Ethyl (4aR*,7S*,8S*,8aS*)-1-oxo-7-phenyl-3,4,4a,7,8,8a-hexa-hydro-1H-isochromene-8-carboxyl-ate.

In the title compound, C(18)H(20)O(4), both the tetra-hydro-pyran-one ring and the cyclo-hexene ring adopt envelope conformations. The crystal packing is stabilized by weak inter-molecular C-H⋯O hydrogen bonding.

Related literature

The title compound is a derivative of 1-oxo-hexa­hydro-1H-isochromene, which has been reported as a key inter­mediate towards the total syntheses of natural products such as eleutherobin and tetronothio­din, see: Kim et al. (2000 ▶); Jung et al. (2000 ▶); Page et al. (2003 ▶). For microwave-assisted intra­molecular Diels–Alder cyclo­addition, see: Wu et al. (2006 ▶, 2007 ▶); Wang et al. (2009 ▶).

Experimental

Crystal data

C18H20O4

M = 300.34

Orthorhombic,

a = 15.5513 (12) Å

b = 9.9178 (7) Å

c = 21.1542 (17) Å

V = 3262.7 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.36 × 0.16 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

26140 measured reflections

3200 independent reflections

1627 reflections with I > 2σ(I)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.069

wR(F 2) = 0.197

S = 1.00

3200 reflections

202 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.28 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); 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 I, global. DOI: 10.1107/S1600536810017009/xu2757sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017009/xu2757Isup2.hkl

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

C18H20O4	F(000) = 1280
Mr = 300.34	Dx = 1.223 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 12675 reflections
a = 15.5513 (12) Å	θ = 3.1–27.4°
b = 9.9178 (7) Å	µ = 0.09 mm−1
c = 21.1542 (17) Å	T = 296 K
V = 3262.7 (4) Å3	Needle, colorless
Z = 8	0.36 × 0.16 × 0.14 mm

Rigaku R-AXIS RAPID IP diffractometer	1627 reflections with I > 2σ(I)
Radiation source: rolling anode	Rint = 0.075
graphite	θmax = 26.0°, θmin = 3.1°
Detector resolution: 10.00 pixels mm-1	h = −19→19
ω scans	k = −11→12
26140 measured reflections	l = −26→26
3200 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.069	H-atom parameters constrained
wR(F2) = 0.197	w = 1/[σ2(Fo2) + (0.0698P)2 + 1.9409P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
3200 reflections	Δρmax = 0.35 e Å−3
202 parameters	Δρmin = −0.28 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0067 (12)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O3	0.16345 (14)	0.3940 (2)	0.39009 (15)	0.1040 (10)
C17	0.0706 (3)	0.3651 (6)	0.3998 (3)	0.146 (2)
H17A	0.0524	0.2860	0.3764	0.175*
H17B	0.0350	0.4414	0.3880	0.175*
C18	0.0687 (4)	0.3407 (8)	0.4701 (3)	0.205 (3)
H18A	0.0993	0.2591	0.4796	0.308*
H18B	0.0102	0.3325	0.4839	0.308*
H18C	0.0955	0.4150	0.4915	0.308*
O4	0.18555 (14)	0.1796 (2)	0.36346 (12)	0.0848 (8)
C1	0.30154 (17)	0.3380 (3)	0.35293 (14)	0.0588 (8)
H1	0.3083	0.4330	0.3645	0.071*
C9	0.36348 (18)	0.2519 (3)	0.39280 (14)	0.0642 (8)
H9	0.3484	0.1571	0.3860	0.077*
C16	0.21088 (19)	0.2931 (3)	0.36799 (15)	0.0660 (8)
C10	0.35139 (19)	0.2824 (3)	0.46291 (15)	0.0680 (8)
C8	0.4540 (2)	0.2708 (3)	0.37126 (18)	0.0765 (9)
H8	0.4978	0.2486	0.3993	0.092*
O2	0.27531 (18)	0.5007 (3)	0.20646 (13)	0.1045 (9)
C2	0.32050 (19)	0.3207 (3)	0.28126 (15)	0.0704 (9)
H2	0.3127	0.2249	0.2714	0.084*
C5	0.4213 (2)	0.5048 (4)	0.24889 (18)	0.0856 (10)
H5A	0.4050	0.5586	0.2853	0.103*
H5B	0.4803	0.5264	0.2381	0.103*
C7	0.4757 (2)	0.3170 (4)	0.31524 (19)	0.0837 (11)
H7	0.5340	0.3258	0.3065	0.100*
C6	0.4140 (2)	0.3561 (3)	0.26494 (16)	0.0730 (9)
H6	0.4293	0.3053	0.2268	0.088*
C15	0.3062 (2)	0.1947 (4)	0.50117 (18)	0.0838 (10)
H15	0.2835	0.1159	0.4842	0.101*
C3	0.2542 (3)	0.3978 (4)	0.24313 (18)	0.0886 (11)
O1	0.17953 (19)	0.3714 (4)	0.24613 (17)	0.1447 (14)
C11	0.3852 (2)	0.3990 (4)	0.48850 (19)	0.0886 (11)
H11	0.4150	0.4592	0.4629	0.106*
C14	0.2948 (3)	0.2231 (6)	0.5638 (2)	0.1138 (14)
H14	0.2636	0.1641	0.5891	0.137*
C13	0.3294 (4)	0.3388 (7)	0.5899 (2)	0.1200 (16)
H13	0.3222	0.3572	0.6326	0.144*
C4	0.3635 (3)	0.5372 (5)	0.1941 (2)	0.1098 (14)
H4A	0.3666	0.6330	0.1853	0.132*
H4B	0.3835	0.4893	0.1570	0.132*
C12	0.3746 (3)	0.4264 (5)	0.5521 (2)	0.1144 (15)
H12	0.3982	0.5043	0.5693	0.137*

	U11	U22	U33	U12	U13	U23
O3	0.0557 (13)	0.0768 (15)	0.179 (3)	−0.0037 (11)	0.0323 (15)	−0.0228 (16)
C17	0.095 (3)	0.127 (4)	0.216 (7)	−0.015 (3)	0.045 (4)	−0.020 (4)
C18	0.146 (6)	0.258 (8)	0.211 (8)	−0.069 (5)	0.052 (5)	0.007 (7)
O4	0.0728 (15)	0.0589 (13)	0.123 (2)	−0.0162 (11)	−0.0052 (13)	−0.0008 (12)
C1	0.0494 (15)	0.0527 (15)	0.074 (2)	−0.0019 (13)	0.0044 (14)	−0.0056 (14)
C9	0.0597 (17)	0.0526 (15)	0.080 (2)	0.0045 (14)	0.0024 (16)	−0.0035 (15)
C16	0.0563 (17)	0.0572 (17)	0.084 (2)	−0.0022 (14)	−0.0007 (16)	0.0004 (16)
C10	0.0599 (18)	0.0660 (19)	0.078 (2)	0.0079 (15)	−0.0042 (16)	−0.0010 (17)
C8	0.0546 (18)	0.079 (2)	0.096 (3)	0.0106 (16)	0.0022 (18)	−0.0019 (19)
O2	0.095 (2)	0.116 (2)	0.103 (2)	−0.0024 (16)	−0.0076 (15)	0.0319 (17)
C2	0.068 (2)	0.0661 (18)	0.077 (2)	−0.0033 (16)	0.0021 (16)	−0.0063 (16)
C5	0.077 (2)	0.083 (2)	0.096 (3)	−0.0076 (19)	0.018 (2)	−0.002 (2)
C7	0.0534 (19)	0.091 (2)	0.106 (3)	0.0064 (17)	0.0163 (19)	−0.010 (2)
C6	0.068 (2)	0.074 (2)	0.077 (2)	0.0017 (16)	0.0155 (17)	−0.0103 (17)
C15	0.081 (2)	0.092 (2)	0.078 (2)	0.003 (2)	0.0015 (19)	0.011 (2)
C3	0.078 (2)	0.106 (3)	0.083 (2)	−0.007 (2)	−0.010 (2)	0.010 (2)
O1	0.0751 (19)	0.195 (3)	0.164 (3)	−0.024 (2)	−0.0326 (19)	0.072 (3)
C11	0.096 (3)	0.078 (2)	0.092 (3)	−0.001 (2)	−0.003 (2)	−0.015 (2)
C14	0.111 (3)	0.133 (4)	0.098 (4)	0.009 (3)	0.005 (3)	0.022 (3)
C13	0.127 (4)	0.155 (5)	0.078 (3)	0.037 (4)	0.003 (3)	−0.012 (3)
C4	0.099 (3)	0.111 (3)	0.119 (3)	−0.008 (3)	0.014 (3)	0.028 (3)
C12	0.128 (4)	0.109 (3)	0.106 (4)	0.014 (3)	−0.015 (3)	−0.031 (3)

O3—C16	1.327 (4)	C2—C3	1.516 (5)
O3—C17	1.486 (5)	C2—C6	1.535 (4)
C17—C18	1.507 (8)	C2—H2	0.9800
C17—H17A	0.9700	C5—C4	1.501 (5)
C17—H17B	0.9700	C5—C6	1.518 (5)
C18—H18A	0.9600	C5—H5A	0.9700
C18—H18B	0.9600	C5—H5B	0.9700
C18—H18C	0.9600	C7—C6	1.485 (5)
O4—C16	1.197 (3)	C7—H7	0.9300
C1—C16	1.512 (4)	C6—H6	0.9800
C1—C9	1.539 (4)	C15—C14	1.367 (6)
C1—C2	1.554 (4)	C15—H15	0.9300
C1—H1	0.9800	C3—O1	1.192 (4)
C9—C8	1.491 (4)	C11—C12	1.382 (6)
C9—C10	1.525 (4)	C11—H11	0.9300
C9—H9	0.9800	C14—C13	1.382 (7)
C10—C15	1.379 (5)	C14—H14	0.9300
C10—C11	1.381 (4)	C13—C12	1.374 (6)
C8—C7	1.314 (4)	C13—H13	0.9300
C8—H8	0.9300	C4—H4A	0.9700
O2—C3	1.323 (4)	C4—H4B	0.9700
O2—C4	1.442 (5)	C12—H12	0.9300
C16—O3—C17	116.3 (3)	C1—C2—H2	106.9
O3—C17—C18	100.7 (4)	C4—C5—C6	109.6 (3)
O3—C17—H17A	111.6	C4—C5—H5A	109.7
C18—C17—H17A	111.6	C6—C5—H5A	109.7
O3—C17—H17B	111.6	C4—C5—H5B	109.7
C18—C17—H17B	111.6	C6—C5—H5B	109.7
H17A—C17—H17B	109.4	H5A—C5—H5B	108.2
C17—C18—H18A	109.5	C8—C7—C6	124.8 (3)
C17—C18—H18B	109.5	C8—C7—H7	117.6
H18A—C18—H18B	109.5	C6—C7—H7	117.6
C17—C18—H18C	109.5	C7—C6—C5	111.5 (3)
H18A—C18—H18C	109.5	C7—C6—C2	113.0 (3)
H18B—C18—H18C	109.5	C5—C6—C2	110.1 (3)
C16—C1—C9	107.8 (2)	C7—C6—H6	107.3
C16—C1—C2	110.5 (2)	C5—C6—H6	107.3
C9—C1—C2	110.8 (2)	C2—C6—H6	107.3
C16—C1—H1	109.3	C14—C15—C10	120.4 (4)
C9—C1—H1	109.3	C14—C15—H15	119.8
C2—C1—H1	109.3	C10—C15—H15	119.8
C8—C9—C10	112.9 (3)	O1—C3—O2	116.3 (4)
C8—C9—C1	110.7 (3)	O1—C3—C2	121.5 (4)
C10—C9—C1	110.2 (2)	O2—C3—C2	122.2 (3)
C8—C9—H9	107.6	C10—C11—C12	120.0 (4)
C10—C9—H9	107.6	C10—C11—H11	120.0
C1—C9—H9	107.6	C12—C11—H11	120.0
O4—C16—O3	123.6 (3)	C15—C14—C13	120.5 (5)
O4—C16—C1	124.5 (3)	C15—C14—H14	119.8
O3—C16—C1	111.8 (2)	C13—C14—H14	119.8
C15—C10—C11	119.4 (3)	C12—C13—C14	119.5 (4)
C15—C10—C9	120.6 (3)	C12—C13—H13	120.3
C11—C10—C9	120.0 (3)	C14—C13—H13	120.3
C7—C8—C9	124.2 (3)	O2—C4—C5	112.1 (3)
C7—C8—H8	117.9	O2—C4—H4A	109.2
C9—C8—H8	117.9	C5—C4—H4A	109.2
C3—O2—C4	122.4 (3)	O2—C4—H4B	109.2
C3—C2—C6	114.1 (3)	C5—C4—H4B	109.2
C3—C2—C1	109.5 (3)	H4A—C4—H4B	107.9
C6—C2—C1	112.0 (2)	C13—C12—C11	120.2 (4)
C3—C2—H2	106.9	C13—C12—H12	119.9
C6—C2—H2	106.9	C11—C12—H12	119.9
C16—O3—C17—C18	100.1 (5)	C8—C7—C6—C2	−7.3 (5)
C16—C1—C9—C8	168.7 (2)	C4—C5—C6—C7	175.1 (3)
C2—C1—C9—C8	47.7 (3)	C4—C5—C6—C2	−58.7 (4)
C16—C1—C9—C10	−65.7 (3)	C3—C2—C6—C7	160.7 (3)
C2—C1—C9—C10	173.3 (2)	C1—C2—C6—C7	35.6 (4)
C17—O3—C16—O4	−9.7 (6)	C3—C2—C6—C5	35.4 (4)
C17—O3—C16—C1	173.5 (3)	C1—C2—C6—C5	−89.8 (3)
C9—C1—C16—O4	−55.5 (4)	C11—C10—C15—C14	0.1 (5)
C2—C1—C16—O4	65.7 (4)	C9—C10—C15—C14	−179.3 (3)
C9—C1—C16—O3	121.3 (3)	C4—O2—C3—O1	−174.7 (4)
C2—C1—C16—O3	−117.5 (3)	C4—O2—C3—C2	7.5 (6)
C8—C9—C10—C15	−133.0 (3)	C6—C2—C3—O1	172.4 (4)
C1—C9—C10—C15	102.6 (3)	C1—C2—C3—O1	−61.2 (5)
C8—C9—C10—C11	47.5 (4)	C6—C2—C3—O2	−9.9 (5)
C1—C9—C10—C11	−76.9 (4)	C1—C2—C3—O2	116.5 (4)
C10—C9—C8—C7	−144.6 (3)	C15—C10—C11—C12	0.9 (5)
C1—C9—C8—C7	−20.5 (4)	C9—C10—C11—C12	−179.7 (3)
C16—C1—C2—C3	56.2 (3)	C10—C15—C14—C13	−1.0 (6)
C9—C1—C2—C3	175.6 (3)	C15—C14—C13—C12	0.8 (7)
C16—C1—C2—C6	−176.1 (2)	C3—O2—C4—C5	−31.0 (5)
C9—C1—C2—C6	−56.7 (3)	C6—C5—C4—O2	56.5 (4)
C9—C8—C7—C6	−0.5 (6)	C14—C13—C12—C11	0.2 (7)
C8—C7—C6—C5	117.3 (4)	C10—C11—C12—C13	−1.0 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4i	0.98	2.45	3.401 (4)	164
C5—H5A···O4i	0.97	2.48	3.412 (4)	161
C7—H7···O1ii	0.93	2.56	3.468 (5)	165
C13—H13···O2iii	0.93	2.59	3.356 (6)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O4i	0.98	2.45	3.401 (4)	164
C5—H5A⋯O4i	0.97	2.48	3.412 (4)	161
C7—H7⋯O1ii	0.93	2.56	3.468 (5)	165
C13—H13⋯O2iii	0.93	2.59	3.356 (6)	140

Symmetry codes: (i) ; (ii) ; (iii) .