Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104034146/fg1803sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104034146/fg1803Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104034146/fg1803IIsup3.hkl |
CCDC references: 264815; 264816
The title compounds were synthesized according to the procedure reported by Nagano et al. (1982), by refluxing 4-chloro-2-fluoro-5-prop-2-ynyloxyphenylamine with the corresponding anhydrides in acetic acid for 1 h. The crude products were purified by silica-gel column chromatography and then grown from acetone to afford colorless single crystals suitable for X-ray diffraction. For (I), m.p. 409–410 K (409.4 K; Nagano et al., 1982). 1H NMR (p.p.m.): 1.82–1.84 (m, 2 H), 2.58 (t, 1 H, J = 2.4 Hz, C*CH), 2.44–2.75 (m, 4 H), 4.75 (d, 2 H, J = 2.4 Hz, CH2C*C), 6.98 (d, 1 H, J = 6.6 Hz, Ph), 7.29 (d, 1 H, J = 9 Hz, Ph). For (II), m.p. 368–369 K. Analysis C17H13ClFNO3 requires: C 61.18, H 3.93, N 4.20%; found: C 61.22, H 4.01, N 4.24%. 1H NMR (p.p.m.): 2.35–2.39 (m, 2 H), 2.58 (t, 1 H, J = 2.4 Hz, C*CH), 2.68–2.73 (m, 2 H), 3.30–3.32 (m, 2 H), 4.75 (d, 2 H, J = 2.4 Hz, CH2C*C), 5.99–6.01 (m, 2 H), 6.96 (d, 1 H, J = 6.6 Hz, Ph), 7.29 (d, 1 H, J = 9 Hz, Ph).
For both (I) and (II), H atoms were found in difference maps and were subsequently allowed for in the refinements as riding atoms, with C—H distances of 0.93, 0.97 and 0.98 Å, and with Uiso(H) = 1.2Ueq(parent atom). In (II), it soon became apparent that the propargyl group was disordered unequally over two orientations (see Supplementary Material for a plot of the electron-density in the relevant plane please provide). DFIX restraints [1.428 (3), 1.158 (3) and 2.396 (3) Å] were used to control the refinement of the propargyl C—C distances in the two components (C17/C18/C19 and C17A/C18A/C19A), whose occupancies refined to 0.549 (5) and 0.451 (5).
For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C17H13ClFNO3 | Z = 2 |
Mr = 333.73 | F(000) = 344 |
Triclinic, P1 | Dx = 1.417 Mg m−3 |
Hall symbol: -P 1 | Melting point: 409(1) K |
a = 9.313 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.380 (5) Å | Cell parameters from 860 reflections |
c = 10.485 (6) Å | θ = 3.3–26.0° |
α = 99.663 (9)° | µ = 0.27 mm−1 |
β = 104.263 (9)° | T = 293 K |
γ = 112.778 (8)° | Prism, colorless |
V = 782.1 (7) Å3 | 0.36 × 0.24 × 0.22 mm |
Bruker SMART CCD area-detector diffractometer | 2747 independent reflections |
Radiation source: fine-focus sealed tube | 2059 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −11→9 |
Tmin = 0.906, Tmax = 0.943 | k = −9→11 |
4071 measured reflections | l = −10→12 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.3951P] where P = (Fo2 + 2Fc2)/3 |
2747 reflections | (Δ/σ)max = 0.002 |
208 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C17H13ClFNO3 | γ = 112.778 (8)° |
Mr = 333.73 | V = 782.1 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.313 (5) Å | Mo Kα radiation |
b = 9.380 (5) Å | µ = 0.27 mm−1 |
c = 10.485 (6) Å | T = 293 K |
α = 99.663 (9)° | 0.36 × 0.24 × 0.22 mm |
β = 104.263 (9)° |
Bruker SMART CCD area-detector diffractometer | 2747 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 2059 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.943 | Rint = 0.017 |
4071 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.39 e Å−3 |
2747 reflections | Δρmin = −0.28 e Å−3 |
208 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 | ||
Cl1 | 1.10934 (8) | 0.63339 (8) | 0.87631 (7) | 0.0561 (2) | |
F1 | 0.88880 (18) | 0.69124 (17) | 0.40938 (15) | 0.0555 (4) | |
O1 | 0.5461 (2) | 0.6103 (2) | 0.32370 (19) | 0.0545 (5) | |
O2 | 0.5902 (2) | 0.13836 (19) | 0.24919 (17) | 0.0479 (4) | |
O3 | 0.8209 (2) | 0.33054 (19) | 0.76829 (16) | 0.0470 (4) | |
N2 | 0.6090 (2) | 0.3948 (2) | 0.32126 (19) | 0.0389 (5) | |
C1 | 0.5233 (3) | 0.4773 (3) | 0.2666 (2) | 0.0390 (5) | |
C3 | 0.5445 (3) | 0.2389 (3) | 0.2296 (2) | 0.0379 (5) | |
C3A | 0.4144 (3) | 0.2288 (3) | 0.1088 (2) | 0.0404 (6) | |
C4 | 0.3108 (4) | 0.0863 (3) | −0.0159 (3) | 0.0578 (7) | |
H4A | 0.2350 | −0.0012 | 0.0079 | 0.069* | |
H4B | 0.3812 | 0.0490 | −0.0509 | 0.069* | |
C5 | 0.2141 (6) | 0.1325 (5) | −0.1248 (4) | 0.1062 (16) | |
H5A | 0.2828 | 0.1767 | −0.1780 | 0.127* | |
H5B | 0.1182 | 0.0346 | −0.1867 | 0.127* | |
C6 | 0.1578 (5) | 0.2458 (5) | −0.0785 (4) | 0.0925 (13) | |
H6A | 0.0691 | 0.1917 | −0.0450 | 0.111* | |
H6B | 0.1101 | 0.2744 | −0.1575 | 0.111* | |
C7 | 0.2833 (3) | 0.4007 (3) | 0.0325 (3) | 0.0521 (7) | |
H7A | 0.3419 | 0.4794 | −0.0087 | 0.063* | |
H7B | 0.2273 | 0.4453 | 0.0816 | 0.063* | |
C7A | 0.4029 (3) | 0.3668 (3) | 0.1298 (2) | 0.0395 (5) | |
C11 | 0.7297 (3) | 0.4524 (3) | 0.4541 (2) | 0.0363 (5) | |
C12 | 0.8663 (3) | 0.6014 (3) | 0.4975 (2) | 0.0392 (5) | |
C13 | 0.9835 (3) | 0.6593 (3) | 0.6260 (2) | 0.0418 (6) | |
H13 | 1.0744 | 0.7603 | 0.6537 | 0.050* | |
C14 | 0.9637 (3) | 0.5642 (3) | 0.7134 (2) | 0.0385 (5) | |
C15 | 0.8289 (3) | 0.4130 (3) | 0.6725 (2) | 0.0368 (5) | |
C16 | 0.7123 (3) | 0.3584 (3) | 0.5431 (2) | 0.0373 (5) | |
H16 | 0.6210 | 0.2576 | 0.5153 | 0.045* | |
C17 | 0.6888 (3) | 0.1711 (3) | 0.7292 (3) | 0.0498 (7) | |
H17A | 0.5853 | 0.1721 | 0.6831 | 0.060* | |
H17B | 0.6807 | 0.1389 | 0.8113 | 0.060* | |
C18 | 0.7120 (3) | 0.0534 (3) | 0.6384 (3) | 0.0556 (7) | |
C19 | 0.7317 (4) | −0.0416 (4) | 0.5683 (4) | 0.0859 (11) | |
H19 | 0.7475 | −0.1179 | 0.5119 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0504 (4) | 0.0462 (4) | 0.0451 (4) | 0.0108 (3) | −0.0030 (3) | 0.0041 (3) |
F1 | 0.0557 (9) | 0.0493 (9) | 0.0580 (9) | 0.0168 (7) | 0.0178 (8) | 0.0262 (7) |
O1 | 0.0559 (11) | 0.0441 (11) | 0.0579 (11) | 0.0287 (9) | 0.0089 (9) | 0.0020 (9) |
O2 | 0.0539 (11) | 0.0374 (9) | 0.0513 (10) | 0.0235 (8) | 0.0118 (9) | 0.0117 (8) |
O3 | 0.0540 (10) | 0.0342 (9) | 0.0377 (9) | 0.0107 (8) | 0.0069 (8) | 0.0099 (7) |
N2 | 0.0414 (11) | 0.0339 (10) | 0.0372 (11) | 0.0178 (9) | 0.0072 (9) | 0.0072 (8) |
C1 | 0.0417 (13) | 0.0361 (13) | 0.0421 (13) | 0.0202 (11) | 0.0151 (11) | 0.0105 (10) |
C3 | 0.0379 (13) | 0.0339 (12) | 0.0393 (13) | 0.0137 (10) | 0.0140 (10) | 0.0095 (10) |
C3A | 0.0412 (13) | 0.0387 (13) | 0.0386 (13) | 0.0166 (11) | 0.0130 (11) | 0.0093 (10) |
C4 | 0.0626 (18) | 0.0456 (15) | 0.0482 (16) | 0.0231 (14) | 0.0012 (14) | 0.0017 (12) |
C5 | 0.124 (3) | 0.080 (3) | 0.070 (2) | 0.057 (3) | −0.033 (2) | −0.0150 (19) |
C6 | 0.091 (3) | 0.086 (3) | 0.070 (2) | 0.053 (2) | −0.0247 (19) | −0.0073 (19) |
C7 | 0.0520 (16) | 0.0560 (16) | 0.0493 (15) | 0.0303 (13) | 0.0094 (13) | 0.0150 (13) |
C7A | 0.0400 (13) | 0.0400 (13) | 0.0401 (13) | 0.0192 (11) | 0.0136 (11) | 0.0123 (10) |
C11 | 0.0372 (12) | 0.0351 (12) | 0.0332 (12) | 0.0173 (10) | 0.0088 (10) | 0.0038 (10) |
C12 | 0.0435 (13) | 0.0341 (12) | 0.0435 (13) | 0.0183 (11) | 0.0172 (11) | 0.0141 (10) |
C13 | 0.0362 (13) | 0.0306 (12) | 0.0480 (14) | 0.0099 (10) | 0.0109 (11) | 0.0042 (11) |
C14 | 0.0370 (13) | 0.0331 (12) | 0.0376 (13) | 0.0146 (10) | 0.0066 (10) | 0.0029 (10) |
C15 | 0.0398 (13) | 0.0322 (12) | 0.0361 (12) | 0.0168 (10) | 0.0109 (10) | 0.0056 (10) |
C16 | 0.0352 (12) | 0.0308 (12) | 0.0383 (13) | 0.0107 (10) | 0.0102 (10) | 0.0049 (10) |
C17 | 0.0548 (16) | 0.0358 (14) | 0.0489 (15) | 0.0121 (12) | 0.0139 (13) | 0.0143 (12) |
C18 | 0.0518 (16) | 0.0370 (15) | 0.0599 (18) | 0.0133 (13) | 0.0045 (14) | 0.0080 (13) |
C19 | 0.076 (2) | 0.059 (2) | 0.098 (3) | 0.0294 (18) | 0.010 (2) | −0.0056 (19) |
Cl1—C14 | 1.728 (2) | C6—C7 | 1.509 (4) |
F1—C12 | 1.352 (3) | C6—H6A | 0.97 |
O1—C1 | 1.201 (3) | C6—H6B | 0.97 |
O2—C3 | 1.202 (3) | C7—C7A | 1.485 (3) |
O3—C15 | 1.366 (3) | C7—H7A | 0.97 |
O3—C17 | 1.428 (3) | C7—H7B | 0.97 |
N2—C1 | 1.402 (3) | C11—C12 | 1.379 (3) |
N2—C3 | 1.409 (3) | C11—C16 | 1.384 (3) |
N2—C11 | 1.414 (3) | C12—C13 | 1.369 (3) |
C1—C7A | 1.482 (3) | C13—C14 | 1.377 (3) |
C3—C3A | 1.481 (3) | C13—H13 | 0.93 |
C3A—C7A | 1.326 (3) | C14—C15 | 1.387 (3) |
C3A—C4 | 1.490 (3) | C15—C16 | 1.375 (3) |
C4—C5 | 1.505 (4) | C16—H16 | 0.93 |
C4—H4A | 0.97 | C17—C18 | 1.451 (4) |
C4—H4B | 0.97 | C17—H17A | 0.97 |
C5—C6 | 1.422 (5) | C17—H17B | 0.97 |
C5—H5A | 0.97 | C18—C19 | 1.158 (4) |
C5—H5B | 0.97 | C19—H19 | 0.93 |
C15—O3—C17 | 118.15 (18) | C6—C7—H7A | 109.8 |
C1—N2—C3 | 109.57 (18) | C7A—C7—H7B | 109.8 |
C1—N2—C11 | 125.20 (18) | C6—C7—H7B | 109.8 |
C3—N2—C11 | 124.93 (18) | H7A—C7—H7B | 108.2 |
O1—C1—N2 | 124.9 (2) | C3A—C7A—C1 | 109.1 (2) |
O1—C1—C7A | 128.9 (2) | C3A—C7A—C7 | 124.7 (2) |
N2—C1—C7A | 106.13 (19) | C1—C7A—C7 | 126.1 (2) |
O2—C3—N2 | 125.2 (2) | C12—C11—C16 | 118.7 (2) |
O2—C3—C3A | 128.8 (2) | C12—C11—N2 | 121.3 (2) |
N2—C3—C3A | 106.02 (19) | C16—C11—N2 | 120.0 (2) |
C7A—C3A—C3 | 109.1 (2) | F1—C12—C13 | 118.6 (2) |
C7A—C3A—C4 | 125.0 (2) | F1—C12—C11 | 119.3 (2) |
C3—C3A—C4 | 125.9 (2) | C13—C12—C11 | 122.0 (2) |
C3A—C4—C5 | 109.7 (2) | C12—C13—C14 | 118.4 (2) |
C3A—C4—H4A | 109.7 | C12—C13—H13 | 120.8 |
C5—C4—H4A | 109.7 | C14—C13—H13 | 120.8 |
C3A—C4—H4B | 109.7 | C13—C14—C15 | 121.1 (2) |
C5—C4—H4B | 109.7 | C13—C14—Cl1 | 119.67 (18) |
H4A—C4—H4B | 108.2 | C15—C14—Cl1 | 119.22 (18) |
C6—C5—C4 | 116.8 (3) | O3—C15—C16 | 124.8 (2) |
C6—C5—H5A | 108.1 | O3—C15—C14 | 116.0 (2) |
C4—C5—H5A | 108.1 | C16—C15—C14 | 119.2 (2) |
C6—C5—H5B | 108.1 | C15—C16—C11 | 120.5 (2) |
C4—C5—H5B | 108.1 | C15—C16—H16 | 119.7 |
H5A—C5—H5B | 107.3 | C11—C16—H16 | 119.7 |
C5—C6—C7 | 117.6 (3) | O3—C17—C18 | 112.5 (2) |
C5—C6—H6A | 107.9 | O3—C17—H17A | 109.1 |
C7—C6—H6A | 107.9 | C18—C17—H17A | 109.1 |
C5—C6—H6B | 107.9 | O3—C17—H17B | 109.1 |
C7—C6—H6B | 107.9 | C18—C17—H17B | 109.1 |
H6A—C6—H6B | 107.2 | H17A—C17—H17B | 107.8 |
C7A—C7—C6 | 109.4 (2) | C19—C18—C17 | 178.6 (3) |
C7A—C7—H7A | 109.8 | C18—C19—H19 | 180.0 |
C3—N2—C1—O1 | 177.0 (2) | C6—C7—C7A—C3A | 10.7 (4) |
C11—N2—C1—O1 | 3.1 (4) | C6—C7—C7A—C1 | −167.0 (3) |
C3—N2—C1—C7A | −2.4 (3) | C1—N2—C11—C12 | −54.8 (3) |
C11—N2—C1—C7A | −176.3 (2) | C3—N2—C11—C12 | 132.3 (2) |
C1—N2—C3—O2 | −178.4 (2) | C1—N2—C11—C16 | 125.5 (2) |
C11—N2—C3—O2 | −4.4 (4) | C3—N2—C11—C16 | −47.5 (3) |
C1—N2—C3—C3A | 2.1 (3) | C16—C11—C12—F1 | 177.0 (2) |
C11—N2—C3—C3A | 176.0 (2) | N2—C11—C12—F1 | −2.7 (3) |
O2—C3—C3A—C7A | 179.6 (2) | C16—C11—C12—C13 | −0.7 (4) |
N2—C3—C3A—C7A | −0.9 (3) | N2—C11—C12—C13 | 179.5 (2) |
O2—C3—C3A—C4 | 0.4 (4) | F1—C12—C13—C14 | −177.3 (2) |
N2—C3—C3A—C4 | 179.9 (2) | C11—C12—C13—C14 | 0.5 (4) |
C7A—C3A—C4—C5 | 10.4 (4) | C12—C13—C14—C15 | 0.3 (4) |
C3—C3A—C4—C5 | −170.5 (3) | C12—C13—C14—Cl1 | 179.94 (18) |
C3A—C4—C5—C6 | −35.1 (5) | C17—O3—C15—C16 | 4.7 (3) |
C4—C5—C6—C7 | 50.8 (6) | C17—O3—C15—C14 | −177.1 (2) |
C5—C6—C7—C7A | −35.8 (5) | C13—C14—C15—O3 | −179.1 (2) |
C3—C3A—C7A—C1 | −0.6 (3) | Cl1—C14—C15—O3 | 1.3 (3) |
C4—C3A—C7A—C1 | 178.6 (2) | C13—C14—C15—C16 | −0.9 (4) |
C3—C3A—C7A—C7 | −178.6 (2) | Cl1—C14—C15—C16 | 179.52 (17) |
C4—C3A—C7A—C7 | 0.6 (4) | O3—C15—C16—C11 | 178.7 (2) |
O1—C1—C7A—C3A | −177.5 (3) | C14—C15—C16—C11 | 0.6 (3) |
N2—C1—C7A—C3A | 1.8 (3) | C12—C11—C16—C15 | 0.2 (3) |
O1—C1—C7A—C7 | 0.5 (4) | N2—C11—C16—C15 | 179.9 (2) |
N2—C1—C7A—C7 | 179.8 (2) | C15—O3—C17—C18 | 73.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O1i | 0.93 | 2.59 | 3.295 (4) | 133 |
Symmetry code: (i) x, y−1, z. |
C17H13ClFNO3 | F(000) = 1376 |
Mr = 333.73 | Dx = 1.418 Mg m−3 |
Monoclinic, C2/c | Melting point: 369(1) K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 22.712 (15) Å | Cell parameters from 885 reflections |
b = 7.474 (5) Å | θ = 3.0–24.4° |
c = 18.655 (12) Å | µ = 0.27 mm−1 |
β = 99.061 (11)° | T = 293 K |
V = 3127 (4) Å3 | Prism, colorless' |
Z = 8 | 0.34 × 0.28 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 3206 independent reflections |
Radiation source: fine-focus sealed tube | 2058 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −28→27 |
Tmin = 0.902, Tmax = 0.948 | k = −5→9 |
8627 measured reflections | l = −22→23 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0569P)2 + 5.1958P] where P = (Fo2 + 2Fc2)/3 |
3206 reflections | (Δ/σ)max < 0.001 |
230 parameters | Δρmax = 0.31 e Å−3 |
9 restraints | Δρmin = −0.25 e Å−3 |
C17H13ClFNO3 | V = 3127 (4) Å3 |
Mr = 333.73 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.712 (15) Å | µ = 0.27 mm−1 |
b = 7.474 (5) Å | T = 293 K |
c = 18.655 (12) Å | 0.34 × 0.28 × 0.20 mm |
β = 99.061 (11)° |
Bruker SMART CCD area-detector diffractometer | 3206 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 2058 reflections with I > 2σ(I) |
Tmin = 0.902, Tmax = 0.948 | Rint = 0.027 |
8627 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 9 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.31 e Å−3 |
3206 reflections | Δρmin = −0.25 e Å−3 |
230 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 | Occ. (<1) | |
Cl1 | 0.38216 (4) | 0.94181 (12) | 0.03497 (5) | 0.0711 (3) | |
F1 | 0.18203 (8) | 0.8311 (3) | 0.10933 (11) | 0.0697 (6) | |
O1 | 0.20485 (12) | 0.6548 (4) | 0.25578 (13) | 0.0871 (9) | |
O2 | 0.20038 (11) | 0.2630 (3) | 0.06959 (13) | 0.0688 (6) | |
O3 | 0.40032 (9) | 0.5794 (3) | 0.07586 (14) | 0.0696 (7) | |
N2 | 0.20966 (10) | 0.4858 (3) | 0.15471 (13) | 0.0497 (6) | |
C1 | 0.19011 (14) | 0.5228 (5) | 0.21999 (17) | 0.0621 (9) | |
C3 | 0.18841 (13) | 0.3225 (4) | 0.12499 (17) | 0.0533 (8) | |
C3A | 0.14951 (16) | 0.2418 (6) | 0.17440 (19) | 0.0718 (10) | |
H3 | 0.1680 | 0.1298 | 0.1938 | 0.086* | |
C4 | 0.0892 (2) | 0.1989 (10) | 0.1331 (3) | 0.128 (2) | |
H4A | 0.0933 | 0.1511 | 0.0858 | 0.153* | |
H4B | 0.0702 | 0.1087 | 0.1589 | 0.153* | |
C5 | 0.0519 (2) | 0.3607 (13) | 0.1240 (3) | 0.151 (3) | |
H5 | 0.0276 | 0.3822 | 0.0800 | 0.181* | |
C6 | 0.0527 (2) | 0.4783 (11) | 0.1791 (4) | 0.145 (3) | |
H6 | 0.0298 | 0.5819 | 0.1730 | 0.174* | |
C7 | 0.09085 (19) | 0.4390 (8) | 0.2494 (2) | 0.1023 (16) | |
H7A | 0.0717 | 0.3496 | 0.2756 | 0.123* | |
H7B | 0.0962 | 0.5467 | 0.2787 | 0.123* | |
C7A | 0.15069 (15) | 0.3709 (6) | 0.23609 (17) | 0.0689 (10) | |
H7 | 0.1700 | 0.3116 | 0.2805 | 0.083* | |
C11 | 0.25059 (13) | 0.5954 (4) | 0.12441 (15) | 0.0476 (7) | |
C12 | 0.23645 (13) | 0.7686 (4) | 0.10352 (15) | 0.0490 (7) | |
C13 | 0.27591 (13) | 0.8775 (4) | 0.07586 (15) | 0.0511 (7) | |
H13 | 0.2659 | 0.9949 | 0.0626 | 0.061* | |
C14 | 0.33070 (13) | 0.8087 (4) | 0.06832 (15) | 0.0476 (7) | |
C15 | 0.34536 (12) | 0.6340 (4) | 0.08740 (16) | 0.0483 (7) | |
C16 | 0.30554 (13) | 0.5278 (4) | 0.11614 (16) | 0.0513 (7) | |
H16 | 0.3156 | 0.4108 | 0.1300 | 0.062* | |
C17 | 0.4128 (2) | 0.3914 (5) | 0.0823 (6) | 0.0705 (18) | 0.549 (5) |
H17A | 0.4077 | 0.3516 | 0.1304 | 0.085* | 0.549 (5) |
H17B | 0.3843 | 0.3272 | 0.0473 | 0.085* | 0.549 (5) |
C18 | 0.47157 (19) | 0.3489 (6) | 0.0703 (3) | 0.0623 (17) | 0.549 (5) |
C19 | 0.5184 (2) | 0.3206 (10) | 0.0571 (4) | 0.076 (2) | 0.549 (5) |
H19 | 0.5563 | 0.2977 | 0.0464 | 0.091* | 0.549 (5) |
C17A | 0.4220 (4) | 0.4110 (12) | 0.1013 (4) | 0.0705 (18) | 0.451 (5) |
H17C | 0.4545 | 0.3773 | 0.0759 | 0.085* | 0.451 (5) |
H17D | 0.3905 | 0.3234 | 0.0893 | 0.085* | 0.451 (5) |
C18A | 0.4428 (4) | 0.4036 (11) | 0.1777 (3) | 0.088 (3) | 0.451 (5) |
C19A | 0.4564 (7) | 0.409 (2) | 0.2399 (4) | 0.155 (7) | 0.451 (5) |
H19A | 0.4674 | 0.4127 | 0.2901 | 0.186* | 0.451 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0766 (6) | 0.0556 (5) | 0.0844 (6) | −0.0070 (4) | 0.0231 (5) | 0.0078 (5) |
F1 | 0.0558 (11) | 0.0611 (12) | 0.0929 (14) | 0.0188 (9) | 0.0138 (10) | −0.0071 (11) |
O1 | 0.0920 (18) | 0.111 (2) | 0.0621 (15) | −0.0254 (18) | 0.0229 (13) | −0.0300 (16) |
O2 | 0.0893 (17) | 0.0551 (14) | 0.0661 (14) | 0.0038 (13) | 0.0248 (13) | −0.0057 (12) |
O3 | 0.0542 (13) | 0.0522 (14) | 0.1066 (19) | 0.0089 (11) | 0.0260 (12) | 0.0020 (13) |
N2 | 0.0489 (13) | 0.0555 (15) | 0.0455 (13) | 0.0029 (12) | 0.0103 (11) | −0.0009 (12) |
C1 | 0.0551 (18) | 0.085 (3) | 0.0453 (17) | −0.0038 (18) | 0.0043 (14) | −0.0042 (18) |
C3 | 0.0514 (17) | 0.0535 (19) | 0.0543 (18) | 0.0060 (15) | 0.0059 (14) | 0.0101 (16) |
C3A | 0.071 (2) | 0.079 (2) | 0.066 (2) | −0.014 (2) | 0.0143 (18) | 0.007 (2) |
C4 | 0.080 (3) | 0.203 (7) | 0.102 (4) | −0.062 (4) | 0.022 (3) | −0.037 (4) |
C5 | 0.047 (2) | 0.317 (11) | 0.086 (3) | 0.002 (4) | 0.000 (2) | 0.007 (5) |
C6 | 0.074 (3) | 0.234 (8) | 0.136 (5) | 0.059 (4) | 0.043 (3) | 0.042 (5) |
C7 | 0.081 (3) | 0.141 (5) | 0.093 (3) | −0.006 (3) | 0.037 (3) | −0.013 (3) |
C7A | 0.062 (2) | 0.099 (3) | 0.0481 (18) | −0.009 (2) | 0.0132 (15) | 0.0073 (19) |
C11 | 0.0500 (17) | 0.0490 (17) | 0.0442 (15) | 0.0053 (14) | 0.0089 (13) | −0.0022 (13) |
C12 | 0.0473 (16) | 0.0489 (17) | 0.0498 (16) | 0.0111 (14) | 0.0041 (13) | −0.0090 (14) |
C13 | 0.0616 (19) | 0.0382 (15) | 0.0513 (17) | 0.0098 (15) | 0.0020 (14) | −0.0023 (14) |
C14 | 0.0582 (18) | 0.0429 (16) | 0.0418 (15) | −0.0001 (14) | 0.0082 (13) | −0.0008 (13) |
C15 | 0.0457 (16) | 0.0464 (17) | 0.0541 (17) | 0.0058 (14) | 0.0119 (13) | −0.0002 (14) |
C16 | 0.0537 (17) | 0.0418 (16) | 0.0592 (18) | 0.0087 (14) | 0.0111 (14) | 0.0023 (14) |
C17 | 0.076 (3) | 0.061 (3) | 0.078 (5) | 0.021 (3) | 0.024 (3) | −0.005 (3) |
C18 | 0.060 (4) | 0.052 (4) | 0.078 (4) | −0.003 (3) | 0.018 (3) | −0.005 (3) |
C19 | 0.052 (4) | 0.083 (5) | 0.098 (5) | 0.010 (3) | 0.029 (3) | −0.009 (4) |
C17A | 0.076 (3) | 0.061 (3) | 0.078 (5) | 0.021 (3) | 0.024 (3) | −0.005 (3) |
C18A | 0.077 (6) | 0.068 (6) | 0.127 (9) | 0.024 (5) | 0.037 (6) | 0.003 (6) |
C19A | 0.202 (14) | 0.162 (14) | 0.097 (8) | 0.085 (11) | 0.012 (10) | 0.005 (9) |
Cl1—C14 | 1.724 (3) | C7—C7A | 1.508 (5) |
F1—C12 | 1.342 (3) | C7—H7A | 0.97 |
O1—C1 | 1.208 (4) | C7—H7B | 0.97 |
O2—C3 | 1.195 (4) | C7A—H7 | 0.98 |
O3—C15 | 1.362 (3) | C11—C12 | 1.375 (4) |
O3—C17A | 1.407 (7) | C11—C16 | 1.378 (4) |
O3—C17 | 1.435 (3) | C12—C13 | 1.370 (4) |
N2—C1 | 1.388 (4) | C13—C14 | 1.374 (4) |
N2—C3 | 1.395 (4) | C13—H13 | 0.93 |
N2—C11 | 1.421 (4) | C14—C15 | 1.380 (4) |
C1—C7A | 1.505 (5) | C15—C16 | 1.374 (4) |
C3—C3A | 1.500 (4) | C16—H16 | 0.93 |
C3A—C4 | 1.497 (6) | C17—C18 | 1.424 (3) |
C3A—C7A | 1.499 (5) | C17—H17A | 0.97 |
C3A—H3 | 0.98 | C17—H17B | 0.97 |
C4—C5 | 1.470 (10) | C18—C19 | 1.148 (3) |
C4—H4A | 0.97 | C19—H19 | 0.93 |
C4—H4B | 0.97 | C17A—C18A | 1.429 (3) |
C5—C6 | 1.349 (9) | C17A—H17C | 0.97 |
C5—H5 | 0.93 | C17A—H17D | 0.97 |
C6—C7 | 1.483 (7) | C18A—C19A | 1.155 (3) |
C6—H6 | 0.93 | C19A—H19A | 0.93 |
C15—O3—C17A | 119.7 (5) | C3A—C7A—H7 | 108.0 |
C15—O3—C17 | 117.0 (2) | C1—C7A—H7 | 108.0 |
C1—N2—C3 | 112.6 (3) | C7—C7A—H7 | 108.0 |
C1—N2—C11 | 123.6 (3) | C12—C11—C16 | 119.3 (3) |
C3—N2—C11 | 123.6 (2) | C12—C11—N2 | 121.1 (3) |
O1—C1—N2 | 123.3 (3) | C16—C11—N2 | 119.6 (3) |
O1—C1—C7A | 128.8 (3) | F1—C12—C13 | 119.3 (3) |
N2—C1—C7A | 107.9 (3) | F1—C12—C11 | 118.8 (3) |
O2—C3—N2 | 123.9 (3) | C13—C12—C11 | 121.9 (3) |
O2—C3—C3A | 128.2 (3) | C12—C13—C14 | 118.2 (3) |
N2—C3—C3A | 107.9 (3) | C12—C13—H13 | 120.9 |
C4—C3A—C7A | 116.0 (4) | C14—C13—H13 | 120.9 |
C4—C3A—C3 | 110.4 (3) | C13—C14—C15 | 120.9 (3) |
C7A—C3A—C3 | 105.8 (3) | C13—C14—Cl1 | 119.8 (2) |
C4—C3A—H3 | 108.1 | C15—C14—Cl1 | 119.3 (2) |
C7A—C3A—H3 | 108.1 | O3—C15—C16 | 124.4 (2) |
C3—C3A—H3 | 108.1 | O3—C15—C14 | 115.6 (3) |
C5—C4—C3A | 110.3 (5) | C16—C15—C14 | 120.0 (2) |
C5—C4—H4A | 109.6 | C15—C16—C11 | 119.7 (3) |
C3A—C4—H4A | 109.6 | C15—C16—H16 | 120.2 |
C5—C4—H4B | 109.6 | C11—C16—H16 | 120.2 |
C3A—C4—H4B | 109.6 | C18—C17—O3 | 112.5 (3) |
H4A—C4—H4B | 108.1 | C18—C17—H17A | 109.1 |
C6—C5—C4 | 120.7 (5) | O3—C17—H17A | 109.1 |
C6—C5—H5 | 119.7 | C18—C17—H17B | 109.1 |
C4—C5—H5 | 119.7 | O3—C17—H17B | 109.1 |
C5—C6—C7 | 118.7 (6) | H17A—C17—H17B | 107.8 |
C5—C6—H6 | 120.7 | C19—C18—C17 | 176.1 (7) |
C7—C6—H6 | 120.7 | C18—C19—H19 | 180.0 |
C6—C7—C7A | 109.7 (3) | O3—C17A—C18A | 114.5 (5) |
C6—C7—H7A | 109.7 | O3—C17A—H17C | 108.6 |
C7A—C7—H7A | 109.7 | C18A—C17A—H17C | 108.6 |
C6—C7—H7B | 109.7 | O3—C17A—H17D | 108.6 |
C7A—C7—H7B | 109.7 | C18A—C17A—H17D | 108.6 |
H7A—C7—H7B | 108.2 | H17C—C17A—H17D | 107.6 |
C3A—C7A—C1 | 105.8 (3) | C19A—C18A—C17A | 174.5 (10) |
C3A—C7A—C7 | 115.8 (3) | C18A—C19A—H19A | 180.0 |
C1—C7A—C7 | 111.0 (4) | ||
C3—N2—C1—O1 | 177.6 (3) | C3—N2—C11—C12 | 121.7 (3) |
C11—N2—C1—O1 | 2.3 (5) | C1—N2—C11—C16 | 116.1 (3) |
C3—N2—C1—C7A | −1.0 (4) | C3—N2—C11—C16 | −58.7 (4) |
C11—N2—C1—C7A | −176.3 (3) | C16—C11—C12—F1 | 177.6 (3) |
C1—N2—C3—O2 | −178.9 (3) | N2—C11—C12—F1 | −2.8 (4) |
C11—N2—C3—O2 | −3.6 (5) | C16—C11—C12—C13 | −1.2 (4) |
C1—N2—C3—C3A | 1.2 (4) | N2—C11—C12—C13 | 178.4 (3) |
C11—N2—C3—C3A | 176.5 (3) | F1—C12—C13—C14 | −178.0 (3) |
O2—C3—C3A—C4 | −54.6 (6) | C11—C12—C13—C14 | 0.8 (4) |
N2—C3—C3A—C4 | 125.3 (4) | C12—C13—C14—C15 | 0.6 (4) |
O2—C3—C3A—C7A | 179.2 (3) | C12—C13—C14—Cl1 | −179.1 (2) |
N2—C3—C3A—C7A | −0.9 (4) | C17A—O3—C15—C16 | −7.2 (6) |
C7A—C3A—C4—C5 | 39.3 (6) | C17—O3—C15—C16 | 11.4 (6) |
C3—C3A—C4—C5 | −81.0 (5) | C17A—O3—C15—C14 | 172.6 (4) |
C3A—C4—C5—C6 | −40.9 (8) | C17—O3—C15—C14 | −168.8 (5) |
C4—C5—C6—C7 | −1.4 (9) | C13—C14—C15—O3 | 178.4 (3) |
C5—C6—C7—C7A | 43.2 (8) | Cl1—C14—C15—O3 | −1.8 (4) |
C4—C3A—C7A—C1 | −122.5 (4) | C13—C14—C15—C16 | −1.7 (4) |
C3—C3A—C7A—C1 | 0.3 (4) | Cl1—C14—C15—C16 | 178.0 (2) |
C4—C3A—C7A—C7 | 0.9 (6) | O3—C15—C16—C11 | −178.9 (3) |
C3—C3A—C7A—C7 | 123.7 (4) | C14—C15—C16—C11 | 1.3 (4) |
O1—C1—C7A—C3A | −178.2 (4) | C12—C11—C16—C15 | 0.1 (4) |
N2—C1—C7A—C3A | 0.4 (4) | N2—C11—C16—C15 | −179.5 (3) |
O1—C1—C7A—C7 | 55.5 (5) | C15—O3—C17—C18 | −179.1 (5) |
N2—C1—C7A—C7 | −126.0 (3) | C17A—O3—C17—C18 | −75.4 (18) |
C6—C7—C7A—C3A | −41.4 (6) | C15—O3—C17A—C18A | −76.5 (9) |
C6—C7—C7A—C1 | 79.2 (5) | C17—O3—C17A—C18A | −162 (3) |
C1—N2—C11—C12 | −63.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O2i | 0.93 | 2.51 | 3.345 (4) | 149 |
C19—H19···O3ii | 0.93 | 2.78 | 3.400 (6) | 125 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C17H13ClFNO3 | C17H13ClFNO3 |
Mr | 333.73 | 333.73 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.313 (5), 9.380 (5), 10.485 (6) | 22.712 (15), 7.474 (5), 18.655 (12) |
α, β, γ (°) | 99.663 (9), 104.263 (9), 112.778 (8) | 90, 99.061 (11), 90 |
V (Å3) | 782.1 (7) | 3127 (4) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.27 | 0.27 |
Crystal size (mm) | 0.36 × 0.24 × 0.22 | 0.34 × 0.28 × 0.20 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996) | Multi-scan SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.906, 0.943 | 0.902, 0.948 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4071, 2747, 2059 | 8627, 3206, 2058 |
Rint | 0.017 | 0.027 |
(sin θ/λ)max (Å−1) | 0.595 | 0.626 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.111, 1.03 | 0.060, 0.155, 1.02 |
No. of reflections | 2747 | 3206 |
No. of parameters | 208 | 230 |
No. of restraints | 0 | 9 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.28 | 0.31, −0.25 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) in WinGX (Farrugia, 1999), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O1i | 0.93 | 2.59 | 3.295 (4) | 133 |
Symmetry code: (i) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O2i | 0.93 | 2.51 | 3.345 (4) | 149 |
C19—H19···O3ii | 0.93 | 2.78 | 3.400 (6) | 125 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z. |
Many 2-substituted phenyl tetrahydroisoindole-1,3-diones show good herbicidal activity (Ohta et al., 1976). One of these types of compounds, chlorophthalim [2-(4-chloro-phenyl)-4,5,6,7-tetrahydroisoindole-1,3-dione], was commercialized in 1973 (Tomlin, 2003). It acts as a competitive inhibitor of the enzyme protoporphyrinogen-IX oxidase (PPO) by binding to the same active site as the substrate protoporphyrinogen-IX (Matringe & Scalla, 1988; Duke et al., 1989). Since 1990, one of the title molecules, (I) [2-(4-chloro-2-fluoro-5-prop-2-ynyloxy-phenyl)- 4,5,6,7-tetrahydro-isoindole-1,3-dione], has been used as a reference compound during structure–activity relationship (SAR) studies because it has better herbicidal activity than chlorophthalim (Boger & Wakabayashi, 1999). The X-ray structures and details of herbicidal activities of three PPO inhibitors, viz. 2-(4-chlorophenyl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (chlorophthalim), 3-(4-chloro-5-cyclopentyloxy-2-fluoro-phenyl)-5 -isopropylidene-oxazolidine-2,4-dione and 2-chloro-1-(3-ethoxy-4-nitro-phenoxy)-4-trifluoromethylbenzene, including chlorophthalim have been published (Kohno et al., 1993). The X-ray structure of chlorophthalim indicated that the angle between the tetrahydroisoindole-1,3-dione and phenyl ring planes is 43.6°, and the longest length is 11.37 Å. It was assumed that both the angle and the length have some bearing on the herbicidal activity of the molecule.
The molecular similarity between (I) and protoporphyrinogen-IX has been investigated on the basis of their computational conformation using MOPAC with MNDO-PM3 parameterizations during a molecular modeling program (Uraguchi et al., 1997).
In an attempt to discover additional herbicidally active compounds (or compounds that are more herbicidally active?), the novel compound (II) [2-(4-chloro-2-fluoro-5-prop-2-ynyloxy-phenyl)- cis-3a,4,7,7a-tetrahydro-isoindole-1,3-dione], an isomer of (I), was prepared. Unfortunately, it was found that (II) is much less active than (I) (Li, 2005). In order to carry out a three-dimensional quantitative structure–activity relationship (three-dimensional-QSAR) study on this series of compounds and to interpret their differences in herbicidal activity, we report here the crystal structures of (I) and (II).
The molecular dimensions in (I) (Fig. 1) are unexceptional; the six-membered ring (C3A/C4–C7/C7A) of the 4,5,6,7-tetrahydroisoindole-1,3-dione moiety adopts a half-chair conformation, with atoms C5 and C6 on opposite sides [deviating by 0.250 (6) and −0.290 (6) Å, respectively] of the C1/N2/C3/C3A/C4/C7/C7A plane. The dihedral angle between the planes of these seven atoms and the C11–C16 phenyl ring is 50.96 (7)°. Any reduction in this value would lead to an impossibly short intramolecular F1···O1 separation [the present value is only 2.838 (3) Å]. The orientation of the propargyl group relative to the aromatic ring is defined by the C15—O3—C17—C18 torsion angle [73.8 (3)°]. The distance between the farthest two atoms (atom Cl1 and the equatorial H atom at C6) is 11.37 Å.
In (I), there is a well defined acetylenic C—H···O hydrogen bond between the C19/H19 group and carbonyl atom O2 of an adjacent molecule (Table 1 and Fig. 2); this interaction leads to the development of chains of molecules along [010]. A search of the current (July, 2004) release of the Cambridge Structural Database (Allen, 2002) revealed 106 compounds with acetylenic C—H···O hydrogen bonds. The hydrogen-bond dimensions in (I) indicate that this C—H···O hydrogen bond is weaker than those in o-chloro- and o-bromobenzoylacetylene (Ferguson & Tyrrell, 1965; Ferguson & Islam, 1966). In the crystal of (I), parallel chains are linked by weak π–π interactions; the centroid–centroid distance between the planes of the phenyl rings at (x, y, z) and (2 − x, 1 − y, 1 − z) (# in Fig. 2) is 3.736 (3) Å, the shortest C···C contacts being C11···C13# [3.452 (5) Å] and C12···C13# [3.477 (4) Å].
Compound (II) has the solid-state conformation shown in Fig. 3(a), with normal dimensions. The six-membered C3A/C4–C7/C7A ring adopts a simple boat conformation. The five-membered C1/N2/C3/C3A/C7A ring is planar; the mean deviation from the plane is 0.005 Å. The dihedral angle between this plane and that of the phenyl ring (C11–C16) is 61.03 (13)°, slightly larger than that found in (I) and with a concomitant small increase in the intramolecular F1···O1 separation to 3.004 (4) Å. The propargyl group is disordered unequally [0.549 (5):0.451 (5)] over two orientations (see Fig 3b), with the orientations relative to the aromatic ring defined by the C15—O3—C17—C18 [- 179.1 (5)°] and C15—O3—C17A—C18A [−76.5 (9)°] torsion angles. The longest atom–atom separation in (II) is 9.97 Å, between atom Cl1 and the axial H atoms at atoms C4 and C7.
The packing of (II) is controlled by weak acetylenic C—H···O hydrogen bonds, which generate centrosymmetric dimers with R22(10) rings (Bernstein et al., 1995) (Table 2 and Fig. 4a). These dimers are linked by C—H···O hydrogen bonds involving the phenyl C13/H13 group and an adjacent carbonyl O atom (O2), generating R22(32) rings. In this way, chains of rings are developed along [010]. These chains are linked by weak π–π interactions, as shown in Fig. 4(b) [e.g. between the phenyl rings at (x, y, z) and (1/2 − x, 3/2 − y, −z) (# in Fig. 4b]; the centroid–centroid separation is 3.830 (3) Å, the shortest C···C separations being C12···C14# [3.376 (5) Å] and C13···C13# [3.461 (5) Å]. The acetylenic moiety of the minor-occupancy propargyl group takes no part in any hydorgen bonding.
From the conformational data made available by this study it might be implied that the almost flat conformation of the tetrahydroisoindole-1,3-dione ring in (I) compared with the folded conformation in (II) plays an important role in maintaining the herbicidal activity of (I) compared with that of (II).