A tetra-tert-butyl­calix­[4]­arene-12-crown-4 N,N-di­methyl­form­amide inclusion complex

The crown ether portion of the title complex, C₅₀H₆₆O₆·C₃H₇NO, is not pre-organized for metal binding to the four calix­[4]­arene O atoms. N,N-Di­methyl­form­amide forms a hydrogen-bond bridge between two calix­[4]­arene-crown mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.058
• wR factor = 0.171
• Data-to-parameter ratio = 14.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



DIFMX_01  Alert C The maximum difference density is > 0.1*ZMAX*0.75
          _refine_diff_density_max given =      0.660
          Test value =      0.600

DIFMX_02  Alert C The minimum difference density is > 0.1*ZMAX*0.75
          The relevant atom site should be identified.

PLAT_213  Alert C Atom C50     has ADP max/min Ratio ...........       3.10 prolate


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

We are beginning a new research effort investigating tight ion pair recognition. As a first step, we prepared the title compound (Arduini et al., 1997) in hopes of using its crown ring to partially bind a metal cation and the two remaining phenolic groups as precursors to appendages containing anion-binding groups. The structure of the title compound, (I), was determined to ascertain the degree of pre-organization for cation binding present in this molecule.

Optimal metal binding will occur when the crown ether adopts a conformation with all O—C—C—O torsion angles anti, and all C—O—C—C torsion angles gauche. Examination of Table 2 shows this is not the case for the structure reported here. The crown-ether is collapsed in upon itself, which is commonly observed in the structures of uncomplexed crown ether molecules (Bryan et al., 2001, and references therein). This collapse forms relatively short C—H···O contacts, one of which is listed in Table 3. As evident in the figures, the two crown O2 and O3 atoms are not well oriented for binding a metal cation together with the O atoms directly attached to the calix[4]arene.

The calix[4]arene adopts the cone conformation, as anticipated when two phenolic groups remain unsubstitutued (Böhmer, 1995). This conformation facilitates hydrogen bonding between the phenolic H atoms and the calix[4]arene O atoms (Table 3).

The N,N-dimethylformamide (DMF) molecule acts as a bridge between two calix–crown molecules. Within the asymmetric unit, C—H···O hydrogen bonds (Table 3) are formed both between the crown ring and the DMF O atom (O7), and between one of the DMF methyl atoms (C53) and a calix phenolic O atom (O5). The DMF molecule is enveloped by a symmetry equivalent (symmetry code: x, 3/2 - y, 1/2 + z) calix[4]arene cavity (Fig. 2). The DMF carbonyl C atom (C51) and one of its methyl groups (C52) form numerous C—H···π interactions with the interior of the calixarene rings (Table 3, where Cg1 represents the centroid for C1–6, Cg2 for C8–13, Cg3 for C15–20, and Cg4 for C22–27).

S2. Experimental

The title compound was prepared as previously described (Arduini et al., 1997) and crystallized from N,N-dimethylformamide.

S3. Refinement

A 1.1 mm collimator was used. The hydroxyl H atoms were located in a difference map, and their coordinates refined, although their O—H bond lengths were restrained to be equal. All other H atoms were placed in calculated positions, and refined using a riding model. All H atoms were given an isotropic displacement parameter equal to 1.2 (CH and CH₂) or 1.5 (OH and CH₃) times the equivalent isotropic displacement parameter of the atom to which they were attached. The C—H distances used depended on the type of C atom: C_methylene—H = 0.99, C_methyl—H = 0.98, and C_sp²—H = 0.95 Å. The largest peak of residual electron density in the final difference map is 0.66 e Å^-3, and is located roughly 1.3 Å from N, C51 and C52. This peak, along with some unuusual variations in the thermal parameters in the the DMF molecule, suggest there is some unresolved disorder in this molecule. The next highest peak is 0.39 e Å^-3, and is located near C49.

Computing details

Data collection: CAD-4-PC (Nonius, 1996); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2001).

Figures

	Fig. 1. The molecular structure of the title compound showing 50% displacement ellipsoids.
	Fig. 2. Space-filling model of the title compound showing DMF (center) surrounded by the calix[4]arene cavity.

(I)

Crystal data

C50H66O6·C3H7NO	F(000) = 1816
Mr = 836.1	Dx = 1.15 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.6115 (13) Å	θ = 10.0–14.4°
b = 20.000 (3) Å	µ = 0.08 mm^−1
c = 19.995 (3) Å	T = 173 K
β = 107.087 (9)°	Fragment, colorless
V = 4820.7 (12) Å^3	0.47 × 0.41 × 0.34 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.022
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.0°
Graphite monochromator	h = −14→0
ω scans	k = −23→13
10485 measured reflections	l = −22→23
8451 independent reflections	3 standard reflections every 120 min
5151 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0742P)^2 + 3.2092P] where P = (Fo^2 + 2Fc^2)/3
8451 reflections	(Δ/σ)max < 0.001
570 parameters	Δρmax = 0.66 e Å^−3
1 restraint	Δρmin = −0.38 e Å^−3
0 constraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.17928 (15)	0.58125 (9)	0.43896 (9)	0.0287 (6)
O2	0.12627 (18)	0.47798 (12)	0.57524 (12)	0.0468 (8)
O3	0.37511 (17)	0.52278 (10)	0.62161 (10)	0.0375 (7)
O4	0.38727 (15)	0.64740 (9)	0.55149 (9)	0.0287 (6)
O5	0.20233 (18)	0.75172 (10)	0.52311 (11)	0.0372 (7)
O6	0.03634 (17)	0.68126 (10)	0.43608 (10)	0.0333 (7)
C1	0.2000 (2)	0.57087 (13)	0.37460 (14)	0.0257 (8)
C2	0.3086 (2)	0.55854 (13)	0.37345 (14)	0.0239 (8)
C3	0.3243 (2)	0.54718 (13)	0.30868 (14)	0.0273 (9)
C4	0.2385 (2)	0.54953 (13)	0.24622 (14)	0.0274 (9)
C5	0.1330 (2)	0.56398 (14)	0.25053 (14)	0.0278 (8)
C6	0.1118 (2)	0.57470 (13)	0.31431 (14)	0.0260 (9)
C7	0.4074 (2)	0.56290 (14)	0.43882 (14)	0.0269 (9)
C8	0.4500 (2)	0.63422 (13)	0.44974 (14)	0.0249 (8)
C9	0.4312 (2)	0.67518 (14)	0.50169 (14)	0.0249 (8)
C10	0.4557 (2)	0.74363 (14)	0.50364 (14)	0.0262 (8)
C11	0.5084 (2)	0.76815 (14)	0.45657 (14)	0.0281 (9)
C12	0.5360 (2)	0.72800 (14)	0.40752 (15)	0.0285 (9)
C13	0.5040 (2)	0.66151 (14)	0.40445 (15)	0.0284 (9)
C14	0.4202 (2)	0.79212 (14)	0.55143 (14)	0.0287 (9)
C15	0.3248 (2)	0.83538 (14)	0.50899 (14)	0.0273 (9)
C16	0.2161 (2)	0.81116 (14)	0.49277 (14)	0.0269 (9)
C17	0.1277 (2)	0.84685 (14)	0.44921 (14)	0.0264 (9)
C18	0.1501 (2)	0.90826 (14)	0.42348 (14)	0.0299 (9)
C19	0.2570 (2)	0.93482 (14)	0.43900 (14)	0.0310 (9)
C20	0.3422 (2)	0.89664 (14)	0.48277 (14)	0.0287 (9)
C21	0.0093 (2)	0.82130 (14)	0.42930 (15)	0.0306 (9)
C22	−0.0201 (2)	0.77652 (14)	0.36464 (14)	0.0270 (9)
C23	−0.0034 (2)	0.70819 (14)	0.36977 (14)	0.0270 (9)
C24	−0.0268 (2)	0.66724 (15)	0.31062 (14)	0.0281 (9)
C25	−0.0694 (2)	0.69807 (15)	0.24568 (15)	0.0314 (9)
C26	−0.0903 (2)	0.76628 (15)	0.23749 (15)	0.0331 (10)
C27	−0.0636 (2)	0.80448 (15)	0.29850 (15)	0.0322 (9)
C28	−0.0042 (2)	0.59253 (14)	0.31581 (15)	0.0287 (9)
C29	0.1631 (3)	0.51908 (15)	0.47143 (16)	0.0362 (10)
C30	0.1353 (3)	0.53710 (16)	0.53759 (16)	0.0392 (10)
C31	0.2271 (3)	0.44354 (17)	0.60868 (18)	0.0463 (11)
C32	0.3120 (3)	0.48630 (16)	0.65895 (16)	0.0415 (11)
C33	0.4209 (3)	0.58260 (16)	0.65607 (15)	0.0387 (10)
C34	0.4726 (2)	0.62166 (15)	0.61038 (15)	0.0330 (9)
C35	0.2591 (3)	0.53424 (15)	0.17581 (15)	0.0338 (10)
C36	0.2667 (6)	0.4596 (2)	0.1695 (2)	0.103 (3)
C37	0.1694 (3)	0.5615 (2)	0.11424 (17)	0.0620 (13)
C38	0.3675 (3)	0.5657 (3)	0.1729 (2)	0.088 (2)
C39	0.5983 (3)	0.75818 (15)	0.35929 (16)	0.0369 (10)
C40	0.6058 (4)	0.7104 (2)	0.3020 (2)	0.0662 (17)
C41	0.5373 (3)	0.82031 (18)	0.3227 (2)	0.0545 (12)
C42	0.7147 (3)	0.7775 (2)	0.4030 (2)	0.0613 (16)
C43	0.2814 (3)	1.00290 (16)	0.41097 (16)	0.0391 (10)
C44	0.3176 (4)	1.05219 (18)	0.4709 (2)	0.0661 (16)
C45	0.3775 (3)	0.9956 (2)	0.3780 (2)	0.0670 (17)
C46	0.1840 (3)	1.02959 (19)	0.3542 (2)	0.0685 (14)
C47	−0.1439 (3)	0.79648 (17)	0.16457 (16)	0.0450 (11)
C48	−0.0719 (4)	0.7828 (3)	0.1175 (2)	0.107 (3)
C49	−0.2556 (4)	0.7622 (3)	0.1315 (2)	0.0814 (19)
C50	−0.1665 (6)	0.8703 (2)	0.1671 (2)	0.127 (3)
O7	0.1823 (4)	0.60657 (18)	0.7189 (2)	0.119 (2)
N	0.2269 (2)	0.71322 (15)	0.75442 (15)	0.0502 (11)
C51	0.2019 (4)	0.6508 (2)	0.7640 (3)	0.0736 (19)
C52	0.2417 (3)	0.7603 (2)	0.8102 (2)	0.0726 (16)
C53	0.2354 (3)	0.7401 (2)	0.6886 (2)	0.0679 (16)
H3	0.39710	0.53730	0.30680	0.0330*
H5	0.149 (3)	0.7320 (17)	0.4973 (17)	0.0560*
H5A	0.07330	0.56660	0.20860	0.0330*
H6	0.076 (3)	0.6476 (15)	0.4367 (18)	0.0500*
H7A	0.38510	0.54810	0.48000	0.0320*
H7B	0.46720	0.53290	0.43390	0.0320*
H11	0.52620	0.81440	0.45800	0.0340*
H13	0.51940	0.63340	0.37010	0.0340*
H14A	0.48360	0.82090	0.57580	0.0350*
H14B	0.39660	0.76690	0.58720	0.0350*
H18	0.09020	0.93310	0.39410	0.0360*
H20	0.41570	0.91380	0.49500	0.0340*
H21A	−0.04190	0.86000	0.42050	0.0370*
H21B	−0.00190	0.79590	0.46920	0.0370*
H25	−0.08490	0.67100	0.20490	0.0380*
H27	−0.07570	0.85140	0.29480	0.0390*
H28A	−0.01510	0.57560	0.35980	0.0340*
H28B	−0.05870	0.56980	0.27640	0.0340*
H29A	0.23150	0.49170	0.48250	0.0430*
H29B	0.10180	0.49320	0.43970	0.0430*
H30A	0.19400	0.56630	0.56710	0.0470*
H30B	0.06430	0.56200	0.52570	0.0470*
H31A	0.25910	0.42640	0.57240	0.0550*
H31B	0.21000	0.40460	0.63430	0.0550*
H32A	0.27460	0.51800	0.68260	0.0500*
H32B	0.36220	0.45780	0.69510	0.0500*
H33A	0.47760	0.57180	0.70080	0.0470*
H33B	0.36190	0.60950	0.66670	0.0470*
H34A	0.51640	0.65910	0.63730	0.0400*
H34B	0.52330	0.59260	0.59390	0.0400*
H36A	0.19340	0.43970	0.16310	0.1550*
H36B	0.31900	0.44170	0.21220	0.1550*
H36C	0.29270	0.44870	0.12920	0.1550*
H37A	0.19050	0.55480	0.07130	0.0930*
H37B	0.15970	0.60940	0.12110	0.0930*
H37C	0.09950	0.53810	0.11030	0.0930*
H38A	0.37800	0.55700	0.12700	0.1310*
H38B	0.42930	0.54620	0.20950	0.1310*
H38C	0.36510	0.61400	0.18020	0.1310*
H40A	0.64680	0.67030	0.32310	0.0990*
H40B	0.64450	0.73230	0.27210	0.0990*
H40C	0.53090	0.69770	0.27390	0.0990*
H41A	0.57460	0.83740	0.28960	0.0810*
H41B	0.53770	0.85470	0.35770	0.0810*
H41C	0.46050	0.80860	0.29750	0.0810*
H42A	0.75470	0.73750	0.42530	0.0920*
H42B	0.71010	0.80960	0.43910	0.0920*
H42C	0.75440	0.79800	0.37280	0.0920*
H44A	0.33840	1.09460	0.45360	0.0990*
H44B	0.38150	1.03410	0.50700	0.0990*
H44C	0.25630	1.05980	0.49080	0.0990*
H45A	0.35640	0.96360	0.33930	0.1000*
H45B	0.44400	0.97950	0.41350	0.1000*
H45C	0.39300	1.03910	0.36040	0.1000*
H46A	0.12390	1.04090	0.37410	0.1030*
H46B	0.15820	0.99550	0.31780	0.1030*
H46C	0.20640	1.06970	0.33380	0.1030*
H48A	−0.10620	0.80250	0.07140	0.1600*
H48B	−0.06440	0.73440	0.11270	0.1600*
H48C	0.00160	0.80250	0.13800	0.1600*
H49A	−0.30360	0.76850	0.16160	0.1230*
H49B	−0.24370	0.71430	0.12630	0.1230*
H49C	−0.29090	0.78180	0.08540	0.1230*
H50A	−0.09620	0.89430	0.18540	0.1910*
H50B	−0.21340	0.87810	0.19770	0.1910*
H50C	−0.20470	0.88640	0.11990	0.1910*
H51	0.19870	0.63880	0.80930	0.0880*
H52A	0.24020	0.73680	0.85290	0.1090*
H52B	0.18180	0.79340	0.79780	0.1090*
H52C	0.31320	0.78290	0.81810	0.1090*
H53A	0.31100	0.75630	0.69490	0.1010*
H53B	0.18300	0.77720	0.67370	0.1010*
H53C	0.21780	0.70500	0.65290	0.1010*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0329 (11)	0.0322 (11)	0.0240 (10)	−0.0033 (9)	0.0129 (9)	0.0021 (8)
O2	0.0372 (13)	0.0591 (15)	0.0465 (13)	0.0009 (11)	0.0158 (11)	0.0253 (12)
O3	0.0394 (12)	0.0381 (12)	0.0364 (12)	−0.0044 (10)	0.0133 (10)	0.0004 (10)
O4	0.0271 (10)	0.0340 (11)	0.0248 (10)	0.0000 (9)	0.0074 (8)	0.0060 (9)
O5	0.0336 (12)	0.0368 (13)	0.0354 (12)	−0.0066 (10)	0.0010 (10)	0.0048 (10)
O6	0.0350 (12)	0.0371 (12)	0.0271 (11)	0.0023 (9)	0.0080 (9)	0.0007 (9)
C1	0.0333 (16)	0.0215 (14)	0.0240 (14)	−0.0037 (12)	0.0111 (13)	0.0007 (12)
C2	0.0280 (15)	0.0193 (14)	0.0248 (14)	−0.0023 (12)	0.0082 (12)	0.0031 (11)
C3	0.0283 (15)	0.0253 (15)	0.0300 (16)	0.0008 (12)	0.0110 (13)	0.0011 (12)
C4	0.0339 (16)	0.0224 (14)	0.0276 (15)	0.0011 (12)	0.0115 (13)	0.0014 (12)
C5	0.0304 (15)	0.0284 (15)	0.0225 (14)	−0.0028 (12)	0.0046 (12)	0.0010 (12)
C6	0.0270 (15)	0.0232 (15)	0.0278 (15)	−0.0033 (12)	0.0080 (12)	0.0009 (12)
C7	0.0274 (15)	0.0273 (15)	0.0258 (15)	0.0005 (12)	0.0073 (12)	0.0024 (12)
C8	0.0204 (14)	0.0267 (15)	0.0256 (15)	0.0025 (11)	0.0037 (12)	0.0048 (12)
C9	0.0188 (14)	0.0302 (16)	0.0232 (14)	−0.0003 (12)	0.0022 (11)	0.0055 (12)
C10	0.0197 (14)	0.0303 (16)	0.0248 (14)	0.0014 (12)	0.0005 (11)	0.0028 (12)
C11	0.0228 (14)	0.0258 (15)	0.0324 (16)	−0.0021 (12)	0.0028 (12)	0.0030 (13)
C12	0.0246 (15)	0.0290 (16)	0.0315 (16)	−0.0004 (12)	0.0078 (12)	0.0050 (13)
C13	0.0258 (15)	0.0308 (16)	0.0293 (15)	0.0030 (12)	0.0094 (12)	0.0016 (13)
C14	0.0271 (15)	0.0327 (16)	0.0227 (14)	−0.0022 (12)	0.0015 (12)	−0.0016 (12)
C15	0.0275 (15)	0.0322 (16)	0.0198 (14)	0.0014 (13)	0.0034 (12)	−0.0045 (12)
C16	0.0311 (16)	0.0295 (16)	0.0200 (14)	−0.0018 (12)	0.0075 (12)	−0.0033 (12)
C17	0.0258 (15)	0.0322 (16)	0.0205 (14)	0.0022 (12)	0.0056 (12)	−0.0074 (12)
C18	0.0259 (15)	0.0357 (17)	0.0239 (15)	0.0048 (13)	0.0006 (12)	−0.0040 (13)
C19	0.0316 (16)	0.0330 (16)	0.0253 (15)	0.0005 (13)	0.0035 (13)	0.0000 (13)
C20	0.0264 (15)	0.0319 (16)	0.0253 (15)	−0.0030 (12)	0.0039 (12)	−0.0039 (12)
C21	0.0243 (15)	0.0351 (17)	0.0318 (16)	0.0045 (13)	0.0071 (12)	−0.0031 (13)
C22	0.0169 (14)	0.0365 (17)	0.0284 (15)	−0.0003 (12)	0.0079 (12)	−0.0040 (13)
C23	0.0203 (14)	0.0364 (17)	0.0242 (15)	−0.0024 (12)	0.0062 (12)	−0.0009 (13)
C24	0.0194 (14)	0.0360 (16)	0.0291 (15)	−0.0046 (12)	0.0076 (12)	−0.0033 (13)
C25	0.0246 (15)	0.0426 (18)	0.0252 (15)	−0.0049 (13)	0.0045 (12)	−0.0049 (13)
C26	0.0283 (16)	0.0382 (18)	0.0309 (16)	−0.0028 (13)	0.0057 (13)	0.0015 (13)
C27	0.0258 (15)	0.0341 (17)	0.0348 (17)	0.0014 (13)	0.0061 (13)	0.0011 (14)
C28	0.0238 (15)	0.0338 (16)	0.0270 (15)	−0.0049 (12)	0.0052 (12)	−0.0030 (12)
C29	0.0388 (18)	0.0371 (18)	0.0361 (17)	−0.0041 (14)	0.0162 (14)	0.0093 (14)
C30	0.0342 (17)	0.049 (2)	0.0357 (17)	0.0018 (15)	0.0125 (14)	0.0130 (15)
C31	0.0431 (19)	0.047 (2)	0.050 (2)	0.0015 (16)	0.0155 (16)	0.0162 (17)
C32	0.049 (2)	0.0395 (19)	0.0370 (18)	−0.0007 (15)	0.0142 (16)	0.0138 (15)
C33	0.0420 (19)	0.0451 (19)	0.0256 (16)	−0.0035 (15)	0.0045 (14)	0.0028 (14)
C34	0.0297 (16)	0.0368 (17)	0.0276 (16)	−0.0023 (13)	0.0008 (13)	0.0035 (13)
C35	0.0396 (18)	0.0364 (17)	0.0276 (16)	0.0034 (14)	0.0134 (14)	0.0006 (13)
C36	0.224 (7)	0.052 (3)	0.054 (3)	0.025 (3)	0.072 (4)	−0.005 (2)
C37	0.061 (2)	0.100 (3)	0.0264 (18)	0.025 (2)	0.0152 (17)	0.0076 (19)
C38	0.055 (3)	0.181 (5)	0.034 (2)	−0.019 (3)	0.0244 (19)	−0.003 (3)
C39	0.0376 (17)	0.0377 (18)	0.0402 (18)	−0.0025 (14)	0.0188 (15)	0.0049 (14)
C40	0.095 (3)	0.062 (3)	0.062 (3)	−0.009 (2)	0.055 (2)	0.005 (2)
C41	0.056 (2)	0.054 (2)	0.060 (2)	0.0030 (18)	0.0272 (19)	0.0257 (19)
C42	0.036 (2)	0.081 (3)	0.071 (3)	−0.0079 (19)	0.0219 (19)	0.021 (2)
C43	0.0383 (18)	0.0366 (18)	0.0359 (18)	−0.0039 (14)	0.0007 (15)	0.0076 (14)
C44	0.087 (3)	0.042 (2)	0.060 (3)	−0.019 (2)	0.007 (2)	0.0008 (18)
C45	0.067 (3)	0.067 (3)	0.072 (3)	−0.001 (2)	0.028 (2)	0.026 (2)
C46	0.056 (2)	0.051 (2)	0.077 (3)	−0.0076 (19)	−0.014 (2)	0.026 (2)
C47	0.052 (2)	0.047 (2)	0.0309 (17)	0.0031 (17)	0.0043 (16)	0.0053 (15)
C48	0.089 (4)	0.190 (6)	0.045 (3)	0.035 (4)	0.025 (3)	0.048 (3)
C49	0.059 (3)	0.110 (4)	0.056 (3)	−0.001 (3)	−0.013 (2)	0.019 (3)
C50	0.238 (8)	0.058 (3)	0.046 (3)	0.030 (4)	−0.019 (4)	0.013 (2)
O7	0.164 (4)	0.069 (2)	0.152 (4)	−0.001 (2)	0.089 (3)	−0.027 (2)
N	0.0533 (18)	0.0499 (19)	0.0513 (18)	0.0084 (15)	0.0212 (15)	0.0091 (15)
C51	0.099 (4)	0.047 (3)	0.095 (3)	0.018 (2)	0.060 (3)	0.021 (2)
C52	0.049 (2)	0.086 (3)	0.082 (3)	0.007 (2)	0.018 (2)	−0.030 (3)
C53	0.067 (3)	0.094 (3)	0.049 (2)	0.017 (2)	0.027 (2)	0.033 (2)

Geometric parameters (Å, º)

O1—C1	1.402 (3)	C14—C15	1.522 (4)
O1—C29	1.445 (4)	C15—C20	1.375 (4)
O2—C30	1.424 (4)	C15—C16	1.399 (4)
O2—C31	1.428 (4)	C16—C17	1.393 (4)
O3—C32	1.440 (4)	C17—C18	1.392 (4)
O3—C33	1.416 (4)	C17—C21	1.517 (4)
O4—C9	1.390 (3)	C18—C19	1.396 (4)
O4—C34	1.437 (3)	C19—C20	1.397 (4)
O5—C16	1.369 (3)	C19—C43	1.538 (4)
O6—C23	1.382 (3)	C21—C22	1.526 (4)
O5—H5	0.82 (3)	C22—C23	1.382 (4)
O6—H6	0.84 (3)	C22—C27	1.391 (4)
O7—C51	1.235 (6)	C23—C24	1.397 (4)
N—C52	1.429 (5)	C24—C25	1.395 (4)
N—C53	1.454 (5)	C24—C28	1.519 (4)
N—C51	1.315 (5)	C25—C26	1.390 (4)
C1—C2	1.398 (4)	C26—C27	1.394 (4)
C1—C6	1.381 (4)	C26—C47	1.539 (4)
C2—C7	1.520 (4)	C29—C30	1.508 (5)
C2—C3	1.385 (4)	C31—C32	1.502 (5)
C3—C4	1.392 (4)	C33—C34	1.490 (4)
C4—C35	1.536 (4)	C35—C38	1.521 (6)
C4—C5	1.389 (4)	C35—C36	1.504 (5)
C5—C6	1.394 (4)	C35—C37	1.508 (5)
C6—C28	1.515 (4)	C39—C41	1.530 (5)
C7—C8	1.517 (4)	C39—C40	1.516 (5)
C8—C13	1.394 (4)	C39—C42	1.521 (5)
C8—C9	1.397 (4)	C43—C45	1.547 (5)
C9—C10	1.401 (4)	C43—C44	1.515 (5)
C10—C14	1.518 (4)	C43—C46	1.504 (5)
C10—C11	1.391 (4)	C47—C49	1.531 (6)
C11—C12	1.389 (4)	C47—C48	1.512 (6)
C12—C13	1.386 (4)	C47—C50	1.507 (5)
C12—C39	1.535 (4)
C1—O1—C29	112.0 (2)	C18—C19—C20	116.5 (3)
C30—O2—C31	116.7 (3)	C18—C19—C43	122.6 (3)
C32—O3—C33	112.6 (2)	C15—C20—C19	123.1 (3)
C9—O4—C34	111.7 (2)	C17—C21—C22	113.3 (2)
C16—O5—H5	109 (2)	C23—C22—C27	118.5 (3)
C23—O6—H6	112 (2)	C21—C22—C23	121.6 (2)
C52—N—C53	115.8 (3)	C21—C22—C27	119.9 (3)
C51—N—C53	124.6 (4)	O6—C23—C24	120.7 (2)
C51—N—C52	119.6 (4)	O6—C23—C22	117.5 (2)
O1—C1—C6	118.3 (2)	C22—C23—C24	121.8 (3)
O1—C1—C2	119.3 (2)	C23—C24—C25	117.2 (3)
C2—C1—C6	122.5 (2)	C23—C24—C28	122.0 (2)
C1—C2—C3	117.0 (2)	C25—C24—C28	120.8 (3)
C1—C2—C7	122.3 (2)	C24—C25—C26	123.5 (3)
C3—C2—C7	120.5 (2)	C25—C26—C47	120.8 (3)
C2—C3—C4	123.1 (2)	C25—C26—C27	116.5 (3)
C3—C4—C35	121.3 (3)	C27—C26—C47	122.7 (3)
C3—C4—C5	117.2 (2)	C22—C27—C26	122.5 (3)
C5—C4—C35	121.4 (3)	C6—C28—C24	113.2 (2)
C4—C5—C6	122.2 (2)	O1—C29—C30	106.8 (2)
C5—C6—C28	120.0 (2)	O2—C30—C29	109.9 (3)
C1—C6—C28	122.0 (2)	O2—C31—C32	113.6 (3)
C1—C6—C5	117.9 (2)	O3—C32—C31	109.6 (3)
C2—C7—C8	110.1 (2)	O3—C33—C34	109.5 (2)
C9—C8—C13	118.4 (2)	O4—C34—C33	109.5 (2)
C7—C8—C9	121.9 (2)	C36—C35—C38	109.1 (4)
C7—C8—C13	119.6 (2)	C37—C35—C38	106.6 (3)
O4—C9—C10	120.1 (2)	C4—C35—C36	107.9 (3)
C8—C9—C10	120.6 (2)	C4—C35—C37	112.8 (3)
O4—C9—C8	119.3 (2)	C4—C35—C38	110.4 (3)
C11—C10—C14	119.2 (2)	C36—C35—C37	110.0 (3)
C9—C10—C14	122.6 (2)	C41—C39—C42	109.5 (3)
C9—C10—C11	118.1 (2)	C12—C39—C40	112.6 (3)
C10—C11—C12	122.9 (3)	C12—C39—C41	110.0 (3)
C11—C12—C13	117.1 (3)	C40—C39—C41	106.6 (3)
C11—C12—C39	119.8 (2)	C40—C39—C42	109.3 (3)
C13—C12—C39	123.1 (3)	C12—C39—C42	108.9 (3)
C8—C13—C12	122.6 (3)	C19—C43—C46	112.5 (3)
C10—C14—C15	110.1 (2)	C19—C43—C44	109.5 (3)
C16—C15—C20	118.4 (2)	C19—C43—C45	109.7 (3)
C14—C15—C20	122.0 (2)	C44—C43—C46	110.8 (3)
C14—C15—C16	119.5 (2)	C45—C43—C46	106.3 (3)
C15—C16—C17	121.1 (3)	C44—C43—C45	107.9 (3)
O5—C16—C15	116.2 (2)	C26—C47—C50	112.8 (3)
O5—C16—C17	122.7 (2)	C48—C47—C49	107.1 (3)
C16—C17—C18	118.1 (2)	C26—C47—C49	109.0 (3)
C18—C17—C21	119.4 (2)	C26—C47—C48	110.0 (3)
C16—C17—C21	122.5 (2)	C48—C47—C50	110.6 (4)
C17—C18—C19	122.7 (3)	C49—C47—C50	107.1 (4)
C20—C19—C43	120.9 (3)	O7—C51—N	125.3 (5)
C29—O1—C1—C2	−85.8 (3)	C11—C12—C39—C42	67.5 (4)
C29—O1—C1—C6	95.5 (3)	C13—C12—C39—C40	8.3 (4)
C1—O1—C29—C30	−176.9 (2)	C11—C12—C39—C41	−52.5 (4)
C31—O2—C30—C29	71.8 (4)	C11—C12—C39—C40	−171.1 (3)
C30—O2—C31—C32	56.6 (4)	C10—C14—C15—C20	−92.7 (3)
C33—O3—C32—C31	154.7 (3)	C10—C14—C15—C16	84.0 (3)
C32—O3—C33—C34	−172.9 (3)	C14—C15—C20—C19	174.6 (3)
C34—O4—C9—C8	87.8 (3)	C14—C15—C16—O5	6.6 (4)
C34—O4—C9—C10	−92.5 (3)	C16—C15—C20—C19	−2.0 (4)
C9—O4—C34—C33	−170.6 (2)	C20—C15—C16—C17	2.2 (4)
C52—N—C51—O7	176.6 (5)	C14—C15—C16—C17	−174.6 (2)
C53—N—C51—O7	0.0 (8)	C20—C15—C16—O5	−176.6 (2)
O1—C1—C2—C3	178.6 (2)	O5—C16—C17—C21	−2.7 (4)
O1—C1—C2—C7	−6.4 (4)	C15—C16—C17—C21	178.6 (3)
C6—C1—C2—C3	−2.8 (4)	O5—C16—C17—C18	177.2 (2)
C6—C1—C2—C7	172.2 (2)	C15—C16—C17—C18	−1.5 (4)
O1—C1—C6—C5	−179.7 (2)	C21—C17—C18—C19	−179.5 (3)
O1—C1—C6—C28	2.7 (4)	C16—C17—C21—C22	−87.6 (3)
C2—C1—C6—C5	1.7 (4)	C16—C17—C18—C19	0.7 (4)
C2—C1—C6—C28	−175.9 (2)	C18—C17—C21—C22	92.5 (3)
C1—C2—C3—C4	1.9 (4)	C17—C18—C19—C43	−179.5 (3)
C7—C2—C3—C4	−173.2 (2)	C17—C18—C19—C20	−0.5 (4)
C1—C2—C7—C8	−86.8 (3)	C18—C19—C20—C15	1.2 (4)
C3—C2—C7—C8	88.1 (3)	C20—C19—C43—C46	168.7 (3)
C2—C3—C4—C5	−0.1 (4)	C20—C19—C43—C45	50.6 (4)
C2—C3—C4—C35	−177.9 (3)	C43—C19—C20—C15	−179.7 (3)
C5—C4—C35—C37	21.9 (4)	C18—C19—C43—C44	111.4 (4)
C3—C4—C5—C6	−1.1 (4)	C20—C19—C43—C44	−67.6 (4)
C3—C4—C35—C37	−160.4 (3)	C18—C19—C43—C45	−130.4 (3)
C3—C4—C35—C38	−41.2 (4)	C18—C19—C43—C46	−12.3 (4)
C5—C4—C35—C36	−99.8 (4)	C17—C21—C22—C23	89.3 (3)
C3—C4—C35—C36	78.0 (4)	C17—C21—C22—C27	−90.0 (3)
C5—C4—C35—C38	141.1 (3)	C27—C22—C23—C24	1.3 (4)
C35—C4—C5—C6	176.7 (3)	C27—C22—C23—O6	−177.9 (2)
C4—C5—C6—C28	178.0 (3)	C21—C22—C23—C24	−177.9 (2)
C4—C5—C6—C1	0.3 (4)	C21—C22—C27—C26	178.9 (2)
C1—C6—C28—C24	89.4 (3)	C23—C22—C27—C26	−0.3 (4)
C5—C6—C28—C24	−88.2 (3)	C21—C22—C23—O6	2.9 (4)
C2—C7—C8—C9	105.7 (3)	O6—C23—C24—C25	178.3 (2)
C2—C7—C8—C13	−70.5 (3)	O6—C23—C24—C28	−3.4 (4)
C7—C8—C9—O4	9.9 (4)	C22—C23—C24—C28	177.5 (2)
C7—C8—C9—C10	−169.8 (2)	C22—C23—C24—C25	−0.8 (4)
C7—C8—C13—C12	174.0 (3)	C23—C24—C28—C6	−88.6 (3)
C13—C8—C9—O4	−173.8 (2)	C25—C24—C28—C6	89.6 (3)
C13—C8—C9—C10	6.5 (4)	C23—C24—C25—C26	−0.7 (4)
C9—C8—C13—C12	−2.3 (4)	C28—C24—C25—C26	−179.0 (3)
O4—C9—C10—C14	−9.7 (4)	C24—C25—C26—C27	1.7 (4)
C8—C9—C10—C11	−5.8 (4)	C24—C25—C26—C47	−176.3 (3)
C8—C9—C10—C14	170.0 (2)	C47—C26—C27—C22	176.8 (3)
O4—C9—C10—C11	174.5 (2)	C25—C26—C27—C22	−1.1 (4)
C14—C10—C11—C12	−175.0 (3)	C25—C26—C47—C49	57.5 (4)
C9—C10—C14—C15	−106.4 (3)	C25—C26—C47—C50	176.3 (4)
C9—C10—C11—C12	0.9 (4)	C27—C26—C47—C48	122.4 (4)
C11—C10—C14—C15	69.4 (3)	C27—C26—C47—C49	−120.4 (3)
C10—C11—C12—C39	−177.5 (3)	C27—C26—C47—C50	−1.6 (5)
C10—C11—C12—C13	3.0 (4)	C25—C26—C47—C48	−59.7 (4)
C13—C12—C39—C41	126.9 (3)	O1—C29—C30—O2	−175.7 (3)
C11—C12—C13—C8	−2.3 (4)	O2—C31—C32—O3	−85.4 (3)
C39—C12—C13—C8	178.3 (3)	O3—C33—C34—O4	69.8 (3)
C13—C12—C39—C42	−113.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O6	0.82 (3)	1.88 (4)	2.694 (3)	175 (4)
O6—H6···O1	0.84 (3)	1.85 (3)	2.682 (3)	172 (4)
C7—H7A···O4	0.99	2.44	2.887 (3)	106
C14—H14B···O4	0.99	2.49	2.924 (3)	106
C21—H21B···O6	0.99	2.47	2.820 (3)	100
C28—H28A···O1	0.99	2.50	2.850 (3)	100
C28—H28A···O2^i	0.99	2.42	3.328 (4)	152
C30—H30A···O3	0.99	2.39	3.011 (4)	120
C32—H32A···O7	0.99	2.35	3.324 (6)	168
C53—H53C···O5	0.98	2.71	3.220 (4)	113
C53—H53C···O7	0.98	2.48	2.861 (6)	103
C51—H51···Cg3^ii	0.95	3.04	3.961 (6)	165
C52—H52A···Cg3^ii	0.98	3.15	4.106 (4)	165
C52—H52B···Cg1^ii	0.98	2.95	3.590 (4)	124
C52—H52B···Cg4^ii	0.98	2.97	3.592 (4)	122
C52—H52C···Cg2^ii	0.98	2.93	3.583 (4)	125

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2.