1-O-Acetyl-3,4,6-tri-O-benzyl-2-C-bromo­methyl-2-de­oxy-α-d-glucopyran­ose

Kinfe, H.H.; Makolo, F.L.; Phasha, Z.H.

doi:10.1107/S1600536812048453

organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page o73

https://doi.org/10.1107/S1600536812048453

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1-O-Acetyl-3,4,6-tri-O-benzyl-2-C-bromomethyl-2-deoxy-α-D-glucopyranose

Henok H. Kinfe,^a Felix L. Makolo ^a and Zanele H. Phasha ^a ^*

^aResearch Center for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
^*Correspondence e-mail: zhphasha@uj.ac.za

(Received 16 November 2012; accepted 26 November 2012; online 12 December 2012)

In the title compound, C₃₀H₃₃BrO₆, the pyranose ring adopts a chair conformation. Two of the O-benzyl phenyl rings lie almost perpendicular to C/C/C/O plane formed by the ring atoms not attached to these O-benzyl phenyl rings, and form dihedral angles of 85.1 (2) and 64.6 (2)°, while the third O-benzyl phenyl ring is twisted so that it makes a dihedral angle 34.9 (2)° to this C/C/C/O plane. This twist is ascribed to the formation of an S(8) loop stabilized by a weak intramolecular C—H⋯O hydrogen bond.

Related literature

For background to derivatization of cyclopropyl carbohydrates, see: Halton & Harvey (2006 ); Beyer & Madsen (1998 ). For details of the synthesis of the title compound, see: Gammon et al. (2007 ). For ring puckering analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₃₀H₃₃BrO₆
M_r = 569.47
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.5097 (4) Å
b = 19.9357 (11) Å
c = 24.4597 (16) Å
V = 2686.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 2.43 mm⁻¹
T = 100 K
0.43 × 0.05 × 0.05 mm

Data collection

Bruker APEX DUO 4K-CCD diffractometer
Absorption correction: multi-scan (SADABS, Bruker, 2008 ) T_min = 0.613, T_max = 0.753
51826 measured reflections
4637 independent reflections
4177 reflections with I > 2σ(I)
R_int = 0.097

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.096
S = 1.04
4637 reflections
335 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.61 e Å⁻³
Absolute structure: Flack (1983 ), 1893 Friedel pairs
Flack parameter: −0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯O4	0.95	2.85	3.663 (7)	144

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: OLEX2 (Dolomanov et al. 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812048453/hg5273sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048453/hg5273Isup2.hkl

checkCIF report

Comment top

The derivatization of cyclopropyl carbohydrates remains a relatively small area of research and, of this work, only a small proportion is devoted to reactions of the cyclopropyl moiety (Halton et al., 2006). Nucleophilic attack by a range of alcohols, including monosaccharides afforded 2-C-branched glycosides (Beyer et al., 1998). The compound of interest is a useful glycosyl donor and a precursor for the extension of the C–2 side chain (Gammon et al., 2007).

In the title compound the pyranose ring adopts a chair conformation with ring puckering parameters of q₂ = 0.0601 Å, q₃ = 0.5555 Å, Q = 0.5587 Å, θ = 6.17 ° and φ₂ = 280.0707° (see Cremer & Pople, 1975) (see Figure 1). The C10 – C15 and C25 – C30 rings, lie almost perpendicular to the C1 C3 C4 O1 plane of the pyranose ring, with dihedral angles of 85.1 (2) and 64.6 (2) ° respectively. The C17 – C22 phenyl ring is twisted to an almost parallel position to the C1 C3 C4 O1 plane with a dihedral angle of 34.9 (2)°. The twist is ascribed to the formation of an S(8) loop stabilized by weak intramolecular C–H···O hydrogen bond (see Figure 1; Table 1).

Related literature top

For background to derivatization of cyclopropyl carbohydrates, see: Halton & Harvey (2006); Beyer & Madsen (1998). For details of the synthesis of the title compound, see: Gammon et al. (2007). For ring puckering analysis, see: Cremer & Pople (1975).

Experimental top

The cyclopropane, 3,4,6–Tri–O–benzyl–1,5–anhydro–2–deoxy–1,2– C–methylene–D–glycero–D–gulo–hexitol (120 mg, 0.28 mmol) was suspended in 1:1 mixture of water and 1,4–dioxane (2 mL), N-Bromosuccinamide(NBS) (163 mg, 0.84 mmol) was added, then stirring was allowed overnight at room temperature. The reaction mixture was diluted with 10% aqueous solution of sodium thiosulfate, Na₂S₂O₃, and the aqueous phase extracted with ethyl acetate; the combined organic extracts were dried over MgSO₄, and concentrated in vacuo. The residue was acetylated without purification, acetic anhydride (0.5 ml) in pyridine (1 mL) at room temperature. After 1 h, water was added to the reaction, and the mixture was extracted with dichloromethane. The combined extracts were washed with 1M HCl and saturated aqueous NaHCO₃, dried over MgSO₄, concentrated under reduced pressure, and purified by flash chromatography to afford the title compound as a white solid.

Analytical data: mp: 115 – 117 °C; ¹H NMR (CDCl₃, 400 MHz): σ 7.45 – 7.10 (m, 15H, Aromatic), 6.39 (d, J = 2.4Hz, 1H, H-1), 4.92 (d, J = 11.2Hz, 1H, CH₂Ph), 4.78 (d, J = 10.8Hz, 1H, CH₂Ph), 4.70 – 4.40 (m, 4H, CH₂Ph), 3.90 – 3.55 (m , 6H, H–3, H–4, H–5, H–6_a, H–6_b, H–7_a), 3.12 (t, J = 10.6Hz, 1H, H7_b), 2.45 – 2.25 (m, 1H, H–2), 2.09 (s, 3H, OCOCH₃); ¹³C NMR (CDCl₃, 100 MHz): σ 168.9 (OCOCH₃), 137.8, 128.6, 128.5, 128.4, 128.0, 128.0, 127.9, 127.8, 127.8, 127.7( Aromatic), 92.1 (C–1), 79.7 (C–3), 78.8 (C–4), 75.4 (C–5), 75.0 (CH₂Ph), 73.6 (CH₂Ph), 73.3 (CH₂Ph), 68.1(C–6), 46.8 (C–2), 29.1(C–7), 20.9 (OCOCH₃).

Structure description top

For background to derivatization of cyclopropyl carbohydrates, see: Halton & Harvey (2006); Beyer & Madsen (1998). For details of the synthesis of the title compound, see: Gammon et al. (2007). For ring puckering analysis, see: Cremer & Pople (1975).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al. 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al. 2009).

Figures top

Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.

1-O-Acetyl-3,4,6-tri-O-benzyl-2-C-bromomethyl- 2-deoxy-α-D-glucopyranose top

Crystal data top

C₃₀H₃₃BrO₆	F(000) = 1184
M_r = 569.47	D_x = 1.408 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9957 reflections
a = 5.5097 (4) Å	θ = 4.2–65.2°
b = 19.9357 (11) Å	µ = 2.43 mm⁻¹
c = 24.4597 (16) Å	T = 100 K
V = 2686.6 (3) Å³	Needle, colourless
Z = 4	0.43 × 0.05 × 0.05 mm

Data collection top

Bruker APEX DUO 4K-CCD diffractometer	4637 independent reflections
Radiation source: fine-focus sealed tube	4177 reflections with I > 2σ(I)
Incoatec Quazar Multilayer Mirror monochromator	R_int = 0.097
Detector resolution: 8.4 pixels mm^-1	θ_max = 66.2°, θ_min = 4.2°
φ and ω scans	h = −6→5
Absorption correction: multi-scan (SADABS, Bruker, 2008)	k = −23→23
T_min = 0.613, T_max = 0.753	l = −28→28
51826 measured reflections

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0448P)² + 1.595P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4637 reflections	Δρ_max = 1.04 e Å⁻³
335 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1893 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

Crystal data top

C₃₀H₃₃BrO₆	V = 2686.6 (3) Å³
M_r = 569.47	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 5.5097 (4) Å	µ = 2.43 mm⁻¹
b = 19.9357 (11) Å	T = 100 K
c = 24.4597 (16) Å	0.43 × 0.05 × 0.05 mm

Data collection top

Bruker APEX DUO 4K-CCD diffractometer	4637 independent reflections
Absorption correction: multi-scan (SADABS, Bruker, 2008)	4177 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.753	R_int = 0.097
51826 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.096	Δρ_max = 1.04 e Å⁻³
S = 1.04	Δρ_min = −0.61 e Å⁻³
4637 reflections	Absolute structure: Flack (1983), 1893 Friedel pairs
335 parameters	Absolute structure parameter: −0.01 (2)
0 restraints

Special details top

Experimental. Absorption correction: SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1272 before and 0.0933 after correction. The Ratio of minimum to maximum transmission is 0.8137. The λ/2 correction factor is 0.0015.

The intensity data was collected on a Bruker Apex DUO 4 K CCD diffractometer using an exposure time of 5 s/frame. A total of 4554 frames were collected with a frame width of 1° covering up to θ = 66.16° with 99.6% completeness accomplished.

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
Br1	1.52718 (7)	0.657227 (17)	0.318194 (16)	0.03952 (13)
O1	1.1736 (6)	0.61572 (12)	0.48483 (10)	0.0340 (6)
O2	1.0466 (5)	0.68570 (10)	0.41379 (9)	0.0326 (6)
O3	1.2526 (6)	0.76628 (11)	0.45934 (11)	0.0400 (7)
O4	1.0000 (6)	0.48064 (10)	0.36332 (9)	0.0351 (6)
O5	0.7051 (6)	0.48859 (11)	0.45817 (11)	0.0392 (7)
O6	1.0735 (6)	0.52549 (12)	0.57192 (10)	0.0396 (7)
C1	1.2250 (8)	0.63710 (16)	0.43169 (15)	0.0316 (9)
H1	1.3896	0.6582	0.431	0.038*
C2	1.2183 (8)	0.57915 (16)	0.39091 (15)	0.0330 (9)
H2	1.3572	0.5485	0.3992	0.04*
C3	0.9832 (8)	0.53928 (14)	0.39714 (13)	0.0297 (8)
H3	0.8448	0.5675	0.384	0.036*
C4	0.9363 (7)	0.51944 (16)	0.45609 (14)	0.0319 (8)
H4	1.0638	0.4873	0.4688	0.038*
C5	0.9433 (8)	0.58369 (16)	0.49090 (14)	0.0338 (9)
H5	0.8151	0.6149	0.4771	0.041*
C6	1.0804 (8)	0.74997 (16)	0.43301 (15)	0.0312 (9)
C7	0.8758 (8)	0.79337 (17)	0.41525 (16)	0.0366 (10)
H7A	0.9038	0.8394	0.4279	0.055*
H7B	0.7239	0.7765	0.4309	0.055*
H7C	0.8646	0.7929	0.3753	0.055*
C8	1.2419 (8)	0.60206 (17)	0.33175 (15)	0.0375 (10)
H8A	1.0952	0.6279	0.3217	0.045*
H8B	1.249	0.562	0.3078	0.045*
C9	0.7950 (8)	0.46920 (17)	0.33029 (15)	0.0355 (9)
H9A	0.7645	0.5089	0.3069	0.043*
H9B	0.6505	0.462	0.3536	0.043*
C10	0.8379 (8)	0.40787 (17)	0.29466 (15)	0.0325 (9)
C11	0.6658 (8)	0.39109 (18)	0.25596 (15)	0.0384 (10)
H11	0.5251	0.4181	0.2515	0.046*
C12	0.6995 (9)	0.3342 (2)	0.22338 (16)	0.0443 (10)
H12	0.5808	0.3224	0.1969	0.053*
C13	0.9042 (9)	0.29499 (18)	0.22953 (17)	0.0436 (11)
H13	0.9269	0.2565	0.2072	0.052*
C14	1.0756 (9)	0.31201 (18)	0.26817 (17)	0.0425 (11)
H14	1.2165	0.2851	0.2726	0.051*
C15	1.0426 (9)	0.36864 (16)	0.30087 (15)	0.0371 (9)
H15	1.1612	0.3802	0.3274	0.045*
C16	0.6728 (10)	0.43619 (19)	0.49772 (17)	0.0467 (11)
H16A	0.5836	0.4537	0.5298	0.056*
H16B	0.8329	0.4197	0.5102	0.056*
C17	0.5316 (9)	0.37961 (16)	0.47184 (15)	0.0367 (9)
C18	0.6145 (8)	0.35048 (19)	0.42360 (16)	0.0412 (10)
H18	0.7611	0.3657	0.4073	0.049*
C19	0.4844 (11)	0.29972 (18)	0.39955 (17)	0.0517 (12)
H19	0.5387	0.2812	0.3659	0.062*
C20	0.2765 (11)	0.2752 (2)	0.4234 (2)	0.0604 (15)
H20	0.1886	0.2398	0.4066	0.072*
C21	0.1970 (10)	0.3025 (2)	0.4719 (2)	0.0552 (13)
H21	0.0544	0.2858	0.4889	0.066*
C22	0.3263 (9)	0.35477 (19)	0.49587 (17)	0.0441 (10)
H22	0.2712	0.3734	0.5294	0.053*
C23	0.9028 (8)	0.57286 (17)	0.55147 (15)	0.0371 (10)
H23A	0.9214	0.616	0.5711	0.045*
H23B	0.7359	0.5562	0.5577	0.045*
C24	1.0720 (10)	0.5265 (2)	0.62974 (16)	0.0533 (12)
H24A	0.9042	0.5199	0.6432	0.064*
H24B	1.1306	0.5705	0.643	0.064*
C25	1.2327 (9)	0.4717 (2)	0.65142 (16)	0.0442 (11)
C26	1.1766 (9)	0.4043 (2)	0.64257 (18)	0.0504 (11)
H26	1.0354	0.3925	0.6225	0.06*
C27	1.3272 (9)	0.3549 (2)	0.66308 (18)	0.0511 (11)
H27	1.288	0.309	0.6572	0.061*
C28	1.5319 (10)	0.37129 (19)	0.69168 (16)	0.0496 (11)
H28	1.635	0.3371	0.7056	0.06*
C29	1.5872 (10)	0.4378 (2)	0.70016 (17)	0.0524 (12)
H29	1.7305	0.4496	0.7195	0.063*
C30	1.4362 (9)	0.48721 (18)	0.68078 (17)	0.0470 (10)
H30	1.4737	0.5329	0.6879	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0362 (2)	0.02898 (18)	0.0534 (2)	0.00229 (17)	−0.00030 (19)	0.00481 (16)
O1	0.0390 (18)	0.0234 (12)	0.0397 (14)	0.0005 (11)	−0.0060 (13)	−0.0011 (10)
O2	0.0385 (17)	0.0174 (10)	0.0419 (12)	0.0030 (11)	−0.0051 (13)	−0.0026 (9)
O3	0.0414 (19)	0.0239 (12)	0.0546 (16)	−0.0036 (12)	−0.0056 (14)	−0.0026 (11)
O4	0.0393 (17)	0.0219 (10)	0.0442 (12)	0.0038 (12)	−0.0062 (14)	−0.0071 (9)
O5	0.0436 (19)	0.0251 (12)	0.0488 (15)	−0.0033 (12)	−0.0060 (13)	0.0063 (11)
O6	0.050 (2)	0.0314 (13)	0.0374 (13)	0.0091 (12)	0.0003 (13)	0.0005 (10)
C1	0.031 (2)	0.0222 (16)	0.041 (2)	0.0025 (15)	−0.0038 (17)	−0.0011 (14)
C2	0.036 (2)	0.0192 (16)	0.044 (2)	0.0052 (15)	−0.0054 (18)	−0.0032 (14)
C3	0.029 (2)	0.0164 (13)	0.0433 (18)	0.0013 (16)	−0.0066 (19)	−0.0051 (12)
C4	0.030 (2)	0.0226 (16)	0.0433 (19)	0.0013 (15)	−0.0044 (17)	−0.0017 (14)
C5	0.035 (3)	0.0235 (16)	0.0432 (19)	0.0036 (16)	−0.0019 (18)	0.0001 (14)
C6	0.034 (3)	0.0189 (15)	0.0402 (19)	−0.0019 (15)	0.0061 (18)	−0.0009 (14)
C7	0.042 (3)	0.0223 (17)	0.045 (2)	0.0051 (16)	0.0039 (19)	−0.0017 (15)
C8	0.045 (3)	0.0234 (17)	0.044 (2)	0.0029 (17)	−0.0037 (19)	−0.0003 (15)
C9	0.040 (2)	0.0240 (17)	0.043 (2)	0.0009 (16)	−0.0043 (18)	−0.0046 (15)
C10	0.035 (2)	0.0242 (17)	0.0384 (19)	−0.0051 (16)	−0.0012 (18)	0.0012 (15)
C11	0.044 (3)	0.0278 (18)	0.044 (2)	−0.0050 (17)	0.000 (2)	−0.0003 (16)
C12	0.053 (3)	0.036 (2)	0.044 (2)	−0.011 (2)	−0.005 (2)	−0.0057 (17)
C13	0.056 (3)	0.0254 (18)	0.049 (2)	−0.0059 (18)	0.005 (2)	−0.0069 (16)
C14	0.043 (3)	0.0265 (18)	0.058 (2)	−0.0018 (17)	0.003 (2)	−0.0060 (17)
C15	0.039 (3)	0.0280 (16)	0.0443 (19)	−0.0057 (17)	−0.0024 (19)	−0.0044 (14)
C16	0.058 (3)	0.033 (2)	0.049 (2)	−0.010 (2)	−0.005 (2)	0.0031 (18)
C17	0.039 (3)	0.0245 (16)	0.047 (2)	0.0043 (18)	−0.002 (2)	0.0058 (14)
C18	0.040 (3)	0.034 (2)	0.049 (2)	0.0060 (19)	−0.0005 (18)	0.0030 (18)
C19	0.068 (4)	0.0322 (19)	0.055 (2)	0.012 (2)	−0.008 (3)	−0.0039 (17)
C20	0.082 (4)	0.027 (2)	0.072 (3)	−0.007 (2)	−0.031 (3)	0.007 (2)
C21	0.045 (3)	0.042 (2)	0.078 (3)	−0.011 (2)	−0.006 (3)	0.021 (2)
C22	0.047 (3)	0.035 (2)	0.050 (2)	0.0075 (19)	0.004 (2)	0.0066 (18)
C23	0.040 (3)	0.0254 (17)	0.046 (2)	0.0060 (16)	−0.0008 (18)	0.0004 (15)
C24	0.057 (4)	0.060 (3)	0.042 (2)	0.015 (2)	0.001 (2)	0.0043 (19)
C25	0.055 (3)	0.041 (2)	0.036 (2)	0.011 (2)	0.011 (2)	0.0016 (17)
C26	0.045 (3)	0.055 (3)	0.051 (2)	0.004 (2)	−0.006 (2)	−0.009 (2)
C27	0.054 (3)	0.034 (2)	0.065 (3)	−0.001 (2)	0.002 (2)	−0.0014 (19)
C28	0.062 (3)	0.0396 (19)	0.047 (2)	0.010 (2)	0.003 (2)	0.0092 (16)
C29	0.062 (4)	0.047 (2)	0.049 (2)	0.000 (2)	−0.011 (2)	0.0013 (19)
C30	0.062 (3)	0.0329 (18)	0.046 (2)	0.0002 (19)	0.000 (3)	0.0022 (18)

Geometric parameters (Å, º) top

Br1—C8	1.947 (4)	C12—C13	1.381 (6)
O1—C1	1.397 (4)	C13—H13	0.95
O1—C5	1.428 (5)	C13—C14	1.378 (6)
O2—C1	1.448 (4)	C14—H14	0.95
O2—C6	1.377 (4)	C14—C15	1.395 (5)
O3—C6	1.192 (5)	C15—H15	0.95
O4—C3	1.435 (3)	C16—H16A	0.99
O4—C9	1.407 (5)	C16—H16B	0.99
O5—C4	1.415 (5)	C16—C17	1.510 (6)
O5—C16	1.435 (5)	C17—C18	1.392 (6)
O6—C23	1.423 (5)	C17—C22	1.367 (6)
O6—C24	1.414 (5)	C18—H18	0.95
C1—H1	1	C18—C19	1.373 (6)
C1—C2	1.527 (5)	C19—H19	0.95
C2—H2	1	C19—C20	1.375 (8)
C2—C3	1.528 (6)	C20—H20	0.95
C2—C8	1.523 (5)	C20—C21	1.375 (7)
C3—H3	1	C21—H21	0.95
C3—C4	1.517 (5)	C21—C22	1.392 (6)
C4—H4	1	C22—H22	0.95
C4—C5	1.538 (5)	C23—H23A	0.99
C5—H5	1	C23—H23B	0.99
C5—C23	1.514 (5)	C24—H24A	0.99
C6—C7	1.486 (5)	C24—H24B	0.99
C7—H7A	0.98	C24—C25	1.503 (6)
C7—H7B	0.98	C25—C26	1.394 (6)
C7—H7C	0.98	C25—C30	1.367 (7)
C8—H8A	0.99	C26—H26	0.95
C8—H8B	0.99	C26—C27	1.383 (7)
C9—H9A	0.99	C27—H27	0.95
C9—H9B	0.99	C27—C28	1.367 (7)
C9—C10	1.520 (5)	C28—H28	0.95
C10—C11	1.381 (6)	C28—C29	1.377 (6)
C10—C15	1.381 (6)	C29—H29	0.95
C11—H11	0.95	C29—C30	1.373 (6)
C11—C12	1.399 (5)	C30—H30	0.95
C12—H12	0.95

C1—O1—C5	114.4 (3)	C13—C12—H12	119.8
C6—O2—C1	115.3 (3)	C12—C13—H13	120.2
C9—O4—C3	114.3 (3)	C14—C13—C12	119.7 (4)
C4—O5—C16	116.9 (3)	C14—C13—H13	120.2
C24—O6—C23	109.8 (3)	C13—C14—H14	119.9
O1—C1—O2	110.3 (3)	C13—C14—C15	120.2 (4)
O1—C1—H1	109.2	C15—C14—H14	119.9
O1—C1—C2	111.8 (3)	C10—C15—C14	120.1 (4)
O2—C1—H1	109.2	C10—C15—H15	119.9
O2—C1—C2	107.0 (3)	C14—C15—H15	119.9
C2—C1—H1	109.2	O5—C16—H16A	109.9
C1—C2—H2	108.1	O5—C16—H16B	109.9
C1—C2—C3	110.4 (3)	O5—C16—C17	109.0 (3)
C3—C2—H2	108.1	H16A—C16—H16B	108.3
C8—C2—C1	113.1 (3)	C17—C16—H16A	109.9
C8—C2—H2	108.1	C17—C16—H16B	109.9
C8—C2—C3	108.9 (3)	C18—C17—C16	119.9 (4)
O4—C3—C2	108.1 (3)	C22—C17—C16	121.1 (4)
O4—C3—H3	108.8	C22—C17—C18	119.0 (4)
O4—C3—C4	110.3 (2)	C17—C18—H18	120
C2—C3—H3	108.8	C19—C18—C17	119.9 (4)
C4—C3—C2	112.0 (3)	C19—C18—H18	120
C4—C3—H3	108.8	C18—C19—H19	119.5
O5—C4—C3	107.5 (3)	C18—C19—C20	121.0 (4)
O5—C4—H4	110.1	C20—C19—H19	119.5
O5—C4—C5	111.4 (3)	C19—C20—H20	120.3
C3—C4—H4	110.1	C19—C20—C21	119.4 (4)
C3—C4—C5	107.7 (3)	C21—C20—H20	120.3
C5—C4—H4	110.1	C20—C21—H21	120.1
O1—C5—C4	109.7 (3)	C20—C21—C22	119.8 (5)
O1—C5—H5	108.3	C22—C21—H21	120.1
O1—C5—C23	107.3 (3)	C17—C22—C21	120.8 (4)
C4—C5—H5	108.3	C17—C22—H22	119.6
C23—C5—C4	114.8 (3)	C21—C22—H22	119.6
C23—C5—H5	108.3	O6—C23—C5	109.9 (3)
O2—C6—C7	109.8 (3)	O6—C23—H23A	109.7
O3—C6—O2	123.1 (3)	O6—C23—H23B	109.7
O3—C6—C7	127.1 (3)	C5—C23—H23A	109.7
C6—C7—H7A	109.5	C5—C23—H23B	109.7
C6—C7—H7B	109.5	H23A—C23—H23B	108.2
C6—C7—H7C	109.5	O6—C24—H24A	109.7
H7A—C7—H7B	109.5	O6—C24—H24B	109.7
H7A—C7—H7C	109.5	O6—C24—C25	109.8 (3)
H7B—C7—H7C	109.5	H24A—C24—H24B	108.2
Br1—C8—H8A	108.8	C25—C24—H24A	109.7
Br1—C8—H8B	108.8	C25—C24—H24B	109.7
C2—C8—Br1	113.6 (3)	C26—C25—C24	121.0 (5)
C2—C8—H8A	108.8	C30—C25—C24	120.3 (4)
C2—C8—H8B	108.8	C30—C25—C26	118.8 (4)
H8A—C8—H8B	107.7	C25—C26—H26	120.1
O4—C9—H9A	109.8	C27—C26—C25	119.8 (5)
O4—C9—H9B	109.8	C27—C26—H26	120.1
O4—C9—C10	109.6 (3)	C26—C27—H27	119.7
H9A—C9—H9B	108.2	C28—C27—C26	120.6 (4)
C10—C9—H9A	109.8	C28—C27—H27	119.7
C10—C9—H9B	109.8	C27—C28—H28	120.3
C11—C10—C9	118.8 (4)	C27—C28—C29	119.4 (4)
C15—C10—C9	121.3 (3)	C29—C28—H28	120.3
C15—C10—C11	119.9 (3)	C28—C29—H29	119.8
C10—C11—H11	120.1	C30—C29—C28	120.3 (5)
C10—C11—C12	119.7 (4)	C30—C29—H29	119.8
C12—C11—H11	120.1	C25—C30—C29	121.0 (4)
C11—C12—H12	119.8	C25—C30—H30	119.5
C13—C12—C11	120.4 (4)	C29—C30—H30	119.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O4	0.95	2.85	3.663 (7)	144

Experimental details

Crystal data
Chemical formula	C₃₀H₃₃BrO₆
M_r	569.47
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.5097 (4), 19.9357 (11), 24.4597 (16)
V (Å³)	2686.6 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.43
Crystal size (mm)	0.43 × 0.05 × 0.05

Data collection
Diffractometer	Bruker APEX DUO 4K-CCD
Absorption correction	Multi-scan (SADABS, Bruker, 2008)
T_min, T_max	0.613, 0.753
No. of measured, independent and observed [I > 2σ(I)] reflections	51826, 4637, 4177
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.096, 1.04
No. of reflections	4637
No. of parameters	335
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.04, −0.61
Absolute structure	Flack (1983), 1893 Friedel pairs
Absolute structure parameter	−0.01 (2)

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT (Bruker, 2008), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al. 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O4	0.95	2.85	3.663 (7)	143.8

Acknowledgements

Support by the research funds of the University of Johannesburg is gratefully acknowledged.

References

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