(4R)-Ethyl 4-(4-chloro­phen­yl)-2-hydr­oxy-5-oxo-2,3,4,5-tetra­hydro­pyrano[3,2-c]chromene-2-carboxyl­ate

Wang, Y.; Zhang, W.; Xu, X.; Zhang, G.

doi:10.1107/S1600536809051976

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o217

doi:10.1107/S1600536809051976

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ADDENDA AND ERRATA

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(4R)-Ethyl 4-(4-chlorophenyl)-2-hydroxy-5-oxo-2,3,4,5-tetrahydropyrano[3,2-c]chromene-2-carboxylate

Yifeng Wang,^a ^* Wei Zhang,^a Xiangsheng Xu ^a and Guangcun Zhang ^a

^aState Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou, 310014, People's Republic of China
^*Correspondence e-mail: yifengwang108@gmail.com

(Received 21 November 2009; accepted 3 December 2009; online 19 December 2009)

The title compound, C₂₁H₁₇ClO₆, is optically pure and adopts an R configuration. It was obtained by an organocatalytic asymmetric Michael addition of 4-hydroxycoumarin with (E)-ethyl 4-(4-chlorophenyl)-2-oxobut-3-enoate. The structure consists of a tetrahydropyran unit fused to the coumarin ring ring system. The hydroxyl and phenyl groups are on the same side of the tetrahydropyrane ring. The benzene ring is almost perpendicular to the coumarin ring [dihedral angle of 72.89 (3)°]. In the crystal structure, intermolecular O—H⋯O hydrogen bonds are observed. An intramolecular O—H⋯O contact also occurs.

Related literature

For general background to the use of coumarin derivatives as intermediates in organic and natural product synthesis, see: Fylaktakidou et al., (2004 ); Hoult et al., (1996 ). For a related structure, see: Zhang et al. (2009 ).

Experimental

Crystal data

C₂₁H₁₇ClO₆
M_r = 400.80
Monoclinic, P 2₁
a = 5.4818 (3) Å
b = 14.8358 (7) Å
c = 11.3403 (6) Å
β = 94.6807 (15)°
V = 919.20 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.37 × 0.31 × 0.08 mm

Data collection

Rigaku RAXIS-RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.905, T_max = 0.981
8978 measured reflections
3606 independent reflections
3027 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.080
S = 1.00
3606 reflections
256 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 1434 Friedel pairs
Flack parameter: 0.07 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ⁱ	0.82	2.27	2.9184 (19)	136
O4—H4⋯O5	0.82	2.19	2.671 (2)	118
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ); 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,1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051976/zq2019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051976/zq2019Isup2.hkl

checkCIF report

Comment top

Coumarin derivatives are common found in a variety of natural products, and are used as versatile intermediates in organic and natural product synthesis (Fylaktakidou et al., 2004; Hoult et al., 1996). The title compound could be synthesized through an asymmetric Michael addition of 4-hydroxycoumarin with (E)-ethyl 4-(4-chlorophenyl)-2-oxobut-3-enoate, catalyzed by a tertiary-amine-squaramide catalyst. As part of our study in organocatalysis, the absolute structure of the title compound was determined, which adopts a R configuration. The structure consists of a tetrahydropyrane fused beside the coumarin ring. The hydroxyl and phenyl groups are on the same side of the tetrahydropyrane ring. The benzene ring is almost perpendicular to the coumarin ring with a dihedral angle of 72.89 (3)° between the mean planes. In addition, intermolecular O—H···O hydrogen bonds are observed in the crystal structure.

Related literature top

For general background, see: Fylaktakidou et al., (2004); Hoult et al., (1996). For a related structure, see: Zhang et al. (2009).

Experimental top

A mixture of 4-hydroxycoumarin (0.1 mmol), (E)-ethyl 4-(4-chlorophenyl)-2-oxobut-3-enoate 2 (0.1 mmol) and the catalyst 3-((1S) -(6-methoxyquinolin-4-yl)(8-vinylquinuclidin-2-yl)methylamino) -4-((R)-1-phenylethylamino)cyclobut-3-ene-1,2-dione (0.0025 mmol) in ClCH₂CH₂Cl (1.0 ml) was stirred at room temperature for 3 h (monitored by TLC). The mixture was purified by column chromatography on silica gel, eluted by petroleum ether/EtOAc (10:1 to 3:1) to give the desired Michael adducts. Suitable crystals of the title compound were obtained by slow evaporation of a mixture solution of CH₂Cl₂ and iPrOH at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); 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: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the structure of the title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular packing of the title compound showing H-bridge interactions.

(4R)-Ethyl 4-(4-chlorophenyl)-2-hydroxy -5-oxo-2,3,4,5-tetrahydropyrano[3,2-c]chromene-2-carboxylate top

Crystal data top

C₂₁H₁₇ClO₆	F(000) = 416
M_r = 400.80	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 7553 reflections
a = 5.4818 (3) Å	θ = 3.3–27.4°
b = 14.8358 (7) Å	µ = 0.25 mm⁻¹
c = 11.3403 (6) Å	T = 296 K
β = 94.6807 (15)°	Platelet, colorless
V = 919.20 (8) Å³	0.37 × 0.31 × 0.08 mm
Z = 2

Data collection top

Rigaku RAXIS-RAPID diffractometer	3606 independent reflections
Radiation source: rolling anode	3027 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.3°
ω scans	h = −7→6
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −19→16
T_min = 0.905, T_max = 0.981	l = −14→14
8978 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0403P)² + 0.110P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.080	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.16 e Å⁻³
3606 reflections	Δρ_min = −0.20 e Å⁻³
256 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.014 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1434 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.07 (6)

Crystal data top

C₂₁H₁₇ClO₆	V = 919.20 (8) Å³
M_r = 400.80	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.4818 (3) Å	µ = 0.25 mm⁻¹
b = 14.8358 (7) Å	T = 296 K
c = 11.3403 (6) Å	0.37 × 0.31 × 0.08 mm
β = 94.6807 (15)°

Data collection top

Rigaku RAXIS-RAPID diffractometer	3606 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3027 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.981	R_int = 0.025
8978 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.080	Δρ_max = 0.16 e Å⁻³
S = 1.00	Δρ_min = −0.20 e Å⁻³
3606 reflections	Absolute structure: Flack (1983), 1434 Friedel pairs
256 parameters	Absolute structure parameter: 0.07 (6)
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C19	0.7695 (3)	0.87640 (13)	0.68614 (17)	0.0368 (4)
O6	0.9549 (3)	0.87424 (10)	0.76723 (12)	0.0456 (3)
O5	0.6200 (3)	0.93532 (10)	0.67137 (15)	0.0542 (4)
C20	0.9886 (5)	0.95257 (18)	0.8444 (2)	0.0577 (6)
H20A	0.8533	0.9579	0.8940	0.069*
H20B	0.9965	1.0072	0.7978	0.069*
C21	1.2228 (5)	0.9388 (2)	0.9187 (2)	0.0677 (7)
H21A	1.3564	0.9380	0.8690	0.081*
H21B	1.2169	0.8825	0.9600	0.081*
H21C	1.2458	0.9871	0.9749	0.081*
Cl1	0.78443 (13)	0.72613 (6)	−0.01510 (5)	0.0714 (2)
O3	0.6428 (2)	0.72598 (9)	0.68482 (11)	0.0369 (3)
C9	0.5060 (3)	0.57839 (13)	0.71703 (16)	0.0345 (4)
O4	0.6019 (2)	0.80479 (9)	0.50872 (12)	0.0396 (3)
H4	0.5259	0.8519	0.5155	0.047*
C10	0.6604 (3)	0.63786 (12)	0.65397 (16)	0.0325 (4)
O2	0.6645 (3)	0.45423 (9)	0.60916 (14)	0.0467 (4)
O1	0.9452 (3)	0.47428 (10)	0.48350 (16)	0.0577 (5)
C14	1.0913 (3)	0.72144 (15)	0.31531 (17)	0.0407 (4)
H14	1.2357	0.7420	0.3552	0.049*
C13	0.9207 (3)	0.67714 (13)	0.37856 (16)	0.0334 (4)
C2	0.8067 (3)	0.60639 (12)	0.57288 (16)	0.0335 (4)
C1	0.9793 (3)	0.66573 (12)	0.51166 (16)	0.0332 (4)
H1	1.1406	0.6370	0.5222	0.040*
C8	0.3482 (4)	0.60857 (15)	0.79984 (18)	0.0429 (5)
H8	0.3403	0.6695	0.8184	0.051*
C15	1.0524 (4)	0.73588 (16)	0.19483 (18)	0.0459 (5)
H15	1.1688	0.7657	0.1540	0.055*
C5	0.3671 (5)	0.42524 (15)	0.7439 (2)	0.0547 (6)
H5	0.3721	0.3644	0.7248	0.066*
C11	0.7569 (3)	0.79097 (12)	0.60903 (16)	0.0320 (4)
C6	0.2158 (5)	0.45589 (17)	0.8250 (2)	0.0603 (7)
H6	0.1184	0.4149	0.8618	0.072*
C16	0.8385 (4)	0.70536 (14)	0.13638 (18)	0.0438 (5)
C17	0.6664 (4)	0.65979 (16)	0.19587 (19)	0.0476 (5)
H17	0.5232	0.6388	0.1554	0.057*
C3	0.8158 (4)	0.51022 (13)	0.54999 (19)	0.0421 (5)
C12	1.0021 (3)	0.75658 (12)	0.57806 (17)	0.0334 (4)
H12A	1.1086	0.7491	0.6500	0.040*
H12B	1.0763	0.8007	0.5289	0.040*
C4	0.5140 (4)	0.48726 (14)	0.69059 (19)	0.0414 (5)
C18	0.7094 (3)	0.64567 (14)	0.31706 (18)	0.0409 (4)
H18	0.5944	0.6146	0.3573	0.049*
C7	0.2036 (4)	0.54659 (17)	0.8539 (2)	0.0544 (6)
H7	0.0988	0.5658	0.9093	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C19	0.0424 (10)	0.0289 (9)	0.0403 (10)	−0.0053 (9)	0.0112 (8)	0.0000 (8)
O6	0.0582 (8)	0.0365 (8)	0.0417 (8)	−0.0048 (7)	0.0013 (6)	−0.0088 (6)
O5	0.0549 (9)	0.0375 (8)	0.0713 (11)	0.0070 (7)	0.0109 (8)	−0.0129 (7)
C20	0.0693 (14)	0.0498 (14)	0.0545 (14)	−0.0138 (12)	0.0078 (11)	−0.0206 (11)
C21	0.0677 (15)	0.081 (2)	0.0540 (15)	−0.0195 (15)	0.0045 (12)	−0.0199 (14)
Cl1	0.0961 (5)	0.0781 (5)	0.0382 (3)	0.0081 (4)	−0.0048 (3)	0.0010 (3)
O3	0.0452 (7)	0.0252 (6)	0.0418 (7)	−0.0039 (6)	0.0128 (5)	0.0007 (6)
C9	0.0382 (9)	0.0321 (10)	0.0327 (9)	−0.0038 (8)	0.0006 (7)	0.0047 (8)
O4	0.0399 (7)	0.0346 (8)	0.0433 (7)	0.0059 (6)	−0.0023 (6)	−0.0007 (6)
C10	0.0375 (9)	0.0238 (8)	0.0355 (9)	−0.0013 (7)	−0.0008 (7)	0.0009 (7)
O2	0.0616 (9)	0.0260 (7)	0.0541 (9)	−0.0058 (6)	0.0140 (7)	−0.0031 (6)
O1	0.0745 (11)	0.0333 (8)	0.0688 (11)	0.0064 (8)	0.0263 (9)	−0.0074 (7)
C14	0.0350 (9)	0.0441 (11)	0.0432 (10)	−0.0005 (9)	0.0046 (8)	−0.0034 (10)
C13	0.0341 (8)	0.0285 (9)	0.0378 (10)	0.0050 (8)	0.0046 (7)	−0.0021 (8)
C2	0.0368 (9)	0.0256 (8)	0.0377 (10)	0.0003 (8)	0.0015 (8)	0.0005 (8)
C1	0.0315 (8)	0.0297 (9)	0.0383 (10)	0.0030 (8)	0.0024 (7)	0.0011 (8)
C8	0.0523 (12)	0.0357 (10)	0.0410 (11)	−0.0040 (9)	0.0060 (9)	0.0030 (8)
C15	0.0470 (11)	0.0466 (12)	0.0450 (11)	0.0027 (10)	0.0091 (9)	0.0025 (10)
C5	0.0785 (15)	0.0323 (11)	0.0547 (14)	−0.0159 (11)	0.0145 (12)	0.0029 (10)
C11	0.0353 (8)	0.0246 (9)	0.0361 (9)	−0.0023 (8)	0.0028 (7)	0.0018 (7)
C6	0.0808 (17)	0.0471 (14)	0.0556 (14)	−0.0241 (12)	0.0221 (12)	0.0057 (11)
C16	0.0553 (12)	0.0407 (12)	0.0353 (10)	0.0113 (9)	0.0035 (9)	−0.0019 (8)
C17	0.0456 (11)	0.0477 (13)	0.0479 (12)	0.0046 (11)	−0.0057 (9)	−0.0086 (10)
C3	0.0492 (12)	0.0293 (10)	0.0481 (12)	−0.0005 (9)	0.0062 (9)	0.0004 (9)
C12	0.0320 (8)	0.0309 (9)	0.0374 (10)	−0.0034 (7)	0.0033 (7)	−0.0021 (7)
C4	0.0518 (11)	0.0322 (10)	0.0400 (11)	−0.0070 (9)	0.0027 (9)	0.0008 (8)
C18	0.0377 (10)	0.0389 (11)	0.0461 (11)	−0.0004 (9)	0.0043 (8)	−0.0044 (9)
C7	0.0644 (14)	0.0506 (13)	0.0506 (13)	−0.0086 (12)	0.0198 (11)	0.0060 (10)

Geometric parameters (Å, º) top

C19—O5	1.201 (3)	C14—H14	0.9300
C19—O6	1.314 (2)	C13—C18	1.384 (3)
C19—C11	1.538 (3)	C13—C1	1.527 (3)
O6—C20	1.457 (3)	C2—C3	1.452 (3)
C20—C21	1.491 (3)	C2—C1	1.503 (3)
C20—H20A	0.9700	C1—C12	1.544 (2)
C20—H20B	0.9700	C1—H1	0.9800
C21—H21A	0.9600	C8—C7	1.389 (3)
C21—H21B	0.9600	C8—H8	0.9300
C21—H21C	0.9600	C15—C16	1.376 (3)
Cl1—C16	1.747 (2)	C15—H15	0.9300
O3—C10	1.359 (2)	C5—C6	1.366 (4)
O3—C11	1.466 (2)	C5—C4	1.393 (3)
C9—C4	1.386 (3)	C5—H5	0.9300
C9—C8	1.401 (3)	C11—C12	1.506 (2)
C9—C10	1.451 (3)	C6—C7	1.388 (4)
O4—C11	1.379 (2)	C6—H6	0.9300
O4—H4	0.8200	C16—C17	1.381 (3)
C10—C2	1.352 (3)	C17—C18	1.391 (3)
O2—C4	1.378 (2)	C17—H17	0.9300
O2—C3	1.385 (3)	C12—H12A	0.9700
O1—C3	1.202 (3)	C12—H12B	0.9700
C14—C15	1.382 (3)	C18—H18	0.9300
C14—C13	1.389 (3)	C7—H7	0.9300

O5—C19—O6	126.54 (19)	C7—C8—H8	120.3
O5—C19—C11	121.49 (18)	C9—C8—H8	120.3
O6—C19—C11	111.95 (17)	C16—C15—C14	118.80 (19)
C19—O6—C20	116.98 (18)	C16—C15—H15	120.6
O6—C20—C21	106.9 (2)	C14—C15—H15	120.6
O6—C20—H20A	110.3	C6—C5—C4	118.5 (2)
C21—C20—H20A	110.3	C6—C5—H5	120.8
O6—C20—H20B	110.3	C4—C5—H5	120.8
C21—C20—H20B	110.3	O4—C11—O3	108.53 (14)
H20A—C20—H20B	108.6	O4—C11—C12	111.09 (15)
C20—C21—H21A	109.5	O3—C11—C12	110.24 (14)
C20—C21—H21B	109.5	O4—C11—C19	110.03 (15)
H21A—C21—H21B	109.5	O3—C11—C19	102.12 (14)
C20—C21—H21C	109.5	C12—C11—C19	114.36 (15)
H21A—C21—H21C	109.5	C5—C6—C7	121.7 (2)
H21B—C21—H21C	109.5	C5—C6—H6	119.2
C10—O3—C11	116.05 (14)	C7—C6—H6	119.2
C4—C9—C8	119.26 (17)	C15—C16—C17	121.02 (19)
C4—C9—C10	117.16 (18)	C15—C16—Cl1	119.04 (17)
C8—C9—C10	123.56 (18)	C17—C16—Cl1	119.94 (16)
C11—O4—H4	109.5	C16—C17—C18	119.28 (18)
C2—C10—O3	124.48 (16)	C16—C17—H17	120.4
C2—C10—C9	121.85 (17)	C18—C17—H17	120.4
O3—C10—C9	113.68 (16)	O1—C3—O2	116.45 (18)
C4—O2—C3	121.76 (15)	O1—C3—C2	125.38 (19)
C15—C14—C13	121.85 (17)	O2—C3—C2	118.17 (17)
C15—C14—H14	119.1	C11—C12—C1	111.80 (14)
C13—C14—H14	119.1	C11—C12—H12A	109.3
C18—C13—C14	118.06 (17)	C1—C12—H12A	109.3
C18—C13—C1	124.12 (17)	C11—C12—H12B	109.3
C14—C13—C1	117.82 (15)	C1—C12—H12B	109.3
C10—C2—C3	119.47 (17)	H12A—C12—H12B	107.9
C10—C2—C1	122.87 (17)	O2—C4—C9	121.55 (17)
C3—C2—C1	117.45 (17)	O2—C4—C5	117.07 (19)
C2—C1—C13	115.59 (15)	C9—C4—C5	121.4 (2)
C2—C1—C12	108.35 (15)	C13—C18—C17	120.96 (19)
C13—C1—C12	112.80 (15)	C13—C18—H18	119.5
C2—C1—H1	106.5	C17—C18—H18	119.5
C13—C1—H1	106.5	C8—C7—C6	119.9 (2)
C12—C1—H1	106.5	C8—C7—H7	120.1
C7—C8—C9	119.3 (2)	C6—C7—H7	120.1

O5—C19—O6—C20	−2.5 (3)	O6—C19—C11—O3	79.70 (17)
C11—C19—O6—C20	178.81 (17)	O5—C19—C11—C12	141.84 (19)
C19—O6—C20—C21	−173.86 (19)	O6—C19—C11—C12	−39.4 (2)
C11—O3—C10—C2	11.5 (3)	C4—C5—C6—C7	0.7 (4)
C11—O3—C10—C9	−168.76 (14)	C14—C15—C16—C17	−1.0 (3)
C4—C9—C10—C2	−0.1 (3)	C14—C15—C16—Cl1	178.24 (17)
C8—C9—C10—C2	−178.63 (19)	C15—C16—C17—C18	0.8 (3)
C4—C9—C10—O3	−179.89 (16)	Cl1—C16—C17—C18	−178.46 (16)
C8—C9—C10—O3	1.6 (3)	C4—O2—C3—O1	177.8 (2)
C15—C14—C13—C18	1.2 (3)	C4—O2—C3—C2	−2.0 (3)
C15—C14—C13—C1	−179.16 (19)	C10—C2—C3—O1	−177.1 (2)
O3—C10—C2—C3	178.07 (17)	C1—C2—C3—O1	−2.2 (3)
C9—C10—C2—C3	−1.7 (3)	C10—C2—C3—O2	2.7 (3)
O3—C10—C2—C1	3.5 (3)	C1—C2—C3—O2	177.59 (16)
C9—C10—C2—C1	−176.26 (16)	O4—C11—C12—C1	−60.5 (2)
C10—C2—C1—C13	−114.25 (19)	O3—C11—C12—C1	59.81 (19)
C3—C2—C1—C13	71.1 (2)	C19—C11—C12—C1	174.18 (15)
C10—C2—C1—C12	13.4 (2)	C2—C1—C12—C11	−44.01 (19)
C3—C2—C1—C12	−161.21 (16)	C13—C1—C12—C11	85.26 (18)
C18—C13—C1—C2	7.8 (3)	C3—O2—C4—C9	0.2 (3)
C14—C13—C1—C2	−171.77 (17)	C3—O2—C4—C5	179.2 (2)
C18—C13—C1—C12	−117.64 (19)	C8—C9—C4—O2	179.47 (18)
C14—C13—C1—C12	62.8 (2)	C10—C9—C4—O2	0.9 (3)
C4—C9—C8—C7	0.1 (3)	C8—C9—C4—C5	0.5 (3)
C10—C9—C8—C7	178.6 (2)	C10—C9—C4—C5	−178.09 (19)
C13—C14—C15—C16	0.0 (3)	C6—C5—C4—O2	−180.0 (2)
C10—O3—C11—O4	79.38 (18)	C6—C5—C4—C9	−0.9 (3)
C10—O3—C11—C12	−42.5 (2)	C14—C13—C18—C17	−1.5 (3)
C10—O3—C11—C19	−164.42 (14)	C1—C13—C18—C17	178.97 (18)
O5—C19—C11—O4	16.0 (2)	C16—C17—C18—C13	0.5 (3)
O6—C19—C11—O4	−165.19 (15)	C9—C8—C7—C6	−0.3 (3)
O5—C19—C11—O3	−99.1 (2)	C5—C6—C7—C8	−0.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.82	2.27	2.9184 (19)	136
O4—H4···O5	0.82	2.19	2.671 (2)	118

Symmetry code: (i) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₇ClO₆
M_r	400.80
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	5.4818 (3), 14.8358 (7), 11.3403 (6)
β (°)	94.6807 (15)
V (Å³)	919.20 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.37 × 0.31 × 0.08

Data collection
Diffractometer	Rigaku RAXIS-RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.905, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	8978, 3606, 3027
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.080, 1.00
No. of reflections	3606
No. of parameters	256
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20
Absolute structure	Flack (1983), 1434 Friedel pairs
Absolute structure parameter	0.07 (6)

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia,1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.82	2.27	2.9184 (19)	136
O4—H4···O5	0.82	2.19	2.671 (2)	118

Symmetry code: (i) −x+1, y+1/2, −z+1.

Acknowledgements

We thank Professor Jian-Ming Gu of Zhejiang University for his help.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fylaktakidou, K. C., Hadjipavlou-Litina, D. J., Litinas, K. E. & Nicolaides, D. N. (2004). Curr. Pharm. Des. 10, 3813–3833. Web of Science CrossRef PubMed CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hoult, J. R. S. & Paya, M. (1996). Gen. Pharmacol. 27, 713–722. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2007). CrystalStructure. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, W., Zhang, G., Li, B. & Wang, Y. (2009). Acta Cryst. E65, o1969. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 66| Part 1| January 2010| Page o217

doi:10.1107/S1600536809051976

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(4R)-Ethyl 4-(4-chloro­phen­yl)-2-hydr­­oxy-5-oxo-2,3,4,5-tetra­hydro­pyrano[3,2-c]chromene-2-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(4R)-Ethyl 4-(4-chlorophenyl)-2-hydroxy-5-oxo-2,3,4,5-tetrahydropyrano[3,2-c]chromene-2-carboxylate