(η5-Cyclo-penta-dien-yl)(3-hydr-oxy-3-methyl-but-1-ynyl-k C 1)(triphenyl-phos-phine-kP)nickel(II): Novel O - H...π bonding in an organo-metallic mol-ecule

Article abstract of DOI:10.1107/S0108270107026522

In the title compound, [Ni(C5H5)(C5H7O)(C18H15P)], the mol-ecule adopts the expected half-sandwich structure with no unusual metal-ligand distances. No classical hydrogen bonds are found in the structure; instead, the OH group of the butynol unit is invol

Full text of DOI:10.1107/S0108270107026522

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
reveals 15 other nickel±alkynyl complexes (for example,
Whittall et al., 1998; Butler et al., 2005), together with an
akynylene (Gallagher et al., 2002) and a butadiynyl derivative
(Gallagher et al., 1998). In addition, a cluster system with
Co2(CO)6 coordinated to the C C group of a nickel±alkyne is
also known (Gallagher et al., 2002). Analysis of the principal
metal±ligand dimensions in these compounds using VISTA
(CCDC, 1994) shows that the Ni1ÐP1 and Ni1ÐC1 distances
and the P1ÐNi1ÐC1 angle (Table 1) compare reasonably well
ISSN 0108-2701
(g5-Cyclopentadienyl)(3-hydroxy-
3-methylbut-1-ynyl-jC1)(triphenyl-
phosphine-jP)nickel(II): novel
OÐHÁ Á Áp bonding in an organo-
metallic molecule
Ê
with the mean values [NiÐP = 2.139 (7) A, NiÐC =
ꢀ
Ê
1.844 (10) A and PÐNiÐC = 92 (3) ] found in the previously
reported complexes, excluding the Co2(CO)6 cluster. The
C1 C2 bond is similar to those in other nickel±alkynyl
Ê
complexes [mean C C = 1.203 (11) A]. These are somewhat
longer than the mean value of the corresponding distance for
C. John McAdam, Brian H. Robinson and Jim Simpson*
the 25 recorded structures containing the HOMe2CÐC
C
Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
Correspondence e-mail: jsimpson@alkali.otago.ac.nz
Ê
fragment, for which the mean C C bond is 1.193 (10) A. This
has previously been attibuted to delocalization of the ꢀ system
in the MÐC C fragment (Gallagher et al., 1998). Inter-
estingly, only one other HOMe2CÐC C structure is of a
metal±alkyne system, namely cis-(HOMe2CÐC C)2Pt-
(PPh3)2, in which the mean C C distance is much shorter at
Received 9 May 2007
Accepted 31 May 2007
Online 23 June 2007
In the title compound, [Ni(C5H5)(C5H7O)(C18H15P)], the
molecule adopts the expected half-sandwich structure with no
unusual metal±ligand distances. No classical hydrogen bonds
are found in the structure; instead, the OH group of the
butynol unit is involved in an unusual OÐHÁ Á Áꢀ interaction
with the C C group of an adjacent molecule. The crystal
structure is further stabilized by CÐHÁ Á ÁO and CÐHÁ Á Áꢀ
interactions, leading to an extensive network of spiral
columns.
Ê
1.16 A (Furlani et al., 1984). The Ni1ÐC1 C2 and C1 C2Ð
C3 angles each deviate somewhat from the mean NiÐC
angle [175.9 (17)ꢀ] in the other nickel complexes and the
CÐC angle [177.2 (18)ꢀ] in the other HOMe2CÐC
structures. This is likely to be a consequence of the formation
of inversion-related dimers involving an OÐHÁ Á Áꢀ interaction
with the alkyne C atoms, as outlined below.
An obvious feature of the packing in this molecule is the
complete absence of classical OÐHÁ Á ÁO hydrogen bonds,
despite the presence of an OH group in the molecule. This is
unusual, but not unprecedented (Steiner et al., 1996), for
alkynyl alcohols and stems from the involvement of the OH
C
C
C
Comment
The title compound, (I), was prepared by reaction of equi-
molar amounts of (ꢁ5-C5H5)Ni(PPh3)Br (Barnett, 1974) and
2-methylbut-3-yn-2-ol in Et3N at ambient temperature in the
presence of a CuI catalyst as a possible precursor to the
terminal alkyne complex (ꢁ5-C5H5)Ni(PPh3)C CH. Deriva-
tives of 2-methylbut-3-yn-2-ol are often used as an alternative
to alkylsilylacetylenes as precursors for the synthesis of
terminal alkynes (Crisp & Jiang, 1998). However, (I) proved
unstable under standard deprotection conditions, the butynol
group proving more robust than the metal centre of the
molecule, with only decomposition products isolated. We
report here the structure of this compound, which provides a
rare organometallic example of an OÐHÁ Á Áꢀ interaction in
the crystal structure.
The molecule of (I) has the expected half-sandwich struc-
ture, with the 3-hydroxy-3-methylbutynyl ligand ꢂ-bound to
the NiII atom (Fig. 1). A search of the Cambridge Structural
Database (CSD, Version 5.28 to January 2007; Allen, 2002)
Figure 1
The molecular structure of (I), showing the atom labels and 50%
probability displacement ellipsoids for non-H atoms.
m338 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107026522
Acta Cryst. (2007). C63, m338±m340

metal-organic compounds
Figure 2
Inversion-related dimers formed through a combination of CÐHÁ Á ÁO and OÐHÁ Á Áꢀ interactions are linked into undulating chains by an additional
C23ÐH23Á Á ÁO1ii interaction [symmetry code: (ii) x 1, y, z 1]. Hydrogen bonds and OÐHÁ Á Áꢀ interactions are shown as dashed lines.
remaining structures from the CSD search showing similar
interactions involved organic alkynyl alcohols and in all cases
Ê
with the HÁ Á ÁCg contact limited to 2.5 A the H atom is found
to be approximately equidistant from each C atom of the
Ê
alkyne. Extending the search to include contacts up to 3.0 A
revealed a further 42 hits but, as the HÁ Á ÁCg distance
increased, there was a trend towards close contact with only
one of the two alkyne C atoms (see, for example, Mondal et al.,
2004; Das et al., 2003).
Figure 3
The crystal packing of (I), showing spiral columns down the c axis.
In the crystal structure, the dimers (Fig. 2) are further linked
by a C23ÐH23Á Á ÁO1ii interaction [symmetry code: (ii) x 1,
y, z 1] to form chains along c (Table 2). The crystal packing
is completed by a C34ÐH34Á Á ÁCg1iii interaction [Cg1 is the
centroid of the C21±C26 benzene ring; symmetry code: (iii)
x + 1, y, z], which adds two additional molecules to the
inversion-related packing synthon. The CÐHÁ Á Áꢀ interactions
link adjacent columns in the crystal structure to form an
extensive columnar network down c (Fig. 3).
group in an unusual OÐHÁ Á Áꢀ interaction with the C1 C2
group. The contact places atom H1 of the OH group almost
equidistant from the C atoms of the C C bond [H1Á Á ÁC1i =
i
Ê
Ê
2.49 (5) A and H1Á Á ÁC2 = 2.45 (4) A; symmetry code: (i)
x + 1, y + 1, z + 1]. This interaction is further stabilized by
a C36ÐH36Á Á ÁO1i hydrogen bond involving a phenyl ring of
the triphenylphosphine ligand, giving a bifurcated arrange-
ment (Table 2) (Desiraju & Steiner, 1999). Complementary
bifurcated interactions involving two adjacent molecules
generate inversion-related dimers (Fig. 2).
Experimental
A solution of Ni(ꢁ5-C5H5)(PPh3)Br (0.466 g, 1 mmol), HOMe2CÐ
A search of the CSD for OÐHÁ Á Áꢀ interactions with
Ê
distances of less than 2.5 A between the H atom and Cg (the
C
CÐH (0.084 g, 1 mmol) and a catalytic amount of CuI (0.010 g,
mid-point of the C C bond) gave 15 examples. Three of these
involved organometallic compounds (Furlani et al., 1984;
Akita et al., 1997; Campbell et al., 2003) and another a zinc±
porphyrin coordination complex (Chen et al., 2005). However,
in each case, the OH group involved in similar interactions
with the alkyne came from either water or methanol solvent
molecules. This would appear, therefore, to be the ®rst
example of this type of intermolecular interaction between
two organometallic systems. OÐHÁ Á Áꢀ interactions of this
type were ®rst reported by Lin et al. (1982) and were subse-
quently con®rmed by a neutron study (Allen et al., 1996). They
are discussed in more detail by Desiraju & Steiner (1999). The
5 mol%) in triethylamine (30 ml) was stirred in the absence of light
for 4 h. The solvent was removed under reduced pressure and the
diethyl ether soluble portion puri®ed using column chromatography
(SiO2/CH2Cl2). Green blocks of (I) suitable for X-ray diffraction
were obtained by slow evaporation from CH2Cl2 layered with hexane.
1H NMR (300 MHz, CDCl3): ꢃ 7.7 (m, 6H, phenyl), 7.4 (m, 9H,
phenyl), 5.18 (s, 5H, cyclopentadiene), 0.94 (s, 6H, ±CMe2±). 13C
NMR (126 MHz, CDCl3): ꢃ 134.3 (phenyl ipso), 134.0, 128.2 (phenyl
o, m), 130.2 (phenyl p), 124.2 (C2), 92.4 (cyclopentadiene), 73.9 (d, J =
50 Hz, C1), 66.4 (C3), 31.9 (Me). 31P NMR (121 MHz, CDCl3): ꢃ 42.4.
IR [ꢄ(CC), cm 1]: 2107 (CH2Cl2). Microanalysis calculated for
C28H27NiOP: C 71.68, H 5.80, P 6.60%; found: C 71.60, H 5.95, P
6.32%. Eopx 0.78 V (CH2Cl2, 0.1 M TBAPF6, Pt, ired/iox 0.3).
ꢁ
Acta Cryst. (2007). C63, m338±m340
McAdam et al.
[Ni(C5H5)(C5H7O)(C18H15P)] m339

metal-organic compounds
Crystal data
structure: SHELXL97 (Sheldrick, 1997) and TITAN2000 (Hunter &
Simpson, 1999); molecular graphics: ORTEP-3 (Farrugia, 1997) and
Mercury (Bruno et al., 2002); software used to prepare material for
publication: SHELXL97, enCIFer (Allen et al., 2004), PLATON
(Spek, 2003) and PARST (Nardelli, 1995).
[Ni(C5H5)(C5H7O)(C18H15P)]
Mr = 469.18
Triclinic, P1
ꢇ = 94.490 (3)ꢀ
V = 1152.13 (18) A
Z = 2
3
Ê
Ê
a = 8.9097 (8) A
Mo Kꢅ radiation
1
Ê
b = 11.0904 (8) A
ꢈ = 0.93 mm
T = 85 (2) K
Ê
c = 12.7489 (14) A
ꢅ = 100.643 (5)ꢀ
ꢆ = 109.694 (4)ꢀ
0.28 Â 0.19 Â 0.10 mm
We thank the New Zealand Foundation for Research
Science and Technology for a Postdoctoral Fellowship to
CJM and the University of Otago for the purchase of the
diffractometer.
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
Tmin = 0.715, Tmax = 0.911
28022 measured re¯ections
7726 independent re¯ections
6277 re¯ections with I > 2ꢂ(I)
Rint = 0.046
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GA3055). Services for accessing these data are
described at the back of the journal.
Re®nement
R[F2 > 2ꢂ(F2)] = 0.060
wR(F2) = 0.186
S = 1.06
7726 re¯ections
286 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
References
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3
Ê
Áꢉmax = 2.45 e A
3
Ê
1.73 e A
Áꢉmin
=
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Table 1
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ꢀ
Ê
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Ni1ÐC1
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C1ÐC2
C2ÐC3
1.855 (2)
2.1253 (6)
1.208 (3)
1.485 (3)
C3ÐO1
C3ÐC4
C3ÐC5
O1ÐH1
1.440 (3)
1.533 (3)
1.531 (3)
0.77 (4)
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Hydrogen-bond geometry (A, ).
ꢀ
Ê
Cg1 is the centroid of the C21±C26 benzene ring.
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DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C36ÐH36Á Á ÁO1i
C23ÐH23Á Á ÁO1ii
C34ÐH34Á Á ÁCg1iii
0.95
0.95
0.95
2.59
2.56
2.63
3.389 (3)
3.475 (3)
3.460 (3)
142
161
147
Symmetry codes: (i) x ‡ 1; y ‡ 1; z ‡ 1; (ii) x 1; y; z 1; (iii) x ‡ 1; y; z.
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The hydroxyl H atom, H1, was located in a difference Fourier map
and re®ned freely with an isotropic displacement parameter. Other H
atoms were re®ned using a riding model, with CÐH distances of
Ê
Ê
0.95 A [Uiso(H) = 1.2Ueq(C)] for aromatic and 0.98 A [Uiso(H) =
1.5Ueq(C)] for methyl H atoms. A rotating group model was used for
the methyl groups. A number of high peaks were found in the ®nal
Ê
difference map, located less than 1.0 A from atom Ni1, but no
chemical signi®cance could be attached to them.
È
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Data collection: APEX2 (Bruker, 2004); cell re®nement: SAINT
(Bruker, 2004); data reduction: SAINT; program(s) used to solve
structure: SIR92 (Altomare et al., 1993); program(s) used to re®ne
ꢁ
m340 McAdam et al. [Ni(C5H5)(C5H7O)(C18H15P)]
Acta Cryst. (2007). C63, m338±m340