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Acta Crystallogr Sect E Struct Rep Online. Aug 1, 2012; 68(Pt 8): o2552.
Published online Jul 25, 2012. doi:  10.1107/S1600536812028632
PMCID: PMC3414996
(E)-N-Ethyl-2-[(E)-3-(hy­droxy­imino)­butan-2-yl­idene]hydrazinecarbothio­amide
Halema Shaban Abduelftah,ab Amna Qasem Ali,cd Naser Eltaher Eltayeb,e Siang Guan Teoh,c* and Hoong-Kun Funf§
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
fX-ray Crystallography Unit, School of Physics,Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
Correspondence e-mail: sgteoh/at/usm.my
Thomson Reuters ResearcherID: E-9395-2011.
§Thomson Reuters ResearcherID: A-3561-2009.
Received June 7, 2012; Accepted June 24, 2012.
Abstract
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 [triangle],b [triangle]); 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]). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is e-68-o2552-scheme1.jpg Object name is e-68-o2552-scheme1.jpg
Crystal data  
  • C7H14N4OS
  • M r = 202.28
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2552-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.093
  • S = 1.08
  • 4093 reflections
  • 121 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.33 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
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028632/ng5276sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028632/ng5276Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812028632/ng5276Isup3.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). HAF and AQA 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). 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).
Experimental
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%).
Refinement
The H atoms were positioned geometrically and refined using a riding model with O—H = 0.85; Uiso(H) = 1.5Ueq(O), N—H = 0.87; Uiso(H) = 1.2Ueq(N), C—H = 0.98; Uiso(H) = 1.5Ueq(C) for methyl groups and C—H = 0.99; Uiso(H) = 1.2Ueq(C) for methylene group. The highest residual electron density peak is located 0.64 Å from C2 and the deepest hole is located 0.16 Å from H4B.
Figures
Fig. 1.
Fig. 1.
The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Fig. 2.
The crystal packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines.
Crystal data
C7H14N4OSZ = 2
Mr = 202.28F(000) = 216
Triclinic, P1Dx = 1.318 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.7065 (2) ÅCell parameters from 8235 reflections
b = 9.0632 (3) Åθ = 3.6–35.1°
c = 10.7109 (4) ŵ = 0.29 mm1
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
Bruker APEXII CCD diffractometer4093 independent reflections
Radiation source: fine-focus sealed tube3648 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
[var phi] and ω scansθmax = 34.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −8→8
Tmin = 0.854, Tmax = 0.979k = −14→14
15442 measured reflectionsl = −16→16
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0432P)2 + 0.1608P] where P = (Fo2 + 2Fc2)/3
4093 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.33 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
S10.44242 (4)0.52051 (3)0.69791 (2)0.02043 (7)
O11.61220 (13)1.04092 (8)0.11132 (7)0.02309 (14)
H1O11.64521.06330.02560.035*
N11.41316 (13)0.94009 (9)0.15010 (7)0.01695 (13)
N21.01528 (13)0.74755 (9)0.45088 (7)0.01587 (13)
N30.81401 (13)0.65358 (9)0.50040 (7)0.01734 (13)
H1N30.74190.62180.45040.021*
N40.82678 (13)0.66298 (9)0.71029 (7)0.01754 (13)
H1N40.96520.70850.66620.021*
C11.41628 (18)0.94145 (12)0.37977 (9)0.02285 (17)
H1A1.58300.97970.34050.034*
H1B1.41110.85180.46130.034*
H1C1.31541.02440.40350.034*
C21.32385 (15)0.89332 (10)0.27889 (8)0.01613 (14)
C31.11201 (15)0.78830 (10)0.32272 (8)0.01645 (14)
C41.02391 (19)0.73958 (13)0.22066 (9)0.0260 (2)
H4A0.96120.63240.26160.039*
H4B1.15760.74530.14250.039*
H4C0.89530.80910.19110.039*
C50.70823 (14)0.61747 (10)0.63536 (8)0.01525 (13)
C60.73697 (16)0.63713 (11)0.85512 (8)0.01993 (15)
H6A0.71650.52400.90360.024*
H6B0.57770.68640.87140.024*
C70.91280 (18)0.70594 (12)0.90870 (10)0.02417 (18)
H7A0.85080.68821.00590.036*
H7B0.93150.81810.86120.036*
H7C1.06960.65590.89360.036*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
S10.01501 (10)0.03141 (12)0.01420 (10)−0.00775 (7)0.00028 (6)−0.00740 (8)
O10.0233 (3)0.0273 (3)0.0159 (3)−0.0142 (2)−0.0004 (2)−0.0031 (2)
N10.0172 (3)0.0177 (3)0.0139 (3)−0.0061 (2)−0.0013 (2)−0.0027 (2)
N20.0154 (3)0.0189 (3)0.0117 (3)−0.0038 (2)−0.0016 (2)−0.0030 (2)
N30.0163 (3)0.0242 (3)0.0109 (3)−0.0066 (2)−0.0010 (2)−0.0050 (2)
N40.0158 (3)0.0247 (3)0.0119 (3)−0.0052 (2)−0.0012 (2)−0.0060 (2)
C10.0260 (4)0.0279 (4)0.0160 (4)−0.0094 (3)−0.0062 (3)−0.0060 (3)
C20.0174 (3)0.0173 (3)0.0129 (3)−0.0041 (2)−0.0032 (2)−0.0032 (3)
C30.0175 (3)0.0197 (3)0.0116 (3)−0.0050 (3)−0.0021 (2)−0.0040 (3)
C40.0287 (4)0.0360 (5)0.0138 (3)−0.0161 (4)−0.0015 (3)−0.0081 (3)
C50.0140 (3)0.0191 (3)0.0117 (3)−0.0020 (2)−0.0017 (2)−0.0040 (3)
C60.0202 (3)0.0278 (4)0.0118 (3)−0.0039 (3)−0.0012 (3)−0.0073 (3)
C70.0253 (4)0.0323 (5)0.0194 (4)−0.0007 (3)−0.0078 (3)−0.0122 (3)
Geometric parameters (Å, º)
S1—C51.6823 (8)C1—H1B0.9800
O1—N11.4004 (9)C1—H1C0.9800
O1—H1O10.8499C2—C31.4753 (11)
N1—C21.2891 (10)C3—C41.4966 (12)
N2—C31.2913 (10)C4—H4A0.9800
N2—N31.3676 (10)C4—H4B0.9800
N3—C51.3674 (10)C4—H4C0.9800
N3—H1N30.8699C6—C71.5182 (13)
N4—C51.3326 (10)C6—H6A0.9900
N4—C61.4594 (11)C6—H6B0.9900
N4—H1N40.8699C7—H7A0.9800
C1—C21.4955 (12)C7—H7B0.9800
C1—H1A0.9800C7—H7C0.9800
N1—O1—H1O1101.9C3—C4—H4A109.5
C2—N1—O1113.41 (7)C3—C4—H4B109.5
C3—N2—N3118.88 (7)H4A—C4—H4B109.5
C5—N3—N2117.92 (7)C3—C4—H4C109.5
C5—N3—H1N3117.7H4A—C4—H4C109.5
N2—N3—H1N3124.1H4B—C4—H4C109.5
C5—N4—C6123.53 (7)N4—C5—N3116.43 (7)
C5—N4—H1N4114.6N4—C5—S1123.74 (6)
C6—N4—H1N4121.9N3—C5—S1119.83 (6)
C2—C1—H1A109.5N4—C6—C7110.08 (7)
C2—C1—H1B109.5N4—C6—H6A109.6
H1A—C1—H1B109.5C7—C6—H6A109.6
C2—C1—H1C109.5N4—C6—H6B109.6
H1A—C1—H1C109.5C7—C6—H6B109.6
H1B—C1—H1C109.5H6A—C6—H6B108.2
N1—C2—C3114.67 (7)C6—C7—H7A109.5
N1—C2—C1124.68 (7)C6—C7—H7B109.5
C3—C2—C1120.63 (7)H7A—C7—H7B109.5
N2—C3—C2114.69 (7)C6—C7—H7C109.5
N2—C3—C4125.37 (8)H7A—C7—H7C109.5
C2—C3—C4119.93 (7)H7B—C7—H7C109.5
C3—N2—N3—C5−177.16 (8)N1—C2—C3—C42.37 (13)
O1—N1—C2—C3179.32 (7)C1—C2—C3—C4−179.18 (9)
O1—N1—C2—C10.93 (13)C6—N4—C5—N3178.54 (8)
N3—N2—C3—C2178.30 (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—S1172.68 (6)
C1—C2—C3—N21.71 (12)C5—N4—C6—C7−178.86 (8)
Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···A
O1—H1O1···N1i0.852.002.7876 (10)154
N3—H1N3···S1ii0.872.753.6124 (8)171
N4—H1N4···N20.872.172.6055 (10)111
C1—H1A···O10.982.302.6970 (11)103
C4—H4A···S1ii0.982.643.4302 (12)138
C4—H4B···N10.982.392.7636 (14)102
Symmetry codes: (i) −x+3, −y+2, −z; (ii) −x+1, −y+1, −z+1.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG5276).
  • Abduelftah, H. S., Ali, A. Q., Eltayeb, N. E., Teoh, S. G. & Fun, H.-K. (2012a). Acta Cryst. E68, m183–m184. [PMC free article] [PubMed]
  • Abduelftah, H. S., Qasem Ali, A., Eltayeb, N. E., Teoh, S. G. & Fun, H.-K. (2012b). Acta Cryst. E68, m108–m109.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • 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]
  • Ming, L.-J. (2003). Med. Res. Rev. 23, 697–762. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
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