The five-membered ring of the title compound, C
14H
15NO
3, has a flattened envelope conformation, while the eight-membered ring can be described as a highly distorted boat. Weak C—H
O hydrogen bonds and van der Waals interactions determine the crystal packing.
Supporting information
CCDC reference: 165648
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.063
- wR factor = 0.137
- Data-to-parameter ratio = 9.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 74.96
From the CIF: _reflns_number_total 1472
Count of symmetry unique reflns 1497
Completeness (_total/calc) 98.33%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
Colourless prismatic crystals were grown from hexane solution by slow
evaporation.
Data collection: CAD-4 Software; cell refinement: CAD-4 Software; data reduction: ENPROC (Rettig, 1978); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989).
8-Oxa-1-aza-7-phenylbicyclo[5.2.1]decane-9,10-dione
top
Crystal data top
C14H15NO3 | Dx = 1.314 Mg m−3 |
Mr = 245.27 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 6.7112 (8) Å | θ = 10–25° |
b = 10.4414 (8) Å | µ = 0.76 mm−1 |
c = 17.687 (2) Å | T = 293 K |
V = 1239.4 (2) Å3 | Plate, colourless |
Z = 4 | 0.25 × 0.2 × 0.1 mm |
F(000) = 520 | |
Data collection top
CAD-4F four-circle diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 75.0°, θmin = 4.9° |
Ni-filter monochromator | h = −8→0 |
ω/2θ scans | k = 0→13 |
1472 measured reflections | l = 0→22 |
1472 independent reflections | 2 standard reflections every 33 min |
1199 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.063 | H-atom parameters not refined |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.01P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
1472 reflections | Δρmax = 0.18 e Å−3 |
164 parameters | Δρmin = −0.18 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: 0.0043 (8) |
Crystal data top
C14H15NO3 | V = 1239.4 (2) Å3 |
Mr = 245.27 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.7112 (8) Å | µ = 0.76 mm−1 |
b = 10.4414 (8) Å | T = 293 K |
c = 17.687 (2) Å | 0.25 × 0.2 × 0.1 mm |
Data collection top
CAD-4F four-circle diffractometer | Rint = 0.000 |
1472 measured reflections | 2 standard reflections every 33 min |
1472 independent reflections | intensity decay: 3% |
1199 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters not refined |
S = 1.10 | Δρmax = 0.18 e Å−3 |
1472 reflections | Δρmin = −0.18 e Å−3 |
164 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 | |
N1 | 0.0144 (5) | 0.2640 (3) | 0.86377 (19) | 0.0510 (8) | |
C2 | 0.0850 (7) | 0.3872 (4) | 0.8327 (3) | 0.0621 (12) | |
H21 | 0.1103 | 0.4470 | 0.8735 | 0.081* | |
H22 | −0.0161 | 0.4236 | 0.7999 | 0.081* | |
C3 | 0.2745 (8) | 0.3645 (4) | 0.7883 (2) | 0.0652 (12) | |
H31 | 0.3350 | 0.4468 | 0.7773 | 0.085* | |
H32 | 0.2399 | 0.3250 | 0.7404 | 0.085* | |
C4 | 0.4287 (7) | 0.2803 (4) | 0.8280 (3) | 0.0658 (12) | |
H41 | 0.4284 | 0.3023 | 0.8813 | 0.086* | |
H42 | 0.5591 | 0.3023 | 0.8082 | 0.086* | |
C5 | 0.4021 (8) | 0.1332 (4) | 0.8212 (2) | 0.0630 (12) | |
H51 | 0.3067 | 0.1172 | 0.7811 | 0.082* | |
H52 | 0.5285 | 0.0975 | 0.8049 | 0.082* | |
C6 | 0.3337 (8) | 0.0574 (4) | 0.8913 (2) | 0.0575 (11) | |
H61 | 0.3562 | −0.0329 | 0.8815 | 0.075* | |
H62 | 0.4185 | 0.0815 | 0.9334 | 0.075* | |
C7 | 0.1171 (7) | 0.0740 (3) | 0.9160 (2) | 0.0474 (10) | |
C71 | 0.0491 (8) | −0.0121 (3) | 0.9802 (2) | 0.0578 (12) | |
C72 | 0.1773 (11) | −0.0245 (5) | 1.0421 (2) | 0.0839 (18) | |
H72 | 0.2983 | 0.0188 | 1.0432 | 0.101* | |
C73 | 0.1203 (15) | −0.1031 (5) | 1.1023 (3) | 0.112 (3) | |
H73 | 0.2041 | −0.1137 | 1.1437 | 0.134* | |
C74 | −0.0623 (13) | −0.1653 (5) | 1.0998 (3) | 0.104 (3) | |
H74 | −0.1022 | −0.2158 | 1.1404 | 0.125* | |
C75 | −0.1825 (10) | −0.1531 (5) | 1.0391 (3) | 0.0907 (18) | |
H75 | −0.3032 | −0.1968 | 1.0376 | 0.109* | |
C76 | −0.1271 (9) | −0.0759 (4) | 0.9791 (3) | 0.0734 (14) | |
H76 | −0.2114 | −0.0676 | 0.9377 | 0.088* | |
O8 | −0.0105 (5) | 0.0538 (2) | 0.85033 (15) | 0.0568 (8) | |
C9 | −0.0398 (6) | 0.1662 (4) | 0.8152 (2) | 0.0555 (10) | |
O9 | −0.1123 (6) | 0.1764 (3) | 0.75395 (17) | 0.0788 (11) | |
C10 | 0.0909 (6) | 0.2164 (3) | 0.9297 (2) | 0.0468 (9) | |
O10 | 0.1485 (5) | 0.2767 (2) | 0.98398 (14) | 0.0628 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.054 (2) | 0.0398 (16) | 0.0598 (19) | 0.0039 (16) | 0.0046 (18) | 0.0027 (14) |
C2 | 0.073 (3) | 0.038 (2) | 0.076 (3) | 0.003 (2) | 0.012 (3) | 0.0095 (19) |
C3 | 0.076 (3) | 0.052 (2) | 0.068 (3) | −0.005 (2) | 0.014 (3) | 0.011 (2) |
C4 | 0.066 (3) | 0.057 (2) | 0.075 (3) | −0.003 (2) | 0.016 (3) | 0.001 (2) |
C5 | 0.063 (3) | 0.064 (3) | 0.062 (2) | 0.005 (2) | 0.018 (2) | −0.007 (2) |
C6 | 0.075 (3) | 0.0380 (19) | 0.059 (2) | 0.005 (2) | 0.001 (2) | −0.0045 (19) |
C7 | 0.061 (3) | 0.0311 (16) | 0.050 (2) | −0.0066 (19) | −0.002 (2) | −0.0066 (15) |
C71 | 0.086 (3) | 0.0314 (17) | 0.056 (2) | −0.002 (2) | 0.009 (2) | −0.0048 (17) |
C72 | 0.138 (5) | 0.060 (3) | 0.054 (2) | −0.031 (3) | −0.004 (3) | 0.001 (2) |
C73 | 0.209 (8) | 0.070 (3) | 0.056 (3) | −0.026 (5) | 0.000 (4) | 0.006 (3) |
C74 | 0.181 (8) | 0.045 (3) | 0.085 (4) | −0.014 (4) | 0.046 (5) | 0.003 (3) |
C75 | 0.114 (5) | 0.052 (3) | 0.107 (4) | −0.019 (3) | 0.030 (4) | 0.009 (3) |
C76 | 0.083 (3) | 0.049 (2) | 0.088 (3) | −0.008 (3) | 0.012 (3) | 0.007 (2) |
O8 | 0.074 (2) | 0.0420 (14) | 0.0538 (15) | −0.0129 (15) | −0.0095 (16) | −0.0033 (12) |
C9 | 0.051 (2) | 0.055 (2) | 0.061 (2) | −0.004 (2) | −0.004 (2) | 0.001 (2) |
O9 | 0.083 (2) | 0.084 (2) | 0.0691 (18) | −0.009 (2) | −0.0246 (19) | 0.0089 (18) |
C10 | 0.054 (2) | 0.0374 (17) | 0.0495 (19) | 0.0019 (18) | 0.0110 (19) | −0.0051 (17) |
O10 | 0.095 (2) | 0.0393 (14) | 0.0540 (16) | −0.0084 (17) | 0.0121 (17) | −0.0108 (13) |
Geometric parameters (Å, º) top
N1—C10 | 1.368 (5) | C7—O8 | 1.459 (4) |
N1—C9 | 1.383 (5) | C7—C10 | 1.517 (5) |
N1—C2 | 1.477 (5) | C7—C71 | 1.519 (5) |
C2—C3 | 1.513 (6) | C71—C76 | 1.357 (7) |
C2—H21 | 0.9700 | C71—C72 | 1.398 (7) |
C2—H22 | 0.9700 | C72—C73 | 1.398 (7) |
C3—C4 | 1.529 (6) | C72—H72 | 0.9300 |
C3—H31 | 0.9700 | C73—C74 | 1.387 (11) |
C3—H32 | 0.9700 | C73—H73 | 0.9300 |
C4—C5 | 1.551 (6) | C74—C75 | 1.349 (8) |
C4—H41 | 0.9700 | C74—H74 | 0.9300 |
C4—H42 | 0.9700 | C75—C76 | 1.384 (7) |
C5—C6 | 1.541 (5) | C75—H75 | 0.9300 |
C5—H51 | 0.9700 | C76—H76 | 0.9300 |
C5—H52 | 0.9700 | O8—C9 | 1.342 (5) |
C6—C7 | 1.528 (6) | C9—O9 | 1.193 (5) |
C6—H61 | 0.9700 | C10—O10 | 1.211 (4) |
C6—H62 | 0.9700 | | |
| | | |
C10—N1—C9 | 111.1 (3) | H61—C6—H62 | 107.3 |
C10—N1—C2 | 120.9 (4) | O8—C7—C10 | 101.6 (3) |
C9—N1—C2 | 119.8 (3) | O8—C7—C71 | 109.5 (3) |
N1—C2—C3 | 109.1 (3) | C10—C7—C71 | 115.2 (3) |
N1—C2—H21 | 109.9 | O8—C7—C6 | 108.3 (3) |
C3—C2—H21 | 109.9 | C10—C7—C6 | 105.5 (3) |
N1—C2—H22 | 109.9 | C71—C7—C6 | 115.6 (4) |
C3—C2—H22 | 109.9 | C76—C71—C72 | 120.1 (4) |
H21—C2—H22 | 108.3 | C76—C71—C7 | 122.8 (4) |
C2—C3—C4 | 114.9 (3) | C72—C71—C7 | 117.1 (4) |
C2—C3—H31 | 108.5 | C73—C72—C71 | 118.8 (6) |
C4—C3—H31 | 108.5 | C73—C72—H72 | 120.6 |
C2—C3—H32 | 108.5 | C71—C72—H72 | 120.6 |
C4—C3—H32 | 108.5 | C74—C73—C72 | 119.5 (7) |
H31—C3—H32 | 107.5 | C74—C73—H73 | 120.2 |
C3—C4—C5 | 117.1 (4) | C72—C73—H73 | 120.2 |
C3—C4—H41 | 108.0 | C75—C74—C73 | 120.6 (5) |
C5—C4—H41 | 108.0 | C75—C74—H74 | 119.7 |
C3—C4—H42 | 108.0 | C73—C74—H74 | 119.7 |
C5—C4—H42 | 108.0 | C74—C75—C76 | 120.3 (6) |
H41—C4—H42 | 107.3 | C74—C75—H75 | 119.8 |
C6—C5—C4 | 118.7 (4) | C76—C75—H75 | 119.8 |
C6—C5—H51 | 107.6 | C71—C76—C75 | 120.6 (5) |
C4—C5—H51 | 107.6 | C71—C76—H76 | 119.7 |
C6—C5—H52 | 107.6 | C75—C76—H76 | 119.7 |
C4—C5—H52 | 107.6 | C9—O8—C7 | 109.2 (3) |
H51—C5—H52 | 107.1 | O9—C9—O8 | 123.9 (4) |
C7—C6—C5 | 117.1 (4) | O9—C9—N1 | 127.3 (4) |
C7—C6—H61 | 108.0 | O8—C9—N1 | 108.7 (3) |
C5—C6—H61 | 108.0 | O10—C10—N1 | 127.3 (3) |
C7—C6—H62 | 108.0 | O10—C10—C7 | 126.8 (4) |
C5—C6—H62 | 108.0 | N1—C10—C7 | 105.3 (3) |
| | | |
C10—N1—C2—C3 | 83.1 (4) | C7—C71—C76—C75 | −179.9 (4) |
C9—N1—C2—C3 | −62.5 (5) | C74—C75—C76—C71 | 0.4 (8) |
N1—C2—C3—C4 | −46.3 (5) | C10—C7—O8—C9 | 20.6 (4) |
C2—C3—C4—C5 | 83.4 (5) | C71—C7—O8—C9 | 142.9 (3) |
C3—C4—C5—C6 | −108.2 (5) | C6—C7—O8—C9 | −90.2 (4) |
C4—C5—C6—C7 | 71.8 (6) | C7—O8—C9—O9 | 168.2 (4) |
C5—C6—C7—O8 | 50.7 (4) | C7—O8—C9—N1 | −15.9 (5) |
C5—C6—C7—C10 | −57.4 (4) | C10—N1—C9—O9 | 179.3 (4) |
C5—C6—C7—C71 | 174.0 (3) | C2—N1—C9—O9 | −32.0 (7) |
O8—C7—C71—C76 | −12.2 (5) | C10—N1—C9—O8 | 3.5 (5) |
C10—C7—C71—C76 | 101.5 (5) | C2—N1—C9—O8 | 152.3 (4) |
C6—C7—C71—C76 | −134.9 (4) | C9—N1—C10—O10 | −178.6 (4) |
O8—C7—C71—C72 | 167.6 (4) | C2—N1—C10—O10 | 33.1 (6) |
C10—C7—C71—C72 | −78.7 (5) | C9—N1—C10—C7 | 9.6 (5) |
C6—C7—C71—C72 | 44.9 (5) | C2—N1—C10—C7 | −138.7 (4) |
C76—C71—C72—C73 | −0.1 (7) | O8—C7—C10—O10 | 170.4 (4) |
C7—C71—C72—C73 | −179.9 (5) | C71—C7—C10—O10 | 52.2 (6) |
C71—C72—C73—C74 | −1.0 (8) | C6—C7—C10—O10 | −76.7 (5) |
C72—C73—C74—C75 | 1.7 (9) | O8—C7—C10—N1 | −17.8 (4) |
C73—C74—C75—C76 | −1.5 (9) | C71—C7—C10—N1 | −136.0 (4) |
C72—C71—C76—C75 | 0.3 (7) | C6—C7—C10—N1 | 95.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H62···O10i | 0.97 | 2.59 | 3.512 (5) | 159 |
C74—H74···O9ii | 0.93 | 2.81 | 3.495 (7) | 132 |
C4—H42···O9iii | 0.97 | 2.74 | 3.519 (6) | 138 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) −x−1/2, −y, z+1/2; (iii) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | C14H15NO3 |
Mr | 245.27 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.7112 (8), 10.4414 (8), 17.687 (2) |
V (Å3) | 1239.4 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.25 × 0.2 × 0.1 |
|
Data collection |
Diffractometer | CAD-4F four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1472, 1472, 1199 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.137, 1.10 |
No. of reflections | 1472 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Selected geometric parameters (Å, º) topN1—C10 | 1.368 (5) | C7—C71 | 1.519 (5) |
N1—C9 | 1.383 (5) | O8—C9 | 1.342 (5) |
N1—C2 | 1.477 (5) | C9—O9 | 1.193 (5) |
C7—O8 | 1.459 (4) | C10—O10 | 1.211 (4) |
| | | |
C10—N1—C9 | 111.1 (3) | C9—N1—C2 | 119.8 (3) |
C10—N1—C2 | 120.9 (4) | C9—O8—C7 | 109.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H62···O10i | 0.97 | 2.59 | 3.512 (5) | 158.5 |
C74—H74···O9ii | 0.93 | 2.81 | 3.495 (7) | 131.7 |
C4—H42···O9iii | 0.97 | 2.74 | 3.519 (6) | 137.7 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) −x−1/2, −y, z+1/2; (iii) x+1, y, z. |
Bicyclic imides with a bridgehead N atom were proposed by Smissman as potential stereoselective anticonvulsants (Smissman et al., 1964) and the synthesis of the first examples of this class of compounds (nicknamed `smissmanones') was reported in 1984 (Brouillette & Einspahr, 1984). The title compound, (I), has significant biological activity and acts as a good antimaximal electroshock anticonvulsant as well as a relatively good binder to a sodium channel (Brouillette et al., 1988). The crystal structure of 1-aza-8,9-dioxo-7-oxa-6-phenylbicyclo[4.2.1]nonane was reported earlier (Brouillette & Einspahr, 1984). We report here the results of X-ray crystallographic studies of the compound with an additional CH2 group in the bicyclic system, namely 8-oxa-1-aza-7-phenylbicyclo[5.2.1]decane-9,10-dione.
Fig. 1 shows the title molecule. The conformation of the five-membered ring is close to a flattened envelope with a relatively small value of the asymmetry parameter (Duax & Norton, 1975) ΔC27 = 4.4°. The four atoms O8, C9, N1 and C10 are close to coplanarity [maximum deviation from the least-squares plane of 0.015 (3) Å], while the fifth atom, C7, is 0.314 (3) Å out of this plane. The conformation of eight-membered ring can be described as a highly distorted boat (approximate point group 222, D2). The phenyl ring is planar within experimental error, with a maximum deviation from the least-squares plane of 0.011 (4) Å. Relatively large values of displacement parameters, especially in the phenyl fragment, can be connected with the low melting point of this compound, 319–320 K (Brouillette & Einspahr, 1984).
A comparison of the cyclononane and cyclodecane derivatives (Fig. 2) shows that an additional atom in the ring does not significantly change the overall shape of the molecule.
The crystal packing is determined by van der Waals interactions and weak C—H···O hydrogen bonds, which connect the molecules into infinite chains and three-molecule rings.