Abstract
In the title compound, C12H9NO3S, the isoindoline-1,3-dione group is almost planar, with an r.m.s. deviation of 0.020 Å, whereas the heterocyclic ring approximates to an envelope with the methylene group not adjacent to the S atom in the flap position. A short intramolecular C—H⋯O contact generates an S(6) ring motif. In the crystal structure, weak aromatic π–π stacking interactions occur between the centroids of the benzene rings at a distance of 3.558 (2) Å.
Related literature
For background to isocoumarins, see: Hussain et al. (2001 ▶); Lee et al. (2001 ▶); Nozawa et al. (1981 ▶). For related crystal structures, see: Beck et al. (2007 ▶); Freer & Kraut (1965 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).
Experimental
Crystal data
C12H9NO3S
M r = 247.26
Monoclinic,
a = 8.0601 (13) Å
b = 6.9860 (11) Å
c = 19.709 (3) Å
β = 99.296 (9)°
V = 1095.2 (3) Å3
Z = 4
Mo Kα radiation
μ = 0.29 mm−1
T = 296 K
0.24 × 0.10 × 0.08 mm
Data collection
Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.968, T max = 0.978
14781 measured reflections
1934 independent reflections
1105 reflections with I > 2σ(I)
R int = 0.093
Refinement
R[F 2 > 2σ(F 2)] = 0.055
wR(F 2) = 0.151
S = 1.02
1934 reflections
154 parameters
H-atom parameters constrained
Δρmax = 0.40 e Å−3
Δρmin = −0.31 e Å−3
Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.
Supplementary Material
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043400/hb5705sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043400/hb5705Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C10—H10B⋯O1 | 0.97 | 2.52 | 3.149 (5) | 122 |
Acknowledgments
The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.
supplementary crystallographic information
Comment
Isocoumarins are important class of naturally occurring compounds. Their structure is similar to coumarin but with inverted lactone ring. They exhibit a wide range of biological activities such as antimicrobial (Hussain et al., 2001), anti-fungal (Nozawa et al., 1981), anti-angiogenic (Lee et al., 2001). The title compound (I, Fig. 1) was obtained as an interesting side-product during the synthesis of isocoumarin.
The crystal structure of D,L-homocysteine thiolactone hydrochloride (Freer & Kraut, 1965) and (R*)-2-(4-Chlorophenyl)-N-(hept-4-yl)-2-((S*)-2- oxotetrahydrothiophen-3-ylamino)acetamide (Beck et al., 2007) have been reported which contain the heterocyclic ring.
The title compound essentially consists of monomers. In (I), the 2-benzoazole-1,3-dione group (C1–C8/N1/O1/O2) is planar with r.m.s. deviation of 0.0196 Å. The heterocyclic ring (C9/C10/C11/S1/C12) is not planar as the r.m.s. deviation of the plane is 0.1511 Å. The dihedral angle between these two groups is 88.05 (10)°. There exist weak intramolecular H-bondings of C—H···O type (Table 1, Fig. 1) completing S(5) and S(6) ring motifs (Bernstein et al., 1995). There exist π–π interaction between the centroids of benzene rings at a distance of 3.558 (2) Å [symmetry: 1 - x, - y, - z].
Experimental
Homophthallic acid (1.0 g, 5.5 mmol, 1 eq) was added to 4-(methylthio)-2-(1,3-dioxoisoindolin-2-yl)butanoyl chloride (6.5 g, 0.022 mol, 4 eq) and the mixture was heated at 473 K with continuous stirring for 6 h. The crude product was added to chilled water (20 ml), partitioned with EtOAc (3 × 25 ml), organic layer was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The column chromatographic separation using EtOAc and n-hexane (3:7) as mobile phase afforded the title compound (I) as colourless needles.
Refinement
The H atoms were positioned geometrically with C—H = 0.93–0.97 Å and were included in the refinement in the riding model approximation, with Uiso(H) = xUeq(C), where x = 1.2 for all H atoms.
Figures
Fig. 1.
View of (I) with displacement ellipsoids drawn at the 50% probability level.
Crystal data
| C12H9NO3S | F(000) = 512 |
| Mr = 247.26 | Dx = 1.500 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1105 reflections |
| a = 8.0601 (13) Å | θ = 2.1–25.0° |
| b = 6.9860 (11) Å | µ = 0.29 mm−1 |
| c = 19.709 (3) Å | T = 296 K |
| β = 99.296 (9)° | Needle, colourless |
| V = 1095.2 (3) Å3 | 0.24 × 0.10 × 0.08 mm |
| Z = 4 |
Data collection
| Bruker Kappa APEXII CCD diffractometer | 1934 independent reflections |
| Radiation source: fine-focus sealed tube | 1105 reflections with I > 2σ(I) |
| graphite | Rint = 0.093 |
| Detector resolution: 8.2 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
| ω scans | h = −9→9 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −8→8 |
| Tmin = 0.968, Tmax = 0.978 | l = −23→23 |
| 14781 measured reflections |
Refinement
| 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.151 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0651P)2 + 0.3208P] where P = (Fo2 + 2Fc2)/3 |
| 1934 reflections | (Δ/σ)max < 0.001 |
| 154 parameters | Δρmax = 0.40 e Å−3 |
| 0 restraints | Δρmin = −0.31 e Å−3 |
Special details
| Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
| 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 | ||
| S1 | 1.27260 (14) | 0.17317 (15) | 0.21281 (6) | 0.0666 (4) | |
| O1 | 1.0043 (4) | 0.2417 (4) | 0.01824 (15) | 0.0690 (11) | |
| O2 | 0.6135 (4) | 0.3134 (4) | 0.15927 (16) | 0.0694 (11) | |
| O3 | 1.0050 (3) | −0.0304 (4) | 0.16664 (14) | 0.0619 (11) | |
| N1 | 0.8391 (4) | 0.2932 (4) | 0.10189 (16) | 0.0463 (11) | |
| C1 | 0.8677 (5) | 0.2558 (5) | 0.0348 (2) | 0.0496 (14) | |
| C2 | 0.6994 (5) | 0.2417 (5) | −0.0077 (2) | 0.0445 (14) | |
| C3 | 0.6538 (6) | 0.2073 (5) | −0.0763 (2) | 0.0600 (16) | |
| C4 | 0.4821 (7) | 0.1996 (6) | −0.1015 (2) | 0.0724 (19) | |
| C5 | 0.3638 (6) | 0.2223 (6) | −0.0585 (3) | 0.073 (2) | |
| C6 | 0.4108 (5) | 0.2546 (5) | 0.0105 (3) | 0.0580 (16) | |
| C7 | 0.5801 (4) | 0.2646 (5) | 0.0350 (2) | 0.0469 (14) | |
| C8 | 0.6676 (5) | 0.2926 (5) | 0.1061 (2) | 0.0486 (14) | |
| C9 | 0.9686 (4) | 0.3132 (5) | 0.1613 (2) | 0.0492 (12) | |
| C10 | 1.0927 (5) | 0.4715 (5) | 0.1568 (2) | 0.0537 (16) | |
| C11 | 1.2487 (5) | 0.4309 (5) | 0.2093 (2) | 0.0553 (16) | |
| C12 | 1.0662 (5) | 0.1259 (5) | 0.17663 (18) | 0.0444 (12) | |
| H3 | 0.73362 | 0.18977 | −0.10491 | 0.0718* | |
| H4 | 0.44640 | 0.17879 | −0.14821 | 0.0870* | |
| H5 | 0.25006 | 0.21559 | −0.07677 | 0.0880* | |
| H6 | 0.33150 | 0.26915 | 0.03956 | 0.0696* | |
| H9 | 0.91266 | 0.34070 | 0.20085 | 0.0591* | |
| H10A | 1.04437 | 0.59374 | 0.16649 | 0.0646* | |
| H10B | 1.12157 | 0.47652 | 0.11092 | 0.0646* | |
| H11A | 1.23521 | 0.48081 | 0.25402 | 0.0667* | |
| H11B | 1.34670 | 0.49028 | 0.19538 | 0.0667* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0529 (7) | 0.0572 (7) | 0.0828 (9) | 0.0032 (5) | −0.0094 (6) | 0.0022 (6) |
| O1 | 0.0456 (18) | 0.086 (2) | 0.078 (2) | −0.0061 (15) | 0.0178 (16) | −0.0142 (16) |
| O2 | 0.0619 (19) | 0.075 (2) | 0.076 (2) | −0.0060 (16) | 0.0255 (17) | −0.0102 (16) |
| O3 | 0.0674 (19) | 0.0400 (16) | 0.078 (2) | −0.0076 (14) | 0.0106 (16) | −0.0004 (14) |
| N1 | 0.0420 (19) | 0.0466 (18) | 0.049 (2) | 0.0011 (14) | 0.0038 (16) | 0.0021 (15) |
| C1 | 0.040 (2) | 0.042 (2) | 0.067 (3) | −0.0027 (18) | 0.009 (2) | 0.0031 (18) |
| C2 | 0.043 (2) | 0.037 (2) | 0.052 (3) | −0.0082 (16) | 0.003 (2) | 0.0049 (17) |
| C3 | 0.069 (3) | 0.051 (2) | 0.058 (3) | −0.013 (2) | 0.004 (2) | 0.009 (2) |
| C4 | 0.091 (4) | 0.056 (3) | 0.059 (3) | −0.017 (3) | −0.022 (3) | 0.010 (2) |
| C5 | 0.054 (3) | 0.044 (3) | 0.111 (5) | −0.006 (2) | −0.019 (3) | 0.018 (3) |
| C6 | 0.041 (2) | 0.037 (2) | 0.092 (4) | −0.0023 (18) | −0.001 (2) | 0.004 (2) |
| C7 | 0.039 (2) | 0.029 (2) | 0.069 (3) | −0.0025 (16) | −0.002 (2) | 0.0051 (17) |
| C8 | 0.042 (2) | 0.038 (2) | 0.068 (3) | −0.0018 (17) | 0.016 (2) | 0.0010 (19) |
| C9 | 0.046 (2) | 0.048 (2) | 0.053 (2) | −0.0043 (18) | 0.006 (2) | −0.0034 (19) |
| C10 | 0.061 (3) | 0.041 (2) | 0.058 (3) | −0.005 (2) | 0.006 (2) | −0.0018 (18) |
| C11 | 0.056 (3) | 0.053 (2) | 0.056 (3) | −0.007 (2) | 0.006 (2) | −0.009 (2) |
| C12 | 0.048 (2) | 0.042 (2) | 0.044 (2) | −0.0006 (18) | 0.0098 (19) | 0.0016 (17) |
Geometric parameters (Å, °)
| S1—C11 | 1.811 (4) | C6—C7 | 1.374 (6) |
| S1—C12 | 1.733 (4) | C7—C8 | 1.477 (5) |
| O1—C1 | 1.202 (5) | C9—C10 | 1.503 (5) |
| O2—C8 | 1.207 (5) | C9—C12 | 1.532 (5) |
| O3—C12 | 1.201 (5) | C10—C11 | 1.521 (6) |
| N1—C1 | 1.403 (5) | C3—H3 | 0.9300 |
| N1—C8 | 1.398 (5) | C4—H4 | 0.9300 |
| N1—C9 | 1.444 (5) | C5—H5 | 0.9300 |
| C1—C2 | 1.478 (6) | C6—H6 | 0.9300 |
| C2—C3 | 1.364 (5) | C9—H9 | 0.9800 |
| C2—C7 | 1.386 (5) | C10—H10A | 0.9700 |
| C3—C4 | 1.394 (7) | C10—H10B | 0.9700 |
| C4—C5 | 1.383 (7) | C11—H11A | 0.9700 |
| C5—C6 | 1.370 (8) | C11—H11B | 0.9700 |
| C11—S1—C12 | 94.86 (18) | S1—C12—O3 | 125.6 (3) |
| C1—N1—C8 | 111.7 (3) | S1—C12—C9 | 110.3 (2) |
| C1—N1—C9 | 125.1 (3) | O3—C12—C9 | 124.1 (3) |
| C8—N1—C9 | 123.0 (3) | C2—C3—H3 | 121.00 |
| O1—C1—N1 | 124.6 (4) | C4—C3—H3 | 122.00 |
| O1—C1—C2 | 129.6 (4) | C3—C4—H4 | 119.00 |
| N1—C1—C2 | 105.7 (3) | C5—C4—H4 | 119.00 |
| C1—C2—C3 | 130.5 (4) | C4—C5—H5 | 119.00 |
| C1—C2—C7 | 108.2 (3) | C6—C5—H5 | 119.00 |
| C3—C2—C7 | 121.3 (4) | C5—C6—H6 | 121.00 |
| C2—C3—C4 | 116.9 (4) | C7—C6—H6 | 121.00 |
| C3—C4—C5 | 121.4 (4) | N1—C9—H9 | 107.00 |
| C4—C5—C6 | 121.3 (5) | C10—C9—H9 | 107.00 |
| C5—C6—C7 | 117.2 (4) | C12—C9—H9 | 107.00 |
| C2—C7—C6 | 121.9 (4) | C9—C10—H10A | 110.00 |
| C2—C7—C8 | 108.7 (3) | C9—C10—H10B | 110.00 |
| C6—C7—C8 | 129.5 (4) | C11—C10—H10A | 110.00 |
| O2—C8—N1 | 123.4 (4) | C11—C10—H10B | 110.00 |
| O2—C8—C7 | 131.0 (4) | H10A—C10—H10B | 108.00 |
| N1—C8—C7 | 105.6 (3) | S1—C11—H11A | 110.00 |
| N1—C9—C10 | 115.1 (3) | S1—C11—H11B | 110.00 |
| N1—C9—C12 | 111.0 (3) | C10—C11—H11A | 110.00 |
| C10—C9—C12 | 108.3 (3) | C10—C11—H11B | 110.00 |
| C9—C10—C11 | 107.9 (3) | H11A—C11—H11B | 109.00 |
| S1—C11—C10 | 106.4 (2) | ||
| C12—S1—C11—C10 | −19.3 (3) | C1—C2—C7—C6 | −178.6 (3) |
| C11—S1—C12—O3 | −178.8 (4) | C1—C2—C7—C8 | −0.4 (4) |
| C11—S1—C12—C9 | −0.9 (3) | C3—C2—C7—C6 | −0.3 (6) |
| C8—N1—C1—O1 | −177.2 (3) | C3—C2—C7—C8 | 178.0 (3) |
| C8—N1—C1—C2 | 3.5 (4) | C2—C3—C4—C5 | −1.2 (6) |
| C9—N1—C1—O1 | −2.4 (6) | C3—C4—C5—C6 | 0.5 (6) |
| C9—N1—C1—C2 | 178.3 (3) | C4—C5—C6—C7 | 0.4 (6) |
| C1—N1—C8—O2 | 176.8 (3) | C5—C6—C7—C2 | −0.5 (5) |
| C1—N1—C8—C7 | −3.8 (4) | C5—C6—C7—C8 | −178.3 (4) |
| C9—N1—C8—O2 | 1.9 (5) | C2—C7—C8—O2 | −178.1 (4) |
| C9—N1—C8—C7 | −178.7 (3) | C2—C7—C8—N1 | 2.5 (4) |
| C1—N1—C9—C10 | 59.6 (4) | C6—C7—C8—O2 | −0.1 (7) |
| C1—N1—C9—C12 | −63.9 (4) | C6—C7—C8—N1 | −179.5 (4) |
| C8—N1—C9—C10 | −126.2 (3) | N1—C9—C10—C11 | −160.7 (3) |
| C8—N1—C9—C12 | 110.3 (4) | C12—C9—C10—C11 | −35.8 (4) |
| O1—C1—C2—C3 | 0.8 (7) | N1—C9—C12—S1 | 148.7 (2) |
| O1—C1—C2—C7 | 178.9 (4) | N1—C9—C12—O3 | −33.4 (5) |
| N1—C1—C2—C3 | −180.0 (4) | C10—C9—C12—S1 | 21.4 (4) |
| N1—C1—C2—C7 | −1.8 (4) | C10—C9—C12—O3 | −160.7 (4) |
| C1—C2—C3—C4 | 179.0 (4) | C9—C10—C11—S1 | 34.4 (4) |
| C7—C2—C3—C4 | 1.1 (5) |
Hydrogen-bond geometry (Å, °)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10B···O1 | 0.97 | 2.52 | 3.149 (5) | 122 |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5705).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043400/hb5705sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043400/hb5705Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report