Meranzin hydrate from Muraya paniculata

Julaeha, E.; Supratman, U.; Mukhtar, M.R.; Awang, K.; Ng, S.W.

doi:10.1107/S1600536810005386

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o620

doi:10.1107/S1600536810005386

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Meranzin hydrate from Muraya paniculata

Euis Julaeha,^a Unang Supratman,^a Mat Ropi Mukhtar,^b Khalijah Awang ^b and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, Faculty of Mathematics and Natural Sciences, Padjadjaran University, Jatinangor 45363, West Java, Indonesia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 8 February 2010; accepted 9 February 2010; online 13 February 2010)

The coumarin ring system in the title compound, C₁₅H₁₈O₅ [IUPAC name: 8-(2,3-dihydroxy-3-methylbutyl)-7-methoxy-2H-1-benzopyran-2-one], isolated from Muraya paniculata, is planar (r.m.s. deviation 0.017 Å). In the crystal, the two hydroxy groups are involved in O—H⋯O hydrogen bonding with adjacent molecules, forming a sheet structure.

Related literature

For the asymmetric synthesis and absolute configuration of meranzin hydrate, see: Grundon & McColl (1975 ).

Experimental

Crystal data

C₁₅H₁₈O₅
M_r = 278.29
Monoclinic, P 2₁
a = 5.8061 (7) Å
b = 10.5146 (13) Å
c = 11.4477 (14) Å
β = 91.547 (2)°
V = 698.61 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.35 × 0.15 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
6694 measured reflections
1699 independent reflections
1338 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.102
S = 1.00
1699 reflections
192 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ⁱ	0.84 (1)	2.01 (1)	2.842 (3)	169 (5)
O5—H5⋯O2ⁱⁱ	0.85 (1)	2.12 (2)	2.936 (3)	163 (4)
Symmetry codes: (i) x-1, y, z; (ii) $[-x+3, y-{\script{1\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005386/bt5194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005386/bt5194Isup2.hkl

checkCIF report

Comment top

Muraya paniculata (Rutaceae, known as kemuning in Indonesia) is a perennial herb having succulent leaves. The plant is used for the treatment of orchitis, bronchitis and urine infections.

Related literature top

For the asymmetric synthesis and absolute configuration of meranzin hydrate, see: Grundon & McColl (1975).

Experimental top

M. paniculata was collected in from Bandung, Indonesia. The plant was identified by the Department of Biology of Padjadjaran University. The dried leaves of M. paniculata (4 kg) was extracted exhaustively by methanol at room temperature and then concentrated to yield a methanol extract (438 g); 200 g was partitioned between n-hexane and methanol containing 10% water. The aqueous extract was extracted with ethyl acetate. The ethyl acetate portion was removed and subjected to column chromatography on silica gel 60 by using a step gradient of n-hexane–ethyl acetate–methanol. The fraction eluted by n-hexane/ethyl acetate (1:4) was further separated by column chromatography on silica gel (chloroform:ethyl acetate 1:1) to give meranzin hydrate, 8-[2,3-dihydroxy-3-methylbutyl]-7-methoxy-2H-1-benzopyran-2-one (12 mg).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₅H₁₈O₅; at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

8-[2,3-dihydroxy-3-methylbutyl]-7-methoxy-2H-1-benzopyran-2-one top

Crystal data top

C₁₅H₁₈O₅	F(000) = 296
M_r = 278.29	D_x = 1.323 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1731 reflections
a = 5.8061 (7) Å	θ = 2.6–22.3°
b = 10.5146 (13) Å	µ = 0.10 mm⁻¹
c = 11.4477 (14) Å	T = 293 K
β = 91.547 (2)°	Prism, colourless
V = 698.61 (15) Å³	0.35 × 0.15 × 0.15 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	1338 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.040
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ω scans	h = −7→7
6694 measured reflections	k = −11→13
1699 independent reflections	l = −14→14

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0603P)²] where P = (F_o² + 2F_c²)/3
1699 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 0.12 e Å⁻³
3 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₅H₁₈O₅	V = 698.61 (15) Å³
M_r = 278.29	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.8061 (7) Å	µ = 0.10 mm⁻¹
b = 10.5146 (13) Å	T = 293 K
c = 11.4477 (14) Å	0.35 × 0.15 × 0.15 mm
β = 91.547 (2)°

Data collection top

Bruker SMART APEX diffractometer	1338 reflections with I > 2σ(I)
6694 measured reflections	R_int = 0.040
1699 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	3 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.12 e Å⁻³
1699 reflections	Δρ_min = −0.16 e Å⁻³
192 parameters

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

	x	y	z	U_iso*/U_eq
O1	1.4383 (3)	0.50000 (16)	0.83522 (15)	0.0436 (4)
O2	1.7272 (3)	0.51296 (19)	0.96204 (18)	0.0592 (5)
O3	0.8098 (4)	0.4410 (2)	0.57958 (18)	0.0677 (6)
O4	1.0213 (3)	0.30444 (18)	0.91374 (15)	0.0500 (5)
O5	1.1435 (3)	0.06759 (16)	0.79342 (17)	0.0490 (4)
C1	1.5866 (4)	0.5712 (3)	0.9034 (2)	0.0461 (6)
C2	1.5618 (5)	0.7069 (3)	0.8999 (3)	0.0553 (7)
H2	1.6632	0.7576	0.9436	0.066*
C3	1.3954 (5)	0.7612 (3)	0.8350 (3)	0.0567 (7)
H3	1.3813	0.8493	0.8345	0.068*
C4	1.2374 (5)	0.6858 (2)	0.7657 (2)	0.0476 (6)
C5	1.0585 (5)	0.7350 (3)	0.6972 (3)	0.0596 (8)
H5A	1.0373	0.8226	0.6939	0.071*
C6	0.9124 (5)	0.6572 (3)	0.6344 (3)	0.0610 (8)
H6	0.7931	0.6918	0.5888	0.073*
C7	0.9433 (5)	0.5268 (3)	0.6391 (2)	0.0513 (7)
C8	1.1185 (4)	0.4708 (2)	0.7080 (2)	0.0415 (5)
C9	1.2625 (4)	0.5534 (2)	0.7693 (2)	0.0400 (5)
C10	0.6251 (5)	0.4863 (4)	0.5056 (3)	0.0792 (11)
H10A	0.5429	0.4153	0.4723	0.119*
H10B	0.6864	0.5372	0.4442	0.119*
H10C	0.5222	0.5367	0.5507	0.119*
C11	1.1382 (4)	0.3280 (2)	0.7160 (2)	0.0419 (5)
H11A	1.2906	0.3052	0.7459	0.050*
H11B	1.1181	0.2912	0.6387	0.050*
C12	0.9563 (4)	0.2742 (2)	0.79647 (19)	0.0388 (5)
H12	0.8090	0.3159	0.7777	0.047*
C13	0.9231 (4)	0.1295 (2)	0.7838 (2)	0.0406 (5)
C14	0.7685 (5)	0.0804 (3)	0.8780 (3)	0.0628 (8)
H14A	0.7520	−0.0100	0.8704	0.094*
H14B	0.6199	0.1200	0.8700	0.094*
H14C	0.8354	0.1002	0.9534	0.094*
C15	0.8225 (5)	0.0987 (3)	0.6642 (3)	0.0628 (8)
H15A	0.7866	0.0096	0.6600	0.094*
H15B	0.9324	0.1193	0.6059	0.094*
H15C	0.6846	0.1474	0.6505	0.094*
H4	0.935 (6)	0.363 (3)	0.937 (4)	0.119 (17)*
H5	1.183 (6)	0.068 (4)	0.8650 (12)	0.089 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0453 (9)	0.0336 (9)	0.0515 (10)	0.0040 (7)	−0.0063 (7)	−0.0039 (7)
O2	0.0526 (10)	0.0556 (12)	0.0683 (12)	0.0103 (9)	−0.0159 (9)	−0.0154 (10)
O3	0.0719 (13)	0.0715 (15)	0.0581 (12)	−0.0035 (11)	−0.0275 (10)	0.0085 (11)
O4	0.0630 (11)	0.0466 (11)	0.0400 (9)	0.0096 (9)	−0.0081 (8)	−0.0065 (8)
O5	0.0460 (9)	0.0389 (10)	0.0616 (12)	0.0071 (7)	−0.0058 (8)	−0.0042 (9)
C1	0.0428 (12)	0.0441 (15)	0.0512 (14)	0.0015 (11)	−0.0013 (11)	−0.0098 (12)
C2	0.0581 (15)	0.0403 (15)	0.0676 (18)	−0.0087 (12)	−0.0002 (14)	−0.0088 (13)
C3	0.0722 (17)	0.0299 (13)	0.0683 (18)	−0.0035 (13)	0.0078 (15)	−0.0034 (12)
C4	0.0567 (14)	0.0356 (14)	0.0508 (15)	0.0018 (12)	0.0047 (12)	0.0054 (12)
C5	0.0716 (18)	0.0427 (16)	0.0645 (18)	0.0122 (14)	0.0013 (15)	0.0140 (14)
C6	0.0656 (17)	0.0572 (19)	0.0599 (17)	0.0137 (14)	−0.0073 (14)	0.0186 (15)
C7	0.0573 (15)	0.0544 (17)	0.0416 (14)	0.0014 (13)	−0.0065 (12)	0.0098 (13)
C8	0.0475 (12)	0.0371 (12)	0.0398 (13)	0.0011 (10)	−0.0002 (10)	0.0037 (10)
C9	0.0450 (12)	0.0345 (13)	0.0406 (13)	0.0035 (10)	0.0023 (10)	0.0042 (10)
C10	0.0586 (16)	0.114 (3)	0.0636 (19)	0.001 (2)	−0.0203 (15)	0.016 (2)
C11	0.0447 (12)	0.0353 (12)	0.0455 (13)	−0.0001 (10)	−0.0016 (10)	−0.0042 (11)
C12	0.0402 (10)	0.0373 (12)	0.0384 (12)	0.0051 (10)	−0.0072 (9)	−0.0023 (10)
C13	0.0373 (10)	0.0343 (12)	0.0499 (13)	−0.0004 (10)	−0.0055 (9)	−0.0011 (11)
C14	0.0524 (15)	0.0546 (17)	0.082 (2)	−0.0116 (13)	0.0071 (14)	0.0101 (16)
C15	0.0668 (17)	0.0530 (17)	0.0672 (18)	−0.0063 (14)	−0.0239 (14)	−0.0130 (15)

Geometric parameters (Å, º) top

O1—C1	1.369 (3)	C7—C8	1.400 (3)
O1—C9	1.373 (3)	C8—C9	1.383 (3)
O2—C1	1.209 (3)	C8—C11	1.509 (3)
O3—C7	1.361 (3)	C10—H10A	0.9600
O3—C10	1.430 (3)	C10—H10B	0.9600
O4—C12	1.421 (3)	C10—H10C	0.9600
O4—H4	0.840 (10)	C11—C12	1.529 (3)
O5—C13	1.437 (3)	C11—H11A	0.9700
O5—H5	0.846 (10)	C11—H11B	0.9700
C1—C2	1.434 (4)	C12—C13	1.540 (3)
C2—C3	1.332 (4)	C12—H12	0.9800
C2—H2	0.9300	C13—C15	1.510 (4)
C3—C4	1.434 (4)	C13—C14	1.512 (4)
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.384 (4)	C14—H14B	0.9600
C4—C9	1.401 (3)	C14—H14C	0.9600
C5—C6	1.369 (4)	C15—H15A	0.9600
C5—H5A	0.9300	C15—H15B	0.9600
C6—C7	1.383 (4)	C15—H15C	0.9600
C6—H6	0.9300

C1—O1—C9	122.44 (19)	O3—C10—H10C	109.5
C7—O3—C10	118.9 (3)	H10A—C10—H10C	109.5
C12—O4—H4	109 (3)	H10B—C10—H10C	109.5
C13—O5—H5	107 (3)	C8—C11—C12	110.6 (2)
O2—C1—O1	116.4 (2)	C8—C11—H11A	109.5
O2—C1—C2	125.8 (3)	C12—C11—H11A	109.5
O1—C1—C2	117.9 (2)	C8—C11—H11B	109.5
C3—C2—C1	120.8 (3)	C12—C11—H11B	109.5
C3—C2—H2	119.6	H11A—C11—H11B	108.1
C1—C2—H2	119.6	O4—C12—C11	108.45 (18)
C2—C3—C4	121.0 (2)	O4—C12—C13	109.84 (19)
C2—C3—H3	119.5	C11—C12—C13	113.30 (19)
C4—C3—H3	119.5	O4—C12—H12	108.4
C5—C4—C9	117.6 (3)	C11—C12—H12	108.4
C5—C4—C3	124.4 (3)	C13—C12—H12	108.4
C9—C4—C3	118.0 (2)	O5—C13—C15	107.1 (2)
C6—C5—C4	121.3 (3)	O5—C13—C14	109.6 (2)
C6—C5—H5A	119.3	C15—C13—C14	110.5 (2)
C4—C5—H5A	119.3	O5—C13—C12	109.36 (17)
C5—C6—C7	119.6 (3)	C15—C13—C12	110.0 (2)
C5—C6—H6	120.2	C14—C13—C12	110.2 (2)
C7—C6—H6	120.2	C13—C14—H14A	109.5
O3—C7—C6	124.5 (2)	C13—C14—H14B	109.5
O3—C7—C8	113.5 (2)	H14A—C14—H14B	109.5
C6—C7—C8	122.0 (3)	C13—C14—H14C	109.5
C9—C8—C7	116.2 (2)	H14A—C14—H14C	109.5
C9—C8—C11	123.4 (2)	H14B—C14—H14C	109.5
C7—C8—C11	120.4 (2)	C13—C15—H15A	109.5
O1—C9—C8	116.90 (19)	C13—C15—H15B	109.5
O1—C9—C4	119.8 (2)	H15A—C15—H15B	109.5
C8—C9—C4	123.3 (2)	C13—C15—H15C	109.5
O3—C10—H10A	109.5	H15A—C15—H15C	109.5
O3—C10—H10B	109.5	H15B—C15—H15C	109.5
H10A—C10—H10B	109.5

C9—O1—C1—O2	176.4 (2)	C1—O1—C9—C4	3.2 (3)
C9—O1—C1—C2	−3.2 (4)	C7—C8—C9—O1	−178.6 (2)
O2—C1—C2—C3	−177.7 (3)	C11—C8—C9—O1	3.6 (3)
O1—C1—C2—C3	1.9 (4)	C7—C8—C9—C4	0.8 (4)
C1—C2—C3—C4	−0.6 (5)	C11—C8—C9—C4	−177.1 (3)
C2—C3—C4—C5	179.2 (3)	C5—C4—C9—O1	179.5 (2)
C2—C3—C4—C9	0.5 (4)	C3—C4—C9—O1	−1.8 (4)
C9—C4—C5—C6	−0.6 (4)	C5—C4—C9—C8	0.1 (4)
C3—C4—C5—C6	−179.2 (3)	C3—C4—C9—C8	178.9 (2)
C4—C5—C6—C7	0.0 (5)	C9—C8—C11—C12	101.1 (3)
C10—O3—C7—C6	0.6 (4)	C7—C8—C11—C12	−76.7 (3)
C10—O3—C7—C8	−179.7 (2)	C8—C11—C12—O4	−73.0 (2)
C5—C6—C7—O3	−179.4 (3)	C8—C11—C12—C13	164.76 (19)
C5—C6—C7—C8	1.0 (5)	O4—C12—C13—O5	−70.5 (2)
O3—C7—C8—C9	179.0 (2)	C11—C12—C13—O5	51.0 (2)
C6—C7—C8—C9	−1.3 (4)	O4—C12—C13—C15	172.2 (2)
O3—C7—C8—C11	−3.1 (4)	C11—C12—C13—C15	−66.4 (3)
C6—C7—C8—C11	176.6 (3)	O4—C12—C13—C14	50.0 (2)
C1—O1—C9—C8	−177.4 (2)	C11—C12—C13—C14	171.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.84 (1)	2.01 (1)	2.842 (3)	169 (5)
O5—H5···O2ⁱⁱ	0.85 (1)	2.12 (2)	2.936 (3)	163 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x+3, y−1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₈O₅
M_r	278.29
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	5.8061 (7), 10.5146 (13), 11.4477 (14)
β (°)	91.547 (2)
V (Å³)	698.61 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6694, 1699, 1338
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.00
No. of reflections	1699
No. of parameters	192
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.84 (1)	2.01 (1)	2.842 (3)	169 (5)
O5—H5···O2ⁱⁱ	0.85 (1)	2.12 (2)	2.936 (3)	163 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x+3, y−1/2, −z+2.

Acknowledgements

This work was supported by the Directorate General of Higher Education, Ministry of National Education, Indonesia (BPPS-Doctoral Program), the I-MHERE Project of Padjadjaran University, the Science Fund of Malaysia (12-02-03-2063) and the University of Malaya.

References

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