1,5-Bis[(2-meth­oxy­eth­oxy)meth­yl]-1,5-naphthyridine-4,8(1H,5H)-dione

Abstract

The complete mol­ecule of the title compound, C₁₆H₂₂N₂O₆, is generated by crystallographic inversion symmetry. The conformation of the N—C—O—C fragment of the side chain is approximately gauche [torsion angle = −74.84 (17)°]. In the crystal, weak C—H⋯O inter­actions link the mol­ecules.

Related literature

The background to the applications of the title compound, see: Shan et al. (2005 ▶). For the synthesis, see: Toshihiro et al. (2002 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₆H₂₂N₂O₆

• M _r = 338.36

• Monoclinic,

• a = 7.1610 (14) Å

• b = 11.497 (2) Å

• c = 10.734 (2) Å

• β = 105.45 (3)°

• V = 851.8 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 293 K

• 0.30 × 0.20 × 0.10 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.970, T _max = 0.990

• 3261 measured reflections

• 1549 independent reflections

• 1246 reflections with I > 2σ(I)

• R _int = 0.047

• 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.140

• S = 1.01

• 1549 reflections

• 110 parameters

• H-atom parameters constrained

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811054547/hb6550Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O3i	0.93	2.45	3.264 (2)	147
C6—H6A⋯O1ii	0.93	2.58	3.397 (2)	147

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Experimental

The title compound was prepared by a method reported in literature (Toshihiro et al., 2002). Colourless blocks were obtained by dissolving it (0.5 g) in methanol (50 ml) and evaporating the solvent slowly at room temperature for about 30 d.

Refinement

H atoms were positioned geometrically and refined as riding groups, with C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C), where x = 1.2 for aromatic H, and x = 1.5 for other H.

Figures

Fig. 1.

The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C16H22N2O6	F(000) = 360
Mr = 338.36	Dx = 1.319 Mg m−3
Monoclinic, P21/n	Melting point: 365 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.1610 (14) Å	Cell parameters from 25 reflections
b = 11.497 (2) Å	θ = 9–13°
c = 10.734 (2) Å	µ = 0.10 mm−1
β = 105.45 (3)°	T = 293 K
V = 851.8 (3) Å3	Block, colourless
Z = 2	0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1246 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
graphite	θmax = 25.3°, θmin = 2.7°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
Tmin = 0.970, Tmax = 0.990	l = −12→12
3261 measured reflections	3 standard reflections every 200 reflections
1549 independent reflections	intensity decay: 1%

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.140	w = 1/[σ2(Fo2) + (0.1P)2 + 0.026P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
1549 reflections	Δρmax = 0.24 e Å−3
110 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.30 (2)

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.03696 (18)	0.64646 (11)	0.57178 (12)	0.0421 (4)
O1	0.25472 (18)	1.00854 (10)	0.36603 (13)	0.0584 (4)
C1	0.2858 (3)	1.0712 (2)	0.2607 (2)	0.0781 (7)
H1A	0.2389	1.1492	0.2623	0.117*
H1B	0.2177	1.0341	0.1815	0.117*
H1C	0.4219	1.0729	0.2665	0.117*
O2	0.06007 (17)	0.80910 (9)	0.43882 (11)	0.0532 (4)
C5	0.1950 (2)	0.62630 (14)	0.67339 (15)	0.0479 (5)
H5A	0.2437	0.6875	0.7292	0.057*
C2	0.3185 (3)	0.89321 (17)	0.3692 (2)	0.0658 (6)
H2B	0.4581	0.8917	0.3836	0.079*
H2C	0.2603	0.8560	0.2869	0.079*
C3	0.2645 (3)	0.82888 (15)	0.4743 (2)	0.0639 (6)
H3A	0.3325	0.7551	0.4890	0.077*
H3B	0.3014	0.8736	0.5537	0.077*
O3	0.32189 (18)	0.33513 (10)	0.62397 (14)	0.0672 (5)
C4	−0.0118 (2)	0.77036 (13)	0.54011 (17)	0.0494 (5)
H4A	−0.1514	0.7797	0.5165	0.059*
H4B	0.0419	0.8177	0.6160	0.059*
C6	0.2837 (2)	0.52236 (14)	0.69674 (16)	0.0489 (5)
H6A	0.3860	0.5132	0.7704	0.059*
C7	0.2259 (2)	0.42641 (13)	0.61247 (15)	0.0449 (4)
C8	0.0437 (2)	0.44520 (12)	0.50952 (13)	0.0380 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0493 (7)	0.0351 (7)	0.0376 (7)	−0.0011 (5)	0.0041 (5)	−0.0016 (5)
O1	0.0678 (8)	0.0436 (7)	0.0690 (9)	0.0043 (5)	0.0273 (7)	0.0064 (5)
C1	0.0727 (13)	0.0781 (15)	0.0928 (16)	0.0075 (11)	0.0385 (12)	0.0289 (12)
O2	0.0602 (8)	0.0402 (6)	0.0513 (7)	−0.0052 (5)	0.0012 (6)	0.0059 (5)
C5	0.0557 (9)	0.0440 (9)	0.0374 (9)	−0.0068 (7)	0.0009 (7)	−0.0030 (6)
C2	0.0697 (11)	0.0493 (11)	0.0836 (14)	0.0087 (9)	0.0291 (10)	0.0052 (9)
C3	0.0577 (11)	0.0523 (11)	0.0756 (13)	0.0029 (8)	0.0071 (9)	0.0127 (9)
O3	0.0602 (8)	0.0429 (7)	0.0812 (10)	0.0086 (5)	−0.0114 (7)	0.0018 (6)
C4	0.0565 (9)	0.0341 (8)	0.0532 (10)	0.0014 (7)	0.0066 (7)	−0.0044 (7)
C6	0.0490 (9)	0.0464 (9)	0.0413 (9)	−0.0051 (7)	−0.0054 (7)	0.0051 (7)
C7	0.0459 (9)	0.0396 (8)	0.0446 (9)	0.0003 (7)	0.0040 (7)	0.0083 (7)
C8	0.0442 (8)	0.0341 (8)	0.0346 (8)	−0.0035 (6)	0.0086 (6)	0.0034 (6)

Geometric parameters (Å, °)

N1—C5	1.366 (2)	C2—H2B	0.9700
N1—C8i	1.3919 (19)	C2—H2C	0.9700
N1—C4	1.4843 (19)	C3—H3A	0.9700
O1—C2	1.400 (2)	C3—H3B	0.9700
O1—C1	1.407 (2)	O3—C7	1.2426 (18)
C1—H1A	0.9600	C4—H4A	0.9700
C1—H1B	0.9600	C4—H4B	0.9700
C1—H1C	0.9600	C6—C7	1.417 (2)
O2—C4	1.394 (2)	C6—H6A	0.9300
O2—C3	1.429 (2)	C7—C8	1.484 (2)
C5—C6	1.345 (2)	C8—N1i	1.3919 (19)
C5—H5A	0.9300	C8—C8i	1.398 (3)
C2—C3	1.484 (3)
C5—N1—C8i	119.30 (13)	O2—C3—H3A	109.8
C5—N1—C4	116.10 (13)	C2—C3—H3A	109.8
C8i—N1—C4	123.37 (13)	O2—C3—H3B	109.8
C2—O1—C1	112.60 (16)	C2—C3—H3B	109.8
O1—C1—H1A	109.5	H3A—C3—H3B	108.2
O1—C1—H1B	109.5	O2—C4—N1	111.85 (13)
H1A—C1—H1B	109.5	O2—C4—H4A	109.2
O1—C1—H1C	109.5	N1—C4—H4A	109.2
H1A—C1—H1C	109.5	O2—C4—H4B	109.2
H1B—C1—H1C	109.5	N1—C4—H4B	109.2
C4—O2—C3	114.06 (14)	H4A—C4—H4B	107.9
C6—C5—N1	123.30 (15)	C5—C6—C7	121.98 (14)
C6—C5—H5A	118.3	C5—C6—H6A	119.0
N1—C5—H5A	118.3	C7—C6—H6A	119.0
O1—C2—C3	109.96 (17)	O3—C7—C6	122.30 (14)
O1—C2—H2B	109.7	O3—C7—C8	123.39 (14)
C3—C2—H2B	109.7	C6—C7—C8	114.30 (13)
O1—C2—H2C	109.7	N1i—C8—C8i	119.73 (16)
C3—C2—H2C	109.7	N1i—C8—C7	119.50 (13)
H2B—C2—H2C	108.2	C8i—C8—C7	120.73 (16)
O2—C3—C2	109.45 (16)
C8i—N1—C5—C6	2.9 (3)	N1—C5—C6—C7	3.7 (3)
C4—N1—C5—C6	−164.78 (16)	C5—C6—C7—O3	170.47 (16)
C1—O1—C2—C3	−174.45 (17)	C5—C6—C7—C8	−8.8 (2)
C4—O2—C3—C2	−167.81 (14)	O3—C7—C8—N1i	6.6 (2)
O1—C2—C3—O2	72.0 (2)	C6—C7—C8—N1i	−174.16 (14)
C3—O2—C4—N1	−74.84 (17)	O3—C7—C8—C8i	−171.19 (18)
C5—N1—C4—O2	97.84 (16)	C6—C7—C8—C8i	8.1 (2)
C8i—N1—C4—O2	−69.31 (19)

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O3ii	0.93	2.45	3.264 (2)	147
C6—H6A···O1iii	0.93	2.58	3.397 (2)	147

Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+3/2, z+1/2.