Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807016832/tk2154sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807016832/tk2154Isup2.hkl |
CCDC reference: 646635
Compound (I) was prepared according to literature methods (Butler et al., 2005) and is compound 1 d in the aforementioned paper.
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 NiII 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—Car 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—Cipso···Cpara 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).
For related literature, see: Butler et al. (1998, 2005); Gallagher et al. (1998, 2002); Orpen et al. (1994); Whittal et al. (1998a,b).
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).
[Ni(C5H5)(C12H7)(C18H15P)] | F(000) = 1120 |
Mr = 537.25 | ? #Insert any comments here. |
Monoclinic, P21/n | Dx = 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 |
Nonius KappaCCD area-detector diffractometer | 5695 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3173 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
φ and ω scans with κ offsets | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −18→15 |
Tmin = 0.813, Tmax = 0.954 | k = −16→16 |
8684 measured reflections | l = −19→19 |
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(Fo2) + (0.0504P)2] where P = (Fo2 + 2Fc2)/3 |
5695 reflections | (Δ/σ)max < 0.001 |
334 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Ni(C5H5)(C12H7)(C18H15P)] | V = 2667.80 (15) Å3 |
Mr = 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)° |
Nonius KappaCCD area-detector diffractometer | 5695 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3173 reflections with I > 2σ(I) |
Tmin = 0.813, Tmax = 0.954 | Rint = 0.083 |
8684 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.54 e Å−3 |
5695 reflections | Δρmin = −0.61 e Å−3 |
334 parameters |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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)] |
Mr | 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) |
Tmin, Tmax | 0.813, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8684, 5695, 3173 |
Rint | 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 |
Δρmax, Δρmin (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).
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) |
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. |
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 NiII 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—Car 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—Cipso···Cpara 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).