Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199009257/fg1556sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199009257/fg1556Isup2.hkl |
CCDC reference: 140956
The title compound was synthesized from a solution of 4-N,N-diethylaminobenzylacetophenone (2.4 mmol), malononitrile (4.8 mmol) and a few drops of pyrrolidine (4.8 mmol) in ethanol refluxed for 25 h. The reaction mixture was concentrated under reduced pressure and purified by column chromatography over silica gel (m.p. 493–495 K) (Murugan et al., 2000). Single crystals were grown by slow evaporation of a methanol solution of the compound.
Naphthyridine derivatives have extensive pharmacological properties. These derivatives have anti-inflammatory (Di Braccio et al., 1997), antibacterial (against gram-positive organisms) (Hong et al., 1997), antitumour (Chen et al., 1997), cardiotonic (Mohan & Mishra, 1997), and anticonvulsant and insecticidal (Damon & Nadelson, 1981) properties. In addition, 1,6-naphthyridine derivatives are also used as novel potent adenosine 3',5'-cyclic phosphate phosphodiesterase III inhibitors (Singh et al., 1995). 1,6-Naphthyridine systems are known (Reed et al., 1988; Vinick, 1989) but few structural data have been reported (Balogh et al., 1986). The structure analysis of the title compound, (I), was carried out in order to determine the stereochemical and conformational changes induced by the substituents on the 1,6-naphthyridine ring system.
The molecule of (I) (Fig.1) consists of a 1,6-naphthyridine ring system substituted with five different chemical substituents, namely a phenyl ring, a diethylaminophenyl ring, a pyrrolidine ring, a cyano group and an amino group. The C25≡N4 bond length [1.145 (3) Å] and the C5—C25—N4 bond angle [177.5 (3)°] are comparable with previously reported values of 1.136 (9) Å and 177.2 (8)°, respectively, in a 1,6-naphthyridine derivative (Gomez de Anderez et al., 1992). The bond distances C1—C9 [1.491 (3) Å] and C3—C15 [1.489 (3) Å] are slightly longer than normal Csp2—Csp2 values. This is due to the π-electron repulsion of the bulky substituted phenyl rings at C1 and C3. The C—N and C—C distances in the structure agree well with literature values (Allen et al., 1987). The bond angles C1—C8—C7 [127.1 (2)°] and N5—C6—C5 [125.1 (2)°] are larger than the normal value of 120°. This is due to the steric interactions imposed by its substituents.
The naphthyridine ring system is almost planar and there is a dihedral angle of 5.4 (1)° between the pyridyl rings. The two phenyl rings substituted at C1 and C3 of the naphthyridine ring system are inclined at angles of 53.1 (1) and 19.8 (1)°, respectively. The dihedral angle between the pyrrolidine and naphthyridine rings is 20.9 (1)°. The pyrrolidine ring adopts a half-chair conformation which was confirmed using the ring-puckering parameters (Cremer & Pople, 1975) q2 = 0.342 (4) Å and φ2 = 91.6 (6)°, and the asymmetry parameter ΔC2(N5) = 0.006 (1) (Nardelli, 1983). The amino N3 atom deviates by 0.244 (3) Å from the mean plane of the 1,6-naphthyridine ring. The orientation of the substituents on the 1,6-naphthyridine ring may be described by using the following torsion angles at C1, C3 and C6: C2—C1—C9—C14 = -124.2 (3), C8—C1—C9—C10 = 51.7 (3), C2—C3—C15—C20 = -166.5 (3), N1—C3—C15—C16 - 158.8 (3), N2—C6—N5—C24 13.4 (4) and C5—C6—N5—C21 = -176.4 (2)°.
The structure is stabilized by weak intermolecular C—H···N interactions [C28—H28B 0.97, H28B···N1i 2.58, C28—N1i 3.478 (4) Å and C28—H28B···N1i 154°; symmetry code: (i) -x, 2 - y, 2 - z] in addition to van der Waals forces.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: PARST (Nardelli, 1995).
Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
C29H30N6 | Z = 2 |
Mr = 462.59 | F(000) = 492 |
Triclinic, P1 | Dx = 1.249 Mg m−3 |
a = 11.117 (3) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.1824 (11) Å | Cell parameters from 24 reflections |
c = 11.3444 (10) Å | θ = 3–25° |
α = 70.906 (8)° | µ = 0.08 mm−1 |
β = 83.953 (12)° | T = 290 K |
γ = 67.355 (12)° | Parallelepiped, yellow |
V = 1229.6 (3) Å3 | 0.63 × 0.36 × 0.30 mm |
Enraf-Nonius CAD-4 diffractometer | 2715 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω/2θ scans | h = −13→13 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = −12→13 |
Tmin = 0.954, Tmax = 0.978 | l = 0→13 |
4564 measured reflections | 3 standard reflections every 200 reflections |
4323 independent reflections | intensity decay: <3% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.02 | Calculated w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
4323 reflections | (Δ/σ)max < 0.001 |
316 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C29H30N6 | γ = 67.355 (12)° |
Mr = 462.59 | V = 1229.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.117 (3) Å | Mo Kα radiation |
b = 11.1824 (11) Å | µ = 0.08 mm−1 |
c = 11.3444 (10) Å | T = 290 K |
α = 70.906 (8)° | 0.63 × 0.36 × 0.30 mm |
β = 83.953 (12)° |
Enraf-Nonius CAD-4 diffractometer | 2715 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.039 |
Tmin = 0.954, Tmax = 0.978 | 3 standard reflections every 200 reflections |
4564 measured reflections | intensity decay: <3% |
4323 independent reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.35 e Å−3 |
4323 reflections | Δρmin = −0.20 e Å−3 |
316 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.3660 (2) | 0.9889 (2) | 1.16472 (18) | 0.0385 (5) | |
N2 | 0.4679 (2) | 0.7877 (2) | 0.89977 (19) | 0.0418 (5) | |
N3 | 0.3201 (2) | 0.9574 (2) | 0.7576 (2) | 0.0526 (6) | |
H3A | 0.3547 | 0.9140 | 0.7048 | 0.063* | |
H3B | 0.2550 | 1.0339 | 0.7350 | 0.063* | |
N4 | 0.6434 (3) | 0.7358 (3) | 1.2940 (2) | 0.0606 (7) | |
N5 | 0.6275 (2) | 0.6066 (2) | 1.0252 (2) | 0.0453 (6) | |
N6 | −0.2059 (2) | 1.2954 (2) | 0.5892 (2) | 0.0569 (7) | |
C1 | 0.1985 (2) | 1.0930 (3) | 0.9551 (2) | 0.0383 (6) | |
C2 | 0.1761 (2) | 1.1567 (3) | 1.0458 (2) | 0.0424 (7) | |
H2 | 0.1034 | 1.2365 | 1.0381 | 0.051* | |
C3 | 0.2606 (2) | 1.1032 (2) | 1.1487 (2) | 0.0371 (6) | |
C4 | 0.3929 (2) | 0.9254 (2) | 1.0762 (2) | 0.0356 (6) | |
C5 | 0.5047 (2) | 0.8017 (2) | 1.0985 (2) | 0.0371 (6) | |
C6 | 0.5331 (2) | 0.7315 (3) | 1.0109 (2) | 0.0373 (6) | |
C7 | 0.3678 (3) | 0.9058 (3) | 0.8753 (2) | 0.0394 (6) | |
C8 | 0.3149 (2) | 0.9762 (2) | 0.9667 (2) | 0.0359 (6) | |
C9 | 0.0954 (2) | 1.1462 (3) | 0.8567 (2) | 0.0396 (6) | |
C10 | 0.0429 (2) | 1.2822 (3) | 0.7881 (2) | 0.0420 (6) | |
H10 | 0.0758 | 1.3419 | 0.8009 | 0.050* | |
C11 | −0.0567 (3) | 1.3332 (3) | 0.7009 (2) | 0.0458 (7) | |
H11 | −0.0894 | 1.4259 | 0.6570 | 0.055* | |
C12 | −0.1094 (2) | 1.2469 (3) | 0.6777 (2) | 0.0425 (7) | |
C13 | −0.0566 (3) | 1.1091 (3) | 0.7487 (3) | 0.0511 (7) | |
H13 | −0.0890 | 1.0485 | 0.7368 | 0.061* | |
C14 | 0.0422 (3) | 1.0612 (3) | 0.8356 (3) | 0.0501 (7) | |
H14 | 0.0742 | 0.9690 | 0.8815 | 0.060* | |
C15 | 0.2355 (3) | 1.1614 (3) | 1.2536 (2) | 0.0409 (6) | |
C16 | 0.1132 (3) | 1.2505 (3) | 1.2732 (3) | 0.0604 (9) | |
H16 | 0.0451 | 1.2795 | 1.2167 | 0.072* | |
C17 | 0.0915 (3) | 1.2964 (4) | 1.3755 (3) | 0.0716 (10) | |
H17 | 0.0086 | 1.3548 | 1.3879 | 0.086* | |
C18 | 0.1905 (3) | 1.2570 (3) | 1.4589 (3) | 0.0632 (9) | |
H18 | 0.1754 | 1.2884 | 1.5276 | 0.076* | |
C19 | 0.3126 (3) | 1.1704 (3) | 1.4399 (3) | 0.0561 (8) | |
H19 | 0.3807 | 1.1443 | 1.4955 | 0.067* | |
C20 | 0.3349 (3) | 1.1222 (3) | 1.3395 (2) | 0.0479 (7) | |
H20 | 0.4177 | 1.0625 | 1.3287 | 0.058* | |
C21 | 0.6571 (3) | 0.5421 (3) | 0.9259 (3) | 0.0546 (8) | |
H21A | 0.6831 | 0.5978 | 0.8505 | 0.065* | |
H21B | 0.5826 | 0.5264 | 0.9066 | 0.065* | |
C22 | 0.7682 (4) | 0.4095 (4) | 0.9821 (3) | 0.0799 (11) | |
H22A | 0.7658 | 0.3388 | 0.9518 | 0.096* | |
H22B | 0.8512 | 0.4200 | 0.9613 | 0.096* | |
C23 | 0.7491 (3) | 0.3752 (3) | 1.1186 (3) | 0.0733 (10) | |
H23A | 0.8308 | 0.3161 | 1.1639 | 0.088* | |
H23B | 0.6869 | 0.3304 | 1.1436 | 0.088* | |
C24 | 0.6971 (3) | 0.5120 (3) | 1.1413 (3) | 0.0554 (8) | |
H24A | 0.6387 | 0.5119 | 1.2112 | 0.066* | |
H24B | 0.7676 | 0.5355 | 1.1579 | 0.066* | |
C25 | 0.5825 (3) | 0.7624 (3) | 1.2070 (3) | 0.0422 (7) | |
C26 | −0.2730 (3) | 1.4395 (3) | 0.5300 (3) | 0.0609 (8) | |
H26A | −0.3121 | 1.4531 | 0.4518 | 0.073* | |
H26B | −0.2100 | 1.4832 | 0.5108 | 0.073* | |
C27 | −0.3768 (4) | 1.5067 (4) | 0.6079 (4) | 0.0932 (13) | |
H27A | −0.4182 | 1.6019 | 0.5631 | 0.140* | |
H27B | −0.3384 | 1.4965 | 0.6843 | 0.140* | |
H27C | −0.4403 | 1.4648 | 0.6264 | 0.140* | |
C28 | −0.2618 (4) | 1.2050 (4) | 0.5687 (3) | 0.0778 (11) | |
H28A | −0.3523 | 1.2572 | 0.5420 | 0.093* | |
H28B | −0.2599 | 1.1349 | 0.6471 | 0.093* | |
C29 | −0.1929 (7) | 1.1395 (6) | 0.4750 (4) | 0.161 (3) | |
H29A | −0.2348 | 1.0827 | 0.4646 | 0.242* | |
H29B | −0.1040 | 1.0847 | 0.5023 | 0.242* | |
H29C | −0.1950 | 1.2082 | 0.3969 | 0.242* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0390 (12) | 0.0432 (13) | 0.0358 (12) | −0.0161 (10) | −0.0009 (9) | −0.0139 (10) |
N2 | 0.0443 (13) | 0.0443 (13) | 0.0375 (12) | −0.0152 (11) | −0.0019 (10) | −0.0142 (10) |
N3 | 0.0579 (15) | 0.0572 (15) | 0.0359 (13) | −0.0087 (12) | −0.0094 (11) | −0.0180 (11) |
N4 | 0.0647 (17) | 0.0613 (17) | 0.0488 (15) | −0.0141 (13) | −0.0195 (13) | −0.0133 (13) |
N5 | 0.0463 (13) | 0.0428 (13) | 0.0449 (13) | −0.0102 (11) | −0.0018 (11) | −0.0181 (11) |
N6 | 0.0555 (15) | 0.0601 (16) | 0.0534 (15) | −0.0248 (13) | −0.0238 (12) | −0.0041 (12) |
C1 | 0.0373 (14) | 0.0431 (15) | 0.0352 (14) | −0.0174 (12) | −0.0013 (11) | −0.0096 (12) |
C2 | 0.0342 (14) | 0.0458 (16) | 0.0452 (16) | −0.0102 (12) | −0.0025 (12) | −0.0162 (13) |
C3 | 0.0358 (14) | 0.0370 (14) | 0.0391 (14) | −0.0138 (12) | 0.0007 (12) | −0.0120 (11) |
C4 | 0.0363 (14) | 0.0405 (14) | 0.0332 (14) | −0.0181 (12) | −0.0006 (11) | −0.0106 (12) |
C5 | 0.0368 (14) | 0.0383 (14) | 0.0350 (14) | −0.0137 (12) | −0.0066 (11) | −0.0082 (12) |
C6 | 0.0355 (14) | 0.0399 (15) | 0.0387 (15) | −0.0164 (12) | 0.0013 (12) | −0.0122 (12) |
C7 | 0.0406 (15) | 0.0462 (16) | 0.0350 (15) | −0.0193 (13) | −0.0030 (12) | −0.0123 (12) |
C8 | 0.0387 (14) | 0.0372 (14) | 0.0343 (14) | −0.0180 (12) | −0.0017 (11) | −0.0089 (11) |
C9 | 0.0328 (14) | 0.0473 (16) | 0.0392 (15) | −0.0135 (12) | −0.0033 (11) | −0.0149 (13) |
C10 | 0.0368 (14) | 0.0414 (15) | 0.0484 (16) | −0.0121 (12) | −0.0057 (12) | −0.0157 (13) |
C11 | 0.0428 (16) | 0.0416 (15) | 0.0468 (16) | −0.0107 (13) | −0.0073 (13) | −0.0094 (13) |
C12 | 0.0374 (15) | 0.0535 (17) | 0.0379 (15) | −0.0191 (13) | −0.0048 (12) | −0.0118 (13) |
C13 | 0.0521 (17) | 0.0532 (18) | 0.0516 (17) | −0.0281 (15) | −0.0118 (14) | −0.0067 (14) |
C14 | 0.0496 (17) | 0.0478 (17) | 0.0492 (17) | −0.0194 (14) | −0.0122 (14) | −0.0048 (13) |
C15 | 0.0428 (15) | 0.0434 (15) | 0.0424 (15) | −0.0201 (13) | 0.0050 (12) | −0.0171 (12) |
C16 | 0.0453 (17) | 0.076 (2) | 0.067 (2) | −0.0139 (16) | −0.0003 (15) | −0.0404 (18) |
C17 | 0.060 (2) | 0.083 (2) | 0.081 (2) | −0.0175 (18) | 0.0144 (19) | −0.052 (2) |
C18 | 0.082 (2) | 0.069 (2) | 0.0539 (19) | −0.0340 (19) | 0.0114 (18) | −0.0340 (17) |
C19 | 0.062 (2) | 0.068 (2) | 0.0444 (17) | −0.0259 (17) | −0.0018 (15) | −0.0224 (15) |
C20 | 0.0450 (16) | 0.0571 (18) | 0.0430 (16) | −0.0192 (14) | −0.0037 (13) | −0.0155 (14) |
C21 | 0.0570 (19) | 0.0540 (18) | 0.0553 (18) | −0.0165 (15) | 0.0071 (15) | −0.0274 (15) |
C22 | 0.074 (2) | 0.064 (2) | 0.082 (3) | 0.0005 (19) | 0.010 (2) | −0.033 (2) |
C23 | 0.061 (2) | 0.056 (2) | 0.088 (3) | 0.0021 (16) | −0.0176 (19) | −0.0265 (19) |
C24 | 0.0465 (17) | 0.0512 (18) | 0.062 (2) | −0.0062 (14) | −0.0128 (15) | −0.0190 (15) |
C25 | 0.0442 (16) | 0.0394 (15) | 0.0399 (16) | −0.0128 (13) | 0.0001 (13) | −0.0117 (12) |
C26 | 0.0542 (19) | 0.067 (2) | 0.0554 (19) | −0.0206 (16) | −0.0179 (16) | −0.0079 (16) |
C27 | 0.060 (2) | 0.109 (3) | 0.103 (3) | −0.009 (2) | −0.015 (2) | −0.046 (3) |
C28 | 0.086 (3) | 0.084 (2) | 0.069 (2) | −0.052 (2) | −0.039 (2) | 0.0050 (19) |
C29 | 0.311 (9) | 0.171 (5) | 0.088 (3) | −0.170 (6) | 0.022 (4) | −0.060 (4) |
N1—C3 | 1.334 (3) | C15—C20 | 1.392 (4) |
N1—C4 | 1.357 (3) | C15—C16 | 1.389 (4) |
N2—C7 | 1.324 (3) | C16—C17 | 1.379 (4) |
N2—C6 | 1.354 (3) | C16—H16 | 0.9300 |
N3—C7 | 1.344 (3) | C17—C18 | 1.370 (5) |
N3—H3A | 0.8600 | C17—H17 | 0.9300 |
N3—H3B | 0.8600 | C18—C19 | 1.374 (4) |
N4—C25 | 1.145 (3) | C18—H18 | 0.9300 |
N5—C6 | 1.356 (3) | C19—C20 | 1.375 (4) |
N5—C24 | 1.458 (3) | C19—H19 | 0.9300 |
N5—C21 | 1.472 (3) | C20—H20 | 0.9300 |
N6—C12 | 1.370 (3) | C21—C22 | 1.506 (4) |
N6—C26 | 1.441 (4) | C21—H21A | 0.9700 |
N6—C28 | 1.458 (4) | C21—H21B | 0.9700 |
C1—C2 | 1.385 (3) | C22—C23 | 1.481 (5) |
C1—C8 | 1.421 (3) | C22—H22A | 0.9700 |
C1—C9 | 1.491 (3) | C22—H22B | 0.9700 |
C2—C3 | 1.394 (3) | C23—C24 | 1.513 (4) |
C2—H2 | 0.9300 | C23—H23A | 0.9700 |
C3—C15 | 1.489 (3) | C23—H23B | 0.9700 |
C4—C5 | 1.427 (3) | C24—H24A | 0.9700 |
C4—C8 | 1.415 (3) | C24—H24B | 0.9700 |
C5—C6 | 1.399 (3) | C26—C27 | 1.493 (5) |
C5—C25 | 1.427 (4) | C26—H26A | 0.9700 |
C7—C8 | 1.446 (3) | C26—H26B | 0.9700 |
C9—C14 | 1.387 (4) | C27—H27A | 0.9600 |
C9—C10 | 1.378 (4) | C27—H27B | 0.9600 |
C10—C11 | 1.380 (3) | C27—H27C | 0.9600 |
C10—H10 | 0.9300 | C28—C29 | 1.470 (6) |
C11—C12 | 1.407 (4) | C28—H28A | 0.9700 |
C11—H11 | 0.9300 | C28—H28B | 0.9700 |
C12—C13 | 1.399 (4) | C29—H29A | 0.9600 |
C13—C14 | 1.377 (4) | C29—H29B | 0.9600 |
C13—H13 | 0.9300 | C29—H29C | 0.9600 |
C14—H14 | 0.9300 | ||
C3—N1—C4 | 118.6 (2) | C18—C17—H17 | 119.6 |
C7—N2—C6 | 120.7 (2) | C16—C17—H17 | 119.6 |
C7—N3—H3A | 120.0 | C17—C18—C19 | 119.2 (3) |
C7—N3—H3B | 120.0 | C17—C18—H18 | 120.4 |
H3A—N3—H3B | 120.0 | C19—C18—H18 | 120.4 |
C6—N5—C24 | 125.9 (2) | C18—C19—C20 | 120.5 (3) |
C6—N5—C21 | 122.1 (2) | C18—C19—H19 | 119.7 |
C24—N5—C21 | 111.4 (2) | C20—C19—H19 | 119.7 |
C12—N6—C26 | 121.6 (2) | C15—C20—C19 | 121.0 (3) |
C12—N6—C28 | 120.8 (2) | C15—C20—H20 | 119.5 |
C26—N6—C28 | 116.6 (2) | C19—C20—H20 | 119.5 |
C2—C1—C8 | 117.5 (2) | N5—C21—C22 | 103.0 (2) |
C2—C1—C9 | 117.9 (2) | N5—C21—H21A | 111.2 |
C8—C1—C9 | 124.5 (2) | C22—C21—H21A | 111.2 |
C1—C2—C3 | 121.1 (2) | N5—C21—H21B | 111.2 |
C1—C2—H2 | 119.4 | C22—C21—H21B | 111.2 |
C3—C2—H2 | 119.4 | H21A—C21—H21B | 109.1 |
N1—C3—C2 | 122.0 (2) | C23—C22—C21 | 105.3 (3) |
N1—C3—C15 | 114.7 (2) | C23—C22—H22A | 110.7 |
C2—C3—C15 | 123.2 (2) | C21—C22—H22A | 110.7 |
N1—C4—C5 | 116.8 (2) | C23—C22—H22B | 110.7 |
N1—C4—C8 | 122.9 (2) | C21—C22—H22B | 110.7 |
C5—C4—C8 | 120.3 (2) | H22A—C22—H22B | 108.8 |
C6—C5—C4 | 118.3 (2) | C22—C23—C24 | 103.9 (3) |
C6—C5—C25 | 124.9 (2) | C22—C23—H23A | 111.0 |
C4—C5—C25 | 116.7 (2) | C24—C23—H23A | 111.0 |
N2—C6—N5 | 113.8 (2) | C22—C23—H23B | 111.0 |
N2—C6—C5 | 121.1 (2) | C24—C23—H23B | 111.0 |
N5—C6—C5 | 125.1 (2) | H23A—C23—H23B | 109.0 |
N2—C7—N3 | 114.9 (2) | N5—C24—C23 | 103.7 (2) |
N2—C7—C8 | 122.9 (2) | N5—C24—H24A | 111.0 |
N3—C7—C8 | 122.1 (2) | C23—C24—H24A | 111.0 |
C4—C8—C1 | 117.7 (2) | N5—C24—H24B | 111.0 |
C4—C8—C7 | 115.1 (2) | C23—C24—H24B | 111.0 |
C1—C8—C7 | 127.1 (2) | H24A—C24—H24B | 109.0 |
C14—C9—C10 | 116.8 (2) | N4—C25—C5 | 177.5 (3) |
C14—C9—C1 | 120.9 (2) | N6—C26—C27 | 113.5 (3) |
C10—C9—C1 | 122.2 (2) | N6—C26—H26A | 108.9 |
C11—C10—C9 | 122.5 (3) | C27—C26—H26A | 108.9 |
C11—C10—H10 | 118.8 | N6—C26—H26B | 108.9 |
C9—C10—H10 | 118.8 | C27—C26—H26B | 108.9 |
C10—C11—C12 | 120.9 (2) | H26A—C26—H26B | 107.7 |
C10—C11—H11 | 119.6 | C26—C27—H27A | 109.5 |
C12—C11—H11 | 119.6 | C26—C27—H27B | 109.5 |
N6—C12—C13 | 122.1 (2) | H27A—C27—H27B | 109.5 |
N6—C12—C11 | 121.6 (2) | C26—C27—H27C | 109.5 |
C13—C12—C11 | 116.3 (2) | H27A—C27—H27C | 109.5 |
C14—C13—C12 | 121.6 (3) | H27B—C27—H27C | 109.5 |
C14—C13—H13 | 119.2 | N6—C28—C29 | 113.3 (3) |
C12—C13—H13 | 119.2 | N6—C28—H28A | 108.9 |
C13—C14—C9 | 121.9 (3) | C29—C28—H28A | 108.9 |
C13—C14—H14 | 119.0 | N6—C28—H28B | 108.9 |
C9—C14—H14 | 119.0 | C29—C28—H28B | 108.9 |
C20—C15—C16 | 117.7 (3) | H28A—C28—H28B | 107.7 |
C20—C15—C3 | 120.0 (2) | C28—C29—H29A | 109.5 |
C16—C15—C3 | 122.2 (2) | C28—C29—H29B | 109.5 |
C15—C16—C17 | 120.7 (3) | H29A—C29—H29B | 109.5 |
C15—C16—H16 | 119.6 | C28—C29—H29C | 109.5 |
C17—C16—H16 | 119.6 | H29A—C29—H29C | 109.5 |
C18—C17—C16 | 120.8 (3) | H29B—C29—H29C | 109.5 |
C8—C1—C2—C3 | −3.9 (4) | C14—C9—C10—C11 | −0.8 (4) |
C9—C1—C2—C3 | 172.4 (2) | C1—C9—C10—C11 | −176.9 (2) |
C4—N1—C3—C2 | 1.7 (4) | C9—C10—C11—C12 | −0.2 (4) |
C4—N1—C3—C15 | 177.0 (2) | C26—N6—C12—C13 | 170.6 (3) |
C1—C2—C3—N1 | −0.1 (4) | C28—N6—C12—C13 | 2.5 (4) |
C1—C2—C3—C15 | −175.1 (2) | C26—N6—C12—C11 | −10.3 (4) |
C3—N1—C4—C5 | −178.4 (2) | C28—N6—C12—C11 | −178.4 (3) |
C3—N1—C4—C8 | 1.0 (3) | C10—C11—C12—N6 | −178.2 (2) |
N1—C4—C5—C6 | 178.3 (2) | C10—C11—C12—C13 | 0.9 (4) |
C8—C4—C5—C6 | −1.2 (4) | N6—C12—C13—C14 | 178.7 (3) |
N1—C4—C5—C25 | −4.5 (3) | C11—C12—C13—C14 | −0.5 (4) |
C8—C4—C5—C25 | 176.1 (2) | C12—C13—C14—C9 | −0.6 (4) |
C7—N2—C6—N5 | 175.9 (2) | C10—C9—C14—C13 | 1.3 (4) |
C7—N2—C6—C5 | −5.8 (4) | C1—C9—C14—C13 | 177.4 (3) |
C24—N5—C6—N2 | −168.4 (2) | N1—C3—C15—C20 | 18.3 (3) |
C21—N5—C6—N2 | 1.8 (4) | C2—C3—C15—C20 | −166.5 (3) |
C24—N5—C6—C5 | 13.4 (4) | N1—C3—C15—C16 | −158.8 (3) |
C21—N5—C6—C5 | −176.4 (2) | C2—C3—C15—C16 | 16.4 (4) |
C4—C5—C6—N2 | 8.9 (4) | C20—C15—C16—C17 | −0.9 (5) |
C25—C5—C6—N2 | −168.1 (2) | C3—C15—C16—C17 | 176.2 (3) |
C4—C5—C6—N5 | −173.0 (2) | C15—C16—C17—C18 | 1.1 (5) |
C25—C5—C6—N5 | 10.0 (4) | C16—C17—C18—C19 | −0.1 (5) |
C6—N2—C7—N3 | 173.3 (2) | C17—C18—C19—C20 | −1.0 (5) |
C6—N2—C7—C8 | −5.3 (4) | C16—C15—C20—C19 | −0.1 (4) |
N1—C4—C8—C1 | −4.9 (3) | C3—C15—C20—C19 | −177.4 (2) |
C5—C4—C8—C1 | 174.4 (2) | C18—C19—C20—C15 | 1.1 (5) |
N1—C4—C8—C7 | 171.9 (2) | C6—N5—C21—C22 | 178.6 (3) |
C5—C4—C8—C7 | −8.7 (3) | C24—N5—C21—C22 | −9.9 (3) |
C2—C1—C8—C4 | 6.1 (3) | N5—C21—C22—C23 | 28.6 (4) |
C9—C1—C8—C4 | −169.9 (2) | C21—C22—C23—C24 | −36.4 (4) |
C2—C1—C8—C7 | −170.3 (2) | C6—N5—C24—C23 | 159.0 (3) |
C9—C1—C8—C7 | 13.7 (4) | C21—N5—C24—C23 | −12.1 (3) |
N2—C7—C8—C4 | 12.3 (4) | C22—C23—C24—N5 | 29.5 (3) |
N3—C7—C8—C4 | −166.2 (2) | C6—C5—C25—N4 | 152 (6) |
N2—C7—C8—C1 | −171.1 (2) | C4—C5—C25—N4 | −25 (7) |
N3—C7—C8—C1 | 10.3 (4) | C12—N6—C26—C27 | −79.6 (4) |
C2—C1—C9—C14 | −124.2 (3) | C28—N6—C26—C27 | 89.0 (4) |
C8—C1—C9—C14 | 51.8 (4) | C12—N6—C28—C29 | −89.8 (4) |
C2—C1—C9—C10 | 51.7 (3) | C26—N6—C28—C29 | 101.5 (4) |
C8—C1—C9—C10 | −132.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C29H30N6 |
Mr | 462.59 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 290 |
a, b, c (Å) | 11.117 (3), 11.1824 (11), 11.3444 (10) |
α, β, γ (°) | 70.906 (8), 83.953 (12), 67.355 (12) |
V (Å3) | 1229.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.63 × 0.36 × 0.30 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.954, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4564, 4323, 2715 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.180, 1.02 |
No. of reflections | 4323 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.20 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), PARST (Nardelli, 1995).
N1—C3 | 1.334 (3) | N5—C6 | 1.356 (3) |
N1—C4 | 1.357 (3) | N5—C24 | 1.458 (3) |
N2—C7 | 1.324 (3) | N5—C21 | 1.472 (3) |
N2—C6 | 1.354 (3) | N6—C12 | 1.370 (3) |
N3—C7 | 1.344 (3) | N6—C26 | 1.441 (4) |
N4—C25 | 1.145 (3) | ||
C6—N5—C24 | 125.9 (2) | N1—C4—C8 | 122.9 (2) |
C6—N5—C21 | 122.1 (2) | C6—C5—C25 | 124.9 (2) |
C24—N5—C21 | 111.4 (2) | C4—C5—C25 | 116.7 (2) |
C26—N6—C28 | 116.6 (2) | N2—C6—N5 | 113.8 (2) |
C2—C1—C8 | 117.5 (2) | N5—C6—C5 | 125.1 (2) |
C2—C1—C9 | 117.9 (2) | C1—C8—C7 | 127.1 (2) |
C8—C1—C9 | 124.5 (2) | C14—C9—C10 | 116.8 (2) |
N1—C3—C15 | 114.7 (2) | N5—C24—C23 | 103.7 (2) |
C2—C3—C15 | 123.2 (2) | N4—C25—C5 | 177.5 (3) |
N1—C4—C5 | 116.8 (2) |
Naphthyridine derivatives have extensive pharmacological properties. These derivatives have anti-inflammatory (Di Braccio et al., 1997), antibacterial (against gram-positive organisms) (Hong et al., 1997), antitumour (Chen et al., 1997), cardiotonic (Mohan & Mishra, 1997), and anticonvulsant and insecticidal (Damon & Nadelson, 1981) properties. In addition, 1,6-naphthyridine derivatives are also used as novel potent adenosine 3',5'-cyclic phosphate phosphodiesterase III inhibitors (Singh et al., 1995). 1,6-Naphthyridine systems are known (Reed et al., 1988; Vinick, 1989) but few structural data have been reported (Balogh et al., 1986). The structure analysis of the title compound, (I), was carried out in order to determine the stereochemical and conformational changes induced by the substituents on the 1,6-naphthyridine ring system.
The molecule of (I) (Fig.1) consists of a 1,6-naphthyridine ring system substituted with five different chemical substituents, namely a phenyl ring, a diethylaminophenyl ring, a pyrrolidine ring, a cyano group and an amino group. The C25≡N4 bond length [1.145 (3) Å] and the C5—C25—N4 bond angle [177.5 (3)°] are comparable with previously reported values of 1.136 (9) Å and 177.2 (8)°, respectively, in a 1,6-naphthyridine derivative (Gomez de Anderez et al., 1992). The bond distances C1—C9 [1.491 (3) Å] and C3—C15 [1.489 (3) Å] are slightly longer than normal Csp2—Csp2 values. This is due to the π-electron repulsion of the bulky substituted phenyl rings at C1 and C3. The C—N and C—C distances in the structure agree well with literature values (Allen et al., 1987). The bond angles C1—C8—C7 [127.1 (2)°] and N5—C6—C5 [125.1 (2)°] are larger than the normal value of 120°. This is due to the steric interactions imposed by its substituents.
The naphthyridine ring system is almost planar and there is a dihedral angle of 5.4 (1)° between the pyridyl rings. The two phenyl rings substituted at C1 and C3 of the naphthyridine ring system are inclined at angles of 53.1 (1) and 19.8 (1)°, respectively. The dihedral angle between the pyrrolidine and naphthyridine rings is 20.9 (1)°. The pyrrolidine ring adopts a half-chair conformation which was confirmed using the ring-puckering parameters (Cremer & Pople, 1975) q2 = 0.342 (4) Å and φ2 = 91.6 (6)°, and the asymmetry parameter ΔC2(N5) = 0.006 (1) (Nardelli, 1983). The amino N3 atom deviates by 0.244 (3) Å from the mean plane of the 1,6-naphthyridine ring. The orientation of the substituents on the 1,6-naphthyridine ring may be described by using the following torsion angles at C1, C3 and C6: C2—C1—C9—C14 = -124.2 (3), C8—C1—C9—C10 = 51.7 (3), C2—C3—C15—C20 = -166.5 (3), N1—C3—C15—C16 - 158.8 (3), N2—C6—N5—C24 13.4 (4) and C5—C6—N5—C21 = -176.4 (2)°.
The structure is stabilized by weak intermolecular C—H···N interactions [C28—H28B 0.97, H28B···N1i 2.58, C28—N1i 3.478 (4) Å and C28—H28B···N1i 154°; symmetry code: (i) -x, 2 - y, 2 - z] in addition to van der Waals forces.