1-(4-Bromo­phen­yl)-3-chloro­propan-1-one

Sonneck, M.; Spannenberg, A.; Wohlrab, S.; Peppel, T.

doi:10.1107/S2414314625006200

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 7| July 2025| x250620

https://doi.org/10.1107/S2414314625006200

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1-(4-Bromophenyl)-3-chloropropan-1-one

Marcel Sonneck,^a Anke Spannenberg,^a Sebastian Wohlrab ^a and Tim Peppel ^a ^*

^aLeibniz-Institut für Katalyse e. V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany
^*Correspondence e-mail: [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 1 July 2025; accepted 14 July 2025; online 23 July 2025)

The title compound, C₉H₈BrClO, crystallizes in the monoclinic space group P2₁/n with four molecules in the unit cell. The molecular structure consists of almost planar molecules with the chlorine atom protruding from this plane.

Keywords: crystal structure; β-chloro ketone; stacking; halogen bond.

CCDC reference: 1495202

Structure description

β-Chloro ketones are useful building blocks for many chemical transformation reactions. They are accessible via different reactions schemes such as Friedel–Crafts acylation (Sartori & Maggi, 2006 ), Wacker-type oxidation (Liu et al., 2017 ), or light-mediated ring opening of aryl cyclopropanes (Petzold et al., 2019 ). The title compound was obtained in moderate yield in single-crystal purity. It can be designated as a suitable building block in the ongoing efforts to synthesize feasible new ligands for Cu-based complexes (Sonneck et al., 2015 , 2016 ).

The molecular structure of the title compound consists of a para-substituted bromophenyl core and a β-chloro-substituted carbonyl side chain (Fig. 1). All carbon atoms, Br1 and O1 form a plane with a mean deviation from the best plane defined by these atoms of 0.029 Å. Cl1 is out of that plane by 1.547 (2) Å. All bond lengths and angles are in expected ranges and the C=O bond length is 1.218 (2) Å. The title compound crystallizes in a layered fashion along the crystallographic a axis (Fig. 2). In the crystal, weak C—H⋯O hydrogen bonds link the molecules (Table 1). The crystal structure is further characterized by type II halogen bonds: Br⋯Clⁱ = 3.4401 (7) Å; θ₁: C—Br⋯Clⁱ = 174.18 (6)°, θ₂: Br⋯Clⁱ—Cⁱ = 103.98 (7)° [symmetry code: (i) x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ] (Metrangolo & Resnati, 2014 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.99	2.31	3.176 (2)	146
C2—H2B⋯O1ⁱⁱ	0.99	2.54	3.535 (2)	178
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title compound with atom labeling and displacement ellipsoids drawn at 50% probability level.

Figure 2
Packing diagram for the title compound along the a axis with displacement ellipsoids drawn at 30% probability level.

Synthesis and crystallization

The title compound was obtained as colorless crystals in moderate yield from the Friedel–Crafts acylation of bromobenzene and 3-chloropropionyl chloride in dichloromethane. AlCl₃ (25.5 g, 191.0 mmol, 1.25 eq.) was suspended in 35 ml of dichloromethane. A solution of 3-chloropropionyl chloride (19.4 g, 152.8 mmol, 1.0 eq.) in 10 ml of dichloromethane was added dropwise under ambient conditions to the AlCl₃ suspension and further stirred for 15 min. Afterwards, a solution of bromobenzene (24.0 g, 152.8 mmol, 1.0 eq.) in 10 ml of dichloromethane was added dropwise at room conditions to the suspension and further stirred for 16 h. The final solution was poured onto ice and concentrated hydrochloric acid (45 g: 15 g). After separation of the organic phase, the aqueous phase was extracted twice with 100 ml portions of diethylether. The combined organic phases were extracted once with 150 ml of saturated aqueous Na₂CO₃ solution, followed by two extractions with 150 ml portions of water, respectively. The organic phase was finally dried over MgSO₄ and the solvent was removed completely under diminished pressure. The solid residue was recrystallized from a solvent mixture of hexanes to yield a slightly yellowish final product (27.8 g, 74%). Colorless single crystals of C₉H₈BrClO were obtained from an acetonic solution by slow evaporation of the solvent at room temperature over the period of one week.

Analytic data for C₉H₈BrClO: m.p. 69°C, elemental analysis % (calc.): C 43.85 (43.67), H 3.18 (3.26); Br 32.37 (32.28); Cl 14.19 (14.32). ¹H NMR (300 MHz, CDCl₃): δ (p.p.m.) = 7.84–7.79 (m, 2H, ArH); 7.65–7.59 (m, 2H, ArH); 3.91 (t, ³J = 6.7 Hz, 2H); 3.42 (t, ³J = 6.7 Hz, 2H); ¹³C NMR (75 MHz, CDCl₃): δ (p.p.m.) = 195.83 (CO); 135.20 (C); 132.22, 132.22, 129.68, 129.68 (CH); 128.96 (C); 41.33, 38.59 (CH₂).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₈BrClO
M_r	247.51
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	4.4730 (7), 9.3707 (15), 22.366 (4)
β (°)	94.989 (3)
V (Å³)	933.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.63
Crystal size (mm)	0.42 × 0.30 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.41, 0.60
No. of measured, independent and observed [I > 2σ(I)] reflections	9215, 2037, 1780
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.058, 1.03
No. of reflections	2037
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.37
Computer programs: APEX2 (Bruker, 2014 ), SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1495202

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625006200/bt4177sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625006200/bt4177Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625006200/bt4177Isup3.cml

checkCIF report

Computing details top

1-(4-Bromophenyl)-3-chloropropan-1-one top

Crystal data top

C₉H₈BrClO	F(000) = 488
M_r = 247.51	D_x = 1.760 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.4730 (7) Å	Cell parameters from 4023 reflections
b = 9.3707 (15) Å	θ = 2.2–28.0°
c = 22.366 (4) Å	µ = 4.63 mm⁻¹
β = 94.989 (3)°	T = 150 K
V = 933.9 (3) Å³	Plate, colourless
Z = 4	0.42 × 0.30 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	2037 independent reflections
Radiation source: fine-focus sealed tube	1780 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.026
φ and ω scans	θ_max = 27.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −5→5
T_min = 0.41, T_max = 0.60	k = −11→11
9215 measured reflections	l = −28→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.028P)² + 0.3453P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.004
2037 reflections	Δρ_max = 0.37 e Å⁻³
109 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints

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. Hydrogen atoms were located in a difference map and refined as riding on their parent atoms with U(H)=1.2U_eq(C) and with C_aromatic—H=0.95 Å or with C_methylene—H=0.99 Å.

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

	x	y	z	U_iso*/U_eq
Br1	1.42604 (5)	0.77477 (2)	1.02881 (2)	0.04497 (9)
C1	0.2245 (5)	0.7340 (2)	0.71439 (11)	0.0405 (5)
H1A	0.077806	0.810098	0.702401	0.049*
H1B	0.111428	0.648575	0.725442	0.049*
C2	0.4251 (4)	0.78300 (19)	0.76779 (9)	0.0323 (4)
H2A	0.301478	0.831498	0.796299	0.039*
H2B	0.569695	0.853619	0.754374	0.039*
C3	0.5973 (4)	0.66257 (19)	0.80011 (9)	0.0326 (4)
C4	0.7958 (4)	0.69450 (19)	0.85496 (9)	0.0317 (4)
C5	0.9448 (4)	0.5819 (2)	0.88552 (10)	0.0391 (5)
H5	0.916508	0.487417	0.870675	0.047*
C6	1.1317 (5)	0.6049 (2)	0.93664 (10)	0.0409 (5)
H6	1.231700	0.527279	0.957094	0.049*
C7	1.1722 (5)	0.7430 (2)	0.95792 (9)	0.0354 (4)
C8	1.0295 (5)	0.8566 (2)	0.92856 (9)	0.0369 (4)
H8	1.060492	0.950893	0.943426	0.044*
C9	0.8415 (4)	0.8323 (2)	0.87750 (9)	0.0356 (4)
H9	0.741597	0.910338	0.857366	0.043*
Cl1	0.43714 (12)	0.69179 (5)	0.65212 (2)	0.04357 (14)
O1	0.5732 (3)	0.54110 (14)	0.78086 (7)	0.0461 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.05104 (15)	0.04894 (15)	0.03549 (13)	0.00654 (9)	0.00697 (9)	0.00511 (9)
C1	0.0265 (9)	0.0303 (10)	0.0646 (14)	0.0023 (8)	0.0027 (9)	−0.0085 (9)
C2	0.0295 (9)	0.0223 (9)	0.0462 (11)	0.0010 (7)	0.0102 (8)	−0.0044 (8)
C3	0.0336 (9)	0.0220 (9)	0.0444 (11)	−0.0017 (7)	0.0162 (8)	0.0018 (8)
C4	0.0362 (10)	0.0219 (9)	0.0394 (10)	0.0001 (7)	0.0168 (8)	0.0037 (7)
C5	0.0461 (11)	0.0209 (9)	0.0517 (13)	0.0034 (8)	0.0122 (10)	0.0036 (8)
C6	0.0462 (11)	0.0304 (10)	0.0478 (12)	0.0090 (8)	0.0129 (10)	0.0093 (9)
C7	0.0377 (10)	0.0380 (11)	0.0323 (10)	0.0027 (8)	0.0138 (8)	0.0046 (8)
C8	0.0519 (12)	0.0258 (9)	0.0344 (10)	0.0018 (8)	0.0116 (9)	0.0000 (8)
C9	0.0479 (11)	0.0230 (9)	0.0371 (11)	0.0034 (8)	0.0112 (9)	0.0043 (8)
Cl1	0.0478 (3)	0.0371 (3)	0.0442 (3)	0.0059 (2)	−0.0056 (2)	−0.0114 (2)
O1	0.0597 (9)	0.0189 (7)	0.0595 (10)	−0.0032 (6)	0.0031 (7)	−0.0020 (6)

Geometric parameters (Å, º) top

Br1—C7	1.892 (2)	C4—C9	1.394 (3)
C1—C2	1.502 (3)	C4—C5	1.395 (3)
C1—Cl1	1.798 (2)	C5—C6	1.374 (3)
C1—H1A	0.9900	C5—H5	0.9500
C1—H1B	0.9900	C6—C7	1.385 (3)
C2—C3	1.514 (3)	C6—H6	0.9500
C2—H2A	0.9900	C7—C8	1.378 (3)
C2—H2B	0.9900	C8—C9	1.377 (3)
C3—O1	1.218 (2)	C8—H8	0.9500
C3—C4	1.481 (3)	C9—H9	0.9500

C2—C1—Cl1	111.33 (14)	C5—C4—C3	118.65 (17)
C2—C1—H1A	109.4	C6—C5—C4	121.30 (18)
Cl1—C1—H1A	109.4	C6—C5—H5	119.4
C2—C1—H1B	109.4	C4—C5—H5	119.4
Cl1—C1—H1B	109.4	C5—C6—C7	118.98 (18)
H1A—C1—H1B	108.0	C5—C6—H6	120.5
C1—C2—C3	113.32 (16)	C7—C6—H6	120.5
C1—C2—H2A	108.9	C8—C7—C6	121.1 (2)
C3—C2—H2A	108.9	C8—C7—Br1	119.80 (15)
C1—C2—H2B	108.9	C6—C7—Br1	119.09 (15)
C3—C2—H2B	108.9	C9—C8—C7	119.43 (18)
H2A—C2—H2B	107.7	C9—C8—H8	120.3
O1—C3—C4	120.65 (17)	C7—C8—H8	120.3
O1—C3—C2	120.12 (18)	C8—C9—C4	120.85 (18)
C4—C3—C2	119.23 (16)	C8—C9—H9	119.6
C9—C4—C5	118.32 (19)	C4—C9—H9	119.6
C9—C4—C3	123.02 (17)

Cl1—C1—C2—C3	−75.11 (19)	C4—C5—C6—C7	−0.1 (3)
C1—C2—C3—O1	2.5 (3)	C5—C6—C7—C8	−0.2 (3)
C1—C2—C3—C4	−177.81 (16)	C5—C6—C7—Br1	179.31 (15)
O1—C3—C4—C9	177.21 (18)	C6—C7—C8—C9	0.6 (3)
C2—C3—C4—C9	−2.4 (3)	Br1—C7—C8—C9	−179.01 (15)
O1—C3—C4—C5	−2.6 (3)	C7—C8—C9—C4	−0.5 (3)
C2—C3—C4—C5	177.73 (17)	C5—C4—C9—C8	0.1 (3)
C9—C4—C5—C6	0.2 (3)	C3—C4—C9—C8	−179.70 (17)
C3—C4—C5—C6	−179.99 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.99	2.31	3.176 (2)	146
C2—H2B···O1ⁱⁱ	0.99	2.54	3.535 (2)	178

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

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