N-(2-Chloro­benzo­yl)-N′-(3-pyrid­yl)thio­urea

In the mol­ecule of the title compound, C₁₃H₁₀ClN₃OS, the dihedral angles between the plane through the thio­urea group and the pyridine and benzene rings are 53.08 (3) and 87.12 (3)°, respectively. The mol­ecules are linked by inter­molecular N—H...N hydrogen-bonding inter­actions to form a supra­molecular chain structure along the a axis. An intra­mol­ecular N—H...O hydrogen bond is also present.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.037
• wR factor = 0.100
• Data-to-parameter ratio = 13.5

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S1. Comment

Thiourea and its substituted derivatives have attracted much attention because of their unique properties, such as the strong coordination ability (Su et al., 2004; Su et al., 2006; Xian et al., 2004; West et al., 2000). They are used as selective analytical reagents, especially for the determination of transition metals in complex interfering matrices (Koch, 2001; Foss et al., 2004). It has been shown that the redox properties of thiourea are markedly influenced by electronic factors (Guillon et al., 1996), and the biological activity of thiourea derivatives has also been reported in the literature (Teoh et al., 1999; Campo et al., 2002). However, the study of S···H interactions may have fundamental importance in biochemical research due to the fact that living systems contain several important sulfur-containing molecules, such as the aminoacids cysteine and methionine (Krepps et al., 2001). Related to the biological relevance of S···H interactions, Uckum and coworkers have recently reported a structural study of a series of thiourea compounds (Venkatachalam et al., 2004). Here we report the synthesis and crystal structure of a new benzoylthiourea derivative, N-(o-chloro)benzoyl-N'-(3-pyridyl)thiourea. The molecular structure of the title compound is shown in Figure 1.

The dihedral angles formed by the plane through the thiourea group and the pyridine and benzene rings of 53.08 (3) and 87.12 (3)°, respectively. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bonding interaction (Table 1), forming a planar six-membered ring. In contrast to other thiourea compounds, the H1···S1 separation is 2.662 (2) Å, indicating that S1 is not involved in hydrogen bonding. This situation is similar to that found in the structure of N-benzoyl-N'-(3-pyridyl)thiourea (Dong et al., 2006). The C=O bond length of 1.217 (3) Å is just significantly longer than the average C=O bond length (1.200 Å) due to the intramolecular hydrogen bond. In the crystal structure, molecules are linked by intermolecular by N—H···N hydrogen interactions to form supramolecular chains along the a axis.

Related literature

For related literature, see: Campo et al. (2002); Dong et al. (2006, 2008); Foss et al. (2004); Guillon et al. (1996); Koch (2001); Krepps et al. (2001); Su et al. (2004, 2006); Teoh et al. (1999); Venkatachalam et al. (2004); West et al. (2000); Xian et al. (2004).

S2. Experimental

N-(o-Chloro)benzoyl-N'-(3-pyridyl)thiourea was synthesized according the method reported in the literature (Dong et al., 2008). o-Chlorobenzoyl chloride (3.61 g, 0.02 mol) was reacted with ammonium thiocyanate (2.28 g, 0.03 mol) in CH₂Cl₂ (25 ml) under solid-liquid phase transfer catalysis, using 3% polyethylene glycol-400 (0.36 g) as catalyst, to give the corresponding benzoyl isothiocyanate, which was reacted with 3-aminopyridine (1.72 g, 0.02 mol). The title compound precipitated immediately. The product was filtered, washed with water and CH₂Cl₂ and dried. Colourless needle-shaped single crystals were obtained by slow evaporation of an acetone solution after several weeks at room temperature. M.p. 442 - 444 K. Anal. Calcd. for C₁₃H₁₀ClN₃OS: C, 53.52; H, 3.45; N, 14.40. Found: C, 53.28; H, 3.48; N, 14.15%.

S3. Refinement

H atoms were treated as riding atoms with C—H = 0.93 Å, N—H = 0.86 Å, and U_iso(H) = 1.2 U_eq(C, N).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecule structure of the title compound with atom numbering. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
	Fig. 2. The supramolecular chain structure of the title compound constructed by intermolecular N—H···N hydrogen bonding interactions (dotted lines).

N-(2-Chlorobenzoyl)-N'-(3-pyridyl)thiourea

Crystal data

C13H10ClN3OS	Z = 2
Mr = 291.75	F(000) = 300
Triclinic, P1	Dx = 1.444 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.421 (3) Å	Cell parameters from 1514 reflections
b = 9.282 (4) Å	θ = 2.5–26.6°
c = 10.512 (4) Å	µ = 0.43 mm^−1
α = 98.336 (4)°	T = 298 K
β = 110.797 (4)°	Needle, colourless
γ = 112.532 (4)°	0.32 × 0.11 × 0.07 mm
V = 670.9 (5) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2319 independent reflections
Radiation source: fine-focus sealed tube	1734 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
Tmin = 0.874, Tmax = 0.972	k = −11→9
3504 measured reflections	l = −12→9

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.2146P] where P = (Fo^2 + 2Fc^2)/3
2319 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.20 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
Cl1	0.41414 (14)	0.64074 (11)	0.50918 (8)	0.0781 (3)
N1	0.4306 (3)	0.5361 (2)	0.1841 (2)	0.0397 (5)
H1	0.3077	0.4966	0.1477	0.048*
N2	0.6871 (3)	0.4903 (2)	0.2029 (2)	0.0416 (5)
H2	0.7561	0.5927	0.2548	0.050*
N3	1.0366 (3)	0.3871 (2)	0.1394 (2)	0.0481 (5)
O1	0.7112 (3)	0.7734 (2)	0.3311 (2)	0.0630 (5)
S1	0.33789 (9)	0.24252 (8)	0.02568 (7)	0.0500 (2)
C1	0.4967 (3)	0.4294 (3)	0.1432 (2)	0.0370 (5)
C2	0.5364 (4)	0.6956 (3)	0.2748 (3)	0.0422 (6)
C3	0.4139 (3)	0.7708 (3)	0.2962 (2)	0.0400 (5)
C4	0.3540 (4)	0.7557 (3)	0.4027 (3)	0.0476 (6)
C5	0.2449 (4)	0.8281 (3)	0.4233 (3)	0.0560 (7)
H5	0.2062	0.8177	0.4955	0.067*
C6	0.1944 (4)	0.9154 (3)	0.3359 (3)	0.0613 (8)
H6	0.1211	0.9644	0.3490	0.074*
C7	0.2513 (4)	0.9307 (3)	0.2296 (3)	0.0593 (7)
H7	0.2157	0.9895	0.1705	0.071*
C8	0.3611 (4)	0.8595 (3)	0.2093 (3)	0.0495 (6)
H8	0.3997	0.8711	0.1371	0.059*
C9	0.9299 (3)	0.4610 (3)	0.1477 (2)	0.0411 (6)
H9	0.9551	0.5586	0.1259	0.049*
C10	0.7848 (3)	0.3985 (3)	0.1872 (2)	0.0380 (5)
C11	0.7442 (4)	0.2524 (3)	0.2178 (3)	0.0481 (6)
H11	0.6456	0.2070	0.2436	0.058*
C12	0.8523 (4)	0.1757 (3)	0.2093 (3)	0.0542 (7)
H12	0.8291	0.0776	0.2300	0.065*
C13	0.9953 (4)	0.2463 (3)	0.1697 (3)	0.0537 (7)
H13	1.0674	0.1930	0.1636	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1271 (8)	0.0975 (6)	0.0704 (5)	0.0861 (6)	0.0617 (5)	0.0496 (5)
N1	0.0341 (10)	0.0395 (11)	0.0488 (11)	0.0192 (9)	0.0225 (9)	0.0076 (9)
N2	0.0372 (11)	0.0368 (10)	0.0569 (12)	0.0195 (9)	0.0271 (10)	0.0101 (9)
N3	0.0439 (12)	0.0496 (12)	0.0650 (14)	0.0268 (10)	0.0339 (11)	0.0184 (11)
O1	0.0406 (11)	0.0539 (11)	0.0758 (13)	0.0192 (9)	0.0209 (10)	−0.0069 (10)
S1	0.0487 (4)	0.0416 (4)	0.0571 (4)	0.0206 (3)	0.0259 (3)	0.0051 (3)
C1	0.0437 (14)	0.0408 (13)	0.0405 (13)	0.0244 (11)	0.0273 (11)	0.0160 (10)
C2	0.0426 (15)	0.0419 (13)	0.0447 (14)	0.0219 (12)	0.0227 (12)	0.0074 (11)
C3	0.0408 (13)	0.0356 (12)	0.0459 (14)	0.0206 (11)	0.0213 (11)	0.0071 (11)
C4	0.0624 (17)	0.0491 (14)	0.0487 (14)	0.0376 (13)	0.0297 (13)	0.0177 (12)
C5	0.0712 (19)	0.0653 (17)	0.0544 (16)	0.0448 (16)	0.0386 (15)	0.0170 (14)
C6	0.0686 (19)	0.0596 (17)	0.0696 (19)	0.0464 (16)	0.0307 (16)	0.0129 (15)
C7	0.0712 (19)	0.0516 (16)	0.0672 (18)	0.0404 (15)	0.0291 (16)	0.0236 (14)
C8	0.0577 (16)	0.0438 (14)	0.0540 (15)	0.0264 (13)	0.0293 (13)	0.0168 (12)
C9	0.0374 (13)	0.0396 (13)	0.0515 (14)	0.0198 (11)	0.0238 (12)	0.0142 (11)
C10	0.0388 (13)	0.0410 (13)	0.0432 (13)	0.0231 (11)	0.0236 (11)	0.0120 (10)
C11	0.0507 (15)	0.0512 (15)	0.0599 (16)	0.0269 (13)	0.0380 (13)	0.0222 (13)
C12	0.0630 (17)	0.0487 (15)	0.0750 (18)	0.0351 (14)	0.0422 (15)	0.0300 (14)
C13	0.0556 (16)	0.0537 (16)	0.0732 (18)	0.0373 (14)	0.0378 (15)	0.0220 (14)

Geometric parameters (Å, º)

Cl1—C4	1.734 (2)	C5—C6	1.372 (4)
N1—C2	1.368 (3)	C5—H5	0.9300
N1—C1	1.394 (3)	C6—C7	1.369 (4)
N1—H1	0.8600	C6—H6	0.9300
N2—C1	1.331 (3)	C7—C8	1.380 (4)
N2—C10	1.422 (3)	C7—H7	0.9300
N2—H2	0.8600	C8—H8	0.9300
N3—C13	1.335 (3)	C9—C10	1.375 (3)
N3—C9	1.340 (3)	C9—H9	0.9300
O1—C2	1.217 (3)	C10—C11	1.381 (3)
S1—C1	1.659 (2)	C11—C12	1.371 (3)
C2—C3	1.508 (3)	C11—H11	0.9300
C3—C4	1.385 (3)	C12—C13	1.373 (3)
C3—C8	1.386 (3)	C12—H12	0.9300
C4—C5	1.384 (3)	C13—H13	0.9300
C2—N1—C1	128.3 (2)	C7—C6—H6	119.8
C2—N1—H1	115.9	C5—C6—H6	119.8
C1—N1—H1	115.9	C6—C7—C8	120.5 (2)
C1—N2—C10	124.83 (19)	C6—C7—H7	119.7
C1—N2—H2	117.6	C8—C7—H7	119.7
C10—N2—H2	117.6	C7—C8—C3	120.1 (2)
C13—N3—C9	117.2 (2)	C7—C8—H8	119.9
N2—C1—N1	115.4 (2)	C3—C8—H8	119.9
N2—C1—S1	125.54 (17)	N3—C9—C10	122.6 (2)
N1—C1—S1	119.02 (17)	N3—C9—H9	118.7
O1—C2—N1	124.8 (2)	C10—C9—H9	118.7
O1—C2—C3	122.1 (2)	C9—C10—C11	119.2 (2)
N1—C2—C3	113.1 (2)	C9—C10—N2	119.10 (19)
C4—C3—C8	118.6 (2)	C11—C10—N2	121.6 (2)
C4—C3—C2	121.6 (2)	C12—C11—C10	118.6 (2)
C8—C3—C2	119.8 (2)	C12—C11—H11	120.7
C5—C4—C3	121.1 (2)	C10—C11—H11	120.7
C5—C4—Cl1	119.9 (2)	C11—C12—C13	118.8 (2)
C3—C4—Cl1	118.97 (18)	C11—C12—H12	120.6
C6—C5—C4	119.2 (2)	C13—C12—H12	120.6
C6—C5—H5	120.4	N3—C13—C12	123.6 (2)
C4—C5—H5	120.4	N3—C13—H13	118.2
C7—C6—C5	120.4 (2)	C12—C13—H13	118.2
C10—N2—C1—N1	173.77 (19)	C4—C5—C6—C7	0.0 (4)
C10—N2—C1—S1	−7.1 (3)	C5—C6—C7—C8	−0.4 (4)
C2—N1—C1—N2	1.6 (3)	C6—C7—C8—C3	0.4 (4)
C2—N1—C1—S1	−177.58 (18)	C4—C3—C8—C7	0.0 (4)
C1—N1—C2—O1	3.2 (4)	C2—C3—C8—C7	−179.1 (2)
C1—N1—C2—C3	−178.6 (2)	C13—N3—C9—C10	0.8 (4)
O1—C2—C3—C4	−93.6 (3)	N3—C9—C10—C11	−1.0 (4)
N1—C2—C3—C4	88.1 (3)	N3—C9—C10—N2	175.7 (2)
O1—C2—C3—C8	85.4 (3)	C1—N2—C10—C9	129.9 (2)
N1—C2—C3—C8	−92.8 (3)	C1—N2—C10—C11	−53.4 (3)
C8—C3—C4—C5	−0.4 (4)	C9—C10—C11—C12	0.8 (4)
C2—C3—C4—C5	178.7 (2)	N2—C10—C11—C12	−175.8 (2)
C8—C3—C4—Cl1	178.40 (18)	C10—C11—C12—C13	−0.5 (4)
C2—C3—C4—Cl1	−2.5 (3)	C9—N3—C13—C12	−0.5 (4)
C3—C4—C5—C6	0.4 (4)	C11—C12—C13—N3	0.4 (4)
Cl1—C4—C5—C6	−178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.98	2.671 (3)	137
N1—H1···N3^i	0.86	2.08	2.886 (4)	157

Symmetry code: (i) x−1, y, z.