organic papers
Acta Cryst.(2005). E61, o295±o297 doi:10.1107/S1600536805000449 Liuet al. C12H13NO2S
o295
Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
4-(Benzoylthiocarbonyl)morpholine
Wei-Wei Liu,a,bYi-Zhi Li,b
Ling-Dong Kongcand Hong-Wen
Hub*
aDepartment of Chemical Engineering, Huaihai
Institute of Technology, Lianyungang 222005, People's Republic of China,bCoordination
Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People's Republic of China, andcSchool of Life Science, Nanjing University,
Nanjing 210093, People's Republic of China
Correspondence e-mail: llyyjz@nju.edu.cn
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.004 AÊ
Rfactor = 0.057
wRfactor = 0.108
Data-to-parameter ratio = 15.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C12H13NO2S, was synthesized from a mixture of morpholine, acetophenone and elemental sulfur dissolved in pyridine. In the crystal structure, the molecules
interact through weak intermolecular CÐH O/S
inter-actions, resulting in a three-dimensional network.
Comment
Thioamides have higher chemical activities than their corre-sponding amides in many chemical reactions as a result of the electronegativity of the S atom. Moreover, they can be synthesized and puri®ed easily (Sosnickiet al., 2001), which is an important consideration for industrial applications. Recently, thioamides have been used as fungistatic reagents (Matysiaket al., 2000) and chain terminators in Sanger±DNA sequencing reactions (Schwarzeret al., 2001). The Willgerodt± Kindler reaction is a more convenient procedure for preparing thioamides than other routes (Kawaiet al., 1999).
We report here the result of the reaction between morpholine, acetophenone and elemental sulfur, which led to the title compound, (I) (Fig. 1). The geometric parameters for (I) (Table 1) are normal.
There are ®ve weak intermolecular CÐH O/S
inter-actions in the crystal structure (Table 2), as shown in Fig. 2, which connect molecules, resulting in a three-dimensional network (Fig. 3).
Received 4 January 2005 Accepted 5 January 2005 Online 15 January 2005
Figure 1
Experimental
A mixture of elemental sulfur (2.6 g, 0.08 mol), morpholine (6.1 ml, 0.07 mol) and acetophenone (6 g, 0.05 mol) in anhydrous pyridine (30 ml) was re¯uxed with stirring until the acetophenone had almost disappeared (monitored by thin-layer chromatography). To the cooled mixture was added iced water, and then the organic phase was extracted with toluene. The solvent was removedin vacuoand the title compound was separated on a column of silica gel with petro-leum ether/ethyl acetate as eluants. Yellow crystals of (I) suitable for X-ray structure analysis were obtained by recrystallizing the crude product from acetone.
Crystal data
C12H13NO2S Mr= 235.29 Monoclinic,P21/c a= 10.715 (2) AÊ b= 9.200 (1) AÊ c= 11.692 (2) AÊ
= 92.02 (4)
V= 1151.8 (3) AÊ3 Z= 4
Dx= 1.357 Mg mÿ3 MoKradiation
Cell parameters from 551 re¯ections
= 2.8±18.8
= 0.27 mmÿ1 T= 293 (2) K Block, yellow 0.300.200.20 mm
Data collection
Bruker SMART APEX CCD diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin= 0.94,Tmax= 0.95 6029 measured re¯ections
2264 independent re¯ections 1578 re¯ections withI> 2(I) Rint= 0.044
max= 26.0 h=ÿ13!10 k=ÿ11!11 l=ÿ14!13
Refinement
Re®nement onF2 R[F2> 2(F2)] = 0.057 wR(F2) = 0.108 S= 1.10 2264 re¯ections 145 parameters
H-atom parameters constrained w= 1/[2(F
o2) + (0.04P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.32 e AÊÿ3
min=ÿ0.26 e AÊÿ3
Table 1
Selected torsion angles ().
O2ÐC7ÐC8ÐN1 ÿ83.7 (3) C1ÐC7ÐC8ÐN1 99.0 (3) O2ÐC7ÐC8ÐS1 93.9 (2) C1ÐC7ÐC8ÐS1 ÿ83.4 (2)
S1ÐC8ÐN1ÐC9 ÿ1.5 (4) C7ÐC8ÐN1ÐC12 ÿ7.1 (4) S1ÐC8ÐN1ÐC12 175.67 (19)
Table 2
Hydrogen-bond geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
C3ÐH3 S1i 0.93 2.90 3.781 (3) 159 C12ÐH12a O2ii 0.97 2.59 3.401 (3) 141 C11ÐH11a S1iii 0.97 2.97 3.890 (3) 159 C11ÐH11b O2iv 0.97 2.54 3.500 (3) 170 C9ÐH9b O1v 0.97 2.57 3.467 (3) 154 Symmetry codes: (i) x;ÿ1
2ÿy;12z; (ii) 1ÿx;ÿy;ÿz; (iii) x;12ÿy;12z; (iv)
1ÿx;1
2y;12ÿz; (v) 1ÿx;1ÿy;ÿz.
All H atoms were placed in calculated positions, with CÐH distances 0.93±0.97 AÊ, and included in the re®nement as riding, with
Uiso(H) = 1.2Ueq(carrier atom).
Data collection:SMART(Bruker, 2000); cell re®nement:SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.
This work was supported by the Education Department, Natural Science Foundation of Jiangsu Province, People's Republic of China (grant No. 03 KJB150009).
References
Bruker (2000).SMART(Version 5.625),SAINT(Version 6.01),SHELXTL (Version 6.10) andSADABS(Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
organic papers
o296
Liuet al. C12H13NO2S Acta Cryst.(2005). E61, o295±o297Figure 3
The three-dimensional structure of (I). Dashed lines indicate the weak intermolecular CÐH O/S interactions. H atoms not involved in the CÐ H O/S bonds have been omitted for clarity.
Figure 2
Weak intermolecular interactions (dashed lines) in (I) [symmetry codes: (i)x,ÿ1
2ÿy,12+z; (ii) 1ÿx,ÿy,ÿz; (iii)x,12ÿy,12+z; (iv) 1ÿx,12+y, 1
2ÿz; (v) 1ÿx, 1ÿy,ÿz]. H atoms not involved in the CÐH O/S
Kawai, Y., Kanbara, T. & Hasegawa, K. (1999).J. Polym. Sci. Polym. Chem.37, 1737±1740.
Matysiak, J., Niewiadomy, A., Macik-Niewiadomy, G. & Kornillowicz, T. (2000).Eur. J. Med. Chem.35, 393±404.
Schwarzer, K., Wojczewski, C. & Engels, J. W. (2001).Nucleosides Nucleotides Nucleic Acids,20, 879±882.
Sosnicki, J. G., Jagodzinski, T. S. & Hansen, P. E. (2001).Tetrahedron,57, 8705± 8718.
organic papers
supporting information
sup-1
Acta Cryst. (2005). E61, o295–o297
supporting information
Acta Cryst. (2005). E61, o295–o297 [https://doi.org/10.1107/S1600536805000449]
4-(Benzoylthiocarbonyl)morpholine
Wei-Wei Liu, Yi-Zhi Li, Ling-Dong Kong and Hong-Wen Hu
4-(Benzoylthiocarbonyl)morpholine
Crystal data
C12H13NO2S
Mr = 235.29
Monoclinic, P21/c
Hall symbol: -P 2ybc a = 10.715 (2) Å b = 9.200 (1) Å c = 11.692 (2) Å β = 92.02 (4)° V = 1151.8 (3) Å3
Z = 4
F(000) = 496 Dx = 1.357 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 551 reflections θ = 2.8–18.8°
µ = 0.27 mm−1
T = 293 K Block, yellow
0.30 × 0.20 × 0.20 mm
Data collection
Bruker Smart Apex CCD diffractometer
Radiation source: sealed tube Graphite monochromator φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin = 0.94, Tmax = 0.95
6029 measured reflections 2264 independent reflections 1578 reflections with I > 2σ(I) Rint = 0.044
θmax = 26.0°, θmin = 1.9°
h = −13→10
k = −11→11
l = −14→13
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.057
wR(F2) = 0.108
S = 1.10 2264 reflections 145 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.04P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.32 e Å−3
supporting information
sup-2
Acta Cryst. (2005). E61, o295–o297
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.
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 9.6516 (0.0058) x + 0.8893 (0.0096) y - 5.3186 (0.0121) z = 3.4255 (0.0042)
* -0.2050 (0.0017) N1 * 0.2544 (0.0017) O1 * 0.2096 (0.0019) C9 * -0.2351 (0.0019) C10 * -0.2347 (0.0019) C11 * 0.2108 (0.0018) C12
Rms deviation of fitted atoms = 0.2256
7.2822 (0.0088) x + 3.8415 (0.0095) y + 6.7677 (0.0101) z = 2.5477 (0.0029) Angle to previous plane (with approximate e.s.d.) = 66.60 (0.07)
* -0.0081 (0.0017) C1 * 0.0016 (0.0018) C2 * 0.0080 (0.0019) C3 * -0.0112 (0.0020) C4 * 0.0047 (0.0019) C5 * 0.0050 (0.0017) C6
Rms deviation of fitted atoms = 0.0071
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
C1 0.2035 (2) −0.0571 (2) 0.18876 (19) 0.0365 (6)
C2 0.2186 (3) −0.1866 (3) 0.2474 (2) 0.0509 (7)
H2 0.2767 −0.2543 0.2236 0.061*
C3 0.1474 (3) −0.2164 (3) 0.3418 (2) 0.0577 (8)
H3 0.1584 −0.3032 0.3818 0.069*
C4 0.0613 (3) −0.1172 (4) 0.3754 (2) 0.0607 (8)
H4 0.0116 −0.1379 0.4370 0.073*
C5 0.0474 (3) 0.0126 (3) 0.3190 (2) 0.0538 (8)
H5 −0.0099 0.0806 0.3436 0.065*
C6 0.1182 (2) 0.0424 (3) 0.2259 (2) 0.0430 (6)
H6 0.1083 0.1306 0.1878 0.052*
C7 0.2821 (2) −0.0276 (2) 0.0897 (2) 0.0361 (6)
C8 0.2632 (2) 0.1145 (3) 0.0261 (2) 0.0416 (6)
C9 0.3381 (3) 0.3597 (3) −0.0098 (2) 0.0465 (7)
H9A 0.2675 0.3618 −0.0640 0.056*
H9B 0.4138 0.3712 −0.0520 0.056*
C10 0.3273 (3) 0.4822 (3) 0.0746 (2) 0.0546 (8)
H10A 0.3293 0.5742 0.0342 0.065*
H10B 0.2477 0.4752 0.1113 0.065*
C11 0.4203 (3) 0.3455 (3) 0.2205 (2) 0.0503 (7)
H11A 0.3409 0.3381 0.2574 0.060*
H11B 0.4860 0.3447 0.2796 0.060*
C12 0.4357 (2) 0.2174 (3) 0.1433 (2) 0.0422 (6)
H12A 0.5183 0.2192 0.1119 0.051*
H12B 0.4276 0.1282 0.1867 0.051*
N1 0.34113 (19) 0.2213 (2) 0.05054 (16) 0.0427 (5)
supporting information
sup-3
Acta Cryst. (2005). E61, o295–o297
S1 0.14719 (7) 0.11239 (7) −0.07143 (6) 0.0479 (2)
O2 0.35731 (18) −0.11459 (19) 0.05521 (15) 0.0600 (5)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0436 (15) 0.0291 (13) 0.0363 (14) −0.0077 (11) −0.0049 (12) −0.0009 (11)
C2 0.0613 (19) 0.0327 (14) 0.0580 (18) −0.0031 (13) −0.0064 (15) 0.0015 (13)
C3 0.078 (2) 0.0390 (16) 0.0551 (19) −0.0130 (17) −0.0127 (17) 0.0102 (14)
C4 0.072 (2) 0.070 (2) 0.0401 (16) −0.0240 (19) 0.0013 (15) 0.0070 (16)
C5 0.0570 (19) 0.0593 (18) 0.0454 (17) −0.0033 (15) 0.0047 (15) −0.0003 (14)
C6 0.0539 (17) 0.0413 (14) 0.0336 (15) −0.0037 (13) −0.0040 (13) −0.0002 (12)
C7 0.0411 (15) 0.0276 (13) 0.0388 (15) 0.0007 (11) −0.0083 (12) −0.0072 (11)
C8 0.0475 (16) 0.0392 (14) 0.0379 (14) −0.0057 (13) −0.0033 (12) −0.0016 (12)
C9 0.0519 (17) 0.0475 (16) 0.0396 (15) −0.0202 (13) −0.0074 (13) 0.0087 (12)
C10 0.0590 (19) 0.0396 (16) 0.0648 (19) −0.0093 (14) −0.0021 (17) 0.0033 (14)
C11 0.0535 (18) 0.0582 (18) 0.0386 (15) −0.0076 (14) −0.0085 (13) −0.0048 (13)
C12 0.0396 (15) 0.0446 (15) 0.0418 (15) −0.0055 (13) −0.0082 (12) −0.0010 (12)
N1 0.0477 (13) 0.0405 (13) 0.0396 (13) −0.0093 (11) −0.0045 (11) −0.0007 (10)
O1 0.0693 (14) 0.0460 (12) 0.0550 (12) −0.0182 (10) −0.0078 (11) −0.0073 (9)
S1 0.0530 (4) 0.0484 (4) 0.0412 (4) −0.0115 (4) −0.0136 (3) 0.0016 (3)
O2 0.0668 (13) 0.0499 (11) 0.0636 (13) 0.0172 (11) 0.0080 (11) −0.0070 (10)
Geometric parameters (Å, º)
C1—C6 1.374 (3) C8—S1 1.657 (3)
C1—C2 1.382 (3) C9—N1 1.455 (3)
C1—C7 1.482 (3) C9—C10 1.505 (4)
C2—C3 1.391 (3) C9—H9A 0.9700
C2—H2 0.9300 C9—H9B 0.9700
C3—C4 1.366 (4) C10—O1 1.410 (3)
C3—H3 0.9300 C10—H10A 0.9700
C4—C5 1.369 (4) C10—H10B 0.9700
C4—H4 0.9300 C11—O1 1.424 (3)
C5—C6 1.375 (3) C11—C12 1.497 (3)
C5—H5 0.9300 C11—H11A 0.9700
C6—H6 0.9300 C11—H11B 0.9700
C7—O2 1.214 (3) C12—N1 1.459 (3)
C7—C8 1.514 (3) C12—H12A 0.9700
C8—N1 1.314 (3) C12—H12B 0.9700
C6—C1—C2 119.1 (2) C10—C9—H9A 109.7
C6—C1—C7 121.9 (2) N1—C9—H9B 109.7
C2—C1—C7 119.1 (2) C10—C9—H9B 109.7
C1—C2—C3 120.4 (3) H9A—C9—H9B 108.2
C1—C2—H2 119.8 O1—C10—C9 111.6 (2)
C3—C2—H2 119.8 O1—C10—H10A 109.3
supporting information
sup-4
Acta Cryst. (2005). E61, o295–o297
C4—C3—H3 120.3 O1—C10—H10B 109.3
C2—C3—H3 120.3 C9—C10—H10B 109.3
C3—C4—C5 120.5 (3) H10A—C10—H10B 108.0
C3—C4—H4 119.8 O1—C11—C12 111.5 (2)
C5—C4—H4 119.8 O1—C11—H11A 109.3
C4—C5—C6 120.1 (3) C12—C11—H11A 109.3
C4—C5—H5 120.0 O1—C11—H11B 109.3
C6—C5—H5 120.0 C12—C11—H11B 109.3
C1—C6—C5 120.5 (2) H11A—C11—H11B 108.0
C1—C6—H6 119.7 N1—C12—C11 109.9 (2)
C5—C6—H6 119.7 N1—C12—H12A 109.7
O2—C7—C1 122.8 (2) C11—C12—H12A 109.7
O2—C7—C8 119.0 (2) N1—C12—H12B 109.7
C1—C7—C8 118.2 (2) C11—C12—H12B 109.7
N1—C8—C7 117.8 (2) H12A—C12—H12B 108.2
N1—C8—S1 127.9 (2) C8—N1—C9 123.1 (2)
C7—C8—S1 114.32 (18) C8—N1—C12 124.2 (2)
N1—C9—C10 109.8 (2) C9—N1—C12 112.63 (19)
N1—C9—H9A 109.7 C10—O1—C11 109.61 (19)
C6—C1—C2—C3 0.8 (4) O2—C7—C8—S1 93.9 (2)
C7—C1—C2—C3 179.0 (2) C1—C7—C8—S1 −83.4 (2)
C1—C2—C3—C4 0.8 (4) N1—C9—C10—O1 56.3 (3)
C2—C3—C4—C5 −2.0 (4) O1—C11—C12—N1 −56.1 (3)
C3—C4—C5—C6 1.7 (4) C7—C8—N1—C9 175.8 (2)
C2—C1—C6—C5 −1.1 (4) S1—C8—N1—C9 −1.5 (4)
C7—C1—C6—C5 −179.3 (2) C7—C8—N1—C12 −7.1 (4)
C4—C5—C6—C1 −0.1 (4) S1—C8—N1—C12 175.67 (19)
C6—C1—C7—O2 −179.5 (2) C10—C9—N1—C8 125.2 (3)
C2—C1—C7—O2 2.3 (3) C10—C9—N1—C12 −52.2 (3)
C6—C1—C7—C8 −2.3 (3) C11—C12—N1—C8 −124.9 (3)
C2—C1—C7—C8 179.5 (2) C11—C12—N1—C9 52.5 (3)
O2—C7—C8—N1 −83.7 (3) C9—C10—O1—C11 −60.5 (3)
C1—C7—C8—N1 99.0 (3) C12—C11—O1—C10 60.5 (3)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C3—H3···S1i 0.93 2.90 3.781 (3) 159
C12—H12A···O2ii 0.97 2.59 3.401 (3) 141
C11—H11A···S1iii 0.97 2.97 3.890 (3) 159
C11—H11B···O2iv 0.97 2.54 3.500 (3) 170
C9—H9B···O1v 0.97 2.57 3.467 (3) 154