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The title compounds, both C
19H
20FN
3O
2, contain essentially planar benzoxazolinone ring systems, within which the C—N bond distances and angles do not differ significantly between the two compounds. In both cases, the piperazine ring adopts an almost perfect chair conformation and the benzoxazolinone ring system lies nearly perpendicular to it. The structures contain intermolecular C—H
O contacts, and the interactions between the benzoxazolinone and fluorophenylpiperazine portions of the molecules are segregated.
Supporting information
CCDC references: 237926; 237927
The title compounds were prepared via the Mannich reaction, using arylpiperazine derivatives, formaldehide and 5-methyl-2-benzoxazolinone. 5-Methyl-2-Benzoxazolinone was prepared using a modificaiton of the procedure described by Bywater et al.(1945), using 4-methyl-2-aminophenol (0.1 mol) and urea (0.12 mol). The mixture was fused at 418–423 °K for 4 h in a preheated oil bath. The residue was recrystallized from water (yield 59.69%?, m.p 394–395 °K). For the preparation of (I) and (II), formalin (0.12 mol, 37% w/v) was added to a vigorously stirred solution of the appropriate substituted piperazine derivative (0.1 mol) and 5-methyl-2-benzoxazolinone (0.1 mol) in methanol, and the mixture was refluxed in a water bath for 1 h. The reaction mixture was poured into crushed ice and the solid mass was seperated by filtration, dried and crystallized from ethanol–water. The structures of the compounds were proved by IR, 1H NMR and elemantal analysis. For (I), yield 82.58%, m.p 440–441°K. Analysis calculated for C19H20FN3O2: C 66.85, H 5.91, O 12.31; found: C 66.92, H 5.78, O 12.12. IR (KBr, cm−1): 3200, 2824 (C—H), 1790 (C=O); 1H NMR (CDCl3): 7.1–6.8 (s, 7H), 4.7 (s, 2H), 3.3–3.0 (s, 4H), 2.9–2.5 (s, 4H), 2.3 (s, 3H). For (II), yield 80.06%, m.p 417–418°K. Analysis calculated for C19H20FN3O2: C 66.85, H 5.91, O 12.31; found: C 66.37, H 6.34, O 11.95. IR (KBr, cm−1): 3200, 2924 (C—H), 1771(C=O); 1H NMR (CDCl3): 7.3–6.8 (m, 7H), 4.8 (s, 2H), 3.3–3.0 (d, 4H), 2.9–2.6 (d, 4H), 2.4 (s, 3H).
H atoms were located geometrically and refined using a riding model, with C—H distances of 0.93 (aromatic), 0.97 (CH2) and 0.96 Å (CH3).
For both compounds, data collection: STOE X-AREA (Stoe & Cie, 2002); cell refinement: STOE X-AREA; data reduction: STOE X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997) and PARST (Nardelli, 1995).
(I) 3-[4-(4-Fluorophenyl)piperazin-1-ylmethyl]-5-methyl-1,3-benzoxazol-2(3
H)-one
top
Crystal data top
C19H20FN3O2 | F(000) = 720 |
Mr = 341.22 | Dx = 1.357 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1788 (6) Å | Cell parameters from 10038 reflections |
b = 6.1512 (4) Å | θ = 0.0–29.4° |
c = 34.090 (3) Å | µ = 0.10 mm−1 |
β = 103.067 (7)° | T = 293 K |
V = 1670.6 (2) Å3 | Prism, colourless |
Z = 4 | 0.62 × 0.48 × 0.35 mm |
Data collection top
STOE IPDS 2 diffractometer | 3072 independent reflections |
Radiation source: fine-focus sealed tube | 2368 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.6° |
ω scan | h = −10→9 |
Absorption correction: integration (STOE X-RED; Stoe & Cie, 2002) | k = −7→7 |
Tmin = 0.940, Tmax = 0.969 | l = −42→42 |
7820 measured reflections | |
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)] = 0.080 | Hydrogen site location: constr |
wR(F2) = 0.250 | See text |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1428P)2 + 0.916P] where P = (Fo2 + 2Fc2)/3 |
3072 reflections | (Δ/σ)max < 0.001 |
240 parameters | Δρmax = 0.95 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
C19H20FN3O2 | V = 1670.6 (2) Å3 |
Mr = 341.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.1788 (6) Å | µ = 0.10 mm−1 |
b = 6.1512 (4) Å | T = 293 K |
c = 34.090 (3) Å | 0.62 × 0.48 × 0.35 mm |
β = 103.067 (7)° | |
Data collection top
STOE IPDS 2 diffractometer | 3072 independent reflections |
Absorption correction: integration (STOE X-RED; Stoe & Cie, 2002) | 2368 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.969 | Rint = 0.028 |
7820 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.080 | 0 restraints |
wR(F2) = 0.250 | See text |
S = 1.07 | Δρmax = 0.95 e Å−3 |
3072 reflections | Δρmin = −0.43 e Å−3 |
240 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 | |
F1 | −0.4451 (3) | 0.1980 (4) | 0.25278 (8) | 0.0883 (8) | |
O1 | 0.6376 (4) | 0.7349 (5) | 0.11743 (9) | 0.0921 (9) | |
O2 | 0.5004 (3) | 0.8047 (3) | 0.05353 (7) | 0.0634 (6) | |
N1 | 0.0705 (3) | 0.2670 (4) | 0.17372 (9) | 0.0623 (7) | |
N2 | 0.3002 (4) | 0.3067 (4) | 0.12303 (9) | 0.0709 (9) | |
N3 | 0.4476 (3) | 0.4915 (4) | 0.08023 (7) | 0.0523 (6) | |
C1 | −0.3220 (4) | 0.2157 (6) | 0.23245 (11) | 0.0624 (8) | |
C2 | −0.2266 (4) | 0.4004 (6) | 0.23707 (11) | 0.0661 (9) | |
H2 | −0.2467 | 0.5116 | 0.2538 | 0.076 (11)* | |
C3 | −0.0995 (4) | 0.4168 (5) | 0.21697 (11) | 0.0613 (8) | |
H3 | −0.0336 | 0.5416 | 0.2201 | 0.064 (9)* | |
C4 | −0.0671 (3) | 0.2523 (4) | 0.19178 (9) | 0.0512 (7) | |
C5 | −0.1692 (4) | 0.0694 (5) | 0.18714 (10) | 0.0584 (8) | |
H5 | −0.1527 | −0.0418 | 0.1700 | 0.065 (9)* | |
C6 | −0.2963 (4) | 0.0526 (6) | 0.20758 (11) | 0.0661 (9) | |
H6 | −0.3639 | −0.0705 | 0.2046 | 0.087 (12)* | |
C7 | 0.1183 (6) | 0.4709 (6) | 0.16319 (14) | 0.0859 (13) | |
H7A | 0.1208 | 0.5700 | 0.1855 | 0.103* | |
H7B | 0.0347 | 0.5239 | 0.1403 | 0.103* | |
C8 | 0.2901 (5) | 0.4735 (5) | 0.15245 (11) | 0.0641 (9) | |
H8A | 0.3007 | 0.6150 | 0.1408 | 0.077 (11)* | |
H8B | 0.3821 | 0.4572 | 0.1757 | 0.123 (18)* | |
C9 | 0.2595 (6) | 0.1032 (6) | 0.13649 (16) | 0.0903 (13) | |
H9A | 0.3419 | 0.0649 | 0.1607 | 0.108* | |
H9B | 0.2652 | −0.0049 | 0.1161 | 0.108* | |
C10 | 0.0904 (4) | 0.0975 (5) | 0.14518 (11) | 0.0650 (9) | |
H10A | 0.0009 | 0.1073 | 0.1216 | 0.093 (13)* | |
H10B | 0.0827 | −0.0417 | 0.1574 | 0.085 (12)* | |
C11 | 0.4556 (4) | 0.3174 (5) | 0.10935 (10) | 0.0619 (8) | |
H11A | 0.4743 | 0.1801 | 0.0971 | 0.064 (9)* | |
H11B | 0.5490 | 0.3426 | 0.1321 | 0.083 (12)* | |
C12 | 0.5398 (4) | 0.6778 (5) | 0.08766 (11) | 0.0621 (8) | |
C13 | 0.3857 (4) | 0.6890 (4) | 0.02439 (10) | 0.0529 (7) | |
C14 | 0.3172 (4) | 0.7473 (5) | −0.01371 (11) | 0.0634 (8) | |
H14 | 0.3420 | 0.8795 | −0.0242 | 0.073 (10)* | |
C15 | 0.2082 (4) | 0.5990 (6) | −0.03666 (11) | 0.0641 (8) | |
H15 | 0.1585 | 0.6333 | −0.0633 | 0.068 (10)* | |
C16 | 0.1698 (4) | 0.4003 (5) | −0.02106 (10) | 0.0556 (7) | |
C17 | 0.2429 (3) | 0.3473 (5) | 0.01838 (9) | 0.0510 (7) | |
H17 | 0.2191 | 0.2157 | 0.0293 | 0.054 (8)* | |
C18 | 0.3520 (3) | 0.4937 (4) | 0.04108 (9) | 0.0473 (6) | |
C19 | 0.0502 (4) | 0.2464 (7) | −0.04739 (12) | 0.0735 (10) | |
H19A | −0.0323 | 0.3280 | −0.0662 | 0.110* | |
H19B | −0.0047 | 0.1585 | −0.0310 | 0.110* | |
H19C | 0.1112 | 0.1545 | −0.0618 | 0.110* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0737 (13) | 0.0909 (16) | 0.1090 (19) | 0.0017 (11) | 0.0390 (13) | 0.0125 (13) |
O1 | 0.107 (2) | 0.0838 (19) | 0.0788 (19) | −0.0306 (16) | 0.0064 (15) | −0.0247 (15) |
O2 | 0.0727 (14) | 0.0458 (11) | 0.0759 (16) | −0.0139 (10) | 0.0258 (11) | −0.0094 (10) |
N1 | 0.0670 (16) | 0.0463 (13) | 0.0774 (19) | −0.0094 (11) | 0.0245 (14) | −0.0192 (12) |
N2 | 0.107 (2) | 0.0521 (15) | 0.0659 (18) | −0.0184 (15) | 0.0459 (17) | −0.0141 (12) |
N3 | 0.0636 (14) | 0.0477 (12) | 0.0476 (13) | −0.0058 (10) | 0.0170 (11) | −0.0057 (10) |
C1 | 0.0516 (15) | 0.0680 (19) | 0.066 (2) | 0.0065 (14) | 0.0096 (14) | 0.0117 (16) |
C2 | 0.0610 (18) | 0.0642 (19) | 0.074 (2) | 0.0031 (15) | 0.0172 (16) | −0.0077 (17) |
C3 | 0.0609 (17) | 0.0521 (16) | 0.072 (2) | −0.0044 (14) | 0.0171 (15) | −0.0109 (15) |
C4 | 0.0486 (14) | 0.0472 (14) | 0.0533 (16) | −0.0017 (12) | 0.0021 (12) | −0.0038 (12) |
C5 | 0.0633 (17) | 0.0474 (15) | 0.0602 (18) | −0.0052 (13) | 0.0049 (14) | −0.0050 (13) |
C6 | 0.0591 (17) | 0.0591 (18) | 0.076 (2) | −0.0087 (15) | 0.0069 (16) | 0.0037 (16) |
C7 | 0.129 (3) | 0.0538 (19) | 0.094 (3) | −0.019 (2) | 0.066 (3) | −0.0174 (18) |
C8 | 0.090 (2) | 0.0450 (15) | 0.063 (2) | −0.0118 (15) | 0.0309 (18) | −0.0095 (14) |
C9 | 0.112 (3) | 0.055 (2) | 0.116 (4) | −0.007 (2) | 0.054 (3) | −0.020 (2) |
C10 | 0.080 (2) | 0.0411 (15) | 0.078 (2) | −0.0082 (14) | 0.0261 (18) | −0.0144 (15) |
C11 | 0.078 (2) | 0.0553 (17) | 0.0538 (18) | −0.0006 (15) | 0.0175 (15) | −0.0008 (13) |
C12 | 0.0718 (19) | 0.0530 (16) | 0.065 (2) | −0.0096 (14) | 0.0229 (16) | −0.0128 (14) |
C13 | 0.0553 (15) | 0.0426 (14) | 0.0669 (19) | −0.0001 (12) | 0.0268 (14) | −0.0011 (13) |
C14 | 0.0672 (18) | 0.0512 (16) | 0.076 (2) | 0.0076 (14) | 0.0251 (16) | 0.0152 (15) |
C15 | 0.0628 (18) | 0.0675 (19) | 0.0616 (19) | 0.0128 (15) | 0.0130 (15) | 0.0130 (16) |
C16 | 0.0482 (14) | 0.0577 (16) | 0.0614 (18) | 0.0057 (12) | 0.0132 (12) | −0.0028 (14) |
C17 | 0.0517 (14) | 0.0449 (14) | 0.0594 (17) | −0.0016 (12) | 0.0190 (12) | −0.0012 (12) |
C18 | 0.0492 (13) | 0.0427 (13) | 0.0551 (16) | 0.0010 (11) | 0.0226 (12) | −0.0022 (11) |
C19 | 0.0630 (19) | 0.078 (2) | 0.072 (2) | 0.0016 (17) | 0.0003 (16) | −0.0102 (18) |
Geometric parameters (Å, º) top
F1—C1 | 1.350 (4) | C7—H7A | 0.9700 |
O1—C12 | 1.194 (4) | C7—H7B | 0.9700 |
O2—C12 | 1.377 (4) | C8—H8A | 0.9680 |
O2—C13 | 1.397 (4) | C8—H8B | 0.9661 |
N1—C7 | 1.385 (4) | C9—C10 | 1.479 (5) |
N1—C4 | 1.402 (4) | C9—H9A | 0.9700 |
N1—C10 | 1.460 (4) | C9—H9B | 0.9700 |
N2—C9 | 1.399 (5) | C10—H10A | 0.9588 |
N2—C8 | 1.450 (4) | C10—H10B | 0.9594 |
N2—C11 | 1.451 (4) | C11—H11A | 0.9701 |
N3—C12 | 1.364 (4) | C11—H11B | 0.9697 |
N3—C18 | 1.386 (4) | C13—C14 | 1.342 (5) |
N3—C11 | 1.452 (4) | C13—C18 | 1.384 (4) |
C1—C6 | 1.360 (5) | C14—C15 | 1.387 (5) |
C1—C2 | 1.366 (5) | C14—H14 | 0.9298 |
C2—C3 | 1.372 (5) | C15—C16 | 1.396 (5) |
C2—H2 | 0.9298 | C15—H15 | 0.9301 |
C3—C4 | 1.391 (4) | C16—C17 | 1.381 (4) |
C3—H3 | 0.9299 | C16—C19 | 1.504 (5) |
C4—C5 | 1.389 (4) | C17—C18 | 1.376 (4) |
C5—C6 | 1.380 (5) | C17—H17 | 0.9299 |
C5—H5 | 0.9296 | C19—H19A | 0.9600 |
C6—H6 | 0.9300 | C19—H19B | 0.9600 |
C7—C8 | 1.530 (5) | C19—H19C | 0.9600 |
| | | |
C12—O2—C13 | 107.7 (2) | N2—C9—H9B | 109.0 |
C7—N1—C4 | 118.3 (3) | C10—C9—H9B | 109.0 |
C7—N1—C10 | 113.2 (3) | H9A—C9—H9B | 107.8 |
C4—N1—C10 | 117.9 (2) | N1—C10—C9 | 111.5 (3) |
C9—N2—C8 | 110.6 (3) | N1—C10—H10A | 109.5 |
C9—N2—C11 | 115.9 (3) | C9—C10—H10A | 113.7 |
C8—N2—C11 | 112.4 (3) | N1—C10—H10B | 108.7 |
C12—N3—C18 | 109.8 (3) | C9—C10—H10B | 105.3 |
C12—N3—C11 | 123.7 (3) | H10A—C10—H10B | 107.9 |
C18—N3—C11 | 126.4 (2) | N2—C11—N3 | 110.2 (3) |
F1—C1—C6 | 119.9 (3) | N2—C11—H11A | 109.6 |
F1—C1—C2 | 118.7 (3) | N3—C11—H11A | 109.5 |
C6—C1—C2 | 121.3 (3) | N2—C11—H11B | 109.9 |
C1—C2—C3 | 118.8 (3) | N3—C11—H11B | 109.5 |
C1—C2—H2 | 120.5 | H11A—C11—H11B | 108.1 |
C3—C2—H2 | 120.8 | O1—C12—N3 | 129.9 (4) |
C2—C3—C4 | 121.8 (3) | O1—C12—O2 | 122.4 (3) |
C2—C3—H3 | 119.2 | N3—C12—O2 | 107.8 (3) |
C4—C3—H3 | 119.1 | C14—C13—C18 | 123.5 (3) |
C5—C4—C3 | 117.8 (3) | C14—C13—O2 | 128.2 (3) |
C5—C4—N1 | 121.6 (3) | C18—C13—O2 | 108.3 (3) |
C3—C4—N1 | 120.5 (3) | C13—C14—C15 | 116.4 (3) |
C6—C5—C4 | 120.3 (3) | C13—C14—H14 | 121.9 |
C6—C5—H5 | 119.7 | C15—C14—H14 | 121.7 |
C4—C5—H5 | 119.9 | C14—C15—C16 | 122.1 (3) |
C1—C6—C5 | 120.0 (3) | C14—C15—H15 | 118.9 |
C1—C6—H6 | 119.9 | C16—C15—H15 | 118.9 |
C5—C6—H6 | 120.1 | C17—C16—C15 | 119.5 (3) |
N1—C7—C8 | 113.6 (3) | C17—C16—C19 | 120.8 (3) |
N1—C7—H7A | 108.9 | C15—C16—C19 | 119.7 (3) |
C8—C7—H7A | 108.9 | C18—C17—C16 | 118.4 (3) |
N1—C7—H7B | 108.9 | C18—C17—H17 | 120.8 |
C8—C7—H7B | 108.9 | C16—C17—H17 | 120.8 |
H7A—C7—H7B | 107.7 | C17—C18—C13 | 120.1 (3) |
N2—C8—C7 | 110.9 (3) | C17—C18—N3 | 133.5 (3) |
N2—C8—H8A | 109.2 | C13—C18—N3 | 106.4 (3) |
C7—C8—H8A | 106.2 | C16—C19—H19A | 109.5 |
N2—C8—H8B | 109.7 | C16—C19—H19B | 109.5 |
C7—C8—H8B | 112.9 | H19A—C19—H19B | 109.5 |
H8A—C8—H8B | 107.6 | C16—C19—H19C | 109.5 |
N2—C9—C10 | 113.0 (3) | H19A—C19—H19C | 109.5 |
N2—C9—H9A | 109.0 | H19B—C19—H19C | 109.5 |
C10—C9—H9A | 109.0 | | |
| | | |
F1—C1—C2—C3 | 178.9 (3) | C18—N3—C11—N2 | −71.4 (4) |
C6—C1—C2—C3 | −2.0 (5) | C18—N3—C12—O1 | −179.2 (3) |
C1—C2—C3—C4 | 0.9 (5) | C11—N3—C12—O1 | −0.9 (5) |
C2—C3—C4—C5 | 0.6 (5) | C18—N3—C12—O2 | 1.7 (3) |
C2—C3—C4—N1 | −175.7 (3) | C11—N3—C12—O2 | 180.0 (2) |
C7—N1—C4—C5 | 150.7 (4) | C13—O2—C12—O1 | 178.9 (3) |
C10—N1—C4—C5 | 8.4 (5) | C13—O2—C12—N3 | −1.9 (3) |
C7—N1—C4—C3 | −33.2 (5) | C12—O2—C13—C14 | −177.9 (3) |
C10—N1—C4—C3 | −175.4 (3) | C12—O2—C13—C18 | 1.5 (3) |
C3—C4—C5—C6 | −1.0 (5) | C18—C13—C14—C15 | −0.4 (4) |
N1—C4—C5—C6 | 175.3 (3) | O2—C13—C14—C15 | 178.9 (3) |
F1—C1—C6—C5 | −179.2 (3) | C13—C14—C15—C16 | 0.7 (5) |
C2—C1—C6—C5 | 1.6 (5) | C14—C15—C16—C17 | −0.5 (5) |
C4—C5—C6—C1 | −0.1 (5) | C14—C15—C16—C19 | 179.8 (3) |
C4—N1—C7—C8 | 167.4 (3) | C15—C16—C17—C18 | 0.0 (4) |
C10—N1—C7—C8 | −48.7 (5) | C19—C16—C17—C18 | 179.7 (3) |
C9—N2—C8—C7 | −54.1 (5) | C16—C17—C18—C13 | 0.3 (4) |
C11—N2—C8—C7 | 174.7 (3) | C16—C17—C18—N3 | −178.4 (3) |
N1—C7—C8—N2 | 50.8 (5) | C14—C13—C18—C17 | −0.1 (4) |
C8—N2—C9—C10 | 57.7 (5) | O2—C13—C18—C17 | −179.5 (2) |
C11—N2—C9—C10 | −172.9 (3) | C14—C13—C18—N3 | 178.9 (3) |
C7—N1—C10—C9 | 50.0 (5) | O2—C13—C18—N3 | −0.4 (3) |
C4—N1—C10—C9 | −165.9 (3) | C12—N3—C18—C17 | 178.1 (3) |
N2—C9—C10—N1 | −54.9 (5) | C11—N3—C18—C17 | −0.1 (5) |
C9—N2—C11—N3 | 153.6 (3) | C12—N3—C18—C13 | −0.8 (3) |
C8—N2—C11—N3 | −77.9 (4) | C11—N3—C18—C13 | −179.0 (3) |
C12—N3—C11—N2 | 110.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.58 | 3.268 (4) | 131 |
C14—H14···O2ii | 0.93 | 2.65 | 3.547 (4) | 163 |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+2, −z. |
(II) 3-[4-(2-Fluorophenyl)piperazin-1-ylmethyl]-5-methyl-1,3-benzoxazol-2(3
H)-one
top
Crystal data top
C19H20FN3O2 | F(000) = 720 |
Mr = 341.22 | Dx = 1.314 Mg m−3 |
Monoclinic, p21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.7467 (10) Å | Cell parameters from 19436 reflections |
b = 9.5470 (4) Å | θ = 0.0–29.5° |
c = 11.4779 (6) Å | µ = 0.09 mm−1 |
β = 91.422 (5)° | T = 293 K |
V = 1724.98 (16) Å3 | Prism, colourless |
Z = 4 | 0.60 × 0.42 × 0.31 mm |
Data collection top
STOE IPDS 2 diffractometer | 3392 independent reflections |
Radiation source: fine-focus sealed tube | 2779 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.5° |
ω scan | h = −19→19 |
Absorption correction: integration (STOE X-RED; Stoe & Cie, 2002) | k = −11→11 |
Tmin = 0.878, Tmax = 0.980 | l = −14→13 |
24265 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: constr |
R[F2 > 2σ(F2)] = 0.041 | See text |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0658P)2 + 0.1274P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3392 reflections | Δρmax = 0.21 e Å−3 |
246 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (2) |
Crystal data top
C19H20FN3O2 | V = 1724.98 (16) Å3 |
Mr = 341.22 | Z = 4 |
Monoclinic, p21/c | Mo Kα radiation |
a = 15.7467 (10) Å | µ = 0.09 mm−1 |
b = 9.5470 (4) Å | T = 293 K |
c = 11.4779 (6) Å | 0.60 × 0.42 × 0.31 mm |
β = 91.422 (5)° | |
Data collection top
STOE IPDS 2 diffractometer | 3392 independent reflections |
Absorption correction: integration (STOE X-RED; Stoe & Cie, 2002) | 2779 reflections with I > 2σ(I) |
Tmin = 0.878, Tmax = 0.980 | Rint = 0.093 |
24265 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.124 | See text |
S = 1.07 | Δρmax = 0.21 e Å−3 |
3392 reflections | Δρmin = −0.15 e Å−3 |
246 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 | |
F1 | −0.02623 (7) | 0.84447 (13) | 0.02487 (12) | 0.1032 (4) | |
O1 | 0.41098 (7) | 0.76653 (12) | −0.10543 (10) | 0.0726 (3) | |
O2 | 0.44069 (6) | 0.54729 (11) | −0.16695 (8) | 0.0625 (3) | |
N1 | 0.07924 (7) | 0.67022 (13) | 0.15050 (9) | 0.0566 (3) | |
N2 | 0.25221 (6) | 0.60123 (11) | 0.11386 (8) | 0.0514 (3) | |
N3 | 0.37578 (6) | 0.56932 (12) | 0.00110 (9) | 0.0525 (3) | |
C1 | −0.06219 (10) | 0.75215 (18) | 0.09803 (15) | 0.0711 (4) | |
C2 | −0.14883 (11) | 0.7532 (2) | 0.10515 (19) | 0.0895 (6) | |
H2 | −0.1814 | 0.8125 | 0.0580 | 0.123 (8)* | |
C3 | −0.18693 (11) | 0.6660 (3) | 0.18300 (19) | 0.0957 (7) | |
H3 | −0.2456 | 0.6656 | 0.1895 | 0.100 (6)* | |
C4 | −0.13785 (12) | 0.5789 (3) | 0.24992 (18) | 0.0979 (7) | |
H4 | −0.1633 | 0.5208 | 0.3039 | 0.117 (7)* | |
C5 | −0.05018 (10) | 0.5767 (2) | 0.23999 (15) | 0.0797 (5) | |
H5 | −0.0182 | 0.5151 | 0.2860 | 0.102 (7)* | |
C6 | −0.00974 (9) | 0.66396 (16) | 0.16311 (12) | 0.0586 (3) | |
C7 | 0.13017 (9) | 0.5996 (2) | 0.23995 (12) | 0.0679 (4) | |
H7A | 0.1108 | 0.6258 | 0.3164 | 0.075 (5)* | |
H7B | 0.1239 | 0.4991 | 0.2315 | 0.085 (6)* | |
C8 | 0.22230 (9) | 0.63949 (19) | 0.22851 (11) | 0.0644 (4) | |
H8A | 0.2562 | 0.5918 | 0.2880 | 0.080 (5)* | |
H8B | 0.2288 | 0.7396 | 0.2401 | 0.083 (5)* | |
C9 | 0.20062 (8) | 0.66981 (17) | 0.02394 (12) | 0.0608 (4) | |
H9A | 0.2201 | 0.6424 | −0.0523 | 0.077 (5)* | |
H9B | 0.2067 | 0.7706 | 0.0310 | 0.071 (5)* | |
C10 | 0.10865 (9) | 0.63019 (18) | 0.03537 (11) | 0.0615 (4) | |
H10A | 0.0747 | 0.6774 | −0.0244 | 0.081 (5)* | |
H10B | 0.1020 | 0.5300 | 0.0246 | 0.077 (5)* | |
C11 | 0.34135 (8) | 0.63315 (15) | 0.10457 (11) | 0.0547 (3) | |
H11A | 0.3491 | 0.7339 | 0.1013 | 0.063 (4)* | |
H11B | 0.3719 | 0.5984 | 0.1731 | 0.061 (4)* | |
C12 | 0.40852 (8) | 0.64277 (16) | −0.08915 (11) | 0.0567 (3) | |
C13 | 0.42527 (8) | 0.41439 (15) | −0.12344 (11) | 0.0547 (3) | |
C14 | 0.44493 (8) | 0.28826 (17) | −0.17164 (13) | 0.0637 (4) | |
H14 | 0.4730 | 0.2815 | −0.2418 | 0.081 (5)* | |
C15 | 0.42038 (9) | 0.17060 (17) | −0.11008 (14) | 0.0651 (4) | |
H15 | 0.4328 | 0.0827 | −0.1401 | 0.073 (5)* | |
C16 | 0.37814 (9) | 0.17879 (15) | −0.00525 (13) | 0.0596 (3) | |
C17 | 0.35979 (8) | 0.30978 (15) | 0.04181 (11) | 0.0550 (3) | |
H17 | 0.3317 | 0.3178 | 0.1118 | 0.054 (4)* | |
C18 | 0.38446 (7) | 0.42639 (14) | −0.01861 (11) | 0.0495 (3) | |
C19 | 0.35196 (13) | 0.04793 (18) | 0.05641 (16) | 0.0813 (5) | |
H19A | 0.3211 | 0.0723 | 0.1246 | 0.122* | |
H19B | 0.4016 | −0.0049 | 0.0789 | 0.122* | |
H19C | 0.3164 | −0.0075 | 0.0053 | 0.122* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0863 (7) | 0.0943 (8) | 0.1281 (10) | 0.0026 (5) | −0.0140 (6) | 0.0365 (7) |
O1 | 0.0836 (7) | 0.0659 (7) | 0.0688 (6) | −0.0086 (5) | 0.0142 (5) | 0.0060 (5) |
O2 | 0.0627 (5) | 0.0744 (6) | 0.0510 (5) | −0.0081 (5) | 0.0152 (4) | −0.0044 (4) |
N1 | 0.0525 (6) | 0.0705 (7) | 0.0470 (6) | 0.0032 (5) | 0.0021 (4) | −0.0039 (5) |
N2 | 0.0538 (6) | 0.0595 (6) | 0.0413 (5) | 0.0023 (5) | 0.0057 (4) | −0.0025 (4) |
N3 | 0.0531 (6) | 0.0580 (6) | 0.0469 (6) | −0.0002 (5) | 0.0096 (4) | −0.0035 (5) |
C1 | 0.0651 (8) | 0.0691 (9) | 0.0785 (10) | 0.0010 (7) | −0.0075 (7) | −0.0073 (8) |
C2 | 0.0625 (9) | 0.1030 (14) | 0.1022 (14) | 0.0110 (9) | −0.0153 (9) | −0.0196 (12) |
C3 | 0.0548 (9) | 0.1387 (19) | 0.0936 (13) | −0.0036 (10) | 0.0030 (9) | −0.0254 (13) |
C4 | 0.0688 (10) | 0.145 (2) | 0.0809 (12) | −0.0152 (11) | 0.0165 (9) | −0.0046 (12) |
C5 | 0.0659 (9) | 0.1091 (14) | 0.0644 (9) | −0.0007 (9) | 0.0112 (7) | 0.0058 (9) |
C6 | 0.0540 (7) | 0.0681 (8) | 0.0539 (7) | 0.0014 (6) | 0.0018 (6) | −0.0129 (6) |
C7 | 0.0609 (8) | 0.0990 (12) | 0.0440 (7) | 0.0111 (7) | 0.0081 (6) | 0.0060 (7) |
C8 | 0.0593 (7) | 0.0932 (12) | 0.0409 (7) | 0.0121 (7) | 0.0018 (6) | −0.0065 (7) |
C9 | 0.0597 (8) | 0.0784 (10) | 0.0445 (7) | −0.0013 (6) | 0.0034 (6) | 0.0056 (6) |
C10 | 0.0601 (7) | 0.0810 (10) | 0.0435 (7) | −0.0025 (7) | 0.0021 (6) | −0.0033 (6) |
C11 | 0.0547 (7) | 0.0603 (8) | 0.0494 (7) | 0.0009 (6) | 0.0056 (5) | −0.0089 (6) |
C12 | 0.0521 (7) | 0.0659 (9) | 0.0524 (7) | −0.0060 (6) | 0.0064 (5) | −0.0011 (6) |
C13 | 0.0460 (6) | 0.0691 (8) | 0.0491 (7) | −0.0021 (6) | 0.0052 (5) | −0.0058 (6) |
C14 | 0.0541 (7) | 0.0811 (10) | 0.0563 (8) | 0.0031 (6) | 0.0091 (6) | −0.0174 (7) |
C15 | 0.0602 (8) | 0.0678 (9) | 0.0674 (9) | 0.0105 (7) | −0.0001 (6) | −0.0175 (7) |
C16 | 0.0587 (7) | 0.0606 (8) | 0.0591 (8) | 0.0069 (6) | −0.0041 (6) | −0.0037 (6) |
C17 | 0.0554 (7) | 0.0617 (8) | 0.0479 (7) | 0.0056 (6) | 0.0034 (5) | −0.0025 (6) |
C18 | 0.0440 (6) | 0.0586 (7) | 0.0458 (6) | 0.0032 (5) | 0.0025 (5) | −0.0054 (5) |
C19 | 0.1041 (13) | 0.0597 (9) | 0.0802 (11) | 0.0072 (8) | 0.0023 (9) | 0.0005 (8) |
Geometric parameters (Å, º) top
F1—C1 | 1.351 (2) | C7—H7A | 0.9691 |
O1—C12 | 1.1970 (18) | C7—H7B | 0.9691 |
O2—C12 | 1.3810 (17) | C8—H8A | 0.9700 |
O2—C13 | 1.3872 (17) | C8—H8B | 0.9699 |
N1—C6 | 1.4134 (17) | C9—C10 | 1.5056 (19) |
N1—C7 | 1.4530 (18) | C9—H9A | 0.9700 |
N1—C10 | 1.4620 (17) | C9—H9B | 0.9699 |
N2—C11 | 1.4429 (16) | C10—H10A | 0.9699 |
N2—C9 | 1.4535 (17) | C10—H10B | 0.9697 |
N2—C8 | 1.4553 (16) | C11—H11A | 0.9700 |
N3—C12 | 1.3628 (17) | C11—H11B | 0.9699 |
N3—C18 | 1.3905 (17) | C13—C14 | 1.364 (2) |
N3—C11 | 1.4518 (15) | C13—C18 | 1.3828 (17) |
C1—C2 | 1.369 (2) | C14—C15 | 1.387 (2) |
C1—C6 | 1.385 (2) | C14—H14 | 0.9297 |
C2—C3 | 1.371 (3) | C15—C16 | 1.391 (2) |
C2—H2 | 0.9289 | C15—H15 | 0.9298 |
C3—C4 | 1.359 (3) | C16—C17 | 1.3953 (19) |
C3—H3 | 0.9293 | C16—C19 | 1.499 (2) |
C4—C5 | 1.388 (2) | C17—C18 | 1.3728 (19) |
C4—H4 | 0.9297 | C17—H17 | 0.9298 |
C5—C6 | 1.381 (2) | C19—H19A | 0.9600 |
C5—H5 | 0.9299 | C19—H19B | 0.9600 |
C7—C8 | 1.509 (2) | C19—H19C | 0.9600 |
| | | |
C12—O2—C13 | 107.49 (10) | N2—C9—H9B | 109.6 |
C6—N1—C7 | 116.06 (11) | C10—C9—H9B | 109.5 |
C6—N1—C10 | 114.75 (11) | H9A—C9—H9B | 108.1 |
C7—N1—C10 | 109.61 (11) | N1—C10—C9 | 109.88 (11) |
C11—N2—C9 | 112.33 (10) | N1—C10—H10A | 109.6 |
C11—N2—C8 | 110.56 (10) | C9—C10—H10A | 109.7 |
C9—N2—C8 | 109.96 (11) | N1—C10—H10B | 109.7 |
C12—N3—C18 | 109.92 (10) | C9—C10—H10B | 109.7 |
C12—N3—C11 | 124.18 (12) | H10A—C10—H10B | 108.2 |
C18—N3—C11 | 125.82 (11) | N2—C11—N3 | 110.83 (10) |
F1—C1—C2 | 117.77 (17) | N2—C11—H11A | 109.6 |
F1—C1—C6 | 118.57 (14) | N3—C11—H11A | 109.5 |
C2—C1—C6 | 123.65 (18) | N2—C11—H11B | 109.4 |
C1—C2—C3 | 119.18 (19) | N3—C11—H11B | 109.4 |
C1—C2—H2 | 120.4 | H11A—C11—H11B | 108.1 |
C3—C2—H2 | 120.4 | O1—C12—N3 | 129.86 (13) |
C4—C3—C2 | 119.20 (17) | O1—C12—O2 | 122.46 (12) |
C4—C3—H3 | 120.4 | N3—C12—O2 | 107.68 (12) |
C2—C3—H3 | 120.4 | C14—C13—C18 | 122.76 (13) |
C3—C4—C5 | 121.0 (2) | C14—C13—O2 | 128.17 (12) |
C3—C4—H4 | 119.6 | C18—C13—O2 | 109.07 (11) |
C5—C4—H4 | 119.4 | C13—C14—C15 | 116.07 (13) |
C6—C5—C4 | 121.22 (19) | C13—C14—H14 | 122.0 |
C6—C5—H5 | 119.5 | C15—C14—H14 | 122.0 |
C4—C5—H5 | 119.3 | C14—C15—C16 | 122.70 (14) |
C5—C6—C1 | 115.68 (14) | C14—C15—H15 | 118.6 |
C5—C6—N1 | 124.40 (14) | C16—C15—H15 | 118.7 |
C1—C6—N1 | 119.90 (14) | C15—C16—C17 | 119.55 (14) |
N1—C7—C8 | 109.66 (12) | C15—C16—C19 | 120.30 (14) |
N1—C7—H7A | 109.8 | C17—C16—C19 | 120.15 (14) |
C8—C7—H7A | 109.8 | C18—C17—C16 | 117.86 (13) |
N1—C7—H7B | 109.6 | C18—C17—H17 | 121.1 |
C8—C7—H7B | 109.7 | C16—C17—H17 | 121.1 |
H7A—C7—H7B | 108.2 | C17—C18—C13 | 121.05 (12) |
N2—C8—C7 | 110.41 (12) | C17—C18—N3 | 133.11 (11) |
N2—C8—H8A | 109.5 | C13—C18—N3 | 105.82 (11) |
C7—C8—H8A | 109.5 | C16—C19—H19A | 109.5 |
N2—C8—H8B | 109.6 | C16—C19—H19B | 109.5 |
C7—C8—H8B | 109.6 | H19A—C19—H19B | 109.5 |
H8A—C8—H8B | 108.1 | C16—C19—H19C | 109.5 |
N2—C9—C10 | 110.30 (11) | H19A—C19—H19C | 109.5 |
N2—C9—H9A | 109.6 | H19B—C19—H19C | 109.5 |
C10—C9—H9A | 109.7 | | |
| | | |
F1—C1—C2—C3 | −176.61 (17) | C12—N3—C11—N2 | 117.10 (13) |
C6—C1—C2—C3 | 2.1 (3) | C18—N3—C11—N2 | −66.38 (16) |
C1—C2—C3—C4 | −1.1 (3) | C18—N3—C12—O1 | 177.94 (14) |
C2—C3—C4—C5 | −0.4 (3) | C11—N3—C12—O1 | −5.1 (2) |
C3—C4—C5—C6 | 0.9 (3) | C18—N3—C12—O2 | −1.47 (14) |
C4—C5—C6—C1 | 0.0 (2) | C11—N3—C12—O2 | 175.53 (11) |
C4—C5—C6—N1 | 178.21 (16) | C13—O2—C12—O1 | −178.22 (13) |
F1—C1—C6—C5 | 177.16 (15) | C13—O2—C12—N3 | 1.24 (13) |
C2—C1—C6—C5 | −1.5 (2) | C12—O2—C13—C14 | 179.13 (13) |
F1—C1—C6—N1 | −1.1 (2) | C12—O2—C13—C18 | −0.57 (14) |
C2—C1—C6—N1 | −179.81 (15) | C18—C13—C14—C15 | 1.0 (2) |
C7—N1—C6—C5 | −12.2 (2) | O2—C13—C14—C15 | −178.70 (13) |
C10—N1—C6—C5 | 117.40 (17) | C13—C14—C15—C16 | 0.0 (2) |
C7—N1—C6—C1 | 165.97 (14) | C14—C15—C16—C17 | −0.6 (2) |
C10—N1—C6—C1 | −64.47 (18) | C14—C15—C16—C19 | 179.02 (14) |
C6—N1—C7—C8 | −168.68 (12) | C15—C16—C17—C18 | 0.17 (19) |
C10—N1—C7—C8 | 59.34 (17) | C19—C16—C17—C18 | −179.43 (13) |
C11—N2—C8—C7 | −177.27 (12) | C16—C17—C18—C13 | 0.77 (18) |
C9—N2—C8—C7 | 58.13 (17) | C16—C17—C18—N3 | 178.97 (13) |
N1—C7—C8—N2 | −59.02 (18) | C14—C13—C18—C17 | −1.4 (2) |
C11—N2—C9—C10 | 178.47 (11) | O2—C13—C18—C17 | 178.32 (11) |
C8—N2—C9—C10 | −57.96 (16) | C14—C13—C18—N3 | 179.97 (12) |
C6—N1—C10—C9 | 167.96 (12) | O2—C13—C18—N3 | −0.31 (14) |
C7—N1—C10—C9 | −59.37 (17) | C12—N3—C18—C17 | −177.29 (13) |
N2—C9—C10—N1 | 58.71 (16) | C11—N3—C18—C17 | 5.8 (2) |
C9—N2—C11—N3 | −68.75 (14) | C12—N3—C18—C13 | 1.10 (14) |
C8—N2—C11—N3 | 168.02 (11) | C11—N3—C18—C13 | −175.84 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 0.93 | 2.57 | 3.4680 (18) | 163 |
Symmetry code: (i) −x+1, y−1/2, −z−1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C19H20FN3O2 | C19H20FN3O2 |
Mr | 341.22 | 341.22 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, p21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.1788 (6), 6.1512 (4), 34.090 (3) | 15.7467 (10), 9.5470 (4), 11.4779 (6) |
β (°) | 103.067 (7) | 91.422 (5) |
V (Å3) | 1670.6 (2) | 1724.98 (16) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.09 |
Crystal size (mm) | 0.62 × 0.48 × 0.35 | 0.60 × 0.42 × 0.31 |
|
Data collection |
Diffractometer | STOE IPDS 2 diffractometer | STOE IPDS 2 diffractometer |
Absorption correction | Integration (STOE X-RED; Stoe & Cie, 2002) | Integration (STOE X-RED; Stoe & Cie, 2002) |
Tmin, Tmax | 0.940, 0.969 | 0.878, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7820, 3072, 2368 | 24265, 3392, 2779 |
Rint | 0.028 | 0.093 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.080, 0.250, 1.07 | 0.041, 0.124, 1.07 |
No. of reflections | 3072 | 3392 |
No. of parameters | 240 | 246 |
H-atom treatment | See text | See text |
Δρmax, Δρmin (e Å−3) | 0.95, −0.43 | 0.21, −0.15 |
Selected geometric parameters (Å, º) for (I) topF1—C1 | 1.350 (4) | N2—C9 | 1.399 (5) |
O1—C12 | 1.194 (4) | N2—C8 | 1.450 (4) |
O2—C12 | 1.377 (4) | N2—C11 | 1.451 (4) |
O2—C13 | 1.397 (4) | N3—C12 | 1.364 (4) |
N1—C7 | 1.385 (4) | N3—C18 | 1.386 (4) |
N1—C4 | 1.402 (4) | N3—C11 | 1.452 (4) |
N1—C10 | 1.460 (4) | | |
| | | |
N1—C7—C8 | 113.6 (3) | N2—C11—N3 | 110.2 (3) |
N2—C8—C7 | 110.9 (3) | O1—C12—N3 | 129.9 (4) |
N2—C9—C10 | 113.0 (3) | O1—C12—O2 | 122.4 (3) |
N1—C10—C9 | 111.5 (3) | | |
| | | |
C7—N1—C4—C5 | 150.7 (4) | N1—C7—C8—N2 | 50.8 (5) |
C10—N1—C4—C5 | 8.4 (5) | N2—C9—C10—N1 | −54.9 (5) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.58 | 3.268 (4) | 131 |
C14—H14···O2ii | 0.93 | 2.65 | 3.547 (4) | 163 |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y+2, −z. |
Selected geometric parameters (Å, º) for (II) topF1—C1 | 1.351 (2) | N2—C11 | 1.4429 (16) |
O1—C12 | 1.1970 (18) | N2—C9 | 1.4535 (17) |
O2—C12 | 1.3810 (17) | N2—C8 | 1.4553 (16) |
O2—C13 | 1.3872 (17) | N3—C12 | 1.3628 (17) |
N1—C6 | 1.4134 (17) | N3—C18 | 1.3905 (17) |
N1—C7 | 1.4530 (18) | N3—C11 | 1.4518 (15) |
N1—C10 | 1.4620 (17) | | |
| | | |
N1—C7—C8 | 109.66 (12) | N1—C10—C9 | 109.88 (11) |
N2—C8—C7 | 110.41 (12) | O1—C12—N3 | 129.86 (13) |
N2—C9—C10 | 110.30 (11) | O1—C12—O2 | 122.46 (12) |
| | | |
C7—N1—C6—C5 | −12.2 (2) | N2—C9—C10—N1 | 58.71 (16) |
C10—N1—C6—C5 | 117.40 (17) | C18—N3—C11—N2 | −66.38 (16) |
N1—C7—C8—N2 | −59.02 (18) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 0.93 | 2.57 | 3.4680 (18) | 163 |
Symmetry code: (i) −x+1, y−1/2, −z−1/2. |
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Benzoxazolinones have been investigated primarily for their medicinal value as central nervous system depressants, exhibiting analgesic, antipyritic, anticonvulsant, hypnotic and skeletal muscle relaxant activity (Sam & Valentine, 1969). In addition, many investigations of 2-benzoxazolinones have shown that compounds with this structure have antiinflammotary, antineplastic and antimicrobial activities (Clark & Pessolano, 1953; Varma & Nobles, 1968; Varma & Kapoor, 1979; Vaccher et al., 1986; Erol et al., 1989; Kalcheva et al., 1990; Gökhan et al., 1996; Köksal et al., 2002). The medical value of these derivatives prompted us to synthesize 3-substituted 2-benzoxazolinones and clarify their structures.
The pharmacological results indicate that the title compounds, (I) and (II) (both C19H20FN3O2), possess good analgesic activity, coupled with notable anti-inflammatory properties (Okun et al., 1963). Moreover, the title compounds show a remarkable gastric tolerance. It also seems that, as far as the chemical structures of the title compounds are concerned, compounds bearing chloro- and fluoro- substituents show increased analgesic–anti-inflammatory activities.
In order to obtain information about the stereochemistry of the molecules and to confirm the assigned structures, X-ray analysis was undertaken.
In (I), because the benzene and oxazolinone rings are almost parallel to one another, the benzoxazolinone ring is essentially planar; this conformation is consistent with the findings of Köysal et al. (2003). The deviations from the plane of the nine-membered benzoxazolinone ring for atoms C12, C13, C15 and C18 are 0.029 (4), −0.011 (3), 0.015 (3) and −0.012 (3) Å. The plane through the C atoms of the piperazine ring makes a dihedral angle of 89.72 (15)° with benzoxazolinone ring. The piperazine moiety adopts an almost perfect chair conformation [the puckering parametres (Cremer & Pople, 1975) are q2=0.0501 (37) Å, q3=0.5079 (40) Å, QT=0.5101 Å, ϕ=201 (5)° and θ=5.32 (42)°].
Compound (II) also contains a planar benzoxazolinone ring, the maximum deviation from planarity being 0.021 (1) Å for atom C12. The benzoxazolinone ring is nearly perpendicular to the piperazine ring, as in (I), the dihedral angle in (II) being 82.64 (6)°. The piperazine ring in (II) also adopts a chair confromation [q2=0.0113 (13) Å, q3=-0.5861 (15) Å, QT=0.5862 (15) Å, ϕ=187 (8)° and θ=178.73 (13)°].
Compound (I) contains intermolecular C5—H5···O1(x − 1,+y − 1,+z) and C14—H14···O2(-x + 1,-y + 2,-z) contacts, which link the molecules into discrete pairs across crystallographic centres of symmetry. Compound (II) contains only an intermolecular C14—H14.·O1(-x + 1,+y − 1/2,-z − 1/2) contact. The compounds differ in that in (I), the acceptor O atom is within oxazolinone ring, while in (II), the acceptor is the C=O group exo to the ring. Therefore, the intermolecular interactions in (II) link the molecules into infinite chains rather than the discrete dimers found in (I).
π-π stacking interactions are present in the ring?. In both cases, the benzoxazolinone rings align in an antiparallel manner. In the closest interaction (with a perpendicular seperation of 3.4 Å) the lateral offset is small, while the longer interaction (with a perpendicular seperation of 3.6 Å) has a somewhat larger lateral offset.