N,N′-Bis(4-methoxy­benzyl­idene)-4,4′-(m-phenyl­enedi­oxy)dianiline

Nadeem, S.; Shah, M.R.; VanDerveer, D.

doi:10.1107/S1600536809010939

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o897

doi:10.1107/S1600536809010939

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N,N′-Bis(4-methoxybenzylidene)-4,4′-(m-phenylenedioxy)dianiline

Said Nadeem,^a Muhammad Raza Shah ^a ^* and Donald VanDerveer ^b

^aHEJ Research Institute of Chemistry, International Center for Chemical & Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bMolecular Structure Center, Chemistry Department, Clemson University, Clemson, SC 29634-0973, USA
^*Correspondence e-mail: raza_shahm@yahoo.com

(Received 21 February 2009; accepted 24 March 2009; online 28 March 2009)

Molecules of the title compound, C₃₄H₂₈N₂O₄, a Schiff base precursor for macrocycles, are located on a mirror plane. The C=N double bond is trans configured. Intermolecular C—H⋯O interactions stabilize the crystal packing.

Related literature

For the importance of Schiff base macrocycles in macrocyclic and supramolecular chemistry, see: Ali et al. (2008 ).

Experimental

Crystal data

C₃₄H₂₈N₂O₄
M_r = 528.58
Orthorhombic, C m c 2₁
a = 59.344 (13) Å
b = 7.484 (3) Å
c = 5.988 (2) Å
V = 2659.4 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 163 K
0.60 × 0.41 × 0.02 mm

Data collection

Rigaku AFC8S Mercury CCD diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.837, T_max = 1.000 (expected range = 0.836–0.998)
7742 measured reflections
1351 independent reflections
1164 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.142
S = 1.09
1351 reflections
185 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O7ⁱ	0.96	2.57	3.411 (5)	147
C13—H13⋯O17ⁱⁱ	0.96	2.52	3.405 (4)	154
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809010939/bt2885sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010939/bt2885Isup2.hkl

checkCIF report

Comment top

Schiff base macrocycles have been of great importance in macrocyclic and supramolecular chemistry (Ali et al., 2008). Here we report the synthesis and crystal structure of the title compound which is a precursor for the synthesis of a Schiff-base macrocycle. The crystal packing is stabilized by some short C—H···O contacts and van der Waals interactions. The methoxy group is coplanar with the benzene ring as revealed by the C6—C1—O7—C8 torsion of 175.5 (3)°. The methoxy oxygen atom acts as an acceptor for a weak C—H···O hydrogen bond from a neighboring molecule. C—H···O interactions stabilize the crystal packing.

Related literature top

For the importance of Schiff base macrocycles in macrocyclic and supramolecular chemistry, see: Ali et al. (2008).

Experimental top

100 mg (0.34 mmol) of 4,4'-(1,3-phenylenebis(oxy))dianiline was dissolved in 2 ml of dichloromethane and then a solution of 4-methoxybenzaldehyde (0.1 ml, 085 mmol) in 2 ml of dichloromethane was added dropwise with stirring. The reaction was stirred at 330 K for 30 min and cooled to room temperature. The solvent was then removed using a rotary evaporator to give a crude solid. The solid was dissolved in dichloromethane and slow evaporation of the dichloromethane afforded needle like crystals in 80% yield.

Computing details top

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalClear (Rigaku, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Crystal Structure of the title compound; anisotropic displacement ellipsoid plot, 50% probability; symmetry operator for generating equivalent atoms -x, y, z).

N,N'-Bis(4-methoxybenzylidene)-4,4'-(m- phenylenedioxy)dianiline top

Crystal data top

C₃₄H₂₈N₂O₄	D_x = 1.320 Mg m⁻³
M_r = 528.58	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmc2₁	Cell parameters from 3132 reflections
a = 59.344 (13) Å	θ = 2.7–26.4°
b = 7.484 (3) Å	µ = 0.09 mm⁻¹
c = 5.988 (2) Å	T = 163 K
V = 2659.4 (15) Å³	Plate, colorless
Z = 4	0.60 × 0.41 × 0.02 mm
F(000) = 1112

Data collection top

Rigaku AFC8S Mercury CCD diffractometer	1351 independent reflections
Radiation source: Sealed Tube	1164 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.046
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.4°, θ_min = 2.7°
ω scans	h = −71→53
Absorption correction: multi-scan (Jacobson, 1998)	k = −8→9
T_min = 0.837, T_max = 1.000	l = −7→7
7742 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0795P)² + 2.3925P] where P = (F_o² + 2F_c²)/3
1351 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.29 e Å⁻³
1 restraint	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃₄H₂₈N₂O₄	V = 2659.4 (15) Å³
M_r = 528.58	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 59.344 (13) Å	µ = 0.09 mm⁻¹
b = 7.484 (3) Å	T = 163 K
c = 5.988 (2) Å	0.60 × 0.41 × 0.02 mm

Data collection top

Rigaku AFC8S Mercury CCD diffractometer	1351 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	1164 reflections with I > 2σ(I)
T_min = 0.837, T_max = 1.000	R_int = 0.046
7742 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	1 restraint
wR(F²) = 0.142	H-atom parameters constrained
S = 1.09	Δρ_max = 0.29 e Å⁻³
1351 reflections	Δρ_min = −0.23 e Å⁻³
185 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
C1	0.20032 (5)	0.2529 (4)	0.2108 (8)	0.0298 (9)
C2	0.18360 (6)	0.1751 (5)	0.0811 (7)	0.0336 (9)
H2	0.1873	0.1211	−0.0596	0.040*
C3	0.16140 (6)	0.1762 (5)	0.1569 (7)	0.0322 (9)
H3	0.1497	0.1270	0.0649	0.039*
C4	0.15600 (6)	0.2481 (4)	0.3652 (7)	0.0266 (8)
C5	0.17305 (6)	0.3287 (4)	0.4920 (7)	0.0309 (8)
H5	0.1695	0.3815	0.6339	0.037*
C6	0.19483 (6)	0.3321 (5)	0.4130 (7)	0.0319 (9)
H6	0.2064	0.3901	0.4990	0.038*
O7	0.22265 (4)	0.2623 (4)	0.1501 (5)	0.0417 (7)
C8	0.22934 (6)	0.1709 (7)	−0.0480 (9)	0.0566 (13)
H8A	0.2260	0.0460	−0.0333	0.085*
H8B	0.2452	0.1864	−0.0706	0.085*
H8C	0.2213	0.2189	−0.1734	0.085*
C9	0.13286 (6)	0.2372 (4)	0.4458 (7)	0.0294 (9)
H9	0.1212	0.2054	0.3420	0.035*
N10	0.12749 (5)	0.2679 (4)	0.6473 (6)	0.0291 (7)
C11	0.10465 (5)	0.2522 (4)	0.7171 (7)	0.0262 (8)
C12	0.08845 (6)	0.1478 (4)	0.6058 (7)	0.0299 (8)
H12	0.0926	0.0816	0.4748	0.036*
C13	0.06651 (6)	0.1403 (4)	0.6851 (7)	0.0298 (8)
H13	0.0555	0.0692	0.6089	0.036*
C14	0.06059 (5)	0.2357 (4)	0.8746 (6)	0.0247 (8)
C15	0.07629 (5)	0.3366 (4)	0.9897 (7)	0.0277 (8)
H15	0.0720	0.4020	1.1210	0.033*
C16	0.09834 (5)	0.3414 (4)	0.9119 (7)	0.0275 (8)
H16	0.1095	0.4075	0.9939	0.033*
O17	0.03923 (4)	0.2212 (3)	0.9705 (4)	0.0297 (6)
C18	0.02009 (5)	0.2435 (4)	0.8384 (7)	0.0265 (8)
C19	0.02040 (6)	0.3185 (4)	0.6262 (7)	0.0282 (8)
H19	0.0344	0.3466	0.5542	0.034*
C20	0.0000	0.3517 (6)	0.5207 (9)	0.0282 (11)
H20	0.0000	0.3988	0.3715	0.034*
C21	0.0000	0.2007 (6)	0.9448 (10)	0.0267 (11)
H21	0.0000	0.1432	1.0881	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0204 (16)	0.037 (2)	0.032 (2)	−0.0001 (13)	0.0009 (16)	0.0060 (16)
C2	0.0318 (18)	0.039 (2)	0.030 (2)	−0.0004 (15)	0.0030 (16)	−0.0016 (16)
C3	0.0286 (18)	0.0354 (19)	0.033 (2)	−0.0043 (13)	−0.0012 (17)	0.0008 (17)
C4	0.0277 (17)	0.0271 (17)	0.025 (2)	0.0007 (12)	0.0006 (15)	0.0032 (14)
C5	0.0312 (17)	0.0318 (18)	0.030 (2)	−0.0006 (13)	−0.0033 (16)	−0.0025 (16)
C6	0.0264 (16)	0.0343 (18)	0.035 (2)	−0.0021 (13)	−0.0005 (17)	−0.0011 (17)
O7	0.0250 (13)	0.0602 (17)	0.0398 (17)	−0.0013 (11)	0.0049 (13)	−0.0029 (14)
C8	0.031 (2)	0.092 (4)	0.046 (3)	0.004 (2)	0.010 (2)	−0.009 (3)
C9	0.0294 (17)	0.0305 (18)	0.028 (2)	−0.0009 (13)	−0.0015 (16)	0.0030 (17)
N10	0.0229 (13)	0.0323 (15)	0.0321 (19)	−0.0009 (11)	0.0007 (14)	−0.0020 (14)
C11	0.0230 (16)	0.0260 (17)	0.030 (2)	0.0013 (12)	0.0016 (16)	0.0015 (15)
C12	0.0281 (17)	0.0298 (17)	0.032 (2)	0.0029 (13)	0.0002 (16)	−0.0040 (17)
C13	0.0255 (16)	0.0296 (16)	0.034 (2)	−0.0031 (13)	−0.0010 (16)	−0.0008 (16)
C14	0.0205 (15)	0.0254 (16)	0.028 (2)	0.0018 (12)	0.0004 (15)	0.0057 (14)
C15	0.0318 (17)	0.0255 (16)	0.0257 (19)	0.0025 (12)	−0.0012 (15)	−0.0004 (15)
C16	0.0265 (15)	0.0254 (16)	0.031 (2)	−0.0001 (12)	−0.0031 (15)	−0.0005 (15)
O17	0.0207 (11)	0.0401 (13)	0.0282 (16)	0.0032 (9)	−0.0002 (11)	0.0020 (12)
C18	0.0223 (17)	0.0264 (15)	0.031 (2)	0.0007 (12)	−0.0016 (14)	−0.0034 (16)
C19	0.0284 (17)	0.0260 (15)	0.030 (2)	−0.0004 (12)	0.0051 (15)	0.0006 (16)
C20	0.028 (2)	0.026 (2)	0.030 (3)	0.000	0.000	0.001 (2)
C21	0.028 (2)	0.025 (2)	0.027 (3)	0.000	0.000	0.002 (2)

Geometric parameters (Å, º) top

C1—O7	1.376 (4)	C11—C12	1.407 (5)
C1—C6	1.387 (6)	C12—C13	1.387 (4)
C1—C2	1.388 (5)	C12—H12	0.9600
C2—C3	1.394 (5)	C13—C14	1.386 (5)
C2—H2	0.9600	C13—H13	0.9600
C3—C4	1.395 (6)	C14—C15	1.384 (5)
C3—H3	0.9600	C14—O17	1.396 (4)
C4—C5	1.402 (5)	C15—C16	1.390 (5)
C4—C9	1.458 (5)	C15—H15	0.9600
C5—C6	1.377 (5)	C16—H16	0.9600
C5—H5	0.9600	O17—C18	1.394 (4)
C6—H6	0.9600	C18—C19	1.389 (6)
O7—C8	1.425 (6)	C18—C21	1.389 (4)
C8—H8A	0.9599	C19—C20	1.388 (4)
C8—H8B	0.9599	C19—H19	0.9600
C8—H8C	0.9599	C20—C19ⁱ	1.388 (4)
C9—N10	1.269 (5)	C20—H20	0.9600
C9—H9	0.9600	C21—C18ⁱ	1.389 (4)
N10—C11	1.423 (4)	C21—H21	0.9600
C11—C16	1.395 (5)

O7—C1—C6	115.8 (3)	C16—C11—N10	117.5 (3)
O7—C1—C2	124.2 (4)	C12—C11—N10	123.9 (3)
C6—C1—C2	120.0 (3)	C13—C12—C11	120.1 (3)
C1—C2—C3	119.4 (4)	C13—C12—H12	119.9
C1—C2—H2	120.3	C11—C12—H12	119.9
C3—C2—H2	120.3	C14—C13—C12	119.8 (3)
C2—C3—C4	120.7 (3)	C14—C13—H13	120.1
C2—C3—H3	119.6	C12—C13—H13	120.1
C4—C3—H3	119.6	C15—C14—C13	121.2 (3)
C3—C4—C5	119.0 (3)	C15—C14—O17	116.7 (3)
C3—C4—C9	119.4 (3)	C13—C14—O17	121.8 (3)
C5—C4—C9	121.7 (3)	C14—C15—C16	118.8 (3)
C6—C5—C4	120.0 (4)	C14—C15—H15	120.6
C6—C5—H5	120.0	C16—C15—H15	120.6
C4—C5—H5	120.0	C15—C16—C11	121.4 (3)
C5—C6—C1	120.8 (3)	C15—C16—H16	119.3
C5—C6—H6	119.6	C11—C16—H16	119.3
C1—C6—H6	119.6	C18—O17—C14	119.8 (3)
C1—O7—C8	117.6 (3)	C19—C18—C21	121.6 (3)
O7—C8—H8A	109.5	C19—C18—O17	123.8 (3)
O7—C8—H8B	109.5	C21—C18—O17	114.3 (4)
H8A—C8—H8B	109.5	C20—C19—C18	118.5 (3)
O7—C8—H8C	109.5	C20—C19—H19	120.7
H8A—C8—H8C	109.5	C18—C19—H19	120.7
H8B—C8—H8C	109.5	C19—C20—C19ⁱ	121.4 (5)
N10—C9—C4	122.8 (3)	C19—C20—H20	119.3
N10—C9—H9	118.6	C19ⁱ—C20—H20	119.3
C4—C9—H9	118.6	C18ⁱ—C21—C18	118.3 (5)
C9—N10—C11	120.3 (3)	C18ⁱ—C21—H21	120.9
C16—C11—C12	118.6 (3)	C18—C21—H21	120.9

O7—C1—C2—C3	−178.7 (3)	N10—C11—C12—C13	−179.8 (3)
C6—C1—C2—C3	−0.6 (5)	C11—C12—C13—C14	−0.2 (5)
C1—C2—C3—C4	−2.6 (5)	C12—C13—C14—C15	−1.1 (5)
C2—C3—C4—C5	3.6 (5)	C12—C13—C14—O17	−174.9 (3)
C2—C3—C4—C9	−176.2 (3)	C13—C14—C15—C16	0.1 (5)
C3—C4—C5—C6	−1.6 (5)	O17—C14—C15—C16	174.1 (3)
C9—C4—C5—C6	178.2 (3)	C14—C15—C16—C11	2.3 (5)
C4—C5—C6—C1	−1.5 (5)	C12—C11—C16—C15	−3.5 (5)
O7—C1—C6—C5	−179.1 (3)	N10—C11—C16—C15	178.6 (3)
C2—C1—C6—C5	2.6 (5)	C15—C14—O17—C18	134.4 (3)
C6—C1—O7—C8	175.3 (4)	C13—C14—O17—C18	−51.6 (4)
C2—C1—O7—C8	−6.4 (5)	C14—O17—C18—C19	−15.0 (4)
C3—C4—C9—N10	166.3 (3)	C14—O17—C18—C21	171.2 (3)
C5—C4—C9—N10	−13.6 (5)	C21—C18—C19—C20	0.4 (5)
C4—C9—N10—C11	−179.0 (3)	O17—C18—C19—C20	−173.0 (3)
C9—N10—C11—C16	−159.2 (3)	C18—C19—C20—C19ⁱ	2.6 (6)
C9—N10—C11—C12	23.0 (5)	C19—C18—C21—C18ⁱ	−3.3 (6)
C16—C11—C12—C13	2.4 (5)	O17—C18—C21—C18ⁱ	170.7 (3)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O7ⁱⁱ	0.96	2.57	3.411 (5)	147
C13—H13···O17ⁱⁱⁱ	0.96	2.52	3.405 (4)	154

Symmetry codes: (ii) −x+1/2, −y+1/2, z−1/2; (iii) x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₃₄H₂₈N₂O₄
M_r	528.58
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	163
a, b, c (Å)	59.344 (13), 7.484 (3), 5.988 (2)
V (Å³)	2659.4 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.60 × 0.41 × 0.02

Data collection
Diffractometer	Rigaku AFC8S Mercury CCD diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.837, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7742, 1351, 1164
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.142, 1.09
No. of reflections	1351
No. of parameters	185
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23

Computer programs: CrystalClear (Rigaku, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O7ⁱ	0.9600	2.5700	3.411 (5)	147.00
C13—H13···O17ⁱⁱ	0.9600	2.5200	3.405 (4)	154.00

Symmetry codes: (i) −x+1/2, −y+1/2, z−1/2; (ii) x, −y, z−1/2.

Acknowledgements

The authors thank the Organization for the Prohibition of Chemical Weapons for financial support.

References

Ali, Q., Hussain, Z., Shah, M. R. & VanDerveer, D. (2008). Acta Cryst. E64, o1377. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jacobson, R. (1998). Private communication to the Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2001). CrystalClear. Rigaku Corporation,Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar