4,4′-(4,5-Dimethyl-1,2-phenyl­ene)bis­(2-methyl­but-3-yn-2-ol): structural variation in vicinal dialkynols

The structure of the title compound, C₁₈H₂₂O₂, contains two non-equivalent mol­ecules which differ primarily in the location of the –OH groups on opposite sides or on the same side of the mol­ecular plane. Inversion-symmetric pairs of mol­ecules form inter­molecular O—H...O hydrogen-bonded tetra­meric synthons that link non-equivalent mol­ecules into an approximately square double layer parallel to (02). Recently reported fluorinated analogues [Kane, Meyers, Yu, Gerken & Etzkorn (2011). Eur. J. Org. Chem. pp. 2969–2980] have significantly different structures of varying complexity that incorporate intra­molecular hydrogen bonding and suggest that further study of structure versus substituents in vicinal dialkynols could be fruitful.

S1. Comment

Dialkynols have been extensively studied as part of a broader survey of gem-alkynol structures (Madhavi, Desiraju et al., 2000a; Nangia, 2010). Since the gem-alkynol moiety provides two functional groups, –OH and –C≡CH, there are several competing ways in which groups on neighboring molecules can interact which, in turn, lead to a wide variety of synthons and structures (Madhavi, Bilton et al., 2000; Banerjee et al., 2006). One recurring structural motif is a tetrameric synthon of functional groups that are hydrogen-bonded together in a square arrangement (Madhavi, Desiraju et al., 2000b; Bilton et al., 2001). The di-gem-alkynols studied often place the alkynol groups on opposite sides of an organic ring, so intramolecular interactions are inhibited. Vicinal dialkynol structures have recently been reported in which the alkynol groups are ortho, but with –C≡CH groups absent, so the –OH groups are positioned to act as molecular tweezers in which intramolecular hydrogen bonding is now possible (Kane et al., 2011). We report here the structure of the title new vicinal dialkynol compound, (I), an intermediate in an effort to prepare cyclic diacetylenes (Zhou et al., 1994), which was synthesized by treatment of 1,2-diiodo-4,5-dimethylbenzene (Hathaway et al., 2009) with excess 2-methyl-3-butyn-2-ol in the presence of copper(I) and palladium catalysts (Melissaris & Litt, 1994).

The two non-equivalent molecules in the asymmetric unit of (I) (the first digit of the atom label denotes assignment to molecule 0 or 1) are each quasi-planar for the core atoms, i.e. those that are, or are bound to atoms that are, sp or sp² hybridized. Bond lengths and angles within each molecule conform to expected values (Ladd & Palmer, 1994). The molecules have no formal site symmetry, although each approximates mm2 symmetry for the core atoms, with half of the nominally equivalent bond lengths agreeing within 1 s.u. and all within 2 s.u. Nominally equivalent bond angles for ring atoms agree within 3 s.u. (with one slight exception), but the angles in the alkynol groups disagree by more. Similar bond lengths between non-equivalent molecules agree (with one slight exception) within 3 s.u. for Csp, Csp² or O atoms, while Csp³—Csp³ bonds agree within 4 s.u. Differences in similar bond angles between non-equivalent molecules are larger and agree within 3–5 s.u. in the ring, with even greater disagreement in the alkynol groups. Bonds in the ring between substituents are elongated compared with the others, with the CX1—CX2 bond between alkynol groups longest. The substituents are scissored outward, as shown by bond angles at the substituted ring atoms <120° for aromatic ring atoms only and interior angles involving the substituent >120°. Angles about the unsubstituted ring atoms of ~122° indicate a slight scissoring inward of these atoms with an outward scissoring of the substituents. The main geometric difference between the non-equivalent molecules is the –OH group conformation on opposite sides of the molecular plane (molecule 0), or on the same side (molecule 1), which reduces the approximate point-group symmetry of molecule 0 to 2, and of molecule 1 to m. A displacement ellipsoid plot of the asymmetric unit of (I) is presented in Fig. 1.

Inversion-related molecular pairs are formed, with interplanar spacings of 3.486 (1) and 3.717 (1) Å for molecules 0 and 1, respectively. The aromatic rings within each pair are offset away from each other, principally along a line parallel to the alkynol arms of O1 or O11, with distances between the ring-atom centroids (measured perpendicular to the mean-plane normal) of 1.394 (2) and 1.547 (2) Å for molecules 0 and 1, respectively. Since the interplanar spacings are greater than the sum of the van der Waals radii (Bondi, 1964) and the large ring displacements lead to only minor (30–35%) overlap, it is unlikely that there is a significant attractive interaction between the molecules of each pair. The long axes of the non-equivalent molecules are almost perpendicular [angle of 86.17 (7)° between least-squares lines formed by the core atoms], with that of molecule 0 parallel to [201] and that of molecule 1 almost parallel to b. These vectors demarcate axes for an approximately square grid (23.0784 (3) Å along [201] versus 22.7966 (3) Å along b) of inversion-related pairs of molecules hydrogen-bonded together to form a double layer in (102). Different types of molecule pairs alternate along each repeat axis, with a given molecule forming hydrogen bonds to molecules of the other type on each side. This results in O—H···O hydrogen bonds arranged in square tetrameric synthons between rows of molecules. Deviations from a true square within the synthon are small, e.g. neighboring O···O distances are in close agreement and O···O···O angles are ~90°, with the largest deviations due to O—H···O angles of 164–171° that place H atoms outside the square. The mean plane of molecule 1 is closer to (102), with both –OH groups directed into the double layer and with the C114 and C125 methyl groups directed outward. The mean-plane normal of molecule 0 forms a 24.86 (2)° angle to that of molecule 1, with the –OH groups hydrogen-bonded to molecules 1 on opposite sides of the double layer. The differences in geometric parameters between the alkynol groups (see above) can thus be ascribed to strains imposed to accommodate hydrogen bonding. The double layer is scored by grooves parallel to [201], generated by the offset of molecules 1, with the tetrameric O—H···O synthons at the floor (or ceiling) of each groove. A diagram of the quasi-square layer is presented in Fig. 2, and hydrogen-bonding parameters are presented in Table 1.

The structure is completed by stacking the double layers so molecule 0 pairs stack along a at the lines of inversion centers passing halfway through the b and c edges, while molecule 1 pairs stack similarly but along the a edges or passing through the center of the bc face. The mean planes within the stacks are tilted relative to a, with the normals forming angles of 60.80 (1) and 36.22 (1)° for molecules 0 and 1, respectively. The stacks of inversion-related molecular pairs are readily observed when the structure is viewed down a, as shown in the packing diagram in Fig. 3. However, the double layers are less obvious from a cursory examination, since the methyl groups projecting away from the layer are nested into the grooves of neighboring layers so as to obscure the boundaries between layers.

The few known vicinal dialkynols exhibit a variety in their structures that is sensitive to molecular geometry and composition, as is already well known among the much larger gem-alkynol family. The structure of (I) is, perhaps, the most conventional, since it contains the recurring tetrameric O—H···O synthon, yet at the same time shows no intramolecular interactions that might be expected for the tweezer-like ortho arrangement of the alkynol groups. In contrast, the difluoro analog [Cambridge Structural Database (Version 5.32; Allen, 2002) refcode OQAZUC (Kane et al., 2011)], in which F replaces the ring CH₃ groups, has quite a complex structure (Z' = 9) in which intramolecular O—H···O interactions are also found. This striking difference in complexity between the dimethyl and difluoro analogs raises the question of what other structures might be observed by replacing substituents in these positions. Meanwhile, the tetrafluoro analog (OQEBUC; Full reference required), in which F replaces the ring CH₃ groups and H atoms, has a simpler structure (Z' = 1) and only localized intra- and intermolecular O—H···O hydrogen bonding between two molecules in the tetrameric synthon, although with a more distorted square than in (I). In contrast, in OQEBOC (Z' = 1; Full reference required), the analog to OQEBIW (Full reference required) with alkynol CH₃ groups replaced by H, a strictly intermolecular O—H···O hydrogen-bonding network of zigzag chains is found. Thus, a two-dimensional hydrogen-bonding network with no intramolecular hydrogen bonding is found in (I), in spite of the presence of alkynol CH₃ groups, the presence of which allows for intramolecular hydrogen bonding in OQAZUC and OQEBIW and localized interactions only in OQEBIW. [Note that the carboxylic acid analog of (I) contains both intra- and intermolecular bonding to form zigzag O—H···O hydrogen-bonded chains (Saravanakumar et al., 2009).] Two other vicinal dialkynols, 1,8-dihydroxyocta-2,4,6-triyne (LILHUJ, Z' = 0.5; Enkelmann, 1994) and 2,9-dimethyldeca-3,5,7-triyne-2,9-diol (LILJAR, Z' = 1; Enkelmann, 1994), contain a –C≡ C– core that dictates a linear geometry, so the –OH groups are at opposite ends (and intramolecular hydrogen bonding is impossible) and O—H···O hydrogen-bonded networks are present as zigzag single or double layers, respectively. This variation of structure within the vicinal dialkynols (in particular ortho dialkynols), where small variations in ring or alkynol substituents lead to large changes in structure from competition between intra- and intermolecular hydrogen bonding, seems a fruitful area for further investigation.

Related literature

For related literature, see: Allen (2002); Banerjee et al. (2006); Bilton et al. (2001); Bondi (1964); Enkelmann (1994); Hathaway et al. (2009); Kane et al. (2011); Ladd & Palmer (1994); Madhavi et al. (2000, 2000a, 2000b); Melissaris & Litt (1994); Nangia (2010); Saravanakumar et al. (2009); Zhou et al. (1994).

S2. Experimental

Nitrogen (N₂) was bubbled through triethylamine (75 ml) for 15 min to remove dissolved oxygen, with the N₂ atmosphere maintained throughout the subsequent reaction. 1,2-Diiodo-4,5-dimethylbenzene (5.0 g, 0.014 mol), 2-methyl-3-butyn-2-ol (5.88 g, 0.070 mol), triphenylphosphane (0.10 g) and copper(I) iodide (0.03 g) were added, and the mixture was stirred for 10 min. Dichloridobis(triphenylphosphane)palladium (0.030 g) was added, and the reaction was heated to ~330 K overnight. The resulting green solution was diluted with diethyl ether and filtered. The filtrate was evaporated to yield a green–brown solid which was recrystallized from toluene to yield (I) as a sand-colored [colourless in CIF?] solid (yield 2.67 g, 70.6%; m.p. 414 K).

S3. Refinement

Solution and refinement of the structure were straightforward: all non-H atoms were found in the initial electron-density map and anisotropic displacement parameters refined. All H atoms were visible in subsequent electron-density difference maps, and the positions and isotropic displacement parameters of those bound to O atoms were freely refined (O—H = 0.886–0.904 Å). Other H-atom positions were calculated to give an idealized geometry, with C—H = 0.96 or 0.93 Å and with U(H) = 1.5 or 1.2U_eq(C) for, respectively, CH₃ or aromatic H atoms. The CH₃ torsion angle was refined to match the electron density. Low-angle reflections obscured by the beam stop (as indicated by F_o² << F_c²) were omitted from the refinement.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures

	Fig. 1. The asymmetric unit of (I), showing the two non-equivalent molecules with atom labels. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the hydrogen bond.
	Fig. 2. A plot of a portion of the quasi-square layer in (I) (with b vertical and [201] horizontal) formed by hydrogen bonding between inversion-related molecule pairs. Atoms are represented by circles of arbitrary radii and H atoms have been omitted for clarity, except for those bound to oxygen. Pairs of type 0 and 1 molecules are identified in the diagram and the inset shows the detail of the square tetrameric hydrogen-bonded moiety. [Symmetry code: (iv) -x + 1, y - 1/2, -z + 1/2.]
	Fig. 3. A unit-cell packing diagram for (I), viewed along a, showing the stacks of inversion–related molecule pairs. Atoms are drawn as circles of arbitrary radii and H atoms have been omitted for clarity.

4,4'-(4,5-Dimethyl-1,2-phenylene)bis(2-methylbut-3-yn-2-ol)

Crystal data

C18H22O2	Dx = 1.106 Mg m^−3
Mr = 270.37	Melting point: 414 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.4720 (1) Å	Cell parameters from 9685 reflections
b = 22.7966 (3) Å	θ = 2.9–30.0°
c = 16.8592 (2) Å	µ = 0.07 mm^−1
β = 93.886 (1)°	T = 100 K
V = 3248.58 (7) Å^3	Block, colourless
Z = 8	0.36 × 0.32 × 0.28 mm
F(000) = 1168

Data collection

Nonius KappaCCD area-detector diffractometer	7185 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	Rint = 0.027
Graphite monochromator	θmax = 30.0°, θmin = 3.3°
Detector resolution: 9 pixels mm^-1	h = −11→11
CCD rotation images, thick slices scans	k = −31→32
18231 measured reflections	l = −23→23
9466 independent reflections

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)] = 0.046	Hydrogen site location: difference Fourier map
wR(F^2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 1.0667P] where P = (Fo^2 + 2Fc^2)/3
9466 reflections	(Δ/σ)max = 0.001
389 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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
C01	0.12189 (12)	0.54679 (5)	0.13956 (6)	0.0178 (2)
C011	0.26338 (13)	0.57407 (5)	0.17362 (7)	0.0207 (2)
C012	0.38019 (13)	0.59732 (5)	0.20290 (7)	0.0205 (2)
C013	0.51886 (13)	0.62516 (5)	0.24553 (6)	0.0191 (2)
C014	0.64755 (14)	0.57975 (5)	0.26529 (8)	0.0268 (2)
H01A	0.7373	0.5985	0.2923	0.040*
H01B	0.6788	0.5621	0.2171	0.040*
H01C	0.6076	0.5500	0.2989	0.040*
C015	0.46812 (15)	0.65488 (6)	0.32068 (7)	0.0296 (3)
H01D	0.3904	0.6844	0.3066	0.044*
H01E	0.5584	0.6728	0.3484	0.044*
H01F	0.4236	0.6262	0.3544	0.044*
O01	0.58867 (9)	0.66772 (3)	0.19515 (5)	0.02060 (16)
H01	0.517 (2)	0.6938 (8)	0.1783 (10)	0.045 (5)*
C02	0.10278 (12)	0.48552 (4)	0.14195 (6)	0.0173 (2)
C021	0.22615 (13)	0.44843 (5)	0.17650 (6)	0.0190 (2)
C022	0.32716 (13)	0.41642 (5)	0.20475 (7)	0.0197 (2)
C023	0.45135 (13)	0.37692 (5)	0.23996 (7)	0.0222 (2)
C024	0.57684 (18)	0.41224 (6)	0.28769 (11)	0.0476 (4)
H02A	0.5283	0.4340	0.3283	0.071*
H02B	0.6265	0.4389	0.2530	0.071*
H02C	0.6550	0.3861	0.3118	0.071*
C025	0.52031 (18)	0.34042 (6)	0.17486 (10)	0.0421 (4)
H02D	0.5976	0.3137	0.1983	0.063*
H02E	0.5696	0.3659	0.1385	0.063*
H02F	0.4372	0.3187	0.1467	0.063*
O02	0.38340 (9)	0.33821 (3)	0.29603 (5)	0.02102 (17)
H02	0.323 (2)	0.3122 (9)	0.2692 (11)	0.055 (5)*
C03	−0.03836 (13)	0.46092 (5)	0.10931 (6)	0.0192 (2)
H03	−0.0513	0.4204	0.1110	0.023*
C04	−0.15985 (12)	0.49517 (5)	0.07439 (6)	0.0188 (2)
C041	−0.31044 (13)	0.46667 (5)	0.04079 (7)	0.0262 (2)
H04A	−0.2979	0.4248	0.0415	0.039*
H04B	−0.3333	0.4797	−0.0129	0.039*
H04C	−0.3960	0.4774	0.0724	0.039*
C05	−0.14007 (13)	0.55618 (5)	0.07100 (6)	0.0199 (2)
C051	−0.26733 (15)	0.59501 (5)	0.03275 (8)	0.0282 (3)
H05A	−0.2321	0.6350	0.0345	0.042*
H05B	−0.3616	0.5914	0.0609	0.042*
H05C	−0.2895	0.5833	−0.0216	0.042*
C06	−0.00020 (13)	0.58079 (5)	0.10354 (7)	0.0209 (2)
H06	0.0126	0.6213	0.1013	0.025*
C11	0.90438 (12)	0.41337 (5)	0.61033 (7)	0.0189 (2)
C111	0.95798 (13)	0.35895 (5)	0.64619 (7)	0.0210 (2)
C112	1.00338 (13)	0.31420 (5)	0.67745 (7)	0.0225 (2)
C113	1.05248 (13)	0.25868 (5)	0.71779 (7)	0.0219 (2)
C114	0.99869 (18)	0.25759 (6)	0.80203 (9)	0.0363 (3)
H11A	1.0478	0.2892	0.8321	0.054*
H11B	1.0285	0.2209	0.8268	0.054*
H11C	0.8858	0.2619	0.8004	0.054*
C115	0.98839 (15)	0.20637 (5)	0.66987 (9)	0.0327 (3)
H11D	1.0224	0.1707	0.6962	0.049*
H11E	1.0274	0.2075	0.6178	0.049*
H11F	0.8749	0.2079	0.6654	0.049*
O11	1.22185 (9)	0.25272 (3)	0.72007 (5)	0.02400 (18)
H11	1.268 (2)	0.2828 (8)	0.7459 (11)	0.056 (5)*
C12	0.79785 (13)	0.41398 (4)	0.54237 (6)	0.0186 (2)
C121	0.73837 (13)	0.36031 (5)	0.50684 (7)	0.0208 (2)
C122	0.68304 (14)	0.31625 (5)	0.47806 (7)	0.0220 (2)
C123	0.60726 (14)	0.26113 (5)	0.44850 (7)	0.0220 (2)
C124	0.70774 (18)	0.20861 (5)	0.47550 (8)	0.0330 (3)
H12A	0.8112	0.2124	0.4561	0.049*
H12B	0.6589	0.1733	0.4549	0.049*
H12C	0.7166	0.2070	0.5325	0.049*
C125	0.44035 (17)	0.25707 (6)	0.47704 (8)	0.0316 (3)
H12D	0.4456	0.2579	0.5341	0.047*
H12E	0.3919	0.2211	0.4584	0.047*
H12F	0.3786	0.2897	0.4566	0.047*
O12	0.59936 (10)	0.25983 (3)	0.36278 (5)	0.02156 (17)
H12	0.532 (2)	0.2884 (8)	0.3450 (10)	0.048 (5)*
C13	0.74574 (14)	0.46813 (5)	0.51116 (7)	0.0216 (2)
H13	0.6743	0.4686	0.4668	0.026*
C14	0.79717 (14)	0.52118 (5)	0.54430 (7)	0.0208 (2)
C141	0.73533 (16)	0.57831 (5)	0.50961 (8)	0.0301 (3)
H14A	0.6619	0.5705	0.4650	0.045*
H14B	0.8219	0.6012	0.4925	0.045*
H14C	0.6828	0.5997	0.5492	0.045*
C15	0.90619 (13)	0.52068 (5)	0.61104 (7)	0.0198 (2)
C151	0.96862 (15)	0.57705 (5)	0.64736 (8)	0.0257 (2)
H15A	1.0350	0.5685	0.6944	0.038*
H15B	0.8817	0.6012	0.6610	0.038*
H15C	1.0291	0.5974	0.6098	0.038*
C16	0.95592 (13)	0.46705 (5)	0.64329 (7)	0.0201 (2)
H16	1.0258	0.4668	0.6883	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C01	0.0179 (5)	0.0175 (5)	0.0176 (5)	−0.0005 (4)	−0.0022 (4)	−0.0008 (4)
C011	0.0226 (5)	0.0178 (5)	0.0213 (5)	−0.0011 (4)	−0.0023 (4)	0.0010 (4)
C012	0.0221 (5)	0.0179 (5)	0.0212 (5)	−0.0007 (4)	−0.0016 (4)	0.0010 (4)
C013	0.0196 (5)	0.0180 (5)	0.0193 (5)	−0.0046 (4)	−0.0010 (4)	0.0009 (4)
C014	0.0250 (6)	0.0214 (5)	0.0329 (6)	−0.0012 (4)	−0.0069 (5)	0.0059 (5)
C015	0.0277 (6)	0.0368 (7)	0.0248 (6)	−0.0098 (5)	0.0041 (5)	−0.0087 (5)
O01	0.0210 (4)	0.0175 (4)	0.0230 (4)	−0.0029 (3)	−0.0004 (3)	0.0039 (3)
C02	0.0163 (5)	0.0175 (5)	0.0176 (5)	0.0009 (4)	−0.0017 (4)	0.0011 (4)
C021	0.0182 (5)	0.0180 (5)	0.0205 (5)	−0.0021 (4)	−0.0019 (4)	0.0010 (4)
C022	0.0194 (5)	0.0168 (5)	0.0222 (5)	−0.0009 (4)	−0.0025 (4)	0.0007 (4)
C023	0.0171 (5)	0.0179 (5)	0.0308 (6)	−0.0001 (4)	−0.0035 (4)	0.0065 (4)
C024	0.0345 (7)	0.0299 (7)	0.0735 (11)	−0.0140 (6)	−0.0321 (7)	0.0216 (7)
C025	0.0427 (8)	0.0343 (7)	0.0524 (9)	0.0157 (6)	0.0253 (7)	0.0148 (6)
O02	0.0223 (4)	0.0166 (4)	0.0234 (4)	−0.0012 (3)	−0.0039 (3)	0.0033 (3)
C03	0.0189 (5)	0.0160 (5)	0.0222 (5)	−0.0011 (4)	−0.0018 (4)	0.0014 (4)
C04	0.0158 (5)	0.0221 (5)	0.0181 (5)	−0.0002 (4)	−0.0016 (4)	−0.0005 (4)
C041	0.0178 (5)	0.0305 (6)	0.0294 (6)	−0.0034 (4)	−0.0052 (4)	0.0006 (5)
C05	0.0190 (5)	0.0207 (5)	0.0194 (5)	0.0053 (4)	−0.0019 (4)	−0.0015 (4)
C051	0.0261 (6)	0.0274 (6)	0.0298 (6)	0.0102 (5)	−0.0075 (5)	−0.0014 (5)
C06	0.0237 (5)	0.0151 (5)	0.0235 (5)	0.0014 (4)	−0.0032 (4)	−0.0007 (4)
C11	0.0162 (5)	0.0161 (5)	0.0244 (5)	0.0003 (4)	0.0016 (4)	−0.0002 (4)
C111	0.0172 (5)	0.0180 (5)	0.0274 (6)	−0.0010 (4)	−0.0006 (4)	−0.0016 (4)
C112	0.0172 (5)	0.0186 (5)	0.0312 (6)	−0.0010 (4)	−0.0032 (4)	−0.0014 (4)
C113	0.0176 (5)	0.0164 (5)	0.0311 (6)	0.0001 (4)	−0.0038 (4)	0.0012 (4)
C114	0.0389 (8)	0.0322 (7)	0.0385 (7)	0.0066 (6)	0.0075 (6)	0.0066 (6)
C115	0.0287 (6)	0.0189 (5)	0.0481 (8)	−0.0032 (5)	−0.0144 (6)	−0.0002 (5)
O11	0.0167 (4)	0.0177 (4)	0.0365 (5)	0.0007 (3)	−0.0061 (3)	−0.0019 (3)
C12	0.0198 (5)	0.0158 (5)	0.0203 (5)	−0.0007 (4)	0.0018 (4)	−0.0012 (4)
C121	0.0243 (5)	0.0179 (5)	0.0200 (5)	0.0009 (4)	0.0002 (4)	0.0003 (4)
C122	0.0268 (6)	0.0185 (5)	0.0204 (5)	0.0003 (4)	−0.0010 (4)	0.0004 (4)
C123	0.0316 (6)	0.0149 (5)	0.0188 (5)	−0.0013 (4)	−0.0037 (4)	0.0001 (4)
C124	0.0522 (8)	0.0178 (5)	0.0266 (6)	0.0049 (5)	−0.0139 (6)	0.0009 (5)
C125	0.0399 (7)	0.0244 (6)	0.0312 (6)	−0.0103 (5)	0.0071 (5)	−0.0047 (5)
O12	0.0269 (4)	0.0189 (4)	0.0179 (4)	0.0034 (3)	−0.0059 (3)	−0.0004 (3)
C13	0.0258 (5)	0.0188 (5)	0.0199 (5)	0.0010 (4)	−0.0014 (4)	0.0006 (4)
C14	0.0241 (5)	0.0153 (5)	0.0235 (5)	0.0009 (4)	0.0045 (4)	0.0006 (4)
C141	0.0397 (7)	0.0180 (5)	0.0324 (6)	0.0042 (5)	0.0006 (5)	0.0050 (5)
C15	0.0193 (5)	0.0161 (5)	0.0247 (5)	−0.0012 (4)	0.0056 (4)	−0.0026 (4)
C151	0.0272 (6)	0.0172 (5)	0.0329 (6)	−0.0035 (4)	0.0044 (5)	−0.0053 (4)
C16	0.0173 (5)	0.0181 (5)	0.0247 (5)	0.0000 (4)	−0.0005 (4)	−0.0020 (4)

Geometric parameters (Å, º)

C01—C06	1.3979 (14)	C11—C16	1.4015 (15)
C01—C02	1.4070 (14)	C11—C12	1.4096 (15)
C01—C011	1.4353 (15)	C11—C111	1.4400 (15)
C011—C012	1.1990 (15)	C111—C112	1.1996 (15)
C012—C013	1.4783 (15)	C112—C113	1.4828 (15)
C013—O01	1.4424 (13)	C113—O11	1.4392 (13)
O01—H01	0.886 (18)	O11—H11	0.886 (19)
C013—C014	1.5239 (16)	C113—C114	1.5210 (19)
C014—H01A	0.9600	C114—H11A	0.9600
C014—H01B	0.9600	C114—H11B	0.9600
C014—H01C	0.9600	C114—H11C	0.9600
C013—C015	1.5240 (16)	C113—C115	1.5198 (16)
C015—H01D	0.9600	C115—H11D	0.9600
C015—H01E	0.9600	C115—H11E	0.9600
C015—H01F	0.9600	C115—H11F	0.9600
C02—C021	1.4368 (14)	C12—C121	1.4383 (15)
C021—C022	1.1985 (15)	C121—C122	1.1971 (15)
C022—C023	1.4783 (15)	C122—C123	1.4818 (15)
C023—O02	1.4414 (14)	C123—O12	1.4425 (13)
O02—H02	0.886 (19)	O12—H12	0.904 (18)
C023—C024	1.5199 (17)	C123—C124	1.5210 (16)
C024—H02A	0.9600	C124—H12A	0.9600
C024—H02B	0.9600	C124—H12B	0.9600
C024—H02C	0.9600	C124—H12C	0.9600
C023—C025	1.5249 (19)	C123—C125	1.5270 (18)
C025—H02D	0.9600	C125—H12D	0.9600
C025—H02E	0.9600	C125—H12E	0.9600
C025—H02F	0.9600	C125—H12F	0.9600
C02—C03	1.3992 (14)	C12—C13	1.4014 (15)
C03—C04	1.3906 (14)	C13—C14	1.3899 (15)
C03—H03	0.9300	C13—H13	0.9300
C04—C041	1.5074 (15)	C14—C141	1.5070 (15)
C041—H04A	0.9600	C141—H14A	0.9600
C041—H04B	0.9600	C141—H14B	0.9600
C041—H04C	0.9600	C141—H14C	0.9600
C04—C05	1.4025 (15)	C14—C15	1.4066 (16)
C05—C051	1.5058 (15)	C15—C151	1.5042 (15)
C051—H05A	0.9600	C151—H15A	0.9600
C051—H05B	0.9600	C151—H15B	0.9600
C051—H05C	0.9600	C151—H15C	0.9600
C05—C06	1.3899 (15)	C15—C16	1.3916 (15)
C06—H06	0.9300	C16—H16	0.9300
C06—C01—C02	118.66 (9)	C16—C11—C12	118.62 (10)
C06—C01—C011	120.46 (10)	C16—C11—C111	120.32 (10)
C02—C01—C011	120.88 (9)	C12—C11—C111	121.06 (10)
C011—C011—C012	178.97 (13)	C11—C111—C112	178.70 (12)
C011—C012—C013	175.22 (12)	C111—C112—C113	177.37 (12)
C012—C013—O01	110.28 (9)	C112—C113—O11	109.94 (9)
C014—C013—O01	105.66 (9)	C114—C113—O11	109.56 (10)
C015—C013—O01	109.91 (9)	C115—C113—O11	105.05 (9)
C013—O01—H01	109.8 (11)	C113—O11—H11	110.0 (12)
C012—C013—C014	110.35 (9)	C112—C113—C114	110.48 (10)
C012—C013—C015	109.59 (9)	C112—C113—C115	110.29 (10)
C014—C013—C015	110.99 (10)	C114—C113—C115	111.38 (11)
C013—C014—H01A	109.5	C113—C114—H11A	109.5
C013—C014—H01B	109.5	C113—C114—H11B	109.5
H01A—C014—H01B	109.5	H11A—C114—H11B	109.5
C013—C014—H01C	109.5	C113—C114—H11C	109.5
H01A—C014—H01C	109.5	H11A—C114—H11C	109.5
H01B—C014—H01C	109.5	H11B—C114—H11C	109.5
C013—C015—H01D	109.5	C113—C115—H11D	109.5
C013—C015—H01E	109.5	C113—C115—H11E	109.5
H01D—C015—H01E	109.5	H11D—C115—H11E	109.5
C013—C015—H01F	109.5	C113—C115—H11F	109.5
H01D—C015—H01F	109.5	H11D—C115—H11F	109.5
H01E—C015—H01F	109.5	H11E—C115—H11F	109.5
C01—C02—C03	118.92 (9)	C11—C12—C13	118.80 (10)
C01—C02—C021	120.92 (9)	C11—C12—C121	121.14 (10)
C03—C02—C021	120.15 (9)	C13—C12—C121	120.02 (10)
C02—C021—C022	178.54 (11)	C12—C121—C122	177.42 (12)
C021—C022—C023	179.71 (13)	C121—C122—C123	175.21 (12)
C022—C023—O02	109.35 (9)	C122—C123—O12	110.12 (9)
C024—C023—O02	105.86 (10)	C124—C123—O12	105.70 (9)
C025—C023—O02	109.12 (9)	C125—C123—O12	109.47 (10)
C023—O02—H02	108.5 (12)	C123—O12—H12	107.6 (11)
C022—C023—C024	110.07 (10)	C122—C123—C124	110.24 (10)
C022—C023—C025	109.89 (10)	C122—C123—C125	109.56 (10)
C024—C023—C025	112.44 (12)	C124—C123—C125	111.68 (11)
C023—C024—H02A	109.5	C123—C124—H12A	109.5
C023—C024—H02B	109.5	C123—C124—H12B	109.5
H02A—C024—H02B	109.5	H12A—C124—H12B	109.5
C023—C024—H02C	109.5	C123—C124—H12C	109.5
H02A—C024—H02C	109.5	H12A—C124—H12C	109.5
H02B—C024—H02C	109.5	H12B—C124—H12C	109.5
C023—C025—H02D	109.5	C123—C125—H12D	109.5
C023—C025—H02E	109.5	C123—C125—H12E	109.5
H02D—C025—H02E	109.5	H12D—C125—H12E	109.5
C023—C025—H02F	109.5	C123—C125—H12F	109.5
H02D—C025—H02F	109.5	H12D—C125—H12F	109.5
H02E—C025—H02F	109.5	H12E—C125—H12F	109.5
C02—C03—C04	121.98 (10)	C12—C13—C14	122.24 (10)
C02—C03—H03	119.0	C12—C13—H13	118.9
C04—C03—H03	119.0	C14—C13—H13	118.9
C03—C04—C041	120.02 (10)	C13—C14—C141	120.32 (11)
C03—C04—C05	119.15 (10)	C13—C14—C15	119.04 (10)
C05—C04—C041	120.83 (10)	C15—C14—C141	120.64 (10)
C04—C041—H04A	109.5	C14—C141—H14A	109.5
C04—C041—H04B	109.5	C14—C141—H14B	109.5
H04A—C041—H04B	109.5	H14A—C141—H14B	109.5
C04—C041—H04C	109.5	C14—C141—H14C	109.5
H04A—C041—H04C	109.5	H14A—C141—H14C	109.5
H04B—C041—H04C	109.5	H14B—C141—H14C	109.5
C04—C05—C051	121.08 (10)	C14—C15—C151	120.82 (10)
C04—C05—C06	119.03 (10)	C14—C15—C16	118.99 (10)
C06—C05—C051	119.89 (10)	C16—C15—C151	120.18 (10)
C05—C051—H05A	109.5	C15—C151—H15A	109.5
C05—C051—H05B	109.5	C15—C151—H15B	109.5
H05A—C051—H05B	109.5	H15A—C151—H15B	109.5
C05—C051—H05C	109.5	C15—C151—H15C	109.5
H05A—C051—H05C	109.5	H15A—C151—H15C	109.5
H05B—C051—H05C	109.5	H15B—C151—H15C	109.5
C05—C06—C01	122.25 (10)	C15—C16—C11	122.29 (10)
C05—C06—H06	118.9	C15—C16—H16	118.9
C01—C06—H06	118.9	C11—C16—H16	118.9

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O01—H01···O12^i	0.886 (18)	1.901 (17)	2.773 (1)	167.5 (16)
O02—H02···O11^ii	0.886 (19)	1.876 (19)	2.752 (1)	169.8 (18)
O11—H11···O01^iii	0.886 (19)	1.892 (19)	2.756 (1)	164.3 (18)
O12—H12···O02	0.904 (18)	1.847 (17)	2.744 (1)	170.7 (17)

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