(Z)-2-Benzyl­idenebenzo[d]thia­zolo[3,2-a]imidazol-3(2H)-one

Fun, H.-K.; Quah, C.K.; Abdel-Aziz, H.A.; Ghabbour, H.A.

doi:10.1107/S1600536812035003

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2705

doi:10.1107/S1600536812035003

Open

access

(Z)-2-Benzylidenebenzo[d]thiazolo[3,2-a]imidazol-3(2H)-one

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Hatem A. Abdel-Aziz ^b and Hazem A. Ghabbour ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: hkfun@usm.my

(Received 24 July 2012; accepted 8 August 2012; online 15 August 2012)

The molecule of the title compound, C₁₆H₁₀N₂OS, is approximately planar, the dihedral angle between the 1,3-benzothiazolo[3,2-a]imidazol-3(2H)-one and the benzylidene moieties being 4.10 (8)°. A weak intramolecular C—H⋯S interaction generates an S(6) ring. No intermolecular hydrogen bonds are observed in the crystal structure.

Related literature

For background to and the biological activity of thiazolo[3,2-a]benzimidazoles, see: Al-Rashood & Abdel-Aziz (2010 ); Chimirri et al. (1988 ), For a related structure, references to our previous work in this area and references to further synthetic details, see: Fun et al. (2012 ).

Experimental

Crystal data

C₁₆H₁₀N₂OS
M_r = 278.32
Orthorhombic, P b c a
a = 12.1721 (5) Å
b = 7.7697 (3) Å
c = 27.2200 (8) Å
V = 2574.29 (16) Å³
Z = 8
Cu Kα radiation
μ = 2.20 mm⁻¹
T = 296 K
0.77 × 0.65 × 0.04 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.282, T_max = 0.917
8750 measured reflections
2270 independent reflections
1912 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 1.03
2270 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯S1	0.93	2.56	3.262 (3)	132

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035003/hb6910sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035003/hb6910Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035003/hb6910Isup3.cml

checkCIF report

Comment top

Thiazolo[3,2-a]benzimidazoles show a variety of interesting biological activity such as antibacterial, antifungal, anti-inflammatory, antiulcer, antiviral, anthelmintic and anticancer activity (Al-Rashood & Abdel-Aziz, 2010; Chimirri et al., 1988). As part on our ongoing studies in this area (Fun et al., 2012), we now describe the crystal structure of the title compound.

In the title molecule, Fig. 1, the benzo[d]thiazolo[3,2-a]imidazol- 3(2H)-one moiety is roughly planar with an r.m.s. deviation 0.062 Å for the thirteen non H-atoms (C1–C9/N1/N2/O1/S1) and the benzilidene moiety is also nearly planar with an r.m.s. deviation 0.005Å for the seven non H-atoms (C10–C16). The dihedral between the two mean planes is 4.10 (8)°. An intramolecular C12—H12A···S1 weak interaction (Fig. 1 and Table 1) generates an S(6) ring, which helps to establish the planarity of the molecule. The bond distances are comparable to those in a related structure (Fun et al., 2012). There are no significant intermolecular hydrogen bond observed in the crystal structure of this compound.

Related literature top

For background to and the biological activity of thiazolo[3,2-a]benzimidazoles, see: Al-Rashood & Abdel-Aziz (2010); Chimirri et al. (1988), For a related structure, references to our previous work in this area and references to further synthetic details, see: Fun et al. (2012).

Experimental top

The one-pot synthesis of the title compound carried out by a cyclocondensation of 2-mercaptobenzimidazole, chloroacetic acid, benzaldehyde, acetic anhydride and glacial acetic acid in the presence of sodium acetate to afford the title compound (Fun et al., 2012). Yellow plates were obtained by slowly evaporating an EtOH/DMF solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms. Intramolecular hydrogen bond is shown as dashed line.

(Z)-2-Benzylidenebenzo[d]thiazolo[3,2-a]imidazol- 3(2H)-one top

Crystal data top

C₁₆H₁₀N₂OS	F(000) = 1152
M_r = 278.32	D_x = 1.436 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1434 reflections
a = 12.1721 (5) Å	θ = 3.3–69.8°
b = 7.7697 (3) Å	µ = 2.20 mm⁻¹
c = 27.2200 (8) Å	T = 296 K
V = 2574.29 (16) Å³	Plate, yellow
Z = 8	0.77 × 0.65 × 0.04 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2270 independent reflections
Radiation source: fine-focus sealed tube	1912 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ϕ and ω scans	θ_max = 67.4°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→14
T_min = 0.282, T_max = 0.917	k = −8→6
8750 measured reflections	l = −32→28

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0558P)² + 0.7634P] where P = (F_o² + 2F_c²)/3
2270 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₀N₂OS	V = 2574.29 (16) Å³
M_r = 278.32	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 12.1721 (5) Å	µ = 2.20 mm⁻¹
b = 7.7697 (3) Å	T = 296 K
c = 27.2200 (8) Å	0.77 × 0.65 × 0.04 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2270 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1912 reflections with I > 2σ(I)
T_min = 0.282, T_max = 0.917	R_int = 0.051
8750 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.03	Δρ_max = 0.45 e Å⁻³
2270 reflections	Δρ_min = −0.20 e Å⁻³
181 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.78126 (4)	0.01576 (8)	0.554734 (19)	0.0518 (2)
O1	1.04329 (12)	−0.1399 (2)	0.62205 (6)	0.0608 (5)
N1	0.89265 (13)	0.0307 (2)	0.63592 (6)	0.0441 (4)
N2	0.72939 (15)	0.1641 (3)	0.64488 (7)	0.0556 (5)
C1	0.95869 (16)	−0.0762 (3)	0.60802 (7)	0.0450 (5)
C2	0.90610 (16)	−0.0989 (3)	0.55886 (7)	0.0440 (5)
C3	0.79414 (17)	0.0814 (3)	0.61580 (8)	0.0470 (5)
C4	0.78928 (17)	0.1704 (3)	0.68946 (8)	0.0488 (5)
C5	0.75984 (19)	0.2391 (3)	0.73449 (9)	0.0580 (6)
H5A	0.6924	0.2931	0.7389	0.070*
C6	0.8340 (2)	0.2249 (3)	0.77273 (8)	0.0591 (6)
H6A	0.8156	0.2700	0.8033	0.071*
C7	0.9350 (2)	0.1456 (3)	0.76682 (8)	0.0569 (6)
H7A	0.9826	0.1387	0.7935	0.068*
C8	0.96661 (18)	0.0763 (3)	0.72232 (8)	0.0506 (5)
H8A	1.0349	0.0248	0.7180	0.061*
C9	0.89105 (17)	0.0880 (3)	0.68454 (7)	0.0439 (5)
C10	0.95483 (17)	−0.1957 (3)	0.52492 (8)	0.0472 (5)
H10A	1.0213	−0.2430	0.5350	0.057*
C11	0.92361 (16)	−0.2417 (3)	0.47492 (8)	0.0460 (5)
C12	0.82753 (19)	−0.1866 (4)	0.45178 (9)	0.0592 (6)
H12A	0.7789	−0.1147	0.4683	0.071*
C13	0.8045 (2)	−0.2387 (4)	0.40425 (10)	0.0714 (7)
H13A	0.7401	−0.2021	0.3892	0.086*
C14	0.8757 (2)	−0.3439 (4)	0.37915 (9)	0.0659 (7)
H14A	0.8594	−0.3784	0.3472	0.079*
C15	0.9707 (2)	−0.3979 (4)	0.40123 (9)	0.0655 (7)
H15A	1.0197	−0.4677	0.3842	0.079*
C16	0.99336 (19)	−0.3485 (3)	0.44864 (8)	0.0554 (6)
H16A	1.0574	−0.3879	0.4635	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0486 (4)	0.0588 (4)	0.0480 (3)	0.0084 (2)	−0.0101 (2)	−0.0030 (2)
O1	0.0484 (8)	0.0820 (12)	0.0522 (9)	0.0157 (8)	−0.0082 (7)	−0.0057 (8)
N1	0.0437 (9)	0.0443 (10)	0.0442 (9)	0.0009 (7)	−0.0052 (7)	−0.0007 (7)
N2	0.0549 (10)	0.0609 (13)	0.0509 (10)	0.0135 (9)	−0.0049 (8)	−0.0033 (9)
C1	0.0437 (11)	0.0476 (12)	0.0438 (11)	−0.0019 (9)	−0.0018 (9)	0.0002 (9)
C2	0.0416 (10)	0.0465 (13)	0.0438 (11)	−0.0023 (9)	−0.0034 (8)	0.0035 (9)
C3	0.0484 (11)	0.0451 (12)	0.0474 (11)	0.0040 (9)	−0.0060 (9)	0.0031 (9)
C4	0.0530 (12)	0.0463 (13)	0.0471 (11)	0.0022 (9)	−0.0013 (9)	0.0029 (9)
C5	0.0586 (13)	0.0613 (15)	0.0542 (13)	0.0076 (11)	0.0057 (11)	−0.0022 (11)
C6	0.0708 (14)	0.0632 (16)	0.0432 (12)	−0.0013 (12)	0.0060 (10)	−0.0032 (11)
C7	0.0656 (14)	0.0616 (15)	0.0437 (12)	−0.0062 (11)	−0.0053 (10)	−0.0001 (11)
C8	0.0499 (11)	0.0527 (14)	0.0492 (11)	−0.0013 (10)	−0.0059 (9)	0.0003 (10)
C9	0.0497 (11)	0.0409 (12)	0.0413 (10)	−0.0030 (9)	0.0006 (8)	0.0001 (9)
C10	0.0449 (10)	0.0520 (13)	0.0446 (11)	0.0002 (9)	−0.0022 (9)	0.0036 (10)
C11	0.0473 (10)	0.0461 (12)	0.0446 (11)	−0.0049 (9)	−0.0009 (9)	0.0016 (9)
C12	0.0542 (12)	0.0716 (17)	0.0519 (12)	0.0081 (11)	−0.0052 (10)	−0.0082 (12)
C13	0.0661 (15)	0.090 (2)	0.0578 (15)	0.0089 (14)	−0.0158 (12)	−0.0099 (14)
C14	0.0783 (16)	0.0715 (18)	0.0478 (12)	−0.0034 (13)	−0.0079 (12)	−0.0104 (12)
C15	0.0772 (16)	0.0656 (17)	0.0538 (13)	0.0069 (13)	0.0063 (12)	−0.0083 (12)
C16	0.0544 (13)	0.0606 (15)	0.0511 (13)	0.0049 (11)	−0.0014 (10)	0.0002 (11)

Geometric parameters (Å, º) top

S1—C3	1.746 (2)	C7—H7A	0.9300
S1—C2	1.765 (2)	C8—C9	1.383 (3)
O1—C1	1.205 (2)	C8—H8A	0.9300
N1—C3	1.376 (3)	C10—C11	1.457 (3)
N1—C1	1.383 (3)	C10—H10A	0.9300
N1—C9	1.396 (3)	C11—C16	1.386 (3)
N2—C3	1.289 (3)	C11—C12	1.396 (3)
N2—C4	1.417 (3)	C12—C13	1.384 (3)
C1—C2	1.494 (3)	C12—H12A	0.9300
C2—C10	1.331 (3)	C13—C14	1.373 (4)
C4—C5	1.384 (3)	C13—H13A	0.9300
C4—C9	1.401 (3)	C14—C15	1.369 (4)
C5—C6	1.382 (3)	C14—H14A	0.9300
C5—H5A	0.9300	C15—C16	1.374 (3)
C6—C7	1.384 (3)	C15—H15A	0.9300
C6—H6A	0.9300	C16—H16A	0.9300
C7—C8	1.380 (3)

C3—S1—C2	90.54 (10)	C7—C8—H8A	121.9
C3—N1—C1	117.37 (17)	C9—C8—H8A	121.9
C3—N1—C9	105.91 (17)	C8—C9—N1	132.4 (2)
C1—N1—C9	136.04 (18)	C8—C9—C4	123.2 (2)
C3—N2—C4	103.21 (17)	N1—C9—C4	104.39 (17)
O1—C1—N1	124.72 (19)	C2—C10—C11	132.1 (2)
O1—C1—C2	127.0 (2)	C2—C10—H10A	113.9
N1—C1—C2	108.28 (17)	C11—C10—H10A	113.9
C10—C2—C1	119.84 (19)	C16—C11—C12	117.6 (2)
C10—C2—S1	128.66 (16)	C16—C11—C10	117.96 (19)
C1—C2—S1	111.49 (15)	C12—C11—C10	124.4 (2)
N2—C3—N1	115.54 (19)	C13—C12—C11	120.1 (2)
N2—C3—S1	132.50 (16)	C13—C12—H12A	119.9
N1—C3—S1	111.95 (15)	C11—C12—H12A	119.9
C5—C4—C9	119.3 (2)	C14—C13—C12	120.7 (2)
C5—C4—N2	129.7 (2)	C14—C13—H13A	119.6
C9—C4—N2	110.95 (18)	C12—C13—H13A	119.6
C6—C5—C4	117.8 (2)	C15—C14—C13	119.8 (2)
C6—C5—H5A	121.1	C15—C14—H14A	120.1
C4—C5—H5A	121.1	C13—C14—H14A	120.1
C5—C6—C7	121.9 (2)	C14—C15—C16	119.8 (2)
C5—C6—H6A	119.1	C14—C15—H15A	120.1
C7—C6—H6A	119.1	C16—C15—H15A	120.1
C8—C7—C6	121.6 (2)	C15—C16—C11	121.9 (2)
C8—C7—H7A	119.2	C15—C16—H16A	119.0
C6—C7—H7A	119.2	C11—C16—H16A	119.0
C7—C8—C9	116.2 (2)

C3—N1—C1—O1	−174.8 (2)	C6—C7—C8—C9	−1.2 (4)
C9—N1—C1—O1	−5.8 (4)	C7—C8—C9—N1	−178.4 (2)
C3—N1—C1—C2	4.5 (3)	C7—C8—C9—C4	2.4 (3)
C9—N1—C1—C2	173.5 (2)	C3—N1—C9—C8	−179.5 (2)
O1—C1—C2—C10	−1.4 (4)	C1—N1—C9—C8	10.7 (4)
N1—C1—C2—C10	179.30 (19)	C3—N1—C9—C4	−0.1 (2)
O1—C1—C2—S1	179.0 (2)	C1—N1—C9—C4	−169.9 (2)
N1—C1—C2—S1	−0.3 (2)	C5—C4—C9—C8	−2.3 (3)
C3—S1—C2—C10	177.7 (2)	N2—C4—C9—C8	179.4 (2)
C3—S1—C2—C1	−2.71 (16)	C5—C4—C9—N1	178.3 (2)
C4—N2—C3—N1	−0.2 (3)	N2—C4—C9—N1	0.0 (2)
C4—N2—C3—S1	178.6 (2)	C1—C2—C10—C11	179.5 (2)
C1—N1—C3—N2	172.3 (2)	S1—C2—C10—C11	−1.0 (4)
C9—N1—C3—N2	0.2 (3)	C2—C10—C11—C16	−179.5 (2)
C1—N1—C3—S1	−6.8 (3)	C2—C10—C11—C12	−0.1 (4)
C9—N1—C3—S1	−178.84 (14)	C16—C11—C12—C13	0.1 (4)
C2—S1—C3—N2	−173.7 (3)	C10—C11—C12—C13	−179.3 (2)
C2—S1—C3—N1	5.20 (17)	C11—C12—C13—C14	−0.4 (5)
C3—N2—C4—C5	−178.0 (3)	C12—C13—C14—C15	−0.1 (5)
C3—N2—C4—C9	0.1 (3)	C13—C14—C15—C16	1.0 (4)
C9—C4—C5—C6	0.9 (4)	C14—C15—C16—C11	−1.3 (4)
N2—C4—C5—C6	178.8 (2)	C12—C11—C16—C15	0.8 (4)
C4—C5—C6—C7	0.2 (4)	C10—C11—C16—C15	−179.7 (2)
C5—C6—C7—C8	0.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···S1	0.93	2.56	3.262 (3)	132

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀N₂OS
M_r	278.32
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	12.1721 (5), 7.7697 (3), 27.2200 (8)
V (Å³)	2574.29 (16)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.77 × 0.65 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.282, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	8750, 2270, 1912
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.03
No. of reflections	2270
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.20

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···S1	0.93	2.56	3.262 (3)	132

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009

Acknowledgements

The authors thank the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University. HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160).

References

Al-Rashood, K. A. & Abdel-Aziz, H. A. (2010). Molecules, 15, 3775–3815. Web of Science CAS PubMed Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chimirri, A., Grasso, S., Romeo, G. & Zappala, M. (1988). Heterocycles, 27, 1975–2003. CAS Google Scholar
Fun, H.-K., Chantrapromma, S. & Abdel-Aziz, H. A. (2012). Acta Cryst. E68, o1393–o1394. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar