An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

Zeller, M.; Lutz Jr, M.R.; Becker, D.P.

doi:10.1107/S0108768109002134

An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

M. Zeller, M. R. Lutz Jr and D. P. Becker

The oxime derivative of [1.1.1]cyclophane cyclotriveratrylene (CTV) was ring expanded utilizing a Beckmann rearrangement to provide a ten-membered N-acetyl macrocyclic amide that crystallizes as a chloroform monosolvate in columnar assemblies manifesting an unusual disorder within the crystal. Columns made up of this structure consist of infinite columnar assemblies of alternating D and L enantiomers and therefore necessarily are made up of a racemate, yet the chiralities of individual molecules in adjacent columns are independent of one another, leading to the overall formation of a two-dimensional solid solution. The random arrangement of the columns within the structure leads to the emergence of a crystallographic mirror plane not reflected by the molecular symmetry, to a change of symmetry from Pna2₁ to Pnma and to whole-molecule disorder of the bowl-shaped molecules within the columns.

Keywords: cyclotriveratrylene; solid solution; whole-molecule disorder; columnar assemblies; Beckmann rearrangement.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768109002134/ry5022sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768109002134/ry5022Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S0108768109002134/ry5022sup3.pdf NMR spectra, and TGA and DSC data

CCDC reference: 737458

Computing details top

Data collection: Apex2 v2.1-4 (Bruker, 2007); cell refinement: Apex2 v2.1-4; data reduction: Apex2 v2.1-4; program(s) used to solve structure: SHELXTL 6.14 (Bruker, 2000-2003); program(s) used to refine structure: SHELXTL 6.14; molecular graphics: SHELXTL 6.14; software used to prepare material for publication: SHELXTL 6.14.

Figures top

(I) top

Crystal data top

C₂₉H₃₁NO₈·CHCl₃	D_x = 1.445 Mg m⁻³
M_r = 640.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 5245 reflections
a = 16.7247 (18) Å	θ = 2.2–30.1°
b = 15.7070 (16) Å	µ = 0.36 mm⁻¹
c = 11.2154 (11) Å	T = 100 K
V = 2946.2 (5) Å³	Plate, yellow
Z = 4	0.60 × 0.60 × 0.27 mm
F(000) = 1336

Data collection top

Bruker AXS SMART APEX CCD diffractometer	3783 independent reflections
Radiation source: fine-focus sealed tube	2924 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan Apex2 v2.1-4 (Bruker, 2007)	h = −22→22
T_min = 0.768, T_max = 0.906	k = −18→20
19031 measured reflections	l = −13→14

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.222	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0991P)² + 5.3522P] where P = (F_o² + 2F_c²)/3
3783 reflections	(Δ/σ)_max < 0.001
310 parameters	Δρ_max = 0.96 e Å⁻³
0 restraints	Δρ_min = −0.95 e Å⁻³

Crystal data top

C₂₉H₃₁NO₈·CHCl₃	V = 2946.2 (5) Å³
M_r = 640.92	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 16.7247 (18) Å	µ = 0.36 mm⁻¹
b = 15.7070 (16) Å	T = 100 K
c = 11.2154 (11) Å	0.60 × 0.60 × 0.27 mm

Data collection top

Bruker AXS SMART APEX CCD diffractometer	3783 independent reflections
Absorption correction: multi-scan Apex2 v2.1-4 (Bruker, 2007)	2924 reflections with I > 2σ(I)
T_min = 0.768, T_max = 0.906	R_int = 0.031
19031 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	0 restraints
wR(F²) = 0.222	H-atom parameters constrained
S = 1.04	Δρ_max = 0.96 e Å⁻³
3783 reflections	Δρ_min = −0.95 e Å⁻³
310 parameters

Special details top

Experimental. The whole molecule is disordered across a mirror plane in a 1:1 ratio. Only modest restraints were necessary to achieve a stable and meaningful refinement: C atoms C5, 12 and 13 were set to have the same ADPs as their mirror related counterparts, and C5 was also restrained to be isotropic within a standard deviation of 0.001.

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)
N1	0.9494 (3)	0.2721 (3)	0.1879 (4)	0.0206 (11)	0.50
C1	0.9456 (3)	0.1835 (4)	0.1743 (5)	0.0244 (12)	0.50
O4	1.0028 (3)	0.1368 (4)	0.1908 (5)	0.0362 (11)	0.50
C17	1.0161 (3)	0.3174 (4)	0.2306 (4)	0.0244 (9)	0.50
O5	1.0161 (3)	0.3940 (3)	0.2221 (5)	0.0333 (11)	0.50
C18	1.0827 (3)	0.2688 (4)	0.2904 (5)	0.0319 (18)	0.50
H18A	1.1148	0.2395	0.2298	0.048*	0.50
H18B	1.0599	0.2268	0.3453	0.048*	0.50
H18C	1.1167	0.3084	0.3349	0.048*	0.50
C2	0.8662 (5)	0.1481 (4)	0.1368 (7)	0.0217 (14)	0.50
C3	0.8556 (6)	0.1304 (6)	0.0162 (7)	0.0255 (16)	0.50
H3	0.8960	0.1453	−0.0395	0.031*	0.50
C4	0.7864 (6)	0.0914 (6)	−0.0224 (10)	0.031 (2)	0.50
C5	0.7270 (4)	0.0713 (5)	0.0581 (8)	0.0259 (12)	0.50
C6	0.7367 (6)	0.0891 (10)	0.1793 (15)	0.028 (2)	0.50
H6	0.6956	0.0750	0.2343	0.034*	0.50
C7	0.8065 (8)	0.1276 (8)	0.2192 (13)	0.024 (2)	0.50
C8	0.8197 (9)	0.1427 (8)	0.3523 (15)	0.026 (2)	0.50
H8A	0.8743	0.1658	0.3636	0.032*	0.50
H8B	0.8173	0.0872	0.3937	0.032*	0.50
C12	0.730 (2)	0.1103 (18)	−0.2070 (13)	0.060 (2)	0.50
H12A	0.6795	0.0780	−0.2105	0.090*	0.50
H12B	0.7506	0.1181	−0.2878	0.090*	0.50
H12C	0.7195	0.1661	−0.1708	0.090*	0.50
C13	0.6094 (11)	0.0167 (13)	0.1043 (17)	0.0661 (18)	0.50
H13A	0.6325	−0.0246	0.1600	0.099*	0.50
H13B	0.5591	−0.0057	0.0724	0.099*	0.50
H13C	0.5991	0.0704	0.1463	0.099*	0.50
O1	0.7819 (6)	0.0686 (6)	−0.1425 (8)	0.061 (3)	0.50
O2	0.6615 (4)	0.0308 (5)	0.0134 (8)	0.0418 (16)	0.50
C2A	0.8822 (4)	0.3234 (4)	0.1490 (6)	0.0181 (13)	0.50
C3A	0.8764 (5)	0.3434 (5)	0.0285 (8)	0.0218 (14)	0.50
H3A	0.9165	0.3248	−0.0255	0.026*	0.50
C4A	0.8125 (5)	0.3898 (6)	−0.0125 (8)	0.0219 (17)	0.50
C5A	0.7533 (4)	0.4186 (4)	0.0663 (8)	0.0259 (12)	0.50
C6A	0.7599 (6)	0.3984 (8)	0.1855 (11)	0.020 (2)	0.50
H6A	0.7198	0.4175	0.2392	0.025*	0.50
C7A	0.8236 (8)	0.3508 (7)	0.2294 (13)	0.0204 (19)	0.50
C8A	0.8300 (10)	0.3349 (8)	0.3635 (14)	0.028 (3)	0.50
H8AA	0.8768	0.2980	0.3792	0.034*	0.50
H8BA	0.8392	0.3899	0.4044	0.034*	0.50
C12A	0.746 (2)	0.3756 (19)	−0.2019 (14)	0.060 (2)	0.50
H12D	0.6947	0.3983	−0.1759	0.090*	0.50
H12E	0.7470	0.3137	−0.1913	0.090*	0.50
H12F	0.7548	0.3894	−0.2862	0.090*	0.50
C13A	0.6203 (12)	0.5015 (15)	0.0823 (19)	0.0661 (18)	0.50
H13D	0.6388	0.5421	0.1427	0.099*	0.50
H13E	0.5899	0.4559	0.1209	0.099*	0.50
H13F	0.5861	0.5310	0.0247	0.099*	0.50
O1A	0.8093 (4)	0.4132 (5)	−0.1316 (6)	0.0332 (13)	0.50
O2A	0.6922 (3)	0.4636 (5)	0.0180 (7)	0.0344 (14)	0.50
C9	0.75798 (15)	0.2056 (2)	0.4143 (2)	0.0313 (6)
C10	0.69566 (15)	0.16229 (17)	0.4709 (2)	0.0286 (5)
H10	0.6959	0.1018	0.4713	0.034*
C11	0.63341 (14)	0.20512 (16)	0.5266 (2)	0.0238 (5)
C14	0.56729 (17)	0.07598 (16)	0.5819 (2)	0.0320 (6)
H14A	0.5647	0.0567	0.4989	0.048*
H14B	0.5196	0.0565	0.6248	0.048*
H14C	0.6152	0.0524	0.6200	0.048*
C15	1.0006 (3)	0.2500	0.6738 (4)	0.0420 (10)
H15	1.0174	0.2500	0.7593	0.050*
Cl1	1.03797 (9)	0.15911 (7)	0.60455 (10)	0.0796 (4)
Cl2	0.89488 (11)	0.2500	0.6660 (2)	0.1029 (7)
O3	0.57083 (11)	0.16755 (11)	0.58510 (15)	0.0271 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0215 (18)	0.020 (3)	0.0201 (19)	0.0030 (16)	−0.0019 (13)	0.0025 (15)
C1	0.033 (3)	0.024 (3)	0.016 (2)	−0.004 (3)	0.0006 (18)	−0.003 (2)
O4	0.032 (2)	0.028 (3)	0.049 (3)	0.010 (2)	−0.005 (2)	−0.005 (2)
C17	0.028 (2)	0.026 (3)	0.019 (2)	−0.003 (2)	0.0008 (18)	0.000 (2)
O5	0.034 (2)	0.027 (3)	0.040 (3)	−0.006 (2)	−0.0076 (19)	0.002 (2)
C18	0.028 (2)	0.044 (6)	0.024 (2)	0.000 (2)	−0.0027 (16)	0.003 (2)
C2	0.025 (3)	0.016 (3)	0.024 (3)	−0.003 (3)	−0.005 (2)	−0.002 (3)
C3	0.031 (5)	0.028 (4)	0.018 (3)	−0.005 (3)	−0.002 (3)	0.000 (3)
C4	0.046 (6)	0.026 (4)	0.022 (3)	0.002 (4)	−0.013 (4)	−0.005 (3)
C5	0.022 (4)	0.0256 (17)	0.0302 (18)	−0.0005 (14)	−0.012 (3)	−0.0001 (18)
C6	0.018 (5)	0.033 (5)	0.034 (3)	−0.006 (4)	−0.003 (4)	0.006 (3)
C7	0.031 (7)	0.023 (5)	0.019 (4)	0.000 (4)	0.003 (4)	−0.002 (4)
C8	0.021 (4)	0.037 (6)	0.021 (4)	0.008 (4)	−0.001 (3)	−0.004 (4)
C12	0.090 (11)	0.056 (8)	0.034 (2)	0.003 (4)	−0.008 (3)	0.009 (4)
C13	0.104 (5)	0.053 (8)	0.041 (6)	−0.009 (4)	−0.004 (5)	0.007 (3)
O1	0.110 (7)	0.047 (4)	0.025 (3)	−0.003 (4)	−0.029 (4)	−0.009 (3)
O2	0.044 (4)	0.035 (3)	0.046 (3)	−0.017 (4)	−0.015 (4)	−0.003 (2)
C2A	0.023 (3)	0.016 (3)	0.016 (2)	0.002 (2)	−0.002 (2)	0.002 (2)
C3A	0.020 (3)	0.024 (4)	0.021 (3)	0.002 (3)	0.000 (2)	0.000 (3)
C4A	0.021 (4)	0.028 (5)	0.016 (4)	−0.003 (3)	0.000 (3)	0.003 (3)
C5A	0.022 (4)	0.0256 (17)	0.0302 (18)	−0.0005 (14)	−0.012 (3)	−0.0001 (18)
C6A	0.016 (5)	0.027 (4)	0.018 (3)	0.004 (4)	0.003 (4)	−0.002 (3)
C7A	0.024 (5)	0.020 (5)	0.017 (3)	−0.005 (3)	−0.003 (3)	0.000 (4)
C8A	0.040 (6)	0.034 (6)	0.011 (4)	−0.003 (4)	−0.001 (3)	−0.002 (4)
C12A	0.090 (11)	0.056 (8)	0.034 (2)	0.003 (4)	−0.008 (3)	0.009 (4)
C13A	0.104 (5)	0.053 (8)	0.041 (6)	−0.009 (4)	−0.004 (5)	0.007 (3)
O1A	0.042 (3)	0.043 (4)	0.014 (2)	−0.005 (2)	−0.001 (2)	0.013 (2)
O2A	0.026 (3)	0.045 (3)	0.032 (3)	0.014 (3)	−0.001 (3)	0.000 (2)
C9	0.0278 (11)	0.0524 (16)	0.0138 (10)	0.0080 (11)	−0.0019 (9)	0.0029 (10)
C10	0.0354 (13)	0.0343 (13)	0.0161 (10)	0.0086 (10)	−0.0003 (9)	0.0036 (9)
C11	0.0284 (11)	0.0287 (12)	0.0144 (10)	0.0009 (9)	−0.0020 (8)	0.0018 (9)
C14	0.0437 (14)	0.0218 (11)	0.0306 (13)	0.0003 (10)	−0.0003 (11)	0.0008 (10)
C15	0.049 (2)	0.048 (2)	0.0291 (19)	0.000	−0.0080 (18)	0.000
Cl1	0.1294 (11)	0.0593 (6)	0.0501 (6)	0.0216 (6)	0.0083 (6)	−0.0069 (5)
Cl2	0.0524 (9)	0.1380 (19)	0.1183 (17)	0.000	−0.0117 (10)	0.000
O3	0.0349 (9)	0.0215 (8)	0.0248 (8)	−0.0003 (7)	0.0055 (7)	0.0008 (6)

Geometric parameters (Å, º) top

N1—C1	1.401 (10)	C3A—H3A	0.9500
N1—C17	1.408 (7)	C4A—O1A	1.386 (11)
N1—C2A	1.450 (7)	C4A—C5A	1.403 (12)
C1—O4	1.220 (8)	C5A—O2A	1.356 (7)
C1—C2	1.500 (8)	C5A—C6A	1.378 (16)
C17—O5	1.208 (7)	C6A—C7A	1.391 (10)
C17—C18	1.507 (7)	C6A—H6A	0.9500
C18—H18A	0.9800	C7A—C8A	1.528 (19)
C18—H18B	0.9800	C8A—C9ⁱ	1.476 (18)
C18—H18C	0.9800	C8A—H8AA	0.9900
C2—C3	1.392 (11)	C8A—H8BA	0.9900
C2—C7	1.398 (17)	C12A—O1A	1.44 (4)
C3—C4	1.379 (10)	C12A—H12D	0.9800
C3—H3	0.9500	C12A—H12E	0.9800
C4—C5	1.379 (14)	C12A—H12F	0.9800
C4—O1	1.395 (13)	C13A—O2A	1.52 (3)
C5—O2	1.364 (7)	C13A—H13D	0.9800
C5—C6	1.40 (2)	C13A—H13E	0.9800
C6—C7	1.388 (11)	C13A—H13F	0.9800
C6—H6	0.9500	C9—C9ⁱ	1.396 (6)
C7—C8	1.53 (2)	C9—C10	1.397 (4)
C8—C9	1.589 (15)	C9—C8Aⁱ	1.476 (18)
C8—H8A	0.9900	C10—C11	1.388 (3)
C8—H8B	0.9900	C10—H10	0.9500
C12—O1	1.31 (4)	C11—O3	1.369 (3)
C12—H12A	0.9800	C11—C11ⁱ	1.410 (5)
C12—H12B	0.9800	C14—O3	1.440 (3)
C12—H12C	0.9800	C14—H14A	0.9800
C13—O2	1.36 (3)	C14—H14B	0.9800
C13—H13A	0.9800	C14—H14C	0.9800
C13—H13B	0.9800	C15—Cl1	1.741 (3)
C13—H13C	0.9800	C15—Cl1ⁱ	1.741 (3)
C2A—C3A	1.391 (11)	C15—Cl2	1.771 (5)
C2A—C7A	1.400 (16)	C15—H15	1.0000
C3A—C4A	1.372 (9)

C1—N1—C17	125.1 (5)	O1A—C4A—C5A	119.6 (8)
C1—N1—C2A	119.0 (5)	O2A—C5A—C6A	124.7 (8)
C17—N1—C2A	115.8 (5)	O2A—C5A—C4A	116.6 (8)
O4—C1—N1	123.0 (6)	C6A—C5A—C4A	118.7 (7)
O4—C1—C2	121.0 (7)	C5A—C6A—C7A	122.0 (9)
N1—C1—C2	116.0 (5)	C5A—C6A—H6A	119.0
O5—C17—N1	118.5 (5)	C7A—C6A—H6A	119.0
O5—C17—C18	122.7 (5)	C6A—C7A—C2A	118.2 (10)
N1—C17—C18	118.8 (5)	C6A—C7A—C8A	119.3 (11)
C3—C2—C7	120.3 (8)	C2A—C7A—C8A	122.4 (10)
C3—C2—C1	117.3 (7)	C9ⁱ—C8A—C7A	113.1 (12)
C7—C2—C1	122.2 (8)	C9ⁱ—C8A—H8AA	109.0
C4—C3—C2	120.1 (8)	C7A—C8A—H8AA	109.0
C4—C3—H3	120.0	C9ⁱ—C8A—H8BA	109.0
C2—C3—H3	120.0	C7A—C8A—H8BA	109.0
C5—C4—C3	120.0 (9)	H8AA—C8A—H8BA	107.8
C5—C4—O1	122.3 (8)	C4A—O1A—C12A	116.6 (10)
C3—C4—O1	117.5 (9)	C5A—O2A—C13A	127.5 (8)
O2—C5—C4	116.4 (8)	C9ⁱ—C9—C10	119.12 (16)
O2—C5—C6	123.0 (8)	C9ⁱ—C9—C8Aⁱ	115.5 (5)
C4—C5—C6	120.5 (7)	C10—C9—C8Aⁱ	125.0 (6)
C7—C6—C5	119.8 (10)	C9ⁱ—C9—C8	128.4 (5)
C7—C6—H6	120.1	C10—C9—C8	112.4 (6)
C5—C6—H6	120.1	C11—C10—C9	121.9 (2)
C6—C7—C2	119.2 (10)	C11—C10—H10	119.1
C6—C7—C8	120.3 (12)	C9—C10—H10	119.1
C2—C7—C8	120.4 (10)	O3—C11—C10	125.5 (2)
C7—C8—C9	115.5 (11)	O3—C11—C11ⁱ	115.54 (12)
C7—C8—H8A	108.4	C10—C11—C11ⁱ	118.99 (15)
C9—C8—H8A	108.4	O3—C14—H14A	109.5
C7—C8—H8B	108.4	O3—C14—H14B	109.5
C9—C8—H8B	108.4	H14A—C14—H14B	109.5
H8A—C8—H8B	107.5	O3—C14—H14C	109.5
C12—O1—C4	116.1 (13)	H14A—C14—H14C	109.5
C13—O2—C5	108.3 (9)	H14B—C14—H14C	109.5
C3A—C2A—C7A	120.5 (7)	Cl1—C15—Cl1ⁱ	110.2 (3)
C3A—C2A—N1	118.2 (6)	Cl1—C15—Cl2	109.66 (18)
C7A—C2A—N1	121.3 (7)	Cl1ⁱ—C15—Cl2	109.66 (18)
C4A—C3A—C2A	120.0 (7)	Cl1—C15—H15	109.1
C4A—C3A—H3A	120.0	Cl1ⁱ—C15—H15	109.1
C2A—C3A—H3A	120.0	Cl2—C15—H15	109.1
C3A—C4A—O1A	119.6 (7)	C11—O3—C14	116.8 (2)
C3A—C4A—C5A	120.7 (7)

C17—N1—C1—O4	−5.3 (9)	C17—N1—C2A—C3A	94.9 (7)
C2A—N1—C1—O4	170.6 (6)	C1—N1—C2A—C7A	97.0 (9)
C17—N1—C1—C2	175.1 (5)	C17—N1—C2A—C7A	−86.6 (9)
C2A—N1—C1—C2	−8.9 (9)	C7A—C2A—C3A—C4A	−0.3 (12)
C1—N1—C17—O5	169.5 (5)	N1—C2A—C3A—C4A	178.2 (7)
C2A—N1—C17—O5	−6.6 (7)	C2A—C3A—C4A—O1A	176.6 (8)
C1—N1—C17—C18	−13.5 (7)	C2A—C3A—C4A—C5A	0.8 (12)
C2A—N1—C17—C18	170.5 (5)	C3A—C4A—C5A—O2A	−179.6 (7)
O4—C1—C2—C3	−81.8 (8)	O1A—C4A—C5A—O2A	4.6 (12)
N1—C1—C2—C3	97.8 (8)	C3A—C4A—C5A—C6A	−0.8 (13)
O4—C1—C2—C7	93.7 (10)	O1A—C4A—C5A—C6A	−176.6 (9)
N1—C1—C2—C7	−86.7 (10)	O2A—C5A—C6A—C7A	179.0 (10)
C7—C2—C3—C4	−0.9 (14)	C4A—C5A—C6A—C7A	0.3 (15)
C1—C2—C3—C4	174.7 (8)	C5A—C6A—C7A—C2A	0.2 (17)
C2—C3—C4—C5	1.3 (14)	C5A—C6A—C7A—C8A	176.5 (12)
C2—C3—C4—O1	−174.6 (8)	C3A—C2A—C7A—C6A	−0.2 (15)
C3—C4—C5—O2	−178.3 (8)	N1—C2A—C7A—C6A	−178.7 (8)
O1—C4—C5—O2	−2.6 (14)	C3A—C2A—C7A—C8A	−176.4 (10)
C3—C4—C5—C6	−0.9 (15)	N1—C2A—C7A—C8A	5.2 (16)
O1—C4—C5—C6	174.8 (11)	C6A—C7A—C8A—C9ⁱ	56.0 (14)
O2—C5—C6—C7	177.4 (10)	C2A—C7A—C8A—C9ⁱ	−127.9 (11)
C4—C5—C6—C7	0.2 (17)	C3A—C4A—O1A—C12A	113.7 (10)
C5—C6—C7—C2	0.1 (19)	C5A—C4A—O1A—C12A	−70.5 (12)
C5—C6—C7—C8	−176.5 (13)	C6A—C5A—O2A—C13A	0.9 (17)
C3—C2—C7—C6	0.2 (17)	C4A—C5A—O2A—C13A	179.6 (12)
C1—C2—C7—C6	−175.2 (10)	C7—C8—C9—C9ⁱ	−80.9 (9)
C3—C2—C7—C8	176.8 (10)	C7—C8—C9—C10	96.6 (10)
C1—C2—C7—C8	1.4 (17)	C7—C8—C9—C8Aⁱ	−113 (5)
C6—C7—C8—C9	−63.1 (15)	C9ⁱ—C9—C10—C11	0.4 (3)
C2—C7—C8—C9	120.3 (12)	C8Aⁱ—C9—C10—C11	173.7 (7)
C5—C4—O1—C12	71.5 (13)	C8—C9—C10—C11	−177.4 (6)
C3—C4—O1—C12	−112.7 (12)	C9—C10—C11—O3	−179.2 (2)
C4—C5—O2—C13	−179.6 (11)	C9—C10—C11—C11ⁱ	−0.4 (3)
C6—C5—O2—C13	3.1 (15)	C10—C11—O3—C14	−4.0 (3)
C1—N1—C2A—C3A	−81.5 (8)	C11ⁱ—C11—O3—C14	177.25 (15)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A···O3ⁱⁱ	0.95	2.67	3.497 (8)	146
C13—H13C···O5ⁱⁱⁱ	0.98	2.10	2.862 (15)	133
C13A—H13E···O4ⁱⁱⁱ	0.98	2.95	3.880 (13)	159
C14—H14A···O4^iv	0.98	2.68	3.381 (7)	129
C13A—H13E···O5^iv	0.98	2.36	3.271 (14)	155
C13—H13C···O4^iv	0.98	2.65	3.466 (14)	141
C18—H18C···C6A^v	0.98	2.79	3.606 (13)	141
C15—H15···O3^vi	1.00	2.35	3.220 (4)	145
C15—H15···O3^vii	1.00	2.35	3.220 (4)	145
C12A—H12D···O2A	0.98	2.40	2.968 (19)	116
C18—H18A···Cg1^viii	0.98	2.63	3.496	148
C18—H18A···Cg1^ix	0.98	2.63	3.496	148

Symmetry codes: (ii) x+1/2, −y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) x+1/2, y, −z+1/2; (vi) x+1/2, y, −z+3/2; (vii) x+1/2, −y+1/2, −z+3/2; (viii) −x, y+1/2, −z; (ix) x−1/2, y, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₉H₃₁NO₈·CHCl₃
M_r	640.92
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	100
a, b, c (Å)	16.7247 (18), 15.7070 (16), 11.2154 (11)
V (Å³)	2946.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.60 × 0.60 × 0.27

Data collection
Diffractometer	Bruker AXS SMART APEX CCD diffractometer
Absorption correction	Multi-scan Apex2 v2.1-4 (Bruker, 2007)
T_min, T_max	0.768, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	19031, 3783, 2924
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.222, 1.04
No. of reflections	3783
No. of parameters	310
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.95

Computer programs: Apex2 v2.1-4 (Bruker, 2007), Apex2 v2.1-4, SHELXTL 6.14 (Bruker, 2000-2003), SHELXTL 6.14.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3A—H3A···O3ⁱ	0.95	2.67	3.497 (8)	146.1
C13—H13C···O5ⁱⁱ	0.98	2.10	2.862 (15)	133.0
C13A—H13E···O4ⁱⁱ	0.98	2.95	3.880 (13)	159.1
C14—H14A···O4ⁱⁱⁱ	0.98	2.68	3.381 (7)	128.8
C13A—H13E···O5ⁱⁱⁱ	0.98	2.36	3.271 (14)	154.5
C13—H13C···O4ⁱⁱⁱ	0.98	2.65	3.466 (14)	140.9
C18—H18C···C6A^iv	0.98	2.79	3.606 (13)	141.1
C15—H15···O3^v	1.00	2.35	3.220 (4)	145.0
C15—H15···O3^vi	1.00	2.35	3.220 (4)	145.0
C12A—H12D···O2A	0.98	2.40	2.968 (19)	116.0
C18—H18A···Cg1^vii	0.98	2.63	3.496	147.65
C18—H18A···Cg1^viii	0.98	2.63	3.496	147.65

Symmetry codes: (i) x+1/2, −y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1/2; (iii) x−1/2, y, −z+1/2; (iv) x+1/2, y, −z+1/2; (v) x+1/2, y, −z+3/2; (vi) x+1/2, −y+1/2, −z+3/2; (vii) −x, y+1/2, −z; (viii) x−1/2, y, −z−1/2.

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