14-Eth-oxy-4,6,9-trimethyl-8,12-dioxa-4,6-diaza-tetra-cyclo-[8.8.0.0(2,7).0(13,18)]octa-deca-2(7),13,15,17-tetra-ene-3,5,11-trione.

In the title compound, C(19)H(20)N(2)O(6), the pyrone and pyran rings adopt envelope conformations with the same common C atom as the flap, the dihedral angle between the planes of the remaining ring atoms being 68.27 (4)°. The planar atoms of the pyran ring and the diaza-cyclic ring are almost coplanar, the dihedral angle between their mean planes being 3.29 (7)°. Moreover, the planar atoms of the pyrone ring and benzene ring of the coumarin unit are also close to coplanar, the dihedral angle between their mean planes being 8.03 (9)°. The meth-oxy group lies in the plane of the benzene ring, with a dihedral angle between their mean planes of 9.4 (2)°. In the crystal, the molecules are linked by C-H⋯O hydrogen bonds resulting in sheets of mol-ecules in the ac plane.

Related literature

For the biological activity of pyran­ocoumarin compounds, see: Kawaii et al. (2001 ▶); Goel et al. (1997 ▶); Su et al. (2009 ▶). For a related structure, see: Pojarová et al. (2012 ▶).

Experimental

Crystal data

C19H20N2O6

M = 372.37

Monoclinic,

a = 9.3526 (3) Å

b = 17.9559 (5) Å

c = 10.9158 (3) Å

β = 101.346 (1)°

V = 1797.31 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2004 ▶) T min = 0.979, T max = 0.983

21571 measured reflections

5615 independent reflections

3743 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.151

S = 1.03

5615 reflections

245 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000743/pv2613sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000743/pv2613Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000743/pv2613Isup3.cml

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

C19H20N2O6	F(000) = 784
Mr = 372.37	Dx = 1.376 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8834 reflections
a = 9.3526 (3) Å	θ = 2.1–31.2°
b = 17.9559 (5) Å	µ = 0.10 mm−1
c = 10.9158 (3) Å	T = 293 K
β = 101.346 (1)°	Block, colourless
V = 1797.31 (9) Å3	0.25 × 0.20 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	5615 independent reflections
Radiation source: fine-focus sealed tube	3743 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω and φ scan	θmax = 31.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker 2004)	h = −13→13
Tmin = 0.979, Tmax = 0.983	k = −26→25
21571 measured reflections	l = −15→9

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)] = 0.049	H-atom parameters constrained
wR(F2) = 0.151	w = 1/[σ2(Fo2) + (0.0701P)2 + 0.3178P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
5615 reflections	Δρmax = 0.31 e Å−3
245 parameters	Δρmin = −0.20 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: 0.0038 (11)

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
C4	0.13936 (13)	0.22959 (7)	0.17644 (11)	0.0356 (3)
H4	0.2334	0.2050	0.2061	0.043*
O2	0.12546 (11)	0.18881 (6)	−0.07686 (9)	0.0488 (3)
O4	−0.00265 (11)	0.37272 (5)	0.16207 (10)	0.0509 (3)
C3	0.15760 (13)	0.28831 (7)	0.07958 (12)	0.0385 (3)
H3	0.2385	0.3211	0.1163	0.046*
C5	0.09372 (13)	0.26778 (7)	0.28399 (12)	0.0383 (3)
N1	0.07800 (14)	0.27406 (8)	0.50011 (11)	0.0533 (3)
O3	0.27612 (11)	0.27910 (7)	−0.09473 (10)	0.0570 (3)
O6	0.18464 (12)	0.17436 (7)	0.42755 (10)	0.0582 (3)
C9	0.03042 (13)	0.17227 (7)	0.11316 (12)	0.0359 (3)
N2	−0.01928 (14)	0.37032 (8)	0.36503 (13)	0.0546 (3)
C2	0.01853 (15)	0.33507 (7)	0.04908 (13)	0.0423 (3)
H2	−0.0645	0.3019	0.0203	0.051*
C6	0.02593 (14)	0.33416 (8)	0.26892 (13)	0.0429 (3)
C8	0.12327 (14)	0.23418 (9)	0.40514 (12)	0.0443 (3)
C15	0.19303 (14)	0.25353 (8)	−0.03619 (12)	0.0422 (3)
C10	0.02937 (14)	0.15529 (7)	−0.01043 (12)	0.0394 (3)
C11	−0.06657 (16)	0.10293 (8)	−0.07638 (13)	0.0454 (3)
C14	−0.07055 (15)	0.13790 (8)	0.17140 (13)	0.0433 (3)
H14	−0.0734	0.1493	0.2540	0.052*
O1	−0.05510 (14)	0.09050 (6)	−0.19682 (10)	0.0605 (3)
C12	−0.16431 (17)	0.06843 (8)	−0.01514 (15)	0.0517 (4)
H12	−0.2285	0.0328	−0.0563	0.062*
C13	−0.16670 (17)	0.08690 (8)	0.10732 (15)	0.0516 (4)
H13	−0.2346	0.0644	0.1471	0.062*
C16	−0.13766 (19)	0.03015 (9)	−0.26109 (15)	0.0594 (4)
H16A	−0.2410	0.0417	−0.2766	0.071*
H16B	−0.1213	−0.0149	−0.2113	0.071*
C7	0.00306 (18)	0.33991 (11)	0.48375 (16)	0.0592 (4)
O5	−0.04221 (16)	0.37072 (9)	0.56792 (13)	0.0855 (5)
C18	0.1006 (2)	0.24059 (13)	0.62469 (15)	0.0734 (5)
H18A	0.1538	0.1948	0.6249	0.110*
H18B	0.0079	0.2307	0.6464	0.110*
H18C	0.1551	0.2743	0.6845	0.110*
C17	−0.0879 (2)	0.01967 (12)	−0.38124 (18)	0.0775 (6)
H17A	−0.1412	−0.0205	−0.4270	0.116*
H17B	0.0144	0.0082	−0.3646	0.116*
H17C	−0.1047	0.0646	−0.4297	0.116*
C19	−0.1050 (2)	0.43883 (11)	0.3431 (2)	0.0813 (6)
H19A	−0.1135	0.4538	0.2575	0.122*
H19B	−0.0574	0.4774	0.3969	0.122*
H19C	−0.2004	0.4302	0.3603	0.122*
C1	0.0188 (2)	0.39517 (9)	−0.04694 (17)	0.0625 (4)
H1A	−0.0728	0.4211	−0.0608	0.094*
H1C	0.0328	0.3732	−0.1238	0.094*
H1B	0.0964	0.4296	−0.0175	0.094*

	U11	U22	U33	U12	U13	U23
C4	0.0312 (5)	0.0409 (6)	0.0348 (6)	0.0038 (5)	0.0069 (5)	0.0008 (5)
O2	0.0530 (6)	0.0568 (6)	0.0407 (5)	−0.0071 (5)	0.0197 (4)	−0.0078 (4)
O4	0.0557 (6)	0.0419 (5)	0.0550 (6)	0.0095 (4)	0.0102 (5)	−0.0018 (4)
C3	0.0338 (6)	0.0433 (7)	0.0378 (6)	−0.0037 (5)	0.0056 (5)	0.0004 (5)
C5	0.0337 (6)	0.0455 (7)	0.0354 (6)	−0.0006 (5)	0.0063 (5)	−0.0050 (5)
N1	0.0478 (7)	0.0770 (9)	0.0351 (6)	−0.0090 (6)	0.0083 (5)	−0.0115 (6)
O3	0.0472 (6)	0.0811 (8)	0.0460 (6)	−0.0100 (5)	0.0172 (5)	0.0057 (5)
O6	0.0537 (6)	0.0729 (7)	0.0452 (6)	0.0102 (6)	0.0027 (5)	0.0103 (5)
C9	0.0362 (6)	0.0346 (6)	0.0373 (6)	0.0044 (5)	0.0082 (5)	−0.0003 (5)
N2	0.0510 (7)	0.0551 (8)	0.0589 (8)	0.0028 (6)	0.0140 (6)	−0.0192 (6)
C2	0.0408 (7)	0.0396 (7)	0.0446 (7)	0.0010 (5)	0.0035 (5)	0.0017 (5)
C6	0.0367 (6)	0.0453 (7)	0.0464 (7)	−0.0019 (5)	0.0073 (5)	−0.0100 (6)
C8	0.0331 (6)	0.0612 (9)	0.0368 (6)	−0.0047 (6)	0.0026 (5)	−0.0045 (6)
C15	0.0351 (6)	0.0540 (8)	0.0373 (6)	0.0001 (6)	0.0069 (5)	0.0043 (6)
C10	0.0416 (7)	0.0382 (6)	0.0402 (6)	0.0013 (5)	0.0126 (5)	−0.0017 (5)
C11	0.0527 (8)	0.0407 (7)	0.0418 (7)	0.0033 (6)	0.0071 (6)	−0.0053 (6)
C14	0.0458 (7)	0.0429 (7)	0.0433 (7)	−0.0003 (6)	0.0135 (6)	0.0008 (6)
O1	0.0773 (8)	0.0580 (7)	0.0462 (6)	−0.0103 (6)	0.0123 (5)	−0.0163 (5)
C12	0.0510 (8)	0.0416 (7)	0.0601 (9)	−0.0067 (6)	0.0052 (7)	−0.0045 (7)
C13	0.0511 (8)	0.0475 (8)	0.0588 (9)	−0.0084 (6)	0.0172 (7)	0.0019 (7)
C16	0.0656 (10)	0.0489 (8)	0.0585 (9)	0.0060 (7)	−0.0005 (7)	−0.0188 (7)
C7	0.0491 (8)	0.0773 (11)	0.0524 (9)	−0.0082 (8)	0.0126 (7)	−0.0248 (8)
O5	0.0845 (9)	0.1113 (11)	0.0661 (8)	0.0010 (8)	0.0283 (7)	−0.0401 (8)
C18	0.0725 (11)	0.1111 (16)	0.0368 (8)	−0.0087 (11)	0.0110 (8)	−0.0010 (9)
C17	0.0926 (14)	0.0744 (12)	0.0624 (11)	0.0085 (11)	0.0076 (10)	−0.0287 (10)
C19	0.0893 (14)	0.0655 (11)	0.0923 (15)	0.0240 (10)	0.0258 (11)	−0.0246 (11)
C1	0.0695 (11)	0.0531 (9)	0.0621 (10)	0.0046 (8)	0.0062 (8)	0.0156 (8)

C4—C5	1.4926 (18)	C10—C11	1.3975 (19)
C4—C9	1.5157 (17)	C11—O1	1.3584 (17)
C4—C3	1.5263 (18)	C11—C12	1.381 (2)
C4—H4	0.9800	C14—C13	1.374 (2)
O2—C15	1.3552 (17)	C14—H14	0.9300
O2—C10	1.3972 (16)	O1—C16	1.4316 (18)
O4—C6	1.3373 (18)	C12—C13	1.382 (2)
O4—C2	1.4538 (17)	C12—H12	0.9300
C3—C15	1.5038 (19)	C13—H13	0.9300
C3—C2	1.5288 (18)	C16—C17	1.487 (3)
C3—H3	0.9800	C16—H16A	0.9700
C5—C6	1.3448 (19)	C16—H16B	0.9700
C5—C8	1.4301 (19)	C7—O5	1.2175 (19)
N1—C7	1.368 (2)	C18—H18A	0.9600
N1—C8	1.3926 (19)	C18—H18B	0.9600
N1—C18	1.464 (2)	C18—H18C	0.9600
O3—C15	1.1910 (16)	C17—H17A	0.9600
O6—C8	1.2197 (19)	C17—H17B	0.9600
C9—C10	1.3812 (18)	C17—H17C	0.9600
C9—C14	1.3832 (18)	C19—H19A	0.9600
N2—C6	1.3695 (18)	C19—H19B	0.9600
N2—C7	1.384 (2)	C19—H19C	0.9600
N2—C19	1.462 (2)	C1—H1A	0.9600
C2—C1	1.505 (2)	C1—H1C	0.9600
C2—H2	0.9800	C1—H1B	0.9600
C5—C4—C9	113.56 (10)	O1—C11—C10	116.37 (13)
C5—C4—C3	108.40 (11)	C12—C11—C10	118.13 (13)
C9—C4—C3	108.06 (10)	C13—C14—C9	120.06 (13)
C5—C4—H4	108.9	C13—C14—H14	120.0
C9—C4—H4	108.9	C9—C14—H14	120.0
C3—C4—H4	108.9	C11—O1—C16	117.45 (13)
C15—O2—C10	120.36 (10)	C11—C12—C13	119.93 (13)
C6—O4—C2	117.52 (10)	C11—C12—H12	120.0
C15—C3—C4	111.61 (11)	C13—C12—H12	120.0
C15—C3—C2	111.33 (11)	C14—C13—C12	121.25 (14)
C4—C3—C2	108.91 (10)	C14—C13—H13	119.4
C15—C3—H3	108.3	C12—C13—H13	119.4
C4—C3—H3	108.3	O1—C16—C17	107.20 (15)
C2—C3—H3	108.3	O1—C16—H16A	110.3
C6—C5—C8	119.19 (13)	C17—C16—H16A	110.3
C6—C5—C4	120.79 (12)	O1—C16—H16B	110.3
C8—C5—C4	120.02 (12)	C17—C16—H16B	110.3
C7—N1—C8	124.76 (13)	H16A—C16—H16B	108.5
C7—N1—C18	116.92 (14)	O5—C7—N1	122.64 (18)
C8—N1—C18	118.10 (16)	O5—C7—N2	121.11 (18)
C10—C9—C14	118.43 (12)	N1—C7—N2	116.25 (13)
C10—C9—C4	118.03 (11)	N1—C18—H18A	109.5
C14—C9—C4	123.51 (11)	N1—C18—H18B	109.5
C6—N2—C7	121.19 (14)	H18A—C18—H18B	109.5
C6—N2—C19	121.01 (15)	N1—C18—H18C	109.5
C7—N2—C19	117.55 (14)	H18A—C18—H18C	109.5
O4—C2—C1	106.06 (12)	H18B—C18—H18C	109.5
O4—C2—C3	108.82 (10)	C16—C17—H17A	109.5
C1—C2—C3	115.33 (13)	C16—C17—H17B	109.5
O4—C2—H2	108.8	H17A—C17—H17B	109.5
C1—C2—H2	108.8	C16—C17—H17C	109.5
C3—C2—H2	108.8	H17A—C17—H17C	109.5
O4—C6—C5	125.03 (13)	H17B—C17—H17C	109.5
O4—C6—N2	112.57 (12)	N2—C19—H19A	109.5
C5—C6—N2	122.39 (14)	N2—C19—H19B	109.5
O6—C8—N1	120.23 (13)	H19A—C19—H19B	109.5
O6—C8—C5	123.69 (13)	N2—C19—H19C	109.5
N1—C8—C5	116.08 (13)	H19A—C19—H19C	109.5
O3—C15—O2	117.79 (13)	H19B—C19—H19C	109.5
O3—C15—C3	124.45 (13)	C2—C1—H1A	109.5
O2—C15—C3	117.76 (11)	C2—C1—H1C	109.5
C9—C10—O2	122.01 (12)	H1A—C1—H1C	109.5
C9—C10—C11	122.15 (13)	C2—C1—H1B	109.5
O2—C10—C11	115.83 (12)	H1A—C1—H1B	109.5
O1—C11—C12	125.50 (13)	H1C—C1—H1B	109.5
C5—C4—C3—C15	−175.85 (10)	C4—C5—C8—N1	179.44 (11)
C9—C4—C3—C15	−52.37 (13)	C10—O2—C15—O3	178.55 (12)
C5—C4—C3—C2	−52.53 (13)	C10—O2—C15—C3	−1.65 (18)
C9—C4—C3—C2	70.95 (13)	C4—C3—C15—O3	−141.90 (14)
C9—C4—C5—C6	−96.05 (15)	C2—C3—C15—O3	96.17 (16)
C3—C4—C5—C6	24.06 (16)	C4—C3—C15—O2	38.32 (15)
C9—C4—C5—C8	84.60 (14)	C2—C3—C15—O2	−83.61 (14)
C3—C4—C5—C8	−155.30 (11)	C14—C9—C10—O2	178.53 (12)
C5—C4—C9—C10	155.04 (11)	C4—C9—C10—O2	0.45 (18)
C3—C4—C9—C10	34.75 (15)	C14—C9—C10—C11	−2.3 (2)
C5—C4—C9—C14	−22.92 (17)	C4—C9—C10—C11	179.67 (12)
C3—C4—C9—C14	−143.22 (12)	C15—O2—C10—C9	−19.32 (19)
C6—O4—C2—C1	−165.09 (12)	C15—O2—C10—C11	161.42 (12)
C6—O4—C2—C3	−40.44 (15)	C9—C10—C11—O1	−179.05 (12)
C15—C3—C2—O4	−174.74 (11)	O2—C10—C11—O1	0.21 (18)
C4—C3—C2—O4	61.77 (13)	C9—C10—C11—C12	1.0 (2)
C15—C3—C2—C1	−55.75 (16)	O2—C10—C11—C12	−179.70 (13)
C4—C3—C2—C1	−179.23 (12)	C10—C9—C14—C13	1.5 (2)
C2—O4—C6—C5	10.88 (19)	C4—C9—C14—C13	179.43 (13)
C2—O4—C6—N2	−170.26 (11)	C12—C11—O1—C16	−8.5 (2)
C8—C5—C6—O4	177.18 (12)	C10—C11—O1—C16	171.64 (13)
C4—C5—C6—O4	−2.2 (2)	O1—C11—C12—C13	−178.93 (14)
C8—C5—C6—N2	−1.6 (2)	C10—C11—C12—C13	1.0 (2)
C4—C5—C6—N2	179.07 (12)	C9—C14—C13—C12	0.5 (2)
C7—N2—C6—O4	−178.82 (13)	C11—C12—C13—C14	−1.7 (2)
C19—N2—C6—O4	7.1 (2)	C11—O1—C16—C17	−170.40 (14)
C7—N2—C6—C5	0.1 (2)	C8—N1—C7—O5	175.43 (15)
C19—N2—C6—C5	−174.03 (15)	C18—N1—C7—O5	0.9 (2)
C7—N1—C8—O6	−177.10 (14)	C8—N1—C7—N2	−4.5 (2)
C18—N1—C8—O6	−2.6 (2)	C18—N1—C7—N2	−179.10 (14)
C7—N1—C8—C5	3.1 (2)	C6—N2—C7—O5	−177.11 (15)
C18—N1—C8—C5	177.62 (13)	C19—N2—C7—O5	−2.8 (2)
C6—C5—C8—O6	−179.70 (13)	C6—N2—C7—N1	2.9 (2)
C4—C5—C8—O6	−0.3 (2)	C19—N2—C7—N1	177.15 (15)
C6—C5—C8—N1	0.07 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O6i	0.98	2.40	3.1480 (17)	132
C18—H18C···O3ii	0.96	2.45	3.252 (2)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O6i	0.98	2.40	3.1480 (17)	132
C18—H18C⋯O3ii	0.96	2.45	3.252 (2)	140

Symmetry codes: (i) ; (ii) .