2-Anilino-5-benzoyl-4-phenyl-1,3-thia­zole

Dridi, K.; El Efrit, M.L.

doi:10.1107/S1600536807035635

2-Anilino-5-benzoyl-4-phenyl-1,3-thiazole

Under basic conditions, methyl-N-phenylthiocarbomylphenylimidate and phenacyl bromide form the title compound, C₂₂H₁₆N₂OS. X-ray diffraction shows that the crystal structure can be described as consisting of pseudo-dimers resulting from intermolecular N—H

N hydrogen bonds, which are further stabilized by van der Waals interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035635/dn2220sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035635/dn2220Isup2.hkl Contains datablock I

CCDC reference: 657865

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.047
wR factor = 0.116
Data-to-parameter ratio = 18.0

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No syntax errors found



Alert level C
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Aminothiazoles constitute excellent precursors of a large variety of biologically active compounds such as inihibitors of human breast cancer cell proliferation (Gorczynski et al., 2004) and as inhibitors of protein phosphatases (Wipf et al., 2001). As a part of our ongoing research focused on the use of N-functionalized imidates in heterocyclic syntheses (El Efrit et al., 1996, Dridi et al., 1998), we show that, in presence of sodium hydride (NaH), the reaction of N-thiocarbamoylimidate, Ph—C(OMe)=N—C(NHPh)=S, with 2-Bromo-1-phenylethanone (Br—CH2—C(O)—Ph) can can theoretically lead to thiazole or diazole isomeric ring.

From the X-Ray diffraction experiment, the title compound was identified as 5-Benzoyl-2-phenylamino-4-phenylthiazole, C₂₂H₁₆N₂OS (I).The bond lengths and bond angles observed in this structure exhibit normal values (Allen, 2002). The four rings constituting the molecule (Fig1) named A(C1, C2, C3, N1, S) for the thiazole and B(C5, C6, C7, C8, C9, C10), C(C11, C12, C13, C14, C15, C16) and D(C17, C18, C19, C20, C21, C22) for the phenyl are as expected planar with the largest deviations being 0.016\%A for the thiazole ring, but they are twisted with respect to each other. The dihedral angles between these planes are A^ B= 51,09 (5), A^D = 55,93 (6), AĈ = 49,99 (7), B^ = 45,51 (7), B^D = 33,57 (8) and C^D = 15,82 (13).

The molecules are organized by pairs forming dimer through N—H···N hydrogen bonds building a graph set motif R²₂(8) (Etter et al., 1990; Bernstein et al., 1995) (Table 1, Fig. 2). The packing is stabilized by van der Waals interactions.

Related literature top

For general background, see: Dridi et al. (1998); El Efrit et al. (1996); Gorczynski et al. (2004); Wipf et al. (2001). For structural information, see: Allen (2002); Etter et al. (1990); Bernstein et al. (1995).

Experimental top

To the suspension of sodium hydride (20 mmol) in THF (50 ml) was added drop wise under nitrogen atmosphere with stirring at room temperature a solution of N-thiocarbamoylimidate: Ph—C(OMe)=N—C(NHPh)=S (10 mmol) in THF (10 ml). After stirring for 1 h, 2-Bromo-1-phenylethanone (10 mmol) dissolved in THF (30 ml) was added. The reaction mixture was stirred for a period of 14 h and hydrolyzed with water (10 ml). The organic layer was extracted with chloroform, dried over MgSO4 and concentrated under reduced pressure to give the 5-Benzoyl-2-phenylamino-4-phenylthiazole. Recristallization from water-ethanol (2:1) afford crystals (mp 473 K) suitable for x-ray diffraction study.

Structure description top

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular view of (I) with the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the formation of pseudo dimer through N—H···N hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

2-Anilino-5-benzoyl-4-phenyl-1,3-thiazole top

Crystal data top

C₂₂H₁₆N₂OS	F(000) = 744
M_r = 356.43	D_x = 1.330 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 13.163 (4) Å	θ = 9–11°
b = 9.433 (4) Å	µ = 0.20 mm⁻¹
c = 14.533 (2) Å	T = 293 K
β = 99.33 (2)°	Prism, colourless
V = 1780.7 (10) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Enraf–Nonius MACH3 diffractometer	R_int = 0.028
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.3°
Graphite monochromator	h = −17→17
non–profiled ω scans	k = 0→12
6093 measured reflections	l = −5→19
4298 independent reflections	2 standard reflections every 120 min
2704 reflections with I > 2σ(I)	intensity decay: 4%

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0501P)² + 0.2524P] where P = (F_o² + 2F_c²)/3
4298 reflections	(Δ/σ)_max = 0.014
239 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₂H₁₆N₂OS	V = 1780.7 (10) Å³
M_r = 356.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.163 (4) Å	µ = 0.20 mm⁻¹
b = 9.433 (4) Å	T = 293 K
c = 14.533 (2) Å	0.20 × 0.18 × 0.16 mm
β = 99.33 (2)°

Data collection top

Enraf–Nonius MACH3 diffractometer	R_int = 0.028
6093 measured reflections	2 standard reflections every 120 min
4298 independent reflections	intensity decay: 4%
2704 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.17 e Å⁻³
4298 reflections	Δρ_min = −0.27 e Å⁻³
239 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
H23	0.4049 (15)	0.014 (2)	0.5334 (15)	0.051 (6)*
S1	0.45331 (4)	0.35859 (5)	0.61163 (4)	0.04442 (15)
N1	0.55404 (11)	0.16658 (16)	0.53728 (11)	0.0406 (4)
N2	0.38926 (12)	0.09407 (19)	0.55532 (13)	0.0474 (4)
C1	0.46481 (13)	0.19246 (19)	0.56396 (13)	0.0393 (4)
C2	0.61980 (13)	0.2793 (2)	0.55837 (13)	0.0393 (4)
C3	0.58128 (13)	0.3926 (2)	0.60089 (14)	0.0419 (5)
C4	0.62158 (16)	0.5284 (2)	0.63774 (14)	0.0485 (5)
C5	0.73535 (16)	0.5524 (2)	0.66124 (14)	0.0473 (5)
C6	0.77439 (18)	0.6847 (2)	0.64381 (15)	0.0582 (6)
H6	0.7307	0.7557	0.6163	0.070*
C7	0.8793 (2)	0.7100 (3)	0.66781 (18)	0.0721 (8)
H7	0.9059	0.7980	0.6553	0.087*
C8	0.9439 (2)	0.6068 (3)	0.70969 (19)	0.0771 (8)
H8	1.0141	0.6246	0.7247	0.093*
C9	0.90544 (18)	0.4770 (3)	0.72957 (17)	0.0698 (7)
H9	0.9491	0.4080	0.7597	0.084*
C10	0.80140 (17)	0.4493 (3)	0.70459 (15)	0.0557 (6)
H10	0.7756	0.3608	0.7170	0.067*
C11	0.30362 (13)	0.0973 (2)	0.60371 (14)	0.0431 (5)
C12	0.28562 (15)	−0.0198 (2)	0.65595 (15)	0.0549 (6)
H12	0.3287	−0.0984	0.6588	0.066*
C13	0.20274 (18)	−0.0194 (3)	0.70408 (17)	0.0692 (7)
H13	0.1900	−0.0985	0.7387	0.083*
C14	0.13943 (16)	0.0965 (3)	0.70108 (17)	0.0674 (7)
H14	0.0850	0.0968	0.7347	0.081*
C15	0.15660 (15)	0.2113 (3)	0.64847 (17)	0.0606 (6)
H15	0.1134	0.2897	0.6461	0.073*
C16	0.23814 (14)	0.2122 (2)	0.59834 (15)	0.0502 (5)
H16	0.2484	0.2898	0.5615	0.060*
C17	0.72450 (13)	0.2650 (2)	0.53328 (13)	0.0408 (4)
C18	0.76104 (16)	0.3639 (2)	0.47657 (16)	0.0547 (5)
H18	0.7196	0.4392	0.4523	0.066*
C19	0.85990 (18)	0.3503 (3)	0.45611 (18)	0.0711 (7)
H19	0.8847	0.4172	0.4183	0.085*
C20	0.92083 (17)	0.2400 (3)	0.49075 (19)	0.0731 (7)
H20	0.9870	0.2318	0.4767	0.088*
C21	0.88460 (16)	0.1402 (3)	0.54673 (18)	0.0671 (7)
H21	0.9266	0.0652	0.5706	0.080*
C22	0.78631 (15)	0.1514 (2)	0.56741 (15)	0.0520 (5)
H22	0.7615	0.0830	0.6042	0.062*
O1	0.56177 (12)	0.62208 (16)	0.65279 (13)	0.0742 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0376 (2)	0.0432 (3)	0.0558 (3)	0.0025 (2)	0.0174 (2)	−0.0052 (3)
N1	0.0362 (8)	0.0400 (9)	0.0481 (10)	−0.0007 (7)	0.0145 (7)	−0.0031 (7)
N2	0.0410 (9)	0.0445 (10)	0.0617 (11)	−0.0052 (7)	0.0230 (8)	−0.0115 (9)
C1	0.0374 (9)	0.0407 (10)	0.0422 (11)	0.0026 (8)	0.0134 (8)	−0.0002 (9)
C2	0.0365 (9)	0.0427 (10)	0.0406 (10)	0.0014 (8)	0.0117 (8)	0.0032 (9)
C3	0.0352 (9)	0.0443 (11)	0.0482 (11)	−0.0001 (8)	0.0127 (8)	−0.0010 (9)
C4	0.0529 (12)	0.0457 (11)	0.0504 (12)	−0.0044 (9)	0.0191 (10)	−0.0063 (10)
C5	0.0546 (12)	0.0509 (12)	0.0397 (11)	−0.0114 (10)	0.0170 (10)	−0.0102 (10)
C6	0.0714 (15)	0.0546 (13)	0.0521 (14)	−0.0146 (11)	0.0207 (12)	−0.0103 (11)
C7	0.0790 (18)	0.0737 (17)	0.0692 (17)	−0.0358 (15)	0.0286 (15)	−0.0197 (14)
C8	0.0570 (14)	0.107 (2)	0.0690 (17)	−0.0226 (15)	0.0163 (13)	−0.0289 (17)
C9	0.0598 (15)	0.0902 (19)	0.0570 (15)	−0.0034 (14)	0.0024 (12)	−0.0135 (14)
C10	0.0585 (13)	0.0642 (14)	0.0458 (12)	−0.0083 (11)	0.0124 (10)	−0.0024 (11)
C11	0.0331 (9)	0.0540 (12)	0.0441 (11)	−0.0052 (8)	0.0118 (8)	−0.0067 (10)
C12	0.0452 (11)	0.0633 (14)	0.0579 (13)	0.0009 (10)	0.0136 (10)	0.0066 (11)
C13	0.0579 (14)	0.0921 (19)	0.0614 (15)	−0.0082 (14)	0.0215 (12)	0.0202 (14)
C14	0.0439 (12)	0.105 (2)	0.0586 (14)	−0.0058 (13)	0.0232 (11)	−0.0032 (15)
C15	0.0382 (11)	0.0757 (16)	0.0706 (16)	0.0028 (11)	0.0165 (11)	−0.0123 (13)
C16	0.0410 (10)	0.0538 (12)	0.0576 (13)	−0.0037 (9)	0.0138 (10)	−0.0061 (11)
C17	0.0335 (9)	0.0454 (11)	0.0452 (11)	−0.0011 (8)	0.0112 (8)	−0.0045 (9)
C18	0.0515 (11)	0.0543 (12)	0.0628 (14)	0.0011 (10)	0.0229 (11)	0.0072 (12)
C19	0.0593 (14)	0.0791 (17)	0.0835 (18)	−0.0054 (13)	0.0375 (13)	0.0095 (15)
C20	0.0392 (11)	0.097 (2)	0.0884 (19)	0.0019 (13)	0.0263 (12)	−0.0029 (17)
C21	0.0428 (11)	0.0779 (16)	0.0802 (17)	0.0152 (12)	0.0090 (12)	0.0066 (15)
C22	0.0427 (10)	0.0573 (13)	0.0570 (13)	0.0026 (10)	0.0111 (10)	0.0042 (11)
O1	0.0654 (10)	0.0550 (10)	0.1070 (14)	0.0013 (8)	0.0286 (10)	−0.0236 (10)

Geometric parameters (Å, º) top

S1—C1	1.730 (2)	C11—C16	1.380 (3)
S1—C3	1.7465 (18)	C11—C12	1.382 (3)
N1—C1	1.318 (2)	C12—C13	1.388 (3)
N1—C2	1.374 (2)	C12—H12	0.9300
N2—C1	1.351 (2)	C13—C14	1.371 (3)
N2—C11	1.423 (2)	C13—H13	0.9300
N2—H23	0.86 (2)	C14—C15	1.366 (3)
C2—C3	1.372 (3)	C14—H14	0.9300
C2—C17	1.488 (2)	C15—C16	1.392 (3)
C3—C4	1.456 (3)	C15—H15	0.9300
C4—O1	1.226 (2)	C16—H16	0.9300
C4—C5	1.498 (3)	C17—C18	1.382 (3)
C5—C10	1.386 (3)	C17—C22	1.387 (3)
C5—C6	1.388 (3)	C18—C19	1.387 (3)
C6—C7	1.389 (3)	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.360 (3)
C7—C8	1.369 (4)	C19—H19	0.9300
C7—H7	0.9300	C20—C21	1.379 (3)
C8—C9	1.374 (4)	C20—H20	0.9300
C8—H8	0.9300	C21—C22	1.379 (3)
C9—C10	1.383 (3)	C21—H21	0.9300
C9—H9	0.9300	C22—H22	0.9300
C10—H10	0.9300

C1—S1—C3	88.98 (9)	C16—C11—N2	121.77 (19)
C1—N1—C2	110.51 (15)	C12—C11—N2	118.35 (18)
C1—N2—C11	124.74 (17)	C11—C12—C13	119.5 (2)
C1—N2—H23	114.9 (13)	C11—C12—H12	120.2
C11—N2—H23	117.4 (14)	C13—C12—H12	120.2
N1—C1—N2	121.53 (17)	C14—C13—C12	120.6 (2)
N1—C1—S1	115.19 (14)	C14—C13—H13	119.7
N2—C1—S1	123.27 (14)	C12—C13—H13	119.7
C3—C2—N1	115.96 (15)	C15—C14—C13	119.7 (2)
C3—C2—C17	127.27 (17)	C15—C14—H14	120.2
N1—C2—C17	116.77 (16)	C13—C14—H14	120.2
C2—C3—C4	135.42 (17)	C14—C15—C16	120.6 (2)
C2—C3—S1	109.24 (14)	C14—C15—H15	119.7
C4—C3—S1	115.35 (14)	C16—C15—H15	119.7
O1—C4—C3	119.58 (19)	C11—C16—C15	119.6 (2)
O1—C4—C5	119.83 (19)	C11—C16—H16	120.2
C3—C4—C5	120.54 (18)	C15—C16—H16	120.2
C10—C5—C6	119.4 (2)	C18—C17—C22	119.60 (18)
C10—C5—C4	121.85 (19)	C18—C17—C2	120.71 (18)
C6—C5—C4	118.7 (2)	C22—C17—C2	119.69 (17)
C5—C6—C7	119.4 (2)	C17—C18—C19	119.6 (2)
C5—C6—H6	120.3	C17—C18—H18	120.2
C7—C6—H6	120.3	C19—C18—H18	120.2
C8—C7—C6	120.7 (2)	C20—C19—C18	120.6 (2)
C8—C7—H7	119.7	C20—C19—H19	119.7
C6—C7—H7	119.7	C18—C19—H19	119.7
C7—C8—C9	120.2 (2)	C19—C20—C21	120.1 (2)
C7—C8—H8	119.9	C19—C20—H20	120.0
C9—C8—H8	119.9	C21—C20—H20	120.0
C8—C9—C10	119.7 (3)	C20—C21—C22	120.2 (2)
C8—C9—H9	120.1	C20—C21—H21	119.9
C10—C9—H9	120.1	C22—C21—H21	119.9
C9—C10—C5	120.5 (2)	C21—C22—C17	119.9 (2)
C9—C10—H10	119.7	C21—C22—H22	120.1
C5—C10—H10	119.7	C17—C22—H22	120.1
C16—C11—C12	119.87 (18)

C2—N1—C1—N2	−176.33 (18)	C7—C8—C9—C10	1.9 (4)
C2—N1—C1—S1	2.8 (2)	C8—C9—C10—C5	−1.2 (3)
C11—N2—C1—N1	162.18 (19)	C6—C5—C10—C9	−0.6 (3)
C11—N2—C1—S1	−16.8 (3)	C4—C5—C10—C9	−176.8 (2)
C3—S1—C1—N1	−3.38 (16)	C1—N2—C11—C16	55.9 (3)
C3—S1—C1—N2	175.70 (18)	C1—N2—C11—C12	−125.2 (2)
C1—N1—C2—C3	−0.3 (2)	C16—C11—C12—C13	−1.3 (3)
C1—N1—C2—C17	179.33 (16)	N2—C11—C12—C13	179.8 (2)
N1—C2—C3—C4	177.6 (2)	C11—C12—C13—C14	−0.7 (4)
C17—C2—C3—C4	−2.1 (4)	C12—C13—C14—C15	1.5 (4)
N1—C2—C3—S1	−2.1 (2)	C13—C14—C15—C16	−0.4 (4)
C17—C2—C3—S1	178.25 (16)	C12—C11—C16—C15	2.4 (3)
C1—S1—C3—C2	2.93 (15)	N2—C11—C16—C15	−178.74 (19)
C1—S1—C3—C4	−176.84 (16)	C14—C15—C16—C11	−1.6 (3)
C2—C3—C4—O1	163.3 (2)	C3—C2—C17—C18	−56.6 (3)
S1—C3—C4—O1	−17.0 (3)	N1—C2—C17—C18	123.8 (2)
C2—C3—C4—C5	−19.4 (4)	C3—C2—C17—C22	123.2 (2)
S1—C3—C4—C5	160.29 (15)	N1—C2—C17—C22	−56.4 (3)
O1—C4—C5—C10	136.6 (2)	C22—C17—C18—C19	−1.4 (3)
C3—C4—C5—C10	−40.7 (3)	C2—C17—C18—C19	178.4 (2)
O1—C4—C5—C6	−39.6 (3)	C17—C18—C19—C20	0.5 (4)
C3—C4—C5—C6	143.1 (2)	C18—C19—C20—C21	0.1 (4)
C10—C5—C6—C7	1.7 (3)	C19—C20—C21—C22	0.3 (4)
C4—C5—C6—C7	178.04 (19)	C20—C21—C22—C17	−1.3 (4)
C5—C6—C7—C8	−1.0 (4)	C18—C17—C22—C21	1.8 (3)
C6—C7—C8—C9	−0.8 (4)	C2—C17—C22—C21	−178.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H23···N1ⁱ	0.858 (19)	2.10 (2)	2.956 (3)	172 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₆N₂OS
M_r	356.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.163 (4), 9.433 (4), 14.533 (2)
β (°)	99.33 (2)
V (Å³)	1780.7 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Enraf–Nonius MACH3
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6093, 4298, 2704
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.116, 1.00
No. of reflections	4298
No. of parameters	239
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.27

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).