anti-2-Hydr­oxy-2-methyl-1-tetra­lone oxime: X-ray and density functional theory study

Crystals of the title racemic compound, C₁₁H₁₃NO₂, consist of two types of mol­ecules (conformers); one mol­ecule has an exocyclic OH group in an equatorial position and the other has this group in an axial position. Consequently, the hydrogen-bond schemes for the two mol­ecules are different. The mol­ecules with equatorial OH groups create infinite parallel chains (formed by the same enantio­mer), connected by centrosymmetric dimers of mol­ecules (of mixed enantio­mers), both with axial OH groups. Possible inter­conversion of the conformers and the flexibility of the mol­ecule were studied by means of different MP2 and density functional theory (DFT) methods. The optimization of the structure by the DFT method confirmed the types of the hydrogen bonds.

S1. Comment

Recently we have found that enantiomerically pure 2-hydroxy-2-methyl-1-tetralone, (I), can be used as a chiral auxiliary for the stereoselective synthesis and/or epimerization of α-amino acids (Solladié-Cavallo et al., 2002). We described the synthesis of (I) in racemic or enantiomerically enriched forms elsewhere (Solladié-Cavallo et al., 2001, 2002; Pažický et al., 2006). The (R)-2-hydroxy-2-methyl-1-tetralone enantiomer was prepared by a stereoselective oxidation with chiral oxazitidines in 95% ee (Davis & Weismiller, 1990). This method is efficient but rather costly, so we decided to attempt to prepare enantiomerically pure (I) via crystallization of its oxime (II). Such an enantioseparation method was successfully applied on a similar compound; enantiometrically pure 2-hydroxypinan-3-one was obtained via crystallization of its enantiomerically enriched oxime, followed by hydrolysis (Markowicz et al., 2002).

During the synthesis of the corresponding oxime from 2-hydroxy-2-methyl-1-tetralone, two racemic diastereoisomeric compounds, syn-(IIa) and anti-(IIb), were formed. Compound syn-(IIa) isomerized easily to the more stable anti-(IIb). By careful crystallization of (IIb), crystals suitable for X-ray structure analysis were prepared. The X-ray experiment revealed that oxime anti-(IIb) did not form a conglomerate but preferentially crystallized as a racemic compound. Therefore, the enantioseparation of anti-(IIb) is not possible starting from its racemic mixture.

The crystal structure and theoretical investigation of the electronic structure of the title racemic compound, (IIb), are presented here.

The numbering scheme for (IIb), together with the atomic displacement ellipsoids plot, is shown in Fig. 1. Selected geometric parameters are presented in Table 1. The two molecules in the asymmetric unit differ in the conformation of the six-membered ring, with a difference in the position of the exocyclic OH group. The molecules of type 1 (containing C11) have OH groups in axial positions, and the molecules of type 2 (containing C21) have OH groups in equatorial positions. From this point of view, the conformational flexibility of this ring is interesting. Although three atoms in this ring formally have sp²-hybridization and further restraint is imposed by conjugation of the ═N—OH bond with the aromatic ring, the molecule is still quite flexible. Calculations at the MP2/6–31+G** (Pople et al., 1976; Frisch et al., 1990; Fletcher et al., 1999; Hehre et al., 1972; Clark et al., 1983) and B3LYP/6–31+G** (Becke, 1988, 1992a,b, 1993; Lee et al., 1988) levels showed that a conformational change between the OH-equatorial and OH-axial configurations is possible (Table 2) with an intermediate skew conformation, as seen in Figs. 2 and 3. A l l combinations of the standard quantum chemical methods and the basis sets used agree with the fact that the saturated ring is quite flexible and with the ordering of all three conformers discussed.

The two molecules in the asymmetric unit have different hydrogen-bonding schemes (Fig. 4). The molecules of type 2, with OH in the equatorial position, form infinite chains in the a direction. These chains are connected by centrosymmetric dimers formed by molecules of type 1. The dimers are formed in a manner similar to those for, for example, (±)dibenzobicyclo[b,f][3.3.1]nona-5a,6a-dien-6,12-dioxime (Field et al., 2002; Levkin et al., 2003), (E)-17-oximino-3-hydroxy-1,3,5(10)-estratriene (Hejaz et al., 1999) and 17α-benzyl-16-hydroxyimino-3-methoxyestra-1,3,5(10)-trien-17β-ol (Stanković et al., 1996). The hydrogen–bonding geometries for (IIb) are compared in Table 3. The theoretical investigation of hydrogen bonds was performed using the Vienna ab-initio simulation package VASP (Kresse & Furthmüller, 1996). The calculations were based on the DFT with periodic boundary conditions (Jones & Gunnarsson, 1989) using generalized gradient approximation (GGA) in exchange-correlation functional. The optimization of the structure by the DFT method was performed mainly to improve the positions of the H atoms. The calculations confirmed the types of the hydrogen bonds found by the experiment and refined their bond lengths.

The hydrogen-bonding pattern can be described using graph-set theory (Bernstein et al., 1995; Grell et al., 1999). The first-level graph-set descriptors are dimers D(2) and D(2), a ring R₂²(6), and a string S(5) for strong hydrogen bonds a–d, respectively, while the second-level descriptors are assigned as C₂²(8) for bonds a and b, D₃³(14) for bonds a and c, and D₃³(12) for bonds b and c. The assignment of graph-set descriptors was performed using PLUTO, as described by Motherwell et al. (1999), and the notation of the hydrogen bonds here is that given in Table 3 and Fig. 4.

S2. Experimental

An ethanol/water solution of an equimolar ratio of racemic 2-hydroxy-2-methyl-1-tetralone, (I), hydroxylamine hydrochloride (NH₂OH·HCl) and sodium acetate (AcONa) was stirred for 6 d at room temperature, whereupon a mixture of diastereoisomers (IIa) and (IIb) was formed. The pure diastereoisomer (IIb) was obtained by flash chromatography on SiO₂, followed by crystallization. To a mixture of II(b) (36 mg 188.3 mmol) and hexsol (5.4 ml, light fraction of petrol ether), toluene (1.2 ml) was added. The mixture was heated to reflux. The solution obtained was left to stand in a cotton-covered flask in a small Dewar flask overnight. Straw-like crystals (32 mg, 167.3 mmol) were obtained in 88.9% yield, m.p. 387–389 K. Recrystallization was performed from a warm solution of II(b) (28 mg, 146.4 mmol) in hexsol (6.0 ml) and toluene (1.5 ml), standing in a cotton-covered flask in a small Dewar flask at room temperature. After 24 h, the solution was seeded with one microscope-selected crystal. In this manner, X-ray quality crystals were obtained after 48 h. The crystals were filtered off, washed with hexsol and dried in air (yield 10.9 mg, 57.0 mmol, 38.9%).

S3. Refinement

C-bound H atoms for compound (IIb) were constrained to the ideal geometry using an appropriate riding model and were refined isotropically with common displacement parameters for respective groups. The C—H distances were kept fixed at 0.95 Å for aromatic H atoms and at 0.99 Å for secondary H atoms. For methyl groups, the C—H distances (0.98 Å) and C—C—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting position based on the threefold averaged circular Fourier synthesis. For the hydroxy groups, the O—H distance (0.84 Å) and C—O—H angle (109.5°) were used for calculating a starting position based on the circular Fourier synthesis; both the torsion angle and the O—H distance were then allowed to refine.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995) and SADABS (Sheldrick, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A perspective drawing showing the atom-numbering scheme of (IIb). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A schematic representation of the relative energies of the conformations of (IIb) and transition states connecting them.
	Fig. 3. A schematic representation of the skew conformation of (IIb).
	Fig. 4. The hydrogen-bonding pattern in the crystal structure of (IIb). H atoms not involved in strong hydrogen bonds have been omitted for clarity. For symmetry codes and notation of hydrogen bonds see Table 3.

anti-2-Hydroxy-2-methyl-1-tetralone oxime

Crystal data

C11H13NO2	Z = 4
Mr = 191.22	F(000) = 408
Triclinic, P1	Dx = 1.283 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3655 (2) Å	Cell parameters from 3464 reflections
b = 9.6851 (2) Å	θ = 2.2–25.5°
c = 14.4720 (1) Å	µ = 0.09 mm^−1
α = 93.375 (1)°	T = 173 K
β = 99.476 (1)°	Plate, colourless
γ = 102.288 (1)°	0.46 × 0.11 × 0.01 mm
V = 990.22 (3) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	3654 independent reflections
Radiation source: fine-focus sealed tube	2215 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→8
Tmin = 0.960, Tmax = 0.999	k = −11→11
11309 measured reflections	l = −17→17

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0551P)^2] where P = (Fo^2 + 2Fc^2)/3
3654 reflections	(Δ/σ)max < 0.001
266 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 3464 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995).

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 (Ų)

	x	y	z	Uiso*/Ueq
O11	0.3489 (2)	0.75256 (16)	0.18986 (10)	0.0241 (4)
H11	0.238 (4)	0.7465 (14)	0.2117 (16)	0.045 (2)*
O12	0.0373 (2)	0.87794 (18)	−0.06966 (10)	0.0301 (4)
H12	−0.041 (3)	0.936 (3)	−0.0787 (7)	0.045 (2)*
O21	0.0573 (3)	0.7526 (2)	0.28386 (11)	0.0375 (5)
H21	−0.048 (4)	0.756 (3)	0.2598 (9)	0.045 (2)*
O22	−0.4307 (2)	0.7460 (2)	0.35495 (11)	0.0364 (5)
H22	−0.511 (3)	0.748 (3)	0.3003 (16)	0.045 (2)*
N11	0.1423 (3)	0.9074 (2)	0.02217 (12)	0.0246 (5)
N21	−0.2541 (3)	0.7382 (2)	0.33542 (13)	0.0273 (5)
C11	0.3873 (3)	0.8794 (2)	0.14159 (15)	0.0224 (5)
C12	0.5965 (3)	0.9124 (2)	0.13849 (16)	0.0260 (6)
H12A	0.6690	0.9340	0.2036	0.036 (2)*
H12B	0.6277	0.9980	0.1049	0.036 (2)*
C13	0.6564 (3)	0.7913 (3)	0.09017 (16)	0.0281 (6)
H13A	0.7847	0.8265	0.0766	0.036 (2)*
H13B	0.6634	0.7168	0.1338	0.036 (2)*
C14	0.5262 (3)	0.7263 (2)	0.00020 (15)	0.0244 (6)
C15	0.3416 (3)	0.7438 (2)	−0.02187 (15)	0.0236 (6)
C16	0.2770 (3)	0.8420 (2)	0.04107 (15)	0.0220 (5)
C17	0.5921 (4)	0.6411 (3)	−0.06167 (17)	0.0340 (6)
H17	0.7190	0.6312	−0.0474	0.045 (3)*
C18	0.4779 (4)	0.5717 (3)	−0.14241 (18)	0.0414 (7)
H18	0.5257	0.5154	−0.1843	0.045 (3)*
C19	0.2933 (4)	0.5838 (3)	−0.16252 (18)	0.0442 (8)
H19	0.2125	0.5338	−0.2177	0.045 (3)*
C110	0.2249 (4)	0.6680 (3)	−0.10315 (17)	0.0374 (7)
H110	0.0967	0.6747	−0.1175	0.045 (3)*
C111	0.3396 (4)	1.0023 (3)	0.19507 (16)	0.0299 (6)
H11A	0.2051	0.9793	0.1989	0.045 (2)*
H11B	0.3678	1.0878	0.1622	0.045 (2)*
H11C	0.4153	1.0193	0.2587	0.045 (2)*
C21	0.0653 (3)	0.7416 (3)	0.38287 (16)	0.0260 (6)
C22	0.2028 (4)	0.8707 (3)	0.43698 (18)	0.0358 (7)
H22A	0.3294	0.8759	0.4208	0.036 (2)*
H22B	0.1612	0.9575	0.4187	0.036 (2)*
C23	0.2152 (4)	0.8641 (3)	0.54285 (18)	0.0406 (7)
H23A	0.3038	0.8039	0.5645	0.036 (2)*
H23B	0.2691	0.9609	0.5748	0.036 (2)*
C24	0.0292 (4)	0.8066 (3)	0.57317 (17)	0.0327 (6)
C25	−0.1370 (3)	0.7500 (2)	0.50857 (15)	0.0254 (6)
C26	−0.1258 (3)	0.7414 (2)	0.40720 (15)	0.0236 (5)
C27	0.0222 (4)	0.8073 (3)	0.66868 (18)	0.0417 (7)
H27	0.1343	0.8452	0.7134	0.045 (3)*
C28	−0.1427 (4)	0.7546 (3)	0.69970 (18)	0.0435 (8)
H28	−0.1439	0.7554	0.7653	0.045 (3)*
C29	−0.3069 (4)	0.7003 (3)	0.63567 (17)	0.0381 (7)
H29	−0.4216	0.6647	0.6570	0.045 (3)*
C210	−0.3042 (4)	0.6979 (3)	0.54069 (16)	0.0310 (6)
H210	−0.4175	0.6604	0.4967	0.045 (3)*
C211	0.1253 (3)	0.6042 (2)	0.40441 (17)	0.0321 (6)
H21A	0.0318	0.5236	0.3684	0.045 (2)*
H21B	0.1337	0.5938	0.4718	0.045 (2)*
H21C	0.2489	0.6068	0.3869	0.045 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0223 (10)	0.0296 (9)	0.0219 (9)	0.0061 (8)	0.0058 (7)	0.0081 (7)
O12	0.0290 (10)	0.0392 (10)	0.0209 (9)	0.0115 (8)	−0.0042 (7)	0.0031 (7)
O21	0.0265 (11)	0.0605 (12)	0.0302 (10)	0.0137 (10)	0.0111 (8)	0.0127 (9)
O22	0.0181 (10)	0.0704 (13)	0.0235 (9)	0.0153 (9)	0.0030 (8)	0.0106 (9)
N11	0.0239 (12)	0.0309 (11)	0.0170 (10)	0.0033 (10)	0.0003 (9)	0.0064 (8)
N21	0.0167 (11)	0.0408 (13)	0.0261 (11)	0.0080 (10)	0.0054 (9)	0.0062 (9)
C11	0.0245 (14)	0.0242 (13)	0.0195 (12)	0.0054 (11)	0.0049 (10)	0.0075 (10)
C12	0.0242 (14)	0.0287 (13)	0.0229 (13)	0.0013 (11)	0.0032 (11)	0.0055 (10)
C13	0.0222 (14)	0.0329 (14)	0.0315 (14)	0.0062 (12)	0.0098 (11)	0.0083 (11)
C14	0.0301 (15)	0.0243 (13)	0.0222 (13)	0.0078 (11)	0.0104 (11)	0.0068 (10)
C15	0.0311 (15)	0.0221 (13)	0.0181 (12)	0.0052 (11)	0.0054 (10)	0.0061 (10)
C16	0.0197 (13)	0.0243 (13)	0.0215 (12)	0.0018 (11)	0.0048 (10)	0.0073 (10)
C17	0.0384 (17)	0.0311 (15)	0.0392 (16)	0.0111 (13)	0.0188 (13)	0.0113 (12)
C18	0.069 (2)	0.0326 (16)	0.0302 (15)	0.0188 (16)	0.0195 (15)	0.0029 (12)
C19	0.067 (2)	0.0363 (16)	0.0254 (15)	0.0157 (15)	−0.0038 (14)	−0.0052 (12)
C110	0.0480 (18)	0.0327 (15)	0.0298 (15)	0.0130 (14)	−0.0018 (13)	−0.0001 (12)
C111	0.0332 (16)	0.0347 (14)	0.0224 (13)	0.0112 (12)	0.0024 (11)	0.0025 (11)
C21	0.0203 (14)	0.0325 (14)	0.0267 (13)	0.0062 (11)	0.0071 (10)	0.0062 (11)
C22	0.0238 (15)	0.0314 (15)	0.0511 (17)	0.0032 (12)	0.0077 (13)	0.0045 (13)
C23	0.0322 (17)	0.0352 (16)	0.0469 (17)	0.0044 (13)	−0.0055 (13)	−0.0076 (13)
C24	0.0347 (16)	0.0318 (15)	0.0297 (15)	0.0135 (13)	−0.0038 (12)	−0.0054 (11)
C25	0.0277 (15)	0.0296 (14)	0.0196 (13)	0.0118 (12)	0.0006 (11)	−0.0009 (10)
C26	0.0247 (14)	0.0237 (13)	0.0218 (13)	0.0048 (11)	0.0032 (11)	0.0030 (10)
C27	0.050 (2)	0.0426 (17)	0.0271 (15)	0.0177 (15)	−0.0143 (14)	−0.0101 (12)
C28	0.065 (2)	0.0530 (18)	0.0188 (14)	0.0318 (17)	0.0034 (15)	−0.0008 (13)
C29	0.0428 (18)	0.0529 (17)	0.0275 (15)	0.0246 (15)	0.0126 (13)	0.0085 (13)
C210	0.0280 (16)	0.0470 (16)	0.0212 (13)	0.0156 (13)	0.0041 (11)	0.0055 (11)
C211	0.0257 (15)	0.0347 (15)	0.0377 (15)	0.0084 (12)	0.0095 (12)	0.0022 (12)

Geometric parameters (Å, º)

O11—C11	1.448 (2)	C19—H19	0.9500
O11—H11	0.9120	C110—H110	0.9500
O12—N11	1.403 (2)	C111—H11A	0.9800
O12—H12	0.8936	C111—H11B	0.9800
O21—C21	1.436 (3)	C111—H11C	0.9800
O21—H21	0.8041	C21—C26	1.506 (3)
O22—N21	1.392 (2)	C21—C211	1.521 (3)
O22—H22	0.9095	C21—C22	1.512 (3)
N11—C16	1.288 (3)	C22—C23	1.526 (4)
N21—C26	1.278 (3)	C22—H22A	0.9900
C11—C12	1.515 (3)	C22—H22B	0.9900
C11—C16	1.527 (3)	C23—C24	1.510 (4)
C11—C111	1.516 (3)	C23—H23A	0.9900
C12—C13	1.512 (3)	C23—H23B	0.9900
C12—H12A	0.9900	C24—C25	1.397 (3)
C12—H12B	0.9900	C24—C27	1.391 (4)
C13—C14	1.499 (3)	C25—C210	1.392 (3)
C13—H13A	0.9900	C25—C26	1.481 (3)
C13—H13B	0.9900	C27—C28	1.372 (4)
C14—C17	1.394 (3)	C27—H27	0.9500
C14—C15	1.393 (3)	C28—C29	1.379 (4)
C15—C110	1.400 (3)	C28—H28	0.9500
C15—C16	1.481 (3)	C29—C210	1.377 (3)
C17—C18	1.367 (4)	C29—H29	0.9500
C17—H17	0.9500	C210—H210	0.9500
C18—C19	1.374 (4)	C211—H21A	0.9800
C18—H18	0.9500	C211—H21B	0.9800
C19—C110	1.375 (3)	C211—H21C	0.9800
C11—O11—H11	109.5	C11—C111—H11C	109.5
N11—O12—H12	109.5	H11A—C111—H11C	109.5
C21—O21—H21	109.5	H11B—C111—H11C	109.5
N21—O22—H22	109.5	O21—C21—C26	109.47 (18)
C16—N11—O12	115.83 (18)	O21—C21—C211	107.29 (19)
C26—N21—O22	115.51 (18)	C26—C21—C211	111.33 (19)
O11—C11—C12	106.75 (17)	O21—C21—C22	109.0 (2)
O11—C11—C16	106.83 (17)	C26—C21—C22	107.37 (19)
C12—C11—C16	108.61 (18)	C211—C21—C22	112.3 (2)
O11—C11—C111	110.26 (17)	C23—C22—C21	110.9 (2)
C12—C11—C111	109.65 (19)	C23—C22—H22A	109.4
C16—C11—C111	114.42 (18)	C21—C22—H22A	109.4
C11—C12—C13	112.67 (19)	C23—C22—H22B	109.4
C11—C12—H12A	109.1	C21—C22—H22B	109.4
C13—C12—H12A	109.1	H22A—C22—H22B	108.0
C11—C12—H12B	109.1	C24—C23—C22	114.8 (2)
C13—C12—H12B	109.1	C24—C23—H23A	108.6
H12A—C12—H12B	107.8	C22—C23—H23A	108.6
C14—C13—C12	113.79 (19)	C24—C23—H23B	108.6
C14—C13—H13A	108.8	C22—C23—H23B	108.6
C12—C13—H13A	108.8	H23A—C23—H23B	107.5
C14—C13—H13B	108.8	C25—C24—C27	118.3 (3)
C12—C13—H13B	108.8	C25—C24—C23	122.4 (2)
H13A—C13—H13B	107.7	C27—C24—C23	119.4 (2)
C17—C14—C15	119.3 (2)	C210—C25—C24	119.8 (2)
C17—C14—C13	118.0 (2)	C210—C25—C26	122.2 (2)
C15—C14—C13	122.6 (2)	C24—C25—C26	117.9 (2)
C14—C15—C110	118.4 (2)	N21—C26—C25	129.7 (2)
C14—C15—C16	118.9 (2)	N21—C26—C21	113.56 (19)
C110—C15—C16	122.7 (2)	C25—C26—C21	116.7 (2)
N11—C16—C15	128.9 (2)	C28—C27—C24	121.5 (3)
N11—C16—C11	113.4 (2)	C28—C27—H27	119.2
C15—C16—C11	117.60 (19)	C24—C27—H27	119.2
C18—C17—C14	121.3 (3)	C27—C28—C29	120.0 (2)
C18—C17—H17	119.3	C27—C28—H28	120.0
C14—C17—H17	119.3	C29—C28—H28	120.0
C19—C18—C17	119.6 (2)	C210—C29—C28	119.8 (3)
C19—C18—H18	120.2	C210—C29—H29	120.1
C17—C18—H18	120.2	C28—C29—H29	120.1
C110—C19—C18	120.4 (3)	C25—C210—C29	120.6 (2)
C110—C19—H19	119.8	C25—C210—H210	119.7
C18—C19—H19	119.8	C29—C210—H210	119.7
C19—C110—C15	120.9 (3)	C21—C211—H21A	109.5
C19—C110—H110	119.5	C21—C211—H21B	109.5
C15—C110—H110	119.5	H21A—C211—H21B	109.5
C11—C111—H11A	109.5	C21—C211—H21C	109.5
C11—C111—H11B	109.5	H21A—C211—H21C	109.5
H11A—C111—H11B	109.5	H21B—C211—H21C	109.5
O11—C11—C12—C13	57.8 (2)	O21—C21—C22—C23	179.7 (2)
C16—C11—C12—C13	−57.1 (2)	C26—C21—C22—C23	61.1 (3)
C111—C11—C12—C13	177.22 (18)	C211—C21—C22—C23	−61.6 (3)
C11—C12—C13—C14	45.0 (3)	C21—C22—C23—C24	−39.2 (3)
C12—C13—C14—C17	163.5 (2)	C22—C23—C24—C25	6.6 (3)
C12—C13—C14—C15	−18.8 (3)	C22—C23—C24—C27	−174.6 (2)
C17—C14—C15—C110	3.8 (3)	C27—C24—C25—C210	0.8 (3)
C13—C14—C15—C110	−173.9 (2)	C23—C24—C25—C210	179.7 (2)
C17—C14—C15—C16	−176.0 (2)	C27—C24—C25—C26	−176.2 (2)
C13—C14—C15—C16	6.3 (3)	C23—C24—C25—C26	2.6 (3)
O12—N11—C16—C15	2.6 (3)	O22—N21—C26—C25	1.0 (4)
O12—N11—C16—C11	179.40 (17)	O22—N21—C26—C21	−176.56 (18)
C14—C15—C16—N11	156.4 (2)	C210—C25—C26—N21	27.7 (4)
C110—C15—C16—N11	−23.4 (4)	C24—C25—C26—N21	−155.3 (2)
C14—C15—C16—C11	−20.4 (3)	C210—C25—C26—C21	−154.8 (2)
C110—C15—C16—C11	159.9 (2)	C24—C25—C26—C21	22.2 (3)
O11—C11—C16—N11	113.0 (2)	O21—C21—C26—N21	5.8 (3)
C12—C11—C16—N11	−132.2 (2)	C211—C21—C26—N21	−112.7 (2)
C111—C11—C16—N11	−9.3 (3)	C22—C21—C26—N21	124.0 (2)
O11—C11—C16—C15	−69.8 (2)	O21—C21—C26—C25	−172.07 (19)
C12—C11—C16—C15	45.0 (3)	C211—C21—C26—C25	69.5 (3)
C111—C11—C16—C15	167.9 (2)	C22—C21—C26—C25	−53.8 (3)
C15—C14—C17—C18	−1.6 (3)	C25—C24—C27—C28	−0.2 (4)
C13—C14—C17—C18	176.2 (2)	C23—C24—C27—C28	−179.1 (2)
C14—C17—C18—C19	−1.1 (4)	C24—C27—C28—C29	−0.5 (4)
C17—C18—C19—C110	1.6 (4)	C27—C28—C29—C210	0.7 (4)
C18—C19—C110—C15	0.6 (4)	C24—C25—C210—C29	−0.7 (4)
C14—C15—C110—C19	−3.3 (4)	C26—C25—C210—C29	176.3 (2)
C16—C15—C110—C19	176.4 (2)	C28—C29—C210—C25	−0.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O21	0.91	1.83	2.725 (2)	165
O12—H12···N11^i	0.89	2.01	2.801 (3)	147
O21—H21···N21	0.80	2.00	2.505 (2)	121
O22—H22···O11^ii	0.91	1.76	2.670 (2)	176
C211—H21C···O22^iii	0.98	2.58	3.474 (3)	151
C110—H110···O12	0.95	2.20	2.753 (3)	116
C210—H210···O22	0.95	2.25	2.796 (3)	116

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