



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808015365/kp2168sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808015365/kp2168Isup2.hkl |
CCDC reference: 700468
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.056
- wR factor = 0.159
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4 PLAT793_ALERT_4_G Check the Absolute Configuration of C2 ..... S PLAT793_ALERT_4_G Check the Absolute Configuration of C3 ..... R PLAT793_ALERT_4_G Check the Absolute Configuration of C6 ..... S PLAT793_ALERT_4_G Check the Absolute Configuration of C7 ..... R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.
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).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C8H10O5·C7H6N2S | Z = 2 |
Mr = 336.36 | F(000) = 352 |
Triclinic, P1 | Dx = 1.472 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3082 (1) Å | Cell parameters from 4303 reflections |
b = 9.0428 (1) Å | θ = 2.0–27.4° |
c = 11.0438 (2) Å | µ = 0.24 mm−1 |
α = 67.1546 (8)° | T = 296 K |
β = 83.0101 (8)° | Block, colourless |
γ = 86.9193 (9)° | 0.43 × 0.27 × 0.16 mm |
V = 758.93 (2) Å3 |
Bruker APEXII area-detector diffractometer | 3416 independent reflections |
Radiation source: fine-focus sealed tube | 2675 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 27.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.92, Tmax = 0.96 | k = −11→11 |
11829 measured reflections | l = −14→14 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0773P)2 + 0.3994P] where P = (Fo2 + 2Fc2)/3 |
3416 reflections | (Δ/σ)max < 0.001 |
214 parameters | Δρmax = 0.67 e Å−3 |
4 restraints | Δρmin = −1.05 e Å−3 |
C8H10O5·C7H6N2S | γ = 86.9193 (9)° |
Mr = 336.36 | V = 758.93 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3082 (1) Å | Mo Kα radiation |
b = 9.0428 (1) Å | µ = 0.24 mm−1 |
c = 11.0438 (2) Å | T = 296 K |
α = 67.1546 (8)° | 0.43 × 0.27 × 0.16 mm |
β = 83.0101 (8)° |
Bruker APEXII area-detector diffractometer | 3416 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2675 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 0.96 | Rint = 0.026 |
11829 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 4 restraints |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.67 e Å−3 |
3416 reflections | Δρmin = −1.05 e Å−3 |
214 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.41626 (8) | 0.33690 (10) | 0.46435 (8) | 0.0645 (3) | |
N1 | 0.5173 (3) | 0.4819 (3) | 0.2070 (3) | 0.0640 (6) | |
H1A | 0.5827 | 0.4957 | 0.1369 | 0.077* | |
H1B | 0.4338 | 0.5433 | 0.2033 | 0.077* | |
N2 | 0.6705 (2) | 0.2670 (2) | 0.33434 (19) | 0.0424 (4) | |
O1 | 0.2197 (2) | 0.5380 (2) | −0.00822 (19) | 0.0616 (5) | |
O2 | 0.28892 (19) | 1.05947 (19) | −0.01033 (17) | 0.0463 (4) | |
H2 | 0.385 (2) | 1.090 (4) | −0.025 (3) | 0.069* | |
O3 | 0.1725 (2) | 0.7920 (2) | −0.13815 (17) | 0.0546 (5) | |
H3 | 0.227 (4) | 0.770 (4) | −0.200 (3) | 0.082* | |
O4 | 0.40832 (17) | 0.81995 (19) | 0.06576 (18) | 0.0489 (4) | |
O5 | 0.17176 (18) | 0.58165 (18) | 0.27645 (15) | 0.0441 (4) | |
C1 | 0.2856 (2) | 0.9053 (2) | 0.0535 (2) | 0.0354 (4) | |
C2 | 0.1220 (2) | 0.8368 (2) | 0.1213 (2) | 0.0342 (4) | |
H2A | 0.0424 | 0.9240 | 0.1093 | 0.041* | |
C3 | 0.1319 (3) | 0.7405 (3) | 0.2703 (2) | 0.0405 (5) | |
H3A | 0.2094 | 0.7840 | 0.3079 | 0.049* | |
C4 | −0.0397 (3) | 0.7220 (3) | 0.3424 (2) | 0.0486 (6) | |
H4A | −0.1005 | 0.8219 | 0.3116 | 0.058* | |
H4B | −0.0381 | 0.6847 | 0.4373 | 0.058* | |
C5 | −0.1091 (3) | 0.5947 (3) | 0.3034 (3) | 0.0498 (6) | |
H5A | −0.1388 | 0.4980 | 0.3802 | 0.060* | |
H5B | −0.2028 | 0.6353 | 0.2554 | 0.060* | |
C6 | 0.0343 (3) | 0.5643 (3) | 0.2149 (2) | 0.0426 (5) | |
H6A | 0.0305 | 0.4601 | 0.2074 | 0.051* | |
C7 | 0.0545 (2) | 0.7055 (3) | 0.0818 (2) | 0.0368 (5) | |
H7A | −0.0530 | 0.7396 | 0.0525 | 0.044* | |
C8 | 0.1598 (3) | 0.6691 (3) | −0.0256 (2) | 0.0416 (5) | |
C9 | 0.5451 (3) | 0.3664 (3) | 0.3202 (3) | 0.0473 (6) | |
C10 | 0.6687 (3) | 0.1569 (3) | 0.4631 (2) | 0.0460 (5) | |
C11 | 0.7797 (4) | 0.0351 (3) | 0.5088 (3) | 0.0623 (7) | |
H11A | 0.8695 | 0.0243 | 0.4536 | 0.075* | |
C12 | 0.7536 (5) | −0.0717 (4) | 0.6404 (3) | 0.0803 (10) | |
H12A | 0.8273 | −0.1547 | 0.6738 | 0.096* | |
C13 | 0.6181 (5) | −0.0553 (4) | 0.7222 (3) | 0.0823 (10) | |
H13A | 0.6013 | −0.1294 | 0.8089 | 0.099* | |
C14 | 0.5100 (5) | 0.0671 (5) | 0.6778 (3) | 0.0788 (9) | |
H14A | 0.4208 | 0.0778 | 0.7335 | 0.095* | |
C15 | 0.5351 (3) | 0.1745 (3) | 0.5489 (3) | 0.0571 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0463 (4) | 0.0910 (6) | 0.0724 (5) | −0.0114 (3) | 0.0153 (3) | −0.0539 (4) |
N1 | 0.0493 (12) | 0.0656 (14) | 0.0688 (16) | 0.0157 (10) | −0.0021 (11) | −0.0202 (12) |
N2 | 0.0411 (9) | 0.0464 (10) | 0.0417 (10) | −0.0012 (8) | 0.0021 (8) | −0.0211 (9) |
O1 | 0.0721 (12) | 0.0542 (10) | 0.0538 (11) | 0.0143 (9) | 0.0059 (9) | −0.0212 (9) |
O2 | 0.0363 (8) | 0.0413 (8) | 0.0499 (10) | −0.0046 (6) | 0.0004 (7) | −0.0062 (7) |
O3 | 0.0684 (11) | 0.0541 (10) | 0.0368 (9) | 0.0106 (8) | 0.0043 (8) | −0.0171 (8) |
O4 | 0.0303 (7) | 0.0460 (9) | 0.0630 (11) | 0.0003 (6) | 0.0053 (7) | −0.0159 (8) |
O5 | 0.0379 (8) | 0.0474 (9) | 0.0401 (9) | 0.0018 (6) | −0.0035 (6) | −0.0098 (7) |
C1 | 0.0315 (9) | 0.0389 (10) | 0.0332 (10) | −0.0018 (8) | 0.0010 (8) | −0.0122 (8) |
C2 | 0.0265 (9) | 0.0372 (10) | 0.0373 (11) | 0.0009 (7) | 0.0013 (7) | −0.0141 (9) |
C3 | 0.0350 (10) | 0.0506 (12) | 0.0368 (11) | −0.0064 (9) | 0.0012 (8) | −0.0184 (10) |
C4 | 0.0433 (12) | 0.0602 (14) | 0.0400 (12) | −0.0075 (10) | 0.0110 (9) | −0.0205 (11) |
C5 | 0.0397 (12) | 0.0591 (14) | 0.0452 (13) | −0.0140 (10) | 0.0079 (10) | −0.0162 (11) |
C6 | 0.0405 (11) | 0.0420 (11) | 0.0440 (12) | −0.0060 (9) | 0.0013 (9) | −0.0162 (10) |
C7 | 0.0296 (9) | 0.0447 (11) | 0.0378 (11) | −0.0007 (8) | −0.0028 (8) | −0.0181 (9) |
C8 | 0.0381 (11) | 0.0503 (13) | 0.0394 (12) | 0.0028 (9) | −0.0046 (9) | −0.0210 (10) |
C9 | 0.0367 (11) | 0.0551 (13) | 0.0583 (15) | −0.0070 (10) | 0.0065 (10) | −0.0335 (12) |
C10 | 0.0556 (14) | 0.0478 (12) | 0.0408 (12) | −0.0131 (10) | −0.0007 (10) | −0.0234 (10) |
C11 | 0.088 (2) | 0.0553 (15) | 0.0482 (15) | −0.0018 (14) | −0.0140 (14) | −0.0224 (12) |
C12 | 0.129 (3) | 0.0528 (16) | 0.062 (2) | −0.0111 (18) | −0.034 (2) | −0.0174 (15) |
C13 | 0.125 (3) | 0.083 (2) | 0.0391 (15) | −0.0536 (16) | −0.0057 (17) | −0.0179 (15) |
C14 | 0.091 (2) | 0.104 (2) | 0.0495 (17) | −0.0510 (15) | 0.0100 (14) | −0.0374 (17) |
C15 | 0.0619 (14) | 0.0761 (14) | 0.0439 (14) | −0.0314 (9) | 0.0091 (9) | −0.0351 (11) |
S1—C15 | 1.734 (3) | C4—C5 | 1.537 (3) |
S1—C9 | 1.743 (2) | C4—H4A | 0.9700 |
N1—C9 | 1.318 (4) | C4—H4B | 0.9700 |
N1—H1A | 0.8600 | C5—C6 | 1.530 (3) |
N1—H1B | 0.8600 | C5—H5A | 0.9700 |
N2—C9 | 1.322 (3) | C5—H5B | 0.9700 |
N2—C10 | 1.382 (3) | C6—C7 | 1.525 (3) |
O1—C8 | 1.214 (3) | C6—H6A | 0.9800 |
O2—C1 | 1.295 (3) | C7—C8 | 1.517 (3) |
O2—H2 | 0.836 (18) | C7—H7A | 0.9800 |
O3—C8 | 1.303 (3) | C10—C11 | 1.375 (4) |
O3—H3 | 0.854 (18) | C10—C15 | 1.413 (3) |
O4—C1 | 1.234 (2) | C11—C12 | 1.396 (4) |
O5—C3 | 1.434 (3) | C11—H11A | 0.9300 |
O5—C6 | 1.443 (3) | C12—C13 | 1.395 (6) |
C1—C2 | 1.508 (3) | C12—H12A | 0.9300 |
C2—C3 | 1.544 (3) | C13—C14 | 1.361 (5) |
C2—C7 | 1.565 (3) | C13—H13A | 0.9300 |
C2—H2A | 0.9800 | C14—C15 | 1.374 (4) |
C3—C4 | 1.530 (3) | C14—H14A | 0.9300 |
C3—H3A | 0.9800 | ||
C15—S1—C9 | 89.18 (12) | O5—C6—C5 | 102.47 (18) |
C9—N1—H1A | 120.0 | C7—C6—C5 | 110.16 (19) |
C9—N1—H1B | 120.0 | O5—C6—H6A | 113.6 |
H1A—N1—H1B | 120.0 | C7—C6—H6A | 113.6 |
C9—N2—C10 | 111.49 (19) | C5—C6—H6A | 113.6 |
C1—O2—H2 | 109 (2) | C8—C7—C6 | 114.11 (18) |
C8—O3—H3 | 112 (2) | C8—C7—C2 | 115.16 (16) |
C3—O5—C6 | 96.24 (15) | C6—C7—C2 | 101.23 (17) |
O4—C1—O2 | 123.04 (18) | C8—C7—H7A | 108.7 |
O4—C1—C2 | 121.43 (18) | C6—C7—H7A | 108.7 |
O2—C1—C2 | 115.39 (17) | C2—C7—H7A | 108.7 |
C1—C2—C3 | 110.23 (17) | O1—C8—O3 | 124.6 (2) |
C1—C2—C7 | 116.64 (16) | O1—C8—C7 | 123.1 (2) |
C3—C2—C7 | 100.43 (16) | O3—C8—C7 | 112.29 (18) |
C1—C2—H2A | 109.7 | N1—C9—N2 | 123.7 (2) |
C3—C2—H2A | 109.7 | N1—C9—S1 | 121.07 (18) |
C7—C2—H2A | 109.7 | N2—C9—S1 | 115.2 (2) |
O5—C3—C4 | 103.13 (17) | C11—C10—N2 | 125.6 (2) |
O5—C3—C2 | 102.91 (16) | C11—C10—C15 | 120.4 (2) |
C4—C3—C2 | 108.53 (18) | N2—C10—C15 | 114.0 (2) |
O5—C3—H3A | 113.7 | C10—C11—C12 | 118.0 (3) |
C4—C3—H3A | 113.7 | C10—C11—H11A | 121.0 |
C2—C3—H3A | 113.7 | C12—C11—H11A | 121.0 |
C3—C4—C5 | 101.17 (18) | C11—C12—C13 | 120.6 (3) |
C3—C4—H4A | 111.5 | C11—C12—H12A | 119.7 |
C5—C4—H4A | 111.5 | C13—C12—H12A | 119.7 |
C3—C4—H4B | 111.5 | C14—C13—C12 | 121.3 (3) |
C5—C4—H4B | 111.5 | C14—C13—H13A | 119.3 |
H4A—C4—H4B | 109.4 | C12—C13—H13A | 119.3 |
C6—C5—C4 | 101.63 (17) | C13—C14—C15 | 118.7 (3) |
C6—C5—H5A | 111.4 | C13—C14—H14A | 120.6 |
C4—C5—H5A | 111.4 | C15—C14—H14A | 120.6 |
C6—C5—H5B | 111.4 | C14—C15—C10 | 120.9 (3) |
C4—C5—H5B | 111.4 | C14—C15—S1 | 128.9 (3) |
H5A—C5—H5B | 109.3 | C10—C15—S1 | 110.1 (2) |
O5—C6—C7 | 102.38 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.13 | 2.953 (3) | 161 |
N1—H1B···O5 | 0.86 | 2.29 | 3.061 (3) | 150 |
N1—H1B···O4 | 0.86 | 2.38 | 2.991 (3) | 128 |
O2—H2···O4ii | 0.84 (2) | 1.87 (2) | 2.700 (2) | 174 (3) |
O3—H3···N2i | 0.85 (2) | 1.76 (2) | 2.611 (2) | 176 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C8H10O5·C7H6N2S |
Mr | 336.36 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.3082 (1), 9.0428 (1), 11.0438 (2) |
α, β, γ (°) | 67.1546 (8), 83.0101 (8), 86.9193 (9) |
V (Å3) | 758.93 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.43 × 0.27 × 0.16 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.92, 0.96 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11829, 3416, 2675 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.159, 1.07 |
No. of reflections | 3416 |
No. of parameters | 214 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.67, −1.05 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.13 | 2.953 (3) | 161.0 |
N1—H1B···O5 | 0.86 | 2.29 | 3.061 (3) | 150.1 |
N1—H1B···O4 | 0.86 | 2.38 | 2.991 (3) | 128.0 |
O2—H2···O4ii | 0.836 (18) | 1.868 (18) | 2.700 (2) | 174 (3) |
O3—H3···N2i | 0.854 (18) | 1.758 (19) | 2.611 (2) | 176 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+2, −z. |
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.