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

Abstract

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,

• a = 24.9797 (14) Å

• b = 31.666 (3) Å

• c = 4.4495 (2) Å

• V = 3519.6 (4) ų

• 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[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 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)

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The OH and C-bound H atoms were included in calculated positions and treated as riding atoms: O-H = 0.82 Å, C-H = 0.93 and 0.96 Å, with U_iso(H) = k × U_eq(O,C) where k = 1.5 for OH and CH₃ H atoms and = 1.2 for other H atoms.

Figures

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).

Crystal data

C17H14Cl4N2O2	F(000) = 1712
Mr = 420.10	Dx = 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

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

Refinement

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(Fo2) + (0.0306P)2 + 1.6825P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1960 reflections	Δρmax = 0.14 e Å−3
115 parameters	Δρmin = −0.16 e Å−3
1 restraint	Absolute structure: Flack (1983), 842 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.08 (7)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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)

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)

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.