Twelve-connected net with face-centered cubic topology: A coordination polymer based on [Cu12(μ4-SCH3) 6]6+ clusters and CN- linkers

Article abstract of DOI:10.1002/anie.200500290

(Chemical Equation Presented) Globular configuration: a microporous coordination polymer based on a dodecanuclear copper(I) cluster (picture: C black, Cu red, N blue, S yellow) as a twelve-connected node, was synthesized by a simultaneous redox, sulfurization, and self-assembly reaction under solvothermal conditions. The synthesis provides a model reaction to simulate the transformation of inorganic sulfur into organic sulfur.

Full text of DOI:10.1002/anie.200500290

Angewandte
Chemie
Topological Networks
Twelve-Connected Net with Face-Centered Cubic
Topology: A Coordination Polymer Based on
[Cu12(m4-SCH3)6]6+ Clusters and CNꢀ Linkers**
Dan Li,* Tao Wu, Xiao-Ping Zhou, Rui Zhou, and
Xiao-Chun Huang
In recent years, the analysis of topological networks of metal–
organic coordination polymers has been a topical area of
research in crystal engineering, not only as an important tool
for simplifying complicated supramolecular coordination
polymers, but also in the rational design of some functional
materials with unique properties.[1–3] Considerable effort has
been invested in the characterization and design of such
coordination polymers.[4] OꢀKeeffe et al. identified five reg-
ular nets, one quasiregular net, and fourteen semiregular
three-periodic nets by transitivity pqrs.[5] Of these nets, the
face-centered cubic net (fcu) is the only quasiregular net with
transitivity 1112, which exhibits the highest coordination
number (12). It has been suggested that among the numerous
topological nets, the most important and plausible targets for
designed synthesis are those with “simple, high-symmetry”
structures.[6] Although many coordination polymers with
different topological networks containing 3 ~ 8-connected
nodes are known,[7] synthetically prepared examples of
higher connected and higher symmetry nets, such as fcu,
have not been reported to date.
Significant interest has also arisen in organic and coordi-
nation chemistry for the design and synthesis of novel
coordination polymers with ligands generated in situ.[8] We
have previously reported[9] the reaction of CuSCN with
acetonitrile and methanol under solvothermal conditions,
which yielded
a novel 3D polymeric photolumines-
cent complex, {[Cu(m3-SCH3)2(CN)]2[Cu10(m3-SCH3)4(m4-
SCH3)2]}n, in which the methyl mercaptide is generated in
situ. The complex contains dodecanuclear copper(i) clusters,
which can be rationalized in terms of an a-Po simple cubic net
(pcu), by defining the decanuclear copper cluster [Cu10(m3-
SCH3)4(m4-SCH3)2] as a node and [Cu(m3-SCH3)2(CN)] as a
[*] Prof. Dr. D. Li, T. Wu, X.-P. Zhou, Dr. X.-C. Huang
Department of Chemistry, Shantou University
Shantou, Guangdong 515063 (P. R. China)
Fax: (+86)754-290—2767
E-mail: dli@stu.edu.cn
R. Zhou
Department of Chemistry, Medical College,
Shantou University
Shantou, Guangdong 515063 (P. R. China)
[**] This work was supported by the National Natural Science
Foundation of China (No. 29901004 and 20271031) and the Natural
Science Foundation of Guangdong Province of China (No. 021240).
Acknowledgment is also made to Dr. Nick Bampos of the Depart-
ment of Chemistry, University of Cambridge for proofreading the
manuscript prior to publication.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2005, 44, 4175 –4178
DOI: 10.1002/anie.200500290
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Communications
linker. In our ongoing research, we have found that the
bond angles and lengths are equal, and thus an ideal 32-face
polyhedron results: eight equilateral triangles and 24 isosceles
triangles (see Supporting Information).
A polymer [Cu13Cl13(SCH2CH2NH3)6·H2O]n containing
(Cu12S6) clusters with a similar globular configuration has
been previously reported[11a] in which the corresponding bond
angles and lengths in each cluster are non-equivalent, for
complex can also be obtained by reaction of Cu(NO3)2·3H2O
or Cu(CH3COO)2·2H2O and NaSCN in the presence of
acetonitrile and methanol under the same solvothermal
conditions (1408C). Interestingly, when the reaction temper-
ature was increased to 1608C, a very different product,
namely, [Cu12(m4-SCH3)6(CN)6]n·2H2O (1), was obtained in
low yield. This compound is very stable in air at ambient
temperature, and relatively insoluble in common solvents.
X-ray single-crystal analysis[10] revealed that the crystal
structure of 1 is composed of a 3D neutral microporous
framework based on the highly symmetrical, spherical
dodecanuclear copper(i) cluster [Cu12(m4-SCH3)6]6+ connected
by CNꢀ ligands and guest water molecules, with space group
ꢀ
example, Cu S bond lengths range from 2.221 to 2.300 ꢁ. In
this complex, ꢀSCH2CH2NH3 is a neutral ligand, and the
+
clusters act as 4-connected nodes linked by CuCl subunits and
chloride ions to form a 2D framework. In contrast, each
[Cu12(m4-SCH3)6]6+ unit in complex 1, which has higher
symmetry, is connected to twelve adjacent clusters by
twelve cyanide ions to give a 3D microporous supramolecular
framework (Figure 2). Approximately 20.3% of the crystal
volume is occupied by free water molecules with a volume of
about 748.1 ꢁ3 in each cell unit.
¯
Fm3m. The basic spherical unit (Figure 1) contains a cen-
Figure 2. The site of each Cu12S6 cluster in the cell unit.
Figure 1. Structure of the basic globular Cu12(SCH3)6(CN)6 unit with a
center of symmetry at the center of the S6 cage; hydrogen atoms are
omitted for clarity.
The 3D framework can be rationalized as a face-centered
cubic net (fcu) with Schlꢂfli symbol (32443656) by assigning the
dodecanuclear copper(i) cluster [Cu12(m4-SCH3)6]6+ as a node
and the CNꢀ ligand as a linker (Figure 3), in accordance with
the quasiregular net structure defined by OꢀKeeffe. In each
trosymmetric Cu12 cubo-octahedron, involving a regular
octahedron of sulfur atoms with each edge bridged by a
CuX unit (X = C or N) from the CNꢀ ligand. All methyl
groups point outwards. Three mutually perpendicular, copla-
nar, eight-membered Cu4S4 rings intersect at the sulfur atoms
to generate an globular configuration. Each CuI center lies in
a planar and trigonal coordination sphere and binds to two
bridging m4-SCH3 ligands and to one N or C atom of the CNꢀ
ꢀ
ꢀ
ꢀ
ligand (S Cu 2.2284(17), Cu X 1.889(15), C N 1.17(3) ꢁ, S-
Cu-S 127.1(2), S-Cu-X 116.44(12)8). The coordination envi-
ronment of all the sulfur atoms in m4 bridging mode is a
square-pyramidal CSCu4 unit, with one carbon atom at the
ꢀ
apex and four copper atoms in the equatorial plane. The C S
bond lengths are all 1.81(2) ꢁ, similar to those in other
mercaptanes.[11] While m2- and m3-thiolate bridging modes are
relatively common, symmetric m4-thiolates remain scarce.[11]
Three adjacent CuI atoms bridged by three sulfur atoms form
an equilateral triangle with a Cu···Cu distance of 2.987(2) ꢁ
that indicates a weak Cu···Cu interaction. The corresponding
Figure 3. The 3D, 12-connected augmented fcu topological network.
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Chemie
cooled to room temperature at a rate of 58Chꢀ1. Yellow cubic crystals
were obtained in 4.5% yield based on Cu(NO3)2·3H2O.
Elemental analysis (%) calcd for 1 (C12H22Cu12N6O2S6): H 1.79, C
11.65, N 6.79%; found: H 1.82, C 11.59, N 6.82%; IR (KBr, cmꢀ1):
2920s, 2825w, 2127s, 1418m, 1305m, 957s, 689w, 645m, 463w.
cell unit, the central node or the center of the central cluster is
located at (0.5, 0.5, 0.5), and the other adjacent twelve nodes
are located at the center of each edge of the cube, respectively
(Figure 2). Eight water molecules occupy the center of the
tetrahedron. The distance from the center of each spherical
pffiffi
unit to adjacent units is a/ 2 (10.918 ꢁ), and each spherical
unit resides at a crystallographic inversion center. To the best
of our knowledge, this is the first fcu topological network
observed in coordination polymers, and represents the highest
connected topology of any known coordination network.
Thermogravimetric analysis of 1 showed that the struc-
tural skeleton remains stable up to 1908C (see Supporting
Information). Initial loss of guest water molecules is followed
by the abrupt loss of organic components (CH3 and CN) from
190 to 2758C (found weight loss 21.9%, calcd 22.8%; see
Supporting Information).
Received: January 25, 2005
Revised: April 17, 2005
Published online: June 1, 2005
Keywords: cluster compounds · copper · S ligands ·
.
solvothermal synthesis · topological networks
[1] a) B. Moulton, M. J. Zaworotko, Chem. Rev. 2001, 101, 1629 –
1658; b) M. Eddaoudi, D. B. Moler, H.-L. Li, B. Chen, T. M.
Reineke, M. OꢀKeeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34,
319 – 330; c) P. J. Hagrman, D. Hagrman, J. Zubieta, Angew.
Chem. 1999, 111, 2798 – 2848; Angew. Chem. Int. Ed. 1999, 38,
2639 – 2684; d) S. R. Batten, R. Robson, Angew. Chem. 1998,
110, 1558 – 1595; Angew. Chem. Int. Ed. 1998, 37, 1460 – 1494.
[2] a) B. F. Abrahams, S. R. Batten, M. J. Grannas, H. Hamit, B. F.
Hoskins, R. Robson, Angew. Chem. 1999, 111, 1538 – 1540;
Angew. Chem. Int. Ed. 1999, 38, 1475 – 1477; b) B. F. Abrahams,
P. A. Jackson, R. Robson, Angew. Chem. 1998, 110, 2801 – 2804;
Angew. Chem. Int. Ed. 1998, 37, 2656 – 2659; c) L. Carlucci, G.
Ciani, D. M. Proserpio, S. Rizzato, Chem. Commun. 2001, 1198 –
1199; d) J.-C. Dai, X.-T. Wu, Z.-Y. Fu, S.-M. Hu, W.-X. Du, C.-P.
Cui, L.-M. Wu, H.-H. Zhang, R.-Q. Sun, Chem. Commun. 2002,
12- 13.
[3] a) L. Carlucci, G. Ciani, P. Macchi, D. M. Proserpio, Chem.
Commun. 1998, 1837- 1838; b) M. Eddaoudi, J. Kim, M.
OꢀKeeffe, O. M. Yaghi, J. Am. Chem. Soc. 2002, 124, 376 – 377;
c) T.-Y. Niu, X.-Q. Wang, A. J. Jacobson, Angew. Chem. 1999,
111, 2059 – 2062; Angew. Chem. Int. Ed. 1999, 38, 1934 – 1937;
d) S. A. Barnett, A. J. Blake, N. R. Champness, C. Wilson, Chem.
Commun. 2002, 1640 – 1641; e) B. Rather, B. Moulton, R. D. B.
Walsh, M. J. Zaworotko, Chem. Commun. 2002, 694 – 695; f) L.
Carlucci, N. Cozzi, G. Ciani, M. Moret, D. M. Proserpio, S.
Rizzato, Chem. Commun. 2002, 1354 – 1355; g) B. Moulton, H.
Abourahma, M. W. Bradner, J.-J. Lu, G. J. McManus, M. J.
Zaworotko, Chem. Commun. 2003, 1342 – 1343; h) S. Banfi, L.
Carlucci, E. Caruso, G. Ciani, D. M. Proserpio, Cryst. Growth
Des. 2004, 4, 29 – 32.
[4] a) R. M. Barrer, H. Villiger, Z. Kristallogr. 1969, 128, 352 – 370;
b) A. F. Wells, Three-Dimensional Nets and Polyhedra, Wiley,
New York, 1977; c) A. F. Wells, Further Studies of Three-
Dimensional Nets, Am. Crystallogr. Assoc. Monogr. 1979, No.
8; d) S. J. Chung, T. Hahn, W. E. Klee, Acta Crystallogr. Sect. A
1985, 40, 42 – 50; e) J. V. Smith, Chem. Rev. 1988, 88, 149 – 182;
f) D. E. Akporiaye, G. D. Price, Zeolites 1989, 9, 23 – 32; g) M.
OꢀKeeffe, Z. Kristallogr. 1991, 196, 21 – 37; h) M. OꢀKeeffe, Acta
Crystallogr. Sect. A 1992, 48, 670 – 673; i) M. OꢀKeeffe, Acta
Crystallogr. Sect. A 1995, 51, 916 – 920; j) M. OꢀKeeffe, N. E.
Brese, Acta Crystallogr. Sect. A 1992, 48, 663 – 669; k) O.
Delgado Friedrichs, A. W. M. Dress, D. H. Huson, J. Klinowsky,
A. L. Mackay, Nature 1999, 400, 644 – 647; l) O. Delgado Frie-
drichs, D. H. Huson, Discrete Comput. Geom. 2000, 4, 279 – 292.
[5] a) O. Delgado Friedrichs, M. OꢀKeeffe, O. M. Yaghi, Acta
Crystallogr. Sect. A 2003, 59, 22 – 27; b) O. Delgado Friedrichs,
M. OꢀKeeffe, O. M. Yaghi, Acta Crystallogr. Sect. A 2003, 59,
515 – 525.
Another interesting feature of 1 is the in situ generation of
ꢀ
SCH3 and CNꢀ ligands. We have previously shown that the
ꢀ
sulfur atom in SCH3 originates from SCNꢀ and the methyl
group from methanol rather than acetonitrile.[9] In an attempt
to understand the mechanism for the transformation of
inorganic sulfur into organic sulfur, we identified the follow-
ing experimental phenomena: 1) the colorless residual solu-
tion has a characteristically pungent smell and quickly
becomes green after the reactor is opened to air; this
indicates reduction of Cu2+ to Cu+ and production of
CH3SH or H2S in the reactions; 2) yellow a-CuSCN single
crystals and yellow S8 single crystals were found in the
residual solid in two analogous reactions.[12] Even though it
cannot be found in the present reactions, we assume that H2S
acts indirectly as the sulfurization reagent, which is generated
by the reaction of S with H2O, and which can then react with
CH3OH to form SCH3ꢀ. Possibly, S from the decomposition
of SCNꢀ and CuSCN from redox reaction of Cu2+ and SCNꢀ
are two important intermediates in the present reactions.
Moreover, it is likely that the frameworks of the two
complexes were determined by the reaction temperature.
The precise mechanism and the effect of the temperature on
the reactions warrant further investigation.
In conclusion, a novel microporous polymer containing a
face-centered cubic (fcu) topological network with the highest
connectivity, based on a dodecanuclear copper(i) cluster as a
twelve-connected node, was synthesized by a simultaneous
redox, sulfurization, and self-assembly reaction under solvo-
thermal conditions. The concept of using a cluster as a
building block to construct high-connectivity networks is
therefore feasible, and the reactions confirm the transforma-
tion of inorganic into organic sulfur. The result provides a new
avenue for designing and generating new solid-state materials
based on networks of high-coordinate nodes linked by
bridging ligands.
Experimental Section
1: A mixture of Cu(NO3)2·3H2O (0.241 g, 1.0 mmol), NaSCN (0.081 g,
1.0 mmol), methanol (5.0 mL), and acetonitrile (5.0 mL) was stirred
for 1 min in air, then transferred and sealed in a 25 mL teflon-lined
reactor, which was heated in an oven to 1608C for 72 h and then
[6] a) M. OꢀKeeffe, M. Eddaoudi, H.-L. Li, T. Reineke, O. M. Yaghi,
J. Solid State Chem. 2000, 152, 3 – 20; b) O. M. Yaghi, M.
OꢀKeeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, J. Kim,
Nature 2003, 423, 705 – 714.
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[7] a) R. J. Hill, D.-L. Long, M. S. Turvey, A. J. Blake, N. R.
Champness, P. Hubberstey, C. Wilson, M. Schrꢃder, Chem.
Commun. 2004, 1792 – 1793; b) J. U. Schutze, R. Eckhardt, R. D.
Fischer, D. C. Apperley, N. A. Davies, R. K. Harris, J. Organo-
met. Chem. 1997, 534, 187 – 194; c) S. M. F. Lo, S. S. Y. Chui,
L. Y. Shek, Z. Y. Lin, X. X. Zhan, G. H. Wen, I. D. Williams, J.
Am. Chem. Soc. 2000, 122, 6293 – 6294; d) D.-L. Long, A. J.
Blake, N. R. Champness, C. Wilson, M. Schrꢃder, Angew. Chem.
2001, 113, 2509 – 2513; Angew. Chem. Int. Ed. 2001, 40, 2444 –
2447; e) D.-L. Long, R. J. Hill, A. J. Blake, N. R. Champness, P.
Hubberstey, D. M. Proserpio, C. Wilson, M. Schrꢃder, Angew.
Chem. 2004, 116, 1887 – 1890; Angew. Chem. Int. Ed. 2004, 43,
1851 – 1854; f) L. Pan, H. Liu, X. Lei, X. Huang, D. H. Olson,
N. J. Turro, J. Li, Angew. Chem. 2003, 115, 560 – 564; Angew.
Chem. Int. Ed. 2003, 42, 542 – 546; g) Q. Fang, X. Shi, G. Wu, G.
Tian, G. Zhu, R. Wang, S. Qiu, J. Solid State Chem. 2003, 176, 1 –
4; h) B. Moulton, J.-J. Lu, R. Hajndl, S. Hariharan, M. J.
Zaworotko, Angew. Chem. 2002, 114, 2945 – 2948; Angew.
Chem. Int. Ed. 2002, 41, 2821 – 2824; i) G. J. McManus, Z.-Q.
Wang, M. J. Zaworotko, Cryst. Growth Des. 2004, 4, 11 – 13.
[8] a) E. C. Constable, Metals and Ligand Reactivity, VCH, Wein-
heim, 1996; b) R. A. Michelin, M. Mozzon, R. Bertani, Coord.
Chem. Rev. 1996, 147, 299 – 338; c) V. Y. Kukushkin, A. J. L.
Pombeiro, Chem. Rev. 2002, 102, 1771 – 1802; d) J.-P. Zhang, S.-
L. Zheng, X.-C. Huang, X.-M. Chen, Angew. Chem. 2004, 116,
208 – 211; Angew. Chem. Int. Ed. 2004, 43, 206 – 209; e) Z. P.
Demko, K. B. Sharpless, Angew. Chem. 2002, 114, 2214 – 2217;
Angew. Chem. Int. Ed. 2002, 41, 2110 – 2113; f) J.-K. Cheng, Y.-
G. Yao, J. Zhang, Z.-J. Li, Z.-W. Cai, X.-Y. Zhang, Z.-N. Chen,
Y.-B. Chen, Y. Kang, Y.-Y. Qin, Y.-H. Wen, J. Am. Chem. Soc.
2004, 126, 7796 – 7797.
[9] D. Li, T. Wu, Inorg. Chem. 2005, 44, 1175 – 1177.
[10] Crystal data for 1: C12H22Cu12N6O2S6, cubic, space group Fm3m
¯
(no. 225), Mr = 1237.20, a = 15.4410(19), b = 15.4410(19), c =
15.4410(19) ꢁ, a = b = g = 908, V= 3681.5(8) ꢁ3, Z = 4, 1calcd
=
2.232 gcmꢀ3, m = 7.137 mmꢀ1, F(000) = 2384, T= 296(2) K; R1 =
0.0634, wR2 = 0.1897 for all data. Data collection was performed
on a Bruker Smart Apex CCD diffractometer (MoKa radiation,
l = 0.71073 ꢁ) by using frames of 0.38 oscillation (4.56 ꢁ 2q ꢁ
508). The structure was solved by direct methods, and all non-
hydrogen atoms were subjected to anisotropic refinement by
full-matrix least-squares methods on F2 by using the SHELXTL
program.[13] The hydrogen atoms were generated geometrically.
[11] a) R. V. Parish, Z. Salehi, R. G. Pritchard, Angew. Chem. 1997,
109, 276 – 278; Angew. Chem. Int. Ed. Engl. 1997, 36, 251 – 253;
b) R. G. Pritchard, R. V. Parish, Z. Salehi, J. Chem. Soc. Dalton
Trans. 1999, 243 – 250; c) W.-P. Su, R. Cao, M.-C. Hong, J.-T.
Chen, J.-X. Lu, Chem. Commun. 1998, 1389 – 1340; d) Z. Salehi,
R. V. Parish, R. Z. Pritchard, J. Chem. Soc. Dalton Trans. 1997,
4241 – 4246; e) G. W. Adamson, N. A. Bell, H. M. M. Shearer,
Acta Crystallogr. Sect. B 1982, 38, 462 – 465; f) M. D. Janssen,
A. L. Spek, D. M. Grove, G. van Koten, J. Am. Chem. Soc. 1996,
118, 4081 – 4084.
[12] Heating a mixture of CuSO4, CH3CN, and CH3OH in a sealed
reactor at 1808C gave yellow single crystals of a-CuSCN (crystal
data at 293 K: orthorhombic, a = 7.2535(6), b = 6.6842(6), c =
11.0466(9) ꢁ, V= 535.58(8) ꢁ3). Heating a mixture of Cu-
(NO3)2·3H2O, NaSCN, CH3OH, and m-phenylenediacetonitrile
in a sealed reactor at 1808C gave pale yellow crystals of S8
(crystal data at 293 K: orthorhombic, a = 10.4612(10), b =
12.8619(12), c = 24.486(2) ꢁ, V= 3294.7(5) ꢁ3).
[13] G. M. Sheldrick, SHELXTL 6.10, Bruker Analytical Instrumen-
tation, Madison, Wisconsin, USA, 2000.
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