Buy article online - an online subscription or single-article purchase is required to access this article.
In the title compounds, 2-methoxyethyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate, C
21H
20N
2O
4, (II), isopropyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate, C
21H
20N
2O
3, (III), and ethyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate, C
20H
18N
2O
3, (IV), the heterocyclic pyran ring adopts a flattened boat conformation. In (II) and (III), the carbonyl group and a double bond of the heterocyclic ring are mutually
anti, but in (IV) they are mutually
syn. The ester O atoms in (II) and (III) and the carbonyl O atom in (IV) participate in intramolecular C—H
O contacts to form six-membered rings. The dihedral angles between the naphthalene substituent and the closest four atoms of the heterocyclic ring are 73.3 (1), 71.0 (1) and 74.3 (1)° for (II)–(IV), respectively. In all three structures, only one H atom of the NH
2 group takes part in N—H
O [in (II) and (III)] or N—H
N [in (IV)] intermolecular hydrogen bonds, and chains [in (II) and (III)] or dimers [in (IV)] are formed. In (II), weak intermolecular C—H
O and C—H
N hydrogen bonds, and in (III) intermolecular C—H
O hydrogen bonds link the chains into ladders along the
a axis.
Supporting information
CCDC references: 672432; 672433; 672434
The title compounds, (II)–(IV), were obtained by the reaction of
(1-naphthylmethylene)malononitrile, (I), with 2-methoxyethyl acetoacetate,
isopropyl acetoacetate and ethyl acetoacetate, respectively, according to a
literature procedure (Nesterov & Viltchinskaia, 2001; Nesterov et al.,
2004). The resulting precipitates were isolated and recrystallized from
acetonitrile [m.p. 437 K, yield 75% for (II); m.p. 451 K, yield 79% for (III);
m.p. 417 K, yield 77% for (IV)]. Crystals of the compounds were grown by slow
isothermic evaporation from absolute ethanol solutions. All compounds were
characterized by 1H and 13C NMR spectroscopy.
For all three title compounds, H atoms were placed in geometrically calculated
positions and refined using a riding model, with C—H distances of 0.95 Å
for aromatic H atoms with Uiso(H) = 1.2Ueq(C), 0.98 Å for
CH3 (AFIX 137 in SHELXTL; Sheldrick, 2001) with Uiso(H) =
1.5Ueq(C), 0.99 Å for CH2 with Uiso(H) =
1.2Ueq(C) and 1.00 Å for CH with Uiso(H) =
1.2Ueq(C), and with N—H distances of 0.88 Å for the NH2 group
with Uiso(H) = 1.2Ueq(C). ##From the Co-editor: The lattice
refinements are based on rather small numbers of reflections. Was
SAINT-Plus actually used for these, or were they done in APEX2?
For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).
(II) 2-methoxyethyl
6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate
top
Crystal data top
C21H20N2O4 | Z = 2 |
Mr = 364.39 | F(000) = 384 |
Triclinic, P1 | Dx = 1.328 Mg m−3 |
a = 8.245 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.962 (3) Å | Cell parameters from 1887 reflections |
c = 11.008 (3) Å | θ = 3–28° |
α = 98.391 (7)° | µ = 0.09 mm−1 |
β = 100.819 (8)° | T = 100 K |
γ = 107.349 (7)° | Square prism, colourless |
V = 910.9 (4) Å3 | 0.22 × 0.17 × 0.14 mm |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3594 independent reflections |
Radiation source: sealed tube | 2533 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.902, Tmax = 0.987 | k = −13→13 |
7926 measured reflections | l = −13→13 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.1P] where P = (Fo2 + 2Fc2)/3 |
3594 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C21H20N2O4 | γ = 107.349 (7)° |
Mr = 364.39 | V = 910.9 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.245 (2) Å | Mo Kα radiation |
b = 10.962 (3) Å | µ = 0.09 mm−1 |
c = 11.008 (3) Å | T = 100 K |
α = 98.391 (7)° | 0.22 × 0.17 × 0.14 mm |
β = 100.819 (8)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3594 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2533 reflections with I > 2σ(I) |
Tmin = 0.902, Tmax = 0.987 | Rint = 0.029 |
7926 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
3594 reflections | Δρmin = −0.26 e Å−3 |
246 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.41018 (15) | 0.31202 (11) | 0.38590 (11) | 0.0211 (3) | |
O2 | 0.99168 (15) | 0.33411 (12) | 0.37665 (11) | 0.0258 (3) | |
O3 | 0.79086 (16) | 0.27279 (14) | 0.19303 (11) | 0.0324 (3) | |
O4 | 0.68966 (17) | 0.09791 (13) | −0.03360 (12) | 0.0333 (3) | |
N1 | 0.31640 (19) | 0.35927 (14) | 0.55706 (14) | 0.0234 (4) | |
H1A | 0.3256 | 0.3807 | 0.6389 | 0.028* | |
H1B | 0.2167 | 0.3462 | 0.5027 | 0.028* | |
N2 | 0.6754 (2) | 0.44120 (16) | 0.82608 (15) | 0.0308 (4) | |
C1 | 0.6502 (2) | 0.40580 (17) | 0.71815 (17) | 0.0214 (4) | |
C2 | 0.5359 (2) | 0.30202 (16) | 0.32044 (16) | 0.0190 (4) | |
C3 | 0.6993 (2) | 0.31493 (16) | 0.38225 (15) | 0.0179 (4) | |
C4 | 0.7578 (2) | 0.33739 (16) | 0.52564 (15) | 0.0178 (4) | |
H4A | 0.8651 | 0.4171 | 0.5560 | 0.021* | |
C5 | 0.6159 (2) | 0.36299 (16) | 0.58482 (16) | 0.0182 (4) | |
C6 | 0.4542 (2) | 0.34660 (16) | 0.51515 (16) | 0.0186 (4) | |
C7 | 0.8057 (2) | 0.22093 (16) | 0.56394 (15) | 0.0177 (4) | |
C8 | 0.7108 (2) | 0.09620 (17) | 0.49691 (16) | 0.0204 (4) | |
H8A | 0.6121 | 0.0832 | 0.4298 | 0.024* | |
C9 | 0.7544 (2) | −0.01314 (17) | 0.52405 (17) | 0.0245 (4) | |
H9A | 0.6845 | −0.0983 | 0.4764 | 0.029* | |
C10 | 0.8967 (2) | 0.00282 (18) | 0.61857 (18) | 0.0262 (4) | |
H10A | 0.9274 | −0.0711 | 0.6351 | 0.031* | |
C11 | 0.9988 (2) | 0.12883 (18) | 0.69210 (16) | 0.0226 (4) | |
C12 | 1.1508 (2) | 0.1489 (2) | 0.78962 (17) | 0.0288 (4) | |
H12A | 1.1851 | 0.0760 | 0.8049 | 0.035* | |
C13 | 1.2476 (2) | 0.2700 (2) | 0.86114 (17) | 0.0316 (5) | |
H13A | 1.3503 | 0.2814 | 0.9239 | 0.038* | |
C14 | 1.1960 (2) | 0.3792 (2) | 0.84245 (17) | 0.0283 (4) | |
H14A | 1.2603 | 0.4629 | 0.8957 | 0.034* | |
C15 | 1.0532 (2) | 0.36457 (18) | 0.74761 (16) | 0.0222 (4) | |
H15A | 1.0210 | 0.4389 | 0.7350 | 0.027* | |
C16 | 0.9525 (2) | 0.24030 (17) | 0.66782 (15) | 0.0191 (4) | |
C17 | 0.4512 (2) | 0.27700 (19) | 0.18317 (16) | 0.0267 (4) | |
H17A | 0.5287 | 0.2543 | 0.1332 | 0.040* | |
H17B | 0.4292 | 0.3558 | 0.1633 | 0.040* | |
H17C | 0.3399 | 0.2044 | 0.1626 | 0.040* | |
C18 | 0.8406 (2) | 0.30847 (16) | 0.31877 (16) | 0.0198 (4) | |
C19 | 0.9213 (2) | 0.2536 (2) | 0.12673 (17) | 0.0292 (5) | |
H19A | 0.9628 | 0.1832 | 0.1526 | 0.035* | |
H19B | 1.0231 | 0.3352 | 0.1453 | 0.035* | |
C20 | 0.8308 (2) | 0.21658 (19) | −0.01109 (17) | 0.0287 (4) | |
H20A | 0.7866 | 0.2864 | −0.0354 | 0.034* | |
H20B | 0.9141 | 0.2054 | −0.0624 | 0.034* | |
C21 | 0.5818 (3) | 0.0644 (2) | −0.15847 (18) | 0.0349 (5) | |
H21A | 0.4788 | −0.0123 | −0.1666 | 0.052* | |
H21B | 0.6482 | 0.0443 | −0.2192 | 0.052* | |
H21C | 0.5440 | 0.1382 | −0.1759 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0180 (6) | 0.0299 (7) | 0.0177 (6) | 0.0116 (6) | 0.0043 (5) | 0.0045 (5) |
O2 | 0.0167 (7) | 0.0373 (8) | 0.0240 (7) | 0.0092 (6) | 0.0050 (5) | 0.0076 (6) |
O3 | 0.0215 (7) | 0.0574 (9) | 0.0180 (7) | 0.0137 (7) | 0.0079 (5) | 0.0019 (6) |
O4 | 0.0306 (8) | 0.0372 (8) | 0.0250 (7) | 0.0021 (6) | 0.0059 (6) | 0.0057 (6) |
N1 | 0.0208 (8) | 0.0329 (9) | 0.0209 (8) | 0.0139 (7) | 0.0066 (6) | 0.0069 (7) |
N2 | 0.0314 (9) | 0.0419 (10) | 0.0218 (9) | 0.0181 (8) | 0.0063 (7) | 0.0031 (8) |
C1 | 0.0182 (9) | 0.0237 (10) | 0.0256 (11) | 0.0108 (8) | 0.0063 (8) | 0.0064 (8) |
C2 | 0.0205 (9) | 0.0184 (9) | 0.0198 (9) | 0.0083 (7) | 0.0064 (7) | 0.0041 (7) |
C3 | 0.0191 (9) | 0.0167 (9) | 0.0177 (9) | 0.0059 (7) | 0.0041 (7) | 0.0039 (7) |
C4 | 0.0167 (9) | 0.0181 (9) | 0.0177 (9) | 0.0056 (7) | 0.0037 (7) | 0.0024 (7) |
C5 | 0.0202 (9) | 0.0184 (9) | 0.0171 (9) | 0.0073 (7) | 0.0050 (7) | 0.0045 (7) |
C6 | 0.0220 (9) | 0.0166 (9) | 0.0191 (9) | 0.0081 (7) | 0.0059 (7) | 0.0046 (7) |
C7 | 0.0154 (8) | 0.0228 (9) | 0.0174 (9) | 0.0078 (7) | 0.0069 (7) | 0.0050 (7) |
C8 | 0.0166 (9) | 0.0247 (9) | 0.0205 (9) | 0.0075 (7) | 0.0049 (7) | 0.0051 (7) |
C9 | 0.0262 (10) | 0.0198 (9) | 0.0297 (10) | 0.0075 (8) | 0.0118 (8) | 0.0060 (8) |
C10 | 0.0275 (10) | 0.0280 (10) | 0.0338 (11) | 0.0167 (9) | 0.0145 (8) | 0.0145 (9) |
C11 | 0.0200 (9) | 0.0318 (10) | 0.0221 (9) | 0.0115 (8) | 0.0108 (7) | 0.0114 (8) |
C12 | 0.0266 (10) | 0.0436 (12) | 0.0264 (10) | 0.0201 (9) | 0.0095 (8) | 0.0176 (9) |
C13 | 0.0212 (10) | 0.0573 (14) | 0.0193 (10) | 0.0167 (10) | 0.0030 (8) | 0.0128 (9) |
C14 | 0.0199 (10) | 0.0420 (12) | 0.0195 (10) | 0.0065 (9) | 0.0048 (7) | 0.0045 (8) |
C15 | 0.0194 (9) | 0.0297 (10) | 0.0197 (9) | 0.0085 (8) | 0.0081 (7) | 0.0067 (8) |
C16 | 0.0161 (9) | 0.0276 (10) | 0.0167 (9) | 0.0086 (8) | 0.0079 (7) | 0.0072 (7) |
C17 | 0.0252 (10) | 0.0391 (11) | 0.0207 (10) | 0.0188 (9) | 0.0042 (8) | 0.0064 (8) |
C18 | 0.0209 (9) | 0.0182 (9) | 0.0205 (9) | 0.0058 (7) | 0.0056 (7) | 0.0056 (7) |
C19 | 0.0203 (10) | 0.0434 (12) | 0.0255 (10) | 0.0105 (9) | 0.0127 (8) | 0.0038 (9) |
C20 | 0.0269 (10) | 0.0334 (11) | 0.0246 (10) | 0.0061 (9) | 0.0111 (8) | 0.0051 (8) |
C21 | 0.0296 (11) | 0.0419 (13) | 0.0292 (11) | 0.0117 (10) | 0.0035 (9) | 0.0013 (9) |
Geometric parameters (Å, º) top
O1—C6 | 1.366 (2) | C9—H9A | 0.9500 |
O1—C2 | 1.389 (2) | C10—C11 | 1.413 (3) |
O2—C18 | 1.215 (2) | C10—H10A | 0.9500 |
O3—C18 | 1.330 (2) | C11—C12 | 1.426 (2) |
O3—C19 | 1.455 (2) | C11—C16 | 1.430 (2) |
O4—C20 | 1.415 (2) | C12—C13 | 1.359 (3) |
O4—C21 | 1.419 (2) | C12—H12A | 0.9500 |
N1—C6 | 1.340 (2) | C13—C14 | 1.414 (3) |
N1—H1A | 0.8800 | C13—H13A | 0.9500 |
N1—H1B | 0.8800 | C14—C15 | 1.370 (2) |
N2—C1 | 1.153 (2) | C14—H14A | 0.9500 |
C1—C5 | 1.421 (2) | C15—C16 | 1.421 (2) |
C2—C3 | 1.347 (2) | C15—H15A | 0.9500 |
C2—C17 | 1.488 (2) | C17—H17A | 0.9800 |
C3—C18 | 1.481 (2) | C17—H17B | 0.9800 |
C3—C4 | 1.521 (2) | C17—H17C | 0.9800 |
C4—C5 | 1.517 (2) | C19—C20 | 1.496 (3) |
C4—C7 | 1.536 (2) | C19—H19A | 0.9900 |
C4—H4A | 1.0000 | C19—H19B | 0.9900 |
C5—C6 | 1.353 (2) | C20—H20A | 0.9900 |
C7—C8 | 1.370 (2) | C20—H20B | 0.9900 |
C7—C16 | 1.440 (2) | C21—H21A | 0.9800 |
C8—C9 | 1.406 (2) | C21—H21B | 0.9800 |
C8—H8A | 0.9500 | C21—H21C | 0.9800 |
C9—C10 | 1.362 (3) | | |
| | | |
C6—O1—C2 | 120.42 (13) | C13—C12—H12A | 119.3 |
C18—O3—C19 | 117.36 (14) | C11—C12—H12A | 119.3 |
C20—O4—C21 | 112.39 (14) | C12—C13—C14 | 120.24 (17) |
C6—N1—H1A | 120.0 | C12—C13—H13A | 119.9 |
C6—N1—H1B | 120.0 | C14—C13—H13A | 119.9 |
H1A—N1—H1B | 120.0 | C15—C14—C13 | 120.09 (18) |
N2—C1—C5 | 178.80 (19) | C15—C14—H14A | 120.0 |
C3—C2—O1 | 121.12 (15) | C13—C14—H14A | 120.0 |
C3—C2—C17 | 131.90 (16) | C14—C15—C16 | 121.28 (17) |
O1—C2—C17 | 106.98 (14) | C14—C15—H15A | 119.4 |
C2—C3—C18 | 123.96 (16) | C16—C15—H15A | 119.4 |
C2—C3—C4 | 123.21 (15) | C15—C16—C11 | 118.38 (15) |
C18—C3—C4 | 112.83 (14) | C15—C16—C7 | 123.27 (15) |
C5—C4—C3 | 109.69 (14) | C11—C16—C7 | 118.35 (16) |
C5—C4—C7 | 112.09 (14) | C2—C17—H17A | 109.5 |
C3—C4—C7 | 110.55 (13) | C2—C17—H17B | 109.5 |
C5—C4—H4A | 108.1 | H17A—C17—H17B | 109.5 |
C3—C4—H4A | 108.1 | C2—C17—H17C | 109.5 |
C7—C4—H4A | 108.1 | H17A—C17—H17C | 109.5 |
C6—C5—C1 | 117.45 (16) | H17B—C17—H17C | 109.5 |
C6—C5—C4 | 122.48 (15) | O2—C18—O3 | 122.03 (16) |
C1—C5—C4 | 120.07 (15) | O2—C18—C3 | 122.77 (16) |
N1—C6—C5 | 127.75 (16) | O3—C18—C3 | 115.20 (15) |
N1—C6—O1 | 110.06 (14) | O3—C19—C20 | 105.69 (15) |
C5—C6—O1 | 122.19 (15) | O3—C19—H19A | 110.6 |
C8—C7—C16 | 118.85 (15) | C20—C19—H19A | 110.6 |
C8—C7—C4 | 119.98 (15) | O3—C19—H19B | 110.6 |
C16—C7—C4 | 121.15 (15) | C20—C19—H19B | 110.6 |
C7—C8—C9 | 122.26 (16) | H19A—C19—H19B | 108.7 |
C7—C8—H8A | 118.9 | O4—C20—C19 | 108.54 (15) |
C9—C8—H8A | 118.9 | O4—C20—H20A | 110.0 |
C10—C9—C8 | 120.14 (17) | C19—C20—H20A | 110.0 |
C10—C9—H9A | 119.9 | O4—C20—H20B | 110.0 |
C8—C9—H9A | 119.9 | C19—C20—H20B | 110.0 |
C9—C10—C11 | 120.33 (16) | H20A—C20—H20B | 108.4 |
C9—C10—H10A | 119.8 | O4—C21—H21A | 109.5 |
C11—C10—H10A | 119.8 | O4—C21—H21B | 109.5 |
C10—C11—C12 | 121.55 (16) | H21A—C21—H21B | 109.5 |
C10—C11—C16 | 119.98 (16) | O4—C21—H21C | 109.5 |
C12—C11—C16 | 118.46 (17) | H21A—C21—H21C | 109.5 |
C13—C12—C11 | 121.38 (17) | H21B—C21—H21C | 109.5 |
| | | |
C6—O1—C2—C3 | 5.7 (2) | C8—C9—C10—C11 | 1.6 (3) |
C6—O1—C2—C17 | −174.15 (14) | C9—C10—C11—C12 | −178.48 (17) |
O1—C2—C3—C18 | −178.53 (15) | C9—C10—C11—C16 | 0.3 (3) |
C17—C2—C3—C18 | 1.3 (3) | C10—C11—C12—C13 | −179.23 (18) |
O1—C2—C3—C4 | 1.7 (3) | C16—C11—C12—C13 | 2.0 (3) |
C17—C2—C3—C4 | −178.44 (17) | C11—C12—C13—C14 | 1.8 (3) |
C2—C3—C4—C5 | −8.6 (2) | C12—C13—C14—C15 | −3.4 (3) |
C18—C3—C4—C5 | 171.62 (14) | C13—C14—C15—C16 | 1.1 (3) |
C2—C3—C4—C7 | 115.52 (18) | C14—C15—C16—C11 | 2.7 (3) |
C18—C3—C4—C7 | −64.28 (18) | C14—C15—C16—C7 | −177.50 (16) |
C3—C4—C5—C6 | 9.4 (2) | C10—C11—C16—C15 | 177.02 (16) |
C7—C4—C5—C6 | −113.85 (18) | C12—C11—C16—C15 | −4.2 (2) |
C3—C4—C5—C1 | −170.67 (15) | C10—C11—C16—C7 | −2.8 (2) |
C7—C4—C5—C1 | 66.1 (2) | C12—C11—C16—C7 | 176.01 (15) |
C1—C5—C6—N1 | −3.9 (3) | C8—C7—C16—C15 | −176.38 (16) |
C4—C5—C6—N1 | 176.11 (16) | C4—C7—C16—C15 | 5.2 (2) |
C1—C5—C6—O1 | 176.71 (15) | C8—C7—C16—C11 | 3.4 (2) |
C4—C5—C6—O1 | −3.3 (3) | C4—C7—C16—C11 | −174.97 (14) |
C2—O1—C6—N1 | 175.55 (14) | C19—O3—C18—O2 | 5.5 (3) |
C2—O1—C6—C5 | −4.9 (2) | C19—O3—C18—C3 | −174.67 (15) |
C5—C4—C7—C8 | 85.72 (19) | C2—C3—C18—O2 | 171.95 (17) |
C3—C4—C7—C8 | −37.0 (2) | C4—C3—C18—O2 | −8.2 (2) |
C5—C4—C7—C16 | −95.89 (18) | C2—C3—C18—O3 | −7.9 (2) |
C3—C4—C7—C16 | 141.40 (15) | C4—C3—C18—O3 | 171.95 (14) |
C16—C7—C8—C9 | −1.6 (3) | C18—O3—C19—C20 | −179.18 (15) |
C4—C7—C8—C9 | 176.79 (15) | C21—O4—C20—C19 | 171.97 (15) |
C7—C8—C9—C10 | −0.9 (3) | O3—C19—C20—O4 | −61.9 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.88 | 2.05 | 2.931 (2) | 175 |
C4—H4A···O2ii | 1.00 | 2.56 | 3.463 (3) | 150 |
C17—H17B···N2iii | 0.98 | 2.61 | 3.552 (2) | 161 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
(III) isopropyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate
top
Crystal data top
C21H20N2O3 | Z = 2 |
Mr = 348.39 | F(000) = 368 |
Triclinic, P1 | Dx = 1.283 Mg m−3 |
a = 8.248 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.184 (4) Å | Cell parameters from 3217 reflections |
c = 11.394 (4) Å | θ = 3–28° |
α = 63.646 (7)° | µ = 0.09 mm−1 |
β = 73.836 (8)° | T = 100 K |
γ = 79.069 (7)° | Plate, colourless |
V = 901.9 (6) Å3 | 0.20 × 0.16 × 0.01 mm |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3528 independent reflections |
Radiation source: sealed tube | 2682 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.913, Tmax = 0.999 | k = −13→13 |
7635 measured reflections | l = −14→14 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.09P)2 + 0.15P] where P = (Fo2 + 2Fc2)/3 |
3528 reflections | (Δ/σ)max < 0.001 |
238 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C21H20N2O3 | γ = 79.069 (7)° |
Mr = 348.39 | V = 901.9 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.248 (3) Å | Mo Kα radiation |
b = 11.184 (4) Å | µ = 0.09 mm−1 |
c = 11.394 (4) Å | T = 100 K |
α = 63.646 (7)° | 0.20 × 0.16 × 0.01 mm |
β = 73.836 (8)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3528 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2682 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.999 | Rint = 0.030 |
7635 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.38 e Å−3 |
3528 reflections | Δρmin = −0.23 e Å−3 |
238 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.05122 (15) | 0.65181 (12) | 0.30744 (13) | 0.0294 (3) | |
O2 | 0.60896 (16) | 0.65576 (12) | 0.34502 (13) | 0.0295 (3) | |
O3 | 0.47402 (16) | 0.85241 (12) | 0.23516 (13) | 0.0312 (3) | |
N1 | −0.0734 (2) | 0.47542 (16) | 0.34278 (17) | 0.0340 (4) | |
H1A | −0.0784 | 0.3911 | 0.3601 | 0.041* | |
H1B | −0.1639 | 0.5317 | 0.3304 | 0.041* | |
N2 | 0.2231 (2) | 0.19285 (16) | 0.41998 (19) | 0.0427 (5) | |
C1 | 0.2254 (2) | 0.30610 (19) | 0.38873 (19) | 0.0298 (4) | |
C2 | 0.1845 (2) | 0.71550 (17) | 0.30085 (17) | 0.0254 (4) | |
C3 | 0.3402 (2) | 0.65344 (17) | 0.30871 (17) | 0.0237 (4) | |
C4 | 0.3826 (2) | 0.50766 (16) | 0.33128 (17) | 0.0236 (4) | |
H4A | 0.4250 | 0.4595 | 0.4160 | 0.028* | |
C5 | 0.2229 (2) | 0.44574 (17) | 0.35133 (17) | 0.0251 (4) | |
C6 | 0.0723 (2) | 0.51821 (17) | 0.33515 (17) | 0.0256 (4) | |
C7 | 0.5248 (2) | 0.49425 (17) | 0.21602 (17) | 0.0245 (4) | |
C8 | 0.5385 (2) | 0.59310 (18) | 0.08794 (18) | 0.0283 (4) | |
H8A | 0.4562 | 0.6672 | 0.0710 | 0.034* | |
C9 | 0.6716 (2) | 0.5875 (2) | −0.01914 (19) | 0.0326 (4) | |
H9A | 0.6783 | 0.6573 | −0.1067 | 0.039* | |
C10 | 0.7905 (2) | 0.4819 (2) | 0.0034 (2) | 0.0337 (5) | |
H10A | 0.8802 | 0.4789 | −0.0689 | 0.040* | |
C11 | 0.7824 (2) | 0.37653 (19) | 0.1331 (2) | 0.0301 (4) | |
C12 | 0.9087 (2) | 0.2675 (2) | 0.1591 (2) | 0.0381 (5) | |
H12A | 0.9994 | 0.2642 | 0.0876 | 0.046* | |
C13 | 0.9018 (3) | 0.1682 (2) | 0.2844 (2) | 0.0418 (5) | |
H13A | 0.9890 | 0.0977 | 0.3001 | 0.050* | |
C14 | 0.7654 (3) | 0.16945 (19) | 0.3913 (2) | 0.0374 (5) | |
H14A | 0.7595 | 0.0982 | 0.4780 | 0.045* | |
C15 | 0.6418 (2) | 0.27265 (18) | 0.37066 (19) | 0.0297 (4) | |
H15A | 0.5511 | 0.2720 | 0.4437 | 0.036* | |
C16 | 0.6463 (2) | 0.38131 (18) | 0.24169 (18) | 0.0261 (4) | |
C17 | 0.1162 (2) | 0.85348 (18) | 0.2884 (2) | 0.0308 (4) | |
H17A | 0.1963 | 0.8932 | 0.3077 | 0.046* | |
H17B | 0.0073 | 0.8488 | 0.3525 | 0.046* | |
H17C | 0.1001 | 0.9089 | 0.1969 | 0.046* | |
C18 | 0.4863 (2) | 0.71888 (17) | 0.29970 (17) | 0.0247 (4) | |
C19 | 0.6152 (2) | 0.92553 (19) | 0.2191 (2) | 0.0349 (5) | |
H19A | 0.6630 | 0.8819 | 0.3014 | 0.042* | |
C20 | 0.5363 (3) | 1.0642 (2) | 0.2024 (3) | 0.0554 (7) | |
H20A | 0.4498 | 1.0582 | 0.2833 | 0.083* | |
H20B | 0.4840 | 1.1040 | 0.1245 | 0.083* | |
H20C | 0.6240 | 1.1202 | 0.1885 | 0.083* | |
C21 | 0.7489 (3) | 0.9241 (3) | 0.0990 (2) | 0.0564 (7) | |
H21A | 0.7933 | 0.8317 | 0.1154 | 0.085* | |
H21B | 0.8411 | 0.9768 | 0.0835 | 0.085* | |
H21C | 0.6993 | 0.9630 | 0.0197 | 0.085* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0214 (6) | 0.0210 (6) | 0.0461 (8) | 0.0019 (5) | −0.0093 (5) | −0.0147 (6) |
O2 | 0.0235 (7) | 0.0269 (7) | 0.0390 (7) | 0.0031 (5) | −0.0103 (5) | −0.0144 (6) |
O3 | 0.0266 (7) | 0.0200 (6) | 0.0469 (8) | −0.0024 (5) | −0.0120 (6) | −0.0111 (6) |
N1 | 0.0220 (8) | 0.0270 (8) | 0.0564 (11) | 0.0008 (6) | −0.0096 (7) | −0.0208 (8) |
N2 | 0.0332 (10) | 0.0248 (9) | 0.0648 (12) | −0.0023 (7) | −0.0058 (8) | −0.0167 (8) |
C1 | 0.0225 (9) | 0.0262 (10) | 0.0383 (10) | −0.0021 (7) | −0.0034 (8) | −0.0131 (8) |
C2 | 0.0253 (9) | 0.0198 (9) | 0.0300 (9) | −0.0010 (7) | −0.0053 (7) | −0.0102 (7) |
C3 | 0.0250 (9) | 0.0195 (9) | 0.0261 (9) | 0.0001 (7) | −0.0046 (7) | −0.0103 (7) |
C4 | 0.0226 (9) | 0.0181 (9) | 0.0287 (9) | 0.0024 (7) | −0.0067 (7) | −0.0093 (7) |
C5 | 0.0244 (9) | 0.0199 (9) | 0.0292 (9) | −0.0015 (7) | −0.0033 (7) | −0.0102 (7) |
C6 | 0.0265 (9) | 0.0210 (9) | 0.0291 (9) | −0.0032 (7) | −0.0035 (7) | −0.0110 (7) |
C7 | 0.0212 (9) | 0.0236 (9) | 0.0326 (10) | −0.0016 (7) | −0.0067 (7) | −0.0148 (8) |
C8 | 0.0266 (9) | 0.0262 (9) | 0.0332 (10) | −0.0020 (7) | −0.0074 (7) | −0.0128 (8) |
C9 | 0.0320 (10) | 0.0342 (11) | 0.0329 (10) | −0.0074 (8) | −0.0047 (8) | −0.0147 (8) |
C10 | 0.0280 (10) | 0.0404 (11) | 0.0390 (11) | −0.0092 (8) | 0.0011 (8) | −0.0244 (9) |
C11 | 0.0217 (9) | 0.0306 (10) | 0.0474 (11) | −0.0020 (7) | −0.0064 (8) | −0.0252 (9) |
C12 | 0.0241 (10) | 0.0394 (12) | 0.0626 (14) | 0.0006 (8) | −0.0058 (9) | −0.0349 (11) |
C13 | 0.0315 (11) | 0.0280 (11) | 0.0744 (16) | 0.0094 (8) | −0.0181 (10) | −0.0294 (11) |
C14 | 0.0377 (11) | 0.0230 (10) | 0.0551 (13) | 0.0032 (8) | −0.0195 (10) | −0.0162 (9) |
C15 | 0.0283 (10) | 0.0235 (9) | 0.0410 (11) | 0.0006 (7) | −0.0108 (8) | −0.0159 (8) |
C16 | 0.0230 (9) | 0.0240 (9) | 0.0368 (10) | −0.0021 (7) | −0.0085 (7) | −0.0161 (8) |
C17 | 0.0256 (9) | 0.0215 (9) | 0.0442 (11) | 0.0015 (7) | −0.0065 (8) | −0.0146 (8) |
C18 | 0.0250 (9) | 0.0217 (9) | 0.0259 (9) | 0.0010 (7) | −0.0029 (7) | −0.0112 (7) |
C19 | 0.0315 (11) | 0.0287 (10) | 0.0450 (11) | −0.0096 (8) | −0.0128 (9) | −0.0102 (9) |
C20 | 0.0550 (15) | 0.0288 (12) | 0.0856 (18) | −0.0100 (11) | −0.0238 (13) | −0.0191 (12) |
C21 | 0.0429 (13) | 0.0662 (17) | 0.0543 (14) | −0.0233 (12) | −0.0008 (11) | −0.0181 (12) |
Geometric parameters (Å, º) top
O1—C6 | 1.370 (2) | C10—C11 | 1.416 (3) |
O1—C2 | 1.388 (2) | C10—H10A | 0.9500 |
O2—C18 | 1.219 (2) | C11—C12 | 1.425 (3) |
O3—C18 | 1.338 (2) | C11—C16 | 1.434 (3) |
O3—C19 | 1.472 (2) | C12—C13 | 1.358 (3) |
N1—C6 | 1.343 (2) | C12—H12A | 0.9500 |
N1—H1A | 0.8800 | C13—C14 | 1.412 (3) |
N1—H1B | 0.8800 | C13—H13A | 0.9500 |
N2—C1 | 1.156 (2) | C14—C15 | 1.369 (3) |
C1—C5 | 1.422 (3) | C14—H14A | 0.9500 |
C2—C3 | 1.345 (3) | C15—C16 | 1.428 (3) |
C2—C17 | 1.497 (2) | C15—H15A | 0.9500 |
C3—C18 | 1.482 (3) | C17—H17A | 0.9800 |
C3—C4 | 1.519 (2) | C17—H17B | 0.9800 |
C4—C5 | 1.518 (2) | C17—H17C | 0.9800 |
C4—C7 | 1.541 (2) | C19—C21 | 1.503 (3) |
C4—H4A | 1.0000 | C19—C20 | 1.513 (3) |
C5—C6 | 1.359 (3) | C19—H19A | 1.0000 |
C7—C8 | 1.374 (3) | C20—H20A | 0.9800 |
C7—C16 | 1.429 (3) | C20—H20B | 0.9800 |
C8—C9 | 1.412 (3) | C20—H20C | 0.9800 |
C8—H8A | 0.9500 | C21—H21A | 0.9800 |
C9—C10 | 1.362 (3) | C21—H21B | 0.9800 |
C9—H9A | 0.9500 | C21—H21C | 0.9800 |
| | | |
C6—O1—C2 | 119.73 (14) | C11—C12—H12A | 119.4 |
C18—O3—C19 | 118.20 (15) | C12—C13—C14 | 120.24 (19) |
C6—N1—H1A | 120.0 | C12—C13—H13A | 119.9 |
C6—N1—H1B | 120.0 | C14—C13—H13A | 119.9 |
H1A—N1—H1B | 120.0 | C15—C14—C13 | 120.4 (2) |
N2—C1—C5 | 178.3 (2) | C15—C14—H14A | 119.8 |
C3—C2—O1 | 122.08 (16) | C13—C14—H14A | 119.8 |
C3—C2—C17 | 130.89 (17) | C14—C15—C16 | 121.40 (18) |
O1—C2—C17 | 107.01 (14) | C14—C15—H15A | 119.3 |
C2—C3—C18 | 123.60 (16) | C16—C15—H15A | 119.3 |
C2—C3—C4 | 123.14 (16) | C15—C16—C7 | 123.66 (16) |
C18—C3—C4 | 113.25 (15) | C15—C16—C11 | 117.61 (17) |
C5—C4—C3 | 109.58 (14) | C7—C16—C11 | 118.72 (17) |
C5—C4—C7 | 112.98 (14) | C2—C17—H17A | 109.5 |
C3—C4—C7 | 110.87 (14) | C2—C17—H17B | 109.5 |
C5—C4—H4A | 107.7 | H17A—C17—H17B | 109.5 |
C3—C4—H4A | 107.7 | C2—C17—H17C | 109.5 |
C7—C4—H4A | 107.7 | H17A—C17—H17C | 109.5 |
C6—C5—C1 | 116.63 (16) | H17B—C17—H17C | 109.5 |
C6—C5—C4 | 122.90 (16) | O2—C18—O3 | 122.87 (16) |
C1—C5—C4 | 120.47 (15) | O2—C18—C3 | 122.58 (16) |
N1—C6—C5 | 127.81 (17) | O3—C18—C3 | 114.53 (15) |
N1—C6—O1 | 110.11 (15) | O3—C19—C21 | 108.28 (17) |
C5—C6—O1 | 122.08 (16) | O3—C19—C20 | 104.65 (16) |
C8—C7—C16 | 119.38 (16) | C21—C19—C20 | 113.47 (19) |
C8—C7—C4 | 120.07 (16) | O3—C19—H19A | 110.1 |
C16—C7—C4 | 120.52 (15) | C21—C19—H19A | 110.1 |
C7—C8—C9 | 121.77 (18) | C20—C19—H19A | 110.1 |
C7—C8—H8A | 119.1 | C19—C20—H20A | 109.5 |
C9—C8—H8A | 119.1 | C19—C20—H20B | 109.5 |
C10—C9—C8 | 119.87 (18) | H20A—C20—H20B | 109.5 |
C10—C9—H9A | 120.1 | C19—C20—H20C | 109.5 |
C8—C9—H9A | 120.1 | H20A—C20—H20C | 109.5 |
C9—C10—C11 | 120.92 (17) | H20B—C20—H20C | 109.5 |
C9—C10—H10A | 119.5 | C19—C21—H21A | 109.5 |
C11—C10—H10A | 119.5 | C19—C21—H21B | 109.5 |
C10—C11—C12 | 121.57 (18) | H21A—C21—H21B | 109.5 |
C10—C11—C16 | 119.31 (17) | C19—C21—H21C | 109.5 |
C12—C11—C16 | 119.10 (18) | H21A—C21—H21C | 109.5 |
C13—C12—C11 | 121.20 (19) | H21B—C21—H21C | 109.5 |
C13—C12—H12A | 119.4 | | |
| | | |
C6—O1—C2—C3 | 6.2 (2) | C8—C9—C10—C11 | 0.4 (3) |
C6—O1—C2—C17 | −172.29 (14) | C9—C10—C11—C12 | −178.00 (18) |
O1—C2—C3—C18 | 178.90 (15) | C9—C10—C11—C16 | 0.3 (3) |
C17—C2—C3—C18 | −3.0 (3) | C10—C11—C12—C13 | 178.65 (18) |
O1—C2—C3—C4 | −2.7 (3) | C16—C11—C12—C13 | 0.4 (3) |
C17—C2—C3—C4 | 175.40 (17) | C11—C12—C13—C14 | 1.7 (3) |
C2—C3—C4—C5 | −3.5 (2) | C12—C13—C14—C15 | −2.0 (3) |
C18—C3—C4—C5 | 175.09 (14) | C13—C14—C15—C16 | 0.1 (3) |
C2—C3—C4—C7 | 121.90 (18) | C14—C15—C16—C7 | −177.17 (17) |
C18—C3—C4—C7 | −59.53 (19) | C14—C15—C16—C11 | 1.9 (3) |
C3—C4—C5—C6 | 6.8 (2) | C8—C7—C16—C15 | −179.13 (16) |
C7—C4—C5—C6 | −117.34 (18) | C4—C7—C16—C15 | 2.7 (3) |
C3—C4—C5—C1 | −173.18 (15) | C8—C7—C16—C11 | 1.8 (3) |
C7—C4—C5—C1 | 62.7 (2) | C4—C7—C16—C11 | −176.40 (15) |
C1—C5—C6—N1 | −4.1 (3) | C10—C11—C16—C15 | 179.52 (16) |
C4—C5—C6—N1 | 175.88 (17) | C12—C11—C16—C15 | −2.2 (3) |
C1—C5—C6—O1 | 175.88 (15) | C10—C11—C16—C7 | −1.3 (3) |
C4—C5—C6—O1 | −4.1 (3) | C12—C11—C16—C7 | 176.99 (16) |
C2—O1—C6—N1 | 177.25 (14) | C19—O3—C18—O2 | −0.2 (2) |
C2—O1—C6—C5 | −2.8 (2) | C19—O3—C18—C3 | −178.76 (14) |
C5—C4—C7—C8 | 90.96 (19) | C2—C3—C18—O2 | 157.71 (17) |
C3—C4—C7—C8 | −32.5 (2) | C4—C3—C18—O2 | −20.8 (2) |
C5—C4—C7—C16 | −90.87 (19) | C2—C3—C18—O3 | −23.8 (2) |
C3—C4—C7—C16 | 145.69 (16) | C4—C3—C18—O3 | 157.69 (14) |
C16—C7—C8—C9 | −1.2 (3) | C18—O3—C19—C21 | 83.1 (2) |
C4—C7—C8—C9 | 177.00 (16) | C18—O3—C19—C20 | −155.61 (17) |
C7—C8—C9—C10 | 0.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.88 | 2.12 | 2.989 (2) | 168 |
C4—H4A···O2ii | 1.00 | 2.40 | 3.325 (3) | 154 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1. |
(IV) ethyl 6-amino-5-cyano-2-methyl-4-(1-naphthyl)-4
H-pyran-3-carboxylate
top
Crystal data top
C20H18N2O3 | F(000) = 704 |
Mr = 334.36 | Dx = 1.329 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8638 (7) Å | Cell parameters from 1424 reflections |
b = 19.4628 (18) Å | θ = 3–26° |
c = 11.0823 (10) Å | µ = 0.09 mm−1 |
β = 99.963 (2)° | T = 100 K |
V = 1670.6 (3) Å3 | Square prism, colourless |
Z = 4 | 0.20 × 0.16 × 0.14 mm |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3413 independent reflections |
Radiation source: sealed tube | 2184 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.918, Tmax = 0.987 | k = −24→24 |
14847 measured reflections | l = −13→13 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
3413 reflections | (Δ/σ)max < 0.001 |
228 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C20H18N2O3 | V = 1670.6 (3) Å3 |
Mr = 334.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.8638 (7) Å | µ = 0.09 mm−1 |
b = 19.4628 (18) Å | T = 100 K |
c = 11.0823 (10) Å | 0.20 × 0.16 × 0.14 mm |
β = 99.963 (2)° | |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 3413 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2184 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.987 | Rint = 0.078 |
14847 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
3413 reflections | Δρmin = −0.22 e Å−3 |
228 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.53777 (17) | 0.39813 (7) | 0.64463 (12) | 0.0215 (3) | |
O2 | 0.86631 (19) | 0.30531 (8) | 0.41465 (13) | 0.0352 (4) | |
O3 | 0.73719 (17) | 0.37998 (7) | 0.27323 (12) | 0.0219 (3) | |
N1 | 0.2869 (2) | 0.44364 (8) | 0.66878 (15) | 0.0227 (4) | |
H1A | 0.1842 | 0.4618 | 0.6442 | 0.027* | |
H1B | 0.3258 | 0.4380 | 0.7475 | 0.027* | |
N2 | 0.0548 (2) | 0.48391 (9) | 0.36791 (16) | 0.0269 (4) | |
C1 | 0.1846 (3) | 0.45905 (10) | 0.41101 (18) | 0.0196 (5) | |
C2 | 0.6565 (2) | 0.37264 (10) | 0.57571 (18) | 0.0198 (5) | |
C3 | 0.6282 (2) | 0.37528 (10) | 0.45345 (18) | 0.0183 (4) | |
C4 | 0.4663 (2) | 0.40611 (10) | 0.37885 (17) | 0.0165 (4) | |
H4A | 0.5012 | 0.4476 | 0.3357 | 0.020* | |
C5 | 0.3448 (2) | 0.42951 (10) | 0.46270 (18) | 0.0166 (4) | |
C6 | 0.3843 (2) | 0.42455 (10) | 0.58600 (18) | 0.0179 (5) | |
C7 | 0.3770 (2) | 0.35613 (10) | 0.28134 (17) | 0.0161 (4) | |
C8 | 0.3710 (3) | 0.28714 (10) | 0.30760 (19) | 0.0210 (5) | |
H8A | 0.4215 | 0.2713 | 0.3868 | 0.025* | |
C9 | 0.2917 (3) | 0.23945 (11) | 0.2197 (2) | 0.0249 (5) | |
H9A | 0.2902 | 0.1920 | 0.2399 | 0.030* | |
C10 | 0.2172 (3) | 0.26125 (11) | 0.10596 (19) | 0.0244 (5) | |
H10A | 0.1650 | 0.2288 | 0.0469 | 0.029* | |
C11 | 0.2170 (2) | 0.33197 (11) | 0.07480 (18) | 0.0207 (5) | |
C12 | 0.1334 (3) | 0.35551 (12) | −0.04164 (19) | 0.0276 (5) | |
H12A | 0.0783 | 0.3234 | −0.1003 | 0.033* | |
C13 | 0.1313 (3) | 0.42384 (12) | −0.0702 (2) | 0.0309 (6) | |
H13A | 0.0733 | 0.4391 | −0.1479 | 0.037* | |
C14 | 0.2147 (3) | 0.47149 (12) | 0.0150 (2) | 0.0294 (5) | |
H14A | 0.2149 | 0.5188 | −0.0061 | 0.035* | |
C15 | 0.2954 (3) | 0.45055 (11) | 0.12795 (19) | 0.0239 (5) | |
H15A | 0.3507 | 0.4836 | 0.1845 | 0.029* | |
C16 | 0.2985 (2) | 0.38032 (10) | 0.16258 (18) | 0.0185 (4) | |
C17 | 0.8089 (3) | 0.34687 (12) | 0.66342 (19) | 0.0280 (5) | |
H17A | 0.8960 | 0.3295 | 0.6177 | 0.042* | |
H17B | 0.7726 | 0.3097 | 0.7129 | 0.042* | |
H17C | 0.8581 | 0.3845 | 0.7172 | 0.042* | |
C18 | 0.7590 (2) | 0.34907 (11) | 0.38227 (18) | 0.0216 (5) | |
C19 | 0.8363 (3) | 0.35576 (11) | 0.18208 (18) | 0.0245 (5) | |
H19A | 0.9110 | 0.3168 | 0.2153 | 0.029* | |
H19B | 0.9107 | 0.3931 | 0.1600 | 0.029* | |
C20 | 0.7104 (3) | 0.33309 (12) | 0.0706 (2) | 0.0322 (6) | |
H20A | 0.7742 | 0.3161 | 0.0081 | 0.048* | |
H20B | 0.6383 | 0.3721 | 0.0377 | 0.048* | |
H20C | 0.6370 | 0.2963 | 0.0935 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0225 (7) | 0.0231 (8) | 0.0184 (8) | 0.0052 (6) | 0.0020 (6) | −0.0005 (6) |
O2 | 0.0325 (9) | 0.0421 (10) | 0.0322 (9) | 0.0203 (8) | 0.0087 (7) | 0.0080 (8) |
O3 | 0.0218 (7) | 0.0227 (8) | 0.0227 (8) | 0.0047 (6) | 0.0076 (6) | 0.0015 (6) |
N1 | 0.0236 (9) | 0.0268 (10) | 0.0181 (9) | 0.0059 (8) | 0.0048 (8) | 0.0012 (8) |
N2 | 0.0264 (10) | 0.0297 (11) | 0.0241 (10) | 0.0066 (8) | 0.0032 (8) | −0.0024 (8) |
C1 | 0.0227 (11) | 0.0196 (11) | 0.0167 (11) | −0.0002 (9) | 0.0042 (9) | −0.0044 (9) |
C2 | 0.0182 (10) | 0.0170 (11) | 0.0247 (12) | 0.0007 (9) | 0.0047 (9) | −0.0021 (9) |
C3 | 0.0173 (10) | 0.0155 (11) | 0.0217 (11) | 0.0001 (9) | 0.0023 (9) | −0.0008 (9) |
C4 | 0.0191 (10) | 0.0137 (10) | 0.0162 (11) | −0.0006 (8) | 0.0019 (8) | 0.0001 (8) |
C5 | 0.0165 (10) | 0.0140 (10) | 0.0189 (11) | 0.0016 (8) | 0.0020 (9) | −0.0022 (8) |
C6 | 0.0179 (10) | 0.0117 (10) | 0.0241 (12) | −0.0005 (8) | 0.0034 (9) | −0.0008 (8) |
C7 | 0.0125 (9) | 0.0187 (11) | 0.0173 (10) | 0.0002 (8) | 0.0030 (8) | −0.0027 (8) |
C8 | 0.0223 (11) | 0.0202 (11) | 0.0208 (11) | −0.0004 (9) | 0.0046 (9) | −0.0001 (9) |
C9 | 0.0271 (12) | 0.0157 (11) | 0.0338 (13) | −0.0041 (9) | 0.0106 (10) | −0.0036 (10) |
C10 | 0.0193 (11) | 0.0271 (12) | 0.0281 (13) | −0.0067 (9) | 0.0083 (10) | −0.0130 (10) |
C11 | 0.0136 (10) | 0.0295 (12) | 0.0199 (11) | −0.0012 (9) | 0.0053 (9) | −0.0068 (9) |
C12 | 0.0193 (11) | 0.0454 (15) | 0.0181 (11) | −0.0031 (10) | 0.0034 (9) | −0.0087 (11) |
C13 | 0.0255 (12) | 0.0499 (16) | 0.0172 (12) | 0.0049 (11) | 0.0036 (10) | 0.0048 (11) |
C14 | 0.0272 (12) | 0.0323 (13) | 0.0288 (13) | 0.0038 (10) | 0.0051 (10) | 0.0082 (11) |
C15 | 0.0228 (11) | 0.0253 (12) | 0.0227 (12) | 0.0007 (9) | 0.0013 (9) | 0.0005 (9) |
C16 | 0.0133 (9) | 0.0231 (11) | 0.0197 (11) | 0.0002 (9) | 0.0044 (8) | −0.0020 (9) |
C17 | 0.0245 (11) | 0.0340 (13) | 0.0232 (12) | 0.0076 (10) | −0.0023 (10) | −0.0018 (10) |
C18 | 0.0178 (11) | 0.0228 (12) | 0.0227 (12) | 0.0017 (9) | −0.0002 (9) | −0.0001 (9) |
C19 | 0.0239 (11) | 0.0270 (12) | 0.0253 (12) | 0.0029 (9) | 0.0116 (10) | 0.0009 (10) |
C20 | 0.0308 (13) | 0.0369 (14) | 0.0302 (13) | −0.0018 (11) | 0.0092 (11) | −0.0069 (11) |
Geometric parameters (Å, º) top
O1—C6 | 1.368 (2) | C9—H9A | 0.9500 |
O1—C2 | 1.395 (2) | C10—C11 | 1.419 (3) |
O2—C18 | 1.209 (2) | C10—H10A | 0.9500 |
O3—C18 | 1.334 (2) | C11—C12 | 1.419 (3) |
O3—C19 | 1.457 (2) | C11—C16 | 1.424 (3) |
N1—C6 | 1.346 (2) | C12—C13 | 1.366 (3) |
N1—H1A | 0.8800 | C12—H12A | 0.9500 |
N1—H1B | 0.8800 | C13—C14 | 1.403 (3) |
N2—C1 | 1.156 (2) | C13—H13A | 0.9500 |
C1—C5 | 1.413 (3) | C14—C15 | 1.364 (3) |
C2—C3 | 1.336 (3) | C14—H14A | 0.9500 |
C2—C17 | 1.493 (3) | C15—C16 | 1.419 (3) |
C3—C18 | 1.490 (3) | C15—H15A | 0.9500 |
C3—C4 | 1.517 (3) | C17—H17A | 0.9800 |
C4—C5 | 1.513 (3) | C17—H17B | 0.9800 |
C4—C7 | 1.531 (3) | C17—H17C | 0.9800 |
C4—H4A | 1.0000 | C19—C20 | 1.510 (3) |
C5—C6 | 1.351 (3) | C19—H19A | 0.9900 |
C7—C8 | 1.376 (3) | C19—H19B | 0.9900 |
C7—C16 | 1.433 (3) | C20—H20A | 0.9800 |
C8—C9 | 1.410 (3) | C20—H20B | 0.9800 |
C8—H8A | 0.9500 | C20—H20C | 0.9800 |
C9—C10 | 1.363 (3) | | |
| | | |
C6—O1—C2 | 119.48 (15) | C12—C11—C16 | 119.40 (19) |
C18—O3—C19 | 118.80 (16) | C13—C12—C11 | 120.7 (2) |
C6—N1—H1A | 120.0 | C13—C12—H12A | 119.7 |
C6—N1—H1B | 120.0 | C11—C12—H12A | 119.7 |
H1A—N1—H1B | 120.0 | C12—C13—C14 | 120.1 (2) |
N2—C1—C5 | 179.0 (2) | C12—C13—H13A | 119.9 |
C3—C2—O1 | 122.16 (17) | C14—C13—H13A | 119.9 |
C3—C2—C17 | 130.31 (19) | C15—C14—C13 | 120.6 (2) |
O1—C2—C17 | 107.50 (16) | C15—C14—H14A | 119.7 |
C2—C3—C18 | 121.01 (18) | C13—C14—H14A | 119.7 |
C2—C3—C4 | 122.99 (18) | C14—C15—C16 | 121.3 (2) |
C18—C3—C4 | 115.99 (17) | C14—C15—H15A | 119.4 |
C5—C4—C3 | 110.12 (16) | C16—C15—H15A | 119.4 |
C5—C4—C7 | 111.32 (15) | C15—C16—C11 | 117.86 (18) |
C3—C4—C7 | 111.87 (15) | C15—C16—C7 | 123.33 (18) |
C5—C4—H4A | 107.8 | C11—C16—C7 | 118.80 (18) |
C3—C4—H4A | 107.8 | C2—C17—H17A | 109.5 |
C7—C4—H4A | 107.8 | C2—C17—H17B | 109.5 |
C6—C5—C1 | 118.17 (18) | H17A—C17—H17B | 109.5 |
C6—C5—C4 | 122.69 (17) | C2—C17—H17C | 109.5 |
C1—C5—C4 | 119.13 (17) | H17A—C17—H17C | 109.5 |
N1—C6—C5 | 127.67 (18) | H17B—C17—H17C | 109.5 |
N1—C6—O1 | 109.86 (16) | O2—C18—O3 | 124.09 (19) |
C5—C6—O1 | 122.47 (18) | O2—C18—C3 | 126.46 (19) |
C8—C7—C16 | 119.32 (18) | O3—C18—C3 | 109.43 (17) |
C8—C7—C4 | 119.91 (17) | O3—C19—C20 | 107.98 (16) |
C16—C7—C4 | 120.76 (17) | O3—C19—H19A | 110.1 |
C7—C8—C9 | 121.55 (19) | C20—C19—H19A | 110.1 |
C7—C8—H8A | 119.2 | O3—C19—H19B | 110.1 |
C9—C8—H8A | 119.2 | C20—C19—H19B | 110.1 |
C10—C9—C8 | 120.1 (2) | H19A—C19—H19B | 108.4 |
C10—C9—H9A | 119.9 | C19—C20—H20A | 109.5 |
C8—C9—H9A | 119.9 | C19—C20—H20B | 109.5 |
C9—C10—C11 | 120.63 (19) | H20A—C20—H20B | 109.5 |
C9—C10—H10A | 119.7 | C19—C20—H20C | 109.5 |
C11—C10—H10A | 119.7 | H20A—C20—H20C | 109.5 |
C10—C11—C12 | 121.02 (19) | H20B—C20—H20C | 109.5 |
C10—C11—C16 | 119.56 (19) | | |
| | | |
C6—O1—C2—C3 | 2.4 (3) | C7—C8—C9—C10 | −0.5 (3) |
C6—O1—C2—C17 | −179.42 (16) | C8—C9—C10—C11 | −0.6 (3) |
O1—C2—C3—C18 | 178.63 (17) | C9—C10—C11—C12 | −177.28 (19) |
C17—C2—C3—C18 | 0.9 (3) | C9—C10—C11—C16 | 1.3 (3) |
O1—C2—C3—C4 | 0.2 (3) | C10—C11—C12—C13 | 178.9 (2) |
C17—C2—C3—C4 | −177.5 (2) | C16—C11—C12—C13 | 0.3 (3) |
C2—C3—C4—C5 | −2.2 (3) | C11—C12—C13—C14 | 1.0 (3) |
C18—C3—C4—C5 | 179.21 (16) | C12—C13—C14—C15 | −1.4 (3) |
C2—C3—C4—C7 | −126.6 (2) | C13—C14—C15—C16 | 0.3 (3) |
C18—C3—C4—C7 | 54.9 (2) | C14—C15—C16—C11 | 1.1 (3) |
C3—C4—C5—C6 | 2.1 (3) | C14—C15—C16—C7 | −178.00 (19) |
C7—C4—C5—C6 | 126.75 (19) | C10—C11—C16—C15 | −179.98 (18) |
C3—C4—C5—C1 | −179.19 (18) | C12—C11—C16—C15 | −1.4 (3) |
C7—C4—C5—C1 | −54.5 (2) | C10—C11—C16—C7 | −0.9 (3) |
C1—C5—C6—N1 | 1.2 (3) | C12—C11—C16—C7 | 177.75 (17) |
C4—C5—C6—N1 | 179.96 (18) | C8—C7—C16—C15 | 178.81 (19) |
C1—C5—C6—O1 | −178.54 (17) | C4—C7—C16—C15 | −0.9 (3) |
C4—C5—C6—O1 | 0.2 (3) | C8—C7—C16—C11 | −0.2 (3) |
C2—O1—C6—N1 | 177.60 (16) | C4—C7—C16—C11 | 179.99 (17) |
C2—O1—C6—C5 | −2.6 (3) | C19—O3—C18—O2 | 6.1 (3) |
C5—C4—C7—C8 | −85.3 (2) | C19—O3—C18—C3 | −172.06 (15) |
C3—C4—C7—C8 | 38.4 (2) | C2—C3—C18—O2 | 26.1 (3) |
C5—C4—C7—C16 | 94.4 (2) | C4—C3—C18—O2 | −155.4 (2) |
C3—C4—C7—C16 | −141.88 (18) | C2—C3—C18—O3 | −155.87 (18) |
C16—C7—C8—C9 | 1.0 (3) | C4—C3—C18—O3 | 22.7 (2) |
C4—C7—C8—C9 | −179.27 (17) | C18—O3—C19—C20 | 120.62 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.88 | 2.14 | 2.999 (2) | 165 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
| (II) | (III) | (IV) |
Crystal data |
Chemical formula | C21H20N2O4 | C21H20N2O3 | C20H18N2O3 |
Mr | 364.39 | 348.39 | 334.36 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 100 | 100 | 100 |
a, b, c (Å) | 8.245 (2), 10.962 (3), 11.008 (3) | 8.248 (3), 11.184 (4), 11.394 (4) | 7.8638 (7), 19.4628 (18), 11.0823 (10) |
α, β, γ (°) | 98.391 (7), 100.819 (8), 107.349 (7) | 63.646 (7), 73.836 (8), 79.069 (7) | 90, 99.963 (2), 90 |
V (Å3) | 910.9 (4) | 901.9 (6) | 1670.6 (3) |
Z | 2 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.22 × 0.17 × 0.14 | 0.20 × 0.16 × 0.01 | 0.20 × 0.16 × 0.14 |
|
Data collection |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.902, 0.987 | 0.913, 0.999 | 0.918, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7926, 3594, 2533 | 7635, 3528, 2682 | 14847, 3413, 2184 |
Rint | 0.029 | 0.030 | 0.078 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.111, 1.00 | 0.053, 0.148, 1.01 | 0.047, 0.111, 1.00 |
No. of reflections | 3594 | 3528 | 3413 |
No. of parameters | 246 | 238 | 228 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.26 | 0.38, −0.23 | 0.27, −0.22 |
Selected geometric parameters (Å, º) for (II) topO2—C18 | 1.215 (2) | C3—C18 | 1.481 (2) |
O3—C18 | 1.330 (2) | C4—C7 | 1.536 (2) |
N1—C6 | 1.340 (2) | C5—C6 | 1.353 (2) |
C2—C3 | 1.347 (2) | | |
| | | |
C2—C3—C18—O2 | 171.95 (17) | C2—C3—C18—O3 | −7.9 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.88 | 2.05 | 2.931 (2) | 175 |
C4—H4A···O2ii | 1.00 | 2.56 | 3.463 (3) | 150 |
C17—H17B···N2iii | 0.98 | 2.61 | 3.552 (2) | 161 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (III) topO2—C18 | 1.219 (2) | C3—C18 | 1.482 (3) |
O3—C18 | 1.338 (2) | C4—C7 | 1.541 (2) |
N1—C6 | 1.343 (2) | C5—C6 | 1.359 (3) |
C2—C3 | 1.345 (3) | | |
| | | |
C2—C3—C18—O2 | 157.71 (17) | C2—C3—C18—O3 | −23.8 (2) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O2i | 0.88 | 2.12 | 2.989 (2) | 168 |
C4—H4A···O2ii | 1.00 | 2.40 | 3.325 (3) | 154 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (IV) topO2—C18 | 1.209 (2) | C3—C18 | 1.490 (3) |
O3—C18 | 1.334 (2) | C4—C7 | 1.531 (3) |
N1—C6 | 1.346 (2) | C5—C6 | 1.351 (3) |
C2—C3 | 1.336 (3) | | |
| | | |
C2—C3—C18—O2 | 26.1 (3) | C2—C3—C18—O3 | −155.87 (18) |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.88 | 2.14 | 2.999 (2) | 165 |
Symmetry code: (i) −x, −y+1, −z+1. |
Geometric parameters (Å, °) for the heterocyclic rings in the
compounds (II)–(IV) topPlane/Compound | (II) | (III) | (IV) |
Δ(C2/C3/C5/C6)a | 0.004 (1) | 0.017 (1) | 0.001 (1) |
Displacement of O1 from plane | -0.054 (1) | -0.046 (1) | 0.026 (1) |
Displacement of C4 from plane | -0.115 (1) | -0.066 (1) | 0.028 (1) |
Hinge angle | | | |
O1—C4 | 7.8 (1) | 5.3 (1) | 2.5 (1) |
C2—C6 | 4.6 (1) | 3.9 (1) | 2.1 (1) |
C3—C5 | 7.5 (1) | 4.4 (1) | 1.8 (1) |
a Δ(C2/C3/C5/C6) is the r.m.s. deviation of the atoms from the
least-squares mean plane through the four atoms specified. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
The present investigation is a continuation of our work on the synthesis and structural study of sterically hindered heterocyclic compounds, such as 4H-pyran derivatives (Nesterov et al., 2004, 2005), 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) or potent apoptosis inducers (Kemnitzer et al., 2004; Zhang et al., 2005).
Synthesis and X-ray structural investigations have been carried out for compounds (II)–(IV) (Figs. 1–3) which were synthesized by the reaction of (1-naphthylmethylene)malononitrile, (I), with different β-ketoesters. Most of the geometric parameters in the molecules (Tables 2, 4 and 6) are very similar to standard values (Allen et al., 1987) and are very close to our previous data for sterically hindered 4H-pyran derivatives (Nesterov et al., 2004, 2005, and literature values cited therein).
X-ray analysis shows that the title molecules have similar structures, with the pyran ring adopting a flattened boat conformation (Table 1). The dihedral angles between the bulky pseudo-axial naphthalene substituent and the closest four atoms (C2/C3/C5/C6) of the pyran ring are 73.3 (1), 71.0 (1) and 74.3 (1)°, respectively. The mutual orientation of these fragments and the flatness of the heterocyclic rings lead to intramolecular H···H steric interactions: H4A···H15A = 2.08, 2.09 and 2.00 Å in (II)–(IV), respectively (Figs. 1–3). These contacts are shorter than the sum of the van der Waals radii of H atoms (2.2 Å; Rowland & Taylor, 1996). As in related compounds (Nesterov et al., 2004, 2005), such steric hindrance causes elongation of the C4—C7 bond to 1.536 (2), 1.541 (2) and 1.531 (3) Å, respectively, in comparison with neighbouring Csp3—Csp2 distances. The latter are only slightly longer than or are equal to the standard value (1.507 Å; Allen et al., 1987).
In (II) and (III), the C═O group adopts an anti orientation relative to the C2═C3 double bond [C2—C3—C18—O2 torsion angles are 172.0 (2) and 157.7 (2)°, respectively]. However, in (IV) it has a syn orientation [C2—C3—C18—O2 torsion angle is 26.1 (3)°]. As seen in Figs. 1–3, in (II) and (III) the O3 atoms of the ester groups and in (IV) atom O2 of the carbonyl group have favourable orientations for the formation of short steric intramolecular contacts with the methyl groups of the heterocyclic ring (O3/O2···H17A distances 2.08, 2.24 and 2.27 Å, respectively). According to literature data (Desiraju & Steiner 1999), these contacts can be considered weak hydrogen bonds. However, in these cases it can be difficult to distinguish between a weak intramolecular hydrogen bond and a contact which is enforced by the rigid molecular framework (Desiraju & Steiner, 1999). In each case, the contact connects the atoms into a six-membered ring. As in related compounds (Nesterov & Viltchinskaia, 2001; Nesterov et al., 2004), in all three title molecules there is conjugation between the donor NH2 and acceptor CN groups via the C5═C6 double bond. Thus, in all three molecules, the C6—N1 bonds are shorter than the average conjugated C—N single-bond length (1.370 Å; Allen, 2002), but variations in the other distances in these flat fragments are less distinct.
In all three compounds, only one H atom of the NH2 group is involved in an N—H···O [(II) and (III)] or N—H···N [(IV)] intermolecular hydrogen bond (Tables 3, 5 and 7) and chains along the a axis are formed in (II) and (III) (Figs. 4 and 5). In (IV), the syn orientation of the C═O group and its participation in the intramolecular steric contacts with the H atoms of the CH3 and CH2 groups (O2···H19A = 2.31 Å), and the different crystal packing, are reasons for the N—H···N hydrogen bonds forming centrosymmetric dimers in the crystal structure (Fig. 6). In addition, (II) exhibits weak C4—H4A··· O2 and C17—H17B···N2 interactions and in (III), C4—H4A··· O2 intermolecular hydrogen bonds link the chains along the a axis into ladders (Figs. 4 and 5; Tables 3 and 5).
Analysis of the crystal packing of the title compounds shows that in (II) and (III) there are short intermolecular steric contacts [C2···C2(1 - x, 1 - y, 1 - z) = 3.302 (3) Å and C10···C10(2 - x, -y, 1 - z) = 3.377 (3) Å in (II), and C8···C9(1 - x, 1 - y, -x) = 3.345 (3) Å in (III)] between atoms of the heterocycle or naphthalene fragments of neighbouring molecules which are less than the sum of the van der Waals radii of C (3.40 Å; Rowland & Taylor, 1996). In (IV), similar contacts are comparable with or slightly exceed the sum of the van der Waals radii of C. Such steric intermolecular contacts can play a role in determining the orientation of the bulky naphthalene substituents in the molecules and can be considered as π–π interactions between them in the crystal structures (Figs. 4 and 5). The other geometric parameters in compounds (II)–(IV) do not differ significantly from standard values (Allen et al., 1987).