4-[2-(2-Meth-oxy-phen-yl)hydrazinyl-idene]-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

In the title mol-ecule, C(12)H(13)N(5)O(2)S, a bifurcated intra-molecular N-H⋯O(O) hydrogen bond forms two S(6) ring motifs. The benzene ring forms a dihedral angle of 14.36 (11)° with the pyrazole ring. In the crystal, pairs of N-H⋯S hydrogen bonds form centrosymmetric dimers, generating R(2) (2)(8) ring motifs, which stack along the b axis.

Related literature

For applications of pyrazole derivatives, see: Rai et al. (2008 ▶); Isloor et al. (2009 ▶); Girisha et al. (2010 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C12H13N5O2S

M = 291.33

Monoclinic,

a = 14.3207 (13) Å

b = 5.2003 (5) Å

c = 19.5919 (18) Å

β = 108.369 (2)°

V = 1384.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 296 K

0.61 × 0.28 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.866, T max = 0.980

26169 measured reflections

4567 independent reflections

3273 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.187

S = 1.05

4567 reflections

195 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.60 e Å−3

Δρmin = −0.34 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 datablock(s) global, I. DOI: 10.1107/S1600536811037883/lh5336sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037883/lh5336Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811037883/lh5336Isup3.cml

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

C12H13N5O2S	F(000) = 608
Mr = 291.33	Dx = 1.397 Mg m−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 5668 reflections
a = 14.3207 (13) Å	θ = 2.2–29.2°
b = 5.2003 (5) Å	µ = 0.24 mm−1
c = 19.5919 (18) Å	T = 296 K
β = 108.369 (2)°	Plate, red
V = 1384.7 (2) Å3	0.61 × 0.28 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4567 independent reflections
Radiation source: fine-focus sealed tube	3273 reflections with I > 2σ(I)
graphite	Rint = 0.061
φ and ω scans	θmax = 31.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −20→20
Tmin = 0.866, Tmax = 0.980	k = −7→7
26169 measured reflections	l = −28→28

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.1052P)2 + 0.245P] where P = (Fo2 + 2Fc2)/3
4567 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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	0.11741 (4)	0.15498 (9)	0.09216 (3)	0.05009 (17)
O1	0.17608 (12)	1.2296 (3)	−0.21073 (8)	0.0635 (4)
O2	0.15180 (10)	0.6859 (3)	−0.08927 (7)	0.0512 (3)
N1	0.28202 (12)	1.0877 (3)	−0.08210 (8)	0.0464 (4)
N2	0.32172 (11)	1.0371 (3)	−0.01384 (8)	0.0435 (3)
N3	0.26013 (11)	0.5730 (3)	0.09587 (7)	0.0431 (3)
N4	0.19132 (10)	0.5181 (3)	0.02795 (7)	0.0402 (3)
N5	0.06446 (14)	0.2838 (4)	−0.04505 (9)	0.0567 (5)
C1	0.40913 (17)	1.3986 (5)	−0.08198 (11)	0.0604 (6)
H1A	0.4474	1.3460	−0.0364	0.072*
C2	0.4416 (2)	1.5936 (5)	−0.11722 (13)	0.0735 (7)
H2A	0.5016	1.6737	−0.0951	0.088*
C3	0.3850 (2)	1.6686 (5)	−0.18496 (12)	0.0669 (6)
H3A	0.4073	1.7994	−0.2083	0.080*
C4	0.29584 (18)	1.5529 (4)	−0.21881 (11)	0.0565 (5)
H4A	0.2584	1.6049	−0.2647	0.068*
C5	0.26225 (15)	1.3592 (4)	−0.18418 (9)	0.0469 (4)
C6	0.31955 (14)	1.2835 (4)	−0.11518 (9)	0.0457 (4)
C7	0.28270 (13)	0.8477 (3)	0.01271 (9)	0.0405 (4)
C8	0.31221 (13)	0.7655 (4)	0.08639 (9)	0.0424 (4)
C9	0.20102 (13)	0.6833 (3)	−0.02533 (9)	0.0399 (3)
C10	0.38820 (17)	0.8850 (4)	0.14794 (11)	0.0603 (6)
H10A	0.3937	0.7893	0.1909	0.090*
H10B	0.3697	1.0591	0.1538	0.090*
H10C	0.4503	0.8840	0.1389	0.090*
C11	0.12283 (13)	0.3225 (3)	0.02151 (9)	0.0398 (3)
C12	0.1117 (2)	1.3083 (6)	−0.27861 (13)	0.0755 (7)
H12A	0.0572	1.1912	−0.2939	0.113*
H12B	0.1465	1.3088	−0.3132	0.113*
H12C	0.0877	1.4782	−0.2747	0.113*
H1N1	0.231 (2)	1.010 (5)	−0.1081 (15)	0.081 (9)*
H1N5	0.0188 (18)	0.171 (5)	−0.0500 (14)	0.060 (7)*
H2N5	0.071 (2)	0.387 (6)	−0.0797 (15)	0.074 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0585 (3)	0.0470 (3)	0.0424 (3)	−0.01645 (19)	0.01250 (19)	0.00532 (18)
O1	0.0680 (9)	0.0748 (10)	0.0413 (7)	−0.0202 (8)	0.0081 (6)	0.0067 (7)
O2	0.0618 (8)	0.0567 (8)	0.0309 (6)	−0.0155 (6)	0.0087 (5)	0.0023 (5)
N1	0.0569 (9)	0.0484 (8)	0.0337 (7)	−0.0151 (7)	0.0141 (6)	0.0030 (6)
N2	0.0532 (8)	0.0441 (8)	0.0353 (7)	−0.0102 (6)	0.0167 (6)	0.0015 (6)
N3	0.0509 (8)	0.0433 (8)	0.0315 (6)	−0.0117 (6)	0.0077 (5)	0.0021 (5)
N4	0.0490 (7)	0.0384 (7)	0.0309 (6)	−0.0117 (6)	0.0095 (5)	0.0003 (5)
N5	0.0659 (10)	0.0568 (10)	0.0396 (8)	−0.0278 (9)	0.0055 (7)	0.0027 (7)
C1	0.0693 (12)	0.0694 (13)	0.0394 (9)	−0.0247 (11)	0.0130 (8)	0.0099 (9)
C2	0.0822 (15)	0.0808 (16)	0.0541 (13)	−0.0374 (13)	0.0167 (11)	0.0121 (11)
C3	0.0923 (16)	0.0626 (13)	0.0486 (11)	−0.0257 (12)	0.0263 (11)	0.0096 (9)
C4	0.0801 (13)	0.0552 (12)	0.0364 (9)	−0.0072 (10)	0.0214 (9)	0.0065 (8)
C5	0.0611 (10)	0.0479 (10)	0.0334 (8)	−0.0078 (8)	0.0173 (7)	−0.0015 (7)
C6	0.0605 (10)	0.0449 (9)	0.0351 (8)	−0.0100 (8)	0.0202 (7)	0.0023 (7)
C7	0.0485 (8)	0.0396 (8)	0.0345 (8)	−0.0097 (7)	0.0148 (6)	0.0002 (6)
C8	0.0498 (9)	0.0432 (9)	0.0330 (7)	−0.0115 (7)	0.0112 (6)	0.0000 (6)
C9	0.0490 (8)	0.0382 (8)	0.0330 (7)	−0.0060 (6)	0.0135 (6)	0.0011 (6)
C10	0.0682 (12)	0.0665 (13)	0.0387 (9)	−0.0277 (10)	0.0060 (8)	0.0003 (9)
C11	0.0457 (8)	0.0332 (8)	0.0394 (8)	−0.0054 (6)	0.0116 (6)	−0.0010 (6)
C12	0.0713 (14)	0.106 (2)	0.0429 (11)	−0.0109 (14)	0.0086 (10)	0.0023 (12)

S1—C11	1.6578 (17)	C1—H1A	0.9300
O1—C5	1.357 (2)	C2—C3	1.375 (3)
O1—C12	1.419 (3)	C2—H2A	0.9300
O2—C9	1.229 (2)	C3—C4	1.378 (3)
N1—N2	1.305 (2)	C3—H3A	0.9300
N1—C6	1.402 (2)	C4—C5	1.383 (3)
N1—H1N1	0.85 (3)	C4—H4A	0.9300
N2—C7	1.317 (2)	C5—C6	1.399 (3)
N3—C8	1.296 (2)	C7—C8	1.435 (2)
N3—N4	1.4131 (18)	C7—C9	1.451 (2)
N4—C11	1.391 (2)	C8—C10	1.482 (2)
N4—C9	1.392 (2)	C10—H10A	0.9600
N5—C11	1.324 (2)	C10—H10B	0.9600
N5—H1N5	0.86 (3)	C10—H10C	0.9600
N5—H2N5	0.89 (3)	C12—H12A	0.9600
C1—C6	1.379 (3)	C12—H12B	0.9600
C1—C2	1.387 (3)	C12—H12C	0.9600
C5—O1—C12	117.38 (18)	C1—C6—C5	120.59 (17)
N2—N1—C6	120.92 (16)	C1—C6—N1	122.18 (17)
N2—N1—H1N1	122.0 (19)	C5—C6—N1	117.23 (16)
C6—N1—H1N1	117.0 (19)	N2—C7—C8	126.34 (16)
N1—N2—C7	116.97 (15)	N2—C7—C9	127.67 (16)
C8—N3—N4	106.45 (13)	C8—C7—C9	105.98 (14)
C11—N4—C9	128.13 (14)	N3—C8—C7	111.94 (15)
C11—N4—N3	119.72 (13)	N3—C8—C10	121.01 (16)
C9—N4—N3	112.12 (13)	C7—C8—C10	126.96 (16)
C11—N5—H1N5	115.8 (17)	O2—C9—N4	127.62 (15)
C11—N5—H2N5	118.4 (18)	O2—C9—C7	128.89 (15)
H1N5—N5—H2N5	125 (2)	N4—C9—C7	103.49 (14)
C6—C1—C2	119.4 (2)	C8—C10—H10A	109.5
C6—C1—H1A	120.3	C8—C10—H10B	109.5
C2—C1—H1A	120.3	H10A—C10—H10B	109.5
C3—C2—C1	120.0 (2)	C8—C10—H10C	109.5
C3—C2—H2A	120.0	H10A—C10—H10C	109.5
C1—C2—H2A	120.0	H10B—C10—H10C	109.5
C2—C3—C4	121.02 (19)	N5—C11—N4	114.13 (15)
C2—C3—H3A	119.5	N5—C11—S1	124.15 (14)
C4—C3—H3A	119.5	N4—C11—S1	121.72 (13)
C3—C4—C5	119.66 (19)	O1—C12—H12A	109.5
C3—C4—H4A	120.2	O1—C12—H12B	109.5
C5—C4—H4A	120.2	H12A—C12—H12B	109.5
O1—C5—C4	126.05 (18)	O1—C12—H12C	109.5
O1—C5—C6	114.59 (16)	H12A—C12—H12C	109.5
C4—C5—C6	119.36 (18)	H12B—C12—H12C	109.5
C6—N1—N2—C7	−179.10 (17)	N1—N2—C7—C9	1.2 (3)
C8—N3—N4—C11	−178.33 (16)	N4—N3—C8—C7	−0.7 (2)
C8—N3—N4—C9	−0.3 (2)	N4—N3—C8—C10	176.20 (18)
C6—C1—C2—C3	−0.7 (4)	N2—C7—C8—N3	−179.65 (18)
C1—C2—C3—C4	0.1 (4)	C9—C7—C8—N3	1.3 (2)
C2—C3—C4—C5	0.3 (4)	N2—C7—C8—C10	3.7 (3)
C12—O1—C5—C4	−3.6 (3)	C9—C7—C8—C10	−175.4 (2)
C12—O1—C5—C6	176.1 (2)	C11—N4—C9—O2	−1.5 (3)
C3—C4—C5—O1	179.7 (2)	N3—N4—C9—O2	−179.33 (18)
C3—C4—C5—C6	0.0 (3)	C11—N4—C9—C7	178.88 (16)
C2—C1—C6—C5	0.9 (4)	N3—N4—C9—C7	1.00 (19)
C2—C1—C6—N1	−179.2 (2)	N2—C7—C9—O2	0.0 (3)
O1—C5—C6—C1	179.7 (2)	C8—C7—C9—O2	179.03 (19)
C4—C5—C6—C1	−0.6 (3)	N2—C7—C9—N4	179.64 (18)
O1—C5—C6—N1	−0.2 (3)	C8—C7—C9—N4	−1.31 (19)
C4—C5—C6—N1	179.53 (19)	C9—N4—C11—N5	4.3 (3)
N2—N1—C6—C1	12.2 (3)	N3—N4—C11—N5	−177.95 (17)
N2—N1—C6—C5	−167.88 (17)	C9—N4—C11—S1	−176.08 (14)
N1—N2—C7—C8	−177.67 (17)	N3—N4—C11—S1	1.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.85 (3)	2.13 (3)	2.775 (2)	133 (2)
N5—H2N5···O2	0.89 (3)	1.98 (3)	2.715 (3)	138 (3)
N5—H1N5···S1i	0.86 (3)	2.52 (3)	3.366 (2)	168 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.85 (3)	2.13 (3)	2.775 (2)	133 (2)
N5—H2N5⋯O2	0.89 (3)	1.98 (3)	2.715 (3)	138 (3)
N5—H1N5⋯S1i	0.86 (3)	2.52 (3)	3.366 (2)	168 (2)

Symmetry code: (i) .