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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o152.
Published online 2007 December 6. doi:  10.1107/S1600536807063593
PMCID: PMC2915220

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

Abstract

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 [R 2 2 (18)] and C—H(...)S=C [R 2 2 (22)] inter­molecular inter­actions. C—H(...)S—C [R 2 2 (14)] inter­actions link these dimers into ribbons in the [011] direction.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0o152-scheme1.jpg

Experimental

Crystal data

  • C12H12N4OS2
  • M r = 292.40
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o152-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2001 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

The authors thank the Natural Science Foundation of Yangzhou University (grant No. 2006XJJ03) for financial support.

supplementary crystallographic information

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).

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 (λmax, in CHCl3, nm): 396 (K-band, 1.87× 104). 1H NMR (600 MHz, CDCl3, δ, p.p.m.): 9.64 (m, 5H, ArH), 6.91 (s, H, NH), 3.96 (s, 3H, SCH3), 1.13 (s, 3H, CH3).

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 Uiso(H) =1.2Ueq(C, N) and 1.5Ueq(methyl C).

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 R22 (18), and R22 (22) and R22 (14) ring via the short intermolecular interaction of C—H···O=C and C—H···S=C, and C—H···S—C, ...
Fig. 3.
The structures of (I) and (II).

Crystal data

C12H12N4OS2Z = 2
Mr = 292.40F000 = 304.0
Triclinic, P1Dx = 1.474 Mg m3
Hall symbol: -P 1Melting point: 397 K
a = 5.0915 (8) ÅMo Kα radiation λ = 0.71073 Å
b = 10.9705 (16) ÅCell parameters from 3332 reflections
c = 11.9398 (18) Åθ = 2.4–28.2º
α = 93.770 (2)ºµ = 0.40 mm1
β = 97.947 (2)ºT = 293 (2) K
γ = 91.422 (2)ºBlock, yellow
V = 658.69 (17) Å30.26 × 0.23 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer2304 independent reflections
Radiation source: fine-focus sealed tube2035 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 293(2) Kθmax = 25.0º
phi and ω scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)h = −5→6
Tmin = 0.816, Tmax = 0.874k = −12→13
4799 measured reflectionsl = −13→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-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 reflectionsΔρmax = 0.25 e Å3
174 parametersΔρmin = −0.30 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
S11.11220 (9)0.25831 (4)−0.01602 (4)0.02887 (16)
S21.21824 (9)0.06971 (4)0.15622 (4)0.03043 (16)
O10.8212 (2)0.13832 (11)0.32205 (10)0.0297 (3)
N20.4418 (3)0.33971 (12)0.35801 (12)0.0232 (3)
N10.4384 (3)0.25235 (13)0.42827 (12)0.0257 (3)
H10.54300.19250.42330.031*
N30.7936 (3)0.36637 (13)0.12557 (13)0.0248 (3)
N40.8960 (3)0.25697 (13)0.16941 (12)0.0237 (3)
C80.6255 (3)0.40665 (15)0.19108 (14)0.0230 (4)
C60.2679 (3)0.25469 (15)0.51098 (14)0.0235 (4)
C100.7816 (3)0.22690 (15)0.26553 (14)0.0229 (4)
C111.0712 (3)0.19198 (15)0.11056 (14)0.0232 (4)
C50.2180 (4)0.14648 (16)0.56018 (16)0.0310 (4)
H50.30120.07550.53970.037*
C70.6034 (3)0.32719 (15)0.28113 (14)0.0225 (4)
C90.4760 (4)0.51969 (16)0.16867 (16)0.0289 (4)
H9A0.52740.55420.10280.043*
H9B0.51530.57790.23280.043*
H9C0.28910.49980.15600.043*
C10.1473 (4)0.36136 (16)0.54284 (15)0.0283 (4)
H1A0.18270.43410.51100.034*
C2−0.0262 (4)0.35827 (17)0.62250 (16)0.0325 (4)
H2−0.10790.42930.64400.039*
C3−0.0791 (4)0.25008 (17)0.67044 (15)0.0315 (4)
H3−0.19740.24850.72320.038*
C121.3501 (4)0.15958 (18)−0.06889 (16)0.0328 (4)
H12A1.50660.1599−0.01390.049*
H12B1.39580.1882−0.13820.049*
H12C1.27510.0779−0.08290.049*
C40.0444 (4)0.14470 (17)0.63963 (16)0.0326 (4)
H40.01070.07240.67240.039*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0259 (3)0.0330 (3)0.0306 (3)0.00503 (19)0.01298 (19)0.00305 (19)
S20.0270 (3)0.0285 (3)0.0381 (3)0.00935 (19)0.0109 (2)0.0028 (2)
O10.0298 (7)0.0309 (7)0.0310 (7)0.0109 (5)0.0090 (5)0.0079 (6)
N20.0242 (8)0.0215 (7)0.0241 (8)0.0028 (6)0.0040 (6)0.0016 (6)
N10.0289 (8)0.0239 (8)0.0274 (8)0.0102 (6)0.0110 (6)0.0060 (6)
N30.0239 (8)0.0216 (7)0.0305 (8)0.0047 (6)0.0081 (6)0.0032 (6)
N40.0205 (8)0.0248 (8)0.0274 (8)0.0068 (6)0.0076 (6)0.0028 (6)
C80.0211 (9)0.0240 (9)0.0245 (9)0.0017 (7)0.0058 (7)0.0000 (7)
C60.0240 (9)0.0262 (9)0.0213 (8)0.0053 (7)0.0049 (7)0.0029 (7)
C100.0186 (9)0.0273 (9)0.0230 (9)0.0022 (7)0.0033 (7)0.0013 (7)
C110.0168 (9)0.0251 (9)0.0278 (9)−0.0009 (7)0.0058 (7)−0.0034 (7)
C50.0372 (11)0.0253 (9)0.0334 (10)0.0102 (8)0.0113 (8)0.0058 (8)
C70.0214 (9)0.0238 (9)0.0234 (9)0.0022 (7)0.0068 (7)0.0013 (7)
C90.0334 (10)0.0244 (9)0.0316 (10)0.0074 (8)0.0124 (8)0.0037 (7)
C10.0320 (10)0.0273 (9)0.0281 (9)0.0062 (8)0.0103 (8)0.0060 (7)
C20.0358 (11)0.0339 (10)0.0310 (10)0.0125 (8)0.0134 (8)0.0042 (8)
C30.0301 (10)0.0410 (11)0.0265 (10)0.0069 (8)0.0116 (8)0.0077 (8)
C120.0268 (10)0.0398 (11)0.0339 (10)0.0033 (8)0.0136 (8)−0.0034 (8)
C40.0370 (11)0.0304 (10)0.0333 (10)0.0041 (8)0.0113 (8)0.0096 (8)

Geometric parameters (Å, °)

S1—C111.7555 (18)C10—C71.462 (2)
S1—C121.7960 (18)C5—C41.384 (3)
S2—C111.6403 (17)C5—H50.9300
O1—C101.224 (2)C9—H9A0.9600
N2—N11.3159 (19)C9—H9B0.9600
N2—C71.318 (2)C9—H9C0.9600
N1—C61.401 (2)C1—C21.386 (3)
N1—H10.8600C1—H1A0.9300
N3—C81.303 (2)C2—C31.387 (3)
N3—N41.4227 (19)C2—H20.9300
N4—C111.392 (2)C3—C41.383 (3)
N4—C101.411 (2)C3—H30.9300
C8—C71.442 (2)C12—H12A0.9600
C8—C91.491 (2)C12—H12B0.9600
C6—C11.390 (2)C12—H12C0.9600
C6—C51.392 (2)C4—H40.9300
C11—S1—C12100.91 (8)C8—C7—C10106.59 (15)
N1—N2—C7116.78 (14)C8—C9—H9A109.5
N2—N1—C6121.45 (14)C8—C9—H9B109.5
N2—N1—H1119.3H9A—C9—H9B109.5
C6—N1—H1119.3C8—C9—H9C109.5
C8—N3—N4107.13 (14)H9A—C9—H9C109.5
C11—N4—C10129.66 (14)H9B—C9—H9C109.5
C11—N4—N3118.47 (14)C2—C1—C6119.35 (17)
C10—N4—N3111.69 (13)C2—C1—H1A120.3
N3—C8—C7111.47 (15)C6—C1—H1A120.3
N3—C8—C9121.65 (16)C1—C2—C3120.54 (17)
C7—C8—C9126.86 (15)C1—C2—H2119.7
C1—C6—C5120.19 (17)C3—C2—H2119.7
C1—C6—N1121.47 (16)C4—C3—C2119.84 (18)
C5—C6—N1118.34 (15)C4—C3—H3120.1
O1—C10—N4128.54 (16)C2—C3—H3120.1
O1—C10—C7128.36 (16)S1—C12—H12A109.5
N4—C10—C7103.10 (14)S1—C12—H12B109.5
N4—C11—S2123.30 (13)H12A—C12—H12B109.5
N4—C11—S1111.28 (12)S1—C12—H12C109.5
S2—C11—S1125.42 (10)H12A—C12—H12C109.5
C4—C5—C6119.86 (17)H12B—C12—H12C109.5
C4—C5—H5120.1C3—C4—C5120.22 (17)
C6—C5—H5120.1C3—C4—H4119.9
N2—C7—C8126.19 (15)C5—C4—H4119.9
N2—C7—C10127.11 (15)
C7—N2—N1—C6−178.00 (16)N1—C6—C5—C4−178.05 (17)
C8—N3—N4—C11176.70 (14)N1—N2—C7—C8175.26 (16)
C8—N3—N4—C101.18 (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—N21.6 (3)
N2—N1—C6—C1−17.1 (3)N3—C8—C7—C10−0.3 (2)
N2—N1—C6—C5162.07 (16)C9—C8—C7—C10178.02 (17)
C11—N4—C10—O13.6 (3)O1—C10—C7—N2−2.5 (3)
N3—N4—C10—O1178.51 (16)N4—C10—C7—N2177.36 (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—C80.97 (18)
C10—N4—C11—S2−9.6 (3)C5—C6—C1—C2−1.1 (3)
N3—N4—C11—S2175.85 (12)N1—C6—C1—C2178.01 (17)
C10—N4—C11—S1170.68 (14)C6—C1—C2—C30.2 (3)
N3—N4—C11—S1−3.90 (19)C1—C2—C3—C40.8 (3)
C12—S1—C11—N4178.32 (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—C41.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.062.751 (2)137
C4—H4···O1i0.932.493.244 (3)139
C4—H4···S2i0.932.993.842 (2)152

Symmetry codes: (i) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2082).

References

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