rac-Dimethyl 2-(tert-butyl-amino)-5-oxo-4,5-dihydro-pyrano[3,2-c]chromene-3,4-dicarboxyl-ate.

The title compound, C(20)H(21)NO(7), is asymmetric with a chiral centre located in the pyran ring and crystallizes as a racemate. The mol-ecular framework is somewhat bent; the coumarin moiety and the pyran ring are inclined by 7.85 (5)°. The mol-ecular structure is characterized by an intra-molecular N-H⋯O hydrogen bond, which generates an S(6) ring motif, and the crystal packing is stabilized by inter-molecular C-H⋯O hydrogen bonds. The 3-carboxyl-ate O atom is involved in both of them, having a bifurcated character.

Related literature

For the biological and pharmacological activity of coumarin and its derivatives, see: Borges et al. (2005 ▶); Gursoy & Karali (2003 ▶); Moffett (1964 ▶). For a related structure, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H21NO7

M = 387.38

Monoclinic,

a = 10.0907 (2) Å

b = 16.3943 (4) Å

c = 11.8266 (2) Å

β = 107.941 (1)°

V = 1861.34 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.969, T max = 0.979

27295 measured reflections

6688 independent reflections

4069 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.158

S = 1.00

6688 reflections

258 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811041493/ld2028sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041493/ld2028Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811041493/ld2028Isup3.cml

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

C20H21NO7	F(000) = 816
Mr = 387.38	Dx = 1.382 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6688 reflections
a = 10.0907 (2) Å	θ = 2.2–32.5°
b = 16.3943 (4) Å	µ = 0.11 mm−1
c = 11.8266 (2) Å	T = 293 K
β = 107.941 (1)°	Block, colourless
V = 1861.34 (7) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	6688 independent reflections
Radiation source: fine-focus sealed tube	4069 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω and φ scans	θmax = 32.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
Tmin = 0.969, Tmax = 0.979	k = −24→24
27295 measured reflections	l = −17→17

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0737P)2 + 0.294P] where P = (Fo2 + 2Fc2)/3
6688 reflections	(Δ/σ)max < 0.001
258 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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
C1	0.60272 (14)	0.10657 (9)	0.40846 (13)	0.0459 (3)
C2	0.68858 (16)	0.12542 (11)	0.52188 (14)	0.0574 (4)
H2	0.7055	0.1794	0.5462	0.069*
C3	0.74773 (16)	0.06267 (13)	0.59709 (15)	0.0632 (5)
H3	0.8049	0.0745	0.6735	0.076*
C4	0.72413 (16)	−0.01784 (12)	0.56175 (14)	0.0593 (4)
H4	0.7647	−0.0595	0.6143	0.071*
C5	0.64022 (15)	−0.03630 (10)	0.44824 (13)	0.0489 (3)
H5	0.6253	−0.0904	0.4241	0.059*
C6	0.57782 (13)	0.02628 (8)	0.36981 (12)	0.0405 (3)
C7	0.48651 (12)	0.01446 (7)	0.25070 (11)	0.0371 (3)
C8	0.42265 (13)	0.07696 (7)	0.18224 (11)	0.0373 (3)
C9	0.44864 (15)	0.15958 (8)	0.22674 (13)	0.0458 (3)
C10	0.32265 (12)	0.06565 (7)	0.06042 (11)	0.0364 (2)
H10	0.3468	0.1037	0.0060	0.044*
C11	0.33327 (13)	−0.02048 (7)	0.01863 (11)	0.0364 (3)
C12	0.40362 (13)	−0.08012 (7)	0.09507 (11)	0.0376 (3)
C13	0.17418 (13)	0.08403 (7)	0.06189 (12)	0.0385 (3)
C14	−0.03365 (16)	0.15297 (11)	−0.03895 (17)	0.0615 (4)
H14A	−0.0825	0.1019	−0.0530	0.092*
H14B	−0.0695	0.1878	−0.1067	0.092*
H14C	−0.0464	0.1786	0.0299	0.092*
C15	0.26488 (14)	−0.04112 (8)	−0.10362 (12)	0.0416 (3)
C16	0.11252 (17)	0.00960 (12)	−0.28374 (14)	0.0625 (4)
H16A	0.1604	−0.0203	−0.3291	0.094*
H16B	0.0811	0.0608	−0.3221	0.094*
H16C	0.0339	−0.0214	−0.2785	0.094*
C17	0.48307 (18)	−0.22850 (8)	0.13618 (14)	0.0519 (4)
C18	0.4116 (3)	−0.24776 (12)	0.2283 (2)	0.0821 (6)
H18A	0.4305	−0.2051	0.2867	0.123*
H18B	0.4460	−0.2986	0.2662	0.123*
H18C	0.3129	−0.2517	0.1904	0.123*
C19	0.6380 (2)	−0.21543 (11)	0.19263 (19)	0.0730 (5)
H19A	0.6809	−0.2064	0.1316	0.109*
H19B	0.6783	−0.2628	0.2380	0.109*
H19C	0.6532	−0.1688	0.2441	0.109*
C20	0.4601 (3)	−0.29789 (10)	0.04631 (19)	0.0820 (6)
H20A	0.3621	−0.3074	0.0117	0.123*
H20B	0.5041	−0.3465	0.0857	0.123*
H20C	0.4998	−0.2834	−0.0150	0.123*
O1	0.54122 (11)	0.17100 (6)	0.33794 (10)	0.0537 (3)
O2	0.39422 (14)	0.21939 (6)	0.17376 (11)	0.0651 (3)
O3	0.12113 (11)	0.05152 (7)	0.12744 (10)	0.0568 (3)
O4	0.11235 (10)	0.13887 (6)	−0.01951 (10)	0.0539 (3)
O5	0.25835 (12)	−0.10881 (7)	−0.14909 (9)	0.0559 (3)
O6	0.20492 (12)	0.02410 (6)	−0.16718 (9)	0.0545 (3)
O7	0.47008 (10)	−0.06485 (5)	0.21316 (8)	0.0433 (2)
N1	0.41676 (14)	−0.15701 (7)	0.06458 (11)	0.0503 (3)
H1	0.3803	−0.1670	−0.0100	0.060*

	U11	U22	U33	U12	U13	U23
C1	0.0359 (6)	0.0521 (8)	0.0470 (7)	−0.0020 (5)	0.0088 (5)	−0.0071 (6)
C2	0.0439 (7)	0.0686 (10)	0.0542 (9)	−0.0058 (7)	0.0069 (7)	−0.0172 (8)
C3	0.0413 (7)	0.0934 (13)	0.0470 (8)	0.0027 (8)	0.0019 (6)	−0.0133 (9)
C4	0.0445 (8)	0.0835 (12)	0.0447 (8)	0.0112 (8)	0.0060 (6)	0.0050 (8)
C5	0.0423 (7)	0.0580 (8)	0.0429 (7)	0.0057 (6)	0.0080 (6)	0.0036 (6)
C6	0.0318 (5)	0.0473 (7)	0.0406 (7)	0.0012 (5)	0.0087 (5)	0.0000 (5)
C7	0.0345 (6)	0.0359 (6)	0.0396 (6)	−0.0013 (5)	0.0094 (5)	−0.0007 (5)
C8	0.0356 (6)	0.0333 (6)	0.0412 (6)	−0.0016 (5)	0.0090 (5)	−0.0004 (5)
C9	0.0456 (7)	0.0386 (6)	0.0497 (8)	−0.0015 (5)	0.0096 (6)	−0.0031 (6)
C10	0.0377 (6)	0.0314 (5)	0.0384 (6)	−0.0020 (4)	0.0092 (5)	0.0047 (5)
C11	0.0375 (6)	0.0330 (5)	0.0381 (6)	−0.0017 (4)	0.0108 (5)	0.0002 (5)
C12	0.0398 (6)	0.0333 (6)	0.0400 (6)	−0.0025 (5)	0.0127 (5)	0.0004 (5)
C13	0.0383 (6)	0.0323 (6)	0.0417 (7)	−0.0004 (5)	0.0074 (5)	0.0020 (5)
C14	0.0401 (7)	0.0598 (9)	0.0757 (11)	0.0082 (7)	0.0047 (7)	0.0113 (8)
C15	0.0404 (6)	0.0427 (7)	0.0416 (7)	−0.0055 (5)	0.0126 (5)	0.0008 (5)
C16	0.0517 (8)	0.0845 (12)	0.0422 (8)	−0.0023 (8)	0.0013 (6)	0.0040 (8)
C17	0.0706 (9)	0.0321 (6)	0.0569 (9)	0.0052 (6)	0.0255 (7)	0.0088 (6)
C18	0.1131 (17)	0.0600 (10)	0.0932 (15)	0.0014 (11)	0.0612 (14)	0.0179 (10)
C19	0.0713 (11)	0.0536 (9)	0.0914 (14)	0.0189 (8)	0.0212 (10)	0.0255 (9)
C20	0.1286 (19)	0.0364 (8)	0.0855 (14)	0.0102 (10)	0.0396 (13)	−0.0010 (8)
O1	0.0546 (6)	0.0424 (5)	0.0553 (6)	−0.0035 (4)	0.0039 (5)	−0.0106 (5)
O2	0.0781 (8)	0.0363 (5)	0.0692 (8)	0.0051 (5)	0.0054 (6)	−0.0007 (5)
O3	0.0503 (6)	0.0632 (7)	0.0625 (7)	0.0087 (5)	0.0255 (5)	0.0193 (5)
O4	0.0411 (5)	0.0509 (6)	0.0659 (7)	0.0077 (4)	0.0108 (5)	0.0225 (5)
O5	0.0677 (7)	0.0489 (6)	0.0474 (6)	−0.0022 (5)	0.0121 (5)	−0.0104 (5)
O6	0.0598 (6)	0.0511 (6)	0.0417 (5)	−0.0015 (5)	−0.0002 (5)	0.0038 (4)
O7	0.0514 (5)	0.0332 (4)	0.0405 (5)	0.0023 (4)	0.0074 (4)	0.0026 (4)
N1	0.0667 (8)	0.0336 (5)	0.0473 (7)	0.0054 (5)	0.0127 (6)	−0.0004 (5)

C1—O1	1.3703 (18)	C13—O4	1.3245 (15)
C1—C2	1.389 (2)	C14—O4	1.4380 (18)
C1—C6	1.3905 (19)	C14—H14A	0.9600
C2—C3	1.371 (3)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.383 (3)	C15—O5	1.2261 (16)
C3—H3	0.9300	C15—O6	1.3395 (17)
C4—C5	1.382 (2)	C16—O6	1.4262 (18)
C4—H4	0.9300	C16—H16A	0.9600
C5—C6	1.3962 (19)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600
C6—C7	1.4392 (18)	C17—N1	1.4797 (18)
C7—C8	1.3415 (17)	C17—C18	1.514 (2)
C7—O7	1.3674 (15)	C17—C19	1.514 (3)
C8—C9	1.4474 (18)	C17—C20	1.525 (2)
C8—C10	1.4942 (17)	C18—H18A	0.9600
C9—O2	1.2016 (17)	C18—H18B	0.9600
C9—O1	1.3714 (18)	C18—H18C	0.9600
C10—C11	1.5107 (17)	C19—H19A	0.9600
C10—C13	1.5335 (17)	C19—H19B	0.9600
C10—H10	0.9800	C19—H19C	0.9600
C11—C12	1.3719 (17)	C20—H20A	0.9600
C11—C15	1.4375 (18)	C20—H20B	0.9600
C12—N1	1.3288 (16)	C20—H20C	0.9600
C12—O7	1.3733 (16)	N1—H1	0.8600
C13—O3	1.1948 (16)
O1—C1—C2	116.55 (14)	H14A—C14—H14B	109.5
O1—C1—C6	121.84 (12)	O4—C14—H14C	109.5
C2—C1—C6	121.59 (14)	H14A—C14—H14C	109.5
C3—C2—C1	118.49 (16)	H14B—C14—H14C	109.5
C3—C2—H2	120.8	O5—C15—O6	121.50 (13)
C1—C2—H2	120.8	O5—C15—C11	126.77 (13)
C2—C3—C4	121.35 (15)	O6—C15—C11	111.74 (11)
C2—C3—H3	119.3	O6—C16—H16A	109.5
C4—C3—H3	119.3	O6—C16—H16B	109.5
C5—C4—C3	119.97 (16)	H16A—C16—H16B	109.5
C5—C4—H4	120.0	O6—C16—H16C	109.5
C3—C4—H4	120.0	H16A—C16—H16C	109.5
C4—C5—C6	120.02 (15)	H16B—C16—H16C	109.5
C4—C5—H5	120.0	N1—C17—C18	110.21 (14)
C6—C5—H5	120.0	N1—C17—C19	111.32 (12)
C1—C6—C5	118.57 (13)	C18—C17—C19	111.62 (16)
C1—C6—C7	116.46 (12)	N1—C17—C20	104.32 (13)
C5—C6—C7	124.96 (13)	C18—C17—C20	110.02 (15)
C8—C7—O7	122.87 (11)	C19—C17—C20	109.10 (16)
C8—C7—C6	122.11 (12)	C17—C18—H18A	109.5
O7—C7—C6	115.02 (11)	C17—C18—H18B	109.5
C7—C8—C9	119.72 (12)	H18A—C18—H18B	109.5
C7—C8—C10	122.91 (11)	C17—C18—H18C	109.5
C9—C8—C10	117.36 (11)	H18A—C18—H18C	109.5
O2—C9—O1	117.10 (12)	H18B—C18—H18C	109.5
O2—C9—C8	124.86 (13)	C17—C19—H19A	109.5
O1—C9—C8	118.04 (12)	C17—C19—H19B	109.5
C8—C10—C11	109.67 (10)	H19A—C19—H19B	109.5
C8—C10—C13	109.67 (10)	C17—C19—H19C	109.5
C11—C10—C13	110.81 (10)	H19A—C19—H19C	109.5
C8—C10—H10	108.9	H19B—C19—H19C	109.5
C11—C10—H10	108.9	C17—C20—H20A	109.5
C13—C10—H10	108.9	C17—C20—H20B	109.5
C12—C11—C15	119.05 (11)	H20A—C20—H20B	109.5
C12—C11—C10	121.68 (11)	C17—C20—H20C	109.5
C15—C11—C10	119.25 (11)	H20A—C20—H20C	109.5
N1—C12—C11	124.89 (12)	H20B—C20—H20C	109.5
N1—C12—O7	112.99 (11)	C1—O1—C9	121.69 (11)
C11—C12—O7	122.12 (11)	C13—O4—C14	117.09 (12)
O3—C13—O4	124.71 (12)	C15—O6—C16	117.20 (12)
O3—C13—C10	123.67 (11)	C7—O7—C12	118.42 (10)
O4—C13—C10	111.61 (11)	C12—N1—C17	131.41 (13)
O4—C14—H14A	109.5	C12—N1—H1	114.3
O4—C14—H14B	109.5	C17—N1—H1	114.3
O1—C1—C2—C3	177.39 (13)	C13—C10—C11—C15	69.62 (14)
C6—C1—C2—C3	−1.0 (2)	C15—C11—C12—N1	1.5 (2)
C1—C2—C3—C4	0.4 (2)	C10—C11—C12—N1	179.80 (12)
C2—C3—C4—C5	0.5 (3)	C15—C11—C12—O7	−179.35 (11)
C3—C4—C5—C6	−0.8 (2)	C10—C11—C12—O7	−1.03 (18)
O1—C1—C6—C5	−177.67 (12)	C8—C10—C13—O3	−54.74 (16)
C2—C1—C6—C5	0.6 (2)	C11—C10—C13—O3	66.48 (17)
O1—C1—C6—C7	1.41 (19)	C8—C10—C13—O4	126.41 (12)
C2—C1—C6—C7	179.72 (13)	C11—C10—C13—O4	−112.38 (12)
C4—C5—C6—C1	0.3 (2)	C12—C11—C15—O5	2.2 (2)
C4—C5—C6—C7	−178.70 (13)	C10—C11—C15—O5	−176.18 (13)
C1—C6—C7—C8	−3.39 (18)	C12—C11—C15—O6	−178.03 (11)
C5—C6—C7—C8	175.63 (13)	C10—C11—C15—O6	3.61 (16)
C1—C6—C7—O7	176.64 (11)	C2—C1—O1—C9	−176.45 (13)
C5—C6—C7—O7	−4.34 (18)	C6—C1—O1—C9	1.9 (2)
O7—C7—C8—C9	−178.01 (11)	O2—C9—O1—C1	176.14 (13)
C6—C7—C8—C9	2.02 (19)	C8—C9—O1—C1	−3.3 (2)
O7—C7—C8—C10	2.75 (19)	O3—C13—O4—C14	−7.5 (2)
C6—C7—C8—C10	−177.22 (11)	C10—C13—O4—C14	171.38 (12)
C7—C8—C9—O2	−178.08 (14)	O5—C15—O6—C16	11.0 (2)
C10—C8—C9—O2	1.2 (2)	C11—C15—O6—C16	−168.79 (12)
C7—C8—C9—O1	1.36 (19)	C8—C7—O7—C12	10.56 (18)
C10—C8—C9—O1	−179.36 (11)	C6—C7—O7—C12	−169.47 (10)
C7—C8—C10—C11	−13.49 (16)	N1—C12—O7—C7	167.98 (11)
C9—C8—C10—C11	167.26 (11)	C11—C12—O7—C7	−11.28 (17)
C7—C8—C10—C13	108.41 (13)	C11—C12—N1—C17	−177.04 (14)
C9—C8—C10—C13	−70.84 (14)	O7—C12—N1—C17	3.7 (2)
C8—C10—C11—C12	12.52 (16)	C18—C17—N1—C12	61.5 (2)
C13—C10—C11—C12	−108.70 (13)	C19—C17—N1—C12	−62.9 (2)
C8—C10—C11—C15	−169.16 (10)	C20—C17—N1—C12	179.60 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.86	1.97	2.6602 (16)	136
C19—H19B···O5i	0.96	2.49	3.4469 (19)	174.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5	0.86	1.97	2.6602 (16)	136
C19—H19B⋯O5i	0.96	2.49	3.4469 (19)	174

Symmetry code: (i) .