Crystals of the title compound, C
11H
9N
5O
4S, 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.
Supporting information
CCDC reference: 691023
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean
(C-C)= 0.002 Å
- R factor = 0.038
- wR factor = 0.120
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
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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.
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).
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).
(
E)-Methyl 1,3-thiazol-2-yl ketone 2,4-dinitrophenylhydrazone
top
Crystal data top
C11H9N5O4S | F(000) = 632 |
Mr = 307.29 | Dx = 1.592 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5366 reflections |
a = 8.0126 (5) Å | θ = 3.1–25.5° |
b = 7.3239 (4) Å | µ = 0.28 mm−1 |
c = 21.8683 (12) Å | T = 295 K |
β = 92.610 (2)° | Prism, orange |
V = 1281.98 (13) Å3 | 0.46 × 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 tube | Rint = 0.039 |
Graphite monochromator | θmax = 27.5°, θmin = 3.1° |
Detector resolution: 10.00 pixels mm-1 | h = −10→10 |
ω scans | k = −9→8 |
12253 measured reflections | l = −28→28 |
2943 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) = 0.119 | w = 1/[σ2(Fo2) + (0.0544P)2 + 0.1169P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
2943 reflections | Δρmax = 0.22 e Å−3 |
192 parameters | Δρmin = −0.19 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: 0.029 (3) |
Crystal data top
C11H9N5O4S | V = 1281.98 (13) Å3 |
Mr = 307.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0126 (5) Å | µ = 0.28 mm−1 |
b = 7.3239 (4) Å | T = 295 K |
c = 21.8683 (12) Å | 0.46 × 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 reflections | Rint = 0.039 |
2943 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.22 e Å−3 |
2943 reflections | Δρmin = −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 | x | y | z | Uiso*/Ueq | |
S1 | 0.18922 (7) | 0.17161 (8) | 0.69372 (2) | 0.0610 (2) | |
N1 | 0.3851 (2) | 0.1710 (2) | 0.39844 (7) | 0.0550 (4) | |
N2 | 0.9262 (2) | 0.3699 (2) | 0.33512 (8) | 0.0614 (5) | |
N3 | 0.49462 (19) | 0.2538 (2) | 0.52598 (6) | 0.0488 (4) | |
H3 | 0.3946 | 0.2130 | 0.5201 | 0.059* | |
N4 | 0.5583 (2) | 0.2973 (2) | 0.58348 (7) | 0.0523 (4) | |
N5 | 0.20975 (19) | 0.1562 (2) | 0.57733 (7) | 0.0508 (4) | |
O1 | 0.28243 (18) | 0.1495 (2) | 0.43763 (7) | 0.0762 (5) | |
O2 | 0.35547 (19) | 0.1322 (2) | 0.34454 (7) | 0.0777 (5) | |
O3 | 0.8766 (2) | 0.3374 (3) | 0.28262 (7) | 0.0865 (5) | |
O4 | 1.0639 (2) | 0.4328 (2) | 0.34849 (8) | 0.0820 (5) | |
C1 | 0.5967 (2) | 0.2783 (2) | 0.47889 (8) | 0.0436 (4) | |
C2 | 0.5482 (2) | 0.2422 (2) | 0.41680 (8) | 0.0439 (4) | |
C3 | 0.6570 (2) | 0.2710 (2) | 0.37046 (8) | 0.0475 (4) | |
H3A | 0.6232 | 0.2463 | 0.3301 | 0.057* | |
C4 | 0.8131 (2) | 0.3355 (2) | 0.38400 (8) | 0.0487 (5) | |
C5 | 0.8673 (2) | 0.3689 (3) | 0.44448 (9) | 0.0565 (5) | |
H5 | 0.9754 | 0.4101 | 0.4534 | 0.068* | |
C6 | 0.7610 (2) | 0.3408 (3) | 0.49027 (8) | 0.0531 (5) | |
H6 | 0.7982 | 0.3638 | 0.5304 | 0.064* | |
C7 | 0.4663 (2) | 0.2727 (3) | 0.62965 (8) | 0.0498 (4) | |
C8 | 0.2965 (2) | 0.2023 (2) | 0.62794 (8) | 0.0469 (4) | |
C9 | 0.0559 (3) | 0.0960 (3) | 0.59096 (9) | 0.0571 (5) | |
H9 | −0.0221 | 0.0579 | 0.5608 | 0.069* | |
C10 | 0.0226 (3) | 0.0947 (3) | 0.65099 (10) | 0.0622 (5) | |
H10 | −0.0778 | 0.0568 | 0.6666 | 0.075* | |
C11 | 0.5480 (3) | 0.3213 (3) | 0.69085 (9) | 0.0675 (6) | |
H11A | 0.6545 | 0.3770 | 0.6849 | 0.101* | |
H11B | 0.5635 | 0.2127 | 0.7150 | 0.101* | |
H11C | 0.4781 | 0.4052 | 0.7116 | 0.101* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0664 (4) | 0.0751 (4) | 0.0428 (3) | 0.0004 (3) | 0.0172 (2) | −0.0027 (2) |
N1 | 0.0516 (9) | 0.0714 (11) | 0.0421 (9) | −0.0039 (8) | 0.0013 (7) | 0.0003 (8) |
N2 | 0.0643 (11) | 0.0655 (11) | 0.0558 (11) | −0.0015 (9) | 0.0195 (9) | 0.0047 (9) |
N3 | 0.0477 (8) | 0.0626 (10) | 0.0361 (8) | −0.0014 (7) | 0.0045 (7) | −0.0016 (7) |
N4 | 0.0549 (10) | 0.0648 (10) | 0.0371 (8) | −0.0011 (8) | 0.0022 (7) | −0.0041 (7) |
N5 | 0.0541 (9) | 0.0563 (9) | 0.0424 (9) | 0.0006 (7) | 0.0060 (7) | 0.0014 (7) |
O1 | 0.0560 (9) | 0.1221 (14) | 0.0507 (9) | −0.0217 (8) | 0.0066 (7) | −0.0024 (8) |
O2 | 0.0684 (9) | 0.1195 (13) | 0.0448 (8) | −0.0168 (8) | −0.0027 (7) | −0.0133 (8) |
O3 | 0.0966 (12) | 0.1204 (14) | 0.0444 (9) | −0.0222 (10) | 0.0232 (8) | −0.0015 (9) |
O4 | 0.0623 (10) | 0.1066 (13) | 0.0786 (11) | −0.0139 (9) | 0.0215 (8) | 0.0070 (10) |
C1 | 0.0478 (10) | 0.0452 (9) | 0.0382 (9) | 0.0027 (8) | 0.0062 (8) | 0.0007 (8) |
C2 | 0.0456 (10) | 0.0477 (10) | 0.0385 (9) | 0.0024 (8) | 0.0026 (8) | 0.0017 (8) |
C3 | 0.0560 (11) | 0.0490 (10) | 0.0377 (9) | 0.0027 (9) | 0.0036 (8) | 0.0003 (8) |
C4 | 0.0529 (11) | 0.0519 (10) | 0.0424 (10) | 0.0016 (9) | 0.0124 (8) | 0.0016 (8) |
C5 | 0.0512 (11) | 0.0659 (12) | 0.0529 (11) | −0.0090 (9) | 0.0073 (9) | −0.0066 (10) |
C6 | 0.0510 (11) | 0.0671 (12) | 0.0412 (10) | −0.0063 (9) | 0.0031 (8) | −0.0078 (9) |
C7 | 0.0556 (11) | 0.0570 (11) | 0.0373 (9) | 0.0036 (9) | 0.0064 (8) | −0.0005 (8) |
C8 | 0.0548 (11) | 0.0487 (10) | 0.0379 (9) | 0.0054 (8) | 0.0088 (8) | 0.0017 (8) |
C9 | 0.0526 (11) | 0.0641 (12) | 0.0551 (12) | −0.0006 (10) | 0.0069 (9) | −0.0011 (10) |
C10 | 0.0585 (12) | 0.0690 (13) | 0.0607 (13) | −0.0011 (10) | 0.0186 (10) | −0.0012 (11) |
C11 | 0.0678 (14) | 0.0945 (16) | 0.0401 (11) | −0.0064 (12) | 0.0029 (10) | −0.0083 (10) |
Geometric parameters (Å, º) top
S1—C10 | 1.691 (2) | C2—C3 | 1.383 (2) |
S1—C8 | 1.7239 (19) | C3—C4 | 1.357 (3) |
N1—O1 | 1.225 (2) | C3—H3A | 0.9300 |
N1—O2 | 1.225 (2) | C4—C5 | 1.395 (3) |
N1—C2 | 1.447 (2) | C5—C6 | 1.359 (3) |
N2—O4 | 1.219 (2) | C5—H5 | 0.9300 |
N2—O3 | 1.221 (2) | C6—H6 | 0.9300 |
N2—C4 | 1.454 (2) | C7—C8 | 1.454 (3) |
N3—C1 | 1.356 (2) | C7—C11 | 1.505 (3) |
N3—N4 | 1.373 (2) | C9—C10 | 1.352 (3) |
N3—H3 | 0.8600 | C9—H9 | 0.9300 |
N4—C7 | 1.290 (2) | C10—H10 | 0.9300 |
N5—C8 | 1.324 (2) | C11—H11A | 0.9600 |
N5—C9 | 1.355 (3) | C11—H11B | 0.9600 |
C1—C6 | 1.405 (2) | C11—H11C | 0.9600 |
C1—C2 | 1.420 (2) | | |
| | | |
C10—S1—C8 | 89.63 (10) | C6—C5—C4 | 119.59 (18) |
O1—N1—O2 | 122.43 (17) | C6—C5—H5 | 120.2 |
O1—N1—C2 | 118.64 (15) | C4—C5—H5 | 120.2 |
O2—N1—C2 | 118.92 (17) | C5—C6—C1 | 122.14 (17) |
O4—N2—O3 | 123.44 (18) | C5—C6—H6 | 118.9 |
O4—N2—C4 | 118.47 (18) | C1—C6—H6 | 118.9 |
O3—N2—C4 | 118.07 (18) | N4—C7—C8 | 126.66 (16) |
C1—N3—N4 | 116.93 (15) | N4—C7—C11 | 114.95 (17) |
C1—N3—H3 | 121.5 | C8—C7—C11 | 118.38 (17) |
N4—N3—H3 | 121.5 | N5—C8—C7 | 124.57 (17) |
C7—N4—N3 | 118.86 (16) | N5—C8—S1 | 113.67 (14) |
C8—N5—C9 | 110.35 (17) | C7—C8—S1 | 121.76 (13) |
N3—C1—C6 | 120.08 (16) | C10—C9—N5 | 115.95 (19) |
N3—C1—C2 | 123.59 (16) | C10—C9—H9 | 122.0 |
C6—C1—C2 | 116.32 (16) | N5—C9—H9 | 122.0 |
C3—C2—C1 | 121.21 (16) | C9—C10—S1 | 110.40 (16) |
C3—C2—N1 | 116.32 (15) | C9—C10—H10 | 124.8 |
C1—C2—N1 | 122.46 (16) | S1—C10—H10 | 124.8 |
C4—C3—C2 | 119.92 (17) | C7—C11—H11A | 109.5 |
C4—C3—H3A | 120.0 | C7—C11—H11B | 109.5 |
C2—C3—H3A | 120.0 | H11A—C11—H11B | 109.5 |
C3—C4—C5 | 120.79 (18) | C7—C11—H11C | 109.5 |
C3—C4—N2 | 119.92 (17) | H11A—C11—H11C | 109.5 |
C5—C4—N2 | 119.30 (18) | H11B—C11—H11C | 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 | 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. |
Experimental details
Crystal data |
Chemical formula | C11H9N5O4S |
Mr | 307.29 |
Crystal system, space group | Monoclinic, 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) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.46 × 0.42 × 0.36 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID IP diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12253, 2943, 1845 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.119, 1.11 |
No. of reflections | 2943 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.19 |
Selected bond lengths (Å) topN3—C1 | 1.356 (2) | N4—C7 | 1.290 (2) |
N3—N4 | 1.373 (2) | | |
Hydrogen-bond geometry (Å, º) top
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. |
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).