9α-Hy­droxy-12-{[4-(4-hy­droxy­phen­yl)piperazin-1-yl]meth­yl}-4,8-dimethyl-3,14-dioxatri­cyclo­[9.3.0.02,4]tetra­dec-7-en-13-one

Loubidi, M.; Benharref, A.; El Ammari, L.; Saadi, M.; Berraho, M.

doi:10.1107/S1600536814007430

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 5| May 2014| Pages o530-o531

doi:10.1107/S1600536814007430

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9α-Hydroxy-12-{[4-(4-hydroxyphenyl)piperazin-1-yl]methyl}-4,8-dimethyl-3,14-dioxatricyclo[9.3.0.0^2,4]tetradec-7-en-13-one

Mohamed Loubidi,^a ^* Ahmed Benharref,^a Lahcen El Ammari,^b Mohamed Saadi ^b and Moha Berraho ^a

^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

(Received 24 March 2014; accepted 3 April 2014; online 9 April 2014)

The title compound, C₂₅H₃₄N₂O₅, was synthesized from 9α-hydroxyparthenolide (9α-hydroxy-4,8-dimethyl-12-methylen-3, 14-dioxa-tricyclo[9.3.0.0^2,4]tetradec-7-en-13-one), which in turn was isolated from the chloroform extract of the aerial parts of Anvillea radiata. The molecule comprises a ten-membered ring fused to a five-membered ring with an additional epoxy ring system fused to the ten-membered ring. The five-membered ring also carries a 4-hydroxyphenyl-piperazin-1-ylmethyl substituent. The ten-membered ring adopts an approximate chair–chair conformation, while the piperazine ring displays a chair conformation and the five-membered ring shows an envelope conformation with the C atom closest to the hydroxy group forming the flap. Two C atoms in the phenyl ring and the O atom of the hydroxyl group are disordered over two sites, with an occupancy ratio of 0.53 (5):0.47 (5). An intramolecular O—H⋯N hydrogen-bond stabilizes the molecular conformation. In the crystal, C—H⋯O hydrogen bonds link the molecules into zigzag chains running along the a-axis direction.

CCDC reference: 995311

Related literature

For background to the medicinal uses of the plant Anvillea radiata, see: Abdel Sattar et al. (1996 ); El Hassany et al. (2004 ). For the reactivity of this sesquiterpene, see: Hwang et al. (2006 ); Neelakantan et al. (2009 ). For a related synthetic procedure, see: Moumou et al. (2012 ). For conformational analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₅H₃₄N₂O₅
M_r = 442.54
Monoclinic, C 2
a = 29.880 (5) Å
b = 6.841 (5) Å
c = 11.999 (5) Å
β = 102.307 (5)°
V = 2396 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.5 × 0.03 × 0.03 mm

Data collection

Bruker X8 APEX Diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.639, T_max = 0.747
13097 measured reflections
2868 independent reflections
1830 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.102
S = 1.08
2868 reflections
322 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N1	0.82	2.22	3.030 (4)	169
C2—H2⋯O4ⁱ	0.98	2.45	3.243 (4)	138
C4—H4A⋯O2ⁱⁱ	0.97	2.43	3.315 (5)	151
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: 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: 995311

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814007430/sj5394sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007430/sj5394Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814007430/sj5394Isup3.cml

checkCIF report

Comment top

Our work lies within the framework of the evaluation of medicinal plants and in particular, Anvillea radiata. The main constituent of the chloroform extract of the aerial parts of this plant is 9α-hydroxypartenolide (Abdel Sattar et al., 1996; El Hassany et al., 2004). 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., 2012), in order to prepare high value added products for use in industrial pharmacology. In this work we present the crystal structure of the title compound (I). The molecule is built up from fused five-and ten-membered rings with the hydroxyphenyl-pyperazine group as a substituent. An additional epoxy ring system is also fused to the ten-membered ring at C2 and C3. The molecular structure of (I), Fig.1, shows the lactone ring to adopt an envelope conformation, as indicated by the Cremer & Pople (1975) puckering parameters QT = 0.208 (3) Å and ϕ2 = 248.2 (7)°. The ten-membered ring displays an approximate chair-chair conformation, while the pyperazine ring has a perfect chair conformation with QT = 0.572 (3) Å, θ = 176.9 (3) and ϕ2 = 184 (5)°. An intramolecular O4—H4···N1 hydrogen bond is observed. In the crystal, C—H···O hydrogen bonds link the molecules into zigzag chains running along the a axis (Table 1, Fig 1).

Related literature top

For background to the medicinal uses of the plant Anvillea radiata, see: Abdel Sattar et al. (1996); El Hassany et al. (2004). For the reactivity of this sesquiterpene, see: Hwang et al. (2006); Neelakantan et al. (2009). For a related synthetic procedure, see: Moumou et al. (2012). For conformational analysis, see: Cremer & Pople (1975)

Experimental top

A mixture of 9α-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-hydroxyphenyl-piperazine) in EtOH (20 ml) was stirred for twelve hours at room temperature. The reaction was stopped by adding water (10 ml) and the solution 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 (3.3 mmol) of the title compound (yield: 90%). Recrystallization was performed from ethyl acetate.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

	Fig. 1. :The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. For clarity only the major disorder components of the disordered C21 C22 and O5 atoms are shown.
	Fig. 2. : Packing view showing the C–H···O and O–H···N hydrogen bonds as dashed lines. H atoms not involved in hydrogen bonding and the atoms of the minor disorder component have been omitted for clarity.

9α-Hydroxy-12-{[4-(4-hydroxyphenyl)piperazin-1-yl]methyl}-4,8-dimethyl-3,14-dioxatricyclo[9.3.0.0^2,4]tetradec-7-en-13-one top

Crystal data top

C₂₅H₃₄N₂O₅	F(000) = 952
M_r = 442.54	D_x = 1.227 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 4801 reflections
a = 29.880 (5) Å	θ = 2.5–27.1°
b = 6.841 (5) Å	µ = 0.09 mm⁻¹
c = 11.999 (5) Å	T = 296 K
β = 102.307 (5)°	Needle, colourless
V = 2396 (2) Å³	0.5 × 0.03 × 0.03 mm
Z = 4

Data collection top

Bruker X8 APEX Diffractometer	2868 independent reflections
Radiation source: fine-focus sealed tube	1830 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ and ω scans	θ_max = 27.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −38→38
T_min = 0.639, T_max = 0.747	k = −8→7
13097 measured reflections	l = −15→15

Refinement top

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0408P)²] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2868 reflections	Δρ_max = 0.14 e Å⁻³
322 parameters	Δρ_min = −0.14 e Å⁻³
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0063 (6)

Crystal data top

C₂₅H₃₄N₂O₅	V = 2396 (2) Å³
M_r = 442.54	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 29.880 (5) Å	µ = 0.09 mm⁻¹
b = 6.841 (5) Å	T = 296 K
c = 11.999 (5) Å	0.5 × 0.03 × 0.03 mm
β = 102.307 (5)°

Data collection top

Bruker X8 APEX Diffractometer	2868 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1830 reflections with I > 2σ(I)
T_min = 0.639, T_max = 0.747	R_int = 0.055
13097 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.102	H-atom parameters constrained
S = 1.08	Δρ_max = 0.14 e Å⁻³
2868 reflections	Δρ_min = −0.14 e Å⁻³
322 parameters

Special details top

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.

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 > 2σ(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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.81526 (10)	0.5109 (5)	0.7206 (2)	0.0388 (7)
H1	0.8380	0.4421	0.7782	0.047*
C2	0.78537 (10)	0.6359 (5)	0.7759 (2)	0.0425 (7)
H2	0.7681	0.7338	0.7245	0.051*
C3	0.79457 (11)	0.6940 (5)	0.8964 (2)	0.0478 (8)
C4	0.77809 (13)	0.8925 (6)	0.9221 (3)	0.0645 (10)
H4A	0.7699	0.8898	0.9961	0.077*
H4B	0.7508	0.9254	0.8655	0.077*
C5	0.81482 (14)	1.0505 (5)	0.9224 (3)	0.0687 (11)
H5A	0.8007	1.1787	0.9185	0.082*
H5B	0.8376	1.0428	0.9931	0.082*
C6	0.83780 (13)	1.0258 (5)	0.8232 (3)	0.0548 (9)
H6	0.8195	1.0503	0.7516	0.066*
C7	0.88024 (13)	0.9743 (5)	0.8241 (3)	0.0544 (9)
C8	0.89540 (12)	0.9174 (5)	0.7157 (3)	0.0545 (9)
H8	0.9283	0.9432	0.7273	0.065*
C9	0.88783 (10)	0.6976 (5)	0.6916 (2)	0.0464 (8)
H9A	0.9070	0.6580	0.6397	0.056*
H9B	0.8985	0.6275	0.7625	0.056*
C10	0.83879 (10)	0.6316 (4)	0.6409 (2)	0.0369 (7)
H10	0.8203	0.7490	0.6184	0.044*
C11	0.83398 (10)	0.5009 (5)	0.5360 (2)	0.0420 (7)
H11	0.8624	0.4278	0.5393	0.050*
C12	0.79599 (11)	0.3623 (5)	0.5444 (2)	0.0452 (8)
C13	0.83375 (13)	0.6105 (6)	0.9824 (2)	0.0674 (11)
H13A	0.8596	0.6970	0.9913	0.101*
H13B	0.8419	0.4852	0.9566	0.101*
H13C	0.8249	0.5957	1.0542	0.101*
C14	0.91847 (14)	0.9532 (7)	0.9290 (3)	0.0855 (13)
H14A	0.9427	1.0427	0.9241	0.128*
H14B	0.9300	0.8218	0.9334	0.128*
H14C	0.9069	0.9817	0.9959	0.128*
C15	0.82137 (11)	0.6135 (5)	0.4222 (2)	0.0498 (8)
H15A	0.8201	0.5223	0.3597	0.060*
H15B	0.7911	0.6702	0.4150	0.060*
C16	0.89578 (11)	0.6953 (5)	0.3813 (3)	0.0574 (9)
H16A	0.8876	0.6275	0.3089	0.069*
H16B	0.9106	0.6023	0.4385	0.069*
C17	0.92853 (12)	0.8583 (6)	0.3722 (3)	0.0620 (10)
H17A	0.9380	0.9213	0.4459	0.074*
H17B	0.9556	0.8049	0.3508	0.074*
C18	0.83255 (11)	0.9076 (5)	0.3240 (3)	0.0559 (9)
H18A	0.8048	0.9589	0.3427	0.067*
H18B	0.8242	0.8397	0.2516	0.067*
C19	0.86433 (12)	1.0737 (5)	0.3134 (3)	0.0585 (10)
H19A	0.8494	1.1610	0.2531	0.070*
H19B	0.8709	1.1471	0.3841	0.070*
C20	0.93639 (12)	1.1478 (5)	0.2585 (3)	0.0524 (8)
C21A	0.9766 (11)	1.167 (5)	0.303 (2)	0.103 (11)	0.47 (5)
H21A	0.9892	1.0838	0.3630	0.124*	0.47 (5)
C22A	1.0052 (11)	1.307 (6)	0.269 (3)	0.184 (19)	0.47 (5)
H22A	1.0353	1.3161	0.3092	0.220*	0.47 (5)
C21B	0.9877 (9)	1.150 (3)	0.3049 (16)	0.059 (4)	0.53 (5)
H21B	1.0010	1.0609	0.3605	0.071*	0.53 (5)
C22B	1.0145 (8)	1.284 (2)	0.2650 (12)	0.066 (5)	0.53 (5)
H22B	1.0462	1.2840	0.2894	0.079*	0.53 (5)
C23	0.99198 (17)	1.4234 (8)	0.1851 (4)	0.0947 (15)
C24	0.94645 (15)	1.4229 (6)	0.1412 (3)	0.0817 (13)
H24	0.9337	1.5159	0.0872	0.098*
C25	0.91882 (13)	1.2851 (6)	0.1763 (3)	0.0616 (10)
H25	0.8876	1.2844	0.1440	0.074*
N1	0.85421 (8)	0.7703 (4)	0.41259 (18)	0.0446 (6)
N2	0.90743 (9)	1.0027 (4)	0.2877 (2)	0.0527 (7)
O1	0.78550 (7)	0.3726 (3)	0.64797 (15)	0.0455 (5)
O2	0.75946 (8)	0.5494 (4)	0.85303 (16)	0.0582 (7)
O3	0.87276 (10)	1.0320 (4)	0.62102 (19)	0.0689 (7)
H3	0.8708	0.9690	0.5620	0.103*
O4	0.77554 (8)	0.2523 (4)	0.47254 (18)	0.0653 (7)
O5A	1.0188 (7)	1.589 (4)	0.174 (3)	0.116 (8)	0.47 (5)
H5A1	1.0053	1.6567	0.1208	0.173*	0.47 (5)
O5B	1.0186 (6)	1.531 (3)	0.1318 (16)	0.080 (4)	0.53 (5)
H5B1	1.0034	1.5704	0.0709	0.120*	0.53 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0456 (18)	0.0352 (17)	0.0330 (13)	−0.0035 (15)	0.0025 (12)	−0.0011 (13)
C2	0.0496 (19)	0.0439 (19)	0.0364 (14)	−0.0019 (15)	0.0147 (13)	0.0051 (13)
C3	0.059 (2)	0.0478 (19)	0.0391 (15)	−0.0061 (18)	0.0159 (15)	−0.0022 (15)
C4	0.075 (2)	0.069 (3)	0.0551 (19)	0.004 (2)	0.0274 (18)	−0.0153 (19)
C5	0.089 (3)	0.044 (2)	0.078 (2)	0.003 (2)	0.028 (2)	−0.0179 (18)
C6	0.080 (3)	0.0266 (18)	0.0600 (19)	0.0035 (18)	0.0194 (18)	−0.0011 (15)
C7	0.068 (2)	0.040 (2)	0.0543 (18)	−0.0102 (19)	0.0107 (17)	−0.0105 (16)
C8	0.061 (2)	0.044 (2)	0.0589 (19)	−0.0102 (18)	0.0134 (16)	−0.0023 (16)
C9	0.051 (2)	0.042 (2)	0.0467 (16)	−0.0034 (16)	0.0113 (14)	−0.0057 (15)
C10	0.0417 (17)	0.0323 (17)	0.0363 (14)	−0.0004 (14)	0.0075 (12)	−0.0029 (12)
C11	0.0441 (18)	0.046 (2)	0.0355 (14)	−0.0034 (16)	0.0082 (12)	−0.0079 (14)
C12	0.050 (2)	0.0412 (19)	0.0432 (16)	0.0006 (17)	0.0074 (14)	−0.0051 (15)
C13	0.091 (3)	0.062 (2)	0.0424 (17)	−0.003 (2)	−0.0015 (17)	−0.0021 (16)
C14	0.084 (3)	0.102 (4)	0.065 (2)	−0.012 (3)	0.003 (2)	−0.029 (2)
C15	0.052 (2)	0.059 (2)	0.0403 (15)	−0.0026 (18)	0.0136 (14)	−0.0042 (15)
C16	0.056 (2)	0.055 (2)	0.068 (2)	0.0122 (19)	0.0284 (17)	0.0078 (18)
C17	0.057 (2)	0.056 (2)	0.079 (2)	0.018 (2)	0.0284 (18)	0.0184 (19)
C18	0.053 (2)	0.065 (2)	0.0532 (18)	0.0101 (19)	0.0180 (16)	0.0112 (17)
C19	0.061 (2)	0.057 (2)	0.0636 (19)	0.0196 (19)	0.0258 (17)	0.0146 (17)
C20	0.051 (2)	0.051 (2)	0.0564 (19)	0.0008 (18)	0.0149 (17)	0.0001 (17)
C21A	0.026 (12)	0.111 (16)	0.168 (17)	0.010 (9)	0.009 (8)	0.088 (13)
C22A	0.034 (10)	0.23 (3)	0.27 (3)	−0.002 (12)	−0.005 (11)	0.13 (3)
C21B	0.025 (9)	0.062 (8)	0.085 (8)	0.017 (6)	0.002 (5)	0.015 (7)
C22B	0.041 (7)	0.049 (8)	0.097 (9)	−0.011 (5)	−0.005 (5)	0.022 (6)
C23	0.072 (3)	0.087 (4)	0.116 (4)	−0.027 (3)	−0.001 (3)	0.033 (3)
C24	0.080 (3)	0.077 (3)	0.079 (2)	−0.025 (3)	−0.003 (2)	0.025 (2)
C25	0.062 (2)	0.058 (2)	0.059 (2)	−0.010 (2)	0.0006 (17)	0.0061 (19)
N1	0.0462 (16)	0.0481 (16)	0.0422 (13)	0.0059 (13)	0.0156 (11)	0.0046 (12)
N2	0.0531 (17)	0.0512 (18)	0.0590 (15)	0.0100 (15)	0.0233 (13)	0.0086 (14)
O1	0.0577 (14)	0.0379 (12)	0.0422 (11)	−0.0094 (11)	0.0136 (9)	−0.0071 (9)
O2	0.0718 (16)	0.0643 (17)	0.0440 (11)	−0.0185 (14)	0.0245 (10)	−0.0059 (11)
O3	0.100 (2)	0.0462 (15)	0.0619 (13)	−0.0122 (15)	0.0210 (14)	0.0062 (12)
O4	0.0738 (17)	0.0670 (17)	0.0549 (13)	−0.0186 (14)	0.0136 (12)	−0.0250 (12)
O5A	0.090 (7)	0.087 (11)	0.138 (16)	−0.065 (8)	−0.048 (9)	0.047 (10)
O5B	0.066 (5)	0.084 (9)	0.080 (6)	−0.054 (5)	−0.010 (5)	0.029 (6)

Geometric parameters (Å, º) top

C1—O1	1.454 (3)	C15—N1	1.475 (4)
C1—C2	1.490 (4)	C15—H15A	0.9700
C1—C10	1.542 (4)	C15—H15B	0.9700
C1—H1	0.9800	C16—N1	1.464 (4)
C2—O2	1.454 (3)	C16—C17	1.503 (5)
C2—C3	1.468 (4)	C16—H16A	0.9700
C2—H2	0.9800	C16—H16B	0.9700
C3—O2	1.455 (4)	C17—N2	1.459 (4)
C3—C13	1.499 (4)	C17—H17A	0.9700
C3—C4	1.499 (5)	C17—H17B	0.9700
C4—C5	1.540 (5)	C18—N1	1.462 (4)
C4—H4A	0.9700	C18—C19	1.504 (5)
C4—H4B	0.9700	C18—H18A	0.9700
C5—C6	1.505 (5)	C18—H18B	0.9700
C5—H5A	0.9700	C19—N2	1.469 (4)
C5—H5B	0.9700	C19—H19A	0.9700
C6—C7	1.314 (5)	C19—H19B	0.9700
C6—H6	0.9300	C20—C21A	1.21 (3)
C7—C14	1.516 (5)	C20—C25	1.381 (5)
C7—C8	1.516 (4)	C20—N2	1.409 (4)
C8—O3	1.426 (4)	C20—C21B	1.52 (3)
C8—C9	1.539 (5)	C21A—C22A	1.41 (4)
C8—H8	0.9800	C21A—H21A	0.9300
C9—C10	1.530 (4)	C22A—C23	1.27 (3)
C9—H9A	0.9700	C22A—H22A	0.9300
C9—H9B	0.9700	C21B—C22B	1.37 (3)
C10—C11	1.526 (4)	C21B—H21B	0.9300
C10—H10	0.9800	C22B—C23	1.415 (18)
C11—C12	1.499 (4)	C22B—H22B	0.9300
C11—C15	1.543 (4)	C23—O5B	1.340 (15)
C11—H11	0.9800	C23—C24	1.350 (6)
C12—O4	1.208 (3)	C23—O5A	1.411 (17)
C12—O1	1.347 (3)	C24—C25	1.377 (5)
C13—H13A	0.9600	C24—H24	0.9300
C13—H13B	0.9600	C25—H25	0.9300
C13—H13C	0.9600	O3—H3	0.8200
C14—H14A	0.9600	O5A—H5A1	0.8200
C14—H14B	0.9600	O5B—H5B1	0.8200
C14—H14C	0.9600

O1—C1—C2	107.0 (2)	N1—C15—C11	113.0 (2)
O1—C1—C10	106.13 (18)	N1—C15—H15A	109.0
C2—C1—C10	111.3 (2)	C11—C15—H15A	109.0
O1—C1—H1	110.7	N1—C15—H15B	109.0
C2—C1—H1	110.7	C11—C15—H15B	109.0
C10—C1—H1	110.7	H15A—C15—H15B	107.8
O2—C2—C3	59.74 (17)	N1—C16—C17	111.1 (3)
O2—C2—C1	120.0 (3)	N1—C16—H16A	109.4
C3—C2—C1	126.1 (3)	C17—C16—H16A	109.4
O2—C2—H2	113.5	N1—C16—H16B	109.4
C3—C2—H2	113.5	C17—C16—H16B	109.4
C1—C2—H2	113.5	H16A—C16—H16B	108.0
O2—C3—C2	59.63 (18)	N2—C17—C16	111.2 (3)
O2—C3—C13	112.6 (3)	N2—C17—H17A	109.4
C2—C3—C13	122.0 (3)	C16—C17—H17A	109.4
O2—C3—C4	116.5 (3)	N2—C17—H17B	109.4
C2—C3—C4	116.6 (3)	C16—C17—H17B	109.4
C13—C3—C4	116.5 (3)	H17A—C17—H17B	108.0
C3—C4—C5	111.8 (3)	N1—C18—C19	111.0 (3)
C3—C4—H4A	109.3	N1—C18—H18A	109.4
C5—C4—H4A	109.3	C19—C18—H18A	109.4
C3—C4—H4B	109.3	N1—C18—H18B	109.4
C5—C4—H4B	109.3	C19—C18—H18B	109.4
H4A—C4—H4B	107.9	H18A—C18—H18B	108.0
C6—C5—C4	111.4 (3)	N2—C19—C18	111.5 (3)
C6—C5—H5A	109.4	N2—C19—H19A	109.3
C4—C5—H5A	109.4	C18—C19—H19A	109.3
C6—C5—H5B	109.4	N2—C19—H19B	109.3
C4—C5—H5B	109.4	C18—C19—H19B	109.3
H5A—C5—H5B	108.0	H19A—C19—H19B	108.0
C7—C6—C5	128.8 (3)	C21A—C20—C25	115.6 (14)
C7—C6—H6	115.6	C21A—C20—N2	124.6 (14)
C5—C6—H6	115.6	C25—C20—N2	119.8 (3)
C6—C7—C14	126.0 (3)	C21A—C20—C21B	7 (2)
C6—C7—C8	121.7 (3)	C25—C20—C21B	117.1 (10)
C14—C7—C8	112.2 (3)	N2—C20—C21B	122.9 (10)
O3—C8—C7	111.4 (3)	C20—C21A—C22A	123 (2)
O3—C8—C9	111.2 (3)	C20—C21A—H21A	118.3
C7—C8—C9	110.7 (3)	C22A—C21A—H21A	118.3
O3—C8—H8	107.8	C23—C22A—C21A	124 (2)
C7—C8—H8	107.8	C23—C22A—H22A	118.2
C9—C8—H8	107.8	C21A—C22A—H22A	118.2
C10—C9—C8	116.9 (3)	C22B—C21B—C20	120.0 (17)
C10—C9—H9A	108.1	C22B—C21B—H21B	120.0
C8—C9—H9A	108.1	C20—C21B—H21B	120.0
C10—C9—H9B	108.1	C21B—C22B—C23	117.2 (17)
C8—C9—H9B	108.1	C21B—C22B—H22B	121.4
H9A—C9—H9B	107.3	C23—C22B—H22B	121.4
C11—C10—C9	114.5 (2)	C22A—C23—O5B	127.0 (17)
C11—C10—C1	102.9 (2)	C22A—C23—C24	115.0 (15)
C9—C10—C1	115.9 (2)	O5B—C23—C24	117.8 (8)
C11—C10—H10	107.7	C22A—C23—O5A	119.3 (17)
C9—C10—H10	107.7	O5B—C23—O5A	26.9 (13)
C1—C10—H10	107.7	C24—C23—O5A	120.6 (10)
C12—C11—C10	104.8 (2)	C22A—C23—C22B	13 (2)
C12—C11—C15	109.2 (2)	O5B—C23—C22B	116.5 (12)
C10—C11—C15	113.6 (3)	C24—C23—C22B	123.9 (9)
C12—C11—H11	109.7	O5A—C23—C22B	114.0 (11)
C10—C11—H11	109.7	C23—C24—C25	120.2 (4)
C15—C11—H11	109.7	C23—C24—H24	119.9
O4—C12—O1	120.6 (3)	C25—C24—H24	119.9
O4—C12—C11	128.4 (3)	C24—C25—C20	121.5 (4)
O1—C12—C11	110.9 (2)	C24—C25—H25	119.3
C3—C13—H13A	109.5	C20—C25—H25	119.3
C3—C13—H13B	109.5	C18—N1—C16	107.9 (2)
H13A—C13—H13B	109.5	C18—N1—C15	109.0 (2)
C3—C13—H13C	109.5	C16—N1—C15	112.3 (3)
H13A—C13—H13C	109.5	C20—N2—C17	116.9 (3)
H13B—C13—H13C	109.5	C20—N2—C19	115.6 (3)
C7—C14—H14A	109.5	C17—N2—C19	110.2 (2)
C7—C14—H14B	109.5	C12—O1—C1	110.8 (2)
H14A—C14—H14B	109.5	C2—O2—C3	60.63 (18)
C7—C14—H14C	109.5	C8—O3—H3	109.5
H14A—C14—H14C	109.5	C23—O5A—H5A1	109.5
H14B—C14—H14C	109.5	C23—O5B—H5B1	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1	0.82	2.22	3.030 (4)	169
C2—H2···O4ⁱ	0.98	2.45	3.243 (4)	138
C4—H4A···O2ⁱⁱ	0.97	2.43	3.315 (5)	151

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N1	0.82	2.22	3.030 (4)	169
C2—H2···O4ⁱ	0.98	2.45	3.243 (4)	138
C4—H4A···O2ⁱⁱ	0.97	2.43	3.315 (5)	151

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

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

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Volume 70| Part 5| May 2014| Pages o530-o531

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

9α-Hy­dr­oxy-12-{[4-(4-hy­dr­oxy­phen­yl)piperazin-1-yl]meth­yl}-4,8-di­methyl-3,14-dioxatri­cyclo­[9.3.0.02,4]tetra­dec-7-en-13-one

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

9α-Hydroxy-12-{[4-(4-hydroxyphenyl)piperazin-1-yl]methyl}-4,8-dimethyl-3,14-dioxatricyclo[9.3.0.0^2,4]tetradec-7-en-13-one