Crystal structure of O-ethyl N-(eth­oxy­carbon­yl)thio­carbamate

Abstract

The title compound, C₆H₁₁NO₃S, provides entries to novel carbamoyl disulfanes and related compounds of inter­est to our laboratory. The atoms of the central O(C=S)N(C=O)O fragment have an r.m.s. deviation of 0.1077 Å from the respective least-squares plane. While several conformational orientations are conceivable, the crystal structure shows only the one in which the carbonyl and the thio­carbonyl moieties are anti to each other across the central conjugated C—N—C moiety. Pairs of 2.54 Å N—H⋯S=C hydrogen bonds between adjacent mol­ecules form centrosymmetric dimers in the crystal.

Related literature  

A variety of methods to prepare the title compound and/or similar structures have been reported; see Delitsch (1874 ▸); Atkins et al. (1973 ▸); Barany (1977 ▸, and references therein); Vallejos et al. (2009 ▸, and references therein); Barany et al. (2015 ▸, and references therein). For closely related structures, see CSD (Groom & Allen, 2014 ▸) refcodes: BORBOA (Vallejos et al., 2009 ▸); GAPPAQ (Kang et al., 2012 ▸). For applications of the title compound in inter­esting chemistry, see: Atkins et al. (1973 ▸); Barany & Merrifield (1977 ▸); Shen et al. (1998 ▸, and references therein); Barany et al. (2006 ▸, 2015 ▸); Vallejos et al. (2009 ▸).

Experimental  

Crystal data  

• C₆H₁₁NO₃S

• M _r = 177.22

• Triclinic,

• a = 4.1782 (17) Å

• b = 9.236 (4) Å

• c = 11.820 (5) Å

• α = 98.190 (5)°

• β = 98.571 (5)°

• γ = 102.360 (5)°

• V = 433.3 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.34 mm⁻¹

• T = 173 K

• 0.50 × 0.10 × 0.05 mm

Data collection  

• Siemens SMART Platform CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▸) T _min = 0.851, T _max = 0.984

• 4216 measured reflections

• 1518 independent reflections

• 1194 reflections with I > 2σ(I)

• R _int = 0.037

Refinement  

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.087

• S = 1.07

• 1518 reflections

• 102 parameters

• H-atom parameters constrained

• Δρ_max = 0.25 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

CCDC reference: 1423537

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1AS1i	0.88	2.54	3.388(2)	161

Symmetry code: (i) .

supplementary crystallographic information

S1. Structural commentary

The title compound, O-ethyl N-(eth­oxy­carbonyl)­thio­carbamate (1), C₆H₁₁NO₃S, CAS registry # 5585-23-9, also known as (N-eth­oxy­thio­carbonyl)­urethane, was of inter­est to a multifaceted organosulfur research program that includes among its goals the development of amino protecting groups removable under mild conditions (Barany, 1977; Barany & Merrifield; 1977; Barany et al., 2006, Barany et al., 2015). Specifically, we have shown that reaction of 1 with (chloro­carbonyl)­sulfenyl chloride gives rise to the novel (chloro­carbonyl)(N-eth­oxy­carbonyl­carbamoyl)disulfane, rather than the expected putative N-eth­oxy­carbonyl-1,2,4-di­thia­zolidine-3,5-dione (Barany et al., 2015). Variations in reaction conditions and/or the nature of sulfenyl chlorides that react with 1 result in additional unusual structures which model previously uncharacterized inter­mediates in the mechanisms of reactions that successfully elaborate N-alkyl-1,2,4-di­thia­zolidine-3,5-dione heterocycles. Thio­carbamate 1 is also useful as an entry to pharmaceutically relevant heterocycles (Atkins et al., 1973), as an additive in the purification of pyrite (Shen et al., 1998), and as a precursor to compounds of inter­est to the agrochemical industry (Vallejos et al., 2009).

X-ray quality crystals of 1 were readily obtained after bulk purification (recrystallization from hot hexane, about 7 mL/g).

All molecular parameters of 1 are within expected ranges. Ignoring the ethyl groups, the central fragment of 1 has a r.m.s. deviation of 0.1077 Å from the least squares plane [i.e., the plane consisting of atoms O1, C1, S1, N1, C2, O2, O3]. The largest deviation of any torsion angle from 0 or 180° is 11.5 (3)° for C2—N1—C1—O1. Although there are multiple theoretically stable conformations of 1 (Vallejos et al., 2009), the molecule uniquely assumes the conformation where the carbonyl and the thio­carbonyl moieties are anti to each other across the central C–N–C moiety.

In the crystal, pairs of inter­molecular N–H···S=C hydrogen bonds between two adjacent molecules form centrosymmetric dimers (see Figure 2).

A search of the Cambridge Structural Database (CSD; Version 5.36, update of November 2014; Groom & Allen, 2014) revealed two similar structures, O-benzyl N-(eth­oxy­carbonyl)­thio­carbamate (2) (Kang et al., 2012) [i.e., BnO(C=S)NH(C=O)OEt], and O-ethyl N-(meth­oxy­carbonyl)­thio­carbamate (3) (Vallejos et al., 2009) [i.e., EtO(C=S)NH(C=O)OMe]. Inter­estingly, both 2 and 3 assume the same conformation as 1, where the thio­carbonyl and carbonyl moieties are anti to each other across the C–N–C moiety. In all three structures, similar length N–H···S=C hydrogen bonds form between adjacent molecules.

Figures

Fig. 1.

Crystallographic structure of O-ethyl N-(ethoxycarbonyl)thiocarbamate (1) showing 50% probability displacement ellipsoids with all non-hydrogen atoms labeled and numbered.

Fig. 2.

View of crystal packing down the a-axis, with hydrogen bonds highlighted and atoms involved in hydrogen bonding labeled and numbered.

Crystal data

C6H11NO3S	Z = 2
Mr = 177.22	F(000) = 188
Triclinic, P1	Dx = 1.358 Mg m−3
a = 4.1782 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.236 (4) Å	Cell parameters from 1518 reflections
c = 11.820 (5) Å	θ = 2.3–25.1°
α = 98.190 (5)°	µ = 0.34 mm−1
β = 98.571 (5)°	T = 173 K
γ = 102.360 (5)°	Thin plates, colorless
V = 433.3 (3) Å3	0.50 × 0.10 × 0.05 mm

Data collection

Siemens SMART Platform CCD diffractometer	1518 independent reflections
Radiation source: normal-focus sealed tube	1194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
area detector, ω scans per phi	θmax = 25.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −4→4
Tmin = 0.851, Tmax = 0.984	k = −10→11
4216 measured reflections	l = −14→14

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0343P)2 + 0.149P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
1518 reflections	Δρmax = 0.25 e Å−3
102 parameters	Δρmin = −0.24 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.08610 (15)	0.30032 (7)	0.46293 (5)	0.0321 (2)
O1	0.0371 (4)	0.25383 (16)	0.67694 (13)	0.0305 (4)
O2	0.5131 (4)	0.40638 (17)	0.85405 (13)	0.0346 (4)
O3	0.8025 (4)	0.61521 (17)	0.80409 (13)	0.0331 (4)
N1	0.4306 (5)	0.4541 (2)	0.66587 (16)	0.0300 (5)
H1A	0.5091	0.5211	0.6247	0.036*
C1	0.1822 (5)	0.3340 (2)	0.60663 (19)	0.0254 (5)
C2	0.5755 (6)	0.4835 (3)	0.78377 (19)	0.0273 (5)
C3	−0.2164 (6)	0.1158 (2)	0.6252 (2)	0.0304 (6)
H3A	−0.1188	0.0435	0.5797	0.037*
H3B	−0.4004	0.1381	0.5728	0.037*
C4	−0.3422 (6)	0.0515 (3)	0.7242 (2)	0.0402 (6)
H4A	−0.5151	−0.0417	0.6936	0.060*
H4B	−0.4363	0.1245	0.7687	0.060*
H4C	−0.1576	0.0295	0.7750	0.060*
C5	0.9980 (6)	0.6597 (3)	0.92221 (18)	0.0301 (6)
H5A	1.1317	0.5862	0.9389	0.036*
H5B	0.8494	0.6647	0.9798	0.036*
C6	1.2223 (7)	0.8123 (3)	0.9279 (2)	0.0413 (7)
H6A	1.3678	0.8447	1.0045	0.062*
H6B	1.0865	0.8850	0.9153	0.062*
H6C	1.3588	0.8068	0.8675	0.062*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0366 (4)	0.0312 (4)	0.0232 (3)	0.0006 (3)	−0.0001 (2)	0.0045 (2)
O1	0.0307 (9)	0.0285 (9)	0.0258 (9)	−0.0040 (7)	0.0025 (7)	0.0037 (7)
O2	0.0404 (10)	0.0341 (9)	0.0241 (9)	−0.0032 (8)	0.0031 (7)	0.0103 (8)
O3	0.0388 (10)	0.0286 (9)	0.0228 (8)	−0.0064 (8)	−0.0022 (7)	0.0054 (7)
N1	0.0348 (11)	0.0271 (10)	0.0229 (10)	−0.0034 (9)	0.0018 (9)	0.0082 (8)
C1	0.0242 (12)	0.0229 (12)	0.0281 (12)	0.0053 (10)	0.0024 (10)	0.0048 (10)
C2	0.0302 (13)	0.0290 (13)	0.0222 (12)	0.0064 (11)	0.0056 (10)	0.0037 (10)
C3	0.0296 (13)	0.0245 (12)	0.0325 (13)	0.0004 (10)	0.0023 (11)	0.0027 (10)
C4	0.0386 (15)	0.0377 (15)	0.0406 (15)	−0.0014 (12)	0.0064 (12)	0.0121 (12)
C5	0.0317 (13)	0.0327 (13)	0.0202 (12)	0.0004 (11)	−0.0021 (10)	0.0047 (10)
C6	0.0447 (15)	0.0356 (15)	0.0337 (14)	−0.0040 (12)	−0.0033 (12)	0.0055 (11)

Geometric parameters (Å, º)

S1—C1	1.654 (2)	C3—H3B	0.9900
O1—C1	1.319 (3)	C4—H4A	0.9800
O1—C3	1.459 (3)	C4—H4B	0.9800
O2—C2	1.191 (3)	C4—H4C	0.9800
O3—C2	1.338 (3)	C5—C6	1.503 (3)
O3—C5	1.462 (3)	C5—H5A	0.9900
N1—C1	1.366 (3)	C5—H5B	0.9900
N1—C2	1.397 (3)	C6—H6A	0.9800
N1—H1A	0.8800	C6—H6B	0.9800
C3—C4	1.498 (3)	C6—H6C	0.9800
C3—H3A	0.9900
C1—O1—C3	118.15 (17)	C3—C4—H4B	109.5
C2—O3—C5	115.13 (16)	H4A—C4—H4B	109.5
C1—N1—C2	128.02 (19)	C3—C4—H4C	109.5
C1—N1—H1A	116.0	H4A—C4—H4C	109.5
C2—N1—H1A	116.0	H4B—C4—H4C	109.5
O1—C1—N1	112.26 (19)	O3—C5—C6	106.43 (18)
O1—C1—S1	126.16 (16)	O3—C5—H5A	110.4
N1—C1—S1	121.57 (17)	C6—C5—H5A	110.4
O2—C2—O3	125.7 (2)	O3—C5—H5B	110.4
O2—C2—N1	127.0 (2)	C6—C5—H5B	110.4
O3—C2—N1	107.34 (18)	H5A—C5—H5B	108.6
O1—C3—C4	106.44 (18)	C5—C6—H6A	109.5
O1—C3—H3A	110.4	C5—C6—H6B	109.5
C4—C3—H3A	110.4	H6A—C6—H6B	109.5
O1—C3—H3B	110.4	C5—C6—H6C	109.5
C4—C3—H3B	110.4	H6A—C6—H6C	109.5
H3A—C3—H3B	108.6	H6B—C6—H6C	109.5
C3—C4—H4A	109.5
C3—O1—C1—N1	−175.56 (18)	C5—O3—C2—N1	−175.86 (18)
C3—O1—C1—S1	4.8 (3)	C1—N1—C2—O2	2.0 (4)
C2—N1—C1—O1	11.6 (3)	C1—N1—C2—O3	−178.5 (2)
C2—N1—C1—S1	−168.77 (18)	C1—O1—C3—C4	−178.52 (19)
C5—O3—C2—O2	3.6 (3)	C2—O3—C5—C6	−177.19 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1i	0.88	2.54	3.388 (2)	161

Symmetry code: (i) −x+1, −y+1, −z+1.