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Acta Crystallogr Sect E Struct Rep Online. 2012 January 1; 68(Pt 1): o184.
Published online 2011 December 21. doi:  10.1107/S1600536811053621
PMCID: PMC3254522

(E)-2-[(E)-3-(Hy­droxy­imino)­butan-2-yl­idene]-N-methyl­hydrazinecarbothio­amide

Abstract

In the title compound, C6H12N4OS, an intra­molecular N—H(...)N hydrogen-bond is present giving rise to an S(5) ring motif. In the crystal, double-stranded chains propagating along [10An external file that holds a picture, illustration, etc.
Object name is e-68-0o184-efi1.jpg] are formed via pairs of O—H(...)S and N—H(...)S hydrogen bonds. The chains are further stabilized by C—H(...)S interactions.

Related literature

For standard bond lengths, see: Allen et al. (1987 [triangle]). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 [triangle]). For related structures, see: Choi et al. (2008 [triangle]). For the biological activity and pharmacological properties of thio­semi­carb­azones and their metal complexes, see: Cowley et al. (2002 [triangle]); Ming (2003 [triangle]); Lobana et al. (2004 [triangle], 2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-0o184-scheme1.jpg

Experimental

Crystal data

  • C6H12N4OS
  • M r = 188.26
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-0o184-efi2.jpg
  • a = 5.5205 (1) Å
  • b = 8.6077 (2) Å
  • c = 9.5650 (2) Å
  • α = 79.750 (1)°
  • β = 89.509 (1)°
  • γ = 85.083 (1)°
  • V = 445.61 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.32 mm−1
  • T = 100 K
  • 0.51 × 0.25 × 0.07 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.854, T max = 0.978
  • 12035 measured reflections
  • 3256 independent reflections
  • 2920 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.081
  • S = 1.08
  • 3256 reflections
  • 124 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811053621/mw2038sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053621/mw2038Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053621/mw2038Isup3.cml

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the RU research Grant (1001/PKIMIA/815067). NEE thanks Universiti Sains Malaysia for a post-doctoral fellowship and the Inter­national University of Africa (Sudan) for providing research leave. HAF and AQA each thank the Ministry of Higher Education and the University of Sabha (Libya) for a scholarship.

supplementary crystallographic information

Comment

Thiosemicarbazones and their metal complexes have attracted significant attention because of their wide-ranging biological and pharmacological activities related to specific structures as well as chemical properties (Cowley et al., 2002; Ming, 2003; Lobana et al., 2007; Lobana et al., 2004). In this paper we report the crystal structure of (E)-2-((E)-3-(hydroxyimino)butan-2-ylidene)-N-methylhydrazinecarbothioamide (Fig. 1).

In the title compound, C6H12N4OS, butane is the longest carbon-carbon chain with the oxime group bound to C2 and the 4-methyl-3-thiosemicarbazide moiety bound to C3. The two methyl groups C1 and C4 are trans to each other. The torsion angles of the chains (O1/N1/C2/C3), (C1/C2/C3/C4) and (N2/N3/C5/N4) are 178.35 (8)°, -176.26 (10)° and -5.71 (13)°, respectively, indicating the near-planarity of the molecular backbone. All bond lengths and angles are normal (Allen et al., 1987).

Cyclic intramolecular N4—H1N4···N2, C1—H1B···N2 and C4—H4B···N1 hydrogen-bonding interactions [graph set S(5), (Bernstein et al., 1995)] are present (Table 1) with the latter two being notably weaker than the first. In the crystal molecules are connected through intermolecular O1—H1O1···S1 hydrogen bonds into infinite one-dimensional chains which propagate along [1 0 -1]. In addition, intermolecular N3—H1N3···S1, C4—H4A···S1 and C6—H6A···O1 hydrogen bonds associate these chains into sheets while the sheets are tied together via C4—H4C···O1 interactions (Fig. 2, Table 1). As a consequence of the C4—H4A···S1 and C4—H4C···O1 interactions, a rather short H4B-H4B contact is forced between adjacent molecules in the sheet.

Experimental

To a hot stirred solution of 2,3-butanedione monoxime (1.01 g, 10 mmole) in ethanol (20 ml) containing a few drops of glacial acetic acid was added 4-methyl-3-thiosemicarbazide (1.05 g, 10 mmole) dissolved in ethanol (20 ml). The reaction mixture was then heated under reflux for 3 h. The mixture was filtered and left to cool, the resulting white solid was collected by suction filtration and washed with cold EtOH. The white crystals were grown from ethanol soultion by slow evaporation at room temperature, yield, 78.8%, m.p., 487.5–490 K.

Refinement

N and O bound H atoms were located in a difference Fourier map and were refined freely. The remaining H atoms were positioned geometrically and refined using a riding model with C—H = 0.98 and Uiso(H) = 1.5Ueq(C) for methyl groups. The highest residual electron density peak is located 0.63 Å from C2 and the deepest hole is located 0.68 Å from C4.

Figures

Fig. 1.
The molecular structure of the title compound with 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The crystal packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C6H12N4OSZ = 2
Mr = 188.26F(000) = 200
Triclinic, P1Dx = 1.403 Mg m3
Hall symbol: -P 1Melting point = 487.5–490 K
a = 5.5205 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.6077 (2) ÅCell parameters from 7387 reflections
c = 9.5650 (2) Åθ = 2.4–32.7°
α = 79.750 (1)°µ = 0.32 mm1
β = 89.509 (1)°T = 100 K
γ = 85.083 (1)°Plate, colourless
V = 445.61 (2) Å30.51 × 0.25 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer3256 independent reflections
Radiation source: fine-focus sealed tube2920 reflections with I > 2σ(I)
graphiteRint = 0.020
[var phi] and ω scansθmax = 32.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −8→8
Tmin = 0.854, Tmax = 0.978k = −13→13
12035 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0347P)2 + 0.1679P] where P = (Fo2 + 2Fc2)/3
3256 reflections(Δ/σ)max = 0.001
124 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = −0.39 e Å3

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
S10.94334 (4)0.16073 (3)0.30007 (2)0.01590 (7)
O1−0.03857 (14)0.29827 (9)0.95645 (8)0.02032 (15)
N10.16712 (15)0.21630 (10)0.90822 (9)0.01569 (15)
N20.44402 (14)0.22893 (9)0.57941 (8)0.01351 (14)
N30.64505 (15)0.16555 (10)0.51705 (8)0.01452 (15)
N40.51169 (15)0.32555 (10)0.31045 (8)0.01554 (15)
C10.02246 (18)0.37515 (12)0.67902 (10)0.01835 (18)
H1A−0.14580.35750.70640.028*
H1B0.04640.36280.57980.028*
H1C0.05560.48250.68950.028*
C20.19230 (17)0.25693 (11)0.77265 (10)0.01371 (16)
C30.40835 (17)0.17983 (11)0.71298 (10)0.01444 (16)
C40.5672 (2)0.05499 (14)0.80647 (11)0.0258 (2)
H4A0.6119−0.03280.75600.039*
H4B0.47910.01580.89320.039*
H4C0.71460.10010.83140.039*
C50.68449 (17)0.22272 (10)0.37711 (9)0.01296 (15)
C60.51377 (18)0.39340 (12)0.15976 (10)0.01718 (18)
H6A0.37030.46860.13620.026*
H6B0.51110.30860.10380.026*
H6C0.66120.44860.13790.026*
H1N30.754 (3)0.0948 (18)0.5626 (16)0.025 (4)*
H1N40.387 (3)0.3399 (18)0.3605 (17)0.026 (4)*
H1O1−0.040 (3)0.263 (2)1.046 (2)0.039 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.01340 (11)0.02020 (11)0.01157 (10)0.00444 (8)0.00346 (7)0.00102 (7)
O10.0191 (3)0.0277 (4)0.0116 (3)0.0092 (3)0.0044 (3)−0.0022 (3)
N10.0146 (4)0.0190 (3)0.0124 (3)0.0039 (3)0.0031 (3)−0.0025 (3)
N20.0128 (3)0.0160 (3)0.0112 (3)0.0009 (3)0.0029 (3)−0.0020 (3)
N30.0135 (3)0.0179 (3)0.0102 (3)0.0041 (3)0.0024 (3)0.0002 (3)
N40.0135 (4)0.0203 (4)0.0103 (3)0.0044 (3)0.0026 (3)0.0012 (3)
C10.0175 (4)0.0223 (4)0.0126 (4)0.0057 (3)0.0007 (3)0.0005 (3)
C20.0134 (4)0.0154 (4)0.0113 (4)0.0017 (3)0.0009 (3)−0.0013 (3)
C30.0151 (4)0.0161 (4)0.0107 (4)0.0028 (3)0.0019 (3)−0.0006 (3)
C40.0265 (5)0.0314 (5)0.0129 (4)0.0159 (4)0.0054 (4)0.0048 (4)
C50.0129 (4)0.0145 (4)0.0108 (4)0.0004 (3)0.0014 (3)−0.0014 (3)
C60.0180 (4)0.0202 (4)0.0106 (4)0.0046 (3)0.0013 (3)0.0017 (3)

Geometric parameters (Å, °)

S1—C51.6914 (9)C1—H1A0.9800
O1—N11.4034 (10)C1—H1B0.9800
O1—H1O10.858 (19)C1—H1C0.9800
N1—C21.2911 (12)C2—C31.4752 (13)
N2—C31.2912 (12)C3—C41.4944 (13)
N2—N31.3733 (11)C4—H4A0.9800
N3—C51.3639 (12)C4—H4B0.9800
N3—H1N30.876 (15)C4—H4C0.9800
N4—C51.3285 (12)C6—H6A0.9800
N4—C61.4560 (12)C6—H6B0.9800
N4—H1N40.847 (16)C6—H6C0.9800
C1—C21.4977 (13)
N1—O1—H1O1104.1 (12)N2—C3—C2115.15 (8)
C2—N1—O1111.22 (8)N2—C3—C4125.00 (9)
C3—N2—N3118.54 (8)C2—C3—C4119.84 (8)
C5—N3—N2117.75 (8)C3—C4—H4A109.5
C5—N3—H1N3118.0 (10)C3—C4—H4B109.5
N2—N3—H1N3124.1 (10)H4A—C4—H4B109.5
C5—N4—C6124.53 (8)C3—C4—H4C109.5
C5—N4—H1N4114.1 (11)H4A—C4—H4C109.5
C6—N4—H1N4120.9 (11)H4B—C4—H4C109.5
C2—C1—H1A109.5N4—C5—N3116.23 (8)
C2—C1—H1B109.5N4—C5—S1124.44 (7)
H1A—C1—H1B109.5N3—C5—S1119.33 (7)
C2—C1—H1C109.5N4—C6—H6A109.5
H1A—C1—H1C109.5N4—C6—H6B109.5
H1B—C1—H1C109.5H6A—C6—H6B109.5
N1—C2—C3115.02 (8)N4—C6—H6C109.5
N1—C2—C1124.30 (8)H6A—C6—H6C109.5
C3—C2—C1120.68 (8)H6B—C6—H6C109.5
C3—N2—N3—C5−177.76 (8)N1—C2—C3—C44.82 (14)
O1—N1—C2—C3178.35 (8)C1—C2—C3—C4−176.26 (10)
O1—N1—C2—C1−0.52 (13)C6—N4—C5—N3−176.61 (9)
N3—N2—C3—C2178.38 (8)C6—N4—C5—S13.43 (14)
N3—N2—C3—C4−1.47 (15)N2—N3—C5—N4−5.71 (13)
N1—C2—C3—N2−175.03 (9)N2—N3—C5—S1174.25 (6)
C1—C2—C3—N23.88 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H1N3···S1i0.877 (16)2.781 (16)3.6519 (9)172.0 (14)
N4—H1N4···N20.848 (16)2.155 (16)2.5932 (11)111.9 (13)
O1—H1O1···S1ii0.857 (19)2.437 (19)3.2930 (8)178.3 (17)
C1—H1B···N20.982.392.7919 (13)104
C4—H4A···S1i0.982.693.3991 (12)129
C4—H4B···N10.982.352.7698 (14)105
C4—H4C···O1iii0.982.713.6173 (16)154
C6—H6A···O1iv0.982.633.6011 (12)170

Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1, y, z+1; (iii) x+1, y, z; (iv) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: MW2038).

References

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  • Choi, K.-Y., Yang, S.-M., Lee, K.-C., Ryu, H., Lee, C. H., Seo, J. & Suh, M. (2008). Transition Met. Chem. 33, 99–105.
  • Cowley, A. R., Dilworth, J. R., Donnelly, P. S., Labisbal, E. & Sousa, A. (2002). J. Am. Chem. Soc. 124, 5270–5271. [PubMed]
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  • Lobana T. S., Rekha, Pannu A.P.S., Hundal G., Butcher R. J. & Castineiras A. (2007). Polyhedron, 26, 2621–2628.
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