(E)-N-Ethyl-2-[(E)-3-(hy­droxy­imino)­butan-2-yl­idene]hydrazinecarbothio­amide

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

doi:10.1107/S1600536812028632

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2552

https://doi.org/10.1107/S1600536812028632

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(E)-N-Ethyl-2-[(E)-3-(hydroxyimino)butan-2-ylidene]hydrazinecarbothioamide

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

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

(Received 7 June 2012; accepted 24 June 2012; online 25 July 2012)

In the crystal structure of the title compound, C₇H₁₄N₄OS, molecules are linked through N—H⋯S and O—H⋯N hydrogen bonds and C—H⋯S interactions, forming chains propagating along [21-1].

Related literature

For related structures, see:Abduelftah et al. (2012a ,b ); Choi et al. (2008 ). For the biological activity and pharmacological properties of thiosemicarbazones and their metal complexes, see: Cowley et al. (2002 ); Ming (2003 ). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₁₄N₄OS
M_r = 202.28
Triclinic, $[P \overline 1]$
a = 5.7065 (2) Å
b = 9.0632 (3) Å
c = 10.7109 (4) Å
α = 71.309 (1)°
β = 76.318 (1)°
γ = 86.420 (1)°
V = 509.80 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.57 × 0.20 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.854, T_max = 0.979
15442 measured reflections
4093 independent reflections
3648 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.093
S = 1.08
4093 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1ⁱ	0.85	2.00	2.7876 (10)	154
N3—H1N3⋯S1ⁱⁱ	0.87	2.75	3.6124 (8)	171
C4—H4A⋯S1ⁱⁱ	0.98	2.64	3.4302 (12)	138
Symmetry codes: (i) -x+3, -y+2, -z; (ii) -x+1, -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: https://doi.org/10.1107/S1600536812028632/ng5276sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028632/ng5276Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028632/ng5276Isup3.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). In this paper we report the crystal structure of the title compound (Fig. 1).

In the title compound, C₇H₁₄N₄OS, the butyl chain is the longest carbon-carbon chain with the hydroxylamine group bound to C2 and the N-ethylhydrazinecarbothioamide moiety bound to C3.

Cyclic intramolecular N4—H1N4···N2, C1—H1A···O1 and C4—H4B···N1 hydrogen-bonding interactions [graph set S(5), (Bernstein et al., 1995)] are present (Table 1). In the crystal molecules are connected through intermolecular O1—H1O1···N1, N3—H1N3···S1 and C4—H4A···S1 hydrogen bonds into infinite chains which propagate along [2 1 - 1] (Table 1, Fig.2).

Related literature top

For related structures, see:Abduelftah et al. (2012a,b); Choi et al. (2008). For the biological activity and pharmacological properties of thiosemicarbazones and their metal complexes, see: Cowley et al. (2002); Ming (2003). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995).

Experimental top

The ligand was prepared by mixing a solution of 2,3-butanedione monoxime (1.01 g, 1 mmol) in EtOH (20 ml) with a solution of 4-ethyl-3-thiosemicarbzide (1.19 g, 1 mmol) in EtOH (20 ml). On adding a few drops of glacial acetic acid to the mixture, a solution of yellowish-white color was formed. The reaction mixture then was heated under reflux with stirring for 3 hrs. The mixture was filtered and left to cool; a white precipitate was formed, then collected by filtration and washed by cold EtOH. Colorless crystal was grown by slow evaporation of EtOH at room temperature, yield (66%).

Structure description top

In the title compound, C₇H₁₄N₄OS, the butyl chain is the longest carbon-carbon chain with the hydroxylamine group bound to C2 and the N-ethylhydrazinecarbothioamide moiety bound to C3.

For related structures, see:Abduelftah et al. (2012a,b); Choi et al. (2008). For the biological activity and pharmacological properties of thiosemicarbazones and their metal complexes, see: Cowley et al. (2002); Ming (2003). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995).

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)-N-Ethyl-2-[(E)-3-(hydroxyimino)butan-2- ylidene]hydrazinecarbothioamide top

Crystal data top

C₇H₁₄N₄OS	Z = 2
M_r = 202.28	F(000) = 216
Triclinic, P1	D_x = 1.318 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7065 (2) Å	Cell parameters from 8235 reflections
b = 9.0632 (3) Å	θ = 3.6–35.1°
c = 10.7109 (4) Å	µ = 0.29 mm⁻¹
α = 71.309 (1)°	T = 100 K
β = 76.318 (1)°	Plate, colourless
γ = 86.420 (1)°	0.57 × 0.20 × 0.07 mm
V = 509.80 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	4093 independent reflections
Radiation source: fine-focus sealed tube	3648 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 34.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.854, T_max = 0.979	k = −14→14
15442 measured reflections	l = −16→16

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0432P)² + 0.1608P] where P = (F_o² + 2F_c²)/3
4093 reflections	(Δ/σ)_max = 0.001
121 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₇H₁₄N₄OS	γ = 86.420 (1)°
M_r = 202.28	V = 509.80 (3) Å³
Triclinic, P1	Z = 2
a = 5.7065 (2) Å	Mo Kα radiation
b = 9.0632 (3) Å	µ = 0.29 mm⁻¹
c = 10.7109 (4) Å	T = 100 K
α = 71.309 (1)°	0.57 × 0.20 × 0.07 mm
β = 76.318 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4093 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3648 reflections with I > 2σ(I)
T_min = 0.854, T_max = 0.979	R_int = 0.023
15442 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	Δρ_max = 0.46 e Å⁻³
4093 reflections	Δρ_min = −0.33 e Å⁻³
121 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	0.44242 (4)	0.52051 (3)	0.69791 (2)	0.02043 (7)
O1	1.61220 (13)	1.04092 (8)	0.11132 (7)	0.02309 (14)
H1O1	1.6452	1.0633	0.0256	0.035*
N1	1.41316 (13)	0.94009 (9)	0.15010 (7)	0.01695 (13)
N2	1.01528 (13)	0.74755 (9)	0.45088 (7)	0.01587 (13)
N3	0.81401 (13)	0.65358 (9)	0.50040 (7)	0.01734 (13)
H1N3	0.7419	0.6218	0.4504	0.021*
N4	0.82678 (13)	0.66298 (9)	0.71029 (7)	0.01754 (13)
H1N4	0.9652	0.7085	0.6662	0.021*
C1	1.41628 (18)	0.94145 (12)	0.37977 (9)	0.02285 (17)
H1A	1.5830	0.9797	0.3405	0.034*
H1B	1.4111	0.8518	0.4613	0.034*
H1C	1.3154	1.0244	0.4035	0.034*
C2	1.32385 (15)	0.89332 (10)	0.27889 (8)	0.01613 (14)
C3	1.11201 (15)	0.78830 (10)	0.32272 (8)	0.01645 (14)
C4	1.02391 (19)	0.73958 (13)	0.22066 (9)	0.0260 (2)
H4A	0.9612	0.6324	0.2616	0.039*
H4B	1.1576	0.7453	0.1425	0.039*
H4C	0.8953	0.8091	0.1911	0.039*
C5	0.70823 (14)	0.61747 (10)	0.63536 (8)	0.01525 (13)
C6	0.73697 (16)	0.63713 (11)	0.85512 (8)	0.01993 (15)
H6A	0.7165	0.5240	0.9036	0.024*
H6B	0.5777	0.6864	0.8714	0.024*
C7	0.91280 (18)	0.70594 (12)	0.90870 (10)	0.02417 (18)
H7A	0.8508	0.6882	1.0059	0.036*
H7B	0.9315	0.8181	0.8612	0.036*
H7C	1.0696	0.6559	0.8936	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01501 (10)	0.03141 (12)	0.01420 (10)	−0.00775 (7)	0.00028 (6)	−0.00740 (8)
O1	0.0233 (3)	0.0273 (3)	0.0159 (3)	−0.0142 (2)	−0.0004 (2)	−0.0031 (2)
N1	0.0172 (3)	0.0177 (3)	0.0139 (3)	−0.0061 (2)	−0.0013 (2)	−0.0027 (2)
N2	0.0154 (3)	0.0189 (3)	0.0117 (3)	−0.0038 (2)	−0.0016 (2)	−0.0030 (2)
N3	0.0163 (3)	0.0242 (3)	0.0109 (3)	−0.0066 (2)	−0.0010 (2)	−0.0050 (2)
N4	0.0158 (3)	0.0247 (3)	0.0119 (3)	−0.0052 (2)	−0.0012 (2)	−0.0060 (2)
C1	0.0260 (4)	0.0279 (4)	0.0160 (4)	−0.0094 (3)	−0.0062 (3)	−0.0060 (3)
C2	0.0174 (3)	0.0173 (3)	0.0129 (3)	−0.0041 (2)	−0.0032 (2)	−0.0032 (3)
C3	0.0175 (3)	0.0197 (3)	0.0116 (3)	−0.0050 (3)	−0.0021 (2)	−0.0040 (3)
C4	0.0287 (4)	0.0360 (5)	0.0138 (3)	−0.0161 (4)	−0.0015 (3)	−0.0081 (3)
C5	0.0140 (3)	0.0191 (3)	0.0117 (3)	−0.0020 (2)	−0.0017 (2)	−0.0040 (3)
C6	0.0202 (3)	0.0278 (4)	0.0118 (3)	−0.0039 (3)	−0.0012 (3)	−0.0073 (3)
C7	0.0253 (4)	0.0323 (5)	0.0194 (4)	−0.0007 (3)	−0.0078 (3)	−0.0122 (3)

Geometric parameters (Å, º) top

S1—C5	1.6823 (8)	C1—H1B	0.9800
O1—N1	1.4004 (9)	C1—H1C	0.9800
O1—H1O1	0.8499	C2—C3	1.4753 (11)
N1—C2	1.2891 (10)	C3—C4	1.4966 (12)
N2—C3	1.2913 (10)	C4—H4A	0.9800
N2—N3	1.3676 (10)	C4—H4B	0.9800
N3—C5	1.3674 (10)	C4—H4C	0.9800
N3—H1N3	0.8699	C6—C7	1.5182 (13)
N4—C5	1.3326 (10)	C6—H6A	0.9900
N4—C6	1.4594 (11)	C6—H6B	0.9900
N4—H1N4	0.8699	C7—H7A	0.9800
C1—C2	1.4955 (12)	C7—H7B	0.9800
C1—H1A	0.9800	C7—H7C	0.9800

N1—O1—H1O1	101.9	C3—C4—H4A	109.5
C2—N1—O1	113.41 (7)	C3—C4—H4B	109.5
C3—N2—N3	118.88 (7)	H4A—C4—H4B	109.5
C5—N3—N2	117.92 (7)	C3—C4—H4C	109.5
C5—N3—H1N3	117.7	H4A—C4—H4C	109.5
N2—N3—H1N3	124.1	H4B—C4—H4C	109.5
C5—N4—C6	123.53 (7)	N4—C5—N3	116.43 (7)
C5—N4—H1N4	114.6	N4—C5—S1	123.74 (6)
C6—N4—H1N4	121.9	N3—C5—S1	119.83 (6)
C2—C1—H1A	109.5	N4—C6—C7	110.08 (7)
C2—C1—H1B	109.5	N4—C6—H6A	109.6
H1A—C1—H1B	109.5	C7—C6—H6A	109.6
C2—C1—H1C	109.5	N4—C6—H6B	109.6
H1A—C1—H1C	109.5	C7—C6—H6B	109.6
H1B—C1—H1C	109.5	H6A—C6—H6B	108.2
N1—C2—C3	114.67 (7)	C6—C7—H7A	109.5
N1—C2—C1	124.68 (7)	C6—C7—H7B	109.5
C3—C2—C1	120.63 (7)	H7A—C7—H7B	109.5
N2—C3—C2	114.69 (7)	C6—C7—H7C	109.5
N2—C3—C4	125.37 (8)	H7A—C7—H7C	109.5
C2—C3—C4	119.93 (7)	H7B—C7—H7C	109.5

C3—N2—N3—C5	−177.16 (8)	N1—C2—C3—C4	2.37 (13)
O1—N1—C2—C3	179.32 (7)	C1—C2—C3—C4	−179.18 (9)
O1—N1—C2—C1	0.93 (13)	C6—N4—C5—N3	178.54 (8)
N3—N2—C3—C2	178.30 (7)	C6—N4—C5—S1	−1.47 (13)
N3—N2—C3—C4	−0.76 (14)	N2—N3—C5—N4	−7.33 (12)
N1—C2—C3—N2	−176.75 (8)	N2—N3—C5—S1	172.68 (6)
C1—C2—C3—N2	1.71 (12)	C5—N4—C6—C7	−178.86 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1ⁱ	0.85	2.00	2.7876 (10)	154
N3—H1N3···S1ⁱⁱ	0.87	2.75	3.6124 (8)	171
N4—H1N4···N2	0.87	2.17	2.6055 (10)	111
C1—H1A···O1	0.98	2.30	2.6970 (11)	103
C4—H4A···S1ⁱⁱ	0.98	2.64	3.4302 (12)	138
C4—H4B···N1	0.98	2.39	2.7636 (14)	102

Symmetry codes: (i) −x+3, −y+2, −z; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₁₄N₄OS
M_r	202.28
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.7065 (2), 9.0632 (3), 10.7109 (4)
α, β, γ (°)	71.309 (1), 76.318 (1), 86.420 (1)
V (Å³)	509.80 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.57 × 0.20 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.854, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	15442, 4093, 3648
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.787

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.093, 1.08
No. of reflections	4093
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.33

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
O1—H1O1···N1ⁱ	0.8500	2.0000	2.7876 (10)	154.00
N3—H1N3···S1ⁱⁱ	0.8700	2.7500	3.6124 (8)	171.00
N4—H1N4···N2	0.8700	2.1700	2.6055 (10)	111.00
C1—H1A···O1	0.9800	2.3000	2.6970 (11)	103.00
C4—H4A···S1ⁱⁱ	0.9800	2.6400	3.4302 (12)	138.00
C4—H4B···N1	0.9800	2.3900	2.7636 (14)	102.00

Symmetry codes: (i) −x+3, −y+2, −z; (ii) −x+1, −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). HAF and AQA thank the Ministry of Higher Education and the University of Sabha (Libya) for a scholarship.

References

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