PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1153.
Published online 2008 May 24. doi:  10.1107/S1600536808015122
PMCID: PMC2961490

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

Abstract

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 [triangle]); Shan et al. (2003a [triangle], 2006 [triangle]). For related structures, see: Vickery et al. (1985 [triangle]); Fan et al. (2004 [triangle]); Shan et al. (2003b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1153-scheme1.jpg

Experimental

Crystal data

  • C12H10N4O5
  • M r = 290.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1153-efi1.jpg
  • 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.111
  • S = 1.03
  • 2858 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.17 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and the torsion angle was refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined in riding mode, Uiso(H) = 1.2Ueq(C,N).

Figures

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].

Crystal data

C12H10N4O5F000 = 600
Mr = 290.24Dx = 1.532 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5266 reflections
a = 9.8917 (8) Åθ = 3.2–26.0º
b = 12.8477 (15) ŵ = 0.12 mm1
c = 10.6549 (12) ÅT = 293 (2) K
β = 111.63 (2)ºPrism, brown
V = 1258.7 (3) Å30.36 × 0.23 × 0.18 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer2858 independent reflections
Radiation source: fine-focus sealed tube1784 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
Detector resolution: 10.00 pixels mm-1θmax = 27.4º
T = 293(2) Kθmin = 3.2º
ω scansh = −12→12
Absorption correction: nonek = −16→16
12121 measured reflectionsl = −13→13

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038  w = 1/[σ2(Fo2) + (0.0649P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.111(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.21 e Å3
2858 reflectionsΔρmin = −0.17 e Å3
192 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0047 (11)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
O10.13582 (13)0.43547 (8)0.14104 (11)0.0648 (4)
O20.15573 (13)0.27996 (8)0.22020 (12)0.0648 (4)
O30.44159 (13)0.19704 (8)0.66737 (13)0.0660 (4)
O40.52296 (15)0.31707 (10)0.81753 (13)0.0742 (4)
O50.09817 (11)0.93990 (8)0.18361 (12)0.0566 (3)
N10.17859 (13)0.37357 (9)0.23615 (12)0.0452 (3)
N20.45693 (14)0.28930 (10)0.70150 (14)0.0498 (3)
N30.21841 (13)0.59367 (8)0.30483 (12)0.0412 (3)
H30.17570.57530.22190.049*
N40.22992 (13)0.69747 (8)0.33900 (12)0.0411 (3)
C10.27421 (13)0.52042 (9)0.40146 (14)0.0349 (3)
C20.25858 (14)0.41229 (10)0.37100 (14)0.0368 (3)
C30.31897 (14)0.33809 (10)0.46968 (15)0.0406 (3)
H3A0.30850.26770.44780.049*
C40.39417 (14)0.36870 (10)0.59975 (15)0.0403 (3)
C50.40955 (15)0.47424 (11)0.63469 (15)0.0412 (3)
H50.45970.49400.72380.049*
C60.35072 (14)0.54818 (10)0.53751 (14)0.0393 (3)
H60.36130.61820.56150.047*
C70.16518 (14)0.76093 (10)0.24031 (14)0.0395 (3)
C80.18273 (16)0.87045 (10)0.27796 (16)0.0431 (4)
C90.26625 (19)0.92158 (12)0.38905 (18)0.0586 (4)
H90.33290.89260.46740.070*
C100.2326 (2)1.02927 (13)0.3632 (2)0.0691 (5)
H100.27341.08420.42180.083*
C110.1335 (2)1.03623 (12)0.2414 (2)0.0662 (5)
H110.09261.09830.19970.079*
C120.07984 (19)0.73130 (12)0.09826 (17)0.0556 (4)
H12A0.14470.70730.05600.083*
H12B0.02680.79070.05020.083*
H12C0.01300.67670.09680.083*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0920 (9)0.0420 (6)0.0438 (7)−0.0007 (6)0.0055 (6)−0.0006 (5)
O20.0836 (8)0.0323 (6)0.0615 (8)−0.0105 (5)0.0068 (6)−0.0098 (5)
O30.0778 (8)0.0408 (6)0.0728 (9)0.0058 (5)0.0200 (7)0.0147 (5)
O40.0884 (9)0.0708 (8)0.0459 (8)0.0053 (7)0.0041 (7)0.0107 (6)
O50.0572 (6)0.0371 (6)0.0754 (8)0.0069 (5)0.0242 (6)0.0136 (5)
N10.0513 (7)0.0333 (6)0.0443 (8)−0.0020 (5)0.0096 (6)−0.0035 (5)
N20.0510 (7)0.0468 (8)0.0489 (9)0.0030 (6)0.0151 (6)0.0111 (6)
N30.0510 (7)0.0272 (5)0.0399 (7)−0.0003 (5)0.0103 (5)−0.0014 (5)
N40.0490 (7)0.0263 (6)0.0468 (7)−0.0013 (5)0.0164 (6)−0.0013 (5)
C10.0349 (7)0.0296 (6)0.0404 (8)−0.0010 (5)0.0142 (6)−0.0009 (5)
C20.0373 (7)0.0305 (6)0.0400 (8)−0.0020 (5)0.0112 (6)−0.0026 (5)
C30.0411 (7)0.0297 (6)0.0492 (9)−0.0020 (5)0.0147 (7)0.0013 (6)
C40.0395 (7)0.0372 (7)0.0434 (9)0.0017 (6)0.0146 (6)0.0064 (6)
C50.0421 (7)0.0439 (8)0.0366 (8)−0.0028 (6)0.0132 (6)−0.0034 (6)
C60.0433 (7)0.0316 (7)0.0448 (9)−0.0023 (6)0.0181 (6)−0.0047 (6)
C70.0428 (7)0.0343 (7)0.0427 (8)−0.0003 (6)0.0171 (6)0.0024 (6)
C80.0507 (8)0.0319 (7)0.0496 (9)0.0045 (6)0.0220 (7)0.0084 (6)
C90.0800 (11)0.0390 (8)0.0549 (10)−0.0056 (8)0.0227 (9)−0.0049 (7)
C100.0959 (14)0.0354 (8)0.0892 (15)−0.0106 (8)0.0495 (13)−0.0130 (9)
C110.0762 (12)0.0289 (8)0.1072 (18)0.0051 (8)0.0499 (13)0.0085 (9)
C120.0682 (10)0.0446 (8)0.0471 (10)0.0010 (8)0.0133 (8)0.0036 (7)

Geometric parameters (Å, °)

O1—N11.2338 (16)C3—H3A0.9300
O2—N11.2239 (15)C4—C51.3995 (19)
O3—N21.2327 (17)C5—C61.367 (2)
O4—N21.2194 (18)C5—H50.9300
O5—C111.369 (2)C6—H60.9300
O5—C81.3735 (18)C7—C81.4560 (19)
N1—C21.4491 (18)C7—C121.485 (2)
N2—C41.4510 (18)C8—C91.339 (2)
N3—C11.3533 (17)C9—C101.426 (2)
N3—N41.3760 (15)C9—H90.9300
N3—H30.8600C10—C111.309 (3)
N4—C71.2977 (18)C10—H100.9300
C1—C61.4115 (19)C11—H110.9300
C1—C21.4221 (17)C12—H12A0.9600
C2—C31.3813 (19)C12—H12B0.9600
C3—C41.367 (2)C12—H12C0.9600
C11—O5—C8105.81 (13)C4—C5—H5120.1
O2—N1—O1121.97 (13)C5—C6—C1121.31 (13)
O2—N1—C2118.71 (12)C5—C6—H6119.3
O1—N1—C2119.32 (11)C1—C6—H6119.3
O4—N2—O3122.83 (14)N4—C7—C8114.26 (13)
O4—N2—C4118.26 (13)N4—C7—C12126.16 (13)
O3—N2—C4118.91 (14)C8—C7—C12119.58 (12)
C1—N3—N4120.13 (12)C9—C8—O5109.82 (13)
C1—N3—H3119.9C9—C8—C7133.59 (14)
N4—N3—H3119.9O5—C8—C7116.59 (13)
C7—N4—N3115.25 (12)C8—C9—C10106.32 (17)
N3—C1—C6121.30 (12)C8—C9—H9126.8
N3—C1—C2121.75 (13)C10—C9—H9126.8
C6—C1—C2116.95 (12)C11—C10—C9107.09 (16)
C3—C2—C1121.36 (13)C11—C10—H10126.5
C3—C2—N1116.28 (12)C9—C10—H10126.5
C1—C2—N1122.37 (12)C10—C11—O5110.96 (14)
C4—C3—C2119.62 (13)C10—C11—H11124.5
C4—C3—H3A120.2O5—C11—H11124.5
C2—C3—H3A120.2C7—C12—H12A109.5
C3—C4—C5120.90 (13)C7—C12—H12B109.5
C3—C4—N2118.57 (13)H12A—C12—H12B109.5
C5—C4—N2120.52 (13)C7—C12—H12C109.5
C6—C5—C4119.84 (13)H12A—C12—H12C109.5
C6—C5—H5120.1H12B—C12—H12C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···O10.861.972.6063 (15)130
C9—H9···O4i0.932.413.334 (2)172
C11—H11···O2ii0.932.413.1530 (19)137

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2233).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography