Nitrosonium hexachlorostannate
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 10, October, 2010
1923
were dried with Na2SO4. The solvent was evaporated and the
products were isolated by chromatography or recrystallization
and characterized spectrally by comparing with the literature
data.2,3,12,15
Xꢀray diffraction phase analysis was carried out on a DRONꢀ3
diffractometer (CuꢀKα radiation, graphite monochromator).
A sample was prepared in a dry box and covered with polystyꢀ
rene film to protect from moisture. The Xꢀray pattern obtained
corresponded completely to the theoretical one calculated for
(NO)2[SnCl6] on the basis of the singleꢀcrystal Xꢀray structure
analysis results.
Singleꢀcrystal Xꢀray diffraction analysis. Single crystals of
(NO)2[SnCl6] with sizes suitable for singleꢀcrystal Xꢀray analyꢀ
sis were obtained by the recrystallization of a small amount of
finely crystalline sample in a sealed glass ampule from a hot
solution in CCl4 (80 °С) with gradual cooling to room temperaꢀ
ture for 24 h. To protect from air moisture, single crystals of
(NO)2[SnCl6] were sampled under a Nujol layer using a polarꢀ
ization microscope. Singleꢀcrystal Xꢀray diffraction analysis was
carried out on an IPDS2 instrument (STOE) (MoꢀKα radiation,
λ = 0.71073 Å, graphite monochromator) at 100 2 K. The strucꢀ
ture of (NO)2[SnCl6] was solved by direct method and refined in
the anisotropic approximation for all atoms. The cation NO+ is
disordered over two positions with additional disordering beꢀ
tween the O and N atoms. The crystallographic data, main charꢀ
acteristics of diffraction experiment, and refinement parameters
for the structure of (NO)2[SnCl6] are presented in Table 1. The
crystallographic data were deposited with the Inorganic Crystal
Structure Database, FIZ Karlsruhe and NIST, Gaithersburg,
No. 421 052.
Experimental
The following reagents were used in the synthesis of
(NO)2[SnCl6]: NaNO2 (reagent grade), SnCl4 (reagent grade),
PCl5 (reagent grade), P2O5 (reagent grade), CCl4 (reagent
grade), and CH2Cl2 (reagent grade) distilled over P2O5. The
1Н NMR spectra of the isoxazolines (CDCl3) were recorded on
Varian XRꢀ400 and Bruker Avanceꢀ400 spectrometers with
a working frequency of 400 MHz (hexamethyldisiloxane was
used as an internal standard).
The starting arylcyclopropanes were synthesized by reducꢀ
tion of the corresponding 1ꢀarylꢀ2,2ꢀdichlorocyclopropanes13
or decomposition of the corresponding pyrazolines.14 Phosphoꢀ
rus oxotrichloride POCl3 was synthesized using the known proꢀ
cedure7 by the reaction of P2O5 with PCl5.
Nitrosonium hexachlorostannate was synthesized from NOCl
and SnCl4 under the conditions excluding contact of the reacꢀ
tants with air moisture. The controlled current of gaseous NOCl
was provided by heating a mixture of NaNO2 and POCl3 acꢀ
cording to the described procedure.7 Formed NOCl was fed into
a reactor cooled to 0 °C and containing a solution of tin tetraꢀ
chloride (5 mL) in dichloromethane (10 mL) with continuous
magnetic stirring. During the reaction the solution became turbid
because of (NO)2[SnCl6] precipitation. The reaction time was
1 h and the overall amount of gaseous NOCl passed through
the reactor within this time corresponded to the mole ratio
NOCl : SnCl4 = 4 : 1. After the end of the reaction, the solvent
was distilled off in vacuo. The yield was ∼96%.
Isoxazolines 2a—f (general procedure). Arylcyclopropane 1
(1.0 mmol) in CH2Cl2 (5 mL) was added with stirring to a susꢀ
pension of (NO)2[SnCl6] (0.5 mmol) in CH2Cl2 (20 mL) at 0 °С.
After the end of the reaction (the reaction course was monitored
by TLC), the reaction mixture was neutralized with a solution of
Na2CO3 and washed with water. Aqueous layers were extracted
with dichloromethane (3×10 mL) and the combined extracts
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 07ꢀ03ꢀ01142
and 08ꢀ03ꢀ00707ꢀa).
References
Table 1. Crystallographic characteristics, the diffraction experiꢀ
mental details, and refinement parameters for the structure of
(NO)2[SnCl6]
1. G. Desimony, G. Faita, Seminars in Organic Synthesis, 16th
Summer School "A. Corbella," (Milan, June 17—21, 1991),
Milan, 1991, p. 4.1.
2. K. Mizuno, N. Ichinose, T. Tamai, Y. Otsuji, J. Org. Chem.,
1992, 57, 4669.
Parameter
Value
3. O. B. Bondarenko, A. Yu. Gavrilova, L. G. Saginova, N. V.
Zyk, N. S. Zefirov, Zh. Org. Khim., 2009, 45, 230 [Russ. J.
Org. Chem. (Engl. Transl.), 2009, 45, 218].
4. V. N. Tikhanushkina, Ph. D. (Chem.) Thesis, Moscow Pedꢀ
agogical State University, Moscow, 2007 (in Russian).
5. H. Henke, Z. Kristallogr., 2002, 217, 474.
Molecular formula
Molecular weight
Crystal system
Space group
a/Å
Cl6N2O2Sn
391.44
Tetragonal
P4/mnc
6.922(1)
10.267(2)
491.9(1)
2
2.642
4.180
0.2×0.2×0.2
100(2)
28.4
3500/330
326
330/22
0.0535/0.1411
c/Å
V/Å3
6. H. Henke, Z. Kristallogr., 2003, 218, 617.
7. Praktikum po neorganicheskoi khimii [Practical Works on Inꢀ
organic Chemistry], Ed. Yu. D. Tret´yakov, Akademiya, Mosꢀ
cow, 2004, 384 pp. (in Russian).
8. Svoistva organicheskikh soedinenii [Properties of Organic Comꢀ
pounds], Ed. A. A. Potekhin, Khimiya, Leningrad, 1984, 518
pp. (in Russian).
9. A. Ellern, K. Seppelt, Z. Anorg. Allg. Chem., 2001, 627, 234.
10. H. Boysen, A. W. Hewat, Acta Crystallogr., Sect. B: Struct.
Sci., 1978, 34, 1412.
11. Inorganic Crystal Structure Database, FIZ Karlsruhe and NIST,
Z
dcalc/g cm–3
μ/mm–1
Crystal size/mm
Т/К
θ
max/deg
Number of measured/independent reflections
Number of reflections with F2 > 2σ(F2)
Number of refined reflections/parameters
R1/wR2