Unprecedented sulfone-functionalized metal-organic frameworks and gas-sorption properties

Article abstract of DOI:10.1002/chem.200900341

A study was conducted to demonstrate significant sulfone-functionalized metal-organic frameworks (MOF) and gas sorption properties. The ligand (1,1'-biphenyl)-4,4'-dicarboxylic acid was functionalized with -SO₃H groups and used as a linker to construct coordination polymers and conduct the investigations. The sulfone (-SO₂) derivative of (1,1'-biphenyl)-4, 4'-dicarboxylic acid was isolated to conduct the investigations. The investigations revealed two novel three dimensional (3D) non-isoreticular porous MOFs with specific structures. The MOFs were isolated from controlled solvothermal reactions between (1,1'-biphenyl)-4,4'-dicarboxylic acid and Zn(NO₃)₂·6H₂O. The unique structures of the MOFs were demonstrated as UoC-1 and UoC-2 that included the formation of novel inorganic secondary building units (SBUs) with significant double organic bridging connectivity in all directions.

Full text of DOI:10.1002/chem.200900341

COMMUNICATION
DOI: 10.1002/chem.200900341
Unprecedented Sulfone-Functionalized Metal–Organic Frameworks and
Gas-Sorption Properties
[
a]
[b]
[a]
Eleftheria Neofotistou, Christos D. Malliakas, and Pantelis N. Trikalitis*
Porous, metal–organic frameworks (MOFs) or coordina-
tion polymers (PCPs) represent a unique class of crystalline
open framework solids with unprecedented structures, di-
verse chemical composition, adjustable pores sizes, large sur-
face areas and pore volumes. These hybrid porous materi-
als result from molecular self-assembly reactions between
metal ions or clusters and bridging multidentade organic lig-
atoms of the ligands towards metal atoms. In some cases,
these problems could be avoided by using tagged frame-
works with non-reactive groups which then can be converted
[8]
to the desired active functional groups.
[1]
We are interested in the development of MOFs with free
À
Lewis base sites and in particular with sulfonate (-SO )
3
groups. In contrast to a number of MOFs with Lewis acid
sites originating from unsaturated metal sites upon solvent
removal, free Lewis base functionalized MOFs are rarely
observed because of the coordination affinity of these
groups towards metal atoms. It is expected that basic porous
surfaces will reveal significant gas sorption and catalytic
properties based on acid–base interactions. Recently, Kita-
gawa and co-workers reported a robust porous coordination
ACHTUNGTRENNUNGa nds, usually performed under hydro ACHTNUGTRENNU(GN solvo)thermal condi-
tions. The combination of accessible porosity and framework
functionalities in these solids, arising from both the inorgan-
ic and organic component, results in unique properties that
could lead to applications in technologically important fields
[2]
[3]
[4]
including gas storage, separation and catalysis.
The availability of a large number of different organic
linkers as building blocks not only offers the potential for
the construction of structurally and topologically diverse
MOFs but also the opportunity to create functionalized
porous frameworks with the functional species (atoms or
groups) being exposed inside the pore space. This could lead
to tailor-made materials for specific applications. For exam-
ple, porous MOFs with metal-free organic groups such as
amines are currently explored for applications in base-cata-
À
polymer, with free -SO3 Lewis base groups, which shows in-
[9]
teresting sorption properties for CO and MeOH.
2
We chose to functionalize the ligand (1,1’-biphenyl)-4,4’-
dicarboxylic acid (H L1) (see Scheme 1) with -SO H groups
2
3
and use it as a linker to construct coordination polymers.
However, using the powerful sulfonating agent fuming sulfu-
ric acid, (oleum: H SO , 20% SO ) we isolated not the sul-
2
4
3
fonated product of H L1 but its sulfone (-SO ) derivative,
2
2
[
5]
lyzed reactions and as sorbents for selective CO capture
namely the ligand 4,4’-bibenzoic acid-2,2’-sulfone (H L2)
2
2
[6]
[10]
and storage. However, post-synthetic functionalization of
MOFs is not straightforward because of the limited stability
of the framework during the post-modification reaction.
(see Scheme 1). This ligand has never been used before in
the entire family of MOFs or PCPs and represents a new,
rigid carboxylate-based linker, in contrast to its flexible
[7]
Alternatively, the direct synthesis of MOFs using functional-
ized organic ligands is limited either by the relative stability
of the functional groups under the specific reaction condi-
tions or by the competition of these groups with the donor
parent H L1. The sulfone group has locked the two phenyl
2
rings and it was expected that H L2 would lead to the for-
2
mation of new functionalized isoreticular MOFs when react-
2
+
ed, for example, with Zn under solvothermal conditions in
dimethylformamide (DMF) or diethylformamide (DEF).
[
a] E. Neofotistou, Prof. Dr. P. N. Trikalitis
Department of Chemistry, University of Crete, Voutes
7
1003 Heraklion (Greece)
Fax : (+30)2810-545001
E-mail: ptrikal@chemistry.uoc.gr
[
b] Dr. C. D. Malliakas
Department of Chemistry, Northwestern University
Sheridan Rd., Evanston, IL 60208 (USA)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200900341.
Scheme 1. Preparation of the sulfone functionalized ligand H
L1 using H SO 20%SO (oleum).
2
L2 from
H
2
2
4
3
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4523

Remarkably, that was not the case and we report here two
novel, three dimensional (3D), non-isoreticular porous
MOFs with unprecedented structures, isolated from con-
trolled solvothermal reactions between H L2 and Zn-
2
ACHTUNGTRENNUNG( NO ) ·6H O. The unique structural features of these
3 2 2
MOFs, denoted here as UoC-1 and UoC-2, include the for-
mation of novel inorganic secondary building units (SBUs)
with an unprecedented double organic bridging connectivity
in all directions, which represents a rare example of an or-
ganic SBU. We also report preliminary sorption properties
for selected gases including N , H , CO and CH .
2
2
2
4
The reaction between Zn ACHTUNGRTENN(NUG NO ) ·6H O and H L2 in DMF/
3 2 2 2
H O (67:1 v/v) at 908C for 24 h afforded UoC-1 as cubic-
2
like, colorless crystals in good yield, suitable for single crys-
tal X-ray analysis. We found that the water content and the
reaction temperature are very crucial parameters in obtain-
ing UoC-1. When the same reaction is performed using only
DMF as a solvent, a new MOF is obtained, UoC-2, as color-
less rod-like crystals in good yield.
¯
UoC-1 crystallizes in the trigonal system (space group R3)
with large unit cell parameters.
[11a]
The inorganic SBU,
shown in Figure 1, is a novel heptanuclear anionic cluster
À
with formula [Zn
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(m -OH)
A
H
N
T
E
N
N
(CO ) ] composed of one octa-
7
3
3
2 6
2
+
hedral and six tetrahedral Zn cations (see Figure 1a,b). In
this cluster, the octahedral zinc atom is located on a three-
fold axis and it is surrounded, through m -OH bridges, with
3
three pairs of tetrahedral, corner shared zinc atoms (see Fig-
ure 1b). This connectivity results in an asymmetric SBU
with a cage-like topology. Each SBU is linked to six other
2À
by twelve L2 ligands, following a pseudo-octahedral con-
nectivity, as shown in Figure 1c. In each direction, two lig-
AHCTUNGTRENNUNG
ands stack in parallel, one on the top of the other and serve
as linkers between two SBUs. The distance between these
two ligands is approximately 3.6 ꢁ which is typical of aro-
matic, face-to-face p–p stacking. (see Figure 1d). Each pair
of ligands is in fact an organic SBU, stabilized by weak p–p
interactions, which link together the six-connected inorganic
SBUs, resulting in the non-interpenetrating 3D open struc-
ture of UoC-1 (see Figure 1e). The three (crystallographi-
cally equivalent), out of the twelve ligands that connect
each SBU, bind from one side in a monodentate fashion
À
Figure 1. a) Novel heptanuclear [Zn
charged balanced by an hydronium cation, b) SBU looking down its C
axis, c) pseudo-octahedral connectivity of six SBUs, d) pair of a p–p sta-
7
A
H
U
G
R
N
U
G
3
-OH)
3
A
T
N
T
E
N
N
2
)
6
]
SBU in UoC-1,
3
(
C1ÀO3 1.273(10), C1ÀO4 1.244(10) ꢁ), while from the
2À
bilized L2 ligands connecting two adjacent SBUs, and e) pore system in
UoC-1 looking down the b axis.
other adopt a bidentate coordination mode, bridging two
tetrahedral zinc atoms. The other nine ligands (crystallo-
graphically equivalent) adopt a bis(bidentate) coordination
mode.
along with charge balance considerations strongly indicate
The single crystal X-ray analysis of UoC-1 revealed the
presence of an oxygen-type atom (O15) located on the
threefold axis of the SBU and close to the cavity of its cage
at a distance of 5.029(5) ꢁ from the central octahedral Zn1
atom (see Figure 1a). In addition, three, crystallographically
equivalent DMF molecules were found below this oxygen
atom. As shown in Figure 1a, this isolated atom is located at
an octahedral site formed by the three, non-coordinated
oxygen atoms (O15ÀO4 2.417(10) ꢁ) of the monodentate
that this isolated oxygen-type atom is in fact a hydronium
+
H O cation that compensates the anionic charge of the
3
SBU. The observed O···O distances indicate the existence of
strong hydrogen bonds, as expected. It is important to note
here that the C axis found on the atom O15 is in agreement
3
+
with the expected C symmetry of hydronium H O cat-
3v
3
[12]
ions.
These results explain why the synthesis of UoC-1
strictly requires the use of a DMF/H O mixture as solvent
2
instead of DMF only.
The 3D open structure of UoC-1 shows parallelogram
shaped 3D intersecting channels, with a window size of ap-
carboxylate groups and the three oxygen atoms from the
DMF molecules (O15ÀO13 2.355(10) ꢁ). These findings,
4524
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Chem. Eur. J. 2009, 15, 4523 – 4527

Functionalized Metal–Organic Frameworks
COMMUNICATION
À
proximately 10ꢂ10 ꢁ (measured between oxygen atoms of
A
H
U
G
R
N
U
(m -O)
A
H
U
G
R
N
U
G
A
H
U
G
R
N
N
(CO ) ] composed of two octahedral and four
4
2
2
2 5
2
+
opposite -SO groups, excluding van der Waals radii) which
tetrahedral Zn cations. In this cluster, one octahedral and
three tetrahedral zinc atoms share a common corned form-
2
are filled with guest DMF molecules and presumably with a
very small amount of H O molecules (see Figure 1e). The
ing a regular Zn O tetrahedron while one of these tetrahe-
2
4
solvent accessible volume, as calculated using the program
dral zinc atoms share a corner with the forth tetrahedral and
[13]
PLATON, is 69% of the total unit cell volume. Thermo-
gravimetric analysis (TGA) data show that the as-made
the second octahedral zinc atom, forming an m -OH bridge
3
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(see Figure 2a,b). In addition, a H O ligand was found in
2
solid contains approximately 13 DMF molecules per formu-
la unit, leading to an overall charged balanced formula
one of the apical positions of the two octahedral zinc atoms
(Zn3ÀO33 2.090(3), Zn5ÀO34 2.039(5) ꢁ) (see Figure 2b).
2À
[
H O]
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
[Zn
7A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(m -OH) (L2) ]
A
T
N
T
E
N
N
(DMF) . The crystals are found to
Each SBU is linked to five other by ten L2 ligands, follow-
3
3
3
6
13
be air sensitive and therefore more accurate elemental anal-
ysis was unable to be performed.
ing a pseudo-square pyramidal connectivity, as shown in Fig-
2À
ure 2c. Remarkably, as in UoC-1, a pair of L2 ligands sta-
bilized by weak p–p interactions (~3.9 ꢁ), serve as a linking
organic SBU between each pair of adjacent inorganic SBUs
(see Figure 2d). One, out of the five crystallographically in-
dependent ligands, binds from one side in a monodentate
fashion while from the other adopts a bidentate coordina-
tion mode, bridging one octahedral and one tetrahedral zinc
atom. The other four ligands adopt a bis(bidentate) coordi-
nation mode.
When only DMF was used instead of a DMF/H O mix-
2
ture, in otherwise similar solvothermal reaction conditions
between Zn
ACHTUNGTRENNUNG( NO ) ·6H O and H L2, a novel MOF was ob-
3 2 2 2
tained in good yield. UoC-2 crystallizes in the triclinic space
[
11b]
¯
group P1.
The inorganic SBU, shown in Figure 2a, is a
(m -OH)-
new hexanuclear anionic cluster with formula [Zn AHCTUNGTRENNUNG
6
3
The non-interpenetrating structure of UoC-2 shows large,
3
D intersecting channels. The window size along the [100]
lattice vector is approximately 16ꢂ10 ꢁ (measured between
oxygen atoms of opposite -SO groups, excluding van der
2
Waals radii), see Figure 2e. The calculated solvent accessible
[13]
volume is 73% of the total unit cell volume.
The single crystal X-ray analysis of UoC-2 did not reveal
an exact location of a charge balancing cation for the cluster
À
[Zn
A
H
U
G
R
N
U
G
A
H
U
G
R
N
U
G
A
H
U
G
R
N
N
(H O)
A
H
U
G
R
N
U
(CO ) ] . Given the fact that it is
6
3
4
2
2
2 5
generally difficult to completely formulate the exact compo-
sition of all guest molecules in highly porous MOFs and also
+
that dimethylammonium cations, (CH ) NH , are formed
3
2
2
[14]
in situ upon heating of DMF,
these as charge balancing cations, leading to an overall
charged balanced formula [(CH ) NH ][Zn6 A( m -OH)(m -O)-
(DMF) . Accurate thermogravimetric and ele-
it is natural to consider
A
H
U
G
R
N
N
C
T
G
R
N
U
ACHTUNGTRENNUNG
3
2
2
3
4
AHCTUNGTRNENUG( H O) L2 ] ACHTGNUTRENNUNG
2 2 5
x
mental analysis was not possible to be performed due to the
limited stability of UoC-2 in air.
The large free volume in both UoC-1 and UoC-2 prompts
us to investigate the possibility to remove the guest mole-
cules and access the pore space. Because of their limited sta-
bility in air, we performed solvent exchange reactions inside
[10]
a moisture-free, nitrogen filled glove-box.
While UoC-2
was not stable upon solvent removal, for UoC-1 we found
that CH Cl is a suitable solvent to remove the guest mole-
2
2
cules. TGA analysis of vacuum-dried, CH Cl -exchanged
2
2
crystals, revealed the formation of a solvent-free solid, de-
[10]
noted here as UoC-1’, which is stable up to 3508C. How-
ever, optical observation of UoC-1’ revealed a significant
loss of the initial transparent, cubic-like morphology of the
crystals. Powder X-ray diffraction measurement shows the
[10]
formation of a different phase with poor crystallinity.
À
Figure 2. a) Novel hexanuclear [Zn
in UoC-2, b) stick representation of the SBU showing the two coordinat-
ed H O molecules and the Zn O tetrahedron, c) pseudo-square pyrami-
6
A
H
U
G
R
N
U
(m
3
-OH)
A
H
U
G
R
N
U
G
4
-O)
A
H
U
G
R
N
U
(H
2
O)
2
A
T
N
R
N
N
(CO
2
)
5
]
SBU
Nevertheless, the nitrogen adsorption recorded at 77 K re-
vealed a mixed type-I/II isotherm, see Figure 3. The sharp
2
4
2À
uptake at low relative pressures (p/p <0.1) indicate the
o
dal connectivity of five SBUs, d) pair of a p–p stabilized L2 ligands
connecting two adjacent SBUs, and e) pore system in UoC-2 looking
down the a axis.
presence of microporosity (type-I isotherm) while the
almost linear uptake between 0.1<p/p <1 (type-II iso-
o
Chem. Eur. J. 2009, 15, 4523 – 4527
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4525

P. N. Trikalitis et al.
Figure 3. Nitrogen and argon adsorption (filled symbols)/desorption
open symbols) isotherms of UoC-1’ recorded at 77 K. Inset shows the
(
low relative pressure region in logarithmic scale.
therm) is characteristic of adsorption by a non-porous
[
15]
solid.
Similar mixed type-I/II nitrogen adsorption iso-
[16]
therms have been observed in some evacuated MOFs.
These results indicate a partial collapse of the framework in
UoC-1 upon solvent removal, in agreement with the powder
Figure 4. a) Hydrogen adsorption isotherms at 77 K and 87 K and b)
carbon dioxide and methane adsorption (filled symbols)/desorption
[10]
X-ray analysis data.
The argon adsorption isotherm re-
(
open symbols) isotherms at 273 K, of UoC-1’.
corded at 77 K confirmed the presence of microporosity in
UoC-1’. (see Figure 3). The apparent Langmuir surface area
2
À1
calculated from the N2 adsorption isotherm, is 649 m g
3
À1
À1
À1 [18]
and the micropore volume 0.24 cm g at 0.019 p/p . De-
(1.5 mmolg ) and ZIF-100 (1.7 mmolg ).
The CH4
o
À1
tailed micropore analysis using N and Ar at 77 K shows a
uptake under the same conditions is 0.57 mmolg . To calcu-
late the CO /CH selectivity from the corresponding
2
sharp uptake at very low relative pressures (onset at 1.0ꢂ
2
4
À5
À4
10
and 1.0ꢂ10 , respectively), see inset of Figure 3. The
Henryꢃs law constants, we performed a nonlinear fitting of
[10]
much lower pore filling pressure for nitrogen clearly indi-
cates that the attractive interactions of nitrogen molecules
with the pore surface in UoC-1’ are much stronger as com-
pared to argon. The estimated pore size, obtained by apply-
ing the Sato and Foley (SF) calculation method on the N2
data, is 7.7 ꢁ. Interestingly, a very similar pore size was
the adsorption isotherms using the Toth model. Accord-
ingly, the selectivity found at 273 K is 15.7 while at 263 K is
21.5. For comparison, the CO /CH selectivity of ZIF-100
2
4
and the prototypical adsorbent BPL carbon at 298 K, is 5.9
[15]
[18]
and 2.5, respectively.
negligible N and H adsorption at near ambient tempera-
Given the fact that UoC-1’ shows
[10]
2
2
obtained from both N and Ar data, when a non-local densi-
ture (data not shown), its large and highly selective CO ad-
2
2
ty functional theory (NLDFT), implementing a carbon equi-
librium transition kernel based on a slit-pore model, was ap-
plied.
sorption is an important property and indicates that this ma-
terial may serve as an efficient adsorbent to capture and
store CO2. Preliminary theoretical calculations show that
[10]
[19]
The accessible porosity found in UoC-1’ prompt us to in-
vestigate further its gas sorption properties. Hydrogen,
carbon dioxide and methane adsorption isotherms were re-
corded at different temperatures. The hydrogen uptake at
the observed selectivity results from a significant stronger
interaction of CO molecules with the polar sulfone (-SO )
groups as compared to the other gases. These results will be
published in detail elsewhere.
2
2
1
bar and 77 K is 0.87 wt% (see Figure 4a). The isosteric
In conclusion, we have shown that the rigid, sulfone func-
heat of adsorption (Q ) calculated from the respective ad-
tionalized dicarboxylate ligand H L2 is capable in directing
st
2
sorption isotherms at 77 and 87 K employing the Clausius–
the formation of novel, non-interpenetrating 3D MOFs, as-
sembled from unprecedented inorganic SBUs. Another
unique feature in both UoC-1 and UoC-2 is that adjacent
SBUs are connected via a double rather than a single organ-
À1
Clapeyron equation, is approximately 6.8 kJmol at zero
[10]
coverage. This value is close to the corresponding values
[17]
found for the most promising MOFs for hydrogen storage.
More interestingly, UoC-1’ shows a completely reversible,
ic ligand. In addition, UoC-1 is a rare anionic MOF charged
+
high CO adsorption at near ambient temperature (see Fig-
balanced by hydronium H O cations. Accessible porosity
2
3
À1
ure 4b). The CO uptake at 1 bar and 273 K is 2 mmolg ,
was found in the solid obtained after solvent removal from
UoC-1. This material shows a remarkable selectivity for
CO over CH , N and H at near ambient temperature.
2
which is higher compared to the corresponding values of
some representative MOFs and ZIFs including MOF-5
2
4
2
2
4526
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Chem. Eur. J. 2009, 15, 4523 – 4527

Functionalized Metal–Organic Frameworks
COMMUNICATION
Finally, the synthesis of UoC-1 and UoC-2 demonstrates
that the isoreticular principle, although valid up to date for
M. OꢃKeeffe, O. M. Yaghi, Science 2008, 319, 939; e) A. R. Millward,
O. M. Yaghi, J. Am. Chem. Soc. 2005, 127, 17998.
3] a) D. Britt, D. Tranchemontagne, O. M. Yaghi, Proc. Natl. Acad. Sci.
USA 2008, 105, 11623; b) B. L. Chen, C. D. Liang, J. Yang, D. S.
Contreras, Y. L. Clancy, E. B. Lobkovsky, O. M. Yaghi, S. Dai,
Angew. Chem. 2006, 118, 1418; Angew. Chem. Int. Ed. 2006, 45,
[
strictly rigid ligands, does not apply in the case of H L2
2
under the specific reaction conditions and a novel family of
sulfone functionalized MOFs with important properties
could be envisioned. The origin of this exception is currently
under investigation and it could be related to the non-linear
bridging mode of the ligand; the sulfone group bends the
two phenyl rings causing the two carboxylate end-groups to
1
390; c) Y. S. Bae, K. L. Mulfort, H. Frost, P. Ryan, S. Punnathanam,
L. J. Broadbelt, J. T. Hupp, R. Q. Snurr, Langmuir 2008, 24, 8592.
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[
[10]
form an angle of 1638.
Another factor that could act
[5] Y. K. Hwang, D. Y. Hong, J. S. Chang, S. H. Jhung, Y. K. Seo, J.
Kim, A. Vimont, M. Daturi, C. Serre, G. Ferey, Angew. Chem. 2008,
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
simultaneously is the increased acidity of the ligand caused
ACHTUNGTRENNUNG
1
20, 4212; Angew. Chem. Int. Ed. 2008, 47, 4144.
by the electronegative sulfone group attached to the phenyl
rings.
[
6] B. Arstad, H. Fjellvaag, K. O. Kongshaug, O. Swang, R. Blom, Ad-
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[
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Experimental Section
[
[
Synthesis of UoC-1: In
.49 mmol) and H L2 (0.05 g, 0.16 mmol) were dissolved in a mixture of
DMF (10 mL) and H O (0.15 mL) at room temperature. The vial was
placed in a temperature controlled oven at 958C. Transparent cubic-like
crystals were formed within 24 h. Yield: 0.136 g, based on Zn-
3 2 2
a 20 mL vial, Zn ACHTUNGRTNNEG(U NO ) ·6H O (0.147 g,
0
2
2
[
[
10] See Supporting Information for details.
11] a) Single crystal X-ray diffraction data for UoC-1: trigonal, space
¯
group R3, a=b=23.0793(6), c=71.787(2) ꢁ, a=90, b=90, g=1208,
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(NO
Synthesis of UoC-2: In
.49 mmol) and L2 (0.05 g, 0.16 mmol) were dissolved in DMF
10 mL) at room temperature. The vial was placed in a temperature con-
trolled oven at 958C. Transparent, rod-like crystals were formed within
4 h. Yield; 0.145 g, based on Zn(NO ·6H O.
3
)
2
·6H
2
O.
3
À3
V=33114.8(2) ꢁ ,
Z=6,
1
calcd =0.769 gcm
,
T=100.0(3) K,
a
20 mL vial, Zn
A
H
U
G
R
N
N
(NO
3
)
2
·6H
2
O
(0.147 g,
2qmax=408. Refinement of 457 parameters on 6848 independent re-
flections out of 63157 measured reflections (Rint =0.0992) led to
R =0.0783 (I>2s(I)), wR =0.2304 (all data), and S=1.207 with the
0
H
2
(
1
2
À3
largest difference peak and hole of 1.738 and À0.48 eꢁ ; b) single
2
A
H
U
G
R
N
N
3
)
2
2
crystal X-ray diffraction data for UoC-2: triclinic, space group P 1¯ ,
a=21.4410(2), b=23.212(2), c=24.646(3) ꢁ, a=68.103(7), b=
3
6
0
7.490(7),
g=79.993(7)8,
V=10507.0(2) ꢁ ,
Z=2,
calcd
1 =
À3
À1
.622 gcm , m=0.757 mm , T=100.0(3) K, 2qmax =408. Refinement
of 1011 parameters on 19544 independent reflections out of 69048
measured reflections (Rint =0.1218) led to R =0.0492 (I>2s(I)),
wR =0.1371 (all data), and S=0.788 with the largest difference
peak and hole of 0.296 and À0.459 eꢁ . Electron density contribu-
tions from disordered guest molecules were handled using the
SQUEEZE procedure from the PLATON software suit. See also
Supplementary Information for details. CCDC 714151 (UoC-1) and
Acknowledgements
1
2
The research was supported financially by the European Union (75%)
and the Greek Government (25%) through the program PENED-2003
code numbers 03ED581 and 03ED450, from Interreg IIIA Greece-
Cyprus program (K2301.004) and European Commission DG RTD (FP6
Integrated Project NESSHY, Contract SES6-518271). We are grateful to
Prof. Mercouri G. Kanatzidis for providing access to a single-crystal
XRD equipment.
À3
7
14152 (UoC-2) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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Chem. Eur. J. 2009, 15, 4523 – 4527
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4527