4-Bromo-N-(4-hy­droxy­benzyl­idene)­aniline

Jothi, L.; Vasuki, G.; Babu, R.R.; Ramamurthi, K.

doi:10.1107/S1600536812006101

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o772

doi:10.1107/S1600536812006101

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4-Bromo-N-(4-hydroxybenzylidene)aniline

L. Jothi,^a G. Vasuki,^b ^* R. Ramesh Babu ^c and K. Ramamurthi ^c

^aDepartment of Physics, NKR Government Arts College for Women, Namakkal-1, India, ^bDepartment of Physics, Kunthavai Naachiar Government Arts College (W) (Autonomous), Thanjavur-7, India, and ^cCrystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli-24, India
^*Correspondence e-mail: vasuki.arasi@yahoo.com

(Received 4 February 2012; accepted 11 February 2012; online 17 February 2012)

In the title compound, C₁₃H₁₀BrNO, the benzene ring planes are inclined at an angle of 48.85 (17)°, resulting in a nonplanar molecule. A characteristic of aromatic Schiff bases with N-aryl substituents is that the terminal phenyl rings are twisted relative to the HC=N plane. In this case, the HC=N unit makes dihedral angles of 11.1 (4) and 38.5 (3)° with the hydroxybenzene and bromobenzene rings, respectively. In the crystal, the molecules are linked by O—H⋯N hydrogen bonds to form infinite (C8) chains along the b axis.

Related literature

For applications of Schiff base compounds and related structures, see: Li et al. (2008 ); Zhang (2010 ). For other related structures, see: Kaitner & Pavlovic (1995 ); Yeap et al. (1993 ). For an early determination of the lattice parameters of this compound, see: Bürgi et al. (1968 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₁₀BrNO
M_r = 276.13
Orthorhombic, P b c n
a = 21.9588 (10) Å
b = 11.0866 (5) Å
c = 9.3132 (4) Å
V = 2267.28 (17) Å³
Z = 8
Mo Kα radiation
μ = 3.60 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.452, T_max = 0.571
20366 measured reflections
2001 independent reflections
1494 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.174
S = 1.03
2001 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 1.32 e Å⁻³
Δρ_min = −1.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.92	2.734	175
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812006101/sj5193sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006101/sj5193Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006101/sj5193Isup3.cml

checkCIF report

Comment top

Schiff base compounds have been used as fine chemicals and medical substrates. They are important ligands in co-ordination chemistry due to their ease of preparation and their ability to be modified both electronically and sterically (Li et al., 2008 and Zhang, 2010). As a part of our study on the co-ordination behaviour of a ligand having a 4-hydroxy substituent on the benzylidene fragment, X- ray structural analysis of the title compound was carried out, the results are reported herein. The lattice parameters of this compound, determined from precession photographs, were reported previously by Bürgi et al. (1968). The title compound, (I), contains two benzene rings bridged by a C ═N imino moiety, the planes of which are inclined at an angle of 48.85 (17)°, showing significant deviation of the molecule from planarity as observed in a related structure N-p-tolylvanillaldimine (Kaitner & Pavlovic, 1995). The molecule exists in the solid state in an E-Configuration with respect to the C7═N1 bond as indicated by the torsion angle C4–C7–N1–C8 = 171.22 (4)°. In order to minimize the interaction between the hydroxy proton and H6 at C6 the O1–C1–C6 angle [123.4 (4)°] is larger than the O1–C1–C2 angle [117.4 (4)°] (Yeap et al., 1993). The N1–C7–C4 [124.70 (4)°] is greater than the normal value of 120°; this might be a consequence of repulsion between the lone pair of electrons on N1 and H5 attached to C5 (N1···H5 = 2.6583 (1) Å). The C4-C7 [1.454 (6)Å] and N1-C8 [1.412 (6)Å] distances confirm a degree of π-electron delocalization between the benzene rings, and the molecule can be regarded as a partially delocalized π-electron system as observed in the related structures 4-[(3-methoxyphenylimino)methyl]phenol) and N-p-tolylvanillaldimine (Yeap, et al.,, 1993; Kaitner & Pavlovic, 1995). All other bond lengths are within the expected ranges (Allen et al., 1987). The crystal structure is stabilized by intermolecular O-H···N hydrogen bonds linking the neighbouring molecules into infinite chains along the b axis.

Related literature top

For applications of Schiff base compounds and related structures, see: Li et al. (2008); Zhang (2010). For other related structures, see: Kaitner & Pavlovic (1995); Yeap et al. (1993). For an early determination of the lattice parameters of this compound, see: Bürgi et al. (1968). For standard bond lengths, see: Allen et al. (1987).

Experimental top

4-Bromo-4'-hydroxybenzylideneaniline was prepared by mixing equimolar amounts of 4-hydroxy benzaldehyde and 4-bromo aniline in ethanol (40 ml). The reaction mixture was refluxed for about 6 h and the resulting solution, kept at room temperature was slowly evaporated. After three days single crystals of the title compound, suitable for X-ray structure analysis were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom numbering and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound viewed down the c axis showing O–H···N interactions as dashed lines (see Table 1 for details).

4-Bromo-N-(4-hydroxybenzylidene)aniline top

Crystal data top

C₁₃H₁₀BrNO	F(000) = 1104
M_r = 276.13	D_x = 1.618 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 6133 reflections
a = 21.9588 (10) Å	θ = 2.7–24.7°
b = 11.0866 (5) Å	µ = 3.60 mm⁻¹
c = 9.3132 (4) Å	T = 293 K
V = 2267.28 (17) Å³	Block, brown
Z = 8	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2001 independent reflections
Radiation source: fine-focus sealed tube	1494 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω and ϕ scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −26→26
T_min = 0.452, T_max = 0.571	k = −12→13
20366 measured reflections	l = −8→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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0898P)² + 6.133P] where P = (F_o² + 2F_c²)/3
2001 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 1.32 e Å⁻³
0 restraints	Δρ_min = −1.62 e Å⁻³

Crystal data top

C₁₃H₁₀BrNO	V = 2267.28 (17) Å³
M_r = 276.13	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 21.9588 (10) Å	µ = 3.60 mm⁻¹
b = 11.0866 (5) Å	T = 293 K
c = 9.3132 (4) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2001 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1494 reflections with I > 2σ(I)
T_min = 0.452, T_max = 0.571	R_int = 0.046
20366 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 1.03	Δρ_max = 1.32 e Å⁻³
2001 reflections	Δρ_min = −1.62 e Å⁻³
145 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.3296 (2)	0.1888 (4)	−0.1451 (5)	0.0340 (10)
C2	0.3501 (2)	0.0799 (4)	−0.0885 (5)	0.0398 (11)
H2	0.3879	0.0493	−0.1156	0.048*
C3	0.3145 (2)	0.0181 (4)	0.0074 (5)	0.0407 (11)
H3	0.3283	−0.0551	0.0437	0.049*
C4	0.2586 (2)	0.0620 (4)	0.0514 (5)	0.0333 (10)
C5	0.2389 (2)	0.1715 (4)	−0.0048 (4)	0.0340 (10)
H5	0.2014	0.2027	0.0231	0.041*
C6	0.2743 (2)	0.2341 (4)	−0.1012 (5)	0.0340 (10)
H6	0.2607	0.3076	−0.1370	0.041*
C7	0.2200 (2)	−0.0109 (4)	0.1437 (5)	0.0360 (10)
H7	0.2321	−0.0899	0.1619	0.043*
C8	0.1337 (2)	−0.0598 (4)	0.2718 (5)	0.0342 (10)
C9	0.1277 (2)	−0.1783 (5)	0.2249 (6)	0.0456 (12)
H9	0.1487	−0.2041	0.1439	0.055*
C10	0.0909 (3)	−0.2569 (5)	0.2975 (6)	0.0518 (13)
H10	0.0870	−0.3359	0.2654	0.062*
C11	0.0598 (2)	−0.2199 (5)	0.4172 (6)	0.0526 (14)
C12	0.0639 (2)	−0.1040 (5)	0.4635 (6)	0.0518 (13)
H12	0.0426	−0.0793	0.5445	0.062*
C13	0.1002 (2)	−0.0229 (5)	0.3893 (5)	0.0450 (12)
H13	0.1020	0.0571	0.4189	0.054*
N1	0.17101 (17)	0.0253 (3)	0.2012 (4)	0.0342 (9)
O1	0.36520 (16)	0.2436 (3)	−0.2426 (4)	0.0465 (9)
H1	0.3522	0.3116	−0.2583	0.070*
Br1	0.01108 (4)	−0.33090 (9)	0.51718 (9)	0.0918 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.034 (2)	0.032 (2)	0.036 (2)	−0.0054 (19)	0.0006 (19)	−0.0038 (19)
C2	0.032 (2)	0.037 (2)	0.050 (3)	−0.001 (2)	0.000 (2)	−0.003 (2)
C3	0.042 (3)	0.031 (2)	0.050 (3)	0.000 (2)	−0.006 (2)	0.005 (2)
C4	0.039 (2)	0.028 (2)	0.033 (2)	−0.0046 (19)	−0.0062 (19)	−0.0008 (19)
C5	0.036 (3)	0.032 (2)	0.034 (2)	−0.0006 (19)	−0.0022 (19)	−0.0030 (18)
C6	0.039 (3)	0.028 (2)	0.035 (2)	0.0001 (18)	−0.001 (2)	0.0015 (19)
C7	0.044 (3)	0.027 (2)	0.037 (3)	−0.003 (2)	−0.008 (2)	0.0033 (19)
C8	0.040 (3)	0.031 (2)	0.031 (2)	−0.0040 (19)	−0.0046 (19)	0.0030 (18)
C9	0.052 (3)	0.043 (3)	0.041 (3)	−0.010 (2)	0.000 (2)	−0.002 (2)
C10	0.057 (3)	0.041 (3)	0.058 (3)	−0.015 (2)	−0.008 (3)	0.005 (3)
C11	0.040 (3)	0.064 (4)	0.053 (3)	−0.014 (3)	−0.006 (2)	0.021 (3)
C12	0.040 (3)	0.069 (4)	0.047 (3)	0.002 (3)	0.006 (2)	0.004 (3)
C13	0.046 (3)	0.046 (3)	0.043 (3)	−0.001 (2)	0.000 (2)	−0.001 (2)
N1	0.041 (2)	0.0301 (19)	0.0314 (19)	−0.0041 (16)	−0.0036 (17)	0.0006 (16)
O1	0.046 (2)	0.0398 (19)	0.053 (2)	−0.0006 (15)	0.0120 (16)	0.0066 (16)
Br1	0.0712 (6)	0.1138 (7)	0.0904 (6)	−0.0442 (4)	0.0008 (4)	0.0423 (5)

Geometric parameters (Å, º) top

C1—O1	1.343 (5)	C8—C13	1.380 (7)
C1—C6	1.376 (6)	C8—C9	1.390 (7)
C1—C2	1.392 (6)	C8—N1	1.412 (6)
C2—C3	1.371 (7)	C9—C10	1.367 (7)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.382 (7)	C10—C11	1.370 (9)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.391 (6)	C11—C12	1.358 (8)
C4—C7	1.454 (6)	C11—Br1	1.878 (5)
C5—C6	1.375 (6)	C12—C13	1.386 (7)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—H13	0.9300
C7—N1	1.267 (6)	O1—H1	0.8200
C7—H7	0.9300

O1—C1—C6	123.4 (4)	C13—C8—C9	118.6 (4)
O1—C1—C2	117.4 (4)	C13—C8—N1	118.7 (4)
C6—C1—C2	119.3 (4)	C9—C8—N1	122.6 (4)
C3—C2—C1	119.7 (4)	C10—C9—C8	120.2 (5)
C3—C2—H2	120.2	C10—C9—H9	119.9
C1—C2—H2	120.2	C8—C9—H9	119.9
C2—C3—C4	121.6 (4)	C9—C10—C11	120.4 (5)
C2—C3—H3	119.2	C9—C10—H10	119.8
C4—C3—H3	119.2	C11—C10—H10	119.8
C3—C4—C5	118.2 (4)	C12—C11—C10	120.5 (5)
C3—C4—C7	119.8 (4)	C12—C11—Br1	120.0 (4)
C5—C4—C7	121.8 (4)	C10—C11—Br1	119.4 (4)
C6—C5—C4	120.6 (4)	C11—C12—C13	119.6 (5)
C6—C5—H5	119.7	C11—C12—H12	120.2
C4—C5—H5	119.7	C13—C12—H12	120.2
C5—C6—C1	120.6 (4)	C8—C13—C12	120.6 (5)
C5—C6—H6	119.7	C8—C13—H13	119.7
C1—C6—H6	119.7	C12—C13—H13	119.7
N1—C7—C4	124.7 (4)	C7—N1—C8	118.6 (4)
N1—C7—H7	117.7	C1—O1—H1	109.5
C4—C7—H7	117.7

O1—C1—C2—C3	−177.6 (4)	N1—C8—C9—C10	179.9 (5)
C6—C1—C2—C3	1.5 (7)	C8—C9—C10—C11	−0.2 (8)
C1—C2—C3—C4	−0.9 (7)	C9—C10—C11—C12	1.5 (8)
C2—C3—C4—C5	0.2 (7)	C9—C10—C11—Br1	−178.6 (4)
C2—C3—C4—C7	174.8 (4)	C10—C11—C12—C13	−0.4 (8)
C3—C4—C5—C6	−0.1 (6)	Br1—C11—C12—C13	179.7 (4)
C7—C4—C5—C6	−174.6 (4)	C9—C8—C13—C12	3.4 (7)
C4—C5—C6—C1	0.7 (6)	N1—C8—C13—C12	−178.7 (4)
O1—C1—C6—C5	177.6 (4)	C11—C12—C13—C8	−2.2 (8)
C2—C1—C6—C5	−1.4 (7)	C4—C7—N1—C8	171.2 (4)
C3—C4—C7—N1	172.7 (4)	C13—C8—N1—C7	147.7 (4)
C5—C4—C7—N1	−12.9 (7)	C9—C8—N1—C7	−34.5 (6)
C13—C8—C9—C10	−2.2 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.92	2.734	175

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀BrNO
M_r	276.13
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	21.9588 (10), 11.0866 (5), 9.3132 (4)
V (Å³)	2267.28 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.60
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.452, 0.571
No. of measured, independent and observed [I > 2σ(I)] reflections	20366, 2001, 1494
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.174, 1.03
No. of reflections	2001
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.32, −1.62

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.916	2.734	174.92

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

Acknowledgements

The authors thank the Sophisticated Analytical Instrument Facility, IIT Madras, Chennai, for the single-crystal X-ray data collection.

References

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