3-Allyl-2-hydr-oxy-5,6,8-trimethoxy-naphthalene-1,4-dione.

In the crystal structure of the title compound, C(16)H(16)O(6), a pair of naphthoquinone rings are linked via O-H⋯O-C hydrogen bonds in a nearly orthogonal arrangement. This dimeric unit is linked to a neighbouring dimer by π-π stacking inter-actions between the naphthoquinone rings, where the distance between the mean plane of the naphtoquinone backbones is 3.468 Å, and O-H⋯O-C hydrogen bonds.

Related literature

For details of the synthesis, see: Brimble et al. (2008 ▶). For related syntheses, see: Reissig et al. (2006 ▶); Kozlowski et al. (2008 ▶). For the biological activity of rubromycins, see: Brockmann et al. (1953 ▶, 1966 ▶).

Experimental

Crystal data

C16H16O6

M = 304.29

Orthorhombic,

a = 4.68110 (10) Å

b = 12.6577 (3) Å

c = 23.3392 (5) Å

V = 1382.89 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 89 (2) K

0.28 × 0.09 × 0.06 mm

Data collection

Bruker SMART diffractometer with APEXII CCD detector

Absorption correction: none

14372 measured reflections

1914 independent reflections

1415 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.085

S = 1.09

1914 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028432/ng2489sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028432/ng2489Isup2.hkl

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

C16H16O6	Dx = 1.462 Mg m−3
Mr = 304.29	Melting point: 429(2) K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 4.6811 (1) Å	Cell parameters from 3251 reflections
b = 12.6577 (3) Å	θ = 1.8–27.9°
c = 23.3392 (5) Å	µ = 0.11 mm−1
V = 1382.89 (5) Å3	T = 89 K
Z = 4	Needle, yellow
F(000) = 640	0.28 × 0.09 × 0.06 mm

Bruker SMART diffractometer with APEXII CCD detector	1415 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
graphite	θmax = 27.9°, θmin = 1.8°
ω scans	h = −6→4
14372 measured reflections	k = −16→16
1914 independent reflections	l = −30→30

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0367P)2 + 0.1796P] where P = (Fo2 + 2Fc2)/3
1914 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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
O16	−0.4858 (4)	0.07396 (13)	0.01234 (6)	0.0192 (4)
H16	−0.4751	0.1330	−0.0020	0.029*
O11	−0.1507 (4)	−0.09214 (12)	0.17755 (7)	0.0183 (4)
O17	0.2562 (4)	−0.00627 (12)	0.24216 (6)	0.0150 (4)
O19	0.2115 (4)	0.33797 (12)	0.09662 (7)	0.0174 (4)
O12	−0.1853 (4)	0.24133 (13)	0.03789 (6)	0.0164 (4)
O18	0.5482 (4)	0.16101 (12)	0.26649 (6)	0.0162 (4)
C5	0.0492 (6)	0.07747 (18)	0.15754 (9)	0.0125 (6)
C4	0.0441 (6)	0.16715 (18)	0.12052 (9)	0.0129 (5)
C2	0.3969 (6)	0.25329 (19)	0.18127 (10)	0.0141 (6)
H2	0.5140	0.3108	0.1891	0.017*
C6	0.2263 (6)	0.07808 (18)	0.20552 (9)	0.0129 (6)
C3	0.2219 (6)	0.25382 (18)	0.13284 (9)	0.0134 (6)
C8	−0.3187 (6)	0.06946 (19)	0.05919 (9)	0.0148 (6)
C21	0.7270 (6)	0.24990 (19)	0.28100 (10)	0.0180 (6)
H21A	0.8237	0.2360	0.3165	0.027*
H21B	0.6110	0.3120	0.2850	0.027*
H21C	0.8653	0.2608	0.2512	0.027*
C9	−0.3109 (6)	−0.01717 (18)	0.09232 (9)	0.0135 (6)
C1	0.3956 (6)	0.16712 (19)	0.21750 (9)	0.0130 (6)
C7	−0.1488 (6)	0.16625 (19)	0.07100 (9)	0.0141 (6)
C20	0.4222 (6)	0.41995 (19)	0.10271 (10)	0.0196 (6)
H20A	0.3889	0.4738	0.0745	0.029*
H20B	0.6093	0.3906	0.0973	0.029*
H20C	0.4089	0.4502	0.1403	0.029*
C10	−0.1373 (6)	−0.01652 (19)	0.14485 (9)	0.0134 (6)
C14	−0.2956 (7)	−0.2026 (2)	0.05618 (11)	0.0214 (7)
H14	−0.2007	−0.1904	0.0218	0.026*
C22	0.0511 (6)	−0.00647 (18)	0.28793 (9)	0.0175 (6)
H22A	0.0825	−0.0669	0.3120	0.026*
H22B	−0.1383	−0.0095	0.2722	0.026*
H22C	0.0719	0.0568	0.3102	0.026*
C15	−0.2583 (7)	−0.2953 (2)	0.08090 (11)	0.0288 (8)
H15A	−0.3497	−0.3104	0.1153	0.035*
H15B	−0.1405	−0.3455	0.0639	0.035*
C13	−0.4799 (6)	−0.11548 (17)	0.07933 (10)	0.0155 (6)
H13A	−0.5731	−0.1396	0.1141	0.019*
H13B	−0.6273	−0.0988	0.0516	0.019*

	U11	U22	U33	U12	U13	U23
O16	0.0252 (12)	0.0179 (9)	0.0146 (8)	−0.0020 (10)	−0.0054 (9)	0.0036 (7)
O11	0.0207 (11)	0.0155 (9)	0.0185 (8)	−0.0029 (9)	−0.0019 (8)	0.0038 (7)
O17	0.0168 (10)	0.0133 (8)	0.0148 (8)	0.0008 (9)	0.0016 (9)	0.0044 (7)
O19	0.0200 (11)	0.0132 (8)	0.0190 (9)	−0.0049 (9)	−0.0026 (9)	0.0042 (7)
O12	0.0164 (10)	0.0170 (9)	0.0157 (8)	−0.0003 (9)	0.0003 (9)	0.0024 (7)
O18	0.0178 (10)	0.0136 (8)	0.0171 (8)	−0.0029 (9)	−0.0039 (9)	0.0014 (7)
C5	0.0116 (15)	0.0122 (11)	0.0136 (11)	0.0032 (12)	0.0041 (12)	−0.0012 (9)
C4	0.0125 (14)	0.0135 (11)	0.0127 (11)	−0.0004 (12)	0.0021 (12)	0.0010 (9)
C2	0.0120 (15)	0.0130 (12)	0.0172 (12)	−0.0016 (12)	0.0018 (12)	−0.0018 (10)
C6	0.0130 (15)	0.0137 (12)	0.0121 (11)	0.0032 (13)	0.0011 (12)	0.0010 (9)
C3	0.0133 (15)	0.0118 (12)	0.0149 (11)	0.0030 (13)	0.0032 (13)	0.0023 (9)
C8	0.0130 (15)	0.0191 (13)	0.0122 (11)	0.0008 (13)	0.0000 (12)	−0.0005 (10)
C21	0.0190 (17)	0.0171 (13)	0.0179 (12)	−0.0043 (14)	−0.0045 (14)	−0.0024 (10)
C9	0.0118 (15)	0.0152 (12)	0.0136 (11)	−0.0009 (12)	−0.0013 (12)	−0.0013 (10)
C1	0.0102 (15)	0.0166 (12)	0.0120 (11)	0.0051 (12)	0.0004 (11)	−0.0014 (10)
C7	0.0135 (15)	0.0149 (12)	0.0140 (11)	0.0009 (13)	0.0056 (12)	0.0011 (10)
C20	0.0220 (17)	0.0168 (13)	0.0198 (12)	−0.0052 (13)	0.0005 (13)	−0.0011 (11)
C10	0.0118 (15)	0.0139 (12)	0.0144 (11)	0.0033 (11)	0.0039 (12)	0.0001 (10)
C14	0.0233 (18)	0.0216 (14)	0.0193 (12)	−0.0058 (14)	−0.0010 (14)	−0.0031 (10)
C22	0.0211 (15)	0.0171 (13)	0.0142 (11)	−0.0003 (13)	0.0024 (13)	0.0034 (10)
C15	0.036 (2)	0.0226 (15)	0.0275 (14)	0.0036 (16)	0.0000 (17)	−0.0033 (12)
C13	0.0155 (16)	0.0153 (12)	0.0156 (11)	−0.0041 (12)	−0.0031 (14)	0.0027 (10)

O16—C8	1.346 (3)	C8—C7	1.486 (3)
O16—H16	0.8200	C21—H21A	0.9600
O11—C10	1.226 (3)	C21—H21B	0.9600
O17—C6	1.375 (3)	C21—H21C	0.9600
O17—C22	1.436 (3)	C9—C10	1.471 (3)
O19—C3	1.361 (3)	C9—C13	1.505 (3)
O19—C20	1.439 (3)	C20—H20A	0.9600
O12—C7	1.237 (3)	C20—H20B	0.9600
O18—C1	1.350 (3)	C20—H20C	0.9600
O18—C21	1.443 (3)	C14—C15	1.318 (4)
C5—C6	1.394 (3)	C14—C13	1.501 (4)
C5—C4	1.427 (3)	C14—H14	0.9300
C5—C10	1.505 (3)	C22—H22A	0.9600
C4—C3	1.407 (3)	C22—H22B	0.9600
C4—C7	1.467 (3)	C22—H22C	0.9600
C2—C1	1.380 (3)	C15—H15A	0.9300
C2—C3	1.396 (3)	C15—H15B	0.9300
C2—H2	0.9300	C13—H13A	0.9700
C6—C1	1.406 (3)	C13—H13B	0.9700
C8—C9	1.342 (3)
C8—O16—H16	109.5	O18—C1—C6	114.9 (2)
C6—O17—C22	113.32 (18)	C2—C1—C6	120.9 (2)
C3—O19—C20	118.60 (19)	O12—C7—C4	124.8 (2)
C1—O18—C21	117.46 (18)	O12—C7—C8	116.3 (2)
C6—C5—C4	119.5 (2)	C4—C7—C8	118.8 (2)
C6—C5—C10	120.5 (2)	O19—C20—H20A	109.5
C4—C5—C10	120.0 (2)	O19—C20—H20B	109.5
C3—C4—C5	119.1 (2)	H20A—C20—H20B	109.5
C3—C4—C7	122.1 (2)	O19—C20—H20C	109.5
C5—C4—C7	118.8 (2)	H20A—C20—H20C	109.5
C1—C2—C3	119.8 (2)	H20B—C20—H20C	109.5
C1—C2—H2	120.1	O11—C10—C9	119.1 (2)
C3—C2—H2	120.1	O11—C10—C5	121.6 (2)
O17—C6—C5	123.8 (2)	C9—C10—C5	119.3 (2)
O17—C6—C1	116.2 (2)	C15—C14—C13	124.9 (3)
C5—C6—C1	120.0 (2)	C15—C14—H14	117.5
O19—C3—C2	121.9 (2)	C13—C14—H14	117.5
O19—C3—C4	117.5 (2)	O17—C22—H22A	109.5
C2—C3—C4	120.6 (2)	O17—C22—H22B	109.5
C9—C8—O16	121.2 (2)	H22A—C22—H22B	109.5
C9—C8—C7	123.5 (2)	O17—C22—H22C	109.5
O16—C8—C7	115.26 (19)	H22A—C22—H22C	109.5
O18—C21—H21A	109.5	H22B—C22—H22C	109.5
O18—C21—H21B	109.5	C14—C15—H15A	120.0
H21A—C21—H21B	109.5	C14—C15—H15B	120.0
O18—C21—H21C	109.5	H15A—C15—H15B	120.0
H21A—C21—H21C	109.5	C14—C13—C9	112.2 (2)
H21B—C21—H21C	109.5	C14—C13—H13A	109.2
C8—C9—C10	119.4 (2)	C9—C13—H13A	109.2
C8—C9—C13	123.0 (2)	C14—C13—H13B	109.2
C10—C9—C13	117.6 (2)	C9—C13—H13B	109.2
O18—C1—C2	124.2 (2)	H13A—C13—H13B	107.9

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16···O12	0.82	2.14	2.612 (2)	117.
O16—H16···O12i	0.82	2.05	2.777 (2)	148.
O16—H16···O19i	0.82	2.40	2.926 (2)	122.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O16—H16⋯O12	0.82	2.14	2.612 (2)	117
O16—H16⋯O12i	0.82	2.05	2.777 (2)	148
O16—H16⋯O19i	0.82	2.40	2.926 (2)	122

Symmetry code: (i) .