Molecular complexes of octafluoronaphthalene with acyclic and heterocyclic sulfur-nitrogen compounds

Article abstract of DOI:10.1016/S0022-1139(02)00127-6

Mismatched molecular 1:1 complexes were prepared from C₁₀F₈ and sulfur diimides Ar-N=S=N-Ar 1 and Ar-N=S=N-SiMe₃ 2, 3 (1, 2: Ar = 2,6-dimethylphenyl; 3: Ar = phenyl). In the case of 2, the complexation is accompanied by th

Full text of DOI:10.1016/S0022-1139(02)00127-6

Journal of Fluorine Chemistry 116 (2002) 149±156
Molecular complexes of octa¯uoronaphthalene with acyclic and
heterocyclic sulfur±nitrogen compounds
a
a
b
b,*
È
Irina Yu. Bagryanskaya , Yuri V. Gatilov , Enno Lork , Rudiger Mews ,
Makhmut M. Shakirova, Paul G. Watsonb, Andrey V. Zibareva,1
aInstitute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Russia
bInstitute for Inorganic and Physical Chemistry, Bremen University, D-28334 Bremen, Germany
Received 28 February 2002; received in revised form 17 June 2002; accepted 17 June 2002
Abstract
Mismatched molecular 1:1 complexes were prepared from C10F8 and sulfur diimides Ar±N=S=N±Ar 1 and Ar±N=S=N±SiMe3 2, 3 (1, 2:
Ar ˆ 2,6±dimethylphenyl; 3: Ar ˆ phenyl). In the case of 2, the complexation is accompanied by the unexpected cyclization of 2 into 7-
methyl-2,1-benzisothiazole 4. The X-ray molecular structures of C10F8Á1, C10F8Á3 and C10F8 are presented; in C10F8Á4 the 7-methyl-2,1-
benzisothiazole 4 is highly disordered. The complexes provide very rare examples of markedly bent (C10F8Á1), polyheteroatom (C10F8Á3) and
heterocyclic (C10F8Á4) molecules involved in non-covalent arene-poly¯uoroarene p-stacking interactions.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Octa¯uoronaphthalene; Sulfur±nitrogen compounds; Molecular complexes; p-Stacking interactions; X-ray structure determination
1. Introduction
Ar±N=S=N±ArF sulfur diimide (Ar ˆ 2,6-dimethylphenyl,
ArF ˆ heptafluoronaphth-2-yl) [9] featuring an unusual
poly¯uoroaryl-poly¯uoroaryl p-stacking along with normal
aryl-poly¯uoroaryl interactions. This and other recent exam-
ples of poly¯uoroaryl-poly¯uoroaryl p-stacking in some
correspondingly substituted organometallics [14±17] are
in obvious contradiction to the established purely electro-
static interpretation [2,18] of the interactions under consid-
eration.
The present work deals with three novel mismatched
molecular complexes prepared from C10F8 and sulfurdii-
mides Ar±N=S=N±Ar 1 and Ar±N=S=N±SiMe3 2, 3 (1, 2:
Ar ˆ 2,6-dimethylphenyl; 3: Ar ˆ phenyl). In the reaction
with 2 the complexation is accompanied by an unexpected
cyclization of 2 into 7-methyl-2,1-benzoisothiazole 4. The
X-ray structures of the 1:1 complexes of C10F8 with 1 and 3
are reported, in C10F8Á4 the 7-methyl-2,1-benzisothiazole is
heavily disordered. For comparison, the structure of C10F8
was also determined.
Non-covalent p-stacking interactions between aromatic
and poly¯uoroaromatic groups [1±3], a special case of
non-covalent interactions between aromatic units that are
known to play a signi®cant role in determining the structures
and properties of molecular assemblies in biology, supramo-
lecular chemistry, and materials science [4±8] have been
extensively studied in recent years, leading to important new
possibilities in crystal engineering for the design of advanced
functional materials. Selected references are given in [9].
Normally, only geometrically matching planar carbocyclic
molecules are involved in arene-poly¯uoroarene interactions
[1±3], although a few mismatched 1:1 complexes, e.g. octa-
¯uoronaphthalene (OFN)/diphenylacetylene [10], OFN/
anthracene [11], OFN/phenanthrene [11], OFN/pyrene
[11], OFN/triphenylene [11], OFN/tetrathiofulvalene [12]
or hexa¯uorobenzene/trans-stilbene [13] are also reported.
Previously, we described a unique molecular complex
between octa¯uoronaphthalene and the tweezer-like (Z,Z)±
2. Results and discussion
* Corresponding author. Tel.: ‡49-421-218-3354;
fax: ‡49-421-218-4267.
The target complexes (Scheme 1) were prepared as single
crystals suitable for X-ray crystallography by co-crystal-
lization of the components from n-hexane.
E-mail addresses: mews@chemie.uni-bremen.de (R. Mews),
zibarev@nioch.nsc.ru (A.V. Zibarev).
1 Co-corresponding author. Fax: ‡7-3832-344-752.
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 2 ) 0 0 1 2 7 - 6

150
I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
Scheme 1.
Table 1 presents the crystal data and details of the
sites connected by rotation around a center of symmetry at
the middle of the C4aC8a bond. In the crystal; C10F8
molecules form chains along the c-axis with average short-
est FÁ Á ÁF distances of 255 pm. Reduced FÁ Á ÁH contacts are
not observed.
structure re®nements for C10F8Á1, C10F8Á3, C10F8Á4 and
C10F8. In Figs. 1±3, the molecular structures of C10F8Á1,
C10F8Á3 and C10F8, the interaction of the p-systems in
the crystal and relevant bond distances and bond angles
are shown. The complex C10F8Á1 displays face-to-face
p-stacking of the markedly bent (tweezer-like) molecule
1 with C10F8 (Fig. 1). The dihedral angle between the
planes of the hydrocarbon and ¯uorocarbon rings is about
98. Arene-poly¯uoroarene separation within the stacks is
ꢀ345 pm (the distance between the centers of the rings is
375 pm) compared with 377 pm for the lowest-temperature
phase of the benzene-hexa¯uorobenzene co-crystals [19]
and 369±377 pm for the naphthalene-octa¯uoronaphtha-
lene co-crystals [20]. Neither the Z,Z-con®guration nor
other essential geometrical parameters of the ¯exible
molecule 1 [21] are affected by this complexation. The
C10F8 molecules are disordered in a 79:21 ratio over two
In contrast to 1, in the case of the related compound 2
the complexation with C10F8 is accompanied by an unex-
pected ring closure to the heterocycle 4 (Scheme 1). In the
absence of C10F8, compound 2 [22] is stable with respect
to cyclization under the conditions employed. The same
complex C10F8Á4 was also obtained by thermal decomposi-
tion of the salt 5 (Scheme 1) in the presence of C10F8.
Additionally it was found that in the absence of external
‡
electrophiles (cf. [9]) the in situ generated Cs and
‡
K analogues of salt 5 also cyclized into compound 4 along
with decomposition to the parent ArNH2 (Scheme 2). The
relative amounts of the two products depend on the reaction
conditions.

I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
151
Table 1
Crystal data and structure refinement for C10F8, C10F8Á1, C10F8Á3, and C10F8Á4
C
10F8
C10F8Á1
C10F8Á3
C10F8Á4
Empirical formula
Formula weight
Temperature (K)
Wavelength (pm)
Crystal system
Space group
C10F8
C26H18F8N2S
542.48
243(2)
C19H14F8N2S Si
482.47
173(2)
C18H7F8NS
421.31
293(2)
272.10
203(2)
71.073
71.073
71.073
71.073
Monoclinic
P21/c
Monoclinic
C2/c
Triclinic
Monoclinic
P21/c
P
740.7(2)
Unit cell dimensions a (pm)
b pm)
1348.78(17)
492.90(12)
2003.7(3)
90
2792.7(6)
736.27(11)
1248.7(2)
90
753.87(5)
804.83(7)
1407.45(10)
90
1180.0(2)
1212.0(2)
96.620(10)
102.33(2)
98.57(2)
c (pm)
a (8)
b (8)
100.446(14)
90
113.199(15)
90
99.240(6)
90
g (8)
Volume (nm3)
Z
1.3100(4)
6
2.3599(7)
4
1.0114(4)
2
0.84287(11)
2
Density (calculated) (mg/m3)
Absorption coefficient (mmÀ1
F(0 0 0)
2.069
1.527
1.584
1.660
)
0.241
0.219
0.301
0.279
792
1104
488
420
0.8 Â 0.22 Â 0.16
2.74±24.99
Crystal size (mm3)
0.60 Â 0.50 Â 0.50
2.79±24.98
À16 ꢁ h ꢁ 1, À1 ꢁ
k ꢁ5, À23 ꢁ l ꢁ 23
3276
1.10 Â 0.70 Â 0.11
2.88±25.00
À32 ꢁ h ꢁ 30, 0
k ꢁ 8, 0 ꢁ l ꢁ 14
2187
1.00 Â 0.30 Â 0.05
2.66±24.99
À1 ꢁ h ꢁ 8, À13 ꢁ
k ꢁ 13, À14 ꢁ l ꢁ 14
4462
Theta range for data collection (8)
Index ranges
À7 ꢁ h ꢁ 8, À7 ꢁ k ꢁ 9,
À16 ꢁ l ꢁ 16
Reflections collected
1644
Independent reflections
2281 (R(int) ˆ 0.0218)
2078 (R(int) ˆ 0.0127)
100.0
3501 (R(int) ˆ 0.0216)
98.6
None
1470 (R(int) ˆ 0.0125)
Completeness to theta ˆ 24.998 (%) 99.0
99.3
None
Absorption correction
None
Integration
0.9761 and 0.8687
2078/19/206
1.037
Maximum and minimum transmission 0.8888 and 0.8687
0.9851 and 0.7531
3501/0/286
1.023
Data/restraints/parameters
Goodness-of-fit on F2
2281/0/245
1.024
1470/17/198
1.251
Final R indices (I > 2 sigma (I))
R indices (all data)
R1 ˆ 0.0483, wR2 ˆ 0.1315 R1 ˆ 0.0497, wR2 ˆ 0.1512 R1 ˆ 0.0461, wR2 ˆ 0.1069 R1 ˆ 0.0935, wR2 ˆ 0.3125
R1 ˆ 0.0710, wR2 ˆ 0.1488 R1 ˆ 0.0684, wR2 ˆ 0.1618 R1 ˆ 0.0724, wR2 ˆ 0.1188 R1 ˆ 0.1317, wR2 ˆ 0.3636
Extinction coefficient
Largest difference peak and
Ê À3
0.0032(17)
0.240 and ±0.225
0.0016(7)
0.246 and À0.195
0.0041(13)
0.223 and ±0.377
0.000(11)
0.247 and ±0.377
hole (e A
)
P
P
Details in common: refinement method full-matrix least-squares on F2o À 2y scans; Siemens P4 diffractometer; R1 ˆ 0jjFoj À jFcjj= 0 jFoj;
wR2ˆ
n
o1=2
, Programs SHELX-97 [28] and DIAMOND [29].
P
P
2
2
‰wꢂFo2 À Fc2† Š= ‰wꢂFo2† Š
The complex C10F8Á4 was also prepared from octa¯uor-
onaphthalene and 4 prepared by standard methods [23] by
co-crystallization from common organic solvents.
to see in the crystal packing the alternating layers of C10F8
and disordered 4 molecules with separation between the
layers of 345 pm implying [1±3] poly¯uoroarene±hetarene
p-stacking interactions. Thus, the C10F8Á4 complex is the
®rst example of a hydrocarbon ring-fused heterocycle
involved in such interactions (for the ®rst example of a
¯uorocarbon ring-fused heterocycle, see [9]).
In the case of 3, the parent compound of sulfur diimide 2,
the complexation with C10F8 is not accompanied by any
chemical transformations. According to the X-ray data
(Table 1) for the C10F8Á3 complex, the phenyl moiety of
the polyheteroatom (NSNSi fragment) molecule 3 in the Z,E
con®guration reveals face-to-face p-stacking with C10F8
(Fig. 2). The dihedral angle between the planes of the
hydrocarbon and ¯uorocarbon rings is 2.58. Arene-poly-
¯uoroarene separation within the stacks is 342 pm. In the
complex, the molecule 3 is virtually planar with the excep-
tion of the CH3 groups at the Si center. Molecule 3 is a liquid
under normal conditions [22]; the compound had not been
previously structurally characterized. The complex C10F8Á3
might be considered to be the ®rst example of an essentially
In the case of 2, the only example of a similar cyclization
has previously been observed for the reaction of ArN(Li)-
SiFMe2 (Ar ˆ 2,4,6-trimethylphenyl) with (Me3Si±N=)2S
to give the 5-methyl derivative of 4 via the corresponding
Ar±N=S=N±SiMe3 [24,25]. The cyclization of the anion
of 5 resembles the transformation of the isoelectronic
Ar±N=S=O containing an ortho-CH3 group into 2,1-ben-
zoisothiazoles in the presence of strong dehydrating agents
[23,26]. Thus, ortho-methylated ArNSX compounds (X=O,
NSiMe3, NÀ) demonstrate a general tendency to cyclize
into 2,1-benzisothiazoles, however, the driving force for
the unexpected C10F8 catalyzed transformation of 2 into
4 is not entirely clear. Among other reasons the crystal lattice
energy of C10F8Á4 might be responsible for this cyclization
(cf. melting points of C10F8Á4 76±77 8C and C10F8Á3 18±
19 8C).
The crystal structure of C10F8Á4 (Table 1) cannot
be completely solved due to disorder. However, it is possible

152
I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
Fig. 1. The structure of C10F8Á1 complex, showing ellipsoids at 50% probability. Within experimental accuracy bond lengths and bond angles are the same as
observed in 1 [21] and C10F8 (Fig. 3) crystals.
Fig. 2. The structure of C10F8Á3 complex, showing ellipsoids at 50% probability. Selected bond lengths (pm), bond and torsion angles (8) of molecule 3 (for
C
10F8, see Fig. 3): C4N1 140.7(3), N1S1 153.0(2), S1N2 152.2(2), N2Si1 176.8(2); C4N1S1 132.14(19), N1S1N2 119.93(12), S1N2Si1 120.42(14);
C4N1S1N2 0.0(3), N1S1N2Si1 177.75(15).

I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
153
Fig. 3. The molecular structure (ellipsoids at 50% probability) and crystal packing of C10F8. Selected bond lengths (pm) and bond angles (8): C1C2 141.1(4),
C2C3 135.6(4), C3C4 139.5(4), C1C6 143.2(4), C2F1 134.4(3), C3F2 133.7(3); C6C1C2 118.0(3), C1C2C3 121.4(3), C2C3C4 120.5(3).
polyheteroatom molecule involved in arene-poly¯uoroarene
p-stacking interactions.
The complexes C10F8Á1, C10F8Á3 and C10F8Á4 can be
sublimed without decomposition under static vacuum.
This was con®rmed by determination of the unit cell para-
meters.
The closest structural analogues of 2±4, i.e. the corre-
sponding Ar±N=S=O and 2,1,3-benzothiadiazole, respec-
tively, do not produce stable complexes with C10F8 under the
conditions of co-crystallization from hexane. The same is
also observed for C10F8 and 1,3,2,4-benzodithiadiazine [27],
a hetero-analogue of naphthalene.
The X-ray crystal structure of C10F8 has also been solved
for comparison (Table 1, Fig. 3; concurrently with us [9].
2
Batsanovand Collings also announced the crystal and
molecular structure of C10F8). In particular, it is obvious
(Fig. 3) that the crystal packing of C10F8 shows only a slight
overlapping of the p-systems, the shortest interactions
(309 pm) are the face-to-edge orientations of neighboring
molecules.
2 In ref. [11] a few structural details were briefly discussed, publication
of the complete structure determination was announced in ref. [10±12] as:
A.S. Batsanov, J.C. Collings, Acta Cryst. (2001) B57, in press.

154
I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
Scheme 2.
3. Conclusions
grams used: SHELX-97 [28] and DIAMOND [29]. The
structures were solved by direct methods (SHELXS) [28].
Subsequent least squares re®nement (SHELXL 97-2) [28]
located the positions of the remaining atoms in the electron
density maps. All non-H atoms were re®ned anisotropi-
cally.3
Suitable single crystals of pure C10F8 (from Novosibirsk
Institute of Organic Chemistry) were obtained by recrys-
tallization from EtOH (mp 85±86 8C). For C10F8Á4 it was not
possible to unequivocally interpret the difference peaks in
the area of molecule 4.
Three novel mismatched molecular complexes of octa-
¯uoronaphthalene have been prepared. Signi®cantly, they
provide very rare examples [9] of markedly bent (tweezer-
like), heterocyclic and polyheteroatom molecules involved
in non-covalent arene-poly¯uoroarene interactions. Since
most heterocycles are bioactive, one can speculate that
the ®ndings of this work might be of some interest for drug
design. As noted above, the alternating stacked aryl-poly-
¯uoroaryl arrangement is recognized to be a general supra-
molecular motif of signi®cant importance for new
developments in crystal engineering. In this and our previous
work [9], we introduced sulfur±nitrogen compounds, which
are also known to act as ligands in coordination chemistry,
into supramolecular chemistry. The combination of these
three aspects might be a new direction for future investiga-
tions.
The crystals were mounted using KEL-F oil on a thin
glass ®ber.
4.2. Preparation of the complexes by co-crystallization
Mixtures of 0.27 g (1 mmol) of C10F8 and 1 mmol of 1
[22] or 2 [22] were dissolved in 2 ml of boiling hexane.
While 1 is stable under these conditions, 2 undergoes an
intramolecular condensation to give 4. The solutions were
gradually cooled in a thermostat to 20 8C and the precipitate
was ®ltered off.
4. Experimental section
The 1H and 19F NMR spectra were recorded with a Bruker
DPX-200 spectrometer, 13C and 15N NMR spectra with a
Bruker DRX-500 spectrometer, at frequencies of 200.13,
188.28, 125.76 and 67.80 MHz, respectively. High-resolu-
tion mass spectra (EI, 70 eV) were measured with a Finnigan
MAT MS 8200 mass spectrometer. GC-MS measurements
were performed with a Hewlett-Packard G1800A GCD
device for solutions in CH2Cl2.
Complex C10F8Á1 forms transparent orange±yellow plates
(0.31 g, 57%), mp 78±79 8C. The composition and stoichio-
metry were con®rmed by GC-MS data. From a C10F8Á1
molar ratio of 2:1 also only the 1:1 complex was isolated.
Complex C10F8Á4 forms transparent yellow prisms
(0.40 g, 95%), mp 76±77 8C. The 1:1 stoichiometry was
1
con®rmed by GC-MS data. NMR d (CDCl3): H: 8.97 (s;
1H), 7.41 (d, J 8.5 Hz; 1H), 7.02 (d, J 6.5 Hz; 1H), 6.97 (t, J
4.1. Crystallographic analysis
3 Crystallographic data (excluding structure factors) for the structures
have been deposited with the Cambridge Crystallographic Data Centre as
supplementary publication nos. CCDC.177483 (C10F8Á1); 177727
(C10F8Á3); 177484 (C10F8Á4) and 177726 (C10F8). Copies of the data
can be obtained, free of charge, on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: ‡44-1223-336033 or e-mail:
deposit@ccdc.cam.ac.uk).
The single crystal X-ray structure determinations (Table 1)
were carried out on a Siemens P4 diffractometer using Mo Ka
(71.073 pm) radiation with a graphite monochromator using
P
y/2y scans. Re®nement based on F2; R1 ˆ 0jjFoj À jFcjj=
Pro-
n
o1=2
.
P
P
P
2
2
0 jFoj; wR2ˆ
‰wꢂFo2 À Fc2† Š= ‰wꢂFo2† Š

I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
155
8.5 Hz; 1H), 2.53 (s; 3H) (cf. 4 prepared by standard
Acknowledgements
methods [23]); 13C: 161.4, 144.0, 134.2, 130.7, 127.5,
124.1, 119.2, 16.8 (cf. 4 prepared by standard methods
[30]); 15N [NH3 (liquid)]: 267.4 (cf. 2,1-benzoisothiazole
[31]); 19F (CFCl3): À147.0, À155.7. Low-resolution MS
The authors are grateful to Mr. Peter Brackmann for
technical assistance, and to the Deutsche Forschungsge-
meinschaft (Germany) (Project 436 RUS 113/486/0±2 R)
and the Russian Foundation for Basic Research (Russia)
(Project 02±03±04001) for joint ®nancial support of this
work. Novosibirsk authors are also grateful to the RFBR
for an access to the Cambridge Structural Database
(grant 99±07±90133) and to the STN International data-
bases via STN Center at their Institute (grant 00±03±
32721).
‡
‡
(m/z): 272 (M , C10F8), 149 (M , 4). High-resolution MS
‡
(m/z): 149.0281 (M ; calculated for C8H7NS 149.0299).
Single crystals of C10F8Á4 suitable for X-ray crystallo-
graphy were obtained by slow evaporation (from 2 to
14 days) of solutions in various organic solvents (CHCl3,
CCl4, MeCN, cyclohexane, ethyl acetate, and 1,4-dioxane).
In all cases the same unit cell parameters were observed
suggesting the same disordering for all samples investi-
gated.
References
Complex C10F8Á3: A mixture of 0.27 g (1 mmol) of C10F8
and 0.21 g (1 mmol) of 3 [22] was dissolved in 5 ml of
hexane and kept at À45 8C for 3 days. At this temperature,
the solvent was removed with a syringe under a stream of
argon, and the crystals were dried in vacuum at the same
temperature. Complex C10F8Á3 was isolated as bright yellow
needle-like thin plates (0.38 g, 80%), mp 18±19 8C (dis-
sociation to the components).
[1] R. Filler, Mol. Struct. Energ. 8 (1988) 19.
[2] J.H. Williams, Acc. Chem. Res. 26 (1993) 593.
[3] T. Dahl, Acta Chem. Scand. 48 (1994) 95.
[4] C.A. Hunter, Angew. Chem. Int. Ed. Engl. 32 (1993) 1584;
C.A. Hunter, Chem. Soc. Rev. 23 (1994) 101.
[5] C.A. Hunter, K.R. Lawson, J. Perkins, C.J. Urch, Perkin Trans. 2
(2001) 651.
[6] K.R. Seddon, M. Zaworotko, Crystal Engineering. The Design and
Application of Functional Solids, Kluwer Academic Publishers,
Boston, MA, 1999.
4.3. Thermal decomposition of
tris(dimethylamino)sulfonium 2,6-dimethylphenylthiazyl-
amide 5 in the presence of octafluoronaphthalene
[7] D. Braga, F. Grepiany, A.G. Orpen, Crystal Engineering: From
Molecules and Crystals to Materials, Kluwer Academic Publishers,
Dordrecht, 1999.
[8] B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629.
[9] E. Lork, R. Mews, M.M. Shakirov, P.G. Watson, A.V. Zibarev, Eur. J.
Inorg. Chem. (2001) 2133.
Under nitrogen, 1.36 g (5 mmol) of C10F8 were added to a
stirred solution of 1.65 g (5 mmol) of salt 5 [32] in 15 ml of
MeCN at À40 8C. After 0.5 h at this temperature the solu-
tion turned in to a thick suspension. The solvent was distilled
off under high vacuum at ambient temperature. The residual
brown tar was extracted with a 5:1 mixture of hexane/Et2O,
the extract then evaporated under reduced pressure, and the
residue sublimed in static vacuum and recrystallized from
hexane. The C10F8Á4 complex, identical to that described
above, was obtained in 0.63 g (30%) yield. Neither com-
pound 6 (Scheme 1) nor its complex with C10F8 [9] are
observed.
[10] J.C. Collings, A.S. Batsanov, J.A.K. Howard, T.B. Marder, Acta
Cryst. C57 (2001) 870.
[11] J.C. Collings, K.P. Roscoe, R.L.I. Thomas, A.S. Batsanov, L.M.
Stimson, J.A.K. Howard, T.B. Marder, New J. Chem. 25 (2001)
1410.
[12] A.S. Batsanov, J.A.K. Howard, T.B. Marder, D.F. Perepichka, Acta
Cryst. C57 (2001) 1306.
[13] A.S. Batsanov, J.C. Collings, J.A.K. Howard, T.B. Marder, E.G.
Robins, Acta Cryst. C57 (2001) 1303.
[14] Y. Sun, W.E. Piers, M. Parvez, Can. J. Chem. 76 (1998) 513.
[15] P.A. Deck, M.J. Lane, J.L. Montgomery, C. Slebodnick, F.R.
Fronczek, Organometallics 19 (2000) 1013.
[16] M.P. Thornberry, C. Slebodnick, P.A. Deck, F.R. Fronczek,
Organometallics 19 (2000) 5352.
4.4. Decomposition of N-(2,6-dimethylphenyl)-N0-
(trimethylsilyl) sulfurdiimide (2) under the action of
CsF or KOBu-t
[17] M.D. Blanchard, R.P. Hughes, T.E. Concolino, A.L. Rheingold,
Chem. Mater. 12 (2000) 1604.
[18] A.P. West, S. Mecozzi, D.A. Dougherty, J. Phys. Org. Chem. 10
(1997) 347.
Under nitrogen, the salts Cs[ArNSN] (10 mmol in 30 ml
of MeCN) and [K(18-crown-6)] [ArNSN] (5 mmol in 30 ml
of THF) (Ar ˆ 2,6-dimethylphenyl), generated in situ from
compound 2 and CsF or [K(18-crown-6)][OBu-t], respec-
tively (detail will be given elsewhere [33]), were decom-
posed by re¯uxing (Cs salt, 1 h; K salt, 0.5 h). After the
usual work-up, the residue was trap-to-trap distilled under
vacuum to give a yellow±orange oil that consisted of a 2:1
[19] J.H. Williams, J.K. Cockroft, A.N. Fitsch, Angew. Chem. Int. Ed.
Engl. 31 (1992) 1655.
[20] J. Potenza, D. Mastropaolo, Acta Cryst. B 31 (1975) 2527.
[21] I.Yu. Bagryanskaya, Yu.V. Gatilov, M.M. Shakirov, A.V. Zibarev,
MendeleevCommun. (1994) 136.
[22] A.V. Zibarev, A.O. Miller, Y.V. Gatilov, G.G. Furin, Heteroatom
Chem. 1 (1990) 413.
‡
‡
[23] G.M. Singerman, J. Heterocycl. Chem. 12 (1975) 877.
[24] U. Klingebiel, D. Bentmann, Z. Naturforsch. B 34 (1979) 123.
È
[25] R. Bussas, G. Kresze, H. MuÈnsterer, A. Schwobel, Sulf. Rep. 2
‡
‡
(Cs salt) or 4:1 (K salt) mixture of 2,6-dimethylaniline
and 7-methyl-2,1-benzisothiazole (4). The yield of the oil
(1983) 215.
[26] D.L. Pain, B.J. Peart, K.R.H. Wooldrige, in: A.R. Katritzky, C.W.
Rees (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 6,
Pergamon Press, Oxford, 1984, pp. 132±175.
‡
is 95% (1.23 g) for the Cs salt, and 80% (0.50 g) for the
‡
K
salt.

156
I.Yu. Bagryanskaya et al. / Journal of Fluorine Chemistry 116 (2002) 149±156
[27] F. Blockhuys, S.L. Hinchley, A.Y. Makarov, Y.V. Gatilov, A.V.
Zibarev, J.D. Woollins, D.W.H. Rankin, Chem. Eur. J. 7 (2001) 3592.
È È
[28] G.M. Sheldrick, SHELX-97, University of Gottingen, Gottingen,
[30] N. Plavac, I.W. Still, M.S. Chauhan, D.M. McKinnon, Can. J. Chem.
53 (1975) 836.
[31] L. Stefaniak, Org. Magn. Reson. 11 (1978) 385.
[32] T. Borrmann, E. Lork, R. Mews, W.D. Stohrer, P.G. Watson, A.V.
Zibarev, Chem. Eur. J. 7 (2001) 3504.
Germany.
[29] DIAMONDÐVisual Crystal Structure Information System, Crystal
Impact, Bonn, Germany.
[33] E. Lork, R. Mews, A.V. Zibarev, to be published.