1-Benzoyl-2-thio­biuret

Kang, S.K.; Cho, N.S.; Jeon, M.K.

doi:10.1107/S1600536812000621

organic compounds

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Volume 68| Part 2| February 2012| Page o395

doi:10.1107/S1600536812000621

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1-Benzoyl-2-thiobiuret

Sung Kwon Kang,^a ^* Nam Sook Cho ^a and Min Kyeong Jeon ^a

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

(Received 31 December 2011; accepted 6 January 2012; online 14 January 2012)

In the title compound [systematic name: N-(carbamoylcarbamothioyl)benzamide], C₉H₉N₃O₂S, the benzoyl and terminal urea fragments adopt cisoid and transoid conformations, respectively, with respect to the S atom. The benzoyl and thiobiuret groups are almost coplanar, making a dihedral angle of 8.48 (5)°. The molecular structure is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, N—H⋯O and N—H⋯S hydrogen bonds link the molecules into a sheet parallel to the bc plane.

Related literature

For structures and reactivity of thiadiazole derivatives, see: Cho et al. (1991a ,b , 1996 ); Parkanyi et al. (1989 ). For the biological activity of thiadiazole derivatives, see: Piskala et al. (2004 ); Castro et al. (2008 ).

Experimental

Crystal data

C₉H₉N₃O₂S
M_r = 223.25
Monoclinic, C 2/c
a = 10.4583 (3) Å
b = 12.8103 (4) Å
c = 16.1830 (5) Å
β = 106.693 (1)°
V = 2076.73 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.29 × 0.24 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.911, T_max = 0.934
7908 measured reflections
1866 independent reflections
1369 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.114
S = 1.09
1866 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O14	0.89 (2)	1.82 (2)	2.617 (2)	147 (2)
N12—H12⋯O8ⁱ	0.88 (2)	2.11 (2)	2.946 (2)	158.7 (18)
N15—H15A⋯O8ⁱ	0.91 (3)	2.22 (3)	3.025 (2)	147 (2)
N15—H15A⋯S11ⁱ	0.91 (3)	2.61 (3)	3.312 (2)	134 (2)
N15—H15B⋯O14ⁱⁱ	0.87 (3)	2.08 (3)	2.943 (2)	177 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y-{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812000621/is5045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000621/is5045Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812000621/is5045Isup3.cml

checkCIF report

Comment top

On the basis of the well known analogy between a –CH=CH– group in benzenoid hydrocarbon and the bivalent sulfur –S–, in their heterocyclic sulfur-containing counterpart (e.g, thiophene is the isoelectronic analog of benzene), 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 et al., 1991a,b, 1996). Within the framework of our interest in the synthesis of novel potential antimetablites of nucleic acid components which would possess cytostatic and/or antiviral activity, we have synthesized acylonuclesides (Parkanyi et al., 1989). Derivatives of 5-amino-2H-1,2,4-thiadiazol-3-one have recently arrested the attention on the antibacterial activity, potential carcinogenicity, and kinase inhibitor activity (Piskala et al., 2004; Castro et al., 2008). The title compound, 1-benzoyl-2-thiobiuret (I), is an intermediate for the formation of the thiobiuret which is a starting material to produce 5-amino-2H-1,2,4-thiadizolin-3-one via oxidative ring closure reaction.

The dihedral angle between the benzoyl unit (C1–C7/O8 atoms) and thiobiuret group (N9–N15 atoms) is 8.48 (5)°. The carbonyl-O8 and S11 atoms are positioned syn to each other, however, carbonyl-O14 atom is anti to S11 atom (Fig. 1). The intramolecular N9—H9···O14 hydrogen bond stabilizes the molecule (Fig. 1 and Table 1). The intermolecular N—H···O and N—H···S hydrogen bonds link the molecules into a sheet parallel to the bc plane (Fig. 2 and Table 1). The carbonyl-O atoms accept two hydrogen bonds from –NH groups.

Related literature top

For structures and reactivity of thiadiazole derivatives, see: Cho et al. (1991a,b, 1996); Parkanyi et al. (1989). For the biological activity of thiadiazole derivatives, see: Piskala et al. (2004); Castro et al. (2008).

Experimental top

To warm solution of potassium thiocyanate (48.0 g, 0.49 mole) in acetone (400 ml), benzoyl chloride (48 mL, 58.2 g, 0.41 mole) was added dropwise. Immediately upon the addition of benzoyl chloride, the solution became milky white and milky yellow when the addition had been completed. The mixture was stirred for 3.5 h at 50 °C and it was left to cool to room temperature. The precipitated potassium chloride was filtered off with suction. The amber filtrate was heated to 55 °C for 5 h with urea (24.0 g, 0.40 mole), the resulting solution was cooled to room temperature and then placed in an ice bath for several hours. The solution was stirred periodically and the walls of the flask were scratched to induce crystallization. The cold mixture was filtered to give 1-benzoyl-2-thiobiuret (27.0 g, 30% yield) as a bright yellow solid. Recrystallization from acetonitrile-methanol (10:1) afforded the yellow crystals suitable for X-ray diffraction, mp 174–175 °C, ¹H NMR (DMSO-d₆, p.p.m.): 3.7 (s, 4H, NH₂ + 2NH), 8.1–8.5 (m, 5H, Ph).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

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

N-(carbamoylcarbamothioyl)benzamide top

Crystal data top

C₉H₉N₃O₂S	F(000) = 928
M_r = 223.25	D_x = 1.428 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2609 reflections
a = 10.4583 (3) Å	θ = 3.2–28.5°
b = 12.8103 (4) Å	µ = 0.30 mm⁻¹
c = 16.1830 (5) Å	T = 296 K
β = 106.693 (1)°	Block, yellow
V = 2076.73 (11) Å³	0.29 × 0.24 × 0.21 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	1369 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→8
T_min = 0.911, T_max = 0.934	k = −13→15
7908 measured reflections	l = −19→10
1866 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0586P)² + 0.3051P] where P = (F_o² + 2F_c²)/3
1866 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₉H₉N₃O₂S	V = 2076.73 (11) Å³
M_r = 223.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 10.4583 (3) Å	µ = 0.30 mm⁻¹
b = 12.8103 (4) Å	T = 296 K
c = 16.1830 (5) Å	0.29 × 0.24 × 0.21 mm
β = 106.693 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1866 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1369 reflections with I > 2σ(I)
T_min = 0.911, T_max = 0.934	R_int = 0.037
7908 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.39 e Å⁻³
1866 reflections	Δρ_min = −0.48 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.61686 (19)	0.18189 (16)	0.04253 (11)	0.0448 (5)
C2	0.5827 (2)	0.28638 (18)	0.03339 (13)	0.0552 (6)
H2	0.5944	0.3279	0.0822	0.066*
C3	0.5314 (2)	0.3297 (2)	−0.04751 (14)	0.0660 (7)
H3	0.5089	0.4001	−0.053	0.079*
C4	0.5136 (2)	0.2690 (2)	−0.11972 (13)	0.0667 (7)
H4	0.4788	0.2983	−0.1742	0.08*
C5	0.5469 (2)	0.1655 (2)	−0.11173 (13)	0.0674 (7)
H5	0.5345	0.1247	−0.1609	0.081*
C6	0.5988 (2)	0.12116 (19)	−0.03144 (12)	0.0587 (6)
H6	0.6217	0.0508	−0.0266	0.07*
C7	0.6705 (2)	0.14132 (16)	0.13236 (11)	0.0470 (5)
O8	0.67319 (17)	0.19421 (11)	0.19501 (8)	0.0635 (5)
N9	0.71681 (18)	0.03965 (14)	0.13835 (10)	0.0505 (5)
H9	0.718 (2)	0.0044 (17)	0.0909 (16)	0.069 (7)*
C10	0.7608 (2)	−0.02204 (16)	0.21000 (12)	0.0483 (5)
S11	0.77062 (8)	0.00861 (5)	0.31016 (3)	0.0797 (3)
N12	0.79787 (18)	−0.12067 (14)	0.19313 (10)	0.0521 (5)
H12	0.8182 (19)	−0.1644 (17)	0.2370 (13)	0.048 (6)*
C13	0.7888 (2)	−0.16766 (17)	0.11369 (12)	0.0487 (5)
O14	0.75791 (17)	−0.11737 (11)	0.04566 (8)	0.0623 (5)
N15	0.8183 (2)	−0.26820 (15)	0.11896 (13)	0.0567 (5)
H15A	0.821 (2)	−0.307 (2)	0.1667 (17)	0.079 (8)*
H15B	0.799 (2)	−0.3006 (19)	0.0700 (16)	0.073 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0499 (12)	0.0499 (13)	0.0359 (9)	−0.0032 (9)	0.0143 (8)	−0.0002 (8)
C2	0.0676 (14)	0.0537 (14)	0.0420 (10)	0.0019 (11)	0.0121 (10)	0.0022 (9)
C3	0.0755 (16)	0.0629 (16)	0.0553 (13)	0.0088 (12)	0.0120 (11)	0.0133 (11)
C4	0.0681 (15)	0.089 (2)	0.0405 (11)	0.0116 (14)	0.0108 (10)	0.0141 (11)
C5	0.0719 (15)	0.091 (2)	0.0353 (10)	0.0112 (14)	0.0090 (10)	−0.0051 (11)
C6	0.0728 (14)	0.0609 (14)	0.0390 (10)	0.0069 (11)	0.0106 (10)	−0.0048 (9)
C7	0.0595 (12)	0.0436 (12)	0.0370 (10)	−0.0049 (9)	0.0123 (9)	−0.0008 (8)
O8	0.1056 (13)	0.0474 (9)	0.0352 (7)	0.0069 (8)	0.0168 (7)	−0.0053 (6)
N9	0.0797 (13)	0.0404 (11)	0.0314 (8)	−0.0001 (9)	0.0160 (8)	−0.0016 (7)
C10	0.0670 (13)	0.0382 (12)	0.0379 (10)	−0.0111 (9)	0.0122 (9)	−0.0014 (8)
S11	0.1564 (8)	0.0453 (4)	0.0330 (3)	0.0008 (4)	0.0199 (3)	−0.0030 (2)
N12	0.0813 (13)	0.0401 (10)	0.0338 (8)	−0.0013 (9)	0.0148 (8)	0.0025 (7)
C13	0.0654 (13)	0.0445 (13)	0.0395 (10)	0.0004 (10)	0.0206 (9)	−0.0001 (8)
O14	0.1069 (13)	0.0474 (9)	0.0381 (7)	0.0104 (8)	0.0296 (7)	0.0046 (6)
N15	0.0886 (14)	0.0447 (12)	0.0414 (10)	0.0072 (10)	0.0262 (9)	0.0034 (8)

Geometric parameters (Å, º) top

C1—C2	1.382 (3)	C7—O8	1.213 (2)
C1—C6	1.394 (3)	C7—N9	1.383 (3)
C1—C7	1.493 (2)	N9—C10	1.369 (2)
C2—C3	1.381 (3)	N9—H9	0.89 (2)
C2—H2	0.93	C10—N12	1.372 (3)
C3—C4	1.371 (3)	C10—S11	1.642 (2)
C3—H3	0.93	N12—C13	1.398 (2)
C4—C5	1.368 (3)	N12—H12	0.88 (2)
C4—H4	0.93	C13—O14	1.236 (2)
C5—C6	1.379 (3)	C13—N15	1.321 (3)
C5—H5	0.93	N15—H15A	0.91 (3)
C6—H6	0.93	N15—H15B	0.87 (3)

C2—C1—C6	118.77 (18)	O8—C7—N9	122.94 (17)
C2—C1—C7	117.03 (17)	O8—C7—C1	122.10 (19)
C6—C1—C7	124.20 (19)	N9—C7—C1	114.96 (16)
C3—C2—C1	120.6 (2)	C10—N9—C7	128.94 (17)
C3—C2—H2	119.7	C10—N9—H9	110.5 (15)
C1—C2—H2	119.7	C7—N9—H9	120.5 (14)
C4—C3—C2	120.1 (2)	N9—C10—N12	114.10 (17)
C4—C3—H3	120	N9—C10—S11	127.48 (17)
C2—C3—H3	120	N12—C10—S11	118.40 (15)
C5—C4—C3	120.0 (2)	C10—N12—C13	129.15 (17)
C5—C4—H4	120	C10—N12—H12	116.3 (13)
C3—C4—H4	120	C13—N12—H12	113.8 (13)
C4—C5—C6	120.6 (2)	O14—C13—N15	124.21 (19)
C4—C5—H5	119.7	O14—C13—N12	121.74 (19)
C6—C5—H5	119.7	N15—C13—N12	114.05 (18)
C5—C6—C1	119.9 (2)	C13—N15—H15A	122.3 (16)
C5—C6—H6	120	C13—N15—H15B	114.8 (16)
C1—C6—H6	120	H15A—N15—H15B	117 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O14	0.89 (2)	1.82 (2)	2.617 (2)	147 (2)
N12—H12···O8ⁱ	0.88 (2)	2.11 (2)	2.946 (2)	158.7 (18)
N15—H15A···O8ⁱ	0.91 (3)	2.22 (3)	3.025 (2)	147 (2)
N15—H15A···S11ⁱ	0.91 (3)	2.61 (3)	3.312 (2)	134 (2)
N15—H15B···O14ⁱⁱ	0.87 (3)	2.08 (3)	2.943 (2)	177 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, −y−1/2, −z.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₂S
M_r	223.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	10.4583 (3), 12.8103 (4), 16.1830 (5)
β (°)	106.693 (1)
V (Å³)	2076.73 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.29 × 0.24 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.911, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	7908, 1866, 1369
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.114, 1.09
No. of reflections	1866
No. of parameters	152
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.48

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O14	0.89 (2)	1.82 (2)	2.617 (2)	147 (2)
N12—H12···O8ⁱ	0.88 (2)	2.11 (2)	2.946 (2)	158.7 (18)
N15—H15A···O8ⁱ	0.91 (3)	2.22 (3)	3.025 (2)	147 (2)
N15—H15A···S11ⁱ	0.91 (3)	2.61 (3)	3.312 (2)	134 (2)
N15—H15B···O14ⁱⁱ	0.87 (3)	2.08 (3)	2.943 (2)	177 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, −y−1/2, −z.

References

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doi:10.1107/S1600536812000621

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