The title compound, 4-methoxy-12-methyl-12-azatetracyclo[9.3
1,10.0
2,7]heptadeca-2(7),3,5-triene, C
18H
25NO, has a T-shaped configuration, with the benzene ring (
A) and the fused carbocyclic ring (
C) forming the upright stock; the other carbocyclic ring (
D) and the piperidine ring (
E) are in the arm positions. Rings
C,
D and
E have sofa, chair and chair conformations, respectively. In the crystal packing, the molecules are joined through C—H
O hydrogen bonding into chains running along the
c axis.
Supporting information
CCDC reference: 277705
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.002 Å
- R factor = 0.038
- wR factor = 0.102
- Data-to-parameter ratio = 11.3
checkCIF/PLATON results
No syntax errors found
Alert level G
REFLT03_ALERT_4_G 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.
From the CIF: _diffrn_reflns_theta_max 27.99
From the CIF: _reflns_number_total 2066
Count of symmetry unique reflns 2097
Completeness (_total/calc) 98.52%
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
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
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).
4-methoxy-12-methyl-12-azatetracyclo[9.3
1.10.0
2.7] heptadeca-2(7),3,5-triene
top
Crystal data top
C18H25NO | F(000) = 592 |
Mr = 271.39 | Dx = 1.195 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 6946 reflections |
a = 14.0356 (12) Å | θ = 2.7–27.8° |
b = 15.0658 (13) Å | µ = 0.07 mm−1 |
c = 7.1354 (6) Å | T = 273 K |
V = 1508.8 (2) Å3 | Needle, colourless |
Z = 4 | 0.22 × 0.18 × 0.16 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 1963 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 28.0°, θmin = 2.0° |
ω scans | h = −18→18 |
13046 measured reflections | k = −19→19 |
2066 independent reflections | l = −9→9 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0624P)2 + 0.1352P] where P = (Fo2 + 2Fc2)/3 |
2066 reflections | (Δ/σ)max = 0.001 |
183 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
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 | |
C1 | 1.13876 (11) | 0.25661 (11) | 0.7611 (2) | 0.0413 (4) | |
H1 | 1.1531 | 0.3167 | 0.7508 | 0.050* | |
C2 | 1.19995 (12) | 0.19619 (12) | 0.6849 (2) | 0.0443 (4) | |
H2 | 1.2549 | 0.2149 | 0.6236 | 0.053* | |
C3 | 1.17914 (11) | 0.10603 (12) | 0.7000 (2) | 0.0406 (4) | |
C4 | 1.09516 (11) | 0.07922 (10) | 0.7868 (2) | 0.0377 (3) | |
H4 | 1.0804 | 0.0191 | 0.7930 | 0.045* | |
C5 | 0.89891 (12) | 0.02597 (11) | 0.8931 (3) | 0.0433 (4) | |
H5A | 0.9470 | −0.0198 | 0.8795 | 0.052* | |
H5B | 0.8510 | 0.0043 | 0.9797 | 0.052* | |
C6 | 0.85252 (14) | 0.04260 (13) | 0.7034 (3) | 0.0547 (5) | |
H6A | 0.9011 | 0.0590 | 0.6131 | 0.066* | |
H6B | 0.8224 | −0.0116 | 0.6600 | 0.066* | |
C7 | 0.77850 (14) | 0.11596 (14) | 0.7154 (3) | 0.0593 (5) | |
H7A | 0.7263 | 0.0969 | 0.7949 | 0.071* | |
H7B | 0.7531 | 0.1278 | 0.5914 | 0.071* | |
C8 | 0.82238 (13) | 0.20085 (12) | 0.7951 (3) | 0.0483 (4) | |
H8A | 0.8693 | 0.2237 | 0.7077 | 0.058* | |
H8B | 0.7730 | 0.2454 | 0.8097 | 0.058* | |
C9 | 0.91478 (11) | 0.26648 (11) | 1.0712 (2) | 0.0384 (3) | |
H9 | 0.8650 | 0.3120 | 1.0783 | 0.046* | |
C10 | 0.99298 (12) | 0.30212 (10) | 0.9411 (2) | 0.0410 (3) | |
H10A | 0.9632 | 0.3360 | 0.8415 | 0.049* | |
H10B | 1.0331 | 0.3424 | 1.0118 | 0.049* | |
C11 | 1.05504 (10) | 0.23151 (10) | 0.8543 (2) | 0.0356 (3) | |
C12 | 1.03261 (10) | 0.14125 (10) | 0.8649 (2) | 0.0342 (3) | |
C13 | 0.94546 (10) | 0.10962 (10) | 0.9759 (2) | 0.0347 (3) | |
C14 | 0.86987 (10) | 0.18396 (10) | 0.9845 (2) | 0.0374 (3) | |
H14 | 0.8199 | 0.1639 | 1.0706 | 0.045* | |
C15 | 0.97785 (12) | 0.09145 (11) | 1.1794 (2) | 0.0419 (4) | |
H15A | 0.9247 | 0.0675 | 1.2499 | 0.050* | |
H15B | 1.0280 | 0.0471 | 1.1782 | 0.050* | |
C16 | 1.01421 (12) | 0.17438 (12) | 1.2771 (2) | 0.0447 (4) | |
H16A | 1.0268 | 0.1612 | 1.4078 | 0.054* | |
H16B | 1.0735 | 0.1931 | 1.2197 | 0.054* | |
C17 | 0.97607 (15) | 0.32453 (13) | 1.3656 (3) | 0.0557 (5) | |
H17A | 1.0355 | 0.3447 | 1.3142 | 0.083* | |
H17B | 0.9846 | 0.3099 | 1.4955 | 0.083* | |
H17C | 0.9293 | 0.3707 | 1.3542 | 0.083* | |
C18 | 1.22770 (17) | −0.04348 (14) | 0.6454 (4) | 0.0662 (6) | |
H18A | 1.1722 | −0.0581 | 0.5731 | 0.099* | |
H18B | 1.2169 | −0.0586 | 0.7744 | 0.099* | |
H18C | 1.2814 | −0.0762 | 0.5989 | 0.099* | |
O1 | 1.24627 (9) | 0.04877 (10) | 0.6304 (2) | 0.0565 (4) | |
N1 | 0.94412 (10) | 0.24632 (9) | 1.2641 (2) | 0.0423 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0389 (7) | 0.0397 (8) | 0.0452 (8) | −0.0099 (6) | −0.0021 (7) | 0.0055 (7) |
C2 | 0.0330 (7) | 0.0566 (9) | 0.0432 (8) | −0.0091 (7) | 0.0036 (7) | 0.0043 (8) |
C3 | 0.0339 (7) | 0.0496 (8) | 0.0384 (8) | −0.0030 (6) | 0.0025 (6) | −0.0032 (7) |
C4 | 0.0354 (7) | 0.0381 (7) | 0.0394 (8) | −0.0041 (6) | 0.0006 (6) | −0.0011 (6) |
C5 | 0.0385 (7) | 0.0369 (8) | 0.0545 (10) | −0.0073 (6) | 0.0045 (7) | 0.0033 (7) |
C6 | 0.0552 (10) | 0.0491 (9) | 0.0599 (11) | −0.0131 (8) | −0.0099 (9) | −0.0073 (9) |
C7 | 0.0521 (9) | 0.0603 (11) | 0.0655 (12) | −0.0104 (9) | −0.0200 (10) | 0.0016 (10) |
C8 | 0.0433 (8) | 0.0466 (9) | 0.0551 (10) | 0.0007 (7) | −0.0133 (8) | 0.0046 (8) |
C9 | 0.0379 (7) | 0.0376 (7) | 0.0397 (7) | 0.0049 (6) | 0.0004 (7) | 0.0018 (6) |
C10 | 0.0459 (8) | 0.0345 (7) | 0.0425 (8) | −0.0017 (6) | 0.0033 (7) | 0.0029 (6) |
C11 | 0.0349 (7) | 0.0374 (7) | 0.0345 (7) | −0.0031 (6) | −0.0021 (6) | 0.0036 (6) |
C12 | 0.0316 (6) | 0.0384 (7) | 0.0325 (7) | −0.0037 (6) | −0.0013 (6) | 0.0027 (6) |
C13 | 0.0319 (6) | 0.0356 (7) | 0.0367 (7) | −0.0021 (6) | 0.0027 (6) | 0.0049 (6) |
C14 | 0.0316 (6) | 0.0402 (8) | 0.0404 (7) | −0.0004 (6) | 0.0019 (6) | 0.0043 (7) |
C15 | 0.0426 (8) | 0.0431 (8) | 0.0402 (8) | 0.0037 (7) | 0.0030 (7) | 0.0105 (7) |
C16 | 0.0450 (8) | 0.0523 (9) | 0.0370 (8) | 0.0039 (7) | −0.0045 (7) | 0.0054 (7) |
C17 | 0.0617 (11) | 0.0564 (11) | 0.0489 (9) | −0.0015 (9) | −0.0027 (9) | −0.0098 (9) |
C18 | 0.0637 (11) | 0.0522 (11) | 0.0827 (15) | 0.0017 (9) | 0.0251 (12) | −0.0183 (11) |
O1 | 0.0439 (6) | 0.0561 (8) | 0.0696 (9) | −0.0027 (6) | 0.0182 (7) | −0.0100 (7) |
N1 | 0.0450 (7) | 0.0445 (7) | 0.0372 (7) | 0.0026 (6) | 0.0009 (6) | −0.0014 (6) |
Geometric parameters (Å, º) top
C1—C2 | 1.365 (2) | C9—C10 | 1.535 (2) |
C1—C11 | 1.402 (2) | C9—H9 | 0.9800 |
C1—H1 | 0.9300 | C10—C11 | 1.508 (2) |
C2—C3 | 1.394 (3) | C10—H10A | 0.9700 |
C2—H2 | 0.9300 | C10—H10B | 0.9700 |
C3—O1 | 1.371 (2) | C11—C12 | 1.398 (2) |
C3—C4 | 1.392 (2) | C12—C13 | 1.533 (2) |
C4—C12 | 1.398 (2) | C13—C14 | 1.544 (2) |
C4—H4 | 0.9300 | C13—C15 | 1.546 (2) |
C5—C6 | 1.522 (3) | C14—H14 | 0.9800 |
C5—C13 | 1.538 (2) | C15—C16 | 1.519 (2) |
C5—H5A | 0.9700 | C15—H15A | 0.9700 |
C5—H5B | 0.9700 | C15—H15B | 0.9700 |
C6—C7 | 1.519 (3) | C16—N1 | 1.467 (2) |
C6—H6A | 0.9700 | C16—H16A | 0.9700 |
C6—H6B | 0.9700 | C16—H16B | 0.9700 |
C7—C8 | 1.529 (3) | C17—N1 | 1.454 (2) |
C7—H7A | 0.9700 | C17—H17A | 0.9600 |
C7—H7B | 0.9700 | C17—H17B | 0.9600 |
C8—C14 | 1.529 (2) | C17—H17C | 0.9600 |
C8—H8A | 0.9700 | C18—O1 | 1.418 (2) |
C8—H8B | 0.9700 | C18—H18A | 0.9600 |
C9—N1 | 1.468 (2) | C18—H18B | 0.9600 |
C9—C14 | 1.525 (2) | C18—H18C | 0.9600 |
| | | |
C2—C1—C11 | 122.45 (15) | H10A—C10—H10B | 107.6 |
C2—C1—H1 | 118.8 | C12—C11—C1 | 118.46 (15) |
C11—C1—H1 | 118.8 | C12—C11—C10 | 122.29 (14) |
C1—C2—C3 | 119.18 (15) | C1—C11—C10 | 119.25 (14) |
C1—C2—H2 | 120.4 | C11—C12—C4 | 119.17 (14) |
C3—C2—H2 | 120.4 | C11—C12—C13 | 120.66 (14) |
O1—C3—C4 | 124.12 (15) | C4—C12—C13 | 119.94 (14) |
O1—C3—C2 | 116.19 (14) | C12—C13—C5 | 113.29 (13) |
C4—C3—C2 | 119.66 (15) | C12—C13—C14 | 110.08 (12) |
C3—C4—C12 | 121.02 (14) | C5—C13—C14 | 108.54 (12) |
C3—C4—H4 | 119.5 | C12—C13—C15 | 107.79 (12) |
C12—C4—H4 | 119.5 | C5—C13—C15 | 109.93 (13) |
C6—C5—C13 | 112.86 (14) | C14—C13—C15 | 107.03 (13) |
C6—C5—H5A | 109.0 | C9—C14—C8 | 113.78 (13) |
C13—C5—H5A | 109.0 | C9—C14—C13 | 108.88 (12) |
C6—C5—H5B | 109.0 | C8—C14—C13 | 112.64 (13) |
C13—C5—H5B | 109.0 | C9—C14—H14 | 107.1 |
H5A—C5—H5B | 107.8 | C8—C14—H14 | 107.1 |
C7—C6—C5 | 111.24 (17) | C13—C14—H14 | 107.1 |
C7—C6—H6A | 109.4 | C16—C15—C13 | 112.60 (13) |
C5—C6—H6A | 109.4 | C16—C15—H15A | 109.1 |
C7—C6—H6B | 109.4 | C13—C15—H15A | 109.1 |
C5—C6—H6B | 109.4 | C16—C15—H15B | 109.1 |
H6A—C6—H6B | 108.0 | C13—C15—H15B | 109.1 |
C6—C7—C8 | 110.72 (14) | H15A—C15—H15B | 107.8 |
C6—C7—H7A | 109.5 | N1—C16—C15 | 110.70 (13) |
C8—C7—H7A | 109.5 | N1—C16—H16A | 109.5 |
C6—C7—H7B | 109.5 | C15—C16—H16A | 109.5 |
C8—C7—H7B | 109.5 | N1—C16—H16B | 109.5 |
H7A—C7—H7B | 108.1 | C15—C16—H16B | 109.5 |
C14—C8—C7 | 111.43 (15) | H16A—C16—H16B | 108.1 |
C14—C8—H8A | 109.3 | N1—C17—H17A | 109.5 |
C7—C8—H8A | 109.3 | N1—C17—H17B | 109.5 |
C14—C8—H8B | 109.3 | H17A—C17—H17B | 109.5 |
C7—C8—H8B | 109.3 | N1—C17—H17C | 109.5 |
H8A—C8—H8B | 108.0 | H17A—C17—H17C | 109.5 |
N1—C9—C14 | 109.12 (13) | H17B—C17—H17C | 109.5 |
N1—C9—C10 | 116.03 (13) | O1—C18—H18A | 109.5 |
C14—C9—C10 | 109.60 (13) | O1—C18—H18B | 109.5 |
N1—C9—H9 | 107.2 | H18A—C18—H18B | 109.5 |
C14—C9—H9 | 107.2 | O1—C18—H18C | 109.5 |
C10—C9—H9 | 107.2 | H18A—C18—H18C | 109.5 |
C11—C10—C9 | 114.50 (13) | H18B—C18—H18C | 109.5 |
C11—C10—H10A | 108.6 | C3—O1—C18 | 117.59 (14) |
C9—C10—H10A | 108.6 | C17—N1—C16 | 111.13 (14) |
C11—C10—H10B | 108.6 | C17—N1—C9 | 112.70 (14) |
C9—C10—H10B | 108.6 | C16—N1—C9 | 113.60 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O1i | 0.96 | 2.60 | 3.480 (3) | 153 |
Symmetry code: (i) −x+5/2, −y, z+1/2. |