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Acta Cryst. (2007). C63, m338-m340
https://doi.org/10.1107/S0108270107026522
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(η5-Cyclo­penta­dien­yl)(3-hydr­oxy-3-methyl­but-1-ynyl-κC1)(triphenyl­phos­phine-κP)nickel(II): novel O—H...π bonding in an organo­metallic mol­ecule

C. J. McAdam, B. H. Robinson and J. Simpson
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 O—H...π inter­action with the C[triple bond]C group of an adjacent mol­ecule. The crystal structure is further stabilized by C—H...O and C—H...π inter­actions, leading to an extensive network of spiral columns.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107026522/ga3055sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107026522/ga3055Isup2.hkl
Contains datablock I

CCDC reference: 655497

Comment top

The title compound, (I), was prepared by reaction of equimolar amounts of (η5-C5H5)Ni(PPh3)Br (Barnett, 1974) and 2-methyl-3-butyn-2-ol in Et3N at ambient temperature in the presence of a CuI catalyst as a possible precursor to the terminal alkyne complex (η5-C5H5)Ni(PPh3)C≡CH. Derivatives of 2-methyl-3-butyn-2-ol are often used as an alternative to alkylsilyl acetylenes 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 O—H···π interaction in the crystal structure.

The molecule of (I) has the expected half-sandwich structure, with the 3-hydroxy-3-methylbutynyl ligand σ-bound to the NiII atom (Fig. 1). A search of the Cambridge Structural Database (CSD; Version 5.28 to January 2007; Allen, 2002) reveals 15 other nickel–alkynyl complexes (for example, Whittall et al., 1998; Butler et al., 2005), together with an akynyl-ene (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 Ni1—P1 and Ni1—C1 distances and the P1—Ni1—C1 angle (Table 1) compare reasonably well with the mean values [Ni—P = 2.139 (7) Å, Ni—C = 1.844 (10) Å and P—Ni—C = 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 complexes [mean C≡C = 1.203 (11) Å]. These are somewhat longer than the mean value of the corresponding distance for the 25 recorded structures containing the HOMe2C—C≡C for which the mean C≡C is 1.193 (10) Å. This has previously been attibuted to delocalization of the π system in the M—C≡C fragment (Gallagher et al., 1998). Interestingly, only one other HOMe2C—C≡C structure is of a metal alkyne system, namely cis(HOMe2C—C≡ C)2Pt(PPh3)2, in which the mean C≡C distance is much shorter at 1.169 Å (Furlani et al., 1984). The Ni1—C1≡C2 and C1≡ C2—C3 angles each deviate somewhat from the mean Ni—C≡C angle [175.9 (17)°] in the other nickel complexes and the C≡C—C angle [177.2 (18)°] in the other HOMe2C—C≡C structures. This is likely to be a consequence of the formation of inversion-related dimers involving an O—H···π interaction with the alkyne C atoms, as outlined below.

An obvious feature of the packing in this molecule is the complete absence of classical O—H···O 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 group in an unusual O—H···π interaction with the C1≡C2 entity. The contact places atom H1 of the OH group almost equidistant from the C atoms of the C≡C bond [H1···C1i = 2.49 (5) Å and H1···C2i = 2.45 (4) Å; symmetry code: (i) -x + 1, -y + 1, -z + 1). This interaction is further stabilized by a C36—H36···O1i hydrogen bond involving a phenyl ring of the triphenylphosphine ligand, giving a bifurcated arrangement (Table 2) (Desiraju & Steiner, 1999). Complementary bifurcated interactions involving two adjacent molecules generate inversion-related dimers (Fig. 2).

A search of the CSD for O—H···π interactions with distances of less than 2.5 Å between the H atom and Cg (the 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 O—H group involved in similar interactions with the alkyne came from either water or methanol solvates. This would appear, therefore, to be the first example of this type of intermolecular interaction between two organometallic systems. O—H···π interactions of this type were first reported by Lin et al. (1982) and were subsequently confirmed by a neutron study (Allen et al., 1996). They are discussed in more detail by Desiraju & Steiner (1999). The remaining structures from the CSD search showing similar interactions involved organic alkynyl alcohols and, in all cases with the H···Cg contact limited to 2.5 Å, the H atom is found to be approximately equidistant from each C atom of the alkyne. Extending the search to include contacts up to 3.0 Å revealed a further 42 hits but, as the H···Cg 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).

In the crystal structure, the dimers (Fig. 2) are further linked by a C23—H23···O1ii interaction [symmetry code: (ii) x - 1, y, z - 1] to form chains along c (Table 2). The crystal packing is completed by a C34—H34···Cg1iii 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 C—H···π interactions link adjacent columns in the crystal structure to form an extensive columnar network down c (Fig. 3).

Related literature top

For related literature, see: Akita et al. (1997); Allen (2002); Allen et al. (1996); Barnett (1974); Butler et al. (2005); CCDC (1994); Campbell et al. (2003); Chen et al. (2005); Crisp & Jiang (1998); Das et al. (2003); Desiraju & Steiner (1999); Furlani et al. (1984); Gallagher et al. (1998, 2002); Lin et al. (1982); Mondal et al. (2004); Steiner et al. (1996); Whittall et al. (1998).

Experimental top

A solution of Ni(η-5-C5H5)(PPh3)Br (0.466 g, 1 mmol), HOMe2C—C≡ C—H (0.084 g, 1 mmol) and a catalytic amount of CuI (0.010 g, 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 purified 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): δ 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): δ 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): δ 42.4. IR [ν(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%. Epox 0.78 V (CH2Cl2, 0.1 M TBAPF6, Pt, ired/iox 0.3).

Refinement top

The hydroxyl H atom, H1, was located in a difference Fourier map and refined freely with an isotropic displacement parameter. Other H atoms were refined using a riding model with C—H distances of 0.95 Å [Uiso(H) = 1.2Ueq(C)] for aromatic and 0.98 Å [Uiso(H) = 1.5Ueq(C)] for CH3 H atoms. A rotating group model was used for the methyl groups. A number of high peaks were found in the final difference map, located less than 1.0 Å from atom Ni1, but no chemical significance could be attached to them.

Structure description top

The title compound, (I), was prepared by reaction of equimolar amounts of (η5-C5H5)Ni(PPh3)Br (Barnett, 1974) and 2-methyl-3-butyn-2-ol in Et3N at ambient temperature in the presence of a CuI catalyst as a possible precursor to the terminal alkyne complex (η5-C5H5)Ni(PPh3)C≡CH. Derivatives of 2-methyl-3-butyn-2-ol are often used as an alternative to alkylsilyl acetylenes 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 O—H···π interaction in the crystal structure.

The molecule of (I) has the expected half-sandwich structure, with the 3-hydroxy-3-methylbutynyl ligand σ-bound to the NiII atom (Fig. 1). A search of the Cambridge Structural Database (CSD; Version 5.28 to January 2007; Allen, 2002) reveals 15 other nickel–alkynyl complexes (for example, Whittall et al., 1998; Butler et al., 2005), together with an akynyl-ene (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 Ni1—P1 and Ni1—C1 distances and the P1—Ni1—C1 angle (Table 1) compare reasonably well with the mean values [Ni—P = 2.139 (7) Å, Ni—C = 1.844 (10) Å and P—Ni—C = 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 complexes [mean C≡C = 1.203 (11) Å]. These are somewhat longer than the mean value of the corresponding distance for the 25 recorded structures containing the HOMe2C—C≡C for which the mean C≡C is 1.193 (10) Å. This has previously been attibuted to delocalization of the π system in the M—C≡C fragment (Gallagher et al., 1998). Interestingly, only one other HOMe2C—C≡C structure is of a metal alkyne system, namely cis(HOMe2C—C≡ C)2Pt(PPh3)2, in which the mean C≡C distance is much shorter at 1.169 Å (Furlani et al., 1984). The Ni1—C1≡C2 and C1≡ C2—C3 angles each deviate somewhat from the mean Ni—C≡C angle [175.9 (17)°] in the other nickel complexes and the C≡C—C angle [177.2 (18)°] in the other HOMe2C—C≡C structures. This is likely to be a consequence of the formation of inversion-related dimers involving an O—H···π interaction with the alkyne C atoms, as outlined below.

An obvious feature of the packing in this molecule is the complete absence of classical O—H···O 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 group in an unusual O—H···π interaction with the C1≡C2 entity. The contact places atom H1 of the OH group almost equidistant from the C atoms of the C≡C bond [H1···C1i = 2.49 (5) Å and H1···C2i = 2.45 (4) Å; symmetry code: (i) -x + 1, -y + 1, -z + 1). This interaction is further stabilized by a C36—H36···O1i hydrogen bond involving a phenyl ring of the triphenylphosphine ligand, giving a bifurcated arrangement (Table 2) (Desiraju & Steiner, 1999). Complementary bifurcated interactions involving two adjacent molecules generate inversion-related dimers (Fig. 2).

A search of the CSD for O—H···π interactions with distances of less than 2.5 Å between the H atom and Cg (the 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 O—H group involved in similar interactions with the alkyne came from either water or methanol solvates. This would appear, therefore, to be the first example of this type of intermolecular interaction between two organometallic systems. O—H···π interactions of this type were first reported by Lin et al. (1982) and were subsequently confirmed by a neutron study (Allen et al., 1996). They are discussed in more detail by Desiraju & Steiner (1999). The remaining structures from the CSD search showing similar interactions involved organic alkynyl alcohols and, in all cases with the H···Cg contact limited to 2.5 Å, the H atom is found to be approximately equidistant from each C atom of the alkyne. Extending the search to include contacts up to 3.0 Å revealed a further 42 hits but, as the H···Cg 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).

In the crystal structure, the dimers (Fig. 2) are further linked by a C23—H23···O1ii interaction [symmetry code: (ii) x - 1, y, z - 1] to form chains along c (Table 2). The crystal packing is completed by a C34—H34···Cg1iii 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 C—H···π interactions link adjacent columns in the crystal structure to form an extensive columnar network down c (Fig. 3).

For related literature, see: Akita et al. (1997); Allen (2002); Allen et al. (1996); Barnett (1974); Butler et al. (2005); CCDC (1994); Campbell et al. (2003); Chen et al. (2005); Crisp & Jiang (1998); Das et al. (2003); Desiraju & Steiner (1999); Furlani et al. (1984); Gallagher et al. (1998, 2002); Lin et al. (1982); Mondal et al. (2004); Steiner et al. (1996); Whittall et al. (1998).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. Inversion-related dimers formed through a combination of C—H···O and O—H···π interactions are linked into undulating chains by an additional C23—H23···O1ii interaction [symmetry code: (ii) x - 1, y, z - 1]. Hydrogen bonds and O—H···π interactions are shown as dashed lines.
[Figure 3] Fig. 3. The crystal packing of (I), showing spiral columns down the c axis.
(η5-Cyclopentadienyl)(3-hydroxy-3-methylbut-1-ynyl- κC1)(triphenylphosphine-κP)nickel(II) top
Crystal data top
[Ni(C5H5)(C5H7O)(C18H15P)]Z = 2
Mr = 469.18F(000) = 492
Triclinic, P1Dx = 1.352 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.9097 (8) ÅCell parameters from 6347 reflections
b = 11.0904 (8) Åθ = 2.3–32.4°
c = 12.7489 (14) ŵ = 0.93 mm−1
α = 100.643 (5)°T = 85 K
β = 109.694 (4)°Rectangular plate, green
γ = 94.490 (3)°0.28 × 0.19 × 0.10 mm
V = 1152.13 (18) Å3
Data collection top
Bruker APEX II CCD area-detector
diffractometer		7726 independent reflections
Radiation source: fine-focus sealed tube6277 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
φ and ω scansθmax = 34.4°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −12→14
Tmin = 0.715, Tmax = 0.911k = −16→15
28022 measured reflectionsl = −19→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.1339P)2 + 0.207P]
where P = (Fo2 + 2Fc2)/3
7726 reflections(Δ/σ)max = 0.001
286 parametersΔρmax = 2.45 e Å−3
0 restraintsΔρmin = −1.73 e Å−3
Crystal data top
[Ni(C5H5)(C5H7O)(C18H15P)]γ = 94.490 (3)°
Mr = 469.18V = 1152.13 (18) Å3
Triclinic, P1Z = 2
a = 8.9097 (8) ÅMo Kα radiation
b = 11.0904 (8) ŵ = 0.93 mm−1
c = 12.7489 (14) ÅT = 85 K
α = 100.643 (5)°0.28 × 0.19 × 0.10 mm
β = 109.694 (4)°
Data collection top
Bruker APEX II CCD area-detector
diffractometer		7726 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		6277 reflections with I > 2σ(I)
Tmin = 0.715, Tmax = 0.911Rint = 0.046
28022 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.186H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 2.45 e Å−3
7726 reflectionsΔρmin = −1.73 e Å−3
286 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.00183 (3)0.45924 (2)0.28343 (2)0.01420 (10)
C10.1783 (3)0.41027 (19)0.38395 (18)0.0171 (4)
C20.2950 (3)0.3709 (2)0.43907 (18)0.0179 (4)
C30.4289 (3)0.3062 (2)0.49585 (18)0.0189 (4)
O10.5384 (2)0.38328 (16)0.60236 (14)0.0209 (3)
H10.584 (5)0.438 (4)0.590 (3)0.043 (10)*
C40.3608 (3)0.1937 (2)0.5288 (2)0.0249 (5)
H4A0.44730.14580.55840.037*
H4B0.27580.14120.46120.037*
H4C0.31590.22210.58780.037*
C50.5204 (3)0.2676 (3)0.4158 (2)0.0275 (5)
H5A0.56530.34150.39820.041*
H5B0.44640.21210.34490.041*
H5C0.60820.22430.45310.041*
C11−0.0306 (3)0.6143 (2)0.38877 (19)0.0221 (4)
H110.00930.62690.46970.027*
C12−0.1853 (3)0.5531 (2)0.31481 (19)0.0214 (4)
H12−0.27070.52250.33620.026*
C13−0.1877 (3)0.5463 (2)0.20206 (19)0.0188 (4)
H13−0.27260.50300.13400.023*
C14−0.0408 (3)0.6157 (2)0.2073 (2)0.0204 (4)
H14−0.01530.63200.14420.024*
C150.0568 (3)0.6543 (2)0.3222 (2)0.0221 (4)
H150.16290.69950.35140.027*
P1−0.01647 (6)0.28870 (5)0.16853 (4)0.01307 (12)
C21−0.1898 (2)0.23487 (19)0.03469 (17)0.0148 (4)
C22−0.2246 (2)0.3098 (2)−0.04507 (18)0.0173 (4)
H22−0.16460.3904−0.02620.021*
C23−0.3464 (3)0.2671 (2)−0.15174 (18)0.0205 (4)
H23−0.36790.3178−0.20600.025*
C24−0.4365 (3)0.1499 (2)−0.17882 (19)0.0220 (4)
H24−0.51960.1209−0.25160.026*
C25−0.4059 (3)0.0753 (2)−0.10029 (19)0.0215 (4)
H25−0.4683−0.0044−0.11880.026*
C26−0.2827 (3)0.1178 (2)0.00634 (18)0.0177 (4)
H26−0.26170.06670.06020.021*
C310.1473 (2)0.29096 (18)0.11290 (17)0.0146 (4)
C320.1464 (3)0.1984 (2)0.02203 (18)0.0175 (4)
H320.06160.1299−0.01000.021*
C330.2701 (3)0.2064 (2)−0.02186 (19)0.0195 (4)
H330.26910.1432−0.08370.023*
C340.3938 (3)0.3058 (2)0.02441 (19)0.0210 (4)
H340.47870.3104−0.00460.025*
C350.3933 (3)0.3990 (2)0.1138 (2)0.0224 (4)
H350.47760.46790.14500.027*
C360.2706 (3)0.3921 (2)0.15750 (18)0.0186 (4)
H360.27070.45650.21810.022*
C41−0.0134 (2)0.15683 (18)0.23507 (17)0.0147 (4)
C420.0757 (3)0.06126 (19)0.22151 (18)0.0176 (4)
H420.14400.06500.17850.021*
C430.0651 (3)−0.0395 (2)0.27061 (19)0.0217 (4)
H430.1258−0.10450.26070.026*
C44−0.0343 (3)−0.0456 (2)0.3343 (2)0.0231 (4)
H44−0.0422−0.11500.36710.028*
C45−0.1218 (3)0.0503 (2)0.34955 (19)0.0222 (4)
H45−0.18870.04690.39360.027*
C46−0.1117 (3)0.1509 (2)0.30057 (19)0.0194 (4)
H46−0.17160.21620.31140.023*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01316 (15)0.01514 (16)0.01567 (15)0.00533 (10)0.00734 (11)0.00128 (10)
C10.0178 (9)0.0161 (9)0.0177 (9)0.0025 (7)0.0083 (7)0.0009 (7)
C20.0166 (9)0.0189 (9)0.0175 (9)0.0035 (7)0.0069 (7)0.0011 (7)
C30.0172 (9)0.0212 (9)0.0170 (9)0.0046 (8)0.0048 (7)0.0029 (7)
O10.0170 (7)0.0236 (8)0.0186 (7)0.0008 (6)0.0030 (6)0.0039 (6)
C40.0255 (11)0.0213 (10)0.0248 (11)0.0034 (9)0.0039 (9)0.0074 (8)
C50.0243 (11)0.0354 (13)0.0267 (11)0.0145 (10)0.0126 (9)0.0057 (9)
C110.0320 (12)0.0178 (9)0.0183 (10)0.0115 (9)0.0112 (9)0.0011 (7)
C120.0216 (10)0.0241 (10)0.0246 (10)0.0110 (8)0.0151 (8)0.0042 (8)
C130.0153 (9)0.0224 (10)0.0217 (10)0.0088 (8)0.0091 (8)0.0052 (8)
C140.0193 (10)0.0205 (10)0.0283 (11)0.0086 (8)0.0146 (8)0.0089 (8)
C150.0182 (9)0.0161 (9)0.0316 (12)0.0061 (8)0.0088 (9)0.0032 (8)
P10.0117 (2)0.0141 (2)0.0148 (2)0.00389 (18)0.00696 (18)0.00163 (17)
C210.0123 (8)0.0182 (9)0.0160 (9)0.0047 (7)0.0086 (7)0.0016 (7)
C220.0142 (8)0.0221 (10)0.0184 (9)0.0047 (7)0.0088 (7)0.0050 (7)
C230.0180 (9)0.0282 (11)0.0179 (9)0.0062 (8)0.0085 (8)0.0067 (8)
C240.0164 (9)0.0293 (11)0.0178 (9)0.0037 (8)0.0055 (8)0.0001 (8)
C250.0182 (9)0.0211 (10)0.0220 (10)0.0013 (8)0.0061 (8)−0.0004 (8)
C260.0151 (9)0.0196 (9)0.0185 (9)0.0031 (7)0.0068 (7)0.0026 (7)
C310.0141 (8)0.0158 (8)0.0156 (8)0.0059 (7)0.0076 (7)0.0018 (7)
C320.0177 (9)0.0177 (9)0.0194 (9)0.0058 (7)0.0106 (7)0.0004 (7)
C330.0195 (10)0.0221 (10)0.0220 (10)0.0081 (8)0.0138 (8)0.0030 (8)
C340.0165 (9)0.0256 (10)0.0254 (10)0.0073 (8)0.0131 (8)0.0048 (8)
C350.0140 (9)0.0265 (11)0.0272 (11)0.0018 (8)0.0112 (8)0.0006 (9)
C360.0142 (9)0.0223 (10)0.0197 (9)0.0034 (8)0.0088 (7)0.0002 (7)
C410.0154 (8)0.0141 (8)0.0152 (8)0.0025 (7)0.0069 (7)0.0021 (6)
C420.0188 (9)0.0178 (9)0.0176 (9)0.0052 (8)0.0087 (7)0.0024 (7)
C430.0245 (11)0.0179 (9)0.0230 (10)0.0074 (8)0.0089 (9)0.0031 (8)
C440.0291 (11)0.0179 (9)0.0227 (10)0.0027 (9)0.0100 (9)0.0048 (8)
C450.0251 (11)0.0226 (10)0.0233 (10)0.0028 (9)0.0143 (9)0.0056 (8)
C460.0213 (10)0.0187 (9)0.0217 (10)0.0063 (8)0.0119 (8)0.0036 (7)
Geometric parameters (Å, º) top
Ni1—C11.855 (2)C21—C221.400 (3)
Ni1—C132.075 (2)C22—C231.392 (3)
Ni1—C112.081 (2)C22—H220.9500
Ni1—C152.108 (2)C23—C241.391 (3)
Ni1—P12.1253 (6)C23—H230.9500
Ni1—C142.138 (2)C24—C251.386 (3)
Ni1—C122.143 (2)C24—H240.9500
C1—C21.208 (3)C25—C261.397 (3)
C2—C31.485 (3)C25—H250.9500
C3—O11.440 (3)C26—H260.9500
C3—C41.533 (3)C31—C361.392 (3)
C3—C51.531 (3)C31—C321.396 (3)
O1—H10.77 (4)C32—C331.397 (3)
C4—H4A0.9800C32—H320.9500
C4—H4B0.9800C33—C341.382 (3)
C4—H4C0.9800C33—H330.9500
C5—H5A0.9800C34—C351.391 (3)
C5—H5B0.9800C34—H340.9500
C5—H5C0.9800C35—C361.388 (3)
C11—C121.411 (3)C35—H350.9500
C11—C151.433 (3)C36—H360.9500
C11—H110.9500C41—C421.393 (3)
C12—C131.418 (3)C41—C461.405 (3)
C12—H120.9500C42—C431.389 (3)
C13—C141.440 (3)C42—H420.9500
C13—H130.9500C43—C441.394 (3)
C14—C151.391 (3)C43—H430.9500
C14—H140.9500C44—C451.390 (3)
C15—H150.9500C44—H440.9500
P1—C411.819 (2)C45—C461.386 (3)
P1—C311.825 (2)C45—H450.9500
P1—C211.832 (2)C46—H460.9500
C21—C261.399 (3)
C1—Ni1—C13167.17 (9)C14—C15—C11108.1 (2)
C1—Ni1—C11101.20 (9)C14—C15—Ni172.07 (13)
C13—Ni1—C1165.98 (9)C11—C15—Ni168.98 (12)
C1—Ni1—C15104.11 (9)C14—C15—H15125.9
C13—Ni1—C1566.01 (9)C11—C15—H15125.9
C11—Ni1—C1540.02 (9)Ni1—C15—H15124.6
C1—Ni1—P186.12 (6)C41—P1—C31108.21 (9)
C13—Ni1—P1106.62 (6)C41—P1—C21102.17 (9)
C11—Ni1—P1168.12 (8)C31—P1—C21100.12 (9)
C15—Ni1—P1147.29 (7)C41—P1—Ni1112.27 (7)
C1—Ni1—C14135.76 (9)C31—P1—Ni1111.33 (7)
C13—Ni1—C1439.94 (9)C21—P1—Ni1121.43 (7)
C11—Ni1—C1465.63 (9)C26—C21—C22118.75 (19)
C15—Ni1—C1438.24 (9)C26—C21—P1122.07 (16)
P1—Ni1—C14115.31 (6)C22—C21—P1119.05 (15)
C1—Ni1—C12130.30 (9)C23—C22—C21120.5 (2)
C13—Ni1—C1239.26 (8)C23—C22—H22119.7
C11—Ni1—C1239.01 (9)C21—C22—H22119.7
C15—Ni1—C1266.06 (9)C24—C23—C22119.9 (2)
P1—Ni1—C12129.49 (7)C24—C23—H23120.1
C14—Ni1—C1265.88 (9)C22—C23—H23120.1
C2—C1—Ni1172.94 (18)C25—C24—C23120.4 (2)
C1—C2—C3172.3 (2)C25—C24—H24119.8
O1—C3—C2111.68 (18)C23—C24—H24119.8
O1—C3—C5109.83 (19)C24—C25—C26119.6 (2)
C2—C3—C5109.55 (18)C24—C25—H25120.2
O1—C3—C4104.86 (18)C26—C25—H25120.2
C2—C3—C4109.50 (19)C25—C26—C21120.8 (2)
C5—C3—C4111.4 (2)C25—C26—H26119.6
C3—O1—H1109 (3)C21—C26—H26119.6
C3—C4—H4A109.5C36—C31—C32119.29 (19)
C3—C4—H4B109.5C36—C31—P1118.81 (14)
H4A—C4—H4B109.5C32—C31—P1121.76 (16)
C3—C4—H4C109.5C31—C32—C33120.1 (2)
H4A—C4—H4C109.5C31—C32—H32119.9
H4B—C4—H4C109.5C33—C32—H32119.9
C3—C5—H5A109.5C34—C33—C32120.22 (19)
C3—C5—H5B109.5C34—C33—H33119.9
H5A—C5—H5B109.5C32—C33—H33119.9
C3—C5—H5C109.5C33—C34—C35119.7 (2)
H5A—C5—H5C109.5C33—C34—H34120.2
H5B—C5—H5C109.5C35—C34—H34120.2
C12—C11—C15109.1 (2)C36—C35—C34120.4 (2)
C12—C11—Ni172.86 (12)C36—C35—H35119.8
C15—C11—Ni171.00 (12)C34—C35—H35119.8
C12—C11—H11125.5C35—C36—C31120.22 (19)
C15—C11—H11125.5C35—C36—H36119.9
Ni1—C11—H11122.3C31—C36—H36119.9
C11—C12—C13106.2 (2)C42—C41—C46119.09 (19)
C11—C12—Ni168.13 (12)C42—C41—P1123.89 (16)
C13—C12—Ni167.79 (12)C46—C41—P1116.99 (16)
C11—C12—H12126.9C43—C42—C41120.3 (2)
C13—C12—H12126.9C43—C42—H42119.9
Ni1—C12—H12128.7C41—C42—H42119.9
C12—C13—C14109.0 (2)C42—C43—C44120.3 (2)
C12—C13—Ni172.95 (13)C42—C43—H43119.8
C14—C13—Ni172.41 (12)C44—C43—H43119.8
C12—C13—H13125.5C45—C44—C43119.7 (2)
C14—C13—H13125.5C45—C44—H44120.2
Ni1—C13—H13120.9C43—C44—H44120.2
C15—C14—C13107.2 (2)C46—C45—C44120.1 (2)
C15—C14—Ni169.69 (13)C46—C45—H45119.9
C13—C14—Ni167.66 (12)C44—C45—H45119.9
C15—C14—H14126.4C45—C46—C41120.4 (2)
C13—C14—H14126.4C45—C46—H46119.8
Ni1—C14—H14127.8C41—C46—H46119.8
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C36—H36···O1i0.952.593.389 (3)142
C23—H23···O1ii0.952.563.475 (3)161
C34—H34···Cg1iii0.952.633.460 (3)147
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z−1; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Ni(C5H5)(C5H7O)(C18H15P)]
Mr469.18
Crystal system, space groupTriclinic, P1
Temperature (K)85
a, b, c (Å)8.9097 (8), 11.0904 (8), 12.7489 (14)
α, β, γ (°)100.643 (5), 109.694 (4), 94.490 (3)
V (Å3)1152.13 (18)
Z2
Radiation typeMo Kα
µ (mm−1)0.93
Crystal size (mm)0.28 × 0.19 × 0.10
Data collection
DiffractometerBruker APEX II CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.715, 0.911
No. of measured, independent and
observed [I > 2σ(I)] reflections		28022, 7726, 6277
Rint0.046
(sin θ/λ)max (Å−1)0.795
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.186, 1.06
No. of reflections7726
No. of parameters286
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)2.45, −1.73

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997) and TITAN2000 (Hunter & Simpson, 1999), ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002), SHELXL97, enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and PARST (Nardelli, 1995).

Selected geometric parameters (Å, º) top
Ni1—C11.855 (2)C3—O11.440 (3)
Ni1—P12.1253 (6)C3—C41.533 (3)
C1—C21.208 (3)C3—C51.531 (3)
C2—C31.485 (3)O1—H10.77 (4)
C1—Ni1—P186.12 (6)C1—C2—C3172.3 (2)
C2—C1—Ni1172.94 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C36—H36···O1i0.952.593.389 (3)142.3
C23—H23···O1ii0.952.563.475 (3)160.8
C34—H34···Cg1iii0.952.633.460 (3)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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