(η5-Cyclo­penta­dien­yl)(2-naphthylethyn­yl)(triphenyl­phosphine-κP)nickel(II)

Butler, P.; Gallagher, J.F.; Lough, A.J.; Manning, A.R.

doi:10.1107/S1600536807016832

(η⁵-Cyclopentadienyl)(2-naphthylethynyl)(triphenylphosphine-κP)nickel(II)

P. Butler, J. F. Gallagher, A. J. Lough and A. R. Manning

The title compound, [Ni(C₅H₅)(C₁₂H₇)(C₁₈H₁₅P)], does not contain strong hydrogen-bond donors or acceptors and the primary interactions are limited to those of the weak C—H

π(arene) type and mainly involving the arene rings.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807016832/tk2154sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807016832/tk2154Isup2.hkl Contains datablock I

CCDC reference: 646635

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.004 Å
R factor = 0.048
wR factor = 0.120
Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.813     0.954
            Tmin(prime) and Tmax expected:      0.875     0.915
            RR(prime) =      0.890
            Please check that your absorption correction is appropriate.
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.93
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.89
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   C1      ..       5.65 su
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C4     ...       1.43 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The acetylide linkage in Ni(η⁵-C₅H₅)(PPh₃)-C≡C–X complexes allows facile electronic communication between the electron-rich Ni(η⁵-C₅H₅)(PPh₃) moiety and the X group (X is alkyl or arene), thus affecting the characteristic chemistry of both X and the acetylide linkage (Gallagher et al., 2002). However, if X is an electron-withdrawing group, the molecule is a donor–π-acceptor (D–π-A) system which may have nonlinear optical (NLO) properties (Whittal et al., 1998a,b), although the phenyl derivative (X = C₆H₅) does not appear to be particularly effective. We have

demonstrated that polycylic hydrocarbons containing one to five aromatic rings

can act as an electron-donor endgroup in D–π-A systems in the presence of suitable acceptors, and have examined their behaviour attached to the Ni(η⁵-C₅H₅)(PPh₃) donor moiety (Butler et al., 2005). The spectroscopic and electrochemical evidence suggests limited communication between either end of these Ni(η⁵-C₅H₅)(PPh₃)-C≡C–X systems, at least in the ground state, and is not sufficient to influence significant changes in the geometric data from diffraction measurements. Here, we present the title 2-naphthyl derivative, (I) (where X = C₁₀H₇).

The molecule of (I) has a half-sandwich structure and contains the σ-bonded ethynyl-2-naphthyl ligand, the η⁵-C₅ ring and triphenyl phosphine bonded to the central Ni^II atom. A view of the molecule with the atomic numbering scheme is presented in Fig. 1 (with selected dimensions in Table 2). The principal Ni–ligand dimensions include Ni1—P1 [2.1484 (9) Å], Ni1—C1 [1.843 (4) Å] and P1—Ni1—C1 [89.04 (9)°], and these are similar to data in related derivatives (Gallagher et al., 1998, 2002; Butler et al., 1998, 2005). The acetylide C≡C and Csp—C_ar bond lengths are 1.211 (4) and 1.433 (5) Å, respectively. The former is slightly longer than the expected value of 1.18 (1) Å for C≡C (Orpen et al., 1994), while the latter is as expected. The bond angles of the Ni—C≡C—C chain deviate slightly from linearity, with Ni—C≡C = 176.8 (3)° and C≡C—C = 173.0 (3)°.

The η⁵-C₅H₅ ring is orthogonal to the P1/Ni1/C1 plane [88.70 (12)°] and to the naphthyl ring [73.83 (10)°]. The naphthyl ring is twisted by 24.23 (9)° from the P1/Ni1/C1 plane.

The closest intramolecular contact to Ni1 involves H42, with H42···Ni1 = 3.11 Å and C42—H42···Ni1 = 113° [C42 is the closest PPh₃ ortho-C atom to Ni1, at 3.586 (3) Å]. Although the three Ni1—P—C angles vary, at 111.85 (10), 114.48 (10) and 118.63 (10)°, there is little asymmetry in the PPh₃ ligand, with all six P—C—C angles in the range 119.1 (2)–122.6 (3)° and three P—C_ipso···C_para angles of 177.20 (18), 177.42 (16) and 178.25 (18)°.

In the absence of strong hydrogen-bond donors or acceptors, C—H···π(arene) interactions involving the phosphine arene rings arise, with C···Cg in the range 3.549 (4)–3.797 (4) Å and with C—H···Cg angles in the range 138–164° (details in Table 2), where Cg is an aromatic ring centroid (Fig. 2).

Related literature top

For related literature, see: Butler et al. (1998, 2005); Gallagher et al. (1998, 2002); Orpen et al. (1994); Whittal et al. (1998a,b).

Experimental top

Compound (I) was prepared according to literature methods (Butler et al., 2005) and is compound 1 d in the aforementioned paper.

Structure description top

demonstrated that polycylic hydrocarbons containing one to five aromatic rings

The η⁵-C₅H₅ ring is orthogonal to the P1/Ni1/C1 plane [88.70 (12)°] and to the naphthyl ring [73.83 (10)°]. The naphthyl ring is twisted by 24.23 (9)° from the P1/Ni1/C1 plane.

For related literature, see: Butler et al. (1998, 2005); Gallagher et al. (1998, 2002); Orpen et al. (1994); Whittal et al. (1998a,b).

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PREP8 (Ferguson, 1998).

Figures top

	Fig. 1. A view of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the intramolecular H42···Ni1 contact.
	Fig. 2. A view of the weak interactions in the crystal structure of (I), with atoms shown as their van der Waals spheres. Three of the C—H···π(arene) interactions have labels.

(η⁵-Cyclopentadienyl)(2-naphthylethynyl)(triphenylphosphine-κP)nickel(II) top

Crystal data top

[Ni(C₅H₅)(C₁₂H₇)(C₁₈H₁₅P)]	F(000) = 1120
M_r = 537.25	? #Insert any comments here.
Monoclinic, P2₁/n	D_x = 1.338 Mg m⁻³
Hall symbol: -p 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 14.4455 (4) Å	Cell parameters from 17521 reflections
b = 12.7392 (5) Å	θ = 2.6–27.5°
c = 15.2816 (4) Å	µ = 0.81 mm⁻¹
β = 108.439 (2)°	T = 150 K
V = 2667.80 (15) Å³	Block, green
Z = 4	0.16 × 0.15 × 0.11 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	5695 independent reflections
Radiation source: fine-focus sealed X-ray tube	3173 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.083
φ and ω scans with κ offsets	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −18→15
T_min = 0.813, T_max = 0.954	k = −16→16
8684 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0504P)²] where P = (F_o² + 2F_c²)/3
5695 reflections	(Δ/σ)_max < 0.001
334 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[Ni(C₅H₅)(C₁₂H₇)(C₁₈H₁₅P)]	V = 2667.80 (15) Å³
M_r = 537.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.4455 (4) Å	µ = 0.81 mm⁻¹
b = 12.7392 (5) Å	T = 150 K
c = 15.2816 (4) Å	0.16 × 0.15 × 0.11 mm
β = 108.439 (2)°

Data collection top

Nonius KappaCCD area-detector diffractometer	5695 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	3173 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.954	R_int = 0.083
8684 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 0.98	Δρ_max = 0.54 e Å⁻³
5695 reflections	Δρ_min = −0.61 e Å⁻³
334 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.07764 (3)	0.09838 (3)	0.27091 (3)	0.02909 (14)
P1	0.18440 (6)	0.08760 (7)	0.40539 (5)	0.0265 (2)
C1	0.1713 (2)	0.0554 (3)	0.2201 (2)	0.0309 (8)
C2	0.2363 (2)	0.0278 (2)	0.1910 (2)	0.0313 (8)
C3	0.4134 (2)	0.0207 (3)	0.2268 (2)	0.0324 (8)
C4	0.3212 (2)	−0.0016 (2)	0.1674 (2)	0.0313 (8)
C5	0.3134 (2)	−0.0539 (3)	0.0825 (2)	0.0339 (8)
C6	0.3948 (2)	−0.0804 (3)	0.0611 (2)	0.0349 (8)
C7	0.4892 (2)	−0.0577 (3)	0.1204 (2)	0.0307 (8)
C8	0.4987 (2)	−0.0065 (2)	0.2054 (2)	0.0292 (8)
C11A	0.5747 (2)	−0.0834 (3)	0.0985 (2)	0.0362 (8)
C12A	0.6643 (3)	−0.0598 (3)	0.1573 (2)	0.0403 (9)
C13A	0.6735 (3)	−0.0100 (3)	0.2418 (2)	0.0421 (9)
C14A	0.5928 (2)	0.0161 (3)	0.2657 (2)	0.0371 (9)
C11	−0.0315 (2)	0.1281 (3)	0.1477 (2)	0.0460 (10)
C12	−0.0613 (2)	0.0393 (3)	0.1885 (2)	0.0430 (9)
C13	−0.0665 (2)	0.0694 (3)	0.2737 (2)	0.0415 (9)
C14	−0.0426 (2)	0.1787 (3)	0.2848 (2)	0.0412 (9)
C15	−0.0263 (2)	0.2162 (3)	0.2053 (3)	0.0478 (10)
C21	0.1570 (2)	0.1480 (2)	0.5034 (2)	0.0276 (7)
C22	0.2256 (2)	0.2058 (3)	0.5702 (2)	0.0327 (8)
C23	0.2028 (2)	0.2488 (3)	0.6449 (2)	0.0359 (8)
C24	0.1112 (2)	0.2351 (3)	0.6528 (2)	0.0359 (8)
C25	0.0422 (2)	0.1784 (3)	0.5873 (2)	0.0384 (9)
C26	0.0648 (2)	0.1347 (3)	0.5127 (2)	0.0363 (8)
C31	0.2103 (2)	−0.0496 (2)	0.4429 (2)	0.0276 (7)
C32	0.2333 (2)	−0.1217 (3)	0.3845 (2)	0.0388 (9)
C33	0.2494 (3)	−0.2259 (3)	0.4093 (2)	0.0428 (9)
C34	0.2427 (2)	−0.2602 (3)	0.4926 (2)	0.0375 (9)
C35	0.2215 (2)	−0.1900 (3)	0.5520 (2)	0.0384 (9)
C36	0.2052 (2)	−0.0857 (3)	0.5267 (2)	0.0346 (8)
C41	0.3034 (2)	0.1433 (2)	0.4134 (2)	0.0270 (7)
C42	0.3077 (2)	0.2302 (3)	0.3603 (2)	0.0330 (8)
C43	0.3962 (2)	0.2780 (3)	0.3678 (2)	0.0406 (9)
C44	0.4815 (2)	0.2370 (3)	0.4286 (2)	0.0408 (9)
C45	0.4781 (2)	0.1507 (3)	0.4819 (2)	0.0384 (9)
C46	0.3893 (2)	0.1032 (3)	0.4742 (2)	0.0319 (8)
H3	0.4195	0.0552	0.2835	0.039*
H5	0.2509	−0.0701	0.0407	0.041*
H6	0.3878	−0.1152	0.0044	0.042*
H11A	0.5692	−0.1176	0.0419	0.043*
H12A	0.7209	−0.0770	0.1415	0.048*
H13A	0.7366	0.0058	0.2827	0.051*
H14A	0.6002	0.0495	0.3231	0.045*
H11	−0.0175	0.1283	0.0910	0.055*
H12	−0.0751	−0.0287	0.1619	0.052*
H13	−0.0830	0.0257	0.3169	0.050*
H14	−0.0385	0.2192	0.3381	0.049*
H15	−0.0142	0.2869	0.1924	0.057*
H22	0.2888	0.2162	0.5650	0.039*
H23	0.2507	0.2876	0.6904	0.043*
H24	0.0958	0.2648	0.7035	0.043*
H25	−0.0210	0.1689	0.5927	0.046*
H26	0.0167	0.0955	0.4677	0.044*
H32	0.2379	−0.0989	0.3269	0.047*
H33	0.2653	−0.2741	0.3688	0.051*
H34	0.2527	−0.3323	0.5090	0.045*
H35	0.2180	−0.2131	0.6101	0.046*
H36	0.1902	−0.0377	0.5678	0.042*
H42	0.2493	0.2574	0.3182	0.040*
H43	0.3985	0.3382	0.3318	0.049*
H44	0.5425	0.2686	0.4335	0.049*
H45	0.5366	0.1235	0.5239	0.046*
H46	0.3872	0.0433	0.5106	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0241 (3)	0.0308 (3)	0.0317 (2)	0.00182 (19)	0.00784 (18)	−0.00069 (19)
P1	0.0234 (5)	0.0257 (5)	0.0306 (4)	0.0002 (4)	0.0086 (4)	−0.0009 (4)
C1	0.032 (2)	0.0265 (19)	0.0322 (17)	−0.0016 (15)	0.0065 (16)	0.0011 (15)
C2	0.034 (2)	0.0252 (19)	0.0358 (18)	−0.0035 (16)	0.0128 (16)	−0.0022 (15)
C3	0.036 (2)	0.0290 (19)	0.0361 (18)	−0.0009 (16)	0.0173 (16)	−0.0010 (15)
C4	0.038 (2)	0.0245 (19)	0.0358 (18)	−0.0002 (16)	0.0175 (17)	0.0039 (15)
C5	0.033 (2)	0.032 (2)	0.0362 (18)	−0.0044 (16)	0.0108 (16)	−0.0012 (15)
C6	0.046 (2)	0.027 (2)	0.0365 (18)	−0.0049 (16)	0.0195 (17)	−0.0055 (15)
C7	0.035 (2)	0.0245 (18)	0.0360 (18)	−0.0004 (15)	0.0159 (16)	0.0037 (15)
C8	0.033 (2)	0.0225 (18)	0.0340 (18)	0.0025 (15)	0.0133 (16)	0.0049 (14)
C11A	0.037 (2)	0.038 (2)	0.0390 (18)	0.0019 (17)	0.0201 (17)	0.0023 (17)
C12A	0.040 (2)	0.040 (2)	0.047 (2)	0.0039 (17)	0.0234 (19)	0.0039 (17)
C13A	0.032 (2)	0.050 (2)	0.044 (2)	−0.0004 (18)	0.0104 (17)	0.0050 (18)
C14A	0.037 (2)	0.039 (2)	0.0338 (18)	0.0021 (17)	0.0099 (17)	0.0001 (16)
C11	0.023 (2)	0.077 (3)	0.0326 (19)	0.0067 (19)	0.0015 (16)	0.006 (2)
C12	0.025 (2)	0.052 (3)	0.048 (2)	−0.0013 (18)	0.0047 (17)	−0.010 (2)
C13	0.0239 (19)	0.053 (3)	0.048 (2)	0.0009 (17)	0.0112 (16)	0.0022 (19)
C14	0.0228 (19)	0.048 (2)	0.049 (2)	0.0098 (17)	0.0070 (16)	−0.0032 (19)
C15	0.037 (2)	0.044 (2)	0.057 (2)	0.0111 (19)	0.0085 (19)	0.012 (2)
C21	0.0261 (18)	0.0245 (18)	0.0317 (17)	0.0017 (14)	0.0084 (14)	−0.0014 (14)
C22	0.0244 (18)	0.035 (2)	0.0370 (18)	0.0006 (15)	0.0072 (15)	−0.0007 (16)
C23	0.037 (2)	0.033 (2)	0.0333 (18)	−0.0006 (16)	0.0051 (16)	−0.0065 (16)
C24	0.042 (2)	0.034 (2)	0.0343 (18)	0.0070 (17)	0.0156 (17)	−0.0035 (16)
C25	0.034 (2)	0.041 (2)	0.042 (2)	−0.0020 (17)	0.0154 (17)	−0.0062 (17)
C26	0.033 (2)	0.036 (2)	0.0381 (19)	−0.0050 (16)	0.0088 (16)	−0.0063 (16)
C31	0.0206 (17)	0.0260 (18)	0.0346 (17)	0.0001 (14)	0.0065 (14)	−0.0025 (15)
C32	0.049 (2)	0.033 (2)	0.0388 (19)	0.0055 (17)	0.0202 (17)	0.0009 (16)
C33	0.057 (2)	0.032 (2)	0.045 (2)	0.0059 (18)	0.0220 (19)	−0.0022 (17)
C34	0.035 (2)	0.027 (2)	0.047 (2)	−0.0010 (16)	0.0076 (17)	0.0030 (17)
C35	0.044 (2)	0.036 (2)	0.0373 (19)	−0.0028 (17)	0.0148 (17)	0.0013 (17)
C36	0.037 (2)	0.034 (2)	0.0335 (18)	0.0012 (16)	0.0124 (15)	−0.0006 (16)
C41	0.0235 (18)	0.0245 (18)	0.0334 (17)	0.0002 (14)	0.0095 (15)	−0.0055 (15)
C42	0.029 (2)	0.0294 (19)	0.0387 (19)	0.0000 (15)	0.0083 (15)	−0.0019 (16)
C43	0.040 (2)	0.031 (2)	0.055 (2)	−0.0044 (17)	0.0203 (19)	0.0004 (17)
C44	0.028 (2)	0.036 (2)	0.060 (2)	−0.0044 (17)	0.0171 (18)	−0.0079 (19)
C45	0.026 (2)	0.036 (2)	0.050 (2)	0.0030 (16)	0.0084 (16)	−0.0024 (18)
C46	0.0298 (19)	0.0293 (19)	0.0360 (17)	0.0000 (16)	0.0093 (15)	0.0015 (15)

Geometric parameters (Å, º) top

Ni1—P1	2.1484 (9)	C33—C34	1.378 (5)
Ni1—C1	1.843 (4)	C34—C35	1.376 (5)
Ni1—C11	2.073 (3)	C35—C36	1.383 (5)
Ni1—C12	2.141 (3)	C41—C42	1.386 (4)
Ni1—C13	2.129 (3)	C41—C46	1.391 (4)
Ni1—C14	2.084 (3)	C42—C43	1.388 (4)
Ni1—C15	2.136 (3)	C43—C44	1.389 (5)
P1—C21	1.835 (3)	C44—C45	1.378 (5)
P1—C31	1.841 (3)	C45—C46	1.390 (4)
P1—C41	1.828 (3)	C3—H3	0.9500
C1—C2	1.211 (4)	C5—H5	0.9500
C2—C4	1.433 (5)	C6—H6	0.9500
C3—C4	1.384 (4)	C11A—H11A	0.9500
C3—C8	1.414 (4)	C12A—H12A	0.9500
C4—C5	1.431 (4)	C13A—H13A	0.9500
C5—C6	1.359 (4)	C14A—H14A	0.9500
C6—C7	1.408 (4)	C11—H11	0.9500
C7—C11A	1.416 (4)	C12—H12	0.9500
C7—C8	1.422 (4)	C13—H13	0.9500
C8—C14A	1.410 (4)	C14—H14	0.9500
C11A—C12A	1.355 (4)	C15—H15	0.9500
C12A—C13A	1.406 (5)	C22—H22	0.9500
C13A—C14A	1.369 (5)	C23—H23	0.9500
C11—C15	1.414 (5)	C24—H24	0.9500
C11—C12	1.422 (5)	C25—H25	0.9500
C12—C13	1.382 (5)	C26—H26	0.9500
C13—C14	1.431 (5)	C32—H32	0.9500
C14—C15	1.393 (5)	C33—H33	0.9500
C21—C22	1.387 (4)	C34—H34	0.9500
C21—C26	1.393 (4)	C35—H35	0.9500
C22—C23	1.397 (4)	C36—H36	0.9500
C23—C24	1.378 (4)	C42—H42	0.9500
C24—C25	1.373 (4)	C43—H43	0.9500
C25—C26	1.397 (5)	C44—H44	0.9500
C31—C36	1.385 (4)	C45—H45	0.9500
C31—C32	1.392 (4)	C46—H46	0.9500
C32—C33	1.379 (5)

C1—Ni1—C11	96.95 (14)	C14—C15—C11	106.3 (3)
C1—Ni1—C14	159.31 (14)	C14—C15—Ni1	68.71 (19)
C11—Ni1—C14	65.39 (14)	C11—C15—Ni1	67.98 (19)
C1—Ni1—C13	144.11 (14)	C22—C21—C26	118.3 (3)
C11—Ni1—C13	65.26 (14)	C22—C21—P1	122.3 (2)
C14—Ni1—C13	39.69 (13)	C26—C21—P1	119.5 (2)
C1—Ni1—C15	120.81 (14)	C21—C22—C23	120.7 (3)
C11—Ni1—C15	39.21 (14)	C24—C23—C22	120.2 (3)
C14—Ni1—C15	38.54 (13)	C25—C24—C23	119.9 (3)
C13—Ni1—C15	65.41 (14)	C24—C25—C26	120.1 (3)
C1—Ni1—C12	108.92 (14)	C21—C26—C25	120.8 (3)
C11—Ni1—C12	39.42 (14)	C36—C31—C32	117.8 (3)
C14—Ni1—C12	64.91 (14)	C36—C31—P1	122.6 (2)
C13—Ni1—C12	37.78 (13)	C32—C31—P1	119.6 (2)
C15—Ni1—C12	65.28 (15)	C33—C32—C31	120.9 (3)
C11—Ni1—P1	171.96 (12)	C34—C33—C32	120.2 (3)
C14—Ni1—P1	107.64 (10)	C35—C34—C33	119.9 (3)
C13—Ni1—P1	112.38 (10)	C34—C35—C36	119.6 (3)
C15—Ni1—P1	132.79 (11)	C35—C36—C31	121.6 (3)
C12—Ni1—P1	142.77 (11)	C42—C41—C46	119.3 (3)
C41—P1—C21	102.95 (14)	C42—C41—P1	119.1 (2)
C41—P1—C31	104.70 (14)	C46—C41—P1	121.6 (2)
C21—P1—C31	102.64 (14)	C41—C42—C43	120.9 (3)
Ni1—P1—C21	118.63 (10)	C42—C43—C44	119.3 (3)
Ni1—P1—C31	111.85 (10)	C45—C44—C43	120.4 (3)
Ni1—P1—C41	114.48 (10)	C44—C45—C46	120.1 (3)
P1—Ni1—C1	89.04 (9)	C45—C46—C41	120.1 (3)
Ni1—C1—C2	176.8 (3)	C4—C3—H3	119.1
C1—C2—C4	173.0 (3)	C8—C3—H3	119.1
C4—C3—C8	121.7 (3)	C6—C5—H5	119.7
C3—C4—C5	118.3 (3)	C4—C5—H5	119.7
C3—C4—C2	120.2 (3)	C5—C6—H6	119.0
C5—C4—C2	121.5 (3)	C7—C6—H6	119.0
C6—C5—C4	120.6 (3)	C12A—C11A—H11A	119.6
C5—C6—C7	122.0 (3)	C7—C11A—H11A	119.6
C6—C7—C11A	122.7 (3)	C11A—C12A—H12A	119.9
C6—C7—C8	118.4 (3)	C13A—C12A—H12A	119.9
C11A—C7—C8	118.9 (3)	C14A—C13A—H13A	119.6
C14A—C8—C3	122.0 (3)	C12A—C13A—H13A	119.6
C14A—C8—C7	119.0 (3)	C13A—C14A—H14A	119.9
C3—C8—C7	119.0 (3)	C8—C14A—H14A	119.9
C12A—C11A—C7	120.9 (3)	C15—C11—H11	125.6
C11A—C12A—C13A	120.2 (3)	C12—C11—H11	125.6
C14A—C13A—C12A	120.8 (3)	Ni1—C11—H11	120.5
C13A—C14A—C8	120.2 (3)	C13—C12—H12	126.1
C15—C11—C12	108.8 (3)	C11—C12—H12	126.1
C15—C11—Ni1	72.80 (19)	Ni1—C12—H12	127.1
C12—C11—Ni1	72.86 (19)	C12—C13—H13	126.3
C13—C12—C11	107.8 (3)	C14—C13—H13	126.3
C13—C12—Ni1	70.64 (19)	Ni1—C13—H13	125.2
C11—C12—Ni1	67.72 (19)	C15—C14—H14	125.3
C12—C13—C14	107.4 (3)	C13—C14—H14	125.3
C12—C13—Ni1	71.6 (2)	Ni1—C14—H14	121.7
C14—C13—Ni1	68.47 (19)	C14—C15—H15	126.9
C15—C14—C13	109.3 (3)	C11—C15—H15	126.9
C15—C14—Ni1	72.8 (2)	Ni1—C15—H15	127.9
C13—C14—Ni1	71.84 (19)

C1—Ni1—P1—C41	44.41 (15)	Ni1—C13—C14—C15	63.5 (2)
C14—Ni1—P1—C41	−123.13 (16)	C12—C13—C14—Ni1	−61.3 (2)
C13—Ni1—P1—C41	−165.20 (15)	C1—Ni1—C14—C15	−4.2 (5)
C15—Ni1—P1—C41	−88.62 (18)	C11—Ni1—C14—C15	−37.5 (2)
C12—Ni1—P1—C41	165.3 (2)	C13—Ni1—C14—C15	−117.8 (3)
C1—Ni1—P1—C21	166.35 (16)	C12—Ni1—C14—C15	−81.2 (2)
C14—Ni1—P1—C21	−1.19 (17)	P1—Ni1—C14—C15	138.1 (2)
C13—Ni1—P1—C21	−43.26 (17)	C1—Ni1—C14—C13	113.6 (4)
C15—Ni1—P1—C21	33.32 (19)	C11—Ni1—C14—C13	80.3 (2)
C12—Ni1—P1—C21	−72.7 (2)	C15—Ni1—C14—C13	117.8 (3)
C1—Ni1—P1—C31	−74.47 (15)	C12—Ni1—C14—C13	36.6 (2)
C14—Ni1—P1—C31	117.99 (15)	P1—Ni1—C14—C13	−104.03 (19)
C13—Ni1—P1—C31	75.91 (16)	C13—C14—C15—C11	−5.1 (4)
C15—Ni1—P1—C31	152.49 (18)	Ni1—C14—C15—C11	57.8 (2)
C12—Ni1—P1—C31	46.5 (2)	C13—C14—C15—Ni1	−62.9 (2)
C8—C3—C4—C5	0.2 (5)	C12—C11—C15—C14	6.2 (4)
C8—C3—C4—C2	−179.5 (3)	Ni1—C11—C15—C14	−58.3 (2)
C3—C4—C5—C6	−0.2 (5)	C12—C11—C15—Ni1	64.4 (2)
C2—C4—C5—C6	179.5 (3)	C1—Ni1—C15—C14	178.3 (2)
C4—C5—C6—C7	−0.2 (5)	C11—Ni1—C15—C14	118.8 (3)
C5—C6—C7—C11A	−179.1 (3)	C13—Ni1—C15—C14	38.4 (2)
C5—C6—C7—C8	0.7 (5)	C12—Ni1—C15—C14	80.1 (2)
C4—C3—C8—C14A	179.9 (3)	P1—Ni1—C15—C14	−60.0 (3)
C4—C3—C8—C7	0.3 (5)	C1—Ni1—C15—C11	59.5 (3)
C6—C7—C8—C14A	179.7 (3)	C14—Ni1—C15—C11	−118.8 (3)
C11A—C7—C8—C14A	−0.6 (5)	C13—Ni1—C15—C11	−80.4 (2)
C6—C7—C8—C3	−0.7 (5)	C12—Ni1—C15—C11	−38.6 (2)
C11A—C7—C8—C3	179.0 (3)	P1—Ni1—C15—C11	−178.84 (18)
C6—C7—C11A—C12A	179.7 (3)	C41—P1—C21—C22	−9.5 (3)
C8—C7—C11A—C12A	0.0 (5)	C31—P1—C21—C22	99.1 (3)
C7—C11A—C12A—C13A	0.5 (5)	Ni1—P1—C21—C22	−137.0 (2)
C11A—C12A—C13A—C14A	−0.4 (5)	C41—P1—C21—C26	171.5 (3)
C12A—C13A—C14A—C8	−0.2 (5)	C31—P1—C21—C26	−80.0 (3)
C3—C8—C14A—C13A	−178.9 (3)	Ni1—P1—C21—C26	43.9 (3)
C7—C8—C14A—C13A	0.7 (5)	C26—C21—C22—C23	0.4 (5)
C1—Ni1—C11—C15	−131.8 (2)	P1—C21—C22—C23	−178.7 (2)
C14—Ni1—C11—C15	36.9 (2)	C21—C22—C23—C24	−0.6 (5)
C13—Ni1—C11—C15	80.8 (2)	C22—C23—C24—C25	0.4 (5)
C12—Ni1—C11—C15	116.7 (3)	C23—C24—C25—C26	0.0 (5)
C1—Ni1—C11—C12	111.5 (2)	C22—C21—C26—C25	−0.1 (5)
C14—Ni1—C11—C12	−79.8 (2)	P1—C21—C26—C25	179.0 (3)
C13—Ni1—C11—C12	−35.9 (2)	C24—C25—C26—C21	−0.1 (5)
C15—Ni1—C11—C12	−116.7 (3)	C41—P1—C31—C36	108.2 (3)
C15—C11—C12—C13	−4.9 (4)	C21—P1—C31—C36	0.9 (3)
Ni1—C11—C12—C13	59.5 (2)	Ni1—P1—C31—C36	−127.3 (2)
C15—C11—C12—Ni1	−64.4 (2)	C41—P1—C31—C32	−73.7 (3)
C1—Ni1—C12—C13	162.9 (2)	C21—P1—C31—C32	179.1 (3)
C11—Ni1—C12—C13	−119.6 (3)	Ni1—P1—C31—C32	50.8 (3)
C14—Ni1—C12—C13	−38.5 (2)	C36—C31—C32—C33	0.7 (5)
C15—Ni1—C12—C13	−81.1 (2)	P1—C31—C32—C33	−177.6 (3)
P1—Ni1—C12—C13	47.9 (3)	C31—C32—C33—C34	0.2 (5)
C1—Ni1—C12—C11	−77.5 (2)	C32—C33—C34—C35	−1.2 (5)
C14—Ni1—C12—C11	81.1 (2)	C33—C34—C35—C36	1.3 (5)
C13—Ni1—C12—C11	119.6 (3)	C34—C35—C36—C31	−0.4 (5)
C15—Ni1—C12—C11	38.4 (2)	C32—C31—C36—C35	−0.6 (5)
P1—Ni1—C12—C11	167.50 (18)	P1—C31—C36—C35	177.6 (2)
C11—C12—C13—C14	1.7 (4)	C21—P1—C41—C42	−96.4 (3)
Ni1—C12—C13—C14	59.3 (2)	C31—P1—C41—C42	156.6 (2)
C11—C12—C13—Ni1	−57.7 (2)	Ni1—P1—C41—C42	33.7 (3)
C1—Ni1—C13—C12	−28.4 (4)	C21—P1—C41—C46	80.9 (3)
C11—Ni1—C13—C12	37.4 (2)	C31—P1—C41—C46	−26.1 (3)
C14—Ni1—C13—C12	118.1 (3)	Ni1—P1—C41—C46	−149.0 (2)
C15—Ni1—C13—C12	80.8 (2)	C46—C41—C42—C43	−0.7 (5)
P1—Ni1—C13—C12	−150.9 (2)	P1—C41—C42—C43	176.7 (3)
C1—Ni1—C13—C14	−146.5 (2)	C41—C42—C43—C44	0.9 (5)
C11—Ni1—C13—C14	−80.6 (2)	C42—C43—C44—C45	−1.0 (5)
C15—Ni1—C13—C14	−37.3 (2)	C43—C44—C45—C46	0.8 (5)
C12—Ni1—C13—C14	−118.1 (3)	C44—C45—C46—C41	−0.6 (5)
P1—Ni1—C13—C14	91.0 (2)	C42—C41—C46—C45	0.5 (5)
C12—C13—C14—C15	2.2 (4)	P1—C41—C46—C45	−176.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg1	0.95	2.84	3.760 (4)	164
C6—H6···Cg2ⁱ	0.95	2.74	3.549 (4)	144
C25—H25···Cg3ⁱⁱ	0.95	2.83	3.722 (3)	157
C23—H23···Cg4ⁱⁱⁱ	0.95	3.04	3.797 (4)	138

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, −y, −z+1; (iii) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₅H₅)(C₁₂H₇)(C₁₈H₁₅P)]
M_r	537.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	14.4455 (4), 12.7392 (5), 15.2816 (4)
β (°)	108.439 (2)
V (Å³)	2667.80 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.16 × 0.15 × 0.11

Data collection
Diffractometer	Nonius KappaCCD area-detector
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.813, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	8684, 5695, 3173
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.120, 0.98
No. of reflections	5695
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.61

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003), SHELXL97 and PREP8 (Ferguson, 1998).

Selected bond angles (º) top

Ni1—P1—C21	118.63 (10)	P1—Ni1—C1	89.04 (9)
Ni1—P1—C31	111.85 (10)	Ni1—C1—C2	176.8 (3)
Ni1—P1—C41	114.48 (10)	C1—C2—C4	173.0 (3)