Matricarin

organic papers

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Structure Reports

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Matricarin

Masood Parvez,a_{* Viqar Uddin} Ahmad,b_{Umar Farooq,}b Amir Reza Jassbib_and Hussaini S. Raziullahb

a_{Department of Chemistry, The University of}

Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4, andb_{HEJ Research} Institute of Chemistry, University of Karachi, Karachi 75270, Pakistan

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 173 K

Mean(C±C) = 0.002 AÊ Rfactor = 0.034 wRfactor = 0.093

Data-to-parameter ratio = 12.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The structure of the sesquiterpene lactone matricarin, C17H20O2, is composed of a seven-membered ring that adopts

a chair conformation, fused to two ®ve-membered rings, one of which is essentially planar and the other exhibits an envelope conformation. The structure is devoid of any classical hydrogen bonds.

Comment

We have isolated a sesquiterpene lactone, matricarin, (I), from Achillea vermacularis (Compositae), collected from Tehran area. Martinezet al.(1988) have reported the NMR spectro-scopic data for (I) and some related guanianolides without quoting the source of (I). In this paper, we report the structure of (I), which has been established by X-ray crystallography.

The structure of (I) is presented in Fig. 1. The molecular dimensions lie within expected ranges (Orpenet al., 1994) for the corresponding bond distances and angles with mean bond distances: Csp3_ÐCsp3 _{1.527 (5), Csp}3_ÐCsp2 _{1.508 (11),}

Csp2_ÐCsp2_{1.480 (16), OÐCsp}3_{1.455 (2), OÐCsp}2_{1.354 (7),}

C C 1.341 (6) and C O 1.205 (15) AÊ. The seven-membered ring adopts a chair conformation wherein atoms C5/C6/C8/C9 are in a plane [maximum deviation 0.0096 (8) AÊ], with C7 0.744 (2) AÊ above and C1 and C10 1.012 (2) and 1.051 (2) AÊ, respectively, below this plane. The C1±C5 ®ve-membered ring is essentially planar, with the maximum deviation of any atom being 0.0114 (10) AÊ. The other ®ve-membered ring, O2/C6/ C7/C11/C12, has a C7-envelope conformation with C7 0.608 (3) AÊ out of the plane of the remaining ring atoms. The structure is devoid of any classical hydrogen bonds.

Experimental

The plants of Achillea vermacularis (Compositae) were collected from Tehran area in July, 1997, and were shade-dried; ground whole plant material (6 kg) was extracted with methanol. The resulting gummy material (600 g) was partitioned into hexane, ethyl acetate

and n-butanol soluble fractions. The ethyl acetate fraction was subjected to ¯ash column chromatography using hexane/ethyl acetate (7:3) over silica gel, affording (I) as colorless needles suitable for X-ray diffraction analysis.

Crystal data

C17H20O5 Mr= 304.33 Monoclinic,P21 a= 10.2083 (2) AÊ

b= 7.5434 (2) AÊ

c= 11.0118 (3) AÊ

= 109.677 (1)

V= 798.45 (3) AÊ3 Z= 2

Dx= 1.266 Mg mÿ3 MoKradiation Cell parameters from 2454

re¯ections

= 1.0±30.0

= 0.09 mmÿ1 T= 173 (2) K Block, colorless 0.250.200.18 mm

Data collection

Nonius KappaCCD diffractometer

!and'scans

Absorption correction: multi-scan (SORTAV: Blessing, 1995, 1997)

Tmin= 0.977,Tmax= 0.983

4575 measured re¯ections 2477 independent re¯ections

2297 re¯ections withI> 2(I)

Rint= 0.016

max= 30.0 h=ÿ14!14

k=ÿ10!10

l=ÿ15!15 Intensity decay: <0.1%

Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.034} wR(F2_{) = 0.093} S= 1.07 2477 re¯ections 203 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.047P)2 + 0.087P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.003

max= 0.21 e AÊÿ3

min=ÿ0.13 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1ÐC2 1.2274 (18)

O2ÐC12 1.361 (2)

O2ÐC6 1.4560 (16)

O3ÐC12 1.195 (2)

O4ÐC16 1.346 (2)

O4ÐC8 1.4531 (16)

O5ÐC16 1.194 (2)

C12ÐO2ÐC6 108.82 (11) C16ÐO4ÐC8 117.07 (13)

The H atoms were located from a difference Fourier synthesis and were included in the re®nement at geometrically idealized positions, with CÐH distances in the range 0.95±1.00 AÊ, utilizing riding models and allowing isotropic displacement parameters 1.2 (non-methyl) and 1.5 (methyl) times the equivalent isotropic displacement parameters of the atoms to which they were bonded. In the absence of signi®cant anomalous dispersion effects, Friedel pairs were averaged and the absolute con®guration cannot be determined from the crystal-lographic experiment. The absolute con®guration depicted in the

Schemeand shown in Fig. 1 was chosen arbitrarily.

Data collection:COLLECT(Hooft, 1998); cell re®nement:HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALE-PACK (Otwinowski & Minor, 1997); program(s) used to solve structure:SAPI91 (Fan, 1991); program(s) used to re®ne structure:

SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN

(Molecular Structure Corporation, 1994); software used to prepare material for publication:SHELXL97.

References

Blessing, R. H. (1995).Acta Cryst.A51, 33±37. Blessing, R. H. (1997).J. Appl. Cryst.30, 421±426.

Fan, H.-F. (1991).SAPI91. Rigaku Corporation, Tokyo, Japan. Hooft, R. (1998).COLLECT. Nonius BV, Delft, The Netherlands.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Martinez, M. V., Munoz-Zamora, A. & Joseph-Nathan, P. (1988).J. Nat. Prod.

51, 221±228.

Molecular Structure Corporation (1994). TEXSAN. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

Orpen, A. G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1994).Structure Correlation, Vol. 2, edited by H.-B. BuÈrgi & J. D. Dunitz, Appendix A. Weinheim: VCH Publishers.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter a& R. M. Sweet, pp. 307±326. London: Academic Press.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Figure 1

supporting information

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Acta Cryst. (2002). E58, o324–o325

supporting information

Acta Cryst. (2002). E58, o324–o325 [doi:10.1107/S1600536802002982]

Matricarin

Masood Parvez, Viqar Uddin Ahmad, Umar Farooq, Amir Reza Jassbi and Hussaini S. Raziullah

S1. Comment

We have isolated a sesqiterpene lactone, matricarin, (I), from Achillea vermacularis (Compositae), collected from Tehran

area. Martinez et al. (1988) have reported the NMR spectroscopic data for (I) and some related guanianolides without

quoting the source of (I). In this paper, we report the structure of (I) which has been established by X-ray crystallographic

method.

The structure of (I) is presented in Fig. 1. The molecular dimensions lie within expected values (Orpen et al., 1994) for

the corresponding bond distances and angles with mean bond distances: Csp3_—Csp3 _{1.527 (5), Csp}3_—Csp2 _{1.508 (11),}

Csp2_—Csp2 _{1.480 (16), O—Csp}3 _{1.455 (2), O—Csp}2 _{1.354 (7), C═C 1.341 (6) and C═O 1.205 (15) Å. The}

seven-membered ring adopts a chair conformation wherein atoms C5/C6/C8/C9 are in a plane [maximum deviation 0.0096 (8)

Å], with C7 0.744 (2) Å above and C1 and C10 1.012 (2) and 1.051 (2) Å, respectively, below this plane. The C1—C5

membered ring is essentially planar, with the maximum deviation of any atom being 0.0114 (10) Å. The other

five-membered ring, O2/C7/C7/C11/C12, has a C7-envelope conformation with C7 0.608 (3) Å out of the plane of the

remaining ring atoms. The structure is devoid of any classical hydrogen bonds.

S2. Experimental

The plants of Achillea vermacularis (Compositae) were collected from Tehran area in July, 1997, shade-dried and ground

whole plant material (6 kg) was extracted with methanol. The resulting gummy material (600 g) was partitioned into

hexane, ethyl acetate and n-butanol soluble fractions. The ethyl acetate fraction was subjected to column chromatography

using hexane/ethyl acetate (7:3) over flash silica which gel afforded (I) as colorless needles suitable XRD analysis.

S3. Refinement

The H atoms were located from difference Fourier synthesis and were included in the refinement at geometrically

idealized positions, with C—H distances in the range 0.95–1.00 Å, utilizing riding models and allowing isotropic

displacement parameters 1.2 (non-methyl) and 1.5 (methyl) times the equivalent isotropic displacement parameters of the

Figure 1

ORTEPII (Johnson, 1976) drawing of (I) with displacement ellipsoids plotted at the 50% probability level.

(I)

Crystal data

C17H20O5 Mr = 304.33

Monoclinic, P21 a = 10.2083 (2) Å

b = 7.5434 (2) Å

c = 11.0118 (3) Å

β = 109.677 (1)°

V = 798.45 (3) Å3 Z = 2

F(000) = 324

Dx = 1.266 Mg m−3

Mo Kα radiation, λ = 0.71069 Å Cell parameters from 2454 reflections

θ = 1.0–30.0°

µ = 0.09 mm−1 T = 173 K Block, colourless 0.25 × 0.20 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2φ scans

Absorption correction: multi-scan (SORTAV: Blessing, 1995, 1997)

Tmin = 0.977, Tmax = 0.983

4575 measured reflections 2477 independent reflections 2297 reflections with I > 2σ(I)

Rint = 0.016

θmax = 30.0°, θmin = 3.3° h = −14→14

k = −10→10

supporting information

sup-3

Acta Cryst. (2002). E58, o324–o325 Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.034} wR(F2_{) = 0.093} S = 1.07 2477 reflections 203 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.047P)2 + 0.087P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.003

Δρmax = 0.21 e Å−3

Δρmin = −0.13 e Å−3

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

x y z Uiso*/Ueq

O1 0.40145 (13) 0.18569 (18) 0.29681 (10) 0.0416 (3) O2 0.41064 (11) 0.28261 (18) 0.81551 (11) 0.0385 (3)

O3 0.44291 (15) 0.3757 (3) 1.01584 (15) 0.0709 (6)

O4 0.88610 (10) 0.22105 (17) 0.88429 (10) 0.0357 (3)

O5 0.99662 (14) 0.3945 (3) 0.78545 (16) 0.0650 (5)

C1 0.50669 (15) 0.1324 (2) 0.52925 (13) 0.0286 (3)

C2 0.39214 (16) 0.1641 (2) 0.40408 (14) 0.0321 (3)

C3 0.26168 (15) 0.1607 (2) 0.43196 (15) 0.0346 (3)

H3 0.1722 0.1748 0.3687 0.042*

C4 0.28403 (15) 0.1353 (2) 0.55720 (15) 0.0323 (3)

C5 0.43934 (14) 0.1164 (2) 0.63346 (13) 0.0278 (3)

H5 0.4585 −0.0035 0.6744 0.033*

C6 0.49748 (14) 0.2601 (2) 0.73539 (14) 0.0289 (3)

H6 0.5011 0.3748 0.6911 0.035*

C7 0.64121 (14) 0.2215 (2) 0.83319 (13) 0.0294 (3)

H7 0.6421 0.0969 0.8645 0.035*

C8 0.75700 (14) 0.2416 (2) 0.77678 (14) 0.0295 (3)

H8 0.7528 0.3610 0.7362 0.035*

C9 0.75161 (15) 0.0953 (2) 0.67924 (15) 0.0330 (3)

H9A 0.8443 0.0850 0.6697 0.040*

H9B 0.7312 −0.0188 0.7136 0.040*

C10 0.64389 (15) 0.1263 (2) 0.54739 (14) 0.0307 (3)

C11 0.64252 (17) 0.3477 (3) 0.94242 (16) 0.0416 (4)

H11 0.6641 0.4702 0.9201 0.050*

C12 0.49165 (19) 0.3396 (3) 0.93434 (18) 0.0464 (4)

C13 0.7393 (2) 0.3019 (5) 1.07851 (18) 0.0672 (8)

H13A 0.7124 0.3708 1.1418 0.101*

H13B 0.8355 0.3304 1.0863 0.101*

H13C 0.7320 0.1751 1.0945 0.101*

C14 0.70502 (18) 0.1503 (3) 0.44187 (16) 0.0383 (4)

H14A 0.6306 0.1782 0.3609 0.058*

H14B 0.7517 0.0407 0.4315 0.058*

H14C 0.7725 0.2476 0.4645 0.058*

H15A 0.0816 0.1087 0.5482 0.065*

H15B 0.1724 0.2274 0.6673 0.065*

H15C 0.1895 0.0163 0.6727 0.065*

C16 0.99833 (16) 0.3077 (3) 0.87667 (18) 0.0396 (4)

C17 1.12117 (17) 0.2786 (4) 0.9959 (2) 0.0574 (6)

H17A 1.2070 0.2955 0.9761 0.086*

H17B 1.1186 0.1577 1.0275 0.086*

H17C 1.1184 0.3636 1.0623 0.086*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O1 0.0498 (6) 0.0426 (7) 0.0316 (5) 0.0048 (6) 0.0126 (5) 0.0008 (5) O2 0.0291 (5) 0.0470 (7) 0.0441 (6) −0.0036 (5) 0.0184 (4) −0.0123 (5) O3 0.0523 (8) 0.1082 (16) 0.0624 (9) −0.0121 (10) 0.0326 (7) −0.0406 (11) O4 0.0247 (5) 0.0387 (6) 0.0395 (6) −0.0043 (4) 0.0055 (4) −0.0007 (5) O5 0.0366 (7) 0.0782 (12) 0.0800 (10) −0.0109 (8) 0.0195 (7) 0.0200 (10) C1 0.0302 (6) 0.0254 (6) 0.0301 (6) 0.0004 (6) 0.0098 (5) −0.0011 (6) C2 0.0370 (7) 0.0251 (7) 0.0324 (7) 0.0016 (6) 0.0093 (5) −0.0013 (6) C3 0.0303 (7) 0.0320 (8) 0.0362 (7) 0.0014 (6) 0.0043 (5) 0.0012 (6) C4 0.0270 (7) 0.0282 (7) 0.0396 (7) −0.0017 (6) 0.0084 (5) −0.0004 (6) C5 0.0258 (6) 0.0260 (7) 0.0310 (6) −0.0016 (5) 0.0089 (5) −0.0006 (5) C6 0.0256 (6) 0.0295 (7) 0.0335 (7) −0.0014 (6) 0.0125 (5) −0.0030 (6) C7 0.0259 (6) 0.0315 (7) 0.0306 (6) −0.0041 (6) 0.0091 (5) −0.0035 (6) C8 0.0230 (6) 0.0303 (7) 0.0340 (7) −0.0005 (5) 0.0082 (5) −0.0015 (6) C9 0.0268 (6) 0.0348 (8) 0.0376 (7) 0.0017 (6) 0.0110 (5) −0.0033 (6) C10 0.0328 (7) 0.0265 (7) 0.0350 (7) −0.0008 (6) 0.0141 (5) −0.0035 (6) C11 0.0327 (7) 0.0529 (11) 0.0415 (8) −0.0090 (7) 0.0154 (6) −0.0185 (8) C12 0.0394 (8) 0.0549 (11) 0.0498 (10) −0.0084 (8) 0.0215 (7) −0.0197 (9) C13 0.0495 (10) 0.113 (2) 0.0363 (9) −0.0085 (13) 0.0101 (8) −0.0244 (13) C14 0.0410 (8) 0.0372 (9) 0.0424 (8) −0.0019 (7) 0.0216 (7) −0.0035 (7) C15 0.0275 (7) 0.0532 (11) 0.0486 (9) −0.0020 (8) 0.0119 (6) 0.0036 (9) C16 0.0260 (7) 0.0386 (9) 0.0544 (9) −0.0029 (6) 0.0137 (6) −0.0057 (8) C17 0.0269 (8) 0.0598 (13) 0.0730 (13) −0.0051 (9) 0.0004 (8) −0.0095 (11)

Geometric parameters (Å, º)

O1—C2 1.2274 (18) C8—C9 1.528 (2)

O2—C12 1.361 (2) C8—H8 1.0000

O2—C6 1.4560 (16) C9—C10 1.516 (2)

O3—C12 1.195 (2) C9—H9A 0.9900

O4—C16 1.346 (2) C9—H9B 0.9900

O4—C8 1.4531 (16) C10—C14 1.503 (2)

O5—C16 1.194 (2) C11—C12 1.514 (2)

C1—C10 1.347 (2) C11—C13 1.531 (3)

C1—C2 1.4964 (19) C11—H11 1.0000

C1—C5 1.5282 (19) C13—H13A 0.9800

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Acta Cryst. (2002). E58, o324–o325

C3—C4 1.334 (2) C13—H13C 0.9800

C3—H3 0.9500 C14—H14A 0.9800

C4—C15 1.497 (2) C14—H14B 0.9800

C4—C5 1.5305 (19) C14—H14C 0.9800

C5—C6 1.529 (2) C15—H15A 0.9800

C5—H5 1.0000 C15—H15B 0.9800

C6—C7 1.5275 (19) C15—H15C 0.9800

C6—H6 1.0000 C16—C17 1.495 (2)

C7—C8 1.5167 (18) C17—H17A 0.9800

C7—C11 1.530 (2) C17—H17B 0.9800

C7—H7 1.0000 C17—H17C 0.9800

C12—O2—C6 108.82 (11) C8—C9—H9B 108.8

C16—O4—C8 117.07 (13) H9A—C9—H9B 107.7

C10—C1—C2 126.36 (13) C1—C10—C14 124.24 (14)

C10—C1—C5 126.45 (12) C1—C10—C9 122.00 (13)

C2—C1—C5 107.14 (12) C14—C10—C9 113.76 (12)

O1—C2—C3 125.08 (14) C12—C11—C13 110.91 (16)

O1—C2—C1 128.17 (14) C12—C11—C7 100.92 (13)

C3—C2—C1 106.73 (12) C13—C11—C7 117.44 (19)

C4—C3—C2 111.61 (13) C12—C11—H11 109.0

C4—C3—H3 124.2 C13—C11—H11 109.0

C2—C3—H3 124.2 C7—C11—H11 109.0

C3—C4—C15 124.82 (14) O3—C12—O2 121.48 (17)

C3—C4—C5 111.45 (13) O3—C12—C11 128.28 (18)

C15—C4—C5 123.70 (14) O2—C12—C11 110.24 (14)

C1—C5—C4 103.03 (11) C11—C13—H13A 109.5

C1—C5—C6 109.48 (12) C11—C13—H13B 109.5

C4—C5—C6 114.26 (13) H13A—C13—H13B 109.5

C1—C5—H5 109.9 C11—C13—H13C 109.5

C4—C5—H5 109.9 H13A—C13—H13C 109.5

C6—C5—H5 109.9 H13B—C13—H13C 109.5

O2—C6—C7 103.37 (11) C10—C14—H14A 109.5

O2—C6—C5 111.25 (11) C10—C14—H14B 109.5

C7—C6—C5 115.19 (12) H14A—C14—H14B 109.5

O2—C6—H6 108.9 C10—C14—H14C 109.5

C7—C6—H6 108.9 H14A—C14—H14C 109.5

C5—C6—H6 108.9 H14B—C14—H14C 109.5

C8—C7—C6 112.84 (12) C4—C15—H15A 109.5

C8—C7—C11 117.26 (13) C4—C15—H15B 109.5

C6—C7—C11 100.82 (12) H15A—C15—H15B 109.5

C8—C7—H7 108.5 C4—C15—H15C 109.5

C6—C7—H7 108.5 H15A—C15—H15C 109.5

C11—C7—H7 108.5 H15B—C15—H15C 109.5

O4—C8—C7 105.89 (11) O5—C16—O4 123.17 (16)

O4—C8—C9 107.70 (12) O5—C16—C17 126.12 (17)

C7—C8—C9 111.55 (12) O4—C16—C17 110.72 (17)

C7—C8—H8 110.5 C16—C17—H17B 109.5

C9—C8—H8 110.5 H17A—C17—H17B 109.5

C10—C9—C8 113.88 (13) C16—C17—H17C 109.5

C10—C9—H9A 108.8 H17A—C17—H17C 109.5

C8—C9—H9A 108.8 H17B—C17—H17C 109.5

C10—C9—H9B 108.8

C10—C1—C2—O1 1.9 (3) C16—O4—C8—C7 −150.66 (14)

C5—C1—C2—O1 179.44 (16) C16—O4—C8—C9 89.89 (16)

C10—C1—C2—C3 −179.45 (16) C6—C7—C8—O4 173.55 (12)

C5—C1—C2—C3 −1.92 (17) C11—C7—C8—O4 57.06 (17)

O1—C2—C3—C4 −179.88 (17) C6—C7—C8—C9 −69.56 (17)

C1—C2—C3—C4 1.43 (19) C11—C7—C8—C9 173.95 (14)

C2—C3—C4—C15 −178.39 (17) O4—C8—C9—C10 −164.72 (12)

C2—C3—C4—C5 −0.3 (2) C7—C8—C9—C10 79.49 (16)

C10—C1—C5—C4 179.21 (16) C2—C1—C10—C14 −0.3 (3)

C2—C1—C5—C4 1.69 (17) C5—C1—C10—C14 −177.38 (17)

C10—C1—C5—C6 57.2 (2) C2—C1—C10—C9 179.25 (16)

C2—C1—C5—C6 −120.27 (13) C5—C1—C10—C9 2.2 (2)

C3—C4—C5—C1 −0.88 (18) C8—C9—C10—C1 −63.6 (2)

C15—C4—C5—C1 177.21 (16) C8—C9—C10—C14 116.04 (15)

C3—C4—C5—C6 117.79 (16) C8—C7—C11—C12 158.30 (15)

C15—C4—C5—C6 −64.1 (2) C6—C7—C11—C12 35.41 (17)

C12—O2—C6—C7 26.98 (18) C8—C7—C11—C13 −81.1 (2)

C12—O2—C6—C5 151.16 (15) C6—C7—C11—C13 156.06 (17)

C1—C5—C6—O2 164.00 (12) C6—O2—C12—O3 176.5 (2)

C4—C5—C6—O2 49.05 (17) C6—O2—C12—C11 −3.5 (2)

C1—C5—C6—C7 −78.81 (15) C13—C11—C12—O3 33.7 (4)

C4—C5—C6—C7 166.25 (12) C7—C11—C12—O3 158.9 (3)

O2—C6—C7—C8 −164.56 (12) C13—C11—C12—O2 −146.3 (2)

C5—C6—C7—C8 73.88 (17) C7—C11—C12—O2 −21.1 (2)

O2—C6—C7—C11 −38.66 (15) C8—O4—C16—O5 −2.1 (3)