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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o249.
Published online 2007 December 12. doi:  10.1107/S160053680706549X
PMCID: PMC2915306

7-[4-(5,7-Dimethyl-1,8-naphthyridin-2-yl­oxy)phen­oxy]-2,4-dimethyl-1,8-naphthyridine methanol disolvate

Abstract

The title compound, C26H22N4O2·2CH3OH, was synthesized and characterized by 1H NMR spectroscopy and X-ray structure analysis. There is one half-mol­ecule in the asymmetric unit with a centre of symmetry located at the centre of the benzene ring. The two bridged naphthyridine ring systems are in an anti­parallel orientation. In the crystal structure, O—H(...)N, C—H(...)O and C—H(...)N inter­actions define the packing.

Related literature

For related literature, see: Ferrarini et al. (2004 [triangle]); Goswami & Mukherjee (1997 [triangle]); Hoock et al. (1999 [triangle]); Jin, Liu & Chen (2007 [triangle]); Jin, Chen & Wang (2007 [triangle]); Nabanita et al. (2006 [triangle]); Nakatani et al. (2000 [triangle]); Nakataniz et al. (2001 [triangle]); Newkome et al. (1981 [triangle]); Stuk et al. (2003 [triangle]); Gavrilova & Bosnich (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o249-scheme1.jpg

Experimental

Crystal data

  • C26H22N4O2·2CH4O
  • M r = 486.56
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o249-efi1.jpg
  • a = 7.009 (3) Å
  • b = 9.244 (3) Å
  • c = 10.239 (4) Å
  • α = 78.679 (6)°
  • β = 79.653 (6)°
  • γ = 82.689 (6)°
  • V = 637.0 (4) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 (2) K
  • 0.27 × 0.24 × 0.19 mm

Data collection

  • Bruker SMART APEX CCD Diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.977, T max = 0.984
  • 3379 measured reflections
  • 2216 independent reflections
  • 1236 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.163
  • S = 1.03
  • 2216 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SMART (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706549X/kp2143sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706549X/kp2143Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Zhejiang Forestry University Science Foundation for financial support.

supplementary crystallographic information

Comment

Derivatives of 1,8-naphthyridine have been investigated over half a century because of their interesting complexation properties and medical uses. They can act as antimycobacterial and antimicrobial agents (Goswami et al., 1997; Nakatani et al., 2000; Ferrarini et al., 2004; Stuk et al., 2003) and as mono-nucleating and dinucleating ligands in coordination chemistry (Gavrilova & Bosnich, 2004). The deriatives of 1,8-naphthyridine have been widely utilized as molecular recognition receptors for urea, carboxylic acids and guanine (Goswami et al., 1997; Nakatani et al., 2000). Recently 1,8-naphthyridine derivatives have been reported to be excellent fluorescent markers of nucleic acids (Hoock et al., 1999) and probe molecules (Nakataniz et al., 2001). Many novel inorganic complexes have been synthesized using this kind of compounds as mono or bidentate ligands (Nabanita et al., 2006; Jin, Liu & Chen, 2007; Jin, Chen & Wang, 2007). However, only a few mono and disubstituted 2,7-naphthyridine derivatives have been prepared. The potential multinucleating abilities of 1,8-naphthyridine derivatives as ligands in preparations of functional metalloorganic compounds stimulated us to explore bridged 1,8-naphthyridine compounds. In this paper, we report the synthesis and structure characterization of 7-(4-(5,7-dimethyl-1,8-naphthyridin-2-yloxy)phenoxy)- 2,4-dimethyl-1,8-naphthyridine dimethanol solvate (I) (Fig. 1). The crystals of (I) were formed by slow evaporation of 7-(4-(5,7-dimethyl-1,8- naphthyridin-2-yloxy)phenoxy)-2,4-dimethyl-1,8-naphthyridine from methanol solution. An X-ray diffraction analysis of (I) is in agreement with the HNMR results. Bond lengths and angles are in the usual range. The bond lengths N(1)—C(8) and N(2)—C(2) are 1.303 (3) and 1.322 (3) Å, respectively, and display double-bond character. The bond lengths N(1)—C(1) and N(2)—C(1), both are 1.361 (3) Å and reveal a single-bond character. The conformations of the two naphthyridine rings towards the benzene ring is described by the torsion angle C(13)—C(12)—O(1)—C(8) (126.06 (2) °); they adopt (+)-anticlinal and (-)-anticlinal conformations. The torsion angle C(7), C(8), O(1), C(12) of 175.56 (2) ° defines the anti-parallel orientation of the two naphthyridine rings being in accord with Ci molecular symmetry. The closest contact between two adjacent naphthyridine carbons (C2···C4i, symmetry code: i) 1 - x, -y, 2 - z.) is 3.512 Å, which is in the range of π···π stacking interaction. The O—H..N, C—H···O and C—H···N interactions define the pcrystal packing (Table 1, Fig.2).

Experimental

Chemicals were obtained from commercial suppliers and used without further purification. 5,7-Dimethyl-2-chloro-1,8-naphthyridine was prepared according to (Newkome et al., 1981). Reactions and product mixtures were routinely monitored by TLC on silica gel (precoated F254 Merck plates) with spot detection under UV light. NMR spectra were recorded on Bruker Avance-400 (400 MHz) spectrometer in deuterated chloroform. Chemical shifts (delta) are expressed in p.p.m. downfield to TMS at delta = 0 p.p.m. and coupling constants (J) are expressed in Hz.

A Schlenck tube was charged with 15 ml DMF and 5,7-dimethyl-2-chloro-1,8-naphthyridine, 0.77 g (4 mmol), sodium carbonate 0.33 g (2.4 mmol), p-hydroquinone 0.22 g (2 mmol). were added. The Schlenck tube was capped, evacuated, and back-filled with Ar three times. While still under Ar, it was immersed into a 413 K– hetaed oil bath. After stirring for 48 h, the mixture was cooled, filtered over celite, and evaporated in vacuo. The residue was washed with sodium hydroxide, then washed with water till the washing is neutral, filtered, dried in vacuum. The product 7-(4-(5,7-dimethyl-1,8- naphthyridin-2-yloxy)phenoxy)-2,4-dimethyl-1,8-naphthyridine precipitated was recrystallized from methanol. Yield: 0.42 g, 49.8%. Anal. Calcd. for (C26H22N4O2): C, 73.92%, H, 5.25%, N, 13.26%. Found: C, 73.78%, H, 5.25%, N, 13.45%. 1H NMR (400 MHz, CDCl3): delta = 2.65(s, 6H), 2.67(s, 6H), 7.09(s, 2H), 7.20(d, 2H, J = 9 Hz), 7.32(s, 4H), 8.30(d, 2H, J = 9 Hz).

Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H)) = 1.2Ueq(C). Hydrogen atoms bound to methanol molecules were located in the Fourier difference map, and their distances were fixed and subject to an O—H = 0.85 Å with deviation of positive and negative 0.01 Å restraint.

Figures

Fig. 1.
The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code to generate the molecule from an asymmetric unit (-x, 1 - y, 1 - z).
Fig. 2.
The crystal packing of (I).

Crystal data

C26H22N4O2·2CH4OZ = 1
Mr = 486.56F000 = 258
Triclinic, P1Dx = 1.268 Mg m3
a = 7.009 (3) ÅMo Kα radiation λ = 0.71073 Å
b = 9.244 (3) ÅCell parameters from 877 reflections
c = 10.239 (4) Åθ = 2.3–24.7º
α = 78.679 (6)ºµ = 0.09 mm1
β = 79.653 (6)ºT = 298 (2) K
γ = 82.689 (6)ºBlock, colourless
V = 637.0 (4) Å30.27 × 0.24 × 0.19 mm

Data collection

Bruker SMART APEX CCD Diffractometer2216 independent reflections
Radiation source: fine-focus sealed tube1236 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 298(2) Kθmax = 25.0º
phi and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −8→5
Tmin = 0.977, Tmax = 0.984k = −10→10
3379 measured reflectionsl = −11→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.163  w = 1/[σ2(Fo2) + (0.0658P)2 + 0.2468P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2216 reflectionsΔρmax = 0.27 e Å3
163 parametersΔρmin = −0.20 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
N10.3076 (3)0.1993 (2)0.6758 (2)0.0483 (6)
N20.5387 (3)0.2103 (2)0.8040 (2)0.0496 (6)
O10.0813 (3)0.19512 (19)0.5388 (2)0.0619 (6)
O20.3944 (3)0.5192 (2)0.7759 (3)0.0967 (10)
H20.43760.43170.78310.145*
C10.4486 (4)0.1239 (3)0.7453 (3)0.0430 (7)
C20.6819 (4)0.1463 (3)0.8699 (3)0.0529 (8)
C30.7375 (4)−0.0058 (3)0.8838 (3)0.0570 (8)
H30.8371−0.04630.93280.068*
C40.6492 (4)−0.0972 (3)0.8273 (3)0.0521 (8)
C50.4982 (4)−0.0297 (3)0.7537 (3)0.0437 (7)
C60.3930 (4)−0.1050 (3)0.6864 (3)0.0530 (8)
H60.4195−0.20680.69030.064*
C70.2544 (4)−0.0296 (3)0.6165 (3)0.0557 (8)
H70.1844−0.07780.57190.067*
C80.2194 (4)0.1241 (3)0.6135 (3)0.0489 (7)
C90.7853 (5)0.2444 (4)0.9283 (4)0.0748 (10)
H9A0.72840.34480.90900.112*
H9B0.92060.23890.88920.112*
H9C0.77320.21231.02420.112*
C100.7114 (5)−0.2600 (3)0.8422 (4)0.0768 (11)
H10A0.6335−0.30560.79650.115*
H10B0.6944−0.30370.93620.115*
H10C0.8461−0.27510.80350.115*
C110.1900 (4)0.4419 (3)0.4653 (3)0.0532 (8)
H110.31770.40260.44180.064*
C120.0463 (4)0.3504 (3)0.5222 (3)0.0470 (7)
C13−0.1421 (4)0.4064 (3)0.5566 (3)0.0498 (7)
H13−0.23790.34280.59470.060*
C140.1928 (5)0.5291 (4)0.8034 (4)0.0744 (10)
H14A0.15190.49050.89700.112*
H14B0.14520.47270.74880.112*
H14C0.14180.63100.78340.112*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0538 (15)0.0380 (13)0.0556 (16)−0.0017 (11)−0.0224 (12)−0.0039 (11)
N20.0545 (15)0.0452 (13)0.0511 (15)−0.0090 (11)−0.0184 (12)−0.0019 (11)
O10.0721 (14)0.0400 (11)0.0834 (16)0.0003 (10)−0.0463 (12)−0.0069 (10)
O20.0614 (16)0.0542 (14)0.176 (3)−0.0057 (11)−0.0178 (16)−0.0239 (16)
C10.0442 (16)0.0406 (15)0.0437 (17)−0.0039 (12)−0.0123 (13)−0.0015 (12)
C20.0496 (18)0.0580 (19)0.0515 (19)−0.0095 (15)−0.0141 (15)−0.0026 (14)
C30.0475 (18)0.065 (2)0.056 (2)0.0036 (15)−0.0188 (15)−0.0011 (15)
C40.0492 (18)0.0499 (17)0.0528 (19)0.0061 (14)−0.0097 (15)−0.0040 (14)
C50.0427 (16)0.0400 (15)0.0458 (17)−0.0005 (12)−0.0083 (13)−0.0024 (12)
C60.0608 (19)0.0353 (15)0.063 (2)0.0006 (14)−0.0152 (16)−0.0075 (14)
C70.064 (2)0.0426 (16)0.067 (2)−0.0048 (15)−0.0239 (17)−0.0114 (14)
C80.0507 (17)0.0432 (16)0.0535 (18)−0.0017 (13)−0.0204 (15)−0.0014 (13)
C90.078 (2)0.078 (2)0.079 (3)−0.0178 (19)−0.038 (2)−0.0080 (19)
C100.079 (2)0.058 (2)0.092 (3)0.0232 (18)−0.035 (2)−0.0121 (18)
C110.0488 (18)0.0544 (18)0.055 (2)0.0034 (14)−0.0140 (15)−0.0070 (14)
C120.0560 (19)0.0397 (15)0.0478 (18)−0.0031 (14)−0.0249 (15)0.0005 (13)
C130.0481 (18)0.0493 (17)0.0497 (19)−0.0110 (14)−0.0121 (14)0.0051 (13)
C140.070 (2)0.074 (2)0.084 (3)−0.0051 (18)−0.016 (2)−0.0227 (19)

Geometric parameters (Å, °)

N1—C81.303 (3)C7—C81.406 (4)
N1—C11.361 (3)C7—H70.9300
N2—C21.322 (3)C9—H9A0.9600
N2—C11.361 (3)C9—H9B0.9600
O1—C81.364 (3)C9—H9C0.9600
O1—C121.406 (3)C10—H10A0.9600
O2—C141.385 (4)C10—H10B0.9600
O2—H20.8200C10—H10C0.9600
C1—C51.407 (4)C11—C121.372 (4)
C2—C31.396 (4)C11—C13i1.383 (4)
C2—C91.498 (4)C11—H110.9300
C3—C41.373 (4)C12—C131.367 (4)
C3—H30.9300C13—C11i1.383 (4)
C4—C51.418 (4)C13—H130.9300
C4—C101.499 (4)C14—H14A0.9600
C5—C61.416 (4)C14—H14B0.9600
C6—C71.350 (4)C14—H14C0.9600
C6—H60.9300
C8—N1—C1117.3 (2)C2—C9—H9A109.5
C2—N2—C1117.9 (2)C2—C9—H9B109.5
C8—O1—C12119.3 (2)H9A—C9—H9B109.5
C14—O2—H2109.5C2—C9—H9C109.5
N2—C1—N1114.1 (2)H9A—C9—H9C109.5
N2—C1—C5123.2 (2)H9B—C9—H9C109.5
N1—C1—C5122.7 (2)C4—C10—H10A109.5
N2—C2—C3122.1 (3)C4—C10—H10B109.5
N2—C2—C9117.1 (3)H10A—C10—H10B109.5
C3—C2—C9120.8 (3)C4—C10—H10C109.5
C4—C3—C2121.9 (3)H10A—C10—H10C109.5
C4—C3—H3119.1H10B—C10—H10C109.5
C2—C3—H3119.1C12—C11—C13i119.0 (3)
C3—C4—C5116.8 (3)C12—C11—H11120.5
C3—C4—C10121.3 (3)C13i—C11—H11120.5
C5—C4—C10122.0 (3)C13—C12—C11121.2 (2)
C1—C5—C6116.9 (2)C13—C12—O1116.5 (2)
C1—C5—C4118.2 (3)C11—C12—O1122.1 (3)
C6—C5—C4124.9 (2)C12—C13—C11i119.8 (3)
C7—C6—C5120.2 (3)C12—C13—H13120.1
C7—C6—H6119.9C11i—C13—H13120.1
C5—C6—H6119.9O2—C14—H14A109.5
C6—C7—C8117.9 (3)O2—C14—H14B109.5
C6—C7—H7121.1H14A—C14—H14B109.5
C8—C7—H7121.1O2—C14—H14C109.5
N1—C8—O1119.7 (2)H14A—C14—H14C109.5
N1—C8—C7124.9 (2)H14B—C14—H14C109.5
O1—C8—C7115.3 (2)
C2—N2—C1—N1−177.8 (2)C10—C4—C5—C6−0.8 (5)
C2—N2—C1—C51.3 (4)C1—C5—C6—C71.0 (4)
C8—N1—C1—N2178.0 (2)C4—C5—C6—C7−178.5 (3)
C8—N1—C1—C5−1.1 (4)C5—C6—C7—C80.0 (5)
C1—N2—C2—C3−2.0 (4)C1—N1—C8—O1−177.9 (2)
C1—N2—C2—C9177.3 (3)C1—N1—C8—C72.2 (4)
N2—C2—C3—C41.5 (5)C12—O1—C8—N14.6 (4)
C9—C2—C3—C4−177.8 (3)C12—O1—C8—C7−175.5 (3)
C2—C3—C4—C50.0 (4)C6—C7—C8—N1−1.7 (5)
C2—C3—C4—C10179.5 (3)C6—C7—C8—O1178.5 (3)
N2—C1—C5—C6−179.4 (3)C13i—C11—C12—C130.3 (5)
N1—C1—C5—C6−0.4 (4)C13i—C11—C12—O1175.5 (2)
N2—C1—C5—C40.1 (4)C8—O1—C12—C13−126.0 (3)
N1—C1—C5—C4179.1 (3)C8—O1—C12—C1158.6 (4)
C3—C4—C5—C1−0.7 (4)C11—C12—C13—C11i−0.3 (5)
C10—C4—C5—C1179.7 (3)O1—C12—C13—C11i−175.7 (2)
C3—C4—C5—C6178.8 (3)

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N20.822.062.882 (3)178
C6—H6···O2ii0.932.533.414 (4)159
C10—H10A···O2ii0.962.543.436 (4)156
C13—H13···N2iii0.932.613.450 (4)151

Symmetry codes: (ii) x, y−1, z; (iii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2143).

References

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