5-Hy-droxy-8,8-dimethyl-10-(2-methyl-but-3-en-2-yl)-2H,6H-7,8-dihydro-pyrano[3,2-g]chromene-2,6-dione.

In the title compound, C(19)H(20)O(5), the pyran ring is in an envelope conformation, whereas the benzene and dihydro-pyran ring system is planar with an r.m.s. deviation of 0.0190 (1) Å. The hy-droxy group is coplanar with the attached benzene ring [r.m.s. deviation = 0.0106 (1) Å]. An intra-molecular O-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol-ecules are linked into chains along the b axis by weak C-H⋯O inter-actions. These chains are stacked along the a axis. C-H⋯π and weak π-π inter-actions [centroid-centroid distance = 3.7698 (7) Å] are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶) and for ring conformations, see: Cremer & Pople (1975 ▶). For background to Rutaceae plants, coumarins and their biological activity, see: Kongkathip et al. (2005 ▶); Laphookhieo et al. (2009 ▶); Maneerat et al. (2010 ▶); Huang et al. (1997 ▶); Su et al. (2009 ▶); Tangyuenyongwatthana et al. (1992 ▶); Yenjai et al. (2000 ▶).

Experimental

Crystal data

C19H20O5

M = 328.35

Monoclinic,

a = 10.2239 (2) Å

b = 11.3090 (3) Å

c = 13.8764 (3) Å

β = 93.108 (1)°

V = 1602.06 (6) Å3

Z = 4

Cu Kα radiation

μ = 0.81 mm−1

T = 100 K

0.43 × 0.43 × 0.33 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.721, T max = 0.774

48432 measured reflections

3114 independent reflections

3088 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.147

S = 1.29

3114 reflections

234 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.84 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001565/bq2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001565/bq2271Isup2.hkl

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

C19H20O5	F(000) = 696
Mr = 328.35	Dx = 1.361 Mg m−3
Monoclinic, P21/c	Melting point = 410–411 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 10.2239 (2) Å	Cell parameters from 3114 reflections
b = 11.3090 (3) Å	θ = 5.8–72.0°
c = 13.8764 (3) Å	µ = 0.81 mm−1
β = 93.108 (1)°	T = 100 K
V = 1602.06 (6) Å3	Block, yellow
Z = 4	0.43 × 0.43 × 0.33 mm

Bruker APEX DUO CCD area-detector diffractometer	3114 independent reflections
Radiation source: sealed tube	3088 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 72.0°, θmin = 5.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.721, Tmax = 0.774	k = −12→13
48432 measured reflections	l = −16→16

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.147	w = 1/[σ2(Fo2) + (0.085P)2 + 0.4129P] where P = (Fo2 + 2Fc2)/3
S = 1.29	(Δ/σ)max = 0.001
3114 reflections	Δρmax = 0.71 e Å−3
234 parameters	Δρmin = −0.84 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.041 (2)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 2sigma(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
O1	0.24205 (9)	1.16069 (8)	0.99936 (7)	0.0182 (3)
O2	0.25452 (9)	0.76187 (8)	0.90044 (6)	0.0178 (3)
O3	0.25906 (11)	1.34713 (9)	1.04469 (8)	0.0251 (3)
O4	0.01977 (10)	0.66004 (9)	1.11316 (7)	0.0228 (3)
O5	0.01904 (10)	0.87092 (9)	1.17530 (7)	0.0216 (3)
H1O5	0.010 (2)	0.789 (2)	1.1695 (16)	0.046 (6)*
C1	0.20676 (12)	1.04507 (12)	1.01109 (9)	0.0155 (3)
C2	0.21353 (13)	1.25150 (12)	1.06206 (10)	0.0188 (3)
C3	0.13341 (13)	1.22145 (13)	1.14119 (10)	0.0201 (3)
H3A	0.1083	1.2802	1.1833	0.024*
C4	0.09493 (13)	1.10932 (12)	1.15431 (10)	0.0186 (3)
H4A	0.0440	1.0912	1.2059	0.022*
C5	0.13116 (12)	1.01699 (12)	1.09000 (9)	0.0164 (3)
C6	0.09425 (12)	0.89887 (12)	1.10224 (9)	0.0165 (3)
C7	0.13559 (12)	0.81207 (12)	1.03860 (9)	0.0162 (3)
C8	0.09306 (12)	0.69006 (12)	1.04907 (10)	0.0180 (3)
C9	0.13851 (13)	0.60284 (12)	0.97689 (10)	0.0194 (3)
H9A	0.0724	0.5956	0.9244	0.023*
H9B	0.1490	0.5260	1.0074	0.023*
C10	0.26803 (14)	0.63988 (11)	0.93635 (10)	0.0183 (3)
C11	0.21402 (12)	0.84528 (12)	0.96178 (9)	0.0154 (3)
C12	0.25049 (12)	0.96284 (12)	0.94385 (9)	0.0154 (3)
C13	0.33249 (13)	0.98950 (12)	0.85555 (9)	0.0176 (3)
C14	0.45881 (13)	0.91792 (13)	0.86498 (10)	0.0211 (3)
H14A	0.5002	0.9134	0.9262	0.025*
C15	0.51505 (15)	0.86207 (14)	0.79547 (11)	0.0258 (4)
H15A	0.473 (2)	0.8581 (18)	0.7301 (16)	0.038 (5)*
H15B	0.598 (2)	0.8228 (18)	0.8085 (14)	0.034 (5)*
C16	0.24997 (13)	0.95973 (13)	0.76241 (9)	0.0204 (3)
H16A	0.2977	0.9812	0.7073	0.031*
H16B	0.1691	1.0029	0.7614	0.031*
H16C	0.2318	0.8765	0.7605	0.031*
C17	0.37739 (16)	1.11907 (13)	0.84519 (11)	0.0273 (4)
H17A	0.4288	1.1263	0.7896	0.041*
H17B	0.4293	1.1419	0.9019	0.041*
H17C	0.3020	1.1695	0.8377	0.041*
C18	0.29707 (16)	0.56754 (13)	0.84802 (11)	0.0252 (3)
H18A	0.3768	0.5951	0.8222	0.038*
H18B	0.2263	0.5759	0.8001	0.038*
H18C	0.3065	0.4858	0.8658	0.038*
C19	0.38167 (14)	0.63524 (12)	1.01187 (10)	0.0213 (3)
H19A	0.4603	0.6615	0.9837	0.032*
H19B	0.3932	0.5555	1.0345	0.032*
H19C	0.3631	0.6857	1.0650	0.032*

	U11	U22	U33	U12	U13	U23
O1	0.0233 (5)	0.0130 (5)	0.0188 (5)	−0.0003 (4)	0.0045 (4)	−0.0003 (3)
O2	0.0241 (5)	0.0126 (5)	0.0169 (5)	0.0009 (4)	0.0044 (4)	−0.0005 (3)
O3	0.0334 (6)	0.0144 (5)	0.0278 (6)	−0.0006 (4)	0.0039 (4)	−0.0006 (4)
O4	0.0219 (5)	0.0208 (5)	0.0261 (5)	−0.0027 (4)	0.0059 (4)	0.0046 (4)
O5	0.0235 (5)	0.0213 (6)	0.0208 (5)	−0.0009 (4)	0.0088 (4)	0.0018 (4)
C1	0.0153 (6)	0.0140 (6)	0.0171 (6)	0.0002 (5)	−0.0007 (5)	0.0011 (5)
C2	0.0205 (7)	0.0156 (7)	0.0201 (7)	0.0024 (5)	−0.0015 (5)	−0.0020 (5)
C3	0.0209 (7)	0.0203 (7)	0.0191 (7)	0.0042 (5)	0.0011 (5)	−0.0048 (5)
C4	0.0165 (6)	0.0225 (7)	0.0168 (6)	0.0024 (5)	0.0018 (5)	−0.0015 (5)
C5	0.0156 (6)	0.0183 (7)	0.0153 (6)	0.0013 (5)	0.0010 (5)	0.0002 (5)
C6	0.0139 (6)	0.0210 (7)	0.0147 (6)	0.0006 (5)	0.0012 (5)	0.0019 (5)
C7	0.0154 (6)	0.0164 (7)	0.0166 (6)	0.0001 (5)	0.0002 (5)	0.0019 (5)
C8	0.0150 (6)	0.0183 (7)	0.0204 (7)	0.0003 (5)	−0.0015 (5)	0.0033 (5)
C9	0.0200 (7)	0.0138 (6)	0.0242 (7)	−0.0017 (5)	0.0011 (5)	0.0014 (5)
C10	0.0227 (7)	0.0120 (6)	0.0206 (7)	0.0008 (5)	0.0028 (5)	0.0009 (5)
C11	0.0152 (6)	0.0161 (7)	0.0148 (6)	0.0014 (5)	−0.0004 (5)	−0.0009 (5)
C12	0.0159 (6)	0.0157 (7)	0.0147 (6)	0.0003 (5)	0.0013 (5)	0.0007 (5)
C13	0.0203 (7)	0.0170 (7)	0.0160 (6)	0.0000 (5)	0.0052 (5)	−0.0003 (5)
C14	0.0180 (7)	0.0267 (7)	0.0187 (7)	−0.0006 (5)	0.0011 (5)	0.0007 (5)
C15	0.0217 (7)	0.0305 (8)	0.0250 (8)	0.0060 (6)	0.0003 (6)	−0.0025 (6)
C16	0.0217 (7)	0.0233 (7)	0.0165 (7)	0.0032 (5)	0.0030 (5)	0.0028 (5)
C17	0.0376 (9)	0.0201 (7)	0.0257 (7)	−0.0052 (6)	0.0160 (6)	−0.0010 (6)
C18	0.0338 (8)	0.0174 (7)	0.0248 (7)	0.0017 (6)	0.0048 (6)	−0.0037 (5)
C19	0.0204 (7)	0.0199 (7)	0.0237 (7)	0.0020 (5)	0.0028 (5)	0.0017 (5)

O1—C1	1.3685 (16)	C10—C18	1.5164 (19)
O1—C2	1.3872 (16)	C10—C19	1.5227 (19)
O2—C11	1.3505 (16)	C11—C12	1.4065 (19)
O2—C10	1.4708 (15)	C12—C13	1.5513 (17)
O3—C2	1.2069 (18)	C13—C14	1.5238 (19)
O4—C8	1.2410 (17)	C13—C16	1.5419 (18)
O5—C6	1.3430 (16)	C13—C17	1.5445 (18)
O5—H1O5	0.93 (2)	C14—C15	1.311 (2)
C1—C12	1.4073 (19)	C14—H14A	0.9300
C1—C5	1.4103 (18)	C15—H15A	0.98 (2)
C2—C3	1.4456 (19)	C15—H15B	0.97 (2)
C3—C4	1.343 (2)	C16—H16A	0.9600
C3—H3A	0.9300	C16—H16B	0.9600
C4—C5	1.4352 (18)	C16—H16C	0.9600
C4—H4A	0.9300	C17—H17A	0.9600
C5—C6	1.4009 (19)	C17—H17B	0.9600
C6—C7	1.4009 (19)	C17—H17C	0.9600
C7—C11	1.4189 (18)	C18—H18A	0.9600
C7—C8	1.4564 (18)	C18—H18B	0.9600
C8—C9	1.4975 (19)	C18—H18C	0.9600
C9—C10	1.5253 (19)	C19—H19A	0.9600
C9—H9A	0.9700	C19—H19B	0.9600
C9—H9B	0.9700	C19—H19C	0.9600
C1—O1—C2	124.55 (11)	C12—C11—C7	123.30 (12)
C11—O2—C10	117.90 (10)	C11—C12—C1	114.24 (12)
C6—O5—H1O5	103.0 (14)	C11—C12—C13	118.90 (11)
O1—C1—C12	117.21 (12)	C1—C12—C13	126.86 (12)
O1—C1—C5	117.81 (12)	C14—C13—C16	112.25 (11)
C12—C1—C5	124.97 (13)	C14—C13—C17	104.91 (11)
O3—C2—O1	116.21 (12)	C16—C13—C17	106.32 (11)
O3—C2—C3	127.09 (13)	C14—C13—C12	108.70 (11)
O1—C2—C3	116.70 (12)	C16—C13—C12	108.97 (11)
C4—C3—C2	120.48 (12)	C17—C13—C12	115.72 (11)
C4—C3—H3A	119.8	C15—C14—C13	126.59 (13)
C2—C3—H3A	119.8	C15—C14—H14A	116.7
C3—C4—C5	121.02 (13)	C13—C14—H14A	116.7
C3—C4—H4A	119.5	C14—C15—H15A	120.7 (12)
C5—C4—H4A	119.5	C14—C15—H15B	120.0 (12)
C6—C5—C1	118.12 (12)	H15A—C15—H15B	119.3 (17)
C6—C5—C4	122.55 (12)	C13—C16—H16A	109.5
C1—C5—C4	119.32 (12)	C13—C16—H16B	109.5
O5—C6—C7	121.03 (12)	H16A—C16—H16B	109.5
O5—C6—C5	119.01 (12)	C13—C16—H16C	109.5
C7—C6—C5	119.95 (12)	H16A—C16—H16C	109.5
C6—C7—C11	119.36 (12)	H16B—C16—H16C	109.5
C6—C7—C8	119.95 (12)	C13—C17—H17A	109.5
C11—C7—C8	120.64 (12)	C13—C17—H17B	109.5
O4—C8—C7	121.72 (13)	H17A—C17—H17B	109.5
O4—C8—C9	121.36 (12)	C13—C17—H17C	109.5
C7—C8—C9	116.89 (12)	H17A—C17—H17C	109.5
C8—C9—C10	111.89 (11)	H17B—C17—H17C	109.5
C8—C9—H9A	109.2	C10—C18—H18A	109.5
C10—C9—H9A	109.2	C10—C18—H18B	109.5
C8—C9—H9B	109.2	H18A—C18—H18B	109.5
C10—C9—H9B	109.2	C10—C18—H18C	109.5
H9A—C9—H9B	107.9	H18A—C18—H18C	109.5
O2—C10—C18	104.54 (11)	H18B—C18—H18C	109.5
O2—C10—C19	108.64 (11)	C10—C19—H19A	109.5
C18—C10—C19	111.23 (12)	C10—C19—H19B	109.5
O2—C10—C9	108.37 (11)	H19A—C19—H19B	109.5
C18—C10—C9	111.21 (12)	C10—C19—H19C	109.5
C19—C10—C9	112.46 (11)	H19A—C19—H19C	109.5
O2—C11—C12	117.10 (12)	H19B—C19—H19C	109.5
O2—C11—C7	119.58 (12)
C2—O1—C1—C12	−176.20 (11)	C11—O2—C10—C19	−68.22 (14)
C2—O1—C1—C5	2.95 (18)	C11—O2—C10—C9	54.25 (14)
C1—O1—C2—O3	175.33 (12)	C8—C9—C10—O2	−52.54 (14)
C1—O1—C2—C3	−4.33 (18)	C8—C9—C10—C18	−166.91 (11)
O3—C2—C3—C4	−176.61 (14)	C8—C9—C10—C19	67.58 (14)
O1—C2—C3—C4	3.01 (19)	C10—O2—C11—C12	154.89 (11)
C2—C3—C4—C5	−0.5 (2)	C10—O2—C11—C7	−26.57 (16)
O1—C1—C5—C6	179.76 (11)	C6—C7—C11—O2	179.76 (11)
C12—C1—C5—C6	−1.2 (2)	C8—C7—C11—O2	−3.05 (18)
O1—C1—C5—C4	−0.19 (18)	C6—C7—C11—C12	−1.79 (19)
C12—C1—C5—C4	178.89 (12)	C8—C7—C11—C12	175.40 (11)
C3—C4—C5—C6	179.13 (12)	O2—C11—C12—C1	−179.17 (10)
C3—C4—C5—C1	−0.9 (2)	C7—C11—C12—C1	2.35 (19)
C1—C5—C6—O5	−178.07 (11)	O2—C11—C12—C13	0.61 (17)
C4—C5—C6—O5	1.87 (19)	C7—C11—C12—C13	−177.87 (11)
C1—C5—C6—C7	1.80 (19)	O1—C1—C12—C11	178.22 (10)
C4—C5—C6—C7	−178.26 (11)	C5—C1—C12—C11	−0.87 (19)
O5—C6—C7—C11	179.45 (11)	O1—C1—C12—C13	−1.54 (19)
C5—C6—C7—C11	−0.42 (19)	C5—C1—C12—C13	179.37 (12)
O5—C6—C7—C8	2.24 (19)	C11—C12—C13—C14	−57.89 (15)
C5—C6—C7—C8	−177.63 (11)	C1—C12—C13—C14	121.86 (14)
C6—C7—C8—O4	0.37 (19)	C11—C12—C13—C16	64.73 (15)
C11—C7—C8—O4	−176.81 (12)	C1—C12—C13—C16	−115.52 (14)
C6—C7—C8—C9	178.52 (11)	C11—C12—C13—C17	−175.57 (12)
C11—C7—C8—C9	1.35 (18)	C1—C12—C13—C17	4.2 (2)
O4—C8—C9—C10	−154.56 (12)	C16—C13—C14—C15	18.3 (2)
C7—C8—C9—C10	27.28 (16)	C17—C13—C14—C15	−96.71 (17)
C11—O2—C10—C18	172.93 (11)	C12—C13—C14—C15	138.93 (16)

Cg1 is the centroid of the C1–C5/O1ring.

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O4	0.93 (2)	1.66 (2)	2.5361 (14)	155 (2)
C9—H9B···O3i	0.97	2.36	3.2621 (17)	155
C16—H16B···O5ii	0.96	2.59	3.4982 (17)	159
C16—H16C···O2	0.96	2.34	2.9441 (16)	121
C15—H15B···Cg1iii	0.97 (2)	2.83 (2)	3.5908 (16)	136.7 (15)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C5/O1ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1O5⋯O4	0.93 (2)	1.66 (2)	2.5361 (14)	155 (2)
C9—H9B⋯O3i	0.97	2.36	3.2621 (17)	155
C16—H16B⋯O5ii	0.96	2.59	3.4982 (17)	159
C16—H16C⋯O2	0.96	2.34	2.9441 (16)	121
C15—H15B⋯Cg1iii	0.97 (2)	2.83 (2)	3.5908 (16)	136.7 (15)

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