Methyl 3-methyl-5-oxo-4-(phenyl-hydrazono)-4,5-dihydro-1H-pyrazole-1-carbodithio-ate.

The title compound, C(12)H(11)N(4)OS(2), has been synthesized by the condensation reaction of 3-oxo-2-(phenyl-hydrazono)butanate and S-methyl-dithio-carbazate. The hydrazine unit and the pyrazole ring are coplanar [dihedral angle 3.8 (4)°] due to extensive conjugation and the N-H⋯O=C intra-molecular hydrogen bond. Two adjacent mol-ecules form dimers due to short C-H⋯O=C [R(2) (2) (18)] and C-H⋯S=C [R(2) (2) (22)] inter-molecular inter-actions. C-H⋯S-C [R(2) (2) (14)] inter-actions link these dimers into ribbons in the [011] direction.

Related literature

For related literature, see: Bao et al. (2006 ▶); Bernstein et al. (1995 ▶); Bose et al. (2005 ▶); Brassy et al. (1974 ▶); Liu et al. (2007 ▶); Shi et al. (2005 ▶); Yang et al. (2003 ▶); Zelenak et al. (1999 ▶).

Experimental

Crystal data

C12H12N4OS2

M = 292.40

Triclinic,

a = 5.0915 (8) Å

b = 10.9705 (16) Å

c = 11.9398 (18) Å

α = 93.770 (2)°

β = 97.947 (2)°

γ = 91.422 (2)°

V = 658.69 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.40 mm−1

T = 293 (2) K

0.26 × 0.23 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.816, T max = 0.874 (expected range = 0.872–0.934)

4799 measured reflections

2304 independent reflections

2035 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.092

S = 1.02

2304 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2001 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807063593/bv2082sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063593/bv2082Isup2.hkl

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

C12H12N4OS2	Z = 2
Mr = 292.40	F000 = 304.0
Triclinic, P1	Dx = 1.474 Mg m−3
Hall symbol: -P 1	Melting point: 397 K
a = 5.0915 (8) Å	Mo Kα radiation λ = 0.71073 Å
b = 10.9705 (16) Å	Cell parameters from 3332 reflections
c = 11.9398 (18) Å	θ = 2.4–28.2º
α = 93.770 (2)º	µ = 0.40 mm−1
β = 97.947 (2)º	T = 293 (2) K
γ = 91.422 (2)º	Block, yellow
V = 658.69 (17) Å3	0.26 × 0.23 × 0.17 mm

Bruker SMART CCD area-detector diffractometer	2304 independent reflections
Radiation source: fine-focus sealed tube	2035 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.033
T = 293(2) K	θmax = 25.0º
phi and ω scans	θmin = 1.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)	h = −5→6
Tmin = 0.816, Tmax = 0.874	k = −12→13
4799 measured reflections	l = −13→14

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)] = 0.031	H-atom parameters constrained
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.0578P)2 + 0.115P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2304 reflections	Δρmax = 0.25 e Å−3
174 parameters	Δρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	1.11220 (9)	0.25831 (4)	−0.01602 (4)	0.02887 (16)
S2	1.21824 (9)	0.06971 (4)	0.15622 (4)	0.03043 (16)
O1	0.8212 (2)	0.13832 (11)	0.32205 (10)	0.0297 (3)
N2	0.4418 (3)	0.33971 (12)	0.35801 (12)	0.0232 (3)
N1	0.4384 (3)	0.25235 (13)	0.42827 (12)	0.0257 (3)
H1	0.5430	0.1925	0.4233	0.031*
N3	0.7936 (3)	0.36637 (13)	0.12557 (13)	0.0248 (3)
N4	0.8960 (3)	0.25697 (13)	0.16941 (12)	0.0237 (3)
C8	0.6255 (3)	0.40665 (15)	0.19108 (14)	0.0230 (4)
C6	0.2679 (3)	0.25469 (15)	0.51098 (14)	0.0235 (4)
C10	0.7816 (3)	0.22690 (15)	0.26553 (14)	0.0229 (4)
C11	1.0712 (3)	0.19198 (15)	0.11056 (14)	0.0232 (4)
C5	0.2180 (4)	0.14648 (16)	0.56018 (16)	0.0310 (4)
H5	0.3012	0.0755	0.5397	0.037*
C7	0.6034 (3)	0.32719 (15)	0.28113 (14)	0.0225 (4)
C9	0.4760 (4)	0.51969 (16)	0.16867 (16)	0.0289 (4)
H9A	0.5274	0.5542	0.1028	0.043*
H9B	0.5153	0.5779	0.2328	0.043*
H9C	0.2891	0.4998	0.1560	0.043*
C1	0.1473 (4)	0.36136 (16)	0.54284 (15)	0.0283 (4)
H1A	0.1827	0.4341	0.5110	0.034*
C2	−0.0262 (4)	0.35827 (17)	0.62250 (16)	0.0325 (4)
H2	−0.1079	0.4293	0.6440	0.039*
C3	−0.0791 (4)	0.25008 (17)	0.67044 (15)	0.0315 (4)
H3	−0.1974	0.2485	0.7232	0.038*
C12	1.3501 (4)	0.15958 (18)	−0.06889 (16)	0.0328 (4)
H12A	1.5066	0.1599	−0.0139	0.049*
H12B	1.3958	0.1882	−0.1382	0.049*
H12C	1.2751	0.0779	−0.0829	0.049*
C4	0.0444 (4)	0.14470 (17)	0.63963 (16)	0.0326 (4)
H4	0.0107	0.0724	0.6724	0.039*

	U11	U22	U33	U12	U13	U23
S1	0.0259 (3)	0.0330 (3)	0.0306 (3)	0.00503 (19)	0.01298 (19)	0.00305 (19)
S2	0.0270 (3)	0.0285 (3)	0.0381 (3)	0.00935 (19)	0.0109 (2)	0.0028 (2)
O1	0.0298 (7)	0.0309 (7)	0.0310 (7)	0.0109 (5)	0.0090 (5)	0.0079 (6)
N2	0.0242 (8)	0.0215 (7)	0.0241 (8)	0.0028 (6)	0.0040 (6)	0.0016 (6)
N1	0.0289 (8)	0.0239 (8)	0.0274 (8)	0.0102 (6)	0.0110 (6)	0.0060 (6)
N3	0.0239 (8)	0.0216 (7)	0.0305 (8)	0.0047 (6)	0.0081 (6)	0.0032 (6)
N4	0.0205 (8)	0.0248 (8)	0.0274 (8)	0.0068 (6)	0.0076 (6)	0.0028 (6)
C8	0.0211 (9)	0.0240 (9)	0.0245 (9)	0.0017 (7)	0.0058 (7)	0.0000 (7)
C6	0.0240 (9)	0.0262 (9)	0.0213 (8)	0.0053 (7)	0.0049 (7)	0.0029 (7)
C10	0.0186 (9)	0.0273 (9)	0.0230 (9)	0.0022 (7)	0.0033 (7)	0.0013 (7)
C11	0.0168 (9)	0.0251 (9)	0.0278 (9)	−0.0009 (7)	0.0058 (7)	−0.0034 (7)
C5	0.0372 (11)	0.0253 (9)	0.0334 (10)	0.0102 (8)	0.0113 (8)	0.0058 (8)
C7	0.0214 (9)	0.0238 (9)	0.0234 (9)	0.0022 (7)	0.0068 (7)	0.0013 (7)
C9	0.0334 (10)	0.0244 (9)	0.0316 (10)	0.0074 (8)	0.0124 (8)	0.0037 (7)
C1	0.0320 (10)	0.0273 (9)	0.0281 (9)	0.0062 (8)	0.0103 (8)	0.0060 (7)
C2	0.0358 (11)	0.0339 (10)	0.0310 (10)	0.0125 (8)	0.0134 (8)	0.0042 (8)
C3	0.0301 (10)	0.0410 (11)	0.0265 (10)	0.0069 (8)	0.0116 (8)	0.0077 (8)
C12	0.0268 (10)	0.0398 (11)	0.0339 (10)	0.0033 (8)	0.0136 (8)	−0.0034 (8)
C4	0.0370 (11)	0.0304 (10)	0.0333 (10)	0.0041 (8)	0.0113 (8)	0.0096 (8)

S1—C11	1.7555 (18)	C10—C7	1.462 (2)
S1—C12	1.7960 (18)	C5—C4	1.384 (3)
S2—C11	1.6403 (17)	C5—H5	0.9300
O1—C10	1.224 (2)	C9—H9A	0.9600
N2—N1	1.3159 (19)	C9—H9B	0.9600
N2—C7	1.318 (2)	C9—H9C	0.9600
N1—C6	1.401 (2)	C1—C2	1.386 (3)
N1—H1	0.8600	C1—H1A	0.9300
N3—C8	1.303 (2)	C2—C3	1.387 (3)
N3—N4	1.4227 (19)	C2—H2	0.9300
N4—C11	1.392 (2)	C3—C4	1.383 (3)
N4—C10	1.411 (2)	C3—H3	0.9300
C8—C7	1.442 (2)	C12—H12A	0.9600
C8—C9	1.491 (2)	C12—H12B	0.9600
C6—C1	1.390 (2)	C12—H12C	0.9600
C6—C5	1.392 (2)	C4—H4	0.9300
C11—S1—C12	100.91 (8)	C8—C7—C10	106.59 (15)
N1—N2—C7	116.78 (14)	C8—C9—H9A	109.5
N2—N1—C6	121.45 (14)	C8—C9—H9B	109.5
N2—N1—H1	119.3	H9A—C9—H9B	109.5
C6—N1—H1	119.3	C8—C9—H9C	109.5
C8—N3—N4	107.13 (14)	H9A—C9—H9C	109.5
C11—N4—C10	129.66 (14)	H9B—C9—H9C	109.5
C11—N4—N3	118.47 (14)	C2—C1—C6	119.35 (17)
C10—N4—N3	111.69 (13)	C2—C1—H1A	120.3
N3—C8—C7	111.47 (15)	C6—C1—H1A	120.3
N3—C8—C9	121.65 (16)	C1—C2—C3	120.54 (17)
C7—C8—C9	126.86 (15)	C1—C2—H2	119.7
C1—C6—C5	120.19 (17)	C3—C2—H2	119.7
C1—C6—N1	121.47 (16)	C4—C3—C2	119.84 (18)
C5—C6—N1	118.34 (15)	C4—C3—H3	120.1
O1—C10—N4	128.54 (16)	C2—C3—H3	120.1
O1—C10—C7	128.36 (16)	S1—C12—H12A	109.5
N4—C10—C7	103.10 (14)	S1—C12—H12B	109.5
N4—C11—S2	123.30 (13)	H12A—C12—H12B	109.5
N4—C11—S1	111.28 (12)	S1—C12—H12C	109.5
S2—C11—S1	125.42 (10)	H12A—C12—H12C	109.5
C4—C5—C6	119.86 (17)	H12B—C12—H12C	109.5
C4—C5—H5	120.1	C3—C4—C5	120.22 (17)
C6—C5—H5	120.1	C3—C4—H4	119.9
N2—C7—C8	126.19 (15)	C5—C4—H4	119.9
N2—C7—C10	127.11 (15)
C7—N2—N1—C6	−178.00 (16)	N1—C6—C5—C4	−178.05 (17)
C8—N3—N4—C11	176.70 (14)	N1—N2—C7—C8	175.26 (16)
C8—N3—N4—C10	1.18 (19)	N1—N2—C7—C10	−0.4 (3)
N4—N3—C8—C7	−0.49 (19)	N3—C8—C7—N2	−176.75 (16)
N4—N3—C8—C9	−178.93 (15)	C9—C8—C7—N2	1.6 (3)
N2—N1—C6—C1	−17.1 (3)	N3—C8—C7—C10	−0.3 (2)
N2—N1—C6—C5	162.07 (16)	C9—C8—C7—C10	178.02 (17)
C11—N4—C10—O1	3.6 (3)	O1—C10—C7—N2	−2.5 (3)
N3—N4—C10—O1	178.51 (16)	N4—C10—C7—N2	177.36 (16)
C11—N4—C10—C7	−176.20 (16)	O1—C10—C7—C8	−178.85 (17)
N3—N4—C10—C7	−1.32 (18)	N4—C10—C7—C8	0.97 (18)
C10—N4—C11—S2	−9.6 (3)	C5—C6—C1—C2	−1.1 (3)
N3—N4—C11—S2	175.85 (12)	N1—C6—C1—C2	178.01 (17)
C10—N4—C11—S1	170.68 (14)	C6—C1—C2—C3	0.2 (3)
N3—N4—C11—S1	−3.90 (19)	C1—C2—C3—C4	0.8 (3)
C12—S1—C11—N4	178.32 (12)	C2—C3—C4—C5	−0.8 (3)
C12—S1—C11—S2	−1.43 (14)	C6—C5—C4—C3	−0.1 (3)
C1—C6—C5—C4	1.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.06	2.751 (2)	137
C4—H4···O1i	0.93	2.49	3.244 (3)	139
C4—H4···S2i	0.93	2.99	3.842 (2)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	2.06	2.751 (2)	137
C4—H4⋯O1i	0.93	2.49	3.244 (3)	139
C4—H4⋯S2i	0.93	2.99	3.842 (2)	152

Symmetry codes: (i) ; (ii) .