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organic compounds
1,3-Benzothiazole–oxalic acid (2/1)
aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: hkfun@usm.my
The 7H5NS·0.5C2H2O4, contains one benzothiazole molecule and half an oxalic acid molecule, the complete molecule being generated by inversion symmetry. The benzothiazole molecule is essentially planar, with a maximum deviation of 0.007 (1) Å. In the crystal, the benzothiazole molecules interact with the oxalic acid molecules via O—H⋯N and C—H⋯O hydrogen bonds generating R22(8) (× 2) and R44(10) motifs, thereby forming supramolecular ribbons along [101].
of the title compound, CRelated literature
For background to the biological activity of benzothiazoles, see: Bradshaw et al. (1998); Dögruer et al. (1998
); Dash et al. (1980
); Cox et al. (1982
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536811032260/tk2778sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811032260/tk2778Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811032260/tk2778Isup3.cml
The juice of Guava (Psidium guajava) was extracted using soxhlet extraction method with methanol as solvent. After 24 hours at room temperature, a precipitate was formed and the filtrate removed. The precipitate was washed by using a mixture (90–100) ml of n-hexane-ethyl acetate. It was recrystallized by dissolving in methanol. Brown crystals were formed which melted at M.pt 323 K.
Atom H1O2 was located from a difference Fourier map and refined with Uiso(H) = 1.5Ueq(O) [O—H = 0.89 (2) Å]. The remaining H atoms were positioned geometrically [C—H = 0.93 Å] and were refined using a riding model, with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2009); cell
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).C7H5NS·0.5C2H2O4 | F(000) = 372 |
Mr = 180.20 | Dx = 1.486 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3803 reflections |
a = 4.0231 (3) Å | θ = 2.8–32.6° |
b = 26.039 (2) Å | µ = 0.35 mm−1 |
c = 8.5605 (6) Å | T = 296 K |
β = 116.064 (3)° | Plate, brown |
V = 805.58 (10) Å3 | 0.62 × 0.40 × 0.04 mm |
Z = 4 |
Bruker APEXII DUO CCD area-detector diffractometer | 3204 independent reflections |
Radiation source: fine-focus sealed tube | 2417 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 33.9°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −6→6 |
Tmin = 0.811, Tmax = 0.985 | k = −40→40 |
10970 measured reflections | l = −13→13 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0557P)2 + 0.1124P] where P = (Fo2 + 2Fc2)/3 |
3204 reflections | (Δ/σ)max = 0.001 |
112 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C7H5NS·0.5C2H2O4 | V = 805.58 (10) Å3 |
Mr = 180.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.0231 (3) Å | µ = 0.35 mm−1 |
b = 26.039 (2) Å | T = 296 K |
c = 8.5605 (6) Å | 0.62 × 0.40 × 0.04 mm |
β = 116.064 (3)° |
Bruker APEXII DUO CCD area-detector diffractometer | 3204 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2417 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.985 | Rint = 0.026 |
10970 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.36 e Å−3 |
3204 reflections | Δρmin = −0.23 e Å−3 |
112 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
S1 | 1.14317 (9) | 0.875823 (14) | 1.21487 (4) | 0.04461 (11) | |
N1 | 1.0034 (3) | 0.91965 (4) | 0.92292 (13) | 0.0385 (2) | |
C1 | 0.8353 (3) | 0.84567 (4) | 1.02665 (14) | 0.0350 (2) | |
C2 | 0.6466 (4) | 0.79950 (5) | 1.00741 (19) | 0.0448 (3) | |
H2A | 0.6763 | 0.7800 | 1.1037 | 0.054* | |
C3 | 0.4144 (4) | 0.78360 (5) | 0.8411 (2) | 0.0493 (3) | |
H3A | 0.2881 | 0.7527 | 0.8252 | 0.059* | |
C4 | 0.3652 (4) | 0.81302 (5) | 0.69656 (18) | 0.0468 (3) | |
H4A | 0.2035 | 0.8017 | 0.5861 | 0.056* | |
C5 | 0.5516 (4) | 0.85854 (5) | 0.71444 (15) | 0.0412 (3) | |
H5A | 0.5187 | 0.8780 | 0.6176 | 0.049* | |
C6 | 0.7919 (3) | 0.87487 (4) | 0.88198 (14) | 0.0329 (2) | |
C7 | 1.1947 (4) | 0.92418 (5) | 1.09000 (16) | 0.0408 (3) | |
H7A | 1.3510 | 0.9520 | 1.1395 | 0.049* | |
O1 | 0.7128 (3) | 0.94803 (4) | 0.47893 (12) | 0.0584 (3) | |
O2 | 1.1410 (3) | 0.98494 (4) | 0.71853 (11) | 0.0468 (2) | |
H1O2 | 1.064 (6) | 0.9617 (8) | 0.771 (3) | 0.070* | |
C8 | 0.9467 (3) | 0.97976 (4) | 0.55062 (14) | 0.0363 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.04724 (18) | 0.0555 (2) | 0.02518 (14) | −0.00784 (13) | 0.01050 (12) | 0.00106 (11) |
N1 | 0.0444 (5) | 0.0389 (5) | 0.0286 (4) | −0.0058 (4) | 0.0128 (4) | −0.0010 (3) |
C1 | 0.0333 (5) | 0.0404 (5) | 0.0298 (5) | 0.0001 (4) | 0.0123 (4) | 0.0004 (4) |
C2 | 0.0428 (6) | 0.0456 (6) | 0.0446 (6) | −0.0034 (5) | 0.0179 (5) | 0.0069 (5) |
C3 | 0.0464 (7) | 0.0420 (6) | 0.0565 (8) | −0.0098 (5) | 0.0199 (6) | −0.0064 (6) |
C4 | 0.0442 (6) | 0.0515 (7) | 0.0390 (6) | −0.0080 (5) | 0.0131 (5) | −0.0136 (5) |
C5 | 0.0447 (6) | 0.0465 (6) | 0.0281 (5) | −0.0032 (5) | 0.0121 (5) | −0.0042 (4) |
C6 | 0.0349 (5) | 0.0351 (5) | 0.0275 (5) | −0.0006 (4) | 0.0126 (4) | −0.0019 (4) |
C7 | 0.0442 (6) | 0.0426 (6) | 0.0315 (5) | −0.0082 (5) | 0.0129 (5) | −0.0038 (4) |
O1 | 0.0705 (7) | 0.0600 (6) | 0.0318 (4) | −0.0320 (5) | 0.0108 (4) | −0.0010 (4) |
O2 | 0.0557 (5) | 0.0486 (5) | 0.0255 (4) | −0.0169 (4) | 0.0081 (4) | 0.0029 (3) |
C8 | 0.0400 (5) | 0.0365 (5) | 0.0265 (5) | −0.0049 (4) | 0.0092 (4) | 0.0009 (4) |
S1—C7 | 1.7222 (13) | C4—C5 | 1.3748 (19) |
S1—C1 | 1.7300 (12) | C4—H4A | 0.9300 |
N1—C7 | 1.2979 (15) | C5—C6 | 1.3979 (15) |
N1—C6 | 1.3944 (14) | C5—H5A | 0.9300 |
C1—C2 | 1.3926 (17) | C7—H7A | 0.9300 |
C1—C6 | 1.3972 (15) | O1—C8 | 1.1989 (14) |
C2—C3 | 1.379 (2) | O2—C8 | 1.3068 (13) |
C2—H2A | 0.9300 | O2—H1O2 | 0.89 (2) |
C3—C4 | 1.394 (2) | C8—C8i | 1.540 (2) |
C3—H3A | 0.9300 | ||
C7—S1—C1 | 89.19 (6) | C4—C5—C6 | 118.30 (12) |
C7—N1—C6 | 110.72 (10) | C4—C5—H5A | 120.9 |
C2—C1—C6 | 121.04 (11) | C6—C5—H5A | 120.9 |
C2—C1—S1 | 129.19 (10) | N1—C6—C1 | 114.05 (10) |
C6—C1—S1 | 109.76 (8) | N1—C6—C5 | 125.65 (10) |
C3—C2—C1 | 117.92 (12) | C1—C6—C5 | 120.30 (11) |
C3—C2—H2A | 121.0 | N1—C7—S1 | 116.28 (9) |
C1—C2—H2A | 121.0 | N1—C7—H7A | 121.9 |
C2—C3—C4 | 121.26 (12) | S1—C7—H7A | 121.9 |
C2—C3—H3A | 119.4 | C8—O2—H1O2 | 108.3 (15) |
C4—C3—H3A | 119.4 | O1—C8—O2 | 126.13 (11) |
C5—C4—C3 | 121.16 (12) | O1—C8—C8i | 122.24 (12) |
C5—C4—H4A | 119.4 | O2—C8—C8i | 111.63 (12) |
C3—C4—H4A | 119.4 | ||
C7—S1—C1—C2 | 179.27 (13) | C2—C1—C6—N1 | −179.17 (11) |
C7—S1—C1—C6 | −0.42 (9) | S1—C1—C6—N1 | 0.55 (13) |
C6—C1—C2—C3 | −0.3 (2) | C2—C1—C6—C5 | 1.12 (18) |
S1—C1—C2—C3 | −179.91 (11) | S1—C1—C6—C5 | −179.16 (9) |
C1—C2—C3—C4 | −0.9 (2) | C4—C5—C6—N1 | 179.48 (12) |
C2—C3—C4—C5 | 1.1 (2) | C4—C5—C6—C1 | −0.85 (19) |
C3—C4—C5—C6 | −0.3 (2) | C6—N1—C7—S1 | 0.05 (15) |
C7—N1—C6—C1 | −0.39 (15) | C1—S1—C7—N1 | 0.22 (11) |
C7—N1—C6—C5 | 179.30 (12) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···N1 | 0.89 (2) | 1.80 (2) | 2.6663 (15) | 166 (2) |
C5—H5A···O1 | 0.93 | 2.48 | 3.3263 (17) | 151 |
C7—H7A···O2ii | 0.93 | 2.48 | 3.4029 (18) | 170 |
Symmetry code: (ii) −x+3, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C7H5NS·0.5C2H2O4 |
Mr | 180.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 4.0231 (3), 26.039 (2), 8.5605 (6) |
β (°) | 116.064 (3) |
V (Å3) | 805.58 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.62 × 0.40 × 0.04 |
Data collection | |
Diffractometer | Bruker APEXII DUO CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.811, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10970, 3204, 2417 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.785 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.114, 1.04 |
No. of reflections | 3204 |
No. of parameters | 112 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.23 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···N1 | 0.89 (2) | 1.80 (2) | 2.6663 (15) | 166 (2) |
C5—H5A···O1 | 0.93 | 2.4800 | 3.3263 (17) | 151 |
C7—H7A···O2i | 0.93 | 2.4800 | 3.4029 (18) | 170 |
Symmetry code: (i) −x+3, −y+2, −z+2. |
Footnotes
‡Thomson Reuters ResearcherID: A-3561-2009.
Acknowledgements
NM gratefully acknowledges funding from the Malaysian Ministry of Science, Technology and Innovation through the Malaysian Institute of Pharmaceutical and Nutraceutical R&D Initiative Grant (grant No. 09-05-IFN-MEB 004). HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.
References
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Benzothiazoles are used as anti-neoplastic agents and show anti-nociceptive, anti-inflammatory and anti-tumour activities (Bradshaw et al., 1998; Dögruer et al., 1998). Some Schiff bases derived from thiazole and benzothiazoles (Dash et al., 1980) and several derivatives of the styryl-benzothiazoles have also shown biological activity (Cox et al., 1982). In view of the above biological activities associated with the benzothiazole, herein, we present the title compound (I), extracted from the juice of Guava (Psidium guajava).
The asymmetric unit of the title compound, (I), contains one benzothiazole molecule and a half of an oxalic acid molecule (which lies on an inversion centre) as detailed in Fig. 1. The benzothiazole (N1/S1/C1–C7) molecule is essentially planar, with a maximum deviation of 0.007 (1) Å for atom C6.
In the crystal structure, Fig. 2, the benzothiazole molecules interact with the oxalic acid molecules via O—H···N and C—H···O hydrogen bonds (Table 1) generating R22(8) and R44(10) motifs and forming supramolecular ribbons along the [1 0 1] direction.