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1992) has been used in particular for intramolecular
addition of the corresponding alkyl (Kulicke et al.,
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ated on the other additional double bond. As a re-
sult of synthetic work in the free-radical cyclization of
1,6- and 1,7-enyne systems through silylation of the
triple bond with TTMS, the six-membered cyclic com-
pound, (E)-dimethyl 4-isopropyl-3-[tris(trimethylsilyl)-
silylmethylene]- 1,1-cyclohexanedicarboxylate, (2), has
been isolated in 51% yield as a colourless crystal with
a melting point of 356 (1) K.
MeOOC COOMe McOOC COOMe
+ HSi(SiMc3) 3 ~,
. . Si(SiMe3)3
Me/~Me M
(1) (2)
Acta Cryst. (1999). C55, 630-632
(E)-Dimethyl 4-isopropyl-3-[tris(trimethyl-
silyl)silylmethylene]-l,l-cyclohexanedi-
carboxylate
RODOLFOMORENO-FUQUEN, Luz MARINA JARAMILLO-
G6MEZ AND JAIME MART[N-FRANCO
Departamento de Quimica, Facultad de Ciencias, Universi-
dad del Valle, Apartado 25360, Santiago de Cali, Colombia.
E-mail: romoreno @ hypatia, univalle, edu. co
(Received 16 April 1998; accepted 21 October 1998)
Abstract
The title isomer carbocyclic compound, C23H48045i4,
was prepared by treatment of the 1,7-enyne sys-
tem dimethyl (4-methylpent-3-enyl)propanodioate with
tris(trimethylsilyl)silicon hydride in the presence of
azobisisobutyronitrile. The C~-----C distance is 1.335 (4) A,
the C==C--Si bond angle is 132.6 (2) ° and the C--
C==C--Si torsion angle is 6.2 (5) °. The E configuration
of the exocyclic double bond has been confirmed by the
present X-ray study.
Comment
Tris(trimethylsilyl)silane (TTMS) has emerged as an al-
ternative to the more common tri-n-butyltin hydride
in free-radical chain processes (Curran, 1988; Chat-
gilialoglu, 1992, 1995). The hydrosilylating ability of
© 1999 International Union of Crystallography
Printed in Great Britain - all rights reserved
No other compounds in which the bulky 'supersilyl'
(Me3Si)3Si group is bonded to the methylene exocyclic
double bond of the cyclohexane ring such as (2) are
available in the literature. The enol system formed
by 2,2-dimethyl-l-tris(trimethylsilyl)silylethanol (Frey
et al., 1994), compound (3), is however the most similar
one to compare with some parameters of the title
compound. Parameters of the title compound can also be
compared with 1-tris(trimethylsilyl)silyl-3,4,5,6-tetrakis-
(trimethylsilyl)cyclohex-l-ene (Puranik & Fink, 1994),
compound (4), where the supersilyl group is bonded
to an endocyclic double bond of the cyclohexene ring.
The crystal-structure determination of compound (2)
was undertaken to confirm the E configurations of the
exocyclic double bond. The Si--Si and C--Si distances
of the tris(trimethylsilyl)silane of the title compound
are close to the distances reported for the 'supersilyl'
(Me3Si)3Si group (Frey et al., 1994). The C1---C7
distance reveals the existence of a double bond. The
C7---Sil distance changes from 1.94,~, in compound
(3) and 1.904(3)A in compound (4) to 1.888(3)A
in the title compound. This difference suggests that
compounds (3) and (4) have more steric strains due to
the presence of large pendant groups in their structures.
The C1---C7--Sil angle is 133.2 ° in compound (3).
This value is close to the value found in the present
structure [132.6(2)°]. This relatively large bond angle
is likely to be due to the steric effects of the bulky
groups in both compounds. A torsion angle of 6.2 (5) °
for C6---C1--C7--Sil shows the E configuration of
compound (2). The cyclohexane backbone adopts a
chair conformation with 0 = 174 (1)° and ~ = 85 (1)°
(Cremer & Pople, 1975). The geminal carboethoxy
groups bonded to C5 of the cyclohexane ring are
oriented in such a way that the C=O groups maintain
Acta Co'stallographica Section C
ISSN 0108-2701 © 1999