Adducts of 1,1,1-tris(4-hydroxy­phenyl)­ethane with 1,2-bis(4-pyridyl)­ethane and 1,2-bis(4-pyridyl)­ethene: continuously interwoven structures in three dimensions

In the adduct 1,2-bis(4-pyridyl)­ethane-1,1,1-tris(4-hydroxy­phenyl)­ethane (1/2), C₁₂H₁₂N₂·2C₂₀H₁₈O₃, the bipyridyl component lies across an inversion centre in P. The tris-phenol mol­ecules [systematic name: 4,4',4''-(ethane-1,1,1-triyl)­triphenol] are linked by O-H...O hydrogen bonds to form sheets built from R(38) rings, and symmetry-related pairs of sheets are linked by the bipyridyl mol­ecules via O-H...N hydrogen bonds to form open bilayers. Each bilayer is interwoven with two adjacent bilayers, forming a continuous three-dimensional structure. In the adduct 1,2-bis(4-pyridyl)­ethene-1,1,1-tris(4-hydroxy­phenyl)­ethane-methanol (1/1/1), C₁₂H₁₀N₂·C₂₀H₁₈O₃·CH₄O, the mol­ecules are linked by O-H...O and O-H...N hydrogen bonds into three interwoven three-dimensional frameworks, generated by single spiral chains along [010] and [001] and a triple-helical spiral along [100].

S1. Comment

When cocrystallized with 4,4'-bipyridyl the threefold symmetric tris-phenol 1,1,1-tris(4-hydroxyphenyl)ethane [systematic name: 4,4',4''-(ethane-1,1,1-triyl)triphenol], CH₃C(C₆H₄OH)₃, forms a hydrogen-bonded adduct of 3:2 stoichiometry, 3C₁₀H₈N₂·2C₂₀H₁₈O₃, in which all the hydrogen bonds are of the O—H···N type and whose supramolecular structure consists of tenfold interwoven nets built from R¹²₁₂(126) rings (Bényei et al., 1998). In a similar way, 4,4'-bipyridyl forms 3:2 adducts both with 1,3,5-benzenetricarboxylic acid (Sharma & Zaworotko, 1996) and with 2,3,5,6-tetrahydroxybenzoquinone (Cowan et al., 2001); in the 1,3,5-benzenetricarboxylic acid adduct, the components are linked into threefold interwoven nets built from R¹²₁₂(102) rings, while the 2,3,5,6-tetrahydroxybenzoquinone adduct has a three-dimensional supramolecular structure consisting of three interpenetrating frameworks. On the basis of the two-dimensional examples above, there seems to be no obvious impediment to the formation of nets containing yet larger rings and, accordingly, we have now investigated the cocrystallization of 1,1,1-tris(4-hydroxyphenyl)ethane with the extended bipyridyl species 1,2-bis(4-pyridyl)ethane and 1,2-bis(4-pyridyl)ethene in the hope, and expectation, of generating nets built from R¹²₁₂(138) rings. In the event, no 3:2 adducts could be found; instead, 1,2-bis(4-pyridyl)ethane yields a 1:2 adduct, C₁₂H₁₂N₂·2C₂₀H₁₈O₃, (I), while 1,2-bis(4-pyridyl)ethene yields a methanol-solvated 1:1 adduct, C₁₂H₁₀N₂·C₂₀H₁₈O₃·CH₄O, (II).

In compound (I), the bis(4-pyridyl)ethane molecule lies across a centre of inversion in space group P1, chosen for the sake of convenience as that at (1/2, 1/2, 1/2), and the tris-phenol component lies in a general position (Fig. 1). The supramolecular structure consists of continuously interwoven bilayers, giving a three-dimensional structure overall; the constitution of the bilayers, and thence of the overall structure, is most simply analysed in terms of the substructure built from just the tris-phenol component.

Atom O2 in the tris-phenol at (x, y, z) acts as a hydrogen-bond donor to O1 in the molecule at (x, y, -1 + z), so generating by translation a C(12) chain running parallel to the [001] direction. Atom O3 at (x, y, z) similarly acts as donor to O2 at (x, -1 + y, z), producing another C(12) chain, this time by translation along the [010] direction. The combination of these two simple chain motifs generates a sheet parallel to (100) built from a single type of R⁴₄(38) ring (Fig. 2). This reference sheet lies in the domain 0.96 < x < 1.56, and there is a symmetry-related sheet, generated by the inversion centres at (1/2, y, z), which lies in the domain -0.56 < x < 0.04. These two sheets are linked into a hydrogen-bonded bilayer by the amines; atoms of type O1 at (x, y, z) and (1 - x, 1 - y, 1 - z) in the domains 0.96 < x < 1.56 and -0.56 < x < 0.04, respectively, act as hydrogen-bond donors to the N1 atoms at (x, y, z) and (1 - x, 1 - y, 1 - z), respectively, which both lie in the reference amine centred at (1/2, 1/2, 1/2). Hence, these two (100) sheets are multiply linked by the series of amines centred at (1/2, m+0.5, n+0.5), where m, n = zero or integer.

Each bilayer is continuously interwoven with the two adjacent bilayers, as the bis(4-pyridyl)ethane linkers in one bilayer pass through the R⁴₄(38) rings in the adjacent sheet. In the (100) sheet containing the tris-phenol at (x, y, z), the centroids of the rings are at approximately (1.30, 0.70, 0.45) and similarly by translation along [010] and [001], and there are bis(4-pyridyl)ethane units centred close to these points, at (1.5, m+0.5, n+0.5), where m, n = zero or integer. In the other component of the reference bilayer, there is a ring centroid at approximately (-0.30, 0.30, 0.55), close to the centre of the bis(4-pyridyl)ethane molecule at (-0.5, 1/2, 1/2), and so on. Thus, the bilayer centred at x = 0.5 is interwoven with the two bilayers centred at x = 1.5 and x = -0.5; with each bilayer interwoven with its two neighbouring bilayers, the overall supramolecular structure is three-dimensional (Fig. 3).

The (100) sheets of tris-phenol molecules are generated by translation and hence are not puckered; nor are they interwoven. It is of interest to compare these sheets, built from a single tris-phenol molecule, with the analogous sheets of R⁴₄(38) rings in the 1:2 adduct C₂H₈N₂·2C₂₀H₁₈O₃, (III), formed with 1,2-diaminoethane (Ferguson et al., 1998). Here the sheets are built from two independent tris-phenol molecules and they are so deeply interwoven as to be pairwise interwoven; nonetheless the individual ring structures containing seven O atoms, but only four O—H···O hydrogen bonds, are identical in compounds (I) and (III).

The interweaving of the two-dimensional hydrogen-bonded bilayers in (I) to form an overall three-dimensional structure may be compared with the interweaving of hydrogen-bonded molecular ladders to form sheets in the 2:1 adduct of 4,4'-sulfonyldiphenol and pyrazine, (IV) (Ferguson et al., 1999), where the ladders have R⁶₆(50) rings between the rungs and each ladder is interwoven with two adjacent ladders. We have previously noted (Ferguson et al., 1999) that for systems of this type based on substituted aryl components and containing interwoven substructures, ring types such as R⁴₄(32) and R⁴₄(38) can permit just one strand of an interwoven substructure to pass through each ring, while larger types such as R⁶₆(48) can accommodate up to three strands; the number apparently depends upon the extent to which the rings are puckered. Consistent with this, in compounds (I) and (III), the R⁴₄(38) rings can accommodate either part of another tris-phenol molecule, as in (III), or part of a bipyridyl, as in (I), but these choices are mutually exclusive. The larger R⁶₆(50) rings in the interwoven ladders of (IV) can readily accommodate two strands from adjacent ladders.

In the methanol solvate (II), atoms O1 and O3 in the tris-phenol component act as hydrogen-bond donors to the methanol O4 and bipyridyl N41 atoms, respectively, within the asymmetric unit (Fig. 4). The two remaining hydrogen bonds (Table 4) serve to link the molecules in three dimensions; the hydrogen bonds having O2 and O4 as donors independently generate spiral chains along [001] and [100], respectively, while their combined action generates a spiral chain long [010].

The tris-phenol O2 atom at (x, y, z) acts as hydrogen-bond donor to O3 at (0.5 - x, 1 - y, 0.5 + z), while O2 at (0.5 - x, 1 - y, 0.5 + z) acts as donor to O3 at (x, y, 1 + z), so producing a C(12) chain running parallel to [001] and generated by the 2₁ screw axis along (1/4, 1/2, z) (Fig. 5). The methanol O4 atom at (x, y, z) acts as donor to N51 at (-1.5 + x, 0.5 - y, 1 - z), while O4 at (-1.5 + x, 0.5 - y, 1 - z),in turn, acts as donor to N51 at (-3 + x, y, z). The resulting C³₃(25) chain parallel to [100] (Fig. 6) is generated by the 2₁ axis along (x, 1/4, 1/2) and it has a repeat vector along [100] of three unit-cell lengths; there are thus three such spiral chains, related by translation, forming a triple helix along [100]. Each of these chains along [001] and [100] involves just one hydrogen bond outside the asymmetric unit; the combination of these two spiral chains generates a third spiral, along [010], involving both of the hydrogen bonds outside the asymmetric unit,

Just as O4 at (x, y, z) acts as donor to N51 at (-1.5 + x, 0.5 - y, 1 - z) to generate the [100] chain, so O4 at (0.5 - x, 1 - y, 0.5 + z) in the [001] chain acts as donor to N51 at (2 - x, 0.5 + y, 1.5 - z); O2 at (2 - x, 0.5 + y, 1.5 - z), in turn, acts as donor to O3 at (1.5 + x, 1.5 - y, 1 - z) and O4 at (1.5 + x, 1.5 - y, 1 - z) acts as donor to N51 at (x, 1 + y, z). In this way, a C⁴₄(35) chain is generated parallel to [010] (Fig. 7), which links the [100] and [001] spirals, so forming a three-dimensional framework. Since there are three unconnected chains in the triple helix along [100], there are three interwoven frameworks in the structure.

In both (I) and (II), the tris-phenol component shows significant deviations from the idealized C₃ molecular symmetry (Tables 1 and 2). While the bipyridyl component in (II) is almost flat, in (I), the bipyridyl skeleton is very far from being planar. The bond lengths and angles present no unusual features.

S2. Experimental

Equimolar quantities of the 1,1,1-tris(4-hydroxyphenyl)ethane and the appropriate bipyridyl were separately dissolved in methanol. For each compound, solutions of the tris-phenol and the appropriate bipyridyl were mixed and set aside to crystallize, providing (I) and (II), respectively. Analyses, (I): found C 77.8, H 6.2, N 3.5%; C₅₀H₄₈N₂O₆ requires C 77.7, H 6.3, N 3.6%; (II): found C 76.0, H 6.7, N 5.4%; C₃₃H₃₂N₂O₄ requires C 76.1, H 6.2, N 5.4%. Crystals suitable for single-crystal X-ray diffraction were selected directly from the analytical samples.

S3. Refinement

Compound (I) crystallized in the triclinic system; space group P1 was assumed and subsequently confirmed by the analysis. For compound (II), space group P2₁2₁2₁ was uniquely assigned from the systematic absences. The refined value, 2(3), of the Flack (1983) parameterwas inconclusive (Flack & Bernardinelli, 2000), hence Friedel equivalents were merged prior to the final refinements. All H atoms were treated as riding atoms, with C—H distances in the range 0.95–0.99 Å and O—H distances of 0.84 Å.

Computing details

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001). Software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999) for (I); SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999) for (II).

Figures

	Fig. 1. The molecular components of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I) showing formation of a (100) sheet built from R^44(38) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (x, y, 1 + z), (x, -1 + y, -1 + z) and (x, y, -1 + z), respectively.
	Fig. 3. Stereoview of part of the crystal structure of (I) showing the interweaving of adjacent bilayers.
	Fig. 4. The molecular components of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. Part of the crystal structure of (II) showing formation of a C(12) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (0.5 - x, 1 - y, 0.5 + z), (x, y, 1 + z) and (0.5 - x, 1 - y, -0.5 + z), respectively.
	Fig. 6. Part of the crystal structure of (II) showing one component of the triple helix along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (-1.5 + x, 0.5 - y, 1 - z) and (1.5 + x, 0.5 - y, 1 - z), respectively.
	Fig. 7. Part of the crystal structure of (II) showing formation of a C^44(35) chain along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (0.5 - x, 1 - y, 0.5 + z), (2 - x, 0.5 + y, 1.5 - z), (1.5 + x, 1.5 - y, 1 - z) and (x, 1 + y, z), respectively.

(I) 1,2-Bis(4'-pyridyl)ethane–1,1,1-tris(4-hydroxyphenyl)ethane (1/2)

Crystal data

C12H12N2·2C20H18O3	Z = 1
Mr = 796.92	F(000) = 422
Triclinic, P1	Dx = 1.255 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2076 (2) Å	Cell parameters from 4446 reflections
b = 10.6559 (2) Å	θ = 3.1–27.5°
c = 10.9341 (2) Å	µ = 0.08 mm^−1
α = 100.9920 (16)°	T = 150 K
β = 109.4530 (14)°	Block, colourless
γ = 101.6700 (11)°	0.30 × 0.20 × 0.18 mm
V = 1054.49 (3) Å^3

Data collection

Kappa-CCD diffractometer	4797 independent reflections
Radiation source: fine-focus sealed X-ray tube	3886 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = 0→13
Tmin = 0.976, Tmax = 0.985	k = −13→13
13679 measured reflections	l = −14→12

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.196P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4797 reflections	Δρmax = 0.22 e Å^−3
276 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.074 (8)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.07976 (11)	0.19588 (11)	0.54229 (9)	0.0364 (3)
O2	1.24756 (12)	0.34767 (10)	−0.20730 (9)	0.0363 (2)
O3	1.07237 (12)	−0.50019 (10)	−0.14460 (11)	0.0426 (3)
C1	1.34508 (13)	0.04092 (12)	0.17400 (12)	0.0237 (3)
C2	1.51061 (13)	0.07340 (14)	0.25400 (13)	0.0299 (3)
C11	1.27299 (13)	0.08509 (12)	0.27198 (12)	0.0241 (3)
C12	1.31224 (17)	0.06065 (16)	0.39778 (14)	0.0392 (4)
C13	1.24684 (18)	0.09705 (18)	0.48618 (14)	0.0443 (4)
C14	1.13922 (14)	0.15989 (13)	0.45060 (12)	0.0280 (3)
C15	1.09683 (13)	0.18381 (13)	0.32569 (12)	0.0259 (3)
C16	1.16273 (13)	0.14611 (13)	0.23781 (12)	0.0262 (3)
C21	1.32052 (13)	0.11895 (12)	0.06746 (12)	0.0234 (3)
C22	1.38429 (14)	0.25688 (13)	0.10620 (12)	0.0281 (3)
C23	1.35965 (15)	0.33185 (13)	0.01504 (13)	0.0300 (3)
C24	1.27008 (14)	0.26951 (13)	−0.11934 (12)	0.0276 (3)
C25	1.20579 (14)	0.13329 (13)	−0.16115 (12)	0.0284 (3)
C26	1.23157 (13)	0.05955 (12)	−0.06776 (12)	0.0261 (3)
C31	1.27828 (13)	−0.10920 (12)	0.10285 (12)	0.0241 (3)
C32	1.35497 (14)	−0.18380 (13)	0.05045 (13)	0.0307 (3)
C33	1.28890 (15)	−0.31416 (13)	−0.03031 (14)	0.0336 (3)
C34	1.14415 (15)	−0.37398 (13)	−0.06062 (13)	0.0307 (3)
C35	1.06642 (14)	−0.30349 (13)	−0.00677 (13)	0.0310 (3)
C36	1.13350 (13)	−0.17336 (13)	0.07377 (13)	0.0281 (3)
N41	0.86824 (12)	0.30647 (12)	0.49551 (11)	0.0327 (3)
C42	0.81396 (16)	0.29772 (16)	0.58974 (15)	0.0395 (3)
C43	0.71869 (17)	0.36662 (18)	0.61082 (15)	0.0457 (4)
C44	0.67745 (15)	0.45044 (15)	0.53263 (16)	0.0406 (4)
C45	0.73375 (16)	0.45926 (15)	0.43425 (17)	0.0408 (3)
C46	0.82787 (15)	0.38664 (14)	0.41886 (15)	0.0360 (3)
C47	0.57473 (17)	0.52853 (18)	0.55278 (19)	0.0561 (5)
H1	1.0110	0.2263	0.5072	0.055*
H2	1.1993	0.2986	−0.2865	0.054*
H3	1.1316	−0.5353	−0.1652	0.064*
H2A	1.5291	0.0120	0.3097	0.045*
H2B	1.5481	0.1654	0.3122	0.045*
H2C	1.5592	0.0634	0.1906	0.045*
H12	1.3860	0.0178	0.4239	0.047*
H13	1.2759	0.0788	0.5714	0.053*
H15	1.0225	0.2261	0.2997	0.031*
H16	1.1316	0.1625	0.1518	0.031*
H22	1.4464	0.3004	0.1979	0.034*
H23	1.4038	0.4255	0.0443	0.036*
H25	1.1443	0.0902	−0.2531	0.034*
H26	1.1870	−0.0341	−0.0975	0.031*
H32	1.4546	−0.1443	0.0706	0.037*
H33	1.3434	−0.3627	−0.0650	0.040*
H35	0.9676	−0.3444	−0.0251	0.037*
H36	1.0793	−0.1262	0.1104	0.034*
H42	0.8421	0.2414	0.6452	0.047*
H43	0.6818	0.3564	0.6786	0.055*
H45	0.7077	0.5151	0.3776	0.049*
H46	0.8654	0.3940	0.3510	0.043*
H47A	0.5706	0.5311	0.6424	0.067*
H47B	0.6133	0.6215	0.5526	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0413 (6)	0.0546 (7)	0.0281 (5)	0.0307 (5)	0.0193 (4)	0.0159 (4)
O2	0.0528 (6)	0.0311 (5)	0.0297 (5)	0.0161 (5)	0.0168 (5)	0.0128 (4)
O3	0.0437 (6)	0.0261 (5)	0.0517 (6)	0.0065 (4)	0.0179 (5)	0.0011 (4)
C1	0.0223 (6)	0.0273 (6)	0.0220 (5)	0.0093 (5)	0.0088 (5)	0.0057 (5)
C2	0.0236 (6)	0.0348 (7)	0.0297 (6)	0.0106 (5)	0.0079 (5)	0.0072 (5)
C11	0.0249 (6)	0.0250 (6)	0.0228 (6)	0.0091 (5)	0.0092 (5)	0.0054 (5)
C12	0.0479 (8)	0.0579 (9)	0.0317 (7)	0.0386 (8)	0.0205 (6)	0.0225 (7)
C13	0.0559 (9)	0.0717 (11)	0.0298 (7)	0.0451 (9)	0.0235 (7)	0.0274 (7)
C14	0.0304 (6)	0.0337 (7)	0.0241 (6)	0.0147 (5)	0.0130 (5)	0.0073 (5)
C15	0.0230 (6)	0.0299 (6)	0.0254 (6)	0.0117 (5)	0.0077 (5)	0.0076 (5)
C16	0.0247 (6)	0.0327 (7)	0.0215 (5)	0.0112 (5)	0.0074 (5)	0.0082 (5)
C21	0.0224 (6)	0.0268 (6)	0.0233 (6)	0.0091 (5)	0.0112 (5)	0.0060 (5)
C22	0.0297 (6)	0.0276 (7)	0.0236 (6)	0.0064 (5)	0.0097 (5)	0.0028 (5)
C23	0.0360 (7)	0.0230 (6)	0.0312 (6)	0.0072 (5)	0.0152 (6)	0.0050 (5)
C24	0.0330 (7)	0.0292 (7)	0.0273 (6)	0.0135 (5)	0.0157 (5)	0.0106 (5)
C25	0.0307 (6)	0.0301 (7)	0.0227 (6)	0.0083 (5)	0.0094 (5)	0.0056 (5)
C26	0.0267 (6)	0.0247 (6)	0.0247 (6)	0.0060 (5)	0.0091 (5)	0.0047 (5)
C31	0.0252 (6)	0.0256 (6)	0.0238 (6)	0.0100 (5)	0.0099 (5)	0.0084 (5)
C32	0.0265 (6)	0.0297 (7)	0.0370 (7)	0.0097 (5)	0.0145 (6)	0.0063 (5)
C33	0.0344 (7)	0.0293 (7)	0.0404 (7)	0.0135 (6)	0.0184 (6)	0.0055 (6)
C34	0.0353 (7)	0.0241 (6)	0.0321 (6)	0.0083 (5)	0.0125 (6)	0.0074 (5)
C35	0.0269 (6)	0.0301 (7)	0.0369 (7)	0.0072 (5)	0.0136 (6)	0.0101 (5)
C36	0.0269 (6)	0.0309 (7)	0.0311 (6)	0.0117 (5)	0.0141 (5)	0.0099 (5)
N41	0.0282 (6)	0.0360 (6)	0.0338 (6)	0.0125 (5)	0.0119 (5)	0.0063 (5)
C42	0.0362 (8)	0.0511 (9)	0.0348 (7)	0.0183 (7)	0.0146 (6)	0.0122 (6)
C43	0.0345 (8)	0.0660 (11)	0.0368 (8)	0.0192 (8)	0.0168 (6)	0.0040 (7)
C44	0.0243 (7)	0.0355 (8)	0.0472 (8)	0.0079 (6)	0.0075 (6)	−0.0091 (6)
C45	0.0315 (7)	0.0302 (7)	0.0567 (9)	0.0099 (6)	0.0123 (7)	0.0110 (7)
C46	0.0302 (7)	0.0376 (8)	0.0428 (8)	0.0110 (6)	0.0164 (6)	0.0119 (6)
C47	0.0320 (8)	0.0480 (10)	0.0690 (11)	0.0165 (7)	0.0107 (8)	−0.0162 (8)

Geometric parameters (Å, º)

O1—C14	1.3688 (14)	C24—C25	1.3814 (18)
O1—H1	0.84	C25—C26	1.3928 (17)
O2—C24	1.3810 (14)	C25—H25	0.95
O2—H2	0.84	C26—H26	0.95
O3—C34	1.3678 (16)	C31—C36	1.3957 (17)
O3—H3	0.84	C31—C32	1.3963 (17)
C1—C31	1.5362 (17)	C32—C33	1.3860 (19)
C1—C21	1.5396 (16)	C32—H32	0.95
C1—C11	1.5439 (15)	C33—C34	1.3826 (19)
C1—C2	1.5503 (17)	C33—H33	0.95
C2—H2A	0.98	C34—C35	1.3872 (18)
C2—H2B	0.98	C35—C36	1.3841 (19)
C2—H2C	0.98	C35—H35	0.95
C11—C12	1.3900 (17)	C36—H36	0.95
C11—C16	1.3920 (16)	N41—C42	1.3316 (18)
C12—C13	1.3864 (18)	N41—C46	1.3369 (17)
C12—H12	0.95	C42—C43	1.383 (2)
C13—C14	1.3852 (18)	C42—H42	0.95
C13—H13	0.95	C43—C44	1.382 (2)
C14—C15	1.3789 (17)	C43—H43	0.95
C15—C16	1.3893 (16)	C44—C45	1.387 (2)
C15—H15	0.95	C44—C47	1.5091 (19)
C16—H16	0.95	C45—C46	1.3817 (19)
C21—C26	1.3884 (17)	C45—H45	0.95
C21—C22	1.3983 (18)	C46—H46	0.95
C22—C23	1.3831 (17)	C47—C47^i	1.488 (3)
C22—H22	0.95	C47—H47A	0.99
C23—C24	1.3869 (18)	C47—H47B	0.99
C23—H23	0.95
C14—O1—H1	109.5	C24—C25—H25	120.2
C24—O2—H2	109.5	C26—C25—H25	120.2
C34—O3—H3	109.5	C21—C26—C25	121.90 (11)
C31—C1—C21	109.27 (9)	C21—C26—H26	119.0
C31—C1—C11	109.93 (9)	C25—C26—H26	119.0
C21—C1—C11	109.30 (9)	C36—C31—C32	116.93 (12)
C31—C1—C2	110.58 (10)	C36—C31—C1	121.58 (10)
C21—C1—C2	108.43 (10)	C32—C31—C1	121.08 (11)
C11—C1—C2	109.29 (10)	C33—C32—C31	121.45 (12)
C1—C2—H2A	109.5	C33—C32—H32	119.3
C1—C2—H2B	109.5	C31—C32—H32	119.3
H2A—C2—H2B	109.5	C34—C33—C32	120.36 (12)
C1—C2—H2C	109.5	C34—C33—H33	119.8
H2A—C2—H2C	109.5	C32—C33—H33	119.8
H2B—C2—H2C	109.5	O3—C34—C33	122.59 (12)
C12—C11—C16	116.72 (11)	O3—C34—C35	117.99 (12)
C12—C11—C1	120.93 (10)	C33—C34—C35	119.41 (12)
C16—C11—C1	122.31 (10)	C36—C35—C34	119.72 (12)
C13—C12—C11	121.87 (12)	C36—C35—H35	120.1
C13—C12—H12	119.1	C34—C35—H35	120.1
C11—C12—H12	119.1	C35—C36—C31	122.09 (11)
C14—C13—C12	120.21 (12)	C35—C36—H36	119.0
C14—C13—H13	119.9	C31—C36—H36	119.0
C12—C13—H13	119.9	C42—N41—C46	117.53 (12)
O1—C14—C15	122.87 (11)	N41—C42—C43	123.19 (14)
O1—C14—C13	117.98 (11)	N41—C42—H42	118.4
C15—C14—C13	119.15 (11)	C43—C42—H42	118.4
C14—C15—C16	120.03 (11)	C44—C43—C42	119.55 (14)
C14—C15—H15	120.0	C44—C43—H43	120.2
C16—C15—H15	120.0	C42—C43—H43	120.2
C15—C16—C11	122.01 (11)	C43—C44—C45	117.24 (12)
C15—C16—H16	119.0	C43—C44—C47	121.42 (15)
C11—C16—H16	119.0	C45—C44—C47	121.35 (16)
C26—C21—C22	116.96 (11)	C46—C45—C44	119.80 (14)
C26—C21—C1	122.94 (11)	C46—C45—H45	120.1
C22—C21—C1	120.04 (10)	C44—C45—H45	120.1
C23—C22—C21	121.98 (11)	N41—C46—C45	122.70 (13)
C23—C22—H22	119.0	N41—C46—H46	118.7
C21—C22—H22	119.0	C45—C46—H46	118.7
C22—C23—C24	119.64 (12)	C47^i—C47—C44	113.21 (16)
C22—C23—H23	120.2	C47^i—C47—H47A	108.9
C24—C23—H23	120.2	C44—C47—H47A	108.9
O2—C24—C25	122.11 (11)	C47^i—C47—H47B	108.9
O2—C24—C23	118.01 (11)	C44—C47—H47B	108.9
C25—C24—C23	119.88 (11)	H47A—C47—H47B	107.7
C24—C25—C26	119.63 (11)
C31—C1—C11—C12	78.67 (15)	C22—C21—C26—C25	−0.33 (17)
C21—C1—C11—C12	−161.39 (13)	C1—C21—C26—C25	177.02 (10)
C2—C1—C11—C12	−42.87 (17)	C24—C25—C26—C21	0.09 (19)
C31—C1—C11—C16	−98.83 (13)	C21—C1—C31—C36	−88.13 (13)
C21—C1—C11—C16	21.11 (16)	C11—C1—C31—C36	31.82 (15)
C2—C1—C11—C16	139.63 (12)	C2—C1—C31—C36	152.59 (11)
C16—C11—C12—C13	−1.0 (2)	C21—C1—C31—C32	84.24 (13)
C1—C11—C12—C13	−178.68 (14)	C11—C1—C31—C32	−155.81 (11)
C11—C12—C13—C14	−0.1 (3)	C2—C1—C31—C32	−35.04 (15)
C12—C13—C14—O1	−178.90 (15)	C36—C31—C32—C33	2.03 (19)
C12—C13—C14—C15	0.9 (2)	C1—C31—C32—C33	−170.68 (12)
O1—C14—C15—C16	179.26 (12)	C31—C32—C33—C34	−0.3 (2)
C13—C14—C15—C16	−0.6 (2)	C32—C33—C34—O3	177.04 (12)
C14—C15—C16—C11	−0.6 (2)	C32—C33—C34—C35	−1.6 (2)
C12—C11—C16—C15	1.4 (2)	O3—C34—C35—C36	−177.11 (12)
C1—C11—C16—C15	179.02 (12)	C33—C34—C35—C36	1.6 (2)
C31—C1—C21—C26	9.19 (15)	C34—C35—C36—C31	0.28 (19)
C11—C1—C21—C26	−111.15 (12)	C32—C31—C36—C35	−2.04 (18)
C2—C1—C21—C26	129.80 (12)	C1—C31—C36—C35	170.63 (11)
C31—C1—C21—C22	−173.54 (10)	C46—N41—C42—C43	0.3 (2)
C11—C1—C21—C22	66.12 (13)	N41—C42—C43—C44	−0.8 (2)
C2—C1—C21—C22	−52.93 (14)	C42—C43—C44—C45	0.9 (2)
C26—C21—C22—C23	0.53 (17)	C42—C43—C44—C47	−179.48 (14)
C1—C21—C22—C23	−176.90 (11)	C43—C44—C45—C46	−0.5 (2)
C21—C22—C23—C24	−0.48 (19)	C47—C44—C45—C46	179.81 (14)
C22—C23—C24—O2	179.74 (11)	C42—N41—C46—C45	0.1 (2)
C22—C23—C24—C25	0.21 (19)	C44—C45—C46—N41	0.1 (2)
O2—C24—C25—C26	−179.53 (11)	C43—C44—C47—C47^i	−104.0 (3)
C23—C24—C25—C26	−0.02 (18)	C45—C44—C47—C47^i	75.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N41	0.84	1.81	2.6145 (18)	159
O2—H2···O1^ii	0.84	1.83	2.6671 (13)	175
O3—H3···O2^iii	0.84	1.98	2.8039 (17)	168

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

(II) 1,2-Bis(4'-pyridyl)ethene–1,1,1-tris(4-hydroxyphenyl)ethane–methanol (1/1/1)

Crystal data

C12H10N2·C20H18O3·CH4O	F(000) = 1104
Mr = 520.61	Dx = 1.223 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2663 reflections
a = 11.8264 (9) Å	θ = 2.6–25.0°
b = 14.2158 (9) Å	µ = 0.08 mm^−1
c = 16.8109 (12) Å	T = 150 K
V = 2826.3 (3) Å^3	Block, colourless
Z = 4	0.30 × 0.26 × 0.16 mm

Data collection

KappaCCD diffractometer	2795 independent reflections
Radiation source: fine-focus sealed X-ray tube	1859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
ϕ scans, and ω scans with κ offsets	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = 0→14
Tmin = 0.976, Tmax = 0.987	k = 0→16
11922 measured reflections	l = 0→20

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)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + 1.525P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2795 reflections	Δρmax = 0.22 e Å^−3
359 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0144 (17)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2045 (3)	−0.0490 (3)	0.2848 (2)	0.0561 (11)
O2	0.1312 (4)	0.2606 (3)	0.7819 (2)	0.0501 (10)
O3	0.4144 (3)	0.5744 (3)	0.3525 (2)	0.0551 (11)
C1	0.0895 (4)	0.2946 (4)	0.4439 (3)	0.0400 (13)
C2	−0.0310 (4)	0.3264 (4)	0.4233 (3)	0.0458 (14)
C11	0.1193 (4)	0.2023 (4)	0.4002 (3)	0.0394 (13)
C12	0.0349 (5)	0.1374 (4)	0.3789 (3)	0.0450 (14)
C13	0.0612 (5)	0.0548 (4)	0.3409 (3)	0.0487 (15)
C14	0.1726 (5)	0.0327 (4)	0.3232 (3)	0.0436 (14)
C15	0.2576 (5)	0.0944 (4)	0.3439 (3)	0.0495 (15)
C16	0.2294 (4)	0.1778 (4)	0.3820 (3)	0.0447 (14)
C21	0.0967 (4)	0.2817 (4)	0.5350 (3)	0.0396 (13)
C22	0.0716 (5)	0.3574 (4)	0.5850 (3)	0.0447 (14)
C23	0.0820 (5)	0.3528 (4)	0.6658 (3)	0.0434 (14)
C24	0.1185 (4)	0.2701 (4)	0.7016 (3)	0.0396 (13)
C25	0.1439 (5)	0.1944 (4)	0.6539 (3)	0.0470 (14)
C26	0.1333 (4)	0.1997 (4)	0.5711 (3)	0.0437 (14)
C31	0.1761 (4)	0.3720 (4)	0.4204 (3)	0.0378 (13)
C32	0.1576 (5)	0.4327 (4)	0.3564 (3)	0.0449 (14)
C33	0.2388 (5)	0.5006 (4)	0.3337 (3)	0.0461 (14)
C34	0.3398 (4)	0.5070 (4)	0.3749 (3)	0.0417 (13)
C35	0.3607 (4)	0.4452 (4)	0.4376 (3)	0.0443 (14)
C36	0.2783 (4)	0.3800 (4)	0.4603 (3)	0.0425 (14)
O4	0.0484 (3)	−0.1821 (3)	0.2977 (3)	0.0622 (12)
C3	0.0843 (6)	−0.2770 (4)	0.3092 (4)	0.0665 (19)
N41	0.6098 (4)	0.5851 (3)	0.4268 (3)	0.0473 (12)
C42	0.6364 (5)	0.6162 (5)	0.4993 (3)	0.0541 (16)
C43	0.7478 (5)	0.6248 (5)	0.5260 (3)	0.0551 (16)
C44	0.8363 (4)	0.5987 (4)	0.4764 (3)	0.0418 (13)
C45	0.8089 (5)	0.5678 (4)	0.4012 (3)	0.0492 (15)
C46	0.6964 (5)	0.5615 (4)	0.3787 (3)	0.0487 (14)
C47	0.9559 (4)	0.6054 (4)	0.5015 (3)	0.0439 (14)
N51	1.3371 (4)	0.6634 (4)	0.6443 (3)	0.0606 (14)
C52	1.3093 (5)	0.6232 (5)	0.5749 (4)	0.069 (2)
C53	1.1983 (5)	0.6113 (5)	0.5487 (4)	0.0608 (18)
C54	1.1125 (5)	0.6423 (4)	0.5952 (3)	0.0470 (15)
C55	1.1392 (5)	0.6828 (5)	0.6674 (4)	0.0625 (18)
C56	1.2518 (6)	0.6925 (5)	0.6894 (4)	0.0626 (18)
C57	0.9919 (5)	0.6339 (4)	0.5706 (3)	0.0489 (15)
H1	0.1477	−0.0734	0.2630	0.084*
H2	0.1109	0.3105	0.8045	0.075*
H3	0.4719	0.5718	0.3818	0.083*
H2A	−0.0856	0.2851	0.4497	0.069*
H2B	−0.0420	0.3233	0.3656	0.069*
H2C	−0.0423	0.3913	0.4415	0.069*
H12	−0.0418	0.1509	0.3910	0.054*
H13	0.0025	0.0124	0.3265	0.058*
H15	0.3343	0.0801	0.3322	0.059*
H16	0.2884	0.2199	0.3962	0.054*
H22	0.0463	0.4145	0.5618	0.054*
H23	0.0643	0.4061	0.6975	0.052*
H25	0.1690	0.1374	0.6776	0.056*
H26	0.1515	0.1465	0.5394	0.052*
H32	0.0889	0.4282	0.3274	0.054*
H33	0.2240	0.5417	0.2903	0.055*
H35	0.4309	0.4474	0.4650	0.053*
H36	0.2927	0.3400	0.5045	0.051*
H4	−0.0118	−0.1728	0.3229	0.093*
H3A	0.1501	−0.2898	0.2754	0.100*
H3B	0.0226	−0.3198	0.2949	0.100*
H3C	0.1048	−0.2864	0.3651	0.100*
H42	0.5769	0.6333	0.5343	0.065*
H43	0.7629	0.6484	0.5777	0.066*
H45	0.8669	0.5509	0.3649	0.059*
H46	0.6795	0.5393	0.3268	0.058*
H47	1.0116	0.5873	0.4638	0.053*
H52	1.3687	0.6016	0.5416	0.083*
H53	1.1831	0.5820	0.4991	0.073*
H55	1.0808	0.7040	0.7018	0.075*
H56	1.2686	0.7212	0.7391	0.075*
H57	0.9362	0.6508	0.6088	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.065 (3)	0.047 (3)	0.056 (2)	−0.002 (2)	0.013 (2)	−0.012 (2)
O2	0.064 (3)	0.048 (3)	0.038 (2)	−0.003 (2)	−0.0025 (19)	0.0007 (18)
O3	0.047 (2)	0.062 (3)	0.056 (2)	−0.019 (2)	−0.0120 (19)	0.018 (2)
C1	0.040 (3)	0.042 (3)	0.038 (3)	−0.003 (3)	−0.001 (2)	0.004 (2)
C2	0.045 (3)	0.048 (4)	0.045 (3)	−0.002 (3)	−0.003 (3)	0.003 (3)
C11	0.040 (3)	0.041 (3)	0.037 (3)	−0.005 (3)	0.002 (2)	0.001 (2)
C12	0.038 (3)	0.052 (4)	0.045 (3)	0.001 (3)	0.003 (3)	−0.002 (3)
C13	0.048 (4)	0.046 (4)	0.052 (3)	−0.011 (3)	0.001 (3)	−0.002 (3)
C14	0.053 (4)	0.039 (3)	0.039 (3)	0.001 (3)	0.014 (3)	−0.005 (3)
C15	0.044 (3)	0.052 (4)	0.053 (3)	−0.004 (3)	0.007 (3)	−0.008 (3)
C16	0.038 (3)	0.048 (4)	0.048 (3)	−0.004 (3)	0.002 (3)	−0.001 (3)
C21	0.041 (3)	0.041 (3)	0.036 (3)	−0.001 (3)	0.000 (2)	0.002 (3)
C22	0.054 (3)	0.038 (3)	0.042 (3)	0.004 (3)	0.003 (3)	0.004 (3)
C23	0.053 (3)	0.037 (3)	0.040 (3)	0.003 (3)	0.005 (3)	−0.006 (3)
C24	0.037 (3)	0.047 (3)	0.035 (3)	−0.002 (3)	0.001 (2)	0.001 (3)
C25	0.051 (3)	0.044 (3)	0.045 (3)	0.002 (3)	−0.001 (3)	0.008 (3)
C26	0.046 (3)	0.039 (3)	0.046 (3)	0.000 (3)	0.001 (3)	0.001 (3)
C31	0.037 (3)	0.041 (3)	0.035 (3)	−0.002 (3)	−0.002 (2)	0.001 (3)
C32	0.043 (3)	0.047 (3)	0.044 (3)	0.001 (3)	−0.007 (3)	0.004 (3)
C33	0.047 (3)	0.049 (4)	0.042 (3)	−0.001 (3)	−0.009 (3)	0.011 (3)
C34	0.037 (3)	0.047 (3)	0.041 (3)	−0.006 (3)	0.002 (3)	0.005 (3)
C35	0.037 (3)	0.055 (4)	0.041 (3)	0.001 (3)	−0.006 (2)	0.006 (3)
C36	0.043 (3)	0.045 (3)	0.039 (3)	0.002 (3)	0.001 (2)	0.011 (3)
O4	0.049 (3)	0.051 (3)	0.086 (3)	−0.007 (2)	0.018 (2)	−0.005 (2)
C3	0.057 (4)	0.047 (4)	0.096 (5)	0.000 (3)	0.014 (4)	−0.001 (4)
N41	0.043 (3)	0.049 (3)	0.050 (3)	−0.007 (2)	−0.002 (2)	0.004 (2)
C42	0.041 (3)	0.069 (4)	0.053 (4)	0.004 (3)	0.003 (3)	−0.003 (3)
C43	0.050 (4)	0.070 (4)	0.045 (3)	−0.003 (3)	−0.001 (3)	−0.005 (3)
C44	0.045 (3)	0.042 (3)	0.038 (3)	0.000 (3)	0.003 (3)	0.006 (3)
C45	0.045 (3)	0.058 (4)	0.045 (3)	0.004 (3)	0.003 (3)	0.002 (3)
C46	0.055 (4)	0.041 (3)	0.050 (3)	−0.004 (3)	−0.006 (3)	0.003 (3)
C47	0.038 (3)	0.048 (4)	0.046 (3)	−0.002 (3)	0.004 (3)	−0.004 (3)
N51	0.051 (3)	0.063 (3)	0.068 (3)	0.006 (3)	−0.012 (3)	−0.011 (3)
C52	0.040 (4)	0.094 (5)	0.074 (5)	−0.002 (4)	−0.010 (3)	−0.033 (4)
C53	0.033 (3)	0.090 (5)	0.059 (4)	−0.001 (3)	0.004 (3)	−0.026 (4)
C54	0.045 (3)	0.045 (3)	0.051 (3)	0.002 (3)	−0.010 (3)	0.000 (3)
C55	0.061 (4)	0.068 (4)	0.059 (4)	0.015 (4)	−0.012 (3)	−0.014 (3)
C56	0.055 (4)	0.068 (4)	0.065 (4)	0.011 (4)	−0.019 (3)	−0.012 (4)
C57	0.043 (3)	0.052 (4)	0.052 (3)	0.007 (3)	0.000 (3)	−0.002 (3)

Geometric parameters (Å, º)

O1—C14	1.381 (6)	C33—C34	1.385 (8)
O1—H1	0.84	C33—H33	0.95
O2—C24	1.364 (6)	C34—C35	1.394 (7)
O2—H2	0.84	C35—C36	1.397 (7)
O3—C34	1.355 (6)	C35—H35	0.95
O3—H3	0.84	C36—H36	0.95
C1—C2	1.535 (7)	O4—C3	1.427 (7)
C1—C21	1.545 (7)	O4—H4	0.84
C1—C11	1.545 (8)	C3—H3A	0.98
C1—C31	1.554 (7)	C3—H3B	0.98
C2—H2A	0.98	C3—H3C	0.98
C2—H2B	0.98	N41—C42	1.333 (7)
C2—H2C	0.98	N41—C46	1.347 (7)
C11—C16	1.382 (7)	C42—C43	1.397 (8)
C11—C12	1.406 (7)	C42—H42	0.95
C12—C13	1.371 (8)	C43—C44	1.388 (7)
C12—H12	0.95	C43—H43	0.95
C13—C14	1.387 (8)	C44—C45	1.377 (7)
C13—H13	0.95	C44—C47	1.480 (7)
C14—C15	1.379 (8)	C45—C46	1.386 (7)
C15—C16	1.388 (7)	C45—H45	0.95
C15—H15	0.95	C46—H46	0.95
C16—H16	0.95	C47—C57	1.301 (7)
C21—C26	1.384 (7)	C47—H47	0.95
C21—C22	1.397 (7)	N51—C56	1.328 (7)
C22—C23	1.365 (7)	N51—C52	1.339 (7)
C22—H22	0.95	C52—C53	1.395 (8)
C23—C24	1.390 (7)	C52—H52	0.95
C23—H23	0.95	C53—C54	1.354 (7)
C24—C25	1.376 (7)	C53—H53	0.95
C25—C26	1.398 (7)	C54—C55	1.379 (8)
C25—H25	0.95	C54—C57	1.490 (7)
C26—H26	0.95	C55—C56	1.390 (8)
C31—C36	1.387 (7)	C55—H55	0.95
C31—C32	1.396 (7)	C56—H56	0.95
C32—C33	1.414 (8)	C57—H57	0.95
C32—H32	0.95
C14—O1—H1	109.5	C34—C33—C32	119.7 (5)
C24—O2—H2	109.5	C34—C33—H33	120.2
C34—O3—H3	109.5	C32—C33—H33	120.2
C2—C1—C21	108.0 (4)	O3—C34—C33	118.0 (5)
C2—C1—C11	110.8 (4)	O3—C34—C35	122.7 (5)
C21—C1—C11	111.0 (4)	C33—C34—C35	119.3 (5)
C2—C1—C31	110.3 (4)	C34—C35—C36	120.1 (5)
C21—C1—C31	107.5 (4)	C34—C35—H35	120.0
C11—C1—C31	109.3 (4)	C36—C35—H35	120.0
C1—C2—H2A	109.5	C31—C36—C35	122.0 (5)
C1—C2—H2B	109.5	C31—C36—H36	119.0
H2A—C2—H2B	109.5	C35—C36—H36	119.0
C1—C2—H2C	109.5	C3—O4—H4	109.5
H2A—C2—H2C	109.5	O4—C3—H3A	109.5
H2B—C2—H2C	109.5	O4—C3—H3B	109.5
C16—C11—C12	116.5 (5)	H3A—C3—H3B	109.5
C16—C11—C1	122.3 (5)	O4—C3—H3C	109.5
C12—C11—C1	121.2 (5)	H3A—C3—H3C	109.5
C13—C12—C11	121.3 (5)	H3B—C3—H3C	109.5
C13—C12—H12	119.3	C42—N41—C46	116.8 (5)
C11—C12—H12	119.3	N41—C42—C43	123.0 (5)
C12—C13—C14	120.6 (5)	N41—C42—H42	118.5
C12—C13—H13	119.7	C43—C42—H42	118.5
C14—C13—H13	119.7	C44—C43—C42	119.6 (5)
C15—C14—O1	117.0 (5)	C44—C43—H43	120.2
C15—C14—C13	119.6 (5)	C42—C43—H43	120.2
O1—C14—C13	123.4 (5)	C45—C44—C43	117.3 (5)
C14—C15—C16	119.0 (5)	C45—C44—C47	120.5 (5)
C14—C15—H15	120.5	C43—C44—C47	122.2 (5)
C16—C15—H15	120.5	C44—C45—C46	119.8 (5)
C11—C16—C15	123.0 (5)	C44—C45—H45	120.1
C11—C16—H16	118.5	C46—C45—H45	120.1
C15—C16—H16	118.5	N41—C46—C45	123.3 (5)
C26—C21—C22	116.8 (5)	N41—C46—H46	118.3
C26—C21—C1	123.6 (5)	C45—C46—H46	118.3
C22—C21—C1	119.5 (5)	C57—C47—C44	125.9 (5)
C23—C22—C21	122.9 (5)	C57—C47—H47	117.0
C23—C22—H22	118.6	C44—C47—H47	117.0
C21—C22—H22	118.6	C56—N51—C52	116.4 (5)
C22—C23—C24	120.0 (5)	N51—C52—C53	123.8 (6)
C22—C23—H23	120.0	N51—C52—H52	118.1
C24—C23—H23	120.0	C53—C52—H52	118.1
O2—C24—C25	118.4 (5)	C54—C53—C52	118.9 (6)
O2—C24—C23	123.1 (5)	C54—C53—H53	120.5
C25—C24—C23	118.5 (4)	C52—C53—H53	120.5
C24—C25—C26	121.3 (5)	C53—C54—C55	118.1 (5)
C24—C25—H25	119.4	C53—C54—C57	122.1 (5)
C26—C25—H25	119.4	C55—C54—C57	119.8 (5)
C21—C26—C25	120.6 (5)	C54—C55—C56	119.7 (6)
C21—C26—H26	119.7	C54—C55—H55	120.2
C25—C26—H26	119.7	C56—C55—H55	120.2
C36—C31—C32	117.3 (5)	N51—C56—C55	123.0 (6)
C36—C31—C1	120.6 (4)	N51—C56—H56	118.5
C32—C31—C1	122.0 (4)	C55—C56—H56	118.5
C31—C32—C33	121.6 (5)	C47—C57—C54	125.8 (5)
C31—C32—H32	119.2	C47—C57—H57	117.1
C33—C32—H32	119.2	C54—C57—H57	117.1
C2—C1—C11—C16	153.9 (5)	C2—C1—C31—C32	−30.6 (7)
C21—C1—C11—C16	−86.1 (6)	C21—C1—C31—C32	−148.1 (5)
C31—C1—C11—C16	32.2 (6)	C11—C1—C31—C32	91.4 (6)
C2—C1—C11—C12	−28.0 (6)	C36—C31—C32—C33	−0.9 (8)
C21—C1—C11—C12	92.0 (6)	C1—C31—C32—C33	−177.7 (5)
C31—C1—C11—C12	−149.6 (5)	C31—C32—C33—C34	0.8 (8)
C16—C11—C12—C13	−1.0 (8)	C32—C33—C34—O3	−178.5 (5)
C1—C11—C12—C13	−179.2 (5)	C32—C33—C34—C35	0.9 (8)
C11—C12—C13—C14	0.7 (8)	O3—C34—C35—C36	177.0 (5)
C12—C13—C14—C15	−0.2 (9)	C33—C34—C35—C36	−2.4 (8)
C12—C13—C14—O1	−179.7 (5)	C32—C31—C36—C35	−0.6 (8)
O1—C14—C15—C16	179.5 (5)	C1—C31—C36—C35	176.2 (5)
C13—C14—C15—C16	−0.1 (8)	C34—C35—C36—C31	2.3 (8)
C12—C11—C16—C15	0.7 (8)	C46—N41—C42—C43	0.1 (9)
C1—C11—C16—C15	179.0 (5)	N41—C42—C43—C44	−1.2 (10)
C14—C15—C16—C11	−0.2 (8)	C42—C43—C44—C45	2.0 (9)
C2—C1—C21—C26	126.1 (5)	C42—C43—C44—C47	−179.4 (6)
C11—C1—C21—C26	4.5 (7)	C43—C44—C45—C46	−1.7 (9)
C31—C1—C21—C26	−114.9 (6)	C47—C44—C45—C46	179.7 (5)
C2—C1—C21—C22	−57.8 (6)	C42—N41—C46—C45	0.2 (9)
C11—C1—C21—C22	−179.4 (5)	C44—C45—C46—N41	0.7 (9)
C31—C1—C21—C22	61.1 (6)	C45—C44—C47—C57	179.7 (6)
C26—C21—C22—C23	0.0 (8)	C43—C44—C47—C57	1.2 (9)
C1—C21—C22—C23	−176.3 (5)	C56—N51—C52—C53	0.2 (11)
C21—C22—C23—C24	−0.3 (9)	N51—C52—C53—C54	0.5 (12)
C22—C23—C24—O2	179.8 (5)	C52—C53—C54—C55	−1.2 (10)
C22—C23—C24—C25	0.3 (8)	C52—C53—C54—C57	178.7 (7)
O2—C24—C25—C26	−179.6 (5)	C53—C54—C55—C56	1.3 (10)
C23—C24—C25—C26	−0.1 (8)	C57—C54—C55—C56	−178.6 (6)
C22—C21—C26—C25	0.2 (8)	C52—N51—C56—C55	−0.1 (10)
C1—C21—C26—C25	176.4 (5)	C54—C55—C56—N51	−0.7 (10)
C24—C25—C26—C21	−0.1 (9)	C44—C47—C57—C54	−178.7 (6)
C2—C1—C31—C36	152.7 (5)	C53—C54—C57—C47	−6.8 (10)
C21—C1—C31—C36	35.2 (7)	C55—C54—C57—C47	173.2 (6)
C11—C1—C31—C36	−85.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.84	2.03	2.652 (6)	131
O2—H2···O3^i	0.84	1.85	2.684 (6)	172
O3—H3···N41	0.84	1.81	2.631 (6)	166
O4—H4···N51^ii	0.84	1.87	2.696 (6)	166

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