(5-Bromo-2-hydroxy­phen­yl)(phen­yl)methanone

Abstract

In the title compound, C₁₃H₉BrO₂, the dihedral angle between the aromatic ring planes is 53.6 (1)°. The crystal structure is stabilized by intra­molecular O—H⋯O and inter­molecular C—H⋯O hydrogen bonding and C—H⋯π inter­actions.

Related literature

For the ability of aroylhydrazones to coordinate to metal ions and their biological activity, see: Singh et al. (1982 ▶); Salem (1998 ▶); Carcelli et al. (1995 ▶).

Experimental

Crystal data

• C₁₃H₉BrO₂

• M _r = 277.11

• Monoclinic,

• a = 15.9510 (18) Å

• b = 5.8956 (6) Å

• c = 12.1260 (14) Å

• β = 106.166 (2)°

• V = 1095.2 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 3.73 mm⁻¹

• T = 298 K

• 0.15 × 0.10 × 0.06 mm

Data collection

• Siemens SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.604, T _max = 0.807

• 5479 measured reflections

• 1933 independent reflections

• 1578 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.072

• S = 1.03

• 1933 reflections

• 146 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.52 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT (Siemens, 1996 ▶); 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	1.85	2.569 (3)	146
C3—H3⋯O1i	0.93	2.60	3.488 (3)	160
C12—H12⋯Cg1ii	0.93	2.93	3.596 (3)	130

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C8–C13 ring.

supplementary crystallographic information

Comment

The chemistry of aroylhydrazones continues to attract much attention due to their coordination ability to metal ions (Singh et al., 1982; Salem, 1998) and their biological activity (Singh et al., 1982; Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives, the title compound, (I), was synthesized and its crystal structure is reported here.

The title molecule displays a trans conformation with respect to the C7=O2 double bond (Fig. 1). The crystal structure is stabilized by intramolecular O—H···O and intermolecular C—H···O hydrogen bonding and C-H···π interactions (Table 1. and Fig. 2).

Experimental

The benzoyl chloride (0.01 mol, 1.4057 g) and the 4-bromophenol, heated up in the oil bath, the reaction mixture was refluxed for 6 h with stirring. Then anhydrous aluminium trichloride (3 mol, 1:3) was added, the backflow agitation responds for 4 h (yield 80%). The compound (2.0 mmol, 0.67 g) was dissolved in dimethylformamide (30 ml) and kept at room temperature for 30 d to obtain brown single crystals suitable for X-ray diffraction.

Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms,with C—H(aromatic) = 0.93 Å, O—H = 0.82 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Figures

Fig. 1.

The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

The crystal packing of (I), viewed down the b axis. Dashed lines show intra-and intermolecular hydrogen bonds.

Crystal data

C13H9BrO2	F000 = 552
Mr = 277.11	Dx = 1.681 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2043 reflections
a = 15.9510 (18) Å	θ = 2.7–23.4º
b = 5.8956 (6) Å	µ = 3.73 mm−1
c = 12.1260 (14) Å	T = 298 K
β = 106.166 (2)º	Block, yellow
V = 1095.2 (2) Å3	0.15 × 0.10 × 0.06 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	1933 independent reflections
Radiation source: fine-focus sealed tube	1578 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.027
T = 273(2) K	θmax = 25.1º
φ and ω scans	θmin = 2.7º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −18→19
Tmin = 0.604, Tmax = 0.807	k = −4→7
5479 measured reflections	l = −14→14

Refinement

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)] = 0.029	H-atom parameters constrained
wR(F2) = 0.073	w = 1/[σ2(Fo2) + (0.0296P)2 + 0.7566P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
1933 reflections	Δρmax = 0.33 e Å−3
146 parameters	Δρmin = −0.52 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.42247 (2)	−0.27591 (5)	0.49702 (3)	0.05526 (14)
O1	0.28452 (15)	0.5186 (4)	0.70204 (17)	0.0548 (6)
H1	0.2528	0.5974	0.6517	0.082*
O2	0.18991 (14)	0.6145 (4)	0.49878 (17)	0.0537 (6)
C1	0.31010 (19)	0.3343 (5)	0.6540 (2)	0.0404 (7)
C2	0.27504 (17)	0.2828 (4)	0.5366 (2)	0.0330 (6)
C3	0.30905 (17)	0.0971 (4)	0.4914 (2)	0.0336 (6)
H3	0.2877	0.0616	0.4139	0.040*
C4	0.37381 (18)	−0.0324 (5)	0.5610 (2)	0.0384 (6)
C5	0.40544 (19)	0.0138 (6)	0.6778 (3)	0.0493 (8)
H5	0.4478	−0.0789	0.7248	0.059*
C6	0.37369 (19)	0.1969 (6)	0.7229 (2)	0.0485 (8)
H6	0.3952	0.2292	0.8008	0.058*
C7	0.20810 (18)	0.4294 (5)	0.4636 (2)	0.0362 (6)
C8	0.16079 (17)	0.3613 (5)	0.3442 (2)	0.0340 (6)
C9	0.15422 (19)	0.5167 (5)	0.2563 (2)	0.0415 (7)
H9	0.1816	0.6569	0.2718	0.050*
C10	0.1068 (2)	0.4626 (6)	0.1452 (3)	0.0503 (8)
H10	0.1042	0.5646	0.0858	0.060*
C11	0.0636 (2)	0.2594 (6)	0.1225 (3)	0.0510 (8)
H11	0.0310	0.2250	0.0481	0.061*
C12	0.06851 (19)	0.1062 (5)	0.2098 (3)	0.0466 (7)
H12	0.0381	−0.0300	0.1942	0.056*
C13	0.11812 (18)	0.1530 (5)	0.3204 (2)	0.0385 (6)
H13	0.1230	0.0464	0.3784	0.046*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0478 (2)	0.0490 (2)	0.0675 (2)	0.01286 (15)	0.01368 (16)	−0.00212 (16)
O1	0.0628 (15)	0.0608 (15)	0.0403 (11)	0.0066 (11)	0.0136 (11)	−0.0127 (10)
O2	0.0641 (15)	0.0420 (13)	0.0519 (13)	0.0133 (10)	0.0108 (11)	−0.0070 (10)
C1	0.0385 (16)	0.0481 (17)	0.0381 (15)	−0.0056 (13)	0.0162 (13)	−0.0043 (13)
C2	0.0326 (14)	0.0341 (15)	0.0329 (13)	−0.0019 (11)	0.0102 (11)	0.0019 (11)
C3	0.0336 (15)	0.0363 (15)	0.0309 (14)	−0.0059 (12)	0.0091 (12)	−0.0005 (12)
C4	0.0330 (15)	0.0396 (16)	0.0450 (16)	0.0014 (12)	0.0146 (13)	0.0027 (13)
C5	0.0364 (17)	0.065 (2)	0.0425 (17)	0.0083 (15)	0.0039 (13)	0.0110 (15)
C6	0.0390 (17)	0.073 (2)	0.0306 (15)	0.0016 (16)	0.0054 (13)	0.0008 (15)
C7	0.0400 (16)	0.0324 (15)	0.0399 (15)	−0.0013 (12)	0.0172 (13)	0.0024 (12)
C8	0.0312 (14)	0.0339 (15)	0.0377 (15)	0.0057 (12)	0.0109 (12)	0.0017 (12)
C9	0.0457 (18)	0.0331 (16)	0.0476 (17)	0.0047 (13)	0.0160 (14)	0.0075 (13)
C10	0.055 (2)	0.057 (2)	0.0378 (17)	0.0142 (16)	0.0116 (15)	0.0143 (15)
C11	0.0438 (17)	0.064 (2)	0.0393 (16)	0.0131 (16)	0.0013 (13)	−0.0034 (16)
C12	0.0351 (16)	0.0453 (18)	0.0565 (19)	−0.0009 (13)	0.0079 (14)	−0.0071 (15)
C13	0.0360 (15)	0.0381 (16)	0.0421 (16)	0.0035 (12)	0.0117 (13)	0.0056 (13)

Geometric parameters (Å, °)

Br1—C4	1.898 (3)	C6—H6	0.9300
O1—C1	1.348 (3)	C7—C8	1.489 (4)
O1—H1	0.8200	C8—C9	1.388 (4)
O2—C7	1.235 (3)	C8—C13	1.395 (4)
C1—C6	1.382 (4)	C9—C10	1.386 (4)
C1—C2	1.411 (4)	C9—H9	0.9300
C2—C3	1.400 (4)	C10—C11	1.371 (4)
C2—C7	1.464 (4)	C10—H10	0.9300
C3—C4	1.370 (4)	C11—C12	1.377 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.391 (4)	C12—C13	1.382 (4)
C5—C6	1.370 (4)	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300
C1—O1—H1	109.5	O2—C7—C8	118.0 (2)
O1—C1—C6	118.1 (3)	C2—C7—C8	121.0 (2)
O1—C1—C2	121.8 (3)	C9—C8—C13	119.6 (3)
C6—C1—C2	120.1 (3)	C9—C8—C7	118.6 (2)
C3—C2—C1	118.4 (2)	C13—C8—C7	121.6 (2)
C3—C2—C7	121.4 (2)	C10—C9—C8	120.0 (3)
C1—C2—C7	120.0 (2)	C10—C9—H9	120.0
C4—C3—C2	120.1 (2)	C8—C9—H9	120.0
C4—C3—H3	119.9	C11—C10—C9	120.3 (3)
C2—C3—H3	119.9	C11—C10—H10	119.9
C3—C4—C5	121.1 (3)	C9—C10—H10	119.9
C3—C4—Br1	119.5 (2)	C10—C11—C12	120.1 (3)
C5—C4—Br1	119.4 (2)	C10—C11—H11	120.0
C6—C5—C4	119.4 (3)	C12—C11—H11	120.0
C6—C5—H5	120.3	C11—C12—C13	120.6 (3)
C4—C5—H5	120.3	C11—C12—H12	119.7
C5—C6—C1	120.8 (3)	C13—C12—H12	119.7
C5—C6—H6	119.6	C12—C13—C8	119.4 (3)
C1—C6—H6	119.6	C12—C13—H13	120.3
O2—C7—C2	121.0 (2)	C8—C13—H13	120.3

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.85	2.569 (3)	146
C3—H3···O1i	0.93	2.60	3.488 (3)	160
C12—H12···Cg1ii	0.93	2.93	3.596 (3)	130

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