Syntheses and X-ray structural investigations have been carried out for the three title compounds, C
19H
16N
2O
2, (III
a), C
19H
16N
2O
3, (III
b), and C
22H
22N
2O
3, (III
c), respectively. In molecules (III
a) and (III
c), the heterocyclic ring is practically flat, while in (III
b) it adopts a flattened-boat conformation. In (III
b) and (III
c), the carbonyl group and a double bond of the heterocyclic ring are
anti, but in (III
a) they are
syn and the carbonyl group participates in an intramolecular C-H
O hydrogen bond which forms a six-membered ring. In molecules (III
a) and (III
c), the dihedral angles between the naphthalene substituent and the flat heterocyclic ring are 96.4 (3) and 102.6 (3)°, respectively. In (III
b), the dihedral angle between the pseudo-axial naphthalene bicycle and the flat part of the pyran ring is 81.6 (3)°. In the crystal structure of (III
a), intermolecular N-H
N and N-H
O hydrogen bonds link the molecules into a three-dimensional framework. In (III
b) and (III
c), only one H atom of the NH
2 group takes part in an N-H
O hydrogen bond and infinite chains are formed along the
a axis.
Supporting information
CCDC references: 248154; 248155; 248156
The title compounds were obtained by the reaction of (1-naphthylmethylene)malononitrile, (I) (Nesterov et al., 2001a), with acetylacetone, (IIa), methyl acetylacetate, (IIb), and tert-butyl acetylacetate, (IIc), respectively, according to the literature procedure of Nesterov & Viltchinskaia (2001) and Nesterov et al. (2004). The precipitates were isolated and recrystallized from acetonitrile [m.p. 468 K and yield 75% for (IIIa); m.p. 453 K and yield 79% for (IIIb); m.p. 479 K and yield 85% for (IIIc)]. All three compounds were characterized by 1H and 13C NMR spectroscopy; these data are available in the archived CIF. The crystals of all three compounds were grown by slow isothermic evaporation of acetonitrile solutions.
For all three compounds, 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, 0.96 Å for CH3, 0.98 Å for CH and 0.86 Å for NH2 groups. In the cases of (IIIb) and (IIIc), the quality of the crystals was not very good and this is probably a reason for the high Rint values. Another reason is likely to be the high thermal motion of the terminal C atoms, especially in (IIIc).
For all compounds, data collection: CAD-4 Software (Enraf-Nonuis, 1989); cell refinement: CAD-4 Software; data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.
(IIIa) 5-Acetyl-2-amino-6-methyl-4-(1-naphthyl)-4
H-pyran-3-carbonitrile
top
Crystal data top
C19H16N2O2 | F(000) = 640 |
Mr = 304.34 | Dx = 1.296 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8630 (16) Å | Cell parameters from 24 reflections |
b = 8.5960 (17) Å | θ = 11–12° |
c = 23.227 (5) Å | µ = 0.09 mm−1 |
β = 96.64 (3)° | T = 295 K |
V = 1559.4 (6) Å3 | Prism, colourless |
Z = 4 | 0.50 × 0.40 × 0.30 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.096 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 1.8° |
Graphite monochromator | h = 0→9 |
θ/2θ scans | k = 0→10 |
3267 measured reflections | l = −28→28 |
3035 independent reflections | 3 standard reflections every 97 reflections |
2151 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.05P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3 |
3035 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C19H16N2O2 | V = 1559.4 (6) Å3 |
Mr = 304.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.8630 (16) Å | µ = 0.09 mm−1 |
b = 8.5960 (17) Å | T = 295 K |
c = 23.227 (5) Å | 0.50 × 0.40 × 0.30 mm |
β = 96.64 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.096 |
3267 measured reflections | 3 standard reflections every 97 reflections |
3035 independent reflections | intensity decay: 3% |
2151 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.23 e Å−3 |
3035 reflections | Δρmin = −0.23 e Å−3 |
210 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.67265 (17) | 0.10516 (16) | 0.19568 (6) | 0.0537 (4) | |
O2 | 0.4328 (2) | 0.42061 (19) | 0.30028 (7) | 0.0736 (5) | |
N1 | 0.7083 (2) | 0.00200 (19) | 0.11063 (7) | 0.0544 (4) | |
H1A | 0.8051 | −0.0292 | 0.1277 | 0.065* | |
H1B | 0.6795 | −0.0197 | 0.0747 | 0.065* | |
N2 | 0.3274 (3) | 0.0902 (2) | 0.01547 (8) | 0.0754 (6) | |
C1 | 0.3809 (2) | 0.1142 (2) | 0.06253 (8) | 0.0479 (5) | |
C2 | 0.6015 (2) | 0.0850 (2) | 0.14023 (8) | 0.0416 (4) | |
C3 | 0.4460 (2) | 0.14247 (19) | 0.12063 (7) | 0.0395 (4) | |
C4 | 0.3402 (2) | 0.23956 (19) | 0.15811 (7) | 0.0389 (4) | |
H4A | 0.2322 | 0.1851 | 0.1613 | 0.047* | |
C5 | 0.4359 (2) | 0.2560 (2) | 0.21816 (7) | 0.0410 (4) | |
C6 | 0.5867 (2) | 0.1902 (2) | 0.23372 (8) | 0.0464 (4) | |
C7 | 0.2991 (2) | 0.3998 (2) | 0.13025 (7) | 0.0392 (4) | |
C8 | 0.4310 (3) | 0.5032 (2) | 0.12907 (9) | 0.0491 (5) | |
H8A | 0.5403 | 0.4742 | 0.1450 | 0.059* | |
C9 | 0.4062 (3) | 0.6517 (2) | 0.10453 (9) | 0.0570 (5) | |
H9A | 0.4984 | 0.7194 | 0.1041 | 0.068* | |
C10 | 0.2484 (3) | 0.6961 (2) | 0.08162 (9) | 0.0572 (5) | |
H10A | 0.2322 | 0.7956 | 0.0662 | 0.069* | |
C11 | 0.1072 (3) | 0.5943 (2) | 0.08066 (8) | 0.0471 (5) | |
C12 | −0.0561 (3) | 0.6381 (3) | 0.05452 (9) | 0.0592 (6) | |
H12A | −0.0727 | 0.7380 | 0.0396 | 0.071* | |
C13 | −0.1888 (3) | 0.5382 (3) | 0.05069 (10) | 0.0659 (6) | |
H13A | −0.2955 | 0.5687 | 0.0327 | 0.079* | |
C14 | −0.1657 (3) | 0.3884 (3) | 0.07384 (10) | 0.0645 (6) | |
H14A | −0.2577 | 0.3198 | 0.0711 | 0.077* | |
C15 | −0.0117 (2) | 0.3416 (3) | 0.10022 (9) | 0.0522 (5) | |
H15A | −0.0003 | 0.2419 | 0.1157 | 0.063* | |
C16 | 0.1333 (2) | 0.4422 (2) | 0.10475 (7) | 0.0410 (4) | |
C17 | 0.6903 (3) | 0.1839 (3) | 0.29159 (10) | 0.0711 (7) | |
H17A | 0.6209 | 0.2155 | 0.3209 | 0.107* | |
H17B | 0.7866 | 0.2526 | 0.2919 | 0.107* | |
H17C | 0.7302 | 0.0795 | 0.2992 | 0.107* | |
C18 | 0.3511 (3) | 0.3450 (2) | 0.26234 (8) | 0.0502 (5) | |
C19 | 0.1608 (3) | 0.3355 (3) | 0.25905 (10) | 0.0641 (6) | |
H19A | 0.1243 | 0.3759 | 0.2941 | 0.096* | |
H19B | 0.1254 | 0.2290 | 0.2542 | 0.096* | |
H19C | 0.1102 | 0.3956 | 0.2267 | 0.096* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0523 (8) | 0.0607 (9) | 0.0462 (8) | 0.0150 (7) | −0.0026 (6) | −0.0072 (6) |
O2 | 0.0907 (12) | 0.0680 (10) | 0.0632 (10) | −0.0070 (9) | 0.0138 (8) | −0.0238 (8) |
N1 | 0.0588 (10) | 0.0539 (10) | 0.0507 (10) | 0.0154 (8) | 0.0072 (8) | −0.0041 (8) |
N2 | 0.0909 (14) | 0.0801 (14) | 0.0509 (11) | 0.0351 (11) | −0.0097 (10) | −0.0136 (10) |
C1 | 0.0565 (11) | 0.0400 (10) | 0.0462 (11) | 0.0133 (9) | 0.0014 (9) | −0.0027 (8) |
C2 | 0.0501 (10) | 0.0339 (9) | 0.0411 (10) | 0.0000 (8) | 0.0063 (8) | 0.0009 (7) |
C3 | 0.0472 (10) | 0.0319 (8) | 0.0393 (9) | 0.0009 (7) | 0.0043 (7) | 0.0013 (7) |
C4 | 0.0423 (9) | 0.0328 (8) | 0.0421 (9) | 0.0004 (7) | 0.0071 (7) | 0.0020 (7) |
C5 | 0.0500 (11) | 0.0343 (9) | 0.0394 (9) | −0.0003 (8) | 0.0080 (8) | 0.0029 (7) |
C6 | 0.0563 (11) | 0.0418 (10) | 0.0405 (10) | 0.0021 (9) | 0.0030 (8) | −0.0032 (8) |
C7 | 0.0482 (10) | 0.0331 (8) | 0.0370 (9) | 0.0008 (8) | 0.0082 (7) | −0.0007 (7) |
C8 | 0.0523 (11) | 0.0390 (10) | 0.0553 (12) | −0.0041 (8) | 0.0033 (9) | 0.0005 (9) |
C9 | 0.0701 (14) | 0.0377 (10) | 0.0625 (13) | −0.0127 (10) | 0.0054 (10) | 0.0028 (9) |
C10 | 0.0824 (15) | 0.0333 (9) | 0.0557 (12) | 0.0026 (10) | 0.0068 (11) | 0.0037 (9) |
C11 | 0.0608 (12) | 0.0428 (10) | 0.0383 (10) | 0.0110 (9) | 0.0081 (8) | 0.0019 (8) |
C12 | 0.0718 (14) | 0.0578 (13) | 0.0487 (12) | 0.0241 (11) | 0.0102 (10) | 0.0091 (10) |
C13 | 0.0558 (13) | 0.0869 (17) | 0.0555 (13) | 0.0211 (13) | 0.0083 (10) | 0.0141 (12) |
C14 | 0.0469 (12) | 0.0835 (16) | 0.0636 (14) | −0.0011 (11) | 0.0082 (10) | 0.0132 (12) |
C15 | 0.0486 (11) | 0.0560 (12) | 0.0526 (11) | −0.0001 (9) | 0.0081 (9) | 0.0107 (9) |
C16 | 0.0477 (10) | 0.0396 (9) | 0.0372 (9) | 0.0047 (8) | 0.0108 (7) | 0.0026 (7) |
C17 | 0.0800 (16) | 0.0753 (15) | 0.0529 (13) | 0.0171 (13) | −0.0137 (11) | −0.0107 (12) |
C18 | 0.0698 (13) | 0.0395 (10) | 0.0424 (10) | 0.0034 (9) | 0.0108 (9) | 0.0033 (8) |
C19 | 0.0737 (15) | 0.0648 (14) | 0.0577 (13) | 0.0143 (12) | 0.0244 (11) | −0.0006 (11) |
Geometric parameters (Å, º) top
O1—C2 | 1.355 (2) | C9—H9A | 0.9300 |
O1—C6 | 1.382 (2) | C10—C11 | 1.412 (3) |
O2—C18 | 1.217 (2) | C10—H10A | 0.9300 |
N1—C2 | 1.349 (2) | C11—C12 | 1.406 (3) |
N1—H1A | 0.8600 | C11—C16 | 1.428 (3) |
N1—H1B | 0.8600 | C12—C13 | 1.347 (3) |
N2—C1 | 1.143 (2) | C12—H12A | 0.9300 |
C1—C3 | 1.408 (3) | C13—C14 | 1.400 (3) |
C2—C3 | 1.348 (3) | C13—H13A | 0.9300 |
C3—C4 | 1.521 (2) | C14—C15 | 1.353 (3) |
C4—C5 | 1.513 (2) | C14—H14A | 0.9300 |
C4—C7 | 1.540 (2) | C15—C16 | 1.425 (3) |
C4—H4A | 0.9800 | C15—H15A | 0.9300 |
C5—C6 | 1.325 (3) | C17—H17A | 0.9600 |
C5—C18 | 1.497 (3) | C17—H17B | 0.9600 |
C6—C17 | 1.490 (3) | C17—H17C | 0.9600 |
C7—C8 | 1.368 (3) | C18—C19 | 1.492 (3) |
C7—C16 | 1.416 (3) | C19—H19A | 0.9600 |
C8—C9 | 1.402 (3) | C19—H19B | 0.9600 |
C8—H8A | 0.9300 | C19—H19C | 0.9600 |
C9—C10 | 1.348 (3) | | |
| | | |
C2—O1—C6 | 119.78 (14) | C11—C10—H10A | 119.4 |
C2—N1—H1A | 120.0 | C12—C11—C10 | 121.18 (18) |
C2—N1—H1B | 120.0 | C12—C11—C16 | 119.79 (19) |
H1A—N1—H1B | 120.0 | C10—C11—C16 | 118.99 (17) |
N2—C1—C3 | 179.5 (2) | C13—C12—C11 | 121.3 (2) |
N1—C2—O1 | 109.82 (16) | C13—C12—H12A | 119.3 |
N1—C2—C3 | 127.98 (17) | C11—C12—H12A | 119.3 |
O1—C2—C3 | 122.20 (16) | C12—C13—C14 | 119.7 (2) |
C2—C3—C1 | 118.38 (17) | C12—C13—H13A | 120.1 |
C2—C3—C4 | 122.85 (16) | C14—C13—H13A | 120.1 |
C1—C3—C4 | 118.75 (15) | C15—C14—C13 | 121.1 (2) |
C5—C4—C3 | 109.40 (14) | C15—C14—H14A | 119.4 |
C5—C4—C7 | 111.19 (14) | C13—C14—H14A | 119.4 |
C3—C4—C7 | 110.62 (14) | C14—C15—C16 | 121.3 (2) |
C5—C4—H4A | 108.5 | C14—C15—H15A | 119.4 |
C3—C4—H4A | 108.5 | C16—C15—H15A | 119.4 |
C7—C4—H4A | 108.5 | C7—C16—C11 | 118.88 (17) |
C6—C5—C18 | 119.11 (17) | C7—C16—C15 | 124.39 (17) |
C6—C5—C4 | 123.05 (16) | C11—C16—C15 | 116.71 (17) |
C18—C5—C4 | 117.78 (16) | C6—C17—H17A | 109.5 |
C5—C6—O1 | 122.66 (17) | C6—C17—H17B | 109.5 |
C5—C6—C17 | 129.78 (19) | H17A—C17—H17B | 109.5 |
O1—C6—C17 | 107.50 (17) | C6—C17—H17C | 109.5 |
C8—C7—C16 | 119.19 (16) | H17A—C17—H17C | 109.5 |
C8—C7—C4 | 117.84 (16) | H17B—C17—H17C | 109.5 |
C16—C7—C4 | 122.95 (15) | O2—C18—C19 | 120.57 (19) |
C7—C8—C9 | 121.97 (19) | O2—C18—C5 | 121.97 (19) |
C7—C8—H8A | 119.0 | C19—C18—C5 | 117.45 (18) |
C9—C8—H8A | 119.0 | C18—C19—H19A | 109.5 |
C10—C9—C8 | 119.78 (19) | C18—C19—H19B | 109.5 |
C10—C9—H9A | 120.1 | H19A—C19—H19B | 109.5 |
C8—C9—H9A | 120.1 | C18—C19—H19C | 109.5 |
C9—C10—C11 | 121.14 (18) | H19A—C19—H19C | 109.5 |
C9—C10—H10A | 119.4 | H19B—C19—H19C | 109.5 |
| | | |
C6—O1—C2—N1 | 178.62 (16) | C4—C7—C8—C9 | 179.87 (18) |
C6—O1—C2—C3 | −1.6 (3) | C7—C8—C9—C10 | 0.5 (3) |
N1—C2—C3—C1 | 0.6 (3) | C8—C9—C10—C11 | −1.4 (3) |
O1—C2—C3—C1 | −179.13 (16) | C9—C10—C11—C12 | −177.2 (2) |
N1—C2—C3—C4 | −177.86 (17) | C9—C10—C11—C16 | 0.3 (3) |
O1—C2—C3—C4 | 2.4 (3) | C10—C11—C12—C13 | 176.3 (2) |
C2—C3—C4—C5 | −0.9 (2) | C16—C11—C12—C13 | −1.2 (3) |
C1—C3—C4—C5 | −179.32 (15) | C11—C12—C13—C14 | 1.0 (3) |
C2—C3—C4—C7 | 121.95 (18) | C12—C13—C14—C15 | 0.1 (4) |
C1—C3—C4—C7 | −56.5 (2) | C13—C14—C15—C16 | −0.9 (3) |
C3—C4—C5—C6 | −1.5 (2) | C8—C7—C16—C11 | −2.6 (3) |
C7—C4—C5—C6 | −123.95 (19) | C4—C7—C16—C11 | 179.18 (15) |
C3—C4—C5—C18 | −178.58 (15) | C8—C7—C16—C15 | 176.14 (18) |
C7—C4—C5—C18 | 58.9 (2) | C4—C7—C16—C15 | −2.1 (3) |
C18—C5—C6—O1 | 179.45 (16) | C12—C11—C16—C7 | 179.24 (17) |
C4—C5—C6—O1 | 2.4 (3) | C10—C11—C16—C7 | 1.7 (3) |
C18—C5—C6—C17 | 2.7 (3) | C12—C11—C16—C15 | 0.4 (3) |
C4—C5—C6—C17 | −174.4 (2) | C10—C11—C16—C15 | −177.12 (17) |
C2—O1—C6—C5 | −0.8 (3) | C14—C15—C16—C7 | −178.1 (2) |
C2—O1—C6—C17 | 176.59 (18) | C14—C15—C16—C11 | 0.6 (3) |
C5—C4—C7—C8 | 51.9 (2) | C6—C5—C18—O2 | 34.9 (3) |
C3—C4—C7—C8 | −69.8 (2) | C4—C5—C18—O2 | −147.83 (19) |
C5—C4—C7—C16 | −129.80 (17) | C6—C5—C18—C19 | −143.94 (19) |
C3—C4—C7—C16 | 108.44 (19) | C4—C5—C18—C19 | 33.3 (2) |
C16—C7—C8—C9 | 1.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.54 | 3.374 (2) | 165 |
N1—H1B···N2ii | 0.86 | 2.18 | 3.016 (2) | 166 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y, −z. |
(IIIb) methyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate
top
Crystal data top
C19H16N2O3 | Z = 2 |
Mr = 320.34 | F(000) = 336 |
Triclinic, P1 | Dx = 1.319 Mg m−3 |
a = 8.3150 (17) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.283 (2) Å | Cell parameters from 24 reflections |
c = 10.793 (2) Å | θ = 11–12° |
α = 112.38 (3)° | µ = 0.09 mm−1 |
β = 96.66 (3)° | T = 295 K |
γ = 103.83 (3)° | Prism, colourless |
V = 806.3 (4) Å3 | 0.45 × 0.40 × 0.25 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.046 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 2.1° |
Graphite monochromator | h = 0→10 |
θ/2θ scans | k = −13→13 |
4108 measured reflections | l = −14→14 |
3841 independent reflections | 3 standard reflections every 97 reflections |
1923 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.08P)2 + 0.1P] where P = (Fo2 + 2Fc2)/3 |
3841 reflections | (Δ/σ)max < 0.001 |
219 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C19H16N2O3 | γ = 103.83 (3)° |
Mr = 320.34 | V = 806.3 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3150 (17) Å | Mo Kα radiation |
b = 10.283 (2) Å | µ = 0.09 mm−1 |
c = 10.793 (2) Å | T = 295 K |
α = 112.38 (3)° | 0.45 × 0.40 × 0.25 mm |
β = 96.66 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.046 |
4108 measured reflections | 3 standard reflections every 97 reflections |
3841 independent reflections | intensity decay: 3% |
1923 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.172 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.20 e Å−3 |
3841 reflections | Δρmin = −0.18 e Å−3 |
219 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.9099 (2) | 0.2278 (2) | 0.46612 (17) | 0.0539 (5) | |
O2 | 0.3788 (2) | 0.3042 (2) | 0.51011 (19) | 0.0635 (6) | |
O3 | 0.4910 (3) | 0.2187 (2) | 0.6480 (2) | 0.0704 (6) | |
N1 | 1.0744 (3) | 0.2997 (3) | 0.3417 (2) | 0.0624 (7) | |
H1A | 1.0995 | 0.3368 | 0.2846 | 0.075* | |
H1B | 1.1450 | 0.2658 | 0.3751 | 0.075* | |
N2 | 0.8599 (4) | 0.4766 (3) | 0.1825 (3) | 0.0884 (9) | |
C1 | 0.8332 (3) | 0.4164 (3) | 0.2508 (3) | 0.0526 (6) | |
C2 | 0.9254 (3) | 0.2946 (3) | 0.3787 (2) | 0.0437 (6) | |
C3 | 0.8017 (3) | 0.3424 (3) | 0.3365 (2) | 0.0402 (5) | |
C4 | 0.6288 (3) | 0.3089 (2) | 0.3695 (2) | 0.0369 (5) | |
H4A | 0.5965 | 0.3998 | 0.3998 | 0.044* | |
C5 | 0.6411 (3) | 0.2633 (2) | 0.4869 (2) | 0.0387 (5) | |
C6 | 0.7738 (3) | 0.2256 (3) | 0.5283 (2) | 0.0438 (6) | |
C7 | 0.4930 (3) | 0.1905 (2) | 0.2419 (2) | 0.0363 (5) | |
C8 | 0.4765 (3) | 0.0452 (3) | 0.2074 (2) | 0.0467 (6) | |
H8A | 0.5469 | 0.0206 | 0.2625 | 0.056* | |
C9 | 0.3565 (3) | −0.0688 (3) | 0.0910 (3) | 0.0563 (7) | |
H9A | 0.3491 | −0.1670 | 0.0691 | 0.068* | |
C10 | 0.2520 (3) | −0.0344 (3) | 0.0111 (3) | 0.0554 (7) | |
H10A | 0.1717 | −0.1100 | −0.0651 | 0.066* | |
C11 | 0.2624 (3) | 0.1132 (3) | 0.0410 (2) | 0.0466 (6) | |
C12 | 0.1510 (3) | 0.1502 (4) | −0.0400 (3) | 0.0608 (8) | |
H12A | 0.0693 | 0.0749 | −0.1154 | 0.073* | |
C13 | 0.1605 (4) | 0.2921 (4) | −0.0104 (3) | 0.0679 (8) | |
H13A | 0.0849 | 0.3137 | −0.0644 | 0.082* | |
C14 | 0.2846 (4) | 0.4066 (4) | 0.1019 (3) | 0.0625 (7) | |
H14A | 0.2927 | 0.5044 | 0.1208 | 0.075* | |
C15 | 0.3936 (3) | 0.3763 (3) | 0.1838 (3) | 0.0484 (6) | |
H15A | 0.4747 | 0.4540 | 0.2581 | 0.058* | |
C16 | 0.3861 (3) | 0.2294 (3) | 0.1584 (2) | 0.0392 (5) | |
C17 | 0.8077 (4) | 0.1729 (4) | 0.6371 (3) | 0.0663 (8) | |
H17A | 0.7023 | 0.1337 | 0.6573 | 0.100* | |
H17B | 0.8816 | 0.2540 | 0.7190 | 0.100* | |
H17C | 0.8612 | 0.0970 | 0.6049 | 0.100* | |
C18 | 0.4921 (3) | 0.2634 (3) | 0.5476 (2) | 0.0447 (6) | |
C19 | 0.3464 (5) | 0.2224 (4) | 0.7114 (4) | 0.0893 (12) | |
H19A | 0.3664 | 0.2024 | 0.7907 | 0.134* | |
H19B | 0.2457 | 0.1489 | 0.6464 | 0.134* | |
H19C | 0.3314 | 0.3184 | 0.7388 | 0.134* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0389 (9) | 0.0852 (13) | 0.0548 (11) | 0.0298 (9) | 0.0146 (8) | 0.0402 (10) |
O2 | 0.0434 (10) | 0.0957 (15) | 0.0593 (11) | 0.0355 (10) | 0.0144 (8) | 0.0318 (11) |
O3 | 0.0772 (14) | 0.0916 (15) | 0.0920 (15) | 0.0536 (12) | 0.0568 (12) | 0.0633 (13) |
N1 | 0.0379 (12) | 0.0996 (19) | 0.0656 (15) | 0.0278 (12) | 0.0177 (11) | 0.0462 (14) |
N2 | 0.080 (2) | 0.102 (2) | 0.129 (3) | 0.0355 (17) | 0.0434 (18) | 0.087 (2) |
C1 | 0.0421 (14) | 0.0539 (15) | 0.0693 (17) | 0.0151 (12) | 0.0145 (12) | 0.0333 (14) |
C2 | 0.0318 (12) | 0.0540 (15) | 0.0419 (13) | 0.0121 (11) | 0.0061 (10) | 0.0180 (12) |
C3 | 0.0320 (11) | 0.0448 (13) | 0.0424 (13) | 0.0095 (10) | 0.0062 (10) | 0.0190 (11) |
C4 | 0.0334 (11) | 0.0384 (12) | 0.0369 (12) | 0.0131 (9) | 0.0039 (9) | 0.0137 (10) |
C5 | 0.0346 (11) | 0.0421 (13) | 0.0369 (12) | 0.0118 (10) | 0.0067 (9) | 0.0146 (10) |
C6 | 0.0377 (13) | 0.0571 (15) | 0.0375 (12) | 0.0163 (11) | 0.0094 (10) | 0.0198 (11) |
C7 | 0.0298 (11) | 0.0413 (13) | 0.0338 (11) | 0.0106 (9) | 0.0077 (9) | 0.0118 (10) |
C8 | 0.0428 (13) | 0.0457 (14) | 0.0463 (14) | 0.0119 (11) | 0.0067 (11) | 0.0161 (12) |
C9 | 0.0567 (16) | 0.0422 (15) | 0.0558 (16) | 0.0056 (12) | 0.0153 (13) | 0.0112 (13) |
C10 | 0.0408 (14) | 0.0573 (17) | 0.0413 (14) | −0.0049 (12) | 0.0076 (11) | 0.0057 (12) |
C11 | 0.0298 (11) | 0.0680 (17) | 0.0372 (13) | 0.0090 (11) | 0.0103 (10) | 0.0203 (12) |
C12 | 0.0377 (14) | 0.094 (2) | 0.0429 (15) | 0.0084 (14) | 0.0025 (11) | 0.0303 (15) |
C13 | 0.0511 (17) | 0.107 (3) | 0.0589 (18) | 0.0284 (17) | 0.0069 (13) | 0.0485 (19) |
C14 | 0.0600 (17) | 0.076 (2) | 0.0634 (18) | 0.0278 (15) | 0.0097 (14) | 0.0396 (16) |
C15 | 0.0447 (14) | 0.0554 (16) | 0.0461 (14) | 0.0178 (12) | 0.0069 (11) | 0.0221 (12) |
C16 | 0.0297 (11) | 0.0527 (14) | 0.0343 (12) | 0.0112 (10) | 0.0094 (9) | 0.0178 (11) |
C17 | 0.0547 (17) | 0.100 (2) | 0.0652 (18) | 0.0324 (16) | 0.0146 (14) | 0.0514 (18) |
C18 | 0.0380 (13) | 0.0451 (14) | 0.0453 (13) | 0.0139 (11) | 0.0097 (10) | 0.0126 (11) |
C19 | 0.097 (3) | 0.106 (3) | 0.128 (3) | 0.064 (2) | 0.084 (2) | 0.080 (3) |
Geometric parameters (Å, º) top
O1—C2 | 1.363 (3) | C8—H8A | 0.9300 |
O1—C6 | 1.381 (3) | C9—C10 | 1.352 (4) |
O2—C18 | 1.207 (3) | C9—H9A | 0.9300 |
O3—C18 | 1.328 (3) | C10—C11 | 1.405 (4) |
O3—C19 | 1.452 (3) | C10—H10A | 0.9300 |
N1—C2 | 1.341 (3) | C11—C12 | 1.414 (3) |
N1—H1A | 0.8600 | C11—C16 | 1.431 (3) |
N1—H1B | 0.8600 | C12—C13 | 1.350 (4) |
N2—C1 | 1.138 (3) | C12—H12A | 0.9300 |
C1—C3 | 1.414 (3) | C13—C14 | 1.401 (4) |
C2—C3 | 1.345 (3) | C13—H13A | 0.9300 |
C3—C4 | 1.512 (3) | C14—C15 | 1.364 (3) |
C4—C5 | 1.510 (3) | C14—H14A | 0.9300 |
C4—C7 | 1.536 (3) | C15—C16 | 1.413 (3) |
C4—H4A | 0.9800 | C15—H15A | 0.9300 |
C5—C6 | 1.337 (3) | C17—H17A | 0.9600 |
C5—C18 | 1.468 (3) | C17—H17B | 0.9600 |
C6—C17 | 1.495 (3) | C17—H17C | 0.9600 |
C7—C8 | 1.363 (3) | C19—H19A | 0.9600 |
C7—C16 | 1.422 (3) | C19—H19B | 0.9600 |
C8—C9 | 1.406 (4) | C19—H19C | 0.9600 |
| | | |
C2—O1—C6 | 119.44 (18) | C11—C10—H10A | 119.3 |
C18—O3—C19 | 116.4 (2) | C10—C11—C12 | 121.8 (2) |
C2—N1—H1A | 120.0 | C10—C11—C16 | 119.3 (2) |
C2—N1—H1B | 120.0 | C12—C11—C16 | 119.0 (3) |
H1A—N1—H1B | 120.0 | C13—C12—C11 | 121.6 (3) |
N2—C1—C3 | 179.5 (3) | C13—C12—H12A | 119.2 |
N1—C2—C3 | 127.5 (2) | C11—C12—H12A | 119.2 |
N1—C2—O1 | 110.2 (2) | C12—C13—C14 | 119.8 (3) |
C3—C2—O1 | 122.2 (2) | C12—C13—H13A | 120.1 |
C2—C3—C1 | 117.9 (2) | C14—C13—H13A | 120.1 |
C2—C3—C4 | 121.8 (2) | C15—C14—C13 | 120.7 (3) |
C1—C3—C4 | 120.21 (19) | C15—C14—H14A | 119.7 |
C5—C4—C3 | 109.19 (17) | C13—C14—H14A | 119.7 |
C5—C4—C7 | 111.85 (18) | C14—C15—C16 | 121.5 (2) |
C3—C4—C7 | 111.26 (18) | C14—C15—H15A | 119.3 |
C5—C4—H4A | 108.1 | C16—C15—H15A | 119.3 |
C3—C4—H4A | 108.1 | C15—C16—C7 | 124.2 (2) |
C7—C4—H4A | 108.1 | C15—C16—C11 | 117.4 (2) |
C6—C5—C18 | 124.5 (2) | C7—C16—C11 | 118.4 (2) |
C6—C5—C4 | 122.8 (2) | C6—C17—H17A | 109.5 |
C18—C5—C4 | 112.69 (19) | C6—C17—H17B | 109.5 |
C5—C6—O1 | 121.4 (2) | H17A—C17—H17B | 109.5 |
C5—C6—C17 | 131.2 (2) | C6—C17—H17C | 109.5 |
O1—C6—C17 | 107.37 (19) | H17A—C17—H17C | 109.5 |
C8—C7—C16 | 119.5 (2) | H17B—C17—H17C | 109.5 |
C8—C7—C4 | 119.08 (19) | O2—C18—O3 | 122.1 (2) |
C16—C7—C4 | 121.45 (19) | O2—C18—C5 | 121.9 (2) |
C7—C8—C9 | 122.1 (2) | O3—C18—C5 | 116.0 (2) |
C7—C8—H8A | 118.9 | O3—C19—H19A | 109.5 |
C9—C8—H8A | 118.9 | O3—C19—H19B | 109.5 |
C10—C9—C8 | 119.4 (2) | H19A—C19—H19B | 109.5 |
C10—C9—H9A | 120.3 | O3—C19—H19C | 109.5 |
C8—C9—H9A | 120.3 | H19A—C19—H19C | 109.5 |
C9—C10—C11 | 121.3 (2) | H19B—C19—H19C | 109.5 |
C9—C10—H10A | 119.3 | | |
| | | |
C6—O1—C2—N1 | 173.0 (2) | C7—C8—C9—C10 | −0.9 (4) |
C6—O1—C2—C3 | −8.7 (3) | C8—C9—C10—C11 | 0.8 (4) |
N1—C2—C3—C1 | −4.9 (4) | C9—C10—C11—C12 | −178.5 (2) |
O1—C2—C3—C1 | 177.1 (2) | C9—C10—C11—C16 | 0.0 (4) |
N1—C2—C3—C4 | 170.5 (2) | C10—C11—C12—C13 | 179.5 (3) |
O1—C2—C3—C4 | −7.5 (4) | C16—C11—C12—C13 | 1.0 (4) |
C2—C3—C4—C5 | 17.9 (3) | C11—C12—C13—C14 | 0.9 (4) |
C1—C3—C4—C5 | −166.8 (2) | C12—C13—C14—C15 | −1.5 (4) |
C2—C3—C4—C7 | −106.0 (2) | C13—C14—C15—C16 | 0.3 (4) |
C1—C3—C4—C7 | 69.2 (3) | C14—C15—C16—C7 | −178.3 (2) |
C3—C4—C5—C6 | −14.6 (3) | C14—C15—C16—C11 | 1.6 (3) |
C7—C4—C5—C6 | 108.9 (2) | C8—C7—C16—C15 | −179.3 (2) |
C3—C4—C5—C18 | 166.16 (19) | C4—C7—C16—C15 | −0.1 (3) |
C7—C4—C5—C18 | −70.3 (2) | C8—C7—C16—C11 | 0.8 (3) |
C18—C5—C6—O1 | 179.9 (2) | C4—C7—C16—C11 | 179.96 (19) |
C4—C5—C6—O1 | 0.8 (4) | C10—C11—C16—C15 | 179.2 (2) |
C18—C5—C6—C17 | 1.5 (4) | C12—C11—C16—C15 | −2.2 (3) |
C4—C5—C6—C17 | −177.6 (3) | C10—C11—C16—C7 | −0.8 (3) |
C2—O1—C6—C5 | 12.1 (3) | C12—C11—C16—C7 | 177.7 (2) |
C2—O1—C6—C17 | −169.2 (2) | C19—O3—C18—O2 | −0.4 (4) |
C5—C4—C7—C8 | −39.6 (3) | C19—O3—C18—C5 | 178.3 (2) |
C3—C4—C7—C8 | 82.8 (2) | C6—C5—C18—O2 | 176.9 (2) |
C5—C4—C7—C16 | 141.2 (2) | C4—C5—C18—O2 | −3.9 (3) |
C3—C4—C7—C16 | −96.4 (2) | C6—C5—C18—O3 | −1.8 (3) |
C16—C7—C8—C9 | 0.0 (3) | C4—C5—C18—O3 | 177.4 (2) |
C4—C7—C8—C9 | −179.2 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.86 | 2.14 | 2.919 (3) | 150 |
Symmetry code: (i) x+1, y, z. |
(IIIc)
tert-butyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate
top
Crystal data top
C22H22N2O3 | Z = 2 |
Mr = 362.42 | F(000) = 384 |
Triclinic, P1 | Dx = 1.273 Mg m−3 |
a = 8.4940 (17) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.938 (2) Å | Cell parameters from 24 reflections |
c = 11.844 (2) Å | θ = 11–12° |
α = 104.69 (3)° | µ = 0.09 mm−1 |
β = 109.84 (3)° | T = 295 K |
γ = 102.30 (3)° | Prism, colourless |
V = 945.6 (5) Å3 | 0.50 × 0.40 × 0.30 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.135 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.0° |
Graphite monochromator | h = 0→10 |
θ/2θ scans | k = −13→13 |
4336 measured reflections | l = −15→14 |
4054 independent reflections | 3 standard reflections every 97 reflections |
2361 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.2P] where P = (Fo2 + 2Fc2)/3 |
4054 reflections | (Δ/σ)max < 0.001 |
248 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C22H22N2O3 | γ = 102.30 (3)° |
Mr = 362.42 | V = 945.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4940 (17) Å | Mo Kα radiation |
b = 10.938 (2) Å | µ = 0.09 mm−1 |
c = 11.844 (2) Å | T = 295 K |
α = 104.69 (3)° | 0.50 × 0.40 × 0.30 mm |
β = 109.84 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.135 |
4336 measured reflections | 3 standard reflections every 97 reflections |
4054 independent reflections | intensity decay: 3% |
2361 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.25 e Å−3 |
4054 reflections | Δρmin = −0.35 e Å−3 |
248 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.3755 (2) | 0.33809 (17) | 0.31858 (19) | 0.0494 (5) | |
O2 | 0.9395 (2) | 0.33586 (18) | 0.33830 (18) | 0.0499 (5) | |
O3 | 0.7117 (2) | 0.14366 (16) | 0.22553 (18) | 0.0482 (5) | |
N1 | 0.2795 (3) | 0.5105 (2) | 0.3444 (2) | 0.0555 (6) | |
H1A | 0.2859 | 0.5926 | 0.3565 | 0.067* | |
H1B | 0.1855 | 0.4538 | 0.3365 | 0.067* | |
N2 | 0.6222 (4) | 0.7949 (2) | 0.3923 (3) | 0.0711 (8) | |
C1 | 0.6016 (3) | 0.6834 (3) | 0.3726 (3) | 0.0466 (6) | |
C2 | 0.4160 (3) | 0.4707 (2) | 0.3378 (2) | 0.0406 (5) | |
C3 | 0.5714 (3) | 0.5454 (2) | 0.3480 (2) | 0.0367 (5) | |
C4 | 0.7117 (3) | 0.4860 (2) | 0.3309 (2) | 0.0351 (5) | |
H4A | 0.8208 | 0.5300 | 0.4100 | 0.042* | |
C5 | 0.6513 (3) | 0.3389 (2) | 0.3088 (2) | 0.0372 (5) | |
C6 | 0.4980 (3) | 0.2746 (2) | 0.3063 (2) | 0.0420 (6) | |
C7 | 0.7514 (3) | 0.5095 (2) | 0.2200 (2) | 0.0366 (5) | |
C8 | 0.6415 (4) | 0.4247 (3) | 0.0971 (2) | 0.0504 (6) | |
H8A | 0.5444 | 0.3551 | 0.0834 | 0.060* | |
C9 | 0.6714 (5) | 0.4397 (4) | −0.0086 (3) | 0.0683 (9) | |
H9A | 0.5938 | 0.3815 | −0.0912 | 0.082* | |
C10 | 0.8134 (5) | 0.5393 (4) | 0.0097 (3) | 0.0724 (10) | |
H10A | 0.8330 | 0.5490 | −0.0606 | 0.087* | |
C11 | 0.9316 (4) | 0.6282 (3) | 0.1339 (3) | 0.0558 (7) | |
C12 | 1.0860 (6) | 0.7301 (4) | 0.1566 (5) | 0.0793 (11) | |
H12A | 1.1076 | 0.7401 | 0.0870 | 0.095* | |
C13 | 1.2017 (5) | 0.8124 (4) | 0.2759 (5) | 0.0868 (13) | |
H13A | 1.3044 | 0.8754 | 0.2881 | 0.104* | |
C14 | 1.1679 (4) | 0.8036 (3) | 0.3815 (4) | 0.0681 (9) | |
H14A | 1.2455 | 0.8635 | 0.4635 | 0.082* | |
C15 | 1.0214 (3) | 0.7074 (2) | 0.3649 (3) | 0.0497 (6) | |
H15A | 1.0008 | 0.7025 | 0.4362 | 0.060* | |
C16 | 0.9010 (3) | 0.6156 (2) | 0.2422 (2) | 0.0408 (6) | |
C17 | 0.4209 (4) | 0.1333 (3) | 0.2938 (3) | 0.0572 (7) | |
H17A | 0.5115 | 0.0921 | 0.3068 | 0.086* | |
H17B | 0.3274 | 0.0850 | 0.2096 | 0.086* | |
H17C | 0.3744 | 0.1320 | 0.3571 | 0.086* | |
C18 | 0.7834 (3) | 0.2730 (2) | 0.2945 (2) | 0.0390 (5) | |
C19 | 0.8191 (3) | 0.0591 (3) | 0.1970 (3) | 0.0515 (7) | |
C20 | 0.9511 (5) | 0.0604 (4) | 0.3198 (3) | 0.0808 (10) | |
H20A | 1.0362 | 0.1487 | 0.3672 | 0.121* | |
H20B | 1.0108 | −0.0020 | 0.3007 | 0.121* | |
H20C | 0.8908 | 0.0355 | 0.3701 | 0.121* | |
C21 | 0.9007 (5) | 0.1050 (4) | 0.1153 (4) | 0.0820 (10) | |
H21A | 0.9892 | 0.1916 | 0.1647 | 0.123* | |
H21B | 0.8109 | 0.1104 | 0.0429 | 0.123* | |
H21C | 0.9548 | 0.0425 | 0.0857 | 0.123* | |
C22 | 0.6785 (5) | −0.0781 (3) | 0.1219 (4) | 0.0848 (11) | |
H22A | 0.5910 | −0.0752 | 0.0467 | 0.127* | |
H22B | 0.6229 | −0.1033 | 0.1746 | 0.127* | |
H22C | 0.7327 | −0.1425 | 0.0968 | 0.127* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0376 (9) | 0.0433 (9) | 0.0790 (13) | 0.0165 (8) | 0.0343 (9) | 0.0236 (9) |
O2 | 0.0326 (9) | 0.0520 (10) | 0.0668 (12) | 0.0155 (8) | 0.0231 (8) | 0.0188 (9) |
O3 | 0.0383 (9) | 0.0400 (9) | 0.0665 (12) | 0.0186 (8) | 0.0234 (9) | 0.0123 (8) |
N1 | 0.0457 (12) | 0.0503 (12) | 0.0904 (18) | 0.0236 (11) | 0.0427 (13) | 0.0301 (12) |
N2 | 0.0706 (17) | 0.0460 (14) | 0.105 (2) | 0.0249 (12) | 0.0449 (16) | 0.0236 (14) |
C1 | 0.0438 (14) | 0.0451 (15) | 0.0580 (16) | 0.0212 (12) | 0.0269 (12) | 0.0161 (12) |
C2 | 0.0406 (13) | 0.0426 (13) | 0.0477 (13) | 0.0195 (11) | 0.0245 (11) | 0.0170 (11) |
C3 | 0.0360 (12) | 0.0401 (12) | 0.0396 (12) | 0.0170 (10) | 0.0206 (10) | 0.0126 (10) |
C4 | 0.0301 (11) | 0.0379 (12) | 0.0386 (12) | 0.0106 (9) | 0.0161 (10) | 0.0138 (10) |
C5 | 0.0352 (12) | 0.0402 (12) | 0.0433 (13) | 0.0172 (10) | 0.0194 (10) | 0.0180 (10) |
C6 | 0.0394 (13) | 0.0388 (12) | 0.0566 (15) | 0.0181 (10) | 0.0267 (12) | 0.0170 (11) |
C7 | 0.0358 (12) | 0.0428 (12) | 0.0412 (12) | 0.0205 (10) | 0.0210 (10) | 0.0179 (10) |
C8 | 0.0470 (14) | 0.0617 (16) | 0.0429 (14) | 0.0220 (13) | 0.0170 (12) | 0.0184 (12) |
C9 | 0.079 (2) | 0.095 (2) | 0.0434 (16) | 0.047 (2) | 0.0276 (15) | 0.0248 (16) |
C10 | 0.103 (3) | 0.103 (3) | 0.067 (2) | 0.068 (2) | 0.059 (2) | 0.055 (2) |
C11 | 0.0702 (18) | 0.0641 (17) | 0.081 (2) | 0.0452 (15) | 0.0553 (17) | 0.0496 (16) |
C12 | 0.096 (3) | 0.080 (2) | 0.140 (4) | 0.055 (2) | 0.093 (3) | 0.081 (3) |
C13 | 0.072 (2) | 0.058 (2) | 0.181 (4) | 0.0338 (18) | 0.083 (3) | 0.070 (3) |
C14 | 0.0491 (17) | 0.0450 (15) | 0.116 (3) | 0.0156 (13) | 0.0376 (18) | 0.0336 (17) |
C15 | 0.0412 (14) | 0.0454 (14) | 0.0706 (18) | 0.0180 (12) | 0.0265 (13) | 0.0263 (13) |
C16 | 0.0411 (13) | 0.0449 (13) | 0.0573 (15) | 0.0258 (11) | 0.0301 (12) | 0.0286 (12) |
C17 | 0.0497 (15) | 0.0426 (14) | 0.094 (2) | 0.0175 (12) | 0.0426 (16) | 0.0282 (14) |
C18 | 0.0345 (12) | 0.0447 (13) | 0.0443 (13) | 0.0161 (10) | 0.0199 (10) | 0.0186 (11) |
C19 | 0.0476 (15) | 0.0492 (14) | 0.0634 (17) | 0.0282 (12) | 0.0268 (13) | 0.0137 (13) |
C20 | 0.090 (2) | 0.085 (2) | 0.085 (2) | 0.063 (2) | 0.034 (2) | 0.0321 (19) |
C21 | 0.089 (2) | 0.092 (3) | 0.079 (2) | 0.037 (2) | 0.054 (2) | 0.019 (2) |
C22 | 0.070 (2) | 0.0506 (18) | 0.119 (3) | 0.0236 (17) | 0.038 (2) | 0.0054 (19) |
Geometric parameters (Å, º) top
O1—C2 | 1.357 (3) | C11—C12 | 1.422 (5) |
O1—C6 | 1.395 (3) | C11—C16 | 1.425 (3) |
O2—C18 | 1.210 (3) | C12—C13 | 1.345 (6) |
O3—C18 | 1.323 (3) | C12—H12A | 0.9300 |
O3—C19 | 1.487 (3) | C13—C14 | 1.396 (5) |
N1—C2 | 1.342 (3) | C13—H13A | 0.9300 |
N1—H1A | 0.8600 | C14—C15 | 1.366 (4) |
N1—H1B | 0.8600 | C14—H14A | 0.9300 |
N2—C1 | 1.144 (3) | C15—C16 | 1.407 (4) |
C1—C3 | 1.410 (3) | C15—H15A | 0.9300 |
C2—C3 | 1.344 (3) | C17—H17A | 0.9600 |
C3—C4 | 1.521 (3) | C17—H17B | 0.9600 |
C4—C5 | 1.505 (3) | C17—H17C | 0.9600 |
C4—C7 | 1.530 (3) | C19—C21 | 1.492 (4) |
C4—H4A | 0.9800 | C19—C20 | 1.499 (4) |
C5—C6 | 1.329 (3) | C19—C22 | 1.519 (4) |
C5—C18 | 1.489 (3) | C20—H20A | 0.9600 |
C6—C17 | 1.491 (3) | C20—H20B | 0.9600 |
C7—C8 | 1.369 (3) | C20—H20C | 0.9600 |
C7—C16 | 1.422 (3) | C21—H21A | 0.9600 |
C8—C9 | 1.401 (4) | C21—H21B | 0.9600 |
C8—H8A | 0.9300 | C21—H21C | 0.9600 |
C9—C10 | 1.353 (5) | C22—H22A | 0.9600 |
C9—H9A | 0.9300 | C22—H22B | 0.9600 |
C10—C11 | 1.405 (5) | C22—H22C | 0.9600 |
C10—H10A | 0.9300 | | |
| | | |
C2—O1—C6 | 119.19 (18) | C14—C13—H13A | 119.9 |
C18—O3—C19 | 122.45 (19) | C15—C14—C13 | 120.3 (3) |
C2—N1—H1A | 120.0 | C15—C14—H14A | 119.9 |
C2—N1—H1B | 120.0 | C13—C14—H14A | 119.9 |
H1A—N1—H1B | 120.0 | C14—C15—C16 | 121.3 (3) |
N2—C1—C3 | 178.4 (3) | C14—C15—H15A | 119.3 |
N1—C2—C3 | 127.7 (2) | C16—C15—H15A | 119.3 |
N1—C2—O1 | 109.3 (2) | C15—C16—C7 | 123.7 (2) |
C3—C2—O1 | 123.0 (2) | C15—C16—C11 | 118.4 (2) |
C2—C3—C1 | 118.1 (2) | C7—C16—C11 | 117.9 (2) |
C2—C3—C4 | 122.4 (2) | C6—C17—H17A | 109.5 |
C1—C3—C4 | 119.5 (2) | C6—C17—H17B | 109.5 |
C5—C4—C3 | 109.68 (18) | H17A—C17—H17B | 109.5 |
C5—C4—C7 | 110.79 (18) | C6—C17—H17C | 109.5 |
C3—C4—C7 | 111.01 (18) | H17A—C17—H17C | 109.5 |
C5—C4—H4A | 108.4 | H17B—C17—H17C | 109.5 |
C3—C4—H4A | 108.4 | O2—C18—O3 | 124.7 (2) |
C7—C4—H4A | 108.4 | O2—C18—C5 | 121.7 (2) |
C6—C5—C18 | 123.1 (2) | O3—C18—C5 | 113.5 (2) |
C6—C5—C4 | 123.5 (2) | O3—C19—C21 | 109.2 (2) |
C18—C5—C4 | 113.32 (19) | O3—C19—C20 | 109.9 (2) |
C5—C6—O1 | 122.0 (2) | C21—C19—C20 | 113.7 (3) |
C5—C6—C17 | 131.3 (2) | O3—C19—C22 | 101.7 (2) |
O1—C6—C17 | 106.7 (2) | C21—C19—C22 | 110.9 (3) |
C8—C7—C16 | 119.6 (2) | C20—C19—C22 | 110.8 (3) |
C8—C7—C4 | 118.9 (2) | C19—C20—H20A | 109.5 |
C16—C7—C4 | 121.5 (2) | C19—C20—H20B | 109.5 |
C7—C8—C9 | 121.8 (3) | H20A—C20—H20B | 109.5 |
C7—C8—H8A | 119.1 | C19—C20—H20C | 109.5 |
C9—C8—H8A | 119.1 | H20A—C20—H20C | 109.5 |
C10—C9—C8 | 119.8 (3) | H20B—C20—H20C | 109.5 |
C10—C9—H9A | 120.1 | C19—C21—H21A | 109.5 |
C8—C9—H9A | 120.1 | C19—C21—H21B | 109.5 |
C9—C10—C11 | 120.7 (3) | H21A—C21—H21B | 109.5 |
C9—C10—H10A | 119.6 | C19—C21—H21C | 109.5 |
C11—C10—H10A | 119.6 | H21A—C21—H21C | 109.5 |
C10—C11—C12 | 122.0 (3) | H21B—C21—H21C | 109.5 |
C10—C11—C16 | 120.1 (3) | C19—C22—H22A | 109.5 |
C12—C11—C16 | 118.0 (3) | C19—C22—H22B | 109.5 |
C13—C12—C11 | 121.8 (3) | H22A—C22—H22B | 109.5 |
C13—C12—H12A | 119.1 | C19—C22—H22C | 109.5 |
C11—C12—H12A | 119.1 | H22A—C22—H22C | 109.5 |
C12—C13—C14 | 120.2 (3) | H22B—C22—H22C | 109.5 |
C12—C13—H13A | 119.9 | | |
| | | |
C6—O1—C2—N1 | 178.9 (2) | C8—C9—C10—C11 | −0.1 (5) |
C6—O1—C2—C3 | −1.2 (4) | C9—C10—C11—C12 | 177.3 (3) |
N1—C2—C3—C1 | 2.2 (4) | C9—C10—C11—C16 | −1.1 (4) |
O1—C2—C3—C1 | −177.7 (2) | C10—C11—C12—C13 | −177.9 (3) |
N1—C2—C3—C4 | −176.3 (2) | C16—C11—C12—C13 | 0.5 (4) |
O1—C2—C3—C4 | 3.8 (4) | C11—C12—C13—C14 | −3.1 (5) |
C2—C3—C4—C5 | −2.8 (3) | C12—C13—C14—C15 | 3.0 (5) |
C1—C3—C4—C5 | 178.7 (2) | C13—C14—C15—C16 | −0.2 (4) |
C2—C3—C4—C7 | 120.0 (2) | C14—C15—C16—C7 | 176.8 (2) |
C1—C3—C4—C7 | −58.5 (3) | C14—C15—C16—C11 | −2.3 (4) |
C3—C4—C5—C6 | −0.5 (3) | C8—C7—C16—C15 | −179.8 (2) |
C7—C4—C5—C6 | −123.4 (2) | C4—C7—C16—C15 | −1.0 (3) |
C3—C4—C5—C18 | −178.45 (18) | C8—C7—C16—C11 | −0.7 (3) |
C7—C4—C5—C18 | 58.7 (3) | C4—C7—C16—C11 | 178.1 (2) |
C18—C5—C6—O1 | −179.3 (2) | C10—C11—C16—C15 | −179.3 (2) |
C4—C5—C6—O1 | 2.9 (4) | C12—C11—C16—C15 | 2.2 (3) |
C18—C5—C6—C17 | 1.9 (4) | C10—C11—C16—C7 | 1.5 (3) |
C4—C5—C6—C17 | −175.9 (3) | C12—C11—C16—C7 | −177.0 (2) |
C2—O1—C6—C5 | −2.2 (4) | C19—O3—C18—O2 | 1.7 (4) |
C2—O1—C6—C17 | 176.9 (2) | C19—O3—C18—C5 | 178.7 (2) |
C5—C4—C7—C8 | 39.9 (3) | C6—C5—C18—O2 | −154.6 (3) |
C3—C4—C7—C8 | −82.2 (3) | C4—C5—C18—O2 | 23.4 (3) |
C5—C4—C7—C16 | −138.9 (2) | C6—C5—C18—O3 | 28.3 (3) |
C3—C4—C7—C16 | 99.0 (2) | C4—C5—C18—O3 | −153.7 (2) |
C16—C7—C8—C9 | −0.5 (4) | C18—O3—C19—C21 | −64.9 (3) |
C4—C7—C8—C9 | −179.3 (2) | C18—O3—C19—C20 | 60.5 (3) |
C7—C8—C9—C10 | 0.9 (4) | C18—O3—C19—C22 | 177.9 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.86 | 2.22 | 3.071 (3) | 171 |
Symmetry code: (i) x−1, y, z. |
Experimental details
| (IIIa) | (IIIb) | (IIIc) |
Crystal data |
Chemical formula | C19H16N2O2 | C19H16N2O3 | C22H22N2O3 |
Mr | 304.34 | 320.34 | 362.42 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 295 | 295 | 295 |
a, b, c (Å) | 7.8630 (16), 8.5960 (17), 23.227 (5) | 8.3150 (17), 10.283 (2), 10.793 (2) | 8.4940 (17), 10.938 (2), 11.844 (2) |
α, β, γ (°) | 90, 96.64 (3), 90 | 112.38 (3), 96.66 (3), 103.83 (3) | 104.69 (3), 109.84 (3), 102.30 (3) |
V (Å3) | 1559.4 (6) | 806.3 (4) | 945.6 (5) |
Z | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.50 × 0.40 × 0.30 | 0.45 × 0.40 × 0.25 | 0.50 × 0.40 × 0.30 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3267, 3035, 2151 | 4108, 3841, 1923 | 4336, 4054, 2361 |
Rint | 0.096 | 0.046 | 0.135 |
(sin θ/λ)max (Å−1) | 0.616 | 0.660 | 0.638 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.123, 1.07 | 0.055, 0.172, 1.02 | 0.059, 0.187, 1.02 |
No. of reflections | 3035 | 3841 | 4054 |
No. of parameters | 210 | 219 | 248 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.23 | 0.20, −0.18 | 0.25, −0.35 |
Selected geometric parameters (Å, º) for (IIIa) topO2—C18 | 1.217 (2) | C3—C4 | 1.521 (2) |
N1—C2 | 1.349 (2) | C4—C5 | 1.513 (2) |
N2—C1 | 1.143 (2) | C4—C7 | 1.540 (2) |
C1—C3 | 1.408 (3) | C5—C6 | 1.325 (3) |
C2—C3 | 1.348 (3) | C5—C18 | 1.497 (3) |
| | | |
N1—C2—C3 | 127.98 (17) | C5—C4—C7 | 111.19 (14) |
O1—C2—C3 | 122.20 (16) | C3—C4—C7 | 110.62 (14) |
C2—C3—C1 | 118.38 (17) | C6—C5—C4 | 123.05 (16) |
C2—C3—C4 | 122.85 (16) | C5—C6—C17 | 129.78 (19) |
C5—C4—C3 | 109.40 (14) | | |
| | | |
C2—C3—C4—C7 | 121.95 (18) | C6—C5—C18—C19 | −143.94 (19) |
C3—C4—C7—C8 | −69.8 (2) | C4—C5—C18—C19 | 33.3 (2) |
C6—C5—C18—O2 | 34.9 (3) | | |
Hydrogen-bond geometry (Å, º) for (IIIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.54 | 3.374 (2) | 165 |
N1—H1B···N2ii | 0.86 | 2.18 | 3.016 (2) | 166 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y, −z. |
Selected geometric parameters (Å, º) for (IIIb) topO2—C18 | 1.207 (3) | C3—C4 | 1.512 (3) |
N1—C2 | 1.341 (3) | C4—C5 | 1.510 (3) |
N2—C1 | 1.138 (3) | C4—C7 | 1.536 (3) |
C1—C3 | 1.414 (3) | C5—C6 | 1.337 (3) |
C2—C3 | 1.345 (3) | C5—C18 | 1.468 (3) |
| | | |
N1—C2—C3 | 127.5 (2) | C5—C4—C3 | 109.19 (17) |
C3—C2—O1 | 122.2 (2) | C5—C4—C7 | 111.85 (18) |
C2—C3—C1 | 117.9 (2) | C3—C4—C7 | 111.26 (18) |
C2—C3—C4 | 121.8 (2) | C6—C5—C4 | 122.8 (2) |
C1—C3—C4 | 120.21 (19) | C5—C6—C17 | 131.2 (2) |
| | | |
C2—C3—C4—C7 | −106.0 (2) | C6—C5—C18—O2 | 176.9 (2) |
C3—C4—C7—C8 | 82.8 (2) | C6—C5—C18—O3 | −1.8 (3) |
C19—O3—C18—C5 | 178.3 (2) | | |
Hydrogen-bond geometry (Å, º) for (IIIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.86 | 2.14 | 2.919 (3) | 150 |
Symmetry code: (i) x+1, y, z. |
Selected geometric parameters (Å, º) for (IIIc) topO2—C18 | 1.210 (3) | C3—C4 | 1.521 (3) |
N1—C2 | 1.342 (3) | C4—C5 | 1.505 (3) |
N2—C1 | 1.144 (3) | C4—C7 | 1.530 (3) |
C1—C3 | 1.410 (3) | C5—C6 | 1.329 (3) |
C2—C3 | 1.344 (3) | C5—C18 | 1.489 (3) |
| | | |
N1—C2—C3 | 127.7 (2) | C5—C4—C3 | 109.68 (18) |
C3—C2—O1 | 123.0 (2) | C5—C4—C7 | 110.79 (18) |
C2—C3—C1 | 118.1 (2) | C3—C4—C7 | 111.01 (18) |
C2—C3—C4 | 122.4 (2) | C6—C5—C4 | 123.5 (2) |
C1—C3—C4 | 119.5 (2) | C5—C6—C17 | 131.3 (2) |
| | | |
C2—C3—C4—C7 | 120.0 (2) | C6—C5—C18—O2 | −154.6 (3) |
C3—C4—C7—C8 | −82.2 (3) | C6—C5—C18—O3 | 28.3 (3) |
Hydrogen-bond geometry (Å, º) for (IIIc) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.86 | 2.22 | 3.071 (3) | 171 |
Symmetry code: (i) x−1, y, z. |
The present investigation of the title compounds, (IIIa), (IIIb) and (IIIc), is a continuation of our work on the synthesis and structural study of heterocyclic compounds, such as 4H-pyran derivatives (Sharanina et al., 1986; Klokol et al., 1987; Nesterov & Viltchinskaia, 2001; Shestopalov et al., 2002, 2003; Nesterov et al., 2004), that can be obtained starting from different unsaturated nitriles (Nesterov et al., 2001a,b). Some 4H-pyran derivatives are potential bioactive compounds, such as calcium antagonists (Suarez et al., 2002). \sch
Syntheses and X-ray structural investigations have been carried out for compounds (IIIa), (IIIb) and (IIIc) (Figs. 1–3), which were synthezized by the reaction of (1-naphthylmethylene)malononitrile, (I) (Nesterov et al., 2001a), with a 1,3-diketone or β-ketoesters, (II). Most of the geometric parameters in the molecules are very similar to the standard values (Allen et al., 1987), and are very close to our data from analogous compounds (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004) and to the literature data cited in those previous works.
The X-ray analyses showed that all three title molecules have slightly different structures. The pyran ring in (IIIa) and (IIIc) is practically flat [planar to within 0.009 (3) and 0.013 (3) Å, respectively]. However, in (IIIb) it adopts a flattened boat conformation: atoms O1 and C4 are displaced out of the C2/C3/C5/C6 plane [planar to within 0.017 (3) Å] by −0.106 (3) and −0.208 (3) Å, respectively. The bending of the pyran ring of (IIIb) along the lines O1···C4, C2···C6 and C3···C5 is 14.7 (3), 8.8 (3) and 13.8 (3)°, respectively.
In molecules (IIIa) and (IIIc), the dihedral angles between the bulky naphthalene substituent and the pyran ring is 96.4 (3) and 102.6 (3)°, respectively. In (IIIb), the naphthalene substituent occupies a pseudo-axial position and the dihedral angle with the flat part of the pyran rings is 81.6 (3)°. The mutual orientation of these fragments and the flatness of the heterocyclic rings lead to H···H intramolecular steric interactions: H4A···H15A 2.06 in (IIIa), 2.06 in (IIIb) and 2.04 Å in (IIIc). These contacts are shorter than the sum of the van der Waals radii of H atoms (Rowland & Taylor, 1996). As mentioned previously by us for related compounds (Nesterov et al., 2004), such steric hindrance causes elongation of the C4—C7 bond lengths to 1.540 (2), 1.536 (3) and 1.530 (3) Å, respectively, in comparison with the neighbouring Csp3—Csp2 distances, which are only slightly longer than or equal to the standard value (Allen et al., 1987).
The C═O group has interesting orientational preferences relative to the C5═C6 double bond in the title molecules. In (IIIb) and (IIIc), the groups are anti [`transoid'; C6—C5—C18—O2 torsion angles 176.9 (2) and −154.6 (3)°, respectively]. However, in (IIIa) they are syn [`cisoid'; C6—C5—C18—O2 torsion angle is 34.9 (3)°]. In the latter case, a short intramolecular contact [O2···H17A 2.32 Å] is present which connects the atoms into a six-membered ring. According to literature data (Desiraju & Steiner 1999), this contact can be considered to be a weak hydrogen bond, with parameters C17···O2 2.894 (3) Å, C17—H17A 0.96 Å and C17—H17A···O2 118°. As seen in Figs. 2 and 3, in (IIIb) and (IIIc) the O3 atoms of the ester groups have favourable orientations for the formation of short intramolecular contacts with the CH3 groups of the heterocyclic ring. The O3···H17A distances are 2.15 and 2.26 Å, respectively. These contacts can also be considered to be weak hydrogen bonds, with parameters C17···O3 2.792 (3) Å, C17—H17A 0.96 Å and C17—H17A···O3 123° in (IIIb), and C17···O3 2.837 (3) Å, C17—H17A 0.96 Å and C17—H17A···O3 118° in (IIIc). In each case, the hydrogen bond connects the atoms into a six-membered ring.
Similar to what we observed in related compounds (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004), in all three title molecules there is conjugation between the donor NH2 and the acceptor CN groups via the C2═C3 double bond.
In the crystal of (IIIa), the active H atoms of the NH2 group participate in intermolecular N—H···N and N—H···O hydrogen bonds, linking the molecules into a three-dimensional framework (Fig. 4). However, in the crystals of (IIIb) and (IIIc), only one H atom of the NH2 group is involved in an N—H···O hydrogen bond, forming infinite chains along the a axis (Figs. 5 and 6).
Analysis of the crystal packings of all three compounds shows that there are intermolecular steric C···C contacts between atoms of the naphthalene substituents of neighbouring molecules which are less than the sum of the van der Waals radii of C (Rowland & Taylor, 1996). Such contacts probably play a role in the orientation of bulky substituents in the molecule and can be considered as π–π-interactions. The remaining geometrical parameters in the title molecules have standard values (Allen et al., 1987).