3 Acetyl 1 phenyl 2 pentene 1,4 dione

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Acta Cryst.(2002). E58, o797±o798 DOI: 10.1107/S1600536802011091 Anwar Usmanet al. C₁₃H₁₂O₃

o797

organic papers

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

3-Acetyl-1-phenyl-2-pentene-1,4-dione

Anwar Usman,a_{Ibrahim Abdul} Razak,a_{Hoong-Kun Fun,}a_* Suchada Chantrapromma,a_² Yun Lib_{and Jian-Hua Xu}b

a_{X-ray Crystallography Unit, School of Physics,}

Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, andb_{Department of Chemistry,} Nanjing University, Nanjing 210093, People's Republic of China

² Permanent address: Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 213 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.054

wRfactor = 0.127

Data-to-parameter ratio = 18.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

The title compound, C13H12O3, crystallizes in the monoclinic system, with two independent molecules in the asymmetric unit. In one of the molecules, the phenyl ring forms a dihedral angle of 23.93 (5)_{with the pentenedione plane, while in the}

other, the dihedral angle is 13.33 (5)_.

Comment

The strong one-electron-oxidant, ceric ammonium nitrate (CAN), has been established as an ef®cient reagent in generating-carbonylalkyl radicals from enolizable ketones, and the addition of these carbon-centered radicals to alkenes has been successfully used in organic synthesis in various CÐC bond-formation reactions (Nair et al., 1997). We have recently investigated the CAN-mediated formation of 1,3-pentanedione with phenylacetylene and we report here the crystal structure of the title compound, (I), which is one of the products of this reaction.

The asymmetric unit of (I) consists of two moleculesAand

B (Fig. 1). The corresponding bond distances and angles of these two molecules agree with each other and show normal values (Allenet al., 1987). A ®t of the non-H atoms of mol-eculeAwith those of the inverted moleculeB resulted in a weighted r.m.s. deviation of 0.121 AÊ. In both molecules, the pentenedione moiety is nearly planar, with the methyl C atom (C13) deviating by a maximum of 0.241 (1) and 0.124 (2) AÊ in moleculesAandB, respectively. The C8ÐC9ÐC10ÐC11 and C8ÐC9ÐC10ÐO2 torsion-angle values [96.4 (2) and

ÿ88.4 (2)_{, respectively, for molecule} _A_{, and} _ÿ_{97.5 (2) and}

86.5 (2) _{for molecule} _B_{] indicate that the acetyl group is}

twisted normal to the pentenedione plane. The dihedral angle between the pentenedione plane and the phenyl ring of mol-ecule A [23.93 (5)_{] is larger than that of molecule} _B

[13.33 (5)_{]. In the solid state, weak CÐH}_{O hydrogen}

bonds link B molecules and inversion-related A molecules (Table 2).

Experimental

The title compound was isolated from the reaction mixture of acetylacetone with ceric ammonium nitrate (CAN) in the presence of

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an excess amount of phenylacetylene in acetonitrile, by column chromatography on silica gel. Single crystals were grown by slow evaporation from a solution of petroleum ether (b.p. 333±353 K)/ ethyl acetate (7:1v/v).

Crystal data

C13H12O3 Mr= 216.23

Monoclinic,P21=c a= 14.1314 (2) AÊ

b= 15.0764 (1) AÊ

c= 10.9229 (2) AÊ

= 102.015 (1) V= 2276.15 (6) AÊ3 Z= 8

Dx= 1.262 Mg mÿ3

MoKradiation Cell parameters from 8192

re¯ections

= 2.5±28.3 = 0.09 mmÿ1 T= 213 (2) K Block, yellow 0.500.400.40 mm

Data collection

Siemens SMART CCD area-detector diffractometer

!scans

Absorption correction: none 13416 measured re¯ections 5495 independent re¯ections

3634 re¯ections withI> 2(I)

Rint= 0.090 max= 28.2 h=ÿ18!15

k=ÿ20!19

l=ÿ14!14

Re®nement

Re®nement onF2 R[F2_{> 2}₍_F2_{)] = 0.054} wR(F2_{) = 0.127} S= 0.91 5495 re¯ections 294 parameters

H-atom parameters constrained

w= 1/[2₍_F

o2) + (0.0326P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.36 e AÊÿ3

min=ÿ0.30 e AÊÿ3

Extinction correction:SHELXTL

Extinction coef®cient: 0.030 (2)

Table 1

Selected geometric parameters (AÊ,_).

C8AÐC9A 1.3424 (19) C8BÐC9B 1.3404 (19) C6AÐC7AÐC8AÐC9A 168.43 (13)

C7AÐC8AÐC9AÐC12A 177.38 (12) C8AÐC9AÐC10AÐC11A 96.37 (18) C8AÐC9AÐC12AÐO3A 167.58 (14) C8AÐC9AÐC12AÐC13A ÿ12.5 (2) C6BÐC7BÐC8BÐC9B ÿ166.06 (13)

C7BÐC8BÐC9BÐC12B 178.90 (13) C8BÐC9BÐC10BÐC11B ÿ97.45 (18) C8BÐC9BÐC12BÐO3B ÿ176.52 (14) C8BÐC9BÐC12BÐC13B 2.6 (2) C10BÐC9BÐC12BÐC13Bÿ179.30 (14)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

C1BÐH1B O3Ai _0.93 _2.54 _{3.415 (2)} ₁₅₈

Symmetry code: (i) 1ÿx;ÿy;1ÿz.

The H atoms were ®xed geometrically and treated as riding on the parent C atoms, with aromatic CÐH = 0.93 AÊ and methyl CÐH = 0.96 AÊ, and with displacement parametersUiso(H) = 1.2Ueq(C).

Data collection:SMART(Siemens, 1996); cell re®nement:SAINT

(Siemens, 1996); data reduction:SAINT and SADABS(Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to re®ne structure: SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publi-cation:SHELXTL, PARST (Nardelli, 1995) andPLATON (Spek, 1990).

The authors thank the Malaysian Government and Universiti Sains Malaysia for research grant R&D No. 305/PFIZIK/610961. AU thanks Universiti Sains Malaysia for a Visiting Post-Doctoral Fellowship.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans.2, pp. S1±19.

Nair, V., Mathew, J. & Prabhakaran, N. (1997).J. Chem. Soc. Rev.26, 127±132. Nardelli, M. (1995).J. Appl. Cryst.28, 659.

Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXTL.Version 5.1. Bruker AXS Inc., Madison,

Wisconsin, USA.

Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Spek, A. L. (1990).Acta Cryst.A46, C-34.

Figure 1

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supporting information

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Acta Cryst. (2002). E58, o797–o798

supporting information

Acta Cryst. (2002). E58, o797–o798 [https://doi.org/10.1107/S1600536802011091]

3-Acetyl-1-phenyl-2-pentene-1,4-dione

Anwar Usman, Ibrahim Abdul Razak, Hoong-Kun Fun, Suchada Chantrapromma, Yun Li and

Jian-Hua Xu

3-Acetyl-1-phenyl-2-pentene-1,4-dione

Crystal data

C13H12O3

Mr = 216.23

Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 14.1314 (2) Å

b = 15.0764 (1) Å

c = 10.9229 (2) Å

β = 102.015 (1)°

V = 2276.15 (6) Å3

Z = 8

F(000) = 912

Dx = 1.262 Mg m−3 Melting point: 344(1) K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8192 reflections

θ = 2.5–28.3°

µ = 0.09 mm−1

T = 213 K Block, yellow

0.50 × 0.40 × 0.40 mm

Data collection

Siemens SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 8.33 pixels mm-1

ω scans

13416 measured reflections

5495 independent reflections 3634 reflections with I > 2σ(I)

Rint = 0.090

θmax = 28.2°, θmin = 2.5°

h = −18→15

k = −20→19

l = −14→14

Refinement

Refinement on F2 Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.054}

wR(F2_{) = 0.127}

S = 0.91 5495 reflections 294 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2₍_F

o2) + (0.0326P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

Δρmax = 0.36 e Å−3 Δρmin = −0.30 e Å−3

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Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different φ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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.

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

x y z Uiso*/Ueq

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Acta Cryst. (2002). E58, o797–o798

C1B 0.07596 (11) −0.03239 (9) 0.65384 (13) 0.0301 (3) H1B 0.1318 −0.0438 0.6241 0.036* C2B 0.02397 (12) −0.10227 (10) 0.68966 (15) 0.0361 (4) H2B 0.0452 −0.1603 0.6842 0.043* C3B −0.05928 (12) −0.08583 (10) 0.73348 (15) 0.0395 (4) H3B −0.0944 −0.1328 0.7567 0.047* C4B −0.09068 (12) 0.00085 (11) 0.74290 (16) 0.0409 (4) H4B −0.1465 0.0118 0.7730 0.049* C5B −0.03904 (11) 0.07064 (10) 0.70768 (15) 0.0345 (4) H5B −0.0603 0.1285 0.7142 0.041* C6B 0.04505 (10) 0.05500 (9) 0.66218 (13) 0.0254 (3) C7B 0.09728 (11) 0.13265 (9) 0.62452 (13) 0.0288 (3) C8B 0.18514 (10) 0.11880 (9) 0.57082 (13) 0.0288 (3) H8B 0.1983 0.0623 0.5445 0.035* C9B 0.24560 (10) 0.18537 (9) 0.55947 (13) 0.0281 (3) C10B 0.23342 (11) 0.27994 (10) 0.60053 (16) 0.0363 (4) C11B 0.18601 (16) 0.34300 (12) 0.5007 (2) 0.0603 (6) H11D 0.1921 0.4024 0.5330 0.091* H11E 0.1187 0.3282 0.4748 0.091* H11F 0.2167 0.3389 0.4304 0.091* C12B 0.33492 (11) 0.17180 (10) 0.50777 (14) 0.0324 (3) C13B 0.35610 (13) 0.08211 (10) 0.46202 (17) 0.0418 (4) H13D 0.4129 0.0851 0.4268 0.063* H13E 0.3022 0.0625 0.3992 0.063* H13F 0.3669 0.0410 0.5307 0.063*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C1B 0.0265 (8) 0.0269 (7) 0.0401 (8) 0.0017 (6) 0.0139 (6) 0.0018 (6) C2B 0.0387 (9) 0.0250 (7) 0.0469 (9) −0.0004 (6) 0.0142 (7) 0.0032 (6) C3B 0.0386 (9) 0.0338 (9) 0.0495 (10) −0.0085 (7) 0.0167 (8) 0.0056 (7) C4B 0.0283 (8) 0.0434 (10) 0.0569 (10) −0.0004 (7) 0.0222 (8) 0.0042 (8) C5B 0.0289 (8) 0.0303 (8) 0.0479 (9) 0.0039 (6) 0.0163 (7) 0.0005 (7) C6B 0.0213 (7) 0.0247 (7) 0.0314 (7) −0.0012 (5) 0.0080 (6) 0.0004 (6) C7B 0.0258 (8) 0.0237 (7) 0.0380 (8) −0.0008 (6) 0.0094 (6) −0.0010 (6) C8B 0.0274 (8) 0.0237 (7) 0.0378 (8) −0.0011 (6) 0.0125 (6) −0.0009 (6) C9B 0.0259 (8) 0.0258 (7) 0.0335 (7) −0.0007 (6) 0.0087 (6) 0.0007 (6) C10B 0.0295 (8) 0.0277 (8) 0.0562 (10) −0.0057 (6) 0.0196 (8) −0.0036 (7) C11B 0.0700 (14) 0.0322 (9) 0.0876 (15) 0.0084 (9) 0.0364 (12) 0.0156 (9) C12B 0.0297 (8) 0.0293 (8) 0.0413 (8) −0.0036 (6) 0.0144 (7) 0.0017 (6) C13B 0.0402 (10) 0.0361 (9) 0.0572 (10) −0.0018 (7) 0.0289 (8) −0.0043 (7)

Geometric parameters (Å, º)

O1A—C7A 1.2255 (17) O1B—C7B 1.2307 (16) O2A—C10A 1.2161 (18) O2B—C10B 1.2107 (19) O3A—C12A 1.2191 (17) O3B—C12B 1.2254 (17) C1A—C2A 1.390 (2) C1B—C2B 1.387 (2) C1A—C6A 1.393 (2) C1B—C6B 1.3969 (19) C1A—H1A 0.93 C1B—H1B 0.93 C2A—C3A 1.384 (2) C2B—C3B 1.382 (2) C2A—H2A 0.93 C2B—H2B 0.93 C3A—C4A 1.387 (2) C3B—C4B 1.391 (2) C3A—H3A 0.93 C3B—H3B 0.93 C4A—C5A 1.378 (2) C4B—C5B 1.380 (2) C4A—H4A 0.93 C4B—H4B 0.93 C5A—C6A 1.3994 (18) C5B—C6B 1.4002 (19) C5A—H5A 0.93 C5B—H5B 0.93 C6A—C7A 1.492 (2) C6B—C7B 1.4868 (19) C7A—C8A 1.4938 (18) C7B—C8B 1.494 (2) C8A—C9A 1.3424 (19) C8B—C9B 1.3404 (19) C8A—H8A 0.93 C8B—H8B 0.93 C9A—C12A 1.5055 (19) C9B—C12B 1.500 (2) C9A—C10A 1.517 (2) C9B—C10B 1.515 (2) C10A—C11A 1.491 (2) C10B—C11B 1.496 (2) C11A—H11A 0.96 C11B—H11D 0.96 C11A—H11B 0.96 C11B—H11E 0.96 C11A—H11C 0.96 C11B—H11F 0.96 C12A—C13A 1.494 (2) C12B—C13B 1.493 (2) C13A—H13A 0.96 C13B—H13D 0.96 C13A—H13B 0.96 C13B—H13E 0.96 C13A—H13C 0.96 C13B—H13F 0.96

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Acta Cryst. (2002). E58, o797–o798

C3A—C2A—C1A 120.29 (15) C3B—C2B—C1B 120.05 (14) C3A—C2A—H2A 119.9 C3B—C2B—H2B 120.0 C1A—C2A—H2A 119.9 C1B—C2B—H2B 120.0 C2A—C3A—C4A 119.85 (15) C2B—C3B—C4B 120.12 (14) C2A—C3A—H3A 120.1 C2B—C3B—H3B 119.9 C4A—C3A—H3A 120.1 C4B—C3B—H3B 119.9 C5A—C4A—C3A 120.19 (14) C5B—C4B—C3B 120.03 (15) C5A—C4A—H4A 119.9 C5B—C4B—H4B 120.0 C3A—C4A—H4A 119.9 C3B—C4B—H4B 120.0 C4A—C5A—C6A 120.54 (15) C4B—C5B—C6B 120.51 (14) C4A—C5A—H5A 119.7 C4B—C5B—H5B 119.7 C6A—C5A—H5A 119.7 C6B—C5B—H5B 119.7 C1A—C6A—C5A 119.03 (13) C1B—C6B—C5B 118.81 (13) C1A—C6A—C7A 123.48 (12) C1B—C6B—C7B 122.99 (13) C5A—C6A—C7A 117.49 (13) C5B—C6B—C7B 118.20 (12) O1A—C7A—C6A 121.16 (12) O1B—C7B—C6B 121.28 (13) O1A—C7A—C8A 119.06 (13) O1B—C7B—C8B 118.75 (13) C6A—C7A—C8A 119.78 (12) C6B—C7B—C8B 119.97 (12) C9A—C8A—C7A 122.01 (13) C9B—C8B—C7B 121.97 (13) C9A—C8A—H8A 119.0 C9B—C8B—H8B 119.0 C7A—C8A—H8A 119.0 C7B—C8B—H8B 119.0 C8A—C9A—C12A 122.25 (13) C8B—C9B—C12B 122.35 (13) C8A—C9A—C10A 124.27 (13) C8B—C9B—C10B 124.29 (13) C12A—C9A—C10A 113.46 (12) C12B—C9B—C10B 113.33 (12) O2A—C10A—C11A 123.77 (16) O2B—C10B—C11B 123.76 (16) O2A—C10A—C9A 119.46 (14) O2B—C10B—C9B 119.77 (15) C11A—C10A—C9A 116.58 (14) C11B—C10B—C9B 116.34 (15) C10A—C11A—H11A 109.5 C10B—C11B—H11D 109.5 C10A—C11A—H11B 109.5 C10B—C11B—H11E 109.5 H11A—C11A—H11B 109.5 H11D—C11B—H11E 109.5 C10A—C11A—H11C 109.5 C10B—C11B—H11F 109.5 H11A—C11A—H11C 109.5 H11D—C11B—H11F 109.5 H11B—C11A—H11C 109.5 H11E—C11B—H11F 109.5 O3A—C12A—C13A 122.31 (13) O3B—C12B—C13B 122.07 (14) O3A—C12A—C9A 118.73 (13) O3B—C12B—C9B 118.42 (14) C13A—C12A—C9A 118.97 (12) C13B—C12B—C9B 119.50 (12) C12A—C13A—H13A 109.5 C12B—C13B—H13D 109.5 C12A—C13A—H13B 109.5 C12B—C13B—H13E 109.5 H13A—C13A—H13B 109.5 H13D—C13B—H13E 109.5 C12A—C13A—H13C 109.5 C12B—C13B—H13F 109.5 H13A—C13A—H13C 109.5 H13D—C13B—H13F 109.5 H13B—C13A—H13C 109.5 H13E—C13B—H13F 109.5

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C2A—C1A—C6A—C7A 179.30 (13) C2B—C1B—C6B—C7B −179.61 (14) C4A—C5A—C6A—C1A 0.1 (2) C4B—C5B—C6B—C1B −0.4 (2) C4A—C5A—C6A—C7A −179.43 (13) C4B—C5B—C6B—C7B 179.45 (14) C1A—C6A—C7A—O1A 170.86 (13) C1B—C6B—C7B—O1B −177.14 (14) C5A—C6A—C7A—O1A −9.67 (19) C5B—C6B—C7B—O1B 3.0 (2) C1A—C6A—C7A—C8A −9.5 (2) C1B—C6B—C7B—C8B 2.2 (2) C5A—C6A—C7A—C8A 169.93 (12) C5B—C6B—C7B—C8B −177.62 (13) O1A—C7A—C8A—C9A −12.0 (2) O1B—C7B—C8B—C9B 13.3 (2) C6A—C7A—C8A—C9A 168.43 (13) C6B—C7B—C8B—C9B −166.06 (13) C7A—C8A—C9A—C12A 177.38 (12) C7B—C8B—C9B—C12B 178.90 (13) C7A—C8A—C9A—C10A −4.4 (2) C7B—C8B—C9B—C10B 1.0 (2) C8A—C9A—C10A—O2A −88.41 (18) C8B—C9B—C10B—O2B 86.5 (2) C12A—C9A—C10A—O2A 89.91 (16) C12B—C9B—C10B—O2B −91.59 (18) C8A—C9A—C10A—C11A 96.37 (18) C8B—C9B—C10B—C11B −97.45 (18) C12A—C9A—C10A—C11A −85.31 (16) C12B—C9B—C10B—C11B 84.48 (17) C8A—C9A—C12A—O3A 167.58 (14) C8B—C9B—C12B—O3B −176.52 (14) C10A—C9A—C12A—O3A −10.78 (19) C10B—C9B—C12B—O3B 1.6 (2) C8A—C9A—C12A—C13A −12.5 (2) C8B—C9B—C12B—C13B 2.6 (2) C10A—C9A—C12A—C13A 169.18 (13) C10B—C9B—C12B—C13B −179.30 (14)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C1B—H1B···O3Ai _0.93 _2.54 _{3.415 (2)} ₁₅₈