(S)-(+)-N-Benzyl-idene-1-(1-naphth-yl)ethyl-amine.

In the title chiral aldimine, C(19)H(17)N, the azomethine group is not fully conjugated with the phenyl substituent: the dihedral angle between phenyl and C(*)-N=C mean planes is ϕ(3) = 23.0 (2)°. Compared with the earlier DFT-B3LYP/6-31 G(d) computations from the literature, the C=N-C(*)-C(naph-thyl) torsion angle, found at ϕ(2) = -118.0 (2)° in the X-ray structure, does not match the angle calculated for the potential minimum energy at ϕ(2) = 0°. However, this angle is close to the second potential energy minimum at ϕ(2) = -120° which is ca. 8.5 kJ mol(-1) above the global energy minimum. Thus, the reported X-ray structure corresponds to the second most likely (according to DFT) conformer, allowing the existence of other polymorphs to be anti-cipated.

Related literature

For a typical synthesis of the title compound, see: Lee & Ahn (2002 ▶). For general background to solvent-free synthesis, see: Tanaka & Toda (2000 ▶). For the structures of related imines, see: Espinosa Leija et al. (2009 ▶); Bernès et al. (2010 ▶). For the DFT study of the title compound (R enanti­omer), see: Fukuda et al. (2007 ▶).

Experimental

Crystal data

C19H17N

M = 259.34

Monoclinic,

a = 8.0761 (8) Å

b = 7.7874 (8) Å

c = 11.7760 (11) Å

β = 95.033 (7)°

V = 737.76 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 298 K

0.4 × 0.2 × 0.2 mm

Data collection

Siemens P4 diffractometer

2470 measured reflections

1595 independent reflections

1276 reflections with I > 2σ(I)

R int = 0.017

3 standard reflections every 97 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.094

S = 1.02

1595 reflections

183 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.09 e Å−3

Δρmin = −0.08 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012980/ld2008sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012980/ld2008Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H17N	F(000) = 276
Mr = 259.34	Dx = 1.167 Mg m−3
Monoclinic, P21	Melting point: 352 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.0761 (8) Å	Cell parameters from 80 reflections
b = 7.7874 (8) Å	θ = 4.9–12.3°
c = 11.7760 (11) Å	µ = 0.07 mm−1
β = 95.033 (7)°	T = 298 K
V = 737.76 (13) Å3	Irregular, colourless
Z = 2	0.4 × 0.2 × 0.2 mm

Siemens P4 diffractometer	Rint = 0.017
Radiation source: fine-focus sealed tube	θmax = 26.2°, θmin = 2.5°
graphite	h = −10→3
2θ/ω scans	k = −1→9
2470 measured reflections	l = −14→14
1595 independent reflections	3 standard reflections every 97 reflections
1276 reflections with I > 2σ(I)	intensity decay: 1%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.0477P)2 + 0.0347P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
1595 reflections	Δρmax = 0.09 e Å−3
183 parameters	Δρmin = −0.08 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.063 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: 223 Friedel pairs merged

	x	y	z	Uiso*/Ueq
N1	0.3971 (2)	0.6059 (3)	0.71942 (14)	0.0646 (5)
C2	0.4226 (3)	0.6094 (3)	0.61588 (18)	0.0643 (6)
H2A	0.3363	0.6432	0.5631	0.077*
C3	0.5833 (3)	0.5624 (3)	0.57416 (18)	0.0662 (6)
C4	0.6202 (4)	0.6121 (4)	0.4665 (2)	0.0906 (8)
H4A	0.5440	0.6761	0.4203	0.109*
C5	0.7722 (5)	0.5659 (5)	0.4274 (3)	0.1090 (11)
H5A	0.7989	0.6028	0.3561	0.131*
C6	0.8809 (4)	0.4676 (5)	0.4930 (3)	0.1058 (12)
H6A	0.9813	0.4356	0.4660	0.127*
C7	0.8442 (3)	0.4155 (5)	0.5982 (3)	0.0977 (10)
H7A	0.9188	0.3468	0.6423	0.117*
C8	0.6973 (3)	0.4640 (4)	0.6394 (2)	0.0748 (7)
H8A	0.6745	0.4301	0.7121	0.090*
C9	0.2278 (2)	0.6405 (3)	0.74826 (16)	0.0583 (5)
H9A	0.1547	0.6558	0.6781	0.070*
C10	0.1713 (3)	0.4844 (3)	0.8128 (2)	0.0747 (7)
H10A	0.1743	0.3844	0.7654	0.112*
H10B	0.0599	0.5025	0.8328	0.112*
H10C	0.2442	0.4681	0.8809	0.112*
C11	0.2202 (3)	0.7992 (3)	0.82185 (16)	0.0538 (5)
C12	0.3561 (3)	0.8538 (3)	0.88883 (18)	0.0648 (6)
H12A	0.4567	0.7968	0.8856	0.078*
C13	0.3473 (3)	0.9946 (3)	0.9628 (2)	0.0760 (7)
H13A	0.4412	1.0271	1.0092	0.091*
C14	0.2046 (3)	1.0830 (3)	0.96724 (19)	0.0729 (7)
H14A	0.2011	1.1765	1.0161	0.087*
C15	0.0608 (3)	1.0349 (3)	0.89846 (17)	0.0595 (5)
C16	−0.0910 (3)	1.1256 (3)	0.90111 (19)	0.0729 (7)
H16A	−0.0950	1.2215	0.9478	0.088*
C17	−0.2301 (3)	1.0758 (4)	0.8373 (2)	0.0776 (7)
H17A	−0.3285	1.1369	0.8407	0.093*
C18	−0.2257 (3)	0.9330 (4)	0.7667 (2)	0.0731 (7)
H18A	−0.3217	0.8987	0.7233	0.088*
C19	−0.0826 (2)	0.8434 (3)	0.76058 (18)	0.0618 (6)
H19A	−0.0822	0.7490	0.7122	0.074*
C20	0.0660 (2)	0.8899 (3)	0.82582 (16)	0.0529 (5)

	U11	U22	U33	U12	U13	U23
N1	0.0602 (10)	0.0696 (13)	0.0646 (10)	0.0073 (10)	0.0089 (8)	−0.0043 (10)
C2	0.0694 (13)	0.0571 (13)	0.0670 (12)	0.0072 (12)	0.0095 (11)	−0.0043 (11)
C3	0.0726 (14)	0.0565 (12)	0.0718 (12)	−0.0021 (11)	0.0185 (11)	−0.0127 (11)
C4	0.121 (2)	0.0679 (16)	0.0887 (16)	0.0076 (18)	0.0422 (16)	−0.0017 (14)
C5	0.139 (3)	0.084 (2)	0.116 (2)	−0.017 (2)	0.074 (2)	−0.023 (2)
C6	0.0783 (18)	0.100 (2)	0.145 (3)	−0.0151 (19)	0.0411 (19)	−0.059 (2)
C7	0.0638 (15)	0.112 (3)	0.117 (2)	0.0058 (16)	0.0057 (15)	−0.052 (2)
C8	0.0638 (14)	0.0823 (17)	0.0782 (13)	0.0047 (14)	0.0061 (11)	−0.0211 (13)
C9	0.0544 (11)	0.0602 (12)	0.0606 (11)	0.0038 (11)	0.0073 (9)	−0.0060 (11)
C10	0.0847 (16)	0.0558 (14)	0.0842 (15)	−0.0062 (13)	0.0114 (12)	−0.0021 (13)
C11	0.0571 (11)	0.0528 (12)	0.0530 (10)	−0.0038 (10)	0.0127 (9)	0.0041 (9)
C12	0.0600 (13)	0.0637 (13)	0.0708 (12)	−0.0029 (12)	0.0060 (11)	0.0000 (12)
C13	0.0773 (17)	0.0729 (17)	0.0765 (14)	−0.0175 (15)	−0.0008 (12)	−0.0106 (14)
C14	0.0912 (17)	0.0565 (14)	0.0723 (13)	−0.0121 (13)	0.0155 (12)	−0.0119 (11)
C15	0.0730 (14)	0.0493 (11)	0.0587 (11)	−0.0047 (11)	0.0209 (10)	0.0048 (10)
C16	0.0884 (18)	0.0584 (13)	0.0768 (14)	0.0041 (14)	0.0341 (13)	−0.0024 (13)
C17	0.0715 (16)	0.0747 (17)	0.0901 (15)	0.0131 (14)	0.0269 (13)	0.0072 (14)
C18	0.0605 (13)	0.0809 (17)	0.0794 (14)	0.0022 (13)	0.0145 (11)	0.0021 (13)
C19	0.0601 (13)	0.0612 (13)	0.0655 (11)	−0.0024 (11)	0.0139 (10)	−0.0031 (11)
C20	0.0591 (11)	0.0495 (11)	0.0520 (9)	−0.0052 (9)	0.0166 (8)	0.0045 (9)

N1—C2	1.255 (2)	C10—H10C	0.9600
N1—C9	1.462 (3)	C11—C12	1.362 (3)
C2—C3	1.473 (3)	C11—C20	1.436 (3)
C2—H2A	0.9300	C12—C13	1.405 (3)
C3—C8	1.379 (3)	C12—H12A	0.9300
C3—C4	1.383 (3)	C13—C14	1.348 (3)
C4—C5	1.395 (4)	C13—H13A	0.9300
C4—H4A	0.9300	C14—C15	1.407 (3)
C5—C6	1.355 (5)	C14—H14A	0.9300
C5—H5A	0.9300	C15—C16	1.418 (3)
C6—C7	1.361 (5)	C15—C20	1.420 (3)
C6—H6A	0.9300	C16—C17	1.352 (3)
C7—C8	1.373 (3)	C16—H16A	0.9300
C7—H7A	0.9300	C17—C18	1.391 (4)
C8—H8A	0.9300	C17—H17A	0.9300
C9—C11	1.514 (3)	C18—C19	1.358 (3)
C9—C10	1.525 (3)	C18—H18A	0.9300
C9—H9A	0.9800	C19—C20	1.414 (3)
C10—H10A	0.9600	C19—H19A	0.9300
C10—H10B	0.9600
C2—N1—C9	117.30 (18)	H10A—C10—H10C	109.5
N1—C2—C3	122.9 (2)	H10B—C10—H10C	109.5
N1—C2—H2A	118.5	C12—C11—C20	118.99 (19)
C3—C2—H2A	118.5	C12—C11—C9	121.04 (19)
C8—C3—C4	118.6 (2)	C20—C11—C9	119.90 (18)
C8—C3—C2	121.2 (2)	C11—C12—C13	121.4 (2)
C4—C3—C2	120.2 (2)	C11—C12—H12A	119.3
C3—C4—C5	119.8 (3)	C13—C12—H12A	119.3
C3—C4—H4A	120.1	C14—C13—C12	120.8 (2)
C5—C4—H4A	120.1	C14—C13—H13A	119.6
C6—C5—C4	120.2 (3)	C12—C13—H13A	119.6
C6—C5—H5A	119.9	C13—C14—C15	120.5 (2)
C4—C5—H5A	119.9	C13—C14—H14A	119.8
C5—C6—C7	120.4 (3)	C15—C14—H14A	119.8
C5—C6—H6A	119.8	C14—C15—C16	121.8 (2)
C7—C6—H6A	119.8	C14—C15—C20	119.5 (2)
C6—C7—C8	120.2 (3)	C16—C15—C20	118.7 (2)
C6—C7—H7A	119.9	C17—C16—C15	121.5 (2)
C8—C7—H7A	119.9	C17—C16—H16A	119.2
C7—C8—C3	120.8 (3)	C15—C16—H16A	119.2
C7—C8—H8A	119.6	C16—C17—C18	119.9 (2)
C3—C8—H8A	119.6	C16—C17—H17A	120.1
N1—C9—C11	111.65 (18)	C18—C17—H17A	120.1
N1—C9—C10	107.2 (2)	C19—C18—C17	120.6 (2)
C11—C9—C10	109.68 (15)	C19—C18—H18A	119.7
N1—C9—H9A	109.4	C17—C18—H18A	119.7
C11—C9—H9A	109.4	C18—C19—C20	121.7 (2)
C10—C9—H9A	109.4	C18—C19—H19A	119.2
C9—C10—H10A	109.5	C20—C19—H19A	119.2
C9—C10—H10B	109.5	C19—C20—C15	117.57 (19)
H10A—C10—H10B	109.5	C19—C20—C11	123.62 (18)
C9—C10—H10C	109.5	C15—C20—C11	118.81 (18)
C9—N1—C2—C3	−174.6 (2)	C11—C12—C13—C14	−1.9 (4)
N1—C2—C3—C8	19.9 (4)	C12—C13—C14—C15	0.6 (4)
N1—C2—C3—C4	−162.2 (3)	C13—C14—C15—C16	−179.9 (2)
C8—C3—C4—C5	−1.6 (4)	C13—C14—C15—C20	1.4 (3)
C2—C3—C4—C5	−179.5 (2)	C14—C15—C16—C17	−178.0 (2)
C3—C4—C5—C6	2.3 (5)	C20—C15—C16—C17	0.7 (3)
C4—C5—C6—C7	−1.1 (5)	C15—C16—C17—C18	−0.3 (4)
C5—C6—C7—C8	−0.8 (5)	C16—C17—C18—C19	−0.4 (4)
C6—C7—C8—C3	1.6 (4)	C17—C18—C19—C20	0.6 (3)
C4—C3—C8—C7	−0.3 (4)	C18—C19—C20—C15	−0.1 (3)
C2—C3—C8—C7	177.6 (3)	C18—C19—C20—C11	−179.8 (2)
C2—N1—C9—C11	−118.0 (2)	C14—C15—C20—C19	178.3 (2)
C2—N1—C9—C10	121.9 (2)	C16—C15—C20—C19	−0.5 (3)
N1—C9—C11—C12	−25.3 (3)	C14—C15—C20—C11	−2.0 (3)
C10—C9—C11—C12	93.4 (2)	C16—C15—C20—C11	179.16 (18)
N1—C9—C11—C20	157.71 (17)	C12—C11—C20—C19	−179.5 (2)
C10—C9—C11—C20	−83.6 (2)	C9—C11—C20—C19	−2.5 (3)
C20—C11—C12—C13	1.1 (3)	C12—C11—C20—C15	0.8 (3)
C9—C11—C12—C13	−175.92 (19)	C9—C11—C20—C15	177.88 (17)