4,4-Dimethyl-1-(3-nitro­phen­yl)pent-1-en-3-one

Chen, P.; Xia, L.; Hu, A.-X.; Ye, J.

doi:10.1107/S1600536809018479

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1346

doi:10.1107/S1600536809018479

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4,4-Dimethyl-1-(3-nitrophenyl)pent-1-en-3-one

Ping Chen,^a Lin Xia,^b Ai-Xi Hu ^b ^* and Jiao Ye ^b

^aCollege of Chemical and Biological Engineering, Changsha University of Science and Technology, 410004 Changsha, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Hunan University, 410082 Changsha, People's Republic of China
^*Correspondence e-mail: axhu0731@yahoo.com.cn

(Received 14 May 2009; accepted 15 May 2009; online 20 May 2009)

All the non-hydrogen atoms except one methyl C atom of the title compound, C₁₃H₁₅NO₃, lie on a crystallographic mirror plane perpendicular to the b axis. The crystal packing is stabilized by two weak intermolecular C—H⋯O hydrogen bonds.

Related literature

The title compound is an important intermediate in the pesticides industry (Wang et al., 2006 ). For related structures, see: Anuradha et al. (2008 ); Butcher et al. (2007 ); Gong et al. (2008 ); Harrison et al. (2007 ); Patil et al. (2007 ); Sarojini et al. (2007 ); Thiruvalluvar et al. (2007 , 2008 ); Xia & Hu (2008 ).

Experimental

Crystal data

C₁₃H₁₅NO₃
M_r = 233.26
Orthorhombic, P n m a
a = 11.3375 (9) Å
b = 7.2163 (6) Å
c = 14.9327 (12) Å
V = 1221.72 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.48 × 0.36 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.958, T_max = 0.987
5485 measured reflections
1280 independent reflections
937 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.123
S = 1.06
1280 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O2ⁱ	0.98	2.44	3.367 (2)	158
C10—H10⋯O2ⁱⁱ	0.95	2.50	3.366 (3)	152
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018479/bt2958sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018479/bt2958Isup2.hkl

checkCIF report

Comment top

The title compound, 1-(3-nitrophenyl)-4,4-dimethylpentan-3-one, is a very important intermediate in the pesticides industry (Wang et al., 2006). Continuing our work (Xia & Hu, 2008), we report the synthesis and crystal structure of the title compound. Several crystal structures containing phenylprop-2-en-1-one moiety have been recently published (Anuradha et al., 2008; Butcher et al., 2007; Gong et al., 2008; Harrison et al., 2007; Patil et al., 2007; Sarojini et al., 2007; Thiruvalluvar et al., 2007, 2008; Xia & Hu, 2008). In the title compound (Fig. 1), the carbonyl, ethenyl and nitro groups are coplanar with the benzene ring. The bond lengths and bond angles in (I) are in excellent agreement with the corresponding bond lengths and angles reported in the related compounds given above. The crystal packing is illustrated in Fig. 2.

Related literature top

For background literature, see: Wang et al. (2006). For related structures, see: Anuradha et al. (2008); Butcher et al. (2007); Gong et al. (2008); Harrison et al. (2007); Patil et al. (2007); Sarojini et al. (2007); Thiruvalluvar et al. (2007, 2008); Xia & Hu (2008).

Experimental top

3,3-dimethylbutan-2-one(0.0105 mol) was added dropwise into the solution of 3-nitrobenzaldehyde (0.01 mol) and 60 ml ethanol. Then 0.1 g 50% NaOH solution as catalyzer was added and the solution was stirred at 333 K for 5 h (monitored by TLC). Part of the solvent was evaporated and the solution was cooled to 277 K and a precipitate formed. It was filtered and dried. Crystals suitable for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound.

4,4-Dimethyl-1-(3-nitrophenyl)pent-1-en-3-one top

Crystal data top

C₁₃H₁₅NO₃	D_x = 1.268 Mg m⁻³
M_r = 233.26	Melting point: 363 K
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1920 reflections
a = 11.3375 (9) Å	θ = 2.3–27.7°
b = 7.2163 (6) Å	µ = 0.09 mm⁻¹
c = 14.9327 (12) Å	T = 173 K
V = 1221.72 (17) Å³	Block, colourless
Z = 4	0.48 × 0.36 × 0.15 mm
F(000) = 496

Data collection top

Bruker SMART 1000 CCD diffractometer	1280 independent reflections
Radiation source: fine-focus sealed tube	937 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→12
T_min = 0.958, T_max = 0.987	k = −3→8
5485 measured reflections	l = −18→17

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0591P)² + 0.3634P] where P = (F_o² + 2F_c²)/3
1280 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₃H₁₅NO₃	V = 1221.72 (17) Å³
M_r = 233.26	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.3375 (9) Å	µ = 0.09 mm⁻¹
b = 7.2163 (6) Å	T = 173 K
c = 14.9327 (12) Å	0.48 × 0.36 × 0.15 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1280 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	937 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.987	R_int = 0.030
5485 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.06	Δρ_max = 0.26 e Å⁻³
1280 reflections	Δρ_min = −0.16 e Å⁻³
101 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	Occ. (<1)
C1	0.64133 (19)	0.2500	0.12364 (15)	0.0363 (6)
H1	0.7249	0.2500	0.1281	0.044*
C2	0.5825 (2)	0.2500	0.19956 (15)	0.0371 (6)
H2	0.4987	0.2500	0.1983	0.045*
C3	0.6446 (2)	0.2500	0.28774 (15)	0.0367 (6)
C4	0.56797 (18)	0.2500	0.37208 (15)	0.0317 (5)
C5	0.6474 (2)	0.2500	0.45437 (16)	0.0392 (6)
H5A	0.5987	0.2500	0.5086	0.059*
H5B	0.6973	0.3609	0.4537	0.059*	0.50
H5C	0.6973	0.1391	0.4537	0.059*	0.50
C6	0.48919 (15)	0.0777 (3)	0.37212 (12)	0.0419 (5)
H6A	0.5385	−0.0338	0.3701	0.063*
H6B	0.4374	0.0803	0.3196	0.063*
H6C	0.4412	0.0761	0.4267	0.063*
C7	0.59173 (19)	0.2500	0.03248 (15)	0.0310 (5)
C8	0.66910 (19)	0.2500	−0.03967 (15)	0.0313 (5)
H8	0.7519	0.2500	−0.0299	0.038*
C9	0.62418 (18)	0.2500	−0.12592 (14)	0.0296 (5)
C10	0.5051 (2)	0.2500	−0.14355 (15)	0.0348 (6)
H10	0.4764	0.2500	−0.2033	0.042*
C11	0.42813 (19)	0.2500	−0.07129 (16)	0.0381 (6)
H11	0.3454	0.2500	−0.0814	0.046*
C12	0.47098 (19)	0.2500	0.01538 (15)	0.0363 (6)
H12	0.4171	0.2500	0.0641	0.044*
N1	0.70773 (17)	0.2500	−0.20150 (12)	0.0359 (5)
O1	0.66864 (16)	0.2500	−0.27777 (11)	0.0501 (5)
O2	0.81309 (15)	0.2500	−0.18457 (12)	0.0570 (6)
O3	0.75145 (14)	0.2500	0.29171 (11)	0.0559 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0277 (11)	0.0469 (15)	0.0344 (13)	0.000	−0.0032 (9)	0.000
C2	0.0283 (11)	0.0495 (15)	0.0337 (13)	0.000	−0.0012 (9)	0.000
C3	0.0319 (12)	0.0453 (15)	0.0328 (13)	0.000	−0.0006 (9)	0.000
C4	0.0315 (11)	0.0347 (13)	0.0290 (12)	0.000	−0.0002 (9)	0.000
C5	0.0373 (12)	0.0471 (15)	0.0333 (13)	0.000	−0.0019 (10)	0.000
C6	0.0415 (9)	0.0424 (10)	0.0418 (10)	−0.0048 (8)	0.0023 (7)	0.0001 (8)
C7	0.0304 (11)	0.0317 (13)	0.0310 (12)	0.000	−0.0015 (9)	0.000
C8	0.0265 (10)	0.0332 (13)	0.0340 (13)	0.000	−0.0030 (9)	0.000
C9	0.0312 (11)	0.0281 (12)	0.0297 (12)	0.000	0.0014 (9)	0.000
C10	0.0352 (12)	0.0387 (14)	0.0306 (12)	0.000	−0.0043 (9)	0.000
C11	0.0279 (11)	0.0494 (15)	0.0372 (13)	0.000	−0.0014 (9)	0.000
C12	0.0321 (12)	0.0447 (14)	0.0322 (13)	0.000	0.0006 (9)	0.000
N1	0.0355 (11)	0.0405 (12)	0.0316 (12)	0.000	0.0020 (8)	0.000
O1	0.0501 (10)	0.0725 (14)	0.0278 (10)	0.000	−0.0010 (8)	0.000
O2	0.0322 (9)	0.0955 (16)	0.0434 (11)	0.000	0.0058 (8)	0.000
O3	0.0300 (10)	0.1027 (17)	0.0350 (10)	0.000	−0.0011 (7)	0.000

Geometric parameters (Å, º) top

C1—C2	1.315 (3)	C6—H6C	0.9800
C1—C7	1.473 (3)	C7—C8	1.389 (3)
C1—H1	0.9500	C7—C12	1.393 (3)
C2—C3	1.493 (3)	C8—C9	1.385 (3)
C2—H2	0.9500	C8—H8	0.9500
C3—O3	1.213 (3)	C9—C10	1.376 (3)
C3—C4	1.530 (3)	C9—N1	1.474 (3)
C4—C5	1.523 (3)	C10—C11	1.388 (3)
C4—C6	1.531 (2)	C10—H10	0.9500
C4—C6ⁱ	1.531 (2)	C11—C12	1.382 (3)
C5—H5A	0.9800	C11—H11	0.9500
C5—H5B	0.9800	C12—H12	0.9500
C5—H5C	0.9800	N1—O2	1.221 (2)
C6—H6A	0.9800	N1—O1	1.222 (2)
C6—H6B	0.9800

C2—C1—C7	127.1 (2)	C4—C6—H6C	109.5
C2—C1—H1	116.5	H6A—C6—H6C	109.5
C7—C1—H1	116.5	H6B—C6—H6C	109.5
C1—C2—C3	121.4 (2)	C8—C7—C12	118.6 (2)
C1—C2—H2	119.3	C8—C7—C1	118.40 (19)
C3—C2—H2	119.3	C12—C7—C1	123.0 (2)
O3—C3—C2	120.9 (2)	C9—C8—C7	119.27 (19)
O3—C3—C4	121.8 (2)	C9—C8—H8	120.4
C2—C3—C4	117.30 (19)	C7—C8—H8	120.4
C5—C4—C3	109.19 (18)	C10—C9—C8	122.6 (2)
C5—C4—C6	110.15 (12)	C10—C9—N1	118.97 (19)
C3—C4—C6	109.36 (12)	C8—C9—N1	118.42 (18)
C5—C4—C6ⁱ	110.15 (12)	C9—C10—C11	117.9 (2)
C3—C4—C6ⁱ	109.36 (12)	C9—C10—H10	121.0
C6—C4—C6ⁱ	108.63 (18)	C11—C10—H10	121.0
C4—C5—H5A	109.5	C12—C11—C10	120.5 (2)
C4—C5—H5B	109.5	C12—C11—H11	119.8
H5A—C5—H5B	109.5	C10—C11—H11	119.8
C4—C5—H5C	109.5	C11—C12—C7	121.1 (2)
H5A—C5—H5C	109.5	C11—C12—H12	119.4
H5B—C5—H5C	109.5	C7—C12—H12	119.4
C4—C6—H6A	109.5	O2—N1—O1	123.22 (19)
C4—C6—H6B	109.5	O2—N1—C9	118.06 (18)
H6A—C6—H6B	109.5	O1—N1—C9	118.73 (18)

C7—C1—C2—C3	180.0	C7—C8—C9—C10	0.0
C1—C2—C3—O3	0.0	C7—C8—C9—N1	180.0
C1—C2—C3—C4	180.0	C8—C9—C10—C11	0.0
O3—C3—C4—C5	0.0	N1—C9—C10—C11	180.0
C2—C3—C4—C5	180.0	C9—C10—C11—C12	0.0
O3—C3—C4—C6	−120.58 (12)	C10—C11—C12—C7	0.0
C2—C3—C4—C6	59.42 (12)	C8—C7—C12—C11	0.0
O3—C3—C4—C6ⁱ	120.58 (12)	C1—C7—C12—C11	180.0
C2—C3—C4—C6ⁱ	−59.42 (12)	C10—C9—N1—O2	180.0
C2—C1—C7—C8	180.0	C8—C9—N1—O2	0.0
C2—C1—C7—C12	0.0	C10—C9—N1—O1	0.0
C12—C7—C8—C9	0.0	C8—C9—N1—O1	180.0
C1—C7—C8—C9	180.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱⁱ	0.98	2.44	3.367 (2)	158
C10—H10···O2ⁱⁱⁱ	0.95	2.50	3.366 (3)	152

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅NO₃
M_r	233.26
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	173
a, b, c (Å)	11.3375 (9), 7.2163 (6), 14.9327 (12)
V (Å³)	1221.72 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.48 × 0.36 × 0.15

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.958, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	5485, 1280, 937
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.123, 1.06
No. of reflections	1280
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.16

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱ	0.9800	2.4400	3.367 (2)	158.00
C10—H10···O2ⁱⁱ	0.9500	2.5000	3.366 (3)	152.00

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

Acknowledgements

The authors express their thanks to the National Key Technology R&D Program (No. 2006BAE01A01-4).

References

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