4,6-Dibromo-2-[(E)-(4-{[(E)-3,5-dibromo-2-hy­droxy­benzyl­idene]amino}­butyl)­imino­meth­yl]phenol

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

doi:10.1107/S1600536812028863

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages o2270-o2271

https://doi.org/10.1107/S1600536812028863

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4,6-Dibromo-2-[(E)-(4-{[(E)-3,5-dibromo-2-hydroxybenzylidene]amino}butyl)iminomethyl]phenol

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

The asymmetric unit of the title compound, C₁₈H₁₆Br₄N₂O₂, comprises half the molecule, which is located adjacent to an inversion centre at the mid-point of the central C—C bond of the butane-1,4-diamine segment. 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⋯Br interactions into chains along [101], which include R₂²(8) ring motifs. These chains are further linked by C—H⋯O hydrogen bonds, 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

C₁₈H₁₆Br₄N₂O₂
M_r = 611.97
Orthorhombic, P b c n
a = 15.9537 (12) Å
b = 12.8784 (10) Å
c = 9.5566 (6) Å
V = 1963.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 8.21 mm⁻¹
T = 291 K
0.35 × 0.14 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.161, T_max = 0.439
15023 measured reflections
2164 independent reflections
1381 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.074
S = 0.99
2164 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.72	1.92	2.574 (4)	151
C6—H6⋯O1ⁱ	0.93	2.56	3.469 (5)	165
C4—H3⋯Br2ⁱⁱ	0.93	2.96	3.849 (4)	161
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) -x, -y, -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/S1600536812028863/su2461sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028863/su2461Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028863/su2461Isup3.cml

checkCIF report

Comment top

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

The asymmetric unit of the title compound, Fig. 1, comprises half of a potential tetradentate Schiff base ligand. The molecule is located about an inversion centre which is situated at the centre of the central C9-C9A bond of the 1,4-butane-diamine segment. 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 (Table 1 and Fig. 1; Bernstein et al., 1995).

In the crystal, molecules are linked by pairs of weak C—H···Br interactions to form chains along direction [101] which include R²₂(8) ring motifs (Table 1 and Fig. 2). These chains are further linked by C—H···O interactions (Table 1) to form a three-dimensional network.

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-dibromosalicylaldehyde (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-like crystals of the title compound, suitable for X-ray structure determination, were obtained by recrystallization from ethanol on slow evaporation of the solvents at room temperature over several days.

Structure description top

In continuation of our work on the crystal structures of Schiff base ligands (Kargar et al., 2011; Kia et al., 2010), we synthesized and analysed 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 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 molecule, showing 40% probability displacement ellipsoids and the atomic numbering [symmetry code for suffix A = -x, -y, -z].
	Fig. 2. The crystal packing of the title compound viewed along the c axis, showing linking of molecules through C—H···O and weak C—H···Br interactions (dashed lines; see Table 1 for details). Only the H atoms involved in hydrogen bonding are shown.

4,6-Dibromo-2-[(E)-(4-{[(E)-3,5-dibromo-2- hydroxybenzylidene]amino}butyl)iminomethyl]phenol top

Crystal data top

C₁₈H₁₆Br₄N₂O₂	F(000) = 1176
M_r = 611.97	D_x = 2.070 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2045 reflections
a = 15.9537 (12) Å	θ = 3.3–27.5°
b = 12.8784 (10) Å	µ = 8.21 mm⁻¹
c = 9.5566 (6) Å	T = 291 K
V = 1963.5 (2) Å³	Needle, yellow
Z = 4	0.35 × 0.14 × 0.12 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2164 independent reflections
Radiation source: fine-focus sealed tube	1381 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
φ and ω scans	θ_max = 27.2°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −20→20
T_min = 0.161, T_max = 0.439	k = −16→16
15023 measured reflections	l = −11→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0269P)² + 1.1226P] where P = (F_o² + 2F_c²)/3
2164 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₁₈H₁₆Br₄N₂O₂	V = 1963.5 (2) Å³
M_r = 611.97	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 15.9537 (12) Å	µ = 8.21 mm⁻¹
b = 12.8784 (10) Å	T = 291 K
c = 9.5566 (6) Å	0.35 × 0.14 × 0.12 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2164 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1381 reflections with I > 2σ(I)
T_min = 0.161, T_max = 0.439	R_int = 0.069
15023 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 0.99	Δρ_max = 0.74 e Å⁻³
2164 reflections	Δρ_min = −0.57 e Å⁻³
118 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Br1	0.13066 (3)	−0.24496 (3)	0.17601 (5)	0.0577 (2)
Br2	0.05752 (3)	0.17551 (3)	0.07666 (5)	0.0549 (2)
O1	0.25622 (17)	−0.15166 (19)	0.3764 (3)	0.0456 (9)
N1	0.3337 (2)	−0.0051 (2)	0.5060 (3)	0.0374 (11)
C1	0.2230 (2)	0.0284 (3)	0.3459 (4)	0.0320 (11)
C2	0.2109 (2)	−0.0776 (3)	0.3154 (4)	0.0324 (11)
C3	0.1493 (2)	−0.1035 (3)	0.2181 (4)	0.0359 (11)
C4	0.1036 (2)	−0.0293 (3)	0.1493 (4)	0.0373 (12)
C5	0.1186 (2)	0.0745 (3)	0.1788 (4)	0.0373 (12)
C6	0.1761 (2)	0.1035 (3)	0.2756 (4)	0.0349 (11)
C7	0.2860 (2)	0.0599 (3)	0.4468 (4)	0.0360 (12)
C8	0.3979 (2)	0.0338 (3)	0.6028 (4)	0.0433 (14)
C9	0.4818 (3)	0.0488 (3)	0.5281 (5)	0.0537 (17)
H1	0.28180	−0.12680	0.42830	0.0680*
H3	0.06320	−0.04820	0.08400	0.0450*
H6	0.18440	0.17350	0.29520	0.0420*
H7	0.29150	0.13000	0.46860	0.0430*
H8A	0.40490	−0.01510	0.67920	0.0520*
H8B	0.37970	0.09950	0.64210	0.0520*
H9A	0.47400	0.09730	0.45150	0.0650*
H9B	0.52140	0.07960	0.59310	0.0650*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0699 (3)	0.0317 (2)	0.0716 (3)	−0.0021 (2)	−0.0215 (3)	−0.0097 (2)
Br2	0.0590 (3)	0.0417 (2)	0.0641 (3)	0.0064 (2)	−0.0152 (2)	0.0100 (2)
O1	0.0460 (17)	0.0348 (14)	0.0561 (18)	0.0052 (13)	−0.0166 (14)	−0.0036 (13)
N1	0.0298 (17)	0.0403 (18)	0.042 (2)	−0.0008 (16)	−0.0012 (16)	−0.0022 (15)
C1	0.027 (2)	0.0309 (19)	0.038 (2)	−0.0025 (17)	0.0029 (19)	0.0002 (17)
C2	0.029 (2)	0.0313 (19)	0.037 (2)	0.0010 (17)	0.0004 (18)	0.0008 (17)
C3	0.037 (2)	0.0267 (18)	0.044 (2)	−0.0035 (18)	0.0021 (19)	−0.0057 (17)
C4	0.035 (2)	0.038 (2)	0.039 (2)	−0.0024 (19)	−0.0080 (19)	−0.0016 (18)
C5	0.033 (2)	0.034 (2)	0.045 (2)	0.0023 (18)	−0.0035 (19)	0.0043 (18)
C6	0.038 (2)	0.0258 (18)	0.041 (2)	−0.0018 (17)	0.005 (2)	−0.0003 (17)
C7	0.037 (2)	0.034 (2)	0.037 (2)	−0.0042 (18)	0.003 (2)	−0.0058 (18)
C8	0.038 (2)	0.053 (3)	0.039 (2)	−0.003 (2)	−0.006 (2)	−0.006 (2)
C9	0.043 (3)	0.049 (3)	0.069 (3)	−0.003 (2)	−0.013 (3)	−0.011 (2)

Geometric parameters (Å, º) top

Br1—C3	1.889 (4)	C4—C5	1.387 (5)
Br2—C5	1.896 (4)	C5—C6	1.355 (5)
O1—C2	1.331 (5)	C8—C9	1.529 (6)
O1—H1	0.7200	C9—C9ⁱ	1.485 (6)
N1—C7	1.265 (5)	C4—H3	0.9300
N1—C8	1.468 (5)	C6—H6	0.9300
C1—C2	1.409 (5)	C7—H7	0.9300
C1—C6	1.395 (5)	C8—H8A	0.9700
C1—C7	1.451 (5)	C8—H8B	0.9700
C2—C3	1.393 (5)	C9—H9A	0.9700
C3—C4	1.370 (5)	C9—H9B	0.9700

C2—O1—H1	107.00	C8—C9—C9ⁱ	113.8 (3)
C7—N1—C8	118.4 (3)	C3—C4—H3	121.00
C2—C1—C6	119.9 (3)	C5—C4—H3	121.00
C2—C1—C7	120.2 (3)	C1—C6—H6	120.00
C6—C1—C7	119.9 (3)	C5—C6—H6	120.00
O1—C2—C3	120.3 (3)	N1—C7—H7	119.00
C1—C2—C3	117.8 (3)	C1—C7—H7	119.00
O1—C2—C1	121.9 (3)	N1—C8—H8A	109.00
Br1—C3—C2	118.9 (3)	N1—C8—H8B	109.00
C2—C3—C4	121.9 (4)	C9—C8—H8A	109.00
Br1—C3—C4	119.1 (3)	C9—C8—H8B	109.00
C3—C4—C5	118.9 (3)	H8A—C8—H8B	108.00
Br2—C5—C6	120.7 (3)	C8—C9—H9A	109.00
C4—C5—C6	121.4 (3)	C8—C9—H9B	109.00
Br2—C5—C4	117.9 (3)	H9A—C9—H9B	108.00
C1—C6—C5	120.0 (4)	C9ⁱ—C9—H9A	109.00
N1—C7—C1	121.9 (3)	C9ⁱ—C9—H9B	109.00
N1—C8—C9	111.1 (3)

C8—N1—C7—C1	177.7 (3)	O1—C2—C3—C4	−177.5 (3)
C7—N1—C8—C9	−94.4 (4)	C1—C2—C3—Br1	−179.4 (3)
C6—C1—C2—O1	177.7 (3)	C1—C2—C3—C4	2.5 (5)
C6—C1—C2—C3	−2.3 (5)	Br1—C3—C4—C5	−178.9 (3)
C7—C1—C2—O1	−0.3 (5)	C2—C3—C4—C5	−0.8 (5)
C7—C1—C2—C3	179.7 (3)	C3—C4—C5—Br2	177.6 (3)
C2—C1—C6—C5	0.4 (5)	C3—C4—C5—C6	−1.2 (5)
C7—C1—C6—C5	178.4 (3)	Br2—C5—C6—C1	−177.4 (3)
C2—C1—C7—N1	2.7 (5)	C4—C5—C6—C1	1.4 (5)
C6—C1—C7—N1	−175.2 (3)	N1—C8—C9—C9ⁱ	−62.9 (5)
O1—C2—C3—Br1	0.6 (5)	C8—C9—C9ⁱ—C8ⁱ	−180.0 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.72	1.92	2.574 (4)	151
C6—H6···O1ⁱⁱ	0.93	2.56	3.469 (5)	165
C4—H3···Br2ⁱⁱⁱ	0.93	2.96	3.849 (4)	161

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆Br₄N₂O₂
M_r	611.97
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	291
a, b, c (Å)	15.9537 (12), 12.8784 (10), 9.5566 (6)
V (Å³)	1963.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.21
Crystal size (mm)	0.35 × 0.14 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.161, 0.439
No. of measured, independent and observed [I > 2σ(I)] reflections	15023, 2164, 1381
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.074, 0.99
No. of reflections	2164
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.57

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	0.72	1.92	2.574 (4)	151
C6—H6···O1ⁱ	0.93	2.56	3.469 (5)	165
C4—H3···Br2ⁱⁱ	0.93	2.96	3.849 (4)	161

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

References

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