4-(7-Acet-oxy-6-meth-oxy-4-methyl-2-oxo-2H-chromen-3-yl)phenyl acetate.

The title compound, C(21)H(18)O(7), is an important inter-mediate in the synthesis of 3-(4-hydroxy-phen-yl)-4-methyl-6-meth-oxy-7-hydroxy-coumarin, which is a nonsteroidal analogue of 2-methoxy-estradiol (2-ME). The substituent benzene ring is not in the same plane as the coumarin ring system, with a dihedral angle of 66.88 (10)°. There are some weak inter-molecular C-H⋯O inter-actions. One carbonyl O atom is disordered over two sites, with occupancies of 0.6 and 0.4.

Related literature

For related literature, see: Gibanananda et al. (2006 ▶); Sutherland et al. (2007 ▶).

Experimental

Crystal data

C21H18O7

M = 382.35

Triclinic,

a = 8.142 (3) Å

b = 11.167 (4) Å

c = 11.756 (4) Å

α = 65.130 (4)°

β = 75.392 (4)°

γ = 79.055 (4)°

V = 934.1 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 293 (2) K

0.15 × 0.12 × 0.04 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.985, T max = 0.996

3893 measured reflections

3245 independent reflections

2279 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.074

wR(F 2) = 0.254

S = 1.09

3245 reflections

266 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SMART; data reduction: SAINT (Bruker, 2000 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012890/cf2199sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012890/cf2199Isup2.hkl

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

C21H18O7	Z = 2
Mr = 382.35	F000 = 400
Triclinic, P1	Dx = 1.359 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 8.142 (3) Å	Cell parameters from 954 reflections
b = 11.167 (4) Å	θ = 2.6–26.3º
c = 11.756 (4) Å	µ = 0.10 mm−1
α = 65.130 (4)º	T = 293 (2) K
β = 75.392 (4)º	Sheet, colorless
γ = 79.055 (4)º	0.15 × 0.12 × 0.04 mm
V = 934.1 (5) Å3

Bruker SMART APEX CCD area-detector diffractometer	3245 independent reflections
Radiation source: fine-focus sealed tube	2279 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.031
T = 293(2) K	θmax = 25.1º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.985, Tmax = 0.996	k = −13→10
3893 measured reflections	l = −13→14

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)] = 0.074	H-atom parameters constrained
wR(F2) = 0.254	w = 1/[σ2(Fo2) + (0.1741P)2] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
3245 reflections	Δρmax = 0.28 e Å−3
266 parameters	Δρmin = −0.50 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
O1	0.3185 (3)	0.17959 (18)	0.16190 (17)	0.0502 (6)
O2	0.3094 (3)	0.3939 (2)	0.1010 (2)	0.0586 (6)
O3	0.2256 (3)	0.8533 (2)	−0.4110 (2)	0.0687 (7)
O5	0.2670 (3)	−0.27608 (18)	0.10771 (19)	0.0563 (6)
O6	0.3460 (2)	−0.28758 (18)	0.31855 (17)	0.0507 (6)
O7	0.0661 (3)	−0.3060 (2)	0.3850 (2)	0.0736 (7)
C2	0.2997 (4)	0.3052 (3)	0.0710 (3)	0.0461 (7)
C3	0.2680 (3)	0.3215 (3)	−0.0519 (3)	0.0422 (7)
C4	0.2529 (3)	0.2128 (3)	−0.0733 (2)	0.0405 (6)
C5	0.2552 (3)	−0.0362 (3)	0.0142 (2)	0.0425 (7)
H5	0.2329	−0.0317	−0.0613	0.051*
C6	0.2753 (3)	−0.1569 (3)	0.1113 (3)	0.0442 (7)
C7	0.3133 (3)	−0.1642 (3)	0.2232 (3)	0.0440 (7)
C8	0.3266 (4)	−0.0521 (3)	0.2393 (3)	0.0481 (7)
H8	0.3507	−0.0578	0.3148	0.058*
C9	0.3036 (3)	0.0699 (3)	0.1407 (2)	0.0413 (6)
C10	0.2678 (3)	0.0826 (3)	0.0268 (2)	0.0399 (6)
C11	0.2208 (4)	0.2260 (3)	−0.1983 (3)	0.0527 (8)
H11A	0.2364	0.3147	−0.2601	0.079*
H11B	0.1061	0.2074	−0.1871	0.079*
H11C	0.2992	0.1644	−0.2276	0.079*
C12	0.2578 (3)	0.4597 (3)	−0.1475 (3)	0.0444 (7)
C13	0.1053 (4)	0.5256 (3)	−0.1852 (3)	0.0592 (8)
H13	0.0075	0.4810	−0.1518	0.071*
C14	0.0962 (4)	0.6549 (3)	−0.2704 (3)	0.0641 (9)
H14	−0.0067	0.6966	−0.2953	0.077*
C15	0.2384 (4)	0.7232 (3)	−0.3192 (3)	0.0524 (8)
C16	0.3906 (4)	0.6615 (3)	−0.2841 (3)	0.0540 (8)
H16	0.4875	0.7072	−0.3181	0.065*
C17	0.3995 (4)	0.5314 (3)	−0.1982 (3)	0.0497 (7)
H17	0.5028	0.4907	−0.1737	0.060*
C18	0.2305 (6)	0.9555 (4)	−0.3829 (4)	0.0864 (13)
O4A	0.1775 (16)	0.9331 (7)	−0.2672 (6)	0.159 (4)	0.55
O4B	0.3254 (11)	0.9405 (7)	−0.3076 (8)	0.094 (2)	0.45
C19	0.2078 (6)	1.0852 (3)	−0.4860 (4)	0.0876 (12)
H19A	0.1643	1.1509	−0.4506	0.131*
H19B	0.1287	1.0822	−0.5329	0.131*
H19C	0.3155	1.1075	−0.5424	0.131*
C20	0.2417 (4)	−0.2736 (3)	−0.0087 (3)	0.0571 (8)
H20A	0.1307	−0.2306	−0.0234	0.086*
H20B	0.2502	−0.3627	−0.0032	0.086*
H20C	0.3270	−0.2258	−0.0781	0.086*
C21	0.2086 (4)	−0.3556 (3)	0.3919 (3)	0.0515 (8)
C22	0.2624 (5)	−0.4899 (3)	0.4777 (3)	0.0720 (10)
H22A	0.2921	−0.4860	0.5500	0.108*
H22B	0.3596	−0.5265	0.4327	0.108*
H22C	0.1707	−0.5449	0.5065	0.108*

	U11	U22	U33	U12	U13	U23
O1	0.0708 (14)	0.0396 (11)	0.0404 (11)	−0.0112 (9)	−0.0212 (9)	−0.0075 (9)
O2	0.0779 (15)	0.0445 (12)	0.0597 (13)	−0.0139 (10)	−0.0268 (11)	−0.0153 (10)
O3	0.113 (2)	0.0374 (12)	0.0452 (12)	−0.0105 (12)	−0.0248 (12)	0.0010 (9)
O5	0.0827 (15)	0.0348 (11)	0.0463 (12)	−0.0121 (10)	−0.0177 (10)	−0.0054 (9)
O6	0.0515 (12)	0.0402 (11)	0.0424 (11)	−0.0096 (9)	−0.0125 (9)	0.0050 (9)
O7	0.0529 (14)	0.0680 (16)	0.0697 (16)	−0.0088 (12)	−0.0070 (11)	0.0002 (12)
C2	0.0489 (16)	0.0437 (16)	0.0429 (16)	−0.0153 (12)	−0.0139 (12)	−0.0068 (13)
C3	0.0420 (15)	0.0379 (15)	0.0410 (15)	−0.0089 (11)	−0.0109 (12)	−0.0064 (12)
C4	0.0398 (14)	0.0402 (15)	0.0345 (14)	−0.0074 (11)	−0.0094 (11)	−0.0052 (11)
C5	0.0492 (16)	0.0401 (15)	0.0345 (14)	−0.0087 (12)	−0.0120 (12)	−0.0072 (12)
C6	0.0464 (15)	0.0364 (15)	0.0426 (15)	−0.0107 (12)	−0.0077 (12)	−0.0062 (12)
C7	0.0437 (15)	0.0378 (14)	0.0361 (14)	−0.0081 (11)	−0.0069 (11)	0.0005 (11)
C8	0.0555 (17)	0.0502 (17)	0.0336 (14)	−0.0113 (14)	−0.0154 (12)	−0.0053 (12)
C9	0.0469 (15)	0.0372 (14)	0.0371 (14)	−0.0089 (11)	−0.0092 (11)	−0.0093 (11)
C10	0.0402 (14)	0.0402 (15)	0.0336 (14)	−0.0096 (11)	−0.0089 (11)	−0.0057 (11)
C11	0.073 (2)	0.0404 (15)	0.0380 (15)	−0.0088 (14)	−0.0198 (14)	−0.0027 (12)
C12	0.0499 (16)	0.0397 (15)	0.0401 (15)	−0.0092 (12)	−0.0122 (12)	−0.0084 (12)
C13	0.0510 (17)	0.0442 (17)	0.065 (2)	−0.0106 (14)	−0.0162 (15)	0.0009 (14)
C14	0.0596 (19)	0.0531 (19)	0.063 (2)	−0.0022 (15)	−0.0246 (16)	−0.0007 (15)
C15	0.072 (2)	0.0405 (16)	0.0363 (15)	−0.0119 (14)	−0.0124 (14)	−0.0031 (12)
C16	0.0615 (19)	0.0416 (16)	0.0510 (17)	−0.0156 (14)	−0.0083 (14)	−0.0075 (13)
C17	0.0490 (16)	0.0442 (16)	0.0510 (17)	−0.0111 (13)	−0.0130 (13)	−0.0092 (13)
C18	0.153 (4)	0.045 (2)	0.057 (2)	−0.003 (2)	−0.040 (3)	−0.0074 (16)
O4A	0.341 (14)	0.060 (4)	0.057 (4)	0.018 (7)	−0.045 (6)	−0.017 (3)
O4B	0.162 (7)	0.044 (3)	0.087 (5)	−0.015 (4)	−0.069 (5)	−0.009 (3)
C19	0.128 (4)	0.0412 (19)	0.070 (2)	−0.002 (2)	−0.020 (2)	−0.0011 (16)
C20	0.071 (2)	0.0475 (17)	0.0543 (18)	−0.0161 (14)	−0.0085 (15)	−0.0191 (14)
C21	0.0548 (19)	0.0492 (17)	0.0397 (16)	−0.0136 (14)	−0.0073 (13)	−0.0047 (13)
C22	0.077 (2)	0.0501 (19)	0.061 (2)	−0.0128 (17)	−0.0088 (17)	0.0060 (16)

O1—C2	1.369 (3)	C11—H11C	0.960
O1—C9	1.380 (3)	C12—C17	1.389 (4)
O2—C2	1.205 (3)	C12—C13	1.392 (4)
O3—C18	1.324 (4)	C13—C14	1.369 (4)
O3—C15	1.402 (3)	C13—H13	0.930
O5—C6	1.364 (3)	C14—C15	1.372 (5)
O5—C20	1.423 (4)	C14—H14	0.930
O6—C21	1.363 (3)	C15—C16	1.369 (5)
O6—C7	1.392 (3)	C16—C17	1.378 (4)
O7—C21	1.194 (4)	C16—H16	0.930
C2—C3	1.461 (4)	C17—H17	0.930
C3—C4	1.371 (4)	C18—O4A	1.248 (7)
C3—C12	1.480 (4)	C18—O4B	1.257 (7)
C4—C10	1.442 (3)	C18—C19	1.461 (5)
C4—C11	1.498 (4)	C19—H19A	0.960
C5—C6	1.364 (4)	C19—H19B	0.960
C5—C10	1.421 (4)	C19—H19C	0.960
C5—H5	0.930	C20—H20A	0.960
C6—C7	1.392 (4)	C20—H20B	0.960
C7—C8	1.369 (4)	C20—H20C	0.960
C8—C9	1.386 (4)	C21—C22	1.470 (4)
C8—H8	0.930	C22—H22A	0.960
C9—C10	1.386 (4)	C22—H22B	0.960
C11—H11A	0.960	C22—H22C	0.960
C11—H11B	0.960
C2—O1—C9	121.4 (2)	C14—C13—H13	119.3
C18—O3—C15	120.8 (2)	C12—C13—H13	119.3
C6—O5—C20	116.9 (2)	C13—C14—C15	120.2 (3)
C21—O6—C7	116.7 (2)	C13—C14—H14	119.9
O2—C2—O1	115.9 (2)	C15—C14—H14	119.9
O2—C2—C3	125.5 (3)	C16—C15—C14	120.0 (3)
O1—C2—C3	118.6 (2)	C16—C15—O3	121.5 (3)
C4—C3—C2	120.2 (2)	C14—C15—O3	118.4 (3)
C4—C3—C12	124.4 (2)	C15—C16—C17	119.7 (3)
C2—C3—C12	115.4 (2)	C15—C16—H16	120.1
C3—C4—C10	119.3 (2)	C17—C16—H16	120.1
C3—C4—C11	121.6 (2)	C16—C17—C12	121.6 (3)
C10—C4—C11	119.1 (2)	C16—C17—H17	119.2
C6—C5—C10	121.0 (2)	C12—C17—H17	119.2
C6—C5—H5	119.5	O4A—C18—O3	113.0 (5)
C10—C5—H5	119.5	O4B—C18—O3	117.6 (5)
O5—C6—C5	125.2 (2)	O4A—C18—C19	123.9 (5)
O5—C6—C7	115.1 (2)	O4B—C18—C19	119.1 (5)
C5—C6—C7	119.6 (2)	O3—C18—C19	114.7 (3)
C8—C7—O6	119.0 (2)	C18—C19—H19A	109.5
C8—C7—C6	121.2 (2)	C18—C19—H19B	109.5
O6—C7—C6	119.7 (2)	H19A—C19—H19B	109.5
C7—C8—C9	118.6 (2)	C18—C19—H19C	109.5
C7—C8—H8	120.7	H19A—C19—H19C	109.5
C9—C8—H8	120.7	H19B—C19—H19C	109.5
O1—C9—C10	121.3 (2)	O5—C20—H20A	109.5
O1—C9—C8	116.2 (2)	O5—C20—H20B	109.5
C10—C9—C8	122.5 (2)	H20A—C20—H20B	109.5
C9—C10—C5	117.0 (2)	O5—C20—H20C	109.5
C9—C10—C4	119.1 (2)	H20A—C20—H20C	109.5
C5—C10—C4	123.8 (2)	H20B—C20—H20C	109.5
C4—C11—H11A	109.5	O7—C21—O6	121.7 (3)
C4—C11—H11B	109.5	O7—C21—C22	127.3 (3)
H11A—C11—H11B	109.5	O6—C21—C22	111.0 (3)
C4—C11—H11C	109.5	C21—C22—H22A	109.5
H11A—C11—H11C	109.5	C21—C22—H22B	109.5
H11B—C11—H11C	109.5	H22A—C22—H22B	109.5
C17—C12—C13	117.1 (3)	C21—C22—H22C	109.5
C17—C12—C3	120.9 (2)	H22A—C22—H22C	109.5
C13—C12—C3	121.9 (2)	H22B—C22—H22C	109.5
C14—C13—C12	121.4 (3)
C9—O1—C2—O2	177.5 (2)	C8—C9—C10—C4	−177.3 (2)
C9—O1—C2—C3	−1.8 (4)	C6—C5—C10—C9	0.9 (4)
O2—C2—C3—C4	−177.4 (3)	C6—C5—C10—C4	178.1 (2)
O1—C2—C3—C4	1.8 (4)	C3—C4—C10—C9	−2.5 (4)
O2—C2—C3—C12	3.8 (4)	C11—C4—C10—C9	177.7 (2)
O1—C2—C3—C12	−177.0 (2)	C3—C4—C10—C5	−179.6 (2)
C2—C3—C4—C10	0.3 (4)	C11—C4—C10—C5	0.6 (4)
C12—C3—C4—C10	179.0 (2)	C4—C3—C12—C17	−113.2 (3)
C2—C3—C4—C11	−179.9 (2)	C2—C3—C12—C17	65.6 (4)
C12—C3—C4—C11	−1.2 (4)	C4—C3—C12—C13	70.4 (4)
C20—O5—C6—C5	2.5 (4)	C2—C3—C12—C13	−110.8 (3)
C20—O5—C6—C7	−175.2 (2)	C17—C12—C13—C14	1.2 (5)
C10—C5—C6—O5	−179.4 (2)	C3—C12—C13—C14	177.8 (3)
C10—C5—C6—C7	−1.8 (4)	C12—C13—C14—C15	−1.0 (5)
C21—O6—C7—C8	106.7 (3)	C13—C14—C15—C16	0.9 (5)
C21—O6—C7—C6	−76.1 (3)	C13—C14—C15—O3	176.9 (3)
O5—C6—C7—C8	179.6 (2)	C18—O3—C15—C16	−74.4 (5)
C5—C6—C7—C8	1.7 (4)	C18—O3—C15—C14	109.6 (4)
O5—C6—C7—O6	2.5 (4)	C14—C15—C16—C17	−1.0 (5)
C5—C6—C7—O6	−175.4 (2)	O3—C15—C16—C17	−176.9 (3)
O6—C7—C8—C9	176.3 (2)	C15—C16—C17—C12	1.1 (5)
C6—C7—C8—C9	−0.8 (4)	C13—C12—C17—C16	−1.2 (4)
C2—O1—C9—C10	−0.4 (4)	C3—C12—C17—C16	−177.8 (3)
C2—O1—C9—C8	179.4 (2)	C15—O3—C18—O4A	−27.7 (9)
C7—C8—C9—O1	−180.0 (2)	C15—O3—C18—O4B	35.1 (8)
C7—C8—C9—C10	−0.1 (4)	C15—O3—C18—C19	−177.3 (3)
O1—C9—C10—C5	179.9 (2)	C7—O6—C21—O7	−8.4 (4)
C8—C9—C10—C5	0.0 (4)	C7—O6—C21—C22	173.1 (3)
O1—C9—C10—C4	2.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20B···O2i	0.96	2.47	3.362 (4)	154
C20—H20C···O4Bi	0.96	2.55	3.297 (9)	134
C11—H11B···O7ii	0.96	2.74	3.349 (4)	122
C13—H13···O2iii	0.93	2.74	3.331 (4)	122
C19—H19A···O7iii	0.96	2.50	3.392 (5)	154
C17—H17···O2iv	0.93	2.66	3.246 (3)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20B⋯O2i	0.96	2.47	3.362 (4)	154
C20—H20C⋯O4Bi	0.96	2.55	3.297 (9)	134
C11—H11B⋯O7ii	0.96	2.74	3.349 (4)	122
C13—H13⋯O2iii	0.93	2.74	3.331 (4)	122
C19—H19A⋯O7iii	0.96	2.50	3.392 (5)	154
C17—H17⋯O2iv	0.93	2.66	3.246 (3)	122

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