Structural diversity of copper(II) coordination polymers based on tosylated isophthalic ligands

Article abstract of DOI:10.1002/zaac.201300195

Two tosylated isophthalic ligands, namely, 5-tosyloxy-isophthalic acid (H₂toip) and 5-tosylamino-isophthalic acid (H₂taip) were synthesized. Self-assembly of Cu^II ions with H₂toip and H₂taip ligands under different reaction conditions (temperature, solvents, and auxiliary ligands) gave rise to three coordination polymers formulated as [Cu(toip)(py)₂]_n (1), [Cu ₆(toip)₆(H₂O)₆]_n· 8n(H₂O) (2), and [Cu₆(taip)₆(py) ₄(dmf)₂]_n·n[(dmf)₆(MeOH) ₂(H₂O)₂] (3) (py = pyridine, dmf = dimethylformamide). Compound 1 is a one-dimensional (1D) coordination polymeric chain. Compounds 2 and 3 are two-dimensional (2D) coordination networks featuring very similar Kagome lattices based on the interconnection of paddle-wheel [Cu₂(COO)₄] secondary building units (SBUs) and toip^2-/taip^2- ligands. However, the arrangement of adjacent Kagome lattices in 2 and 3 are distinct, making them crystallize in different space groups and thereby have different crystal structures. Copyright

Full text of DOI:10.1002/zaac.201300195

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Date: 11-06-13 17:43:11
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ARTICLE
DOI: 10.1002/zaac.201300195
Structural Diversity of Copper(II) Coordination Polymers Based on
Tosylated Isophthalic Ligands
Xinfa Li*[a] and Qingyan Liu[b]
Keywords: Coordination polymer; Structure diversity; Tosylation; Copper; Isophthalic ligand
Abstract. Two tosylated isophthalic ligands, namely, 5-tosyloxy-
coordination polymeric chain. Compounds 2 and 3 are two-dimen-
isophthalic acid (H2toip) and 5-tosylamino-isophthalic acid (H2taip)
sional (2D) coordination networks featuring very similar Kagomé lat-
were synthesized. Self-assembly of CuII ions with H2toip and H2taip tices based on the interconnection of paddle-wheel [Cu2(COO)4] sec-
ligands under different reaction conditions (temperature, solvents, and
auxiliary ligands) gave rise to three coordination polymers formulated
ondary building units (SBUs) and toip2–/taip2– ligands. However, the
arrangement of adjacent Kagomé lattices in 2 and 3 are distinct, mak-
as [Cu(toip)(py)2]n (1), [Cu6(toip)6(H2O)6]n·8n(H2O) (2), and ing them crystallize in different space groups and thereby have dif-
[Cu6(taip)6(py)4(dmf)2]n·n[(dmf)6(MeOH)2(H2O)2] (3) (py = pyridine,
dmf = dimethylformamide). Compound 1 is a one-dimensional (1D)
ferent crystal structures.
On the other hand, the synthesis conditions including tem-
perature, crystallization solvents, counterions, and auxiliary li-
gands have a crucial influence on the structure of the resulting
coordination polymers, and these always lead to structurally
diversified isomer crystals even for a fixed chemical composi-
tion. The investigation on such isomer crystals may help to
understand the effect of reaction conditions on the resultant
crystal structures and to reach the final control over the physi-
cal properties of coordination polymers even though such con-
trol remains a challenge for chemists.
Herein we report two tosylated isophthalic ligands (H2toip
and H2taip) and three coordination polymers: [Cu(toip)(py)2]n
(1), [Cu6(toip)6(H2O)6]n·8n(H2O) (2), and [Cu6(taip)6(py)4-
(dmf)2]n·n[(dmf)6(MeOH)2(H2O)2] (3), regarding their synthe-
ses and X-ray crystal structures. The results show that different
crystallization solvents and auxiliary ligands give rise to dif-
ferent crystal structures.
Introduction
Functional coordination polymers have stayed on the focus
of materials research in recent decades not only for their aes-
thetically pleasing architectures and topologies but also due to
their potential applications in magnetism, luminescence, ad-
sorption, catalysis, and chemical sensing.[1–10] The great suc-
cess of coordination polymers in these application areas is as-
cribed to their excellent porosity, structural controllability, and
modifiability.[11,12] The rational choice and design of ligands
play a very important role in the acquisition of functional coor-
dination polymers with desired structures and physical proper-
ties. Up to now, angular and linear aromatic polycarboxylic
ligands have been widely explored and successfully used for
the construction of functional coordination polymers.[13–23]
Isophthalic acid and analogues are one of the most popular
ligands of this kind, and many interesting coordination poly-
mers with the well-known dinuclear tetracarboxylate paddle-
wheel [M2(COO)4] SBUs have been reported.[24–28] However,
as far as we known, the tosylation strategy has rarely been
introduced for modification of 5-hydroxyisophthalic and 5-
aminoisophthalic ligands. It is expected that tosylation can
change the solubility and coordination behavior of carboxylic
ligands and thereby the structures and properties of coordina-
tion polymers.
Results and Discussion
Structure Description
Crystal Structure of H2toip
According to X-ray single-crystal diffraction, H2toip crys-
tallizes in the centrosymmetric P21/c space group. As shown
in Figure 1, the asymmetric unit contains only one H2toip mo-
lecule. Each H2toip molecule is hydrogen-bonded to two
neighboring equivalents by two carboxyl groups, forming a 1D
supramolecular “zigzag” chain extending along the direction
of b axis (Figure 2). The hydrogen bonds featuring eight-mem-
bered [···HOCO···HOCO···] rings are very common in carbox-
ylic dimers. The sulfonate group is also involved in the forma-
tion of weak inter-chain C(sp2)–H···O–S hydrogen bonds. De-
tailed hydrogen-bonding parameters are listed in Table S1
* Dr. X. Li
E-Mail: xflichem@163.com
[a] Department of Chemistry
Zunyi Normal College
Zunyi 563002, P. R. China
[b] College of Chemistry and Chemical Engineering
Jiangxi Normal University
Nanchang 330022, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300195 or from the au-
thor.
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X. Li, Q. Liu
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(Supporting Information). The C–O bond lengths for two pro- by weak hydrogen bonds and van der Waals interactions to
tonated and two unprotonated carboxyl oxygen atoms are form 3D supramolecular structure.
1.270(4), 1.274(4) Å, and 1.245(4), 1.238(4) Å, respectively
(Table 2). All of them are shorter than the length of a C–O
single bond but longer than a C=O double bond, which is at-
tributed to the dual effects of electronic delocalization (p–π
conjugation) and hydrogen-bonding formation.
Figure 3. ORTEP drawing of 1 with 30% probability of thermal ellip-
soids.
Figure 1. ORTEP drawing of H2toip with 30% probability of thermal
ellipsoids.
Scheme 1. Coordination modes of toip2– and taip2– ligands exhibited
in 1 (a), 2 (b), and 3 (c).
Figure 2. View of the 1D supramolecular chain in the structure of
H2toip along the c axis.
Crystal Structure of [Cu(toip)(py)2]n (1)
Compound 1 crystallizes in the P21/c space group. As dis-
played in Figure 3, the asymmetric unit of 1 is composed of
one CuII ion, one toip2–, and two py ligands. All atoms stay
on general positions. The toip2– ligand bridges three identical
CuII ions tridentately by three carboxyl oxygen atoms
[Scheme 1(a)]. The CuII ion adopts square pyramid coordina-
tion arrangement with a [N2O3] donor set (Figure S1, Support-
ing Information). The four coordination sites on the equatorial
Figure 4. 1D coordination polymeric chain of 1. Inversion centers are
plane are occupied by two py nitrogen atoms and two carboxyl
oxygen atoms in a trans form, and the apical position is taken
up by a carboxyl oxygen atom. The Cu–O and Cu–N bond
lengths on the equatorial plane are 1.965(3), 1.995(3) Å, and
2.023(4), 2.032(4) Å, respectively, shorter than the value
drawn as dark gray balls linked to copper by dashed lines.
Crystal Structure of [Cu6(toip)6(H2O)6]n·8n(H2O) (2)
Low temperature (150 K) X-ray single-crystal structure
2.238(4) Å of the Cu–O bond on the apical position (Table 2). analysis reveals that compound 2 crystallizes in the centrosym-
All of the bond angles deviate from 90° more or less, indicat- metric C2/c space group with a unit cell volume of about
ing the square pyramid is distorted. As exhibited in Figure 4, 21313 Å3. As displayed in Figure 5, the asymmetric unit con-
the interlinkage between CuII ions and toip2– ligands give rise sists of six crystallographically independent CuII ions, six
to a centrosymmetric 1D coordination polymeric chain propa- toip2– ligands, six aqua ligands and several lattice water mole-
gating along the direction perpendicular to the (101) plane. cules. Like the other angular benzene dicarboxylate li-
The shortest Cu–Cu separation within the chain is about gands,[24–28] every toip2– coordinates to four CuII ions tetra-
4.603 Å. The tail OTs groups point to the direction of the a dentately by two carboxyl groups [Scheme 1(b)], and thereby
axis, playing the role of C(sp2)–H···O–S hydrogen-bond ac- the six CuII ions, with the aid of twelve toip2– carboxyl groups,
ceptor. Adjacent chains are further interconnected to each other make up three dimetal tetracarboxylate paddle-wheel
2
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CuII Coordination Polymers Based on Tosylated Isophthalic Ligands
Figure 7. ORTEP drawing of 3 with 30% probability of thermal ellip-
soids. Hydrogen atoms, lattice DMF, CH3OH, and H2O molecules are
omitted.
Figure 5. ORTEP drawing of 2 with 30% probability of thermal ellip-
soids. Hydrogen atoms and lattice H2O molecules are omitted.
kinds of cavities: triangle composed of three paddle-wheels
and hexagon composed of six paddle-wheels (Figure S2, Sup-
porting Information). The large tail OTs moieties are accom-
modated into the cavities of adjacent Kagomé lattices, and all
the cavity windows are closed by OTs groups from up and
down layers even though they are hydrophilic and filled up by
hydrogen-bonded lattice water molecules. It is interesting that
every two closest neighboring Kagomé lattices are packed with
each other in an eclipsed arrangement to form a bilayer (Figure
S3), while every two adjacent bilayers are packed with one
another in a staggered arrangement (Figure S4). The inter-layer
distance within the bilayer is about 6.868 Å, while the shortest
separation of two adjacent bilayers is about 11.394 Å. This
Kagomé lattice is comparable but distinct from a previously
reported Kagomé lattice [{Cu2(py)2(5-bo-1,3-bdc)2}3]n (5-bo-
1,3-bdc = 5-benzyloxy-1,3-benzene dicarboxylatic acid) with
similar sterically demanding ligands.[28] First, they belong to
¯
different space groups (the reported is a P3 space group). Sec-
ond, different from the hydrophobicity of benzyloxy groups in
5-bo-1,3-bdc ligand, the OTs groups in toip2– ligands show
both hydrophobicity and hydrophilicity, resulting in the encap-
sulation of several lattice water melocules in the cavities (the
reported [{Cu2(py)2(5-bo-1,3-bdc)2}3]n captures no guest mo-
lecules). Finally, the most remarkable difference is the arrange-
ment of adjacent Kagomé lattices: eclipsed for the reported,
while both eclipsed and staggered for this.
Crystal Structure of [Cu6(taip)6(py)4(dmf)2]n·n[(dmf)6-
(MeOH)2(H2O)2] (3)
Figure 6. (a) 2D structure of 2 viewed down the a axis. Cu[O5Cu] are
drawn as octahedra. (b) Schematic drawing of the Kagomé lattice. The
paddle-wheel Cu2(COO)4 SBUs are simplified as 4-connected nodes
(small gray balls).
Compound 3 crystallizes in the centrosymmetric P21/n
space group. Althouth compound 2 and 3 belong to two dif-
ferent space groups, their crystal structures are comparable. As
shown in Figure 7, the asymmetric unit of 3 is comprised of
three crystallographically unique CuII ions, three taip2– ligands,
two py ligands, one dmf ligand, and several lattice dmf,
MeOH, and water molecules. The coordination modes of taip2–
ligands are identical to those of toip2– ligands in compound 2
[Scheme 1(c)]. Cu(1) and Cu(2), two equivalent Cu(3) ions
consist of two kinds of paddle-wheel [Cu2(COO)4] SBUs,
respectively. Different from the case in 2, there are no coordi-
nated water molecules, and the axial sites of the two paddle-
[Cu2(COO)4] SBUs. Two water molecules function as axially
coordinated ligands in each paddle-wheel. The Cu–O bond
lengths vary from 1.935(3) to 2.182(3) Å (Table 2), similar to
those of some previously reported [Cu2(COO)4] paddle-
wheels.[26] The bond lengths on the axial sites are longer than
those on the equatorial positions due to the so-called “Jahn-
Teller” effect of CuII with a 3d9 electronic configuration. The
interconnection between toip2– ligands and CuII ions results in
the formation of a 2D porous Kagomé lattice on the crystallo-
graphic bc plane (Figure 6). The Kagomé lattice contains two wheels are occupied by py and dmf ligands. The coordination
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X. Li, Q. Liu
ARTICLE
between CuII ions and taip2– ligands generates a 2D porous curve shows a plateau in the temperature range of 155–290 °C.
Kagomé lattice similar to that of 2 (Figure 8). The Kagomé Upon further heating, a sharp drop in weight is observed in
lattice is also composed of trigonal and hexagonal cavities the range of 290–410 °C, which is attributed to the decomposi-
(Figure S5). However, neighboring Kagomé lattices are eclips- tion of ligands and collapse of the network. The residue contin-
edly packed with each other in the aid of interlayer hydrogen ues to loss weight slowly above 410 °C. The TGA curve of
bonds and van der Waals interactions (the separation of neigh- 3 displays one step of continuous weight loss covering the
boring layers is about 13.002 Å), which is different from the temperature range of 40–900 °C. The lattice MeOH, H2O, and
case in 2 but similar to the situation in [{Cu2(py)2(5-bo-1,3- dmf molecules are gradually lost in the range of 40–185 °C
bdc)2}3]n.[28] On the other hand, the conformation of the flexi- (theoretical value: 15.9%). Above 185 °C, the weight loss is
ble NHTs groups is also different from that of the OTs groups attributed to the release of coordinated py and dmf ligands.
in 2 (as compared from Figure S2 and Figure S5, Supporting The decomposition of the bulky ligands and collapse of the
Information).
network occur after 320 °C, where a sharp drop of weight is
observed. The residue continues to loss weight slowly. How-
ever, complete decomposition is not achieved at 900 °C for all
the three coordination polymers.
Conclusions
A tosylation strategy was employed for the modification of
5-substituted isophthalic ligands, and three structural types of
CuII-based coordination polymers 1–3 were synthesized by
variation of the reaction conditions. The structural diversity
of the complexes suggests that reaction conditions including
solvent, temperature, and auxiliary ligands significantly influ-
ence the final crystal structure of coordination polymers. This
strategy may provide enlightening ideas on the rational design
and synthesis of structurally diversified coordination polymers.
Experimental Section
Figure 8. The 2D structure of 3. Cu[O5Cu] and Cu[O4CuN] are drawn
as light gray octahedra.
Materials and Methods: All chemicals were obtained from commer-
cial sources and used without further purification. Infrared (IR) spectra
were recorded with a Perkin-Elmer Spectrum One instrument as KBr
pellets in the range of 4000–400cm–1. Elemental analyses of C, H and
N were measured with a Vario MICRO E III elemental analyzer. The
1H-NMR spectra of H2toip and H2taip ligands were recorded with a
BRUKER AVANCE III-400M NMR spectrometer in deuterated
[D6]DMSO. Thermogravimetric analyses were performed with an
NETZSCH STA 449C unit at a heating rate of 10 °C·min–1 in a nitro-
gen atmosphere.
IR Spectroscopy and Thermogravimetric Analysis
In the IR spectra of H2toip, H2taip, 1, 2, and 3 (Figure S6),
the peaks in the region 1050–1400 cm–1 are the typical stretch-
ing vibrations of sulfonate groups ν(O=S=O).[29] The peaks at
1694, 1464 cm–1 for H2toip and 1710, 1426 cm–1 for H2taip
are ascribed to the asymmetric and symmetric stretching vi-
brations of protonated –CO2H groups, respectively. As com-
pared to the free ligands, the asymmetric stretching vibrations
Synthesis of H2toip Ligand: 5-Hydroxyisophthalic acid (10.0 mmol)
and NaOH (30.0 mmol) were stirred in distilled water (13.0 mL) to
obtain a light yellow clear solution, to which TsCl (11.0 mmol) dis-
solved in THF (13.0 mL) was added dropwise. The mixture was stirred
for 18 h at room temperature, and distilled on a rotary evaporator to
remove THF. Afterwards 6 m HCl was added to a pH value of 3.0. The
white precipitate appeared was collected by vacuum filtration, washed
repeatedly by distilled water, and dried in a vacuum desiccator
equipped with allochroic silica gel. Yield 84% (based on 5-hydroxy-
isophthalic acid). C15H12O7S: calcd. C, 53.57; H, 3.60%; found: C,
53.53; H, 3.68%. IR (KBr): ν˜ = 3422 (br), 1694 (vs), 1594 (w), 1464
–
of coordinated –CO2 groups occurred at much lower wave-
numbers: 1634 (for 1), 1630 (for 2), and 1648 cm–1 (for 3).
The broad absorption bands centered at about 3430 cm–1 for
all the compounds are due to the presence of hydrogen-bonded
O–H and/or N–H groups.
The thermal stabilities of coordination polymers 1–3 were
examined by thermogravimetric analysis (TGA) in nitrogen at-
mosphere from 40–900 °C at a heating rate of 10 °C·min–1. As
shown in Figure S7, compound 1 maintains stable to about
160 °C. Further heating results in a continuous weight loss step
in the temperature range 160–410 °C, which implies decompo-
sition of the organic ligands. The residue continues to lose
weight slowly after 410 °C. The TGA curve of 2 displays two
main stages of weight losses. The weight loss from 40 to
155 °C is about 5.6%, corresponding to the release of all the
1
(w), 1389 (s), 1281 (m), 1194 (m), 1092 (w) cm–1. H NMR (deuter-
ated DMSO): δ = 8.37 (s, H4A), 7.78 (d, H10A and H14A), 7.71 (s,
H6A and H8A), 7.49 (d, H11A and H13A), 2.42 (s, H15A, H15B and
H15C) ppm (Scheme 1).
Synthesis of H2taip Ligand: Dimethyl 5-aminoisophthalate
(6.0 mmol) was stirred in py (10.0 mL), to which TsCl (6.6 mmol) was
lattice water molecules (theoretical value 5.5%). Then the added in small portions. An orange clear solution was obtained 20 min
4
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CuII Coordination Polymers Based on Tosylated Isophthalic Ligands
later. It was put on a 90 °C oil bath and stirred for another 30 min. Synthesis of [Cu6(taip)6(py)4(dmf)2]n·n[(dmf)6(MeOH)2(H2O)2] (3):
The mixture was poured into distilled water (50 mL) to obtain a light
yellow solid, which was collected by vacuum filtration, washed repeat-
edly with H2O and finally C2H5OH. H2taip was obtained by saponifi-
cation of the light yellow solid in aqueous NaOH overnight. Yield
49% (based on dimethyl 5-aminoisophthalate). C15H13NO6S: calcd. C
53.73; H 3.91; N, 4.18%; found: C 53.82; H 3.88; N, 4.11%. IR
(KBr): ν˜ = 3433 (br), 1710 (vs), 1604 (m), 1504 (w), 1426 (m), 1342
(m), 1280 (m), 1158 (s), 1090 (w) cm–1. 1H NMR (deuterated DMSO):
δ = 8.10 (s, H4A), 7.91 (s, H6A and H8A), 7.65 (d, H10A and H14A),
7.36 (d, H11A and H13A), 2.33 (s, H15A, H15B and H15C) ppm
(Scheme 1). H2taip ligand is unstable under hydrothermal and solvent
thermal conditions. The two tosylated ligands are insoluble in water,
MeOH, and EtOH at room temperature, while soluble in DMF and
DMSO.
H2taip (0.3 mmol) and py (0.1 mL) were dissolved in a mixture of
DMF (4.5 mL) and CH3OH (1 mL). It was transferred into a 25 mL
test-tube, upon which CH3OH (6 mL) was layered carefully. After-
wards Cu(NO3)2·3H2O (0.3 mmol) dissolved in CH3OH (6 mL) was
added slowly as the top layer. The mixture was left undisturbed for
slow diffusion. Several weeks later, green crystals appeared on the tube
wall and were collected by vacuum filtration, washed with small
amount of CH3OH and air-dried. Yield 61% (based on H2taip).
C136H154Cu6N18O48S6: calcd. C 48.29; H 4.59; N 7.45%; found: C
48.38; H 4.64; N 7.37%. IR (KBr): ν˜ = 3426 (br), 1648 (s), 1594 (m),
1418 (s), 1376 (s), 1162 (m), 1092 (w) cm–1.
X-ray Crystallographic Studies: Crystal structure determination of
H2toip was performed with an Oxford Xcalibur E CCD-based dif-
fractometer equipped with graphite-monochromated Mo-Kα radiation
(λ = 0.71073 Å) at room temperature. The intensity data set was col-
lected with the ω-scan technique. The CrysAlisPro (Version
1.171.34.49) software was used for data reduction and empirical ab-
sorption correction. Crystal structure determinations of 1, 2, and 3
were performed with Rigaku SCX-mini, Saturn-70 and Mercury CCD-
based diffractometers, respectively. These instruments were equipped
with graphite-monochromated Mo-Kα radiations (λ = 0.71073 Å). The
intensity data collection of 1 and 3 were conducted at room tempera-
ture, while that of 2 was performed at 150 K. Compound 3 crystals
are unstable in air, so a suitable crystal was selected and sealed in a
glass capillary with the mother liquid for data collection. The Crys-
Synthesis of [Cu(toip)(py)2]n (1): A mixture of Cu(NO3)2·3H2O
(0.3 mmol), H2toip ligand (0.3 mmol), py (0.2 mL), DMF (1.8 mL),
C2H5OH (3.0 mL), and H2O (3.0 mL) was placed in a 23 mL Teflon-
lined stainless autoclave. After 10 min of stirring, it was sealed and
heated at 120 °C for 100 h, and slowly cooled down to room tempera-
ture at a rate of 2 °C·h–1. Blue block-shaped crystals were collected by
filtration, washed with distilled water, and air-dried. Yield 52% (based
on H2toip). C25H20CuN2O7S: calcd. C 54.00; H 3.63; N 5.04%; found:
C 53.96; H 3.71; N 5.07%. IR (KBr): ν˜ = 3434 (br), 1634 (s), 1450
(m), 1358 (vs), 1180 (s), 1092 (w) cm–1.
Synthesis of [Cu6(toip)6(H2O)6]n·8n(H2O) (2):
A mixture of talClear software was used for data reduction and empirical absorption
Cu(CH3CO2)2·H2O (0.2 mmol), H2toip ligand (0.2 mmol) and 4- correction. All the four structures were solved by direct methods and
amino-3,5-dihydroxymethyl-1,2,4-triazole (0.14 mmol) was dissolved
in distilled water (9 mL) and magnetically stirred for 10 min. Then it
successive Fourier difference syntheses, and refined by full-matrix le-
ast-squares on F2 (SHELXL Version 5.1).[30] All non-hydrogen atoms
was transferred into a 23 mL Teflon-lined stainless autoclave and were refined with anisotropic displacement parameters. Hydrogen
heated at 120 °C for 80 h. Large amount of hexagonal blue crystals atoms attached to carbon atoms were generated theoretically and re-
were harvested after slowly cooling to room temperature at a rate of
fined by a riding-mode with isotropic thermal parameters fixed at 1.2-
2 °C·h–1. The crystals were collected by filtration, washed with dis- times that of the mother atoms. Hydrogen atoms bonding to water
tilled water, and air-dried. Yield 75% (based on H2toip).
C90H88Cu6O56S6: calcd. C 40.96; H 3.36%; found: C 41.02; H 3.33%.
molecules were placed on calculated positions and refined with iso-
tropic thermal parameters fixed at 1.5 times that of the oxygen atoms.
IR (KBr): ν˜ = 3434 (br), 1630 (m), 1582 (m), 1458 (w), 1376 (vs), Two OTs groups of toip2– ligands in 2 are disordered even though
1178 (m), 1093(w) cm–1. 4-Amino-3,5-dihydroxymethyl-1,2,4-triazole
did not involve in coordination to CuII, and it might play the role of
base.
the data was collected at 150 K. They were refined with the PART
instructions, and the corresponding bond lengths and anisotropic dis-
placement parameters were restrained to be approximate to a normal
Table 1. Crystallographic data for H2toip and compounds 1–3.
H2toip
1
2
3
Empirical formula
Formula weight
Crystal system
Space group
T /K
C15H12O7S
336.31
monoclinic
P21/c
C25H20CuN2O7S
556.03
monoclinic
P21/c
C90H88Cu6O56S6
2639.20
monoclinic
C2/c
C136H154Cu6N18O48S6
3382.37
monoclinic
P21/n
293(2)
293(2)
150(2)
293(2)
a /Å
b /Å
c /Å
13.6672(12)
16.5709(13)
6.9452(6)
103.318(10)
1530.6(2)
4
9.7802(14)
30.103(3)
8.9867(14)
113.715(7)
2422.4(6)
4
36.797(5)
18.299(3)
32.135(5)
99.948(3)
21313(6)
8
18.2505(9)
19.0852(7)
23.3236(11)
101.2170(10)
7968.8(6)
2
β /°
V /Å3
Z
Dc /g·cm–3
1.459
0.246
1.525
1.037
1.645
1.396
1.410
0.950
μ /mm–1
θ range /°
Rint
2.46–26.50
0.0334
2.27–27.48
0.0622
2.02–27.50
0.0477
2.08–27.48
0.0519
Data /parameters
GOF on F2
R1, wR2 [I Ͼ 2σ(I)]a)
3171 / 209
1.002
0.0630, 0.1371
0.363 / –0.317
5494 / 326
1.052
0.0595, 0.1668
1.154 / –1.793
24243 / 1552
1.018
0.0631, 0.1579
1.730 / –1.440
18137 / 927
1.007
0.0700, 0.1714
0.893 / –1.339
Δρmin
/
/e·Å–3
max
2
2 2
2 2 1/2
a) R = ∑||Fo|–|Fc||)/∑|Fo|, wR = [∑w(Fo –Fc ) /∑w(Fo ) ]
.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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5

Job/Unit: Z13195
/KAP1
Date: 11-06-13 17:43:11
Pages: 7
X. Li, Q. Liu
ARTICLE
Table 2. Selected bond lengths /Å and angles /° in H2toip and com-
pounds 1–3.
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H2toip
O(1)–C(1)
O(3)–C(2)
1.270(4)
1.274(4)
O(2)–C(1)
O(4)–C(2)
1.245(4)
1.238(4)
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1
Cu(1)–O(1)
Cu(1)–N(2)
1.965(3)
2.023(4)
2.238(4)
90.41(16)
Cu(1)–O(3)#1
Cu(1)–N(1)
O(1)–Cu(1)–N(1)
O(3)#1–Cu(1)–N(1) 88.43(16)
O(1)–Cu(1)–O(2)#2 107.21(16)
N(1)–Cu(1)–O(2)#2 90.47(16)
1.995(3)
2.032(4)
86.60(16)
Cu(1)–O(2)#2
O(1)–Cu(1)–N(2)
O(3)#1–Cu(1)–N(2) 92.08(16)
O(3)#1–Cu(1)–O(2) 90.85(15)
#2
N(2)–Cu(1)–O(2)#2 97.53(17)
2
Cu(1)–O(31)#1
Cu(1)–O(1)
Cu(1)–O(43)
Cu(2)–O(2)
1.950(3)
1.989(3)
2.163(3)
1.956(3)
1.988(3)
1.944(3)
1.966(3)
2.178(3)
1.961(3)
1.969(3)
1.954(3)
1.976(3)
2.182(3)
1.961(3)
1.989(3)
Cu(1)–O(8)
1.961(3)
1.990(3)
1.935(3)
1.972(3)
2.124(3)
1.949(3)
1.974(3)
1.960(3)
1.961(3)
2.154(4)
1.957(3)
1.992(3)
1.951(3)
1.968(3)
2.155(3)
Cu(1)–O(15)
Cu(2)–O(16)
Cu(2)–O(9)
Cu(2)–O(32)#1
Cu(3)–O(17)#2
Cu(3)–O(23)
Cu(3)–O(45)
Cu(4)–O(22)
Cu(4)–O(3)#3
Cu(5)–O(11)
Cu(5)–O(39)
Cu(5)–O(47)
Cu(6)–O(38)
Cu(6)–O(10)
Cu(2)–O(44)
Cu(3)–O(37)#2
Cu(3)–O(4)#3
Cu(4)–O(36)#2
Cu(4)–O(18)#2
Cu(4)–O(46)
Cu(5)–O(25)
Cu(5)–O(30)
Cu(6)–O(29)
Cu(6)–O(24)
Cu(6)–O(48)
3
Cu(1)–O(13)
Cu(1)–O(10)#1
Cu(1)–O(19)
Cu(2)–O(9)#1
Cu(2)–O(14)
Cu(3)–O(3)#2
Cu(3)–O(4)#1
Cu(3)–N(5)
1.951(3)
1.984(3)
2.157(4)
1.975(3)
1.993(3)
1.959(3)
1.970(3)
2.168(3)
Cu(1)–O(1)
Cu(1)–O(7)
Cu(2)–O(8)
Cu(2)–O(2)
Cu(2)–N(4)
Cu(3)–O(15)#3
Cu(3)–O(16)
1.952(3)
1.985(3)
1.964(3)
1.985(3)
2.144(4)
1.966(3)
1.978(3)
Symmetry codes for: 1 (#1) x+1, y, z+1. (#2) –x+1, –y, –z. 2 (#1)
x, –y+1, z–1/2. (#2) x, –y, z+1/2. (#3) x, –y+1, z+1/2. 3 (#1) –x+1/2,
y+1/2, –z+1/2. (#2) x–1/2, –y+1/2, z+1/2. (#3) –x, –y+1, –z+1.
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11042.
OTs group with the help of SADI, DELU and SIMU instructions.
Some lattice water molecules in 2 are also disordered. Detailed crystal-
lographic data and structure refinement parameters of H2toip and 1–3
are summarized in Table 1. Selected bond lengths and angles are listed
in Table 2.
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Supporting Information (see footnote on the first page of this article):
Additional Figures S1–S7 and Table S1 are available in the online
version.
2004, 2534.
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Göttingen: Germany, 1997.
Acknowledgements
This work was supported by the Science and Technology Department
of Guizhou Province (J-LKZS[2012]29), Zunyi Science and Technol-
ogy Bureau ([2010]04) and Initial Fund for Ph. D from Zunyi Normal
College.
Received: April 6, 2013
Published Online: ᭿
6
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Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z13195
/KAP1
Date: 11-06-13 17:43:11
Pages: 7
CuII Coordination Polymers Based on Tosylated Isophthalic Ligands
X. Li,* Q. Liu .................................................................... 1–8
Structural Diversity of Copper(II) Coordination Polymers
Based on Tosylated Isophthalic Ligands
Z. Anorg. Allg. Chem. 0000, 0–0
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