Comment
The title compound, (I
), has a planar benzo[d][1,3]oxazin-4-one heterocycle that lies on a crystallographic mirror plane. The molecular structure of (I) is shown in Fig. 1
and selected bond distances and angles are given in Table 1
. Within the oxazin-4-one group the C=O and C=N double bonds are clearly localized, but of the two formally single C—O bonds, O2—C2 is significantly shorter than O2—C1. The bicyclic heterocycle is planar despite the unfavourable steric interaction between the 5-methyl and 4-carbonyl groups, but the planarity allows π-stacking of these groups in the direction of the b axis (Fig. 2
), with an inter-layer distance of 3.3662 (4) Å (Table 2
). The widened bond angles of 128.39 (12), 121.75 (11) and 123.51 (12)° for O1—C1—C4, C1—C4—C5 and C4—C5—C9, respectively, still result in a short O1⋯C9 distance of 2.838 (2) Å.![[link]](../../../../../../logos/arrows/e_arr.gif)
| Figure 1 View of the molecular structure of (I ), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by spheres of arbitrary size. Only one orientation of the disordered methyl group is shown. |
| Figure 2 Packing diagram for (I ), viewed down the b axis. Only one orientation for the disordered methyl group is shown. |
Experimental
Suitable crystals of the title compound, (I
), were prepared by the attempted recrystallization of 2-[(adamantane-1-carbonyl)-amino]-6-methylbenzoic acid from petroleum ether (80/100)–toluene.
Data collection
Stoe IPDSII area-detector diffractometer φ and ω scans Absorption correction: none 10561 measured reflections 3325 independent reflections 2132 reflections with I > 2σ(I) Rint = 0.061 θmax = 34.7° h = −13 → 13 k = −10 → 9 l = −21 → 17
|
Refinement
Refinement on F2 R[F2 > 2σ(F2)] = 0.048 wR(F2) = 0.141 S = 1.00 3325 reflections 126 parameters H-atom parameters constrained w = 1/[σ2(Fo2) + (0.081P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.49 e Å−3 Δρmin = −0.37 e Å−3 Extinction correction: SHELXL97 Extinction coefficient: 0.032 (7)
|
O1—C1 | 1.2010 (16) | O2—C2 | 1.3750 (15) | O2—C1 | 1.3940 (15) | N1—C2 | 1.2762 (15) | N1—C3 | 1.4019 (16) | C1—C4 | 1.4625 (17) | C3—C4 | 1.4082 (18) | | C2—O2—C1 | 122.07 (9) | C2—N1—C3 | 117.81 (11) | O1—C1—O2 | 116.33 (11) | O1—C1—C4 | 128.39 (12) | O2—C1—C4 | 115.28 (10) | N1—C2—O2 | 124.64 (11) | N1—C2—C10 | 123.61 (11) | O2—C2—C10 | 111.75 (9) | N1—C3—C4 | 122.43 (10) | C3—C4—C1 | 117.77 (11) | C5—C4—C1 | 121.75 (11) | C4—C5—C9 | 123.51 (12) | | |
C1⋯C7i | 3.3984 (4) | C3⋯C5i | 3.4038 (4) | C4⋯C8i | 3.4884 (5) | N1⋯C6i | 3.5083 (5) | Symmetry code: (i) -x,-y,1-z. | |
All H atoms were initially located in a difference Fourier map. The methyl H atoms were constrained to an ideal geometry with a C—H distance of 0.98 Å, but the group was allowed to rotate freely about its X—C bond. In its final position, the methyl group is not bisected exactly by the mirror plane and hence is disordered 50:50 about the mirror plane. All other H atoms were placed in geometrically idealized positions, with C—H distances of 0.95–1.00 Å. Uiso(H) values were set at 1.2Ueq(C) for all of the H atoms.
Data collection: X-AREA (Stoe & Cie, 2001
); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001
); program(s) used to solve structure: X-STEP32 (Stoe & Cie, 2001
) and WinGX (Farrugia, 1999
); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997
); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997
); software used to prepare material for publication: WinGX.
Supporting information
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: X-STEP32 (Stoe & Cie, 2001) and WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX.
2-(Adamantan-1-yl)-5-methylbenzo[
d][1,3]oxazin-4-one
top Crystal data top C19H21NO2 | F(000) = 316 |
Mr = 295.37 | Dx = 1.352 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yb | Cell parameters from 8117 reflections |
a = 8.3514 (12) Å | θ = 2.5–34.7° |
b = 6.7324 (5) Å | µ = 0.09 mm−1 |
c = 13.3203 (19) Å | T = 150 K |
β = 104.275 (11)° | Block, colourless |
V = 725.81 (16) Å3 | 0.60 × 0.25 × 0.20 mm |
Z = 2 | |
Data collection top Stoe IPDS-II area-detector diffractometer | 2132 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 34.7°, θmin = 2.5° |
φ and ω scans | h = −13→13 |
10561 measured reflections | k = −10→9 |
3325 independent reflections | l = −21→17 |
Refinement top 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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.081P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
3325 reflections | Δρmax = 0.49 e Å−3 |
126 parameters | Δρmin = −0.37 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: 0.032 (7) |
Special details top Experimental. The crystal was mounted under the perfluoro-polyether PFO-XR75 (Lancaster Synthesis). A total of 160 frames (2 minute exposure) were collected (phi/omega: 35/90–160, 120/90–180, delta-omega = 1 °.) |
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 | Occ. (<1) |
O1 | 0.39794 (12) | 0.2500 | 0.58496 (8) | 0.0299 (2) | |
O2 | 0.30446 (10) | 0.2500 | 0.41487 (7) | 0.0219 (2) | |
N1 | 0.02377 (13) | 0.2500 | 0.32687 (8) | 0.0197 (2) | |
C1 | 0.27710 (15) | 0.2500 | 0.51396 (10) | 0.0208 (2) | |
C2 | 0.17667 (14) | 0.2500 | 0.32710 (10) | 0.0187 (2) | |
C3 | −0.01715 (14) | 0.2500 | 0.42282 (10) | 0.0189 (2) | |
C4 | 0.10352 (15) | 0.2500 | 0.51764 (10) | 0.0188 (2) | |
C5 | 0.05645 (16) | 0.2500 | 0.61268 (10) | 0.0219 (2) | |
C6 | −0.11190 (18) | 0.2500 | 0.60815 (11) | 0.0242 (3) | |
H6 | −0.1462 | 0.2500 | 0.6710 | 0.029* | |
C7 | −0.23170 (16) | 0.2500 | 0.51463 (12) | 0.0254 (3) | |
H7 | −0.3455 | 0.2500 | 0.5144 | 0.030* | |
C8 | −0.18492 (15) | 0.2500 | 0.42207 (11) | 0.0233 (3) | |
H8 | −0.2664 | 0.2500 | 0.3582 | 0.028* | |
C9 | 0.1785 (2) | 0.2500 | 0.71724 (11) | 0.0317 (3) | |
H9A | 0.1207 | 0.2201 | 0.7711 | 0.038* | 0.50 |
H9B | 0.2307 | 0.3810 | 0.7303 | 0.038* | 0.50 |
H9C | 0.2633 | 0.1490 | 0.7182 | 0.038* | 0.50 |
C10 | 0.23881 (14) | 0.2500 | 0.22986 (9) | 0.0179 (2) | |
C11 | 0.09153 (15) | 0.2500 | 0.13392 (10) | 0.0248 (3) | |
H11A | 0.0224 | 0.1309 | 0.1349 | 0.030* | 0.50 |
H11B | 0.0224 | 0.3691 | 0.1349 | 0.030* | 0.50 |
C12 | 0.15514 (16) | 0.2500 | 0.03505 (10) | 0.0265 (3) | |
H12 | 0.0589 | 0.2500 | −0.0269 | 0.032* | |
C13 | 0.25990 (13) | 0.43563 (16) | 0.03269 (8) | 0.0273 (2) | |
H13A | 0.1923 | 0.5562 | 0.0334 | 0.033* | |
H13B | 0.2993 | 0.4370 | −0.0316 | 0.033* | |
C14 | 0.40801 (12) | 0.43543 (14) | 0.12743 (7) | 0.02358 (19) | |
H14 | 0.4765 | 0.5567 | 0.1258 | 0.028* | |
C15 | 0.34586 (12) | 0.43626 (14) | 0.22713 (7) | 0.02296 (19) | |
H15A | 0.2797 | 0.5575 | 0.2293 | 0.028* | |
H15B | 0.4412 | 0.4371 | 0.2884 | 0.028* | |
C16 | 0.51278 (16) | 0.2500 | 0.12420 (10) | 0.0235 (3) | |
H16A | 0.5524 | 0.2500 | 0.0600 | 0.028* | |
H16B | 0.6103 | 0.2500 | 0.1842 | 0.028* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0196 (4) | 0.0484 (7) | 0.0209 (5) | 0.000 | 0.0036 (3) | 0.000 |
O2 | 0.0149 (4) | 0.0333 (5) | 0.0184 (4) | 0.000 | 0.0059 (3) | 0.000 |
N1 | 0.0169 (4) | 0.0230 (5) | 0.0202 (5) | 0.000 | 0.0067 (4) | 0.000 |
C1 | 0.0186 (5) | 0.0250 (6) | 0.0198 (5) | 0.000 | 0.0068 (4) | 0.000 |
C2 | 0.0173 (5) | 0.0201 (5) | 0.0193 (5) | 0.000 | 0.0058 (4) | 0.000 |
C3 | 0.0171 (5) | 0.0193 (5) | 0.0219 (5) | 0.000 | 0.0079 (4) | 0.000 |
C4 | 0.0180 (5) | 0.0191 (5) | 0.0212 (5) | 0.000 | 0.0086 (4) | 0.000 |
C5 | 0.0257 (6) | 0.0207 (6) | 0.0220 (6) | 0.000 | 0.0111 (5) | 0.000 |
C6 | 0.0284 (6) | 0.0217 (6) | 0.0286 (6) | 0.000 | 0.0184 (5) | 0.000 |
C7 | 0.0207 (5) | 0.0241 (6) | 0.0362 (7) | 0.000 | 0.0165 (5) | 0.000 |
C8 | 0.0172 (5) | 0.0258 (6) | 0.0284 (6) | 0.000 | 0.0085 (5) | 0.000 |
C9 | 0.0353 (7) | 0.0427 (8) | 0.0191 (6) | 0.000 | 0.0105 (5) | 0.000 |
C10 | 0.0167 (5) | 0.0210 (5) | 0.0174 (5) | 0.000 | 0.0069 (4) | 0.000 |
C11 | 0.0175 (5) | 0.0374 (7) | 0.0200 (6) | 0.000 | 0.0058 (4) | 0.000 |
C12 | 0.0206 (5) | 0.0414 (8) | 0.0179 (5) | 0.000 | 0.0055 (4) | 0.000 |
C13 | 0.0314 (5) | 0.0293 (5) | 0.0245 (4) | 0.0079 (4) | 0.0133 (4) | 0.0080 (4) |
C14 | 0.0278 (4) | 0.0209 (4) | 0.0259 (4) | −0.0046 (3) | 0.0140 (3) | −0.0008 (3) |
C15 | 0.0264 (4) | 0.0212 (4) | 0.0246 (4) | −0.0038 (3) | 0.0126 (3) | −0.0035 (3) |
C16 | 0.0193 (5) | 0.0315 (7) | 0.0221 (6) | 0.000 | 0.0095 (4) | 0.000 |
Geometric parameters (Å, º) top O1—C1 | 1.2010 (16) | C10—C11 | 1.5398 (17) |
O2—C2 | 1.3750 (15) | C10—C15 | 1.5457 (11) |
O2—C1 | 1.3940 (15) | C10—C15i | 1.5457 (11) |
N1—C2 | 1.2762 (15) | C11—C12 | 1.5368 (18) |
N1—C3 | 1.4019 (16) | C11—H11A | 0.9900 |
C1—C4 | 1.4625 (17) | C11—H11B | 0.9900 |
C2—C10 | 1.5094 (16) | C12—C13 | 1.5303 (13) |
C3—C8 | 1.3988 (17) | C12—C13i | 1.5303 (13) |
C3—C4 | 1.4082 (18) | C12—H12 | 1.0000 |
C4—C5 | 1.4151 (17) | C13—C14 | 1.5339 (14) |
C5—C6 | 1.3923 (19) | C13—H13A | 0.9900 |
C5—C9 | 1.510 (2) | C13—H13B | 0.9900 |
C6—C7 | 1.392 (2) | C14—C16 | 1.5311 (12) |
C6—H6 | 0.9500 | C14—C15 | 1.5405 (12) |
C7—C8 | 1.3821 (19) | C14—H14 | 1.0000 |
C7—H7 | 0.9500 | C15—H15A | 0.9900 |
C8—H8 | 0.9500 | C15—H15B | 0.9900 |
C9—H9A | 0.9800 | C16—C14i | 1.5311 (12) |
C9—H9B | 0.9800 | C16—H16A | 0.9900 |
C9—H9C | 0.9800 | C16—H16B | 0.9900 |
| | | |
C1···C7ii | 3.3984 (4) | C4···C8ii | 3.4884 (5) |
C3···C5ii | 3.4038 (4) | N1···C6ii | 3.5083 (5) |
| | | |
C2—O2—C1 | 122.07 (9) | C15—C10—C15i | 108.44 (10) |
C2—N1—C3 | 117.81 (11) | C12—C11—C10 | 109.70 (10) |
O1—C1—O2 | 116.33 (11) | C12—C11—H11A | 109.7 |
O1—C1—C4 | 128.39 (12) | C10—C11—H11A | 109.7 |
O2—C1—C4 | 115.28 (10) | C12—C11—H11B | 109.7 |
N1—C2—O2 | 124.64 (11) | C10—C11—H11B | 109.7 |
N1—C2—C10 | 123.61 (11) | H11A—C11—H11B | 108.2 |
O2—C2—C10 | 111.75 (9) | C13—C12—C13i | 109.51 (11) |
C8—C3—N1 | 117.55 (11) | C13—C12—C11 | 109.74 (7) |
C8—C3—C4 | 120.03 (11) | C13i—C12—C11 | 109.74 (7) |
N1—C3—C4 | 122.43 (10) | C13—C12—H12 | 109.3 |
C3—C4—C5 | 120.48 (11) | C13i—C12—H12 | 109.3 |
C3—C4—C1 | 117.77 (11) | C11—C12—H12 | 109.3 |
C5—C4—C1 | 121.75 (11) | C12—C13—C14 | 109.36 (8) |
C6—C5—C4 | 117.48 (12) | C12—C13—H13A | 109.8 |
C6—C5—C9 | 119.01 (12) | C14—C13—H13A | 109.8 |
C4—C5—C9 | 123.51 (12) | C12—C13—H13B | 109.8 |
C7—C6—C5 | 122.28 (12) | C14—C13—H13B | 109.8 |
C7—C6—H6 | 118.9 | H13A—C13—H13B | 108.2 |
C5—C6—H6 | 118.9 | C16—C14—C13 | 109.15 (9) |
C8—C7—C6 | 119.96 (12) | C16—C14—C15 | 110.09 (8) |
C8—C7—H7 | 120.0 | C13—C14—C15 | 109.54 (8) |
C6—C7—H7 | 120.0 | C16—C14—H14 | 109.3 |
C7—C8—C3 | 119.78 (12) | C13—C14—H14 | 109.3 |
C7—C8—H8 | 120.1 | C15—C14—H14 | 109.3 |
C3—C8—H8 | 120.1 | C14—C15—C10 | 109.70 (8) |
C5—C9—H9A | 109.5 | C14—C15—H15A | 109.7 |
C5—C9—H9B | 109.5 | C10—C15—H15A | 109.7 |
H9A—C9—H9B | 109.5 | C14—C15—H15B | 109.7 |
C5—C9—H9C | 109.5 | C10—C15—H15B | 109.7 |
H9A—C9—H9C | 109.5 | H15A—C15—H15B | 108.2 |
H9B—C9—H9C | 109.5 | C14i—C16—C14 | 109.24 (10) |
C2—C10—C11 | 109.81 (9) | C14i—C16—H16A | 109.8 |
C2—C10—C15 | 110.08 (6) | C14—C16—H16A | 109.8 |
C11—C10—C15 | 109.19 (7) | C14i—C16—H16B | 109.8 |
C2—C10—C15i | 110.08 (6) | C14—C16—H16B | 109.8 |
C11—C10—C15i | 109.19 (7) | H16A—C16—H16B | 108.3 |
| | | |
C2—O2—C1—O1 | 180.0 | N1—C3—C8—C7 | 180.0 |
C2—O2—C1—C4 | 0.0 | C4—C3—C8—C7 | 0.0 |
C3—N1—C2—O2 | 0.0 | N1—C2—C10—C11 | 0.0 |
C3—N1—C2—C10 | 180.0 | O2—C2—C10—C11 | 180.0 |
C1—O2—C2—N1 | 0.0 | N1—C2—C10—C15 | 120.25 (7) |
C1—O2—C2—C10 | 180.0 | O2—C2—C10—C15 | −59.75 (7) |
C2—N1—C3—C8 | 180.0 | N1—C2—C10—C15i | −120.25 (7) |
C2—N1—C3—C4 | 0.0 | O2—C2—C10—C15i | 59.75 (7) |
C8—C3—C4—C5 | 0.0 | C2—C10—C11—C12 | 180.0 |
N1—C3—C4—C5 | 180.0 | C15—C10—C11—C12 | 59.21 (6) |
C8—C3—C4—C1 | 180.0 | C15i—C10—C11—C12 | −59.21 (6) |
N1—C3—C4—C1 | 0.0 | C10—C11—C12—C13 | −60.19 (7) |
O1—C1—C4—C3 | 180.0 | C10—C11—C12—C13i | 60.19 (7) |
O2—C1—C4—C3 | 0.0 | C13i—C12—C13—C14 | −60.07 (12) |
O1—C1—C4—C5 | 0.0 | C11—C12—C13—C14 | 60.45 (11) |
O2—C1—C4—C5 | 180.0 | C12—C13—C14—C16 | 60.38 (10) |
C3—C4—C5—C6 | 0.0 | C12—C13—C14—C15 | −60.23 (10) |
C1—C4—C5—C6 | 180.0 | C16—C14—C15—C10 | −60.25 (10) |
C3—C4—C5—C9 | 180.0 | C13—C14—C15—C10 | 59.79 (10) |
C1—C4—C5—C9 | 0.0 | C2—C10—C15—C14 | −179.74 (8) |
C4—C5—C6—C7 | 0.0 | C11—C10—C15—C14 | −59.12 (10) |
C9—C5—C6—C7 | 180.0 | C15i—C10—C15—C14 | 59.77 (12) |
C5—C6—C7—C8 | 0.0 | C13—C14—C16—C14i | −60.82 (12) |
C6—C7—C8—C3 | 0.0 | C15—C14—C16—C14i | 59.45 (13) |
Symmetry codes: (i) x, −y+1/2, z; (ii) −x, −y, −z+1. |
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ISSN: 2056-9890