organic compounds
of 2-methylsulfanyl-1-(thiomorpholin-4-yl)ethanone
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
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
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2013); cell 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
https://doi.org/10.1107/S2056989015015418/hb7480sup1.cif
contains datablocks global, I. DOI: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
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.
(silica gel, ethyl acetate/hexane = 20/80 (v/v), Rf 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.All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.99 Å, Uiso = 1.2Ueq(C) for CH2 groups and d(C—H) = 0.98 Å, Uiso = 1.5Ueq(C) for CH3 group.
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For further information on the synthesis, see: Kim et al. (2008). For related crystal structures, see: Kim et al. (2006); Ujam et al. (2010).
Data collection: APEX2 (Bruker, 2013); cell
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).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. |
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 |
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 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 |
C7H13NOS2 | V = 924.40 (16) Å3 |
Mr = 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)° |
Bruker APEXII CCD diffractometer | 2111 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 1865 reflections with I > 2σ(I) |
Tmin = 0.890, Tmax = 0.959 | Rint = 0.026 |
8512 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.22 e Å−3 |
2111 reflections | Δρmin = −0.27 e Å−3 |
101 parameters |
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. |
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* |
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) |
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) |
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. |
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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