Unique (3,12)-Connected Inorganic Lanthanide Cluster Polymer
Based on Octahedral Hexanuclear Europium Hydroxide Clusters
and Sulfate Anions: Synthesis, Structure and Luminescence
Yan-Qiong Sun,*† Hong-Xin Mei,† Han-Hui Zhang, † Yi-Ping Chen, † and Rui-Qing Sun†
†
Department of Chemistry, Fuzhou University, Fuzhou 350108, P. R. China,
*Corresponding author. Tel: (+86)-591-22866340. Fax: (+86)-591-22866340.
E-mail: sunyq@fzu.edu.cn
Figure S1. The asymmetric unit of 1 with labeling scheme.
As shown in Figure S1, In the asymmetrical units of 1, there are three
crystallographically independent Eu3+ ions and two SO42- anions.
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Figure S2. The coordination environments of Eu1 atom in 1. (left) The ball-stick representation.
(right) The polyhedral representation. Atoms having “A”, in their labels are symmetry-generated.
Symmetry code: A: 1-x, 1-y, 1-z.
Figure S3. The coordination environments of Eu2 atom in 1. (left) The ball-stick representation.
(right) The polyhedral representation. Atoms having “A”, “B”, or “C” in their labels are
symmetry-generated. Symmetry code: A: 1-x, 1-y, 1-z; B: 1-x, -y, 1-z; C: x, y, 1+z.
Figure S4. The coordination environments of Eu3 atom in 1. (left) The ball-stick representation.
(right) The polyhedral representation. Atoms having “A”, “B”, “C” or “D” in their labels are
symmetry-generated. Symmetry code: A: 1-x, 1-y, 1-z; B: 1-x, -y, 1-z; C: x, y, 1+z ; D : -1+x,
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1+y, z.
All the Eu3+ cations are nine-coordinated in a tricapped trigonal prism. In addition
to one interstitial and four hydroxide O atoms, The Eu1 ions are coordinated by two
OS atoms from two distinct SO42- anions and two water molecules; the Eu2 ions are
bonded to three OS atoms of three SO42- anions and one water molecules; and the
remaining coordination positions of Eu3 atoms are occupied by the four OS atoms of
three SO42- anions. The Eu-O bond distances are in the range of 2.34 to 2.68 Å.
Figure S5. Two types of coordination modes of SO42- anions in 1.
The two unique SO42- anions adopt two different coordinations: one behaves as a
μ5-SO4 mode linking four Eu atoms in one bidentate and three monodentate modes;
the other acts as μ4-SO4 mode connecting four Eu centers in four monodentate modes.
Figure S6. 1-D zigzag inorganic lanthanide cluster chain running along the a axis.
Figure S7. 1-D ladderlike chain running along the c axis.
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Figure S8. 1-D ladderlike chain running along the b axis.
The hexanuclear [Eu6(μ6-O)(μ3-OH)8]8+ cluster units are connected through
bridging μ2-OS to form an interesting 1-D zigzag inorganic lanthanide cluster chain
running along the a axis, furthermore, there are two types of ladderlike chains built
from hexanuclear [Eu6(μ6-O)(μ3-OH)8]8+ cluster units bridged by SO42- anions running
along the b and c axis.
Figure S9. 3-D framework viewed along the [100]
Figure S10. 3-D framework viewed along the [010]
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Figure S11. 3-D framework viewed along the [001]
(a)
(b)
Figure S12. (a) Schematic representation of lanthanide cluster as a 12-connected node. (b)
(3,12)-Connected topological net of 1. Yellow triangles and cyan octahedrons represent
3-connected
SO42-
anions
and
12-connected
[Eu6(μ6-O)(μ3-OH)8]8+ cluster units,
respectively.
Complex 1 exhibits a novel (3,12)-connected topological net with a point symbol
of (43)4(420.628.818) and a vertex symbol of symbol: [4.4.4.4.4.4.4.
4.4.4.4.4.4.4.4.4.4.4.4.4.6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2)
.6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(4).6(4).6(4).6(4).8(8).8(8).8(1
6).8(16).8(16).8(16).8(20).8(20).8(20).8(20).8(20).8(20).8(20).8(20).8(32).8(32).8(32
).8(32)] by TOPOS,[2,3] whose topological type is 3,12T2(binary ttd).
The computed results of (3, 12)-connected net of 1 by TOPOS 4.0 are as follows:
Structure consists of 3D framework with TiSc2S2
Coordination sequences
----------------------
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S1: 1 2 3 4 5 6 7
8
9 10
Num 3 28 19 126 51 286 99 510 163 798
Cum 4 32 51 177 228 514 613 1123 1286 2084
---------------------Sc1: 1 2 3 4 5 6 7
8
9 10
Num 3 28 19 126 51 286 99 510 163 798
Cum 4 32 51 177 228 514 613 1123 1286 2084
---------------------Ti1: 1 2 3 4 5 6 7 8
9 10
Num 12 10 76 34 204 74 396 130 652 202
Cum 13 23 99 133 337 411 807 937 1589 1791
---------------------TD10=2025
Vertex symbols for selected sublattice
-------------------------------------S1 Point (Schlafli) symbol:{4^3}
Extended point symbol:[4.4.4(3)]
-------------------------------------Sc1 Point (Schlafli) symbol:{4^3}
Extended point symbol:[4.4.4(3)]
-------------------------------------Ti1 Point (Schlafli) symbol:{4^20.6^28.8^18}
Extended
point
symbol:[4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2)
.6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(2).6(4).6(4).6(4).6(4).8(8).8(8).8(16).
8(16).8(16).8(16).8(20).8(20).8(20).8(20).8(20).8(20).8(20).8(20).8(32).8(32).8(32).8(32)]
-------------------------------------Point (Schlafli) symbol for net: {4^20.6^28.8^18}{4^3}4
3,12-c net with stoichiometry (3-c)4(12-c); 2-nodal net
Topological
type:
3,12T2
(binary.ttd)
{4^20.6^28.8^18}{4^3}4
VS
[4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.4.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6.6(3).6(3).6(3).
6(3).8(4).8(4).8(4).8(4).8(4).8(4).8(4).8(4).8(24).8(24).8(24).8(24).*.*.*.*.*.*] [4.4.4(3)] (71251
types in 10 databases)
Elapsed time: 4.13 sec.
The computed results of (3,12)-connected net of 1 by SYSTRE are as follows:
Structure of dimension 3.
Given space group is P-1.
5 nodes and 12 edges in repeat unit as given.
Given repeat unit is accurate.
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Point group has 16 elements.
2 kinds of node.
Equivalences for non-unique nodes:
2 --> 1
Coordination sequences:
Node 1:
3 28 19 126 51 286 99 510 163 798
Node 3:
12 10 76 34 204 74 396 130 652 202
TD10 = 2025.4000
Ideal space group is I4/mmm.
Ideal group differs from given (I4/mmm vs P-1).
Structure is new for this run.
Relaxed cell parameters:
a = 2.35870, b = 2.35870, c = 1.48972
alpha = 90.0000, beta = 90.0000, gamma = 90.0000
Cell volume: 8.28798
Relaxed positions:
Node 1:
0.30054 0.30054 0.00000
Node 3:
0.00000 0.00000 1.00000
Edges:
0.00000 0.00000 1.00000 <-> 0.19946 0.19946 0.50000
0.00000 0.00000 1.00000 <-> 0.30054 0.30054 1.00000
Edge centers:
0.09973 0.09973 0.75000
0.15027 0.15027 1.00000
Edge statistics: minimum = 0.99874, maximum = 1.00252, average = 1.00000
Angle statistics: minimum = 48.22758, maximum = 180.00000, average = 101.53846
Shortest non-bonded distance = 0.81762
Degrees of freedom: 3
References
1. Sheldrick, G. M. SHELXL-97, program for the refinement of the crystal
structures. University of Göttingen, Germany, 1997.
2. Dolomanov, O. V.; Blake, A. J.; Charmpness, N. R.; Schröder, M. J.; Appl.
Crystallogr., 2003, 36, 1283;
3. Blatov, V. A. ; 2007, http://www.topos.ssu.samara.ru/.
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