Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010100422X/na1495sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010100422X/na1495Isup2.hkl |
CCDC reference: 166982
For related literature, see: Allen et al. (1987); Brown et al. (1993); Chinnakali et al. (1998); Damon & Nadelson (1981); Domagala et al. (1993); Ferrarini et al. (1998); Govindasamy et al. (2000); Mohan & Mishra (1997); Nardelli (1999); Natsugari et al. (1999); Sankaranarayanan et al. (1999); Sheldrick (1997); Singh et al. (1995); Thirumurugan et al. (1999).
A solution of 4-methoxy-4'-hydroxybenzalacetophenone (2.4 mmol), malononitrile (4.8 mmol) and pyrrolidine (4.8 mmol) in ethanol (20 ml) was refluxed for 25 hrs. The solvent was removed under reduced pressure. The residue was purified by column chromatography. The solid thus obtained was recrystallized from ethanol-ethylacetate (1:1) solvent using slow evaporation technique.
The coordinates of hydroxyl H atom (H36) have been calculated with the computer program HYDROGEN (Nardelli, 1999). The calculated coordinates were 1.09571 0.80793 0.33758. By accepting these coordinates as such and keeping the distance between the O36 and H36 as 0.85 Å using the command DFIX in SHELXL (Sheldrick, 1997), the structure has been further refined. All other hydrogen atoms were included in calculated positions and allowed to ride on their corresponding parent atoms.
Naphthyridine derivatives constitute an important class of compounds possessing diverse types of biological properties. They have been reported as potential drugs for the treatment of bladder function disorders (Natsugari et al., 1999). They also possess anti-tumor (el-Subbah et al., 1999), antibacterial (Domagala et al., 1993), tuberculostatic (Ferrarini et al., 1998), cardio-tonic (Mohan & Mishra, 1997), anticonvulsant and insecticidal (Damon & Nadelson, 1981) properties. 1,6-Naphthyridine derivatives have been tested pharmacologically as potent antagonists at adrenoreceptors (Brown et al., 1993), they are also used as novel potent adenosine 3',5'-cyclic phosphate phosphodiesterase III inhibitors (Singh et al., 1995). As a continuation of the studies on 1,6-napthyridine derivatives (Sankaranarayanan et al., 1999) and to have a better understanding of the influence of structural and conformational change on its biological activity, the X-ray crystal structure analysis of the title compound, (I), has been carried out. \sch
The five rings of the molecule are identified as: A (C5,N6,C7—C10), B (N1,C2—C4,C10,C9), C (C19—C24), D (N14,C15—C18), E (C25—C30). The N—C and the other bond distances are comparable with the related structures previously studied (Sankaranarayanan et al., 1999; Thirumurugan et al., 1999; Govindasamy et al., 2000). The bond distance C5—N11 is shorter than the typical C—N single bond distance (1.47 Å) indicating conjugation of amino group with the aromatic system of naphthyridine. The naphthyridine ring is planar with the dihedral angle between the fused pyridine rings (rings A and B) being 1.9 (1)°.
The least squares plane through the phenyl rings make a dihedral angle of 1.9 (1) (ring C) and 89.5 (1)° (ring E) with the ring B to which they are attached indicating the perpendicular orientation of the ring E. The best plane through the pyrrolidine ring makes a dihedral angle of 11.3 (1)° with the pyridine ring (A). The sum of the bond angles around N14 and N31 are 359.6 (3) and 358.2 (3)°, respectively, indicating sp2 hybridization. The cyano bond distance C12≡N13 agrees well with the literature value of 1.138 (7) Å (Allen et al., 1987). The orientation of the diethyl substituent with respect to the phenyl ring (E) can be described by the torsional angles C28—N31—C32—C33 = -122.5 (3), C28—N31—C34—C35 = 82.0 (3)°. O36 is co-planar [C20—C21—C22—O36 = 177.3 (2)°] with the phenyl ring (C) to which it is attached. Due to steric interactions, bond angles C4—C10—C5 [127.3 (2)°], C8—C7—N14 [125.1 (2)°] are widened and the bond angles N1—C9—C8 [116.7 (2)°], N1—C2—C19 = 116.3 (2) are narrowed from 120° and these observations are also found in related structures (Chinnakali et al., 1998).
Apart from the normal van der Waals interactions, the molecular structure is stabilized by an intramolecular C—H···N type hydrogen bond and the molecular packing by the intermolecular N—H···O and O—H···N hydrogen bonds and C—H···π interaction (Table 2), where Cg1 is a centroid of ring E.
For related literature, see: Allen et al. (1987); Brown et al. (1993); Chinnakali et al. (1998); Damon & Nadelson (1981); Domagala et al. (1993); Ferrarini et al. (1998); Govindasamy et al. (2000); Mohan & Mishra (1997); Nardelli (1999); Natsugari et al. (1999); Sankaranarayanan et al. (1999); Sheldrick (1997); Singh et al. (1995); Thirumurugan et al. (1999).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
Fig. 1. Molecular structure showing 50% probability displacement ellipsoids with the atom-numbering scheme. |
C29H30N6O | Z = 2 |
Mr = 478.59 | F(000) = 508 |
Triclinic, P1 | Dx = 1.255 Mg m−3 |
a = 9.9502 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.3680 (2) Å | Cell parameters from 4453 reflections |
c = 12.4995 (2) Å | θ = 2.8–33.1° |
α = 94.692 (1)° | µ = 0.08 mm−1 |
β = 94.319 (1)° | T = 293 K |
γ = 98.505 (1)° | Block, yellow |
V = 1266.03 (4) Å3 | 0.42 × 0.38 × 0.32 mm |
Siemens SMART CCD area detector diffractometer | 3707 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 2.7° |
ω scans | h = −11→10 |
6716 measured reflections | k = −12→12 |
4298 independent reflections | l = −14→14 |
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) = 0.170 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.090P)2 + 0.5843P] where P = (Fo2 + 2Fc2)/3 |
4298 reflections | (Δ/σ)max < 0.001 |
329 parameters | Δρmax = 0.36 e Å−3 |
1 restraint | Δρmin = −0.36 e Å−3 |
C29H30N6O | γ = 98.505 (1)° |
Mr = 478.59 | V = 1266.03 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.9502 (2) Å | Mo Kα radiation |
b = 10.3680 (2) Å | µ = 0.08 mm−1 |
c = 12.4995 (2) Å | T = 293 K |
α = 94.692 (1)° | 0.42 × 0.38 × 0.32 mm |
β = 94.319 (1)° |
Siemens SMART CCD area detector diffractometer | 3707 reflections with I > 2σ(I) |
6716 measured reflections | Rint = 0.020 |
4298 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 1 restraint |
wR(F2) = 0.170 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.36 e Å−3 |
4298 reflections | Δρmin = −0.36 e Å−3 |
329 parameters |
Experimental. Data were collected over a hemisphere of reciprocal space, by a combination of three sets of exposures; each set had a different φ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set was over 99% complete. Crystal decay was monitored by repeating 30 initial frames at the end of data collection and analysing the duplicate reflections, it was found negligible. |
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 | 0.57700 (15) | 0.37368 (15) | 0.43346 (13) | 0.0417 (4) | |
C2 | 0.56388 (18) | 0.45321 (18) | 0.35720 (15) | 0.0409 (4) | |
C3 | 0.4413 (2) | 0.4458 (2) | 0.29186 (17) | 0.0486 (5) | |
H3 | 0.4345 | 0.5050 | 0.2404 | 0.058* | |
C4 | 0.33098 (19) | 0.35222 (18) | 0.30291 (16) | 0.0431 (4) | |
C5 | 0.24082 (19) | 0.16081 (19) | 0.40907 (17) | 0.0461 (5) | |
N6 | 0.25887 (16) | 0.08749 (16) | 0.48850 (15) | 0.0500 (4) | |
C7 | 0.3767 (2) | 0.10697 (19) | 0.55294 (16) | 0.0450 (4) | |
C8 | 0.48739 (18) | 0.20140 (19) | 0.53321 (15) | 0.0421 (4) | |
C9 | 0.46881 (18) | 0.28304 (18) | 0.44878 (15) | 0.0397 (4) | |
C10 | 0.34287 (18) | 0.26662 (18) | 0.38433 (16) | 0.0415 (4) | |
N11 | 0.11865 (18) | 0.13013 (19) | 0.35167 (18) | 0.0679 (6) | |
H11A | 0.0600 | 0.0670 | 0.3682 | 0.081* | |
H11B | 0.0992 | 0.1737 | 0.2984 | 0.081* | |
C12 | 0.6196 (2) | 0.2199 (2) | 0.58869 (16) | 0.0474 (5) | |
N13 | 0.72898 (19) | 0.2373 (2) | 0.62899 (17) | 0.0663 (6) | |
N14 | 0.37627 (17) | 0.02959 (17) | 0.63451 (15) | 0.0515 (4) | |
C15 | 0.2551 (2) | −0.0644 (2) | 0.6511 (2) | 0.0641 (6) | |
H15A | 0.2386 | −0.1359 | 0.5943 | 0.077* | |
H15B | 0.1748 | −0.0218 | 0.6532 | 0.077* | |
C16 | 0.2908 (4) | −0.1118 (4) | 0.7565 (3) | 0.1075 (12) | |
H16A | 0.2239 | −0.0933 | 0.8059 | 0.129* | |
H16B | 0.2886 | −0.2059 | 0.7474 | 0.129* | |
C17 | 0.4186 (4) | −0.0522 (5) | 0.7992 (3) | 0.1378 (19) | |
H17A | 0.4756 | −0.1183 | 0.8130 | 0.165* | |
H17B | 0.4115 | −0.0023 | 0.8671 | 0.165* | |
C18 | 0.4824 (2) | 0.0372 (3) | 0.7223 (2) | 0.0633 (6) | |
H18A | 0.5067 | 0.1261 | 0.7560 | 0.076* | |
H18B | 0.5633 | 0.0075 | 0.6969 | 0.076* | |
C19 | 0.68580 (19) | 0.55076 (18) | 0.34467 (15) | 0.0416 (4) | |
C20 | 0.8039 (2) | 0.5581 (2) | 0.41341 (16) | 0.0468 (5) | |
H20 | 0.8068 | 0.4991 | 0.4654 | 0.056* | |
C21 | 0.9171 (2) | 0.6510 (2) | 0.40619 (17) | 0.0489 (5) | |
H21 | 0.9948 | 0.6541 | 0.4532 | 0.059* | |
C22 | 0.91470 (19) | 0.73884 (18) | 0.32936 (18) | 0.0465 (5) | |
C23 | 0.7996 (2) | 0.7310 (2) | 0.25819 (19) | 0.0528 (5) | |
H23 | 0.7984 | 0.7882 | 0.2047 | 0.063* | |
C24 | 0.6870 (2) | 0.63865 (19) | 0.26630 (18) | 0.0489 (5) | |
H24 | 0.6101 | 0.6350 | 0.2183 | 0.059* | |
C25 | 0.20639 (19) | 0.34633 (18) | 0.22683 (16) | 0.0438 (4) | |
C26 | 0.1037 (2) | 0.4193 (2) | 0.24879 (17) | 0.0522 (5) | |
H26 | 0.1127 | 0.4741 | 0.3125 | 0.063* | |
C27 | −0.0112 (2) | 0.4125 (2) | 0.17857 (17) | 0.0521 (5) | |
H27 | −0.0785 | 0.4619 | 0.1965 | 0.063* | |
C28 | −0.0293 (2) | 0.3329 (2) | 0.08068 (16) | 0.0481 (5) | |
C29 | 0.0751 (2) | 0.2598 (2) | 0.05904 (19) | 0.0602 (6) | |
H29 | 0.0667 | 0.2045 | −0.0043 | 0.072* | |
C30 | 0.1896 (2) | 0.2682 (2) | 0.12968 (19) | 0.0582 (6) | |
H30 | 0.2579 | 0.2201 | 0.1118 | 0.070* | |
N31 | −0.1439 (2) | 0.3241 (2) | 0.00989 (16) | 0.0658 (5) | |
C32 | −0.2421 (3) | 0.4153 (3) | 0.0209 (3) | 0.0909 (10) | |
H32A | −0.2119 | 0.4766 | 0.0840 | 0.109* | |
H32B | −0.2420 | 0.4652 | −0.0414 | 0.109* | |
C33 | −0.3797 (4) | 0.3548 (5) | 0.0309 (5) | 0.1393 (18) | |
H33A | −0.4373 | 0.4210 | 0.0373 | 0.209* | |
H33B | −0.3818 | 0.3075 | 0.0938 | 0.209* | |
H33C | −0.4118 | 0.2953 | −0.0319 | 0.209* | |
C34 | −0.1551 (3) | 0.2462 (3) | −0.0928 (2) | 0.0727 (7) | |
H34A | −0.0670 | 0.2579 | −0.1220 | 0.087* | |
H34B | −0.2192 | 0.2786 | −0.1423 | 0.087* | |
C35 | −0.2010 (4) | 0.1021 (3) | −0.0870 (3) | 0.0954 (10) | |
H35A | −0.2061 | 0.0569 | −0.1577 | 0.143* | |
H35B | −0.2893 | 0.0892 | −0.0599 | 0.143* | |
H35C | −0.1369 | 0.0684 | −0.0398 | 0.143* | |
O36 | 1.02009 (16) | 0.83594 (15) | 0.32032 (15) | 0.0636 (5) | |
H36 | 1.091 (3) | 0.810 (3) | 0.349 (3) | 0.110 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0345 (8) | 0.0418 (8) | 0.0472 (9) | 0.0000 (6) | 0.0036 (6) | 0.0067 (7) |
C2 | 0.0361 (9) | 0.0398 (9) | 0.0453 (10) | 0.0021 (8) | 0.0029 (8) | 0.0025 (8) |
C3 | 0.0430 (11) | 0.0480 (11) | 0.0532 (11) | −0.0001 (8) | −0.0012 (9) | 0.0129 (9) |
C4 | 0.0369 (9) | 0.0414 (10) | 0.0490 (11) | 0.0021 (8) | 0.0000 (8) | 0.0028 (8) |
C5 | 0.0370 (10) | 0.0426 (10) | 0.0561 (12) | −0.0008 (8) | 0.0012 (8) | 0.0053 (9) |
N6 | 0.0379 (9) | 0.0476 (9) | 0.0622 (11) | −0.0030 (7) | 0.0016 (8) | 0.0109 (8) |
C7 | 0.0391 (10) | 0.0443 (10) | 0.0514 (11) | 0.0038 (8) | 0.0064 (8) | 0.0069 (8) |
C8 | 0.0352 (9) | 0.0448 (10) | 0.0463 (10) | 0.0039 (8) | 0.0038 (8) | 0.0075 (8) |
C9 | 0.0332 (9) | 0.0399 (9) | 0.0448 (10) | 0.0024 (7) | 0.0047 (7) | 0.0020 (8) |
C10 | 0.0356 (9) | 0.0386 (9) | 0.0484 (10) | 0.0016 (8) | 0.0021 (8) | 0.0011 (8) |
N11 | 0.0449 (10) | 0.0633 (12) | 0.0869 (14) | −0.0196 (9) | −0.0170 (9) | 0.0278 (10) |
C12 | 0.0400 (11) | 0.0520 (11) | 0.0499 (11) | 0.0006 (8) | 0.0037 (9) | 0.0142 (9) |
N13 | 0.0425 (10) | 0.0824 (14) | 0.0713 (13) | −0.0039 (9) | −0.0069 (9) | 0.0275 (11) |
N14 | 0.0419 (9) | 0.0542 (10) | 0.0588 (10) | 0.0005 (7) | 0.0069 (8) | 0.0188 (8) |
C15 | 0.0567 (13) | 0.0601 (13) | 0.0741 (15) | −0.0073 (11) | 0.0141 (11) | 0.0201 (12) |
C16 | 0.101 (2) | 0.122 (3) | 0.093 (2) | −0.029 (2) | 0.0064 (18) | 0.060 (2) |
C17 | 0.083 (2) | 0.204 (4) | 0.118 (3) | −0.044 (3) | −0.021 (2) | 0.114 (3) |
C18 | 0.0532 (13) | 0.0720 (15) | 0.0662 (14) | 0.0025 (11) | 0.0047 (11) | 0.0301 (12) |
C19 | 0.0365 (10) | 0.0406 (10) | 0.0463 (10) | 0.0013 (8) | 0.0042 (8) | 0.0032 (8) |
C20 | 0.0417 (10) | 0.0488 (11) | 0.0485 (11) | 0.0003 (8) | 0.0026 (8) | 0.0109 (9) |
C21 | 0.0369 (10) | 0.0523 (11) | 0.0548 (12) | −0.0012 (8) | 0.0003 (8) | 0.0061 (9) |
C22 | 0.0371 (10) | 0.0382 (10) | 0.0636 (12) | 0.0006 (8) | 0.0098 (9) | 0.0055 (9) |
C23 | 0.0478 (11) | 0.0470 (11) | 0.0647 (13) | 0.0033 (9) | 0.0055 (10) | 0.0197 (10) |
C24 | 0.0393 (10) | 0.0477 (11) | 0.0589 (12) | 0.0030 (8) | −0.0017 (9) | 0.0118 (9) |
C25 | 0.0384 (10) | 0.0421 (10) | 0.0487 (11) | 0.0000 (8) | −0.0016 (8) | 0.0073 (8) |
C26 | 0.0531 (12) | 0.0528 (12) | 0.0482 (11) | 0.0089 (9) | −0.0041 (9) | −0.0042 (9) |
C27 | 0.0461 (11) | 0.0542 (12) | 0.0556 (12) | 0.0138 (9) | −0.0047 (9) | −0.0003 (9) |
C28 | 0.0424 (10) | 0.0516 (11) | 0.0476 (11) | 0.0007 (8) | −0.0035 (8) | 0.0081 (9) |
C29 | 0.0545 (13) | 0.0696 (14) | 0.0515 (12) | 0.0071 (11) | −0.0038 (10) | −0.0120 (10) |
C30 | 0.0461 (12) | 0.0625 (13) | 0.0636 (13) | 0.0117 (10) | −0.0019 (10) | −0.0068 (11) |
N31 | 0.0580 (11) | 0.0751 (13) | 0.0603 (12) | 0.0157 (10) | −0.0199 (9) | −0.0050 (10) |
C32 | 0.0761 (19) | 0.094 (2) | 0.098 (2) | 0.0290 (16) | −0.0347 (16) | −0.0123 (17) |
C33 | 0.104 (3) | 0.127 (3) | 0.208 (5) | 0.045 (3) | 0.053 (3) | 0.055 (3) |
C34 | 0.0722 (16) | 0.0873 (18) | 0.0524 (13) | 0.0064 (14) | −0.0156 (12) | −0.0008 (12) |
C35 | 0.097 (2) | 0.086 (2) | 0.090 (2) | −0.0018 (17) | −0.0158 (17) | −0.0208 (17) |
O36 | 0.0425 (8) | 0.0505 (9) | 0.0960 (13) | −0.0062 (7) | 0.0051 (8) | 0.0215 (8) |
N1—C2 | 1.322 (2) | C20—C21 | 1.383 (3) |
N1—C9 | 1.357 (2) | C20—H20 | 0.9300 |
C2—C3 | 1.405 (3) | C21—C22 | 1.378 (3) |
C2—C19 | 1.487 (3) | C21—H21 | 0.9300 |
C3—C4 | 1.377 (3) | C22—O36 | 1.360 (2) |
C3—H3 | 0.9300 | C22—C23 | 1.384 (3) |
C4—C10 | 1.414 (3) | C23—C24 | 1.378 (3) |
C4—C25 | 1.495 (3) | C23—H23 | 0.9300 |
C5—N6 | 1.316 (3) | C24—H24 | 0.9300 |
C5—N11 | 1.346 (3) | C25—C30 | 1.388 (3) |
C5—C10 | 1.450 (3) | C25—C26 | 1.389 (3) |
N6—C7 | 1.351 (3) | C26—C27 | 1.378 (3) |
C7—N14 | 1.348 (3) | C26—H26 | 0.9300 |
C7—C8 | 1.412 (3) | C27—C28 | 1.403 (3) |
C8—C12 | 1.419 (3) | C27—H27 | 0.9300 |
C8—C9 | 1.424 (3) | C28—N31 | 1.377 (3) |
C9—C10 | 1.418 (3) | C28—C29 | 1.403 (3) |
N11—H11A | 0.8600 | C29—C30 | 1.376 (3) |
N11—H11B | 0.8600 | C29—H29 | 0.9300 |
C12—N13 | 1.147 (3) | C30—H30 | 0.9300 |
N14—C18 | 1.453 (3) | N31—C34 | 1.447 (3) |
N14—C15 | 1.473 (3) | N31—C32 | 1.463 (3) |
C15—C16 | 1.480 (4) | C32—C33 | 1.438 (5) |
C15—H15A | 0.9700 | C32—H32A | 0.9700 |
C15—H15B | 0.9700 | C32—H32B | 0.9700 |
C16—C17 | 1.377 (4) | C33—H33A | 0.9600 |
C16—H16A | 0.9700 | C33—H33B | 0.9600 |
C16—H16B | 0.9700 | C33—H33C | 0.9600 |
C17—C18 | 1.500 (4) | C34—C35 | 1.505 (4) |
C17—H17A | 0.9700 | C34—H34A | 0.9700 |
C17—H17B | 0.9700 | C34—H34B | 0.9700 |
C18—H18A | 0.9700 | C35—H35A | 0.9600 |
C18—H18B | 0.9700 | C35—H35B | 0.9600 |
C19—C24 | 1.391 (3) | C35—H35C | 0.9600 |
C19—C20 | 1.391 (3) | O36—H36 | 0.85 (2) |
C2—N1—C9 | 118.9 (2) | C21—C20—H20 | 119.2 |
N1—C2—C3 | 121.7 (2) | C19—C20—H20 | 119.2 |
N1—C2—C19 | 116.3 (2) | C22—C21—C20 | 120.0 (2) |
C3—C2—C19 | 122.0 (2) | C22—C21—H21 | 120.0 |
C4—C3—C2 | 121.0 (2) | C20—C21—H21 | 120.0 |
C4—C3—H3 | 119.5 | O36—C22—C21 | 123.2 (2) |
C2—C3—H3 | 119.5 | O36—C22—C23 | 117.4 (2) |
C3—C4—C10 | 118.2 (2) | C21—C22—C23 | 119.4 (2) |
C3—C4—C25 | 117.8 (2) | C24—C23—C22 | 120.2 (2) |
C10—C4—C25 | 124.0 (2) | C24—C23—H23 | 119.9 |
N6—C5—N11 | 114.5 (2) | C22—C23—H23 | 119.9 |
N6—C5—C10 | 123.5 (2) | C23—C24—C19 | 121.4 (2) |
N11—C5—C10 | 122.0 (2) | C23—C24—H24 | 119.3 |
C5—N6—C7 | 121.1 (2) | C19—C24—H24 | 119.3 |
N14—C7—N6 | 114.0 (2) | C30—C25—C26 | 117.0 (2) |
N14—C7—C8 | 125.1 (2) | C30—C25—C4 | 120.9 (2) |
N6—C7—C8 | 121.0 (2) | C26—C25—C4 | 122.0 (2) |
C7—C8—C12 | 125.3 (2) | C27—C26—C25 | 121.6 (2) |
C7—C8—C9 | 118.5 (2) | C27—C26—H26 | 119.2 |
C12—C8—C9 | 116.1 (2) | C25—C26—H26 | 119.2 |
N1—C9—C10 | 123.0 (2) | C26—C27—C28 | 121.6 (2) |
N1—C9—C8 | 116.7 (2) | C26—C27—H27 | 119.2 |
C10—C9—C8 | 120.4 (2) | C28—C27—H27 | 119.2 |
C4—C10—C9 | 117.3 (2) | N31—C28—C27 | 122.4 (2) |
C4—C10—C5 | 127.3 (2) | N31—C28—C29 | 121.2 (2) |
C9—C10—C5 | 115.4 (2) | C27—C28—C29 | 116.4 (2) |
C5—N11—H11A | 120.0 | C30—C29—C28 | 121.3 (2) |
C5—N11—H11B | 120.0 | C30—C29—H29 | 119.3 |
H11A—N11—H11B | 120.0 | C28—C29—H29 | 119.3 |
N13—C12—C8 | 176.5 (2) | C29—C30—C25 | 122.0 (2) |
C7—N14—C18 | 126.3 (2) | C29—C30—H30 | 119.0 |
C7—N14—C15 | 121.7 (2) | C25—C30—H30 | 119.0 |
C18—N14—C15 | 111.6 (2) | C28—N31—C34 | 120.5 (2) |
N14—C15—C16 | 103.7 (2) | C28—N31—C32 | 122.0 (2) |
N14—C15—H15A | 111.0 | C34—N31—C32 | 115.7 (2) |
C16—C15—H15A | 111.0 | C33—C32—N31 | 114.8 (3) |
N14—C15—H15B | 111.0 | C33—C32—H32A | 108.6 |
C16—C15—H15B | 111.0 | N31—C32—H32A | 108.6 |
H15A—C15—H15B | 109.0 | C33—C32—H32B | 108.6 |
C17—C16—C15 | 110.8 (2) | N31—C32—H32B | 108.6 |
C17—C16—H16A | 109.5 | H32A—C32—H32B | 107.5 |
C15—C16—H16A | 109.5 | C32—C33—H33A | 109.5 |
C17—C16—H16B | 109.5 | C32—C33—H33B | 109.5 |
C15—C16—H16B | 109.5 | H33A—C33—H33B | 109.5 |
H16A—C16—H16B | 108.1 | C32—C33—H33C | 109.5 |
C16—C17—C18 | 110.1 (3) | H33A—C33—H33C | 109.5 |
C16—C17—H17A | 109.6 | H33B—C33—H33C | 109.5 |
C18—C17—H17A | 109.6 | N31—C34—C35 | 114.2 (2) |
C16—C17—H17B | 109.6 | N31—C34—H34A | 108.7 |
C18—C17—H17B | 109.6 | C35—C34—H34A | 108.7 |
H17A—C17—H17B | 108.2 | N31—C34—H34B | 108.7 |
N14—C18—C17 | 103.7 (2) | C35—C34—H34B | 108.7 |
N14—C18—H18A | 111.0 | H34A—C34—H34B | 107.6 |
C17—C18—H18A | 111.0 | C34—C35—H35A | 109.5 |
N14—C18—H18B | 111.0 | C34—C35—H35B | 109.5 |
C17—C18—H18B | 111.0 | H35A—C35—H35B | 109.5 |
H18A—C18—H18B | 109.0 | C34—C35—H35C | 109.5 |
C24—C19—C20 | 117.4 (2) | H35A—C35—H35C | 109.5 |
C24—C19—C2 | 122.3 (2) | H35B—C35—H35C | 109.5 |
C20—C19—C2 | 120.3 (2) | C22—O36—H36 | 106 (2) |
C21—C20—C19 | 121.5 (2) | ||
C9—N1—C2—C3 | −0.2 (3) | C15—C16—C17—C18 | −2.5 (6) |
C9—N1—C2—C19 | 179.7 (2) | C7—N14—C18—C17 | 169.6 (3) |
N1—C2—C3—C4 | −2.0 (3) | C15—N14—C18—C17 | −3.0 (3) |
C19—C2—C3—C4 | 178.1 (2) | C16—C17—C18—N14 | 3.4 (5) |
C2—C3—C4—C10 | 2.2 (3) | N1—C2—C19—C24 | 178.7 (2) |
C2—C3—C4—C25 | −177.0 (2) | C3—C2—C19—C24 | −1.4 (3) |
N11—C5—N6—C7 | 180.0 (2) | N1—C2—C19—C20 | −2.2 (3) |
C10—C5—N6—C7 | −0.2 (3) | C3—C2—C19—C20 | 177.7 (2) |
C5—N6—C7—N14 | 176.1 (2) | C24—C19—C20—C21 | 1.6 (3) |
C5—N6—C7—C8 | −3.8 (3) | C2—C19—C20—C21 | −177.6 (2) |
N14—C7—C8—C12 | 7.1 (3) | C19—C20—C21—C22 | −0.2 (3) |
N6—C7—C8—C12 | −173.0 (2) | C20—C21—C22—O36 | 177.3 (2) |
N14—C7—C8—C9 | −175.1 (2) | C20—C21—C22—C23 | −1.6 (3) |
N6—C7—C8—C9 | 4.8 (3) | O36—C22—C23—C24 | −177.0 (2) |
C2—N1—C9—C10 | 2.1 (3) | C21—C22—C23—C24 | 2.0 (3) |
C2—N1—C9—C8 | −178.9 (2) | C22—C23—C24—C19 | −0.6 (3) |
C7—C8—C9—N1 | 179.1 (2) | C20—C19—C24—C23 | −1.2 (3) |
C12—C8—C9—N1 | −2.9 (3) | C2—C19—C24—C23 | 178.0 (2) |
C7—C8—C9—C10 | −1.8 (3) | C3—C4—C25—C30 | 90.1 (2) |
C12—C8—C9—C10 | 176.2 (2) | C10—C4—C25—C30 | −89.1 (3) |
C3—C4—C10—C9 | −0.4 (3) | C3—C4—C25—C26 | −89.0 (2) |
C25—C4—C10—C9 | 178.8 (2) | C10—C4—C25—C26 | 91.9 (3) |
C3—C4—C10—C5 | −179.2 (2) | C30—C25—C26—C27 | 1.4 (3) |
C25—C4—C10—C5 | −0.1 (3) | C4—C25—C26—C27 | −179.5 (2) |
N1—C9—C10—C4 | −1.8 (3) | C25—C26—C27—C28 | −0.9 (3) |
C8—C9—C10—C4 | 179.2 (2) | C26—C27—C28—N31 | 179.5 (2) |
N1—C9—C10—C5 | 177.2 (2) | C26—C27—C28—C29 | 0.7 (3) |
C8—C9—C10—C5 | −1.8 (3) | N31—C28—C29—C30 | −179.9 (2) |
N6—C5—C10—C4 | −178.1 (2) | C27—C28—C29—C30 | −1.1 (3) |
N11—C5—C10—C4 | 1.7 (3) | C28—C29—C30—C25 | 1.7 (4) |
N6—C5—C10—C9 | 3.0 (3) | C26—C25—C30—C29 | −1.8 (3) |
N11—C5—C10—C9 | −177.2 (2) | C4—C25—C30—C29 | 179.1 (2) |
C7—C8—C12—N13 | 153 (4) | C27—C28—N31—C34 | 176.7 (2) |
C9—C8—C12—N13 | −25 (4) | C29—C28—N31—C34 | −4.5 (3) |
N6—C7—N14—C18 | −173.4 (2) | C27—C28—N31—C32 | 12.2 (4) |
C8—C7—N14—C18 | 6.5 (3) | C29—C28—N31—C32 | −169.0 (3) |
N6—C7—N14—C15 | −1.4 (3) | C28—N31—C32—C33 | −122.5 (3) |
C8—C7—N14—C15 | 178.5 (2) | C34—N31—C32—C33 | 72.3 (4) |
C7—N14—C15—C16 | −171.4 (3) | C28—N31—C34—C35 | 82.0 (3) |
C18—N14—C15—C16 | 1.7 (3) | C32—N31—C34—C35 | −112.6 (3) |
N14—C15—C16—C17 | 0.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···N1 | 0.93 | 2.44 | 2.775 (2) | 101 |
N11—H11A···O36i | 0.86 | 2.39 | 3.047 (2) | 134 |
O36—H36···N13ii | 0.85 | 1.94 | 2.759 (3) | 163 |
C32—H32B···Cg1iii | 0.97 | 2.87 | 3.716 (7) | 146 |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C29H30N6O |
Mr | 478.59 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.9502 (2), 10.3680 (2), 12.4995 (2) |
α, β, γ (°) | 94.692 (1), 94.319 (1), 98.505 (1) |
V (Å3) | 1266.03 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.42 × 0.38 × 0.32 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6716, 4298, 3707 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.170, 1.01 |
No. of reflections | 4298 |
No. of parameters | 329 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.36 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97 and PARST (Nardelli, 1995).
N1—C2 | 1.322 (2) | C7—N14 | 1.348 (3) |
N1—C9 | 1.357 (2) | C8—C12 | 1.419 (3) |
C3—C4 | 1.377 (3) | C12—N13 | 1.147 (3) |
C5—N6 | 1.316 (3) | N14—C18 | 1.453 (3) |
C5—N11 | 1.346 (3) | N14—C15 | 1.473 (3) |
N6—C7 | 1.351 (3) | ||
C2—N1—C9 | 118.9 (2) | C28—N31—C34 | 120.5 (2) |
C7—N14—C18 | 126.3 (2) | C28—N31—C32 | 122.0 (2) |
C7—N14—C15 | 121.7 (2) | C34—N31—C32 | 115.7 (2) |
C18—N14—C15 | 111.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···N1 | 0.93 | 2.44 | 2.775 (2) | 101 |
N11—H11A···O36i | 0.86 | 2.39 | 3.047 (2) | 134 |
O36—H36···N13ii | 0.85 | 1.94 | 2.759 (3) | 163 |
C32—H32B···Cg1iii | 0.97 | 2.87 | 3.716 (7) | 146 |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x, −y+1, −z. |
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Naphthyridine derivatives constitute an important class of compounds possessing diverse types of biological properties. They have been reported as potential drugs for the treatment of bladder function disorders (Natsugari et al., 1999). They also possess anti-tumor (el-Subbah et al., 1999), antibacterial (Domagala et al., 1993), tuberculostatic (Ferrarini et al., 1998), cardio-tonic (Mohan & Mishra, 1997), anticonvulsant and insecticidal (Damon & Nadelson, 1981) properties. 1,6-Naphthyridine derivatives have been tested pharmacologically as potent antagonists at adrenoreceptors (Brown et al., 1993), they are also used as novel potent adenosine 3',5'-cyclic phosphate phosphodiesterase III inhibitors (Singh et al., 1995). As a continuation of the studies on 1,6-napthyridine derivatives (Sankaranarayanan et al., 1999) and to have a better understanding of the influence of structural and conformational change on its biological activity, the X-ray crystal structure analysis of the title compound, (I), has been carried out. \sch
The five rings of the molecule are identified as: A (C5,N6,C7—C10), B (N1,C2—C4,C10,C9), C (C19—C24), D (N14,C15—C18), E (C25—C30). The N—C and the other bond distances are comparable with the related structures previously studied (Sankaranarayanan et al., 1999; Thirumurugan et al., 1999; Govindasamy et al., 2000). The bond distance C5—N11 is shorter than the typical C—N single bond distance (1.47 Å) indicating conjugation of amino group with the aromatic system of naphthyridine. The naphthyridine ring is planar with the dihedral angle between the fused pyridine rings (rings A and B) being 1.9 (1)°.
The least squares plane through the phenyl rings make a dihedral angle of 1.9 (1) (ring C) and 89.5 (1)° (ring E) with the ring B to which they are attached indicating the perpendicular orientation of the ring E. The best plane through the pyrrolidine ring makes a dihedral angle of 11.3 (1)° with the pyridine ring (A). The sum of the bond angles around N14 and N31 are 359.6 (3) and 358.2 (3)°, respectively, indicating sp2 hybridization. The cyano bond distance C12≡N13 agrees well with the literature value of 1.138 (7) Å (Allen et al., 1987). The orientation of the diethyl substituent with respect to the phenyl ring (E) can be described by the torsional angles C28—N31—C32—C33 = -122.5 (3), C28—N31—C34—C35 = 82.0 (3)°. O36 is co-planar [C20—C21—C22—O36 = 177.3 (2)°] with the phenyl ring (C) to which it is attached. Due to steric interactions, bond angles C4—C10—C5 [127.3 (2)°], C8—C7—N14 [125.1 (2)°] are widened and the bond angles N1—C9—C8 [116.7 (2)°], N1—C2—C19 = 116.3 (2) are narrowed from 120° and these observations are also found in related structures (Chinnakali et al., 1998).
Apart from the normal van der Waals interactions, the molecular structure is stabilized by an intramolecular C—H···N type hydrogen bond and the molecular packing by the intermolecular N—H···O and O—H···N hydrogen bonds and C—H···π interaction (Table 2), where Cg1 is a centroid of ring E.