metal-organic compounds
Ê
Ê
Table 1
Selected geometric parameters (A, ).
1.397 (3) A and C22ÐC23 = 1.419 (3) A] in the diene ligand
also support the assignment of a predominantly ꢁ-bound
diene ligand (Dahlmann et al., 2000; Devore et al., 1995). A
C20ÐC21ÐC22ÐC23 torsion angle of 0.6 (4)ꢁ re¯ects the
coplanarity of these atoms.
ꢁ
Ê
Cp is the centroid of the indenyl ®ve-membered ring.
TiÐN1
TiÐC1
TiÐC2
TiÐC3
TiÐC8
TiÐC9
TiÐC20
1.963 (2)
2.242 (2)
2.355 (2)
2.476 (2)
2.334 (2)
2.490 (2)
2.217 (2)
TiÐC21
TiÐC22
TiÐC23
C20ÐC21
C21ÐC22
C22ÐC23
2.295 (2)
2.295 (2)
2.233 (2)
1.416 (3)
1.397 (3)
1.419 (3)
Ê
The TiÐN distance of 1.963 (2) A compares well with those
t
in typical BuN constrained-geometry TiII complexes (Dahl-
mann et al., 2000; Devore et al., 1995), but is considerably
longer than in typical TiIV±amide complexes (Lappert et al.,
1980).
CpÐTiÐN1
N1ÐTiÐC20
N1ÐTiÐC23
110.40 (8)
99.09 (8)
99.33 (8)
C20ÐTiÐC23
C20ÐC21ÐC22
C21ÐC22ÐC23
86.82 (8)
125.7 (2)
126.1 (2)
Experimental
Me2Si(ꢀ5-2,3,4,6-Me4C9H2)(C4H7N)Ti(1,4-Ph2C4H4) was prepared
C12ÐC13ÐC14ÐC15
20.5 (2)
C20ÐC21ÐC22ÐC23
0.6 (4)
from the reaction of Me2Si(ꢀ5-2,3,4,6-Me4C9H2)(C4H7N)TiCl2 with
n
two equivalents of BuMgBr in the presence of one equivalent of
trans-1,4-diphenyl-1,3-butadiene in hexanes under inert atomos-
pheric conditions, using a similar procedure to that described
previously by Devore et al. (1995). The resulting dark-red solution
was stored at 238 K in a glove-box for 5 d, after which time dark
crystals of the title complex had formed. The selected crystal was
immersed in Paratone N oil and mounted on a thin glass ®ber in a
glove-box.
atoms on atoms C20±C23, as well as the methyl H atoms on C10 and
C11, were obtained from a difference Fourier map and re®ned
Ê
without constraints [CÐH = 0.93 (2)±1.02 (3) A]. Full data collection
details are in the relevant _special_details section of the archived CIF
and have also been reported elsewhere (Abboud et al., 1997).
Data collection: SMART (Bruker, 1998); cell re®nement: SMART
and SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker,
1998); program(s) used to solve structure: SHELXTL; program(s)
used to re®ne structure: SHELXTL; molecular graphics: SHELXTL;
software used to prepare material for publication: SHELXTL.
Crystal data
3
[Ti(C19H27NSi)(C16H14)]
Mr = 551.68
Monoclinic, P21/n
Dx = 1.249 Mg m
Mo Kꢂ radiation
Cell parameters from 4542
re¯ections
Ê
a = 11.0726 (6) A
ꢄ = 2.0±27.5ꢁ
ꢅ = 0.36 mm
T = 173 (2) K
KAA wishes to acknowledge the National Science Foun-
dation and the University of Florida for funding of the
purchase of the X-ray equipment.
Ê
b = 20.509 (1) A
1
Ê
c = 13.9311 (8) A
ꢃ = 112.020 (1)ꢁ
Ê
V = 2932.9 (3) A
Z = 4
3
Needle, black
0.19 Â 0.15 Â 0.09 mm
Data collection
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FR1316). Services for accessing these data are
described at the back of the journal.
Bruker SMART diffractometer
! scans
Absorption correction: analytical,
integration based on measured
indexed faces (SHELXTL; Shel-
drick, 1998)
6740 independent re¯ections
4070 re¯ections with I > 2ꢆ(I)
Rint = 0.055
ꢄ
max = 27.5ꢁ
h = 14 ! 13
k = 26 ! 15
l = 17 ! 18
Tmin = 0.931, Tmax = 0.973
20 107 measured re¯ections
References
Abboud, K. A., Ortiz, C. G., Palenik, R. C. & Palenik, G. J. (1997). Acta Cryst.
C53, 1322±1323.
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Dahlmann, M., Schottek, J., Frohlich, R., Kunz, D., Nissinen, M., Erker, G.,
Fink, G. & Kleinschmidt, R. (2000). J. Chem. Soc. Dalton Trans. pp. 1881±
1886.
Devore, D. D., Timmers, F. J., Hasha, D. L., Rosen, R. K., Marks, T. J., Deck,
P. A. & Stern, C. L. (1995). Organometallics, 14, 3132±3134.
Erker, G., Kruger, C. & Muller, G. (1985). Adv. Organomet. Chem. 24, 1±39.
Lappert, M. F., Power, P. P., Sanger, A. R. & Srivastava, R. R. (1980). Metal and
Metalloid Amides, pp. 472±475. West Sussex, England: Ellis Horwood.
McKnight, A. L. & Waymouth, R. M. (1998). Chem. Rev. 98, 2587±2598.
Sheldrick, G. M. (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison,
Wisconsin, USA.
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.044
wR(F2) = 0.103
S = 0.96
6740 re¯ections
383 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢆ2(Fo2) + (0.0458P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max = 0.007
3
Ê
Áꢇmax = 0.32 e A
3
Ê
0.31 e A
Áꢇmin
=
Ê
CÐH distances of 0.98 and 0.99 A were used for methyl and
Ê
secondary H atoms, respectively. A distance of 0.95 A was used for H
Stevens, J. C., Timmers, F. J., Wilson, D. R., Schmidt, G. F., Nickias, P. N.,
Rosen, R. K., Knight, G. W. & Lai, S. (1991). Eur. Pat. Appl. EP 416 815-A2.
Yasuda, H., Tatsumi, K. & Nakamura, A. (1985). Acc. Chem. Res. 18, 120±126.
atoms on Csp2 atoms. The H-atom displacement parameters were set
at 1.2Ueq (1.5Ueq for methyl H atoms) of the parent C atom. The H
ꢀ
Acta Cryst. (2001). C57, 1408±1409
Khalil A. Abboud et al.
[Ti(C19H27NSi)(C16H14)] 1409