Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104006924/gg1213sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104006924/gg1213IIIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104006924/gg1213IIIbsup3.hkl |
CCDC references: 241229; 241230
Compounds (IIIa) and (IIIb) were obtained by the reaction of (1-naphthylmethylene)malononitrile, (I) (Nesterov et al., 2001a), with 1,3-diketones (IIa) and (IIb) according to a literature procedure (Nesterov & Viltchinskaia, 2001). The precipitates were isolated and recrystallized from acetonitrile [m.p. 501 K, yield 95% for (IIIa), and 484 K, 92% for (IIIb)]. Crystals were grown by slow isothermic evaporation of CH3CN solutions of (IIIa) and (IIIb). For (IIIa), 1H NMR (DMDO-d6, 300 MHz): δ 8.38 (d, 1H, J = 8.1 Hz), 7.91 (dd, 1H, J = 7.7, 1.5 Hz), 7.76 (d, 1H, J = 8.1 Hz), 7.56 (td, 1H, J = 6.6, 1.5), 7.51 (td, 1H, J = 6.6, 1.1 Hz), 7.43 (t, 1H, J = 7.5 Hz), 7.24 (dd, 1H, J = 7.4, 1.1 Hz), 6.95 (br s, 2H, NH2), 5.14 (s, 1H, H4), 2.68 (m, 2H, H6), 2.25 (m, 2H, H8), 1.95 (m, 2H, H7); 13C NMR (CDCl3, 75 MHz): δ 195.9 (C5), 164.8 (C8a), 158.4 (C2), 142.0, 133.3, 130.7, 128.3, 126.9, 125.8 (2 C), 125.6, 124.9, 123.6 (naphthalene), 119.7 (CN), 114.5 (C4a), 58.8 (C3), 36.3 (C6), 30.0 (C4), 26.5 (C8), 19.9 (C7). For (IIIb), 1H NMR (DMDO-d6, 300 MHz): δ 8.36 (d, 1H, J = 8.5 Hz), 7.91 (dd, 1H, J = 7.4, 1.8 Hz), 7.76 (d, 1H, J = 8.1 Hz), 7.56 (td, 1H, J = 7.0, 1.5 Hz), 7.51 (td, 1H, J = 6.6, 1.1 Hz), 7.44 (t, 1H, J = 7.7 Hz), 7.23 (d, 1H, J = 7.4 Hz), 6.96 (br s, 2H, NH2), 5.13 (s, 1H, H4), 2.58 (s, 2H, H6), 2.23 (d, 1H, H8a, J = 16.2 Hz), 2.06 (d, 1H, H8b, J = 15.8 Hz), 1.05 (s, 3H, CH3), 0.98 (s, 3H, CH3); 13C NMR (CDCl3, 75 MHz): δ 195.7 (C5), 162.7 (C8a), 158.4 (C2), 141.9, 133.3, 130.7, 128.3, 126.9, 125.8, 125.63, 125.56, 125.1, 123.6 (naphthalene), 119.6 (CN), 113.4 (C4a), 58.9 (C3), 50.0 (C6), 39.8 (C8), 31.8 (C7), 30.1 (C4), 28.4 (CH3), 27.0 (CH3).
For both compounds, data collection: CAD-4 Software (Enraf–Nonuis, 1989); cell refinement: CAD-4 Software; data reduction: SHELXTL (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.
C20H16N2O2 | F(000) = 664 |
Mr = 316.35 | Dx = 1.361 Mg m−3 |
Monoclinic, P21/n | Melting point: 501 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4410 (13) Å | Cell parameters from 24 reflections |
b = 9.6330 (19) Å | θ = 12–13° |
c = 24.911 (5) Å | µ = 0.09 mm−1 |
β = 92.98 (3)° | T = 295 K |
V = 1543.5 (5) Å3 | Prism, colorless |
Z = 4 | 0.50 × 0.40 × 0.30 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.061 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 1.6° |
Graphite monochromator | h = 0→8 |
θ/2θ scans | k = 0→12 |
3619 measured reflections | l = −31→31 |
3318 independent reflections | 3 standard reflections every 97 reflections |
2287 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.085P)2 + 0.45P] where P = (Fo2 + 2Fc2)/3 |
3318 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C20H16N2O2 | V = 1543.5 (5) Å3 |
Mr = 316.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.4410 (13) Å | µ = 0.09 mm−1 |
b = 9.6330 (19) Å | T = 295 K |
c = 24.911 (5) Å | 0.50 × 0.40 × 0.30 mm |
β = 92.98 (3)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.061 |
3619 measured reflections | 3 standard reflections every 97 reflections |
3318 independent reflections | intensity decay: 3% |
2287 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.33 e Å−3 |
3318 reflections | Δρmin = −0.24 e Å−3 |
217 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. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.93 Å for aromatic H atoms, 0.97 Å for CH2, 0.98 Å for CH, 0.86 Å for NH2 groups. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.7842 (2) | 0.05532 (13) | 0.04423 (6) | 0.0419 (4) | |
O2 | 0.1552 (2) | 0.13142 (16) | 0.12749 (7) | 0.0534 (4) | |
N1 | 0.9767 (3) | 0.20903 (18) | 0.00261 (7) | 0.0475 (5) | |
H1A | 1.0097 | 0.2902 | −0.0085 | 0.057* | |
H1B | 1.0491 | 0.1379 | −0.0057 | 0.057* | |
N2 | 0.7643 (3) | 0.54278 (19) | 0.02512 (9) | 0.0554 (5) | |
C1 | 0.7258 (3) | 0.4310 (2) | 0.03638 (8) | 0.0379 (4) | |
C2 | 0.8107 (3) | 0.19329 (18) | 0.03322 (7) | 0.0346 (4) | |
C3 | 0.6815 (3) | 0.29156 (18) | 0.04988 (7) | 0.0328 (4) | |
C4 | 0.5021 (3) | 0.26263 (18) | 0.08544 (7) | 0.0322 (4) | |
H4A | 0.3739 | 0.2996 | 0.0680 | 0.039* | |
C5 | 0.4804 (3) | 0.10746 (18) | 0.09143 (7) | 0.0321 (4) | |
C6 | 0.2958 (3) | 0.0534 (2) | 0.11718 (8) | 0.0381 (4) | |
C7 | 0.2842 (4) | −0.0995 (2) | 0.12787 (11) | 0.0589 (7) | |
H7A | 0.2228 | −0.1134 | 0.1622 | 0.071* | |
H7B | 0.1921 | −0.1414 | 0.1004 | 0.071* | |
C8 | 0.4867 (4) | −0.1729 (2) | 0.12888 (11) | 0.0592 (6) | |
H8A | 0.4617 | −0.2722 | 0.1286 | 0.071* | |
H8B | 0.5649 | −0.1504 | 0.1621 | 0.071* | |
C9 | 0.6153 (3) | −0.1363 (2) | 0.08213 (9) | 0.0462 (5) | |
H9A | 0.7565 | −0.1693 | 0.0890 | 0.055* | |
H9B | 0.5582 | −0.1816 | 0.0499 | 0.055* | |
C10 | 0.6174 (3) | 0.01656 (19) | 0.07370 (7) | 0.0339 (4) | |
C11 | 0.5372 (3) | 0.33147 (18) | 0.14068 (7) | 0.0329 (4) | |
C12 | 0.7123 (3) | 0.2976 (2) | 0.17090 (8) | 0.0404 (5) | |
H12A | 0.8041 | 0.2333 | 0.1575 | 0.048* | |
C13 | 0.7587 (4) | 0.3566 (2) | 0.22170 (9) | 0.0490 (5) | |
H13A | 0.8798 | 0.3321 | 0.2414 | 0.059* | |
C14 | 0.6246 (4) | 0.4501 (2) | 0.24190 (9) | 0.0512 (6) | |
H14A | 0.6550 | 0.4891 | 0.2755 | 0.061* | |
C15 | 0.4408 (4) | 0.4886 (2) | 0.21269 (8) | 0.0434 (5) | |
C16 | 0.3004 (4) | 0.5849 (2) | 0.23369 (10) | 0.0566 (7) | |
H16A | 0.3308 | 0.6240 | 0.2673 | 0.068* | |
C17 | 0.1224 (4) | 0.6213 (2) | 0.20577 (12) | 0.0636 (7) | |
H17A | 0.0310 | 0.6836 | 0.2205 | 0.076* | |
C18 | 0.0759 (4) | 0.5649 (2) | 0.15439 (12) | 0.0578 (6) | |
H18A | −0.0452 | 0.5914 | 0.1351 | 0.069* | |
C19 | 0.2071 (3) | 0.4716 (2) | 0.13260 (10) | 0.0467 (5) | |
H19A | 0.1737 | 0.4351 | 0.0987 | 0.056* | |
C20 | 0.3938 (3) | 0.42953 (19) | 0.16079 (8) | 0.0368 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0457 (8) | 0.0265 (7) | 0.0560 (9) | −0.0005 (5) | 0.0259 (7) | 0.0010 (6) |
O2 | 0.0412 (8) | 0.0495 (9) | 0.0716 (11) | 0.0032 (7) | 0.0236 (7) | 0.0045 (8) |
N1 | 0.0532 (11) | 0.0332 (9) | 0.0592 (11) | −0.0007 (7) | 0.0334 (9) | 0.0013 (8) |
N2 | 0.0594 (12) | 0.0343 (10) | 0.0748 (14) | −0.0017 (8) | 0.0245 (10) | 0.0114 (9) |
C1 | 0.0415 (11) | 0.0328 (10) | 0.0408 (10) | 0.0015 (8) | 0.0152 (8) | 0.0029 (8) |
C2 | 0.0415 (10) | 0.0265 (9) | 0.0368 (9) | −0.0035 (7) | 0.0126 (8) | 0.0005 (7) |
C3 | 0.0381 (10) | 0.0272 (8) | 0.0342 (9) | −0.0014 (7) | 0.0113 (7) | 0.0018 (7) |
C4 | 0.0346 (9) | 0.0269 (8) | 0.0360 (10) | −0.0007 (7) | 0.0103 (7) | 0.0007 (7) |
C5 | 0.0373 (10) | 0.0277 (9) | 0.0322 (9) | −0.0047 (7) | 0.0088 (7) | −0.0002 (7) |
C6 | 0.0391 (10) | 0.0359 (10) | 0.0402 (10) | −0.0052 (8) | 0.0101 (8) | −0.0005 (8) |
C7 | 0.0606 (14) | 0.0393 (12) | 0.0801 (17) | −0.0100 (10) | 0.0352 (13) | 0.0047 (11) |
C8 | 0.0702 (16) | 0.0380 (12) | 0.0718 (15) | −0.0008 (11) | 0.0265 (13) | 0.0150 (11) |
C9 | 0.0524 (12) | 0.0258 (10) | 0.0620 (13) | −0.0008 (8) | 0.0183 (10) | 0.0016 (9) |
C10 | 0.0378 (10) | 0.0281 (9) | 0.0368 (9) | −0.0044 (7) | 0.0120 (8) | −0.0002 (7) |
C11 | 0.0363 (9) | 0.0269 (8) | 0.0366 (9) | −0.0045 (7) | 0.0122 (7) | 0.0013 (7) |
C12 | 0.0423 (11) | 0.0381 (10) | 0.0416 (10) | −0.0002 (8) | 0.0093 (8) | 0.0012 (8) |
C13 | 0.0520 (13) | 0.0511 (13) | 0.0436 (11) | −0.0062 (10) | 0.0003 (10) | 0.0005 (10) |
C14 | 0.0721 (16) | 0.0454 (12) | 0.0364 (11) | −0.0138 (11) | 0.0077 (10) | −0.0053 (9) |
C15 | 0.0584 (13) | 0.0309 (10) | 0.0431 (11) | −0.0088 (9) | 0.0237 (10) | −0.0026 (8) |
C16 | 0.0789 (18) | 0.0387 (11) | 0.0556 (13) | −0.0070 (11) | 0.0364 (13) | −0.0114 (10) |
C17 | 0.0679 (17) | 0.0369 (12) | 0.0906 (19) | 0.0019 (11) | 0.0472 (15) | −0.0092 (12) |
C18 | 0.0471 (13) | 0.0404 (12) | 0.0880 (18) | 0.0056 (10) | 0.0225 (12) | −0.0013 (12) |
C19 | 0.0445 (12) | 0.0370 (10) | 0.0597 (13) | 0.0023 (9) | 0.0135 (10) | −0.0046 (10) |
C20 | 0.0423 (10) | 0.0274 (9) | 0.0422 (10) | −0.0048 (8) | 0.0171 (8) | −0.0013 (7) |
O1—C2 | 1.370 (2) | C9—C10 | 1.487 (3) |
O1—C10 | 1.384 (2) | C9—H9A | 0.9700 |
O2—C6 | 1.215 (2) | C9—H9B | 0.9700 |
N1—C2 | 1.353 (2) | C11—C12 | 1.363 (3) |
N1—H1A | 0.8600 | C11—C20 | 1.430 (3) |
N1—H1B | 0.8600 | C12—C13 | 1.406 (3) |
N2—C1 | 1.143 (3) | C12—H12A | 0.9300 |
C1—C3 | 1.417 (2) | C13—C14 | 1.362 (3) |
C2—C3 | 1.341 (3) | C13—H13A | 0.9300 |
C3—C4 | 1.518 (2) | C14—C15 | 1.407 (3) |
C4—C5 | 1.509 (2) | C14—H14A | 0.9300 |
C4—C11 | 1.534 (3) | C15—C16 | 1.415 (3) |
C4—H4A | 0.9800 | C15—C20 | 1.430 (3) |
C5—C10 | 1.335 (3) | C16—C17 | 1.356 (4) |
C5—C6 | 1.475 (2) | C16—H16A | 0.9300 |
C6—C7 | 1.500 (3) | C17—C18 | 1.408 (4) |
C7—C8 | 1.483 (3) | C17—H17A | 0.9300 |
C7—H7A | 0.9700 | C18—C19 | 1.365 (3) |
C7—H7B | 0.9700 | C18—H18A | 0.9300 |
C8—C9 | 1.506 (3) | C19—C20 | 1.420 (3) |
C8—H8A | 0.9700 | C19—H19A | 0.9300 |
C8—H8B | 0.9700 | ||
C2—O1—C10 | 118.46 (14) | C8—C9—H9A | 109.5 |
C2—N1—H1A | 120.0 | C10—C9—H9B | 109.5 |
C2—N1—H1B | 120.0 | C8—C9—H9B | 109.5 |
H1A—N1—H1B | 120.0 | H9A—C9—H9B | 108.1 |
N2—C1—C3 | 178.9 (2) | C5—C10—O1 | 122.93 (16) |
C3—C2—N1 | 128.06 (17) | C5—C10—C9 | 126.28 (17) |
C3—C2—O1 | 122.50 (17) | O1—C10—C9 | 110.79 (16) |
N1—C2—O1 | 109.40 (16) | C12—C11—C20 | 119.74 (17) |
C2—C3—C1 | 117.36 (17) | C12—C11—C4 | 118.12 (16) |
C2—C3—C4 | 123.70 (16) | C20—C11—C4 | 122.14 (17) |
C1—C3—C4 | 118.78 (15) | C11—C12—C13 | 122.09 (19) |
C5—C4—C3 | 108.47 (15) | C11—C12—H12A | 119.0 |
C5—C4—C11 | 110.46 (15) | C13—C12—H12A | 119.0 |
C3—C4—C11 | 111.28 (15) | C14—C13—C12 | 119.4 (2) |
C5—C4—H4A | 108.9 | C14—C13—H13A | 120.3 |
C3—C4—H4A | 108.9 | C12—C13—H13A | 120.3 |
C11—C4—H4A | 108.9 | C13—C14—C15 | 121.1 (2) |
C10—C5—C6 | 118.32 (16) | C13—C14—H14A | 119.5 |
C10—C5—C4 | 123.42 (16) | C15—C14—H14A | 119.5 |
C6—C5—C4 | 118.25 (16) | C14—C15—C16 | 121.2 (2) |
O2—C6—C5 | 120.05 (18) | C14—C15—C20 | 119.71 (19) |
O2—C6—C7 | 121.70 (18) | C16—C15—C20 | 119.1 (2) |
C5—C6—C7 | 118.20 (17) | C17—C16—C15 | 121.3 (2) |
C8—C7—C6 | 114.82 (19) | C17—C16—H16A | 119.4 |
C8—C7—H7A | 108.6 | C15—C16—H16A | 119.4 |
C6—C7—H7A | 108.6 | C16—C17—C18 | 120.0 (2) |
C8—C7—H7B | 108.6 | C16—C17—H17A | 120.0 |
C6—C7—H7B | 108.6 | C18—C17—H17A | 120.0 |
H7A—C7—H7B | 107.5 | C19—C18—C17 | 120.6 (2) |
C7—C8—C9 | 113.2 (2) | C19—C18—H18A | 119.7 |
C7—C8—H8A | 108.9 | C17—C18—H18A | 119.7 |
C9—C8—H8A | 108.9 | C18—C19—C20 | 121.1 (2) |
C7—C8—H8B | 108.9 | C18—C19—H19A | 119.4 |
C9—C8—H8B | 108.9 | C20—C19—H19A | 119.4 |
H8A—C8—H8B | 107.8 | C19—C20—C11 | 124.15 (18) |
C10—C9—C8 | 110.53 (17) | C19—C20—C15 | 117.87 (18) |
C10—C9—H9A | 109.5 | C11—C20—C15 | 117.97 (18) |
C10—O1—C2—C3 | 0.0 (3) | C8—C9—C10—C5 | −20.0 (3) |
C10—O1—C2—N1 | −177.82 (16) | C8—C9—C10—O1 | 159.99 (19) |
N1—C2—C3—C1 | −3.1 (3) | C5—C4—C11—C12 | 62.7 (2) |
O1—C2—C3—C1 | 179.51 (18) | C3—C4—C11—C12 | −57.8 (2) |
N1—C2—C3—C4 | −178.48 (18) | C5—C4—C11—C20 | −117.69 (18) |
O1—C2—C3—C4 | 4.2 (3) | C3—C4—C11—C20 | 121.78 (18) |
C2—C3—C4—C5 | −7.6 (3) | C20—C11—C12—C13 | −0.4 (3) |
C1—C3—C4—C5 | 177.11 (17) | C4—C11—C12—C13 | 179.24 (18) |
C2—C3—C4—C11 | 114.1 (2) | C11—C12—C13—C14 | 0.5 (3) |
C1—C3—C4—C11 | −61.2 (2) | C12—C13—C14—C15 | −0.1 (3) |
C3—C4—C5—C10 | 8.1 (3) | C13—C14—C15—C16 | 179.6 (2) |
C11—C4—C5—C10 | −114.1 (2) | C13—C14—C15—C20 | −0.4 (3) |
C3—C4—C5—C6 | −170.49 (16) | C14—C15—C16—C17 | −179.5 (2) |
C11—C4—C5—C6 | 67.3 (2) | C20—C15—C16—C17 | 0.4 (3) |
C10—C5—C6—O2 | −170.5 (2) | C15—C16—C17—C18 | −1.1 (3) |
C4—C5—C6—O2 | 8.2 (3) | C16—C17—C18—C19 | 1.1 (4) |
C10—C5—C6—C7 | 7.0 (3) | C17—C18—C19—C20 | −0.3 (3) |
C4—C5—C6—C7 | −174.3 (2) | C18—C19—C20—C11 | 179.4 (2) |
O2—C6—C7—C8 | −162.4 (2) | C18—C19—C20—C15 | −0.4 (3) |
C5—C6—C7—C8 | 20.1 (3) | C12—C11—C20—C19 | −179.89 (18) |
C6—C7—C8—C9 | −47.1 (3) | C4—C11—C20—C19 | 0.5 (3) |
C7—C8—C9—C10 | 46.0 (3) | C12—C11—C20—C15 | −0.1 (3) |
C6—C5—C10—O1 | 173.28 (17) | C4—C11—C20—C15 | −179.70 (16) |
C4—C5—C10—O1 | −5.3 (3) | C14—C15—C20—C19 | −179.75 (18) |
C6—C5—C10—C9 | −6.7 (3) | C16—C15—C20—C19 | 0.3 (3) |
C4—C5—C10—C9 | 174.6 (2) | C14—C15—C20—C11 | 0.5 (3) |
C2—O1—C10—C5 | 0.6 (3) | C16—C15—C20—C11 | −179.45 (18) |
C2—O1—C10—C9 | −179.37 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.22 | 3.016 (3) | 153 |
N1—H1B···O1ii | 0.86 | 2.38 | 3.226 (3) | 170 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y, −z. |
C22H20N2O2 | F(000) = 728 |
Mr = 344.40 | Dx = 1.288 Mg m−3 |
Monoclinic, P21/n | Melting point: 484 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.456 (3) Å | Cell parameters from 24 reflections |
b = 14.854 (7) Å | θ = 13–14° |
c = 16.133 (9) Å | µ = 0.08 mm−1 |
β = 96.16 (2)° | T = 298 K |
V = 1776.4 (15) Å3 | Prism, colorless |
Z = 4 | 0.55 × 0.45 × 0.30 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.015 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 2.5° |
Graphite monochromator | h = 0→9 |
θ/2θ scans | k = 0→19 |
4563 measured reflections | l = −21→21 |
4255 independent reflections | 3 standard reflections every 97 reflections |
3299 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.4P] where P = (Fo2 + 2Fc2)/3 |
4255 reflections | (Δ/σ)max < 0.001 |
237 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C22H20N2O2 | V = 1776.4 (15) Å3 |
Mr = 344.40 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.456 (3) Å | µ = 0.08 mm−1 |
b = 14.854 (7) Å | T = 298 K |
c = 16.133 (9) Å | 0.55 × 0.45 × 0.30 mm |
β = 96.16 (2)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.015 |
4563 measured reflections | 3 standard reflections every 97 reflections |
4255 independent reflections | intensity decay: 3% |
3299 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.24 e Å−3 |
4255 reflections | Δρmin = −0.18 e Å−3 |
237 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. All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.93 Å for aromatic H atoms, 0.97 Å for CH2, 0.98 Å for CH, 0.86 Å for NH2and 0.96 Å for CH3 groups. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.03730 (14) | 0.17320 (8) | 0.35918 (7) | 0.0501 (3) | |
O2 | 0.39171 (15) | 0.39902 (9) | 0.25107 (8) | 0.0581 (3) | |
N1 | 0.1342 (2) | 0.04963 (9) | 0.42773 (9) | 0.0590 (4) | |
H1A | 0.2134 | 0.0148 | 0.4538 | 0.071* | |
H1B | 0.0227 | 0.0337 | 0.4210 | 0.071* | |
N2 | 0.6250 (2) | 0.06985 (10) | 0.45543 (12) | 0.0704 (5) | |
C1 | 0.5008 (2) | 0.11197 (10) | 0.43221 (10) | 0.0481 (4) | |
C2 | 0.1847 (2) | 0.12901 (10) | 0.39753 (9) | 0.0438 (3) | |
C3 | 0.35144 (19) | 0.16558 (9) | 0.40175 (8) | 0.0403 (3) | |
C4 | 0.38082 (17) | 0.26304 (9) | 0.37565 (8) | 0.0357 (3) | |
H4A | 0.4927 | 0.2654 | 0.3489 | 0.043* | |
C5 | 0.22615 (17) | 0.28676 (9) | 0.31091 (8) | 0.0354 (3) | |
C6 | 0.25066 (18) | 0.35663 (10) | 0.24856 (9) | 0.0391 (3) | |
C7 | 0.09945 (19) | 0.36981 (11) | 0.17965 (9) | 0.0452 (3) | |
H7A | 0.1157 | 0.3279 | 0.1349 | 0.054* | |
H7B | 0.1072 | 0.4302 | 0.1576 | 0.054* | |
C8 | −0.08908 (18) | 0.35615 (10) | 0.20703 (8) | 0.0400 (3) | |
C9 | −0.09483 (19) | 0.26327 (10) | 0.24800 (9) | 0.0426 (3) | |
H9A | −0.2010 | 0.2596 | 0.2777 | 0.051* | |
H9B | −0.1058 | 0.2175 | 0.2049 | 0.051* | |
C10 | 0.06802 (18) | 0.24414 (9) | 0.30709 (8) | 0.0379 (3) | |
C11 | 0.40036 (17) | 0.32780 (9) | 0.45053 (8) | 0.0349 (3) | |
C12 | 0.25813 (19) | 0.37887 (10) | 0.46955 (9) | 0.0419 (3) | |
H12A | 0.1501 | 0.3760 | 0.4350 | 0.050* | |
C13 | 0.2698 (2) | 0.43596 (11) | 0.53992 (10) | 0.0499 (4) | |
H13A | 0.1713 | 0.4711 | 0.5501 | 0.060* | |
C14 | 0.4236 (2) | 0.43977 (11) | 0.59268 (10) | 0.0495 (4) | |
H14A | 0.4296 | 0.4767 | 0.6395 | 0.059* | |
C15 | 0.5748 (2) | 0.38784 (10) | 0.57677 (9) | 0.0426 (3) | |
C16 | 0.7364 (2) | 0.39001 (12) | 0.63227 (11) | 0.0574 (4) | |
H16A | 0.7415 | 0.4251 | 0.6802 | 0.069* | |
C17 | 0.8832 (2) | 0.34170 (14) | 0.61626 (12) | 0.0640 (5) | |
H17A | 0.9872 | 0.3430 | 0.6536 | 0.077* | |
C18 | 0.8786 (2) | 0.28992 (13) | 0.54372 (11) | 0.0573 (4) | |
H18A | 0.9806 | 0.2579 | 0.5327 | 0.069* | |
C19 | 0.72578 (19) | 0.28585 (10) | 0.48869 (10) | 0.0440 (3) | |
H19A | 0.7260 | 0.2516 | 0.4404 | 0.053* | |
C20 | 0.56721 (18) | 0.33288 (9) | 0.50394 (8) | 0.0373 (3) | |
C21 | −0.1316 (2) | 0.43017 (13) | 0.26767 (11) | 0.0584 (4) | |
H21A | −0.0433 | 0.4292 | 0.3156 | 0.088* | |
H21B | −0.2493 | 0.4202 | 0.2849 | 0.088* | |
H21C | −0.1289 | 0.4877 | 0.2406 | 0.088* | |
C22 | −0.2308 (2) | 0.35838 (13) | 0.13085 (10) | 0.0553 (4) | |
H22A | −0.2284 | 0.4161 | 0.1043 | 0.083* | |
H22B | −0.3482 | 0.3482 | 0.1483 | 0.083* | |
H22C | −0.2045 | 0.3122 | 0.0923 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0442 (6) | 0.0522 (6) | 0.0526 (6) | −0.0066 (5) | −0.0003 (5) | 0.0160 (5) |
O2 | 0.0428 (6) | 0.0695 (8) | 0.0608 (7) | −0.0112 (5) | 0.0008 (5) | 0.0188 (6) |
N1 | 0.0652 (9) | 0.0463 (8) | 0.0617 (9) | −0.0126 (6) | −0.0108 (7) | 0.0136 (6) |
N2 | 0.0684 (10) | 0.0438 (8) | 0.0931 (12) | 0.0088 (7) | −0.0183 (8) | 0.0074 (8) |
C1 | 0.0565 (9) | 0.0346 (7) | 0.0507 (8) | 0.0019 (6) | −0.0065 (7) | −0.0004 (6) |
C2 | 0.0536 (8) | 0.0401 (7) | 0.0361 (7) | −0.0013 (6) | −0.0024 (6) | 0.0018 (6) |
C3 | 0.0469 (8) | 0.0361 (7) | 0.0364 (7) | 0.0032 (6) | −0.0021 (6) | −0.0011 (5) |
C4 | 0.0331 (6) | 0.0387 (7) | 0.0351 (6) | 0.0018 (5) | 0.0021 (5) | 0.0021 (5) |
C5 | 0.0351 (6) | 0.0390 (7) | 0.0318 (6) | 0.0028 (5) | 0.0027 (5) | 0.0002 (5) |
C6 | 0.0346 (7) | 0.0458 (7) | 0.0374 (7) | 0.0023 (6) | 0.0060 (5) | 0.0032 (6) |
C7 | 0.0415 (7) | 0.0567 (9) | 0.0372 (7) | 0.0009 (6) | 0.0028 (6) | 0.0107 (6) |
C8 | 0.0352 (7) | 0.0478 (8) | 0.0360 (7) | 0.0030 (6) | −0.0006 (5) | 0.0002 (6) |
C9 | 0.0375 (7) | 0.0510 (8) | 0.0385 (7) | −0.0045 (6) | 0.0003 (5) | −0.0004 (6) |
C10 | 0.0400 (7) | 0.0410 (7) | 0.0326 (6) | −0.0010 (5) | 0.0037 (5) | 0.0016 (5) |
C11 | 0.0354 (6) | 0.0336 (6) | 0.0352 (6) | −0.0041 (5) | 0.0022 (5) | 0.0040 (5) |
C12 | 0.0401 (7) | 0.0443 (8) | 0.0405 (7) | 0.0009 (6) | 0.0008 (6) | −0.0010 (6) |
C13 | 0.0530 (9) | 0.0458 (8) | 0.0517 (9) | 0.0058 (7) | 0.0096 (7) | −0.0059 (7) |
C14 | 0.0617 (10) | 0.0435 (8) | 0.0434 (8) | −0.0052 (7) | 0.0067 (7) | −0.0088 (6) |
C15 | 0.0480 (8) | 0.0387 (7) | 0.0398 (7) | −0.0110 (6) | −0.0005 (6) | 0.0026 (6) |
C16 | 0.0600 (10) | 0.0607 (10) | 0.0479 (9) | −0.0171 (8) | −0.0104 (7) | −0.0007 (8) |
C17 | 0.0472 (9) | 0.0772 (13) | 0.0630 (11) | −0.0131 (9) | −0.0148 (8) | 0.0093 (9) |
C18 | 0.0373 (8) | 0.0668 (11) | 0.0659 (11) | −0.0014 (7) | −0.0031 (7) | 0.0115 (9) |
C19 | 0.0385 (7) | 0.0459 (8) | 0.0472 (8) | −0.0027 (6) | 0.0029 (6) | 0.0060 (6) |
C20 | 0.0365 (7) | 0.0358 (7) | 0.0388 (7) | −0.0063 (5) | 0.0009 (5) | 0.0060 (5) |
C21 | 0.0500 (9) | 0.0607 (10) | 0.0629 (10) | 0.0128 (8) | −0.0013 (7) | −0.0149 (8) |
C22 | 0.0459 (8) | 0.0722 (11) | 0.0450 (8) | −0.0004 (8) | −0.0082 (6) | 0.0075 (8) |
O1—C2 | 1.3695 (18) | C11—C12 | 1.365 (2) |
O1—C10 | 1.3821 (17) | C11—C20 | 1.4373 (18) |
O2—C6 | 1.2228 (18) | C12—C13 | 1.412 (2) |
N1—C2 | 1.345 (2) | C12—H12A | 0.9300 |
N1—H1A | 0.8600 | C13—C14 | 1.354 (2) |
N1—H1B | 0.8600 | C13—H13A | 0.9300 |
N2—C1 | 1.147 (2) | C14—C15 | 1.412 (2) |
C1—C3 | 1.414 (2) | C14—H14A | 0.9300 |
C2—C3 | 1.352 (2) | C15—C16 | 1.423 (2) |
C3—C4 | 1.530 (2) | C15—C20 | 1.427 (2) |
C4—C5 | 1.5122 (18) | C16—C17 | 1.357 (3) |
C4—C11 | 1.5388 (19) | C16—H16A | 0.9300 |
C4—H4A | 0.9800 | C17—C18 | 1.398 (3) |
C5—C10 | 1.3338 (19) | C17—H17A | 0.9300 |
C5—C6 | 1.470 (2) | C18—C19 | 1.369 (2) |
C6—C7 | 1.5087 (19) | C18—H18A | 0.9300 |
C7—C8 | 1.532 (2) | C19—C20 | 1.417 (2) |
C7—H7A | 0.9700 | C19—H19A | 0.9300 |
C7—H7B | 0.9700 | C21—H21A | 0.9600 |
C8—C21 | 1.527 (2) | C21—H21B | 0.9600 |
C8—C9 | 1.532 (2) | C21—H21C | 0.9600 |
C8—C22 | 1.533 (2) | C22—H22A | 0.9600 |
C9—C10 | 1.4884 (19) | C22—H22B | 0.9600 |
C9—H9A | 0.9700 | C22—H22C | 0.9600 |
C9—H9B | 0.9700 | ||
C2—O1—C10 | 117.57 (11) | O1—C10—C9 | 110.97 (12) |
C2—N1—H1A | 120.0 | C12—C11—C20 | 118.64 (13) |
C2—N1—H1B | 120.0 | C12—C11—C4 | 120.89 (12) |
H1A—N1—H1B | 120.0 | C20—C11—C4 | 120.42 (12) |
N2—C1—C3 | 178.0 (2) | C11—C12—C13 | 122.15 (14) |
N1—C2—C3 | 128.74 (14) | C11—C12—H12A | 118.9 |
N1—C2—O1 | 109.98 (13) | C13—C12—H12A | 118.9 |
C3—C2—O1 | 121.28 (13) | C14—C13—C12 | 120.35 (14) |
C2—C3—C1 | 118.51 (14) | C14—C13—H13A | 119.8 |
C2—C3—C4 | 121.63 (12) | C12—C13—H13A | 119.8 |
C1—C3—C4 | 119.86 (13) | C13—C14—C15 | 120.11 (14) |
C5—C4—C3 | 106.82 (11) | C13—C14—H14A | 119.9 |
C5—C4—C11 | 113.42 (11) | C15—C14—H14A | 119.9 |
C3—C4—C11 | 112.32 (11) | C14—C15—C16 | 120.80 (15) |
C5—C4—H4A | 108.0 | C14—C15—C20 | 120.04 (13) |
C3—C4—H4A | 108.0 | C16—C15—C20 | 119.16 (15) |
C11—C4—H4A | 108.0 | C17—C16—C15 | 120.96 (16) |
C10—C5—C6 | 118.53 (12) | C17—C16—H16A | 119.5 |
C10—C5—C4 | 121.75 (12) | C15—C16—H16A | 119.5 |
C6—C5—C4 | 119.70 (12) | C16—C17—C18 | 120.19 (15) |
O2—C6—C5 | 120.70 (13) | C16—C17—H17A | 119.9 |
O2—C6—C7 | 121.98 (13) | C18—C17—H17A | 119.9 |
C5—C6—C7 | 117.25 (12) | C19—C18—C17 | 120.75 (17) |
C6—C7—C8 | 114.00 (12) | C19—C18—H18A | 119.6 |
C6—C7—H7A | 108.8 | C17—C18—H18A | 119.6 |
C8—C7—H7A | 108.8 | C18—C19—C20 | 121.17 (15) |
C6—C7—H7B | 108.8 | C18—C19—H19A | 119.4 |
C8—C7—H7B | 108.8 | C20—C19—H19A | 119.4 |
H7A—C7—H7B | 107.6 | C19—C20—C15 | 117.71 (13) |
C21—C8—C7 | 110.45 (13) | C19—C20—C11 | 123.68 (13) |
C21—C8—C9 | 110.77 (13) | C15—C20—C11 | 118.61 (13) |
C7—C8—C9 | 108.22 (12) | C8—C21—H21A | 109.5 |
C21—C8—C22 | 108.99 (13) | C8—C21—H21B | 109.5 |
C7—C8—C22 | 109.94 (13) | H21A—C21—H21B | 109.5 |
C9—C8—C22 | 108.45 (13) | C8—C21—H21C | 109.5 |
C10—C9—C8 | 112.92 (12) | H21A—C21—H21C | 109.5 |
C10—C9—H9A | 109.0 | H21B—C21—H21C | 109.5 |
C8—C9—H9A | 109.0 | C8—C22—H22A | 109.5 |
C10—C9—H9B | 109.0 | C8—C22—H22B | 109.5 |
C8—C9—H9B | 109.0 | H22A—C22—H22B | 109.5 |
H9A—C9—H9B | 107.8 | C8—C22—H22C | 109.5 |
C5—C10—O1 | 122.49 (12) | H22A—C22—H22C | 109.5 |
C5—C10—C9 | 126.53 (13) | H22B—C22—H22C | 109.5 |
C10—O1—C2—N1 | −164.20 (13) | C2—O1—C10—C5 | −19.6 (2) |
C10—O1—C2—C3 | 16.2 (2) | C2—O1—C10—C9 | 159.47 (12) |
N1—C2—C3—C1 | 8.7 (2) | C8—C9—C10—C5 | −17.8 (2) |
O1—C2—C3—C1 | −171.78 (13) | C8—C9—C10—O1 | 163.21 (12) |
N1—C2—C3—C4 | −170.47 (15) | C5—C4—C11—C12 | 21.74 (18) |
O1—C2—C3—C4 | 9.1 (2) | C3—C4—C11—C12 | −99.52 (15) |
C2—C3—C4—C5 | −27.62 (17) | C5—C4—C11—C20 | −160.86 (11) |
C1—C3—C4—C5 | 153.24 (13) | C3—C4—C11—C20 | 77.89 (15) |
C2—C3—C4—C11 | 97.34 (15) | C20—C11—C12—C13 | −0.2 (2) |
C1—C3—C4—C11 | −81.80 (16) | C4—C11—C12—C13 | 177.21 (13) |
C3—C4—C5—C10 | 24.51 (17) | C11—C12—C13—C14 | −1.9 (2) |
C11—C4—C5—C10 | −99.78 (15) | C12—C13—C14—C15 | 1.2 (2) |
C3—C4—C5—C6 | −153.60 (12) | C13—C14—C15—C16 | −179.01 (15) |
C11—C4—C5—C6 | 82.11 (15) | C13—C14—C15—C20 | 1.5 (2) |
C10—C5—C6—O2 | 178.06 (14) | C14—C15—C16—C17 | −178.57 (16) |
C4—C5—C6—O2 | −3.8 (2) | C20—C15—C16—C17 | 0.9 (2) |
C10—C5—C6—C7 | −5.12 (19) | C15—C16—C17—C18 | 1.1 (3) |
C4—C5—C6—C7 | 173.06 (12) | C16—C17—C18—C19 | −1.1 (3) |
O2—C6—C7—C8 | −147.84 (15) | C17—C18—C19—C20 | −0.8 (3) |
C5—C6—C7—C8 | 35.37 (19) | C18—C19—C20—C15 | 2.7 (2) |
C6—C7—C8—C21 | 67.28 (17) | C18—C19—C20—C11 | −176.96 (14) |
C6—C7—C8—C9 | −54.13 (17) | C14—C15—C20—C19 | 176.73 (13) |
C6—C7—C8—C22 | −172.41 (13) | C16—C15—C20—C19 | −2.7 (2) |
C21—C8—C9—C10 | −76.59 (15) | C14—C15—C20—C11 | −3.6 (2) |
C7—C8—C9—C10 | 44.62 (16) | C16—C15—C20—C11 | 176.97 (13) |
C22—C8—C9—C10 | 163.85 (12) | C12—C11—C20—C19 | −177.41 (13) |
C6—C5—C10—O1 | 175.18 (12) | C4—C11—C20—C19 | 5.12 (19) |
C4—C5—C10—O1 | −3.0 (2) | C12—C11—C20—C15 | 2.90 (19) |
C6—C5—C10—C9 | −3.7 (2) | C4—C11—C20—C15 | −174.57 (12) |
C4—C5—C10—C9 | 178.13 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.19 | 3.033 (2) | 166 |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
(IIIa) | (IIIb) | |
Crystal data | ||
Chemical formula | C20H16N2O2 | C22H20N2O2 |
Mr | 316.35 | 344.40 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 295 | 298 |
a, b, c (Å) | 6.4410 (13), 9.6330 (19), 24.911 (5) | 7.456 (3), 14.854 (7), 16.133 (9) |
β (°) | 92.98 (3) | 96.16 (2) |
V (Å3) | 1543.5 (5) | 1776.4 (15) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.08 |
Crystal size (mm) | 0.50 × 0.40 × 0.30 | 0.55 × 0.45 × 0.30 |
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 | 3619, 3318, 2287 | 4563, 4255, 3299 |
Rint | 0.061 | 0.015 |
(sin θ/λ)max (Å−1) | 0.639 | 0.661 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.157, 1.05 | 0.048, 0.132, 1.08 |
No. of reflections | 3318 | 4255 |
No. of parameters | 217 | 237 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.24 | 0.24, −0.18 |
Computer programs: CAD-4 Software (Enraf–Nonuis, 1989), CAD-4 Software, SHELXTL (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL, SHELXL97.
O1—C2 | 1.370 (2) | N2—C1 | 1.143 (3) |
O1—C10 | 1.384 (2) | C1—C3 | 1.417 (2) |
O2—C6 | 1.215 (2) | C2—C3 | 1.341 (3) |
N1—C2 | 1.353 (2) | ||
C2—O1—C10 | 118.46 (14) | C2—C3—C4 | 123.70 (16) |
N2—C1—C3 | 178.9 (2) | C1—C3—C4 | 118.78 (15) |
C3—C2—N1 | 128.06 (17) | O2—C6—C5 | 120.05 (18) |
C3—C2—O1 | 122.50 (17) | O2—C6—C7 | 121.70 (18) |
N1—C2—O1 | 109.40 (16) | C5—C6—C7 | 118.20 (17) |
C2—C3—C1 | 117.36 (17) | ||
C2—C3—C4—C5 | −7.6 (3) | C3—C4—C5—C10 | 8.1 (3) |
C2—C3—C4—C11 | 114.1 (2) | C3—C4—C11—C12 | −57.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.22 | 3.016 (3) | 153 |
N1—H1B···O1ii | 0.86 | 2.38 | 3.226 (3) | 170 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+2, −y, −z. |
O1—C2 | 1.3695 (18) | N2—C1 | 1.147 (2) |
O1—C10 | 1.3821 (17) | C1—C3 | 1.414 (2) |
O2—C6 | 1.2228 (18) | C2—C3 | 1.352 (2) |
N1—C2 | 1.345 (2) | ||
C2—O1—C10 | 117.57 (11) | C1—C3—C4 | 119.86 (13) |
N2—C1—C3 | 178.0 (2) | O2—C6—C5 | 120.70 (13) |
N1—C2—C3 | 128.74 (14) | O2—C6—C7 | 121.98 (13) |
N1—C2—O1 | 109.98 (13) | C5—C6—C7 | 117.25 (12) |
C3—C2—O1 | 121.28 (13) | C5—C10—O1 | 122.49 (12) |
C2—C3—C1 | 118.51 (14) | C5—C10—C9 | 126.53 (13) |
C2—C3—C4 | 121.63 (12) | O1—C10—C9 | 110.97 (12) |
C2—C3—C4—C5 | −27.62 (17) | C3—C4—C5—C10 | 24.51 (17) |
C2—C3—C4—C11 | 97.34 (15) | C3—C4—C11—C12 | −99.52 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.19 | 3.033 (2) | 166 |
Symmetry code: (i) −x+1, −y, −z+1. |
The present investigation is a continuation of our work that includes syntheses and structural studies of unsaturated nitriles as potential non-linear optical materials (Nesterov et al., 2001a,b) and heterocyclic compounds that can be obtained using such nitriles (Nesterov & Viltchinskaia, 2001). Some 4H-pyran derivatives are potential bioactive compounds, for instance, as calcium antagonists (Suarez et al., 2002). Such heterocyclic compounds have structures similar to the well known 1,4-dihydropyridines (Triggle et al., 1980; Bossert et al., 1981; Kokubun & Reuter, 1984; Bossert et al., 1989; Wang et al., 1989), which exhibit high bioactivities. Thus, there has been a growing interest in the structures of 4H-pyran derivatives (Bellanato et al., 1987; Florencio & Garcia-Blanco, 1987; Bellanato et al., 1988; Lokaj et al., 1990; Marco et al., 1993).
Syntheses and X-ray structural investigations have been carried out for the title compounds, (IIIa) and (IIIb) (Figs. 1 and 2), which were synthezized from (1-naphthylmethylene)malononitrile, (I) (Nesterov et al., 2001a). Most of the geometric parameters in the two molecules are very similar to the standard values (Allen et al., 1987) and very close to our and literature data for similar 4H-pyran derivatives (Sharanina et al., 1986; Klokol et al., 1987; Martin-Leon et al., 1990; Shestopalov et al., 1991; Samet et al., 1996; Kislyi et al., 1999; Nesterov & Viltchinskaia, 2001; Shestopalov et al., 2002; Suarez et al., 2002; Shestopalov et al., 2003).
X-ray analysis shows that the molecules of (IIIa) and (IIIb) have slightly different molecular structures. The pyran ring in (IIIa) adopts a `sofa' conformation; atom C4 lies 0.100 (1) Å out of the O1/C2/C3/C5/C10 plane [planar within 0.003 (1) Å] and the dihedral angle between this plane and the C3/C4/C5 plane is 6.5 (2)°. However, (IIIb) has a flattened boat conformation, with atoms O1 and C4 deviating from the C2/C3/C5/C10 plane [planar within 0.015 (2) Å] by 0.186 (2) and 0.340 (2) Å, respectively, and the heterocycle bending along the O1···C4, C2···C10 and C3···C5 lines by 24.5 (2), 15.1 (2) and 22.0 (2)°, respectively. Our previous work and literature data show that the pyran ring is flexible but usually adopts a flattened boat conformation.
In both molecules, the fused cyclohexanone ring adopts a sofa conformation; in (IIIa) and (IIIb), atom C8 lies 0.572 (1) and 0.620 (2) Å, resepctively, out of the C7/C6/C5/C10/C9 plane (planar within 0.005 (1) and 0.040 (1) Å, respectively). The dihedral angles between these two flat fragments are 3.5 (2) and 17.5 (2)°, respectively. In both molecules, the bulky naphthalene substituents occupy pseudo-axial positions, forming dihedral angles with the flat moieties of the pyran rings of 90.9 (1) and 96.7 (1)°, respectively. Such mutual orientation of these fragments and the flatness of the heterocyclic rings leads to intramolecular H4A···H19A steric interactions [2.01 Å in (IIIa) and 2.17 Å in (IIIb)]. These contacts are shorter than the sum of the van der Waals radii of two H atoms (Rowland & Taylor, 1996), especially in the case of (IIIa). In addition, (IIIb) contains a short intramolecular contact [C1···C19 = 3.160 (2) Å] that is shorter than the sum of the van der Waals radii (Rowland & Taylor, 1996). Such steric hindrances cause elongation of the C4—C11 bond lengths to 1.534 (3) and 1.539 (2) Å in (IIIa) an (IIIb), respectively, whereas the neighbouring Csp3—Csp2 distances are only slightly longer than the standard value (Allen et al., 1987).
As we described previously for related compounds (Sharanina et al., 1986; Klokol et al., 1987; Shestopalov et al., 1991; Samet et al., 1996; Kislyi et al., 1999; Nesterov & Viltchinskaia, 2001; Shestopalov et al., 2002; Shestopalov et al., 2003), there is conjugation between NH2 donor and CN acceptor groups via the C2=C3 double bond. Thus, in both molecules, the C2—N1 distances are shorter than the average conjugated C—N single bond (1.370 Å) found in the Cambridge Structural Database (Allen, 2002). However, variations of other bond lengths in these flat fragments are less distinct.
In the crystal structure of (IIIa), intermolecular N—H···N and N—H···O hydrogen bonds link molecules into infinite tapes along the b axis (Fig. 3), while molecules of (IIIb) form only centrosymmetric dimers via N—H···N hydrogen bonds (Fig. 4), involving only one of the NH donor atoms. These dimers are further linked by weak C—H···O contacts along the a axis.
Analysis of the crystal packing showed that there is only one intermolecular steric contact in (IIIa). This contact, C13···C18(1 − x, y, z), is shorter than the sum of the van der Waals radii (Rowland & Taylor, 1996). The other geometric parameters in the investigated molecules have standard values (Allen et al., 1987).