Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003580/om6007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003580/om6007Isup2.hkl |
CCDC reference: 159877
Key indicators
- Single-crystal X-ray study
- T = 180 K
- Mean (C-C) = 0.004 Å
- R factor = 0.065
- wR factor = 0.148
- Data-to-parameter ratio = 14.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
1-Naphthoyl chloride (5.4 ml, 35.8 mmol) was added dropwise to diisopropylamine (9.8 ml, 74.7 mmol) in Et2O (50 ml) at 273 K and the mixture was stirred for 24 h at room temperature after which time H2O (40 ml) was added. The aqueous phase was extracted with Et2O (3 × 30 ml) and the organic extracts washed with H2O, 1M HCl and saturated NaHCO3 (25 ml each) and dried (MgSO4). Removal of the solvent afforded the title compound, which was recrystallized from tetrahydrofuran.
All H atoms were placed geometrically and allowed to ride during subsequent refinement with an isotropic displacement parameter fixed at 1.2Ueq for the carbon to which the hydrogen was attached. For the methyl groups, Uiso was fixed at 1.5Ueq for the carbon.
Data collection: COLLECT (Nonius BV, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick 1997); program(s) used to refine structure: SHELXL97 (Sheldrick 1997); software used to prepare material for publication: SHELXL97.
C17H21NO | F(000) = 552 |
Mr = 255.35 | Dx = 1.169 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5403 (10) Å | Cell parameters from 13372 reflections |
b = 13.6498 (19) Å | θ = 1.0–25.0° |
c = 14.4042 (11) Å | µ = 0.07 mm−1 |
β = 101.958 (8)° | T = 180 K |
V = 1450.4 (3) Å3 | Plate, colourless |
Z = 4 | 0.21 × 0.14 × 0.05 mm |
Nonius KappaCCD diffractometer | 2494 independent reflections |
Radiation source: fine-focus sealed tube | 1725 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Thin–slice ω and ϕ scans | θmax = 24.9°, θmin = 3.6° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −7→8 |
Tmin = 0.992, Tmax = 0.997 | k = −16→16 |
8393 measured reflections | l = −17→16 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.8144P] where P = (Fo2 + 2Fc2)/3 |
2494 reflections | (Δ/σ)max = 0.026 |
176 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C17H21NO | V = 1450.4 (3) Å3 |
Mr = 255.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5403 (10) Å | µ = 0.07 mm−1 |
b = 13.6498 (19) Å | T = 180 K |
c = 14.4042 (11) Å | 0.21 × 0.14 × 0.05 mm |
β = 101.958 (8)° |
Nonius KappaCCD diffractometer | 2494 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1725 reflections with I > 2σ(I) |
Tmin = 0.992, Tmax = 0.997 | Rint = 0.064 |
8393 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.27 e Å−3 |
2494 reflections | Δρmin = −0.21 e Å−3 |
176 parameters |
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. All H atoms placed geometrically and allowed to ride during subsequent refinement. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.6333 (2) | 0.64758 (14) | 0.11239 (14) | 0.0524 (5) | |
N1 | 0.9299 (3) | 0.60519 (15) | 0.15704 (14) | 0.0374 (5) | |
C1 | 0.6901 (3) | 0.48566 (19) | 0.17037 (17) | 0.0376 (6) | |
C2 | 0.6366 (3) | 0.41683 (19) | 0.10165 (17) | 0.0378 (6) | |
H2 | 0.6462 | 0.4308 | 0.0383 | 0.045* | |
C3 | 0.5673 (3) | 0.3252 (2) | 0.1226 (2) | 0.0465 (7) | |
H3 | 0.5313 | 0.2781 | 0.0738 | 0.056* | |
C4 | 0.5523 (3) | 0.3046 (2) | 0.21413 (19) | 0.0435 (7) | |
H4 | 0.5060 | 0.2429 | 0.2286 | 0.052* | |
C5 | 0.5937 (3) | 0.3556 (2) | 0.38114 (19) | 0.0466 (7) | |
H5 | 0.5480 | 0.2942 | 0.3964 | 0.056* | |
C6 | 0.6457 (4) | 0.4225 (2) | 0.4516 (2) | 0.0565 (8) | |
H6 | 0.6385 | 0.4073 | 0.5150 | 0.068* | |
C7 | 0.7099 (4) | 0.5135 (2) | 0.4295 (2) | 0.0547 (8) | |
H7 | 0.7443 | 0.5607 | 0.4784 | 0.066* | |
C8 | 0.7242 (3) | 0.5364 (2) | 0.33956 (18) | 0.0420 (6) | |
H8 | 0.7680 | 0.5991 | 0.3265 | 0.050* | |
C9 | 0.6744 (3) | 0.4673 (2) | 0.26480 (18) | 0.0404 (6) | |
C10 | 0.6050 (3) | 0.37428 (18) | 0.28635 (18) | 0.0364 (6) | |
C11 | 0.7507 (3) | 0.5863 (2) | 0.14439 (17) | 0.0401 (6) | |
C12 | 1.0706 (3) | 0.53121 (19) | 0.19379 (17) | 0.0390 (6) | |
H12 | 1.0062 | 0.4682 | 0.1998 | 0.047* | |
C13 | 1.1959 (3) | 0.5129 (2) | 0.12596 (19) | 0.0484 (7) | |
H13A | 1.1238 | 0.5016 | 0.0620 | 0.073* | |
H13B | 1.2710 | 0.4552 | 0.1467 | 0.073* | |
H13C | 1.2741 | 0.5702 | 0.1252 | 0.073* | |
C14 | 1.1776 (4) | 0.5570 (2) | 0.29204 (18) | 0.0514 (8) | |
H14A | 1.2410 | 0.6192 | 0.2893 | 0.077* | |
H14B | 1.2663 | 0.5052 | 0.3143 | 0.077* | |
H14C | 1.0947 | 0.5631 | 0.3359 | 0.077* | |
C15 | 0.9942 (3) | 0.70360 (19) | 0.13482 (19) | 0.0438 (7) | |
H15 | 1.1296 | 0.7013 | 0.1522 | 0.053* | |
C16 | 0.9362 (4) | 0.7839 (2) | 0.1954 (3) | 0.0667 (9) | |
H16A | 0.8038 | 0.7901 | 0.1800 | 0.100* | |
H16B | 0.9912 | 0.8462 | 0.1825 | 0.100* | |
H16C | 0.9761 | 0.7672 | 0.2627 | 0.100* | |
C17 | 0.9454 (4) | 0.7262 (2) | 0.0292 (2) | 0.0631 (9) | |
H17A | 0.9901 | 0.6736 | −0.0062 | 0.095* | |
H17B | 1.0012 | 0.7884 | 0.0168 | 0.095* | |
H17C | 0.8134 | 0.7312 | 0.0089 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0343 (10) | 0.0399 (11) | 0.0816 (14) | 0.0065 (9) | 0.0085 (9) | 0.0088 (10) |
N1 | 0.0316 (11) | 0.0340 (13) | 0.0466 (13) | 0.0001 (9) | 0.0078 (9) | 0.0052 (9) |
C1 | 0.0276 (13) | 0.0396 (16) | 0.0454 (15) | 0.0027 (11) | 0.0070 (10) | −0.0016 (12) |
C2 | 0.0326 (13) | 0.0426 (17) | 0.0393 (15) | 0.0022 (12) | 0.0100 (11) | −0.0001 (12) |
C3 | 0.0356 (14) | 0.0428 (17) | 0.0597 (19) | 0.0013 (12) | 0.0068 (12) | −0.0117 (13) |
C4 | 0.0323 (14) | 0.0409 (17) | 0.0575 (18) | −0.0013 (12) | 0.0098 (12) | 0.0002 (13) |
C5 | 0.0395 (15) | 0.0482 (17) | 0.0524 (17) | −0.0010 (13) | 0.0100 (12) | 0.0026 (14) |
C6 | 0.0546 (18) | 0.069 (2) | 0.0467 (17) | −0.0065 (16) | 0.0129 (13) | 0.0021 (15) |
C7 | 0.0520 (17) | 0.064 (2) | 0.0493 (18) | −0.0067 (15) | 0.0126 (13) | −0.0099 (15) |
C8 | 0.0362 (14) | 0.0424 (17) | 0.0482 (16) | −0.0061 (12) | 0.0105 (11) | −0.0067 (13) |
C9 | 0.0269 (13) | 0.0457 (17) | 0.0476 (16) | 0.0055 (12) | 0.0053 (10) | −0.0022 (13) |
C10 | 0.0261 (12) | 0.0361 (15) | 0.0476 (16) | 0.0012 (11) | 0.0090 (10) | 0.0023 (12) |
C11 | 0.0344 (14) | 0.0409 (16) | 0.0459 (15) | 0.0015 (12) | 0.0104 (11) | 0.0008 (12) |
C12 | 0.0318 (13) | 0.0339 (15) | 0.0504 (15) | 0.0007 (11) | 0.0061 (11) | 0.0087 (12) |
C13 | 0.0367 (14) | 0.0510 (18) | 0.0570 (17) | 0.0043 (13) | 0.0081 (12) | −0.0020 (14) |
C14 | 0.0422 (15) | 0.060 (2) | 0.0515 (17) | 0.0029 (14) | 0.0093 (12) | 0.0059 (14) |
C15 | 0.0342 (14) | 0.0329 (15) | 0.0634 (18) | −0.0038 (12) | 0.0085 (12) | 0.0019 (13) |
C16 | 0.0521 (18) | 0.0435 (18) | 0.103 (3) | −0.0033 (15) | 0.0129 (17) | −0.0186 (17) |
C17 | 0.0573 (19) | 0.051 (2) | 0.078 (2) | −0.0096 (15) | 0.0069 (15) | 0.0216 (16) |
O1—C11 | 1.236 (3) | C8—H8 | 0.9500 |
N1—C11 | 1.351 (3) | C9—C10 | 1.432 (4) |
N1—C12 | 1.481 (3) | C12—C13 | 1.514 (4) |
N1—C15 | 1.485 (3) | C12—C14 | 1.518 (3) |
C1—C2 | 1.364 (3) | C12—H12 | 1.0000 |
C1—C9 | 1.412 (3) | C13—H13A | 0.9800 |
C1—C11 | 1.519 (4) | C13—H13B | 0.9800 |
C2—C3 | 1.411 (4) | C13—H13C | 0.9800 |
C2—H2 | 0.9500 | C14—H14A | 0.9800 |
C3—C4 | 1.376 (4) | C14—H14B | 0.9800 |
C3—H3 | 0.9500 | C14—H14C | 0.9800 |
C4—C10 | 1.405 (4) | C15—C16 | 1.521 (4) |
C4—H4 | 0.9500 | C15—C17 | 1.521 (4) |
C5—C6 | 1.360 (4) | C15—H15 | 1.0000 |
C5—C10 | 1.409 (4) | C16—H16A | 0.9800 |
C5—H5 | 0.9500 | C16—H16B | 0.9800 |
C6—C7 | 1.394 (4) | C16—H16C | 0.9800 |
C6—H6 | 0.9500 | C17—H17A | 0.9800 |
C7—C8 | 1.358 (4) | C17—H17B | 0.9800 |
C7—H7 | 0.9500 | C17—H17C | 0.9800 |
C8—C9 | 1.422 (3) | ||
C11—N1—C12 | 122.7 (2) | N1—C12—C13 | 112.2 (2) |
C11—N1—C15 | 120.4 (2) | N1—C12—C14 | 112.2 (2) |
C12—N1—C15 | 116.88 (19) | C13—C12—C14 | 110.9 (2) |
C2—C1—C9 | 120.4 (2) | N1—C12—H12 | 107.0 |
C2—C1—C11 | 120.2 (2) | C13—C12—H12 | 107.0 |
C9—C1—C11 | 119.2 (2) | C14—C12—H12 | 107.0 |
C1—C2—C3 | 121.5 (2) | C12—C13—H13A | 109.5 |
C1—C2—H2 | 119.3 | C12—C13—H13B | 109.5 |
C3—C2—H2 | 119.3 | H13A—C13—H13B | 109.5 |
C4—C3—C2 | 119.6 (2) | C12—C13—H13C | 109.5 |
C4—C3—H3 | 120.2 | H13A—C13—H13C | 109.5 |
C2—C3—H3 | 120.2 | H13B—C13—H13C | 109.5 |
C3—C4—C10 | 120.3 (2) | C12—C14—H14A | 109.5 |
C3—C4—H4 | 119.9 | C12—C14—H14B | 109.5 |
C10—C4—H4 | 119.9 | H14A—C14—H14B | 109.5 |
C6—C5—C10 | 122.4 (3) | C12—C14—H14C | 109.5 |
C6—C5—H5 | 118.8 | H14A—C14—H14C | 109.5 |
C10—C5—H5 | 118.8 | H14B—C14—H14C | 109.5 |
C5—C6—C7 | 119.2 (3) | N1—C15—C16 | 112.5 (2) |
C5—C6—H6 | 120.4 | N1—C15—C17 | 112.1 (2) |
C7—C6—H6 | 120.4 | C16—C15—C17 | 112.9 (2) |
C8—C7—C6 | 121.5 (3) | N1—C15—H15 | 106.2 |
C8—C7—H7 | 119.3 | C16—C15—H15 | 106.2 |
C6—C7—H7 | 119.3 | C17—C15—H15 | 106.2 |
C7—C8—C9 | 120.6 (3) | C15—C16—H16A | 109.5 |
C7—C8—H8 | 119.7 | C15—C16—H16B | 109.5 |
C9—C8—H8 | 119.7 | H16A—C16—H16B | 109.5 |
C1—C9—C8 | 123.4 (2) | C15—C16—H16C | 109.5 |
C1—C9—C10 | 118.3 (2) | H16A—C16—H16C | 109.5 |
C8—C9—C10 | 118.4 (2) | H16B—C16—H16C | 109.5 |
C4—C10—C5 | 122.0 (2) | C15—C17—H17A | 109.5 |
C4—C10—C9 | 120.0 (2) | C15—C17—H17B | 109.5 |
C5—C10—C9 | 117.9 (2) | H17A—C17—H17B | 109.5 |
O1—C11—N1 | 122.7 (2) | C15—C17—H17C | 109.5 |
O1—C11—C1 | 118.4 (2) | H17A—C17—H17C | 109.5 |
N1—C11—C1 | 118.9 (2) | H17B—C17—H17C | 109.5 |
C9—C1—C2—C3 | −1.1 (4) | C1—C9—C10—C5 | 178.5 (2) |
C11—C1—C2—C3 | −175.4 (2) | C8—C9—C10—C5 | −1.3 (3) |
C1—C2—C3—C4 | 0.3 (4) | C12—N1—C11—O1 | −178.9 (2) |
C2—C3—C4—C10 | 0.2 (4) | C15—N1—C11—O1 | 1.7 (4) |
C10—C5—C6—C7 | 1.1 (4) | C12—N1—C11—C1 | 1.1 (3) |
C5—C6—C7—C8 | −1.1 (4) | C15—N1—C11—C1 | −178.4 (2) |
C6—C7—C8—C9 | −0.2 (4) | C2—C1—C11—O1 | 80.6 (3) |
C2—C1—C9—C8 | −178.8 (2) | C9—C1—C11—O1 | −93.8 (3) |
C11—C1—C9—C8 | −4.5 (3) | C2—C1—C11—N1 | −99.4 (3) |
C2—C1—C9—C10 | 1.4 (3) | C9—C1—C11—N1 | 86.2 (3) |
C11—C1—C9—C10 | 175.7 (2) | C11—N1—C12—C13 | 122.4 (2) |
C7—C8—C9—C1 | −178.4 (2) | C15—N1—C12—C13 | −58.1 (3) |
C7—C8—C9—C10 | 1.4 (4) | C11—N1—C12—C14 | −111.8 (3) |
C3—C4—C10—C5 | −179.3 (2) | C15—N1—C12—C14 | 67.7 (3) |
C3—C4—C10—C9 | 0.1 (4) | C11—N1—C15—C16 | 61.7 (3) |
C6—C5—C10—C4 | 179.5 (2) | C12—N1—C15—C16 | −117.7 (2) |
C6—C5—C10—C9 | 0.1 (4) | C11—N1—C15—C17 | −66.8 (3) |
C1—C9—C10—C4 | −0.9 (3) | C12—N1—C15—C17 | 113.8 (2) |
C8—C9—C10—C4 | 179.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.95 | 2.41 | 3.327 (3) | 162 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H21NO |
Mr | 255.35 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 180 |
a, b, c (Å) | 7.5403 (10), 13.6498 (19), 14.4042 (11) |
β (°) | 101.958 (8) |
V (Å3) | 1450.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.21 × 0.14 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.992, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8393, 2494, 1725 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.593 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.148, 1.07 |
No. of reflections | 2494 |
No. of parameters | 176 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 |
Computer programs: COLLECT (Nonius BV, 1998), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997), SHELXS97 (Sheldrick 1997), SHELXL97 (Sheldrick 1997), SHELXL97.
O1—C11 | 1.236 (3) | C5—C6 | 1.360 (4) |
N1—C11 | 1.351 (3) | C5—C10 | 1.409 (4) |
N1—C12 | 1.481 (3) | C6—C7 | 1.394 (4) |
N1—C15 | 1.485 (3) | C7—C8 | 1.358 (4) |
C1—C2 | 1.364 (3) | C8—C9 | 1.422 (3) |
C1—C9 | 1.412 (3) | C9—C10 | 1.432 (4) |
C1—C11 | 1.519 (4) | C12—C13 | 1.514 (4) |
C2—C3 | 1.411 (4) | C12—C14 | 1.518 (3) |
C3—C4 | 1.376 (4) | C15—C16 | 1.521 (4) |
C4—C10 | 1.405 (4) | C15—C17 | 1.521 (4) |
C11—N1—C12 | 122.7 (2) | C1—C9—C10 | 118.3 (2) |
C11—N1—C15 | 120.4 (2) | C8—C9—C10 | 118.4 (2) |
C12—N1—C15 | 116.88 (19) | C4—C10—C5 | 122.0 (2) |
C2—C1—C9 | 120.4 (2) | C4—C10—C9 | 120.0 (2) |
C2—C1—C11 | 120.2 (2) | C5—C10—C9 | 117.9 (2) |
C9—C1—C11 | 119.2 (2) | O1—C11—N1 | 122.7 (2) |
C1—C2—C3 | 121.5 (2) | O1—C11—C1 | 118.4 (2) |
C4—C3—C2 | 119.6 (2) | N1—C11—C1 | 118.9 (2) |
C3—C4—C10 | 120.3 (2) | N1—C12—C13 | 112.2 (2) |
C6—C5—C10 | 122.4 (3) | N1—C12—C14 | 112.2 (2) |
C5—C6—C7 | 119.2 (3) | C13—C12—C14 | 110.9 (2) |
C8—C7—C6 | 121.5 (3) | N1—C15—C16 | 112.5 (2) |
C7—C8—C9 | 120.6 (3) | N1—C15—C17 | 112.1 (2) |
C1—C9—C8 | 123.4 (2) | C16—C15—C17 | 112.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.95 | 2.41 | 3.327 (3) | 161.7 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
The use of directed orthometallation involving amide-type functional groups in general, and tertiary amides in particular, has revolutionized the synthesis of complex benzenoid aromatic compounds (Snieckus, 1990).
It is generally assumed that O—Li coordination is maintained from the reactive complex through to the products, but in the case of the tertiary amides such coordination is problematic. A tertiary amide group, even in a simple aromatic amide, lies twisted out of the plane of the benzene ring for steric reasons (Bowles et al., 1997), discouraging direct coordination of an oxygen lone pair to a 2-lithio substituent. It is clear that the twist angle affects the rate of lithiation (Beak et al., 1993), but even amides which are nearly perpendicular, e.g. naphthamides, undergo efficient ortholithiation (Clayden et al., 1999).
In light of the effect of amide twist angle on lithiation, we have investigated both aromatic tertiary amides and their litihated derivatives. We report here the structure of N,N-diisopropyl-1-naphthamide, (I), determined at 180 K.
The molecular conformation in (I) is such that the plane of the amide group forms an angle of 83.4 (2)° with the least-squares plane through the naphthalene unit. C—H···O interactions exist between the H atom in the 5-position of the napthalene ring and the carboxyl group of a neighbouring molecule [H5···O1i = 2.41 Å, C5—H5···O1i = 161.7°; symmetry code: (i) 1 - x, -0.5 + y, 0.5 - z]. These interactions link the molecules into chains running along the b direction.