1-(1,3-Benzothia­zol-2-yl)-3-benzoyl­thio­urea

The title compound, C₁₅H₁₁N₃OS₂, was synthesized from benzoyl thio­cyanate and 2-amino­benzothia­zole in dry acetone. The thio­urea group is in the thio­amide form. The mol­ecules are stabilized by two inter­molecular C—H...S and C—H...O hydrogen bonds. Intra­molecular N—H...O hydrogen bonding results in a pseudo-S(6) planar ring with dihedral angles of 11.23 and 11.91° with the benzothiazole ring system and the phenyl ring, respectively.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.102
• Data-to-parameter ratio = 18.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.93
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.928
            Tmax scaled      0.928 Tmin scaled      0.866
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Thiourea and its derivatives have found extensive applications in the fields of medicine, agriculture and analytical chemistry. They are known to exhibit a wide variety of biological activities such as antiviral, antibacterial, antifungal, antitubercular, herbicidal and insecticidal (Koketsu & Ishihara, 2006). Thioureas are also widely used as precursors or intermediates towards the syntheisis of a variety of heterocyclic compounds (Zeng et al.2003; D'hooghe, et al. 2005). Among thiourea derivatives acylthiourea with potential donor atoms (O and S) have been found to display remarkably rich coordination chemistry. Such coordination compounds of thiourea have been studied for different biological systems (Rodríguez-Fernández et al. 2005). In recent years some attention has also been paid for potential use of acylthioureas as highly selective reagents for the enrichment and separation of metal cations (del Campo et al. 2002). The condensation of acyl / aroyl thiocyanates with primary amine affords 1,3-disubstituted thioureas in excellent yield in a single step. However, our attempt to synthesize thiourea derivative by treating benzoyl thiocyanate with 2-aminothiazole resulted in a fused 1,3,5-triazine instead of the expected thiourea product (Yunus et al. 2007). This observation prompted us to explore the outcome of the reaction with 2-aminothiazole derivatives such as 2-aminobenzothiazole. The reaction of the benzoyl thiocyanate with 2-aminobenzothiazole yielded the title compound (I) which is reported here.

The title compound crystallizes in the thioamide form. The conformation of the molecule with respect to the carbonyl and thiocarbonyl part is nearly planar as reflected by the torsion angles O1—C7—N1—C8, C7—N1—C8—S2 and C7—N1—C8—N2 of -0.42(°), -179.58(°) and -0.06(°) respectively. The benzoyl and benzothiazole groups are trans and cis, respectively, to the S atom across the thiourea C—N bonds (Figure 1 and Table 1). The C8—S2 and C7—O1 bonds show a typical double bond character with bond lengths of 1.6578 (15) and 1.2179 (19) Å respectively, closely related to other thiourea derivatives (Yamin & Hassan, 2004). All of the C—N bonds of thiourea fragment C7—N1, C8—N1, C8—N2 and C9—N2 are in the range 1.3933 (19) - 1.338 (2) Å, intermediate between those expected for single and double C—N bonds (1.47 and 1.27 Å respectively). Among these C—N bonds the C7—N1 is the longest indicating Csp²-Nsp² single bond while C8—N2 is the shortest bond with more double bond character. This further demonstrate that there is π conjugation only along S2—C8—N2 system but not along O1—C7—N1 and C7—N1—C8 as found in 1-(3-methoxybenzoyl)-3,3-diethylthiourea (Morales et al., 2000). The bond lengths in the benzothizole ring system are normal and agree with the corresponding values found in 2-(benzothiazole-2-yliminomethyl)-6-methoxyphenol and N,N-(2-benzothia-zole)(2-pyridylmethyl)amine (Büyükgüngör et al. 2004; Chen et al. 2003). The bond length C9—N2 is very close to the value determined for the 2-(benzothiazole-2-yliminomethyl)-6-methoxyphenol suggesting the existence of a delocalized double bond in the benzothiazole moiety (Büyükgüngör et al. 2004). All bond lengths and angles confirm the sp² hybridization for all C and N atoms of the benzothiazole ring with all C—C and C—N bond lengths intermediate between single and double bonds. The benzothiazole ring bonded to N2 is essentially planar and inclined at an angle -11.23(°) with respect to the plane of thiourea moiety. Similarly the phenyl ring bonded to C7 is at an angle of 11.91(°) with respect to the plane formed by the thiourea moiety.

The molecule is further stabilized by intermolecular and intramolecular hydrogen bonding. There are two types of intermolecular C1—H1A···S2i and C5—H5A···O1ii [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z + 1] hydrogen bonds. The intramolecular N2—H2B···O1 hydrogen bond is also observed. As a result, a pseudo six membered (O1—C7—N1—C8—N2^···H2B) ring is formed.

Related literature

For related literature see: Büyükgüngör et al. (2004); del Campo et al. (2002); Chen et al. (2003); D'hooghe et al. (2005); Koketsu & Ishihara (2006); Morales et al. (2000); Rodríguez-Fernández et al. (2005); Yamin & Hassan (2004); Yunus et al. (2007); Zeng et al. (2003).

S2. Experimental

A mixture of ammonium thiocyanate (26 mmol) and benzoyl chloride (26 mmol) in dry acetone (60 ml) was stirred for 30 min. Then 2-aminobenzothiazole (26 mmol) was added and the reaction mixture was refluxed for 2 h. After cooling, the reaction mixture was poured in an acidified cold water. The resulting yellow solid was filtered and washed with cold acetone. The title compound (I) was obtained as suitable single crystals for X-Ray analysis after recrystallization of the solid from an 1:1 ethanol-dichloromethane mixture.

S3. Refinement

H atoms were placed in idealized positions and refined using a riding model approximation. Bond lengths were fixed to 0.86 (amine NH) or 0.93 Å (aromatic CH). Isotropic displacement parameters were fixed to U_iso(H) = 1.2U_eq(carrier atom).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures

Fig. 1. The molecular structure of (I) with atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

1-(1,3-Benzothiazol-2-yl)-3-benzoylthiourea

Crystal data

C15H11N3OS2	F(000) = 648
Mr = 313.39	Dx = 1.447 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 8487 reflections
a = 12.4402 (8) Å	θ = 2.6–28.3°
b = 5.8608 (4) Å	µ = 0.37 mm^−1
c = 19.7240 (13) Å	T = 293 K
β = 90.223 (1)°	Block, pale-yellow
V = 1438.06 (16) Å^3	0.32 × 0.26 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	3508 independent reflections
Radiation source: fine-focus sealed tube	2724 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −16→16
Tmin = 0.933, Tmax = 1.000	k = −7→7
8487 measured reflections	l = −19→26

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0541P)^2 + 0.2538P] where P = (Fo^2 + 2Fc^2)/3
3508 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.21573 (13)	0.0594 (3)	0.53895 (8)	0.0416 (4)
H1A	0.1480	0.0792	0.5197	0.050*
C2	0.23408 (16)	−0.1206 (3)	0.58247 (9)	0.0515 (4)
H2A	0.1785	−0.2203	0.5932	0.062*
C3	0.33485 (18)	−0.1525 (4)	0.61000 (10)	0.0602 (5)
H3A	0.3473	−0.2749	0.6390	0.072*
C4	0.41698 (17)	−0.0051 (4)	0.59497 (11)	0.0646 (5)
H4A	0.4848	−0.0280	0.6137	0.078*
C5	0.39901 (14)	0.1779 (3)	0.55189 (9)	0.0529 (5)
H5A	0.4547	0.2781	0.5419	0.063*
C6	0.29787 (12)	0.2116 (3)	0.52370 (8)	0.0378 (3)
C7	0.28504 (12)	0.4117 (3)	0.47818 (8)	0.0380 (3)
C8	0.14589 (12)	0.6519 (3)	0.42051 (8)	0.0372 (3)
C9	0.22056 (12)	0.9776 (3)	0.35659 (7)	0.0354 (3)
C10	0.29090 (13)	1.2734 (3)	0.30503 (8)	0.0388 (3)
C11	0.36820 (14)	1.4337 (3)	0.28664 (9)	0.0472 (4)
H11A	0.4382	1.4225	0.3030	0.057*
C12	0.33920 (16)	1.6082 (3)	0.24397 (9)	0.0517 (4)
H12A	0.3902	1.7159	0.2313	0.062*
C13	0.23408 (17)	1.6266 (3)	0.21919 (9)	0.0551 (5)
H13A	0.2164	1.7450	0.1898	0.066*
C14	0.15669 (15)	1.4723 (3)	0.23769 (9)	0.0514 (4)
H14A	0.0867	1.4855	0.2214	0.062*
C15	0.18525 (13)	1.2952 (3)	0.28139 (8)	0.0412 (4)
N1	0.18011 (10)	0.4716 (2)	0.46078 (7)	0.0395 (3)
H1B	0.1303	0.3861	0.4770	0.047*
N2	0.22510 (10)	0.7819 (2)	0.39602 (7)	0.0385 (3)
H2B	0.2889	0.7372	0.4064	0.046*
N3	0.30872 (10)	1.0881 (2)	0.34739 (7)	0.0397 (3)
O1	0.36174 (9)	0.5195 (2)	0.45724 (6)	0.0482 (3)
S1	0.10503 (3)	1.08096 (8)	0.31634 (2)	0.04440 (13)
S2	0.01565 (3)	0.69188 (9)	0.40697 (2)	0.05128 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0415 (8)	0.0417 (9)	0.0415 (8)	0.0026 (7)	0.0017 (7)	−0.0018 (7)
C2	0.0636 (11)	0.0424 (10)	0.0486 (10)	−0.0033 (8)	0.0075 (8)	0.0042 (8)
C3	0.0734 (13)	0.0535 (11)	0.0536 (11)	0.0096 (10)	−0.0028 (10)	0.0161 (9)
C4	0.0549 (11)	0.0708 (13)	0.0680 (13)	0.0098 (10)	−0.0134 (9)	0.0184 (11)
C5	0.0423 (9)	0.0610 (12)	0.0553 (11)	0.0008 (8)	−0.0066 (8)	0.0146 (9)
C6	0.0389 (8)	0.0385 (8)	0.0362 (8)	0.0038 (6)	0.0000 (6)	0.0004 (6)
C7	0.0358 (7)	0.0394 (8)	0.0388 (8)	0.0009 (6)	−0.0025 (6)	0.0003 (7)
C8	0.0360 (8)	0.0391 (8)	0.0366 (8)	0.0027 (6)	−0.0012 (6)	−0.0027 (6)
C9	0.0359 (7)	0.0363 (8)	0.0339 (7)	0.0054 (6)	−0.0023 (6)	−0.0005 (6)
C10	0.0422 (8)	0.0398 (8)	0.0343 (8)	0.0048 (7)	0.0034 (6)	0.0000 (6)
C11	0.0471 (9)	0.0494 (10)	0.0451 (9)	−0.0003 (8)	0.0056 (7)	0.0020 (8)
C12	0.0631 (11)	0.0460 (10)	0.0460 (10)	−0.0016 (8)	0.0126 (8)	0.0040 (8)
C13	0.0740 (13)	0.0474 (10)	0.0441 (10)	0.0154 (9)	0.0092 (9)	0.0106 (8)
C14	0.0511 (10)	0.0554 (11)	0.0476 (10)	0.0141 (8)	0.0005 (8)	0.0088 (8)
C15	0.0442 (9)	0.0414 (9)	0.0381 (8)	0.0061 (7)	0.0022 (7)	0.0018 (7)
N1	0.0324 (6)	0.0398 (7)	0.0461 (7)	−0.0007 (5)	−0.0018 (5)	0.0073 (6)
N2	0.0323 (6)	0.0392 (7)	0.0441 (7)	0.0031 (5)	−0.0024 (5)	0.0046 (6)
N3	0.0380 (7)	0.0413 (7)	0.0399 (7)	0.0021 (6)	−0.0018 (5)	0.0030 (6)
O1	0.0351 (6)	0.0515 (7)	0.0581 (7)	−0.0035 (5)	−0.0043 (5)	0.0143 (6)
S1	0.0367 (2)	0.0473 (3)	0.0491 (2)	0.00442 (17)	−0.00595 (17)	0.00779 (18)
S2	0.0328 (2)	0.0624 (3)	0.0586 (3)	0.00376 (19)	−0.00173 (18)	0.0142 (2)

Geometric parameters (Å, º)

C1—C2	1.379 (2)	C9—N3	1.287 (2)
C1—C6	1.390 (2)	C9—N2	1.387 (2)
C1—H1A	0.9300	C9—S1	1.7476 (15)
C2—C3	1.377 (3)	C10—N3	1.387 (2)
C2—H2A	0.9300	C10—C11	1.393 (2)
C3—C4	1.371 (3)	C10—C15	1.399 (2)
C3—H3A	0.9300	C11—C12	1.372 (2)
C4—C5	1.386 (3)	C11—H11A	0.9300
C4—H4A	0.9300	C12—C13	1.398 (3)
C5—C6	1.388 (2)	C12—H12A	0.9300
C5—H5A	0.9300	C13—C14	1.371 (3)
C6—C7	1.486 (2)	C13—H13A	0.9300
C7—O1	1.2179 (19)	C14—C15	1.395 (2)
C7—N1	1.3933 (19)	C14—H14A	0.9300
C8—N2	1.338 (2)	C15—S1	1.7471 (17)
C8—N1	1.388 (2)	N1—H1B	0.8600
C8—S2	1.6578 (15)	N2—H2B	0.8600
C2—C1—C6	120.37 (16)	N3—C10—C11	125.14 (15)
C2—C1—H1A	119.8	N3—C10—C15	114.84 (14)
C6—C1—H1A	119.8	C11—C10—C15	120.01 (15)
C3—C2—C1	119.85 (18)	C12—C11—C10	118.83 (17)
C3—C2—H2A	120.1	C12—C11—H11A	120.6
C1—C2—H2A	120.1	C10—C11—H11A	120.6
C4—C3—C2	120.47 (18)	C11—C12—C13	121.01 (18)
C4—C3—H3A	119.8	C11—C12—H12A	119.5
C2—C3—H3A	119.8	C13—C12—H12A	119.5
C3—C4—C5	120.11 (18)	C14—C13—C12	120.85 (17)
C3—C4—H4A	119.9	C14—C13—H13A	119.6
C5—C4—H4A	119.9	C12—C13—H13A	119.6
C4—C5—C6	119.95 (18)	C13—C14—C15	118.55 (17)
C4—C5—H5A	120.0	C13—C14—H14A	120.7
C6—C5—H5A	120.0	C15—C14—H14A	120.7
C5—C6—C1	119.24 (15)	C14—C15—C10	120.72 (16)
C5—C6—C7	116.71 (15)	C14—C15—S1	129.37 (14)
C1—C6—C7	124.06 (14)	C10—C15—S1	109.89 (12)
O1—C7—N1	121.35 (14)	C8—N1—C7	128.15 (13)
O1—C7—C6	122.16 (14)	C8—N1—H1B	115.9
N1—C7—C6	116.49 (14)	C7—N1—H1B	115.9
N2—C8—N1	114.57 (13)	C8—N2—C9	130.20 (13)
N2—C8—S2	125.60 (12)	C8—N2—H2B	114.9
N1—C8—S2	119.83 (12)	C9—N2—H2B	114.9
N3—C9—N2	117.53 (13)	C9—N3—C10	110.14 (13)
N3—C9—S1	117.47 (12)	C15—S1—C9	87.62 (7)
N2—C9—S1	124.97 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1	0.86	1.86	2.5878 (17)	142
C1—H1A···S2^i	0.93	2.84	3.4017 (17)	120
C5—H5A···O1^ii	0.93	2.57	3.470 (2)	162

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.