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The molecular structures of 2-[4-chloro-2-fluoro-5-(prop-2-ynyloxy)phenyl]-1,3,4,5,6,7-hexahydro­isoindole-1,3-dione, C17H13ClFNO3, (I), and the isomeric compound 2-[4-chloro-2-fluoro-5-(prop-2-ynyloxy)phenyl]-cis-1,3,3a,4,7,7a-hexahydro­isoindole-1,3-dione, (II), are, as anticipated, significantly different in their conformations and in the distances between the farthest two atoms. The six-membered ring of the 1,3,4,5,6,7-hexahydro­isoindole-1,3-dione moiety in (I) adopts a half-chair conformation. The dihedral angle between the five-membered dione ring of (I) and the benzene ring is 50.96 (7)°. The six-membered ring of the cis-1,3,3a,4,7,7a-hexahydro­isoindole-1,3-dione moiety in (II) adopts a boat conformation. The dihedral angle in (II) between the five-membered dione ring and the benzene ring is 61.03 (13)°. In the crystal structures, the molecules are linked by C—H...O hydrogen bonds and weak π–π interactions. Compound (I) is a much more potent herbicide than (II). The Cl...H distances between the farthest two atoms in (I) and (II) are 11.37 and 9.97 Å, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104034146/fg1803sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104034146/fg1803Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104034146/fg1803IIsup3.hkl
Contains datablock II

CCDC references: 264815; 264816

Comment top

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 ππ 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 ππ 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).

Experimental top

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).

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. A view showing the C—H···O hydrogen-bonded chains in (I) and the centroid–centroid separations. Atoms marked with the symbols * or # are at symmetry positions (x, y − 1, z) and (2 − x, 1 − y, 1 − z), respectively.
[Figure 3] Fig. 3. (a) The structure of (II), showing 30% probability displacement ellipsoids, the atom-numbering scheme and the major orientation of the disordered propargyl group. (b) A view of part of the molecule of (II), showing the disorder of the propargyl group.
[Figure 4] Fig. 4. A view showing (a) a chain of rings extending along [010] and (b) the weak centroid–centroid interactions between chains. Atoms marked with the symbols *, $ and # are at symmetry positions (x, 1 + y, z), (1 − x, 1 − y, −z) and (1/2 − x, 3/2 − y, −z), respectively.
(I) 2-[4-chloro-2-fluoro-5-(prop-2-ynyloxy)phenyl]-1,3,4,5,6,7- hexahydroisoindole-1,3-dione top
Crystal data top
C17H13ClFNO3Z = 2
Mr = 333.73F(000) = 344
Triclinic, P1Dx = 1.417 Mg m3
Hall symbol: -P 1Melting point: 409(1) K
a = 9.313 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.380 (5) ÅCell parameters from 860 reflections
c = 10.485 (6) Åθ = 3.3–26.0°
α = 99.663 (9)°µ = 0.27 mm1
β = 104.263 (9)°T = 293 K
γ = 112.778 (8)°Prism, colorless
V = 782.1 (7) Å30.36 × 0.24 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2747 independent reflections
Radiation source: fine-focus sealed tube2059 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ϕ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)
h = 119
Tmin = 0.906, Tmax = 0.943k = 911
4071 measured reflectionsl = 1012
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-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 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C17H13ClFNO3γ = 112.778 (8)°
Mr = 333.73V = 782.1 (7) Å3
Triclinic, P1Z = 2
a = 9.313 (5) ÅMo Kα radiation
b = 9.380 (5) ŵ = 0.27 mm1
c = 10.485 (6) ÅT = 293 K
α = 99.663 (9)°0.36 × 0.24 × 0.22 mm
β = 104.263 (9)°
Data collection top
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 = 0.943Rint = 0.017
4071 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.111H-atom parameters constrained
S = 1.03Δρmax = 0.39 e Å3
2747 reflectionsΔρmin = 0.28 e Å3
208 parameters
Special details top

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) top
xyzUiso*/Ueq
Cl11.10934 (8)0.63339 (8)0.87631 (7)0.0561 (2)
F10.88880 (18)0.69124 (17)0.40938 (15)0.0555 (4)
O10.5461 (2)0.6103 (2)0.32370 (19)0.0545 (5)
O20.5902 (2)0.13836 (19)0.24919 (17)0.0479 (4)
O30.8209 (2)0.33054 (19)0.76829 (16)0.0470 (4)
N20.6090 (2)0.3948 (2)0.32126 (19)0.0389 (5)
C10.5233 (3)0.4773 (3)0.2666 (2)0.0390 (5)
C30.5445 (3)0.2389 (3)0.2296 (2)0.0379 (5)
C3A0.4144 (3)0.2288 (3)0.1088 (2)0.0404 (6)
C40.3108 (4)0.0863 (3)0.0159 (3)0.0578 (7)
H4A0.23500.00120.00790.069*
H4B0.38120.04900.05090.069*
C50.2141 (6)0.1325 (5)0.1248 (4)0.1062 (16)
H5A0.28280.17670.17800.127*
H5B0.11820.03460.18670.127*
C60.1578 (5)0.2458 (5)0.0785 (4)0.0925 (13)
H6A0.06910.19170.04500.111*
H6B0.11010.27440.15750.111*
C70.2833 (3)0.4007 (3)0.0325 (3)0.0521 (7)
H7A0.34190.47940.00870.063*
H7B0.22730.44530.08160.063*
C7A0.4029 (3)0.3668 (3)0.1298 (2)0.0395 (5)
C110.7297 (3)0.4524 (3)0.4541 (2)0.0363 (5)
C120.8663 (3)0.6014 (3)0.4975 (2)0.0392 (5)
C130.9835 (3)0.6593 (3)0.6260 (2)0.0418 (6)
H131.07440.76030.65370.050*
C140.9637 (3)0.5642 (3)0.7134 (2)0.0385 (5)
C150.8289 (3)0.4130 (3)0.6725 (2)0.0368 (5)
C160.7123 (3)0.3584 (3)0.5431 (2)0.0373 (5)
H160.62100.25760.51530.045*
C170.6888 (3)0.1711 (3)0.7292 (3)0.0498 (7)
H17A0.58530.17210.68310.060*
H17B0.68070.13890.81130.060*
C180.7120 (3)0.0534 (3)0.6384 (3)0.0556 (7)
C190.7317 (4)0.0416 (4)0.5683 (4)0.0859 (11)
H190.74750.11790.51190.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0504 (4)0.0462 (4)0.0451 (4)0.0108 (3)0.0030 (3)0.0041 (3)
F10.0557 (9)0.0493 (9)0.0580 (9)0.0168 (7)0.0178 (8)0.0262 (7)
O10.0559 (11)0.0441 (11)0.0579 (11)0.0287 (9)0.0089 (9)0.0020 (9)
O20.0539 (11)0.0374 (9)0.0513 (10)0.0235 (8)0.0118 (9)0.0117 (8)
O30.0540 (10)0.0342 (9)0.0377 (9)0.0107 (8)0.0069 (8)0.0099 (7)
N20.0414 (11)0.0339 (10)0.0372 (11)0.0178 (9)0.0072 (9)0.0072 (8)
C10.0417 (13)0.0361 (13)0.0421 (13)0.0202 (11)0.0151 (11)0.0105 (10)
C30.0379 (13)0.0339 (12)0.0393 (13)0.0137 (10)0.0140 (10)0.0095 (10)
C3A0.0412 (13)0.0387 (13)0.0386 (13)0.0166 (11)0.0130 (11)0.0093 (10)
C40.0626 (18)0.0456 (15)0.0482 (16)0.0231 (14)0.0012 (14)0.0017 (12)
C50.124 (3)0.080 (3)0.070 (2)0.057 (3)0.033 (2)0.0150 (19)
C60.091 (3)0.086 (3)0.070 (2)0.053 (2)0.0247 (19)0.0073 (19)
C70.0520 (16)0.0560 (16)0.0493 (15)0.0303 (13)0.0094 (13)0.0150 (13)
C7A0.0400 (13)0.0400 (13)0.0401 (13)0.0192 (11)0.0136 (11)0.0123 (10)
C110.0372 (12)0.0351 (12)0.0332 (12)0.0173 (10)0.0088 (10)0.0038 (10)
C120.0435 (13)0.0341 (12)0.0435 (13)0.0183 (11)0.0172 (11)0.0141 (10)
C130.0362 (13)0.0306 (12)0.0480 (14)0.0099 (10)0.0109 (11)0.0042 (11)
C140.0370 (13)0.0331 (12)0.0376 (13)0.0146 (10)0.0066 (10)0.0029 (10)
C150.0398 (13)0.0322 (12)0.0361 (12)0.0168 (10)0.0109 (10)0.0056 (10)
C160.0352 (12)0.0308 (12)0.0383 (13)0.0107 (10)0.0102 (10)0.0049 (10)
C170.0548 (16)0.0358 (14)0.0489 (15)0.0121 (12)0.0139 (13)0.0143 (12)
C180.0518 (16)0.0370 (15)0.0599 (18)0.0133 (13)0.0045 (14)0.0080 (13)
C190.076 (2)0.059 (2)0.098 (3)0.0294 (18)0.010 (2)0.0056 (19)
Geometric parameters (Å, º) top
Cl1—C141.728 (2)C6—C71.509 (4)
F1—C121.352 (3)C6—H6A0.97
O1—C11.201 (3)C6—H6B0.97
O2—C31.202 (3)C7—C7A1.485 (3)
O3—C151.366 (3)C7—H7A0.97
O3—C171.428 (3)C7—H7B0.97
N2—C11.402 (3)C11—C121.379 (3)
N2—C31.409 (3)C11—C161.384 (3)
N2—C111.414 (3)C12—C131.369 (3)
C1—C7A1.482 (3)C13—C141.377 (3)
C3—C3A1.481 (3)C13—H130.93
C3A—C7A1.326 (3)C14—C151.387 (3)
C3A—C41.490 (3)C15—C161.375 (3)
C4—C51.505 (4)C16—H160.93
C4—H4A0.97C17—C181.451 (4)
C4—H4B0.97C17—H17A0.97
C5—C61.422 (5)C17—H17B0.97
C5—H5A0.97C18—C191.158 (4)
C5—H5B0.97C19—H190.93
C15—O3—C17118.15 (18)C6—C7—H7A109.8
C1—N2—C3109.57 (18)C7A—C7—H7B109.8
C1—N2—C11125.20 (18)C6—C7—H7B109.8
C3—N2—C11124.93 (18)H7A—C7—H7B108.2
O1—C1—N2124.9 (2)C3A—C7A—C1109.1 (2)
O1—C1—C7A128.9 (2)C3A—C7A—C7124.7 (2)
N2—C1—C7A106.13 (19)C1—C7A—C7126.1 (2)
O2—C3—N2125.2 (2)C12—C11—C16118.7 (2)
O2—C3—C3A128.8 (2)C12—C11—N2121.3 (2)
N2—C3—C3A106.02 (19)C16—C11—N2120.0 (2)
C7A—C3A—C3109.1 (2)F1—C12—C13118.6 (2)
C7A—C3A—C4125.0 (2)F1—C12—C11119.3 (2)
C3—C3A—C4125.9 (2)C13—C12—C11122.0 (2)
C3A—C4—C5109.7 (2)C12—C13—C14118.4 (2)
C3A—C4—H4A109.7C12—C13—H13120.8
C5—C4—H4A109.7C14—C13—H13120.8
C3A—C4—H4B109.7C13—C14—C15121.1 (2)
C5—C4—H4B109.7C13—C14—Cl1119.67 (18)
H4A—C4—H4B108.2C15—C14—Cl1119.22 (18)
C6—C5—C4116.8 (3)O3—C15—C16124.8 (2)
C6—C5—H5A108.1O3—C15—C14116.0 (2)
C4—C5—H5A108.1C16—C15—C14119.2 (2)
C6—C5—H5B108.1C15—C16—C11120.5 (2)
C4—C5—H5B108.1C15—C16—H16119.7
H5A—C5—H5B107.3C11—C16—H16119.7
C5—C6—C7117.6 (3)O3—C17—C18112.5 (2)
C5—C6—H6A107.9O3—C17—H17A109.1
C7—C6—H6A107.9C18—C17—H17A109.1
C5—C6—H6B107.9O3—C17—H17B109.1
C7—C6—H6B107.9C18—C17—H17B109.1
H6A—C6—H6B107.2H17A—C17—H17B107.8
C7A—C7—C6109.4 (2)C19—C18—C17178.6 (3)
C7A—C7—H7A109.8C18—C19—H19180.0
C3—N2—C1—O1177.0 (2)C6—C7—C7A—C3A10.7 (4)
C11—N2—C1—O13.1 (4)C6—C7—C7A—C1167.0 (3)
C3—N2—C1—C7A2.4 (3)C1—N2—C11—C1254.8 (3)
C11—N2—C1—C7A176.3 (2)C3—N2—C11—C12132.3 (2)
C1—N2—C3—O2178.4 (2)C1—N2—C11—C16125.5 (2)
C11—N2—C3—O24.4 (4)C3—N2—C11—C1647.5 (3)
C1—N2—C3—C3A2.1 (3)C16—C11—C12—F1177.0 (2)
C11—N2—C3—C3A176.0 (2)N2—C11—C12—F12.7 (3)
O2—C3—C3A—C7A179.6 (2)C16—C11—C12—C130.7 (4)
N2—C3—C3A—C7A0.9 (3)N2—C11—C12—C13179.5 (2)
O2—C3—C3A—C40.4 (4)F1—C12—C13—C14177.3 (2)
N2—C3—C3A—C4179.9 (2)C11—C12—C13—C140.5 (4)
C7A—C3A—C4—C510.4 (4)C12—C13—C14—C150.3 (4)
C3—C3A—C4—C5170.5 (3)C12—C13—C14—Cl1179.94 (18)
C3A—C4—C5—C635.1 (5)C17—O3—C15—C164.7 (3)
C4—C5—C6—C750.8 (6)C17—O3—C15—C14177.1 (2)
C5—C6—C7—C7A35.8 (5)C13—C14—C15—O3179.1 (2)
C3—C3A—C7A—C10.6 (3)Cl1—C14—C15—O31.3 (3)
C4—C3A—C7A—C1178.6 (2)C13—C14—C15—C160.9 (4)
C3—C3A—C7A—C7178.6 (2)Cl1—C14—C15—C16179.52 (17)
C4—C3A—C7A—C70.6 (4)O3—C15—C16—C11178.7 (2)
O1—C1—C7A—C3A177.5 (3)C14—C15—C16—C110.6 (3)
N2—C1—C7A—C3A1.8 (3)C12—C11—C16—C150.2 (3)
O1—C1—C7A—C70.5 (4)N2—C11—C16—C15179.9 (2)
N2—C1—C7A—C7179.8 (2)C15—O3—C17—C1873.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C19—H19···O1i0.932.593.295 (4)133
Symmetry code: (i) x, y1, z.
(II) 2-[4-chloro-2-fluoro-5-(prop-2-ynyloxy)phenyl]-cis-1,3,3a,4,7,7a- hexahydroisoindole-1,3-dione top
Crystal data top
C17H13ClFNO3F(000) = 1376
Mr = 333.73Dx = 1.418 Mg m3
Monoclinic, C2/cMelting point: 369(1) K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 22.712 (15) ÅCell parameters from 885 reflections
b = 7.474 (5) Åθ = 3.0–24.4°
c = 18.655 (12) ŵ = 0.27 mm1
β = 99.061 (11)°T = 293 K
V = 3127 (4) Å3Prism, colorless'
Z = 80.34 × 0.28 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3206 independent reflections
Radiation source: fine-focus sealed tube2058 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ϕ and ω scansθmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)
h = 2827
Tmin = 0.902, Tmax = 0.948k = 59
8627 measured reflectionsl = 2223
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H-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 parametersΔρmax = 0.31 e Å3
9 restraintsΔρmin = 0.25 e Å3
Crystal data top
C17H13ClFNO3V = 3127 (4) Å3
Mr = 333.73Z = 8
Monoclinic, C2/cMo Kα radiation
a = 22.712 (15) ŵ = 0.27 mm1
b = 7.474 (5) ÅT = 293 K
c = 18.655 (12) Å0.34 × 0.28 × 0.20 mm
β = 99.061 (11)°
Data collection top
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 = 0.948Rint = 0.027
8627 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0609 restraints
wR(F2) = 0.155H-atom parameters constrained
S = 1.02Δρmax = 0.31 e Å3
3206 reflectionsΔρmin = 0.25 e Å3
230 parameters
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
Cl10.38216 (4)0.94181 (12)0.03497 (5)0.0711 (3)
F10.18203 (8)0.8311 (3)0.10933 (11)0.0697 (6)
O10.20485 (12)0.6548 (4)0.25578 (13)0.0871 (9)
O20.20038 (11)0.2630 (3)0.06959 (13)0.0688 (6)
O30.40032 (9)0.5794 (3)0.07586 (14)0.0696 (7)
N20.20966 (10)0.4858 (3)0.15471 (13)0.0497 (6)
C10.19011 (14)0.5228 (5)0.21999 (17)0.0621 (9)
C30.18841 (13)0.3225 (4)0.12499 (17)0.0533 (8)
C3A0.14951 (16)0.2418 (6)0.17440 (19)0.0718 (10)
H30.16800.12980.19380.086*
C40.0892 (2)0.1989 (10)0.1331 (3)0.128 (2)
H4A0.09330.15110.08580.153*
H4B0.07020.10870.15890.153*
C50.0519 (2)0.3607 (13)0.1240 (3)0.151 (3)
H50.02760.38220.08000.181*
C60.0527 (2)0.4783 (11)0.1791 (4)0.145 (3)
H60.02980.58190.17300.174*
C70.09085 (19)0.4390 (8)0.2494 (2)0.1023 (16)
H7A0.07170.34960.27560.123*
H7B0.09620.54670.27870.123*
C7A0.15069 (15)0.3709 (6)0.23609 (17)0.0689 (10)
H70.17000.31160.28050.083*
C110.25059 (13)0.5954 (4)0.12441 (15)0.0476 (7)
C120.23645 (13)0.7686 (4)0.10352 (15)0.0490 (7)
C130.27591 (13)0.8775 (4)0.07586 (15)0.0511 (7)
H130.26590.99490.06260.061*
C140.33070 (13)0.8087 (4)0.06832 (15)0.0476 (7)
C150.34536 (12)0.6340 (4)0.08740 (16)0.0483 (7)
C160.30554 (13)0.5278 (4)0.11614 (16)0.0513 (7)
H160.31560.41080.13000.062*
C170.4128 (2)0.3914 (5)0.0823 (6)0.0705 (18)0.549 (5)
H17A0.40770.35160.13040.085*0.549 (5)
H17B0.38430.32720.04730.085*0.549 (5)
C180.47157 (19)0.3489 (6)0.0703 (3)0.0623 (17)0.549 (5)
C190.5184 (2)0.3206 (10)0.0571 (4)0.076 (2)0.549 (5)
H190.55630.29770.04640.091*0.549 (5)
C17A0.4220 (4)0.4110 (12)0.1013 (4)0.0705 (18)0.451 (5)
H17C0.45450.37730.07590.085*0.451 (5)
H17D0.39050.32340.08930.085*0.451 (5)
C18A0.4428 (4)0.4036 (11)0.1777 (3)0.088 (3)0.451 (5)
C19A0.4564 (7)0.409 (2)0.2399 (4)0.155 (7)0.451 (5)
H19A0.46740.41270.29010.186*0.451 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0766 (6)0.0556 (5)0.0844 (6)0.0070 (4)0.0231 (5)0.0078 (5)
F10.0558 (11)0.0611 (12)0.0929 (14)0.0188 (9)0.0138 (10)0.0071 (11)
O10.0920 (18)0.111 (2)0.0621 (15)0.0254 (18)0.0229 (13)0.0300 (16)
O20.0893 (17)0.0551 (14)0.0661 (14)0.0038 (13)0.0248 (13)0.0057 (12)
O30.0542 (13)0.0522 (14)0.1066 (19)0.0089 (11)0.0260 (12)0.0020 (13)
N20.0489 (13)0.0555 (15)0.0455 (13)0.0029 (12)0.0103 (11)0.0009 (12)
C10.0551 (18)0.085 (3)0.0453 (17)0.0038 (18)0.0043 (14)0.0042 (18)
C30.0514 (17)0.0535 (19)0.0543 (18)0.0060 (15)0.0059 (14)0.0101 (16)
C3A0.071 (2)0.079 (2)0.066 (2)0.014 (2)0.0143 (18)0.007 (2)
C40.080 (3)0.203 (7)0.102 (4)0.062 (4)0.022 (3)0.037 (4)
C50.047 (2)0.317 (11)0.086 (3)0.002 (4)0.000 (2)0.007 (5)
C60.074 (3)0.234 (8)0.136 (5)0.059 (4)0.043 (3)0.042 (5)
C70.081 (3)0.141 (5)0.093 (3)0.006 (3)0.037 (3)0.013 (3)
C7A0.062 (2)0.099 (3)0.0481 (18)0.009 (2)0.0132 (15)0.0073 (19)
C110.0500 (17)0.0490 (17)0.0442 (15)0.0053 (14)0.0089 (13)0.0022 (13)
C120.0473 (16)0.0489 (17)0.0498 (16)0.0111 (14)0.0041 (13)0.0090 (14)
C130.0616 (19)0.0382 (15)0.0513 (17)0.0098 (15)0.0020 (14)0.0023 (14)
C140.0582 (18)0.0429 (16)0.0418 (15)0.0001 (14)0.0082 (13)0.0008 (13)
C150.0457 (16)0.0464 (17)0.0541 (17)0.0058 (14)0.0119 (13)0.0002 (14)
C160.0537 (17)0.0418 (16)0.0592 (18)0.0087 (14)0.0111 (14)0.0023 (14)
C170.076 (3)0.061 (3)0.078 (5)0.021 (3)0.024 (3)0.005 (3)
C180.060 (4)0.052 (4)0.078 (4)0.003 (3)0.018 (3)0.005 (3)
C190.052 (4)0.083 (5)0.098 (5)0.010 (3)0.029 (3)0.009 (4)
C17A0.076 (3)0.061 (3)0.078 (5)0.021 (3)0.024 (3)0.005 (3)
C18A0.077 (6)0.068 (6)0.127 (9)0.024 (5)0.037 (6)0.003 (6)
C19A0.202 (14)0.162 (14)0.097 (8)0.085 (11)0.012 (10)0.005 (9)
Geometric parameters (Å, º) top
Cl1—C141.724 (3)C7—C7A1.508 (5)
F1—C121.342 (3)C7—H7A0.97
O1—C11.208 (4)C7—H7B0.97
O2—C31.195 (4)C7A—H70.98
O3—C151.362 (3)C11—C121.375 (4)
O3—C17A1.407 (7)C11—C161.378 (4)
O3—C171.435 (3)C12—C131.370 (4)
N2—C11.388 (4)C13—C141.374 (4)
N2—C31.395 (4)C13—H130.93
N2—C111.421 (4)C14—C151.380 (4)
C1—C7A1.505 (5)C15—C161.374 (4)
C3—C3A1.500 (4)C16—H160.93
C3A—C41.497 (6)C17—C181.424 (3)
C3A—C7A1.499 (5)C17—H17A0.97
C3A—H30.98C17—H17B0.97
C4—C51.470 (10)C18—C191.148 (3)
C4—H4A0.97C19—H190.93
C4—H4B0.97C17A—C18A1.429 (3)
C5—C61.349 (9)C17A—H17C0.97
C5—H50.93C17A—H17D0.97
C6—C71.483 (7)C18A—C19A1.155 (3)
C6—H60.93C19A—H19A0.93
C15—O3—C17A119.7 (5)C3A—C7A—H7108.0
C15—O3—C17117.0 (2)C1—C7A—H7108.0
C1—N2—C3112.6 (3)C7—C7A—H7108.0
C1—N2—C11123.6 (3)C12—C11—C16119.3 (3)
C3—N2—C11123.6 (2)C12—C11—N2121.1 (3)
O1—C1—N2123.3 (3)C16—C11—N2119.6 (3)
O1—C1—C7A128.8 (3)F1—C12—C13119.3 (3)
N2—C1—C7A107.9 (3)F1—C12—C11118.8 (3)
O2—C3—N2123.9 (3)C13—C12—C11121.9 (3)
O2—C3—C3A128.2 (3)C12—C13—C14118.2 (3)
N2—C3—C3A107.9 (3)C12—C13—H13120.9
C4—C3A—C7A116.0 (4)C14—C13—H13120.9
C4—C3A—C3110.4 (3)C13—C14—C15120.9 (3)
C7A—C3A—C3105.8 (3)C13—C14—Cl1119.8 (2)
C4—C3A—H3108.1C15—C14—Cl1119.3 (2)
C7A—C3A—H3108.1O3—C15—C16124.4 (2)
C3—C3A—H3108.1O3—C15—C14115.6 (3)
C5—C4—C3A110.3 (5)C16—C15—C14120.0 (2)
C5—C4—H4A109.6C15—C16—C11119.7 (3)
C3A—C4—H4A109.6C15—C16—H16120.2
C5—C4—H4B109.6C11—C16—H16120.2
C3A—C4—H4B109.6C18—C17—O3112.5 (3)
H4A—C4—H4B108.1C18—C17—H17A109.1
C6—C5—C4120.7 (5)O3—C17—H17A109.1
C6—C5—H5119.7C18—C17—H17B109.1
C4—C5—H5119.7O3—C17—H17B109.1
C5—C6—C7118.7 (6)H17A—C17—H17B107.8
C5—C6—H6120.7C19—C18—C17176.1 (7)
C7—C6—H6120.7C18—C19—H19180.0
C6—C7—C7A109.7 (3)O3—C17A—C18A114.5 (5)
C6—C7—H7A109.7O3—C17A—H17C108.6
C7A—C7—H7A109.7C18A—C17A—H17C108.6
C6—C7—H7B109.7O3—C17A—H17D108.6
C7A—C7—H7B109.7C18A—C17A—H17D108.6
H7A—C7—H7B108.2H17C—C17A—H17D107.6
C3A—C7A—C1105.8 (3)C19A—C18A—C17A174.5 (10)
C3A—C7A—C7115.8 (3)C18A—C19A—H19A180.0
C1—C7A—C7111.0 (4)
C3—N2—C1—O1177.6 (3)C3—N2—C11—C12121.7 (3)
C11—N2—C1—O12.3 (5)C1—N2—C11—C16116.1 (3)
C3—N2—C1—C7A1.0 (4)C3—N2—C11—C1658.7 (4)
C11—N2—C1—C7A176.3 (3)C16—C11—C12—F1177.6 (3)
C1—N2—C3—O2178.9 (3)N2—C11—C12—F12.8 (4)
C11—N2—C3—O23.6 (5)C16—C11—C12—C131.2 (4)
C1—N2—C3—C3A1.2 (4)N2—C11—C12—C13178.4 (3)
C11—N2—C3—C3A176.5 (3)F1—C12—C13—C14178.0 (3)
O2—C3—C3A—C454.6 (6)C11—C12—C13—C140.8 (4)
N2—C3—C3A—C4125.3 (4)C12—C13—C14—C150.6 (4)
O2—C3—C3A—C7A179.2 (3)C12—C13—C14—Cl1179.1 (2)
N2—C3—C3A—C7A0.9 (4)C17A—O3—C15—C167.2 (6)
C7A—C3A—C4—C539.3 (6)C17—O3—C15—C1611.4 (6)
C3—C3A—C4—C581.0 (5)C17A—O3—C15—C14172.6 (4)
C3A—C4—C5—C640.9 (8)C17—O3—C15—C14168.8 (5)
C4—C5—C6—C71.4 (9)C13—C14—C15—O3178.4 (3)
C5—C6—C7—C7A43.2 (8)Cl1—C14—C15—O31.8 (4)
C4—C3A—C7A—C1122.5 (4)C13—C14—C15—C161.7 (4)
C3—C3A—C7A—C10.3 (4)Cl1—C14—C15—C16178.0 (2)
C4—C3A—C7A—C70.9 (6)O3—C15—C16—C11178.9 (3)
C3—C3A—C7A—C7123.7 (4)C14—C15—C16—C111.3 (4)
O1—C1—C7A—C3A178.2 (4)C12—C11—C16—C150.1 (4)
N2—C1—C7A—C3A0.4 (4)N2—C11—C16—C15179.5 (3)
O1—C1—C7A—C755.5 (5)C15—O3—C17—C18179.1 (5)
N2—C1—C7A—C7126.0 (3)C17A—O3—C17—C1875.4 (18)
C6—C7—C7A—C3A41.4 (6)C15—O3—C17A—C18A76.5 (9)
C6—C7—C7A—C179.2 (5)C17—O3—C17A—C18A162 (3)
C1—N2—C11—C1263.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O2i0.932.513.345 (4)149
C19—H19···O3ii0.932.783.400 (6)125
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC17H13ClFNO3C17H13ClFNO3
Mr333.73333.73
Crystal system, space groupTriclinic, P1Monoclinic, C2/c
Temperature (K)293293
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
V3)782.1 (7)3127 (4)
Z28
Radiation typeMo KαMo Kα
µ (mm1)0.270.27
Crystal size (mm)0.36 × 0.24 × 0.220.34 × 0.28 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
SADABS (Sheldrick, 1996)
Multi-scan
SADABS (Sheldrick, 1996)
Tmin, Tmax0.906, 0.9430.902, 0.948
No. of measured, independent and
observed [I > 2σ(I)] reflections
4071, 2747, 2059 8627, 3206, 2058
Rint0.0170.027
(sin θ/λ)max1)0.5950.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.111, 1.03 0.060, 0.155, 1.02
No. of reflections27473206
No. of parameters208230
No. of restraints09
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.280.31, 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.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C19—H19···O1i0.932.593.295 (4)133
Symmetry code: (i) x, y1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O2i0.932.513.345 (4)149
C19—H19···O3ii0.932.783.400 (6)125
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z.
 

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