2-(3H-1,3-Benzothia­zol-2-yl­idene)­propane­dial

Ennajih, H.; Bouhfid, R.; Massip, S.; Leger, J.M.; Essassi, E.M.

doi:10.1107/S1600536811030248

organic compounds

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Volume 67| Part 9| September 2011| Page o2260

doi:10.1107/S1600536811030248

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2-(3H-1,3-Benzothiazol-2-ylidene)propanedial

Hamid Ennajih,^a Rachid Bouhfid,^a ^* Stephane Massip,^b Jean Michel Leger ^b and El Mokhtar Essassi ^c

^aMoroccan Advanced Science, Innovation and Research (MASCIR) Foundation – INANOTECH, ENSET, Avenue de l'Armée Royale, Madinat El Irfane 10100, Rabat, Morocco, ^bLaboratoire de Chimie Physique et Minérale, EA4138 Pharmacochimie, Université Victor Ségalen Bordeaux 2, 146 Rue Léo Saignat, 33076 Bordeaux Cedex, France, and ^cLaboratoire de Chimie Organique Hétérocyclique, Faculté des Sciences, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: gbouhfid@yahoo.fr

(Received 29 June 2011; accepted 26 July 2011; online 6 August 2011)

In the title compound, C₁₀H₇NO₂S, the dihedral angle between the benzimidazole and malonaldehyde group is 1.41 (2)°. An intramolecular hydrogen bond is formed between the NH group and one of the adjacent carbonyl O atoms. In addition, the NH group forms an intermolecular hydrogen bond to a symmetry equivalent of this carbonyl O atom, connecting the molecules into centrosymmetric dimers. The structure also contains C—H⋯O intermolecular interactions.

Related literature

For biological activities of benzothiazole derivatives, see: Mortimer et al. (2006 ); Yoshida et al. (2005 ); Vicini et al. (2003 ).

Experimental

Crystal data

C₁₀H₇NO₂S
M_r = 205.23
Monoclinic, P 2₁ /c
a = 8.3927 (10) Å
b = 5.0972 (8) Å
c = 20.739 (2) Å
β = 100.098 (8)°
V = 873.4 (2) Å³
Z = 4
Cu Kα radiation
μ = 3.05 mm⁻¹
T = 133 K
0.12 × 0.12 × 0.02 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.711, T_max = 0.942
10660 measured reflections
1569 independent reflections
1475 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.165
S = 1.02
1569 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯O11	0.88	2.13	2.731 (3)	125
N6—H6⋯O11ⁱ	0.88	2.13	2.926 (3)	151
C3—H3⋯O14ⁱⁱ	0.95	2.43	3.297 (4)	152
Symmetry codes: (i) -x+1, -y, -z; (ii) -x+2, -y+2, -z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (van der Sluis & Spek, 1990 ; Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030248/hg5064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030248/hg5064Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030248/hg5064Isup3.cml

checkCIF report

Comment top

Benzothiazole and its derivatives are good candidates that have fluorescent properties and possess diverse biological properties, such as antibacterial, anti-inflammatory and antitumor. (Mortimer et al. (2006); Yoshida et al. (2005); Vicini et al. (2003)). In the present paper, we report the synthesis of 1,3-benzothiazol-2(3H)-ylidenemalonaldehyde using the Vilsmeier reaction. This molecule can be used as a precursor for the synthesis of a variety of fluorescent molecules. The crystal structure of the title compound is characterized by bifurcated hydrogen bonds between the amine and aldehyde groups. The donor atom N6 gives the mean interactions with 2 acceptor atom O11. One is intramolecular (x, y, z) but the other one is intermolecular (1 - x, -y, -z). These interactions form a coplanar dimer around the centre in 1/2, 1/2, 0.5. Atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor via atom H3 to atom O14 in the molecule at (2 - x, 2 - y, -z)

Related literature top

For biological activities of benzothiazole derivatives, see: Mortimer et al. (2006); Yoshida et al. (2005); Vicini et al. (2003)).

Experimental top

To N,N-dimethylformamide (2 ml) cooled in an ice bath was added dropwise phosphorus oxychloride (1.6 ml, 17.4 mmol) with stirring at below 5 °C. After this addition, a solution of 2-methybenzothiazole (2.9 mmol, 0.432 g) in DMF (2 ml) was added dropwise. The cooling bath was removed and the reaction mixture was stirred at 80 °C for 12 h. The resulting solution was added to ice-cooled water and made alkaline with NaOH (aq.) solution. The resulting precipitate was collected by filtration after 24 h, dried in air, recrystallized from ethanol, to give 1,3-benzothiazol-2(3H)-ylidenemalonaldehyde as colourless crystals.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (van der Sluis & Spek, 1990; Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP diagram of the title molecule with the atom numbering scheme. Displacement ellipsoid are drawn at 30% probability level.
	Fig. 2. Packing diagram of the title compound viewed down the b axis. Dashed lines indicate hydrogen bonds intra and intermolecular interactions.

2-(3H-1,3-Benzothiazol-2-ylidene)propanedial top

Crystal data top

C₁₀H₇NO₂S	F(000) = 424
M_r = 205.23	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 1475 reflections
a = 8.3927 (10) Å	θ = 7.5–71.9°
b = 5.0972 (8) Å	µ = 3.05 mm⁻¹
c = 20.739 (2) Å	T = 133 K
β = 100.098 (8)°	Plate, colourless
V = 873.4 (2) Å³	0.12 × 0.12 × 0.02 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1569 independent reflections
Radiation source: micro-focus rotating anode	1475 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.082
ω scans	θ_max = 71.9°, θ_min = 7.5°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −10→10
T_min = 0.711, T_max = 0.942	k = −4→5
10660 measured reflections	l = −25→25

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.098P)² + 1.503P] where P = (F_o² + 2F_c²)/3
1569 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₀H₇NO₂S	V = 873.4 (2) Å³
M_r = 205.23	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 8.3927 (10) Å	µ = 3.05 mm⁻¹
b = 5.0972 (8) Å	T = 133 K
c = 20.739 (2) Å	0.12 × 0.12 × 0.02 mm
β = 100.098 (8)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1569 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1475 reflections with I > 2σ(I)
T_min = 0.711, T_max = 0.942	R_int = 0.082
10660 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.02	Δρ_max = 0.60 e Å⁻³
1569 reflections	Δρ_min = −0.45 e Å⁻³
128 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
C1	0.6870 (3)	0.3667 (6)	0.16032 (14)	0.0291 (7)
H1	0.6162	0.2210	0.1600	0.035*
C2	0.7501 (3)	0.4952 (7)	0.21783 (13)	0.0311 (7)
H2	0.7216	0.4366	0.2578	0.037*
C3	0.8986 (3)	0.7993 (6)	0.16137 (14)	0.0272 (6)
H3	0.9706	0.9434	0.1619	0.033*
C4	0.8343 (3)	0.6732 (6)	0.10311 (13)	0.0256 (6)
C5	0.7315 (3)	0.4596 (6)	0.10291 (13)	0.0255 (6)
N6	0.6804 (3)	0.3641 (5)	0.03972 (11)	0.0248 (6)
H6	0.6145	0.2294	0.0313	0.030*
C7	0.7391 (3)	0.4926 (6)	−0.00706 (13)	0.0248 (6)
S8	0.86490 (8)	0.74932 (13)	0.02434 (3)	0.0253 (3)
C9	0.7044 (3)	0.4279 (6)	−0.07455 (13)	0.0267 (7)
C10	0.6013 (3)	0.2122 (6)	−0.09676 (14)	0.0267 (7)
H10	0.5856	0.1748	−0.1423	0.032*
O11	0.5306 (2)	0.0694 (4)	−0.06329 (9)	0.0303 (5)
C12	0.8543 (4)	0.7080 (6)	0.21876 (14)	0.0308 (7)
H12	0.8955	0.7919	0.2592	0.037*
C13	0.7714 (3)	0.5777 (6)	−0.12103 (14)	0.0303 (7)
H13	0.7447	0.5248	−0.1655	0.036*
O14	0.8605 (3)	0.7691 (4)	−0.10910 (11)	0.0343 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0248 (13)	0.0302 (18)	0.0337 (14)	0.0004 (12)	0.0085 (11)	0.0039 (12)
C2	0.0296 (14)	0.037 (2)	0.0280 (14)	0.0031 (13)	0.0094 (11)	0.0059 (12)
C3	0.0231 (13)	0.0296 (17)	0.0300 (14)	0.0009 (12)	0.0079 (11)	−0.0012 (12)
C4	0.0205 (12)	0.0312 (17)	0.0266 (13)	0.0034 (11)	0.0087 (10)	0.0026 (12)
C5	0.0197 (12)	0.0278 (17)	0.0294 (14)	0.0042 (11)	0.0052 (10)	−0.0001 (11)
N6	0.0200 (11)	0.0268 (15)	0.0287 (11)	−0.0004 (10)	0.0071 (8)	−0.0004 (9)
C7	0.0176 (12)	0.0264 (17)	0.0318 (14)	0.0032 (11)	0.0084 (10)	0.0007 (11)
S8	0.0225 (4)	0.0277 (5)	0.0274 (5)	−0.0021 (2)	0.0090 (3)	0.0003 (2)
C9	0.0213 (13)	0.0307 (18)	0.0295 (14)	0.0040 (11)	0.0082 (10)	0.0010 (11)
C10	0.0218 (13)	0.0316 (18)	0.0277 (14)	0.0040 (11)	0.0070 (11)	0.0002 (11)
O11	0.0262 (10)	0.0315 (13)	0.0341 (10)	−0.0017 (8)	0.0083 (8)	0.0019 (9)
C12	0.0295 (15)	0.0367 (19)	0.0263 (14)	0.0045 (12)	0.0053 (11)	−0.0022 (12)
C13	0.0276 (14)	0.0352 (19)	0.0303 (14)	0.0030 (13)	0.0109 (11)	0.0003 (12)
O14	0.0333 (12)	0.0377 (15)	0.0353 (12)	−0.0053 (9)	0.0151 (9)	0.0016 (9)

Geometric parameters (Å, º) top

C1—C2	1.382 (4)	N6—C7	1.334 (4)
C1—C5	1.392 (4)	N6—H6	0.8800
C1—H1	0.9500	C7—C9	1.418 (4)
C2—C12	1.391 (4)	C7—S8	1.735 (3)
C2—H2	0.9500	C9—C13	1.421 (4)
C3—C12	1.388 (4)	C9—C10	1.425 (4)
C3—C4	1.391 (4)	C10—O11	1.228 (4)
C3—H3	0.9500	C10—H10	0.9500
C4—C5	1.388 (4)	C12—H12	0.9500
C4—S8	1.741 (3)	C13—O14	1.228 (4)
C5—N6	1.393 (3)	C13—H13	0.9500

C2—C1—C5	117.2 (3)	C5—N6—H6	122.6
C2—C1—H1	121.4	N6—C7—C9	124.4 (3)
C5—C1—H1	121.4	N6—C7—S8	112.0 (2)
C1—C2—C12	121.8 (3)	C9—C7—S8	123.5 (2)
C1—C2—H2	119.1	C7—S8—C4	90.23 (13)
C12—C2—H2	119.1	C7—C9—C13	120.5 (3)
C12—C3—C4	117.9 (3)	C7—C9—C10	120.4 (3)
C12—C3—H3	121.0	C13—C9—C10	119.1 (3)
C4—C3—H3	121.0	O11—C10—C9	126.9 (3)
C5—C4—C3	120.7 (3)	O11—C10—H10	116.5
C5—C4—S8	111.4 (2)	C9—C10—H10	116.5
C3—C4—S8	127.8 (2)	C3—C12—C2	120.8 (3)
C4—C5—C1	121.6 (3)	C3—C12—H12	119.6
C4—C5—N6	111.4 (2)	C2—C12—H12	119.6
C1—C5—N6	126.9 (3)	O14—C13—C9	126.2 (3)
C7—N6—C5	114.9 (2)	O14—C13—H13	116.9
C7—N6—H6	122.6	C9—C13—H13	116.9

C5—C1—C2—C12	−0.2 (4)	C9—C7—S8—C4	−179.5 (2)
C12—C3—C4—C5	−1.2 (4)	C5—C4—S8—C7	0.0 (2)
C12—C3—C4—S8	178.5 (2)	C3—C4—S8—C7	−179.7 (3)
C3—C4—C5—C1	1.1 (4)	N6—C7—C9—C13	179.4 (2)
S8—C4—C5—C1	−178.7 (2)	S8—C7—C9—C13	−1.0 (4)
C3—C4—C5—N6	179.7 (3)	N6—C7—C9—C10	−0.3 (4)
S8—C4—C5—N6	−0.1 (3)	S8—C7—C9—C10	179.3 (2)
C2—C1—C5—C4	−0.3 (4)	C7—C9—C10—O11	2.1 (4)
C2—C1—C5—N6	−178.7 (3)	C13—C9—C10—O11	−177.7 (3)
C4—C5—N6—C7	0.2 (3)	C4—C3—C12—C2	0.7 (4)
C1—C5—N6—C7	178.7 (3)	C1—C2—C12—C3	0.0 (5)
C5—N6—C7—C9	179.4 (2)	C7—C9—C13—O14	−0.4 (5)
C5—N6—C7—S8	−0.2 (3)	C10—C9—C13—O14	179.3 (3)
N6—C7—S8—C4	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O11	0.88	2.13	2.731 (3)	125
N6—H6···O11ⁱ	0.88	2.13	2.926 (3)	151
C3—H3···O14ⁱⁱ	0.95	2.43	3.297 (4)	152

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₇NO₂S
M_r	205.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	133
a, b, c (Å)	8.3927 (10), 5.0972 (8), 20.739 (2)
β (°)	100.098 (8)
V (Å³)	873.4 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.05
Crystal size (mm)	0.12 × 0.12 × 0.02

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.711, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	10660, 1569, 1475
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.165, 1.02
No. of reflections	1569
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.45

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (van der Sluis & Spek, 1990; Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O11	0.8800	2.1271	2.731 (3)	125.24
N6—H6···O11ⁱ	0.8800	2.1276	2.926 (3)	150.61
C3—H3···O14ⁱⁱ	0.9500	2.4284	3.297 (4)	151.90

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y+2, −z.

References

Mortimer, C. G., Wells, G., Crochard, J.-P., Stone, E. L., Bradshaw, T. D., Stevens, M. G. F. & Westwell, A. D. (2006). J. Med. Chem. 49, 179–185. Web of Science CrossRef CAS Google Scholar
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Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194–201. CrossRef Web of Science IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vicini, P., Gernonikaki, A., Incerti, M., Busonera, B., Poni, G., Cabras, C. A. & Colla, P. L. (2003). Bioorg. Med. Chem. 11, 4785–4789. CrossRef CAS Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2260

doi:10.1107/S1600536811030248

Open

access