organic compounds
4-Bromo-2-{(E)-[(3,4-dimethylphenyl)imino]methyl}phenol
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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
10.1107/S1600536812035635/hb6936sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035635/hb6936Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035635/hb6936Isup3.cml
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.
The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = xUeq(C, O) where x = 1.5 for hydroxy & methyl and x = 1.2 for other H-atoms.
Data collection: APEX2 (Bruker, 2007); cell
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).Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line represents the intramolecular hydrogen bond. |
C15H14BrNO | F(000) = 616 |
Mr = 304.18 | Dx = 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 |
Bruker Kappa APEXII CCD diffractometer | 2545 independent reflections |
Radiation source: fine-focus sealed tube | 1931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 8.00 pixels mm-1 | θmax = 26.0°, θmin = 2.0° |
ω scans | h = −10→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −9→8 |
Tmin = 0.454, Tmax = 0.546 | l = −17→17 |
9488 measured reflections |
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(Fo2) + (0.0371P)2 + 0.1325P] where P = (Fo2 + 2Fc2)/3 |
2545 reflections | (Δ/σ)max = 0.001 |
166 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C15H14BrNO | V = 1310.00 (18) Å3 |
Mr = 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)° |
Bruker Kappa APEXII CCD diffractometer | 2545 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1931 reflections with I > 2σ(I) |
Tmin = 0.454, Tmax = 0.546 | Rint = 0.026 |
9488 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.30 e Å−3 |
2545 reflections | Δρmin = −0.34 e Å−3 |
166 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.454, 0.546 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9488, 2545, 1931 |
Rint | 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 |
Δρmax, Δρmin (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).
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
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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.