4,6-Dichloro-2-[(E)-(2-{[(E)-3,5-dichloro-2-oxidobenzyl­idene]aza­nium­yl}eth­yl)iminiumylmeth­yl]phenolate

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

doi:10.1107/S160053681202870X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages o2242-o2243

https://doi.org/10.1107/S160053681202870X

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4,6-Dichloro-2-[(E)-(2-{[(E)-3,5-dichloro-2-oxidobenzylidene]azaniumyl}ethyl)iminiumylmethyl]phenolate

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

^aDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, ^bDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 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 9 June 2012; accepted 25 June 2012; online 30 June 2012)

The asymmetric unit of the title compound, C₁₆H₁₂Cl₄N₂O₂, comprises half of a potentially tetradentate Schiff base ligand, located about a twofold rotation axis which bisects the central C—C bond of the ethane-1,2-diamine group. In the solid state, the compound exists in the zwitterionic form. There are two intramolecular N—H⋯O hydrogen bonds making S(6) ring motifs. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming two-dimensional frameworks which lie parallel to (100). There are also short Cl⋯Cl [3.4395 (9) Å] contacts present.

Related literature

For standard bond lengths, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For van der Waals radii, see: Bondi (1964 ). For related Schiff base ligands, see: Kargar et al. (2011 ); Kia et al. (2010 ).

Experimental

Crystal data

C₁₆H₁₂Cl₄N₂O₂
M_r = 406.08
Monoclinic, C 2/c
a = 20.0505 (14) Å
b = 10.1460 (9) Å
c = 9.0579 (6) Å
β = 114.955 (4)°
V = 1670.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 291 K
0.21 × 0.14 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.864, T_max = 0.932
6453 measured reflections
1838 independent reflections
1146 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.097
S = 0.97
1838 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.97	1.74	2.585 (3)	143
C8—H8A⋯O1ⁱ	0.97	2.55	3.436 (3)	152
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

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/S160053681202870X/su2459sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202870X/su2459Isup2.hkl

checkCIF report

Comment top

In continuation of our work on the crystal structure 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 that exists in the keto-amine tautomeric form. The molecule is located about a two-fold rotation axis which bisects the central C8-C8a bond of the ethane-1,2-diamine group. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. The intramolecular N—H···O hydrogen bonds make S(6) ring motifs (Table 1; Bernstein et al., 1995).

In the crystal, molecules are linked by C—H···O hydrogen bonds along the b and c axes directions, forming two dimensional networks which lie parallel to the bc plane [Table 1 and Fig. 2]. There are also short Cl···Clⁱⁱ [3.4384 (10)Å; symmetry code: (ii) -x, y, 1/2 - z] contacts present, which are shorter than the sum of the van der waals radius of Cl atoms (Bondi, 1964; Fig. 3).

Related literature top

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For van der Waals radii, see: Bondi (1964). 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 ethylenediamine (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Yellow 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

In continuation of our work on the crystal structure of Schiff base ligands (Kargar et al., (2011); Kia et al., (2010), we report herein on the crystal structure of the title compound.

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For van der Waals radii, see: Bondi (1964). 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 + 1/2, -y + 3/2, -z + 2].
	Fig. 2. The crystal packing of the title compound viewed down the c-axis, showing hoe the molecules are linked via C—H···O interactions (dashed lines), so forming two dimensional networks (see Table 1 for details).
	Fig. 3. The crystal packing diagram of the title compound viewed down the b-axis, showing the short intermolecular Cl···Cl contacts (dashed lines). All H atoms have been omitted for clarity.

4,6-Dichloro-2-[(E)-(2-{[(E)-3,5-dichloro-2- oxidobenzylidene]azaniumyl}ethyl)iminiumylmethyl]phenolate top

Crystal data top

C₁₆H₁₂Cl₄N₂O₂	F(000) = 824
M_r = 406.08	D_x = 1.614 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 936 reflections
a = 20.0505 (14) Å	θ = 2.5–27.5°
b = 10.1460 (9) Å	µ = 0.72 mm⁻¹
c = 9.0579 (6) Å	T = 291 K
β = 114.955 (4)°	Block, yellow
V = 1670.6 (2) Å³	0.21 × 0.14 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1838 independent reflections
Radiation source: fine-focus sealed tube	1146 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
φ and ω scans	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −25→25
T_min = 0.864, T_max = 0.932	k = −7→12
6453 measured reflections	l = −9→11

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0431P)²] where P = (F_o² + 2F_c²)/3
1838 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₆H₁₂Cl₄N₂O₂	V = 1670.6 (2) Å³
M_r = 406.08	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.0505 (14) Å	µ = 0.72 mm⁻¹
b = 10.1460 (9) Å	T = 291 K
c = 9.0579 (6) Å	0.21 × 0.14 × 0.10 mm
β = 114.955 (4)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1838 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1146 reflections with I > 2σ(I)
T_min = 0.864, T_max = 0.932	R_int = 0.040
6453 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 0.97	Δρ_max = 0.24 e Å⁻³
1838 reflections	Δρ_min = −0.28 e Å⁻³
109 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
C1	0.15792 (12)	0.3326 (2)	0.9612 (3)	0.0382 (6)
C2	0.13797 (12)	0.1976 (3)	0.9247 (3)	0.0402 (6)
C3	0.09283 (12)	0.1562 (3)	0.7713 (3)	0.0451 (6)
H3	0.0814	0.0672	0.7511	0.054*
C4	0.06374 (12)	0.2481 (3)	0.6446 (3)	0.0456 (7)
C5	0.07928 (12)	0.3784 (3)	0.6728 (3)	0.0444 (6)
H5	0.0591	0.4384	0.5877	0.053*
C6	0.12553 (12)	0.4231 (2)	0.8292 (3)	0.0376 (6)
C7	0.14430 (12)	0.5599 (3)	0.8529 (3)	0.0413 (6)
H7	0.1217	0.6175	0.7661	0.050*
Cl1	0.17398 (4)	0.08447 (7)	1.08141 (8)	0.0568 (2)
Cl2	0.00981 (4)	0.19341 (9)	0.44794 (8)	0.0718 (3)
N1	0.19105 (10)	0.6061 (2)	0.9888 (2)	0.0432 (5)
H1	0.2100	0.5376	1.0712	0.052*
C8	0.21355 (13)	0.7436 (3)	1.0075 (3)	0.0479 (6)
H8A	0.2193	0.7756	1.1130	0.057*
H8B	0.1761	0.7963	0.9242	0.057*
O1	0.20257 (9)	0.37045 (17)	1.10541 (17)	0.0482 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0382 (12)	0.0382 (16)	0.0418 (14)	−0.0014 (11)	0.0203 (11)	−0.0028 (12)
C2	0.0407 (12)	0.0379 (16)	0.0450 (13)	0.0008 (11)	0.0210 (11)	0.0003 (12)
C3	0.0474 (14)	0.0370 (16)	0.0545 (16)	−0.0089 (12)	0.0250 (13)	−0.0078 (13)
C4	0.0430 (14)	0.0510 (19)	0.0432 (15)	−0.0101 (12)	0.0185 (12)	−0.0109 (13)
C5	0.0411 (13)	0.0533 (19)	0.0395 (13)	−0.0013 (12)	0.0176 (11)	0.0036 (13)
C6	0.0385 (12)	0.0374 (16)	0.0408 (13)	−0.0017 (11)	0.0206 (11)	0.0008 (12)
C7	0.0443 (14)	0.0415 (17)	0.0424 (13)	0.0029 (11)	0.0224 (12)	0.0030 (12)
Cl1	0.0654 (4)	0.0412 (4)	0.0622 (4)	0.0037 (3)	0.0253 (4)	0.0099 (3)
Cl2	0.0669 (5)	0.0858 (7)	0.0498 (4)	−0.0168 (4)	0.0119 (4)	−0.0205 (4)
N1	0.0539 (12)	0.0323 (14)	0.0452 (12)	−0.0036 (10)	0.0227 (10)	0.0003 (10)
C8	0.0610 (15)	0.0300 (16)	0.0576 (16)	−0.0066 (12)	0.0298 (14)	−0.0038 (12)
O1	0.0571 (10)	0.0443 (12)	0.0361 (9)	−0.0042 (9)	0.0128 (8)	0.0005 (8)

Geometric parameters (Å, º) top

C1—O1	1.292 (2)	C5—H5	0.9300
C1—C2	1.426 (3)	C6—C7	1.430 (3)
C1—C6	1.429 (3)	C7—N1	1.281 (3)
C2—C3	1.366 (3)	C7—H7	0.9300
C2—Cl1	1.729 (2)	N1—C8	1.453 (3)
C3—C4	1.401 (3)	N1—H1	0.9724
C3—H3	0.9300	C8—C8ⁱ	1.529 (5)
C4—C5	1.358 (4)	C8—H8A	0.9700
C4—Cl2	1.740 (2)	C8—H8B	0.9700
C5—C6	1.401 (3)

O1—C1—C2	121.8 (2)	C5—C6—C1	120.7 (2)
O1—C1—C6	122.1 (2)	C5—C6—C7	119.1 (2)
C2—C1—C6	116.1 (2)	C1—C6—C7	120.0 (2)
C3—C2—C1	122.2 (2)	N1—C7—C6	122.7 (2)
C3—C2—Cl1	119.9 (2)	N1—C7—H7	118.7
C1—C2—Cl1	117.91 (18)	C6—C7—H7	118.7
C2—C3—C4	119.8 (2)	C7—N1—C8	121.9 (2)
C2—C3—H3	120.1	C7—N1—H1	111.5
C4—C3—H3	120.1	C8—N1—H1	126.5
C5—C4—C3	120.8 (2)	N1—C8—C8ⁱ	109.5 (3)
C5—C4—Cl2	119.8 (2)	N1—C8—H8A	109.8
C3—C4—Cl2	119.4 (2)	C8ⁱ—C8—H8A	109.8
C4—C5—C6	120.5 (2)	N1—C8—H8B	109.8
C4—C5—H5	119.8	C8ⁱ—C8—H8B	109.8
C6—C5—H5	119.8	H8A—C8—H8B	108.2

O1—C1—C2—C3	−177.7 (2)	C4—C5—C6—C1	0.8 (3)
C6—C1—C2—C3	2.4 (3)	C4—C5—C6—C7	176.3 (2)
O1—C1—C2—Cl1	1.4 (3)	O1—C1—C6—C5	177.77 (19)
C6—C1—C2—Cl1	−178.53 (15)	C2—C1—C6—C5	−2.3 (3)
C1—C2—C3—C4	−1.0 (3)	O1—C1—C6—C7	2.3 (3)
Cl1—C2—C3—C4	180.00 (17)	C2—C1—C6—C7	−177.81 (19)
C2—C3—C4—C5	−0.7 (3)	C5—C6—C7—N1	−173.9 (2)
C2—C3—C4—Cl2	177.00 (17)	C1—C6—C7—N1	1.6 (3)
C3—C4—C5—C6	0.8 (3)	C6—C7—N1—C8	175.4 (2)
Cl2—C4—C5—C6	−176.92 (17)	C7—N1—C8—C8ⁱ	−97.9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.97	1.74	2.585 (3)	143
C8—H8A···O1ⁱⁱ	0.97	2.55	3.436 (3)	152

Symmetry code: (ii) −x+1/2, y+1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₄N₂O₂
M_r	406.08
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	20.0505 (14), 10.1460 (9), 9.0579 (6)
β (°)	114.955 (4)
V (Å³)	1670.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.21 × 0.14 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.864, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	6453, 1838, 1146
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.097, 0.97
No. of reflections	1838
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.28

Computer programs: APEX2 (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
N1—H1···O1	0.97	1.74	2.585 (3)	143
C8—H8A···O1ⁱ	0.97	2.55	3.436 (3)	152

Symmetry code: (i) −x+1/2, y+1/2, −z+5/2.

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

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