The structures of two diastereoisomers of 9-chloro-8-fluoro-4-phenyl-2,3,3a,4,5,9b-hexahydrofuro[3,2-c]quinoline, C17H15ClFNO, are very similar. The orientation of the furan ring, as a result of its fusion to the quinoline nucleus, constitutes the significant difference between the two structures. The dihedral angles between the furan and phenyl rings are 73.4 (1) and 63.8 (1)°.
Supporting information
CCDC references: 259045; 259046
To a solution of 3-chloro-4-fluoro-N-benzylideneaniline (5.5 mmol) in dichloromethane (5 ml) at room temperature were added 2,3-dihydrofuran (5.5 mmol) and ZrCl4 (10 mol%), and the resulting solution was stirred for 90 min. The reaction was quenched with water and the crude product was purified by column chromatography, using 2% ethyl acetate and hexane, to yield the title compounds. Crystals for X-ray study were obtained by recystallization from methanol–water (3:1) solutions.
All H atoms were positioned geometrically and treated as riding on their parent atoms, with aromatic C—H = 0.93 Å, methylene C—H = 0.98 Å, ethylene C—H = 0.97 Å and N—H = 0.90 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C,N) for other H.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(I) 9-Chloro-8-fluoro-4-phenyl-2,3,3a,4,5,9 b-hexahydrofuro[3,2-
c]quinoline
top
Crystal data top
C17H15ClFNO | F(000) = 1264 |
Mr = 303.75 | Dx = 1.424 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 448 reflections |
a = 17.0056 (17) Å | θ = 2.2–27.5° |
b = 10.7527 (11) Å | µ = 0.28 mm−1 |
c = 15.7079 (16) Å | T = 293 K |
β = 99.367 (2)° | Needle, yellow |
V = 2834.0 (5) Å3 | 0.20 × 0.15 × 0.11 mm |
Z = 8 | |
Data collection top
CCD area-etector diffractometer | 2244 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 28.0°, θmin = 2.3° |
ω scans | h = −22→21 |
8450 measured reflections | k = −14→13 |
3079 independent reflections | l = −18→20 |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0731P)2 + 1.4718P] where P = (Fo2 + 2Fc2)/3 |
3079 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C17H15ClFNO | V = 2834.0 (5) Å3 |
Mr = 303.75 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.0056 (17) Å | µ = 0.28 mm−1 |
b = 10.7527 (11) Å | T = 293 K |
c = 15.7079 (16) Å | 0.20 × 0.15 × 0.11 mm |
β = 99.367 (2)° | |
Data collection top
CCD area-etector diffractometer | 2244 reflections with I > 2σ(I) |
8450 measured reflections | Rint = 0.025 |
3079 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.30 e Å−3 |
3079 reflections | Δρmin = −0.19 e Å−3 |
190 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 | x | y | z | Uiso*/Ueq | |
Cl1 | 1.13249 (4) | 0.74432 (7) | −0.00429 (5) | 0.0727 (3) | |
F1 | 1.20787 (8) | 0.97953 (17) | 0.04091 (10) | 0.0831 (5) | |
O1 | 1.01402 (8) | 0.62954 (14) | 0.11530 (11) | 0.0568 (4) | |
N1 | 0.91876 (10) | 0.93423 (16) | 0.15223 (12) | 0.0496 (5) | |
H1 | 0.9205 | 0.9788 | 0.2010 | 0.059* | |
C1 | 1.13700 (13) | 0.9681 (3) | 0.06821 (16) | 0.0576 (6) | |
C2 | 1.09425 (12) | 0.8610 (2) | 0.05275 (14) | 0.0489 (5) | |
C3 | 1.02190 (11) | 0.84542 (19) | 0.08229 (13) | 0.0414 (5) | |
C4 | 0.97463 (11) | 0.72846 (19) | 0.06420 (15) | 0.0433 (5) | |
H4 | 0.9711 | 0.7074 | 0.0030 | 0.052* | |
C5 | 0.95679 (16) | 0.5377 (3) | 0.1223 (3) | 0.0977 (12) | |
H5A | 0.9648 | 0.5046 | 0.1806 | 0.117* | |
H5B | 0.9621 | 0.4699 | 0.0829 | 0.117* | |
C6 | 0.87559 (13) | 0.5936 (2) | 0.10118 (17) | 0.0556 (6) | |
H6A | 0.8459 | 0.5819 | 0.1483 | 0.067* | |
H6B | 0.8460 | 0.5565 | 0.0494 | 0.067* | |
C7 | 0.89060 (11) | 0.73187 (18) | 0.08725 (14) | 0.0424 (5) | |
H7 | 0.8523 | 0.7646 | 0.0391 | 0.051* | |
C8 | 0.88984 (11) | 0.80933 (19) | 0.16835 (14) | 0.0428 (5) | |
H8 | 0.9265 | 0.7716 | 0.2160 | 0.051* | |
C9 | 0.99256 (12) | 0.94399 (19) | 0.12591 (13) | 0.0440 (5) | |
C10 | 1.03724 (15) | 1.0536 (2) | 0.13955 (15) | 0.0547 (6) | |
H10 | 1.0177 | 1.1199 | 0.1679 | 0.066* | |
C11 | 1.10942 (15) | 1.0646 (2) | 0.11180 (16) | 0.0622 (7) | |
H11 | 1.1393 | 1.1370 | 0.1225 | 0.075* | |
C12 | 0.80798 (12) | 0.8189 (2) | 0.19416 (14) | 0.0460 (5) | |
C13 | 0.79063 (15) | 0.7511 (2) | 0.26345 (16) | 0.0559 (6) | |
H13 | 0.8293 | 0.6998 | 0.2941 | 0.067* | |
C14 | 0.71607 (17) | 0.7591 (3) | 0.28757 (19) | 0.0721 (8) | |
H14 | 0.7047 | 0.7126 | 0.3340 | 0.086* | |
C15 | 0.65904 (16) | 0.8351 (3) | 0.2435 (2) | 0.0752 (9) | |
H15 | 0.6091 | 0.8405 | 0.2601 | 0.090* | |
C16 | 0.67533 (15) | 0.9035 (3) | 0.1747 (2) | 0.0745 (8) | |
H16 | 0.6365 | 0.9552 | 0.1448 | 0.089* | |
C17 | 0.74990 (14) | 0.8954 (2) | 0.14955 (18) | 0.0597 (6) | |
H17 | 0.7608 | 0.9415 | 0.1027 | 0.072* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0521 (4) | 0.0957 (5) | 0.0778 (5) | −0.0148 (3) | 0.0328 (3) | −0.0158 (4) |
F1 | 0.0508 (8) | 0.1176 (13) | 0.0827 (12) | −0.0397 (8) | 0.0167 (8) | 0.0114 (9) |
O1 | 0.0371 (8) | 0.0502 (9) | 0.0842 (12) | −0.0054 (6) | 0.0132 (8) | 0.0054 (8) |
N1 | 0.0508 (10) | 0.0478 (10) | 0.0516 (12) | −0.0075 (8) | 0.0131 (9) | −0.0095 (8) |
C1 | 0.0446 (12) | 0.0776 (16) | 0.0498 (15) | −0.0237 (11) | 0.0049 (11) | 0.0118 (12) |
C2 | 0.0404 (11) | 0.0659 (14) | 0.0402 (13) | −0.0110 (10) | 0.0056 (9) | 0.0038 (10) |
C3 | 0.0362 (10) | 0.0511 (11) | 0.0362 (12) | −0.0102 (8) | 0.0041 (9) | 0.0019 (9) |
C4 | 0.0362 (10) | 0.0506 (11) | 0.0442 (13) | −0.0093 (8) | 0.0095 (9) | −0.0053 (9) |
C5 | 0.0497 (15) | 0.0603 (16) | 0.184 (4) | −0.0088 (12) | 0.0204 (19) | 0.028 (2) |
C6 | 0.0438 (11) | 0.0533 (13) | 0.0733 (17) | −0.0151 (10) | 0.0202 (11) | −0.0111 (11) |
C7 | 0.0329 (9) | 0.0507 (11) | 0.0437 (13) | −0.0070 (8) | 0.0070 (9) | −0.0047 (9) |
C8 | 0.0349 (10) | 0.0494 (11) | 0.0445 (13) | −0.0040 (8) | 0.0080 (9) | −0.0012 (9) |
C9 | 0.0438 (11) | 0.0478 (11) | 0.0390 (12) | −0.0091 (9) | 0.0026 (9) | 0.0037 (9) |
C10 | 0.0667 (14) | 0.0496 (12) | 0.0458 (14) | −0.0152 (11) | 0.0035 (11) | 0.0007 (10) |
C11 | 0.0652 (15) | 0.0649 (16) | 0.0515 (15) | −0.0344 (12) | −0.0051 (12) | 0.0119 (12) |
C12 | 0.0408 (10) | 0.0520 (12) | 0.0473 (13) | −0.0033 (9) | 0.0132 (10) | −0.0096 (10) |
C13 | 0.0562 (13) | 0.0676 (15) | 0.0472 (14) | −0.0054 (11) | 0.0183 (11) | −0.0061 (11) |
C14 | 0.0743 (17) | 0.0850 (19) | 0.0668 (18) | −0.0158 (15) | 0.0412 (15) | −0.0200 (14) |
C15 | 0.0565 (15) | 0.0787 (18) | 0.101 (2) | −0.0076 (14) | 0.0440 (16) | −0.0371 (17) |
C16 | 0.0496 (14) | 0.0671 (16) | 0.109 (2) | 0.0099 (12) | 0.0182 (15) | −0.0180 (16) |
C17 | 0.0487 (12) | 0.0623 (14) | 0.0703 (17) | 0.0050 (11) | 0.0161 (12) | 0.0001 (12) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.729 (2) | C7—C8 | 1.524 (3) |
F1—C1 | 1.349 (2) | C7—H7 | 0.9800 |
O1—C5 | 1.404 (3) | C8—C12 | 1.516 (3) |
O1—C4 | 1.432 (3) | C8—H8 | 0.9800 |
N1—C9 | 1.388 (3) | C9—C10 | 1.399 (3) |
N1—C8 | 1.466 (3) | C10—C11 | 1.373 (3) |
N1—H1 | 0.9000 | C10—H10 | 0.9300 |
C1—C2 | 1.363 (3) | C11—H11 | 0.9300 |
C1—C11 | 1.367 (4) | C12—C13 | 1.381 (3) |
C2—C3 | 1.394 (3) | C12—C17 | 1.385 (3) |
C3—C9 | 1.398 (3) | C13—C14 | 1.384 (3) |
C3—C4 | 1.495 (3) | C13—H13 | 0.9300 |
C4—C7 | 1.531 (3) | C14—C15 | 1.367 (4) |
C4—H4 | 0.9800 | C14—H14 | 0.9300 |
C5—C6 | 1.493 (4) | C15—C16 | 1.372 (4) |
C5—H5A | 0.9700 | C15—H15 | 0.9300 |
C5—H5B | 0.9700 | C16—C17 | 1.391 (3) |
C6—C7 | 1.530 (3) | C16—H16 | 0.9300 |
C6—H6A | 0.9700 | C17—H17 | 0.9300 |
C6—H6B | 0.9700 | | |
| | | |
C5—O1—C4 | 107.45 (18) | C6—C7—H7 | 110.8 |
C9—N1—C8 | 117.75 (17) | C4—C7—H7 | 110.8 |
C9—N1—H1 | 107.9 | N1—C8—C12 | 109.43 (16) |
C8—N1—H1 | 107.9 | N1—C8—C7 | 107.91 (17) |
F1—C1—C2 | 119.9 (2) | C12—C8—C7 | 113.19 (16) |
F1—C1—C11 | 119.1 (2) | N1—C8—H8 | 108.7 |
C2—C1—C11 | 121.0 (2) | C12—C8—H8 | 108.7 |
C1—C2—C3 | 121.1 (2) | C7—C8—H8 | 108.7 |
C1—C2—Cl1 | 118.10 (17) | N1—C9—C3 | 120.07 (17) |
C3—C2—Cl1 | 120.83 (17) | N1—C9—C10 | 120.9 (2) |
C2—C3—C9 | 118.51 (18) | C3—C9—C10 | 119.03 (19) |
C2—C3—C4 | 120.93 (19) | C11—C10—C9 | 121.0 (2) |
C9—C3—C4 | 120.49 (17) | C11—C10—H10 | 119.5 |
O1—C4—C3 | 109.30 (16) | C9—C10—H10 | 119.5 |
O1—C4—C7 | 104.77 (16) | C1—C11—C10 | 119.4 (2) |
C3—C4—C7 | 115.39 (17) | C1—C11—H11 | 120.3 |
O1—C4—H4 | 109.1 | C10—C11—H11 | 120.3 |
C3—C4—H4 | 109.1 | C13—C12—C17 | 119.1 (2) |
C7—C4—H4 | 109.1 | C13—C12—C8 | 119.9 (2) |
O1—C5—C6 | 109.1 (2) | C17—C12—C8 | 121.0 (2) |
O1—C5—H5A | 109.9 | C12—C13—C14 | 120.4 (3) |
C6—C5—H5A | 109.9 | C12—C13—H13 | 119.8 |
O1—C5—H5B | 109.9 | C14—C13—H13 | 119.8 |
C6—C5—H5B | 109.9 | C15—C14—C13 | 120.3 (3) |
H5A—C5—H5B | 108.3 | C15—C14—H14 | 119.9 |
C5—C6—C7 | 104.69 (17) | C13—C14—H14 | 119.9 |
C5—C6—H6A | 110.8 | C14—C15—C16 | 120.1 (2) |
C7—C6—H6A | 110.8 | C14—C15—H15 | 119.9 |
C5—C6—H6B | 110.8 | C16—C15—H15 | 119.9 |
C7—C6—H6B | 110.8 | C15—C16—C17 | 120.0 (3) |
H6A—C6—H6B | 108.9 | C15—C16—H16 | 120.0 |
C8—C7—C6 | 112.78 (19) | C17—C16—H16 | 120.0 |
C8—C7—C4 | 110.25 (16) | C12—C17—C16 | 120.1 (2) |
C6—C7—C4 | 101.21 (16) | C12—C17—H17 | 119.9 |
C8—C7—H7 | 110.8 | C16—C17—H17 | 119.9 |
| | | |
F1—C1—C2—C3 | 178.2 (2) | C6—C7—C8—C12 | −68.8 (2) |
C11—C1—C2—C3 | −1.3 (4) | C4—C7—C8—C12 | 178.91 (17) |
F1—C1—C2—Cl1 | −1.5 (3) | C8—N1—C9—C3 | 26.3 (3) |
C11—C1—C2—Cl1 | 178.99 (19) | C8—N1—C9—C10 | −156.1 (2) |
C1—C2—C3—C9 | 2.1 (3) | C2—C3—C9—N1 | 176.61 (19) |
Cl1—C2—C3—C9 | −178.17 (16) | C4—C3—C9—N1 | −0.5 (3) |
C1—C2—C3—C4 | 179.2 (2) | C2—C3—C9—C10 | −1.0 (3) |
Cl1—C2—C3—C4 | −1.1 (3) | C4—C3—C9—C10 | −178.1 (2) |
C5—O1—C4—C3 | 158.3 (2) | N1—C9—C10—C11 | −178.5 (2) |
C5—O1—C4—C7 | 34.1 (3) | C3—C9—C10—C11 | −0.8 (3) |
C2—C3—C4—O1 | 71.9 (2) | F1—C1—C11—C10 | 179.9 (2) |
C9—C3—C4—O1 | −111.1 (2) | C2—C1—C11—C10 | −0.7 (4) |
C2—C3—C4—C7 | −170.42 (19) | C9—C10—C11—C1 | 1.7 (4) |
C9—C3—C4—C7 | 6.6 (3) | N1—C8—C12—C13 | −134.6 (2) |
C4—O1—C5—C6 | −18.8 (3) | C7—C8—C12—C13 | 105.0 (2) |
O1—C5—C6—C7 | −4.1 (4) | N1—C8—C12—C17 | 45.0 (3) |
C5—C6—C7—C8 | −94.4 (3) | C7—C8—C12—C17 | −75.4 (3) |
C5—C6—C7—C4 | 23.3 (3) | C17—C12—C13—C14 | 0.4 (3) |
O1—C4—C7—C8 | 84.7 (2) | C8—C12—C13—C14 | 180.0 (2) |
C3—C4—C7—C8 | −35.5 (3) | C12—C13—C14—C15 | −0.6 (4) |
O1—C4—C7—C6 | −34.9 (2) | C13—C14—C15—C16 | 0.3 (4) |
C3—C4—C7—C6 | −155.13 (19) | C14—C15—C16—C17 | 0.1 (4) |
C9—N1—C8—C12 | −178.64 (18) | C13—C12—C17—C16 | 0.1 (3) |
C9—N1—C8—C7 | −55.1 (2) | C8—C12—C17—C16 | −179.6 (2) |
C6—C7—C8—N1 | 169.97 (17) | C15—C16—C17—C12 | −0.3 (4) |
C4—C7—C8—N1 | 57.7 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···F1i | 0.97 | 2.47 | 3.108 (2) | 123 |
C17—H17···F1ii | 0.93 | 2.55 | 3.460 (3) | 167 |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+2, −y+2, −z. |
(II) 9-Chloro-8-fluoro-4-phenyl-2,3,3a,4,5,9 b-hexahydrofuro[3,2-
c]quinoline
top
Crystal data top
C17H15ClFNO | F(000) = 632 |
Mr = 303.75 | Dx = 1.427 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6613 reflections |
a = 8.1796 (6) Å | θ = 2.3–27.8° |
b = 17.9041 (12) Å | µ = 0.28 mm−1 |
c = 9.6562 (7) Å | T = 293 K |
β = 91.017 (1)° | Needle, colourless |
V = 1413.91 (17) Å3 | 0.18 × 0.15 × 0.13 mm |
Z = 4 | |
Data collection top
CCD area-detector diffractometer | 2940 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 28.0°, θmin = 2.3° |
ω scans | h = −10→10 |
16081 measured reflections | k = −23→23 |
3334 independent reflections | l = −12→12 |
Refinement top
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0746P)2 + 0.326P] where P = (Fo2 + 2Fc2)/3 |
3334 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C17H15ClFNO | V = 1413.91 (17) Å3 |
Mr = 303.75 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1796 (6) Å | µ = 0.28 mm−1 |
b = 17.9041 (12) Å | T = 293 K |
c = 9.6562 (7) Å | 0.18 × 0.15 × 0.13 mm |
β = 91.017 (1)° | |
Data collection top
CCD area-detector diffractometer | 2940 reflections with I > 2σ(I) |
16081 measured reflections | Rint = 0.020 |
3334 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.34 e Å−3 |
3334 reflections | Δρmin = −0.19 e Å−3 |
190 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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.28950 (5) | 0.39744 (3) | 0.62978 (5) | 0.05489 (17) | |
F1 | 0.43418 (15) | 0.48664 (7) | 0.84949 (12) | 0.0697 (3) | |
O1 | 0.5172 (2) | 0.27339 (8) | 0.49004 (15) | 0.0712 (5) | |
N1 | 0.88428 (17) | 0.39391 (8) | 0.46759 (15) | 0.0463 (3) | |
H1 | 0.9695 | 0.4257 | 0.4699 | 0.056* | |
C1 | 0.5449 (2) | 0.46426 (9) | 0.75549 (17) | 0.0482 (4) | |
C2 | 0.4946 (2) | 0.42132 (8) | 0.64381 (16) | 0.0413 (3) | |
C3 | 0.60589 (19) | 0.39669 (8) | 0.54643 (15) | 0.0381 (3) | |
C4 | 0.55288 (19) | 0.34529 (9) | 0.43037 (16) | 0.0438 (4) | |
H4 | 0.4540 | 0.3653 | 0.3851 | 0.053* | |
C5 | 0.5883 (3) | 0.21687 (11) | 0.4092 (2) | 0.0631 (5) | |
H5A | 0.5134 | 0.2011 | 0.3359 | 0.076* | |
H5B | 0.6162 | 0.1739 | 0.4660 | 0.076* | |
C6 | 0.7387 (2) | 0.25067 (10) | 0.3499 (2) | 0.0604 (5) | |
H6A | 0.7699 | 0.2253 | 0.2656 | 0.072* | |
H6B | 0.8294 | 0.2493 | 0.4158 | 0.072* | |
C7 | 0.68430 (19) | 0.33091 (9) | 0.32040 (16) | 0.0428 (3) | |
H7 | 0.6315 | 0.3325 | 0.2285 | 0.051* | |
C8 | 0.82138 (19) | 0.38918 (8) | 0.32491 (16) | 0.0401 (3) | |
H8 | 0.7740 | 0.4377 | 0.2999 | 0.048* | |
C9 | 0.77051 (19) | 0.41740 (8) | 0.56399 (16) | 0.0402 (3) | |
C10 | 0.8184 (2) | 0.46077 (9) | 0.67783 (17) | 0.0491 (4) | |
H10 | 0.9277 | 0.4741 | 0.6893 | 0.059* | |
C11 | 0.7064 (2) | 0.48409 (10) | 0.77341 (18) | 0.0531 (4) | |
H11 | 0.7395 | 0.5129 | 0.8490 | 0.064* | |
C12 | 0.95399 (19) | 0.37150 (9) | 0.22314 (17) | 0.0417 (3) | |
C13 | 1.0879 (2) | 0.32682 (10) | 0.2567 (2) | 0.0530 (4) | |
H13 | 1.1016 | 0.3088 | 0.3465 | 0.064* | |
C14 | 1.2011 (2) | 0.30906 (11) | 0.1568 (2) | 0.0603 (5) | |
H14 | 1.2897 | 0.2787 | 0.1796 | 0.072* | |
C15 | 1.1829 (2) | 0.33619 (12) | 0.0239 (2) | 0.0617 (5) | |
H15 | 1.2586 | 0.3238 | −0.0431 | 0.074* | |
C16 | 1.0530 (3) | 0.38150 (13) | −0.0093 (2) | 0.0610 (5) | |
H16 | 1.0413 | 0.4002 | −0.0987 | 0.073* | |
C17 | 0.9392 (2) | 0.39948 (10) | 0.08972 (18) | 0.0496 (4) | |
H17 | 0.8520 | 0.4306 | 0.0665 | 0.059* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0430 (2) | 0.0612 (3) | 0.0605 (3) | 0.00534 (18) | 0.00292 (19) | −0.00376 (19) |
F1 | 0.0742 (8) | 0.0817 (8) | 0.0534 (6) | 0.0198 (6) | 0.0029 (6) | −0.0177 (6) |
O1 | 0.0907 (10) | 0.0469 (7) | 0.0773 (9) | −0.0286 (7) | 0.0360 (8) | −0.0198 (6) |
N1 | 0.0385 (7) | 0.0528 (8) | 0.0473 (8) | −0.0065 (6) | −0.0043 (6) | −0.0029 (6) |
C1 | 0.0611 (10) | 0.0433 (9) | 0.0400 (8) | 0.0117 (7) | −0.0013 (7) | −0.0014 (6) |
C2 | 0.0449 (8) | 0.0351 (7) | 0.0438 (8) | 0.0042 (6) | −0.0030 (6) | 0.0038 (6) |
C3 | 0.0428 (8) | 0.0320 (7) | 0.0393 (7) | 0.0000 (5) | −0.0043 (6) | 0.0017 (5) |
C4 | 0.0388 (8) | 0.0462 (8) | 0.0464 (8) | −0.0058 (6) | −0.0019 (6) | −0.0074 (7) |
C5 | 0.0685 (12) | 0.0479 (10) | 0.0731 (12) | −0.0083 (9) | 0.0090 (10) | −0.0062 (9) |
C6 | 0.0586 (11) | 0.0427 (9) | 0.0801 (13) | −0.0020 (8) | 0.0097 (9) | −0.0063 (9) |
C7 | 0.0406 (8) | 0.0464 (8) | 0.0412 (8) | −0.0028 (6) | −0.0026 (6) | −0.0055 (6) |
C8 | 0.0400 (8) | 0.0373 (7) | 0.0429 (8) | 0.0010 (6) | −0.0013 (6) | 0.0014 (6) |
C9 | 0.0448 (8) | 0.0349 (7) | 0.0407 (8) | −0.0036 (6) | −0.0054 (6) | 0.0036 (6) |
C10 | 0.0533 (9) | 0.0458 (9) | 0.0479 (9) | −0.0087 (7) | −0.0116 (7) | −0.0001 (7) |
C11 | 0.0719 (12) | 0.0438 (9) | 0.0432 (9) | −0.0034 (8) | −0.0124 (8) | −0.0050 (7) |
C12 | 0.0391 (8) | 0.0376 (7) | 0.0485 (8) | −0.0023 (6) | 0.0000 (6) | −0.0010 (6) |
C13 | 0.0493 (9) | 0.0499 (9) | 0.0600 (10) | 0.0069 (7) | 0.0012 (8) | 0.0057 (8) |
C14 | 0.0473 (10) | 0.0524 (10) | 0.0815 (14) | 0.0099 (8) | 0.0046 (9) | −0.0051 (9) |
C15 | 0.0520 (10) | 0.0692 (12) | 0.0643 (11) | −0.0020 (9) | 0.0117 (9) | −0.0186 (10) |
C16 | 0.0592 (11) | 0.0753 (13) | 0.0486 (10) | −0.0031 (9) | 0.0040 (8) | 0.0004 (9) |
C17 | 0.0444 (9) | 0.0551 (10) | 0.0493 (9) | 0.0024 (7) | 0.0002 (7) | 0.0039 (7) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.7342 (17) | C7—C8 | 1.531 (2) |
F1—C1 | 1.354 (2) | C7—H7 | 0.9800 |
O1—C5 | 1.410 (2) | C8—C12 | 1.510 (2) |
O1—C4 | 1.442 (2) | C8—H8 | 0.9800 |
N1—C9 | 1.393 (2) | C9—C10 | 1.396 (2) |
N1—C8 | 1.465 (2) | C10—C11 | 1.377 (3) |
N1—H1 | 0.9000 | C10—H10 | 0.9300 |
C1—C11 | 1.376 (3) | C11—H11 | 0.9300 |
C1—C2 | 1.381 (2) | C12—C17 | 1.386 (2) |
C2—C3 | 1.392 (2) | C12—C13 | 1.390 (2) |
C3—C9 | 1.404 (2) | C13—C14 | 1.385 (3) |
C3—C4 | 1.508 (2) | C13—H13 | 0.9300 |
C4—C7 | 1.546 (2) | C14—C15 | 1.378 (3) |
C4—H4 | 0.9800 | C14—H14 | 0.9300 |
C5—C6 | 1.494 (3) | C15—C16 | 1.370 (3) |
C5—H5A | 0.9700 | C15—H15 | 0.9300 |
C5—H5B | 0.9700 | C16—C17 | 1.384 (3) |
C6—C7 | 1.529 (2) | C16—H16 | 0.9300 |
C6—H6A | 0.9700 | C17—H17 | 0.9300 |
C6—H6B | 0.9700 | | |
| | | |
C5—O1—C4 | 109.33 (14) | C8—C7—H7 | 108.5 |
C9—N1—C8 | 114.73 (13) | C4—C7—H7 | 108.5 |
C9—N1—H1 | 108.6 | N1—C8—C12 | 112.32 (13) |
C8—N1—H1 | 108.6 | N1—C8—C7 | 108.11 (13) |
F1—C1—C11 | 119.44 (15) | C12—C8—C7 | 111.89 (13) |
F1—C1—C2 | 119.62 (16) | N1—C8—H8 | 108.1 |
C11—C1—C2 | 120.94 (16) | C12—C8—H8 | 108.1 |
C1—C2—C3 | 120.95 (16) | C7—C8—H8 | 108.1 |
C1—C2—Cl1 | 118.22 (13) | N1—C9—C10 | 120.84 (15) |
C3—C2—Cl1 | 120.82 (12) | N1—C9—C3 | 119.35 (14) |
C2—C3—C9 | 118.16 (14) | C10—C9—C3 | 119.81 (15) |
C2—C3—C4 | 120.84 (14) | C11—C10—C9 | 121.04 (16) |
C9—C3—C4 | 120.90 (14) | C11—C10—H10 | 119.5 |
O1—C4—C3 | 107.78 (13) | C9—C10—H10 | 119.5 |
O1—C4—C7 | 105.89 (13) | C1—C11—C10 | 119.09 (15) |
C3—C4—C7 | 114.70 (13) | C1—C11—H11 | 120.5 |
O1—C4—H4 | 109.4 | C10—C11—H11 | 120.5 |
C3—C4—H4 | 109.4 | C17—C12—C13 | 118.70 (16) |
C7—C4—H4 | 109.4 | C17—C12—C8 | 118.52 (14) |
O1—C5—C6 | 105.8 (2) | C13—C12—C8 | 122.75 (15) |
O1—C5—H5A | 110.6 | C14—C13—C12 | 120.20 (18) |
C6—C5—H5A | 110.6 | C14—C13—H13 | 119.9 |
O1—C5—H5B | 110.6 | C12—C13—H13 | 119.9 |
C6—C5—H5B | 110.6 | C15—C14—C13 | 120.36 (18) |
H5A—C5—H5B | 108.7 | C15—C14—H14 | 119.8 |
C5—C6—C7 | 102.31 (16) | C13—C14—H14 | 119.8 |
C5—C6—H6A | 111.3 | C16—C15—C14 | 119.80 (18) |
C7—C6—H6A | 111.3 | C16—C15—H15 | 120.1 |
C5—C6—H6B | 111.3 | C14—C15—H15 | 120.1 |
C7—C6—H6B | 111.3 | C15—C16—C17 | 120.28 (18) |
H6A—C6—H6B | 109.2 | C15—C16—H16 | 119.9 |
C6—C7—C8 | 115.10 (14) | C17—C16—H16 | 119.9 |
C6—C7—C4 | 103.42 (14) | C16—C17—C12 | 120.63 (17) |
C8—C7—C4 | 112.63 (13) | C16—C17—H17 | 119.7 |
C6—C7—H7 | 108.5 | C12—C17—H17 | 119.7 |
| | | |
F1—C1—C2—C3 | −179.19 (14) | C6—C7—C8—C12 | 58.1 (2) |
C11—C1—C2—C3 | 0.2 (2) | C4—C7—C8—C12 | 176.34 (13) |
F1—C1—C2—Cl1 | −0.3 (2) | C8—N1—C9—C10 | −146.11 (15) |
C11—C1—C2—Cl1 | 179.04 (13) | C8—N1—C9—C3 | 34.3 (2) |
C1—C2—C3—C9 | −0.7 (2) | C2—C3—C9—N1 | −179.61 (13) |
Cl1—C2—C3—C9 | −179.52 (11) | C4—C3—C9—N1 | 4.1 (2) |
C1—C2—C3—C4 | 175.58 (14) | C2—C3—C9—C10 | 0.8 (2) |
Cl1—C2—C3—C4 | −3.2 (2) | C4—C3—C9—C10 | −175.50 (14) |
C5—O1—C4—C3 | −134.74 (16) | N1—C9—C10—C11 | −179.97 (15) |
C5—O1—C4—C7 | −11.54 (19) | C3—C9—C10—C11 | −0.4 (2) |
C2—C3—C4—O1 | −69.75 (18) | F1—C1—C11—C10 | 179.64 (15) |
C9—C3—C4—O1 | 106.42 (16) | C2—C1—C11—C10 | 0.2 (3) |
C2—C3—C4—C7 | 172.60 (14) | C9—C10—C11—C1 | −0.2 (3) |
C9—C3—C4—C7 | −11.2 (2) | N1—C8—C12—C17 | −148.88 (15) |
C4—O1—C5—C6 | 31.0 (2) | C7—C8—C12—C17 | 89.30 (18) |
O1—C5—C6—C7 | −37.0 (2) | N1—C8—C12—C13 | 32.8 (2) |
C5—C6—C7—C8 | 152.09 (15) | C7—C8—C12—C13 | −89.01 (19) |
C5—C6—C7—C4 | 28.82 (18) | C17—C12—C13—C14 | −2.0 (3) |
O1—C4—C7—C6 | −11.65 (17) | C8—C12—C13—C14 | 176.35 (16) |
C3—C4—C7—C6 | 107.07 (16) | C12—C13—C14—C15 | 0.8 (3) |
O1—C4—C7—C8 | −136.54 (14) | C13—C14—C15—C16 | 0.6 (3) |
C3—C4—C7—C8 | −17.8 (2) | C14—C15—C16—C17 | −0.6 (3) |
C9—N1—C8—C12 | 173.88 (13) | C15—C16—C17—C12 | −0.6 (3) |
C9—N1—C8—C7 | −62.18 (17) | C13—C12—C17—C16 | 1.9 (3) |
C6—C7—C8—N1 | −66.10 (18) | C8—C12—C17—C16 | −176.51 (17) |
C4—C7—C8—N1 | 52.13 (17) | | |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C17H15ClFNO | C17H15ClFNO |
Mr | 303.75 | 303.75 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 17.0056 (17), 10.7527 (11), 15.7079 (16) | 8.1796 (6), 17.9041 (12), 9.6562 (7) |
β (°) | 99.367 (2) | 91.017 (1) |
V (Å3) | 2834.0 (5) | 1413.91 (17) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.28 | 0.28 |
Crystal size (mm) | 0.20 × 0.15 × 0.11 | 0.18 × 0.15 × 0.13 |
|
Data collection |
Diffractometer | CCD area-etector diffractometer | CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8450, 3079, 2244 | 16081, 3334, 2940 |
Rint | 0.025 | 0.020 |
(sin θ/λ)max (Å−1) | 0.661 | 0.661 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.147, 1.03 | 0.050, 0.136, 1.08 |
No. of reflections | 3079 | 3334 |
No. of parameters | 190 | 190 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.19 | 0.34, −0.19 |
Selected geometric parameters (Å, º) for (I) topC1—C2 | 1.363 (3) | C4—C7 | 1.531 (3) |
| | | |
O1—C5—C6 | 109.1 (2) | | |
| | | |
C6—C7—C8—C12 | −68.8 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···F1i | 0.97 | 2.47 | 3.108 (2) | 123 |
C17—H17···F1ii | 0.93 | 2.55 | 3.460 (3) | 167 |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+2, −y+2, −z. |
Selected geometric parameters (Å, º) for (II) topC1—C2 | 1.381 (2) | C4—C7 | 1.546 (2) |
| | | |
O1—C5—C6 | 105.8 (2) | | |
| | | |
C6—C7—C8—C12 | 58.1 (2) | | |
Pyrano- and furoquinoline moieties have been extensively studied for a range of biological applications such as psychotropic (Nesterova et al., 1995), anti-allergic (Yamada et al., 1992) and anti-inflammatory (Faber et al., 1984) applications. Hence, efforts have been directed to the synthesis of these compounds. We have recently synthesized and purified four diastereoisomers of disubstituted pyrano- and furoquinolines by the application of the imino Diels-Alder reaction using ZrCl4 as a new catalyst (Mahesh et al., 2004). These diastereoisomers differ according to the stereochemistry (cis/trans) of the ring-junction H atoms and the orientation (endo/exo) of the furan ring. The contrasting responses of the different isomers to bactericidal and bacteriolytic activity prompted us to carry out crystal structure determinations, with a view to understanding the structure-activity relationships. We present here the structures of the two title diastereoisomers, (I) (Fig. 1) and (II) (Fig. 2). \sch
In all essential details, the two structures are similar as far as bond distances and angles are concerned (Tables 1 and 3). The greatest differences are 0.018 Å in the bond distances (for C2—C1) and 3.3° in the angles (for O1—C5—C6). Atoms H7 and H8 have a trans arrangement in (I); the H7—C7—C8—H8 torsion angle of −176.9° is in accordance with a larger coupling constant J = 10.8 Hz. In contrast, the other stereoisomer, (II), with a corresponding torsion angle of 55.3°, shows a coupling constant J = 5.2 Hz and is in a cis configuration.
The chloro- and fluoro-substituted phenyl ring of the quinoline ring system is planar, with deviations of 0.047 (1) and −0.018 (1) Å for (I) and (II), respectively. The non-planar pyridine ring adopts a sofa conformation in both structures, with asymmetry parameters (Nardelli, 1983) of ΔCS(C3) = 0.053 (1) and ΔC2(C3—C9) = 0.069 (1) in (I), and ΔCS(C3) = 0.057 (1) and ΔC2(C4—C3) = 0.088 (1) in (II).
The most significant distinctive pattern in both structures is the perpendicular orientation of the furan ring (Fig. 3). This is oriented above the least-squares plane (N1/C9/C3/C4/C7) of the quinoline ring system in (I), with atom O1 displaced by 1.325 (2) Å, and below in (II), with atom O1 displaced by −1.394 (2) Å. The C6—C7—C8—C12 torsion angle, between the furan and phenyl rings, shows the role of ring fusion, with values of −68.8 (2)° in (I) and 58.1 (2)° in (II).
The furan ring adopts a distorted envelope conformation in (I) [q2 = 0.341 (2) Å and ϕ = 171.9 (5)°] and twist conformation in (II) [q2 = 0.345 (2) Å and ϕ = 92.3 (2)°] (Cremer & Pople, 1975).
The phenyl substituent at C8 rotated through the C8—C12 bond by −134.6 (2)° in (I) and 32.8 (2)° in (II), perhaps to facilitate the cis/trans orientation for the H atoms at C8. A non-bonded interaction between atoms H17 and H8 of 2.36 Å is observed in (II), while this distance is 3.58 Å in (I).
The crystal structure is stabilized by a C—H···F intermolecular interaction in (I) (Table 2), whereas no such interaction is observed in (II). Furthermore, symmetry-related molecules are interlinked by weak C—H···π interactions in both compounds. In (I), atom H11 is 2.87 Å from the centroid of the phenyl substituent (C12—C17) at symmetry position (1/2 + x, 1/2 + y, z), with an angle of 159° and a C11···centroid distance of 3.752 (3) Å. Similarly in (II), atom H11 is 2.86 Å from the centroid of the phenyl substituent at symmetry position (2 − x, 1 − y, 1 − z), with an angle of 133° and a C11···.centroid distance of 3.561 (2) Å.