Three closely-related cyclo­hexa­nols (C₃₅H₂₇X₂N₃O₃; X = F, Cl or Br): similar mol­ecular structures but different crystal structures

Three highly-substituted cyclo­hexa­nol derivatives have been prepared from 2-acetyl­pyridine and 4-halogenobenzaldehydes under mild conditions. (1RS,2SR,3SR,4RS,5RS)-3,5-Bis(4-fluoro­phen­yl)-2,4-bis­(pyridine-2-carbon­yl)-1-(pyridin-2-yl)cy­clo­hexa­nol, C₃₅H₂₇F₂N₃O₃, (I), (1RS,2SR,3SR,4RS,5RS)-3,5-bis­(4-chloro­phen­yl)-2,4-bis­(pyridine-2-carbon­yl)-1-(pyridin-2-yl)cyclo­hexa­nol acetone 0.951-solvate, C₃₅H₂₇Cl₂N₃O₃·0.951C₃H₆O, (II), and (1RS,2SR,3SR,4RS,5RS)-3,5-bis­(4-bromo­phen­yl)-2,4-bis­(pyridine-2-carbon­yl)-1-(pyridin-2-yl)cy­clo­hexa­nol, C₃₅H₂₇Br₂N₃O₃, (III), all crystallize in different space groups, viz. Pbca, Fdd2 and P, respectively. In compound (II), the acetone molecule is disordered over two sets of atomic sites having occupancies of 0.690 (13) and 0.261 (13). Each of the cyclo­hexa­nol mol­ecules contains an intra­molecular O-H...N hydrogen bond and their overall mol­ecular conformations are fairly similar. The mol­ecules of (I) are linked by two independent C-H...O hydrogen bonds to form a C(5)C(10)[R₂²(15)] chain of rings, and those of (III) are linked by a combination of C-H...O and C-H...N hydrogen bonds, forming a chain of alternating R₂²(16) and R₂²(18) rings. The cyclo­hexa­nol mol­ecules in (II) are linked by a single C-H...N hydrogen bond to form simple C(4) chains and these chains are linked by a [pi]-[pi] stacking inter­action to form sheets, to which the disordered acetone molecules are weakly linked via a number of C-H...O contacts.

S1. Introduction

Chalcones, i.e. 1,3-disubstituted prop-2-en-1-one derivatives of the form R¹COCH═CHR², are versatile inter­mediates for organic synthesis which are readily prepared via Claisen reactions between acetyl compounds R¹COCH₃ and aldehydes R²CHO. Their versatility stems from their dual modes of reactivity, involving either Michael-type addition across the C═C double bond or condensation reactions at the carbonyl function. When these two modes are active in tandem, new cyclic structures result which can be either carbocyclic (Tabba et al., 1995; Ravindran et al., 2008; Fischer et al., 2008; Fun, Hemamalini et al., 2010b) or heterocyclic (Fun, Hemamalini et al., 2010a; Jasinski, Guild et al., 2010; Jasinski, Pek et al., 2010; Samshuddin et al., 2010).

We now report the synthesis and structures of three closely related cyclo­hexanol derivatives, namely (1RS,2SR,3SR,4RS,5RS)-3,5-bis­(4-fluoro­phenyl)-2,4-bis­(pyridine-2-carbonyl)1-(pyridin-2-yl)cyclo­hexanol, (I), (1RS,2SR,3SR,4RS,5RS)-3,5-bis­(4-chloro­phenyl)-2,4-bis­(pyridine-2-carbonyl)-1-(pyridin-2-yl)cyclo­hexanol acetone 0.951-solvate, (II), and (1RS,2SR,3SR,4RS,5RS)- 3,5-bis­(4-bromo­phenyl)-2,4-bis­(pyridine-2-carbonyl)-1-(pyridin-2-yl)cyclo­hexanol, (III) (see Scheme 1). These cyclo­hexanols were prepared, in a one-pot procedure exploiting the dual reactivity of chalcones and giving satisfactory yields, by the reaction of 3:2 molar ratios of 2-acetyl­pyridine with a 4-halogenobenzaldehyde in alkaline aqueous ethanol, without the need for any form of heating. The purposes of this study were the definition of the relative stereochemistry of the five stereogenic centres, the comparison of the molecular conformations, and the exploration of the supra­molecular assembly. In addition, we compare the structures of compounds (I)–(III) with that of the recently reported analogue (IV) (Fun et al., 2012) (see Scheme 1).

S2. Experimental

S2.1. Synthesis and crystallization

For the synthesis of the solvent-free forms (I), (IIa) and (III) (see Scheme 1), 2-acetyl­pyridine (0.03 mol) and the appropriate 4-halogenobenzaldehyde (0.02 mol) were dissolved in ethanol (30 ml). Aqueous potassium hydroxide solution (10 ml of 10% w/v solution) was added and the mixtures were then stirred at 293 K for 4 h, and then permitted to stand overnight at ambient temperature. The resulting colourless products were collected by filtration and dried in air. Compound (I): yield 64%, m.p. 493–495 K; NMR (di­methyl sulfoxide-d₆): δ(H) 1.69 (m, 2H, CH₂), 3.62 (dd, 1H, H-3), 4.04 (m, 1H, H-5), 4.40 (dd, 1H, H-4), 5.52 (s, 1H, OH), 6.04 (d, 1H, H-2), 6.61–8.44 (m, 20H, aryl and pyridyl); IR (KBr, cm^-1): 3430 (OH), 1682 (C═ O); analysis found: C 72.9, H 4.7, N 6.5%; C₃₅H₂₇F₂N₃O₃ requires: C 73.0, H 4.7, N 6.6%. Compound (IIa): yield 66%, m.p. 416–419 K; NMR (di­methyl sulfoxide-d₆): δ(H) 1.75 (m, 2H, CH₂), 3.70 (dd, 1H, H-3), 4.05 (m, 1H, H-5), 4.45 (dd, 1H, H-4), 5.50 (s, 1H, OH), 6.05 (d, 1H, H-2), 6.84–8.44 (m, 20H, aryl and pyridyl); IR (KBr, cm^-1): 3434 (OH), 1689 (C═O); analysis found:C 68.9, H 4.5, N 6.9%; C₃₅H₂₇Cl₂N₃O₃ requires: C 69.3, H 4.5, N 6.9%. Compound (III): yield 72%, m.p. 508–510 K; NMR (chloro­form-d₃): δ(H) 1.95 (m, 2H, CH₂), 3.50 (dd, 1H, H-3), 4.15 (m, 1H, H-5), 4.40 (dd, 1H, H-4), 5.50 (s, 1H, OH), 6.22 (m, 1H, H-2), 6.86–7.49 (m, 20H, aryl and pyridyl); δ(C) 37.9, 40.6, 47.7, 199.9, 120.9, 121.0, 121.6, 121.8, 126.0, 126.1, 126.5, 130.2, 130.7, 130.8, 136.0, 136.1, 139.7, 141.0, 146.9, 147.9, 148.0, 153.7, 153.9, 162.2, 203.0, 205.0; IR (KBr, cm^-1): 3429 (OH), 1682 (C═O); analysis found: C 60.2, H 3.9, N 6.0%; C₃₅H₂₇Br₂N₃O₃ requires: C 60.3, H 3.9, N 6.0%. Crystals of (I)–(III) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of solutions in acetone.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms in the cyco­hexanol components were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic and heteroaromatic), 0.99 (CH₂) or 1.00 Å (aliphatic), and with U_iso(H) = 1.2U_eq(C). H atoms bonded to O atoms were permitted to ride at the positions located in difference maps, with U_iso(H) = 1.5U_eq(O), giving the O—H distances shown in Table 3. Chloro compound (II) crystallizes as an acetone solvate where the solvent molecules are over two sets of atomic sites. For the minor component, the bonded distances and the one-angle nonbonded distances were restrained to the corresponding values in the major component, subject to variations of 0.005 and 0.01 Å, respectively. In addition, the anisotropic displacement parameters for atoms C71 and C81 were constrained to be identical, as were those of atoms O71 and O81, and those of methyl atoms C72, C73, C82 and C83. The H atoms for both components of the acetone component were included in calculated positions as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.5U_eq(C). Subject to these conditions, the occupancies of the major and minor components refined to 0.690 (13) and 0.261 (13), respectively. The correct orientation of the structure of (II) with respect to the polar-axis direction was determined using the Flack x parameter (Flack, 1983), calculated using 613 quotients of the type [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013), although this has no chemical significance. Examination of the refined structures using PLATON (Spek, 2009) showed that none of them contained any solvent-accessible voids.

S3. Results and discussion

Although all of the cyclo­hexanols reported here, (I)–(III), were recrystallized from acetone, fluoro and bromo derivatives (I) and (III) crystallized in solvent-free form but chloro derivative (II) crystallized as a nonstoichiometric acetone solvate, in which the acetone solvent component is disordered over two adjacent sets of atomic sites having occupancies of 0.690 (13) and 0.261 (13) in the crystal selected for data collection. In addition to the contrast between solvate (II) and solvent-free forms (I) and (III), all of these compounds crystallize in different space groups, viz. Pbca, Fdd2 and P1, respectively, for compounds (I), (II) and (III), despite the very small differences in their overall molecular constitutions. This behaviour contrasts with the isomorphous behaviour sometimes seen in compounds which differ only in the identity of their halogen substituents (e.g. Glidewell et al., 2005; Nayak et al., 2014). Compound (IV) crystallizes in the space group P2₁/c as a stoichiometric 1:1 solvate with butanone, although the reported synthetic procedure for (IV) specifies that the compound was crystallized from acetone (Fun et al., 2012).

The cyclo­hexanol components in compounds (I)–(III) contain five stereogenic centres and, for each compound, the reference molecule was selected as one having the R configuration at atom C1 (Figs. 1–3). On this basis, the reference molecules all have the configuration (1R,2S,3S,4R,5R) and the space groups confirm that all three compounds crystallize as racemic mixtures. Compound (IV) has exactly the same stereochemistry, although this aspect of its structure was not mentioned in the original structure report (Fun et al., 2012). The isolated yields of the (1RS,2SR,3SR,4RS,5RS) forms for compounds (I)–(IV), in the range 64–74%, suggest a high degree of stereoselectivity in the formation of the substituted cyclo­hexane ring.

The formation of these polysubstituted cyclo­hexanols from very simple precursors can be envisaged as starting with a condensation reaction between the substituted benzaldehyde, ArCHO, and 2-acetyl­pyridine, MeCOPy, to form a chalcone inter­mediate (A) (see Scheme 2). This step is followed by two Michael additions, the first of which is addition of MeCOPy to the chalcone (A) to form the inter­mediate (B), and the second addition is that of (B) to a further molecule of (A) giving (C). Finally, an intra­molecular aldol reaction converts inter­mediate (C) to the cyclo­hexanol product. The formation of inter­mediate (B) introduces a stereogenic centre, at the site which will eventually become atom C5 of the cyclo­hexane ring (cf. Figs 1–3). Inter­mediate (B) is necessary racemic, as no component in the initial reaction mixtures is capable of inducing enanti­oselectivity. However, the presence of a stereogenic centre in (B) appears to control the relative stereochemistry at the remaining stereogenic centres subsequently formed at the final positions C1, C2, C3 and C4. This reaction scheme accounts for the reaction stoichiometry, the formation of five adjacent stereogenic centres and the formation of the final products as racemic mixtures, but it must be emphasized that this scheme is largely conjectural, albeit firmly based on the straightforward application of simple organic processes.

Within the cyclo­hexanol components, the cyclo­hexane rings all adopt chair conformations and the ring-puckering angles θ, calculated (Cremer & Pople, 1975) for the atom sequence C1–C2–C3–C4–C5–C6 are 5.36 (17), 5.5 (3) and 0.0 (3)° for compounds (I), (II) and (III), respectively; the corresponding value for compound (IV) is 4.69 (15)°. The ideal value for a perfect chair conformation is θ = 0.0° (Boeyens, 1978). The organic substituents at atoms C1, C2, C3 and C5 all occupy equatorial sites, and both the hy­droxy group at atom C1 and the acyl substituent at atom C4 occupy axial sites.

In each of compounds (I)–(III) there is an intra­molecular O—H···N hydrogen bond (Table 3), which may serve effectively to lock the orientation of the pyridine ring bonded to atom C1. The overall molecular conformation can be conveniently summarized in terms of the dihedral angles between the successive rings bonded to the central cyclo­hexane ring (Table 2); the corresponding values for (I)–(III) are in general similar, although with some small differences in detail. The overall similarity between compounds (I)–(III) in terms of their molecular constitutions, stereochemistry and molecular conformations makes their marked differences in crystallization behavior difficult to understand.

The supra­molecular assembly in compounds (I)–(III) is fairly simple for molecules of this complexity. Thus, for example, despite the presence in each cyclo­hexanol molecule of five independent aryl or pyridyl rings, there are no π–π inter­actions in the structure of (I) and only one such inter­action in each of (II) and (III). Similarly, there are no C—H···π inter­actions in the structures of (I) and (III), while the single inter­action of this type in (II) has long H···Cg and C···Cg distances (Table 3), and it is not considered to be structurally significant. The principal inter­molecular inter­actions are thus C—H···N and C—H···O hydrogen bonds, augmented by the π–π inter­actions in (II) and (III). In the structure of compound (I), a combination of two C—H···O hydrogen bonds (Table 3) links molecules related by a b-glide plane to form a C(5)C(10)[R₂²(15)] chain of rings (Bernstein et al., 1995) running parallel to the [010] direction (Fig. 4).

There are several C—H···O contacts between the molecular components in compound (II) (Table 3). Within the selected asymmetric unit, the cyclo­hexanol molecule forms rather long C—H···O contacts with the two partial-occupancy components of the disordered acetone molecule, one of them with an H···O distance beyond the sum (2.65 Å) of the van der Waals radii for H and O (Rowland & Taylor, 1996). A third such contact has a C—H···O angle of only 129°, so that this contact is probably not structurally significant (Wood et al., 2009). The weak bonding of the acetone to the cyclo­hexanol component may account for the nonstoichiometric nature of the solvation, for the positional disorder of the solvent molecule, and for the relatively large displacement parameters for the solvent component. Subject to these provisos, and that mentioned above concerning the C—H···π contact, the sole significant inter­molecular hydrogen bond, of C—H···N type, links cyclo­hexanol molecules related by the d-glide plane at y = 0.375 to form a simple C(4) chain running parallel to the [101] direction (Fig. 5). These simple chains are linked into sheets by a single π–π stacking inter­action. The pyridyl rings containing atoms N11 and N41 in the molecules at (x, y, z) and (x+1/2, y, z+1/2), respectively, make a dihedral angle of 4.7 (2)°. The ring-centroid separation is 3.846 (2) Å and the shortest perpendicular distance from the centroid of one ring to the plane of the other is 3.3909 (17) Å, corresponding to a nearly ideal ring-centroid offset of ca 1.52 Å. This inter­action links cyclo­hexanol molecules related by translation to form a π-stacked chain running parallel to the [101] direction (Fig. 6). The combination of the hydrogen-bonded chains along [101] and the π-stacked chains along [101] links the cyclo­hexanol molecules into a sheet parallel to (010) to which the acetone molecules are linked only weakly, if at all.

A combination of one C—H···N hydrogen bond and one C—H···O hydrogen bond links the molecules of compound (III) into a chain of centrosymmetric rings running parallel to the [011] direction (Fig. 7). Inversion-related pairs of C—H···N hydrogen bonds link pairs of molecules into R₂²(18) rings centred at (0, 0.5-n, n), where n represents an integer, and these rings alternate with R₂²(16) rings containing inversion-related pairs of C—H···O hydrogen bonds which are centred at (0, n, 0.5-n), where n again represents an integer. There is a single π–π inter­action in this structure; the pyridine rings containing atom N21 in the molecules at (x, y, z) and (-x+1, -y, -z+1) are parallel. The inter­planar spacing is 3.555 (2) Å, the ring-centroid separation is 3.680 (3) and the ring-centroid offset is 0.951 (3) Å, and the effect of this inter­action is to link the hydrogen-bonded chain into a sheet parallel to (011).

In the structure of compound (III), there is a short inter­molecular Br···Br contact between inversion-related molecules, with Br54···Br54ⁱ = 3.3802 (6) Å and C54—Br54···Br54ⁱ= 159.23 (9)° [symmetry code: (i) -x, -y+1, -z]. A database study of the angular distribution of such contacts (Ramasubbu et al., 1986) has shown that the C—X···X angles (where X = Cl, Br or I) are clustered either around 100° or around 165°, and the angle observed in compound (III) is consistent with this finding. Although the observed Br···Br distance in (III) is shorter that the conventional sum of van der Waals radii (3.70 Å; Rowland & Taylor, 1996), a database study of the non-bonded distances in such contacts (Nyburg & Faerman, 1985) found that atoms such as halogens bonded to C atoms do not behave in this context as though they were spherical but instead they behave as oblate ellipsoids, with the major axis normal to the direction of the C—X bond and the minor axis parallel to the C—X bond. For Br, these characteristic radii were found to be 2.01 and 1.64 Å, respectively, and, on this basis, the observed Br···Br distance in compound (III) does not seem to be exceptional.

In compound (IV) (Fun et al., 2012), the supra­molecular assembly consists of C(5) chains built from a single C—H···O hydrogen bond, to which the butanone solvent molecules are linked, also via C—H···O hydrogen bonds. Although the presence of a π–π stacking inter­action was mentioned in the original structure report, no discussion of its action was given. In fact, this inter­action links the hydrogen-bonded chains into a sheet lying parallel to (100) (Fig. 8).

Related literature

For related literature, see: Bernstein et al. (1995); Boeyens (1978); Cremer & Pople (1975); Fischer et al. (2008); Flack (1983); Fun et al. (2010a, 2010b, 2012); Glidewell et al. (2005); Jasinski, Guild, Samshuddin, Narayana & Yathirajan (2010); Jasinski, Pek, Samshuddin, Narayana & Yathirajan (2010); Nayak et al. (2014); Nyburg & Faerman (1985); Parsons et al. (2013); Ramasubbu et al. (1986); Ravindran et al. (2008); Rowland & Taylor (1996); Samshuddin et al. (2010); Spek (2009); Tabba et al. (1995); Wood et al. (2009).

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the (1R,2S,3S,4R,5R) enantiomer of compound (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. [some lines/H atoms missing in ??? ring; please revise]
	Fig. 2. The independent molecular components of compound (II), showing the atom-labelling scheme for the (1R,2S,3S,4R,5R) enantiomer of the cyclohexanol component and the disordered acetone component. Unlabelled atoms C15 and C16 are below O71. The occupancies of the two acetone components are 0.690 (13) and 0.261 (13) and the displacement ellipsoids are drawn at the 30% probability level. [some lines/H atoms missing in ??? ring; please revise]
	Fig. 3. The molecular structure of the (1R,2S,3S,4R,5R) enantiomer of compound (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded C(5)C(10)[R2^2(15)] chain of rings parallel to [010]. Hydrogen bonds are shown as dashed lines and H atoms not involved in the motifs shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded C(4) chain parallel to [101]. Hydrogen bonds are shown as dashed lines and the the acetone components and H atoms not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of compound (II), showing the formation of a π-stacked chain parallel to [101]. The acetone components and all of the H atoms have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of compound (III), showing the formation of a hydrogen-bonded chain of centrosymmetric R2^2(16) and R2^2(18) rings parallel to [011]. Hydrogen bonds are shown as dashed lines and H atoms not involved in the motifs shown have been omitted.
	Fig. 8. A stereoview of part of the crystal structure of compound (IV), showing the formation of a π-stacked sheet of hydrogen-bonded chains parallel to (100). The original atomic coordinates (Fun et al., 2012) have been used. Hydrogen bonds are shown as dashed lines and the butanone solvent molecules and H atoms not involved in the motif shown have been omitted.

(I) (1RS,2SR,3SR,4RS,5RS)-3,5-Bis(4-fluorophenyl)-2,4-bis(pyridine-2-carbonyl)1-(pyridin-2-yl)cyclohexanol

Crystal data

C35H27F2N3O3	Dx = 1.282 Mg m^−3
Mr = 575.60	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 5754 reflections
a = 21.8864 (9) Å	θ = 3.6–71.2°
b = 11.2268 (4) Å	µ = 0.75 mm^−1
c = 24.2670 (9) Å	T = 200 K
V = 5962.7 (4) Å^3	Needle, colourless
Z = 8	0.40 × 0.09 × 0.08 mm
F(000) = 2400

Data collection

Agilent Eos Gemini diffractometer	4489 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	Rint = 0.036
ω scans	θmax = 71.2°, θmin = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −18→26
Tmin = 0.693, Tmax = 0.942	k = −13→13
37077 measured reflections	l = −27→29
5754 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0634P)^2 + 1.1285P] where P = (Fo^2 + 2Fc^2)/3
5754 reflections	(Δ/σ)max < 0.001
388 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.19695 (8)	0.56058 (14)	0.29755 (6)	0.0469 (4)
O11	0.20061 (6)	0.43914 (10)	0.28039 (5)	0.0587 (3)
H11	0.1716	0.4286	0.2598	0.088*
C2	0.15217 (7)	0.57345 (13)	0.34750 (6)	0.0436 (3)
H2	0.1509	0.6589	0.3590	0.052*
C3	0.17385 (7)	0.49773 (13)	0.39661 (6)	0.0434 (3)
H3	0.1731	0.4128	0.3842	0.052*
C4	0.24067 (7)	0.52586 (13)	0.41351 (6)	0.0433 (3)
H4	0.2539	0.4617	0.4395	0.052*
C5	0.28430 (7)	0.52110 (13)	0.36324 (7)	0.0463 (3)
H5	0.2842	0.4368	0.3500	0.056*
C6	0.26119 (7)	0.59731 (15)	0.31527 (7)	0.0495 (4)
H6A	0.2609	0.6821	0.3265	0.059*
H6B	0.2894	0.5890	0.2836	0.059*
N11	0.13521 (8)	0.57704 (16)	0.21601 (6)	0.0662 (4)
C12	0.17203 (8)	0.63612 (16)	0.25019 (7)	0.0513 (4)
C13	0.18284 (11)	0.75631 (19)	0.24506 (9)	0.0716 (5)
H13	0.2101	0.7960	0.2694	0.086*
C14	0.15306 (14)	0.8180 (2)	0.20361 (11)	0.0942 (8)
H14	0.1597	0.9010	0.1990	0.113*
C15	0.11414 (13)	0.7586 (3)	0.16938 (10)	0.0927 (8)
H15	0.0927	0.7995	0.1411	0.111*
C16	0.10686 (12)	0.6393 (3)	0.17684 (9)	0.0853 (7)
H16	0.0800	0.5980	0.1527	0.102*
C27	0.08834 (8)	0.53511 (15)	0.33041 (7)	0.0493 (4)
O27	0.07514 (6)	0.43068 (11)	0.32607 (6)	0.0646 (3)
N21	0.05596 (9)	0.74111 (16)	0.32838 (8)	0.0758 (5)
C22	0.04146 (8)	0.62888 (18)	0.31706 (7)	0.0573 (4)
C23	−0.01306 (10)	0.5955 (3)	0.29329 (10)	0.0846 (7)
H23	−0.0222	0.5142	0.2861	0.102*
C24	−0.05428 (13)	0.6857 (4)	0.28028 (13)	0.1123 (10)
H24	−0.0920	0.6669	0.2630	0.135*
C25	−0.04035 (15)	0.8010 (3)	0.29238 (13)	0.1112 (10)
H25	−0.0684	0.8633	0.2847	0.133*
C26	0.01477 (14)	0.8246 (3)	0.31575 (11)	0.1002 (9)
H26	0.0246	0.9052	0.3236	0.120*
C31	0.13233 (7)	0.50623 (14)	0.44664 (7)	0.0473 (4)
C32	0.10194 (9)	0.60966 (17)	0.46100 (8)	0.0604 (4)
H32	0.1041	0.6769	0.4373	0.072*
C33	0.06841 (10)	0.6169 (2)	0.50932 (9)	0.0737 (6)
H33	0.0479	0.6885	0.5190	0.088*
C34	0.06538 (10)	0.5205 (2)	0.54226 (9)	0.0771 (6)
F34	0.03235 (8)	0.52803 (18)	0.58975 (6)	0.1177 (6)
C35	0.09327 (12)	0.4160 (2)	0.52967 (9)	0.0830 (7)
H35	0.0899	0.3491	0.5535	0.100*
C36	0.12679 (10)	0.40895 (18)	0.48118 (8)	0.0649 (5)
H36	0.1462	0.3362	0.4716	0.078*
C47	0.24466 (7)	0.64265 (13)	0.44453 (7)	0.0456 (3)
O47	0.23444 (6)	0.73801 (9)	0.42281 (5)	0.0575 (3)
N41	0.28713 (11)	0.54117 (16)	0.52388 (8)	0.0865 (6)
C42	0.26141 (9)	0.63990 (15)	0.50466 (7)	0.0561 (4)
C43	0.25094 (12)	0.73865 (19)	0.53713 (8)	0.0764 (6)
H43	0.2322	0.8079	0.5223	0.092*
C44	0.26832 (17)	0.7342 (3)	0.59181 (10)	0.1086 (10)
H44	0.2610	0.8002	0.6154	0.130*
C45	0.29594 (18)	0.6346 (3)	0.61140 (11)	0.1234 (12)
H45	0.3091	0.6302	0.6486	0.148*
C46	0.30429 (18)	0.5414 (3)	0.57659 (12)	0.1228 (12)
H46	0.3236	0.4719	0.5907	0.147*
C51	0.34937 (7)	0.54824 (14)	0.38108 (7)	0.0481 (4)
C52	0.37957 (9)	0.46579 (17)	0.41399 (9)	0.0653 (5)
H52	0.3597	0.3934	0.4234	0.078*
C53	0.43805 (9)	0.48691 (19)	0.43340 (9)	0.0705 (5)
H53	0.4584	0.4302	0.4560	0.085*
C54	0.46566 (8)	0.59140 (18)	0.41921 (8)	0.0598 (4)
F54	0.52375 (5)	0.61192 (12)	0.43809 (5)	0.0820 (4)
C55	0.43852 (8)	0.67500 (17)	0.38715 (8)	0.0621 (5)
H55	0.4592	0.7468	0.3780	0.074*
C56	0.37968 (8)	0.65291 (15)	0.36802 (8)	0.0550 (4)
H56	0.3599	0.7106	0.3456	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0533 (9)	0.0418 (8)	0.0455 (8)	0.0003 (6)	−0.0003 (7)	−0.0037 (7)
O11	0.0640 (7)	0.0490 (6)	0.0631 (7)	0.0062 (5)	−0.0044 (6)	−0.0149 (6)
C2	0.0496 (8)	0.0366 (7)	0.0447 (8)	0.0021 (6)	−0.0022 (6)	−0.0004 (6)
C3	0.0501 (8)	0.0328 (7)	0.0474 (8)	0.0012 (6)	−0.0015 (6)	0.0008 (6)
C4	0.0496 (8)	0.0340 (7)	0.0462 (8)	0.0013 (6)	−0.0034 (6)	0.0028 (6)
C5	0.0495 (9)	0.0381 (7)	0.0514 (8)	0.0022 (6)	−0.0018 (7)	−0.0023 (6)
C6	0.0483 (9)	0.0523 (9)	0.0478 (8)	0.0008 (7)	0.0011 (7)	0.0016 (7)
N11	0.0690 (10)	0.0781 (11)	0.0516 (8)	−0.0047 (8)	−0.0112 (7)	−0.0038 (8)
C12	0.0541 (9)	0.0577 (10)	0.0421 (8)	−0.0008 (7)	0.0008 (7)	−0.0011 (7)
C13	0.0880 (14)	0.0628 (12)	0.0641 (12)	−0.0082 (10)	−0.0169 (10)	0.0112 (9)
C14	0.119 (2)	0.0785 (15)	0.0852 (16)	−0.0030 (14)	−0.0186 (15)	0.0296 (13)
C15	0.0962 (18)	0.116 (2)	0.0661 (14)	0.0048 (15)	−0.0201 (12)	0.0294 (14)
C16	0.0844 (15)	0.113 (2)	0.0583 (12)	−0.0039 (14)	−0.0201 (11)	0.0039 (12)
C27	0.0525 (9)	0.0505 (9)	0.0450 (8)	−0.0014 (7)	0.0009 (7)	0.0017 (7)
O27	0.0643 (8)	0.0548 (7)	0.0748 (8)	−0.0110 (6)	−0.0088 (6)	0.0017 (6)
N21	0.0841 (12)	0.0654 (11)	0.0780 (11)	0.0245 (9)	−0.0153 (9)	−0.0006 (9)
C22	0.0535 (9)	0.0708 (12)	0.0476 (9)	0.0096 (8)	0.0003 (7)	0.0047 (8)
C23	0.0627 (12)	0.1074 (18)	0.0838 (15)	0.0044 (12)	−0.0151 (11)	0.0066 (13)
C24	0.0685 (15)	0.160 (3)	0.109 (2)	0.0285 (18)	−0.0282 (14)	0.014 (2)
C25	0.104 (2)	0.126 (3)	0.104 (2)	0.058 (2)	−0.0170 (17)	0.0143 (19)
C26	0.112 (2)	0.0883 (17)	0.1003 (18)	0.0465 (16)	−0.0226 (16)	0.0019 (14)
C31	0.0469 (8)	0.0490 (8)	0.0461 (8)	−0.0031 (7)	−0.0036 (7)	0.0001 (7)
C32	0.0650 (11)	0.0566 (10)	0.0595 (10)	0.0019 (8)	0.0082 (8)	−0.0039 (8)
C33	0.0722 (13)	0.0803 (14)	0.0686 (12)	−0.0002 (11)	0.0124 (10)	−0.0182 (11)
C34	0.0707 (13)	0.1070 (18)	0.0534 (11)	−0.0127 (12)	0.0120 (9)	−0.0094 (11)
F34	0.1163 (12)	0.1697 (16)	0.0670 (8)	−0.0229 (11)	0.0383 (8)	−0.0117 (9)
C35	0.0904 (16)	0.0956 (17)	0.0630 (12)	−0.0111 (13)	0.0090 (11)	0.0248 (12)
C36	0.0704 (12)	0.0625 (11)	0.0619 (11)	0.0012 (9)	0.0033 (9)	0.0128 (9)
C47	0.0474 (8)	0.0381 (8)	0.0513 (8)	−0.0013 (6)	0.0000 (7)	0.0017 (7)
O47	0.0793 (8)	0.0351 (6)	0.0580 (7)	0.0012 (5)	−0.0048 (6)	0.0018 (5)
N41	0.1270 (17)	0.0641 (11)	0.0682 (11)	0.0086 (10)	−0.0376 (11)	0.0004 (9)
C42	0.0673 (11)	0.0477 (9)	0.0531 (9)	−0.0099 (8)	−0.0066 (8)	0.0002 (7)
C43	0.1111 (18)	0.0619 (12)	0.0562 (11)	−0.0032 (11)	0.0002 (11)	−0.0056 (9)
C44	0.173 (3)	0.0959 (19)	0.0572 (13)	−0.0161 (19)	−0.0056 (16)	−0.0175 (13)
C45	0.196 (4)	0.112 (2)	0.0613 (15)	−0.022 (2)	−0.0468 (19)	0.0030 (15)
C46	0.196 (4)	0.0907 (19)	0.0821 (17)	0.010 (2)	−0.066 (2)	0.0076 (15)
C51	0.0480 (9)	0.0433 (8)	0.0529 (9)	0.0031 (6)	0.0018 (7)	−0.0014 (7)
C52	0.0575 (10)	0.0523 (10)	0.0862 (13)	−0.0029 (8)	−0.0101 (9)	0.0141 (9)
C53	0.0605 (11)	0.0714 (13)	0.0795 (13)	0.0020 (9)	−0.0142 (10)	0.0209 (10)
C54	0.0480 (9)	0.0718 (12)	0.0597 (10)	−0.0051 (8)	−0.0060 (8)	−0.0029 (9)
F54	0.0588 (6)	0.1041 (9)	0.0831 (8)	−0.0149 (6)	−0.0181 (6)	0.0077 (7)
C55	0.0576 (10)	0.0542 (10)	0.0744 (12)	−0.0093 (8)	−0.0008 (9)	0.0043 (9)
C56	0.0523 (9)	0.0492 (9)	0.0634 (10)	0.0012 (7)	−0.0025 (8)	0.0062 (8)

Geometric parameters (Å, º)

C1—O11	1.4279 (19)	C25—C26	1.359 (4)
C1—C6	1.527 (2)	C25—H25	0.9500
C1—C12	1.529 (2)	C26—H26	0.9500
C1—C2	1.565 (2)	C31—C36	1.382 (2)
O11—H11	0.8158	C31—C32	1.383 (2)
C2—C27	1.519 (2)	C32—C33	1.386 (3)
C2—C3	1.539 (2)	C32—H32	0.9500
C2—H2	1.0000	C33—C34	1.347 (3)
C3—C31	1.520 (2)	C33—H33	0.9500
C3—C4	1.551 (2)	C34—C35	1.357 (4)
C3—H3	1.0000	C34—F34	1.363 (2)
C4—C47	1.514 (2)	C35—C36	1.389 (3)
C4—C5	1.550 (2)	C35—H35	0.9500
C4—H4	1.0000	C36—H36	0.9500
C5—C51	1.519 (2)	C47—O47	1.2140 (19)
C5—C6	1.531 (2)	C47—C42	1.505 (2)
C5—H5	1.0000	N41—C42	1.328 (3)
C6—H6A	0.9900	N41—C46	1.333 (3)
C6—H6B	0.9900	C42—C43	1.379 (3)
N11—C12	1.333 (2)	C43—C44	1.381 (3)
N11—C16	1.333 (3)	C43—H43	0.9500
C12—C13	1.376 (3)	C44—C45	1.357 (4)
C13—C14	1.384 (3)	C44—H44	0.9500
C13—H13	0.9500	C45—C46	1.357 (4)
C14—C15	1.364 (4)	C45—H45	0.9500
C14—H14	0.9500	C46—H46	0.9500
C15—C16	1.361 (4)	C51—C56	1.386 (2)
C15—H15	0.9500	C51—C52	1.390 (2)
C16—H16	0.9500	C52—C53	1.384 (3)
C27—O27	1.212 (2)	C52—H52	0.9500
C27—C22	1.505 (2)	C53—C54	1.364 (3)
N21—C22	1.328 (3)	C53—H53	0.9500
N21—C26	1.336 (3)	C54—C55	1.356 (3)
C22—C23	1.378 (3)	C54—F54	1.371 (2)
C23—C24	1.393 (4)	C55—C56	1.391 (2)
C23—H23	0.9500	C55—H55	0.9500
C24—C25	1.362 (4)	C56—H56	0.9500
C24—H24	0.9500
O11—C1—C6	106.76 (13)	C25—C24—H24	120.1
O11—C1—C12	109.29 (13)	C23—C24—H24	120.1
C6—C1—C12	112.97 (13)	C26—C25—C24	118.3 (2)
O11—C1—C2	110.43 (13)	C26—C25—H25	120.9
C6—C1—C2	109.49 (13)	C24—C25—H25	120.9
C12—C1—C2	107.91 (13)	N21—C26—C25	123.9 (3)
C1—O11—H11	105.9	N21—C26—H26	118.0
C27—C2—C3	109.78 (12)	C25—C26—H26	118.0
C27—C2—C1	109.77 (13)	C36—C31—C32	117.94 (17)
C3—C2—C1	110.82 (12)	C36—C31—C3	119.17 (15)
C27—C2—H2	108.8	C32—C31—C3	122.80 (15)
C3—C2—H2	108.8	C31—C32—C33	121.13 (19)
C1—C2—H2	108.8	C31—C32—H32	119.4
C31—C3—C2	113.55 (13)	C33—C32—H32	119.4
C31—C3—C4	109.86 (12)	C34—C33—C32	118.8 (2)
C2—C3—C4	112.52 (12)	C34—C33—H33	120.6
C31—C3—H3	106.8	C32—C33—H33	120.6
C2—C3—H3	106.8	C33—C34—C35	122.59 (19)
C4—C3—H3	106.8	C33—C34—F34	118.6 (2)
C47—C4—C5	112.67 (12)	C35—C34—F34	118.9 (2)
C47—C4—C3	111.22 (12)	C34—C35—C36	118.5 (2)
C5—C4—C3	111.44 (12)	C34—C35—H35	120.7
C47—C4—H4	107.1	C36—C35—H35	120.7
C5—C4—H4	107.1	C31—C36—C35	121.0 (2)
C3—C4—H4	107.1	C31—C36—H36	119.5
C51—C5—C6	114.48 (13)	C35—C36—H36	119.5
C51—C5—C4	110.25 (13)	O47—C47—C42	118.94 (15)
C6—C5—C4	112.07 (13)	O47—C47—C4	122.49 (14)
C51—C5—H5	106.5	C42—C47—C4	118.56 (13)
C6—C5—H5	106.5	C42—N41—C46	117.1 (2)
C4—C5—H5	106.5	N41—C42—C43	122.75 (18)
C1—C6—C5	111.55 (13)	N41—C42—C47	117.45 (16)
C1—C6—H6A	109.3	C43—C42—C47	119.79 (17)
C5—C6—H6A	109.3	C42—C43—C44	118.3 (2)
C1—C6—H6B	109.3	C42—C43—H43	120.9
C5—C6—H6B	109.3	C44—C43—H43	120.9
H6A—C6—H6B	108.0	C45—C44—C43	119.3 (3)
C12—N11—C16	117.64 (19)	C45—C44—H44	120.4
N11—C12—C13	122.39 (17)	C43—C44—H44	120.4
N11—C12—C1	114.04 (15)	C44—C45—C46	118.5 (2)
C13—C12—C1	123.42 (16)	C44—C45—H45	120.7
C12—C13—C14	118.4 (2)	C46—C45—H45	120.7
C12—C13—H13	120.8	N41—C46—C45	124.1 (3)
C14—C13—H13	120.8	N41—C46—H46	118.0
C15—C14—C13	119.5 (2)	C45—C46—H46	118.0
C15—C14—H14	120.3	C56—C51—C52	117.92 (16)
C13—C14—H14	120.3	C56—C51—C5	123.61 (15)
C16—C15—C14	118.2 (2)	C52—C51—C5	118.43 (15)
C16—C15—H15	120.9	C53—C52—C51	121.41 (18)
C14—C15—H15	120.9	C53—C52—H52	119.3
N11—C16—C15	123.8 (2)	C51—C52—H52	119.3
N11—C16—H16	118.1	C54—C53—C52	118.12 (18)
C15—C16—H16	118.1	C54—C53—H53	120.9
O27—C27—C22	119.69 (16)	C52—C53—H53	120.9
O27—C27—C2	121.13 (15)	C55—C54—C53	123.09 (17)
C22—C27—C2	119.16 (15)	C55—C54—F54	118.79 (17)
C22—N21—C26	117.2 (2)	C53—C54—F54	118.11 (17)
N21—C22—C23	123.49 (19)	C54—C55—C56	118.26 (17)
N21—C22—C27	117.14 (16)	C54—C55—H55	120.9
C23—C22—C27	119.36 (19)	C56—C55—H55	120.9
C22—C23—C24	117.3 (3)	C51—C56—C55	121.20 (16)
C22—C23—H23	121.4	C51—C56—H56	119.4
C24—C23—H23	121.4	C55—C56—H56	119.4
C25—C24—C23	119.8 (3)
O11—C1—C2—C27	−61.80 (16)	C22—C23—C24—C25	−1.5 (4)
C6—C1—C2—C27	−179.08 (13)	C23—C24—C25—C26	1.7 (5)
C12—C1—C2—C27	57.59 (16)	C22—N21—C26—C25	0.1 (4)
O11—C1—C2—C3	59.62 (16)	C24—C25—C26—N21	−1.0 (5)
C6—C1—C2—C3	−57.65 (16)	C2—C3—C31—C36	148.77 (15)
C12—C1—C2—C3	179.02 (13)	C4—C3—C31—C36	−84.24 (18)
C27—C2—C3—C31	−58.61 (16)	C2—C3—C31—C32	−34.7 (2)
C1—C2—C3—C31	179.97 (12)	C4—C3—C31—C32	92.30 (18)
C27—C2—C3—C4	175.80 (12)	C36—C31—C32—C33	1.9 (3)
C1—C2—C3—C4	54.37 (16)	C3—C31—C32—C33	−174.72 (17)
C31—C3—C4—C47	−51.99 (16)	C31—C32—C33—C34	−0.5 (3)
C2—C3—C4—C47	75.59 (16)	C32—C33—C34—C35	−0.8 (4)
C31—C3—C4—C5	−178.62 (12)	C32—C33—C34—F34	180.0 (2)
C2—C3—C4—C5	−51.05 (16)	C33—C34—C35—C36	0.7 (4)
C47—C4—C5—C51	54.51 (16)	F34—C34—C35—C36	179.9 (2)
C3—C4—C5—C51	−179.66 (12)	C32—C31—C36—C35	−1.9 (3)
C47—C4—C5—C6	−74.26 (16)	C3—C31—C36—C35	174.78 (19)
C3—C4—C5—C6	51.57 (16)	C34—C35—C36—C31	0.7 (3)
O11—C1—C6—C5	−60.66 (17)	C5—C4—C47—O47	58.7 (2)
C12—C1—C6—C5	179.18 (13)	C3—C4—C47—O47	−67.30 (19)
C2—C1—C6—C5	58.90 (17)	C5—C4—C47—C42	−121.88 (15)
C51—C5—C6—C1	176.87 (13)	C3—C4—C47—C42	112.16 (16)
C4—C5—C6—C1	−56.61 (17)	C46—N41—C42—C43	−1.6 (4)
C16—N11—C12—C13	−2.1 (3)	C46—N41—C42—C47	177.1 (3)
C16—N11—C12—C1	173.54 (18)	O47—C47—C42—N41	−163.26 (19)
O11—C1—C12—N11	28.5 (2)	C4—C47—C42—N41	17.3 (3)
C6—C1—C12—N11	147.25 (15)	O47—C47—C42—C43	15.5 (3)
C2—C1—C12—N11	−91.57 (17)	C4—C47—C42—C43	−164.01 (18)
O11—C1—C12—C13	−155.82 (18)	N41—C42—C43—C44	0.3 (4)
C6—C1—C12—C13	−37.1 (2)	C47—C42—C43—C44	−178.3 (2)
C2—C1—C12—C13	84.1 (2)	C42—C43—C44—C45	1.2 (5)
N11—C12—C13—C14	1.6 (3)	C43—C44—C45—C46	−1.4 (6)
C1—C12—C13—C14	−173.7 (2)	C42—N41—C46—C45	1.4 (5)
C12—C13—C14—C15	0.1 (4)	C44—C45—C46—N41	0.1 (6)
C13—C14—C15—C16	−1.1 (4)	C6—C5—C51—C56	18.5 (2)
C12—N11—C16—C15	1.0 (4)	C4—C5—C51—C56	−108.96 (18)
C14—C15—C16—N11	0.6 (4)	C6—C5—C51—C52	−163.96 (16)
C3—C2—C27—O27	−45.1 (2)	C4—C5—C51—C52	68.6 (2)
C1—C2—C27—O27	76.93 (19)	C56—C51—C52—C53	0.1 (3)
C3—C2—C27—C22	136.74 (14)	C5—C51—C52—C53	−177.57 (19)
C1—C2—C27—C22	−101.21 (16)	C51—C52—C53—C54	−0.2 (3)
C26—N21—C22—C23	0.1 (3)	C52—C53—C54—C55	0.0 (3)
C26—N21—C22—C27	179.0 (2)	C52—C53—C54—F54	−179.53 (19)
O27—C27—C22—N21	172.63 (17)	C53—C54—C55—C56	0.2 (3)
C2—C27—C22—N21	−9.2 (2)	F54—C54—C55—C56	179.70 (17)
O27—C27—C22—C23	−8.4 (3)	C52—C51—C56—C55	0.1 (3)
C2—C27—C22—C23	169.76 (18)	C5—C51—C56—C55	177.62 (16)
N21—C22—C23—C24	0.6 (4)	C54—C55—C56—C51	−0.2 (3)
C27—C22—C23—C24	−178.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N11	0.82	2.13	2.624 (2)	119
C13—H13···O11^i	0.95	2.54	3.385 (3)	148
C55—H55···O27^i	0.95	2.53	3.244 (2)	132

Symmetry code: (i) −x+1/2, y+1/2, z.

(II) (1RS,2SR,3SR,4RS,5RS)-3,5-Bis(4-chlorophenyl)-2,4-bis(pyridine-2-carbonyl)-1-(pyridin-2-yl)cyclohexanol acetone 0.951-solvate

Crystal data

C35H27Cl2N3O3·0.951C3H6O	Dx = 1.280 Mg m^−3
Mr = 663.73	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Fdd2	Cell parameters from 4224 reflections
a = 16.5446 (6) Å	θ = 4.6–70.1°
b = 53.4204 (17) Å	µ = 2.05 mm^−1
c = 15.5857 (4) Å	T = 200 K
V = 13774.9 (8) Å^3	Block, colourless
Z = 16	0.30 × 0.25 × 0.20 mm
F(000) = 5543

Data collection

Agilent Xcalibur Ruby Gemini diffractometer	3490 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	Rint = 0.027
ω scans	θmax = 70.1°, θmin = 4.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −19→20
Tmin = 0.388, Tmax = 0.664	k = −56→64
9544 measured reflections	l = −18→6
4224 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0744P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
4224 reflections	Δρmax = 0.16 e Å^−3
436 parameters	Δρmin = −0.16 e Å^−3
7 restraints	Absolute structure: Flack x determined using 613 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.089 (18)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.25172 (19)	0.35490 (6)	0.4632 (2)	0.0505 (6)
O11	0.20607 (15)	0.35606 (5)	0.54074 (15)	0.0647 (6)
H11	0.2379	0.3467	0.5731	0.097*
C2	0.21280 (17)	0.33568 (5)	0.40064 (19)	0.0481 (6)
H2	0.2440	0.3357	0.3457	0.058*
C3	0.12475 (17)	0.34306 (5)	0.38147 (19)	0.0460 (6)
H3	0.0962	0.3435	0.4380	0.055*
C4	0.11812 (16)	0.36986 (5)	0.34352 (19)	0.0454 (6)
H4	0.0596	0.3745	0.3438	0.054*
C5	0.16302 (18)	0.38897 (5)	0.4017 (2)	0.0489 (6)
H5	0.1336	0.3891	0.4577	0.059*
C6	0.24983 (19)	0.38087 (5)	0.4218 (2)	0.0526 (6)
H6A	0.2818	0.3806	0.3681	0.063*
H6B	0.2750	0.3932	0.4611	0.063*
N11	0.3517 (2)	0.33975 (6)	0.5638 (2)	0.0679 (7)
C12	0.33845 (19)	0.34663 (6)	0.4829 (2)	0.0546 (7)
C13	0.3972 (2)	0.34512 (7)	0.4207 (3)	0.0649 (8)
H13	0.3865	0.3509	0.3642	0.078*
C14	0.4712 (2)	0.33528 (9)	0.4409 (3)	0.0809 (11)
H14	0.5121	0.3338	0.3984	0.097*
C15	0.4854 (3)	0.32758 (9)	0.5246 (4)	0.0876 (13)
H15	0.5356	0.3204	0.5407	0.105*
C16	0.4251 (3)	0.33070 (9)	0.5827 (3)	0.0862 (13)
H16	0.4357	0.3262	0.6405	0.103*
C27	0.21686 (19)	0.30956 (6)	0.4398 (2)	0.0541 (7)
O27	0.16848 (16)	0.30235 (5)	0.4917 (2)	0.0735 (7)
N21	0.3165 (2)	0.29660 (7)	0.3350 (3)	0.0837 (10)
C22	0.2864 (2)	0.29305 (6)	0.4138 (3)	0.0620 (8)
C23	0.3160 (3)	0.27562 (7)	0.4698 (4)	0.0841 (12)
H23	0.2924	0.2736	0.5249	0.101*
C24	0.3807 (4)	0.26106 (10)	0.4446 (5)	0.1104 (18)
H24	0.4038	0.2492	0.4829	0.132*
C25	0.4108 (4)	0.26401 (11)	0.3641 (5)	0.116 (2)
H25	0.4540	0.2537	0.3445	0.139*
C26	0.3785 (3)	0.28192 (12)	0.3115 (4)	0.1066 (17)
H26	0.4009	0.2841	0.2559	0.128*
C31	0.08089 (18)	0.32368 (6)	0.3270 (2)	0.0513 (6)
C32	0.1182 (2)	0.31044 (7)	0.2615 (3)	0.0637 (8)
H32	0.1729	0.3141	0.2477	0.076*
C33	0.0783 (2)	0.29211 (8)	0.2158 (3)	0.0746 (10)
H33	0.1049	0.2832	0.1712	0.090*
C34	−0.0008 (3)	0.28699 (7)	0.2360 (3)	0.0757 (10)
Cl34	−0.05239 (11)	0.26346 (3)	0.18053 (12)	0.1225 (6)
C35	−0.0399 (2)	0.29974 (8)	0.2996 (3)	0.0764 (11)
H35	−0.0946	0.2960	0.3126	0.092*
C36	0.0003 (2)	0.31802 (7)	0.3446 (3)	0.0631 (8)
H36	−0.0272	0.3269	0.3884	0.076*
C47	0.14717 (16)	0.37140 (5)	0.25098 (19)	0.0451 (6)
O47	0.21661 (12)	0.36662 (5)	0.23092 (16)	0.0607 (6)
N41	0.01329 (16)	0.38537 (6)	0.2066 (2)	0.0646 (7)
C42	0.08830 (17)	0.37945 (5)	0.1827 (2)	0.0488 (6)
C43	0.1135 (2)	0.38102 (7)	0.0983 (2)	0.0618 (8)
H43	0.1672	0.3765	0.0831	0.074*
C44	0.0603 (2)	0.38919 (8)	0.0363 (3)	0.0751 (10)
H44	0.0768	0.3907	−0.0218	0.090*
C45	−0.0167 (3)	0.39508 (8)	0.0603 (3)	0.0782 (11)
H45	−0.0553	0.4005	0.0192	0.094*
C46	−0.0367 (2)	0.39294 (9)	0.1454 (3)	0.0794 (11)
H46	−0.0903	0.3972	0.1616	0.095*
C51	0.15672 (19)	0.41541 (6)	0.3660 (2)	0.0508 (6)
C52	0.0822 (2)	0.42707 (7)	0.3642 (3)	0.0706 (10)
H52	0.0362	0.4185	0.3856	0.085*
C53	0.0733 (3)	0.45099 (8)	0.3318 (4)	0.0804 (11)
H53	0.0215	0.4587	0.3302	0.096*
C54	0.1397 (3)	0.46354 (7)	0.3021 (3)	0.0725 (10)
Cl54	0.12896 (10)	0.49384 (2)	0.26117 (12)	0.1142 (5)
C55	0.2146 (3)	0.45280 (7)	0.3033 (3)	0.0726 (10)
H55	0.2603	0.4617	0.2825	0.087*
C56	0.2225 (2)	0.42862 (6)	0.3355 (3)	0.0623 (8)
H56	0.2744	0.4210	0.3366	0.075*
C71	0.6495 (16)	0.2977 (7)	0.2767 (10)	0.125 (3)	0.690 (13)
O71	0.5974 (5)	0.3120 (2)	0.2778 (8)	0.159 (4)	0.690 (13)
C72	0.7036 (14)	0.2906 (3)	0.2035 (9)	0.174 (5)	0.690 (13)
H72A	0.7137	0.2726	0.2047	0.261*	0.690 (13)
H72B	0.7550	0.2996	0.2087	0.261*	0.690 (13)
H72C	0.6776	0.2951	0.1492	0.261*	0.690 (13)
C73	0.6809 (14)	0.2869 (3)	0.3563 (8)	0.174 (5)	0.690 (13)
H73A	0.7396	0.2893	0.3587	0.261*	0.690 (13)
H73B	0.6686	0.2690	0.3581	0.261*	0.690 (13)
H73C	0.6557	0.2953	0.4055	0.261*	0.690 (13)
C81	0.664 (4)	0.293 (2)	0.285 (2)	0.125 (3)	0.261 (11)
O81	0.6093 (14)	0.2987 (6)	0.326 (2)	0.159 (4)	0.261 (11)
C82	0.680 (3)	0.2969 (10)	0.1916 (17)	0.174 (5)	0.261 (11)
H82A	0.7179	0.2841	0.1711	0.261*	0.261 (11)
H82B	0.7035	0.3135	0.1825	0.261*	0.261 (11)
H82C	0.6291	0.2956	0.1599	0.261*	0.261 (11)
C83	0.731 (2)	0.2787 (7)	0.323 (2)	0.174 (5)	0.261 (11)
H83A	0.7726	0.2758	0.2799	0.261*	0.261 (11)
H83B	0.7101	0.2626	0.3440	0.261*	0.261 (11)
H83C	0.7539	0.2881	0.3714	0.261*	0.261 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0563 (14)	0.0556 (15)	0.0397 (13)	0.0015 (13)	0.0020 (13)	0.0001 (12)
O11	0.0749 (13)	0.0745 (14)	0.0445 (12)	0.0068 (12)	0.0082 (11)	−0.0015 (11)
C2	0.0501 (13)	0.0502 (13)	0.0440 (14)	0.0029 (12)	0.0040 (12)	0.0005 (12)
C3	0.0469 (13)	0.0504 (13)	0.0409 (13)	0.0026 (11)	0.0056 (11)	0.0026 (11)
C4	0.0413 (12)	0.0505 (14)	0.0443 (14)	0.0055 (11)	0.0058 (11)	0.0000 (12)
C5	0.0552 (14)	0.0497 (13)	0.0419 (13)	0.0031 (12)	0.0075 (13)	−0.0010 (11)
C6	0.0576 (15)	0.0507 (14)	0.0495 (15)	−0.0007 (13)	−0.0049 (13)	−0.0007 (13)
N11	0.0849 (19)	0.0655 (15)	0.0533 (15)	0.0078 (15)	−0.0128 (16)	0.0091 (13)
C12	0.0625 (16)	0.0502 (14)	0.0512 (16)	−0.0030 (13)	−0.0109 (15)	0.0016 (13)
C13	0.0551 (16)	0.080 (2)	0.0597 (19)	−0.0013 (16)	−0.0068 (16)	0.0029 (17)
C14	0.0621 (19)	0.092 (3)	0.088 (3)	0.0039 (19)	−0.008 (2)	0.002 (2)
C15	0.074 (2)	0.086 (3)	0.104 (3)	0.015 (2)	−0.029 (3)	0.006 (3)
C16	0.105 (3)	0.084 (3)	0.070 (2)	0.019 (2)	−0.030 (3)	0.015 (2)
C27	0.0583 (15)	0.0555 (15)	0.0485 (15)	−0.0016 (13)	−0.0029 (14)	0.0026 (13)
O27	0.0774 (14)	0.0687 (14)	0.0743 (17)	0.0041 (12)	0.0120 (14)	0.0199 (13)
N21	0.088 (2)	0.093 (2)	0.070 (2)	0.0334 (19)	0.0021 (18)	−0.0136 (18)
C22	0.0672 (17)	0.0499 (15)	0.069 (2)	0.0054 (14)	−0.0081 (17)	−0.0079 (15)
C23	0.097 (3)	0.0609 (19)	0.094 (3)	0.019 (2)	−0.003 (3)	0.011 (2)
C24	0.123 (4)	0.077 (3)	0.131 (5)	0.042 (3)	−0.014 (4)	0.004 (3)
C25	0.122 (4)	0.102 (4)	0.123 (5)	0.061 (3)	−0.013 (4)	−0.039 (4)
C26	0.110 (3)	0.128 (4)	0.081 (3)	0.047 (3)	0.011 (3)	−0.030 (3)
C31	0.0516 (14)	0.0498 (14)	0.0526 (16)	0.0002 (12)	−0.0016 (13)	0.0070 (13)
C32	0.0637 (16)	0.0635 (17)	0.064 (2)	0.0005 (15)	−0.0012 (17)	−0.0067 (16)
C33	0.086 (2)	0.067 (2)	0.071 (2)	0.0000 (18)	−0.016 (2)	−0.0121 (18)
C34	0.090 (2)	0.0581 (17)	0.079 (3)	−0.0081 (18)	−0.031 (2)	0.0038 (18)
Cl34	0.1446 (11)	0.0949 (8)	0.1281 (12)	−0.0398 (8)	−0.0502 (10)	−0.0146 (8)
C35	0.0620 (18)	0.081 (2)	0.086 (3)	−0.0154 (19)	−0.0148 (19)	0.014 (2)
C36	0.0564 (16)	0.0667 (19)	0.066 (2)	−0.0026 (15)	−0.0054 (16)	0.0083 (17)
C47	0.0442 (13)	0.0472 (12)	0.0440 (15)	0.0009 (11)	0.0069 (12)	−0.0014 (11)
O47	0.0481 (10)	0.0849 (15)	0.0491 (11)	0.0098 (10)	0.0084 (10)	0.0015 (11)
N41	0.0513 (13)	0.0835 (18)	0.0588 (16)	0.0139 (13)	0.0057 (13)	0.0086 (15)
C42	0.0477 (13)	0.0507 (13)	0.0479 (15)	−0.0038 (11)	0.0003 (13)	0.0001 (12)
C43	0.0542 (16)	0.082 (2)	0.0494 (17)	−0.0068 (15)	0.0071 (15)	0.0027 (16)
C44	0.079 (2)	0.093 (3)	0.0528 (19)	−0.010 (2)	−0.0045 (18)	0.0080 (19)
C45	0.080 (2)	0.083 (2)	0.072 (2)	0.003 (2)	−0.022 (2)	0.016 (2)
C46	0.0548 (17)	0.101 (3)	0.083 (3)	0.0193 (19)	−0.0018 (19)	0.014 (2)
C51	0.0590 (15)	0.0487 (14)	0.0448 (14)	0.0031 (13)	0.0035 (13)	−0.0028 (12)
C52	0.0645 (18)	0.0581 (17)	0.089 (3)	0.0055 (16)	0.0117 (19)	0.0037 (18)
C53	0.076 (2)	0.062 (2)	0.103 (3)	0.0158 (18)	−0.003 (2)	0.008 (2)
C54	0.098 (3)	0.0495 (16)	0.070 (2)	0.0066 (18)	−0.007 (2)	0.0090 (16)
Cl54	0.1386 (10)	0.0630 (5)	0.1409 (12)	0.0055 (6)	−0.0158 (10)	0.0338 (6)
C55	0.084 (2)	0.0572 (17)	0.077 (2)	−0.0077 (18)	0.006 (2)	0.0091 (17)
C56	0.0596 (16)	0.0565 (16)	0.071 (2)	0.0020 (14)	0.0073 (17)	0.0020 (16)
C71	0.138 (11)	0.106 (16)	0.132 (7)	−0.032 (6)	0.022 (7)	0.008 (6)
O71	0.130 (5)	0.161 (8)	0.186 (11)	0.012 (5)	0.014 (6)	0.015 (7)
C72	0.286 (14)	0.131 (8)	0.104 (5)	−0.013 (8)	0.028 (7)	0.016 (4)
C73	0.286 (14)	0.131 (8)	0.104 (5)	−0.013 (8)	0.028 (7)	0.016 (4)
C81	0.138 (11)	0.106 (16)	0.132 (7)	−0.032 (6)	0.022 (7)	0.008 (6)
O81	0.130 (5)	0.161 (8)	0.186 (11)	0.012 (5)	0.014 (6)	0.015 (7)
C82	0.286 (14)	0.131 (8)	0.104 (5)	−0.013 (8)	0.028 (7)	0.016 (4)
C83	0.286 (14)	0.131 (8)	0.104 (5)	−0.013 (8)	0.028 (7)	0.016 (4)

Geometric parameters (Å, º)

C1—O11	1.426 (4)	C34—C35	1.365 (7)
C1—C6	1.531 (4)	C34—Cl34	1.748 (4)
C1—C12	1.533 (4)	C35—C36	1.374 (6)
C1—C2	1.556 (4)	C35—H35	0.9500
O11—H11	0.8847	C36—H36	0.9500
C2—C27	1.524 (4)	C47—O47	1.218 (3)
C2—C3	1.539 (4)	C47—C42	1.506 (4)
C2—H2	1.0000	N41—C46	1.326 (5)
C3—C31	1.523 (4)	N41—C42	1.334 (4)
C3—C4	1.552 (4)	C42—C43	1.382 (5)
C3—H3	1.0000	C43—C44	1.378 (5)
C4—C47	1.523 (4)	C43—H43	0.9500
C4—C5	1.555 (4)	C44—C45	1.364 (6)
C4—H4	1.0000	C44—H44	0.9500
C5—C51	1.521 (4)	C45—C46	1.372 (7)
C5—C6	1.532 (4)	C45—H45	0.9500
C5—H5	1.0000	C46—H46	0.9500
C6—H6A	0.9900	C51—C52	1.381 (5)
C6—H6B	0.9900	C51—C56	1.382 (5)
N11—C12	1.331 (5)	C52—C53	1.382 (5)
N11—C16	1.340 (5)	C52—H52	0.9500
C12—C13	1.375 (5)	C53—C54	1.368 (6)
C13—C14	1.370 (6)	C53—H53	0.9500
C13—H13	0.9500	C54—C55	1.365 (6)
C14—C15	1.387 (8)	C54—Cl54	1.749 (4)
C14—H14	0.9500	C55—C56	1.392 (5)
C15—C16	1.357 (7)	C55—H55	0.9500
C15—H15	0.9500	C56—H56	0.9500
C16—H16	0.9500	C71—O71	1.151 (13)
C27—O27	1.201 (4)	C71—C73	1.464 (17)
C27—C22	1.506 (5)	C71—C72	1.498 (14)
N21—C22	1.338 (6)	C72—H72A	0.9800
N21—C26	1.342 (5)	C72—H72B	0.9800
C22—C23	1.366 (6)	C72—H72C	0.9800
C23—C24	1.380 (7)	C73—H73A	0.9800
C23—H23	0.9500	C73—H73B	0.9800
C24—C25	1.360 (10)	C73—H73C	0.9800
C24—H24	0.9500	C81—O81	1.150 (13)
C25—C26	1.369 (9)	C81—C83	1.463 (18)
C25—H25	0.9500	C81—C82	1.497 (15)
C26—H26	0.9500	C82—H82A	0.9800
C31—C32	1.386 (5)	C82—H82B	0.9800
C31—C36	1.394 (5)	C82—H82C	0.9800
C32—C33	1.380 (5)	C83—H83A	0.9800
C32—H32	0.9500	C83—H83B	0.9800
C33—C34	1.373 (6)	C83—H83C	0.9800
C33—H33	0.9500
O11—C1—C6	107.9 (2)	C34—C33—H33	120.7
O11—C1—C12	109.8 (3)	C32—C33—H33	120.7
C6—C1—C12	111.4 (3)	C35—C34—C33	121.2 (4)
O11—C1—C2	109.9 (2)	C35—C34—Cl34	119.1 (3)
C6—C1—C2	109.0 (2)	C33—C34—Cl34	119.6 (4)
C12—C1—C2	108.8 (2)	C34—C35—C36	119.7 (3)
C1—O11—H11	98.2	C34—C35—H35	120.1
C27—C2—C3	110.7 (2)	C36—C35—H35	120.1
C27—C2—C1	109.6 (2)	C35—C36—C31	121.1 (4)
C3—C2—C1	110.1 (2)	C35—C36—H36	119.5
C27—C2—H2	108.8	C31—C36—H36	119.5
C3—C2—H2	108.8	O47—C47—C42	119.2 (3)
C1—C2—H2	108.8	O47—C47—C4	122.0 (3)
C31—C3—C2	112.6 (2)	C42—C47—C4	118.8 (2)
C31—C3—C4	112.4 (2)	C46—N41—C42	116.8 (3)
C2—C3—C4	112.2 (2)	N41—C42—C43	122.2 (3)
C31—C3—H3	106.4	N41—C42—C47	118.1 (3)
C2—C3—H3	106.4	C43—C42—C47	119.6 (3)
C4—C3—H3	106.4	C44—C43—C42	119.5 (3)
C47—C4—C3	112.9 (2)	C44—C43—H43	120.2
C47—C4—C5	111.5 (2)	C42—C43—H43	120.2
C3—C4—C5	110.5 (2)	C45—C44—C43	118.6 (4)
C47—C4—H4	107.2	C45—C44—H44	120.7
C3—C4—H4	107.2	C43—C44—H44	120.7
C5—C4—H4	107.2	C44—C45—C46	118.1 (4)
C51—C5—C6	113.7 (2)	C44—C45—H45	121.0
C51—C5—C4	111.3 (2)	C46—C45—H45	121.0
C6—C5—C4	112.4 (2)	N41—C46—C45	124.8 (4)
C51—C5—H5	106.3	N41—C46—H46	117.6
C6—C5—H5	106.3	C45—C46—H46	117.6
C4—C5—H5	106.3	C52—C51—C56	117.7 (3)
C1—C6—C5	111.2 (2)	C52—C51—C5	119.2 (3)
C1—C6—H6A	109.4	C56—C51—C5	123.1 (3)
C5—C6—H6A	109.4	C51—C52—C53	121.4 (4)
C1—C6—H6B	109.4	C51—C52—H52	119.3
C5—C6—H6B	109.4	C53—C52—H52	119.3
H6A—C6—H6B	108.0	C54—C53—C52	119.4 (4)
C12—N11—C16	117.2 (4)	C54—C53—H53	120.3
N11—C12—C13	122.3 (3)	C52—C53—H53	120.3
N11—C12—C1	115.1 (3)	C55—C54—C53	121.2 (3)
C13—C12—C1	122.5 (3)	C55—C54—Cl54	119.1 (3)
C14—C13—C12	119.5 (4)	C53—C54—Cl54	119.7 (3)
C14—C13—H13	120.3	C54—C55—C56	118.7 (4)
C12—C13—H13	120.3	C54—C55—H55	120.6
C13—C14—C15	118.7 (5)	C56—C55—H55	120.6
C13—C14—H14	120.6	C51—C56—C55	121.6 (3)
C15—C14—H14	120.6	C51—C56—H56	119.2
C16—C15—C14	117.8 (4)	C55—C56—H56	119.2
C16—C15—H15	121.1	O71—C71—C73	120.9 (14)
C14—C15—H15	121.1	O71—C71—C72	128.7 (13)
N11—C16—C15	124.3 (4)	C73—C71—C72	109.5 (11)
N11—C16—H16	117.8	C71—C72—H72A	109.5
C15—C16—H16	117.8	C71—C72—H72B	109.5
O27—C27—C22	120.2 (3)	H72A—C72—H72B	109.5
O27—C27—C2	122.2 (3)	C71—C72—H72C	109.5
C22—C27—C2	117.5 (3)	H72A—C72—H72C	109.5
C22—N21—C26	116.8 (4)	H72B—C72—H72C	109.5
N21—C22—C23	123.3 (4)	C71—C73—H73A	109.5
N21—C22—C27	116.6 (3)	C71—C73—H73B	109.5
C23—C22—C27	120.1 (4)	H73A—C73—H73B	109.5
C22—C23—C24	118.7 (5)	C71—C73—H73C	109.5
C22—C23—H23	120.6	H73A—C73—H73C	109.5
C24—C23—H23	120.6	H73B—C73—H73C	109.5
C25—C24—C23	118.8 (5)	O81—C81—C83	120.7 (17)
C25—C24—H24	120.6	O81—C81—C82	129.5 (16)
C23—C24—H24	120.6	C83—C81—C82	109.7 (13)
C24—C25—C26	119.3 (5)	C81—C82—H82A	109.5
C24—C25—H25	120.3	C81—C82—H82B	109.5
C26—C25—H25	120.3	H82A—C82—H82B	109.5
N21—C26—C25	123.0 (6)	C81—C82—H82C	109.5
N21—C26—H26	118.5	H82A—C82—H82C	109.5
C25—C26—H26	118.5	H82B—C82—H82C	109.5
C32—C31—C36	117.4 (3)	C81—C83—H83A	109.5
C32—C31—C3	123.0 (3)	C81—C83—H83B	109.5
C36—C31—C3	119.5 (3)	H83A—C83—H83B	109.5
C33—C32—C31	121.9 (3)	C81—C83—H83C	109.5
C33—C32—H32	119.0	H83A—C83—H83C	109.5
C31—C32—H32	119.0	H83B—C83—H83C	109.5
C34—C33—C32	118.6 (4)
O11—C1—C2—C27	−63.9 (3)	C22—C23—C24—C25	−2.2 (8)
C6—C1—C2—C27	178.1 (2)	C23—C24—C25—C26	2.5 (10)
C12—C1—C2—C27	56.4 (3)	C22—N21—C26—C25	0.0 (8)
O11—C1—C2—C3	58.2 (3)	C24—C25—C26—N21	−1.4 (10)
C6—C1—C2—C3	−59.9 (3)	C2—C3—C31—C32	−36.8 (4)
C12—C1—C2—C3	178.5 (2)	C4—C3—C31—C32	91.0 (4)
C27—C2—C3—C31	−53.4 (3)	C2—C3—C31—C36	140.7 (3)
C1—C2—C3—C31	−174.8 (2)	C4—C3—C31—C36	−91.4 (3)
C27—C2—C3—C4	178.6 (2)	C36—C31—C32—C33	−0.8 (5)
C1—C2—C3—C4	57.3 (3)	C3—C31—C32—C33	176.8 (3)
C31—C3—C4—C47	−55.0 (3)	C31—C32—C33—C34	0.2 (6)
C2—C3—C4—C47	73.1 (3)	C32—C33—C34—C35	0.3 (6)
C31—C3—C4—C5	179.5 (2)	C32—C33—C34—Cl34	−178.8 (3)
C2—C3—C4—C5	−52.4 (3)	C33—C34—C35—C36	−0.1 (6)
C47—C4—C5—C51	54.1 (3)	Cl34—C34—C35—C36	179.0 (3)
C3—C4—C5—C51	−179.6 (2)	C34—C35—C36—C31	−0.6 (6)
C47—C4—C5—C6	−74.7 (3)	C32—C31—C36—C35	1.0 (5)
C3—C4—C5—C6	51.6 (3)	C3—C31—C36—C35	−176.7 (3)
O11—C1—C6—C5	−59.7 (3)	C3—C4—C47—O47	−61.9 (4)
C12—C1—C6—C5	179.7 (3)	C5—C4—C47—O47	63.1 (4)
C2—C1—C6—C5	59.6 (3)	C3—C4—C47—C42	119.0 (3)
C51—C5—C6—C1	176.0 (3)	C5—C4—C47—C42	−116.0 (3)
C4—C5—C6—C1	−56.4 (3)	C46—N41—C42—C43	−0.1 (5)
C16—N11—C12—C13	−1.2 (5)	C46—N41—C42—C47	178.5 (3)
C16—N11—C12—C1	175.4 (3)	O47—C47—C42—N41	−177.8 (3)
O11—C1—C12—N11	6.8 (4)	C4—C47—C42—N41	1.3 (4)
C6—C1—C12—N11	126.3 (3)	O47—C47—C42—C43	0.8 (4)
C2—C1—C12—N11	−113.6 (3)	C4—C47—C42—C43	179.9 (3)
O11—C1—C12—C13	−176.6 (3)	N41—C42—C43—C44	0.7 (5)
C6—C1—C12—C13	−57.1 (4)	C47—C42—C43—C44	−177.9 (3)
C2—C1—C12—C13	63.1 (4)	C42—C43—C44—C45	−1.1 (6)
N11—C12—C13—C14	2.7 (6)	C43—C44—C45—C46	1.0 (7)
C1—C12—C13—C14	−173.7 (4)	C42—N41—C46—C45	0.0 (7)
C12—C13—C14—C15	−1.4 (7)	C44—C45—C46—N41	−0.5 (7)
C13—C14—C15—C16	−1.3 (7)	C6—C5—C51—C52	−165.0 (3)
C12—N11—C16—C15	−1.7 (7)	C4—C5—C51—C52	66.9 (4)
C14—C15—C16—N11	2.9 (8)	C6—C5—C51—C56	14.5 (4)
C3—C2—C27—O27	−39.9 (4)	C4—C5—C51—C56	−113.6 (3)
C1—C2—C27—O27	81.8 (4)	C56—C51—C52—C53	1.0 (6)
C3—C2—C27—C22	142.5 (3)	C5—C51—C52—C53	−179.5 (4)
C1—C2—C27—C22	−95.8 (3)	C51—C52—C53—C54	−0.9 (7)
C26—N21—C22—C23	0.3 (7)	C52—C53—C54—C55	0.4 (7)
C26—N21—C22—C27	−179.9 (4)	C52—C53—C54—Cl54	−179.9 (4)
O27—C27—C22—N21	152.5 (4)	C53—C54—C55—C56	0.0 (7)
C2—C27—C22—N21	−29.9 (5)	Cl54—C54—C55—C56	−179.7 (3)
O27—C27—C22—C23	−27.8 (5)	C52—C51—C56—C55	−0.5 (6)
C2—C27—C22—C23	149.9 (4)	C5—C51—C56—C55	180.0 (4)
N21—C22—C23—C24	0.8 (7)	C54—C55—C56—C51	0.0 (6)
C27—C22—C23—C24	−178.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N11	0.88	1.92	2.587 (4)	130
C14—H14···O71	0.95	2.62	3.517 (12)	157
C14—H14···O81	0.95	2.72	3.499 (12)	140
C43—H43···N41^i	0.95	2.61	3.433 (4)	145
C45—H45···O71^ii	0.95	2.57	3.251 (11)	129
C16—H16···Cg1^iii	0.95	3.00	3.869 (5)	153

Symmetry codes: (i) x+1/4, −y+3/4, z−1/4; (ii) x−3/4, −y+3/4, z−1/4; (iii) x+1/2, y, z+1/2.

(III) (1RS,2SR,3SR,4RS,5RS)- 3,5-Bis(4-bromophenyl)-2,4-bis(pyridine-2-carbonyl)-1-(pyridin-2-yl)cyclohexanol

Crystal data

C35H27Br2N3O3	Z = 2
Mr = 697.41	F(000) = 704
Triclinic, P1	Dx = 1.471 Mg m^−3
a = 9.5741 (4) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.7061 (3) Å	Cell parameters from 5922 reflections
c = 15.9952 (6) Å	θ = 4.8–70.0°
α = 92.863 (3)°	µ = 3.58 mm^−1
β = 97.443 (3)°	T = 200 K
γ = 103.618 (3)°	Block, colourless
V = 1574.49 (10) Å^3	0.25 × 0.20 × 0.15 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer	4948 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	Rint = 0.026
ω scans	θmax = 70.0°, θmin = 4.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −10→11
Tmin = 0.109, Tmax = 0.584	k = −13→13
11667 measured reflections	l = −19→19
5922 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0808P)^2 + 0.8269P] where P = (Fo^2 + 2Fc^2)/3
5922 reflections	(Δ/σ)max < 0.001
388 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.1094 (3)	0.2890 (3)	0.37522 (18)	0.0469 (6)
O11	−0.0179 (2)	0.1914 (2)	0.34356 (14)	0.0597 (5)
H11	−0.0388	0.1511	0.3839	0.075*
C2	0.2459 (3)	0.2500 (3)	0.34883 (17)	0.0431 (6)
H2	0.3345	0.3181	0.3736	0.052*
C3	0.2393 (3)	0.2382 (2)	0.25268 (17)	0.0423 (5)
H3	0.1509	0.1686	0.2300	0.051*
C4	0.2191 (3)	0.3631 (3)	0.21229 (17)	0.0428 (6)
H4	0.2020	0.3448	0.1494	0.051*
C5	0.0830 (3)	0.3990 (3)	0.23934 (18)	0.0474 (6)
H5	−0.0014	0.3245	0.2185	0.057*
C6	0.0928 (3)	0.4136 (3)	0.33570 (19)	0.0505 (6)
H6A	0.0040	0.4358	0.3508	0.061*
H6B	0.1771	0.4851	0.3592	0.061*
N11	0.0326 (3)	0.2241 (3)	0.50752 (18)	0.0679 (8)
C12	0.1245 (3)	0.3091 (3)	0.47110 (19)	0.0496 (6)
C13	0.2307 (4)	0.4069 (4)	0.5184 (2)	0.0618 (8)
H13	0.2964	0.4669	0.4914	0.074*
C14	0.2392 (4)	0.4156 (4)	0.6059 (2)	0.0722 (9)
H14	0.3110	0.4819	0.6396	0.087*
C15	0.1442 (4)	0.3286 (5)	0.6429 (2)	0.0778 (11)
H15	0.1477	0.3333	0.7026	0.093*
C16	0.0443 (5)	0.2349 (5)	0.5928 (2)	0.0857 (13)
H16	−0.0211	0.1735	0.6190	0.103*
C27	0.2561 (3)	0.1226 (3)	0.38517 (19)	0.0489 (6)
O27	0.1950 (3)	0.0192 (2)	0.34738 (15)	0.0666 (6)
N21	0.4626 (4)	0.2257 (3)	0.4895 (2)	0.0679 (8)
C22	0.3450 (4)	0.1270 (3)	0.4699 (2)	0.0541 (7)
C23	0.3069 (5)	0.0303 (4)	0.5227 (3)	0.0768 (11)
H23	0.2229	−0.0384	0.5068	0.092*
C24	0.3957 (7)	0.0364 (6)	0.6000 (3)	0.1017 (17)
H24	0.3722	−0.0276	0.6384	0.122*
C25	0.5172 (7)	0.1359 (5)	0.6197 (3)	0.0977 (17)
H25	0.5802	0.1416	0.6715	0.117*
C26	0.5455 (6)	0.2268 (4)	0.5633 (3)	0.0884 (14)
H26	0.6300	0.2954	0.5776	0.106*
C31	0.3678 (3)	0.1972 (2)	0.22351 (17)	0.0439 (6)
C32	0.5090 (3)	0.2443 (3)	0.2641 (2)	0.0550 (7)
H32	0.5266	0.2992	0.3148	0.066*
C33	0.6256 (3)	0.2124 (3)	0.2318 (2)	0.0597 (8)
H33	0.7222	0.2468	0.2593	0.072*
C34	0.5991 (4)	0.1310 (3)	0.1601 (2)	0.0575 (7)
Br34	0.75694 (5)	0.09296 (5)	0.11223 (4)	0.0979 (2)
C35	0.4591 (4)	0.0767 (4)	0.1205 (2)	0.0655 (9)
H35	0.4417	0.0171	0.0721	0.079*
C36	0.3452 (4)	0.1110 (3)	0.1528 (2)	0.0561 (7)
H36	0.2487	0.0745	0.1257	0.067*
C47	0.3521 (3)	0.4760 (3)	0.23542 (18)	0.0441 (6)
O47	0.4088 (2)	0.5068 (2)	0.30802 (13)	0.0568 (5)
N41	0.3478 (4)	0.5267 (3)	0.0881 (2)	0.0725 (8)
C42	0.4133 (3)	0.5553 (3)	0.1677 (2)	0.0512 (6)
C43	0.5344 (4)	0.6559 (4)	0.1917 (3)	0.0752 (10)
H43	0.5767	0.6742	0.2495	0.090*
C44	0.5924 (6)	0.7290 (5)	0.1310 (4)	0.1031 (17)
H44	0.6775	0.7971	0.1456	0.124*
C45	0.5261 (6)	0.7024 (6)	0.0496 (4)	0.113 (2)
H45	0.5621	0.7530	0.0064	0.135*
C46	0.4060 (6)	0.6008 (6)	0.0310 (3)	0.1027 (17)
H46	0.3615	0.5822	−0.0263	0.123*
C51	0.0525 (3)	0.5151 (3)	0.19609 (18)	0.0466 (6)
C52	−0.0392 (4)	0.4954 (3)	0.1203 (2)	0.0611 (8)
H52	−0.0860	0.4096	0.0980	0.073*
C53	−0.0653 (4)	0.5979 (3)	0.0755 (2)	0.0643 (8)
H53	−0.1278	0.5828	0.0229	0.077*
C54	0.0009 (3)	0.7206 (3)	0.1089 (2)	0.0544 (7)
Br54	−0.03457 (5)	0.86020 (4)	0.04693 (3)	0.07606 (16)
C55	0.0917 (4)	0.7454 (3)	0.1847 (2)	0.0577 (7)
H55	0.1369	0.8315	0.2068	0.069*
C56	0.1159 (4)	0.6418 (3)	0.2283 (2)	0.0553 (7)
H56	0.1772	0.6578	0.2813	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0392 (13)	0.0497 (15)	0.0488 (15)	0.0037 (11)	0.0059 (11)	0.0116 (11)
O11	0.0459 (11)	0.0660 (13)	0.0585 (12)	−0.0037 (10)	0.0042 (9)	0.0149 (10)
C2	0.0421 (13)	0.0399 (13)	0.0450 (14)	0.0050 (10)	0.0043 (10)	0.0108 (10)
C3	0.0393 (13)	0.0383 (12)	0.0457 (14)	0.0030 (10)	0.0023 (10)	0.0102 (10)
C4	0.0433 (13)	0.0421 (13)	0.0408 (13)	0.0061 (11)	0.0027 (10)	0.0114 (10)
C5	0.0409 (14)	0.0458 (14)	0.0525 (15)	0.0062 (11)	0.0005 (11)	0.0126 (11)
C6	0.0473 (15)	0.0552 (16)	0.0536 (16)	0.0161 (12)	0.0129 (12)	0.0159 (13)
N11	0.0625 (17)	0.0764 (19)	0.0571 (16)	−0.0042 (14)	0.0157 (13)	0.0159 (13)
C12	0.0454 (15)	0.0543 (16)	0.0517 (16)	0.0126 (12)	0.0119 (12)	0.0139 (12)
C13	0.0581 (18)	0.0651 (19)	0.0566 (18)	0.0054 (15)	0.0049 (14)	0.0089 (14)
C14	0.063 (2)	0.085 (3)	0.063 (2)	0.0140 (18)	0.0011 (16)	−0.0032 (18)
C15	0.068 (2)	0.114 (3)	0.0501 (19)	0.018 (2)	0.0123 (16)	0.0069 (19)
C16	0.079 (3)	0.113 (3)	0.057 (2)	−0.004 (2)	0.0232 (19)	0.022 (2)
C27	0.0526 (16)	0.0413 (14)	0.0510 (15)	0.0072 (12)	0.0066 (12)	0.0116 (11)
O27	0.0818 (16)	0.0433 (11)	0.0637 (14)	−0.0001 (11)	−0.0038 (12)	0.0116 (10)
N21	0.077 (2)	0.0548 (15)	0.0665 (18)	0.0189 (14)	−0.0131 (15)	0.0022 (13)
C22	0.0646 (19)	0.0483 (15)	0.0513 (16)	0.0208 (14)	0.0012 (13)	0.0073 (12)
C23	0.096 (3)	0.068 (2)	0.067 (2)	0.020 (2)	0.0048 (19)	0.0260 (18)
C24	0.148 (5)	0.104 (4)	0.064 (2)	0.053 (4)	0.004 (3)	0.037 (2)
C25	0.133 (4)	0.095 (3)	0.066 (2)	0.056 (3)	−0.031 (3)	−0.006 (2)
C26	0.102 (3)	0.069 (2)	0.083 (3)	0.028 (2)	−0.033 (2)	−0.008 (2)
C31	0.0465 (14)	0.0387 (13)	0.0453 (14)	0.0083 (11)	0.0038 (11)	0.0105 (10)
C32	0.0480 (16)	0.0565 (17)	0.0559 (17)	0.0096 (13)	0.0012 (12)	−0.0086 (13)
C33	0.0432 (15)	0.0594 (18)	0.073 (2)	0.0076 (13)	0.0068 (14)	−0.0022 (15)
C34	0.0583 (18)	0.0496 (16)	0.0683 (19)	0.0139 (13)	0.0215 (15)	0.0060 (14)
Br34	0.0719 (3)	0.0935 (3)	0.1280 (4)	0.0138 (2)	0.0402 (3)	−0.0285 (3)
C35	0.070 (2)	0.0626 (19)	0.0597 (19)	0.0105 (16)	0.0115 (16)	−0.0109 (15)
C36	0.0533 (17)	0.0572 (17)	0.0509 (16)	0.0043 (13)	0.0014 (13)	−0.0014 (13)
C47	0.0407 (13)	0.0398 (13)	0.0507 (16)	0.0072 (10)	0.0049 (11)	0.0102 (11)
O47	0.0561 (12)	0.0521 (11)	0.0518 (12)	−0.0030 (9)	−0.0009 (9)	0.0071 (9)
N41	0.0667 (18)	0.081 (2)	0.0631 (18)	0.0009 (15)	0.0096 (14)	0.0287 (15)
C42	0.0459 (15)	0.0511 (15)	0.0564 (17)	0.0085 (12)	0.0079 (12)	0.0181 (13)
C43	0.064 (2)	0.068 (2)	0.084 (3)	−0.0065 (17)	0.0105 (18)	0.0255 (19)
C44	0.085 (3)	0.093 (3)	0.115 (4)	−0.020 (3)	0.021 (3)	0.045 (3)
C45	0.098 (4)	0.121 (4)	0.113 (4)	−0.007 (3)	0.033 (3)	0.068 (3)
C46	0.099 (3)	0.128 (4)	0.071 (3)	−0.002 (3)	0.013 (2)	0.049 (3)
C51	0.0423 (14)	0.0468 (14)	0.0518 (15)	0.0126 (11)	0.0049 (11)	0.0117 (11)
C52	0.065 (2)	0.0478 (16)	0.0630 (19)	0.0093 (14)	−0.0101 (15)	0.0076 (14)
C53	0.071 (2)	0.0616 (19)	0.0572 (18)	0.0187 (16)	−0.0089 (15)	0.0128 (15)
C54	0.0542 (17)	0.0510 (16)	0.0645 (18)	0.0192 (13)	0.0126 (14)	0.0249 (14)
Br54	0.0745 (3)	0.0655 (2)	0.0962 (3)	0.02530 (19)	0.0135 (2)	0.0409 (2)
C55	0.0626 (19)	0.0443 (15)	0.0655 (19)	0.0107 (13)	0.0079 (15)	0.0117 (13)
C56	0.0569 (17)	0.0517 (16)	0.0535 (17)	0.0111 (13)	−0.0026 (13)	0.0080 (13)

Geometric parameters (Å, º)

C1—O11	1.422 (3)	C25—C26	1.364 (7)
C1—C12	1.521 (4)	C25—H25	0.9500
C1—C6	1.537 (4)	C26—H26	0.9500
C1—C2	1.563 (4)	C31—C36	1.384 (4)
O11—H11	0.8144	C31—C32	1.387 (4)
C2—C27	1.528 (4)	C32—C33	1.394 (4)
C2—C3	1.529 (4)	C32—H32	0.9500
C2—H2	1.0000	C33—C34	1.363 (5)
C3—C31	1.519 (4)	C33—H33	0.9500
C3—C4	1.555 (3)	C34—C35	1.383 (5)
C3—H3	1.0000	C34—Br34	1.896 (3)
C4—C47	1.526 (4)	C35—C36	1.381 (5)
C4—C5	1.548 (4)	C35—H35	0.9500
C4—H4	1.0000	C36—H36	0.9500
C5—C51	1.521 (4)	C47—O47	1.211 (4)
C5—C6	1.530 (4)	C47—C42	1.503 (4)
C5—H5	1.0000	N41—C46	1.330 (5)
C6—H6A	0.9900	N41—C42	1.331 (4)
C6—H6B	0.9900	C42—C43	1.382 (5)
N11—C12	1.322 (4)	C43—C44	1.369 (6)
N11—C16	1.351 (5)	C43—H43	0.9500
C12—C13	1.387 (5)	C44—C45	1.358 (8)
C13—C14	1.388 (5)	C44—H44	0.9500
C13—H13	0.9500	C45—C46	1.373 (7)
C14—C15	1.357 (6)	C45—H45	0.9500
C14—H14	0.9500	C46—H46	0.9500
C15—C16	1.353 (6)	C51—C52	1.377 (4)
C15—H15	0.9500	C51—C56	1.391 (4)
C16—H16	0.9500	C52—C53	1.394 (4)
C27—O27	1.213 (4)	C52—H52	0.9500
C27—C22	1.496 (4)	C53—C54	1.364 (5)
N21—C26	1.333 (5)	C53—H53	0.9500
N21—C22	1.341 (5)	C54—C55	1.372 (5)
C22—C23	1.381 (5)	C54—Br54	1.905 (3)
C23—C24	1.397 (6)	C55—C56	1.388 (4)
C23—H23	0.9500	C55—H55	0.9500
C24—C25	1.369 (8)	C56—H56	0.9500
C24—H24	0.9500
O11—C1—C12	110.1 (2)	C25—C24—H24	120.5
O11—C1—C6	107.2 (2)	C23—C24—H24	120.5
C12—C1—C6	109.9 (2)	C26—C25—C24	118.5 (4)
O11—C1—C2	109.9 (2)	C26—C25—H25	120.7
C12—C1—C2	110.0 (2)	C24—C25—H25	120.7
C6—C1—C2	109.7 (2)	N21—C26—C25	124.4 (4)
C1—O11—H11	105.3	N21—C26—H26	117.8
C27—C2—C3	110.6 (2)	C25—C26—H26	117.8
C27—C2—C1	108.8 (2)	C36—C31—C32	117.9 (3)
C3—C2—C1	111.4 (2)	C36—C31—C3	119.4 (3)
C27—C2—H2	108.6	C32—C31—C3	122.7 (3)
C3—C2—H2	108.6	C31—C32—C33	121.1 (3)
C1—C2—H2	108.6	C31—C32—H32	119.4
C31—C3—C2	113.6 (2)	C33—C32—H32	119.4
C31—C3—C4	110.4 (2)	C34—C33—C32	119.0 (3)
C2—C3—C4	112.4 (2)	C34—C33—H33	120.5
C31—C3—H3	106.7	C32—C33—H33	120.5
C2—C3—H3	106.7	C33—C34—C35	121.4 (3)
C4—C3—H3	106.7	C33—C34—Br34	119.6 (3)
C47—C4—C5	110.4 (2)	C35—C34—Br34	119.0 (3)
C47—C4—C3	112.7 (2)	C36—C35—C34	118.6 (3)
C5—C4—C3	109.4 (2)	C36—C35—H35	120.7
C47—C4—H4	108.1	C34—C35—H35	120.7
C5—C4—H4	108.1	C35—C36—C31	121.8 (3)
C3—C4—H4	108.1	C35—C36—H36	119.1
C51—C5—C6	113.8 (3)	C31—C36—H36	119.1
C51—C5—C4	111.2 (2)	O47—C47—C42	118.1 (2)
C6—C5—C4	111.4 (2)	O47—C47—C4	121.7 (2)
C51—C5—H5	106.6	C42—C47—C4	120.1 (2)
C6—C5—H5	106.6	C46—N41—C42	116.2 (4)
C4—C5—H5	106.6	N41—C42—C43	123.2 (3)
C5—C6—C1	111.5 (3)	N41—C42—C47	118.9 (3)
C5—C6—H6A	109.3	C43—C42—C47	117.9 (3)
C1—C6—H6A	109.3	C44—C43—C42	118.9 (4)
C5—C6—H6B	109.3	C44—C43—H43	120.6
C1—C6—H6B	109.3	C42—C43—H43	120.6
H6A—C6—H6B	108.0	C45—C44—C43	118.7 (4)
C12—N11—C16	118.2 (3)	C45—C44—H44	120.6
N11—C12—C13	121.5 (3)	C43—C44—H44	120.6
N11—C12—C1	115.7 (3)	C44—C45—C46	118.7 (4)
C13—C12—C1	122.7 (3)	C44—C45—H45	120.7
C12—C13—C14	118.8 (3)	C46—C45—H45	120.7
C12—C13—H13	120.6	N41—C46—C45	124.2 (5)
C14—C13—H13	120.6	N41—C46—H46	117.9
C15—C14—C13	119.4 (4)	C45—C46—H46	117.9
C15—C14—H14	120.3	C52—C51—C56	117.8 (3)
C13—C14—H14	120.3	C52—C51—C5	119.1 (3)
C16—C15—C14	118.5 (4)	C56—C51—C5	123.2 (3)
C16—C15—H15	120.7	C51—C52—C53	121.7 (3)
C14—C15—H15	120.7	C51—C52—H52	119.2
N11—C16—C15	123.5 (4)	C53—C52—H52	119.2
N11—C16—H16	118.2	C54—C53—C52	118.6 (3)
C15—C16—H16	118.2	C54—C53—H53	120.7
O27—C27—C22	119.5 (3)	C52—C53—H53	120.7
O27—C27—C2	122.0 (3)	C53—C54—C55	122.0 (3)
C22—C27—C2	118.4 (2)	C53—C54—Br54	118.3 (2)
C26—N21—C22	116.9 (4)	C55—C54—Br54	119.8 (2)
N21—C22—C23	123.1 (3)	C54—C55—C56	118.5 (3)
N21—C22—C27	116.8 (3)	C54—C55—H55	120.7
C23—C22—C27	120.1 (3)	C56—C55—H55	120.7
C22—C23—C24	118.1 (4)	C55—C56—C51	121.5 (3)
C22—C23—H23	121.0	C55—C56—H56	119.3
C24—C23—H23	121.0	C51—C56—H56	119.3
C25—C24—C23	119.0 (4)
O11—C1—C2—C27	−59.6 (3)	C22—C23—C24—C25	−1.0 (8)
C12—C1—C2—C27	61.8 (3)	C23—C24—C25—C26	1.0 (8)
C6—C1—C2—C27	−177.2 (2)	C22—N21—C26—C25	−0.9 (7)
O11—C1—C2—C3	62.6 (3)	C24—C25—C26—N21	0.0 (8)
C12—C1—C2—C3	−176.0 (2)	C2—C3—C31—C36	140.5 (3)
C6—C1—C2—C3	−55.0 (3)	C4—C3—C31—C36	−92.2 (3)
C27—C2—C3—C31	−57.4 (3)	C2—C3—C31—C32	−40.6 (4)
C1—C2—C3—C31	−178.5 (2)	C4—C3—C31—C32	86.7 (3)
C27—C2—C3—C4	176.4 (2)	C36—C31—C32—C33	4.0 (5)
C1—C2—C3—C4	55.2 (3)	C3—C31—C32—C33	−174.9 (3)
C31—C3—C4—C47	−59.7 (3)	C31—C32—C33—C34	−1.6 (5)
C2—C3—C4—C47	68.3 (3)	C32—C33—C34—C35	−1.9 (5)
C31—C3—C4—C5	177.1 (2)	C32—C33—C34—Br34	177.0 (3)
C2—C3—C4—C5	−54.9 (3)	C33—C34—C35—C36	2.9 (6)
C47—C4—C5—C51	59.7 (3)	Br34—C34—C35—C36	−176.1 (3)
C3—C4—C5—C51	−175.8 (2)	C34—C35—C36—C31	−0.3 (5)
C47—C4—C5—C6	−68.5 (3)	C32—C31—C36—C35	−3.0 (5)
C3—C4—C5—C6	56.0 (3)	C3—C31—C36—C35	175.9 (3)
C51—C5—C6—C1	174.7 (2)	C5—C4—C47—O47	72.3 (3)
C4—C5—C6—C1	−58.6 (3)	C3—C4—C47—O47	−50.3 (4)
O11—C1—C6—C5	−62.5 (3)	C5—C4—C47—C42	−105.5 (3)
C12—C1—C6—C5	177.9 (2)	C3—C4—C47—C42	131.9 (3)
C2—C1—C6—C5	56.8 (3)	C46—N41—C42—C43	0.4 (6)
C16—N11—C12—C13	0.1 (6)	C46—N41—C42—C47	179.4 (4)
C16—N11—C12—C1	177.9 (4)	O47—C47—C42—N41	−176.7 (3)
O11—C1—C12—N11	8.8 (4)	C4—C47—C42—N41	1.3 (4)
C6—C1—C12—N11	126.6 (3)	O47—C47—C42—C43	2.5 (5)
C2—C1—C12—N11	−112.5 (3)	C4—C47—C42—C43	−179.6 (3)
O11—C1—C12—C13	−173.5 (3)	N41—C42—C43—C44	−1.3 (7)
C6—C1—C12—C13	−55.7 (4)	C47—C42—C43—C44	179.7 (4)
C2—C1—C12—C13	65.2 (4)	C42—C43—C44—C45	2.0 (9)
N11—C12—C13—C14	−0.4 (5)	C43—C44—C45—C46	−1.9 (10)
C1—C12—C13—C14	−178.0 (3)	C42—N41—C46—C45	−0.3 (9)
C12—C13—C14—C15	0.1 (6)	C44—C45—C46—N41	1.1 (11)
C13—C14—C15—C16	0.5 (7)	C6—C5—C51—C52	−141.5 (3)
C12—N11—C16—C15	0.6 (7)	C4—C5—C51—C52	91.7 (3)
C14—C15—C16—N11	−0.9 (8)	C6—C5—C51—C56	40.2 (4)
C3—C2—C27—O27	−34.8 (4)	C4—C5—C51—C56	−86.7 (4)
C1—C2—C27—O27	88.0 (4)	C56—C51—C52—C53	1.9 (5)
C3—C2—C27—C22	145.0 (3)	C5—C51—C52—C53	−176.6 (3)
C1—C2—C27—C22	−92.3 (3)	C51—C52—C53—C54	−0.9 (6)
C26—N21—C22—C23	0.9 (6)	C52—C53—C54—C55	0.0 (6)
C26—N21—C22—C27	−177.2 (4)	C52—C53—C54—Br54	179.7 (3)
O27—C27—C22—N21	146.8 (3)	C53—C54—C55—C56	−0.1 (5)
C2—C27—C22—N21	−32.9 (4)	Br54—C54—C55—C56	−179.8 (3)
O27—C27—C22—C23	−31.3 (5)	C54—C55—C56—C51	1.1 (5)
C2—C27—C22—C23	148.9 (3)	C52—C51—C56—C55	−2.0 (5)
N21—C22—C23—C24	0.1 (7)	C5—C51—C56—C55	176.4 (3)
C27—C22—C23—C24	178.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N11	0.81	2.06	2.595 (4)	123
C16—H16···O27^i	0.95	2.46	3.385 (6)	165
C53—H53···N41^ii	0.95	2.57	3.473 (5)	158

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