Formation of a silicon-containing macrocycle with a pyridoxalimine Schiff base ligand

The reaction of dichloro­diphenyl­silane with a polydentate Schiff base ligand derived from pyridoxal and 2-hydroxy­aniline yields the macrocyclic centrosymmetric silicon com­pound 9,27-dimethyl-3,3,21,21-tetra­phenyl-2,4,20,22-tetra­oxa-8,13,26,31-tetra­aza-3,21-disilapenta­cyclo­[30.4.0.0^6,11.0^14,19.0^24,29]hexa­trideca-1(32),6,8,10,12,14,16,18,24,26,28,30,33,35-tetra­deca­ene-10,28-diol chloro­form tetra­solvate, C₅₂H₄₄N₄O₆Si₂·4CHCl₃. The asymmetric unit contains half of the macrocycle and two mol­ecules of chloro­form, with C—H...O and C—H...N contacts binding the two guests to the host in the crystal structure. This macrocyclic silicon compound represents a promising host for mol­ecular-recognition processes and for the construction of nanostructures.

S1. Comment

Carbon-based macrocycles are used frequently as hosts for molecular-recognition processes (Weber & Vögtle, 1996). The macrocycle provides the necessary preorganization of the host for the inclusion process (König, Rödel, Bubenitschek, Jones & Thondorf, 1995). The incorporation of other main group elements into the macrocycles gives these compounds new binding properties (König, Rödel, Bubenitschek & Jones, 1995). Earlier work has shown the coordinative ability of silicon (Jung & Xia, 1988), phosporous (Caminade & Majoral, 1994) and tin (Blanda et al., 1989) as bridging atoms in macrocycles. During our work on silicon complexes with tridentate O,N,O-ligands of Schiff base type, we used pyridoxal as a component of the ligand system. The reaction of pyridoxal hydrocloride with o-aminophenole in the presence of sodium methanolate gives the polydentate ligand, (I). There are numerous potential docking sites in the ligand molecule: the pyridine N atom, one aliphatic and two phenolic hydroxyl groups, and the imino N atom. The presence of diverse functional groups in (I) makes it difficult to predict the molecular structure of the reaction product with halogenosilanes. It was our initial goal to prepare a pentacoordinate silicon complex like (II). Surprisingly, the macrocyclic silicon compound, (III), was obtained from the reaction of (I) with Ph₂SiCl₂ in tetrahydrofuran in the presence of NEt₃ as a supporting base to remove the hydrogen chloride which is formed during the reaction. The first hint of the formation of a tetracoordinate silicon complex was found in the ²⁹Si NMR spectrum: compound (III) has a single resonance signal at -32.8 p.p.m. The ¹H and ¹³C NMR spectra did not give further information apart from the presence of the ligand system including one hydroxyl group.

Crystallization of (III) from a chloroform solution over several weeks at 278 K yielded single crystals of the title chloroform solvate, (III).4CHCl₃, which crystallizes in the triclinic space group P1 with half of the macrocycle and two molecules of CHCl₃ in the asymmetric unit (Fig. 1). The macrocycle is thus generated by a crystallographic inversion centre (Fig. 2). The Si atom is bound to the two phenyl groups, to phenolic atom O3 and to the aliphatic O atom from the next ligand molecule, thus forming a macrocycle (Fig. 2). The Si—O bonds are short (Table 1), but in the range for comparable Si—O bonds (Wagler et al., 2005; Böhme et al., 2006; Böhme & Günther, 2007; Böhme & Foehn, 2007). The coordination geometry around Si is distorted tetrahedral, with bond angles between 104.9 (1) and 117.1 (1)° (Table 1). The O₂Si(Ph)₂ moiety is a common structural motif. Some macrocycles with a similar distorted tetrahedral coordination environment at Si have been described earlier (Cragg et al., 1991; Rezzonico et al. 1998; Gómez & Farfán, 1999). The rather large bond angles at O (Table 1) are explained by the ionic character of the Si—O bonds (Gillespie & Johnson, 1997).

Two planes can be used to characterize the conformation of the dianion of the ligand molecule, (II). The plane of the C9–C14 phenyl ring makes an angle of 17.5 (2)° with the plane of the pyridine ring (C1–C5/N1). Nearly planar with this latter ring is the six-membered pseudo-ring (Fig. 1) consisting of atoms H1/O1/C2/C3/C7/N2 [at an angle of 2.1 (1)° to the pyridine ring]. The planarity of the six-membered pseudo-ring is caused by a strong intramolecular O—H···N interaction (entry 1, Table 2). The formation of hydrogen bonds between the imine N atom and an ortho hydroxyl group is a feature which is often observed in Schiff bases with o-hydroxy groups (Hökelek et al., 2004; Filarowski et al., 1999).

Two independent chloroform molecules are incorporated into the crystal structure. Contacts with the disordered Cl atoms of the C28-based solvate (Fig. 1) are not considered important for crystal structure formation. The non-disordered solvate shows only one very weak chlorine contact (C22—H22···Cl1 2.90 Å and 144°) but is bound to the guest via a C28—H28···O1 intermolecular contact (entry 3, Table 2). The other guest is connected to the host via a C—H···N contact (Fig. 3; entry 2, Table 2). One C8—H8A···π contact between one of the aliphatic H atoms, H8A, and the pyridine unit is localized with an H-to-centre distance of 2.94 Å and a C8—H8A···Cg angle of 109°, where Cg is the centre of the C1–C5/N1 ring at the symmetry position (2-x, 1-y, -z). This contact forms intermolecular chains of the host molecule along the crystallographic a axis (not shown in Fig. 3). These intermolecular contacts of weak to moderate strength in the crystal structure of (III).4CHCl₃ indicate potential coordination sites for interactions with other guest molecules.

Numerous potential bonding sites in the ligand system, along with the cavity of the macrocycle, provide promise for (III) as a host molecule in supramolecular recognition processes. Furthermore, the available OH, azomethine-N and pyridine-N groups could be useful for the construction of nanostructures via complexation with transition metals (Leininger et al., 2000).

Related literature

For related literature, see: Böhme & Foehn (2007); Böhme & Günther (2007); Böhme et al. (2006); Blanda et al. (1989); Caminade & Majoral (1994); Cragg et al. (1991); Filarowski et al. (1999); Gómez & Farfán (1999); Gillespie & Johnson (1997); Hökelek et al. (2004); Jung & Xia (1988); König, Rödel, Bubenitschek & Jones (1995); König, Rödel, Bubenitschek, Jones & Thondorf (1995); Leininger et al. (2000); Rezzonico et al. (1998); Sheldrick (2008); Wagler et al. (2005); Weber & Vögtle (1996).

S2. Experimental

Pyridoxal-N-(o-hydroxypenyl)imine, (I), was prepared as follows. To pyridoxal hydrochloride (4.06 g, 20 mmol) dissolved in methanol was added a solution of sodium methanolate (1.08 g, 20 mmol) in methanol. A solution of o-aminophenol (2.18 g, 20 mmol) in methanol was added dropwise. The suspension was boiled at reflux temperature. The colour of the solution became orange and a precipitate was formed. After 2 h, the suspension was cooled to room temperature and the precipitate was filtered off. The solid was washed with small amounts of water to remove sodium chloride, followed by diethyl ether. Compound (I) was obtained as an orange solid (yield 4.13 g, 80%; m.p. 495 K).

The preparation of (III) was performed in Schlenk tubes under argon with dry and air-free solvents. Compound (III) was prepared by the reaction of triethylamine (1.7 ml, 1.21 g, 12.0 mmol) and dichlorodiphenylsilane (1.22 g, 4.8 mmol) with (I) (1.25 g, 4.8 mmol) in dry tetrahydrofuran at room temperature. A white precipitate of triethylamine hydrocloride formed upon stirring the mixture for 6 d. After this period, the triethylamine hydrocloride was filtered off and washed with tetrahydrofuran. The solvent was removed in vacuo from the resulting clear red solution. The remaining solid was extracted with 1,2-dimethoxyethane. Addition of hexane, cooling to 278 K and filtration of this sample gave a red solid product (yield 1.48 g, 70.3%; m.p. 485 K). Single crystals of the title compound, (III).4CHCl₃, were obtained by recrystallization from CHCl₃.

NMR data are available in the archived CIF.

S3. Refinement

The final automatic data collection scan could not be completed due to loss of the crystal from the beam, with a subsequent gap in the inner-shell data.

One of the two symmetry-independent chloroform molecules is disordered over two orientations. The site occupation factors were refined and gave a final value of 0.739 (11) for the major orientation (Cl4A-Cl6A). Rigid bond restraints were applied to the U_ij-values of one phenyl ring (C24-C26) and to the disordered chloroform molecule at C28 [12 restraints with the DELU command in SHELXL (Sheldrick, 2008)]. Further restraints were used to generate similar U_ij-values and to restrain the atoms to be approximately isotropic for the atoms of one phenyl ring and for both chloroform molecules (30 restraints with the SIMU command and 84 restraints with the ISOR command in SHELXL).

All C-bound H atoms were positioned geometrically, with C—H = 0.95, 0.98, 0.99 or 1.00 Å for aryl-H, CH₃, CH₂ or tertiary C—H, respectively, and refined in riding mode, with U_iso(H) = 1.5U_eq(C) for methyl H or 1.2U_eq(C) for all other H. The H atom bonded to O1 was positioned geometrically, with O—H = 0.84 Å, and refined in riding mode, with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (III).4CHCl3, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. The molecular structure of (III).4CHCl3. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the intramolecular hydrogen bond. Chloroform molecules have been omitted.
	Fig. 3. A partial packing diagram for (III).4CHCl3, showing key intermolecular interactions. H atoms not involved in the hydrogen bonds have been omitted for clarity.

9,27-dimethyl-3,3,21,21-tetraphenyl-2,4,20,22-tetraoxa-8,13,26,31-tetraaza- 3,21-disilapentacyclo[30.4.0.0^6,11.0^14,19.0^24,29]hexatrideca- 1(32),6,8,10,12,14,16,18,24,26,28,30,33,35-tetradecaene-10,28-diol chloroform tetrasolvate

Crystal data

C52H44N4O6Si2·4CHCl3	Z = 1
Mr = 1354.56	F(000) = 692
Triclinic, P1	Dx = 1.474 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8831 (3) Å	Cell parameters from 8116 reflections
b = 11.2094 (3) Å	θ = 2.2–30.5°
c = 14.7584 (4) Å	µ = 0.64 mm^−1
α = 102.853 (2)°	T = 153 K
β = 101.899 (1)°	Prism, orange
γ = 98.733 (1)°	0.33 × 0.30 × 0.22 mm
V = 1525.91 (8) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	6493 independent reflections
Radiation source: sealed tube	5116 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.818, Tmax = 0.873	k = −13→12
14146 measured reflections	l = −18→18

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 1.0265P] where P = (Fo^2 + 2Fc^2)/3
6493 reflections	(Δ/σ)max = 0.001
391 parameters	Δρmax = 0.62 e Å^−3
126 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. Pyridoxal-N-(o-hydroxypenyl)imine, (I): ¹H NMR (DMSO, δ, p.p.m.): 14.72, 10.04 (s, OH, 2H), 9.25 (s, HC═N, 1H), 8.0–6.89 (m, CH_aromatic, 5H), 5.43 (CH₂—OH, 1H), 4.78 (CH₂—OH, 2H), 2.44 (CH₃, 3H); ¹³C NMR (DMSO, δ, p.p.m.): 158.6 (C═N), 153.8, 151.7, 148.5, 137.6, 134.1, 133.3, 129.2, 120.1, 119.7 (2 C), 116.8 (10 signals for aromatic C), 58.5 (CH₂—OH), 18.9 (CH₃).

Cyclo-bis{5-(oxymethyl)-4-{(E)-[(2-oxyphenyl)imino]methyl}- 2-methylpyridin-3-ol}diphenylsilane}, (III): ¹H NMR (CDCl₃, δ, p.p.m.): 14.31 (s, OH, 1H), 8.90 (s, HC═N, 1H), 7.97–6.56 (m, CH_aromatic, 15H), 5.13 (CH₂—O, 1H), 2.37 (CH₃, 3H); ¹³C NMR (CDCl₃, δ, p.p.m.): 157.4 (C═N), 154.3, 150.7, 148.0, 139.7, 137.1, 135.2, 134.9, 131.5, 131.2, 129.9, 129.4, 128.4, 122.1, 119.8, 119.5, 119.0 (signals for aromatic C), 60.8 (CH₂—O), 19.1 (CH₃); ²⁹Si NMR (CDCl₃, δ, p.p.m.): -32.8.

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Si1	0.40784 (8)	0.74702 (7)	0.22233 (5)	0.02333 (17)
O1	0.7646 (2)	0.54183 (18)	0.18553 (13)	0.0302 (4)
H1	0.7257	0.5863	0.1537	0.045*
O2	0.75599 (19)	0.24697 (16)	−0.17905 (13)	0.0254 (4)
O3	0.49024 (19)	0.69992 (17)	0.13786 (13)	0.0260 (4)
N1	0.9600 (3)	0.3049 (2)	0.12183 (17)	0.0306 (5)
N2	0.6701 (2)	0.61316 (19)	0.03971 (15)	0.0230 (4)
C1	0.8957 (3)	0.3828 (3)	0.17146 (19)	0.0292 (6)
C2	0.8220 (3)	0.4631 (2)	0.12955 (18)	0.0244 (5)
C3	0.8101 (3)	0.4583 (2)	0.03194 (18)	0.0221 (5)
C4	0.8774 (3)	0.3740 (2)	−0.01919 (18)	0.0233 (5)
C5	0.9512 (3)	0.3025 (2)	0.0296 (2)	0.0279 (6)
H5	0.9991	0.2479	−0.0046	0.033*
C6	0.9035 (4)	0.3833 (3)	0.2737 (2)	0.0458 (8)
H6A	0.9479	0.3153	0.2887	0.069*
H6B	0.8078	0.3715	0.2837	0.069*
H6C	0.9597	0.4635	0.3158	0.069*
C7	0.7281 (3)	0.5382 (2)	−0.01164 (18)	0.0227 (5)
H7	0.7177	0.5347	−0.0777	0.027*
C8	0.8687 (3)	0.3516 (2)	−0.12524 (19)	0.0256 (5)
H8A	0.8517	0.4273	−0.1459	0.031*
H8B	0.9595	0.3345	−0.1378	0.031*
C9	0.5879 (3)	0.6924 (2)	0.00303 (18)	0.0230 (5)
C10	0.4977 (3)	0.7404 (2)	0.05728 (18)	0.0225 (5)
C11	0.4162 (3)	0.8214 (2)	0.0269 (2)	0.0273 (6)
H11	0.3564	0.8548	0.0641	0.033*
C12	0.4223 (3)	0.8534 (2)	−0.0580 (2)	0.0300 (6)
H12	0.3648	0.9073	−0.0794	0.036*
C13	0.5112 (3)	0.8077 (3)	−0.1116 (2)	0.0325 (6)
H13	0.5151	0.8301	−0.1695	0.039*
C14	0.5947 (3)	0.7289 (3)	−0.0806 (2)	0.0289 (6)
H14	0.6576	0.6993	−0.1168	0.035*
C15	0.4068 (3)	0.6253 (2)	0.28974 (19)	0.0272 (6)
C16	0.4871 (3)	0.5331 (3)	0.2805 (2)	0.0355 (7)
H16	0.5501	0.5331	0.2398	0.043*
C17	0.4764 (4)	0.4414 (3)	0.3299 (2)	0.0456 (8)
H17	0.5321	0.3795	0.3230	0.055*
C18	0.3851 (4)	0.4399 (3)	0.3890 (2)	0.0464 (8)
H18	0.3772	0.3768	0.4223	0.056*
C19	0.3055 (4)	0.5306 (4)	0.3995 (2)	0.0485 (8)
H19	0.2429	0.5304	0.4405	0.058*
C20	0.3164 (4)	0.6220 (3)	0.3505 (2)	0.0407 (7)
H20	0.2610	0.6840	0.3585	0.049*
C21	0.4954 (3)	0.9093 (2)	0.29126 (19)	0.0263 (5)
C22	0.6293 (4)	0.9606 (3)	0.2866 (2)	0.0445 (8)
H22	0.6755	0.9125	0.2459	0.053*
C23	0.6980 (4)	1.0810 (3)	0.3400 (3)	0.0525 (9)
H23	0.7901	1.1144	0.3358	0.063*
C24	0.6330 (4)	1.1509 (3)	0.3983 (3)	0.0466 (8)
H24	0.6799	1.2330	0.4353	0.056*
C25	0.5015 (4)	1.1036 (4)	0.4034 (3)	0.0670 (12)
H25	0.4562	1.1531	0.4438	0.080*
C26	0.4319 (4)	0.9835 (3)	0.3503 (3)	0.0551 (10)
H26	0.3393	0.9519	0.3547	0.066*
C27	1.0270 (3)	0.0594 (3)	0.1747 (2)	0.0359 (7)
H27	0.9915	0.1322	0.1572	0.043*
Cl1	0.88490 (10)	−0.07058 (9)	0.13523 (7)	0.0545 (2)
Cl2	1.16119 (9)	0.03107 (9)	0.11692 (7)	0.0524 (2)
Cl3	1.09058 (11)	0.09797 (9)	0.30019 (6)	0.0538 (2)
C28	0.8845 (4)	0.7219 (3)	0.4064 (2)	0.0460 (8)
H28	0.8334	0.6530	0.3480	0.055*
Cl4A	0.7605 (3)	0.7944 (4)	0.45433 (12)	0.0590 (7)	0.739 (11)
Cl5A	0.9835 (4)	0.6569 (2)	0.49168 (15)	0.0449 (5)	0.739 (11)
Cl6A	1.0098 (4)	0.8238 (4)	0.3757 (3)	0.0964 (10)	0.739 (11)
Cl4B	0.7961 (10)	0.8394 (9)	0.4523 (5)	0.0694 (18)	0.261 (11)
Cl5B	0.9414 (9)	0.6478 (7)	0.4918 (5)	0.0435 (14)	0.261 (11)
Cl6B	0.9858 (8)	0.8023 (7)	0.3529 (5)	0.0538 (17)	0.261 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0247 (4)	0.0214 (4)	0.0237 (4)	0.0059 (3)	0.0060 (3)	0.0049 (3)
O1	0.0381 (11)	0.0319 (11)	0.0235 (9)	0.0173 (9)	0.0085 (8)	0.0058 (8)
O2	0.0240 (9)	0.0231 (9)	0.0259 (9)	0.0045 (7)	0.0041 (7)	0.0022 (7)
O3	0.0314 (10)	0.0244 (9)	0.0265 (10)	0.0101 (8)	0.0101 (8)	0.0098 (7)
N1	0.0340 (13)	0.0253 (12)	0.0312 (12)	0.0108 (10)	0.0033 (10)	0.0060 (9)
N2	0.0221 (11)	0.0207 (10)	0.0257 (11)	0.0051 (8)	0.0043 (9)	0.0059 (8)
C1	0.0331 (15)	0.0263 (14)	0.0258 (13)	0.0082 (11)	0.0016 (11)	0.0055 (11)
C2	0.0247 (13)	0.0212 (12)	0.0240 (13)	0.0028 (10)	0.0034 (10)	0.0029 (10)
C3	0.0199 (12)	0.0183 (12)	0.0249 (13)	0.0013 (9)	0.0031 (10)	0.0032 (10)
C4	0.0212 (12)	0.0205 (12)	0.0251 (13)	0.0010 (10)	0.0049 (10)	0.0027 (10)
C5	0.0276 (14)	0.0213 (13)	0.0324 (14)	0.0065 (10)	0.0064 (11)	0.0026 (11)
C6	0.069 (2)	0.048 (2)	0.0267 (15)	0.0298 (17)	0.0080 (15)	0.0130 (14)
C7	0.0224 (13)	0.0203 (12)	0.0229 (12)	0.0016 (10)	0.0031 (10)	0.0049 (10)
C8	0.0243 (13)	0.0231 (13)	0.0277 (13)	0.0040 (10)	0.0068 (10)	0.0032 (10)
C9	0.0229 (13)	0.0181 (12)	0.0250 (13)	0.0029 (9)	0.0014 (10)	0.0049 (10)
C10	0.0229 (13)	0.0181 (12)	0.0238 (12)	0.0009 (9)	0.0041 (10)	0.0038 (9)
C11	0.0260 (14)	0.0220 (13)	0.0346 (15)	0.0058 (10)	0.0076 (11)	0.0083 (11)
C12	0.0302 (15)	0.0222 (13)	0.0376 (15)	0.0067 (11)	0.0029 (12)	0.0119 (11)
C13	0.0404 (17)	0.0306 (15)	0.0286 (14)	0.0067 (12)	0.0074 (12)	0.0136 (12)
C14	0.0337 (15)	0.0283 (14)	0.0278 (14)	0.0088 (11)	0.0110 (11)	0.0086 (11)
C15	0.0277 (14)	0.0264 (14)	0.0247 (13)	0.0030 (11)	0.0032 (11)	0.0059 (10)
C16	0.0398 (17)	0.0360 (16)	0.0366 (16)	0.0130 (13)	0.0130 (13)	0.0148 (13)
C17	0.062 (2)	0.0389 (18)	0.0443 (19)	0.0213 (16)	0.0134 (16)	0.0198 (15)
C18	0.066 (2)	0.0386 (18)	0.0364 (17)	0.0049 (16)	0.0103 (16)	0.0189 (14)
C19	0.056 (2)	0.057 (2)	0.0415 (19)	0.0114 (17)	0.0238 (16)	0.0223 (16)
C20	0.0487 (19)	0.0459 (19)	0.0376 (17)	0.0195 (15)	0.0198 (15)	0.0167 (14)
C21	0.0271 (14)	0.0249 (13)	0.0260 (13)	0.0073 (11)	0.0030 (11)	0.0067 (10)
C22	0.0408 (18)	0.0389 (17)	0.0490 (19)	−0.0013 (14)	0.0213 (15)	−0.0011 (15)
C23	0.042 (2)	0.0424 (19)	0.061 (2)	−0.0114 (15)	0.0145 (17)	0.0021 (17)
C24	0.050 (2)	0.0270 (16)	0.050 (2)	−0.0013 (14)	0.0017 (16)	0.0006 (14)
C25	0.059 (2)	0.0407 (19)	0.088 (3)	0.0083 (17)	0.031 (2)	−0.0194 (19)
C26	0.0391 (18)	0.0397 (18)	0.078 (2)	0.0035 (14)	0.0256 (17)	−0.0092 (17)
C27	0.0429 (17)	0.0337 (16)	0.0371 (16)	0.0168 (13)	0.0141 (13)	0.0118 (13)
Cl1	0.0489 (5)	0.0575 (5)	0.0541 (5)	0.0015 (4)	0.0250 (4)	0.0039 (4)
Cl2	0.0475 (5)	0.0516 (5)	0.0648 (5)	0.0118 (4)	0.0289 (4)	0.0137 (4)
Cl3	0.0656 (5)	0.0547 (5)	0.0400 (4)	0.0184 (4)	0.0073 (4)	0.0119 (4)
C28	0.056 (2)	0.049 (2)	0.0309 (16)	0.0113 (16)	0.0061 (15)	0.0120 (14)
Cl4A	0.0505 (9)	0.0732 (12)	0.0538 (8)	0.0194 (8)	0.0102 (6)	0.0158 (7)
Cl5A	0.0490 (10)	0.0475 (8)	0.0372 (7)	0.0103 (7)	0.0035 (7)	0.0156 (5)
Cl6A	0.0993 (14)	0.1004 (14)	0.1016 (15)	−0.0004 (9)	0.0286 (10)	0.0619 (11)
Cl4B	0.069 (2)	0.069 (2)	0.071 (2)	0.0206 (13)	0.0150 (11)	0.0179 (12)
Cl5B	0.0456 (19)	0.0456 (17)	0.0402 (16)	0.0078 (12)	0.0106 (12)	0.0144 (10)
Cl6B	0.057 (2)	0.056 (2)	0.0489 (19)	0.0023 (11)	0.0145 (11)	0.0203 (12)

Geometric parameters (Å, º)

Si1—O2^i	1.6310 (19)	C13—H13	0.9500
Si1—O3	1.6591 (19)	C14—H14	0.9500
Si1—C21	1.852 (3)	C15—C20	1.392 (4)
Si1—C15	1.859 (3)	C15—C16	1.395 (4)
O1—C2	1.344 (3)	C16—C17	1.391 (4)
O1—H1	0.8400	C16—H16	0.9500
O2—C8	1.439 (3)	C17—C18	1.378 (5)
O2—Si1^i	1.6310 (19)	C17—H17	0.9500
O3—C10	1.376 (3)	C18—C19	1.379 (5)
N1—C1	1.334 (4)	C18—H18	0.9500
N1—C5	1.339 (4)	C19—C20	1.383 (5)
N2—C7	1.285 (3)	C19—H19	0.9500
N2—C9	1.412 (3)	C20—H20	0.9500
C1—C2	1.408 (4)	C21—C26	1.381 (4)
C1—C6	1.494 (4)	C21—C22	1.383 (4)
C2—C3	1.409 (4)	C22—C23	1.389 (5)
C3—C4	1.409 (4)	C22—H22	0.9500
C3—C7	1.460 (3)	C23—C24	1.359 (5)
C4—C5	1.382 (4)	C23—H23	0.9500
C4—C8	1.511 (4)	C24—C25	1.351 (5)
C5—H5	0.9500	C24—H24	0.9500
C6—H6A	0.9800	C25—C26	1.388 (5)
C6—H6B	0.9800	C25—H25	0.9500
C6—H6C	0.9800	C26—H26	0.9500
C7—H7	0.9500	C27—Cl2	1.749 (3)
C8—H8A	0.9900	C27—Cl3	1.759 (3)
C8—H8B	0.9900	C27—Cl1	1.760 (3)
C9—C14	1.395 (4)	C27—H27	1.0000
C9—C10	1.404 (4)	C28—Cl6B	1.676 (8)
C10—C11	1.388 (4)	C28—Cl5B	1.705 (8)
C11—C12	1.388 (4)	C28—Cl4A	1.751 (4)
C11—H11	0.9500	C28—Cl6A	1.755 (5)
C12—C13	1.380 (4)	C28—Cl4B	1.776 (7)
C12—H12	0.9500	C28—Cl5A	1.785 (4)
C13—C14	1.384 (4)	C28—H28	1.0000
O2^i—Si1—O3	113.09 (10)	C20—C15—Si1	118.4 (2)
O2^i—Si1—C21	105.25 (11)	C16—C15—Si1	124.1 (2)
O3—Si1—C21	109.07 (11)	C17—C16—C15	121.1 (3)
O2^i—Si1—C15	107.75 (11)	C17—C16—H16	119.5
O3—Si1—C15	104.87 (11)	C15—C16—H16	119.5
C21—Si1—C15	117.06 (12)	C18—C17—C16	120.2 (3)
C2—O1—H1	109.5	C18—C17—H17	119.9
C8—O2—Si1^i	126.29 (16)	C16—C17—H17	119.9
C10—O3—Si1	129.71 (16)	C17—C18—C19	119.6 (3)
C1—N1—C5	118.5 (2)	C17—C18—H18	120.2
C7—N2—C9	123.4 (2)	C19—C18—H18	120.2
N1—C1—C2	121.5 (2)	C18—C19—C20	120.1 (3)
N1—C1—C6	118.3 (2)	C18—C19—H19	119.9
C2—C1—C6	120.2 (3)	C20—C19—H19	119.9
O1—C2—C1	117.7 (2)	C19—C20—C15	121.6 (3)
O1—C2—C3	122.4 (2)	C19—C20—H20	119.2
C1—C2—C3	119.9 (2)	C15—C20—H20	119.2
C2—C3—C4	117.4 (2)	C26—C21—C22	117.1 (3)
C2—C3—C7	119.3 (2)	C26—C21—Si1	122.0 (2)
C4—C3—C7	123.3 (2)	C22—C21—Si1	120.9 (2)
C5—C4—C3	118.1 (2)	C21—C22—C23	121.5 (3)
C5—C4—C8	117.4 (2)	C21—C22—H22	119.2
C3—C4—C8	124.5 (2)	C23—C22—H22	119.2
N1—C5—C4	124.6 (2)	C24—C23—C22	119.8 (3)
N1—C5—H5	117.7	C24—C23—H23	120.1
C4—C5—H5	117.7	C22—C23—H23	120.1
C1—C6—H6A	109.5	C25—C24—C23	119.9 (3)
C1—C6—H6B	109.5	C25—C24—H24	120.0
H6A—C6—H6B	109.5	C23—C24—H24	120.0
C1—C6—H6C	109.5	C24—C25—C26	120.8 (3)
H6A—C6—H6C	109.5	C24—C25—H25	119.6
H6B—C6—H6C	109.5	C26—C25—H25	119.6
N2—C7—C3	119.7 (2)	C21—C26—C25	120.9 (3)
N2—C7—H7	120.1	C21—C26—H26	119.6
C3—C7—H7	120.1	C25—C26—H26	119.6
O2—C8—C4	110.2 (2)	Cl2—C27—Cl3	111.41 (17)
O2—C8—H8A	109.6	Cl2—C27—Cl1	110.61 (17)
C4—C8—H8A	109.6	Cl3—C27—Cl1	110.63 (17)
O2—C8—H8B	109.6	Cl2—C27—H27	108.0
C4—C8—H8B	109.6	Cl3—C27—H27	108.0
H8A—C8—H8B	108.1	Cl1—C27—H27	108.0
C14—C9—C10	118.7 (2)	Cl6B—C28—Cl5B	126.5 (5)
C14—C9—N2	124.4 (2)	Cl6B—C28—Cl4A	117.4 (3)
C10—C9—N2	116.9 (2)	Cl5B—C28—Cl4A	100.8 (3)
O3—C10—C11	122.5 (2)	Cl5B—C28—Cl6A	118.7 (4)
O3—C10—C9	117.4 (2)	Cl4A—C28—Cl6A	113.9 (3)
C11—C10—C9	120.1 (2)	Cl6B—C28—Cl4B	99.4 (5)
C12—C11—C10	119.9 (3)	Cl5B—C28—Cl4B	110.3 (3)
C12—C11—H11	120.0	Cl6A—C28—Cl4B	95.0 (4)
C10—C11—H11	120.0	Cl6B—C28—Cl5A	113.1 (4)
C13—C12—C11	120.5 (3)	Cl4A—C28—Cl5A	110.5 (2)
C13—C12—H12	119.7	Cl6A—C28—Cl5A	105.7 (3)
C11—C12—H12	119.7	Cl4B—C28—Cl5A	116.7 (3)
C12—C13—C14	119.7 (3)	Cl6B—C28—H28	96.9
C12—C13—H13	120.1	Cl5B—C28—H28	105.0
C14—C13—H13	120.1	Cl4A—C28—H28	108.9
C13—C14—C9	120.9 (3)	Cl6A—C28—H28	108.9
C13—C14—H14	119.5	Cl4B—C28—H28	119.6
C9—C14—H14	119.5	Cl5A—C28—H28	108.9
C20—C15—C16	117.4 (3)
O2^i—Si1—O3—C10	49.2 (2)	C9—C10—C11—C12	0.9 (4)
C21—Si1—O3—C10	−67.6 (2)	C10—C11—C12—C13	−1.4 (4)
C15—Si1—O3—C10	166.3 (2)	C11—C12—C13—C14	0.2 (4)
C5—N1—C1—C2	−1.1 (4)	C12—C13—C14—C9	1.6 (4)
C5—N1—C1—C6	178.8 (3)	C10—C9—C14—C13	−2.1 (4)
N1—C1—C2—O1	−177.7 (2)	N2—C9—C14—C13	−179.5 (2)
C6—C1—C2—O1	2.4 (4)	O2^i—Si1—C15—C20	−44.2 (3)
N1—C1—C2—C3	2.7 (4)	O3—Si1—C15—C20	−164.9 (2)
C6—C1—C2—C3	−177.3 (3)	C21—Si1—C15—C20	74.1 (3)
O1—C2—C3—C4	178.6 (2)	O2^i—Si1—C15—C16	133.1 (2)
C1—C2—C3—C4	−1.8 (4)	O3—Si1—C15—C16	12.4 (3)
O1—C2—C3—C7	−2.3 (4)	C21—Si1—C15—C16	−108.6 (3)
C1—C2—C3—C7	177.3 (2)	C20—C15—C16—C17	0.3 (5)
C2—C3—C4—C5	−0.4 (3)	Si1—C15—C16—C17	−177.0 (3)
C7—C3—C4—C5	−179.5 (2)	C15—C16—C17—C18	0.2 (5)
C2—C3—C4—C8	176.4 (2)	C16—C17—C18—C19	−0.6 (5)
C7—C3—C4—C8	−2.6 (4)	C17—C18—C19—C20	0.4 (6)
C1—N1—C5—C4	−1.3 (4)	C18—C19—C20—C15	0.1 (6)
C3—C4—C5—N1	2.1 (4)	C16—C15—C20—C19	−0.4 (5)
C8—C4—C5—N1	−175.0 (2)	Si1—C15—C20—C19	177.1 (3)
C9—N2—C7—C3	−179.2 (2)	O2^i—Si1—C21—C26	42.7 (3)
C2—C3—C7—N2	1.2 (4)	O3—Si1—C21—C26	164.3 (3)
C4—C3—C7—N2	−179.7 (2)	C15—Si1—C21—C26	−76.9 (3)
Si1^i—O2—C8—C4	90.4 (2)	O2^i—Si1—C21—C22	−138.3 (3)
C5—C4—C8—O2	83.2 (3)	O3—Si1—C21—C22	−16.6 (3)
C3—C4—C8—O2	−93.7 (3)	C15—Si1—C21—C22	102.1 (3)
C7—N2—C9—C14	−21.0 (4)	C26—C21—C22—C23	0.9 (5)
C7—N2—C9—C10	161.5 (2)	Si1—C21—C22—C23	−178.2 (3)
Si1—O3—C10—C11	−9.1 (4)	C21—C22—C23—C24	−0.2 (6)
Si1—O3—C10—C9	173.52 (18)	C22—C23—C24—C25	−0.6 (6)
C14—C9—C10—O3	178.2 (2)	C23—C24—C25—C26	0.5 (7)
N2—C9—C10—O3	−4.2 (3)	C22—C21—C26—C25	−0.9 (6)
C14—C9—C10—C11	0.8 (4)	Si1—C21—C26—C25	178.1 (3)
N2—C9—C10—C11	178.4 (2)	C24—C25—C26—C21	0.2 (7)
O3—C10—C11—C12	−176.3 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.84	1.77	2.511 (3)	147
C27—H27···N1	1.00	2.16	3.149 (4)	168
C28—H28···O1	1.00	2.35	3.295 (4)	158