Crystal structure of bis(phenylethynyl)tetrakis(dimethylphenylphos-
phine)ruthenium(II), C
48
H
54
P
4
Ru
Frederick P. Malan, Eric Singleton and Reinout Meijboom
*
Research Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg, P. O Box 524, Auckland Park, 2006, Johannesburg,
South Africa
Received January 23, 2014, accepted May 15, 2014, available online May 28, 2014, CCDC no. 1267/4112
Abstract
C
48
H
54
P
4
Ru, triclinic, P1 (no. 2), a = 12.029(5) Å,
b = 13.439(5) Å, c = 14.582(7) Å, a = 79.962(17)°,
b = 80.974(18)°, g = 71.343(13)°, V = 2186.2 Å
3
, Z = 2,
R
gt
(F) = 0.0416, wR
ref
(F
2
) = 0.1067, T = 223 K.
Source of material
All reagents were obtained from Sigma-Aldrich and used without
fur ther pu ri fi ca tion. The pre cur sor com plex,
[RuH(PMe
2
Ph)
5
](PF
6
), was synthesised according to literature
procedures [3]. The latter complex (293 mg, 0.3 mmol) was re-
acted with 2.1 molar equivalents of phenylacetylene in boiling
MeOH in air. A clear light yellow solution was obtained from
which yellow prisms crystallized overnight (144 mg, 54%).
Experimental details
The aromatic H atoms were placed in geometrically idealized po-
sitions (C–H = 0.97 Å) and constrained to ride on their parent at-
oms, with U
iso
(H) = 1.2U
eq
(C) for all H atoms. The highest
calculated residual electron density is 0.56 e×Å
–3
at 1.54 Å from
C104, which bears no physical meaning.
Discussion
Ongoing research in s-alkynyl-metal complexes is stimulated by
their expanded use in nonlinear optics, luminescence, and liquid
crystalline materials brought about by their rigid linear structures,
intrinsic stability and unique p-electron configurations [4, 5]. As
seen in the figure, the Ru atom exhibits an slightly disordered oc-
tahedral geometry with P1–Ru1–P3 = 92.094(2)°, P1–Ru1–P4 =
91.702(2)°, P2–Ru1–P3 = 91.753(2)°, and P1–Ru1–C9 =
90.763(2)°. The two acetylide moieties are coordinated trans to
each other (C1–Ru1–C9 = 177.072(3)°), with the four remaining
PMe
2
Ph occupying the same plane. An average Ru–C and Ru–P
bond length of 2.07 Å and 2.38 Å, respectively are comparable to
the similar complex trans-[Ru(C
8
H
5
)
2
(PMe
3
)
4
] reported by Field
et al. [6].
Z. Kristallogr. NCS 229 (2014) xxx-xxx / DOI 10.1515/ncrs-2014-0109 1
© 2014 by Walter de Gruyter Berlin/Boston
Crystal: colourless prisms, size 0.2´0.2´0.2 mm
Wavelength: Mo K
a
radiation (0.71075 Å)
m: 5.37 cm
-1
Diffractometer, scan mode: Rigaku XtaLAB mini, w
2q
max
: 55.02°
N(hkl)
measured
, N(hkl)
unique
: 12594, 9760
Criterion for I
obs
, N(hkl)
gt
: I
obs
> 2 s(I
obs
), 8187
N(param)
refined
: 486
Programs: SHELX [1], OLEX2 [2]
Table 1. Data collection and handling.
_____________
* Correspondence author (e-mail: rmeijboom@uj.ac.za)
H(20A) 2i 0.9123 0.0791 0.5671 0.088
H(20B) 2i 1.0518 0.0384 0.5612 0.088
H(20C) 2i 0.9870 0.1546 0.5156 0.088
H(104) 2i 0.5769 0.1990 0.8425 0.067
H(7) 2i 0.5175 -0.1529 0.8213 0.080
H(30A) 2i 1.0203 0.1564 0.8807 0.083
H(30B) 2i 0.9686 0.2076 0.9743 0.083
H(30C) 2i 0.9950 0.2796 0.8804 0.083
H(20D) 2i 1.0009 0.0307 0.8172 0.078
H(20E) 2i 1.0666 -0.0295 0.7306 0.078
H(20F) 2i 0.9279 -0.0028 0.7531 0.078
H(208) 2i 1.0742 0.3090 0.7145 0.062
H(4) 2i 0.7193 -0.0188 0.5564 0.063
H(6) 2i 0.5637 -0.2362 0.6877 0.081
H(308) 2i 0.7689 0.0488 0.8580 0.058
H(205) 2i 1.4034 0.0383 0.6230 0.069
H(204) 2i 1.2166 0.0229 0.6262 0.060
H(306) 2i 0.7101 -0.0926 1.1197 0.084
H(8) 2i 0.5705 -0.0022 0.8227 0.061
H(206) 2i 1.4275 0.1852 0.6687 0.079
H(307) 2i 0.7290 -0.0922 0.9593 0.073
H(30D) 2i 0.7538 0.4189 0.9097 0.095
H(30E) 2i 0.7713 0.3408 1.0047 0.095
H(30F) 2i 0.6569 0.3625 0.9541 0.095
H(404) 2i 0.6715 0.2368 0.5407 0.081
H(5) 2i 0.6621 -0.1672 0.5552 0.080
Table 2. Atomic coordinates and displacement parameters (in Å
2
).
Atom Site x y z U
iso
Unauthenticated | 152.106.99.20
Download Date | 7/8/14 10:36 AM