A monoclinic polymorph of 1-benzoyl-4-thio­biuret

Kim, N.; Kim, H.; Kang, S.K.

doi:10.1107/S1600536813030250

organic compounds

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A monoclinic polymorph of 1-benzoyl-4-thiobiuret

Namhun Kim,^a Haneol Kim ^a and Sung Kwon Kang ^a ^*

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

(Received 18 October 2013; accepted 5 November 2013; online 13 November 2013)

The title compound, C₉H₉N₃O₂S, is a monoclinic (C2/c) polymorph of the previously reported triclinic structure [Kang (2013 ). Acta Cryst. E69, o1327]. The molecule is almost planar with an r.m.s. deviation of 0.069 Å from the mean plane of all non-H atoms. The benzoyl and terminal thiourea fragments adopt a transoid conformation with respect to the central carbonyl O atom. Two intramolecular N—H⋯O hydrogen bonds are present. In the crystal, N—H⋯O and N—H⋯S interactions link the molecules into zigzag chains extending along the c-axis direction.

CCDC reference: 970260

Related literature

For the biological activity of thiadiazole derivatives, see: Piskala et al. (2004 ); Castro et al. (2008 ). For the structure and reactivity of thiadiazole derivatives, see: Cho et al. (1996 ). For the structure of a thiobiuret compound, see: Kang et al. (2012 ) and of the monoclinic polymorph, see: Kang (2013).

Experimental

Crystal data

C₉H₉N₃O₂S
M_r = 223.25
Monoclinic, C 2/c
a = 14.4259 (14) Å
b = 6.6145 (6) Å
c = 21.722 (2) Å
β = 94.166 (3)°
V = 2067.2 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 296 K
0.18 × 0.12 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.96, T_max = 0.99
7756 measured reflections
1973 independent reflections
1293 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.115
S = 1.03
1973 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O11ⁱ	0.81 (3)	2.20 (3)	2.945 (3)	151 (2)
N12—H12⋯O8	0.86 (3)	1.97 (3)	2.661 (3)	136 (2)
N15—H15A⋯S14ⁱⁱ	0.98 (4)	2.41 (4)	3.358 (3)	163 (3)
N15—H15B⋯O11	0.81 (3)	2.06 (3)	2.653 (3)	130 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 970260

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813030250/lr2116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030250/lr2116Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813030250/lr2116Isup3.cml

checkCIF report

Comment top

Derivatives of 5-amino-2H-1,2,4-thiadizolin-3-one have arrested the attention on the antibacterial activity, potential carcinogenicity, and kinase inhibitor activity (Piskala et al., 2004; Castro et al., 2008). As a part of our continuous 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 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.

In (I), Fig. 1, the dihedral angle between the benzoyl unit (C1 —C7/O8 atoms, r.m.s. deviation = 0.068 Å) and thiobiuret group (N9 — N15 atoms) is 9.67 (13) °. The carbonyl-O8 and O11 atoms are positioned anti to each other, and S14 atom is also positioned anti to carbonyl-O11 atom. The molecular structure is stabilized by two intramolecular N—H···O hydrogen bonds (Fig. 1 and Table 1). In the crystal packing, the intermolecular N—H···O and N—H···S interactions link the molecules into zigzag chains extending along the c axis (Fig. 2).

Related literature top

For the biological activity of thiadiazole derivatives, see: Piskala et al. (2004); Castro et al. (2008). For the structure and reactivity of thiadiazole derivatives, see: Cho et al. (1996). For the structure of a thiobiuret compound, see: Kang et al. (2012) and of the monoclinic polymorph, see: Kang (2013).

Experimental top

Benzoyl chloride (48 ml, 58.1 g, 0.41mole) was added to warm solution of potassium thiocyanate (48.0 g, 0.49mole) 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 mole). 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. The title compound (I) was obtained after recrystallization from its acetonitrile-methanol (10: 1) solution.

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, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); 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 (I) with ellipsoids drawn at the 30% probability level . Two intramolecular N—H···O hydrogen bonds are indicated by dashed lines.
	Fig. 2. Part of the packing diagram of (I), showing molecules linked by intermolecular N—H···O and N—H···S hydrogen bonds (dashed lines).

{[(Phenylformamido)carbonyl]amino}methanethioamide top

Crystal data top

C₉H₉N₃O₂S	F(000) = 928
M_r = 223.25	D_x = 1.435 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 883 reflections
a = 14.4259 (14) Å	θ = 2.8–20.7°
b = 6.6145 (6) Å	µ = 0.30 mm⁻¹
c = 21.722 (2) Å	T = 296 K
β = 94.166 (3)°	Block, yellow
V = 2067.2 (3) Å³	0.18 × 0.12 × 0.04 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	1293 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→17
T_min = 0.96, T_max = 0.99	k = −8→3
7756 measured reflections	l = −26→14
1973 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0483P)² + 0.5497P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1973 reflections	Δρ_max = 0.21 e Å⁻³
152 parameters	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₉N₃O₂S	V = 2067.2 (3) Å³
M_r = 223.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.4259 (14) Å	µ = 0.30 mm⁻¹
b = 6.6145 (6) Å	T = 296 K
c = 21.722 (2) Å	0.18 × 0.12 × 0.04 mm
β = 94.166 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1973 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1293 reflections with I > 2σ(I)
T_min = 0.96, T_max = 0.99	R_int = 0.059
7756 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.21 e Å⁻³
1973 reflections	Δρ_min = −0.23 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	0.33533 (17)	1.0358 (4)	0.65485 (12)	0.0376 (6)
C2	0.3931 (2)	1.1557 (4)	0.69320 (13)	0.0488 (7)
H2	0.4542	1.1162	0.7031	0.059*
C3	0.3604 (2)	1.3340 (4)	0.71691 (15)	0.0589 (9)
H3	0.3994	1.4133	0.7429	0.071*
C4	0.2704 (2)	1.3943 (4)	0.70214 (14)	0.0573 (9)
H4	0.2492	1.5159	0.7174	0.069*
C5	0.2120 (2)	1.2761 (4)	0.66512 (15)	0.0563 (8)
H5	0.1508	1.3161	0.6559	0.068*
C6	0.24417 (19)	1.0959 (4)	0.64118 (13)	0.0486 (7)
H6	0.2043	1.0158	0.616	0.058*
C7	0.37532 (18)	0.8447 (4)	0.63138 (13)	0.0396 (7)
O8	0.44757 (13)	0.7726 (3)	0.65381 (9)	0.0561 (6)
N9	0.32479 (17)	0.7544 (3)	0.58270 (11)	0.0439 (6)
H9	0.2806 (18)	0.812 (4)	0.5652 (12)	0.039 (8)*
C10	0.34054 (18)	0.5751 (4)	0.55260 (13)	0.0384 (6)
O11	0.28343 (12)	0.5116 (3)	0.51289 (9)	0.0472 (5)
N12	0.42172 (15)	0.4788 (3)	0.57068 (11)	0.0393 (6)
H12	0.4561 (17)	0.535 (4)	0.6002 (12)	0.037 (8)*
C13	0.45494 (17)	0.3010 (4)	0.54659 (13)	0.0382 (7)
S14	0.55856 (5)	0.21601 (11)	0.57483 (4)	0.0510 (3)
N15	0.40313 (19)	0.2107 (4)	0.50312 (13)	0.0521 (7)
H15A	0.425 (2)	0.083 (5)	0.4869 (15)	0.086 (11)*
H15B	0.351 (2)	0.248 (5)	0.4927 (15)	0.068 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0416 (16)	0.0347 (14)	0.0363 (16)	−0.0008 (11)	0.0021 (12)	−0.0012 (12)
C2	0.0482 (18)	0.0489 (17)	0.0488 (19)	−0.0032 (13)	0.0008 (14)	−0.0116 (15)
C3	0.071 (2)	0.0495 (18)	0.056 (2)	−0.0128 (16)	0.0079 (17)	−0.0189 (16)
C4	0.076 (2)	0.0399 (17)	0.057 (2)	0.0053 (15)	0.0172 (17)	−0.0096 (15)
C5	0.058 (2)	0.0545 (19)	0.057 (2)	0.0191 (15)	0.0040 (15)	−0.0054 (16)
C6	0.0497 (18)	0.0467 (17)	0.0487 (19)	0.0032 (13)	−0.0009 (14)	−0.0070 (14)
C7	0.0392 (17)	0.0348 (14)	0.0440 (18)	0.0001 (11)	−0.0025 (13)	−0.0001 (13)
O8	0.0495 (13)	0.0491 (12)	0.0667 (15)	0.0115 (10)	−0.0165 (11)	−0.0113 (10)
N9	0.0457 (15)	0.0362 (13)	0.0476 (16)	0.0126 (11)	−0.0111 (12)	−0.0071 (11)
C10	0.0351 (15)	0.0319 (14)	0.0476 (18)	0.0022 (11)	−0.0005 (13)	−0.0022 (13)
O11	0.0416 (11)	0.0413 (11)	0.0568 (13)	0.0059 (9)	−0.0097 (10)	−0.0098 (10)
N12	0.0349 (13)	0.0330 (12)	0.0488 (16)	0.0047 (10)	−0.0054 (11)	−0.0070 (11)
C13	0.0353 (15)	0.0312 (13)	0.0486 (18)	0.0004 (11)	0.0059 (13)	−0.0012 (13)
S14	0.0368 (4)	0.0439 (4)	0.0713 (6)	0.0082 (3)	−0.0014 (4)	−0.0077 (4)
N15	0.0417 (17)	0.0421 (15)	0.071 (2)	0.0092 (12)	−0.0036 (14)	−0.0195 (13)

Geometric parameters (Å, º) top

C1—C2	1.384 (4)	C7—O8	1.216 (3)
C1—C6	1.385 (3)	C7—N9	1.376 (3)
C1—C7	1.494 (3)	N9—C10	1.381 (3)
C2—C3	1.383 (4)	N9—H9	0.81 (3)
C2—H2	0.93	C10—O11	1.223 (3)
C3—C4	1.373 (4)	C10—N12	1.366 (3)
C3—H3	0.93	N12—C13	1.386 (3)
C4—C5	1.367 (4)	N12—H12	0.86 (3)
C4—H4	0.93	C13—N15	1.306 (4)
C5—C6	1.393 (4)	C13—S14	1.671 (3)
C5—H5	0.93	N15—H15A	0.98 (4)
C6—H6	0.93	N15—H15B	0.81 (3)

C2—C1—C6	119.0 (2)	O8—C7—N9	121.9 (2)
C2—C1—C7	117.4 (2)	O8—C7—C1	122.4 (2)
C6—C1—C7	123.6 (2)	N9—C7—C1	115.7 (2)
C3—C2—C1	120.4 (3)	C7—N9—C10	129.8 (2)
C3—C2—H2	119.8	C7—N9—H9	120.5 (19)
C1—C2—H2	119.8	C10—N9—H9	109.4 (19)
C4—C3—C2	120.2 (3)	O11—C10—N12	124.2 (2)
C4—C3—H3	119.9	O11—C10—N9	120.2 (2)
C2—C3—H3	119.9	N12—C10—N9	115.6 (2)
C5—C4—C3	120.2 (3)	C10—N12—C13	126.9 (2)
C5—C4—H4	119.9	C10—N12—H12	116.6 (17)
C3—C4—H4	119.9	C13—N12—H12	116.5 (17)
C4—C5—C6	120.1 (3)	N15—C13—N12	117.7 (2)
C4—C5—H5	120	N15—C13—S14	124.1 (2)
C6—C5—H5	120	N12—C13—S14	118.1 (2)
C1—C6—C5	120.1 (3)	C13—N15—H15A	118.2 (18)
C1—C6—H6	119.9	C13—N15—H15B	122 (2)
C5—C6—H6	119.9	H15A—N15—H15B	119 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O11ⁱ	0.81 (3)	2.20 (3)	2.945 (3)	151 (2)
N12—H12···O8	0.86 (3)	1.97 (3)	2.661 (3)	136 (2)
N15—H15A···S14ⁱⁱ	0.98 (4)	2.41 (4)	3.358 (3)	163 (3)
N15—H15B···O11	0.81 (3)	2.06 (3)	2.653 (3)	130 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O11ⁱ	0.81 (3)	2.20 (3)	2.945 (3)	151 (2)
N12—H12···O8	0.86 (3)	1.97 (3)	2.661 (3)	136 (2)
N15—H15A···S14ⁱⁱ	0.98 (4)	2.41 (4)	3.358 (3)	163 (3)
N15—H15B···O11	0.81 (3)	2.06 (3)	2.653 (3)	130 (3)

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

References

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doi:10.1107/S1600536813030250

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