Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104007930/tr1074sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007930/tr1074Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007930/tr1074IIsup3.hkl |
CCDC references: 243594; 243595
Both title compounds were synthesized as described by Martirosyan et al. (2000). Recrystallization from ethanol afforded colourless crystals suitable for X-ray analysis.
Data sets were collected corresponding to a full sphere of reciprocal space. In (I), the trimethyl group (atoms C10, C11 and C12) shows rotational disorder. H atoms in (I) were refined at idealized positions (C—H = 0.93–0.97 Å and O—H = 0.82 Å Please check added text), with isotropic displacement parameters of 1.5 (CH3, OH) and 1.2 (CH, CH2) times Ueq of the parent atom. In (II), the positional and isotropic diplacement parameters of all H atoms were refined independently.
For both compounds, data collection: CAD-4 Manual (Enraf-Nonius, 1988); cell refinement: CAD-4 Manual; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 2000); software used to prepare material for publication: SHELXTL-NT.
C16H21NO4 | F(000) = 624 |
Mr = 291.34 | Dx = 1.236 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C-2yc | Cell parameters from 25 reflections |
a = 19.309 (4) Å | θ = 10.0–17.2° |
b = 6.4210 (13) Å | µ = 0.09 mm−1 |
c = 13.735 (3) Å | T = 293 K |
β = 113.20 (3)° | Prism, colourless |
V = 1565.2 (7) Å3 | 0.3 × 0.24 × 0.18 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.036 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.3° |
Graphite monochromator | h = −26→26 |
θ/2θ scans | k = −8→9 |
8331 measured reflections | l = −19→19 |
2273 independent reflections | 3 standard reflections every 60 min |
1635 reflections with I > 2σ(I) | intensity decay: no decay, variation < 1.0% |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0494P)2 + 0.13P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2273 reflections | Δρmax = 0.13 e Å−3 |
220 parameters | Δρmin = −0.12 e Å−3 |
17 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0054 (8) |
C16H21NO4 | V = 1565.2 (7) Å3 |
Mr = 291.34 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 19.309 (4) Å | µ = 0.09 mm−1 |
b = 6.4210 (13) Å | T = 293 K |
c = 13.735 (3) Å | 0.3 × 0.24 × 0.18 mm |
β = 113.20 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.036 |
8331 measured reflections | 3 standard reflections every 60 min |
2273 independent reflections | intensity decay: no decay, variation < 1.0% |
1635 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.041 | 17 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.13 e Å−3 |
2273 reflections | Δρmin = −0.12 e Å−3 |
220 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 16.4635 (0.0154) x − 3.1265 (0.0071) y − 7.0063 (0.0152) z = 9.1171 (0.0205) * 0.1741 (0.0014) C1 * −0.0645 (0.0014) N2 * −0.0737 (0.0015) C3 * 0.1897 (0.0017) C4 * −0.2256 (0.0016) C5 Rms deviation of fitted atoms = 0.1592 3.9275 (0.0177) x − 2.3844 (0.0059) y + 10.3363 (0.0099) z = 10.8903 (0.0168) Angle to previous plane (with approximate e.s.d.) = 79.48 (0.09) * 0.0008 (0.0014) C16 * 0.0012 (0.0015) C17 * −0.0024 (0.0017) C18 * 0.0015 (0.0018) C19 * 0.0005 (0.0018) C20 * −0.0016 (0.0016) C21 Rms deviation of fitted atoms = 0.0015 |
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 | Occ. (<1) | |
C1 | 0.99477 (11) | 0.4888 (3) | 0.79329 (15) | 0.0397 (4) | |
N2 | 0.94542 (9) | 0.3128 (3) | 0.78992 (13) | 0.0395 (3) | |
C3 | 0.96748 (13) | 0.2043 (3) | 0.89149 (16) | 0.0492 (5) | |
H3A | 0.9792 | 0.0594 | 0.8848 | 0.059* | |
H3B | 0.9276 | 0.2106 | 0.9176 | 0.059* | |
C4 | 1.03636 (15) | 0.3196 (5) | 0.96428 (18) | 0.0639 (7) | |
H4A | 1.0820 | 0.2493 | 0.9688 | 0.077* | |
H4B | 1.0366 | 0.3308 | 1.0349 | 0.077* | |
C5 | 1.03030 (14) | 0.5324 (4) | 0.91435 (17) | 0.0543 (5) | |
H5A | 1.0796 | 0.5962 | 0.9350 | 0.065* | |
H5B | 0.9983 | 0.6235 | 0.9349 | 0.065* | |
C6 | 0.88397 (10) | 0.2527 (3) | 0.70638 (15) | 0.0386 (4) | |
O7 | 0.84372 (7) | 0.1085 (2) | 0.71039 (12) | 0.0500 (4) | |
O8 | 0.87270 (8) | 0.3682 (2) | 0.62149 (10) | 0.0460 (3) | |
C9 | 0.81211 (12) | 0.3243 (4) | 0.51839 (18) | 0.0525 (6) | |
C10A | 0.7327 (3) | 0.3062 (17) | 0.5103 (6) | 0.067 (2) | 0.432 (8) |
H10A | 0.7187 | 0.4319 | 0.5359 | 0.101* | 0.432 (8) |
H10B | 0.7288 | 0.1904 | 0.5521 | 0.101* | 0.432 (8) |
H10C | 0.6995 | 0.2847 | 0.4376 | 0.101* | 0.432 (8) |
C11A | 0.8403 (4) | 0.1299 (9) | 0.4803 (5) | 0.0547 (18) | 0.432 (8) |
H11A | 0.8842 | 0.1648 | 0.4670 | 0.082* | 0.432 (8) |
H11B | 0.8015 | 0.0794 | 0.4162 | 0.082* | 0.432 (8) |
H11C | 0.8530 | 0.0239 | 0.5338 | 0.082* | 0.432 (8) |
C12A | 0.8124 (7) | 0.4982 (13) | 0.4444 (8) | 0.075 (3) | 0.432 (8) |
H12A | 0.7963 | 0.6252 | 0.4658 | 0.113* | 0.432 (8) |
H12B | 0.7787 | 0.4641 | 0.3734 | 0.113* | 0.432 (8) |
H12C | 0.8625 | 0.5158 | 0.4469 | 0.113* | 0.432 (8) |
C10B | 0.7426 (3) | 0.379 (2) | 0.5381 (7) | 0.143 (5) | 0.568 (8) |
H10D | 0.7472 | 0.5178 | 0.5655 | 0.215* | 0.568 (8) |
H10E | 0.7374 | 0.2829 | 0.5885 | 0.215* | 0.568 (8) |
H10F | 0.6990 | 0.3697 | 0.4728 | 0.215* | 0.568 (8) |
C11B | 0.8134 (7) | 0.0988 (11) | 0.4852 (8) | 0.143 (5) | 0.568 (8) |
H11D | 0.7722 | 0.0246 | 0.4917 | 0.215* | 0.568 (8) |
H11E | 0.8601 | 0.0354 | 0.5301 | 0.215* | 0.568 (8) |
H11F | 0.8086 | 0.0940 | 0.4130 | 0.215* | 0.568 (8) |
C12B | 0.8271 (5) | 0.4893 (13) | 0.4505 (5) | 0.068 (2) | 0.568 (8) |
H12D | 0.8125 | 0.6230 | 0.4673 | 0.102* | 0.568 (8) |
H12E | 0.7985 | 0.4586 | 0.3771 | 0.102* | 0.568 (8) |
H12F | 0.8798 | 0.4909 | 0.4641 | 0.102* | 0.568 (8) |
C13 | 0.94951 (11) | 0.6821 (3) | 0.73730 (16) | 0.0431 (5) | |
O14 | 0.89222 (9) | 0.7196 (2) | 0.76473 (13) | 0.0559 (4) | |
H14 | 0.8753 | 0.8361 | 0.7443 | 0.084* | |
O15 | 0.96694 (9) | 0.7932 (3) | 0.68045 (14) | 0.0581 (4) | |
C16 | 1.05564 (11) | 0.4345 (3) | 0.75280 (14) | 0.0424 (4) | |
C17 | 1.11241 (12) | 0.5778 (4) | 0.76433 (17) | 0.0540 (6) | |
H17 | 1.1120 | 0.7071 | 0.7946 | 0.065* | |
C18 | 1.16967 (13) | 0.5291 (5) | 0.7310 (2) | 0.0654 (7) | |
H18 | 1.2072 | 0.6260 | 0.7386 | 0.079* | |
C19 | 1.17091 (14) | 0.3391 (6) | 0.6871 (2) | 0.0710 (8) | |
H19 | 1.2095 | 0.3066 | 0.6652 | 0.085* | |
C21 | 1.05759 (13) | 0.2436 (4) | 0.70779 (17) | 0.0511 (5) | |
H21 | 1.0201 | 0.1459 | 0.6992 | 0.061* | |
C20 | 1.11565 (15) | 0.1967 (5) | 0.6751 (2) | 0.0660 (7) | |
H20 | 1.1167 | 0.0676 | 0.6450 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0425 (10) | 0.0361 (9) | 0.0374 (9) | −0.0086 (8) | 0.0123 (8) | −0.0031 (8) |
N2 | 0.0437 (8) | 0.0353 (8) | 0.0406 (7) | −0.0059 (7) | 0.0178 (6) | 0.0022 (7) |
C3 | 0.0592 (12) | 0.0435 (11) | 0.0480 (10) | 0.0048 (10) | 0.0245 (9) | 0.0094 (9) |
C4 | 0.0605 (13) | 0.0811 (18) | 0.0430 (11) | −0.0011 (13) | 0.0130 (10) | 0.0081 (12) |
C5 | 0.0614 (12) | 0.0581 (13) | 0.0398 (10) | −0.0107 (11) | 0.0160 (9) | −0.0072 (10) |
C6 | 0.0371 (8) | 0.0326 (9) | 0.0516 (10) | 0.0037 (8) | 0.0234 (8) | 0.0010 (8) |
O7 | 0.0400 (7) | 0.0396 (8) | 0.0725 (9) | −0.0048 (6) | 0.0244 (7) | 0.0055 (7) |
O8 | 0.0470 (7) | 0.0441 (7) | 0.0417 (7) | −0.0133 (6) | 0.0119 (6) | −0.0021 (6) |
C9 | 0.0438 (11) | 0.0543 (13) | 0.0486 (11) | −0.0075 (10) | 0.0067 (9) | −0.0007 (10) |
C10A | 0.034 (3) | 0.105 (6) | 0.059 (4) | −0.015 (3) | 0.014 (3) | −0.012 (4) |
C11A | 0.080 (4) | 0.043 (3) | 0.043 (3) | 0.000 (3) | 0.026 (3) | −0.013 (2) |
C12A | 0.072 (5) | 0.052 (5) | 0.085 (6) | −0.011 (4) | 0.012 (4) | 0.003 (4) |
C10B | 0.041 (3) | 0.254 (14) | 0.110 (6) | 0.014 (5) | 0.002 (3) | 0.086 (8) |
C11B | 0.190 (11) | 0.077 (5) | 0.089 (5) | −0.041 (6) | −0.023 (6) | −0.023 (4) |
C12B | 0.062 (3) | 0.103 (6) | 0.038 (3) | −0.001 (3) | 0.017 (2) | 0.015 (3) |
C13 | 0.0453 (10) | 0.0350 (9) | 0.0477 (10) | −0.0082 (8) | 0.0170 (8) | −0.0048 (9) |
O14 | 0.0644 (9) | 0.0397 (8) | 0.0744 (10) | 0.0040 (7) | 0.0389 (8) | 0.0060 (7) |
O15 | 0.0624 (9) | 0.0466 (9) | 0.0714 (9) | 0.0006 (7) | 0.0328 (8) | 0.0149 (8) |
C16 | 0.0379 (9) | 0.0471 (10) | 0.0372 (9) | −0.0026 (8) | 0.0096 (8) | 0.0059 (9) |
C17 | 0.0428 (11) | 0.0606 (14) | 0.0520 (12) | −0.0098 (10) | 0.0115 (10) | 0.0050 (11) |
C18 | 0.0410 (11) | 0.091 (2) | 0.0607 (14) | −0.0090 (12) | 0.0160 (10) | 0.0172 (14) |
C19 | 0.0471 (12) | 0.106 (2) | 0.0651 (14) | 0.0132 (15) | 0.0282 (11) | 0.0180 (16) |
C21 | 0.0504 (11) | 0.0520 (12) | 0.0519 (11) | −0.0015 (10) | 0.0212 (9) | −0.0006 (10) |
C20 | 0.0622 (14) | 0.0760 (17) | 0.0634 (15) | 0.0113 (13) | 0.0285 (12) | −0.0010 (13) |
C1—N2 | 1.467 (2) | C11A—H11C | 0.9600 |
C1—C16 | 1.526 (3) | C12A—H12A | 0.9600 |
C1—C13 | 1.538 (3) | C12A—H12B | 0.9600 |
C1—C5 | 1.554 (3) | C12A—H12C | 0.9600 |
N2—C6 | 1.342 (2) | C10B—H10D | 0.9600 |
N2—C3 | 1.465 (3) | C10B—H10E | 0.9600 |
C3—C4 | 1.507 (3) | C10B—H10F | 0.9600 |
C3—H3A | 0.9700 | C11B—H11D | 0.9600 |
C3—H3B | 0.9700 | C11B—H11E | 0.9600 |
C4—C5 | 1.513 (4) | C11B—H11F | 0.9600 |
C4—H4A | 0.9700 | C12B—H12D | 0.9600 |
C4—H4B | 0.9700 | C12B—H12E | 0.9600 |
C5—H5A | 0.9700 | C12B—H12F | 0.9600 |
C5—H5B | 0.9700 | C13—O15 | 1.200 (3) |
C6—O7 | 1.224 (2) | C13—O14 | 1.324 (3) |
C6—O8 | 1.326 (2) | O14—H14 | 0.8200 |
O8—C9 | 1.466 (3) | C16—C21 | 1.380 (3) |
C9—C10A | 1.498 (6) | C16—C17 | 1.392 (3) |
C9—C10B | 1.511 (7) | C17—C18 | 1.389 (4) |
C9—C12A | 1.512 (7) | C17—H17 | 0.9300 |
C9—C12B | 1.512 (6) | C18—C19 | 1.365 (5) |
C9—C11B | 1.521 (7) | C18—H18 | 0.9300 |
C9—C11A | 1.534 (6) | C19—C20 | 1.365 (4) |
C10A—H10A | 0.9600 | C19—H19 | 0.9300 |
C10A—H10B | 0.9600 | C21—C20 | 1.395 (4) |
C10A—H10C | 0.9600 | C21—H21 | 0.9300 |
C11A—H11A | 0.9600 | C20—H20 | 0.9300 |
C11A—H11B | 0.9600 | ||
N2—C1—C16 | 113.36 (16) | H11A—C11A—H11B | 109.5 |
N2—C1—C13 | 111.82 (16) | C9—C11A—H11C | 109.5 |
C16—C1—C13 | 111.71 (16) | H11A—C11A—H11C | 109.5 |
N2—C1—C5 | 100.37 (16) | H11B—C11A—H11C | 109.5 |
C16—C1—C5 | 110.64 (17) | C9—C12A—H12A | 109.5 |
C13—C1—C5 | 108.29 (17) | C9—C12A—H12B | 109.5 |
C6—N2—C3 | 120.31 (17) | H12A—C12A—H12B | 109.5 |
C6—N2—C1 | 126.38 (16) | C9—C12A—H12C | 109.5 |
C3—N2—C1 | 113.27 (16) | H12A—C12A—H12C | 109.5 |
N2—C3—C4 | 104.32 (18) | H12B—C12A—H12C | 109.5 |
N2—C3—H3A | 110.9 | C9—C10B—H10D | 109.5 |
C4—C3—H3A | 110.9 | C9—C10B—H10E | 109.5 |
N2—C3—H3B | 110.9 | H10D—C10B—H10E | 109.5 |
C4—C3—H3B | 110.9 | C9—C10B—H10F | 109.5 |
H3A—C3—H3B | 108.9 | H10D—C10B—H10F | 109.5 |
C3—C4—C5 | 104.66 (18) | H10E—C10B—H10F | 109.5 |
C3—C4—H4A | 110.8 | C9—C11B—H11D | 109.5 |
C5—C4—H4A | 110.8 | C9—C11B—H11E | 109.5 |
C3—C4—H4B | 110.8 | H11D—C11B—H11E | 109.5 |
C5—C4—H4B | 110.8 | C9—C11B—H11F | 109.5 |
H4A—C4—H4B | 108.9 | H11D—C11B—H11F | 109.5 |
C4—C5—C1 | 104.18 (18) | H11E—C11B—H11F | 109.5 |
C4—C5—H5A | 110.9 | C9—C12B—H12D | 109.5 |
C1—C5—H5A | 110.9 | C9—C12B—H12E | 109.5 |
C4—C5—H5B | 110.9 | H12D—C12B—H12E | 109.5 |
C1—C5—H5B | 110.9 | C9—C12B—H12F | 109.5 |
H5A—C5—H5B | 108.9 | H12D—C12B—H12F | 109.5 |
O7—C6—O8 | 125.15 (17) | H12E—C12B—H12F | 109.5 |
O7—C6—N2 | 122.85 (18) | O15—C13—O14 | 123.86 (19) |
O8—C6—N2 | 111.99 (16) | O15—C13—C1 | 123.74 (19) |
C6—O8—C9 | 122.30 (16) | O14—C13—C1 | 112.24 (17) |
O8—C9—C10A | 119.4 (4) | C13—O14—H14 | 109.5 |
O8—C9—C10B | 102.1 (4) | C21—C16—C17 | 118.6 (2) |
O8—C9—C12A | 107.1 (4) | C21—C16—C1 | 121.82 (18) |
C10A—C9—C12A | 106.4 (6) | C17—C16—C1 | 119.53 (19) |
O8—C9—C12B | 100.8 (3) | C18—C17—C16 | 120.5 (3) |
C10B—C9—C12B | 110.4 (6) | C18—C17—H17 | 119.8 |
O8—C9—C11B | 111.8 (4) | C16—C17—H17 | 119.8 |
C10B—C9—C11B | 113.2 (7) | C19—C18—C17 | 120.1 (2) |
C12B—C9—C11B | 116.9 (6) | C19—C18—H18 | 119.9 |
O8—C9—C11A | 103.3 (3) | C17—C18—H18 | 119.9 |
C10A—C9—C11A | 113.7 (5) | C18—C19—C20 | 120.2 (2) |
C12A—C9—C11A | 106.0 (6) | C18—C19—H19 | 119.9 |
C9—C10A—H10A | 109.5 | C20—C19—H19 | 119.9 |
C9—C10A—H10B | 109.5 | C16—C21—C20 | 120.2 (2) |
H10A—C10A—H10B | 109.5 | C16—C21—H21 | 119.9 |
C9—C10A—H10C | 109.5 | C20—C21—H21 | 119.9 |
H10A—C10A—H10C | 109.5 | C19—C20—C21 | 120.4 (3) |
H10B—C10A—H10C | 109.5 | C19—C20—H20 | 119.8 |
C9—C11A—H11A | 109.5 | C21—C20—H20 | 119.8 |
C9—C11A—H11B | 109.5 | ||
C16—C1—N2—C6 | −85.0 (2) | C6—O8—C9—C11B | −51.9 (7) |
C13—C1—N2—C6 | 42.3 (3) | C6—O8—C9—C11A | −73.3 (4) |
C5—C1—N2—C6 | 156.97 (19) | N2—C1—C13—O15 | −138.3 (2) |
C16—C1—N2—C3 | 97.2 (2) | C16—C1—C13—O15 | −10.1 (3) |
C13—C1—N2—C3 | −135.47 (17) | C5—C1—C13—O15 | 112.0 (2) |
C5—C1—N2—C3 | −20.8 (2) | N2—C1—C13—O14 | 46.0 (2) |
C6—N2—C3—C4 | −178.40 (19) | C16—C1—C13—O14 | 174.26 (15) |
C1—N2—C3—C4 | −0.4 (2) | C5—C1—C13—O14 | −63.7 (2) |
N2—C3—C4—C5 | 22.5 (3) | N2—C1—C16—C21 | 6.3 (3) |
C3—C4—C5—C1 | −35.6 (3) | C13—C1—C16—C21 | −121.1 (2) |
N2—C1—C5—C4 | 33.8 (2) | C5—C1—C16—C21 | 118.1 (2) |
C16—C1—C5—C4 | −86.2 (2) | N2—C1—C16—C17 | −171.58 (16) |
C13—C1—C5—C4 | 151.10 (19) | C13—C1—C16—C17 | 61.0 (2) |
C3—N2—C6—O7 | 0.4 (3) | C5—C1—C16—C17 | −59.7 (2) |
C1—N2—C6—O7 | −177.22 (19) | C21—C16—C17—C18 | 0.1 (3) |
C3—N2—C6—O8 | 179.98 (18) | C1—C16—C17—C18 | 178.0 (2) |
C1—N2—C6—O8 | 2.3 (3) | C16—C17—C18—C19 | −0.4 (3) |
O7—C6—O8—C9 | −4.7 (3) | C17—C18—C19—C20 | 0.4 (4) |
N2—C6—O8—C9 | 175.81 (18) | C17—C16—C21—C20 | 0.2 (3) |
C6—O8—C9—C10A | 54.1 (6) | C1—C16—C21—C20 | −177.7 (2) |
C6—O8—C9—C10B | 69.4 (6) | C18—C19—C20—C21 | −0.1 (4) |
C6—O8—C9—C12A | 175.0 (5) | C16—C21—C20—C19 | −0.2 (4) |
C6—O8—C9—C12B | −176.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14···O7i | 0.82 | 1.85 | 2.668 (2) | 175 |
Symmetry code: (i) x, y+1, z. |
C18H21N2O+·Cl− | Z = 2 |
Mr = 316.82 | F(000) = 336 |
Triclinic, P1 | Dx = 1.285 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8302 (18) Å | Cell parameters from 25 reflections |
b = 10.077 (2) Å | θ = 12.5–17.8° |
c = 10.094 (2) Å | µ = 0.24 mm−1 |
α = 99.74 (3)° | T = 293 K |
β = 92.53 (3)° | Sphere, colourless |
γ = 111.39 (3)° | 0.23 mm (radius) |
V = 818.7 (4) Å3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.017 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.1° |
Graphite monochromator | h = −12→12 |
θ/2θ scans | k = −14→14 |
9597 measured reflections | l = −14→14 |
4767 independent reflections | 3 standard reflections every 60 min |
3895 reflections with I > 2σ(I) | intensity decay: no decay, variation < 1.0% |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | All H-atom parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.1106P] where P = (Fo2 + 2Fc2)/3 |
4767 reflections | (Δ/σ)max < 0.001 |
283 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C18H21N2O+·Cl− | γ = 111.39 (3)° |
Mr = 316.82 | V = 818.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8302 (18) Å | Mo Kα radiation |
b = 10.077 (2) Å | µ = 0.24 mm−1 |
c = 10.094 (2) Å | T = 293 K |
α = 99.74 (3)° | 0.23 mm (radius) |
β = 92.53 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.017 |
9597 measured reflections | 3 standard reflections every 60 min |
4767 independent reflections | intensity decay: no decay, variation < 1.0% |
3895 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.107 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.26 e Å−3 |
4767 reflections | Δρmin = −0.16 e Å−3 |
283 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 3.9131 (0.0057) x + 5.5447 (0.0066) y + 7.1991 (0.0063) z = 3.0604 (0.0034) * −0.0042 (0.0009) C16 * 0.0006 (0.0011) C17 * 0.0025 (0.0012) C18 * −0.0020 (0.0013) C19 * −0.0016 (0.0012) C20 * 0.0047 (0.0011) C21 Rms deviation of fitted atoms = 0.0030 − 5.5031 (0.0049) x + 9.6185 (0.0053) y − 1.6835 (0.0057) z = 4.2826 (0.0051) Angle to previous plane (with approximate e.s.d.) = 55.20 (0.06) * −0.0055 (0.0008) C7 * 0.0072 (0.0009) C8 * −0.0027 (0.0010) C9 * −0.0036 (0.0010) C10 * 0.0053 (0.0010) C11 * −0.0008 (0.0009) C12 Rms deviation of fitted atoms = 0.0047 3.0322 (0.0060) x + 7.0377 (0.0061) y − 5.0482 (0.0054) z = 6.0450 (0.0045) Angle to previous plane (with approximate e.s.d.) = 60.70 (0.05) * 0.0424 (0.0007) C1 * −0.0240 (0.0006) N2 * −0.0069 (0.0008) C3 * 0.0349 (0.0009) C4 * −0.0465 (0.0008) C5 Rms deviation of fitted atoms = 0.0341 − 3.9131 (0.0057) x + 5.5447 (0.0066) y + 7.1991 (0.0063) z = 3.0604 (0.0034) Angle to previous plane (with approximate e.s.d.) = 88.09 (0.06) * −0.0042 (0.0009) C16 * 0.0006 (0.0011) C17 * 0.0025 (0.0012) C18 * −0.0020 (0.0013) C19 * −0.0016 (0.0012) C20 * 0.0047 (0.0011) C21 Rms deviation of fitted atoms = 0.0030 |
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 | ||
Cl1 | 0.14123 (4) | 0.85572 (4) | 0.03042 (3) | 0.04903 (10) | |
C1 | 0.69819 (13) | 0.73955 (11) | 0.24450 (10) | 0.0330 (2) | |
N2 | 0.73860 (10) | 0.81544 (9) | 0.38775 (8) | 0.03181 (17) | |
C3 | 0.87058 (13) | 0.80799 (12) | 0.45323 (11) | 0.0362 (2) | |
C4 | 0.93727 (18) | 0.71681 (18) | 0.35789 (16) | 0.0549 (3) | |
H4B | 1.048 (3) | 0.780 (3) | 0.347 (2) | 0.100 (7)* | |
H4A | 0.945 (2) | 0.645 (2) | 0.397 (2) | 0.084 (6)* | |
C5 | 0.82233 (15) | 0.66214 (13) | 0.22876 (12) | 0.0414 (2) | |
H5B | 0.7636 (18) | 0.5563 (18) | 0.2169 (16) | 0.053 (4)* | |
H5A | 0.883 (2) | 0.6862 (18) | 0.1523 (17) | 0.059 (4)* | |
C6 | 0.65558 (15) | 0.90841 (12) | 0.44887 (12) | 0.0382 (2) | |
H6B | 0.736 (2) | 0.9997 (18) | 0.4965 (17) | 0.056 (4)* | |
H6A | 0.6008 (16) | 0.9299 (15) | 0.3783 (14) | 0.040 (3)* | |
C7 | 0.53920 (14) | 0.84941 (12) | 0.54986 (11) | 0.0374 (2) | |
C8 | 0.37941 (15) | 0.75191 (14) | 0.50758 (13) | 0.0450 (3) | |
H8 | 0.342 (2) | 0.7135 (18) | 0.4074 (18) | 0.061 (4)* | |
C9 | 0.27242 (18) | 0.70622 (16) | 0.60215 (16) | 0.0539 (3) | |
H9 | 0.170 (2) | 0.640 (2) | 0.5736 (19) | 0.070 (5)* | |
C10 | 0.3219 (2) | 0.75825 (18) | 0.73827 (16) | 0.0577 (4) | |
H10 | 0.249 (2) | 0.7268 (19) | 0.8051 (19) | 0.067 (5)* | |
C11 | 0.4789 (2) | 0.85651 (19) | 0.78105 (14) | 0.0576 (4) | |
H11 | 0.515 (2) | 0.895 (2) | 0.875 (2) | 0.076 (5)* | |
C12 | 0.58783 (17) | 0.90176 (16) | 0.68722 (12) | 0.0479 (3) | |
H12 | 0.698 (2) | 0.9713 (17) | 0.7182 (17) | 0.054 (4)* | |
C13 | 0.72724 (15) | 0.85107 (13) | 0.15286 (11) | 0.0385 (2) | |
H13B | 0.7096 (18) | 0.8047 (17) | 0.0624 (17) | 0.051 (4)* | |
H13A | 0.6545 (17) | 0.8999 (15) | 0.1607 (14) | 0.042 (3)* | |
N14 | 0.89545 (13) | 0.96403 (11) | 0.17746 (10) | 0.0411 (2) | |
H14C | 0.972 (2) | 0.9311 (19) | 0.1478 (17) | 0.060 (5)* | |
H14B | 0.895 (2) | 1.0285 (19) | 0.1280 (18) | 0.061 (5)* | |
H14A | 0.9261 (18) | 1.0069 (16) | 0.2624 (16) | 0.047 (4)* | |
O15 | 0.92545 (11) | 0.86771 (10) | 0.57096 (8) | 0.0477 (2) | |
C16 | 0.52005 (14) | 0.63198 (12) | 0.22045 (11) | 0.0380 (2) | |
C17 | 0.39834 (17) | 0.64927 (16) | 0.14166 (14) | 0.0529 (3) | |
H17 | 0.422 (2) | 0.7283 (19) | 0.0899 (17) | 0.060 (4)* | |
C18 | 0.23676 (19) | 0.5517 (2) | 0.12922 (18) | 0.0691 (4) | |
H18 | 0.158 (2) | 0.570 (2) | 0.076 (2) | 0.081 (6)* | |
C19 | 0.1960 (2) | 0.43702 (18) | 0.1948 (2) | 0.0722 (5) | |
H19 | 0.091 (3) | 0.371 (2) | 0.186 (2) | 0.091 (6)* | |
C20 | 0.3150 (2) | 0.41861 (16) | 0.2737 (2) | 0.0674 (4) | |
H20 | 0.290 (3) | 0.342 (2) | 0.320 (2) | 0.088 (6)* | |
C21 | 0.47608 (17) | 0.51574 (14) | 0.28732 (16) | 0.0512 (3) | |
H21 | 0.556 (2) | 0.5037 (18) | 0.3447 (17) | 0.057 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.05513 (18) | 0.05757 (19) | 0.03706 (15) | 0.02119 (14) | 0.01222 (12) | 0.01499 (12) |
C1 | 0.0378 (5) | 0.0334 (5) | 0.0285 (4) | 0.0132 (4) | 0.0056 (4) | 0.0078 (4) |
N2 | 0.0351 (4) | 0.0336 (4) | 0.0283 (4) | 0.0140 (3) | 0.0052 (3) | 0.0075 (3) |
C3 | 0.0347 (5) | 0.0370 (5) | 0.0370 (5) | 0.0101 (4) | 0.0044 (4) | 0.0154 (4) |
C4 | 0.0491 (7) | 0.0631 (8) | 0.0609 (8) | 0.0336 (7) | 0.0017 (6) | 0.0076 (7) |
C5 | 0.0454 (6) | 0.0396 (6) | 0.0440 (6) | 0.0205 (5) | 0.0136 (5) | 0.0088 (5) |
C6 | 0.0457 (6) | 0.0358 (5) | 0.0370 (5) | 0.0195 (4) | 0.0093 (4) | 0.0070 (4) |
C7 | 0.0418 (5) | 0.0414 (5) | 0.0355 (5) | 0.0231 (4) | 0.0082 (4) | 0.0073 (4) |
C8 | 0.0446 (6) | 0.0479 (6) | 0.0449 (6) | 0.0211 (5) | 0.0080 (5) | 0.0066 (5) |
C9 | 0.0458 (7) | 0.0536 (7) | 0.0672 (9) | 0.0215 (6) | 0.0189 (6) | 0.0155 (6) |
C10 | 0.0653 (9) | 0.0679 (9) | 0.0591 (8) | 0.0385 (7) | 0.0314 (7) | 0.0263 (7) |
C11 | 0.0716 (9) | 0.0790 (10) | 0.0362 (6) | 0.0430 (8) | 0.0146 (6) | 0.0133 (6) |
C12 | 0.0499 (7) | 0.0610 (7) | 0.0367 (6) | 0.0272 (6) | 0.0060 (5) | 0.0052 (5) |
C13 | 0.0451 (6) | 0.0400 (5) | 0.0302 (5) | 0.0134 (5) | 0.0048 (4) | 0.0121 (4) |
N14 | 0.0491 (6) | 0.0404 (5) | 0.0316 (5) | 0.0112 (4) | 0.0092 (4) | 0.0130 (4) |
O15 | 0.0468 (5) | 0.0536 (5) | 0.0355 (4) | 0.0098 (4) | −0.0027 (3) | 0.0127 (4) |
C16 | 0.0399 (5) | 0.0342 (5) | 0.0360 (5) | 0.0110 (4) | 0.0045 (4) | 0.0032 (4) |
C17 | 0.0486 (7) | 0.0563 (7) | 0.0454 (7) | 0.0115 (6) | −0.0060 (5) | 0.0098 (6) |
C18 | 0.0470 (8) | 0.0774 (11) | 0.0644 (9) | 0.0101 (7) | −0.0124 (7) | 0.0007 (8) |
C19 | 0.0458 (8) | 0.0524 (8) | 0.0918 (12) | −0.0025 (6) | 0.0025 (8) | −0.0069 (8) |
C20 | 0.0624 (9) | 0.0376 (7) | 0.0969 (13) | 0.0096 (6) | 0.0256 (9) | 0.0165 (7) |
C21 | 0.0482 (7) | 0.0395 (6) | 0.0690 (9) | 0.0164 (5) | 0.0139 (6) | 0.0178 (6) |
C1—N2 | 1.4779 (14) | C10—C11 | 1.375 (2) |
C1—C16 | 1.5302 (16) | C10—H10 | 0.965 (19) |
C1—C13 | 1.5319 (15) | C11—C12 | 1.392 (2) |
C1—C5 | 1.5596 (16) | C11—H11 | 0.95 (2) |
N2—C3 | 1.3466 (14) | C12—H12 | 0.969 (16) |
N2—C6 | 1.4632 (14) | C13—N14 | 1.4839 (16) |
C3—O15 | 1.2262 (14) | C13—H13B | 0.931 (16) |
C3—C4 | 1.5042 (18) | C13—H13A | 0.939 (15) |
C4—C5 | 1.505 (2) | N14—H14C | 0.896 (18) |
C4—H4B | 0.98 (2) | N14—H14B | 0.885 (18) |
C4—H4A | 0.90 (2) | N14—H14A | 0.874 (16) |
C5—H5B | 0.984 (16) | C16—C17 | 1.3877 (18) |
C5—H5A | 0.973 (17) | C16—C21 | 1.3918 (17) |
C6—C7 | 1.5168 (16) | C17—C18 | 1.392 (2) |
C6—H6B | 0.962 (17) | C17—H17 | 0.990 (17) |
C6—H6A | 0.941 (14) | C18—C19 | 1.371 (3) |
C7—C12 | 1.3855 (17) | C18—H18 | 0.95 (2) |
C7—C8 | 1.3899 (18) | C19—C20 | 1.376 (3) |
C8—C9 | 1.3881 (19) | C19—H19 | 0.92 (2) |
C8—H8 | 1.013 (18) | C20—C21 | 1.386 (2) |
C9—C10 | 1.375 (2) | C20—H20 | 0.93 (2) |
C9—H9 | 0.901 (18) | C21—H21 | 0.950 (16) |
N2—C1—C16 | 109.65 (9) | C9—C10—C11 | 119.62 (13) |
N2—C1—C13 | 109.65 (9) | C9—C10—H10 | 121.5 (11) |
C16—C1—C13 | 110.89 (9) | C11—C10—H10 | 118.9 (11) |
N2—C1—C5 | 102.41 (9) | C10—C11—C12 | 120.23 (14) |
C16—C1—C5 | 112.54 (9) | C10—C11—H11 | 120.7 (12) |
C13—C1—C5 | 111.35 (9) | C12—C11—H11 | 119.0 (12) |
C3—N2—C6 | 121.94 (10) | C7—C12—C11 | 120.53 (14) |
C3—N2—C1 | 115.18 (9) | C7—C12—H12 | 119.8 (10) |
C6—N2—C1 | 122.37 (9) | C11—C12—H12 | 119.7 (10) |
O15—C3—N2 | 124.49 (11) | N14—C13—C1 | 113.43 (10) |
O15—C3—C4 | 126.83 (11) | N14—C13—H13B | 107.5 (9) |
N2—C3—C4 | 108.68 (10) | C1—C13—H13B | 110.2 (10) |
C3—C4—C5 | 106.41 (10) | N14—C13—H13A | 107.0 (9) |
C3—C4—H4B | 106.9 (14) | C1—C13—H13A | 113.2 (9) |
C5—C4—H4B | 113.5 (14) | H13B—C13—H13A | 105.0 (13) |
C3—C4—H4A | 108.8 (14) | C13—N14—H14C | 113.7 (11) |
C5—C4—H4A | 113.3 (14) | C13—N14—H14B | 105.8 (11) |
H4B—C4—H4A | 107.7 (19) | H14C—N14—H14B | 105.5 (15) |
C4—C5—C1 | 106.72 (10) | C13—N14—H14A | 113.5 (10) |
C4—C5—H5B | 109.3 (9) | H14C—N14—H14A | 108.1 (14) |
C1—C5—H5B | 109.8 (9) | H14B—N14—H14A | 109.9 (14) |
C4—C5—H5A | 110.2 (10) | C17—C16—C21 | 118.35 (12) |
C1—C5—H5A | 110.0 (10) | C17—C16—C1 | 123.25 (11) |
H5B—C5—H5A | 110.7 (13) | C21—C16—C1 | 118.29 (11) |
N2—C6—C7 | 116.17 (9) | C16—C17—C18 | 120.59 (15) |
N2—C6—H6B | 109.2 (10) | C16—C17—H17 | 122.2 (10) |
C7—C6—H6B | 106.3 (10) | C18—C17—H17 | 117.2 (10) |
N2—C6—H6A | 107.8 (8) | C19—C18—C17 | 120.24 (16) |
C7—C6—H6A | 110.5 (8) | C19—C18—H18 | 122.5 (12) |
H6B—C6—H6A | 106.4 (13) | C17—C18—H18 | 117.2 (12) |
C12—C7—C8 | 118.79 (12) | C18—C19—C20 | 119.92 (15) |
C12—C7—C6 | 119.70 (11) | C18—C19—H19 | 121.2 (14) |
C8—C7—C6 | 121.31 (11) | C20—C19—H19 | 118.9 (14) |
C9—C8—C7 | 120.17 (13) | C19—C20—C21 | 120.21 (16) |
C9—C8—H8 | 120.1 (10) | C19—C20—H20 | 121.6 (13) |
C7—C8—H8 | 119.7 (10) | C21—C20—H20 | 118.2 (13) |
C10—C9—C8 | 120.65 (14) | C20—C21—C16 | 120.69 (15) |
C10—C9—H9 | 120.0 (12) | C20—C21—H21 | 119.3 (10) |
C8—C9—H9 | 119.3 (12) | C16—C21—H21 | 120.0 (10) |
C16—C1—N2—C3 | 125.64 (9) | C8—C9—C10—C11 | 0.0 (2) |
C13—C1—N2—C3 | −112.39 (10) | C9—C10—C11—C12 | −0.8 (2) |
C5—C1—N2—C3 | 5.94 (11) | C8—C7—C12—C11 | 0.53 (18) |
C16—C1—N2—C6 | −62.39 (12) | C6—C7—C12—C11 | 175.49 (12) |
C13—C1—N2—C6 | 59.58 (12) | C10—C11—C12—C7 | 0.5 (2) |
C5—C1—N2—C6 | 177.91 (9) | N2—C1—C13—N14 | 55.21 (13) |
C6—N2—C3—O15 | 5.74 (16) | C16—C1—C13—N14 | 176.45 (9) |
C1—N2—C3—O15 | 177.74 (10) | C5—C1—C13—N14 | −57.41 (13) |
C6—N2—C3—C4 | −173.77 (11) | N2—C1—C16—C17 | 111.94 (13) |
C1—N2—C3—C4 | −1.76 (13) | C13—C1—C16—C17 | −9.29 (15) |
O15—C3—C4—C5 | 177.04 (11) | C5—C1—C16—C17 | −134.77 (12) |
N2—C3—C4—C5 | −3.47 (15) | N2—C1—C16—C21 | −64.16 (13) |
C3—C4—C5—C1 | 6.93 (15) | C13—C1—C16—C21 | 174.61 (11) |
N2—C1—C5—C4 | −7.59 (12) | C5—C1—C16—C21 | 49.13 (14) |
C16—C1—C5—C4 | −125.25 (12) | C21—C16—C17—C18 | −0.6 (2) |
C13—C1—C5—C4 | 109.52 (12) | C1—C16—C17—C18 | −176.65 (13) |
C3—N2—C6—C7 | −79.67 (13) | C16—C17—C18—C19 | −0.1 (3) |
C1—N2—C6—C7 | 108.90 (12) | C17—C18—C19—C20 | 0.3 (3) |
N2—C6—C7—C12 | 102.59 (13) | C18—C19—C20—C21 | 0.1 (3) |
N2—C6—C7—C8 | −82.58 (14) | C19—C20—C21—C16 | −0.7 (2) |
C12—C7—C8—C9 | −1.29 (18) | C17—C16—C21—C20 | 1.0 (2) |
C6—C7—C8—C9 | −176.16 (11) | C1—C16—C21—C20 | 177.24 (13) |
C7—C8—C9—C10 | 1.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N14—H14A···O15i | 0.87 (2) | 2.01 (2) | 2.839 (2) | 159 (1) |
N14—H14B···Cl1ii | 0.88 (2) | 2.21 (2) | 3.077 (1) | 167 (1) |
N14—H14C···Cl1iii | 0.90 (2) | 2.21 (2) | 3.093 (1) | 167 (1) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z; (iii) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H21NO4 | C18H21N2O+·Cl− |
Mr | 291.34 | 316.82 |
Crystal system, space group | Monoclinic, Cc | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 19.309 (4), 6.4210 (13), 13.735 (3) | 8.8302 (18), 10.077 (2), 10.094 (2) |
α, β, γ (°) | 90, 113.20 (3), 90 | 99.74 (3), 92.53 (3), 111.39 (3) |
V (Å3) | 1565.2 (7) | 818.7 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.24 |
Crystal size (mm) | 0.3 × 0.24 × 0.18 | 0.23 (radius) |
Data collection | ||
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8331, 2273, 1635 | 9597, 4767, 3895 |
Rint | 0.036 | 0.017 |
(sin θ/λ)max (Å−1) | 0.703 | 0.703 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.098, 1.04 | 0.037, 0.107, 1.03 |
No. of reflections | 2273 | 4767 |
No. of parameters | 220 | 283 |
No. of restraints | 17 | 0 |
H-atom treatment | H-atom parameters constrained | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.13, −0.12 | 0.26, −0.16 |
Computer programs: CAD-4 Manual (Enraf-Nonius, 1988), CAD-4 Manual, HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Bruker, 2000), SHELXTL-NT.
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14···O7i | 0.82 | 1.85 | 2.668 (2) | 175 |
Symmetry code: (i) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N14—H14A···O15i | 0.87 (2) | 2.01 (2) | 2.839 (2) | 159 (1) |
N14—H14B···Cl1ii | 0.88 (2) | 2.21 (2) | 3.077 (1) | 167 (1) |
N14—H14C···Cl1iii | 0.90 (2) | 2.21 (2) | 3.093 (1) | 167 (1) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z; (iii) x+1, y, z. |
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The title compounds belong to a family of non-nucleoside reverse transcriptase inhibitors (NNRTIs), with potential properties as inhibitors of HIV-1 RT. The characteristic structural feature of these compounds is their butterfly-like conformation, with a hydrophilic `body' and two hydrophobic `wing' moieties, as depicted in the scheme (De Clercq, 1996). Both (I) and (II) were synthesized as racemic mixtures. Views of the molecules of (I) and (II) with their atomic numbering schemes are depicted in Figs. 1 and 2, respectively. Details of the hydrogen-bonding interactions are given in Tables 1 and 2. \sch
It has been observed that the anti-HIV-1 activity of compounds with butterfly-like structures depends on the orientational relationship between the wings and the body of the structure. These relationships may be described by the dihedral angles between the aryl groups (`wing' planes W1 and W2 in the scheme) and the pyrrolidine ring (part of the `body', plane B in the scheme) (Karapetyan et al., 2002; Tamazyan et al., 2002).
In contrast with other compounds in this class, the almost flat `wing' (W2) is replaced by a bulky and non-planar tert-butoxycarbonyl group in (I). For this reason, two of the above-described dihedral angles, W1/W2 and B/W2, are no longer defined. The B/W1 dihedral angle is 79.48 (9)°. The pyrrolidine ring has the same half-chair conformation as in 1-(2-chlorobenzoyl)-2-phenylpyrrolidine-2-carboxamide (Tamazyan et al., 2002), but its biological activity is substantially lower.
Molecules of the same chirality in (I) form infinite chains along [010] via O14—H14···O7i and O7···H14ii—O14ii hydrogen bonds (Fig. 3; symmetry codes as defined in Fig. 3). The crystal packing of (I) creates two hydrophobic planes parallel to the ab and ac planes. This packing evidently allows for the detected rotational disorder around the C9—O8 bond for the trimethyl group of the tert-butoxycarbonyl moiety.
In the crystals of (II), two neighbouring molecules related by an inversion centre are connected into dimers via double hydrogen bonding, N14—H14A···O15i and N14i—H14Ai···O15 (Fig.4; symmetry codes as defined in Fig. 4). Simultaneously, these dimers are connected into infinite chains via hydrogen bonding between two ammonio H atoms and two Cl− ions.
The dihedral angles W1/W2, B/W1 and B/W2 are 55.20 (6), 88.09 (6) and 60.70 (5)°, respectively, in (II). The structure of (II) may be derived from the structure of 1-benzyl-5-oxo-2-phenylpyrrolidine-2-carboxamide (Karapetyan et al., 2002) by simply replacing the carboxamide group in the body by an aminomethyl group. This replacement does not have a great effect on the conformation of the pyrrolidine ring, as both compounds still retain an envelope conformation. However, the dihedral angles and the hydrogen-bonding properties between neighbouring molecules change drastically. Nonetheless, these changes have only a minor effect on the biological activity of the compound.