Sulfonic acid analogs of terephthalic and trimesic acid as linkers in metal-organic frameworks - synthesis of thermally robust MOFs

Article abstract of DOI:10.1002/ejic.200900914

p-Benzenedisulfonic acid and 1,3,5-benzenetrisulfonic acid are prepared in an efficient and scalable two-step protocol from, respective bromobenzene derivatives. These acids are used in analogy to terephthalic and trimesic acid for the formation of metal-

Full text of DOI:10.1002/ejic.200900914

FULL PAPER
DOI: 10.1002/ejic.200900914
Sulfonic Acid Analogs of Terephthalic and Trimesic Acid as Linkers in
Metal-Organic Frameworks – Synthesis of Thermally Robust MOFs
Andrea Mietrach,[a] Thomas W. T. Muesmann,[a] Jens Christoffers,*[a] and
Mathias S. Wickleder*[a]
Keywords: Aromatic substitution / Copper / Metal-organic frameworks / Sulfonic acids / Thermal analysis
p-Benzenedisulfonic acid and 1,3,5-benzenetrisulfonic acid
are prepared in an efficient and scalable two-step protocol
from respective bromobenzene derivatives. These acids are
used in analogy to terephthalic and trimesic acid for the for-
mation of metal-organic frameworks with copper(II) centers.
Due to the enhanced acidity of sulfonic acids, weakly basic
malachite can be used as inorganic precursor material. After
dehydration at about 100 °C, the anhydrous frameworks ex-
hibit significantly increased thermal stability (up to 400 °C)
relative to the commonly known carboxylate MOFs.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
Introduction
Metal-organic frameworks (MOF)[1] are porous materi-
als, which lately attracted attention because of their poten-
tial applicability as catalysts or media for gas storage, in
particular hydrogen.[2] Either neutral molecules or anions of
di-, tri- or oligocarboxylic acids are used as organic linkers
between the knots (metal ions or metal-oxo clusters). The
variety of available carboxylic acids leads to a large number
of known frameworks with tunable properties. One example
is the well known and so far most investigated MOF-5,
which consists of [Zn4O] clusters as knots linked by di-
anions of terephthalic acid (1) (Figure 1).[3] Furthermore,
the trianion of benzenetricarboxylic acid (2) plays an im-
portant role in the field of MOFs.[4] Many present and fu-
ture applications of MOFs, in particular their use as hydro-
gen storage devices, require thermally stable frameworks.
Thus, heat of sorption, which is produced during the charg-
ing of the materials, must not lead to a damage of the skel-
eton, and thermal processing of the compounds needs to
be possible. The low stability of carboxylates towards heat
is a significant disadvantage in this context, because it limits
their applicability as linkers. For example, copper(II)
terephthalate decomposes between 160 and 200 °C with for-
mation of carbon dioxide.[5]
Figure 1. Carboxylic and sulfonic acids as linkers for metal-organic
frameworks.
have shown that these materials are stable up to 400 °C;[6]
structural investigations on such compounds have, however,
not been made so far. Di- and trisulfonates as linkers in
MOFs have so far rarely been reported.[7] This might be due
to the lack of availability of sulfonic acids with substitution
patterns similar to the carboxylic acids used in MOFs.
While m-disulfonic acid 3 is commercially available as its
sodium salt, no efficient and scalable procedures exist for
the preparation of p-disulfonic acid 4 or 1,3,5-trisulfonic
acid 5.
In the present work, we have developed a convenient pre-
parative route for the synthesis of di- and trisulfonic acids
for the use instead of the analogous carboxylates in the
preparation of more stable MOFs. Investigations on the
thermal stability of salts from m-benzenedisulfonic acid (3)
Results and Discussion
Preparation of Sulfonic Acids
The synthesis of organic oligosulfonic acids is limited by
the regioselectivity as well as the deactivating nature of
sulfo groups. Therefore, we have decided to oxidize dithiol
7 in order to prepare 1,4-disulfonic acid 4, the sulfo analog
of terephthalic acid (1). As the purification of reaction
product 4 turned out to be very tedious, the use of hydrogen
[a] Institut für Reine und Angewandte Chemie, Carl von Ossietzky-
Universität Oldenburg,
26111 Oldenburg, Germany
Fax: +49-441-798-3873
E-mail: jens.christoffers@uni-oldenburg.de
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Synthesis of Thermally Robust Metal-Organic Frameworks
Scheme 1. Synthesis of sulfonic acids p-BDSH2 (4) and BTSH3 (5).
peroxide in a mixture of water and methanol was beneficial the crystal structure of I the Cu2+ ions are Jahn–Teller dis-
for the oxidation of dithiol 7. All other components of the torted and coordinated by six oxygen atoms (Figure 2).
reaction mixture could be removed in high vacuum after These belong to five molecules of water and one 1,3-
full conversion was achieved, and disulfonic acid 4 as the benzenedisulfonic acid molecule. Four water molecules oc-
only nonvolatile material was obtained in high purity cupy the equatorial sites, whereas the sulfonate oxygen
(Scheme 1). Trisulfonic acid 5 was prepared from trithiol 9 atom and one water molecule coordinate axially. Linkage
in the same manner. Dithiol 7[8] and trithiol 9[9] have been to a 3D network occurs through hydrogen bonds (Figure 3).
prepared before by multi-step procedures, which are not
suitable for up-scaling. We herein report on a sequential
one-pot protocol for the synthesis of both intermediates 7
and 9 from bromobenzenes 6 and 8. First, a nucleophilic
aromatic substitution with iPrSNa takes place in dimethyl-
acetamide (DMA) with formation of the dithioether and
trithioether, respectively. Subsequently, an excess of sodium
is added to the reaction mixture and the isopropyl groups
are reductively cleaved. Acidic workup afforded the prod-
ucts 7 and 9 in good yields.
Copper m-Disulfonate
Our first study on a framework structure was ac-
complished by conversion of m-benzenedisulfonic acid (3,
m-BDSH2) (prepared from its commercially available so-
dium salt) with basic copper carbonate Cu2(OH)2(CO3)
(malachite) in aqueous solution. The copper salts crys-
tallized as the hexahydrate [Cu(m-BDS)(H2O)5]·H2O (I). In
Figure 3. Projection of the crystal structure of [Cu(m-BDS)-
(H2O)5]·H2O (I) onto the (100) plane. Hydrogen bonds are repre-
sented by dashed lines.
Copper p-Disulfonate
A direct link between the copper(II) ions is achieved, if
the two sulfo groups are in p-positions. Blue single crystals
of [Cu(p-BDS)(H2O)4] (II) are obtained by conversion of
1,4-benzenedisulfonic acid 4 (p-BDSH2) with Cu2(OH)2-
(CO3) in aqueous solution. The crystal structure shows dis-
torted octahedral coordination (Jahn–Teller effect) of Cu2+
ions by four molecules of H2O and two benzenedisulfonate
ions. The linear organic linker connects the Cu2+ ions to
form a chain by monodentate ligation of both sulfo func-
tions. These chains form a 3D network by hydrogen bond-
Figure 2. Typically distorted Cu2+ polyhedron shown for [Cu-
(m-BDS)(H2O)5]·H2O (I).
ing, which involves the free donor atoms of the sulfo groups
(see Figures 4 and 5).
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A. Mietrach, T. W. T. Muesmann, J. Christoffers, M. S. Wickleder
FULL PAPER
Figure 4. Connection of Cu2+ ions to form chains and formation of the network of [Cu(p-BDS)(H2O)4] (II) by hydrogen bonds (dashed
lines) of the 1,4-benzene disulfonate linker.
cated. The network is formed by hydrogen bonding between
the layers. The noncoordinated water molecules are also in-
volved in these hydrogen bonds.
Figure 5. Projection of the crystal structure of [Cu(p-BDS)(H2O)4]
(II) onto the (001) plane which shows the linkage of the chains to
a 3D network through hydrogen bonds.
Copper Trisulfonate
Figure 6. View onto a single layer of compound (III). Rotation
Following the protocols for the synthesis of compounds (60°) and superposition of these layers generates the complete
I and II, [Cu3(BTS)2(H2O)12]·6H2O (III) was prepared by
structure.
conversion of benzenetrisulfonic acid (5) (BTSH3) with
Cu2(OH)2(CO3) in aqueous solution. Similar to the pre-
vious example, Cu2+ ions are coordinated by four molecules
of water and two benzene trisulfonate ligands. The third
Thermal Analyses
sulfo function enlarges the coordination capacity and en-
The thermal decomposition of [Cu(m-BDS)(H2O)5]·H2O
ables the linker to bind to two additional Cu2+ ions with (I), [Cu(p-BDS)(H2O)4] (II) and [Cu3(BTS)2(H2O)12]·6H2O
formation of 2D layers (Figure 6 and 7). Superposition of (III) has been studied by TG and DTA techniques under
the layers forms a network with channels along the a axis nitrogen flow. The degradation products of the anhydrous
(Figure 8), in which noncoordinated water molecules are lo- salts were identified by X-ray diffraction. The decomposi-
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Synthesis of Thermally Robust Metal-Organic Frameworks
culated values, the number of water molecules lost in each
case, and the temperature ranges are shown in Table 1.
The dehydration process of [Cu(m-BDS)(H2O)5]·H2O (I)
takes place in three successive steps corresponding to the
loss of two water molecules in each step. The dehydrated
salt is stable in a long temperature interval up to 340 °C
and decomposes in the 340–420 °C temperature range with
one endothermic effect shown in the DTA curve centered
at 375 °C (Figure 9).
Figure 7. Projection of [Cu3(BTS)2(H2O)12]·6H2O (III) onto the
(100)-plane.
Figure 9. Thermal analysis of [Cu(m-BDS)(H2O)5]·H2O (I).
The curves (TG and DTA) for [Cu(p-BDS)(H2O)4] (II)
show two thermogravimetric nondistinguishable steps cor-
responding to the loss of water starting at 120 °C. The ob-
served mass loss is consistent with the calculation for four
equivalents of H2O (Figure 10). The anhydrous framework
itself is stable. Its decomposition does not start below
400 °C and reaches a maximum at 430 °C. This value is
about 200 K above the temperature observed for copper(II)
terephthalate.[5]
For [Cu3(BTS)2(H2O)12]·6H2O (III) the dehydration pro-
cess takes place in three successive steps (Figure 11). The
first corresponds to the elimination of six solvent water
molecules (presumably the noncoordinated ones in the
Figure 8. Space-filling representation of compound III, showing
the open channels that permeate the solid down the a axis (solvent
molecules are omitted).
tion of all samples occurs by two processes. The first stage channels along the a axis), the second and third to the loss
is the dehydration of the compounds to their anhydrous of the twelve remaining water molecules. The anhydrous de-
forms, the second is the decomposition of these anhydrous hydrated framework itself is again stable up to 440 °C. The
compounds to a mixture of carbon and copper metal. The thermal decomposition of the framework proceeds above
weight losses found during dehydration, as well as the cal- 440 °C.
Table 1. Data for thermal degradation.
Compound
Stage
Tonset [°C]
Tend [°C]
Tmax [°C]
Mass loss
obsd.
Mass loss
calcd.
[Cu(m-BDS)(H2O)5]·H2O (I)
1. loss of six equiv. of H2O 70
210
420
90; 120; 155 25.7%
26.5%
–
2. decomposition to Cu
340
375
64.9%
(calcd. 15.6%) and C
1. loss of four equiv. of H2O 120
2. decomposition to Cu
(calcd. 17.1%) and C
[Cu(p-BDS)(H2O)4] (II)
180
480
145; 170
450
19.4%
67.3%
19.4%
–
400
100; 125;
180
455
[Cu3(BTS)2(H2O)12]·6H2O (III)
1. loss of 18 equiv. of H2O
65
210
470
24.6%
73.8%
28.9%
2. decomposition to Cu
(calcd. 17.0%) and C
440
–
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A. Mietrach, T. W. T. Muesmann, J. Christoffers, M. S. Wickleder
FULL PAPER
Experimental Section
General Methods: Preparative column chromatography was carried
out using Merck SiO2 (0.035–0.070 mm, type 60 A) with hexane
and tert-butyl methyl ether (MTBE) as eluents. TLC was per-
formed with Merck SiO2 F254 plates on aluminum sheets. All start-
ing materials were commercially available and were used without
1
further purification. H and 13C NMR spectra were recorded with
a Bruker Avance DRX 500 and Avance DPX 300. Multiplicities
were determined with DEPT experiments. EI-MS and HRMS spec-
tra were obtained with a Finnigan MAT 95 spectrometer, ESI-MS
(HRMS) spectra with a Waters Q-TOF Premier. A Thermo system
equipped with AS 3000 autosampler and Finnigan MAT ESI-MS
was used for LCMS. IR spectra were recorded with a Bruker Ten-
sor 27 spectrometer equipped with a “GoldenGate” diamond ATR
unit. Elemental analyses were measured with a Euro EA-CHNS
from HEKAtech. Thermal analyses (TG and DTA) were per-
formed with a Mettler-Toledo SDTA 851e. Data for X-ray single
crystal structure determination were collected on a Bruker Apex II
CCD diffractometer at 153(2) K with Mo-Kα radiation (graphite
monochromator, λ = 71.07 pm). The structure was solved by direct
methods and refined by full-matrix least-squares methods with
SHELXL.
Figure 10. Thermal analysis of [Cu(p-BDS)(H2O)4] (II).
CCDC-738980 (for I), -738979 (for II) and -738978 (for III) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
1,4-Dimercaptobenzene (7): 1,4-Dibromobenzene (6) (2.4 g,
10 mmol, 1.0 equiv.) and NaSiPr (4.7 g, 50 mmol, 5.0 equiv.) were
suspended under an inert atmosphere (N2) in dimethylacetamide
(DMA) (30 mL) and the mixture was heated for 12 h to 100 °C.
Subsequently, Na (1.6 g, 70 mmol, 7.0 equiv.) was added under vig-
orous stirring. In order to prevent foaming, more DMA (up to
5 mL) could be added. The resulting suspension was stirred for
16 h at 100 °C. If the conversion was incomplete (monitored by
GLC), more Na (up to 1.6 g, 70 mmol, 7.0 equiv.) and (if neces-
sary) DMA could be added and the mixture further stirred for 4–
16 h at 100 °C. The mixture was carefully diluted with H2O
(250 mL) and tert-butyl methyl ether (MTBE) (150 mL) and acidi-
fied with concd. hydrochloric acid (pH Ͻ 1). The layers were sepa-
rated and the aqueous layer extracted with MTBE (2ϫ75 mL). The
combined organic layers were washed twice with H2O (2ϫ100 mL)
and dried (MgSO4). After filtration, the solvent was evaporated
and the crude product chromatographed twice [SiO2, first with
MTBE, then with hexane/MTBE, 5:1, Rf(hexane/MTBE, 10:1) =
0.20] to yield the title compound (1.3 g, 9.0 mmol, 90%) as a light
yellow solid, m.p. 87 °C. 1H NMR (300 MHz, CDCl3): δ = 3.41 (s,
2 H, S-H), 7.16 (s, 4 H, 1-H) ppm. 13C{1H} NMR (75 MHz,
CDCl3): δ = 127.94 (C-2), 130.36 (C-1) ppm. MS (EI, 70 eV): m/z
(%) = 142 (100) [M+], 109 (24), 97 (25), 78 (58), 69 (25). IR (ATR):
Figure 11. Thermal analysis of [Cu3(BTS)2(H2O)12]·6H2O (III).
Conclusions
A new route for synthesis of di- and trisulfonic acids was
developed. 1,4-Benzenedisulfonate and 1,3,5-benzenetrisul-
fonate can be used as linkers for metal-organic frameworks.
Their use in networks with copper(II) centers leads to a
significant improvement of the thermal stability (with more
than 400 °C) of the framework. Moreover, sulfonic acids
exhibit clearly increased acidity (pKa ≈ 0.7) compared to
the usually applied carboxylic acids (pKa ≈ 4.2). On the one
hand, this feature overcomes synthetic limitations, since
now weakly basic metal oxides or carbonates can be used
as inorganic precursor compounds. On the other hand,
chemical properties of the resulting frameworks could be
different. MOFs with sulfonate linker units define therefore
a new class of materials with unique and interesting proper-
ties. The significantly increased thermal stability is para-
mount. A condition for these new and promising materials
is, however, the availability of sulfonic acids with suitable
substitution patterns. The new two-step protocol for di- and
trisulfonic acid synthesis from bromobenzene derivatives is
a significant advance toward fulfilling this requirement. We
will report on further sulfonic acid syntheses as well as
novel framework structures derived from them in due
course.
ν = 3443 (w), 3069 (w), 2560 (m), 1899 (w), 1646 (w), 1477 (s),
˜
1397 (m), 1263 (w), 1114 (s), 1013 (m), 906 (s), 812 (vs), 731 (s),
650 (w) cm–1. C6H6S2 (142.24 g/mol).
1,4-Benzenedisulfonic Acid Dihydrate (p-BDSH2·2H2O) (4): Di-
thiole 7 (1.3 g, 9.0 mmol, 1.0 equiv.) was dissolved with gentle
warming in MeOH (18 mL) and H2O2 (30% in H2O, 15.0 mL,
161 mmol, 17.7 equiv.) was added. The suspension was stirred for
16 h at 23 °C. Subsequently, all volatile materials were removed in
high vacuum to yield the title compound (2.3 g, 8.4 mmol, 93%)
as a colorless solid, mp. 83–84 °C. Thermal analysis (TG and DTA)
showed this material to be the dihydrate, which is further confirmed
by
a
single crystal structure analysis. 1H NMR (CD3OD,
500 MHz): δ = 5.44 (6 H, HDO), 7.90 (s, 4 H, 1-H) ppm. 13C{1H}
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Synthesis of Thermally Robust Metal-Organic Frameworks
NMR (CD3OD, 125 MHz): δ = 127.04 (C-2), 147.92 (C-1) ppm.
Phase purity of the bulk material was proved by XRD at 23 °C.
Lattice parameters were refined from the observed reflections as
follows: a = 634.2(4) pm, b = 2020.2(12) pm, c = 1129.1(6) pm, β
= 99.20°(4), V = 1427.9(14) Å3.
LC-MS (ESI, negative mode): m/z = 237 [M – H+]. IR (ATR): ν =
˜
3512–1504 [br, vs, ν(OH)], 3096 (w), 2561 (m), 2170 (m), 1809 (m),
1636 (m), 1395 (m), 1088 (vs), 1031 (vs), 990 (vs), 832 (s), 649 (vs)
cm–1. C6H10S2O8 (274.26 g/mol).
Copper(II) (1,4-Benzenedisulfonate) Tetrahydrate [Cu(p-BDS)-
(H2O)4] (II): A solution of Cu2(OH)2(CO3) (40 mg) and 1,4-
benzenedisulfonic acid (0.1 g) in 5 mL water was heated at 50 °C
whilst stirring for one day. If the reaction was incomplete (pH Ͻ
5), more Cu2(OH)2(CO3) was added. The resulting solution was
filtered. After a few days in air at room temperature in a small petri
dish blue crystals were obtained from the blue solution.
1,3,5-Trimercaptobenzene (9): 1,3,5-Tribromobenzene (8) (3.2 g,
10 mmol, 1.0 equiv.) and NaSiPr (7.4 g, 75 mmol, 7.5 equiv.) were
suspended under an inert atmosphere (N2) in DMA (35 mL) and
the mixture was heated for 12 h to 100 °C. Subsequently, Na (2.3 g,
100 mmol, 10 equiv.) was added under vigorous stirring. In order
to prevent foaming, more DMA (up to 5 mL) could be added and
the suspension was stirred for 16 h at 100 °C. More Na (2.3 g,
100 mmol, 10 equiv.) and (if necessary) DMA were added and the
mixture was further stirred for 16 h at 100 °C. If the conversion was
incomplete (monitored by GLC), more Na (up to 1.1 g, 50 mmol,
5.0 equiv.) and DMA (10 mL) were added and the mixture stirred
for 4–16 h at 100 °C. The mixture was then carefully diluted with
H2O (250 mL) and MTBE (150 mL) and acidified with concd. hy-
drochloric acid (pH Ͻ 1). The layers were separated and the aque-
ous layer extracted with MTBE (2ϫ75 mL). The combined organic
layers were washed with H2O (2ϫ100 mL) and dried (MgSO4).
After filtration, the solvent was evaporated and the crude product
chromatographed twice [SiO2, first with MTBE, then with hexane/
MTBE 5,:1, Rf(hexane/MTBE 10:1) = 0.35] to yield the title com-
pound (1.3 g, 7.5 mmol, 75%) as a light yellow solid, mp. 57 °C.
1H NMR (300 MHz, CDCl3): δ = 3.41 (s, 3 H), 7.16 (s, 3 H) ppm.
13C{1H} NMR (75 MHz, CDCl3): δ = 126.33 (CH), 132.98 (C)
ppm. HR-MS (EI, 70 eV), calcd. for C6H6S3: 173.9631; found
Crystal Data for [Cu(p-BDS)(H2O)4] (II): 371.82 g/mol, crystal size:
0.312ϫ0.072ϫ0.0674 mm3, monoclinic, P21/n, a = 597.51(2) pm,
b = 1093.60(3) pm, c = 992.16(3) pm, β = 105.165°(2), V =
625.74(3) Å3, Z = 2, 1.973 g/cm3, µ = 21.24 cm–1, 7.24° Ͻ 2θ Ͻ
65.1°, 11842 measured reflections, 2267 independent, Rint = 0.0339,
R1 = 0.0237, wR2 = 0.0583, max./min. residual electron density:
0.462/–0.351.
Phase purity of the bulk material was proved by XRD at 23 °C.
Lattice parameters were refined from the observed reflections as
follows: a = 598.8(3) pm, b = 1092.0(8) pm, c = 1000.0(5) pm, β =
105.12°(4), V = 631.3(3) Å3.
Tricopper(II) Bis(1,3,5-benzenetrisulfonate) Octadecahydrate [Cu3-
(BTS)2(H2O)12]·6 H2O (III): To an aqueous solution of 1,3,5-ben-
zenetrisulfonic acid (0.1 g in 10 mL water) Cu2(OH)2(CO3)
(45.5 mg) was added under vigorous stirring. The reaction mixture
was heated to 50 °C for one day. If the reaction was incomplete
(pH Ͻ 5), more Cu2(OH)2(CO3) was added. the blue solution was
allowed to crystallize in air at room temperature. Blue plate-shaped
crystals were obtained after a few days.
173.9632 [M+]. IR (ATR): ν = 3461 (m), 2559 (s), 2533 (s), 1552
˜
(vs), 1409 (s), 1370 (m), 1348 (m), 1293 (w), 1113 (s), 911 (m), 825
(s), 798 (s), 666 (s) cm–1. C6H6S3 (174.31 g/mol).
1,3,5-Benzenetrisulfonic Acid Trihydrate (BTSH3·3H2O) (5): Tri-
thiole 9 (1.3 g, 7.2 mmol, 1.0 equiv.) was dissolved with gentle
warming in MeOH (15 mL) and H2O2 (30% in H2O, 16.0 mL,
155 mmol, 21.5 equiv.) was added. The suspension was stirred for
16 h at 23 °C. Subsequently, all volatile materials were removed in
high vacuum to yield the title compound (2.5 g, 6.8 mmol, 95%)
as a colorless solid, mp. 123–124 °C. Thermal analysis (TG and
DTA) showed this material to be the trihydrate. 1H NMR (CD3OD,
500 MHz): δ = 5.52 (9 H, HDO), 8.35 (s, 3 H, 2-H) ppm. 13C{1H}
NMR (CD3OD, 125 MHz): δ = 126.15 (CH), 146.92 (C) ppm. LC-
MS (ESI, negative mode): m/z = 317 [M – H+]. C6H12S3O12 (trih-
ydrate, 372.35 g/mol).
Crystal Data for [Cu3(BTS)2(H2O)12]·6 H2O (III): 1145.44 g/mol,
crystal size: 0.313ϫ0.204ϫ0.089 mm , triclinic, P1, a = 815.45(4)
3
¯
pm, b = 1146.06(9) pm, c = 1146.97(6) pm, α = 114.593°(3), β =
102.453°(2), γ = 103.841°(3), V = 884.00(9) Å3, Z = 1, 1.973 g/cm3,
µ = 22.70 cm–1, 7.00° Ͻ 2θ Ͻ 72.26°, 31444 measured reflections,
8322 independent, Rint = 0.0355, R1 = 0.0877, wR2 = 0.1612, max./
min. residual electron density: 1.313/–1.579.
Phase purity of the bulk material was proved by XRD at 23 °C.
Lattice parameters were refined from the observed reflections as
follows: a = 817.7(2) pm, b = 1151.8(4) pm, c = 1150.9(5) pm, α =
114.59°(6), β = 103.51°(7), γ = 103.69°(3), V = 887.4(8) Å3.
Copper(II) (1,3-Benzenedisulfonate) Hexahydrate [Cu(m-BDS)-
(H2O)5]·H2O (I): Commercially available disodium m-benzenedis-
ulfonate Na2(m-BDS) was converted into the acid by ion exchange
and the content of the aqueous solution was determined by ti-
tration with aqueous NaOH solution. [Cu(m-BDS)(H2O)5]·H2O (I)
was obtained by adding Cu2(OH)2(CO3) to an equimolar solution
of 1,3-benzenedisulfonic acid in water at ambient temperature. The
reaction mixture was stirred for 24 h at 50 °C and the pH-value
was checked. If the reaction was incomplete (pH Ͻ 5), more
Cu2(OH)2(CO3) was added. After filtration the blue solution was
allowed to crystallize in air at room temperature. Blue, needle-
shaped crystals were obtained after a few days.
Acknowledgments
We are grateful to Christina Zitzer and Willi Rathje for initial ex-
periments on this project and to Wolfgang Saak and Detlev Haase
for help with the single-crystal X-ray analysis.
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Crystal Data for [Cu(m-BDS)(H2O)5]·H2O (I): Mr = 407.85 g/mol,
crystal size: 0.4ϫ0.24ϫ0.18 mm3, monoclinic, P21/n, a = 632.05(4)
pm, b = 2022.64(12) pm, c = 1128.30(8) pm, β = 99.263°(8), V =
1423.6(2) Å3, Z = 4, 1.903 g/cm3, µ = 18.86 cm–1, 5.44° Ͻ 2θ Ͻ
5.18°, 13546 measured reflections, 2807 independent, Rint = 0.0375,
R1 = 0.0238, wR2 = 0.0530, max./min. residual electron density:
0.411/–0.448.
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A. Mietrach, T. W. T. Muesmann, J. Christoffers, M. S. Wickleder
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Received: September 14, 2009
Published Online: October 29, 2009
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2009, 5328–5334