6-Methyl-pyridine-2(1H)-thione.

There are two unique mol-ecules in the asymmetric unit of the title pyridine-thione derivative, C(6)H(7)NS, each of which adopts the thione rather than the mercaptan form. The rings in both mol-ecules are essentially planar, with maximum deviations from the least-squares planes through all non-H atoms of 0.021 (2) and 0.017 (2) Å. In the crystal structure, the mol-ecules form centrosymmetric cyclic dimers through inter-molecular N-H⋯S hydrogen bonds. Additional C-H(meth-yl)⋯S inter-actions generate a three-dimensional network.

Related literature

For the synthesis of 2-mercaptopyridines, see: Thirtle (1946 ▶). For background to the applications of organic sulfur-containing compounds, see: Cui et al. (2009 ▶); Saadat et al. (2004 ▶); Qian et al. (2007 ▶). For metal complexes of 2-mercapto pyridine N-oxide and 6-methyl substituted derivatives, see: Hamaguchi et al. (2007 ▶); Chunchuryukin et al. (2006 ▶); Cotton et al. (1978 ▶); West et al. (1998 ▶); Fielding et al. (1997 ▶); Berardini et al. (1997 ▶); Tylicki et al. (1995 ▶); Hong et al. (1999 ▶); Cabeza et al. (2007 ▶).

Experimental

Crystal data

C6H7NS

M = 125.19

Monoclinic,

a = 7.4608 (15) Å

b = 14.902 (3) Å

c = 11.665 (2) Å

β = 94.85 (3)°

V = 1292.3 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.39 mm−1

T = 295 K

0.33 × 0.33 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.880, T max = 0.926

12472 measured reflections

2944 independent reflections

2088 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.148

S = 1.12

2944 reflections

146 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.26 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810014273/sj2766sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014273/sj2766Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H7NS	F(000) = 528
Mr = 125.19	Dx = 1.287 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12782 reflections
a = 7.4608 (15) Å	θ = 3.1–27.4°
b = 14.902 (3) Å	µ = 0.39 mm−1
c = 11.665 (2) Å	T = 295 K
β = 94.85 (3)°	Block, yellow
V = 1292.3 (4) Å3	0.33 × 0.33 × 0.20 mm
Z = 8

Rigaku R-AXIS RAPID diffractometer	2944 independent reflections
Radiation source: fine-focus sealed tube	2088 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 0 pixels mm-1	θmax = 27.4°, θmin = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −19→19
Tmin = 0.880, Tmax = 0.926	l = −15→15
12472 measured reflections

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) = 0.148	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0738P)2 + 0.3029P] where P = (Fo2 + 2Fc2)/3
2944 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
S1	0.52754 (9)	0.10281 (4)	0.87258 (5)	0.0561 (2)
S2	0.90012 (12)	0.13575 (4)	0.50014 (6)	0.0743 (3)
N1	0.5873 (2)	−0.07318 (12)	0.85963 (15)	0.0470 (4)
H1A	0.5725	−0.0723	0.9319	0.056*
N2	0.9262 (2)	0.02468 (12)	0.32400 (15)	0.0488 (4)
H2A	0.9555	−0.0139	0.3771	0.059*
C1	0.6385 (5)	−0.23318 (17)	0.8905 (2)	0.0746 (8)
H1B	0.6160	−0.2149	0.9669	0.112*
H1C	0.7568	−0.2587	0.8916	0.112*
H1D	0.5509	−0.2772	0.8633	0.112*
C2	0.6257 (3)	−0.15375 (16)	0.8125 (2)	0.0541 (6)
C3	0.6503 (4)	−0.15630 (18)	0.6979 (2)	0.0626 (6)
H3A	0.6773	−0.2102	0.6631	0.075*
C4	0.6350 (4)	−0.0782 (2)	0.6339 (2)	0.0658 (7)
H4A	0.6513	−0.0800	0.5557	0.079*
C5	0.5961 (3)	0.00181 (18)	0.68372 (19)	0.0593 (6)
H5A	0.5868	0.0536	0.6392	0.071*
C6	0.5702 (3)	0.00646 (15)	0.80167 (18)	0.0469 (5)
C7	0.9694 (4)	−0.10058 (16)	0.1955 (2)	0.0609 (6)
H7A	0.9963	−0.1291	0.2687	0.091*
H7B	1.0723	−0.1042	0.1516	0.091*
H7C	0.8693	−0.1303	0.1546	0.091*
C8	0.9229 (3)	−0.00394 (16)	0.21353 (19)	0.0499 (5)
C9	0.8776 (3)	0.05620 (18)	0.1275 (2)	0.0590 (6)
H9A	0.8744	0.0386	0.0508	0.071*
C10	0.8365 (4)	0.14393 (18)	0.1558 (2)	0.0634 (7)
H10A	0.8072	0.1853	0.0975	0.076*
C11	0.8384 (3)	0.17037 (16)	0.2678 (2)	0.0581 (6)
H11A	0.8074	0.2290	0.2849	0.070*
C12	0.8870 (3)	0.10976 (15)	0.3583 (2)	0.0517 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0712 (4)	0.0439 (3)	0.0542 (4)	0.0043 (3)	0.0104 (3)	0.0009 (2)
S2	0.1163 (7)	0.0487 (4)	0.0574 (4)	0.0151 (4)	0.0044 (4)	−0.0032 (3)
N1	0.0524 (11)	0.0453 (9)	0.0438 (9)	0.0011 (8)	0.0076 (7)	−0.0034 (8)
N2	0.0570 (11)	0.0408 (9)	0.0485 (10)	0.0023 (8)	0.0037 (8)	0.0057 (8)
C1	0.108 (2)	0.0494 (14)	0.0673 (16)	0.0165 (14)	0.0117 (15)	−0.0044 (12)
C2	0.0553 (14)	0.0508 (13)	0.0567 (13)	0.0033 (10)	0.0078 (10)	−0.0093 (10)
C3	0.0703 (17)	0.0623 (15)	0.0561 (13)	0.0028 (12)	0.0102 (11)	−0.0160 (12)
C4	0.0716 (17)	0.0807 (18)	0.0463 (12)	−0.0021 (14)	0.0114 (11)	−0.0101 (12)
C5	0.0671 (16)	0.0642 (15)	0.0468 (12)	−0.0044 (12)	0.0059 (10)	0.0038 (11)
C6	0.0424 (12)	0.0508 (12)	0.0475 (11)	−0.0029 (9)	0.0044 (8)	−0.0009 (9)
C7	0.0648 (16)	0.0570 (14)	0.0614 (14)	0.0012 (12)	0.0087 (11)	−0.0063 (11)
C8	0.0442 (12)	0.0530 (12)	0.0531 (12)	−0.0045 (9)	0.0073 (9)	−0.0001 (10)
C9	0.0590 (15)	0.0682 (16)	0.0502 (12)	−0.0028 (12)	0.0057 (10)	0.0077 (11)
C10	0.0646 (16)	0.0623 (15)	0.0619 (15)	−0.0042 (12)	−0.0030 (11)	0.0229 (12)
C11	0.0595 (15)	0.0423 (11)	0.0716 (15)	−0.0034 (10)	−0.0006 (11)	0.0120 (11)
C12	0.0534 (13)	0.0418 (11)	0.0601 (13)	−0.0022 (10)	0.0053 (10)	0.0047 (10)

S1—C6	1.700 (2)	C4—C5	1.368 (4)
S2—C12	1.694 (3)	C4—H4A	0.9300
N1—C2	1.361 (3)	C5—C6	1.407 (3)
N1—C6	1.367 (3)	C5—H5A	0.9300
N1—H1A	0.8600	C7—C8	1.500 (3)
N2—C8	1.356 (3)	C7—H7A	0.9600
N2—C12	1.369 (3)	C7—H7B	0.9600
N2—H2A	0.8600	C7—H7C	0.9600
C1—C2	1.491 (4)	C8—C9	1.367 (3)
C1—H1B	0.9600	C9—C10	1.389 (4)
C1—H1C	0.9600	C9—H9A	0.9300
C1—H1D	0.9600	C10—C11	1.363 (4)
C2—C3	1.366 (3)	C10—H10A	0.9300
C3—C4	1.383 (4)	C11—C12	1.413 (3)
C3—H3A	0.9300	C11—H11A	0.9300
C2—N1—C6	125.47 (18)	N1—C6—C5	115.2 (2)
C2—N1—H1A	117.3	N1—C6—S1	120.41 (15)
C6—N1—H1A	117.3	C5—C6—S1	124.34 (19)
C8—N2—C12	125.61 (19)	C8—C7—H7A	109.5
C8—N2—H2A	117.2	C8—C7—H7B	109.5
C12—N2—H2A	117.2	H7A—C7—H7B	109.5
C2—C1—H1B	109.5	C8—C7—H7C	109.5
C2—C1—H1C	109.5	H7A—C7—H7C	109.5
H1B—C1—H1C	109.5	H7B—C7—H7C	109.5
C2—C1—H1D	109.5	N2—C8—C9	118.4 (2)
H1B—C1—H1D	109.5	N2—C8—C7	116.7 (2)
H1C—C1—H1D	109.5	C9—C8—C7	124.9 (2)
N1—C2—C3	118.1 (2)	C8—C9—C10	119.2 (2)
N1—C2—C1	117.3 (2)	C8—C9—H9A	120.4
C3—C2—C1	124.6 (2)	C10—C9—H9A	120.4
C2—C3—C4	119.6 (2)	C11—C10—C9	121.0 (2)
C2—C3—H3A	120.2	C11—C10—H10A	119.5
C4—C3—H3A	120.2	C9—C10—H10A	119.5
C5—C4—C3	121.0 (2)	C10—C11—C12	120.8 (2)
C5—C4—H4A	119.5	C10—C11—H11A	119.6
C3—C4—H4A	119.5	C12—C11—H11A	119.6
C4—C5—C6	120.7 (2)	N2—C12—C11	114.9 (2)
C4—C5—H5A	119.7	N2—C12—S2	120.08 (17)
C6—C5—H5A	119.7	C11—C12—S2	125.00 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1i	0.86	2.50	3.3376 (19)	165
N2—H2A···S2ii	0.86	2.50	3.340 (2)	166
C1—H1B···S1i	0.96	2.79	3.678 (3)	154
C7—H7A···S2ii	0.96	2.74	3.639 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1i	0.86	2.50	3.3376 (19)	165
N2—H2A⋯S2ii	0.86	2.50	3.340 (2)	166
C1—H1B⋯S1i	0.96	2.79	3.678 (3)	154
C7—H7A⋯S2ii	0.96	2.74	3.639 (3)	156

Symmetry codes: (i) ; (ii) .