organic compounds
12-{[4-(4-Bromophenyl)piperazin-1-yl]methyl}-9α-hydroxy-4,8-dimethyl-3,14-dioxatricyclo[9.3.0.02,4]tetradec-7-en-13-one
aLaboratoire de Chimie Biomoleculaire, Substances Naturelles et Réactivité, URAC16, Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, 40000 Marrakech, Morocco, and bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, BP 1014, Avenue Ibn Battouta, Rabat, Morocco
*Correspondence e-mail: loubidim@gmail.com
The title compound, C25H33BrN2O4, was synthesized from 9α-hydroxyparthenolide (9α-hydroxy-4,8-dimethyl-12-methylen-3,14-dioxa-tricyclo[9.3.0.02,4]tetradec-7-en-13-one), which was isolated from the chloroform extract of the aerial parts of Anvillea radiata. The molecule is built up from two fused five- and ten-membered rings with an additional epoxy ring system and a bromophenylpiperazine group as a substituent. The ten-membered ring adopts an approximate chair–chair–chair conformation, while the piperazine ring displays a chair conformation and the five-membered ring shows an with the C atom closest to the hydroxy group forming the flap. An intramolecular O—H⋯N hydrogen bond stabilizes the molecular conformation. The crystal packing features C—H⋯O hydrogen bonds, which link the molecules into zigzag chains running along the b-axis direction.
CCDC reference: 993318
Related literature
For background to the medicinal uses of the plant Anvillea radiata, see: Abdel Sattar et al. (1996); El Hassany et al. (2004); Qureshi et al. (1990). For the reactivity of this sesquiterpene, see: Neukirch et al. (2003); Hwang et al. (2006); Neelakantan et al. (2009). For the synthetic procedure, see: Moumou et al. (2010). For see: Cremer & Pople (1975)
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 993318
10.1107/S1600536814006473/bt6970sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814006473/bt6970Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814006473/bt6970Isup3.cml
The mixture of 9?-hydoxypartenolide (9α-hydroxy-4,8-dimethyl- 12-methylene- 3,14-dioxatricyclo[9.3.0.02,4]tetradec-7-en-13-one) (1 g, 3.8 mmol) and one equivalent of 1-(4-bromophenyl-piperazine) in EtOH (20 ml) was stirred for twelve hours at room temperature. Then, the reaction was stopped by adding water (10 ml) and the solution was extracted with chloroform (3 x 20 ml). The combined organic layers were dried over anhydrous MgSO4, filtered and concentrated under vacuum to give 1.5 g (3 mmol) of the title compound (yield: 79%). Recrystallization was performed from in ethyl acetate.
All H atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl), 0.97 Å (methylene), 0.98 Å (methine) and O–H = 0.82 Å with Uiso(H) = 1.2Ueq (methylene, methine) or Uiso(H) = 1.5Ueq(Cmethyl, O). The torsion angles about the C-Cmethyl and C-O bonds were refined.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).C25H33BrN2O4 | F(000) = 528 |
Mr = 505.44 | Dx = 1.422 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 5899 reflections |
a = 9.6790 (4) Å | θ = 2.4–28.7° |
b = 7.0710 (3) Å | µ = 1.78 mm−1 |
c = 17.3117 (7) Å | T = 296 K |
β = 94.872 (2)° | Box, colourless |
V = 1180.54 (8) Å3 | 0.5 × 0.03 × 0.03 mm |
Z = 2 |
Bruker X8 APEX diffractometer | 5899 independent reflections |
Radiation source: fine-focus sealed tube | 5216 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 28.7°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −12→13 |
Tmin = 0.634, Tmax = 0.746 | k = −9→9 |
14527 measured reflections | l = −23→23 |
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0313P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
5899 reflections | Δρmax = 0.44 e Å−3 |
292 parameters | Δρmin = −0.44 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (2000), 2614 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.007 (5) |
C25H33BrN2O4 | V = 1180.54 (8) Å3 |
Mr = 505.44 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.6790 (4) Å | µ = 1.78 mm−1 |
b = 7.0710 (3) Å | T = 296 K |
c = 17.3117 (7) Å | 0.5 × 0.03 × 0.03 mm |
β = 94.872 (2)° |
Bruker X8 APEX diffractometer | 5899 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 5216 reflections with I > 2σ(I) |
Tmin = 0.634, Tmax = 0.746 | Rint = 0.024 |
14527 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.076 | Δρmax = 0.44 e Å−3 |
S = 1.03 | Δρmin = −0.44 e Å−3 |
5899 reflections | Absolute structure: Flack & Bernardinelli (2000), 2614 Friedel pairs |
292 parameters | Absolute structure parameter: 0.007 (5) |
1 restraint |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.81297 (2) | 0.79383 (4) | −0.080172 (12) | 0.06016 (9) | |
O1 | 0.06025 (14) | −0.47571 (19) | 0.48432 (7) | 0.0400 (3) | |
O3 | 0.29861 (12) | −0.1832 (2) | 0.50486 (6) | 0.0367 (3) | |
O4 | 0.34442 (13) | −0.25359 (19) | 0.21350 (8) | 0.0418 (3) | |
H4 | 0.4035 | −0.1779 | 0.2306 | 0.063* | |
N1 | 0.53704 (14) | 0.0338 (2) | 0.29071 (8) | 0.0302 (3) | |
N2 | 0.63915 (15) | 0.2755 (2) | 0.17458 (8) | 0.0351 (3) | |
C1 | 0.20134 (15) | −0.2018 (3) | 0.43565 (8) | 0.0280 (3) | |
H1 | 0.1227 | −0.1152 | 0.4376 | 0.034* | |
O2 | 0.51010 (17) | −0.0713 (3) | 0.53716 (9) | 0.0637 (5) | |
C11 | 0.40639 (17) | −0.0352 (2) | 0.40481 (10) | 0.0301 (3) | |
H11 | 0.3778 | 0.0978 | 0.4024 | 0.036* | |
C10 | 0.28736 (16) | −0.1544 (2) | 0.36682 (9) | 0.0257 (3) | |
H10 | 0.3270 | −0.2728 | 0.3492 | 0.031* | |
C2 | 0.15415 (18) | −0.4034 (2) | 0.43110 (10) | 0.0302 (3) | |
H2 | 0.2277 | −0.4925 | 0.4205 | 0.036* | |
C9 | 0.20719 (17) | −0.0612 (2) | 0.29633 (10) | 0.0275 (3) | |
H9A | 0.2462 | 0.0630 | 0.2885 | 0.033* | |
H9B | 0.1115 | −0.0439 | 0.3075 | 0.033* | |
C20 | 0.66722 (19) | 0.3843 (3) | 0.11021 (10) | 0.0333 (4) | |
C15 | −0.1053 (2) | −0.3330 (3) | 0.38362 (13) | 0.0416 (4) | |
H15A | −0.1899 | −0.3920 | 0.3961 | 0.062* | |
H15B | −0.1117 | −0.3022 | 0.3294 | 0.062* | |
H15C | −0.0903 | −0.2196 | 0.4136 | 0.062* | |
C8 | 0.21012 (17) | −0.1764 (2) | 0.22029 (9) | 0.0311 (3) | |
H8 | 0.1889 | −0.0899 | 0.1766 | 0.037* | |
C7 | 0.09765 (18) | −0.3259 (3) | 0.21770 (10) | 0.0315 (3) | |
C14 | −0.0380 (2) | −0.2547 (3) | 0.18031 (13) | 0.0460 (5) | |
H14A | −0.1099 | −0.3441 | 0.1886 | 0.069* | |
H14B | −0.0312 | −0.2393 | 0.1257 | 0.069* | |
H14C | −0.0595 | −0.1353 | 0.2027 | 0.069* | |
C3 | 0.01452 (19) | −0.4672 (2) | 0.40199 (10) | 0.0319 (4) | |
C16 | 0.5343 (2) | 0.2401 (3) | 0.29620 (11) | 0.0392 (4) | |
H16A | 0.6185 | 0.2834 | 0.3253 | 0.047* | |
H16B | 0.4563 | 0.2783 | 0.3242 | 0.047* | |
C17 | 0.5224 (2) | 0.3318 (3) | 0.21754 (11) | 0.0421 (5) | |
H17A | 0.4361 | 0.2940 | 0.1891 | 0.051* | |
H17B | 0.5215 | 0.4683 | 0.2233 | 0.051* | |
C5 | 0.0058 (2) | −0.6297 (2) | 0.27166 (12) | 0.0395 (4) | |
H5A | 0.0218 | −0.7510 | 0.2478 | 0.047* | |
H5B | −0.0839 | −0.5833 | 0.2507 | 0.047* | |
C6 | 0.1169 (2) | −0.4925 (2) | 0.25258 (10) | 0.0343 (4) | |
H6 | 0.2081 | −0.5278 | 0.2666 | 0.041* | |
C13 | 0.54475 (19) | −0.0520 (3) | 0.36882 (11) | 0.0364 (4) | |
H13A | 0.6166 | 0.0107 | 0.4020 | 0.044* | |
H13B | 0.5696 | −0.1844 | 0.3653 | 0.044* | |
C21 | 0.5923 (2) | 0.5468 (3) | 0.08862 (11) | 0.0379 (4) | |
H21 | 0.5133 | 0.5762 | 0.1133 | 0.046* | |
C22 | 0.6333 (2) | 0.6657 (3) | 0.03105 (11) | 0.0420 (4) | |
H22 | 0.5826 | 0.7745 | 0.0179 | 0.050* | |
C18 | 0.6578 (2) | −0.0185 (3) | 0.24953 (12) | 0.0387 (4) | |
H18A | 0.6627 | −0.1551 | 0.2451 | 0.046* | |
H18B | 0.7419 | 0.0249 | 0.2786 | 0.046* | |
C4 | 0.0055 (2) | −0.6550 (2) | 0.36027 (12) | 0.0398 (4) | |
H4A | −0.0788 | −0.7194 | 0.3717 | 0.048* | |
H4B | 0.0835 | −0.7333 | 0.3790 | 0.048* | |
C12 | 0.4169 (2) | −0.0961 (3) | 0.48858 (11) | 0.0389 (4) | |
C24 | 0.8214 (2) | 0.4589 (4) | 0.01092 (13) | 0.0514 (5) | |
H24 | 0.8976 | 0.4280 | −0.0158 | 0.062* | |
C23 | 0.7487 (2) | 0.6225 (3) | −0.00648 (11) | 0.0414 (4) | |
C19 | 0.6466 (2) | 0.0693 (3) | 0.16953 (11) | 0.0383 (4) | |
H19A | 0.7265 | 0.0336 | 0.1427 | 0.046* | |
H19B | 0.5642 | 0.0220 | 0.1399 | 0.046* | |
C25 | 0.7808 (2) | 0.3408 (3) | 0.06823 (12) | 0.0471 (5) | |
H25 | 0.8299 | 0.2297 | 0.0793 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.06273 (15) | 0.07268 (15) | 0.04532 (12) | −0.01813 (12) | 0.00605 (9) | 0.02022 (11) |
O1 | 0.0448 (8) | 0.0446 (7) | 0.0312 (7) | −0.0100 (6) | 0.0071 (6) | 0.0077 (5) |
O3 | 0.0389 (6) | 0.0481 (7) | 0.0232 (5) | −0.0105 (6) | 0.0036 (4) | 0.0038 (5) |
O4 | 0.0341 (7) | 0.0539 (8) | 0.0390 (7) | 0.0043 (6) | 0.0129 (6) | −0.0079 (6) |
N1 | 0.0268 (7) | 0.0342 (7) | 0.0301 (7) | 0.0026 (6) | 0.0059 (6) | 0.0041 (6) |
N2 | 0.0405 (8) | 0.0358 (7) | 0.0306 (7) | 0.0071 (7) | 0.0129 (6) | 0.0049 (6) |
C1 | 0.0287 (7) | 0.0316 (7) | 0.0241 (7) | −0.0003 (7) | 0.0043 (5) | 0.0015 (7) |
O2 | 0.0577 (10) | 0.0973 (13) | 0.0334 (8) | −0.0328 (10) | −0.0125 (7) | 0.0183 (9) |
C11 | 0.0295 (9) | 0.0359 (8) | 0.0245 (8) | −0.0029 (7) | 0.0003 (6) | 0.0029 (6) |
C10 | 0.0262 (8) | 0.0286 (7) | 0.0227 (7) | 0.0038 (6) | 0.0043 (6) | 0.0011 (5) |
C2 | 0.0328 (9) | 0.0299 (7) | 0.0283 (8) | 0.0024 (7) | 0.0045 (7) | 0.0058 (6) |
C9 | 0.0280 (8) | 0.0271 (7) | 0.0274 (8) | 0.0050 (6) | 0.0014 (6) | 0.0022 (6) |
C20 | 0.0325 (9) | 0.0395 (9) | 0.0281 (9) | 0.0016 (7) | 0.0033 (7) | 0.0017 (7) |
C15 | 0.0328 (10) | 0.0442 (10) | 0.0484 (12) | 0.0042 (8) | 0.0058 (8) | −0.0078 (9) |
C8 | 0.0338 (8) | 0.0362 (9) | 0.0232 (7) | 0.0060 (7) | 0.0028 (6) | 0.0036 (7) |
C7 | 0.0332 (9) | 0.0361 (8) | 0.0252 (8) | 0.0059 (7) | 0.0015 (7) | −0.0057 (6) |
C14 | 0.0394 (10) | 0.0482 (11) | 0.0478 (11) | 0.0022 (8) | −0.0109 (8) | 0.0045 (9) |
C3 | 0.0338 (9) | 0.0315 (8) | 0.0310 (9) | −0.0022 (7) | 0.0065 (7) | 0.0005 (7) |
C16 | 0.0476 (11) | 0.0376 (9) | 0.0346 (9) | 0.0001 (7) | 0.0158 (8) | −0.0007 (7) |
C17 | 0.0503 (11) | 0.0362 (10) | 0.0428 (10) | 0.0128 (8) | 0.0219 (9) | 0.0053 (8) |
C5 | 0.0468 (11) | 0.0280 (8) | 0.0428 (11) | 0.0010 (7) | −0.0005 (8) | −0.0059 (7) |
C6 | 0.0372 (9) | 0.0337 (8) | 0.0321 (9) | 0.0074 (7) | 0.0035 (7) | −0.0058 (7) |
C13 | 0.0274 (9) | 0.0472 (10) | 0.0343 (9) | −0.0015 (7) | 0.0016 (7) | 0.0097 (8) |
C21 | 0.0371 (10) | 0.0421 (9) | 0.0353 (9) | 0.0033 (8) | 0.0073 (8) | 0.0044 (8) |
C22 | 0.0491 (12) | 0.0412 (9) | 0.0353 (10) | 0.0011 (9) | 0.0019 (8) | 0.0077 (8) |
C18 | 0.0330 (9) | 0.0410 (10) | 0.0435 (11) | 0.0087 (8) | 0.0119 (8) | 0.0073 (8) |
C4 | 0.0444 (11) | 0.0303 (9) | 0.0447 (11) | −0.0045 (7) | 0.0047 (8) | 0.0019 (7) |
C12 | 0.0408 (11) | 0.0483 (10) | 0.0273 (9) | −0.0103 (8) | 0.0003 (7) | 0.0050 (8) |
C24 | 0.0478 (12) | 0.0690 (14) | 0.0397 (11) | 0.0096 (11) | 0.0177 (9) | 0.0107 (10) |
C23 | 0.0443 (11) | 0.0519 (12) | 0.0275 (9) | −0.0110 (9) | −0.0005 (8) | 0.0069 (8) |
C19 | 0.0432 (11) | 0.0365 (9) | 0.0374 (10) | 0.0094 (8) | 0.0161 (8) | 0.0013 (7) |
C25 | 0.0480 (11) | 0.0559 (13) | 0.0396 (10) | 0.0154 (9) | 0.0160 (9) | 0.0120 (9) |
Br1—C23 | 1.9020 (19) | C8—H8 | 0.9800 |
O1—C2 | 1.442 (2) | C7—C6 | 1.329 (3) |
O1—C3 | 1.457 (2) | C7—C14 | 1.500 (3) |
O3—C12 | 1.351 (2) | C14—H14A | 0.9600 |
O3—C1 | 1.465 (2) | C14—H14B | 0.9600 |
O4—C8 | 1.424 (2) | C14—H14C | 0.9600 |
O4—H4 | 0.8200 | C3—C4 | 1.510 (3) |
N1—C16 | 1.462 (3) | C16—C17 | 1.504 (3) |
N1—C18 | 1.467 (2) | C16—H16A | 0.9700 |
N1—C13 | 1.478 (2) | C16—H16B | 0.9700 |
N2—C20 | 1.400 (2) | C17—H17A | 0.9700 |
N2—C17 | 1.460 (2) | C17—H17B | 0.9700 |
N2—C19 | 1.462 (3) | C5—C6 | 1.505 (3) |
C1—C2 | 1.497 (3) | C5—C4 | 1.545 (3) |
C1—C10 | 1.5473 (19) | C5—H5A | 0.9700 |
C1—H1 | 0.9800 | C5—H5B | 0.9700 |
O2—C12 | 1.193 (3) | C6—H6 | 0.9300 |
C11—C12 | 1.508 (2) | C13—H13A | 0.9700 |
C11—C13 | 1.529 (2) | C13—H13B | 0.9700 |
C11—C10 | 1.530 (2) | C21—C22 | 1.387 (3) |
C11—H11 | 0.9800 | C21—H21 | 0.9300 |
C10—C9 | 1.538 (2) | C22—C23 | 1.374 (3) |
C10—H10 | 0.9800 | C22—H22 | 0.9300 |
C2—C3 | 1.473 (3) | C18—C19 | 1.513 (3) |
C2—H2 | 0.9800 | C18—H18A | 0.9700 |
C9—C8 | 1.550 (2) | C18—H18B | 0.9700 |
C9—H9A | 0.9700 | C4—H4A | 0.9700 |
C9—H9B | 0.9700 | C4—H4B | 0.9700 |
C20—C21 | 1.393 (3) | C24—C23 | 1.373 (3) |
C20—C25 | 1.402 (2) | C24—C25 | 1.379 (3) |
C15—C3 | 1.511 (3) | C24—H24 | 0.9300 |
C15—H15A | 0.9600 | C19—H19A | 0.9700 |
C15—H15B | 0.9600 | C19—H19B | 0.9700 |
C15—H15C | 0.9600 | C25—H25 | 0.9300 |
C8—C7 | 1.516 (3) | ||
C2—O1—C3 | 61.05 (11) | O1—C3—C15 | 113.30 (14) |
C12—O3—C1 | 111.57 (12) | C2—C3—C15 | 123.01 (16) |
C8—O4—H4 | 109.5 | C4—C3—C15 | 116.06 (17) |
C16—N1—C18 | 107.64 (14) | N1—C16—C17 | 111.83 (16) |
C16—N1—C13 | 110.47 (15) | N1—C16—H16A | 109.2 |
C18—N1—C13 | 111.14 (14) | C17—C16—H16A | 109.2 |
C20—N2—C17 | 117.81 (15) | N1—C16—H16B | 109.2 |
C20—N2—C19 | 119.11 (14) | C17—C16—H16B | 109.2 |
C17—N2—C19 | 110.26 (14) | H16A—C16—H16B | 107.9 |
O3—C1—C2 | 107.50 (14) | N2—C17—C16 | 109.89 (15) |
O3—C1—C10 | 105.06 (12) | N2—C17—H17A | 109.7 |
C2—C1—C10 | 110.33 (13) | C16—C17—H17A | 109.7 |
O3—C1—H1 | 111.2 | N2—C17—H17B | 109.7 |
C2—C1—H1 | 111.2 | C16—C17—H17B | 109.7 |
C10—C1—H1 | 111.2 | H17A—C17—H17B | 108.2 |
C12—C11—C13 | 112.33 (15) | C6—C5—C4 | 110.75 (16) |
C12—C11—C10 | 104.05 (13) | C6—C5—H5A | 109.5 |
C13—C11—C10 | 115.82 (14) | C4—C5—H5A | 109.5 |
C12—C11—H11 | 108.1 | C6—C5—H5B | 109.5 |
C13—C11—H11 | 108.1 | C4—C5—H5B | 109.5 |
C10—C11—H11 | 108.1 | H5A—C5—H5B | 108.1 |
C11—C10—C9 | 114.56 (13) | C7—C6—C5 | 126.55 (18) |
C11—C10—C1 | 102.89 (13) | C7—C6—H6 | 116.7 |
C9—C10—C1 | 115.83 (13) | C5—C6—H6 | 116.7 |
C11—C10—H10 | 107.7 | N1—C13—C11 | 111.29 (14) |
C9—C10—H10 | 107.7 | N1—C13—H13A | 109.4 |
C1—C10—H10 | 107.7 | C11—C13—H13A | 109.4 |
O1—C2—C3 | 59.99 (11) | N1—C13—H13B | 109.4 |
O1—C2—C1 | 120.69 (14) | C11—C13—H13B | 109.4 |
C3—C2—C1 | 125.25 (15) | H13A—C13—H13B | 108.0 |
O1—C2—H2 | 113.5 | C22—C21—C20 | 121.23 (17) |
C3—C2—H2 | 113.5 | C22—C21—H21 | 119.4 |
C1—C2—H2 | 113.5 | C20—C21—H21 | 119.4 |
C10—C9—C8 | 113.85 (13) | C23—C22—C21 | 119.91 (19) |
C10—C9—H9A | 108.8 | C23—C22—H22 | 120.0 |
C8—C9—H9A | 108.8 | C21—C22—H22 | 120.0 |
C10—C9—H9B | 108.8 | N1—C18—C19 | 110.06 (15) |
C8—C9—H9B | 108.8 | N1—C18—H18A | 109.6 |
H9A—C9—H9B | 107.7 | C19—C18—H18A | 109.6 |
C21—C20—N2 | 122.36 (15) | N1—C18—H18B | 109.6 |
C21—C20—C25 | 117.07 (17) | C19—C18—H18B | 109.6 |
N2—C20—C25 | 120.38 (16) | H18A—C18—H18B | 108.2 |
C3—C15—H15A | 109.5 | C3—C4—C5 | 111.61 (15) |
C3—C15—H15B | 109.5 | C3—C4—H4A | 109.3 |
H15A—C15—H15B | 109.5 | C5—C4—H4A | 109.3 |
C3—C15—H15C | 109.5 | C3—C4—H4B | 109.3 |
H15A—C15—H15C | 109.5 | C5—C4—H4B | 109.3 |
H15B—C15—H15C | 109.5 | H4A—C4—H4B | 108.0 |
O4—C8—C7 | 112.85 (15) | O2—C12—O3 | 121.57 (17) |
O4—C8—C9 | 110.74 (14) | O2—C12—C11 | 128.41 (17) |
C7—C8—C9 | 109.07 (12) | O3—C12—C11 | 109.99 (16) |
O4—C8—H8 | 108.0 | C23—C24—C25 | 119.72 (18) |
C7—C8—H8 | 108.0 | C23—C24—H24 | 120.1 |
C9—C8—H8 | 108.0 | C25—C24—H24 | 120.1 |
C6—C7—C14 | 125.23 (18) | C24—C23—C22 | 120.37 (18) |
C6—C7—C8 | 122.16 (17) | C24—C23—Br1 | 119.54 (15) |
C14—C7—C8 | 112.24 (16) | C22—C23—Br1 | 120.05 (16) |
C7—C14—H14A | 109.5 | N2—C19—C18 | 110.77 (16) |
C7—C14—H14B | 109.5 | N2—C19—H19A | 109.5 |
H14A—C14—H14B | 109.5 | C18—C19—H19A | 109.5 |
C7—C14—H14C | 109.5 | N2—C19—H19B | 109.5 |
H14A—C14—H14C | 109.5 | C18—C19—H19B | 109.5 |
H14B—C14—H14C | 109.5 | H19A—C19—H19B | 108.1 |
O1—C3—C2 | 58.95 (11) | C24—C25—C20 | 121.58 (19) |
O1—C3—C4 | 115.59 (15) | C24—C25—H25 | 119.2 |
C2—C3—C4 | 116.57 (15) | C20—C25—H25 | 119.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···N1 | 0.82 | 2.18 | 2.995 (4) | 171 |
C1—H1···O1i | 0.98 | 2.52 | 3.389 (3) | 148 |
C15—H15C···O1i | 0.96 | 2.47 | 3.410 (3) | 167 |
Symmetry code: (i) −x, y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···N1 | 0.82 | 2.18 | 2.995 (4) | 171 |
C1—H1···O1i | 0.98 | 2.52 | 3.389 (3) | 148 |
C15—H15C···O1i | 0.96 | 2.47 | 3.410 (3) | 167 |
Symmetry code: (i) −x, y+1/2, −z+1. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
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The natural sesquiterpene lactone 9α-hydroxypartenolide is the main constituent of the chloroform extract of the aerial parts of Anvillea radiata (El Hassany et al., 2004) and of Anvillea garcini (Abdel Sattar et al., 1996). The reactivity of this sesquiterpene lactone and its derivatives has been the subject of several studies (Hwang et al., 2006; Neelakantan et al., 2009; Moumou et al., 2010), in order to prepare products with a high added value that can be used in the pharmacological industry. In this context, we have treated 9α-hydroxyparthenolide with an equivalent amount of 1- (4-bromophenyl)piperazine gives the title compound. The molecule contains a fused ring system and the bromophenyl-pyperazine group as a substituent to the lactone ring. The molecular structure (Fig. 1) shows the lactone ring to adopt an envelope conformation, as indicated by Cremer & Pople (1975) puckering parameters QT = 0.2525 (19) Å and ϕ2 = 259.3 (4)°. The ten-membered ring displays an approximate chair-chair-chair conformation, while the pyperazine ring has a perfect chair conformation with QT = 0.586 (2) Å, θ = 177.96 (18) and ϕ2 = 165 (4)°. In the crystal, C—H···O hydrogen bonding links the molecules to zigzag chains running along the b-axis (Table 1, Fig. 2). In addition, an intramolecular O4—H4···N1 hydrogen bond is also observed. Owing to the presence of a Br atom, the absolute configuration could be fully confirmed, by refining the Flack parameter (Flack & Bernardinelli, 2000) as C1(S), C2(R) C3(R), C8(R), C10(S) and C11(R).