(1RS,2SR,3RS,5SR)-2-Benzoyl-4,4-di­cyano-1,3,5-triphenylcyclohexanol at 120 K: complex sheets built from C—H...O and C—H...N hydrogen bonds

At 120 K, the title compound [systematic name: (2RS,3SR,4RS,6SR)-3-benzoyl-4-hydroxy-2,4,6-triphenyl­cyclo­hexane-1,1-dicarbonitrile], C₃₃H₂₆N₂O₂, has unit-cell dimensions apparently different from those reported at 294 K [Rong, Li, Yang, Wang & Shi (2006). Acta Cryst. E62, o1766–o1767]. The mol­ecules are linked by two C—H...O hydrogen bonds and three C—H...N hydrogen bonds into complex sheets, and the hydrogen-bonded structures at the two temperatures are the same, although incorrectly described in the earlier report. The significance of the present study lies in its correct description of the hydrogen bonding and in its analysis of the unit-cell dimensions; the differences between the cell angles at 120 and 294 K arise from the fact that one such angle in the triclinic cell is extremely close to 90° so that a very small change in this angle can induce significant changes in the reduced cell.

S1. Comment

As part of a programme for the synthesis of highly-substituted hydropyridone derivatives as potential bioactive compounds, we have considered the use, as a synthetic intermediate, of the Michael adduct obtained from malononitrile and 1,3-diphenyl-2-propen-1-one (chalcone). However, we have now found that under basic conditions this reaction provides not the expected simple adduct (López et al., 2001) but instead a mixture of compounds (Victory et al., 1991), from which the title compound, (I), was obtained in crystalline form. We report here the molecular and crystal structures of (I) (Fig. 1) at 120 K.

The structure of (I) has been reported using diffraction data collected at 294 K (Rong et al., 2006), but the unit cell reported by these authors [a = 10.996 (2) Å, b = 12.017 (2) Å, c = 12.109 (2) Å, α = 89.950 (4)°, β = 67.150 (3)° and γ = 67.821 (3)°] appears to differ significantly from that found here. While the repeat vectors are very similar, the reduced unit-cell angles at 294 K are all close to the supplementary values of the reduced angles at 120 K, i.e. each reduced angle θ (θ = α, β or γ) at 294 K corresponds closely to (180° - θ) at 120 K, with a maximum difference of ca 0.57° occurring in the angles γ; the corresponding atomic coordinates at the two temperatures are very precisely related by the transformation (1 - x, y, z). Furthermore, the crystal structure was described as a three-dimensional array of C—H···O and C—H···N hydrogen bonds (Rong et al., 2006), whereas at 120 K we find that the hydrogen-bonded structure is two-dimensional. We first describe the structure at 120 K, and we shall return below to both these points concerning the structure reported at 294 K.

The cyclohexane ring in (I) adopts the usual chair conformation, and the benzoyl and the three phenyl substituents all occupy equatorial sites, so that the hydroxy substituent necessarily occupies an axial site. There are four stereogenic centres and the configuration in the selected asymmetric unit is (1R,2S,3R,5S); since the compound crystallizes in a centrosymmetric space group, the overall configuration for the racemic mixture can be described as (1RS,2SR,3RS,5SR). The bond lengths and angles present no unusual features.

There is an intramolecular O—H···O hydrogen bond (Table 1), and the molecules are linked into complex sheets by a combination of three C—H···N hydrogen bonds and two C—H···O hydrogen bonds. The sheet formation is readily analysed in terms of two one-dimensional substructures, one of which utilizes just one hydrogen bond while the other utilizes four hydrogen bonds. In the simpler of the two substructures, atom C24 in the benzoyl group of the molecule at (x, y, z) acts as a hydrogen-bond donor to atom N41 in the equatorial cyano substituent of the molecule at (-1 + x, y, -1 + z); in this way a C(11) (Bernstein et al., 1995) chain is generated by translation along the [101] direction (Fig. 2).

The second and more complex of the one-dimensional substructures is built from two C—H···O and two C—H···N hydrogen bonds. The aryl atoms C32 and C56 in the molecule at (x, y, z) act as donors, respectively, to atoms O1 and O2 both in the molecule at (1 - x, 1 - y, 1 - z). Within the resulting dimeric unit the two hydrogen bonds acting independently generate centrosymmetric R²₂(14) and R²₂(18) rings, respectively, while their combination generates a noncentrosymmetric R²₂(14) motif. In addition, the aryl atoms C12 and C26 in the molecule at (x, y, z) both act as hydrogen-bond donors to the axial cyano atom N42 in the molecule at (1 - x, 2 - y, 1 - z); in combination, these interactions generate an R¹₂(10) motif, while individually, each independently generates a centrosymmetric R²₂(18) ring. The combination of these four hydrogen bonds then generates a complex chain of rings running parallel to the [010] direction, with the centrosymmetric rings built from C—H···O hydrogen bonds and centred at (1/2, 1/2 + n, 1/2) (where n represents zero or an integer) alternating with the corresponding rings built from C—H···N hydrogen bonds and centred at (1/2, n, 1/2) (where n represents zero or an integer) (Fig. 3). The combination of the chains along [010] and [101] generates a complex sheet lying parallel to (101) (Fig. 4). The only direction-specific interaction linking the adjacent sheets is a single C—H···π(arene) interaction (Table 1).

As expected the repeat vectors reported at 294 K (Rong et al., 2006) are greater than those found here at 120 K, with the maximum difference of 0.240 (3) Å (ca 2%) occurring in the vector b. Similarly, for the unit-cell angles the magnitudes of the differences between θ at 294 K and (180° - θ) at 120 K range from 0.234 (9)° in β to 0.57 (2)° in γ. However, at both temperatures the cell angle α is very close to 90°, and the angle reported at 294 K is 89.950 (4)°. If this value is artificially set to be 90.050 (4)°, then the resulting reduced cell has values of β and γ corresponding almost exactly to those found at 120 K. Hence the apparently substantial differences between the unit-cell dimensions at 120 and 294 K are most plausibly explained as a consequence of a small change in the angle α from one side of 90° to the other, resulting in a change in the reduced cell angles and a concomitant change in the atom coordinates. It has been suggested, although without formal proof (Andrews et al., 1980), that the combination of reduced cell lengths in real and reciprocal spaces together with the reduced cell volume provides a unique description of a crystal lattice. Accordingly, the use of this set of parameters enables comparison of lattices or of unit cells without reference to the cell angles. This proposal was developed specifically in response to the large and discontinuous jumps in the unit-cell angles which can occur when there are only very small changes in the overall lattice, exactly as in the example described here.

The overall hydrogen-bonded structures are the same at the two temperatures. Although Rong et al. (2006) described their hydrogen-bonded structure as three-dimensional, an analysis based on the hydrogen bonds found at 294 K shows clearly that the structure is two-dimensional, exactly as at 120 K (Fig. 5). The packing diagram presented in the earlier report (Rong et al., 2006) in fact shows a centrosymmetric aggregate of four molecules, those at (x, y, z), (-1 + x, y, 1 + z), (1 - x, 1 - y, 1 - z) and (2 - x, 1 - y, -z), which does not illustrate a repeating unit even in one dimension, far less the three-dimensional network postulated.

An interesting comparison can be made with the 3,5-bis(4-methylphenyl) analogue (II) [Cambridge Structural Database (CSD; Allen, 2002) refcode JEVYEO (Al-Arab, 1990)], which also crystallizes in space group P1. The unit-cell angles for (II) are rather similar to those reported for (I) at 294 K, except that now it is the cell angle γ = 89.46 (2)° which is very close to 90°, while the atomic coordinates can be related to those reported here for corresponding atoms by the transformation (1/2 - z, y, x). The a and b unit-cell vectors reported for (II) at 130 K are almost identical to the values of b and c, respectively, found here for (I) at 120 K, but there has been a reordering of the repeat vectors, thus (cab). This, and the interchange of the x and z coordinates, results from the slight `stretching' of the crystal structure, predominantly in one direction, which is a consequence of the introduction of methyl groups into two of the aryl rings. As a result of this stretching of the structure of (II) as compared with that of (I), only two of the intermolecular contacts found in (I) are still within effective hydrogen-bonding distances in (II), one each of the C—H···O and C—H···N types. These form, respectively, a centrosymmetric R²₂(14) ring and a C(11) chain generated by translation, exactly analogous to the corresponding motifs in (I). In combination, these two hydrogen bonds link the molecules of (II) into a chain of alternating centrosymmetric R²₂(14) and R⁴₄(36) rings (Fig. 6).

In the more heavily-substituted analogue (III) [CSD refcode PEHYUW (Al-Arab et al., 1992)], which crystallizes in P1 as a stoichiometric acetic acid solvate, with the cyano group occupying an axial site, the molecules of the cyclohexanol component are linked by paired C—H···N hydrogen bonds into a centrosymmetric R²₂(14) dimer (Fig. 7), while the acetic acid component independently forms the usual R²₂(8) dimer. The structure of the trifluoromethyl derivative (IV) has been reported [CSD code NAVZAL (Sanin et al., 1997)], but no H-atom coordinates are deposited in the CSD, so that useful discussion of the intermolecular aggregation is not possible.

Related literature

For related literature, see: Al-Arab (1990); Al-Arab, Ghanem & Olmstead (1992); Allen (2002); Andrews et al. (1980); Bernstein et al. (1995); López et al. (2001); Rong et al. (2006).

S2. Experimental

Sodium methoxide (1.44 mmol) was added to a mixture of malononitrile (1.44 mmol) and 1,3-diphenyl-2-propen-1-one (chalcone, 1.44 mmol) dissolved in methanol (20 ml), and the reaction mixture was then stirred at ambient temperature for 6 h. The mixture was neutralized with 10% aqueous acetic acid solution and then evaporated to dryness under reduced pressure. The resulting solid product was recrystallized from aqueous methanol to give the title compound, (I), in 38% yield as colourless crystals suitable for single-crystal X-ray diffraction.

S3. Refinement

Crystals of (I) are triclinic; the space group P1 was selected and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms with C—H distances of 0.95 (aromatic), 0.99 (CH₂) or 1.00 Å (aliphatic C—H) and O—H distances of 0.84 Å, and with U_iso(H) equal to 1.2U_eq(C) or 1.5U_eq(O).

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The (1R,2S,3R,5S) isomer of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(11) chain along [101]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain of rings along [010]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet parallel to (101). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of (I) at 294 K, using the atomic coordinates of Rong et al. (2006), showing the formation of a hydrogen-bonded sheet parallel to (101). Note the different orientation of the unit cell in comparison with that in Fig. 4. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded chain of alternating R^22(14) and R^44(36) rings. The original atom coordinates (Al-Arab, 1990) have been used and, for the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded dimer containing an R^22(14) ring. The original atom coordinates (Al-Arab et al., 1992) have been used and, for the sake of clarity, H atoms not involved in the motif shown have been omitted, along with the solvent molecules.

(2RS,3SR,4RS,6SR)-3-Benzoyl-4-hydroxy-2,4,6-triphenylcyclohexane-1,1- dicarbonitrile

Crystal data

C33H26N2O2	Z = 2
Mr = 482.56	F(000) = 508
Triclinic, P1	Dx = 1.246 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.9251 (18) Å	Cell parameters from 5800 reflections
b = 11.777 (3) Å	θ = 6.5–27.5°
c = 11.9438 (12) Å	µ = 0.08 mm^−1
α = 90.417 (13)°	T = 120 K
β = 112.616 (9)°	Block, colourless
γ = 112.750 (14)°	0.59 × 0.47 × 0.35 mm
V = 1286.1 (5) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	5800 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 6.5°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→15
Tmin = 0.946, Tmax = 0.973	l = −15→14
33243 measured 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.7168P] where P = (Fo^2 + 2Fc^2)/3
5800 reflections	(Δ/σ)max = 0.001
334 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.53960 (15)	0.58734 (12)	0.35717 (12)	0.0251 (3)
O2	0.25019 (15)	0.48131 (13)	0.30028 (13)	0.0309 (4)
N41	0.6343 (2)	0.69770 (19)	0.81250 (18)	0.0376 (5)
N42	0.5983 (2)	0.99903 (17)	0.63209 (17)	0.0322 (4)
C1	0.5207 (2)	0.69971 (17)	0.34195 (17)	0.0210 (4)
C2	0.3978 (2)	0.69596 (17)	0.37755 (17)	0.0201 (4)
C3	0.4313 (2)	0.67677 (17)	0.51117 (17)	0.0206 (4)
C4	0.5857 (2)	0.77537 (17)	0.60374 (17)	0.0199 (4)
C5	0.7070 (2)	0.78034 (18)	0.56326 (17)	0.0217 (4)
C6	0.6651 (2)	0.80289 (18)	0.43170 (17)	0.0232 (4)
C11	0.4932 (2)	0.72289 (18)	0.21140 (18)	0.0237 (4)
C12	0.4560 (2)	0.8192 (2)	0.17013 (19)	0.0290 (5)
C13	0.4355 (2)	0.8418 (2)	0.0523 (2)	0.0339 (5)
C14	0.4551 (2)	0.7698 (2)	−0.0248 (2)	0.0364 (6)
C15	0.4956 (2)	0.6761 (2)	0.0163 (2)	0.0348 (5)
C16	0.5140 (2)	0.65207 (19)	0.13308 (19)	0.0280 (5)
C21	0.1251 (2)	0.60207 (19)	0.21120 (18)	0.0247 (4)
C22	−0.0006 (2)	0.4945 (2)	0.14290 (18)	0.0299 (5)
C23	−0.1243 (2)	0.5023 (2)	0.0614 (2)	0.0365 (5)
C24	−0.1258 (2)	0.6167 (2)	0.0457 (2)	0.0395 (6)
C25	−0.0020 (3)	0.7243 (2)	0.1116 (2)	0.0394 (6)
C26	0.1225 (2)	0.7172 (2)	0.19504 (19)	0.0318 (5)
C27	0.2542 (2)	0.58626 (18)	0.29525 (17)	0.0228 (4)
C31	0.3125 (2)	0.67000 (18)	0.55012 (17)	0.0218 (4)
C32	0.2588 (2)	0.57233 (19)	0.60622 (18)	0.0260 (5)
C33	0.1529 (2)	0.5644 (2)	0.6448 (2)	0.0333 (5)
C34	0.0992 (2)	0.6538 (2)	0.6283 (2)	0.0341 (5)
C35	0.1514 (2)	0.7506 (2)	0.5723 (2)	0.0335 (5)
C36	0.2571 (2)	0.75928 (19)	0.53292 (19)	0.0282 (5)
C41	0.6150 (2)	0.73616 (19)	0.72437 (19)	0.0249 (4)
C42	0.5907 (2)	0.90076 (19)	0.61915 (17)	0.0228 (4)
C51	0.8587 (2)	0.87208 (18)	0.65243 (18)	0.0240 (4)
C52	0.9193 (2)	0.9951 (2)	0.6380 (2)	0.0308 (5)
C53	1.0587 (2)	1.0758 (2)	0.7199 (2)	0.0389 (6)
C54	1.1391 (3)	1.0350 (2)	0.8156 (2)	0.0447 (6)
C55	1.0802 (3)	0.9137 (2)	0.8309 (2)	0.0460 (6)
C56	0.9408 (2)	0.8325 (2)	0.7494 (2)	0.0339 (5)
H1	0.4543	0.5300	0.3257	0.038*
H2	0.3865	0.7761	0.3675	0.024*
H3	0.4349	0.5933	0.5149	0.025*
H5	0.7066	0.6953	0.5624	0.026*
H6A	0.7431	0.8084	0.4062	0.028*
H6B	0.6576	0.8840	0.4280	0.028*
H12	0.4442	0.8705	0.2233	0.035*
H13	0.4079	0.9072	0.0245	0.041*
H14	0.4405	0.7851	−0.1059	0.044*
H15	0.5112	0.6274	−0.0361	0.042*
H16	0.5411	0.5862	0.1602	0.034*
H22	−0.0004	0.4146	0.1530	0.036*
H23	−0.2095	0.4280	0.0156	0.044*
H24	−0.2120	0.6220	−0.0106	0.047*
H25	−0.0025	0.8038	0.0994	0.047*
H26	0.2068	0.7918	0.2416	0.038*
H32	0.2955	0.5101	0.6183	0.031*
H33	0.1166	0.4967	0.6830	0.040*
H34	0.0265	0.6485	0.6555	0.041*
H35	0.1142	0.8125	0.5604	0.040*
H36	0.2922	0.8267	0.4939	0.034*
H52	0.8647	1.0240	0.5714	0.037*
H53	1.0992	1.1603	0.7098	0.047*
H54	1.2355	1.0907	0.8713	0.054*
H55	1.1355	0.8854	0.8977	0.055*
H56	0.9009	0.7483	0.7603	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0256 (7)	0.0213 (7)	0.0276 (7)	0.0112 (6)	0.0091 (6)	0.0020 (6)
O2	0.0267 (8)	0.0207 (8)	0.0360 (8)	0.0065 (6)	0.0076 (7)	0.0013 (6)
N41	0.0372 (11)	0.0511 (13)	0.0336 (11)	0.0247 (10)	0.0175 (9)	0.0174 (10)
N42	0.0334 (11)	0.0255 (10)	0.0350 (10)	0.0120 (8)	0.0124 (8)	0.0010 (8)
C1	0.0231 (10)	0.0204 (10)	0.0208 (10)	0.0100 (8)	0.0097 (8)	0.0019 (8)
C2	0.0205 (10)	0.0188 (10)	0.0201 (10)	0.0081 (8)	0.0079 (8)	0.0026 (8)
C3	0.0207 (10)	0.0172 (10)	0.0222 (10)	0.0069 (8)	0.0084 (8)	0.0033 (8)
C4	0.0204 (10)	0.0200 (10)	0.0183 (10)	0.0084 (8)	0.0071 (8)	0.0043 (8)
C5	0.0193 (10)	0.0204 (10)	0.0230 (10)	0.0073 (8)	0.0076 (8)	0.0023 (8)
C6	0.0216 (10)	0.0218 (10)	0.0249 (10)	0.0069 (8)	0.0108 (9)	0.0027 (8)
C11	0.0183 (10)	0.0249 (11)	0.0225 (10)	0.0045 (8)	0.0080 (8)	0.0015 (8)
C12	0.0286 (12)	0.0313 (12)	0.0275 (11)	0.0116 (10)	0.0132 (9)	0.0068 (9)
C13	0.0274 (12)	0.0395 (13)	0.0315 (12)	0.0107 (10)	0.0124 (10)	0.0148 (10)
C14	0.0300 (12)	0.0447 (14)	0.0226 (11)	0.0042 (11)	0.0109 (10)	0.0054 (10)
C15	0.0316 (12)	0.0358 (13)	0.0275 (12)	0.0021 (10)	0.0155 (10)	−0.0055 (10)
C16	0.0249 (11)	0.0250 (11)	0.0289 (11)	0.0047 (9)	0.0121 (9)	−0.0004 (9)
C21	0.0218 (10)	0.0291 (11)	0.0228 (10)	0.0087 (9)	0.0108 (9)	0.0034 (9)
C22	0.0255 (11)	0.0360 (12)	0.0221 (11)	0.0075 (10)	0.0097 (9)	0.0055 (9)
C23	0.0245 (12)	0.0489 (15)	0.0272 (12)	0.0099 (11)	0.0076 (10)	0.0050 (10)
C24	0.0257 (12)	0.0654 (17)	0.0259 (12)	0.0227 (12)	0.0062 (10)	0.0075 (11)
C25	0.0404 (14)	0.0478 (15)	0.0362 (13)	0.0281 (12)	0.0127 (11)	0.0119 (11)
C26	0.0301 (12)	0.0324 (12)	0.0288 (12)	0.0139 (10)	0.0076 (10)	0.0015 (9)
C27	0.0250 (11)	0.0220 (11)	0.0224 (10)	0.0083 (9)	0.0124 (9)	0.0044 (8)
C31	0.0197 (10)	0.0229 (10)	0.0204 (10)	0.0080 (8)	0.0070 (8)	0.0017 (8)
C32	0.0251 (11)	0.0261 (11)	0.0274 (11)	0.0114 (9)	0.0111 (9)	0.0043 (9)
C33	0.0353 (13)	0.0339 (13)	0.0362 (13)	0.0131 (10)	0.0220 (11)	0.0112 (10)
C34	0.0319 (12)	0.0432 (14)	0.0389 (13)	0.0183 (11)	0.0238 (11)	0.0098 (11)
C35	0.0338 (12)	0.0383 (13)	0.0398 (13)	0.0221 (11)	0.0198 (11)	0.0111 (10)
C36	0.0299 (12)	0.0278 (11)	0.0312 (11)	0.0134 (9)	0.0157 (10)	0.0087 (9)
C41	0.0210 (10)	0.0268 (11)	0.0279 (12)	0.0108 (9)	0.0106 (9)	0.0035 (9)
C42	0.0188 (10)	0.0258 (11)	0.0204 (10)	0.0079 (9)	0.0066 (8)	0.0006 (8)
C51	0.0199 (10)	0.0235 (11)	0.0271 (11)	0.0078 (8)	0.0099 (9)	−0.0008 (8)
C52	0.0257 (11)	0.0294 (12)	0.0327 (12)	0.0067 (9)	0.0128 (10)	0.0028 (9)
C53	0.0295 (12)	0.0316 (13)	0.0462 (14)	0.0014 (10)	0.0186 (11)	−0.0021 (11)
C54	0.0227 (12)	0.0382 (14)	0.0518 (16)	0.0015 (11)	0.0063 (11)	−0.0111 (12)
C55	0.0270 (13)	0.0466 (15)	0.0470 (15)	0.0141 (11)	−0.0001 (11)	−0.0013 (12)
C56	0.0239 (11)	0.0289 (12)	0.0380 (13)	0.0096 (10)	0.0041 (10)	−0.0013 (10)

Geometric parameters (Å, º)

O1—C1	1.419 (2)	C21—C22	1.390 (3)
O1—H1	0.8402	C21—C27	1.466 (3)
O2—C27	1.222 (2)	C22—C23	1.367 (3)
N41—C41	1.126 (3)	C22—H22	0.95
N42—C42	1.132 (2)	C23—C24	1.367 (3)
C1—C11	1.518 (3)	C23—H23	0.95
C1—C6	1.521 (3)	C24—C25	1.376 (3)
C1—C2	1.542 (3)	C24—H24	0.95
C2—C27	1.525 (3)	C25—C26	1.378 (3)
C2—C3	1.534 (3)	C25—H25	0.95
C2—H2	1.00	C26—H26	0.95
C3—C31	1.514 (3)	C31—C32	1.381 (3)
C3—C4	1.565 (3)	C31—C36	1.383 (3)
C3—H3	1.00	C32—C33	1.374 (3)
C4—C42	1.464 (3)	C32—H32	0.95
C4—C41	1.470 (3)	C33—C34	1.371 (3)
C4—C5	1.558 (3)	C33—H33	0.95
C5—C51	1.513 (3)	C34—C35	1.370 (3)
C5—C6	1.515 (3)	C34—H34	0.95
C5—H5	1.00	C35—C36	1.376 (3)
C6—H6A	0.99	C35—H35	0.95
C6—H6B	0.99	C36—H36	0.95
C11—C12	1.380 (3)	C51—C56	1.377 (3)
C11—C16	1.385 (3)	C51—C52	1.384 (3)
C12—C13	1.382 (3)	C52—C53	1.379 (3)
C12—H12	0.95	C52—H52	0.95
C13—C14	1.375 (3)	C53—C54	1.368 (3)
C13—H13	0.95	C53—H53	0.95
C14—C15	1.369 (3)	C54—C55	1.368 (4)
C14—H14	0.95	C54—H54	0.95
C15—C16	1.379 (3)	C55—C56	1.379 (3)
C15—H15	0.95	C55—H55	0.95
C16—H16	0.95	C56—H56	0.95
C21—C26	1.380 (3)
C1—O1—H1	104.7	C22—C21—C27	117.67 (19)
O1—C1—C11	110.44 (15)	C23—C22—C21	120.8 (2)
O1—C1—C6	105.13 (15)	C23—C22—H22	119.6
C11—C1—C6	109.13 (16)	C21—C22—H22	119.6
O1—C1—C2	110.36 (15)	C24—C23—C22	120.1 (2)
C11—C1—C2	112.43 (16)	C24—C23—H23	119.9
C6—C1—C2	109.08 (15)	C22—C23—H23	119.9
C27—C2—C3	107.17 (15)	C23—C24—C25	119.9 (2)
C27—C2—C1	109.90 (15)	C23—C24—H24	120.0
C3—C2—C1	111.12 (15)	C25—C24—H24	120.0
C27—C2—H2	109.5	C24—C25—C26	120.3 (2)
C3—C2—H2	109.5	C24—C25—H25	119.9
C1—C2—H2	109.5	C26—C25—H25	119.9
C31—C3—C2	113.25 (16)	C25—C26—C21	120.2 (2)
C31—C3—C4	111.96 (15)	C25—C26—H26	119.9
C2—C3—C4	112.02 (15)	C21—C26—H26	119.9
C31—C3—H3	106.3	O2—C27—C21	119.88 (18)
C2—C3—H3	106.3	O2—C27—C2	117.02 (17)
C4—C3—H3	106.3	C21—C27—C2	123.09 (17)
C42—C4—C41	107.31 (16)	C32—C31—C36	118.81 (18)
C42—C4—C5	109.65 (16)	C32—C31—C3	118.96 (17)
C41—C4—C5	109.01 (15)	C36—C31—C3	122.23 (18)
C42—C4—C3	112.23 (15)	C33—C32—C31	120.5 (2)
C41—C4—C3	107.08 (16)	C33—C32—H32	119.7
C5—C4—C3	111.40 (15)	C31—C32—H32	119.7
C51—C5—C6	113.80 (16)	C34—C33—C32	120.4 (2)
C51—C5—C4	113.03 (16)	C34—C33—H33	119.8
C6—C5—C4	108.78 (15)	C32—C33—H33	119.8
C51—C5—H5	106.9	C35—C34—C33	119.4 (2)
C6—C5—H5	106.9	C35—C34—H34	120.3
C4—C5—H5	106.9	C33—C34—H34	120.3
C5—C6—C1	112.37 (16)	C34—C35—C36	120.7 (2)
C5—C6—H6A	109.1	C34—C35—H35	119.7
C1—C6—H6A	109.1	C36—C35—H35	119.7
C5—C6—H6B	109.1	C35—C36—C31	120.1 (2)
C1—C6—H6B	109.1	C35—C36—H36	119.9
H6A—C6—H6B	107.9	C31—C36—H36	119.9
C12—C11—C16	118.28 (19)	N41—C41—C4	175.0 (2)
C12—C11—C1	121.26 (18)	N42—C42—C4	178.2 (2)
C16—C11—C1	120.34 (18)	C56—C51—C52	118.57 (19)
C11—C12—C13	120.8 (2)	C56—C51—C5	119.62 (18)
C11—C12—H12	119.6	C52—C51—C5	121.80 (18)
C13—C12—H12	119.6	C53—C52—C51	120.3 (2)
C14—C13—C12	120.2 (2)	C53—C52—H52	119.8
C14—C13—H13	119.9	C51—C52—H52	119.8
C12—C13—H13	119.9	C54—C53—C52	120.4 (2)
C15—C14—C13	119.5 (2)	C54—C53—H53	119.8
C15—C14—H14	120.3	C52—C53—H53	119.8
C13—C14—H14	120.3	C53—C54—C55	119.8 (2)
C14—C15—C16	120.5 (2)	C53—C54—H54	120.1
C14—C15—H15	119.8	C55—C54—H54	120.1
C16—C15—H15	119.8	C54—C55—C56	120.1 (2)
C15—C16—C11	120.7 (2)	C54—C55—H55	119.9
C15—C16—H16	119.6	C56—C55—H55	119.9
C11—C16—H16	119.6	C51—C56—C55	120.8 (2)
C26—C21—C22	118.63 (19)	C51—C56—H56	119.6
C26—C21—C27	123.69 (18)	C55—C56—H56	119.6
O1—C1—C2—C27	−60.36 (19)	C26—C21—C22—C23	0.0 (3)
C11—C1—C2—C27	63.4 (2)	C27—C21—C22—C23	−179.02 (19)
C6—C1—C2—C27	−175.38 (15)	C21—C22—C23—C24	0.3 (3)
O1—C1—C2—C3	58.09 (19)	C22—C23—C24—C25	0.4 (3)
C11—C1—C2—C3	−178.12 (15)	C23—C24—C25—C26	−1.2 (3)
C6—C1—C2—C3	−56.9 (2)	C24—C25—C26—C21	1.5 (3)
C27—C2—C3—C31	−58.9 (2)	C22—C21—C26—C25	−0.8 (3)
C1—C2—C3—C31	−178.94 (15)	C27—C21—C26—C25	178.1 (2)
C27—C2—C3—C4	173.34 (15)	C26—C21—C27—O2	−176.55 (19)
C1—C2—C3—C4	53.3 (2)	C22—C21—C27—O2	2.4 (3)
C31—C3—C4—C42	−57.2 (2)	C26—C21—C27—C2	2.5 (3)
C2—C3—C4—C42	71.3 (2)	C22—C21—C27—C2	−178.59 (18)
C31—C3—C4—C41	60.3 (2)	C3—C2—C27—O2	−59.3 (2)
C2—C3—C4—C41	−171.22 (16)	C1—C2—C27—O2	61.5 (2)
C31—C3—C4—C5	179.41 (15)	C3—C2—C27—C21	121.62 (19)
C2—C3—C4—C5	−52.1 (2)	C1—C2—C27—C21	−117.52 (19)
C42—C4—C5—C51	56.8 (2)	C2—C3—C31—C32	130.31 (19)
C41—C4—C5—C51	−60.4 (2)	C4—C3—C31—C32	−101.9 (2)
C3—C4—C5—C51	−178.38 (16)	C2—C3—C31—C36	−50.6 (2)
C42—C4—C5—C6	−70.64 (19)	C4—C3—C31—C36	77.3 (2)
C41—C4—C5—C6	172.16 (16)	C36—C31—C32—C33	−0.3 (3)
C3—C4—C5—C6	54.2 (2)	C3—C31—C32—C33	178.84 (18)
C51—C5—C6—C1	172.70 (16)	C31—C32—C33—C34	−0.2 (3)
C4—C5—C6—C1	−60.3 (2)	C32—C33—C34—C35	0.5 (3)
O1—C1—C6—C5	−56.50 (19)	C33—C34—C35—C36	−0.2 (3)
C11—C1—C6—C5	−174.97 (16)	C34—C35—C36—C31	−0.3 (3)
C2—C1—C6—C5	61.9 (2)	C32—C31—C36—C35	0.5 (3)
O1—C1—C11—C12	172.97 (17)	C3—C31—C36—C35	−178.59 (19)
C6—C1—C11—C12	−71.9 (2)	C6—C5—C51—C56	−145.95 (19)
C2—C1—C11—C12	49.2 (2)	C4—C5—C51—C56	89.3 (2)
O1—C1—C11—C16	−11.0 (2)	C6—C5—C51—C52	32.7 (3)
C6—C1—C11—C16	104.1 (2)	C4—C5—C51—C52	−92.1 (2)
C2—C1—C11—C16	−134.75 (18)	C56—C51—C52—C53	−0.4 (3)
C16—C11—C12—C13	1.9 (3)	C5—C51—C52—C53	−179.03 (19)
C1—C11—C12—C13	178.05 (19)	C51—C52—C53—C54	0.6 (3)
C11—C12—C13—C14	−1.3 (3)	C52—C53—C54—C55	−0.7 (4)
C12—C13—C14—C15	−0.3 (3)	C53—C54—C55—C56	0.6 (4)
C13—C14—C15—C16	1.3 (3)	C52—C51—C56—C55	0.3 (3)
C14—C15—C16—C11	−0.7 (3)	C5—C51—C56—C55	179.0 (2)
C12—C11—C16—C15	−1.0 (3)	C54—C55—C56—C51	−0.4 (4)
C1—C11—C16—C15	−177.10 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84	1.97	2.702 (2)	145
C12—H12···N42^i	0.95	2.59	3.536 (3)	177
C24—H24···N41^ii	0.95	2.56	3.449 (3)	157
C26—H26···N42^i	0.95	2.51	3.451 (3)	171
C32—H32···O1^iii	0.95	2.42	3.325 (3)	159
C56—H56···O2^iii	0.95	2.48	3.379 (3)	157
C54—H54···Cg^iv	0.95	2.85	3.690 (3)	148

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