3-Methyl-5-oxo-4-(2-phenyl-hydrazinyl-idene)-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

In the title compound, C(11)H(11)N(5)OS, the pyrazole ring is approximately planar, with a maximum deviation of 0.010 (2) Å. The dihedral angles between the benzene ring and the pyrazole and carbothio-amide groups are 5.42 (9) and 10.61 (18)°, respectively. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are connected by inter-molecular N-H⋯O and C-H⋯S hydrogen bonds, forming R(2) (2)(12) ring motifs. In addition, there is a π-π stacking inter-action [centroid-centroid distance = 3.5188 (11) Å] between the pyrazole and benzene rings. These inter-actions link the mol-ecules into infinite chains along [001].

Related literature

For general background to and applications of pyrazole derivatives, see: Rai & Kalluraya (2006 ▶); Rai et al. (2008 ▶); Sridhar & Perumal (2003 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C11H11N5OS

M = 261.31

Monoclinic,

a = 7.7388 (1) Å

b = 16.1103 (3) Å

c = 11.3575 (2) Å

β = 121.058 (1)°

V = 1213.00 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.53 × 0.39 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.874, T max = 0.967

16258 measured reflections

4393 independent reflections

3037 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.135

S = 1.05

4393 reflections

164 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009779/sj5118sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009779/sj5118Isup2.hkl

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

C11H11N5OS	F(000) = 544
Mr = 261.31	Dx = 1.431 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5770 reflections
a = 7.7388 (1) Å	θ = 2.5–31.9°
b = 16.1103 (3) Å	µ = 0.26 mm−1
c = 11.3575 (2) Å	T = 296 K
β = 121.058 (1)°	Plate, orange
V = 1213.00 (3) Å3	0.53 × 0.39 × 0.13 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4393 independent reflections
Radiation source: sealed tube	3037 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 32.6°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.874, Tmax = 0.967	k = −24→23
16258 measured reflections	l = −17→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0587P)2 + 0.2537P] where P = (Fo2 + 2Fc2)/3
4393 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.35472 (10)	0.29034 (2)	0.30227 (5)	0.07026 (19)
O1	0.36818 (17)	0.14963 (6)	0.49606 (10)	0.0434 (2)
N1	0.26541 (17)	0.00165 (7)	0.57723 (11)	0.0346 (2)
H1B	0.3036	0.0523	0.5989	0.041*
N2	0.23279 (17)	−0.02868 (7)	0.46071 (11)	0.0340 (2)
N3	0.25183 (18)	0.05536 (7)	0.18342 (11)	0.0340 (2)
N4	0.30783 (17)	0.12552 (6)	0.27173 (11)	0.0324 (2)
N5	0.3303 (2)	0.19488 (8)	0.10601 (13)	0.0478 (3)
H5B	0.3161	0.1470	0.0685	0.057*
H5C	0.3439	0.2384	0.0678	0.057*
C1	0.2876 (2)	−0.01706 (10)	0.79423 (14)	0.0413 (3)
H1A	0.3376	0.0367	0.8182	0.050*
C2	0.2625 (3)	−0.06542 (11)	0.88499 (15)	0.0494 (4)
H2A	0.2961	−0.0441	0.9703	0.059*
C3	0.1883 (3)	−0.14496 (11)	0.84978 (17)	0.0509 (4)
H3A	0.1732	−0.1775	0.9115	0.061*
C4	0.1363 (3)	−0.17618 (10)	0.72246 (19)	0.0523 (4)
H4A	0.0839	−0.2296	0.6983	0.063*
C5	0.1611 (2)	−0.12903 (9)	0.62989 (16)	0.0433 (3)
H5A	0.1272	−0.1505	0.5446	0.052*
C6	0.23757 (19)	−0.04923 (8)	0.66727 (13)	0.0337 (3)
C7	0.25637 (19)	0.01943 (7)	0.37735 (12)	0.0308 (2)
C8	0.31689 (19)	0.10634 (8)	0.39492 (12)	0.0313 (3)
C9	0.2218 (2)	−0.00556 (8)	0.24546 (13)	0.0328 (3)
C10	0.1592 (3)	−0.08981 (9)	0.18412 (16)	0.0481 (4)
H10A	0.0995	−0.0862	0.0863	0.072*
H10B	0.0625	−0.1121	0.2046	0.072*
H10C	0.2751	−0.1255	0.2219	0.072*
C11	0.3313 (2)	0.20147 (8)	0.22208 (14)	0.0356 (3)

	U11	U22	U33	U12	U13	U23
S1	0.1363 (5)	0.0316 (2)	0.0759 (3)	−0.0167 (2)	0.0783 (4)	−0.01097 (18)
O1	0.0638 (7)	0.0371 (5)	0.0345 (5)	−0.0008 (4)	0.0291 (5)	−0.0053 (4)
N1	0.0439 (6)	0.0335 (5)	0.0316 (5)	0.0008 (4)	0.0233 (5)	0.0044 (4)
N2	0.0390 (6)	0.0347 (5)	0.0320 (5)	0.0033 (4)	0.0210 (5)	0.0043 (4)
N3	0.0454 (6)	0.0316 (5)	0.0304 (5)	−0.0027 (4)	0.0233 (5)	−0.0037 (4)
N4	0.0459 (6)	0.0276 (5)	0.0302 (5)	−0.0019 (4)	0.0242 (5)	−0.0015 (4)
N5	0.0785 (10)	0.0355 (6)	0.0431 (6)	−0.0039 (6)	0.0411 (7)	0.0037 (5)
C1	0.0478 (8)	0.0442 (7)	0.0362 (6)	−0.0027 (6)	0.0247 (6)	0.0024 (6)
C2	0.0543 (9)	0.0645 (10)	0.0351 (7)	0.0010 (7)	0.0271 (7)	0.0084 (7)
C3	0.0547 (9)	0.0569 (9)	0.0507 (8)	0.0075 (7)	0.0339 (7)	0.0219 (7)
C4	0.0645 (10)	0.0377 (7)	0.0662 (10)	0.0024 (7)	0.0420 (9)	0.0121 (7)
C5	0.0561 (9)	0.0370 (7)	0.0448 (8)	0.0019 (6)	0.0318 (7)	0.0042 (6)
C6	0.0345 (6)	0.0375 (6)	0.0330 (6)	0.0050 (5)	0.0202 (5)	0.0091 (5)
C7	0.0368 (6)	0.0298 (5)	0.0298 (5)	0.0014 (5)	0.0201 (5)	0.0018 (4)
C8	0.0381 (6)	0.0309 (5)	0.0297 (5)	0.0024 (5)	0.0208 (5)	0.0004 (4)
C9	0.0397 (7)	0.0310 (6)	0.0314 (6)	−0.0003 (5)	0.0210 (5)	−0.0015 (4)
C10	0.0700 (10)	0.0342 (7)	0.0471 (8)	−0.0090 (6)	0.0351 (8)	−0.0083 (6)
C11	0.0441 (7)	0.0307 (6)	0.0377 (6)	−0.0003 (5)	0.0252 (6)	0.0024 (5)

S1—C11	1.6560 (13)	C1—H1A	0.9300
O1—C8	1.2218 (15)	C2—C3	1.377 (3)
N1—N2	1.3073 (15)	C2—H2A	0.9300
N1—C6	1.4111 (16)	C3—C4	1.380 (3)
N1—H1B	0.8600	C3—H3A	0.9300
N2—C7	1.3072 (16)	C4—C5	1.389 (2)
N3—C9	1.2972 (17)	C4—H4A	0.9300
N3—N4	1.4222 (14)	C5—C6	1.387 (2)
N4—C11	1.3979 (16)	C5—H5A	0.9300
N4—C8	1.3988 (16)	C7—C9	1.4366 (17)
N5—C11	1.3185 (18)	C7—C8	1.4572 (17)
N5—H5B	0.8602	C9—C10	1.4880 (19)
N5—H5C	0.8600	C10—H10A	0.9600
C1—C2	1.383 (2)	C10—H10B	0.9600
C1—C6	1.3863 (19)	C10—H10C	0.9600
N2—N1—C6	119.64 (11)	C6—C5—H5A	120.7
N2—N1—H1B	120.2	C4—C5—H5A	120.7
C6—N1—H1B	120.2	C1—C6—C5	120.73 (13)
C7—N2—N1	119.04 (11)	C1—C6—N1	118.13 (12)
C9—N3—N4	107.04 (10)	C5—C6—N1	121.13 (12)
C11—N4—C8	130.31 (11)	N2—C7—C9	124.65 (12)
C11—N4—N3	117.83 (10)	N2—C7—C8	128.73 (12)
C8—N4—N3	111.70 (10)	C9—C7—C8	106.61 (10)
C11—N5—H5B	120.0	O1—C8—N4	129.69 (12)
C11—N5—H5C	120.0	O1—C8—C7	127.07 (12)
H5B—N5—H5C	120.0	N4—C8—C7	103.20 (10)
C2—C1—C6	119.56 (14)	N3—C9—C7	111.42 (11)
C2—C1—H1A	120.2	N3—C9—C10	122.83 (12)
C6—C1—H1A	120.2	C7—C9—C10	125.75 (12)
C3—C2—C1	120.38 (15)	C9—C10—H10A	109.5
C3—C2—H2A	119.8	C9—C10—H10B	109.5
C1—C2—H2A	119.8	H10A—C10—H10B	109.5
C2—C3—C4	119.73 (14)	C9—C10—H10C	109.5
C2—C3—H3A	120.1	H10A—C10—H10C	109.5
C4—C3—H3A	120.1	H10B—C10—H10C	109.5
C3—C4—C5	120.96 (16)	N5—C11—N4	113.45 (11)
C3—C4—H4A	119.5	N5—C11—S1	124.20 (10)
C5—C4—H4A	119.5	N4—C11—S1	122.34 (10)
C6—C5—C4	118.63 (15)
C6—N1—N2—C7	179.04 (11)	C11—N4—C8—C7	173.49 (13)
C9—N3—N4—C11	−174.52 (12)	N3—N4—C8—C7	−1.73 (14)
C9—N3—N4—C8	1.36 (15)	N2—C7—C8—O1	4.4 (2)
C6—C1—C2—C3	−0.1 (2)	C9—C7—C8—O1	−176.61 (13)
C1—C2—C3—C4	−0.8 (3)	N2—C7—C8—N4	−177.54 (13)
C2—C3—C4—C5	1.2 (3)	C9—C7—C8—N4	1.46 (13)
C3—C4—C5—C6	−0.7 (2)	N4—N3—C9—C7	−0.33 (15)
C2—C1—C6—C5	0.6 (2)	N4—N3—C9—C10	179.58 (13)
C2—C1—C6—N1	−179.84 (13)	N2—C7—C9—N3	178.31 (12)
C4—C5—C6—C1	−0.2 (2)	C8—C7—C9—N3	−0.73 (15)
C4—C5—C6—N1	−179.78 (13)	N2—C7—C9—C10	−1.6 (2)
N2—N1—C6—C1	175.36 (12)	C8—C7—C9—C10	179.36 (14)
N2—N1—C6—C5	−5.05 (19)	C8—N4—C11—N5	174.38 (13)
N1—N2—C7—C9	−178.74 (12)	N3—N4—C11—N5	−10.64 (18)
N1—N2—C7—C8	0.1 (2)	C8—N4—C11—S1	−6.4 (2)
C11—N4—C8—O1	−8.5 (2)	N3—N4—C11—S1	168.56 (10)
N3—N4—C8—O1	176.27 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1	0.86	2.16	2.8147 (16)	132
N5—H5C···O1i	0.86	2.03	2.8806 (15)	172
C1—H1A···S1ii	0.93	2.80	3.6838 (16)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1	0.86	2.16	2.8147 (16)	132
N5—H5C⋯O1i	0.86	2.03	2.8806 (15)	172
C1—H1A⋯S1ii	0.93	2.80	3.6838 (16)	159

Symmetry codes: (i) ; (ii) .