Literature DB >> 22220121

2-(4-Bromo-phen-yl)-2-oxoethyl 2-methyl-benzoate.

Hoong-Kun Fun, Chin Wei Ooi, B Garudachari, Arun M Isloor, M N Satyanarayan.

Abstract

In the title compound, C(16)H(13)BrO(3), the dihedral angle formed between the bromo- and methyl-substituted benzene rings is 66.66 (8)°. In the crystal, mol-ecules are linked by inter-molecular C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the ac plane. The crystal packing is further consolidated by C-H⋯π inter-actions.

Entities: Chemical Disease Gene

Year: 2011 PMID： 22220121 PMCID： PMC3247503 DOI： 10.1107/S1600536811044564

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For background and applications of phenacyl benzoates, see: Rather & Reid (1919 ▶); Sheehan & Umezaw (1973 ▶); Ruzicka et al. (2002 ▶); Litera et al. (2006 ▶); Huang et al. (1996 ▶); Gandhi et al. (1995 ▶). For a related structure, see: Fun et al. (2011 ▶). For the synthesis, see: Judefind & Reid (1920 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C16H13BrO3 M = 333.17 Monoclinic, a = 5.4519 (1) Å b = 31.2382 (5) Å c = 9.7206 (1) Å β = 120.410 (1)° V = 1427.74 (4) Å3 Z = 4 Mo Kα radiation μ = 2.88 mm−1 T = 100 K 0.51 × 0.36 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.323, T max = 0.811 20164 measured reflections 5211 independent reflections 4181 reflections with I > 2σ(I) R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.040 wR(F 2) = 0.094 S = 1.04 5211 reflections 182 parameters H-atom parameters constrained Δρmax = 0.85 e Å−3 Δρmin = −0.43 e Å−3 Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶). Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811044564/is2797sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044564/is2797Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536811044564/is2797Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₆H₁₃BrO₃	F(000) = 672
M_r = 333.17	D_x = 1.550 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7724 reflections
a = 5.4519 (1) Å	θ = 2.6–32.6°
b = 31.2382 (5) Å	µ = 2.88 mm⁻¹
c = 9.7206 (1) Å	T = 100 K
β = 120.410 (1)°	Plate, colourless
V = 1427.74 (4) Å³	0.51 × 0.36 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5211 independent reflections
Radiation source: fine-focus sealed tube	4181 reflections with I > 2σ(I)
graphite	R_int = 0.032
φ and ω scans	θ_max = 32.7°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.323, T_max = 0.811	k = −35→47
20164 measured reflections	l = −14→14

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0391P)² + 0.9854P] where P = (F_o² + 2F_c²)/3
5211 reflections	(Δ/σ)_max = 0.003
182 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	U_iso*/U_eq
Br1	0.17278 (4)	0.970131 (6)	0.70447 (3)	0.03247 (7)
O1	0.2143 (2)	0.70425 (4)	0.82251 (14)	0.0169 (2)
O2	0.4582 (2)	0.75657 (4)	0.70793 (14)	0.0185 (2)
O3	−0.1113 (3)	0.70407 (4)	0.56018 (15)	0.0219 (3)
C1	0.1466 (3)	0.84316 (5)	0.81729 (19)	0.0167 (3)
H1A	0.0726	0.8273	0.8715	0.020*
C2	0.1160 (3)	0.88749 (6)	0.8057 (2)	0.0194 (3)
H2A	0.0232	0.9020	0.8526	0.023*
C3	0.2231 (3)	0.91002 (6)	0.7248 (2)	0.0197 (3)
C4	0.3636 (4)	0.88967 (6)	0.6568 (2)	0.0202 (3)
H4A	0.4370	0.9057	0.6024	0.024*
C5	0.3940 (3)	0.84555 (6)	0.6701 (2)	0.0177 (3)
H5A	0.4897	0.8312	0.6246	0.021*
C6	0.2854 (3)	0.82191 (5)	0.74968 (18)	0.0145 (3)
C7	0.3187 (3)	0.77446 (5)	0.75677 (18)	0.0147 (3)
C8	0.1688 (4)	0.74932 (5)	0.8257 (2)	0.0170 (3)
H8A	0.2405	0.7585	0.9371	0.020*
H8B	−0.0376	0.7554	0.7635	0.020*
C9	0.0627 (3)	0.68539 (5)	0.67839 (19)	0.0156 (3)
C10	0.1268 (3)	0.63882 (5)	0.68481 (19)	0.0154 (3)
C11	0.4045 (3)	0.62214 (6)	0.7696 (2)	0.0178 (3)
C12	0.4349 (4)	0.57773 (6)	0.7654 (2)	0.0234 (3)
H12A	0.6203	0.5657	0.8198	0.028*
C13	0.2030 (4)	0.55090 (6)	0.6846 (2)	0.0259 (4)
H13A	0.2306	0.5208	0.6866	0.031*
C14	−0.0708 (4)	0.56778 (6)	0.6002 (2)	0.0239 (3)
H14A	−0.2306	0.5495	0.5440	0.029*
C15	−0.1062 (3)	0.61174 (6)	0.5995 (2)	0.0191 (3)
H15A	−0.2917	0.6236	0.5400	0.023*
C16	0.6654 (3)	0.64980 (6)	0.8579 (2)	0.0223 (3)
H16A	0.8327	0.6338	0.8739	0.033*
H16B	0.6905	0.6579	0.9616	0.033*
H16C	0.6428	0.6757	0.7954	0.033*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03491 (11)	0.01766 (9)	0.04329 (13)	0.00216 (7)	0.01866 (9)	0.00472 (8)
O1	0.0187 (5)	0.0162 (5)	0.0144 (5)	0.0007 (4)	0.0074 (4)	−0.0001 (4)
O2	0.0168 (5)	0.0230 (6)	0.0175 (6)	0.0007 (4)	0.0101 (4)	−0.0028 (4)
O3	0.0182 (5)	0.0211 (6)	0.0189 (6)	0.0023 (4)	0.0038 (5)	0.0018 (5)
C1	0.0155 (7)	0.0202 (7)	0.0153 (7)	−0.0010 (6)	0.0085 (6)	−0.0001 (6)
C2	0.0162 (7)	0.0205 (8)	0.0207 (8)	0.0020 (6)	0.0086 (6)	−0.0017 (6)
C3	0.0161 (7)	0.0180 (7)	0.0214 (8)	−0.0003 (6)	0.0068 (6)	0.0011 (6)
C4	0.0191 (7)	0.0228 (8)	0.0190 (8)	−0.0032 (6)	0.0099 (6)	0.0020 (6)
C5	0.0149 (7)	0.0244 (8)	0.0157 (7)	−0.0013 (6)	0.0090 (6)	−0.0012 (6)
C6	0.0106 (6)	0.0193 (7)	0.0117 (6)	−0.0006 (5)	0.0044 (5)	−0.0008 (5)
C7	0.0111 (6)	0.0203 (7)	0.0094 (6)	−0.0006 (5)	0.0028 (5)	−0.0020 (5)
C8	0.0210 (7)	0.0163 (7)	0.0168 (7)	−0.0002 (6)	0.0118 (6)	−0.0016 (6)
C9	0.0135 (6)	0.0182 (7)	0.0151 (7)	−0.0016 (5)	0.0073 (5)	−0.0007 (5)
C10	0.0163 (7)	0.0168 (7)	0.0139 (7)	0.0002 (5)	0.0081 (6)	0.0007 (5)
C11	0.0173 (7)	0.0226 (8)	0.0154 (7)	0.0020 (6)	0.0096 (6)	0.0026 (6)
C12	0.0226 (8)	0.0229 (8)	0.0282 (9)	0.0072 (6)	0.0155 (7)	0.0058 (7)
C13	0.0307 (9)	0.0178 (8)	0.0343 (10)	0.0040 (7)	0.0203 (8)	0.0044 (7)
C14	0.0258 (8)	0.0201 (8)	0.0280 (9)	−0.0044 (7)	0.0152 (7)	−0.0018 (7)
C15	0.0168 (7)	0.0211 (8)	0.0185 (8)	−0.0005 (6)	0.0082 (6)	0.0000 (6)
C16	0.0140 (7)	0.0303 (9)	0.0204 (8)	0.0018 (6)	0.0072 (6)	−0.0009 (7)

Br1—C3	1.8935 (18)	C8—H8A	0.9900
O1—C9	1.3493 (19)	C8—H8B	0.9900
O1—C8	1.433 (2)	C9—C10	1.490 (2)
O2—C7	1.2170 (19)	C10—C15	1.397 (2)
O3—C9	1.207 (2)	C10—C11	1.407 (2)
C1—C2	1.392 (2)	C11—C12	1.400 (2)
C1—C6	1.396 (2)	C11—C16	1.507 (2)
C1—H1A	0.9500	C12—C13	1.383 (3)
C2—C3	1.386 (2)	C12—H12A	0.9500
C2—H2A	0.9500	C13—C14	1.393 (3)
C3—C4	1.393 (2)	C13—H13A	0.9500
C4—C5	1.386 (2)	C14—C15	1.386 (2)
C4—H4A	0.9500	C14—H14A	0.9500
C5—C6	1.399 (2)	C15—H15A	0.9500
C5—H5A	0.9500	C16—H16A	0.9800
C6—C7	1.491 (2)	C16—H16B	0.9800
C7—C8	1.512 (2)	C16—H16C	0.9800

C9—O1—C8	115.46 (13)	O3—C9—O1	123.39 (15)
C2—C1—C6	120.43 (15)	O3—C9—C10	124.51 (15)
C2—C1—H1A	119.8	O1—C9—C10	112.05 (13)
C6—C1—H1A	119.8	C15—C10—C11	120.62 (15)
C3—C2—C1	118.88 (15)	C15—C10—C9	116.27 (14)
C3—C2—H2A	120.6	C11—C10—C9	123.10 (14)
C1—C2—H2A	120.6	C12—C11—C10	117.24 (15)
C2—C3—C4	121.92 (16)	C12—C11—C16	119.55 (15)
C2—C3—Br1	118.84 (13)	C10—C11—C16	123.17 (15)
C4—C3—Br1	119.24 (13)	C13—C12—C11	121.96 (16)
C5—C4—C3	118.51 (15)	C13—C12—H12A	119.0
C5—C4—H4A	120.7	C11—C12—H12A	119.0
C3—C4—H4A	120.7	C12—C13—C14	120.28 (17)
C4—C5—C6	120.84 (15)	C12—C13—H13A	119.9
C4—C5—H5A	119.6	C14—C13—H13A	119.9
C6—C5—H5A	119.6	C15—C14—C13	118.89 (17)
C1—C6—C5	119.42 (15)	C15—C14—H14A	120.6
C1—C6—C7	122.24 (14)	C13—C14—H14A	120.6
C5—C6—C7	118.33 (14)	C14—C15—C10	120.96 (16)
O2—C7—C6	121.60 (15)	C14—C15—H15A	119.5
O2—C7—C8	121.25 (15)	C10—C15—H15A	119.5
C6—C7—C8	117.14 (13)	C11—C16—H16A	109.5
O1—C8—C7	111.25 (13)	C11—C16—H16B	109.5
O1—C8—H8A	109.4	H16A—C16—H16B	109.5
C7—C8—H8A	109.4	C11—C16—H16C	109.5
O1—C8—H8B	109.4	H16A—C16—H16C	109.5
C7—C8—H8B	109.4	H16B—C16—H16C	109.5
H8A—C8—H8B	108.0

C6—C1—C2—C3	0.6 (2)	C8—O1—C9—O3	−3.7 (2)
C1—C2—C3—C4	−0.9 (3)	C8—O1—C9—C10	178.78 (12)
C1—C2—C3—Br1	178.42 (12)	O3—C9—C10—C15	−40.3 (2)
C2—C3—C4—C5	0.5 (3)	O1—C9—C10—C15	137.23 (15)
Br1—C3—C4—C5	−178.80 (12)	O3—C9—C10—C11	139.03 (17)
C3—C4—C5—C6	0.2 (2)	O1—C9—C10—C11	−43.5 (2)
C2—C1—C6—C5	0.0 (2)	C15—C10—C11—C12	−0.6 (2)
C2—C1—C6—C7	−178.94 (14)	C9—C10—C11—C12	−179.87 (15)
C4—C5—C6—C1	−0.4 (2)	C15—C10—C11—C16	177.21 (16)
C4—C5—C6—C7	178.59 (15)	C9—C10—C11—C16	−2.1 (2)
C1—C6—C7—O2	−174.45 (15)	C10—C11—C12—C13	−1.3 (3)
C5—C6—C7—O2	6.6 (2)	C16—C11—C12—C13	−179.19 (17)
C1—C6—C7—C8	6.2 (2)	C11—C12—C13—C14	1.8 (3)
C5—C6—C7—C8	−172.78 (14)	C12—C13—C14—C15	−0.3 (3)
C9—O1—C8—C7	−75.92 (17)	C13—C14—C15—C10	−1.6 (3)
O2—C7—C8—O1	−0.4 (2)	C11—C10—C15—C14	2.0 (3)
C6—C7—C8—O1	178.89 (12)	C9—C10—C15—C14	−178.63 (15)

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱ	0.99	2.32	3.224 (2)	151
C8—H8B···O2ⁱⁱ	0.99	2.52	3.447 (3)	156
C15—H15A···Cg1ⁱⁱⁱ	0.95	2.74	3.5472 (19)	143
C16—H16B···Cg1^iv	0.98	2.98	3.4909 (19)	114
C2—H2A···Cg2^v	0.95	2.91	3.5915 (19)	130

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O2ⁱ	0.99	2.32	3.224 (2)	151
C8—H8B⋯O2ⁱⁱ	0.99	2.52	3.447 (3)	156
C15—H15A⋯Cg1ⁱⁱⁱ	0.95	2.74	3.5472 (19)	143
C16—H16B⋯Cg1^iv	0.98	2.98	3.4909 (19)	114
C2—H2A⋯Cg2^v	0.95	2.91	3.5915 (19)	130

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

4 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Chain mechanism in the photocleavage of phenacyl and pyridacyl esters in the presence of hydrogen donors.

Authors: Jaromír Literák; Anna Dostálová; Petr Klán
Journal: J Org Chem Date: 2006-01-20 Impact factor: 4.354

3. 2-(4-Bromo-phen-yl)-2-oxoethyl 4-meth-oxy-benzoate.

Authors: Hoong-Kun Fun; Wan-Sin Loh; B Garudachari; Arun M Isloor; M N Satyanarayan
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2011-05-25

4. Structure validation in chemical crystallography.

Authors: Anthony L Spek
Journal: Acta Crystallogr D Biol Crystallogr Date: 2009-01-20