Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680504208X/ci6691sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680504208X/ci6691Isup2.hkl |
CCDC reference: 296529
A solution of 3-(2-chloro-1-oxoethyl)-1-methyl-1-phenylcyclobutane (2.225 g, 10 mmol) and piperidine (1.70 g, 20 mmol) in absolute ethanol (50 ml) was refluxed with continuous stirring. After completion of the reaction, NH2OH·HCl (0.695 g, 10 mmol) was added. The course of both reactions was monitored by IR. The mixture was cooled to room temperature and neutralized with aqueous dilute ammonia (5%) to obtain the target product. It was filtered, washed with copious cold ethanol, recrystallized from ethanol and dried in air (yield 2.29 g, 80%; m.p. 425 K). IR (KBr, ν, cm−1): 3253 (–OH, oxime), 1613 (C═N); 1H NMR (CDCl3, TMS, δ, p.p.m.): 1.26–1.65 (m, 6H, –CH2– piperidine), 1.53 (s, 3H, –CH3 on cyclobutane), 2.25–2.60 (m, 8H, –CH2–, cyclobutane –CH2– plus piperidine –CH2– adjacent to N), 3.22 (s, 2H, –CH2–, adjacent to oxime), 3.79 (q, 1H, j = 3.67 Hz, >CH–), 7.01–7.35 (m, 5H, aromatics), 10.48 (s, 1H, –OH, D2O exchangeable).
H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.82 Å for OH, 0.93 Å for aromatic CH, 0.96 Å for CH3, 0.97 Å for CH2, and at 0.98 Å for CH group. The Uiso values were constrained to be 1.5Ueq of the carrier atom for hydroxyl and methyl H atoms and 1.2Ueq for the remaining H atoms. The same anisotropic displacement parameters were used for the atoms N2 and C11. Owing to the absence of any significant anomalous scatterers in the molecule, Friedel pairs were merged before the final refinement and the configuration is arbitrarily assigned.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
C18H26N2O | F(000) = 1248 |
Mr = 286.41 | Dx = 1.114 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 14206 reflections |
a = 10.8782 (5) Å | θ = 1.2–21.5° |
b = 5.8899 (3) Å | µ = 0.07 mm−1 |
c = 53.307 (3) Å | T = 296 K |
V = 3415.5 (3) Å3 | Prism, colourless |
Z = 8 | 0.64 × 0.45 × 0.13 mm |
Stoe IPDS-II diffractometer | 1661 reflections with I > 2σ(I) |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | Rint = 0.124 |
Plane graphite monochromator | θmax = 21.5°, θmin = 1.5° |
Detector resolution: 6.67 pixels mm-1 | h = −11→11 |
ω scans | k = −6→6 |
16092 measured reflections | l = −54→54 |
1988 independent reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0796P)2] where P = (Fo2 + 2Fc2)/3 |
1988 reflections | (Δ/σ)max = 0.001 |
374 parameters | Δρmax = 0.18 e Å−3 |
1 restraint | Δρmin = −0.11 e Å−3 |
C18H26N2O | V = 3415.5 (3) Å3 |
Mr = 286.41 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 10.8782 (5) Å | µ = 0.07 mm−1 |
b = 5.8899 (3) Å | T = 296 K |
c = 53.307 (3) Å | 0.64 × 0.45 × 0.13 mm |
Stoe IPDS-II diffractometer | 1661 reflections with I > 2σ(I) |
16092 measured reflections | Rint = 0.124 |
1988 independent reflections | θmax = 21.5° |
R[F2 > 2σ(F2)] = 0.046 | 1 restraint |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.18 e Å−3 |
1988 reflections | Δρmin = −0.11 e Å−3 |
374 parameters |
Experimental. Because of the long c cell parameter, the reflection spots were rather close to each other and to prevent the overlopping of these reflections the crystal to detector distance was increased to 180 mm resulting in the decrease of 2θmaximum. Attempts to decrease the crystal to detector distance from 180 mm resulted in the partial overlapping of peaks. The poor data/parameter ratio (5.32), low precision on C—C bonds (0.008 Å) and high displacement parameters may be due to low resolution. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 1.0890 (3) | 0.0766 (6) | 0.20274 (7) | 0.0993 (9) | |
H1 | 1.1559 | 0.0151 | 0.2047 | 0.149* | |
N1 | 0.7813 (3) | 0.2120 (6) | 0.21340 (7) | 0.0804 (9) | |
N2 | 1.0216 (3) | −0.0413 (7) | 0.18447 (8) | 0.0861 (8) | |
C1 | 0.8266 (4) | −0.1345 (8) | 0.12084 (10) | 0.0876 (13) | |
C2 | 0.8964 (4) | −0.2409 (8) | 0.14313 (9) | 0.0923 (13) | |
H2A | 0.8713 | −0.3952 | 0.1469 | 0.111* | |
H2B | 0.9851 | −0.2301 | 0.1417 | 0.111* | |
C3 | 0.8397 (4) | −0.0624 (9) | 0.16066 (9) | 0.0887 (13) | |
H3 | 0.7639 | −0.1216 | 0.1681 | 0.106* | |
C4 | 0.8090 (5) | 0.0807 (9) | 0.13700 (10) | 0.0988 (14) | |
H4A | 0.7258 | 0.1398 | 0.1368 | 0.119* | |
H4B | 0.8683 | 0.1997 | 0.1335 | 0.119* | |
C5 | 0.8440 (4) | 0.1039 (9) | 0.23447 (9) | 0.0906 (13) | |
H5A | 0.9083 | 0.2034 | 0.2407 | 0.109* | |
H5B | 0.8821 | −0.0363 | 0.2289 | 0.109* | |
C6 | 0.7538 (6) | 0.0538 (10) | 0.25537 (10) | 0.1057 (16) | |
H6A | 0.6926 | −0.0532 | 0.2494 | 0.127* | |
H6B | 0.7971 | −0.0160 | 0.2693 | 0.127* | |
C7 | 0.6908 (5) | 0.2660 (11) | 0.26430 (11) | 0.1155 (17) | |
H7A | 0.7502 | 0.3650 | 0.2723 | 0.139* | |
H7B | 0.6284 | 0.2270 | 0.2766 | 0.139* | |
C8 | 0.6318 (5) | 0.3884 (9) | 0.24234 (11) | 0.1073 (16) | |
H8A | 0.6002 | 0.5340 | 0.2479 | 0.129* | |
H8B | 0.5633 | 0.2995 | 0.2361 | 0.129* | |
C9 | 0.7248 (4) | 0.4251 (9) | 0.22141 (10) | 0.0967 (14) | |
H9A | 0.6841 | 0.4952 | 0.2072 | 0.116* | |
H9B | 0.7884 | 0.5279 | 0.2272 | 0.116* | |
C10 | 0.8686 (4) | 0.2593 (8) | 0.19264 (9) | 0.0872 (13) | |
H10A | 0.9373 | 0.3464 | 0.1992 | 0.105* | |
H10B | 0.8276 | 0.3514 | 0.1801 | 0.105* | |
C11 | 0.9170 (4) | 0.0473 (8) | 0.18038 (9) | 0.0861 (8) | |
C12 | 0.7055 (5) | −0.2525 (11) | 0.11516 (12) | 0.1171 (18) | |
H12A | 0.6656 | −0.1776 | 0.1014 | 0.176* | |
H12B | 0.6534 | −0.2465 | 0.1297 | 0.176* | |
H12C | 0.7209 | −0.4081 | 0.1108 | 0.176* | |
C13 | 0.9004 (4) | −0.1024 (9) | 0.09683 (10) | 0.0882 (13) | |
C14 | 0.8871 (5) | 0.0901 (10) | 0.08221 (11) | 0.1075 (16) | |
H14 | 0.8307 | 0.2010 | 0.0869 | 0.129* | |
C15 | 0.9570 (6) | 0.1200 (12) | 0.06054 (11) | 0.1183 (18) | |
H15 | 0.9480 | 0.2506 | 0.0509 | 0.142* | |
C16 | 1.0368 (7) | −0.0406 (16) | 0.05377 (13) | 0.127 (2) | |
H16 | 1.0841 | −0.0199 | 0.0394 | 0.153* | |
C17 | 1.0507 (6) | −0.2358 (12) | 0.06755 (12) | 0.1179 (17) | |
H17 | 1.1057 | −0.3476 | 0.0625 | 0.141* | |
C18 | 0.9822 (5) | −0.2633 (9) | 0.08893 (11) | 0.1034 (15) | |
H18 | 0.9916 | −0.3953 | 0.0983 | 0.124* | |
O2 | 0.6441 (3) | 0.4251 (6) | 0.36612 (7) | 0.0987 (9) | |
H2 | 0.5784 | 0.4901 | 0.3638 | 0.148* | |
N3 | 0.9494 (3) | 0.2861 (6) | 0.35525 (6) | 0.0802 (10) | |
N4 | 0.7120 (4) | 0.5424 (7) | 0.38445 (8) | 0.0941 (11) | |
C19 | 0.9078 (4) | 0.6470 (9) | 0.44767 (9) | 0.0925 (13) | |
C20 | 0.9178 (4) | 0.4234 (9) | 0.43260 (9) | 0.0963 (14) | |
H20A | 0.8540 | 0.3139 | 0.4365 | 0.116* | |
H20B | 0.9986 | 0.3539 | 0.4333 | 0.116* | |
C21 | 0.8935 (4) | 0.5610 (9) | 0.40819 (10) | 0.0947 (14) | |
H21 | 0.9719 | 0.6090 | 0.4009 | 0.114* | |
C22 | 0.8423 (4) | 0.7506 (8) | 0.42458 (9) | 0.0928 (13) | |
H22A | 0.7533 | 0.7497 | 0.4259 | 0.111* | |
H22B | 0.8721 | 0.9003 | 0.4201 | 0.111* | |
C23 | 1.0068 (4) | 0.0759 (8) | 0.34713 (10) | 0.0974 (14) | |
H23A | 0.9437 | −0.0283 | 0.3414 | 0.117* | |
H23B | 1.0484 | 0.0063 | 0.3613 | 0.117* | |
C24 | 1.0978 (5) | 0.1147 (9) | 0.32631 (11) | 0.1078 (16) | |
H24A | 1.1659 | 0.2045 | 0.3326 | 0.129* | |
H24B | 1.1303 | −0.0303 | 0.3208 | 0.129* | |
C25 | 1.0408 (6) | 0.2344 (11) | 0.30446 (12) | 0.1190 (18) | |
H25A | 0.9815 | 0.1354 | 0.2964 | 0.143* | |
H25B | 1.1037 | 0.2729 | 0.2923 | 0.143* | |
C26 | 0.9776 (5) | 0.4479 (10) | 0.31339 (10) | 0.1047 (16) | |
H26A | 0.9341 | 0.5175 | 0.2995 | 0.126* | |
H26B | 1.0386 | 0.5550 | 0.3194 | 0.126* | |
C27 | 0.8874 (4) | 0.3957 (8) | 0.33434 (9) | 0.0877 (13) | |
H27A | 0.8495 | 0.5355 | 0.3401 | 0.105* | |
H27B | 0.8231 | 0.2970 | 0.3281 | 0.105* | |
C28 | 0.8644 (4) | 0.2399 (8) | 0.37602 (8) | 0.0858 (12) | |
H28A | 0.9062 | 0.1472 | 0.3884 | 0.103* | |
H28B | 0.7952 | 0.1533 | 0.3697 | 0.103* | |
C29 | 0.8167 (4) | 0.4522 (8) | 0.38864 (9) | 0.0856 (13) | |
C30 | 1.0350 (5) | 0.7532 (12) | 0.45217 (14) | 0.141 (2) | |
H30A | 1.0807 | 0.7535 | 0.4368 | 0.211* | |
H30B | 1.0786 | 0.6661 | 0.4645 | 0.211* | |
H30C | 1.0253 | 0.9063 | 0.4580 | 0.211* | |
C31 | 0.8381 (4) | 0.6423 (9) | 0.47188 (10) | 0.0950 (14) | |
C32 | 0.7628 (6) | 0.8196 (10) | 0.47849 (10) | 0.1110 (16) | |
H32 | 0.7546 | 0.9416 | 0.4675 | 0.133* | |
C33 | 0.6981 (6) | 0.8225 (13) | 0.50121 (13) | 0.134 (2) | |
H33 | 0.6487 | 0.9460 | 0.5053 | 0.160* | |
C34 | 0.7076 (7) | 0.6463 (14) | 0.51713 (13) | 0.139 (2) | |
H34 | 0.6660 | 0.6496 | 0.5324 | 0.167* | |
C35 | 0.7769 (7) | 0.4659 (14) | 0.51115 (13) | 0.141 (2) | |
H35 | 0.7814 | 0.3427 | 0.5220 | 0.169* | |
C36 | 0.8428 (6) | 0.4629 (11) | 0.48844 (13) | 0.123 (2) | |
H36 | 0.8907 | 0.3369 | 0.4845 | 0.148* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0867 (18) | 0.111 (2) | 0.100 (2) | 0.0044 (16) | −0.0038 (17) | −0.0075 (19) |
N1 | 0.0729 (19) | 0.087 (2) | 0.081 (2) | 0.0055 (18) | 0.0010 (19) | 0.0003 (18) |
N2 | 0.0771 (16) | 0.099 (2) | 0.082 (2) | −0.0025 (16) | 0.0015 (16) | 0.0012 (16) |
C1 | 0.076 (2) | 0.097 (3) | 0.090 (3) | 0.003 (2) | −0.007 (2) | −0.009 (3) |
C2 | 0.096 (3) | 0.091 (3) | 0.090 (3) | 0.004 (2) | 0.000 (3) | 0.004 (3) |
C3 | 0.079 (3) | 0.105 (3) | 0.083 (3) | 0.001 (2) | 0.003 (2) | 0.000 (3) |
C4 | 0.088 (3) | 0.106 (4) | 0.102 (4) | 0.017 (3) | −0.005 (3) | −0.007 (3) |
C5 | 0.085 (3) | 0.106 (3) | 0.080 (3) | 0.003 (3) | −0.001 (2) | 0.011 (2) |
C6 | 0.107 (3) | 0.125 (4) | 0.085 (4) | 0.003 (3) | 0.009 (3) | 0.010 (3) |
C7 | 0.122 (4) | 0.135 (4) | 0.090 (3) | 0.003 (4) | 0.017 (3) | −0.011 (3) |
C8 | 0.100 (3) | 0.113 (4) | 0.108 (4) | 0.009 (3) | 0.014 (3) | −0.019 (3) |
C9 | 0.091 (3) | 0.094 (3) | 0.104 (4) | 0.012 (3) | 0.007 (3) | 0.004 (3) |
C10 | 0.084 (3) | 0.091 (3) | 0.086 (3) | 0.000 (2) | 0.004 (2) | 0.006 (2) |
C11 | 0.0771 (16) | 0.099 (2) | 0.082 (2) | −0.0025 (16) | 0.0015 (16) | 0.0012 (16) |
C12 | 0.099 (3) | 0.136 (5) | 0.116 (4) | −0.018 (3) | −0.001 (3) | −0.007 (3) |
C13 | 0.084 (3) | 0.095 (3) | 0.085 (3) | −0.003 (2) | −0.016 (3) | −0.001 (3) |
C14 | 0.117 (4) | 0.116 (4) | 0.090 (4) | 0.012 (3) | −0.010 (3) | 0.001 (3) |
C15 | 0.141 (5) | 0.122 (4) | 0.091 (4) | −0.007 (4) | −0.015 (4) | 0.012 (3) |
C16 | 0.139 (5) | 0.146 (6) | 0.096 (4) | −0.015 (5) | 0.004 (4) | 0.003 (4) |
C17 | 0.121 (4) | 0.135 (5) | 0.098 (4) | 0.012 (3) | 0.009 (3) | −0.008 (4) |
C18 | 0.103 (3) | 0.109 (4) | 0.099 (4) | 0.008 (3) | 0.000 (3) | 0.002 (3) |
O2 | 0.0896 (18) | 0.110 (2) | 0.097 (2) | 0.0034 (17) | −0.0006 (18) | −0.009 (2) |
N3 | 0.0721 (18) | 0.089 (2) | 0.079 (2) | 0.0039 (18) | 0.0017 (18) | 0.0051 (18) |
N4 | 0.088 (2) | 0.101 (3) | 0.093 (3) | −0.004 (2) | 0.006 (2) | −0.003 (2) |
C19 | 0.083 (3) | 0.102 (3) | 0.093 (3) | 0.001 (2) | −0.003 (2) | −0.004 (3) |
C20 | 0.088 (3) | 0.110 (4) | 0.091 (4) | 0.016 (3) | −0.008 (3) | −0.003 (3) |
C21 | 0.082 (3) | 0.114 (3) | 0.089 (4) | −0.008 (3) | 0.008 (3) | −0.003 (3) |
C22 | 0.104 (3) | 0.091 (3) | 0.084 (3) | −0.006 (3) | 0.004 (3) | 0.000 (2) |
C23 | 0.095 (3) | 0.093 (3) | 0.104 (4) | 0.010 (3) | 0.010 (3) | −0.002 (3) |
C24 | 0.098 (3) | 0.111 (4) | 0.115 (4) | 0.016 (3) | 0.012 (3) | −0.014 (3) |
C25 | 0.121 (4) | 0.134 (5) | 0.102 (4) | 0.002 (4) | 0.021 (4) | −0.011 (4) |
C26 | 0.111 (4) | 0.117 (4) | 0.086 (4) | 0.002 (3) | 0.009 (3) | 0.011 (3) |
C27 | 0.083 (3) | 0.100 (3) | 0.080 (3) | 0.004 (2) | −0.001 (2) | 0.003 (2) |
C28 | 0.087 (3) | 0.089 (3) | 0.081 (3) | 0.005 (2) | 0.006 (2) | 0.008 (2) |
C29 | 0.075 (3) | 0.098 (3) | 0.084 (3) | 0.006 (3) | 0.013 (2) | 0.010 (3) |
C30 | 0.102 (3) | 0.181 (6) | 0.140 (5) | −0.033 (4) | −0.004 (3) | −0.036 (5) |
C31 | 0.099 (3) | 0.094 (3) | 0.093 (3) | 0.005 (3) | −0.010 (3) | 0.001 (3) |
C32 | 0.125 (4) | 0.115 (4) | 0.094 (4) | 0.009 (4) | 0.009 (3) | 0.014 (3) |
C33 | 0.149 (5) | 0.140 (5) | 0.112 (5) | 0.018 (4) | 0.012 (4) | −0.001 (4) |
C34 | 0.172 (6) | 0.152 (6) | 0.094 (4) | −0.002 (5) | 0.017 (4) | −0.003 (5) |
C35 | 0.180 (6) | 0.149 (6) | 0.095 (5) | 0.019 (5) | −0.003 (5) | 0.031 (4) |
C36 | 0.143 (5) | 0.115 (4) | 0.113 (5) | 0.024 (4) | −0.014 (4) | 0.014 (4) |
O1—N2 | 1.403 (5) | O2—N4 | 1.406 (5) |
O1—H1 | 0.82 | O2—H2 | 0.82 |
N1—C5 | 1.460 (6) | N3—C27 | 1.453 (6) |
N1—C9 | 1.461 (6) | N3—C23 | 1.452 (6) |
N1—C10 | 1.485 (5) | N3—C28 | 1.468 (5) |
N2—C11 | 1.271 (6) | N4—C29 | 1.276 (6) |
C1—C12 | 1.520 (7) | C19—C31 | 1.497 (7) |
C1—C13 | 1.523 (7) | C19—C30 | 1.537 (7) |
C1—C2 | 1.543 (7) | C19—C20 | 1.546 (7) |
C1—C4 | 1.544 (7) | C19—C22 | 1.548 (7) |
C2—C3 | 1.536 (7) | C20—C21 | 1.556 (7) |
C2—H2A | 0.97 | C20—H20A | 0.97 |
C2—H2B | 0.97 | C20—H20B | 0.97 |
C3—C11 | 1.493 (7) | C21—C29 | 1.481 (7) |
C3—C4 | 1.554 (7) | C21—C22 | 1.524 (7) |
C3—H3 | 0.98 | C21—H21 | 0.98 |
C4—H4A | 0.97 | C22—H22A | 0.97 |
C4—H4B | 0.97 | C22—H22B | 0.97 |
C5—C6 | 1.514 (7) | C23—C24 | 1.505 (7) |
C5—H5A | 0.97 | C23—H23A | 0.97 |
C5—H5B | 0.97 | C23—H23B | 0.97 |
C6—C7 | 1.503 (8) | C24—C25 | 1.497 (8) |
C6—H6A | 0.97 | C24—H24A | 0.97 |
C6—H6B | 0.97 | C24—H24B | 0.97 |
C7—C8 | 1.517 (8) | C25—C26 | 1.510 (8) |
C7—H7A | 0.97 | C25—H25A | 0.97 |
C7—H7B | 0.97 | C25—H25B | 0.97 |
C8—C9 | 1.522 (7) | C26—C27 | 1.518 (7) |
C8—H8A | 0.97 | C26—H26A | 0.97 |
C8—H8B | 0.97 | C26—H26B | 0.97 |
C9—H9A | 0.97 | C27—H27A | 0.97 |
C9—H9B | 0.97 | C27—H27B | 0.97 |
C10—C11 | 1.504 (7) | C28—C29 | 1.512 (7) |
C10—H10A | 0.97 | C28—H28A | 0.97 |
C10—H10B | 0.97 | C28—H28B | 0.97 |
C12—H12A | 0.96 | C30—H30A | 0.96 |
C12—H12B | 0.96 | C30—H30B | 0.96 |
C12—H12C | 0.96 | C30—H30C | 0.96 |
C13—C18 | 1.366 (7) | C31—C32 | 1.373 (7) |
C13—C14 | 1.383 (8) | C31—C36 | 1.378 (8) |
C14—C15 | 1.394 (8) | C32—C33 | 1.401 (8) |
C14—H14 | 0.93 | C32—H32 | 0.93 |
C15—C16 | 1.334 (9) | C33—C34 | 1.344 (9) |
C15—H15 | 0.93 | C33—H33 | 0.93 |
C16—C17 | 1.372 (10) | C34—C35 | 1.341 (9) |
C16—H16 | 0.93 | C34—H34 | 0.93 |
C17—C18 | 1.371 (8) | C35—C36 | 1.407 (9) |
C17—H17 | 0.93 | C35—H35 | 0.93 |
C18—H18 | 0.93 | C36—H36 | 0.93 |
N2—O1—H1 | 109.5 | N4—O2—H2 | 109.5 |
C5—N1—C9 | 110.2 (4) | C27—N3—C23 | 110.4 (4) |
C5—N1—C10 | 110.8 (3) | C27—N3—C28 | 111.6 (3) |
C9—N1—C10 | 109.0 (3) | C23—N3—C28 | 109.7 (4) |
C11—N2—O1 | 112.5 (4) | C29—N4—O2 | 112.7 (4) |
C12—C1—C13 | 110.3 (4) | C31—C19—C30 | 109.2 (5) |
C12—C1—C2 | 113.2 (5) | C31—C19—C20 | 117.9 (4) |
C13—C1—C2 | 116.0 (4) | C30—C19—C20 | 111.4 (4) |
C12—C1—C4 | 112.3 (4) | C31—C19—C22 | 117.3 (4) |
C13—C1—C4 | 115.6 (4) | C30—C19—C22 | 112.2 (5) |
C2—C1—C4 | 88.0 (4) | C20—C19—C22 | 87.4 (4) |
C3—C2—C1 | 89.6 (3) | C19—C20—C21 | 88.8 (4) |
C3—C2—H2A | 113.7 | C19—C20—H20A | 113.9 |
C1—C2—H2A | 113.7 | C21—C20—H20A | 113.9 |
C3—C2—H2B | 113.7 | C19—C20—H20B | 113.9 |
C1—C2—H2B | 113.7 | C21—C20—H20B | 113.9 |
H2A—C2—H2B | 111.0 | H20A—C20—H20B | 111.1 |
C11—C3—C2 | 119.9 (4) | C29—C21—C22 | 120.9 (4) |
C11—C3—C4 | 117.3 (4) | C29—C21—C20 | 117.3 (4) |
C2—C3—C4 | 87.9 (4) | C22—C21—C20 | 88.0 (4) |
C11—C3—H3 | 110.0 | C29—C21—H21 | 109.6 |
C2—C3—H3 | 110.0 | C22—C21—H21 | 109.6 |
C4—C3—H3 | 110.0 | C20—C21—H21 | 109.6 |
C1—C4—C3 | 88.9 (4) | C21—C22—C19 | 89.9 (4) |
C1—C4—H4A | 113.8 | C21—C22—H22A | 113.7 |
C3—C4—H4A | 113.8 | C19—C22—H22A | 113.7 |
C1—C4—H4B | 113.8 | C21—C22—H22B | 113.7 |
C3—C4—H4B | 113.8 | C19—C22—H22B | 113.7 |
H4A—C4—H4B | 111.1 | H22A—C22—H22B | 110.9 |
N1—C5—C6 | 110.3 (4) | N3—C23—C24 | 111.9 (4) |
N1—C5—H5A | 109.6 | N3—C23—H23A | 109.2 |
C6—C5—H5A | 109.6 | C24—C23—H23A | 109.2 |
N1—C5—H5B | 109.6 | N3—C23—H23B | 109.2 |
C6—C5—H5B | 109.6 | C24—C23—H23B | 109.2 |
H5A—C5—H5B | 108.1 | H23A—C23—H23B | 107.9 |
C7—C6—C5 | 111.5 (5) | C25—C24—C23 | 111.9 (4) |
C7—C6—H6A | 109.3 | C25—C24—H24A | 109.2 |
C5—C6—H6A | 109.3 | C23—C24—H24A | 109.2 |
C7—C6—H6B | 109.3 | C25—C24—H24B | 109.2 |
C5—C6—H6B | 109.3 | C23—C24—H24B | 109.2 |
H6A—C6—H6B | 108.0 | H24A—C24—H24B | 107.9 |
C6—C7—C8 | 110.1 (5) | C24—C25—C26 | 109.6 (5) |
C6—C7—H7A | 109.6 | C24—C25—H25A | 109.7 |
C8—C7—H7A | 109.6 | C26—C25—H25A | 109.7 |
C6—C7—H7B | 109.6 | C24—C25—H25B | 109.7 |
C8—C7—H7B | 109.6 | C26—C25—H25B | 109.7 |
H7A—C7—H7B | 108.2 | H25A—C25—H25B | 108.2 |
C7—C8—C9 | 110.6 (4) | C25—C26—C27 | 110.9 (5) |
C7—C8—H8A | 109.5 | C25—C26—H26A | 109.4 |
C9—C8—H8A | 109.5 | C27—C26—H26A | 109.4 |
C7—C8—H8B | 109.5 | C25—C26—H26B | 109.4 |
C9—C8—H8B | 109.5 | C27—C26—H26B | 109.4 |
H8A—C8—H8B | 108.1 | H26A—C26—H26B | 108.0 |
N1—C9—C8 | 111.8 (4) | N3—C27—C26 | 110.8 (4) |
N1—C9—H9A | 109.2 | N3—C27—H27A | 109.5 |
C8—C9—H9A | 109.2 | C26—C27—H27A | 109.5 |
N1—C9—H9B | 109.2 | N3—C27—H27B | 109.5 |
C8—C9—H9B | 109.2 | C26—C27—H27B | 109.5 |
H9A—C9—H9B | 107.9 | H27A—C27—H27B | 108.1 |
N1—C10—C11 | 113.1 (4) | N3—C28—C29 | 113.5 (4) |
N1—C10—H10A | 109.0 | N3—C28—H28A | 108.9 |
C11—C10—H10A | 109.0 | C29—C28—H28A | 108.9 |
N1—C10—H10B | 109.0 | N3—C28—H28B | 108.9 |
C11—C10—H10B | 109.0 | C29—C28—H28B | 108.9 |
H10A—C10—H10B | 107.8 | H28A—C28—H28B | 107.7 |
N2—C11—C3 | 116.6 (4) | N4—C29—C21 | 116.5 (4) |
N2—C11—C10 | 125.4 (4) | N4—C29—C28 | 124.9 (5) |
C3—C11—C10 | 117.9 (4) | C21—C29—C28 | 118.5 (4) |
C1—C12—H12A | 109.5 | C19—C30—H30A | 109.5 |
C1—C12—H12B | 109.5 | C19—C30—H30B | 109.5 |
H12A—C12—H12B | 109.5 | H30A—C30—H30B | 109.5 |
C1—C12—H12C | 109.5 | C19—C30—H30C | 109.5 |
H12A—C12—H12C | 109.5 | H30A—C30—H30C | 109.5 |
H12B—C12—H12C | 109.5 | H30B—C30—H30C | 109.5 |
C18—C13—C14 | 117.6 (5) | C32—C31—C36 | 116.2 (5) |
C18—C13—C1 | 121.1 (5) | C32—C31—C19 | 120.6 (5) |
C14—C13—C1 | 121.3 (5) | C36—C31—C19 | 123.2 (5) |
C13—C14—C15 | 120.9 (6) | C31—C32—C33 | 122.0 (6) |
C13—C14—H14 | 119.6 | C31—C32—H32 | 119.0 |
C15—C14—H14 | 119.6 | C33—C32—H32 | 119.0 |
C16—C15—C14 | 119.3 (6) | C34—C33—C32 | 119.8 (7) |
C16—C15—H15 | 120.4 | C34—C33—H33 | 120.1 |
C14—C15—H15 | 120.4 | C32—C33—H33 | 120.1 |
C15—C16—C17 | 121.4 (7) | C35—C34—C33 | 120.3 (7) |
C15—C16—H16 | 119.3 | C35—C34—H34 | 119.8 |
C17—C16—H16 | 119.3 | C33—C34—H34 | 119.8 |
C16—C17—C18 | 118.9 (6) | C34—C35—C36 | 120.0 (7) |
C16—C17—H17 | 120.5 | C34—C35—H35 | 120.0 |
C18—C17—H17 | 120.5 | C36—C35—H35 | 120.0 |
C13—C18—C17 | 121.9 (5) | C31—C36—C35 | 121.5 (6) |
C13—C18—H18 | 119.1 | C31—C36—H36 | 119.3 |
C17—C18—H18 | 119.1 | C35—C36—H36 | 119.3 |
C12—C1—C2—C3 | −95.6 (4) | C31—C19—C20—C21 | 137.8 (4) |
C13—C1—C2—C3 | 135.5 (4) | C30—C19—C20—C21 | −94.9 (5) |
C4—C1—C2—C3 | 17.9 (4) | C22—C19—C20—C21 | 18.0 (3) |
C1—C2—C3—C11 | −138.3 (4) | C19—C20—C21—C29 | −142.4 (4) |
C1—C2—C3—C4 | −17.8 (4) | C19—C20—C21—C22 | −18.3 (3) |
C12—C1—C4—C3 | 96.7 (5) | C29—C21—C22—C19 | 139.3 (5) |
C13—C1—C4—C3 | −135.6 (4) | C20—C21—C22—C19 | 18.3 (4) |
C2—C1—C4—C3 | −17.7 (4) | C31—C19—C22—C21 | −138.7 (4) |
C11—C3—C4—C1 | 140.6 (4) | C30—C19—C22—C21 | 93.7 (5) |
C2—C3—C4—C1 | 17.8 (4) | C20—C19—C22—C21 | −18.4 (4) |
C9—N1—C5—C6 | 60.0 (5) | C27—N3—C23—C24 | 58.2 (5) |
C10—N1—C5—C6 | −179.3 (4) | C28—N3—C23—C24 | −178.3 (4) |
N1—C5—C6—C7 | −58.2 (6) | N3—C23—C24—C25 | −55.6 (6) |
C5—C6—C7—C8 | 54.1 (6) | C23—C24—C25—C26 | 52.6 (6) |
C6—C7—C8—C9 | −52.2 (6) | C24—C25—C26—C27 | −53.7 (6) |
C5—N1—C9—C8 | −59.4 (5) | C23—N3—C27—C26 | −59.3 (5) |
C10—N1—C9—C8 | 178.8 (4) | C28—N3—C27—C26 | 178.4 (4) |
C7—C8—C9—N1 | 55.5 (6) | C25—C26—C27—N3 | 57.7 (6) |
C5—N1—C10—C11 | 67.4 (5) | C27—N3—C28—C29 | −67.1 (5) |
C9—N1—C10—C11 | −171.1 (4) | C23—N3—C28—C29 | 170.2 (4) |
O1—N2—C11—C3 | 178.3 (4) | O2—N4—C29—C21 | −178.4 (4) |
O1—N2—C11—C10 | 2.0 (7) | O2—N4—C29—C28 | −1.2 (6) |
C2—C3—C11—N2 | −11.7 (7) | C22—C21—C29—N4 | 7.7 (7) |
C4—C3—C11—N2 | −116.1 (5) | C20—C21—C29—N4 | 113.0 (5) |
C2—C3—C11—C10 | 164.9 (4) | C22—C21—C29—C28 | −169.8 (4) |
C4—C3—C11—C10 | 60.5 (6) | C20—C21—C29—C28 | −64.5 (5) |
N1—C10—C11—N2 | −100.9 (5) | N3—C28—C29—N4 | 99.5 (5) |
N1—C10—C11—C3 | 82.9 (5) | N3—C28—C29—C21 | −83.3 (5) |
C12—C1—C13—C18 | −90.5 (6) | C30—C19—C31—C32 | 91.4 (6) |
C2—C1—C13—C18 | 39.8 (6) | C20—C19—C31—C32 | −140.2 (5) |
C4—C1—C13—C18 | 140.8 (4) | C22—C19—C31—C32 | −37.7 (7) |
C12—C1—C13—C14 | 89.4 (6) | C30—C19—C31—C36 | −89.9 (7) |
C2—C1—C13—C14 | −140.3 (5) | C20—C19—C31—C36 | 38.5 (7) |
C4—C1—C13—C14 | −39.3 (6) | C22—C19—C31—C36 | 141.0 (5) |
C18—C13—C14—C15 | −1.5 (8) | C36—C31—C32—C33 | 2.4 (9) |
C1—C13—C14—C15 | 178.6 (5) | C19—C31—C32—C33 | −178.8 (5) |
C13—C14—C15—C16 | 0.6 (9) | C31—C32—C33—C34 | −0.9 (10) |
C14—C15—C16—C17 | 0.7 (9) | C32—C33—C34—C35 | −1.3 (11) |
C15—C16—C17—C18 | −1.1 (10) | C33—C34—C35—C36 | 1.8 (12) |
C14—C13—C18—C17 | 1.1 (8) | C32—C31—C36—C35 | −1.9 (9) |
C1—C13—C18—C17 | −179.0 (4) | C19—C31—C36—C35 | 179.3 (5) |
C16—C17—C18—C13 | 0.2 (9) | C34—C35—C36—C31 | −0.1 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O1 | 0.97 | 2.30 | 2.682 (5) | 102 |
C28—H28B···O2 | 0.97 | 2.30 | 2.685 (5) | 102 |
O2—H2···N3i | 0.82 | 1.98 | 2.778 (5) | 164 |
O1—H1···N1ii | 0.82 | 1.97 | 2.754 (5) | 161 |
Symmetry codes: (i) x−1/2, −y+1, z; (ii) x+1/2, −y, z. |
Experimental details
Crystal data | |
Chemical formula | C18H26N2O |
Mr | 286.41 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 296 |
a, b, c (Å) | 10.8782 (5), 5.8899 (3), 53.307 (3) |
V (Å3) | 3415.5 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.64 × 0.45 × 0.13 |
Data collection | |
Diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16092, 1988, 1661 |
Rint | 0.124 |
θmax (°) | 21.5 |
(sin θ/λ)max (Å−1) | 0.517 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.122, 1.06 |
No. of reflections | 1988 |
No. of parameters | 374 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.11 |
Absolute structure parameter | 0 (10) |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
O1—N2 | 1.403 (5) | O2—N4 | 1.406 (5) |
N1—C5 | 1.460 (6) | N3—C27 | 1.453 (6) |
N1—C9 | 1.461 (6) | N3—C23 | 1.452 (6) |
N1—C10 | 1.485 (5) | N3—C28 | 1.468 (5) |
N2—C11 | 1.271 (6) | N4—C29 | 1.276 (6) |
C1—C12 | 1.520 (7) | C19—C31 | 1.497 (7) |
C1—C13 | 1.523 (7) | C19—C30 | 1.537 (7) |
C1—C2 | 1.543 (7) | C19—C20 | 1.546 (7) |
C1—C4 | 1.544 (7) | C19—C22 | 1.548 (7) |
C2—C3 | 1.536 (7) | C20—C21 | 1.556 (7) |
C3—C11 | 1.493 (7) | C21—C29 | 1.481 (7) |
C3—C4 | 1.554 (7) | C21—C22 | 1.524 (7) |
C5—N1—C9 | 110.2 (4) | C27—N3—C23 | 110.4 (4) |
C5—N1—C10 | 110.8 (3) | C27—N3—C28 | 111.6 (3) |
C9—N1—C10 | 109.0 (3) | C23—N3—C28 | 109.7 (4) |
C11—N2—O1 | 112.5 (4) | C29—N4—O2 | 112.7 (4) |
C2—C1—C4 | 88.0 (4) | C20—C19—C22 | 87.4 (4) |
C3—C2—C1 | 89.6 (3) | C19—C20—C21 | 88.8 (4) |
C2—C3—C4 | 87.9 (4) | C22—C21—C20 | 88.0 (4) |
C1—C4—C3 | 88.9 (4) | C21—C22—C19 | 89.9 (4) |
N1—C10—C11 | 113.1 (4) | N3—C28—C29 | 113.5 (4) |
N2—C11—C3 | 116.6 (4) | N4—C29—C21 | 116.5 (4) |
N2—C11—C10 | 125.4 (4) | N4—C29—C28 | 124.9 (5) |
C3—C11—C10 | 117.9 (4) | C21—C29—C28 | 118.5 (4) |
C5—N1—C10—C11 | 67.4 (5) | C27—N3—C28—C29 | −67.1 (5) |
C9—N1—C10—C11 | −171.1 (4) | C23—N3—C28—C29 | 170.2 (4) |
O1—N2—C11—C10 | 2.0 (7) | O2—N4—C29—C28 | −1.2 (6) |
C2—C3—C11—N2 | −11.7 (7) | C22—C21—C29—N4 | 7.7 (7) |
C4—C3—C11—N2 | −116.1 (5) | C20—C21—C29—N4 | 113.0 (5) |
C2—C3—C11—C10 | 164.9 (4) | C22—C21—C29—C28 | −169.8 (4) |
C4—C3—C11—C10 | 60.5 (6) | C20—C21—C29—C28 | −64.5 (5) |
N1—C10—C11—N2 | −100.9 (5) | N3—C28—C29—N4 | 99.5 (5) |
N1—C10—C11—C3 | 82.9 (5) | N3—C28—C29—C21 | −83.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O1 | 0.97 | 2.30 | 2.682 (5) | 102 |
C28—H28B···O2 | 0.97 | 2.30 | 2.685 (5) | 102 |
O2—H2···N3i | 0.82 | 1.98 | 2.778 (5) | 164 |
O1—H1···N1ii | 0.82 | 1.97 | 2.754 (5) | 161 |
Symmetry codes: (i) x−1/2, −y+1, z; (ii) x+1/2, −y, z. |
3-Substituted cyclobutane carboxylic acid derivatives exhibit anti-inflammatory and antidepressant activities (Dehmlow & Schmidt, 1990), and also liquid crystal properties (Coghi et al., 1976). Owing to their unique biological properties, the piperidines have been target molecules in organic synthesis (Weintraub et al., 2003). In recent years, polyhydroxylated piperidine alkaloids have attracted much attention because some of them have the ability to act as selective glycosidase inhibitors (Stutz, 1999). Oximes show geometric isomerism due to the double bond between the N and C atoms (Mixich & Thiele, 1979; Migrdichian, 1957). Because of significant differences in the physical, chemical and biological properties of these geometric isomers, the determination of the configuration of the isomers is important (Mathison et al., 1989). Oximes and oxime ethers also have a broad pharmacological activity spectrum, encompassing antifungal, antibacterial, antidepressant and insecticidal activities, as well as activity as a nerve-gas antidote, depending on the pharmacophoric group of the molecule (Polak, 1982; Balsamo et al., 1990; Holan et al., 1984; Forman, 1964). The oxime group (C═N—OH) possesses stronger hydrogen-bonding capabilities than the alcohol, phenol or carboxylic acid group (Marsman et al., 1999). Hydrogen bonding plays a key role in molecular recognition in chemical engineering (Bertolasi et al., 1982; Gilli et al., 1983; Hökelek et al., 2001). As part of our ongoing study of the relationship between the molecular and crystal structures of cyclobutane and oxime derivatives, a crystal-structure determination of the title compound, (I), has been undertaken and the results are presented here.
Previously we have reported the crystal structures of similar compounds, viz. 2-[2-hydroxyimino-2-(3-methyl-3-phenylcyclobutyl)ethyl]isoindole-1,3-dione, (II) (Özdemir et al., 2004) and 3-[1-hydroxyimino-2-(succinimido)ethyl]1-methyl-1-phenylcyclobutane,(III) (Dinçer et al., 2004). The main aim of the present investigation is to study the differences between the structures of (I), (II) and (III), and also to determine the strength of the hydrogen-bonding capabilities of the oxime group.
The structures of the two independent molecules, A (O1/N1/N2/C1–C18) and B (O2/N3/N4/C19–C36), of (I) have very similar molecular dimensions (Fig. 1 and Table 1). In the following discussion, values for molecule B are quoted in square brackets. In the crystal structure, the phenyl and (piperidin-1-yl)acetaldehyde oxime groups are in cis positions with respect to the cyclobutane ring. The four-atom bridge linking the cyclobutane and piperidine rings is not planar, and the ΦCC torsion angle is 82.9 (5)° [−83.3 (5)°], which shows that the conformation about the C—C bond is synclinal.
Although close to being planar, the cyclobutane ring in (I) is more puckered than in (II) and (III), because of the steric hindrance of the substituents. The C4/C1/C2 plane forms a dihedral angle of 25.0 (4)° [25.7 (4)°] with the C2/C3/C4 plane [11.55 (3)° in (II), 19.26 (17)° in (III)]. However, when the bond lengths of the cylobutane ring in (I) are compared with those in (II) and (III), it is seen that there are no significant differences. The piperidine ring adopts a chair conformation, as is evident from the Cremer and Pople (1975) puckering parameters Q = 0.569 (5) Å [0.562 (5) Å], θ = 176.8 (5)° [177.6 (6)°] and ϕ2 = 207 (10)° [138 (11)°]. The oxime moiety has an E configuration, with a C3—C11—N2—O1 torsion angle of 178.3 (4)° [−178.4 (4)°]. In (I), the plane of the oxime moiety is twisted by 45.2 (4)° [46.4 (4)°] out of the mean plane of the cyclobutane ring. The bond lengths and angles of the oxime moiety in (I) are close to those in (II) and (III).
In each independent molecule, a intramolecular C—H···O interaction generate a five-membered ring (Fig. 1). Atom O1 acts as hydrogen-bond donor to atom N1 of the piperidine ring at (x + 1/2, −y, z). Similiarly, atom O2 acts as hydrogen-bond donor to atom N3 of the piperidine ring at (x − 1/2, 1 − y, z). There are no intermolecular π–π and C—H···π interactions in the crystal structure of (I).