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Acta Cryst. (2009). E65, o56    [ doi:10.1107/S160053680803910X ]

(E)-N-(2,3,4-Trimethoxy-6-methylbenzylidene)naphthalen-1-amine

C.-Y. Wang

Abstract top

In the title compound, C21H21NO3, the dihedral angle between the naphthalene ring system and the substituted benzene ring is 55.7 (2)°. The molecules are linked into a zigzag chain running along the b axis by C-H...O hydrogen bonds.

Comment top

The preparation, properties and applications of Schiff bases are important in the development of coordination chemistry. In this paper, the crystal structure of the title compound is reported.

Bond lengths and angles of the title molecule (Fig.1) agree with those observed in a related compound, (E)-N-(2,3,4-trimethoxy-6-methylbenzylidene)aniline (Zhang, 2008). The dihedral angle between the naphthalene ring system and the substituted benzene ring is 55.7 (2)°. One of the methoxy groups is coplanar (C10—O3—C5—C6 = 2.4 (4)°) with the attached ring whereas the other two methoxy groups are twisted (C8—O1—C3—C4 = -78.3 (4)° and C9—O2—C4—C3 = 109.1 (3)°).

The molecules are linked into a zigzag chain running along the b axis by C—H···O hydrogen bonds (Table 1).

Related literature top

For a related structure, see: Zhang (2008).

Experimental top

A mixture of 1-naphthylamine (0.715 g, 5 mmol) and 2,3,4-trimethoxy-6-methylbenzaldehyde (1.04 g, 5 mmol) in ethanol (30 ml) was refluxed for 2 h. After cooling, the precipitate obtained was filtered and dried. The crude product was (20 mg) was dissolved in ethanol (20 ml) and the solution was filtered to remove impurities, and then left for crystallization at room temperature. Single crystals suitable for X-ray crystal structure determination were obtained after a week.

Refinement top

H atoms were positioned geometrically (C-H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5 Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
(E)-N-(2,3,4-Trimethoxy-6-methylbenzylidene)naphthalen-1-amine top
Crystal data top
C21H21NO3F(000) = 1424
Mr = 335.39Dx = 1.227 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3424 reflections
a = 10.9225 (14) Åθ = 2.5–25.3°
b = 14.7630 (16) ŵ = 0.08 mm−1
c = 22.514 (2) ÅT = 298 K
V = 3630.3 (7) Å3Plate, light yellow
Z = 80.23 × 0.19 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3195 independent reflections
Radiation source: fine-focus sealed tube1918 reflections with I > 2σ(I)
graphiteRint = 0.071
φ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −12→8
Tmin = 0.981, Tmax = 0.994k = −17→15
17242 measured reflectionsl = −26→25
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0824P)2]
where P = (Fo2 + 2Fc2)/3
3195 reflections(Δ/σ)max = 0.001
226 parametersΔρmax = 0.19 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C21H21NO3V = 3630.3 (7) Å3
Mr = 335.39Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 10.9225 (14) ŵ = 0.08 mm−1
b = 14.7630 (16) ÅT = 298 K
c = 22.514 (2) Å0.23 × 0.19 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3195 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1918 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.994Rint = 0.071
17242 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.166Δρmax = 0.19 e Å−3
S = 1.07Δρmin = −0.25 e Å−3
3195 reflectionsAbsolute structure: ?
226 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
N10.1079 (2)0.32182 (15)0.65758 (10)0.0437 (6)
O1−0.20286 (18)0.26652 (12)0.57093 (9)0.0494 (6)
O2−0.34730 (17)0.11513 (12)0.58640 (8)0.0463 (5)
O3−0.29401 (19)−0.00497 (13)0.67264 (8)0.0521 (6)
C10.0044 (3)0.30050 (17)0.63498 (12)0.0404 (7)
H1−0.02710.33930.60630.048*
C2−0.0689 (2)0.22122 (17)0.64990 (12)0.0374 (7)
C3−0.1715 (3)0.20404 (17)0.61366 (11)0.0360 (7)
C4−0.2445 (2)0.12749 (19)0.62117 (11)0.0354 (7)
C5−0.2172 (3)0.06808 (17)0.66764 (12)0.0382 (7)
C6−0.1196 (3)0.08606 (19)0.70516 (12)0.0429 (8)
H6−0.10400.04670.73650.051*
C7−0.0440 (3)0.16116 (18)0.69743 (12)0.0397 (7)
C8−0.1737 (5)0.2453 (3)0.51222 (15)0.1067 (17)
H8A−0.10210.20760.51140.160*
H8B−0.15790.30010.49050.160*
H8C−0.24090.21360.49430.160*
C9−0.3371 (3)0.0441 (2)0.54325 (14)0.0654 (10)
H9A−0.26050.04950.52270.098*
H9B−0.40320.04870.51530.098*
H9C−0.3408−0.01360.56290.098*
C10−0.2751 (4)−0.0653 (2)0.72126 (16)0.0843 (13)
H10A−0.1990−0.09690.71600.126*
H10B−0.3410−0.10830.72290.126*
H10C−0.2725−0.03150.75760.126*
C110.0612 (3)0.1741 (2)0.73974 (14)0.0616 (10)
H11A0.13700.16490.71900.092*
H11B0.05480.13130.77170.092*
H11C0.05900.23450.75550.092*
C120.1640 (3)0.40259 (17)0.63702 (12)0.0367 (7)
C130.1017 (3)0.48289 (18)0.63178 (13)0.0450 (8)
H130.01910.48550.64150.054*
C140.1619 (3)0.56103 (19)0.61192 (15)0.0539 (9)
H140.11810.61480.60860.065*
C150.2820 (3)0.56022 (19)0.59751 (14)0.0530 (8)
H150.31980.61300.58430.064*
C160.3507 (3)0.47867 (18)0.60249 (13)0.0423 (7)
C170.2925 (3)0.39934 (17)0.62421 (11)0.0375 (7)
C180.3634 (3)0.32002 (19)0.63141 (13)0.0463 (8)
H180.32720.26810.64690.056*
C190.4841 (3)0.3187 (2)0.61596 (15)0.0582 (9)
H190.52940.26590.62090.070*
C200.5401 (3)0.3956 (2)0.59289 (15)0.0613 (9)
H200.62200.39340.58180.074*
C210.4760 (3)0.4741 (2)0.58642 (14)0.0562 (9)
H210.51480.52520.57130.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0416 (16)0.0425 (14)0.0471 (15)−0.0020 (12)−0.0009 (13)0.0028 (11)
O10.0476 (13)0.0498 (12)0.0507 (13)0.0062 (10)−0.0107 (10)0.0102 (10)
O20.0382 (12)0.0539 (12)0.0468 (12)0.0001 (9)−0.0099 (10)−0.0034 (10)
O30.0574 (15)0.0524 (12)0.0465 (12)−0.0163 (11)−0.0104 (10)0.0093 (10)
C10.0432 (19)0.0409 (16)0.0370 (16)0.0035 (14)−0.0001 (15)−0.0002 (12)
C20.0364 (17)0.0391 (15)0.0367 (16)0.0038 (13)−0.0001 (14)−0.0028 (13)
C30.0373 (17)0.0377 (15)0.0332 (15)0.0073 (13)0.0001 (14)0.0003 (12)
C40.0285 (15)0.0461 (16)0.0315 (15)0.0027 (13)−0.0040 (13)−0.0034 (12)
C50.0368 (18)0.0422 (16)0.0357 (16)−0.0041 (13)−0.0011 (14)0.0002 (13)
C60.0488 (19)0.0471 (17)0.0328 (16)−0.0029 (15)−0.0055 (15)0.0091 (13)
C70.0406 (18)0.0445 (16)0.0341 (15)−0.0010 (14)−0.0075 (14)0.0040 (13)
C80.198 (5)0.085 (3)0.038 (2)0.004 (3)0.004 (3)0.012 (2)
C90.062 (2)0.087 (2)0.0472 (19)−0.015 (2)−0.0120 (18)−0.0113 (18)
C100.102 (3)0.079 (3)0.072 (2)−0.041 (2)−0.030 (2)0.036 (2)
C110.057 (2)0.071 (2)0.057 (2)−0.0187 (17)−0.0196 (18)0.0195 (17)
C120.0378 (17)0.0367 (15)0.0357 (16)0.0000 (13)−0.0035 (14)−0.0031 (12)
C130.0394 (18)0.0420 (17)0.0534 (19)0.0042 (14)−0.0036 (15)−0.0067 (13)
C140.051 (2)0.0357 (17)0.075 (2)0.0031 (15)−0.0084 (19)−0.0022 (15)
C150.053 (2)0.0359 (17)0.070 (2)−0.0102 (15)−0.0104 (18)0.0042 (15)
C160.0410 (18)0.0396 (16)0.0462 (17)−0.0063 (14)−0.0066 (15)−0.0045 (13)
C170.0373 (17)0.0382 (16)0.0369 (16)−0.0005 (14)−0.0074 (14)−0.0061 (12)
C180.045 (2)0.0382 (16)0.0555 (19)0.0033 (14)−0.0038 (16)−0.0039 (14)
C190.044 (2)0.054 (2)0.077 (2)0.0105 (16)−0.0064 (19)−0.0060 (17)
C200.0356 (19)0.063 (2)0.085 (3)−0.0022 (17)0.0030 (19)−0.0095 (19)
C210.0411 (19)0.0558 (19)0.072 (2)−0.0134 (16)−0.0018 (18)0.0003 (16)
Geometric parameters (Å, °) top
N1—C11.279 (4)C10—H10A0.96
N1—C121.418 (3)C10—H10B0.96
O1—C31.376 (3)C10—H10C0.96
O1—C81.395 (4)C11—H11A0.96
O2—C41.381 (3)C11—H11B0.96
O2—C91.434 (3)C11—H11C0.96
O3—C51.371 (3)C12—C131.372 (4)
O3—C101.426 (3)C12—C171.434 (4)
C1—C21.457 (4)C13—C141.401 (4)
C1—H10.93C13—H130.93
C2—C31.410 (4)C14—C151.351 (4)
C2—C71.416 (4)C14—H140.93
C3—C41.393 (4)C15—C161.423 (4)
C4—C51.397 (4)C15—H150.93
C5—C61.386 (4)C16—C211.417 (4)
C6—C71.393 (4)C16—C171.419 (4)
C6—H60.93C17—C181.413 (4)
C7—C111.505 (4)C18—C191.364 (4)
C8—H8A0.96C18—H180.93
C8—H8B0.96C19—C201.390 (4)
C8—H8C0.96C19—H190.93
C9—H9A0.96C20—C211.362 (4)
C9—H9B0.96C20—H200.93
C9—H9C0.96C21—H210.93
C1—N1—C12117.3 (2)O3—C10—H10C109.5
C3—O1—C8117.1 (2)H10A—C10—H10C109.5
C4—O2—C9114.7 (2)H10B—C10—H10C109.5
C5—O3—C10117.8 (2)C7—C11—H11A109.5
N1—C1—C2126.3 (3)C7—C11—H11B109.5
N1—C1—H1116.9H11A—C11—H11B109.5
C2—C1—H1116.9C7—C11—H11C109.5
C3—C2—C7118.5 (2)H11A—C11—H11C109.5
C3—C2—C1116.6 (2)H11B—C11—H11C109.5
C7—C2—C1124.9 (3)C13—C12—N1122.7 (3)
O1—C3—C4119.1 (2)C13—C12—C17119.8 (3)
O1—C3—C2118.8 (2)N1—C12—C17117.4 (2)
C4—C3—C2122.0 (2)C12—C13—C14120.4 (3)
O2—C4—C3120.2 (2)C12—C13—H13119.8
O2—C4—C5121.0 (2)C14—C13—H13119.8
C3—C4—C5118.6 (2)C15—C14—C13121.6 (3)
O3—C5—C6124.8 (2)C15—C14—H14119.2
O3—C5—C4115.2 (2)C13—C14—H14119.2
C6—C5—C4120.0 (3)C14—C15—C16120.0 (3)
C5—C6—C7122.2 (2)C14—C15—H15120.0
C5—C6—H6118.9C16—C15—H15120.0
C7—C6—H6118.9C21—C16—C17118.7 (3)
C6—C7—C2118.6 (3)C21—C16—C15121.9 (3)
C6—C7—C11118.3 (2)C17—C16—C15119.3 (3)
C2—C7—C11123.0 (3)C18—C17—C16118.6 (3)
O1—C8—H8A109.5C18—C17—C12122.8 (3)
O1—C8—H8B109.5C16—C17—C12118.7 (2)
H8A—C8—H8B109.5C19—C18—C17120.8 (3)
O1—C8—H8C109.5C19—C18—H18119.6
H8A—C8—H8C109.5C17—C18—H18119.6
H8B—C8—H8C109.5C18—C19—C20120.6 (3)
O2—C9—H9A109.5C18—C19—H19119.7
O2—C9—H9B109.5C20—C19—H19119.7
H9A—C9—H9B109.5C21—C20—C19120.6 (3)
O2—C9—H9C109.5C21—C20—H20119.7
H9A—C9—H9C109.5C19—C20—H20119.7
H9B—C9—H9C109.5C20—C21—C16120.6 (3)
O3—C10—H10A109.5C20—C21—H21119.7
O3—C10—H10B109.5C16—C21—H21119.7
H10A—C10—H10B109.5
C12—N1—C1—C2−179.6 (2)C1—C2—C7—C6−177.7 (3)
N1—C1—C2—C3−171.3 (3)C3—C2—C7—C11−178.5 (3)
N1—C1—C2—C78.5 (4)C1—C2—C7—C111.7 (4)
C8—O1—C3—C4−78.3 (4)C1—N1—C12—C1347.2 (4)
C8—O1—C3—C2103.9 (3)C1—N1—C12—C17−135.8 (3)
C7—C2—C3—O1174.0 (2)N1—C12—C13—C14179.2 (3)
C1—C2—C3—O1−6.2 (4)C17—C12—C13—C142.3 (4)
C7—C2—C3—C4−3.7 (4)C12—C13—C14—C15−0.2 (5)
C1—C2—C3—C4176.1 (2)C13—C14—C15—C16−0.2 (5)
C9—O2—C4—C3109.1 (3)C14—C15—C16—C21178.3 (3)
C9—O2—C4—C5−76.4 (3)C14—C15—C16—C17−1.7 (4)
O1—C3—C4—O2−0.5 (4)C21—C16—C17—C182.8 (4)
C2—C3—C4—O2177.2 (2)C15—C16—C17—C18−177.2 (3)
O1—C3—C4—C5−175.2 (2)C21—C16—C17—C12−176.2 (3)
C2—C3—C4—C52.5 (4)C15—C16—C17—C123.8 (4)
C10—O3—C5—C62.4 (4)C13—C12—C17—C18176.9 (3)
C10—O3—C5—C4−176.5 (3)N1—C12—C17—C18−0.1 (4)
O2—C4—C5—O34.6 (4)C13—C12—C17—C16−4.1 (4)
C3—C4—C5—O3179.2 (2)N1—C12—C17—C16178.8 (2)
O2—C4—C5—C6−174.4 (2)C16—C17—C18—C19−2.2 (4)
C3—C4—C5—C60.2 (4)C12—C17—C18—C19176.8 (3)
O3—C5—C6—C7179.4 (3)C17—C18—C19—C200.1 (5)
C4—C5—C6—C7−1.7 (4)C18—C19—C20—C211.3 (5)
C5—C6—C7—C20.6 (4)C19—C20—C21—C16−0.7 (5)
C5—C6—C7—C11−178.9 (3)C17—C16—C21—C20−1.4 (5)
C3—C2—C7—C62.1 (4)C15—C16—C21—C20178.6 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O3i0.932.563.489 (4)178
Symmetry codes: (i) −x−1/2, y+1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O3i0.932.563.489 (4)178
Symmetry codes: (i) −x−1/2, y+1/2, z.
references
References top

Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhang, H. (2008). Acta Cryst. E64, o1219.