(E) 4 (4 Hydr­­oxy 3 meth­oxy­phen­yl)but 3 en 2 one

organic papers

Acta Cryst.(2006). E62, o871–o872 doi:10.1107/S1600536806001735 Wanget al. _C

11H12O3

o871

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

(

E

)-4-(4-Hydroxy-3-methoxyphenyl)but-3-en-2-one

Shi-Fan Wang,a* Li-Jun Zhoub and Xian Yangb

a

Department of Pharmaceutical Engineering, School of Ocean, Hainan University, Haikou 570228, People’s Republic of China, and

b_{Laboratory for Drug Design and Synthesis,}

School of Ocean, Hainan University, Haikou 570228, People’s Republic of China

Correspondence e-mail: wangsf777@163.com

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.046

wRfactor = 0.140

Data-to-parameter ratio = 18.0

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

Received 30 November 2005 Accepted 16 January 2006

#2006 International Union of Crystallography

All rights reserved

The title compound, C11H12O3, was synthesized from

4-hydroxy-3-methoxybenzaldehyde and acetone. The molecule has a high degree of conjugation throughout the system and intermolecular hydrogen bonds connect adjacent molecules to form one-dimensional chains.

Comment

,-Unsaturated ketones are an important class of pharma-ceutical intermediates and have extensive application in the synthesis of natural products and drugs by 1,4 addition. As a precursor for further synthesis, we have synthesized the title compound, (I).

All the bond lengths and angles (Table 1) are within normal ranges (Allenet al., 1987) and the structural data confirm the

E configuration about the C3 C4 double bond. Atoms C2, C3, C4 and O1 constitute a well defined plane and the benzene ring plane is inclined at 5.34 (1)_{to this plane (Fig. 1). A weak}

intermolecular O2—H2 O1 hydrogen bond links adjacent molecules, forming one-dimensional chains (Fig. 2).

Experimental

4-Hydroxy-3-methoxybenzaldehyde (3.04 g, 20 mmol) was dissolved in 25 ml of acetone and 12 ml of dilute aqueous NaOH solution (10%) was added to the acetone solution with stirring. The mixture was allowed to stand overnight at room temperature and then the mixture was acidified with dilute aqueous HCl to give (E )-4-(4-hydroxy-3-methoxyphenyl)but-3-en-2-one as a yellow solid (yield 73%). The resultant precipitate was filtered off, washed with water and recrystallized from ethanol and dichloromethane (2:1), in air over a period of four days. After about three-quarters of the original solvent had evaporated, large colourless prisms of (I) were obtained (yield 61%).

Crystal data

C11H12O3 Mr= 192.21

Monoclinic,P21=c a= 9.602 (5) A˚ b= 7.780 (4) A˚ c= 13.478 (7) A˚ = 97.466 (8)

V= 998.2 (9) A˚3 Z= 4

Dx= 1.279 Mg m

3 MoKradiation Cell parameters from 2995

reflections = 2.6–27.9

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: none 8188 measured reflections 2355 independent reflections

1816 reflections withI> 2(I) Rint= 0.020

max= 28.4 h=12!12 k=10!10 l=17!17

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.046} wR(F2_{) = 0.140} S= 1.04 2355 reflections 131 parameters

H-atom parameters constrained

w= 1/[2

(Fo2) + (0.07P)2 + 0.1629P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001

max= 0.20 e A˚

3

min=0.19 e A˚

3

Extinction correction:SHELXL97 Extinction coefficient: 0.024 (5)

Table 1

Selected geometric parameters (A˚ ,_).

O2—C8 1.3556 (18)

C4—C3 1.336 (2)

C4—C5 1.459 (2)

C5—C6 1.388 (2)

C5—C10 1.400 (2)

O3—C9 1.3686 (17)

O3—C11 1.413 (2)

C10—C9 1.3785 (19)

C8—C7 1.380 (2)

C8—C9 1.394 (2)

C6—C7 1.379 (2)

O1—C2 1.2243 (18)

C3—C2 1.454 (2)

C2—C1 1.490 (2)

C3—C4—C5 127.19 (15)

C6—C5—C10 118.55 (12)

C6—C5—C4 122.60 (13)

C10—C5—C4 118.85 (13)

C9—O3—C11 117.63 (12)

C9—C10—C5 120.79 (13)

O2—C8—C7 118.81 (13)

O2—C8—C9 121.70 (13)

C7—C8—C9 119.48 (13)

O3—C9—C10 125.48 (13)

O3—C9—C8 114.63 (12)

C10—C9—C8 119.89 (13)

C7—C6—C5 120.63 (14)

C4—C3—C2 124.57 (15)

O1—C2—C3 119.85 (15)

O1—C2—C1 119.74 (14)

C3—C2—C1 120.40 (14)

C6—C7—C8 120.64 (14)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O2—H2 O1i 0.82 2.08 2.772 (2) 141

Symmetry code: (i)xþ1;yþ1 2;z

1 2.

H atoms were positioned geometrically [C—H distances of 0.93 (Csp2—H) and 0.96 A˚ (methyl), and O—H = 0.82 A˚].Uiso(H) values

were set equal toxUeq(carrier atom), wherex= 1.2 for CH and 1.5 for

O and methyl C.

Data collection:SMART(Bruker, 2002); cell refinement:SAINT

(Bruker, 2002); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL(Sheldrick, 2000); software used to prepare material for publication:SHELXTL.

This project is sponsored by the Scientific Research Foundation of Hainan University, China.

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.

Bruker (2002).SAINTandSMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Sheldrick, G. M. (2000).SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Figure 1

The structure of the title compound (1), showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Figure 2

supporting information

sup-1 Acta Cryst. (2006). E62, o871–o872

supporting information

Acta Cryst. (2006). E62, o871–o872 [https://doi.org/10.1107/S1600536806001735]

(

E

)-4-(4-Hydroxy-3-methoxyphenyl)but-3-en-2-one

Shi-Fan Wang, Li-Jun Zhou and Xian Yang

(E)-4-(4-hydroxy-3-methoxyphenyl) but-3-en-2-one

Crystal data

C11H12O3

Mr = 192.21

Monoclinic, P21/c

a = 9.602 (5) Å

b = 7.780 (4) Å

c = 13.478 (7) Å

β = 97.466 (8)°

V = 998.2 (9) Å3

Z = 4

F(000) = 408

Dx = 1.279 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2995 reflections

θ = 2.6–27.9°

µ = 0.09 mm−1

T = 293 K Prism, colourless 0.36 × 0.28 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

8188 measured reflections 2355 independent reflections

1816 reflections with I > 2σ(I)

Rint = 0.020

θmax = 28.4°, θmin = 2.1°

h = −12→12

k = −10→10

l = −17→17

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.046}

wR(F2_{) = 0.140}

S = 1.04 2355 reflections 131 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) + (0.07P)2 + 0.1629P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.20 e Å−3

Δρmin = −0.19 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.024 (5)

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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

O2 1.20118 (12) 0.80293 (18) 0.28139 (8) 0.0676 (4)

H2 1.2674 0.7414 0.2716 0.101*

C4 0.80091 (15) 0.82090 (19) −0.06027 (11) 0.0519 (4)

H4 0.8317 0.7829 −0.1191 0.062*

C5 0.90466 (13) 0.82078 (18) 0.02899 (10) 0.0471 (3) O3 1.26019 (11) 0.64976 (17) 0.11386 (8) 0.0683 (4) C10 1.03328 (14) 0.73781 (19) 0.02537 (10) 0.0494 (4)

H10 1.0519 0.6873 −0.0340 0.059*

C8 1.10596 (14) 0.80697 (19) 0.19783 (10) 0.0491 (4) C9 1.13266 (14) 0.73009 (19) 0.10883 (10) 0.0481 (3) C6 0.88071 (15) 0.8990 (2) 0.11778 (11) 0.0536 (4)

H6 0.7965 0.9563 0.1212 0.064*

O1 0.44087 (11) 0.88424 (18) −0.15226 (9) 0.0725 (4) C3 0.66655 (15) 0.8696 (2) −0.06681 (12) 0.0539 (4)

H3 0.6358 0.9171 −0.0102 0.065*

C2 0.56503 (15) 0.8534 (2) −0.15629 (12) 0.0550 (4) C7 0.98065 (16) 0.8924 (2) 0.20102 (11) 0.0564 (4)

H7 0.9635 0.9462 0.2599 0.068*

C11 1.31211 (18) 0.6130 (3) 0.02279 (13) 0.0686 (5)

H11A 1.3154 0.7170 −0.0152 0.103*

H11B 1.2513 0.5316 −0.0148 0.103*

H11C 1.4049 0.5656 0.0366 0.103*

C1 0.61088 (19) 0.7969 (3) −0.25261 (14) 0.0864 (7)

H1A 0.5309 0.7915 −0.3033 0.130*

H1B 0.6534 0.6853 −0.2442 0.130*

H1C 0.6778 0.8775 −0.2724 0.130*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2006). E62, o871–o872

C2 0.0413 (8) 0.0594 (9) 0.0625 (9) −0.0014 (6) −0.0004 (6) 0.0014 (7) C7 0.0564 (8) 0.0674 (10) 0.0464 (8) 0.0073 (7) 0.0098 (6) −0.0028 (7) C11 0.0530 (9) 0.0917 (13) 0.0630 (10) 0.0170 (8) 0.0150 (7) 0.0022 (9) C1 0.0538 (10) 0.1337 (19) 0.0680 (11) 0.0088 (11) −0.0059 (8) −0.0250 (12)

Geometric parameters (Å, º)

O2—C8 1.3556 (18) C6—C7 1.379 (2)

O2—H2 0.8200 C6—H6 0.9300

C4—C3 1.336 (2) O1—C2 1.2243 (18)

C4—C5 1.459 (2) C3—C2 1.454 (2)

C4—H4 0.9300 C3—H3 0.9300

C5—C6 1.388 (2) C2—C1 1.490 (2)

C5—C10 1.400 (2) C7—H7 0.9300

O3—C9 1.3686 (17) C11—H11A 0.9600

O3—C11 1.413 (2) C11—H11B 0.9600

C10—C9 1.3785 (19) C11—H11C 0.9600

C10—H10 0.9300 C1—H1A 0.9600

C8—C7 1.380 (2) C1—H1B 0.9600

C8—C9 1.394 (2) C1—H1C 0.9600

C8—O2—H2 109.5 C4—C3—H3 117.7

C3—C4—C5 127.19 (15) C2—C3—H3 117.7

C3—C4—H4 116.4 O1—C2—C3 119.85 (15)

C5—C4—H4 116.4 O1—C2—C1 119.74 (14)

C6—C5—C10 118.55 (12) C3—C2—C1 120.40 (14) C6—C5—C4 122.60 (13) C6—C7—C8 120.64 (14)

C10—C5—C4 118.85 (13) C6—C7—H7 119.7

C9—O3—C11 117.63 (12) C8—C7—H7 119.7

C9—C10—C5 120.79 (13) O3—C11—H11A 109.5

C9—C10—H10 119.6 O3—C11—H11B 109.5

C5—C10—H10 119.6 H11A—C11—H11B 109.5

O2—C8—C7 118.81 (13) O3—C11—H11C 109.5 O2—C8—C9 121.70 (13) H11A—C11—H11C 109.5 C7—C8—C9 119.48 (13) H11B—C11—H11C 109.5 O3—C9—C10 125.48 (13) C2—C1—H1A 109.5

O3—C9—C8 114.63 (12) C2—C1—H1B 109.5

C10—C9—C8 119.89 (13) H1A—C1—H1B 109.5

C7—C6—C5 120.63 (14) C2—C1—H1C 109.5

C7—C6—H6 119.7 H1A—C1—H1C 109.5

C5—C6—H6 119.7 H1B—C1—H1C 109.5

C4—C3—C2 124.57 (15)

C11—O3—C9—C8 −162.13 (15) C4—C3—C2—O1 172.18 (17) C5—C10—C9—O3 178.73 (14) C4—C3—C2—C1 −6.9 (3) C5—C10—C9—C8 −0.6 (2) C5—C6—C7—C8 −0.5 (2) O2—C8—C9—O3 0.9 (2) O2—C8—C7—C6 −179.72 (14) C7—C8—C9—O3 179.65 (13) C9—C8—C7—C6 1.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O2—H2···O1i _{0.82 2.08 2.772 (2) 141}