2-(2-Pyridylsulfan­yl)-N-p-tolyl­acetamide

The title compound, C₁₄H₁₄N₂OS, contains a pyridine and a benzene ring almost perpendicular to each other, subtending a dihedral angle of 88.2 (2)°. Inter­molecular hydrogen bonds between adjacent NH groups and carbonyl O atoms link mol­ecules together into chains parallel to [100], the shortest axis.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.004 Å
• R factor = 0.045
• wR factor = 0.130
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

S1. Comment

2-Mercaptopyridine is an important class of medical intermediate. Recently, many biological copmpounds (Koike et al.,1999) have been prepared having 2-mercaptopyridine as raw material. We have synthesized the title compound, C₁₄H₁₄N₂ O S, (I), from 2-mercaptopyridine with p-tolylcarbamic chloride, and we are reporing herein its crystal structure.

The molecular structure of (I) contains a pyridinyl and a benzene rings, almost perpendicular to each other, subtending a dihedral angle of 91.8 (2)%. The methyl carbon is coplanar to the benzene ring (r.m.s deviation: 0.0075 (3) Å). Due to the π–π conjugation bwtween the S atom and pyridinyl ring, the S1—C5 bond distance [1.772 (3) Å] is slightly shorter than the S1—C6 one [1.801 (2) Å]. Intermolecular hydrogen bonds between adjacent N—H groups and carbonyl O atoms link molecules together into chains parallel to [100], the shortest axis direction.

Related literature

For related literature, see: Koike et al. (1999).

S2. Experimental

The title compound was synthesized by the reaction of pyridine-2-thiol with p-tolylcarbamic chloride in refluxing ethanol. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform/acetone.

S3. Refinement

The H atom attached to N atom was located in a difference density map and the atomic coordinates allowed to refine freely. Other H atoms attached to carbon were positioned geometrically and refined as riding (C—H = 0.93–0.97%A). For the CH and CH₂ groups, U_iso(H) values were set equal to 1.2U_eq(C) and for the methyl groups they were set equal to 1.5U_eq(C).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level.

2-(2-Pyridylsulfanyl)-N-p-tolylacetamide

Crystal data

C14H14N2OS	Dx = 1.281 Mg m^−3
Mr = 258.33	Melting point: 403 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2537 reflections
a = 9.348 (2) Å	θ = 2.8–22.6°
b = 12.361 (3) Å	µ = 0.23 mm^−1
c = 23.184 (6) Å	T = 294 K
V = 2678.9 (11) Å^3	Plate, colourless
Z = 8	0.20 × 0.18 × 0.14 mm
F(000) = 1088

Data collection

Bruker SMART CCD area-detector diffractometer	2366 independent reflections
Radiation source: fine-focus sealed tube	1535 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.95, Tmax = 0.97	k = −14→14
12855 measured reflections	l = −27→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0661P)^2 + 0.6597P] where P = (Fo^2 + 2Fc^2)/3
2366 reflections	(Δ/σ)max = 0.001
168 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.15494 (7)	0.53279 (5)	0.32262 (3)	0.0510 (3)
O1	0.09884 (17)	0.36599 (16)	0.22875 (8)	0.0607 (6)
N1	0.1009 (3)	0.4497 (2)	0.42221 (10)	0.0619 (7)
N2	0.3332 (2)	0.33742 (17)	0.20810 (9)	0.0453 (5)
C1	0.1150 (4)	0.3798 (3)	0.46624 (14)	0.0786 (10)
H1	0.0559	0.3888	0.4981	0.094*
C2	0.2108 (4)	0.2963 (3)	0.46715 (14)	0.0789 (10)
H2	0.2156	0.2494	0.4984	0.095*
C3	0.3000 (4)	0.2838 (3)	0.42029 (13)	0.0691 (9)
H3	0.3672	0.2283	0.4198	0.083*
C4	0.2894 (3)	0.3536 (2)	0.37423 (12)	0.0538 (7)
H4	0.3489	0.3464	0.3423	0.065*
C5	0.1877 (3)	0.4347 (2)	0.37679 (11)	0.0439 (6)
C6	0.2722 (3)	0.4933 (2)	0.26470 (11)	0.0479 (7)
H6A	0.2788	0.5525	0.2374	0.057*
H6B	0.3671	0.4811	0.2803	0.057*
C7	0.2246 (2)	0.39226 (19)	0.23277 (10)	0.0407 (6)
C8	0.3274 (2)	0.24390 (19)	0.17239 (10)	0.0408 (6)
C9	0.4569 (3)	0.1969 (2)	0.15700 (12)	0.0554 (7)
H9	0.5421	0.2262	0.1705	0.067*
C10	0.4597 (3)	0.1067 (2)	0.12164 (13)	0.0625 (8)
H10	0.5475	0.0775	0.1110	0.075*
C11	0.3352 (3)	0.0589 (2)	0.10166 (12)	0.0517 (7)
C12	0.2078 (3)	0.1059 (2)	0.11785 (11)	0.0523 (7)
H12	0.1227	0.0754	0.1049	0.063*
C13	0.2016 (3)	0.1970 (2)	0.15273 (11)	0.0480 (6)
H13	0.1137	0.2265	0.1629	0.058*
C14	0.3383 (3)	−0.0406 (2)	0.06350 (15)	0.0742 (9)
H14A	0.2519	−0.0813	0.0689	0.111*
H14B	0.4191	−0.0846	0.0735	0.111*
H14C	0.3458	−0.0188	0.0239	0.111*
H2A	0.420 (3)	0.3602 (19)	0.2169 (10)	0.050 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0496 (4)	0.0530 (4)	0.0504 (4)	0.0121 (3)	0.0049 (3)	0.0018 (3)
O1	0.0300 (10)	0.0814 (14)	0.0706 (13)	−0.0041 (9)	0.0053 (9)	−0.0170 (10)
N1	0.0601 (14)	0.0777 (17)	0.0479 (14)	0.0104 (13)	0.0075 (12)	−0.0002 (12)
N2	0.0268 (11)	0.0523 (13)	0.0567 (14)	−0.0019 (10)	0.0002 (10)	−0.0017 (11)
C1	0.092 (2)	0.095 (3)	0.0492 (19)	0.004 (2)	0.0129 (17)	0.0102 (18)
C2	0.111 (3)	0.074 (2)	0.052 (2)	0.000 (2)	−0.005 (2)	0.0160 (17)
C3	0.086 (2)	0.0578 (18)	0.064 (2)	0.0111 (17)	−0.0137 (18)	−0.0023 (16)
C4	0.0583 (16)	0.0549 (16)	0.0481 (16)	0.0061 (14)	−0.0032 (13)	−0.0012 (13)
C5	0.0413 (14)	0.0496 (15)	0.0406 (14)	−0.0019 (12)	−0.0018 (11)	−0.0055 (12)
C6	0.0440 (15)	0.0504 (15)	0.0494 (16)	−0.0016 (12)	0.0052 (12)	0.0055 (12)
C7	0.0331 (13)	0.0514 (15)	0.0375 (14)	−0.0019 (11)	0.0016 (11)	0.0098 (11)
C8	0.0323 (13)	0.0427 (13)	0.0474 (15)	−0.0009 (11)	0.0024 (11)	0.0071 (12)
C9	0.0356 (14)	0.0513 (16)	0.079 (2)	−0.0003 (12)	−0.0004 (13)	−0.0028 (15)
C10	0.0449 (16)	0.0543 (17)	0.088 (2)	0.0103 (14)	0.0033 (15)	−0.0050 (16)
C11	0.0544 (17)	0.0455 (15)	0.0552 (17)	0.0018 (13)	−0.0038 (13)	0.0054 (13)
C12	0.0449 (15)	0.0626 (18)	0.0494 (16)	−0.0110 (13)	−0.0046 (12)	0.0009 (14)
C13	0.0339 (13)	0.0624 (17)	0.0477 (15)	0.0010 (12)	0.0011 (11)	0.0013 (14)
C14	0.081 (2)	0.0598 (19)	0.082 (2)	0.0022 (17)	−0.0014 (17)	−0.0118 (17)

Geometric parameters (Å, º)

S1—C5	1.772 (3)	C6—H6A	0.9700
S1—C6	1.801 (2)	C6—H6B	0.9700
O1—C7	1.224 (3)	C8—C13	1.388 (3)
N1—C5	1.342 (3)	C8—C9	1.389 (3)
N1—C1	1.344 (4)	C9—C10	1.384 (4)
N2—C7	1.347 (3)	C9—H9	0.9300
N2—C8	1.423 (3)	C10—C11	1.385 (4)
N2—H2A	0.89 (3)	C10—H10	0.9300
C1—C2	1.366 (5)	C11—C12	1.377 (4)
C1—H1	0.9300	C11—C14	1.515 (4)
C2—C3	1.378 (4)	C12—C13	1.388 (4)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.376 (4)	C13—H13	0.9300
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.384 (3)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C6—C7	1.518 (3)
C5—S1—C6	103.77 (12)	O1—C7—C6	122.4 (2)
C5—N1—C1	116.6 (3)	N2—C7—C6	113.6 (2)
C7—N2—C8	128.8 (2)	C13—C8—C9	118.6 (2)
C7—N2—H2A	115.8 (16)	C13—C8—N2	124.2 (2)
C8—N2—H2A	115.2 (16)	C9—C8—N2	117.2 (2)
N1—C1—C2	124.2 (3)	C10—C9—C8	120.4 (2)
N1—C1—H1	117.9	C10—C9—H9	119.8
C2—C1—H1	117.9	C8—C9—H9	119.8
C1—C2—C3	118.0 (3)	C9—C10—C11	121.7 (2)
C1—C2—H2	121.0	C9—C10—H10	119.1
C3—C2—H2	121.0	C11—C10—H10	119.1
C4—C3—C2	119.8 (3)	C12—C11—C10	117.1 (2)
C4—C3—H3	120.1	C12—C11—C14	121.2 (2)
C2—C3—H3	120.1	C10—C11—C14	121.7 (2)
C3—C4—C5	118.1 (3)	C11—C12—C13	122.5 (2)
C3—C4—H4	121.0	C11—C12—H12	118.8
C5—C4—H4	121.0	C13—C12—H12	118.8
N1—C5—C4	123.3 (3)	C12—C13—C8	119.7 (2)
N1—C5—S1	110.94 (19)	C12—C13—H13	120.2
C4—C5—S1	125.7 (2)	C8—C13—H13	120.2
C7—C6—S1	114.11 (17)	C11—C14—H14A	109.5
C7—C6—H6A	108.7	C11—C14—H14B	109.5
S1—C6—H6A	108.7	H14A—C14—H14B	109.5
C7—C6—H6B	108.7	C11—C14—H14C	109.5
S1—C6—H6B	108.7	H14A—C14—H14C	109.5
H6A—C6—H6B	107.6	H14B—C14—H14C	109.5
O1—C7—N2	123.9 (2)
C5—N1—C1—C2	0.0 (5)	S1—C6—C7—N2	−153.34 (18)
N1—C1—C2—C3	0.9 (6)	C7—N2—C8—C13	5.5 (4)
C1—C2—C3—C4	−0.8 (5)	C7—N2—C8—C9	−173.9 (2)
C2—C3—C4—C5	−0.1 (4)	C13—C8—C9—C10	1.6 (4)
C1—N1—C5—C4	−1.0 (4)	N2—C8—C9—C10	−179.0 (2)
C1—N1—C5—S1	179.7 (2)	C8—C9—C10—C11	−1.6 (4)
C3—C4—C5—N1	1.1 (4)	C9—C10—C11—C12	0.9 (4)
C3—C4—C5—S1	−179.8 (2)	C9—C10—C11—C14	−179.3 (3)
C6—S1—C5—N1	−176.38 (19)	C10—C11—C12—C13	−0.2 (4)
C6—S1—C5—C4	4.4 (3)	C14—C11—C12—C13	−180.0 (3)
C5—S1—C6—C7	72.68 (19)	C11—C12—C13—C8	0.1 (4)
C8—N2—C7—O1	2.0 (4)	C9—C8—C13—C12	−0.8 (4)
C8—N2—C7—C6	−175.9 (2)	N2—C8—C13—C12	179.8 (2)
S1—C6—C7—O1	28.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^i	0.89 (3)	2.09 (3)	2.904 (3)	152 (2)

Symmetry code: (i) x+1/2, y, −z+1/2.