The crystal structures of the p-bromobenzoates of cis-4-oxa-1-decalinyl (C16H19BrO3), trans-4-oxa-1-decalinyl (C16H19BrO3), N-benzyl-cis-4-aza-1-decalinyl (C23H26BrNO2), N-benzyl-trans-4-aza-1-decalinyl (C23H26BrNO2) and trans-4-thia-1-decalinyl (C16H19BrO2S) (decalin is perhydronaphthalene) have been determined as part of a study directed at predicting and interpreting the π-facial selectivities of diastereotopic ketones in reactions with nucleophiles. All five structures are composed of molecules that are separated by normal van der Waals distances. In all five structures, the heterocyclic and cyclohexyl rings adopt chair conformations, and the p-bromobenzoate groups are planar.
Supporting information
CCDC references: 173376; 173377; 173378; 173379; 173380
The cis-ketone (I) was synthesized using the method of Kozikowski & Li
(1985). However, copper(II) trifluoromethanesulfonate was used instead of
zinc(II) trifluoromethanesulfonate for the closure of the heterocyclic ring,
as the latter was found ineffective in our hands. The product was isomerized
to a mixture of cis-(I) and trans-(II) by reflux in EtOH-Et3N.
The trans-ketone (II) was separated from this mixture by chromatography
over silica gel. The trans-ketone (IV) was prepared by following the
literature protocol of Traverso (1955) for the formation of trans-(V)
and isomerized to a mixture of cis-(III) (minor) and trans-(IV)
(major) by treatment with 1,8-diazabicyclo[5.4.0]undec-6-ene (DBU) in
CH2Cl2 at 297 K. The cis-(III) compound was isolated from this
mixture by chromatographic methods. The trans-ketone (V) was fully
resistant to isomerization (DBU/CH2Cl2/297 K) to its cis-analogue.
All the reductions were carried out following standard procedures. The
alcohols (VI), (VIII), (X), (XII) and (XIV) were esterified with
p-bromobenzoyl chloride (p-Br—C6H4COCl) following standard
methods, and the resulting benzoates, (XVI)-(XX), were recrystallized from
benzene, EtOAc/petroleum ether, EtOAc, petroleum ether and
C6H5Cl/petroleum ether, respectively.
In all five structures, most of the H atoms were located from difference maps.
All H atoms were placed at geometrically idealized positions (C—H =
0.93–1.00 Å) and refined utilizing riding models.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (XVI), (XVII), (XVIII); CAD-4 Software (Enraf-Nonius, 1989) for (XIX), (XX). Cell refinement: MSC/AFC Diffractometer Control Software for (XVI), (XVII), (XVIII); CAD-4 Software for (XIX), (XX). For all compounds, data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
(XVI)
cis-4-oxa-1-decalinyl
p-bromobenzoate
top
Crystal data top
C16H19BrO3 | F(000) = 696 |
Mr = 339.22 | Dx = 1.500 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 10.906 (2) Å | Cell parameters from 12 reflections |
b = 8.052 (4) Å | θ = 10–20° |
c = 17.195 (3) Å | µ = 2.74 mm−1 |
β = 95.98 (2)° | T = 170 K |
V = 1501.8 (8) Å3 | Prismatic, colourless |
Z = 4 | 0.48 × 0.42 × 0.33 mm |
Data collection top
Rigaku AFC-6S diffractometer | 693 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.08 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = 0→12 |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | k = 0→9 |
Tmin = 0.28, Tmax = 0.41 | l = −20→20 |
2646 measured reflections | 3 standard reflections every 200 reflections |
2646 independent reflections | intensity decay: < 1.1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2)] |
S = 0.94 | (Δ/σ)max < 0.001 |
2646 reflections | Δρmax = 0.53 e Å−3 |
182 parameters | Δρmin = −0.77 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00061 (16) |
Crystal data top
C16H19BrO3 | V = 1501.8 (8) Å3 |
Mr = 339.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.906 (2) Å | µ = 2.74 mm−1 |
b = 8.052 (4) Å | T = 170 K |
c = 17.195 (3) Å | 0.48 × 0.42 × 0.33 mm |
β = 95.98 (2)° | |
Data collection top
Rigaku AFC-6S diffractometer | 693 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.08 |
Tmin = 0.28, Tmax = 0.41 | 3 standard reflections every 200 reflections |
2646 measured reflections | intensity decay: < 1.1% |
2646 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.53 e Å−3 |
2646 reflections | Δρmin = −0.77 e Å−3 |
182 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 1.25240 (10) | 0.68612 (17) | 0.45505 (6) | 0.0543 (4) | |
O1 | 0.4194 (6) | 0.8678 (8) | 0.7348 (4) | 0.034 (2) | |
O2 | 0.7075 (4) | 0.8592 (7) | 0.5949 (3) | 0.0336 (19) | |
O3 | 0.6305 (5) | 0.8035 (11) | 0.4705 (3) | 0.052 (2) | |
C1 | 0.4739 (8) | 1.0231 (12) | 0.7195 (5) | 0.035 (3) | |
H1A | 0.4839 | 1.0896 | 0.7682 | 0.042* | |
H1B | 0.4186 | 1.0849 | 0.6804 | 0.042* | |
C2 | 0.5994 (8) | 1.0001 (12) | 0.6891 (5) | 0.032 (3) | |
H2A | 0.6325 | 1.1091 | 0.6748 | 0.038* | |
H2B | 0.6581 | 0.9497 | 0.7302 | 0.038* | |
C3 | 0.5842 (7) | 0.8877 (12) | 0.6178 (5) | 0.027 (3) | |
H3 | 0.5340 | 0.9471 | 0.5744 | 0.032* | |
C4 | 0.5209 (7) | 0.7262 (10) | 0.6336 (5) | 0.019 (2) | |
H4 | 0.5020 | 0.6674 | 0.5826 | 0.022* | |
C5 | 0.6007 (8) | 0.6103 (12) | 0.6887 (6) | 0.037 (3) | |
H5A | 0.6764 | 0.5807 | 0.6648 | 0.044* | |
H5B | 0.6255 | 0.6685 | 0.7386 | 0.044* | |
C6 | 0.5303 (9) | 0.4530 (12) | 0.7048 (5) | 0.042 (3) | |
H6A | 0.5826 | 0.3817 | 0.7416 | 0.051* | |
H6B | 0.5114 | 0.3906 | 0.6554 | 0.051* | |
C7 | 0.4101 (9) | 0.4927 (12) | 0.7396 (6) | 0.042 (3) | |
H7A | 0.4290 | 0.5456 | 0.7915 | 0.050* | |
H7B | 0.3644 | 0.3886 | 0.7469 | 0.050* | |
C8 | 0.3300 (8) | 0.6100 (12) | 0.6852 (5) | 0.035 (3) | |
H8A | 0.3022 | 0.5503 | 0.6362 | 0.042* | |
H8B | 0.2558 | 0.6409 | 0.7106 | 0.042* | |
C9 | 0.3976 (7) | 0.7690 (11) | 0.6650 (6) | 0.035 (3) | |
H9 | 0.3447 | 0.8329 | 0.6244 | 0.042* | |
C10 | 0.7178 (8) | 0.8213 (15) | 0.5210 (5) | 0.036 (3) | |
C11 | 0.8490 (7) | 0.7872 (13) | 0.5057 (5) | 0.026 (3) | |
C12 | 0.9439 (7) | 0.8096 (13) | 0.5648 (5) | 0.036 (3) | |
H12 | 0.9267 | 0.8426 | 0.6155 | 0.043* | |
C13 | 1.0652 (8) | 0.7831 (12) | 0.5487 (5) | 0.043 (3) | |
H13 | 1.1317 | 0.8065 | 0.5874 | 0.052* | |
C14 | 1.0881 (8) | 0.7237 (13) | 0.4774 (5) | 0.034 (3) | |
C15 | 0.9931 (8) | 0.7037 (13) | 0.4177 (5) | 0.038 (3) | |
H15 | 1.0100 | 0.6692 | 0.3671 | 0.045* | |
C16 | 0.8733 (8) | 0.7350 (11) | 0.4335 (5) | 0.041 (3) | |
H16 | 0.8074 | 0.7200 | 0.3935 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0407 (6) | 0.0746 (9) | 0.0506 (7) | 0.0074 (10) | 0.0188 (5) | −0.0010 (11) |
O1 | 0.036 (4) | 0.030 (6) | 0.035 (5) | 0.003 (4) | 0.004 (4) | −0.006 (4) |
O2 | 0.016 (3) | 0.046 (6) | 0.040 (4) | 0.003 (3) | 0.006 (3) | 0.000 (4) |
O3 | 0.033 (4) | 0.080 (6) | 0.039 (4) | −0.004 (5) | −0.009 (3) | −0.004 (6) |
C1 | 0.033 (6) | 0.034 (8) | 0.037 (7) | 0.003 (6) | 0.003 (5) | 0.001 (6) |
C2 | 0.035 (7) | 0.029 (7) | 0.031 (7) | −0.005 (6) | 0.002 (6) | 0.004 (6) |
C3 | 0.016 (5) | 0.031 (7) | 0.034 (6) | 0.009 (5) | 0.003 (5) | 0.005 (6) |
C4 | 0.020 (5) | 0.013 (7) | 0.022 (5) | −0.002 (5) | −0.001 (4) | −0.012 (5) |
C5 | 0.020 (6) | 0.032 (8) | 0.057 (8) | 0.004 (6) | 0.001 (6) | 0.021 (7) |
C6 | 0.055 (7) | 0.031 (8) | 0.042 (7) | 0.014 (7) | 0.008 (6) | 0.009 (6) |
C7 | 0.048 (8) | 0.035 (8) | 0.045 (8) | −0.008 (7) | 0.016 (6) | −0.005 (7) |
C8 | 0.031 (6) | 0.032 (7) | 0.041 (7) | −0.003 (6) | 0.000 (5) | −0.005 (6) |
C9 | 0.019 (5) | 0.030 (8) | 0.056 (7) | 0.002 (5) | −0.001 (5) | 0.006 (6) |
C10 | 0.043 (7) | 0.037 (7) | 0.032 (6) | −0.015 (7) | 0.019 (5) | −0.013 (7) |
C11 | 0.029 (5) | 0.028 (7) | 0.021 (5) | 0.004 (6) | 0.004 (4) | 0.011 (6) |
C12 | 0.027 (5) | 0.054 (7) | 0.028 (5) | 0.012 (7) | 0.006 (4) | 0.006 (7) |
C13 | 0.036 (6) | 0.058 (9) | 0.034 (6) | −0.002 (6) | 0.000 (5) | 0.008 (7) |
C14 | 0.035 (6) | 0.043 (9) | 0.028 (6) | 0.006 (6) | 0.014 (5) | 0.005 (6) |
C15 | 0.039 (6) | 0.048 (8) | 0.027 (6) | 0.009 (7) | 0.010 (5) | 0.006 (7) |
C16 | 0.037 (6) | 0.049 (10) | 0.038 (6) | −0.008 (6) | 0.001 (5) | −0.025 (6) |
Geometric parameters (Å, º) top
Br1—C14 | 1.895 (8) | C6—H6A | 0.9900 |
O1—C1 | 1.421 (9) | C6—H6B | 0.9900 |
O1—C9 | 1.439 (10) | C7—C8 | 1.537 (12) |
O2—C10 | 1.324 (9) | C7—H7A | 0.9900 |
O2—C3 | 1.458 (7) | C7—H7B | 0.9900 |
O3—C10 | 1.228 (9) | C8—C9 | 1.535 (10) |
C1—C2 | 1.527 (10) | C8—H8A | 0.9900 |
C1—H1A | 0.9900 | C8—H8B | 0.9900 |
C1—H1B | 0.9900 | C9—H9 | 1.0000 |
C2—C3 | 1.519 (11) | C10—C11 | 1.507 (10) |
C2—H2A | 0.9900 | C11—C16 | 1.363 (10) |
C2—H2B | 0.9900 | C11—C12 | 1.385 (10) |
C3—C4 | 1.510 (10) | C12—C13 | 1.396 (9) |
C3—H3 | 1.0000 | C12—H12 | 0.9500 |
C4—C5 | 1.534 (10) | C13—C14 | 1.364 (10) |
C4—C9 | 1.539 (9) | C13—H13 | 0.9500 |
C4—H4 | 1.0000 | C14—C15 | 1.389 (10) |
C5—C6 | 1.521 (11) | C15—C16 | 1.385 (9) |
C5—H5A | 0.9900 | C15—H15 | 0.9500 |
C5—H5B | 0.9900 | C16—H16 | 0.9500 |
C6—C7 | 1.531 (11) | | |
| | | |
C1—O1—C9 | 111.6 (7) | C6—C7—H7A | 109.6 |
C10—O2—C3 | 117.9 (7) | C8—C7—H7A | 109.6 |
O1—C1—C2 | 111.3 (8) | C6—C7—H7B | 109.6 |
O1—C1—H1A | 109.4 | C8—C7—H7B | 109.6 |
C2—C1—H1A | 109.4 | H7A—C7—H7B | 108.1 |
O1—C1—H1B | 109.4 | C9—C8—C7 | 113.3 (8) |
C2—C1—H1B | 109.4 | C9—C8—H8A | 108.9 |
H1A—C1—H1B | 108.0 | C7—C8—H8A | 108.9 |
C3—C2—C1 | 108.8 (7) | C9—C8—H8B | 108.9 |
C3—C2—H2A | 109.9 | C7—C8—H8B | 108.9 |
C1—C2—H2A | 109.9 | H8A—C8—H8B | 107.7 |
C3—C2—H2B | 109.9 | O1—C9—C8 | 108.3 (7) |
C1—C2—H2B | 109.9 | O1—C9—C4 | 109.9 (7) |
H2A—C2—H2B | 108.3 | C8—C9—C4 | 110.5 (7) |
O2—C3—C4 | 111.4 (7) | O1—C9—H9 | 109.4 |
O2—C3—C2 | 106.5 (7) | C8—C9—H9 | 109.4 |
C4—C3—C2 | 112.4 (7) | C4—C9—H9 | 109.4 |
O2—C3—H3 | 108.8 | O3—C10—O2 | 124.6 (8) |
C4—C3—H3 | 108.8 | O3—C10—C11 | 122.4 (8) |
C2—C3—H3 | 108.8 | O2—C10—C11 | 112.8 (8) |
C3—C4—C5 | 113.2 (7) | C16—C11—C12 | 120.5 (8) |
C3—C4—C9 | 107.7 (7) | C16—C11—C10 | 119.6 (8) |
C5—C4—C9 | 112.3 (7) | C12—C11—C10 | 119.9 (8) |
C3—C4—H4 | 107.8 | C11—C12—C13 | 119.1 (8) |
C5—C4—H4 | 107.8 | C11—C12—H12 | 120.4 |
C9—C4—H4 | 107.8 | C13—C12—H12 | 120.4 |
C6—C5—C4 | 110.7 (8) | C14—C13—C12 | 119.8 (8) |
C6—C5—H5A | 109.5 | C14—C13—H13 | 120.1 |
C4—C5—H5A | 109.5 | C12—C13—H13 | 120.1 |
C6—C5—H5B | 109.5 | C13—C14—C15 | 120.8 (8) |
C4—C5—H5B | 109.5 | C13—C14—Br1 | 120.2 (7) |
H5A—C5—H5B | 108.1 | C15—C14—Br1 | 118.7 (6) |
C5—C6—C7 | 111.5 (8) | C16—C15—C14 | 118.7 (8) |
C5—C6—H6A | 109.3 | C16—C15—H15 | 120.6 |
C7—C6—H6A | 109.3 | C14—C15—H15 | 120.6 |
C5—C6—H6B | 109.3 | C11—C16—C15 | 120.8 (9) |
C7—C6—H6B | 109.3 | C11—C16—H16 | 119.6 |
H6A—C6—H6B | 108.0 | C15—C16—H16 | 119.6 |
C6—C7—C8 | 110.2 (8) | | |
| | | |
C9—O1—C1—C2 | −61.7 (10) | C5—C4—C9—O1 | 66.8 (9) |
O1—C1—C2—C3 | 55.0 (10) | C3—C4—C9—C8 | −178.0 (8) |
C10—O2—C3—C4 | 82.3 (10) | C5—C4—C9—C8 | −52.7 (11) |
C10—O2—C3—C2 | −154.8 (9) | C3—O2—C10—O3 | −2.2 (17) |
C1—C2—C3—O2 | −175.6 (7) | C3—O2—C10—C11 | −177.3 (8) |
C1—C2—C3—C4 | −53.3 (10) | O3—C10—C11—C16 | 0.2 (17) |
O2—C3—C4—C5 | 49.7 (10) | O2—C10—C11—C16 | 175.4 (9) |
C2—C3—C4—C5 | −69.8 (9) | O3—C10—C11—C12 | 179.9 (12) |
O2—C3—C4—C9 | 174.5 (7) | O2—C10—C11—C12 | −4.9 (15) |
C2—C3—C4—C9 | 55.0 (10) | C16—C11—C12—C13 | 2.0 (16) |
C3—C4—C5—C6 | 177.9 (7) | C10—C11—C12—C13 | −177.7 (10) |
C9—C4—C5—C6 | 55.7 (10) | C11—C12—C13—C14 | −5.0 (16) |
C4—C5—C6—C7 | −57.4 (11) | C12—C13—C14—C15 | 6.1 (16) |
C5—C6—C7—C8 | 56.4 (11) | C12—C13—C14—Br1 | −179.6 (8) |
C6—C7—C8—C9 | −54.4 (11) | C13—C14—C15—C16 | −4.1 (16) |
C1—O1—C9—C8 | −175.7 (7) | Br1—C14—C15—C16 | −178.5 (7) |
C1—O1—C9—C4 | 63.5 (9) | C12—C11—C16—C15 | −0.1 (16) |
C7—C8—C9—O1 | −68.0 (9) | C10—C11—C16—C15 | 179.6 (10) |
C7—C8—C9—C4 | 52.4 (11) | C14—C15—C16—C11 | 1.1 (16) |
C3—C4—C9—O1 | −58.6 (9) | | |
(XVII)
trans-4-oxa-1-decalinyl
p-bromobenzoate
top
Crystal data top
C16H19BrO3 | Z = 2 |
Mr = 339.22 | F(000) = 348 |
Triclinic, P1 | Dx = 1.485 Mg m−3 |
a = 9.643 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 10.679 (2) Å | Cell parameters from 25 reflections |
c = 8.772 (2) Å | θ = 10–15° |
α = 96.32 (2)° | µ = 2.71 mm−1 |
β = 111.32 (2)° | T = 293 K |
γ = 110.49 (2)° | Plate, colourless |
V = 758.5 (3) Å3 | 0.60 × 0.40 × 0.15 mm |
Data collection top
Rigaku AFC-6S diffractometer | 1169 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.03 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = 0→11 |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | k = −12→11 |
Tmin = 0.28, Tmax = 0.67 | l = −10→9 |
2702 measured reflections | 3 standard reflections every 200 reflections |
2702 independent reflections | intensity decay: < 0.8% |
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)] = 0.039 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0513P)2] where P = (Fo2 + 2Fc2)/3 |
2702 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
Crystal data top
C16H19BrO3 | γ = 110.49 (2)° |
Mr = 339.22 | V = 758.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.643 (2) Å | Mo Kα radiation |
b = 10.679 (2) Å | µ = 2.71 mm−1 |
c = 8.772 (2) Å | T = 293 K |
α = 96.32 (2)° | 0.60 × 0.40 × 0.15 mm |
β = 111.32 (2)° | |
Data collection top
Rigaku AFC-6S diffractometer | 1169 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.03 |
Tmin = 0.28, Tmax = 0.67 | 3 standard reflections every 200 reflections |
2702 measured reflections | intensity decay: < 0.8% |
2702 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.42 e Å−3 |
2702 reflections | Δρmin = −0.38 e Å−3 |
181 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.62706 (9) | 1.28442 (7) | 0.24217 (9) | 0.0785 (3) | |
O1 | −0.0142 (4) | 0.1901 (4) | 0.1044 (5) | 0.0590 (10) | |
O2 | 0.2942 (4) | 0.6079 (4) | 0.2383 (5) | 0.0635 (11) | |
O3 | 0.5457 (5) | 0.6687 (4) | 0.4412 (5) | 0.0817 (14) | |
C1 | 0.0561 (7) | 0.2611 (6) | 0.2776 (7) | 0.0618 (16) | |
H1A | 0.1439 | 0.2365 | 0.3410 | 0.074* | |
H1B | −0.0263 | 0.2323 | 0.3206 | 0.074* | |
C2 | 0.1241 (7) | 0.4177 (6) | 0.3055 (7) | 0.0669 (17) | |
H2A | 0.1763 | 0.4638 | 0.4262 | 0.080* | |
H2B | 0.0354 | 0.4440 | 0.2505 | 0.080* | |
C3 | 0.2466 (6) | 0.4616 (5) | 0.2328 (7) | 0.0526 (15) | |
H3 | 0.3433 | 0.4465 | 0.2980 | 0.063* | |
C4 | 0.1697 (7) | 0.3806 (5) | 0.0479 (7) | 0.0545 (15) | |
H4 | 0.0761 | 0.4013 | −0.0121 | 0.065* | |
C5 | 0.2765 (8) | 0.4151 (7) | −0.0409 (9) | 0.083 (2) | |
H5A | 0.3736 | 0.4004 | 0.0188 | 0.099* | |
H5B | 0.3117 | 0.5127 | −0.0380 | 0.099* | |
C6 | 0.1901 (9) | 0.3276 (8) | −0.2258 (9) | 0.091 (2) | |
H6A | 0.1014 | 0.3510 | −0.2899 | 0.109* | |
H6B | 0.2672 | 0.3481 | −0.2761 | 0.109* | |
C7 | 0.1229 (9) | 0.1762 (8) | −0.2353 (9) | 0.088 (2) | |
H7A | 0.2134 | 0.1511 | −0.1837 | 0.105* | |
H7B | 0.0619 | 0.1228 | −0.3537 | 0.105* | |
C8 | 0.0128 (8) | 0.1386 (6) | −0.1477 (8) | 0.0769 (18) | |
H8A | −0.0215 | 0.0411 | −0.1507 | 0.092* | |
H8B | −0.0846 | 0.1531 | −0.2070 | 0.092* | |
C9 | 0.1009 (7) | 0.2262 (5) | 0.0354 (7) | 0.0565 (15) | |
H9 | 0.1913 | 0.2026 | 0.0979 | 0.068* | |
C10 | 0.4493 (7) | 0.6999 (6) | 0.3404 (7) | 0.0511 (14) | |
C11 | 0.4874 (6) | 0.8392 (5) | 0.3144 (6) | 0.0418 (13) | |
C12 | 0.3821 (6) | 0.8653 (5) | 0.1799 (6) | 0.0486 (14) | |
H12 | 0.2823 | 0.7935 | 0.1035 | 0.058* | |
C13 | 0.4238 (7) | 0.9973 (6) | 0.1577 (7) | 0.0579 (16) | |
H13 | 0.3526 | 1.0138 | 0.0659 | 0.070* | |
C14 | 0.5702 (7) | 1.1043 (5) | 0.2710 (7) | 0.0487 (14) | |
C15 | 0.6768 (7) | 1.0807 (6) | 0.4077 (7) | 0.0558 (15) | |
H15 | 0.7752 | 1.1533 | 0.4854 | 0.067* | |
C16 | 0.6356 (6) | 0.9484 (6) | 0.4274 (7) | 0.0528 (15) | |
H16 | 0.7081 | 0.9317 | 0.5179 | 0.063* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0961 (6) | 0.0456 (4) | 0.0837 (5) | 0.0225 (4) | 0.0340 (4) | 0.0227 (3) |
O1 | 0.052 (3) | 0.048 (2) | 0.052 (2) | 0.0060 (19) | 0.011 (2) | 0.0137 (19) |
O2 | 0.047 (3) | 0.040 (2) | 0.075 (3) | 0.009 (2) | 0.005 (2) | 0.014 (2) |
O3 | 0.059 (3) | 0.057 (3) | 0.088 (3) | 0.011 (2) | −0.002 (2) | 0.031 (2) |
C1 | 0.054 (4) | 0.059 (4) | 0.060 (4) | 0.009 (3) | 0.025 (3) | 0.018 (3) |
C2 | 0.071 (4) | 0.063 (4) | 0.054 (4) | 0.018 (3) | 0.024 (3) | 0.010 (3) |
C3 | 0.049 (4) | 0.032 (3) | 0.057 (4) | 0.011 (3) | 0.007 (3) | 0.014 (3) |
C4 | 0.053 (4) | 0.047 (3) | 0.061 (4) | 0.014 (3) | 0.028 (3) | 0.018 (3) |
C5 | 0.074 (5) | 0.078 (5) | 0.108 (6) | 0.028 (4) | 0.049 (5) | 0.044 (5) |
C6 | 0.113 (6) | 0.100 (6) | 0.078 (5) | 0.042 (5) | 0.059 (5) | 0.034 (5) |
C7 | 0.112 (6) | 0.083 (5) | 0.081 (5) | 0.046 (5) | 0.051 (5) | 0.020 (4) |
C8 | 0.097 (5) | 0.059 (4) | 0.079 (5) | 0.031 (4) | 0.044 (4) | 0.022 (4) |
C9 | 0.073 (4) | 0.045 (3) | 0.049 (3) | 0.025 (3) | 0.023 (3) | 0.014 (3) |
C10 | 0.048 (4) | 0.049 (4) | 0.049 (3) | 0.015 (3) | 0.018 (3) | 0.013 (3) |
C11 | 0.039 (3) | 0.043 (3) | 0.044 (3) | 0.018 (3) | 0.018 (3) | 0.016 (3) |
C12 | 0.044 (3) | 0.041 (3) | 0.044 (3) | 0.009 (3) | 0.014 (3) | 0.004 (3) |
C13 | 0.063 (4) | 0.053 (4) | 0.050 (4) | 0.026 (3) | 0.013 (3) | 0.019 (3) |
C14 | 0.052 (4) | 0.039 (3) | 0.052 (3) | 0.016 (3) | 0.023 (3) | 0.011 (3) |
C15 | 0.045 (4) | 0.044 (3) | 0.055 (4) | 0.005 (3) | 0.013 (3) | 0.005 (3) |
C16 | 0.041 (4) | 0.052 (4) | 0.051 (3) | 0.013 (3) | 0.011 (3) | 0.014 (3) |
Geometric parameters (Å, º) top
Br1—C14 | 1.880 (5) | C6—H6A | 0.9700 |
O1—C9 | 1.410 (6) | C6—H6B | 0.9700 |
O1—C1 | 1.407 (6) | C7—C8 | 1.497 (8) |
O2—C10 | 1.344 (6) | C7—H7A | 0.9700 |
O2—C3 | 1.456 (6) | C7—H7B | 0.9700 |
O3—C10 | 1.200 (6) | C8—C9 | 1.516 (8) |
C1—C2 | 1.520 (7) | C8—H8A | 0.9700 |
C1—H1A | 0.9700 | C8—H8B | 0.9700 |
C1—H1B | 0.9700 | C9—H9 | 0.9800 |
C2—C3 | 1.500 (7) | C10—C11 | 1.468 (7) |
C2—H2A | 0.9700 | C11—C12 | 1.378 (7) |
C2—H2B | 0.9700 | C11—C16 | 1.390 (7) |
C3—C4 | 1.516 (7) | C12—C13 | 1.381 (7) |
C3—H3 | 0.9800 | C12—H12 | 0.9300 |
C4—C5 | 1.477 (7) | C13—C14 | 1.373 (7) |
C4—C9 | 1.521 (7) | C13—H13 | 0.9300 |
C4—H4 | 0.9800 | C14—C15 | 1.382 (7) |
C5—C6 | 1.529 (9) | C15—C16 | 1.377 (7) |
C5—H5A | 0.9700 | C15—H15 | 0.9300 |
C5—H5B | 0.9700 | C16—H16 | 0.9300 |
C6—C7 | 1.497 (9) | | |
| | | |
C9—O1—C1 | 111.9 (4) | C6—C7—H7A | 109.1 |
C10—O2—C3 | 119.2 (4) | C8—C7—H7A | 109.1 |
O1—C1—C2 | 111.7 (4) | C6—C7—H7B | 109.1 |
O1—C1—H1A | 109.3 | C8—C7—H7B | 109.1 |
C2—C1—H1A | 109.3 | H7A—C7—H7B | 107.8 |
O1—C1—H1B | 109.3 | C7—C8—C9 | 110.6 (6) |
C2—C1—H1B | 109.3 | C7—C8—H8A | 109.5 |
H1A—C1—H1B | 107.9 | C9—C8—H8A | 109.5 |
C1—C2—C3 | 109.3 (5) | C7—C8—H8B | 109.5 |
C1—C2—H2A | 109.8 | C9—C8—H8B | 109.5 |
C3—C2—H2A | 109.8 | H8A—C8—H8B | 108.1 |
C1—C2—H2B | 109.8 | O1—C9—C8 | 106.7 (5) |
C3—C2—H2B | 109.8 | O1—C9—C4 | 111.4 (4) |
H2A—C2—H2B | 108.3 | C8—C9—C4 | 111.7 (4) |
O2—C3—C2 | 109.1 (5) | O1—C9—H9 | 109.0 |
O2—C3—C4 | 107.3 (4) | C8—C9—H9 | 109.0 |
C2—C3—C4 | 110.1 (4) | C4—C9—H9 | 109.0 |
O2—C3—H3 | 110.1 | O3—C10—O2 | 122.3 (5) |
C2—C3—H3 | 110.1 | O3—C10—C11 | 124.3 (5) |
C4—C3—H3 | 110.1 | O2—C10—C11 | 113.4 (5) |
C5—C4—C9 | 111.1 (5) | C12—C11—C16 | 118.7 (5) |
C5—C4—C3 | 115.9 (5) | C12—C11—C10 | 122.2 (5) |
C9—C4—C3 | 108.7 (4) | C16—C11—C10 | 119.1 (4) |
C5—C4—H4 | 106.9 | C11—C12—C13 | 120.5 (5) |
C9—C4—H4 | 106.9 | C11—C12—H12 | 119.8 |
C3—C4—H4 | 106.9 | C13—C12—H12 | 119.8 |
C4—C5—C6 | 112.4 (5) | C14—C13—C12 | 120.1 (5) |
C4—C5—H5A | 109.1 | C14—C13—H13 | 119.9 |
C6—C5—H5A | 109.1 | C12—C13—H13 | 119.9 |
C4—C5—H5B | 109.1 | C13—C14—C15 | 120.3 (5) |
C6—C5—H5B | 109.1 | C13—C14—Br1 | 120.3 (4) |
H5A—C5—H5B | 107.9 | C15—C14—Br1 | 119.3 (4) |
C7—C6—C5 | 110.4 (5) | C16—C15—C14 | 119.2 (5) |
C7—C6—H6A | 109.6 | C16—C15—H15 | 120.4 |
C5—C6—H6A | 109.6 | C14—C15—H15 | 120.4 |
C7—C6—H6B | 109.6 | C15—C16—C11 | 121.1 (5) |
C5—C6—H6B | 109.6 | C15—C16—H16 | 119.4 |
H6A—C6—H6B | 108.1 | C11—C16—H16 | 119.4 |
C6—C7—C8 | 112.7 (6) | | |
| | | |
C9—O1—C1—C2 | 59.9 (6) | C3—C4—C9—O1 | 57.4 (6) |
O1—C1—C2—C3 | −56.7 (6) | C5—C4—C9—C8 | −54.7 (7) |
C10—O2—C3—C2 | 113.6 (5) | C3—C4—C9—C8 | 176.6 (5) |
C10—O2—C3—C4 | −127.1 (5) | C3—O2—C10—O3 | −8.3 (8) |
C1—C2—C3—O2 | 172.1 (4) | C3—O2—C10—C11 | 171.2 (4) |
C1—C2—C3—C4 | 54.6 (6) | O3—C10—C11—C12 | 169.5 (5) |
O2—C3—C4—C5 | 60.4 (6) | O2—C10—C11—C12 | −9.9 (7) |
C2—C3—C4—C5 | 179.1 (5) | O3—C10—C11—C16 | −9.4 (8) |
O2—C3—C4—C9 | −173.6 (4) | O2—C10—C11—C16 | 171.1 (5) |
C2—C3—C4—C9 | −55.0 (6) | C16—C11—C12—C13 | 0.3 (8) |
C9—C4—C5—C6 | 54.6 (7) | C10—C11—C12—C13 | −178.7 (5) |
C3—C4—C5—C6 | 179.3 (5) | C11—C12—C13—C14 | −0.7 (8) |
C4—C5—C6—C7 | −54.5 (8) | C12—C13—C14—C15 | 0.1 (8) |
C5—C6—C7—C8 | 54.7 (8) | C12—C13—C14—Br1 | −179.7 (4) |
C6—C7—C8—C9 | −55.4 (8) | C13—C14—C15—C16 | 0.9 (8) |
C1—O1—C9—C8 | 177.4 (5) | Br1—C14—C15—C16 | −179.3 (4) |
C1—O1—C9—C4 | −60.5 (6) | C14—C15—C16—C11 | −1.3 (8) |
C7—C8—C9—O1 | 176.4 (5) | C12—C11—C16—C15 | 0.7 (8) |
C7—C8—C9—C4 | 54.5 (7) | C10—C11—C16—C15 | 179.7 (5) |
C5—C4—C9—O1 | −173.9 (5) | | |
(XVIII)
N-benzyl-
cis-4-aza-1-decalinyl
p-bromobenzoate
top
Crystal data top
C23H26BrNO2 | Z = 2 |
Mr = 428.36 | F(000) = 444 |
Triclinic, P1 | Dx = 1.409 Mg m−3 |
a = 11.914 (3) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 13.144 (3) Å | Cell parameters from 12 reflections |
c = 6.922 (2) Å | θ = 10–15° |
α = 96.06 (2)° | µ = 2.05 mm−1 |
β = 106.22 (2)° | T = 170 K |
γ = 100.42 (3)° | Prismatic, colourless |
V = 1009.6 (5) Å3 | 0.60 × 0.40 × 0.32 mm |
Data collection top
Rigaku AFC-6S diffractometer | 1407 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.09 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = 0→14 |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | k = −15→15 |
Tmin = 0.39, Tmax = 0.52 | l = −8→7 |
3574 measured reflections | 3 standard reflections every 200 reflections |
3574 independent reflections | intensity decay: <1.1% |
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)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.018P)2] where P = (Fo2 + 2Fc2)/3 |
3574 reflections | (Δ/σ)max < 0.001 |
244 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.76 e Å−3 |
Crystal data top
C23H26BrNO2 | γ = 100.42 (3)° |
Mr = 428.36 | V = 1009.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.914 (3) Å | Mo Kα radiation |
b = 13.144 (3) Å | µ = 2.05 mm−1 |
c = 6.922 (2) Å | T = 170 K |
α = 96.06 (2)° | 0.60 × 0.40 × 0.32 mm |
β = 106.22 (2)° | |
Data collection top
Rigaku AFC-6S diffractometer | 1407 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.09 |
Tmin = 0.39, Tmax = 0.52 | 3 standard reflections every 200 reflections |
3574 measured reflections | intensity decay: <1.1% |
3574 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.43 e Å−3 |
3574 reflections | Δρmin = −0.76 e Å−3 |
244 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.42113 (7) | 0.14473 (6) | 0.24555 (11) | 0.0465 (2) | |
O1 | 0.6728 (3) | 0.4668 (3) | −0.2993 (6) | 0.0341 (11) | |
O2 | 0.7113 (4) | 0.3176 (3) | −0.4277 (6) | 0.0430 (12) | |
N1 | 0.8553 (4) | 0.7240 (3) | −0.4752 (6) | 0.0246 (12) | |
C1 | 0.7295 (5) | 0.6837 (4) | −0.5911 (9) | 0.0348 (16) | |
H1A | 0.7232 | 0.6443 | −0.7251 | 0.042* | |
H1B | 0.6894 | 0.7429 | −0.6155 | 0.042* | |
C2 | 0.6676 (5) | 0.6120 (4) | −0.4755 (9) | 0.0338 (16) | |
H2A | 0.6676 | 0.6529 | −0.3469 | 0.041* | |
H2B | 0.5832 | 0.5826 | −0.5587 | 0.041* | |
C3 | 0.7303 (5) | 0.5240 (4) | −0.4280 (9) | 0.0304 (16) | |
H3 | 0.7191 | 0.4763 | −0.5576 | 0.036* | |
C4 | 0.8648 (5) | 0.5656 (4) | −0.3186 (8) | 0.0279 (15) | |
H4 | 0.9037 | 0.5042 | −0.3122 | 0.034* | |
C5 | 0.8946 (5) | 0.6231 (4) | −0.1002 (8) | 0.0323 (16) | |
H5A | 0.8563 | 0.6840 | −0.1017 | 0.039* | |
H5B | 0.8620 | 0.5754 | −0.0178 | 0.039* | |
C6 | 1.0306 (5) | 0.6610 (5) | −0.0026 (9) | 0.0441 (18) | |
H6A | 1.0478 | 0.7014 | 0.1353 | 0.053* | |
H6B | 1.0680 | 0.5997 | 0.0117 | 0.053* | |
C7 | 1.0843 (5) | 0.7299 (5) | −0.1330 (9) | 0.0397 (18) | |
H7A | 1.0534 | 0.7949 | −0.1350 | 0.048* | |
H7B | 1.1726 | 0.7499 | −0.0725 | 0.048* | |
C8 | 1.0528 (5) | 0.6724 (4) | −0.3489 (9) | 0.0364 (16) | |
H8A | 1.0888 | 0.6101 | −0.3468 | 0.044* | |
H8B | 1.0877 | 0.7190 | −0.4307 | 0.044* | |
C9 | 0.9177 (5) | 0.6375 (4) | −0.4502 (8) | 0.0271 (15) | |
H9 | 0.9026 | 0.5957 | −0.5879 | 0.032* | |
C10 | 0.9084 (5) | 0.8056 (4) | −0.5720 (8) | 0.0291 (15) | |
H10A | 0.8963 | 0.7765 | −0.7160 | 0.035* | |
H10B | 0.9958 | 0.8267 | −0.5023 | 0.035* | |
C11 | 0.8556 (5) | 0.9003 (4) | −0.5654 (9) | 0.0293 (15) | |
C12 | 0.8504 (5) | 0.9502 (5) | −0.3834 (10) | 0.0433 (18) | |
H12 | 0.8808 | 0.9241 | −0.2609 | 0.052* | |
C13 | 0.8017 (6) | 1.0370 (5) | −0.3769 (12) | 0.057 (2) | |
H13 | 0.7965 | 1.0690 | −0.2510 | 0.068* | |
C14 | 0.7601 (6) | 1.0783 (5) | −0.5517 (14) | 0.061 (2) | |
H14 | 0.7287 | 1.1396 | −0.5459 | 0.074* | |
C15 | 0.7647 (6) | 1.0300 (6) | −0.7330 (13) | 0.055 (2) | |
H15 | 0.7348 | 1.0569 | −0.8548 | 0.066* | |
C16 | 0.8130 (5) | 0.9419 (5) | −0.7394 (10) | 0.0371 (17) | |
H16 | 0.8167 | 0.9094 | −0.8661 | 0.044* | |
C17 | 0.6702 (5) | 0.3632 (5) | −0.3126 (9) | 0.0263 (14) | |
C18 | 0.6095 (5) | 0.3139 (5) | −0.1750 (8) | 0.0252 (15) | |
C19 | 0.5804 (5) | 0.3723 (5) | −0.0246 (9) | 0.0341 (16) | |
H19 | 0.5987 | 0.4467 | −0.0075 | 0.041* | |
C20 | 0.5238 (5) | 0.3212 (5) | 0.1023 (9) | 0.0407 (18) | |
H20 | 0.5033 | 0.3604 | 0.2056 | 0.049* | |
C21 | 0.4985 (5) | 0.2126 (5) | 0.0742 (9) | 0.0337 (16) | |
C22 | 0.5246 (5) | 0.1556 (5) | −0.0765 (9) | 0.0367 (17) | |
H22 | 0.5041 | 0.0812 | −0.0959 | 0.044* | |
C23 | 0.5807 (5) | 0.2051 (4) | −0.2011 (8) | 0.0290 (15) | |
H23 | 0.5996 | 0.1648 | −0.3051 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0549 (5) | 0.0436 (5) | 0.0430 (4) | −0.0009 (3) | 0.0237 (3) | 0.0128 (3) |
O1 | 0.037 (3) | 0.026 (3) | 0.050 (3) | 0.004 (2) | 0.028 (2) | 0.014 (2) |
O2 | 0.053 (3) | 0.032 (3) | 0.055 (3) | 0.012 (2) | 0.032 (3) | 0.009 (2) |
N1 | 0.016 (3) | 0.028 (3) | 0.032 (3) | 0.005 (2) | 0.009 (2) | 0.010 (2) |
C1 | 0.023 (4) | 0.036 (4) | 0.047 (4) | 0.008 (3) | 0.009 (3) | 0.020 (3) |
C2 | 0.017 (3) | 0.030 (4) | 0.052 (4) | 0.000 (3) | 0.009 (3) | 0.011 (3) |
C3 | 0.030 (4) | 0.026 (4) | 0.040 (4) | 0.003 (3) | 0.017 (3) | 0.012 (3) |
C4 | 0.028 (4) | 0.022 (3) | 0.041 (4) | 0.012 (3) | 0.015 (3) | 0.011 (3) |
C5 | 0.039 (4) | 0.034 (4) | 0.031 (4) | 0.010 (3) | 0.017 (3) | 0.010 (3) |
C6 | 0.045 (5) | 0.037 (4) | 0.047 (4) | 0.007 (4) | 0.010 (4) | 0.004 (3) |
C7 | 0.022 (4) | 0.038 (4) | 0.055 (5) | 0.002 (3) | 0.008 (3) | 0.013 (4) |
C8 | 0.025 (4) | 0.036 (4) | 0.055 (4) | 0.010 (3) | 0.016 (3) | 0.018 (4) |
C9 | 0.026 (4) | 0.025 (4) | 0.031 (4) | 0.006 (3) | 0.011 (3) | 0.002 (3) |
C10 | 0.030 (4) | 0.025 (4) | 0.038 (4) | 0.008 (3) | 0.014 (3) | 0.014 (3) |
C11 | 0.027 (4) | 0.021 (4) | 0.043 (4) | 0.004 (3) | 0.015 (3) | 0.010 (3) |
C12 | 0.045 (4) | 0.037 (4) | 0.059 (5) | 0.015 (4) | 0.030 (4) | 0.007 (4) |
C13 | 0.059 (5) | 0.041 (5) | 0.091 (6) | 0.014 (4) | 0.056 (5) | 0.007 (5) |
C14 | 0.045 (5) | 0.019 (5) | 0.137 (8) | 0.007 (4) | 0.053 (6) | 0.022 (5) |
C15 | 0.036 (5) | 0.041 (5) | 0.095 (7) | 0.017 (4) | 0.022 (4) | 0.029 (5) |
C16 | 0.028 (4) | 0.030 (4) | 0.053 (5) | 0.005 (3) | 0.010 (3) | 0.012 (4) |
C17 | 0.019 (4) | 0.021 (4) | 0.038 (4) | 0.003 (3) | 0.009 (3) | 0.008 (3) |
C18 | 0.019 (4) | 0.031 (4) | 0.026 (4) | 0.007 (3) | 0.006 (3) | 0.010 (3) |
C19 | 0.033 (4) | 0.019 (4) | 0.042 (4) | −0.001 (3) | 0.007 (3) | −0.005 (3) |
C20 | 0.040 (4) | 0.040 (5) | 0.047 (4) | 0.000 (3) | 0.026 (4) | 0.009 (4) |
C21 | 0.029 (4) | 0.041 (4) | 0.028 (4) | −0.003 (3) | 0.007 (3) | 0.015 (3) |
C22 | 0.045 (4) | 0.024 (4) | 0.042 (4) | 0.000 (3) | 0.018 (4) | 0.010 (3) |
C23 | 0.028 (4) | 0.029 (4) | 0.030 (4) | 0.008 (3) | 0.009 (3) | 0.002 (3) |
Geometric parameters (Å, º) top
Br1—C21 | 1.894 (5) | C8—H8A | 0.9900 |
O1—C17 | 1.348 (6) | C8—H8B | 0.9900 |
O1—C3 | 1.457 (6) | C9—H9 | 1.0000 |
O2—C17 | 1.207 (6) | C10—C11 | 1.495 (7) |
N1—C1 | 1.457 (6) | C10—H10A | 0.9900 |
N1—C10 | 1.464 (6) | C10—H10B | 0.9900 |
N1—C9 | 1.467 (6) | C11—C12 | 1.380 (7) |
C1—C2 | 1.520 (6) | C11—C16 | 1.381 (7) |
C1—H1A | 0.9900 | C12—C13 | 1.373 (8) |
C1—H1B | 0.9900 | C12—H12 | 0.9500 |
C2—C3 | 1.503 (7) | C13—C14 | 1.379 (9) |
C2—H2A | 0.9900 | C13—H13 | 0.9500 |
C2—H2B | 0.9900 | C14—C15 | 1.365 (9) |
C3—C4 | 1.536 (7) | C14—H14 | 0.9500 |
C3—H3 | 1.0000 | C15—C16 | 1.385 (8) |
C4—C5 | 1.531 (7) | C15—H15 | 0.9500 |
C4—C9 | 1.551 (7) | C16—H16 | 0.9500 |
C4—H4 | 1.0000 | C17—C18 | 1.482 (7) |
C5—C6 | 1.535 (7) | C18—C19 | 1.387 (7) |
C5—H5A | 0.9900 | C18—C23 | 1.389 (7) |
C5—H5B | 0.9900 | C19—C20 | 1.403 (7) |
C6—C7 | 1.527 (7) | C19—H19 | 0.9500 |
C6—H6A | 0.9900 | C20—C21 | 1.386 (7) |
C6—H6B | 0.9900 | C20—H20 | 0.9500 |
C7—C8 | 1.513 (7) | C21—C22 | 1.359 (7) |
C7—H7A | 0.9900 | C22—C23 | 1.377 (7) |
C7—H7B | 0.9900 | C22—H22 | 0.9500 |
C8—C9 | 1.526 (7) | C23—H23 | 0.9500 |
| | | |
C17—O1—C3 | 117.3 (4) | N1—C9—C8 | 114.2 (4) |
C1—N1—C10 | 109.5 (4) | N1—C9—C4 | 108.7 (4) |
C1—N1—C9 | 110.1 (4) | C8—C9—C4 | 108.3 (5) |
C10—N1—C9 | 113.9 (4) | N1—C9—H9 | 108.5 |
N1—C1—C2 | 110.4 (4) | C8—C9—H9 | 108.5 |
N1—C1—H1A | 109.6 | C4—C9—H9 | 108.5 |
C2—C1—H1A | 109.6 | N1—C10—C11 | 112.7 (4) |
N1—C1—H1B | 109.6 | N1—C10—H10A | 109.1 |
C2—C1—H1B | 109.6 | C11—C10—H10A | 109.1 |
H1A—C1—H1B | 108.1 | N1—C10—H10B | 109.1 |
C3—C2—C1 | 110.7 (4) | C11—C10—H10B | 109.1 |
C3—C2—H2A | 109.5 | H10A—C10—H10B | 107.8 |
C1—C2—H2A | 109.5 | C12—C11—C16 | 117.9 (6) |
C3—C2—H2B | 109.5 | C12—C11—C10 | 120.8 (6) |
C1—C2—H2B | 109.5 | C16—C11—C10 | 121.3 (6) |
H2A—C2—H2B | 108.1 | C13—C12—C11 | 120.9 (6) |
O1—C3—C2 | 106.5 (4) | C13—C12—H12 | 119.6 |
O1—C3—C4 | 110.8 (4) | C11—C12—H12 | 119.6 |
C2—C3—C4 | 111.4 (5) | C14—C13—C12 | 120.6 (7) |
O1—C3—H3 | 109.4 | C14—C13—H13 | 119.7 |
C2—C3—H3 | 109.4 | C12—C13—H13 | 119.7 |
C4—C3—H3 | 109.4 | C15—C14—C13 | 119.3 (7) |
C3—C4—C5 | 114.4 (5) | C15—C14—H14 | 120.4 |
C3—C4—C9 | 108.4 (4) | C13—C14—H14 | 120.4 |
C5—C4—C9 | 110.7 (4) | C14—C15—C16 | 120.0 (7) |
C3—C4—H4 | 107.7 | C14—C15—H15 | 120.0 |
C5—C4—H4 | 107.7 | C16—C15—H15 | 120.0 |
C9—C4—H4 | 107.7 | C15—C16—C11 | 121.3 (6) |
C6—C5—C4 | 110.8 (5) | C15—C16—H16 | 119.4 |
C6—C5—H5A | 109.5 | C11—C16—H16 | 119.4 |
C4—C5—H5A | 109.5 | O2—C17—O1 | 122.6 (5) |
C6—C5—H5B | 109.5 | O2—C17—C18 | 125.2 (5) |
C4—C5—H5B | 109.5 | O1—C17—C18 | 112.2 (5) |
H5A—C5—H5B | 108.1 | C19—C18—C23 | 119.7 (5) |
C7—C6—C5 | 110.6 (5) | C19—C18—C17 | 122.4 (5) |
C7—C6—H6A | 109.5 | C23—C18—C17 | 117.9 (5) |
C5—C6—H6A | 109.5 | C18—C19—C20 | 119.8 (6) |
C7—C6—H6B | 109.5 | C18—C19—H19 | 120.1 |
C5—C6—H6B | 109.5 | C20—C19—H19 | 120.1 |
H6A—C6—H6B | 108.1 | C21—C20—C19 | 118.8 (6) |
C8—C7—C6 | 110.7 (5) | C21—C20—H20 | 120.6 |
C8—C7—H7A | 109.5 | C19—C20—H20 | 120.6 |
C6—C7—H7A | 109.5 | C22—C21—C20 | 121.1 (5) |
C8—C7—H7B | 109.5 | C22—C21—Br1 | 120.5 (5) |
C6—C7—H7B | 109.5 | C20—C21—Br1 | 118.3 (5) |
H7A—C7—H7B | 108.1 | C21—C22—C23 | 120.4 (5) |
C7—C8—C9 | 112.3 (5) | C21—C22—H22 | 119.8 |
C7—C8—H8A | 109.2 | C23—C22—H22 | 119.8 |
C9—C8—H8A | 109.2 | C22—C23—C18 | 120.0 (5) |
C7—C8—H8B | 109.2 | C22—C23—H23 | 120.0 |
C9—C8—H8B | 109.2 | C18—C23—H23 | 120.0 |
H8A—C8—H8B | 107.9 | | |
| | | |
C10—N1—C1—C2 | −170.8 (4) | C9—N1—C10—C11 | −170.8 (5) |
C9—N1—C1—C2 | 63.2 (6) | N1—C10—C11—C12 | 52.6 (7) |
N1—C1—C2—C3 | −56.6 (6) | N1—C10—C11—C16 | −128.7 (5) |
C17—O1—C3—C2 | 149.8 (5) | C16—C11—C12—C13 | 1.4 (9) |
C17—O1—C3—C4 | −88.9 (6) | C10—C11—C12—C13 | −179.8 (5) |
C1—C2—C3—O1 | 174.0 (4) | C11—C12—C13—C14 | −2.0 (10) |
C1—C2—C3—C4 | 53.1 (6) | C12—C13—C14—C15 | 1.9 (10) |
O1—C3—C4—C5 | −48.7 (6) | C13—C14—C15—C16 | −1.3 (10) |
C2—C3—C4—C5 | 69.7 (6) | C14—C15—C16—C11 | 0.8 (9) |
O1—C3—C4—C9 | −172.8 (4) | C12—C11—C16—C15 | −0.9 (8) |
C2—C3—C4—C9 | −54.4 (6) | C10—C11—C16—C15 | −179.6 (5) |
C3—C4—C5—C6 | 179.5 (5) | C3—O1—C17—O2 | −1.3 (8) |
C9—C4—C5—C6 | −57.6 (6) | C3—O1—C17—C18 | −179.9 (4) |
C4—C5—C6—C7 | 56.0 (7) | O2—C17—C18—C19 | 170.0 (6) |
C5—C6—C7—C8 | −55.6 (7) | O1—C17—C18—C19 | −11.4 (8) |
C6—C7—C8—C9 | 58.1 (7) | O2—C17—C18—C23 | −10.6 (9) |
C1—N1—C9—C8 | 174.3 (4) | O1—C17—C18—C23 | 168.1 (5) |
C10—N1—C9—C8 | 50.8 (6) | C23—C18—C19—C20 | 1.1 (9) |
C1—N1—C9—C4 | −64.8 (5) | C17—C18—C19—C20 | −179.5 (5) |
C10—N1—C9—C4 | 171.8 (4) | C18—C19—C20—C21 | 0.2 (9) |
C7—C8—C9—N1 | 62.9 (6) | C19—C20—C21—C22 | −1.7 (9) |
C7—C8—C9—C4 | −58.3 (6) | C19—C20—C21—Br1 | −179.6 (4) |
C3—C4—C9—N1 | 59.4 (6) | C20—C21—C22—C23 | 2.0 (9) |
C5—C4—C9—N1 | −66.8 (6) | Br1—C21—C22—C23 | 179.9 (4) |
C3—C4—C9—C8 | −176.0 (5) | C21—C22—C23—C18 | −0.8 (9) |
C5—C4—C9—C8 | 57.7 (6) | C19—C18—C23—C22 | −0.8 (8) |
C1—N1—C10—C11 | 65.4 (6) | C17—C18—C23—C22 | 179.7 (5) |
(XIX)
N-benzyl-
trans-4-aza-1-decalinyl
p-bromobenzoate
top
Crystal data top
C23H26BrNO2 | Z = 2 |
Mr = 428.36 | F(000) = 444 |
Triclinic, P1 | Dx = 1.339 Mg m−3 |
a = 9.561 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 9.822 (2) Å | Cell parameters from 25 reflections |
c = 13.202 (3) Å | θ = 20–25° |
α = 78.34 (2)° | µ = 2.76 mm−1 |
β = 78.21 (2)° | T = 293 K |
γ = 61.92 (3)° | Plate, colourless |
V = 1062.7 (4) Å3 | 0.52 × 0.40 × 0.17 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2585 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.02 |
Graphite monochromator | θmax = 68.0°, θmin = 5.0° |
ω/2θ scans | h = 0→11 |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | k = −9→11 |
Tmin = 0.31, Tmax = 0.63 | l = −15→15 |
3862 measured reflections | 3 standard reflections every 200 reflections |
3862 independent reflections | intensity decay: <2.0% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.43P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3862 reflections | Δρmax = 0.33 e Å−3 |
245 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0052 (5) |
Crystal data top
C23H26BrNO2 | γ = 61.92 (3)° |
Mr = 428.36 | V = 1062.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.561 (2) Å | Cu Kα radiation |
b = 9.822 (2) Å | µ = 2.76 mm−1 |
c = 13.202 (3) Å | T = 293 K |
α = 78.34 (2)° | 0.52 × 0.40 × 0.17 mm |
β = 78.21 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2585 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.02 |
Tmin = 0.31, Tmax = 0.63 | 3 standard reflections every 200 reflections |
3862 measured reflections | intensity decay: <2.0% |
3862 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.33 e Å−3 |
3862 reflections | Δρmin = −0.38 e Å−3 |
245 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.25821 (6) | 0.62098 (7) | −0.47532 (4) | 0.1162 (3) | |
O1 | 0.1876 (3) | 1.0899 (2) | −0.13734 (18) | 0.0700 (6) | |
O2 | −0.0586 (3) | 1.2222 (4) | −0.1795 (3) | 0.1267 (12) | |
N1 | 0.2782 (3) | 1.2606 (3) | 0.09296 (19) | 0.0590 (6) | |
C1 | 0.1219 (4) | 1.2634 (4) | 0.1065 (3) | 0.0703 (8) | |
H1A | 0.0421 | 1.3689 | 0.0887 | 0.084* | |
H1B | 0.0945 | 1.2307 | 0.1790 | 0.084* | |
C2 | 0.1193 (4) | 1.1574 (4) | 0.0386 (3) | 0.0703 (9) | |
H2A | 0.1944 | 1.0507 | 0.0587 | 0.084* | |
H2B | 0.0135 | 1.1632 | 0.0481 | 0.084* | |
C3 | 0.1636 (4) | 1.2062 (3) | −0.0735 (2) | 0.0621 (8) | |
H3 | 0.0778 | 1.3066 | −0.0969 | 0.075* | |
C4 | 0.3180 (4) | 1.2184 (3) | −0.0909 (2) | 0.0592 (7) | |
H4 | 0.4038 | 1.1131 | −0.0774 | 0.071* | |
C5 | 0.3545 (4) | 1.2808 (4) | −0.2030 (3) | 0.0774 (9) | |
H5A | 0.3554 | 1.2155 | −0.2495 | 0.093* | |
H5B | 0.2707 | 1.3848 | −0.2186 | 0.093* | |
C6 | 0.5141 (5) | 1.2855 (5) | −0.2225 (3) | 0.0921 (12) | |
H6A | 0.5286 | 1.3344 | −0.2928 | 0.110* | |
H6B | 0.5996 | 1.1803 | −0.2164 | 0.110* | |
C7 | 0.5224 (5) | 1.3756 (5) | −0.1450 (3) | 0.0907 (11) | |
H7A | 0.6290 | 1.3679 | −0.1543 | 0.109* | |
H7B | 0.4480 | 1.4845 | −0.1588 | 0.109* | |
C8 | 0.4828 (4) | 1.3158 (4) | −0.0333 (3) | 0.0768 (9) | |
H8A | 0.4841 | 1.3800 | 0.0132 | 0.092* | |
H8B | 0.5639 | 1.2105 | −0.0170 | 0.092* | |
C9 | 0.3192 (4) | 1.3172 (3) | −0.0150 (2) | 0.0599 (7) | |
H9 | 0.2384 | 1.4245 | −0.0307 | 0.072* | |
C10 | 0.2780 (5) | 1.3522 (4) | 0.1687 (3) | 0.0740 (9) | |
H10A | 0.1867 | 1.4539 | 0.1629 | 0.089* | |
H10B | 0.3738 | 1.3671 | 0.1513 | 0.089* | |
C11 | 0.2711 (4) | 1.2776 (4) | 0.2795 (2) | 0.0618 (8) | |
C12 | 0.3500 (4) | 1.1180 (4) | 0.3037 (3) | 0.0686 (8) | |
H12 | 0.4019 | 1.0554 | 0.2504 | 0.082* | |
C13 | 0.3526 (4) | 1.0509 (5) | 0.4060 (3) | 0.0807 (10) | |
H13 | 0.4058 | 0.9434 | 0.4215 | 0.097* | |
C14 | 0.2774 (5) | 1.1417 (6) | 0.4843 (3) | 0.0892 (12) | |
H14 | 0.2801 | 1.0960 | 0.5533 | 0.107* | |
C15 | 0.1984 (5) | 1.2990 (6) | 0.4626 (3) | 0.0966 (12) | |
H15 | 0.1468 | 1.3604 | 0.5166 | 0.116* | |
C16 | 0.1947 (5) | 1.3676 (5) | 0.3602 (3) | 0.0844 (10) | |
H16 | 0.1403 | 1.4751 | 0.3456 | 0.101* | |
C17 | 0.0707 (4) | 1.1123 (4) | −0.1872 (3) | 0.0677 (8) | |
C18 | 0.1175 (4) | 0.9899 (4) | −0.2533 (2) | 0.0608 (7) | |
C19 | 0.2705 (4) | 0.8695 (4) | −0.2630 (3) | 0.0692 (9) | |
H19 | 0.3455 | 0.8618 | −0.2242 | 0.083* | |
C20 | 0.3128 (4) | 0.7614 (4) | −0.3290 (3) | 0.0772 (9) | |
H20 | 0.4168 | 0.6824 | −0.3364 | 0.093* | |
C21 | 0.2012 (4) | 0.7699 (4) | −0.3842 (3) | 0.0724 (9) | |
C22 | 0.0483 (4) | 0.8872 (5) | −0.3756 (3) | 0.0781 (10) | |
H22 | −0.0269 | 0.8926 | −0.4131 | 0.094* | |
C23 | 0.0076 (4) | 0.9969 (4) | −0.3105 (3) | 0.0744 (9) | |
H23 | −0.0957 | 1.0774 | −0.3048 | 0.089* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.1135 (4) | 0.1417 (5) | 0.1110 (4) | −0.0579 (3) | −0.0048 (3) | −0.0603 (3) |
O1 | 0.0696 (13) | 0.0622 (13) | 0.0825 (15) | −0.0247 (11) | −0.0311 (11) | −0.0085 (11) |
O2 | 0.0685 (17) | 0.117 (2) | 0.196 (3) | −0.0082 (16) | −0.0480 (19) | −0.076 (2) |
N1 | 0.0674 (16) | 0.0518 (14) | 0.0609 (15) | −0.0276 (12) | −0.0133 (12) | −0.0053 (11) |
C1 | 0.070 (2) | 0.071 (2) | 0.067 (2) | −0.0299 (17) | −0.0094 (16) | −0.0077 (16) |
C2 | 0.069 (2) | 0.079 (2) | 0.073 (2) | −0.0420 (18) | −0.0140 (16) | −0.0031 (17) |
C3 | 0.0628 (18) | 0.0528 (17) | 0.070 (2) | −0.0210 (14) | −0.0183 (15) | −0.0075 (15) |
C4 | 0.0617 (18) | 0.0489 (16) | 0.0653 (19) | −0.0228 (14) | −0.0123 (14) | −0.0043 (14) |
C5 | 0.089 (2) | 0.075 (2) | 0.070 (2) | −0.0379 (19) | −0.0052 (18) | −0.0111 (18) |
C6 | 0.101 (3) | 0.096 (3) | 0.084 (3) | −0.056 (2) | 0.013 (2) | −0.017 (2) |
C7 | 0.097 (3) | 0.089 (3) | 0.102 (3) | −0.059 (2) | 0.008 (2) | −0.022 (2) |
C8 | 0.077 (2) | 0.072 (2) | 0.093 (3) | −0.0420 (18) | −0.0089 (19) | −0.0141 (19) |
C9 | 0.0639 (18) | 0.0447 (15) | 0.0667 (19) | −0.0210 (14) | −0.0115 (14) | −0.0031 (14) |
C10 | 0.096 (3) | 0.0589 (19) | 0.074 (2) | −0.0353 (18) | −0.0190 (18) | −0.0106 (16) |
C11 | 0.0643 (19) | 0.0622 (19) | 0.0639 (19) | −0.0294 (16) | −0.0139 (15) | −0.0100 (15) |
C12 | 0.0634 (19) | 0.070 (2) | 0.073 (2) | −0.0279 (16) | −0.0152 (16) | −0.0081 (17) |
C13 | 0.071 (2) | 0.088 (3) | 0.084 (3) | −0.038 (2) | −0.0257 (19) | 0.008 (2) |
C14 | 0.091 (3) | 0.130 (4) | 0.069 (2) | −0.070 (3) | −0.020 (2) | 0.005 (3) |
C15 | 0.107 (3) | 0.124 (4) | 0.073 (3) | −0.057 (3) | −0.005 (2) | −0.032 (3) |
C16 | 0.091 (3) | 0.079 (2) | 0.085 (3) | −0.034 (2) | −0.011 (2) | −0.024 (2) |
C17 | 0.061 (2) | 0.071 (2) | 0.078 (2) | −0.0336 (18) | −0.0159 (16) | −0.0058 (17) |
C18 | 0.0586 (18) | 0.071 (2) | 0.0618 (18) | −0.0375 (16) | −0.0129 (14) | −0.0007 (15) |
C19 | 0.066 (2) | 0.074 (2) | 0.075 (2) | −0.0335 (18) | −0.0236 (17) | −0.0052 (17) |
C20 | 0.068 (2) | 0.078 (2) | 0.083 (2) | −0.0269 (18) | −0.0174 (18) | −0.0130 (19) |
C21 | 0.078 (2) | 0.088 (2) | 0.065 (2) | −0.048 (2) | −0.0055 (17) | −0.0132 (17) |
C22 | 0.071 (2) | 0.111 (3) | 0.073 (2) | −0.054 (2) | −0.0118 (17) | −0.018 (2) |
C23 | 0.0559 (19) | 0.095 (2) | 0.081 (2) | −0.0376 (18) | −0.0134 (16) | −0.016 (2) |
Geometric parameters (Å, º) top
Br1—C21 | 1.891 (3) | C8—H8A | 0.9700 |
O1—C17 | 1.320 (4) | C8—H8B | 0.9700 |
O1—C3 | 1.459 (3) | C9—H9 | 0.9800 |
O2—C17 | 1.200 (4) | C10—C11 | 1.501 (4) |
N1—C1 | 1.456 (4) | C10—H10A | 0.9700 |
N1—C9 | 1.467 (4) | C10—H10B | 0.9700 |
N1—C10 | 1.473 (4) | C11—C16 | 1.380 (5) |
C1—C2 | 1.515 (5) | C11—C12 | 1.382 (4) |
C1—H1A | 0.9700 | C12—C13 | 1.377 (5) |
C1—H1B | 0.9700 | C12—H12 | 0.9300 |
C2—C3 | 1.499 (4) | C13—C14 | 1.359 (6) |
C2—H2A | 0.9700 | C13—H13 | 0.9300 |
C2—H2B | 0.9700 | C14—C15 | 1.360 (6) |
C3—C4 | 1.504 (4) | C14—H14 | 0.9300 |
C3—H3 | 0.9800 | C15—C16 | 1.382 (6) |
C4—C5 | 1.520 (4) | C15—H15 | 0.9300 |
C4—C9 | 1.535 (4) | C16—H16 | 0.9300 |
C4—H4 | 0.9800 | C17—C18 | 1.472 (5) |
C5—C6 | 1.515 (5) | C18—C23 | 1.382 (4) |
C5—H5A | 0.9700 | C18—C19 | 1.383 (4) |
C5—H5B | 0.9700 | C19—C20 | 1.370 (5) |
C6—C7 | 1.518 (5) | C19—H19 | 0.9300 |
C6—H6A | 0.9700 | C20—C21 | 1.373 (5) |
C6—H6B | 0.9700 | C20—H20 | 0.9300 |
C7—C8 | 1.514 (5) | C21—C22 | 1.370 (5) |
C7—H7A | 0.9700 | C22—C23 | 1.377 (5) |
C7—H7B | 0.9700 | C22—H22 | 0.9300 |
C8—C9 | 1.527 (4) | C23—H23 | 0.9300 |
| | | |
C17—O1—C3 | 119.5 (2) | N1—C9—C8 | 112.5 (3) |
C1—N1—C9 | 110.5 (2) | N1—C9—C4 | 110.6 (2) |
C1—N1—C10 | 108.9 (3) | C8—C9—C4 | 108.6 (3) |
C9—N1—C10 | 112.5 (2) | N1—C9—H9 | 108.3 |
N1—C1—C2 | 111.6 (3) | C8—C9—H9 | 108.3 |
N1—C1—H1A | 109.3 | C4—C9—H9 | 108.3 |
C2—C1—H1A | 109.3 | N1—C10—C11 | 113.5 (3) |
N1—C1—H1B | 109.3 | N1—C10—H10A | 108.9 |
C2—C1—H1B | 109.3 | C11—C10—H10A | 108.9 |
H1A—C1—H1B | 108.0 | N1—C10—H10B | 108.9 |
C3—C2—C1 | 109.5 (3) | C11—C10—H10B | 108.9 |
C3—C2—H2A | 109.8 | H10A—C10—H10B | 107.7 |
C1—C2—H2A | 109.8 | C16—C11—C12 | 118.4 (3) |
C3—C2—H2B | 109.8 | C16—C11—C10 | 120.6 (3) |
C1—C2—H2B | 109.8 | C12—C11—C10 | 120.9 (3) |
H2A—C2—H2B | 108.2 | C13—C12—C11 | 120.6 (3) |
O1—C3—C2 | 109.8 (2) | C13—C12—H12 | 119.7 |
O1—C3—C4 | 106.3 (2) | C11—C12—H12 | 119.7 |
C2—C3—C4 | 112.3 (3) | C14—C13—C12 | 120.0 (4) |
O1—C3—H3 | 109.5 | C14—C13—H13 | 120.0 |
C2—C3—H3 | 109.5 | C12—C13—H13 | 120.0 |
C4—C3—H3 | 109.5 | C13—C14—C15 | 120.5 (4) |
C3—C4—C5 | 111.8 (3) | C13—C14—H14 | 119.8 |
C3—C4—C9 | 111.9 (2) | C15—C14—H14 | 119.8 |
C5—C4—C9 | 110.5 (2) | C14—C15—C16 | 120.0 (4) |
C3—C4—H4 | 107.5 | C14—C15—H15 | 120.0 |
C5—C4—H4 | 107.5 | C16—C15—H15 | 120.0 |
C9—C4—H4 | 107.5 | C11—C16—C15 | 120.5 (4) |
C6—C5—C4 | 112.1 (3) | C11—C16—H16 | 119.8 |
C6—C5—H5A | 109.2 | C15—C16—H16 | 119.8 |
C4—C5—H5A | 109.2 | O2—C17—O1 | 122.9 (3) |
C6—C5—H5B | 109.2 | O2—C17—C18 | 124.4 (3) |
C4—C5—H5B | 109.2 | O1—C17—C18 | 112.7 (3) |
H5A—C5—H5B | 107.9 | C23—C18—C19 | 118.4 (3) |
C5—C6—C7 | 110.7 (3) | C23—C18—C17 | 119.6 (3) |
C5—C6—H6A | 109.5 | C19—C18—C17 | 122.0 (3) |
C7—C6—H6A | 109.5 | C20—C19—C18 | 120.7 (3) |
C5—C6—H6B | 109.5 | C20—C19—H19 | 119.7 |
C7—C6—H6B | 109.5 | C18—C19—H19 | 119.7 |
H6A—C6—H6B | 108.1 | C19—C20—C21 | 119.8 (3) |
C8—C7—C6 | 112.2 (3) | C19—C20—H20 | 120.1 |
C8—C7—H7A | 109.2 | C21—C20—H20 | 120.1 |
C6—C7—H7A | 109.2 | C22—C21—C20 | 120.8 (3) |
C8—C7—H7B | 109.2 | C22—C21—Br1 | 119.1 (3) |
C6—C7—H7B | 109.2 | C20—C21—Br1 | 120.2 (3) |
H7A—C7—H7B | 107.9 | C21—C22—C23 | 119.0 (3) |
C7—C8—C9 | 111.7 (3) | C21—C22—H22 | 120.5 |
C7—C8—H8A | 109.3 | C23—C22—H22 | 120.5 |
C9—C8—H8A | 109.3 | C22—C23—C18 | 121.3 (3) |
C7—C8—H8B | 109.3 | C22—C23—H23 | 119.4 |
C9—C8—H8B | 109.3 | C18—C23—H23 | 119.4 |
H8A—C8—H8B | 107.9 | | |
| | | |
C9—N1—C1—C2 | 61.9 (3) | C9—N1—C10—C11 | −167.7 (3) |
C10—N1—C1—C2 | −174.0 (3) | N1—C10—C11—C16 | −148.1 (3) |
N1—C1—C2—C3 | −58.3 (4) | N1—C10—C11—C12 | 36.3 (4) |
C17—O1—C3—C2 | 97.8 (3) | C16—C11—C12—C13 | −0.2 (5) |
C17—O1—C3—C4 | −140.5 (3) | C10—C11—C12—C13 | 175.5 (3) |
C1—C2—C3—O1 | 170.5 (2) | C11—C12—C13—C14 | −0.2 (5) |
C1—C2—C3—C4 | 52.5 (4) | C12—C13—C14—C15 | 0.5 (6) |
O1—C3—C4—C5 | 64.7 (3) | C13—C14—C15—C16 | −0.3 (6) |
C2—C3—C4—C5 | −175.2 (3) | C12—C11—C16—C15 | 0.4 (5) |
O1—C3—C4—C9 | −170.7 (2) | C10—C11—C16—C15 | −175.3 (3) |
C2—C3—C4—C9 | −50.7 (3) | C14—C15—C16—C11 | −0.1 (6) |
C3—C4—C5—C6 | −177.0 (3) | C3—O1—C17—O2 | −3.0 (5) |
C9—C4—C5—C6 | 57.7 (4) | C3—O1—C17—C18 | 176.2 (2) |
C4—C5—C6—C7 | −54.1 (4) | O2—C17—C18—C23 | −0.9 (5) |
C5—C6—C7—C8 | 53.0 (5) | O1—C17—C18—C23 | 179.9 (3) |
C6—C7—C8—C9 | −56.0 (4) | O2—C17—C18—C19 | 177.0 (4) |
C1—N1—C9—C8 | −179.7 (3) | O1—C17—C18—C19 | −2.2 (4) |
C10—N1—C9—C8 | 58.3 (3) | C23—C18—C19—C20 | 1.1 (5) |
C1—N1—C9—C4 | −58.1 (3) | C17—C18—C19—C20 | −176.8 (3) |
C10—N1—C9—C4 | 180.0 (3) | C18—C19—C20—C21 | −1.8 (5) |
C7—C8—C9—N1 | −179.6 (3) | C19—C20—C21—C22 | 1.2 (6) |
C7—C8—C9—C4 | 57.6 (3) | C19—C20—C21—Br1 | −179.8 (3) |
C3—C4—C9—N1 | 52.7 (3) | C20—C21—C22—C23 | 0.0 (5) |
C5—C4—C9—N1 | 177.9 (3) | Br1—C21—C22—C23 | −179.0 (3) |
C3—C4—C9—C8 | 176.6 (3) | C21—C22—C23—C18 | −0.6 (5) |
C5—C4—C9—C8 | −58.1 (3) | C19—C18—C23—C22 | 0.1 (5) |
C1—N1—C10—C11 | 69.4 (4) | C17—C18—C23—C22 | 178.1 (3) |
(XX)
trans-4-thia-1-decalinyl
p-bromobenzoate
top
Crystal data top
C16H19BrO2S | F(000) = 364 |
Mr = 355.28 | Dx = 1.491 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 8.886 (2) Å | Cell parameters from 25 reflections |
b = 5.3714 (9) Å | θ = 15–25° |
c = 16.599 (3) Å | µ = 4.76 mm−1 |
β = 92.70 (2)° | T = 293 K |
V = 791.4 (3) Å3 | Prismatic, colourless |
Z = 2 | 0.40 × 0.25 × 0.20 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2563 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 68.0°, θmin = 5.0° |
ω/2θ scans | h = 0→10 |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | k = −6→5 |
Tmin = 0.28, Tmax = 0.39 | l = −19→19 |
2984 measured reflections | 3 standard reflections every 200 reflections |
2797 independent reflections | intensity decay: <0.1% |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | w = 1/[σ2(Fo2) + (0.08P)2 + 0.65P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.133 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.38 e Å−3 |
2797 reflections | Δρmin = −0.52 e Å−3 |
182 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0237 (16) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.05 (3) |
Crystal data top
C16H19BrO2S | V = 791.4 (3) Å3 |
Mr = 355.28 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 8.886 (2) Å | µ = 4.76 mm−1 |
b = 5.3714 (9) Å | T = 293 K |
c = 16.599 (3) Å | 0.40 × 0.25 × 0.20 mm |
β = 92.70 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2563 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.014 |
Tmin = 0.28, Tmax = 0.39 | 3 standard reflections every 200 reflections |
2984 measured reflections | intensity decay: <0.1% |
2797 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.133 | Δρmax = 0.38 e Å−3 |
S = 1.04 | Δρmin = −0.52 e Å−3 |
2797 reflections | Absolute structure: Flack (1983) |
182 parameters | Absolute structure parameter: −0.05 (3) |
1 restraint | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | −0.32605 (6) | −0.09427 (17) | 0.57524 (4) | 0.0915 (3) | |
S1 | 0.29850 (18) | −0.3767 (3) | 0.02450 (7) | 0.0716 (4) | |
O1 | 0.0979 (3) | −0.0869 (7) | 0.24798 (16) | 0.0512 (7) | |
O2 | −0.0165 (5) | 0.2766 (8) | 0.2242 (3) | 0.0870 (13) | |
C1 | 0.1403 (6) | −0.1702 (12) | 0.0246 (3) | 0.0691 (15) | |
H1A | 0.1732 | −0.0021 | 0.0134 | 0.083* | |
H1B | 0.0670 | −0.2188 | −0.0176 | 0.083* | |
C2 | 0.0670 (5) | −0.1755 (11) | 0.1060 (3) | 0.0625 (14) | |
H2A | −0.0239 | −0.0751 | 0.1030 | 0.075* | |
H2B | 0.0388 | −0.3451 | 0.1186 | 0.075* | |
C3 | 0.1739 (4) | −0.0765 (10) | 0.1719 (2) | 0.0488 (9) | |
H3 | 0.1999 | 0.0966 | 0.1599 | 0.059* | |
C4 | 0.3172 (5) | −0.2278 (8) | 0.1853 (2) | 0.0447 (9) | |
H4 | 0.2886 | −0.3983 | 0.1990 | 0.054* | |
C5 | 0.4182 (5) | −0.1259 (11) | 0.2546 (3) | 0.0550 (10) | |
H5A | 0.4444 | 0.0452 | 0.2429 | 0.066* | |
H5B | 0.3629 | −0.1265 | 0.3036 | 0.066* | |
C6 | 0.5607 (5) | −0.2754 (13) | 0.2683 (3) | 0.0667 (14) | |
H6A | 0.5355 | −0.4439 | 0.2837 | 0.080* | |
H6B | 0.6221 | −0.2019 | 0.3119 | 0.080* | |
C7 | 0.6499 (6) | −0.2815 (14) | 0.1917 (4) | 0.0760 (16) | |
H7A | 0.6824 | −0.1145 | 0.1787 | 0.091* | |
H7B | 0.7388 | −0.3845 | 0.2005 | 0.091* | |
C8 | 0.5521 (6) | −0.3860 (12) | 0.1218 (3) | 0.0698 (14) | |
H8A | 0.5279 | −0.5584 | 0.1329 | 0.084* | |
H8B | 0.6079 | −0.3815 | 0.0730 | 0.084* | |
C9 | 0.4066 (5) | −0.2382 (9) | 0.1086 (3) | 0.0521 (10) | |
H9 | 0.4329 | −0.0676 | 0.0937 | 0.062* | |
C10 | 0.0045 (5) | 0.0959 (10) | 0.2649 (3) | 0.0526 (11) | |
C11 | −0.0737 (4) | 0.0460 (9) | 0.3406 (3) | 0.0468 (10) | |
C12 | −0.0441 (5) | −0.1642 (9) | 0.3862 (3) | 0.0504 (11) | |
H12 | 0.0265 | −0.2794 | 0.3700 | 0.060* | |
C13 | −0.1197 (5) | −0.2043 (10) | 0.4567 (3) | 0.0559 (12) | |
H13 | −0.0989 | −0.3445 | 0.4881 | 0.067* | |
C14 | −0.2245 (5) | −0.0359 (10) | 0.4791 (3) | 0.0565 (12) | |
C15 | −0.2567 (6) | 0.1731 (12) | 0.4354 (3) | 0.0677 (14) | |
H15 | −0.3286 | 0.2854 | 0.4520 | 0.081* | |
C16 | −0.1798 (5) | 0.2168 (10) | 0.3648 (3) | 0.0613 (12) | |
H16 | −0.1999 | 0.3594 | 0.3344 | 0.074* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0710 (4) | 0.1398 (7) | 0.0671 (4) | −0.0211 (4) | 0.0381 (3) | −0.0163 (4) |
S1 | 0.0916 (10) | 0.0786 (9) | 0.0463 (6) | −0.0072 (7) | 0.0204 (6) | −0.0129 (6) |
O1 | 0.0470 (14) | 0.0640 (17) | 0.0443 (14) | 0.0101 (16) | 0.0201 (11) | 0.0065 (15) |
O2 | 0.096 (3) | 0.078 (3) | 0.091 (3) | 0.030 (2) | 0.041 (2) | 0.032 (2) |
C1 | 0.065 (3) | 0.097 (4) | 0.045 (2) | −0.015 (3) | 0.005 (2) | 0.003 (2) |
C2 | 0.049 (2) | 0.091 (4) | 0.048 (2) | −0.006 (2) | 0.0052 (19) | 0.010 (2) |
C3 | 0.0449 (19) | 0.063 (3) | 0.0400 (19) | −0.004 (2) | 0.0176 (15) | 0.007 (2) |
C4 | 0.043 (2) | 0.051 (2) | 0.0410 (19) | −0.0018 (17) | 0.0144 (17) | 0.0011 (17) |
C5 | 0.051 (2) | 0.068 (3) | 0.047 (2) | −0.005 (2) | 0.0095 (17) | −0.004 (2) |
C6 | 0.043 (2) | 0.098 (4) | 0.059 (3) | 0.002 (3) | 0.006 (2) | 0.009 (3) |
C7 | 0.046 (3) | 0.103 (4) | 0.081 (4) | 0.016 (3) | 0.021 (3) | 0.023 (3) |
C8 | 0.068 (3) | 0.078 (3) | 0.066 (3) | 0.021 (3) | 0.032 (3) | 0.009 (3) |
C9 | 0.056 (3) | 0.057 (3) | 0.045 (2) | 0.001 (2) | 0.0213 (19) | 0.0021 (19) |
C10 | 0.042 (2) | 0.064 (3) | 0.053 (2) | 0.0070 (19) | 0.0138 (18) | 0.006 (2) |
C11 | 0.035 (2) | 0.056 (2) | 0.050 (2) | 0.0044 (17) | 0.0107 (17) | −0.0007 (19) |
C12 | 0.042 (2) | 0.061 (3) | 0.049 (2) | 0.0079 (19) | 0.0136 (17) | 0.0001 (18) |
C13 | 0.051 (2) | 0.071 (3) | 0.046 (2) | 0.000 (2) | 0.011 (2) | 0.003 (2) |
C14 | 0.041 (2) | 0.077 (4) | 0.053 (2) | −0.009 (2) | 0.0156 (18) | −0.010 (2) |
C15 | 0.044 (2) | 0.086 (4) | 0.075 (3) | 0.011 (2) | 0.020 (2) | −0.016 (3) |
C16 | 0.048 (2) | 0.067 (3) | 0.070 (3) | 0.014 (2) | 0.014 (2) | 0.000 (2) |
Geometric parameters (Å, º) top
Br1—C14 | 1.897 (4) | C6—H6A | 0.9700 |
S1—C1 | 1.790 (6) | C6—H6B | 0.9700 |
S1—C9 | 1.816 (5) | C7—C8 | 1.524 (9) |
O1—C10 | 1.324 (6) | C7—H7A | 0.9700 |
O1—C3 | 1.462 (4) | C7—H7B | 0.9700 |
O2—C10 | 1.193 (6) | C8—C9 | 1.524 (7) |
C1—C2 | 1.527 (7) | C8—H8A | 0.9700 |
C1—H1A | 0.9700 | C8—H8B | 0.9700 |
C1—H1B | 0.9700 | C9—H9 | 0.9800 |
C2—C3 | 1.512 (6) | C10—C11 | 1.488 (6) |
C2—H2A | 0.9700 | C11—C12 | 1.378 (6) |
C2—H2B | 0.9700 | C11—C16 | 1.388 (6) |
C3—C4 | 1.518 (6) | C12—C13 | 1.393 (6) |
C3—H3 | 0.9800 | C12—H12 | 0.9300 |
C4—C5 | 1.527 (6) | C13—C14 | 1.362 (7) |
C4—C9 | 1.533 (5) | C13—H13 | 0.9300 |
C4—H4 | 0.9800 | C14—C15 | 1.359 (8) |
C5—C6 | 1.507 (7) | C15—C16 | 1.404 (8) |
C5—H5A | 0.9700 | C15—H15 | 0.9300 |
C5—H5B | 0.9700 | C16—H16 | 0.9300 |
C6—C7 | 1.530 (7) | | |
| | | |
C1—S1—C9 | 97.6 (2) | C8—C7—H7A | 109.7 |
C10—O1—C3 | 118.3 (4) | C6—C7—H7A | 109.7 |
C2—C1—S1 | 111.0 (4) | C8—C7—H7B | 109.7 |
C2—C1—H1A | 109.4 | C6—C7—H7B | 109.7 |
S1—C1—H1A | 109.4 | H7A—C7—H7B | 108.2 |
C2—C1—H1B | 109.4 | C7—C8—C9 | 111.5 (5) |
S1—C1—H1B | 109.4 | C7—C8—H8A | 109.3 |
H1A—C1—H1B | 108.0 | C9—C8—H8A | 109.3 |
C3—C2—C1 | 110.7 (4) | C7—C8—H8B | 109.3 |
C3—C2—H2A | 109.5 | C9—C8—H8B | 109.3 |
C1—C2—H2A | 109.5 | H8A—C8—H8B | 108.0 |
C3—C2—H2B | 109.5 | C8—C9—C4 | 111.6 (4) |
C1—C2—H2B | 109.5 | C8—C9—S1 | 108.2 (4) |
H2A—C2—H2B | 108.1 | C4—C9—S1 | 112.2 (3) |
O1—C3—C2 | 108.2 (3) | C8—C9—H9 | 108.3 |
O1—C3—C4 | 105.7 (3) | C4—C9—H9 | 108.3 |
C2—C3—C4 | 114.3 (4) | S1—C9—H9 | 108.3 |
O1—C3—H3 | 109.5 | O2—C10—O1 | 124.5 (4) |
C2—C3—H3 | 109.5 | O2—C10—C11 | 123.9 (4) |
C4—C3—H3 | 109.5 | O1—C10—C11 | 111.6 (4) |
C3—C4—C5 | 112.2 (4) | C12—C11—C16 | 119.8 (4) |
C3—C4—C9 | 111.2 (3) | C12—C11—C10 | 121.8 (4) |
C5—C4—C9 | 109.2 (3) | C16—C11—C10 | 118.4 (4) |
C3—C4—H4 | 108.0 | C11—C12—C13 | 120.1 (4) |
C5—C4—H4 | 108.0 | C11—C12—H12 | 120.0 |
C9—C4—H4 | 108.0 | C13—C12—H12 | 120.0 |
C6—C5—C4 | 112.5 (4) | C14—C13—C12 | 119.3 (5) |
C6—C5—H5A | 109.1 | C14—C13—H13 | 120.4 |
C4—C5—H5A | 109.1 | C12—C13—H13 | 120.4 |
C6—C5—H5B | 109.1 | C15—C14—C13 | 122.2 (4) |
C4—C5—H5B | 109.1 | C15—C14—Br1 | 119.3 (4) |
H5A—C5—H5B | 107.8 | C13—C14—Br1 | 118.6 (4) |
C5—C6—C7 | 110.5 (4) | C14—C15—C16 | 119.0 (5) |
C5—C6—H6A | 109.5 | C14—C15—H15 | 120.5 |
C7—C6—H6A | 109.5 | C16—C15—H15 | 120.5 |
C5—C6—H6B | 109.5 | C11—C16—C15 | 119.7 (5) |
C7—C6—H6B | 109.5 | C11—C16—H16 | 120.2 |
H6A—C6—H6B | 108.1 | C15—C16—H16 | 120.2 |
C8—C7—C6 | 110.0 (4) | | |
| | | |
C9—S1—C1—C2 | −58.3 (4) | C5—C4—C9—S1 | 176.2 (3) |
S1—C1—C2—C3 | 64.7 (5) | C1—S1—C9—C8 | 179.7 (3) |
C10—O1—C3—C2 | −82.3 (5) | C1—S1—C9—C4 | 56.2 (4) |
C10—O1—C3—C4 | 154.9 (4) | C3—O1—C10—O2 | −4.1 (7) |
C1—C2—C3—O1 | −179.8 (4) | C3—O1—C10—C11 | 174.8 (4) |
C1—C2—C3—C4 | −62.3 (6) | O2—C10—C11—C12 | −179.1 (5) |
O1—C3—C4—C5 | −58.9 (5) | O1—C10—C11—C12 | 2.0 (6) |
C2—C3—C4—C5 | −177.7 (4) | O2—C10—C11—C16 | 1.3 (8) |
O1—C3—C4—C9 | 178.5 (4) | O1—C10—C11—C16 | −177.6 (4) |
C2—C3—C4—C9 | 59.6 (5) | C16—C11—C12—C13 | −0.4 (7) |
C3—C4—C5—C6 | 180.0 (4) | C10—C11—C12—C13 | −180.0 (5) |
C9—C4—C5—C6 | −56.3 (5) | C11—C12—C13—C14 | 1.0 (7) |
C4—C5—C6—C7 | 58.0 (6) | C12—C13—C14—C15 | −0.9 (7) |
C5—C6—C7—C8 | −56.7 (7) | C12—C13—C14—Br1 | −180.0 (4) |
C6—C7—C8—C9 | 56.2 (6) | C13—C14—C15—C16 | 0.1 (8) |
C7—C8—C9—C4 | −56.1 (6) | Br1—C14—C15—C16 | 179.2 (4) |
C7—C8—C9—S1 | −180.0 (4) | C12—C11—C16—C15 | −0.4 (7) |
C3—C4—C9—C8 | 179.0 (4) | C10—C11—C16—C15 | 179.2 (5) |
C5—C4—C9—C8 | 54.7 (5) | C14—C15—C16—C11 | 0.5 (8) |
C3—C4—C9—S1 | −59.4 (4) | | |
Experimental details
| (XVI) | (XVII) | (XVIII) | (XIX) |
Crystal data |
Chemical formula | C16H19BrO3 | C16H19BrO3 | C23H26BrNO2 | C23H26BrNO2 |
Mr | 339.22 | 339.22 | 428.36 | 428.36 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 170 | 293 | 170 | 293 |
a, b, c (Å) | 10.906 (2), 8.052 (4), 17.195 (3) | 9.643 (2), 10.679 (2), 8.772 (2) | 11.914 (3), 13.144 (3), 6.922 (2) | 9.561 (2), 9.822 (2), 13.202 (3) |
α, β, γ (°) | 90, 95.98 (2), 90 | 96.32 (2), 111.32 (2), 110.49 (2) | 96.06 (2), 106.22 (2), 100.42 (3) | 78.34 (2), 78.21 (2), 61.92 (3) |
V (Å3) | 1501.8 (8) | 758.5 (3) | 1009.6 (5) | 1062.7 (4) |
Z | 4 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Cu Kα |
µ (mm−1) | 2.74 | 2.71 | 2.05 | 2.76 |
Crystal size (mm) | 0.48 × 0.42 × 0.33 | 0.60 × 0.40 × 0.15 | 0.60 × 0.40 × 0.32 | 0.52 × 0.40 × 0.17 |
|
Data collection |
Diffractometer | Rigaku AFC-6S diffractometer | Rigaku AFC-6S diffractometer | Rigaku AFC-6S diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) |
Tmin, Tmax | 0.28, 0.41 | 0.28, 0.67 | 0.39, 0.52 | 0.31, 0.63 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2646, 2646, 693 | 2702, 2702, 1169 | 3574, 3574, 1407 | 3862, 3862, 2585 |
Rint | 0.08 | 0.03 | 0.09 | 0.02 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 | 0.601 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.109, 0.94 | 0.039, 0.130, 0.98 | 0.040, 0.110, 0.95 | 0.046, 0.135, 1.03 |
No. of reflections | 2646 | 2702 | 3574 | 3862 |
No. of parameters | 182 | 181 | 244 | 245 |
No. of restraints | 0 | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.77 | 0.42, −0.38 | 0.43, −0.76 | 0.33, −0.38 |
Absolute structure | ? | ? | ? | ? |
Absolute structure parameter | ? | ? | ? | ? |
| (XX) |
Crystal data |
Chemical formula | C16H19BrO2S |
Mr | 355.28 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 8.886 (2), 5.3714 (9), 16.599 (3) |
α, β, γ (°) | 90, 92.70 (2), 90 |
V (Å3) | 791.4 (3) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 4.76 |
Crystal size (mm) | 0.40 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) |
Tmin, Tmax | 0.28, 0.39 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2984, 2797, 2563 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.601 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.133, 1.04 |
No. of reflections | 2797 |
No. of parameters | 182 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.52 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.05 (3) |
Selected geometric parameters (Å, º) for (XVI) topBr1—C14 | 1.895 (8) | O2—C10 | 1.324 (9) |
O1—C1 | 1.421 (9) | O2—C3 | 1.458 (7) |
O1—C9 | 1.439 (10) | O3—C10 | 1.228 (9) |
| | | |
C1—O1—C9 | 111.6 (7) | C10—O2—C3 | 117.9 (7) |
Selected geometric parameters (Å, º) for (XVII) topBr1—C14 | 1.880 (5) | O2—C10 | 1.344 (6) |
O1—C9 | 1.410 (6) | O2—C3 | 1.456 (6) |
O1—C1 | 1.407 (6) | O3—C10 | 1.200 (6) |
| | | |
C9—O1—C1 | 111.9 (4) | C10—O2—C3 | 119.2 (4) |
Selected geometric parameters (Å, º) for (XVIII) topBr1—C21 | 1.894 (5) | N1—C1 | 1.457 (6) |
O1—C17 | 1.348 (6) | N1—C10 | 1.464 (6) |
O1—C3 | 1.457 (6) | N1—C9 | 1.467 (6) |
O2—C17 | 1.207 (6) | | |
| | | |
C17—O1—C3 | 117.3 (4) | C1—N1—C9 | 110.1 (4) |
C1—N1—C10 | 109.5 (4) | C10—N1—C9 | 113.9 (4) |
Selected geometric parameters (Å, º) for (XIX) topBr1—C21 | 1.891 (3) | N1—C1 | 1.456 (4) |
O1—C17 | 1.320 (4) | N1—C9 | 1.467 (4) |
O1—C3 | 1.459 (3) | N1—C10 | 1.473 (4) |
O2—C17 | 1.200 (4) | | |
| | | |
C17—O1—C3 | 119.5 (2) | C1—N1—C10 | 108.9 (3) |
C1—N1—C9 | 110.5 (2) | C9—N1—C10 | 112.5 (2) |
Selected geometric parameters (Å, º) for (XX) topBr1—C14 | 1.897 (4) | O1—C10 | 1.324 (6) |
S1—C1 | 1.790 (6) | O1—C3 | 1.462 (4) |
S1—C9 | 1.816 (5) | O2—C10 | 1.193 (6) |
| | | |
C1—S1—C9 | 97.6 (2) | C10—O1—C3 | 118.3 (4) |
In studies directed at the evaluation of the cation complexation model (Jeyaraj et al., 1997; Jeyaraj & Yadav, 1997; Yadav & Jeyaraj, 1998; Yadav et al., 1999, 2000) in order to predict and interpret the π-facial selectivities of diastereotopic ketones in reactions with nucleophiles, we have determined the experimental selectivities of cis-4-oxa-1-decalone, (I), trans-4-oxa-1-decalone, (II), cis-N-benzyl-4-aza-1-decalone, (III), trans-N-benzyl-4-aza-1-decalone, (IV), and trans-4-thia-1-decalone, (V), from reductions with LiAlH4 in Et2O at 267–273 K, NaBH4 in MeOH at 267–273 K and NaCNBH3 in aqueous MeOH at 297 K and pH 3–4. In each case, a mixture of two isomers was produced; the results of the study dealing with the ratios of the products formed will be reported elsewhere (Yadav et al., 2001). The isomers were separated by careful chromatography over silica gel and the relative stereostructure of the major isomer was determined by single-crystal X-ray diffraction. The alcohols cis-4-oxa-1-decalinol, (VI), trans-4-oxa-1-decalinol, (VIII), N-benzyl-cis-4-aza-1-decalinol, (X), and N-benzyl-trans-4-aza-1-decalone, (XII), are liquids at room temperature. Trans-4-thia-1-decalinol, (XIV), produced crystals of very poor quality. All of the alcohols were therefore converted to the p-bromobenzoate esters, cis-4-oxa-1-decalinyl p-bromobenzoate, (XVI), trans-4-oxa-1-decalinyl p-bromobenzoate, (XVII), N-benzyl-cis-4-aza-1-decalinyl p-bromobenzoate, (XVIII), N-benzyl-trans-4-aza-1-decalinyl p-bromobenzoate, (XIX) and trans-4-thia-1-decalinyl p-bromobenzoate, (XX), and the structures of these five compounds are presented in this paper. \sch
The structures of compounds (XVI)-(XX) (Figs. 1–5) are composed of independent molecules which are separated by normal van der Waals distances. The heterocyclic rings in all of the structures exhibit chair conformations, with torsion angles in the range ±53.3 (10)–63.5 (9), ±54.6 (6)–60.5 (6), ±53.1 (6)–64.8 (5), ±50.7 (3)–61.9 (3) and ±56.2 (4)–64.7 (5)°, for (XVI)-(XX), respectively. The heterocyclic ring in (XIX) exhibits the highest degree of flattening amongst the rest of the structures, having three torsion angles of -50.7 (3), 52.5 (4) and 52.7 (3)°. The cyclohexyl rings in all of the structures also exhibit chair conformations, with torsion angles in the range ±52.4 (11)–57.4 (11), ±54.5 (8)–55.4 (8), ±55.6 (7)–58.3 (6), ±53.0 (5)–58.1 (3) and ±54.7 (5)–58.0 (6)°, for (XVI)-(XX), respectively.
The p-bromobenzoate groups in (XVI) and (XX) are essentially planar, with maximum deviations of 0.074 (7) and 0.066 (8) Å, respectively, from the least-squares planes of the phenyl ring C atoms. The O atoms of the corresponding groups in (XVII) and (XVIII) lie 0.179 (9) and 0.205 (9) Å in the former, and 0.229 (9) and 0.203 (9) Å in the latter, on opposite sides from the least-squares planes of the phenyl rings. On the other hand, in (XIX), the carbonyl O atom lies 0.117 (7) Å out of the least-squares plane of the phenyl ring; the rest of the atoms of the p-bromobenzoate group lie in this plane, with a maximum deviation of 0.043 (6) Å. These small but significant differences are also supported by a comparison of the angles between the mean planes of the phenyl rings and the oxalate atoms, e.g. the mean planes between phenyl ring C11—C16 and atoms O2, O3, C10 and C11 in (XVI) are inclined at 3.34 (14)°. The corresponding angles in (XVII)-(XX) are 9.9 (3), 11.2 (4), 2.8 (3) and 2.1 (4)°, respectively.
The conformational differences in the five structures are evident from a comparison of torsion angles. For example, the angle C2—C3—O2—C10 in (XVI) is -154.8 (9)°. The corresponding angles in the structures of (XVII)-(XX) are 113.6 (5), 149.8 (5), 97.8 (3) and -82.3 (5)°, respectively. The bond distances and angles in the five structures are normal and agree well with the expected values (Orpen et al., 1994).
The crystal of (XX) chosen for analysis in this study belongs to a noncentrosymmetric space group, although the starting material was a racemic mixture. An absolute structure was established by the Flack (1983) method; the Flack parameter for the inverted structure was 1.04 (4).