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

Abstract

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.

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 ▸).

Experimental  

Crystal data  

• C₇H₁₃NOS₂

• M _r = 191.30

• Monoclinic,

• a = 15.0461 (15) Å

• b = 6.1525 (6) Å

• c = 10.4751 (10) Å

• β = 107.581 (6)°

• V = 924.40 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 0.52 mm⁻¹

• T = 173 K

• 0.23 × 0.18 × 0.08 mm

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

Refinement  

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 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

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 ▸).

Supplementary Material

CCDC reference: 1419333

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C1H1BO1i	0.99	2.46	3.3490(19)	150
C6H6BO1i	0.99	2.59	3.4427(18)	144
C7H7BO1ii	0.98	2.45	3.3237(19)	148
C3H3AS2iii	0.99	2.88	3.8201(15)	159

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

S1. Comment

..

S2. Experimental

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.

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.99 Å, U_iso = 1.2U_eq(C) for CH₂ groups and d(C—H) = 0.98 Å, U_iso = 1.5U_eq(C) for CH₃ group.

Figures

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.

Crystal data

C7H13NOS2	F(000) = 408
Mr = 191.30	Dx = 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

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

Refinement

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(Fo2) + (0.0406P)2 + 0.2667P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
2111 reflections	Δρmax = 0.22 e Å−3
101 parameters	Δρmin = −0.27 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	0.57059 (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 (Ų)

	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)

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)

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.