rac-(1S,2R)-Diethyl 6-hydr-oxy-1-(4-methoxy-phen-yl)-3-oxo-2,3-di-hydro-1H-benzo[f]chromen-2-yl]-phospho-nate.

In the title compound, C(24)H(25)O(7)P, the δ-valerolactonyl ring exists in a distorted screw-boat conformation with the diethoxy-phosphoryl substituent occupying an axial position. The latter adopts an almost syn-periplanar conformation around the P-C bond. The mol-ecules form centrosymmetric dimers connected by O-H⋯O hydrogen bonds.

Related literature

For the biological activity of 4-aryl-3,4-dihydro­coumarins, see: Bailly et al. (2003 ▶); Roelens et al. (2005 ▶); Zhang et al. (2006 ▶). For their synthesis, see: Aoki et al. (2005 ▶); Krawczyk et al. (2007a ▶); Li et al. (2005 ▶); Rizzi et al. (2006 ▶). For a comparison structure, see: Krawczyk et al. (2007b ▶).

For the atomic charges fitted to electrostatic potential, see: Frisch et al. (2004 ▶); Breneman & Wiberg (1990 ▶). For repulsive interactions between O atoms, see: Gillespie & Popelier, (2001 ▶). For hydrogen-bond graph-set terminology, see: Bernstein et al. (1995 ▶); Etter (1990 ▶). For ring puckering analysis, see: Boeyens (1978 ▶); Cremer & Pople (1975 ▶); Frisch et al. (2004 ▶). For details of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C24H25O7P

M = 456.41

Monoclinic,

a = 21.6231 (17) Å

b = 10.0018 (8) Å

c = 22.4011 (17) Å

β = 111.806 (1)°

V = 4498.0 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.17 mm−1

T = 293 (2) K

0.30 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.951, T max = 0.976

37601 measured reflections

5076 independent reflections

3585 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.137

S = 1.05

5076 reflections

310 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.36 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; 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 and publCIF (Westrip, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015857/ng2458sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015857/ng2458Isup2.hkl

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

Enhanced figure: interactive version of Fig. 4

C24H25O7P	Dx = 1.348 Mg m−3
Mr = 456.41	Melting point = 396–398 K
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
a = 21.6231 (17) Å	Cell parameters from 8721 reflections
b = 10.0018 (8) Å	θ = 2.2–23.3º
c = 22.4011 (17) Å	µ = 0.17 mm−1
β = 111.8060 (10)º	T = 293 (2) K
V = 4498.0 (6) Å3	Prism, colourless
Z = 8	0.30 × 0.20 × 0.15 mm
F000 = 1920

Bruker SMART APEX diffractometer	5076 independent reflections
Radiation source: fine-focus sealed tube	3585 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.044
T = 293(2) K	θmax = 27.4º
ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 2003)	h = −27→27
Tmin = 0.951, Tmax = 0.976	k = −12→12
37601 measured reflections	l = −28→28

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.137	w = 1/[σ2(Fo2) + (0.0691P)2 + 2.0425P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
5076 reflections	Δρmax = 0.30 e Å−3
310 parameters	Δρmin = −0.36 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
P	0.85826 (2)	0.18689 (5)	0.93687 (3)	0.04719 (16)
O1	0.86909 (7)	0.50338 (13)	0.99316 (6)	0.0501 (3)
O2	0.82123 (8)	0.38041 (16)	1.04447 (7)	0.0612 (4)
O3	0.82989 (9)	0.07064 (16)	0.96515 (11)	0.0843 (6)
O4	0.92748 (7)	0.22132 (16)	0.97264 (8)	0.0645 (4)
O5	0.84281 (8)	0.14572 (19)	0.86632 (8)	0.0751 (5)
O6	1.00680 (7)	0.72224 (17)	0.90165 (8)	0.0694 (5)
O7	0.54354 (8)	0.70103 (17)	0.84382 (11)	0.0838 (6)
C1	0.82904 (10)	0.40053 (19)	0.99520 (10)	0.0464 (4)
C2	0.79907 (9)	0.31862 (18)	0.93467 (9)	0.0445 (4)
C3	0.77848 (9)	0.40694 (18)	0.87347 (9)	0.0433 (4)
C4	0.83847 (9)	0.49031 (17)	0.87772 (9)	0.0411 (4)
C5	0.85316 (9)	0.53228 (18)	0.82352 (9)	0.0432 (4)
C6	0.91093 (9)	0.60975 (19)	0.83255 (9)	0.0457 (4)
C7	0.95280 (9)	0.6475 (2)	0.89610 (10)	0.0492 (5)
C8	0.93774 (10)	0.60900 (19)	0.94736 (10)	0.0484 (5)
C9	0.88100 (9)	0.53133 (18)	0.93693 (9)	0.0435 (4)
C10	0.81079 (11)	0.5026 (2)	0.75920 (10)	0.0540 (5)
C11	0.82642 (13)	0.5444 (2)	0.70810 (11)	0.0616 (6)
C12	0.88486 (13)	0.6152 (2)	0.71814 (12)	0.0636 (6)
C13	0.92573 (12)	0.6490 (2)	0.77862 (11)	0.0567 (5)
C14	0.71632 (9)	0.48976 (18)	0.86470 (9)	0.0436 (4)
C15	0.65938 (10)	0.4277 (2)	0.86667 (12)	0.0596 (6)
C16	0.60208 (11)	0.4993 (2)	0.85812 (13)	0.0667 (6)
C17	0.60088 (11)	0.6368 (2)	0.84824 (11)	0.0589 (5)
C18	0.65601 (11)	0.6988 (2)	0.84519 (11)	0.0586 (5)
C19	0.71301 (11)	0.6250 (2)	0.85320 (10)	0.0525 (5)
C20	0.85865 (19)	−0.0622 (3)	0.97519 (18)	0.0957 (10)
C21	0.80938 (19)	−0.1530 (3)	0.98260 (16)	0.0963 (10)
C22	0.89018 (18)	0.1465 (3)	0.83444 (15)	0.0930 (9)
C23	0.90252 (16)	0.0103 (4)	0.81830 (16)	0.0989 (10)
C24	0.54361 (16)	0.8430 (3)	0.84361 (19)	0.1038 (12)
H6	1.0276	0.7404	0.9401	0.083*
H21	0.7610	0.2782	0.9357	0.053*
H31	0.7679	0.3463	0.8355	0.049*
H81	0.9632	0.6325	0.9862	0.058*
H101	0.7706	0.4525	0.7514	0.065*
H111	0.7983	0.5257	0.6674	0.074*
H121	0.8960	0.6395	0.6832	0.076*
H131	0.9646	0.6994	0.7848	0.068*
H151	0.6601	0.3230	0.8750	0.071*
H161	0.5596	0.4502	0.8591	0.080*
H181	0.6553	0.7910	0.8377	0.070*
H191	0.7487	0.6669	0.8508	0.063*
H201	0.9030	−0.0639	1.0173	0.115*
H202	0.8708	−0.0913	0.9351	0.115*
H211	0.7686	−0.1586	0.9396	0.116*
H212	0.7941	−0.1177	1.0185	0.116*
H213	0.8303	−0.2473	0.9950	0.116*
H221	0.9333	0.1881	0.8636	0.112*
H222	0.8721	0.2019	0.7940	0.112*
H231	0.8583	−0.0365	0.7950	0.119*
H232	0.9286	−0.0405	0.8593	0.119*
H233	0.9293	0.0130	0.7894	0.119*
H241	0.5474	0.8736	0.8060	0.125*
H242	0.5793	0.8740	0.8787	0.125*
H243	0.5042	0.8741	0.8460	0.125*

	U11	U22	U33	U12	U13	U23
P	0.0439 (3)	0.0381 (3)	0.0599 (3)	−0.0019 (2)	0.0197 (2)	−0.0012 (2)
O1	0.0655 (8)	0.0447 (7)	0.0433 (7)	−0.0119 (6)	0.0239 (6)	−0.0030 (6)
O2	0.0725 (10)	0.0645 (9)	0.0561 (9)	−0.0060 (7)	0.0350 (8)	0.0033 (7)
O3	0.0837 (12)	0.0446 (9)	0.1457 (18)	0.0093 (8)	0.0673 (12)	0.0225 (10)
O4	0.0446 (8)	0.0607 (9)	0.0785 (11)	−0.0006 (7)	0.0117 (7)	−0.0075 (8)
O5	0.0616 (9)	0.0879 (12)	0.0692 (11)	0.0157 (8)	0.0167 (8)	−0.0224 (9)
O6	0.0543 (9)	0.0794 (11)	0.0696 (10)	−0.0216 (8)	0.0174 (7)	0.0139 (8)
O7	0.0596 (10)	0.0626 (11)	0.1338 (17)	0.0164 (8)	0.0414 (10)	0.0119 (10)
C1	0.0509 (10)	0.0410 (9)	0.0514 (11)	0.0028 (8)	0.0236 (9)	0.0050 (8)
C2	0.0418 (9)	0.0380 (9)	0.0562 (11)	−0.0040 (8)	0.0213 (8)	0.0010 (8)
C3	0.0451 (10)	0.0381 (9)	0.0464 (10)	−0.0037 (7)	0.0169 (8)	−0.0037 (8)
C4	0.0412 (9)	0.0383 (9)	0.0445 (10)	−0.0008 (7)	0.0170 (8)	0.0002 (7)
C5	0.0448 (10)	0.0414 (9)	0.0437 (10)	0.0087 (8)	0.0169 (8)	0.0033 (8)
C6	0.0461 (10)	0.0426 (10)	0.0511 (11)	0.0087 (8)	0.0214 (8)	0.0098 (8)
C7	0.0418 (10)	0.0459 (10)	0.0584 (12)	−0.0003 (8)	0.0169 (9)	0.0101 (9)
C8	0.0493 (11)	0.0459 (10)	0.0443 (11)	−0.0060 (8)	0.0106 (8)	0.0032 (8)
C9	0.0514 (10)	0.0378 (9)	0.0433 (10)	−0.0006 (8)	0.0198 (8)	0.0018 (7)
C10	0.0553 (12)	0.0562 (12)	0.0483 (12)	0.0062 (9)	0.0167 (9)	−0.0012 (9)
C11	0.0753 (15)	0.0636 (14)	0.0431 (11)	0.0190 (11)	0.0189 (10)	0.0050 (10)
C12	0.0793 (16)	0.0655 (14)	0.0563 (13)	0.0187 (12)	0.0371 (12)	0.0177 (11)
C13	0.0600 (12)	0.0579 (12)	0.0601 (14)	0.0096 (10)	0.0316 (11)	0.0160 (10)
C14	0.0445 (10)	0.0403 (9)	0.0432 (10)	−0.0030 (8)	0.0129 (8)	−0.0045 (8)
C15	0.0497 (12)	0.0424 (11)	0.0826 (16)	−0.0040 (9)	0.0200 (11)	−0.0020 (10)
C16	0.0469 (12)	0.0520 (12)	0.0978 (19)	−0.0041 (10)	0.0231 (12)	−0.0002 (12)
C17	0.0513 (12)	0.0538 (12)	0.0698 (14)	0.0071 (9)	0.0204 (10)	0.0034 (10)
C18	0.0631 (13)	0.0425 (11)	0.0710 (14)	0.0055 (9)	0.0262 (11)	0.0090 (10)
C19	0.0526 (11)	0.0445 (10)	0.0634 (13)	−0.0034 (9)	0.0248 (10)	0.0045 (9)
C20	0.134 (3)	0.0501 (14)	0.134 (3)	0.0191 (15)	0.085 (2)	0.0209 (15)
C21	0.150 (3)	0.0501 (14)	0.093 (2)	−0.0089 (17)	0.050 (2)	−0.0010 (14)
C22	0.128 (3)	0.091 (2)	0.0795 (19)	0.0193 (19)	0.0617 (19)	0.0055 (16)
C23	0.093 (2)	0.109 (2)	0.102 (2)	0.0270 (19)	0.0449 (18)	−0.0189 (19)
C24	0.084 (2)	0.0640 (17)	0.169 (4)	0.0255 (15)	0.053 (2)	0.0175 (19)

P—O4	1.4524 (15)	C11—C12	1.392 (3)
P—O5	1.5449 (17)	C11—H111	0.9082
P—O3	1.5551 (16)	C12—C13	1.357 (3)
P—C2	1.8248 (19)	C12—H121	0.9322
O1—C1	1.356 (2)	C13—H131	0.9462
O1—C9	1.404 (2)	C14—C19	1.374 (3)
O2—C1	1.194 (2)	C14—C15	1.394 (3)
O3—C20	1.449 (3)	C15—C16	1.381 (3)
O5—C22	1.450 (3)	C15—H151	1.0672
O6—C7	1.352 (2)	C16—C17	1.391 (3)
O6—H6	0.8309	C16—H161	1.0483
O7—C17	1.367 (3)	C17—C18	1.368 (3)
O7—C24	1.420 (3)	C18—C19	1.390 (3)
C1—C2	1.509 (3)	C18—H181	0.9346
C2—C3	1.551 (3)	C19—H191	0.8967
C2—H21	0.9241	C20—C21	1.455 (4)
C3—C4	1.515 (2)	C20—H201	1.0668
C3—C14	1.528 (3)	C20—H202	1.0668
C3—H31	1.0001	C21—H211	1.0385
C4—C9	1.366 (3)	C21—H212	1.0385
C4—C5	1.428 (3)	C21—H213	1.0385
C5—C6	1.419 (3)	C22—C23	1.459 (4)
C5—C10	1.422 (3)	C22—H221	1.0092
C6—C13	1.415 (3)	C22—H222	1.0092
C6—C7	1.425 (3)	C23—H231	1.0166
C7—C8	1.360 (3)	C23—H232	1.0166
C8—C9	1.397 (3)	C23—H233	1.0166
C8—H81	0.8711	C24—H241	0.9270
C10—C11	1.374 (3)	C24—H242	0.9270
C10—H101	0.9613	C24—H243	0.9270
O4—P—O5	114.48 (10)	C11—C12—H121	119.9
O4—P—O3	115.74 (11)	C12—C13—C6	120.9 (2)
O5—P—O3	104.43 (11)	C12—C13—H131	119.6
O4—P—C2	114.36 (9)	C6—C13—H131	119.6
O5—P—C2	106.37 (9)	C19—C14—C15	117.34 (18)
O3—P—C2	99.90 (9)	C19—C14—C3	122.67 (17)
C1—O1—C9	120.89 (15)	C15—C14—C3	119.98 (17)
C20—O3—P	122.52 (17)	C16—C15—C14	121.5 (2)
C22—O5—P	125.35 (18)	C16—C15—H151	119.3
C7—O6—H6	109.5	C14—C15—H151	119.3
C17—O7—C24	117.9 (2)	C15—C16—C17	119.8 (2)
O2—C1—O1	118.05 (18)	C15—C16—H161	120.1
O2—C1—C2	125.32 (18)	C17—C16—H161	120.1
O1—C1—C2	116.61 (16)	O7—C17—C18	124.5 (2)
C1—C2—C3	111.81 (15)	O7—C17—C16	116.0 (2)
C1—C2—P	107.75 (13)	C18—C17—C16	119.4 (2)
C3—C2—P	113.78 (13)	C17—C18—C19	120.0 (2)
C1—C2—H21	107.8	C17—C18—H181	120.0
C3—C2—H21	107.8	C19—C18—H181	120.0
P—C2—H21	107.8	C14—C19—C18	121.9 (2)
C4—C3—C14	113.67 (15)	C14—C19—H191	119.0
C4—C3—C2	107.47 (15)	C18—C19—H191	119.0
C14—C3—C2	111.86 (15)	O3—C20—C21	107.4 (3)
C4—C3—H31	107.9	O3—C20—H201	110.2
C14—C3—H31	107.9	C21—C20—H201	110.2
C2—C3—H31	107.9	O3—C20—H202	110.2
C9—C4—C5	117.07 (17)	C21—C20—H202	110.2
C9—C4—C3	118.56 (16)	H201—C20—H202	108.5
C5—C4—C3	124.35 (16)	C20—C21—H211	109.5
C6—C5—C10	117.40 (18)	C20—C21—H212	109.5
C6—C5—C4	120.10 (17)	H211—C21—H212	109.5
C10—C5—C4	122.48 (18)	C20—C21—H213	109.5
C13—C6—C5	119.73 (19)	H211—C21—H213	109.5
C13—C6—C7	121.19 (19)	H212—C21—H213	109.5
C5—C6—C7	119.08 (17)	O5—C22—C23	110.2 (3)
O6—C7—C8	123.23 (19)	O5—C22—H221	109.6
O6—C7—C6	116.41 (18)	C23—C22—H221	109.6
C8—C7—C6	120.37 (18)	O5—C22—H222	109.6
C7—C8—C9	119.15 (19)	C23—C22—H222	109.6
C7—C8—H81	120.4	H221—C22—H222	108.1
C9—C8—H81	120.4	C22—C23—H231	109.5
C4—C9—C8	124.20 (17)	C22—C23—H232	109.5
C4—C9—O1	121.96 (17)	H231—C23—H232	109.5
C8—C9—O1	113.77 (16)	C22—C23—H233	109.5
C11—C10—C5	121.0 (2)	H231—C23—H233	109.5
C11—C10—H101	119.5	H232—C23—H233	109.5
C5—C10—H101	119.5	O7—C24—H241	109.5
C10—C11—C12	120.7 (2)	O7—C24—H242	109.5
C10—C11—H111	119.7	H241—C24—H242	109.5
C12—C11—H111	119.7	O7—C24—H243	109.5
C13—C12—C11	120.2 (2)	H241—C24—H243	109.5
C13—C12—H121	119.9	H242—C24—H243	109.5
O4—P—C2—C1	−28.73 (16)	C13—C6—C7—C8	179.94 (18)
O5—P—C2—C3	−31.54 (16)	C5—C6—C7—C8	0.4 (3)
O4—P—O3—C20	−58.5 (3)	O6—C7—C8—C9	−179.72 (18)
O5—P—O3—C20	68.3 (3)	C6—C7—C8—C9	0.4 (3)
C2—P—O3—C20	178.2 (2)	C5—C4—C9—C8	−1.1 (3)
O4—P—O5—C22	−3.4 (3)	C3—C4—C9—C8	−179.64 (17)
O3—P—O5—C22	−131.0 (2)	C5—C4—C9—O1	175.78 (15)
C2—P—O5—C22	123.9 (2)	C3—C4—C9—O1	−2.8 (3)
C9—O1—C1—O2	179.21 (17)	C7—C8—C9—C4	−0.1 (3)
C9—O1—C1—C2	0.5 (2)	C7—C8—C9—O1	−177.13 (17)
O2—C1—C2—C3	143.09 (19)	C1—O1—C9—C4	22.1 (3)
O1—C1—C2—C3	−38.3 (2)	C1—O1—C9—C8	−160.77 (17)
O2—C1—C2—P	−91.2 (2)	C6—C5—C10—C11	1.8 (3)
O1—C1—C2—P	87.41 (17)	C4—C5—C10—C11	−179.95 (18)
O5—P—C2—C1	−156.12 (13)	C5—C10—C11—C12	1.1 (3)
O3—P—C2—C1	95.53 (15)	C10—C11—C12—C13	−3.0 (3)
O4—P—C2—C3	95.84 (15)	C11—C12—C13—C6	1.9 (3)
O5—P—C2—C3	−31.54 (16)	C5—C6—C13—C12	1.0 (3)
O3—P—C2—C3	−139.90 (15)	C7—C6—C13—C12	−178.5 (2)
C1—C2—C3—C4	52.53 (19)	C4—C3—C14—C19	8.2 (3)
P—C2—C3—C4	−69.83 (17)	C2—C3—C14—C19	130.13 (19)
C1—C2—C3—C14	−72.89 (19)	C4—C3—C14—C15	−173.41 (18)
P—C2—C3—C14	164.74 (12)	C2—C3—C14—C15	−51.5 (2)
C14—C3—C4—C9	90.9 (2)	C19—C14—C15—C16	−0.7 (3)
C2—C3—C4—C9	−33.4 (2)	C3—C14—C15—C16	−179.2 (2)
C14—C3—C4—C5	−87.6 (2)	C14—C15—C16—C17	−1.0 (4)
C2—C3—C4—C5	148.11 (17)	C24—O7—C17—C18	−7.7 (4)
C9—C4—C5—C6	1.9 (3)	C24—O7—C17—C16	170.6 (3)
C3—C4—C5—C6	−179.65 (16)	C15—C16—C17—O7	−176.4 (2)
C9—C4—C5—C10	−176.39 (17)	C15—C16—C17—C18	2.0 (4)
C3—C4—C5—C10	2.1 (3)	O7—C17—C18—C19	177.0 (2)
C10—C5—C6—C13	−2.8 (3)	C16—C17—C18—C19	−1.3 (4)
C4—C5—C6—C13	178.90 (17)	C15—C14—C19—C18	1.4 (3)
C10—C5—C6—C7	176.76 (17)	C3—C14—C19—C18	179.84 (19)
C4—C5—C6—C7	−1.6 (3)	C17—C18—C19—C14	−0.4 (3)
C13—C6—C7—O6	0.0 (3)	P—O3—C20—C21	−162.7 (2)
C5—C6—C7—O6	−179.46 (17)	P—O5—C22—C23	114.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O4i	0.83	1.87	2.701 (2)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6⋯O4i	0.83	1.87	2.701 (2)	178

Symmetry code: (i) .