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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 6| June 2008| Page o1156
doi:10.1107/S1600536808015298

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

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

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 16 May 2008; accepted 21 May 2008; online 24 May 2008)

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[Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678-1680.]); Shan et al. (2003[Shan, S., Xu, D.-J., Hung, C.-H., Wu, J.-Y. & Chiang, M. Y. (2003). Acta Cryst. C59, o135-o136.], 2006[Shan, S., Fan, Z. & Xu, D.-J. (2006). Acta Cryst. E62, o1123-o1125.]). For a related structure, see: Shan et al. (2008[Shan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008). Acta Cryst. E64, o1153.]).

[Scheme 1]

Experimental

Crystal data

  • C11H9N5O4S

  • Mr = 307.29

  • Monoclinic, P 21 /c

  • 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)

  • Rint = 0.039
Refinement

  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H3⋯O1 0.86 2.03 2.628 (2) 126
N3—H3⋯N5 0.86 2.03 2.686 (2) 133
C9—H9⋯O1i 0.93 2.58 3.289 (3) 133
Symmetry code: (i) -x, -y, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015298/om2236sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015298/om2236Isup2.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., 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).

Related literature top

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

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-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 top

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).

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
[Figure 1] Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms, dashed lines indicate hydrogen bonding.
[Figure 2] Fig. 2. A diagram showing the partially overlapped arrangement of benzene and thiazole rings [symmetry code: (i) 1 - x,1 - y,1 - z].
(E)-Methyl 1,3-thiazol-2-yl ketone 2,4-dinitrophenylhydrazone top
Crystal data top
C11H9N5O4SF(000) = 632
Mr = 307.29Dx = 1.592 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5366 reflections
a = 8.0126 (5) Åθ = 3.1–25.5°
b = 7.3239 (4) ŵ = 0.28 mm−1
c = 21.8683 (12) ÅT = 295 K
β = 92.610 (2)°Prism, orange
V = 1281.98 (13) Å30.46 × 0.42 × 0.36 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		1845 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
Graphite monochromatorθmax = 27.5°, θmin = 3.1°
Detector resolution: 10.00 pixels mm-1h = −10→10
ω scansk = −9→8
12253 measured reflectionsl = −28→28
2943 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.119 w = 1/[σ2(Fo2) + (0.0544P)2 + 0.1169P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2943 reflectionsΔρmax = 0.22 e Å−3
192 parametersΔρmin = −0.19 e Å−3
0 restraintsExtinction 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)
Crystal data top
C11H9N5O4SV = 1281.98 (13) Å3
Mr = 307.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.0126 (5) ŵ = 0.28 mm−1
b = 7.3239 (4) ÅT = 295 K
c = 21.8683 (12) Å0.46 × 0.42 × 0.36 mm
β = 92.610 (2)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		1845 reflections with I > 2σ(I)
12253 measured reflectionsRint = 0.039
2943 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.11Δρmax = 0.22 e Å−3
2943 reflectionsΔρmin = −0.19 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
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) top
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, º) top
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, º) top
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 code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formulaC11H9N5O4S
Mr307.29
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.0126 (5), 7.3239 (4), 21.8683 (12)
β (°) 92.610 (2)
V (Å3)1281.98 (13)
Z4
Radiation typeMo Kα
µ (mm−1)0.28
Crystal size (mm)0.46 × 0.42 × 0.36
Data collection
DiffractometerRigaku R-AXIS RAPID IP
diffractometer
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		12253, 2943, 1845
Rint0.039
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.119, 1.11
No. of reflections2943
No. of parameters192
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.22, −0.19

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—C11.356 (2)N4—C71.290 (2)
N3—N41.373 (2)
Hydrogen-bond geometry (Å, º) top
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 code: (i) −x, −y, −z+1.
 

Acknowledgements

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

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350.  CrossRef Web of Science IUCr Journals Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
 First citationOkabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationRigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar
 First citationShan, S., Fan, Z. & Xu, D.-J. (2006). Acta Cryst. E62, o1123–o1125.  CSD CrossRef IUCr Journals Google Scholar
 First citationShan, S., Tian, Y.-L., Wang, S.-H., Wang, W.-L. & Xu, Y.-L. (2008). Acta Cryst. E64, o1153.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationShan, S., Xu, D.-J., Hung, C.-H., Wu, J.-Y. & Chiang, M. Y. (2003). Acta Cryst. C59, o135–o136.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 6| June 2008| Page o1156
doi:10.1107/S1600536808015298
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