Asymmetric rotations and dimerization driven by normal to modulated phase transition in 4-bi­phenylcarb­oxy coupled L-phenylalaninate

Amongst the derivatives of 4-biphenylcarboxylic acid and amino acid esters, the crystal structure of 4-biphenylcarboxy-(L)-phenylalaninate is unusual owing to its monoclinic symmetry within a pseudo-orthorhombic crystal system. The distortion is described by a disparate rotational property around the chiral centers (φ_chiral ≃ −129° and 58°) of the two molecules in the asymmetric unit. Each of these molecules comprises planar biphenyl moieties (φ_biphenyl = 0°). Using temperature-dependent single-crystal X-ray diffraction experiments we show that the compound undergoes a phase transition below T ∼ 124 K that is characterized by a commensurate modulation wavevector, q = δ(101), δ = ½. The (3+1)-dimensional modulated structure at T = 100 K suggests that the phase transition drives the biphenyl moieties towards noncoplanar conformations with significant variation of internal torsion angle (φ^max_biphenyl ≤ 20°). These intramolecular rotations lead to dimerization of the molecular stacks that are described predominantly by distortions in intermolecular tilts (θ_max ≤ 20°) and small variations in intermolecular distances (Δd_max ≃ 0.05 Å) between biphenyl molecules. Atypical of modulated structures and superstructures of biphenyl and other polyphenyls, the rotations of individual molecules are asymmetric (Δφ_biphenyl ≈ 5°) while φ_biphenyl of one independent molecule is two to four times larger than the other. Crystal-chemical analysis and phase relations in superspace suggest multiple competing factors involving intramolecular steric factors, intermolecular H—C⋯C—H contacts and weak C—H⋯O hydrogen bonds that govern the distinctively unequal torsional properties of the molecules.

1. Introduction

Molecular biphenyl has been investigated extensively for its stability and conformation in different thermodynamic states. At ambient conditions, the differences in the conjugation states of the π electrons are governed primarily by the twist about the central C—C single bond in the order 40°–45° in gas phase, 20°–25° in solution and 0° (mutually coplanar) in solid state in centrosymmetric monoclinic space group P2₁/a (Bastiansen, 1949; Suzuki, 1959; Trotter, 1961; Hargreaves & Rizvi, 1962).

The planar conformation due to constraints from intermolecular interactions is energetically unfavorable and steric hindrance between the ortho hydrogen atoms is compensated for by out-of-plane dynamic disorder and in-plane displacements of those hydrogen atoms away from each other (Hargreaves & Rizvi, 1962; Casalone et al., 1968; Charbonneau & Delugeard, 1976; Charbonneau & Delugeard, 1977; Busing, 1983; Lenstra et al., 1994). A recent study has also suggested the role of intramolecular exchange energy between single-bonded carbon atoms in stabilizing the planar conformation (Popelier et al., 2019).

Absorption and fluorescence studies showed additional bands in their spectra at low temperatures (Hochstrasser et al., 1973; Wakayama, 1981).

Temperature-dependent Raman spectroscopy and Brillouin scattering experiments both suggested two phase transitions at T_c1 = 42 K and T_c2 = 17 K (Friedman et al., 1974; Bree & Edelson, 1977, 1978; Ecolivet et al., 1983). The phase transition at T_c1 is continuous and governed by a soft mode associated with the torsion about the central C—C single bond followed by discontinuous changes at T_c2.

Inelastic neutron scattering experiments on its deuterated form confirmed the phase transitions with the appearance of additional satellite reflections (Cailleau et al., 1979). The modulation wavevector q was determined to be q_I = and q_II = at the intermediate- and low-temperature phases, respectively. The wavevectors were found to vary with temperature, suggesting the incommensurate nature of the modulation (Cailleau et al., 1979).

The modulated structure of low-temperature phase II was described within a noncentrosymmetric superspace group Pa(0σ₂0)0 (de Wolff, 1974; Stokes et al., 2011; van Smaalen et al., 2013) and found to be essentially associated with a small modulation of translation and a rotation (ω) normal to the mean molecular plane, and a significant torsion angle (φ) between the phenyl rings (Baudour & Sanquer, 1983; Petricek et al., 1985; Pinheiro & Abakumov, 2015; Schoenleber, 2011).

Theoretical studies have suggested that competition between intramolecular and intermolecular forces drives the phase transition towards the incommensurately modulated states (Ishibashi, 1981; Benkert et al., 1987; Benkert & Heine, 1987; Parlinski et al., 1989).

The fundamental property of flexibility in conformations has made biphenyl an excellent candidate to tune multifaceted properties in materials.

Twisting between the rings has been demonstrated to regulate conductivity of single molecule biphenyl–dithiol junctions (Vonlanthen et al., 2009; Mishchenko et al., 2010; Bürkle et al., 2012; Jeong et al., 2020), tune thermopower as a function of the twist angle (Bürkle et al., 2012), degeneracy of energy states on substrates (Cranney et al., 2007) and theoretically suggest wide band gap semiconducting properties of its derivatives (Khatua et al., 2020). On the other hand, biphenyl derivatives have also been reported to influence and increase the efficiency of photophysical properties (Oniwa et al., 2013; Wei et al., 2016).

Planar biphenyl molecules in the solid state favor maximum intramolecular conjugation of π electrons as well as increasing the probability of interactions between delocalized electrons that could aid in optimal stacking of molecules.

A coupling reaction mechanism (Seechurn et al., 2012) was successfully employed to synthesize 4-biphenylcarboxy protected amino acid esters of L-serine, L-tyrosine, L-alanine, L-leucine and L-phenylalanine via the formation of peptide-type linker O=C—NH groups (Sasmal et al., 2019b,a).

In the solid state, the compounds crystallize either in noncentrosymmetric space group P2₁2₁2₁ or the monoclinic subgroup P2₁ (Sasmal et al., 2019b,a). Crystal packing in these systems is determined by π⋯π stacking between the biphenyl fragments and strong linear hydrogen bonds between the amino acid ester moieties.

We presumed that the biphenyl moieties in these chemically coupled systems could influence the bioactive amino acid esters and vice versa with respect to evolution or suppression of translational and rotational degrees of freedom in their crystal structures at some thermodynamic condition.

Reanalyzing all their crystal structures, the system of 4-biphenylcarboxy-(L)-phenylalaninate attracted our attention because the structure appeared to be similar to the L-tyrosine analog albeit the monoclinic distortion [Table 1, Sasmal et al. (2019a)] and two crystallographically-independent formula units [Z′ = 2 (Steed & Steed, 2015), Fig. 1(a)] in the crystal structure of the former.

Table 1
Temperature dependence of unit-cell parameters and the components of the modulation wavevector, σ₁ and σ₃

See Table S1 in supporting information for reflections used.

T (K)	a (Å)	b (Å)	c (Å)	β (°)	σ1	σ3	V (Å^3)
200†	5.0560 (3)	8.6622 (4)	42.242 (3)	90.349 (4)			1850.00 (18)
160	5.0479 (2)	8.6330 (4)	42.1525 (15)	90.513 (3)			1836.87 (13)
150	5.0498 (7)	8.6161 (8)	42.136 (11)	90.607 (11)			1833.2 (5)
140	5.0484 (6)	8.6093 (7)	42.145 (10)	90.661 (10)			1831.6 (5)
130	5.0451 (7)	8.6014 (8)	42.120 (11)	90.713 (11)			1827.6 (6)
128	5.0446 (7)	8.6002 (8)	42.113 (11)	90.723 (11)			1826.9 (6)
126	5.0440 (6)	8.5992 (7)	42.114 (10)	90.720 (9)			1826.5 (5)
124	5.0443 (6)	8.5978 (7)	42.100 (10)	90.733 (9)	0.499 (9)	0.51 (7)	1825.7 (5)
122	5.0440 (7)	8.5970 (7)	42.100 (10)	90.745 (10)	0.498 (6)	0.49 (4)	1825.5 (5)
120	5.0433 (7)	8.5984 (7)	42.100 (10)	90.746 (10)	0.497 (5)	0.52 (3)	1825.5 (5)
118	5.0441 (7)	8.5958 (8)	42.092 (11)	90.764 (10)	0.500 (4)	0.50 (3)	1824.8 (5)
116	5.0432 (6)	8.5926 (7)	42.087 (9)	90.775 (9)	0.500 (4)	0.51 (3)	1823.6 (5)
114	5.0422 (6)	8.5923 (7)	42.090 (10)	90.787 (10)	0.500 (4)	0.53 (3)	1823.3 (5)
100	5.0377 (2)	8.5898 (3)	42.0432 (14)	90.884 (3)	0.5	0.5	1819.11 (11)

†Sasmal et al. (2019a).

Figure 1 (a) Two independent formula units of 4-biphenylcarboxy-(L)-phenylalaninate (C23H21NO3) with atomic labels of non-hydrogen atoms (a and b for molecule A and B, respectively) in phase I at T = 160 K. = −130.1°, = 56.1°; = 32.8°, = 30.8°; = = 0°; ψA = 36.4°, ψB = 36.2°. Viewing direction along . (b) Crystal packing in phase I viewed along [111] emphasizing biphenyl stacks (AA)n and (BB)n along a (horizontal arrows), (ABAB)n along b (zigzag vertical arrows) and intermolecular N—H⋯O bonds between amide groups (dashed orange) along [∓100] directions. Phenyl rings of the ester groups (transparent) are stacked only along a.

The torsion angle about the chiral center is significantly different for the independent molecules while the remainder of the rotations are similar [Fig. 1(a), (Sasmal et al., 2019a)].

Each of these molecules consists of coplanar biphenyl moieties which are stacked along a and b, while the amide groups are connected by intermolecular N—H⋯O hydrogen bonds [Fig. 1(b), Sasmal et al. (2019a)].

In the present study, the temperature-dependent phase transition of 4-biphenylcarboxy-(L)-phenylalaninate has been investigated using single-crystal X-ray diffraction experiments. Low-temperature phase II is found to be a 2a × b × 2c superstructure of the high-temperature (phase I) structure.

The superstructure is described within the (3 + 1)D-superspace approach as a commensurately modulated structure (de Wolff, 1974; Janner & Janssen, 1977; Wagner & Schönleber, 2009; van Smaalen, 2012; Janssen et al., 2018).

Structural properties of phase I and the modulated structure have been tabulated and compiled within t-plots (t = phase of the modulation). The origin and stability of phase II is discussed in terms of intramolecular steric factors and intermolecular HC⋯CH contacts and intermolecular hydrogen bonds. It is suggested that the order parameter of the phase transition is correlated with the suppression of dynamic disorder.

2. Experimental

2.1. Temperature-dependent single-crystal X-ray diffraction

Single crystals of the compound used in this study were obtained from those reported in Sasmal et al. (2019a). The crystals were protected in oil under mild refrigeration. Single-crystal X-ray diffraction (SCXRD) experiments were performed on an Agilent SuperNova, Eos diffractometer employing Cu Kα radiation. The temperature of the crystal was maintained by an Oxford Cryosystems open flow nitrogen cryostat.

During cooling, visual inspection of diffraction images revealed weaker reflections in addition to strong reflections at low temperatures.

Diffraction images collected at 150 K, 140 K and 130 K–114 K in steps of ΔT = 2 K showed that the weaker diffuse features appear at 124 K and condense into satellite reflections at 122 K (Table 1 and Fig. S1 in supporting information). The transition temperature is significantly higher than that of molecular biphenyl (T_{c, biphenyl} = 42 K). On the other hand, related polyphenyls p-terphenyl and p-quarterphenyl undergo phase transition towards superstructure phases at much higher critical temperatures [T_{c, terphenyl} ≈ 190 K (Yamamura et al., 1998), T_{c, quarterphenyl} ≈ 233 K (Saito et al., 1985)]. Complete diffraction data were collected at T = 160 K and 100 K.

Determination of unit-cell parameters and data reductions were performed using the software suite CrysAlisPro (Rigaku Oxford Diffraction, 2019) (Tables 1 and S1).

Satellite reflections of first order (m = 1) observed below T_c could be indexed with modulation wavevector q = (σ₁, 0, σ₃), σ₁ = σ₃ ≃ with respect to the basic monoclinic crystal system. Here, q = (101) is perpendicular to the b axis consistent with monoclinic symmetry while in molecular biphenyl q_I violates monoclinic symmetry and q_II is parallel to b (Cailleau et al., 1979).

Using the plugin program NADA (Schönleber et al., 2001) in CrysAlisPro, deviations of the σ values as a function of T from a rational value of 0.5 were found to be within their standard uncertainities (Table 1), indicating a commensurate nature of the modulation.

Reflections at T = 100 K were indexed by four integers (hklm) using a basic monoclinic b-unique lattice (Tables 1 and S1) and modulation wavevector, q = (, 0, ) and data integration was performed. Empirical absorption correction was performed using the AbsPack program embedded in CrysAlisPro.

The ratio of the average intensities (〈I〉) between main and satellite reflections is 13:1 and that of their average significance [〈I/σ(I)〉] is 3:1. This indicates pronounced modulation which is characteristic of modulated molecular crystals (Schönleber & Chapuis, 2001; Schönleber et al., 2003; Dey et al., 2016, 2018; Rekis et al., 2020, 2021).

The monoclinic crystal system in addition to the reflection conditions suggest the superspace group P2₁(σ₁0σ₃)0 with σ₁ = σ₃ = ½ (Stokes et al., 2011; van Smaalen et al., 2013).

2.2. Structure refinement of the modulated structure

The crystal structure of the room-temperature phase (phase I hereon) was redetermined at 160 K using Superflip (Palatinus & Chapuis, 2007) and refined using Jana2006 and Jana2020 (Petříček et al., 2014).

Atoms were renamed with suffixes a and b for the two independent molecules A and B [Fig. 1(a)]. Anisotropic atomic displacement parameters (ADPs) of all non-hydrogen atoms were refined. Hydrogen atoms were added to carbon and nitrogen atoms using a riding model in ideal chemical geometry with constraints for isotropic ADPs [U_iso(H) = 1.2U_eq(N), U_iso(H) = 1.2U_eq(C_aromatic) and U_iso(H) = 1.5U_eq(C_sp3)].

Owing to the pseudoorthorhombic crystal system, the integrated data was tested for twinning employing twofold rotation along the [100] direction as twin law. This twin law is a true symmetry element in the case of a hypothetical ortho­rhombic crystal system with point group symmetry 222 (Petříček et al., 2016; Nespolo, 2019). The fit of the structure model improved (compare = 0.0463 to 0.0408) and volume of the second component refined to 0.0240 (8) (Table S2). Finally, positions of the H atoms of NH groups and the parameter corresponding to isotropic extinction correction were refined that further improved values (= 0.0393, Table S2 in supporting information).

The crystal structure reproduced the values for intramolecular rotations reported those for the structure at T = 200 K [φ_chiral = φ₁ (hereon) and ψ in Fig. 1(a)]. In addition, we also observe that the coplanar biphenyl rings are significantly rotated with respect to the amide groups [at T = 200 K: φ₂ = 32.8° and 31.2° (Sasmal et al., 2019a) and at T = 160 K in Fig. 1(a)] which also remains invariant as a function of temperature.

The modulated structure of phase II at 100 K was refined using Jana2006 and Jana2020. Fractional coordinates of all atoms from the crystal structure at T = 160 K were used in the starting model while retaining the same riding model geometry for hydrogen atoms as in phase I and the average structure was refined as main reflections. In successive steps, an incommensurate (IC) model described by one harmonic wave for displacive modulation describing the atomic modulation functions (AMFs) and basic parameters for anisotropic ADPs for non-hydrogen atoms was refined against main and satellite reflections that resulted in good fit to the diffraction pattern ( = 0.0425). However, ADPs of four non-hydrogen atoms were found to be non-positive definite.

Since the components of q (σ₁ and σ₃) are rational, three commensurately modulated structures were pursued by fixing the initial phase of the modulation to values t₀ = 0, and , respectively. While the former two t₀ values describe monoclinic space group B2₁ symmetry for the equivalent 3D 2a × b × 2c superstructure, the third corresponds to triclinic B1 symmetry. The commensurately modulated structure (C) model corresponding to t₀ = resulted in the best fit to the diffraction data ( = 0.0426) including ADPs of all atoms positive definite.

As the atomic modulation functions (AMFs) have sinusoidal character, the residual values are similar to the IC model (Fig. 2, Figs. S2–S4 and Table S2 in supporting information). However, the C model at t₀ = is described with either cosine or sine waves for the AMFs (equal to number of refinable fractional coordinates in the equivalent superstructure) reducing significantly the number of refinable parameters as compared with the IC model (compare N_C = 649 with N_IC = 811, further tests in supporting information).

Figure 2 (xs1,xs4)-sections of a Fourier map centered on carbon atoms (black): (a) C23a of molecule A and (b) C23b of molecule B. The contour lines and the width of the maps are 0.5 e Å^−3 and 2.5 Å, respectively.

The final C model was further improved by refining the parameter corresponding to isotropic extinction correction and AMFs and positions of hydrogen atoms of NH groups ( = 0.0419, Table S2). The refined twin volume in phase II reproduced the value similar to that in phase I [T = 100 K, twvol2 = 0.0242 (7) in Table S2]. Presumably, the crystal possesses pseudo-merohedral growth twins.

3. Results and discussion

3.1. Structural phase transition and unequal distortion of molecules

In the present case, the monoclinic symmetry is retained below T_c unlike monoclinic to triclinic distortion at the disorder–order phase transition of p-terphenyl (Rice et al., 2013) and p-quarterphenyl (Baudour et al., 1978).

In the final commensurately modulated structure model with t₀ = , sections corresponding to t = and (Figs. 3 and S5) are physically relevant. These sections represent the atomic coordinates in the equivalent twofold superstructure in 3D (Figs. 4, S6 and S7).

Figure 3 t-plots of intramolecular rotations of molecule A (blue) and B (red) as well as intermolecular tilts and distances between stacks of 4-biphenylcarboxy-(L)-phenylalaninate. (a) Dihedral angle |φ^3| represents internal torsion within the biphenyl rings, (b) dihedral angle |φ^2| represents the torsion angle between the inner ring of the biphenyl and the amide groups, (c) φ^1 represents the torsion angle of the amide groups with respect to the –COOCH3 groups and (d) ψ represents the torsion angle of –COOCH3 groups with respect to amide groups. (e) | θAA/BB| represents tilt between biphenyl rings of A and A^ii (blue), and of B and B^ii (red) and |θAB/BA| (dashed-dotted black curve) represent tilt between inner aromatic rings of biphenyl (bonded to amide groups) of A and outer ring of B and vice versa. (f) Intermolecular distances (d) between biphenyl rings of A and A^ii (blue), between those of B and B^ii (red) and between those of A and B (black). Horizontal dashed lines represent those angles and distances in phase I (|φ^3| = | θAA/BB| = 0°). Vertical dashed lines indicate t values corresponding to angles and distances in the 3D superstructure. Symmetry code (ii): x + 1, y, z, t.

Figure 4 Comparison of structures in phase I and phase II across the phase transition highlighting the effect of internal torsion (φ^3) within biphenyl on the stacking arrangements along a. The tilt between the biphenyl stacks, θAA/BB are different for the inner rings (bonded to amide rings) and the outer rings. Corresponding values of φ^3 and θ are in Fig. 3(e) and those for C—H⋯O and C—H⋯H—C in Table 2. See full unit cells in Figs. S6 and S7. Viewed along .

Crystal structures of phase I and phase II have group–subgroup relations and the doubling of the a and c axes describes the additional B-centering of the superstructure in phase II.

The superstructure derived using Jana2006 comprises four molecules in the asymmetric unit (Z′ = 4); two each corresponding to molecules A and B of phase I (Fig. 4).

The covalent bond distances are similar for the independent set of molecules and are practically unaffected by modulation Table S7).

In the present study, discussion is based on the modulated structure in order to establish unique relations between phase I and phase II (Rekis et al., 2021; Chapuis, 2020; Ramakrishnan et al., 2019; Dey et al., 2016; Noohinejad et al., 2015; Schoenleber, 2011; Schönleber et al., 2003).

The modulated structure suggests that the phase transition is dominated by evolution of internal torsional degrees of freedom (φ³ > 0°) within the biphenyl moieties [Fig. 3(a)]. The twists about the central C—C bond are significantly different for the two molecules where the torsional modulation of A are 2–4 times larger than those of B (dihedral angles = 15.6°, 20.5° and = 4.1°, 9.3°). These distortions are described by highly anisotropic AMFs (u) along the three basis vectors where the maximum amplitude are along b for the carbon atoms of biphenyl (Fig. 2 and Table S4). Notably, the rotations in the present structure are significantly larger than those reported for molecular biphenyl [φ ≃  ±  5.5° (Petricek et al., 1985; Baudour & Sanquer, 1983)]. These values are smaller than those in the low-temperature superstructure of p-terphenyl and p-quarterphenyl [maximum φ_{terphenyl, quarterphenyl} ≃ 23° (Rice et al., 2013; Baudour et al., 1976, 1978)].

The nature of structural changes in the present system and molecular biphenyl below the phase transition temperature is different to p-(n > 2)-phenyl systems described by the property that in the later cases two disordered conformations of the molecules freeze by superstructure formation and breaking the monoclinic symmetry of their high-temperature phase.

A distinctive property of the present modulated structure is the unequal modulation for the two different moieties where u_biphenyl > u_{phenylalaninate} (Table S4). Compared to , the distortions in torsion angles φ¹ are lesser and those in ψ are very small and virtually equal for both A and B [ = −133.7°, −127.6°; = 55°, 56.2°; = 36.8°, 37.7°; = 36°, 36.6° in Figs. 3(c) and 3(d)].

A possible reason for the weaker modulations of the atoms around the chiral centers is the directional strong intermolecular N—H⋯O bonds makes large intramolecular rotations unfavorable.

Note that the observed changes in the rotations of φ² of molecule A [compare = 39.1°, 25.8° with = 32.9°, 28.9° in Fig. 3(b)] are predominantly described by strong modulations of the molecule's biphenyl moiety. The asymmetry in rotations of individual molecules (Δ|φ³| ≈ 5°) is determined by the disparate bonding environments of the biphenyl moieties where the inner rings are that are covalently bonded to amide groups while the outer interact weakly via C—H⋯H—C interactions with the phenyl rings of phenylalaninate groups (Fig. 4). Subsequently, the unequal values at the relevant t-sections of φ³ are correlated with those of φ² [compare Figs. 3(a) and 3(b)].

It is also observed that the variation in φ¹ is greater for molecule A than that of B [compare ≃ 6° with ≃ 1° in Fig. 3(c)]. The origin of disparate distortions in intramolecular rotations is explained in §3.2.

In the modulated structure, the biphenyl moieties in (AA)_n and (BB)_n stacks which are parallel (θ = 0°) in phase I are tilted with respect to each other [Fig. 3(e)]. These tilts (θ_AA/BB) are of the order of the internal twists (φ³) of the independent biphenyl moieties [θ_AA = 19.5° and 16.6°; θ_BB = 5° and 7.2° for inner and outer rings of biphenyl respectively, compare Fig. 3(e) with Fig. 3(a)] The orientation between the biphenyl moieties within the (ABAB)_n stacks also vary with Δθ_AA/BB ≃ 12° where the value is intermediate to and [compare Fig. 3(e) with Fig. 3(a)]. In addition, intermolecular distances between the biphenyl moieties within the stacks at the two t-sections are different and vary up to Δd_AA/BB ≃ 0.05 Å and Δd_ABAB ≃ 0.02 Å [Fig. 3(f)].

Overall distortions in d_AA and d_BB are nearly equal although θ_AA is greater than θ_BB. These variations in d may arise to compensate for the mutual rotations of aromatic rings within the stacks. For example, the comparison θ_AA for outer rings > θ_AA for inner rings as opposed to θ_BB for outer rings < θ_BB for inner rings could explain the complimentary variations of d_AA and of d_BB [sets of distances (Å) in t = (, ): d_AA = (5.01, 5.06); d_BB = (5.06, 5.02) in Fig. 3(f)]. It could therefore be argued that the dimerization of biphenyl molecular stacks below T_c is predominantly governed by distortion described by molecular rotations rather than intermolecular distances. On the other hand, variation of intermolecular distances between aromatic rings of L-phenylalaninate are similar to those of the biphenyls albeit the interstack rotations of the former are significantly smaller (θ < 3°, Fig. S5 in supporting information).

3.2. Competitive forces governing modulations

Structural studies in the 3D phase of molecular biphenyl have suggested that the ortho-hydrogen atoms are displaced away in the plane of the rings to minimize steric hindrance (Trotter, 1961; Hargreaves & Rizvi, 1962; Charbonneau & Delugeard, 1976). On the other hand, dynamic disorder predominantly governed by torsional vibrations around the long molecular axis (Petricek et al., 1985) is predicted to balance the planar conformation of biphenyl favorable for crystal packing (Lenstra et al., 1994).

As short as 1.98 Å in phase I (Table 2), these contacts are shorter than the predicted values for twice van der Waals radius for hydrogen [r = 1.1–1.2 Å (Rowland & Taylor, 1996; Alvarez, 2013)]. In the modulated structure, we observe that the distances between the ortho-hydrogen atoms are marginally but consistently larger than those in phase I (Table 2) that could suggest that the torsional modulations aid in minimization of the presumed steric hindrance below T_c (Dey et al., 2022, 2018).

Table 2
Comparison of nonbonded hydrogen⋯acceptor and hydrogen⋯hydrogen distances (Å) involved in hydrogen bonds and steric factors in phase I (T₁) and phase II (T₂)

The two values for distances in phase II (T₂) correspond to t = and t = , respectively.

Interaction class	Atom labels	Phase	Distance (Å)
N—H⋯O	H1n1a⋯O3a^i	I	2.00
		II	1.97, 1.95
	H1n1b⋯O3b^ii	I	2.00
		II	2.00, 1.98
C—H⋯O	H1c10a⋯O2a^iii	I	2.72
		II	2.72, 2.68
	H1c10b⋯O2b^iv	I	2.78
		II	2.74, 2.73
Intra H⋯H	H1c14a⋯H1c19a	I	1.98
		II	2.08, 2.09
	H1c14b⋯H1c19b	I	1.98
		II	2.00, 1.99
	H1c16a⋯H1c23a	I	2.03
		II	2.10, 2.16
	H1c16b⋯H1c23b	I	2.02
		II	2.03, 2.06
Intra H⋯O	H1C13a⋯O3a	I	2.59
		II	2.66, 2.54
	H1C13b⋯O3b	I	2.59
		II	2.61, 2.56
Intra H⋯O	H1C3a⋯O3a	I	2.37
		II	2.38, 2.38
	H1C3b⋯O3b	I	3.65
		II	3.65, 3.65
Inter H⋯H	H1c21a⋯H1c7b	I	2.59
		II	2.61, 2.56
	H1c21b⋯H1c7a^ii	I	2.45
		II	2.39, 2.46
Symmetry codes. Phase I: (i) x − 1, y, z; (ii) x + 1, y, z; (iii) ; (iv) . Phase II: (i) x − 1, y, z, t; (ii) x+ 1, y, z, t; (iii) ; (iv) .

A peculiar property of the modulated structure under discussion is the significant difference in the torsional amplitude φ³ of the independent molecules. This aspect cannot be explained solely based on the intramolecular steric factors. Analysis of the crystal packing shows that each of these independent biphenyl moieties maintains close intermolecular CH⋯HC contacts with the phenyl rings of L-phenylalaninate in AB and BA fashion (Fig. 4).

These distances are significantly longer (intermolecular d_H⋯H ≥ 2.4 Å, Table 2) compared with the intramolecular H⋯H distances. On the other hand, the aromatic rings of L-phenylalaninate interact with adjacent oxygen atoms of –COOCH₃ via C—H⋯O hydrogen bonds (Fig. 4 and Table 2). These hydrogen bonds are weaker (Desiraju & Steiner, 2001) but highly directional [∠(C—H⋯O) = 159–164°] with very little variation in the distances.

Interestingly, those H⋯H distances involving biphenyl moieties of molecule B are consistently smaller than those of molecule A in both phases (Table 2). We argue that in the presence of both the van der Waals interactions and weak C—H⋯O bonds, the larger distortions of A is favored by weaker CH⋯HC interactions while that is suppressed in B.

The variations in φ² and asymmetry in φ³ can be explained with respect to the intramolecular nonbonded nearest distances between the hydrogen atoms bonded to C13 atoms (Fig. 1) of inner rings of biphenyl and the oxygen atoms O3 of the amide groups. The distances are short (d_H13⋯O3 = 2.59 Å in phase I, Table 2) and are in the range of the sum of the van der Waals radii of oxygen and hydrogens [r_H = 1.1–1.2 Å, r_O = 1.4–1.56 Å (Rowland & Taylor, 1996; Alvarez, 2013)]. In the modulated structure, the larger distortions of requires the amide groups to rotate with respect to the inner phenyl ring to optimize these C—H⋯O=C contacts to avoid steric effects (compare d_H13a⋯O3a = 2.66 Å, 2.54 Å in Table 2 with = 39.1°, 25.8° in Fig. 3). Although the variation in is smaller, the positive correlation that is larger rotations with greater H⋯O distances and vice versa are observed (compare d_H13b⋯O3b = 2.61 Å, 2.56 Å in Table 2 with = 32.9°, 28.9° in Fig. 3). Alternatively, it could be argued that the asymmetric distortion of φ³ within individual molecules is a result of the constraint of the amide groups, where rotations are hindered when the C—H⋯O=C contact distances are short and favored when those are longer. Therefore, the four different values of intramolecular torsion φ³ within the biphenyl moieties are distinctively governed by intramolecular nonbonded H⋯H and H⋯O; and intermolecular nonbonded H⋯H contacts and weak C—H⋯O hydrogen bonds.

The independent molecules A and B differ from each other with respect to their torsion around the chiral center namely φ¹ (= −130.1° and 56.1° for A and B, respectively, in phase I). The difference in twist angles has remarkable effects on the molecular conformation with respect to the distance between the O3 atoms of the amide groups and hydrogen atoms of the chiral centers C3 carbon atoms (d_H3⋯O3 = 2.37 Å, 3.65 Å for A and B, respectively, in phase I, Table 2). In phase II, the modulations of L-phenylalaninate moieties are weaker than that of the biphenyl groups possibly due to the presence of strong intermolecular N—H⋯O hydrogen bonds. However, the variations in ( ≃6°) as compared with ( ≃1°) are greater which could arise to optimize significantly shorter H3⋯O3 nonbonded contacts of A as compared with B (d_H3⋯O3 = 2.38 Å, and 3.65 Å for A and B, respectively, in phase II, Table 2).

As noted in §2.2 the average intensities of the satellite reflections are an order of magnitude smaller than the main reflections. The order parameter of the phase transition might be expressed as proportional to the amplitude of the modulation which is approximately proportional to square root of the intensities of the satellite reflections (van Smaalen, 2005). The pronounced AMFs of the biphenyl moieties describing the predominant distortions in the crystal structure are accompanied by suppression of dynamic disorder in phase II as compared with phase I. For example, the carbon atoms at ortho (C14, C16, C19, C23) and meta (C13, C17, C20, C22) positions are strongly displaced [Fig. 5(b), Tables S4 and S5]. Subsequently, the ADPs are significantly reduced as compared with phase I [Fig. 5(a), Table S5]. Notably, the decrease of the ADPs (U_eq) from T = 160 K to T = 100 K is larger for those of molecule A than those for B in conjunction with the fact that overall the ADPs are smaller or similar for the former as opposed to phase I, while the square of the amplitude of modulations (u²) are greater for A than those for B [compare Figs. 5(b) with 5(a)].

Figure 5 Scatter plots of equivalent value of anisotropic ADPs (Ueq) and square of the amplitude of modulations (u^2) of the carbon atoms of biphenyl moieties (C12 through to C23) and non-hydrogen atoms of L-phenylalaninate moieties [see Fig. 1(a)] of molecules A (blue) and B (red). (a) and (c) Ueq of the biphenyl carbon atoms and L-phenylalaninate non-hydrogen atoms, respectively, at T = 160 K (open circles) and at T = 100 K (full circles). (b) and (d) u^2 (diamonds) of the corresponding biphenyl carbon atoms and L-phenylalaninate non-hydrogen atoms of molecules A and B, respectively, at T = 100 K. See Tables S5 and S6.

The decrease in ADPs of atoms of L-phenylalaninate moieties of A are greater than B from T = 160 K to T = 100 K [Fig. 5(c)]. Unlike the biphenyl moieties, such apparent switch-over of the ADPs is not observed where the overall values of A are greater than those of B in both phases I and II, while the squares of the AMFs in II are larger for A than those for B [compare Figs. 5(d) with 5(c), Tables S4 and S6]. It is possible that the superstructure formation below the phase transition aids in optimal conformation of the biphenyl moieties by significant distortions of their internal torsion while the modulations in L-phenylalaninate groups compensates for the former.

In hindsight, the observed larger mean-squared displacements of atoms of molecule A than B in high-T phase I possibly arises to optimize the short nonbonded H⋯O distances around the chiral center that is largely minimized in phase II by greater intramolecular distortions of torsional angles in the former than the later. This hypothesis is supported by the small but observable distortion of (∼ 6°) as compared with (∼ 1°) while those for ψ are significantly smaller (∼ 1°) for both molecules in phase II.

4. Conclusions

The 2a  ×  b  ×  2c superstructure of 4-biphenylcarboxy-(L)-phenylalaninate at T = 100 K has been successfully described as a commensurately modulated structure within (3+1)D superspace with superspace group symmetry P2₁(σ₁0σ₃)0. The single crystal to single crystal phase transition below T = 124 K drives the 3D structure directly to a locked-in twofold superstructure accompanied by significant distortion of torsional rotations within biphenyl away from coplanarity that is also a property of incommensurately modulated structure of biphenyl but with amplitudes four times smaller than the present system.

The phase transition temperature is significantly higher than that in biphenyl yet significantly lower than for p-terphenyl and p-quarterphenyl. Consistent with the T_c, the maximum amplitude of torsion is also intermediate and in the order φ_{quarterphenyl} ≥ φ_terphenyl > φ_{4-biphenylcarboxy-L-phenylalaninate} > φ_biphenyl.

Topologically separated, conformations of both the weaker C—H⋯O bonds and stronger N—H⋯O bonds are rigid and that underlines their role in stabilizing the crystal packing in both phases. A unique property of the present polyphenyl coupled amino acid ester is the distinctively unequal torsional amplitude (φ_A > φ_B) within the independent molecules which is governed by multiple level of competitions involving unequal van der Waals constraints in the presence of weak hydrogen bonds between the biphenyl and L-phenylalaninate moieties while the asymmetry of φ³ is determined by intramolecular nonbonded constraints between phenyl rings and amide groups.

The unusual nature of the phase transition is rationalised by the fact that unequal intramolecular distortions of the two molecules are complemented by unequal suppression of the dynamic disorder of their atoms below T_c.

The present investigation of the phase transition in the biphenylcarboxy coupled amino acid ester system also shows consequences for crystal packing where significant distortions in conjugations represented by mutual intramolecular rotations between homo aromatic groups as well as with aliphatic amide groups results in modulated π⋯π stacking arrangements (θ_AA/BB > 0°) of phenyl groups but preserves the conformations of intermolecular directional N—H⋯O hydrogen bonds of the high-temperature structure.

5. Related literature

The following references are cited in the supporting information: Becker & Coppens (1974), Coelho (2003, 2018), Petříček et al. (2014).

Supporting information

Computing details

Data collection: CrysAlis PRO 1.171.41.122a (Rigaku OD, 2021) for I_phaseII_modulated; CrysAlis PRO 1.171.40.54a (Rigaku OD, 2019) for I_phaseI. Cell refinement: CrysAlis PRO 1.171.41.122a (Rigaku OD, 2021) for I_phaseII_modulated; CrysAlis PRO 1.171.40.54a (Rigaku OD, 2019) for I_phaseI. Data reduction: CrysAlis PRO 1.171.41.122a (Rigaku OD, 2021) for I_phaseII_modulated; CrysAlis PRO 1.171.40.54a (Rigaku OD, 2019) for I_phaseI.

(I_phaseII_modulated)

Crystal data

C23H21NO3	F(000) = 760
Mr = 359.4	Dx = 1.312 Mg m^−3
Monoclinic, P21(α0γ)0†	Cu Kα radiation, λ = 1.54184 Å
q = 0.500000a* + 0.500000c*	Cell parameters from 3948 reflections
a = 5.0377 (2) Å	θ = 4.2–65.7°
b = 8.5898 (3) Å	µ = 0.70 mm^−1
c = 42.0432 (14) Å	T = 100 K
β = 90.884 (3)°	Rectangular, colorless
V = 1819.11 (11) Å^3	0.24 × 0.16 × 0.11 mm
Z = 4

† Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, x₂+1/2, −x₃, −x₄.

Data collection

SuperNova, Dual, Cu at home/near, Eos diffractometer	8898 independent reflections
Radiation source: X-ray tube	5940 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 7.9580 pixels mm^-1	θmax = 65.8°, θmin = 3.2°
ω scans	h = −5→6
Absorption correction: multi-scan CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −10→7
Tmin = 0.966, Tmax = 1	l = −43→49
13838 measured reflections

Refinement

Refinement on F	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.042	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
wR(F^2) = 0.053	(Δ/σ)max = 0.001
S = 1.40	Δρmax = 0.28 e Å^−3
8898 reflections	Δρmin = −0.26 e Å^−3
662 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 2000 (200)
403 constraints	Absolute structure: 2293 of Friedel pairs used in the refinement

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

	x	y	z	Uiso*/Ueq
O1a	0.3281 (4)	0.0586 (3)	0.45604 (4)	0.0324 (6)
O1b	0.8601 (3)	0.5767 (3)	0.04224 (4)	0.0245 (5)
O2a	0.1716 (5)	0.2539 (3)	0.48497 (5)	0.0528 (8)
O2b	0.6592 (4)	0.3891 (3)	0.01379 (4)	0.0357 (6)
O3a	0.8641 (3)	0.2662 (3)	0.39922 (4)	0.0268 (5)
O3b	0.5649 (3)	0.4034 (3)	0.09454 (4)	0.0242 (5)
N1a	0.4221 (4)	0.253675	0.40734 (4)	0.0202 (6)
N1b	1.0017 (4)	0.3687 (3)	0.08786 (4)	0.0174 (5)
C1a	0.2019 (6)	−0.0493 (4)	0.47735 (6)	0.0344 (9)
C1b	0.7017 (5)	0.6894 (4)	0.02465 (6)	0.0290 (8)
C2a	0.2943 (5)	0.2079 (4)	0.46273 (5)	0.0246 (7)
C2b	0.8090 (4)	0.4294 (4)	0.03488 (5)	0.0214 (7)
C3a	0.4348 (5)	0.3147 (4)	0.43962 (5)	0.0215 (7)
C3b	0.9674 (5)	0.3156 (4)	0.05526 (5)	0.0193 (6)
C4a	0.3236 (5)	0.4818 (4)	0.44133 (5)	0.0229 (7)
C4b	0.8374 (5)	0.1516 (3)	0.05272 (5)	0.0220 (7)
C5a	0.4652 (5)	0.5942 (4)	0.41993 (5)	0.0232 (7)
C5b	0.9455 (5)	0.0347 (3)	0.07633 (5)	0.0223 (7)
C6a	0.3934 (5)	0.6056 (4)	0.38805 (6)	0.0271 (7)
C6b	0.8291 (5)	0.0212 (4)	0.10608 (5)	0.0245 (7)
C7a	0.5263 (5)	0.7059 (4)	0.36807 (6)	0.0287 (8)
C7b	0.9184 (5)	−0.0881 (4)	0.12781 (6)	0.0273 (7)
C8a	0.7338 (5)	0.7984 (4)	0.37965 (6)	0.0273 (7)
C8b	1.1270 (5)	−0.1852 (4)	0.12056 (6)	0.0290 (8)
C9a	0.8041 (5)	0.7890 (4)	0.41150 (6)	0.0288 (8)
C9b	1.2478 (5)	−0.1728 (4)	0.09106 (6)	0.0285 (8)
C10a	0.6718 (5)	0.6877 (4)	0.43153 (6)	0.0254 (7)
C10b	1.1568 (5)	−0.0635 (4)	0.06929 (5)	0.0246 (7)
C11a	0.6357 (4)	0.2417 (4)	0.38927 (5)	0.0193 (7)
C11b	0.7942 (4)	0.4048 (4)	0.10536 (5)	0.0177 (6)
C12a	0.5851 (4)	0.1990 (4)	0.35516 (5)	0.0193 (6)
C12b	0.8486 (4)	0.4459 (4)	0.13957 (5)	0.0182 (6)
C13a	0.7508 (5)	0.2571 (4)	0.33255 (5)	0.0250 (7)
C13b	0.6799 (5)	0.5475 (4)	0.15426 (6)	0.0369 (9)
C14a	0.7120 (5)	0.2217 (4)	0.30072 (6)	0.0267 (8)
C14b	0.7182 (5)	0.5891 (4)	0.18587 (6)	0.0371 (9)
C15a	0.5115 (4)	0.1245 (4)	0.29032 (5)	0.0203 (6)
C15b	0.9251 (4)	0.5269 (3)	0.20397 (5)	0.0185 (6)
C16a	0.3465 (5)	0.0658 (4)	0.31327 (6)	0.0256 (8)
C16b	1.0894 (5)	0.4230 (4)	0.18885 (5)	0.0334 (8)
C17a	0.3818 (5)	0.1034 (4)	0.34520 (5)	0.0233 (7)
C17b	1.0577 (5)	0.3836 (4)	0.15712 (6)	0.0310 (8)
C18a	0.4741 (4)	0.0871 (4)	0.25609 (5)	0.0193 (6)
C18b	0.9603 (4)	0.5671 (4)	0.23844 (5)	0.0202 (7)
C19a	0.6345 (5)	0.1510 (4)	0.23310 (6)	0.0286 (8)
C19b	0.7931 (5)	0.6736 (4)	0.25293 (5)	0.0304 (8)
C20a	0.6015 (6)	0.1174 (4)	0.20114 (6)	0.0314 (8)
C20b	0.8211 (5)	0.7084 (4)	0.28498 (6)	0.0311 (8)
C21a	0.4041 (5)	0.0168 (4)	0.19119 (6)	0.0270 (7)
C21b	1.0142 (4)	0.6378 (4)	0.30348 (5)	0.0232 (7)
C22a	0.2431 (5)	−0.0484 (4)	0.21341 (6)	0.0311 (8)
C22b	1.1828 (5)	0.5347 (4)	0.28921 (6)	0.0293 (8)
C23a	0.2771 (5)	−0.0138 (4)	0.24536 (6)	0.0272 (8)
C23b	1.1584 (5)	0.4989 (4)	0.25727 (6)	0.0262 (7)
H1c3a	0.618836	0.318816	0.445839	0.0322*
H1c3b	1.144647	0.308885	0.047295	0.029*
H1c4a	0.137775	0.480681	0.435915	0.0343*
H2c4a	0.334422	0.518391	0.462889	0.0343*
H1c4b	0.64889	0.160976	0.055154	0.033*
H2c4b	0.857399	0.112158	0.031532	0.033*
H1c6a	0.250178	0.543224	0.379746	0.0325*
H1c6b	0.684882	0.088689	0.111512	0.0294*
H1c7a	0.475132	0.711883	0.346022	0.0345*
H1c7b	0.834829	−0.096535	0.148107	0.0328*
H1c8a	0.826414	0.867424	0.365715	0.0327*
H1c8b	1.188658	−0.260863	0.13576	0.0347*
H1c9a	0.945149	0.853008	0.419823	0.0346*
H1c9b	1.393387	−0.239779	0.08587	0.0342*
H1c10a	0.722958	0.681826	0.453577	0.0305*
H1c10b	1.240567	−0.055308	0.049001	0.0295*
H1n1a	0.253 (5)	0.254 (3)	0.3989 (6)	0.0243*
H1n1b	1.172 (5)	0.381 (3)	0.0954 (5)	0.0208*
H1c13a	0.893824	0.322492	0.339022	0.03*
H1c13b	0.532889	0.590411	0.14245	0.0443*
H1c14a	0.826301	0.26514	0.285403	0.032*
H1c14b	0.599656	0.662307	0.195409	0.0446*
H1c16a	0.206194	−0.001581	0.306925	0.0307*
H1c16b	1.231637	0.376016	0.200867	0.0401*
H1c17a	0.263687	0.062576	0.360572	0.028*
H1c17b	1.180054	0.313485	0.147303	0.0371*
H1c19a	0.772211	0.220388	0.239673	0.0343*
H1c19b	0.656647	0.723683	0.240543	0.0365*
H1c20a	0.714746	0.16355	0.185851	0.0376*
H1c20b	0.704435	0.7827	0.294451	0.0373*
H1c22a	0.106273	−0.118415	0.206696	0.0374*
H1c22b	1.320725	0.486353	0.301714	0.0352*
H1c23a	0.162843	−0.059866	0.26048	0.0326*
H1c23b	1.279065	0.426399	0.247926	0.0314*
H1c21a	0.380038	−0.007098	0.169026	0.0324*
H1c21b	1.030215	0.660313	0.325786	0.0279*
H1c1a	0.237302	−0.153941	0.470628	0.0516*
H2c1a	0.270779	−0.034204	0.498543	0.0516*
H3c1a	0.013797	−0.031416	0.477042	0.0516*
H1c1b	0.75009	0.792587	0.031285	0.0436*
H2c1b	0.733216	0.677993	0.002307	0.0436*
H3c1b	0.517047	0.672102	0.028702	0.0436*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1a	0.0429 (11)	0.0232 (9)	0.0314 (9)	0.0014 (8)	0.0128 (8)	0.0012 (7)
O1b	0.0298 (9)	0.0186 (8)	0.0249 (8)	−0.0019 (7)	−0.0074 (6)	0.0017 (7)
O2a	0.0936 (17)	0.0291 (11)	0.0369 (11)	0.0007 (12)	0.0360 (11)	−0.0019 (9)
O2b	0.0507 (11)	0.0247 (9)	0.0309 (9)	−0.0020 (9)	−0.0218 (8)	−0.0008 (8)
O3a	0.0145 (8)	0.0396 (10)	0.0265 (9)	−0.0001 (8)	−0.0001 (6)	−0.0032 (8)
O3b	0.0147 (8)	0.0325 (9)	0.0252 (8)	−0.0002 (7)	−0.0029 (6)	−0.0009 (8)
N1a	0.0163 (10)	0.0250 (10)	0.0193 (9)	0.0005 (8)	−0.0008 (7)	−0.0013 (8)
N1b	0.0137 (9)	0.0189 (9)	0.0193 (9)	−0.0022 (8)	−0.0018 (7)	0.0001 (7)
C1a	0.0492 (17)	0.0277 (14)	0.0265 (13)	−0.0096 (13)	0.0037 (11)	0.0022 (11)
C1b	0.0399 (15)	0.0202 (12)	0.0269 (12)	0.0048 (12)	−0.0037 (10)	0.0032 (10)
C2a	0.0254 (13)	0.0282 (13)	0.0202 (11)	−0.0010 (11)	0.0001 (9)	−0.0050 (10)
C2b	0.0229 (12)	0.0230 (12)	0.0184 (11)	−0.0007 (10)	0.0019 (9)	0.0003 (9)
C3a	0.0217 (12)	0.0235 (12)	0.0192 (11)	0.0012 (10)	−0.0020 (9)	−0.0028 (9)
C3b	0.0193 (12)	0.0210 (11)	0.0177 (11)	−0.0004 (10)	−0.0013 (8)	−0.0008 (9)
C4a	0.0210 (12)	0.0249 (12)	0.0228 (12)	0.0033 (10)	0.0020 (9)	−0.0042 (10)
C4b	0.0248 (13)	0.0161 (11)	0.0249 (12)	−0.0011 (10)	−0.0056 (9)	−0.0016 (9)
C5a	0.0253 (13)	0.0184 (12)	0.0261 (12)	0.0040 (10)	0.0043 (9)	−0.0010 (9)
C5b	0.0248 (13)	0.0151 (11)	0.0270 (12)	−0.0039 (10)	−0.0048 (9)	−0.0040 (9)
C6a	0.0227 (13)	0.0277 (13)	0.0308 (13)	0.0028 (11)	−0.0041 (9)	−0.0032 (11)
C6b	0.0243 (13)	0.0182 (11)	0.0310 (13)	0.0012 (10)	−0.0021 (9)	−0.0027 (10)
C7a	0.0297 (13)	0.0321 (14)	0.0245 (12)	0.0009 (12)	0.0002 (10)	0.0034 (11)
C7b	0.0331 (13)	0.0229 (12)	0.0259 (12)	0.0006 (11)	−0.0010 (10)	−0.0001 (10)
C8a	0.0309 (14)	0.0206 (12)	0.0304 (13)	0.0022 (11)	0.0032 (10)	0.0034 (10)
C8b	0.0313 (14)	0.0213 (12)	0.0340 (14)	0.0003 (11)	−0.0081 (10)	0.0030 (11)
C9a	0.0294 (14)	0.0249 (13)	0.0321 (13)	−0.0023 (11)	−0.0020 (10)	−0.0046 (11)
C9b	0.0265 (13)	0.0217 (12)	0.0372 (14)	0.0038 (10)	−0.0026 (10)	−0.0031 (10)
C10a	0.0271 (13)	0.0245 (12)	0.0244 (12)	0.0006 (11)	−0.0022 (9)	−0.0024 (10)
C10b	0.0255 (12)	0.0217 (12)	0.0264 (12)	−0.0030 (11)	−0.0001 (9)	−0.0051 (10)
C11a	0.0121 (11)	0.0200 (12)	0.0259 (11)	−0.0001 (9)	0.0008 (8)	0.0012 (9)
C11b	0.0116 (11)	0.0157 (11)	0.0258 (11)	0.0002 (9)	−0.0005 (8)	0.0030 (9)
C12a	0.0165 (11)	0.0194 (11)	0.0221 (11)	0.0013 (10)	0.0005 (8)	0.0000 (9)
C12b	0.0168 (11)	0.0174 (11)	0.0204 (11)	−0.0020 (9)	0.0040 (8)	0.0018 (9)
C13a	0.0166 (12)	0.0324 (14)	0.0260 (12)	−0.0046 (11)	−0.0011 (9)	−0.0031 (11)
C13b	0.0315 (15)	0.0518 (18)	0.0272 (13)	0.0237 (14)	−0.0088 (10)	−0.0068 (13)
C14a	0.0248 (13)	0.0309 (14)	0.0245 (12)	−0.0032 (12)	0.0057 (10)	0.0018 (11)
C14b	0.0381 (15)	0.0444 (16)	0.0287 (13)	0.0247 (14)	−0.0076 (11)	−0.0112 (12)
C15a	0.0195 (11)	0.0169 (11)	0.0244 (11)	0.0031 (10)	0.0002 (8)	0.0005 (9)
C15b	0.0166 (11)	0.0162 (11)	0.0227 (11)	−0.0004 (9)	0.0009 (8)	0.0006 (9)
C16a	0.0244 (13)	0.0254 (13)	0.0268 (13)	−0.0040 (11)	0.0001 (10)	−0.0021 (11)
C16b	0.0297 (14)	0.0460 (16)	0.0243 (12)	0.0194 (13)	−0.0057 (10)	−0.0048 (12)
C17a	0.0180 (12)	0.0249 (13)	0.0272 (12)	−0.0028 (11)	0.0063 (9)	−0.0005 (10)
C17b	0.0239 (13)	0.0430 (16)	0.0258 (12)	0.0144 (12)	−0.0041 (9)	−0.0079 (11)
C18a	0.0164 (11)	0.0168 (11)	0.0247 (11)	0.0038 (9)	−0.0014 (8)	−0.0023 (9)
C18b	0.0212 (12)	0.0179 (11)	0.0217 (11)	−0.0053 (10)	0.0042 (8)	−0.0004 (9)
C19a	0.0279 (14)	0.0289 (14)	0.0290 (13)	−0.0055 (12)	0.0015 (10)	−0.0032 (11)
C19b	0.0287 (14)	0.0391 (16)	0.0233 (12)	0.0120 (12)	−0.0030 (10)	−0.0001 (11)
C20a	0.0376 (15)	0.0338 (15)	0.0227 (12)	−0.0031 (13)	0.0025 (11)	−0.0038 (11)
C20b	0.0298 (14)	0.0365 (15)	0.0271 (12)	0.0071 (12)	0.0044 (10)	−0.0069 (11)
C21a	0.0321 (14)	0.0258 (13)	0.0228 (12)	0.0068 (11)	−0.0048 (9)	−0.0063 (10)
C21b	0.0211 (12)	0.0266 (12)	0.0220 (12)	−0.0074 (10)	0.0003 (9)	−0.0018 (10)
C22a	0.0315 (15)	0.0300 (15)	0.0318 (14)	−0.0040 (12)	−0.0048 (11)	−0.0057 (12)
C22b	0.0290 (14)	0.0314 (14)	0.0273 (13)	0.0038 (12)	−0.0078 (10)	−0.0003 (11)
C23a	0.0245 (13)	0.0297 (14)	0.0273 (13)	−0.0045 (12)	0.0007 (10)	−0.0015 (11)
C23b	0.0266 (13)	0.0259 (13)	0.0260 (12)	0.0056 (11)	−0.0008 (9)	−0.0039 (10)

Geometric parameters (Å, º)

	Average	Minimum	Maximum
O1a—C1a	1.443 (4)	1.438 (4)	1.448 (4)
O1a—C2a	1.324 (5)	1.324 (5)	1.324 (5)
O1b—C1b	1.450 (5)	1.450 (5)	1.450 (5)
O1b—C2b	1.327 (5)	1.326 (5)	1.327 (5)
O2a—C2a	1.196 (5)	1.193 (5)	1.199 (5)
O2b—C2b	1.206 (4)	1.205 (4)	1.206 (4)
O3a—C11a	1.238 (6)	1.236 (6)	1.239 (6)
O3b—C11b	1.235 (6)	1.230 (6)	1.240 (6)
N1a—C3a	1.455 (4)	1.454 (4)	1.457 (4)
N1a—C11a	1.332 (6)	1.331 (6)	1.334 (6)
N1a—H1n1a	0.92 (3)	0.91 (3)	0.92 (3)
N1b—C3b	1.453 (4)	1.453 (4)	1.453 (4)
N1b—C11b	1.324 (5)	1.320 (5)	1.329 (5)
N1b—H1n1b	0.92 (3)	0.91 (3)	0.92 (3)
C1a—H1c1a	1.0 (5)	1.0 (6)	1.0 (6)
C1a—H2c1a	1(2)	1(2)	1(2)
C1a—H3c1a	0.960 (6)	0.960 (6)	0.960 (6)
C1b—H1c1b	1.0 (9)	1.0 (9)	1.0 (9)
C1b—H2c1b	1.0 (19)	1.0 (19)	1.0 (19)
C1b—H3c1b	0.96 (2)	0.96 (2)	0.96 (2)
C2a—C3a	1.519 (5)	1.519 (5)	1.520 (5)
C2b—C3b	1.519 (5)	1.518 (5)	1.520 (5)
C3a—C4a	1.543 (5)	1.542 (5)	1.545 (5)
C3a—H1c3a	1.0 (11)	1.0 (12)	1.0 (12)
C3b—C4b	1.556 (5)	1.555 (5)	1.556 (5)
C3b—H1c3b	1.0 (11)	1.0 (11)	1.0 (11)
C4a—C5a	1.507 (5)	1.504 (5)	1.509 (5)
C4a—H1c4a	0.96 (6)	0.96 (6)	0.96 (6)
C4a—H2c4a	1(3)	1(3)	1(3)
C4b—C5b	1.508 (5)	1.506 (5)	1.511 (5)
C4b—H1c4b	1.0 (3)	1.0 (3)	1.0 (3)
C4b—H2c4b	1(3)	1(3)	1(3)
C5a—C6a	1.387 (5)	1.385 (5)	1.389 (5)
C5a—C10a	1.397 (6)	1.390 (6)	1.404 (6)
C5b—C6b	1.395 (5)	1.392 (5)	1.397 (5)
C5b—C10b	1.394 (6)	1.392 (6)	1.395 (6)
C6a—C7a	1.383 (5)	1.383 (5)	1.384 (5)
C6a—H1c6a	1.0 (3)	1.0 (3)	1.0 (3)
C6b—C7b	1.380 (5)	1.376 (5)	1.384 (5)
C6b—H1c6b	1.0 (8)	1.0 (8)	1.0 (8)
C7a—C8a	1.395 (6)	1.393 (6)	1.396 (6)
C7a—H1c7a	1(3)	1(3)	1(3)
C7b—C8b	1.379 (6)	1.379 (6)	1.380 (6)
C7b—H1c7b	1(4)	1(4)	1(4)
C8a—C9a	1.382 (5)	1.379 (5)	1.386 (5)
C8a—H1c8a	1.0 (18)	1.0 (18)	1.0 (18)
C8b—C9b	1.394 (5)	1.391 (5)	1.397 (5)
C8b—H1c8b	1.0 (8)	1.0 (8)	1.0 (8)
C9a—C10a	1.389 (5)	1.386 (5)	1.392 (5)
C9a—H1c9a	1.0 (3)	1.0 (3)	1.0 (3)
C9b—C10b	1.384 (5)	1.383 (5)	1.385 (5)
C9b—H1c9b	0.960 (7)	0.960 (7)	0.960 (7)
C10a—H1c10a	1(3)	1(3)	1(3)
C10b—H1c10b	1.0 (14)	1.0 (14)	1.0 (14)
C11a—C12a	1.498 (5)	1.498 (5)	1.498 (5)
C11b—C12b	1.502 (5)	1.497 (5)	1.508 (5)
C12a—C13a	1.385 (6)	1.383 (6)	1.388 (6)
C12a—C17a	1.386 (6)	1.384 (6)	1.388 (6)
C12b—C13b	1.373 (6)	1.371 (6)	1.374 (6)
C12b—C17b	1.385 (6)	1.383 (6)	1.387 (6)
C13a—C14a	1.384 (5)	1.381 (5)	1.386 (5)
C13a—H1c13a	1.0 (7)	1.0 (7)	1.0 (7)
C13b—C14b	1.387 (5)	1.387 (5)	1.387 (5)
C13b—H1c13b	1.0 (6)	1.0 (6)	1.0 (6)
C14a—C15a	1.392 (6)	1.388 (7)	1.396 (7)
C14a—H1c14a	1(3)	1(3)	1(3)
C14b—C15b	1.389 (6)	1.386 (6)	1.392 (6)
C14b—H1c14b	1.0 (12)	1.0 (13)	1.0 (13)
C15a—C16a	1.394 (5)	1.384 (6)	1.404 (6)
C15a—C18a	1.484 (4)	1.476 (4)	1.491 (4)
C15b—C16b	1.380 (5)	1.377 (5)	1.383 (5)
C15b—C18b	1.498 (4)	1.497 (4)	1.499 (4)
C16a—C17a	1.389 (5)	1.386 (5)	1.393 (5)
C16a—H1c16a	0.960 (5)	0.960 (5)	0.960 (5)
C16b—C17b	1.383 (4)	1.376 (4)	1.390 (4)
C16b—H1c16b	0.96 (10)	0.96 (10)	0.96 (10)
C17a—H1c17a	1.0 (4)	1.0 (4)	1.0 (4)
C17b—H1c17b	1.0 (5)	1.0 (5)	1.0 (5)
C18a—C19a	1.394 (5)	1.390 (5)	1.399 (5)
C18a—C23a	1.399 (6)	1.393 (6)	1.404 (6)
C18b—C19b	1.392 (6)	1.391 (6)	1.394 (6)
C18b—C23b	1.396 (6)	1.392 (6)	1.399 (6)
C19a—C20a	1.382 (5)	1.381 (5)	1.383 (5)
C19a—H1c19a	1.0 (13)	1.0 (13)	1.0 (13)
C19b—C20b	1.385 (5)	1.378 (5)	1.392 (5)
C19b—H1c19b	1(2)	1(2)	1(2)
C20a—C21a	1.389 (6)	1.386 (7)	1.392 (7)
C20a—H1c20a	1(3)	1(3)	1(3)
C20b—C21b	1.380 (6)	1.375 (6)	1.384 (6)
C20b—H1c20b	1.0 (19)	1(2)	1(2)
C21a—C22a	1.376 (6)	1.371 (6)	1.381 (6)
C21a—H1c21a	0.96 (10)	0.96 (10)	0.96 (10)
C21b—C22b	1.373 (6)	1.371 (6)	1.375 (6)
C21b—H1c21b	1.0 (8)	1.0 (8)	1.0 (8)
C22a—C23a	1.384 (5)	1.382 (5)	1.387 (5)
C22a—H1c22a	1.0 (4)	1.0 (4)	1.0 (4)
C22b—C23b	1.381 (5)	1.374 (5)	1.389 (5)
C22b—H1c22b	1.0 (3)	1.0 (3)	1.0 (3)
C23a—H1c23a	0.96 (16)	0.96 (17)	0.96 (17)
C23b—H1c23b	0.960 (14)	0.960 (15)	0.960 (15)
C1a—O1a—C2a	115.5 (3)	115.5 (3)	115.6 (3)
C1b—O1b—C2b	114.5 (3)	114.4 (3)	114.5 (3)
C3a—N1a—C11a	122.4 (3)	122.0 (3)	122.7 (3)
C3a—N1a—H1n1a	113 (4)	112 (4)	113 (4)
C11a—N1a—H1n1a	122 (4)	121 (4)	124 (4)
C3b—N1b—C11b	121.0 (2)	120.4 (2)	121.5 (2)
C3b—N1b—H1n1b	117.3 (15)	117.2 (15)	117.5 (15)
C11b—N1b—H1n1b	121.6 (15)	121.0 (15)	122.2 (15)
O1a—C1a—H1c1a	109.47	109.47	109.47
O1a—C1a—H2c1a	109.47	109.47	109.47
O1a—C1a—H3c1a	109.47	109.47	109.47
H1c1a—C1a—H2c1a	109.47	109.47	109.47
H1c1a—C1a—H3c1a	109.47	109.47	109.47
H2c1a—C1a—H3c1a	109.47	109.47	109.47
O1b—C1b—H1c1b	109.47	109.47	109.47
O1b—C1b—H2c1b	109.47	109.47	109.47
O1b—C1b—H3c1b	109.47	109.47	109.47
H1c1b—C1b—H2c1b	109.47	109.47	109.47
H1c1b—C1b—H3c1b	109.47	109.47	109.47
H2c1b—C1b—H3c1b	109.47	109.47	109.47
O1a—C2a—O2a	123.8 (3)	123.4 (3)	124.2 (3)
O1a—C2a—C3a	112.7 (3)	112.5 (3)	112.9 (3)
O2a—C2a—C3a	123.5 (4)	123.4 (4)	123.7 (4)
O1b—C2b—O2b	124.2 (4)	124.1 (4)	124.3 (4)
O1b—C2b—C3b	112.6 (3)	112.5 (3)	112.6 (3)
O2b—C2b—C3b	123.2 (4)	123.2 (4)	123.3 (4)
N1a—C3a—C2a	111.4 (3)	111.0 (3)	111.8 (3)
N1a—C3a—C4a	111.6 (3)	111.4 (3)	111.7 (3)
N1a—C3a—H1c3a	107.2	107.06	107.35
C2a—C3a—C4a	111.0 (3)	110.9 (3)	111.1 (3)
C2a—C3a—H1c3a	107.81	107.43	108.19
C4a—C3a—H1c3a	107.62	107.44	107.8
N1b—C3b—C2b	112.6 (3)	112.5 (3)	112.7 (3)
N1b—C3b—C4b	113.1 (3)	112.9 (3)	113.4 (3)
N1b—C3b—H1c3b	104.51	104.21	104.81
C2b—C3b—C4b	109.1 (3)	109.0 (3)	109.1 (3)
C2b—C3b—H1c3b	108.98	108.94	109.01
C4b—C3b—H1c3b	108.35	108.22	108.48
C3a—C4a—C5a	113.1 (3)	112.6 (3)	113.6 (3)
C3a—C4a—H1c4a	109.47	109.47	109.47
C3a—C4a—H2c4a	109.47	109.47	109.47
C5a—C4a—H1c4a	109.47	109.47	109.47
C5a—C4a—H2c4a	109.47	109.47	109.47
H1c4a—C4a—H2c4a	105.58	105.05	106.1
C3b—C4b—C5b	114.2 (3)	114.1 (3)	114.3 (3)
C3b—C4b—H1c4b	109.47	109.47	109.47
C3b—C4b—H2c4b	109.47	109.47	109.47
C5b—C4b—H1c4b	109.47	109.47	109.47
C5b—C4b—H2c4b	109.47	109.47	109.47
H1c4b—C4b—H2c4b	104.28	104.2	104.36
C4a—C5a—C6a	120.3 (3)	120.1 (3)	120.5 (3)
C4a—C5a—C10a	121.1 (3)	120.9 (3)	121.3 (3)
C6a—C5a—C10a	118.6 (3)	118.6 (3)	118.6 (3)
C4b—C5b—C6b	119.5 (3)	119.2 (3)	119.9 (3)
C4b—C5b—C10b	122.2 (3)	122.1 (3)	122.3 (3)
C6b—C5b—C10b	118.3 (4)	118.0 (3)	118.5 (4)
C5a—C6a—C7a	120.7 (3)	120.5 (3)	120.8 (3)
C5a—C6a—H1c6a	119.68	119.62	119.73
C7a—C6a—H1c6a	119.67	119.61	119.73
C5b—C6b—C7b	120.9 (3)	120.7 (3)	121.0 (3)
C5b—C6b—H1c6b	119.57	119.5	119.63
C7b—C6b—H1c6b	119.57	119.5	119.63
C6a—C7a—C8a	120.7 (3)	120.3 (3)	121.1 (3)
C6a—C7a—H1c7a	119.67	119.47	119.87
C8a—C7a—H1c7a	119.67	119.46	119.87
C6b—C7b—C8b	120.4 (4)	120.4 (4)	120.4 (4)
C6b—C7b—H1c7b	119.79	119.78	119.8
C8b—C7b—H1c7b	119.79	119.78	119.8
C7a—C8a—C9a	119.0 (4)	118.6 (4)	119.4 (4)
C7a—C8a—H1c8a	120.51	120.32	120.69
C9a—C8a—H1c8a	120.51	120.33	120.7
C7b—C8b—C9b	119.7 (4)	119.7 (4)	119.7 (4)
C7b—C8b—H1c8b	120.16	120.14	120.17
C9b—C8b—H1c8b	120.16	120.14	120.17
C8a—C9a—C10a	120.4 (3)	120.1 (3)	120.6 (3)
C8a—C9a—H1c9a	119.81	119.68	119.94
C10a—C9a—H1c9a	119.81	119.68	119.94
C8b—C9b—C10b	119.7 (3)	119.6 (3)	119.7 (3)
C8b—C9b—H1c9b	120.16	120.13	120.19
C10b—C9b—H1c9b	120.16	120.13	120.19
C5a—C10a—C9a	120.7 (3)	120.5 (3)	120.9 (3)
C5a—C10a—H1c10a	119.64	119.54	119.74
C9a—C10a—H1c10a	119.64	119.54	119.74
C5b—C10b—C9b	121.1 (4)	121.1 (4)	121.1 (4)
C5b—C10b—H1c10b	119.46	119.45	119.47
C9b—C10b—H1c10b	119.46	119.45	119.47
O3a—C11a—N1a	123.5 (3)	123.3 (3)	123.6 (3)
O3a—C11a—C12a	120.6 (3)	120.3 (3)	120.8 (3)
N1a—C11a—C12a	116.0 (3)	115.8 (3)	116.1 (3)
O3b—C11b—N1b	122.3 (3)	122.0 (3)	122.7 (3)
O3b—C11b—C12b	120.7 (3)	120.7 (3)	120.8 (3)
N1b—C11b—C12b	116.9 (3)	116.7 (3)	117.2 (3)
C11a—C12a—C13a	118.2 (3)	117.8 (3)	118.5 (3)
C11a—C12a—C17a	123.3 (3)	122.7 (3)	123.9 (3)
C13a—C12a—C17a	118.5 (3)	118.2 (3)	118.8 (3)
C11b—C12b—C13b	118.3 (3)	118.2 (3)	118.5 (3)
C11b—C12b—C17b	123.1 (3)	123.0 (3)	123.1 (3)
C13b—C12b—C17b	118.6 (3)	118.4 (3)	118.7 (3)
C12a—C13a—C14a	120.5 (3)	120.4 (4)	120.6 (3)
C12a—C13a—H1c13a	119.75	119.71	119.79
C14a—C13a—H1c13a	119.75	119.71	119.79
C12b—C13b—C14b	121.2 (4)	121.1 (4)	121.2 (4)
C12b—C13b—H1c13b	119.42	119.4	119.45
C14b—C13b—H1c13b	119.42	119.39	119.45
C13a—C14a—C15a	121.7 (3)	121.6 (4)	121.9 (3)
C13a—C14a—H1c14a	119.13	119.06	119.2
C15a—C14a—H1c14a	119.13	119.06	119.2
C13b—C14b—C15b	121.2 (4)	121.0 (4)	121.4 (4)
C13b—C14b—H1c14b	119.41	119.32	119.51
C15b—C14b—H1c14b	119.41	119.32	119.51
C14a—C15a—C16a	117.3 (3)	117.3 (3)	117.3 (3)
C14a—C15a—C18a	121.0 (3)	121.0 (3)	121.1 (3)
C16a—C15a—C18a	121.6 (3)	121.5 (3)	121.7 (3)
C14b—C15b—C16b	116.6 (3)	116.3 (3)	117.0 (3)
C14b—C15b—C18b	121.2 (3)	120.6 (3)	121.8 (3)
C16b—C15b—C18b	122.1 (3)	121.8 (3)	122.4 (3)
C15a—C16a—C17a	121.0 (3)	120.9 (3)	121.0 (3)
C15a—C16a—H1c16a	119.52	119.48	119.56
C17a—C16a—H1c16a	119.52	119.48	119.56
C15b—C16b—C17b	122.7 (3)	122.3 (3)	123.2 (3)
C15b—C16b—H1c16b	118.63	118.42	118.83
C17b—C16b—H1c16b	118.63	118.42	118.83
C12a—C17a—C16a	120.9 (3)	120.9 (3)	120.9 (3)
C12a—C17a—H1c17a	119.54	119.54	119.54
C16a—C17a—H1c17a	119.54	119.53	119.54
C12b—C17b—C16b	119.7 (4)	119.6 (4)	119.7 (4)
C12b—C17b—H1c17b	120.16	120.13	120.2
C16b—C17b—H1c17b	120.17	120.13	120.2
C15a—C18a—C19a	121.4 (3)	120.9 (3)	121.9 (3)
C15a—C18a—C23a	121.7 (3)	121.6 (3)	121.9 (3)
C19a—C18a—C23a	116.9 (3)	116.3 (3)	117.4 (3)
C15b—C18b—C19b	120.8 (3)	120.7 (3)	120.9 (3)
C15b—C18b—C23b	121.7 (3)	121.7 (3)	121.7 (3)
C19b—C18b—C23b	117.5 (3)	117.4 (3)	117.7 (3)
C18a—C19a—C20a	122.0 (4)	121.4 (4)	122.6 (4)
C18a—C19a—H1c19a	118.99	118.71	119.28
C20a—C19a—H1c19a	118.99	118.71	119.28
C18b—C19b—C20b	120.9 (4)	120.4 (3)	121.5 (4)
C18b—C19b—H1c19b	119.54	119.26	119.82
C20b—C19b—H1c19b	119.53	119.25	119.81
C19a—C20a—C21a	119.8 (3)	119.5 (3)	120.1 (3)
C19a—C20a—H1c20a	120.09	119.95	120.24
C21a—C20a—H1c20a	120.09	119.95	120.24
C19b—C20b—C21b	121.0 (4)	120.6 (4)	121.3 (4)
C19b—C20b—H1c20b	119.52	119.36	119.69
C21b—C20b—H1c20b	119.52	119.36	119.69
C20a—C21a—C22a	119.4 (3)	119.4 (3)	119.4 (3)
C20a—C21a—H1c21a	120.31	120.3	120.32
C22a—C21a—H1c21a	120.31	120.3	120.32
C20b—C21b—C22b	118.4 (3)	118.3 (3)	118.5 (3)
C20b—C21b—H1c21b	120.8	120.75	120.86
C22b—C21b—H1c21b	120.8	120.75	120.85
C21a—C22a—C23a	120.5 (4)	120.0 (3)	121.0 (4)
C21a—C22a—H1c22a	119.76	119.51	120.01
C23a—C22a—H1c22a	119.76	119.51	120
C21b—C22b—C23b	121.4 (3)	121.3 (3)	121.6 (3)
C21b—C22b—H1c22b	119.29	119.2	119.37
C23b—C22b—H1c22b	119.29	119.2	119.38
C18a—C23a—C22a	121.4 (3)	120.7 (3)	122.2 (3)
C18a—C23a—H1c23a	119.28	118.9	119.66
C22a—C23a—H1c23a	119.28	118.9	119.66
C18b—C23b—C22b	120.7 (3)	120.6 (3)	120.8 (3)
C18b—C23b—H1c23b	119.64	119.6	119.68
C22b—C23b—H1c23b	119.64	119.6	119.68

(I_phaseI)

Crystal data

C23H21NO3	F(000) = 760
Mr = 359.4	Dx = 1.300 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 3437 reflections
a = 5.0479 (2) Å	θ = 4.2–65.4°
b = 8.6330 (4) Å	µ = 0.69 mm^−1
c = 42.1525 (15) Å	T = 160 K
β = 90.513 (3)°	Rectrangular, colorless
V = 1836.87 (13) Å^3	0.24 × 0.16 × 0.11 mm
Z = 4

Data collection

SuperNova, Dual, Cu at home/near, Eos diffractometer	4555 independent reflections
Radiation source: X-ray tube	4219 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.020
Detector resolution: 7.9580 pixels mm^-1	θmax = 65.3°, θmin = 2.1°
ω scans	h = −5→5
Absorption correction: multi-scan CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −10→10
Tmin = 0.898, Tmax = 1	l = −27→49
6108 measured reflections

Refinement

Refinement on F	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
wR(F^2) = 0.049	(Δ/σ)max = 0.0003
S = 1.54	Δρmax = 0.17 e Å^−3
4555 reflections	Δρmin = −0.15 e Å^−3
494 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 3400 (300)
163 constraints	Absolute structure: 1218 of Friedel pairs used in the refinement

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

	x	y	z	Uiso*/Ueq
O1a	0.3209 (5)	0.0596 (4)	0.45564 (5)	0.0488 (8)
O1b	0.8559 (4)	0.5788 (4)	0.04235 (4)	0.0340 (6)
O2a	0.1752 (8)	0.2511 (5)	0.48507 (7)	0.0852 (14)
O2b	0.6560 (6)	0.3932 (4)	0.01419 (5)	0.0533 (9)
O3a	0.8541 (4)	0.2654 (4)	0.39851 (5)	0.0383 (7)
O3b	0.5560 (4)	0.4070 (4)	0.09509 (4)	0.0330 (6)
N1a	0.4147 (5)	0.253675	0.40714 (5)	0.0265 (7)
N1b	0.9919 (4)	0.3722 (4)	0.08810 (5)	0.0235 (7)
C1a	0.1977 (9)	−0.0488 (6)	0.47710 (8)	0.0552 (14)
C1b	0.7025 (7)	0.6917 (5)	0.02466 (7)	0.0414 (11)
C2a	0.2913 (6)	0.2070 (5)	0.46255 (6)	0.0335 (9)
C2b	0.8031 (6)	0.4325 (5)	0.03514 (6)	0.0291 (9)
C3a	0.4295 (6)	0.3143 (5)	0.43929 (6)	0.0281 (8)
C3b	0.9592 (6)	0.3187 (5)	0.05575 (6)	0.0255 (8)
C4a	0.3154 (6)	0.4788 (5)	0.44110 (7)	0.0336 (9)
C4b	0.8291 (6)	0.1568 (5)	0.05334 (6)	0.0296 (9)
C5a	0.4559 (6)	0.5923 (5)	0.41986 (6)	0.0316 (9)
C5b	0.9369 (6)	0.0394 (5)	0.07655 (6)	0.0288 (8)
C6a	0.3833 (7)	0.6055 (5)	0.38816 (7)	0.0388 (10)
C6b	0.8186 (6)	0.0248 (5)	0.10632 (7)	0.0331 (9)
C7a	0.5160 (7)	0.7071 (6)	0.36839 (7)	0.0431 (11)
C7b	0.9087 (6)	−0.0847 (5)	0.12755 (7)	0.0384 (10)
C8a	0.7185 (7)	0.7981 (5)	0.37988 (7)	0.0414 (11)
C8b	1.1171 (7)	−0.1809 (5)	0.12010 (8)	0.0398 (10)
C9a	0.7912 (7)	0.7871 (5)	0.41144 (8)	0.0435 (11)
C9b	1.2378 (6)	−0.1683 (5)	0.09081 (8)	0.0380 (10)
C10a	0.6598 (6)	0.6856 (5)	0.43137 (7)	0.0369 (10)
C10b	1.1468 (6)	−0.0567 (5)	0.06921 (7)	0.0352 (10)
C11a	0.6282 (5)	0.2414 (5)	0.38875 (6)	0.0275 (8)
C11b	0.7833 (5)	0.4085 (5)	0.10570 (6)	0.0236 (8)
C12a	0.5746 (5)	0.1993 (5)	0.35478 (6)	0.0271 (8)
C12b	0.8386 (5)	0.4494 (5)	0.13964 (6)	0.0235 (8)
C13a	0.7404 (7)	0.2577 (6)	0.33210 (7)	0.0489 (12)
C13b	0.6711 (7)	0.5509 (6)	0.15456 (7)	0.0430 (11)
C14a	0.7010 (7)	0.2228 (6)	0.30031 (7)	0.0505 (13)
C14b	0.7094 (7)	0.5917 (6)	0.18620 (7)	0.0439 (11)
C15a	0.5008 (6)	0.1252 (5)	0.29014 (6)	0.0274 (8)
C15b	0.9146 (5)	0.5288 (5)	0.20401 (6)	0.0248 (8)
C16a	0.3368 (7)	0.0662 (6)	0.31326 (7)	0.0439 (11)
C16b	1.0803 (6)	0.4268 (6)	0.18894 (7)	0.0414 (11)
C17a	0.3717 (7)	0.1040 (5)	0.34503 (7)	0.0430 (11)
C17b	1.0469 (6)	0.3877 (6)	0.15710 (7)	0.0393 (10)
C18a	0.4636 (6)	0.0879 (5)	0.25594 (6)	0.0275 (8)
C18b	0.9493 (5)	0.5681 (5)	0.23843 (6)	0.0279 (8)
C19a	0.6213 (7)	0.1549 (6)	0.23294 (7)	0.0482 (12)
C19b	0.7833 (7)	0.6755 (6)	0.25305 (7)	0.0419 (11)
C20a	0.5851 (8)	0.1201 (6)	0.20106 (7)	0.0535 (13)
C20b	0.8104 (7)	0.7094 (6)	0.28491 (7)	0.0442 (11)
C21a	0.3936 (7)	0.0194 (5)	0.19124 (7)	0.0363 (10)
C21b	1.0040 (6)	0.6387 (5)	0.30308 (7)	0.0354 (10)
C22a	0.2357 (8)	−0.0474 (6)	0.21338 (8)	0.0497 (13)
C22b	1.1728 (7)	0.5358 (6)	0.28887 (7)	0.0418 (11)
C23a	0.2706 (7)	−0.0139 (6)	0.24550 (7)	0.0488 (12)
C23b	1.1471 (7)	0.5003 (5)	0.25696 (7)	0.0356 (10)
H1c1a	0.251308	−0.152259	0.471816	0.0828*
H2c1a	0.25145	−0.025677	0.498482	0.0828*
H3c1a	0.008574	−0.040418	0.475241	0.0828*
H1c1b	0.742097	0.793688	0.032416	0.062*
H2c1b	0.746415	0.685269	0.002591	0.062*
H3c1b	0.517087	0.670854	0.02725	0.062*
H1c3a	0.613348	0.319577	0.445211	0.0421*
H1c3b	1.136613	0.311321	0.047862	0.0382*
H1c4a	0.130402	0.476416	0.435663	0.0504*
H2c4a	0.323956	0.514785	0.462634	0.0504*
H1c4b	0.641145	0.166454	0.056025	0.0444*
H2c4b	0.846895	0.117959	0.032128	0.0444*
H1c6a	0.240255	0.543918	0.379864	0.0465*
H1c6b	0.674133	0.091404	0.111932	0.0397*
H1c7a	0.465776	0.714034	0.346419	0.0517*
H1c7b	0.825345	−0.094164	0.147836	0.0461*
H1c8a	0.80861	0.868643	0.366076	0.0497*
H1c8b	1.178532	−0.256411	0.13517	0.0477*
H1c9a	0.933146	0.849834	0.419618	0.0522*
H1c9b	1.382187	−0.2354	0.085392	0.0456*
H1c10a	0.710185	0.679619	0.453352	0.0442*
H1c10b	1.231312	−0.046782	0.048999	0.0422*
H1n1a	0.248 (7)	0.240 (4)	0.3988 (7)	0.0319*
H1n1b	1.162 (7)	0.384 (4)	0.0961 (7)	0.0282*
H1c13a	0.885181	0.323399	0.338318	0.0586*
H1c13b	0.524743	0.594576	0.142923	0.0515*
H1c14a	0.816527	0.267965	0.284877	0.0606*
H1c14b	0.591423	0.664648	0.195856	0.0527*
H1c16a	0.195607	−0.002446	0.307208	0.0527*
H1c16b	1.223823	0.38108	0.200739	0.0496*
H1c17a	0.251917	0.062771	0.360457	0.0516*
H1c17b	1.168626	0.317575	0.147232	0.0472*
H1c19a	0.757737	0.226421	0.239165	0.0578*
H1c19b	0.648297	0.726572	0.24074	0.0503*
H1c20a	0.697303	0.167937	0.185617	0.0642*
H1c20b	0.693164	0.782965	0.294526	0.0531*
H1c21a	0.370444	−0.004103	0.169127	0.0436*
H1c21b	1.02055	0.661099	0.325313	0.0425*
H1c22a	0.099024	−0.118109	0.206831	0.0596*
H1c22b	1.310666	0.487709	0.301235	0.0502*
H1c23a	0.157745	−0.062754	0.260734	0.0586*
H1c23b	1.267223	0.427894	0.247501	0.0427*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1a	0.0640 (16)	0.0383 (14)	0.0445 (12)	0.0019 (13)	0.0228 (10)	0.0012 (11)
O1b	0.0440 (12)	0.0249 (11)	0.0329 (10)	−0.0020 (10)	−0.0108 (8)	0.0036 (9)
O2a	0.158 (3)	0.0436 (17)	0.0553 (16)	0.001 (2)	0.0651 (19)	−0.0016 (14)
O2b	0.0797 (18)	0.0361 (14)	0.0434 (12)	−0.0009 (14)	−0.0347 (12)	−0.0036 (12)
O3a	0.0195 (10)	0.0602 (16)	0.0353 (10)	−0.0008 (10)	−0.0001 (7)	−0.0064 (10)
O3b	0.0208 (10)	0.0468 (14)	0.0313 (9)	0.0018 (10)	−0.0034 (7)	−0.0025 (10)
N1a	0.0209 (12)	0.0303 (14)	0.0284 (11)	−0.0013 (10)	−0.0008 (8)	−0.0034 (10)
N1b	0.0198 (11)	0.0259 (13)	0.0249 (10)	−0.0004 (9)	−0.0014 (8)	0.0007 (9)
C1a	0.085 (3)	0.043 (2)	0.0381 (18)	−0.013 (2)	0.0091 (17)	0.0025 (16)
C1b	0.061 (2)	0.0283 (18)	0.0349 (16)	0.0089 (17)	−0.0082 (14)	0.0049 (14)
C2a	0.0415 (17)	0.0342 (18)	0.0249 (13)	−0.0037 (15)	0.0040 (11)	−0.0021 (13)
C2b	0.0370 (16)	0.0278 (16)	0.0223 (13)	0.0022 (14)	−0.0005 (11)	−0.0006 (11)
C3a	0.0256 (14)	0.0322 (16)	0.0263 (13)	0.0045 (12)	−0.0004 (10)	−0.0023 (12)
C3b	0.0254 (14)	0.0271 (15)	0.0239 (12)	−0.0002 (12)	−0.0019 (10)	−0.0021 (11)
C4a	0.0326 (16)	0.0375 (18)	0.0308 (14)	0.0030 (14)	0.0045 (11)	−0.0038 (13)
C4b	0.0318 (15)	0.0243 (16)	0.0326 (14)	−0.0010 (13)	−0.0085 (11)	−0.0028 (12)
C5a	0.0329 (16)	0.0294 (17)	0.0326 (13)	0.0073 (14)	0.0033 (11)	−0.0013 (13)
C5b	0.0310 (15)	0.0199 (15)	0.0353 (14)	−0.0038 (12)	−0.0068 (10)	−0.0042 (12)
C6a	0.0339 (17)	0.046 (2)	0.0368 (15)	0.0045 (15)	−0.0047 (12)	−0.0014 (15)
C6b	0.0351 (17)	0.0240 (16)	0.0402 (15)	0.0008 (14)	0.0001 (12)	−0.0006 (13)
C7a	0.0454 (19)	0.049 (2)	0.0349 (16)	−0.0011 (18)	−0.0040 (13)	0.0042 (16)
C7b	0.0430 (18)	0.0356 (19)	0.0367 (15)	0.0029 (16)	0.0008 (12)	0.0040 (15)
C8a	0.0457 (18)	0.037 (2)	0.0415 (17)	0.0004 (16)	0.0035 (14)	0.0080 (15)
C8b	0.0402 (17)	0.0327 (18)	0.0463 (17)	0.0021 (15)	−0.0080 (13)	0.0059 (15)
C9a	0.0418 (18)	0.039 (2)	0.0498 (18)	−0.0041 (17)	−0.0031 (14)	−0.0038 (16)
C9b	0.0302 (15)	0.0296 (17)	0.0541 (18)	0.0079 (14)	−0.0053 (13)	−0.0047 (15)
C10a	0.0410 (17)	0.0364 (19)	0.0332 (14)	0.0029 (15)	−0.0050 (12)	−0.0035 (13)
C10b	0.0363 (17)	0.0317 (18)	0.0375 (15)	−0.0026 (14)	−0.0012 (12)	−0.0049 (13)
C11a	0.0212 (14)	0.0305 (17)	0.0310 (13)	0.0052 (12)	0.0016 (10)	−0.0016 (12)
C11b	0.0198 (13)	0.0196 (14)	0.0313 (13)	−0.0011 (12)	−0.0013 (10)	0.0048 (12)
C12a	0.0227 (14)	0.0294 (16)	0.0292 (13)	0.0027 (13)	0.0016 (10)	−0.0006 (12)
C12b	0.0234 (14)	0.0205 (14)	0.0266 (13)	−0.0004 (11)	0.0027 (10)	0.0043 (11)
C13a	0.0408 (18)	0.075 (3)	0.0307 (15)	−0.030 (2)	−0.0011 (12)	−0.0045 (17)
C13b	0.0400 (18)	0.055 (2)	0.0342 (15)	0.0240 (18)	−0.0087 (12)	−0.0056 (15)
C14a	0.0467 (19)	0.076 (3)	0.0287 (15)	−0.030 (2)	0.0036 (13)	−0.0016 (17)
C14b	0.051 (2)	0.048 (2)	0.0327 (15)	0.0240 (18)	−0.0020 (13)	−0.0091 (15)
C15a	0.0240 (14)	0.0252 (15)	0.0329 (14)	0.0049 (12)	−0.0006 (10)	0.0004 (12)
C15b	0.0245 (14)	0.0210 (14)	0.0289 (13)	−0.0025 (12)	0.0029 (10)	0.0020 (11)
C16a	0.0418 (18)	0.054 (2)	0.0364 (16)	−0.0222 (18)	0.0073 (12)	−0.0131 (16)
C16b	0.0320 (16)	0.062 (2)	0.0299 (14)	0.0177 (17)	−0.0071 (11)	−0.0015 (15)
C17a	0.0427 (18)	0.051 (2)	0.0360 (15)	−0.0205 (17)	0.0161 (13)	−0.0070 (15)
C17b	0.0368 (17)	0.052 (2)	0.0290 (14)	0.0170 (16)	−0.0018 (11)	−0.0084 (14)
C18a	0.0284 (14)	0.0230 (15)	0.0311 (13)	0.0058 (12)	−0.0018 (10)	−0.0019 (12)
C18b	0.0266 (14)	0.0295 (16)	0.0276 (13)	−0.0071 (12)	0.0038 (10)	0.0010 (12)
C19a	0.049 (2)	0.062 (3)	0.0340 (16)	−0.0229 (19)	0.0062 (14)	−0.0102 (16)
C19b	0.0378 (18)	0.056 (2)	0.0322 (15)	0.0116 (17)	0.0000 (12)	−0.0031 (15)
C20a	0.057 (2)	0.073 (3)	0.0305 (16)	−0.020 (2)	0.0074 (14)	−0.0092 (17)
C20b	0.0421 (18)	0.056 (2)	0.0348 (15)	0.0056 (18)	0.0049 (13)	−0.0107 (16)
C21a	0.0432 (18)	0.0365 (18)	0.0292 (14)	0.0057 (15)	−0.0022 (11)	−0.0042 (13)
C21b	0.0386 (17)	0.0373 (18)	0.0305 (14)	−0.0119 (15)	0.0021 (12)	−0.0024 (13)
C22a	0.056 (2)	0.053 (3)	0.0402 (17)	−0.0184 (19)	−0.0129 (15)	−0.0022 (17)
C22b	0.0415 (18)	0.047 (2)	0.0372 (15)	0.0021 (17)	−0.0076 (12)	0.0007 (15)
C23a	0.053 (2)	0.059 (2)	0.0346 (16)	−0.0252 (19)	−0.0022 (14)	0.0054 (16)
C23b	0.0422 (18)	0.0329 (18)	0.0316 (15)	0.0049 (15)	−0.0021 (12)	−0.0058 (13)

Geometric parameters (Å, º)

O1a—C1a	1.446 (5)	C9b—C10b	1.400 (5)
O1a—C2a	1.314 (6)	C9b—H1c9b	0.96
O1b—C1b	1.447 (5)	C10a—H1c10a	0.96
O1b—C2b	1.326 (5)	C10b—H1c10b	0.96
O2a—C2a	1.183 (5)	C11a—C12a	1.500 (4)
O2b—C2b	1.198 (4)	C11b—C12b	1.498 (4)
O3a—C11a	1.227 (3)	C12a—C13a	1.372 (5)
O3b—C11b	1.228 (3)	C12a—C17a	1.374 (5)
N1a—C3a	1.454 (3)	C12b—C13b	1.374 (5)
N1a—C11a	1.337 (3)	C12b—C17b	1.384 (4)
N1a—H1n1a	0.92 (3)	C13a—C14a	1.386 (4)
N1b—C3b	1.448 (3)	C13a—H1c13a	0.96
N1b—C11b	1.331 (4)	C13b—C14b	1.391 (4)
N1b—H1n1b	0.92 (3)	C13b—H1c13b	0.96
C1a—H1c1a	0.96	C14a—C15a	1.381 (5)
C1a—H2c1a	0.96	C14a—H1c14a	0.96
C1a—H3c1a	0.96	C14b—C15b	1.385 (5)
C1b—H1c1b	0.96	C14b—H1c14b	0.96
C1b—H2c1b	0.96	C15a—C16a	1.381 (5)
C1b—H3c1b	0.96	C15a—C18a	1.487 (4)
C2a—C3a	1.523 (5)	C15b—C16b	1.374 (5)
C2b—C3b	1.526 (5)	C15b—C18b	1.499 (4)
C3a—C4a	1.534 (6)	C16a—C17a	1.388 (4)
C3a—H1c3a	0.96	C16a—H1c16a	0.96
C3b—C4b	1.547 (5)	C16b—C17b	1.393 (4)
C3b—H1c3b	0.96	C16b—H1c16b	0.96
C4a—C5a	1.509 (5)	C17a—H1c17a	0.96
C4a—H1c4a	0.96	C17b—H1c17b	0.96
C4a—H2c4a	0.96	C18a—C19a	1.386 (5)
C4b—C5b	1.507 (5)	C18a—C23a	1.381 (5)
C4b—H1c4b	0.96	C18b—C19b	1.397 (5)
C4b—H2c4b	0.96	C18b—C23b	1.391 (5)
C5a—C6a	1.387 (4)	C19a—C20a	1.387 (5)
C5a—C10a	1.391 (5)	C19a—H1c19a	0.96
C5b—C6b	1.400 (4)	C19b—C20b	1.380 (4)
C5b—C10b	1.383 (5)	C19b—H1c19b	0.96
C6a—C7a	1.387 (5)	C20a—C21a	1.362 (6)
C6a—H1c6a	0.96	C20a—H1c20a	0.96
C6b—C7b	1.376 (5)	C20b—C21b	1.379 (5)
C6b—H1c6b	0.96	C20b—H1c20b	0.96
C7a—C8a	1.373 (5)	C21a—C22a	1.361 (5)
C7a—H1c7a	0.96	C21a—H1c21a	0.96
C7b—C8b	1.379 (5)	C21b—C22b	1.372 (6)
C7b—H1c7b	0.96	C21b—H1c21b	0.96
C8a—C9a	1.380 (5)	C22a—C23a	1.394 (5)
C8a—H1c8a	0.96	C22a—H1c22a	0.96
C8b—C9b	1.386 (5)	C22b—C23b	1.385 (4)
C8b—H1c8b	0.96	C22b—H1c22b	0.96
C9a—C10a	1.387 (5)	C23a—H1c23a	0.96
C9a—H1c9a	0.96	C23b—H1c23b	0.96
C1a—O1a—C2a	115.9 (3)	C9a—C10a—H1c10a	119.64
C1b—O1b—C2b	114.7 (3)	C5b—C10b—C9b	121.0 (3)
C3a—N1a—C11a	122.3 (2)	C5b—C10b—H1c10b	119.51
C3a—N1a—H1n1a	116.2 (19)	C9b—C10b—H1c10b	119.51
C11a—N1a—H1n1a	120.6 (19)	O3a—C11a—N1a	122.9 (3)
C3b—N1b—C11b	121.1 (2)	O3a—C11a—C12a	121.4 (2)
C3b—N1b—H1n1b	118.5 (19)	N1a—C11a—C12a	115.7 (2)
C11b—N1b—H1n1b	120.4 (19)	O3b—C11b—N1b	122.4 (2)
O1a—C1a—H1c1a	109.47	O3b—C11b—C12b	121.1 (2)
O1a—C1a—H2c1a	109.47	N1b—C11b—C12b	116.5 (2)
O1a—C1a—H3c1a	109.47	C11a—C12a—C13a	118.1 (3)
H1c1a—C1a—H2c1a	109.47	C11a—C12a—C17a	123.9 (3)
H1c1a—C1a—H3c1a	109.47	C13a—C12a—C17a	118.0 (3)
H2c1a—C1a—H3c1a	109.47	C11b—C12b—C13b	118.5 (3)
O1b—C1b—H1c1b	109.47	C11b—C12b—C17b	123.5 (3)
O1b—C1b—H2c1b	109.47	C13b—C12b—C17b	118.0 (3)
O1b—C1b—H3c1b	109.47	C12a—C13a—C14a	120.7 (4)
H1c1b—C1b—H2c1b	109.47	C12a—C13a—H1c13a	119.64
H1c1b—C1b—H3c1b	109.47	C14a—C13a—H1c13a	119.64
H2c1b—C1b—H3c1b	109.47	C12b—C13b—C14b	121.3 (3)
O1a—C2a—O2a	123.2 (4)	C12b—C13b—H1c13b	119.37
O1a—C2a—C3a	113.1 (3)	C14b—C13b—H1c13b	119.37
O2a—C2a—C3a	123.6 (4)	C13a—C14a—C15a	122.0 (3)
O1b—C2b—O2b	124.1 (3)	C13a—C14a—H1c14a	118.98
O1b—C2b—C3b	112.4 (2)	C15a—C14a—H1c14a	118.98
O2b—C2b—C3b	123.5 (4)	C13b—C14b—C15b	121.2 (4)
N1a—C3a—C2a	111.2 (3)	C13b—C14b—H1c14b	119.41
N1a—C3a—C4a	111.3 (2)	C15b—C14b—H1c14b	119.41
N1a—C3a—H1c3a	107.52	C14a—C15a—C16a	116.6 (3)
C2a—C3a—C4a	110.9 (3)	C14a—C15a—C18a	121.2 (3)
C2a—C3a—H1c3a	107.97	C16a—C15a—C18a	122.2 (3)
C4a—C3a—H1c3a	107.8	C14b—C15b—C16b	117.1 (3)
N1b—C3b—C2b	112.6 (3)	C14b—C15b—C18b	121.1 (3)
N1b—C3b—C4b	113.2 (3)	C16b—C15b—C18b	121.8 (3)
N1b—C3b—H1c3b	104.4	C15a—C16a—C17a	121.5 (4)
C2b—C3b—C4b	109.1 (2)	C15a—C16a—H1c16a	119.25
C2b—C3b—H1c3b	108.93	C17a—C16a—H1c16a	119.24
C4b—C3b—H1c3b	108.3	C15b—C16b—C17b	122.1 (3)
C3a—C4a—C5a	113.1 (3)	C15b—C16b—H1c16b	118.93
C3a—C4a—H1c4a	109.47	C17b—C16b—H1c16b	118.93
C3a—C4a—H2c4a	109.47	C12a—C17a—C16a	121.1 (3)
C5a—C4a—H1c4a	109.47	C12a—C17a—H1c17a	119.44
C5a—C4a—H2c4a	109.47	C16a—C17a—H1c17a	119.45
H1c4a—C4a—H2c4a	105.54	C12b—C17b—C16b	120.2 (3)
C3b—C4b—C5b	114.5 (2)	C12b—C17b—H1c17b	119.88
C3b—C4b—H1c4b	109.47	C16b—C17b—H1c17b	119.88
C3b—C4b—H2c4b	109.47	C15a—C18a—C19a	121.3 (3)
C5b—C4b—H1c4b	109.47	C15a—C18a—C23a	121.9 (3)
C5b—C4b—H2c4b	109.47	C19a—C18a—C23a	116.7 (3)
H1c4b—C4b—H2c4b	103.95	C15b—C18b—C19b	120.8 (3)
C4a—C5a—C6a	120.2 (3)	C15b—C18b—C23b	121.7 (3)
C4a—C5a—C10a	121.3 (3)	C19b—C18b—C23b	117.5 (3)
C6a—C5a—C10a	118.5 (3)	C18a—C19a—C20a	121.1 (4)
C4b—C5b—C6b	119.2 (3)	C18a—C19a—H1c19a	119.47
C4b—C5b—C10b	122.1 (3)	C20a—C19a—H1c19a	119.47
C6b—C5b—C10b	118.7 (3)	C18b—C19b—C20b	121.0 (3)
C5a—C6a—C7a	120.4 (3)	C18b—C19b—H1c19b	119.48
C5a—C6a—H1c6a	119.81	C20b—C19b—H1c19b	119.48
C7a—C6a—H1c6a	119.81	C19a—C20a—C21a	121.3 (4)
C5b—C6b—C7b	120.2 (3)	C19a—C20a—H1c20a	119.35
C5b—C6b—H1c6b	119.89	C21a—C20a—H1c20a	119.35
C7b—C6b—H1c6b	119.89	C19b—C20b—C21b	120.7 (4)
C6a—C7a—C8a	120.8 (3)	C19b—C20b—H1c20b	119.67
C6a—C7a—H1c7a	119.61	C21b—C20b—H1c20b	119.67
C8a—C7a—H1c7a	119.61	C20a—C21a—C22a	118.7 (3)
C6b—C7b—C8b	120.9 (3)	C20a—C21a—H1c21a	120.64
C6b—C7b—H1c7b	119.54	C22a—C21a—H1c21a	120.64
C8b—C7b—H1c7b	119.54	C20b—C21b—C22b	119.0 (3)
C7a—C8a—C9a	119.4 (4)	C20b—C21b—H1c21b	120.52
C7a—C8a—H1c8a	120.29	C22b—C21b—H1c21b	120.52
C9a—C8a—H1c8a	120.29	C21a—C22a—C23a	120.6 (4)
C7b—C8b—C9b	119.9 (3)	C21a—C22a—H1c22a	119.72
C7b—C8b—H1c8b	120.06	C23a—C22a—H1c22a	119.72
C9b—C8b—H1c8b	120.06	C21b—C22b—C23b	120.9 (3)
C8a—C9a—C10a	120.2 (4)	C21b—C22b—H1c22b	119.53
C8a—C9a—H1c9a	119.9	C23b—C22b—H1c22b	119.53
C10a—C9a—H1c9a	119.9	C18a—C23a—C22a	121.6 (3)
C8b—C9b—C10b	119.3 (3)	C18a—C23a—H1c23a	119.19
C8b—C9b—H1c9b	120.37	C22a—C23a—H1c23a	119.19
C10b—C9b—H1c9b	120.37	C18b—C23b—C22b	120.8 (3)
C5a—C10a—C9a	120.7 (3)	C18b—C23b—H1c23b	119.58
C5a—C10a—H1c10a	119.64	C22b—C23b—H1c23b	119.58
O1a—C2a—C3a—N1a	36.2 (3)	C2a—C3a—N1a—C11a	−130.1 (3)
O1b—C2b—C3b—N1b	36.4 (3)	C2b—C3b—N1b—C11b	56.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4a—H1c4a···O3a^i	0.96	2.77	3.459 (4)	129.24
C10a—H1c10a···O2a^ii	0.96	2.72	3.656 (4)	163.61
C10b—H1c10b···O2b^iii	0.96	2.78	3.688 (4)	158.56
N1a—H1n1a···O3a^i	0.92 (3)	2.00 (3)	2.852 (3)	154 (3)
N1b—H1n1b···O3b^iv	0.92 (3)	2.00 (3)	2.876 (3)	157 (3)

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

(I_phaseII)

Crystal data

C23H21NO3	F(000) = 3040
Mr = 359.4	Dx = 1.312 Mg m^−3
Monoclinic, B21	Cu Kα radiation, λ = 1.54184 Å
a = 10.0754 (2) Å	Cell parameters from 3948 reflections
b = 8.5898 (3) Å	θ = 4.2–65.7°
c = 84.0864 (14) Å	µ = 0.70 mm^−1
β = 90.884 (3)°	T = 100 K
V = 7276.4 (3) Å^3	Rectrangular, colorless
Z = 16	0.24 × 0.16 × 0.11 mm

Data collection

SuperNova, Dual, Cu at home/near, Eos diffractometer	8898 independent reflections
Radiation source: X-ray tube	5940 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 7.9580 pixels mm^-1	θmax = 65.8°, θmin = 3.2°
ω scans	h = −11→11
Absorption correction: multi-scan	k = −10→7
Tmin = 0.966, Tmax = 1	l = −87→98
13838 measured reflections

Refinement

Refinement on F	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
wR(F^2) = 0.053	(Δ/σ)max < 0.001
S = 1.35	Δρmax = 0.22 e Å^−3
8898 reflections	Δρmin = −0.21 e Å^−3
1 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 1998.78
1309 constraints	Absolute structure: 2293 of Friedel pairs used in the refinement

Special details

Refinement. The superstructure model was derived from the commensurately modulated structure model using JANA2006. The scale factor has been refined with a damping factor of 1.

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

	x	y	z	Uiso*/Ueq
O1a-1	0.163487	0.052529	0.228295	0.0324
O1a-2	0.664614	0.064725	0.227747	0.0324
O1b-1	0.430515	0.577937	0.021036	0.0246
O1b-2	0.929536	0.575363	0.021203	0.0246
O2a-1	0.084228	0.246474	0.242814	0.0528
O2a-2	0.587399	0.26123	0.24216	0.0528
O2b-1	0.331843	0.390845	0.006598	0.0356
O2b-2	0.827385	0.387425	0.007195	0.0356
O3a-1	0.43166	0.274224	0.199869	0.0268
O3a-2	0.932486	0.25823	0.19935	0.0268
O3b-1	0.282052	0.405893	0.04691	0.0241
O3b-2	0.782848	0.400887	0.047626	0.0241
N1a-1	0.211317	0.247607	0.204082	0.0202
N1a-2	0.710829	0.259743	0.203261	0.0202
N1b-1	0.500153	0.369328	0.043804	0.0174
N1b-2	0.001505	0.368136	0.044058	0.0174
C1a-1	0.100894	0.944551	0.23889	0.0344
C1a-2	0.60104	0.956921	0.238457	0.0344
C1b-1	0.351409	0.690829	0.012251	0.029
C1b-2	0.850318	0.687877	0.012396	0.029
C2a-1	0.14603	0.201635	0.231639	0.0246
C2a-2	0.648296	0.214085	0.231092	0.0246
C2b-1	0.405925	0.430677	0.017232	0.0214
C2b-2	0.903035	0.428071	0.017644	0.0214
C3a-1	0.216302	0.309353	0.220179	0.0215
C3a-2	0.718538	0.319971	0.219442	0.0215
C3b-1	0.484508	0.316487	0.027472	0.0193
C3b-2	0.982939	0.314639	0.027789	0.0193
C4a-1	0.158771	0.475486	0.220967	0.0229
C4a-2	0.664785	0.488078	0.220368	0.0229
C4b-1	0.419107	0.152866	0.026168	0.0221
C4b-2	0.918275	0.150434	0.026552	0.0221
C5a-1	0.229353	0.587552	0.21026	0.0232
C5a-2	0.735811	0.60076	0.20967	0.0232
C5b-1	0.473491	0.035571	0.037878	0.0223
C5b-2	0.972047	0.033825	0.038454	0.0223
C6a-1	0.194869	0.597681	0.194289	0.0271
C6a-2	0.698568	0.613437	0.193756	0.0271
C6b-1	0.414649	0.021264	0.05268	0.0246
C6b-2	0.914428	0.021042	0.053399	0.0246
C7a-1	0.26359	0.695481	0.184279	0.0287
C7a-2	0.762692	0.716269	0.183793	0.0287
C7b-1	0.459853	0.911893	0.063573	0.0273
C7b-2	0.958555	0.911945	0.064241	0.0273
C8a-1	0.367291	0.788099	0.190015	0.0273
C8a-2	0.866526	0.808613	0.189635	0.0273
C8b-1	0.56489	0.815782	0.05996	0.029
C8b-2	0.06208	0.813908	0.060604	0.029
C9a-1	0.400367	0.780795	0.206053	0.0289
C9a-2	0.903725	0.797301	0.205446	0.0289
C9b-1	0.625762	0.829213	0.045206	0.0285
C9b-2	0.122021	0.825157	0.045855	0.0285
C10a-1	0.332722	0.681949	0.216134	0.0254
C10a-2	0.839083	0.693409	0.215393	0.0254
C10b-1	0.579408	0.938201	0.034321	0.0246
C10b-2	0.077377	0.934709	0.034965	0.0246
C11a-1	0.318083	0.243194	0.194968	0.0193
C11a-2	0.817629	0.240256	0.194303	0.0193
C11b-1	0.396749	0.406579	0.052466	0.0177
C11b-2	0.897428	0.403107	0.05289	0.0177
C12a-1	0.294194	0.200624	0.177882	0.0194
C12a-2	0.790885	0.19742	0.17728	0.0194
C12b-1	0.422945	0.447288	0.069534	0.0182
C12b-2	0.925695	0.444504	0.070034	0.0182
C13a-1	0.365049	0.278518	0.166312	0.0251
C13a-2	0.885782	0.23577	0.166243	0.0251
C13b-1	0.341469	0.553878	0.076683	0.0369
C13b-2	0.838477	0.541066	0.077577	0.0369
C14a-1	0.345082	0.243792	0.150358	0.0266
C14a-2	0.866869	0.199564	0.150363	0.0266
C14b-1	0.360514	0.595601	0.092492	0.0371
C14b-2	0.857707	0.582685	0.093377	0.0371
C15a-1	0.257305	0.127034	0.145429	0.0203
C15a-2	0.75423	0.12205	0.144896	0.0203
C15b-1	0.460215	0.528879	0.101764	0.0185
C15b-2	0.964887	0.524965	0.102202	0.0185
C16a-1	0.186303	0.049166	0.15726	0.0256
C16a-2	0.660159	0.082366	0.156014	0.0256
C16b-1	0.539487	0.42035	0.094326	0.0334
C16b-2	0.049938	0.425602	0.094526	0.0334
C17a-1	0.203339	0.087675	0.173167	0.0233
C17a-2	0.678455	0.119107	0.172033	0.0233
C17b-1	0.524686	0.381024	0.078531	0.0309
C17b-2	0.03304	0.386204	0.078585	0.0309
C18a-1	0.238591	0.089201	0.128414	0.0193
C18a-2	0.735507	0.084931	0.127681	0.0193
C18b-1	0.478159	0.568063	0.119009	0.0203
C18b-2	0.982124	0.566101	0.119431	0.0203
C19a-1	0.328726	0.136433	0.117037	0.0286
C19a-2	0.805763	0.165611	0.116062	0.0286
C19b-1	0.390287	0.668374	0.126518	0.0304
C19b-2	0.90284	0.678854	0.126417	0.0304
C20a-1	0.312446	0.102443	0.101053	0.0313
C20a-2	0.789079	0.132399	0.100084	0.0313
C20b-1	0.406594	0.702864	0.142607	0.0311
C20b-2	0.914526	0.713984	0.142371	0.0311
C21a-1	0.202813	0.017388	0.095973	0.027
C21a-2	0.701251	0.016128	0.095218	0.027
C21b-1	0.508855	0.639448	0.151483	0.0232
C21b-2	0.005305	0.63623	0.151997	0.0232
C22a-1	0.111974	0.967204	0.106991	0.0312
C22a-2	0.631089	0.936044	0.106417	0.0312
C22b-1	0.595985	0.541221	0.144036	0.0293
C22b-2	0.086864	0.528113	0.145179	0.0293
C23a-1	0.129465	0.004474	0.12287	0.0271
C23a-2	0.647678	0.967932	0.122491	0.0271
C23b-1	0.582533	0.505886	0.12816	0.0262
C23b-2	0.075902	0.49196	0.129113	0.0262
H1c3a-1	0.308079	0.315318	0.22336	0.0322*
H1c3a-2	0.810757	0.322314	0.222479	0.0322*
H1c3b-1	0.573299	0.309717	0.02355	0.029*
H1c3b-2	0.071348	0.308053	0.023745	0.029*
H1c4a-1	0.066109	0.472973	0.218143	0.0343*
H1c4a-2	0.571666	0.488389	0.217772	0.0343*
H2c4a-1	0.163778	0.512583	0.231728	0.0343*
H2c4a-2	0.670644	0.524199	0.231161	0.0343*
H1c4b-1	0.324951	0.16239	0.027458	0.033*
H1c4b-2	0.823939	0.159562	0.027696	0.033*
H2c4b-1	0.428636	0.113769	0.015551	0.033*
H2c4b-2	0.928763	0.110547	0.015981	0.033*
H1c6a-1	0.122659	0.5363	0.190133	0.0325*
H1c6a-2	0.627519	0.550148	0.189613	0.0325*
H1c6b-1	0.341911	0.087998	0.055361	0.0294*
H1c6b-2	0.842971	0.08938	0.056151	0.0294*
H1c7a-1	0.23947	0.699648	0.173198	0.0345*
H1c7a-2	0.735662	0.724118	0.172824	0.0345*
H1c7b-1	0.417869	0.902862	0.073703	0.0328*
H1c7b-2	0.91696	0.904068	0.074404	0.0328*
H1c8a-1	0.414822	0.855555	0.183001	0.0327*
H1c8a-2	0.911592	0.879293	0.182714	0.0327*
H1c8b-1	0.595982	0.740072	0.067543	0.0347*
H1c8b-2	0.092676	0.738202	0.068217	0.0347*
H1c9a-1	0.470817	0.844811	0.210225	0.0346*
H1c9a-2	0.974332	0.861205	0.209598	0.0346*
H1c9b-1	0.699297	0.763289	0.042627	0.0342*
H1c9b-2	0.19409	0.757153	0.043243	0.0342*
H1c10a-1	0.356763	0.678027	0.227218	0.0305*
H1c10a-2	0.866195	0.685625	0.226359	0.0305*
H1c10b-1	0.620997	0.94671	0.024162	0.0295*
H1c10b-2	0.11957	0.942674	0.024839	0.0295*
H1n1a-1	0.127816	0.249207	0.19967	0.0243*
H1n1a-2	0.624953	0.257895	0.199267	0.0243*
H1n1b-1	0.585063	0.380409	0.047749	0.0208*
H1n1b-2	0.086833	0.382395	0.04762	0.0208*
H1c13a-1	0.428304	0.356965	0.169377	0.03*
H1c13a-2	0.96552	0.288019	0.169645	0.03*
H1c13b-1	0.270187	0.60023	0.070637	0.0443*
H1c13b-2	0.762702	0.580592	0.071813	0.0443*
H1c14a-1	0.392772	0.301432	0.142507	0.032*
H1c14a-2	0.933529	0.228848	0.142896	0.032*
H1c14b-1	0.30346	0.672277	0.097105	0.0446*
H1c14b-2	0.796196	0.652337	0.098304	0.0446*
H1c16a-1	0.125129	0.968157	0.154293	0.0307*
H1c16a-2	0.581065	0.028681	0.152632	0.0307*
H1c16b-1	0.608131	0.370041	0.100477	0.0401*
H1c16b-2	0.123506	0.381991	0.10039	0.0401*
H1c17a-1	0.151548	0.035466	0.181034	0.028*
H1c17a-2	0.612139	0.089686	0.179538	0.028*
H1c17b-1	0.584427	0.308168	0.07377	0.0371*
H1c17b-2	0.095627	0.318802	0.073533	0.0371*
H1c19a-1	0.405301	0.194961	0.120408	0.0343*
H1c19a-2	0.86691	0.245815	0.119265	0.0343*
H1c19b-1	0.318109	0.713946	0.120563	0.0365*
H1c19b-2	0.838538	0.73342	0.11998	0.0365*
H1c20a-1	0.376603	0.137492	0.093527	0.0376*
H1c20a-2	0.838143	0.189608	0.092324	0.0376*
H1c20b-1	0.345269	0.772259	0.147603	0.0373*
H1c20b-2	0.859166	0.793141	0.146848	0.0373*
H1c22a-1	0.036695	0.906439	0.103616	0.0374*
H1c22a-2	0.569578	0.856731	0.10308	0.0374*
H1c22b-1	0.667944	0.496266	0.150079	0.0352*
H1c22b-2	0.152781	0.47644	0.151635	0.0352*
H1c23a-1	0.064232	0.970852	0.13033	0.0326*
H1c23a-2	0.598611	0.909416	0.13015	0.0326*
H1c23b-1	0.645499	0.43771	0.123283	0.0314*
H1c23b-2	0.133566	0.415088	0.124643	0.0314*
H1c21a-1	0.190142	0.993581	0.084899	0.0324*
H1c21a-2	0.689896	0.992223	0.084127	0.0324*
H1c21b-1	0.519154	0.663135	0.162591	0.0279*
H1c21b-2	0.011061	0.657491	0.163195	0.0279*
H1c1a-1	0.119033	0.840002	0.235523	0.0516*
H1c1a-2	0.618269	0.852116	0.235105	0.0516*
H2c1a-1	0.135119	0.959694	0.249495	0.0516*
H2c1a-2	0.63566	0.971898	0.249048	0.0516*
H3c1a-1	0.006755	0.96189	0.238721	0.0516*
H3c1a-2	0.507042	0.975278	0.238321	0.0516*
H1c1b-1	0.374943	0.793967	0.015669	0.0436*
H1c1b-2	0.875147	0.791207	0.015616	0.0436*
H2c1b-1	0.367915	0.680374	0.001088	0.0436*
H2c1b-2	0.865301	0.675612	0.001219	0.0436*
H3c1b-1	0.259001	0.672879	0.014181	0.0436*
H3c1b-2	0.758046	0.671325	0.014521	0.0436*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1a-1	0.04287	0.023246	0.031514	0.001385	0.01283	0.001207
O1a-2	0.04287	0.023246	0.031514	0.001385	0.01283	0.001207
O1b-1	0.029795	0.018585	0.025068	−0.001925	−0.007423	0.00172
O1b-2	0.029795	0.018585	0.025068	−0.001925	−0.007423	0.00172
O2a-1	0.093617	0.029089	0.036885	0.000701	0.035958	−0.001939
O2a-2	0.093617	0.029089	0.036885	0.000701	0.035958	−0.001939
O2b-1	0.050726	0.024678	0.030798	−0.00199	−0.021841	−0.000842
O2b-2	0.050726	0.024678	0.030798	−0.00199	−0.021841	−0.000842
O3a-1	0.014473	0.039555	0.0265	−0.000132	−0.000129	−0.00322
O3a-2	0.014473	0.039555	0.0265	−0.000132	−0.000129	−0.00322
O3b-1	0.014694	0.032498	0.025068	−0.000237	−0.002918	−0.000915
O3b-2	0.014694	0.032498	0.025068	−0.000237	−0.002918	−0.000915
N1a-1	0.016299	0.025018	0.019338	0.000495	−0.000772	−0.001281
N1a-2	0.016299	0.025018	0.019338	0.000495	−0.000772	−0.001281
N1b-1	0.013733	0.018933	0.019338	−0.002183	−0.001845	0.000146
N1b-2	0.013733	0.018933	0.019338	−0.002183	−0.001845	0.000146
C1a-1	0.049199	0.027665	0.0265	−0.009592	0.00369	0.002159
C1a-2	0.049199	0.027665	0.0265	−0.009592	0.00369	0.002159
C1b-1	0.039919	0.020163	0.026858	0.004752	−0.00369	0.00322
C1b-2	0.039919	0.020163	0.026858	0.004752	−0.00369	0.00322
C2a-1	0.025425	0.02824	0.020054	−0.000964	0.000129	−0.005012
C2a-2	0.025425	0.02824	0.020054	−0.000964	0.000129	−0.005012
C2b-1	0.022926	0.022977	0.018264	−0.000719	0.001931	0.000293
C2b-2	0.022926	0.022977	0.018264	−0.000719	0.001931	0.000293
C3a-1	0.021707	0.023512	0.019338	0.001175	−0.001974	−0.002817
C3a-2	0.021707	0.023512	0.019338	0.001175	−0.001974	−0.002817
C3b-1	0.01926	0.020951	0.017547	−0.000368	−0.001287	−0.000768
C3b-2	0.01926	0.020951	0.017547	−0.000368	−0.001287	−0.000768
C4a-1	0.020967	0.024929	0.022919	0.003349	0.002017	−0.004244
C4a-2	0.020967	0.024929	0.022919	0.003349	0.002017	−0.004244
C4b-1	0.024777	0.016144	0.025068	−0.001083	−0.005621	−0.00161
C4b-2	0.024777	0.016144	0.025068	−0.001083	−0.005621	−0.00161
C5a-1	0.025286	0.018406	0.026142	0.003959	0.004291	−0.000988
C5a-2	0.025286	0.018406	0.026142	0.003959	0.004291	−0.000988
C5b-1	0.024792	0.01506	0.026858	−0.003858	−0.004806	−0.004025
C5b-2	0.024792	0.01506	0.026858	−0.003858	−0.004806	−0.004025
C6a-1	0.022659	0.027657	0.030798	0.002762	−0.004076	−0.003256
C6a-2	0.022659	0.027657	0.030798	0.002762	−0.004076	−0.003256
C6b-1	0.024294	0.018178	0.031156	0.001162	−0.002103	−0.002707
C6b-2	0.024294	0.018178	0.031156	0.001162	−0.002103	−0.002707
C7a-1	0.029667	0.032076	0.024352	0.000947	0.000257	0.003403
C7a-2	0.029667	0.032076	0.024352	0.000947	0.000257	0.003403
C7b-1	0.033127	0.022914	0.025784	0.000561	−0.00103	−0.00011
C7b-2	0.033127	0.022914	0.025784	0.000561	−0.00103	−0.00011
C8a-1	0.030931	0.020645	0.030439	0.002218	0.003175	0.003366
C8a-2	0.030931	0.020645	0.030439	0.002218	0.003175	0.003366
C8b-1	0.031332	0.021262	0.034021	0.000329	−0.008067	0.002964
C8b-2	0.031332	0.021262	0.034021	0.000329	−0.008067	0.002964
C9a-1	0.029389	0.024869	0.03223	−0.002275	−0.001974	−0.004573
C9a-2	0.029389	0.024869	0.03223	−0.002275	−0.001974	−0.004573
C9b-1	0.02651	0.021706	0.037244	0.003775	−0.002575	−0.00311
C9b-2	0.02651	0.021706	0.037244	0.003775	−0.002575	−0.00311
C10a-1	0.027137	0.024521	0.024352	0.000636	−0.002188	−0.002378
C10a-2	0.027137	0.024521	0.024352	0.000636	−0.002188	−0.002378
C10b-1	0.025538	0.021718	0.0265	−0.003051	−0.000086	−0.005049
C10b-2	0.025538	0.021718	0.0265	−0.003051	−0.000086	−0.005049
C11a-1	0.012134	0.019979	0.025784	−0.000092	0.000815	0.001171
C11a-2	0.012134	0.019979	0.025784	−0.000092	0.000815	0.001171
C11b-1	0.011568	0.015662	0.025784	0.000219	−0.000515	0.003037
C11b-2	0.011568	0.015662	0.025784	0.000219	−0.000515	0.003037
C12a-1	0.016484	0.019393	0.022203	0.001306	0.000515	0
C12a-2	0.016484	0.019393	0.022203	0.001306	0.000515	0
C12b-1	0.016823	0.017426	0.020412	−0.001999	0.004034	0.001829
C12b-2	0.016823	0.017426	0.020412	−0.001999	0.004034	0.001829
C13a-1	0.016623	0.032371	0.026142	−0.004599	−0.001073	−0.00311
C13a-2	0.016623	0.032371	0.026142	−0.004599	−0.001073	−0.00311
C13b-1	0.031523	0.051782	0.027216	0.023748	−0.008796	−0.006769
C13b-2	0.031523	0.051782	0.027216	0.023748	−0.008796	−0.006769
C14a-1	0.024767	0.030894	0.024352	−0.003187	0.005664	0.001756
C14a-2	0.024767	0.030894	0.024352	−0.003187	0.005664	0.001756
C14b-1	0.038068	0.044441	0.028649	0.024682	−0.007595	−0.011232
C14b-2	0.038068	0.044441	0.028649	0.024682	−0.007595	−0.011232
C15a-1	0.019512	0.016948	0.024352	0.00313	0.000172	0.000549
C15a-2	0.019512	0.016948	0.024352	0.00313	0.000172	0.000549
C15b-1	0.016617	0.01623	0.022561	−0.000416	0.000944	0.000585
C15b-2	0.016617	0.01623	0.022561	−0.000416	0.000944	0.000585
C16a-1	0.024433	0.02537	0.026858	−0.003954	0.000043	−0.002049
C16a-2	0.024433	0.02537	0.026858	−0.003954	0.000043	−0.002049
C16b-1	0.029723	0.045985	0.024352	0.019355	−0.005707	−0.004829
C16b-2	0.029723	0.045985	0.024352	0.019355	−0.005707	−0.004829
C17a-1	0.01797	0.024891	0.027216	−0.002845	0.006308	−0.000476
C17a-2	0.01797	0.024891	0.027216	−0.002845	0.006308	−0.000476
C17b-1	0.023872	0.043002	0.025784	0.014353	−0.004119	−0.007939
C17b-2	0.023872	0.043002	0.025784	0.014353	−0.004119	−0.007939
C18a-1	0.016437	0.016825	0.02471	0.003832	−0.001416	−0.002342
C18a-2	0.016437	0.016825	0.02471	0.003832	−0.001416	−0.002342
C18b-1	0.021178	0.017939	0.021845	−0.0053	0.004248	−0.000402
C18b-2	0.021178	0.017939	0.021845	−0.0053	0.004248	−0.000402
C19a-1	0.027877	0.028861	0.029007	−0.005449	0.001459	−0.00322
C19a-2	0.027877	0.028861	0.029007	−0.005449	0.001459	−0.00322
C19b-1	0.028715	0.039137	0.023277	0.011951	−0.003004	−0.000073
C19b-2	0.028715	0.039137	0.023277	0.011951	−0.003004	−0.000073
C20a-1	0.037615	0.033776	0.022561	−0.003104	0.002446	−0.003805
C20a-2	0.037615	0.033776	0.022561	−0.003104	0.002446	−0.003805
C20b-1	0.02979	0.036456	0.027216	0.007128	0.00442	−0.006878
C20b-2	0.02979	0.036456	0.027216	0.007128	0.00442	−0.006878
C21a-1	0.032063	0.025841	0.022919	0.006795	−0.004806	−0.00633
C21a-2	0.032063	0.025841	0.022919	0.006795	−0.004806	−0.00633
C21b-1	0.021106	0.026641	0.021845	−0.007378	0.000257	−0.001793
C21b-2	0.021106	0.026641	0.021845	−0.007378	0.000257	−0.001793
C22a-1	0.031456	0.030027	0.031872	−0.004007	−0.004763	−0.005671
C22a-2	0.031456	0.030027	0.031872	−0.004007	−0.004763	−0.005671
C22b-1	0.029039	0.031425	0.027216	0.003753	−0.00781	−0.000293
C22b-2	0.029039	0.031425	0.027216	0.003753	−0.00781	−0.000293
C23a-1	0.024489	0.029721	0.027216	−0.004537	0.000644	−0.0015
C23a-2	0.024489	0.029721	0.027216	−0.004537	0.000644	−0.0015
C23b-1	0.026602	0.025908	0.026142	0.005611	−0.000815	−0.003915
C23b-2	0.026602	0.025908	0.026142	0.005611	−0.000815	−0.003915

Geometric parameters (Å, º)

O1a-1—C1a-1^i	1.4384 (1)	C9b-1—C10b-1	1.3853 (1)
O1a-1—C2a-1	1.3236 (1)	C9b-1—H1c9b-1	0.9600 (1)
O1a-2—C1a-2^i	1.4480 (1)	C9b-2—C10b-2	1.3834 (1)
O1a-2—C2a-2	1.3242 (1)	C9b-2—H1c9b-2	0.9600 (1)
O1b-1—C1b-1	1.4502 (1)	C10a-1—H1c10a-1	0.9599 (1)
O1b-1—C2b-1	1.3271 (1)	C10a-2—H1c10a-2	0.9600 (1)
O1b-2—C1b-2	1.4496 (1)	C10b-1—H1c10b-1	0.9600 (1)
O1b-2—C2b-2	1.3263 (1)	C10b-2—H1c10b-2	0.9600 (1)
O2a-1—C2a-1	1.1988 (1)	C11a-1—C12a-1	1.4984 (1)
O2a-2—C2a-2	1.1934 (1)	C11a-2—C12a-2	1.4983 (1)
O2b-1—C2b-1	1.2055 (1)	C11b-1—C12b-1	1.4967 (1)
O2b-2—C2b-2	1.2059 (1)	C11b-2—C12b-2	1.5077 (1)
O3a-1—C11a-1	1.2393 (1)	C12a-1—C13a-1	1.3875 (1)
O3a-2—C11a-2	1.2361 (1)	C12a-1—C17a-1	1.3875 (1)
O3b-1—C11b-1	1.2398 (1)	C12a-2—C13a-2	1.3825 (1)
O3b-2—C11b-2	1.2301 (1)	C12a-2—C17a-2	1.3838 (1)
N1a-1—C3a-1	1.4539 (1)	C12b-1—C13b-1	1.3743 (1)
N1a-1—C11a-1	1.3309 (1)	C12b-1—C17b-1	1.3868 (1)
N1a-1—H1n1a-1	0.9143 (1)	C12b-2—C13b-2	1.3710 (1)
N1a-2—C3a-2	1.4566 (1)	C12b-2—C17b-2^iii	1.3833 (1)
N1a-2—C11a-2	1.3335 (1)	C13a-1—C14a-1	1.3859 (1)
N1a-2—H1n1a-2	0.9234 (1)	C13a-1—H1c13a-1	0.9600 (1)
N1b-1—C3b-1	1.4526 (1)	C13a-2—C14a-2	1.3814 (1)
N1b-1—C11b-1	1.3198 (1)	C13a-2—H1c13a-2	0.9600 (1)
N1b-1—H1n1b-1	0.9177 (1)	C13b-1—C14b-1	1.3873 (1)
N1b-2—C3b-2^ii	1.4525 (1)	C13b-1—H1c13b-1	0.9600 (1)
N1b-2—C11b-2^ii	1.3287 (1)	C13b-2—C14b-2	1.3865 (1)
N1b-2—H1n1b-2	0.9143 (1)	C13b-2—H1c13b-2	0.9600 (1)
C1a-1—H1c1a-1	0.9600 (1)	C14a-1—C15a-1	1.3959 (1)
C1a-1—H2c1a-1	0.9600 (1)	C14a-1—H1c14a-1	0.9600 (1)
C1a-1—H3c1a-1	0.9600 (1)	C14a-2—C15a-2	1.3880 (1)
C1a-2—H1c1a-2	0.9600 (1)	C14a-2—H1c14a-2	0.9600 (1)
C1a-2—H2c1a-2	0.9601 (1)	C14b-1—C15b-1	1.3861 (1)
C1a-2—H3c1a-2	0.9600 (1)	C14b-1—H1c14b-1	0.9600 (1)
C1b-1—H1c1b-1	0.9600 (1)	C14b-2—C15b-2	1.3921 (1)
C1b-1—H2c1b-1	0.9600 (1)	C14b-2—H1c14b-2	0.9600 (1)
C1b-1—H3c1b-1	0.9600 (1)	C15a-1—C16a-1	1.4039 (1)
C1b-2—H1c1b-2	0.9600 (1)	C15a-1—C18a-1	1.4764 (1)
C1b-2—H2c1b-2	0.9600 (1)	C15a-2—C16a-2	1.3841 (1)
C1b-2—H3c1b-2	0.9600 (1)	C15a-2—C18a-2	1.4914 (1)
C2a-1—C3a-1	1.5189 (1)	C15b-1—C16b-1	1.3833 (1)
C2a-2—C3a-2	1.5196 (1)	C15b-1—C18b-1	1.4969 (1)
C2b-1—C3b-1	1.5197 (1)	C15b-2—C16b-2^iii	1.3771 (1)
C2b-2—C3b-2	1.5179 (1)	C15b-2—C18b-2	1.4987 (1)
C3a-1—C4a-1	1.5421 (1)	C16a-1—C17a-1	1.3860 (1)
C3a-1—H1c3a-1	0.9600 (1)	C16a-1—H1c16a-1^i	0.9600 (1)
C3a-2—C4a-2	1.5446 (1)	C16a-2—C17a-2	1.3929 (1)
C3a-2—H1c3a-2	0.9600 (1)	C16a-2—H1c16a-2	0.9600 (1)
C3b-1—C4b-1	1.5554 (1)	C16b-1—C17b-1	1.3763 (1)
C3b-1—H1c3b-1	0.9600 (1)	C16b-1—H1c16b-1	0.9600 (1)
C3b-2—C4b-2	1.5565 (1)	C16b-2—C17b-2	1.3904 (1)
C3b-2—H1c3b-2^iii	0.9600 (1)	C16b-2—H1c16b-2	0.9600 (1)
C4a-1—C5a-1	1.5042 (1)	C17a-1—H1c17a-1	0.9600 (1)
C4a-1—H1c4a-1	0.9600 (1)	C17a-2—H1c17a-2	0.9600 (1)
C4a-1—H2c4a-1	0.9599 (1)	C17b-1—H1c17b-1	0.9600 (1)
C4a-2—C5a-2	1.5093 (1)	C17b-2—H1c17b-2	0.9600 (1)
C4a-2—H1c4a-2	0.9600 (1)	C18a-1—C19a-1	1.3897 (1)
C4a-2—H2c4a-2	0.9601 (1)	C18a-1—C23a-1	1.3929 (1)
C4b-1—C5b-1	1.5061 (1)	C18a-2—C19a-2	1.3990 (1)
C4b-1—H1c4b-1	0.9600 (1)	C18a-2—C23a-2^i	1.4042 (1)
C4b-1—H2c4b-1	0.9600 (1)	C18b-1—C19b-1	1.3936 (1)
C4b-2—C5b-2	1.5105 (1)	C18b-1—C23b-1	1.3994 (1)
C4b-2—H1c4b-2	0.9600 (1)	C18b-2—C19b-2	1.3913 (1)
C4b-2—H2c4b-2	0.9600 (1)	C18b-2—C23b-2^iii	1.3919 (1)
C5a-1—C6a-1	1.3847 (1)	C19a-1—C20a-1	1.3827 (1)
C5a-1—C10a-1	1.4037 (1)	C19a-1—H1c19a-1	0.9600 (1)
C5a-2—C6a-2	1.3885 (1)	C19a-2—C20a-2	1.3812 (1)
C5a-2—C10a-2	1.3900 (1)	C19a-2—H1c19a-2	0.9600 (1)
C5b-1—C6b-1	1.3923 (1)	C19b-1—C20b-1	1.3922 (1)
C5b-1—C10b-1^i	1.3920 (1)	C19b-1—H1c19b-1	0.9600 (1)
C5b-2—C6b-2	1.3967 (1)	C19b-2—C20b-2	1.3783 (1)
C5b-2—C10b-2^iv	1.3953 (1)	C19b-2—H1c19b-2	0.9600 (1)
C6a-1—C7a-1	1.3826 (1)	C20a-1—C21a-1	1.3863 (1)
C6a-1—H1c6a-1	0.9600 (1)	C20a-1—H1c20a-1	0.9600 (1)
C6a-2—C7a-2	1.3843 (1)	C20a-2—C21a-2	1.3917 (1)
C6a-2—H1c6a-2	0.9600 (1)	C20a-2—H1c20a-2	0.9600 (1)
C6b-1—C7b-1^i	1.3843 (1)	C20b-1—C21b-1	1.3754 (1)
C6b-1—H1c6b-1	0.9600 (1)	C20b-1—H1c20b-1	0.9600 (1)
C6b-2—C7b-2^i	1.3764 (1)	C20b-2—C21b-2^iii	1.3838 (1)
C6b-2—H1c6b-2	0.9600 (1)	C20b-2—H1c20b-2	0.9600 (1)
C7a-1—C8a-1	1.3934 (1)	C21a-1—C22a-1^i	1.3813 (1)
C7a-1—H1c7a-1	0.9600 (1)	C21a-1—H1c21a-1^i	0.9600 (1)
C7a-2—C8a-2	1.3961 (1)	C21a-2—C22a-2^i	1.3712 (1)
C7a-2—H1c7a-2	0.9600 (1)	C21a-2—H1c21a-2^i	0.9601 (1)
C7b-1—C8b-1	1.3798 (1)	C21b-1—C22b-1	1.3754 (1)
C7b-1—H1c7b-1	0.9600 (1)	C21b-1—H1c21b-1	0.9600 (1)
C7b-2—C8b-2^iii	1.3786 (1)	C21b-2—C22b-2	1.3715 (1)
C7b-2—H1c7b-2	0.9600 (1)	C21b-2—H1c21b-2	0.9600 (1)
C8a-1—C9a-1	1.3856 (1)	C22a-1—C23a-1^v	1.3817 (1)
C8a-1—H1c8a-1	0.9600 (1)	C22a-1—H1c22a-1	0.9600 (1)
C8a-2—C9a-2	1.3792 (1)	C22a-2—C23a-2	1.3867 (1)
C8a-2—H1c8a-2	0.9600 (1)	C22a-2—H1c22a-2	0.9600 (1)
C8b-1—C9b-1	1.3972 (1)	C22b-1—C23b-1	1.3737 (1)
C8b-1—H1c8b-1	0.9599 (1)	C22b-1—H1c22b-1	0.9600 (1)
C8b-2—C9b-2	1.3911 (1)	C22b-2—C23b-2	1.3889 (1)
C8b-2—H1c8b-2	0.9600 (1)	C22b-2—H1c22b-2	0.9600 (1)
C9a-1—C10a-1	1.3863 (1)	C23a-1—H1c23a-1^i	0.9600 (1)
C9a-1—H1c9a-1	0.9600 (1)	C23a-2—H1c23a-2	0.9600 (1)
C9a-2—C10a-2	1.3918 (1)	C23b-1—H1c23b-1	0.9600 (1)
C9a-2—H1c9a-2	0.9600 (1)	C23b-2—H1c23b-2	0.9600 (1)
C1a-1^i—O1a-1—C2a-1	115.5571 (17)	C5a-2—C10a-2—H1c10a-2	119.541 (2)
C1a-2^i—O1a-2—C2a-2	115.4634 (17)	C9a-2—C10a-2—H1c10a-2	119.5413 (19)
C1b-1—O1b-1—C2b-1	114.5492 (19)	C5b-1^v—C10b-1—C9b-1	121.054 (2)
C1b-2—O1b-2—C2b-2	114.4180 (19)	C5b-1^v—C10b-1—H1c10b-1	119.473 (2)
C3a-1—N1a-1—C11a-1	121.995 (2)	C9b-1—C10b-1—H1c10b-1	119.4725 (17)
C3a-1—N1a-1—H1n1a-1	112.993 (3)	C5b-2^vi—C10b-2—C9b-2	121.098 (2)
C11a-1—N1a-1—H1n1a-1	120.904 (2)	C5b-2^vi—C10b-2—H1c10b-2	119.451 (2)
C3a-2—N1a-2—C11a-2	122.707 (2)	C9b-2—C10b-2—H1c10b-2	119.4511 (17)
C3a-2—N1a-2—H1n1a-2	112.457 (3)	O3a-1—C11a-1—N1a-1	123.557 (2)
C11a-2—N1a-2—H1n1a-2	123.513 (2)	O3a-1—C11a-1—C12a-1	120.344 (3)
C3b-1—N1b-1—C11b-1	121.496 (3)	N1a-1—C11a-1—C12a-1	116.089 (3)
C3b-1—N1b-1—H1n1b-1	117.457 (3)	O3a-2—C11a-2—N1a-2	123.347 (2)
C11b-1—N1b-1—H1n1b-1	120.984 (2)	O3a-2—C11a-2—C12a-2	120.815 (3)
C3b-2^ii—N1b-2—C11b-2^ii	120.443 (3)	N1a-2—C11a-2—C12a-2	115.827 (3)
C3b-2^ii—N1b-2—H1n1b-2	117.240 (3)	O3b-1—C11b-1—N1b-1	122.009 (2)
C11b-2^ii—N1b-2—H1n1b-2	122.198 (2)	O3b-1—C11b-1—C12b-1	120.798 (3)
O1a-1^v—C1a-1—H1c1a-1	109.4666 (19)	N1b-1—C11b-1—C12b-1	117.183 (3)
O1a-1^v—C1a-1—H2c1a-1	109.4709 (19)	O3b-2—C11b-2—N1b-2^iii	122.666 (2)
O1a-1^v—C1a-1—H3c1a-1	109.470 (2)	O3b-2—C11b-2—C12b-2	120.670 (3)
H1c1a-1—C1a-1—H2c1a-1	109.4760 (8)	N1b-2^iii—C11b-2—C12b-2	116.660 (3)
H1c1a-1—C1a-1—H3c1a-1	109.4692 (9)	C11a-1—C12a-1—C13a-1	118.545 (2)
H2c1a-1—C1a-1—H3c1a-1	109.475 (3)	C11a-1—C12a-1—C17a-1	122.6925 (19)
O1a-2^v—C1a-2—H1c1a-2	109.4754 (19)	C13a-1—C12a-1—C17a-1	118.7599 (19)
O1a-2^v—C1a-2—H2c1a-2	109.4722 (19)	C11a-2—C12a-2—C13a-2	117.823 (2)
O1a-2^v—C1a-2—H3c1a-2	109.472 (2)	C11a-2—C12a-2—C17a-2	123.933 (2)
H1c1a-2—C1a-2—H2c1a-2	109.4669 (8)	C13a-2—C12a-2—C17a-2	118.229 (2)
H1c1a-2—C1a-2—H3c1a-2	109.4732 (9)	C11b-1—C12b-1—C13b-1	118.516 (2)
H2c1a-2—C1a-2—H3c1a-2	109.468 (3)	C11b-1—C12b-1—C17b-1	123.035 (2)
O1b-1—C1b-1—H1c1b-1	109.470 (2)	C13b-1—C12b-1—C17b-1	118.4445 (19)
O1b-1—C1b-1—H2c1b-1	109.4726 (19)	C11b-2—C12b-2—C13b-2	118.168 (2)
O1b-1—C1b-1—H3c1b-1	109.4704 (19)	C11b-2—C12b-2—C17b-2^iii	123.111 (2)
H1c1b-1—C1b-1—H2c1b-1	109.4716 (9)	C13b-2—C12b-2—C17b-2^iii	118.694 (2)
H1c1b-1—C1b-1—H3c1b-1	109.4701 (10)	C12a-1—C13a-1—C14a-1	120.420 (2)
H2c1b-1—C1b-1—H3c1b-1	109.472 (3)	C12a-1—C13a-1—H1c13a-1	119.7925 (19)
O1b-2—C1b-2—H1c1b-2	109.470 (2)	C14a-1—C13a-1—H1c13a-1	119.788 (2)
O1b-2—C1b-2—H2c1b-2	109.4703 (19)	C12a-2—C13a-2—C14a-2	120.579 (2)
O1b-2—C1b-2—H3c1b-2	109.4716 (19)	C12a-2—C13a-2—H1c13a-2	119.710 (2)
H1c1b-2—C1b-2—H2c1b-2	109.4728 (9)	C14a-2—C13a-2—H1c13a-2	119.711 (2)
H1c1b-2—C1b-2—H3c1b-2	109.4709 (10)	C12b-1—C13b-1—C14b-1	121.099 (2)
H2c1b-2—C1b-2—H3c1b-2	109.472 (3)	C12b-1—C13b-1—H1c13b-1	119.4538 (19)
O1a-1—C2a-1—O2a-1	123.3494 (1)	C14b-1—C13b-1—H1c13b-1	119.447 (2)
O1a-1—C2a-1—C3a-1	112.9495 (17)	C12b-2—C13b-2—C14b-2	121.210 (2)
O2a-1—C2a-1—C3a-1	123.6704 (18)	C12b-2—C13b-2—H1c13b-2	119.394 (2)
O1a-2—C2a-2—O2a-2	124.1537 (2)	C14b-2—C13b-2—H1c13b-2	119.396 (2)
O1a-2—C2a-2—C3a-2	112.4815 (17)	C13a-1—C14a-1—C15a-1	121.5932 (19)
O2a-2—C2a-2—C3a-2	123.3520 (19)	C13a-1—C14a-1—H1c14a-1	119.203 (2)
O1b-1—C2b-1—O2b-1	124.09	C15a-1—C14a-1—H1c14a-1	119.2036 (19)
O1b-1—C2b-1—C3b-1	112.6403 (19)	C13a-2—C14a-2—C15a-2	121.873 (2)
O2b-1—C2b-1—C3b-1	123.2516 (18)	C13a-2—C14a-2—H1c14a-2	119.062 (2)
O1b-2—C2b-2—O2b-2	124.29	C15a-2—C14a-2—H1c14a-2	119.064 (2)
O1b-2—C2b-2—C3b-2	112.4791 (19)	C13b-1—C14b-1—C15b-1	121.366 (2)
O2b-2—C2b-2—C3b-2	123.1901 (18)	C13b-1—C14b-1—H1c14b-1	119.314 (2)
N1a-1—C3a-1—C2a-1	111.018 (2)	C15b-1—C14b-1—H1c14b-1	119.3206 (19)
N1a-1—C3a-1—C4a-1	111.7145 (13)	C13b-2—C14b-2—C15b-2	120.979 (2)
N1a-1—C3a-1—H1c3a-1	107.347 (3)	C13b-2—C14b-2—H1c14b-2	119.512 (2)
C2a-1—C3a-1—C4a-1	110.9325 (19)	C15b-2—C14b-2—H1c14b-2	119.509 (2)
C2a-1—C3a-1—H1c3a-1	108.190 (2)	C14a-1—C15a-1—C16a-1	117.3464 (19)
C4a-1—C3a-1—H1c3a-1	107.4408 (9)	C14a-1—C15a-1—C18a-1	121.1133 (19)
N1a-2—C3a-2—C2a-2	111.773 (2)	C16a-1—C15a-1—C18a-1	121.533 (2)
N1a-2—C3a-2—C4a-2	111.4350 (13)	C14a-2—C15a-2—C16a-2	117.345 (2)
N1a-2—C3a-2—H1c3a-2	107.060 (3)	C14a-2—C15a-2—C18a-2	120.968 (2)
C2a-2—C3a-2—C4a-2	111.0949 (18)	C16a-2—C15a-2—C18a-2	121.684 (2)
C2a-2—C3a-2—H1c3a-2	107.430 (2)	C14b-1—C15b-1—C16b-1	116.2843 (19)
C4a-2—C3a-2—H1c3a-2	107.7979 (8)	C14b-1—C15b-1—C18b-1	121.842 (2)
N1b-1—C3b-1—C2b-1	112.456 (2)	C16b-1—C15b-1—C18b-1	121.8421 (19)
N1b-1—C3b-1—C4b-1	112.8710 (13)	C14b-2—C15b-2—C16b-2^iii	117.007 (2)
N1b-1—C3b-1—H1c3b-1	104.809 (3)	C14b-2—C15b-2—C18b-2	120.576 (2)
C2b-1—C3b-1—C4b-1	109.077 (2)	C16b-2^iii—C15b-2—C18b-2	122.380 (2)
C2b-1—C3b-1—H1c3b-1	108.941 (2)	C15a-1—C16a-1—C17a-1	120.884 (2)
C4b-1—C3b-1—H1c3b-1	108.4857 (11)	C15a-1—C16a-1—H1c16a-1^i	119.5603 (19)
N1b-2^iii—C3b-2—C2b-2	112.688 (2)	C17a-1—C16a-1—H1c16a-1^i	119.5552 (19)
N1b-2^iii—C3b-2—C4b-2	113.4114 (13)	C15a-2—C16a-2—C17a-2	121.034 (2)
N1b-2^iii—C3b-2—H1c3b-2^iii	104.213 (3)	C15a-2—C16a-2—H1c16a-2	119.483 (2)
C2b-2—C3b-2—C4b-2	109.045 (2)	C17a-2—C16a-2—H1c16a-2	119.483 (2)
C2b-2—C3b-2—H1c3b-2^iii	109.010 (2)	C15b-1—C16b-1—C17b-1	123.1610 (19)
C4b-2—C3b-2—H1c3b-2^iii	108.2185 (11)	C15b-1—C16b-1—H1c16b-1	118.4227 (19)
C3a-1—C4a-1—C5a-1	112.6439 (19)	C17b-1—C16b-1—H1c16b-1	118.416 (2)
C3a-1—C4a-1—H1c4a-1	109.4703 (9)	C15b-2^ii—C16b-2—C17b-2	122.335 (2)
C3a-1—C4a-1—H2c4a-1	109.4739 (13)	C15b-2^ii—C16b-2—H1c16b-2	118.830 (2)
C5a-1—C4a-1—H1c4a-1	109.468 (2)	C17b-2—C16b-2—H1c16b-2	118.834 (2)
C5a-1—C4a-1—H2c4a-1	109.469 (2)	C12a-1—C17a-1—C16a-1	120.929 (2)
H1c4a-1—C4a-1—H2c4a-1	106.104 (3)	C12a-1—C17a-1—H1c17a-1	119.5354 (19)
C3a-2—C4a-2—C5a-2	113.5559 (19)	C16a-1—C17a-1—H1c17a-1	119.535 (2)
C3a-2—C4a-2—H1c4a-2	109.4717 (8)	C12a-2—C17a-2—C16a-2	120.925 (2)
C3a-2—C4a-2—H2c4a-2	109.4683 (12)	C12a-2—C17a-2—H1c17a-2	119.539 (2)
C5a-2—C4a-2—H1c4a-2	109.475 (2)	C16a-2—C17a-2—H1c17a-2	119.536 (2)
C5a-2—C4a-2—H2c4a-2	109.472 (2)	C12b-1—C17b-1—C16b-1	119.595 (2)
H1c4a-2—C4a-2—H2c4a-2	105.050 (3)	C12b-1—C17b-1—H1c17b-1	120.1985 (19)
C3b-1—C4b-1—C5b-1	114.138 (2)	C16b-1—C17b-1—H1c17b-1	120.206 (2)
C3b-1—C4b-1—H1c4b-1	109.4713 (11)	C12b-2^ii—C17b-2—C16b-2	119.743 (2)
C3b-1—C4b-1—H2c4b-1	109.4700 (15)	C12b-2^ii—C17b-2—H1c17b-2	120.131 (2)
C5b-1—C4b-1—H1c4b-1	109.471 (2)	C16b-2—C17b-2—H1c17b-2	120.126 (2)
C5b-1—C4b-1—H2c4b-1	109.4722 (19)	C15a-1—C18a-1—C19a-1	121.855 (2)
H1c4b-1—C4b-1—H2c4b-1	104.363 (3)	C15a-1—C18a-1—C23a-1	121.850 (2)
C3b-2—C4b-2—C5b-2	114.277 (2)	C19a-1—C18a-1—C23a-1	116.295 (2)
C3b-2—C4b-2—H1c4b-2	109.4715 (11)	C15a-2—C18a-2—C19a-2	120.940 (2)
C3b-2—C4b-2—H2c4b-2	109.4729 (15)	C15a-2—C18a-2—C23a-2^i	121.6248 (19)
C5b-2—C4b-2—H1c4b-2	109.470 (2)	C19a-2—C18a-2—C23a-2^i	117.4349 (19)
C5b-2—C4b-2—H2c4b-2	109.4710 (19)	C15b-1—C18b-1—C19b-1	120.654 (2)
H1c4b-2—C4b-2—H2c4b-2	104.195 (3)	C15b-1—C18b-1—C23b-1	121.693 (2)
C4a-1—C5a-1—C6a-1	120.4522 (18)	C19b-1—C18b-1—C23b-1	117.653 (2)
C4a-1—C5a-1—C10a-1	120.940 (2)	C15b-2—C18b-2—C19b-2	120.9003 (19)
C6a-1—C5a-1—C10a-1	118.599 (2)	C15b-2—C18b-2—C23b-2^iii	121.669 (2)
C4a-2—C5a-2—C6a-2	120.0749 (19)	C19b-2—C18b-2—C23b-2^iii	117.4222 (19)
C4a-2—C5a-2—C10a-2	121.339 (2)	C18a-1—C19a-1—C20a-1	122.583 (2)
C6a-2—C5a-2—C10a-2	118.586 (2)	C18a-1—C19a-1—H1c19a-1	118.709 (2)
C4b-1—C5b-1—C6b-1	119.2000 (17)	C20a-1—C19a-1—H1c19a-1	118.708 (2)
C4b-1—C5b-1—C10b-1^i	122.268 (2)	C18a-2—C19a-2—C20a-2	121.446 (2)
C6b-1—C5b-1—C10b-1^i	118.520 (2)	C18a-2—C19a-2—H1c19a-2	119.2752 (19)
C4b-2—C5b-2—C6b-2	119.8970 (17)	C20a-2—C19a-2—H1c19a-2	119.2792 (19)
C4b-2—C5b-2—C10b-2^iv	122.107 (2)	C18b-1—C19b-1—C20b-1	120.369 (2)
C6b-2—C5b-2—C10b-2^iv	117.986 (2)	C18b-1—C19b-1—H1c19b-1	119.816 (2)
C5a-1—C6a-1—C7a-1	120.5364 (19)	C20b-1—C19b-1—H1c19b-1	119.814 (2)
C5a-1—C6a-1—H1c6a-1	119.732 (2)	C18b-2—C19b-2—C20b-2	121.4917 (19)
C7a-1—C6a-1—H1c6a-1	119.731 (2)	C18b-2—C19b-2—H1c19b-2	119.2560 (19)
C5a-2—C6a-2—C7a-2	120.7703 (18)	C20b-2—C19b-2—H1c19b-2	119.252 (2)
C5a-2—C6a-2—H1c6a-2	119.619 (2)	C19a-1—C20a-1—C21a-1	119.526 (2)
C7a-2—C6a-2—H1c6a-2	119.611 (2)	C19a-1—C20a-1—H1c20a-1	120.237 (2)
C5b-1—C6b-1—C7b-1^i	120.7397 (17)	C21a-1—C20a-1—H1c20a-1	120.237 (2)
C5b-1—C6b-1—H1c6b-1	119.627 (2)	C19a-2—C20a-2—C21a-2	120.0995 (19)
C7b-1^i—C6b-1—H1c6b-1	119.633 (2)	C19a-2—C20a-2—H1c20a-2	119.948 (2)
C5b-2—C6b-2—C7b-2^i	120.9956 (17)	C21a-2—C20a-2—H1c20a-2	119.9525 (19)
C5b-2—C6b-2—H1c6b-2	119.503 (2)	C19b-1—C20b-1—C21b-1	121.281 (2)
C7b-2^i—C6b-2—H1c6b-2	119.501 (2)	C19b-1—C20b-1—H1c20b-1	119.359 (2)
C6a-1—C7a-1—C8a-1	121.068 (2)	C21b-1—C20b-1—H1c20b-1	119.360 (2)
C6a-1—C7a-1—H1c7a-1	119.4654 (19)	C19b-2—C20b-2—C21b-2^iii	120.624 (2)
C8a-1—C7a-1—H1c7a-1	119.467 (2)	C19b-2—C20b-2—H1c20b-2	119.6901 (19)
C6a-2—C7a-2—C8a-2	120.252 (2)	C21b-2^iii—C20b-2—H1c20b-2	119.6859 (19)
C6a-2—C7a-2—H1c7a-2	119.8756 (19)	C20a-1—C21a-1—C22a-1^i	119.396 (2)
C8a-2—C7a-2—H1c7a-2	119.872 (2)	C20a-1—C21a-1—H1c21a-1^i	120.302 (2)
C6b-1^v—C7b-1—C8b-1	120.400 (2)	C22a-1^i—C21a-1—H1c21a-1^i	120.301 (2)
C6b-1^v—C7b-1—H1c7b-1	119.7996 (17)	C20a-2—C21a-2—C22a-2^i	119.3616 (19)
C8b-1—C7b-1—H1c7b-1	119.800 (2)	C20a-2—C21a-2—H1c21a-2^i	120.3176 (19)
C6b-2^v—C7b-2—C8b-2^iii	120.447 (2)	C22a-2^i—C21a-2—H1c21a-2^i	120.321 (2)
C6b-2^v—C7b-2—H1c7b-2	119.7769 (17)	C20b-1—C21b-1—C22b-1	118.293 (2)
C8b-2^iii—C7b-2—H1c7b-2	119.776 (2)	C20b-1—C21b-1—H1c21b-1	120.855 (2)
C7a-1—C8a-1—C9a-1	118.610 (2)	C22b-1—C21b-1—H1c21b-1	120.852 (2)
C7a-1—C8a-1—H1c8a-1	120.693 (2)	C20b-2^ii—C21b-2—C22b-2	118.5023 (19)
C9a-1—C8a-1—H1c8a-1	120.6975 (19)	C20b-2^ii—C21b-2—H1c21b-2	120.748 (2)
C7a-2—C8a-2—C9a-2	119.352 (2)	C22b-2—C21b-2—H1c21b-2	120.7501 (19)
C7a-2—C8a-2—H1c8a-2	120.324 (2)	C21a-1^v—C22a-1—C23a-1^v	119.993 (2)
C9a-2—C8a-2—H1c8a-2	120.3242 (19)	C21a-1^v—C22a-1—H1c22a-1	120.003 (2)
C7b-1—C8b-1—C9b-1	119.656 (2)	C23a-1^v—C22a-1—H1c22a-1	120.004 (2)
C7b-1—C8b-1—H1c8b-1	120.176 (2)	C21a-2^v—C22a-2—C23a-2	120.972 (2)
C9b-1—C8b-1—H1c8b-1	120.1676 (17)	C21a-2^v—C22a-2—H1c22a-2	119.5131 (19)
C7b-2^ii—C8b-2—C9b-2	119.716 (2)	C23a-2—C22a-2—H1c22a-2	119.5145 (19)
C7b-2^ii—C8b-2—H1c8b-2	120.141 (2)	C21b-1—C22b-1—C23b-1	121.594 (2)
C9b-2—C8b-2—H1c8b-2	120.1432 (17)	C21b-1—C22b-1—H1c22b-1	119.204 (2)
C8a-1—C9a-1—C10a-1	120.6469 (19)	C23b-1—C22b-1—H1c22b-1	119.202 (2)
C8a-1—C9a-1—H1c9a-1	119.677 (2)	C21b-2—C22b-2—C23b-2	121.254 (2)
C10a-1—C9a-1—H1c9a-1	119.676 (2)	C21b-2—C22b-2—H1c22b-2	119.3688 (19)
C8a-2—C9a-2—C10a-2	120.1175 (18)	C23b-2—C22b-2—H1c22b-2	119.378 (2)
C8a-2—C9a-2—H1c9a-2	119.942 (2)	C18a-1—C23a-1—C22a-1^i	122.192 (2)
C10a-2—C9a-2—H1c9a-2	119.941 (2)	C18a-1—C23a-1—H1c23a-1^i	118.905 (2)
C8b-1—C9b-1—C10b-1	119.6262 (17)	C22a-1^i—C23a-1—H1c23a-1^i	118.903 (2)
C8b-1—C9b-1—H1c9b-1	120.183 (2)	C18a-2^v—C23a-2—C22a-2	120.6793 (19)
C10b-1—C9b-1—H1c9b-1	120.191 (2)	C18a-2^v—C23a-2—H1c23a-2	119.6587 (19)
C8b-2—C9b-2—C10b-2	119.7471 (17)	C22a-2—C23a-2—H1c23a-2	119.662 (2)
C8b-2—C9b-2—H1c9b-2	120.132 (2)	C18b-1—C23b-1—C22b-1	120.802 (2)
C10b-2—C9b-2—H1c9b-2	120.121 (2)	C18b-1—C23b-1—H1c23b-1	119.596 (2)
C5a-1—C10a-1—C9a-1	120.514 (2)	C22b-1—C23b-1—H1c23b-1	119.602 (2)
C5a-1—C10a-1—H1c10a-1	119.743 (2)	C18b-2^ii—C23b-2—C22b-2	120.643 (2)
C9a-1—C10a-1—H1c10a-1	119.7425 (19)	C18b-2^ii—C23b-2—H1c23b-2	119.6810 (19)
C5a-2—C10a-2—C9a-2	120.918 (2)	C22b-2—C23b-2—H1c23b-2	119.676 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3b-1—H1c3b-1···O2b-2	0.96	3.00	3.9236	161.88
C4a-1—H1c4a-1···O3a-2^ii	0.96	2.77	3.4434	128.27
C4a-1—H1c4a-1···C10a-2^ii	0.96	2.98	3.7486	138.45
C4a-2—H1c4a-2···O3a-1	0.96	2.75	3.4260	127.83
C4a-2—H1c4a-2···C10a-1	0.96	2.93	3.7492	144.34
C6b-1—H1c6b-1···O3b-1	0.96	2.88	3.5939	131.70
C6b-2—H1c6b-2···O3b-2	0.96	2.83	3.5523	132.43
C7a-1—H1c7a-1···C21b-2	0.96	2.99	3.7658	139.35
C7a-2—H1c7a-2···C21b-1	0.96	2.97	3.7607	140.04
C7b-2—H1c7b-2···C21a-2^v	0.96	2.97	3.8098	146.59
C9a-1—H1c9a-1···C1a-2	0.96	2.86	3.6920	145.38
C9a-2—H1c9a-2···O1a-1^vii	0.96	2.95	3.8977	168.76
C9a-2—H1c9a-2···C1a-1^iii	0.96	2.85	3.6445	141.06
C10a-1—H1c10a-1···O2a-2^viii	0.96	2.72	3.6500	162.63
C10a-2—H1c10a-2···O2a-1^viii	0.96	2.68	3.6154	163.78
C10b-1—H1c10b-1···O2b-2^ix	0.96	2.74	3.6551	158.90
C10b-2—H1c10b-2···O2b-1^x	0.96	2.73	3.6457	159.21
N1a-1—H1n1a-1···O3a-2^ii	0.91	1.97	2.8328	156.81
N1a-2—H1n1a-2···O3a-1	0.92	1.95	2.8255	156.64
N1b-1—H1n1b-1···O3b-2	0.92	2.00	2.8742	158.48
N1b-2—H1n1b-2···O3b-1	0.91	1.98	2.8516	159.03
C13a-1—H1c13a-1···C21b-1	0.96	2.97	3.6499	128.46
C13b-1—H1c13b-1···C8b-2	0.96	2.90	3.8241	161.36
C13b-2—H1c13b-2···C8b-1	0.96	3.00	3.9032	157.77
C14a-1—H1c14a-1···C22b-1	0.96	2.91	3.6389	134.03
C14a-1—H1c14a-1···C23b-1	0.96	2.88	3.7966	161.21
C14a-2—H1c14a-2···C23b-2^iii	0.96	2.93	3.7487	144.46
C16b-1—H1c16b-1···C19a-2	0.96	2.95	3.8955	169.74
C16b-1—H1c16b-1···C20a-2	0.96	2.74	3.5551	143.47
C17a-2—H1c17a-2···O3a-1	0.96	2.97	3.6900	132.51
C19a-2—H1c19a-2···C15b-2	0.96	2.97	3.6762	131.32
C19a-2—H1c19a-2···C18b-2	0.96	2.99	3.8803	155.54
C19b-2—H1c19b-2···C22a-2	0.96	2.94	3.8812	168.06
C19b-2—H1c19b-2···C23a-2	0.96	2.80	3.5858	140.21
C20a-1—H1c20a-1···C16b-1	0.96	2.93	3.6124	128.84
C20a-1—H1c20a-1···C17b-1	0.96	2.87	3.7430	151.33
C20a-2—H1c20a-2···C16b-2^iii	0.96	2.95	3.6752	133.58
C20a-2—H1c20a-2···C17b-2^iii	0.96	2.85	3.7683	160.85
C20b-1—H1c20b-1···C16a-1^v	0.96	2.99	3.9214	164.76
C22a-2—H1c22a-2···C18b-1	0.96	2.97	3.6792	131.58
C22b-2—H1c22b-2···C13a-1	0.96	2.98	3.9315	169.21
C22b-2—H1c22b-2···C14a-1	0.96	2.79	3.5900	141.73
C23a-1^v—H1c23a-1···C20b-2^ii	0.96	2.87	3.7033	146.27
C23a-2—H1c23a-2···C19b-1	0.96	2.96	3.6726	131.95
C23a-2—H1c23a-2···C20b-1	0.96	2.84	3.7513	159.42
C23b-1—H1c23b-1···C19a-2	0.96	2.91	3.8350	162.08
C21a-1^v—H1c21a-1···C7b-2^ii	0.96	2.97	3.7140	135.14
C21a-1^v—H1c21a-1···C8b-2	0.96	2.85	3.7122	149.51
C21a-2^v—H1c21a-2···C7b-1	0.96	2.95	3.6875	134.39
C21a-2^v—H1c21a-2···C8b-1	0.96	2.82	3.6760	149.45
C21b-1—H1c21b-1···C8a-1	0.96	2.99	3.7822	141.12
C21b-2—H1c21b-2···C8a-2^ii	0.96	2.97	3.7816	142.49
C1b-1—H1c1b-1···C5b-1^v	0.96	2.95	3.8528	156.47
C1b-1—H1c1b-1···C10b-1	0.96	2.85	3.6200	137.59
C1b-2—H1c1b-2···C5b-2^v	0.96	2.99	3.8798	155.14
C1b-2—H1c1b-2···C10b-2^iii	0.96	2.87	3.6327	137.52

Symmetry codes: (ii) x−1, y, z; (iii) x+1, y, z; (v) x, y+1, z; (vii) x+1, y+1, z; (viii) −x+1, y+1/2, −z+1/2; (ix) −x+3/2, y+1/2, −z; (x) −x+1/2, y+1/2, −z.