(±)-1-{[(4-Methoxy­benzyl­idene)­amino](4-methoxy­phen­yl)meth­yl}-2-naphthol

Huang, X.-T.; Lin, K.; Ji, T.; Tang, G.; Zhao, Y.-F.

doi:10.1107/S1600536807025214

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(±)-1-{[(4-Methoxybenzylidene)amino](4-methoxyphenyl)methyl}-2-naphthol

X.-T. Huang, K. Lin, T. Ji, G. Tang and Y.-F. Zhao

The title compound, C₂₆H₂₃NO₃, is a key intermediate used in the synthesis of 1-[amino(4-methoxyphenyl)methyl]-2-naphthol, which has been found to be a potent chiral catalyst in the addition reactions of dialkylzinc compounds with aldehydes. The π-conjugated system formed by the methoxybenzylidene–imine tautomer is essentially planar. An intramolecular O—H

N hydrogen bond is formed between the hydroxyl OH group attached to the naphthalene group and the Schiff base N atom. The crystal packing is stabilized by van der Waals forces.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025214/dn2180sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025214/dn2180Isup2.hkl Contains datablock I

CCDC reference: 651524

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.004 Å
R factor = 0.071
wR factor = 0.156
Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C11    = ...          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound, (1), is a key intermediate used in the sythesis of amino naphthol,which was found to be potent chiral catalyst in the addition reactions of dialkylzincs to aldehydes.

In the title compound, C₂₆H₂₃NO₃, the π-conjugated system formed by the methoxy-benzylidene-imine tautomer is essentially planar with the largest deviation being -0.104 (2)Å at N1. This plane makes dihedral angles of 67.46 (4)° and 72.51 (7)° with the methoxy-phenyl and the naphtalene planes respectively (Fig. 1). An intramolecular O—HN hydrogen bond is formed between the hydroxyl OH attached to the naphtalene group and the Schiff base N atom (Table 1). The crystal packing is stabilized by van der Waals forces.

Related literature top

For related literature, see: Szatmari et al. (2003).

Experimental top

To a solution of 2-naphthol (1, 14.42 g, 0.1 mol) in absolute EtOH (50 ml) was added the benzaldehyde and 25% ethanolic ammonia solution (20 ml). The mixture was left to stand at ambient temperature for 12 h, during which a crystalline product (1) separated out (Szatmari et al., 2003). The crystals were filtered off and washed with cool ethanol, and then recrystallized from ethanol.

Structure description top

The title compound, (1), is a key intermediate used in the sythesis of amino naphthol,which was found to be potent chiral catalyst in the addition reactions of dialkylzincs to aldehydes.

For related literature, see: Szatmari et al. (2003).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); 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 ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. Molecular view of C₂₆H₂₃NO₃ with the atom labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Intramolecular hydrogen bond is represented as dashed line.
	Fig. 2. Preparation of the title compound.

(±)-1-{[(4-Methoxybenzylidene)amino](4-methoxyphenyl)methyl}-2-naphthol top

Crystal data top

C₂₆H₂₃NO₃	F(000) = 840
M_r = 397.45	D_x = 1.284 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3850 reflections
a = 20.790 (5) Å	θ = 2.6–27.8°
b = 10.717 (3) Å	µ = 0.08 mm⁻¹
c = 9.470 (2) Å	T = 298 K
β = 102.952 (4)°	Block, colourless
V = 2056.4 (9) Å³	0.46 × 0.45 × 0.16 mm
Z = 4

Data collection top

Bruker APEX area-detector diffractometer	3595 independent reflections
Radiation source: fine-focus sealed tube	3150 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.0°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −24→24
T_min = 0.963, T_max = 0.987	k = −8→12
10108 measured reflections	l = −11→11

Refinement top

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.048P)² + 0.9676P] where P = (F_o² + 2F_c²)/3
3594 reflections	(Δ/σ)_max = 0.001
274 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₆H₂₃NO₃	V = 2056.4 (9) Å³
M_r = 397.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.790 (5) Å	µ = 0.08 mm⁻¹
b = 10.717 (3) Å	T = 298 K
c = 9.470 (2) Å	0.46 × 0.45 × 0.16 mm
β = 102.952 (4)°

Data collection top

Bruker APEX area-detector diffractometer	3595 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3150 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.987	R_int = 0.022
10108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.22	Δρ_max = 0.19 e Å⁻³
3594 reflections	Δρ_min = −0.22 e Å⁻³
274 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C11	0.27872 (11)	0.4519 (2)	0.0544 (3)	0.0431 (6)
H11	0.2940	0.3665	0.0444	0.052*
C1	0.25378 (11)	0.5060 (2)	−0.0956 (3)	0.0422 (6)
N1	0.22533 (9)	0.44746 (19)	0.1312 (2)	0.0473 (5)
C9	0.28741 (12)	0.4774 (2)	−0.2060 (3)	0.0450 (6)
C15	0.33480 (11)	0.5258 (2)	0.1447 (2)	0.0416 (6)
O3	0.16486 (9)	0.6186 (2)	−0.0324 (2)	0.0700 (6)
H3	0.1771	0.5794	0.0433	0.105*
C19	0.20777 (12)	0.3448 (3)	0.1721 (3)	0.0496 (6)
H19	0.2293	0.2730	0.1526	0.060*
C14	0.39236 (12)	0.4702 (2)	0.2144 (3)	0.0485 (6)
H14	0.3982	0.3852	0.2015	0.058*
O2	0.48452 (9)	0.71911 (19)	0.4146 (2)	0.0688 (6)
C23	0.15520 (12)	0.3332 (3)	0.2488 (3)	0.0509 (6)
C13	0.44148 (12)	0.5365 (3)	0.3026 (3)	0.0520 (6)
H13	0.4804	0.4967	0.3481	0.062*
C2	0.20013 (12)	0.5824 (2)	−0.1284 (3)	0.0518 (6)
C12	0.43377 (12)	0.6605 (3)	0.3241 (3)	0.0488 (6)
C8	0.34508 (12)	0.4043 (2)	−0.1819 (3)	0.0516 (6)
H8	0.3618	0.3716	−0.0901	0.062*
O1	0.00340 (10)	0.3040 (2)	0.4600 (3)	0.0894 (8)
C24	0.12699 (14)	0.4356 (3)	0.3000 (3)	0.0617 (7)
H24	0.1426	0.5150	0.2865	0.074*
C16	0.32864 (12)	0.6507 (3)	0.1655 (3)	0.0584 (7)
H16	0.2904	0.6913	0.1176	0.070*
C17	0.37703 (13)	0.7179 (3)	0.2549 (3)	0.0621 (8)
H17	0.3712	0.8028	0.2684	0.074*
C10	0.26409 (14)	0.5238 (3)	−0.3472 (3)	0.0565 (7)
C4	0.20852 (16)	0.6009 (3)	−0.3738 (3)	0.0700 (9)
H4	0.1926	0.6328	−0.4663	0.084*
C3	0.17802 (15)	0.6293 (3)	−0.2683 (4)	0.0664 (8)
H3A	0.1413	0.6813	−0.2884	0.080*
C22	0.13130 (13)	0.2173 (3)	0.2716 (3)	0.0622 (8)
H22	0.1495	0.1470	0.2383	0.075*
C7	0.37670 (15)	0.3805 (3)	−0.2887 (4)	0.0665 (8)
H7	0.4152	0.3332	−0.2687	0.080*
C21	0.08089 (14)	0.2029 (3)	0.3429 (3)	0.0704 (9)
H21	0.0655	0.1237	0.3582	0.085*
C5	0.2979 (2)	0.4947 (3)	−0.4552 (3)	0.0783 (10)
H5	0.2820	0.5243	−0.5488	0.094*
C25	0.07700 (14)	0.4224 (3)	0.3697 (3)	0.0698 (8)
H25	0.0585	0.4924	0.4031	0.084*
C6	0.3529 (2)	0.4250 (4)	−0.4264 (4)	0.0841 (11)
H6	0.3748	0.4069	−0.4995	0.101*
C20	0.05380 (13)	0.3057 (3)	0.3907 (3)	0.0639 (8)
C18	0.47447 (15)	0.8432 (3)	0.4520 (4)	0.0748 (9)
H18A	0.4674	0.8945	0.3668	0.112*
H18B	0.5126	0.8724	0.5210	0.112*
H18C	0.4365	0.8476	0.4939	0.112*
C26	−0.01964 (17)	0.1877 (4)	0.4935 (4)	0.1035 (14)
H26A	−0.0367	0.1424	0.4057	0.155*
H26B	−0.0540	0.1991	0.5451	0.155*
H26C	0.0160	0.1415	0.5528	0.155*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.0411 (13)	0.0409 (13)	0.0499 (14)	0.0025 (11)	0.0156 (11)	−0.0014 (11)
C1	0.0360 (12)	0.0380 (13)	0.0503 (14)	−0.0050 (10)	0.0048 (10)	−0.0027 (11)
N1	0.0422 (11)	0.0527 (13)	0.0500 (12)	−0.0042 (10)	0.0166 (9)	−0.0037 (10)
C9	0.0477 (14)	0.0381 (13)	0.0493 (14)	−0.0145 (11)	0.0110 (11)	−0.0054 (11)
C15	0.0400 (13)	0.0460 (14)	0.0416 (13)	0.0027 (11)	0.0150 (10)	0.0013 (11)
O3	0.0528 (11)	0.0709 (14)	0.0869 (15)	0.0181 (10)	0.0167 (11)	−0.0049 (11)
C19	0.0415 (14)	0.0586 (16)	0.0471 (15)	0.0015 (12)	0.0067 (11)	0.0033 (12)
C14	0.0515 (15)	0.0448 (14)	0.0490 (15)	0.0082 (12)	0.0106 (12)	0.0054 (11)
O2	0.0471 (11)	0.0767 (14)	0.0738 (13)	0.0016 (10)	−0.0048 (10)	−0.0210 (11)
C23	0.0415 (14)	0.0624 (17)	0.0471 (15)	−0.0023 (12)	0.0061 (11)	0.0079 (13)
C13	0.0418 (14)	0.0623 (17)	0.0485 (15)	0.0108 (13)	0.0032 (11)	0.0062 (13)
C2	0.0451 (14)	0.0436 (14)	0.0628 (17)	−0.0031 (12)	0.0041 (13)	−0.0050 (12)
C12	0.0416 (14)	0.0594 (16)	0.0450 (14)	0.0027 (12)	0.0089 (11)	−0.0055 (12)
C8	0.0509 (15)	0.0515 (15)	0.0562 (16)	−0.0106 (12)	0.0203 (12)	−0.0082 (12)
O1	0.0590 (13)	0.131 (2)	0.0864 (16)	−0.0128 (13)	0.0337 (12)	0.0164 (15)
C24	0.0603 (17)	0.0684 (19)	0.0603 (18)	−0.0131 (15)	0.0221 (14)	−0.0063 (14)
C16	0.0404 (14)	0.0519 (16)	0.0747 (19)	0.0104 (12)	−0.0043 (13)	−0.0091 (14)
C17	0.0522 (16)	0.0472 (16)	0.081 (2)	0.0068 (13)	0.0027 (15)	−0.0147 (14)
C10	0.0691 (18)	0.0505 (16)	0.0467 (15)	−0.0215 (14)	0.0061 (13)	−0.0002 (12)
C4	0.087 (2)	0.0587 (18)	0.0534 (18)	−0.0173 (17)	−0.0086 (17)	0.0079 (14)
C3	0.0602 (18)	0.0526 (17)	0.075 (2)	0.0024 (14)	−0.0099 (16)	0.0052 (15)
C22	0.0514 (16)	0.0642 (18)	0.0703 (19)	0.0080 (14)	0.0120 (14)	0.0200 (15)
C7	0.0680 (19)	0.0654 (19)	0.077 (2)	−0.0162 (15)	0.0395 (17)	−0.0199 (16)
C21	0.0553 (17)	0.076 (2)	0.080 (2)	−0.0058 (16)	0.0140 (16)	0.0311 (17)
C5	0.110 (3)	0.082 (2)	0.0457 (17)	−0.032 (2)	0.0229 (18)	−0.0029 (16)
C25	0.0616 (18)	0.086 (2)	0.069 (2)	−0.0114 (16)	0.0295 (16)	−0.0113 (16)
C6	0.105 (3)	0.091 (3)	0.070 (2)	−0.032 (2)	0.050 (2)	−0.0225 (19)
C20	0.0419 (15)	0.097 (2)	0.0540 (17)	−0.0034 (16)	0.0123 (13)	0.0135 (16)
C18	0.0595 (18)	0.081 (2)	0.082 (2)	−0.0133 (16)	0.0116 (16)	−0.0308 (18)
C26	0.063 (2)	0.157 (4)	0.094 (3)	−0.034 (2)	0.0249 (19)	0.029 (3)

Geometric parameters (Å, º) top

C11—N1	1.458 (3)	O1—C26	1.398 (4)
C11—C15	1.507 (3)	C24—C25	1.357 (4)
C11—C1	1.514 (3)	C24—H24	0.9300
C11—H11	0.9800	C16—C17	1.366 (4)
C1—C2	1.363 (3)	C16—H16	0.9300
C1—C9	1.416 (3)	C17—H17	0.9300
N1—C19	1.247 (3)	C10—C4	1.396 (4)
C9—C10	1.407 (4)	C10—C5	1.400 (4)
C9—C8	1.407 (4)	C4—C3	1.332 (4)
C15—C16	1.364 (3)	C4—H4	0.9300
C15—C14	1.367 (3)	C3—H3A	0.9300
O3—C2	1.347 (3)	C22—C21	1.376 (4)
O3—H3	0.8200	C22—H22	0.9300
C19—C23	1.447 (3)	C7—C6	1.373 (5)
C19—H19	0.9300	C7—H7	0.9300
C14—C13	1.365 (4)	C21—C20	1.360 (4)
C14—H14	0.9300	C21—H21	0.9300
O2—C12	1.355 (3)	C5—C6	1.340 (5)
O2—C18	1.404 (4)	C5—H5	0.9300
C23—C22	1.373 (4)	C25—C20	1.371 (4)
C23—C24	1.382 (4)	C25—H25	0.9300
C13—C12	1.360 (4)	C6—H6	0.9300
C13—H13	0.9300	C18—H18A	0.9600
C2—C3	1.395 (4)	C18—H18B	0.9600
C12—C17	1.362 (4)	C18—H18C	0.9600
C8—C7	1.348 (4)	C26—H26A	0.9600
C8—H8	0.9300	C26—H26B	0.9600
O1—C20	1.356 (3)	C26—H26C	0.9600

N1—C11—C15	108.21 (19)	C12—C17—C16	119.9 (3)
N1—C11—C1	109.98 (19)	C12—C17—H17	120.1
C15—C11—C1	112.93 (19)	C16—C17—H17	120.1
N1—C11—H11	108.5	C4—C10—C5	122.1 (3)
C15—C11—H11	108.5	C4—C10—C9	118.4 (3)
C1—C11—H11	108.5	C5—C10—C9	119.5 (3)
C2—C1—C9	118.4 (2)	C3—C4—C10	120.9 (3)
C2—C1—C11	122.4 (2)	C3—C4—H4	119.5
C9—C1—C11	119.2 (2)	C10—C4—H4	119.5
C19—N1—C11	119.5 (2)	C4—C3—C2	121.2 (3)
C10—C9—C8	116.8 (2)	C4—C3—H3A	119.4
C10—C9—C1	120.2 (2)	C2—C3—H3A	119.4
C8—C9—C1	123.0 (2)	C23—C22—C21	121.4 (3)
C16—C15—C14	117.3 (2)	C23—C22—H22	119.3
C16—C15—C11	120.8 (2)	C21—C22—H22	119.3
C14—C15—C11	121.8 (2)	C8—C7—C6	120.9 (3)
C2—O3—H3	109.5	C8—C7—H7	119.5
N1—C19—C23	122.6 (2)	C6—C7—H7	119.5
N1—C19—H19	118.7	C20—C21—C22	119.4 (3)
C23—C19—H19	118.7	C20—C21—H21	120.3
C13—C14—C15	121.5 (2)	C22—C21—H21	120.3
C13—C14—H14	119.2	C6—C5—C10	121.4 (3)
C15—C14—H14	119.2	C6—C5—H5	119.3
C12—O2—C18	117.4 (2)	C10—C5—H5	119.3
C22—C23—C24	117.8 (2)	C24—C25—C20	119.8 (3)
C22—C23—C19	119.9 (3)	C24—C25—H25	120.1
C24—C23—C19	122.4 (3)	C20—C25—H25	120.1
C12—C13—C14	120.2 (2)	C5—C6—C7	119.8 (3)
C12—C13—H13	119.9	C5—C6—H6	120.1
C14—C13—H13	119.9	C7—C6—H6	120.1
O3—C2—C1	124.1 (2)	O1—C20—C21	125.0 (3)
O3—C2—C3	115.1 (3)	O1—C20—C25	114.7 (3)
C1—C2—C3	120.8 (3)	C21—C20—C25	120.4 (3)
O2—C12—C13	116.5 (2)	O2—C18—H18A	109.5
O2—C12—C17	124.2 (2)	O2—C18—H18B	109.5
C13—C12—C17	119.2 (2)	H18A—C18—H18B	109.5
C7—C8—C9	121.7 (3)	O2—C18—H18C	109.5
C7—C8—H8	119.2	H18A—C18—H18C	109.5
C9—C8—H8	119.2	H18B—C18—H18C	109.5
C20—O1—C26	117.6 (3)	O1—C26—H26A	109.5
C25—C24—C23	121.3 (3)	O1—C26—H26B	109.5
C25—C24—H24	119.4	H26A—C26—H26B	109.5
C23—C24—H24	119.4	O1—C26—H26C	109.5
C15—C16—C17	121.9 (2)	H26A—C26—H26C	109.5
C15—C16—H16	119.1	H26B—C26—H26C	109.5
C17—C16—H16	119.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1	0.82	1.82	2.544 (3)	146

Experimental details

Crystal data
Chemical formula	C₂₆H₂₃NO₃
M_r	397.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	20.790 (5), 10.717 (3), 9.470 (2)
β (°)	102.952 (4)
V (Å³)	2056.4 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.46 × 0.45 × 0.16

Data collection
Diffractometer	Bruker APEX area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.963, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	10108, 3595, 3150
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.156, 1.22
No. of reflections	3594
No. of parameters	274
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1	0.82	1.82	2.544 (3)	145.8

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