organic compounds

Acta Crystallographica Section E Monoclinic, P21 =c Z=4

Structure Reports a = 8.3927 (10) Å Cu K radiation
b = 5.0972 (8) Å  = 3.05 mm1
Online c = 20.739 (2) Å T = 133 K
ISSN 1600-5368  = 100.098 (8) 0.12  0.12  0.02 mm
V = 873.4 (2) Å3

Data collection
2-(3H-1,3-Benzothiazol-2-ylidene)-
Rigaku R-AXIS RAPID 10660 measured reflections
propanedial diffractometer 1569 independent reflections
Absorption correction: multi-scan 1475 reflections with I > 2(I)
(CrystalClear; Rigaku/MSC, Rint = 0.082
Hamid Ennajih,a Rachid Bouhfid,a* Stephane Massip,b 2005)
Jean Michel Legerb and El Mokhtar Essassic Tmin = 0.711, Tmax = 0.942

a
Moroccan Advanced Science, Innovation and Research (MASCIR) Foundation – Refinement
INANOTECH, ENSET, Avenue de l’Armée Royale, Madinat El Irfane 10100, Rabat, R[F 2 > 2(F 2)] = 0.067 128 parameters
Morocco, bLaboratoire de Chimie Physique et Minérale, EA4138 Pharmacochimie, wR(F 2) = 0.165 H-atom parameters constrained
Université Victor Ségalen Bordeaux 2, 146 Rue Léo Saignat, 33076 Bordeaux Cedex, S = 1.02
max = 0.60 e Å3
France, and cLaboratoire de Chimie Organique Hétérocyclique, Faculté des 1569 reflections
min = 0.45 e Å3
Sciences, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
Correspondence e-mail: [email protected]
Table 1
Received 29 June 2011; accepted 26 July 2011
Hydrogen-bond geometry (Å,  ).
Key indicators: single-crystal X-ray study; T = 133 K; mean (C–C) = 0.004 Å; D—H  A D—H H  A D  A D—H  A
R factor = 0.067; wR factor = 0.165; data-to-parameter ratio = 12.3.
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
In the title compound, C10H7NO2S, the dihedral angle
Symmetry codes: (i) x þ 1; y; z; (ii) x þ 2; y þ 2; z.
between the benzimidazole and malonaldehyde group is
1.41 (2) . An intramolecular hydrogen bond is formed Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement:
between the NH group and one of the adjacent carbonyl O CrystalClear; data reduction: CrystalClear; program(s) used to solve
atoms. In addition, the NH group forms an intermolecular structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
hydrogen bond to a symmetry equivalent of this carbonyl O structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
atom, connecting the molecules into centrosymmetric dimers. PLATON (van der Sluis & Spek, 1990; Spek, 2009); software used to
The structure also contains C—H  O intermolecular inter- prepare material for publication: publCIF (Westrip, 2010).
actions.

Supplementary data and figures for this paper are available from the
Related literature IUCr electronic archives (Reference: HG5064).
For biological activities of benzothiazole derivatives, see:
Mortimer et al. (2006); Yoshida et al. (2005); Vicini et al. References
(2003).
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.
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas,
USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sluis, P. van der & Spek, A. L. (1990). Acta Cryst. A46, 194–201.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Vicini, P., Gernonikaki, A., Incerti, M., Busonera, B., Poni, G., Cabras, C. A. &
Colla, P. L. (2003). Bioorg. Med. Chem. 11, 4785–4789.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Yoshida, M., Hayakawa, I., Hayashi, N., Agatsuma, T., Oda, Y., Tanzawa, F.,
Iwasaki, S., Koyama, K., Furukawa, H., Kurakata, Y. & Sugano, Y. (2005).
Bioorg. Med. Chem. Lett. 15, 3328–3332.

Experimental
Crystal data
C10H7NO2S Mr = 205.23

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Acta Cryst. (2011). E67, o2260 [doi:10.1107/S1600536811030248]

2-(3H-1,3-Benzothiazol-2-ylidene)propanedial
Hamid Ennajih, Rachid Bouhfid, Stephane Massip, Jean Michel Leger and El Mokhtar Essassi

S1. Comment
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)

S2. Experimental
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.

S3. Refinement
Carbon and Nitrogen H-atoms were located from Fourier Fourier synthesis and placed in calculated positions (C—H 0.95
Å, N—H 0.88 Å) and included in the refinement in the riding model approximation with Uiso(H) = 1.2Ueq(C,N).

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Figure 1
ORTEP diagram of the title molecule with the atom numbering scheme. Displacement ellipsoid are drawn at 30%
probability level.

Figure 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

Crystal data
C10H7NO2S Monoclinic, P21/c
Mr = 205.23 Hall symbol: -P 2ybc

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a = 8.3927 (10) Å Cu Kα radiation, λ = 1.54180 Å
b = 5.0972 (8) Å Cell parameters from 1475 reflections
c = 20.739 (2) Å θ = 7.5–71.9°
β = 100.098 (8)° µ = 3.05 mm−1
V = 873.4 (2) Å3 T = 133 K
Z=4 Plate, colourless
F(000) = 424 0.12 × 0.12 × 0.02 mm
Dx = 1.561 Mg m−3
Data collection
Rigaku R-AXIS RAPID 10660 measured reflections
diffractometer 1569 independent reflections
Radiation source: micro-focus rotating anode 1475 reflections with I > 2σ(I)
Confocal monochromator Rint = 0.082
ω scans θmax = 71.9°, θmin = 7.5°
Absorption correction: multi-scan h = −10→10
(CrystalClear; Rigaku/MSC, 2005) k = −4→5
Tmin = 0.711, Tmax = 0.942 l = −25→25

Refinement
Refinement on F2 Secondary atom site location: difference Fourier
Least-squares matrix: full map
R[F2 > 2σ(F2)] = 0.067 Hydrogen site location: inferred from
wR(F2) = 0.165 neighbouring sites
S = 1.02 H-atom parameters constrained
1569 reflections w = 1/[σ2(Fo2) + (0.098P)2 + 1.503P]
128 parameters where P = (Fo2 + 2Fc2)/3
0 restraints (Δ/σ)max < 0.001
Primary atom site location: structure-invariant Δρmax = 0.60 e Å−3
direct methods Δρmin = −0.45 e Å−3

Special details
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)

x y z Uiso*/Ueq
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)

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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)

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)

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)

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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)

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.

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