3-(3-Nitro­benzyl­idene)pentane-2,4-dione

Wu, C.

doi:10.1107/S1600536808043456

organic compounds

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Volume 65| Part 1| January 2009| Page o210

doi:10.1107/S1600536808043456

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3-(3-Nitrobenzylidene)pentane-2,4-dione

Chuanbing Wu ^a ^*

^aDepartment of Chemistry and Biology, Xiangfan University, Xiangfan 441053, People's Republic of China
^*Correspondence e-mail: wuchuanbing2008@yahoo.com.cn

(Received 9 December 2008; accepted 20 December 2008; online 24 December 2008)

In the title molecule, C₁₂H₁₁NO₄, the two acetyl C—C=O planes are inclined to the benzene ring at angles of 18.03 (8) and 80.75 (7)°. In the crystal, adjacent molecules are linked into centrosymmetric dimers by pairs of C—H⋯O interactions.

Related literature

For metal-complexes with β-diketones, see: Youngme et al. (2007 ); Ma et al. (2005 ); Soldatov et al. (2003 ); Hinckley (1969 ).

Experimental

Crystal data

C₁₂H₁₁NO₄
M_r = 233.22
Monoclinic, P 2₁ /c
a = 16.0634 (9) Å
b = 5.2470 (3) Å
c = 14.9774 (9) Å
β = 114.117 (1)°
V = 1152.18 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
Absorption correction: none
4779 measured reflections
1998 independent reflections
1400 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.171
S = 1.07
1998 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.42	3.282 (4)	153
Symmetry code: (i) -x+1, -y-1, -z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; 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/S1600536808043456/is2374sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043456/is2374Isup2.hkl

checkCIF report

Comment top

β-Diketone as an excellent chelating group has been widely used in supramolecular chemistry. It can form a variety of complexes with various transition-metals (e.g. Cu, Co, Ni, Mn, Pd, etc.) or rare-earth metals (e.g. Eu, Sm, La, Gd, etc.) (Youngme et al., 2007; Ma et al., 2005). These metal complexes have significant applications in material science or act as chemical shift reagents (Soldatov et al., 2003; Hinckley, 1969). Herein, we prepared and crystallized 3-(3-nitrobenzylidene)pentane-2,4-dione, (I).

The title compound can be considered as an alkene having two CH₃C(O)- substituents on one side of the double bond and the (NO₂)C₆H₃– unit substituend on the other. The acetyl group trans to the H substituent is not coplanar with the double bond and the aromatic system as a twist is necessary to avoid crowding with the H atom of the aromatic ring. The molecules are connected mainly by intermolecular C—H···O interactions.

Related literature top

For metal-complexes with β-diketones, see: Youngme et al. (2007); Ma et al. (2005); Soldatov et al. (2003); Hinckley (1969).

Experimental top

Piperidine (0.85 g, 10 mmol) was added to a dimethylformamide solution (30 ml) of acetylacetone (1 ml, 10 mmol) and 3-nitrobenzaldehyde (1.51 g, 10 mmol). The mixture was heated at 413 K for 6 h. The mixture was poured into water (300 ml) and the organic phase was extracted with ethyl acetate. The ethyl acetate extract was dried over sodium sulfate and the solvent removed under reduced pressure to yield the crude product, which was recrystallized from ethanol to afford colourless crystals in 50% yield.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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. View of the title molecule, showing the atom-labelling scheme. The displacement ellipsoids are drawn at the 30% probability level.

3-(3-Nitrobenzylidene)pentane-2,4-dione top

Crystal data top

C₁₂H₁₁NO₄	F(000) = 488
M_r = 233.22	D_x = 1.344 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1131 reflections
a = 16.0634 (9) Å	θ = 2.7–24.3°
b = 5.2470 (3) Å	µ = 0.10 mm⁻¹
c = 14.9774 (9) Å	T = 298 K
β = 114.117 (1)°	Block, colorless
V = 1152.18 (12) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1400 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 25.0°, θ_min = 2.7°
ϕ and ω scans	h = −19→17
4779 measured reflections	k = −6→6
1998 independent reflections	l = −11→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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.085P)² + 0.2322P] where P = (F_o² + 2F_c²)/3
1998 reflections	(Δ/σ)_max = 0.015
156 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₂H₁₁NO₄	V = 1152.18 (12) Å³
M_r = 233.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.0634 (9) Å	µ = 0.10 mm⁻¹
b = 5.2470 (3) Å	T = 298 K
c = 14.9774 (9) Å	0.20 × 0.10 × 0.10 mm
β = 114.117 (1)°

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1400 reflections with I > 2σ(I)
4779 measured reflections	R_int = 0.048
1998 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.07	Δρ_max = 0.21 e Å⁻³
1998 reflections	Δρ_min = −0.17 e Å⁻³
156 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
C1	0.37414 (19)	−0.0732 (5)	0.46603 (19)	0.0328 (7)
C2	0.31796 (19)	0.1238 (5)	0.4642 (2)	0.0359 (7)
C3	0.30722 (19)	0.1886 (5)	0.54900 (19)	0.0348 (7)
C4	0.3576 (2)	0.0531 (6)	0.6342 (2)	0.0405 (8)
C5	0.4149 (2)	−0.1425 (6)	0.6345 (2)	0.0458 (8)
C6	0.4239 (2)	−0.2098 (6)	0.5501 (2)	0.0399 (8)
C7	0.2427 (2)	0.3821 (5)	0.5535 (2)	0.0389 (8)
C8	0.1758 (2)	0.5058 (5)	0.4812 (2)	0.0361 (7)
C9	0.1551 (2)	0.4824 (5)	0.3737 (2)	0.0374 (7)
C10	0.0895 (2)	0.2825 (6)	0.3165 (2)	0.0536 (9)
C11	0.1120 (2)	0.6808 (6)	0.5006 (2)	0.0434 (8)
C12	0.1252 (3)	0.7457 (7)	0.6020 (2)	0.0606 (10)
H2	0.2871	0.2142	0.4066	0.043*
H4	0.3524	0.0957	0.6919	0.049*
H5	0.4478	−0.2299	0.6923	0.055*
H6	0.4621	−0.3426	0.5496	0.048*
H7	0.2494	0.4254	0.6163	0.047*
H10A	0.0808	0.2920	0.2492	0.080*
H10B	0.0322	0.3087	0.3211	0.080*
H10C	0.1132	0.1177	0.3423	0.080*
H12A	0.0831	0.8774	0.6004	0.091*
H12B	0.1865	0.8045	0.6380	0.091*
H12C	0.1146	0.5971	0.6333	0.091*
O1	0.34549 (17)	−0.0057 (5)	0.30328 (15)	0.0605 (7)
O2	0.4208 (2)	−0.3406 (5)	0.37212 (17)	0.0735 (9)
O3	0.19108 (17)	0.6251 (4)	0.33704 (16)	0.0612 (7)
O4	0.04744 (19)	0.7640 (5)	0.43075 (17)	0.0764 (9)
N1	0.38064 (17)	−0.1449 (5)	0.37404 (18)	0.0446 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0375 (16)	0.0307 (15)	0.0255 (15)	−0.0020 (13)	0.0081 (12)	0.0000 (12)
C2	0.0389 (18)	0.0356 (17)	0.0271 (15)	0.0044 (14)	0.0073 (13)	0.0059 (13)
C3	0.0415 (18)	0.0329 (16)	0.0252 (15)	0.0022 (14)	0.0086 (13)	0.0008 (12)
C4	0.0454 (19)	0.0436 (18)	0.0279 (16)	0.0054 (16)	0.0101 (14)	0.0034 (13)
C5	0.053 (2)	0.0437 (19)	0.0331 (18)	0.0134 (16)	0.0098 (15)	0.0120 (14)
C6	0.0411 (18)	0.0362 (17)	0.0372 (17)	0.0087 (14)	0.0106 (14)	0.0055 (13)
C7	0.0489 (19)	0.0360 (17)	0.0276 (15)	0.0043 (15)	0.0113 (14)	0.0002 (13)
C8	0.0436 (18)	0.0282 (15)	0.0318 (16)	0.0010 (14)	0.0106 (13)	−0.0005 (12)
C9	0.0459 (19)	0.0255 (15)	0.0337 (17)	0.0109 (14)	0.0090 (14)	0.0030 (13)
C10	0.060 (2)	0.049 (2)	0.0380 (18)	−0.0040 (17)	0.0067 (16)	−0.0081 (15)
C11	0.051 (2)	0.0351 (17)	0.0397 (18)	0.0093 (16)	0.0144 (16)	0.0029 (15)
C12	0.067 (2)	0.069 (2)	0.049 (2)	0.024 (2)	0.0270 (19)	−0.0043 (18)
O1	0.0875 (19)	0.0624 (16)	0.0339 (13)	0.0208 (14)	0.0272 (13)	0.0112 (12)
O2	0.099 (2)	0.0719 (18)	0.0522 (15)	0.0440 (16)	0.0329 (14)	−0.0027 (13)
O3	0.0875 (19)	0.0539 (15)	0.0387 (13)	−0.0124 (14)	0.0223 (13)	0.0093 (11)
O4	0.085 (2)	0.080 (2)	0.0463 (15)	0.0496 (16)	0.0092 (14)	0.0050 (13)
N1	0.0504 (17)	0.0471 (16)	0.0372 (15)	0.0072 (14)	0.0187 (13)	−0.0009 (13)

Geometric parameters (Å, º) top

C1—C6	1.384 (4)	C8—C9	1.511 (4)
C2—C1	1.365 (4)	C9—C10	1.485 (4)
C2—H2	0.9300	C10—H10A	0.9600
C3—C2	1.392 (4)	C10—H10B	0.9600
C3—C4	1.394 (4)	C10—H10C	0.9600
C3—C7	1.472 (4)	C11—C12	1.486 (4)
C4—C5	1.377 (4)	C12—H12A	0.9600
C4—H4	0.9300	C12—H12B	0.9600
C5—C6	1.376 (4)	C12—H12C	0.9600
C5—H5	0.9300	O3—C9	1.206 (4)
C6—H6	0.9300	O4—C11	1.214 (3)
C7—H7	0.9300	N1—O1	1.219 (3)
C8—C7	1.341 (4)	N1—O2	1.219 (3)
C8—C11	1.490 (4)	N1—C1	1.472 (4)

C1—C6—H6	121.2	C9—C10—H10A	109.5
C1—C2—C3	119.6 (3)	C9—C10—H10B	109.5
C1—C2—H2	120.2	C9—C10—H10C	109.5
C2—C3—C4	117.9 (3)	C10—C9—C8	117.8 (3)
C2—C3—C7	124.2 (2)	C11—C8—C9	112.9 (2)
C2—C1—C6	122.8 (3)	C11—C12—H12A	109.5
C2—C1—N1	118.3 (2)	C11—C12—H12B	109.5
C3—C2—H2	120.2	C11—C12—H12C	109.5
C3—C7—H7	114.9	C12—C11—C8	121.2 (3)
C3—C4—H4	119.3	H10A—C10—H10B	109.5
C4—C3—C7	117.8 (3)	H10A—C10—H10C	109.5
C4—C5—H5	119.7	H10B—C10—H10C	109.5
C5—C6—C1	117.7 (3)	H12A—C12—H12B	109.5
C5—C6—H6	121.1	H12A—C12—H12C	109.5
C5—C4—C3	121.4 (3)	H12B—C12—H12C	109.5
C5—C4—H4	119.3	O1—N1—O2	123.1 (3)
C6—C1—N1	118.9 (3)	O1—N1—C1	118.4 (2)
C6—C5—C4	120.6 (3)	O2—N1—C1	118.5 (3)
C6—C5—H5	119.7	O3—C9—C10	122.4 (3)
C7—C8—C11	121.9 (3)	O3—C9—C8	119.8 (3)
C7—C8—C9	125.2 (3)	O4—C11—C12	120.9 (3)
C8—C7—C3	130.1 (3)	O4—C11—C8	117.8 (3)
C8—C7—H7	114.9

C2—C1—C6—C5	0.5 (5)	C7—C8—C11—O4	−172.3 (3)
C2—C3—C4—C5	−1.3 (5)	C7—C8—C11—C12	6.0 (5)
C2—C3—C7—C8	9.8 (5)	C9—C8—C11—O4	6.7 (4)
C3—C2—C1—C6	−1.9 (5)	C9—C8—C11—C12	−175.1 (3)
C3—C2—C1—N1	177.1 (2)	C9—C8—C7—C3	−4.2 (5)
C3—C4—C5—C6	−0.1 (5)	C11—C8—C7—C3	174.6 (3)
C4—C5—C6—C1	0.5 (5)	C11—C8—C9—O3	90.6 (4)
C4—C3—C2—C1	2.3 (4)	C11—C8—C9—C10	−88.8 (3)
C4—C3—C7—C8	−167.0 (3)	O1—N1—C1—C2	9.6 (4)
C7—C3—C4—C5	175.7 (3)	O1—N1—C1—C6	−171.4 (3)
C7—C8—C9—O3	−90.5 (4)	O2—N1—C1—C6	8.7 (4)
C7—C3—C2—C1	−174.5 (3)	O2—N1—C1—C2	−170.3 (3)
C7—C8—C9—C10	90.1 (4)	N1—C1—C6—C5	−178.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.42	3.282 (4)	153

Symmetry code: (i) −x+1, −y−1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁NO₄
M_r	233.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	16.0634 (9), 5.2470 (3), 14.9774 (9)
β (°)	114.117 (1)
V (Å³)	1152.18 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART 4K CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4779, 1998, 1400
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.171, 1.07
No. of reflections	1998
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), 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—H6···O2ⁱ	0.93	2.42	3.282 (4)	153

Symmetry code: (i) −x+1, −y−1, −z+1.

Acknowledgements

The author is grateful to Xiangfan University for financial support.

References

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