Hydro­gen-bond networks in tris(4-hydroxy­phenyl)­methane and its 1:1 molecular complex with 4,4′-bi­pyridine

In tris(4-hydroxy­phenyl)­methane (or 4,4′,4′′-methane­triyl­tri­phenol), C₁₉H₁₆O₃, mol­ecules are connected by O—H...O hydrogen bonds [O...O = 2.662 (2) and 2.648 (2) Å] into two-dimensional square networks that are twofold interpenetrated. In tris(4-hydroxy­phenyl)­methane–4,4′-bi­pyridine (1/1), C₁₉H₁₆O₃·C₁₀H₈N₂, trisphenol mol­ecules form rectangular networks via O—H...O [O...O = 2.694 (3) Å] and C—H...O [C...O = 3.384 (3) Å] hydrogen bonds. Bi­pyridine mol­ecules hydrogen bonded to phenol moieties [O...N = 2.622 (3) and 2.764 (3) Å] fill the voids to complete the structure.

S1. Comment

The crystal structures of 1,1,1-tris(4-hydroxyphenyl)ethane and its adducts with many nitrogen bases have been reported (Ferguson et al., 1997, Bényei et al., 1998, Zakaria et al., 2002a, Zakaria et al., 2002b). These structures contain sheets and open networks of O—H···O, O—H···N and N⁺—H···O⁻ hydrogen bonds, with up to tenfold interpenetration of giant hexagons in 1,1,1-tris(4-hydroxyphenyl)ethane:4,4'-bipyridine (2:3) (Bényei et al., 1998). Molecules with C₃ symmetry are important in crystal engineering (Desiraju, 1989; Moberg, 1998) for building supramolecular architectures, in host–guest systems and in the design of non-linear optical materials. In this context, we have determined the crystal structure of tris(4-hydroxyphenyl)methane, (I). Cocrystallization of (I) with 4,4'-bipyridine in a 2:3 stoichiometry gave the 1:1 adduct (II). The crystal structure of (I) is similar to that of 1,1,1-tris(4-hydroxyphenyl)ethane.

The crystal structure of (I) contains one molecule of tris(4-hydroxyphenyl)methane in the asymmetric unit (Fig. 1). The phenolic groups act as donors and acceptors of hydrogen bonds, such that each molecule is bonded to six others by O—H···O hydrogen bonds. Hydroxyl atom O1 acts as a hydrogen bond donor to atom O2 at (x − 1/2, y − 1/2, z), thus generating chains of molecules running parallel to [110]. Atom O3 acts as a hydrogen bond donor to atom O1 at (1 + x, y, 1 + z) and generates chains of molecules parallel to [101]. The intersection of these two linear motifs generates two-dimensional square networks parallel to the (111) plane (Fig. 2), which are similar to the square nets observed in the crystal structure of 1,1,1-tris(4-hydroxyphenyl)ethane (Ferguson et al., 1997). The third hydroxyl group (O2) acts as a hydrogen-bond donor to atom O3 at (x − 1/2, 1/2 − y, z − 3/2), thus generating an identical square network parallel to the (111) plane. These two square networks interpenetrate in the structure at an angle of \sim160°, being connected via the O2—H2···O3 hydrogen bond (Fig. 3).

The crystal structure of (II) contains one molecule of trisphenol (I) and one molecule of 4,4'-bipyridine in the asymmetric unit (Fig 4). One of the hydroxyl groups of the trisphenol acts as a hydrogen-bond donor to a d-glide-related O atom, and the other two hydroxyl groups act as hydrogen-bond donors to 4,4'-bipyridine molecules. Each molecule of trisphenol is connected to two others, thus forming zigzag chains via O—H···O hydrogen bonds. Atom O2 acts as a hydrogen-bond donor to atom O1 in the molecule at (3/4 − x, 1/4 + y, −1/4 + z), thus generating a zigzag chain parallel to [011] and produced by the d-glide plane. The zigzag chain related by the twofold rotation axis runs parallel to [011]. Atom C15 acts as a hydrogen bond donor to atom O2 of the d-glide-related molecule at (−1/4 + x, 5/4 − y, −1/4 + z), resulting in a zigzag chain parallel to [101]. The net result of the O—H···O and C—H···O hydrogen-bonded chains is a rectangular grid parallel to the ab plane, with voids of 9.6 Å × 12.5 Å (Fig. 5). This two-dimensional network is not flat but has undulated layers, with trisphenol molecules occupying a thickness approximately equal to the length of the c axis. Atoms O1 and O3 act as hydrogen-bond donors to atoms N1 and N2, respectively. Thus, each rectangular network is connected to two others by a bipyridine molecule parallel to [001]. The threading of two bipyridine molecules through a rectangular void is shown as a stereoview in Fig. 6. The crystal structure of (II) may be compared with the 2:1 adduct of 1,1,1-tris(4-hydroxyphenyl)ethane:bis-(4-pyridyl)ethane (Zakaria et al., 2002a), in which the supramolecular structure consists of continuously interwoven bilayers.

The conformation of the trisphenol molecule in the two crystal structures is different (Tables 1 and 3). Whereas the torsion angles about the C1—C(aryl) bond are similar in (II), they are very different in (I). In (II), the dihedral angle between bipyridine rings is −32.2 (3)°.

S2. Experimental

Tris(4-hydroxyphenyl)methane was prepared according to the procedure of Kolasa et al. (2000). A mixture of 4-hydroxybenzaldehyde (1.0 g, 8 mmol) and phenol (2.6 g, 28 mmol) in 1,4-dioxane (15 ml) and water (15 ml) at 273 K was treated dropwise with concentrated H₂SO₄ (10 ml). The reaction mixture was allowed to warm to room temperature and was stirred for 6 h. The reaction mixture was neutralized with NaHCO₃ solution and extracted with ether. The ether layer was washed with water and brine, dried with MgSO₄, and concentrated in vacuo to yield trisphenol (I). The product was purified by column chromatography to yield pure (I), which was crystallized from methanol (m.p. 513 K). Crystals of the 1:1 molecular complex, (II) (m.p. 470 K), of (I) and 4,4'-bipyridine were obtained upon complexation of the components in a 2:3 ratio from acetonitrile.

S3. Refinement

Both structures are non-centrosymmetric. However, because the anomalous dispersion effects were insignificant, Friedel opposite reflections were merged. The Flack parameters are thus indeterminate.

Computing details

For both compounds, data collection: KM-4 Software (Kuma, 1999); cell refinement: KM-4 Software; data reduction: CrysAlis (Kuma, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at 50% the probability level for non-H atoms.
	Fig. 2. A view of the cystal structure of (I), showing the two-dimensional square network.
	Fig. 3. A stereoview of (I), showing the concatenation of two square nets. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 4. A view of the molecular components of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms.
	Fig. 5. A view of the crystal structure of (II), showing the rectangular voids in the ab plane. H atoms bonded to C atoms, except that involved in hydrogen bonding (C15), have been omitted for clarity.
	Fig. 6. A view of the crystal structure of (II), showing two bipyridine linkers connecting the hydrogen-bonded networks of (I) and passing through the rectangular void of a third network. H atoms bonded to C atoms, except that involved in hydrogen bonding (C15), have been omitted for clarity.

(I) 4,4',4''-methanetriyltriphenol

Crystal data

C19H16O3	Dx = 1.242 Mg m^−3
Mr = 292.32	Melting point: 513 K
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 12.326 (3) Å	Cell parameters from 1475 reflections
b = 18.573 (4) Å	θ = 3.7–29.7°
c = 7.4961 (15) Å	µ = 0.08 mm^−1
β = 114.36 (3)°	T = 100 K
V = 1563.4 (7) Å^3	Needles, brown
Z = 4	0.40 × 0.35 × 0.20 mm
F(000) = 616

Data collection

KUMA KM-4 CCD diffractometer	1844 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 29.7°, θmin = 3.7°
oscillation method scans	h = −16→16
7459 measured reflections	k = −25→14
2056 independent reflections	l = −10→10

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	All H-atom parameters refined
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 0.0272P] where P = (Fo^2 + 2Fc^2)/3
2056 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.18 e Å^−3
2 restraints	Δρmin = −0.20 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
O1	−0.00969 (14)	0.01158 (9)	0.7987 (2)	0.0288 (4)
H1	−0.025 (3)	−0.0280 (18)	0.734 (5)	0.036 (8)*
O2	0.41243 (17)	0.38869 (9)	0.6051 (2)	0.0343 (4)
H2	0.365 (3)	0.3886 (16)	0.477 (5)	0.031 (7)*
O3	0.80622 (15)	0.09900 (10)	1.7171 (2)	0.0330 (4)
H3	0.866 (3)	0.0746 (17)	1.727 (5)	0.044 (9)*
C1	0.45666 (18)	0.10807 (12)	0.9324 (3)	0.0234 (4)
H1A	0.484 (3)	0.0762 (16)	0.856 (4)	0.032 (7)*
C2	0.33246 (18)	0.08214 (12)	0.9020 (3)	0.0236 (4)
C3	0.3015 (2)	0.01062 (12)	0.8562 (3)	0.0249 (4)
H3A	0.360 (2)	−0.0212 (14)	0.851 (4)	0.024 (6)*
C4	0.1881 (2)	−0.01444 (12)	0.8227 (3)	0.0251 (4)
H4A	0.169 (2)	−0.0634 (16)	0.787 (4)	0.027 (7)*
C5	0.10443 (18)	0.03358 (12)	0.8329 (3)	0.0240 (4)
C6	0.1334 (2)	0.10513 (12)	0.8810 (3)	0.0268 (5)
H6A	0.077 (3)	0.1359 (15)	0.895 (4)	0.029 (7)*
C7	0.2471 (2)	0.12927 (12)	0.9144 (3)	0.0263 (4)
H7A	0.269 (3)	0.1820 (17)	0.945 (5)	0.037 (8)*
C8	0.45157 (19)	0.18336 (12)	0.8465 (3)	0.0251 (4)
C9	0.3746 (2)	0.19511 (13)	0.6498 (3)	0.0290 (5)
H9A	0.323 (3)	0.1554 (17)	0.568 (4)	0.037 (8)*
C10	0.3616 (2)	0.26245 (14)	0.5666 (3)	0.0294 (5)
H10A	0.313 (3)	0.2678 (18)	0.434 (5)	0.039 (8)*
C11	0.4258 (2)	0.31983 (12)	0.6796 (3)	0.0269 (5)
C12	0.5042 (2)	0.30960 (14)	0.8723 (3)	0.0325 (5)
H12A	0.545 (3)	0.3501 (16)	0.948 (4)	0.035 (8)*
C13	0.5166 (2)	0.24113 (14)	0.9542 (3)	0.0310 (5)
H13A	0.573 (3)	0.2352 (19)	1.092 (5)	0.046 (9)*
C14	0.54637 (19)	0.10264 (11)	1.1439 (3)	0.0235 (4)
C15	0.5233 (2)	0.12951 (13)	1.2987 (3)	0.0270 (4)
H15A	0.444 (3)	0.1498 (17)	1.273 (5)	0.042 (8)*
C16	0.6101 (2)	0.12828 (13)	1.4903 (3)	0.0276 (5)
H16A	0.591 (2)	0.1452 (14)	1.599 (4)	0.022 (6)*
C17	0.72154 (18)	0.09961 (12)	1.5275 (3)	0.0247 (4)
C18	0.7458 (2)	0.07210 (13)	1.3767 (3)	0.0292 (5)
H18A	0.823 (2)	0.0504 (15)	1.407 (4)	0.025 (6)*
C19	0.6582 (2)	0.07355 (12)	1.1860 (3)	0.0266 (4)
H19A	0.679 (2)	0.0545 (15)	1.080 (4)	0.028 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0215 (7)	0.0289 (9)	0.0304 (9)	−0.0027 (6)	0.0053 (6)	−0.0015 (7)
O2	0.0405 (10)	0.0319 (9)	0.0221 (8)	−0.0088 (7)	0.0043 (7)	0.0038 (6)
O3	0.0267 (8)	0.0443 (10)	0.0209 (8)	0.0077 (7)	0.0027 (6)	−0.0027 (7)
C1	0.0209 (9)	0.0271 (10)	0.0190 (10)	−0.0001 (8)	0.0049 (8)	−0.0029 (8)
C2	0.0223 (10)	0.0289 (11)	0.0164 (9)	0.0005 (8)	0.0047 (8)	0.0006 (8)
C3	0.0247 (10)	0.0271 (11)	0.0208 (10)	0.0021 (8)	0.0072 (8)	−0.0011 (8)
C4	0.0261 (11)	0.0241 (11)	0.0208 (10)	−0.0005 (8)	0.0053 (8)	0.0008 (8)
C5	0.0196 (9)	0.0300 (11)	0.0178 (9)	−0.0026 (8)	0.0031 (8)	0.0008 (8)
C6	0.0235 (10)	0.0275 (11)	0.0266 (11)	0.0034 (8)	0.0074 (9)	0.0016 (8)
C7	0.0250 (10)	0.0236 (10)	0.0260 (11)	−0.0014 (8)	0.0060 (8)	−0.0010 (8)
C8	0.0207 (9)	0.0325 (11)	0.0205 (10)	−0.0004 (8)	0.0068 (8)	0.0010 (8)
C9	0.0295 (11)	0.0323 (12)	0.0202 (10)	−0.0045 (9)	0.0052 (9)	−0.0023 (9)
C10	0.0272 (11)	0.0354 (12)	0.0195 (10)	−0.0030 (9)	0.0035 (9)	0.0011 (9)
C11	0.0265 (10)	0.0315 (11)	0.0217 (10)	−0.0045 (9)	0.0090 (8)	0.0030 (9)
C12	0.0334 (12)	0.0347 (13)	0.0210 (11)	−0.0116 (10)	0.0025 (9)	0.0009 (9)
C13	0.0289 (11)	0.0374 (13)	0.0197 (11)	−0.0102 (10)	0.0030 (9)	0.0021 (9)
C14	0.0220 (10)	0.0239 (10)	0.0214 (10)	−0.0009 (8)	0.0059 (8)	0.0008 (8)
C15	0.0207 (9)	0.0325 (11)	0.0260 (11)	0.0019 (8)	0.0081 (8)	0.0000 (9)
C16	0.0258 (11)	0.0327 (12)	0.0239 (11)	0.0012 (9)	0.0098 (9)	−0.0020 (8)
C17	0.0214 (10)	0.0270 (11)	0.0208 (10)	−0.0002 (7)	0.0038 (8)	0.0000 (8)
C18	0.0237 (10)	0.0332 (12)	0.0273 (11)	0.0044 (9)	0.0071 (9)	0.0005 (9)
C19	0.0266 (10)	0.0292 (12)	0.0230 (10)	0.0034 (8)	0.0093 (9)	−0.0011 (8)

Geometric parameters (Å, º)

O1—C5	1.383 (3)	C8—C13	1.382 (3)
O1—H1	0.86 (3)	C8—C9	1.403 (3)
O2—C11	1.378 (3)	C9—C10	1.377 (3)
O2—H2	0.90 (3)	C9—H9A	1.00 (3)
O3—C17	1.373 (2)	C10—C11	1.388 (3)
O3—H3	0.84 (3)	C10—H10A	0.93 (3)
C1—C14	1.516 (3)	C11—C12	1.380 (3)
C1—C2	1.530 (3)	C12—C13	1.393 (3)
C1—C8	1.530 (3)	C12—H12A	0.95 (3)
C1—H1A	0.98 (3)	C13—H13A	0.98 (3)
C2—C3	1.385 (3)	C14—C19	1.391 (3)
C2—C7	1.402 (3)	C14—C15	1.396 (3)
C3—C4	1.394 (3)	C15—C16	1.393 (3)
C3—H3A	0.95 (3)	C15—H15A	0.99 (3)
C4—C5	1.390 (3)	C16—C17	1.390 (3)
C4—H4A	0.95 (3)	C16—H16A	0.99 (3)
C5—C6	1.385 (3)	C17—C18	1.381 (3)
C6—C7	1.392 (3)	C18—C19	1.391 (3)
C6—H6A	0.94 (3)	C18—H18A	0.97 (3)
C7—H7A	1.02 (3)	C19—H19A	0.99 (3)
C5—O1—H1	109 (2)	C8—C9—H9A	120.8 (17)
C11—O2—H2	110.4 (19)	C9—C10—C11	119.4 (2)
C17—O3—H3	111 (2)	C9—C10—H10A	119 (2)
C14—C1—C2	112.86 (17)	C11—C10—H10A	122 (2)
C14—C1—C8	112.72 (18)	O2—C11—C12	117.8 (2)
C2—C1—C8	111.11 (17)	O2—C11—C10	121.5 (2)
C14—C1—H1A	107.0 (17)	C12—C11—C10	120.7 (2)
C2—C1—H1A	106.9 (17)	C11—C12—C13	119.3 (2)
C8—C1—H1A	105.7 (16)	C11—C12—H12A	118.9 (18)
C3—C2—C7	118.5 (2)	C13—C12—H12A	121.7 (17)
C3—C2—C1	119.68 (19)	C8—C13—C12	121.3 (2)
C7—C2—C1	121.76 (19)	C8—C13—H13A	121 (2)
C2—C3—C4	121.2 (2)	C12—C13—H13A	118 (2)
C2—C3—H3A	118.1 (16)	C19—C14—C15	118.2 (2)
C4—C3—H3A	120.7 (16)	C19—C14—C1	119.38 (19)
C5—C4—C3	119.2 (2)	C15—C14—C1	122.31 (19)
C5—C4—H4A	121.4 (17)	C16—C15—C14	121.2 (2)
C3—C4—H4A	119.3 (17)	C16—C15—H15A	119.1 (19)
O1—C5—C6	117.7 (2)	C14—C15—H15A	119.7 (19)
O1—C5—C4	121.4 (2)	C17—C16—C15	119.2 (2)
C6—C5—C4	120.8 (2)	C17—C16—H16A	120.4 (15)
C5—C6—C7	119.3 (2)	C15—C16—H16A	120.3 (15)
C5—C6—H6A	119.1 (17)	O3—C17—C18	121.04 (19)
C7—C6—H6A	121.6 (17)	O3—C17—C16	118.51 (19)
C6—C7—C2	121.0 (2)	C18—C17—C16	120.45 (19)
C6—C7—H7A	120.4 (17)	C17—C18—C19	119.7 (2)
C2—C7—H7A	118.6 (17)	C17—C18—H18A	118.9 (16)
C13—C8—C9	118.1 (2)	C19—C18—H18A	121.3 (16)
C13—C8—C1	123.41 (19)	C14—C19—C18	121.2 (2)
C9—C8—C1	118.49 (19)	C14—C19—H19A	120.9 (16)
C10—C9—C8	121.3 (2)	C18—C19—H19A	117.9 (16)
C10—C9—H9A	117.7 (17)
H1A—C1—C2—C3	26.9 (13)	H1A—C1—C8—C9	61.2 (14)
H1A—C1—C14—C19	16.9 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.87 (2)	1.81 (3)	2.662 (2)	168 (3)
O2—H2···O3^ii	0.88 (2)	1.81 (2)	2.662 (2)	163 (2)
O3—H3···O1^iii	0.86 (3)	1.81 (3)	2.648 (2)	166 (3)

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

(II) 4,4',4''-methanetriyltriphenol–bipyridine (1/1)

Crystal data

C19H16O3·C10H8N2	Dx = 1.259 Mg m^−3
Mr = 448.50	Melting point: 470 K
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
a = 26.483 (5) Å	Cell parameters from 2377 reflections
b = 34.102 (7) Å	θ = 3.5–29.9°
c = 10.483 (2) Å	µ = 0.08 mm^−1
V = 9468 (3) Å^3	T = 100 K
Z = 16	Needles, brown
F(000) = 3776	0.45 × 0.40 × 0.25 mm

Data collection

KUMA KM-4 CCD diffractometer	2951 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 29.9°, θmin = 3.5°
oscillation method scans	h = −36→34
22391 measured reflections	k = −46→45
3352 independent reflections	l = −14→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	All H-atom parameters refined
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0517P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.069
3352 reflections	Δρmax = 0.18 e Å^−3
404 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00029 (7)

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
O1	0.32160 (6)	0.39098 (5)	0.89242 (16)	0.0303 (4)
H1	0.3221 (12)	0.3717 (9)	0.816 (3)	0.056 (9)*
O2	0.35329 (7)	0.65343 (5)	0.81091 (18)	0.0385 (4)
H2	0.3773 (16)	0.6485 (11)	0.750 (4)	0.077 (13)*
O3	0.03987 (6)	0.53753 (5)	1.12242 (17)	0.0325 (4)
H3	0.0440 (12)	0.5188 (10)	1.191 (3)	0.056 (9)*
N1	0.33181 (7)	0.34733 (6)	0.68810 (19)	0.0294 (4)
N2	0.30547 (7)	0.26211 (6)	0.0771 (2)	0.0340 (5)
C1	0.20948 (8)	0.53011 (6)	0.7881 (2)	0.0214 (4)
H1A	0.1927 (9)	0.5288 (6)	0.701 (2)	0.016 (5)*
C2	0.24083 (7)	0.49326 (6)	0.8093 (2)	0.0212 (4)
C3	0.28385 (8)	0.49363 (6)	0.8867 (2)	0.0247 (4)
H3A	0.2968 (9)	0.5190 (7)	0.919 (2)	0.023 (6)*
C4	0.31023 (8)	0.45962 (6)	0.9129 (2)	0.0247 (4)
H4A	0.3403 (10)	0.4607 (7)	0.968 (3)	0.030 (7)*
C5	0.29460 (8)	0.42415 (6)	0.8622 (2)	0.0246 (4)
C6	0.25207 (9)	0.42300 (7)	0.7848 (2)	0.0302 (5)
H6A	0.2406 (10)	0.3966 (8)	0.749 (2)	0.035 (7)*
C7	0.22584 (9)	0.45750 (7)	0.7586 (2)	0.0284 (5)
H7A	0.1952 (10)	0.4561 (7)	0.699 (3)	0.031 (7)*
C8	0.24278 (8)	0.56651 (6)	0.7910 (2)	0.0220 (4)
C9	0.27123 (8)	0.57619 (6)	0.6835 (2)	0.0258 (4)
H9A	0.2658 (9)	0.5611 (7)	0.600 (2)	0.026 (6)*
C10	0.30781 (9)	0.60531 (7)	0.6881 (2)	0.0291 (5)
H10A	0.3280 (10)	0.6107 (8)	0.611 (3)	0.039 (7)*
C11	0.31647 (9)	0.62539 (6)	0.8005 (2)	0.0277 (5)
C12	0.28728 (9)	0.61733 (7)	0.9071 (2)	0.0288 (5)
H12A	0.2932 (11)	0.6320 (9)	0.989 (3)	0.045 (8)*
C13	0.25068 (8)	0.58800 (7)	0.9018 (2)	0.0264 (5)
H13A	0.2312 (10)	0.5809 (7)	0.983 (3)	0.027 (6)*
C14	0.16504 (8)	0.53237 (6)	0.8806 (2)	0.0215 (4)
C15	0.12119 (8)	0.55249 (6)	0.8466 (2)	0.0218 (4)
H15A	0.1183 (10)	0.5654 (7)	0.765 (3)	0.030 (7)*
C16	0.07994 (8)	0.55433 (6)	0.9280 (2)	0.0241 (4)
H16A	0.0501 (9)	0.5676 (7)	0.905 (2)	0.021 (6)*
C17	0.08175 (8)	0.53613 (6)	1.0468 (2)	0.0237 (4)
C18	0.12580 (8)	0.51712 (7)	1.0836 (2)	0.0264 (5)
H18A	0.1267 (10)	0.5038 (7)	1.172 (3)	0.032 (7)*
C19	0.16668 (8)	0.51531 (7)	1.0007 (2)	0.0262 (5)
H19A	0.1985 (11)	0.5017 (8)	1.028 (3)	0.045 (8)*
C20	0.35052 (10)	0.36524 (7)	0.5848 (3)	0.0329 (5)
H20A	0.3669 (10)	0.3906 (8)	0.592 (3)	0.032 (7)*
C21	0.34862 (9)	0.34921 (7)	0.4643 (2)	0.0298 (5)
H21A	0.3620 (10)	0.3630 (7)	0.391 (3)	0.034 (7)*
C22	0.32576 (8)	0.31292 (6)	0.4468 (2)	0.0242 (4)
C23	0.30760 (9)	0.29379 (7)	0.5549 (2)	0.0266 (5)
H23A	0.2926 (10)	0.2676 (8)	0.546 (3)	0.039 (7)*
C24	0.31091 (9)	0.31190 (7)	0.6727 (2)	0.0272 (5)
H24A	0.2980 (9)	0.2993 (7)	0.749 (2)	0.023 (6)*
C25	0.31977 (8)	0.29545 (6)	0.3182 (2)	0.0253 (5)
C26	0.31204 (9)	0.31861 (8)	0.2109 (2)	0.0315 (5)
H26A	0.3090 (11)	0.3475 (8)	0.213 (3)	0.035 (7)*
C27	0.30519 (10)	0.30098 (8)	0.0936 (2)	0.0348 (6)
H27A	0.2994 (10)	0.3168 (7)	0.019 (3)	0.029 (6)*
C28	0.31299 (9)	0.23976 (8)	0.1804 (3)	0.0323 (5)
H28A	0.3135 (10)	0.2119 (8)	0.164 (3)	0.035 (7)*
C29	0.32015 (8)	0.25481 (7)	0.3014 (2)	0.0282 (5)
H29A	0.3242 (10)	0.2387 (8)	0.376 (3)	0.030 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0351 (8)	0.0279 (8)	0.0279 (9)	0.0100 (6)	−0.0073 (7)	−0.0056 (7)
O2	0.0448 (10)	0.0361 (9)	0.0346 (10)	−0.0194 (8)	0.0139 (8)	−0.0125 (8)
O3	0.0240 (8)	0.0438 (10)	0.0297 (9)	0.0050 (7)	0.0056 (7)	0.0115 (8)
N1	0.0336 (10)	0.0278 (9)	0.0268 (10)	0.0054 (8)	−0.0029 (8)	−0.0050 (8)
N2	0.0269 (10)	0.0482 (12)	0.0268 (11)	−0.0001 (9)	0.0041 (8)	−0.0113 (9)
C1	0.0216 (9)	0.0235 (10)	0.0192 (10)	0.0002 (8)	0.0003 (8)	0.0015 (8)
C2	0.0222 (9)	0.0218 (9)	0.0195 (10)	−0.0001 (8)	0.0021 (8)	0.0006 (8)
C3	0.0255 (10)	0.0235 (10)	0.0250 (11)	−0.0022 (8)	−0.0005 (9)	−0.0018 (9)
C4	0.0224 (10)	0.0285 (11)	0.0232 (11)	0.0004 (8)	−0.0016 (8)	−0.0032 (9)
C5	0.0264 (10)	0.0261 (10)	0.0213 (11)	0.0046 (8)	0.0009 (8)	−0.0012 (9)
C6	0.0313 (12)	0.0261 (11)	0.0333 (13)	−0.0001 (9)	−0.0074 (10)	−0.0069 (9)
C7	0.0257 (11)	0.0281 (11)	0.0315 (12)	−0.0005 (9)	−0.0070 (9)	−0.0023 (9)
C8	0.0225 (9)	0.0208 (9)	0.0228 (10)	0.0015 (8)	0.0025 (8)	0.0024 (8)
C9	0.0298 (11)	0.0268 (11)	0.0208 (11)	−0.0024 (9)	0.0016 (9)	−0.0016 (9)
C10	0.0320 (11)	0.0319 (12)	0.0234 (12)	−0.0073 (9)	0.0074 (9)	−0.0018 (9)
C11	0.0326 (11)	0.0240 (10)	0.0264 (12)	−0.0052 (9)	0.0062 (9)	−0.0022 (9)
C12	0.0357 (12)	0.0275 (11)	0.0233 (12)	−0.0048 (9)	0.0058 (9)	−0.0085 (9)
C13	0.0294 (11)	0.0275 (11)	0.0222 (11)	−0.0014 (9)	0.0067 (9)	−0.0013 (9)
C14	0.0202 (9)	0.0233 (10)	0.0210 (10)	−0.0009 (8)	0.0007 (8)	0.0010 (8)
C15	0.0247 (10)	0.0220 (10)	0.0187 (10)	−0.0015 (8)	−0.0011 (8)	0.0027 (8)
C16	0.0209 (10)	0.0252 (10)	0.0263 (11)	0.0005 (8)	−0.0029 (8)	0.0040 (9)
C17	0.0205 (10)	0.0276 (11)	0.0229 (11)	−0.0013 (8)	0.0011 (8)	0.0015 (8)
C18	0.0258 (10)	0.0317 (11)	0.0216 (11)	0.0003 (9)	−0.0013 (9)	0.0080 (9)
C19	0.0218 (10)	0.0310 (11)	0.0257 (11)	0.0020 (9)	−0.0005 (8)	0.0075 (9)
C20	0.0409 (13)	0.0242 (11)	0.0336 (13)	−0.0010 (10)	−0.0028 (11)	−0.0039 (10)
C21	0.0332 (12)	0.0254 (11)	0.0307 (12)	−0.0013 (9)	−0.0005 (10)	0.0014 (9)
C22	0.0235 (10)	0.0253 (10)	0.0238 (11)	0.0047 (8)	−0.0007 (9)	−0.0019 (9)
C23	0.0279 (11)	0.0240 (11)	0.0278 (12)	0.0006 (8)	−0.0006 (9)	−0.0019 (9)
C24	0.0298 (11)	0.0291 (11)	0.0229 (12)	0.0028 (9)	0.0024 (9)	−0.0005 (9)
C25	0.0226 (10)	0.0290 (11)	0.0242 (11)	0.0011 (8)	0.0029 (8)	−0.0044 (9)
C26	0.0357 (12)	0.0305 (12)	0.0283 (13)	−0.0027 (10)	0.0026 (10)	−0.0009 (10)
C27	0.0373 (13)	0.0444 (15)	0.0227 (12)	−0.0052 (11)	0.0022 (10)	−0.0002 (11)
C28	0.0238 (10)	0.0364 (13)	0.0367 (14)	0.0032 (9)	−0.0006 (10)	−0.0133 (11)
C29	0.0244 (11)	0.0301 (12)	0.0301 (12)	0.0029 (9)	−0.0016 (9)	−0.0034 (10)

Geometric parameters (Å, º)

O1—C5	1.375 (3)	C12—C13	1.394 (3)
O1—H1	1.04 (3)	C12—H12A	1.01 (3)
O2—C11	1.370 (3)	C13—H13A	1.02 (3)
O2—H2	0.92 (4)	C14—C19	1.387 (3)
O3—C17	1.364 (3)	C14—C15	1.395 (3)
O3—H3	0.97 (3)	C15—C16	1.388 (3)
N1—C20	1.338 (3)	C15—H15A	0.96 (3)
N1—C24	1.339 (3)	C16—C17	1.392 (3)
N2—C27	1.337 (3)	C16—H16A	0.94 (2)
N2—C28	1.339 (3)	C17—C18	1.389 (3)
C1—C8	1.523 (3)	C18—C19	1.390 (3)
C1—C2	1.522 (3)	C18—H18A	1.03 (3)
C1—C14	1.527 (3)	C19—H19A	1.00 (3)
C1—H1A	1.01 (3)	C20—C21	1.377 (4)
C2—C7	1.388 (3)	C20—H20A	0.97 (3)
C2—C3	1.399 (3)	C21—C22	1.390 (3)
C3—C4	1.381 (3)	C21—H21A	0.97 (3)
C3—H3A	0.99 (2)	C22—C23	1.393 (3)
C4—C5	1.384 (3)	C22—C25	1.483 (3)
C4—H4A	0.99 (3)	C23—C24	1.383 (3)
C5—C6	1.389 (3)	C23—H23A	0.98 (3)
C6—C7	1.393 (3)	C24—H24A	0.97 (3)
C6—H6A	1.02 (3)	C25—C26	1.389 (3)
C7—H7A	1.03 (3)	C25—C29	1.397 (3)
C8—C13	1.389 (3)	C26—C27	1.381 (4)
C8—C9	1.396 (3)	C26—H26A	0.99 (3)
C9—C10	1.388 (3)	C27—H27A	0.97 (3)
C9—H9A	1.03 (3)	C28—C29	1.381 (3)
C10—C11	1.382 (3)	C28—H28A	0.96 (3)
C10—H10A	0.98 (3)	C29—H29A	0.96 (3)
C11—C12	1.386 (3)
C5—O1—H1	110.5 (18)	C19—C14—C1	122.08 (19)
C11—O2—H2	108 (2)	C15—C14—C1	120.24 (19)
C17—O3—H3	108.5 (19)	C16—C15—C14	121.3 (2)
C20—N1—C24	117.8 (2)	C16—C15—H15A	117.5 (16)
C27—N2—C28	117.4 (2)	C14—C15—H15A	121.2 (16)
C8—C1—C2	110.74 (17)	C15—C16—C17	120.20 (19)
C8—C1—C14	113.08 (17)	C15—C16—H16A	121.9 (15)
C2—C1—C14	111.66 (17)	C17—C16—H16A	117.9 (15)
C8—C1—H1A	108.0 (12)	O3—C17—C18	122.53 (19)
C2—C1—H1A	109.5 (12)	O3—C17—C16	118.42 (18)
C14—C1—H1A	103.5 (13)	C18—C17—C16	119.05 (19)
C7—C2—C3	117.57 (19)	C19—C18—C17	120.1 (2)
C7—C2—C1	120.90 (19)	C19—C18—H18A	121.7 (15)
C3—C2—C1	121.42 (18)	C17—C18—H18A	118.2 (15)
C4—C3—C2	121.3 (2)	C14—C19—C18	121.6 (2)
C4—C3—H3A	119.2 (14)	C14—C19—H19A	118.5 (18)
C2—C3—H3A	119.4 (14)	C18—C19—H19A	119.8 (18)
C3—C4—C5	120.4 (2)	N1—C20—C21	123.2 (2)
C3—C4—H4A	119.5 (14)	N1—C20—H20A	120.6 (16)
C5—C4—H4A	120.1 (15)	C21—C20—H20A	116.2 (16)
O1—C5—C4	118.36 (19)	C20—C21—C22	119.4 (2)
O1—C5—C6	122.2 (2)	C20—C21—H21A	121.2 (16)
C4—C5—C6	119.4 (2)	C22—C21—H21A	119.4 (16)
C5—C6—C7	119.7 (2)	C21—C22—C23	117.4 (2)
C5—C6—H6A	118.6 (15)	C21—C22—C25	121.7 (2)
C7—C6—H6A	121.7 (15)	C23—C22—C25	120.96 (19)
C2—C7—C6	121.6 (2)	C24—C23—C22	119.7 (2)
C2—C7—H7A	120.0 (14)	C24—C23—H23A	120.9 (17)
C6—C7—H7A	118.4 (14)	C22—C23—H23A	119.5 (17)
C13—C8—C9	117.99 (19)	N1—C24—C23	122.5 (2)
C13—C8—C1	122.30 (19)	N1—C24—H24A	116.6 (14)
C9—C8—C1	119.26 (19)	C23—C24—H24A	120.9 (14)
C10—C9—C8	121.2 (2)	C26—C25—C29	117.6 (2)
C10—C9—H9A	119.1 (13)	C26—C25—C22	121.55 (19)
C8—C9—H9A	119.7 (13)	C29—C25—C22	120.8 (2)
C11—C10—C9	120.0 (2)	C27—C26—C25	119.5 (2)
C11—C10—H10A	120.9 (16)	C27—C26—H26A	116.1 (16)
C9—C10—H10A	119.1 (16)	C25—C26—H26A	124.3 (16)
O2—C11—C10	122.1 (2)	N2—C27—C26	123.1 (2)
O2—C11—C12	118.1 (2)	N2—C27—H27A	116.8 (15)
C10—C11—C12	119.8 (2)	C26—C27—H27A	120.1 (15)
C11—C12—C13	119.9 (2)	N2—C28—C29	123.4 (2)
C11—C12—H12A	120.3 (17)	N2—C28—H28A	114.6 (18)
C13—C12—H12A	119.8 (17)	C29—C28—H28A	121.9 (18)
C8—C13—C12	121.1 (2)	C28—C29—C25	118.9 (2)
C8—C13—H13A	119.5 (14)	C28—C29—H29A	123.4 (16)
C12—C13—H13A	119.2 (14)	C25—C29—H29A	117.7 (16)
C19—C14—C15	117.7 (2)
C23—C22—C25—C29	−32.2 (3)	H1A—C1—C14—C15	−34.6 (12)
H1A—C1—C2—C7	−33.0 (14)	H1A—C1—C8—C9	−40.7 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O2^i	0.97 (3)	2.42 (3)	3.384 (3)	175 (2)
O2—H2···O1^ii	0.92 (4)	1.78 (4)	2.694 (3)	174 (3)
O1—H1···N1	1.04 (3)	1.60 (3)	2.622 (3)	169 (3)
O3—H3···N2^iii	0.97 (3)	1.80 (3)	2.764 (3)	174 (3)

Symmetry codes: (i) x−1/4, −y+5/4, z−1/4; (ii) −x+3/4, y+1/4, z−1/4; (iii) x−1/4, −y+3/4, z+5/4.