Hamigerin A and a hamigerin D decomposition product

The sponge Hamigera tarangaensis has yielded eight new compounds and we report here the structure of one of these compounds, hamigeran A, C₂₀H₂₅BrO₅, or methyl 7-bromo-4β,6-di­hydroxy-1β-iso­propyl-3aα,8-di­methyl-5-oxo-1a,3a,4,5-tetra­hydro­cyclo­penta­[a]­naphthalene-4-carboxyl­ate, and the decomposition product of hamigeran D, C₂₁H₂₈BrNO₄, namely 2-(8-bromo-2β,7-di­methyl-4-oxo-1,3α-benzox­aza­n-5-yl)-3-iso­propylcyclo­pentyl­acetic acid.

S1. Comment

As part of a search for biologically active compounds from New Zealand sponges, extracts from Hamigera taragaensis yielded eight new compounds. Details have been published elsewhere (Wellington et al., 2000) in which the structural elucidation, by NMR spectroscopy, of the seven compounds and the structural revision of an eighth compound was described. In order to confirm the structure assignments and establish the absolute stereochemistries, single-crystal X-ray studies were carried out on hamigeran A, (I), and the decomposition product, (II), of hamigeran D, (III). \sch

The structure of (I) is illustrated in Figure 1 which shows the absolute stereochemistry and confirms the chemical assignment. The six-membered ring and the five-membered ring are cis fused at the ring junction C5—C9. There is some strain in the molecule at this point evidenced by the bond lengths C5—C6 1.565 (5), C5—C9 1.562 (5) and C8—C9 1.575 (6) Å which are slightly longer than the remaining C - C single bonds. These distances are consistent with tabulated values for a pentasubstituted C—C bond (Allen et al., 1987). The C6—C12 bond is staggered, C5—C6—C12—C13 172.3 (4)°, orienting the isopropyl group well clear of the five-membered ring. The torsion angle C9—C10—C17—O5 is 163.3 (3)°, which orients the ester group so as to minimize steric interactions in this area.

There is an intramolecular hydrogen bond between the phenolic proton, H3A, and the carbonyl oxygen O2, O3—O2 separation 2.580 (6) Å. The hydroxyl proton, H1A, does not seem to be involved in a hydrogen bond, the closest approach to an acceptor atom being 2.80 Å to O5. There are no significant intermolecular interactions.

The structure of (II) contains two independent molecules in the unit cell which are linked into a dimer through hydrogen bonds. Figure 2 shows the structure of the dimeric unit. The numbering of the oxygen and carbon atoms of the second molecule are obtained by adding 20 to those of the first molecule. The crystal structure confirms the structural assignment and establishes the absolute configuration. The two molecules have a remarkably similar conformation, even though there is the possibility of free rotation about the C4A—C5, C6—C13 and C9—C10 bonds. The torsion angles within the two molecules are C5—C9—C10—C12 65.2 (3) and 72.9 (3)°; C5—C6—C13—C14, -63.1 (3) and -60.1 (3)°, respectively. The same bond lengthing around the penta-substituted bond C5—C9 as shown in [1] is seen again here; C5—C6, 1.568 (4) and 1.576 (3); C5—C9, 1.576 (4), 1.573 (4); C8—C9, 1.553 (4) and 1.551 (4), even though the constraint on the configuration imposed by the ring junction is absent.

The two independent molecules are linked by intermolecular hydrogen bonds. There is a strong interaction between the carboxylic acid groups; O4—O24 2.599 (4) and O3—O23 2.643 (3) Å. There is a somewhat weaker interaction between the amide groups; N1—O22 2.903 (3) and N2—O2 2.858 (3), as evidenced by the longer approach.

Related literature

For related literature, see: Allen et al. (1987); Flack (1983); Wellington et al. (2000).

S2. Experimental

The compounds were obtained from extracts of Hamigera taragaensis as previously described (Wellington et al., 2000). Hamigarin D underwent a spontaneous decomposition in CDCl₃ solvent in the NMR tube yielding the decomposition product. Crystals suitable for X-ray diffraction studies were obtained from methanol.

S3. Refinement

H atoms were located geometrically and initally refined using a riding model. In the final refinement the coordinates of H atoms involved in hydrogen bonding were allowed to refine with their displacement parameters tied to the carrier atom.

Final refinement allowed the fraction contribution of the inverted enantiomer to vary (Flack, 1983), the absolute structure parameter quoted being the refined value of this contribution. In both structures the contribution of the inverted enantiomer is negligible.

Computing details

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Structure of (I) showing 50% probability displacement ellipsoids. The hydrogen atoms are omitted for clarity.
	Fig. 2. Structure of (II) showing the hydrogen bonding with 50% probability displacement ellipsoids. H atoms and the label for C29, which is bonded to C25 and C28, have been omitted to avoid crowding.

(I) 7-bromo-4β,6-dihydro-1β-isopropyl-4α-methoxycarbonyl-3aα,8- dimethylcyclopenta[a-1a,3a,4,5-tetrahydronaphthalen-5-one]

Crystal data

C20H25BrO5	Dx = 1.472 Mg m^−3
Mr = 425.31	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 6757 reflections
a = 7.0958 (13) Å	θ = 2–26°
b = 16.050 (3) Å	µ = 2.17 mm^−1
c = 16.856 (4) Å	T = 203 K
V = 1919.7 (7) Å^3	Needle, yellow
Z = 4	0.32 × 0.16 × 0.10 mm
F(000) = 880

Data collection

Siemens SMART diffractometer	3020 independent reflections
Radiation source: fine-focus sealed tube	2738 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Area detector ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan Blessing (1995)	h = −6→6
Tmin = 0.544, Tmax = 0.812	k = 0→19
8269 measured reflections	l = 0→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.107	Calculated w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 1.620P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.003
3020 reflections	Δρmax = 0.38 e Å^−3
239 parameters	Δρmin = −0.47 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.000 (13)

Special details

Experimental. The data collection nominally covered a hemisphere of reciprocal space, by a combination of three sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.17413 (10)	0.12957 (4)	0.49179 (3)	0.0873 (3)
O1	0.0612 (5)	−0.2713 (2)	0.25439 (19)	0.0661 (10)
H1	−0.0136	−0.3074	0.2387	0.099*
O2	0.2661 (6)	−0.1571 (2)	0.3248 (2)	0.0694 (11)
O3	0.3027 (5)	−0.0233 (2)	0.4081 (2)	0.0673 (10)
H3A	0.335 (10)	−0.068 (4)	0.378 (4)	0.101*
O4	−0.3056 (6)	−0.2094 (2)	0.3777 (2)	0.0784 (12)
O5	−0.0482 (5)	−0.2816 (2)	0.40302 (19)	0.0649 (10)
C1	0.1220 (7)	−0.0049 (3)	0.3868 (2)	0.0472 (12)
C2	0.0338 (8)	0.0645 (3)	0.4183 (2)	0.0515 (13)
C3	−0.1486 (8)	0.0843 (2)	0.3992 (2)	0.0462 (11)
C4	−0.2463 (7)	0.0330 (2)	0.3462 (2)	0.0402 (10)
H4A	−0.3722	0.0460	0.3339	0.048*
C4A	−0.1646 (6)	−0.0360 (2)	0.31115 (19)	0.0341 (9)
C5	−0.2706 (6)	−0.0850 (2)	0.2487 (2)	0.0330 (9)
H5A	−0.3968	−0.0998	0.2694	0.040*
C6	−0.2935 (6)	−0.0378 (2)	0.1681 (2)	0.0368 (10)
H6A	−0.3774	−0.0726	0.1349	0.044*
C7	−0.0964 (7)	−0.0467 (3)	0.1329 (2)	0.0486 (11)
H7A	−0.0989	−0.0374	0.0754	0.058*
H7B	−0.0095	−0.0066	0.1570	0.058*
C8	−0.0366 (7)	−0.1351 (3)	0.1514 (2)	0.0519 (12)
H8A	0.0958	−0.1366	0.1678	0.062*
H8B	−0.0520	−0.1707	0.1047	0.062*
C9	−0.1677 (7)	−0.1659 (2)	0.2209 (2)	0.0396 (9)
C10	−0.0399 (7)	−0.2038 (2)	0.2861 (2)	0.0425 (10)
C11	0.0993 (7)	−0.1377 (3)	0.3147 (2)	0.0467 (11)
C11A	0.0203 (7)	−0.0568 (3)	0.3343 (2)	0.0401 (10)
C12	−0.3795 (7)	0.0495 (2)	0.1681 (2)	0.0429 (11)
H12A	−0.3099	0.0845	0.2066	0.051*
C13	−0.3655 (8)	0.0897 (3)	0.0862 (3)	0.0624 (14)
H13A	−0.4208	0.1449	0.0878	0.094*
H13B	−0.4328	0.0558	0.0479	0.094*
H13C	−0.2342	0.0938	0.0708	0.094*
C14	−0.5874 (8)	0.0467 (3)	0.1926 (3)	0.0598 (13)
H14A	−0.5984	0.0213	0.2446	0.090*
H14B	−0.6580	0.0142	0.1543	0.090*
H14C	−0.6373	0.1030	0.1945	0.090*
C15	−0.3108 (9)	−0.2304 (3)	0.1928 (3)	0.0589 (13)
H15A	−0.2453	−0.2803	0.1758	0.088*
H15B	−0.3825	−0.2078	0.1488	0.088*
H15C	−0.3956	−0.2440	0.2360	0.088*
C16	−0.2478 (9)	0.1595 (3)	0.4321 (3)	0.0699 (16)
H16A	−0.3742	0.1625	0.4104	0.105*
H16B	−0.1786	0.2094	0.4177	0.105*
H16C	−0.2546	0.1552	0.4895	0.105*
C17	−0.1532 (8)	−0.2308 (2)	0.3603 (2)	0.0423 (10)
C18	−0.1335 (8)	−0.3129 (3)	0.4761 (3)	0.0671 (15)
H18A	−0.0456	−0.3498	0.5027	0.101*
H18B	−0.2478	−0.3433	0.4634	0.101*
H18C	−0.1638	−0.2665	0.5106	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.1108 (6)	0.1028 (4)	0.0483 (2)	−0.0569 (4)	−0.0195 (3)	−0.0002 (3)
O1	0.088 (3)	0.0558 (18)	0.0547 (18)	0.0325 (18)	0.0157 (17)	0.0008 (15)
O2	0.038 (3)	0.092 (3)	0.078 (2)	0.015 (2)	0.0069 (17)	0.0266 (19)
O3	0.041 (3)	0.101 (3)	0.0596 (19)	−0.017 (2)	−0.0155 (17)	0.0249 (18)
O4	0.065 (3)	0.103 (3)	0.067 (2)	0.032 (2)	0.026 (2)	0.0431 (19)
O5	0.054 (2)	0.087 (2)	0.0540 (18)	0.0143 (19)	0.0068 (16)	0.0330 (17)
C1	0.033 (3)	0.073 (3)	0.0362 (19)	−0.018 (2)	−0.0047 (17)	0.0193 (19)
C2	0.066 (4)	0.060 (3)	0.0286 (18)	−0.028 (2)	−0.008 (2)	0.0046 (17)
C3	0.063 (4)	0.048 (2)	0.0274 (16)	−0.013 (2)	−0.001 (2)	0.0023 (15)
C4	0.035 (3)	0.047 (2)	0.0381 (19)	0.002 (2)	0.0006 (16)	−0.0007 (16)
C4A	0.030 (3)	0.0406 (19)	0.0314 (15)	−0.0031 (18)	0.0000 (16)	0.0055 (14)
C5	0.030 (3)	0.0357 (17)	0.0330 (16)	−0.0013 (16)	0.0012 (15)	0.0010 (14)
C6	0.036 (3)	0.0387 (19)	0.0354 (17)	−0.0042 (19)	−0.0061 (16)	0.0038 (15)
C7	0.048 (3)	0.059 (3)	0.038 (2)	0.004 (2)	0.0033 (19)	0.0110 (19)
C8	0.051 (3)	0.071 (3)	0.0339 (18)	0.013 (3)	0.0086 (18)	0.002 (2)
C9	0.047 (3)	0.0394 (19)	0.0322 (16)	0.008 (2)	0.0044 (18)	0.0005 (14)
C10	0.040 (3)	0.049 (2)	0.0387 (19)	0.014 (2)	0.0067 (17)	0.0028 (17)
C11	0.032 (3)	0.068 (3)	0.0398 (19)	0.007 (2)	0.0073 (17)	0.019 (2)
C11A	0.034 (3)	0.051 (2)	0.0354 (19)	−0.003 (2)	0.0009 (17)	0.0109 (17)
C12	0.044 (3)	0.039 (2)	0.046 (2)	−0.0029 (19)	−0.0098 (18)	0.0038 (17)
C13	0.073 (4)	0.057 (3)	0.058 (3)	−0.001 (3)	−0.008 (3)	0.017 (2)
C14	0.049 (4)	0.058 (3)	0.072 (3)	0.010 (2)	−0.005 (2)	0.010 (2)
C15	0.083 (4)	0.041 (2)	0.053 (2)	0.001 (3)	−0.009 (3)	−0.0059 (18)
C16	0.101 (5)	0.059 (3)	0.049 (2)	−0.009 (3)	0.008 (3)	−0.018 (2)
C17	0.045 (3)	0.042 (2)	0.0395 (19)	0.003 (2)	−0.001 (2)	0.0037 (15)
C18	0.071 (4)	0.082 (3)	0.049 (2)	−0.012 (3)	−0.003 (2)	0.029 (2)

Geometric parameters (Å, º)

Br1—C2	1.902 (4)	C4A—C5	1.514 (5)
O1—C10	1.404 (5)	C5—C9	1.562 (5)
O2—C11	1.235 (5)	C5—C6	1.565 (5)
O3—C1	1.364 (6)	C6—C7	1.526 (6)
O4—C17	1.172 (6)	C6—C12	1.528 (5)
O5—C17	1.318 (5)	C7—C8	1.513 (6)
O5—C18	1.462 (5)	C8—C9	1.575 (6)
C1—C2	1.384 (7)	C9—C15	1.525 (6)
C1—C11A	1.413 (6)	C9—C10	1.549 (5)
C2—C3	1.371 (7)	C10—C11	1.527 (7)
C3—C4	1.399 (6)	C10—C17	1.549 (6)
C3—C16	1.504 (7)	C11—C11A	1.453 (6)
C4—C4A	1.382 (5)	C12—C13	1.527 (6)
C4A—C11A	1.409 (6)	C12—C14	1.532 (7)
C17—O5—C18	116.0 (4)	C15—C9—C5	110.3 (4)
O3—C1—C2	119.9 (4)	C10—C9—C5	112.8 (3)
O3—C1—C11A	121.2 (5)	C15—C9—C8	112.0 (3)
C2—C1—C11A	118.9 (4)	C10—C9—C8	107.7 (4)
C3—C2—C1	121.5 (4)	C5—C9—C8	103.8 (3)
C3—C2—Br1	121.3 (4)	O1—C10—C11	109.0 (4)
C1—C2—Br1	117.1 (4)	O1—C10—C9	109.4 (3)
C2—C3—C4	118.8 (4)	C11—C10—C9	109.3 (3)
C2—C3—C16	122.8 (4)	O1—C10—C17	110.9 (3)
C4—C3—C16	118.4 (5)	C11—C10—C17	106.0 (3)
C4A—C4—C3	122.4 (4)	C9—C10—C17	112.2 (4)
C4—C4A—C11A	117.5 (4)	O2—C11—C11A	124.3 (5)
C4—C4A—C5	120.3 (4)	O2—C11—C10	119.2 (4)
C11A—C4A—C5	122.1 (3)	C11A—C11—C10	116.3 (4)
C4A—C5—C9	114.1 (3)	C4A—C11A—C1	120.6 (4)
C4A—C5—C6	113.8 (3)	C4A—C11A—C11	120.6 (4)
C9—C5—C6	101.0 (3)	C1—C11A—C11	118.2 (4)
C7—C6—C12	116.9 (3)	C13—C12—C14	108.6 (4)
C7—C6—C5	101.4 (3)	C13—C12—C6	111.1 (4)
C12—C6—C5	119.0 (3)	C14—C12—C6	111.0 (4)
C8—C7—C6	105.3 (3)	O4—C17—O5	124.5 (4)
C7—C8—C9	106.4 (3)	O4—C17—C10	126.8 (4)
C15—C9—C10	110.1 (3)	O5—C17—C10	108.7 (4)
C5—C6—C12—C13	172.3 (4)	C6—C5—C9—C8	34.9 (4)
C9—C10—C17—O5	163.3 (3)	C4A—C5—C9—C10	28.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.92 (6)	1.75 (6)	2.580 (6)	149 (7)

(II) 8-bromo-5-(2'α-carboxymethyl-5'α-isopropyl-2'β-methyl)-3-imono- 7-methyl-2,3-dihydrobenzopyran-4-one

Crystal data

C21H28BrNO4	F(000) = 912
Mr = 438.35	Dx = 1.363 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.0979 (1) Å	Cell parameters from 8192 reflections
b = 20.5473 (2) Å	θ = 2–26°
c = 10.7452 (1) Å	µ = 1.95 mm^−1
β = 106.685 (1)°	T = 203 K
V = 2135.60 (4) Å^3	Irregular fragment, colourless
Z = 4	0.60 × 0.35 × 0.31 mm

Data collection

Siemens SMART diffractometer	8833 independent reflections
Radiation source: fine-focus sealed tube	6885 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Area detector ω scans	θmax = 28.2°, θmin = 2.0°
Absorption correction: multi-scan Blessing (1995)	h = −12→12
Tmin = 0.388, Tmax = 0.583	k = −26→27
13334 measured reflections	l = 0→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.065	Calculated w = 1/[σ^2(Fo^2)]
S = 0.85	(Δ/σ)max = 0.003
8833 reflections	Δρmax = 0.27 e Å^−3
500 parameters	Δρmin = −0.26 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.86968 (4)	0.109620 (12)	0.35140 (3)	0.06056 (10)
N1	1.0478 (3)	0.24379 (11)	0.0200 (2)	0.0421 (5)
H1A	1.062 (3)	0.2473 (14)	−0.045 (3)	0.051*
O1	0.98529 (18)	0.16708 (8)	0.15221 (17)	0.0415 (4)
O2	0.96619 (19)	0.34623 (8)	0.01116 (16)	0.0412 (4)
O3	1.2698 (2)	0.34602 (12)	0.22643 (19)	0.0640 (6)
O4	1.4452 (3)	0.33072 (16)	0.4019 (2)	0.0907 (9)
H4	1.496 (4)	0.313 (2)	0.350 (4)	0.109*
C1	0.9611 (3)	0.21611 (11)	0.2297 (2)	0.0342 (6)
C2	0.9111 (3)	0.19843 (11)	0.3333 (3)	0.0377 (6)
C3	0.8911 (3)	0.24468 (12)	0.4192 (3)	0.0419 (6)
C4	0.9215 (3)	0.30953 (12)	0.3972 (3)	0.0420 (6)
H4A	0.9127	0.3410	0.4579	0.050*
C4A	0.9637 (3)	0.33023 (11)	0.2915 (2)	0.0350 (6)
C5	0.9972 (3)	0.40187 (11)	0.2768 (2)	0.0410 (6)
H5A	1.0116	0.4084	0.1903	0.049*
C6	0.8842 (3)	0.45091 (12)	0.2927 (3)	0.0493 (7)
H6A	0.8982	0.4912	0.2475	0.059*
C7	0.9243 (3)	0.46827 (14)	0.4393 (3)	0.0588 (8)
H7A	0.9159	0.5153	0.4507	0.071*
H7B	0.8633	0.4458	0.4816	0.071*
C8	1.0742 (4)	0.44649 (15)	0.4987 (3)	0.0596 (8)
H8A	1.0782	0.4100	0.5583	0.072*
H8B	1.1296	0.4824	0.5472	0.072*
C9	1.1301 (3)	0.42546 (13)	0.3845 (3)	0.0487 (7)
C10	1.2449 (3)	0.37569 (15)	0.4347 (3)	0.0516 (7)
H10A	1.3136	0.3954	0.5087	0.062*
H10B	1.2047	0.3387	0.4687	0.062*
C11	1.0009 (3)	0.29512 (11)	0.0720 (2)	0.0362 (6)
C12	1.3203 (3)	0.34922 (14)	0.3457 (3)	0.0503 (7)
C12A	0.9803 (3)	0.28155 (11)	0.2028 (2)	0.0330 (5)
C13	0.7338 (3)	0.43136 (14)	0.2315 (3)	0.0554 (8)
H13A	0.7192	0.3884	0.2670	0.066*
C14	0.6986 (4)	0.42522 (16)	0.0847 (3)	0.0682 (9)
H14A	0.7637	0.3960	0.0625	0.102*
H14B	0.7037	0.4677	0.0471	0.102*
H14C	0.6057	0.4080	0.0508	0.102*
C15	0.6329 (4)	0.48002 (19)	0.2646 (4)	0.0905 (13)
H15A	0.5387	0.4681	0.2181	0.136*
H15B	0.6522	0.5235	0.2391	0.136*
H15C	0.6443	0.4791	0.3573	0.136*
C16	1.1906 (4)	0.48575 (15)	0.3321 (3)	0.0718 (10)
H16A	1.2725	0.5008	0.3977	0.108*
H16B	1.1221	0.5202	0.3119	0.108*
H16C	1.2150	0.4738	0.2542	0.108*
C17	0.8410 (4)	0.22786 (15)	0.5352 (3)	0.0623 (9)
H17A	0.8758	0.1853	0.5681	0.093*
H17B	0.7407	0.2273	0.5092	0.093*
H17C	0.8743	0.2602	0.6028	0.093*
C18	1.0891 (3)	0.18423 (12)	0.0908 (3)	0.0435 (6)
H18A	1.1787	0.1908	0.1578	0.052*
C19	1.1020 (3)	0.12918 (13)	0.0018 (3)	0.0613 (8)
H19A	1.1301	0.0898	0.0524	0.092*
H19B	1.1707	0.1403	−0.0419	0.092*
H19C	1.0135	0.1220	−0.0623	0.092*
Br2	0.47909 (4)	0.012408 (12)	0.27702 (3)	0.06196 (10)
N2	0.8356 (2)	−0.12704 (10)	0.1259 (2)	0.0414 (5)
H2A	0.906 (3)	−0.1369 (14)	0.105 (3)	0.050*
O21	0.6995 (2)	−0.04923 (8)	0.18604 (17)	0.0434 (4)
O22	0.83974 (18)	−0.23090 (8)	0.19543 (17)	0.0422 (4)
O23	0.6026 (2)	−0.21710 (14)	−0.0798 (2)	0.0718 (7)
H23	0.639 (4)	−0.2019 (19)	−0.128 (4)	0.086*
O24	0.4314 (3)	−0.23139 (15)	−0.2561 (2)	0.0901 (9)
C21	0.6138 (3)	−0.09704 (11)	0.2085 (2)	0.0354 (6)
C22	0.5018 (3)	−0.07744 (12)	0.2498 (2)	0.0386 (6)
C23	0.4072 (3)	−0.12306 (12)	0.2689 (3)	0.0426 (6)
C24	0.4316 (3)	−0.18804 (12)	0.2453 (2)	0.0400 (6)
H24A	0.3668	−0.2190	0.2550	0.048*
C24A	0.5447 (3)	−0.21029 (11)	0.2085 (2)	0.0347 (6)
C25	0.5569 (3)	−0.28223 (11)	0.1757 (2)	0.0355 (6)
H25A	0.6486	−0.2894	0.1619	0.043*
C26	0.5388 (3)	−0.33209 (12)	0.2812 (3)	0.0431 (6)
H26A	0.5881	−0.3721	0.2688	0.052*
C27	0.3836 (3)	−0.34970 (14)	0.2416 (3)	0.0553 (8)
H27A	0.3719	−0.3969	0.2465	0.066*
H27B	0.3381	−0.3286	0.3000	0.066*
C28	0.3205 (3)	−0.32609 (15)	0.1029 (3)	0.0572 (8)
H28A	0.2587	−0.2891	0.1014	0.069*
H28B	0.2672	−0.3610	0.0491	0.069*
C29	0.4424 (3)	−0.30528 (13)	0.0507 (3)	0.0446 (6)
C30	0.3882 (3)	−0.25396 (15)	−0.0562 (3)	0.0529 (7)
H30A	0.3021	−0.2707	−0.1154	0.064*
H30B	0.3643	−0.2149	−0.0148	0.064*
C31	0.7773 (3)	−0.17810 (11)	0.1705 (2)	0.0338 (6)
C32	0.4791 (3)	−0.23343 (14)	−0.1363 (3)	0.0477 (7)
C32A	0.6418 (3)	−0.16350 (11)	0.1943 (2)	0.0333 (5)
C33	0.6005 (3)	−0.31241 (13)	0.4228 (3)	0.0479 (7)
H33A	0.5569	−0.2711	0.4376	0.057*
C34	0.7554 (3)	−0.30182 (16)	0.4557 (3)	0.0623 (8)
H34A	0.7745	−0.2677	0.4009	0.093*
H34B	0.7997	−0.3418	0.4410	0.093*
H34C	0.7911	−0.2892	0.5461	0.093*
C35	0.5722 (4)	−0.36446 (16)	0.5160 (3)	0.0712 (10)
H35A	0.4734	−0.3719	0.4957	0.107*
H35B	0.6073	−0.3493	0.6049	0.107*
H35C	0.6181	−0.4047	0.5058	0.107*
C36	0.4957 (3)	−0.36449 (15)	−0.0084 (3)	0.0593 (8)
H36A	0.4223	−0.3812	−0.0807	0.089*
H36B	0.5251	−0.3981	0.0572	0.089*
H36C	0.5734	−0.3514	−0.0388	0.089*
C37	0.2820 (4)	−0.10412 (15)	0.3091 (3)	0.0643 (9)
H37A	0.2221	−0.1416	0.3028	0.096*
H37B	0.2324	−0.0699	0.2525	0.096*
H37C	0.3105	−0.0886	0.3981	0.096*
C38	0.7614 (3)	−0.06752 (11)	0.0866 (3)	0.0415 (6)
H38A	0.6887	−0.0740	0.0033	0.050*
C39	0.8582 (4)	−0.01349 (13)	0.0722 (3)	0.0615 (9)
H39A	0.8989	−0.0245	0.0035	0.092*
H39B	0.9307	−0.0082	0.1533	0.092*
H39C	0.8067	0.0268	0.0507	0.092*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0853 (2)	0.03239 (14)	0.0704 (2)	−0.00629 (15)	0.03257 (17)	0.01026 (13)
N1	0.0500 (14)	0.0407 (12)	0.0404 (13)	−0.0056 (10)	0.0204 (12)	−0.0045 (10)
O1	0.0454 (11)	0.0303 (9)	0.0524 (11)	−0.0032 (8)	0.0199 (9)	−0.0048 (8)
O2	0.0478 (12)	0.0407 (10)	0.0360 (10)	−0.0013 (8)	0.0135 (8)	0.0045 (8)
O3	0.0529 (13)	0.0946 (17)	0.0403 (12)	−0.0041 (12)	0.0065 (10)	−0.0062 (11)
O4	0.076 (2)	0.145 (3)	0.0465 (15)	0.0250 (17)	0.0110 (14)	0.0061 (16)
C1	0.0316 (14)	0.0303 (12)	0.0382 (14)	−0.0014 (10)	0.0063 (12)	−0.0033 (10)
C2	0.0385 (15)	0.0269 (13)	0.0470 (16)	−0.0039 (11)	0.0112 (13)	0.0069 (11)
C3	0.0438 (16)	0.0401 (14)	0.0444 (15)	0.0039 (12)	0.0168 (13)	0.0100 (12)
C4	0.0526 (17)	0.0332 (13)	0.0430 (16)	0.0034 (12)	0.0180 (14)	−0.0010 (11)
C4A	0.0396 (15)	0.0292 (12)	0.0366 (14)	0.0015 (10)	0.0119 (12)	0.0032 (10)
C5	0.0569 (18)	0.0306 (13)	0.0343 (14)	−0.0070 (12)	0.0111 (13)	−0.0016 (10)
C6	0.074 (2)	0.0265 (13)	0.0454 (16)	0.0017 (13)	0.0141 (15)	0.0001 (11)
C7	0.084 (2)	0.0392 (15)	0.0520 (19)	0.0002 (16)	0.0168 (17)	−0.0107 (13)
C8	0.084 (3)	0.0473 (16)	0.0449 (18)	−0.0071 (16)	0.0144 (17)	−0.0124 (13)
C9	0.064 (2)	0.0419 (15)	0.0372 (15)	−0.0152 (14)	0.0092 (14)	−0.0035 (11)
C10	0.0547 (19)	0.0616 (18)	0.0354 (15)	−0.0131 (15)	0.0079 (14)	−0.0016 (13)
C11	0.0356 (15)	0.0348 (13)	0.0378 (15)	−0.0086 (11)	0.0097 (12)	−0.0041 (11)
C12	0.0494 (19)	0.0577 (18)	0.0380 (17)	−0.0129 (15)	0.0032 (14)	0.0045 (13)
C12A	0.0323 (14)	0.0312 (12)	0.0359 (14)	−0.0043 (10)	0.0104 (11)	0.0008 (10)
C13	0.065 (2)	0.0373 (15)	0.0594 (19)	0.0143 (14)	0.0103 (16)	−0.0019 (13)
C14	0.072 (2)	0.066 (2)	0.059 (2)	0.0138 (18)	0.0076 (17)	−0.0087 (16)
C15	0.104 (3)	0.082 (2)	0.077 (3)	0.051 (2)	0.011 (2)	−0.012 (2)
C16	0.089 (3)	0.0552 (18)	0.063 (2)	−0.0346 (18)	0.0091 (19)	−0.0057 (16)
C17	0.089 (3)	0.0514 (17)	0.060 (2)	−0.0002 (17)	0.0427 (19)	0.0097 (14)
C18	0.0415 (16)	0.0376 (14)	0.0538 (17)	−0.0040 (12)	0.0174 (14)	−0.0057 (12)
C19	0.072 (2)	0.0422 (16)	0.079 (2)	−0.0003 (15)	0.0350 (18)	−0.0146 (14)
Br2	0.0893 (2)	0.03447 (14)	0.0758 (2)	0.01116 (15)	0.04558 (19)	−0.00452 (14)
N2	0.0424 (14)	0.0394 (12)	0.0468 (13)	0.0005 (10)	0.0201 (11)	−0.0022 (10)
O21	0.0582 (12)	0.0312 (9)	0.0472 (11)	−0.0027 (8)	0.0257 (9)	−0.0047 (8)
O22	0.0416 (10)	0.0425 (10)	0.0420 (10)	0.0079 (8)	0.0114 (8)	0.0050 (8)
O23	0.0507 (15)	0.120 (2)	0.0416 (13)	−0.0131 (14)	0.0088 (11)	0.0011 (13)
O24	0.0717 (16)	0.150 (3)	0.0408 (14)	−0.0255 (17)	0.0037 (12)	−0.0069 (14)
C21	0.0464 (16)	0.0304 (12)	0.0292 (13)	0.0016 (11)	0.0104 (12)	0.0008 (10)
C22	0.0535 (17)	0.0279 (13)	0.0353 (14)	0.0082 (12)	0.0141 (13)	0.0011 (10)
C23	0.0535 (17)	0.0413 (14)	0.0385 (15)	0.0098 (13)	0.0218 (13)	0.0020 (11)
C24	0.0453 (16)	0.0371 (14)	0.0411 (15)	−0.0003 (12)	0.0179 (13)	0.0012 (11)
C24A	0.0393 (15)	0.0330 (13)	0.0292 (14)	0.0045 (11)	0.0058 (11)	0.0025 (10)
C25	0.0367 (15)	0.0293 (12)	0.0413 (15)	0.0010 (11)	0.0124 (12)	−0.0028 (10)
C26	0.0488 (16)	0.0299 (13)	0.0522 (17)	−0.0032 (12)	0.0170 (13)	−0.0006 (11)
C27	0.057 (2)	0.0452 (16)	0.067 (2)	−0.0139 (14)	0.0224 (16)	−0.0011 (14)
C28	0.0450 (17)	0.0610 (19)	0.063 (2)	−0.0122 (15)	0.0121 (15)	−0.0157 (15)
C29	0.0387 (16)	0.0462 (15)	0.0481 (17)	−0.0019 (12)	0.0111 (13)	−0.0101 (12)
C30	0.0401 (16)	0.069 (2)	0.0450 (17)	0.0083 (15)	0.0044 (13)	−0.0083 (14)
C31	0.0369 (15)	0.0350 (13)	0.0276 (13)	−0.0023 (11)	0.0063 (11)	−0.0042 (10)
C32	0.0388 (17)	0.0593 (17)	0.0394 (17)	0.0078 (14)	0.0023 (14)	−0.0090 (13)
C32A	0.0422 (15)	0.0325 (12)	0.0254 (12)	0.0033 (11)	0.0102 (11)	−0.0012 (10)
C33	0.0607 (19)	0.0362 (14)	0.0450 (17)	−0.0004 (13)	0.0123 (14)	0.0090 (12)
C34	0.070 (2)	0.0588 (19)	0.0523 (19)	−0.0062 (16)	0.0079 (16)	0.0135 (15)
C35	0.084 (3)	0.063 (2)	0.066 (2)	−0.0059 (18)	0.0218 (19)	0.0229 (17)
C36	0.059 (2)	0.0533 (18)	0.062 (2)	0.0003 (15)	0.0112 (16)	−0.0205 (15)
C37	0.072 (2)	0.0515 (18)	0.087 (3)	0.0092 (16)	0.052 (2)	0.0056 (16)
C38	0.0549 (17)	0.0348 (13)	0.0393 (15)	−0.0011 (12)	0.0207 (13)	−0.0035 (11)
C39	0.081 (2)	0.0352 (15)	0.084 (2)	−0.0094 (15)	0.048 (2)	−0.0039 (14)

Geometric parameters (Å, º)

Br1—C2	1.895 (2)	Br2—C22	1.894 (2)
N1—C11	1.342 (3)	N2—C31	1.356 (3)
N1—C18	1.438 (3)	N2—C38	1.433 (3)
O1—C1	1.373 (3)	O21—C21	1.376 (3)
O1—C18	1.434 (3)	O21—C38	1.434 (3)
O2—C11	1.233 (3)	O22—C31	1.245 (3)
O3—C12	1.238 (3)	O23—C32	1.265 (4)
O4—C12	1.289 (4)	O24—C32	1.239 (3)
C1—C2	1.396 (3)	C21—C22	1.387 (3)
C1—C12A	1.401 (3)	C21—C32A	1.412 (3)
C2—C3	1.380 (4)	C22—C23	1.395 (4)
C3—C4	1.403 (3)	C23—C24	1.394 (3)
C3—C17	1.514 (4)	C23—C37	1.501 (4)
C4—C4A	1.390 (3)	C24—C24A	1.389 (3)
C4A—C12A	1.425 (3)	C24A—C32A	1.413 (3)
C4A—C5	1.529 (3)	C24A—C25	1.533 (3)
C5—C6	1.568 (4)	C25—C29	1.573 (4)
C5—C9	1.576 (4)	C25—C26	1.576 (3)
C6—C13	1.525 (4)	C26—C33	1.524 (4)
C6—C7	1.551 (4)	C26—C27	1.545 (4)
C7—C8	1.531 (4)	C27—C28	1.522 (4)
C8—C9	1.553 (4)	C28—C29	1.551 (4)
C9—C10	1.523 (4)	C29—C30	1.540 (4)
C9—C16	1.556 (4)	C29—C36	1.540 (4)
C10—C12	1.487 (4)	C30—C32	1.489 (4)
C11—C12A	1.504 (3)	C31—C32A	1.493 (3)
C13—C14	1.519 (4)	C33—C34	1.517 (4)
C13—C15	1.540 (4)	C33—C35	1.547 (4)
C18—C19	1.511 (4)	C38—C39	1.516 (4)
C11—N1—C18	122.1 (2)	C31—N2—C38	121.4 (2)
C1—O1—C18	112.33 (18)	C21—O21—C38	111.97 (18)
O1—C1—C2	117.4 (2)	O21—C21—C22	117.4 (2)
O1—C1—C12A	121.3 (2)	O21—C21—C32A	121.1 (2)
C2—C1—C12A	121.2 (2)	C22—C21—C32A	121.5 (2)
C3—C2—C1	120.7 (2)	C21—C22—C23	120.5 (2)
C3—C2—Br1	121.03 (19)	C21—C22—Br2	118.60 (19)
C1—C2—Br1	118.28 (18)	C23—C22—Br2	120.90 (19)
C2—C3—C4	117.4 (2)	C22—C23—C24	116.9 (2)
C2—C3—C17	122.8 (2)	C22—C23—C37	122.5 (2)
C4—C3—C17	119.8 (2)	C24—C23—C37	120.5 (3)
C4A—C4—C3	124.2 (2)	C24A—C24—C23	124.7 (2)
C4—C4A—C12A	117.1 (2)	C24—C24A—C32A	117.4 (2)
C4—C4A—C5	120.5 (2)	C24—C24A—C25	120.7 (2)
C12A—C4A—C5	122.3 (2)	C32A—C24A—C25	121.8 (2)
C4A—C5—C6	114.7 (2)	C24A—C25—C29	113.5 (2)
C4A—C5—C9	112.8 (2)	C24A—C25—C26	115.3 (2)
C6—C5—C9	102.5 (2)	C29—C25—C26	102.11 (19)
C13—C6—C7	115.8 (3)	C33—C26—C27	115.4 (2)
C13—C6—C5	116.7 (2)	C33—C26—C25	116.5 (2)
C7—C6—C5	105.8 (2)	C27—C26—C25	105.8 (2)
C8—C7—C6	107.2 (2)	C28—C27—C26	107.5 (2)
C7—C8—C9	107.0 (2)	C27—C28—C29	106.8 (2)
C10—C9—C8	108.6 (2)	C30—C29—C36	109.0 (2)
C10—C9—C16	109.0 (3)	C30—C29—C28	108.0 (2)
C8—C9—C16	109.5 (2)	C36—C29—C28	109.8 (2)
C10—C9—C5	117.1 (2)	C30—C29—C25	116.6 (2)
C8—C9—C5	103.8 (2)	C36—C29—C25	109.4 (2)
C16—C9—C5	108.6 (2)	C28—C29—C25	103.9 (2)
C12—C10—C9	119.7 (2)	C32—C30—C29	118.6 (2)
O2—C11—N1	121.9 (2)	O22—C31—N2	120.4 (2)
O2—C11—C12A	123.9 (2)	O22—C31—C32A	124.8 (2)
N1—C11—C12A	113.8 (2)	N2—C31—C32A	114.7 (2)
O3—C12—O4	121.8 (3)	O24—C32—O23	121.6 (3)
O3—C12—C10	123.4 (3)	O24—C32—C30	119.4 (3)
O4—C12—C10	114.8 (3)	O23—C32—C30	119.0 (3)
C1—C12A—C4A	119.1 (2)	C21—C32A—C24A	118.7 (2)
C1—C12A—C11	115.8 (2)	C21—C32A—C31	115.8 (2)
C4A—C12A—C11	124.7 (2)	C24A—C32A—C31	125.5 (2)
C14—C13—C6	112.2 (3)	C34—C33—C26	111.6 (2)
C14—C13—C15	108.7 (3)	C34—C33—C35	108.6 (2)
C6—C13—C15	111.9 (3)	C26—C33—C35	111.4 (2)
O1—C18—N1	108.2 (2)	O21—C38—N2	107.88 (19)
O1—C18—C19	108.3 (2)	O21—C38—C39	108.4 (2)
N1—C18—C19	111.5 (2)	N2—C38—C39	110.9 (2)
C4—C4A—C5—C6	−49.4 (3)	C5—C9—C10—C12	65.2 (3)
C24—C24A—C25—C26	−51.6 (3)	C25—C29—C30—C32	72.9 (3)
C4—C4A—C5—C9	67.4 (3)	C5—C6—C13—C14	−63.1 (3)
C24—C24A—C25—C29	65.7 (3)	C25—C26—C33—C34	−60.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O22^i	0.75 (3)	2.18 (3)	2.903 (3)	163 (3)
O4—H4···O24^i	0.94 (4)	1.67 (4)	2.599 (4)	170 (4)
N2—H2A···O2^ii	0.83 (3)	2.06 (3)	2.858 (3)	160 (3)
O23—H23···O3^ii	0.78 (4)	1.87 (4)	2.643 (3)	171 (4)

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