4,4′,6,6′-Tetra­chloro-2,2′-[(1E,1′E)-propane-1,3-diylbis(nitrilo­methanylyl­idene)]diphenol

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

doi:10.1107/S1600536812029443

organic compounds

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Volume 68| Part 8| August 2012| Page o2323

https://doi.org/10.1107/S1600536812029443

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4,4′,6,6′-Tetrachloro-2,2′-[(1E,1′E)-propane-1,3-diylbis(nitrilomethanylylidene)]diphenol

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

^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, and ^cDepartment of Physics, University of Sargodha, Punjab, Pakistan
^*Correspondence e-mail: zsrkk@yahoo.com, dmntahir_uos@yahoo.com

(Received 16 June 2012; accepted 28 June 2012; online 4 July 2012)

The title compound, C₁₇H₁₄Cl₄N₂O₂, is generated by crystallographic twofold symmetry. The two benzene rings are inclined to one another by 80.17 (10)°. There are two intramolecular O—H⋯N hydrogen bonds, which make S(6) ring motifs. In the crystal, molecules are linked by C—H⋯O and weak C—H⋯Cl interactions, forming a three-dimensional network.

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

C₁₇H₁₄Cl₄N₂O₂
M_r = 420.10
Orthorhombic, F d d 2
a = 24.9797 (14) Å
b = 31.666 (3) Å
c = 4.4495 (2) Å
V = 3519.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 291 K
0.26 × 0.23 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.842, T_max = 0.886
7926 measured reflections
1960 independent reflections
1634 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.068
S = 1.04
1960 reflections
115 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 842 Friedel pairs
Flack parameter: 0.08 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.84	2.574 (2)	147
C5—H2⋯O1ⁱ	0.93	2.43	3.336 (2)	166
C8—H5B⋯Cl1ⁱⁱ	0.97	2.89	3.851 (2)	169
Symmetry codes: (i) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (ii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{5\over 4}}]$ .

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/S1600536812029443/su2464sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812029443/su2464Isup2.hkl

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 synthesized the title compound and report herein on its crystal structure.

The title compound, Fig. 1, a potential tetradentate Schiff base ligand, possesses two-fold rotation symmetry, atom C9 is located on the 2-fold axis. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. The two symmetry related benzene rings are inclined to one another by 80.17 (10) °. There are two intramolecular O—H···N hydrogen bonds which make S(6) ring motifs (Table 1; Bernstein et al., 1995).

In the crystal, molecules are linked by C—H···O and weak C—H···Cl interactions to form a three-dimensional network (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 propylenediamine (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Light-yellow prismatic single crystals of the title compound, suitable for X-ray structure determination, were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.

Structure description top

In the crystal, molecules are linked by C—H···O and weak C—H···Cl interactions to form a three-dimensional network (Table 1 and Fig. 2).

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, z].
	Fig. 2. The crystal packing diagram of the title compound viewed down the c-axis, showing linking of molecules through C—H···O and weak C—H···Cl interactions (dashed lines).

4,4',6,6'-Tetrachloro-2,2'-[(1E,1'E)-propane-1,3- diylbis(nitrilomethanylylidene)]diphenol top

Crystal data top

C₁₇H₁₄Cl₄N₂O₂	F(000) = 1712
M_r = 420.10	D_x = 1.586 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1234 reflections
a = 24.9797 (14) Å	θ = 2.5–27.5°
b = 31.666 (3) Å	µ = 0.69 mm⁻¹
c = 4.4495 (2) Å	T = 291 K
V = 3519.6 (4) Å³	Prism, light-yellow
Z = 8	0.26 × 0.23 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1960 independent reflections
Radiation source: fine-focus sealed tube	1634 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 27.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −32→32
T_min = 0.842, T_max = 0.886	k = −40→40
7926 measured reflections	l = −5→5

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0306P)² + 1.6825P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1960 reflections	Δρ_max = 0.14 e Å⁻³
115 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 842 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (7)

Crystal data top

C₁₇H₁₄Cl₄N₂O₂	V = 3519.6 (4) Å³
M_r = 420.10	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 24.9797 (14) Å	µ = 0.69 mm⁻¹
b = 31.666 (3) Å	T = 291 K
c = 4.4495 (2) Å	0.26 × 0.23 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1960 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1634 reflections with I > 2σ(I)
T_min = 0.842, T_max = 0.886	R_int = 0.028
7926 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.068	Δρ_max = 0.14 e Å⁻³
S = 1.03	Δρ_min = −0.16 e Å⁻³
1960 reflections	Absolute structure: Flack (1983), 842 Friedel pairs
115 parameters	Absolute structure parameter: 0.08 (7)
1 restraint

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	Occ. (<1)
C1	−0.04810 (7)	0.14212 (6)	0.7828 (4)	0.0378 (4)
C2	−0.05597 (7)	0.17577 (6)	0.5854 (5)	0.0405 (5)
C3	−0.01420 (7)	0.19985 (6)	0.4810 (5)	0.0429 (5)
H9	−0.0203	0.2218	0.3466	0.052*
C4	0.03720 (8)	0.19078 (6)	0.5799 (5)	0.0419 (5)
C5	0.04673 (7)	0.15902 (6)	0.7793 (5)	0.0409 (5)
H2	0.0814	0.1538	0.8453	0.049*
C6	0.00437 (7)	0.13440 (6)	0.8845 (4)	0.0374 (4)
C7	0.01466 (8)	0.10036 (6)	1.0958 (4)	0.0401 (5)
H4	0.0489	0.0972	1.1753	0.048*
C8	−0.00878 (9)	0.03959 (6)	1.3730 (4)	0.0458 (5)
H5A	−0.0378	0.0351	1.5143	0.055*
H5B	0.0234	0.0461	1.4863	0.055*
C9	0.0000	0.0000	1.1876 (7)	0.0465 (7)
H6A	−0.0309	−0.0043	1.0589	0.056*	0.50
H6B	0.0309	0.0043	1.0589	0.056*	0.50
Cl1	−0.12035 (2)	0.187207 (19)	0.46609 (15)	0.05937 (17)
Cl2	0.09006 (2)	0.220654 (18)	0.43888 (16)	0.06188 (18)
N1	−0.02186 (7)	0.07479 (5)	1.1743 (4)	0.0424 (4)
O1	−0.08951 (5)	0.11861 (4)	0.8692 (4)	0.0503 (4)
H1	−0.0790	0.0999	0.9826	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0349 (9)	0.0355 (9)	0.0429 (12)	−0.0002 (8)	−0.0034 (8)	−0.0052 (9)
C2	0.0322 (9)	0.0401 (10)	0.0490 (12)	0.0056 (8)	−0.0083 (8)	−0.0044 (9)
C3	0.0415 (10)	0.0356 (9)	0.0518 (13)	0.0015 (8)	−0.0029 (10)	0.0001 (10)
C4	0.0349 (10)	0.0359 (10)	0.0550 (13)	−0.0016 (8)	0.0015 (9)	−0.0067 (9)
C5	0.0314 (9)	0.0402 (10)	0.0512 (13)	0.0052 (8)	−0.0060 (8)	−0.0087 (9)
C6	0.0368 (9)	0.0344 (9)	0.0409 (11)	0.0028 (7)	−0.0035 (8)	−0.0085 (9)
C7	0.0374 (10)	0.0420 (11)	0.0410 (11)	0.0067 (8)	−0.0083 (8)	−0.0084 (9)
C8	0.0521 (12)	0.0446 (11)	0.0407 (12)	0.0032 (9)	−0.0053 (9)	−0.0001 (10)
C9	0.0567 (17)	0.0430 (15)	0.0399 (15)	0.0048 (13)	0.000	0.000
Cl1	0.0371 (3)	0.0610 (3)	0.0800 (4)	0.0024 (2)	−0.0162 (3)	0.0145 (3)
Cl2	0.0434 (3)	0.0532 (3)	0.0891 (5)	−0.0076 (2)	0.0080 (3)	0.0055 (3)
N1	0.0464 (9)	0.0411 (9)	0.0397 (9)	0.0039 (7)	−0.0062 (8)	−0.0015 (8)
O1	0.0366 (7)	0.0503 (9)	0.0639 (10)	−0.0058 (6)	−0.0093 (6)	0.0124 (7)

Geometric parameters (Å, º) top

C1—O1	1.331 (2)	C6—C7	1.453 (3)
C1—C2	1.395 (3)	C7—N1	1.269 (2)
C1—C6	1.408 (2)	C7—H4	0.9300
C2—C3	1.373 (3)	C8—N1	1.460 (3)
C2—Cl1	1.7318 (19)	C8—C9	1.517 (3)
C3—C4	1.387 (3)	C8—H5A	0.9700
C3—H9	0.9300	C8—H5B	0.9700
C4—C5	1.362 (3)	C9—C8ⁱ	1.517 (3)
C4—Cl2	1.741 (2)	C9—H6A	0.9700
C5—C6	1.395 (3)	C9—H6B	0.9700
C5—H2	0.9300	O1—H1	0.8200

O1—C1—C2	119.98 (16)	N1—C7—C6	121.61 (17)
O1—C1—C6	122.23 (17)	N1—C7—H4	119.2
C2—C1—C6	117.79 (17)	C6—C7—H4	119.2
C3—C2—C1	122.02 (17)	N1—C8—C9	109.52 (18)
C3—C2—Cl1	119.06 (15)	N1—C8—H5A	109.8
C1—C2—Cl1	118.92 (15)	C9—C8—H5A	109.8
C2—C3—C4	118.75 (19)	N1—C8—H5B	109.8
C2—C3—H9	120.6	C9—C8—H5B	109.8
C4—C3—H9	120.6	H5A—C8—H5B	108.2
C5—C4—C3	121.42 (18)	C8ⁱ—C9—C8	114.1 (3)
C5—C4—Cl2	120.22 (15)	C8ⁱ—C9—H6A	108.7
C3—C4—Cl2	118.35 (16)	C8—C9—H6A	108.7
C4—C5—C6	119.90 (17)	C8ⁱ—C9—H6B	108.7
C4—C5—H2	120.1	C8—C9—H6B	108.7
C6—C5—H2	120.1	H6A—C9—H6B	107.6
C5—C6—C1	120.07 (18)	C7—N1—C8	119.53 (17)
C5—C6—C7	119.82 (17)	C1—O1—H1	109.5
C1—C6—C7	120.10 (18)

O1—C1—C2—C3	−177.41 (19)	C4—C5—C6—C7	179.60 (17)
C6—C1—C2—C3	2.7 (3)	O1—C1—C6—C5	177.77 (18)
O1—C1—C2—Cl1	2.0 (2)	C2—C1—C6—C5	−2.4 (3)
C6—C1—C2—Cl1	−177.84 (15)	O1—C1—C6—C7	−1.3 (3)
C1—C2—C3—C4	−1.2 (3)	C2—C1—C6—C7	178.59 (16)
Cl1—C2—C3—C4	179.35 (16)	C5—C6—C7—N1	−173.18 (19)
C2—C3—C4—C5	−0.7 (3)	C1—C6—C7—N1	5.9 (3)
C2—C3—C4—Cl2	178.41 (15)	N1—C8—C9—C8ⁱ	−174.57 (19)
C3—C4—C5—C6	1.0 (3)	C6—C7—N1—C8	176.32 (17)
Cl2—C4—C5—C6	−178.09 (15)	C9—C8—N1—C7	−97.64 (19)
C4—C5—C6—C1	0.5 (3)

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.84	2.574 (2)	147
C5—H2···O1ⁱⁱ	0.93	2.43	3.336 (2)	166
C8—H5B···Cl1ⁱⁱⁱ	0.97	2.89	3.851 (2)	169

Symmetry codes: (ii) x+1/4, −y+1/4, z+1/4; (iii) x+1/4, −y+1/4, z+5/4.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₄Cl₄N₂O₂
M_r	420.10
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	291
a, b, c (Å)	24.9797 (14), 31.666 (3), 4.4495 (2)
V (Å³)	3519.6 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.26 × 0.23 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.842, 0.886
No. of measured, independent and observed [I > 2σ(I)] reflections	7926, 1960, 1634
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.645

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.068, 1.03
No. of reflections	1960
No. of parameters	115
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.16
Absolute structure	Flack (1983), 842 Friedel pairs
Absolute structure parameter	0.08 (7)

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
O1—H1···N1	0.82	1.84	2.574 (2)	147
C5—H2···O1ⁱ	0.93	2.43	3.336 (2)	166
C8—H5B···Cl1ⁱⁱ	0.97	2.89	3.851 (2)	169

Symmetry codes: (i) x+1/4, −y+1/4, z+1/4; (ii) x+1/4, −y+1/4, z+5/4.

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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