A cocrystal of 3α-hy­droxy­tirucalla-8,24-dien-21-oic acid and 3β-fluoro­tirucalla-7,24-dien-21-oic acid (0.897:0.103)

Yousuf, S.; Kamdem, R.S.T.; Wafo, P.; Ngadjui, B.T.; Fun, H.-K.

doi:10.1107/S1600536811011159

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o1015-o1016

doi:10.1107/S1600536811011159

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A cocrystal of 3α-hydroxytirucalla-8,24-dien-21-oic acid and 3β-fluorotirucalla-7,24-dien-21-oic acid (0.897:0.103)

S. Yousuf,^a R. S. T. Kamdem,^b P. Wafo,^b B. T. Ngadjui ^c and Hoong-Kun Fun ^d ^*‡

^aH.E.J Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, ^bDepartment of Chemistry, Higher Teachers Training College, University of Yaounde I, PO Box 48 Yaounde, Cameroon, ^cDepartment of Organic Chemistry, University of Yaounde I, PO Box 812 Yaounde, Cameroon, and ^dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 11 March 2011; accepted 25 March 2011; online 31 March 2011)

The title compound, 0.897C₃₀H₄₈O₃.0.103C₃₀H₄₇O₂F is a co-crystal of two triterpenes isolated from the resin of Canarium schweinfurthiiand Engl. Both triterpenes consists of four trans-fused rings having chair/half-chair/half-chair and envelope conformations. The molecular conformations are stabilized by intramolecular C—H⋯O hydrogen bonds, forming rings of S(7) graph-set motif. In the crystal, molecules are linked by intermolecular O—H⋯O and C—H⋯O interactions, forming sheets parallel to (001). All atoms. excepting the axially-oriented hydroxyl group in the major component and the equatorially-oriented fluorine atom in the minor component, are overlapping.

Related literature

For the crystal structure of 3α-hydroxytirucalla-7,24-diene-21-oic acid, see: Mora et al. (2001 ). For the crystal structure of 3α-hydroxytirucalla-8,24-diene-21-oic acid, see: Yousuf et al. (2011 ). For the biological activity of canarium schweinfurthiiand, see: Atawodi (2010); Dongmo et al. (2010 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

0.897C₃₀H₄₈O₃·0.103C₃₀H₄₇O₂F
M_r = 455.88
Trigonal, P 3₁ 21
a = 11.2868 (9) Å
c = 36.446 (3) Å
V = 4020.9 (5) Å³
Z = 6
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 100 K
0.29 × 0.24 × 0.13 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.980, T_max = 0.991
27808 measured reflections
4454 independent reflections
4347 reflections with I > 2σ(I)
R_int = 0.105

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.153
S = 1.18
4454 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2ⁱ	0.87	1.81	2.654 (3)	165
O3—H3A⋯O2ⁱⁱ	0.84	2.04	2.818 (4)	154
C12—H12B⋯O1	0.99	2.56	3.262 (4)	128
C22—H22A⋯O3ⁱⁱⁱ	0.99	2.40	3.300 (5)	151
Symmetry codes: (i) $[-x, -x+y, -z+{\script{1\over 3}}]$ ; (ii) x+1, y+1, z; (iii) x-1, y-1, z.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011159/rz2572sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011159/rz2572Isup2.hkl

checkCIF report

Comment top

The title compound is a co-crystal of two triterpenes namely 3α-hydroxytirucalla-7,24-dien-21-oic acid (or epielemadienolic acid, I) as a major component (89.7%) and 3β-fluorotirucalla- 7,24-dien-21-oic acid (II) as minor component (10.3%). The co-crystal was isolated during the phytochemical investigation of the dichloromethane soluble part of the resins of the medicinally important plant Canarium schweinfurthii of Cameroon. The plant has been used for the treatment of a wide range of ailments including malaria, fever and diarrhea (Atawodi, 2010; Dongmo et al., 2010). The refinement of the crystal structure revealed I and II as major (89.7%) and minor (10.3%) component, respectively with the difference that in II the axially oriented hydroxyl group attached to C3 has been replaced by the equatorially oriented fluorine atom. The asymmetric unit of the co-crystal (Fig. 1) consists of the mixture of I (Fig. 2) and II (Fig. 3). The crystal structure of the major component I has already been reported and the space group (P3₁21) and cell parameters were found to be similar to those previously reported (Mora et al.. 2001, Yousuf et al., 2011). However the minor component II was found to be a new triterpene. In both components the molecular structure showed that the trans fused rings A/B/C and D adopt chair [Q= 0.550 (4) Å, θ = 7.1 (4)° and ϕ = 88 (3)°] / half-chair [Q= 0.530 (4) Å, θ = 49.5 (4)° and ϕ = 323.5 (6)°] / half-chair [Q= 0.652 (4) Å, θ = 100.4 (4)° and ϕ = 83.8 (3)°] and envelope [Q= 0.483 (2)Å and ϕ = 10.7 (4)°] conformations respectively. The chair and envelop conformations of rings C and D are stabilized by C12—H12B···O1 intramolecular hydrogen bond. In the crystal structure, the molecules are linked to form two-dimensional molecular sheets via O3—H3A···O2, O1—H1O1···O2 and C22—H22A···O3 intermolecular hydrogen bonds (symmetry codes as in Table 1) and arranged parallel to the (001) plane (Fig.2).The absolute configuration was assigned on the basis of our recently published triterpene crystal data (Yousuf et al., 2011).

Related literature top

For the crystal structure of 3α-hydroxytirucalla-7,24-diene-21-oic acid, see: Mora et al. (2001). For the crystal structure of 3α-hydroxytirucalla-8,24-diene-21-oic acid, see: Yousuf et al. (2011). For the biological activity of canarium schweinfurthiiand, see: Atawodi (2010); Dongmo et al. (2010). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

The resin (100 g) of Canarium schweinfurthii Engl. was collected in Yaounde, Cameroon, in May 2010 and identified by Professor Noumi, a botanist at the Department of Biology, University of Yaounde-1. A voucher specimen (HNC 25918.) was deposited at the National Herbarium of Cameroon in Yaounde. The resin (100 g) of C. schweinfurthii was allowed to dry under shade and extracted with dichloromethane. The extract (70 g) was subjected to column chromatography over silica gel (300 g, 60 × 5 cm) eluting with hexane followed by a mixture of n-hexane–EtOAc in order to increase polarity. The fractions eluted were monitored by thin layer chromatography and similar fractions were combined to give seven fraction FrA-FrG. Fraction FrA (200 mg), obtained on elution with a mixture of n-hexane-EtOAc (8:2 v/v), was subjected to further column chromatography over silica gel (70 g, 60 cm³ × 3, hexane-acetone equimolar solution) to yield crystals of the title compound. Recrystallization from n-hexane gave colourless crystals (60 mg).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids. The intramolecular hydrogen bond is shown as a dashed line. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.
	Fig. 2. The molecular structure of the major component I, showing 50% probability displacement ellipsoids. The intramolecular hydrogen bond is shown as a dashed line. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.
	Fig. 3. The molecular structure of the minor component II, showing 50% probability displacement ellipsoids. Hydrogen atoms are omitted for clarity.
	Fig. 4. Crystal packing of the major component of the title compound, showing a two-dimensional molecular sheet parallel to the (001) plane. Only hydrogen atoms involved in hydrogen bonding (dashed lines) are shown.

3α-Hydroxytirucalla-8,24-dien-21-oic acid– 3β-fluorotirucalla-7,24-dien-21-oic acid (0.897:0.103) top

Crystal data top

0.897C₃₀H₄₈O₃·0.103C₃₀H₄₇O₂F	D_x = 1.130 Mg m⁻³
M_r = 455.88	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 10350 reflections
Hall symbol: p 31 2"	θ = 2.1–30.1°
a = 11.2868 (9) Å	µ = 0.07 mm⁻¹
c = 36.446 (3) Å	T = 100 K
V = 4020.9 (5) Å³	Block, colourles
Z = 6	0.29 × 0.24 × 0.13 mm
F(000) = 1506

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	4454 independent reflections
Radiation source: fine-focus sealed tube	4347 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.105
ϕ and ω scans	θ_max = 30.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→15
T_min = 0.980, T_max = 0.991	k = −13→15
27808 measured reflections	l = −51→38

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0644P)² + 1.6942P] where P = (F_o² + 2F_c²)/3
4454 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

0.897C₃₀H₄₈O₃·0.103C₃₀H₄₇O₂F	Z = 6
M_r = 455.88	Mo Kα radiation
Trigonal, P3₁21	µ = 0.07 mm⁻¹
a = 11.2868 (9) Å	T = 100 K
c = 36.446 (3) Å	0.29 × 0.24 × 0.13 mm
V = 4020.9 (5) Å³

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	4454 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4347 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.991	R_int = 0.105
27808 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.18	Δρ_max = 0.39 e Å⁻³
4454 reflections	Δρ_min = −0.33 e Å⁻³
316 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)
O1	0.1191 (2)	0.0008 (2)	0.12753 (5)	0.0221 (4)
H1O1	0.1119	−0.0077	0.1511	0.033*
O2	−0.1057 (2)	−0.0844 (2)	0.13357 (5)	0.0230 (4)
O3	0.6534 (3)	0.8965 (3)	0.10496 (7)	0.0330 (8)	0.898 (8)
H3A	0.7204	0.9158	0.1187	0.049*	0.898 (8)
F1	0.693 (3)	1.048 (3)	0.1287 (7)	0.042 (7)	0.102 (8)
C1	0.4098 (3)	0.7220 (4)	0.14860 (7)	0.0268 (7)
H1A	0.3651	0.6772	0.1720	0.032*
H1B	0.4651	0.6811	0.1403	0.032*
C2	0.5056 (4)	0.8752 (4)	0.15562 (8)	0.0335 (8)
H2A	0.4524	0.9153	0.1660	0.040*
H2B	0.5761	0.8875	0.1738	0.040*
C3	0.5750 (3)	0.9496 (4)	0.12011 (8)	0.0278 (7)
H3B	0.6369	1.0487	0.1257	0.033*	0.898 (8)
H3C	0.6079	0.8925	0.1103	0.033*	0.102 (8)
C4	0.4725 (3)	0.9373 (3)	0.09109 (9)	0.0249 (6)
C5	0.3685 (3)	0.7821 (3)	0.08498 (8)	0.0241 (6)
H5A	0.4249	0.7444	0.0746	0.029*
C6	0.2630 (5)	0.7560 (4)	0.05513 (13)	0.0500 (13)
H6A	0.2107	0.8014	0.0622	0.060*
H6B	0.3116	0.7979	0.0319	0.060*
C7	0.1654 (3)	0.6078 (3)	0.04875 (8)	0.0257 (6)
H7A	0.1104	0.5813	0.0273	0.031*
C8	0.1521 (3)	0.5079 (3)	0.07283 (8)	0.0217 (5)
C9	0.2374 (4)	0.5422 (3)	0.10692 (8)	0.0299 (7)
H9A	0.3193	0.5367	0.0989	0.036*
C10	0.2987 (3)	0.6922 (3)	0.11976 (8)	0.0206 (5)
C11	0.1746 (4)	0.4342 (3)	0.13671 (7)	0.0252 (6)
H11A	0.1766	0.4589	0.1617	0.030*
C12	0.1076 (4)	0.2838 (3)	0.12501 (7)	0.0277 (7)
H12A	0.0164	0.2323	0.1367	0.033*
H12B	0.1639	0.2453	0.1342	0.033*
C13	0.0908 (3)	0.2624 (3)	0.08335 (7)	0.0180 (5)
C14	0.0440 (3)	0.3596 (3)	0.06687 (7)	0.0176 (5)
C15	0.0125 (4)	0.3087 (3)	0.02691 (8)	0.0273 (6)
H15A	0.0967	0.3517	0.0119	0.033*
H15B	−0.0549	0.3301	0.0159	0.033*
C16	−0.0472 (3)	0.1517 (3)	0.02956 (7)	0.0237 (6)
H16A	0.0009	0.1221	0.0124	0.028*
H16B	−0.1458	0.1027	0.0234	0.028*
C17	−0.0255 (3)	0.1210 (3)	0.06995 (7)	0.0180 (5)
H17A	−0.1100	0.1000	0.0840	0.022*
C18	0.2267 (3)	0.2887 (4)	0.06574 (10)	0.0294 (7)
H18A	0.2646	0.2420	0.0801	0.044*
H18B	0.2920	0.3872	0.0654	0.044*
H18C	0.2094	0.2536	0.0406	0.044*
C19	0.1860 (4)	0.7155 (4)	0.13545 (15)	0.0473 (11)
H19A	0.1395	0.6511	0.1556	0.071*
H19B	0.1197	0.7011	0.1161	0.071*
H19C	0.2267	0.8094	0.1447	0.071*
C20	−0.0046 (3)	−0.0042 (3)	0.07384 (7)	0.0191 (5)
H20A	0.0854	0.0187	0.0627	0.023*
C21	−0.0021 (3)	−0.0331 (3)	0.11447 (7)	0.0184 (5)
C22	−0.1189 (3)	−0.1329 (3)	0.05494 (7)	0.0215 (5)
H22A	−0.2073	−0.1581	0.0668	0.026*
H22B	−0.1249	−0.1112	0.0289	0.026*
C23	−0.0965 (4)	−0.2561 (4)	0.05649 (9)	0.0274 (6)
H23A	−0.0041	−0.2285	0.0470	0.033*
H23B	−0.1006	−0.2846	0.0824	0.033*
C24	−0.2013 (4)	−0.3758 (4)	0.03450 (8)	0.0269 (6)
H24A	−0.1861	−0.3718	0.0088	0.032*
C25	−0.3113 (4)	−0.4852 (4)	0.04663 (8)	0.0288 (6)
C26	−0.3528 (5)	−0.5105 (6)	0.08649 (10)	0.0518 (12)
H26A	−0.2775	−0.4437	0.1018	0.078*
H26B	−0.3741	−0.6031	0.0933	0.078*
H26C	−0.4337	−0.5013	0.0903	0.078*
C27	−0.4081 (5)	−0.5985 (4)	0.02111 (11)	0.0418 (9)
H27A	−0.3788	−0.5722	−0.0043	0.063*
H27B	−0.5010	−0.6138	0.0242	0.063*
H27C	−0.4072	−0.6828	0.0269	0.063*
C28	0.5494 (4)	0.9980 (4)	0.05503 (9)	0.0338 (8)
H28A	0.6234	1.0919	0.0593	0.051*
H28B	0.4860	0.9982	0.0367	0.051*
H28C	0.5880	0.9425	0.0461	0.051*
C29	0.4101 (4)	1.0252 (4)	0.10225 (15)	0.0462 (10)
H29A	0.4819	1.1217	0.1028	0.069*
H29B	0.3689	0.9975	0.1267	0.069*
H29C	0.3397	1.0127	0.0844	0.069*
C30	−0.0905 (3)	0.3400 (3)	0.08398 (10)	0.0267 (6)
H30A	−0.1171	0.4003	0.0716	0.040*
H30B	−0.0763	0.3627	0.1102	0.040*
H30C	−0.1631	0.2446	0.0810	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0217 (10)	0.0320 (12)	0.0167 (7)	0.0165 (9)	0.0016 (8)	0.0012 (8)
O2	0.0198 (10)	0.0313 (11)	0.0140 (7)	0.0099 (9)	0.0026 (7)	0.0030 (8)
O3	0.0163 (12)	0.053 (2)	0.0305 (13)	0.0177 (13)	−0.0012 (10)	−0.0023 (13)
F1	0.040 (13)	0.043 (14)	0.053 (14)	0.029 (11)	−0.008 (11)	−0.003 (10)
C1	0.0229 (14)	0.0342 (17)	0.0131 (10)	0.0067 (13)	−0.0047 (10)	−0.0013 (11)
C2	0.0304 (16)	0.0350 (18)	0.0138 (11)	0.0003 (15)	−0.0012 (12)	−0.0055 (12)
C3	0.0149 (12)	0.0386 (18)	0.0187 (11)	0.0049 (13)	−0.0020 (11)	−0.0049 (12)
C4	0.0150 (12)	0.0214 (14)	0.0306 (14)	0.0033 (11)	−0.0048 (11)	−0.0039 (12)
C5	0.0181 (13)	0.0188 (13)	0.0281 (13)	0.0037 (11)	−0.0092 (11)	−0.0005 (11)
C6	0.042 (2)	0.0203 (16)	0.064 (3)	−0.0024 (15)	−0.035 (2)	0.0129 (17)
C7	0.0215 (13)	0.0218 (14)	0.0230 (12)	0.0027 (12)	−0.0109 (11)	0.0036 (12)
C8	0.0145 (12)	0.0195 (13)	0.0246 (12)	0.0036 (10)	−0.0066 (10)	0.0032 (11)
C9	0.0392 (18)	0.0205 (14)	0.0191 (11)	0.0068 (14)	−0.0115 (13)	0.0016 (11)
C10	0.0146 (12)	0.0222 (13)	0.0229 (11)	0.0078 (10)	−0.0029 (10)	−0.0015 (10)
C11	0.0350 (17)	0.0234 (13)	0.0114 (10)	0.0103 (13)	0.0001 (12)	0.0007 (10)
C12	0.045 (2)	0.0203 (13)	0.0131 (10)	0.0129 (14)	−0.0069 (13)	0.0013 (10)
C13	0.0182 (12)	0.0217 (13)	0.0133 (9)	0.0093 (11)	−0.0010 (9)	0.0026 (9)
C14	0.0158 (12)	0.0164 (12)	0.0139 (10)	0.0031 (10)	−0.0026 (9)	0.0020 (10)
C15	0.0366 (17)	0.0253 (14)	0.0160 (11)	0.0125 (14)	−0.0072 (12)	0.0045 (11)
C16	0.0257 (14)	0.0232 (14)	0.0157 (10)	0.0075 (12)	−0.0049 (11)	0.0005 (11)
C17	0.0177 (12)	0.0189 (12)	0.0128 (9)	0.0056 (10)	0.0007 (9)	0.0007 (9)
C18	0.0154 (13)	0.0244 (16)	0.0435 (17)	0.0062 (12)	0.0006 (13)	0.0051 (14)
C19	0.0253 (17)	0.0253 (17)	0.090 (3)	0.0118 (15)	0.022 (2)	0.010 (2)
C20	0.0190 (12)	0.0225 (13)	0.0137 (9)	0.0088 (11)	0.0023 (9)	0.0024 (10)
C21	0.0219 (13)	0.0179 (12)	0.0159 (9)	0.0104 (11)	0.0010 (10)	−0.0002 (9)
C22	0.0256 (14)	0.0227 (13)	0.0142 (9)	0.0107 (12)	−0.0007 (10)	−0.0005 (10)
C23	0.0264 (15)	0.0269 (16)	0.0289 (14)	0.0134 (13)	0.0018 (12)	−0.0012 (12)
C24	0.0357 (18)	0.0276 (15)	0.0185 (11)	0.0166 (14)	0.0020 (12)	−0.0010 (11)
C25	0.0286 (16)	0.0325 (16)	0.0245 (13)	0.0147 (14)	−0.0019 (12)	−0.0009 (12)
C26	0.033 (2)	0.068 (3)	0.0296 (16)	0.007 (2)	0.0078 (16)	0.0082 (19)
C27	0.040 (2)	0.036 (2)	0.0409 (18)	0.0125 (18)	−0.0050 (17)	−0.0098 (17)
C28	0.0324 (18)	0.0280 (16)	0.0263 (14)	0.0041 (14)	−0.0089 (13)	0.0011 (13)
C29	0.0299 (19)	0.0209 (16)	0.084 (3)	0.0097 (15)	0.005 (2)	0.0034 (19)
C30	0.0164 (13)	0.0207 (14)	0.0383 (16)	0.0059 (12)	0.0006 (12)	0.0005 (13)

Geometric parameters (Å, º) top

O1—C21	1.312 (4)	C14—C30	1.552 (4)
O1—H1O1	0.8651	C15—C16	1.552 (5)
O2—C21	1.229 (3)	C15—H15A	0.9900
O3—C3	1.406 (5)	C15—H15B	0.9900
O3—H3A	0.8400	C16—C17	1.559 (4)
O3—H3C	0.5288	C16—H16A	0.9900
F1—C3	1.27 (3)	C16—H16B	0.9900
C1—C2	1.534 (5)	C17—C20	1.551 (4)
C1—C10	1.539 (4)	C17—H17A	1.0000
C1—H1A	0.9900	C18—H18A	0.9800
C1—H1B	0.9900	C18—H18B	0.9800
C2—C3	1.529 (4)	C18—H18C	0.9800
C2—H2A	0.9900	C19—H19A	0.9800
C2—H2B	0.9900	C19—H19B	0.9800
C3—C4	1.521 (4)	C19—H19C	0.9800
C3—H3B	1.0000	C20—C21	1.519 (3)
C3—H3C	0.9601	C20—C22	1.541 (4)
C4—C29	1.532 (5)	C20—H20A	1.0000
C4—C28	1.535 (5)	C22—C23	1.533 (5)
C4—C5	1.562 (4)	C22—H22A	0.9900
C5—C6	1.528 (4)	C22—H22B	0.9900
C5—C10	1.568 (4)	C23—C24	1.506 (5)
C5—H5A	1.0000	C23—H23A	0.9900
C6—C7	1.491 (5)	C23—H23B	0.9900
C6—H6A	0.9900	C24—C25	1.314 (5)
C6—H6B	0.9900	C24—H24A	0.9500
C7—C8	1.376 (4)	C25—C26	1.509 (5)
C7—H7A	0.9500	C25—C27	1.516 (5)
C8—C9	1.499 (4)	C26—H26A	0.9800
C8—C14	1.516 (4)	C26—H26B	0.9800
C9—C11	1.517 (4)	C26—H26C	0.9800
C9—C10	1.547 (4)	C27—H27A	0.9800
C9—H9A	1.0000	C27—H27B	0.9800
C10—C19	1.533 (5)	C27—H27C	0.9800
C11—C12	1.534 (4)	C28—H28A	0.9800
C11—H11A	0.9500	C28—H28B	0.9800
C12—C13	1.534 (4)	C28—H28C	0.9800
C12—H12A	0.9900	C29—H29A	0.9800
C12—H12B	0.9900	C29—H29B	0.9800
C13—C18	1.548 (4)	C29—H29C	0.9800
C13—C17	1.554 (4)	C30—H30A	0.9800
C13—C14	1.556 (4)	C30—H30B	0.9800
C14—C15	1.540 (4)	C30—H30C	0.9800

C21—O1—H1O1	107.6	C14—C15—C16	104.7 (2)
C3—O3—H3A	109.5	C14—C15—H15A	110.8
C3—O3—H3C	26.1	C16—C15—H15A	110.8
H3A—O3—H3C	121.0	C14—C15—H15B	110.8
C2—C1—C10	113.4 (3)	C16—C15—H15B	110.8
C2—C1—H1A	108.9	H15A—C15—H15B	108.9
C10—C1—H1A	108.9	C15—C16—C17	106.6 (2)
C2—C1—H1B	108.9	C15—C16—H16A	110.4
C10—C1—H1B	108.9	C17—C16—H16A	110.4
H1A—C1—H1B	107.7	C15—C16—H16B	110.4
C3—C2—C1	110.9 (2)	C17—C16—H16B	110.4
C3—C2—H2A	109.5	H16A—C16—H16B	108.6
C1—C2—H2A	109.5	C20—C17—C13	118.1 (2)
C3—C2—H2B	109.5	C20—C17—C16	113.6 (2)
C1—C2—H2B	109.5	C13—C17—C16	102.4 (2)
H2A—C2—H2B	108.0	C20—C17—H17A	107.4
F1—C3—O3	82.0 (11)	C13—C17—H17A	107.4
F1—C3—C4	131.7 (11)	C16—C17—H17A	107.4
O3—C3—C4	107.4 (2)	C13—C18—H18A	109.5
F1—C3—C2	107.2 (11)	C13—C18—H18B	109.5
O3—C3—C2	110.9 (3)	H18A—C18—H18B	109.5
C4—C3—C2	112.4 (3)	C13—C18—H18C	109.5
F1—C3—H3B	30.0	H18A—C18—H18C	109.5
O3—C3—H3B	108.7	H18B—C18—H18C	109.5
C4—C3—H3B	108.7	C10—C19—H19A	109.5
C2—C3—H3B	108.7	C10—C19—H19B	109.5
F1—C3—H3C	95.1	H19A—C19—H19B	109.5
O3—C3—H3C	14.0	C10—C19—H19C	109.5
C4—C3—H3C	102.1	H19A—C19—H19C	109.5
C2—C3—H3C	102.2	H19B—C19—H19C	109.5
H3B—C3—H3C	122.6	C21—C20—C22	109.3 (2)
C3—C4—C29	109.3 (3)	C21—C20—C17	108.2 (2)
C3—C4—C28	108.7 (3)	C22—C20—C17	112.4 (2)
C29—C4—C28	106.2 (3)	C21—C20—H20A	109.0
C3—C4—C5	108.2 (3)	C22—C20—H20A	109.0
C29—C4—C5	115.7 (3)	C17—C20—H20A	109.0
C28—C4—C5	108.6 (3)	O2—C21—O1	122.7 (2)
C6—C5—C4	113.2 (3)	O2—C21—C20	122.5 (3)
C6—C5—C10	111.1 (3)	O1—C21—C20	114.8 (2)
C4—C5—C10	117.6 (2)	C23—C22—C20	113.5 (3)
C6—C5—H5A	104.5	C23—C22—H22A	108.9
C4—C5—H5A	104.5	C20—C22—H22A	108.9
C10—C5—H5A	104.5	C23—C22—H22B	108.9
C7—C6—C5	113.2 (3)	C20—C22—H22B	108.9
C7—C6—H6A	108.9	H22A—C22—H22B	107.7
C5—C6—H6A	108.9	C24—C23—C22	112.5 (3)
C7—C6—H6B	108.9	C24—C23—H23A	109.1
C5—C6—H6B	108.9	C22—C23—H23A	109.1
H6A—C6—H6B	107.7	C24—C23—H23B	109.1
C8—C7—C6	122.4 (3)	C22—C23—H23B	109.1
C8—C7—H7A	118.8	H23A—C23—H23B	107.8
C6—C7—H7A	118.8	C25—C24—C23	127.8 (3)
C7—C8—C9	121.6 (3)	C25—C24—H24A	116.1
C7—C8—C14	120.8 (2)	C23—C24—H24A	116.1
C9—C8—C14	117.5 (2)	C24—C25—C26	124.0 (3)
C8—C9—C11	113.8 (3)	C24—C25—C27	122.0 (3)
C8—C9—C10	114.3 (3)	C26—C25—C27	114.0 (3)
C11—C9—C10	115.9 (2)	C25—C26—H26A	109.5
C8—C9—H9A	103.6	C25—C26—H26B	109.5
C11—C9—H9A	103.6	H26A—C26—H26B	109.5
C10—C9—H9A	103.6	C25—C26—H26C	109.5
C19—C10—C1	111.3 (3)	H26A—C26—H26C	109.5
C19—C10—C9	110.2 (3)	H26B—C26—H26C	109.5
C1—C10—C9	108.4 (3)	C25—C27—H27A	109.5
C19—C10—C5	112.4 (3)	C25—C27—H27B	109.5
C1—C10—C5	108.7 (2)	H27A—C27—H27B	109.5
C9—C10—C5	105.6 (2)	C25—C27—H27C	109.5
C9—C11—C12	117.6 (2)	H27A—C27—H27C	109.5
C9—C11—H11A	121.2	H27B—C27—H27C	109.5
C12—C11—H11A	121.2	C4—C28—H28A	109.5
C11—C12—C13	113.8 (2)	C4—C28—H28B	109.5
C11—C12—H12A	108.8	H28A—C28—H28B	109.5
C13—C12—H12A	108.8	C4—C28—H28C	109.5
C11—C12—H12B	108.8	H28A—C28—H28C	109.5
C13—C12—H12B	108.8	H28B—C28—H28C	109.5
H12A—C12—H12B	107.7	C4—C29—H29A	109.5
C12—C13—C18	110.3 (3)	C4—C29—H29B	109.5
C12—C13—C17	116.6 (2)	H29A—C29—H29B	109.5
C18—C13—C17	108.3 (2)	C4—C29—H29C	109.5
C12—C13—C14	109.3 (2)	H29A—C29—H29C	109.5
C18—C13—C14	111.0 (2)	H29B—C29—H29C	109.5
C17—C13—C14	101.1 (2)	C14—C30—H30A	109.5
C8—C14—C15	117.1 (2)	C14—C30—H30B	109.5
C8—C14—C30	106.8 (3)	H30A—C30—H30B	109.5
C15—C14—C30	107.4 (3)	C14—C30—H30C	109.5
C8—C14—C13	110.7 (2)	H30A—C30—H30C	109.5
C15—C14—C13	101.5 (2)	H30B—C30—H30C	109.5
C30—C14—C13	113.4 (2)

C10—C1—C2—C3	−57.4 (4)	C9—C11—C12—C13	−10.5 (5)
C1—C2—C3—F1	−148.0 (12)	C11—C12—C13—C18	81.3 (4)
C1—C2—C3—O3	−60.1 (4)	C11—C12—C13—C17	−154.6 (3)
C1—C2—C3—C4	60.2 (4)	C11—C12—C13—C14	−40.9 (4)
F1—C3—C4—C29	−70.9 (16)	C7—C8—C14—C15	35.8 (4)
O3—C3—C4—C29	−165.7 (3)	C9—C8—C14—C15	−147.8 (3)
C2—C3—C4—C29	72.0 (4)	C7—C8—C14—C30	−84.6 (4)
F1—C3—C4—C28	44.6 (16)	C9—C8—C14—C30	91.8 (3)
O3—C3—C4—C28	−50.3 (4)	C7—C8—C14—C13	151.4 (3)
C2—C3—C4—C28	−172.6 (3)	C9—C8—C14—C13	−32.2 (4)
F1—C3—C4—C5	162.4 (15)	C12—C13—C14—C8	63.1 (3)
O3—C3—C4—C5	67.5 (3)	C18—C13—C14—C8	−58.8 (3)
C2—C3—C4—C5	−54.8 (4)	C17—C13—C14—C8	−173.5 (2)
C3—C4—C5—C6	−177.7 (3)	C12—C13—C14—C15	−171.9 (3)
C29—C4—C5—C6	59.3 (5)	C18—C13—C14—C15	66.2 (3)
C28—C4—C5—C6	−59.9 (4)	C17—C13—C14—C15	−48.5 (3)
C3—C4—C5—C10	50.5 (4)	C12—C13—C14—C30	−57.0 (3)
C29—C4—C5—C10	−72.5 (4)	C18—C13—C14—C30	−178.9 (3)
C28—C4—C5—C10	168.3 (3)	C17—C13—C14—C30	66.4 (3)
C4—C5—C6—C7	178.8 (4)	C8—C14—C15—C16	156.0 (3)
C10—C5—C6—C7	−46.3 (5)	C30—C14—C15—C16	−83.9 (3)
C5—C6—C7—C8	14.2 (6)	C13—C14—C15—C16	35.4 (3)
C6—C7—C8—C9	−1.1 (6)	C14—C15—C16—C17	−9.2 (3)
C6—C7—C8—C14	175.2 (4)	C12—C13—C17—C20	−73.7 (3)
C7—C8—C9—C11	157.2 (3)	C18—C13—C17—C20	51.4 (3)
C14—C8—C9—C11	−19.2 (4)	C14—C13—C17—C20	168.0 (2)
C7—C8—C9—C10	21.0 (5)	C12—C13—C17—C16	160.6 (3)
C14—C8—C9—C10	−155.4 (3)	C18—C13—C17—C16	−74.3 (3)
C2—C1—C10—C19	−74.9 (3)	C14—C13—C17—C16	42.4 (3)
C2—C1—C10—C9	163.8 (3)	C15—C16—C17—C20	−149.2 (3)
C2—C1—C10—C5	49.5 (3)	C15—C16—C17—C13	−20.7 (3)
C8—C9—C10—C19	71.6 (4)	C13—C17—C20—C21	66.8 (3)
C11—C9—C10—C19	−63.7 (4)	C16—C17—C20—C21	−173.3 (2)
C8—C9—C10—C1	−166.4 (3)	C13—C17—C20—C22	−172.4 (2)
C11—C9—C10—C1	58.4 (4)	C16—C17—C20—C22	−52.5 (3)
C8—C9—C10—C5	−50.0 (4)	C22—C20—C21—O2	−49.3 (4)
C11—C9—C10—C5	174.7 (3)	C17—C20—C21—O2	73.4 (4)
C6—C5—C10—C19	−56.8 (4)	C22—C20—C21—O1	130.6 (3)
C4—C5—C10—C19	75.9 (4)	C17—C20—C21—O1	−106.7 (3)
C6—C5—C10—C1	179.5 (3)	C21—C20—C22—C23	−63.1 (3)
C4—C5—C10—C1	−47.7 (4)	C17—C20—C22—C23	176.8 (2)
C6—C5—C10—C9	63.4 (4)	C20—C22—C23—C24	−174.0 (2)
C4—C5—C10—C9	−163.9 (3)	C22—C23—C24—C25	−99.7 (4)
C8—C9—C11—C12	42.2 (5)	C23—C24—C25—C26	−0.2 (7)
C10—C9—C11—C12	177.7 (3)	C23—C24—C25—C27	−179.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	0.87	1.81	2.654 (3)	165
O3—H3A···O2ⁱⁱ	0.84	2.04	2.818 (4)	154
C12—H12B···O1	0.99	2.56	3.262 (4)	128
C22—H22A···O3ⁱⁱⁱ	0.99	2.40	3.300 (5)	151

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

Experimental details

Crystal data
Chemical formula	0.897C₃₀H₄₈O₃·0.103C₃₀H₄₇O₂F
M_r	455.88
Crystal system, space group	Trigonal, P3₁21
Temperature (K)	100
a, c (Å)	11.2868 (9), 36.446 (3)
V (Å³)	4020.9 (5)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.29 × 0.24 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.980, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	27808, 4454, 4347
R_int	0.105
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.153, 1.18
No. of reflections	4454
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.33

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	0.87	1.81	2.654 (3)	165
O3—H3A···O2ⁱⁱ	0.84	2.04	2.818 (4)	154
C12—H12B···O1	0.99	2.56	3.262 (4)	128
C22—H22A···O3ⁱⁱⁱ	0.99	2.40	3.300 (5)	151

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

RSTK thanks the H.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, for providing research facilities. SY thanks the School of Physics, Universiti Sains Malaysia, for providing X-ray diffraction research facilities. HKF thanks the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

References

Atawodi, S. E. (2010). Adv. Biol. Res. 4, 314–322. CAS Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Dongmo, P. M., Tchoumbougnang, F., Ndongson, B., Agwannande, W., Sandjon, B., Zollo, P. H. A. & Menut, C. (2010). Agri. Biol. J. N. Am. 1 pp. 606–6011. Google Scholar
Mora, A. J., Delgado, G., Díaz de Delgado, G., Usubillaga, A., Khouri, N. & Bahsas, A. (2001). Acta Cryst. C57, 638–640. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yousuf, S., Kamdem, R. S. T., Ngadjui, B. T., Wafo, P. & Fun, H.-K. (2011). Acta Cryst. E67, o937–o938. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 67| Part 4| April 2011| Pages o1015-o1016

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

A cocrystal of 3α-hy­dr­oxy­tirucalla-8,24-dien-21-oic acid and 3β-fluoro­tirucalla-7,24-dien-21-oic acid (0.897:0.103)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

A cocrystal of 3α-hydroxytirucalla-8,24-dien-21-oic acid and 3β-fluorotirucalla-7,24-dien-21-oic acid (0.897:0.103)