2-methyl-1-phenylsulfanyl-1,2-dicarba-closo-dodecaborane(1 2)

Article abstract of DOI:10.1107/S0108270102012982

Synthesis and characterization of 2-methyl-1-phenylsulfanyl-1,2-dicarba-closo-dodecaborane(12) was presented and its crystal structure was determined. Reaction of 1-Me-1,2-C₂B₁₀H₁₁ in diethyl ether with a solution of n-butyllithium in hexane, and a subsequent reaction with phenyl disulfide in diethyl ether resulted in a white solid. After purification, the solid was recrystallized from dichloromethane-n-hexane and pale yellow crystals of the title compound were obtained. Crystal structure revealed that the methyl and phenylsulfanyl groups were connected to the C atoms of the carborane cage. The C_cage-C_cage distance was found to be 1.708 (4) A.

Full text of DOI:10.1107/S0108270102012982

organic compounds
the B3ÐC1ÐS angle is signi®cantly smaller [113.19 (18)ꢀ]
than the B6ÐC1ÐS angle [122.48 (19)ꢀ], and the C13ÐC2Ð
C1ÐS torsion angle is 5.3 (3)ꢀ. Thus, the variation of the
C13ÐC2ÐX angles [116.8 (3)±121.7 (3)ꢀ; X is Ccage or B] is
less than that of the SÐC1ÐX angles. The contribution of the
phenylsulfanyl and methyl substituents on the cluster C atoms
to the C1ÐC2 bond is indicated by the bond distance of
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
2-Methyl-1-phenylsulfanyl-1,2-
dicarba-closo-dodecaborane(12)
Ê
1.708 (4) A.
Comparison of (I) with the relevant sul®do-substituted
È
monoanion [2-Me-1-S-C2B10H10] (Kivekas et al., 1999)
reveals two marked differences. The C1ÐC2 distance is
signi®cantly shorter in (I) than in the latter compound
Raikko Kivekas,a* Miquel Angles Flores,b Clara Vinasb and
Ä
È
Reijo Sillanpaac
ÈÈ
Ê
[1.792 (5) A], but the C1ÐS distance in (I) [1.784 (3) A] is
Ê
signi®cantly longer than in the latter compound [1.735 (4) A].
Ê
aDepartment of Chemistry, PO Box 55, FIN-00014 University of Helsinki, Finland,
b
Á
Institut de Ciencia de Materials de Barcelona, CSCI, Campus UAB, 08193 Bellaterra,
Spain, and cDepartment of Chemistry, University of Jyvaskyla, FIN-40351 Jyvaskyla,
È
È
È
È
Finland
Correspondence e-mail: raikko.kivekas@helsinki.fi
Received 8 May 2002
Accepted 18 July 2002
Online 21 August 2002
In the title o-carborane derivative, C9H18B10S, the methyl and
phenylsulfanyl groups are connected to the C atoms of the
Ê
carborane cage. The CcageÐCcage distance is 1.708 (4) A.
Comment
In 1,2-dicarba-closo-dodecaboranes, the CcageÐCcage (or C1Ð
C2) bond length is considerably in¯uenced by the number of
substituents and atom species connected to the cluster C
atoms. These distances are shortest for 1,2-H2 compounds
Ê Æ
Figure 1
A view of the structure of (I), with displacement ellipsoids at the 20%
probability level. H atoms are shown as small spheres of arbitrary radii.
Â
[1.57 (1)±1.634 (3) A; Subrtova et al., 1980; Novak et al., 1983],
while much longer distances [1.799 (3)±1.858 (5) A] are
Â
Ê
observed for 1,2-S2-substituted compounds (Llop et al., 2002;
Teixidor, Romerosa et al., 1990; Teixidor, VinÄas et al., 1990).
Continuing our studies of the elongation of the C1ÐC2
The observed C1ÐC2 distance in (I) is in line with our
earlier results obtained for neutral 1,2-disubstituted
o-carboranes. The distance is slightly longer than that in
È
distance caused by different Ccage substituents (Kivekas et al.,
1994, 1995, 1998; Sillanpaa et al., 1996), and in order to prepare
compounds with aliphatic C atoms connected to both cluster C
Ê
È È
È
atoms [1.670 (3) and 1.684 (6) A; Kivekas et al., 1998; Holbray
new ligands or ligand precursors for complexation, we have
now synthesized and characterized the title compound, (I),
and determined its crystal structure.
et al., 1993], but is much shorter than the corresponding
distance in 1,2-S2-substituted closo compounds [1.799 (3)±
Ê
1.858 (5) A; Llop et al., 2002; Teixidor, Romerosa et al., 1990;
Teixidor, VinÄas et al., 1990].
The C1ÐC2 distance in (I) is comparable with the corre-
Ê
sponding distance of 1.702 (6) A in 1-Me-2-PPh2-C2B10H10
È
(Kivekas et al., 1994), and indicates that the contribution of
one Me and one SPh substituent to the lengthening of the
C1ÐC2 distance is equivalent to that of one Me and one PPh2
substituent.
In (I), the phenylsulfanyl and methyl groups are connected
to the cluster C atoms of the 1,2-dicarba-closo-dodecaborane
moiety. The phenyl group is oriented away from atom B3 and,
in order to reduce the repulsion between the phenyl group and
the carborane cage, the S atom is moved slightly from its
idealized radial position towards atom B3. As a consequence,
Experimental
Reaction of 1-Me-1,2-C2B10H11 in diethyl ether with a solution of
n-butyllithium in hexane, and subsequent reaction with phenyl
disul®de in diethyl ether, resulted in a white solid. After puri®cation,
the solid was recrystallized from dichloromethane±n-hexane and
pale-yellow crystals of (I) were obtained. Full details of the synthesis,
o570 # 2002 International Union of Crystallography
DOI: 10.1107/S0108270102012982
Acta Cryst. (2002). C58, o570±o571

organic compounds
together with the spectral data and elemental analysis, are given in
the archived CIF.
The methyl group was re®ned as a rotating group, with CÐH =
Ê
0.96 A and Uiso(H) = 1.5Ueq(C). The other H atoms were re®ned
Ê
Ê
using a riding model, with BÐH = 1.10 A and CÐH = 0.93 A, and
with Uiso(H) = 1.2Ueq(B or C), starting from idealized positions.
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1995); cell re®nement: MSC/AFC
Diffractometer Control Software; data reduction: TEXSAN for
Windows (Molecular Structure Corporation, 1997); program(s) used
to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL/PC (Sheldrick, 1990b); software used to prepare material
for publication: SHELXL97.
Crystal data
3
C9H18B10S
Mr = 266.39
Dx = 1.162 Mg m
Mo Kꢁ radiation
Cell parameters from 25
re¯ections
Monoclinic, P21=n
Ê
a = 7.2391 (14) A
b = 17.2093 (11) A
ꢂ = 10.1±15.9ꢀ
ꢃ = 0.19 mm
T = 296 (2) K
Ê
1
Ê
c = 12.3461 (10) A
ꢀ = 98.066 (10)ꢀ
3
Ê
V = 1522.9 (3) A
Z = 4
Prism, pale yellow
0.38 Â 0.26 Â 0.24 mm
This work was supported by the Academy of Finland
(Project 41519, RK).
Data collection
Rigaku AFC-5S diffractometer
!/2ꢂ scans
Rint = 0.020
max = 25ꢀ
ꢂ
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FR1379). Services for accessing these data are
described at the back of the journal.
Absorption correction: scan
(North et al., 1968)
Tmin = 0.943, Tmax = 0.956
2906 measured re¯ections
2681 independent re¯ections
1708 re¯ections with I > 2ꢄ(I)
h = 0 ! 8
k = 0 ! 20
l = 14 ! 14
3 standard re¯ections
every 150 re¯ections
intensity decay: <1%
References
Re®nement
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Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.050
wR(F2) = 0.135
S = 1.03
2681 re¯ections
w = 1/[ꢄ2(Fo2) + (0.0544P)2
+ 0.4580P]
È
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Ä
È È
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Ê
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3
Ê
0.22 e A
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È È
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Ä
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ꢀ
Ê
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359.
SÐC1
1.784 (3)
1.778 (3)
1.708 (4)
1.726 (4)
C1ÐB4
C1ÐB5
C1ÐB6
C2ÐC13
1.718 (4)
1.702 (4)
1.717 (4)
1.513 (4)
SÐC14
C1ÐC2
C1ÐB3
Æ
Â
 Â
Ï
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X-ray Instruments Inc., Madison, Wisconsin, USA.
C14ÐSÐC1
C2ÐC1ÐS
B3ÐC1ÐS
B5ÐC1ÐS
B4ÐC1ÐS
B6ÐC1ÐS
104.33 (12)
119.59 (18)
113.19 (18)
124.1 (2)
117.93 (19)
122.48 (19)
C13ÐC2ÐC1
C13ÐC2ÐB3
C13ÐC2ÐB6
C13ÐC2ÐB7
C13ÐC2ÐB11
118.3 (2)
116.8 (3)
117.8 (3)
121.2 (3)
121.7 (3)
È
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È È
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Ä
Ä
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Æ
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Â
Â
Ï
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Â
Sanchez, E. (1990). J. Chem. Soc. Dalton Trans. pp. 525±529.
C13ÐC2ÐC1ÐS
C2ÐC1ÐSÐC14
5.3 (3)
90.4 (2)
C1ÐSÐC14ÐC15
C1ÐSÐC14ÐC19
99.0 (2)
84.2 (2)
Â
Teixidor, F., VinÄas, C., Rius, J., Miravitlles, C. & Casabo, J. (1990). Inorg. Chem.
29, 149±152.
ꢁ
Acta Cryst. (2002). C58, o570±o571
Raikko Kivekas et al.
C9H18B10
S
o571
È