Ethyl 2-amino-5-oxo-4-(p-tolyl)-4H,5H-pyrano[3,2-c]chromene-8-carboxyl­ate

The title compound, C₂₂H₁₉NO₅, was synthesized by the reaction of 4-hydroxy­coumarin and ethyl 4′-methyl-2-cyano­cinnamate in the presence of triethyl­benzyl­ammonium chloride in an aqueous medium. In the crystal structure, the amino group is involved in both intra- and intermolecular N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.101
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.54 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11    -   C12     ..       5.13 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Ethyl 9-amino-7-(p-tolyl)-7H-pyrano[3,2-c]coumarin-8-carboxylate

Crystal data

C22H19NO5	F(000) = 792
Mr = 377.38	Dx = 1.347 Mg m^−3
Monoclinic, P21/c	Melting point = 464–465 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.239 (2) Å	Cell parameters from 39 reflections
b = 7.850 (1) Å	θ = 3.1–14.8°
c = 15.846 (3) Å	µ = 0.10 mm^−1
β = 101.00 (1)°	T = 296 K
V = 1860.7 (5) Å^3	Block, colourless
Z = 4	0.58 × 0.52 × 0.12 mm

Data collection

Siemens P4 diffractometer	Rint = 0.014
Radiation source: normal-focus sealed tube	θmax = 25.3°, θmin = 1.4°
Graphite monochromator	h = 0→18
ω scans	k = 0→9
3918 measured reflections	l = −19→18
3379 independent reflections	3 standard reflections every 97 reflections
2173 reflections with I > 2σ(I)	intensity decay: 4.9%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0538P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max < 0.001
3379 reflections	Δρmax = 0.17 e Å^−3
263 parameters	Δρmin = −0.15 e Å^−3
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0124 (9)

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	Occ. (<1)
O1	0.64193 (8)	0.19343 (14)	0.21859 (7)	0.0418 (3)
O2	0.50048 (7)	0.62681 (16)	0.13568 (8)	0.0463 (3)
O3	0.59842 (9)	0.78971 (16)	0.21782 (9)	0.0546 (4)
O4	0.80705 (9)	0.47615 (17)	0.45982 (8)	0.0561 (4)
O5	0.80808 (9)	0.18976 (18)	0.46140 (8)	0.0575 (4)
N	0.72474 (12)	0.0314 (2)	0.31677 (12)	0.0498 (4)
C1	0.59831 (10)	0.3425 (2)	0.19417 (10)	0.0347 (4)
C2	0.51913 (11)	0.3223 (2)	0.12928 (11)	0.0375 (4)
C3	0.48594 (12)	0.1657 (2)	0.09449 (12)	0.0476 (5)
H3	0.5162	0.0653	0.1124	0.057*
C4	0.40829 (13)	0.1611 (3)	0.03366 (13)	0.0570 (6)
H4	0.3862	0.0574	0.0104	0.068*
C5	0.36301 (13)	0.3104 (3)	0.00695 (13)	0.0581 (6)
H5	0.3107	0.3055	−0.0343	0.070*
C6	0.39402 (12)	0.4661 (3)	0.04026 (12)	0.0520 (5)
H6	0.3636	0.5660	0.0218	0.062*
C7	0.47204 (11)	0.4694 (2)	0.10215 (11)	0.0409 (5)
C8	0.57810 (11)	0.6455 (2)	0.19591 (11)	0.0398 (4)
C9	0.62770 (11)	0.4938 (2)	0.22716 (10)	0.0345 (4)
C10	0.71228 (11)	0.5094 (2)	0.29399 (11)	0.0359 (4)
H10	0.7022	0.5937	0.3367	0.043*
C11	0.73056 (10)	0.3380 (2)	0.33873 (11)	0.0366 (4)
C12	0.70185 (11)	0.1916 (2)	0.29591 (11)	0.0377 (4)
C13	0.79247 (11)	0.5667 (2)	0.25616 (11)	0.0347 (4)
C14	0.80562 (11)	0.5081 (2)	0.17688 (11)	0.0409 (5)
H14	0.7624	0.4392	0.1441	0.049*
C15	0.88149 (12)	0.5500 (2)	0.14544 (12)	0.0466 (5)
H15	0.8883	0.5089	0.0920	0.056*
C16	0.94745 (11)	0.6521 (2)	0.19214 (13)	0.0477 (5)
C17	0.93370 (12)	0.7113 (2)	0.27057 (13)	0.0520 (5)
H17	0.9769	0.7806	0.3031	0.062*
C18	0.85807 (11)	0.6713 (2)	0.30227 (12)	0.0446 (5)
H18	0.8509	0.7148	0.3551	0.054*
C19	1.03096 (13)	0.6967 (3)	0.15922 (15)	0.0724 (7)
H19A	1.0289	0.6446	0.1041	0.087*	0.50
H19B	1.0823	0.6558	0.1988	0.087*	0.50
H19C	1.0349	0.8181	0.1538	0.087*	0.50
H19D	1.0685	0.7678	0.2004	0.087*	0.50
H19E	1.0151	0.7565	0.1056	0.087*	0.50
H19F	1.0625	0.5942	0.1507	0.087*	0.50
C20	0.78447 (11)	0.3229 (3)	0.42353 (11)	0.0426 (5)
C21	0.86360 (16)	0.4768 (3)	0.54441 (13)	0.0740 (7)
H21A	0.8995	0.5798	0.5512	0.089*
H21B	0.9040	0.3802	0.5494	0.089*
C22	0.81160 (18)	0.4685 (3)	0.61317 (14)	0.0873 (9)
H22A	0.7750	0.5684	0.6112	0.105*
H22B	0.8515	0.4625	0.6678	0.105*
H22C	0.7743	0.3690	0.6055	0.105*
H1A	0.7590 (11)	0.017 (2)	0.3679 (8)	0.060 (7)*
H1B	0.6907 (12)	−0.050 (2)	0.2891 (12)	0.076 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0407 (7)	0.0363 (7)	0.0444 (7)	0.0006 (6)	−0.0025 (6)	−0.0030 (6)
O2	0.0350 (7)	0.0485 (8)	0.0527 (8)	0.0066 (6)	0.0012 (6)	0.0011 (6)
O3	0.0557 (8)	0.0364 (8)	0.0669 (9)	0.0026 (7)	0.0001 (7)	−0.0038 (7)
O4	0.0665 (9)	0.0555 (9)	0.0395 (7)	−0.0112 (7)	−0.0073 (7)	−0.0036 (7)
O5	0.0599 (9)	0.0572 (10)	0.0501 (8)	0.0028 (7)	−0.0034 (7)	0.0114 (7)
N	0.0532 (11)	0.0389 (10)	0.0528 (11)	0.0005 (9)	−0.0010 (9)	0.0033 (9)
C1	0.0290 (9)	0.0382 (10)	0.0373 (9)	0.0002 (8)	0.0075 (8)	0.0004 (8)
C2	0.0298 (9)	0.0465 (11)	0.0367 (10)	−0.0059 (8)	0.0076 (8)	−0.0008 (8)
C3	0.0425 (11)	0.0517 (12)	0.0484 (11)	−0.0063 (10)	0.0079 (9)	−0.0057 (10)
C4	0.0456 (12)	0.0690 (15)	0.0537 (13)	−0.0134 (11)	0.0025 (10)	−0.0136 (11)
C5	0.0355 (11)	0.0861 (18)	0.0493 (12)	−0.0085 (12)	−0.0002 (9)	−0.0063 (12)
C6	0.0332 (10)	0.0749 (15)	0.0467 (11)	0.0055 (10)	0.0043 (9)	0.0059 (11)
C7	0.0308 (9)	0.0537 (12)	0.0393 (10)	−0.0027 (9)	0.0095 (8)	−0.0020 (9)
C8	0.0334 (10)	0.0430 (12)	0.0431 (10)	0.0012 (9)	0.0076 (8)	−0.0010 (9)
C9	0.0287 (9)	0.0372 (10)	0.0378 (9)	−0.0031 (8)	0.0073 (7)	0.0001 (8)
C10	0.0343 (9)	0.0347 (10)	0.0372 (10)	−0.0020 (8)	0.0034 (8)	−0.0048 (8)
C11	0.0324 (9)	0.0386 (10)	0.0380 (10)	−0.0024 (8)	0.0047 (8)	−0.0004 (8)
C12	0.0327 (9)	0.0412 (11)	0.0391 (10)	0.0017 (8)	0.0065 (8)	0.0038 (9)
C13	0.0304 (9)	0.0312 (9)	0.0400 (10)	0.0013 (8)	0.0002 (8)	0.0012 (8)
C14	0.0320 (9)	0.0420 (11)	0.0461 (11)	−0.0037 (8)	0.0010 (8)	−0.0021 (9)
C15	0.0374 (10)	0.0540 (12)	0.0485 (11)	0.0012 (10)	0.0081 (9)	0.0038 (10)
C16	0.0317 (10)	0.0488 (12)	0.0606 (13)	−0.0008 (9)	0.0039 (9)	0.0160 (10)
C17	0.0386 (11)	0.0454 (12)	0.0661 (14)	−0.0142 (9)	−0.0048 (10)	0.0012 (11)
C18	0.0425 (11)	0.0385 (11)	0.0494 (11)	−0.0063 (9)	0.0001 (9)	−0.0043 (9)
C19	0.0393 (11)	0.0846 (18)	0.0936 (18)	−0.0044 (12)	0.0133 (12)	0.0229 (14)
C20	0.0366 (10)	0.0480 (12)	0.0425 (11)	−0.0034 (9)	0.0062 (9)	0.0016 (10)
C21	0.0792 (16)	0.0827 (18)	0.0489 (13)	−0.0132 (14)	−0.0160 (12)	−0.0066 (13)
C22	0.126 (2)	0.0778 (18)	0.0509 (14)	0.0013 (17)	−0.0015 (15)	0.0004 (13)

Geometric parameters (Å, º)

O1—C1	1.365 (2)	C10—H10	0.9800
O1—C12	1.381 (2)	C11—C12	1.364 (2)
O2—C8	1.379 (2)	C11—C20	1.440 (2)
O2—C7	1.382 (2)	C13—C14	1.388 (2)
O3—C8	1.207 (2)	C13—C18	1.389 (2)
O4—C20	1.349 (2)	C14—C15	1.383 (2)
O4—C21	1.449 (2)	C14—H14	0.9300
O5—C20	1.224 (2)	C15—C16	1.384 (2)
N—C12	1.330 (2)	C15—H15	0.9300
N—H1A	0.883 (9)	C16—C17	1.380 (3)
N—H1B	0.883 (9)	C16—C19	1.506 (3)
C1—C9	1.339 (2)	C17—C18	1.379 (3)
C1—C2	1.437 (2)	C17—H17	0.9300
C2—C7	1.384 (2)	C18—H18	0.9300
C2—C3	1.402 (2)	C19—H19A	0.9600
C3—C4	1.377 (2)	C19—H19B	0.9600
C3—H3	0.9300	C19—H19C	0.9600
C4—C5	1.385 (3)	C19—H19D	0.9600
C4—H4	0.9300	C19—H19E	0.9600
C5—C6	1.378 (3)	C19—H19F	0.9600
C5—H5	0.9300	C21—C22	1.466 (3)
C6—C7	1.390 (2)	C21—H21A	0.9700
C6—H6	0.9300	C21—H21B	0.9700
C8—C9	1.447 (2)	C22—H22A	0.9600
C9—C10	1.509 (2)	C22—H22B	0.9600
C10—C11	1.521 (2)	C22—H22C	0.9600
C10—C13	1.528 (2)
C1—O1—C12	117.65 (13)	C13—C14—H14	119.2
C8—O2—C7	121.75 (14)	C14—C15—C16	121.10 (18)
C20—O4—C21	117.13 (16)	C14—C15—H15	119.4
C12—N—H1A	115.4 (13)	C16—C15—H15	119.4
C12—N—H1B	117.2 (14)	C17—C16—C15	117.19 (17)
H1A—N—H1B	124 (2)	C17—C16—C19	121.14 (18)
C9—C1—O1	122.75 (15)	C15—C16—C19	121.7 (2)
C9—C1—C2	123.37 (16)	C18—C17—C16	122.18 (17)
O1—C1—C2	113.88 (15)	C18—C17—H17	118.9
C7—C2—C3	118.87 (16)	C16—C17—H17	118.9
C7—C2—C1	116.40 (16)	C17—C18—C13	120.73 (18)
C3—C2—C1	124.70 (17)	C17—C18—H18	119.6
C4—C3—C2	119.71 (19)	C13—C18—H18	119.6
C4—C3—H3	120.1	C16—C19—H19A	109.5
C2—C3—H3	120.1	C16—C19—H19B	109.5
C3—C4—C5	120.2 (2)	H19A—C19—H19B	109.5
C3—C4—H4	119.9	C16—C19—H19C	109.5
C5—C4—H4	119.9	H19A—C19—H19C	109.5
C6—C5—C4	121.26 (18)	H19B—C19—H19C	109.5
C6—C5—H5	119.4	C16—C19—H19D	109.5
C4—C5—H5	119.4	H19A—C19—H19D	141.1
C5—C6—C7	118.1 (2)	H19B—C19—H19D	56.3
C5—C6—H6	120.9	H19C—C19—H19D	56.3
C7—C6—H6	120.9	C16—C19—H19E	109.5
O2—C7—C2	121.38 (15)	H19A—C19—H19E	56.3
O2—C7—C6	116.85 (17)	H19B—C19—H19E	141.1
C2—C7—C6	121.77 (18)	H19C—C19—H19E	56.3
O3—C8—O2	115.99 (16)	H19D—C19—H19E	109.5
O3—C8—C9	125.82 (16)	C16—C19—H19F	109.5
O2—C8—C9	118.19 (16)	H19A—C19—H19F	56.3
C1—C9—C8	118.84 (16)	H19B—C19—H19F	56.3
C1—C9—C10	121.54 (15)	H19C—C19—H19F	141.1
C8—C9—C10	119.60 (15)	H19D—C19—H19F	109.5
C9—C10—C11	108.14 (13)	H19E—C19—H19F	109.5
C9—C10—C13	112.86 (13)	O5—C20—O4	121.66 (16)
C11—C10—C13	110.74 (13)	O5—C20—C11	126.13 (18)
C9—C10—H10	108.3	O4—C20—C11	112.21 (16)
C11—C10—H10	108.3	O4—C21—C22	112.2 (2)
C13—C10—H10	108.3	O4—C21—H21A	109.2
C12—C11—C20	117.82 (16)	C22—C21—H21A	109.2
C12—C11—C10	120.04 (15)	O4—C21—H21B	109.2
C20—C11—C10	121.92 (16)	C22—C21—H21B	109.2
N—C12—C11	128.99 (17)	H21A—C21—H21B	107.9
N—C12—O1	109.15 (16)	C21—C22—H22A	109.5
C11—C12—O1	121.84 (16)	C21—C22—H22B	109.5
C14—C13—C18	117.28 (16)	H22A—C22—H22B	109.5
C14—C13—C10	121.47 (15)	C21—C22—H22C	109.5
C18—C13—C10	121.13 (16)	H22A—C22—H22C	109.5
C15—C14—C13	121.50 (16)	H22B—C22—H22C	109.5
C15—C14—H14	119.2
C12—O1—C1—C9	19.3 (2)	C8—C9—C10—C13	−78.19 (19)
C12—O1—C1—C2	−161.54 (14)	C9—C10—C11—C12	28.4 (2)
C9—C1—C2—C7	−1.0 (3)	C13—C10—C11—C12	−95.70 (18)
O1—C1—C2—C7	179.88 (14)	C9—C10—C11—C20	−157.01 (15)
C9—C1—C2—C3	−178.96 (17)	C13—C10—C11—C20	78.86 (19)
O1—C1—C2—C3	1.9 (2)	C20—C11—C12—N	−8.7 (3)
C7—C2—C3—C4	0.8 (3)	C10—C11—C12—N	166.09 (18)
C1—C2—C3—C4	178.73 (17)	C20—C11—C12—O1	172.70 (15)
C2—C3—C4—C5	−0.1 (3)	C10—C11—C12—O1	−12.5 (2)
C3—C4—C5—C6	−0.1 (3)	C1—O1—C12—N	168.35 (14)
C4—C5—C6—C7	−0.4 (3)	C1—O1—C12—C11	−12.8 (2)
C8—O2—C7—C2	1.7 (2)	C9—C10—C13—C14	−38.7 (2)
C8—O2—C7—C6	−178.43 (16)	C11—C10—C13—C14	82.71 (19)
C3—C2—C7—O2	178.48 (15)	C9—C10—C13—C18	145.38 (16)
C1—C2—C7—O2	0.4 (2)	C11—C10—C13—C18	−93.23 (18)
C3—C2—C7—C6	−1.3 (3)	C18—C13—C14—C15	0.9 (3)
C1—C2—C7—C6	−179.46 (16)	C10—C13—C14—C15	−175.17 (16)
C5—C6—C7—O2	−178.68 (16)	C13—C14—C15—C16	0.1 (3)
C5—C6—C7—C2	1.2 (3)	C14—C15—C16—C17	−0.7 (3)
C7—O2—C8—O3	176.84 (15)	C14—C15—C16—C19	179.17 (18)
C7—O2—C8—C9	−3.2 (2)	C15—C16—C17—C18	0.3 (3)
O1—C1—C9—C8	178.61 (15)	C19—C16—C17—C18	−179.58 (18)
C2—C1—C9—C8	−0.5 (3)	C16—C17—C18—C13	0.7 (3)
O1—C1—C9—C10	0.3 (3)	C14—C13—C18—C17	−1.3 (3)
C2—C1—C9—C10	−178.77 (15)	C10—C13—C18—C17	174.79 (16)
O3—C8—C9—C1	−177.49 (18)	C21—O4—C20—O5	2.4 (3)
O2—C8—C9—C1	2.5 (2)	C21—O4—C20—C11	−178.24 (17)
O3—C8—C9—C10	0.8 (3)	C12—C11—C20—O5	0.6 (3)
O2—C8—C9—C10	−179.16 (14)	C10—C11—C20—O5	−174.05 (17)
C1—C9—C10—C11	−22.8 (2)	C12—C11—C20—O4	−178.69 (15)
C8—C9—C10—C11	158.96 (15)	C10—C11—C20—O4	6.6 (2)
C1—C9—C10—C13	100.09 (18)	C20—O4—C21—C22	−88.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1A···O5	0.88 (1)	2.04 (2)	2.702 (2)	131 (2)
N—H1B···O3^i	0.88 (1)	2.06 (1)	2.935 (2)	171 (2)

Symmetry code: (i) x, y−1, z.