organic compounds
9-Fluoro-2,4,4a,6-tetrahydrospiro[benzo[c]chromene-3,2′-[1,3]dioxolane]
aDepartment of Physics, Thiagarajar College, Madurai 625 009, India, and bDepartment of Physics, M.G.R. College, Hosur 635 109, India
*Correspondence e-mail: vasan692000@yahoo.co.in
In the title compound, C15H15FO3, the dihedral angle between the mean plane through all the non-H atoms of the dioxolane ring with those of the rest of the atoms of the chromene ring system, including the substituent F atom, is 81.1 (1)°. The pyran ring has an with the O atom as the flap. The cyclohexene ring has a half-chair conformation, while the dioxolane ring has a twisted conformation on an –O—CH2– bond. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming chains along [100]. The chains are linked by C—H⋯π interactions, involving the fluorobenzene ring, forming layers parallel to the ac plane.
Keywords: crystal structure; 1,3-dioxolane derivative; spiro; isochromane; C—H⋯O hydrogen bonding; C—H⋯π interactions.
CCDC reference: 1444815
Structure description
The title compound belongs to a novel class of spiro heterocycles consisting of a chromene ring system with a fused 4-fluorobenzene on one side and a spiro-fused 1,3-dioxolane ring on the other. Several dioxolane–indoline derivatives are known to be anticonvulsants (Rajopadhye & Popp, 1988) and the crystal structures of a few of them, closely related to the title compound, have been elucidated (De, 2008; Bjerrum et al., 2009; Meng & Miao, 2010; Wang et al., 2010). Chromene scaffolds are basic components of innumerable natural products which exhibit a variety of biological activities, in particular as anti-JH activity in the context of safe inspect-specific pesticides (Bowers et al., 1976) and antiprotozoal agents (Harel et al., 2013). In a recent study, several chromene derivatives were evaluated and shown to possess antiproliferative activity against cancer cells (Parthiban et al., 2016). The importance of chromene as a promising pharmacophore with numerous activities such as anticancer, antimicrobial, antiviral, anti-inflammatory, antioxidant and antithrombotic was emphasized in a recent review on structurally diversified chromenes (Costa et al., 2016). 1,3-Dioxolane is regarded as a green solvent as it produces stable carbon nanotube dispersions, which leave no residue on electrodes when it evaporates (Moscoso et al., 2014). A survey of the Cambridge Structural Database (Groom et al., 2016) shows that crystal structures incorporating spiro-fused dioxolane-chromene ring systems are scarce and, to the best of our knowledge, the title structure is the first of its kind. Details of its molecular and are presented herein.
The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the mean plane through all non-H atoms of the dioxolane ring with those of the rest of the fused benzo[c]chromene unit, including atom F1, is 81.1 (1)°. The puckering parameters of the pyran ring (O3/C5–C7/C12/C13), viz. Q = 0.5012 (2) Å, θ = 129.8 (2)° and φ = 196.7 (3)°, describe a distorted Those for the cyclohexene ring (C3/C4/C5/C13/C14/C15), viz. Q = 0.480 (2) Å, θ = 130.4 (2)° and φ = 212.8 (3)°, described a half-chair conformation. The dioxolane ring (C3/C2/C1/O1/O2) has a slightly twisted conformation about the C2—O2 bond, and is close to 3T4 with puckering parameters of Q = 0.295 (2) Å and φ = 98.2 (2)°.
In the crystal, molecules are linked by C—H⋯O hydrogen bonds, involving the pyran O atom, O3, forming chains propagating along the a-axis direction (Table 1 and Fig. 2). The chains are linked by C—H⋯π interactions, forming layers parallel to the ac plane (Table 1 and Fig. 3).
Synthesis and crystallization
To a solution of 8-[5-fluoro-2-(hydroxymethyl)phenyl]-1,4-dioxaspiro[4,5]dec-8-en-7-ol (100 mmol) in dry THF (10 vol), cooled to 273 K, was added triphenylphosphane (15 mmol) and diisopropyl azodicarboxylate (120 mmol) under N2. The reaction mixture was heated to 353 K for 6 h. The reaction mixture was quenched with ice and extracted with ethyl acetate, washed with saturated brine solution, dried over sodium sulfate and concentrated under vacuum. The crude product was purified by flash (silica gel, 50% EtOAc in hexanes), to give the title compound as colourless needle-like crystals on evaporation of the solvent.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1444815
https://doi.org/10.1107/S2414314617000451/hg4019sup1.cif
contains datablocks Global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000451/hg4019Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617000451/hg4019Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2013/1 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013/1 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).C15H15FO3 | F(000) = 552 |
Mr = 262.28 | Dx = 1.412 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0373 (4) Å | Cell parameters from 2803 reflections |
b = 20.7068 (14) Å | θ = 1.0–27.8° |
c = 8.4725 (6) Å | µ = 0.11 mm−1 |
β = 92.088 (3)° | T = 295 K |
V = 1233.79 (14) Å3 | Needle, colourless |
Z = 4 | 0.30 × 0.23 × 0.18 mm |
Bruker Smart APEXII CCD diffractometer | 1702 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.045 |
φ and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −9→8 |
Tmin = 0.978, Tmax = 0.986 | k = −26→26 |
23436 measured reflections | l = −11→11 |
2802 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.5912P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2802 reflections | Δρmax = 0.23 e Å−3 |
173 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL-2013/1 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0044 (11) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.63642 (19) | 0.01685 (6) | 0.13314 (18) | 0.0690 (4) | |
O1 | 0.89547 (19) | 0.36864 (7) | 0.30809 (15) | 0.0458 (4) | |
O2 | 0.86401 (19) | 0.43734 (7) | 0.10063 (17) | 0.0507 (4) | |
O3 | 0.34019 (17) | 0.30048 (6) | 0.20342 (15) | 0.0381 (3) | |
C1 | 1.0345 (3) | 0.41731 (11) | 0.3309 (3) | 0.0524 (6) | |
H1A | 1.1568 | 0.3985 | 0.3609 | 0.063* | |
H1B | 0.9982 | 0.4472 | 0.4128 | 0.063* | |
C2 | 1.0432 (3) | 0.45101 (12) | 0.1753 (3) | 0.0562 (6) | |
H2A | 1.0608 | 0.4971 | 0.1895 | 0.067* | |
H2B | 1.1461 | 0.4342 | 0.1141 | 0.067* | |
C3 | 0.8108 (3) | 0.37529 (9) | 0.1533 (2) | 0.0376 (5) | |
C4 | 0.5986 (3) | 0.37102 (9) | 0.1610 (3) | 0.0418 (5) | |
H4A | 0.5413 | 0.3758 | 0.0558 | 0.050* | |
H4B | 0.5525 | 0.4058 | 0.2262 | 0.050* | |
C5 | 0.5414 (2) | 0.30716 (9) | 0.2291 (2) | 0.0314 (4) | |
H5 | 0.5707 | 0.3075 | 0.3430 | 0.038* | |
C6 | 0.2724 (3) | 0.24662 (9) | 0.2886 (2) | 0.0388 (5) | |
H6A | 0.1367 | 0.2421 | 0.2675 | 0.047* | |
H6B | 0.2930 | 0.2543 | 0.4009 | 0.047* | |
C7 | 0.3699 (3) | 0.18527 (9) | 0.2448 (2) | 0.0338 (4) | |
C8 | 0.2831 (3) | 0.12635 (10) | 0.2685 (3) | 0.0472 (5) | |
H8 | 0.1625 | 0.1253 | 0.3098 | 0.057* | |
C9 | 0.3712 (3) | 0.06928 (11) | 0.2324 (3) | 0.0523 (6) | |
H9 | 0.3129 | 0.0297 | 0.2496 | 0.063* | |
C10 | 0.5467 (3) | 0.07270 (10) | 0.1707 (3) | 0.0463 (5) | |
C11 | 0.6385 (3) | 0.12945 (10) | 0.1444 (2) | 0.0400 (5) | |
H11 | 0.7585 | 0.1295 | 0.1019 | 0.048* | |
C12 | 0.5501 (2) | 0.18748 (9) | 0.1821 (2) | 0.0318 (4) | |
C13 | 0.6407 (2) | 0.25062 (9) | 0.1568 (2) | 0.0307 (4) | |
C14 | 0.7963 (3) | 0.25918 (10) | 0.0756 (2) | 0.0376 (5) | |
H14 | 0.8534 | 0.2229 | 0.0334 | 0.045* | |
C15 | 0.8856 (3) | 0.32319 (10) | 0.0475 (2) | 0.0406 (5) | |
H15A | 0.8617 | 0.3355 | −0.0619 | 0.049* | |
H15B | 1.0221 | 0.3196 | 0.0654 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0713 (9) | 0.0369 (8) | 0.0983 (11) | 0.0132 (7) | −0.0042 (8) | −0.0096 (7) |
O1 | 0.0481 (8) | 0.0513 (9) | 0.0376 (8) | −0.0185 (7) | −0.0033 (6) | 0.0042 (6) |
O2 | 0.0455 (8) | 0.0425 (9) | 0.0635 (10) | −0.0123 (7) | −0.0051 (7) | 0.0165 (7) |
O3 | 0.0275 (7) | 0.0374 (8) | 0.0496 (8) | 0.0016 (6) | 0.0034 (6) | 0.0049 (6) |
C1 | 0.0508 (13) | 0.0471 (14) | 0.0588 (14) | −0.0138 (11) | −0.0034 (11) | −0.0039 (11) |
C2 | 0.0477 (13) | 0.0528 (15) | 0.0681 (15) | −0.0177 (11) | −0.0005 (11) | 0.0059 (12) |
C3 | 0.0361 (10) | 0.0362 (11) | 0.0402 (10) | −0.0058 (9) | −0.0024 (8) | 0.0085 (8) |
C4 | 0.0351 (11) | 0.0343 (11) | 0.0557 (12) | 0.0009 (9) | −0.0008 (9) | 0.0034 (9) |
C5 | 0.0245 (9) | 0.0331 (11) | 0.0366 (9) | 0.0003 (8) | 0.0000 (7) | −0.0007 (8) |
C6 | 0.0304 (10) | 0.0408 (12) | 0.0458 (11) | −0.0021 (9) | 0.0083 (8) | 0.0034 (9) |
C7 | 0.0343 (10) | 0.0346 (11) | 0.0324 (9) | −0.0012 (8) | 0.0006 (8) | 0.0007 (8) |
C8 | 0.0425 (12) | 0.0452 (13) | 0.0543 (13) | −0.0058 (10) | 0.0085 (10) | 0.0022 (10) |
C9 | 0.0568 (14) | 0.0353 (13) | 0.0647 (15) | −0.0093 (11) | 0.0015 (11) | 0.0033 (11) |
C10 | 0.0524 (13) | 0.0312 (12) | 0.0546 (13) | 0.0082 (10) | −0.0070 (10) | −0.0052 (10) |
C11 | 0.0369 (11) | 0.0401 (12) | 0.0430 (11) | 0.0041 (9) | −0.0007 (9) | −0.0016 (9) |
C12 | 0.0322 (10) | 0.0341 (11) | 0.0289 (9) | 0.0023 (8) | −0.0020 (7) | 0.0003 (8) |
C13 | 0.0271 (9) | 0.0350 (10) | 0.0298 (9) | 0.0012 (8) | −0.0022 (7) | 0.0005 (7) |
C14 | 0.0323 (10) | 0.0401 (12) | 0.0405 (11) | −0.0009 (8) | 0.0028 (8) | −0.0050 (9) |
C15 | 0.0325 (10) | 0.0526 (13) | 0.0370 (10) | −0.0059 (9) | 0.0039 (8) | 0.0031 (9) |
F1—C10 | 1.361 (2) | C6—C7 | 1.497 (3) |
O1—C1 | 1.413 (2) | C6—H6A | 0.9700 |
O1—C3 | 1.427 (2) | C6—H6B | 0.9700 |
O2—C3 | 1.415 (2) | C7—C8 | 1.382 (3) |
O2—C2 | 1.419 (2) | C7—C12 | 1.393 (2) |
O3—C6 | 1.420 (2) | C8—C9 | 1.374 (3) |
O3—C5 | 1.431 (2) | C8—H8 | 0.9300 |
C1—C2 | 1.495 (3) | C9—C10 | 1.361 (3) |
C1—H1A | 0.9700 | C9—H9 | 0.9300 |
C1—H1B | 0.9700 | C10—C11 | 1.363 (3) |
C2—H2A | 0.9700 | C11—C12 | 1.395 (3) |
C2—H2B | 0.9700 | C11—H11 | 0.9300 |
C3—C4 | 1.500 (3) | C12—C13 | 1.474 (3) |
C3—C15 | 1.510 (3) | C13—C14 | 1.326 (2) |
C4—C5 | 1.503 (3) | C14—C15 | 1.490 (3) |
C4—H4A | 0.9700 | C14—H14 | 0.9300 |
C4—H4B | 0.9700 | C15—H15A | 0.9700 |
C5—C13 | 1.505 (2) | C15—H15B | 0.9700 |
C5—H5 | 0.9800 | ||
C1—O1—C3 | 108.71 (15) | C7—C6—H6A | 109.2 |
C3—O2—C2 | 106.36 (15) | O3—C6—H6B | 109.2 |
C6—O3—C5 | 110.31 (14) | C7—C6—H6B | 109.2 |
O1—C1—C2 | 105.23 (17) | H6A—C6—H6B | 107.9 |
O1—C1—H1A | 110.7 | C8—C7—C12 | 119.84 (18) |
C2—C1—H1A | 110.7 | C8—C7—C6 | 120.27 (17) |
O1—C1—H1B | 110.7 | C12—C7—C6 | 119.88 (17) |
C2—C1—H1B | 110.7 | C9—C8—C7 | 121.4 (2) |
H1A—C1—H1B | 108.8 | C9—C8—H8 | 119.3 |
O2—C2—C1 | 103.62 (17) | C7—C8—H8 | 119.3 |
O2—C2—H2A | 111.0 | C10—C9—C8 | 117.7 (2) |
C1—C2—H2A | 111.0 | C10—C9—H9 | 121.2 |
O2—C2—H2B | 111.0 | C8—C9—H9 | 121.2 |
C1—C2—H2B | 111.0 | C9—C10—F1 | 118.76 (19) |
H2A—C2—H2B | 109.0 | C9—C10—C11 | 123.34 (19) |
O2—C3—O1 | 105.74 (15) | F1—C10—C11 | 117.90 (19) |
O2—C3—C4 | 110.03 (16) | C10—C11—C12 | 119.15 (19) |
O1—C3—C4 | 109.72 (16) | C10—C11—H11 | 120.4 |
O2—C3—C15 | 111.08 (16) | C12—C11—H11 | 120.4 |
O1—C3—C15 | 109.50 (16) | C7—C12—C11 | 118.59 (17) |
C4—C3—C15 | 110.65 (16) | C7—C12—C13 | 119.29 (16) |
C3—C4—C5 | 110.45 (15) | C11—C12—C13 | 122.12 (16) |
C3—C4—H4A | 109.6 | C14—C13—C12 | 124.32 (17) |
C5—C4—H4A | 109.6 | C14—C13—C5 | 120.78 (17) |
C3—C4—H4B | 109.6 | C12—C13—C5 | 114.90 (15) |
C5—C4—H4B | 109.6 | C13—C14—C15 | 124.24 (18) |
H4A—C4—H4B | 108.1 | C13—C14—H14 | 117.9 |
O3—C5—C4 | 107.68 (14) | C15—C14—H14 | 117.9 |
O3—C5—C13 | 109.54 (14) | C14—C15—C3 | 112.52 (16) |
C4—C5—C13 | 113.16 (15) | C14—C15—H15A | 109.1 |
O3—C5—H5 | 108.8 | C3—C15—H15A | 109.1 |
C4—C5—H5 | 108.8 | C14—C15—H15B | 109.1 |
C13—C5—H5 | 108.8 | C3—C15—H15B | 109.1 |
O3—C6—C7 | 112.04 (15) | H15A—C15—H15B | 107.8 |
O3—C6—H6A | 109.2 | ||
C3—O1—C1—C2 | −4.9 (2) | C8—C9—C10—C11 | 0.5 (3) |
C3—O2—C2—C1 | −32.3 (2) | C9—C10—C11—C12 | 0.0 (3) |
O1—C1—C2—O2 | 22.7 (2) | F1—C10—C11—C12 | −179.87 (17) |
C2—O2—C3—O1 | 29.8 (2) | C8—C7—C12—C11 | 0.1 (3) |
C2—O2—C3—C4 | 148.23 (18) | C6—C7—C12—C11 | 179.13 (16) |
C2—O2—C3—C15 | −88.89 (19) | C8—C7—C12—C13 | 179.76 (17) |
C1—O1—C3—O2 | −14.9 (2) | C6—C7—C12—C13 | −1.2 (3) |
C1—O1—C3—C4 | −133.47 (17) | C10—C11—C12—C7 | −0.3 (3) |
C1—O1—C3—C15 | 104.90 (18) | C10—C11—C12—C13 | −179.96 (18) |
O2—C3—C4—C5 | −175.51 (16) | C7—C12—C13—C14 | −168.76 (18) |
O1—C3—C4—C5 | −59.6 (2) | C11—C12—C13—C14 | 10.9 (3) |
C15—C3—C4—C5 | 61.4 (2) | C7—C12—C13—C5 | 10.4 (2) |
C6—O3—C5—C4 | −169.93 (15) | C11—C12—C13—C5 | −169.99 (16) |
C6—O3—C5—C13 | 66.62 (18) | O3—C5—C13—C14 | 137.18 (17) |
C3—C4—C5—O3 | −168.26 (15) | C4—C5—C13—C14 | 17.0 (2) |
C3—C4—C5—C13 | −47.0 (2) | O3—C5—C13—C12 | −42.0 (2) |
C5—O3—C6—C7 | −57.3 (2) | C4—C5—C13—C12 | −162.16 (15) |
O3—C6—C7—C8 | −156.86 (17) | C12—C13—C14—C15 | 178.77 (17) |
O3—C6—C7—C12 | 24.1 (2) | C5—C13—C14—C15 | −0.3 (3) |
C12—C7—C8—C9 | 0.4 (3) | C13—C14—C15—C3 | 14.2 (3) |
C6—C7—C8—C9 | −178.6 (2) | O2—C3—C15—C14 | −166.59 (15) |
C7—C8—C9—C10 | −0.7 (3) | O1—C3—C15—C14 | 76.99 (19) |
C8—C9—C10—F1 | −179.63 (19) | C4—C3—C15—C14 | −44.1 (2) |
Cg is the centroid of the C7–C12 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15B···O3i | 0.97 | 2.52 | 3.448 (2) | 161 |
C4—H4A···Cgii | 0.97 | 2.99 | 3.933 (3) | 164 |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z−1/2. |
Acknowledgements
The authors thank the Sophisticated Analytical Instrumentation Centre (SAIF), Indian Institute of Technology (IIT), Chennai, for the
data collection and the School of Physics, Madurai Kamaraj University, Madurai, for access to the Cambridge Structural Database.References
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