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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 3| March 2011| Pages o100-o103
doi:10.1107/S0108270110053357

Optically active di­aryl tetra­hydro­iso­quinoline derivatives

CROSSMARK_Color_square_no_text.svg
Tricia Naicker,a Thavendran Govender,a Hendrik G. Krugerb and Glenn E. M. Maguireb*

aSchool of Pharmacy and Pharmacology, University of KwaZulu Natal, Durban 4000, South Africa, and bSchool of Chemistry, University of KwaZulu Natal, Durban 4000, South Africa
*Correspondence e-mail: maguireg@ukzn.ac.za

(Received 23 October 2010; accepted 20 December 2010; online 8 February 2011)

In (1R,3S)-6,7-dimeth­oxy-3-(meth­oxy­diphenyl­methyl)-1-phenyl-1,2,3,4-tetra­hydro­isoquinoline, C31H31NO3, (I)[link], and (1R,3S)-2-benzyl-3-[diphenyl(trimethyl­siloxy)methyl]-6,7-dimeth­oxy-1-phenyl-1,2,3,4-tetra­hydro­isoquinoline, C40H43NO3Si, (II)[link], the absolute configurations have been confirmed to be R and S at the isoquinoline 1- and 3-positions, respectively, by NMR spectroscopy experiments. Both structures have monoclinic (P21) symmetry and the N-containing six-membered ring assumes a half-chair conformation. The asymmetric unit of (I)[link] contains one mol­ecule, while (II)[link] has two mol­ecules within the asymmetric unit. These structures are of inter­est with respect to the conformation around the exocyclic C—C bond: (I)[link] displays an ap (anti­periplanar) conformation, while (II)[link] displays an sc-exo (synclinal) conformation around this bond. These conformations are significant for stereocontrol when these compounds are used as catalysts. Various C—H⋯π and C—H⋯O bonds link the mol­ecules together in the crystal structure of (I)[link]. In the crystal structure of (II)[link], three inter­molecular C—H⋯π hydrogen bonds help to establish the packing.

Comment

The tetra­hydro­isoquinoline (TIQ) mol­ecule and its derivatives have been widely investigated due to their biological and pharmaceutical properties. Given our recent success with TIQ-based ligands for catalytic asymmetric transfer hydrogenation of prochiral ketones, Henry reactions and hydrogenation of olefins (Peters et al., 2010[Peters, B. K., Chakka, S. K., Naicker, T., Maguire, G. E. M., Kruger, H. G., Andersson, P. G. & Govender, T. (2010). Tetrahedron Asymmetry, 21, 679-687.]). We decided to investigate the potential of TIQ derivatives as organocatalysts. Compound (I)[link] has recently been synthesized and evaluated as a novel iminium-activated organocatalyst in an asymmetric Diels–Alder reaction (Naicker, Petzold et al., 2010[Naicker, T., Petzold, K., Singh, T., Arvidsson, P. I., Kruger, H. G., Maguire, G. E. M. & Govender, T. (2010). Tetrahedron Asymmetry, 21, 2859-2867.]). Com­pound (II)[link] is novel and is the precursor to the same class of organocatalysts based on a (1R,3S)-6,7-dimeth­oxy-1-phenyl-1,2,3,4-tetra­hydro­isoquinoline backbone.

Derived from commercially available L-DOPA, the absolute stereochemistry of (I)[link] and (II)[link] was confirmed to be R and S at the C1 and C9 positions by 1H NMR, as shown in Figs. 1[link] and 2[link], respectively.

[Scheme 1]

Both structures have monoclinic (P21) symmetry. Com­pound (I)[link] has a single mol­ecule in the asymmetric unit, while (II)[link] has two mol­ecules within the asymmetric unit. Mol­ecule (I)[link] has a methyl group at the O3 position, whilst (II)[link] has a trimethyl­silyl group in this position. In addition, (II)[link] has a benzyl group on the N atom.

In the structure of (I)[link], inter­molecular C—H⋯π and C—H⋯O inter­actions involving atoms O1 and O2 link the mol­ecules into extended chains which run parallel to the b axis (Table 1[link] and Fig. 3[link]). In the chain, the mol­ecules are arranged so that their tails, linked by the C—H⋯O inter­actions, point towards the core of the chain and their heads protrude to the outer edges of the chain, with adjacent mol­ecules alternating from side-to-side. The C—H⋯π inter­actions link the heads of those mol­ecules lying on the same side of the chain core.

In the structure of (II)[link], each independent mol­ecule displays an intra­molecular C—H⋯π inter­action, while a single inter­molecular C—H⋯π inter­action involving C35A—H links just the two independent mol­ecules (Table 2[link]). An extended network of inter­actions is not present. The crystal packing of (II)[link] reveals that the pseudosymmetry relates the two independent mol­ecules within the asymmetric unit resulting in a layered packing along the a axis (Fig. 4[link]).

From the crystal structures, it is evident that the N-containing six-membered rings assume half-chair conformations (Figs. 1[link] and 2[link]). This result differs from two analogous compounds, namely (1R,3S)-methyl 2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate and (1R,3S)-methyl 6,7-dimethoxy-1-(4-methoxyphenyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxylate, which assume half-boat conformations (Naicker et al., 2009[Naicker, T., McKay, M., Govender, T., Kruger, H. G. & Maguire, G. E. M. (2009). Acta Cryst. E65, o3278.]; Naicker, Govender et al., 2010a[Naicker, T., Govender, T., Kruger, H. G. & Maguire, G. E. M. (2010a). Acta Cryst. E66, o3105.]). The current study confirms our previous postulation that the change in conformation is a result of the introduction of the phenyl groups at the C1 position.

According to the Cambridge Structural Database (Version 5.31; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]), the only other crystal structure of a tetra­hydro­isoquinoline derivative with diaryl substitution at the C10 position is compound (III)[link] (see Scheme[link]), which we reported recently (Naicker, Govender et al., 2010b[Naicker, T., Govender, T., Kruger, H. G. & Maguire, G. E. M. (2010b). Acta Cryst. E66, o638.]). In this crystal structure, the methanol O atom is a free OH group. Due to the lack of analogous structures, these diaryl tetra­hydro­isoquinoline alcohols were compared with proline diaryl alcohols (Seebach et al., 2008[Seebach, D., Groselj, U., Badine, D. M., Schweizer, W. B. & Beck, A. K. (2008). Helv. Chim. Acta, 91, 1999-2034.]). Compound (III)[link] displays a similar conformation to its proline analogue, which displays a gauche or sc-endo (synclinal) conformation around the O3—C10—C9—N1 bond, with the OH group partially covering the piperidine ring with a torsion angle of −77.0 (2)°.

Compound (I)[link] displays an ap (anti­periplanar) conformation around the exocyclic C9—C10 bond, with an O3—C10—C9—N1 torsion angle of 171.5 (1)°. This conformation has only been found in a few examples of N-amino prolinol methyl esters (Seebach et al., 2008[Seebach, D., Groselj, U., Badine, D. M., Schweizer, W. B. & Beck, A. K. (2008). Helv. Chim. Acta, 91, 1999-2034.]).

Proline diphenyl OTMS (OTMS is trimethylsiloxy) analogues exhibit an sc-exo conformation around the exocyclic ethane bond, with a torsion angle of 61.0°. Both mol­ecules of (II)[link] (Fig. 2[link]) display an sc-endo conformation, with torsion angles of −81.1 (3) and −84.8 (2)°. A possible reason for this change could be that the benzyl group on the N atom forces the phenyl rings at the C10 atom to be the furthest away from it, hence adopting the sc-endo conformation.

Proline diaryl alcohols have been used as successful chiral catalysts by exploiting the same rotation along the C9—C10 bond (Diner et al., 2008[Diner, P., Kjaersgaard, A., Lie, M. A. & Jorgensen, K. A. (2008). Chem. Eur. J. 14, 122-127.]). This change, which is brought about by different groups on the methanol O atom, makes the current study particularly useful. This feature is found in (I)[link] which, when tested for its catalytic activity in the Diels–Alder reaction, showed poor yields. The structural data demonstrated how we could improve the catalytic reactivity by reducing the steric bulk of the ligand. A successful catalyst was obtained by removing the phenyl moieties from (I)[link] (Naicker, Petzold et al., 2010[Naicker, T., Petzold, K., Singh, T., Arvidsson, P. I., Kruger, H. G., Maguire, G. E. M. & Govender, T. (2010). Tetrahedron Asymmetry, 21, 2859-2867.]).

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], showing the atom-numbering scheme. There are two mol­ecules in the asymmetric unit, labelled with suffixes A and B. Displacement ellipsoids are drawn at the 50% probability level. H atoms and some atom labels have been omitted for clarity.
[Figure 3]
Figure 3
A partial projection of the structure of (I)[link], viewed along [010]. Dashed lines indicate intermolecular interactions. H atoms not involved in intermolecular interactions have been omitted for clarity.
[Figure 4]
Figure 4
A partial projection of the structure of (II)[link], viewed along [100]. The top and bottom layers contain only B mol­ecules, while the central layer contains A mol­ecules. Dashed lines indicate intermolecular interactions. H atoms not involved in intermolecular interactions have been omitted for clarity.

Experimental

To (1R,3S)-2-benzyl-3-(1,1-diphenyl­ethyl)-6,7-dimeth­oxy-1-phenyl-1,2,3,4-tetra­hydro­isoquinoline (0.4 g, 0.72 mmol), derived from L-DOPA (Naicker, Petzold et al., 2010[Naicker, T., Petzold, K., Singh, T., Arvidsson, P. I., Kruger, H. G., Maguire, G. E. M. & Govender, T. (2010). Tetrahedron Asymmetry, 21, 2859-2867.]), in MeOH–THF (1:1 v/v, 20 ml) was added half an equivalent by mass of 10% palladium on carbon Pd/C under hydrogen (approximately 1 atm). The reaction was stirred for 2 h. The crude product was obtained by filtering the Pd/C through a plug of Celite and the filtrate was then concentrated to dryness. The resulting residue was purified by column chromatography (50:50 EtOAc–hexane, RF = 0.6) to yield (I)[link] as a white solid [yield 0.2 g, 60%; m.p. 463–465 K; [α]20D −10.0 (c 0.11 in CHCl3)]. Recrystallization from ethyl acetate afforded colourless crystals suitable for X-ray analysis. IR (neat, νmax, cm−1): 2934, 1514, 1448, 1244, 1224, 1063, 698; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.47–7.12 (m, 12H), 7.08 (t, J = 7.6 Hz, 2H), 6.92 (d, J = 7.6 Hz, 2H), 6.65 (s, 1H), 6.40 (s, 1H), 5.23 (s, 1H), 3.95 (dd, J = 11.5 and 3.6 Hz, 1H), 3.86 (s, 3H), 3.70 (s, 3H), 2.92–2.75 (m, 4H), 2.52 (dd, J = 16.2 and 11.5 Hz, 3H).

To a stirred solution of [(1R,3S)-3-(hy­droxy­diphenyl­methyl)-6,7-dimeth­oxy-1-phenyl-1,2,3,4-tetra­hydro­isoquinolin-2-yl](phenyl)methanone (0.6 g, 1.1 mmol), derived from L-DOPA (Naicker, Petzold et al., 2010[Naicker, T., Petzold, K., Singh, T., Arvidsson, P. I., Kruger, H. G., Maguire, G. E. M. & Govender, T. (2010). Tetrahedron Asymmetry, 21, 2859-2867.]), in dry dichloro­methane (20 ml) and triethyl­amine (0.18 ml, 1.3 mmol), trimethyl­silyl trifluoro­methane­sulfonate (0.24 ml, 1.33 mmol) was added dropwise at 273 K under an inert atmosphere. The mixture was allowed to warm to room temperature and was stirred overnight. The mixture was washed with water, the organic extracts were combined and dried over anhydrous Na2SO4, and the solvent was removed in vacuo. The resulting residue was purified by column chromatography (20:80 EtOAc–hexane, RF = 0.55) to afford (II)[link] as a white solid [yield 0.5 g, 75%; m.p. 458–460 K; [α]20D 57.58 (c 0.33 in CHCl3)]. Recrystallization from acetone afforded colourless crystals suitable for X-ray analysis. IR (neat, νmax, cm−1): 2956, 1513, 1245, 839, 696; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.17 (m, 14H), 6.84 (m, 5H), 6.63 (m, 2H), 6.36 (s, 1H), 4.57 (s, 1H), 4.38 (d, J = 13.63 Hz, 1H), 4.24 (dd, J = 3.38 and 12.13 Hz, 1H), 4.00 (s, 3H), 3.73 (s, 3H), 3.39 (dd, J = 4.32 and 12.58 Hz, 1H), 3.31 (d, J = 13.85 Hz, 1H), 2.29 (dd, J = 3.38 and 16.88 Hz, 1H), 0.0 (s, 9H).

Compound (I)[link]

Crystal data

  • C31H31NO3

  • Mr = 465.57

  • Monoclinic, P 21

  • a = 11.4071 (14) Å

  • b = 6.4750 (8) Å

  • c = 16.961 (2) Å

  • β = 101.707 (2)°

  • V = 1226.7 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 173 K

  • 0.22 × 0.14 × 0.09 mm
Data collection

  • Bruker APEXII DUO diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) Tmin = 0.645, Tmax = 0.746

  • 11498 measured reflections

  • 3737 independent reflections

  • 3191 reflections with I > 2σ(I)

  • Rint = 0.051
Refinement

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.108

  • S = 1.05

  • 3737 reflections

  • 320 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

Cg is the centroid of the C18–C23 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C11—H11A⋯Cgi 0.98 2.57 3.45 (2) 150
C30—H30A⋯O1ii 0.98 2.54 3.356 (2) 140
C30—H30A⋯O2ii 0.98 2.59 3.400 (2) 140
Symmetry codes: (i) x, y+1, z; (ii) [-x, y-{\script{1\over 2}}, -z+1].

Compound (II)[link]

Crystal data

  • C40H43NO3Si

  • Mr = 613.84

  • Monoclinic, P 21

  • a = 11.045 (10) Å

  • b = 17.008 (15) Å

  • c = 18.489 (15) Å

  • β = 105.287 (15)°

  • V = 3350 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 100 K

  • 0.22 × 0.12 × 0.10 mm
Data collection

  • Bruker APEXII DUO diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) Tmin = 0.976, Tmax = 0.989

  • 37993 measured reflections

  • 17263 independent reflections

  • 11255 reflections with I > 2σ(I)

  • Rint = 0.064
Refinement

  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.124

  • S = 0.99

  • 17263 reflections

  • 812 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.41 e Å−3

  • Absolute structure: Flack (1983)

  • Flack parameter: 0.00 (10), 8119 Friedel pairs

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

Cg1, Cg2, Cg3 and the centroids of the C26B–C31B, C32A–C37A and C32B–C37B rings, respectively.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C35A—H35A⋯Cg1i 0.95 2.80 3.669 (3) 152
C40A—H40A⋯Cg2 0.98 2.71 3.540 (3) 143
C40B—H40D⋯Cg3 0.98 2.64 3.449 (4) 140
Symmetry code: (i) x+1, y, z+1.

Atom H1N on N1 of (I)[link] was located in a difference electron-density map and refined isotropically with a simple bond-length restraint of N1—H1N = 0.96 (1) Å. All remaining H atoms were positioned geometrically, with C—H = 0.95 (aromatic), 0.98 (methyl), 0.99 (methyl­ene) or 1.00 Å (methine), and refined as riding on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. For (I)[link], the Flack x parameter (Flack, 1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) based on refinement with 3080 Friedel pairs was −0.5 (10), which indicated that no conclusions can be drawn regarding the absolute structure. Consequently, the Friedel pairs were merged before the final refinement. For (II)[link], the Flack parameter refined to 0.00 (10) using 8119 Friedel pairs, which indicated that the refined model represents the true absolute configuration and is in accordance with expecta­tion from the known chirality of the starting material in the synthesis.

For both compounds, data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2006[Bruker (2006). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S0108270110053357/sf3143sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270110053357/sf3143Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270110053357/sf3143IIsup3.hkl


Comment top

The tetrahydroisoquinoline (TIQ) molecule and its derivatives have been widely investigated, due to their biological and pharmaceutical properties. Given our recent success with TIQ-based ligands for catalytic asymmetric transfer hydrogenation of prochiral ketones, Henry reactions and hydrogenation of olefins, we decided to investigate the potential of TIQ derivatives as organocatalysts (Peters et al. 2010). Compound (I) has recently been synthesized and evaluated as a novel iminium activated organocatalyst in an asymmetric Diels–Alder reaction (Naicker, Petzold et al., 2010). Compound (II) is novel and is the precursor to the same class of organocatalysts based on a (1R,3S)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline backbone.

Derived from commercially available L-DOPA, the absolute stereochemistry of (I) and (II) was confirmed to be R,S at the C1 and C9 positions by 1H NMR, as shown in Figs. 1 and 2, respectively.

Both structures have monoclinic (P21) symmetry. Compound (I) has a single molecule in the asymmetric unit, while (II) has two molecules within the asymmetric unit. Molecule (I) has a methyl group at the O3 position, whilst (II) has a trimethylsilyl group in this position. In addition, (II) has a benzyl group on the N atom.

In the structure of (I), intermolecular C—H···π and C—H···O interactions involving atoms O1 and O2 link the molecules into extended chains which run parallel to the b axis (Table 1 and Fig. 3). In the chain, the molecules are arranged so that their tails, linked by the C—H···O interactions, point towards the core of the chain and their heads protrude to the outer edges of the chain, with adjacent molecules alternating from side-to-side. The C—H···π interactions link the heads of those molecules lying on the same side of the chain core.

In the structure of (I), intermolecular C—H···π and C—H···O bonds involving atoms O1 and O2 link the molecules together, as illustrated in Fig. 3 (see Table 1).

In the structure of (II), each independent molecule displays an intramolecular C—H···π interaction, while a single intermolecular C—H···π interaction involving C30A—H links just the two independent molecules (Table 2). An extended network of interactions is not present. The crystal packing of (II) reveals that the pseudosymmetry relates the two independent molecules within the asymmetric unit resulting in a layered packing along the a axis (Fig 4).

Intermolecular C—H···π bonds link the molecules in the crystal structure of (II) (see Table 2), as shown in Fig. 4.

From the crystal structures, it is evident that the N-containing six-membered rings assume half-chair conformations (Figs. 1 and 2). This result differs from two analogous compounds which assume a half-boat conformation (Naicker et al., 2009; Naicker, Govender et al., 2010a). The current study confirms our previous postulation that the change in conformation is a result of the introduction of the phenyl groups at the C1 position.

According to the Cambridge Structural Database (Version?; Allen, 2002), the only other crystal structure of a tetrahydroisoquinoline derivative with diaryl substitution at the C10 position is compound (III) (see scheme), which we reported recently (Naicker, Govender et al., 2010b). In this crystal structure, the methanol O atom is a free OH. Due to the lack of analogous structures, these diaryl tetrahydroisoquinoline alcohols were compared with proline diaryl alcohols (Seebach et al., 2008). Compound (III) displayed a similar conformation to its proline analogue, which displays a gauche or sc-endo (synclinal) conformation around the O3—C10—C9—N1 bond, with the OH group partially covering the piperidine ring with a torsion angle of -77.0 (2)°.

Compound (I) displays an ap (antiperiplanar) conformation around the exocyclic C9—C10 bond, with an O3—C10—C9—N1 torsion angle of 171.5 (1)°. This conformation has only been found in a few examples of N-amino prolinol methyl esters (Seebach et al., 2008).

Proline diphenyl OTMS (Define OTMS?) analogues exhibit an sc-exo conformation around the exocyclic ethane bond, with a torsion angle of 61.0°. Both molecules of (II) (Fig. 2) display an sc-endo conformation, with torsion angles of -81.1 (3) and -84.8 (2)°. A possible reason for this change could be that the benzyl group on the N atom forces the phenyl rings at the C10 atom to be the furthest away from it, hence adopting the sc-endo conformation.

Proline diaryl alcohols have been used as successful chiral catalysts by exploiting the same rotation along the C9—C10 bond (Diner et al., 2008). This change, which is brought about by different groups on the methanol oxygen, makes the current study particularly useful. This feature is found in (I) which, when tested for its catalytic activity in the Diels–Alder reaction, showed poor yields. The structural data demonstrated how we could improve the catalytic reactivity by reducing the steric bulk of the ligand. A successful catalyst was obtained by removing the phenyl moieties from (I) (Naicker, Petzold et al., 2010).

Related literature top

For related literature, see: Allen (2002); Diner et al. (2008); Flack (1983); Naicker et al. (2009, 2010, 2010a, 2010b); Peters et al. (2010); Seebach et al. (2008).

Experimental top

To (1R,3S)-2-benzyl-3-(1,1-diphenylethyl)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline (0.4 g, 0.72 mmol) derived from L-DOPA (Naicker, Petzold et al., 2010) in MeOH–THF (1:1 v/v, 20 ml) was added half an equivalent by mass of 10% palladium on carbon Pd/C under hydrogen (approximately 1 atm). The reaction was stirred for 2 h. The crude product was obtained by filtering the Pd/C through a plug of Celite and the filtrate was then concentrated to dryness. The resulting residue was purified by column chromatography (50:50 EtOAc–hexane, Rf = 0.6) to yield (I) as a white solid [yield 0.2 g, 60%; m.p. 463–465 K; [α]20D -10.0 (c 0.11 in CHCl3)]. Recrystallization from ethyl acetate afforded colourless crystals suitable for X-ray analysis. Spectroscopic analysis: IR (neat, νmax, cm-1): 2934, 1514, 1448, 1244, 1224, 1063, 698; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.47–7.12 (m, 12H), 7.08 (t, J = 7.6 Hz, 2H), 6.92 (d, J = 7.6 Hz, 2H), 6.65 (s, 1H), 6.40 (s, 1H), 5.23 (s, 1H), 3.95 (dd, J = 11.5 and 3.6 Hz, 1H), 3.86 (s, 3H), 3.70 (s, 3H), 2.92–2.75 (m, 4H), 2.52 (dd, J = 16.2 and 11.5 Hz, 3H).

To a stirred solution of [(1R,3S)-3-(hydroxydiphenylmethyl)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinolin-2-yl](phenyl)methanone (0.6 g, 1.1 mmol) derived from L-DOPA (Naicker, Petzold et al., 2010) in dry dichloromethane (20 ml) and triethylamine (0.18 ml, 1.3 mmol), trimethylsilyl trifluoromethanesulfonate (0.24 ml, 1.33 mmol) was added dropwise at 273 K under an inert atmosphere. The mixture was allowed to warm to room temperature and stirred overnight. The mixture was washed with water, the organic extracts were combined and dried over anhydrous Na2SO4, and the solvent was removed in vacuo. The resulting residue was purified by column chromatography (20:80 EtOAc–hexane, Rf 0.55) to afford (II) as a white solid [yield 0.5 g, 75%; m.p. 458–460 K; [α]20D 57.58 (c 0.33 in CHCl3)]. Recrystallization from acetone afforded colourless crystals suitable for X-ray analysis. Spectroscopic analysis: IR (neat, νmax, cm-1): 2956, 1513, 1245, 839, 696; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.17 (m, 14H), 6.84 (m, 5H), 6.63 (m, 2H), 6.36 (s, 1H), 4.57 (s, 1H), 4.38 (d, J = 13.63 Hz, 1H), 4.24 (dd, J = 3.38 and 12.13 Hz, 1H), 4.00 (s, 3H), 3.73 (s, 3H), 3.39 (dd, J = 4.32 and 12.58 Hz, 1H), 3.31 (d, J = 13.85 Hz, 1H), 2.29 (dd, J = 3.38 and 16.88 Hz, 1H), 0.0 (s, 9H).

Refinement top

Atom H1N on N1 of (I) was located in a difference electron-density map and refined isotropically with a simple bond-length restraint of N1—H1N = 0.??(?) Å. All remaining H atoms were positioned geometrically, with C—H = 0.95 (aromatic), 0.98 (methyl), 0.99 (methylene) or 1.00 Å (methine), and refined as riding on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. For (I), the Flack x parameter (Flack, 1983) based on refinement with xxxx Friedel pairs was -0.5 (10), which indicated that no conclusions can be drawn regarding the absolute structure. Consequently, the Friedel pairs were merged before the final refinement. For (II), the Flack parameter refined to 0.00 (10) using xxxx Friedel pairs, which indicated that the refined model represents the true absolute configuration and is in accordance with expectation from the known chirality of the starting material in the synthesis.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. There are two molecules in the asymmetric unit, labelled with suffixes A and B. Displacement ellipsoids are drawn at the 50% probability level. H atoms and some atom labels have been omitted for clarity.
[Figure 3] Fig. 3. A partial projection of the structure of (I), viewed along [010]. [Please supply revision with no grey areas around labels]
[Figure 4] Fig. 4. A partial projection of the structure of (II), viewed along [100]. The top and bottom layers contain only B molecules, while the central layer contains A molecules. [Please supply revision with no grey areas around labels]
(I) (1R,3S)-6,7-dimethoxy-3-(methoxydiphenylmethyl)-1-phenyl- 1,2,3,4-tetrahydroisoquinoline top
Crystal data top
C31H31NO3F(000) = 496
Mr = 465.57Dx = 1.260 Mg m−3
Monoclinic, P21Melting point: 464 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 11.4071 (14) ÅCell parameters from 11498 reflections
b = 6.4750 (8) Åθ = 1.8–29.7°
c = 16.961 (2) ŵ = 0.08 mm−1
β = 101.707 (2)°T = 173 K
V = 1226.7 (3) Å3Block, colourless
Z = 20.22 × 0.14 × 0.09 mm
Data collection top
Bruker APEXII DUO
diffractometer		3737 independent reflections
Radiation source: fine-focus sealed tube3191 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
0.5° ϕ scans and ωθmax = 29.7°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		h = −15→13
Tmin = 0.645, Tmax = 0.746k = −8→8
11498 measured reflectionsl = −23→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0591P)2]
where P = (Fo2 + 2Fc2)/3
3737 reflections(Δ/σ)max < 0.001
320 parametersΔρmax = 0.23 e Å−3
2 restraintsΔρmin = −0.23 e Å−3
Crystal data top
C31H31NO3V = 1226.7 (3) Å3
Mr = 465.57Z = 2
Monoclinic, P21Mo Kα radiation
a = 11.4071 (14) ŵ = 0.08 mm−1
b = 6.4750 (8) ÅT = 173 K
c = 16.961 (2) Å0.22 × 0.14 × 0.09 mm
β = 101.707 (2)°
Data collection top
Bruker APEXII DUO
diffractometer		3737 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		3191 reflections with I > 2σ(I)
Tmin = 0.645, Tmax = 0.746Rint = 0.051
11498 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0432 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.23 e Å−3
3737 reflectionsΔρmin = −0.23 e Å−3
320 parameters
Special details top

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of ϕ and ω scans of 0.5°, 20 s per °, 2 iterations.

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.

Refinement. For both crystals, X-ray diffraction data were collected on a Bruker APEXII Duo diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Data collection was carried out at 173 (2) K and 100 (2) K for structures (I) and (II), respectively, to minimize thermal motion effects. Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). Cell refinement and data reduction were performed using the program SAINT (Bruker, 2006). The data were scaled and empirical absorption corrections were performed using SADABS (Bruker, 2006). The structure was solved by direct methods using SHELXS97 (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F2 using SHELXL97 (Sheldrick, 2008). All non-H atoms were refined anisotropically.

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 (Å2) top
xyzUiso*/Ueq
O10.09437 (12)0.2273 (2)0.57983 (9)0.0308 (4)
O20.07975 (12)0.5778 (3)0.65284 (9)0.0290 (3)
O30.73707 (12)0.7122 (2)0.82876 (8)0.0240 (3)
N10.59801 (14)0.2003 (3)0.79457 (9)0.0213 (3)
H1N0.6724 (14)0.127 (4)0.8040 (15)0.039 (7)*
C10.51525 (16)0.1256 (3)0.72126 (11)0.0197 (4)
H10.4934−0.01980.73200.024*
C20.40066 (16)0.2505 (3)0.70663 (11)0.0197 (4)
C30.30026 (16)0.1747 (3)0.65138 (11)0.0223 (4)
H30.30510.04500.62600.027*
C40.19499 (17)0.2868 (3)0.63373 (11)0.0235 (4)
C50.18738 (17)0.4768 (3)0.67285 (12)0.0220 (4)
C60.28581 (17)0.5516 (3)0.72644 (12)0.0223 (4)
H60.28040.68040.75230.027*
C70.39424 (16)0.4399 (3)0.74336 (11)0.0202 (4)
C80.50033 (16)0.5275 (3)0.80131 (12)0.0213 (4)
H8A0.48930.50680.85720.026*
H8B0.50560.67790.79200.026*
C90.61606 (16)0.4240 (3)0.79094 (11)0.0192 (4)
H90.62860.45790.73570.023*
C100.72847 (16)0.4988 (3)0.85243 (11)0.0184 (4)
C110.84475 (19)0.8166 (3)0.86491 (13)0.0286 (4)
H11A0.84200.95910.84510.043*
H11B0.91350.74510.85090.043*
H11C0.85280.81740.92350.043*
C120.70428 (16)0.4858 (3)0.93825 (11)0.0203 (4)
C130.65850 (17)0.6563 (3)0.97170 (12)0.0262 (4)
H130.64850.78350.94310.031*
C140.62723 (19)0.6421 (4)1.04692 (13)0.0342 (5)
H140.59580.75921.06920.041*
C150.6419 (2)0.4581 (5)1.08902 (14)0.0386 (6)
H150.62100.44911.14040.046*
C160.6866 (2)0.2885 (4)1.05673 (13)0.0343 (5)
H160.69680.16221.08580.041*
C170.71712 (18)0.3007 (4)0.98122 (12)0.0263 (4)
H170.74690.18190.95890.032*
C180.84221 (16)0.3857 (3)0.84109 (12)0.0196 (4)
C190.93859 (18)0.3513 (3)0.90463 (12)0.0253 (4)
H190.93200.38760.95780.030*
C201.04428 (18)0.2646 (4)0.89128 (13)0.0321 (5)
H201.10880.24080.93540.039*
C211.05638 (18)0.2124 (4)0.81417 (14)0.0313 (5)
H211.12880.15350.80520.038*
C220.96216 (18)0.2470 (4)0.75069 (13)0.0279 (4)
H220.96960.21100.69760.033*
C230.85646 (18)0.3341 (3)0.76349 (12)0.0231 (4)
H230.79280.35910.71890.028*
C240.57492 (16)0.1204 (3)0.64812 (11)0.0224 (4)
C250.6553 (2)−0.0382 (4)0.64257 (14)0.0342 (5)
H250.6682−0.14430.68200.041*
C260.7170 (2)−0.0424 (5)0.57963 (16)0.0453 (7)
H260.7723−0.15040.57670.054*
C270.6978 (2)0.1107 (5)0.52141 (15)0.0468 (7)
H270.73950.10730.47830.056*
C280.6183 (2)0.2676 (5)0.52613 (14)0.0412 (6)
H280.60540.37290.48630.049*
C290.55619 (19)0.2729 (4)0.58943 (12)0.0299 (5)
H290.50100.38130.59220.036*
C300.1034 (2)0.0483 (4)0.53183 (14)0.0338 (5)
H30A0.02590.02220.49600.051*
H30B0.1259−0.07130.56700.051*
H30C0.16440.07160.49960.051*
C310.05904 (19)0.7391 (4)0.70544 (14)0.0344 (5)
H31A−0.02030.79920.68540.052*
H31B0.12030.84610.70750.052*
H31C0.06280.68290.75960.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0239 (7)0.0337 (9)0.0308 (8)0.0000 (6)−0.0038 (6)−0.0068 (7)
O20.0221 (7)0.0330 (9)0.0301 (8)0.0057 (6)0.0010 (6)−0.0018 (6)
O30.0260 (7)0.0179 (7)0.0270 (7)−0.0005 (6)0.0028 (5)0.0042 (6)
N10.0246 (8)0.0179 (8)0.0196 (8)0.0013 (6)0.0002 (6)0.0007 (6)
C10.0209 (8)0.0166 (9)0.0207 (9)0.0018 (7)0.0020 (7)−0.0023 (7)
C20.0193 (8)0.0217 (9)0.0184 (8)0.0000 (7)0.0043 (6)0.0005 (7)
C30.0243 (9)0.0224 (10)0.0203 (9)−0.0016 (8)0.0045 (7)−0.0025 (7)
C40.0230 (9)0.0276 (11)0.0195 (9)−0.0011 (8)0.0036 (7)0.0002 (8)
C50.0190 (9)0.0257 (10)0.0213 (9)0.0015 (7)0.0039 (7)0.0019 (8)
C60.0242 (9)0.0218 (10)0.0210 (9)0.0015 (8)0.0051 (7)−0.0003 (7)
C70.0186 (9)0.0231 (10)0.0190 (9)−0.0008 (7)0.0042 (7)0.0002 (7)
C80.0205 (9)0.0197 (9)0.0231 (9)0.0018 (7)0.0030 (7)−0.0009 (7)
C90.0209 (9)0.0193 (9)0.0172 (8)0.0012 (7)0.0034 (7)0.0000 (7)
C100.0204 (9)0.0170 (9)0.0174 (8)−0.0001 (7)0.0033 (7)0.0011 (7)
C110.0282 (10)0.0207 (10)0.0373 (11)−0.0049 (8)0.0073 (9)0.0010 (9)
C120.0168 (8)0.0266 (10)0.0173 (8)−0.0017 (7)0.0029 (7)−0.0015 (7)
C130.0214 (9)0.0289 (11)0.0282 (10)−0.0026 (8)0.0046 (7)−0.0052 (8)
C140.0296 (11)0.0452 (15)0.0298 (11)−0.0010 (10)0.0108 (9)−0.0128 (10)
C150.0386 (13)0.0563 (17)0.0239 (11)−0.0113 (12)0.0134 (9)−0.0041 (11)
C160.0381 (12)0.0398 (14)0.0253 (10)−0.0075 (10)0.0073 (9)0.0053 (10)
C170.0274 (10)0.0296 (11)0.0216 (9)−0.0019 (9)0.0045 (8)0.0002 (8)
C180.0187 (9)0.0185 (9)0.0224 (9)−0.0009 (7)0.0057 (7)0.0024 (7)
C190.0225 (9)0.0280 (11)0.0248 (10)0.0002 (8)0.0035 (7)−0.0008 (8)
C200.0215 (10)0.0402 (13)0.0323 (11)0.0047 (9)0.0000 (8)0.0010 (10)
C210.0225 (10)0.0322 (12)0.0419 (12)0.0044 (9)0.0125 (8)−0.0011 (10)
C220.0301 (10)0.0300 (11)0.0262 (10)0.0014 (9)0.0121 (8)−0.0002 (8)
C230.0241 (9)0.0230 (10)0.0224 (9)0.0005 (8)0.0052 (7)0.0017 (8)
C240.0231 (9)0.0240 (10)0.0197 (9)0.0006 (8)0.0032 (7)−0.0043 (8)
C250.0397 (12)0.0317 (12)0.0309 (11)0.0110 (10)0.0068 (9)−0.0024 (9)
C260.0432 (14)0.0538 (17)0.0413 (14)0.0142 (13)0.0144 (11)−0.0168 (13)
C270.0463 (14)0.067 (2)0.0316 (12)−0.0049 (14)0.0191 (11)−0.0143 (13)
C280.0446 (13)0.0528 (16)0.0288 (11)−0.0037 (12)0.0132 (10)0.0056 (11)
C290.0305 (10)0.0334 (12)0.0265 (10)0.0025 (9)0.0073 (8)0.0022 (9)
C300.0375 (12)0.0324 (12)0.0269 (11)−0.0027 (10)−0.0044 (9)−0.0058 (9)
C310.0260 (10)0.0361 (13)0.0411 (12)0.0092 (9)0.0069 (9)−0.0045 (10)
Geometric parameters (Å, º) top
O1—C41.370 (2)C14—C151.381 (4)
O1—C301.432 (3)C14—H140.9500
O2—C51.372 (2)C15—C161.371 (4)
O2—C311.424 (3)C15—H150.9500
O3—C111.427 (2)C16—C171.396 (3)
O3—C101.448 (2)C16—H160.9500
N1—C91.466 (3)C17—H170.9500
N1—C11.482 (2)C18—C191.392 (3)
N1—H1N0.959 (10)C18—C231.399 (3)
C1—C21.514 (3)C19—C201.390 (3)
C1—C241.532 (3)C19—H190.9500
C1—H11.0000C20—C211.385 (3)
C2—C71.384 (3)C20—H200.9500
C2—C31.413 (3)C21—C221.377 (3)
C3—C41.383 (3)C21—H210.9500
C3—H30.9500C22—C231.387 (3)
C4—C51.408 (3)C22—H220.9500
C5—C61.381 (3)C23—H230.9500
C6—C71.411 (3)C24—C291.388 (3)
C6—H60.9500C24—C251.392 (3)
C7—C81.507 (3)C25—C261.393 (3)
C8—C91.522 (3)C25—H250.9500
C8—H8A0.9900C26—C271.385 (4)
C8—H8B0.9900C26—H260.9500
C9—C101.557 (3)C27—C281.375 (4)
C9—H91.0000C27—H270.9500
C10—C181.536 (3)C28—C291.402 (3)
C10—C121.538 (2)C28—H280.9500
C11—H11A0.9800C29—H290.9500
C11—H11B0.9800C30—H30A0.9800
C11—H11C0.9800C30—H30B0.9800
C12—C131.391 (3)C30—H30C0.9800
C12—C171.395 (3)C31—H31A0.9800
C13—C141.396 (3)C31—H31B0.9800
C13—H130.9500C31—H31C0.9800
C4—O1—C30117.41 (16)C15—C14—C13120.2 (2)
C5—O2—C31116.66 (16)C15—C14—H14119.9
C11—O3—C10115.71 (15)C13—C14—H14119.9
C9—N1—C1111.01 (15)C16—C15—C14120.00 (19)
C9—N1—H1N111.8 (17)C16—C15—H15120.0
C1—N1—H1N111.7 (16)C14—C15—H15120.0
N1—C1—C2110.18 (15)C15—C16—C17120.2 (2)
N1—C1—C24112.01 (15)C15—C16—H16119.9
C2—C1—C24112.94 (15)C17—C16—H16119.9
N1—C1—H1107.1C12—C17—C16120.6 (2)
C2—C1—H1107.1C12—C17—H17119.7
C24—C1—H1107.1C16—C17—H17119.7
C7—C2—C3119.78 (17)C19—C18—C23117.77 (17)
C7—C2—C1121.49 (16)C19—C18—C10122.26 (17)
C3—C2—C1118.68 (17)C23—C18—C10119.61 (17)
C4—C3—C2120.84 (18)C20—C19—C18120.89 (19)
C4—C3—H3119.6C20—C19—H19119.6
C2—C3—H3119.6C18—C19—H19119.6
O1—C4—C3124.74 (19)C21—C20—C19120.6 (2)
O1—C4—C5115.90 (17)C21—C20—H20119.7
C3—C4—C5119.36 (18)C19—C20—H20119.7
O2—C5—C6124.25 (19)C22—C21—C20119.18 (19)
O2—C5—C4115.94 (17)C22—C21—H21120.4
C6—C5—C4119.80 (17)C20—C21—H21120.4
C5—C6—C7121.05 (19)C21—C22—C23120.61 (19)
C5—C6—H6119.5C21—C22—H22119.7
C7—C6—H6119.5C23—C22—H22119.7
C2—C7—C6119.14 (17)C22—C23—C18120.98 (19)
C2—C7—C8121.22 (16)C22—C23—H23119.5
C6—C7—C8119.64 (17)C18—C23—H23119.5
C7—C8—C9111.07 (16)C29—C24—C25118.95 (18)
C7—C8—H8A109.4C29—C24—C1122.43 (18)
C9—C8—H8A109.4C25—C24—C1118.55 (18)
C7—C8—H8B109.4C24—C25—C26120.6 (2)
C9—C8—H8B109.4C24—C25—H25119.7
H8A—C8—H8B108.0C26—C25—H25119.7
N1—C9—C8107.30 (16)C27—C26—C25120.1 (2)
N1—C9—C10112.49 (15)C27—C26—H26120.0
C8—C9—C10113.68 (15)C25—C26—H26120.0
N1—C9—H9107.7C28—C27—C26119.9 (2)
C8—C9—H9107.7C28—C27—H27120.1
C10—C9—H9107.7C26—C27—H27120.1
O3—C10—C18108.30 (15)C27—C28—C29120.3 (3)
O3—C10—C12110.48 (15)C27—C28—H28119.9
C18—C10—C12114.26 (15)C29—C28—H28119.9
O3—C10—C9101.76 (14)C24—C29—C28120.3 (2)
C18—C10—C9111.71 (15)C24—C29—H29119.9
C12—C10—C9109.61 (14)C28—C29—H29119.9
O3—C11—H11A109.5O1—C30—H30A109.5
O3—C11—H11B109.5O1—C30—H30B109.5
H11A—C11—H11B109.5H30A—C30—H30B109.5
O3—C11—H11C109.5O1—C30—H30C109.5
H11A—C11—H11C109.5H30A—C30—H30C109.5
H11B—C11—H11C109.5H30B—C30—H30C109.5
C13—C12—C17118.51 (17)O2—C31—H31A109.5
C13—C12—C10119.80 (18)O2—C31—H31B109.5
C17—C12—C10121.45 (17)H31A—C31—H31B109.5
C12—C13—C14120.5 (2)O2—C31—H31C109.5
C12—C13—H13119.8H31A—C31—H31C109.5
C14—C13—H13119.8H31B—C31—H31C109.5
C9—N1—C1—C2−52.4 (2)O3—C10—C12—C1319.5 (2)
C9—N1—C1—C2474.18 (19)C18—C10—C12—C13141.86 (18)
N1—C1—C2—C717.3 (2)C9—C10—C12—C13−91.9 (2)
C24—C1—C2—C7−108.82 (19)O3—C10—C12—C17−166.31 (17)
N1—C1—C2—C3−165.58 (16)C18—C10—C12—C17−43.9 (2)
C24—C1—C2—C368.3 (2)C9—C10—C12—C1782.3 (2)
C7—C2—C3—C4−0.4 (3)C17—C12—C13—C140.5 (3)
C1—C2—C3—C4−177.58 (17)C10—C12—C13—C14174.93 (17)
C30—O1—C4—C3−7.4 (3)C12—C13—C14—C150.2 (3)
C30—O1—C4—C5172.58 (17)C13—C14—C15—C16−0.4 (3)
C2—C3—C4—O1178.58 (18)C14—C15—C16—C17−0.2 (4)
C2—C3—C4—C5−1.4 (3)C13—C12—C17—C16−1.1 (3)
C31—O2—C5—C6−17.1 (3)C10—C12—C17—C16−175.41 (18)
C31—O2—C5—C4164.18 (19)C15—C16—C17—C120.9 (3)
O1—C4—C5—O20.7 (2)O3—C10—C18—C1998.0 (2)
C3—C4—C5—O2−179.31 (17)C12—C10—C18—C19−25.5 (3)
O1—C4—C5—C6−178.13 (17)C9—C10—C18—C19−150.69 (18)
C3—C4—C5—C61.9 (3)O3—C10—C18—C23−74.9 (2)
O2—C5—C6—C7−179.24 (17)C12—C10—C18—C23161.55 (17)
C4—C5—C6—C7−0.5 (3)C9—C10—C18—C2336.4 (2)
C3—C2—C7—C61.7 (3)C23—C18—C19—C20−1.3 (3)
C1—C2—C7—C6178.84 (17)C10—C18—C19—C20−174.4 (2)
C3—C2—C7—C8−178.75 (17)C18—C19—C20—C210.7 (4)
C1—C2—C7—C8−1.6 (3)C19—C20—C21—C22−0.2 (4)
C5—C6—C7—C2−1.3 (3)C20—C21—C22—C230.4 (4)
C5—C6—C7—C8179.19 (17)C21—C22—C23—C18−1.1 (3)
C2—C7—C8—C919.0 (2)C19—C18—C23—C221.5 (3)
C6—C7—C8—C9−161.53 (17)C10—C18—C23—C22174.74 (19)
C1—N1—C9—C871.30 (19)N1—C1—C24—C29−100.9 (2)
C1—N1—C9—C10−162.95 (14)C2—C1—C24—C2924.2 (3)
C7—C8—C9—N1−51.7 (2)N1—C1—C24—C2575.9 (2)
C7—C8—C9—C10−176.70 (15)C2—C1—C24—C25−158.95 (19)
C11—O3—C10—C18−51.5 (2)C29—C24—C25—C260.7 (3)
C11—O3—C10—C1274.29 (19)C1—C24—C25—C26−176.2 (2)
C11—O3—C10—C9−169.37 (15)C24—C25—C26—C27−0.7 (4)
N1—C9—C10—O3171.51 (15)C25—C26—C27—C280.4 (4)
C8—C9—C10—O3−66.28 (18)C26—C27—C28—C29−0.3 (4)
N1—C9—C10—C1856.2 (2)C25—C24—C29—C28−0.6 (3)
C8—C9—C10—C18178.38 (16)C1—C24—C29—C28176.2 (2)
N1—C9—C10—C12−71.52 (19)C27—C28—C29—C240.4 (4)
C8—C9—C10—C1250.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···Cgi0.982.573.45 (2)150
C30—H30A···O1ii0.982.543.356 (2)140
C30—H30A···O2ii0.982.593.400 (2)140
Symmetry codes: (i) x, y+1, z; (ii) −x, y−1/2, −z+1.
(II) (1R,3S)-2-benzyl-3-[diphenyl(trimethylsiloxy)methyl]- 6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline top
Crystal data top
C40H43NO3SiF(000) = 1312
Mr = 613.84Dx = 1.217 Mg m−3
Monoclinic, P21Melting point: 459 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 11.045 (10) ÅCell parameters from 37993 reflections
b = 17.008 (15) Åθ = 1.9–29.0°
c = 18.489 (15) ŵ = 0.11 mm−1
β = 105.287 (15)°T = 100 K
V = 3350 (5) Å3Flat, colourless
Z = 40.22 × 0.12 × 0.10 mm
Data collection top
Bruker APEXII DUO
diffractometer		17263 independent reflections
Radiation source: fine-focus sealed tube11255 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
0.5° ϕ scans and ωθmax = 29.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		h = −14→14
Tmin = 0.976, Tmax = 0.989k = −22→23
37993 measured reflectionsl = −24→25
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.057 w = 1/[σ2(Fo2) + (0.0476P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124(Δ/σ)max = 0.001
S = 0.99Δρmax = 0.38 e Å−3
17263 reflectionsΔρmin = −0.41 e Å−3
812 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0031 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.00 (10)
Crystal data top
C40H43NO3SiV = 3350 (5) Å3
Mr = 613.84Z = 4
Monoclinic, P21Mo Kα radiation
a = 11.045 (10) ŵ = 0.11 mm−1
b = 17.008 (15) ÅT = 100 K
c = 18.489 (15) Å0.22 × 0.12 × 0.10 mm
β = 105.287 (15)°
Data collection top
Bruker APEXII DUO
diffractometer		17263 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		11255 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.989Rint = 0.064
37993 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.38 e Å−3
S = 0.99Δρmin = −0.41 e Å−3
17263 reflectionsAbsolute structure: Flack (1983)
812 parametersAbsolute structure parameter: 0.00 (10)
1 restraint
Special details top

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.

Refinement. For both crystals, X-ray diffraction data were collected on a Bruker APEXII Duo diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Data collection was carried out at 173 (2) K and 100 (2) K for structures (I) and (II), respectively, to minimize thermal motion effects. Temperature was controlled by an Oxford Cryostream cooling system (Oxford Cryostat). Cell refinement and data reduction were performed using the program SAINT (Bruker, 2006). The data were scaled and empirical absorption corrections were performed using SADABS (Bruker, 2006). The structure was solved by direct methods using SHELXS97 (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F2 using SHELXL97 (Sheldrick, 2008). All non-H atoms were refined anisotropically.

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 (Å2) top
xyzUiso*/Ueq
Si1A1.33135 (7)0.65151 (5)0.94622 (4)0.02577 (17)
O1A0.53787 (16)0.84257 (11)0.86009 (10)0.0312 (4)
O2A0.59340 (16)0.70165 (11)0.82795 (10)0.0296 (4)
O3A1.30017 (16)0.73494 (10)0.98233 (10)0.0248 (4)
N1A1.11113 (19)0.87142 (13)0.99536 (11)0.0226 (5)
C1A0.9826 (2)0.89809 (16)0.99376 (15)0.0233 (6)
H1A0.97010.95020.96780.028*
C2A0.8812 (2)0.84407 (16)0.94961 (13)0.0225 (5)
C3A0.7568 (2)0.87099 (17)0.92318 (14)0.0253 (6)
H3A0.73790.92400.93200.030*
C4A0.6618 (2)0.82236 (16)0.88484 (14)0.0239 (6)
C5A0.6912 (2)0.74529 (16)0.86895 (14)0.0249 (6)
C6A0.8132 (2)0.71878 (16)0.89415 (14)0.0247 (6)
H6A0.83280.66650.88310.030*
C7A0.9088 (2)0.76756 (16)0.93568 (14)0.0243 (6)
C8A1.0403 (2)0.73529 (16)0.96360 (15)0.0249 (6)
H8A11.07710.72850.92060.030*
H8A21.03670.68300.98640.030*
C9A1.1248 (2)0.78935 (16)1.02147 (15)0.0241 (6)
H9A1.09210.78741.06700.029*
C10A1.2633 (2)0.76114 (16)1.04698 (14)0.0226 (5)
C11A1.1400 (2)0.88310 (16)0.92310 (14)0.0263 (6)
H11A1.07520.85630.88350.032*
H11B1.22170.85800.92510.032*
C12A1.1459 (2)0.96783 (17)0.90178 (14)0.0256 (6)
C13A1.1142 (3)0.98735 (19)0.82648 (16)0.0365 (7)
H13A1.08810.94750.78960.044*
C14A1.1205 (3)1.0649 (2)0.80471 (18)0.0468 (8)
H14A1.10051.07750.75280.056*
C15A1.1551 (3)1.1236 (2)0.85646 (19)0.0443 (8)
H15A1.15651.17680.84090.053*
C16A1.1876 (3)1.10468 (18)0.93105 (18)0.0365 (7)
H16A1.21221.14490.96760.044*
C17A1.1848 (3)1.02749 (18)0.95335 (16)0.0336 (7)
H17A1.21021.01511.00530.040*
C18A0.9739 (2)0.91196 (16)1.07361 (14)0.0249 (6)
C19A1.0499 (3)0.96910 (19)1.11667 (16)0.0362 (7)
H19A1.10680.99781.09620.043*
C20A1.0438 (3)0.9848 (2)1.18886 (17)0.0411 (8)
H20A1.09701.02381.21750.049*
C21A0.9622 (3)0.9449 (2)1.21979 (16)0.0404 (8)
H21A0.95730.95671.26920.048*
C22A0.8871 (3)0.88726 (19)1.17808 (16)0.0353 (7)
H22A0.83080.85861.19910.042*
C23A0.8935 (2)0.87094 (17)1.10526 (15)0.0280 (6)
H23A0.84160.83101.07720.034*
C24A0.5037 (3)0.91827 (17)0.88058 (17)0.0340 (7)
H24A0.41330.92610.85980.051*
H24B0.54970.95860.86080.051*
H24C0.52450.92240.93530.051*
C25A0.6170 (3)0.62008 (16)0.81876 (15)0.0293 (6)
H25A0.54040.59490.78870.044*
H25B0.64310.59480.86810.044*
H25C0.68390.61460.79320.044*
C26A1.3508 (2)0.82724 (15)1.08281 (14)0.0242 (6)
C27A1.3299 (3)0.86698 (17)1.14408 (15)0.0299 (6)
H27A1.25730.85551.16050.036*
C28A1.4142 (3)0.92320 (17)1.18143 (17)0.0363 (7)
H28A1.39890.95031.22300.044*
C29A1.5203 (3)0.93986 (18)1.15842 (19)0.0402 (8)
H29A1.57890.97761.18470.048*
C30A1.5407 (3)0.90201 (18)1.0979 (2)0.0411 (8)
H30A1.61340.91411.08170.049*
C31A1.4568 (2)0.84619 (17)1.05963 (17)0.0324 (6)
H31A1.47200.82061.01720.039*
C32A1.2823 (2)0.69397 (15)1.10513 (14)0.0238 (6)
C33A1.1858 (3)0.65404 (18)1.12427 (14)0.0300 (6)
H33A1.10130.66981.10310.036*
C34A1.2113 (3)0.59145 (17)1.17387 (17)0.0354 (7)
H34A1.14400.56371.18540.042*
C35A1.3331 (3)0.56905 (18)1.20664 (16)0.0381 (7)
H35A1.34990.52621.24080.046*
C36A1.4316 (3)0.60949 (16)1.18957 (15)0.0321 (7)
H36A1.51610.59481.21230.039*
C37A1.4053 (2)0.67123 (17)1.13930 (14)0.0283 (6)
H37A1.47270.69881.12780.034*
C38A1.2849 (3)0.6699 (2)0.84373 (14)0.0399 (8)
H38A1.33190.71500.83230.060*
H38B1.19480.68120.82740.060*
H38C1.30350.62330.81740.060*
C39A1.5018 (3)0.6298 (2)0.97843 (17)0.0385 (7)
H39A1.54950.67480.96730.058*
H39B1.52070.58310.95240.058*
H39C1.52520.62021.03260.058*
C40A1.2444 (3)0.56648 (18)0.96826 (18)0.0385 (7)
H40A1.26950.55691.02240.058*
H40B1.26330.51990.94190.058*
H40C1.15410.57730.95210.058*
Si1B0.38084 (8)0.66516 (6)0.54431 (4)0.0387 (2)
O1B−0.32660 (18)0.48951 (12)0.64426 (11)0.0372 (5)
O2B−0.2299 (2)0.62700 (12)0.67946 (11)0.0388 (5)
O3B0.31506 (17)0.58420 (12)0.50317 (10)0.0328 (5)
N1B0.1118 (2)0.45253 (14)0.49797 (12)0.0270 (5)
C1B−0.0135 (2)0.42695 (17)0.50334 (14)0.0262 (6)
H1B−0.00020.37650.53210.031*
C2B−0.0730 (2)0.48319 (17)0.54735 (14)0.0271 (6)
C3B−0.1721 (2)0.45851 (17)0.57508 (15)0.0281 (6)
H3B−0.20290.40640.56510.034*
C4B−0.2268 (3)0.50776 (17)0.61670 (15)0.0288 (6)
C5B−0.1769 (3)0.58327 (17)0.63382 (15)0.0321 (7)
C6B−0.0803 (3)0.60837 (18)0.60552 (15)0.0306 (6)
H6B−0.04770.65990.61680.037*
C7B−0.0289 (2)0.55947 (17)0.56035 (14)0.0268 (6)
C8B0.0742 (3)0.59037 (17)0.52872 (16)0.0303 (6)
H8B10.15140.59770.56990.036*
H8B20.04930.64230.50520.036*
C9B0.1011 (2)0.53415 (17)0.47056 (15)0.0268 (6)
H9B0.02560.53580.42660.032*
C10B0.2137 (2)0.56176 (17)0.44107 (14)0.0271 (6)
C11B0.2086 (3)0.44284 (18)0.56911 (15)0.0334 (7)
H11C0.18200.47170.60880.040*
H11D0.28740.46720.56410.040*
C12B0.2349 (2)0.35864 (18)0.59348 (16)0.0319 (7)
C13B0.2207 (3)0.2966 (2)0.54393 (18)0.0439 (8)
H13B0.19350.30600.49150.053*
C14B0.2460 (3)0.2202 (2)0.5705 (2)0.0520 (9)
H14B0.23240.17750.53620.062*
C15B0.2902 (3)0.2060 (2)0.6456 (2)0.0588 (10)
H15B0.30840.15380.66340.071*
C16B0.3079 (3)0.2670 (2)0.6944 (2)0.0572 (10)
H16B0.34050.25750.74660.069*
C17B0.2793 (3)0.3423 (2)0.66951 (17)0.0433 (8)
H17B0.28990.38400.70480.052*
C18B−0.0976 (2)0.40728 (16)0.42588 (15)0.0268 (6)
C19B−0.0678 (3)0.3434 (2)0.38787 (17)0.0411 (8)
H19B0.00820.31570.40830.049*
C20B−0.1469 (3)0.3190 (2)0.32044 (18)0.0504 (9)
H20B−0.12570.27400.29590.061*
C21B−0.2553 (3)0.3592 (2)0.28871 (18)0.0458 (8)
H21B−0.31040.34140.24310.055*
C22B−0.2835 (3)0.4254 (2)0.32355 (17)0.0429 (8)
H22B−0.35630.45530.30090.051*
C23B−0.2048 (3)0.44862 (19)0.39232 (16)0.0345 (7)
H23B−0.22560.49400.41650.041*
C24B−0.3904 (3)0.4183 (2)0.61850 (19)0.0423 (8)
H24D−0.46000.41140.64160.063*
H24E−0.33200.37410.63220.063*
H24F−0.42330.42030.56390.063*
C25B−0.1827 (4)0.70334 (19)0.6976 (2)0.0527 (10)
H25D−0.22810.72860.73020.079*
H25E−0.19380.73420.65150.079*
H25F−0.09320.70040.72360.079*
C26B0.2586 (2)0.49462 (17)0.39940 (14)0.0270 (6)
C27B0.3819 (3)0.4690 (2)0.42015 (18)0.0404 (8)
H27B0.43890.49080.46320.048*
C28B0.4227 (3)0.4120 (2)0.3787 (2)0.0492 (9)
H28B0.50720.39420.39390.059*
C29B0.3414 (3)0.38082 (19)0.3155 (2)0.0478 (9)
H29B0.36990.34250.28650.057*
C30B0.2189 (3)0.40568 (17)0.29503 (18)0.0385 (7)
H30B0.16220.38370.25200.046*
C31B0.1773 (3)0.46200 (17)0.33600 (15)0.0306 (6)
H31B0.09230.47880.32090.037*
C32B0.1799 (3)0.63189 (16)0.38652 (14)0.0275 (6)
C33B0.2748 (3)0.65991 (18)0.35603 (15)0.0317 (6)
H33B0.35410.63440.36810.038*
C34B0.2547 (3)0.72437 (18)0.30844 (16)0.0370 (7)
H34B0.31990.74260.28790.044*
C35B0.1408 (3)0.76182 (18)0.29110 (17)0.0392 (7)
H35B0.12740.80670.25930.047*
C36B0.0459 (3)0.73433 (18)0.31978 (17)0.0373 (7)
H36B−0.03330.76010.30730.045*
C37B0.0649 (3)0.66940 (18)0.36666 (15)0.0322 (6)
H37B−0.00190.65040.38540.039*
C38B0.4147 (4)0.6441 (3)0.64494 (17)0.0623 (11)
H38D0.46610.59650.65650.093*
H38E0.33580.63620.65870.093*
H38F0.46040.68850.67340.093*
C39B0.5308 (3)0.6801 (3)0.5205 (2)0.0605 (10)
H39D0.51450.69160.46680.091*
H39E0.58190.63240.53230.091*
H39F0.57590.72430.54950.091*
C40B0.2853 (3)0.7554 (2)0.52123 (19)0.0472 (8)
H40D0.26700.76550.46720.071*
H40E0.33180.80000.54880.071*
H40F0.20650.74860.53540.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Si1A0.0261 (4)0.0277 (4)0.0248 (4)0.0030 (3)0.0089 (3)0.0001 (3)
O1A0.0248 (10)0.0287 (11)0.0363 (11)0.0017 (8)0.0015 (8)−0.0033 (9)
O2A0.0277 (10)0.0255 (11)0.0319 (10)−0.0064 (8)0.0014 (8)−0.0046 (9)
O3A0.0300 (10)0.0221 (10)0.0256 (9)0.0008 (8)0.0132 (8)0.0011 (8)
N1A0.0235 (11)0.0215 (12)0.0224 (10)0.0010 (9)0.0056 (8)0.0012 (9)
C1A0.0227 (13)0.0202 (15)0.0266 (13)−0.0020 (11)0.0054 (10)0.0004 (11)
C2A0.0261 (13)0.0224 (15)0.0197 (12)−0.0041 (11)0.0073 (10)−0.0018 (11)
C3A0.0293 (14)0.0226 (15)0.0247 (13)0.0013 (11)0.0083 (11)0.0007 (11)
C4A0.0228 (13)0.0272 (16)0.0215 (12)−0.0010 (11)0.0056 (10)0.0002 (11)
C5A0.0251 (13)0.0278 (16)0.0219 (13)−0.0049 (11)0.0066 (10)0.0013 (11)
C6A0.0290 (14)0.0228 (15)0.0225 (13)0.0003 (11)0.0073 (11)−0.0032 (11)
C7A0.0267 (13)0.0262 (15)0.0210 (13)−0.0010 (11)0.0083 (10)0.0012 (11)
C8A0.0243 (13)0.0243 (15)0.0282 (13)−0.0018 (11)0.0104 (11)−0.0038 (12)
C9A0.0251 (13)0.0210 (15)0.0276 (14)−0.0027 (11)0.0093 (11)0.0007 (12)
C10A0.0232 (13)0.0223 (14)0.0244 (13)−0.0011 (11)0.0101 (10)−0.0024 (11)
C11A0.0297 (14)0.0250 (15)0.0248 (13)−0.0013 (12)0.0080 (11)0.0006 (12)
C12A0.0209 (13)0.0284 (16)0.0279 (14)−0.0007 (11)0.0072 (11)0.0004 (12)
C13A0.0453 (18)0.0342 (18)0.0277 (15)−0.0014 (14)0.0055 (13)0.0040 (13)
C14A0.066 (2)0.040 (2)0.0291 (16)0.0030 (17)0.0042 (15)0.0107 (15)
C15A0.0494 (19)0.0308 (18)0.0496 (19)−0.0036 (15)0.0079 (15)0.0107 (16)
C16A0.0380 (17)0.0300 (18)0.0415 (17)−0.0095 (13)0.0106 (14)−0.0034 (14)
C17A0.0351 (16)0.0354 (18)0.0294 (15)−0.0069 (13)0.0069 (12)0.0019 (13)
C18A0.0255 (13)0.0220 (15)0.0261 (13)0.0031 (11)0.0050 (11)−0.0017 (11)
C19A0.0361 (16)0.0366 (18)0.0358 (16)−0.0037 (14)0.0093 (13)−0.0057 (14)
C20A0.0429 (18)0.044 (2)0.0342 (16)−0.0063 (15)0.0059 (14)−0.0171 (15)
C21A0.0430 (17)0.051 (2)0.0270 (15)0.0102 (16)0.0080 (13)−0.0075 (15)
C22A0.0344 (16)0.042 (2)0.0316 (15)0.0051 (14)0.0119 (12)0.0060 (14)
C23A0.0304 (14)0.0251 (16)0.0273 (14)0.0013 (12)0.0054 (11)−0.0005 (12)
C24A0.0271 (14)0.0266 (16)0.0455 (17)−0.0011 (12)0.0048 (13)−0.0026 (14)
C25A0.0325 (15)0.0279 (16)0.0273 (14)−0.0068 (12)0.0075 (12)−0.0034 (12)
C26A0.0244 (13)0.0211 (15)0.0255 (13)0.0013 (11)0.0037 (10)0.0048 (11)
C27A0.0294 (14)0.0267 (16)0.0307 (14)−0.0016 (12)0.0029 (11)0.0014 (12)
C28A0.0450 (17)0.0231 (16)0.0359 (16)0.0001 (13)0.0019 (13)−0.0007 (13)
C29A0.0320 (16)0.0238 (17)0.055 (2)−0.0078 (13)−0.0058 (14)0.0012 (15)
C30A0.0288 (15)0.0265 (18)0.067 (2)−0.0047 (13)0.0104 (15)0.0064 (16)
C31A0.0263 (14)0.0263 (16)0.0450 (17)−0.0035 (12)0.0099 (12)0.0037 (14)
C32A0.0317 (14)0.0169 (14)0.0226 (13)−0.0023 (11)0.0070 (11)−0.0032 (10)
C33A0.0362 (15)0.0270 (16)0.0299 (14)−0.0058 (13)0.0142 (11)−0.0006 (13)
C34A0.0496 (18)0.0234 (16)0.0405 (16)−0.0034 (14)0.0247 (14)0.0034 (13)
C35A0.061 (2)0.0254 (17)0.0297 (15)0.0039 (15)0.0152 (14)0.0044 (13)
C36A0.0431 (17)0.0200 (16)0.0307 (15)0.0023 (13)0.0053 (13)0.0004 (12)
C37A0.0317 (14)0.0250 (16)0.0277 (13)−0.0042 (12)0.0072 (11)−0.0005 (12)
C38A0.0474 (18)0.046 (2)0.0241 (14)0.0100 (16)0.0065 (12)0.0006 (14)
C39A0.0319 (15)0.047 (2)0.0391 (16)0.0116 (14)0.0135 (13)0.0041 (15)
C40A0.0439 (17)0.0254 (17)0.0500 (19)0.0005 (14)0.0191 (15)−0.0037 (15)
Si1B0.0361 (4)0.0450 (6)0.0311 (4)−0.0035 (4)0.0022 (3)−0.0033 (4)
O1B0.0424 (12)0.0347 (13)0.0427 (12)0.0006 (10)0.0256 (10)0.0028 (10)
O2B0.0571 (13)0.0303 (12)0.0369 (11)0.0082 (10)0.0264 (10)0.0011 (9)
O3B0.0280 (10)0.0446 (13)0.0226 (9)−0.0032 (9)0.0009 (8)0.0003 (9)
N1B0.0275 (11)0.0311 (14)0.0223 (11)0.0023 (10)0.0067 (9)0.0001 (10)
C1B0.0303 (13)0.0250 (15)0.0239 (13)0.0020 (12)0.0083 (10)0.0006 (12)
C2B0.0294 (14)0.0284 (16)0.0227 (13)0.0032 (12)0.0057 (11)0.0001 (12)
C3B0.0311 (14)0.0263 (16)0.0278 (14)0.0009 (12)0.0093 (11)0.0008 (12)
C4B0.0305 (14)0.0338 (18)0.0255 (13)0.0057 (12)0.0136 (11)0.0061 (12)
C5B0.0429 (17)0.0302 (17)0.0263 (14)0.0110 (13)0.0146 (12)0.0029 (12)
C6B0.0391 (16)0.0282 (17)0.0264 (14)0.0003 (13)0.0123 (12)−0.0001 (12)
C7B0.0313 (14)0.0289 (16)0.0221 (13)0.0001 (12)0.0102 (11)−0.0005 (12)
C8B0.0336 (15)0.0277 (16)0.0319 (14)−0.0046 (12)0.0129 (12)−0.0055 (13)
C9B0.0252 (14)0.0301 (16)0.0254 (13)−0.0006 (12)0.0073 (11)−0.0040 (12)
C10B0.0235 (13)0.0348 (17)0.0221 (13)−0.0031 (12)0.0045 (10)−0.0023 (12)
C11B0.0339 (15)0.0420 (19)0.0223 (13)0.0013 (13)0.0040 (11)−0.0029 (13)
C12B0.0251 (14)0.0366 (18)0.0328 (15)0.0023 (13)0.0055 (12)0.0011 (13)
C13B0.0461 (19)0.044 (2)0.0371 (17)0.0172 (16)0.0031 (14)−0.0041 (16)
C14B0.047 (2)0.047 (2)0.058 (2)0.0106 (17)0.0059 (17)−0.0102 (19)
C15B0.058 (2)0.054 (3)0.061 (2)0.0184 (19)0.0101 (19)0.015 (2)
C16B0.066 (2)0.067 (3)0.0361 (19)0.010 (2)0.0094 (17)0.015 (2)
C17B0.0442 (18)0.054 (2)0.0298 (15)0.0042 (16)0.0071 (13)0.0048 (16)
C18B0.0276 (14)0.0266 (16)0.0275 (14)−0.0030 (12)0.0097 (11)−0.0028 (12)
C19B0.0357 (16)0.045 (2)0.0382 (16)0.0070 (15)0.0014 (13)−0.0083 (15)
C20B0.057 (2)0.049 (2)0.0388 (18)0.0030 (17)0.0020 (16)−0.0164 (16)
C21B0.0474 (19)0.051 (2)0.0333 (16)−0.0082 (17)0.0016 (14)−0.0050 (16)
C22B0.0383 (17)0.053 (2)0.0334 (16)0.0078 (16)0.0020 (13)0.0083 (16)
C23B0.0373 (16)0.0371 (19)0.0294 (14)0.0043 (14)0.0095 (12)0.0000 (13)
C24B0.0363 (16)0.045 (2)0.0494 (19)−0.0015 (15)0.0189 (14)0.0072 (16)
C25B0.093 (3)0.030 (2)0.052 (2)0.0032 (18)0.048 (2)−0.0019 (16)
C26B0.0286 (14)0.0295 (16)0.0254 (13)0.0016 (12)0.0113 (11)0.0050 (12)
C27B0.0375 (17)0.046 (2)0.0383 (17)0.0103 (15)0.0111 (14)0.0064 (15)
C28B0.0470 (19)0.044 (2)0.063 (2)0.0194 (17)0.0255 (18)0.0134 (19)
C29B0.068 (2)0.0264 (19)0.064 (2)0.0080 (17)0.044 (2)0.0017 (17)
C30B0.056 (2)0.0257 (17)0.0398 (17)−0.0032 (15)0.0226 (15)−0.0018 (14)
C31B0.0315 (15)0.0291 (16)0.0329 (15)0.0039 (12)0.0119 (12)0.0041 (13)
C32B0.0386 (15)0.0235 (16)0.0199 (12)−0.0044 (12)0.0069 (11)−0.0063 (11)
C33B0.0352 (15)0.0296 (16)0.0311 (14)0.0047 (13)0.0101 (11)−0.0016 (13)
C34B0.0508 (19)0.0323 (18)0.0308 (15)−0.0063 (15)0.0160 (14)−0.0001 (14)
C35B0.054 (2)0.0253 (17)0.0379 (17)−0.0001 (15)0.0119 (15)0.0013 (14)
C36B0.0400 (17)0.0317 (18)0.0372 (16)0.0014 (14)0.0050 (13)−0.0034 (14)
C37B0.0344 (15)0.0322 (17)0.0308 (14)−0.0008 (13)0.0100 (11)−0.0017 (13)
C38B0.070 (2)0.076 (3)0.0331 (17)−0.003 (2)0.0000 (16)−0.0083 (19)
C39B0.0418 (19)0.066 (3)0.066 (2)−0.0136 (18)0.0020 (17)−0.001 (2)
C40B0.056 (2)0.041 (2)0.0415 (18)0.0014 (16)0.0073 (15)−0.0086 (16)
Geometric parameters (Å, º) top
Si1A—O3A1.643 (2)Si1B—O3B1.647 (2)
Si1A—C40A1.840 (3)Si1B—C38B1.834 (4)
Si1A—C38A1.855 (3)Si1B—C39B1.841 (4)
Si1A—C39A1.856 (3)Si1B—C40B1.848 (4)
O1A—C4A1.368 (3)O1B—C4B1.366 (3)
O1A—C24A1.421 (4)O1B—C24B1.419 (4)
O2A—C5A1.364 (3)O2B—C5B1.367 (3)
O2A—C25A1.430 (3)O2B—C25B1.406 (4)
O3A—C10A1.432 (3)O3B—C10B1.428 (3)
N1A—C11A1.467 (3)N1B—C11B1.469 (3)
N1A—C9A1.472 (4)N1B—C9B1.472 (4)
N1A—C1A1.483 (3)N1B—C1B1.479 (4)
C1A—C2A1.511 (4)C1B—C2B1.513 (4)
C1A—C18A1.523 (4)C1B—C18B1.524 (4)
C1A—H1A1.0000C1B—H1B1.0000
C2A—C7A1.376 (4)C2B—C7B1.384 (4)
C2A—C3A1.409 (4)C2B—C3B1.390 (4)
C3A—C4A1.376 (4)C3B—C4B1.380 (4)
C3A—H3A0.9500C3B—H3B0.9500
C4A—C5A1.400 (4)C4B—C5B1.401 (4)
C5A—C6A1.380 (4)C5B—C6B1.374 (4)
C6A—C7A1.402 (4)C6B—C7B1.400 (4)
C6A—H6A0.9500C6B—H6B0.9500
C7A—C8A1.511 (4)C7B—C8B1.505 (4)
C8A—C9A1.528 (4)C8B—C9B1.526 (4)
C8A—H8A10.9900C8B—H8B10.9900
C8A—H8A20.9900C8B—H8B20.9900
C9A—C10A1.553 (4)C9B—C10B1.556 (4)
C9A—H9A1.0000C9B—H9B1.0000
C10A—C26A1.516 (4)C10B—C26B1.532 (4)
C10A—C32A1.545 (4)C10B—C32B1.543 (4)
C11A—C12A1.500 (4)C11B—C12B1.507 (4)
C11A—H11A0.9900C11B—H11C0.9900
C11A—H11B0.9900C11B—H11D0.9900
C12A—C17A1.381 (4)C12B—C13B1.379 (4)
C12A—C13A1.384 (4)C12B—C17B1.389 (4)
C13A—C14A1.387 (5)C13B—C14B1.391 (5)
C13A—H13A0.9500C13B—H13B0.9500
C14A—C15A1.365 (5)C14B—C15B1.366 (5)
C14A—H14A0.9500C14B—H14B0.9500
C15A—C16A1.369 (4)C15B—C16B1.356 (5)
C15A—H15A0.9500C15B—H15B0.9500
C16A—C17A1.379 (4)C16B—C17B1.369 (5)
C16A—H16A0.9500C16B—H16B0.9500
C17A—H17A0.9500C17B—H17B0.9500
C18A—C23A1.376 (4)C18B—C23B1.376 (4)
C18A—C19A1.389 (4)C18B—C19B1.380 (4)
C19A—C20A1.380 (4)C19B—C20B1.384 (4)
C19A—H19A0.9500C19B—H19B0.9500
C20A—C21A1.368 (4)C20B—C21B1.369 (5)
C20A—H20A0.9500C20B—H20B0.9500
C21A—C22A1.380 (4)C21B—C22B1.374 (5)
C21A—H21A0.9500C21B—H21B0.9500
C22A—C23A1.394 (4)C22B—C23B1.395 (4)
C22A—H22A0.9500C22B—H22B0.9500
C23A—H23A0.9500C23B—H23B0.9500
C24A—H24A0.9800C24B—H24D0.9800
C24A—H24B0.9800C24B—H24E0.9800
C24A—H24C0.9800C24B—H24F0.9800
C25A—H25A0.9800C25B—H25D0.9800
C25A—H25B0.9800C25B—H25E0.9800
C25A—H25C0.9800C25B—H25F0.9800
C26A—C31A1.387 (4)C26B—C27B1.383 (4)
C26A—C27A1.390 (4)C26B—C31B1.391 (4)
C27A—C28A1.385 (4)C27B—C28B1.383 (5)
C27A—H27A0.9500C27B—H27B0.9500
C28A—C29A1.377 (5)C28B—C29B1.378 (5)
C28A—H28A0.9500C28B—H28B0.9500
C29A—C30A1.361 (5)C29B—C30B1.372 (5)
C29A—H29A0.9500C29B—H29B0.9500
C30A—C31A1.383 (4)C30B—C31B1.374 (4)
C30A—H30A0.9500C30B—H30B0.9500
C31A—H31A0.9500C31B—H31B0.9500
C32A—C33A1.386 (4)C32B—C37B1.382 (4)
C32A—C37A1.393 (4)C32B—C33B1.398 (4)
C33A—C34A1.385 (4)C33B—C34B1.386 (4)
C33A—H33A0.9500C33B—H33B0.9500
C34A—C35A1.375 (4)C34B—C35B1.371 (4)
C34A—H34A0.9500C34B—H34B0.9500
C35A—C36A1.392 (4)C35B—C36B1.375 (4)
C35A—H35A0.9500C35B—H35B0.9500
C36A—C37A1.381 (4)C36B—C37B1.385 (4)
C36A—H36A0.9500C36B—H36B0.9500
C37A—H37A0.9500C37B—H37B0.9500
C38A—H38A0.9800C38B—H38D0.9800
C38A—H38B0.9800C38B—H38E0.9800
C38A—H38C0.9800C38B—H38F0.9800
C39A—H39A0.9800C39B—H39D0.9800
C39A—H39B0.9800C39B—H39E0.9800
C39A—H39C0.9800C39B—H39F0.9800
C40A—H40A0.9800C40B—H40D0.9800
C40A—H40B0.9800C40B—H40E0.9800
C40A—H40C0.9800C40B—H40F0.9800
O3A—Si1A—C40A114.29 (13)O3B—Si1B—C38B104.64 (16)
O3A—Si1A—C38A103.77 (13)O3B—Si1B—C39B108.67 (16)
C40A—Si1A—C38A109.83 (15)C38B—Si1B—C39B108.31 (18)
O3A—Si1A—C39A110.17 (13)O3B—Si1B—C40B115.63 (14)
C40A—Si1A—C39A108.50 (15)C38B—Si1B—C40B110.35 (18)
C38A—Si1A—C39A110.21 (14)C39B—Si1B—C40B108.98 (19)
C4A—O1A—C24A116.8 (2)C4B—O1B—C24B116.5 (2)
C5A—O2A—C25A116.8 (2)C5B—O2B—C25B117.2 (2)
C10A—O3A—Si1A138.11 (16)C10B—O3B—Si1B138.74 (19)
C11A—N1A—C9A113.5 (2)C11B—N1B—C9B112.8 (2)
C11A—N1A—C1A112.2 (2)C11B—N1B—C1B112.3 (2)
C9A—N1A—C1A108.1 (2)C9B—N1B—C1B108.0 (2)
N1A—C1A—C2A113.2 (2)N1B—C1B—C2B113.4 (2)
N1A—C1A—C18A109.4 (2)N1B—C1B—C18B110.5 (2)
C2A—C1A—C18A113.0 (2)C2B—C1B—C18B113.6 (2)
N1A—C1A—H1A106.9N1B—C1B—H1B106.2
C2A—C1A—H1A106.9C2B—C1B—H1B106.2
C18A—C1A—H1A106.9C18B—C1B—H1B106.2
C7A—C2A—C3A119.1 (2)C7B—C2B—C3B119.6 (3)
C7A—C2A—C1A120.5 (2)C7B—C2B—C1B120.2 (2)
C3A—C2A—C1A120.4 (2)C3B—C2B—C1B120.2 (3)
C4A—C3A—C2A121.6 (3)C4B—C3B—C2B121.7 (3)
C4A—C3A—H3A119.2C4B—C3B—H3B119.2
C2A—C3A—H3A119.2C2B—C3B—H3B119.2
O1A—C4A—C3A125.5 (2)O1B—C4B—C3B125.8 (3)
O1A—C4A—C5A115.6 (2)O1B—C4B—C5B115.6 (2)
C3A—C4A—C5A118.9 (2)C3B—C4B—C5B118.6 (3)
O2A—C5A—C6A124.7 (3)O2B—C5B—C6B124.6 (3)
O2A—C5A—C4A115.7 (2)O2B—C5B—C4B115.5 (3)
C6A—C5A—C4A119.6 (2)C6B—C5B—C4B119.9 (3)
C5A—C6A—C7A121.3 (3)C5B—C6B—C7B121.3 (3)
C5A—C6A—H6A119.4C5B—C6B—H6B119.3
C7A—C6A—H6A119.4C7B—C6B—H6B119.3
C2A—C7A—C6A119.3 (2)C2B—C7B—C6B118.8 (2)
C2A—C7A—C8A121.3 (2)C2B—C7B—C8B121.8 (2)
C6A—C7A—C8A119.3 (2)C6B—C7B—C8B119.4 (3)
C7A—C8A—C9A112.0 (2)C7B—C8B—C9B111.3 (2)
C7A—C8A—H8A1109.2C7B—C8B—H8B1109.4
C9A—C8A—H8A1109.2C9B—C8B—H8B1109.4
C7A—C8A—H8A2109.2C7B—C8B—H8B2109.4
C9A—C8A—H8A2109.2C9B—C8B—H8B2109.4
H8A1—C8A—H8A2107.9H8B1—C8B—H8B2108.0
N1A—C9A—C8A110.5 (2)N1B—C9B—C8B111.2 (2)
N1A—C9A—C10A113.6 (2)N1B—C9B—C10B114.0 (2)
C8A—C9A—C10A113.4 (2)C8B—C9B—C10B112.3 (2)
N1A—C9A—H9A106.2N1B—C9B—H9B106.2
C8A—C9A—H9A106.2C8B—C9B—H9B106.2
C10A—C9A—H9A106.2C10B—C9B—H9B106.2
O3A—C10A—C26A107.9 (2)O3B—C10B—C26B108.3 (2)
O3A—C10A—C32A109.5 (2)O3B—C10B—C32B108.8 (2)
C26A—C10A—C32A106.9 (2)C26B—C10B—C32B107.6 (2)
O3A—C10A—C9A108.5 (2)O3B—C10B—C9B109.2 (2)
C26A—C10A—C9A111.5 (2)C26B—C10B—C9B110.3 (2)
C32A—C10A—C9A112.5 (2)C32B—C10B—C9B112.6 (2)
N1A—C11A—C12A113.9 (2)N1B—C11B—C12B114.3 (2)
N1A—C11A—H11A108.8N1B—C11B—H11C108.7
C12A—C11A—H11A108.8C12B—C11B—H11C108.7
N1A—C11A—H11B108.8N1B—C11B—H11D108.7
C12A—C11A—H11B108.8C12B—C11B—H11D108.7
H11A—C11A—H11B107.7H11C—C11B—H11D107.6
C17A—C12A—C13A117.9 (3)C13B—C12B—C17B117.8 (3)
C17A—C12A—C11A123.5 (2)C13B—C12B—C11B123.4 (3)
C13A—C12A—C11A118.6 (3)C17B—C12B—C11B118.8 (3)
C12A—C13A—C14A120.1 (3)C12B—C13B—C14B120.2 (3)
C12A—C13A—H13A119.9C12B—C13B—H13B119.9
C14A—C13A—H13A119.9C14B—C13B—H13B119.9
C15A—C14A—C13A121.2 (3)C15B—C14B—C13B120.6 (4)
C15A—C14A—H14A119.4C15B—C14B—H14B119.7
C13A—C14A—H14A119.4C13B—C14B—H14B119.7
C14A—C15A—C16A119.0 (3)C16B—C15B—C14B119.5 (4)
C14A—C15A—H15A120.5C16B—C15B—H15B120.3
C16A—C15A—H15A120.5C14B—C15B—H15B120.3
C15A—C16A—C17A120.3 (3)C15B—C16B—C17B120.8 (3)
C15A—C16A—H16A119.9C15B—C16B—H16B119.6
C17A—C16A—H16A119.9C17B—C16B—H16B119.6
C16A—C17A—C12A121.4 (3)C16B—C17B—C12B121.1 (3)
C16A—C17A—H17A119.3C16B—C17B—H17B119.5
C12A—C17A—H17A119.3C12B—C17B—H17B119.5
C23A—C18A—C19A118.1 (3)C23B—C18B—C19B117.7 (3)
C23A—C18A—C1A123.1 (2)C23B—C18B—C1B123.4 (3)
C19A—C18A—C1A118.8 (2)C19B—C18B—C1B118.9 (2)
C20A—C19A—C18A120.9 (3)C18B—C19B—C20B121.1 (3)
C20A—C19A—H19A119.6C18B—C19B—H19B119.5
C18A—C19A—H19A119.6C20B—C19B—H19B119.5
C21A—C20A—C19A121.0 (3)C21B—C20B—C19B120.6 (3)
C21A—C20A—H20A119.5C21B—C20B—H20B119.7
C19A—C20A—H20A119.5C19B—C20B—H20B119.7
C20A—C21A—C22A118.9 (3)C20B—C21B—C22B119.3 (3)
C20A—C21A—H21A120.6C20B—C21B—H21B120.4
C22A—C21A—H21A120.6C22B—C21B—H21B120.4
C21A—C22A—C23A120.3 (3)C21B—C22B—C23B119.7 (3)
C21A—C22A—H22A119.8C21B—C22B—H22B120.1
C23A—C22A—H22A119.8C23B—C22B—H22B120.1
C18A—C23A—C22A120.8 (3)C18B—C23B—C22B121.4 (3)
C18A—C23A—H23A119.6C18B—C23B—H23B119.3
C22A—C23A—H23A119.6C22B—C23B—H23B119.3
O1A—C24A—H24A109.5O1B—C24B—H24D109.5
O1A—C24A—H24B109.5O1B—C24B—H24E109.5
H24A—C24A—H24B109.5H24D—C24B—H24E109.5
O1A—C24A—H24C109.5O1B—C24B—H24F109.5
H24A—C24A—H24C109.5H24D—C24B—H24F109.5
H24B—C24A—H24C109.5H24E—C24B—H24F109.5
O2A—C25A—H25A109.5O2B—C25B—H25D109.5
O2A—C25A—H25B109.5O2B—C25B—H25E109.5
H25A—C25A—H25B109.5H25D—C25B—H25E109.5
O2A—C25A—H25C109.5O2B—C25B—H25F109.5
H25A—C25A—H25C109.5H25D—C25B—H25F109.5
H25B—C25A—H25C109.5H25E—C25B—H25F109.5
C31A—C26A—C27A118.3 (3)C27B—C26B—C31B118.6 (3)
C31A—C26A—C10A122.0 (2)C27B—C26B—C10B121.4 (3)
C27A—C26A—C10A119.6 (2)C31B—C26B—C10B119.9 (2)
C28A—C27A—C26A120.5 (3)C28B—C27B—C26B120.5 (3)
C28A—C27A—H27A119.7C28B—C27B—H27B119.7
C26A—C27A—H27A119.7C26B—C27B—H27B119.7
C29A—C28A—C27A120.2 (3)C29B—C28B—C27B120.3 (3)
C29A—C28A—H28A119.9C29B—C28B—H28B119.8
C27A—C28A—H28A119.9C27B—C28B—H28B119.8
C30A—C29A—C28A119.7 (3)C30B—C29B—C28B119.3 (3)
C30A—C29A—H29A120.1C30B—C29B—H29B120.3
C28A—C29A—H29A120.1C28B—C29B—H29B120.3
C29A—C30A—C31A120.7 (3)C29B—C30B—C31B120.8 (3)
C29A—C30A—H30A119.6C29B—C30B—H30B119.6
C31A—C30A—H30A119.6C31B—C30B—H30B119.6
C30A—C31A—C26A120.5 (3)C30B—C31B—C26B120.5 (3)
C30A—C31A—H31A119.7C30B—C31B—H31B119.8
C26A—C31A—H31A119.7C26B—C31B—H31B119.8
C33A—C32A—C37A118.1 (3)C37B—C32B—C33B118.0 (3)
C33A—C32A—C10A124.5 (2)C37B—C32B—C10B125.2 (2)
C37A—C32A—C10A117.3 (2)C33B—C32B—C10B116.7 (2)
C34A—C33A—C32A120.7 (3)C34B—C33B—C32B121.0 (3)
C34A—C33A—H33A119.7C34B—C33B—H33B119.5
C32A—C33A—H33A119.7C32B—C33B—H33B119.5
C35A—C34A—C33A120.6 (3)C35B—C34B—C33B119.9 (3)
C35A—C34A—H34A119.7C35B—C34B—H34B120.0
C33A—C34A—H34A119.7C33B—C34B—H34B120.0
C34A—C35A—C36A119.7 (3)C34B—C35B—C36B119.9 (3)
C34A—C35A—H35A120.2C34B—C35B—H35B120.1
C36A—C35A—H35A120.2C36B—C35B—H35B120.1
C37A—C36A—C35A119.3 (3)C35B—C36B—C37B120.5 (3)
C37A—C36A—H36A120.3C35B—C36B—H36B119.8
C35A—C36A—H36A120.3C37B—C36B—H36B119.8
C36A—C37A—C32A121.5 (3)C32B—C37B—C36B120.7 (3)
C36A—C37A—H37A119.2C32B—C37B—H37B119.6
C32A—C37A—H37A119.2C36B—C37B—H37B119.6
Si1A—C38A—H38A109.5Si1B—C38B—H38D109.5
Si1A—C38A—H38B109.5Si1B—C38B—H38E109.5
H38A—C38A—H38B109.5H38D—C38B—H38E109.5
Si1A—C38A—H38C109.5Si1B—C38B—H38F109.5
H38A—C38A—H38C109.5H38D—C38B—H38F109.5
H38B—C38A—H38C109.5H38E—C38B—H38F109.5
Si1A—C39A—H39A109.5Si1B—C39B—H39D109.5
Si1A—C39A—H39B109.5Si1B—C39B—H39E109.5
H39A—C39A—H39B109.5H39D—C39B—H39E109.5
Si1A—C39A—H39C109.5Si1B—C39B—H39F109.5
H39A—C39A—H39C109.5H39D—C39B—H39F109.5
H39B—C39A—H39C109.5H39E—C39B—H39F109.5
Si1A—C40A—H40A109.5Si1B—C40B—H40D109.5
Si1A—C40A—H40B109.5Si1B—C40B—H40E109.5
H40A—C40A—H40B109.5H40D—C40B—H40E109.5
Si1A—C40A—H40C109.5Si1B—C40B—H40F109.5
H40A—C40A—H40C109.5H40D—C40B—H40F109.5
H40B—C40A—H40C109.5H40E—C40B—H40F109.5
C40A—Si1A—O3A—C10A30.2 (3)C38B—Si1B—O3B—C10B138.9 (3)
C38A—Si1A—O3A—C10A149.7 (2)C39B—Si1B—O3B—C10B−105.6 (3)
C39A—Si1A—O3A—C10A−92.3 (3)C40B—Si1B—O3B—C10B17.3 (3)
C11A—N1A—C1A—C2A72.9 (3)C11B—N1B—C1B—C2B73.3 (3)
C9A—N1A—C1A—C2A−53.1 (3)C9B—N1B—C1B—C2B−51.7 (3)
C11A—N1A—C1A—C18A−160.1 (2)C11B—N1B—C1B—C18B−157.9 (2)
C9A—N1A—C1A—C18A74.0 (3)C9B—N1B—C1B—C18B77.1 (3)
N1A—C1A—C2A—C7A20.3 (3)N1B—C1B—C2B—C7B17.6 (3)
C18A—C1A—C2A—C7A−104.8 (3)C18B—C1B—C2B—C7B−109.7 (3)
N1A—C1A—C2A—C3A−160.8 (2)N1B—C1B—C2B—C3B−162.3 (2)
C18A—C1A—C2A—C3A74.1 (3)C18B—C1B—C2B—C3B70.5 (3)
C7A—C2A—C3A—C4A1.0 (4)C7B—C2B—C3B—C4B−1.2 (4)
C1A—C2A—C3A—C4A−177.9 (2)C1B—C2B—C3B—C4B178.7 (2)
C24A—O1A—C4A—C3A−4.8 (4)C24B—O1B—C4B—C3B−9.8 (4)
C24A—O1A—C4A—C5A175.1 (2)C24B—O1B—C4B—C5B170.9 (2)
C2A—C3A—C4A—O1A177.0 (2)C2B—C3B—C4B—O1B177.9 (2)
C2A—C3A—C4A—C5A−2.9 (4)C2B—C3B—C4B—C5B−2.8 (4)
C25A—O2A—C5A—C6A8.1 (4)C25B—O2B—C5B—C6B0.9 (4)
C25A—O2A—C5A—C4A−172.5 (2)C25B—O2B—C5B—C4B−179.7 (3)
O1A—C4A—C5A—O2A2.9 (3)O1B—C4B—C5B—O2B3.7 (4)
C3A—C4A—C5A—O2A−177.2 (2)C3B—C4B—C5B—O2B−175.7 (2)
O1A—C4A—C5A—C6A−177.7 (2)O1B—C4B—C5B—C6B−176.9 (2)
C3A—C4A—C5A—C6A2.3 (4)C3B—C4B—C5B—C6B3.8 (4)
O2A—C5A—C6A—C7A179.6 (2)O2B—C5B—C6B—C7B178.6 (2)
C4A—C5A—C6A—C7A0.2 (4)C4B—C5B—C6B—C7B−0.9 (4)
C3A—C2A—C7A—C6A1.4 (4)C3B—C2B—C7B—C6B4.2 (4)
C1A—C2A—C7A—C6A−179.6 (2)C1B—C2B—C7B—C6B−175.7 (2)
C3A—C2A—C7A—C8A−179.2 (2)C3B—C2B—C7B—C8B−177.2 (2)
C1A—C2A—C7A—C8A−0.2 (4)C1B—C2B—C7B—C8B2.9 (4)
C5A—C6A—C7A—C2A−2.0 (4)C5B—C6B—C7B—C2B−3.2 (4)
C5A—C6A—C7A—C8A178.6 (2)C5B—C6B—C7B—C8B178.2 (3)
C2A—C7A—C8A—C9A13.2 (3)C2B—C7B—C8B—C9B11.4 (4)
C6A—C7A—C8A—C9A−167.4 (2)C6B—C7B—C8B—C9B−170.0 (2)
C11A—N1A—C9A—C8A−57.8 (3)C11B—N1B—C9B—C8B−56.9 (3)
C1A—N1A—C9A—C8A67.3 (3)C1B—N1B—C9B—C8B67.8 (3)
C11A—N1A—C9A—C10A70.9 (3)C11B—N1B—C9B—C10B71.3 (3)
C1A—N1A—C9A—C10A−163.9 (2)C1B—N1B—C9B—C10B−163.9 (2)
C7A—C8A—C9A—N1A−46.8 (3)C7B—C8B—C9B—N1B−46.9 (3)
C7A—C8A—C9A—C10A−175.7 (2)C7B—C8B—C9B—C10B−176.0 (2)
Si1A—O3A—C10A—C26A130.4 (2)Si1B—O3B—C10B—C26B137.0 (2)
Si1A—O3A—C10A—C32A14.4 (3)Si1B—O3B—C10B—C32B20.3 (3)
Si1A—O3A—C10A—C9A−108.7 (3)Si1B—O3B—C10B—C9B−103.0 (3)
N1A—C9A—C10A—O3A−84.8 (3)N1B—C9B—C10B—O3B−81.1 (3)
C8A—C9A—C10A—O3A42.4 (3)C8B—C9B—C10B—O3B46.5 (3)
N1A—C9A—C10A—C26A33.8 (3)N1B—C9B—C10B—C26B37.7 (3)
C8A—C9A—C10A—C26A161.1 (2)C8B—C9B—C10B—C26B165.3 (2)
N1A—C9A—C10A—C32A153.9 (2)N1B—C9B—C10B—C32B157.9 (2)
C8A—C9A—C10A—C32A−78.9 (3)C8B—C9B—C10B—C32B−74.5 (3)
C9A—N1A—C11A—C12A−171.0 (2)C9B—N1B—C11B—C12B−171.9 (2)
C1A—N1A—C11A—C12A66.1 (3)C1B—N1B—C11B—C12B65.8 (3)
N1A—C11A—C12A—C17A31.6 (4)N1B—C11B—C12B—C13B29.3 (4)
N1A—C11A—C12A—C13A−150.3 (2)N1B—C11B—C12B—C17B−152.6 (3)
C17A—C12A—C13A—C14A−0.8 (4)C17B—C12B—C13B—C14B2.3 (5)
C11A—C12A—C13A—C14A−179.0 (3)C11B—C12B—C13B—C14B−179.6 (3)
C12A—C13A—C14A—C15A−1.5 (5)C12B—C13B—C14B—C15B−2.8 (5)
C13A—C14A—C15A—C16A2.0 (5)C13B—C14B—C15B—C16B0.8 (6)
C14A—C15A—C16A—C17A−0.3 (5)C14B—C15B—C16B—C17B1.5 (6)
C15A—C16A—C17A—C12A−2.0 (5)C15B—C16B—C17B—C12B−1.9 (5)
C13A—C12A—C17A—C16A2.5 (4)C13B—C12B—C17B—C16B0.0 (5)
C11A—C12A—C17A—C16A−179.4 (3)C11B—C12B—C17B—C16B−178.2 (3)
N1A—C1A—C18A—C23A−118.5 (3)N1B—C1B—C18B—C23B−115.4 (3)
C2A—C1A—C18A—C23A8.6 (4)C2B—C1B—C18B—C23B13.3 (4)
N1A—C1A—C18A—C19A62.0 (3)N1B—C1B—C18B—C19B66.7 (3)
C2A—C1A—C18A—C19A−170.8 (2)C2B—C1B—C18B—C19B−164.6 (3)
C23A—C18A—C19A—C20A−0.7 (4)C23B—C18B—C19B—C20B−3.7 (5)
C1A—C18A—C19A—C20A178.8 (3)C1B—C18B—C19B—C20B174.3 (3)
C18A—C19A—C20A—C21A−0.5 (5)C18B—C19B—C20B—C21B1.8 (5)
C19A—C20A—C21A—C22A1.2 (5)C19B—C20B—C21B—C22B1.7 (5)
C20A—C21A—C22A—C23A−0.9 (4)C20B—C21B—C22B—C23B−3.1 (5)
C19A—C18A—C23A—C22A1.0 (4)C19B—C18B—C23B—C22B2.3 (4)
C1A—C18A—C23A—C22A−178.5 (2)C1B—C18B—C23B—C22B−175.6 (3)
C21A—C22A—C23A—C18A−0.2 (4)C21B—C22B—C23B—C18B1.1 (5)
O3A—C10A—C26A—C31A−8.9 (3)O3B—C10B—C26B—C27B−4.4 (4)
C32A—C10A—C26A—C31A108.8 (3)C32B—C10B—C26B—C27B113.0 (3)
C9A—C10A—C26A—C31A−127.9 (3)C9B—C10B—C26B—C27B−123.8 (3)
O3A—C10A—C26A—C27A175.6 (2)O3B—C10B—C26B—C31B−179.7 (2)
C32A—C10A—C26A—C27A−66.7 (3)C32B—C10B—C26B—C31B−62.3 (3)
C9A—C10A—C26A—C27A56.6 (3)C9B—C10B—C26B—C31B60.9 (3)
C31A—C26A—C27A—C28A−0.9 (4)C31B—C26B—C27B—C28B−0.3 (5)
C10A—C26A—C27A—C28A174.8 (2)C10B—C26B—C27B—C28B−175.6 (3)
C26A—C27A—C28A—C29A−0.5 (4)C26B—C27B—C28B—C29B1.0 (5)
C27A—C28A—C29A—C30A1.3 (4)C27B—C28B—C29B—C30B−1.4 (5)
C28A—C29A—C30A—C31A−0.8 (5)C28B—C29B—C30B—C31B1.1 (5)
C29A—C30A—C31A—C26A−0.6 (4)C29B—C30B—C31B—C26B−0.3 (4)
C27A—C26A—C31A—C30A1.4 (4)C27B—C26B—C31B—C30B−0.1 (4)
C10A—C26A—C31A—C30A−174.2 (3)C10B—C26B—C31B—C30B175.3 (3)
O3A—C10A—C32A—C33A−111.0 (3)O3B—C10B—C32B—C37B−119.0 (3)
C26A—C10A—C32A—C33A132.4 (3)C26B—C10B—C32B—C37B123.8 (3)
C9A—C10A—C32A—C33A9.7 (4)C9B—C10B—C32B—C37B2.1 (4)
O3A—C10A—C32A—C37A67.6 (3)O3B—C10B—C32B—C33B59.9 (3)
C26A—C10A—C32A—C37A−49.0 (3)C26B—C10B—C32B—C33B−57.2 (3)
C9A—C10A—C32A—C37A−171.7 (2)C9B—C10B—C32B—C33B−178.9 (2)
C37A—C32A—C33A—C34A−2.4 (4)C37B—C32B—C33B—C34B1.2 (4)
C10A—C32A—C33A—C34A176.2 (2)C10B—C32B—C33B—C34B−177.8 (2)
C32A—C33A—C34A—C35A1.8 (4)C32B—C33B—C34B—C35B0.4 (4)
C33A—C34A—C35A—C36A−0.2 (4)C33B—C34B—C35B—C36B−1.3 (4)
C34A—C35A—C36A—C37A−0.6 (4)C34B—C35B—C36B—C37B0.6 (5)
C35A—C36A—C37A—C32A−0.1 (4)C33B—C32B—C37B—C36B−2.0 (4)
C33A—C32A—C37A—C36A1.6 (4)C10B—C32B—C37B—C36B177.0 (3)
C10A—C32A—C37A—C36A−177.2 (2)C35B—C36B—C37B—C32B1.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C35A—H35A···Cgi0.952.803.669 (3)152
C40A—H40B···Cg0.982.713.540 (3)143
C40B—H40D···Cg0.982.643.449 (4)140
Symmetry code: (i) −x+1, y+1/2, −z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC31H31NO3C40H43NO3Si
Mr465.57613.84
Crystal system, space groupMonoclinic, P21Monoclinic, P21
Temperature (K)173100
a, b, c (Å)11.4071 (14), 6.4750 (8), 16.961 (2)11.045 (10), 17.008 (15), 18.489 (15)
β (°) 101.707 (2) 105.287 (15)
V (Å3)1226.7 (3)3350 (5)
Z24
Radiation typeMo KαMo Kα
µ (mm−1)0.080.11
Crystal size (mm)0.22 × 0.14 × 0.090.22 × 0.12 × 0.10
Data collection
DiffractometerBruker APEXII DUO
diffractometer		Bruker APEXII DUO
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)		Multi-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.645, 0.7460.976, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections		11498, 3737, 3191 37993, 17263, 11255
Rint0.0510.064
(sin θ/λ)max (Å−1)0.6970.681
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.108, 1.05 0.057, 0.124, 0.99
No. of reflections373717263
No. of parameters320812
No. of restraints21
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.23, −0.230.38, −0.41
Absolute structure?Flack (1983)
Absolute structure parameter?0.00 (10)

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···Cgi0.982.573.45 (2)150
C30—H30A···O1ii0.982.543.356 (2)140
C30—H30A···O2ii0.982.593.400 (2)140
Symmetry codes: (i) x, y+1, z; (ii) −x, y−1/2, −z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C35A—H35A···Cgi0.952.803.669 (3)152
C40A—H40B···Cg0.982.713.540 (3)143
C40B—H40D···Cg0.982.643.449 (4)140
Symmetry code: (i) −x+1, y+1/2, −z+1.
 

Acknowledgements

The authors thank Dr Hong Su of the Chemistry Department of the University of Cape Town for her assistance with the crystallographic data collection.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 3| March 2011| Pages o100-o103
doi:10.1107/S0108270110053357
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