research communications
of 1-(4-bromophenyl)but-3-yn-1-one
aDivision of Organic Synthesis, CSIR-National Chemical Laboratory, Dr. Homi, Bhabha Road, Pashan, Pune-411008, India, bAcademy of Scientific and Innovative Research (AcSIR), Sector 19, Kamla Nehru Nagar, Ghaziabad, Uttar Pradesh 201002, India, and cPhysical & Materials Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune-411008, India
*Correspondence e-mail: rg.gonnade@ncl.res.in
The title compound, 1-(4-bromophenyl)but-3-yn-1-one, C10H7BrO, crystallizes in the monoclinic P21/n with one molecule in the The structure displays a planar geometry. The is consolidated by C—H⋯O hydrogen bonding and a short C=O⋯C≡C (acetylene) contacts. Hirshfeld surface analysis indicates that H⋯H, C⋯H/H⋯C and H⋯Br/Br⋯H interactions play a more important role in consolidating the compared to H⋯O/O⋯H and C⋯C contacts.
CCDC reference: 2268276
1. Chemical context
The title compound 1-(4-bromophenyl)but-3-yn-1-one (1) was obtained as a side product during the synthesis of 5-(4-bromophenyl)isoxazole-3-carboxylic acid (2) from the NaOH-mediated hydrolysis of ethyl 5-(4-bromophenyl)isoxazole-3-carboxylate (3). These arylisoxazole carboxylic acids have been identified as potential isosteres of aryl diketo acid in the design of novel HIV-1 integrase inhibitors (Zeng et al., 2008). The presence of three distinct functional groups, viz. alkyne, bromo, and carbonyl, offers an intriguing opportunity to explore how intermolecular interactions contribute to the cohesion of the crystal structure.
2. Structural commentary
The title compound crystallizes in the monoclinic P21/n centrosymmetric with one molecule of 1 in the (Fig. 1). The structure displays a planar geometry [torsion angle C5—C1—C8—C9 = 175.4 (3)o, only the C5 atom of phenyl ring is considered and not the full fragment]. The phenyl ring makes a dihedral angle of 5.4 (2)° with the least-squares plane through the O1/C1/C8–C10 fragment.
3. Supramolecular features
In the crystal, the closely associated molecules of 1 generate two different helical assemblies across the crystallographic 21-screw axis (b-axis). The helical assembly generated using C1=O1⋯C9i≡C10i (acetylene, C=O⋯π) contacts [symmetry code: (i) −x + , y + , −z + ] (Li et al., 2019; Mooibroek, et al., 2008) has a sheet structure (Fig. 2, Table 1), while the helical assembly created using C—H⋯O (C8—H8A⋯O1ii) contacts [symmetry code: (ii) −x + , y − , −z + ] (Desiraju & Steiner, 2001) has a proper helical structure (Fig. 3, Table 1). The helical assembly created using the short C1=O1⋯C9≡C10 contacts is further supported by marginal C—H⋯π [symmetry code: (iii) −x + , y − , −z + ] contacts involving the phenyl ring (C7—H7) and the π cloud of the acetylene moiety. Both helices are intertwined and form a two-dimensional sheet structure roughly along the a-axis direction. Along the longer c-axis, molecules are loosely connected using weak C—H⋯Br (C10—H10⋯Br1iv contacts [symmetry code: (iv) x − , −y + , z − ] (van den Berg & Seddon, 2003), generating the extended assembly (Figs. 2 and 3, Table 1).
In order to visualize and quantify intermolecular interactions in 1, a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) was performed using Crystal Explorer 21.5 (Spackman et al., 2021), and the associated two-dimensional fingerprint plots (McKinnon et al., 2007) were generated. The Hirshfeld surfaces for the molecule in 1 are shown in Fig. 4 in which the two-dimensional fingerprint plots of the most dominant contacts are also presented. H⋯H (27.4%), H⋯C/C⋯H (22.3%) and H⋯Br/Br⋯H (22.0%) contacts are responsible for the largest contributions to the Hirshfeld surface. Besides these contacts, H⋯O/O⋯H (11.8%) and C⋯C (7.8%) interactions contribute significantly to the total Hirshfeld surface. The contributions of further contacts are only minor and amount to C⋯Br/Br⋯C (4.5%) and C⋯O/O⋯C (3.6%).
4. Database survey
A survey of the Cambridge Structural Database (version 5.43, update 4, November 2022; Groom et al., 2016) revealed that no of compound 1 has been reported. Moreover, no similar to that of compound 1 has been reported. However, focusing only on the 1-phenylbut-3-yn-1-one unit yielded 24 hits with not much similarity with the title compound. The most similar structure with respect to compound 1 is 3-phenyl-2-(phenylethynyl)-1H-inden-1-one (FEGDOO; Kumar et al., 2022).
5. Synthesis and crystallization
A solution of methyl ester 3 (100 mg, 0.35 mmol) and 1N NaOH (3 mL) and methanol (3 mL) was heated to reflux for 3 h. After completion of the reaction as indicated by TLC, the reaction mixture was cooled to room temperature and neutralized with a solution of 3N HCl and then extracted with dichloromethane (3 × 10 mL). The combined organic layer was washed with brine and concentrated. The resulting crude was purified by (30% ethyl acetate in petroleum ether) to afford the acid 2 (70 mg, 74% yield) and an alkyne, the title compound 1 (8 mg, 11% yield) as colourless solids. Colourless crystals of the title compound 1 suitable for single crystal X-ray were obtained by slow evaporation of an ethanol solution.
6. Refinement
Crystal data, data collection and structure . All H atoms (except the acetylene H atom) were located in difference-Fourier map and refined isotropically. The acetylene (—C≡C—H) H atom was placed in a geometrically idealized position using HFIX 163. It was constrained to ride on its parent atom, with Uiso(H) = 1.2Ueq(C) for acetylene. The long C8—H8A distance [1.02 (4) Å] could be the result of its involvement in the directional C— H⋯O hydrogen-bond formation with O1.
details are summarized in Table 2
|
Supporting information
CCDC reference: 2268276
https://doi.org/10.1107/S205698902300508X/dx2053sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300508X/dx2053Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S205698902300508X/dx2053Isup3.cml
Data collection: APEX3 (Bruker, 2016); cell
SAINT-Plus (Bruker, 2016); data reduction: SAINT-Plus (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2020) and publCIF (Westrip, 2010).C10H7BrO | F(000) = 440 |
Mr = 223.07 | Dx = 1.696 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.471 (2) Å | Cell parameters from 1876 reflections |
b = 9.032 (4) Å | θ = 2.4–24.9° |
c = 21.652 (11) Å | µ = 4.65 mm−1 |
β = 92.252 (8)° | T = 297 K |
V = 873.7 (7) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.28 × 0.13 mm |
Bruker SMART APEX diffractometer | 1965 independent reflections |
Radiation source: fine-focus sealed tube | 1397 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Phi and ω Scan scans | θmax = 28.2°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker 2016) | h = −4→5 |
Tmin = 0.293, Tmax = 0.583 | k = −11→11 |
4994 measured reflections | l = −27→27 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0812P)2 + 0.1069P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.002 |
1965 reflections | Δρmax = 0.40 e Å−3 |
133 parameters | Δρmin = −0.62 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5990 (7) | 0.3666 (3) | 0.79382 (16) | 0.0508 (8) | |
Br1 | 1.37959 (10) | 0.22006 (5) | 1.02549 (2) | 0.0743 (2) | |
C2 | 0.7972 (7) | 0.3261 (3) | 0.84766 (16) | 0.0488 (7) | |
C3 | 0.9384 (9) | 0.4391 (4) | 0.88181 (17) | 0.0581 (9) | |
H3 | 0.887 (9) | 0.545 (5) | 0.8679 (19) | 0.080 (12)* | |
C4 | 1.1186 (9) | 0.4079 (4) | 0.93323 (18) | 0.0615 (9) | |
H4 | 1.217 (9) | 0.494 (5) | 0.9555 (19) | 0.077 (11)* | |
C5 | 1.1578 (9) | 0.2628 (4) | 0.95122 (18) | 0.0556 (8) | |
C6 | 1.0233 (9) | 0.1475 (4) | 0.91808 (18) | 0.0609 (9) | |
H6 | 1.065 (9) | 0.051 (5) | 0.9319 (19) | 0.070 (11)* | |
C7 | 0.8439 (9) | 0.1783 (4) | 0.86619 (17) | 0.0560 (8) | |
H7 | 0.752 (8) | 0.096 (4) | 0.8364 (15) | 0.054 (9)* | |
C8 | 0.4544 (9) | 0.2439 (4) | 0.7551 (2) | 0.0555 (9) | |
H8B | 0.342 (9) | 0.184 (4) | 0.7824 (18) | 0.056 (10)* | |
C9 | 0.2564 (10) | 0.3048 (4) | 0.7064 (2) | 0.0666 (11) | |
H8A | 0.617 (10) | 0.187 (5) | 0.734 (2) | 0.068 (12)* | |
C10 | 0.1011 (10) | 0.3516 (5) | 0.6698 (2) | 0.0783 (12) | |
H10 | −0.0283 | 0.3905 | 0.6393 | 0.094* | |
O1 | 0.5514 (7) | 0.4954 (2) | 0.77985 (13) | 0.0718 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0553 (18) | 0.0353 (15) | 0.0622 (19) | −0.0025 (13) | 0.0097 (15) | −0.0018 (14) |
Br1 | 0.0827 (4) | 0.0702 (3) | 0.0688 (3) | −0.00322 (18) | −0.0116 (2) | −0.00504 (18) |
C2 | 0.0542 (18) | 0.0368 (14) | 0.0563 (18) | −0.0031 (13) | 0.0125 (15) | −0.0051 (14) |
C3 | 0.076 (2) | 0.0382 (16) | 0.061 (2) | −0.0070 (15) | 0.0057 (18) | −0.0033 (15) |
C4 | 0.074 (2) | 0.0484 (19) | 0.062 (2) | −0.0152 (17) | 0.0072 (18) | −0.0110 (17) |
C5 | 0.060 (2) | 0.0547 (19) | 0.0524 (19) | −0.0042 (15) | 0.0068 (15) | −0.0065 (16) |
C6 | 0.077 (2) | 0.0415 (18) | 0.064 (2) | −0.0030 (17) | 0.0016 (18) | −0.0003 (16) |
C7 | 0.069 (2) | 0.0386 (15) | 0.060 (2) | −0.0030 (15) | 0.0009 (17) | −0.0053 (15) |
C8 | 0.057 (2) | 0.0396 (15) | 0.069 (2) | 0.0016 (15) | −0.0034 (19) | −0.0029 (16) |
C9 | 0.067 (2) | 0.0464 (18) | 0.087 (3) | −0.0048 (17) | 0.002 (2) | −0.0019 (19) |
C10 | 0.084 (3) | 0.060 (2) | 0.088 (3) | 0.005 (2) | −0.032 (2) | 0.017 (2) |
O1 | 0.0875 (18) | 0.0377 (12) | 0.0895 (19) | 0.0002 (12) | −0.0066 (16) | 0.0024 (13) |
C1—O1 | 1.218 (4) | C5—C6 | 1.388 (5) |
C1—C2 | 1.482 (5) | C6—C7 | 1.383 (5) |
C1—C8 | 1.518 (5) | C6—H6 | 0.93 (4) |
Br1—C5 | 1.895 (4) | C7—H7 | 1.06 (3) |
C2—C3 | 1.397 (5) | C8—C9 | 1.458 (7) |
C2—C7 | 1.407 (5) | C8—H8B | 0.96 (4) |
C3—C4 | 1.378 (6) | C8—H8A | 1.02 (4) |
C3—H3 | 1.03 (5) | C9—C10 | 1.117 (6) |
C4—C5 | 1.377 (5) | C10—H10 | 0.9300 |
C4—H4 | 1.01 (5) | ||
O1—C1—C2 | 121.6 (3) | C7—C6—C5 | 119.7 (3) |
O1—C1—C8 | 119.6 (3) | C7—C6—H6 | 123 (3) |
C2—C1—C8 | 118.8 (3) | C5—C6—H6 | 117 (3) |
C3—C2—C7 | 118.9 (3) | C6—C7—C2 | 119.8 (3) |
C3—C2—C1 | 118.7 (3) | C6—C7—H7 | 123.5 (18) |
C7—C2—C1 | 122.4 (3) | C2—C7—H7 | 116.4 (18) |
C4—C3—C2 | 121.1 (3) | C9—C8—C1 | 110.9 (3) |
C4—C3—H3 | 123 (2) | C9—C8—H8B | 110 (2) |
C2—C3—H3 | 116 (2) | C1—C8—H8B | 107 (2) |
C5—C4—C3 | 119.2 (3) | C9—C8—H8A | 107 (2) |
C5—C4—H4 | 123 (2) | C1—C8—H8A | 109 (2) |
C3—C4—H4 | 117 (3) | H8B—C8—H8A | 113 (3) |
C4—C5—C6 | 121.3 (4) | C10—C9—C8 | 178.8 (6) |
C4—C5—Br1 | 119.4 (3) | C9—C10—H10 | 180.0 |
C6—C5—Br1 | 119.2 (3) | ||
O1—C1—C2—C3 | −1.9 (5) | C3—C4—C5—Br1 | −175.1 (3) |
C8—C1—C2—C3 | 177.7 (3) | C4—C5—C6—C7 | −0.6 (6) |
O1—C1—C2—C7 | 177.0 (3) | Br1—C5—C6—C7 | 175.5 (3) |
C8—C1—C2—C7 | −3.4 (5) | C5—C6—C7—C2 | −0.5 (6) |
C7—C2—C3—C4 | −0.7 (5) | C3—C2—C7—C6 | 1.1 (6) |
C1—C2—C3—C4 | 178.3 (3) | C1—C2—C7—C6 | −177.8 (3) |
C2—C3—C4—C5 | −0.4 (6) | O1—C1—C8—C9 | −3.3 (6) |
C3—C4—C5—C6 | 1.0 (6) | C2—C1—C8—C9 | 177.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—O1···C9i | 3.13 (1) | 154 (1) | ||
C8—H8A···O1ii | 1.02 (4) | 2.31 (4) | 3.259 (5) | 156 (3) |
C7—H7···C10iii | 1.06 (3) | 2.71 (4) | 3.626 (5) | 144 (3) |
C10—H10···Br1iv | 0.93 | 2.68 | 3.305 (5) | 126 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+1/2, y−1/2, −z+3/2; (iv) x−3/2, −y+1/2, z−1/2. |
Acknowledgements
SKS thanks the DST–INSPIRE program for a research fellowship.
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