(E)-N-(2,3,4-Trimeth­oxy-6-methyl­benzyl­idene)aniline

Zhang, H.

doi:10.1107/S1600536808016620

organic compounds

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Volume 64| Part 7| July 2008| Page o1219

doi:10.1107/S1600536808016620

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(E)-N-(2,3,4-Trimethoxy-6-methylbenzylidene)aniline

Hui Zhang ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: zhanghuiwfu@163.com

(Received 20 April 2008; accepted 30 May 2008; online 7 June 2008)

In the title compound, C₁₇H₁₉NO₃, the C—C=N—C torsion angle between the benzene and phenyl rings is −177.3 (2)°, and the dihedral angle between the rings is 54.6 (2)°. The crystal structure is stabilized by intramolecular hydrogen bonds and weak π–π and C—H⋯π interactions.

Related literature

For related literature, see: Zhang et al. (2005 ).

Experimental

Crystal data

C₁₇H₁₉NO₃
M_r = 285.33
Triclinic, $[P \overline 1]$
a = 8.3126 (13) Å
b = 9.9938 (17) Å
c = 10.8661 (19) Å
α = 110.102 (2)°
β = 111.995 (2)°
γ = 92.7000 (10)°
V = 769.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 (2) K
0.50 × 0.48 × 0.47 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.959, T_max = 0.962
3966 measured reflections
2650 independent reflections
1571 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.170
S = 1.00
2650 reflections
194 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the ring C12–C17.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1	0.93	2.32	2.714 (3)	105
C8—H8C⋯O2	0.96	2.47	3.062 (5)	120
C9—H9C⋯O1	0.96	2.53	3.079 (4)	116
C10—H10C⋯Cg2ⁱ	0.96	2.98	3.894 (4)	160
Symmetry code: (i) x, y+1, z.

Table 2
π–π interactions (Å, °)

Cg1 is the centroid of the ring C2–C7. The offset is defined as the distance between CgI and the perpendicular projection of CgJ on ring I.

CgI⋯CgJ	CgI⋯CgJ	Dihedral angle	Interplanar distance	Offset
Cg1⋯Cg1ⁱ	4.236 (1)	0	3.523 (1)	2.352
Symmetry code: (i) 1-x, 1-y, 2-z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016620/bx2141sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016620/bx2141Isup2.hkl

checkCIF report

Comment top

The preparation, properties and applications of Schiff bases are important in the development of coordination chemistry. In this paper, the structure of the title compound, (I), is reported. The molecular structure of (I) is illustrated in Fig. 1. The bond lengths and angles of the title compound agree with those in the related compound 2,3,4-Trimethoxy-6-methylbenzaldehyde (Zhang et al., 2005), as representative example. The dihedral angle between the two phenyl rings is 125.4 (2)°. The crystal structure is stabilized by an intramolecular hydrogen bonding and weak π–π and C—H···π interactions ( Table 1 and Table 2).

Related literature top

For related literature, see: Zhang et al. (2005).

Experimental top

To a solution of p-toluidine (0.535 g, 5 mmol) and potassium acetate (0.980 g, 10 mmol) in distilled water (10 ml), 2,3,4-Trimethoxy-6-methylbenzaldehyde (1.04 g, 5 mmol) in ethylalcohol (20 ml) was added drop by drop, the solution was stirred for 1 h at reflux temperature. The precipitate was filtered and dried. 10 mg of (I) was dissolved in 15 ml ethanol and the solution was allowed to evaporate at room temperature. Straw yellow single crystals of the title compound were formed after one week.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (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

Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids.

(E)-N-(2,3,4-Trimethoxy-6-methylbenzylidene)aniline top

Crystal data top

C₁₇H₁₉NO₃	Z = 2
M_r = 285.33	F(000) = 304
Triclinic, P1	D_x = 1.231 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3126 (13) Å	Cell parameters from 1209 reflections
b = 9.9938 (17) Å	θ = 2.4–26.5°
c = 10.8661 (19) Å	µ = 0.08 mm⁻¹
α = 110.102 (2)°	T = 298 K
β = 111.995 (2)°	Block, yellow
γ = 92.700 (1)°	0.50 × 0.48 × 0.47 mm
V = 769.8 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2650 independent reflections
Radiation source: fine-focus sealed tube	1571 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→9
T_min = 0.959, T_max = 0.962	k = −7→11
3966 measured reflections	l = −12→12

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.170	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0809P)² + 0.0591P] where P = (F_o² + 2F_c²)/3
2650 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₇H₁₉NO₃	γ = 92.700 (1)°
M_r = 285.33	V = 769.8 (2) Å³
Triclinic, P1	Z = 2
a = 8.3126 (13) Å	Mo Kα radiation
b = 9.9938 (17) Å	µ = 0.08 mm⁻¹
c = 10.8661 (19) Å	T = 298 K
α = 110.102 (2)°	0.50 × 0.48 × 0.47 mm
β = 111.995 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2650 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1571 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.962	R_int = 0.034
3966 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
2650 reflections	Δρ_min = −0.22 e Å⁻³
194 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
N1	0.6434 (3)	0.0882 (2)	0.7849 (2)	0.0637 (6)
O1	0.1396 (2)	0.11706 (18)	0.64766 (19)	0.0619 (5)
O2	0.0101 (2)	0.3729 (2)	0.67375 (19)	0.0642 (5)
O3	0.2329 (2)	0.62688 (18)	0.78978 (19)	0.0626 (5)
C1	0.4895 (3)	0.1089 (3)	0.7390 (3)	0.0489 (6)
H1	0.3988	0.0268	0.6846	0.059*
C2	0.4379 (3)	0.2505 (2)	0.7625 (2)	0.0424 (6)
C3	0.2546 (3)	0.2493 (2)	0.7129 (2)	0.0457 (6)
C4	0.1898 (3)	0.3749 (3)	0.7225 (2)	0.0468 (6)
C5	0.3079 (3)	0.5078 (3)	0.7853 (2)	0.0471 (6)
C6	0.4884 (3)	0.5112 (3)	0.8370 (2)	0.0470 (6)
H6	0.5664	0.6004	0.8804	0.056*
C7	0.5564 (3)	0.3853 (3)	0.8261 (2)	0.0452 (6)
C8	0.0442 (5)	0.0901 (4)	0.7236 (4)	0.0963 (11)
H8A	0.1254	0.0873	0.8125	0.144*
H8B	−0.0376	−0.0015	0.6660	0.144*
H8C	−0.0198	0.1663	0.7438	0.144*
C9	−0.0840 (4)	0.3143 (4)	0.5226 (3)	0.0889 (11)
H9A	−0.0245	0.3586	0.4815	0.133*
H9B	−0.2018	0.3333	0.4977	0.133*
H9C	−0.0900	0.2112	0.4858	0.133*
C10	0.3479 (4)	0.7643 (3)	0.8476 (3)	0.0751 (9)
H10A	0.4278	0.7854	0.9456	0.113*
H10B	0.2790	0.8385	0.8448	0.113*
H10C	0.4144	0.7616	0.7915	0.113*
C11	0.7545 (3)	0.4004 (3)	0.8838 (3)	0.0616 (7)
H11A	0.8096	0.5015	0.9259	0.092*
H11B	0.7866	0.3496	0.8066	0.092*
H11C	0.7936	0.3599	0.9558	0.092*
C12	0.6728 (3)	−0.0566 (3)	0.7476 (3)	0.0504 (6)
C13	0.7910 (3)	−0.0901 (3)	0.8552 (3)	0.0649 (8)
H13	0.8417	−0.0205	0.9492	0.078*
C14	0.8357 (4)	−0.2241 (3)	0.8266 (4)	0.0736 (8)
H14	0.9156	−0.2451	0.9009	0.088*
C15	0.7636 (5)	−0.3261 (3)	0.6901 (4)	0.0758 (9)
H15	0.7945	−0.4169	0.6708	0.091*
C16	0.6450 (4)	−0.2958 (3)	0.5803 (3)	0.0746 (9)
H16	0.5953	−0.3660	0.4867	0.090*
C17	0.5994 (4)	−0.1610 (3)	0.6089 (3)	0.0614 (7)
H17	0.5190	−0.1404	0.5345	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0507 (14)	0.0530 (14)	0.0845 (16)	0.0168 (11)	0.0250 (12)	0.0260 (12)
O1	0.0464 (10)	0.0564 (11)	0.0774 (13)	0.0030 (8)	0.0300 (9)	0.0160 (9)
O2	0.0420 (10)	0.0785 (13)	0.0730 (13)	0.0211 (9)	0.0266 (9)	0.0264 (10)
O3	0.0661 (12)	0.0558 (11)	0.0766 (12)	0.0272 (9)	0.0343 (10)	0.0311 (9)
C1	0.0447 (15)	0.0542 (15)	0.0534 (14)	0.0107 (12)	0.0250 (12)	0.0224 (12)
C2	0.0423 (13)	0.0477 (14)	0.0424 (13)	0.0130 (11)	0.0208 (11)	0.0194 (10)
C3	0.0430 (14)	0.0489 (15)	0.0461 (13)	0.0089 (11)	0.0227 (11)	0.0150 (11)
C4	0.0398 (14)	0.0578 (16)	0.0471 (14)	0.0158 (12)	0.0220 (11)	0.0202 (11)
C5	0.0522 (15)	0.0507 (15)	0.0475 (14)	0.0196 (12)	0.0266 (12)	0.0219 (11)
C6	0.0465 (14)	0.0481 (14)	0.0461 (13)	0.0063 (11)	0.0197 (11)	0.0181 (11)
C7	0.0427 (14)	0.0535 (15)	0.0458 (13)	0.0130 (12)	0.0214 (11)	0.0230 (11)
C8	0.110 (3)	0.081 (2)	0.134 (3)	0.0123 (19)	0.084 (3)	0.046 (2)
C9	0.0557 (18)	0.108 (3)	0.075 (2)	0.0228 (18)	0.0085 (16)	0.0230 (19)
C10	0.094 (2)	0.0561 (18)	0.080 (2)	0.0248 (16)	0.0366 (18)	0.0302 (15)
C11	0.0456 (15)	0.0611 (17)	0.0775 (18)	0.0098 (12)	0.0219 (14)	0.0304 (14)
C12	0.0419 (14)	0.0499 (15)	0.0683 (17)	0.0136 (11)	0.0293 (13)	0.0256 (13)
C13	0.0525 (16)	0.0590 (17)	0.0702 (18)	0.0132 (13)	0.0153 (14)	0.0215 (14)
C14	0.0603 (18)	0.071 (2)	0.094 (2)	0.0209 (15)	0.0252 (17)	0.0437 (18)
C15	0.094 (2)	0.0582 (19)	0.104 (3)	0.0350 (17)	0.061 (2)	0.0383 (18)
C16	0.099 (2)	0.0641 (19)	0.0689 (19)	0.0214 (17)	0.0485 (18)	0.0202 (15)
C17	0.0710 (18)	0.0653 (18)	0.0662 (18)	0.0230 (14)	0.0393 (15)	0.0334 (15)

Geometric parameters (Å, º) top

N1—C1	1.244 (3)	C9—H9A	0.9600
N1—C12	1.422 (3)	C9—H9B	0.9600
O1—C3	1.376 (3)	C9—H9C	0.9600
O1—C8	1.416 (3)	C10—H10A	0.9600
O2—C4	1.382 (3)	C10—H10B	0.9600
O2—C9	1.409 (3)	C10—H10C	0.9600
O3—C5	1.363 (3)	C11—H11A	0.9600
O3—C10	1.423 (3)	C11—H11B	0.9600
C1—C2	1.464 (3)	C11—H11C	0.9600
C1—H1	0.9300	C12—C13	1.373 (4)
C2—C7	1.410 (3)	C12—C17	1.379 (4)
C2—C3	1.411 (3)	C13—C14	1.370 (4)
C3—C4	1.375 (3)	C13—H13	0.9300
C4—C5	1.396 (3)	C14—C15	1.355 (4)
C5—C6	1.385 (3)	C14—H14	0.9300
C6—C7	1.389 (3)	C15—C16	1.372 (4)
C6—H6	0.9300	C15—H15	0.9300
C7—C11	1.505 (3)	C16—C17	1.380 (4)
C8—H8A	0.9600	C16—H16	0.9300
C8—H8B	0.9600	C17—H17	0.9300
C8—H8C	0.9600

C1—N1—C12	119.4 (2)	O2—C9—H9C	109.5
C3—O1—C8	116.2 (2)	H9A—C9—H9C	109.5
C4—O2—C9	114.82 (19)	H9B—C9—H9C	109.5
C5—O3—C10	117.8 (2)	O3—C10—H10A	109.5
N1—C1—C2	126.0 (2)	O3—C10—H10B	109.5
N1—C1—H1	117.0	H10A—C10—H10B	109.5
C2—C1—H1	117.0	O3—C10—H10C	109.5
C7—C2—C3	118.4 (2)	H10A—C10—H10C	109.5
C7—C2—C1	125.0 (2)	H10B—C10—H10C	109.5
C3—C2—C1	116.5 (2)	C7—C11—H11A	109.5
C4—C3—O1	120.0 (2)	C7—C11—H11B	109.5
C4—C3—C2	121.8 (2)	H11A—C11—H11B	109.5
O1—C3—C2	118.1 (2)	C7—C11—H11C	109.5
C3—C4—O2	121.5 (2)	H11A—C11—H11C	109.5
C3—C4—C5	119.4 (2)	H11B—C11—H11C	109.5
O2—C4—C5	119.1 (2)	C13—C12—C17	118.6 (2)
O3—C5—C6	124.8 (2)	C13—C12—N1	117.4 (2)
O3—C5—C4	115.7 (2)	C17—C12—N1	123.8 (2)
C6—C5—C4	119.5 (2)	C14—C13—C12	121.1 (3)
C5—C6—C7	122.0 (2)	C14—C13—H13	119.4
C5—C6—H6	119.0	C12—C13—H13	119.4
C7—C6—H6	119.0	C15—C14—C13	120.0 (3)
C6—C7—C2	118.9 (2)	C15—C14—H14	120.0
C6—C7—C11	117.9 (2)	C13—C14—H14	120.0
C2—C7—C11	123.2 (2)	C14—C15—C16	120.2 (3)
O1—C8—H8A	109.5	C14—C15—H15	119.9
O1—C8—H8B	109.5	C16—C15—H15	119.9
H8A—C8—H8B	109.5	C15—C16—C17	119.9 (3)
O1—C8—H8C	109.5	C15—C16—H16	120.0
H8A—C8—H8C	109.5	C17—C16—H16	120.0
H8B—C8—H8C	109.5	C12—C17—C16	120.1 (3)
O2—C9—H9A	109.5	C12—C17—H17	119.9
O2—C9—H9B	109.5	C16—C17—H17	119.9
H9A—C9—H9B	109.5

C12—N1—C1—C2	−177.3 (2)	O2—C4—C5—C6	178.8 (2)
N1—C1—C2—C7	8.3 (4)	O3—C5—C6—C7	−178.4 (2)
N1—C1—C2—C3	−173.8 (2)	C4—C5—C6—C7	1.2 (3)
C8—O1—C3—C4	−70.8 (3)	C5—C6—C7—C2	−1.1 (3)
C8—O1—C3—C2	112.1 (3)	C5—C6—C7—C11	179.2 (2)
C7—C2—C3—C4	1.3 (3)	C3—C2—C7—C6	−0.2 (3)
C1—C2—C3—C4	−176.7 (2)	C1—C2—C7—C6	177.7 (2)
C7—C2—C3—O1	178.33 (19)	C3—C2—C7—C11	179.6 (2)
C1—C2—C3—O1	0.3 (3)	C1—C2—C7—C11	−2.6 (4)
O1—C3—C4—O2	3.0 (3)	C1—N1—C12—C13	−136.1 (3)
C2—C3—C4—O2	−180.0 (2)	C1—N1—C12—C17	48.6 (4)
O1—C3—C4—C5	−178.2 (2)	C17—C12—C13—C14	−0.1 (4)
C2—C3—C4—C5	−1.2 (3)	N1—C12—C13—C14	−175.7 (2)
C9—O2—C4—C3	−72.5 (3)	C12—C13—C14—C15	0.3 (4)
C9—O2—C4—C5	108.7 (3)	C13—C14—C15—C16	−0.3 (5)
C10—O3—C5—C6	2.1 (3)	C14—C15—C16—C17	0.2 (4)
C10—O3—C5—C4	−177.6 (2)	C13—C12—C17—C16	0.0 (4)
C3—C4—C5—O3	179.6 (2)	N1—C12—C17—C16	175.2 (2)
O2—C4—C5—O3	−1.6 (3)	C15—C16—C17—C12	0.0 (4)
C3—C4—C5—C6	−0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1	0.93	2.32	2.714 (3)	105
C8—H8C···O2	0.96	2.47	3.062 (5)	120
C9—H9C···O1	0.96	2.53	3.079 (4)	116
C10—H10C···Cg2ⁱ	0.96	2.98	3.894 (4)	160

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₉NO₃
M_r	285.33
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.3126 (13), 9.9938 (17), 10.8661 (19)
α, β, γ (°)	110.102 (2), 111.995 (2), 92.700 (1)
V (Å³)	769.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.48 × 0.47

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.959, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	3966, 2650, 1571
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.170, 1.00
No. of reflections	2650
No. of parameters	194
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1	0.93	2.32	2.714 (3)	105
C8—H8C···O2	0.96	2.47	3.062 (5)	120.1
C9—H9C···O1	0.96	2.53	3.079 (4)	116.2
C10—H10C···Cg2ⁱ	0.96	2.98	3.894 (4)	160

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

π–π interactions (Å, °) top

Cg1 is the centroid of ring C2–C7. The offset is defined as the distance between CgI and the perpendicular projection of CgJ on ring I.

CgI-CgJ	CgI···CgJ	Dihedral angle	Interplanar distance	Offset
Cg1-Cg1i	4.236 (1)	0	3.523 (1)	2.352

Symmetry code: (i) 1-x, 1-y, 2-z.

References

Bruker (1997). SADABS, SMART and SAINT . Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, W.-J., Lu, M., Li, C.-B. & Zhou, W.-Y. (2005). Acta Cryst. E61, o3222–o3223. Web of Science CSD CrossRef IUCr Journals Google Scholar