Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051306/cs2047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051306/cs2047Isup2.hkl |
CCDC reference: 667418
2,6-Diisopropylaniline (3.94 g, 22.2 mmol) was added via syringe to a solution of 5-tert-Butyl-2-hydroxy-3-(1-phenyl-ethyl)-benzaldehyde (6.26 g, 22.2 mmol) in EtOH (100 ml). Formic acid (0.01 g, 0.22 mmol) was added and the solution refluxed for 20 h. The solution was dried over magnesium sulfate, filtered and the volatiles removed under reduced pressure. Extraction into pentane (5 ml) followed by cooling to 243 K afforded yellow crystals of (I) (yield 76%). Spectroscopic analysis: IR (KBr, ν, cm-1): 3055.8, 3027.2, 2965.6, 2871.9, 1621.5, 1591.1, 1460.4, 1361.9, 1269.7, 1176.9, 855.7; 1H NMR (CDCl3, δ, p.p.m.): 1.188 (s, 12H), 1.305 (s, 9H), 1.692 (s, 3H), 3.021 (s, 2H), 4.756 (s, 1H), 7.182–7.369 (m, 10H), 8.287 (s, 1H), 13.146 (s, 1H)
Except the hydroxyl H atom, all H atoms were positioned geometrically (C—H=0.93–0.97 Å) and refined as riding. Uiso(H) values are equal to 1.2Ueq(carrier atom). In absence of significant anomalous dispersion effects, Friedel-pair reflections were merged prior to refinement.
Late-metal catalysts bearing salicylaldiminato-type ligands play an important role in the catalytic oligomerization and polymerization of olefins (Ittel et al., 2000). Increasing the size of the imino substituent and the o-phenoxy substituent has a pronounced effect on the activity of the catalyst and the molecular weight of the polymer (Gibson et al., 2003). We have recently prepared a novel ligand, (I), and report its crystal structure here.
The molecular structure of (I) is shown in Fig. 1. In (I) the phenyl ring and the phenoxy ring form a dihedral angle of 75.18 (1)°, the phenylimino ring is nearly perpendicular to the phenoxy ring, with a dihedral angle of 81.51 (2)°. The dihedral angle between the phenyl and the phenylimino ring is 62.88 (1)°. Three C atoms of isopropyl attaching to the phenylimino ring are disordered in two locations with 55% and 45% probabilities. An intramolecular hydrogen bond is formed between the hydroxyl group and the N atom stabilizing the crystal structure.
For related literature, see: Gibson & Spitzmesser (2003); Ittel & Johnson (2000); Shriner et al. (1946).
Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. |
C31H39NO | Dx = 1.093 Mg m−3 |
Mr = 441.63 | Melting point: 400 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
a = 25.273 (4) Å | Cell parameters from 3934 reflections |
b = 9.5496 (18) Å | θ = 2.3–24.1° |
c = 11.115 (2) Å | µ = 0.07 mm−1 |
V = 2682.6 (8) Å3 | T = 294 K |
Z = 4 | Block, yellow |
F(000) = 960 | 0.24 × 0.20 × 0.16 mm |
Bruker SMART APEX CCD diffractometer | 2505 independent reflections |
Radiation source: fine-focus sealed tube | 1964 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→30 |
Tmin = 0.974, Tmax = 0.990 | k = −11→9 |
13332 measured reflections | l = −11→13 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0512P)2 + 0.4436P] where P = (Fo2 + 2Fc2)/3 |
2505 reflections | (Δ/σ)max = 0.003 |
319 parameters | Δρmax = 0.13 e Å−3 |
41 restraints | Δρmin = −0.12 e Å−3 |
C31H39NO | V = 2682.6 (8) Å3 |
Mr = 441.63 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 25.273 (4) Å | µ = 0.07 mm−1 |
b = 9.5496 (18) Å | T = 294 K |
c = 11.115 (2) Å | 0.24 × 0.20 × 0.16 mm |
Bruker SMART APEX CCD diffractometer | 2505 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1964 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.990 | Rint = 0.039 |
13332 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 41 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.13 e Å−3 |
2505 reflections | Δρmin = −0.12 e Å−3 |
319 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.44217 (8) | 0.0843 (2) | 0.9096 (2) | 0.0504 (5) | |
H1 | 0.4093 (15) | 0.115 (4) | 0.937 (4) | 0.076* | |
N1 | 0.34993 (8) | 0.2094 (3) | 0.9030 (2) | 0.0441 (6) | |
C1 | 0.29497 (10) | 0.2202 (3) | 0.9371 (3) | 0.0420 (7) | |
C2 | 0.26067 (11) | 0.1171 (3) | 0.8930 (3) | 0.0456 (7) | |
C3 | 0.20812 (12) | 0.1214 (4) | 0.9313 (3) | 0.0571 (9) | |
H3A | 0.1845 | 0.0538 | 0.9039 | 0.069* | |
C4 | 0.19064 (13) | 0.2234 (4) | 1.0087 (4) | 0.0647 (10) | |
H4A | 0.1555 | 0.2246 | 1.0331 | 0.078* | |
C5 | 0.22512 (13) | 0.3240 (4) | 1.0501 (3) | 0.0597 (9) | |
H5A | 0.2126 | 0.3936 | 1.1012 | 0.072* | |
C6 | 0.27828 (12) | 0.3240 (3) | 1.0173 (3) | 0.0489 (8) | |
C7 | 0.31638 (13) | 0.4301 (4) | 1.0708 (3) | 0.0585 (9) | 0.55 |
H7A | 0.3432 | 0.4506 | 1.0096 | 0.070* | 0.55 |
C8 | 0.3442 (4) | 0.3728 (10) | 1.1771 (9) | 0.093 (3) | 0.55 |
H8A | 0.3612 | 0.2864 | 1.1558 | 0.140* | 0.55 |
H8B | 0.3192 | 0.3560 | 1.2404 | 0.140* | 0.55 |
H8C | 0.3703 | 0.4387 | 1.2042 | 0.140* | 0.55 |
C9 | 0.2903 (4) | 0.5695 (8) | 1.1056 (11) | 0.094 (3) | 0.55 |
H9A | 0.2724 | 0.6078 | 1.0370 | 0.141* | 0.55 |
H9B | 0.3169 | 0.6340 | 1.1324 | 0.141* | 0.55 |
H9C | 0.2653 | 0.5539 | 1.1692 | 0.141* | 0.55 |
C7' | 0.31638 (13) | 0.4301 (4) | 1.0708 (3) | 0.0585 (9) | 0.45 |
H7'A | 0.3517 | 0.4052 | 1.0413 | 0.070* | 0.45 |
C8' | 0.3184 (5) | 0.4162 (15) | 1.2099 (8) | 0.101 (4) | 0.45 |
H8'A | 0.3426 | 0.4838 | 1.2420 | 0.152* | 0.45 |
H8'B | 0.3299 | 0.3237 | 1.2311 | 0.152* | 0.45 |
H8'C | 0.2837 | 0.4325 | 1.2426 | 0.152* | 0.45 |
C9' | 0.3053 (5) | 0.5723 (10) | 1.0256 (14) | 0.101 (4) | 0.45 |
H9'A | 0.3053 | 0.5715 | 0.9392 | 0.152* | 0.45 |
H9'B | 0.3320 | 0.6356 | 1.0540 | 0.152* | 0.45 |
H9'C | 0.2712 | 0.6023 | 1.0540 | 0.152* | 0.45 |
C10 | 0.27988 (12) | 0.0008 (3) | 0.8111 (3) | 0.0538 (8) | |
H10A | 0.3106 | 0.0365 | 0.7670 | 0.065* | |
C11 | 0.23939 (16) | −0.0449 (5) | 0.7194 (4) | 0.0823 (13) | |
H11A | 0.2287 | 0.0343 | 0.6720 | 0.124* | |
H11B | 0.2091 | −0.0831 | 0.7599 | 0.124* | |
H11C | 0.2546 | −0.1149 | 0.6679 | 0.124* | |
C12 | 0.29860 (19) | −0.1216 (4) | 0.8871 (4) | 0.0941 (14) | |
H12A | 0.3245 | −0.0896 | 0.9440 | 0.141* | |
H12B | 0.3141 | −0.1915 | 0.8360 | 0.141* | |
H12C | 0.2690 | −0.1613 | 0.9293 | 0.141* | |
C13 | 0.36706 (10) | 0.2802 (3) | 0.8142 (3) | 0.0403 (6) | |
H13A | 0.3447 | 0.3457 | 0.7788 | 0.048* | |
C14 | 0.42028 (10) | 0.2630 (3) | 0.7657 (2) | 0.0344 (6) | |
C15 | 0.43582 (11) | 0.3420 (3) | 0.6666 (3) | 0.0390 (6) | |
H15A | 0.4126 | 0.4092 | 0.6367 | 0.047* | |
C16 | 0.48415 (11) | 0.3248 (3) | 0.6105 (3) | 0.0394 (7) | |
C17 | 0.51775 (11) | 0.2242 (3) | 0.6607 (3) | 0.0415 (7) | |
H17A | 0.5506 | 0.2102 | 0.6251 | 0.050* | |
C18 | 0.50481 (10) | 0.1442 (3) | 0.7606 (3) | 0.0378 (6) | |
C19 | 0.45548 (10) | 0.1634 (3) | 0.8132 (2) | 0.0351 (6) | |
C20 | 0.50008 (12) | 0.4134 (3) | 0.5021 (3) | 0.0501 (8) | |
C21 | 0.45576 (16) | 0.4140 (5) | 0.4080 (4) | 0.0873 (13) | |
H21A | 0.4237 | 0.4480 | 0.4440 | 0.131* | |
H21B | 0.4502 | 0.3205 | 0.3788 | 0.131* | |
H21C | 0.4655 | 0.4738 | 0.3423 | 0.131* | |
C22 | 0.50891 (19) | 0.5640 (4) | 0.5434 (4) | 0.0891 (14) | |
H22A | 0.4775 | 0.5980 | 0.5823 | 0.134* | |
H22B | 0.5168 | 0.6218 | 0.4751 | 0.134* | |
H22C | 0.5380 | 0.5669 | 0.5990 | 0.134* | |
C23 | 0.55002 (16) | 0.3593 (5) | 0.4403 (4) | 0.0898 (14) | |
H23A | 0.5787 | 0.3581 | 0.4969 | 0.135* | |
H23B | 0.5589 | 0.4197 | 0.3742 | 0.135* | |
H23C | 0.5439 | 0.2662 | 0.4109 | 0.135* | |
C24 | 0.54360 (11) | 0.0404 (3) | 0.8163 (3) | 0.0484 (7) | |
H24A | 0.5223 | −0.0311 | 0.8570 | 0.058* | |
C25 | 0.57752 (15) | −0.0359 (4) | 0.7233 (4) | 0.0720 (11) | |
H25A | 0.6009 | −0.0999 | 0.7635 | 0.108* | |
H25B | 0.5980 | 0.0310 | 0.6787 | 0.108* | |
H25C | 0.5550 | −0.0869 | 0.6692 | 0.108* | |
C26 | 0.57654 (11) | 0.1120 (3) | 0.9126 (3) | 0.0453 (7) | |
C27 | 0.61133 (12) | 0.2191 (4) | 0.8845 (3) | 0.0595 (9) | |
H27A | 0.6149 | 0.2469 | 0.8047 | 0.071* | |
C28 | 0.64090 (15) | 0.2858 (4) | 0.9719 (4) | 0.0753 (12) | |
H28A | 0.6639 | 0.3579 | 0.9511 | 0.090* | |
C29 | 0.63612 (18) | 0.2449 (5) | 1.0891 (4) | 0.0883 (14) | |
H29A | 0.6560 | 0.2889 | 1.1485 | 0.106* | |
C30 | 0.60198 (18) | 0.1388 (5) | 1.1194 (4) | 0.0839 (12) | |
H30A | 0.5987 | 0.1112 | 1.1993 | 0.101* | |
C31 | 0.57252 (13) | 0.0728 (4) | 1.0313 (3) | 0.0631 (9) | |
H31A | 0.5496 | 0.0007 | 1.0526 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0451 (11) | 0.0618 (13) | 0.0441 (12) | 0.0068 (10) | 0.0068 (10) | 0.0183 (11) |
N1 | 0.0306 (11) | 0.0593 (15) | 0.0424 (14) | −0.0006 (11) | 0.0055 (11) | 0.0033 (13) |
C1 | 0.0327 (14) | 0.0546 (17) | 0.0388 (16) | 0.0000 (13) | 0.0058 (12) | 0.0033 (15) |
C2 | 0.0379 (16) | 0.0617 (18) | 0.0373 (16) | −0.0015 (13) | 0.0073 (13) | 0.0017 (15) |
C3 | 0.0375 (16) | 0.079 (2) | 0.055 (2) | −0.0110 (15) | 0.0061 (16) | −0.0081 (19) |
C4 | 0.0375 (17) | 0.083 (2) | 0.073 (2) | −0.0009 (17) | 0.0173 (18) | −0.004 (2) |
C5 | 0.0496 (19) | 0.068 (2) | 0.062 (2) | 0.0047 (16) | 0.0191 (18) | −0.0052 (19) |
C6 | 0.0430 (17) | 0.0568 (19) | 0.0468 (18) | −0.0007 (14) | 0.0076 (15) | −0.0001 (16) |
C7 | 0.054 (2) | 0.058 (2) | 0.063 (2) | −0.0073 (16) | 0.0126 (17) | −0.0091 (18) |
C8 | 0.088 (6) | 0.087 (5) | 0.105 (6) | −0.007 (4) | −0.039 (5) | 0.009 (5) |
C9 | 0.103 (6) | 0.062 (4) | 0.117 (7) | 0.002 (4) | −0.016 (5) | −0.004 (5) |
C7' | 0.054 (2) | 0.058 (2) | 0.063 (2) | −0.0073 (16) | 0.0126 (17) | −0.0091 (18) |
C8' | 0.097 (7) | 0.107 (8) | 0.100 (7) | −0.017 (6) | −0.023 (6) | −0.001 (6) |
C9' | 0.104 (7) | 0.076 (6) | 0.123 (8) | −0.008 (5) | 0.000 (7) | 0.017 (6) |
C10 | 0.0483 (17) | 0.071 (2) | 0.0425 (17) | −0.0054 (15) | 0.0089 (16) | −0.0042 (18) |
C11 | 0.078 (3) | 0.102 (3) | 0.067 (2) | −0.020 (2) | 0.001 (2) | −0.028 (2) |
C12 | 0.129 (4) | 0.083 (3) | 0.070 (3) | 0.034 (3) | 0.023 (3) | −0.001 (3) |
C13 | 0.0318 (14) | 0.0524 (16) | 0.0368 (15) | 0.0004 (12) | −0.0002 (13) | 0.0025 (15) |
C14 | 0.0303 (14) | 0.0432 (14) | 0.0298 (13) | −0.0047 (11) | −0.0031 (11) | 0.0008 (13) |
C15 | 0.0345 (15) | 0.0472 (15) | 0.0351 (15) | 0.0012 (12) | −0.0038 (13) | 0.0037 (14) |
C16 | 0.0347 (15) | 0.0487 (16) | 0.0346 (15) | −0.0063 (12) | −0.0004 (13) | 0.0021 (13) |
C17 | 0.0293 (14) | 0.0566 (17) | 0.0385 (15) | −0.0018 (12) | 0.0038 (12) | 0.0012 (15) |
C18 | 0.0327 (15) | 0.0434 (15) | 0.0371 (16) | 0.0001 (11) | −0.0028 (12) | 0.0002 (14) |
C19 | 0.0337 (14) | 0.0413 (14) | 0.0303 (14) | −0.0061 (11) | −0.0007 (12) | 0.0023 (13) |
C20 | 0.0473 (18) | 0.062 (2) | 0.0412 (18) | −0.0058 (14) | 0.0078 (14) | 0.0118 (16) |
C21 | 0.081 (3) | 0.131 (4) | 0.051 (2) | −0.006 (2) | −0.005 (2) | 0.026 (3) |
C22 | 0.116 (4) | 0.070 (3) | 0.081 (3) | −0.027 (2) | 0.019 (3) | 0.021 (2) |
C23 | 0.073 (3) | 0.116 (3) | 0.081 (3) | 0.012 (2) | 0.038 (2) | 0.038 (3) |
C24 | 0.0387 (16) | 0.0498 (17) | 0.0567 (19) | 0.0062 (13) | 0.0012 (15) | 0.0023 (16) |
C25 | 0.067 (2) | 0.077 (3) | 0.072 (2) | 0.024 (2) | −0.003 (2) | −0.007 (2) |
C26 | 0.0308 (14) | 0.0571 (18) | 0.0479 (18) | 0.0103 (13) | 0.0022 (14) | 0.0090 (16) |
C27 | 0.0482 (19) | 0.073 (2) | 0.057 (2) | 0.0023 (17) | −0.0059 (17) | 0.0125 (19) |
C28 | 0.055 (2) | 0.080 (3) | 0.091 (3) | −0.0040 (18) | −0.025 (2) | 0.013 (2) |
C29 | 0.082 (3) | 0.099 (3) | 0.084 (3) | 0.009 (3) | −0.044 (3) | 0.000 (3) |
C30 | 0.089 (3) | 0.106 (3) | 0.057 (2) | 0.011 (3) | −0.021 (2) | 0.018 (2) |
C31 | 0.057 (2) | 0.079 (2) | 0.054 (2) | 0.0035 (17) | −0.0029 (18) | 0.0169 (19) |
O1—C19 | 1.354 (3) | C13—H13A | 0.9300 |
O1—H1 | 0.93 (4) | C14—C15 | 1.392 (4) |
N1—C13 | 1.272 (4) | C14—C19 | 1.405 (4) |
N1—C1 | 1.443 (3) | C15—C16 | 1.381 (4) |
C1—C6 | 1.398 (4) | C15—H15A | 0.9300 |
C1—C2 | 1.400 (4) | C16—C17 | 1.398 (4) |
C2—C3 | 1.395 (4) | C16—C20 | 1.526 (4) |
C2—C10 | 1.516 (4) | C17—C18 | 1.387 (4) |
C3—C4 | 1.372 (5) | C17—H17A | 0.9300 |
C3—H3A | 0.9300 | C18—C19 | 1.389 (4) |
C4—C5 | 1.376 (5) | C18—C24 | 1.525 (4) |
C4—H4A | 0.9300 | C20—C22 | 1.527 (5) |
C5—C6 | 1.392 (4) | C20—C23 | 1.527 (5) |
C5—H5A | 0.9300 | C20—C21 | 1.532 (5) |
C6—C7 | 1.520 (5) | C21—H21A | 0.9600 |
C7—C8 | 1.480 (7) | C21—H21B | 0.9600 |
C7—C9 | 1.535 (7) | C21—H21C | 0.9600 |
C7—H7A | 0.9800 | C22—H22A | 0.9600 |
C8—H8A | 0.9600 | C22—H22B | 0.9600 |
C8—H8B | 0.9600 | C22—H22C | 0.9600 |
C8—H8C | 0.9600 | C23—H23A | 0.9600 |
C9—H9A | 0.9600 | C23—H23B | 0.9600 |
C9—H9B | 0.9600 | C23—H23C | 0.9600 |
C9—H9C | 0.9600 | C24—C26 | 1.519 (5) |
C8'—H8'A | 0.9600 | C24—C25 | 1.528 (5) |
C8'—H8'B | 0.9600 | C24—H24A | 0.9800 |
C8'—H8'C | 0.9600 | C25—H25A | 0.9600 |
C9'—H9'A | 0.9600 | C25—H25B | 0.9600 |
C9'—H9'B | 0.9600 | C25—H25C | 0.9600 |
C9'—H9'C | 0.9600 | C26—C31 | 1.375 (5) |
C10—C11 | 1.509 (5) | C26—C27 | 1.385 (4) |
C10—C12 | 1.517 (5) | C27—C28 | 1.381 (5) |
C10—H10A | 0.9800 | C27—H27A | 0.9300 |
C11—H11A | 0.9600 | C28—C29 | 1.366 (6) |
C11—H11B | 0.9600 | C28—H28A | 0.9300 |
C11—H11C | 0.9600 | C29—C30 | 1.373 (6) |
C12—H12A | 0.9600 | C29—H29A | 0.9300 |
C12—H12B | 0.9600 | C30—C31 | 1.383 (6) |
C12—H12C | 0.9600 | C30—H30A | 0.9300 |
C13—C14 | 1.458 (4) | C31—H31A | 0.9300 |
C19—O1—H1 | 108 (2) | C16—C15—H15A | 118.6 |
C13—N1—C1 | 119.5 (2) | C14—C15—H15A | 118.6 |
C6—C1—C2 | 122.3 (3) | C15—C16—C17 | 116.0 (3) |
C6—C1—N1 | 120.6 (3) | C15—C16—C20 | 121.6 (3) |
C2—C1—N1 | 117.0 (3) | C17—C16—C20 | 122.4 (2) |
C3—C2—C1 | 117.5 (3) | C18—C17—C16 | 123.7 (3) |
C3—C2—C10 | 120.6 (3) | C18—C17—H17A | 118.1 |
C1—C2—C10 | 121.8 (2) | C16—C17—H17A | 118.1 |
C4—C3—C2 | 121.2 (3) | C17—C18—C19 | 118.4 (2) |
C4—C3—H3A | 119.4 | C17—C18—C24 | 122.1 (3) |
C2—C3—H3A | 119.4 | C19—C18—C24 | 119.5 (3) |
C3—C4—C5 | 120.1 (3) | O1—C19—C18 | 118.8 (2) |
C3—C4—H4A | 120.0 | O1—C19—C14 | 121.2 (2) |
C5—C4—H4A | 120.0 | C18—C19—C14 | 120.0 (2) |
C4—C5—C6 | 121.6 (3) | C16—C20—C22 | 108.8 (3) |
C4—C5—H5A | 119.2 | C16—C20—C23 | 112.7 (3) |
C6—C5—H5A | 119.2 | C22—C20—C23 | 109.5 (3) |
C5—C6—C1 | 117.3 (3) | C16—C20—C21 | 110.4 (3) |
C5—C6—C7 | 120.6 (3) | C22—C20—C21 | 108.0 (3) |
C1—C6—C7 | 122.1 (3) | C23—C20—C21 | 107.4 (3) |
C8—C7—C6 | 111.5 (5) | C20—C21—H21A | 109.5 |
C8—C7—C9 | 108.9 (7) | C20—C21—H21B | 109.5 |
C6—C7—C9 | 113.9 (4) | H21A—C21—H21B | 109.5 |
C8—C7—H7A | 107.4 | C20—C21—H21C | 109.5 |
C6—C7—H7A | 107.4 | H21A—C21—H21C | 109.5 |
C9—C7—H7A | 107.4 | H21B—C21—H21C | 109.5 |
C7—C8—H8A | 109.5 | C20—C22—H22A | 109.5 |
C7—C8—H8B | 109.5 | C20—C22—H22B | 109.5 |
H8A—C8—H8B | 109.5 | H22A—C22—H22B | 109.5 |
C7—C8—H8C | 109.5 | C20—C22—H22C | 109.5 |
H8A—C8—H8C | 109.5 | H22A—C22—H22C | 109.5 |
H8B—C8—H8C | 109.5 | H22B—C22—H22C | 109.5 |
C7—C9—H9A | 109.5 | C20—C23—H23A | 109.5 |
C7—C9—H9B | 109.5 | C20—C23—H23B | 109.5 |
H9A—C9—H9B | 109.5 | H23A—C23—H23B | 109.5 |
C7—C9—H9C | 109.5 | C20—C23—H23C | 109.5 |
H9A—C9—H9C | 109.5 | H23A—C23—H23C | 109.5 |
H9B—C9—H9C | 109.5 | H23B—C23—H23C | 109.5 |
H8'A—C8'—H8'B | 109.5 | C26—C24—C18 | 110.2 (2) |
H8'A—C8'—H8'C | 109.5 | C26—C24—C25 | 112.6 (3) |
H8'B—C8'—H8'C | 109.5 | C18—C24—C25 | 113.4 (3) |
H9'A—C9'—H9'B | 109.5 | C26—C24—H24A | 106.7 |
H9'A—C9'—H9'C | 109.5 | C18—C24—H24A | 106.7 |
H9'B—C9'—H9'C | 109.5 | C25—C24—H24A | 106.7 |
C11—C10—C2 | 113.6 (3) | C24—C25—H25A | 109.5 |
C11—C10—C12 | 111.4 (3) | C24—C25—H25B | 109.5 |
C2—C10—C12 | 109.3 (3) | H25A—C25—H25B | 109.5 |
C11—C10—H10A | 107.4 | C24—C25—H25C | 109.5 |
C2—C10—H10A | 107.4 | H25A—C25—H25C | 109.5 |
C12—C10—H10A | 107.4 | H25B—C25—H25C | 109.5 |
C10—C11—H11A | 109.5 | C31—C26—C27 | 117.7 (3) |
C10—C11—H11B | 109.5 | C31—C26—C24 | 120.9 (3) |
H11A—C11—H11B | 109.5 | C27—C26—C24 | 121.4 (3) |
C10—C11—H11C | 109.5 | C28—C27—C26 | 121.7 (3) |
H11A—C11—H11C | 109.5 | C28—C27—H27A | 119.1 |
H11B—C11—H11C | 109.5 | C26—C27—H27A | 119.1 |
C10—C12—H12A | 109.5 | C29—C28—C27 | 119.4 (4) |
C10—C12—H12B | 109.5 | C29—C28—H28A | 120.3 |
H12A—C12—H12B | 109.5 | C27—C28—H28A | 120.3 |
C10—C12—H12C | 109.5 | C28—C29—C30 | 120.0 (4) |
H12A—C12—H12C | 109.5 | C28—C29—H29A | 120.0 |
H12B—C12—H12C | 109.5 | C30—C29—H29A | 120.0 |
N1—C13—C14 | 122.7 (3) | C29—C30—C31 | 120.1 (4) |
N1—C13—H13A | 118.6 | C29—C30—H30A | 120.0 |
C14—C13—H13A | 118.6 | C31—C30—H30A | 120.0 |
C15—C14—C19 | 119.0 (2) | C26—C31—C30 | 121.1 (4) |
C15—C14—C13 | 119.5 (2) | C26—C31—H31A | 119.5 |
C19—C14—C13 | 121.4 (2) | C30—C31—H31A | 119.5 |
C16—C15—C14 | 122.9 (3) | ||
C13—N1—C1—C6 | −87.7 (3) | C16—C17—C18—C19 | 0.9 (4) |
C13—N1—C1—C2 | 96.7 (3) | C16—C17—C18—C24 | −177.1 (3) |
C6—C1—C2—C3 | 0.5 (4) | C17—C18—C19—O1 | 179.0 (2) |
N1—C1—C2—C3 | 176.1 (3) | C24—C18—C19—O1 | −3.0 (4) |
C6—C1—C2—C10 | −176.7 (3) | C17—C18—C19—C14 | −0.7 (4) |
N1—C1—C2—C10 | −1.2 (4) | C24—C18—C19—C14 | 177.3 (3) |
C1—C2—C3—C4 | 0.4 (5) | C15—C14—C19—O1 | 179.9 (2) |
C10—C2—C3—C4 | 177.8 (3) | C13—C14—C19—O1 | −3.3 (4) |
C2—C3—C4—C5 | −0.1 (6) | C15—C14—C19—C18 | −0.4 (4) |
C3—C4—C5—C6 | −1.3 (6) | C13—C14—C19—C18 | 176.4 (3) |
C4—C5—C6—C1 | 2.2 (5) | C15—C16—C20—C22 | 69.1 (4) |
C4—C5—C6—C7 | −175.8 (3) | C17—C16—C20—C22 | −109.4 (3) |
C2—C1—C6—C5 | −1.8 (4) | C15—C16—C20—C23 | −169.3 (3) |
N1—C1—C6—C5 | −177.2 (3) | C17—C16—C20—C23 | 12.2 (4) |
C2—C1—C6—C7 | 176.2 (3) | C15—C16—C20—C21 | −49.2 (4) |
N1—C1—C6—C7 | 0.8 (4) | C17—C16—C20—C21 | 132.3 (3) |
C5—C6—C7—C8 | 94.5 (6) | C17—C18—C24—C26 | 90.3 (3) |
C1—C6—C7—C8 | −83.4 (6) | C19—C18—C24—C26 | −87.6 (3) |
C5—C6—C7—C9 | −29.2 (7) | C17—C18—C24—C25 | −37.0 (4) |
C1—C6—C7—C9 | 152.9 (6) | C19—C18—C24—C25 | 145.1 (3) |
C3—C2—C10—C11 | 36.4 (4) | C18—C24—C26—C31 | 115.0 (3) |
C1—C2—C10—C11 | −146.4 (3) | C25—C24—C26—C31 | −117.3 (4) |
C3—C2—C10—C12 | −88.6 (4) | C18—C24—C26—C27 | −64.6 (4) |
C1—C2—C10—C12 | 88.6 (4) | C25—C24—C26—C27 | 63.1 (4) |
C1—N1—C13—C14 | −172.8 (3) | C31—C26—C27—C28 | −0.5 (5) |
N1—C13—C14—C15 | 178.5 (3) | C24—C26—C27—C28 | 179.2 (3) |
N1—C13—C14—C19 | 1.7 (4) | C26—C27—C28—C29 | 0.4 (6) |
C19—C14—C15—C16 | 1.4 (4) | C27—C28—C29—C30 | −0.3 (7) |
C13—C14—C15—C16 | −175.5 (3) | C28—C29—C30—C31 | 0.2 (7) |
C14—C15—C16—C17 | −1.2 (4) | C27—C26—C31—C30 | 0.4 (5) |
C14—C15—C16—C20 | −179.8 (3) | C24—C26—C31—C30 | −179.2 (3) |
C15—C16—C17—C18 | 0.1 (4) | C29—C30—C31—C26 | −0.3 (6) |
C20—C16—C17—C18 | 178.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.93 (4) | 1.79 (4) | 2.620 (3) | 147 (3) |
Experimental details
Crystal data | |
Chemical formula | C31H39NO |
Mr | 441.63 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 294 |
a, b, c (Å) | 25.273 (4), 9.5496 (18), 11.115 (2) |
V (Å3) | 2682.6 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.24 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.974, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13332, 2505, 1964 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.105, 1.06 |
No. of reflections | 2505 |
No. of parameters | 319 |
No. of restraints | 41 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.13, −0.12 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.93 (4) | 1.79 (4) | 2.620 (3) | 147 (3) |
Late-metal catalysts bearing salicylaldiminato-type ligands play an important role in the catalytic oligomerization and polymerization of olefins (Ittel et al., 2000). Increasing the size of the imino substituent and the o-phenoxy substituent has a pronounced effect on the activity of the catalyst and the molecular weight of the polymer (Gibson et al., 2003). We have recently prepared a novel ligand, (I), and report its crystal structure here.
The molecular structure of (I) is shown in Fig. 1. In (I) the phenyl ring and the phenoxy ring form a dihedral angle of 75.18 (1)°, the phenylimino ring is nearly perpendicular to the phenoxy ring, with a dihedral angle of 81.51 (2)°. The dihedral angle between the phenyl and the phenylimino ring is 62.88 (1)°. Three C atoms of isopropyl attaching to the phenylimino ring are disordered in two locations with 55% and 45% probabilities. An intramolecular hydrogen bond is formed between the hydroxyl group and the N atom stabilizing the crystal structure.