3-Bromo-5-tert-butyl-2-hy­droxy­benz­alde­hyde

Balasubramani, V.; Vinuchakkaravarthy, T.; Gopi, S.; Narasimhan, S.; Velmurugan, D.

doi:10.1107/S1600536811048847

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3375

https://doi.org/10.1107/S1600536811048847

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3-Bromo-5-tert-butyl-2-hydroxybenzaldehyde

V. Balasubramani,^a T. Vinuchakkaravarthy,^b Sreeraj Gopi,^a S. Narasimhan ^a and D. Velmurugan ^b ^*

^aAsthagiri Herbal Research Foundation, 162-A, Industrial Estate, Perungudi, Chennai 600 092, India, and ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Maraimalai Campus (Guindy Campus), Chennai 600 025, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 24 October 2011; accepted 16 November 2011; online 19 November 2011)

The molecular conformation of the title compound, C₁₁H₁₃BrO₂, is stabilized by an intramolecular O—H⋯O hydrogen bond. All non-H atoms except the methyl groups lie approximately in a common plane (r.m.s. deviation = 0.011 Å).

Related literature

For the biological activity of substituted salicylaldehyde and its derivatives, see: Mounika et al. (2010 ); Dueke-Eze et al. (2010 ); Jesmin et al. (2010 ). For a related structure, see: Wang et al. (2010 ).

Experimental

Crystal data

C₁₁H₁₃BrO₂
M_r = 257.11
Orthorhombic, P b c a
a = 9.9727 (19) Å
b = 12.174 (2) Å
c = 18.558 (3) Å
V = 2253.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 3.62 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
11555 measured reflections
2808 independent reflections
1442 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.162
S = 1.02
2808 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1	0.82	1.93	2.650 (6)	145

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811048847/bt5688sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048847/bt5688Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048847/bt5688Isup3.cml

checkCIF report

Comment top

The crystal structure determination of the title compound was undertaken as a part of the synthesis, structure and properties of new substituted salicylaldehyde derivatives.

In the title compound, the substituted aldehyde group, hydroxy group and and bromine are essentially coplanar with the benzene ring with a plane mean deviation of 0.025 (6)°, -0.029 (4)°, -0.015 (1)° and -0.015 (1)°, respectively. An intramolecular O2—H2A···O(1) hydrogen bonding observed between the oxygen atoms of the hydroxy group and the aldehyde group stabilizes the molecular structure.

Related literature top

For the biological activity of substituted salicylaldehyde and its derivatives, see: Mounika et al. (2010); Dueke-Eze et al. (2010); Jesmin et al. (2010). For a related structure, see: Wang et al. (2010).

Experimental top

The synthesis of the title compound follows the modified Riemmer-Tiemann reaction, in which the substituted salicylaldehydes were synthesized from substituted phenols. To 80 mL of water 60g of sodium hydroxide was added and dissolved completely. Then 15g of 4-tert-butyl phenol was added and heated to 60-65°C. 30 mL chloroform was added step by step to the mixture. The resulting reaction mixture was heated for one hour, until the formation of precipitate. The liquid layer containing 5-tert-butyl-2-hydroxy benzaldehyde as the product was separated through suction pump. It was then brominated using liquid bromine and acetic acid. The final product 3-bromo-5-tert-butyl-2-hydroxy benzaldehyde with a maximum yield of 83% was checked for purity using TLC.

Structure description top

The crystal structure determination of the title compound was undertaken as a part of the synthesis, structure and properties of new substituted salicylaldehyde derivatives.

For the biological activity of substituted salicylaldehyde and its derivatives, see: Mounika et al. (2010); Dueke-Eze et al. (2010); Jesmin et al. (2010). For a related structure, see: Wang et al. (2010).

Computing details top

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

Figures top

Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

3-Bromo-5-tert-butyl-2-hydroxybenzaldehyde top

Crystal data top

C₁₁H₁₃BrO₂	F(000) = 1040
M_r = 257.11	D_x = 1.516 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2808 reflections
a = 9.9727 (19) Å	θ = 2.2–28.3°
b = 12.174 (2) Å	µ = 3.62 mm⁻¹
c = 18.558 (3) Å	T = 293 K
V = 2253.0 (7) Å³	Block, red
Z = 8	0.2 × 0.2 × 0.2 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	1442 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.079
Graphite monochromator	θ_max = 28.3°, θ_min = 2.2°
ω and φ scans	h = −13→13
11555 measured reflections	k = −16→16
2808 independent reflections	l = −24→24

Refinement top

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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.0685P)² + 1.3566P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2808 reflections	Δρ_max = 0.59 e Å⁻³
131 parameters	Δρ_min = −0.49 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0228 (17)

Crystal data top

C₁₁H₁₃BrO₂	V = 2253.0 (7) Å³
M_r = 257.11	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.9727 (19) Å	µ = 3.62 mm⁻¹
b = 12.174 (2) Å	T = 293 K
c = 18.558 (3) Å	0.2 × 0.2 × 0.2 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	1442 reflections with I > 2σ(I)
11555 measured reflections	R_int = 0.079
2808 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.162	H-atom parameters constrained
S = 1.02	Δρ_max = 0.59 e Å⁻³
2808 reflections	Δρ_min = −0.49 e Å⁻³
131 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2770 (5)	0.1032 (4)	0.2246 (2)	0.0474 (11)
C2	0.3680 (5)	0.0161 (4)	0.2178 (2)	0.0507 (12)
C3	0.4296 (4)	−0.0219 (3)	0.2794 (2)	0.0454 (10)
C4	0.4025 (4)	0.0242 (3)	0.3456 (2)	0.0462 (10)
H4	0.4468	−0.0027	0.3860	0.055*
C5	0.3112 (4)	0.1097 (3)	0.3540 (2)	0.0422 (10)
C6	0.2493 (5)	0.1482 (3)	0.2924 (2)	0.0473 (11)
H2	0.1878	0.2054	0.2960	0.057*
C7	0.2094 (6)	0.1487 (4)	0.1612 (3)	0.0656 (14)
H7	0.1509	0.2073	0.1680	0.079*
C8	0.2802 (5)	0.1613 (4)	0.4275 (2)	0.0526 (12)
C9	0.1367 (8)	0.1334 (7)	0.4478 (4)	0.136 (3)
H9A	0.1272	0.1358	0.4992	0.204*
H9B	0.1153	0.0610	0.4308	0.204*
H9C	0.0770	0.1857	0.4262	0.204*
C10	0.3682 (8)	0.1149 (6)	0.4877 (3)	0.104 (2)
H10A	0.4604	0.1319	0.4780	0.156*
H10B	0.3570	0.0367	0.4901	0.156*
H10C	0.3423	0.1471	0.5328	0.156*
C11	0.3014 (10)	0.2826 (5)	0.4242 (3)	0.131 (4)
H11A	0.3899	0.2977	0.4063	0.196*
H11B	0.2919	0.3133	0.4716	0.196*
H11C	0.2362	0.3149	0.3926	0.196*
O1	0.2253 (5)	0.1147 (3)	0.1006 (2)	0.0919 (14)
O2	0.3953 (4)	−0.0316 (3)	0.15377 (18)	0.0749 (10)
H2A	0.3523	−0.0009	0.1219	0.112*
Br1	0.55350 (5)	−0.13980 (4)	0.27226 (4)	0.0729 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.050 (3)	0.052 (2)	0.040 (2)	−0.012 (2)	0.001 (2)	−0.0048 (19)
C2	0.050 (3)	0.056 (2)	0.047 (3)	−0.017 (2)	0.013 (2)	−0.012 (2)
C3	0.041 (2)	0.0376 (19)	0.057 (3)	−0.0019 (17)	0.005 (2)	−0.0125 (18)
C4	0.046 (2)	0.045 (2)	0.047 (3)	−0.004 (2)	−0.005 (2)	−0.0026 (19)
C5	0.047 (3)	0.042 (2)	0.038 (2)	−0.0035 (18)	0.001 (2)	−0.0045 (16)
C6	0.052 (3)	0.043 (2)	0.047 (3)	0.001 (2)	0.000 (2)	−0.0012 (17)
C7	0.073 (4)	0.076 (3)	0.048 (3)	−0.003 (3)	−0.010 (3)	0.002 (2)
C8	0.065 (3)	0.057 (3)	0.036 (2)	0.010 (2)	0.007 (3)	−0.0029 (19)
C9	0.095 (5)	0.231 (10)	0.081 (5)	−0.019 (6)	0.037 (5)	−0.059 (5)
C10	0.142 (7)	0.119 (5)	0.052 (3)	0.040 (5)	−0.007 (4)	−0.004 (3)
C11	0.276 (12)	0.059 (3)	0.057 (3)	0.006 (5)	−0.001 (5)	−0.017 (3)
O1	0.111 (4)	0.119 (3)	0.046 (2)	−0.009 (3)	−0.015 (2)	−0.001 (2)
O2	0.080 (2)	0.092 (2)	0.053 (2)	−0.007 (2)	0.019 (2)	−0.0289 (18)
Br1	0.0566 (4)	0.0588 (4)	0.1033 (6)	0.0078 (2)	0.0097 (3)	−0.0204 (3)

Geometric parameters (Å, º) top

C1—C6	1.400 (6)	C8—C11	1.494 (7)
C1—C2	1.401 (7)	C8—C9	1.518 (9)
C1—C7	1.465 (7)	C8—C10	1.528 (8)
C2—O2	1.350 (5)	C9—H9A	0.9600
C2—C3	1.377 (6)	C9—H9B	0.9600
C3—C4	1.377 (6)	C9—H9C	0.9600
C3—Br1	1.899 (4)	C10—H10A	0.9600
C4—C5	1.392 (6)	C10—H10B	0.9600
C4—H4	0.9300	C10—H10C	0.9600
C5—C6	1.381 (6)	C11—H11A	0.9600
C5—C8	1.533 (6)	C11—H11B	0.9600
C6—H2	0.9300	C11—H11C	0.9600
C7—O1	1.209 (6)	O2—H2A	0.8200
C7—H7	0.9300

C6—C1—C2	120.3 (4)	C9—C8—C10	106.1 (5)
C6—C1—C7	118.9 (4)	C11—C8—C5	109.8 (4)
C2—C1—C7	120.8 (4)	C9—C8—C5	108.6 (5)
O2—C2—C3	119.8 (4)	C10—C8—C5	112.6 (4)
O2—C2—C1	122.3 (4)	C8—C9—H9A	109.5
C3—C2—C1	117.9 (4)	C8—C9—H9B	109.5
C4—C3—C2	121.1 (4)	H9A—C9—H9B	109.5
C4—C3—Br1	119.8 (4)	C8—C9—H9C	109.5
C2—C3—Br1	119.1 (3)	H9A—C9—H9C	109.5
C3—C4—C5	122.2 (4)	H9B—C9—H9C	109.5
C3—C4—H4	118.9	C8—C10—H10A	109.5
C5—C4—H4	118.9	C8—C10—H10B	109.5
C6—C5—C4	116.9 (4)	H10A—C10—H10B	109.5
C6—C5—C8	120.5 (4)	C8—C10—H10C	109.5
C4—C5—C8	122.5 (4)	H10A—C10—H10C	109.5
C5—C6—C1	121.6 (4)	H10B—C10—H10C	109.5
C5—C6—H2	119.2	C8—C11—H11A	109.5
C1—C6—H2	119.2	C8—C11—H11B	109.5
O1—C7—C1	123.9 (5)	H11A—C11—H11B	109.5
O1—C7—H7	118.1	C8—C11—H11C	109.5
C1—C7—H7	118.1	H11A—C11—H11C	109.5
C11—C8—C9	111.4 (6)	H11B—C11—H11C	109.5
C11—C8—C10	108.3 (5)	C2—O2—H2A	109.5

C6—C1—C2—O2	178.4 (4)	C4—C5—C6—C1	0.1 (6)
C7—C1—C2—O2	−1.7 (7)	C8—C5—C6—C1	179.4 (4)
C6—C1—C2—C3	−0.8 (6)	C2—C1—C6—C5	0.8 (7)
C7—C1—C2—C3	179.0 (4)	C7—C1—C6—C5	−179.1 (4)
O2—C2—C3—C4	−179.2 (4)	C6—C1—C7—O1	−179.1 (5)
C1—C2—C3—C4	0.0 (6)	C2—C1—C7—O1	1.0 (8)
O2—C2—C3—Br1	0.7 (6)	C6—C5—C8—C11	−53.8 (7)
C1—C2—C3—Br1	180.0 (3)	C4—C5—C8—C11	125.4 (6)
C2—C3—C4—C5	0.9 (7)	C6—C5—C8—C9	68.3 (6)
Br1—C3—C4—C5	−179.1 (3)	C4—C5—C8—C9	−112.5 (6)
C3—C4—C5—C6	−0.9 (6)	C6—C5—C8—C10	−174.5 (5)
C3—C4—C5—C8	179.8 (4)	C4—C5—C8—C10	4.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	1.93	2.650 (6)	145

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃BrO₂
M_r	257.11
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	9.9727 (19), 12.174 (2), 18.558 (3)
V (Å³)	2253.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.62
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11555, 2808, 1442
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.162, 1.02
No. of reflections	2808
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.49

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	1.93	2.650 (6)	145

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection.

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dueke-Eze, C. U., Fasina, T. M. & Idika, N. (2010). Afr. J. Pure Appl. Chem. 5, 13–18. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Jesmin, M., Ali, M. M. & Khanam, J. A. (2010). Thai J. Pharm. Sci. 34, 20–31. CAS Google Scholar
Mounika, K., Anupama, B., Pragathi, J. & Gyanakumari, C. (2010). J. Sci. Res. 2, 513-524. CAS 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
Wang, Y., Qiu, Z. & Liang, H. (2010). Acta Cryst. E66, o2218. Web of Science CSD CrossRef IUCr Journals Google Scholar