(E)-Methyl 1,3-thia-zol-2-yl ketone 2,4-dinitro-phenyl-hydrazone.

Crystals of the title compound, C(11)H(9)N(5)O(4)S, were obtained from a condensation reaction of 2,4-dinitro-phenyl-hydrazine and methyl 1,3-thia-zol-2-yl ketone. Excluding two methyl H atoms, the mol-ecule displays a planar structure, the dihedral angle between the terminal thia-zole and benzene rings being 1.82 (8)°. The imino group links with adjacent nitro and thia-zole groups by intra-molecular bifurcated hydrogen bonding. The centroid-centroid separation of 3.7273 (11) Å between nearly parallel benzene and thia-zole rings of adjacent mol-ecules indicates the existence of π-π stacking in the crystal structure. Weak inter-molecular C-H⋯O hydrogen bonding is also observed.

Related literature

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

Experimental

Crystal data

C11H9N5O4S

M = 307.29

Monoclinic,

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 ▶); 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 ▶).

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

C11H9N5O4S	F000 = 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 = 3.1–25.5º
b = 7.3239 (4) Å	µ = 0.28 mm−1
c = 21.8683 (12) Å	T = 295 (2) K
β = 92.610 (2)º	Prism, orange
V = 1281.98 (13) Å3	0.46 × 0.42 × 0.36 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	2943 independent reflections
Radiation source: fine-focus sealed tube	1845 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.039
Detector resolution: 10.00 pixels mm-1	θmax = 27.5º
T = 295(2) K	θmin = 3.1º
ω scans	h = −10→10
Absorption correction: none	k = −9→8
12253 measured reflections	l = −28→28

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-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 = 1.11	Δρmax = 0.22 e Å−3
2943 reflections	Δρmin = −0.19 e Å−3
192 parameters	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)
Secondary atom site location: difference Fourier map

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.

	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*

	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)

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

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

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) .