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

Henley, M.J.; Schrader, A.M.; Young Jr, V.G.; Barany, G.

doi:10.1107/S2056989015016989

organic compounds

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages o782-o783

doi:10.1107/S2056989015016989

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

Matthew J. Henley,^a Alex M. Schrader,^a Victor G. Young Jr ^a and George Barany ^a ^*

^aDepartment of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA
^*Correspondence e-mail: barany@umn.edu

Edited by S. V. Lindeman, Marquette University, USA (Received 26 July 2015; accepted 10 September 2015; online 26 September 2015)

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.

Keywords: crystal structure; thiocarbamate; hydrogen bonding.

CCDC reference: 1423537

1. 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).

2. Experimental

2.1. Crystal data

C₆H₁₁NO₃S
M_r = 177.22
Triclinic, $[P \overline 1]$
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) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 173 K
0.50 × 0.10 × 0.05 mm

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

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.

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).

Supporting information

CCDC reference: 1423537

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015016989/ld2135sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016989/ld2135Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016989/ld2135Isup3.cdx

Supporting information file. DOI: 10.1107/S2056989015016989/ld2135Isup4.cml

checkCIF report

Structural commentary top

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.

Related literature top

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).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

	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.

O-Ethyl N-(ethoxycarbonyl)thiocarbamate top

Crystal data top

C₆H₁₁NO₃S	Z = 2
M_r = 177.22	F(000) = 188
Triclinic, P1	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0343P)² + 0.149P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1518 reflections	Δρ_max = 0.25 e Å⁻³
102 parameters	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₁₁NO₃S	γ = 102.360 (5)°
M_r = 177.22	V = 433.3 (3) Å³
Triclinic, P1	Z = 2
a = 4.1782 (17) Å	Mo Kα radiation
b = 9.236 (4) Å	µ = 0.34 mm⁻¹
c = 11.820 (5) Å	T = 173 K
α = 98.190 (5)°	0.50 × 0.10 × 0.05 mm
β = 98.571 (5)°

Data collection top

Siemens SMART Platform CCD diffractometer	1518 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1194 reflections with I > 2σ(I)
T_min = 0.851, T_max = 0.984	R_int = 0.037
4216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.07	Δρ_max = 0.25 e Å⁻³
1518 reflections	Δρ_min = −0.24 e Å⁻³
102 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
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.88	2.54	3.388 (2)	161.2

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We thank the University of Minnesota CHEM 5755 class and X-Ray Crystallographic Laboratory for assistance with this structure determination.

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