Crystal structure of (2E)-N-methyl-2-[(4-oxo-4H-chromen-3-yl)methyl­idene]hydrazine­carbo­thio­amide

Vimala, G.; Govindaraj, J.; Haribabu, J.; Karvembu, R.; SubbiahPandi, A.

doi:10.1107/S1600536814021667

organic compounds

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Crystal structure of (2E)-N-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]hydrazinecarbothioamide

G. Vimala,^a J. Govindaraj,^b J. Haribabu,^c R. Karvembu ^d and A. SubbiahPandi ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^bDepartment of Physics, Pachaiyappa's College for Men, Kancheepuram 631 501, India, ^cDepartment of Chemistry, National Institute of Technology, Trichy 620 015, India, and ^dDeparment of Chemistry, National Institute of Technology, Trichy 620 015, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 20 September 2014; accepted 1 October 2014; online 8 October 2014)

In the title compound, C₁₂H₁₁N₃O₂S, the dihedral angle between the 4H-chromen-4-one ring system and the –CH=N—NH—CS—NH– unit is 6.22 (1)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(14) loops. The dimers are reinforced by a pair of C—H⋯O interactions, which generate R₂²(10) loops.

Keywords: crystal structure; hydrazinecarbothioamide; 4H-chromen-4-one; biological properties; hydrogen bonding.

CCDC reference: 1027156

1. Related literature

For the biological properties of related compounds, see: Khan et al. (2009 ); Tu et al. (2013 ); Kelly et al. (1996 ). For a related structure, see: Ishikawa & Watanabe (2014 ).

2. Experimental

2.1. Crystal data

C₁₂H₁₁N₃O₂S
M_r = 261.30
Monoclinic, P 2₁ /n
a = 6.3702 (7) Å
b = 20.647 (2) Å
c = 9.2717 (10) Å
β = 98.365 (3)°
V = 1206.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

2.2. Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.924, T_max = 0.948
17429 measured reflections
3560 independent reflections
2257 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.131
S = 1.06
3560 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.11	2.897 (2)	152
C10—H10⋯O2ⁱ	0.93	2.44	3.219 (2)	141
Symmetry code: (i) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1027156

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814021667/hb7287sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021667/hb7287Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814021667/hb7287Isup3.cml

checkCIF report

Comment top

Thiosemicarbazones are of considerable interest because of their versatile chemistry and various biological activites such as antitumor, antibacterial, antiviral, antiamoebic and antimalarial (Kelly et al., 1996). Schiff bases derived from 3-formylchromones have attracted much attention due to their biological functions such as enzyme inhibition (Khan et al., 2009; Tu et al., 2013).

The structure of the title compound (Figure 1) shows that the atoms of both 4H-chromen-4-one and the –CH=N—NH—CS—NH– segments are roughly planar and the largest deviations are -0.144 (2) and -0.114 (2) Å for O2 and C12 respectively. The dihedral angles between 4H-chromen-4-one and –CH=N—NH—CS—NH—C– unit and the benzene ring of 4H-chromen-4-one and –CH=N—NH—CS—NH—C– unit are 6.22 (1) and 7.12 (1)°, respectively.

In the crystal, inversion dimers linked by pairs of N—H···O hydrogen bonds generate R₂²(14) loops. The dimers are reinforced by a pair of C—H···O interactions, which generate R₂²(10) loops.

Related literature top

For the biological properties of related compounds, see: Khan et al. (2009); Tu et al. (2013); Kelly et al. (1996). For a related structure, see: Ishikawa & Watanabe (2014).

Experimental top

1.05 g (0.01 mol) of N-methylhydrazinecarbothioamide was dissolved in 20 ml of hot ethanol and to this 1.74 g of 4-oxo-4H-Chromene-3-carbaldehydein 10 ml of ethanol was added and continuously stirred for a period of 10 min with continuous stirring. The reaction mixture was refluxed for 2 h and allowed to cool whereby shining white was filtered and washed thoroughly with ethanol and then dried in vaccum. The compound was recrystallized from hot ethanol to yield colourless blocks in 92% yield.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

The packing of the title compound with hydrogen bonds represented by dashed lines. Hydrogen atoms not involved in these bonds are omitted for clarity.

(2E)-N-Methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]hydrazinecarbothioamide top

Crystal data top

C₁₂H₁₁N₃O₂S	Z = 4
M_r = 261.30	F(000) = 544
Monoclinic, P2₁/n	D_x = 1.439 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.3702 (7) Å	µ = 0.27 mm⁻¹
b = 20.647 (2) Å	T = 293 K
c = 9.2717 (10) Å	Block, colourless
β = 98.365 (3)°	0.30 × 0.25 × 0.20 mm
V = 1206.5 (2) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	3560 independent reflections
Radiation source: fine-focus sealed tube	2257 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω and ϕ scans	θ_max = 30.2°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.924, T_max = 0.948	k = −28→28
17429 measured reflections	l = −12→12

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.056P)² + 0.3687P] where P = (F_o² + 2F_c²)/3
3560 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₁N₃O₂S	V = 1206.5 (2) Å³
M_r = 261.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.3702 (7) Å	µ = 0.27 mm⁻¹
b = 20.647 (2) Å	T = 293 K
c = 9.2717 (10) Å	0.30 × 0.25 × 0.20 mm
β = 98.365 (3)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3560 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2257 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.948	R_int = 0.031
17429 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
3560 reflections	Δρ_min = −0.24 e Å⁻³
164 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
C1	1.1216 (3)	−0.01086 (8)	−0.30947 (18)	0.0402 (4)
C2	1.2628 (3)	−0.03414 (11)	−0.3973 (2)	0.0536 (5)
H2	1.3795	−0.0097	−0.4138	0.064*
C3	1.2268 (4)	−0.09395 (12)	−0.4591 (2)	0.0615 (6)
H3	1.3198	−0.1102	−0.5187	0.074*
C4	1.0550 (4)	−0.13046 (11)	−0.4344 (2)	0.0590 (6)
H4	1.0321	−0.1708	−0.4784	0.071*
C5	0.9167 (3)	−0.10774 (9)	−0.3453 (2)	0.0485 (5)
H5	0.8020	−0.1329	−0.3279	0.058*
C6	0.9493 (3)	−0.04658 (8)	−0.28081 (17)	0.0359 (4)
C7	0.8095 (3)	−0.02066 (8)	−0.18335 (17)	0.0353 (4)
C8	0.8552 (3)	0.04523 (7)	−0.13502 (17)	0.0336 (3)
C9	1.0264 (3)	0.07560 (8)	−0.1711 (2)	0.0429 (4)
H9	1.0518	0.1177	−0.1376	0.051*
C10	0.7153 (3)	0.07618 (8)	−0.04415 (18)	0.0373 (4)
H10	0.5918	0.0552	−0.0274	0.045*
C11	0.6662 (3)	0.21399 (7)	0.16614 (18)	0.0367 (4)
C12	0.9249 (4)	0.30201 (10)	0.2112 (3)	0.0619 (6)
H12A	0.8427	0.3380	0.1689	0.093*
H12B	1.0703	0.3075	0.1976	0.093*
H12C	0.9158	0.2998	0.3136	0.093*
N1	0.7607 (2)	0.13156 (6)	0.01244 (15)	0.0367 (3)
N2	0.6206 (2)	0.15691 (6)	0.09629 (16)	0.0400 (3)
H2A	0.5048	0.1368	0.1046	0.048*
N3	0.8432 (3)	0.24283 (7)	0.14142 (18)	0.0456 (4)
H3A	0.9141	0.2252	0.0797	0.055*
O1	1.1633 (2)	0.04988 (6)	−0.25169 (15)	0.0482 (3)
O2	0.6644 (2)	−0.05230 (6)	−0.14399 (16)	0.0550 (4)
S1	0.49924 (9)	0.24309 (2)	0.27366 (6)	0.05253 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0460 (10)	0.0399 (9)	0.0355 (9)	0.0073 (7)	0.0089 (7)	0.0057 (7)
C2	0.0545 (12)	0.0624 (12)	0.0470 (11)	0.0127 (10)	0.0180 (9)	0.0078 (9)
C3	0.0724 (15)	0.0678 (14)	0.0469 (12)	0.0299 (12)	0.0167 (10)	0.0005 (10)
C4	0.0805 (16)	0.0484 (11)	0.0468 (11)	0.0189 (11)	0.0050 (11)	−0.0096 (9)
C5	0.0583 (12)	0.0403 (9)	0.0451 (10)	0.0052 (8)	0.0011 (9)	−0.0057 (8)
C6	0.0422 (9)	0.0336 (8)	0.0307 (8)	0.0050 (7)	0.0018 (7)	0.0015 (6)
C7	0.0365 (9)	0.0348 (8)	0.0339 (8)	−0.0016 (6)	0.0024 (7)	−0.0008 (6)
C8	0.0377 (9)	0.0302 (7)	0.0328 (8)	−0.0005 (6)	0.0052 (7)	0.0005 (6)
C9	0.0517 (11)	0.0329 (8)	0.0463 (10)	−0.0033 (7)	0.0147 (8)	0.0002 (7)
C10	0.0397 (9)	0.0353 (8)	0.0375 (9)	−0.0028 (7)	0.0080 (7)	−0.0028 (7)
C11	0.0430 (10)	0.0274 (7)	0.0401 (9)	0.0026 (6)	0.0072 (7)	0.0012 (6)
C12	0.0564 (13)	0.0406 (10)	0.0913 (17)	−0.0104 (9)	0.0190 (12)	−0.0151 (10)
N1	0.0445 (8)	0.0310 (7)	0.0357 (7)	0.0011 (6)	0.0097 (6)	−0.0006 (5)
N2	0.0427 (8)	0.0328 (7)	0.0469 (8)	−0.0036 (6)	0.0150 (7)	−0.0058 (6)
N3	0.0500 (9)	0.0330 (7)	0.0578 (10)	−0.0036 (6)	0.0213 (8)	−0.0072 (6)
O1	0.0510 (8)	0.0410 (7)	0.0572 (8)	−0.0043 (5)	0.0233 (6)	0.0007 (6)
O2	0.0539 (8)	0.0445 (7)	0.0712 (10)	−0.0181 (6)	0.0241 (7)	−0.0158 (6)
S1	0.0572 (3)	0.0399 (3)	0.0659 (4)	0.0015 (2)	0.0269 (3)	−0.0093 (2)

Geometric parameters (Å, º) top

C1—O1	1.374 (2)	C8—C10	1.460 (2)
C1—C6	1.380 (2)	C9—O1	1.338 (2)
C1—C2	1.384 (3)	C9—H9	0.9300
C2—C3	1.367 (3)	C10—N1	1.274 (2)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.375 (3)	C11—N3	1.324 (2)
C3—H3	0.9300	C11—N2	1.356 (2)
C4—C5	1.375 (3)	C11—S1	1.6715 (17)
C4—H4	0.9300	C12—N3	1.444 (2)
C5—C6	1.400 (2)	C12—H12A	0.9600
C5—H5	0.9300	C12—H12B	0.9600
C6—C7	1.459 (2)	C12—H12C	0.9600
C7—O2	1.230 (2)	N1—N2	1.3695 (18)
C7—C8	1.449 (2)	N2—H2A	0.8600
C8—C9	1.342 (2)	N3—H3A	0.8600

O1—C1—C6	121.78 (15)	O1—C9—C8	124.97 (16)
O1—C1—C2	116.17 (17)	O1—C9—H9	117.5
C6—C1—C2	122.05 (17)	C8—C9—H9	117.5
C3—C2—C1	118.5 (2)	N1—C10—C8	120.64 (15)
C3—C2—H2	120.8	N1—C10—H10	119.7
C1—C2—H2	120.8	C8—C10—H10	119.7
C2—C3—C4	121.0 (2)	N3—C11—N2	115.89 (15)
C2—C3—H3	119.5	N3—C11—S1	124.97 (13)
C4—C3—H3	119.5	N2—C11—S1	119.14 (13)
C5—C4—C3	120.5 (2)	N3—C12—H12A	109.5
C5—C4—H4	119.7	N3—C12—H12B	109.5
C3—C4—H4	119.7	H12A—C12—H12B	109.5
C4—C5—C6	119.8 (2)	N3—C12—H12C	109.5
C4—C5—H5	120.1	H12A—C12—H12C	109.5
C6—C5—H5	120.1	H12B—C12—H12C	109.5
C1—C6—C5	118.20 (16)	C10—N1—N2	116.71 (14)
C1—C6—C7	119.82 (15)	C11—N2—N1	119.45 (14)
C5—C6—C7	121.97 (16)	C11—N2—H2A	120.3
O2—C7—C8	122.21 (15)	N1—N2—H2A	120.3
O2—C7—C6	122.79 (15)	C11—N3—C12	124.28 (16)
C8—C7—C6	115.00 (14)	C11—N3—H3A	117.9
C9—C8—C7	119.72 (15)	C12—N3—H3A	117.9
C9—C8—C10	121.73 (15)	C9—O1—C1	118.35 (14)
C7—C8—C10	118.52 (14)

O1—C1—C2—C3	−179.09 (17)	C6—C7—C8—C9	−5.2 (2)
C6—C1—C2—C3	1.2 (3)	O2—C7—C8—C10	−4.0 (2)
C1—C2—C3—C4	−0.3 (3)	C6—C7—C8—C10	176.46 (14)
C2—C3—C4—C5	−0.8 (3)	C7—C8—C9—O1	0.6 (3)
C3—C4—C5—C6	0.9 (3)	C10—C8—C9—O1	178.80 (16)
O1—C1—C6—C5	179.29 (15)	C9—C8—C10—N1	−5.1 (3)
C2—C1—C6—C5	−1.0 (3)	C7—C8—C10—N1	173.16 (15)
O1—C1—C6—C7	−1.8 (2)	C8—C10—N1—N2	−179.90 (14)
C2—C1—C6—C7	177.85 (16)	N3—C11—N2—N1	3.0 (2)
C4—C5—C6—C1	−0.1 (3)	S1—C11—N2—N1	−177.53 (12)
C4—C5—C6—C7	−178.91 (17)	C10—N1—N2—C11	176.29 (15)
C1—C6—C7—O2	−173.71 (17)	N2—C11—N3—C12	−176.58 (18)
C5—C6—C7—O2	5.1 (3)	S1—C11—N3—C12	4.0 (3)
C1—C6—C7—C8	5.8 (2)	C8—C9—O1—C1	3.8 (3)
C5—C6—C7—C8	−175.36 (16)	C6—C1—O1—C9	−3.1 (2)
O2—C7—C8—C9	174.28 (17)	C2—C1—O1—C9	177.22 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.11	2.897 (2)	152
C10—H10···O2ⁱ	0.93	2.44	3.219 (2)	141

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.11	2.897 (2)	152
C10—H10···O2ⁱ	0.93	2.44	3.219 (2)	141

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

References

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ishikawa, Y. & Watanabe, K. (2014). Acta Cryst. E70, o472. CSD CrossRef IUCr Journals Google Scholar
Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1996). J. Chem. Soc. Dalton Trans. pp. 53–59. CSD CrossRef Web of Science Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (2E)-N-methyl-2-[(4-oxo-4H-chromen-3-yl)methyl­­idene]hydrazine­carbo­thio­amide

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (2E)-N-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]hydrazinecarbothioamide