1-(1,3-Benzodioxol-5-yl)pentan-1-one

Wang, X.-M.; Cheng, W.; Han, Y.-W.

doi:10.1107/S1600536808040257

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o176

doi:10.1107/S1600536808040257

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1-(1,3-Benzodioxol-5-yl)pentan-1-one

Xiao-Ming Wang,^a Wei Cheng ^a and Yu-Wang Han ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: hanyw@njut.edu.cn

(Received 27 November 2008; accepted 30 November 2008; online 20 December 2008)

In the molecule of title compound, C₁₂H₁₄O₃, the benzodioxole ring system is essentially planar. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link molecules into chains along the c axis, and π–π contacts between dioxole rings and between dioxole and benzene rings of the benzodioxole ring systems [centroid–centroid distances 3.702 (3) and 3.903 (3) Å] may further stabilize the structure. Two C—H⋯π interactions are also found.

Related literature

For general background, see: Koeppe et al. (1969 ). For a related structure, see: May et al. (2000 ). For bond-length data, see: Allen et al. (1987 );

Experimental

Crystal data

C₁₂H₁₄O₃
M_r = 206.23
Monoclinic, P 2₁ /n
a = 6.7940 (14) Å
b = 12.960 (3) Å
c = 12.244 (2) Å
β = 93.46 (3)°
V = 1076.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.991
2133 measured reflections
1961 independent reflections
1079 reflections with I > 2σ(I)
R_int = 0.031
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.171
S = 1.00
1961 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.93	2.60	3.419 (4)	148
C3—H3A⋯Cg2ⁱⁱ	0.97	2.99	3.831 (3)	145
C12—H12A⋯Cg2ⁱⁱⁱ	0.97	2.84	3.633 (3)	139
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) -x+1, -y+1, -z. Cg2 is the centroid of the C6–C11 ring.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040257/hk2587sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040257/hk2587Isup2.hkl

checkCIF report

Comment top

The title compound is an important medicine intermediate used to synthesize methylenedioxypyrovalerone (Koeppe et al., 1969). As part of our studies in this area, we report herein its crystal structure.

In the molecule of title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (O2/O3/C9/C10/C12) and B (C6-C11) are, of course, planar, and the dihedral angle between them is A/B = 0.56 (3)°. So, they are also coplanar. Atoms O1, C5 and C4 are 0.011 (3), -0.049 (3) and -0.119 (3) Å away from the plane of the benzodioxole ring system.

In the crystal structure, weak intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into chains along the c axis (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contacts between the dioxole rings and the dioxole and benzene rings of the benzodioxole ring systems, Cg1—Cg1ⁱ and Cg1—Cg2ⁱ [symmetry code: (i) 1 - x, 1 - y, -z where Cg1 and Cg2 are centroids of the rings A (O2/O3/C9/C10/C12) and B (C6-C11), respectively] may further stabilize the structure, with centroid-centroid distances of 3.702 (3) Å and 3.903 (3) Å. There also exist two C–H···π interactions (Table 1).

Related literature top

For general background, see: Koeppe et al. (1969). For a related structure, see: May et al. (2000). For bond-length data, see: Allen et al. (1987);

Experimental top

The title compound was synthesized according to a literature method (May et al., 2000). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.2 g) in methanol (25 ml), and evaporating the solvent slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1-(1,3-Benzodioxol-5-yl)pentan-1-one top

Crystal data top

C₁₂H₁₄O₃	F(000) = 440
M_r = 206.23	D_x = 1.273 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.7940 (14) Å	θ = 9–12°
b = 12.960 (3) Å	µ = 0.09 mm⁻¹
c = 12.244 (2) Å	T = 298 K
β = 93.46 (3)°	Needle, colorless
V = 1076.1 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1079 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.973, T_max = 0.991	l = −14→14
2133 measured reflections	3 standard reflections every 120 min
1961 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.06P)² + 0.6P] where P = (F_o² + 2F_c²)/3
1961 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₁₄O₃	V = 1076.1 (4) Å³
M_r = 206.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7940 (14) Å	µ = 0.09 mm⁻¹
b = 12.960 (3) Å	T = 298 K
c = 12.244 (2) Å	0.30 × 0.20 × 0.10 mm
β = 93.46 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1079 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.031
T_min = 0.973, T_max = 0.991	3 standard reflections every 120 min
2133 measured reflections	intensity decay: 1%
1961 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
1961 reflections	Δρ_min = −0.20 e Å⁻³
136 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.0098 (4)	0.8069 (2)	1.06817 (19)	0.0789 (9)
O2	0.7749 (3)	0.5827 (2)	0.94774 (18)	0.0650 (7)
O3	0.6590 (4)	0.6096 (2)	1.11889 (18)	0.0666 (8)
C1	−0.4973 (6)	1.0228 (4)	0.8325 (3)	0.0911 (14)
H1A	−0.5608	1.0466	0.7650	0.137*
H1B	−0.4467	1.0809	0.8741	0.137*
H1C	−0.5909	0.9864	0.8738	0.137*
C2	−0.3317 (5)	0.9524 (3)	0.8088 (3)	0.0678 (11)
H2A	−0.2416	0.9894	0.7644	0.081*
H2B	−0.3849	0.8951	0.7655	0.081*
C3	−0.2171 (5)	0.9099 (3)	0.9067 (3)	0.0589 (9)
H3A	−0.3054	0.8699	0.9495	0.071*
H3B	−0.1680	0.9670	0.9519	0.071*
C4	−0.0454 (5)	0.8428 (3)	0.8797 (3)	0.0567 (9)
H4A	−0.0947	0.7866	0.8333	0.068*
H4B	0.0435	0.8833	0.8379	0.068*
C5	0.0698 (5)	0.7978 (3)	0.9768 (3)	0.0519 (9)
C6	0.2532 (5)	0.7393 (2)	0.9607 (2)	0.0458 (8)
C7	0.3230 (5)	0.7220 (3)	0.8582 (2)	0.0507 (9)
H7A	0.2519	0.7472	0.7966	0.061*
C8	0.4974 (5)	0.6678 (3)	0.8456 (3)	0.0566 (9)
H8A	0.5421	0.6546	0.7766	0.068*
C9	0.5996 (5)	0.6350 (3)	0.9378 (3)	0.0501 (8)
C10	0.5302 (5)	0.6509 (3)	1.0409 (2)	0.0503 (8)
C11	0.3604 (5)	0.7021 (3)	1.0545 (2)	0.0514 (9)
H11A	0.3155	0.7125	1.1239	0.062*
C12	0.8125 (5)	0.5645 (3)	1.0614 (3)	0.0627 (10)
H12A	0.8183	0.4908	1.0754	0.075*
H12B	0.9382	0.5945	1.0860	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0840 (19)	0.098 (2)	0.0557 (15)	0.0266 (17)	0.0117 (13)	0.0023 (14)
O2	0.0596 (16)	0.0744 (18)	0.0610 (15)	0.0185 (14)	0.0035 (12)	−0.0015 (13)
O3	0.0670 (17)	0.0770 (18)	0.0552 (14)	0.0171 (14)	−0.0010 (12)	0.0033 (13)
C1	0.101 (3)	0.085 (3)	0.085 (3)	0.032 (3)	−0.015 (3)	−0.012 (2)
C2	0.074 (3)	0.064 (2)	0.065 (2)	0.014 (2)	0.0040 (19)	0.0096 (19)
C3	0.063 (2)	0.046 (2)	0.067 (2)	−0.0010 (18)	0.0010 (18)	−0.0020 (18)
C4	0.055 (2)	0.058 (2)	0.0580 (19)	−0.0002 (18)	0.0049 (16)	0.0037 (18)
C5	0.059 (2)	0.048 (2)	0.0497 (18)	−0.0008 (17)	0.0083 (16)	−0.0009 (16)
C6	0.049 (2)	0.0390 (18)	0.0498 (17)	−0.0036 (16)	0.0070 (15)	0.0020 (14)
C7	0.055 (2)	0.050 (2)	0.0460 (17)	−0.0029 (18)	−0.0016 (15)	0.0032 (15)
C8	0.063 (2)	0.060 (2)	0.0479 (18)	−0.0032 (19)	0.0119 (17)	−0.0051 (16)
C9	0.054 (2)	0.044 (2)	0.0521 (18)	−0.0044 (17)	0.0040 (16)	−0.0030 (15)
C10	0.059 (2)	0.044 (2)	0.0469 (17)	−0.0014 (17)	−0.0016 (16)	0.0008 (15)
C11	0.057 (2)	0.053 (2)	0.0443 (17)	0.0006 (18)	0.0054 (16)	−0.0015 (15)
C12	0.062 (2)	0.061 (2)	0.064 (2)	0.006 (2)	0.0000 (18)	0.0036 (19)

Geometric parameters (Å, º) top

O1—C5	1.220 (4)	C4—C5	1.501 (4)
O2—C9	1.370 (4)	C4—H4A	0.9700
O2—C12	1.419 (4)	C4—H4B	0.9700
O3—C10	1.365 (4)	C5—C6	1.482 (4)
O3—C12	1.419 (4)	C6—C7	1.387 (4)
C1—C2	1.491 (5)	C6—C11	1.407 (4)
C1—H1A	0.9600	C7—C8	1.394 (5)
C1—H1B	0.9600	C7—H7A	0.9300
C1—H1C	0.9600	C8—C9	1.358 (5)
C2—C3	1.495 (4)	C8—H8A	0.9300
C2—H2A	0.9700	C9—C10	1.389 (4)
C2—H2B	0.9700	C10—C11	1.349 (4)
C3—C4	1.508 (4)	C11—H11A	0.9300
C3—H3A	0.9700	C12—H12A	0.9700
C3—H3B	0.9700	C12—H12B	0.9700

C9—O2—C12	105.9 (3)	O1—C5—C4	120.1 (3)
C10—O3—C12	105.9 (2)	C6—C5—C4	119.8 (3)
C2—C1—H1A	109.5	C7—C6—C11	119.6 (3)
C2—C1—H1B	109.5	C7—C6—C5	122.6 (3)
H1A—C1—H1B	109.5	C11—C6—C5	117.8 (3)
C2—C1—H1C	109.5	C6—C7—C8	121.4 (3)
H1A—C1—H1C	109.5	C6—C7—H7A	119.3
H1B—C1—H1C	109.5	C8—C7—H7A	119.3
C1—C2—C3	115.6 (3)	C9—C8—C7	117.4 (3)
C1—C2—H2A	108.4	C9—C8—H8A	121.3
C3—C2—H2A	108.4	C7—C8—H8A	121.3
C1—C2—H2B	108.4	C8—C9—O2	128.8 (3)
C3—C2—H2B	108.4	C8—C9—C10	121.7 (3)
H2A—C2—H2B	107.5	O2—C9—C10	109.5 (3)
C2—C3—C4	114.1 (3)	C11—C10—O3	128.6 (3)
C2—C3—H3A	108.7	C11—C10—C9	121.6 (3)
C4—C3—H3A	108.7	O3—C10—C9	109.8 (3)
C2—C3—H3B	108.7	C10—C11—C6	118.2 (3)
C4—C3—H3B	108.7	C10—C11—H11A	120.9
H3A—C3—H3B	107.6	C6—C11—H11A	120.9
C5—C4—C3	115.1 (3)	O3—C12—O2	108.9 (3)
C5—C4—H4A	108.5	O3—C12—H12A	109.9
C3—C4—H4A	108.5	O2—C12—H12A	109.9
C5—C4—H4B	108.5	O3—C12—H12B	109.9
C3—C4—H4B	108.5	O2—C12—H12B	109.9
H4A—C4—H4B	107.5	H12A—C12—H12B	108.3
O1—C5—C6	120.1 (3)

C1—C2—C3—C4	−177.5 (3)	C12—O2—C9—C10	0.9 (4)
C2—C3—C4—C5	−179.0 (3)	C12—O3—C10—C11	180.0 (4)
C3—C4—C5—O1	8.2 (5)	C12—O3—C10—C9	−1.2 (4)
C3—C4—C5—C6	−173.9 (3)	C8—C9—C10—C11	−1.8 (5)
O1—C5—C6—C7	176.7 (3)	O2—C9—C10—C11	179.1 (3)
C4—C5—C6—C7	−1.3 (5)	C8—C9—C10—O3	179.3 (3)
O1—C5—C6—C11	−4.6 (5)	O2—C9—C10—O3	0.2 (4)
C4—C5—C6—C11	177.5 (3)	O3—C10—C11—C6	179.0 (3)
C11—C6—C7—C8	0.4 (5)	C9—C10—C11—C6	0.2 (5)
C5—C6—C7—C8	179.1 (3)	C7—C6—C11—C10	0.4 (5)
C6—C7—C8—C9	−1.8 (5)	C5—C6—C11—C10	−178.4 (3)
C7—C8—C9—O2	−178.6 (3)	C10—O3—C12—O2	1.8 (4)
C7—C8—C9—C10	2.5 (5)	C9—O2—C12—O3	−1.7 (4)
C12—O2—C9—C8	−178.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.93	2.60	3.419 (4)	148
C3—H3A···Cg2ⁱⁱ	0.97	2.99	3.831 (3)	145
C12—H12A···Cg2ⁱⁱⁱ	0.97	2.84	3.633 (3)	139

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₃
M_r	206.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.7940 (14), 12.960 (3), 12.244 (2)
β (°)	93.46 (3)
V (Å³)	1076.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2133, 1961, 1079
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.171, 1.00
No. of reflections	1961
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.93	2.60	3.419 (4)	148.00
C3—H3A···Cg2ⁱⁱ	0.97	2.99	3.831 (3)	145.08
C12—H12A···Cg2ⁱⁱⁱ	0.97	2.84	3.633 (3)	139.26

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

Acknowledgements

This work was supported by the Science Fundamental Research Fund of the Education Department, Jiangsu Province (grant No. 06KJB150024). The authors thank the Center of Testing and Analysis, Nanjing University, for data collection.

References

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