organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aSchool of Chemical Sciences, Universiti Sains Malaysia, Minden, Penang, Malaysia, bFaculty of Science, Sabha University, Libya, cDepartment of Chemistry, International University of Africa, Khartoum, Sudan, and dX-ray Crystallography Unit, School of Physics,Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: sgteoh@usm.my

(Received 3 November 2011; accepted 13 December 2011; online 21 December 2011)

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 [10[\overline{1}]] 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[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For related structures, see: Choi et al. (2008[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.]). For the biological activity and pharmacological properties of thio­semi­carb­azones and their metal complexes, see: Cowley et al. (2002[Cowley, A. R., Dilworth, J. R., Donnelly, P. S., Labisbal, E. & Sousa, A. (2002). J. Am. Chem. Soc. 124, 5270-5271.]); Ming (2003[Ming, L.-J. (2003). Med. Res. Rev. 23, 697-762.]); Lobana et al. (2004[Lobana T. S., Rekha & Butcher, R. J. (2004). Transition Met. Chem. 29, 291-295.], 2007[Lobana T. S., Rekha, Pannu A.P.S., Hundal G., Butcher R. J. & Castineiras A. (2007). Polyhedron, 26, 2621-2628.]).

[Scheme 1]

Experimental

Crystal data
  • C6H12N4OS

  • Mr = 188.26

  • Triclinic, [P \overline 1]

  • 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.854, Tmax = 0.978

  • 12035 measured reflections

  • 3256 independent reflections

  • 2920 reflections with I > 2σ(I)

  • Rint = 0.020

Refinement
  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H1N3⋯S1i 0.877 (16) 2.781 (16) 3.6519 (9) 172.0 (14)
N4—H1N4⋯N2 0.848 (16) 2.155 (16) 2.5932 (11) 111.9 (13)
O1—H1O1⋯S1ii 0.857 (19) 2.437 (19) 3.2930 (8) 178.3 (17)
C4—H4A⋯S1i 0.98 2.69 3.3991 (12) 129
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.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines.
(E)-2-[(E)-3-(Hydroxyimino)butan-2-ylidene]-N- methylhydrazinecarbothioamide top
Crystal data top
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 top
Bruker APEXII CCD
diffractometer
3256 independent reflections
Radiation source: fine-focus sealed tube2920 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ϕ and ω scansθmax = 32.7°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 88
Tmin = 0.854, Tmax = 0.978k = 1313
12035 measured reflectionsl = 1414
Refinement top
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 = 1.08 w = 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
Crystal data top
C6H12N4OSγ = 85.083 (1)°
Mr = 188.26V = 445.61 (2) Å3
Triclinic, P1Z = 2
a = 5.5205 (1) ÅMo Kα radiation
b = 8.6077 (2) ŵ = 0.32 mm1
c = 9.5650 (2) ÅT = 100 K
α = 79.750 (1)°0.51 × 0.25 × 0.07 mm
β = 89.509 (1)°
Data collection top
Bruker APEXII CCD
diffractometer
3256 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
2920 reflections with I > 2σ(I)
Tmin = 0.854, Tmax = 0.978Rint = 0.020
12035 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.40 e Å3
3256 reflectionsΔρmin = 0.39 e Å3
124 parameters
Special details top

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) top
xyzUiso*/Ueq
S10.94334 (4)0.16073 (3)0.30007 (2)0.01590 (7)
O10.03857 (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)
H1A0.14580.35750.70640.028*
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)
H4A0.61190.03280.75600.039*
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)*
H1O10.040 (3)0.263 (2)1.046 (2)0.039 (4)*
Atomic displacement parameters (Å2) top
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, º) top
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—C5177.76 (8)N1—C2—C3—C44.82 (14)
O1—N1—C2—C3178.35 (8)C1—C2—C3—C4176.26 (10)
O1—N1—C2—C10.52 (13)C6—N4—C5—N3176.61 (9)
N3—N2—C3—C2178.38 (8)C6—N4—C5—S13.43 (14)
N3—N2—C3—C41.47 (15)N2—N3—C5—N45.71 (13)
N1—C2—C3—N2175.03 (9)N2—N3—C5—S1174.25 (6)
C1—C2—C3—N23.88 (13)
Hydrogen-bond geometry (Å, º) top
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) x1, y, z+1; (iii) x+1, y, z; (iv) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC6H12N4OS
Mr188.26
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)5.5205 (1), 8.6077 (2), 9.5650 (2)
α, β, γ (°)79.750 (1), 89.509 (1), 85.083 (1)
V3)445.61 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.51 × 0.25 × 0.07
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.854, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
12035, 3256, 2920
Rint0.020
(sin θ/λ)max1)0.761
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.081, 1.08
No. of reflections3256
No. of parameters124
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40, 0.39

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
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) x1, y, z+1; (iii) x+1, y, z; (iv) x, y+1, z+1.
 

Footnotes

Thomson Reuters ResearcherID: E-9395-2011.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

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.

References

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