2,7-Dihydr­oxy-3,6-dimethoxy­phenanthrene from Dehaasia longipedicellata

Mukhtar, M.R.; Nafiah, M.A.; Awang, K.; Hadi, A.H.A.; Ng, S.W.

doi:10.1107/S1600536808014451

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1135

doi:10.1107/S1600536808014451

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2,7-Dihydroxy-3,6-dimethoxyphenanthrene from Dehaasia longipedicellata

Mat Ropi Mukhtar,^a Mohd Azlan Nafiah,^a Khalijah Awang,^a A. Hamid A. Hadi ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 13 May 2008; accepted 14 May 2008; online 21 May 2008)

The hydroxy groups in the title compound, C₁₆H₁₄O₄, are each hydrogen bonded to the adjacent methoxy O atom; one of the two hydroxy groups is additionally linked to the O atom of the methoxy group of another molecule, forming a linear chain.

Related literature

For related compounds isolated from other plants, see: Bhandari et al. (1985 ); Mujumder et al. (1985 ); Theuns et al. (1985 ); Zurinah Mahmud et al. (1992 ). For the crystal structure of 2,3-dimethoxy-6,7-methylenedioxyphenanthrene, see: Wang et al. (2007 ).

Experimental

Crystal data

C₁₆H₁₄O₄
M_r = 270.27
Monoclinic, P 2₁ /c
a = 11.6268 (2) Å
b = 7.2207 (1) Å
c = 16.5351 (2) Å
β = 109.196 (1)°
V = 1311.00 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 (2) K
0.30 × 0.25 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
15710 measured reflections
2991 independent reflections
2671 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.150
S = 1.10
2991 reflections
237 parameters
14 restraints
All H-atom parameters refined
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2o⋯O1	0.85 (1)	2.20 (3)	2.670 (2)	115 (2)
O2—H2o⋯O3ⁱ	0.85 (1)	1.95 (1)	2.754 (2)	159 (3)
O3—H3o⋯O4	0.85 (1)	2.08 (3)	2.614 (2)	121 (3)
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014451/bt2712sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014451/bt2712Isup2.hkl

checkCIF report

Comment top

2,7-Dihydroxy-3,6-dimethoxylphenanthrene (Scheme I, Fig. 1) is a new compound isolated from Dehaasia longipedicellata (Ridl.) Kosterm. The hydroxy groups are each hydrogen-bonded to the adjacent methoxy oxygen; one of the two hydroxy groups is additionally linked to the oxygen atom of the methoxy group of another molecule to form a linear chain.

Related literature top

For related compounds isolated from other plants, see: Bhandari et al. (1985); Mujumder et al. (1985); Theuns et al. (1985); Zurinah Mahmud et al. (1992). For the crystal structure of 2,3-dimethoxy-6,7-methylenedioxyphenanthrene, see: Wang et al. (2007).

Experimental top

Dehaasia longipedicellata (Ridl.) Kosterm. was collected in Raub Forest Reserve, Pahang, Malaysia, in 1997. Specimens (KL4719) were deposited at the herbarium, Department of Chemistry, University of Malaya and the herbarium of the Forest Research Institute of Malaysia.

Some 1.4 kg of dried and ground leaves of D. longipedicellata was extracted with dichloromethane. The dichloromethane extract was concentrated under reduced pressure to a volume of 500 ml. This was repeatedly extracted with a solution of 5% hydrochloric acid. The combined extracts were then basified with 10% ammonium hydroxide to pH 11 and then re-extracted with dichloromethane. The brown alkaloid fraction amounted to (8.83 g). A portion (3 g) was subjected to column chromatography on silica gel 60 GF₂₅₄by using a step gradient of dichloromethane and methanol. The separation afforded 15 fractions, the first (100% dichloromethane) gave 2,7-dihydroxy-3,6-dimethoxyphenanthrene (8 mg), whose formulation was established by spectroscopic analysis. Light brown prisms were obtained upon recrystallization from dichloromethane.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of the molecule of C₁₆H₁₆O₄ drawn at the 70% probability level. Hydrogen atoms are shown as spheres of arbitrary radii.
	Fig. 2. Hydrogen-bonded chain structure.

2,7-Dihydroxy-3,6-dimethoxyphenanthrene top

Crystal data top

C₁₆H₁₄O₄	F(000) = 568
M_r = 270.27	D_x = 1.369 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8700 reflections
a = 11.6268 (2) Å	θ = 2.6–28.3°
b = 7.2207 (1) Å	µ = 0.10 mm⁻¹
c = 16.5351 (2) Å	T = 100 K
β = 109.196 (1)°	Prism, pale brown
V = 1311.00 (3) Å³	0.30 × 0.25 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2671 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −11→15
15710 measured reflections	k = −9→9
2991 independent reflections	l = −21→21

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	All H-atom parameters refined
S = 1.11	w = 1/[σ²(F_o²) + (0.07P)² + 1.2422P] where P = (F_o² + 2F_c²)/3
2991 reflections	(Δ/σ)_max = 0.001
237 parameters	Δρ_max = 0.42 e Å⁻³
14 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₆H₁₄O₄	V = 1311.00 (3) Å³
M_r = 270.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6268 (2) Å	µ = 0.10 mm⁻¹
b = 7.2207 (1) Å	T = 100 K
c = 16.5351 (2) Å	0.30 × 0.25 × 0.05 mm
β = 109.196 (1)°

Data collection top

Bruker SMART APEX diffractometer	2671 reflections with I > 2σ(I)
15710 measured reflections	R_int = 0.020
2991 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	14 restraints
wR(F²) = 0.150	All H-atom parameters refined
S = 1.11	Δρ_max = 0.42 e Å⁻³
2991 reflections	Δρ_min = −0.23 e Å⁻³
237 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.71900 (10)	0.23952 (17)	0.51347 (7)	0.0175 (3)
O2	0.85160 (11)	0.40262 (19)	0.65922 (8)	0.0213 (3)
O3	−0.02829 (12)	0.2974 (2)	0.54817 (9)	0.0277 (3)
O4	0.05316 (11)	0.19182 (19)	0.42576 (8)	0.0236 (3)
C1	0.47440 (14)	0.3578 (2)	0.60344 (10)	0.0137 (3)
C2	0.53118 (14)	0.2890 (2)	0.54541 (10)	0.0141 (3)
C3	0.65507 (14)	0.3029 (2)	0.56408 (10)	0.0147 (3)
C4	0.72887 (14)	0.3887 (2)	0.64087 (10)	0.0160 (3)
C5	0.67565 (15)	0.4568 (2)	0.69713 (10)	0.0164 (3)
C6	0.54872 (14)	0.4405 (2)	0.68039 (10)	0.0148 (3)
C7	0.49473 (15)	0.5060 (2)	0.74130 (10)	0.0161 (3)
C8	0.37442 (15)	0.4861 (2)	0.72813 (10)	0.0174 (3)
C9	0.29560 (15)	0.4047 (2)	0.65046 (10)	0.0159 (3)
C10	0.16910 (16)	0.3874 (2)	0.63624 (11)	0.0197 (4)
C11	0.09423 (15)	0.3145 (2)	0.56196 (11)	0.0197 (4)
C12	0.14106 (15)	0.2572 (2)	0.49676 (11)	0.0180 (3)
C13	0.26312 (15)	0.2727 (2)	0.50896 (10)	0.0157 (3)
C14	0.34417 (14)	0.3444 (2)	0.58698 (10)	0.0142 (3)
C15	0.64950 (15)	0.1659 (2)	0.43192 (10)	0.0172 (3)
C16	0.09098 (17)	0.1296 (3)	0.35617 (11)	0.0234 (4)
H2O	0.870 (2)	0.361 (4)	0.6173 (12)	0.042 (7)*
H3O	−0.059 (3)	0.257 (4)	0.4974 (10)	0.060 (9)*
H2	0.4840 (17)	0.236 (3)	0.4925 (9)	0.019 (5)*
H5	0.7270 (16)	0.513 (3)	0.7485 (9)	0.019 (5)*
H7	0.5458 (16)	0.571 (3)	0.7897 (10)	0.019 (5)*
H8	0.3392 (18)	0.525 (3)	0.7698 (11)	0.019 (5)*
H10	0.1355 (19)	0.429 (3)	0.6789 (11)	0.027 (6)*
H13	0.2932 (18)	0.230 (3)	0.4656 (10)	0.019 (5)*
H151	0.7096 (16)	0.132 (3)	0.4069 (14)	0.028 (6)*
H152	0.5945 (16)	0.259 (2)	0.4015 (12)	0.019 (5)*
H153	0.6033 (16)	0.058 (2)	0.4361 (13)	0.015 (5)*
H161	0.0189 (14)	0.090 (3)	0.3123 (11)	0.030 (6)*
H162	0.1507 (18)	0.034 (3)	0.3737 (15)	0.034 (6)*
H163	0.128 (2)	0.234 (2)	0.3382 (15)	0.032 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0127 (5)	0.0242 (6)	0.0160 (6)	0.0004 (4)	0.0053 (4)	−0.0032 (4)
O2	0.0122 (6)	0.0314 (7)	0.0193 (6)	−0.0021 (5)	0.0038 (4)	−0.0035 (5)
O3	0.0126 (6)	0.0442 (8)	0.0273 (7)	−0.0017 (5)	0.0079 (5)	−0.0053 (6)
O4	0.0135 (6)	0.0342 (7)	0.0207 (6)	−0.0026 (5)	0.0025 (5)	−0.0061 (5)
C1	0.0140 (7)	0.0133 (7)	0.0138 (7)	0.0008 (6)	0.0046 (6)	0.0016 (5)
C2	0.0148 (7)	0.0151 (7)	0.0122 (7)	0.0001 (6)	0.0039 (6)	0.0004 (5)
C3	0.0152 (7)	0.0153 (7)	0.0143 (7)	0.0014 (6)	0.0058 (6)	0.0013 (6)
C4	0.0126 (7)	0.0174 (7)	0.0171 (7)	−0.0008 (6)	0.0037 (6)	0.0023 (6)
C5	0.0164 (8)	0.0169 (7)	0.0137 (7)	−0.0017 (6)	0.0019 (6)	−0.0004 (6)
C6	0.0163 (8)	0.0145 (7)	0.0132 (7)	0.0009 (6)	0.0043 (6)	0.0023 (5)
C7	0.0199 (8)	0.0154 (7)	0.0111 (7)	0.0007 (6)	0.0027 (6)	−0.0002 (5)
C8	0.0216 (8)	0.0177 (7)	0.0148 (7)	0.0033 (6)	0.0086 (6)	0.0013 (6)
C9	0.0157 (8)	0.0165 (7)	0.0160 (7)	0.0024 (6)	0.0061 (6)	0.0028 (6)
C10	0.0175 (8)	0.0242 (8)	0.0197 (8)	0.0028 (6)	0.0094 (6)	0.0010 (6)
C11	0.0129 (8)	0.0243 (8)	0.0231 (8)	0.0019 (6)	0.0076 (6)	0.0029 (7)
C12	0.0154 (8)	0.0197 (8)	0.0173 (8)	0.0000 (6)	0.0033 (6)	−0.0002 (6)
C13	0.0156 (8)	0.0176 (7)	0.0146 (7)	0.0011 (6)	0.0059 (6)	0.0013 (6)
C14	0.0136 (7)	0.0138 (7)	0.0152 (7)	0.0017 (5)	0.0048 (6)	0.0026 (6)
C15	0.0181 (8)	0.0198 (8)	0.0142 (7)	0.0003 (6)	0.0061 (6)	−0.0021 (6)
C16	0.0197 (8)	0.0295 (9)	0.0177 (8)	−0.0019 (7)	0.0016 (6)	−0.0054 (7)

Geometric parameters (Å, º) top

O1—C3	1.3679 (19)	C7—C8	1.351 (2)
O1—C15	1.4273 (19)	C7—H7	0.949 (10)
O2—C4	1.3615 (19)	C8—C9	1.436 (2)
O2—H2O	0.848 (10)	C8—H8	0.951 (9)
O3—C11	1.372 (2)	C9—C10	1.417 (2)
O3—H3O	0.849 (10)	C9—C14	1.414 (2)
O4—C12	1.363 (2)	C10—C11	1.357 (2)
O4—C16	1.432 (2)	C10—H10	0.959 (10)
C1—C6	1.414 (2)	C11—C12	1.420 (2)
C1—C2	1.421 (2)	C12—C13	1.371 (2)
C1—C14	1.451 (2)	C13—C14	1.422 (2)
C2—C3	1.374 (2)	C13—H13	0.946 (9)
C2—H2	0.947 (9)	C15—H151	0.954 (10)
C3—C4	1.420 (2)	C15—H152	0.948 (9)
C4—C5	1.367 (2)	C15—H153	0.959 (9)
C5—C6	1.414 (2)	C16—H161	0.955 (10)
C5—H5	0.954 (9)	C16—H162	0.952 (10)
C6—C7	1.431 (2)	C16—H163	0.959 (10)

C3—O1—C15	116.73 (12)	C10—C9—C8	120.47 (15)
C4—O2—H2O	108.9 (19)	C14—C9—C8	119.79 (14)
C11—O3—H3O	105 (2)	C11—C10—C9	120.43 (15)
C12—O4—C16	117.34 (13)	C11—C10—H10	119.4 (14)
C6—C1—C2	118.23 (14)	C9—C10—H10	120.1 (14)
C6—C1—C14	119.23 (14)	C10—C11—O3	120.48 (16)
C2—C1—C14	122.54 (14)	C10—C11—C12	120.56 (15)
C3—C2—C1	120.55 (14)	O3—C11—C12	118.95 (15)
C3—C2—H2	118.9 (13)	O4—C12—C13	127.02 (15)
C1—C2—H2	120.6 (13)	O4—C12—C11	112.88 (15)
O1—C3—C2	125.36 (14)	C13—C12—C11	120.09 (15)
O1—C3—C4	113.75 (14)	C12—C13—C14	120.56 (15)
C2—C3—C4	120.89 (14)	C12—C13—H13	119.0 (13)
O2—C4—C5	119.84 (15)	C14—C13—H13	120.4 (13)
O2—C4—C3	120.83 (14)	C9—C14—C13	118.58 (14)
C5—C4—C3	119.33 (15)	C9—C14—C1	119.15 (14)
C4—C5—C6	120.91 (15)	C13—C14—C1	122.27 (14)
C4—C5—H5	117.9 (13)	O1—C15—H151	103.7 (14)
C6—C5—H5	121.1 (13)	O1—C15—H152	108.2 (13)
C5—C6—C1	120.07 (14)	H151—C15—H152	114.5 (19)
C5—C6—C7	120.38 (14)	O1—C15—H153	112.9 (12)
C1—C6—C7	119.55 (14)	H151—C15—H153	109.3 (19)
C8—C7—C6	121.47 (15)	H152—C15—H153	108.3 (18)
C8—C7—H7	121.1 (13)	O4—C16—H161	106.3 (14)
C6—C7—H7	117.4 (13)	O4—C16—H162	111.6 (15)
C7—C8—C9	120.69 (15)	H161—C16—H162	112 (2)
C7—C8—H8	121.4 (13)	O4—C16—H163	106.8 (15)
C9—C8—H8	117.9 (13)	H161—C16—H163	112 (2)
C10—C9—C14	119.73 (15)	H162—C16—H163	108 (2)

C6—C1—C2—C3	0.0 (2)	C14—C9—C10—C11	−0.4 (2)
C14—C1—C2—C3	−179.27 (14)	C8—C9—C10—C11	178.42 (16)
C15—O1—C3—C2	5.0 (2)	C9—C10—C11—O3	179.88 (15)
C15—O1—C3—C4	−174.81 (13)	C9—C10—C11—C12	−1.0 (3)
C1—C2—C3—O1	179.19 (14)	C16—O4—C12—C13	0.9 (3)
C1—C2—C3—C4	−1.0 (2)	C16—O4—C12—C11	−179.78 (15)
O1—C3—C4—O2	−0.1 (2)	C10—C11—C12—O4	−178.39 (16)
C2—C3—C4—O2	−179.89 (14)	O3—C11—C12—O4	0.7 (2)
O1—C3—C4—C5	−179.60 (14)	C10—C11—C12—C13	1.0 (3)
C2—C3—C4—C5	0.6 (2)	O3—C11—C12—C13	−179.95 (15)
O2—C4—C5—C6	−178.64 (14)	O4—C12—C13—C14	179.82 (16)
C3—C4—C5—C6	0.9 (2)	C11—C12—C13—C14	0.6 (2)
C4—C5—C6—C1	−1.9 (2)	C10—C9—C14—C13	1.9 (2)
C4—C5—C6—C7	177.63 (15)	C8—C9—C14—C13	−176.96 (14)
C2—C1—C6—C5	1.4 (2)	C10—C9—C14—C1	−178.18 (14)
C14—C1—C6—C5	−179.26 (14)	C8—C9—C14—C1	3.0 (2)
C2—C1—C6—C7	−178.10 (14)	C12—C13—C14—C9	−1.9 (2)
C14—C1—C6—C7	1.2 (2)	C12—C13—C14—C1	178.09 (15)
C5—C6—C7—C8	−177.65 (15)	C6—C1—C14—C9	−3.6 (2)
C1—C6—C7—C8	1.9 (2)	C2—C1—C14—C9	175.69 (14)
C6—C7—C8—C9	−2.5 (2)	C6—C1—C14—C13	176.38 (14)
C7—C8—C9—C10	−178.78 (15)	C2—C1—C14—C13	−4.3 (2)
C7—C8—C9—C14	0.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O1	0.85 (1)	2.20 (3)	2.670 (2)	115 (2)
O2—H2o···O3ⁱ	0.85 (1)	1.95 (1)	2.754 (2)	159 (3)
O3—H3o···O4	0.85 (1)	2.08 (3)	2.614 (2)	121 (3)

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄O₄
M_r	270.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.6268 (2), 7.2207 (1), 16.5351 (2)
β (°)	109.196 (1)
V (Å³)	1311.00 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.25 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15710, 2991, 2671
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.150, 1.11
No. of reflections	2991
No. of parameters	237
No. of restraints	14
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O1	0.85 (1)	2.20 (3)	2.670 (2)	115 (2)
O2—H2o···O3ⁱ	0.85 (1)	1.95 (1)	2.754 (2)	159 (3)
O3—H3o···O4	0.85 (1)	2.08 (3)	2.614 (2)	121 (3)

Symmetry code: (i) x+1, y, z.

Acknowledgements

We thank the University of Malaya for supporting this study (grants PPF/FP092/2005 C and 02–01-03-SF0370).

References

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