2–N3
O9–Cu2–N4
O5–Cu2–O3
O5–Cu2–N3
N4–Cu2–N3
N4–Cu2–O3
92.35(14)
88.66(12)
93.37(13)
81.20(14)
92.76(13)
95.06(14)
105.52(13)
90.73(14)
107.29(14)
89.77(12)
93.18(13)
81.49(14)
92.31(13)
ganic compound 2-oxo-5-sulfoisophthalic acid (SIP-O4–), Cu1–N1
Cu1–N2
which is indicative of the catalytic oxidation properties of
Cu1–O10
Cu2+ ions at elevated temperatures. The similar in situ
Cu2–O3
metal/ligand redox reaction with isophthalic acid was re-
Cu2–O5
Cu2–N3
ported previously.[8]
Cu2–N4
Cu2–O9
O10–Cu1–O1
O10–Cu1–O5
O10–Cu1–N1
Crystal Structure of [Cu2(SIP-O)(bpy)2(H2O)2]·7(H2O) (1)
X-ray structural analysis clearly reveals the existence of
an additional oxygen atom attached to SIP to form SIP-
O4–, which achieves the charge balance. The structure of the
host [Cu2(SIP-O)(bpy)2(H2O)2] motif is shown in Figure 1,
wherein the two crystallographically independent but geo-
metrically similar CuII atoms are bridged by two unidentate
carboxylate groups and one bridging phenyl oxygen atom
(O6). One bpy ligand and one water oxygen atom complete
Compound 2
Mn1–O5
Mn1–O3C
Mn1–N1
2.192(3)
2.149(3)
2.278(4)
Mn1–O1A
Mn1–O6B
Mn1–N2
O1A–Mn1–N2
N1–Mn1–N2
O5–Mn1–O1A
O5–Mn1–N1
O6B–Mn1–N1
2.156(3)
2.185(3)
2.272(4)
86.11(14)
71.81(15)
93.74(13)
88.77(14)
88.38(15)
O3C–Mn1–O1A 105.76(13)
O3C–Mn1–N1
O5–Mn1–O6B
O5–Mn1–O3C
96.29(15)
173.39(13)
88.51(14)
92.14(15)
92.64(15)
a distorted square-pyramidal coordination geometry of O5–Mn1–N2
O6B–Mn1–N2
O6B–Mn1–O1A 91.14(14)
each Cu center. The Cu–O bond lengths range from
O6B–Mn1–O3C 85.87(14)
1.902(3) to 2.197(4) Å, and the Cu–N bond lengths vary
from 1.978(3) to 2.007(3) Å (Table 1). The bond dimensions
involving Cu are normal, and they are comparable to the
values in related copper(II) complexes.[5,9] The dinuclear
copper units are interconnected through the hydrogen
bonds between the coordinating water molecules and the
carboxylate groups [O···O = 2.938(5) and 2.856(5) Å] into
a 1D chain parallel to the c axis (Figure 2a and Table 2).
The adjacent chains are linked together through hydrogen
bonds [O···O = 2.800(7) and 2.814(7) Å] between the sulfo-
nate groups and the two lattice water molecules (O6W and
O7W) to form a 2D supramolecular layer in the bc plane
(Figure 2b).
[a] Symmetry transformation for equivalent atoms: Compound 2:
A: x – 1/2, –y + 2/3, –z; B: –x + 1/2, y – 1/2, z; C: x, –y + 3/2, z –
1/2.
Figure 1. ORTEP drawing of [Cu2(SIP-O)(bpy)2(H2O)2] with 30%
probability thermal ellipsoids.
Figure 2. (a) 1D Hydrogen-bonded chain, (b) 2D hydrogen-bonded
layer parallel to the bc plane (bpy has been omitted for clarity).
The hydrogen-bonding association of four of the seven
lattice water molecules leads to the formation of a 2D-lay-
ered water consisting of fused four- and sixteen-membered metric 16-membered water ring formed by O3W, O5W,
water rings (Figure 3). The geometrical parameters of the O6W, O7W, and their equivalents are illustrated in Fig-
water clusters are summarized in Table 2. The centrosym- ure 3a with the dimension of approximately 9ϫ10 Å, which
1158
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 1157–1163

CuII and MnII Compounds Constructed from H3SIP and bpy Ligands
Table 2. Hydrogen bonds parameters in compound 1.[a]
D–H···A
O1W–H1WA···O2WA 0.90(2)
O1W–H1WB···O2W 0.89(2)
O3W–H3WB···O5WB 0.93(6)
O4W–H4WB···O1WA 0.92(9)
D–H [Å] H···A [Å] ЄDHA [°] D···A [Å]
2.02(2)
1.93(5)
1.96(4)
2.09(9)
1.92(4)
1.82(3)
1.74(2)
1.83(2)
1.86(2)
1.92(2)
2.06(5)
2.00(2)
1.98(3)
176(7)
178(9)
156(8)
166(1)
167(5)
169(6)
168(6)
172(5)
170(5)
168(5)
170(6)
166(4)
157(5)
2.918(7)
2.827(7)
2.824(8)
2.981(8)
2.805(7)
2.706(7)
2.678(8)
2.714(8)
2.736(6)
2.781(5)
2.938(5)
2.856(5)
2.823(6)
3.014(6)
2.759(6)
2.919(7)
2.800(7)
2.814(7)
O5W–H5WA···O3W
O5W–H5WB···O7WB 0.89(5)
O6W–H6WB···O3W 0.95(2)
O7W–H7WA···O6WC 0.89(4)
0.91(5)
O9–H9C···O5W
O10–H10B···O1W
O9–H9B···O4C
O10–H10C···O2D
O2W–H2WA···O8A
O2W–H2WB···O2
O3W–H3WA···O4
O4W–H4WA···O6
O6W–H6WA···O7B
O7W–H7WB···O7B
0.89(2)
0.88(2)
0.88(5)
0.88(4)
0.89(2)
0.90(2)
0.92(5)
0.90(2)
0.91(2)
0.90(5)
2.25(11) 143(15)
1.85(3)
2.08(3)
1.91(6)
1.96(3)
168(8)
155(5)
168(0)
158(6)
[a] Symmetry transformations used to generate equivalent atoms:
A: –x, –y + 1, –z; B: –x + 1, –y + 1, –z; C: x, –y + 1/2, z – 1/2; D:
x, –y + 1/2, z + 1/2.
represents a unique cyclic (H2O)16. A discrete acyclic
(H2O)16 cluster, however is known.[10] Theoretical calcula-
tions proposed five lowest energy (H2O)16 clusters, and the
most stable one is the linear fused cube derived from the
D2d and S4 forms of (H2O)8.[11] However, its existence is not
confirmed experimentally to date. Thus, our observation of
the cyclic sixteen-membered ring in the 2D-layered water
may be attributed to its different modes of connectivity with
the surrounding water molecules and the interactions with
the dinuclear copper motifs. As depicted in Figure 3b, O3W
and O5W are hydrogen bonded to their symmetry-related
equivalents to form a D2h-symmetric cyclic water tetramer.
Within the tetramer, the four water oxygen atoms are com-
pletely coplanar, and each water monomer acts as both a
single hydrogen-bond donor and a single hydrogen-bond
acceptor. The remaining hydrogen atoms are alternatively
oriented above or below the ring plane to achieve the mini-
mum H–H repulsion. In the 2D water sheet, the O···O sepa-
rations range from 2.678(8) to 2.824(8) Å with an average
distance of 2.745 Å, which is close to the corresponding
value of 2.748 Å in the 2D supramolecular ice-like layer
containing (H2O)12 rings in the organic compound
bpedo·5H2O [bpedo = trans-bis(4-pyridyl)ethylene diox-
ide].[12] Moreover, the average O···O···O angle of 110.7° is
similar to the tetrahedral geometry. From a topology view-
point, the hydrogen-bonded 2D water layer can be regarded
to have 4.82 topology (Figure 3c). This type of net, pre-
dicted by Wells[13] but commonly observed for coordination
frameworks[14] and not previously observed for the water
cluster, consists of three-connected nodes (O3W and O5W)
shared by one tetragonal square unit (cyclic water tetramer)
and two octagons (cyclic water hexadecamer). This type of
water layer, to the best of our knowledge, is unprecedented.
Additional O9–H9C···O5W hydrogen bonds anchor the 2D
Figure 3. (a) The centrosymmetric (H2O)16 water ring; (b) the
D2h-symmetric cyclic water tetramer cluster in 1; (c) view of the 2D
water layer with 4.82 topology parallel to the bc plane.
The remaining three lattice water molecules (O1W, O2W,
O4W) and one coordinating water molecule (O10) form the
discrete water octamer consisting of cyclic tetramer and
four dangling water molecules (Figure 4). This water octa-
mer and the above-described 2D water layers are alterna-
tively placed between the host supramolecular layers. In the
centrosymmetric cyclic water tetramer formed by O1W and
O2W and their equivalents, O1W acts as a hydrogen-bond
donor and O2W as an acceptor. This type of cyclic (H2O)4
cluster is different from the one in the above-mentioned 2D
water layer, but similar to that in the solid state complex
{[Cd(dpp)(SIP)(H2O)3]·0.5Cd(H2O)6·5H2O}n [dpp = 1,3-
bis(4-pyridyl)propane].[15] This unusual conformation is be-
water layer to the host metal–organic supramolecular layer. Figure 4. The centrosymmetric water octamer in 1.
Eur. J. Inorg. Chem. 2008, 1157–1163
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1159

Q.-Y. Liu, Y.-L. Wang, J. Zhao, L. Xu
FULL PAPER
lieved to result from the fact that the two water molecules water octamer consisting of a cyclic water hexamer and two
(O4W and O10) both act as single hydrogen donors in the dangling water molecules.[20] The remaining six hydrogen
hydrogen bonds to O1W in the resulting centrosymmetric atoms per (H2O)8 cluster unit are bonded to the carboxylate
(H2O)8 cluster. The common patterns for the water octamer oxygen atoms and sulfonate oxygen atoms of the SIP-O li-
experimentally found are cubane,[16] opened cube,[17] and gand to form a 3D supramolecular network (Figure 5).
cyclic ring.[18] Theoretical calculations show that the cub- Thus, the 2D-layered water and discrete water octamers oc-
ane-like conformation with S4 symmetry has an energy cupy the voids between the layers and act as “glue” to as-
minimum, and it has been observed experimentally.[16,19] semble the dinuclear coordination units around them to
Interestingly, the centrosymmetric (H2O)8 cluster observed give a 3D structure.
here is quite different from those theoretically predicted or
experimentally found, which indicates that the conforma-
tion of water clusters varies with the host environment. The
averaged O···O separation of 2.877 Å is slightly longer than
Crystal Structure of [Mn(HSIP)(bpy)]n (2)
The asymmetric unit in compound 2 consists of one
manganese(II) ion, one HSIP dianion, and one bpy mole-
cule. As depicted in Figure 6, the four equatorial positions
of Mn2+ are occupied by two carboxylate oxygen atoms
from two HSIP2– ligands and one chelating bpy nitrogen
atom; the benzene and bpy moieties are almost coplanar.
Two sulfonate oxygen atoms from two HSIP2– ligands take
up the apical positions to complete the octahedral coordi-
nation geometry, and the O6B–Mn1–O5 angle is 173.3(1)°.
The Mn–O bond lengths range from 2.152(3) to 2.192(2) Å,
and the Mn–N bond lengths are 2.270(3) and 2.273(3) Å,
which are comparable with the values in related Mn(II)
complexes.[21] The HSIP2– ligand adopts a tetradentate
bridging coordination mode through its monodentate car-
boxylate groups and bidentate sulfonate group (Scheme 1).
To the best of our knowledge, this coordination mode has
not been observed previously for the HSIP2– ligand.[5–7,15]
One of the carboxylate groups is protonated for charge bal-
ance, as suggested by the strong absorption at 1693 cm–1 in
the IR spectrum and strong H+-assisted hydrogen bonds
between the free carboxylate oxygen atoms (O2AЈ···O4
2.344 and O2A···O4 2.436 Å, A: x – 1/2, y, –z + 1/2). As
the value of 2.745 Å in the cyclic (H2O)8 cluster in the or-
ganic calix[4]resorcinarene supramolecular complex,[18]
2.846 Å in the cubane water octamer,[16] and 2.85 Å in the
Figure 5. The hydrogen-bonded 3D supramolecular framework
of 1.
Figure 6. Molecule structure of 2 with 30% probability displacement ellipsoids.
1160
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 1157–1163

CuII and MnII Compounds Constructed from H3SIP and bpy Ligands
depicted in Figure 7a, the Mn(bpy) units are connected by (Schäfli) notation is (4.62.6.6.6.6). Thus, the 3D structure is
the carboxylate groups of HSIP2– to yield almost planar 1D a binodal net with the short symbol of (4.65). This type
chains propagating along the a axis. The infinite chains are of topology, to the best of our knowledge, has never been
displaced parallel to each other so that the peripheral sulfo- documented for a coordination complex. A large number
nate oxygen atoms of each chain are able to apically bond of potential 4-connected nets have been identified. By far
to Mn2+ from the four neighboring chains to form a 3D the most common of these are the diamond net[23] and to
[24]
framework, as shown in Figure 7a,b. The 3D structure fea- a lesser extent the CdSO4 and NbO nets.[25] All of the 4-
tures four types of rings, A–D, as depicted in Figure 7c that connected nets contain six-membered and larger rings, and
are characteristic of the metal–SIP compounds.[22]
examples of four-membered rings are comparatively rare in
3D coordination frameworks. Therefore, the topologic
structure shown in Figure 8 presents a rare example of a 4-
connected net.
Figure 8. View of the topological net observed in 2 illustrating the
4-connected (4.65) network (metal nodes are in black; ligand nodes
are in gray).
Magnetic Properties
The magnetic susceptibility of 2 was recorded over 5–
300 K. The plots of molar magnetic susceptibility (χM) and
magnetic moment (µB) vs. temperature are shown in Fig-
ure 9. The magnetic moment per Mn2+ is 5.72 µB at 300 K,
which is close to the spin-only value for the magnetically
isolated high-spin Mn2+ (5.92 µB). The value remains al-
most constant over the temperature range 300–90 K
(5.57 µB) and then decreases to 3.26 µB at 5 K. The mag-
netic susceptibility data between 300 and 5 K obey the Cu-
rie–Weiss law, χM = C/(T – θ), where the Curie constant
C and Weiss constant θ are 4.03 emuKmol–1 and –5.79 K,
respectively. The small Weiss constants in these complexes
Figure 7. (a) Infinite chain formed by Mn2+ and the carboxylate
arms; (b) 3D structure formed by interchain bonds between sulfo-
nate oxygen atoms and Mn2+ at apical positions (bpy is omitted
for clarity); (c) The A–D rings in the 3D framework.
Better insight into the nature of this intricate 3D frame-
work can be achieved by the topological approach, that is,
by reducing the multidimensional structures to simple node
and connection nets. As depicted in Figure 8, each Mn
atom is coordinated by four oxygen atoms from four
HSIP2– ligands and each HSIP2– ligand bridges four neigh-
boring Mn atoms (Figure 6). Therefore, the Mn atom and
the HSIP2– ligand both act as 4-connected nodes in a 1:1
ratio in this structure. It is interesting that the two 4-con-
Figure 9. Plots of χM and magnetic moment (per mol) vs. tempera-
nected nodes are topologically equivalent, and the long ture.
Eur. J. Inorg. Chem. 2008, 1157–1163
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1161

Q.-Y. Liu, Y.-L. Wang, J. Zhao, L. Xu
FULL PAPER
indicate the weak antiferromagnetic interactions between different metals. In situ hydroxylation of SIP was observed
the Mn2+ centers, which is consistent with the slow decrease for the first time in the case of Cu2+, which produced the
in the magnetic moment.
SIP-O4–-bridged dicopper(II) compound [Cu2(SIP-O)(bpy)2-
(H2O)2]·7H2O (1). The similar reaction of MnCl2 produced
the 3D coordination polymer [Mn(HSIP)(bpy)]n (2). The
lattice water molecules in 1, which form 2D-layered water
with a unique 4.82 topology, and a discrete water octamer
are alternatively located between the 2D supramolecular
host sheets. Compound 2 has a 3D coordination framework
with a rare 4.65 topology. The Mn2+ ions are linked by the
carboxylate arms of the HSIP ligand into an infinite chain
that are further pillared by the sulfonate group through api-
cal coordination to yield a 3D architecture. This presum-
ably provides a new strategy to build 3D frameworks based
on infinite chains.
FTIR Spectra, Thermogravimetric Analyses, and Powder X-
ray Diffraction
The FTIR spectrum of 1 shows a broad band centered
at 3357 cm–1, which is attributable to the O–H stretching
frequency of the water cluster. This value is very close to
the value of 3359 cm–1 in the extended water tapes.[12] The
strong absorptions at 1601 and 1563 [vasym(CO2)] and
1445 cm–1 [vsym(CO2)] are due to the carboxylate groups.
The IR spectrum of 2 shows a strong absorption at
1693 cm–1, which clearly indicates the existence of a proton-
ated carboxylate group in the structure of 2. The strong
bands at 1664 and 1443 cm–1 correspond to the asymmetric
and symmetric stretching bands of the carboxylate groups,
Experimental Section
respectively. The absorptions in the region 1000–1200 cm–1 General Remarks: All chemicals, including 5-sulfoisophthalic acid
monosodium salt (Alfa), were purchased commercially and used
without further purication. Elemental analyses were carried out
with an Elementar Vario EL III analyzer, and IR spectra (KBr
pellets) were recorded with a PerkinElmer Spectrum One. Thermo-
for the two complexes are typical for the sulfonate group.
The strong absorption bands at 618 and 622 cm–1 for 1 and
2, respectively, are due to νS–O stretching.
To examine the thermal stability of the two compounds
and their structural variation as a function of temperature,
thermogravimetric analyses (TGA) were performed on sin-
gle-phase polycrystalline samples of these materials (Fig-
ure 10). The results of compound 1 show a weight loss of
14.9% in the temperature range 40–115 °C, which is due to
the loss of all lattice water molecules (calcd. 14.7%). Com-
plete decomposition was observed above 280 °C. Thermo-
gravimetric analysis of 2 showed that the initial weight loss
occurred in the temperature range 400–455 °C, which is at-
tributable to the release of the bpy molecule (calcd. 34.3%;
found 35.4%). Increasing the temperature led to the decom-
position of the Mn–HSIP framework at 460 °C.
gravimetric measurements were performed with
a Netzsch
STA449C apparatus under a nitrogen atmosphere with a heating
rate of 10 °Cmin–1 from 25 to 800 °C. Variable-temperature suscep-
tibility measurements were carried out in the temperature range 5–
300 K at a magnetic field of 0.5 T on polycrystalline samples with
a Quantum Design MPMS-5 magnetometer.
[Cu2(SIP-O)(bpy)2(H2O)2]·7(H2O) (1): The hydrothermal reaction
of fresh Cu(OH)2 (0.001 g, 0.1 mmol) with NaH2SIP (0.015 g,
0.6 mmol), bpy (0.015 g, 0.1 mmol), and water (18 mL) at 165 °C
for 120 h produced green crystals of 1 (0.002 g, 5%). IR (KBr pel-
let): ν = 3357 (m), 1601 (vs), 1563 (s), 1496 (m), 1476 (m), 1445
˜
(vs), 1361 (m), 1313 (m), 1280 (m), 1285 (m), 1109 (s), 1101 (m),
1033 (s), 1101 (m), 938 (w), 815 (w), 778 (m), 731 (m), 662 (m),
618 (s) cm–1. C28H36Cu2N4O17S (859.75): calcd. C 39.08, H 4.19,
N 6.51; found C 39.03, H 4.17, N 6.49.
[Mn(HSIP)(bpy)]n (2): The hydrothermal reaction of MnCl2
(0.012 g, 0.1 mmol) with NaH2SIP (0.026 g, 0.1 mmol), bpy
(0.015 g, 0.1 mmol), triethylamine (0.1 mL), and water (18 mL) at
165 °C for 120 h produced pale yellow crystals of 2 (0.025 g, 56%).
IR (KBr pellet): ν = 3472 (w), 3106 (w), 3083 (w), 1693 (s), 1664
˜
(vs), 1590 (s), 1573 (s), 1471 (m), 1443 (vs), 1388 (m), 1320 (m),
1268 (s), 1154 (s), 1097 (s), 1047 (s), 1009 (s), 907 (m), 994 (w),
761 (s), 734 (m), 669 (m), 631 (s), 622 (s), 572 (w), 551 (w) cm–1.
C18H12MnN2O7S (455.30): calcd. C 47.48, H 2.66, N 6.15; found
C 47.40, H 2.67, N 6.13.
X-ray Crystallographic Studies: X-ray diffraction data of com-
pounds 1 and 2 were collected with a Rigaku Mercury CCD dif-
fractometer equipped with a graphite-monochromated Mo-Kα ra-
diation (λ = 0.71073 Å). The CrystalClear software was used for
data reduction and empirical absorption correction.[26] The struc-
tures were solved by direct methods and successive Fourier differ-
ence syntheses and refined by the full-matrix least-squares method
on F2 (SHELXTL Version 5.1).[27] The O2 carboxylate oxygen
atom in 2 was found to be disordered over two positions. Aromatic
hydrogen atoms were assigned to calculated positions with isotropic
thermal parameters fixed at 1.2 times that of the attached carbon
Figure 10. TG curve of compounds 1 and 2.
Conclusions
The hydrothermal reaction system of M2+–SIP, where
M = Cu or Mn, affords quite distinct outcomes for the two atom. Hydrogen atoms attached to water oxygen atoms were lo-
1162 Eur. J. Inorg. Chem. 2008, 1157–1163
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

CuII and MnII Compounds Constructed from H3SIP and bpy Ligands
[2] O. R. Evans, R. Xiong, Z. Wang, G. K. Wong, W. Lin, Angew.
Chem. 1999, 111, 557–559; Angew. Chem. Int. Ed. 1999, 38,
536–538.
Table 3. Crystallographic data for compounds 1 and 2.
1
2
[3] M. Eddaoudi, D. B. Moler, H. L. Li, B. L. Chen, T. M. Rein-
eke, M. O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319–
330.
Empirical Formula
Molecular mass
Temperature [K]
Crystal size [mm]
Crystal system
Space group
Z
a [Å]
b [Å]
c [Å]
α [°]
C28H36N4O17SCu2 C18H12N2O7SMn
859.75
293(2)
455.30
293(2)
[4] a) C.-D. Wu, W.-B. Lin, Angew. Chem. Int. Ed. 2005, 44, 1958–
1961; b) T. J. Prior, M. J. Rosseinsky, Chem. Commun. 2001,
1222–1223; c) D. F. Sun, R. Cao, Y. Q. Sun, W. H. Bi, X. J. Li,
Y. Q. Wang, Q. Shi, X. Li, Inorg. Chem. 2003, 42, 7512–7518.
[5] a) A. D. Kulynych, G. K. H. Shimizu, CrystEngComm 2002, 4,
102–105; b) D.-F. Sun, R. Cao, Y.-Q. Sun, X. Li, W.-H. Bi, M.-
C. Hong, Y.-J. Zhao, Eur. J. Inorg. Chem. 2003, 94–98; c) A. P.
Côté, G. K. H. Shimizu, Chem. Commun. 2001, 251–252.
[6] Q.-Y. Liu, L. Xu, Eur. J. Inorg. Chem. 2005, 3458–3466.
[7] Q.-Y. Liu, L. Xu, Eur. J. Inorg. Chem. 2006, 1620–1628.
[8] J. Tao, Y. Zhang, M.-L. Tong, X.-M. Chen, T. Yuen, C.-L. Lin,
X.-Y. Huang, J. Li, Chem. Commun. 2002, 1342–1343.
[9] a) S. H. Gou, M. Qian, Z. Yu, C. Y. Duan, X. F. Sun, W. Hu-
ang, J. Chem. Soc., Dalton Trans. 2001, 3232–3237; b) Q.-Y.
Liu, L. Xu, Cryst. Growth Des. 2007, 7, 1832–1843.
[10] S. K. Ghosh, P. K. Bharadwaj, Inorg. Chem. 2004, 43, 6887–
6889.
[11] S. Maheshwary, N. Patel, N. Sathyamurthy, A. D. Kulkarni,
S. R. Gadre, J. Chem. Phys. 2001, 115, 10525–10531.
[12] B. Q. Ma, H. L. Sun, S. Gao, Angew. Chem. Int. Ed. 2004, 43,
1374–1376.
[13] A. F. Wells, Structural Inorganic Chemistry, 5th ed., Clarendon,
Oxford, 1984.
[14] a) D. L. Long, A. J. Blake, N. R. Champness, M. Schröder,
Chem. Commun. 2000, 1369–1370; b) J. Fan, W.-Y. Sun, T. Ok-
amura, W.-X. Tang, N. Ueyama, Inorg. Chem. 2003, 42, 3168–
3175.
[15] Q.-Y. Liu, L. Xu, CrystEngComm 2005, 7, 87–89.
[16] W. B. Blanton, S. W. Gordon-Wylie, G. R. Clark, K. D. Jordan,
J. T. Wood, U. Geiser, T. J. Collins, J. Am. Chem. Soc. 1999,
121, 3551–3552.
0.20ϫ0.16ϫ0.12 0.12ϫ0.08ϫ0.05
monoclinic
P21/c
4
orthorhombic
Pbca
8
19.1828(17)
14.1577(11)
12.6442(11)
90
95.598(4)
90
15.9207(13)
13.4252(10)
16.7567(13)
90
90
90
β [°]
γ [°]
V [Å3]
3417.6(5)
1.671
1.389
3581.6(5)
1.689
0.901
Dcalcd. [gcm–3]
µ [mm–1]
Measured reflections
Independent reflections
Observed reflections
[IϾ2σ(I)]
Parameters
F(000)
Completeness [%]
2θ range [°]
Index ranges
20803
5776
20706
3023
4661
2405
541
1768
271
1848
99.0
98.3
5.08 to 24.71
–19ՅhՅ22
–16ՅkՅ15
13ՅlՅ14
0.0530
3.14 to 25.03
–18ՅhՅ–18
15ՅkՅ15
–19ՅlՅ19
0.0870
R [int]
R1 [obsd. refl.]
wR2 [all refl.]
Largest diff. peak and
hole [eÅ–3]
0.0550
0.1249
0.0659
0.0960
0.418/–0.331
0.616/–0.366
[17] R. J. Doedens, E. Yphannes, M. I. Khan, Chem. Commun.
2002, 62–63.
[18] J. L. Atwood, L. J. Barbour, T. J. Ness, C. L. Raston, P. L. Ras-
ton, J. Am. Chem. Soc. 2001, 123, 7192–7193.
[19] C. J. Tsai, K. D. Jordan, J. Chem. Phys. 1993, 99, 6957–6970.
[20] B.-Q. Ma, H.-L. Sun, S. Gao, Chem. Commun. 2005, 2336–
2338.
[21] C.-M. Ma, C.-N. Chen, Q.-T. Liu, D.-Z. Liao, L.-C. Li, L.-C.
Sun, New J. Chem. 2003, 27, 890–894.
cated from difference maps and refined with O–H distances re-
strained to 0.90 Å, and isotropic thermal parameters fixed at 1.5
times that of the respective oxygen atom. The R1 values are
defined as R1 = Σ||Fo| – |Fc||/Σ|Fo| and wR2 = {Σ[w(Fo2 – Fc2)2]/
Σ[w(Fo2)2]}1/2. Details of the crystal parameters, data collection,
and refinement are summarized in Table 3, and selected bond
lengths and bond angles are listed in Table 1.
[22] Z.-M. Sun, J.-G. Mao, Y.-Q. Sun, H.-Y. Zeng, A. Clearfield,
Inorg. Chem. 2004, 43, 336–341.
CCDC-294696 (for 1) and -649721 (for 2) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[23] a) L. Carlucci, G. Ciani, D. M. Proserpio, S. Rizzato, Chem.
Eur. J. 2002, 8, 1519–1526; b) Y. H. Liu, H. C. Wu, H. M. Lin,
W. H. Hou, K. L. Lu, Chem. Commun. 2003, 60–61.
[24] a) G. E. Kostakis, L. Casella, N. Hadjiliadis, E. Monzani, N.
Kourkoumelisc, J. C. Plakatouras, Chem. Commun. 2005,
3859–3861; b) B. R. Bhogala, P. K. Thallapally, A. Nangia,
Cryst. Growth Des. 2004, 4, 215–218.
Acknowledgments
[25] M. Eddaoudi, J. Kim, M. O’Keeffe, O. M. Yaghi, J. Am. Chem.
Soc. 2002, 124, 376–377.
[26] CrystalClear, version 1.3, Rigaku Corp. 2000.
[27] G. M. Sheldrick, SHELXS 97: Program for Crystal Structure
Solution, University of Göttingen, 1997.
This work was supported by the National Science Foundation of
China (Grant No. 20773129 and 20473092) and 973 Program
(Grant No. 2006CB932900).
[1] B. Moulton, M. J. Zaworotko, Chem. Rev. 2001, 101, 1629–
Received: October 23, 2007
Published Online: January 7, 2008
1658.
Eur. J. Inorg. Chem. 2008, 1157–1163
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1163