

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810021781/fj2311sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810021781/fj2311Isup2.hkl |
CCDC reference: 786595
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean
(C-C) = 0.002 Å
- R factor = 0.036
- wR factor = 0.110
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 82 PLAT031_ALERT_4_C Refined Extinction Parameter within Range ...... 3.29 Sigma PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 51
Alert level G PLAT154_ALERT_1_G The su's on the Cell Angles are Equal (x 10000) 100 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: The contributions of the various authors was as follows: |
Jean Fotie: Advisor and experimentalist in the preparation of the compound, and growing crystals. He was also involved in the preparation of the manuscript. Chris F. Fronczek: (undergraduate researcher): collected X-ray data, Solved and refined crystal structure. Kyle A. Burns: (undergraduate researcher): participated in the purification of the compound and growing the crystal. He also measured the melting point. Frank R. Fronczek: Advisor on X-ray work, manuscript editing. Cheryl Bain: Carried out the NMR data collection. D. Scott Bohle: Advisor NMR data collection and interpretation Ferdinand P. Poudeu: collected the Masspec data.
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
The title compound was prepared by heating to reflux for three days, a mixture of p-phenitidine (500 mg, 3.6 mmol) and cyclopentanone (10 ml, large excess) in the presence of catalytic amounts of iodine (93 mg) and benzoyl peroxide (8.8 mg). After appropriate work-up, and purification on a silica gel column, crystals were carefully grown at room temperature, in a mixture of hexanes-dichloromethane, over the course of a week.
Mp: 131.3 - 131.6 °C. The melting point was recorded on a MEL-TEMP ELECTROTHERMAL digital melting point apparatus, and is not corrected.
ESIMS m/z (%): 316 (90) [M + CH3]+, 302 (43) [M + H]+, 286 (100) [M -16]+, 284 (94) [M - H2O]+. These fragment ions are consistent with a molecular formula of C18H23NO3. The ESIMS spectrum was recorded on a Finnigan LCQDUO spectrometer.
NMR data were collected on a Bruker AC 300 Spectrometer. 1H-NMR (300 MHz, CDCl3) δ: 1.47 (3H, t, J = 6.7 Hz), 1.68 (2H, m), 1.85 (2H, m), 2.23 (2H, m), 3.04 (4H, t, J = 7.9 Hz), 3.13 (2H, t, J = 7.3 Hz), 4.10 (2H, t, 6.7 Hz), 4.15 (2H, q, J = 6.7 Hz), 6.90 (1H, d, J = 2.4 Hz), 7.23 (1H, dd, J = 9.2 Hz and 2,4 Hz), 7.83 (1H, d, 9.2 Hz), 13.6 (1H, brs). 13C-NMR (75 MHz, CDCl3) δ: 14.9, 24.0, 25.0, 25.9, 31.4, 31.5, 35.0, 63.8, 103.0, 121.1, 125.9, 129.2, 136.0, 141.6, 149.7, 155.9, 156.6. 162.3.
H atoms on C were placed in idealized positions with C—H distances 0.95 - 1.00 Å and thereafter treated as riding. The OH H atom was located from a difference map in the expected circle. Torsional parameters were refined for the methyl and hydroperoxy OH groups. Uiso for H were assigned as 1.2 times Ueq of the attached atoms (1.5 for methyl and OH).
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![]() | Fig. 1. Ellipsoids at the 50% level, with H atoms having arbitrary radius. |
![]() | Fig. 2. The hydrogen-bonded dimer, with graph set R22(18). |
C18H23NO3 | Z = 2 |
Mr = 301.37 | F(000) = 324 |
Triclinic, P1 | Dx = 1.268 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 8.0113 (2) Å | Cell parameters from 4518 reflections |
b = 8.5091 (2) Å | θ = 3.7–68.3° |
c = 12.6334 (3) Å | µ = 0.69 mm−1 |
α = 73.605 (1)° | T = 90 K |
β = 74.936 (1)° | Prism, colourless |
γ = 78.136 (1)° | 0.19 × 0.17 × 0.15 mm |
V = 789.63 (3) Å3 |
Bruker APEXII CCD diffractometer | 2798 independent reflections |
Radiation source: fine-focus sealed tube | 2400 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 68.8°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −9→9 |
Tmin = 0.880, Tmax = 0.904 | k = −9→10 |
9369 measured reflections | l = −15→15 |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0626P)2 + 0.1754P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2798 reflections | Δρmax = 0.22 e Å−3 |
202 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0023 (7) |
C18H23NO3 | γ = 78.136 (1)° |
Mr = 301.37 | V = 789.63 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0113 (2) Å | Cu Kα radiation |
b = 8.5091 (2) Å | µ = 0.69 mm−1 |
c = 12.6334 (3) Å | T = 90 K |
α = 73.605 (1)° | 0.19 × 0.17 × 0.15 mm |
β = 74.936 (1)° |
Bruker APEXII CCD diffractometer | 2798 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2400 reflections with I > 2σ(I) |
Tmin = 0.880, Tmax = 0.904 | Rint = 0.030 |
9369 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.22 e Å−3 |
2798 reflections | Δρmin = −0.27 e Å−3 |
202 parameters |
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 | 0.54940 (12) | 0.44045 (11) | 1.21141 (7) | 0.0202 (2) | |
O2 | 0.43514 (12) | 0.35072 (12) | 1.31138 (8) | 0.0233 (3) | |
H2 | 0.3429 | 0.4140 | 1.3292 | 0.035* | |
O3 | 0.98882 (12) | 0.17854 (11) | 0.27498 (8) | 0.0201 (2) | |
N1 | 0.84064 (14) | 0.40032 (13) | 0.66551 (9) | 0.0180 (3) | |
C1 | 0.96537 (17) | 0.22269 (16) | 0.37459 (11) | 0.0177 (3) | |
C2 | 1.08402 (17) | 0.17863 (16) | 0.44285 (11) | 0.0175 (3) | |
H2A | 1.1914 | 0.1104 | 0.4233 | 0.021* | |
C3 | 1.04475 (17) | 0.23589 (15) | 0.54275 (11) | 0.0166 (3) | |
C4 | 0.88489 (17) | 0.33756 (16) | 0.57160 (11) | 0.0171 (3) | |
C5 | 0.76525 (17) | 0.37924 (16) | 0.49902 (11) | 0.0184 (3) | |
H5 | 0.6573 | 0.4473 | 0.5172 | 0.022* | |
C6 | 0.80419 (17) | 0.32234 (16) | 0.40359 (11) | 0.0198 (3) | |
H6 | 0.7225 | 0.3498 | 0.3562 | 0.024* | |
C7 | 1.15889 (17) | 0.19861 (16) | 0.61825 (11) | 0.0173 (3) | |
C8 | 1.33845 (17) | 0.09920 (17) | 0.60806 (11) | 0.0203 (3) | |
H8A | 1.4123 | 0.1362 | 0.5321 | 0.024* | |
H8B | 1.3323 | −0.0203 | 0.6226 | 0.024* | |
C9 | 1.40947 (18) | 0.13488 (18) | 0.69997 (12) | 0.0235 (3) | |
H9A | 1.4726 | 0.0323 | 0.7404 | 0.028* | |
H9B | 1.4909 | 0.2177 | 0.6656 | 0.028* | |
C10 | 1.25038 (18) | 0.20199 (18) | 0.78213 (12) | 0.0229 (3) | |
H10A | 1.2155 | 0.1143 | 0.8507 | 0.027* | |
H10B | 1.2753 | 0.2956 | 0.8047 | 0.027* | |
C11 | 1.11048 (17) | 0.25808 (16) | 0.71348 (11) | 0.0188 (3) | |
C12 | 0.95014 (17) | 0.36144 (16) | 0.73497 (11) | 0.0184 (3) | |
C13 | 0.89624 (18) | 0.43704 (17) | 0.83518 (11) | 0.0209 (3) | |
H13A | 0.8268 | 0.5471 | 0.8139 | 0.025* | |
H13B | 1.0025 | 0.4540 | 0.8543 | 0.025* | |
C14 | 0.78889 (17) | 0.33287 (16) | 0.94029 (11) | 0.0186 (3) | |
H14A | 0.6851 | 0.3105 | 0.9213 | 0.022* | |
H14B | 0.8601 | 0.2254 | 0.9657 | 0.022* | |
C15 | 0.73048 (17) | 0.42275 (16) | 1.03551 (11) | 0.0190 (3) | |
H15A | 0.8351 | 0.4403 | 1.0561 | 0.023* | |
H15B | 0.6655 | 0.5329 | 1.0079 | 0.023* | |
C16 | 0.61601 (18) | 0.32967 (16) | 1.13985 (11) | 0.0194 (3) | |
H16A | 0.5194 | 0.2962 | 1.1196 | 0.023* | |
H16B | 0.6850 | 0.2291 | 1.1779 | 0.023* | |
C17 | 1.15683 (18) | 0.09386 (16) | 0.23380 (11) | 0.0201 (3) | |
H17A | 1.1735 | −0.0203 | 0.2812 | 0.024* | |
H17B | 1.2503 | 0.1526 | 0.2357 | 0.024* | |
C18 | 1.1631 (2) | 0.09065 (18) | 0.11403 (12) | 0.0256 (3) | |
H18A | 1.0682 | 0.0347 | 0.1132 | 0.038* | |
H18B | 1.2755 | 0.0309 | 0.0835 | 0.038* | |
H18C | 1.1496 | 0.2043 | 0.0676 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0200 (5) | 0.0214 (5) | 0.0171 (5) | −0.0013 (4) | 0.0010 (4) | −0.0070 (4) |
O2 | 0.0197 (5) | 0.0255 (5) | 0.0176 (5) | 0.0011 (4) | 0.0027 (4) | −0.0033 (4) |
O3 | 0.0201 (5) | 0.0229 (5) | 0.0180 (5) | 0.0001 (4) | −0.0048 (4) | −0.0076 (4) |
N1 | 0.0179 (6) | 0.0168 (6) | 0.0179 (6) | −0.0021 (4) | −0.0017 (4) | −0.0044 (4) |
C1 | 0.0208 (7) | 0.0161 (7) | 0.0153 (6) | −0.0040 (5) | −0.0026 (5) | −0.0027 (5) |
C2 | 0.0164 (7) | 0.0150 (6) | 0.0183 (7) | −0.0013 (5) | −0.0018 (5) | −0.0023 (5) |
C3 | 0.0171 (7) | 0.0141 (6) | 0.0166 (7) | −0.0038 (5) | −0.0023 (5) | −0.0006 (5) |
C4 | 0.0181 (7) | 0.0141 (6) | 0.0168 (7) | −0.0033 (5) | −0.0004 (5) | −0.0022 (5) |
C5 | 0.0151 (7) | 0.0165 (7) | 0.0210 (7) | 0.0002 (5) | −0.0027 (5) | −0.0029 (5) |
C6 | 0.0187 (7) | 0.0193 (7) | 0.0199 (7) | −0.0030 (5) | −0.0051 (5) | −0.0017 (5) |
C7 | 0.0173 (7) | 0.0148 (6) | 0.0175 (7) | −0.0039 (5) | −0.0023 (5) | −0.0003 (5) |
C8 | 0.0176 (7) | 0.0211 (7) | 0.0201 (7) | 0.0016 (5) | −0.0045 (5) | −0.0045 (5) |
C9 | 0.0183 (7) | 0.0282 (8) | 0.0235 (7) | −0.0008 (6) | −0.0065 (6) | −0.0056 (6) |
C10 | 0.0222 (7) | 0.0259 (8) | 0.0219 (7) | −0.0011 (6) | −0.0075 (6) | −0.0071 (6) |
C11 | 0.0194 (7) | 0.0180 (7) | 0.0175 (7) | −0.0052 (5) | −0.0029 (5) | −0.0012 (5) |
C12 | 0.0193 (7) | 0.0164 (7) | 0.0182 (7) | −0.0043 (5) | −0.0017 (5) | −0.0032 (5) |
C13 | 0.0215 (7) | 0.0203 (7) | 0.0212 (7) | −0.0037 (5) | −0.0020 (6) | −0.0075 (6) |
C14 | 0.0194 (7) | 0.0188 (7) | 0.0182 (7) | −0.0005 (5) | −0.0043 (5) | −0.0067 (5) |
C15 | 0.0181 (7) | 0.0203 (7) | 0.0192 (7) | −0.0006 (5) | −0.0041 (5) | −0.0072 (5) |
C16 | 0.0213 (7) | 0.0195 (7) | 0.0179 (7) | 0.0005 (5) | −0.0043 (5) | −0.0075 (5) |
C17 | 0.0214 (7) | 0.0180 (7) | 0.0197 (7) | −0.0001 (5) | −0.0029 (5) | −0.0058 (5) |
C18 | 0.0307 (8) | 0.0246 (8) | 0.0226 (7) | −0.0005 (6) | −0.0046 (6) | −0.0106 (6) |
O1—C16 | 1.4193 (15) | C9—H9B | 0.9900 |
O1—O2 | 1.4690 (13) | C10—C11 | 1.5125 (18) |
O2—H2 | 0.8400 | C10—H10A | 0.9900 |
O3—C1 | 1.3693 (15) | C10—H10B | 0.9900 |
O3—C17 | 1.4319 (16) | C11—C12 | 1.4094 (19) |
N1—C12 | 1.3288 (17) | C12—C13 | 1.5048 (18) |
N1—C4 | 1.3709 (17) | C13—C14 | 1.5310 (18) |
C1—C2 | 1.3729 (18) | C13—H13A | 0.9900 |
C1—C6 | 1.4142 (19) | C13—H13B | 0.9900 |
C2—C3 | 1.4166 (18) | C14—C15 | 1.5266 (17) |
C2—H2A | 0.9500 | C14—H14A | 0.9900 |
C3—C4 | 1.4147 (18) | C14—H14B | 0.9900 |
C3—C7 | 1.4176 (18) | C15—C16 | 1.5122 (18) |
C4—C5 | 1.4208 (18) | C15—H15A | 0.9900 |
C5—C6 | 1.3628 (19) | C15—H15B | 0.9900 |
C5—H5 | 0.9500 | C16—H16A | 0.9900 |
C6—H6 | 0.9500 | C16—H16B | 0.9900 |
C7—C11 | 1.3691 (19) | C17—C18 | 1.5087 (18) |
C7—C8 | 1.5054 (18) | C17—H17A | 0.9900 |
C8—C9 | 1.5420 (19) | C17—H17B | 0.9900 |
C8—H8A | 0.9900 | C18—H18A | 0.9800 |
C8—H8B | 0.9900 | C18—H18B | 0.9800 |
C9—C10 | 1.5413 (19) | C18—H18C | 0.9800 |
C9—H9A | 0.9900 | ||
C16—O1—O2 | 105.80 (9) | C7—C11—C12 | 120.33 (12) |
O1—O2—H2 | 109.5 | C7—C11—C10 | 111.14 (12) |
C1—O3—C17 | 117.05 (10) | C12—C11—C10 | 128.50 (12) |
C12—N1—C4 | 119.06 (11) | N1—C12—C11 | 121.27 (12) |
O3—C1—C2 | 125.10 (12) | N1—C12—C13 | 116.62 (11) |
O3—C1—C6 | 114.06 (11) | C11—C12—C13 | 122.09 (12) |
C2—C1—C6 | 120.84 (12) | C12—C13—C14 | 114.07 (11) |
C1—C2—C3 | 119.32 (12) | C12—C13—H13A | 108.7 |
C1—C2—H2A | 120.3 | C14—C13—H13A | 108.7 |
C3—C2—H2A | 120.3 | C12—C13—H13B | 108.7 |
C4—C3—C2 | 120.22 (12) | C14—C13—H13B | 108.7 |
C4—C3—C7 | 116.10 (12) | H13A—C13—H13B | 107.6 |
C2—C3—C7 | 123.68 (12) | C15—C14—C13 | 110.73 (11) |
N1—C4—C3 | 123.16 (12) | C15—C14—H14A | 109.5 |
N1—C4—C5 | 118.20 (12) | C13—C14—H14A | 109.5 |
C3—C4—C5 | 118.63 (12) | C15—C14—H14B | 109.5 |
C6—C5—C4 | 120.53 (12) | C13—C14—H14B | 109.5 |
C6—C5—H5 | 119.7 | H14A—C14—H14B | 108.1 |
C4—C5—H5 | 119.7 | C16—C15—C14 | 113.20 (11) |
C5—C6—C1 | 120.44 (12) | C16—C15—H15A | 108.9 |
C5—C6—H6 | 119.8 | C14—C15—H15A | 108.9 |
C1—C6—H6 | 119.8 | C16—C15—H15B | 108.9 |
C11—C7—C3 | 120.02 (12) | C14—C15—H15B | 108.9 |
C11—C7—C8 | 111.83 (11) | H15A—C15—H15B | 107.8 |
C3—C7—C8 | 128.14 (12) | O1—C16—C15 | 106.06 (11) |
C7—C8—C9 | 103.20 (11) | O1—C16—H16A | 110.5 |
C7—C8—H8A | 111.1 | C15—C16—H16A | 110.5 |
C9—C8—H8A | 111.1 | O1—C16—H16B | 110.5 |
C7—C8—H8B | 111.1 | C15—C16—H16B | 110.5 |
C9—C8—H8B | 111.1 | H16A—C16—H16B | 108.7 |
H8A—C8—H8B | 109.1 | O3—C17—C18 | 107.10 (11) |
C10—C9—C8 | 106.77 (11) | O3—C17—H17A | 110.3 |
C10—C9—H9A | 110.4 | C18—C17—H17A | 110.3 |
C8—C9—H9A | 110.4 | O3—C17—H17B | 110.3 |
C10—C9—H9B | 110.4 | C18—C17—H17B | 110.3 |
C8—C9—H9B | 110.4 | H17A—C17—H17B | 108.6 |
H9A—C9—H9B | 108.6 | C17—C18—H18A | 109.5 |
C11—C10—C9 | 103.12 (11) | C17—C18—H18B | 109.5 |
C11—C10—H10A | 111.1 | H18A—C18—H18B | 109.5 |
C9—C10—H10A | 111.1 | C17—C18—H18C | 109.5 |
C11—C10—H10B | 111.1 | H18A—C18—H18C | 109.5 |
C9—C10—H10B | 111.1 | H18B—C18—H18C | 109.5 |
H10A—C10—H10B | 109.1 | ||
C17—O3—C1—C2 | −6.48 (18) | C3—C7—C8—C9 | 168.11 (13) |
C17—O3—C1—C6 | 173.01 (11) | C7—C8—C9—C10 | 18.58 (14) |
O3—C1—C2—C3 | 178.62 (11) | C8—C9—C10—C11 | −19.42 (14) |
C6—C1—C2—C3 | −0.8 (2) | C3—C7—C11—C12 | −2.3 (2) |
C1—C2—C3—C4 | −0.07 (19) | C8—C7—C11—C12 | 176.70 (12) |
C1—C2—C3—C7 | −179.45 (12) | C3—C7—C11—C10 | 179.39 (11) |
C12—N1—C4—C3 | −1.71 (19) | C8—C7—C11—C10 | −1.59 (16) |
C12—N1—C4—C5 | 179.37 (11) | C9—C10—C11—C7 | 13.27 (15) |
C2—C3—C4—N1 | −178.41 (11) | C9—C10—C11—C12 | −164.84 (13) |
C7—C3—C4—N1 | 1.02 (19) | C4—N1—C12—C11 | 0.34 (19) |
C2—C3—C4—C5 | 0.51 (19) | C4—N1—C12—C13 | 178.70 (11) |
C7—C3—C4—C5 | 179.94 (11) | C7—C11—C12—N1 | 1.7 (2) |
N1—C4—C5—C6 | 178.92 (11) | C10—C11—C12—N1 | 179.63 (12) |
C3—C4—C5—C6 | −0.05 (19) | C7—C11—C12—C13 | −176.59 (12) |
C4—C5—C6—C1 | −0.8 (2) | C10—C11—C12—C13 | 1.4 (2) |
O3—C1—C6—C5 | −178.21 (11) | N1—C12—C13—C14 | 89.79 (14) |
C2—C1—C6—C5 | 1.3 (2) | C11—C12—C13—C14 | −91.87 (15) |
C4—C3—C7—C11 | 1.01 (19) | C12—C13—C14—C15 | −176.62 (11) |
C2—C3—C7—C11 | −179.59 (12) | C13—C14—C15—C16 | 177.09 (10) |
C4—C3—C7—C8 | −177.84 (12) | O2—O1—C16—C15 | 178.71 (9) |
C2—C3—C7—C8 | 1.6 (2) | C14—C15—C16—O1 | −170.23 (10) |
C11—C7—C8—C9 | −10.82 (15) | C1—O3—C17—C18 | −168.40 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1i | 0.84 | 1.93 | 2.7466 (14) | 165 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C18H23NO3 |
Mr | 301.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 90 |
a, b, c (Å) | 8.0113 (2), 8.5091 (2), 12.6334 (3) |
α, β, γ (°) | 73.605 (1), 74.936 (1), 78.136 (1) |
V (Å3) | 789.63 (3) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.19 × 0.17 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.880, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9369, 2798, 2400 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.110, 1.08 |
No. of reflections | 2798 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.27 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N1i | 0.84 | 1.93 | 2.7466 (14) | 165 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Dihydroquinolines are mainly known for their antioxidant activity (Thorisson et al., 1992, Lockhart et al., 2001) although they have also been reported to possess anti-inflammatory (Dillard et al., 1973), fungicidal (Cracknell et al., 1998), antiatherosclerotic (Babiak et al., 1999), and hormone receptor modulator (Takahashi et al., 2006) properties. Furthermore, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, also known as ethoxyquin, is a FDA approved antioxidant commonly used as a preservative in the food processing industry (Shah et al., 2005). We have recently reported some dihydroquinoline derivatives with outstanding antitrypanosomal activity (Fotie et al., 2010). In our effort to optimize the trypanocidal activity of this family of compound, we have synthesized the title compound, an unusual hydroperoxybutylquinoline derivative. Here we are reporting the characterization of that compound using 1H– and 13C-NMR spectroscopy, mass spectrometry, and single-crystal diffraction.
The molecular structure of the title compound is illustrated in Fig. 1. The 10-atom quinoline ring system is essentially planar, with mean deviation 0.009 Å and maximum deviation 0.017 (1) Å for both N1 and C11. The five-membered ring has the envelope conformation, with C9 at the flap position, 0.340 (2) Å out of the quinoline plane. The hydroperoxybutyl chain is extended, with torsion angle magnitudes in the range 170.23 (10) to 178.71 (9)°, and the best plane of its four C and two O atoms is approximately perpendicular to the quinoline plane, forming a dihedral angle of 89.53 (3)°. The hydroperoxy O—O distance, 1.4690 (13) Å agrees well with literature values for this group. The mean value of the 135 such distances in the Cambridge Structural Database (version 5.31, Nov. 2009; Allen 2002), after rejecting eight outliers, is 1.462 Å.
The hydroperoxide donates an intermolecular hydrogen bond to quinoline N1, with O···N distance 2.7466 (14) Å, forming discrete dimers having graph set (Etter, 1990) R22(18) about inversion centers, as illustrated in Fig. 2.