Three scandium compounds with unsaturated coordinative metal sites - Structures and catalysis

Article abstract of DOI:10.1002/ejic.201402740

Two scandium coordination polymers, a 2D supermolecule structure {[Sc(OH)(L¹)₂(H₂O)]}_n (1) (HL¹ = isonicotinic acid), a 1D infinite chain structure {[Sc₃(L²)₄(H_2<

Full text of DOI:10.1002/ejic.201402740

FULL PAPER
DOI:10.1002/ejic.201402740
Three Scandium Compounds with Unsaturated
Coordinative Metal Sites – Structures and Catalysis
[
a]
[a]
[a]
[a]
Liying Zhang, Li Wang, PengCheng Wang, Tianyou Song,
[
a]
[b]
[a]
[a]
Da Li, Xiaobo Chen, Yong Fan,* and Jianing Xu*
Keywords: Scandium / Organic–inorganic hybrid composites / Heterogeneous catalysis / Cyanosilylation
Two scandium coordination polymers, a 2D supermolecule
terized by X-ray crystallography. Compounds 1–3 are active
heterogeneous catalysts for high-yield cyanosilylation of aro-
matic aldehydes in acetonitrile, particularly for p-nitrobenz-
aldehyde. Moreover, these three catalysts can be reused
three times without significant loss in activity or mass.
1
1
structure {[Sc(OH)(L )
2
(H
2
O)]}
n
(1) (HL = isonicotinic acid),
2
a 1D infinite chain structure {[Sc
3
(L )
4
(H
2
O)
4
]·NO
3
·H
2
O}
n
(2)
2
2
(H L = 4,5-imidazole dicarboxylic acid), as well as a scan-
3
3
2 2 2 2 4 n 2
dium complex {[Sc (OH) (L ) (H O) ]} (3) (H L = 1,2,3-tri-
azole-4,5-dicarboxylic acid), were synthesized and charac-
Introduction
and can easily be recycled and reused without any appreci-
[
6]
able loss in activity. Although the interest in Sc has been
increasing recently because of the successful utilization of
Heterogeneous catalysis is a vital component that has
been exploited by about 90% of the existing chemical
manufacturing processes.[ Metal coordination polymers
are emerging solid materials for heterogeneous catalysis,
with regard to their high surface area, well-defined porous
structure, and chemical tunability.[ Coordination polymers
can act as heterogeneous Lewis acid catalysts, because they
can provide unsaturated coordinative nodes or form active
metal complexes that are incorporated into the linking
ligands. Moreover, metals and ligands are strongly bound
within the framework, which prevents decomposition in
solutions. Therefore, compared to discrete molecular con-
tainers, coordination polymers have a number of advan-
tages, such as high thermal stability, easy crystallization in
[7]
its compounds in organic chemistry and the preparation
1]
of some polymer-supported Sc catalysts, there are only a
few examples of Sc-CP-based heterogeneous catalysts show-
[5,8]
ing a high stability and desirable properties.
2]
The cyanosilylation reaction is an important C–C bond-
[9]
forming reaction that is catalyzed by Lewis acids. It pro-
vides a convenient route to prepare cyanohydrins, which are
key derivatives in the synthesis of fine chemicals and phar-
[10]
maceuticals. In coordination polymers, vacant coordina-
tion site(s) associated with the metal centers and/or func-
tional organic sites for possible interactions with reactants
[11]
have been reported to catalyze this reaction. Thus we aim
to design and synthesize robust Sc compounds containing
coordinative unsaturated metal sites.
[
3]
high yields, and low solubility in common solvents.
Recently, scandium coordination polymers (Sc-CPs) with
thermally stable frameworks have demonstrated interesting
catalytic properties in green chemistry.[ For example, a Sc- Results and Discussion
4]
CP built from squaric acid, Sc (C O ) , can act as an ef-
2
4
4 3
1
Two Sc-CPs and one Sc complex, {[Sc(OH)(L ) (H O)]}
2
2
n
n
ficient heterogeneous catalyst both in cyanosilylation and
1
2
acetalization of carbonyl compounds.[5] A new hybrid or-
(1) (HL = isonicotinic acid), {[Sc
3
(L )
(H
4
2
O)
4
]·NO
3
·H O}
2
2
(
{
2) (H L
=
4,5-imidazole dicarboxylic acid), and
[Sc (OH) (L ) (H O) ]} (3) (H L = 1,2,3-triazole-4,5-di-
carboxylic acid), were synthesized on the basis of three dif-
ferent carboxylate ligands. These three new Sc compounds
display good catalytic activity for the cyanosilylation of aro-
matic aldehydes, especially for p-nitrobenzaldehyde.
2
ganic–inorganic polymer, Sc (OOCC H COO)2.5(OH), pre-
2
2
4
3
3
2 2 2 2 4 n 2
pared by Snejko and co-workers can be used as an effective
Lewis acid catalyst in the Friedel–Crafts acylation reaction
[
a] State Key Laboratory of Inorganic Synthesis and Preparative
Chemistry, College of Chemistry, Jilin University
Jiefang road 2519, Changchun, China
E-mail: mrfy@jlu.edu.cn
xujn@jlu.edu.cn
Crystallographic Structure of 1
[
b] Department of Materials Engineering, Monash University
Clayton, VIC 3800, Australia
Compound 1 crystallizes in the monoclinic space group
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402740.
III
P2 /c, and its asymmetric unit contains one Sc ion, two
1
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1
L ligands, one OH group, and one coordinated water mo- whereas the other one remains uncoordinated. The nitrogen
lecule (Figure S1). The 2D structure of 1 is constructed atom does not provide a coordinated site in 1. The ScO4
1
from the infinite chains Sc(OH)(L ) (H O) by π···π stacking units are linked to each other through OH groups, and this
2
2
1
interactions of L ligands. There are two kinds of six-coor- generates an infinite bent –Sc–OH–Sc–OH– chain with a
III
dinate Sc ions. The coordination geometry of Sc1 can be Sc–OH–Sc angle of 158° (Figure 2a). As shown in Fig-
1
described as an octahedron with two oxygen atoms from ure 2b, the –Sc–OH–Sc–OH– chains are linked by L
1
1
two independent L ligands, two oxygen atoms from two ligands to form a new infinite 1D chain, Sc(OH)(L ) (H O).
2
2
OH groups, and two oxygen atoms from two terminal water The plane-to-plane distances between the benzene rings of
1
molecules to complete the coordination sphere. The Sc2 the L ligands in adjoining chains are about 3.3 Å. This
octahedron is linked by four oxygen atoms from four inde- suggests that contiguous chains are packed though strong
1
1
pendent L ligands and two oxygen atoms from two OH π–π stacking interactions. The rings of the L ligand in-
groups (Figure 1). The Sc–O bond lengths fall in the region volved in the π–π stacking arrange in such a way that the
of 2.0619(18)–2.1331(18) Å; these values are consistent with six atoms of the ring do not completely overlap those of the
those of similar compounds.[
12]
Figure 1. The coordination environment of the ScIII ions in 1. All
hydrogen atoms are omitted for clarity. Symmetry codes: A, –x, 1 –
y, 2 – z; B, 1 – x, 1 – y, 2 – z.
Figure 2. (a) The –Sc–OH–Sc–OH– chain in 1. (b) The infinite 1D
1
The L ligand exhibits two distinct types of coordination
1
chain Sc(OH)(L )
2
(H
2
O). (c) The π···π interactions in 1, in which
1
modes, A and B, in 1 (Scheme 1). A (purple): two oxygen L ligands of coordination mode B (yellow) were omitted (Sc, pink;
O, green; C, purple and yellow; N, blue).
atoms of the carboxy group act in a monodentate mode,
bridging two Sc centers; B (yellow): only one of the
III
carboxy groups acts in a monodentate coordination mode,
Figure 3. The packing diagram of 1 showing the projection along
Scheme 1. The two different coordination modes in 1 (Sc, pink; O,
green; C, purple and yellow; N, blue).
the bc direction. Hydrogen atoms are omitted for clarity (Sc, pink;
O, green; C, purple and yellow; N, blue).
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other rings. This means that the π–π interaction is not “per- Crystal Structure of 2
fect face alignment” but “slipped stacking”. To more clearly
1
describe the π–π interactions in 1, L ligands of coordina-
Compound 2 crystallizes in the orthorhombic space
tion mode B (yellow) are omitted in Figure 2c. The packing group Fddd and shows a 1D infinite chain. The asymmetric
III
2
diagrams of 1 display triangular windows showing the pro- unit consists of three-quarters of a Sc ion, one L ligand,
jection along the bc direction as depicted in Figure 3. This and one coordinated water molecule (Figure S2). As shown
III
π–π stacking plays an important role to stabilize the pack- in Figure 4a, there are two types of Sc ions with different
ing of such low-dimensional lattices. To the best of our coordination environments. Sc1 is eight-coordinate, and its
knowledge, the –Sc–OH–Sc–OH– chain has rarely been re- coordination geometry can be described as a triangular
ported in scandium coordination polymers.
dodecahedron with four oxygen atoms and four nitrogen
Figure 4. (a) The coordination environment of the ScIII ions in 2. (b) An infinite 1D chain along the ac direction. (c) The packing diagram
of 2 showing the projection along the ab direction; black spheres are six-coordinate Sc2 ions, and green spheres are eight-coordinate Sc1
ions. Hydrogen atoms and guest molecules are omitted for clarity (Sc, black and green; O, red; C, dark gray; N, blue). Symmetry codes:
A, –0.5 + x, 1.75 – y, 0.25 – z; B, 1.25 – x, 1.75 – y, –1.5 + z; C, 1–0.5 + x, 1.75 – y, –0.75 – z; D, 1.25 – x, y, 0.75 – z.
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2
atoms from four different L ligands. Sc2 is six-coordinate, vary from 2.042(2) to 2.153(3) Å; these values are consistent
[
14]
and its coordination geometry can be described as an octa- with those of analogous compounds.
Sc1 and its corre-
hedron with four monodentate carboxylate oxygen atoms sponding centrosymmetrically generated atom Sc1A are
2
from two independent L ligands, and two oxygen atoms joined by two μ -O atoms of OH groups to give a binuclear
2
3
from two OH groups to complete the coordination sphere. unit of [Sc (OH) (L ) (H O) ] (Figure 5b), in which the dis-
2
2
2
2
4
The Sc–O bond lengths fall in the region of 2.064(4)– tance between two Sc atoms is 3.1884(13) Å and the angle
.262(4) Å and the Sc–N bond is 2.276(5) Å. These bond Sc1–O7–Sc1A is 78.16°. The packing diagram of compound
2
III
lengths are in agreement with those reported for other Sc
compounds.
3 shows the projection along the ac direction as depicted in
[
12]
2
Sc1 and Sc2 are connected with L ligands Figure 5c. No intra- and interchain hydrogen bonds or π–π
to form an infinite 1D chain along the ac direction (Fig- stacking interactions were observed in 3.
ure 4b). The 1D chain is butterfly-shaped and the neigh-
boring chains are alternately stacked along the ab direction
(
Figure 4c). No intra- and interchain hydrogen bonds or Thermogravimetric Analysis
π–π stacking interactions were observed in 2.
Thermogravimetric analysis (TGA) was carried out at
temperatures varying from 20 to 800 °C in air with a heat-
ing rate of 10 °Cmin–1 (Figures S10–S12). As shown in Fig-
ure S10, compound 1 gradually loses lattice water from 80
Crystal Structure of 3
Compound 3 crystallizes in the orthorhombic space to 300 °C, and then it decomposes rapidly. The weight loss
III
group Pbca. The asymmetric unit consists of one Sc ion, of 78.48% (calcd. 78.72%) is in agreement with the decom-
3
1
one L ligand, one OH group, and two coordinated water position of [Sc(OH)(L ) (H O)] to ScO1.5. Compound 2 dis-
2
2
III
molecules (Figure S3). As shown in Figure 5a, the Sc ion plays a continuous weight loss of 77.31% (cal. 77.10%) in
displays an octahedral geometry, being coordinated by two the temperature range 100–550 °C, which corresponds to
3
carboxylate oxygen atoms of one L ligand, two oxygen the loss of guest molecules (nitrate anion and water
atoms from two OH groups, and two oxygen atoms from molecule), coordinated water molecules, and L2 ligands.
two coordinated water molecules. The Sc–O bond lengths The remaining weight of 22.69% is attributed to the final
product of Sc O (cal. 22.90%). The TGA plot of 3 also
2
3
shows a continuing weight loss. The weight loss from 220
to 800 °C amounts to 72.50% (calcd. 72.75%), correspond-
3
ing to the decomposition of [Sc (OH) (L ) (H O) ] to
2
2
2
2
4
ScO1.5
.
Catalytic Properties
The presence of unsaturated coordinated metal sites in
solid materials is beneficial for catalytic reactions, providing
Lewis acid sites in the structure. In the present work, there
III
are unsaturated coordinated Sc ions (the six-coordinate
III
Sc ions) in all of the compounds. Therefore, catalytic
properties are expected for these compounds. To character-
ize the possible acid-type catalytic behavior of the unsatu-
rated coordination in compounds 1–3, the carbonyl cyano-
silylation reaction was performed in the presence of all
–
three compounds. The addition of CN to a carbonyl com-
pound to form a cyanohydrin is one of the fundamental
C–C bond formation reactions in organic chemistry.[
Compounds 1–3 were demonstrated to act as catalyst in
the cyanosilylation reaction of aldehydes with trimethylsilyl
13]
cyanide (TMSCN) in CH CN. The reaction conditions
3
were first established by using benzaldehyde as model sub-
strate. The best conversion rate was obtained when 20%
catalyst was used at room temperature. In order to further
investigate the generality of the catalysts, we studied the in-
fluence of the different substituents of the aromatic alde-
hydes on the reaction under the same conditions. Kinetics
results are shown in Figure 6, and the data are summarized
in Table 1. Electron-withdrawing groups are known to im-
prove the electropositivity of the carbon atom of the aro-
III
Figure 5. (a) The coordination environment of the Sc ions in 3.
2
(
b) A binuclear unit of [Sc
2
(OH)
2
(L )
2
(H
2
O)
4
] in 3. (c) The packing
diagram of 3 showing the projection along the ac direction.
Hydrogen atoms are omitted for clarity (Sc, green; O, red; C, dark
gray; N, blue). Symmetry codes: A, –x, –y, –z.
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matic aldehyde, which favors the nucleophilic addition reac- for 1, and after 24 h for 2 and 3. Moreover, the value of the
tion between the aromatic aldehyde and TMSCN. There- conversion rate is in agreement with the electron-with-
fore, the conversion rate of the cyanosilylation reaction of drawing ability of the substituent groups. For example, for
p-nitrobenzaldehyde and TMSCN reaches 100% after 5 h 3, the conversion rate decreases in the order p-nitrobenz-
aldehyde Ͼ p-bromobenzaldehyde Ͼ benzaldehyde Ͼ p-
methoxybenzaldehyde Ͼ 1-naphthaldehyde. As shown in
Figure 7, the catalytic activity of 1–3 for the cyanosilylation
of aldehydes is rather high for p-nitrobenzaldehyde (100%,
5
h for 1 and 100%, 24 h for 2 and 3). For the four remain-
ing substrates, the order of the catalytic activity is 1 Ͼ 2 Ͼ
(Figure 7). This may correspond to the windows in the
packing arrangement of 1 along the bc or ab directions
Figure 3 and Figure S13), and the six-coordinate Sc1 and
3
(
Sc2 are exposed in this window. Compared to 3, the free
space surrounding the coordinated unsaturated metal sites
(
six-coordinate Sc2) in 2 is larger, which can provide a
III
larger contact area for the reaction. Although the Sc ion
is also six-coordinate in 3, probably geometrical constraints
(Figure 5c and Figure S14) do not allow the reactants to
diffuse inside the structure of the catalyst, and only the ex-
ternal surface area of this material becomes available for
the reactants.
Table 1. Results for the cyanosilylation of carbonyl substrates in
the presence of 1–3.
Catalyst
Ar
Time (h)
Yield (%)
1
phenyl
20
5
24
24
24
24
8
24
24
24
24
8
24
24
24
100
100
100
100
74
55
98
42
37
33
25
p-nitrophenyl
p-bromophenyl
p-methoxyphenyl
1-naphthyl
2
3
phenyl
p-nitrophenyl
p-bromophenyl
p-methoxyphenyl
1-naphthyl
phenyl
p-nitrophenyl
p-bromophenyl
p-methoxyphenyl
98
30
13
6
1-naphthyl
After the reactions, the solid catalyst was recovered by
centrifugation and washed with anhydrous acetonitrile and
then characterized by powder X-ray diffraction (Fig-
ure S15). The powder diffraction patterns of the recovered
catalysts are similar to those of the as-synthesized com-
pounds. Reutilization is one of the greatest advantages of
heterogeneous catalysts and can also provide useful infor-
mation about the anchoring process and catalyst stability
along the catalytic cycle. Recycling tests were carried out
for all three compounds for the cyanosilylation of p-
nitrobenzaldehyde. The catalyst was recycled after three
runs. During the successive cycles, a small decrease in the
activity was observed.
Figure 6. Plots of conversion vs. time for the cyanosilylation reac-
tion with five different substrates for 1 (a), 2 (b), and 3 (c).
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(
PL) spectra were measured with an Edinburgh Instruments
1
FLS920 spectrophotometer. H NMR spectra were measured with
a Bruker Avance 400 console at a frequency of 400 MHz.
3 3 2 2
Compound 1: Sc(NO ) ·6H O (0.2 mmol in 2.5 mL H O) and iso-
nicotinic acid (0.0369 g, 0.3 mmol) were dispersed in water (5 mL)
in a 20 mL glass jar with a lid and heated at 80 °C for 16 h. The
mixture was then cooled to room temperature under ambient con-
ditions. Colorless block crystals of 1 were recovered by filtration,
washed with distilled water, and dried in air. The yield of the prod-
11 2 6
uct was 82% in weight percent based on Sc. C12H N O Sc (324):
calcd. C 44.46, H 3.42, N 8.64; found C 44.25, H 3.61, N 8.49.
Selected IR data (KBr pellet): ν˜ = 3442 (s), 3000 (s), 2368 (w), 1554
–
1
(
s), 1385 (s), 1158 (w), 1021 (m), 761 (m), 669 (m), 458 (m) cm .
Compound 2: Sc(NO ·6H O (0.2 mmol in 2.5 mL H O) and 4,5-
3
)
3
2
2
imidazole dicarboxylic acid (0.0624 g, 0.4 mmol) were dispersed in
acetonitrile (5 mL) and concentrated hydrochloric acid (0.05 mL)
in a 23 mL Teflon-lined autoclave. The mixture was heated under
autogenous pressure at 105 °C for 3 d and then cooled to room
temperature under ambient conditions. Yellow block crystals of 2
were recovered by filtration, washed with distilled water, and dried
in air. The yield of product was 82% in weight percent based on
Figure 7. A comparison of conversion between catalysts 1, 2, and
(reaction time = 24 h).
3
Sc. C20
H
18
N
9
O
24Sc
3
(903): calcd. C 26.59, H 2.01, N 13.96; found
As we know, the solvent has also a certain influence on C 26.25, H 2.07, N 13.64. Selected IR data (KBr pellet): ν = 3442
˜
catalyst activity. These three catalysts can maintain stability (s), 3149 (s), 1572 (s), 1500 (w), 1408 (m), 1242 (m), 1120 (m), 980
–
1
and activity in the presence of acetonitrile, dichlorometh- (w), 841 (m), 648 (m), 523 (m) cm .
ane, chloroform, tetrahydrofuran, or dioxane. When using
3 3 2 2
Compound 3: Sc(NO ) ·6H O (0.2 mmol in 2.5 mL H O) and 1,2,3-
acetonitrile as solvent, a better catalytic effect can be
triazole-4,5-dicarboxylic acid (0.0393 g, 0.25 mmol) were dispersed
obtained. But when using tetrahydrofuran or dioxane as in CH CN (8 mL) and NaOH (1 m, 0.3 mL) in a 23 mL Teflon-
3
solvent, there are side reactions observed in the reaction lined autoclave and heated under autogenous pressure at 120 °C
system.
for 3 d. The mixture was then cooled to room temperature under
ambient conditions. Yellow block crystals of 3 were recovered by
filtration, washed with distilled water, and dried in air. The yield
8 12 6 2
of product was 85% in weight percent based on Sc. C H N O14Sc
(
1
506): calcd. C 18.98, H 2.39, N 16.60; found C 19.75, H 2.41, N
6.64. Selected IR data (KBr pellet): ν˜ = 3394 (s), 1624 (s), 1478
Conclusions
(
(
w), 1357 (m), 1393 (m), 1131 (w), 981 (w), 838 (m), 616 (w), 510
m) cm .
In summary, three Sc compounds were prepared by using
discrete carboxylate ligands under solvothermal conditions.
–
1
These three new solid materials show high chemical stability Single-Crystal X-ray Structure Determination: Suitable single crys-
tals of 1–3 were selected for single-crystal X-ray diffraction analy-
in CH CN, as well as good Lewis acid catalytic ability for
3
sis. The intensity data collection was performed with a Rigaku R-
the cyanosilylation of aromatic aldehydes by virtue of their
AXIS RAPID diffractometer equipped with graphite-monochro-
coordinative unsaturated metal sites. Moreover, they could
α
mated Mo-K (λ = 0.71073 Å) radiation in the ω scanning mode
be easily recovered by filtration and reused at least after
three cycles without significant loss of yield. In addition,
they also display intense fluorescence in the solid state at
room temperature.
at room temperature. No significant decay was observed during the
data collection. Data processing was accomplished with the
RAPID AUTO processing program. The structures were solved by
2
direct methods and refined by full-matrix least-squares on F by
using the SHELXTL crystallographic software package.[ All the
non-hydrogen atoms were refined anisotropically. All the hydrogen
atoms attached to carbon atoms were placed geometrically and lo-
cated theoretically on the basis of a riding model. The unit cell
volume of 2 includes a large region of disordered nitrate anion and
water molecule, which could not be modeled as discrete atomic
sites. We employed PLATON/SQUEEZE[ to calculate the contri-
bution to the diffraction from the solvent region. The final formula
was calculated from the SQUEEZE results combined with elemen-
tal analysis data and TGA data.[ Experimental details for the
structural determinations of 1–3 are summarized in Table 2, while
selected bond lengths and angles are presented in Tables S1–S3.
CCDC-980253 (for 1), -978974 (for 2), and -978973 (for 3) 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.
14]
Experimental Section
General Procedures: All the chemicals used in this work were of
reagent grade and were used without purification. Powder X-ray
diffraction (PXRD) data were collected with a Rigaku D/max-2550
15]
α
diffractometer with Cu-K radiation (λ = 1.5418 Å). Elemental
16]
analyses (C, H, and N) were performed with a Perkin–Elmer 2400
CHN Elemental Analyzer. IR spectra were recorded in the range
4
00–4000 cm–1 with a Nicolet Impact 410 spectrometer by using
the KBr pellet method. Thermogravimetric analyses (TGA) were
conducted with a Perkin–Elmer TGA 7 thermogravimetric analyzer
by starting with ambient conditions and heating at a rate of
1
0 °Cmin–1 from room temperature to 800 °C. Photoluminescence
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Chem. Asian J. 2012, 7, 2796–2804; c) L. Ma, W. Lin, Top.
Curr. Chem. 2010, 293, 175–205; d) M. Ranocchiari, J. A.
van Bokhoven, Phys. Chem. Chem. Phys. 2011, 13, 6388–6396;
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Table 2. Crystal and structure refinement details for 1–3.
Compound
1
2
3
Formula
Formula weight
T (K)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
C
12
H
11
O
6
N
2
ScC20
H
18
O
24
N
9
Sc
3
C
506
293(2)
8 12 14 6 2
H O N Sc
7
638–7649; f) D. Farrusseng, S. Aguado, C. Pinel, Angew.
Chem. Int. Ed. 2009, 48, 7502–7513; Angew. Chem. 2009, 121,
638; g) Y. Huang, Z. Zheng, T. Liu, J. Lü, Z. Lin, H. Li, R.
324
293(2)
monoclinic
P2 /C
7.4582(15)
18.454(4)
10.380(2)
90
903
293(2)
orthorhombic orthorhombic
7
Cao, Catal. Commun. 2011, 14, 27–31; h) Y. Huang, S. Liu, Z.
Lin, W. Li, X. Li, R. Cao, J. Catal. 2012, 292, 111–117; i) Y.
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Y. Huang, T. Liu, J. Lin, J. Lü, Z. Lin, R. Cao, Inorg. Chem.
1
Fddd
Pbca
31.8861(12)
20.2788(6)
10.5793(3)
90
14.121(3)
6.7919(14)
17.397(3)
90
β (°)
92.01(3)
90
6840.7(4)
4
1.494
652.0
0.543
0.0648
1.071
0.0469,
0.1341
0.0689,
0.1465
90
90
6840.7(4)
8
1.567
3256.0
0.669
0.0472
1.092
0.0953,
0.2189
0.0988,
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