(E)-2-Furyl methyl ketone 2,4-dinitro­phenyl­hydrazone

Shan, S.; Tian, Y.-L.; Wang, S.-H.; Wang, W.-L.; Xu, Y.-L.

doi:10.1107/S1600536808015122

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1153

doi:10.1107/S1600536808015122

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(E)-2-Furyl methyl ketone 2,4-dinitrophenylhydrazone

Shang Shan,^a ^* Yu-Liang Tian,^a Shan-Heng Wang,^a Wen-Long Wang ^a and Ying-Li Xu ^a

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 2 May 2008; accepted 19 May 2008; online 24 May 2008)

Crystals of the title compound, C₁₂H₁₀N₄O₅, were obtained from a condensation reaction of 2,4-dinitrophenylhydrazine and 2-furyl methyl ketone. The molecule displays a nearly planar structure, and the furan ring is slightly twisted by a dihedral angle of 12.62 (6)° with respect to the phenylhydrazone plane. The face-to-face separation of 3.287 (7) Å between parallel benzene rings of adjacent molecules indicates the existence of π–π stacking between dinitrophenyl rings in the crystal structure.

Related literature

For general background, see: Okabe et al. (1993 ); Shan et al. (2003a , 2006 ). For related structures, see: Vickery et al. (1985 ); Fan et al. (2004 ); Shan et al. (2003b ).

Experimental

Crystal data

C₁₂H₁₀N₄O₅
M_r = 290.24
Monoclinic, P 2₁ /c
a = 9.8917 (8) Å
b = 12.8477 (15) Å
c = 10.6549 (12) Å
β = 111.63 (2)°
V = 1258.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.36 × 0.23 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: none
12121 measured reflections
2858 independent reflections
1784 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.03
2858 reflections
192 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
N3—H3⋯O1	0.86	1.97	2.6063 (15)	130
C9—H9⋯O4ⁱ	0.93	2.41	3.334 (2)	172
C11—H11⋯O2ⁱⁱ	0.93	2.41	3.1530 (19)	137
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015122/om2233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015122/om2233Isup2.hkl

checkCIF report

Comment top

As some phenylhydrazone derivatives have shown to be potentially DNA damaging and mutagenic agents (Okabe et al., 1993), a series of new phenylhydrazone derivatives have been synthesized in our laboratory (Shan et al., 2003a; Shan et al., 2006). As part of the ongoing investigation, the title compound has recently been prepared and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The molecule displays an approximately planar structure, the furan ring is slightly twisted with respect to the phenylhydrazone plane with a dihedral angle of 12.62 (6)°. The N4—C7 bond distance (Table 1) indicates a typical C=N double dond. The molecule assumes an E configuration with the phenylhydrazine and furan located on the opposite sides of the C=N bond. An intramolecular hydrogen bond is observed between the N3-imino and the adjacent N1-nitro groups; such a hydrogen bonding is a common feature in o-nitrophenylhydrazine compounds (Vickery et al., 1985; Fan et al., 2004).

A partially overlapped arrangement of parallel benzene rings of adjacent molecules is illustrated in Fig. 2. The face-to-face separation of 3.287 (7) Å strongly indicates the existence of π-π stacking between parallel dinitrophenyl rings of adjacent molecules in the crystal. It agrees with that found in a related dinitrophenylhydrazine compound, isobutylaldehyde 2,4-dinitrophenylhydrazone (Shan et al., 2003b).

The crystal structure also contains intermolecular weak C—H···O hydrogen bonding (Table 2).

Related literature top

For general background, see: Okabe et al. (1993); Shan et al. (2003a, 2006). For related structures, see: Vickery et al. (1985); Fan et al. (2004); Shan et al. (2003b).

Experimental top

2,4-Dinitrophenylhydrazine (0.4 g, 2 mmol) was dissolved in ethanol (10 ml), and H₂SO₄ solution (98%, 0.5 ml) was slowly added to the ethanol solution with stirring. The solution was heated at 333 K for several min until the solution cleared. 2-Furyl methylketone (0.22 g, 2 mmol) was added to the above solution with continuous stirring, and the mixture was refluxed for 30 min. When the solution had cooled to room temperature brown powder crystals appeared. The powder crystals were separated and washed with water three times. Recrystallization from an absolute ethanol solution yielded well shaped single crystals.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A diagram showing the overlapped arrangement of parallel benzene rings of neighboring molecules [symmetry code: (i) 1 - x,1 - y,1 - z].

(E)-2-Furyl methyl ketone 2,4-dinitrophenylhydrazone top

Crystal data top

C₁₂H₁₀N₄O₅	F(000) = 600
M_r = 290.24	D_x = 1.532 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5266 reflections
a = 9.8917 (8) Å	θ = 3.2–26.0°
b = 12.8477 (15) Å	µ = 0.12 mm⁻¹
c = 10.6549 (12) Å	T = 293 K
β = 111.63 (2)°	Prism, brown
V = 1258.7 (3) Å³	0.36 × 0.23 × 0.18 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1784 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 27.4°, θ_min = 3.2°
Detector resolution: 10.00 pixels mm^-1	h = −12→12
ω scans	k = −16→16
12121 measured reflections	l = −13→13
2858 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0649P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2858 reflections	Δρ_max = 0.21 e Å⁻³
192 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (11)

Crystal data top

C₁₂H₁₀N₄O₅	V = 1258.7 (3) Å³
M_r = 290.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8917 (8) Å	µ = 0.12 mm⁻¹
b = 12.8477 (15) Å	T = 293 K
c = 10.6549 (12) Å	0.36 × 0.23 × 0.18 mm
β = 111.63 (2)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1784 reflections with I > 2σ(I)
12121 measured reflections	R_int = 0.026
2858 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
2858 reflections	Δρ_min = −0.17 e Å⁻³
192 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	0.13582 (13)	0.43547 (8)	0.14104 (11)	0.0648 (4)
O2	0.15573 (13)	0.27996 (8)	0.22020 (12)	0.0648 (4)
O3	0.44159 (13)	0.19704 (8)	0.66737 (13)	0.0660 (4)
O4	0.52296 (15)	0.31707 (10)	0.81753 (13)	0.0742 (4)
O5	0.09817 (11)	0.93990 (8)	0.18361 (12)	0.0566 (3)
N1	0.17859 (13)	0.37357 (9)	0.23615 (12)	0.0452 (3)
N2	0.45693 (14)	0.28930 (10)	0.70150 (14)	0.0498 (3)
N3	0.21841 (13)	0.59367 (8)	0.30483 (12)	0.0412 (3)
H3	0.1757	0.5753	0.2219	0.049*
N4	0.22992 (13)	0.69747 (8)	0.33900 (12)	0.0411 (3)
C1	0.27421 (13)	0.52042 (9)	0.40146 (14)	0.0349 (3)
C2	0.25858 (14)	0.41229 (10)	0.37100 (14)	0.0368 (3)
C3	0.31897 (14)	0.33809 (10)	0.46968 (15)	0.0406 (3)
H3A	0.3085	0.2677	0.4478	0.049*
C4	0.39417 (14)	0.36870 (10)	0.59975 (15)	0.0403 (3)
C5	0.40955 (15)	0.47424 (11)	0.63469 (15)	0.0412 (3)
H5	0.4597	0.4940	0.7238	0.049*
C6	0.35072 (14)	0.54818 (10)	0.53751 (14)	0.0393 (3)
H6	0.3613	0.6182	0.5615	0.047*
C7	0.16518 (14)	0.76093 (10)	0.24031 (14)	0.0395 (3)
C8	0.18273 (16)	0.87045 (10)	0.27796 (16)	0.0431 (4)
C9	0.26625 (19)	0.92158 (12)	0.38905 (18)	0.0586 (4)
H9	0.3329	0.8926	0.4674	0.070*
C10	0.2326 (2)	1.02927 (13)	0.3632 (2)	0.0691 (5)
H10	0.2734	1.0842	0.4218	0.083*
C11	0.1335 (2)	1.03623 (12)	0.2414 (2)	0.0662 (5)
H11	0.0926	1.0983	0.1997	0.079*
C12	0.07984 (19)	0.73130 (12)	0.09826 (17)	0.0556 (4)
H12A	0.1447	0.7073	0.0560	0.083*
H12B	0.0268	0.7907	0.0502	0.083*
H12C	0.0130	0.6767	0.0968	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0920 (9)	0.0420 (6)	0.0438 (7)	−0.0007 (6)	0.0055 (6)	−0.0006 (5)
O2	0.0836 (8)	0.0323 (6)	0.0615 (8)	−0.0105 (5)	0.0068 (6)	−0.0098 (5)
O3	0.0778 (8)	0.0408 (6)	0.0728 (9)	0.0058 (5)	0.0200 (7)	0.0147 (5)
O4	0.0884 (9)	0.0708 (8)	0.0459 (8)	0.0053 (7)	0.0041 (7)	0.0107 (6)
O5	0.0572 (6)	0.0371 (6)	0.0754 (8)	0.0069 (5)	0.0242 (6)	0.0136 (5)
N1	0.0513 (7)	0.0333 (6)	0.0443 (8)	−0.0020 (5)	0.0096 (6)	−0.0035 (5)
N2	0.0510 (7)	0.0468 (8)	0.0489 (9)	0.0030 (6)	0.0151 (6)	0.0111 (6)
N3	0.0510 (7)	0.0272 (5)	0.0399 (7)	−0.0003 (5)	0.0103 (5)	−0.0014 (5)
N4	0.0490 (7)	0.0263 (6)	0.0468 (7)	−0.0013 (5)	0.0164 (6)	−0.0013 (5)
C1	0.0349 (7)	0.0296 (6)	0.0404 (8)	−0.0010 (5)	0.0142 (6)	−0.0009 (5)
C2	0.0373 (7)	0.0305 (6)	0.0400 (8)	−0.0020 (5)	0.0112 (6)	−0.0026 (5)
C3	0.0411 (7)	0.0297 (6)	0.0492 (9)	−0.0020 (5)	0.0147 (7)	0.0013 (6)
C4	0.0395 (7)	0.0372 (7)	0.0434 (9)	0.0017 (6)	0.0146 (6)	0.0064 (6)
C5	0.0421 (7)	0.0439 (8)	0.0366 (8)	−0.0028 (6)	0.0132 (6)	−0.0034 (6)
C6	0.0433 (7)	0.0316 (7)	0.0448 (9)	−0.0023 (6)	0.0181 (6)	−0.0047 (6)
C7	0.0428 (7)	0.0343 (7)	0.0427 (8)	−0.0003 (6)	0.0171 (6)	0.0024 (6)
C8	0.0507 (8)	0.0319 (7)	0.0496 (9)	0.0045 (6)	0.0220 (7)	0.0084 (6)
C9	0.0800 (11)	0.0390 (8)	0.0549 (10)	−0.0056 (8)	0.0227 (9)	−0.0049 (7)
C10	0.0959 (14)	0.0354 (8)	0.0892 (15)	−0.0106 (8)	0.0495 (13)	−0.0130 (9)
C11	0.0762 (12)	0.0289 (8)	0.1072 (18)	0.0051 (8)	0.0499 (13)	0.0085 (9)
C12	0.0682 (10)	0.0446 (8)	0.0471 (10)	0.0010 (8)	0.0133 (8)	0.0036 (7)

Geometric parameters (Å, º) top

O1—N1	1.2338 (16)	C3—H3A	0.9300
O2—N1	1.2239 (15)	C4—C5	1.3995 (19)
O3—N2	1.2327 (17)	C5—C6	1.367 (2)
O4—N2	1.2194 (18)	C5—H5	0.9300
O5—C11	1.369 (2)	C6—H6	0.9300
O5—C8	1.3735 (18)	C7—C8	1.4560 (19)
N1—C2	1.4491 (18)	C7—C12	1.485 (2)
N2—C4	1.4510 (18)	C8—C9	1.339 (2)
N3—C1	1.3533 (17)	C9—C10	1.426 (2)
N3—N4	1.3760 (15)	C9—H9	0.9300
N3—H3	0.8600	C10—C11	1.309 (3)
N4—C7	1.2977 (18)	C10—H10	0.9300
C1—C6	1.4115 (19)	C11—H11	0.9300
C1—C2	1.4221 (17)	C12—H12A	0.9600
C2—C3	1.3813 (19)	C12—H12B	0.9600
C3—C4	1.367 (2)	C12—H12C	0.9600

C11—O5—C8	105.81 (13)	C4—C5—H5	120.1
O2—N1—O1	121.97 (13)	C5—C6—C1	121.31 (13)
O2—N1—C2	118.71 (12)	C5—C6—H6	119.3
O1—N1—C2	119.32 (11)	C1—C6—H6	119.3
O4—N2—O3	122.83 (14)	N4—C7—C8	114.26 (13)
O4—N2—C4	118.26 (13)	N4—C7—C12	126.16 (13)
O3—N2—C4	118.91 (14)	C8—C7—C12	119.58 (12)
C1—N3—N4	120.13 (12)	C9—C8—O5	109.82 (13)
C1—N3—H3	119.9	C9—C8—C7	133.59 (14)
N4—N3—H3	119.9	O5—C8—C7	116.59 (13)
C7—N4—N3	115.25 (12)	C8—C9—C10	106.32 (17)
N3—C1—C6	121.30 (12)	C8—C9—H9	126.8
N3—C1—C2	121.75 (13)	C10—C9—H9	126.8
C6—C1—C2	116.95 (12)	C11—C10—C9	107.09 (16)
C3—C2—C1	121.36 (13)	C11—C10—H10	126.5
C3—C2—N1	116.28 (12)	C9—C10—H10	126.5
C1—C2—N1	122.37 (12)	C10—C11—O5	110.96 (14)
C4—C3—C2	119.62 (13)	C10—C11—H11	124.5
C4—C3—H3A	120.2	O5—C11—H11	124.5
C2—C3—H3A	120.2	C7—C12—H12A	109.5
C3—C4—C5	120.90 (13)	C7—C12—H12B	109.5
C3—C4—N2	118.57 (13)	H12A—C12—H12B	109.5
C5—C4—N2	120.52 (13)	C7—C12—H12C	109.5
C6—C5—C4	119.84 (13)	H12A—C12—H12C	109.5
C6—C5—H5	120.1	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.86	1.97	2.6063 (15)	130
C9—H9···O4ⁱ	0.93	2.41	3.334 (2)	172
C11—H11···O2ⁱⁱ	0.93	2.41	3.1530 (19)	137

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₄O₅
M_r	290.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.8917 (8), 12.8477 (15), 10.6549 (12)
β (°)	111.63 (2)
V (Å³)	1258.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.36 × 0.23 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12121, 2858, 1784
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.03
No. of reflections	2858
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

N3—C1	1.3533 (17)	N4—C7	1.2977 (18)
N3—N4	1.3760 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.86	1.97	2.6063 (15)	130
C9—H9···O4ⁱ	0.93	2.41	3.334 (2)	172
C11—H11···O2ⁱⁱ	0.93	2.41	3.1530 (19)	137

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

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Fan, Z., Shan, S., Hu, W.-X. & Xu, D.-J. (2004). Acta Cryst. E60, o1102–o1104. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Shan, S., Fan, Z. & Xu, D.-J. (2006). Acta Cryst. E62, o1123–o1125. CSD CrossRef IUCr Journals Google Scholar
Shan, S., Xu, D.-J. & Hu, W.-X. (2003b). Acta Cryst. E59, o838–o840. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shan, S., Xu, D.-J., Hung, C.-H., Wu, J.-Y. & Chiang, M. Y. (2003a). Acta Cryst. C59, o135–o136. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vickery, B., Willey, G. R. & Drew, M. G. B. (1985). Acta Cryst. C41, 1072–1075. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar