Crystal structure of 2-methyl­sulfanyl-1-(thio­morpholin-4-yl)­ethanone

Kang, G.; Kim, J.; Kwon, E.; Kim, T.H.

doi:10.1107/S2056989015015418

organic compounds

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ISSN: 2056-9890

Volume 71| Part 9| September 2015| Page o679

https://doi.org/10.1107/S2056989015015418

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Crystal structure of 2-methylsulfanyl-1-(thiomorpholin-4-yl)ethanone

Gihaeng Kang,^a Jineun Kim,^a ^* Eunjin Kwon ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang, National University, Jinju 52828, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 August 2015; accepted 18 August 2015; online 22 August 2015)

In the title compound, C₇H₁₃NOS₂, the thiomorpholine ring adopts a chair conformation and the bond-angle sum at the N atom is 360°. The dihedral angle between the amide group and the thiomorpholine ring (all atoms) is 36.48 (12)°. In the crystal, C—H⋯O and C—H⋯S hydrogen bonds link adjacent molecules, forming two-dimensional networks extending parellel to the (011) plane.

Keywords: crystal structure; thiomorpholine; hydrogen bonding.

CCDC reference: 1419333

1. Related literature

For further information on the synthesis, see: Kim et al. (2008 ). For related crystal structures, see: Kim et al. (2006 ); Ujam et al. (2010 ).

2. Experimental

2.1. Crystal data

C₇H₁₃NOS₂
M_r = 191.30
Monoclinic, P 2₁ /c
a = 15.0461 (15) Å
b = 6.1525 (6) Å
c = 10.4751 (10) Å
β = 107.581 (6)°
V = 924.40 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 173 K
0.23 × 0.18 × 0.08 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.890, T_max = 0.959
8512 measured reflections
2111 independent reflections
1865 reflections with I > 2σ(I)
R_int = 0.026

2.3. Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.078
S = 1.05
2111 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O1ⁱ	0.99	2.46	3.3490 (19)	150
C6—H6B⋯O1ⁱ	0.99	2.59	3.4427 (18)	144
C7—H7B⋯O1ⁱⁱ	0.98	2.45	3.3237 (19)	148
C3—H3A⋯S2ⁱⁱⁱ	0.99	2.88	3.8201 (15)	159
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) x, y-1, z.

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1419333

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015015418/hb7480sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015418/hb7480Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015015418/hb7480Isup3.cml

checkCIF report

Comment top

Related literature top

For further information on the synthesis, see: Kim et al. (2008). For related crystal structures, see: Kim et al. (2006); Ujam et al. (2010).

Experimental top

Thionyl chloride (2.38 g, 20.0 mmol) was added dropwise to 2-methylthioacetic acid (2.12 g, 20.0 mmol) in the pesence of triethylamine (2.02 g, 20.0 mmol) in chloroform. The mixture was refluxed for 2 h and cooled down to room temperature. Then, thiomorpholine (2.38 g, 20.0 mmol) and triethylamine (2.02 g, 20.0 mmol) in chloroform were added dropwise to the resulting acid chloride solution, cooled by salt and ice water. The solution was stirred for 2 h, and then water was added. Organic layer was collected and water layer was extracted with chloroform. The combined organic layers dried with anhydrous sodium sulfate were evaporated to give crude oil. Column chromatography (silica gel, ethyl acetate/hexane = 20/80 (v/v), R_f 0.1) gave pure title compound (3.42 g, 89%) (Kim et al., 2008). Slow evaporation of a solution in acetone/ethyl acetate gave colourless blocks.

Structure description top

For further information on the synthesis, see: Kim et al. (2008). For related crystal structures, see: Kim et al. (2006); Ujam et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing viewed along the b axis. The intermolecular C—H···O and C—H···S hydrogen bonds are shown as dashed lines.

2-Methylsulfanyl-1-(thiomorpholin-4-yl)ethanone top

Crystal data top

C₇H₁₃NOS₂	F(000) = 408
M_r = 191.30	D_x = 1.375 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.0461 (15) Å	Cell parameters from 4186 reflections
b = 6.1525 (6) Å	θ = 2.8–27.5°
c = 10.4751 (10) Å	µ = 0.52 mm⁻¹
β = 107.581 (6)°	T = 173 K
V = 924.40 (16) Å³	Block, colourless
Z = 4	0.23 × 0.18 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	1865 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.026
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 27.5°, θ_min = 2.8°
T_min = 0.890, T_max = 0.959	h = −19→19
8512 measured reflections	k = −7→7
2111 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0406P)² + 0.2667P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2111 reflections	Δρ_max = 0.22 e Å⁻³
101 parameters	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₇H₁₃NOS₂	V = 924.40 (16) Å³
M_r = 191.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.0461 (15) Å	µ = 0.52 mm⁻¹
b = 6.1525 (6) Å	T = 173 K
c = 10.4751 (10) Å	0.23 × 0.18 × 0.08 mm
β = 107.581 (6)°

Data collection top

Bruker APEXII CCD diffractometer	2111 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1865 reflections with I > 2σ(I)
T_min = 0.890, T_max = 0.959	R_int = 0.026
8512 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
2111 reflections	Δρ_min = −0.27 e Å⁻³
101 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	0.57059 (2)	0.35556 (6)	0.41078 (4)	0.03060 (12)
S2	0.87043 (3)	1.06954 (6)	0.40092 (4)	0.03528 (13)
O1	0.82963 (8)	0.59419 (17)	0.21785 (11)	0.0333 (2)
N1	0.72025 (8)	0.62668 (19)	0.32412 (12)	0.0264 (3)
C1	0.68637 (10)	0.7095 (2)	0.43112 (15)	0.0315 (3)
H1A	0.6300	0.7989	0.3920	0.038*
H1B	0.7346	0.8037	0.4909	0.038*
C2	0.66298 (11)	0.5254 (3)	0.51228 (15)	0.0325 (3)
H2A	0.6437	0.5870	0.5871	0.039*
H2B	0.7193	0.4357	0.5510	0.039*
C3	0.62268 (10)	0.2963 (2)	0.28028 (15)	0.0280 (3)
H3A	0.6779	0.2023	0.3172	0.034*
H3B	0.5774	0.2148	0.2078	0.034*
C4	0.65213 (10)	0.5000 (2)	0.22214 (14)	0.0296 (3)
H4A	0.6795	0.4586	0.1507	0.036*
H4B	0.5965	0.5909	0.1812	0.036*
C5	0.80749 (9)	0.6585 (2)	0.31488 (14)	0.0243 (3)
C6	0.87815 (10)	0.7787 (2)	0.42581 (15)	0.0297 (3)
H6A	0.9416	0.7294	0.4300	0.036*
H6B	0.8679	0.7434	0.5125	0.036*
C7	0.91981 (12)	1.0968 (3)	0.26585 (18)	0.0385 (4)
H7A	0.9862	1.0593	0.2975	0.058*
H7B	0.9127	1.2471	0.2334	0.058*
H7C	0.8876	0.9988	0.1928	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0255 (2)	0.0330 (2)	0.0357 (2)	−0.00719 (13)	0.01283 (16)	−0.00026 (15)
S2	0.0262 (2)	0.0305 (2)	0.0515 (3)	−0.00455 (14)	0.01529 (18)	−0.01097 (16)
O1	0.0347 (6)	0.0363 (5)	0.0344 (6)	−0.0013 (4)	0.0187 (5)	−0.0022 (4)
N1	0.0262 (6)	0.0290 (6)	0.0263 (6)	−0.0077 (5)	0.0115 (5)	−0.0052 (5)
C1	0.0313 (8)	0.0309 (7)	0.0369 (8)	−0.0085 (6)	0.0173 (7)	−0.0101 (6)
C2	0.0323 (8)	0.0403 (8)	0.0279 (8)	−0.0093 (6)	0.0134 (6)	−0.0064 (6)
C3	0.0251 (7)	0.0268 (7)	0.0325 (8)	−0.0050 (5)	0.0092 (6)	−0.0058 (6)
C4	0.0288 (7)	0.0341 (7)	0.0248 (7)	−0.0081 (6)	0.0065 (6)	−0.0028 (6)
C5	0.0251 (7)	0.0212 (6)	0.0278 (7)	0.0011 (5)	0.0099 (6)	0.0051 (5)
C6	0.0229 (7)	0.0349 (7)	0.0300 (8)	−0.0034 (6)	0.0059 (6)	0.0037 (6)
C7	0.0374 (9)	0.0309 (8)	0.0490 (10)	−0.0021 (6)	0.0157 (8)	0.0058 (7)

Geometric parameters (Å, º) top

S1—C2	1.8061 (15)	C2—H2B	0.9900
S1—C3	1.8065 (14)	C3—C4	1.517 (2)
S2—C7	1.7935 (17)	C3—H3A	0.9900
S2—C6	1.8067 (16)	C3—H3B	0.9900
O1—C5	1.2267 (17)	C4—H4A	0.9900
N1—C5	1.3592 (17)	C4—H4B	0.9900
N1—C1	1.4563 (17)	C5—C6	1.511 (2)
N1—C4	1.4622 (18)	C6—H6A	0.9900
C1—C2	1.520 (2)	C6—H6B	0.9900
C1—H1A	0.9900	C7—H7A	0.9800
C1—H1B	0.9900	C7—H7B	0.9800
C2—H2A	0.9900	C7—H7C	0.9800

C2—S1—C3	97.45 (6)	H3A—C3—H3B	107.8
C7—S2—C6	100.51 (7)	N1—C4—C3	111.87 (12)
C5—N1—C1	125.07 (12)	N1—C4—H4A	109.2
C5—N1—C4	120.24 (11)	C3—C4—H4A	109.2
C1—N1—C4	114.68 (11)	N1—C4—H4B	109.2
N1—C1—C2	111.34 (12)	C3—C4—H4B	109.2
N1—C1—H1A	109.4	H4A—C4—H4B	107.9
C2—C1—H1A	109.4	O1—C5—N1	121.49 (13)
N1—C1—H1B	109.4	O1—C5—C6	119.42 (12)
C2—C1—H1B	109.4	N1—C5—C6	119.09 (12)
H1A—C1—H1B	108.0	C5—C6—S2	111.99 (10)
C1—C2—S1	111.64 (11)	C5—C6—H6A	109.2
C1—C2—H2A	109.3	S2—C6—H6A	109.2
S1—C2—H2A	109.3	C5—C6—H6B	109.2
C1—C2—H2B	109.3	S2—C6—H6B	109.2
S1—C2—H2B	109.3	H6A—C6—H6B	107.9
H2A—C2—H2B	108.0	S2—C7—H7A	109.5
C4—C3—S1	112.52 (10)	S2—C7—H7B	109.5
C4—C3—H3A	109.1	H7A—C7—H7B	109.5
S1—C3—H3A	109.1	S2—C7—H7C	109.5
C4—C3—H3B	109.1	H7A—C7—H7C	109.5
S1—C3—H3B	109.1	H7B—C7—H7C	109.5

C5—N1—C1—C2	−115.63 (15)	C1—N1—C5—O1	−175.84 (13)
C4—N1—C1—C2	64.06 (16)	C4—N1—C5—O1	4.5 (2)
N1—C1—C2—S1	−62.22 (15)	C1—N1—C5—C6	3.2 (2)
C3—S1—C2—C1	53.57 (12)	C4—N1—C5—C6	−176.45 (12)
C2—S1—C3—C4	−52.50 (12)	O1—C5—C6—S2	92.67 (14)
C5—N1—C4—C3	117.12 (14)	N1—C5—C6—S2	−86.42 (13)
C1—N1—C4—C3	−62.59 (16)	C7—S2—C6—C5	−73.01 (11)
S1—C3—C4—N1	59.54 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.99	2.46	3.3490 (19)	150
C6—H6B···O1ⁱ	0.99	2.59	3.4427 (18)	144
C7—H7B···O1ⁱⁱ	0.98	2.45	3.3237 (19)	148
C3—H3A···S2ⁱⁱⁱ	0.99	2.88	3.8201 (15)	159

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.99	2.46	3.3490 (19)	150
C6—H6B···O1ⁱ	0.99	2.59	3.4427 (18)	144
C7—H7B···O1ⁱⁱ	0.98	2.45	3.3237 (19)	148
C3—H3A···S2ⁱⁱⁱ	0.99	2.88	3.8201 (15)	159

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2014R1A1A4A01009105).

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