A new polymorph of the title compound {systematic name: 2-[(S)-1-azoniabicyclo[2.2.2]oct-3-yl]-2,3,3a,4,5,6-hexahydro-1H-benz[de]isoquinolin-1-one chloride}, C19H25ON2+·Cl−, an anti-emetic and antinausea agent, has been obtained by crystallization from dimethylformamide. In the orthorhombic polymorph reported here, molecules are arranged into polar (001) layers, with adjacent layers in an antiparallel arrangement, whereas in the earlier reported monoclinic form, adjacent layers are arranged in a parallel manner.
Supporting information
CCDC reference: 640334
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.002 Å
- R factor = 0.028
- wR factor = 0.073
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5 .. CL1 .. 3.00 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A .. CL1 .. 3.00 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13 .. CL1 .. 2.98 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H16A .. CL1 .. 3.00 Ang.
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 24.99
From the CIF: _reflns_number_total 2980
Count of symmetry unique reflns 1743
Completeness (_total/calc) 170.97%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1237
Fraction of Friedel pairs measured 0.710
Are heavy atom types Z>Si present yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C10 = . S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C13 = . S
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
3 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
5 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
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: SHELXTL/PC (Sheldrick, 1990), DIAMOND (Brandenburg & Putz, 2005)
and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
2-[(
S)-1-azoniabicyclo[2.2.2]oct-3-yl]-2,3,3a,4,5,6-hexahydro-1
H-
benz[de]isoquinolin-1-one chloride
top
Crystal data top
C19H25ON2+·Cl− | F(000) = 712 |
Mr = 332.86 | Dx = 1.304 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8390 reflections |
a = 7.4972 (7) Å | θ = 2.4–27.7° |
b = 9.0288 (8) Å | µ = 0.23 mm−1 |
c = 25.045 (2) Å | T = 294 K |
V = 1695.3 (3) Å3 | Needles, colourless |
Z = 4 | 0.17 × 0.13 × 0.07 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2914 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 1.6° |
ω scans | h = −8→8 |
12219 measured reflections | k = −10→10 |
2980 independent reflections | l = −29→29 |
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)] = 0.028 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0386P)2 + 0.2731P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2980 reflections | Δρmax = 0.19 e Å−3 |
212 parameters | Δρmin = −0.12 e Å−3 |
0 restraints | Absolute structure: Flack & Bernardinelli (2000), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.14 (5) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.1060 (2) | 0.60091 (17) | 0.08432 (6) | 0.0373 (3) | |
C2 | −0.1624 (2) | 0.57056 (18) | 0.02805 (6) | 0.0355 (3) | |
C3 | −0.3327 (2) | 0.61272 (19) | 0.01219 (7) | 0.0423 (4) | |
H3 | −0.4073 | 0.6627 | 0.0358 | 0.051* | |
C4 | −0.3903 (2) | 0.5800 (2) | −0.03872 (7) | 0.0453 (4) | |
H4 | −0.5039 | 0.6086 | −0.0495 | 0.054* | |
C5 | −0.2808 (2) | 0.50515 (18) | −0.07368 (6) | 0.0435 (4) | |
H5 | −0.3231 | 0.4809 | −0.1075 | 0.052* | |
C6 | −0.1073 (2) | 0.46498 (18) | −0.05924 (6) | 0.0396 (4) | |
C7 | 0.0101 (3) | 0.3825 (2) | −0.09796 (7) | 0.0510 (5) | |
H7A | −0.0024 | 0.4265 | −0.1331 | 0.061* | |
H7B | −0.0303 | 0.2806 | −0.1002 | 0.061* | |
C8 | 0.2058 (3) | 0.3840 (2) | −0.08219 (7) | 0.0538 (5) | |
H8A | 0.2554 | 0.4817 | −0.0886 | 0.065* | |
H8B | 0.2710 | 0.3134 | −0.1038 | 0.065* | |
C9 | 0.2260 (3) | 0.34429 (19) | −0.02333 (6) | 0.0463 (4) | |
H9A | 0.1723 | 0.2483 | −0.0167 | 0.056* | |
H9B | 0.3516 | 0.3381 | −0.0143 | 0.056* | |
C10 | 0.1361 (2) | 0.46076 (18) | 0.01153 (6) | 0.0375 (4) | |
H10 | 0.2086 | 0.5509 | 0.0098 | 0.045* | |
C11 | 0.1238 (2) | 0.41481 (18) | 0.06975 (6) | 0.0406 (4) | |
H11A | 0.0498 | 0.3271 | 0.0729 | 0.049* | |
H11B | 0.2418 | 0.3908 | 0.0831 | 0.049* | |
C12 | −0.0483 (2) | 0.49938 (17) | −0.00776 (6) | 0.0359 (3) | |
C13 | 0.0831 (2) | 0.54892 (18) | 0.15961 (6) | 0.0362 (4) | |
H13 | −0.0182 | 0.5061 | 0.1789 | 0.043* | |
C14 | 0.2531 (2) | 0.47102 (16) | 0.17879 (6) | 0.0395 (3) | |
H14 | 0.2505 | 0.3663 | 0.1685 | 0.047* | |
C15 | 0.4210 (2) | 0.5453 (2) | 0.15660 (7) | 0.0453 (4) | |
H15A | 0.5261 | 0.4943 | 0.1697 | 0.054* | |
H15B | 0.4210 | 0.5393 | 0.1179 | 0.054* | |
C16 | 0.4261 (3) | 0.7062 (2) | 0.17383 (8) | 0.0511 (5) | |
H16A | 0.5329 | 0.7247 | 0.1947 | 0.061* | |
H16B | 0.4289 | 0.7699 | 0.1426 | 0.061* | |
C17 | 0.0975 (2) | 0.71324 (19) | 0.17526 (7) | 0.0415 (4) | |
H17A | 0.0982 | 0.7740 | 0.1433 | 0.050* | |
H17B | −0.0051 | 0.7412 | 0.1966 | 0.050* | |
C18 | 0.2643 (3) | 0.6481 (2) | 0.25577 (6) | 0.0524 (4) | |
H18A | 0.1615 | 0.6727 | 0.2775 | 0.063* | |
H18B | 0.3712 | 0.6673 | 0.2765 | 0.063* | |
C19 | 0.2573 (3) | 0.48537 (19) | 0.23969 (7) | 0.0508 (4) | |
H19A | 0.1517 | 0.4396 | 0.2548 | 0.061* | |
H19B | 0.3611 | 0.4343 | 0.2537 | 0.061* | |
N1 | 0.04677 (17) | 0.53553 (14) | 0.10178 (5) | 0.0370 (3) | |
N2 | 0.2649 (2) | 0.73983 (15) | 0.20648 (5) | 0.0411 (3) | |
H2N | 0.272 (3) | 0.837 (2) | 0.2147 (7) | 0.050 (5)* | |
O1 | −0.19598 (16) | 0.68199 (15) | 0.11324 (5) | 0.0492 (3) | |
Cl1 | 0.23764 (6) | 1.07041 (4) | 0.224403 (16) | 0.04833 (12) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0320 (8) | 0.0363 (8) | 0.0437 (8) | −0.0014 (7) | 0.0006 (7) | 0.0001 (7) |
C2 | 0.0336 (7) | 0.0326 (8) | 0.0402 (8) | −0.0022 (7) | −0.0034 (6) | 0.0035 (7) |
C3 | 0.0373 (8) | 0.0419 (9) | 0.0477 (9) | 0.0022 (7) | 0.0001 (7) | 0.0067 (7) |
C4 | 0.0367 (8) | 0.0481 (10) | 0.0512 (9) | 0.0003 (8) | −0.0097 (7) | 0.0121 (8) |
C5 | 0.0478 (10) | 0.0439 (8) | 0.0387 (8) | −0.0062 (8) | −0.0104 (8) | 0.0064 (7) |
C6 | 0.0431 (9) | 0.0366 (8) | 0.0392 (8) | −0.0060 (7) | −0.0046 (7) | 0.0049 (7) |
C7 | 0.0532 (11) | 0.0582 (11) | 0.0416 (9) | 0.0003 (9) | −0.0058 (8) | −0.0072 (8) |
C8 | 0.0494 (10) | 0.0670 (11) | 0.0451 (9) | 0.0034 (9) | 0.0024 (8) | −0.0099 (9) |
C9 | 0.0417 (10) | 0.0509 (9) | 0.0464 (9) | 0.0062 (8) | −0.0023 (8) | −0.0085 (7) |
C10 | 0.0342 (8) | 0.0356 (8) | 0.0427 (8) | −0.0003 (7) | −0.0035 (7) | −0.0044 (7) |
C11 | 0.0423 (9) | 0.0359 (8) | 0.0436 (9) | 0.0053 (7) | −0.0077 (7) | −0.0059 (7) |
C12 | 0.0361 (8) | 0.0317 (7) | 0.0398 (8) | −0.0044 (6) | −0.0021 (7) | 0.0033 (6) |
C13 | 0.0374 (8) | 0.0361 (9) | 0.0351 (8) | −0.0017 (7) | 0.0014 (6) | 0.0028 (7) |
C14 | 0.0463 (9) | 0.0318 (7) | 0.0403 (8) | 0.0027 (8) | −0.0053 (8) | 0.0019 (6) |
C15 | 0.0403 (9) | 0.0495 (11) | 0.0462 (9) | 0.0024 (8) | −0.0020 (7) | −0.0076 (8) |
C16 | 0.0464 (10) | 0.0451 (11) | 0.0617 (11) | −0.0062 (8) | 0.0052 (9) | −0.0007 (9) |
C17 | 0.0454 (9) | 0.0388 (9) | 0.0403 (8) | 0.0049 (7) | −0.0081 (7) | −0.0030 (8) |
C18 | 0.0661 (12) | 0.0577 (10) | 0.0335 (8) | 0.0052 (11) | −0.0052 (9) | 0.0006 (7) |
C19 | 0.0614 (11) | 0.0484 (9) | 0.0425 (8) | −0.0016 (10) | −0.0090 (9) | 0.0120 (7) |
N1 | 0.0376 (7) | 0.0372 (7) | 0.0364 (7) | 0.0047 (6) | −0.0048 (6) | −0.0025 (6) |
N2 | 0.0485 (8) | 0.0351 (7) | 0.0396 (7) | −0.0003 (7) | −0.0054 (7) | −0.0037 (5) |
O1 | 0.0407 (7) | 0.0606 (7) | 0.0465 (6) | 0.0092 (6) | 0.0010 (5) | −0.0075 (6) |
Cl1 | 0.0555 (2) | 0.0391 (2) | 0.0504 (2) | −0.0016 (2) | 0.0080 (2) | −0.00779 (16) |
Geometric parameters (Å, º) top
C1—O1 | 1.2313 (19) | C11—H11A | 0.9700 |
C1—N1 | 1.361 (2) | C11—H11B | 0.9700 |
C1—C2 | 1.497 (2) | C13—N1 | 1.4787 (19) |
C2—C3 | 1.390 (2) | C13—C14 | 1.533 (2) |
C2—C12 | 1.397 (2) | C13—C17 | 1.538 (2) |
C3—C4 | 1.378 (3) | C13—H13 | 0.9800 |
C3—H3 | 0.9300 | C14—C15 | 1.531 (2) |
C4—C5 | 1.377 (2) | C14—C19 | 1.531 (2) |
C4—H4 | 0.9300 | C14—H14 | 0.9800 |
C5—C6 | 1.398 (2) | C15—C16 | 1.516 (3) |
C5—H5 | 0.9300 | C15—H15A | 0.9700 |
C6—C12 | 1.398 (2) | C15—H15B | 0.9700 |
C6—C7 | 1.506 (3) | C16—N2 | 1.491 (2) |
C7—C8 | 1.520 (3) | C16—H16A | 0.9700 |
C7—H7A | 0.9700 | C16—H16B | 0.9700 |
C7—H7B | 0.9700 | C17—N2 | 1.498 (2) |
C8—C9 | 1.525 (2) | C17—H17A | 0.9700 |
C8—H8A | 0.9700 | C17—H17B | 0.9700 |
C8—H8B | 0.9700 | C18—N2 | 1.486 (2) |
C9—C10 | 1.524 (2) | C18—C19 | 1.524 (3) |
C9—H9A | 0.9700 | C18—H18A | 0.9700 |
C9—H9B | 0.9700 | C18—H18B | 0.9700 |
C10—C12 | 1.505 (2) | C19—H19A | 0.9700 |
C10—C11 | 1.519 (2) | C19—H19B | 0.9700 |
C10—H10 | 0.9800 | N2—H2N | 0.90 (2) |
C11—N1 | 1.471 (2) | | |
| | | |
O1—C1—N1 | 122.01 (15) | N1—C13—C14 | 114.99 (13) |
O1—C1—C2 | 120.52 (14) | N1—C13—C17 | 109.96 (12) |
N1—C1—C2 | 117.47 (14) | C14—C13—C17 | 107.71 (13) |
C3—C2—C12 | 120.36 (15) | N1—C13—H13 | 108.0 |
C3—C2—C1 | 118.59 (15) | C14—C13—H13 | 108.0 |
C12—C2—C1 | 121.04 (14) | C17—C13—H13 | 108.0 |
C4—C3—C2 | 119.55 (17) | C15—C14—C19 | 107.91 (15) |
C4—C3—H3 | 120.2 | C15—C14—C13 | 111.67 (12) |
C2—C3—H3 | 120.2 | C19—C14—C13 | 106.89 (14) |
C5—C4—C3 | 120.45 (16) | C15—C14—H14 | 110.1 |
C5—C4—H4 | 119.8 | C19—C14—H14 | 110.1 |
C3—C4—H4 | 119.8 | C13—C14—H14 | 110.1 |
C4—C5—C6 | 121.15 (15) | C16—C15—C14 | 109.71 (14) |
C4—C5—H5 | 119.4 | C16—C15—H15A | 109.7 |
C6—C5—H5 | 119.4 | C14—C15—H15A | 109.7 |
C12—C6—C5 | 118.38 (16) | C16—C15—H15B | 109.7 |
C12—C6—C7 | 121.25 (15) | C14—C15—H15B | 109.7 |
C5—C6—C7 | 120.34 (15) | H15A—C15—H15B | 108.2 |
C6—C7—C8 | 113.08 (15) | N2—C16—C15 | 109.31 (15) |
C6—C7—H7A | 109.0 | N2—C16—H16A | 109.8 |
C8—C7—H7A | 109.0 | C15—C16—H16A | 109.8 |
C6—C7—H7B | 109.0 | N2—C16—H16B | 109.8 |
C8—C7—H7B | 109.0 | C15—C16—H16B | 109.8 |
H7A—C7—H7B | 107.8 | H16A—C16—H16B | 108.3 |
C7—C8—C9 | 110.18 (16) | N2—C17—C13 | 110.27 (13) |
C7—C8—H8A | 109.6 | N2—C17—H17A | 109.6 |
C9—C8—H8A | 109.6 | C13—C17—H17A | 109.6 |
C7—C8—H8B | 109.6 | N2—C17—H17B | 109.6 |
C9—C8—H8B | 109.6 | C13—C17—H17B | 109.6 |
H8A—C8—H8B | 108.1 | H17A—C17—H17B | 108.1 |
C10—C9—C8 | 110.34 (14) | N2—C18—C19 | 108.53 (13) |
C10—C9—H9A | 109.6 | N2—C18—H18A | 110.0 |
C8—C9—H9A | 109.6 | C19—C18—H18A | 110.0 |
C10—C9—H9B | 109.6 | N2—C18—H18B | 110.0 |
C8—C9—H9B | 109.6 | C19—C18—H18B | 110.0 |
H9A—C9—H9B | 108.1 | H18A—C18—H18B | 108.4 |
C12—C10—C11 | 108.41 (13) | C18—C19—C14 | 110.20 (13) |
C12—C10—C9 | 112.45 (13) | C18—C19—H19A | 109.6 |
C11—C10—C9 | 112.86 (13) | C14—C19—H19A | 109.6 |
C12—C10—H10 | 107.6 | C18—C19—H19B | 109.6 |
C11—C10—H10 | 107.6 | C14—C19—H19B | 109.6 |
C9—C10—H10 | 107.6 | H19A—C19—H19B | 108.1 |
N1—C11—C10 | 110.18 (13) | C1—N1—C11 | 118.45 (13) |
N1—C11—H11A | 109.6 | C1—N1—C13 | 115.75 (13) |
C10—C11—H11A | 109.6 | C11—N1—C13 | 121.49 (12) |
N1—C11—H11B | 109.6 | C18—N2—C16 | 110.18 (15) |
C10—C11—H11B | 109.6 | C18—N2—C17 | 109.96 (15) |
H11A—C11—H11B | 108.1 | C16—N2—C17 | 111.11 (12) |
C2—C12—C6 | 120.04 (15) | C18—N2—H2N | 110.6 (12) |
C2—C12—C10 | 117.59 (14) | C16—N2—H2N | 105.9 (13) |
C6—C12—C10 | 122.36 (15) | C17—N2—H2N | 109.0 (13) |
| | | |
O1—C1—C2—C3 | −11.6 (2) | C9—C10—C12—C6 | −17.1 (2) |
N1—C1—C2—C3 | 168.30 (14) | N1—C13—C14—C15 | 67.37 (16) |
O1—C1—C2—C12 | 169.42 (16) | C17—C13—C14—C15 | −55.61 (16) |
N1—C1—C2—C12 | −10.7 (2) | N1—C13—C14—C19 | −174.83 (13) |
C12—C2—C3—C4 | 1.9 (2) | C17—C13—C14—C19 | 62.19 (16) |
C1—C2—C3—C4 | −177.13 (16) | C19—C14—C15—C16 | −58.45 (18) |
C2—C3—C4—C5 | 0.4 (3) | C13—C14—C15—C16 | 58.73 (18) |
C3—C4—C5—C6 | −2.1 (3) | C14—C15—C16—N2 | −0.4 (2) |
C4—C5—C6—C12 | 1.5 (2) | N1—C13—C17—N2 | −129.46 (13) |
C4—C5—C6—C7 | 179.68 (16) | C14—C13—C17—N2 | −3.46 (18) |
C12—C6—C7—C8 | −17.4 (2) | N2—C18—C19—C14 | −0.1 (3) |
C5—C6—C7—C8 | 164.55 (17) | C15—C14—C19—C18 | 58.9 (2) |
C6—C7—C8—C9 | 47.5 (2) | C13—C14—C19—C18 | −61.3 (2) |
C7—C8—C9—C10 | −63.6 (2) | O1—C1—N1—C11 | 166.11 (15) |
C8—C9—C10—C12 | 47.19 (19) | C2—C1—N1—C11 | −13.7 (2) |
C8—C9—C10—C11 | 170.21 (14) | O1—C1—N1—C13 | 9.0 (2) |
C12—C10—C11—N1 | −58.46 (17) | C2—C1—N1—C13 | −170.81 (13) |
C9—C10—C11—N1 | 176.30 (14) | C10—C11—N1—C1 | 49.09 (19) |
C3—C2—C12—C6 | −2.5 (2) | C10—C11—N1—C13 | −155.21 (13) |
C1—C2—C12—C6 | 176.53 (14) | C14—C13—N1—C1 | 178.42 (13) |
C3—C2—C12—C10 | 178.26 (14) | C17—C13—N1—C1 | −59.81 (17) |
C1—C2—C12—C10 | −2.7 (2) | C14—C13—N1—C11 | 22.1 (2) |
C5—C6—C12—C2 | 0.8 (2) | C17—C13—N1—C11 | 143.87 (15) |
C7—C6—C12—C2 | −177.36 (16) | C19—C18—N2—C16 | −61.6 (2) |
C5—C6—C12—C10 | 179.99 (14) | C19—C18—N2—C17 | 61.2 (2) |
C7—C6—C12—C10 | 1.9 (2) | C15—C16—N2—C18 | 62.29 (19) |
C11—C10—C12—C2 | 36.68 (19) | C15—C16—N2—C17 | −59.84 (18) |
C9—C10—C12—C2 | 162.16 (14) | C13—C17—N2—C18 | −59.74 (17) |
C11—C10—C12—C6 | −142.57 (15) | C13—C17—N2—C16 | 62.51 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···Cl1 | 0.90 (2) | 2.14 (2) | 3.025 (1) | 168 (2) |
C5—H5···Cl1i | 0.93 | 3.00 | 3.839 (2) | 151 |
C7—H7A···Cl1i | 0.97 | 3.00 | 3.792 (2) | 139 |
C13—H13···Cl1ii | 0.98 | 2.98 | 3.776 (2) | 139 |
C16—H16A···Cl1iii | 0.97 | 3.00 | 3.789 (2) | 139 |
C9—H9A···Cg1iv | 0.97 | 2.89 | 3.672 (2) | 138 |
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2. |