Crystal structure of 2-(4-chloro­phen­yl)-2-oxoethyl 3-bromo­benzoate

Khan, I.; Ibrar, A.; Hameed, S.; White, J.M.; Simpson, J.

doi:10.1107/S1600536814021643

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 301-304

doi:10.1107/S1600536814021643

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Crystal structure of 2-(4-chlorophenyl)-2-oxoethyl 3-bromobenzoate

Imtiaz Khan,^a,^b Aliya Ibrar,^a Shahid Hameed,^a Jonathan M. White ^c and Jim Simpson ^d ^*

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bSchool of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, England, ^cSchool of Chemistry and Bio-21 Institute, University of Melbourne, Parkville, Victoria 3052, Australia, and ^dDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

Edited by P. C. Healy, Griffith University, Australia (Received 27 September 2014; accepted 1 October 2014; online 8 October 2014)

2-(4-Chlorophenyl)-2-oxoethyl 3-bromobenzoate, C₁₅H₁₀BrClO₃, was synthesized in a single-step reaction by condensation of 3-bromobenzoic acid with 2-bromo-1-(4-chlorophenyl)ethanone in dimethylformamide in the presence of triethylamine as a catalyst. The structure consists of an aryl ketone moiety linked to an aryl ester unit by a methylene group. Both units are reasonably planar (r.m.s. deviations of 0.119 and 0.010 Å for the aryl ketone and aryl ester units, respectively) and are almost orthogonal, with an angle of 88.60 (3)° between them. In the crystal, molecules form five separate sets of inversion dimers. Three of these are generated by two C—H⋯O interactions and a C—H⋯Br contact, and form chains along c and along the ab cell diagonal. In addition, two inversion-related π–π stacking interactions between like aryl rings again form chains of molecules but in this instance along the bc diagonal. These contacts generate infinite layers of molecules parallel to (011) and stack the molecules along the a-axis direction.

Keywords: crystal structure; 2-(4-chlorophenyl)-2-oxoethyl 3-bromobenzoate; synthesis; π–π interactions; inversion dimers.

CCDC reference: 864789

1. Chemical context

Keto esters, an important class of versatile intermediates, have been reported to show antitumor activity against Ehrlich cells and HeLa cells (Kinoshita & Umezawa, 1960 ). They also regulate the flowering times of some plants (Kai et al., 2007 ). Recent studies have revealed that they also exhibit inhibitory activity against two isozymes of 11β-hydroxysteroid dehydrogenases (11β-HSD1 and 11β-HSD2), which catalyse the interconversion of active cortisol and inactive cortisone (Zhang et al., 2009 ). Dicarbonyl compounds and their derivatives are also among the most versatile and frequently employed synthons in organic synthesis, especially in heterocyclic chemistry (Stanovnik & Svete, 2004 ; Sheibani et al., 2006a ,b , 2007 ; Pal et al., 2008 ). In this work, we report the synthesis of 2-(4-chlorophenyl)-2-oxoethyl 3-bromobenzoate, (1), which may be used as an effective synthon in organic chemistry.

Figure 1
Fig, 1. The structure of (1) with displacement ellipsoids drawn at the 50% probability level.

2. Structural commentary

The structure of (1) consists of an aryl ketone moiety linked to an aryl ester unit by the C8 methylene group and both groupings are reasonably planar. There is an r.m.s. deviation of 0.119 Å from the best-fit plane through atoms Br1, C1–C8, O1, O2 [maximum deviation 0.2477 (11) Å for O1] while the plane of the carboxylate unit subtends an angle of 15.5 (2)° to that of the bromobenzene ring. In addition, the plane of the aryl ketone unit C8–C15, O3, Cl1 has an r.m.s. deviation of 0.010 Å [maximum deviation 0.0171 (15) Å for C15]. The aryl ketone and aryl ester planes are almost orthogonal with an angle of 88.61 (3)° between them. Bond lengths and angles in the molecule are normal and are generally similar to those found in closely related molecules (see for example Fun et al., 2011a ; Chidan Kumar et al., 2014c ).

3. Supramolecular features

In the crystal structure, each molecule forms five separate inversion dimers. C8—H8B⋯O1 and C15—H15 O3 hydrogen bonds each generate R₂²(10) rings, forming zigzag chains along c. Additional C4—H4⋯Br1 contacts also form inversion dimers with R₂²(8) rings and these combine with the C8—H8B⋯O1 contacts to link alternating pairs of dimers into infinite chains approximately along the ab cell diagonal, Table 1, Fig. 2. Interestingly, infinite chains of alternating inversion dimers also result from a pair of π–π stacking interactions between adjacent 3-bromophenyl rings, Cg1⋯Cg1^iv = 3.6987 (10) Å, and neighbouring 4-chlorophenyl rings Cg2⋯Cg2^v = 3.8585 (11) Å, in this case along the bc diagonal, Fig. 3 [Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively; symmetry codes (iv) −x, 2 − y, −z; (v) 2 − x, 1 − y, 1 − z]. These contacts combine to generate extended layers of molecules parallel to (011), Fig. 4, and to stack molecules along the a-axis direction, Fig. 5.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Br1ⁱ	0.95	2.97	3.8762 (18)	160
C8—H8B⋯O1ⁱⁱ	0.99	2.42	3.396 (2)	168
C15—H15⋯O3ⁱⁱⁱ	0.95	2.60	3.418 (2)	144
Symmetry codes: (i) -x-1, -y+2, -z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1.

Figure 2
Chains of linked inversion dimers generated by C—H⋯O and C—H⋯Br hydrogen bonds, drawn as dashed lines.

Figure 3
A chain of inversion dimers generated by π–π contacts, dotted green lines, between 3-bromophenyl and 4-chlorophenyl rings. Ring centroids are displayed as coloured spheres.

Figure 4
Overall packing of (1) viewed at right angles to (011).

Figure 5
Overall packing of (1) viewed along the a-axis direction.

4. Database survey

A search of the Cambridge Crystallographic Database (Groom & Allen, 2014 ) reveals only eight structures with the 2-oxo-2-phenylethyl benzoate skeleton. These include the archetypal 2-oxo-2-phenylethyl benzoate (Fun et al., 2011a), three additional 2-(4-chlorophenyl)-2-oxoethyl derivatives (Fun et al., 2011b ; Chidan Kumar et al., 2014a ,b ) and the corresponding compound 2-(4-bromophenyl)-2-oxoethyl 3-chlorobenzoate with the chloro- and bromo-substituents reversed (Chidan Kumar et al., 2014c). Interestingly, inversion-dimer formation is a feature of the packing in several of these structures.

5. Synthesis and crystallization

The preparation followed a procedure developed for the preparation of a related compound (Khan et al., 2012 ). Triethylamine (4–5 drops) was added at room temperature to a stirred solution of 3-bromobenzoic acid (1.0 mmol) in N,N-dimethylformamide (DMF), followed by a solution of 2-bromo-1-(4-chlorophenyl)ethanone (1.0 mmol). The reaction mixture was stirred for 2 h. Progress of the reaction was monitored by TLC. After completion, the mixture was poured into water and the precipitated solid was filtered, dried and recrystallized (EtOAc/hexane) to afford 2-(4-chlorophenyl)-2-oxoethyl 3-bromobenzoate (1). The formation of keto ester (3) was indicated by the appearance of two typical stretching vibrations ν(C=O) ester (1724) and ν(C=O) keto (1698) cm⁻¹, respectively and the disappearance of characteristic IR stretching absorptions ascribable to the carboxylic acid group in the region of 3400–2400 cm⁻¹. In the ¹H NMR spectrum, the signals for the aromatic protons appeared in their respective regions and the disappearance of a characteristic signal for the COOH proton confirmed the formation of the title compound (1). The ¹³C NMR spectrum displayed two characteristic signals for the keto and ester carbonyl carbon atoms at 190.7 and 165.3 p.p.m., respectively. Yield: 88%; m.p. 372–373 K; R_f: 0.72 (10% EtOAc/hexane); IR (ATR, cm⁻¹): 3089 (Csp²-H), 2933, 2856 (Csp³-H), 1724 (C=O ester), 1698 (C=O ketone), 1585, 1479 (C=C Ar), 1225 (C—O); ¹H NMR (300 MHz, CDCl₃): δ 8.06–8.03 (m, 1H, Ar-H), 7.94–7.90 (m, 2H, Ar-H), 7.73–7.70 (m, 1H, Ar-H), 7.52–7.48 (m, 2H, Ar-H), 7.46–7.36 (m, 2H, Ar-H), 5.57 (s, 2H, CH₂); ¹³C NMR (75 MHz, CDCl₃): δ 190.7, 165.3, 140.6, 134.5, 133.1, 132.4, 132.0, 131.0, 129.3, 129.3, 127.3, 122.1, 66.5.

6. Refinement

All H atoms were refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic, and C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C) for the methylene H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₀BrClO₃
M_r	353.59
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	130
a, b, c (Å)	6.6797 (3), 10.0238 (4), 10.7851 (5)
α, β, γ (°)	90.980 (4), 107.573 (4), 92.138 (3)
V (Å³)	687.64 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.19
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas CCD)
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011 )
T_min, T_max	0.505, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10822, 3327, 3062
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.064, 1.05
No. of reflections	3327
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.60
Computer programs: CrysAlis PRO, (Agilent, 2011), SHELXS97 and SHELXL2014 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), enCIFer (Allen et al., 2004 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 864789

Crystal structure: contains datablocks global, 1. DOI: 10.1107/S1600536814021643/hg5410sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S1600536814021643/hg54101sup2.hkl

checkCIF report

Chemical context top

Keto esters, an important class of versatile intermediates, have been reported to show antitumor activity against Ehrlich cells and HeLa cells (Kinoshita & Umezawa, 1960). They also regulate the flowering times of some plants (Kai et al., 2007). Recent studies have revealed that they also exhibit inhibitory activity against two isozymes of 11β-hydroxysteroid dehydrogenases (11β-HSD1 and 11β-HSD2), which catalyse the interconversion of active cortisol and inactive cortisone (Zhang et al., 2009). Dicarbonyl compounds and their derivatives are also among the most versatile and frequently employed synthons in organic synthesis, especially in heterocyclic chemistry (Stanovnik & Svete, 2004; Sheibani et al., 2006a,b, 2007; Pal et al., 2008). In this work, we report the synthesis of 2-(4-chlorophenyl)-2-oxoethyl 3-bromobenzoate, (1), which may be used as an effective synthon in heterocyclic chemistry.

Structural commentary top

Supramolecular features top

In the crystal structure, each molecule forms three discrete inversion dimers. C8—H8B···O1 and C15—H15 O3 hydrogen bonds each generate R²₂(10) rings, forming zigzag chains along c. Additional C4—H4···Br1 contacts also form inversion dimers with R²₂(8) rings and these combine with the C8—H8B···O1 contacts to link alternating pairs of dimers into infinite chains approximately along the ab cell diagonal, Table 1, Fig. 2. Interestingly, infinite chains of alternating inversion dimers also result from a pair of π–π stacking interactions between adjacent 3-bromophenyl rings, Cg1···Cg1^iv = 3.6987 (10) Å, and neighbouring 4-chlorophenyl rings Cg2···Cg2^v = 3.8585 (11) Å, in this case along the bc diagonal, Fig. 3 [Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively; symmetry codes (iv) -x, 2-y, -z; (v) 2-x, 1-y, 1-z]. These contacts combine to generate extended layers of molecules parallel to (011), Fig. 4, and to stack molecules along the a-axis direction, Fig. 5.

Database survey top

A search of the Cambridge Crystallographic Database (Groom & Allen, 2014) reveals only eight structures with the 2-oxo-2-phenylethyl benzoate skeleton. These include the archetypal 2-oxo-2-phenylethyl benzoate (Fun et al., 2011a), three additional 2-(4-chlorophenyl)-2-oxoethyl derivatives (Fun et al., 2011b; Chidan Kumar et al., 2014a,b) and the corresponding compound 2-(4-bromophenyl)-2-oxoethyl 3-chlorobenzoate with the chloro- and bromo-substituents reversed (Chidan Kumar et al., 2014c).

Synthesis and crystallization top

Triethylamine (4–5 drops) was added at room temperature to a stirred solution of 3-bromobenzoic acid (1.0 mmol) in N,N-dimethylformamide (DMF), followed by a solution of 2-bromo-1-(4-chlorophenyl)ethanone (1.0 mmol). The reaction mixture was stirred for 2 h (Khan et al., 2012). Progress of the reaction was monitored by TLC. After completion, the mixture was poured into water and the precipitated solid was filtered, dried and recrystallized (EtOAc/hexane) to afford 2-(4-chlorophenyl)-2-oxoethyl 3-bromobenzoate (1). The formation of keto ester (3) was indicated by the appearance of two typical stretching vibrations ν(C=O) ester (1724) and ν(C=O) keto (1698) cm^-1, respectively and the disappearance of characteristic IR stretching absorptions ascribable to the carboxylic acid group in the region of 3400–2400 cm^-1. In the ¹H NMR spectrum, the signals for the aromatic protons appeared in their respective regions and the disappearance of a characteristic signal for the COOH proton confirmed the formation of the title compound (1). The ¹³C NMR spectrum displayed two characteristic signals for the keto and ester carbonyl carbon atoms at 190.7 and 165.3 p.p.m., respectively. Yield: 88%; m.p. 372–373 K; R_f: 0.72 (10% EtOAc/hexane); IR (ATR, cm^-1): 3089 (Csp²-H), 2933, 2856 (Csp³-H), 1724 (C=O ester), 1698 (C=O ketone), 1585, 1479 (C=C Ar), 1225 (C—O); ¹H NMR (300 MHz, CDCl₃): δ 8.06–8.03 (m, 1H, Ar—H), 7.94–7.90 (m, 2H, Ar—H), 7.73–7.70 (m, 1H, Ar—H), 7.52–7.48 (m, 2H, Ar—H), 7.46–7.36 (m, 2H, Ar—H), 5.57 (s, 2H, CH₂); ¹³C NMR (75 MHz, CDCl₃): δ 190.7, 165.3, 140.6, 134.5, 133.1, 132.4, 132.0, 131.0, 129.3, 129.3, 127.3, 122.1, 66.5.

Refinement top

All H atoms were refined using a riding model, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic, and C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C) for the methylene H atoms.

Related literature top

For related literature, see: Chidan Kumar, Chia, Chandraju, Ooi, Quah & Fun (2014c); Chidan Kumar, Yohannan Panicker, Fun, Sheena Mary, Harikumar, Chandraju, Quah & Ooi (2014a, 2014b); Fun et al. (2011a, 2011b); Kai et al. (2007); Khan et al. (2012); Kinoshita & Umezawa (1960); Pal et al. (2008); Sheibani et al. (2006a, 2006b, 2007); Stanovnik & Svete (2004); Zhang et al. (2009).

Computing details top

Data collection: CrysAlis PRO, (Agilent, 2011); cell refinement: CrysAlis PRO, (Agilent, 2011); data reduction: CrysAlis PRO, (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

Fig, 1. The structure of (1) with displacement ellipsoids drawn at the 50% probability level.

Fig. 2. Chains of linked inversion dimers generated by C—H···O and C—H···Br hydrogen bonds, drawn as dashed lines.

Fig. 3. A chain of inversion dimers generated by π–π contacts, dotted green lines, between 3-bromophenyl and 4-chlorophenyl rings. Ring centroids are displayed as coloured spheres.

Fig 4. Overall packing of (1) viewed at right angles to (011).

Fig. 5 Overall packing of (1) viewed along the a-axis direction.

2-(4-Chlorophenyl)-2-oxoethyl 3-bromobenzoate top

Crystal data top

C₁₅H₁₀BrClO₃	Z = 2
M_r = 353.59	F(000) = 352
Triclinic, P1	D_x = 1.708 Mg m⁻³
a = 6.6797 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0238 (4) Å	Cell parameters from 6648 reflections
c = 10.7851 (5) Å	θ = 3.2–29.2°
α = 90.980 (4)°	µ = 3.19 mm⁻¹
β = 107.573 (4)°	T = 130 K
γ = 92.138 (3)°	Block, colourless
V = 687.64 (5) Å³	0.50 × 0.40 × 0.20 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer	3327 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3062 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.033
ω scans	θ_max = 29.2°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −8→8
T_min = 0.504, T_max = 1.000	k = −13→13
10822 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0307P)² + 0.1071P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3327 reflections	Δρ_max = 0.35 e Å⁻³
181 parameters	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₅H₁₀BrClO₃	γ = 92.138 (3)°
M_r = 353.59	V = 687.64 (5) Å³
Triclinic, P1	Z = 2
a = 6.6797 (3) Å	Mo Kα radiation
b = 10.0238 (4) Å	µ = 3.19 mm⁻¹
c = 10.7851 (5) Å	T = 130 K
α = 90.980 (4)°	0.50 × 0.40 × 0.20 mm
β = 107.573 (4)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer	3327 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3062 reflections with I > 2σ(I)
T_min = 0.504, T_max = 1.000	R_int = 0.033
10822 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.05	Δρ_max = 0.35 e Å⁻³
3327 reflections	Δρ_min = −0.60 e Å⁻³
181 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent (2011), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1452 (3)	0.76183 (16)	0.09834 (16)	0.0153 (3)
C2	−0.0463 (3)	0.73719 (17)	0.00240 (16)	0.0165 (3)
H2	−0.0671	0.6625	−0.0562	0.020*
C3	−0.2052 (3)	0.82374 (17)	−0.00564 (16)	0.0164 (3)
C4	−0.1816 (3)	0.93075 (18)	0.08011 (17)	0.0200 (4)
H4	−0.2944	0.9879	0.0739	0.024*
C5	0.0097 (3)	0.95371 (18)	0.17577 (17)	0.0213 (4)
H5	0.0280	1.0271	0.2356	0.026*
C6	0.1742 (3)	0.87044 (17)	0.18485 (17)	0.0189 (3)
H6	0.3057	0.8874	0.2496	0.023*
C7	0.3120 (3)	0.66531 (17)	0.10555 (16)	0.0169 (3)
C8	0.6639 (3)	0.62000 (17)	0.20718 (17)	0.0182 (3)
H8A	0.8031	0.6678	0.2388	0.022*
H8B	0.6573	0.5687	0.1266	0.022*
C9	0.6368 (3)	0.52539 (17)	0.30950 (16)	0.0176 (3)
C10	0.8001 (3)	0.42573 (17)	0.35889 (16)	0.0166 (3)
C11	0.9739 (3)	0.41710 (18)	0.31370 (17)	0.0201 (4)
H11	0.9919	0.4770	0.2502	0.024*
C12	1.1213 (3)	0.32135 (19)	0.36109 (18)	0.0231 (4)
H12	1.2400	0.3152	0.3305	0.028*
C13	1.0919 (3)	0.23586 (18)	0.45295 (18)	0.0229 (4)
C14	0.9204 (3)	0.24247 (19)	0.49972 (18)	0.0242 (4)
H14	0.9029	0.1821	0.5630	0.029*
C15	0.7757 (3)	0.33824 (19)	0.45280 (17)	0.0215 (4)
H15	0.6584	0.3446	0.4848	0.026*
O1	0.28187 (18)	0.55756 (12)	0.05094 (12)	0.0222 (3)
O2	0.50195 (18)	0.71409 (12)	0.17991 (12)	0.0186 (3)
O3	0.48450 (19)	0.53074 (14)	0.34811 (13)	0.0257 (3)
Cl1	1.27582 (8)	0.11559 (5)	0.51284 (5)	0.03372 (13)
Br1	−0.46435 (2)	0.79269 (2)	−0.13927 (2)	0.02456 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0181 (8)	0.0132 (8)	0.0156 (8)	0.0008 (6)	0.0067 (7)	0.0013 (6)
C2	0.0189 (8)	0.0136 (8)	0.0178 (8)	−0.0008 (6)	0.0069 (7)	−0.0010 (6)
C3	0.0165 (8)	0.0160 (9)	0.0160 (8)	−0.0002 (6)	0.0039 (7)	0.0007 (6)
C4	0.0244 (9)	0.0160 (9)	0.0213 (9)	0.0033 (7)	0.0091 (7)	−0.0003 (7)
C5	0.0288 (9)	0.0157 (9)	0.0196 (9)	0.0016 (7)	0.0078 (8)	−0.0043 (7)
C6	0.0219 (8)	0.0167 (9)	0.0164 (8)	−0.0014 (7)	0.0035 (7)	−0.0012 (6)
C7	0.0166 (8)	0.0178 (9)	0.0159 (8)	−0.0010 (6)	0.0043 (7)	0.0009 (6)
C8	0.0159 (8)	0.0179 (9)	0.0206 (9)	0.0023 (6)	0.0049 (7)	−0.0008 (7)
C9	0.0181 (8)	0.0192 (9)	0.0142 (8)	−0.0007 (6)	0.0035 (7)	−0.0043 (6)
C10	0.0179 (8)	0.0154 (9)	0.0144 (8)	−0.0023 (6)	0.0021 (7)	−0.0035 (6)
C11	0.0217 (8)	0.0187 (9)	0.0204 (9)	0.0004 (7)	0.0071 (7)	−0.0001 (7)
C12	0.0187 (8)	0.0241 (10)	0.0256 (10)	0.0009 (7)	0.0055 (8)	−0.0029 (7)
C13	0.0258 (9)	0.0169 (9)	0.0188 (9)	0.0036 (7)	−0.0041 (7)	−0.0050 (7)
C14	0.0314 (10)	0.0206 (10)	0.0181 (9)	−0.0022 (7)	0.0037 (8)	0.0015 (7)
C15	0.0227 (9)	0.0238 (10)	0.0174 (9)	−0.0021 (7)	0.0058 (7)	−0.0024 (7)
O1	0.0204 (6)	0.0167 (7)	0.0272 (7)	0.0018 (5)	0.0043 (5)	−0.0065 (5)
O2	0.0154 (6)	0.0162 (6)	0.0218 (6)	0.0014 (5)	0.0019 (5)	−0.0017 (5)
O3	0.0224 (6)	0.0325 (8)	0.0262 (7)	0.0046 (5)	0.0127 (6)	0.0037 (6)
Cl1	0.0352 (3)	0.0251 (3)	0.0316 (3)	0.0110 (2)	−0.0049 (2)	−0.0012 (2)
Br1	0.01750 (10)	0.02591 (12)	0.02626 (12)	0.00457 (7)	0.00057 (8)	−0.00652 (8)

Geometric parameters (Å, º) top

C1—C6	1.391 (2)	C8—H8A	0.9900
C1—C2	1.391 (2)	C8—H8B	0.9900
C1—C7	1.488 (2)	C9—O3	1.212 (2)
C2—C3	1.380 (2)	C9—C10	1.490 (2)
C2—H2	0.9500	C10—C11	1.393 (2)
C3—C4	1.377 (2)	C10—C15	1.393 (2)
C3—Br1	1.8995 (16)	C11—C12	1.391 (2)
C4—C5	1.387 (3)	C11—H11	0.9500
C4—H4	0.9500	C12—C13	1.374 (3)
C5—C6	1.386 (2)	C12—H12	0.9500
C5—H5	0.9500	C13—C14	1.387 (3)
C6—H6	0.9500	C13—Cl1	1.7429 (18)
C7—O1	1.202 (2)	C14—C15	1.379 (3)
C7—O2	1.348 (2)	C14—H14	0.9500
C8—O2	1.4283 (19)	C15—H15	0.9500
C8—C9	1.515 (2)

C6—C1—C2	120.59 (15)	C9—C8—H8B	109.7
C6—C1—C7	122.35 (15)	H8A—C8—H8B	108.2
C2—C1—C7	117.04 (15)	O3—C9—C10	121.67 (15)
C3—C2—C1	118.46 (16)	O3—C9—C8	120.25 (15)
C3—C2—H2	120.8	C10—C9—C8	118.08 (14)
C1—C2—H2	120.8	C11—C10—C15	119.46 (16)
C4—C3—C2	122.08 (16)	C11—C10—C9	122.21 (15)
C4—C3—Br1	119.44 (13)	C15—C10—C9	118.33 (15)
C2—C3—Br1	118.49 (13)	C12—C11—C10	120.38 (16)
C3—C4—C5	118.85 (16)	C12—C11—H11	119.8
C3—C4—H4	120.6	C10—C11—H11	119.8
C5—C4—H4	120.6	C13—C12—C11	118.76 (17)
C6—C5—C4	120.58 (17)	C13—C12—H12	120.6
C6—C5—H5	119.7	C11—C12—H12	120.6
C4—C5—H5	119.7	C12—C13—C14	122.01 (17)
C5—C6—C1	119.41 (16)	C12—C13—Cl1	119.05 (15)
C5—C6—H6	120.3	C14—C13—Cl1	118.94 (14)
C1—C6—H6	120.3	C15—C14—C13	118.85 (17)
O1—C7—O2	124.03 (15)	C15—C14—H14	120.6
O1—C7—C1	124.27 (15)	C13—C14—H14	120.6
O2—C7—C1	111.69 (15)	C14—C15—C10	120.54 (17)
O2—C8—C9	109.80 (13)	C14—C15—H15	119.7
O2—C8—H8A	109.7	C10—C15—H15	119.7
C9—C8—H8A	109.7	C7—O2—C8	114.81 (13)
O2—C8—H8B	109.7

C6—C1—C2—C3	0.7 (2)	C8—C9—C10—C11	−0.3 (2)
C7—C1—C2—C3	179.07 (14)	O3—C9—C10—C15	−0.7 (3)
C1—C2—C3—C4	−1.8 (2)	C8—C9—C10—C15	−179.85 (16)
C1—C2—C3—Br1	178.47 (11)	C15—C10—C11—C12	0.5 (3)
C2—C3—C4—C5	1.4 (3)	C9—C10—C11—C12	−179.10 (16)
Br1—C3—C4—C5	−178.85 (12)	C10—C11—C12—C13	0.0 (3)
C3—C4—C5—C6	0.1 (3)	C11—C12—C13—C14	−0.1 (3)
C4—C5—C6—C1	−1.1 (3)	C11—C12—C13—Cl1	180.00 (14)
C2—C1—C6—C5	0.7 (2)	C12—C13—C14—C15	−0.3 (3)
C7—C1—C6—C5	−177.59 (15)	Cl1—C13—C14—C15	179.61 (14)
C6—C1—C7—O1	164.73 (17)	C13—C14—C15—C10	0.8 (3)
C2—C1—C7—O1	−13.6 (2)	C11—C10—C15—C14	−0.9 (3)
C6—C1—C7—O2	−15.9 (2)	C9—C10—C15—C14	178.71 (16)
C2—C1—C7—O2	165.76 (13)	O1—C7—O2—C8	−9.5 (2)
O2—C8—C9—O3	5.4 (2)	C1—C7—O2—C8	171.15 (13)
O2—C8—C9—C10	−175.45 (14)	C9—C8—O2—C7	−75.86 (17)
O3—C9—C10—C11	178.89 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Br1ⁱ	0.95	2.97	3.8762 (18)	160
C8—H8B···O1ⁱⁱ	0.99	2.42	3.396 (2)	168
C15—H15···O3ⁱⁱⁱ	0.95	2.60	3.418 (2)	144

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Br1ⁱ	0.95	2.97	3.8762 (18)	159.5
C8—H8B···O1ⁱⁱ	0.99	2.42	3.396 (2)	168.3
C15—H15···O3ⁱⁱⁱ	0.95	2.60	3.418 (2)	144.2

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀BrClO₃
M_r	353.59
Crystal system, space group	Triclinic, P1
Temperature (K)	130
a, b, c (Å)	6.6797 (3), 10.0238 (4), 10.7851 (5)
α, β, γ (°)	90.980 (4), 107.573 (4), 92.138 (3)
V (Å³)	687.64 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.19
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.504, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10822, 3327, 3062
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.064, 1.05
No. of reflections	3327
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.60

Computer programs: CrysAlis PRO, (Agilent, 2011), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

We thank the Chemistry Department, University of Otago, for support of the work of JS.

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Volume 70| Part 11| November 2014| Pages 301-304

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