4-Bromo-2-{(E)-[(3,4-dimethyl­phen­yl)imino]­meth­yl}phenol

Tahir, M.N.; Khan, A.H.; Tariq, M.I.; Hussain, I.; Shafiq, M.

doi:10.1107/S1600536812035635

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2730

doi:10.1107/S1600536812035635

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4-Bromo-2-{(E)-[(3,4-dimethylphenyl)imino]methyl}phenol

M. Nawaz Tahir,^a ^* Abdul Haleem Khan,^b Muhammad Ilyas Tariq,^c Ishtiaq Hussain ^c and Muhammad Shafiq ^d

^aDepartment of Physics, University of Sargodha, Sargodha, Pakistan, ^bDepartment of Pharmacy Services, Jinnah Hospital, Lahore, Pakistan, ^cDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^dDepartment of Chemistry, Government College University, Faisalabad 38000, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 13 August 2012; accepted 13 August 2012; online 23 August 2012)

In the title compound, C₁₅H₁₄BrNO, the dihedral angle between the aromatic rings is 4.10 (11)° and the molecule is close to planar (r.m.s. deviation for the non-H atoms = 0.053 Å). An intramolecular O—H⋯N hydrogen bond closes an S(6) ring. In the crystal, very weak C—H⋯π interactions are observed.

Related literature

For related structures, see: Unver et al. (2010 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₅H₁₄BrNO
M_r = 304.18
Monoclinic, P 2₁ /n
a = 12.2633 (10) Å
b = 7.4805 (6) Å
c = 14.5767 (11) Å
β = 101.576 (4)°
V = 1310.00 (18) Å³
Z = 4
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.454, T_max = 0.546
9488 measured reflections
2545 independent reflections
1931 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.073
S = 1.04
2545 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.87	2.601 (2)	147
C7—H7B⋯Cg1ⁱ	0.96	2.95	3.668 (3)	133
C12—H12⋯Cg1ⁱⁱ	0.93	2.96	3.612 (2)	128
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035635/hb6936sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035635/hb6936Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035635/hb6936Isup3.cml

checkCIF report

Comment top

The title compound, (Fig. 1) has been synthesized as a possible ligand for forming different metal complexes. its sturcture is now described. The crystal structures of 3,4-dimethyl-N-(3-nitrobenzylidene)aniline and 3,4-dimethyl-N-(4-nitrobenzylidene) aniline (Unver et al., 2010) have been published which are related to the title compound.

The title compound is almost planar with r.m.s. deviation of 0.0487 Å, with maximum deviation of 0.1043 (11) Å for Br atom from the mean square plane. There exist intramolecular H-bonding of O—H···N type with S(6) ring motif (Bernstein et al., 1995). There exist weak C—H···π interactions (Table 1) in the crystal.

Related literature top

For related structures, see: Unver et al. (2010). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Equimolar quantities of 3,4-dimethylaniline and 5-bromosalicylaldehyde were refluxed in methanol along with few drops of acetic acid as catalyst for 1 h. The solution was kept at room temperature which affoarded yellow prisms of the title compound after two days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line represents the intramolecular hydrogen bond.

4-Bromo-2-{(E)-[(3,4-dimethylphenyl)imino]methyl}phenol top

Crystal data top

C₁₅H₁₄BrNO	F(000) = 616
M_r = 304.18	D_x = 1.542 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1931 reflections
a = 12.2633 (10) Å	θ = 2.0–26.0°
b = 7.4805 (6) Å	µ = 3.13 mm⁻¹
c = 14.5767 (11) Å	T = 296 K
β = 101.576 (4)°	Prism, yellow
V = 1310.00 (18) Å³	0.30 × 0.25 × 0.22 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2545 independent reflections
Radiation source: fine-focus sealed tube	1931 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.00 pixels mm^-1	θ_max = 26.0°, θ_min = 2.0°
ω scans	h = −10→15
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→8
T_min = 0.454, T_max = 0.546	l = −17→17
9488 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0371P)² + 0.1325P] where P = (F_o² + 2F_c²)/3
2545 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₅H₁₄BrNO	V = 1310.00 (18) Å³
M_r = 304.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.2633 (10) Å	µ = 3.13 mm⁻¹
b = 7.4805 (6) Å	T = 296 K
c = 14.5767 (11) Å	0.30 × 0.25 × 0.22 mm
β = 101.576 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2545 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1931 reflections with I > 2σ(I)
T_min = 0.454, T_max = 0.546	R_int = 0.026
9488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	Δρ_max = 0.30 e Å⁻³
2545 reflections	Δρ_min = −0.34 e Å⁻³
166 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 e.s.d.'s 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 > 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
Br1	0.18394 (2)	0.52508 (4)	0.05809 (2)	0.0611 (1)
O1	0.04873 (13)	0.3558 (3)	0.42252 (10)	0.0649 (7)
N1	0.23707 (15)	0.4902 (2)	0.50899 (13)	0.0433 (6)
C1	0.30890 (17)	0.5327 (3)	0.59525 (15)	0.0377 (7)
C2	0.26822 (18)	0.4991 (3)	0.67585 (15)	0.0402 (7)
C3	0.32937 (18)	0.5327 (3)	0.76461 (15)	0.0386 (7)
C4	0.43689 (17)	0.6028 (3)	0.77377 (14)	0.0413 (7)
C5	0.47658 (17)	0.6376 (3)	0.69271 (14)	0.0445 (8)
C6	0.41546 (16)	0.6041 (3)	0.60481 (15)	0.0437 (7)
C7	0.2812 (2)	0.4915 (3)	0.85007 (17)	0.0559 (9)
C8	0.50899 (19)	0.6368 (3)	0.86868 (15)	0.0595 (9)
C9	0.26191 (19)	0.5199 (3)	0.42938 (15)	0.0411 (7)
C10	0.18689 (18)	0.4725 (3)	0.34246 (15)	0.0384 (7)
C11	0.08370 (17)	0.3910 (3)	0.34249 (15)	0.0442 (7)
C12	0.01435 (18)	0.3464 (3)	0.25816 (16)	0.0495 (8)
C13	0.04434 (18)	0.3849 (3)	0.17425 (15)	0.0462 (7)
C14	0.14496 (18)	0.4672 (3)	0.17412 (15)	0.0407 (7)
C15	0.21649 (18)	0.5098 (3)	0.25677 (15)	0.0406 (7)
H1	0.09704	0.38542	0.46739	0.0974*
H2	0.19695	0.45203	0.66987	0.0483*
H5	0.54756	0.68561	0.69831	0.0534*
H6	0.44489	0.62870	0.55214	0.0524*
H7A	0.32881	0.40851	0.88946	0.0838*
H7B	0.20851	0.44010	0.83078	0.0838*
H7C	0.27580	0.59987	0.88418	0.0838*
H8A	0.47412	0.72447	0.90136	0.0893*
H8B	0.58039	0.68003	0.86120	0.0893*
H8C	0.51838	0.52756	0.90395	0.0893*
H9	0.32978	0.57328	0.42700	0.0493*
H12	−0.05316	0.28997	0.25835	0.0594*
H13	−0.00291	0.35554	0.11803	0.0554*
H15	0.28458	0.56350	0.25552	0.0487*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0679 (2)	0.0809 (2)	0.0349 (2)	−0.0060 (1)	0.0114 (1)	0.0038 (1)
O1	0.0642 (11)	0.0893 (14)	0.0442 (9)	−0.0253 (10)	0.0179 (8)	0.0017 (9)
N1	0.0464 (10)	0.0475 (11)	0.0355 (10)	−0.0011 (8)	0.0073 (8)	−0.0028 (8)
C1	0.0431 (12)	0.0358 (11)	0.0349 (11)	0.0024 (9)	0.0094 (9)	−0.0005 (9)
C2	0.0409 (12)	0.0401 (13)	0.0407 (12)	−0.0035 (9)	0.0105 (10)	−0.0015 (9)
C3	0.0461 (12)	0.0359 (12)	0.0359 (11)	0.0004 (10)	0.0135 (9)	0.0012 (9)
C4	0.0468 (12)	0.0348 (12)	0.0411 (12)	0.0005 (10)	0.0059 (10)	0.0003 (10)
C5	0.0379 (12)	0.0455 (14)	0.0498 (14)	−0.0034 (10)	0.0080 (10)	0.0022 (10)
C6	0.0436 (13)	0.0494 (13)	0.0413 (12)	−0.0001 (10)	0.0160 (10)	0.0036 (10)
C7	0.0664 (16)	0.0653 (17)	0.0388 (13)	−0.0078 (12)	0.0173 (12)	0.0006 (10)
C8	0.0621 (15)	0.0662 (18)	0.0460 (14)	−0.0063 (13)	0.0005 (12)	−0.0015 (12)
C9	0.0439 (12)	0.0426 (13)	0.0371 (12)	−0.0022 (10)	0.0091 (9)	−0.0008 (9)
C10	0.0435 (12)	0.0362 (12)	0.0352 (12)	0.0007 (9)	0.0074 (9)	0.0001 (9)
C11	0.0487 (13)	0.0442 (13)	0.0420 (12)	−0.0054 (11)	0.0146 (10)	0.0032 (10)
C12	0.0444 (13)	0.0498 (15)	0.0529 (14)	−0.0121 (10)	0.0063 (11)	−0.0003 (11)
C13	0.0487 (13)	0.0445 (13)	0.0414 (12)	−0.0010 (11)	−0.0006 (10)	−0.0014 (10)
C14	0.0460 (13)	0.0399 (12)	0.0365 (12)	0.0045 (10)	0.0089 (10)	−0.0001 (9)
C15	0.0414 (12)	0.0416 (13)	0.0391 (12)	−0.0006 (9)	0.0091 (10)	0.0009 (9)

Geometric parameters (Å, º) top

Br1—C14	1.898 (2)	C12—C13	1.377 (3)
O1—C11	1.347 (3)	C13—C14	1.379 (3)
O1—H1	0.8200	C14—C15	1.378 (3)
N1—C1	1.419 (3)	C2—H2	0.9300
N1—C9	1.277 (3)	C5—H5	0.9300
C1—C6	1.393 (3)	C6—H6	0.9300
C1—C2	1.388 (3)	C7—H7A	0.9600
C2—C3	1.382 (3)	C7—H7B	0.9600
C3—C4	1.400 (3)	C7—H7C	0.9600
C3—C7	1.514 (3)	C8—H8A	0.9600
C4—C8	1.507 (3)	C8—H8B	0.9600
C4—C5	1.390 (3)	C8—H8C	0.9600
C5—C6	1.372 (3)	C9—H9	0.9300
C9—C10	1.452 (3)	C12—H12	0.9300
C10—C15	1.397 (3)	C13—H13	0.9300
C10—C11	1.405 (3)	C15—H15	0.9300
C11—C12	1.388 (3)

C11—O1—H1	109.00	C1—C2—H2	119.00
C1—N1—C9	123.19 (19)	C3—C2—H2	119.00
N1—C1—C6	125.30 (19)	C4—C5—H5	119.00
C2—C1—C6	118.3 (2)	C6—C5—H5	119.00
N1—C1—C2	116.41 (19)	C1—C6—H6	120.00
C1—C2—C3	122.7 (2)	C5—C6—H6	120.00
C2—C3—C7	120.4 (2)	C3—C7—H7A	109.00
C4—C3—C7	120.89 (19)	C3—C7—H7B	109.00
C2—C3—C4	118.8 (2)	C3—C7—H7C	109.00
C3—C4—C8	121.25 (19)	H7A—C7—H7B	110.00
C5—C4—C8	120.53 (19)	H7A—C7—H7C	109.00
C3—C4—C5	118.22 (19)	H7B—C7—H7C	109.00
C4—C5—C6	122.8 (2)	C4—C8—H8A	109.00
C1—C6—C5	119.3 (2)	C4—C8—H8B	109.00
N1—C9—C10	121.7 (2)	C4—C8—H8C	109.00
C9—C10—C11	121.2 (2)	H8A—C8—H8B	109.00
C9—C10—C15	119.9 (2)	H8A—C8—H8C	109.00
C11—C10—C15	118.9 (2)	H8B—C8—H8C	109.00
O1—C11—C10	121.90 (19)	N1—C9—H9	119.00
O1—C11—C12	118.36 (19)	C10—C9—H9	119.00
C10—C11—C12	119.7 (2)	C11—C12—H12	120.00
C11—C12—C13	120.8 (2)	C13—C12—H12	120.00
C12—C13—C14	119.6 (2)	C12—C13—H13	120.00
Br1—C14—C13	119.24 (16)	C14—C13—H13	120.00
C13—C14—C15	121.0 (2)	C10—C15—H15	120.00
Br1—C14—C15	119.77 (17)	C14—C15—H15	120.00
C10—C15—C14	120.1 (2)

C9—N1—C1—C2	177.4 (2)	N1—C9—C10—C11	−0.3 (3)
C9—N1—C1—C6	−2.7 (3)	N1—C9—C10—C15	179.0 (2)
C1—N1—C9—C10	179.2 (2)	C9—C10—C11—O1	1.1 (3)
N1—C1—C2—C3	179.5 (2)	C9—C10—C11—C12	−179.6 (2)
C6—C1—C2—C3	−0.4 (3)	C15—C10—C11—O1	−178.2 (2)
N1—C1—C6—C5	−179.5 (2)	C15—C10—C11—C12	1.1 (3)
C2—C1—C6—C5	0.4 (3)	C9—C10—C15—C14	−179.2 (2)
C1—C2—C3—C4	−0.3 (3)	C11—C10—C15—C14	0.2 (3)
C1—C2—C3—C7	−179.3 (2)	O1—C11—C12—C13	177.8 (2)
C2—C3—C4—C5	0.8 (3)	C10—C11—C12—C13	−1.5 (3)
C2—C3—C4—C8	−178.0 (2)	C11—C12—C13—C14	0.6 (3)
C7—C3—C4—C5	179.9 (2)	C12—C13—C14—Br1	−178.45 (17)
C7—C3—C4—C8	1.0 (3)	C12—C13—C14—C15	0.7 (3)
C3—C4—C5—C6	−0.8 (3)	Br1—C14—C15—C10	178.07 (17)
C8—C4—C5—C6	178.1 (2)	C13—C14—C15—C10	−1.1 (3)
C4—C5—C6—C1	0.2 (4)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.601 (2)	147
C7—H7B···Cg1ⁱ	0.96	2.95	3.668 (3)	133
C12—H12···Cg1ⁱⁱ	0.93	2.96	3.612 (2)	128

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄BrNO
M_r	304.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.2633 (10), 7.4805 (6), 14.5767 (11)
β (°)	101.576 (4)
V (Å³)	1310.00 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.13
Crystal size (mm)	0.30 × 0.25 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.454, 0.546
No. of measured, independent and observed [I > 2σ(I)] reflections	9488, 2545, 1931
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.073, 1.04
No. of reflections	2545
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.34

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.601 (2)	147
C7—H7B···Cg1ⁱ	0.96	2.95	3.668 (3)	133
C12—H12···Cg1ⁱⁱ	0.93	2.96	3.612 (2)	128

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Unver, H., Karakas, A. & Durlu, T. N. (2010). Z. Naturforsch. Teil B, 65, 185–190. CAS Google Scholar

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doi:10.1107/S1600536812035635

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