Ethyl N-[(benz­yloxy)thio­carbon­yl]carbamate

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

doi:10.1107/S1600536811055942

organic compounds

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Volume 68| Part 2| February 2012| Page o300

doi:10.1107/S1600536811055942

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Ethyl N-[(benzyloxy)thiocarbonyl]carbamate

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 19 December 2011; accepted 28 December 2011; online 7 January 2012)

In the title compound, C₁₁H₁₃NO₃S, the dihedral angle between the benzyl and carbamate groups is 12.67 (10)°. The S atom and the carbonyl O atom are positioned anti to each other. In the crystal, pairs of N—H⋯S hydrogen bonds link molecules into inversion dimers.

Related literature

For the synthesis and reactivity of pyrimidine and its derivatives, see: Cho et al. (1996 ); Ra et al. (1999 ). For the synthesis of oxadiazole derivatives, see: Renaut et al. (1991 ).

Experimental

Crystal data

C₁₁H₁₃NO₃S
M_r = 239.28
Triclinic, $[P \overline 1]$
a = 6.608 (4) Å
b = 7.963 (7) Å
c = 12.369 (6) Å
α = 87.451 (13)°
β = 80.725 (17)°
γ = 77.324 (18)°
V = 626.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.26 × 0.24 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.927, T_max = 0.956
13629 measured reflections
2930 independent reflections
2143 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.106
S = 1.02
2930 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 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
N11—H11⋯S10ⁱ	0.83 (2)	2.66 (2)	3.481 (2)	174.3 (17)
Symmetry code: (i) -x+2, -y+1, -z+1.

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/S1600536811055942/tk5038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055942/tk5038Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811055942/tk5038Isup3.cml

checkCIF report

Comment top

Within the framework of our systematic studies to obtain new analogues of pyrimidine and their derivatives, we reported the synthesis and reactivity of 5-amino-2H-1,2,4-thiadiazolin-3-one and 5-amino-2H-1,2,4-oxadiazolin-3-one (Cho et al., 1996; Ra et al., 1999). These compounds are 5-membered analogues of cytosine on the basis of the well known analogy between a –CH═ CH– group in a benzenoid hydrocarbon and either the divalent oxygen or sulfur in their oxygen- and sulfur-containing counterparts, respectively. On the same basis, 1,2,4-oxadiazolidine-3,5-dione is 5-membered analog of uracil. The title compound, ethyl N-(Benzyloxythiocarbonyl)carbamate (I) is an intermediate for the formation of 3-benzyloxy-1,2,4-oxadiazole-5-one and 1,2,4-oxadiazolidine-3,5-dione (Renaut et al., 1991).

In (I), the benzyl unit is almost planar, with an r.m.s. deviation of 0.020 Å from the corresponding least-squares plane defined by the seven constituent atoms. The dihedral angle between the benzyl unit (C1—C7 atoms) and the carbamate group (N11—O14 atoms) is 12.67 (10)°. The S10 and carbonyl-O13 atoms are positioned anti to each other (Fig. 1). The intermolecular N11—H···S10ⁱ [symmetry codes: (i) -x + 2, -y + 1, -z + 1] hydrogen bonds link two molecules into a centrosymmetric dimer (Fig. 2 and Table 1), which stabilizes the crystal structure.

Related literature top

For the synthesis and reactivity of pyrimidine and its derivatives, see: Cho et al. (1996); Ra et al. (1999). For the synthesis of oxadiazole derivatives, see: Renaut et al. (1991).

Experimental top

Benzyl alcohol (BnOH, 11.8 ml, 114 mmol) was added under N₂, drop-wise, at r.t., over 15 min to a solution of ethyl isothiocyanatoformate (13.54 g, 103 mmol) in EtOAc (200 ml). After refluxing for 5 h, the solvent was evaporated under reduced pressure. The crude yellow solid obtained was stirred with Et₂O (25 ml) for 2 h and placed at -18 °C overnight. The precipitated product was isolated by suction and washed with hexane. Colourless crystals of (I) were obtained from its DMSO solution by slow evaporation of the solvent at room temperature.

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 (I), showing the atom-numbering scheme and 30% probability ellipsoids.
	Fig. 2. Part of the crystal structure of (I), showing molecules linked by intermolecular N—H···S hydrogen bonds (dashed lines).

Ethyl N-[(benzyloxy)thiocarbonyl]carbamate top

Crystal data top

C₁₁H₁₃NO₃S	Z = 2
M_r = 239.28	F(000) = 252
Triclinic, P1	D_x = 1.268 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.608 (4) Å	Cell parameters from 3416 reflections
b = 7.963 (7) Å	θ = 2.6–27.5°
c = 12.369 (6) Å	µ = 0.25 mm⁻¹
α = 87.451 (13)°	T = 296 K
β = 80.725 (17)°	Block, colourless
γ = 77.324 (18)°	0.26 × 0.24 × 0.15 mm
V = 626.7 (7) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 27.7°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.927, T_max = 0.956	k = −10→10
13629 measured reflections	l = −16→16
2930 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0609P)²] where P = (F_o² + 2F_c²)/3
2930 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₁H₁₃NO₃S	γ = 77.324 (18)°
M_r = 239.28	V = 626.7 (7) Å³
Triclinic, P1	Z = 2
a = 6.608 (4) Å	Mo Kα radiation
b = 7.963 (7) Å	µ = 0.25 mm⁻¹
c = 12.369 (6) Å	T = 296 K
α = 87.451 (13)°	0.26 × 0.24 × 0.15 mm
β = 80.725 (17)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2930 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2143 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.956	R_int = 0.054
13629 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.21 e Å⁻³
2930 reflections	Δρ_min = −0.20 e Å⁻³
149 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.2095 (2)	0.85565 (18)	0.30806 (11)	0.0469 (3)
C2	0.0200 (2)	0.9802 (2)	0.33462 (13)	0.0618 (4)
H2	−0.0073	1.0385	0.4007	0.074*
C3	−0.1272 (2)	1.0161 (2)	0.26156 (15)	0.0694 (5)
H3	−0.2525	1.0962	0.2802	0.083*
C4	−0.0860 (2)	0.9320 (2)	0.16136 (15)	0.0686 (5)
H4	−0.184	0.9554	0.1135	0.082*
C5	0.1039 (2)	0.8120 (2)	0.13283 (14)	0.0638 (4)
H5	0.1332	0.7582	0.0651	0.077*
C6	0.2500 (2)	0.7728 (2)	0.20631 (13)	0.0546 (4)
H6	0.3741	0.6915	0.1875	0.065*
C7	0.3573 (2)	0.8143 (2)	0.39377 (12)	0.0578 (4)
H7A	0.3882	0.9193	0.4172	0.069*
H7B	0.292	0.7591	0.4573	0.069*
O8	0.55155 (14)	0.69857 (13)	0.34312 (7)	0.0515 (3)
C9	0.6988 (2)	0.63279 (18)	0.40536 (11)	0.0444 (3)
S10	0.68670 (6)	0.67360 (6)	0.53914 (3)	0.05991 (16)
N11	0.87013 (18)	0.52354 (16)	0.34747 (9)	0.0497 (3)
H11	0.976 (3)	0.484 (2)	0.3762 (15)	0.070 (5)*
C12	0.9048 (2)	0.47201 (19)	0.23650 (11)	0.0467 (3)
O13	0.77902 (16)	0.49923 (16)	0.17264 (8)	0.0646 (3)
O14	1.10760 (14)	0.38449 (13)	0.21449 (7)	0.0534 (3)
C15	1.1791 (2)	0.3185 (2)	0.10216 (12)	0.0613 (4)
H15A	1.1634	0.4125	0.0494	0.074*
H15B	1.097	0.2379	0.0865	0.074*
C16	1.4076 (3)	0.2296 (3)	0.09575 (16)	0.0833 (6)
H16A	1.4598	0.1837	0.0237	0.125*
H16B	1.4209	0.1377	0.1488	0.125*
H16C	1.4872	0.3109	0.1107	0.125*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0442 (7)	0.0508 (8)	0.0428 (7)	−0.0034 (6)	−0.0082 (6)	0.0039 (6)
C2	0.0559 (9)	0.0692 (10)	0.0497 (8)	0.0089 (7)	−0.0075 (7)	0.0005 (7)
C3	0.0467 (8)	0.0775 (11)	0.0721 (11)	0.0127 (8)	−0.0126 (8)	0.0073 (9)
C4	0.0535 (8)	0.0833 (12)	0.0692 (11)	−0.0047 (8)	−0.0263 (8)	0.0083 (9)
C5	0.0608 (9)	0.0748 (11)	0.0571 (9)	−0.0073 (8)	−0.0218 (7)	−0.0050 (8)
C6	0.0459 (7)	0.0597 (9)	0.0561 (9)	−0.0007 (6)	−0.0152 (6)	−0.0059 (7)
C7	0.0519 (8)	0.0648 (9)	0.0479 (8)	0.0117 (7)	−0.0128 (6)	−0.0089 (7)
O8	0.0445 (5)	0.0661 (6)	0.0383 (5)	0.0052 (4)	−0.0127 (4)	−0.0044 (4)
C9	0.0422 (7)	0.0515 (8)	0.0388 (7)	−0.0043 (6)	−0.0118 (5)	−0.0008 (6)
S10	0.0581 (2)	0.0760 (3)	0.0394 (2)	0.00832 (19)	−0.01693 (16)	−0.01291 (18)
N11	0.0424 (6)	0.0670 (8)	0.0363 (6)	0.0024 (6)	−0.0146 (5)	−0.0053 (5)
C12	0.0438 (7)	0.0568 (8)	0.0384 (7)	−0.0040 (6)	−0.0112 (5)	−0.0031 (6)
O13	0.0510 (6)	0.0927 (8)	0.0468 (6)	0.0035 (5)	−0.0210 (5)	−0.0135 (6)
O14	0.0451 (5)	0.0698 (7)	0.0399 (5)	0.0050 (5)	−0.0115 (4)	−0.0113 (5)
C15	0.0581 (8)	0.0785 (11)	0.0414 (8)	0.0012 (8)	−0.0092 (7)	−0.0127 (7)
C16	0.0579 (9)	0.1058 (15)	0.0729 (12)	0.0090 (10)	−0.0010 (9)	−0.0257 (11)

Geometric parameters (Å, º) top

C1—C6	1.407 (2)	O8—C9	1.3402 (16)
C1—C2	1.418 (2)	C9—N11	1.3830 (18)
C1—C7	1.532 (2)	C9—S10	1.6864 (16)
C2—C3	1.408 (2)	N11—C12	1.4186 (18)
C2—H2	0.93	N11—H11	0.83 (2)
C3—C4	1.394 (2)	C12—O13	1.2160 (17)
C3—H3	0.93	C12—O14	1.3586 (17)
C4—C5	1.405 (2)	O14—C15	1.4745 (17)
C4—H4	0.93	C15—C16	1.512 (2)
C5—C6	1.407 (2)	C15—H15A	0.97
C5—H5	0.93	C15—H15B	0.97
C6—H6	0.93	C16—H16A	0.96
C7—O8	1.4708 (17)	C16—H16B	0.96
C7—H7A	0.97	C16—H16C	0.96
C7—H7B	0.97

C6—C1—C2	118.77 (13)	C9—O8—C7	118.80 (11)
C6—C1—C7	123.26 (12)	O8—C9—N11	112.36 (12)
C2—C1—C7	117.95 (13)	O8—C9—S10	125.94 (10)
C3—C2—C1	120.36 (15)	N11—C9—S10	121.70 (10)
C3—C2—H2	119.8	C9—N11—C12	129.29 (11)
C1—C2—H2	119.8	C9—N11—H11	120.3 (13)
C4—C3—C2	120.30 (14)	C12—N11—H11	110.2 (13)
C4—C3—H3	119.9	O13—C12—O14	126.01 (13)
C2—C3—H3	119.9	O13—C12—N11	127.36 (12)
C3—C4—C5	119.82 (15)	O14—C12—N11	106.63 (11)
C3—C4—H4	120.1	C12—O14—C15	116.03 (10)
C5—C4—H4	120.1	O14—C15—C16	106.93 (13)
C4—C5—C6	120.23 (16)	O14—C15—H15A	110.3
C4—C5—H5	119.9	C16—C15—H15A	110.3
C6—C5—H5	119.9	O14—C15—H15B	110.3
C1—C6—C5	120.47 (13)	C16—C15—H15B	110.3
C1—C6—H6	119.8	H15A—C15—H15B	108.6
C5—C6—H6	119.8	C15—C16—H16A	109.5
O8—C7—C1	107.80 (12)	C15—C16—H16B	109.5
O8—C7—H7A	110.1	H16A—C16—H16B	109.5
C1—C7—H7A	110.1	C15—C16—H16C	109.5
O8—C7—H7B	110.1	H16A—C16—H16C	109.5
C1—C7—H7B	110.1	H16B—C16—H16C	109.5
H7A—C7—H7B	108.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···S10ⁱ	0.83 (2)	2.66 (2)	3.481 (2)	174.3 (17)

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃NO₃S
M_r	239.28
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.608 (4), 7.963 (7), 12.369 (6)
α, β, γ (°)	87.451 (13), 80.725 (17), 77.324 (18)
V (Å³)	626.7 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.26 × 0.24 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.927, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	13629, 2930, 2143
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.106, 1.02
No. of reflections	2930
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

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
N11—H11···S10ⁱ	0.83 (2)	2.66 (2)	3.481 (2)	174.3 (17)

Symmetry code: (i) −x+2, −y+1, −z+1.

References

Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. 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. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Ra, D. Y., Cho, N. S., Kang, S. K., Choi, E. S. & Suh, I. H. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 81–83. CrossRef Google Scholar
Renaut, P., Thomas, D. & Bellamy, F. D. (1991). Synthesis, pp. 265–266. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o300

doi:10.1107/S1600536811055942

Open

access