(2-Bromophenyl)diphenylphosphine

Article (PDF Available)inActa Crystallographica Section E Structure Reports Online 58(3) · March 2002with18 Reads
DOI: 10.1107/S1600536802002945 · Source: OAI
Abstract
The crystal structure of (2-bromophenyl)diphenylphosphine, C18H14BrP, (I), has been determined at 295 (1) K. The structure of (I) is isomorphous with the analogous methyl compound (2-methylphenyl)diphenylphosphine. Yes Yes
organic papers
o306 Michael L. Williams et al.
C
18
H
14
BrP DOI: 10.1107/S1600536802002945 Acta Cryst. (2002). E58, o306±o307
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
(2-Bromophenyl)diphenylphosphine
Michael L. Williams,
Cassandra L. Noack, Rodney J.
Saverin and Peter C. Healy*
School of Science, Griffith University, Nathan,
Brisbane 4111, Australia
Correspondence e-mail: p.healy@sct.g u.edu.au
Key indicators
Single-crystal X-ray study
T = 295 K
Mean (C±C) = 0.007 A
Ê
R factor = 0.043
wR factor = 0.150
Data-to-parameter ratio = 19.5
For details of how these key indicators were
automatically derived from the article, see
http://journals.iucr.org/e.
# 2002 International Union of Crystallography
Printed in Great Britain ± all rights reserved
The crystal structure of (2-bromophenyl)diphenylphosphine,
C
18
H
14
BrP, (I), has been determined at 295 (1) K. The
structure of (I) is isomorphous with the analogous methyl
compound (2-methylphenyl)diphenylphosphine.
Comment
(2-Bromophenyl)diphenylphosphine, (I), has been shown to
coordinate to metal centres as both a monodentate ligand
through the P-donor atom, and as a chelating hemilabile
ligand through both the phosphine and the aryl bromide
donor groups (Burk et al., 1988). The solid-state structure of
(I) is isomorphous with the structure reported for (2-methyl-
phenyl)diphenylphosphine, (II) (Bowmaker et al., 1987).
The structure consists of discrete molecular species which
adopt a propeller-shaped conformation with the phenyl rings
twisted away from the normal to the base of the PC
3
pyramid
by 36, 27 and 53
[cf. (II): 36, 26 and 47
]. The bromide is
located cis to the phosphorus lone pair. The PÐC bond
lengths [mean value 1.836 (6) A
Ê
] are similar to those recorded
for triphenylphosphine [mean value 1.831 (2) A
Ê
; Dunne &
Orpen, 1991], while the mean value of the CÐPÐC bond
angles, 101.9 (8)
, is marginally smaller than the value of
102.8 (5)
observed for triphenylphosphine. Introduction of
the bromo substituent on ring 1 in (I) results in a small
increase in the PÐC11ÐC12 angle to 119.8 (3)
compared to
117.1 (3) and 116.4 (3)
for PÐC21ÐC22 and PÐC31ÐC32.
The corresponding angles in triphenylphosphine are 116.6 (1),
116.8 (1) and 117.5 (1)
. The molecules are linked in the
crystal lattice through edge-to-face CÐH interactions
between the phenyl groups (Scudder & Dance, 1998). In
accord with previous studies demonstrating the poor
hydrogen-bond acceptor properties of X bonds (Aullo
Â
n et
al., 1998), there is no evidence of signi®cant CÐHBr
intermolecular interactions in (I), with the shortest HBr
distances being greater than 3.1 A
Ê
.
Received 6 February 2002
Accepted 12 February 2002
Online 22 February 2002
Experimental
The title compound was obtained as a white crystalline powder from
the PdCl
2
(CH
3
CN)
4
-catalysed reaction between ortho-bromoiodo-
benzene and diphenyl(trimethylsilyl)phosphine (Tunney et al., 1987);
m.p. 386±388 K. Crystals of the compound suitable for X-ray
diffraction studies were obtained during an attempt to recrystallize
the 1:2 copper(I) bromide complex by diffusion of ether into a
solution of the complex in dichloromethane.
Crystal data
C
18
H
14
BrP
M
r
= 341.16
Monoclinic, P2
1
=c
a = 10.371 (5) A
Ê
b = 8.9735 (19) A
Ê
c = 16.556 (6) A
Ê
= 92.33 (4)
V = 1539.5 (10) A
Ê
3
Z =4
D
x
= 1.472 Mg m
ÿ3
Mo K radiation
Cell parameters from 25
re¯ections
= 13.2±16.0
= 2.76 mm
ÿ1
T = 295 (1) K
Plate, colourless
0.40 0.30 0.20 mm
Data collection
Rigaku AFC-7R diffractometer
!±2 scans
Absorption correction: scan
(North et al., 1968)
T
min
= 0.383, T
max
= 0.576
4223 measured re¯ections
3540 independent re¯ections
1823 re¯ections with I >2(I)
R
int
= 0.033
max
= 27.5
h = ÿ13 ! 13
k = ÿ11 ! 0
l = ÿ12 ! 21
3 standard re¯ections
every 150 re¯ections
intensity decay: 0.8%
Re®nement
Re®nement on F
2
R[F
2
>2(F
2
)] = 0.043
wR(F
2
) = 0.150
S = 1.01
3540 re¯ections
182 parameters
H-atom parameters constrained
w = 1/[
2
(F
o
2
) + (0.0553P)
2
+ 1.0428P]
where P =(F
o
2
+2F
c
2
)/3
(/)
max
< 0.001
max
= 0.79 e A
Ê
ÿ3
min
= ÿ0.70 e A
Ê
ÿ3
Extinction correction: SHELXL97
Extinction coef®cient: 0.0033 (9)
Table 1
Selected geometric parameters (A
Ê
,
).
BrÐC12 1.905 (5)
PÐC11 1.844 (4)
PÐC21 1.833 (4)
PÐC31 1.832 (4)
C11ÐPÐC21 101.51 (18)
C11ÐPÐC31 101.32 (18)
C21ÐPÐC31 102.83 (16)
PÐC11ÐC12 119.8 (3)
PÐC11ÐC16 123.1 (3)
BrÐC12ÐC11 120.8 (3)
BrÐC12ÐC13 117.7 (3)
PÐC21ÐC22 117.2 (3)
PÐC21ÐC26 124.7 (3)
PÐC31ÐC32 116.4 (3)
PÐC31ÐC36 125.1 (3)
H atoms were located at calculated positions, with CÐH distances
set to 0.95 A
Ê
, and were constrained in re®nement.
Data collection: MSC/AFC-7 Diffractometer Control Software
(Molecular Structure Corporation, 1999); cell re®nement:
MSC/AFC-7 Diffractometer Control Software; data reduction:
TEXSAN for Windows (Molecular Structure Corporation, 2001);
program(s) used to solve structure: TEXSAN for Windows;
program(s) used to re®ne structure: TEXSAN for Windows and
SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3
(Farrugia, 1997); software used to prepare material for publication:
TEXSAN and PLATON (Spek, 2001).
References
Aullo
Â
n, G., Bellamy, D., Brammer, L., Bruton, E. A. & Orpen, A. G. (1998).
Chem. Commun. pp. 653±654.
Bowmaker, G. A., Engelhardt, L. M., Healy, P. C., Kildea, J. D., Papsergio, R. I
& White, A. H. (1987). Inorg. Chem. 26, 3533±3538.
Burk, M. J., Crabtree, R. H. & Holt, E. M. (1988). J. Organomet. Chem. 341,
495±509.
Dunne, B. J. & Orpen, A. G. (1991). Acta Cryst. C47, 345±347.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Molecular Structure Corporation (1999).MSC/AFC-7 Diffractometer Control
Software for Windows. Version 1.02. MSC, 9009 New Trails Drive, The
Woodlands, TX 77381, USA.
Molecular Structure Corporation (2001). TEXSAN for Windows. Version 1.06.
MSC, 9009 New Trails Drive, The Woodlands, TX 77381, USA.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351±
359.
Scudder, M. & Dance, I. (1998). J. Chem. Soc. Dalton Trans. pp. 3155±3165.
Sheldrick, G. M. (1997). SHELXL97. University of Go
È
ttingen, Germany.
Spek, A. L. (2001). PLATON for Windows. Version 121201. University of
Utrecht, The Netherlands.
Tunney, S. E. & Stille, J. K. (1987). J. Org. Chem. 52, 748±753.
Acta Cryst. (2002). E58, o306±o307 Michael L. Williams et al.
C
18
H
14
BrP o307
organic papers
Figure 1
ORTEP-3 (Farrugia, 1997) plot of the title compound, showing the atom-
numbering scheme. Displacement ellipsoids for non-H atoms are drawn
at the 30% probability level.
  • [Show abstract] [Hide abstract] ABSTRACT: 1,2-Dibromo-4,5-dimethoxybenzene was explored as a platform for the buildup of ditopic ligands. Low temperature reactions with n-butyllithium followed by quenches with various electrophiles led to the syntheses (2-bromo-4,5-dimethoxyphenyl)diphenylphosphine (1), (4,5-dimethoxy-2-(methylthio)phenyl)diphenylphosphine (2), 1,2-bis(diphenylphosphino)-4,5-dimethoxybenzene (3), and (2-(dicyclohexylboryl)-4,5-dimethoxyphenyl)diphenylphosphine (4). Oxidation of 3 produced 1,2-bis(diphenylphosphoryl)-4,5-dimethoxybenzene (5). All compounds were characterized by multinuclear (1H/13C/31P{1H}) NMR spectroscopy and by high resolution mass spectrometry. In addition, single crystal X-ray diffraction characterizations of 1, 3, 4, and 5 were also carried out. Reactivity of o-phosphinophenylborane 4 toward molecular hydrogen was also probed.
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