oligomeric structure. Furthermore, based on the structure
formed, the linear arrangement of triiodide and iodide ions
stabilizes the oligomeric structure in the first dimension.
DMSO is an ambidentate ligand, and its bonding mode has
been well rationalized through Pearson’s concepts for the
hardness and softness of acids and bases. According to these
concepts, coordination occurs through sulfur (a soft donor)
with metal ions that are soft Lewis acids, and it occurs through
oxygen (a hard donor) with metal ions that are hard acids.12,16
Therefore, in the synthesis of complex 1, the Na+ ion (a hard
acid) prefers to coordinate to the oxygen atom of DMSO
instead of forming NaI because the Iꢀ ion is a soft Lewis
base.17
The crystals of 1 were filtered and dried in a vacuum. The yield
obtained was 0.762 g, 28%.
z Crystal data for 1: C30H90 10
Space group P63/m, a = 12.0292(4), b = 12.0292(3), c = 32.9777(7) A,
V = 4132.61(19) A3, Z = 2, dcalcd = 2.035 Mg mꢀ3, crystal size 0.35 ꢁ
0.15 ꢁ 0.08 mm3, T = 233(2) K, l = 0.71073 A, 16 891 reflections
collected, 2729 independent reflections (Rint = 0.0499), R1 = 0.0352
[I 4 2s(I)], wR2 = 0.0902 (all data), GOF = 1.081. CCDC 820376.
I
Na4O15S15, M = 2532.88, hexagonal,
1 R. A. Smaldone, R. S. Forgan, H. Furukawa, J. J. Gassensmith,
A. M. Z. Slawin, O. M. Yaghi and J. F. Stoddart, Angew. Chem.,
Int. Ed., 2010, 49, 8630.
2 (a) K. M. Fromm, Coord. Chem. Rev., 2008, 252, 856;
(b) M. P. Suh, Y. E. Cheon and E. Y. Lee, Coord. Chem. Rev.,
2008, 252, 1007.
3 (a) J.-M. Lehn, Supramolecular Chemistry: Concepts
and Perspectives, VCH, Weinheim, 1995; (b) S. Kitagawa and
S. Noro, Compr. Coord. Chem. II, 2004, 7, 231; (c) A. Y. Robin
and K. M. Fromm, Coord. Chem. Rev., 2006, 250, 2127.
4 A. K. Bar, R. Chakrabarty and P. S. Mukherjee, Inorg. Chem.,
2009, 48, 10880.
5 J. W. Steed and J. L. Atwood, Supramolecular Chemistry, Wiley,
United Kingdom, 2009.
6 A. W. Coleman, S. G. Bott, S. D. Morley, C. M. Means,
K. D. Robinson, H. Zhang and J. L. Atwood, Angew. Chem.,
Int. Ed. Engl., 1988, 27, 1361.
To obtain similar complexes to 1 with other hard acids, such
as a lithium ion (Li+), potassium ion (K+), rubidium ion
(Rb+) and cesium ion (Cs+), additional experiments were
conducted using similar conditions to the synthesis of 1.
Unfortunately, we did not obtain the complexes containing
these cations. However, by adding NaI to the final solutions of
these experiments and keeping the solution at 4 1C, 1 resulted.
This compound likely formed because K+ (138 pm),18 Rb+
(166 pm) and Cs+ (181 pm) have ionic radii greater than Na+
(102 pm) and because Li+ has an ionic radius (76 pm) smaller
than Na+. In other words, the intermediate ionic radius of the
Na+ ion is optimal for the self-assembly process. Similar
results have also been reported by Chen et al.19 for the
synthesis of 2D hybrid transition metal–alkali complexes,
where only the Na+ ion induces the organization.
7 CSD v5.32 Nov 2010+2 updates.
8 (a) M. Calligaris, Coord. Chem. Rev., 2004, 248, 351;
(b) M. Calligaris and O. Carugo, Coord. Chem. Rev., 1996, 153, 83.
9 (a) F. A. Cotton and R. Francis, J. Am. Chem. Soc., 1960, 82, 2986;
(b) M. J. Bennett, F. A. Cotton, D. L. Weaver, R. J. Williams and
W. H. Watson, Acta Crystallogr., 1967, 23, 788; (c) F. A. Cotton,
R. Francis and W. D. Horrocks, J. Phys. Chem., 1960, 64,
1534.
10 H. E. Gottlieb, V. Kotlyar and A. Nudelman, J. Org. Chem., 1997,
62, 7512.
In conclusion, a novel supramolecular compound with the
formula [Na4(DMSO)15][(I3)3(I)] has been synthesized. In this
structure, the sodium is hexacoordinated, and there is an
arrangement of two linearly alternating anions. Future work
within our group will focus on the application of this novel
compound and the collateral reactions in the synthesis.
We would like to acknowledge the financial support given
11 H. H. Szmant, in Chemistry of Dimethyl Sulfoxide, in Dimethyl
Sulfoxide, ed. S. W. Jacob, E. E. Rosenbaum and D. C. Wood,
Marcel Dekker Inc., New York, 1971, pp. 1–97.
12 K. Wakabayashi, Y. Maeda, K. Ozutsumi and H. Ohtaki, J. Mol.
Liq., 2004, 110, 43.
13 T. Megyes, I. Bako, T. Radnai, T. Grosz, T. Kosztolanyi, B. Mroz
´ ´ ´
and M. Probst, Chem. Phys., 2006, 321, 100.
14 (a) R. Kuhn, Angew. Chem., 1957, 17, 570; (b) R. Kuhn and
H. Trischmann, Justus Liebigs Ann. Chem., 1958, 611, 117;
(c) O. Knop, A. Linden, B. R. Vincent, S. C. Choi,
S. T. Cameron and R. J. Boyd, Can. J. Chem., 1989, 67,
1984; (d) S. G. Smith and S. Winstein, Tetrahedron, 1958, 3,
317.
15 N. Davidson and T. Carrington, J. Am. Chem. Soc., 1952, 74(24),
6277.
16 N. S. Panina and M. Calligaris, Inorg. Chim. Acta, 2002, 334, 165.
17 (a) R. G. Pearson, Inorg. Chem., 1988, 27, 734; (b) R. G. Pearson,
J. Am. Chem. Soc., 1985, 107, 6801.
by the Universidad Nacional de Colombia, Bogota.
´
Notes and references
y Synthesis of 1. NaOH powder (0.170 g, 4.24 mmol) was added
to a DMSO (11.010 g, 140.91 mmol) and distilled water (0.130 g,
7.20 mmol) solution. The mixture was ultrasonicated for 30 min, CH3I
(3.420 g, 24.09 mmol) was added, and ultrasonication was continued
for 1.5 h. The obtained yellow solution was maintained at 20 1C for
6 d, with continuous agitation. The color of the solution changed from
yellow to red, and a white precipitate formed. The precipitate was
filtered, washed with ethanol and identified as [(CH3)3SO]I (2)
(0.694 g, 13%) (see ESIz). The filtrate was kept refrigerated at 4 1C
for 8 d, where green crystals formed with metallic luster for 1.
18 R. D. Shannon, Acta Crystallogr., Sect. A: Cryst. Phys., Diffr.,
Theor. Gen. Crystallogr., 1976, A32, 751.
19 G. J. Chen, F. X. Gao, F. P. Huang, J. L. Tian, W. Gu, X. Liu,
S. P. Yan and D. Z. Liao, Cryst. Growth Des., 2009, 9, 2662.
c
7112 Chem. Commun., 2011, 47, 7110–7112
This journal is The Royal Society of Chemistry 2011