organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

3-(2-Amino­phenyl­sulfanyl)-1,3-di­phenyl­propan-1-one

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 27 May 2011; accepted 7 June 2011; online 18 June 2011)

In the title compound, C21H19NOS, the three aromatic rings are not coplanar, the dihedral angles between them being 84.75 (7), 88.01 (8) and 8.36 (16)°. In the crystal, two types of C—H⋯ π inter­actions, one of which is weak, and N—H⋯π inter­actions link the mol­ecules into layers parallel to the ab plane.

Related literature

For a similar structure, see: Morgant et al. (1996[Morgant, G., Labouze, X., Viossat, B., Lancelot, J.-C. & Nguyen Huy Dung (1996). Acta Cryst. C52, 923-925.]).

[Scheme 1]

Experimental

Crystal data
  • C21H19NOS

  • Mr = 333.43

  • Monoclinic, P 21 /n

  • a = 11.1741 (16) Å

  • b = 5.6788 (8) Å

  • c = 27.308 (4) Å

  • β = 95.266 (2)°

  • V = 1725.5 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.19 mm−1

  • T = 296 K

  • 0.18 × 0.07 × 0.02 mm

Data collection
  • Bruker APEX-II CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.966, Tmax = 0.996

  • 7303 measured reflections

  • 3195 independent reflections

  • 1784 reflections with I > 2σ(I)

  • Rint = 0.065

Refinement
  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.101

  • S = 0.95

  • 3195 reflections

  • 223 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C10–C15 and C16–C21 rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1BCg1i 0.91 (3) 2.55 (3) 3.400 (3) 155 (2)
C12—H12⋯Cg1ii 0.93 2.86 3.581 (4) 135
C14—H14⋯Cg2i 0.93 2.93 3.587 (3) 128
Symmetry codes: (i) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem, 1, 189-191.]); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The title compound (Fig. 1) was obtained during the synthesis of benzothiazepines II in an ionic liquid media (Fig. 2) and is suggested to be the intermediate compound which upon subsequent cyclization would form the seven-membered thiazepine ring. The three aromatic rings of the molecule are non-planar as are in the structure of a related compound (Morgant et al., 1996). The dihedral angles between the phenyl rings plane are 84.75 (7)° (between C1/C6 and C10/C15), 88.01 (8) ° (between C1/C6 and C16/C21) and 8.36 (16) ° (between C10/C15 and C16/C21). The amino hydrogen, H1B, is involved in an N—H··· π interaction (Table 1). In the crystal, the N—H···π interactions connect the adjacent molecules into infinite chains along the b axis. The one-dimensional link is supplemented by weak C14—H14··· π interactions. The chains are connected into two-dimensional-arrays parallel to the ab plane via C12—H12··· π interactions (Table 1).

Related literature top

For a similar structure, see: Morgant et al. (1996).

Experimental top

The title compound was synthesized as illustrated in Fig. 2. A mixture of the chalcone (0.208 g, 1 mmol), o-aminothiophenol (0.088 ml, 1.1 mmol) and ionic liquid, IL, (0.1 g) was heated at 80°C for 80 min. The two products, I & II, were extracted with diethyether and separated by column chromatography (hexane: ethylacatate, 8:2). The second fraction, containing (I), was evaporated and the resulting solid was recrystallized from ethanol at room temperature to give the colorless crystals of the title compound.

Refinement top

The C-bound hydrogen atoms were placed at calculated positions and refined as riding atoms with C—H distances of 0.93 (phenyl), 0.97 (methylene) and 0.98 (methine) Å. The N-bound hydrogen atoms were located in a difference Fourier map and refined freely. For all hydrogen atoms Uiso(H) were set to1.2 Ueq(carrier atom).

Computing details top

Data collection: APEX2 (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: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at 30% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. Synthetic route to compounds I and II.
3-(2-Aminophenylsulfanyl)-1,3-diphenylpropan-1-one top
Crystal data top
C21H19NOSF(000) = 704
Mr = 333.43Dx = 1.284 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 713 reflections
a = 11.1741 (16) Åθ = 3.0–20.6°
b = 5.6788 (8) ŵ = 0.19 mm1
c = 27.308 (4) ÅT = 296 K
β = 95.266 (2)°Lath, colorless
V = 1725.5 (4) Å30.18 × 0.07 × 0.02 mm
Z = 4
Data collection top
Bruker APEX-II CCD
diffractometer
3195 independent reflections
Radiation source: fine-focus sealed tube1784 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
ϕ and ω scansθmax = 25.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1213
Tmin = 0.966, Tmax = 0.996k = 65
7303 measured reflectionsl = 2933
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 0.95 w = 1/[σ2(Fo2) + (0.0336P)2]
where P = (Fo2 + 2Fc2)/3
3195 reflections(Δ/σ)max < 0.001
223 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C21H19NOSV = 1725.5 (4) Å3
Mr = 333.43Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.1741 (16) ŵ = 0.19 mm1
b = 5.6788 (8) ÅT = 296 K
c = 27.308 (4) Å0.18 × 0.07 × 0.02 mm
β = 95.266 (2)°
Data collection top
Bruker APEX-II CCD
diffractometer
3195 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1784 reflections with I > 2σ(I)
Tmin = 0.966, Tmax = 0.996Rint = 0.065
7303 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 0.95Δρmax = 0.17 e Å3
3195 reflectionsΔρmin = 0.23 e Å3
223 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.

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) top
xyzUiso*/Ueq
S10.80339 (6)0.87951 (14)0.18814 (3)0.0447 (2)
O11.0501 (2)0.3126 (4)0.13496 (8)0.0647 (7)
N10.6375 (2)0.4530 (5)0.18086 (10)0.0544 (8)
H1A0.684 (3)0.492 (5)0.2078 (11)0.065*
H1B0.576 (3)0.353 (5)0.1859 (10)0.065*
C11.0977 (3)0.7137 (6)0.03620 (11)0.0486 (8)
H11.04850.83840.04360.058*
C21.1576 (3)0.7203 (6)0.00593 (11)0.0583 (9)
H21.14830.84970.02680.070*
C31.2307 (3)0.5382 (7)0.01713 (11)0.0576 (10)
H31.26980.54290.04570.069*
C41.2458 (3)0.3503 (6)0.01372 (11)0.0567 (9)
H41.29700.22850.00650.068*
C51.1859 (2)0.3390 (5)0.05554 (10)0.0479 (8)
H51.19570.20840.07610.057*
C61.1110 (2)0.5215 (5)0.06716 (10)0.0372 (7)
C71.0446 (3)0.4961 (6)0.11240 (11)0.0421 (8)
C80.9699 (2)0.7008 (5)0.12804 (9)0.0407 (8)
H8A0.90490.73010.10270.049*
H8B1.01980.84090.13100.049*
C90.9174 (2)0.6565 (5)0.17669 (9)0.0389 (7)
H90.87890.50130.17530.047*
C101.0071 (2)0.6649 (5)0.22161 (9)0.0330 (7)
C111.0841 (2)0.8534 (5)0.23096 (10)0.0397 (7)
H111.08410.97550.20830.048*
C121.1609 (2)0.8630 (6)0.27341 (11)0.0484 (8)
H121.21200.99120.27920.058*
C131.1620 (3)0.6835 (6)0.30718 (11)0.0511 (9)
H131.21420.68890.33570.061*
C141.0852 (3)0.4954 (6)0.29848 (11)0.0502 (9)
H141.08500.37430.32140.060*
C151.0089 (2)0.4857 (5)0.25623 (10)0.0436 (8)
H150.95770.35740.25070.052*
C160.6144 (2)0.6174 (5)0.14430 (10)0.0378 (7)
C170.5196 (3)0.5843 (6)0.10811 (11)0.0507 (9)
H170.47280.44900.10840.061*
C180.4949 (3)0.7500 (7)0.07200 (11)0.0577 (9)
H180.43070.72630.04830.069*
C190.5635 (3)0.9510 (6)0.07023 (11)0.0559 (9)
H190.54541.06360.04600.067*
C200.6588 (3)0.9817 (6)0.10486 (10)0.0465 (8)
H200.70621.11570.10350.056*
C210.6864 (2)0.8180 (5)0.14189 (9)0.0338 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0366 (4)0.0552 (6)0.0419 (5)0.0055 (4)0.0013 (3)0.0142 (4)
O10.0848 (17)0.0482 (16)0.0659 (16)0.0140 (14)0.0324 (13)0.0095 (12)
N10.0539 (18)0.055 (2)0.0551 (19)0.0092 (15)0.0070 (14)0.0093 (15)
C10.0494 (19)0.046 (2)0.051 (2)0.0072 (17)0.0098 (16)0.0029 (16)
C20.066 (2)0.062 (3)0.049 (2)0.007 (2)0.0129 (18)0.0073 (17)
C30.056 (2)0.076 (3)0.043 (2)0.011 (2)0.0160 (17)0.011 (2)
C40.054 (2)0.064 (3)0.054 (2)0.005 (2)0.0158 (17)0.0135 (19)
C50.0485 (18)0.048 (2)0.0475 (19)0.0047 (17)0.0076 (15)0.0042 (15)
C60.0360 (16)0.041 (2)0.0340 (17)0.0026 (16)0.0022 (13)0.0057 (15)
C70.0443 (18)0.041 (2)0.0407 (19)0.0012 (17)0.0034 (14)0.0034 (16)
C80.0407 (17)0.045 (2)0.0359 (17)0.0067 (16)0.0029 (14)0.0011 (14)
C90.0352 (16)0.0400 (19)0.0422 (18)0.0033 (15)0.0077 (14)0.0058 (14)
C100.0278 (15)0.039 (2)0.0333 (17)0.0005 (15)0.0076 (12)0.0016 (14)
C110.0399 (17)0.040 (2)0.0396 (18)0.0015 (17)0.0046 (14)0.0029 (14)
C120.0359 (17)0.055 (2)0.054 (2)0.0087 (17)0.0011 (15)0.0067 (18)
C130.0375 (18)0.080 (3)0.0357 (18)0.0085 (19)0.0028 (15)0.0006 (19)
C140.0458 (19)0.060 (2)0.046 (2)0.0026 (18)0.0103 (16)0.0154 (16)
C150.0386 (17)0.043 (2)0.050 (2)0.0052 (16)0.0071 (16)0.0022 (16)
C160.0350 (16)0.045 (2)0.0346 (17)0.0033 (17)0.0080 (14)0.0009 (15)
C170.0433 (18)0.059 (2)0.050 (2)0.0076 (18)0.0053 (16)0.0097 (18)
C180.047 (2)0.081 (3)0.043 (2)0.003 (2)0.0101 (16)0.0156 (19)
C190.062 (2)0.066 (3)0.039 (2)0.015 (2)0.0013 (17)0.0046 (16)
C200.0484 (19)0.049 (2)0.0423 (19)0.0011 (17)0.0056 (16)0.0006 (16)
C210.0306 (15)0.0382 (19)0.0334 (17)0.0019 (15)0.0069 (13)0.0054 (14)
Geometric parameters (Å, º) top
S1—C211.767 (3)C9—H90.9800
S1—C91.843 (3)C10—C111.382 (3)
O1—C71.209 (3)C10—C151.388 (4)
N1—C161.374 (4)C11—C121.379 (4)
N1—H1A0.89 (3)C11—H110.9300
N1—H1B0.91 (3)C12—C131.374 (4)
C1—C61.380 (4)C12—H120.9300
C1—C21.384 (4)C13—C141.377 (4)
C1—H10.9300C13—H130.9300
C2—C31.370 (4)C14—C151.371 (4)
C2—H20.9300C14—H140.9300
C3—C41.360 (4)C15—H150.9300
C3—H30.9300C16—C171.393 (4)
C4—C51.377 (4)C16—C211.400 (4)
C4—H40.9300C17—C181.373 (4)
C5—C61.387 (4)C17—H170.9300
C5—H50.9300C18—C191.378 (4)
C6—C71.505 (4)C18—H180.9300
C7—C81.515 (4)C19—C201.369 (4)
C8—C91.522 (3)C19—H190.9300
C8—H8A0.9700C20—C211.387 (4)
C8—H8B0.9700C20—H200.9300
C9—C101.512 (3)
C21—S1—C9102.73 (12)C11—C10—C15118.2 (3)
C16—N1—H1A119 (2)C11—C10—C9121.9 (2)
C16—N1—H1B116.2 (19)C15—C10—C9119.8 (3)
H1A—N1—H1B115 (3)C12—C11—C10121.0 (3)
C6—C1—C2119.8 (3)C12—C11—H11119.5
C6—C1—H1120.1C10—C11—H11119.5
C2—C1—H1120.1C13—C12—C11120.1 (3)
C3—C2—C1120.6 (3)C13—C12—H12120.0
C3—C2—H2119.7C11—C12—H12120.0
C1—C2—H2119.7C12—C13—C14119.5 (3)
C4—C3—C2119.8 (3)C12—C13—H13120.2
C4—C3—H3120.1C14—C13—H13120.2
C2—C3—H3120.1C15—C14—C13120.4 (3)
C3—C4—C5120.5 (3)C15—C14—H14119.8
C3—C4—H4119.7C13—C14—H14119.8
C5—C4—H4119.7C14—C15—C10120.8 (3)
C4—C5—C6120.3 (3)C14—C15—H15119.6
C4—C5—H5119.9C10—C15—H15119.6
C6—C5—H5119.9N1—C16—C17120.2 (3)
C1—C6—C5118.9 (3)N1—C16—C21121.1 (3)
C1—C6—C7123.0 (3)C17—C16—C21118.7 (3)
C5—C6—C7118.0 (3)C18—C17—C16120.5 (3)
O1—C7—C6119.7 (3)C18—C17—H17119.8
O1—C7—C8121.4 (3)C16—C17—H17119.8
C6—C7—C8118.9 (3)C17—C18—C19121.1 (3)
C7—C8—C9112.7 (2)C17—C18—H18119.4
C7—C8—H8A109.1C19—C18—H18119.4
C9—C8—H8A109.1C20—C19—C18118.8 (3)
C7—C8—H8B109.1C20—C19—H19120.6
C9—C8—H8B109.1C18—C19—H19120.6
H8A—C8—H8B107.8C19—C20—C21121.7 (3)
C10—C9—C8115.0 (2)C19—C20—H20119.1
C10—C9—S1104.94 (17)C21—C20—H20119.1
C8—C9—S1111.25 (19)C20—C21—C16119.3 (3)
C10—C9—H9108.5C20—C21—S1119.3 (2)
C8—C9—H9108.5C16—C21—S1121.2 (2)
S1—C9—H9108.5
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C10–C15 and C16–C21 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cg1i0.91 (3)2.55 (3)3.400 (3)155 (2)
C12—H12···Cg1ii0.932.863.581 (4)135
C14—H14···Cg2i0.932.933.587 (3)128
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+5/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC21H19NOS
Mr333.43
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)11.1741 (16), 5.6788 (8), 27.308 (4)
β (°) 95.266 (2)
V3)1725.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.19
Crystal size (mm)0.18 × 0.07 × 0.02
Data collection
DiffractometerBruker APEX-II CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.966, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
7303, 3195, 1784
Rint0.065
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.101, 0.95
No. of reflections3195
No. of parameters223
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C10–C15 and C16–C21 rings, respectively.
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cg1i0.91 (3)2.55 (3)3.400 (3)155 (2)
C12—H12···Cg1ii0.932.863.581 (4)135
C14—H14···Cg2i0.932.933.587 (3)128
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+5/2, y+1/2, z+1/2.
 

Acknowledgements

The authors would like to thank the Ministry of Science, Technology and Innovation (MOSTI) for funding this study (Science fund grant No. 53–02-03–1059).

References

First citationBarbour, L. J. (2001). J. Supramol. Chem, 1, 189–191.  CrossRef CAS
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationMorgant, G., Labouze, X., Viossat, B., Lancelot, J.-C. & Nguyen Huy Dung (1996). Acta Cryst. C52, 923–925.
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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