N,N′-Bis(3,4-dimethoxy­benzyl­idene)butane-1,4-diamine

Dehno Khalaji, A.; Fejfarova, K.; Dusek, M.

doi:10.1107/S1600536809025069

organic compounds

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Volume 65| Part 8| August 2009| Page o1773

doi:10.1107/S1600536809025069

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N,N′-Bis(3,4-dimethoxybenzylidene)butane-1,4-diamine

Aliakbar Dehno Khalaji,^a Karla Fejfarova ^b and Michal Dusek ^b ^*

^aDepartment of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran, and ^bInstitute of Physics of the ASCR, Na Slovance 2, 182 21 Praha 8, Czech Republic
^*Correspondence e-mail: dusek@fzu.cz

(Received 26 June 2009; accepted 29 June 2009; online 4 July 2009)

The title Schiff base compound, C₂₂H₂₈N₂O₄, was synthesized by the reaction of 3,4-dimethoxybenzaldehyde and 1,4-diaminobutane in methanol. The molecule is located on a center of inversion with one half-molecule in the asymmetric unit. Both C=N double bonds are in a trans configuration. Intermolecular C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For related structures, see: Khalaji & Ng (2008 ); Khalaji et al. (2007 ).

Experimental

Crystal data

C₂₂H₂₈N₂O₄
M_r = 384.5
Monoclinic, P 2₁ /c
a = 14.5770 (4) Å
b = 7.6201 (2) Å
c = 9.4456 (3) Å
β = 101.725 (2)°
V = 1027.31 (5) Å³
Z = 2
Cu Kα radiation
μ = 0.69 mm⁻¹
T = 120 K
0.29 × 0.16 × 0.09 mm

Data collection

Oxford Diffraction Gemini diffractometer with Xcalibur goniometer, an Atlas detector and a Gemini ultra Cu source
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.765, T_max = 0.935
5312 measured reflections
1594 independent reflections
1293 reflections with I > 3σ(I)
R_int = 0.024
θ_max = 62.3°

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.67
1594 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O1ⁱ	0.96	2.54	3.4945 (17)	171
C11—H11B⋯O1ⁱⁱ	0.96	2.58	3.4830 (17)	158
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: JANA2006.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025069/bt2985sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025069/bt2985Isup2.hkl

checkCIF report

Comment top

Recently, we have synthesized Schiff base compounds with a 1,2-diaminoethane unit and analyzed their crystal structures (Khalaji & Ng, 2008; Khalaji et al., 2007). In continuation of these studies, the title compound was prepared and its structure was determined.

The molecule of the title compound is shown in Fig.1. A l l bond lengths and angles are comparable with those observed in similar compounds (Khalaji & Ng, 2008; Khalaji et al., 2007). The C7—N1 and C8—N1 bond lengths of 1.2657 (19) and 1.4620 (17) Å, respectively, conform to the value for a double and single bond. The molecule displays an E configuration about the C=N double bond.

Oxygen O1 and methyl C11H₃ participate in two symmetry independent hydrogen bonds C—H···O which connect the molecules into a three-dimensional network (Fig. 2).

Related literature top

For related structures, see: Khalaji & Ng (2008); Khalaji et al. (2007).

Experimental top

A solution of 3,4-dimethoxybenzaldehyde (3.30 g, 0.02 mol) in 40 ml me thanol was heated for 25 min at 65°C and then stirred for about 30 min. To this stirring solution, a solution of 1,4-diaminobutane (0.84 g, 0.01 mol) in 5 ml me thanol was added dropwise with constant stirring. The mixture was refluxed for 1 h and then allowed to cool for overnight at 298 K. The resulting crude solid was collected by filtration and dried at room temperature. Crystals were grown by the slow evaporation technique at room temperature by using a mixture of 40 ml of chloroform-methanole (5:3 v/v) as a solvent. At the period of super saturation, tiny crystals were nucleated. They were allowed to grow to a maximum possible dimension and then filtered. Yield: 3.28 g, 85%. 1H-NMR (CDCl3, δ(p.p.m.)): 1.75 (t, 2H8), 3.61 (t, 4H1), 3.87 (s, 6H6), 3.90 (s, 6H7), 6.84 (d, 2H3), 7.10 (dd, 2H4), 7.39 (d, 2H5), 8.16 (S, 2H2).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).

Figures top

	Fig. 1. The molecular structure of the title compound with atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, -y, -x]
	Fig. 2. The packing of (I) viewed along b, with hydrogen bonds shown as dashed lines.

N,N'-Bis(3,4-dimethoxybenzylidene)butane-1,4-diamine top

Crystal data top

C₂₂H₂₈N₂O₄	F(000) = 412
M_r = 384.5	D_x = 1.243 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 3320 reflections
a = 14.5770 (4) Å	θ = 3.1–62.2°
b = 7.6201 (2) Å	µ = 0.69 mm⁻¹
c = 9.4456 (3) Å	T = 120 K
β = 101.725 (2)°	Prism, colorless
V = 1027.31 (5) Å³	0.29 × 0.16 × 0.09 mm
Z = 2

Data collection top

Oxford Diffraction Gemini diffractometer with Xcalibur goniometer, an Atlas detector and a Gemini ultra Cu source	1594 independent reflections
Radiation source: X-ray tube	1293 reflections with I > 3σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 20.7567 pixels mm^-1	θ_max = 62.3°, θ_min = 6.2°
Rotation method data acquisition using ω scans	h = −15→16
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −6→8
T_min = 0.765, T_max = 0.935	l = −10→8
5312 measured reflections

Refinement top

Refinement on F²	56 constraints
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.096	Weighting scheme based on measured s.u.'s w = 1/[σ²(I) + 0.0016I²]
S = 1.67	(Δ/σ)_max = 0.010
1594 reflections	Δρ_max = 0.13 e Å⁻³
127 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints

Crystal data top

C₂₂H₂₈N₂O₄	V = 1027.31 (5) Å³
M_r = 384.5	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 14.5770 (4) Å	µ = 0.69 mm⁻¹
b = 7.6201 (2) Å	T = 120 K
c = 9.4456 (3) Å	0.29 × 0.16 × 0.09 mm
β = 101.725 (2)°

Data collection top

Oxford Diffraction Gemini diffractometer with Xcalibur goniometer, an Atlas detector and a Gemini ultra Cu source	1594 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1293 reflections with I > 3σ(I)
T_min = 0.765, T_max = 0.935	R_int = 0.024
5312 measured reflections	θ_max = 62.3°

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.67	Δρ_max = 0.13 e Å⁻³
1594 reflections	Δρ_min = −0.14 e Å⁻³
127 parameters

Special details top

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.32039 (6)	−0.14609 (12)	0.79180 (10)	0.0270 (3)
O2	0.44401 (6)	0.09623 (12)	0.85186 (10)	0.0273 (3)
N1	0.09135 (9)	0.06805 (17)	0.32350 (12)	0.0300 (4)
C1	0.22426 (10)	0.16821 (19)	0.50087 (14)	0.0249 (4)
C2	0.23245 (10)	0.01522 (19)	0.58506 (14)	0.0253 (5)
C3	0.30568 (10)	−0.00345 (17)	0.70163 (14)	0.0230 (4)
C4	0.37318 (9)	0.13126 (18)	0.73672 (14)	0.0238 (4)
C5	0.36408 (10)	0.28352 (19)	0.65593 (14)	0.0267 (5)
C6	0.28914 (10)	0.30120 (19)	0.53867 (14)	0.0268 (5)
C7	0.14929 (10)	0.1882 (2)	0.37154 (14)	0.0271 (5)
C8	0.02298 (10)	0.1056 (2)	0.19086 (15)	0.0328 (5)
C9	0.03674 (10)	−0.01461 (19)	0.06882 (14)	0.0280 (5)
C10	0.25804 (11)	−0.2911 (2)	0.75602 (16)	0.0335 (5)
C11	0.50866 (10)	0.2352 (2)	0.89969 (16)	0.0334 (5)
H2	0.186873	−0.076684	0.56133	0.0303*
H5	0.40895	0.376514	0.680225	0.032*
H6	0.282503	0.407674	0.483197	0.0322*
H7	0.144082	0.298205	0.320967	0.0325*
H8a	0.02928	0.225547	0.163206	0.0393*
H8b	−0.039196	0.0907	0.208212	0.0393*
H9a	0.098065	0.003565	0.048977	0.0337*
H9b	0.034701	−0.13463	0.098931	0.0337*
H10a	0.278325	−0.386148	0.821663	0.0402*
H10b	0.195898	−0.256261	0.763371	0.0402*
H10c	0.257961	−0.328557	0.658943	0.0402*
H11a	0.55323	0.197841	0.983561	0.0401*
H11b	0.540945	0.265307	0.82402	0.0401*
H11c	0.475258	0.335902	0.923628	0.0401*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0291 (6)	0.0255 (5)	0.0232 (5)	−0.0036 (4)	−0.0026 (4)	0.0037 (4)
O2	0.0245 (5)	0.0302 (6)	0.0231 (5)	−0.0033 (4)	−0.0049 (4)	0.0017 (4)
N1	0.0301 (7)	0.0343 (7)	0.0218 (6)	0.0028 (6)	−0.0036 (5)	−0.0020 (5)
C1	0.0275 (8)	0.0271 (8)	0.0189 (7)	0.0039 (6)	0.0018 (6)	−0.0010 (6)
C2	0.0246 (7)	0.0285 (8)	0.0213 (7)	−0.0002 (6)	0.0014 (6)	−0.0043 (6)
C3	0.0264 (7)	0.0236 (8)	0.0182 (7)	0.0025 (6)	0.0024 (5)	0.0000 (6)
C4	0.0230 (7)	0.0293 (8)	0.0176 (7)	0.0017 (6)	0.0009 (6)	−0.0020 (6)
C5	0.0276 (8)	0.0278 (8)	0.0234 (7)	−0.0032 (6)	0.0021 (6)	−0.0005 (6)
C6	0.0319 (8)	0.0272 (8)	0.0208 (7)	0.0021 (6)	0.0037 (6)	0.0019 (6)
C7	0.0308 (8)	0.0284 (8)	0.0200 (7)	0.0057 (7)	0.0003 (6)	−0.0008 (6)
C8	0.0307 (8)	0.0365 (9)	0.0262 (8)	0.0043 (7)	−0.0059 (6)	−0.0004 (7)
C9	0.0252 (8)	0.0302 (8)	0.0258 (8)	−0.0001 (6)	−0.0019 (6)	0.0027 (6)
C10	0.0362 (9)	0.0277 (8)	0.0326 (8)	−0.0072 (7)	−0.0022 (7)	0.0042 (6)
C11	0.0283 (8)	0.0373 (9)	0.0299 (8)	−0.0088 (7)	−0.0052 (6)	0.0016 (7)

Geometric parameters (Å, º) top

O1—C3	1.3706 (16)	C6—H6	0.96
O1—C10	1.4272 (18)	C7—H7	0.96
O2—C4	1.3651 (14)	C8—C9	1.517 (2)
O2—C11	1.4287 (17)	C8—H8a	0.96
N1—C7	1.2657 (19)	C8—H8b	0.96
N1—C8	1.4620 (17)	C9—C9ⁱ	1.5236 (17)
C1—C2	1.403 (2)	C9—H9a	0.96
C1—C6	1.383 (2)	C9—H9b	0.96
C1—C7	1.4722 (17)	C10—H10a	0.96
C2—C3	1.3763 (17)	C10—H10b	0.96
C2—H2	0.96	C10—H10c	0.96
C3—C4	1.4139 (19)	C11—H11a	0.96
C4—C5	1.380 (2)	C11—H11b	0.96
C5—C6	1.3951 (18)	C11—H11c	0.96
C5—H5	0.96

C3—O1—C10	117.08 (10)	N1—C8—C9	111.13 (12)
C4—O2—C11	116.78 (10)	N1—C8—H8a	109.4714
C7—N1—C8	117.04 (12)	N1—C8—H8b	109.4713
C2—C1—C6	119.20 (11)	C9—C8—H8a	109.4714
C2—C1—C7	121.32 (13)	C9—C8—H8b	109.471
C6—C1—C7	119.46 (13)	H8a—C8—H8b	107.7587
C1—C2—C3	120.15 (13)	C8—C9—C9ⁱ	112.43 (12)
C1—C2—H2	119.9235	C8—C9—H9a	109.4708
C3—C2—H2	119.9231	C8—C9—H9b	109.4709
O1—C3—C2	125.24 (12)	C9ⁱ—C9—H9a	109.4717
O1—C3—C4	114.61 (11)	C9ⁱ—C9—H9b	109.4713
C2—C3—C4	120.14 (12)	H9a—C9—H9b	106.344
O2—C4—C3	114.99 (11)	O1—C10—H10a	109.4718
O2—C4—C5	125.24 (12)	O1—C10—H10b	109.4712
C3—C4—C5	119.77 (11)	O1—C10—H10c	109.4714
C4—C5—C6	119.46 (13)	H10a—C10—H10b	109.471
C4—C5—H5	120.2676	H10a—C10—H10c	109.4712
C6—C5—H5	120.2684	H10b—C10—H10c	109.4707
C1—C6—C5	121.22 (13)	O2—C11—H11a	109.4712
C1—C6—H6	119.3878	O2—C11—H11b	109.4717
C5—C6—H6	119.3886	O2—C11—H11c	109.4713
N1—C7—C1	123.46 (13)	H11a—C11—H11b	109.4716
N1—C7—H7	118.272	H11a—C11—H11c	109.4708
C1—C7—H7	118.2721	H11b—C11—H11c	109.4708

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱⁱ	0.96	2.54	3.4945 (17)	171
C11—H11B···O1ⁱⁱⁱ	0.96	2.58	3.4830 (17)	158

Symmetry codes: (ii) −x+1, −y, −z+2; (iii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₈N₂O₄
M_r	384.5
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	14.5770 (4), 7.6201 (2), 9.4456 (3)
β (°)	101.725 (2)
V (Å³)	1027.31 (5)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.29 × 0.16 × 0.09

Data collection
Diffractometer	Oxford Diffraction Gemini diffractometer with Xcalibur goniometer, an Atlas detector and a Gemini ultra Cu source
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.765, 0.935
No. of measured, independent and observed [I > 3σ(I)] reflections	5312, 1594, 1293
R_int	0.024
θ_max (°)	62.3
(sin θ/λ)_max (Å⁻¹)	0.574

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.67
No. of reflections	1594
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.14

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SIR2002 (Burla et al., 2003), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.96	2.54	3.4945 (17)	171
C11—H11B···O1ⁱⁱ	0.96	2.58	3.4830 (17)	158

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, y+1/2, −z+3/2.

Acknowledgements

We acknowledge Golestan University (GU) for partial support of this work, the institutional research plan No. AVOZ10100521 of the Institute of Physics and project 202/07/J007 of the Grant Agency of the Czech Republic.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Khalaji, A. D., Brad, K. & Zhang, Y. (2007). Acta Cryst. E63, o4389. Web of Science CSD CrossRef IUCr Journals Google Scholar
Khalaji, A. D. & Ng, S. W. (2008). Acta Cryst. E64, o1771. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Petříček, V., Dušek, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Praha, Czech Republic. Google Scholar