4-Methyl­phenyl 4-bromo­benzoate

Abstract

In the title compound, C₁₄H₁₁BrO₂, an ester formed from the reaction of 4-methyl­phenol with 4-bromo­benzoyl­chloride, the dihedral angle between the benzene rings is 54.43 (7)°, indicating a twist in the mol­ecule. In the crystal, weak C—H⋯O inter­actions link the mol­ecules into supra­molecular layers in the bc plane, and these are connected along the a axis by Br⋯Br contacts [3.6328 (5) Å].

Related literature

For industrial applications of ester systems, see: Gowda et al. (2007a ▶); Brüning et al. (2009 ▶). For related structures, see: Gowda et al. (2007b ▶, 2008 ▶). For hydrogen bonding, see: Nardelli (1995 ▶). For halogen inter­actions, see: Ritter (2009 ▶).

Experimental

Crystal data

• C₁₄H₁₁BrO₂

• M _r = 291.13

• Monoclinic,

• a = 15.0219 (9) Å

• b = 11.3585 (8) Å

• c = 7.5077 (4) Å

• β = 99.730 (4)°

• V = 1262.58 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 3.24 mm⁻¹

• T = 293 K

• 0.47 × 0.18 × 0.10 mm

Data collection

• Bruker–Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.472, T _max = 0.698

• 9090 measured reflections

• 2829 independent reflections

• 1811 reflections with I > 2σ(I)

• R _int = 0.052

Refinement

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.125

• S = 1.01

• 2829 reflections

• 156 parameters

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.36 e Å⁻³

Data collection: COLLECT (Nonius, 2004 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811040426/tk2795Isup3.cml

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
C3—H3⋯O1i	0.93	2.67	3.483 (4)	147
C13—H13⋯O1ii	0.93	2.77	3.422 (4)	128

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

This work is part of the study of the effect of substituents on the ester system. Similar work, involving ester systems with an emphasis on industrial applications has been published (Gowda et al., 2007a; Brüning et al., 2009). The molecular structure of the title compound (I) is similar to that of 4-bromophenyl benzoate (4BPB) (Gowda et al., 2008) and 4-methylphenyl 4-methylbenzoate (4MPB) (Gowda et al., 2007b). Compound (I) shows a dihedral angle of 54.43 (7)° between the mean planes of the benzene rings (Fig. 1). This dihedral angle is close to the values presented in the 4BPB and 4MPB molecules [58.43 (17) and 60.17 (7)°, respectively].

The crystal packing is stabilized by C—H···O interactions (Nardelli, 1995); Table 1. These weak interactions link the molecules into supramolecular layers in the bc plane. The layers are connected by Br···Br interactions (Ritter, 2009).

Experimental

A solution containing equimolar quantities (3.4 mmol) of 4-bromobenzoyl chloride and 4-methylphenol in acetonitrile (60 ml) was gradually heated to reflux for 2 h and then allowed to cool. At room temperature, triethylamine was added to get a solid which was poured in cold water. The solid was recrystallized from its dichlorometane solution to yield colourless crystals; M.pt. 385 (1) K.

Refinement

The H-atoms were positioned geometrically [C—H = 0.93–0.96 Å, and with U_iso(H) =1.2–1.5U_eq(C).

Figures

Fig. 1.

Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

Crystal data

C14H11BrO2	F(000) = 584
Mr = 291.13	Dx = 1.532 Mg m−3
Monoclinic, P21/c	Melting point: 385(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.0219 (9) Å	Cell parameters from 9005 reflections
b = 11.3585 (8) Å	θ = 2.9–27.5°
c = 7.5077 (4) Å	µ = 3.24 mm−1
β = 99.730 (4)°	T = 293 K
V = 1262.58 (14) Å3	Prism, colourless
Z = 4	0.47 × 0.18 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	2829 independent reflections
Radiation source: fine-focus sealed tube	1811 reflections with I > 2σ(I)
horizonally mounted graphite crystal	Rint = 0.052
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 3.7°
CCD scans	h = −19→19
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→10
Tmin = 0.472, Tmax = 0.698	l = −9→9
9090 measured reflections

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)] = 0.042	H-atom parameters constrained
wR(F2) = 0.125	w = 1/[σ2(Fo2) + (0.0577P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2829 reflections	Δρmax = 0.31 e Å−3
156 parameters	Δρmin = −0.36 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: 0.020 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.61020 (2)	0.93326 (4)	0.00395 (6)	0.0970 (2)
C14	1.4444 (2)	0.8443 (4)	0.4571 (6)	0.1050 (13)
H14A	1.4685	0.8902	0.5615	0.158*
H14B	1.4718	0.8687	0.3564	0.158*
H14C	1.4572	0.7625	0.4817	0.158*
O2	1.06435 (14)	0.91018 (16)	0.2775 (3)	0.0640 (5)
O1	1.02822 (15)	0.7422 (2)	0.4071 (3)	0.0864 (7)
C5	0.8438 (2)	0.7772 (2)	0.2633 (4)	0.0615 (7)
H5	0.8594	0.7079	0.3270	0.074*
C1	0.7324 (2)	0.9019 (3)	0.0998 (4)	0.0631 (7)
C3	0.8867 (2)	0.9613 (2)	0.1444 (4)	0.0590 (6)
H3	0.9309	1.0156	0.1275	0.071*
C2	0.7978 (2)	0.9834 (3)	0.0749 (4)	0.0619 (7)
H2	0.7815	1.0526	0.0116	0.074*
C8	1.15716 (19)	0.8889 (2)	0.3280 (3)	0.0558 (6)
C7	1.0054 (2)	0.8281 (3)	0.3177 (4)	0.0617 (7)
C4	0.91105 (18)	0.8576 (2)	0.2403 (3)	0.0545 (6)
C6	0.7555 (2)	0.7987 (3)	0.1938 (4)	0.0663 (7)
H6	0.7111	0.7444	0.2095	0.080*
C11	1.3432 (2)	0.8623 (3)	0.4124 (4)	0.0723 (8)
C13	1.1971 (2)	0.7893 (2)	0.2718 (4)	0.0641 (7)
H13	1.1624	0.7313	0.2056	0.077*
C9	1.2087 (2)	0.9753 (3)	0.4252 (4)	0.0636 (7)
H9	1.1814	1.0422	0.4630	0.076*
C12	1.2891 (2)	0.7777 (3)	0.3156 (4)	0.0710 (8)
H12	1.3161	0.7103	0.2789	0.085*
C10	1.3008 (2)	0.9615 (3)	0.4656 (4)	0.0720 (8)
H10	1.3355	1.0202	0.5302	0.086*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0691 (3)	0.1091 (4)	0.1086 (4)	0.00332 (19)	0.00328 (19)	0.0103 (2)
C14	0.067 (2)	0.107 (3)	0.140 (3)	0.002 (2)	0.014 (2)	0.004 (3)
O2	0.0677 (12)	0.0511 (11)	0.0726 (11)	0.0013 (9)	0.0099 (9)	0.0076 (9)
O1	0.0789 (14)	0.0797 (15)	0.0998 (15)	0.0048 (12)	0.0129 (11)	0.0395 (13)
C5	0.0802 (19)	0.0442 (14)	0.0603 (14)	−0.0036 (13)	0.0130 (13)	0.0073 (11)
C1	0.0668 (16)	0.0635 (17)	0.0598 (15)	0.0025 (14)	0.0127 (12)	−0.0013 (13)
C3	0.0727 (17)	0.0450 (14)	0.0630 (14)	−0.0011 (12)	0.0221 (13)	0.0035 (11)
C2	0.0724 (17)	0.0500 (15)	0.0656 (15)	0.0088 (14)	0.0187 (13)	0.0065 (13)
C8	0.0665 (16)	0.0492 (14)	0.0530 (13)	0.0001 (12)	0.0137 (11)	0.0047 (11)
C7	0.0760 (18)	0.0527 (15)	0.0577 (14)	−0.0008 (14)	0.0145 (12)	0.0066 (13)
C4	0.0695 (16)	0.0446 (14)	0.0507 (13)	0.0012 (12)	0.0141 (11)	0.0017 (10)
C6	0.0751 (18)	0.0569 (17)	0.0677 (15)	−0.0106 (14)	0.0144 (13)	0.0014 (13)
C11	0.0743 (18)	0.066 (2)	0.0790 (18)	0.0034 (15)	0.0196 (15)	0.0049 (15)
C13	0.0816 (19)	0.0510 (15)	0.0596 (14)	0.0004 (14)	0.0118 (13)	−0.0032 (12)
C9	0.0733 (18)	0.0506 (15)	0.0700 (16)	−0.0020 (14)	0.0212 (13)	−0.0066 (13)
C12	0.086 (2)	0.0580 (17)	0.0729 (17)	0.0097 (16)	0.0240 (15)	−0.0012 (14)
C10	0.078 (2)	0.0616 (18)	0.0766 (18)	−0.0107 (15)	0.0145 (15)	−0.0076 (14)

Geometric parameters (Å, °)

Br1—C1	1.889 (3)	C3—H3	0.9300
C14—C11	1.515 (5)	C2—H2	0.9300
C14—H14A	0.9600	C8—C9	1.380 (4)
C14—H14B	0.9600	C8—C13	1.380 (4)
C14—H14C	0.9600	C7—C4	1.477 (4)
O2—C7	1.355 (3)	C6—H6	0.9300
O2—C8	1.402 (3)	C11—C10	1.386 (5)
O1—C7	1.200 (3)	C11—C12	1.383 (5)
C5—C6	1.363 (4)	C13—C12	1.372 (4)
C5—C4	1.394 (4)	C13—H13	0.9300
C5—H5	0.9300	C9—C10	1.375 (4)
C1—C6	1.382 (4)	C9—H9	0.9300
C1—C2	1.384 (4)	C12—H12	0.9300
C3—C2	1.373 (4)	C10—H10	0.9300
C3—C4	1.397 (4)
C11—C14—H14A	109.5	O1—C7—C4	124.7 (3)
C11—C14—H14B	109.5	O2—C7—C4	112.1 (2)
H14A—C14—H14B	109.5	C5—C4—C3	119.0 (3)
C11—C14—H14C	109.5	C5—C4—C7	118.0 (2)
H14A—C14—H14C	109.5	C3—C4—C7	123.0 (2)
H14B—C14—H14C	109.5	C5—C6—C1	119.4 (3)
C7—O2—C8	118.6 (2)	C5—C6—H6	120.3
C6—C5—C4	120.9 (3)	C1—C6—H6	120.3
C6—C5—H5	119.6	C10—C11—C12	117.3 (3)
C4—C5—H5	119.6	C10—C11—C14	122.6 (3)
C6—C1—C2	120.9 (3)	C12—C11—C14	120.1 (3)
C6—C1—Br1	119.9 (2)	C12—C13—C8	118.5 (3)
C2—C1—Br1	119.2 (2)	C12—C13—H13	120.7
C2—C3—C4	120.2 (3)	C8—C13—H13	120.7
C2—C3—H3	119.9	C10—C9—C8	119.3 (3)
C4—C3—H3	119.9	C10—C9—H9	120.3
C3—C2—C1	119.6 (3)	C8—C9—H9	120.3
C3—C2—H2	120.2	C13—C12—C11	122.6 (3)
C1—C2—H2	120.2	C13—C12—H12	118.7
C9—C8—C13	120.7 (3)	C11—C12—H12	118.7
C9—C8—O2	117.6 (2)	C9—C10—C11	121.6 (3)
C13—C8—O2	121.5 (3)	C9—C10—H10	119.2
O1—C7—O2	123.3 (3)	C11—C10—H10	119.2
C4—C3—C2—C1	−0.3 (4)	O2—C7—C4—C3	−2.8 (4)
C6—C1—C2—C3	0.1 (4)	C4—C5—C6—C1	−0.2 (4)
Br1—C1—C2—C3	179.9 (2)	C2—C1—C6—C5	0.2 (4)
C7—O2—C8—C9	−128.0 (3)	Br1—C1—C6—C5	−179.6 (2)
C7—O2—C8—C13	56.6 (3)	C9—C8—C13—C12	0.4 (4)
C8—O2—C7—O1	6.1 (4)	O2—C8—C13—C12	175.6 (2)
C8—O2—C7—C4	−174.3 (2)	C13—C8—C9—C10	0.2 (4)
C6—C5—C4—C3	0.0 (4)	O2—C8—C9—C10	−175.2 (2)
C6—C5—C4—C7	−179.4 (2)	C8—C13—C12—C11	−0.6 (4)
C2—C3—C4—C5	0.3 (4)	C10—C11—C12—C13	0.2 (5)
C2—C3—C4—C7	179.7 (2)	C14—C11—C12—C13	179.8 (3)
O1—C7—C4—C5	−3.8 (4)	C8—C9—C10—C11	−0.6 (5)
O2—C7—C4—C5	176.6 (2)	C12—C11—C10—C9	0.4 (5)
O1—C7—C4—C3	176.7 (3)	C14—C11—C10—C9	−179.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1i	0.93	2.67	3.483 (4)	147.
C13—H13···O1ii	0.93	2.77	3.422 (4)	128.

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