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

Yaeghoobi, M.; Khaledi, H.; Abdullah, Z.; Abd.Rahman, N.

doi:10.1107/S1600536811022112

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1693

doi:10.1107/S1600536811022112

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

Marzieh Yaeghoobi,^a Hamid Khaledi,^a ^* Zanariah Abdullah ^a and Noorsaadah Abd.Rahman ^a

^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 ).

Experimental

Crystal data

C₂₁H₁₉NOS
M_r = 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 ) T_min = 0.966, T_max = 0.996
7303 measured reflections
3195 independent reflections
1784 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.17 e Å⁻³
Δρ_min = −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	D⋯A	D—H⋯A
N1—H1B⋯Cg1ⁱ	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 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536811022112/go2015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022112/go2015Isup2.hkl

checkCIF report

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.

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

	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.
	Fig. 2. Synthetic route to compounds I and II.

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

Crystal data top

C₂₁H₁₉NOS	F(000) = 704
M_r = 333.43	D_x = 1.284 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 713 reflections
a = 11.1741 (16) Å	θ = 3.0–20.6°
b = 5.6788 (8) Å	µ = 0.19 mm⁻¹
c = 27.308 (4) Å	T = 296 K
β = 95.266 (2)°	Lath, colorless
V = 1725.5 (4) Å³	0.18 × 0.07 × 0.02 mm
Z = 4

Data collection top

Bruker APEX-II CCD diffractometer	3195 independent reflections
Radiation source: fine-focus sealed tube	1784 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
T_min = 0.966, T_max = 0.996	k = −6→5
7303 measured reflections	l = −29→33

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ²(F_o²) + (0.0336P)²] where P = (F_o² + 2F_c²)/3
3195 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₁H₁₉NOS	V = 1725.5 (4) Å³
M_r = 333.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.1741 (16) Å	µ = 0.19 mm⁻¹
b = 5.6788 (8) Å	T = 296 K
c = 27.308 (4) Å	0.18 × 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)
T_min = 0.966, T_max = 0.996	R_int = 0.065
7303 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.17 e Å⁻³
3195 reflections	Δρ_min = −0.23 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.80339 (6)	0.87951 (14)	0.18814 (3)	0.0447 (2)
O1	1.0501 (2)	0.3126 (4)	0.13496 (8)	0.0647 (7)
N1	0.6375 (2)	0.4530 (5)	0.18086 (10)	0.0544 (8)
H1A	0.684 (3)	0.492 (5)	0.2078 (11)	0.065*
H1B	0.576 (3)	0.353 (5)	0.1859 (10)	0.065*
C1	1.0977 (3)	0.7137 (6)	0.03620 (11)	0.0486 (8)
H1	1.0485	0.8384	0.0436	0.058*
C2	1.1576 (3)	0.7203 (6)	−0.00593 (11)	0.0583 (9)
H2	1.1483	0.8497	−0.0268	0.070*
C3	1.2307 (3)	0.5382 (7)	−0.01713 (11)	0.0576 (10)
H3	1.2698	0.5429	−0.0457	0.069*
C4	1.2458 (3)	0.3503 (6)	0.01372 (11)	0.0567 (9)
H4	1.2970	0.2285	0.0065	0.068*
C5	1.1859 (2)	0.3390 (5)	0.05554 (10)	0.0479 (8)
H5	1.1957	0.2084	0.0761	0.057*
C6	1.1110 (2)	0.5215 (5)	0.06716 (10)	0.0372 (7)
C7	1.0446 (3)	0.4961 (6)	0.11240 (11)	0.0421 (8)
C8	0.9699 (2)	0.7008 (5)	0.12804 (9)	0.0407 (8)
H8A	0.9049	0.7301	0.1027	0.049*
H8B	1.0198	0.8409	0.1310	0.049*
C9	0.9174 (2)	0.6565 (5)	0.17669 (9)	0.0389 (7)
H9	0.8789	0.5013	0.1753	0.047*
C10	1.0071 (2)	0.6649 (5)	0.22161 (9)	0.0330 (7)
C11	1.0841 (2)	0.8534 (5)	0.23096 (10)	0.0397 (7)
H11	1.0841	0.9755	0.2083	0.048*
C12	1.1609 (2)	0.8630 (6)	0.27341 (11)	0.0484 (8)
H12	1.2120	0.9912	0.2792	0.058*
C13	1.1620 (3)	0.6835 (6)	0.30718 (11)	0.0511 (9)
H13	1.2142	0.6889	0.3357	0.061*
C14	1.0852 (3)	0.4954 (6)	0.29848 (11)	0.0502 (9)
H14	1.0850	0.3743	0.3214	0.060*
C15	1.0089 (2)	0.4857 (5)	0.25623 (10)	0.0436 (8)
H15	0.9577	0.3574	0.2507	0.052*
C16	0.6144 (2)	0.6174 (5)	0.14430 (10)	0.0378 (7)
C17	0.5196 (3)	0.5843 (6)	0.10811 (11)	0.0507 (9)
H17	0.4728	0.4490	0.1084	0.061*
C18	0.4949 (3)	0.7500 (7)	0.07200 (11)	0.0577 (9)
H18	0.4307	0.7263	0.0483	0.069*
C19	0.5635 (3)	0.9510 (6)	0.07023 (11)	0.0559 (9)
H19	0.5454	1.0636	0.0460	0.067*
C20	0.6588 (3)	0.9817 (6)	0.10486 (10)	0.0465 (8)
H20	0.7062	1.1157	0.1035	0.056*
C21	0.6864 (2)	0.8180 (5)	0.14189 (9)	0.0338 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0366 (4)	0.0552 (6)	0.0419 (5)	0.0055 (4)	0.0013 (3)	−0.0142 (4)
O1	0.0848 (17)	0.0482 (16)	0.0659 (16)	0.0140 (14)	0.0324 (13)	0.0095 (12)
N1	0.0539 (18)	0.055 (2)	0.0551 (19)	−0.0092 (15)	0.0070 (14)	0.0093 (15)
C1	0.0494 (19)	0.046 (2)	0.051 (2)	0.0072 (17)	0.0098 (16)	−0.0029 (16)
C2	0.066 (2)	0.062 (3)	0.049 (2)	−0.007 (2)	0.0129 (18)	0.0073 (17)
C3	0.056 (2)	0.076 (3)	0.043 (2)	−0.011 (2)	0.0160 (17)	−0.011 (2)
C4	0.054 (2)	0.064 (3)	0.054 (2)	0.005 (2)	0.0158 (17)	−0.0135 (19)
C5	0.0485 (18)	0.048 (2)	0.0475 (19)	0.0047 (17)	0.0076 (15)	−0.0042 (15)
C6	0.0360 (16)	0.041 (2)	0.0340 (17)	−0.0026 (16)	0.0022 (13)	−0.0057 (15)
C7	0.0443 (18)	0.041 (2)	0.0407 (19)	0.0012 (17)	0.0034 (14)	−0.0034 (16)
C8	0.0407 (17)	0.045 (2)	0.0359 (17)	0.0067 (16)	0.0029 (14)	−0.0011 (14)
C9	0.0352 (16)	0.0400 (19)	0.0422 (18)	0.0033 (15)	0.0077 (14)	−0.0058 (14)
C10	0.0278 (15)	0.039 (2)	0.0333 (17)	−0.0005 (15)	0.0076 (12)	−0.0016 (14)
C11	0.0399 (17)	0.040 (2)	0.0396 (18)	0.0015 (17)	0.0046 (14)	0.0029 (14)
C12	0.0359 (17)	0.055 (2)	0.054 (2)	−0.0087 (17)	0.0011 (15)	−0.0067 (18)
C13	0.0375 (18)	0.080 (3)	0.0357 (18)	0.0085 (19)	0.0028 (15)	−0.0006 (19)
C14	0.0458 (19)	0.060 (2)	0.046 (2)	0.0026 (18)	0.0103 (16)	0.0154 (16)
C15	0.0386 (17)	0.043 (2)	0.050 (2)	−0.0052 (16)	0.0071 (16)	0.0022 (16)
C16	0.0350 (16)	0.045 (2)	0.0346 (17)	0.0033 (17)	0.0080 (14)	−0.0009 (15)
C17	0.0433 (18)	0.059 (2)	0.050 (2)	−0.0076 (18)	0.0053 (16)	−0.0097 (18)
C18	0.047 (2)	0.081 (3)	0.043 (2)	0.003 (2)	−0.0101 (16)	−0.0156 (19)
C19	0.062 (2)	0.066 (3)	0.039 (2)	0.015 (2)	0.0013 (17)	0.0046 (16)
C20	0.0484 (19)	0.049 (2)	0.0423 (19)	0.0011 (17)	0.0056 (16)	0.0006 (16)
C21	0.0306 (15)	0.0382 (19)	0.0334 (17)	0.0019 (15)	0.0069 (13)	−0.0054 (14)

Geometric parameters (Å, º) top

S1—C21	1.767 (3)	C9—H9	0.9800
S1—C9	1.843 (3)	C10—C11	1.382 (3)
O1—C7	1.209 (3)	C10—C15	1.388 (4)
N1—C16	1.374 (4)	C11—C12	1.379 (4)
N1—H1A	0.89 (3)	C11—H11	0.9300
N1—H1B	0.91 (3)	C12—C13	1.374 (4)
C1—C6	1.380 (4)	C12—H12	0.9300
C1—C2	1.384 (4)	C13—C14	1.377 (4)
C1—H1	0.9300	C13—H13	0.9300
C2—C3	1.370 (4)	C14—C15	1.371 (4)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.360 (4)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.393 (4)
C4—C5	1.377 (4)	C16—C21	1.400 (4)
C4—H4	0.9300	C17—C18	1.373 (4)
C5—C6	1.387 (4)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.378 (4)
C6—C7	1.505 (4)	C18—H18	0.9300
C7—C8	1.515 (4)	C19—C20	1.369 (4)
C8—C9	1.522 (3)	C19—H19	0.9300
C8—H8A	0.9700	C20—C21	1.387 (4)
C8—H8B	0.9700	C20—H20	0.9300
C9—C10	1.512 (3)

C21—S1—C9	102.73 (12)	C11—C10—C15	118.2 (3)
C16—N1—H1A	119 (2)	C11—C10—C9	121.9 (2)
C16—N1—H1B	116.2 (19)	C15—C10—C9	119.8 (3)
H1A—N1—H1B	115 (3)	C12—C11—C10	121.0 (3)
C6—C1—C2	119.8 (3)	C12—C11—H11	119.5
C6—C1—H1	120.1	C10—C11—H11	119.5
C2—C1—H1	120.1	C13—C12—C11	120.1 (3)
C3—C2—C1	120.6 (3)	C13—C12—H12	120.0
C3—C2—H2	119.7	C11—C12—H12	120.0
C1—C2—H2	119.7	C12—C13—C14	119.5 (3)
C4—C3—C2	119.8 (3)	C12—C13—H13	120.2
C4—C3—H3	120.1	C14—C13—H13	120.2
C2—C3—H3	120.1	C15—C14—C13	120.4 (3)
C3—C4—C5	120.5 (3)	C15—C14—H14	119.8
C3—C4—H4	119.7	C13—C14—H14	119.8
C5—C4—H4	119.7	C14—C15—C10	120.8 (3)
C4—C5—C6	120.3 (3)	C14—C15—H15	119.6
C4—C5—H5	119.9	C10—C15—H15	119.6
C6—C5—H5	119.9	N1—C16—C17	120.2 (3)
C1—C6—C5	118.9 (3)	N1—C16—C21	121.1 (3)
C1—C6—C7	123.0 (3)	C17—C16—C21	118.7 (3)
C5—C6—C7	118.0 (3)	C18—C17—C16	120.5 (3)
O1—C7—C6	119.7 (3)	C18—C17—H17	119.8
O1—C7—C8	121.4 (3)	C16—C17—H17	119.8
C6—C7—C8	118.9 (3)	C17—C18—C19	121.1 (3)
C7—C8—C9	112.7 (2)	C17—C18—H18	119.4
C7—C8—H8A	109.1	C19—C18—H18	119.4
C9—C8—H8A	109.1	C20—C19—C18	118.8 (3)
C7—C8—H8B	109.1	C20—C19—H19	120.6
C9—C8—H8B	109.1	C18—C19—H19	120.6
H8A—C8—H8B	107.8	C19—C20—C21	121.7 (3)
C10—C9—C8	115.0 (2)	C19—C20—H20	119.1
C10—C9—S1	104.94 (17)	C21—C20—H20	119.1
C8—C9—S1	111.25 (19)	C20—C21—C16	119.3 (3)
C10—C9—H9	108.5	C20—C21—S1	119.3 (2)
C8—C9—H9	108.5	C16—C21—S1	121.2 (2)
S1—C9—H9	108.5

Hydrogen-bond geometry (Å, º) top

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

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cg1ⁱ	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+3/2, y−1/2, −z+1/2; (ii) −x+5/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₉NOS
M_r	333.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.1741 (16), 5.6788 (8), 27.308 (4)
β (°)	95.266 (2)
V (Å³)	1725.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.18 × 0.07 × 0.02

Data collection
Diffractometer	Bruker APEX-II CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	7303, 3195, 1784
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.101, 0.95
No. of reflections	3195
No. of parameters	223
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cg1ⁱ	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+3/2, y−1/2, −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

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Volume 67| Part 7| July 2011| Page o1693

doi:10.1107/S1600536811022112

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