N,N-Diiso­propyl-1-naphth­amide

The crystal structure of N,N-diiso­propyl-1-naphth­amide, C₁₇H₂₁NO, has been determined at 180 K. The molecular conformation is such that the plane of the amide group is approximately perpendicular to the plane of the naphthalene unit. C—H...O interactions link the mol­ecules into chains running along the b direction.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](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

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S1. Comment

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.

S2. Experimental

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.

S3. Refinement

All H atoms were placed geometrically and allowed to ride during subsequent refinement with an isotropic displacement parameter fixed at 1.2U_eq for the carbon to which the hydrogen was attached. For the methyl groups, U_iso was fixed at 1.5U_eq for the carbon.

Computing details

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.

Figures

	Fig. 1. The molecular unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
	Fig. 2. Projection onto (100) showing molecules of (I) linked by C—H···O interactions into chains running along the b direction. (CAMERON; Watkin et al.)

N,N-diisopropyl-1-naphthamide

Crystal data

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) Å^3	Plate, colourless
Z = 4	0.21 × 0.14 × 0.05 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0467P)^2 + 0.8144P] where P = (Fo^2 + 2Fc^2)/3
2494 reflections	(Δ/σ)max = 0.026
176 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1^i	0.95	2.41	3.327 (3)	162

Symmetry code: (i) −x+1, y−1/2, −z+1/2.