Ethyl 2-hydr-oxy-5-oxo-4-phenyl-2,3,4,5-tetra-hydro-pyrano[3,2-c]chromene-2-carboxyl-ate.

The main structural unit of the title compoud, C(21)H(18)O(6), is a fused three-ring group consisting of coumarin and tetra-hydro-pyrane ring systems. Two C atoms of the tetra-hydro-pyran ring are displaced by 0.295 (3) and -0.360 (2) Å from the mean plane of coumarin ring. The dihedral angle between the phenyl and coumarin rings is 73.94 (3)°. Inter-molecular O-H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For the synthesis of (E)-ethyl 2-oxo-4-phenyl­but-3-enoate, see: Vaijayanthi & Chadha (2007 ▶).

Experimental

Crystal data

C21H18O6

M = 366.37

Monoclinic,

a = 5.4988 (2) Å

b = 14.9975 (5) Å

c = 21.342 (1) Å

β = 98.5487 (13)°

V = 1740.48 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.41 × 0.39 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 2005 ▶) T min = 0.954, T max = 0.986

16523 measured reflections

3422 independent reflections

2568 reflections with F 2 > 2σ(F 2)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.080

S = 1.00

3422 reflections

246 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.19 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028311/pk2181sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028311/pk2181Isup2.hkl

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

C21H18O6	F(000) = 768.00
Mr = 366.37	Dx = 1.398 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 11365 reflections
a = 5.4988 (2) Å	θ = 3.2–27.4°
b = 14.9975 (5) Å	µ = 0.10 mm−1
c = 21.342 (1) Å	T = 296 K
β = 98.5487 (13)°	Platelet, colorless
V = 1740.48 (12) Å3	0.41 × 0.39 × 0.14 mm
Z = 4

Rigaku R-AXIS RAPID diffractometer	2568 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1	Rint = 0.026
ω scans	θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 2005)	h = −7→7
Tmin = 0.954, Tmax = 0.986	k = −19→16
16523 measured reflections	l = −27→27
3422 independent reflections

Refinement on F2	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035	w = 1/[σ2(Fo2) + (0.013P)2 + P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.21 e Å−3
3422 reflections	Δρmin = −0.19 e Å−3
246 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0057 (4)

Geometry. The tetrahydropyrane structure in the crystal displays an envelope configuration, with atom C2 at the flap position, displaced by 0.603 (2) Å from the mean plane of the other atoms.

Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

	x	y	z	Uiso*/Ueq
O1	0.3270 (2)	0.47260 (6)	0.24846 (5)	0.0400 (2)
O2	0.3755 (2)	0.12605 (6)	0.19275 (5)	0.0442 (3)
O3	0.2981 (2)	0.39483 (6)	0.15453 (5)	0.0369 (2)
O4	0.7169 (2)	0.14798 (8)	0.25944 (6)	0.0548 (3)
O5	0.2708 (2)	0.60253 (9)	0.16249 (6)	0.0562 (3)
O6	0.5597 (2)	0.54329 (8)	0.11100 (6)	0.0483 (3)
C1	0.4400 (2)	0.46019 (10)	0.19571 (6)	0.0320 (3)
C2	0.7020 (2)	0.42864 (10)	0.21432 (8)	0.0344 (3)
C3	0.7153 (2)	0.33839 (10)	0.24884 (6)	0.0326 (3)
C4	0.5223 (2)	0.27767 (10)	0.21402 (6)	0.0322 (3)
C5	0.5514 (3)	0.18281 (11)	0.22491 (8)	0.0383 (3)
C6	0.1792 (3)	0.15776 (11)	0.15092 (6)	0.0390 (3)
C7	0.0084 (3)	0.09575 (12)	0.12389 (8)	0.0504 (4)
C8	−0.1910 (3)	0.12559 (12)	0.08244 (9)	0.0548 (5)
C9	−0.2214 (3)	0.21535 (12)	0.06798 (8)	0.0490 (4)
C10	−0.0505 (2)	0.27653 (11)	0.09506 (6)	0.0394 (3)
C11	0.1532 (2)	0.24823 (10)	0.13760 (6)	0.0335 (3)
C12	0.3355 (2)	0.30795 (10)	0.17075 (6)	0.0312 (3)
C13	0.7091 (2)	0.34673 (10)	0.31968 (6)	0.0334 (3)
C14	0.9040 (3)	0.38961 (12)	0.35684 (8)	0.0429 (4)
C15	0.9097 (3)	0.39905 (12)	0.42137 (9)	0.0526 (4)
C16	0.7198 (3)	0.36628 (13)	0.45022 (9)	0.0554 (5)
C17	0.5260 (3)	0.32322 (13)	0.41407 (9)	0.0526 (4)
C18	0.5209 (3)	0.31326 (12)	0.34917 (8)	0.0427 (4)
C19	0.4127 (2)	0.54477 (11)	0.15467 (8)	0.0368 (3)
C20	0.5607 (4)	0.62325 (13)	0.07224 (10)	0.0632 (5)
C21	0.7368 (4)	0.60702 (17)	0.02723 (11)	0.0822 (7)
H3	0.8750	0.3122	0.2443	0.039*
H7	0.0279	0.0354	0.1335	0.060*
H8	−0.3073	0.0848	0.0638	0.066*
H9	−0.3574	0.2343	0.0400	0.059*
H10	−0.0706	0.3367	0.0851	0.047*
H11	0.7910	0.4727	0.2421	0.041*
H12	0.7781	0.4226	0.1763	0.041*
H14	1.0325	0.4123	0.3378	0.051*
H15	1.0420	0.4276	0.4455	0.063*
H16	0.7223	0.3731	0.4936	0.066*
H17	0.3979	0.3007	0.4333	0.063*
H18	0.3898	0.2838	0.3253	0.051*
H101	0.2350	0.5159	0.2417	0.048*
H201	0.6127	0.6743	0.0988	0.076*
H202	0.3976	0.6341	0.0492	0.076*
H211	0.8950	0.5924	0.0504	0.099*
H212	0.7504	0.6597	0.0025	0.099*
H213	0.6791	0.5585	−0.0003	0.099*

	U11	U22	U33	U12	U13	U23
O1	0.0426 (6)	0.0374 (6)	0.0417 (6)	0.0076 (5)	0.0117 (5)	0.0020 (5)
O2	0.0565 (7)	0.0292 (5)	0.0443 (6)	−0.0051 (5)	−0.0012 (5)	0.0017 (5)
O3	0.0413 (6)	0.0266 (5)	0.0394 (6)	−0.0019 (4)	−0.0047 (4)	0.0001 (4)
O4	0.0603 (8)	0.0355 (6)	0.0628 (8)	0.0082 (6)	−0.0107 (6)	0.0050 (6)
O5	0.0556 (7)	0.0415 (7)	0.0723 (9)	0.0130 (6)	0.0120 (6)	0.0145 (6)
O6	0.0652 (8)	0.0371 (6)	0.0445 (7)	−0.0020 (5)	0.0149 (6)	0.0096 (5)
C1	0.0357 (8)	0.0282 (7)	0.0322 (8)	−0.0027 (6)	0.0054 (6)	−0.0020 (6)
C2	0.0326 (7)	0.0315 (8)	0.0393 (8)	−0.0032 (6)	0.0056 (6)	0.0008 (6)
C3	0.0293 (7)	0.0318 (8)	0.0364 (8)	0.0025 (6)	0.0041 (6)	−0.0009 (6)
C4	0.0358 (8)	0.0281 (7)	0.0329 (8)	−0.0006 (6)	0.0059 (6)	−0.0011 (6)
C5	0.0457 (9)	0.0324 (8)	0.0365 (8)	−0.0014 (7)	0.0053 (7)	−0.0002 (7)
C6	0.0492 (9)	0.0373 (9)	0.0303 (8)	−0.0064 (7)	0.0049 (7)	−0.0005 (6)
C7	0.0719 (12)	0.0364 (9)	0.0404 (10)	−0.0173 (9)	0.0005 (9)	0.0006 (7)
C8	0.0683 (12)	0.0529 (11)	0.0398 (10)	−0.0267 (10)	−0.0031 (9)	−0.0026 (8)
C9	0.0507 (10)	0.0559 (11)	0.0376 (9)	−0.0111 (9)	−0.0025 (7)	−0.0013 (8)
C10	0.0457 (9)	0.0386 (9)	0.0333 (8)	−0.0048 (7)	0.0040 (7)	−0.0014 (7)
C11	0.0401 (8)	0.0331 (8)	0.0276 (7)	−0.0054 (7)	0.0064 (6)	−0.0032 (6)
C12	0.0370 (8)	0.0273 (7)	0.0304 (7)	−0.0023 (6)	0.0089 (6)	−0.0010 (6)
C13	0.0335 (7)	0.0303 (8)	0.0355 (8)	0.0065 (6)	0.0016 (6)	0.0027 (6)
C14	0.0405 (9)	0.0452 (10)	0.0408 (9)	0.0015 (7)	−0.0014 (7)	−0.0003 (7)
C15	0.0515 (10)	0.0561 (11)	0.0445 (10)	0.0083 (9)	−0.0117 (8)	−0.0060 (8)
C16	0.0647 (12)	0.0645 (12)	0.0351 (9)	0.0220 (10)	0.0014 (9)	−0.0008 (9)
C17	0.0525 (10)	0.0642 (12)	0.0433 (10)	0.0116 (9)	0.0146 (8)	0.0081 (9)
C18	0.0394 (9)	0.0465 (10)	0.0416 (9)	0.0015 (7)	0.0042 (7)	0.0010 (7)
C19	0.0398 (8)	0.0317 (8)	0.0372 (9)	−0.0057 (7)	0.0005 (7)	0.0013 (6)
C20	0.0818 (14)	0.0490 (11)	0.0601 (13)	−0.0083 (10)	0.0147 (11)	0.0222 (9)
C21	0.1051 (19)	0.0793 (16)	0.0674 (15)	−0.0195 (14)	0.0301 (14)	0.0151 (13)

O1—C1	1.3772 (19)	C13—C18	1.383 (2)
O2—C5	1.3906 (19)	C14—C15	1.380 (2)
O2—C6	1.3791 (18)	C15—C16	1.379 (2)
O3—C1	1.4623 (17)	C16—C17	1.379 (2)
O3—C12	1.3560 (18)	C17—C18	1.389 (2)
O4—C5	1.2019 (19)	C20—C21	1.482 (3)
O5—C19	1.194 (2)	O1—H101	0.822
O6—C19	1.321 (2)	C2—H11	0.970
O6—C20	1.457 (2)	C2—H12	0.970
C1—C2	1.512 (2)	C3—H3	0.980
C1—C19	1.536 (2)	C7—H7	0.930
C2—C3	1.538 (2)	C8—H8	0.930
C3—C4	1.508 (2)	C9—H9	0.930
C3—C13	1.522 (2)	C10—H10	0.930
C4—C5	1.447 (2)	C14—H14	0.930
C4—C12	1.353 (2)	C15—H15	0.930
C6—C7	1.385 (2)	C16—H16	0.930
C6—C11	1.389 (2)	C17—H17	0.930
C7—C8	1.377 (2)	C18—H18	0.930
C8—C9	1.386 (2)	C20—H201	0.970
C9—C10	1.378 (2)	C20—H202	0.970
C10—C11	1.399 (2)	C21—H211	0.960
C11—C12	1.448 (2)	C21—H212	0.960
C13—C14	1.392 (2)	C21—H213	0.960
C5—O2—C6	121.90 (12)	O5—C19—C1	122.00 (16)
C1—O3—C12	116.34 (10)	O6—C19—C1	111.72 (13)
C19—O6—C20	116.16 (14)	O6—C20—C21	106.91 (17)
O1—C1—O3	108.45 (12)	C1—O1—H101	107.7
O1—C1—C2	110.84 (12)	C1—C2—H11	108.8
O1—C1—C19	109.68 (12)	C1—C2—H12	108.8
O3—C1—C2	110.52 (12)	C3—C2—H11	108.8
O3—C1—C19	102.28 (11)	C3—C2—H12	108.8
C2—C1—C19	114.63 (13)	H11—C2—H12	109.5
C1—C2—C3	112.15 (12)	C2—C3—H3	106.5
C2—C3—C4	108.40 (11)	C4—C3—H3	106.5
C2—C3—C13	113.39 (12)	C13—C3—H3	106.5
C4—C3—C13	114.91 (12)	C6—C7—H7	120.8
C3—C4—C5	117.50 (12)	C8—C7—H7	120.8
C3—C4—C12	122.74 (13)	C7—C8—H8	119.4
C5—C4—C12	119.62 (13)	C9—C8—H8	119.4
O2—C5—O4	116.37 (14)	C8—C9—H9	119.9
O2—C5—C4	118.06 (13)	C10—C9—H9	119.9
O4—C5—C4	125.57 (14)	C9—C10—H10	120.0
O2—C6—C7	117.07 (14)	C11—C10—H10	120.0
O2—C6—C11	121.07 (13)	C13—C14—H14	119.4
C7—C6—C11	121.85 (14)	C15—C14—H14	119.4
C6—C7—C8	118.37 (16)	C14—C15—H15	119.9
C7—C8—C9	121.12 (17)	C16—C15—H15	119.9
C8—C9—C10	120.10 (15)	C15—C16—H16	120.3
C9—C10—C11	120.05 (15)	C17—C16—H16	120.3
C6—C11—C10	118.50 (13)	C16—C17—H17	119.8
C6—C11—C12	117.48 (12)	C18—C17—H17	119.8
C10—C11—C12	123.97 (13)	C13—C18—H18	119.7
O3—C12—C4	124.57 (13)	C17—C18—H18	119.7
O3—C12—C11	113.70 (12)	O6—C20—H201	110.1
C4—C12—C11	121.72 (13)	O6—C20—H202	110.1
C3—C13—C14	118.36 (14)	C21—C20—H201	110.1
C3—C13—C18	123.41 (13)	C21—C20—H202	110.1
C14—C13—C18	118.23 (14)	H201—C20—H202	109.5
C13—C14—C15	121.16 (16)	C20—C21—H211	109.5
C14—C15—C16	120.15 (16)	C20—C21—H212	109.5
C15—C16—C17	119.36 (17)	C20—C21—H213	109.5
C16—C17—C18	120.49 (18)	H211—C21—H212	109.5
C13—C18—C17	120.61 (15)	H211—C21—H213	109.5
O5—C19—O6	126.28 (16)	H212—C21—H213	109.5
C5—O2—C6—C7	−176.87 (15)	C3—C4—C5—O2	−179.57 (14)
C5—O2—C6—C11	2.1 (2)	C3—C4—C5—O4	−0.0 (2)
C6—O2—C5—O4	−178.82 (15)	C3—C4—C12—O3	−1.0 (2)
C6—O2—C5—C4	0.8 (2)	C3—C4—C12—C11	179.57 (14)
C1—O3—C12—C4	−12.7 (2)	C5—C4—C12—O3	−176.60 (15)
C1—O3—C12—C11	166.76 (13)	C5—C4—C12—C11	4.0 (2)
C12—O3—C1—O1	−79.87 (15)	C12—C4—C5—O2	−3.8 (2)
C12—O3—C1—C2	41.82 (17)	C12—C4—C5—O4	175.79 (17)
C12—O3—C1—C19	164.28 (13)	O2—C6—C7—C8	179.32 (16)
C19—O6—C20—C21	179.82 (15)	O2—C6—C11—C10	−179.62 (14)
C20—O6—C19—O5	5.1 (2)	O2—C6—C11—C12	−1.9 (2)
C20—O6—C19—C1	−175.90 (13)	C7—C6—C11—C10	−0.7 (2)
O1—C1—C2—C3	61.60 (16)	C7—C6—C11—C12	176.99 (16)
O1—C1—C19—O5	−14.1 (2)	C11—C6—C7—C8	0.4 (2)
O1—C1—C19—O6	166.88 (12)	C6—C7—C8—C9	−0.1 (2)
O3—C1—C2—C3	−58.67 (16)	C7—C8—C9—C10	0.1 (2)
O3—C1—C19—O5	100.86 (17)	C8—C9—C10—C11	−0.5 (2)
O3—C1—C19—O6	−78.16 (14)	C9—C10—C11—C6	0.8 (2)
C2—C1—C19—O5	−139.51 (16)	C9—C10—C11—C12	−176.80 (16)
C2—C1—C19—O6	41.46 (18)	C6—C11—C12—O3	179.34 (14)
C19—C1—C2—C3	−173.59 (12)	C6—C11—C12—C4	−1.2 (2)
C1—C2—C3—C4	43.95 (17)	C10—C11—C12—O3	−3.1 (2)
C1—C2—C3—C13	−84.91 (15)	C10—C11—C12—C4	176.41 (16)
C2—C3—C4—C5	160.47 (14)	C3—C13—C14—C15	−179.77 (15)
C2—C3—C4—C12	−15.2 (2)	C3—C13—C18—C17	−179.88 (15)
C2—C3—C13—C14	−64.76 (18)	C14—C13—C18—C17	0.7 (2)
C2—C3—C13—C18	115.79 (16)	C18—C13—C14—C15	−0.3 (2)
C4—C3—C13—C14	169.80 (14)	C13—C14—C15—C16	−0.4 (2)
C4—C3—C13—C18	−9.7 (2)	C14—C15—C16—C17	0.7 (2)
C13—C3—C4—C5	−71.53 (18)	C15—C16—C17—C18	−0.4 (3)
C13—C3—C4—C12	112.80 (17)	C16—C17—C18—C13	−0.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H101···O2i	0.82	2.30	2.9198 (15)	132
O1—H101···O5	0.82	2.17	2.6628 (17)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H101⋯O2i	0.82	2.30	2.9198 (15)	132
O1—H101⋯O5	0.82	2.17	2.6628 (17)	119

Symmetry code: (i) .