Polysubstituted piperidones,
viz. the title compounds, C
27H
25NO, (I), C
27H
23Cl
2NO, (II), and C
27H
23Cl
2NO, (III), adopt sofa conformations. The molecular packing in (I) and (II) is a result of van der Waals interactions, whereas in (III), a C—H
O interaction is also found.
Supporting information
CCDC references: 649097; 649098; 649099
For the preparation of (I), a mixture of (R)-(1-phenylethyl)tetrahydro-
4(1H)-pyridinone (1 mmol 0.5 ml) and benzaldehyde (2 mmol, 0.50 ml) in
alcoholic [specify which alcohol] NaOH (30 ml, 10%) was stirred at room
temperature for 10 min. The separated solid was filtered off and
recrystallized from alcohol (yield 0.740 g, 80%; m.p. 385–386 K). For
the preparation of (II), a mixture of
(R)-(1-phenylethyl)tetrahydro-4(1H)-pyridinone (1 mmol, 0.5 ml)
and 4-chlorobenzaldehyde (2 mmol, 0.69 g) in alcoholic NaOH (30 ml,
10%) was stirred at room temperature for 10 min. The separated solid was
filtered off and recrystallized from alcohol (yield 0.905 g, 83%; m.p.
412–413 K). For the preparation of (III), a mixture of
(R)-(1-phenylethyl)tetrahydro-4(1H)-pyridinone (1 mmol, 0.5 ml)
and 2-chlorobenzaldehyde (2 mmol, 0.55 ml) in alcoholic NaOH (30 ml,
10%) was stirred at room temperature for 10 min. The separated solid was
filtered and recrystallized from alcohol (yield 0.927 g, 85%; m.p.
358–359 K).
In the absence of significant anomalous scattering for compound (I), the
absolute configuration could not be reliably determined; Friedel pairs were
merged and any references to the Flack parameter were removed. The absolute
configuration was established from the configuration of the starting reagents.
For compounds (II) and (III), the absolute configuration expected from the
starting reagents has been confirmed by the refinement of the Flack (1983)
parameter. H atoms were placed at calculated positions and allowed to ride on
their carrier atoms [C—H = 0.93–0.98 Å, and Uiso(H) =
1.2Ueq(C) for CH2 and CH groups, and Uiso(H) =
1.5Ueq(C) for CH3 groups].
For all compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
(I) (
R)-3,5-Bis[(
E)-benzylidene]-1-(1-phenylethyl)piperidin-4-one
top
Crystal data top
C27H25NO | F(000) = 808 |
Mr = 379.48 | Dx = 1.164 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 6.0890 (7) Å | θ = 2–25° |
b = 15.3562 (9) Å | µ = 0.07 mm−1 |
c = 23.1522 (11) Å | T = 293 K |
V = 2164.8 (3) Å3 | Block, colourless |
Z = 4 | 0.19 × 0.17 × 0.12 mm |
Data collection top
Nonius MACH3 four-circle diffractometer | 1421 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω–scans | h = 0→7 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.987, Tmax = 0.992 | l = −1→27 |
2330 measured reflections | 3 standard reflections every 60 min |
2213 independent reflections | intensity decay: none |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0424P)2 + 0.2202P] where P = (Fo2 + 2Fc2)/3 |
2213 reflections | (Δ/σ)max = 0.001 |
263 parameters | Δρmax = 0.11 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C27H25NO | V = 2164.8 (3) Å3 |
Mr = 379.48 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0890 (7) Å | µ = 0.07 mm−1 |
b = 15.3562 (9) Å | T = 293 K |
c = 23.1522 (11) Å | 0.19 × 0.17 × 0.12 mm |
Data collection top
Nonius MACH3 four-circle diffractometer | 1421 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.987, Tmax = 0.992 | 3 standard reflections every 60 min |
2330 measured reflections | intensity decay: none |
2213 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.11 e Å−3 |
2213 reflections | Δρmin = −0.17 e Å−3 |
263 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 0.3698 (5) | 0.35243 (16) | 0.41022 (12) | 0.0451 (7) | |
H2A | 0.3988 | 0.4097 | 0.3944 | 0.054* | |
H2B | 0.4781 | 0.3408 | 0.4400 | 0.054* | |
C3 | 0.1432 (5) | 0.35019 (16) | 0.43599 (10) | 0.0388 (6) | |
C4 | 0.0325 (5) | 0.26432 (17) | 0.44107 (11) | 0.0394 (6) | |
C5 | 0.1429 (5) | 0.18739 (16) | 0.41508 (10) | 0.0398 (6) | |
C6 | 0.3691 (5) | 0.19984 (15) | 0.39133 (12) | 0.0439 (7) | |
H6A | 0.4761 | 0.1946 | 0.4222 | 0.053* | |
H6B | 0.3999 | 0.1551 | 0.3629 | 0.053* | |
C7 | 0.5931 (5) | 0.29374 (17) | 0.33043 (12) | 0.0501 (7) | |
H7 | 0.7171 | 0.2793 | 0.3556 | 0.060* | |
C8 | 0.6272 (8) | 0.3858 (2) | 0.30650 (16) | 0.0905 (13) | |
H8A | 0.6553 | 0.4252 | 0.3378 | 0.136* | |
H8B | 0.4976 | 0.4039 | 0.2862 | 0.136* | |
H8C | 0.7501 | 0.3858 | 0.2805 | 0.136* | |
C31 | 0.0311 (5) | 0.42052 (16) | 0.45274 (11) | 0.0439 (7) | |
H31 | −0.1122 | 0.4107 | 0.4650 | 0.053* | |
C32 | 0.1055 (5) | 0.51147 (17) | 0.45426 (11) | 0.0463 (7) | |
C33 | −0.0375 (6) | 0.57729 (18) | 0.43711 (13) | 0.0592 (9) | |
H33 | −0.1773 | 0.5631 | 0.4239 | 0.071* | |
C34 | 0.0270 (7) | 0.6640 (2) | 0.43955 (15) | 0.0695 (10) | |
H34 | −0.0679 | 0.7076 | 0.4271 | 0.083* | |
C35 | 0.2306 (7) | 0.6853 (2) | 0.46037 (15) | 0.0696 (10) | |
H35 | 0.2732 | 0.7434 | 0.4622 | 0.084* | |
C36 | 0.3712 (6) | 0.62171 (19) | 0.47835 (14) | 0.0641 (9) | |
H36 | 0.5084 | 0.6365 | 0.4931 | 0.077* | |
C37 | 0.3092 (5) | 0.53524 (19) | 0.47465 (12) | 0.0541 (8) | |
H37 | 0.4073 | 0.4922 | 0.4862 | 0.065* | |
C51 | 0.0279 (5) | 0.11336 (16) | 0.41242 (11) | 0.0453 (7) | |
H51 | −0.1154 | 0.1166 | 0.4262 | 0.054* | |
C52 | 0.0965 (5) | 0.02732 (17) | 0.39074 (12) | 0.0479 (7) | |
C53 | 0.3022 (6) | −0.00757 (19) | 0.40145 (14) | 0.0589 (9) | |
H53 | 0.4059 | 0.0250 | 0.4215 | 0.071* | |
C54 | 0.3549 (7) | −0.0907 (2) | 0.38244 (16) | 0.0760 (11) | |
H54 | 0.4930 | −0.1138 | 0.3902 | 0.091* | |
C55 | 0.2031 (8) | −0.1388 (2) | 0.35216 (17) | 0.0814 (13) | |
H55 | 0.2385 | −0.1944 | 0.3392 | 0.098* | |
C56 | 0.0002 (8) | −0.1047 (2) | 0.34112 (17) | 0.0866 (12) | |
H56 | −0.1022 | −0.1369 | 0.3204 | 0.104* | |
C57 | −0.0532 (6) | −0.0225 (2) | 0.36072 (15) | 0.0699 (10) | |
H57 | −0.1927 | −0.0004 | 0.3535 | 0.084* | |
C71 | 0.5879 (5) | 0.22929 (17) | 0.28064 (12) | 0.0473 (7) | |
C72 | 0.4087 (6) | 0.2220 (2) | 0.24545 (14) | 0.0680 (10) | |
H72 | 0.2834 | 0.2548 | 0.2530 | 0.082* | |
C73 | 0.4133 (8) | 0.1658 (3) | 0.19840 (16) | 0.0919 (14) | |
H73 | 0.2908 | 0.1612 | 0.1746 | 0.110* | |
C74 | 0.5960 (10) | 0.1175 (3) | 0.18676 (17) | 0.0969 (16) | |
H74 | 0.5994 | 0.0808 | 0.1548 | 0.116* | |
C75 | 0.7723 (9) | 0.1234 (2) | 0.22221 (18) | 0.0906 (14) | |
H75 | 0.8957 | 0.0894 | 0.2151 | 0.109* | |
C76 | 0.7708 (6) | 0.1793 (2) | 0.26863 (15) | 0.0674 (10) | |
H76 | 0.8941 | 0.1834 | 0.2922 | 0.081* | |
N1 | 0.3870 (4) | 0.28653 (13) | 0.36433 (9) | 0.0436 (6) | |
O1 | −0.1455 (3) | 0.25753 (12) | 0.46554 (8) | 0.0515 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0477 (17) | 0.0371 (14) | 0.0506 (16) | −0.0060 (14) | 0.0067 (15) | −0.0039 (12) |
C3 | 0.0392 (16) | 0.0402 (15) | 0.0370 (13) | 0.0031 (14) | −0.0009 (13) | −0.0003 (11) |
C4 | 0.0359 (16) | 0.0466 (16) | 0.0357 (14) | −0.0012 (14) | −0.0037 (14) | 0.0013 (12) |
C5 | 0.0427 (16) | 0.0379 (14) | 0.0387 (13) | 0.0014 (14) | 0.0014 (14) | 0.0031 (11) |
C6 | 0.0478 (17) | 0.0385 (14) | 0.0455 (15) | −0.0006 (14) | 0.0030 (15) | −0.0046 (12) |
C7 | 0.0477 (19) | 0.0540 (16) | 0.0486 (16) | −0.0072 (15) | 0.0110 (15) | −0.0044 (14) |
C8 | 0.130 (4) | 0.060 (2) | 0.082 (2) | −0.029 (3) | 0.049 (3) | −0.0129 (18) |
C31 | 0.0390 (17) | 0.0457 (16) | 0.0470 (16) | 0.0030 (14) | 0.0010 (14) | −0.0014 (13) |
C32 | 0.054 (2) | 0.0398 (15) | 0.0454 (16) | 0.0038 (15) | 0.0050 (15) | −0.0047 (12) |
C33 | 0.064 (2) | 0.0473 (18) | 0.066 (2) | 0.0128 (17) | −0.0081 (18) | −0.0050 (15) |
C34 | 0.089 (3) | 0.0456 (19) | 0.074 (2) | 0.023 (2) | 0.000 (2) | −0.0001 (17) |
C35 | 0.094 (3) | 0.0416 (18) | 0.073 (2) | −0.004 (2) | 0.006 (2) | −0.0079 (17) |
C36 | 0.067 (2) | 0.0505 (19) | 0.075 (2) | −0.0021 (19) | −0.004 (2) | −0.0109 (16) |
C37 | 0.063 (2) | 0.0419 (17) | 0.0574 (18) | 0.0055 (16) | −0.0034 (17) | −0.0064 (14) |
C51 | 0.0449 (17) | 0.0437 (15) | 0.0474 (16) | −0.0045 (15) | 0.0055 (14) | 0.0006 (12) |
C52 | 0.059 (2) | 0.0367 (14) | 0.0483 (16) | −0.0107 (15) | 0.0091 (16) | 0.0020 (13) |
C53 | 0.060 (2) | 0.0471 (17) | 0.069 (2) | −0.0005 (16) | 0.0002 (18) | −0.0005 (16) |
C54 | 0.081 (3) | 0.0478 (19) | 0.099 (3) | 0.012 (2) | 0.024 (2) | 0.0063 (18) |
C55 | 0.117 (4) | 0.0423 (19) | 0.085 (3) | −0.011 (2) | 0.036 (3) | −0.0116 (18) |
C56 | 0.108 (4) | 0.057 (2) | 0.095 (3) | −0.017 (2) | −0.003 (3) | −0.023 (2) |
C57 | 0.068 (2) | 0.0512 (18) | 0.090 (2) | −0.0106 (18) | −0.003 (2) | −0.0094 (18) |
C71 | 0.055 (2) | 0.0476 (16) | 0.0399 (15) | −0.0050 (16) | 0.0083 (15) | 0.0022 (13) |
C72 | 0.062 (2) | 0.084 (2) | 0.058 (2) | −0.007 (2) | −0.0003 (19) | −0.0052 (18) |
C73 | 0.107 (4) | 0.114 (3) | 0.054 (2) | −0.043 (3) | −0.002 (2) | −0.016 (2) |
C74 | 0.157 (5) | 0.072 (3) | 0.062 (2) | −0.031 (3) | 0.036 (3) | −0.023 (2) |
C75 | 0.126 (4) | 0.068 (2) | 0.077 (3) | 0.017 (3) | 0.036 (3) | −0.007 (2) |
C76 | 0.068 (2) | 0.074 (2) | 0.060 (2) | 0.012 (2) | 0.0105 (18) | 0.0015 (18) |
N1 | 0.0489 (14) | 0.0380 (11) | 0.0440 (12) | −0.0014 (12) | 0.0084 (11) | −0.0010 (10) |
O1 | 0.0429 (11) | 0.0520 (11) | 0.0596 (11) | −0.0032 (10) | 0.0086 (11) | −0.0037 (9) |
Geometric parameters (Å, º) top
C2—N1 | 1.471 (3) | C35—H35 | 0.9300 |
C2—C3 | 1.503 (4) | C36—C37 | 1.383 (4) |
C2—H2A | 0.9700 | C36—H36 | 0.9300 |
C2—H2B | 0.9700 | C37—H37 | 0.9300 |
C3—C31 | 1.335 (3) | C51—C52 | 1.474 (4) |
C3—C4 | 1.486 (4) | C51—H51 | 0.9300 |
C4—O1 | 1.228 (3) | C52—C57 | 1.378 (4) |
C4—C5 | 1.486 (4) | C52—C53 | 1.385 (4) |
C5—C51 | 1.337 (4) | C53—C54 | 1.388 (4) |
C5—C6 | 1.495 (4) | C53—H53 | 0.9300 |
C6—N1 | 1.475 (3) | C54—C55 | 1.376 (5) |
C6—H6A | 0.9700 | C54—H54 | 0.9300 |
C6—H6B | 0.9700 | C55—C56 | 1.366 (5) |
C7—N1 | 1.484 (3) | C55—H55 | 0.9300 |
C7—C71 | 1.520 (4) | C56—C57 | 1.380 (5) |
C7—C8 | 1.532 (4) | C56—H56 | 0.9300 |
C7—H7 | 0.9800 | C57—H57 | 0.9300 |
C8—H8A | 0.9600 | C71—C72 | 1.367 (4) |
C8—H8B | 0.9600 | C71—C76 | 1.381 (4) |
C8—H8C | 0.9600 | C72—C73 | 1.390 (5) |
C31—C32 | 1.469 (4) | C72—H72 | 0.9300 |
C31—H31 | 0.9300 | C73—C74 | 1.365 (6) |
C32—C37 | 1.376 (4) | C73—H73 | 0.9300 |
C32—C33 | 1.392 (4) | C74—C75 | 1.354 (6) |
C33—C34 | 1.390 (4) | C74—H74 | 0.9300 |
C33—H33 | 0.9300 | C75—C76 | 1.375 (5) |
C34—C35 | 1.369 (5) | C75—H75 | 0.9300 |
C34—H34 | 0.9300 | C76—H76 | 0.9300 |
C35—C36 | 1.363 (5) | | |
| | | |
N1—C2—C3 | 109.6 (2) | C35—C36—C37 | 119.8 (3) |
N1—C2—H2A | 109.7 | C35—C36—H36 | 120.1 |
C3—C2—H2A | 109.7 | C37—C36—H36 | 120.1 |
N1—C2—H2B | 109.7 | C32—C37—C36 | 121.5 (3) |
C3—C2—H2B | 109.7 | C32—C37—H37 | 119.3 |
H2A—C2—H2B | 108.2 | C36—C37—H37 | 119.3 |
C31—C3—C4 | 117.6 (3) | C5—C51—C52 | 129.0 (3) |
C31—C3—C2 | 124.5 (3) | C5—C51—H51 | 115.5 |
C4—C3—C2 | 117.9 (2) | C52—C51—H51 | 115.5 |
O1—C4—C3 | 120.8 (2) | C57—C52—C53 | 118.3 (3) |
O1—C4—C5 | 121.2 (2) | C57—C52—C51 | 118.8 (3) |
C3—C4—C5 | 117.9 (2) | C53—C52—C51 | 122.8 (3) |
C51—C5—C4 | 117.2 (3) | C52—C53—C54 | 120.6 (3) |
C51—C5—C6 | 125.0 (2) | C52—C53—H53 | 119.7 |
C4—C5—C6 | 117.6 (2) | C54—C53—H53 | 119.7 |
N1—C6—C5 | 109.8 (2) | C55—C54—C53 | 120.0 (4) |
N1—C6—H6A | 109.7 | C55—C54—H54 | 120.0 |
C5—C6—H6A | 109.7 | C53—C54—H54 | 120.0 |
N1—C6—H6B | 109.7 | C56—C55—C54 | 119.8 (3) |
C5—C6—H6B | 109.7 | C56—C55—H55 | 120.1 |
H6A—C6—H6B | 108.2 | C54—C55—H55 | 120.1 |
N1—C7—C71 | 109.6 (2) | C55—C56—C57 | 120.1 (4) |
N1—C7—C8 | 112.0 (3) | C55—C56—H56 | 119.9 |
C71—C7—C8 | 109.2 (2) | C57—C56—H56 | 119.9 |
N1—C7—H7 | 108.7 | C52—C57—C56 | 121.2 (4) |
C71—C7—H7 | 108.7 | C52—C57—H57 | 119.4 |
C8—C7—H7 | 108.7 | C56—C57—H57 | 119.4 |
C7—C8—H8A | 109.5 | C72—C71—C76 | 118.6 (3) |
C7—C8—H8B | 109.5 | C72—C71—C7 | 121.5 (3) |
H8A—C8—H8B | 109.5 | C76—C71—C7 | 119.9 (3) |
C7—C8—H8C | 109.5 | C71—C72—C73 | 120.1 (4) |
H8A—C8—H8C | 109.5 | C71—C72—H72 | 119.9 |
H8B—C8—H8C | 109.5 | C73—C72—H72 | 119.9 |
C3—C31—C32 | 128.2 (3) | C74—C73—C72 | 120.6 (4) |
C3—C31—H31 | 115.9 | C74—C73—H73 | 119.7 |
C32—C31—H31 | 115.9 | C72—C73—H73 | 119.7 |
C37—C32—C33 | 118.0 (3) | C75—C74—C73 | 119.3 (3) |
C37—C32—C31 | 122.6 (3) | C75—C74—H74 | 120.3 |
C33—C32—C31 | 119.4 (3) | C73—C74—H74 | 120.3 |
C34—C33—C32 | 120.5 (3) | C74—C75—C76 | 120.7 (4) |
C34—C33—H33 | 119.8 | C74—C75—H75 | 119.6 |
C32—C33—H33 | 119.8 | C76—C75—H75 | 119.6 |
C35—C34—C33 | 119.9 (3) | C75—C76—C71 | 120.6 (4) |
C35—C34—H34 | 120.0 | C75—C76—H76 | 119.7 |
C33—C34—H34 | 120.0 | C71—C76—H76 | 119.7 |
C36—C35—C34 | 120.3 (3) | C2—N1—C6 | 108.03 (19) |
C36—C35—H35 | 119.8 | C2—N1—C7 | 113.0 (2) |
C34—C35—H35 | 119.8 | C6—N1—C7 | 110.7 (2) |
| | | |
N1—C2—C3—C31 | −142.0 (3) | C57—C52—C53—C54 | −0.2 (5) |
N1—C2—C3—C4 | 35.4 (3) | C51—C52—C53—C54 | 176.8 (3) |
C31—C3—C4—O1 | −7.7 (4) | C52—C53—C54—C55 | 0.7 (5) |
C2—C3—C4—O1 | 174.6 (2) | C53—C54—C55—C56 | −0.3 (5) |
C31—C3—C4—C5 | 171.6 (2) | C54—C55—C56—C57 | −0.6 (6) |
C2—C3—C4—C5 | −6.0 (3) | C53—C52—C57—C56 | −0.7 (5) |
O1—C4—C5—C51 | 8.9 (4) | C51—C52—C57—C56 | −177.9 (3) |
C3—C4—C5—C51 | −170.4 (2) | C55—C56—C57—C52 | 1.1 (6) |
O1—C4—C5—C6 | −174.1 (2) | N1—C7—C71—C72 | 47.7 (3) |
C3—C4—C5—C6 | 6.6 (3) | C8—C7—C71—C72 | −75.3 (4) |
C51—C5—C6—N1 | 140.2 (3) | N1—C7—C71—C76 | −135.2 (3) |
C4—C5—C6—N1 | −36.5 (3) | C8—C7—C71—C76 | 101.8 (4) |
C4—C3—C31—C32 | 177.3 (3) | C76—C71—C72—C73 | −0.6 (5) |
C2—C3—C31—C32 | −5.2 (5) | C7—C71—C72—C73 | 176.5 (3) |
C3—C31—C32—C37 | −43.6 (5) | C71—C72—C73—C74 | 0.0 (6) |
C3—C31—C32—C33 | 139.5 (3) | C72—C73—C74—C75 | 1.2 (6) |
C37—C32—C33—C34 | 1.4 (5) | C73—C74—C75—C76 | −1.7 (6) |
C31—C32—C33—C34 | 178.4 (3) | C74—C75—C76—C71 | 1.1 (6) |
C32—C33—C34—C35 | −1.7 (5) | C72—C71—C76—C75 | 0.1 (5) |
C33—C34—C35—C36 | 0.5 (6) | C7—C71—C76—C75 | −177.1 (3) |
C34—C35—C36—C37 | 1.1 (5) | C3—C2—N1—C6 | −66.3 (3) |
C33—C32—C37—C36 | 0.2 (5) | C3—C2—N1—C7 | 170.9 (2) |
C31—C32—C37—C36 | −176.7 (3) | C5—C6—N1—C2 | 67.1 (3) |
C35—C36—C37—C32 | −1.4 (5) | C5—C6—N1—C7 | −168.7 (2) |
C4—C5—C51—C52 | −178.1 (3) | C71—C7—N1—C2 | −174.7 (2) |
C6—C5—C51—C52 | 5.2 (5) | C8—C7—N1—C2 | −53.3 (3) |
C5—C51—C52—C57 | −142.3 (3) | C71—C7—N1—C6 | 64.0 (3) |
C5—C51—C52—C53 | 40.7 (4) | C8—C7—N1—C6 | −174.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···O1 | 0.93 | 2.36 | 2.740 (3) | 104 |
C51—H51···O1 | 0.93 | 2.36 | 2.744 (3) | 105 |
C55—H55···Cg1i | 0.93 | 2.84 | 3.725 (4) | 159 |
C74—H74···Cg2i | 0.93 | 2.97 | 3.645 (5) | 130 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
(II) 3,5-bis[(
E)-4-chlorobenzylidene]-1-[(
R)-1-phenylethyl]piperidin-4-one
top
Crystal data top
C27H23Cl2NO | F(000) = 468 |
Mr = 448.36 | Dx = 1.323 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 6.6409 (3) Å | θ = 2–25° |
b = 12.9466 (1) Å | µ = 0.31 mm−1 |
c = 13.1274 (8) Å | T = 293 K |
β = 94.200 (16)° | Block, colourless |
V = 1125.62 (9) Å3 | 0.22 × 0.13 × 0.12 mm |
Z = 2 | |
Data collection top
Nonius MACH3 four-circle diffractometer | 1918 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.078 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω–scans | h = −3→7 |
Absorption correction: ψ scan (North et al., 1968) | k = −2→15 |
Tmin = 0.935, Tmax = 0.964 | l = −15→15 |
2678 measured reflections | 3 standard reflections every 60 min |
2256 independent reflections | intensity decay: none |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.1087P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2256 reflections | Δρmax = 0.34 e Å−3 |
281 parameters | Δρmin = −0.40 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 189 Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.08 (10) |
Crystal data top
C27H23Cl2NO | V = 1125.62 (9) Å3 |
Mr = 448.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.6409 (3) Å | µ = 0.31 mm−1 |
b = 12.9466 (1) Å | T = 293 K |
c = 13.1274 (8) Å | 0.22 × 0.13 × 0.12 mm |
β = 94.200 (16)° | |
Data collection top
Nonius MACH3 four-circle diffractometer | 1918 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.078 |
Tmin = 0.935, Tmax = 0.964 | 3 standard reflections every 60 min |
2678 measured reflections | intensity decay: none |
2256 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.139 | Δρmax = 0.34 e Å−3 |
S = 1.07 | Δρmin = −0.40 e Å−3 |
2256 reflections | Absolute structure: Flack (1983), 189 Friedel pairs? |
281 parameters | Absolute structure parameter: −0.08 (10) |
1 restraint | |
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 | |
C2 | 0.7147 (6) | 0.3566 (4) | 0.2292 (3) | 0.0422 (9) | |
H2A | 0.6093 | 0.3399 | 0.2739 | 0.051* | |
H2B | 0.6559 | 0.3991 | 0.1739 | 0.051* | |
C3 | 0.8809 (6) | 0.4158 (3) | 0.2882 (3) | 0.0404 (9) | |
C4 | 1.0596 (6) | 0.3536 (4) | 0.3292 (3) | 0.0433 (9) | |
C5 | 1.0356 (6) | 0.2392 (3) | 0.3332 (3) | 0.0395 (9) | |
C6 | 0.8580 (6) | 0.1932 (4) | 0.2718 (3) | 0.0388 (9) | |
H6A | 0.8950 | 0.1265 | 0.2451 | 0.047* | |
H6B | 0.7475 | 0.1829 | 0.3152 | 0.047* | |
C7 | 0.6488 (6) | 0.2134 (4) | 0.1104 (3) | 0.0439 (10) | |
H7 | 0.6212 | 0.2652 | 0.0568 | 0.053* | |
C8 | 0.4443 (7) | 0.1857 (5) | 0.1501 (4) | 0.0677 (15) | |
H8A | 0.4634 | 0.1347 | 0.2030 | 0.102* | |
H8B | 0.3567 | 0.1587 | 0.0951 | 0.102* | |
H8C | 0.3847 | 0.2465 | 0.1771 | 0.102* | |
C31 | 0.8819 (7) | 0.5177 (4) | 0.3060 (3) | 0.0445 (10) | |
H31 | 0.9953 | 0.5428 | 0.3439 | 0.053* | |
C32 | 0.7287 (7) | 0.5955 (4) | 0.2738 (3) | 0.0446 (10) | |
C37 | 0.5243 (7) | 0.5735 (4) | 0.2522 (3) | 0.0502 (10) | |
H37 | 0.4772 | 0.5067 | 0.2613 | 0.060* | |
C36 | 0.3915 (7) | 0.6498 (4) | 0.2175 (4) | 0.0509 (11) | |
H36 | 0.2561 | 0.6341 | 0.2019 | 0.061* | |
C35 | 0.4591 (7) | 0.7486 (4) | 0.2060 (3) | 0.0491 (10) | |
C34 | 0.6610 (8) | 0.7744 (4) | 0.2283 (4) | 0.0588 (12) | |
H34 | 0.7063 | 0.8417 | 0.2206 | 0.071* | |
C33 | 0.7915 (7) | 0.6970 (4) | 0.2621 (4) | 0.0562 (12) | |
H33 | 0.9267 | 0.7132 | 0.2777 | 0.067* | |
C51 | 1.1738 (6) | 0.1862 (4) | 0.3903 (3) | 0.0457 (10) | |
H51 | 1.2768 | 0.2256 | 0.4225 | 0.055* | |
C52 | 1.1874 (6) | 0.0746 (4) | 0.4098 (3) | 0.0449 (10) | |
C57 | 1.3770 (7) | 0.0315 (5) | 0.4363 (5) | 0.0645 (14) | |
H57 | 1.4888 | 0.0749 | 0.4432 | 0.077* | |
C56 | 1.4041 (8) | −0.0713 (5) | 0.4523 (4) | 0.0611 (14) | |
H56 | 1.5326 | −0.0976 | 0.4691 | 0.073* | |
C55 | 1.2392 (7) | −0.1364 (4) | 0.4436 (3) | 0.0479 (11) | |
C54 | 1.0470 (7) | −0.0973 (4) | 0.4210 (3) | 0.0488 (10) | |
H54 | 0.9356 | −0.1411 | 0.4167 | 0.059* | |
C53 | 1.0228 (6) | 0.0075 (4) | 0.4048 (3) | 0.0461 (10) | |
H53 | 0.8936 | 0.0339 | 0.3903 | 0.055* | |
C71 | 0.7509 (6) | 0.1236 (4) | 0.0606 (3) | 0.0409 (9) | |
C72 | 0.9345 (7) | 0.1385 (4) | 0.0186 (3) | 0.0489 (10) | |
H72 | 0.9945 | 0.2034 | 0.0225 | 0.059* | |
C73 | 1.0301 (8) | 0.0590 (5) | −0.0287 (4) | 0.0613 (14) | |
H73 | 1.1534 | 0.0710 | −0.0560 | 0.074* | |
C74 | 0.9441 (9) | −0.0382 (5) | −0.0360 (4) | 0.0628 (14) | |
H74 | 1.0089 | −0.0921 | −0.0671 | 0.075* | |
C75 | 0.7608 (9) | −0.0535 (5) | 0.0038 (4) | 0.0681 (14) | |
H75 | 0.6999 | −0.1182 | −0.0015 | 0.082* | |
C76 | 0.6662 (8) | 0.0255 (4) | 0.0511 (4) | 0.0595 (13) | |
H76 | 0.5423 | 0.0131 | 0.0776 | 0.071* | |
Cl1 | 0.2885 (2) | 0.84431 (11) | 0.16353 (11) | 0.0683 (4) | |
Cl2 | 1.2708 (2) | −0.26869 (10) | 0.45888 (10) | 0.0653 (4) | |
N1 | 0.7940 (5) | 0.2619 (3) | 0.1878 (2) | 0.0391 (8) | |
O1 | 1.2164 (5) | 0.3962 (3) | 0.3610 (3) | 0.0639 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.041 (2) | 0.045 (2) | 0.041 (2) | −0.001 (2) | −0.0006 (16) | −0.0056 (19) |
C3 | 0.039 (2) | 0.044 (2) | 0.037 (2) | −0.0029 (18) | 0.0016 (16) | 0.0024 (18) |
C4 | 0.0357 (19) | 0.049 (2) | 0.044 (2) | −0.004 (2) | −0.0015 (16) | 0.003 (2) |
C5 | 0.0378 (19) | 0.047 (2) | 0.0337 (17) | −0.0020 (19) | −0.0002 (15) | −0.0011 (18) |
C6 | 0.039 (2) | 0.044 (2) | 0.0322 (18) | −0.0030 (18) | −0.0060 (15) | 0.0007 (17) |
C7 | 0.0402 (19) | 0.049 (3) | 0.0407 (19) | 0.0018 (19) | −0.0085 (16) | −0.0043 (19) |
C8 | 0.040 (2) | 0.081 (4) | 0.081 (4) | −0.002 (3) | −0.005 (2) | −0.031 (3) |
C31 | 0.042 (2) | 0.046 (3) | 0.044 (2) | −0.006 (2) | −0.0017 (17) | −0.0019 (19) |
C32 | 0.045 (2) | 0.045 (2) | 0.043 (2) | −0.0005 (19) | 0.0004 (17) | −0.0068 (19) |
C37 | 0.049 (2) | 0.044 (2) | 0.059 (2) | −0.003 (2) | 0.0106 (19) | −0.004 (2) |
C36 | 0.042 (2) | 0.052 (3) | 0.058 (2) | 0.002 (2) | 0.0020 (18) | −0.005 (2) |
C35 | 0.052 (2) | 0.051 (3) | 0.043 (2) | 0.007 (2) | −0.0017 (18) | 0.003 (2) |
C34 | 0.061 (3) | 0.042 (3) | 0.072 (3) | −0.006 (2) | −0.003 (2) | 0.002 (2) |
C33 | 0.047 (2) | 0.049 (3) | 0.070 (3) | −0.006 (2) | −0.010 (2) | −0.002 (2) |
C51 | 0.040 (2) | 0.052 (3) | 0.044 (2) | 0.000 (2) | −0.0091 (17) | −0.004 (2) |
C52 | 0.038 (2) | 0.052 (2) | 0.043 (2) | 0.004 (2) | −0.0113 (16) | 0.0046 (19) |
C57 | 0.039 (2) | 0.063 (3) | 0.089 (4) | 0.000 (2) | −0.014 (2) | 0.002 (3) |
C56 | 0.043 (2) | 0.067 (3) | 0.071 (3) | 0.011 (2) | −0.016 (2) | 0.011 (3) |
C55 | 0.056 (3) | 0.048 (3) | 0.039 (2) | 0.012 (2) | −0.0019 (18) | 0.0052 (19) |
C54 | 0.044 (2) | 0.054 (3) | 0.047 (2) | −0.003 (2) | −0.0040 (18) | 0.003 (2) |
C53 | 0.038 (2) | 0.050 (3) | 0.049 (2) | 0.0052 (19) | −0.0052 (17) | 0.007 (2) |
C71 | 0.045 (2) | 0.046 (2) | 0.0296 (17) | 0.0010 (19) | −0.0102 (15) | −0.0006 (17) |
C72 | 0.049 (2) | 0.052 (3) | 0.044 (2) | −0.003 (2) | −0.0047 (18) | −0.007 (2) |
C73 | 0.055 (3) | 0.079 (4) | 0.049 (2) | 0.012 (3) | 0.002 (2) | −0.005 (3) |
C74 | 0.083 (4) | 0.057 (3) | 0.048 (2) | 0.016 (3) | −0.002 (2) | −0.009 (2) |
C75 | 0.085 (4) | 0.050 (3) | 0.068 (3) | −0.004 (3) | −0.002 (3) | −0.010 (3) |
C76 | 0.063 (3) | 0.055 (3) | 0.060 (3) | −0.007 (3) | 0.005 (2) | 0.001 (2) |
Cl1 | 0.0672 (8) | 0.0590 (7) | 0.0771 (8) | 0.0133 (6) | −0.0056 (6) | 0.0101 (7) |
Cl2 | 0.0813 (9) | 0.0532 (7) | 0.0610 (7) | 0.0189 (7) | 0.0031 (6) | 0.0127 (6) |
N1 | 0.0396 (17) | 0.0389 (18) | 0.0377 (16) | 0.0001 (14) | −0.0047 (13) | −0.0018 (14) |
O1 | 0.0466 (19) | 0.052 (2) | 0.090 (3) | −0.0103 (16) | −0.0148 (16) | 0.0011 (19) |
Geometric parameters (Å, º) top
C2—N1 | 1.456 (6) | C35—Cl1 | 1.742 (5) |
C2—C3 | 1.511 (6) | C34—C33 | 1.377 (7) |
C2—H2A | 0.9700 | C34—H34 | 0.9300 |
C2—H2B | 0.9700 | C33—H33 | 0.9300 |
C3—C31 | 1.339 (6) | C51—C52 | 1.468 (7) |
C3—C4 | 1.501 (6) | C51—H51 | 0.9300 |
C4—O1 | 1.224 (5) | C52—C53 | 1.395 (7) |
C4—C5 | 1.491 (6) | C52—C57 | 1.397 (6) |
C5—C51 | 1.332 (6) | C57—C56 | 1.358 (9) |
C5—C6 | 1.502 (5) | C57—H57 | 0.9300 |
C6—N1 | 1.456 (5) | C56—C55 | 1.380 (7) |
C6—H6A | 0.9700 | C56—H56 | 0.9300 |
C6—H6B | 0.9700 | C55—C54 | 1.385 (6) |
C7—N1 | 1.487 (5) | C55—Cl2 | 1.736 (5) |
C7—C71 | 1.518 (6) | C54—C53 | 1.381 (7) |
C7—C8 | 1.532 (7) | C54—H54 | 0.9300 |
C7—H7 | 0.9800 | C53—H53 | 0.9300 |
C8—H8A | 0.9600 | C71—C72 | 1.388 (6) |
C8—H8B | 0.9600 | C71—C76 | 1.391 (7) |
C8—H8C | 0.9600 | C72—C73 | 1.381 (7) |
C31—C32 | 1.471 (6) | C72—H72 | 0.9300 |
C31—H31 | 0.9300 | C73—C74 | 1.383 (9) |
C32—C33 | 1.391 (7) | C73—H73 | 0.9300 |
C32—C37 | 1.396 (6) | C74—C75 | 1.374 (8) |
C37—C36 | 1.379 (7) | C74—H74 | 0.9300 |
C37—H37 | 0.9300 | C75—C76 | 1.373 (8) |
C36—C35 | 1.368 (7) | C75—H75 | 0.9300 |
C36—H36 | 0.9300 | C76—H76 | 0.9300 |
C35—C34 | 1.392 (7) | | |
| | | |
N1—C2—C3 | 110.4 (3) | C33—C34—C35 | 117.9 (5) |
N1—C2—H2A | 109.6 | C33—C34—H34 | 121.1 |
C3—C2—H2A | 109.6 | C35—C34—H34 | 121.1 |
N1—C2—H2B | 109.6 | C34—C33—C32 | 122.5 (4) |
C3—C2—H2B | 109.6 | C34—C33—H33 | 118.8 |
H2A—C2—H2B | 108.1 | C32—C33—H33 | 118.8 |
C31—C3—C4 | 118.2 (4) | C5—C51—C52 | 129.5 (4) |
C31—C3—C2 | 125.7 (4) | C5—C51—H51 | 115.2 |
C4—C3—C2 | 116.1 (4) | C52—C51—H51 | 115.2 |
O1—C4—C5 | 121.7 (4) | C53—C52—C57 | 116.9 (5) |
O1—C4—C3 | 120.7 (4) | C53—C52—C51 | 124.5 (4) |
C5—C4—C3 | 117.5 (4) | C57—C52—C51 | 118.6 (5) |
C51—C5—C4 | 117.4 (4) | C56—C57—C52 | 122.5 (5) |
C51—C5—C6 | 125.3 (4) | C56—C57—H57 | 118.8 |
C4—C5—C6 | 117.2 (4) | C52—C57—H57 | 118.8 |
N1—C6—C5 | 109.7 (3) | C57—C56—C55 | 119.4 (5) |
N1—C6—H6A | 109.7 | C57—C56—H56 | 120.3 |
C5—C6—H6A | 109.7 | C55—C56—H56 | 120.3 |
N1—C6—H6B | 109.7 | C56—C55—C54 | 120.6 (5) |
C5—C6—H6B | 109.7 | C56—C55—Cl2 | 120.3 (4) |
H6A—C6—H6B | 108.2 | C54—C55—Cl2 | 119.1 (4) |
N1—C7—C71 | 109.3 (3) | C53—C54—C55 | 119.1 (4) |
N1—C7—C8 | 114.4 (4) | C53—C54—H54 | 120.4 |
C71—C7—C8 | 113.7 (4) | C55—C54—H54 | 120.4 |
N1—C7—H7 | 106.3 | C54—C53—C52 | 121.5 (4) |
C71—C7—H7 | 106.3 | C54—C53—H53 | 119.2 |
C8—C7—H7 | 106.3 | C52—C53—H53 | 119.2 |
C7—C8—H8A | 109.5 | C72—C71—C76 | 116.9 (4) |
C7—C8—H8B | 109.5 | C72—C71—C7 | 119.8 (4) |
H8A—C8—H8B | 109.5 | C76—C71—C7 | 123.2 (4) |
C7—C8—H8C | 109.5 | C73—C72—C71 | 121.4 (5) |
H8A—C8—H8C | 109.5 | C73—C72—H72 | 119.3 |
H8B—C8—H8C | 109.5 | C71—C72—H72 | 119.3 |
C3—C31—C32 | 129.0 (4) | C72—C73—C74 | 120.5 (5) |
C3—C31—H31 | 115.5 | C72—C73—H73 | 119.7 |
C32—C31—H31 | 115.5 | C74—C73—H73 | 119.7 |
C33—C32—C37 | 117.7 (4) | C75—C74—C73 | 118.6 (5) |
C33—C32—C31 | 118.2 (4) | C75—C74—H74 | 120.7 |
C37—C32—C31 | 124.1 (4) | C73—C74—H74 | 120.7 |
C36—C37—C32 | 120.7 (5) | C76—C75—C74 | 120.8 (5) |
C36—C37—H37 | 119.7 | C76—C75—H75 | 119.6 |
C32—C37—H37 | 119.7 | C74—C75—H75 | 119.6 |
C35—C36—C37 | 120.0 (4) | C75—C76—C71 | 121.7 (5) |
C35—C36—H36 | 120.0 | C75—C76—H76 | 119.1 |
C37—C36—H36 | 120.0 | C71—C76—H76 | 119.1 |
C36—C35—C34 | 121.3 (4) | C2—N1—C6 | 109.0 (3) |
C36—C35—Cl1 | 119.3 (3) | C2—N1—C7 | 112.1 (3) |
C34—C35—Cl1 | 119.4 (4) | C6—N1—C7 | 113.5 (3) |
| | | |
N1—C2—C3—C31 | 155.7 (4) | C53—C52—C57—C56 | 2.8 (8) |
N1—C2—C3—C4 | −23.8 (5) | C51—C52—C57—C56 | −177.8 (5) |
C31—C3—C4—O1 | −13.3 (6) | C52—C57—C56—C55 | −0.8 (9) |
C2—C3—C4—O1 | 166.3 (4) | C57—C56—C55—C54 | −1.5 (8) |
C31—C3—C4—C5 | 164.5 (4) | C57—C56—C55—Cl2 | 177.5 (5) |
C2—C3—C4—C5 | −15.9 (5) | C56—C55—C54—C53 | 1.5 (7) |
O1—C4—C5—C51 | 12.9 (6) | Cl2—C55—C54—C53 | −177.5 (4) |
C3—C4—C5—C51 | −164.8 (4) | C55—C54—C53—C52 | 0.6 (7) |
O1—C4—C5—C6 | −166.6 (4) | C57—C52—C53—C54 | −2.7 (7) |
C3—C4—C5—C6 | 15.7 (5) | C51—C52—C53—C54 | 177.9 (5) |
C51—C5—C6—N1 | −155.1 (4) | N1—C7—C71—C72 | −52.7 (5) |
C4—C5—C6—N1 | 24.4 (5) | C8—C7—C71—C72 | 178.2 (4) |
C4—C3—C31—C32 | 179.3 (4) | N1—C7—C71—C76 | 129.6 (4) |
C2—C3—C31—C32 | −0.2 (8) | C8—C7—C71—C76 | 0.4 (6) |
C3—C31—C32—C33 | −153.3 (5) | C76—C71—C72—C73 | −1.1 (6) |
C3—C31—C32—C37 | 25.3 (7) | C7—C71—C72—C73 | −179.0 (4) |
C33—C32—C37—C36 | 1.9 (7) | C71—C72—C73—C74 | 0.3 (7) |
C31—C32—C37—C36 | −176.7 (4) | C72—C73—C74—C75 | 0.8 (7) |
C32—C37—C36—C35 | −1.3 (7) | C73—C74—C75—C76 | −1.0 (8) |
C37—C36—C35—C34 | 0.3 (7) | C74—C75—C76—C71 | 0.2 (8) |
C37—C36—C35—Cl1 | −179.2 (3) | C72—C71—C76—C75 | 0.9 (7) |
C36—C35—C34—C33 | 0.2 (7) | C7—C71—C76—C75 | 178.7 (4) |
Cl1—C35—C34—C33 | 179.7 (4) | C3—C2—N1—C6 | 66.5 (4) |
C35—C34—C33—C32 | 0.4 (8) | C3—C2—N1—C7 | −167.1 (3) |
C37—C32—C33—C34 | −1.4 (7) | C5—C6—N1—C2 | −66.6 (4) |
C31—C32—C33—C34 | 177.2 (5) | C5—C6—N1—C7 | 167.7 (3) |
C4—C5—C51—C52 | 178.9 (4) | C71—C7—N1—C2 | 172.6 (3) |
C6—C5—C51—C52 | −1.6 (7) | C8—C7—N1—C2 | −58.6 (5) |
C5—C51—C52—C53 | −26.0 (8) | C71—C7—N1—C6 | −63.4 (4) |
C5—C51—C52—C57 | 154.6 (5) | C8—C7—N1—C6 | 65.4 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···O1 | 0.93 | 2.40 | 2.774 (6) | 104 |
C51—H51···O1 | 0.93 | 2.38 | 2.763 (6) | 105 |
(III) 3,5-bis[(
E)-2-chlorobenzylidene]-1-[(
R)-1-phenylethyl]piperidin-4-one
top
Crystal data top
C27H23Cl2NO | F(000) = 936 |
Mr = 448.36 | Dx = 1.273 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 25 reflections |
a = 25.746 (5) Å | θ = 2–25° |
b = 6.1251 (9) Å | µ = 0.30 mm−1 |
c = 16.1829 (19) Å | T = 293 K |
β = 113.55 (1)° | Block, colourless |
V = 2339.4 (7) Å3 | 0.22 × 0.18 × 0.11 mm |
Z = 4 | |
Data collection top
Nonius MACH3 four-circle diffractometer | 1990 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
ω–scans | h = 0→30 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→7 |
Tmin = 0.938, Tmax = 0.968 | l = −19→17 |
2735 measured reflections | 3 standard reflections every 60 min |
2680 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0336P)2 + 1.3089P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.086 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2680 reflections | Δρmin = −0.23 e Å−3 |
282 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0017 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 407 Friedel pairs? |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.04 (9) |
Crystal data top
C27H23Cl2NO | V = 2339.4 (7) Å3 |
Mr = 448.36 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 25.746 (5) Å | µ = 0.30 mm−1 |
b = 6.1251 (9) Å | T = 293 K |
c = 16.1829 (19) Å | 0.22 × 0.18 × 0.11 mm |
β = 113.55 (1)° | |
Data collection top
Nonius MACH3 four-circle diffractometer | 1990 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.014 |
Tmin = 0.938, Tmax = 0.968 | 3 standard reflections every 60 min |
2735 measured reflections | intensity decay: none |
2680 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.086 | Δρmax = 0.29 e Å−3 |
S = 1.04 | Δρmin = −0.23 e Å−3 |
2680 reflections | Absolute structure: Flack (1983), 407 Friedel pairs? |
282 parameters | Absolute structure parameter: −0.04 (9) |
1 restraint | |
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 | |
O1 | 0.21215 (9) | 0.6348 (4) | 0.46839 (13) | 0.0487 (6) | |
N1 | 0.12083 (10) | 0.0660 (5) | 0.40098 (15) | 0.0409 (6) | |
Cl1 | 0.07738 (5) | 0.7167 (2) | 0.61796 (9) | 0.0983 (4) | |
Cl2 | 0.11540 (5) | 0.7128 (2) | 0.13066 (7) | 0.0981 (4) | |
C2 | 0.15440 (12) | 0.1038 (6) | 0.49819 (19) | 0.0418 (8) | |
C3 | 0.17134 (11) | 0.3401 (6) | 0.51699 (19) | 0.0371 (8) | |
C4 | 0.18959 (11) | 0.4554 (6) | 0.45188 (19) | 0.0383 (7) | |
C5 | 0.17932 (11) | 0.3425 (6) | 0.36435 (19) | 0.0382 (8) | |
C6 | 0.15883 (12) | 0.1083 (6) | 0.3543 (2) | 0.0421 (8) | |
C7 | 0.06808 (11) | 0.1962 (7) | 0.36424 (17) | 0.0443 (8) | |
C8 | 0.03231 (13) | 0.1528 (8) | 0.4189 (2) | 0.0651 (12) | |
C31 | 0.16691 (11) | 0.4604 (6) | 0.58276 (19) | 0.0450 (8) | |
C32 | 0.15182 (12) | 0.3823 (6) | 0.6562 (2) | 0.0473 (9) | |
C33 | 0.17726 (14) | 0.1992 (8) | 0.7057 (2) | 0.0648 (11) | |
C34 | 0.16464 (18) | 0.1296 (9) | 0.7774 (2) | 0.0837 (15) | |
C35 | 0.12579 (19) | 0.2417 (11) | 0.7994 (2) | 0.0865 (16) | |
C36 | 0.10020 (17) | 0.4242 (9) | 0.7515 (3) | 0.0784 (14) | |
C37 | 0.11302 (14) | 0.4943 (7) | 0.6809 (2) | 0.0595 (11) | |
C51 | 0.18626 (12) | 0.4580 (6) | 0.30027 (19) | 0.0464 (8) | |
C52 | 0.18514 (13) | 0.3782 (7) | 0.2133 (2) | 0.0538 (9) | |
C53 | 0.15768 (15) | 0.4914 (8) | 0.1331 (2) | 0.0642 (11) | |
C54 | 0.1624 (2) | 0.4252 (11) | 0.0540 (3) | 0.0928 (17) | |
C55 | 0.1949 (2) | 0.2464 (12) | 0.0556 (3) | 0.1002 (19) | |
C56 | 0.22136 (17) | 0.1271 (10) | 0.1329 (3) | 0.0893 (16) | |
C57 | 0.21620 (15) | 0.1939 (8) | 0.2109 (2) | 0.0658 (11) | |
C71 | 0.03538 (12) | 0.1428 (6) | 0.2651 (2) | 0.0454 (9) | |
C72 | 0.02589 (14) | 0.2996 (7) | 0.2010 (2) | 0.0575 (10) | |
C73 | −0.00639 (16) | 0.2586 (8) | 0.1110 (2) | 0.0700 (12) | |
C74 | −0.02890 (16) | 0.0550 (9) | 0.0844 (3) | 0.0715 (13) | |
C75 | −0.01960 (15) | −0.1034 (8) | 0.1479 (3) | 0.0733 (12) | |
C76 | 0.01277 (14) | −0.0628 (7) | 0.2388 (2) | 0.0619 (10) | |
H2A | 0.1882 | 0.0135 | 0.5183 | 0.050* | |
H2B | 0.1322 | 0.0614 | 0.5319 | 0.050* | |
H6A | 0.1389 | 0.0750 | 0.2907 | 0.050* | |
H6B | 0.1913 | 0.0117 | 0.3785 | 0.050* | |
H7 | 0.0782 | 0.3513 | 0.3696 | 0.053* | |
H8A | 0.0306 | −0.0015 | 0.4279 | 0.098* | |
H8B | −0.0053 | 0.2083 | 0.3867 | 0.098* | |
H8C | 0.0493 | 0.2244 | 0.4763 | 0.098* | |
H31 | 0.1741 | 0.6090 | 0.5820 | 0.054* | |
H33 | 0.2033 | 0.1211 | 0.6909 | 0.078* | |
H34 | 0.1825 | 0.0070 | 0.8105 | 0.100* | |
H35 | 0.1169 | 0.1940 | 0.8467 | 0.104* | |
H36 | 0.0741 | 0.5010 | 0.7666 | 0.094* | |
H51 | 0.1926 | 0.6067 | 0.3113 | 0.056* | |
H54 | 0.1437 | 0.5015 | 0.0006 | 0.111* | |
H55 | 0.1991 | 0.2053 | 0.0033 | 0.120* | |
H56 | 0.2424 | 0.0036 | 0.1329 | 0.107* | |
H57 | 0.2340 | 0.1133 | 0.2634 | 0.079* | |
H72 | 0.0415 | 0.4376 | 0.2182 | 0.069* | |
H73 | −0.0129 | 0.3690 | 0.0686 | 0.084* | |
H74 | −0.0502 | 0.0252 | 0.0238 | 0.086* | |
H75 | −0.0352 | −0.2413 | 0.1303 | 0.088* | |
H76 | 0.0191 | −0.1730 | 0.2813 | 0.074* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0569 (13) | 0.0361 (15) | 0.0567 (13) | −0.0081 (12) | 0.0263 (10) | −0.0035 (12) |
N1 | 0.0423 (13) | 0.0398 (17) | 0.0438 (13) | −0.0049 (13) | 0.0206 (11) | −0.0048 (13) |
Cl1 | 0.0995 (8) | 0.0842 (9) | 0.1346 (9) | 0.0281 (8) | 0.0712 (7) | 0.0059 (9) |
Cl2 | 0.1153 (9) | 0.0876 (9) | 0.0804 (7) | 0.0228 (9) | 0.0275 (6) | 0.0321 (8) |
C2 | 0.0429 (16) | 0.038 (2) | 0.0463 (17) | 0.0024 (16) | 0.0201 (14) | 0.0039 (16) |
C3 | 0.0335 (15) | 0.040 (2) | 0.0364 (15) | 0.0005 (16) | 0.0123 (12) | −0.0018 (15) |
C4 | 0.0330 (15) | 0.037 (2) | 0.0425 (16) | 0.0054 (16) | 0.0131 (13) | 0.0045 (16) |
C5 | 0.0336 (15) | 0.044 (2) | 0.0408 (16) | 0.0043 (15) | 0.0186 (13) | 0.0001 (16) |
C6 | 0.0418 (16) | 0.040 (2) | 0.0476 (17) | −0.0003 (16) | 0.0208 (14) | −0.0045 (16) |
C7 | 0.0367 (15) | 0.048 (2) | 0.0484 (16) | −0.0045 (17) | 0.0170 (13) | −0.0021 (18) |
C8 | 0.0445 (17) | 0.098 (4) | 0.0564 (19) | 0.002 (2) | 0.0244 (15) | −0.002 (2) |
C31 | 0.0399 (16) | 0.047 (2) | 0.0462 (17) | −0.0045 (17) | 0.0156 (14) | −0.0028 (18) |
C32 | 0.0452 (17) | 0.056 (2) | 0.0400 (16) | −0.0091 (18) | 0.0164 (14) | −0.0065 (18) |
C33 | 0.063 (2) | 0.083 (3) | 0.0491 (18) | 0.002 (2) | 0.0233 (17) | 0.006 (2) |
C34 | 0.090 (3) | 0.102 (4) | 0.053 (2) | −0.005 (3) | 0.022 (2) | 0.016 (3) |
C35 | 0.088 (3) | 0.131 (5) | 0.050 (2) | −0.035 (4) | 0.037 (2) | −0.005 (3) |
C36 | 0.073 (3) | 0.109 (4) | 0.070 (3) | −0.022 (3) | 0.045 (2) | −0.021 (3) |
C37 | 0.054 (2) | 0.076 (3) | 0.0525 (19) | −0.010 (2) | 0.0251 (17) | −0.016 (2) |
C51 | 0.0467 (17) | 0.047 (2) | 0.0445 (16) | −0.0029 (18) | 0.0172 (14) | 0.0009 (17) |
C52 | 0.0503 (18) | 0.065 (3) | 0.0457 (18) | −0.008 (2) | 0.0188 (15) | 0.0019 (19) |
C53 | 0.059 (2) | 0.085 (3) | 0.0456 (18) | −0.007 (2) | 0.0184 (16) | 0.009 (2) |
C54 | 0.101 (3) | 0.128 (5) | 0.043 (2) | −0.004 (4) | 0.022 (2) | 0.005 (3) |
C55 | 0.101 (3) | 0.152 (6) | 0.051 (2) | 0.000 (4) | 0.034 (2) | −0.020 (4) |
C56 | 0.089 (3) | 0.121 (5) | 0.066 (2) | 0.010 (3) | 0.039 (2) | −0.015 (3) |
C57 | 0.067 (2) | 0.082 (3) | 0.0501 (18) | 0.006 (2) | 0.0245 (17) | 0.000 (2) |
C71 | 0.0401 (17) | 0.050 (2) | 0.0486 (17) | −0.0017 (17) | 0.0206 (14) | −0.0015 (18) |
C72 | 0.066 (2) | 0.059 (3) | 0.0531 (19) | −0.008 (2) | 0.0295 (17) | −0.005 (2) |
C73 | 0.085 (3) | 0.079 (4) | 0.048 (2) | −0.001 (3) | 0.0282 (19) | 0.007 (2) |
C74 | 0.069 (2) | 0.095 (4) | 0.0461 (19) | 0.000 (3) | 0.0190 (18) | −0.018 (3) |
C75 | 0.070 (2) | 0.073 (3) | 0.067 (2) | −0.018 (2) | 0.017 (2) | −0.024 (2) |
C76 | 0.062 (2) | 0.056 (3) | 0.062 (2) | −0.006 (2) | 0.0188 (18) | −0.001 (2) |
Geometric parameters (Å, º) top
Cl2—C53 | 1.730 (5) | C2—H2A | 0.9700 |
Cl1—C37 | 1.729 (4) | C2—H2B | 0.9700 |
C3—C31 | 1.336 (4) | C33—C34 | 1.391 (5) |
C3—C4 | 1.492 (4) | C33—H33 | 0.9300 |
C3—C2 | 1.507 (4) | C76—C75 | 1.392 (5) |
C5—C51 | 1.325 (4) | C76—H76 | 0.9300 |
C5—C4 | 1.502 (4) | C72—C73 | 1.381 (5) |
C5—C6 | 1.515 (4) | C72—H72 | 0.9300 |
O1—C4 | 1.221 (4) | C8—H8A | 0.9600 |
C31—C32 | 1.470 (4) | C8—H8B | 0.9600 |
C31—H31 | 0.9300 | C8—H8C | 0.9600 |
C71—C72 | 1.363 (5) | C73—C74 | 1.371 (7) |
C71—C76 | 1.381 (5) | C73—H73 | 0.9300 |
C71—C7 | 1.520 (4) | C35—C36 | 1.370 (7) |
C51—C52 | 1.480 (4) | C35—C34 | 1.372 (6) |
C51—H51 | 0.9300 | C35—H35 | 0.9300 |
C7—N1 | 1.480 (4) | C75—C74 | 1.364 (6) |
C7—C8 | 1.533 (4) | C75—H75 | 0.9300 |
C7—H7 | 0.9800 | C74—H74 | 0.9300 |
C6—N1 | 1.478 (3) | C54—C55 | 1.372 (7) |
C6—H6A | 0.9700 | C54—C53 | 1.393 (6) |
C6—H6B | 0.9700 | C54—H54 | 0.9300 |
N1—C2 | 1.479 (3) | C56—C55 | 1.373 (7) |
C57—C56 | 1.382 (5) | C56—H56 | 0.9300 |
C57—C52 | 1.392 (6) | C55—H55 | 0.9300 |
C57—H57 | 0.9300 | C37—C36 | 1.377 (5) |
C52—C53 | 1.390 (5) | C34—H34 | 0.9300 |
C32—C33 | 1.382 (5) | C36—H36 | 0.9300 |
C32—C37 | 1.396 (5) | | |
| | | |
C31—C3—C4 | 116.9 (3) | C32—C33—C34 | 121.2 (4) |
C31—C3—C2 | 125.5 (3) | C32—C33—H33 | 119.4 |
C4—C3—C2 | 117.3 (3) | C34—C33—H33 | 119.4 |
C51—C5—C4 | 117.6 (3) | C71—C76—C75 | 119.3 (4) |
C51—C5—C6 | 124.9 (3) | C71—C76—H76 | 120.4 |
C4—C5—C6 | 117.4 (3) | C75—C76—H76 | 120.4 |
C3—C31—C32 | 126.8 (4) | C71—C72—C73 | 121.6 (4) |
C3—C31—H31 | 116.6 | C71—C72—H72 | 119.2 |
C32—C31—H31 | 116.6 | C73—C72—H72 | 119.2 |
O1—C4—C3 | 121.8 (3) | C7—C8—H8A | 109.5 |
O1—C4—C5 | 120.7 (3) | C7—C8—H8B | 109.5 |
C3—C4—C5 | 117.5 (3) | H8A—C8—H8B | 109.5 |
C72—C71—C76 | 118.8 (3) | C7—C8—H8C | 109.5 |
C72—C71—C7 | 120.5 (3) | H8A—C8—H8C | 109.5 |
C76—C71—C7 | 120.6 (3) | H8B—C8—H8C | 109.5 |
C5—C51—C52 | 127.6 (4) | C74—C73—C72 | 119.9 (4) |
C5—C51—H51 | 116.2 | C74—C73—H73 | 120.1 |
C52—C51—H51 | 116.2 | C72—C73—H73 | 120.1 |
N1—C7—C71 | 109.9 (3) | C36—C35—C34 | 119.8 (4) |
N1—C7—C8 | 109.9 (3) | C36—C35—H35 | 120.1 |
C71—C7—C8 | 111.3 (2) | C34—C35—H35 | 120.1 |
N1—C7—H7 | 108.5 | C74—C75—C76 | 121.4 (4) |
C71—C7—H7 | 108.5 | C74—C75—H75 | 119.3 |
C8—C7—H7 | 108.5 | C76—C75—H75 | 119.3 |
N1—C6—C5 | 112.6 (3) | C75—C74—C73 | 119.0 (4) |
N1—C6—H6A | 109.1 | C75—C74—H74 | 120.5 |
C5—C6—H6A | 109.1 | C73—C74—H74 | 120.5 |
N1—C6—H6B | 109.1 | C55—C54—C53 | 119.4 (4) |
C5—C6—H6B | 109.1 | C55—C54—H54 | 120.3 |
H6A—C6—H6B | 107.8 | C53—C54—H54 | 120.3 |
C6—N1—C2 | 106.9 (2) | C52—C53—C54 | 120.9 (4) |
C6—N1—C7 | 112.9 (2) | C52—C53—Cl2 | 119.5 (3) |
C2—N1—C7 | 113.3 (2) | C54—C53—Cl2 | 119.5 (4) |
C56—C57—C52 | 122.1 (4) | C55—C56—C57 | 118.7 (5) |
C56—C57—H57 | 119.0 | C55—C56—H56 | 120.6 |
C52—C57—H57 | 119.0 | C57—C56—H56 | 120.6 |
C53—C52—C57 | 117.5 (3) | C54—C55—C56 | 121.3 (4) |
C53—C52—C51 | 122.2 (4) | C54—C55—H55 | 119.4 |
C57—C52—C51 | 120.1 (3) | C56—C55—H55 | 119.4 |
C33—C32—C37 | 117.4 (3) | C36—C37—C32 | 121.4 (4) |
C33—C32—C31 | 121.1 (3) | C36—C37—Cl1 | 119.2 (3) |
C37—C32—C31 | 121.5 (3) | C32—C37—Cl1 | 119.3 (3) |
N1—C2—C3 | 111.3 (3) | C35—C34—C33 | 120.0 (5) |
N1—C2—H2A | 109.4 | C35—C34—H34 | 120.0 |
C3—C2—H2A | 109.4 | C33—C34—H34 | 120.0 |
N1—C2—H2B | 109.4 | C35—C36—C37 | 120.2 (4) |
C3—C2—H2B | 109.4 | C35—C36—H36 | 119.9 |
H2A—C2—H2B | 108.0 | C37—C36—H36 | 119.9 |
| | | |
C4—C3—C31—C32 | −177.6 (3) | C7—N1—C2—C3 | −59.4 (3) |
C2—C3—C31—C32 | 8.3 (5) | C31—C3—C2—N1 | 133.5 (3) |
C31—C3—C4—O1 | 16.9 (4) | C4—C3—C2—N1 | −40.5 (3) |
C2—C3—C4—O1 | −168.6 (3) | C37—C32—C33—C34 | 0.0 (5) |
C31—C3—C4—C5 | −163.2 (3) | C31—C32—C33—C34 | 177.6 (4) |
C2—C3—C4—C5 | 11.3 (4) | C72—C71—C76—C75 | −0.9 (5) |
C51—C5—C4—O1 | −11.5 (4) | C7—C71—C76—C75 | 176.5 (3) |
C6—C5—C4—O1 | 171.6 (3) | C76—C71—C72—C73 | 1.1 (5) |
C51—C5—C4—C3 | 168.6 (3) | C7—C71—C72—C73 | −176.3 (3) |
C6—C5—C4—C3 | −8.3 (4) | C71—C72—C73—C74 | −1.2 (6) |
C4—C5—C51—C52 | 172.4 (3) | C71—C76—C75—C74 | 0.7 (6) |
C6—C5—C51—C52 | −11.0 (5) | C76—C75—C74—C73 | −0.8 (6) |
C72—C71—C7—N1 | −117.1 (3) | C72—C73—C74—C75 | 1.0 (6) |
C76—C71—C7—N1 | 65.5 (4) | C57—C52—C53—C54 | −1.6 (6) |
C72—C71—C7—C8 | 120.8 (4) | C51—C52—C53—C54 | 173.0 (4) |
C76—C71—C7—C8 | −56.6 (4) | C57—C52—C53—Cl2 | 176.6 (3) |
C51—C5—C6—N1 | −142.1 (3) | C51—C52—C53—Cl2 | −8.9 (5) |
C4—C5—C6—N1 | 34.6 (3) | C55—C54—C53—C52 | −0.4 (7) |
C5—C6—N1—C2 | −62.7 (3) | C55—C54—C53—Cl2 | −178.5 (4) |
C5—C6—N1—C7 | 62.5 (3) | C52—C57—C56—C55 | −0.1 (7) |
C71—C7—N1—C6 | 60.0 (3) | C53—C54—C55—C56 | 2.2 (8) |
C8—C7—N1—C6 | −177.1 (3) | C57—C56—C55—C54 | −2.0 (8) |
C71—C7—N1—C2 | −178.3 (3) | C33—C32—C37—C36 | −0.5 (5) |
C8—C7—N1—C2 | −55.4 (4) | C31—C32—C37—C36 | −178.1 (3) |
C56—C57—C52—C53 | 1.8 (6) | C33—C32—C37—Cl1 | −176.9 (3) |
C56—C57—C52—C51 | −172.9 (4) | C31—C32—C37—Cl1 | 5.5 (4) |
C5—C51—C52—C53 | 137.5 (4) | C36—C35—C34—C33 | −1.0 (7) |
C5—C51—C52—C57 | −48.0 (5) | C32—C33—C34—C35 | 0.8 (6) |
C3—C31—C32—C33 | 47.3 (5) | C34—C35—C36—C37 | 0.5 (7) |
C3—C31—C32—C37 | −135.3 (4) | C32—C37—C36—C35 | 0.3 (6) |
C6—N1—C2—C3 | 65.6 (3) | Cl1—C37—C36—C35 | 176.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O1i | 0.97 | 2.60 | 3.263 (4) | 126 |
C31—H31···O1 | 0.93 | 2.41 | 2.765 (4) | 103 |
C51—H51···O1 | 0.93 | 2.39 | 2.751 (4) | 103 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C27H25NO | C27H23Cl2NO | C27H23Cl2NO |
Mr | 379.48 | 448.36 | 448.36 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21 | Monoclinic, C2 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 6.0890 (7), 15.3562 (9), 23.1522 (11) | 6.6409 (3), 12.9466 (1), 13.1274 (8) | 25.746 (5), 6.1251 (9), 16.1829 (19) |
α, β, γ (°) | 90, 90, 90 | 90, 94.200 (16), 90 | 90, 113.55 (1), 90 |
V (Å3) | 2164.8 (3) | 1125.62 (9) | 2339.4 (7) |
Z | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.31 | 0.30 |
Crystal size (mm) | 0.19 × 0.17 × 0.12 | 0.22 × 0.13 × 0.12 | 0.22 × 0.18 × 0.11 |
|
Data collection |
Diffractometer | Nonius MACH3 four-circle diffractometer | Nonius MACH3 four-circle diffractometer | Nonius MACH3 four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.987, 0.992 | 0.935, 0.964 | 0.938, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2330, 2213, 1421 | 2678, 2256, 1918 | 2735, 2680, 1990 |
Rint | 0.016 | 0.078 | 0.014 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.093, 1.06 | 0.049, 0.139, 1.07 | 0.034, 0.086, 1.04 |
No. of reflections | 2213 | 2256 | 2680 |
No. of parameters | 263 | 281 | 282 |
No. of restraints | 0 | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.17 | 0.34, −0.40 | 0.29, −0.23 |
Absolute structure | ? | Flack (1983), 189 Friedel pairs? | Flack (1983), 407 Friedel pairs? |
Absolute structure parameter | ? | −0.08 (10) | −0.04 (9) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···O1 | 0.93 | 2.36 | 2.740 (3) | 104 |
C51—H51···O1 | 0.93 | 2.36 | 2.744 (3) | 105 |
C55—H55···Cg1i | 0.93 | 2.84 | 3.725 (4) | 159 |
C74—H74···Cg2i | 0.93 | 2.97 | 3.645 (5) | 130 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···O1 | 0.93 | 2.40 | 2.774 (6) | 104 |
C51—H51···O1 | 0.93 | 2.38 | 2.763 (6) | 105 |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O1i | 0.97 | 2.60 | 3.263 (4) | 126 |
C31—H31···O1 | 0.93 | 2.41 | 2.765 (4) | 103 |
C51—H51···O1 | 0.93 | 2.39 | 2.751 (4) | 103 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1. |
Comparison of of selected geometric parameters (°) of (I),
(II) and (III) topAtoms | Compound(I) | Compound(II) | Compound(III) |
C31-C3-C2 | 124.5 (3) | 125.7 (4) | 125.5 (3) |
C51-C5-C6 | 125.0 (2) | 125.3 (4) | 124.9 (3) |
C37-C32-C31 | 122.6 (3) | 124.1 (4) | 121.5 (3) |
C53-C52-C51 | 122.8 (3) | 124.5 (4) | 122.2 (4) |
C2-C3-C31-C32 | -5.2 (5) | -0.2 (8) | 8.3 (5) |
C8-C7-N1-C2 | -53.3 (3) | -58.6 (5) | -55.4 (4) |
C6-C5-C51-C52 | 5.2 (5) | -1.6 (7) | -11.0 (5) |
C71-C7-N1-C6 | 64.0 (3) | -63.4 (4) | 60.0 (3) |
Piperidine ring systems are of great interest in the pharmaceutical industry as they exhibit a wide range of biological activities (Guengerich et al., 1973; Puder et al., 2000). A number of α,β-unsaturated ketones display cytotoxic and anticancer properties (Dimmock, Elias et al., 1999; Dimmock, Kandepu et al., 1999), and also serve as precursors for various complex heterocycles. (R)-1-Phenylethylamine is one of the most promising and less expensive chiral auxiliaries (Juaristi et al., 1999). It is obvious that the design of a specific chiral environment utilizing chiral auxiliaries provides a useful protocol to prepare optically active substances. The three title substituted piperidones, (I)–(III), being enantiomerically pure, have enormous potential in the construction of more complex optically active compounds, and hence the struture determination of these compounds is of paramount importance.
The piperidone rings in (I), (II) and (III) adopt sofa conformations. Atom N1 deviates from the mean plane passing through atoms C2–C6 by -0.731 (3) Å in (I), -0.774 (5) Å in (II) and -0.705 (4) Å in (III). The differences in the deviations are due to steric factors and the different substitutions at the C3 and C5 positions of the piperidone ring. Both olefinic double bonds have an E configuration, and the aryl rings are not coplanar with the adjacent olefinic double bonds and the planar portion of the piperidone ring in (I), (II) and (III). The aryl rings are rotated to move atoms C53 and C37 in the opposite direction with respect to the displacement of atom N1 from the plane of the other five atoms in the piperidone ring. As a result, the torsion angles C5—C51—C52—C53 (θ1) and C3—C31—C32—C37 (θ2) have the values 40.7 (4) and -43.6 (5)° in (I), -26.0 (8) and 25.3 (7)° in (II), and 137.5 (4) and -135.3 (4)° in (III), respectively. This lack of coplanarity is caused by non-bonded interactions between one of the ortho H atoms in the aryl rings and the equatorial H atoms at the 2- and 6-positions of the piperidone ring (H53/H6A or H6B and H37/H2A or H2B). These steric repulsions are reduced by the expansion of the bond angles C5—C51—C52 (ψ1) and C3—C31—C32 (ψ2) [129.0 (3) and 128.2 (3) in (I), 129.5 (4) and 129.0 (4) in (II), 127.6 (4) and 126.8 (4) in (III), respectively], which are otherwise 120°. Similar effects have been observed in related compounds (Ompraba et al., 2003). The steric repulsion on the C71–C76 phenyl rings and methyl groups in (I), (II) and (III) could be understood in terms of the torsion angles C6—N1—C7—C71 and C2—N1—C7—C8 (Table 4). The dihedral angles between the N1/C7/C71 planes and C71–C77 phenyl rings are 46.4 (2)° in (I), 51.6 (2)° in (II) and 64.2 (2)° in (III).
The data presented here are useful in the design of additional analogues. The replacement of the equatorial H atoms at the 2- and 6-positions, and the inclusion of substituents of varying sizes at atoms C33, C37, C53 and C57, are likely to alter the θ and ψ values. Correlations have been established between the θ values and bioactivity (Pandeya & Dimmock, 1997). In addition, the increased ψ values would lead to variations in the relative locations of the aryl rings, which could affect the alignment (or possibly cause nonalignment) of these rings at a binding site and hence influence bioactivity (Quail et al., 2005).
In (I) and (II), the packing the molecules is governed by van der Waals interactions. Additionally, in (I), two weak C—H···π interactions are observed (Table 1; Cg1 and Cg2 are C71–C76 and C32–C37 ring centroids). In (III), the packing of the molecules is effected by C2—H2A···O1 interactions (Table 3 and Fig. 4) generating a C11(5) graph-set motif (Etter, 1990; Bernstein et al.,1995) to form a linear chain running along the b axis. No C—H···π interactions are observed in (II) and (III) and no π–.π interactions in any of the three compounds. The intramolecular C—H···O interactions (Tables 1, 2 and 3) C51—H51···O1 and C31—H31···O1, each of them generating an S(5) graph-set motif (Etter, 1990; Bernstein et al., 1995), are observed in compounds (I), (II) and (III).