N-[N-(2-Pyridylmeth­yl)thio­carbamo­yl]­benzamide

In the title compound, C₁₄H₁₃N₃OS, the phenyl ring forms a dihedral angle of 33.22 (12)° with the remaining part of the mol­ecule, which is approximately planar. The trans–cis geometry of the thio­urea fragment is stabilized by an intra­molecular N—H...O hydrogen bond involving the O atom of the benzoyl group and the H atom of the trans-thio­amide unit. Inter­molecular N—H...S hydrogen bonds between the cis-thio­amide fragments connect mol­ecules into centrosymmetric dimers.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.057
• wR factor = 0.171
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound (I) is an analog of N-(benzylaminothiocarbonyl)benzamide (II) (Sabino et al., 2006), which like the title compound has the tiourea fragment in trans-cis configuration (Fig.1). The bond lengths and angles are in normal ranges. In contrast to (II), the molecule of (I) is more planar with only the phenyl ring of the benzoyl group twisted with respect to the plane defined by the remaining atoms of the molecule. This planar conformation is due to two intramolecular hydrogen bonds, one relatively strong (N2—H2···O1) and one weak (N2—H2···N3). The N1—H1···S1 hydrogen bonds between the cis-thioamide fragments of (I) connect molecules into centrosymmetric dimers (Fig.2).

Related literature

For the crystal structure of the benzene analogue, see: Sabino et al. (2006).

S2. Experimental

The mixture of benzoyl chloride (7.03 g, 0.05 mol), ammonium thiocyanate (3.8 g, 0.05 mol) and 2-picolylamine (5.4 g, 0.05 mol) in 30 ml dry acetone was refluxed with stirring for 4 h. The solution was filtered and left to evaporate at room temperature. The colourless solid obtained after a few days was washed with water and cold ethanol (yield 80%; m.p 424.4- 427.2 K). Crystals suitablefor X-ray investigation were obtained by recrystallization from chloroform.

S3. Refinement

All H atoms were positioned geometrically (C—H = 0.93–0.97 Å, N—H = 0.86 Å and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsods are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) viewed down the a axis. Hydrogen bonds are shown by dashed lines.

N-[N-(2-Pyridylmethyl)thiocarbamoyl]benzamide

Crystal data

C14H13N3OS	Z = 2
Mr = 271.33	F(000) = 284
Triclinic, P1	Dx = 1.354 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.533 (3) Å	Cell parameters from 3526 reflections
b = 8.813 (4) Å	θ = 2.3–25.0°
c = 9.028 (4) Å	µ = 0.24 mm^−1
α = 98.904 (6)°	T = 298 K
β = 96.978 (8)°	Block, colourless
γ = 90.197 (7)°	0.50 × 0.34 × 0.20 mm
V = 665.6 (4) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2336 independent reflections
Radiation source: fine-focus sealed tube	2172 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 83.66 pixels mm^-1	θmax = 25.0°, θmin = 2.3°
ω scan	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −10→10
Tmin = 0.890, Tmax = 0.953	l = −10→10
6204 measured reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.37	w = 1/[σ^2(Fo^2) + (0.0661P)^2 + 0.2921P] where P = (Fo^2 + 2Fc^2)/3
2336 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.18 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	1.04589 (10)	0.52568 (10)	0.23600 (9)	0.0589 (3)
O1	0.6410 (3)	0.8417 (3)	0.1405 (2)	0.0636 (7)
N1	0.8063 (3)	0.6462 (3)	0.0833 (3)	0.0485 (6)
H1	0.8340	0.5833	0.0088	0.058*
N2	0.8620 (3)	0.7491 (3)	0.3356 (3)	0.0471 (6)
H2	0.7860	0.8104	0.3189	0.056*
N3	0.7395 (4)	0.9462 (4)	0.5396 (3)	0.0676 (9)
C1	0.5694 (4)	0.5341 (4)	−0.1708 (3)	0.0497 (7)
H1A	0.6330	0.4600	−0.1329	0.060*
C2	0.4673 (4)	0.4948 (4)	−0.3016 (4)	0.0597 (9)
H2A	0.4621	0.3941	−0.3518	0.072*
C3	0.3730 (4)	0.6038 (5)	−0.3584 (4)	0.0656 (10)
H3	0.3039	0.5767	−0.4466	0.079*
C4	0.3810 (4)	0.7525 (5)	−0.2849 (4)	0.0654 (10)
H4	0.3181	0.8265	−0.3241	0.078*
C5	0.4815 (4)	0.7924 (4)	−0.1536 (4)	0.0552 (8)
H5	0.4851	0.8930	−0.1032	0.066*
C6	0.5777 (3)	0.6835 (3)	−0.0957 (3)	0.0439 (7)
C7	0.6763 (4)	0.7318 (3)	0.0517 (3)	0.0455 (7)
C8	0.8989 (3)	0.6492 (3)	0.2221 (3)	0.0441 (7)
C9	0.9426 (4)	0.7609 (4)	0.4868 (3)	0.0524 (8)
H9A	1.0525	0.7893	0.4872	0.063*
H9B	0.9387	0.6620	0.5208	0.063*
C10	0.8672 (4)	0.8796 (3)	0.5936 (3)	0.0468 (7)
C11	0.6733 (5)	1.0521 (5)	0.6354 (4)	0.0749 (11)
H11	0.5833	1.0999	0.5979	0.090*
C12	0.7290 (4)	1.0929 (4)	0.7814 (4)	0.0638 (9)
H12	0.6788	1.1662	0.8437	0.077*
C13	0.8605 (6)	1.0240 (6)	0.8352 (4)	0.0936 (16)
H13	0.9033	1.0503	0.9358	0.112*
C14	0.9302 (5)	0.9150 (5)	0.7405 (4)	0.0830 (13)
H14	1.0199	0.8658	0.7766	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0578 (5)	0.0722 (6)	0.0469 (5)	0.0331 (4)	0.0069 (4)	0.0094 (4)
O1	0.0709 (15)	0.0614 (14)	0.0520 (13)	0.0340 (12)	−0.0037 (11)	−0.0030 (11)
N1	0.0484 (14)	0.0553 (15)	0.0395 (13)	0.0201 (12)	0.0043 (11)	0.0010 (11)
N2	0.0449 (13)	0.0522 (14)	0.0421 (13)	0.0165 (11)	0.0020 (10)	0.0036 (11)
N3	0.0681 (19)	0.077 (2)	0.0521 (16)	0.0328 (16)	−0.0010 (14)	−0.0019 (14)
C1	0.0469 (17)	0.0496 (17)	0.0531 (17)	0.0073 (14)	0.0109 (14)	0.0060 (14)
C2	0.0520 (19)	0.063 (2)	0.060 (2)	−0.0034 (16)	0.0101 (16)	−0.0051 (16)
C3	0.0518 (19)	0.090 (3)	0.0504 (19)	0.0006 (18)	−0.0022 (15)	0.0017 (18)
C4	0.060 (2)	0.081 (2)	0.055 (2)	0.0182 (18)	−0.0033 (16)	0.0170 (18)
C5	0.0586 (19)	0.0554 (19)	0.0499 (17)	0.0167 (15)	0.0013 (14)	0.0075 (14)
C6	0.0423 (15)	0.0501 (17)	0.0410 (15)	0.0089 (13)	0.0091 (12)	0.0086 (13)
C7	0.0473 (16)	0.0459 (16)	0.0440 (16)	0.0142 (13)	0.0075 (13)	0.0073 (13)
C8	0.0431 (15)	0.0468 (16)	0.0435 (15)	0.0075 (13)	0.0080 (12)	0.0086 (13)
C9	0.0515 (17)	0.0586 (19)	0.0452 (16)	0.0154 (15)	0.0003 (13)	0.0068 (14)
C10	0.0455 (16)	0.0481 (16)	0.0457 (16)	0.0066 (13)	0.0044 (13)	0.0046 (13)
C11	0.075 (2)	0.078 (3)	0.067 (2)	0.036 (2)	0.0035 (19)	−0.0020 (19)
C12	0.067 (2)	0.062 (2)	0.059 (2)	0.0136 (18)	0.0142 (17)	−0.0054 (16)
C13	0.101 (3)	0.118 (4)	0.048 (2)	0.043 (3)	−0.009 (2)	−0.018 (2)
C14	0.077 (3)	0.104 (3)	0.055 (2)	0.044 (2)	−0.0145 (19)	−0.012 (2)

Geometric parameters (Å, º)

S1—C8	1.670 (3)	C4—C5	1.374 (5)
O1—C7	1.221 (3)	C4—H4	0.9300
N1—C7	1.370 (4)	C5—C6	1.388 (4)
N1—C8	1.394 (4)	C5—H5	0.9300
N1—H1	0.8600	C6—C7	1.487 (4)
N2—C8	1.314 (4)	C9—C10	1.510 (4)
N2—C9	1.440 (4)	C9—H9A	0.9700
N2—H2	0.8600	C9—H9B	0.9700
N3—C10	1.317 (4)	C10—C14	1.357 (5)
N3—C11	1.345 (4)	C11—C12	1.339 (5)
C1—C2	1.376 (5)	C11—H11	0.9300
C1—C6	1.382 (4)	C12—C13	1.352 (5)
C1—H1A	0.9300	C12—H12	0.9300
C2—C3	1.375 (5)	C13—C14	1.372 (5)
C2—H2A	0.9300	C13—H13	0.9300
C3—C4	1.372 (5)	C14—H14	0.9300
C3—H3	0.9300
C7—N1—C8	127.6 (2)	O1—C7—C6	121.1 (3)
C7—N1—H1	116.2	N1—C7—C6	116.9 (2)
C8—N1—H1	116.2	N2—C8—N1	117.0 (2)
C8—N2—C9	123.3 (2)	N2—C8—S1	123.9 (2)
C8—N2—H2	118.4	N1—C8—S1	119.1 (2)
C9—N2—H2	118.4	N2—C9—C10	110.8 (2)
C10—N3—C11	117.6 (3)	N2—C9—H9A	109.5
C2—C1—C6	120.1 (3)	C10—C9—H9A	109.5
C2—C1—H1A	119.9	N2—C9—H9B	109.5
C6—C1—H1A	119.9	C10—C9—H9B	109.5
C3—C2—C1	120.3 (3)	H9A—C9—H9B	108.1
C3—C2—H2A	119.9	N3—C10—C14	121.7 (3)
C1—C2—H2A	119.9	N3—C10—C9	117.9 (3)
C4—C3—C2	119.9 (3)	C14—C10—C9	120.4 (3)
C4—C3—H3	120.0	C12—C11—N3	124.0 (3)
C2—C3—H3	120.0	C12—C11—H11	118.0
C3—C4—C5	120.2 (3)	N3—C11—H11	118.0
C3—C4—H4	119.9	C11—C12—C13	117.8 (3)
C5—C4—H4	119.9	C11—C12—H12	121.1
C4—C5—C6	120.4 (3)	C13—C12—H12	121.1
C4—C5—H5	119.8	C12—C13—C14	119.5 (4)
C6—C5—H5	119.8	C12—C13—H13	120.2
C1—C6—C5	119.1 (3)	C14—C13—H13	120.2
C1—C6—C7	123.1 (3)	C10—C14—C13	119.4 (3)
C5—C6—C7	117.6 (3)	C10—C14—H14	120.3
O1—C7—N1	122.0 (3)	C13—C14—H14	120.3
C6—C1—C2—C3	0.1 (5)	C9—N2—C8—S1	−1.5 (4)
C1—C2—C3—C4	0.2 (5)	C7—N1—C8—N2	−2.7 (5)
C2—C3—C4—C5	−0.8 (6)	C7—N1—C8—S1	176.1 (3)
C3—C4—C5—C6	1.1 (6)	C8—N2—C9—C10	−176.7 (3)
C2—C1—C6—C5	0.2 (5)	C11—N3—C10—C14	0.4 (6)
C2—C1—C6—C7	175.4 (3)	C11—N3—C10—C9	−179.9 (3)
C4—C5—C6—C1	−0.8 (5)	N2—C9—C10—N3	3.8 (4)
C4—C5—C6—C7	−176.2 (3)	N2—C9—C10—C14	−176.4 (4)
C8—N1—C7—O1	12.3 (5)	C10—N3—C11—C12	−0.3 (7)
C8—N1—C7—C6	−166.9 (3)	N3—C11—C12—C13	0.5 (7)
C1—C6—C7—O1	−152.7 (3)	C11—C12—C13—C14	−0.8 (8)
C5—C6—C7—O1	22.5 (5)	N3—C10—C14—C13	−0.7 (7)
C1—C6—C7—N1	26.5 (4)	C9—C10—C14—C13	179.5 (4)
C5—C6—C7—N1	−158.3 (3)	C12—C13—C14—C10	0.9 (8)
C9—N2—C8—N1	177.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.96	2.641 (4)	135
N2—H2···N3	0.86	2.24	2.644 (4)	109
N1—H1···S1^i	0.86	2.60	3.426 (3)	162

Symmetry code: (i) −x+2, −y+1, −z.