Hydrogen-bonding controls the solid-state and enanti­omeric comformations of the amino alcohol ligand 2-[(2-hy­droxy­ethyl)amino]cyclo­hexa­nol

The crystal structure of the title compound, C₈H₁₇NO₂, con­sists of (R,R) and (S,S) enantio­meric pairs packed in adjacent double layers which are characterized by centrosymmetric hydrogen-bonded dimers, generated via N—H...O and O—H...O inter­actions, respectively. Inter­molecular inter­actions, related to acceptor and donor mol­ecule chirality, link the achiral double layers into tubular columns, which consist of a staggered hydro­philic inner core surrounded by a hydro­phobic cyclo­alkyl outer surface and extend in the [011] direction.

S1. Comment

Our investigation of reinforced β-amino alcohols as potential metal chelators has highlighted the need for a detailed understanding of the hydrogen-bonding topology associated with these compounds. The relationship between ligand backbone architecture and complex stability indicates that metal ions of smaller ionic radii are preferred upon grafting of cyclohexyl groups across donor atoms (de Sousa et al., 1991; de Sousa & Hancock, 1995). Short non-bonding hydrogen contacts have been reported to cause the observed dependency on metal ion radius (de Sousa et al., 1997a; Hancock et al., 1996), with complexes of larger metal ions being destabilized by hydrogen–hydrogen repulsions. The conformations of amino alcohol chelates and their respective inter- and intramolecular interactions in the solid state may contribute towards a better understanding of this observation. Solid-state analysis of a cycloalkyl-reinforced amino alcohol in which all donor atoms are linked via cyclohexyl bridges suggests that stronger intramolecular hydrogen bonding within the chelating cavity is accompanied by weakening of H···H repulsions (de Sousa & Fernandes, 2003; de Sousa et al., 1997b). The presence of intramolecular hydrogen bonds (Varadwaj et al., 2009), typically defined by string motifs S(n), is implied as relevant in rationalizing the observed trends in the relative stabilities of amino alcohol metal ion complexes. Recent studies of hydrogen-bonding arrays prevalent in a series of N-alkyldiethanolamine ligands relate intramolecular interactions to the steric constraints imposed by ligand backbone architectures (Churakov et al., 2009). Ligand backbone alterations include C-alkyl substitution of hydroxyethyl pendents and varied substituents on the amine N donor atom.

We report here a solid-state study of a reinforced diethanolamine derivative, (I), comprising a cyclohexyl bridge between the amine N atom and a single hydroxy O donor atom, representing C-alkyl substitution across an hydroxyethyl bridge in diethanolamine. Based on a previous study of N,N'-bis(2-hydroxycyclohexyl)-trans-cyclohexane-1,2-diamine (de Sousa & Fernandes, 2003), a crystal structure of (I) containing enantiomeric layers might be expected. In fact, both syn and anti conformations of (I) (Fig. 1), the latter disordered, occur in the structure, with alternating anti- and syn-enantiomeric double layers. The syn O1—C1—C2—N1 torsion angle of 58.99 (10)° suggests minimal torsional strain for the hydroxycyclohexyl pendent, accommodating a N1—C7—C8—O2 torsion angle of -65.11 (13)° for a gauche orientation of the hydroxyethyl pendent. In the anti conformer, the corresponding O1A—C1A—C2A—N1A torsion angle of -54.21 (10)° deviates from that of minimal strain for a cyclohexyl bridge [Reference?]. In addition, a distorted gauche hydroxyethyl pendent has torsion angle N1A—C7A—C8A—O2A = -68.9 (5)°. The hydroxyethyl groups of the predominantly anti conformers are disordered over two positions (Fig. 1), corresponding to anti and syn conformations [N11—C27—C28—O22 65.6 (16)°], with site occupancies of 0.736 (2) and 0.264 (2), respectively.

Pairs of syn enantiomers related by the inversion centre at (1/2, 0, 0) generate an R₂²(16) dimer (Bernstein et al., 1995) via strong O—H···O hydrogen bonds (Table 1, Fig. 2a), while anti enantiomeric pairs related by the inversion centre at (1/2, 1/2, 1/2) generate an R₂²(10) dimer via N—H···O hydrogen bonds (Table 1, Fig. 2b). Molecular planes, separated by 3.2 Å, of syn molecule pairs reveal significant puckering in the centrosymmetric 16-membered rings, compared with 0.72 Å in the structure of diethanolamine (Mootz et al., 1989).

Puckering of the R₂²(10) dimers is minimal, as evidenced by the molecular plane separation of 0.91 Å for pairs of anti molecules. The inversion centres of the R₂²(10) and R₂²(16) dimers are separated by 5.66 Å. Alternating R₂²(16) dimers are therefore significantly separated (11.32 Å) compared with their counterparts in the diethanolamine structure (4.46 Å), largely as a consequence of enantiomeric crystallization into separate layers. The tubular stacks observed in the structure of diethanolamine result from R₂²(16) dimers weakly linked via N—H···O hydrogen bonds.

Hydrogen bonding in (I) links R₂²(16) and R₂²(10) dimers, predominantly via O—H···O and O—H···N hydrogen bonds, to generate a tubular column extending in the [011] direction (Table 1, Fig. 3). Hydroxyethyl atom O12 acts as a hydrogen donor via atom H2 to hydroxyethyl atom O2ⁱⁱ (see Table 1 for details and symmetry codes) in an O—H···O interaction between anti and syn molecules of R₂²(10) and R₂²(16) dimers centred at (1/2, 1/2, 1/2) and (1/2, 1, 1), respectively. A symmetrically equivalent hydrogen bond involving atoms O12ⁱⁱ and O2 links R₂²(10) and R₂²(16) dimers centred at (1/2, 1/2, 1/2) and (1/2, 0, 0), respectively. These O12—H12···O2ⁱⁱ hydrogen bonds are stereospecific, occuring only between molecules of like chirality.

O—H···N hydrogen bonds between centrosymmetric dimers are restricted to the N and O atoms connected via the cyclohexyl bridge (Fig. 3). Stereospecificity originates from the conformation of the O donor atom. O11—H11···N1 hydrogen bonds occur only between syn and anti molecules of opposite chirality where the donor atom, O11, originates from an anti conformer. Hydroxycyclohexyl atom O11 of an anti (R,R) molecule acts as a donor via atom H11 to amine atom N1 of a syn (S,S) molecule (see Fig. 1), linking R₂²(10) and R₂²(16) dimers centred at (1/2, 1/2, 1/2) and (1/2, 0, 0), respectively. An equivalent interaction, between atom O11 of an anti (S,S) molecule and atom N1 of a syn (R,R) molecule, both at (1 - x, 1 - y, 1 - z), links R₂²(10) and R₂²(16) dimers centred at (1/2, 1/2, 1/2) and (1/2, 1, 1), respectively. O1—H1···N11ⁱⁱ hydrogen bonds occur between syn and anti molecules of like chirality, where donor atom O1 originates from a syn conformer. The R₂²(16) dimer centred at (1/2, 0, 0) is linked to the R₂²(10) dimer centred at (1/2, 1/2, 1/2) via atom O1 of a syn (S,S) molecule, hydrogen-bonded to N11ⁱⁱ of an anti (S,S) molecule. The R₂²(16) dimer centred at (1/2, 1, 1) is linked to the R₂²(10) dimer centred at (1/2, 1/2, 1/2) through an equivalent interaction between a syn (R,R) and anti (R,R) molecule. The intricate hydrogen-bonding array within the tubular columns is completed by very weak N—H···O interactions (Fig. 3). In the N1—H3···O12ⁱⁱ hydrogen bonds, donor atom N1 of a syn molecule is hydrogen-bonded to hydroxyethyl atom O12ⁱⁱ of an anti molecule with like chirality.

In conclusion, the anti conformation of (I), observed when grafting a cyclohexyl bridge across a hydroxylethyl pendent, facilitates stronger O—H···O hydrogen bonds between centrosymmetric dimers and favours the formation of tubular columns. Grafting of cyclohexyl bridges into the carbon backbone of amino alcohols may prove to be a useful synthetic strategy in designing self-assembled supramolecular structures of β-amino alcohols.

S2. Experimental

Ethanolamine and cyclohexene oxide were used as obtained from Merck and Aldrich, respectively. Equimolar quantities of ethanolamine (1 g, 16.4 mmol) and cyclohexene oxide (1.61 g, 16.4 mmol) were added to a round-bottomed flask containing absolute ethanol (10 ml). A CaCl₂ drying tube and condenser were fitted to the flask and the mixture was refluxed with stirring at 358 K for 48 h. After completion of the reaction, the solvent was removed under reduced pressure to yield a yellow oil. The oil was dissolved in deionised water (15 ml) and washed with chloroform (30 ml). Upon removal of the solvent under reduced pressure the aqueous layer yielded a light-yellow oil, which was characterized by NMR and FAB-MS to be the product 2-[(2-hydroxyethyl)amino]cyclohexanol, (I). Crystals of (I) formed from the crude oil and the extractant when left unattended for several days (yield 96%). Spectroscopic analysis: ¹H NMR (D₂O, 300 MHz, δ, p.p.m.): 3.61 (2H, m, CH₂), 3.28 (1H, m, CH), 2.66 (2H, m, CH₂), 2.31 (1H, m, CH), 1.89 (2H, m, CH₂), 1.62 (2H, m, CH₂), 1.09 (4H, m, 2 × CH₂); ¹³C NMR (CDCl₃, 300 MHz, δ, p.p.m.): 73.42, 63.15, 60.95, 48.30, 34.16, 30.13, 24.73, 24.63; MS, m/z (FAB) 160 (M+, 100%)

S3. Refinement

H atoms were first located in the difference map and then positioned geometrically. They were allowed to ride on their respective parent atoms, with C—H = 1.00 (CH) or 0.99 Å (CH₂), N—H = 0.92 Å and O—H = 0.84 Å, and with U_iso(H) = 1.2U_eq(C). The disordered hydroxyethyl groups were refined over two positions with similarity restraints, of standard uncertainty 0.001 Å, applied to chemically equivalent bond lengths and angles for disordered hydroxyethyl groups C17—C18—O12 and C27—C28—O22. The N11—C17 and N11—C27 bonds were restrained to have similar lengths within an effective standard uncertainty of 0.001 Å. Atom C27 was restrained to approximate isotropic behaviour with a standard uncertainty of 0.003 Ų. A rigid bond restraint with a standard uncertainty of 0.003 Å was applied to atoms C27, C28 and O22 of the minor conformation of the hydroxyethyl group, of site occupancy 0.264 (2), because the components of the displacement parameters along bond directions between atoms C27 and C28 and C28 and O22 were irregular. In addition, similarity restraints were applied to the displacement parameters of the atoms of the minor conformation of the hydroxyethyl group with a standard uncertainty of 0.01 Ų.

Computing details

Data collection: SMART [APEX2?] (Bruker, 2005); cell refinement: SMART [APEX2?] (Bruker, 2005); data reduction: SAINT [SAINT-Plus?] (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1997); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 2. (a) The R2^2(16) dimers for syn enantiomeric pairs of (I). (b) The R2^2(10) dimers for anti enantiomeric pairs of (I). Dashed lines indicate hydrogen bonds.
	Fig. 3. Intermolecular O—H···N and O—H···O interactions (dashed lines) linking R2^2(10) and R2^2(16) dimers of (I) into tubular columns along [011]. [Symmetry codes: (i) 1 - x, -y, -z; (ii) 1 - x, 1 - y, 1 - z; (iii) 1 - x, 2 - y, 2 - z; (iv) x, 1 + y, 1 + z; (v) x, y - 1, z - 1].

2-[(2-hydroxyethyl)amino]cyclohexanol

Crystal data

C8H17NO2	Z = 4
Mr = 159.23	F(000) = 352
Triclinic, P1	Dx = 1.198 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4334 (2) Å	Cell parameters from 5097 reflections
b = 10.0280 (3) Å	θ = 2.2–28.3°
c = 10.4651 (3) Å	µ = 0.09 mm^−1
α = 112.954 (1)°	T = 173 K
β = 92.429 (1)°	Plate, colourless
γ = 102.055 (1)°	0.48 × 0.40 × 0.15 mm
V = 883.02 (4) Å^3

Data collection

Bruker SMART [APEXII?] CCD area-detector diffractometer	3495 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 28.0°, θmin = 2.1°
ϕ and ω scans	h = −12→12
20934 measured reflections	k = −13→13
4253 independent reflections	l = −13→13

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 0.2058P] where P = (Fo^2 + 2Fc^2)/3
4253 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.33 e Å^−3
31 restraints	Δρmin = −0.19 e Å^−3

Special details

Experimental. Intensity data were collected on a Bruker APEXII CCD area-detector diffractometer with graphite monochromated Mo Kα radiation (50 kV, 30 mA) using the APEX2 (Bruker, 2005a) data collection software. The collection method involved ω scans of width 0.5° and 512 × 512 bit data frames. Data reduction was carried out using the program SAINT-Plus (Bruker, 2005). The crystal structure was solved by direct methods using SHELXTL (Sheldrick, 2008). Non-H atoms were first refined isotropically, followed by anisotropic refinement by full-matrix least-squares calculations based on F² using SHELXTL.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
C1	0.39086 (10)	0.34950 (11)	0.15841 (10)	0.0200 (2)
H1A	0.4014	0.4098	0.2617	0.024*
C2	0.28564 (11)	0.19757 (11)	0.12241 (10)	0.0219 (2)
H2A	0.2781	0.1362	0.0196	0.026*
C3	0.13388 (11)	0.21742 (13)	0.15719 (12)	0.0277 (2)
H3A	0.0660	0.1183	0.1310	0.033*
H3B	0.1390	0.2749	0.2593	0.033*
C4	0.07589 (12)	0.29927 (14)	0.07892 (12)	0.0301 (3)
H4A	−0.0210	0.3139	0.1054	0.036*
H4B	0.0632	0.2378	−0.0232	0.036*
C5	0.18021 (12)	0.45048 (13)	0.11260 (12)	0.0295 (2)
H5A	0.1838	0.5161	0.2126	0.035*
H5B	0.1433	0.4981	0.0555	0.035*
C6	0.33419 (12)	0.43401 (12)	0.08271 (11)	0.0249 (2)
H6A	0.3329	0.3801	−0.0194	0.030*
H6B	0.4011	0.5343	0.1131	0.030*
C7	0.27026 (12)	−0.03677 (12)	0.15081 (13)	0.0318 (3)
H7A	0.2536	−0.0838	0.0471	0.038*
H7B	0.1736	−0.0447	0.1845	0.038*
C8	0.35789 (14)	−0.11912 (13)	0.20404 (13)	0.0347 (3)
H8A	0.3786	−0.0686	0.3075	0.042*
H8B	0.2989	−0.2221	0.1788	0.042*
N1	0.34610 (10)	0.12143 (10)	0.19865 (9)	0.0238 (2)
H3	0.4434	0.1285	0.1883	0.029*
O1	0.53151 (8)	0.33006 (8)	0.12066 (8)	0.02352 (17)
H1	0.5906	0.3568	0.1935	0.035*
O2	0.49166 (9)	−0.12558 (10)	0.14837 (9)	0.0385 (2)
H2	0.4752	−0.1892	0.0650	0.058*
C11	0.32669 (11)	0.30623 (11)	0.58756 (10)	0.0200 (2)
H11A	0.3878	0.3497	0.6814	0.024*
C12	0.21699 (10)	0.40040 (11)	0.59533 (10)	0.0185 (2)
H12A	0.1521	0.3562	0.5035	0.022*
C13	0.12302 (11)	0.39830 (11)	0.70980 (11)	0.0227 (2)
H13A	0.0511	0.4585	0.7138	0.027*
H13B	0.1860	0.4440	0.8016	0.027*
C14	0.04220 (12)	0.23922 (12)	0.68246 (12)	0.0263 (2)
H14A	−0.0144	0.2408	0.7603	0.032*
H14B	−0.0276	0.1967	0.5950	0.032*
C15	0.14871 (12)	0.14127 (12)	0.66941 (12)	0.0270 (2)
H15A	0.0932	0.0370	0.6436	0.032*
H15B	0.2096	0.1758	0.7610	0.032*
C16	0.24777 (12)	0.14630 (11)	0.55875 (12)	0.0263 (2)
H16A	0.3208	0.0881	0.5580	0.032*
H16B	0.1882	0.0995	0.4652	0.032*
N11	0.29472 (9)	0.55411 (9)	0.62213 (9)	0.01932 (18)
H13	0.3728	0.5518	0.5722	0.023*
O11	0.42248 (8)	0.31328 (8)	0.48741 (8)	0.02631 (18)
H11	0.3815	0.2520	0.4069	0.039*
C17	0.1977 (2)	0.63305 (17)	0.5819 (2)	0.0227 (5)	0.736 (2)
H17A	0.1068	0.6233	0.6250	0.027*	0.736 (2)
H17B	0.1707	0.5871	0.4789	0.027*	0.736 (2)
C18	0.2728 (7)	0.7966 (2)	0.6294 (2)	0.0268 (7)	0.736 (2)
H8C	0.3696	0.8062	0.5963	0.032*	0.736 (2)
H8D	0.2135	0.8439	0.5877	0.032*	0.736 (2)
O12	0.29099 (14)	0.87110 (12)	0.77732 (11)	0.0360 (3)	0.736 (2)
H12	0.3499	0.9551	0.8028	0.054*	0.736 (2)
C27	0.1984 (5)	0.6517 (6)	0.6199 (6)	0.0188 (13)	0.264 (2)
H27A	0.1557	0.6820	0.7087	0.023*	0.264 (2)
H27B	0.1168	0.5934	0.5426	0.023*	0.264 (2)
C28	0.273 (2)	0.7909 (5)	0.6017 (10)	0.0309 (16)	0.264 (2)
H28A	0.2036	0.8554	0.6128	0.037*	0.264 (2)
H28B	0.3579	0.8474	0.6756	0.037*	0.264 (2)
O22	0.3202 (4)	0.7557 (5)	0.4685 (4)	0.0497 (12)	0.264 (2)
H2D	0.4005	0.7322	0.4701	0.075*	0.264 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0180 (4)	0.0213 (5)	0.0178 (5)	0.0038 (4)	0.0033 (4)	0.0055 (4)
C2	0.0211 (5)	0.0222 (5)	0.0179 (5)	0.0023 (4)	0.0022 (4)	0.0049 (4)
C3	0.0206 (5)	0.0313 (6)	0.0258 (5)	0.0020 (4)	0.0046 (4)	0.0081 (5)
C4	0.0200 (5)	0.0375 (6)	0.0273 (6)	0.0076 (4)	0.0015 (4)	0.0074 (5)
C5	0.0260 (5)	0.0328 (6)	0.0296 (6)	0.0114 (4)	0.0025 (4)	0.0109 (5)
C6	0.0238 (5)	0.0267 (5)	0.0245 (5)	0.0061 (4)	0.0029 (4)	0.0108 (4)
C7	0.0322 (6)	0.0208 (5)	0.0365 (6)	0.0008 (4)	0.0089 (5)	0.0079 (5)
C8	0.0432 (7)	0.0230 (5)	0.0389 (7)	0.0092 (5)	0.0181 (5)	0.0118 (5)
N1	0.0245 (4)	0.0194 (4)	0.0246 (5)	0.0025 (3)	0.0042 (3)	0.0074 (3)
O1	0.0175 (3)	0.0282 (4)	0.0217 (4)	0.0049 (3)	0.0027 (3)	0.0072 (3)
O2	0.0348 (5)	0.0325 (5)	0.0343 (5)	0.0061 (4)	0.0079 (4)	−0.0004 (4)
C11	0.0200 (5)	0.0195 (5)	0.0197 (5)	0.0058 (4)	0.0055 (4)	0.0064 (4)
C12	0.0186 (4)	0.0178 (4)	0.0175 (5)	0.0038 (3)	0.0022 (4)	0.0061 (4)
C13	0.0228 (5)	0.0224 (5)	0.0240 (5)	0.0078 (4)	0.0086 (4)	0.0090 (4)
C14	0.0234 (5)	0.0274 (5)	0.0292 (6)	0.0043 (4)	0.0075 (4)	0.0132 (5)
C15	0.0307 (6)	0.0213 (5)	0.0303 (6)	0.0050 (4)	0.0083 (4)	0.0122 (4)
C16	0.0304 (5)	0.0183 (5)	0.0289 (6)	0.0071 (4)	0.0095 (4)	0.0073 (4)
N11	0.0184 (4)	0.0172 (4)	0.0229 (4)	0.0050 (3)	0.0037 (3)	0.0083 (3)
O11	0.0249 (4)	0.0248 (4)	0.0254 (4)	0.0051 (3)	0.0113 (3)	0.0059 (3)
C17	0.0265 (9)	0.0195 (9)	0.0187 (12)	0.0056 (6)	−0.0048 (7)	0.0049 (8)
C18	0.0282 (13)	0.0234 (11)	0.0342 (13)	0.0096 (9)	0.0052 (14)	0.0157 (8)
O12	0.0447 (7)	0.0240 (6)	0.0315 (6)	0.0064 (5)	0.0058 (5)	0.0041 (5)
C27	0.020 (2)	0.0218 (19)	0.010 (2)	0.0064 (14)	−0.0062 (14)	0.0017 (15)
C28	0.031 (4)	0.032 (3)	0.038 (3)	0.011 (3)	0.003 (3)	0.022 (3)
O22	0.043 (2)	0.078 (3)	0.055 (2)	0.0238 (19)	0.0152 (17)	0.049 (2)

Geometric parameters (Å, º)

C1—O1	1.4307 (12)	C12—N11	1.4716 (12)
C1—C6	1.5194 (14)	C12—C13	1.5243 (14)
C1—C2	1.5289 (13)	C12—H12A	1.0000
C1—H1A	1.0000	C13—C14	1.5249 (14)
C2—N1	1.4708 (13)	C13—H13A	0.9900
C2—C3	1.5258 (14)	C13—H13B	0.9900
C2—H2A	1.0000	C14—C15	1.5206 (16)
C3—C4	1.5224 (16)	C14—H14A	0.9900
C3—H3A	0.9900	C14—H14B	0.9900
C3—H3B	0.9900	C15—C16	1.5279 (15)
C4—C5	1.5239 (16)	C15—H15A	0.9900
C4—H4A	0.9900	C15—H15B	0.9900
C4—H4B	0.9900	C16—H16A	0.9900
C5—C6	1.5276 (15)	C16—H16B	0.9900
C5—H5A	0.9900	N11—C17	1.4733 (15)
C5—H5B	0.9900	N11—C27	1.4736 (17)
C6—H6A	0.9900	N11—H13	0.9200
C6—H6B	0.9900	O11—H11	0.8400
C7—N1	1.4681 (13)	C17—C18	1.5126 (15)
C7—C8	1.5101 (14)	C17—H17A	0.9900
C7—H7A	0.9900	C17—H17B	0.9900
C7—H7B	0.9900	C18—O12	1.4161 (17)
C8—O2	1.4152 (14)	C18—H8C	0.9900
C8—H8A	0.9900	C18—H8D	0.9900
C8—H8B	0.9900	O12—H12	0.8400
N1—H3	0.9200	C27—C28	1.5117 (16)
O1—H1	0.8400	C27—H27A	0.9900
O2—H2	0.8400	C27—H27B	0.9900
C11—O11	1.4253 (12)	C28—O22	1.4158 (17)
C11—C16	1.5240 (14)	C28—H28A	0.9900
C11—C12	1.5247 (13)	C28—H28B	0.9900
C11—H11A	1.0000	O22—H2D	0.8400
O1—C1—C6	109.13 (8)	N11—C12—C11	109.96 (8)
O1—C1—C2	110.00 (8)	C13—C12—C11	109.62 (8)
C6—C1—C2	111.32 (8)	N11—C12—H12A	108.8
O1—C1—H1A	108.8	C13—C12—H12A	108.8
C6—C1—H1A	108.8	C11—C12—H12A	108.8
C2—C1—H1A	108.8	C12—C13—C14	111.16 (8)
N1—C2—C3	112.09 (9)	C12—C13—H13A	109.4
N1—C2—C1	108.79 (8)	C14—C13—H13A	109.4
C3—C2—C1	110.17 (8)	C12—C13—H13B	109.4
N1—C2—H2A	108.6	C14—C13—H13B	109.4
C3—C2—H2A	108.6	H13A—C13—H13B	108.0
C1—C2—H2A	108.6	C15—C14—C13	111.01 (9)
C4—C3—C2	110.73 (9)	C15—C14—H14A	109.4
C4—C3—H3A	109.5	C13—C14—H14A	109.4
C2—C3—H3A	109.5	C15—C14—H14B	109.4
C4—C3—H3B	109.5	C13—C14—H14B	109.4
C2—C3—H3B	109.5	H14A—C14—H14B	108.0
H3A—C3—H3B	108.1	C14—C15—C16	111.26 (9)
C3—C4—C5	111.12 (9)	C14—C15—H15A	109.4
C3—C4—H4A	109.4	C16—C15—H15A	109.4
C5—C4—H4A	109.4	C14—C15—H15B	109.4
C3—C4—H4B	109.4	C16—C15—H15B	109.4
C5—C4—H4B	109.4	H15A—C15—H15B	108.0
H4A—C4—H4B	108.0	C11—C16—C15	111.40 (8)
C4—C5—C6	111.20 (9)	C11—C16—H16A	109.3
C4—C5—H5A	109.4	C15—C16—H16A	109.3
C6—C5—H5A	109.4	C11—C16—H16B	109.3
C4—C5—H5B	109.4	C15—C16—H16B	109.3
C6—C5—H5B	109.4	H16A—C16—H16B	108.0
H5A—C5—H5B	108.0	C12—N11—C17	111.51 (10)
C1—C6—C5	111.48 (9)	C12—N11—C27	114.4 (2)
C1—C6—H6A	109.3	C12—N11—H13	109.3
C5—C6—H6A	109.3	C17—N11—H13	109.3
C1—C6—H6B	109.3	C27—N11—H13	118.9
C5—C6—H6B	109.3	C11—O11—H11	109.5
H6A—C6—H6B	108.0	N11—C17—C18	110.7 (3)
N1—C7—C8	111.38 (9)	N11—C17—H17A	109.5
N1—C7—H7A	109.4	C18—C17—H17A	109.5
C8—C7—H7A	109.4	N11—C17—H17B	109.5
N1—C7—H7B	109.4	C18—C17—H17B	109.5
C8—C7—H7B	109.4	H17A—C17—H17B	108.1
H7A—C7—H7B	108.0	O12—C18—C17	110.83 (13)
O2—C8—C7	112.50 (9)	O12—C18—H8C	109.5
O2—C8—H8A	109.1	C17—C18—H8C	109.5
C7—C8—H8A	109.1	O12—C18—H8D	109.5
O2—C8—H8B	109.1	C17—C18—H8D	109.5
C7—C8—H8B	109.1	H8C—C18—H8D	108.1
H8A—C8—H8B	107.8	N11—C27—C28	114.8 (9)
C7—N1—C2	113.46 (8)	N11—C27—H27A	108.6
C7—N1—H3	108.9	C28—C27—H27A	108.6
C2—N1—H3	108.9	N11—C27—H27B	108.6
C1—O1—H1	109.5	C28—C27—H27B	108.6
C8—O2—H2	109.5	H27A—C27—H27B	107.5
O11—C11—C16	112.33 (8)	O22—C28—C27	111.51 (17)
O11—C11—C12	111.09 (8)	O22—C28—H28A	109.3
C16—C11—C12	110.59 (8)	C27—C28—H28A	109.3
O11—C11—H11A	107.5	O22—C28—H28B	109.3
C16—C11—H11A	107.5	C27—C28—H28B	109.3
C12—C11—H11A	107.5	H28A—C28—H28B	108.0
N11—C12—C13	110.96 (8)	C28—O22—H2D	109.5
O1—C1—C2—N1	58.98 (10)	C16—C11—C12—C13	58.18 (11)
C6—C1—C2—N1	−179.93 (8)	N11—C12—C13—C14	179.99 (8)
O1—C1—C2—C3	−177.78 (8)	C11—C12—C13—C14	−58.38 (11)
C6—C1—C2—C3	−56.69 (11)	C12—C13—C14—C15	56.64 (12)
N1—C2—C3—C4	178.85 (8)	C13—C14—C15—C16	−54.18 (12)
C1—C2—C3—C4	57.55 (11)	O11—C11—C16—C15	178.58 (9)
C2—C3—C4—C5	−57.19 (12)	C12—C11—C16—C15	−56.69 (12)
C3—C4—C5—C6	55.21 (12)	C14—C15—C16—C11	54.54 (12)
O1—C1—C6—C5	176.79 (8)	C13—C12—N11—C17	−78.63 (13)
C2—C1—C6—C5	55.19 (12)	C11—C12—N11—C17	159.93 (12)
C4—C5—C6—C1	−54.22 (12)	C13—C12—N11—C27	−63.4 (3)
N1—C7—C8—O2	−65.06 (13)	C11—C12—N11—C27	175.1 (2)
C8—C7—N1—C2	165.35 (9)	C12—N11—C17—C18	171.76 (15)
C3—C2—N1—C7	69.67 (11)	C27—N11—C17—C18	67.1 (10)
C1—C2—N1—C7	−168.25 (8)	N11—C17—C18—O12	−68.9 (5)
O11—C11—C12—N11	−54.15 (10)	C12—N11—C27—C28	−161.7 (5)
C16—C11—C12—N11	−179.58 (8)	C17—N11—C27—C28	−80.4 (10)
O11—C11—C12—C13	−176.38 (8)	N11—C27—C28—O22	65.7 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1^i	0.84	1.89	2.7270 (11)	172
N11—H13···O11^ii	0.92	2.37	3.1884 (11)	148
O12—H12···O2^ii	0.84	1.90	2.7299 (14)	170
O11—H11···N1	0.84	2.03	2.8379 (12)	162
O1—H1···N11^ii	0.84	1.94	2.7701 (11)	169
N1—H3···O12^ii	0.92	2.52	3.4051 (16)	163

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