Dihalogenated trichodermin (4β-acet-oxy-9,10-dibromo-12,13-epoxy-tri-chothec).

In the title dihalogenated trichodermin mol-ecule, C(17)H(24)Br(2)O(4) (systematic name: 9,10-dibromo-12,13-epoxy-trichothec-9-en-4β-yl acetate), the five-membered ring displays an envelope conformation, whereas the two six-membered rings show the same conformation, viz. chair. As for the seven-membered ring, the dihedral angle between the mean planes formed by the four C atoms of the envelope unit and the three C and one O atoms of the six-membered chair is 69.08 (4)°; these two mean planes are nearly perpendicular to the ep-oxy ring with angles of 87.53 (4) and 88.67 (4)°, respectively.

Related literature

For the fungicidal activity of trichodermin, see: Zhang et al. (2007 ▶). Trichodermin is a member of the 4β-ace­oxy-12,13-epoxy­trichothecene family, see: Nielsen et al. (2005 ▶). For the structure of trichodermin, see: Chen et al. (2008 ▶) and for the structure of a trichodermin derivative, see: Cheng et al. (2009 ▶).

Experimental

Crystal data

C17H24Br2O4

M = 452.18

Monoclinic,

a = 10.0120 (4) Å

b = 8.3397 (4) Å

c = 11.1235 (6) Å

β = 106.6220 (10)°

V = 889.97 (7) Å3

Z = 2

Mo Kα radiation

μ = 4.57 mm−1

T = 296 K

0.26 × 0.20 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR: Higashi, 1995 ▶) T min = 0.323, T max = 0.633

8698 measured reflections

3667 independent reflections

2752 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.095

S = 1.00

3667 reflections

213 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.67 e Å−3

Δρmin = −0.65 e Å−3

Absolute structure: Flack (1983 ▶), 1506 Friedel pairs

Flack parameter: 0.000 (15)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054178/si2228sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054178/si2228Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H24Br2O4	F(000) = 456
Mr = 452.18	Dx = 1.687 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6808 reflections
a = 10.0120 (4) Å	θ = 3.1–27.4°
b = 8.3397 (4) Å	µ = 4.57 mm−1
c = 11.1235 (6) Å	T = 296 K
β = 106.622 (1)°	Chunk, colorless
V = 889.97 (7) Å3	0.26 × 0.20 × 0.10 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	3667 independent reflections
Radiation source: rolling anode	2752 reflections with I > 2σ(I)
graphite	Rint = 0.032
Detector resolution: 10.00 pixels mm-1	θmax = 27.4°, θmin = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR: Higashi, 1995)	k = −10→10
Tmin = 0.323, Tmax = 0.633	l = −14→14
8698 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2) + (0.0003P)2 + 1.980P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.095	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.67 e Å−3
3667 reflections	Δρmin = −0.65 e Å−3
213 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0189 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1506 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.000 (15)

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.

	x	y	z	Uiso*/Ueq
Br2	0.88801 (4)	0.21090 (8)	0.71835 (5)	0.06304 (15)
Br1	0.75860 (5)	−0.28303 (7)	0.84118 (5)	0.05950 (14)
O2	0.2048 (3)	−0.0632 (4)	0.6936 (3)	0.0520 (9)
O1	0.5492 (3)	−0.0758 (3)	0.6377 (3)	0.0377 (7)
O3	0.2174 (3)	0.2951 (4)	0.5751 (3)	0.0459 (9)
C11	0.6197 (4)	0.0702 (5)	0.6879 (5)	0.0376 (10)
H11	0.6071	0.1471	0.6189	0.045*
O4	0.3167 (4)	0.5380 (4)	0.6153 (5)	0.0713 (13)
C7	0.6122 (5)	0.0479 (6)	0.9123 (4)	0.0408 (11)
H7A	0.5826	0.1011	0.9779	0.049*
H7B	0.5681	−0.0567	0.8986	0.049*
C6	0.5623 (4)	0.1472 (5)	0.7900 (4)	0.0353 (10)
C12	0.3494 (4)	−0.0260 (5)	0.7073 (4)	0.0378 (10)
C2	0.3997 (4)	−0.0627 (5)	0.5960 (4)	0.0351 (10)
H2	0.3575	−0.1619	0.5549	0.042*
C5	0.3968 (4)	0.1468 (5)	0.7378 (4)	0.0344 (9)
C13	0.3133 (5)	−0.1439 (7)	0.7910 (5)	0.0545 (14)
H13A	0.3312	−0.2561	0.7786	0.065*
H13B	0.3253	−0.1129	0.8775	0.065*
C15	0.6110 (5)	0.3216 (6)	0.8173 (5)	0.0486 (14)
H15A	0.7107	0.3243	0.8497	0.073*
H15B	0.5702	0.3664	0.8781	0.073*
H15C	0.5825	0.3831	0.7413	0.073*
C8	0.7705 (5)	0.0260 (6)	0.9561 (4)	0.0430 (12)
H8A	0.8141	0.1303	0.9755	0.052*
H8B	0.7950	−0.0367	1.0328	0.052*
C17	0.2139 (5)	0.4560 (6)	0.5912 (5)	0.0469 (12)
C10	0.7743 (5)	0.0191 (6)	0.7299 (5)	0.0419 (11)
H10	0.7879	−0.0600	0.6693	0.050*
C18	0.0687 (6)	0.5157 (7)	0.5733 (6)	0.0670 (17)
H18A	0.0335	0.4743	0.6388	0.100*
H18B	0.0103	0.4804	0.4934	0.100*
H18C	0.0692	0.6307	0.5762	0.100*
C4	0.3545 (4)	0.2220 (7)	0.6039 (4)	0.0385 (9)
H4	0.4240	0.3011	0.5963	0.046*
C14	0.3263 (4)	0.2247 (8)	0.8282 (4)	0.0471 (10)
H14A	0.2275	0.2070	0.7987	0.071*
H14B	0.3448	0.3378	0.8327	0.071*
H14C	0.3623	0.1781	0.9100	0.071*
C9	0.8282 (5)	−0.0555 (6)	0.8612 (5)	0.0431 (12)
C3	0.3483 (5)	0.0813 (5)	0.5121 (4)	0.0401 (11)
H3A	0.2538	0.0644	0.4596	0.048*
H3B	0.4080	0.1018	0.4588	0.048*
C16	0.9878 (5)	−0.0734 (8)	0.9074 (6)	0.0654 (17)
H16A	1.0299	0.0307	0.9240	0.098*
H16B	1.0199	−0.1260	0.8441	0.098*
H16C	1.0130	−0.1361	0.9829	0.098*

	U11	U22	U33	U12	U13	U23
Br2	0.0445 (2)	0.0665 (3)	0.0795 (3)	−0.0133 (4)	0.0199 (2)	0.0144 (4)
Br1	0.0729 (3)	0.0375 (2)	0.0607 (3)	0.0006 (4)	0.0071 (2)	0.0039 (3)
O2	0.0365 (16)	0.058 (2)	0.060 (2)	−0.0100 (17)	0.0112 (15)	0.0042 (18)
O1	0.0380 (15)	0.0318 (16)	0.0433 (17)	−0.0010 (14)	0.0116 (12)	−0.0068 (13)
O3	0.0347 (16)	0.0360 (17)	0.061 (2)	0.0020 (14)	0.0032 (15)	0.0043 (15)
C11	0.032 (2)	0.030 (2)	0.049 (3)	−0.0038 (19)	0.0086 (19)	0.0006 (19)
O4	0.058 (2)	0.036 (2)	0.118 (4)	−0.0057 (19)	0.021 (2)	−0.010 (2)
C7	0.038 (2)	0.047 (3)	0.036 (2)	−0.006 (2)	0.0077 (18)	0.0024 (19)
C6	0.036 (2)	0.031 (2)	0.038 (2)	−0.0035 (18)	0.0074 (17)	−0.0069 (18)
C12	0.0303 (19)	0.031 (2)	0.049 (3)	−0.0030 (19)	0.0062 (18)	0.0009 (19)
C2	0.036 (2)	0.034 (2)	0.034 (2)	−0.007 (2)	0.0081 (17)	−0.0089 (18)
C5	0.0346 (19)	0.030 (2)	0.038 (2)	−0.0037 (18)	0.0105 (17)	0.0000 (17)
C13	0.056 (3)	0.047 (3)	0.054 (3)	−0.014 (3)	0.006 (2)	0.007 (2)
C15	0.048 (3)	0.033 (2)	0.062 (3)	−0.005 (2)	0.010 (2)	−0.006 (2)
C8	0.040 (2)	0.043 (3)	0.041 (3)	−0.005 (2)	0.0032 (19)	0.000 (2)
C17	0.045 (3)	0.034 (2)	0.060 (3)	0.003 (2)	0.014 (2)	0.004 (2)
C10	0.037 (2)	0.038 (2)	0.052 (3)	−0.004 (2)	0.016 (2)	0.005 (2)
C18	0.052 (3)	0.053 (3)	0.097 (5)	0.014 (3)	0.024 (3)	0.012 (3)
C4	0.0332 (17)	0.033 (2)	0.047 (2)	−0.003 (3)	0.0073 (15)	0.001 (3)
C14	0.0443 (19)	0.052 (3)	0.049 (2)	0.001 (3)	0.0197 (17)	−0.012 (3)
C9	0.032 (2)	0.042 (3)	0.049 (3)	0.000 (2)	0.0023 (19)	−0.001 (2)
C3	0.046 (2)	0.043 (3)	0.030 (2)	−0.001 (2)	0.0093 (19)	−0.0010 (18)
C16	0.040 (3)	0.075 (4)	0.075 (4)	0.008 (3)	0.005 (3)	0.005 (3)

Br2—C10	1.989 (5)	C13—H13A	0.9700
Br1—C9	2.012 (5)	C13—H13B	0.9700
O2—C12	1.445 (5)	C15—H15A	0.9600
O2—C13	1.461 (6)	C15—H15B	0.9600
O1—C11	1.438 (5)	C15—H15C	0.9600
O1—C2	1.439 (5)	C8—C9	1.503 (7)
O3—C17	1.355 (6)	C8—H8A	0.9700
O3—C4	1.451 (5)	C8—H8B	0.9700
C11—C10	1.544 (6)	C17—C18	1.494 (7)
C11—C6	1.551 (7)	C10—C9	1.536 (7)
C11—H11	0.9800	C10—H10	0.9800
O4—C17	1.200 (6)	C18—H18A	0.9600
C7—C8	1.530 (6)	C18—H18B	0.9600
C7—C6	1.548 (6)	C18—H18C	0.9600
C7—H7A	0.9700	C4—C3	1.546 (7)
C7—H7B	0.9700	C4—H4	0.9800
C6—C15	1.536 (6)	C14—H14A	0.9600
C6—C5	1.592 (6)	C14—H14B	0.9600
C12—C13	1.469 (7)	C14—H14C	0.9600
C12—C2	1.496 (6)	C9—C16	1.539 (6)
C12—C5	1.524 (6)	C3—H3A	0.9700
C2—C3	1.518 (6)	C3—H3B	0.9700
C2—H2	0.9800	C16—H16A	0.9600
C5—C14	1.529 (6)	C16—H16B	0.9600
C5—C4	1.558 (6)	C16—H16C	0.9600
C12—O2—C13	60.7 (3)	C9—C8—C7	113.7 (4)
C11—O1—C2	114.3 (3)	C9—C8—H8A	108.8
C17—O3—C4	116.4 (4)	C7—C8—H8A	108.8
O1—C11—C10	102.8 (3)	C9—C8—H8B	108.8
O1—C11—C6	113.1 (3)	C7—C8—H8B	108.8
C10—C11—C6	116.2 (4)	H8A—C8—H8B	107.7
O1—C11—H11	108.1	O4—C17—O3	122.7 (4)
C10—C11—H11	108.1	O4—C17—C18	125.4 (5)
C6—C11—H11	108.1	O3—C17—C18	111.9 (4)
C8—C7—C6	112.9 (4)	C9—C10—C11	116.7 (4)
C8—C7—H7A	109.0	C9—C10—Br2	109.6 (3)
C6—C7—H7A	109.0	C11—C10—Br2	107.5 (3)
C8—C7—H7B	109.0	C9—C10—H10	107.6
C6—C7—H7B	109.0	C11—C10—H10	107.6
H7A—C7—H7B	107.8	Br2—C10—H10	107.6
C15—C6—C7	109.1 (4)	C17—C18—H18A	109.5
C15—C6—C11	112.0 (4)	C17—C18—H18B	109.5
C7—C6—C11	109.2 (4)	H18A—C18—H18B	109.5
C15—C6—C5	108.2 (3)	C17—C18—H18C	109.5
C7—C6—C5	111.1 (4)	H18A—C18—H18C	109.5
C11—C6—C5	107.3 (3)	H18B—C18—H18C	109.5
O2—C12—C13	60.2 (3)	O3—C4—C3	108.5 (3)
O2—C12—C2	115.7 (4)	O3—C4—C5	111.2 (3)
C13—C12—C2	126.1 (4)	C3—C4—C5	105.9 (4)
O2—C12—C5	117.7 (4)	O3—C4—H4	110.4
C13—C12—C5	127.5 (4)	C3—C4—H4	110.4
C2—C12—C5	102.8 (4)	C5—C4—H4	110.4
O1—C2—C12	108.3 (3)	C5—C14—H14A	109.5
O1—C2—C3	113.3 (4)	C5—C14—H14B	109.5
C12—C2—C3	102.2 (4)	H14A—C14—H14B	109.5
O1—C2—H2	110.9	C5—C14—H14C	109.5
C12—C2—H2	110.9	H14A—C14—H14C	109.5
C3—C2—H2	110.9	H14B—C14—H14C	109.5
C12—C5—C14	112.0 (4)	C8—C9—C10	112.6 (4)
C12—C5—C4	100.7 (4)	C8—C9—C16	112.4 (4)
C14—C5—C4	114.0 (4)	C10—C9—C16	113.9 (4)
C12—C5—C6	108.0 (3)	C8—C9—Br1	108.3 (3)
C14—C5—C6	112.8 (3)	C10—C9—Br1	105.1 (3)
C4—C5—C6	108.5 (3)	C16—C9—Br1	103.8 (3)
O2—C13—C12	59.1 (3)	C2—C3—C4	104.6 (4)
O2—C13—H13A	117.9	C2—C3—H3A	110.8
C12—C13—H13A	117.9	C4—C3—H3A	110.8
O2—C13—H13B	117.9	C2—C3—H3B	110.8
C12—C13—H13B	117.9	C4—C3—H3B	110.8
H13A—C13—H13B	115.0	H3A—C3—H3B	108.9
C6—C15—H15A	109.5	C9—C16—H16A	109.5
C6—C15—H15B	109.5	C9—C16—H16B	109.5
H15A—C15—H15B	109.5	H16A—C16—H16B	109.5
C6—C15—H15C	109.5	C9—C16—H16C	109.5
H15A—C15—H15C	109.5	H16A—C16—H16C	109.5
H15B—C15—H15C	109.5	H16B—C16—H16C	109.5
C2—O1—C11—C10	177.3 (4)	C11—C6—C5—C14	−178.3 (4)
C2—O1—C11—C6	51.2 (5)	C15—C6—C5—C4	70.1 (5)
C8—C7—C6—C15	−68.6 (5)	C7—C6—C5—C4	−170.1 (4)
C8—C7—C6—C11	54.1 (5)	C11—C6—C5—C4	−50.9 (5)
C8—C7—C6—C5	172.2 (4)	C2—C12—C13—O2	−101.5 (5)
O1—C11—C6—C15	−165.1 (3)	C5—C12—C13—O2	103.6 (5)
C10—C11—C6—C15	76.2 (5)	C6—C7—C8—C9	−58.6 (5)
O1—C11—C6—C7	73.9 (4)	C4—O3—C17—O4	7.5 (7)
C10—C11—C6—C7	−44.7 (5)	C4—O3—C17—C18	−173.4 (4)
O1—C11—C6—C5	−46.6 (5)	O1—C11—C10—C9	−85.2 (5)
C10—C11—C6—C5	−165.2 (4)	C6—C11—C10—C9	38.9 (6)
C13—O2—C12—C2	118.6 (5)	O1—C11—C10—Br2	151.3 (3)
C13—O2—C12—C5	−119.5 (5)	C6—C11—C10—Br2	−84.6 (4)
C11—O1—C2—C12	−63.9 (5)	C17—O3—C4—C3	−145.6 (4)
C11—O1—C2—C3	48.7 (5)	C17—O3—C4—C5	98.4 (5)
O2—C12—C2—O1	−159.2 (3)	C12—C5—C4—O3	94.1 (4)
C13—C12—C2—O1	−88.6 (5)	C14—C5—C4—O3	−26.0 (6)
C5—C12—C2—O1	71.2 (4)	C6—C5—C4—O3	−152.6 (4)
O2—C12—C2—C3	80.9 (4)	C12—C5—C4—C3	−23.5 (4)
C13—C12—C2—C3	151.5 (4)	C14—C5—C4—C3	−143.6 (4)
C5—C12—C2—C3	−48.7 (4)	C6—C5—C4—C3	89.8 (4)
O2—C12—C5—C14	37.6 (5)	C7—C8—C9—C10	48.9 (5)
C13—C12—C5—C14	−34.7 (6)	C7—C8—C9—C16	179.1 (4)
C2—C12—C5—C14	165.9 (3)	C7—C8—C9—Br1	−66.8 (4)
O2—C12—C5—C4	−84.0 (4)	C11—C10—C9—C8	−39.4 (6)
C13—C12—C5—C4	−156.2 (4)	Br2—C10—C9—C8	83.1 (4)
C2—C12—C5—C4	44.3 (4)	C11—C10—C9—C16	−168.8 (4)
O2—C12—C5—C6	162.4 (4)	Br2—C10—C9—C16	−46.3 (5)
C13—C12—C5—C6	90.1 (5)	C11—C10—C9—Br1	78.3 (4)
C2—C12—C5—C6	−69.3 (4)	Br2—C10—C9—Br1	−159.3 (2)
C15—C6—C5—C12	178.4 (4)	O1—C2—C3—C4	−83.8 (4)
C7—C6—C5—C12	−61.8 (5)	C12—C2—C3—C4	32.6 (4)
C11—C6—C5—C12	57.4 (4)	O3—C4—C3—C2	−124.6 (4)
C15—C6—C5—C14	−57.3 (5)	C5—C4—C3—C2	−5.1 (4)
C7—C6—C5—C14	62.5 (5)