Penta­coordination versus tetra­coordination in silicon derivatives of an O,N,O′-tridentate ligand

Bis[2-(2-hydr­oxy-3-methoxy­benzyl­ideneamino)phenolato-κO]dimethyl­silicon, C₃₀H₃₀N₂O₆Si, (II), was isolated from the reaction of 2-(2-hydr­oxy-3-methoxy­benzyl­ideneamino)phenol, (I), with dichloro­dimethyl­silane at 339 K. It consists of two ligand mol­ecules and the Me₂Si unit forming a dialkoxy­dimethyl­silane with a tetra­coordinate Si atom. [2-(3-Meth­oxy-2-oxidobenzyl­ideneamino)phenolato-κ³O,N,O′]­dimethyl­sili­con, C₁₆H₁₇NO₃Si, (III), was isolated from the same reaction conducted at 263 K. In this complex, the dianion of (I) is coordinated via two O atoms and an azomethine N atom to the penta­coordinate Si atom. According to quantum chemical calculations, (II) is the thermodynamically stable product and (III) is the kinetically favoured product.

S1. Comment

The chemistry of hypercoordinate silicon complexes is currently one of the main research areas in silicon chemistry (Chuit et al., 1993; Corriu & Young, 1989; Holmes, 1996; Kost & Kalikhman, 1998, 2004; Pestunovich et al., 1998; Tacke et al., 1999). In our work on penta- and hexacoordinate silicon complexes with tridentate O,N,O ligands (Böhme et al., 2006; Böhme & Günther, 2007; Böhme & Foehn, 2007) we used 2-(2-hydroxy-3-methoxybenzylideneamino)phenol, (I), as a potential ligand molecule. The reaction of (I) with dichlorodimethylsilane in the presence of triethylamine in THF [tetrahydrofuran?] under reflux conditions yields product mixtures. This was proven by a ²⁹Si NMR spectrum of the reaction solution. Extraction with n-hexane was attempted during the workup procedure. The raw product shows poor solubility in the non-polar solvent. The hexane solution was decanted from the product mixture, the solvent was removed in vacuo and the residue was recrystallized from a hexane/chloroform mixture (3:1) and stored for several weeks at 258 K. During that time an orange crystal formed. X-ray crystal structure analysis shows the formation of (II) as an unexpected side product from this reaction batch [Fig. 1 and reaction (a) in the Scheme]. Two ligand molecules and the Me₂Si unit form a dialkoxydimethylsilane with a tetracoordinate silicon atom. The Si—O bonds [Si1—O2 1.654 (1) and Si1—O5 1.650 (1) Å] and the Si—C bonds [Si1—C29 1.842 (2) and Si1—C30 1.837 (2) Å] are in the average range for compounds of this type (Kaftory et al., 1998). The coordination geometry at the Si atom is distorted tetrahedral with bond angles between 104.50 (7) (O5—Si1—C30) and 116.2 (1)° (C30—Si1—C29). The compound is further stabilized by two intramolecular O—H···N hydrogen bonds between the ortho-hydroxy groups and the azomethine N atoms (see Table 2). Repeated attempts to prepare compound (II) selectively by choosing the appropriate ratio of educts failed.

On the other hand, it was possible to obtain the desired pentacoordinate product by choosing suitable reaction conditions [Scheme, reaction (b)]. The reaction between (I) and dichlorodimethylsilane was carried out at 263 K with a short reaction time (0.5 h) followed by immediate workup of the reaction batch. A red crystalline product was obtained after workup. The X-ray crystal structure analysis of a suitable crystal verified the formation of the pentacoordinate Si complex, (III) (Fig. 2). The Si atom is bound to the C atoms of the methyl groups (C15 and C16), to the O atoms (O1 and O2) and to the N atom, N1, of a single imine ligand. The Si—O [Si1—O1 1.7125 (9), Si1—O2 1.367 (9) Å] and the Si—C distances [Si1—C15 1.872 (1), Si1—C16 1.882 (1) Å] are comparable with those in similar pentacoordinate compounds (Böhme & Günther, 2007). The Si—N distance is longer [Si1—N1 2.068 (1) Å], which is easily explained by the coordinative character of this bond. The coordination geometry at the Si atom can be deduced from the bond angles at Si. A suitable parameter for the description of the coordination geometry in pentacoordinate complexes is defined as τ = (β-α)/60 (Addison et al., 1984). Angle β is the largest angle at the central atom and angle α is the second largest. For a perfect square pyramid, τ is equal to zero, whereas it becomes one for a perfect trigonal bipyramid. The two largest bond angles at Si in (III) are O1—Si—O2 135.57 (5) and C16—Si1—N1 163.39 (6)°. This gives a value of τ = 0.46 for complex (III), which is right between both coordination geometries. If we were to consider (III) as a strongly distorted square pyramid, the apex of the pyramid would be formed by atom C15, while atoms O1, O2, N1 and C16 would represent the base of the pyramid. The coordination geometry of (III) is far more distorted than the geometries of comparable Si complexes with o-hydroxyacetophenone-N-(2-hydroxyethyl)imine as the tridentate O,N,O ligand. Complexes with this ligand have τ values from 0.78 (Böhme & Günther, 2007) to 0.94 (Böhme & Foehn, 2007) as a result of a more flexible ethylene group instead of the phenylene group used in (III). The ethylene group allows for the occurrence of a relaxed coordination geometry close to that of an ideal trigonal bipyramid.

Bond lengthening through higher coordination is a known effect in Si chemistry (Chuit et al., 1993), and it is interesting to compare the bond lengths of the pentacoordinate derivative (III) with the bond lengths of the tetracoordinate compound (II). The bond Si1—O2 in (III) is 4.8% and 5.0% longer, respectively, than the comparable bonds Si1—O2 and Si1—O5 in (II). The average value of the Si—C bonds in (III) is 2% longer than the average of the Si—C bonds in (II).

It is possible to explain the preferred formation of a product mixture containing (II) on the basis of quantum chemical calculations. The geometries of (II), (III), and four different conformations of the ligand molecule (I) have been optimized with B3PW91/6–31 G(d,p). If we assume an equilibrium between (II) and a mixture of (I) and (III) [equilibrium (c) in the Scheme], we can calculate the enthalpy (Δ_RH) and free energy (Δ_RG) for this reaction (see Table 4). According to the quantum chemical analysis, the enthalpy of (II) is 42.3 kJ mol^-1 lower than the sum of the enthalpies of (I) and (III). That means an individual molecule of (II) is thermodynamically more stable at 0 K than the mixture of (I) and (III). This picture becomes diversified if we consider the entropy of the system, which is 0.14 kJ mol^-1 K^-1, and calculate the free energy. The difference in free energy is only 1.6 kJ mol^-1 at 298 K. Thus, at room temperature, (II) is only a tiny bit lower in energy than the mixture of (I) and (III). Raising the temperature above 298 K leads to a free energy of nearly zero (Δ_RG ≈ 0), i.e. the compounds (II), (III) and (I) are in equilibrium. This explains the formation of product mixtures during the syntheses under reflux conditions.

The synthesis at low temperatures favours the formation of (III), which therefore should be considered as the kinetically preferred product if we take into consideration the competition between reactions (a) and (b). The influence of solvents, the solubility of intermediates and products, and the varying ratio of starting materials are not accounted for in this quantum chemical analysis and would complicate things further.

The isolation of (II) and (III) from the same starting materials represents a rare case, which allows insight into the complicated interplay between thermodynamic and kinetic factors determining the formation of tetra- or pentacoordinated compounds of silicon.

Related literature

For related literature, see: Addison et al. (1984); Böhme & Foehn (2007); Böhme & Günther (2007); Böhme et al. (2006); Chuit et al. (1993); Corriu & Young (1989); Holmes (1996); Kaftory et al. (1998); Kost & Kalikhman (1998, 2004); Pestunovich et al. (1998); Tacke et al. (1999).

S2. Experimental

The preparation of (II) and (III) was performed in Schlenk tubes under an argon atmosphere with anhydrous and air-free solvents.

For the preparation of (II), product mixtures were obtained when the reaction of 2-(2-hydroxy-3-methoxybenzylideneamino)phenol, (I), with dichlorodimethylsilane was performed in tetrahydrofuran (THF) under reflux. The composition of the reaction mixture was analysed by ²⁹Si NMR. The reaction mixture was filtered over a Schlenk filter and the residue was washed with THF. The solvent was removed completely in vacuo. Subsequent extraction of the red oily residue with hexane and diethyl ether also yielded product mixtures. The hexane was removed in vacuo from the extracted solution. Recrystallization from a hexane/chloroform mixture (3:1 v/v) gave one orange crystal of (II), which was characterized by X-ray structure analysis. Further spectroscopic characterization was not possible since only one crystal of (II) was obtained.

For the preparation of (III), 2-(2-hydroxy-3-methoxybenzylideneamino)phenol, (I) (1.50 g, 6.2 mmol), was dissolved in THF (70 ml). Triethylamine (1.87 g, 18.5 mmol, 50% excess) was added with a syringe. The reaction mixture was cooled to 263 K. After a few minutes, dichlorodimethylsilane (0.84 g, 6.5 mmol, 5% excess) was added with a syringe and this reaction mixture was stirred for 0.5 h at 263 K. After that time, a red suspension had formed. The suspension was filtered over a G3 filter at room temperature, and the residue was washed with THF (3 × 10 ml). The solvent was removed completely from the red filtrate in vacuo. The residue was dissolved in chloroform (5 ml), and n-hexane (8 ml) was added. A red crystalline precipitate deposited. The precipitate was filtered off, washed with n-hexane (2 × 2 ml) and dried in vacuo. Red prisms (1.23 g, 67%, m.p. 416–419 K). ¹H NMR (CDCl₃): δ 8.63 (s, CH═N), 7.37–6.82 (m, CH_ar), 3.89 (s, OCH₃), 0.33 (s, Si—CH₃). ¹³C NMR (CDCl₃): δ 155.9 (C1), 154.7 (C4), 152.2 (C9), 151.0 (C3), 131.1, 130.7, 123.5, 119.5, 118.9, 118.8, 118.1, 116.0, 113.6 (9 signals C_ar), 56.6 (C14), 3.6 (C15 and C16). ²⁹Si NMR (CDCl₃): δ -59.2.

S3. Refinement

The two H atoms in (II) forming the hydrogen bonds between the phenolic O and azomethine N atoms and the H atom at C1 in (III) were located in difference Fourier maps, and their positions and isotropic displacement parameters were refined. All other H atoms were positioned geometrically and were allowed to ride on their parent atoms, with C—H = 0.95 (phenyl) or 0.98 Å (methyl) and with U_iso(H) = 1.2U_eq(phenyl C) or 1.5U_eq(methyl C).

Computing details

For both compounds, data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 molecular structure of (II) at 153 K shown with 50% probability displacement ellipsoids.
	Fig. 2. The molecular structure of (III) at 153 K shown with 50% probability displacement ellipsoids.

(II) Bis[2-(2-hydroxy-3-methoxybenzylideneamino)phenolato- κO]dimethylsilicon

Crystal data

C30H30N2O6Si	F(000) = 1144
Mr = 542.65	Dx = 1.268 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6120 reflections
a = 16.5171 (8) Å	θ = 2.2–30.4°
b = 10.4952 (5) Å	µ = 0.13 mm^−1
c = 18.2931 (9) Å	T = 153 K
β = 116.272 (1)°	Prism, orange
V = 2843.5 (2) Å^3	0.52 × 0.50 × 0.38 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	6204 independent reflections
Radiation source: sealed tube	4889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
phi and ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick 1996)	h = −21→21
Tmin = 0.932, Tmax = 0.956	k = −13→12
39389 measured reflections	l = −23→23

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.8424P] where P = (Fo^2 + 2Fc^2)/3
6204 reflections	(Δ/σ)max < 0.001
364 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

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
Si1	0.53656 (3)	0.07019 (4)	0.23894 (3)	0.03330 (11)
N1	0.69541 (7)	−0.19583 (11)	0.28919 (7)	0.0249 (2)
O1	0.72108 (7)	−0.12172 (9)	0.43346 (6)	0.0320 (2)
H3	0.7149 (13)	−0.1208 (19)	0.3824 (13)	0.056 (6)*
O2	0.62900 (6)	0.03719 (9)	0.22884 (6)	0.0311 (2)
O3	0.73044 (7)	−0.17849 (10)	0.57621 (6)	0.0370 (3)
C1	0.68459 (9)	−0.31039 (13)	0.30851 (8)	0.0262 (3)
H1	0.6691	−0.3759	0.2687	0.031*
C2	0.69550 (9)	−0.34171 (13)	0.38953 (8)	0.0253 (3)
C3	0.71198 (9)	−0.24611 (13)	0.44832 (8)	0.0254 (3)
C4	0.71701 (9)	−0.27888 (14)	0.52442 (8)	0.0280 (3)
C5	0.70757 (10)	−0.40518 (14)	0.54197 (9)	0.0334 (3)
H5	0.7122	−0.4273	0.5940	0.040*
C6	0.69133 (11)	−0.49967 (14)	0.48354 (9)	0.0365 (3)
H6	0.6849	−0.5858	0.4960	0.044*
C7	0.68464 (10)	−0.46875 (14)	0.40807 (9)	0.0319 (3)
H7	0.6726	−0.5334	0.3683	0.038*
C8	0.67679 (9)	−0.16843 (13)	0.20750 (8)	0.0256 (3)
C9	0.63758 (8)	−0.05022 (13)	0.17644 (8)	0.0269 (3)
C10	0.60975 (9)	−0.02155 (16)	0.09452 (9)	0.0361 (3)
H10	0.5815	0.0578	0.0731	0.043*
C11	0.62330 (10)	−0.10896 (18)	0.04440 (9)	0.0403 (4)
H11	0.6028	−0.0903	−0.0118	0.048*
C12	0.66649 (10)	−0.22344 (17)	0.07565 (9)	0.0379 (4)
H12	0.6774	−0.2817	0.0413	0.046*
C13	0.69375 (10)	−0.25312 (14)	0.15697 (8)	0.0306 (3)
H13	0.7241	−0.3312	0.1784	0.037*
C14	0.72906 (14)	−0.20337 (19)	0.65254 (10)	0.0506 (5)
H14A	0.6709	−0.2412	0.6427	0.076*
H14B	0.7375	−0.1234	0.6827	0.076*
H14C	0.7779	−0.2626	0.6845	0.076*
C15	0.25485 (9)	0.37213 (13)	0.08815 (8)	0.0275 (3)
H15	0.2465	0.4473	0.0567	0.033*
N2	0.33386 (7)	0.32268 (11)	0.12616 (7)	0.0262 (2)
O4	0.27086 (6)	0.14112 (10)	0.17731 (6)	0.0292 (2)
H17	0.3102 (15)	0.193 (2)	0.1675 (13)	0.071 (7)*
O5	0.47136 (7)	0.16523 (10)	0.16416 (7)	0.0366 (3)
O6	0.13233 (7)	0.02422 (10)	0.17973 (6)	0.0338 (2)
C16	0.17841 (9)	0.31227 (13)	0.09362 (8)	0.0273 (3)
C17	0.18987 (9)	0.19776 (13)	0.13724 (8)	0.0245 (3)
C18	0.11392 (9)	0.13672 (13)	0.13723 (8)	0.0278 (3)
C19	0.02911 (10)	0.18977 (15)	0.09573 (10)	0.0365 (3)
H19	−0.0219	0.1482	0.0958	0.044*
C20	0.01814 (10)	0.30480 (16)	0.05345 (11)	0.0447 (4)
H20	−0.0402	0.3415	0.0255	0.054*
C21	0.09143 (10)	0.36473 (15)	0.05225 (10)	0.0396 (4)
H21	0.0833	0.4424	0.0232	0.047*
C22	0.41178 (9)	0.37233 (13)	0.12320 (8)	0.0259 (3)
C23	0.48460 (9)	0.28828 (13)	0.14653 (8)	0.0287 (3)
C24	0.56500 (10)	0.32787 (15)	0.14659 (10)	0.0371 (3)
H24	0.6144	0.2705	0.1624	0.045*
C25	0.57279 (10)	0.45131 (15)	0.12355 (10)	0.0381 (4)
H25	0.6276	0.4783	0.1234	0.046*
C26	0.50134 (10)	0.53535 (15)	0.10078 (10)	0.0381 (3)
H26	0.5073	0.6198	0.0851	0.046*
C27	0.42097 (10)	0.49673 (14)	0.10074 (9)	0.0334 (3)
H27	0.3721	0.5550	0.0854	0.040*
C28	0.05704 (11)	−0.04755 (17)	0.17525 (11)	0.0456 (4)
H28A	0.0237	0.0026	0.1982	0.068*
H28B	0.0784	−0.1267	0.2063	0.068*
H28C	0.0172	−0.0679	0.1182	0.068*
C29	0.57717 (14)	0.15255 (19)	0.33776 (11)	0.0528 (5)
H29A	0.6055	0.2334	0.3352	0.079*
H29B	0.6215	0.0988	0.3806	0.079*
H29C	0.5261	0.1693	0.3501	0.079*
C30	0.46764 (12)	−0.07294 (17)	0.22650 (14)	0.0531 (5)
H30A	0.4120	−0.0494	0.2299	0.080*
H30B	0.5017	−0.1341	0.2697	0.080*
H30C	0.4525	−0.1116	0.1733	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0327 (2)	0.0273 (2)	0.0446 (2)	0.00628 (16)	0.02135 (18)	0.00860 (17)
N1	0.0246 (5)	0.0262 (6)	0.0247 (5)	0.0007 (4)	0.0116 (4)	0.0013 (4)
O1	0.0451 (6)	0.0241 (5)	0.0281 (5)	−0.0061 (4)	0.0173 (5)	−0.0011 (4)
O2	0.0290 (5)	0.0273 (5)	0.0369 (5)	0.0030 (4)	0.0147 (4)	0.0021 (4)
O3	0.0491 (6)	0.0375 (6)	0.0267 (5)	−0.0105 (5)	0.0189 (5)	−0.0049 (4)
C1	0.0262 (6)	0.0256 (7)	0.0286 (7)	0.0018 (5)	0.0136 (5)	−0.0025 (5)
C2	0.0241 (6)	0.0252 (7)	0.0289 (7)	0.0027 (5)	0.0137 (5)	0.0018 (5)
C3	0.0226 (6)	0.0246 (7)	0.0279 (6)	−0.0003 (5)	0.0102 (5)	0.0023 (5)
C4	0.0254 (6)	0.0302 (7)	0.0282 (7)	−0.0012 (5)	0.0116 (5)	−0.0002 (6)
C5	0.0377 (8)	0.0337 (8)	0.0312 (7)	0.0048 (6)	0.0176 (6)	0.0092 (6)
C6	0.0472 (9)	0.0250 (7)	0.0436 (8)	0.0052 (6)	0.0258 (7)	0.0097 (6)
C7	0.0390 (8)	0.0238 (7)	0.0386 (8)	0.0040 (6)	0.0222 (6)	0.0010 (6)
C8	0.0232 (6)	0.0292 (7)	0.0247 (6)	−0.0037 (5)	0.0108 (5)	−0.0006 (5)
C9	0.0204 (6)	0.0312 (7)	0.0284 (6)	−0.0021 (5)	0.0102 (5)	0.0015 (5)
C10	0.0277 (7)	0.0440 (9)	0.0328 (7)	0.0013 (6)	0.0099 (6)	0.0107 (7)
C11	0.0339 (8)	0.0606 (11)	0.0240 (7)	−0.0076 (7)	0.0108 (6)	0.0036 (7)
C12	0.0386 (8)	0.0482 (10)	0.0315 (7)	−0.0107 (7)	0.0195 (6)	−0.0100 (7)
C13	0.0327 (7)	0.0307 (7)	0.0320 (7)	−0.0047 (6)	0.0174 (6)	−0.0031 (6)
C14	0.0735 (12)	0.0536 (11)	0.0295 (8)	−0.0082 (9)	0.0270 (8)	−0.0035 (7)
C15	0.0299 (7)	0.0221 (7)	0.0306 (7)	0.0003 (5)	0.0134 (6)	0.0011 (5)
N2	0.0269 (6)	0.0243 (6)	0.0292 (6)	−0.0007 (4)	0.0140 (5)	−0.0017 (4)
O4	0.0260 (5)	0.0296 (5)	0.0312 (5)	0.0026 (4)	0.0118 (4)	0.0048 (4)
O5	0.0275 (5)	0.0257 (5)	0.0528 (6)	0.0020 (4)	0.0143 (5)	0.0089 (5)
O6	0.0327 (5)	0.0330 (6)	0.0366 (5)	−0.0016 (4)	0.0161 (4)	0.0081 (4)
C16	0.0274 (7)	0.0254 (7)	0.0293 (7)	0.0006 (5)	0.0127 (5)	−0.0007 (5)
C17	0.0253 (6)	0.0259 (7)	0.0227 (6)	0.0022 (5)	0.0109 (5)	−0.0033 (5)
C18	0.0311 (7)	0.0273 (7)	0.0273 (7)	−0.0006 (6)	0.0149 (6)	−0.0002 (5)
C19	0.0274 (7)	0.0364 (8)	0.0474 (9)	−0.0015 (6)	0.0181 (6)	0.0046 (7)
C20	0.0256 (7)	0.0399 (9)	0.0642 (11)	0.0065 (6)	0.0158 (7)	0.0141 (8)
C21	0.0319 (8)	0.0298 (8)	0.0533 (9)	0.0044 (6)	0.0155 (7)	0.0122 (7)
C22	0.0260 (6)	0.0259 (7)	0.0257 (6)	−0.0015 (5)	0.0115 (5)	−0.0008 (5)
C23	0.0288 (7)	0.0238 (7)	0.0321 (7)	−0.0008 (5)	0.0122 (6)	0.0012 (5)
C24	0.0285 (7)	0.0324 (8)	0.0514 (9)	0.0028 (6)	0.0184 (7)	0.0035 (7)
C25	0.0315 (7)	0.0351 (8)	0.0523 (9)	−0.0063 (6)	0.0228 (7)	−0.0008 (7)
C26	0.0382 (8)	0.0285 (8)	0.0483 (9)	−0.0042 (6)	0.0199 (7)	0.0058 (7)
C27	0.0304 (7)	0.0272 (7)	0.0416 (8)	0.0016 (6)	0.0151 (6)	0.0032 (6)
C28	0.0401 (9)	0.0453 (10)	0.0528 (10)	−0.0053 (7)	0.0219 (8)	0.0164 (8)
C29	0.0640 (12)	0.0525 (11)	0.0496 (10)	0.0196 (9)	0.0322 (9)	0.0043 (8)
C30	0.0452 (10)	0.0367 (9)	0.0869 (14)	0.0032 (8)	0.0378 (10)	0.0189 (9)

Geometric parameters (Å, º)

Si1—O5	1.650 (1)	C15—C16	1.4528 (19)
Si1—O2	1.654 (1)	C15—H15	0.9500
Si1—C30	1.837 (2)	N2—C22	1.4116 (17)
Si1—C29	1.842 (2)	O4—C17	1.3460 (16)
N1—C1	1.2879 (18)	O4—H17	0.93 (2)
N1—C8	1.4154 (17)	O5—C23	1.3719 (17)
O1—C3	1.3554 (17)	O6—C18	1.3717 (17)
O1—H3	0.89 (2)	O6—C28	1.4250 (18)
O2—C9	1.3787 (17)	C16—C21	1.4062 (19)
O3—C4	1.3678 (17)	C16—C17	1.4082 (19)
O3—C14	1.4306 (18)	C17—C18	1.4086 (19)
C1—C2	1.4495 (19)	C18—C19	1.381 (2)
C1—H1	0.9500	C19—C20	1.402 (2)
C2—C3	1.4065 (19)	C19—H19	0.9500
C2—C7	1.4066 (19)	C20—C21	1.373 (2)
C3—C4	1.4001 (19)	C20—H20	0.9500
C4—C5	1.389 (2)	C21—H21	0.9500
C5—C6	1.394 (2)	C22—C27	1.397 (2)
C5—H5	0.9500	C22—C23	1.3974 (19)
C6—C7	1.374 (2)	C23—C24	1.391 (2)
C6—H6	0.9500	C24—C25	1.386 (2)
C7—H7	0.9500	C24—H24	0.9500
C8—C13	1.397 (2)	C25—C26	1.382 (2)
C8—C9	1.3985 (19)	C25—H25	0.9500
C9—C10	1.3920 (19)	C26—C27	1.388 (2)
C10—C11	1.383 (2)	C26—H26	0.9500
C10—H10	0.9500	C27—H27	0.9500
C11—C12	1.385 (2)	C28—H28A	0.9800
C11—H11	0.9500	C28—H28B	0.9800
C12—C13	1.385 (2)	C28—H28C	0.9800
C12—H12	0.9500	C29—H29A	0.9800
C13—H13	0.9500	C29—H29B	0.9800
C14—H14A	0.9800	C29—H29C	0.9800
C14—H14B	0.9800	C30—H30A	0.9800
C14—H14C	0.9800	C30—H30B	0.9800
C15—N2	1.2855 (17)	C30—H30C	0.9800
O5—Si1—O2	109.28 (6)	C15—N2—C22	123.70 (12)
O5—Si1—C30	104.50 (7)	C17—O4—H17	104.3 (14)
O2—Si1—C30	111.53 (7)	C23—O5—Si1	130.58 (9)
O5—Si1—C29	110.53 (7)	C18—O6—C28	116.96 (11)
O2—Si1—C29	104.76 (7)	C21—C16—C17	119.22 (13)
C30—Si1—C29	116.2 (1)	C21—C16—C15	120.37 (13)
C1—N1—C8	119.19 (12)	C17—C16—C15	120.34 (12)
C3—O1—H3	104.4 (13)	O4—C17—C16	122.51 (12)
C9—O2—Si1	126.95 (9)	O4—C17—C18	118.00 (12)
C4—O3—C14	117.89 (12)	C16—C17—C18	119.46 (12)
N1—C1—C2	121.52 (12)	O6—C18—C19	125.11 (13)
N1—C1—H1	119.2	O6—C18—C17	114.67 (12)
C2—C1—H1	119.2	C19—C18—C17	120.22 (13)
C3—C2—C7	119.60 (12)	C18—C19—C20	120.17 (14)
C3—C2—C1	120.96 (12)	C18—C19—H19	119.9
C7—C2—C1	119.35 (12)	C20—C19—H19	119.9
O1—C3—C4	118.23 (12)	C21—C20—C19	120.26 (14)
O1—C3—C2	122.33 (12)	C21—C20—H20	119.9
C4—C3—C2	119.42 (12)	C19—C20—H20	119.9
O3—C4—C5	125.13 (13)	C20—C21—C16	120.66 (14)
O3—C4—C3	114.81 (12)	C20—C21—H21	119.7
C5—C4—C3	120.06 (13)	C16—C21—H21	119.7
C4—C5—C6	120.32 (13)	C27—C22—C23	119.26 (12)
C4—C5—H5	119.8	C27—C22—N2	125.16 (12)
C6—C5—H5	119.8	C23—C22—N2	115.56 (12)
C7—C6—C5	120.32 (14)	O5—C23—C24	122.18 (13)
C7—C6—H6	119.8	O5—C23—C22	117.43 (12)
C5—C6—H6	119.8	C24—C23—C22	120.27 (13)
C6—C7—C2	120.26 (14)	C25—C24—C23	119.75 (14)
C6—C7—H7	119.9	C25—C24—H24	120.1
C2—C7—H7	119.9	C23—C24—H24	120.1
C13—C8—C9	119.21 (12)	C26—C25—C24	120.43 (14)
C13—C8—N1	123.76 (13)	C26—C25—H25	119.8
C9—C8—N1	117.02 (12)	C24—C25—H25	119.8
O2—C9—C10	121.20 (13)	C25—C26—C27	120.19 (14)
O2—C9—C8	118.65 (12)	C25—C26—H26	119.9
C10—C9—C8	120.13 (13)	C27—C26—H26	119.9
C11—C10—C9	119.80 (15)	C26—C27—C22	120.09 (13)
C11—C10—H10	120.1	C26—C27—H27	120.0
C9—C10—H10	120.1	C22—C27—H27	120.0
C12—C11—C10	120.44 (14)	O6—C28—H28A	109.5
C12—C11—H11	119.8	O6—C28—H28B	109.5
C10—C11—H11	119.8	H28A—C28—H28B	109.5
C11—C12—C13	120.09 (15)	O6—C28—H28C	109.5
C11—C12—H12	120.0	H28A—C28—H28C	109.5
C13—C12—H12	120.0	H28B—C28—H28C	109.5
C12—C13—C8	120.15 (14)	Si1—C29—H29A	109.5
C12—C13—H13	119.9	Si1—C29—H29B	109.5
C8—C13—H13	119.9	H29A—C29—H29B	109.5
O3—C14—H14A	109.5	Si1—C29—H29C	109.5
O3—C14—H14B	109.5	H29A—C29—H29C	109.5
H14A—C14—H14B	109.5	H29B—C29—H29C	109.5
O3—C14—H14C	109.5	Si1—C30—H30A	109.5
H14A—C14—H14C	109.5	Si1—C30—H30B	109.5
H14B—C14—H14C	109.5	H30A—C30—H30B	109.5
N2—C15—C16	119.56 (12)	Si1—C30—H30C	109.5
N2—C15—H15	120.2	H30A—C30—H30C	109.5
C16—C15—H15	120.2	H30B—C30—H30C	109.5
O5—Si1—O2—C9	−79.12 (12)	C16—C15—N2—C22	178.67 (12)
C30—Si1—O2—C9	35.91 (14)	O2—Si1—O5—C23	−65.70 (14)
C29—Si1—O2—C9	162.43 (12)	C30—Si1—O5—C23	174.83 (13)
C8—N1—C1—C2	−174.88 (11)	C29—Si1—O5—C23	49.09 (15)
N1—C1—C2—C3	4.6 (2)	N2—C15—C16—C21	−179.78 (14)
N1—C1—C2—C7	−178.79 (13)	N2—C15—C16—C17	−2.8 (2)
C7—C2—C3—O1	−178.53 (12)	C21—C16—C17—O4	179.05 (13)
C1—C2—C3—O1	−1.9 (2)	C15—C16—C17—O4	2.0 (2)
C7—C2—C3—C4	−0.23 (19)	C21—C16—C17—C18	1.3 (2)
C1—C2—C3—C4	176.36 (12)	C15—C16—C17—C18	−175.74 (12)
C14—O3—C4—C5	−4.2 (2)	C28—O6—C18—C19	5.0 (2)
C14—O3—C4—C3	175.10 (14)	C28—O6—C18—C17	−174.17 (13)
O1—C3—C4—O3	0.34 (18)	O4—C17—C18—O6	0.43 (17)
C2—C3—C4—O3	−178.04 (11)	C16—C17—C18—O6	178.31 (12)
O1—C3—C4—C5	179.66 (12)	O4—C17—C18—C19	−178.79 (13)
C2—C3—C4—C5	1.3 (2)	C16—C17—C18—C19	−0.9 (2)
O3—C4—C5—C6	178.02 (14)	O6—C18—C19—C20	−179.23 (15)
C3—C4—C5—C6	−1.2 (2)	C17—C18—C19—C20	−0.1 (2)
C4—C5—C6—C7	0.1 (2)	C18—C19—C20—C21	0.7 (3)
C5—C6—C7—C2	1.0 (2)	C19—C20—C21—C16	−0.4 (3)
C3—C2—C7—C6	−0.9 (2)	C17—C16—C21—C20	−0.6 (2)
C1—C2—C7—C6	−177.55 (13)	C15—C16—C21—C20	176.36 (15)
C1—N1—C8—C13	−35.55 (19)	C15—N2—C22—C27	19.9 (2)
C1—N1—C8—C9	143.19 (13)	C15—N2—C22—C23	−161.36 (13)
Si1—O2—C9—C10	80.09 (15)	Si1—O5—C23—C24	46.9 (2)
Si1—O2—C9—C8	−101.24 (13)	Si1—O5—C23—C22	−136.98 (12)
C13—C8—C9—O2	−173.94 (12)	C27—C22—C23—O5	−176.78 (13)
N1—C8—C9—O2	7.26 (17)	N2—C22—C23—O5	4.42 (18)
C13—C8—C9—C10	4.75 (19)	C27—C22—C23—C24	−0.6 (2)
N1—C8—C9—C10	−174.05 (12)	N2—C22—C23—C24	−179.39 (13)
O2—C9—C10—C11	176.85 (13)	O5—C23—C24—C25	176.11 (14)
C8—C9—C10—C11	−1.8 (2)	C22—C23—C24—C25	0.1 (2)
C9—C10—C11—C12	−1.7 (2)	C23—C24—C25—C26	0.2 (2)
C10—C11—C12—C13	2.2 (2)	C24—C25—C26—C27	−0.1 (2)
C11—C12—C13—C8	0.8 (2)	C25—C26—C27—C22	−0.4 (2)
C9—C8—C13—C12	−4.2 (2)	C23—C22—C27—C26	0.8 (2)
N1—C8—C13—C12	174.47 (12)	N2—C22—C27—C26	179.43 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H3···N1	0.89 (2)	1.77 (2)	2.600 (2)	153 (2)
O4—H17···N2	0.93 (2)	1.68 (2)	2.540 (2)	152 (2)

(III) [2-(3-methoxy-2-oxidobenzylideneamino)phenolato- κ³O,N,O']dimethylsilicon

Crystal data

C16H17NO3Si	F(000) = 632
Mr = 299.40	Dx = 1.330 Mg m^−3
Monoclinic, P21/c	Melting point: 419 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.0207 (3) Å	Cell parameters from 7351 reflections
b = 12.8134 (5) Å	θ = 2.3–35.7°
c = 12.9427 (5) Å	µ = 0.17 mm^−1
β = 91.303 (2)°	T = 153 K
V = 1495.61 (10) Å^3	Cube, orange
Z = 4	0.40 × 0.34 × 0.32 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3975 independent reflections
Radiation source: sealed tube	3463 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
phi and ω scans	θmax = 29.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick 1996)	h = −12→12
Tmin = 0.932, Tmax = 0.950	k = −17→17
17497 measured reflections	l = −17→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0611P)^2 + 0.5981P] where P = (Fo^2 + 2Fc^2)/3
3975 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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
Si1	0.64343 (4)	0.79634 (3)	0.14766 (2)	0.01718 (10)
O1	0.67900 (10)	0.92436 (7)	0.11941 (6)	0.01935 (19)
O2	0.49030 (10)	0.72605 (7)	0.18738 (7)	0.0220 (2)
N1	0.51860 (11)	0.79782 (8)	0.01170 (8)	0.0174 (2)
C1	0.53489 (13)	0.85781 (10)	−0.06723 (9)	0.0182 (2)
H1	0.4762 (18)	0.8479 (13)	−0.1279 (13)	0.023 (4)*
C2	0.64141 (13)	0.94176 (9)	−0.06502 (9)	0.0176 (2)
C3	0.70831 (13)	0.97075 (9)	0.02932 (9)	0.0171 (2)
C4	0.80827 (13)	1.05568 (10)	0.03205 (10)	0.0198 (2)
C5	0.84307 (14)	1.10653 (11)	−0.05865 (11)	0.0237 (3)
H5	0.9131	1.1619	−0.0571	0.028*
C6	0.77565 (15)	1.07685 (11)	−0.15251 (10)	0.0252 (3)
H6	0.8000	1.1124	−0.2142	0.030*
C7	0.67431 (14)	0.99650 (10)	−0.15618 (10)	0.0218 (2)
H7	0.6268	0.9780	−0.2198	0.026*
C8	0.41379 (13)	0.71671 (9)	0.01407 (10)	0.0186 (2)
C9	0.40041 (13)	0.68027 (10)	0.11521 (10)	0.0202 (2)
C10	0.29886 (15)	0.60240 (11)	0.13756 (11)	0.0266 (3)
H10	0.2880	0.5780	0.2063	0.032*
C11	0.21344 (17)	0.56113 (12)	0.05649 (12)	0.0305 (3)
H11	0.1427	0.5084	0.0705	0.037*
C12	0.22946 (16)	0.59548 (11)	−0.04458 (11)	0.0293 (3)
H12	0.1713	0.5650	−0.0987	0.035*
C13	0.32988 (15)	0.67404 (11)	−0.06695 (10)	0.0239 (3)
H13	0.3410	0.6980	−0.1358	0.029*
O3	0.86130 (11)	1.08060 (8)	0.12815 (7)	0.0263 (2)
C14	0.97863 (15)	1.15522 (12)	0.13530 (12)	0.0288 (3)
H14A	1.0632	1.1304	0.0959	0.043*
H14B	1.0090	1.1644	0.2079	0.043*
H14C	0.9442	1.2221	0.1070	0.043*
C15	0.78151 (15)	0.70660 (11)	0.08845 (11)	0.0270 (3)
H15A	0.8122	0.7352	0.0220	0.040*
H15B	0.7363	0.6378	0.0774	0.040*
H15C	0.8683	0.6998	0.1349	0.040*
C16	0.70998 (15)	0.81718 (11)	0.28499 (10)	0.0249 (3)
H16A	0.8058	0.8532	0.2853	0.037*
H16B	0.7211	0.7495	0.3196	0.037*
H16C	0.6377	0.8597	0.3215	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.02031 (17)	0.01753 (17)	0.01364 (17)	−0.00043 (11)	−0.00075 (12)	0.00124 (11)
O1	0.0259 (4)	0.0185 (4)	0.0136 (4)	−0.0030 (3)	−0.0006 (3)	0.0013 (3)
O2	0.0253 (4)	0.0257 (5)	0.0150 (4)	−0.0065 (4)	−0.0014 (3)	0.0011 (3)
N1	0.0188 (4)	0.0166 (5)	0.0167 (5)	−0.0003 (3)	−0.0003 (4)	−0.0007 (4)
C1	0.0202 (5)	0.0189 (6)	0.0156 (5)	0.0018 (4)	−0.0001 (4)	−0.0010 (4)
C2	0.0199 (5)	0.0170 (5)	0.0159 (5)	0.0020 (4)	0.0009 (4)	0.0010 (4)
C3	0.0189 (5)	0.0167 (5)	0.0157 (5)	0.0023 (4)	0.0019 (4)	0.0016 (4)
C4	0.0198 (5)	0.0203 (6)	0.0192 (6)	0.0003 (4)	0.0006 (4)	−0.0015 (4)
C5	0.0242 (6)	0.0216 (6)	0.0253 (6)	−0.0038 (5)	0.0030 (5)	0.0027 (5)
C6	0.0303 (6)	0.0254 (7)	0.0201 (6)	−0.0017 (5)	0.0037 (5)	0.0058 (5)
C7	0.0257 (6)	0.0235 (6)	0.0164 (5)	0.0008 (5)	0.0007 (4)	0.0027 (5)
C8	0.0213 (5)	0.0163 (5)	0.0182 (6)	−0.0013 (4)	−0.0003 (4)	−0.0004 (4)
C9	0.0226 (5)	0.0195 (6)	0.0183 (6)	−0.0013 (4)	−0.0005 (4)	−0.0005 (4)
C10	0.0310 (6)	0.0264 (7)	0.0225 (6)	−0.0072 (5)	0.0010 (5)	0.0041 (5)
C11	0.0338 (7)	0.0268 (7)	0.0308 (7)	−0.0119 (5)	−0.0028 (6)	0.0037 (6)
C12	0.0347 (7)	0.0259 (7)	0.0268 (7)	−0.0088 (5)	−0.0075 (6)	−0.0009 (5)
C13	0.0299 (6)	0.0226 (6)	0.0189 (6)	−0.0032 (5)	−0.0038 (5)	0.0001 (5)
O3	0.0289 (5)	0.0298 (5)	0.0200 (5)	−0.0110 (4)	−0.0012 (4)	−0.0026 (4)
C14	0.0254 (6)	0.0282 (7)	0.0327 (7)	−0.0073 (5)	−0.0036 (5)	−0.0023 (6)
C15	0.0273 (6)	0.0272 (7)	0.0265 (7)	0.0059 (5)	0.0005 (5)	0.0000 (5)
C16	0.0317 (6)	0.0263 (6)	0.0165 (6)	−0.0054 (5)	−0.0040 (5)	0.0027 (5)

Geometric parameters (Å, º)

Si1—O1	1.7125 (9)	C8—C13	1.3912 (17)
Si1—O2	1.7367 (9)	C8—C9	1.3975 (17)
Si1—C15	1.872 (1)	C9—C10	1.3895 (18)
Si1—C16	1.882 (1)	C10—C11	1.3919 (19)
Si1—N1	2.068 (1)	C10—H10	0.9500
O1—C3	1.3405 (14)	C11—C12	1.391 (2)
O2—C9	1.3564 (15)	C11—H11	0.9500
N1—C1	1.2895 (16)	C12—C13	1.3891 (19)
N1—C8	1.4058 (15)	C12—H12	0.9500
C1—C2	1.4423 (17)	C13—H13	0.9500
C1—H1	0.946 (17)	O3—C14	1.4278 (15)
C2—C3	1.3998 (16)	C14—H14A	0.9800
C2—C7	1.4100 (16)	C14—H14B	0.9800
C3—C4	1.4132 (17)	C14—H14C	0.9800
C4—O3	1.3604 (15)	C15—H15A	0.9800
C4—C5	1.3849 (18)	C15—H15B	0.9800
C5—C6	1.3988 (19)	C15—H15C	0.9800
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.3769 (18)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800
C7—H7	0.9500
O1—Si1—O2	135.57 (5)	C13—C8—N1	128.96 (11)
O1—Si1—C15	111.80 (6)	C9—C8—N1	109.87 (10)
O2—Si1—C15	110.10 (6)	O2—C9—C10	123.63 (11)
O1—Si1—C16	90.48 (5)	O2—C9—C8	115.95 (11)
O2—Si1—C16	91.88 (5)	C10—C9—C8	120.42 (11)
C15—Si1—C16	105.83 (7)	C9—C10—C11	118.17 (12)
O1—Si1—N1	84.87 (4)	C9—C10—H10	120.9
O2—Si1—N1	80.52 (4)	C11—C10—H10	120.9
C15—Si1—N1	90.68 (5)	C12—C11—C10	121.42 (13)
C16—Si1—N1	163.39 (6)	C12—C11—H11	119.3
C3—O1—Si1	130.70 (8)	C10—C11—H11	119.3
C9—O2—Si1	119.18 (8)	C13—C12—C11	120.50 (12)
C1—N1—C8	123.15 (10)	C13—C12—H12	119.7
C1—N1—Si1	127.59 (8)	C11—C12—H12	119.7
C8—N1—Si1	109.16 (8)	C12—C13—C8	118.29 (12)
N1—C1—C2	121.12 (11)	C12—C13—H13	120.9
N1—C1—H1	120.4 (10)	C8—C13—H13	120.9
C2—C1—H1	118.5 (10)	C4—O3—C14	117.46 (11)
C3—C2—C7	120.21 (11)	O3—C14—H14A	109.5
C3—C2—C1	119.28 (11)	O3—C14—H14B	109.5
C7—C2—C1	120.48 (11)	H14A—C14—H14B	109.5
O1—C3—C2	123.47 (11)	O3—C14—H14C	109.5
O1—C3—C4	117.26 (10)	H14A—C14—H14C	109.5
C2—C3—C4	119.23 (11)	H14B—C14—H14C	109.5
O3—C4—C5	125.65 (11)	Si1—C15—H15A	109.5
O3—C4—C3	114.49 (11)	Si1—C15—H15B	109.5
C5—C4—C3	119.86 (11)	H15A—C15—H15B	109.5
C4—C5—C6	120.39 (12)	Si1—C15—H15C	109.5
C4—C5—H5	119.8	H15A—C15—H15C	109.5
C6—C5—H5	119.8	H15B—C15—H15C	109.5
C7—C6—C5	120.56 (12)	Si1—C16—H16A	109.5
C7—C6—H6	119.7	Si1—C16—H16B	109.5
C5—C6—H6	119.7	H16A—C16—H16B	109.5
C6—C7—C2	119.69 (12)	Si1—C16—H16C	109.5
C6—C7—H7	120.2	H16A—C16—H16C	109.5
C2—C7—H7	120.2	H16B—C16—H16C	109.5
C13—C8—C9	121.17 (11)
O2—Si1—O1—C3	−111.65 (11)	O1—C3—C4—C5	179.85 (11)
C15—Si1—O1—C3	47.89 (12)	C2—C3—C4—C5	−2.42 (18)
C16—Si1—O1—C3	155.18 (11)	O3—C4—C5—C6	−176.84 (12)
N1—Si1—O1—C3	−40.79 (10)	C3—C4—C5—C6	2.39 (19)
O1—Si1—O2—C9	92.91 (10)	C4—C5—C6—C7	−0.3 (2)
C15—Si1—O2—C9	−66.87 (11)	C5—C6—C7—C2	−1.8 (2)
C16—Si1—O2—C9	−174.48 (10)	C3—C2—C7—C6	1.75 (18)
N1—Si1—O2—C9	20.36 (9)	C1—C2—C7—C6	179.61 (12)
O1—Si1—N1—C1	25.75 (11)	C1—N1—C8—C13	12.0 (2)
O2—Si1—N1—C1	163.65 (11)	Si1—N1—C8—C13	−164.56 (11)
C15—Si1—N1—C1	−86.08 (11)	C1—N1—C8—C9	−167.62 (11)
C16—Si1—N1—C1	100.0 (2)	Si1—N1—C8—C9	15.80 (12)
O1—Si1—N1—C8	−157.87 (8)	Si1—O2—C9—C10	163.41 (11)
O2—Si1—N1—C8	−19.97 (8)	Si1—O2—C9—C8	−17.18 (15)
C15—Si1—N1—C8	90.31 (9)	C13—C8—C9—O2	178.48 (11)
C16—Si1—N1—C8	−83.6 (2)	N1—C8—C9—O2	−1.85 (15)
C8—N1—C1—C2	178.38 (11)	C13—C8—C9—C10	−2.1 (2)
Si1—N1—C1—C2	−5.70 (17)	N1—C8—C9—C10	177.58 (12)
N1—C1—C2—C3	−11.82 (18)	O2—C9—C10—C11	−179.62 (13)
N1—C1—C2—C7	170.30 (11)	C8—C9—C10—C11	1.0 (2)
Si1—O1—C3—C2	36.77 (17)	C9—C10—C11—C12	0.7 (2)
Si1—O1—C3—C4	−145.61 (9)	C10—C11—C12—C13	−1.3 (2)
C7—C2—C3—O1	177.94 (11)	C11—C12—C13—C8	0.3 (2)
C1—C2—C3—O1	0.05 (18)	C9—C8—C13—C12	1.4 (2)
C7—C2—C3—C4	0.36 (17)	N1—C8—C13—C12	−178.18 (13)
C1—C2—C3—C4	−177.53 (11)	C5—C4—O3—C14	−9.63 (19)
O1—C3—C4—O3	−0.83 (16)	C3—C4—O3—C14	171.10 (11)
C2—C3—C4—O3	176.90 (11)