2-Sulfanyl­idene-1,2-dihydro­pyridine-3-carbohydrazide

Mansor, S.; Yehye, W.A.; Ariffin, A.; Ng, S.W.

doi:10.1107/S160053681003521X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2516

doi:10.1107/S160053681003521X

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2-Sulfanylidene-1,2-dihydropyridine-3-carbohydrazide

Shahirah Mansor,^a Wagee A. Yehye,^a Azhar Ariffin ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 24 August 2010; accepted 1 September 2010; online 8 September 2010)

All non-H atoms of the title compound, C₆H₇N₃OS, which exists in the thione form, lie in a common plane (r.m.s. of non-H atoms = 0.08 Å). The amino group of the –NH–NH₂ substituent forms an intramolecular hydrogen bond to the S atom. The terminal –NH₂ group is pyramidally coordinated; it forms a weak N—H⋯O and a weak N—H⋯S hydrogen bond. Furthermore, the N atom is an acceptor for a C—H⋯N contact. The amino group of the ring is a hydrogen-bond donor to the carbonyl O atom of an adjacent molecule, this interaction giving rise to a linear chain motif running along the b axis.

Related literature

For the synthesis of 3-mercaptonicotinoylhydrazide from 3-mercaptonicotinic acid, see: Katz et al. (1958 ). For the synthesis of 2-(3,5-di-tert-butyl-4-hydroxybenzylsulfanyl)nicotinic acid, see: Mansor et al. (2008 ).

Experimental

Crystal data

C₆H₇N₃OS
M_r = 169.21
Triclinic, $[P \overline 1]$
a = 7.1952 (2) Å
b = 7.4279 (2) Å
c = 7.7492 (2) Å
α = 88.205 (2)°
β = 64.201 (2)°
γ = 72.072 (2)°
V = 352.22 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 123 K
0.35 × 0.05 × 0.01 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.874, T_max = 0.996
3311 measured reflections
1619 independent reflections
1391 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.08
1619 reflections
128 parameters
7 restraints
All H-atom parameters refined
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88 (1)	1.95 (2)	2.751 (2)	152 (2)
N2—H2⋯S1	0.89 (1)	2.24 (2)	3.007 (2)	145 (2)
N3—H3⋯O1ⁱⁱ	0.88 (2)	2.36 (3)	3.214 (2)	166 (3)
N3—H4⋯S1ⁱⁱⁱ	0.88 (3)	2.85 (3)	3.4173 (18)	124 (2)
C2—H2A⋯N3^iv	0.94 (1)	2.69 (2)	3.323 (4)	125 (2)
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+2, -z+1; (iii) x, y+1, z; (iv) x+1, y-1, z-1.

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681003521X/bt5335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681003521X/bt5335Isup2.hkl

checkCIF report

Comment top

3-Mercaptonicotinylcarbohydrazide is mentioned in the chemical (patent) literature in the context of its synthesis from 3-mercaptonicotinic acid (Katz et al., 1958). This compound was the surprise product of the reaction between ethyl 2-(3,5-di-tert-butyl-4-hydroxybenzylsulfanyl)nicotinate and hydrazine. The compound exists in the thione form. The molecule of pryidyl-2(1H)-thione-3-carbohydrazide (Scheme I, Fig. 1) is planar (r.m.s. of non-H atoms 0.08 Å). In the six-membered ring, the two carbon–carbon double bonds are regarded as being localized. The amino –NH– group of the –NH–NH₂ substituent forms an intramolecular hydrogen bond to the double-bond sulfur atom. The terminal –NH₂ group is pyramidally coordinated; it does not engage in hydrogen bonding. The amino –NH– group of the ring is hydrogen-bond donor to the double-bond oxygen atom an adjacent molecule, this interaction giving rise to a linear chain motif running along the b-axis of the triclinic unit cell (Fig. 2).

Related literature top

For the synthesis of 3-mercaptonicotinoylhydrazide from 3-mercaptonicotinic acid, see: Katz et al. (1958).

For related literature, see: Mansor et al. (2008); Westrip (2009).

Experimental top

The synthesis of colorless 2-(3,5-di-tert-butyl-4-hydroxybenzylsulfanyl)nicotinic acid was described earlier (Mansor et al., 2008); the acid was first converted to the ethyl ester. The ester (0.80 g, 2 mmol) was dissolved in ethanol (15 ml) and to this was added hydrazine hydrate (0.20 ml, 4 mmol). The mixture was heated for 24 h. The solvent was removed to give a brown gummy solid; this was recrystallized from hexane to afford orange plate-like crystals.

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₆H₇N₃OS at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded chain structure.

2-Sulfanylidene-1,2-dihydropyridine-3-carbohydrazide top

Crystal data top

C₆H₇N₃OS	Z = 2
M_r = 169.21	F(000) = 176
Triclinic, P1	D_x = 1.595 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1952 (2) Å	Cell parameters from 1745 reflections
b = 7.4279 (2) Å	θ = 2.9–28.3°
c = 7.7492 (2) Å	µ = 0.40 mm⁻¹
α = 88.205 (2)°	T = 123 K
β = 64.201 (2)°	Plate, orange
γ = 72.072 (2)°	0.35 × 0.05 × 0.01 mm
V = 352.22 (2) Å³

Data collection top

Bruker SMART APEX diffractometer	1619 independent reflections
Radiation source: fine-focus sealed tube	1391 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.874, T_max = 0.996	k = −9→9
3311 measured reflections	l = −10→10

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0372P)² + 0.3308P] where P = (F_o² + 2F_c²)/3
1619 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.67 e Å⁻³
7 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₆H₇N₃OS	γ = 72.072 (2)°
M_r = 169.21	V = 352.22 (2) Å³
Triclinic, P1	Z = 2
a = 7.1952 (2) Å	Mo Kα radiation
b = 7.4279 (2) Å	µ = 0.40 mm⁻¹
c = 7.7492 (2) Å	T = 123 K
α = 88.205 (2)°	0.35 × 0.05 × 0.01 mm
β = 64.201 (2)°

Data collection top

Bruker SMART APEX diffractometer	1619 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1391 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.996	R_int = 0.015
3311 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	7 restraints
wR(F²) = 0.090	All H-atom parameters refined
S = 1.08	Δρ_max = 0.67 e Å⁻³
1619 reflections	Δρ_min = −0.19 e Å⁻³
128 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.58477 (8)	0.32161 (7)	0.76922 (7)	0.02102 (15)
O1	0.7744 (2)	0.81569 (18)	0.44198 (19)	0.0210 (3)
N1	0.8505 (3)	0.1589 (2)	0.4153 (2)	0.0165 (3)
N2	0.5443 (3)	0.7318 (2)	0.7129 (2)	0.0191 (3)
N3	0.4375 (3)	0.9211 (2)	0.8063 (2)	0.0218 (4)
C1	1.0002 (3)	0.1308 (3)	0.2289 (3)	0.0182 (4)
C2	1.0636 (3)	0.2790 (3)	0.1432 (3)	0.0199 (4)
C3	0.9635 (3)	0.4575 (3)	0.2526 (3)	0.0181 (4)
C4	0.8069 (3)	0.4870 (2)	0.4421 (3)	0.0147 (4)
C5	0.7505 (3)	0.3285 (2)	0.5345 (3)	0.0148 (4)
C6	0.7070 (3)	0.6906 (2)	0.5353 (3)	0.0160 (4)
H1	0.805 (4)	0.064 (3)	0.466 (3)	0.036 (7)*
H2	0.505 (4)	0.638 (3)	0.776 (3)	0.039 (7)*
H3	0.404 (4)	0.991 (3)	0.724 (3)	0.036 (7)*
H4	0.533 (3)	0.956 (4)	0.827 (4)	0.032 (7)*
H1A	1.059 (3)	0.0051 (17)	0.165 (3)	0.020 (5)*
H2A	1.171 (3)	0.260 (3)	0.0141 (17)	0.027 (6)*
H3A	1.002 (4)	0.565 (2)	0.199 (3)	0.021 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0251 (3)	0.0148 (2)	0.0172 (2)	−0.00847 (18)	−0.00306 (19)	0.00297 (16)
O1	0.0259 (7)	0.0123 (6)	0.0214 (7)	−0.0081 (5)	−0.0063 (6)	0.0033 (5)
N1	0.0190 (8)	0.0107 (7)	0.0189 (8)	−0.0055 (6)	−0.0072 (6)	0.0025 (6)
N2	0.0210 (8)	0.0102 (7)	0.0194 (8)	−0.0041 (6)	−0.0039 (7)	−0.0003 (6)
N3	0.0250 (9)	0.0114 (7)	0.0216 (8)	−0.0023 (6)	−0.0061 (7)	−0.0017 (6)
C1	0.0199 (9)	0.0125 (8)	0.0192 (9)	−0.0020 (7)	−0.0080 (8)	−0.0016 (7)
C2	0.0196 (9)	0.0176 (9)	0.0161 (9)	−0.0041 (7)	−0.0036 (7)	0.0011 (7)
C3	0.0208 (9)	0.0138 (8)	0.0200 (9)	−0.0065 (7)	−0.0090 (8)	0.0047 (7)
C4	0.0155 (8)	0.0110 (8)	0.0171 (8)	−0.0034 (7)	−0.0075 (7)	0.0016 (6)
C5	0.0143 (8)	0.0137 (8)	0.0160 (8)	−0.0041 (7)	−0.0067 (7)	0.0016 (7)
C6	0.0163 (8)	0.0125 (8)	0.0199 (9)	−0.0041 (7)	−0.0091 (7)	0.0023 (7)

Geometric parameters (Å, º) top

S1—C5	1.696 (2)	N3—H4	0.88 (1)
O1—C6	1.246 (2)	C1—C2	1.365 (3)
N1—C1	1.348 (2)	C1—H1A	0.95 (1)
N1—C5	1.376 (2)	C2—C3	1.395 (3)
N1—H1	0.88 (1)	C2—H2A	0.94 (1)
N2—C6	1.327 (2)	C3—C4	1.380 (3)
N2—N3	1.416 (2)	C3—H3A	0.95 (1)
N2—H2	0.89 (1)	C4—C5	1.433 (2)
N3—H3	0.88 (1)	C4—C6	1.507 (2)

C1—N1—C5	125.85 (15)	C3—C2—H2A	121.7 (14)
C1—N1—H1	118.5 (17)	C4—C3—C2	122.34 (17)
C5—N1—H1	115.6 (17)	C4—C3—H3A	116.8 (14)
C6—N2—N3	121.63 (15)	C2—C3—H3A	120.9 (14)
C6—N2—H2	119.0 (17)	C3—C4—C5	119.45 (16)
N3—N2—H2	119.3 (17)	C3—C4—C6	115.35 (15)
N2—N3—H3	106.3 (17)	C5—C4—C6	125.20 (16)
N2—N3—H4	107.0 (17)	N1—C5—C4	114.58 (15)
H3—N3—H4	109 (2)	N1—C5—S1	116.57 (13)
N1—C1—C2	119.76 (16)	C4—C5—S1	128.82 (14)
N1—C1—H1A	116.8 (14)	O1—C6—N2	121.97 (16)
C2—C1—H1A	123.4 (14)	O1—C6—C4	119.33 (16)
C1—C2—C3	117.83 (17)	N2—C6—C4	118.66 (15)
C1—C2—H2A	120.5 (14)

C5—N1—C1—C2	−0.3 (3)	C3—C4—C5—S1	173.23 (15)
N1—C1—C2—C3	−2.1 (3)	C6—C4—C5—S1	−7.1 (3)
C1—C2—C3—C4	0.7 (3)	N3—N2—C6—O1	0.2 (3)
C2—C3—C4—C5	3.0 (3)	N3—N2—C6—C4	−177.57 (17)
C2—C3—C4—C6	−176.77 (17)	C3—C4—C6—O1	−2.5 (3)
C1—N1—C5—C4	3.8 (3)	C5—C4—C6—O1	177.77 (17)
C1—N1—C5—S1	−174.60 (15)	C3—C4—C6—N2	175.28 (17)
C3—C4—C5—N1	−4.9 (3)	C5—C4—C6—N2	−4.4 (3)
C6—C4—C5—N1	174.76 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (1)	1.95 (2)	2.751 (2)	152 (2)
N2—H2···S1	0.89 (1)	2.24 (2)	3.007 (2)	145 (2)
N3—H3···O1ⁱⁱ	0.88 (2)	2.36 (3)	3.214 (2)	166 (3)
N3—H4···S1ⁱⁱⁱ	0.88 (3)	2.85 (3)	3.4173 (18)	124 (2)
C2—H2A···N3^iv	0.94 (1)	2.69 (2)	3.323 (4)	125 (2)

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

Experimental details

Crystal data
Chemical formula	C₆H₇N₃OS
M_r	169.21
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	7.1952 (2), 7.4279 (2), 7.7492 (2)
α, β, γ (°)	88.205 (2), 64.201 (2), 72.072 (2)
V (Å³)	352.22 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.35 × 0.05 × 0.01

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.874, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	3311, 1619, 1391
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.08
No. of reflections	1619
No. of parameters	128
No. of restraints	7
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.19

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

S1—C5	1.696 (2)	C1—C2	1.365 (3)
O1—C6	1.246 (2)	C2—C3	1.395 (3)
N1—C1	1.348 (2)	C3—C4	1.380 (3)
N1—C5	1.376 (2)	C4—C5	1.433 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88 (1)	1.95 (2)	2.751 (2)	152 (2)
N2—H2···S1	0.89 (1)	2.24 (2)	3.007 (2)	145 (2)
N3—H3···O1ⁱⁱ	0.88 (2)	2.36 (3)	3.214 (2)	166 (3)
N3—H4···S1ⁱⁱⁱ	0.88 (3)	2.85 (3)	3.4173 (18)	124 (2)
C2—H2A···N3^iv	0.94 (1)	2.69 (2)	3.323 (4)	125 (2)

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

Acknowledgements

We thank the University of Malaya for supporting this study.

References

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