1-Benzoyl-4-thio­biuret

Kang, S.K.

doi:10.1107/S1600536813019983

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1327

doi:10.1107/S1600536813019983

Open

access

1-Benzoyl-4-thiobiuret

Sung Kwon Kang ^a ^*

^aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

(Received 16 July 2013; accepted 19 July 2013; online 27 July 2013)

In the title compound (systematic name: {[(phenylformamido)carbonyl]amino}methanethioamide), C₉H₉N₃O₂S, both benzoyl and terminal thiourea fragments adopt transoid conformations with respect to the central carbonyl O atom. The benzoyl and thiobiuret groups are almost coplanar, making a dihedral angle of 4.40 (8)°. The molecular structure is stabilized by two intramolecular N—H⋯O hydrogen bonds. In the crystal, N—H⋯O and N—H⋯S hydrogen bonds link the molecules into a tape running along [101].

Related literature

For the structure and reactivity of thiadiazole derivatives, see: Cho, Ra et al. (1996 ); Cho, Cho et al. (1996 ). For the structure of a thiobiuret isomer, see: Kang et al. (2012 ).

Experimental

Crystal data

C₉H₉N₃O₂S
M_r = 223.25
Triclinic, $[P \overline 1]$
a = 5.6616 (1) Å
b = 7.8407 (2) Å
c = 11.7631 (3) Å
α = 97.169 (2)°
β = 94.992 (3)°
γ = 101.390 (2)°
V = 504.53 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.2 × 0.15 × 0.07 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.94, T_max = 0.97
17356 measured reflections
2516 independent reflections
1485 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.097
S = 0.87
2516 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O11ⁱ	0.843 (18)	2.172 (18)	2.9891 (18)	163.3 (16)
N12—H12⋯O8	0.882 (19)	1.919 (19)	2.6171 (17)	135.0 (17)
N15—H15A⋯O11	0.91 (2)	1.99 (2)	2.684 (2)	132.0 (17)
N15—H15B⋯S14ⁱⁱ	0.85 (2)	2.58 (2)	3.4295 (17)	171.3 (17)
Symmetry codes: (i) -x-1, -y+1, -z; (ii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2013 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019983/is5292sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019983/is5292Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019983/is5292Isup3.cml

checkCIF report

Comment top

5-Amino-2H-1,2,4-thiadiazol-3-one is the analog of cytosine. As an analog of cytosine, the tautomeric structure and reactivity of this compound have been examined (Cho, Ra et al., 1996). Within the framework of our interest in the synthesis of novel potential anti-metabolites of nucleic acid components which would possess cytostatic activity, we have synthesized derivatives of 5-amino-3H-1,3,4-thiadiazol-2-one (Cho, Cho et al., 1996). The title compound, 1-benzoyl-4-thiobiuret, is an isomer of 1-benzoyl-2-thiobiuret (Kang et al., 2012). This compound is an intermediate for the formation of the thiobiuret which is a good starting material to make 5-amino-2H-1,2,4-thiadizolin-3-one via oxidative ring-closure reaction.

The dihedral angle between the benzoyl unit (C1–C7/O8) and thiobiuret group (N9/C10/O11/N12/C13/S14/N15) is 4.40 (8)°. Both carbonyl O8 and S14 atoms are positioned anti conformations with respect to the O11 atom (Fig. 1). The intramolecular O8···H12—N12 and O11···H15—N15 hydrogen bonds stabilize the molecule (Fig. 1 and Table 1). The intermolecular N—H···O and N—H···S hydrogen bonds link the molecules into a tape along the [101] direction (Fig. 2 and Table 1).

Related literature top

For the structure and reactivity of thiadiazole derivatives, see: Cho, Ra et al. (1996); Cho, Cho et al. (1996). For the structure of a thiobiuret isomer, see: Kang et al. (2012).

Experimental top

Benzoyl chloride (48 ml, 58.1 g, 0.41 mol) was added to warm solution of potassium thiocyanate (48.0 g, 0.49 mol) in acetone (400 ml). The solution became milky white and yellow when the addition had been completed. The mixture was stirred for 3.5 h at 50°C and left to cool to room temperature. The filtrate was heated to 55°C for 5 h with urea (24.0 g, 0.40 mol). And the resulting solution was cooled to room temperature and then placed in an ice bath for several hours. The cold mixture was filtered to give 1-benzoyl-4-thiobiuret as a bright yellow solid. Recrystallization from methyl alcohol afforded the yellow crystals suitable for X-ray diffraction.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2013); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids. Two intramolecular N—H···O hydrogen bonds are indicated by dashed lines.
	Fig. 2. Part of the packing diagram of the title compound, showing a molecular tape formed by intermolecular N—H···O and N—H···S hydrogen bonds (dashed lines).

{[(Phenylformamido)carbonyl]amino}methanethioamide top

Crystal data top

C₉H₉N₃O₂S	Z = 2
M_r = 223.25	F(000) = 232
Triclinic, P1	D_x = 1.47 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6616 (1) Å	Cell parameters from 3132 reflections
b = 7.8407 (2) Å	θ = 2.7–22.3°
c = 11.7631 (3) Å	µ = 0.30 mm⁻¹
α = 97.169 (2)°	T = 296 K
β = 94.992 (3)°	Block, yellow
γ = 101.390 (2)°	0.2 × 0.15 × 0.07 mm
V = 504.53 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	1485 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.055
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→7
T_min = 0.94, T_max = 0.97	k = −10→10
17356 measured reflections	l = −15→15
2516 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.052P)²] where P = (F_o² + 2F_c²)/3
S = 0.87	(Δ/σ)_max < 0.001
2516 reflections	Δρ_max = 0.16 e Å⁻³
152 parameters	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₉N₃O₂S	γ = 101.390 (2)°
M_r = 223.25	V = 504.53 (2) Å³
Triclinic, P1	Z = 2
a = 5.6616 (1) Å	Mo Kα radiation
b = 7.8407 (2) Å	µ = 0.30 mm⁻¹
c = 11.7631 (3) Å	T = 296 K
α = 97.169 (2)°	0.2 × 0.15 × 0.07 mm
β = 94.992 (3)°

Data collection top

Bruker SMART CCD diffractometer	2516 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1485 reflections with I > 2σ(I)
T_min = 0.94, T_max = 0.97	R_int = 0.055
17356 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	Δρ_max = 0.16 e Å⁻³
2516 reflections	Δρ_min = −0.20 e Å⁻³
152 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.0374 (3)	0.8224 (2)	−0.12506 (14)	0.0447 (4)
C2	0.2488 (3)	0.9206 (2)	−0.15393 (16)	0.0597 (5)
H2	0.3881	0.9477	−0.1014	0.072*
C3	0.2552 (4)	0.9785 (3)	−0.25952 (19)	0.0729 (6)
H3	0.398	1.0453	−0.2778	0.087*
C4	0.0539 (4)	0.9383 (3)	−0.33677 (18)	0.0723 (6)
H4	0.06	0.9763	−0.4085	0.087*
C5	−0.1598 (4)	0.8419 (3)	−0.31035 (18)	0.0753 (6)
H5	−0.2979	0.8154	−0.3636	0.09*
C6	−0.1672 (3)	0.7846 (3)	−0.20373 (16)	0.0615 (5)
H6	−0.3114	0.7203	−0.1851	0.074*
C7	0.0480 (3)	0.7661 (2)	−0.00927 (14)	0.0442 (4)
O8	0.2338 (2)	0.80629 (17)	0.05733 (11)	0.0633 (4)
N9	−0.1594 (2)	0.66558 (19)	0.02071 (12)	0.0467 (4)
H9	−0.284 (3)	0.634 (2)	−0.0281 (16)	0.054 (5)*
C10	−0.1998 (3)	0.6059 (2)	0.12532 (14)	0.0446 (4)
O11	−0.3996 (2)	0.52249 (17)	0.13780 (10)	0.0603 (4)
N12	−0.0057 (2)	0.64570 (19)	0.20766 (11)	0.0467 (4)
H12	0.131 (4)	0.707 (2)	0.1906 (17)	0.067 (6)*
C13	0.0039 (3)	0.6057 (2)	0.31929 (13)	0.0447 (4)
S14	0.27039 (8)	0.66392 (7)	0.40142 (4)	0.05930 (19)
N15	−0.1971 (3)	0.5267 (3)	0.35341 (15)	0.0646 (5)
H15A	−0.336 (4)	0.507 (2)	0.3052 (18)	0.075 (6)*
H15B	−0.199 (3)	0.486 (2)	0.4173 (18)	0.066 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0468 (9)	0.0459 (10)	0.0402 (9)	0.0048 (8)	0.0046 (7)	0.0100 (8)
C2	0.0539 (10)	0.0726 (13)	0.0505 (11)	0.0013 (9)	0.0049 (8)	0.0214 (10)
C3	0.0714 (13)	0.0858 (16)	0.0630 (14)	0.0016 (12)	0.0175 (11)	0.0337 (12)
C4	0.0944 (16)	0.0782 (15)	0.0503 (12)	0.0174 (13)	0.0138 (12)	0.0294 (11)
C5	0.0810 (15)	0.0890 (16)	0.0523 (12)	0.0069 (13)	−0.0107 (11)	0.0263 (11)
C6	0.0564 (11)	0.0714 (13)	0.0518 (12)	−0.0029 (9)	−0.0038 (9)	0.0230 (10)
C7	0.0403 (9)	0.0483 (10)	0.0410 (9)	0.0009 (7)	0.0013 (7)	0.0102 (8)
O8	0.0426 (6)	0.0882 (10)	0.0501 (7)	−0.0140 (6)	−0.0047 (6)	0.0269 (7)
N9	0.0392 (7)	0.0609 (10)	0.0353 (8)	−0.0021 (7)	−0.0023 (6)	0.0141 (7)
C10	0.0411 (9)	0.0546 (11)	0.0349 (9)	0.0016 (8)	0.0012 (7)	0.0099 (8)
O11	0.0397 (6)	0.0898 (10)	0.0432 (7)	−0.0107 (6)	−0.0017 (5)	0.0213 (6)
N12	0.0370 (7)	0.0637 (10)	0.0359 (8)	−0.0022 (7)	0.0008 (6)	0.0165 (7)
C13	0.0401 (8)	0.0588 (11)	0.0355 (9)	0.0069 (8)	0.0047 (7)	0.0129 (8)
S14	0.0402 (2)	0.0911 (4)	0.0424 (3)	0.0002 (2)	−0.00342 (18)	0.0213 (2)
N15	0.0403 (8)	0.1120 (15)	0.0414 (9)	0.0026 (9)	0.0021 (7)	0.0336 (10)

Geometric parameters (Å, º) top

C1—C6	1.377 (2)	C7—O8	1.2181 (18)
C1—C2	1.383 (2)	C7—N9	1.378 (2)
C1—C7	1.483 (2)	N9—C10	1.391 (2)
C2—C3	1.376 (3)	N9—H9	0.843 (18)
C2—H2	0.93	C10—O11	1.2205 (18)
C3—C4	1.353 (3)	C10—N12	1.3591 (19)
C3—H3	0.93	N12—C13	1.387 (2)
C4—C5	1.377 (3)	N12—H12	0.882 (19)
C4—H4	0.93	C13—N15	1.305 (2)
C5—C6	1.385 (3)	C13—S14	1.6679 (16)
C5—H5	0.93	N15—H15A	0.91 (2)
C6—H6	0.93	N15—H15B	0.85 (2)

C6—C1—C2	118.74 (16)	O8—C7—N9	120.79 (15)
C6—C1—C7	124.45 (15)	O8—C7—C1	121.33 (14)
C2—C1—C7	116.81 (15)	N9—C7—C1	117.87 (14)
C3—C2—C1	120.69 (18)	C7—N9—C10	128.80 (14)
C3—C2—H2	119.7	C7—N9—H9	119.4 (12)
C1—C2—H2	119.7	C10—N9—H9	111.8 (12)
C4—C3—C2	120.02 (18)	O11—C10—N12	124.46 (15)
C4—C3—H3	120	O11—C10—N9	119.83 (14)
C2—C3—H3	120	N12—C10—N9	115.71 (14)
C3—C4—C5	120.70 (19)	C10—N12—C13	127.81 (14)
C3—C4—H4	119.7	C10—N12—H12	117.8 (13)
C5—C4—H4	119.7	C13—N12—H12	114.4 (13)
C4—C5—C6	119.38 (19)	N15—C13—N12	117.68 (14)
C4—C5—H5	120.3	N15—C13—S14	124.41 (13)
C6—C5—H5	120.3	N12—C13—S14	117.91 (12)
C1—C6—C5	120.46 (18)	C13—N15—H15A	118.8 (13)
C1—C6—H6	119.8	C13—N15—H15B	121.9 (13)
C5—C6—H6	119.8	H15A—N15—H15B	119.1 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O11ⁱ	0.843 (18)	2.172 (18)	2.9891 (18)	163.3 (16)
N12—H12···O8	0.882 (19)	1.919 (19)	2.6171 (17)	135.0 (17)
N15—H15A···O11	0.91 (2)	1.99 (2)	2.684 (2)	132.0 (17)
N15—H15B···S14ⁱⁱ	0.85 (2)	2.58 (2)	3.4295 (17)	171.3 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O11ⁱ	0.843 (18)	2.172 (18)	2.9891 (18)	163.3 (16)
N12—H12···O8	0.882 (19)	1.919 (19)	2.6171 (17)	135.0 (17)
N15—H15A···O11	0.91 (2)	1.99 (2)	2.684 (2)	132.0 (17)
N15—H15B···S14ⁱⁱ	0.85 (2)	2.58 (2)	3.4295 (17)	171.3 (17)

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

References

Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cho, N. S., Cho, J. J., Ra, D. Y., Moon, J. H., Song, J. S. & Kang, S. K. (1996). Bull. Korean Chem. Soc. 17, 1170–1174. CAS Google Scholar
Cho, N. S., Ra, C. S., Ra, D. Y., Song, J. S. & Kang, S. K. (1996). J. Heterocycl. Chem. 33, 1201–1206. CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kang, S. K., Cho, N. S. & Jeon, M. K. (2012). Acta Cryst. E68, o395. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2013). University of Göttingen, Germany. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1327

doi:10.1107/S1600536813019983

Open

access