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Two closely related oximes, namely 1-chloroacetyl-3-ethyl-2,6-diphenylpiperidin-4-one oxime, C
21H
23ClN
2O
2, (I), and 1-chloroacetyl-2,6-diphenyl-3-(propan-2-yl)piperidin-4-one oxime, C
22H
25ClN
2O
2, (II), despite their identical sets of hydrogen-bond donors and acceptors, display basically different hydrogen-bonding patterns in their crystal structures. While the molecules of (I) are organized into typical centrosymmetric dimers, created by oxime–oxime O—H
N hydrogen bonds, in the structure of (II) there are infinite chains of molecules connected by O—H
O hydrogen bonds, in which the carbonyl O atom from the chloroacetyl group acts as the hydrogen-bond acceptor. Despite the differences in the hydrogen-bond schemes, the –OH groups are always in typical
anti positions (C—N—O—H torsion angles of
ca 180°). The oxime group in (I) is disordered, with the hydroxy groups occupying two distinct positions and C—C—N—O torsion angles of approximately 0 and 180° for the two alternatives. This disorder, even though the site-occupancy factor of the less occupied position is as low as
ca 0.06, is also observed at lower temperatures, which seems to favour the statistical and not the dynamic nature of this phenomenon.
Supporting information
CCDC references: 762464; 762465; 762466
N-Chloroacetyl-3-ethyl-2,6-diphenylpiperidin-4-one (17.75 g, 50 mmol) for
(I) or N-chloroacetyl-3-(propan-2-yl)-2,6-diphenylpiperidin-4-one
(18.49 g, 50 mmol) for (II), sodium acetate trihydrate (20.4 g, 150 mmol),
hydroxyamine hydrochloride (4.02 g, 60 mmol) and ethanol (50 ml) were placed
in a round-bottomed flask. The reaction mixture was refluxed for about half an
hour and the progress of the reaction was monitored by thin-layer
chromatography. After completion of the reaction, the resulting substance was
poured into water, filtered off and dried. The obtained crude products were
subjected to column chromatography on silica gel (100–200 mesh) using a
benzene–ethyl acetate mixture (9:1 v/v) as eluent. Crystals of
(I) and (II) were grown from absolute alcohol [ethanol?] [m.p. 460 K
for (I) and 458 K for (II)].
Methyl H atoms in (I) and (II) and disordered hydroxy H atoms in (I) were
positioned geometrically in idealized positions, with C—H = 0.96 Å and
O—H = 0.82 Å [Please check added data], and refined as rigid
groups, with Uiso(H) = 1.2Ueq(hydroxy O) or
1.5Ueq(methyl C). All other H atoms in both (I) and (II) were found
in subsequent difference Fourier maps and refined isotropically.
For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 1-chloroacetyl-3-ethyl-2,6-diphenylpiperidin-4-one oxime
top
Crystal data top
C21H23ClN2O2 | F(000) = 1568 |
Mr = 370.86 | Dx = 1.304 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1945 reflections |
a = 34.176 (3) Å | θ = 2.0–27.0° |
b = 9.1227 (9) Å | µ = 0.22 mm−1 |
c = 12.1235 (11) Å | T = 293 K |
β = 91.962 (8)° | Block, colourless |
V = 3777.6 (6) Å3 | 0.3 × 0.15 × 0.1 mm |
Z = 8 | |
Data collection top
Oxford Xcalibur diffractometer with Sapphire2 (large Be window) detector | 3304 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1743 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 8.1929 pixels mm-1 | θmax = 25.0°, θmin = 2.9° |
ω scans | h = −38→40 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −10→9 |
Tmin = 0.993, Tmax = 1.000 | l = −14→11 |
8775 measured reflections | |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3 |
3304 reflections | (Δ/σ)max < 0.001 |
297 parameters | Δρmax = 0.21 e Å−3 |
1 restraint | Δρmin = −0.29 e Å−3 |
Crystal data top
C21H23ClN2O2 | V = 3777.6 (6) Å3 |
Mr = 370.86 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 34.176 (3) Å | µ = 0.22 mm−1 |
b = 9.1227 (9) Å | T = 293 K |
c = 12.1235 (11) Å | 0.3 × 0.15 × 0.1 mm |
β = 91.962 (8)° | |
Data collection top
Oxford Xcalibur diffractometer with Sapphire2 (large Be window) detector | 3304 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 1743 reflections with I > 2σ(I) |
Tmin = 0.993, Tmax = 1.000 | Rint = 0.051 |
8775 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 1 restraint |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.21 e Å−3 |
3304 reflections | Δρmin = −0.29 e Å−3 |
297 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell esds are taken into
account individually in the estimation of esds in distances, angles and
torsion angles; correlations between esds in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | Occ. (<1) |
N1 | 0.14039 (5) | 0.8808 (2) | 0.25714 (14) | 0.0334 (5) | |
C11 | 0.17344 (7) | 0.9094 (3) | 0.3196 (2) | 0.0450 (7) | |
O11 | 0.17310 (5) | 0.9306 (2) | 0.41882 (15) | 0.0661 (6) | |
C12 | 0.21218 (8) | 0.9178 (3) | 0.2636 (3) | 0.0602 (9) | |
H121 | 0.2150 (7) | 0.849 (3) | 0.211 (2) | 0.072* | |
H122 | 0.2346 (7) | 0.910 (3) | 0.3184 (19) | 0.072* | |
Cl12 | 0.21874 (2) | 1.09441 (9) | 0.20989 (8) | 0.0972 (3) | |
C2 | 0.10233 (7) | 0.9071 (3) | 0.31010 (18) | 0.0333 (6) | |
H2 | 0.1102 (5) | 0.961 (2) | 0.3781 (16) | 0.040* | |
C21 | 0.08363 (7) | 0.7656 (3) | 0.34717 (17) | 0.0344 (6) | |
C22 | 0.10702 (8) | 0.6571 (3) | 0.3953 (2) | 0.0450 (7) | |
H22 | 0.1358 (6) | 0.675 (2) | 0.4017 (17) | 0.054* | |
C23 | 0.09114 (10) | 0.5277 (3) | 0.4301 (2) | 0.0577 (8) | |
H23 | 0.1087 (7) | 0.451 (3) | 0.4588 (19) | 0.069* | |
C24 | 0.05162 (10) | 0.5033 (3) | 0.4204 (2) | 0.0569 (8) | |
H24 | 0.0410 (7) | 0.416 (3) | 0.4414 (19) | 0.068* | |
C25 | 0.02783 (8) | 0.6110 (4) | 0.3763 (2) | 0.0579 (9) | |
H25 | −0.0004 (7) | 0.603 (3) | 0.3698 (18) | 0.069* | |
C26 | 0.04378 (8) | 0.7410 (3) | 0.3398 (2) | 0.0490 (8) | |
H26 | 0.0274 (6) | 0.818 (3) | 0.3097 (18) | 0.059* | |
C3 | 0.07702 (7) | 1.0088 (3) | 0.23571 (19) | 0.0344 (6) | |
H3 | 0.0523 (6) | 1.023 (2) | 0.2723 (15) | 0.041* | |
C31 | 0.09602 (9) | 1.1589 (3) | 0.2216 (2) | 0.0501 (8) | |
H311 | 0.1077 (6) | 1.197 (3) | 0.2934 (18) | 0.060* | |
H312 | 0.1211 (6) | 1.152 (2) | 0.1719 (17) | 0.060* | |
C32 | 0.06809 (8) | 1.2736 (3) | 0.1766 (2) | 0.0722 (9) | |
H321 | 0.0812 | 1.3665 | 0.1741 | 0.108* | |
H322 | 0.0461 | 1.2810 | 0.2235 | 0.108* | |
H323 | 0.0591 | 1.2465 | 0.1035 | 0.108* | |
C4 | 0.06877 (7) | 0.9335 (3) | 0.12681 (18) | 0.0319 (6) | |
N41 | 0.03678 (5) | 0.9611 (2) | 0.07310 (15) | 0.0365 (5) | |
O41 | 0.03337 (4) | 0.88015 (19) | −0.02603 (13) | 0.0448 (7) | 0.939 (3) |
H41 | 0.0129 | 0.9021 | −0.0592 | 0.054* | 0.939 (3) |
O41A | 0.0119 (6) | 1.065 (2) | 0.1172 (19) | 0.053 (11)* | 0.061 (3) |
H41A | −0.0076 | 1.0740 | 0.0766 | 0.064* | 0.061 (3) |
C5 | 0.09830 (7) | 0.8237 (3) | 0.09157 (19) | 0.0360 (7) | |
H51 | 0.0992 (5) | 0.823 (2) | 0.0129 (16) | 0.043* | |
H52 | 0.0894 (6) | 0.726 (2) | 0.1166 (16) | 0.043* | |
C6 | 0.14029 (7) | 0.8499 (3) | 0.13637 (19) | 0.0346 (6) | |
H6 | 0.1511 (6) | 0.939 (2) | 0.0995 (15) | 0.041* | |
C61 | 0.16423 (6) | 0.7168 (3) | 0.10500 (19) | 0.0338 (6) | |
C62 | 0.16198 (8) | 0.5855 (3) | 0.1604 (2) | 0.0473 (7) | |
H62 | 0.1479 (6) | 0.580 (3) | 0.2297 (17) | 0.057* | |
C63 | 0.18101 (9) | 0.4619 (3) | 0.1222 (3) | 0.0606 (9) | |
H63 | 0.1783 (7) | 0.375 (3) | 0.162 (2) | 0.073* | |
C64 | 0.20225 (9) | 0.4696 (4) | 0.0284 (3) | 0.0680 (10) | |
H64 | 0.2144 (7) | 0.387 (3) | 0.006 (2) | 0.082* | |
C65 | 0.20463 (9) | 0.5997 (5) | −0.0259 (3) | 0.0720 (10) | |
H65 | 0.2196 (8) | 0.608 (3) | −0.085 (2) | 0.086* | |
C66 | 0.18590 (8) | 0.7225 (3) | 0.0111 (2) | 0.0572 (8) | |
H66 | 0.1874 (7) | 0.812 (3) | −0.024 (2) | 0.069* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0314 (12) | 0.0355 (14) | 0.0333 (12) | 0.0014 (10) | −0.0017 (9) | −0.0028 (10) |
C11 | 0.0403 (17) | 0.0390 (17) | 0.0550 (19) | 0.0000 (14) | −0.0082 (14) | −0.0064 (16) |
O11 | 0.0608 (13) | 0.0855 (16) | 0.0506 (12) | −0.0054 (11) | −0.0164 (10) | −0.0189 (12) |
C12 | 0.0424 (19) | 0.052 (2) | 0.086 (3) | −0.0055 (17) | −0.0088 (16) | −0.0158 (18) |
Cl12 | 0.0779 (6) | 0.0686 (6) | 0.1475 (9) | −0.0006 (5) | 0.0366 (5) | 0.0270 (6) |
C2 | 0.0353 (15) | 0.0353 (17) | 0.0291 (14) | 0.0050 (14) | −0.0004 (11) | −0.0020 (13) |
C21 | 0.0375 (16) | 0.0376 (17) | 0.0281 (14) | 0.0015 (14) | 0.0014 (11) | 0.0000 (13) |
C22 | 0.0430 (16) | 0.0470 (19) | 0.0452 (17) | 0.0032 (17) | 0.0039 (13) | 0.0142 (15) |
C23 | 0.065 (2) | 0.051 (2) | 0.058 (2) | 0.0069 (18) | 0.0096 (15) | 0.0194 (16) |
C24 | 0.081 (3) | 0.047 (2) | 0.0435 (18) | −0.012 (2) | 0.0109 (16) | 0.0103 (16) |
C25 | 0.0510 (19) | 0.069 (2) | 0.0535 (19) | −0.017 (2) | 0.0012 (15) | 0.0117 (18) |
C26 | 0.0455 (19) | 0.052 (2) | 0.0492 (17) | −0.0023 (16) | −0.0004 (13) | 0.0141 (16) |
C3 | 0.0358 (15) | 0.0343 (16) | 0.0332 (15) | 0.0078 (14) | 0.0039 (11) | −0.0012 (13) |
C31 | 0.068 (2) | 0.0324 (18) | 0.0499 (18) | 0.0030 (17) | −0.0016 (15) | 0.0006 (15) |
C32 | 0.109 (3) | 0.0394 (18) | 0.068 (2) | 0.0161 (19) | −0.0014 (18) | 0.0051 (17) |
C4 | 0.0320 (14) | 0.0299 (16) | 0.0340 (15) | 0.0045 (12) | 0.0027 (11) | 0.0060 (13) |
N41 | 0.0391 (13) | 0.0400 (14) | 0.0305 (12) | 0.0057 (11) | 0.0020 (10) | −0.0009 (11) |
O41 | 0.0431 (12) | 0.0553 (14) | 0.0352 (11) | 0.0114 (10) | −0.0112 (8) | −0.0074 (10) |
C5 | 0.0379 (16) | 0.0393 (17) | 0.0308 (15) | 0.0073 (14) | 0.0000 (12) | −0.0006 (14) |
C6 | 0.0364 (16) | 0.0311 (16) | 0.0365 (16) | 0.0013 (13) | 0.0048 (11) | 0.0024 (13) |
C61 | 0.0275 (14) | 0.0335 (17) | 0.0403 (15) | 0.0022 (13) | −0.0021 (11) | −0.0030 (14) |
C62 | 0.0479 (17) | 0.0422 (19) | 0.0523 (18) | 0.0119 (16) | 0.0071 (13) | −0.0004 (16) |
C63 | 0.059 (2) | 0.044 (2) | 0.079 (2) | 0.0114 (18) | −0.0082 (18) | 0.0023 (18) |
C64 | 0.056 (2) | 0.062 (3) | 0.085 (3) | 0.0289 (19) | −0.0058 (19) | −0.025 (2) |
C65 | 0.057 (2) | 0.086 (3) | 0.074 (2) | 0.021 (2) | 0.0260 (16) | −0.011 (2) |
C66 | 0.0537 (19) | 0.055 (2) | 0.064 (2) | 0.0151 (18) | 0.0213 (15) | 0.0025 (18) |
Geometric parameters (Å, º) top
N1—C11 | 1.364 (3) | C31—H312 | 1.07 (2) |
N1—C2 | 1.490 (3) | C32—H321 | 0.9600 |
N1—C6 | 1.491 (3) | C32—H322 | 0.9600 |
C11—O11 | 1.218 (3) | C32—H323 | 0.9600 |
C11—C12 | 1.510 (4) | C4—N41 | 1.278 (2) |
C12—Cl12 | 1.755 (3) | C4—C5 | 1.495 (3) |
C12—H121 | 0.90 (2) | N41—O41A | 1.391 (10) |
C12—H122 | 1.00 (2) | N41—O41 | 1.412 (2) |
C2—C21 | 1.515 (3) | O41—H41 | 0.8200 |
C2—C3 | 1.539 (3) | O41A—H41A | 0.8200 |
C2—H2 | 0.988 (19) | C5—C6 | 1.536 (3) |
C21—C26 | 1.380 (3) | C5—H51 | 0.955 (19) |
C21—C22 | 1.388 (3) | C5—H52 | 0.99 (2) |
C22—C23 | 1.371 (3) | C6—C61 | 1.520 (3) |
C22—H22 | 1.00 (2) | C6—H6 | 1.00 (2) |
C23—C24 | 1.370 (4) | C61—C62 | 1.377 (3) |
C23—H23 | 0.98 (2) | C61—C66 | 1.380 (3) |
C24—C25 | 1.372 (4) | C62—C63 | 1.389 (4) |
C24—H24 | 0.91 (2) | C62—H62 | 0.98 (2) |
C25—C26 | 1.384 (4) | C63—C64 | 1.371 (4) |
C25—H25 | 0.97 (2) | C63—H63 | 0.93 (2) |
C26—H26 | 0.96 (2) | C64—C65 | 1.361 (4) |
C3—C4 | 1.506 (3) | C64—H64 | 0.90 (3) |
C3—C31 | 1.528 (3) | C65—C66 | 1.373 (4) |
C3—H3 | 0.975 (19) | C65—H65 | 0.90 (2) |
C31—C32 | 1.506 (3) | C66—H66 | 0.92 (2) |
C31—H311 | 1.01 (2) | | |
| | | |
C11—N1—C2 | 116.65 (19) | C3—C31—H312 | 111.1 (13) |
C11—N1—C6 | 123.77 (19) | H311—C31—H312 | 102.0 (17) |
C2—N1—C6 | 118.76 (17) | C31—C32—H321 | 109.5 |
O11—C11—N1 | 122.9 (2) | C31—C32—H322 | 109.5 |
O11—C11—C12 | 118.3 (2) | H321—C32—H322 | 109.5 |
N1—C11—C12 | 118.8 (2) | C31—C32—H323 | 109.5 |
C11—C12—Cl12 | 109.8 (2) | H321—C32—H323 | 109.5 |
C11—C12—H121 | 113.7 (17) | H322—C32—H323 | 109.5 |
Cl12—C12—H121 | 110.8 (17) | N41—C4—C5 | 124.1 (2) |
C11—C12—H122 | 111.2 (14) | N41—C4—C3 | 119.2 (2) |
Cl12—C12—H122 | 102.1 (14) | C5—C4—C3 | 116.6 (2) |
H121—C12—H122 | 109 (2) | C4—N41—O41A | 117.5 (11) |
N1—C2—C21 | 112.0 (2) | C4—N41—O41 | 112.01 (19) |
N1—C2—C3 | 109.03 (18) | O41A—N41—O41 | 130.5 (11) |
C21—C2—C3 | 116.93 (19) | N41—O41—H41 | 109.5 |
N1—C2—H2 | 102.9 (11) | N41—O41A—H41A | 109.5 |
C21—C2—H2 | 106.3 (12) | C4—C5—C6 | 115.2 (2) |
C3—C2—H2 | 108.7 (11) | C4—C5—H51 | 109.7 (13) |
C26—C21—C22 | 117.7 (2) | C6—C5—H51 | 107.0 (12) |
C26—C21—C2 | 123.0 (2) | C4—C5—H52 | 107.2 (12) |
C22—C21—C2 | 119.3 (2) | C6—C5—H52 | 109.0 (12) |
C23—C22—C21 | 121.0 (3) | H51—C5—H52 | 108.5 (17) |
C23—C22—H22 | 121.3 (13) | N1—C6—C61 | 114.42 (19) |
C21—C22—H22 | 117.7 (13) | N1—C6—C5 | 110.33 (18) |
C24—C23—C22 | 120.9 (3) | C61—C6—C5 | 106.9 (2) |
C24—C23—H23 | 120.4 (15) | N1—C6—H6 | 107.3 (11) |
C22—C23—H23 | 118.7 (15) | C61—C6—H6 | 108.9 (11) |
C23—C24—C25 | 119.1 (3) | C5—C6—H6 | 108.9 (12) |
C23—C24—H24 | 121.1 (16) | C62—C61—C66 | 118.4 (3) |
C25—C24—H24 | 119.8 (16) | C62—C61—C6 | 122.3 (2) |
C24—C25—C26 | 120.2 (3) | C66—C61—C6 | 119.0 (2) |
C24—C25—H25 | 123.6 (15) | C61—C62—C63 | 120.6 (3) |
C26—C25—H25 | 116.2 (15) | C61—C62—H62 | 119.7 (14) |
C21—C26—C25 | 121.1 (3) | C63—C62—H62 | 119.7 (15) |
C21—C26—H26 | 118.0 (14) | C64—C63—C62 | 120.1 (3) |
C25—C26—H26 | 120.9 (14) | C64—C63—H63 | 122.5 (16) |
C4—C3—C31 | 112.2 (2) | C62—C63—H63 | 117.4 (16) |
C4—C3—C2 | 108.88 (19) | C65—C64—C63 | 119.2 (3) |
C31—C3—C2 | 111.9 (2) | C65—C64—H64 | 122.8 (18) |
C4—C3—H3 | 108.6 (12) | C63—C64—H64 | 118.0 (18) |
C31—C3—H3 | 108.1 (13) | C64—C65—C66 | 121.2 (3) |
C2—C3—H3 | 106.9 (12) | C64—C65—H65 | 120 (2) |
C32—C31—C3 | 113.4 (2) | C66—C65—H65 | 119 (2) |
C32—C31—H311 | 107.6 (14) | C65—C66—C61 | 120.5 (3) |
C3—C31—H311 | 111.6 (13) | C65—C66—H66 | 122.7 (16) |
C32—C31—H312 | 110.5 (12) | C61—C66—H66 | 116.8 (16) |
| | | |
C2—N1—C11—O11 | 12.5 (4) | C31—C3—C4—N41 | −85.8 (3) |
C6—N1—C11—O11 | −178.0 (2) | C2—C3—C4—N41 | 149.7 (2) |
C2—N1—C11—C12 | −166.4 (2) | C31—C3—C4—C5 | 97.3 (2) |
C6—N1—C11—C12 | 3.0 (4) | C2—C3—C4—C5 | −27.1 (3) |
O11—C11—C12—Cl12 | −94.6 (3) | C5—C4—N41—O41A | 179.1 (12) |
N1—C11—C12—Cl12 | 84.4 (3) | C3—C4—N41—O41A | 2.6 (12) |
C11—N1—C2—C21 | −102.6 (2) | C5—C4—N41—O41 | −2.5 (3) |
C6—N1—C2—C21 | 87.4 (2) | C3—C4—N41—O41 | −179.10 (18) |
C11—N1—C2—C3 | 126.5 (2) | N41—C4—C5—C6 | 155.7 (2) |
C6—N1—C2—C3 | −43.5 (3) | C3—C4—C5—C6 | −27.6 (3) |
N1—C2—C21—C26 | −142.4 (2) | C11—N1—C6—C61 | 59.8 (3) |
C3—C2—C21—C26 | −15.6 (3) | C2—N1—C6—C61 | −130.9 (2) |
N1—C2—C21—C22 | 40.5 (3) | C11—N1—C6—C5 | −179.6 (2) |
C3—C2—C21—C22 | 167.3 (2) | C2—N1—C6—C5 | −10.3 (3) |
C26—C21—C22—C23 | 2.6 (4) | C4—C5—C6—N1 | 47.2 (3) |
C2—C21—C22—C23 | 179.8 (2) | C4—C5—C6—C61 | 172.20 (19) |
C21—C22—C23—C24 | −1.4 (4) | N1—C6—C61—C62 | 45.7 (3) |
C22—C23—C24—C25 | −0.7 (4) | C5—C6—C61—C62 | −76.7 (3) |
C23—C24—C25—C26 | 1.5 (4) | N1—C6—C61—C66 | −141.0 (2) |
C22—C21—C26—C25 | −1.8 (4) | C5—C6—C61—C66 | 96.5 (3) |
C2—C21—C26—C25 | −178.9 (2) | C66—C61—C62—C63 | −0.3 (4) |
C24—C25—C26—C21 | −0.2 (4) | C6—C61—C62—C63 | 173.0 (2) |
N1—C2—C3—C4 | 62.2 (2) | C61—C62—C63—C64 | −0.1 (4) |
C21—C2—C3—C4 | −66.0 (2) | C62—C63—C64—C65 | 0.5 (5) |
N1—C2—C3—C31 | −62.4 (3) | C63—C64—C65—C66 | −0.5 (5) |
C21—C2—C3—C31 | 169.4 (2) | C64—C65—C66—C61 | 0.2 (5) |
C4—C3—C31—C32 | 73.0 (3) | C62—C61—C66—C65 | 0.2 (4) |
C2—C3—C31—C32 | −164.2 (2) | C6—C61—C66—C65 | −173.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···N41i | 0.82 | 2.11 | 2.842 (2) | 149 |
O41A—H41A···N41i | 0.82 | 2.07 | 2.81 (3) | 151 |
C66—H66···O11ii | 0.92 (2) | 2.50 (2) | 3.380 (4) | 162 (2) |
Symmetry codes: (i) −x, −y+2, −z; (ii) x, −y+2, z−1/2. |
(I_100K) 1-chloroacetyl-3-ethyl-2,6-diphenylpiperidin-4-one oxime
top
Crystal data top
C21H23ClN2O2 | F(000) = 1568 |
Mr = 370.86 | Dx = 1.347 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 10444 reflections |
a = 33.849 (3) Å | θ = 2.9–26.9° |
b = 9.025 (1) Å | µ = 0.23 mm−1 |
c = 11.980 (1) Å | T = 100 K |
β = 92.51 (1)° | Block, colourless |
V = 3656.2 (6) Å3 | 0.3 × 0.15 × 0.1 mm |
Z = 8 | |
Data collection top
Oxford Xcalibur diffractometer with Eos detector | 3729 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3245 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
Detector resolution: 16.1544 pixels mm-1 | θmax = 27.0°, θmin = 2.9° |
ω scans | h = −40→42 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −11→11 |
Tmin = 0.957, Tmax = 1.000 | l = −15→14 |
14395 measured reflections | |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.037P)2 + 2.8415P] where P = (Fo2 + 2Fc2)/3 |
3729 reflections | (Δ/σ)max = 0.001 |
312 parameters | Δρmax = 0.31 e Å−3 |
1 restraint | Δρmin = −0.26 e Å−3 |
Crystal data top
C21H23ClN2O2 | V = 3656.2 (6) Å3 |
Mr = 370.86 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 33.849 (3) Å | µ = 0.23 mm−1 |
b = 9.025 (1) Å | T = 100 K |
c = 11.980 (1) Å | 0.3 × 0.15 × 0.1 mm |
β = 92.51 (1)° | |
Data collection top
Oxford Xcalibur diffractometer with Eos detector | 3729 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 3245 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 1.000 | Rint = 0.013 |
14395 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 1 restraint |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.31 e Å−3 |
3729 reflections | Δρmin = −0.26 e Å−3 |
312 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell esds are taken into
account individually in the estimation of esds in distances, angles and
torsion angles; correlations between esds in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 >
2σ(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 | Occ. (<1) |
N1 | 0.14160 (3) | 0.87917 (11) | 0.26109 (8) | 0.0131 (2) | |
C11 | 0.17495 (4) | 0.90281 (13) | 0.32592 (10) | 0.0162 (3) | |
O11 | 0.17461 (3) | 0.92002 (10) | 0.42733 (7) | 0.0225 (2) | |
C12 | 0.21427 (4) | 0.91166 (14) | 0.27036 (12) | 0.0194 (3) | |
H122 | 0.2353 (5) | 0.9008 (16) | 0.3286 (13) | 0.023* | |
H121 | 0.2169 (5) | 0.843 (2) | 0.2114 (14) | 0.035 (5)* | |
Cl12 | 0.219554 (10) | 1.09233 (4) | 0.21218 (3) | 0.03063 (11) | |
C2 | 0.10346 (3) | 0.90836 (13) | 0.31385 (10) | 0.0134 (2) | |
H2 | 0.1103 (4) | 0.9614 (16) | 0.3812 (12) | 0.016* | |
C21 | 0.08383 (3) | 0.76504 (13) | 0.34909 (9) | 0.0142 (2) | |
C22 | 0.10734 (4) | 0.65140 (14) | 0.39432 (10) | 0.0174 (3) | |
H22 | 0.1357 (5) | 0.6658 (17) | 0.4048 (12) | 0.021* | |
C23 | 0.09088 (4) | 0.51899 (15) | 0.42738 (10) | 0.0202 (3) | |
H23 | 0.1074 (5) | 0.4434 (18) | 0.4580 (13) | 0.024* | |
C24 | 0.05031 (4) | 0.49812 (15) | 0.41856 (10) | 0.0216 (3) | |
H24 | 0.0390 (5) | 0.4071 (18) | 0.4419 (13) | 0.026* | |
C25 | 0.02654 (4) | 0.61224 (16) | 0.37743 (11) | 0.0224 (3) | |
H25 | −0.0020 (5) | 0.5998 (17) | 0.3708 (13) | 0.027* | |
C26 | 0.04310 (4) | 0.74471 (15) | 0.34294 (10) | 0.0182 (3) | |
H26 | 0.0259 (4) | 0.8215 (18) | 0.3156 (12) | 0.022* | |
C3 | 0.07812 (3) | 1.01219 (13) | 0.23808 (10) | 0.0142 (2) | |
H3 | 0.0532 (4) | 1.0299 (16) | 0.2756 (12) | 0.017* | |
C31 | 0.09819 (4) | 1.16357 (14) | 0.22331 (11) | 0.0187 (3) | |
H311 | 0.1211 (4) | 1.1522 (17) | 0.1741 (12) | 0.022* | |
H312 | 0.1090 (4) | 1.1959 (17) | 0.2960 (13) | 0.022* | |
C32 | 0.07000 (4) | 1.28025 (15) | 0.17442 (12) | 0.0237 (3) | |
H321 | 0.0827 (5) | 1.377 (2) | 0.1710 (14) | 0.035* | |
H322 | 0.0465 (5) | 1.2894 (19) | 0.2230 (14) | 0.035* | |
H323 | 0.0602 (5) | 1.2513 (19) | 0.0987 (15) | 0.035* | |
C4 | 0.06947 (3) | 0.93607 (13) | 0.12786 (10) | 0.0131 (2) | |
N41 | 0.03702 (3) | 0.96303 (11) | 0.07331 (8) | 0.0143 (2) | |
O41 | 0.03308 (3) | 0.87978 (10) | −0.02713 (7) | 0.0154 (3) | 0.943 (3) |
H41 | 0.0119 | 0.9030 | −0.0618 | 0.018* | 0.943 (3) |
O41A | 0.0111 (5) | 1.0662 (19) | 0.1174 (16) | 0.048 (7) | 0.057 (3) |
H41A | −0.0091 | 1.0744 | 0.0744 | 0.058* | 0.057 (3) |
C5 | 0.09921 (3) | 0.82528 (13) | 0.09185 (10) | 0.0137 (2) | |
H51 | 0.0902 (4) | 0.7266 (17) | 0.1155 (11) | 0.016* | |
H52 | 0.0998 (4) | 0.8236 (16) | 0.0111 (12) | 0.016* | |
C6 | 0.14158 (3) | 0.85183 (13) | 0.13869 (9) | 0.0131 (2) | |
H6 | 0.1522 (4) | 0.9381 (16) | 0.1030 (12) | 0.016* | |
C61 | 0.16548 (3) | 0.71765 (13) | 0.10467 (10) | 0.0141 (2) | |
C62 | 0.16256 (4) | 0.58173 (14) | 0.15821 (11) | 0.0178 (3) | |
H62 | 0.1471 (4) | 0.5728 (16) | 0.2242 (13) | 0.021* | |
C63 | 0.18113 (4) | 0.45731 (15) | 0.11712 (12) | 0.0219 (3) | |
H63 | 0.1785 (5) | 0.3666 (19) | 0.1537 (13) | 0.026* | |
C64 | 0.20287 (4) | 0.46749 (16) | 0.02189 (12) | 0.0236 (3) | |
H64 | 0.2150 (5) | 0.3827 (18) | −0.0076 (13) | 0.028* | |
C65 | 0.20617 (4) | 0.60243 (16) | −0.03116 (12) | 0.0256 (3) | |
H65 | 0.2211 (5) | 0.6118 (18) | −0.0981 (14) | 0.031* | |
C66 | 0.18769 (4) | 0.72744 (15) | 0.00977 (11) | 0.0212 (3) | |
H66 | 0.1901 (4) | 0.8213 (19) | −0.0264 (13) | 0.025* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0126 (5) | 0.0131 (5) | 0.0136 (5) | 0.0003 (4) | 0.0005 (4) | −0.0002 (4) |
C11 | 0.0177 (6) | 0.0106 (6) | 0.0201 (6) | −0.0002 (5) | −0.0027 (5) | −0.0002 (5) |
O11 | 0.0235 (5) | 0.0252 (5) | 0.0183 (5) | −0.0014 (4) | −0.0051 (4) | −0.0029 (4) |
C12 | 0.0162 (6) | 0.0153 (6) | 0.0263 (7) | −0.0009 (5) | −0.0028 (5) | −0.0020 (5) |
Cl12 | 0.02359 (18) | 0.02278 (19) | 0.0462 (2) | −0.00070 (13) | 0.00939 (15) | 0.00927 (15) |
C2 | 0.0148 (6) | 0.0137 (6) | 0.0119 (5) | 0.0011 (4) | 0.0007 (4) | −0.0010 (5) |
C21 | 0.0179 (6) | 0.0149 (6) | 0.0098 (5) | −0.0002 (5) | 0.0017 (4) | −0.0002 (4) |
C22 | 0.0183 (6) | 0.0188 (6) | 0.0152 (6) | 0.0009 (5) | 0.0013 (5) | 0.0017 (5) |
C23 | 0.0285 (7) | 0.0164 (6) | 0.0159 (6) | 0.0029 (5) | 0.0029 (5) | 0.0036 (5) |
C24 | 0.0325 (7) | 0.0174 (7) | 0.0151 (6) | −0.0075 (5) | 0.0053 (5) | 0.0004 (5) |
C25 | 0.0208 (7) | 0.0282 (7) | 0.0182 (6) | −0.0061 (5) | 0.0022 (5) | 0.0011 (5) |
C26 | 0.0181 (6) | 0.0208 (6) | 0.0158 (6) | 0.0014 (5) | 0.0008 (5) | 0.0022 (5) |
C3 | 0.0154 (6) | 0.0136 (6) | 0.0138 (5) | 0.0027 (5) | 0.0024 (4) | 0.0007 (5) |
C31 | 0.0250 (6) | 0.0128 (6) | 0.0181 (6) | 0.0003 (5) | 0.0002 (5) | −0.0004 (5) |
C32 | 0.0352 (8) | 0.0139 (7) | 0.0218 (7) | 0.0047 (6) | 0.0002 (6) | 0.0013 (5) |
C4 | 0.0142 (5) | 0.0108 (6) | 0.0144 (5) | 0.0003 (4) | 0.0029 (4) | 0.0024 (4) |
N41 | 0.0167 (5) | 0.0129 (5) | 0.0133 (5) | 0.0012 (4) | 0.0017 (4) | −0.0005 (4) |
O41 | 0.0144 (5) | 0.0173 (5) | 0.0142 (5) | 0.0038 (3) | −0.0031 (3) | −0.0040 (4) |
O41A | 0.027 (11) | 0.061 (15) | 0.056 (14) | −0.005 (10) | −0.013 (9) | 0.026 (11) |
C5 | 0.0147 (6) | 0.0137 (6) | 0.0127 (5) | 0.0018 (5) | −0.0002 (4) | −0.0009 (5) |
C6 | 0.0141 (5) | 0.0124 (6) | 0.0130 (5) | 0.0001 (4) | 0.0010 (4) | 0.0008 (4) |
C61 | 0.0107 (5) | 0.0155 (6) | 0.0158 (6) | 0.0009 (4) | −0.0018 (4) | −0.0022 (5) |
C62 | 0.0153 (6) | 0.0172 (6) | 0.0208 (6) | 0.0007 (5) | 0.0002 (5) | −0.0001 (5) |
C63 | 0.0198 (6) | 0.0151 (6) | 0.0302 (7) | 0.0028 (5) | −0.0043 (5) | −0.0003 (5) |
C64 | 0.0172 (6) | 0.0223 (7) | 0.0308 (7) | 0.0077 (5) | −0.0032 (5) | −0.0103 (6) |
C65 | 0.0209 (7) | 0.0301 (8) | 0.0263 (7) | 0.0054 (6) | 0.0068 (5) | −0.0046 (6) |
C66 | 0.0200 (6) | 0.0207 (7) | 0.0231 (6) | 0.0026 (5) | 0.0045 (5) | 0.0012 (5) |
Geometric parameters (Å, º) top
N1—C11 | 1.3587 (16) | C31—H312 | 0.975 (15) |
N1—C2 | 1.4855 (15) | C32—H321 | 0.976 (18) |
N1—C6 | 1.4869 (14) | C32—H322 | 1.008 (17) |
C11—O11 | 1.2254 (15) | C32—H323 | 0.988 (17) |
C11—C12 | 1.5163 (18) | C4—N41 | 1.2766 (15) |
C12—Cl12 | 1.7853 (13) | C4—C5 | 1.4959 (16) |
C12—H122 | 0.980 (16) | N41—O41A | 1.399 (10) |
C12—H121 | 0.945 (18) | N41—O41 | 1.4198 (13) |
C2—C21 | 1.5224 (16) | O41—H41 | 0.8400 |
C2—C3 | 1.5394 (16) | O41A—H41A | 0.8400 |
C2—H2 | 0.958 (15) | C5—C6 | 1.5357 (16) |
C21—C26 | 1.3893 (17) | C5—H51 | 0.987 (15) |
C21—C22 | 1.3933 (17) | C5—H52 | 0.969 (14) |
C22—C23 | 1.3839 (19) | C6—C61 | 1.5219 (16) |
C22—H22 | 0.971 (15) | C6—H6 | 0.965 (15) |
C23—C24 | 1.3853 (19) | C61—C62 | 1.3898 (17) |
C23—H23 | 0.946 (16) | C61—C66 | 1.3930 (17) |
C24—C25 | 1.384 (2) | C62—C63 | 1.3876 (18) |
C24—H24 | 0.954 (16) | C62—H62 | 0.970 (15) |
C25—C26 | 1.3909 (19) | C63—C64 | 1.387 (2) |
C25—H25 | 0.973 (17) | C63—H63 | 0.935 (17) |
C26—H26 | 0.954 (16) | C64—C65 | 1.380 (2) |
C3—C4 | 1.5058 (16) | C64—H64 | 0.945 (17) |
C3—C31 | 1.5394 (17) | C65—C66 | 1.3898 (19) |
C3—H3 | 0.987 (14) | C65—H65 | 0.969 (17) |
C31—C32 | 1.5211 (18) | C66—H66 | 0.956 (17) |
C31—H311 | 1.001 (15) | | |
| | | |
C11—N1—C2 | 116.40 (10) | C3—C31—H312 | 108.3 (9) |
C11—N1—C6 | 123.66 (10) | H311—C31—H312 | 106.6 (12) |
C2—N1—C6 | 119.09 (9) | C31—C32—H321 | 111.5 (10) |
O11—C11—N1 | 122.89 (11) | C31—C32—H322 | 109.4 (10) |
O11—C11—C12 | 118.37 (11) | H321—C32—H322 | 108.1 (14) |
N1—C11—C12 | 118.73 (11) | C31—C32—H323 | 110.5 (10) |
C11—C12—Cl12 | 108.93 (9) | H321—C32—H323 | 109.2 (14) |
C11—C12—H122 | 107.9 (9) | H322—C32—H323 | 108.0 (14) |
Cl12—C12—H122 | 106.7 (9) | N41—C4—C5 | 123.68 (11) |
C11—C12—H121 | 114.1 (10) | N41—C4—C3 | 119.47 (10) |
Cl12—C12—H121 | 106.9 (11) | C5—C4—C3 | 116.76 (10) |
H122—C12—H121 | 112.1 (13) | C4—N41—O41A | 118.3 (8) |
N1—C2—C21 | 111.43 (9) | C4—N41—O41 | 112.32 (9) |
N1—C2—C3 | 109.23 (9) | O41A—N41—O41 | 129.4 (8) |
C21—C2—C3 | 116.23 (10) | N41—O41—H41 | 109.5 |
N1—C2—H2 | 105.3 (8) | N41—O41A—H41A | 109.5 |
C21—C2—H2 | 106.5 (9) | C4—C5—C6 | 114.83 (10) |
C3—C2—H2 | 107.5 (9) | C4—C5—H51 | 107.5 (8) |
C26—C21—C22 | 118.17 (11) | C6—C5—H51 | 109.3 (8) |
C26—C21—C2 | 122.80 (11) | C4—C5—H52 | 110.1 (8) |
C22—C21—C2 | 118.96 (11) | C6—C5—H52 | 107.8 (8) |
C23—C22—C21 | 121.10 (12) | H51—C5—H52 | 107.0 (11) |
C23—C22—H22 | 119.1 (9) | N1—C6—C61 | 114.76 (9) |
C21—C22—H22 | 119.7 (9) | N1—C6—C5 | 110.26 (9) |
C22—C23—C24 | 120.39 (12) | C61—C6—C5 | 106.08 (9) |
C22—C23—H23 | 119.7 (9) | N1—C6—H6 | 108.6 (8) |
C24—C23—H23 | 119.9 (9) | C61—C6—H6 | 108.1 (8) |
C25—C24—C23 | 118.99 (12) | C5—C6—H6 | 108.8 (8) |
C25—C24—H24 | 120.7 (9) | C62—C61—C66 | 118.98 (11) |
C23—C24—H24 | 120.3 (9) | C62—C61—C6 | 121.96 (11) |
C24—C25—C26 | 120.65 (12) | C66—C61—C6 | 118.70 (11) |
C24—C25—H25 | 120.2 (9) | C63—C62—C61 | 120.53 (12) |
C26—C25—H25 | 119.1 (9) | C63—C62—H62 | 119.4 (9) |
C21—C26—C25 | 120.63 (12) | C61—C62—H62 | 120.1 (9) |
C21—C26—H26 | 120.8 (9) | C64—C63—C62 | 120.20 (13) |
C25—C26—H26 | 118.6 (9) | C64—C63—H63 | 120.6 (10) |
C4—C3—C31 | 111.96 (10) | C62—C63—H63 | 119.2 (10) |
C4—C3—C2 | 108.74 (10) | C65—C64—C63 | 119.57 (12) |
C31—C3—C2 | 111.76 (10) | C65—C64—H64 | 119.8 (10) |
C4—C3—H3 | 109.6 (8) | C63—C64—H64 | 120.6 (10) |
C31—C3—H3 | 107.4 (9) | C64—C65—C66 | 120.46 (13) |
C2—C3—H3 | 107.2 (8) | C64—C65—H65 | 120.9 (10) |
C32—C31—C3 | 112.71 (11) | C66—C65—H65 | 118.6 (10) |
C32—C31—H311 | 109.5 (9) | C65—C66—C61 | 120.25 (13) |
C3—C31—H311 | 109.6 (9) | C65—C66—H66 | 120.7 (9) |
C32—C31—H312 | 110.0 (9) | C61—C66—H66 | 119.0 (9) |
| | | |
C2—N1—C11—O11 | 13.36 (17) | C31—C3—C4—N41 | −87.31 (13) |
C6—N1—C11—O11 | −177.36 (11) | C2—C3—C4—N41 | 148.71 (11) |
C2—N1—C11—C12 | −165.28 (10) | C31—C3—C4—C5 | 95.94 (12) |
C6—N1—C11—C12 | 4.00 (17) | C2—C3—C4—C5 | −28.04 (14) |
O11—C11—C12—Cl12 | −98.47 (12) | C5—C4—N41—O41A | 178.2 (10) |
N1—C11—C12—Cl12 | 80.23 (12) | C3—C4—N41—O41A | 1.7 (10) |
C11—N1—C2—C21 | −102.07 (12) | C5—C4—N41—O41 | −2.06 (16) |
C6—N1—C2—C21 | 88.14 (12) | C3—C4—N41—O41 | −178.57 (10) |
C11—N1—C2—C3 | 128.16 (11) | N41—C4—C5—C6 | 156.61 (11) |
C6—N1—C2—C3 | −41.63 (13) | C3—C4—C5—C6 | −26.80 (15) |
N1—C2—C21—C26 | −144.21 (11) | C11—N1—C6—C61 | 58.74 (15) |
C3—C2—C21—C26 | −18.22 (16) | C2—N1—C6—C61 | −132.25 (11) |
N1—C2—C21—C22 | 38.84 (14) | C11—N1—C6—C5 | 178.43 (10) |
C3—C2—C21—C22 | 164.83 (10) | C2—N1—C6—C5 | −12.56 (14) |
C26—C21—C22—C23 | 3.03 (18) | C4—C5—C6—N1 | 48.02 (13) |
C2—C21—C22—C23 | −179.88 (11) | C4—C5—C6—C61 | 172.84 (10) |
C21—C22—C23—C24 | −1.56 (19) | N1—C6—C61—C62 | 46.18 (15) |
C22—C23—C24—C25 | −0.73 (19) | C5—C6—C61—C62 | −75.81 (13) |
C23—C24—C25—C26 | 1.50 (19) | N1—C6—C61—C66 | −140.69 (11) |
C22—C21—C26—C25 | −2.25 (18) | C5—C6—C61—C66 | 97.32 (12) |
C2—C21—C26—C25 | −179.23 (11) | C66—C61—C62—C63 | −0.67 (18) |
C24—C25—C26—C21 | 0.02 (19) | C6—C61—C62—C63 | 172.44 (11) |
N1—C2—C3—C4 | 61.95 (12) | C61—C62—C63—C64 | 0.00 (19) |
C21—C2—C3—C4 | −65.15 (13) | C62—C63—C64—C65 | 0.5 (2) |
N1—C2—C3—C31 | −62.15 (12) | C63—C64—C65—C66 | −0.4 (2) |
C21—C2—C3—C31 | 170.75 (10) | C64—C65—C66—C61 | −0.3 (2) |
C4—C3—C31—C32 | 72.25 (13) | C62—C61—C66—C65 | 0.80 (18) |
C2—C3—C31—C32 | −165.48 (10) | C6—C61—C66—C65 | −172.54 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···N41i | 0.84 | 2.05 | 2.7991 (13) | 148 |
O41A—H41A···N41i | 0.84 | 2.00 | 2.76 (2) | 150 |
C66—H66···O11ii | 0.956 (17) | 2.451 (17) | 3.3550 (17) | 157.6 (13) |
Symmetry codes: (i) −x, −y+2, −z; (ii) x, −y+2, z−1/2. |
(II) 1-chloroacetyl-2,6-diphenyl-3-(propan-2-yl)piperidin-4-one oxime
top
Crystal data top
C22H25ClN2O2 | F(000) = 816 |
Mr = 384.89 | Dx = 1.281 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2yn | Cell parameters from 8550 reflections |
a = 9.469 (1) Å | θ = 3.5–75.3° |
b = 16.658 (2) Å | µ = 1.84 mm−1 |
c = 12.653 (2) Å | T = 295 K |
β = 90.29 (1)° | Block, colourless |
V = 1995.8 (4) Å3 | 0.4 × 0.2 × 0.2 mm |
Z = 4 | |
Data collection top
Oxford SuperNova diffractometer (single source at offset) with Atlas detector | 3877 independent reflections |
Radiation source: Nova (Cu) X-ray Source | 3643 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.016 |
Detector resolution: 5.2679 pixels mm-1 | θmax = 76.0°, θmin = 4.4° |
ω–scan | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −19→20 |
Tmin = 0.448, Tmax = 1.000 | l = −14→15 |
10226 measured reflections | |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0619P)2 + 0.628P] where P = (Fo2 + 2Fc2)/3 |
3877 reflections | (Δ/σ)max = 0.001 |
322 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C22H25ClN2O2 | V = 1995.8 (4) Å3 |
Mr = 384.89 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 9.469 (1) Å | µ = 1.84 mm−1 |
b = 16.658 (2) Å | T = 295 K |
c = 12.653 (2) Å | 0.4 × 0.2 × 0.2 mm |
β = 90.29 (1)° | |
Data collection top
Oxford SuperNova diffractometer (single source at offset) with Atlas detector | 3877 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 3643 reflections with I > 2σ(I) |
Tmin = 0.448, Tmax = 1.000 | Rint = 0.016 |
10226 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.25 e Å−3 |
3877 reflections | Δρmin = −0.24 e Å−3 |
322 parameters | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell s.u.'s are taken into
account individually in the estimation of s.u.'s in distances, angles and
torsion angles; correlations between s.u.'s in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors
based on F2 are statistically about twice as large as those based on
F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.78576 (11) | 0.92571 (7) | 0.78049 (9) | 0.0319 (3) | |
C11 | 0.74589 (14) | 0.86786 (8) | 0.84921 (11) | 0.0340 (3) | |
O11 | 0.62220 (10) | 0.84585 (6) | 0.85791 (9) | 0.0433 (3) | |
C12 | 0.85572 (17) | 0.82716 (10) | 0.91839 (13) | 0.0421 (3) | |
H12A | 0.818 (2) | 0.7767 (13) | 0.9446 (15) | 0.052 (5)* | |
H12B | 0.941 (2) | 0.8195 (11) | 0.8854 (15) | 0.046 (5)* | |
Cl12 | 0.89127 (6) | 0.88632 (4) | 1.03268 (4) | 0.07258 (19) | |
C2 | 0.67172 (13) | 0.96699 (8) | 0.71944 (11) | 0.0334 (3) | |
H2 | 0.5835 (16) | 0.9442 (9) | 0.7493 (12) | 0.029 (4)* | |
C21 | 0.67635 (14) | 0.94218 (9) | 0.60345 (12) | 0.0369 (3) | |
C22 | 0.6644 (2) | 0.86071 (11) | 0.58016 (15) | 0.0512 (4) | |
H22 | 0.657 (2) | 0.8251 (13) | 0.6346 (18) | 0.062 (6)* | |
C23 | 0.6691 (2) | 0.83338 (13) | 0.47693 (16) | 0.0638 (5) | |
H23 | 0.663 (3) | 0.7736 (18) | 0.464 (2) | 0.089 (8)* | |
C24 | 0.6854 (2) | 0.88749 (14) | 0.39500 (16) | 0.0636 (5) | |
H24 | 0.690 (3) | 0.8666 (16) | 0.325 (2) | 0.089 (8)* | |
C25 | 0.6928 (2) | 0.96777 (14) | 0.41612 (15) | 0.0609 (5) | |
H25 | 0.698 (3) | 1.0070 (15) | 0.3601 (19) | 0.076 (7)* | |
C26 | 0.68789 (18) | 0.99569 (11) | 0.52001 (13) | 0.0482 (4) | |
H26 | 0.694 (2) | 1.0525 (13) | 0.5345 (15) | 0.053 (5)* | |
C3 | 0.67526 (14) | 1.05722 (8) | 0.74382 (12) | 0.0363 (3) | |
H3 | 0.6044 (19) | 1.0822 (11) | 0.6987 (14) | 0.041 (4)* | |
C31 | 0.63681 (18) | 1.07317 (10) | 0.86154 (13) | 0.0450 (4) | |
H31 | 0.694 (2) | 1.0358 (13) | 0.9061 (17) | 0.064 (6)* | |
C32 | 0.6756 (3) | 1.15714 (13) | 0.89813 (19) | 0.0756 (6) | |
H32A | 0.6447 | 1.1647 | 0.9696 | 0.113* | |
H32B | 0.6306 | 1.1959 | 0.8531 | 0.113* | |
H32C | 0.7762 | 1.1639 | 0.8948 | 0.113* | |
C33 | 0.4810 (2) | 1.05874 (15) | 0.87974 (17) | 0.0677 (5) | |
H33A | 0.4267 | 1.0941 | 0.8354 | 0.102* | |
H33B | 0.4591 | 1.0690 | 0.9525 | 0.102* | |
H33C | 0.4584 | 1.0040 | 0.8628 | 0.102* | |
C4 | 0.81671 (15) | 1.09051 (8) | 0.71143 (13) | 0.0393 (3) | |
N41 | 0.81935 (14) | 1.16369 (8) | 0.68143 (13) | 0.0483 (3) | |
O41 | 0.95614 (12) | 1.18733 (7) | 0.65091 (12) | 0.0598 (4) | |
H41 | 0.943 (3) | 1.2426 (15) | 0.6404 (19) | 0.074 (7)* | |
C5 | 0.94019 (15) | 1.03451 (9) | 0.70844 (14) | 0.0415 (3) | |
H5A | 0.9493 (19) | 1.0172 (11) | 0.6361 (15) | 0.043 (5)* | |
H5B | 1.025 (2) | 1.0623 (12) | 0.7258 (16) | 0.056 (5)* | |
C6 | 0.93036 (14) | 0.96136 (8) | 0.78195 (12) | 0.0338 (3) | |
H6 | 0.9467 (16) | 0.9799 (9) | 0.8513 (13) | 0.030 (4)* | |
C61 | 1.04678 (14) | 0.90329 (8) | 0.75142 (12) | 0.0358 (3) | |
C62 | 1.03821 (18) | 0.85701 (11) | 0.66064 (14) | 0.0501 (4) | |
H62 | 0.955 (2) | 0.8593 (12) | 0.6177 (16) | 0.054 (5)* | |
C63 | 1.1484 (2) | 0.80675 (13) | 0.63292 (19) | 0.0655 (5) | |
H63 | 1.139 (3) | 0.7738 (16) | 0.572 (2) | 0.084 (8)* | |
C64 | 1.2694 (2) | 0.80332 (13) | 0.69455 (19) | 0.0654 (5) | |
H64 | 1.344 (3) | 0.7673 (15) | 0.6755 (19) | 0.077 (7)* | |
C65 | 1.27954 (18) | 0.85004 (12) | 0.78348 (17) | 0.0573 (5) | |
H65 | 1.364 (3) | 0.8485 (14) | 0.8276 (18) | 0.069 (6)* | |
C66 | 1.16901 (16) | 0.89970 (10) | 0.81251 (14) | 0.0448 (4) | |
H66 | 1.173 (2) | 0.9323 (12) | 0.8769 (16) | 0.051 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0265 (5) | 0.0295 (5) | 0.0397 (6) | 0.0000 (4) | −0.0018 (4) | 0.0020 (4) |
C11 | 0.0335 (7) | 0.0275 (6) | 0.0411 (7) | 0.0019 (5) | 0.0017 (5) | −0.0012 (5) |
O11 | 0.0325 (5) | 0.0338 (5) | 0.0636 (7) | −0.0018 (4) | 0.0034 (5) | 0.0075 (5) |
C12 | 0.0393 (8) | 0.0406 (8) | 0.0463 (8) | 0.0018 (6) | −0.0007 (6) | 0.0092 (6) |
Cl12 | 0.0845 (4) | 0.0805 (4) | 0.0525 (3) | −0.0091 (3) | −0.0199 (2) | −0.0002 (2) |
C2 | 0.0259 (6) | 0.0331 (7) | 0.0411 (7) | 0.0012 (5) | −0.0027 (5) | 0.0028 (5) |
C21 | 0.0275 (6) | 0.0404 (7) | 0.0426 (8) | 0.0012 (5) | −0.0050 (5) | 0.0003 (6) |
C22 | 0.0598 (10) | 0.0452 (9) | 0.0486 (10) | 0.0010 (7) | −0.0142 (8) | −0.0027 (7) |
C23 | 0.0767 (13) | 0.0555 (11) | 0.0588 (11) | 0.0099 (9) | −0.0219 (10) | −0.0149 (9) |
C24 | 0.0610 (11) | 0.0842 (14) | 0.0454 (10) | 0.0140 (10) | −0.0100 (8) | −0.0127 (9) |
C25 | 0.0591 (11) | 0.0802 (14) | 0.0433 (9) | 0.0007 (9) | 0.0020 (8) | 0.0085 (9) |
C26 | 0.0477 (9) | 0.0504 (9) | 0.0464 (9) | −0.0019 (7) | −0.0005 (7) | 0.0049 (7) |
C3 | 0.0312 (7) | 0.0324 (7) | 0.0451 (8) | 0.0038 (5) | −0.0026 (6) | 0.0020 (6) |
C31 | 0.0473 (8) | 0.0406 (8) | 0.0469 (9) | 0.0074 (6) | −0.0015 (7) | −0.0025 (6) |
C32 | 0.0954 (17) | 0.0581 (12) | 0.0734 (14) | −0.0068 (11) | 0.0117 (12) | −0.0222 (10) |
C33 | 0.0561 (11) | 0.0886 (15) | 0.0586 (11) | −0.0001 (10) | 0.0157 (9) | −0.0093 (10) |
C4 | 0.0366 (7) | 0.0303 (7) | 0.0509 (9) | −0.0003 (5) | −0.0035 (6) | 0.0013 (6) |
N41 | 0.0398 (7) | 0.0365 (7) | 0.0685 (9) | −0.0022 (5) | 0.0012 (6) | 0.0057 (6) |
O41 | 0.0426 (6) | 0.0368 (6) | 0.1001 (10) | −0.0020 (5) | 0.0075 (6) | 0.0126 (6) |
C5 | 0.0306 (7) | 0.0365 (7) | 0.0575 (10) | −0.0019 (6) | 0.0019 (6) | 0.0067 (6) |
C6 | 0.0269 (6) | 0.0338 (7) | 0.0406 (8) | −0.0016 (5) | −0.0030 (5) | −0.0003 (5) |
C61 | 0.0284 (6) | 0.0345 (7) | 0.0447 (8) | −0.0003 (5) | 0.0009 (5) | 0.0047 (6) |
C62 | 0.0387 (8) | 0.0556 (10) | 0.0561 (10) | 0.0048 (7) | −0.0024 (7) | −0.0102 (8) |
C63 | 0.0532 (10) | 0.0684 (12) | 0.0751 (13) | 0.0095 (9) | 0.0092 (9) | −0.0222 (10) |
C64 | 0.0438 (9) | 0.0609 (11) | 0.0917 (15) | 0.0172 (8) | 0.0133 (9) | −0.0013 (10) |
C65 | 0.0326 (8) | 0.0637 (11) | 0.0754 (13) | 0.0095 (7) | −0.0036 (8) | 0.0146 (9) |
C66 | 0.0324 (7) | 0.0496 (9) | 0.0524 (9) | 0.0023 (6) | −0.0042 (6) | 0.0057 (7) |
Geometric parameters (Å, º) top
N1—C11 | 1.3530 (18) | C31—H31 | 1.00 (2) |
N1—C2 | 1.4924 (16) | C32—H32A | 0.9600 |
N1—C6 | 1.4925 (16) | C32—H32B | 0.9600 |
C11—O11 | 1.2327 (17) | C32—H32C | 0.9600 |
C11—C12 | 1.516 (2) | C33—H33A | 0.9600 |
C12—Cl12 | 1.7807 (18) | C33—H33B | 0.9600 |
C12—H12A | 0.97 (2) | C33—H33C | 0.9600 |
C12—H12B | 0.92 (2) | C4—N41 | 1.2770 (19) |
C2—C21 | 1.526 (2) | C4—C5 | 1.496 (2) |
C2—C3 | 1.5348 (19) | N41—O41 | 1.4096 (18) |
C2—H2 | 0.994 (15) | O41—H41 | 0.94 (3) |
C21—C26 | 1.386 (2) | C5—C6 | 1.536 (2) |
C21—C22 | 1.393 (2) | C5—H5A | 0.964 (19) |
C22—C23 | 1.384 (3) | C5—H5B | 0.95 (2) |
C22—H22 | 0.91 (2) | C6—C61 | 1.5181 (19) |
C23—C24 | 1.383 (3) | C6—H6 | 0.943 (16) |
C23—H23 | 1.01 (3) | C61—C62 | 1.385 (2) |
C24—C25 | 1.365 (3) | C61—C66 | 1.390 (2) |
C24—H24 | 0.96 (3) | C62—C63 | 1.384 (2) |
C25—C26 | 1.395 (3) | C62—H62 | 0.96 (2) |
C25—H25 | 0.97 (2) | C63—C64 | 1.384 (3) |
C26—H26 | 0.97 (2) | C63—H63 | 0.95 (3) |
C3—C4 | 1.508 (2) | C64—C65 | 1.371 (3) |
C3—C31 | 1.558 (2) | C64—H64 | 0.96 (3) |
C3—H3 | 0.972 (19) | C65—C66 | 1.385 (2) |
C31—C33 | 1.514 (3) | C65—H65 | 0.97 (2) |
C31—C32 | 1.518 (3) | C66—H66 | 0.98 (2) |
| | | |
C11—N1—C2 | 117.21 (11) | C31—C32—H32A | 109.5 |
C11—N1—C6 | 122.30 (11) | C31—C32—H32B | 109.5 |
C2—N1—C6 | 118.98 (10) | H32A—C32—H32B | 109.5 |
O11—C11—N1 | 122.52 (13) | C31—C32—H32C | 109.5 |
O11—C11—C12 | 117.69 (13) | H32A—C32—H32C | 109.5 |
N1—C11—C12 | 119.79 (12) | H32B—C32—H32C | 109.5 |
C11—C12—Cl12 | 110.34 (11) | C31—C33—H33A | 109.5 |
C11—C12—H12A | 109.2 (12) | C31—C33—H33B | 109.5 |
Cl12—C12—H12A | 105.7 (11) | H33A—C33—H33B | 109.5 |
C11—C12—H12B | 113.7 (12) | C31—C33—H33C | 109.5 |
Cl12—C12—H12B | 106.3 (12) | H33A—C33—H33C | 109.5 |
H12A—C12—H12B | 111.2 (16) | H33B—C33—H33C | 109.5 |
N1—C2—C21 | 110.42 (11) | N41—C4—C5 | 124.83 (14) |
N1—C2—C3 | 109.40 (11) | N41—C4—C3 | 116.77 (13) |
C21—C2—C3 | 117.26 (12) | C5—C4—C3 | 118.21 (12) |
N1—C2—H2 | 103.6 (9) | C4—N41—O41 | 111.56 (13) |
C21—C2—H2 | 106.9 (9) | N41—O41—H41 | 101.2 (15) |
C3—C2—H2 | 108.3 (9) | C4—C5—C6 | 115.44 (13) |
C26—C21—C22 | 118.15 (15) | C4—C5—H5A | 106.5 (11) |
C26—C21—C2 | 124.14 (14) | C6—C5—H5A | 110.1 (11) |
C22—C21—C2 | 117.69 (14) | C4—C5—H5B | 110.4 (12) |
C23—C22—C21 | 121.13 (18) | C6—C5—H5B | 107.5 (12) |
C23—C22—H22 | 120.2 (14) | H5A—C5—H5B | 106.6 (16) |
C21—C22—H22 | 118.6 (14) | N1—C6—C61 | 114.25 (11) |
C24—C23—C22 | 119.82 (19) | N1—C6—C5 | 111.50 (11) |
C24—C23—H23 | 122.1 (16) | C61—C6—C5 | 107.76 (12) |
C22—C23—H23 | 118.0 (16) | N1—C6—H6 | 106.8 (9) |
C25—C24—C23 | 119.84 (19) | C61—C6—H6 | 109.3 (9) |
C25—C24—H24 | 122.4 (17) | C5—C6—H6 | 107.0 (9) |
C23—C24—H24 | 117.8 (17) | C62—C61—C66 | 118.84 (14) |
C24—C25—C26 | 120.59 (19) | C62—C61—C6 | 121.73 (13) |
C24—C25—H25 | 121.5 (14) | C66—C61—C6 | 119.32 (14) |
C26—C25—H25 | 117.9 (14) | C63—C62—C61 | 120.37 (17) |
C21—C26—C25 | 120.41 (17) | C63—C62—H62 | 120.1 (12) |
C21—C26—H26 | 119.4 (12) | C61—C62—H62 | 119.5 (12) |
C25—C26—H26 | 120.2 (12) | C64—C63—C62 | 120.34 (19) |
C4—C3—C2 | 108.90 (11) | C64—C63—H63 | 120.7 (16) |
C4—C3—C31 | 114.16 (13) | C62—C63—H63 | 119.0 (17) |
C2—C3—C31 | 110.74 (12) | C65—C64—C63 | 119.56 (17) |
C4—C3—H3 | 107.1 (10) | C65—C64—H64 | 120.9 (15) |
C2—C3—H3 | 106.7 (11) | C63—C64—H64 | 119.6 (15) |
C31—C3—H3 | 108.9 (10) | C64—C65—C66 | 120.45 (17) |
C33—C31—C32 | 109.55 (17) | C64—C65—H65 | 120.6 (14) |
C33—C31—C3 | 110.55 (14) | C66—C65—H65 | 118.9 (14) |
C32—C31—C3 | 113.04 (15) | C65—C66—C61 | 120.43 (17) |
C33—C31—H31 | 110.1 (13) | C65—C66—H66 | 121.5 (12) |
C32—C31—H31 | 105.8 (13) | C61—C66—H66 | 118.1 (11) |
C3—C31—H31 | 107.7 (12) | | |
| | | |
C2—N1—C11—O11 | 4.2 (2) | C4—C3—C31—C32 | 41.4 (2) |
C6—N1—C11—O11 | 170.04 (13) | C2—C3—C31—C32 | 164.71 (15) |
C2—N1—C11—C12 | −176.33 (12) | C2—C3—C4—N41 | 149.75 (15) |
C6—N1—C11—C12 | −10.5 (2) | C31—C3—C4—N41 | −85.92 (18) |
O11—C11—C12—Cl12 | −97.36 (14) | C2—C3—C4—C5 | −25.49 (18) |
N1—C11—C12—Cl12 | 83.14 (15) | C31—C3—C4—C5 | 98.83 (16) |
C11—N1—C2—C21 | −109.29 (13) | C5—C4—N41—O41 | −3.7 (2) |
C6—N1—C2—C21 | 84.39 (14) | C3—C4—N41—O41 | −178.61 (13) |
C11—N1—C2—C3 | 120.23 (13) | N41—C4—C5—C6 | 159.26 (16) |
C6—N1—C2—C3 | −46.09 (16) | C3—C4—C5—C6 | −25.9 (2) |
N1—C2—C21—C26 | −124.11 (14) | C11—N1—C6—C61 | 66.74 (17) |
C3—C2—C21—C26 | 2.1 (2) | C2—N1—C6—C61 | −127.67 (13) |
N1—C2—C21—C22 | 57.69 (17) | C11—N1—C6—C5 | −170.78 (13) |
C3—C2—C21—C22 | −176.11 (13) | C2—N1—C6—C5 | −5.19 (17) |
C26—C21—C22—C23 | 2.4 (3) | C4—C5—C6—N1 | 41.84 (18) |
C2—C21—C22—C23 | −179.31 (16) | C4—C5—C6—C61 | 167.98 (13) |
C21—C22—C23—C24 | −0.3 (3) | N1—C6—C61—C62 | 50.09 (19) |
C22—C23—C24—C25 | −1.7 (3) | C5—C6—C61—C62 | −74.41 (17) |
C23—C24—C25—C26 | 1.7 (3) | N1—C6—C61—C66 | −133.78 (14) |
C22—C21—C26—C25 | −2.5 (2) | C5—C6—C61—C66 | 101.72 (16) |
C2—C21—C26—C25 | 179.35 (15) | C66—C61—C62—C63 | 1.5 (3) |
C24—C25—C26—C21 | 0.5 (3) | C6—C61—C62—C63 | 177.65 (17) |
N1—C2—C3—C4 | 60.54 (15) | C61—C62—C63—C64 | −1.2 (3) |
C21—C2—C3—C4 | −66.15 (15) | C62—C63—C64—C65 | 0.1 (3) |
N1—C2—C3—C31 | −65.77 (14) | C63—C64—C65—C66 | 0.8 (3) |
C21—C2—C3—C31 | 167.54 (12) | C64—C65—C66—C61 | −0.5 (3) |
C4—C3—C31—C33 | 164.59 (15) | C62—C61—C66—C65 | −0.7 (2) |
C2—C3—C31—C33 | −72.07 (17) | C6—C61—C66—C65 | −176.90 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···O11i | 0.94 (3) | 1.83 (3) | 2.7449 (16) | 165 (2) |
C65—H65···O11ii | 0.97 (2) | 2.47 (2) | 3.375 (2) | 153.9 (18) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x+1, y, z. |
Experimental details
| (I) | (I_100K) | (II) |
Crystal data |
Chemical formula | C21H23ClN2O2 | C21H23ClN2O2 | C22H25ClN2O2 |
Mr | 370.86 | 370.86 | 384.89 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, P21/n |
Temperature (K) | 293 | 100 | 295 |
a, b, c (Å) | 34.176 (3), 9.1227 (9), 12.1235 (11) | 33.849 (3), 9.025 (1), 11.980 (1) | 9.469 (1), 16.658 (2), 12.653 (2) |
β (°) | 91.962 (8) | 92.51 (1) | 90.29 (1) |
V (Å3) | 3777.6 (6) | 3656.2 (6) | 1995.8 (4) |
Z | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Cu Kα |
µ (mm−1) | 0.22 | 0.23 | 1.84 |
Crystal size (mm) | 0.3 × 0.15 × 0.1 | 0.3 × 0.15 × 0.1 | 0.4 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Oxford Xcalibur diffractometer with Sapphire2 (large Be window) detector | Oxford Xcalibur diffractometer with Eos detector | Oxford SuperNova diffractometer (single source at offset) with Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.993, 1.000 | 0.957, 1.000 | 0.448, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8775, 3304, 1743 | 14395, 3729, 3245 | 10226, 3877, 3643 |
Rint | 0.051 | 0.013 | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 | 0.639 | 0.629 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.079, 1.00 | 0.030, 0.078, 1.08 | 0.045, 0.120, 1.05 |
No. of reflections | 3304 | 3729 | 3877 |
No. of parameters | 297 | 312 | 322 |
No. of restraints | 1 | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.29 | 0.31, −0.26 | 0.25, −0.24 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···N41i | 0.82 | 2.11 | 2.842 (2) | 148.8 |
O41A—H41A···N41i | 0.82 | 2.07 | 2.81 (3) | 150.5 |
C66—H66···O11ii | 0.92 (2) | 2.50 (2) | 3.380 (4) | 162 (2) |
Symmetry codes: (i) −x, −y+2, −z; (ii) x, −y+2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (I_100K) top
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···N41i | 0.84 | 2.05 | 2.7991 (13) | 148.3 |
O41A—H41A···N41i | 0.84 | 2.00 | 2.76 (2) | 150.3 |
C66—H66···O11ii | 0.956 (17) | 2.451 (17) | 3.3550 (17) | 157.6 (13) |
Symmetry codes: (i) −x, −y+2, −z; (ii) x, −y+2, z−1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···O11i | 0.94 (3) | 1.83 (3) | 2.7449 (16) | 165 (2) |
C65—H65···O11ii | 0.97 (2) | 2.47 (2) | 3.375 (2) | 153.9 (18) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x+1, y, z. |
Selected torsion angles (°); the second line, where present, refers to the
minor-occupancy part top | (I) | (II) |
C6—N1—C2—C3 | -43.5 (3) | -46.09 (16) |
N1—C2—C3—C4 | 62.2 (2) | 60.54 (15) |
C2—C3—C4—C5 | -27.1 (3) | -25.49 (18) |
C3—C4—C5—C6 | -27.6 (3) | -25.9 (2) |
C4—C5—C6—N1 | 47.2 (3) | 41.84 (18) |
C5—C6—N1—C2 | -10.3 (3) | -5.19 (17) |
C2—N1—C11—O11 | 12.5 (4) | 4.2 (2) |
C2—N1—C11—C12 | -166.4 (2) | -17633 (12) |
O11—C11—C12—Cl12 | -94.6 (3) | -97.36 (14) |
N1—C11—C12—Cl12 | 84.4 (3) | 83.14 (15) |
C6—N1—C2—C21 | 87.4 (2) | 84.39 (14) |
C11—N1—C2—C3 | 126.5 (2) | 120.23 (13) |
N1—C2—C21—C26 | -142.4 (2) | -124.11 (14) |
C3—C2—C21—C26 | -15.6 (3) | 2.1 (2) |
N1—C2—C21—C22 | 40.5 (3) | 57.69 (17) |
C3—C2—C21—C22 | 167.3 (2) | -176.11 (13) |
C21—C2—C3—C4 | -66.0 (2) | -66.15 (15) |
N1—C2—C3—C31 | -62.4 (3) | -65.77 (14) |
C4—C3—C31—C32 | 73.0 (3) | 41.4 (2) |
C2—C3—C4—N41 | 149.7 (2) | 149.75 (15) |
C31—C3—C4—C5 | 97.3 (2) | 98.83 (16) |
C5—C4—N41—O41 | -2.5 (3) | -3.7 (2) |
| 179 (1) | |
C3—C4—N41—O41 | -179.10 (18) | -178.61 (13) |
| 3(1) | |
N41—C4—C5—C6 | 155.7 (2) | 159.26 (16) |
C2—N1—C6—C61 | -130.9 (2) | -127.67 (13) |
C4—C5—C6—C61 | 172.20 (19) | 167.98 (13) |
N1—C6—C61—C62 | 45.7 (3) | 50.09 (19) |
C5—C6—C61—C62 | -76.7 (3) | -74.41 (17) |
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The oxime functional group, R1R2C═N—OH, despite its good hydrogen-bonding functionalities, is far less well explored in crystal engineering (i.e. constructing crystals of chosen architecture and properties) than, for instance, carboxyl or amide groups. The hydrogen-bonded structures of oximes were studied by e.g. Bertolasi et al. (1982), and more recently by Bruton et al. (2003). The results of these studies show that in cases when there are no competing hydrogen-bond acceptors, the main structural motifs are created by O—H···N oxime-to-oxime hydrogen bonds, and these can be either the R22(6) ring (Etter et al., 1990; Bernstein et al., 1995) or the C(3) chain motif (Fig. 1). Both these motifs are found in structures deposited in the Cambridge Structural Database (Version of November 2009; Allen, 2002), with ca 4:1 preference for the ring motif (Bruton et al., 2003). The presence of additional substituents capable of donating to or accepting a hydrogen bond can of course change this simple pattern. For instance, it is known that when there are both oxime and carboxyl groups, almost exclusively the mixed `carboxime' motif R22(7) is formed (see, for example, Desiraju, 1995; Maurin et al., 1995; Kubicki et al., 2000).
There are some examples of oxime crystal structures in which the oxime function adopts two alternative configurations with more or less equal probability, for instance in violuric acid [pyrimidine-2,4,5,6(1H,3H)-tetrone-5-oxime; Nichol & Clegg, 2005], 1,2,3-indantrionemonooxime (Ivanova et al., 2002), or in a series of three trans-2,6-diaryl derivatives of oximes of N-hydroxy-4-piperidone (Díaz et al., 1997). In the majority of cases, the disorder affects the whole N—OH fragment and both alternative positions are similarly occupied, but this is not always the case. Ciunik (1996) has shown, by careful study of the low-temperature crystal structures of 1-(3,4-di-O-acetyl-2-deoxy-2-hydroxyimino-α-D-erythro-pentopyranosyl)pyrazole and 2-benzoyloxycyclohexanone oxime, that the distributions of the electron densities in these structures can be accurately described by the assumption that there are only ca 3–5% of molecules with an alternative configuration of the oxime group.
The crystal structures of N-chloroacetyl-3-ethyl-2,6-diphenylpiperidin-4-one oxime, (I), and N-chloroacetyl-3-(propane-2-yl)-2,6-diphenylpiperidin-4-one oxime, (II), provide an example of two very closely related oximes with one additional hydrogen-bond accepting carbonyl group, but different structural motifs are formed.
In (I) the difference Fourier maps show relatively large peaks in the vicinity of the oxime group, and this was the main reason for repeating the data collection for this compound at a lower temperature. These features are also observed at 100 K, and it turns out that the oxime group is slightly disordered over two positions, with site-occupancy factors of 0.943 (3) and 0.057 (3) at 100 K, and 0.937 (3) and 0.063 (3) at room temperature. It might be noted that in this case only the hydroxy group is described as disordered and the position of the N atom is described as unique; no strange features in displacement parameters or geometries are observed. The stability of the occupancies over this temperature range suggests that the disorder is of a statistical rather than a dynamic nature. Fig. 2 compares the difference Fourier maps calculated for (I) at 100 K before (Fig. 2a) and after (Fig. 2b) taking this slight disorder into account.
Figs. 3 and 4 show perspective views of the molecules of (I) and (II), respectively. The bond lengths and angles in both compounds are very similar; when comparing the two room-temperature structures, the vast majority of these data differ by less than 3σ. These geometric parameters even produce quite good results in the normal probability plot test (Abrahams & Keve, 1971; International Tables for X-ray Crystallography, 1974) which, in a sense, describes the deviation from a statistical nature of the differences between the structures under consideration. In the case of (I) and (II), the correlation coefficient R2 between the set of experimental differences between the geometric parameters and the theoretical values for a pure statistical distribution is 0.91 for the bond lengths and is even better - as high as 0.967 - for the angles.
The conformations of the piperidine rings in (I) and (II) are best described as distorted twist-boat. The distortions from the ideal conformation are quite severe, as can be seen from the large values of the asymmetry parameters (Duax & Norton, 1975), which quantitatively describe the distortion from ideal symmetry of a certain conformation. A twisted boat should have the Cs symmetry, and the values of the ΔCs2,3 parameter are 13.9° for (I) and 18.1° for (II) (this is the best approximate symmetry which can be found). Both phenyl substituents are in axial positions (cf. Table 1 for the torsion angles), the chloroacetyl groups occupy (pseudo)-equatorial positions, the ethyl [in (I)] and 2-propyl [in (II)] groups are axial, and the position of the oxime function is closer to equatorial. The phenyl rings are planar to a good approximation. Interestingly, in all three cases the largest deviation from the mean plane of the phenyl ring at C2 is at least twice as large as that for the phenyl ring at C6. These mean planes make dihedral angles of 60.71 (9)° in (I) and 72.09 (6)° in (II). The acetyl groups are also planar to within 3σ, and their planes are almost perpendicular to the phenyl ring planes [dihedral angles in the range 74.53 (10)–87.36 (11)°]. The C—Cl bond from the chloroacetyl group is almost perpendicular to the plane of the rest of the group, and the Cl atom is ca 1.65 Å out of the plane.
These very closely related molecules turn out to show different organization in their crystal structures. In both cases, the main driving force of the packing is provided by the relatively strong hydrogen bonds. Also in both cases, there are - along with the oxime function, which can act as both hydrogen-bond donor and acceptor - additional relatively good hydrogen-bond acceptors, namely the carbonyl C═O groups. As discussed above, the geometric features of both molecules are almost identical, so for instance, there are no additional steric hindrances which might influence the hydrogen bonding. And still, despite all these similarities, the hydrogen-bond patterns are essentially different in the two structures. The molecules of (I) are connected into centrosymmetric pairs by means of relatively short O—H···N hydrogen bonds. The graph set connected with this motif is R22(6), typical for oxime functions and mostly preferred in the absence of other hydrogen-bond donors and/or acceptors. Interestingly, the disorder present in the structure does not influence the hydrogen-bond motif. A relatively short and linear C66—H66···O11 interaction connects neighbouring dimers into a kind of `ladder', forming C(7) chains and large R44(32) rings (Fig. 5). Some additional C—H···O, C—H···Cl and even C—H···π contacts might add stability to the packing (cf. Table 3 [Please clarify - none of these bond types occurs in any table given]). In (II), by contrast, there are no oxime-to-oxime bonds. The hydrogen-bonded chains along the [010] direction are created by means of N—H···O(carbonyl) hydrogen bonds. These C(9) chains are connected into layers parallel to (001) by weak C—H···O(carbonyl) hydrogen bonds (Fig. 6), which form C(8) chains on their own, and also a second-order R44(38) ring. In this case there are far fewer weak intermolecular contacts, and not even the N atom of the oxime group is involved in any such contacts.