N-Butyl­pyridine-4-thio­carboxamide

Kavitha, T.; Revathi, C.; Hemalatha, M.; Dayalan, A.; Ponnuswamy, M.N.

doi:10.1107/S1600536807062125

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o114

https://doi.org/10.1107/S1600536807062125

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N-Butylpyridine-4-thiocarboxamide

T. Kavitha,^a C. Revathi,^b M. Hemalatha,^b A. Dayalan ^b and M. N. Ponnuswamy ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bDepartment of Chemistry, Loyola College (Autonomous), Chennai 600 034, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

(Received 17 November 2007; accepted 22 November 2007; online 6 December 2007)

In the title molecule, C₁₀H₁₄N₂S, the n-butyl chain assumes a trans zigzag conformation. The dihedral angle between the pyridine ring and the thioamide plane is 23.38 (8)°. The molecules in the crystal structure are linked by an intermolecular N—H⋯N hydrogen bond.

Related literature

For related literature, see: Allen et al. (1987 ); Klimsova et al. (1999 ); Ramachandran (2005 ); Vannelli et al. (2002 ); Desiraju (1989 ); Dodge et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₄N₂S
M_r = 194.29
Monoclinic, P 2₁ /c
a = 8.0895 (3) Å
b = 13.5947 (4) Å
c = 10.4936 (3) Å
β = 111.895 (2)°
V = 1070.78 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 (2) K
0.26 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.935, T_max = 0.949
11437 measured reflections
2182 independent reflections
1744 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.120
S = 1.06
2182 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8⋯N1ⁱ	0.859 (19)	2.182 (19)	3.033 (2)	171 (2)
Symmetry code: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807062125/is2253sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062125/is2253Isup2.hkl

checkCIF report

Comment top

Drugs containing carbothioamide (–CSNH₂) functional groups are clinically effective for the treatment of M. tuberculosis, M. leprae and M. avium complex infections (Dodge et al., 2006; Klimsova et al., 1999). In general, the carbothioamide drugs are considered as second line drugs. The carbothioamide groups have significant effects in biological systems. Their use, especially as pyridine carbothioamides in the field of multi drug resistant systems, has increased a lot (Vannelli et al., 2002). Depending on the position of the carbothioamide group at the pyridine ring and also depending on the nature of N-alkyl substitution at the thioamide, the pyridine carbothioamides have been found to play a vital role in their biological activities and drug action. We report here the crystal structure of a typical pyridinecarbothioamide, viz., 4-(N-1-butylcarbothioamido) pyridine.

The pyridine ring is planar. The n-butyl amide group assumes an extended conformation [C4—C7—N8—C9 = -178.06 (15)°, C7—N8—C9—C10 = -168.50 (16)°, N8—C9—C10—C11 = -178.86 (16)°, C9—C10—C11—C12 = -171.50 (18)°]. The C=S bond length [1.6608 (16) Å] is comparable with the literature values (Allen et al., 1987). The pyridine and thioamide planes orient at an angle of 23.38 (8)° to each other.

The sum of the bond angles around N8 is 359.94 (4)° thus conforming sp² hybridized state of N atom. The molecules in the unit cell are stabilized by N—H···N (Desiraju, 1989) type of intermolecular interactions in addition to van der Waal's forces.

Related literature top

For related literature, see: Allen et al. (1987); Klimsova et al. (1999); Ramachandran (2005); Vannelli et al. (2002); Desiraju (1989); Dodge et al. (2006).

Experimental top

About 5 g of 4- pyridinecarbonitrile was dissolved in 15 ml of ethanol. To this about 10 ml of 1-aminobutane was added and purified and H₂S gas was passed for 3 h. The yellow solid separate was filtered, washed with ethanol and dried in vacuum desicator (yield 80%) (Ramachandran, 2005).

Structure description top

For related literature, see: Allen et al. (1987); Klimsova et al. (1999); Ramachandran (2005); Vannelli et al. (2002); Desiraju (1989); Dodge et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 20% probability displacement ellipsoids.
	Fig. 2. A packing diagram, viewed approximately along the a axis. Dashed lines indicated N—H···N hydrogen bonds.

N-Butylpyridine-4-thiocarboxamide top

Crystal data top

C₁₀H₁₄N₂S	F(000) = 416
M_r = 194.29	D_x = 1.205 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2182 reflections
a = 8.0895 (3) Å	θ = 2.6–26.3°
b = 13.5947 (4) Å	µ = 0.26 mm⁻¹
c = 10.4936 (3) Å	T = 293 K
β = 111.895 (2)°	Block, brown
V = 1070.78 (6) Å³	0.26 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII kappa diffractometer	2182 independent reflections
Radiation source: fine-focus sealed tube	1744 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scan	θ_max = 26.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→10
T_min = 0.935, T_max = 0.949	k = −15→16
11437 measured reflections	l = −13→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0579P)² + 0.2939P] where P = (F_o² + 2F_c²)/3
2182 reflections	(Δ/σ)_max < 0.001
122 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₀H₁₄N₂S	V = 1070.78 (6) Å³
M_r = 194.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0895 (3) Å	µ = 0.26 mm⁻¹
b = 13.5947 (4) Å	T = 293 K
c = 10.4936 (3) Å	0.26 × 0.20 × 0.20 mm
β = 111.895 (2)°

Data collection top

Bruker APEXII kappa diffractometer	2182 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1744 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.949	R_int = 0.027
11437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.37 e Å⁻³
2182 reflections	Δρ_min = −0.38 e Å⁻³
122 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
H8	0.753 (2)	−0.0813 (14)	0.501 (2)	0.055 (5)*
C2	0.6652 (3)	−0.27758 (12)	0.74847 (18)	0.0533 (4)
H2	0.5953	−0.3302	0.7016	0.064*
C3	0.6682 (2)	−0.19391 (12)	0.67438 (17)	0.0461 (4)
H3	0.6041	−0.1917	0.5802	0.055*
C4	0.7670 (2)	−0.11385 (11)	0.74138 (15)	0.0406 (4)
C5	0.8613 (3)	−0.12389 (14)	0.88113 (18)	0.0561 (5)
H5	0.9304	−0.0721	0.9312	0.067*
C6	0.8525 (3)	−0.21036 (14)	0.94534 (19)	0.0606 (5)
H6	0.9185	−0.2154	1.0390	0.073*
C7	0.7739 (2)	−0.01937 (11)	0.67065 (17)	0.0446 (4)
C9	0.7746 (3)	0.06103 (12)	0.46367 (18)	0.0519 (4)
H9A	0.8954	0.0864	0.5005	0.062*
H9B	0.6965	0.1116	0.4748	0.062*
C10	0.7241 (3)	0.04039 (12)	0.31368 (18)	0.0514 (4)
H10A	0.6022	0.0168	0.2754	0.062*
H10B	0.8008	−0.0107	0.3017	0.062*
C11	0.7414 (3)	0.13253 (14)	0.23755 (19)	0.0590 (5)
H11A	0.6797	0.1862	0.2618	0.071*
H11B	0.8663	0.1503	0.2673	0.071*
C12	0.6671 (4)	0.1204 (2)	0.0840 (2)	0.0914 (8)
H12A	0.6822	0.1806	0.0417	0.137*
H12B	0.5427	0.1046	0.0533	0.137*
H12C	0.7292	0.0683	0.0590	0.137*
N1	0.7559 (2)	−0.28736 (10)	0.88235 (15)	0.0544 (4)
N8	0.7638 (2)	−0.02581 (10)	0.54257 (14)	0.0450 (3)
S1	0.79203 (10)	0.08676 (3)	0.75316 (5)	0.0775 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0742 (12)	0.0386 (9)	0.0445 (10)	−0.0106 (8)	0.0193 (9)	−0.0039 (7)
C3	0.0591 (10)	0.0420 (8)	0.0351 (8)	−0.0019 (7)	0.0152 (7)	−0.0010 (6)
C4	0.0507 (9)	0.0356 (8)	0.0393 (9)	−0.0011 (7)	0.0212 (7)	−0.0016 (6)
C5	0.0744 (13)	0.0482 (10)	0.0396 (9)	−0.0177 (9)	0.0143 (9)	−0.0047 (7)
C6	0.0829 (14)	0.0548 (11)	0.0359 (9)	−0.0104 (9)	0.0126 (9)	0.0045 (8)
C7	0.0563 (10)	0.0371 (8)	0.0420 (9)	−0.0009 (7)	0.0201 (8)	−0.0013 (6)
C9	0.0716 (12)	0.0354 (8)	0.0507 (10)	0.0021 (8)	0.0253 (9)	0.0062 (7)
C10	0.0649 (11)	0.0424 (9)	0.0485 (10)	0.0035 (8)	0.0228 (8)	0.0079 (7)
C11	0.0721 (13)	0.0510 (11)	0.0593 (12)	0.0064 (9)	0.0307 (10)	0.0166 (8)
C12	0.1018 (19)	0.107 (2)	0.0593 (14)	−0.0033 (15)	0.0234 (13)	0.0293 (13)
N1	0.0776 (11)	0.0426 (8)	0.0432 (8)	−0.0073 (7)	0.0227 (8)	0.0025 (6)
N8	0.0662 (9)	0.0316 (7)	0.0405 (7)	0.0033 (6)	0.0235 (7)	0.0021 (6)
S1	0.1429 (6)	0.0376 (3)	0.0602 (4)	−0.0080 (3)	0.0474 (4)	−0.0114 (2)

Geometric parameters (Å, º) top

C2—N1	1.327 (2)	C9—C10	1.498 (2)
C2—C3	1.383 (2)	C9—H9A	0.9700
C2—H2	0.9300	C9—H9B	0.9700
C3—C4	1.378 (2)	C10—C11	1.520 (2)
C3—H3	0.9300	C10—H10A	0.9700
C4—C5	1.384 (2)	C10—H10B	0.9700
C4—C7	1.495 (2)	C11—C12	1.504 (3)
C5—C6	1.370 (3)	C11—H11A	0.9700
C5—H5	0.9300	C11—H11B	0.9700
C6—N1	1.326 (2)	C12—H12A	0.9600
C6—H6	0.9300	C12—H12B	0.9600
C7—N8	1.318 (2)	C12—H12C	0.9600
C7—S1	1.6608 (16)	N8—H8	0.86 (2)
C9—N8	1.463 (2)

N1—C2—C3	123.97 (16)	H9A—C9—H9B	107.8
N1—C2—H2	118.0	C9—C10—C11	110.82 (15)
C3—C2—H2	118.0	C9—C10—H10A	109.5
C4—C3—C2	119.42 (15)	C11—C10—H10A	109.5
C4—C3—H3	120.3	C9—C10—H10B	109.5
C2—C3—H3	120.3	C11—C10—H10B	109.5
C3—C4—C5	116.63 (15)	H10A—C10—H10B	108.1
C3—C4—C7	123.18 (14)	C12—C11—C10	113.24 (19)
C5—C4—C7	120.18 (15)	C12—C11—H11A	108.9
C6—C5—C4	119.76 (16)	C10—C11—H11A	108.9
C6—C5—H5	120.1	C12—C11—H11B	108.9
C4—C5—H5	120.1	C10—C11—H11B	108.9
N1—C6—C5	124.15 (17)	H11A—C11—H11B	107.7
N1—C6—H6	117.9	C11—C12—H12A	109.5
C5—C6—H6	117.9	C11—C12—H12B	109.5
N8—C7—C4	116.70 (13)	H12A—C12—H12B	109.5
N8—C7—S1	123.30 (12)	C11—C12—H12C	109.5
C4—C7—S1	120.00 (12)	H12A—C12—H12C	109.5
N8—C9—C10	113.15 (14)	H12B—C12—H12C	109.5
N8—C9—H9A	108.9	C6—N1—C2	116.05 (15)
C10—C9—H9A	108.9	C7—N8—C9	121.94 (14)
N8—C9—H9B	108.9	C7—N8—H8	122.2 (13)
C10—C9—H9B	108.9	C9—N8—H8	115.8 (13)

N1—C2—C3—C4	−1.5 (3)	C5—C4—C7—S1	−33.5 (2)
C2—C3—C4—C5	1.2 (2)	N8—C9—C10—C11	−178.86 (16)
C2—C3—C4—C7	−178.13 (16)	C9—C10—C11—C12	−171.50 (18)
C3—C4—C5—C6	−0.1 (3)	C5—C6—N1—C2	0.6 (3)
C7—C4—C5—C6	179.24 (18)	C3—C2—N1—C6	0.6 (3)
C4—C5—C6—N1	−0.9 (3)	C4—C7—N8—C9	−178.06 (15)
C3—C4—C7—N8	−33.7 (2)	S1—C7—N8—C9	2.4 (3)
C5—C4—C7—N8	146.99 (17)	C10—C9—N8—C7	−168.50 (16)
C3—C4—C7—S1	145.88 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···N1ⁱ	0.859 (19)	2.182 (19)	3.033 (2)	171 (2)

Symmetry code: (i) x, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₂S
M_r	194.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.0895 (3), 13.5947 (4), 10.4936 (3)
β (°)	111.895 (2)
V (Å³)	1070.78 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.26 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII kappa
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.935, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	11437, 2182, 1744
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.120, 1.06
No. of reflections	2182
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.38

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···N1ⁱ	0.859 (19)	2.182 (19)	3.033 (2)	171 (2)

Symmetry code: (i) x, −y−1/2, z−1/2.

Acknowledgements

AD, MH and CR are grateful to Rev. Fr A. Albert Muthumali S. J., Principal, Loyola College (Autonomous), Chennai, India, for providing the necessary facilities.

References

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