(4R)-Ethyl 4-(4-chloro-phen-yl)-2-hydr-oxy-5-oxo-2,3,4,5-tetra-hydro-pyrano[3,2-c]chromene-2-carboxyl-ate.

The title compound, C(21)H(17)ClO(6), is optically pure and adopts an R configuration. It was obtained by an organocatalytic asymmetric Michael addition of 4-hydroxy-coumarin with (E)-ethyl 4-(4-chloro-phen-yl)-2-oxobut-3-enoate. The structure consists of a tetra-hydro-pyran unit fused to the coumarin ring ring system. The hydroxyl and phenyl groups are on the same side of the tetra-hydro-pyrane ring. The benzene ring is almost perpendicular to the coumarin ring [dihedral angle of 72.89 (3)°]. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds are observed. An intra-molecular 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 = 400.80

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.080

S = 1.00

3606 reflections

256 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 1434 Friedel pairs

Flack parameter: 0.07 (6)

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 ▶).

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

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

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

C21H17ClO6	F(000) = 416
Mr = 400.80	Dx = 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

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

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(Fo2) + (0.0403P)2 + 0.110P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.16 e Å−3
3606 reflections	Δρmin = −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	Flack parameter: 0.07 (6)

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
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*

	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)

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)

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

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) .