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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1442.
Published online 2008 July 9. doi:  10.1107/S1600536808015365
PMCID: PMC2962073

The 1:1 cocrystal of rac-7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxylic acid and 2-amino­benzothia­zole

Abstract

In the crystal structure of the title compound, rac-7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxylic acid–2-amino­benzo­thia­zole (1/1), C8H10O5·C7H6N2S, mol­ecules of each component are linked into centrosymmetric dimers by inter­molecular N—H(...)O hydrogen bonds. These dimers are connected by O—H(...)O hydrogen bonds into a chain along the b axis. In addition, π–π inter­actions between aromatic heterocycles occur [centroid–centroid distance of 3.4709 Å and inter­planar spacing of 3.4374 Å between symmetry-related benzothia­zole ring systems.

Related literature

For related literature, see: Liu et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1442-scheme1.jpg

Experimental

Crystal data

  • C8H10O5·C7H6N2S
  • M r = 336.36
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1442-efi1.jpg
  • a = 8.3082 (1) Å
  • b = 9.0428 (1) Å
  • c = 11.0438 (2) Å
  • α = 67.1546 (8)°
  • β = 83.0101 (8)°
  • γ = 86.9193 (9)°
  • V = 758.92 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 296 (2) K
  • 0.43 × 0.27 × 0.16 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.92, T max = 0.96
  • 11829 measured reflections
  • 3416 independent reflections
  • 2675 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.159
  • S = 1.06
  • 3416 reflections
  • 214 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.67 e Å−3
  • Δρmin = −1.05 e Å−3

Data collection: SMART (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015365/kp2168sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015365/kp2168Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge financial support from the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301).

supplementary crystallographic information

Comment

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin), a traditional Chinese drug, has great anti-cancer activity. In order to prepare compounds with pronounced anti-cancer activity, some derivatives were synthesized (Liu et al., 2002). 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride can react with 2-aminobenzothiazole to form an acylamide acid derivative which has strong anti-cancer activity. However, a crystal suitable for X-ray diffraction was obtained during the synthesis unexpectedly.

The crystal structure of the title compound (I) is characterized by alternating molecules of 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid and 2-aminobenzothiazole, linked by N—H···O and O—H···O hydrogen bonds. The centrosymmetric dimer composed of two 2-aminobenzothiazole and two acids is generated by bifurcated hydrogen bonds of amino group of 2-aminobenzothiazole and the acid component (N1—H1B···O4 and N1—H1B···O5, O3—H3···N2 and N1—H1A···O1). These dimers are connected into a chain by hydrogen bonds O2—H2···O4. Furthermore, there are short distances [centroid separation of 3.4709 Å and interplanar spacing of 3.4374 Å] between the benzothiazole-ring planes and the symmetry-related planes at (-x + 1,-y + 1,-z; -x + 1,-y + 2,-z) of adjacent chains, implying π···π interactions (Fig. 2). In the molecule, the conformation of 7-oxabicyclo[2.2.1]heptane ring is discussed as follows, the six-membered ring adopts a boat conformation and the two oxygen-bearing five-membered heterocycles are in an envelope conformation.

Experimental

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride and 2-aminobenzothiazole were dissolved in acetonitrile and the mixture was stirred for 2 h at room temperature. The precipitate has been proved to exhibit anticancer activity. However, colourless crystals of (I) were obtained in the filtrate after several days, unexpectedly.

Refinement

The structure was solved by direct methods and successive Fourier difference synthesis. The H atoms bonded to C and Natoms were positioned geometrically and refined using a riding model [aromatic C—H 0.93 Å, aliphatic C—H = 0.97 (2) Å and N—H = 0.86 Å Uiso(H) = 1.2Ueq(C)]. The H atoms bonded to O atoms were located in a differenceFourier maps and refined with O—H distance restraints of 0.85 (2) and Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
A view of the molecule of (I) showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability.
Fig. 2.
The crystal packing diagram, showing the π···π stacking and hydrogen bonds as dash lines.

Crystal data

C8H10O5·C7H6N2SZ = 2
Mr = 336.36F000 = 352
Triclinic, P1Dx = 1.472 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.3082 (1) ÅCell parameters from 4303 reflections
b = 9.0428 (1) Åθ = 2.0–27.4º
c = 11.0438 (2) ŵ = 0.24 mm1
α = 67.1546 (8)ºT = 296 (2) K
β = 83.0101 (8)ºBlock, colourless
γ = 86.9193 (9)º0.43 × 0.27 × 0.16 mm
V = 758.93 (2) Å3

Data collection

Bruker APEXII area-detector diffractometer3416 independent reflections
Radiation source: fine-focus sealed tube2675 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 296(2) Kθmax = 27.4º
ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.92, Tmax = 0.96k = −11→11
11829 measured reflectionsl = −14→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.159  w = 1/[σ2(Fo2) + (0.0773P)2 + 0.3994P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
3416 reflectionsΔρmax = 0.67 e Å3
214 parametersΔρmin = −1.05 e Å3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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)

xyzUiso*/Ueq
S10.41626 (8)0.33690 (10)0.46435 (8)0.0645 (3)
N10.5173 (3)0.4819 (3)0.2070 (3)0.0640 (6)
H1A0.58270.49570.13690.077*
H1B0.43380.54330.20330.077*
N20.6705 (2)0.2670 (2)0.33434 (19)0.0424 (4)
O10.2197 (2)0.5380 (2)−0.00822 (19)0.0616 (5)
O20.28892 (19)1.05947 (19)−0.01033 (17)0.0463 (4)
H20.385 (2)1.090 (4)−0.025 (3)0.069*
O30.1725 (2)0.7920 (2)−0.13815 (17)0.0546 (5)
H30.227 (4)0.770 (4)−0.200 (3)0.082*
O40.40832 (17)0.81995 (19)0.06576 (18)0.0489 (4)
O50.17176 (18)0.58165 (18)0.27645 (15)0.0441 (4)
C10.2856 (2)0.9053 (2)0.0535 (2)0.0354 (4)
C20.1220 (2)0.8368 (2)0.1213 (2)0.0342 (4)
H2A0.04240.92400.10930.041*
C30.1319 (3)0.7405 (3)0.2703 (2)0.0405 (5)
H3A0.20940.78400.30790.049*
C4−0.0397 (3)0.7220 (3)0.3424 (2)0.0486 (6)
H4A−0.10050.82190.31160.058*
H4B−0.03810.68470.43730.058*
C5−0.1091 (3)0.5947 (3)0.3034 (3)0.0498 (6)
H5A−0.13880.49800.38020.060*
H5B−0.20280.63530.25540.060*
C60.0343 (3)0.5643 (3)0.2149 (2)0.0426 (5)
H6A0.03050.46010.20740.051*
C70.0545 (2)0.7055 (3)0.0818 (2)0.0368 (5)
H7A−0.05300.73960.05250.044*
C80.1598 (3)0.6691 (3)−0.0256 (2)0.0416 (5)
C90.5451 (3)0.3664 (3)0.3202 (3)0.0473 (6)
C100.6687 (3)0.1569 (3)0.4631 (2)0.0460 (5)
C110.7797 (4)0.0351 (3)0.5088 (3)0.0623 (7)
H11A0.86950.02430.45360.075*
C120.7536 (5)−0.0717 (4)0.6404 (3)0.0803 (10)
H12A0.8273−0.15470.67380.096*
C130.6181 (5)−0.0553 (4)0.7222 (3)0.0823 (10)
H13A0.6013−0.12940.80890.099*
C140.5100 (5)0.0671 (5)0.6778 (3)0.0788 (9)
H14A0.42080.07780.73350.095*
C150.5351 (3)0.1745 (3)0.5489 (3)0.0571 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0463 (4)0.0910 (6)0.0724 (5)−0.0114 (3)0.0153 (3)−0.0539 (4)
N10.0493 (12)0.0656 (14)0.0688 (16)0.0157 (10)−0.0021 (11)−0.0202 (12)
N20.0411 (9)0.0464 (10)0.0417 (10)−0.0012 (8)0.0021 (8)−0.0211 (9)
O10.0721 (12)0.0542 (10)0.0538 (11)0.0143 (9)0.0059 (9)−0.0212 (9)
O20.0363 (8)0.0413 (8)0.0499 (10)−0.0046 (6)0.0004 (7)−0.0062 (7)
O30.0684 (11)0.0541 (10)0.0368 (9)0.0106 (8)0.0043 (8)−0.0171 (8)
O40.0303 (7)0.0460 (9)0.0630 (11)0.0003 (6)0.0053 (7)−0.0159 (8)
O50.0379 (8)0.0474 (9)0.0401 (9)0.0018 (6)−0.0035 (6)−0.0098 (7)
C10.0315 (9)0.0389 (10)0.0332 (10)−0.0018 (8)0.0010 (8)−0.0122 (8)
C20.0265 (9)0.0372 (10)0.0373 (11)0.0009 (7)0.0013 (7)−0.0141 (9)
C30.0350 (10)0.0506 (12)0.0368 (11)−0.0064 (9)0.0012 (8)−0.0184 (10)
C40.0433 (12)0.0602 (14)0.0400 (12)−0.0075 (10)0.0110 (9)−0.0205 (11)
C50.0397 (12)0.0591 (14)0.0452 (13)−0.0140 (10)0.0079 (10)−0.0162 (11)
C60.0405 (11)0.0420 (11)0.0440 (12)−0.0060 (9)0.0013 (9)−0.0162 (10)
C70.0296 (9)0.0447 (11)0.0378 (11)−0.0007 (8)−0.0028 (8)−0.0181 (9)
C80.0381 (11)0.0503 (13)0.0394 (12)0.0028 (9)−0.0046 (9)−0.0210 (10)
C90.0367 (11)0.0551 (13)0.0583 (15)−0.0070 (10)0.0065 (10)−0.0335 (12)
C100.0556 (14)0.0478 (12)0.0408 (12)−0.0131 (10)−0.0007 (10)−0.0234 (10)
C110.088 (2)0.0553 (15)0.0482 (15)−0.0018 (14)−0.0140 (14)−0.0224 (12)
C120.129 (3)0.0528 (16)0.062 (2)−0.0111 (18)−0.034 (2)−0.0174 (15)
C130.125 (3)0.083 (2)0.0391 (15)−0.0536 (16)−0.0057 (17)−0.0179 (15)
C140.091 (2)0.104 (2)0.0495 (17)−0.0510 (15)0.0100 (14)−0.0374 (17)
C150.0619 (14)0.0761 (14)0.0439 (14)−0.0314 (9)0.0091 (9)−0.0351 (11)

Geometric parameters (Å, °)

S1—C151.734 (3)C4—C51.537 (3)
S1—C91.743 (2)C4—H4A0.9700
N1—C91.318 (4)C4—H4B0.9700
N1—H1A0.8600C5—C61.530 (3)
N1—H1B0.8600C5—H5A0.9700
N2—C91.322 (3)C5—H5B0.9700
N2—C101.382 (3)C6—C71.525 (3)
O1—C81.214 (3)C6—H6A0.9800
O2—C11.295 (3)C7—C81.517 (3)
O2—H20.836 (18)C7—H7A0.9800
O3—C81.303 (3)C10—C111.375 (4)
O3—H30.854 (18)C10—C151.413 (3)
O4—C11.234 (2)C11—C121.396 (4)
O5—C31.434 (3)C11—H11A0.9300
O5—C61.443 (3)C12—C131.395 (6)
C1—C21.508 (3)C12—H12A0.9300
C2—C31.544 (3)C13—C141.361 (5)
C2—C71.565 (3)C13—H13A0.9300
C2—H2A0.9800C14—C151.374 (4)
C3—C41.530 (3)C14—H14A0.9300
C3—H3A0.9800
C15—S1—C989.18 (12)O5—C6—C5102.47 (18)
C9—N1—H1A120.0C7—C6—C5110.16 (19)
C9—N1—H1B120.0O5—C6—H6A113.6
H1A—N1—H1B120.0C7—C6—H6A113.6
C9—N2—C10111.49 (19)C5—C6—H6A113.6
C1—O2—H2109 (2)C8—C7—C6114.11 (18)
C8—O3—H3112 (2)C8—C7—C2115.16 (16)
C3—O5—C696.24 (15)C6—C7—C2101.23 (17)
O4—C1—O2123.04 (18)C8—C7—H7A108.7
O4—C1—C2121.43 (18)C6—C7—H7A108.7
O2—C1—C2115.39 (17)C2—C7—H7A108.7
C1—C2—C3110.23 (17)O1—C8—O3124.6 (2)
C1—C2—C7116.64 (16)O1—C8—C7123.1 (2)
C3—C2—C7100.43 (16)O3—C8—C7112.29 (18)
C1—C2—H2A109.7N1—C9—N2123.7 (2)
C3—C2—H2A109.7N1—C9—S1121.07 (18)
C7—C2—H2A109.7N2—C9—S1115.2 (2)
O5—C3—C4103.13 (17)C11—C10—N2125.6 (2)
O5—C3—C2102.91 (16)C11—C10—C15120.4 (2)
C4—C3—C2108.53 (18)N2—C10—C15114.0 (2)
O5—C3—H3A113.7C10—C11—C12118.0 (3)
C4—C3—H3A113.7C10—C11—H11A121.0
C2—C3—H3A113.7C12—C11—H11A121.0
C3—C4—C5101.17 (18)C11—C12—C13120.6 (3)
C3—C4—H4A111.5C11—C12—H12A119.7
C5—C4—H4A111.5C13—C12—H12A119.7
C3—C4—H4B111.5C14—C13—C12121.3 (3)
C5—C4—H4B111.5C14—C13—H13A119.3
H4A—C4—H4B109.4C12—C13—H13A119.3
C6—C5—C4101.63 (17)C13—C14—C15118.7 (3)
C6—C5—H5A111.4C13—C14—H14A120.6
C4—C5—H5A111.4C15—C14—H14A120.6
C6—C5—H5B111.4C14—C15—C10120.9 (3)
C4—C5—H5B111.4C14—C15—S1128.9 (3)
H5A—C5—H5B109.3C10—C15—S1110.1 (2)
O5—C6—C7102.38 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.862.132.953 (3)161
N1—H1B···O50.862.293.061 (3)150
N1—H1B···O40.862.382.991 (3)128
O2—H2···O4ii0.836 (18)1.868 (18)2.700 (2)174 (3)
O3—H3···N2i0.854 (18)1.758 (19)2.611 (2)176 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2168).

References

  • Bruker (2004). SAINT and SMART Bruker AXS Inc., Madison,Wisconsin, USA.
  • Liu, F.-L., Jiang, T. & Zuo, D.-S. (2002). Chin. J. Org. Chem.22, 751–767.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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