SUPRAMOLECULAR ENSEMBLES OF INDIUM THIOCYANATES
571
‡
·
5
10
15
20
25
30
35
40
45
θ, deg
2
Fig. 5. X-Ray diffraction patterns of the (a) product of synthesis 2 and (b) isolated single crystals K[K(18C6)] [In(NCS) ].
2
6
thesis 2 a deficient of the macrocycle in the reaction
medium results in the insertion of the free potassium
cation into the heterometallic chain binding the indium
and potassium cations by the NCS bridging group.
ACKNOWLEDGMENTS
This work was supported by the the Division of Chem-
istry and Materials Science (Program for Fundamental
Research, grant no. OKh2.17) and the Presidium of the
Russian Academy of Sciences (Program for Fundamental
Research, grant no. 18P13).
In spite of the seeming structural rigidity, the thiocy-
anate pseudooctahedral complexes are rather labile: the
InNC bond angles vary in two considered structures
from 147.4° to –175.6°. The structural diversity of the
REFERENCES
+
[
K(18C6)] cationic complex is described by one
1
. Ilyukhin, A.B. and Petrosyants, S.P., Koord. Khim.,
007, vol. 33, no. 4, p. 275 [Russ. J. Coord. Chem. (Engl.
Transl.), vol. 33, no. 4, p. 265].
parameter: the deviation of the potassium atom from
the root-mean-square plane of the oxygen atoms of the
crown ether. The combination of two structurally labile
fragments in the solution is a reason for the heterogene-
ity of the crystalline reaction products. The difference
in the solubility of the complexes can lead to the situa-
tion when the single crystal suitable for X-ray diffrac-
tion analysis gives an impurity product, and the hetero-
geneity of the finely crystalline phase does not allow
one to identify all reaction products.
2
2. Petrosyants, S.P. and Ilyukhin, A.B., Koord. Khim.,
2007, vol. 33, no. 10, p. 747 [Russ. J. Coord. Chem.
(
Engl. Transl.), vol. 33, no. 10, p. 734].
3. Ilyukhin, A.B., Dobrokhotova, Zh.V., and Petrosyants, S.P.,
Koord. Khim., 2008, vol 34, no. 9, p. 651 [Russ. J. Coord.
Chem. (Engl. Transl.), vol. 34, no. 9, p. 641].
. Petrosyants, S.P. and Ilyukhin, A.B., Koord. Khim.,
007, vol. 33, no. 3, p. 163 [Russ. J. Coord. Chem. (Engl.
Transl.), vol. 33, no. 3, p. 155].
4
2
Thus, the heterogeneous products are formed, as a rule,
in syntheses 1 and 2, when the [K(18C6)] cations are
present in the reaction solutions. The primary crystalliza-
5. SMART (control) and SAINT (integration) Software.
Version 5.0, Madison (WI, USA): Bruker AXS Inc.,
+
1
997.
6
7
8
9
. Sheldrick, G.M., SADABS. Program for Scaling and
Correction of Area Detector Data, Göttingen (Ger-
many): Univ. of Göttingen, 1997.
. Sheldrick, G.M., SHELXS-97. Program for the Solution
of Crystal Structures, Göttingen (Germany): Univ. of
Göttingen, 1997.
. Sheldrick, G.M., SHELXL-97. Program for the Refine-
ment of Crystal Structures,Göttingen (Germany): Univ.
of Göttingen, 1997.
tion of the hydrate [K(18C6)] [In(NCS) ] · 2H O is due,
3
6
2
most likely, to a lower solubility compared to that of the
[
K(18C6)] [In(NCS) ] complex, which is the major com-
3 6
ponent of the second crystallization. The heterometallic
polymeric fragments In–NCS–K are formed in the impu-
rity structures [K(18C6)] [In(MeOH)(NCS) ], and
2
5
K[K(18C6)] [In(NCS) ] due to the bridging function of the
2
6
NCS groups. It cannot be excluded that similar polymer
motifs are also observed in the structures
. Spek, A.L., J. Appl. Crystallogr., 2003, vol. 36, no. 1,
p. 7.
[
K(18C6)] [In(NCS) ] · 2H O and [K(18C6)] [In(NCS) ].
3
6
2
3
6
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 35 No. 8 2009