(E,E)-N,N′-Bis­(4-methoxy­benzyl­idene)cyclo­hexane-1,2-diamine

Wang, G.-X.

doi:10.1107/S1600536808023751

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1647

doi:10.1107/S1600536808023751

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(E,E)-N,N′-Bis(4-methoxybenzylidene)cyclohexane-1,2-diamine

Guo-Xi Wang ^a ^*

^aDepartment of Chemical Engineering, Anyang Institute of Technology, Anyang, 455000, People's Republic of China
^*Correspondence e-mail: aywgx@yahoo.com.cn

(Received 24 July 2008; accepted 27 July 2008; online 31 July 2008)

In the title compound, C₂₂H₂₆N₂O₂, the methoxy and the benzylidene groups are essentially coplanar, and the cyclohexane ring has a chair conformation. The two halves of the molecule are related by a twofold rotation. The crystal structure is stabilized only by van der Waals interactions.

Related literature

For the chemistry of Schiff base derivatives, see: Negm & Zaki (2008 ); Feng et al. (2008 ); Lee & Do (2007 ).

Experimental

Crystal data

C₂₂H₂₆N₂O₂
M_r = 350.45
Orthorhombic, P c c n
a = 19.674 (3) Å
b = 5.4097 (9) Å
c = 18.662 (3) Å
V = 1986.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 (2) K
0.35 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.978, T_max = 0.985
18603 measured reflections
2262 independent reflections
1588 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.154
S = 1.12
2262 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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, New_Global_Publ_Block. DOI: 10.1107/S1600536808023751/wk2089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808023751/wk2089Isup2.hkl

checkCIF report

Comment top

In the past five years, we have focused on the chemistry of schiff-base derivatives because of their biological behaviors and their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Negm & Zaki, 2008; Feng et al. 2008; Lee & Do, 2007). We report here the crystal structure of the title compound, (N¹E,N²E)-N¹,N²-bis(4-methoxybenzylidene)cyclohexane-1,2-diamine.

In the title compound (Fig.1), there is a rotation axis bisecting the molecule through the cyclohexane ring. The methoxy and the benzylidene groups are essentially coplanar, and the cyclohexane-1,2-diamine group is in the chair form. The C4=N1 bond length of 1.249 (2) Å is consistent with the value for a double bond. The crystal structure is stabilized only by van der Waals interactions.

Related literature top

For the chemistry of schiff-base derivatives, see: Negm & Zaki (2008); Feng et al. (2008); Lee & Do (2007).

Experimental top

rac-Diaminocyclohexane (1.20 g, 10.5 mmol) and p-anisaldehyde (1.36 g, 10.0 mmol) were dissolved in ethanol (20 mL) under magnetic stirring. The mixture was heated to reflux for 12 h. After cooled to room temperature, the resulting content was put to a refrigerator to stand over night. Then, the precipitate was filtered off and recrystallized from ethanol affording colorless block crystals of this compound suitable for X-ray analysis were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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. A view of the title compound with the atom numbering scheme, symmetry related atoms, (-x+1/2, -y+1/2, z) denoted by A. Displacement ellipsoids were drawn at the 30% probability level.

(E,E)-N,N'-Bis(4- methoxybenzylidene)cyclohexane-1,2-diamine top

Crystal data top

C₂₂H₂₆N₂O₂	F(000) = 752
M_r = 350.45	D_x = 1.172 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 3131 reflections
a = 19.674 (3) Å	θ = 3.0–27.4°
b = 5.4097 (9) Å	µ = 0.08 mm⁻¹
c = 18.662 (3) Å	T = 298 K
V = 1986.2 (6) Å³	Block, colorless
Z = 4	0.35 × 0.30 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	2262 independent reflections
Radiation source: fine-focus sealed tube	1588 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −25→25
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −7→7
T_min = 0.978, T_max = 0.985	l = −24→24
18603 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0572P)² + 0.4317P] where P = (F_o² + 2F_c²)/3
2262 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₂₂H₂₆N₂O₂	V = 1986.2 (6) Å³
M_r = 350.45	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 19.674 (3) Å	µ = 0.08 mm⁻¹
b = 5.4097 (9) Å	T = 298 K
c = 18.662 (3) Å	0.35 × 0.30 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	2262 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1588 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.985	R_int = 0.060
18603 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.12	Δρ_max = 0.13 e Å⁻³
2262 reflections	Δρ_min = −0.14 e Å⁻³
118 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
O1	0.47992 (8)	0.4625 (3)	0.41000 (8)	0.0713 (5)
N1	0.32205 (8)	0.3062 (3)	0.11039 (9)	0.0558 (5)
C5	0.36446 (9)	0.4561 (4)	0.22382 (10)	0.0493 (5)
C2	0.32123 (10)	0.3262 (5)	−0.02019 (11)	0.0629 (6)
H2A	0.3454	0.1699	−0.0204	0.075*
H2B	0.3547	0.4577	−0.0203	0.075*
C7	0.45135 (10)	0.2643 (4)	0.29659 (11)	0.0535 (5)
H7	0.4827	0.1380	0.3034	0.064*
C4	0.32303 (10)	0.4677 (4)	0.15823 (10)	0.0553 (5)
H4	0.2955	0.6057	0.1519	0.066*
C8	0.44380 (10)	0.4485 (4)	0.34762 (10)	0.0513 (5)
C6	0.41180 (10)	0.2704 (4)	0.23553 (10)	0.0539 (5)
H6	0.4170	0.1467	0.2014	0.065*
C3	0.27888 (9)	0.3439 (4)	0.04791 (10)	0.0532 (5)
H3	0.2592	0.5101	0.0506	0.064*
C10	0.35804 (10)	0.6392 (4)	0.27558 (11)	0.0591 (5)
H10	0.3270	0.7666	0.2688	0.071*
C1	0.27826 (11)	0.3452 (4)	−0.08769 (11)	0.0636 (6)
H1B	0.2587	0.5095	−0.0908	0.076*
H1A	0.3069	0.3204	−0.1294	0.076*
C11	0.52945 (14)	0.2748 (6)	0.42442 (13)	0.0871 (8)
H11A	0.5509	0.3076	0.4696	0.131*
H11B	0.5631	0.2746	0.3872	0.131*
H11C	0.5075	0.1164	0.4262	0.131*
C9	0.39688 (10)	0.6346 (4)	0.33659 (11)	0.0595 (6)
H9	0.3916	0.7580	0.3708	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0718 (9)	0.0912 (12)	0.0509 (9)	0.0097 (9)	−0.0096 (7)	−0.0121 (8)
N1	0.0534 (9)	0.0608 (11)	0.0532 (10)	0.0022 (8)	−0.0042 (8)	−0.0036 (8)
C5	0.0448 (9)	0.0533 (11)	0.0497 (11)	−0.0015 (9)	0.0020 (8)	−0.0005 (9)
C2	0.0514 (11)	0.0790 (16)	0.0583 (13)	−0.0074 (10)	0.0038 (10)	0.0038 (11)
C7	0.0538 (11)	0.0521 (12)	0.0544 (11)	0.0079 (9)	0.0001 (10)	−0.0009 (9)
C4	0.0490 (11)	0.0572 (12)	0.0597 (13)	0.0051 (9)	−0.0020 (9)	0.0010 (10)
C8	0.0510 (10)	0.0593 (12)	0.0436 (10)	−0.0043 (9)	0.0035 (9)	−0.0025 (9)
C6	0.0574 (11)	0.0524 (12)	0.0518 (11)	0.0006 (9)	0.0032 (10)	−0.0101 (9)
C3	0.0528 (11)	0.0543 (12)	0.0524 (11)	0.0028 (9)	−0.0044 (9)	0.0016 (9)
C10	0.0572 (12)	0.0541 (12)	0.0661 (13)	0.0088 (10)	0.0001 (10)	−0.0060 (10)
C1	0.0680 (13)	0.0694 (14)	0.0535 (12)	−0.0003 (11)	0.0036 (10)	0.0037 (10)
C11	0.0886 (17)	0.110 (2)	0.0625 (15)	0.0236 (16)	−0.0193 (13)	0.0001 (14)
C9	0.0628 (12)	0.0580 (13)	0.0578 (13)	0.0034 (10)	0.0017 (10)	−0.0148 (10)

Geometric parameters (Å, º) top

O1—C8	1.366 (2)	C4—H4	0.9300
O1—C11	1.433 (3)	C8—C9	1.381 (3)
N1—C4	1.249 (2)	C6—H6	0.9300
N1—C3	1.457 (2)	C3—C3ⁱ	1.525 (4)
C5—C10	1.389 (3)	C3—H3	0.9800
C5—C6	1.387 (3)	C10—C9	1.371 (3)
C5—C4	1.472 (3)	C10—H10	0.9300
C2—C3	1.523 (3)	C1—C1ⁱ	1.516 (4)
C2—C1	1.521 (3)	C1—H1B	0.9700
C2—H2A	0.9700	C1—H1A	0.9700
C2—H2B	0.9700	C11—H11A	0.9600
C7—C6	1.380 (3)	C11—H11B	0.9600
C7—C8	1.386 (3)	C11—H11C	0.9600
C7—H7	0.9300	C9—H9	0.9300

C8—O1—C11	118.35 (17)	N1—C3—C2	109.88 (15)
C4—N1—C3	118.88 (17)	C3ⁱ—C3—C2	111.46 (14)
C10—C5—C6	117.90 (18)	N1—C3—H3	108.5
C10—C5—C4	119.83 (18)	C3ⁱ—C3—H3	108.5
C6—C5—C4	122.25 (18)	C2—C3—H3	108.5
C3—C2—C1	112.52 (16)	C9—C10—C5	120.92 (19)
C3—C2—H2A	109.1	C9—C10—H10	119.5
C1—C2—H2A	109.1	C5—C10—H10	119.5
C3—C2—H2B	109.1	C1ⁱ—C1—C2	111.22 (15)
C1—C2—H2B	109.1	C1ⁱ—C1—H1B	109.4
H2A—C2—H2B	107.8	C2—C1—H1B	109.4
C6—C7—C8	119.32 (19)	C1ⁱ—C1—H1A	109.4
C6—C7—H7	120.3	C2—C1—H1A	109.4
C8—C7—H7	120.3	H1B—C1—H1A	108.0
N1—C4—C5	124.96 (19)	O1—C11—H11A	109.5
N1—C4—H4	117.5	O1—C11—H11B	109.5
C5—C4—H4	117.5	H11A—C11—H11B	109.5
O1—C8—C9	115.75 (17)	O1—C11—H11C	109.5
O1—C8—C7	124.70 (18)	H11A—C11—H11C	109.5
C9—C8—C7	119.55 (18)	H11B—C11—H11C	109.5
C7—C6—C5	121.71 (18)	C8—C9—C10	120.61 (19)
C7—C6—H6	119.1	C8—C9—H9	119.7
C5—C6—H6	119.1	C10—C9—H9	119.7
N1—C3—C3ⁱ	109.94 (14)

C3—N1—C4—C5	−179.41 (17)	C4—N1—C3—C3ⁱ	−112.3 (2)
C10—C5—C4—N1	−175.8 (2)	C4—N1—C3—C2	124.6 (2)
C6—C5—C4—N1	6.0 (3)	C1—C2—C3—N1	175.80 (18)
C11—O1—C8—C9	−179.9 (2)	C1—C2—C3—C3ⁱ	53.7 (3)
C11—O1—C8—C7	0.1 (3)	C6—C5—C10—C9	−0.6 (3)
C6—C7—C8—O1	−179.97 (18)	C4—C5—C10—C9	−178.92 (19)
C6—C7—C8—C9	0.0 (3)	C3—C2—C1—C1ⁱ	−54.7 (3)
C8—C7—C6—C5	−0.1 (3)	O1—C8—C9—C10	179.73 (18)
C10—C5—C6—C7	0.4 (3)	C7—C8—C9—C10	−0.3 (3)
C4—C5—C6—C7	178.64 (18)	C5—C10—C9—C8	0.6 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₆N₂O₂
M_r	350.45
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	298
a, b, c (Å)	19.674 (3), 5.4097 (9), 18.662 (3)
V (Å³)	1986.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.978, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	18603, 2262, 1588
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.154, 1.12
No. of reflections	2262
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.14

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Feng, Y., Wang, C., Xu, J., Xu, L., Liao, D., Yan, S. & Jiang, Z. (2008). Inorg. Chem. Commun. 11, 549–552. Web of Science CSD CrossRef CAS Google Scholar
Lee, J., Kim, Y. & Do, Y. (2007). Inorg. Chem. 46, 7701–7703. Web of Science CSD CrossRef PubMed CAS Google Scholar
Negm, N.-A. & Zaki, M.-F. (2008). Colloid Surf. B, 64, 179–183. Web of Science CrossRef CAS Google Scholar
Rigaku (2005). 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