


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009241/gg1112sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009241/gg1112IIIsup2.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009241/gg1112IVsup3.hkl |
CCDC references: 192978; 192979
The title compounds were synthesized as described by Martirosyan et al. (2000). Recrystallization from ethanol afforded colourless crystals suitable for X-ray analysis.
Both molecules (III) and (IV) crystallized in the monoclinic system. The space groups determined from the systematic absences were both P21/c. The positional and isotropic displacement parameters of all H atoms were refined independently, apart from the methyl H atoms on C15, C24 and C25 in (IV), which were treated as riding, with C—H = 0.96 Å. Is this added text OK?
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: SETANG in CAD-4 Software; data reduction: local program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C18H18N2O2 | F(000) = 624 |
Mr = 294.34 | Dx = 1.289 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 11.959 (2) Å | θ = 14.3–15.9° |
b = 10.303 (2) Å | µ = 0.09 mm−1 |
c = 21.489 (4) Å | T = 293 K |
β = 145.05 (3)° | Prism, colourless |
V = 1516.7 (12) Å3 | 0.25 × 0.15 × 0.10 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.025 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 1.9° |
Graphite monochromator | h = 0→16 |
ω/2θ scans | k = 0→14 |
4601 measured reflections | l = −30→17 |
4411 independent reflections | 3 standard reflections every 60 min |
2559 reflections with I > 2σ(I) | intensity 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)] = 0.048 | All H-atom parameters refined |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4411 reflections | Δρmax = 0.20 e Å−3 |
272 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0150 (17) |
Primary atom site location: structure-invariant direct methods |
C18H18N2O2 | V = 1516.7 (12) Å3 |
Mr = 294.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.959 (2) Å | µ = 0.09 mm−1 |
b = 10.303 (2) Å | T = 293 K |
c = 21.489 (4) Å | 0.25 × 0.15 × 0.10 mm |
β = 145.05 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.025 |
4601 measured reflections | 3 standard reflections every 60 min |
4411 independent reflections | intensity decay: variation +−1.0% |
2559 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.121 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.20 e Å−3 |
4411 reflections | Δρmin = −0.16 e Å−3 |
272 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 9.7401(0.0072)x + 5.8400(0.0067)y + 15.8704(0.0131)z = 15.0765(0.0089) * 0.0016 (0.0011) C16 * -0.0023 (0.0012) C17 * 0.0022 (0.0013) C18 * -0.0013 (0.0014) C19 * 0.0007 (0.0013) C20 * -0.0008 (0.0012) C21 Rms deviation of fitted atoms = 0.0016 -1.9925(0.0082)x + 3.8377(0.0075)y + 14.1729 (0.0134)z = 10.7279(0.0073) Angle to previous plane (with approximate e.s.d.) = 62.62 (0.07) * 0.0023 (0.0011) C10 * -0.0002 (0.0012) C11 * -0.0025 (0.0013) C12 * 0.0031 (0.0013) C13 * -0.0010 (0.0013) C14 * -0.0017 (0.0012) C15 Rms deviation of fitted atoms = 0.0021 - 8.5711(0.0090)x - 6.6200(0.0078)y + 9.2876(0.0194)z = 2.1794(0.0156) Angle to previous plane (with approximate e.s.d.) = 68.45 (0.10) * 0.1188 (0.0010) C1 * -0.1036 (0.0010) N2 * 0.0371 (0.0011) C3 * 0.0442 (0.0012) C4 * -0.0965 (0.0013) C5 Rms deviation of fitted atoms = 0.0866 - 9.7401(0.0072)x + 5.8400(0.0067)y + 15.8704(0.0131)z = 15.0765(0.0089) Angle to previous plane (with approximate e.s.d.) = 79.28 (0.06) * 0.0016 (0.0011) C16 * -0.0023 (0.0012) C17 * 0.0022 (0.0013) C18 * -0.0013 (0.0014) C19 * 0.0007 (0.0013) C20 * -0.0008 (0.0012) C21 Rms deviation of fitted atoms = 0.0016 |
x | y | z | Uiso*/Ueq | ||
C1 | −0.0371 (2) | 0.65500 (14) | 0.68005 (11) | 0.0357 (3) | |
N2 | 0.08982 (17) | 0.56065 (12) | 0.70601 (10) | 0.0386 (3) | |
C3 | 0.2231 (2) | 0.50549 (16) | 0.80483 (12) | 0.0408 (4) | |
C4 | 0.2324 (3) | 0.5814 (2) | 0.86831 (15) | 0.0549 (5) | |
H4B | 0.357 (4) | 0.612 (2) | 0.935 (2) | 0.102 (8)* | |
H4A | 0.197 (4) | 0.523 (2) | 0.887 (2) | 0.097 (8)* | |
C5 | 0.0860 (3) | 0.68926 (18) | 0.79491 (14) | 0.0515 (4) | |
H5B | 0.006 (3) | 0.7011 (19) | 0.7938 (16) | 0.070 (6)* | |
H5A | 0.155 (3) | 0.769 (2) | 0.8207 (18) | 0.082 (7)* | |
C6 | −0.2286 (2) | 0.58553 (15) | 0.61218 (13) | 0.0396 (3) | |
O7 | −0.26259 (17) | 0.47483 (10) | 0.57911 (10) | 0.0528 (3) | |
N8 | −0.3505 (2) | 0.65171 (15) | 0.59320 (14) | 0.0508 (4) | |
H8B | −0.326 (3) | 0.730 (2) | 0.6158 (15) | 0.054 (5)* | |
H8A | −0.467 (3) | 0.6151 (18) | 0.5468 (15) | 0.056 (5)* | |
C9 | 0.0408 (2) | 0.50055 (17) | 0.62371 (13) | 0.0434 (4) | |
H9B | −0.083 (3) | 0.5341 (16) | 0.5548 (14) | 0.045 (4)* | |
H9A | 0.028 (2) | 0.4055 (17) | 0.6265 (13) | 0.046 (5)* | |
C10 | 0.1896 (2) | 0.52620 (15) | 0.64126 (11) | 0.0412 (4) | |
C11 | 0.1923 (3) | 0.64239 (18) | 0.61001 (14) | 0.0509 (4) | |
H11 | 0.101 (3) | 0.7103 (18) | 0.5776 (14) | 0.053 (5)* | |
C12 | 0.3257 (3) | 0.6624 (2) | 0.62318 (16) | 0.0597 (5) | |
H12 | 0.324 (3) | 0.741 (2) | 0.5997 (16) | 0.070 (6)* | |
C13 | 0.4573 (3) | 0.5671 (2) | 0.66788 (15) | 0.0602 (5) | |
H13 | 0.547 (3) | 0.580 (2) | 0.6749 (18) | 0.079 (7)* | |
C14 | 0.4558 (3) | 0.4515 (2) | 0.69869 (15) | 0.0569 (5) | |
H14 | 0.544 (3) | 0.3792 (19) | 0.7272 (15) | 0.062 (5)* | |
C15 | 0.3229 (2) | 0.43054 (18) | 0.68562 (14) | 0.0487 (4) | |
H15 | 0.316 (2) | 0.3487 (18) | 0.7048 (14) | 0.050 (5)* | |
C16 | −0.0823 (2) | 0.76929 (14) | 0.61646 (12) | 0.0355 (3) | |
C17 | −0.2595 (2) | 0.77757 (17) | 0.50444 (13) | 0.0447 (4) | |
H17 | −0.363 (3) | 0.7138 (18) | 0.4652 (15) | 0.057 (5)* | |
C18 | −0.2962 (3) | 0.87665 (19) | 0.44572 (17) | 0.0581 (5) | |
H18 | −0.418 (3) | 0.880 (2) | 0.3696 (19) | 0.079 (7)* | |
C19 | −0.1562 (3) | 0.96808 (19) | 0.49780 (18) | 0.0604 (5) | |
H19 | −0.186 (3) | 1.038 (2) | 0.4551 (17) | 0.077 (6)* | |
C20 | 0.0197 (3) | 0.96190 (18) | 0.60813 (19) | 0.0591 (5) | |
H20 | 0.122 (3) | 1.026 (2) | 0.6472 (17) | 0.078 (6)* | |
C21 | 0.0576 (3) | 0.86323 (16) | 0.66764 (15) | 0.0486 (4) | |
H21 | 0.182 (2) | 0.8586 (16) | 0.7458 (14) | 0.046 (5)* | |
O22 | 0.31807 (18) | 0.40861 (12) | 0.83481 (10) | 0.0567 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0360 (7) | 0.0325 (7) | 0.0326 (7) | 0.0002 (6) | 0.0269 (7) | −0.0005 (6) |
N2 | 0.0336 (6) | 0.0361 (7) | 0.0307 (6) | 0.0033 (5) | 0.0234 (6) | 0.0010 (5) |
C3 | 0.0307 (7) | 0.0425 (8) | 0.0366 (7) | −0.0023 (7) | 0.0250 (7) | 0.0067 (7) |
C4 | 0.0472 (10) | 0.0718 (12) | 0.0384 (9) | 0.0024 (9) | 0.0336 (9) | 0.0072 (9) |
C5 | 0.0593 (11) | 0.0464 (10) | 0.0391 (9) | −0.0028 (9) | 0.0384 (9) | −0.0039 (8) |
C6 | 0.0453 (8) | 0.0337 (7) | 0.0437 (8) | −0.0009 (7) | 0.0372 (8) | 0.0018 (6) |
O7 | 0.0538 (7) | 0.0341 (6) | 0.0694 (8) | −0.0068 (5) | 0.0503 (7) | −0.0080 (5) |
N8 | 0.0534 (9) | 0.0416 (8) | 0.0700 (10) | −0.0106 (7) | 0.0531 (9) | −0.0126 (7) |
C9 | 0.0352 (8) | 0.0416 (9) | 0.0347 (8) | 0.0015 (7) | 0.0249 (7) | −0.0050 (7) |
C10 | 0.0336 (7) | 0.0440 (9) | 0.0302 (7) | −0.0010 (6) | 0.0230 (7) | −0.0075 (6) |
C11 | 0.0529 (10) | 0.0452 (9) | 0.0475 (10) | 0.0034 (8) | 0.0397 (9) | −0.0021 (8) |
C12 | 0.0644 (12) | 0.0597 (12) | 0.0523 (11) | −0.0098 (10) | 0.0473 (11) | −0.0075 (10) |
C13 | 0.0470 (10) | 0.0851 (15) | 0.0454 (10) | −0.0071 (10) | 0.0373 (9) | −0.0098 (10) |
C14 | 0.0433 (9) | 0.0738 (13) | 0.0462 (10) | 0.0095 (9) | 0.0352 (9) | −0.0002 (9) |
C15 | 0.0425 (9) | 0.0499 (10) | 0.0419 (9) | 0.0060 (8) | 0.0323 (8) | 0.0011 (8) |
C16 | 0.0356 (7) | 0.0326 (7) | 0.0386 (8) | 0.0013 (6) | 0.0305 (7) | 0.0004 (6) |
C17 | 0.0415 (9) | 0.0466 (9) | 0.0382 (8) | −0.0015 (7) | 0.0311 (8) | 0.0014 (7) |
C18 | 0.0585 (11) | 0.0633 (12) | 0.0482 (10) | 0.0120 (10) | 0.0428 (10) | 0.0167 (9) |
C19 | 0.0763 (14) | 0.0512 (11) | 0.0800 (14) | 0.0156 (10) | 0.0694 (13) | 0.0216 (10) |
C20 | 0.0634 (12) | 0.0448 (10) | 0.0855 (14) | −0.0044 (9) | 0.0643 (13) | 0.0029 (10) |
C21 | 0.0376 (9) | 0.0440 (9) | 0.0514 (10) | −0.0019 (7) | 0.0339 (9) | 0.0002 (8) |
O22 | 0.0497 (7) | 0.0534 (7) | 0.0586 (7) | 0.0163 (6) | 0.0427 (7) | 0.0226 (6) |
C1—N2 | 1.4740 (19) | C10—C15 | 1.389 (2) |
C1—C16 | 1.528 (2) | C11—C12 | 1.388 (3) |
C1—C6 | 1.552 (2) | C11—H11 | 0.957 (18) |
C1—C5 | 1.558 (2) | C12—C13 | 1.373 (3) |
N2—C3 | 1.351 (2) | C12—H12 | 0.94 (2) |
N2—C9 | 1.468 (2) | C13—C14 | 1.370 (3) |
C3—O22 | 1.2255 (19) | C13—H13 | 0.97 (2) |
C3—C4 | 1.495 (3) | C14—C15 | 1.386 (3) |
C4—C5 | 1.504 (3) | C14—H14 | 0.989 (19) |
C4—H4B | 0.94 (3) | C15—H15 | 0.972 (18) |
C4—H4A | 0.99 (3) | C16—C17 | 1.389 (2) |
C5—H5B | 0.94 (2) | C16—C21 | 1.389 (2) |
C5—H5A | 0.96 (2) | C17—C18 | 1.385 (2) |
C6—O7 | 1.2237 (18) | C17—H17 | 0.979 (19) |
C6—N8 | 1.335 (2) | C18—C19 | 1.368 (3) |
N8—H8B | 0.86 (2) | C18—H18 | 0.94 (2) |
N8—H8A | 0.89 (2) | C19—C20 | 1.369 (3) |
C9—C10 | 1.509 (2) | C19—H19 | 0.98 (2) |
C9—H9B | 0.953 (17) | C20—C21 | 1.387 (3) |
C9—H9A | 1.002 (17) | C20—H20 | 0.98 (2) |
C10—C11 | 1.386 (2) | C21—H21 | 0.969 (17) |
N2—C1—C16 | 110.27 (12) | C11—C10—C15 | 118.40 (16) |
N2—C1—C6 | 108.67 (12) | C11—C10—C9 | 121.41 (15) |
C16—C1—C6 | 110.31 (12) | C15—C10—C9 | 120.13 (16) |
N2—C1—C5 | 101.95 (13) | C10—C11—C12 | 120.58 (18) |
C16—C1—C5 | 115.11 (13) | C10—C11—H11 | 121.3 (11) |
C6—C1—C5 | 110.11 (14) | C12—C11—H11 | 118.1 (11) |
C3—N2—C9 | 120.52 (13) | C13—C12—C11 | 120.2 (2) |
C3—N2—C1 | 113.24 (13) | C13—C12—H12 | 119.7 (13) |
C9—N2—C1 | 123.50 (12) | C11—C12—H12 | 120.0 (13) |
O22—C3—N2 | 124.06 (16) | C14—C13—C12 | 119.89 (19) |
O22—C3—C4 | 127.05 (15) | C14—C13—H13 | 120.0 (13) |
N2—C3—C4 | 108.89 (14) | C12—C13—H13 | 120.1 (14) |
C3—C4—C5 | 106.12 (14) | C13—C14—C15 | 120.29 (18) |
C3—C4—H4B | 114.4 (16) | C13—C14—H14 | 121.8 (11) |
C5—C4—H4B | 112.4 (17) | C15—C14—H14 | 117.9 (11) |
C3—C4—H4A | 108.1 (14) | C14—C15—C10 | 120.61 (19) |
C5—C4—H4A | 111.1 (15) | C14—C15—H15 | 122.1 (10) |
H4B—C4—H4A | 105 (2) | C10—C15—H15 | 117.2 (10) |
C4—C5—C1 | 105.68 (15) | C17—C16—C21 | 117.75 (15) |
C4—C5—H5B | 114.0 (12) | C17—C16—C1 | 121.07 (14) |
C1—C5—H5B | 111.5 (13) | C21—C16—C1 | 121.02 (15) |
C4—C5—H5A | 108.6 (14) | C18—C17—C16 | 121.21 (17) |
C1—C5—H5A | 111.0 (13) | C18—C17—H17 | 118.4 (11) |
H5B—C5—H5A | 106.1 (18) | C16—C17—H17 | 120.4 (11) |
O7—C6—N8 | 122.60 (15) | C19—C18—C17 | 120.05 (19) |
O7—C6—C1 | 120.51 (14) | C19—C18—H18 | 120.6 (14) |
N8—C6—C1 | 116.89 (14) | C17—C18—H18 | 119.4 (14) |
C6—N8—H8B | 121.7 (12) | C18—C19—C20 | 119.83 (18) |
C6—N8—H8A | 115.8 (12) | C18—C19—H19 | 118.8 (13) |
H8B—N8—H8A | 121.7 (17) | C20—C19—H19 | 121.4 (13) |
N2—C9—C10 | 113.60 (13) | C19—C20—C21 | 120.54 (18) |
N2—C9—H9B | 107.3 (10) | C19—C20—H20 | 121.4 (12) |
C10—C9—H9B | 109.6 (10) | C21—C20—H20 | 118.1 (13) |
N2—C9—H9A | 105.5 (10) | C20—C21—C16 | 120.62 (18) |
C10—C9—H9A | 111.3 (9) | C20—C21—H21 | 120.7 (10) |
H9B—C9—H9A | 109.1 (14) | C16—C21—H21 | 118.7 (10) |
C16—C1—N2—C3 | 143.19 (13) | N2—C9—C10—C11 | −80.13 (19) |
C6—C1—N2—C3 | −95.79 (15) | N2—C9—C10—C15 | 102.47 (17) |
C5—C1—N2—C3 | 20.47 (17) | C15—C10—C11—C12 | −0.2 (2) |
C16—C1—N2—C9 | −55.53 (18) | C9—C10—C11—C12 | −177.63 (15) |
C6—C1—N2—C9 | 65.48 (18) | C10—C11—C12—C13 | −0.3 (3) |
C5—C1—N2—C9 | −178.25 (15) | C11—C12—C13—C14 | 0.6 (3) |
C9—N2—C3—O22 | 4.0 (2) | C12—C13—C14—C15 | −0.4 (3) |
C1—N2—C3—O22 | 165.94 (14) | C13—C14—C15—C10 | 0.0 (3) |
C9—N2—C3—C4 | −175.78 (15) | C11—C10—C15—C14 | 0.3 (2) |
C1—N2—C3—C4 | −13.89 (18) | C9—C10—C15—C14 | 177.81 (15) |
O22—C3—C4—C5 | −179.26 (17) | N2—C1—C16—C17 | 100.93 (16) |
N2—C3—C4—C5 | 0.6 (2) | C6—C1—C16—C17 | −19.10 (19) |
C3—C4—C5—C1 | 11.7 (2) | C5—C1—C16—C17 | −144.44 (16) |
N2—C1—C5—C4 | −18.57 (19) | N2—C1—C16—C21 | −74.30 (18) |
C16—C1—C5—C4 | −137.92 (16) | C6—C1—C16—C21 | 165.66 (14) |
C6—C1—C5—C4 | 96.64 (18) | C5—C1—C16—C21 | 40.3 (2) |
N2—C1—C6—O7 | −7.89 (19) | C21—C16—C17—C18 | −0.5 (2) |
C16—C1—C6—O7 | 113.10 (16) | C1—C16—C17—C18 | −175.90 (15) |
C5—C1—C6—O7 | −118.77 (16) | C16—C17—C18—C19 | 0.6 (3) |
N2—C1—C6—N8 | 171.58 (13) | C17—C18—C19—C20 | −0.5 (3) |
C16—C1—C6—N8 | −67.43 (17) | C18—C19—C20—C21 | 0.3 (3) |
C5—C1—C6—N8 | 60.70 (18) | C19—C20—C21—C16 | −0.3 (3) |
C3—N2—C9—C10 | −78.84 (19) | C17—C16—C21—C20 | 0.4 (2) |
C1—N2—C9—C10 | 121.18 (16) | C1—C16—C21—C20 | 175.76 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8A···O7i | 0.89 (2) | 2.07 (2) | 2.955 (2) | 169 (2) |
N8—H8B···O22ii | 0.86 (2) | 2.08 (2) | 2.927 (2) | 165 (2) |
C5—H5A···O7ii | 0.96 (3) | 2.50 (2) | 3.329 (2) | 145 (4) |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2. |
C21H22N2O2 | F(000) = 712 |
Mr = 334.41 | Dx = 1.153 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 7.5182 (15) Å | θ = 14.4–18.5° |
b = 25.125 (5) Å | µ = 0.08 mm−1 |
c = 10.612 (2) Å | T = 293 K |
β = 106.07 (3)° | Sphere, colourless |
V = 1926.3 (7) Å3 | 0.17 mm (radius) |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.027 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 1.6° |
Graphite monochromator | h = −9→0 |
ω/2θ scans | k = 0→33 |
5212 measured reflections | l = 0→13 |
4621 independent reflections | 3 standard reflections every 60 min |
3067 reflections with I > 2σ(I) | intensity 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)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.142 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
4621 reflections | Δρmax = 0.18 e Å−3 |
282 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0064 (12) |
Primary atom site location: structure-invariant direct methods |
C21H22N2O2 | V = 1926.3 (7) Å3 |
Mr = 334.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5182 (15) Å | µ = 0.08 mm−1 |
b = 25.125 (5) Å | T = 293 K |
c = 10.612 (2) Å | 0.17 mm (radius) |
β = 106.07 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.027 |
5212 measured reflections | 3 standard reflections every 60 min |
4621 independent reflections | intensity decay: variation +−1.0% |
3067 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.18 e Å−3 |
4621 reflections | Δρmin = −0.20 e Å−3 |
282 parameters |
Geometry. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 4.1633 (0.0048) x + 3.4424 (0.0196) y + 10.0021 (0.0058) z = 8.8817 (0.0100) * 0.0066 (0.0012) C16 * -0.0032 (0.0014) C17 * -0.0028 (0.0014) C18 * 0.0052 (0.0013) C19 * -0.0016 (0.0012) C20 * -0.0043 (0.0012) C21 Rms deviation of fitted atoms = 0.0043 1.6974 (0.0071) x + 22.9531 (0.0159) y + 2.7868 (0.0092) z = 10.3939 (0.0065) Angle to previous plane (with approximate e.s.d.) = 73.86 (0.08) * 0.0054 (0.0014) C9 * -0.0002 (0.0016) C10 * -0.0048 (0.0017) C11 * 0.0045 (0.0017) C12 * 0.0007 (0.0017) C13 * -0.0057 (0.0015) C14 Rms deviation of fitted atoms = 0.0042 - 4.5455 (0.0067) x + 16.1467 (0.0213) y - 3.0230 (0.0107) z = 0.4438 (0.0126) Angle to previous plane (with approximate e.s.d.) = 73.06 (0.07) * 0.1851 (0.0011) C1 * -0.1067 (0.0011) N2 * -0.0193 (0.0012) C3 * 0.1372 (0.0014) C4 * -0.1963 (0.0014) C5 Rms deviation of fitted atoms = 0.1438 - 4.1633 (0.0048) x + 3.4424 (0.0196) y + 10.0021 (0.0058) z = 8.8817 (0.0100) Angle to previous plane (with approximate e.s.d.) = 87.92 (0.07) * 0.0066 (0.0012) C16 * -0.0032 (0.0014) C17 * -0.0028 (0.0014) C18 * 0.0052 (0.0013) C19 * -0.0016 (0.0012) C20 * -0.0043 (0.0012) C21 Rms deviation of fitted atoms = 0.0043 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4694 (2) | 0.35322 (7) | 0.97282 (16) | 0.0421 (4) | |
N2 | 0.45809 (18) | 0.31272 (5) | 0.87004 (13) | 0.0422 (3) | |
C3 | 0.3170 (2) | 0.27728 (7) | 0.86394 (18) | 0.0499 (4) | |
C4 | 0.2408 (3) | 0.28702 (10) | 0.9788 (2) | 0.0565 (5) | |
H4B | 0.119 (3) | 0.3068 (9) | 0.945 (2) | 0.070 (6)* | |
H4A | 0.218 (3) | 0.2543 (10) | 1.021 (2) | 0.081 (7)* | |
C5 | 0.3826 (3) | 0.32297 (9) | 1.06784 (19) | 0.0527 (5) | |
H5B | 0.334 (3) | 0.3477 (8) | 1.1171 (19) | 0.059 (6)* | |
H5A | 0.483 (3) | 0.3011 (9) | 1.128 (2) | 0.069 (6)* | |
C6 | 0.3435 (3) | 0.39776 (8) | 0.9125 (2) | 0.0614 (5) | |
N7 | 0.2384 (3) | 0.42897 (9) | 0.8638 (3) | 0.1005 (8) | |
O8 | 0.2639 (2) | 0.24484 (6) | 0.77767 (14) | 0.0749 (5) | |
C9 | 0.5338 (2) | 0.32114 (7) | 0.76151 (16) | 0.0450 (4) | |
C10 | 0.4264 (3) | 0.34283 (9) | 0.64623 (19) | 0.0613 (5) | |
H10 | 0.296 (3) | 0.3521 (9) | 0.641 (2) | 0.072 (6)* | |
C11 | 0.5008 (4) | 0.34988 (10) | 0.5412 (2) | 0.0746 (7) | |
H11 | 0.422 (3) | 0.3650 (10) | 0.460 (2) | 0.091 (8)* | |
C12 | 0.6809 (4) | 0.33590 (9) | 0.5500 (2) | 0.0706 (6) | |
C13 | 0.7859 (3) | 0.31389 (11) | 0.6659 (2) | 0.0725 (6) | |
H13 | 0.917 (3) | 0.3057 (10) | 0.676 (2) | 0.084 (7)* | |
C14 | 0.7128 (3) | 0.30627 (9) | 0.7710 (2) | 0.0595 (5) | |
H14 | 0.786 (3) | 0.2902 (9) | 0.852 (2) | 0.068 (6)* | |
C15 | 0.7614 (5) | 0.34374 (14) | 0.4349 (3) | 0.1120 (11) | |
H15A | 0.8739 | 0.3236 | 0.4493 | 0.168* | |
H15B | 0.7872 | 0.3808 | 0.4268 | 0.168* | |
H15C | 0.6740 | 0.3317 | 0.3558 | 0.168* | |
C16 | 0.6632 (2) | 0.37380 (6) | 1.03602 (15) | 0.0404 (4) | |
C17 | 0.7079 (3) | 0.42681 (7) | 1.03542 (18) | 0.0515 (4) | |
H17 | 0.618 (3) | 0.4528 (9) | 0.989 (2) | 0.071 (6)* | |
C18 | 0.8823 (3) | 0.44570 (8) | 1.1015 (2) | 0.0569 (5) | |
H18 | 0.908 (3) | 0.4828 (10) | 1.104 (2) | 0.075 (7)* | |
C19 | 1.0153 (2) | 0.41069 (7) | 1.16977 (16) | 0.0466 (4) | |
C20 | 0.9732 (2) | 0.35670 (7) | 1.17012 (16) | 0.0445 (4) | |
H20 | 1.067 (3) | 0.3345 (8) | 1.2167 (18) | 0.050 (5)* | |
C21 | 0.8000 (2) | 0.33879 (7) | 1.10394 (17) | 0.0437 (4) | |
H21 | 0.766 (3) | 0.3020 (8) | 1.1070 (18) | 0.056 (5)* | |
O22 | 1.19148 (18) | 0.42441 (6) | 1.23838 (13) | 0.0614 (4) | |
C23 | 1.2387 (3) | 0.47973 (9) | 1.2584 (3) | 0.0751 (7) | |
H23 | 1.191 (3) | 0.4974 (10) | 1.171 (2) | 0.087 (7)* | |
C24 | 1.4478 (4) | 0.48140 (13) | 1.2958 (3) | 0.1030 (10) | |
H24A | 1.4909 | 0.4652 | 1.2278 | 0.155* | |
H24D | 1.4966 | 0.4624 | 1.3764 | 0.155* | |
H24B | 1.4887 | 0.5177 | 1.3070 | 0.155* | |
C25 | 1.1600 (5) | 0.50233 (15) | 1.3620 (3) | 0.1234 (13) | |
H25D | 1.0275 | 0.4996 | 1.3340 | 0.185* | |
H25A | 1.1950 | 0.5391 | 1.3762 | 0.185* | |
H25B | 1.2070 | 0.4828 | 1.4421 | 0.185* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0415 (8) | 0.0404 (9) | 0.0447 (9) | 0.0011 (7) | 0.0123 (7) | −0.0037 (7) |
N2 | 0.0453 (7) | 0.0430 (8) | 0.0396 (7) | −0.0053 (6) | 0.0141 (6) | −0.0036 (6) |
C3 | 0.0496 (10) | 0.0493 (10) | 0.0503 (10) | −0.0098 (8) | 0.0129 (8) | −0.0033 (8) |
C4 | 0.0489 (11) | 0.0686 (13) | 0.0554 (11) | −0.0128 (10) | 0.0200 (9) | −0.0035 (10) |
C5 | 0.0495 (10) | 0.0627 (12) | 0.0512 (11) | −0.0066 (9) | 0.0226 (9) | −0.0086 (9) |
C6 | 0.0478 (10) | 0.0528 (11) | 0.0770 (14) | 0.0049 (9) | 0.0061 (9) | −0.0093 (10) |
N7 | 0.0759 (13) | 0.0633 (13) | 0.141 (2) | 0.0239 (11) | −0.0049 (13) | −0.0004 (13) |
O8 | 0.0893 (11) | 0.0740 (10) | 0.0658 (9) | −0.0381 (8) | 0.0291 (8) | −0.0253 (8) |
C9 | 0.0516 (10) | 0.0461 (9) | 0.0384 (8) | −0.0096 (8) | 0.0142 (7) | −0.0038 (7) |
C10 | 0.0605 (12) | 0.0708 (14) | 0.0506 (11) | −0.0045 (10) | 0.0119 (9) | 0.0082 (9) |
C11 | 0.0947 (18) | 0.0827 (16) | 0.0453 (11) | −0.0084 (14) | 0.0174 (11) | 0.0105 (11) |
C12 | 0.0939 (17) | 0.0759 (15) | 0.0508 (12) | −0.0210 (13) | 0.0348 (11) | −0.0095 (10) |
C13 | 0.0672 (14) | 0.0962 (18) | 0.0634 (14) | −0.0081 (13) | 0.0334 (11) | −0.0140 (12) |
C14 | 0.0564 (12) | 0.0774 (14) | 0.0472 (10) | 0.0018 (10) | 0.0186 (9) | −0.0023 (10) |
C15 | 0.154 (3) | 0.129 (3) | 0.0764 (17) | −0.020 (2) | 0.0715 (19) | −0.0030 (17) |
C16 | 0.0432 (8) | 0.0411 (9) | 0.0381 (8) | −0.0009 (7) | 0.0131 (7) | −0.0032 (7) |
C17 | 0.0537 (10) | 0.0396 (9) | 0.0549 (10) | 0.0033 (8) | 0.0043 (8) | 0.0033 (8) |
C18 | 0.0598 (11) | 0.0380 (10) | 0.0649 (12) | −0.0069 (8) | 0.0040 (9) | −0.0016 (8) |
C19 | 0.0448 (9) | 0.0510 (10) | 0.0430 (9) | −0.0027 (8) | 0.0105 (7) | −0.0054 (7) |
C20 | 0.0436 (9) | 0.0456 (10) | 0.0452 (9) | 0.0054 (8) | 0.0137 (7) | 0.0028 (7) |
C21 | 0.0473 (9) | 0.0395 (9) | 0.0477 (9) | 0.0020 (7) | 0.0190 (7) | 0.0003 (7) |
O22 | 0.0495 (7) | 0.0592 (8) | 0.0674 (9) | −0.0066 (6) | 0.0026 (6) | −0.0073 (6) |
C23 | 0.0766 (15) | 0.0621 (14) | 0.0686 (14) | −0.0235 (11) | −0.0099 (12) | −0.0015 (11) |
C24 | 0.0766 (17) | 0.115 (2) | 0.101 (2) | −0.0424 (16) | −0.0033 (14) | 0.0027 (17) |
C25 | 0.109 (2) | 0.112 (2) | 0.123 (3) | 0.0133 (19) | −0.0106 (19) | −0.062 (2) |
C1—N2 | 1.477 (2) | C15—H15A | 0.9600 |
C1—C6 | 1.491 (3) | C15—H15B | 0.9600 |
C1—C16 | 1.516 (2) | C15—H15C | 0.9600 |
C1—C5 | 1.544 (2) | C16—C17 | 1.374 (2) |
N2—C3 | 1.373 (2) | C16—C21 | 1.393 (2) |
N2—C9 | 1.434 (2) | C17—C18 | 1.388 (3) |
C3—O8 | 1.208 (2) | C17—H17 | 0.97 (2) |
C3—C4 | 1.503 (3) | C18—C19 | 1.377 (3) |
C4—C5 | 1.513 (3) | C18—H18 | 0.95 (2) |
C4—H4B | 1.02 (2) | C19—O22 | 1.367 (2) |
C4—H4A | 0.97 (2) | C19—C20 | 1.393 (3) |
C5—H5B | 0.95 (2) | C20—C21 | 1.373 (2) |
C5—H5A | 1.01 (2) | C20—H20 | 0.927 (19) |
C6—N7 | 1.132 (3) | C21—H21 | 0.96 (2) |
C9—C14 | 1.374 (3) | O22—C23 | 1.436 (3) |
C9—C10 | 1.378 (3) | C23—C25 | 1.497 (4) |
C10—C11 | 1.390 (3) | C23—C24 | 1.512 (3) |
C10—H10 | 1.00 (2) | C23—H23 | 1.00 (3) |
C11—C12 | 1.376 (4) | C24—H24A | 0.9600 |
C11—H11 | 0.98 (2) | C24—H24D | 0.9600 |
C12—C13 | 1.380 (3) | C24—H24B | 0.9600 |
C12—C15 | 1.519 (3) | C25—H25D | 0.9600 |
C13—C14 | 1.386 (3) | C25—H25A | 0.9600 |
C13—H13 | 0.99 (2) | C25—H25B | 0.9600 |
C14—H14 | 0.97 (2) | ||
N2—C1—C6 | 107.47 (14) | C12—C15—H15A | 109.5 |
N2—C1—C16 | 114.43 (13) | C12—C15—H15B | 109.5 |
C6—C1—C16 | 110.60 (15) | H15A—C15—H15B | 109.5 |
N2—C1—C5 | 101.23 (14) | C12—C15—H15C | 109.5 |
C6—C1—C5 | 108.51 (16) | H15A—C15—H15C | 109.5 |
C16—C1—C5 | 114.01 (14) | H15B—C15—H15C | 109.5 |
C3—N2—C9 | 122.07 (14) | C17—C16—C21 | 117.88 (16) |
C3—N2—C1 | 111.56 (13) | C17—C16—C1 | 122.35 (15) |
C9—N2—C1 | 122.47 (13) | C21—C16—C1 | 119.67 (15) |
O8—C3—N2 | 124.20 (17) | C16—C17—C18 | 121.81 (17) |
O8—C3—C4 | 127.19 (17) | C16—C17—H17 | 121.1 (13) |
N2—C3—C4 | 108.60 (15) | C18—C17—H17 | 117.1 (13) |
C3—C4—C5 | 104.08 (15) | C19—C18—C17 | 119.61 (18) |
C3—C4—H4B | 107.4 (12) | C19—C18—H18 | 119.9 (14) |
C5—C4—H4B | 109.9 (12) | C17—C18—H18 | 120.4 (14) |
C3—C4—H4A | 112.9 (14) | O22—C19—C18 | 125.05 (17) |
C5—C4—H4A | 113.6 (14) | O22—C19—C20 | 115.57 (16) |
H4B—C4—H4A | 108.8 (19) | C18—C19—C20 | 119.37 (16) |
C4—C5—C1 | 103.75 (15) | C21—C20—C19 | 120.14 (16) |
C4—C5—H5B | 115.1 (12) | C21—C20—H20 | 123.3 (12) |
C1—C5—H5B | 109.5 (12) | C19—C20—H20 | 116.5 (12) |
C4—C5—H5A | 110.3 (13) | C20—C21—C16 | 121.17 (17) |
C1—C5—H5A | 107.5 (12) | C20—C21—H21 | 121.3 (11) |
H5B—C5—H5A | 110.3 (17) | C16—C21—H21 | 117.5 (11) |
N7—C6—C1 | 175.1 (2) | C19—O22—C23 | 119.09 (16) |
C14—C9—C10 | 119.60 (18) | O22—C23—C25 | 110.1 (2) |
C14—C9—N2 | 119.96 (16) | O22—C23—C24 | 105.2 (2) |
C10—C9—N2 | 120.41 (17) | C25—C23—C24 | 113.0 (2) |
C9—C10—C11 | 119.7 (2) | O22—C23—H23 | 106.5 (15) |
C9—C10—H10 | 117.8 (12) | C25—C23—H23 | 113.3 (15) |
C11—C10—H10 | 122.4 (12) | C24—C23—H23 | 108.2 (14) |
C12—C11—C10 | 121.3 (2) | C23—C24—H24A | 109.5 |
C12—C11—H11 | 120.2 (15) | C23—C24—H24D | 109.5 |
C10—C11—H11 | 118.5 (15) | H24A—C24—H24D | 109.5 |
C11—C12—C13 | 118.2 (2) | C23—C24—H24B | 109.5 |
C11—C12—C15 | 121.0 (2) | H24A—C24—H24B | 109.5 |
C13—C12—C15 | 120.8 (2) | H24D—C24—H24B | 109.5 |
C12—C13—C14 | 121.1 (2) | C23—C25—H25D | 109.5 |
C12—C13—H13 | 119.1 (14) | C23—C25—H25A | 109.5 |
C14—C13—H13 | 119.7 (14) | H25D—C25—H25A | 109.5 |
C9—C14—C13 | 120.1 (2) | C23—C25—H25B | 109.5 |
C9—C14—H14 | 118.9 (13) | H25D—C25—H25B | 109.5 |
C13—C14—H14 | 120.9 (13) | H25A—C25—H25B | 109.5 |
C6—C1—N2—C3 | −87.82 (18) | C11—C12—C13—C14 | −0.3 (4) |
C16—C1—N2—C3 | 148.95 (15) | C15—C12—C13—C14 | −179.5 (2) |
C5—C1—N2—C3 | 25.88 (18) | C10—C9—C14—C13 | 1.1 (3) |
C6—C1—N2—C9 | 70.32 (19) | N2—C9—C14—C13 | 179.42 (18) |
C16—C1—N2—C9 | −52.9 (2) | C12—C13—C14—C9 | −0.7 (4) |
C5—C1—N2—C9 | −175.99 (15) | N2—C1—C16—C17 | 121.97 (18) |
C9—N2—C3—O8 | 11.7 (3) | C6—C1—C16—C17 | 0.4 (2) |
C1—N2—C3—O8 | 169.96 (18) | C5—C1—C16—C17 | −122.15 (19) |
C9—N2—C3—C4 | −166.93 (16) | N2—C1—C16—C21 | −61.8 (2) |
C1—N2—C3—C4 | −8.7 (2) | C6—C1—C16—C21 | 176.72 (15) |
O8—C3—C4—C5 | 168.5 (2) | C5—C1—C16—C21 | 54.1 (2) |
N2—C3—C4—C5 | −12.9 (2) | C21—C16—C17—C18 | −1.0 (3) |
C3—C4—C5—C1 | 28.0 (2) | C1—C16—C17—C18 | 175.34 (17) |
N2—C1—C5—C4 | −32.24 (19) | C16—C17—C18—C19 | 0.1 (3) |
C6—C1—C5—C4 | 80.66 (19) | C17—C18—C19—O22 | 179.94 (18) |
C16—C1—C5—C4 | −155.61 (16) | C17—C18—C19—C20 | 0.7 (3) |
C3—N2—C9—C14 | −113.3 (2) | O22—C19—C20—C21 | −179.90 (15) |
C1—N2—C9—C14 | 90.8 (2) | C18—C19—C20—C21 | −0.6 (3) |
C3—N2—C9—C10 | 65.0 (2) | C19—C20—C21—C16 | −0.3 (3) |
C1—N2—C9—C10 | −90.9 (2) | C17—C16—C21—C20 | 1.1 (2) |
C14—C9—C10—C11 | −0.6 (3) | C1—C16—C21—C20 | −175.34 (15) |
N2—C9—C10—C11 | −178.88 (19) | C18—C19—O22—C23 | 9.3 (3) |
C9—C10—C11—C12 | −0.4 (4) | C20—C19—O22—C23 | −171.41 (18) |
C10—C11—C12—C13 | 0.8 (4) | C19—O22—C23—C25 | 75.7 (2) |
C10—C11—C12—C15 | −180.0 (2) | C19—O22—C23—C24 | −162.24 (18) |
Experimental details
(III) | (IV) | |
Crystal data | ||
Chemical formula | C18H18N2O2 | C21H22N2O2 |
Mr | 294.34 | 334.41 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 11.959 (2), 10.303 (2), 21.489 (4) | 7.5182 (15), 25.125 (5), 10.612 (2) |
β (°) | 145.05 (3) | 106.07 (3) |
V (Å3) | 1516.7 (12) | 1926.3 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.08 |
Crystal size (mm) | 0.25 × 0.15 × 0.10 | 0.17 (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 | 4601, 4411, 2559 | 5212, 4621, 3067 |
Rint | 0.025 | 0.027 |
(sin θ/λ)max (Å−1) | 0.703 | 0.661 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.121, 1.01 | 0.049, 0.142, 1.05 |
No. of reflections | 4411 | 4621 |
No. of parameters | 272 | 282 |
H-atom treatment | All H-atom parameters refined | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 | 0.18, −0.20 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1988), SETANG in CAD-4 Software, local program, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8A···O7i | 0.89 (2) | 2.07 (2) | 2.955 (2) | 169 (2) |
N8—H8B···O22ii | 0.86 (2) | 2.08 (2) | 2.927 (2) | 165 (2) |
C5—H5A···O7ii | 0.96 (3) | 2.50 (2) | 3.329 (2) | 145 (4) |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2. |
In the last few years, interest in non-nucleoside reverse transcriptase inhibitors (NNRTIs) has expanded, primarily because of their anti-HIV-1 activity. One of the best representatives of this class of compounds is loviride, (I) (Pauvels et al., 1993). The common structural feature of these compounds is their butterfly-like conformation, and the molecular structure consists of a hydrophilic (`body') and two hydrophobic (`wing') moieties. According to the literature, the anti-HIV-1 activity of the compounds depends on the conformational rigidity and on the orientation of the wings relative to the body (De Clercq, 1996).
The inclusion of a pyrrolidine ring into the structure of loviride might increase the conformational rigidity. For this reason, a new method of synthesis of 1,2-substituted derivatives of 5-oxo-2-pyrrolidine carboxylic acid, (II), has been developed (Martirosyan et al., 2000). Using this method, 1-benzyl-5-oxo-2-phenylpyrrolidine-2-carboxamide, (III), and 2-(4-isopropoxyphenyl)-5-oxo-1-(4-tolyl)pyrrolidine-2-carbonitrile, (IV), were synthesized as racemic mixtures, since (III) and (IV) contain structural fragments from loviride, (I). \sch
Views of molecules (III) and (IV), with the atomic numbering schemes, are depicted in Figs. 1 and 2, respectively. In the crystal structure of (III), two neighbouring asymmetric molecules of (III) are related by an inversion centre and connected into a dimer via double hydrogen bonding through the amide groups (Fig. 3). Just one of H atoms of the amide (H8A) of each molecule takes part in this double hydrogen bonding, leading to the formation of dimers with graph set R22(8). The dimers are connected into a chain through hydrogen bonding between the other H atom of the amide (H8B) and the O atom (O22) of the carbonyl group of the pyrrolidine ring (Fig. 3). The geometry of the hydrogen bonds is listed in Table 1. A weaker interaction, C5—H5A···O7, is also present; details are also given in Table 1.
In contrast with (III), compound (IV) does not have active H atoms such as NH2, and for this reason, no strong hydrogen bonding is observed in the crystal structure, apart from two C—H···N/O interactions involving atoms N7 and O8. Nevertheless, (IV) also crystallizes in a centrosymmetric space group.
As mentioned previously, the anti-HIV-1 activity of the compounds under investigation depends on the orientational relationship between the wings and the body of the butterfly-like structures. 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). The dihedral angles W1/W2, B/W1 and B/W2 are 62.62 (8), 79.27 (6) and 68.45 (9)°, respectively, for (III), and 73.85 (13), 87.90 (13) and 73.06 (13)°, respectively, for (IV).
In the structures of (III) and (IV), the conformation of the pyrrolidine ring is markedly different, having an envelope conformation in (III) and a half-chair conformation in (IV). This difference in conformation may play an essential role in the orientation of the wings and body.