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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1156.
Published online 2008 May 24. doi:  10.1107/S1600536808015298
PMCID: PMC2961542

(E)-Methyl 1,3-thia­zol-2-yl ketone 2,4-dinitro­phenyl­hydrazone

Abstract

Crystals of the title compound, C11H9N5O4S, were obtained from a condensation reaction of 2,4-dinitro­phenyl­hydrazine and methyl 1,3-thia­zol-2-yl ketone. Excluding two methyl H atoms, the mol­ecule displays a planar structure, the dihedral angle between the terminal thia­zole and benzene rings being 1.82 (8)°. The imino group links with adjacent nitro and thia­zole groups by intra­molecular bifurcated hydrogen bonding. The centroid–centroid separation of 3.7273 (11) Å between nearly parallel benzene and thia­zole rings of adjacent mol­ecules indicates the existence of π–π stacking in the crystal structure. Weak inter­molecular C—H(...)O hydrogen bonding is also observed.

Related literature

For general background, see: Okabe et al. (1993 [triangle]); Shan et al. (2003 [triangle], 2006 [triangle]). For a related structure, see: Shan et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1156-scheme1.jpg

Experimental

Crystal data

  • C11H9N5O4S
  • M r = 307.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1156-efi1.jpg
  • a = 8.0126 (5) Å
  • b = 7.3239 (4) Å
  • c = 21.8683 (12) Å
  • β = 92.610 (2)°
  • V = 1281.98 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 295 (2) K
  • 0.46 × 0.42 × 0.36 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: none
  • 12253 measured reflections
  • 2943 independent reflections
  • 1845 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.119
  • S = 1.11
  • 2943 reflections
  • 192 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.19 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/S1600536808015298/om2236sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015298/om2236Isup2.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., 2003; 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 a coplanar structure, except methyl H atoms, the dihedral angle between the thiazole and benzene rings being 1.82 (8)°. The N4—C7 bond distance is significantly shorter than N3—N4 and N3—C1 bond distances (Table 1), and indicates the typical C?N double bond. The phenylhydrazone and thiazole are located on the opposite sides of the C?N double bond, the molecule has an E-configuration, similar to that found in a related compound, (E)-2-furlyl methylketone 2,4-dinitrophenylhydrazone (Shan et al., 2008). The imino group links with adjacent nitro and thiazole groups by intra-molecular bifurcated hydrogen bonding (Fig. 1 and Table 2).

A partially overlapped arrangement between nearly parallel benzene ring and thiazole ring of the adjacent molecule is illustrated in Fig. 2. The dihedral angle and centroid-to-centroid separation are 1.82 (8)° and 3.7273 (11) Å, these suggest the existence of π-π stacking between adjacent molecules in the crystal. 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-Thiazolyl methyl ketone (0.25 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 yellow powder crystals appeared. The powder crystals were separated and washed with water three times. Recrystallization from an absolute ethanol 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 with 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, dashed lines indicate hydrogen bonding.
Fig. 2.
A diagram showing the partially overlapped arrangement of benzene and thiazole rings [symmetry code: (i) 1 - x,1 - y,1 - z].

Crystal data

C11H9N5O4SF000 = 632
Mr = 307.29Dx = 1.592 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5366 reflections
a = 8.0126 (5) Åθ = 3.1–25.5º
b = 7.3239 (4) ŵ = 0.28 mm1
c = 21.8683 (12) ÅT = 295 (2) K
β = 92.610 (2)ºPrism, orange
V = 1281.98 (13) Å30.46 × 0.42 × 0.36 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer2943 independent reflections
Radiation source: fine-focus sealed tube1845 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.039
Detector resolution: 10.00 pixels mm-1θmax = 27.5º
T = 295(2) Kθmin = 3.1º
ω scansh = −10→10
Absorption correction: nonek = −9→8
12253 measured reflectionsl = −28→28

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) + (0.0544P)2 + 0.1169P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.119(Δ/σ)max < 0.001
S = 1.11Δρmax = 0.22 e Å3
2943 reflectionsΔρmin = −0.19 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: 0.029 (3)
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
S10.18922 (7)0.17161 (8)0.69372 (2)0.0610 (2)
N10.3851 (2)0.1710 (2)0.39844 (7)0.0550 (4)
N20.9262 (2)0.3699 (2)0.33512 (8)0.0614 (5)
N30.49462 (19)0.2538 (2)0.52598 (6)0.0488 (4)
H30.39460.21300.52010.059*
N40.5583 (2)0.2973 (2)0.58348 (7)0.0523 (4)
N50.20975 (19)0.1562 (2)0.57733 (7)0.0508 (4)
O10.28243 (18)0.1495 (2)0.43763 (7)0.0762 (5)
O20.35547 (19)0.1322 (2)0.34454 (7)0.0777 (5)
O30.8766 (2)0.3374 (3)0.28262 (7)0.0865 (5)
O41.0639 (2)0.4328 (2)0.34849 (8)0.0820 (5)
C10.5967 (2)0.2783 (2)0.47889 (8)0.0436 (4)
C20.5482 (2)0.2422 (2)0.41680 (8)0.0439 (4)
C30.6570 (2)0.2710 (2)0.37046 (8)0.0475 (4)
H3A0.62320.24630.33010.057*
C40.8131 (2)0.3355 (2)0.38400 (8)0.0487 (5)
C50.8673 (2)0.3689 (3)0.44448 (9)0.0565 (5)
H50.97540.41010.45340.068*
C60.7610 (2)0.3408 (3)0.49027 (8)0.0531 (5)
H60.79820.36380.53040.064*
C70.4663 (2)0.2727 (3)0.62965 (8)0.0498 (4)
C80.2965 (2)0.2023 (2)0.62794 (8)0.0469 (4)
C90.0559 (3)0.0960 (3)0.59096 (9)0.0571 (5)
H9−0.02210.05790.56080.069*
C100.0226 (3)0.0947 (3)0.65099 (10)0.0622 (5)
H10−0.07780.05680.66660.075*
C110.5480 (3)0.3213 (3)0.69085 (9)0.0675 (6)
H11A0.65450.37700.68490.101*
H11B0.56350.21270.71500.101*
H11C0.47810.40520.71160.101*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0664 (4)0.0751 (4)0.0428 (3)0.0004 (3)0.0172 (2)−0.0027 (2)
N10.0516 (9)0.0714 (11)0.0421 (9)−0.0039 (8)0.0013 (7)0.0003 (8)
N20.0643 (11)0.0655 (11)0.0558 (11)−0.0015 (9)0.0195 (9)0.0047 (9)
N30.0477 (8)0.0626 (10)0.0361 (8)−0.0014 (7)0.0045 (7)−0.0016 (7)
N40.0549 (10)0.0648 (10)0.0371 (8)−0.0011 (8)0.0022 (7)−0.0041 (7)
N50.0541 (9)0.0563 (9)0.0424 (9)0.0006 (7)0.0060 (7)0.0014 (7)
O10.0560 (9)0.1221 (14)0.0507 (9)−0.0217 (8)0.0066 (7)−0.0024 (8)
O20.0684 (9)0.1195 (13)0.0448 (8)−0.0168 (8)−0.0027 (7)−0.0133 (8)
O30.0966 (12)0.1204 (14)0.0444 (9)−0.0222 (10)0.0232 (8)−0.0015 (9)
O40.0623 (10)0.1066 (13)0.0786 (11)−0.0139 (9)0.0215 (8)0.0070 (10)
C10.0478 (10)0.0452 (9)0.0382 (9)0.0027 (8)0.0062 (8)0.0007 (8)
C20.0456 (10)0.0477 (10)0.0385 (9)0.0024 (8)0.0026 (8)0.0017 (8)
C30.0560 (11)0.0490 (10)0.0377 (9)0.0027 (9)0.0036 (8)0.0003 (8)
C40.0529 (11)0.0519 (10)0.0424 (10)0.0016 (9)0.0124 (8)0.0016 (8)
C50.0512 (11)0.0659 (12)0.0529 (11)−0.0090 (9)0.0073 (9)−0.0066 (10)
C60.0510 (11)0.0671 (12)0.0412 (10)−0.0063 (9)0.0031 (8)−0.0078 (9)
C70.0556 (11)0.0570 (11)0.0373 (9)0.0036 (9)0.0064 (8)−0.0005 (8)
C80.0548 (11)0.0487 (10)0.0379 (9)0.0054 (8)0.0088 (8)0.0017 (8)
C90.0526 (11)0.0641 (12)0.0551 (12)−0.0006 (10)0.0069 (9)−0.0011 (10)
C100.0585 (12)0.0690 (13)0.0607 (13)−0.0011 (10)0.0186 (10)−0.0012 (11)
C110.0678 (14)0.0945 (16)0.0401 (11)−0.0064 (12)0.0029 (10)−0.0083 (10)

Geometric parameters (Å, °)

S1—C101.691 (2)C2—C31.383 (2)
S1—C81.7239 (19)C3—C41.357 (3)
N1—O11.225 (2)C3—H3A0.9300
N1—O21.225 (2)C4—C51.395 (3)
N1—C21.447 (2)C5—C61.359 (3)
N2—O41.219 (2)C5—H50.9300
N2—O31.221 (2)C6—H60.9300
N2—C41.454 (2)C7—C81.454 (3)
N3—C11.356 (2)C7—C111.505 (3)
N3—N41.373 (2)C9—C101.352 (3)
N3—H30.8600C9—H90.9300
N4—C71.290 (2)C10—H100.9300
N5—C81.324 (2)C11—H11A0.9600
N5—C91.355 (3)C11—H11B0.9600
C1—C61.405 (2)C11—H11C0.9600
C1—C21.420 (2)
C10—S1—C889.63 (10)C6—C5—C4119.59 (18)
O1—N1—O2122.43 (17)C6—C5—H5120.2
O1—N1—C2118.64 (15)C4—C5—H5120.2
O2—N1—C2118.92 (17)C5—C6—C1122.14 (17)
O4—N2—O3123.44 (18)C5—C6—H6118.9
O4—N2—C4118.47 (18)C1—C6—H6118.9
O3—N2—C4118.07 (18)N4—C7—C8126.66 (16)
C1—N3—N4116.93 (15)N4—C7—C11114.95 (17)
C1—N3—H3121.5C8—C7—C11118.38 (17)
N4—N3—H3121.5N5—C8—C7124.57 (17)
C7—N4—N3118.86 (16)N5—C8—S1113.67 (14)
C8—N5—C9110.35 (17)C7—C8—S1121.76 (13)
N3—C1—C6120.08 (16)C10—C9—N5115.95 (19)
N3—C1—C2123.59 (16)C10—C9—H9122.0
C6—C1—C2116.32 (16)N5—C9—H9122.0
C3—C2—C1121.21 (16)C9—C10—S1110.40 (16)
C3—C2—N1116.32 (15)C9—C10—H10124.8
C1—C2—N1122.46 (16)S1—C10—H10124.8
C4—C3—C2119.92 (17)C7—C11—H11A109.5
C4—C3—H3A120.0C7—C11—H11B109.5
C2—C3—H3A120.0H11A—C11—H11B109.5
C3—C4—C5120.79 (18)C7—C11—H11C109.5
C3—C4—N2119.92 (17)H11A—C11—H11C109.5
C5—C4—N2119.30 (18)H11B—C11—H11C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···O10.862.032.628 (2)126
N3—H3···N50.862.032.686 (2)133
C9—H9···O1i0.932.583.289 (3)133

Symmetry codes: (i) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2236).

References

  • Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst.26, 343–350.
  • 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., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008). Acta Cryst. E64, o1153. [PMC free article] [PubMed]
  • Shan, S., Xu, D.-J., Hung, C.-H., Wu, J.-Y. & Chiang, M. Y. (2003). Acta Cryst. C59, o135–o136. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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