N,N′-Bis(4-methyl­benzyl­idene)benzene-1,4-diamine

Li, H.; Xiang, Y.; Han, H.

doi:10.1107/S1600536811041675

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2953

doi:10.1107/S1600536811041675

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N,N′-Bis(4-methylbenzylidene)benzene-1,4-diamine

Haoyang Li,^a Yonggang Xiang ^a and Hongfei Han ^a ^*

^aDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China
^*Correspondence e-mail: hhf_2222@yahoo.com.cn

(Received 8 October 2011; accepted 10 October 2011; online 12 October 2011)

The centrosymmetric title compound, C₂₂H₂₀N₂, crystallizes with one half-molecule in the asymmetric unit. The dihedral angle between the central and outer benzene rings is 46.2 (2)°.

Related literature

For the use of Schiff bases as ligands in metal complexes, see: Chen et al. (2008 ); May et al. (2004 ).

Experimental

Crystal data

C₂₂H₂₀N₂
M_r = 312.40
Monoclinic, P 2₁ /c
a = 6.4750 (6) Å
b = 7.1561 (8) Å
c = 19.594 (2) Å
β = 107.555 (1)°
V = 865.61 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.46 × 0.40 × 0.37 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.968, T_max = 0.974
4151 measured reflections
1532 independent reflections
844 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.145
S = 1.04
1532 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 I, global. DOI: 10.1107/S1600536811041675/bt5670sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041675/bt5670Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041675/bt5670Isup3.cml

checkCIF report

Comment top

Schiff bases containing the C═N bond have been receiving considerable attention for many years, primarily due to their importance as ligands in metal complexes with special biological (May et al., 2004), and catalytic properties (Chen et al., 2008).

As a part of our studies on synthesis and structural peculiarities of Schiff bases derived from 1,4-benzenediamine and 4-methyl benzaldehyde, we determined the structure of the title compound (Fig. 1). The molecule includes two C═ N bonds, which are coplanar. The distance between the C atom and the N atom in the C═N bond is 1.266 (2) Å. In the structure the dihedral angle between adjacent benzene rings planes is 46.2 (2)°.

Related literature top

For the use of Schiff bases as ligands in metal complexes, see: Chen et al. (2008); May et al. (2004).

Experimental top

1,4-benzenediamine (0.324 g, 3 mmol) was added dropwise with stirring at 273K to a solution of 4-methyl benzaldehyde (0.721 g, 6 mmol) in ethanol. The mixture were warmed to room temperature and stirred for 2 h. The reaction mixture was filtered and the filter cake was recrystallized from ethanol (yield 75%). Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a tetrahydrofuran solution.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, showing the atom–numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

N,N'-Bis(4-methylbenzylidene)benzene-1,4-diamine top

Crystal data top

C₂₂H₂₀N₂	F(000) = 332
M_r = 312.40	D_x = 1.199 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.4750 (6) Å	Cell parameters from 954 reflections
b = 7.1561 (8) Å	θ = 2.9–23.3°
c = 19.594 (2) Å	µ = 0.07 mm⁻¹
β = 107.555 (1)°	T = 293 K
V = 865.61 (16) Å³	Block, colorless
Z = 2	0.46 × 0.40 × 0.37 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1532 independent reflections
Radiation source: fine-focus sealed tube	844 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.968, T_max = 0.974	k = −8→6
4151 measured reflections	l = −23→23

Refinement top

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.0581P)² + 0.1422P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1532 reflections	Δρ_max = 0.13 e Å⁻³
111 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.069 (8)

Crystal data top

C₂₂H₂₀N₂	V = 865.61 (16) Å³
M_r = 312.40	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.4750 (6) Å	µ = 0.07 mm⁻¹
b = 7.1561 (8) Å	T = 293 K
c = 19.594 (2) Å	0.46 × 0.40 × 0.37 mm
β = 107.555 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1532 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	844 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.974	R_int = 0.034
4151 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.04	Δρ_max = 0.13 e Å⁻³
1532 reflections	Δρ_min = −0.17 e Å⁻³
111 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	0.3167 (3)	0.4579 (2)	0.61261 (9)	0.0604 (6)
C1	0.4131 (3)	0.4803 (3)	0.55707 (11)	0.0543 (6)
C2	0.2944 (3)	0.5650 (3)	0.49390 (11)	0.0604 (6)
H2	0.1554	0.6084	0.4891	0.072*
C3	0.6190 (3)	0.4146 (3)	0.56201 (11)	0.0602 (6)
H3	0.7002	0.3558	0.6038	0.072*
C4	0.4309 (4)	0.4832 (3)	0.67687 (11)	0.0558 (6)
H4	0.5734	0.5226	0.6857	0.067*
C5	0.3491 (3)	0.4533 (3)	0.73774 (11)	0.0504 (5)
C6	0.4766 (4)	0.4939 (3)	0.80622 (11)	0.0609 (6)
H6	0.6167	0.5381	0.8135	0.073*
C7	0.3996 (4)	0.4699 (3)	0.86443 (12)	0.0678 (7)
H7	0.4889	0.4982	0.9101	0.081*
C8	0.1925 (4)	0.4049 (3)	0.85571 (12)	0.0621 (6)
C9	0.0668 (4)	0.3596 (3)	0.78732 (13)	0.0645 (6)
H9	−0.0723	0.3134	0.7802	0.077*
C10	0.1436 (3)	0.3814 (3)	0.72947 (12)	0.0609 (6)
H10	0.0564	0.3476	0.6841	0.073*
C11	0.1042 (5)	0.3887 (4)	0.91853 (13)	0.0913 (9)
H11A	0.2211	0.3657	0.9614	0.137*
H11B	0.0028	0.2872	0.9105	0.137*
H11C	0.0326	0.5030	0.9236	0.137*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0561 (12)	0.0671 (13)	0.0566 (11)	0.0008 (9)	0.0150 (10)	0.0079 (9)
C1	0.0510 (14)	0.0562 (13)	0.0538 (13)	−0.0039 (10)	0.0131 (11)	0.0040 (10)
C2	0.0483 (13)	0.0689 (15)	0.0620 (14)	0.0065 (10)	0.0137 (11)	0.0091 (11)
C3	0.0513 (14)	0.0707 (15)	0.0540 (13)	0.0037 (11)	0.0090 (11)	0.0118 (11)
C4	0.0535 (14)	0.0499 (13)	0.0631 (14)	−0.0004 (10)	0.0162 (12)	0.0037 (10)
C5	0.0527 (13)	0.0424 (11)	0.0553 (13)	0.0031 (9)	0.0153 (11)	0.0031 (9)
C6	0.0574 (14)	0.0571 (14)	0.0659 (15)	−0.0033 (10)	0.0151 (12)	−0.0020 (11)
C7	0.0766 (17)	0.0665 (15)	0.0560 (14)	0.0031 (12)	0.0137 (13)	−0.0026 (11)
C8	0.0741 (16)	0.0499 (13)	0.0678 (15)	0.0103 (12)	0.0299 (13)	0.0089 (11)
C9	0.0597 (15)	0.0599 (14)	0.0774 (16)	−0.0007 (11)	0.0261 (13)	0.0070 (12)
C10	0.0555 (14)	0.0619 (14)	0.0609 (14)	−0.0018 (11)	0.0113 (11)	0.0006 (11)
C11	0.114 (2)	0.0928 (19)	0.0806 (18)	0.0107 (17)	0.0488 (17)	0.0172 (14)

Geometric parameters (Å, º) top

N1—C4	1.266 (2)	C6—C7	1.387 (3)
N1—C1	1.418 (3)	C6—H6	0.9300
C1—C2	1.384 (3)	C7—C8	1.380 (3)
C1—C3	1.389 (3)	C7—H7	0.9300
C2—C3ⁱ	1.381 (3)	C8—C9	1.380 (3)
C2—H2	0.9300	C8—C11	1.510 (3)
C3—C2ⁱ	1.381 (3)	C9—C10	1.377 (3)
C3—H3	0.9300	C9—H9	0.9300
C4—C5	1.459 (3)	C10—H10	0.9300
C4—H4	0.9300	C11—H11A	0.9600
C5—C6	1.378 (3)	C11—H11B	0.9600
C5—C10	1.390 (3)	C11—H11C	0.9600

C4—N1—C1	119.14 (19)	C8—C7—C6	121.1 (2)
C2—C1—C3	118.22 (19)	C8—C7—H7	119.4
C2—C1—N1	118.79 (19)	C6—C7—H7	119.4
C3—C1—N1	122.94 (19)	C7—C8—C9	117.8 (2)
C3ⁱ—C2—C1	120.5 (2)	C7—C8—C11	121.2 (2)
C3ⁱ—C2—H2	119.8	C9—C8—C11	121.1 (2)
C1—C2—H2	119.8	C10—C9—C8	121.3 (2)
C2ⁱ—C3—C1	121.3 (2)	C10—C9—H9	119.4
C2ⁱ—C3—H3	119.3	C8—C9—H9	119.4
C1—C3—H3	119.3	C9—C10—C5	121.1 (2)
N1—C4—C5	123.0 (2)	C9—C10—H10	119.4
N1—C4—H4	118.5	C5—C10—H10	119.4
C5—C4—H4	118.5	C8—C11—H11A	109.5
C6—C5—C10	117.6 (2)	C8—C11—H11B	109.5
C6—C5—C4	120.4 (2)	H11A—C11—H11B	109.5
C10—C5—C4	122.0 (2)	C8—C11—H11C	109.5
C5—C6—C7	121.1 (2)	H11A—C11—H11C	109.5
C5—C6—H6	119.5	H11B—C11—H11C	109.5
C7—C6—H6	119.5

C4—N1—C1—C2	−140.7 (2)	C4—C5—C6—C7	178.63 (19)
C4—N1—C1—C3	41.9 (3)	C5—C6—C7—C8	−0.1 (3)
C3—C1—C2—C3ⁱ	−0.9 (3)	C6—C7—C8—C9	1.8 (3)
N1—C1—C2—C3ⁱ	−178.49 (19)	C6—C7—C8—C11	−176.6 (2)
C2—C1—C3—C2ⁱ	0.9 (4)	C7—C8—C9—C10	−1.1 (3)
N1—C1—C3—C2ⁱ	178.39 (19)	C11—C8—C9—C10	177.3 (2)
C1—N1—C4—C5	−176.51 (17)	C8—C9—C10—C5	−1.2 (3)
N1—C4—C5—C6	−176.06 (19)	C6—C5—C10—C9	2.8 (3)
N1—C4—C5—C10	4.8 (3)	C4—C5—C10—C9	−178.00 (19)
C10—C5—C6—C7	−2.2 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀N₂
M_r	312.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.4750 (6), 7.1561 (8), 19.594 (2)
β (°)	107.555 (1)
V (Å³)	865.61 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.46 × 0.40 × 0.37

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.968, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	4151, 1532, 844
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.145, 1.04
No. of reflections	1532
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.17

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was carried out under the sponsorship of the ShanXi scientific technology project (20110321044).

References

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