4,6-Dichloro-2-((E)-{4-[(E)-3,5-dichloro-2-hy­droxy­benzyl­idene­amino]­butyl­imino}­meth­yl)phenol

Kargar, H.; Kia, R.; Adabi Ardakani, A.; Tahir, M.N.

doi:10.1107/S1600536812028693

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages o2244-o2245

https://doi.org/10.1107/S1600536812028693

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4,6-Dichloro-2-((E)-{4-[(E)-3,5-dichloro-2-hydroxybenzylideneamino]butylimino}methyl)phenol

Hadi Kargar,^a ^* Reza Kia,^b ‡ Amir Adabi Ardakani ^c and Muhammad Nawaz Tahir ^d ^*

^aDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran, I. R. of IRAN, ^bDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, ^cArdakan Branch, Islamic Azad University, Ardakan, Iran, and ^dDepartment of Physics, University of Sargodha, Punjab, Pakistan
^*Correspondence e-mail: h.kargar@pnu.ac.ir, dmntahir_uos@yahoo.com

(Received 10 June 2012; accepted 25 June 2012; online 30 June 2012)

The asymmetric unit of the title compound, C₁₈H₁₆Cl₄N₂O₂, comprises half of a potentially tetradentate Schiff base ligand. It is located about a twofold rotation axis that bisects the central C—C bond of the butane-1,4-diamine group. There are two intramolecular O—H⋯N hydrogen bonds making S(6) ring motifs. In the crystal, molecules are linked by pairs of weak C—H⋯Cl interactions, forming inversion dimers, which are further connected by C—H⋯O hydrogen bonds into two-dimensional frameworks that lie parallel to (001).

Related literature

For standard bond lengths, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related Schiff base ligands, see: Kargar et al. (2011 ); Kia et al. (2010 ).

Experimental

Crystal data

C₁₈H₁₆Cl₄N₂O₂
M_r = 434.13
Orthorhombic, P b c n
a = 15.871 (3) Å
b = 12.505 (3) Å
c = 9.4133 (18) Å
V = 1868.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 291 K
0.35 × 0.16 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.805, T_max = 0.915
8772 measured reflections
2057 independent reflections
1264 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.095
S = 1.02
2057 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.95	1.71	2.565 (3)	149
C5—H5⋯O1ⁱ	0.93	2.48	3.370 (3)	160
C3—H3⋯Cl2ⁱⁱ	0.93	2.83	3.738 (3)	165
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005)'; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812028693/su2460sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028693/su2460Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028693/su2460Isup3.cml

checkCIF report

Comment top

In continuation of our work on the crystal structure analyses of Schiff base ligands (Kargar et al., (2011); Kia et al., (2010), we report herein on the crystal structure of the title compound. The asymmetric unit of the title compound, Fig. 1, comprises half of a potentially tetradentate Schiff base ligand. It is located about a two-fold rotation axis that bisects the central C9-C9a bond of the butane-1,4-diamine group. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. The intramolecular O—H···N hydrogen bonds make S(6) ring motifs (Fig. 2 and Table 1; Bernstein et al., 1995).

In the crystal, molecules are linked by pairs of weak C—H···Cl interactions to form inversion dimers which are further connected by C—H···O hydrogen bonds along the b axis direction, forming two dimensional networks that lie parallel to the ab plane (Table 1 and Fig. 2).

Related literature top

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related Schiff base ligands, see: Kargar et al. (2011); Kia et al. (2010).

Experimental top

The title compound was synthesized by adding 3,5-dichlorosalicylaldehyde (2 mmol) to a solution of butylenediamine (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Yellow-needle single crystals of the title compound, suitable for X-ray structure determination, were obtained by recrystallization from ethanol by slow evaporation of the solvents at room temperature over several days.

Structure description top

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related Schiff base ligands, see: Kargar et al. (2011); Kia et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005)'; data reduction: SAINT (Bruker, 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering [symmetry code for suffix A = -x, -y + 1, -z + 1].
	Fig. 2. The crystal packing of the title compound showing the C—H···O and weak C—H···Cl interactions (dashed lines; see Table 1 for details) forming two dimensional networks. Only the H atoms involved in hydrogen bonding are shown.

4,6-Dichloro-2-((E)-{4-[(E)-3,5-dichloro-2- hydroxybenzylideneamino]butylimino}methyl)phenol top

Crystal data top

C₁₈H₁₆Cl₄N₂O₂	F(000) = 888
M_r = 434.13	D_x = 1.543 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 851 reflections
a = 15.871 (3) Å	θ = 2.8–27.5°
b = 12.505 (3) Å	µ = 0.65 mm⁻¹
c = 9.4133 (18) Å	T = 291 K
V = 1868.3 (6) Å³	Needle, yellow
Z = 4	0.35 × 0.16 × 0.14 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2057 independent reflections
Radiation source: fine-focus sealed tube	1264 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 27.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −20→12
T_min = 0.805, T_max = 0.915	k = −16→15
8772 measured reflections	l = −10→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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0259P)² + 0.896P] where P = (F_o² + 2F_c²)/3
2057 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₈H₁₆Cl₄N₂O₂	V = 1868.3 (6) Å³
M_r = 434.13	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 15.871 (3) Å	µ = 0.65 mm⁻¹
b = 12.505 (3) Å	T = 291 K
c = 9.4133 (18) Å	0.35 × 0.16 × 0.14 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2057 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1264 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.915	R_int = 0.058
8772 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.02	Δρ_max = 0.31 e Å⁻³
2057 reflections	Δρ_min = −0.27 e Å⁻³
118 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.37204 (6)	0.74164 (6)	0.18745 (9)	0.0673 (3)
Cl2	0.44335 (5)	0.32968 (6)	0.08251 (9)	0.0613 (3)
O1	0.24660 (12)	0.65449 (13)	0.3845 (2)	0.0492 (5)
H1	0.2062	0.6189	0.4413	0.074*
N1	0.16734 (13)	0.50222 (17)	0.5089 (2)	0.0383 (5)
C1	0.29214 (16)	0.57913 (19)	0.3202 (3)	0.0356 (6)
C2	0.35462 (17)	0.60699 (19)	0.2224 (3)	0.0404 (7)
C3	0.40082 (17)	0.5318 (2)	0.1515 (3)	0.0428 (7)
H3	0.4418	0.5526	0.0866	0.051*
C4	0.38606 (17)	0.4244 (2)	0.1772 (3)	0.0413 (7)
C5	0.32680 (17)	0.3932 (2)	0.2738 (3)	0.0402 (7)
H5	0.3181	0.3209	0.2910	0.048*
C6	0.27940 (16)	0.46897 (19)	0.3465 (3)	0.0344 (6)
C7	0.21558 (16)	0.4352 (2)	0.4470 (3)	0.0379 (6)
H7	0.2096	0.3628	0.4670	0.046*
C8	0.10183 (16)	0.4624 (2)	0.6055 (3)	0.0435 (7)
H8A	0.0946	0.5125	0.6833	0.052*
H8B	0.1194	0.3944	0.6452	0.052*
C9	0.01787 (17)	0.4483 (2)	0.5280 (3)	0.0481 (8)
H9A	0.0258	0.3993	0.4492	0.058*
H9B	−0.0225	0.4163	0.5926	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0782 (6)	0.0361 (4)	0.0874 (6)	−0.0057 (4)	0.0253 (5)	0.0114 (4)
Cl2	0.0628 (5)	0.0484 (4)	0.0727 (6)	0.0047 (4)	0.0223 (4)	−0.0103 (4)
O1	0.0497 (12)	0.0349 (10)	0.0630 (12)	0.0051 (9)	0.0161 (11)	0.0044 (9)
N1	0.0308 (12)	0.0419 (12)	0.0421 (13)	−0.0032 (11)	0.0016 (11)	0.0050 (11)
C1	0.0305 (15)	0.0343 (13)	0.0420 (15)	0.0009 (12)	−0.0014 (13)	0.0019 (12)
C2	0.0410 (17)	0.0321 (13)	0.0481 (17)	−0.0052 (13)	0.0009 (14)	0.0058 (12)
C3	0.0362 (16)	0.0458 (16)	0.0465 (17)	−0.0041 (13)	0.0077 (14)	0.0027 (13)
C4	0.0394 (17)	0.0371 (14)	0.0475 (16)	−0.0003 (13)	0.0042 (14)	−0.0056 (13)
C5	0.0408 (16)	0.0324 (13)	0.0473 (17)	−0.0022 (12)	0.0036 (14)	0.0013 (12)
C6	0.0309 (15)	0.0353 (13)	0.0371 (15)	−0.0014 (12)	−0.0007 (12)	0.0026 (11)
C7	0.0354 (16)	0.0330 (13)	0.0453 (16)	−0.0042 (13)	−0.0035 (13)	0.0041 (12)
C8	0.0383 (16)	0.0475 (16)	0.0446 (16)	−0.0011 (14)	0.0032 (15)	0.0056 (13)
C9	0.0408 (18)	0.0456 (16)	0.0578 (19)	−0.0038 (14)	0.0128 (16)	0.0048 (14)

Geometric parameters (Å, º) top

Cl1—C2	1.738 (2)	C4—C5	1.365 (3)
Cl2—C4	1.739 (3)	C5—C6	1.390 (3)
O1—C1	1.333 (3)	C5—H5	0.9300
O1—H1	0.9457	C6—C7	1.449 (3)
N1—C7	1.276 (3)	C7—H7	0.9300
N1—C8	1.468 (3)	C8—C9	1.530 (4)
C1—C2	1.397 (4)	C8—H8A	0.9700
C1—C6	1.414 (3)	C8—H8B	0.9700
C2—C3	1.366 (4)	C9—C9ⁱ	1.506 (5)
C3—C4	1.385 (3)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700

C1—O1—H1	106.9	C5—C6—C7	120.1 (2)
C7—N1—C8	119.0 (2)	C1—C6—C7	119.9 (2)
O1—C1—C2	120.5 (2)	N1—C7—C6	121.8 (2)
O1—C1—C6	122.1 (2)	N1—C7—H7	119.1
C2—C1—C6	117.4 (2)	C6—C7—H7	119.1
C3—C2—C1	122.1 (2)	N1—C8—C9	111.1 (2)
C3—C2—Cl1	119.3 (2)	N1—C8—H8A	109.4
C1—C2—Cl1	118.6 (2)	C9—C8—H8A	109.4
C2—C3—C4	119.4 (3)	N1—C8—H8B	109.4
C2—C3—H3	120.3	C9—C8—H8B	109.4
C4—C3—H3	120.3	H8A—C8—H8B	108.0
C5—C4—C3	120.7 (2)	C9ⁱ—C9—C8	113.3 (3)
C5—C4—Cl2	120.5 (2)	C9ⁱ—C9—H9A	108.9
C3—C4—Cl2	118.9 (2)	C8—C9—H9A	108.9
C4—C5—C6	120.4 (2)	C9ⁱ—C9—H9B	108.9
C4—C5—H5	119.8	C8—C9—H9B	108.9
C6—C5—H5	119.8	H9A—C9—H9B	107.7
C5—C6—C1	120.0 (2)

O1—C1—C2—C3	−178.1 (2)	C4—C5—C6—C7	178.9 (2)
C6—C1—C2—C3	1.5 (4)	O1—C1—C6—C5	178.1 (2)
O1—C1—C2—Cl1	0.4 (4)	C2—C1—C6—C5	−1.5 (4)
C6—C1—C2—Cl1	−180.0 (2)	O1—C1—C6—C7	−0.5 (4)
C1—C2—C3—C4	−0.4 (4)	C2—C1—C6—C7	179.9 (2)
Cl1—C2—C3—C4	−178.8 (2)	C8—N1—C7—C6	177.7 (2)
C2—C3—C4—C5	−0.9 (4)	C5—C6—C7—N1	−175.5 (2)
C2—C3—C4—Cl2	178.2 (2)	C1—C6—C7—N1	3.1 (4)
C3—C4—C5—C6	1.0 (4)	C7—N1—C8—C9	−93.8 (3)
Cl2—C4—C5—C6	−178.2 (2)	N1—C8—C9—C9ⁱ	−63.4 (4)
C4—C5—C6—C1	0.3 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.95	1.71	2.565 (3)	149
C5—H5···O1ⁱⁱ	0.93	2.48	3.370 (3)	160
C3—H3···Cl2ⁱⁱⁱ	0.93	2.83	3.738 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆Cl₄N₂O₂
M_r	434.13
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	291
a, b, c (Å)	15.871 (3), 12.505 (3), 9.4133 (18)
V (Å³)	1868.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.35 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.805, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	8772, 2057, 1264
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.095, 1.02
No. of reflections	2057
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.27

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005)', SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.95	1.7100	2.565 (3)	149
C5—H5···O1ⁱ	0.93	2.4800	3.370 (3)	160
C3—H3···Cl2ⁱⁱ	0.93	2.83	3.738 (3)	165

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

Footnotes

‡Present address: Structural Dynamics of (Bio)Chemical Systems, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany.

Acknowledgements

HK and AAA thank PNU for financial support. MNT thanks GC University of Sargodha, Pakistan, for the research facility.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kargar, H., Kia, R., Pahlavani, E. & Tahir, M. N. (2011). Acta Cryst. E67, o614. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kia, R., Kargar, H., Tahir, M. N. & Kianoosh, F. (2010). Acta Cryst. E66, o2296. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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