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

Abduelftah, H.S.; Ali, A.Q.; Eltayeb, N.E.; Teoh, S.G.; Fun, H.-K.

doi:10.1107/S1600536811053621

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o184

doi:10.1107/S1600536811053621

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

Halema Shaban Abduelftah,^a,^b Amna Qasem Ali,^a,^b Naser Eltaher Eltayeb,^a,^c ‡ Siang Guan Teoh ^a ^* and Hoong-Kun Fun ^d §

^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 ). 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 et al. (2004 , 2007 ).

Experimental

Crystal data

C₆H₁₂N₄OS
M_r = 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 ) 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[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
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053621/mw2038sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811053621/mw2038Isup3.cml

checkCIF report

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.

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

	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.

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

Crystal data top

C₆H₁₂N₄OS	Z = 2
M_r = 188.26	F(000) = 200
Triclinic, P1	D_x = 1.403 Mg m⁻³
Hall symbol: -P 1	Melting point = 487.5–490 K
a = 5.5205 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6077 (2) Å	Cell parameters from 7387 reflections
c = 9.5650 (2) Å	θ = 2.4–32.7°
α = 79.750 (1)°	µ = 0.32 mm⁻¹
β = 89.509 (1)°	T = 100 K
γ = 85.083 (1)°	Plate, colourless
V = 445.61 (2) Å³	0.51 × 0.25 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	3256 independent reflections
Radiation source: fine-focus sealed tube	2920 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 32.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.854, T_max = 0.978	k = −13→13
12035 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0347P)² + 0.1679P] where P = (F_o² + 2F_c²)/3
3256 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₆H₁₂N₄OS	γ = 85.083 (1)°
M_r = 188.26	V = 445.61 (2) Å³
Triclinic, P1	Z = 2
a = 5.5205 (1) Å	Mo Kα radiation
b = 8.6077 (2) Å	µ = 0.32 mm⁻¹
c = 9.5650 (2) Å	T = 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)
T_min = 0.854, T_max = 0.978	R_int = 0.020
12035 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.40 e Å⁻³
3256 reflections	Δρ_min = −0.39 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.94334 (4)	0.16073 (3)	0.30007 (2)	0.01590 (7)
O1	−0.03857 (14)	0.29827 (9)	0.95645 (8)	0.02032 (15)
N1	0.16712 (15)	0.21630 (10)	0.90822 (9)	0.01569 (15)
N2	0.44402 (14)	0.22893 (9)	0.57941 (8)	0.01351 (14)
N3	0.64505 (15)	0.16555 (10)	0.51705 (8)	0.01452 (15)
N4	0.51169 (15)	0.32555 (10)	0.31045 (8)	0.01554 (15)
C1	0.02246 (18)	0.37515 (12)	0.67902 (10)	0.01835 (18)
H1A	−0.1458	0.3575	0.7064	0.028*
H1B	0.0464	0.3628	0.5798	0.028*
H1C	0.0556	0.4825	0.6895	0.028*
C2	0.19230 (17)	0.25693 (11)	0.77265 (10)	0.01371 (16)
C3	0.40835 (17)	0.17983 (11)	0.71298 (10)	0.01444 (16)
C4	0.5672 (2)	0.05499 (14)	0.80647 (11)	0.0258 (2)
H4A	0.6119	−0.0328	0.7560	0.039*
H4B	0.4791	0.0158	0.8932	0.039*
H4C	0.7146	0.1001	0.8314	0.039*
C5	0.68449 (17)	0.22272 (10)	0.37711 (9)	0.01296 (15)
C6	0.51377 (18)	0.39340 (12)	0.15976 (10)	0.01718 (18)
H6A	0.3703	0.4686	0.1362	0.026*
H6B	0.5111	0.3086	0.1038	0.026*
H6C	0.6612	0.4486	0.1379	0.026*
H1N3	0.754 (3)	0.0948 (18)	0.5626 (16)	0.025 (4)*
H1N4	0.387 (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) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01340 (11)	0.02020 (11)	0.01157 (10)	0.00444 (8)	0.00346 (7)	0.00102 (7)
O1	0.0191 (3)	0.0277 (4)	0.0116 (3)	0.0092 (3)	0.0044 (3)	−0.0022 (3)
N1	0.0146 (4)	0.0190 (3)	0.0124 (3)	0.0039 (3)	0.0031 (3)	−0.0025 (3)
N2	0.0128 (3)	0.0160 (3)	0.0112 (3)	0.0009 (3)	0.0029 (3)	−0.0020 (3)
N3	0.0135 (3)	0.0179 (3)	0.0102 (3)	0.0041 (3)	0.0024 (3)	0.0002 (3)
N4	0.0135 (4)	0.0203 (4)	0.0103 (3)	0.0044 (3)	0.0026 (3)	0.0012 (3)
C1	0.0175 (4)	0.0223 (4)	0.0126 (4)	0.0057 (3)	0.0007 (3)	0.0005 (3)
C2	0.0134 (4)	0.0154 (4)	0.0113 (4)	0.0017 (3)	0.0009 (3)	−0.0013 (3)
C3	0.0151 (4)	0.0161 (4)	0.0107 (4)	0.0028 (3)	0.0019 (3)	−0.0006 (3)
C4	0.0265 (5)	0.0314 (5)	0.0129 (4)	0.0159 (4)	0.0054 (4)	0.0048 (4)
C5	0.0129 (4)	0.0145 (4)	0.0108 (4)	0.0004 (3)	0.0014 (3)	−0.0014 (3)
C6	0.0180 (4)	0.0202 (4)	0.0106 (4)	0.0046 (3)	0.0013 (3)	0.0017 (3)

Geometric parameters (Å, º) top

S1—C5	1.6914 (9)	C1—H1A	0.9800
O1—N1	1.4034 (10)	C1—H1B	0.9800
O1—H1O1	0.858 (19)	C1—H1C	0.9800
N1—C2	1.2911 (12)	C2—C3	1.4752 (13)
N2—C3	1.2912 (12)	C3—C4	1.4944 (13)
N2—N3	1.3733 (11)	C4—H4A	0.9800
N3—C5	1.3639 (12)	C4—H4B	0.9800
N3—H1N3	0.876 (15)	C4—H4C	0.9800
N4—C5	1.3285 (12)	C6—H6A	0.9800
N4—C6	1.4560 (12)	C6—H6B	0.9800
N4—H1N4	0.847 (16)	C6—H6C	0.9800
C1—C2	1.4977 (13)

N1—O1—H1O1	104.1 (12)	N2—C3—C2	115.15 (8)
C2—N1—O1	111.22 (8)	N2—C3—C4	125.00 (9)
C3—N2—N3	118.54 (8)	C2—C3—C4	119.84 (8)
C5—N3—N2	117.75 (8)	C3—C4—H4A	109.5
C5—N3—H1N3	118.0 (10)	C3—C4—H4B	109.5
N2—N3—H1N3	124.1 (10)	H4A—C4—H4B	109.5
C5—N4—C6	124.53 (8)	C3—C4—H4C	109.5
C5—N4—H1N4	114.1 (11)	H4A—C4—H4C	109.5
C6—N4—H1N4	120.9 (11)	H4B—C4—H4C	109.5
C2—C1—H1A	109.5	N4—C5—N3	116.23 (8)
C2—C1—H1B	109.5	N4—C5—S1	124.44 (7)
H1A—C1—H1B	109.5	N3—C5—S1	119.33 (7)
C2—C1—H1C	109.5	N4—C6—H6A	109.5
H1A—C1—H1C	109.5	N4—C6—H6B	109.5
H1B—C1—H1C	109.5	H6A—C6—H6B	109.5
N1—C2—C3	115.02 (8)	N4—C6—H6C	109.5
N1—C2—C1	124.30 (8)	H6A—C6—H6C	109.5
C3—C2—C1	120.68 (8)	H6B—C6—H6C	109.5

C3—N2—N3—C5	−177.76 (8)	N1—C2—C3—C4	4.82 (14)
O1—N1—C2—C3	178.35 (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—C2	178.38 (8)	C6—N4—C5—S1	3.43 (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—S1	174.25 (6)
C1—C2—C3—N2	3.88 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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)
C1—H1B···N2	0.98	2.39	2.7919 (13)	104
C4—H4A···S1ⁱ	0.98	2.69	3.3991 (12)	129
C4—H4B···N1	0.98	2.35	2.7698 (14)	105
C4—H4C···O1ⁱⁱⁱ	0.98	2.71	3.6173 (16)	154
C6—H6A···O1^iv	0.98	2.63	3.6011 (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.

Experimental details

Crystal data
Chemical formula	C₆H₁₂N₄OS
M_r	188.26
Crystal system, space group	Triclinic, 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)
V (Å³)	445.61 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.51 × 0.25 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.854, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	12035, 3256, 2920
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.761

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.081, 1.08
No. of reflections	3256
No. of parameters	124
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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)
C1—H1B···N2	0.98	2.39	2.7919 (13)	104
C4—H4A···S1ⁱ	0.98	2.69	3.3991 (12)	129
C4—H4B···N1	0.98	2.35	2.7698 (14)	105
C4—H4C···O1ⁱⁱⁱ	0.98	2.71	3.6173 (16)	154
C6—H6A···O1^iv	0.98	2.63	3.6011 (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

‡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.

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