Methyl 3-methyl-5-oxo-4-(phenyl­hydrazono)-4,5-dihydro-1H-pyrazole-1-carbodithio­ate

The title compound, C₁₂H₁₁N₄OS₂, has been synthesized by the condensation reaction of 3-oxo-2-(phenyl­hydrazono)butanate and S-methyl­dithio­carbazate. The hydrazine unit and the pyrazole ring are coplanar [dihedral angle 3.8 (4)°] due to extensive conjugation and the N—H...O=C intra­molecular hydrogen bond. Two adjacent mol­ecules form dimers due to short C—H...O=C [R²₂ (18)] and C—H...S=C [R²₂ (22)] inter­molecular inter­actions. C—H...S—C [R²₂ (14)] inter­actions link these dimers into ribbons in the [011] direction.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.092
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.07
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      1.069
            Tmax scaled      0.934 Tmin scaled      0.872
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Pyrazolones compounds are finding increasing numbers of applications as ligands in coordination chemistry (Brassy et al., 1974; Zelenak et al., 1999; Yang et al.,2003). For example, they have been applied to the solvent extraction of metal ions (Bose et al., 2005) as ligands in complexes with catalytic activity (Bao et al., 2006) and in the synthesis of rare earth metal complexes with interesting photophysical properties (Shi et al. 2005). A related compound, (II), has already been studied (Liu et al., 2007).

Similar to (II), the title compound, (I), has been shown by UV spectroscopy to have extensive conjugation involving four carbon atoms (C2—C5), four nitrogen atoms (N1—N4) and one oxygen (O1). And this has been further confirmed by the determination of its crystal structure (Fig. 1) The bond lengths and angles of the large conjugated system in (I) are similar to the corresponding values in (II). The dihedral angle between the conjugated system and with plane of C1–S1–C2=S2 in (I) is 3.8 (4)° while the value in (II) is 13.1 (3)°. The bond distances of C11—N4 is 1.392 (2) in (I), and the value in (II) is the same with (I), which is shorter than the range of C—N single bonds (1.47–1.40 Å) and might be attributed to a nonclassical sp²-hybrid nitrogen atom and the conjugated system.

Two adjacent molecules form dimers due to short C—H···O=C [R²₂ (18)] and C—H···S=C [R²₂ (22)] (Bernstein et al., 1995) intermolecular interactions. C—H···S—C [R²₂ (14)] interactions link these dimers into ribbons in the (011) direction (Table 1).

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).

S2. Experimental

The title compound was synthesized by refluxing an ethanol solution of ethyl 3-oxo-2-(phenylhydrazono)butanate and S-methyldithiocarbazate (1:1) for 24 h. After 12 h at room temperature, the precipitate was collected by filtration and recrystallized from ethanol (yield 86.7%).The yellow crystals suitable for X-ray analysis were obtained by slow evaporation of a dichloromethane solution at 293 K (m.p. 396.2–397.7 K). Analysis calculated for C₁₂H₁₁N₄OS₂: C49.47, H 3.81, N 19.23%; found: C 49.63, H 3.56, N 19.14%. IR (KBr,cm^-1): 3250(w, NH), 1630 (vs, O?C), 1520 (s, N?C), 1275(S?C). UV (λ_max, in CHCl₃, nm): 396 (K-band, 1.87× 10⁴). ¹H NMR (600 MHz, CDCl_3, δ, p.p.m.): 9.64 (m, 5H, ArH), 6.91 (s, H, NH), 3.96 (s, 3H, SCH₃), 1.13 (s, 3H, CH₃).

S3. Refinement

The H atoms were placed in calculated positions and refined as riding, with C—H=0.93–0.97 Å and N—H=0.91 Å, and refined using a riding model, with U_iso(H) =1.2U_eq(C, N) and 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).

Figures

	Fig. 1. The molecular of (I) structure of the title compound, showing 50% probability ellipsoids. The C — H ··· N intramolecular hydrogen bond is shown dashed.
	Fig. 2. Packing diagram of (I), showing the formation of R^22 (18), and R^22 (22) and R^22 (14) ring via the short intermolecular interaction of C—H···O=C and C—H···S=C, and C—H···S—C, respectively, viewed along a axis. H atoms not involved in hydrogen bonding have been omitted.
	Fig. 3. The structures of (I) and (II).

Methyl 3-methyl-5-oxo-4-(phenylhydrazono)-4,5-dihydro-1H-pyrazole-1-carbodithioate

Crystal data

C12H12N4OS2	Z = 2
Mr = 292.40	F(000) = 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 = 2.4–28.2°
α = 93.770 (2)°	µ = 0.40 mm^−1
β = 97.947 (2)°	T = 293 K
γ = 91.422 (2)°	Block, yellow
V = 658.69 (17) Å^3	0.26 × 0.23 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2304 independent reflections
Radiation source: fine-focus sealed tube	2035 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
phi and ω scans	θmax = 25.0°, θmin = 1.9°
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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0578P)^2 + 0.115P] where P = (Fo^2 + 2Fc^2)/3
2304 reflections	(Δ/σ)max < 0.001
174 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O1^i	0.93	2.49	3.244 (3)	139
C4—H4···S2^i	0.93	2.99	3.842 (2)	152

Symmetry code: (i) −x+1, −y, −z+1.