Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108036238/ga3110sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108036238/ga3110IIIsup2.hkl |
CCDC reference: 718139
Pyridoxal-N-(o-hydroxypenyl)imine, (I), was prepared as follows. To pyridoxal hydrochloride (4.06 g, 20 mmol) dissolved in methanol was added a solution of sodium methanolate (1.08 g, 20 mmol) in methanol. A solution of o-aminophenol (2.18 g, 20 mmol) in methanol was added dropwise. The suspension was boiled at reflux temperature. The colour of the solution became orange and a precipitate was formed. After 2 h, the suspension was cooled to room temperature and the precipitate was filtered off. The solid was washed with small amounts of water to remove sodium chloride, followed by diethyl ether. Compound (I) was obtained as an orange solid (yield 4.13 g, 80%; m.p. 495 K).
The preparation of (III) was performed in Schlenk tubes under argon with dry and air-free solvents. Compound (III) was prepared by the reaction of triethylamine (1.7 ml, 1.21 g, 12.0 mmol) and dichlorodiphenylsilane (1.22 g, 4.8 mmol) with (I) (1.25 g, 4.8 mmol) in dry tetrahydrofuran at room temperature. A white precipitate of triethylamine hydrocloride formed upon stirring the mixture for 6 d. After this period, the triethylamine hydrocloride was filtered off and washed with tetrahydrofuran. The solvent was removed in vacuo from the resulting clear red solution. The remaining solid was extracted with 1,2-dimethoxyethane. Addition of hexane, cooling to 278 K and filtration of this sample gave a red solid product (yield 1.48 g, 70.3%; m.p. 485 K). Single crystals of the title compound, (III).4CHCl3, were obtained by recrystallization from CHCl3.
NMR data are available in the archived CIF.
The final automatic data collection scan could not be completed due to loss of the crystal from the beam, with a subsequent gap in the inner-shell data.
One of the two symmetry-independent chloroform molecules is disordered over two orientations. The site occupation factors were refined and gave a final value of 0.739 (11) for the major orientation (Cl4A-Cl6A). Rigid bond restraints were applied to the Uij-values of one phenyl ring (C24-C26) and to the disordered chloroform molecule at C28 [12 restraints with the DELU command in SHELXL (Sheldrick, 2008)]. Further restraints were used to generate similar Uij-values and to restrain the atoms to be approximately isotropic for the atoms of one phenyl ring and for both chloroform molecules (30 restraints with the SIMU command and 84 restraints with the ISOR command in SHELXL).
All C-bound H atoms were positioned geometrically, with C—H = 0.95, 0.98, 0.99 or 1.00 Å for aryl-H, CH3, CH2 or tertiary C—H, respectively, and refined in riding mode, with Uiso(H) = 1.5Ueq(C) for methyl H or 1.2Ueq(C) for all other H. The H atom bonded to O1 was positioned geometrically, with O—H = 0.84 Å, and refined in riding mode, with Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C52H44N4O6Si2·4CHCl3 | Z = 1 |
Mr = 1354.56 | F(000) = 692 |
Triclinic, P1 | Dx = 1.474 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8831 (3) Å | Cell parameters from 8116 reflections |
b = 11.2094 (3) Å | θ = 2.2–30.5° |
c = 14.7584 (4) Å | µ = 0.64 mm−1 |
α = 102.853 (2)° | T = 153 K |
β = 101.899 (1)° | Prism, orange |
γ = 98.733 (1)° | 0.33 × 0.30 × 0.22 mm |
V = 1525.91 (8) Å3 |
Bruker SMART CCD area-detector diffractometer | 6493 independent reflections |
Radiation source: sealed tube | 5116 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.818, Tmax = 0.873 | k = −13→12 |
14146 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.048P)2 + 1.0265P] where P = (Fo2 + 2Fc2)/3 |
6493 reflections | (Δ/σ)max = 0.001 |
391 parameters | Δρmax = 0.62 e Å−3 |
126 restraints | Δρmin = −0.44 e Å−3 |
C52H44N4O6Si2·4CHCl3 | γ = 98.733 (1)° |
Mr = 1354.56 | V = 1525.91 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.8831 (3) Å | Mo Kα radiation |
b = 11.2094 (3) Å | µ = 0.64 mm−1 |
c = 14.7584 (4) Å | T = 153 K |
α = 102.853 (2)° | 0.33 × 0.30 × 0.22 mm |
β = 101.899 (1)° |
Bruker SMART CCD area-detector diffractometer | 6493 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5116 reflections with I > 2σ(I) |
Tmin = 0.818, Tmax = 0.873 | Rint = 0.019 |
14146 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 126 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.62 e Å−3 |
6493 reflections | Δρmin = −0.44 e Å−3 |
391 parameters |
Experimental. Pyridoxal-N-(o-hydroxypenyl)imine, (I): 1H NMR (DMSO, δ, p.p.m.): 14.72, 10.04 (s, OH, 2H), 9.25 (s, HC═N, 1H), 8.0–6.89 (m, CHaromatic, 5H), 5.43 (CH2—OH, 1H), 4.78 (CH2—OH, 2H), 2.44 (CH3, 3H); 13C NMR (DMSO, δ, p.p.m.): 158.6 (C═N), 153.8, 151.7, 148.5, 137.6, 134.1, 133.3, 129.2, 120.1, 119.7 (2 C), 116.8 (10 signals for aromatic C), 58.5 (CH2—OH), 18.9 (CH3). Cyclo-bis{5-(oxymethyl)-4-{(E)-[(2-oxyphenyl)imino]methyl}- 2-methylpyridin-3-ol}diphenylsilane}, (III): 1H NMR (CDCl3, δ, p.p.m.): 14.31 (s, OH, 1H), 8.90 (s, HC═N, 1H), 7.97–6.56 (m, CHaromatic, 15H), 5.13 (CH2—O, 1H), 2.37 (CH3, 3H); 13C NMR (CDCl3, δ, p.p.m.): 157.4 (C═N), 154.3, 150.7, 148.0, 139.7, 137.1, 135.2, 134.9, 131.5, 131.2, 129.9, 129.4, 128.4, 122.1, 119.8, 119.5, 119.0 (signals for aromatic C), 60.8 (CH2—O), 19.1 (CH3); 29Si NMR (CDCl3, δ, p.p.m.): -32.8. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Si1 | 0.40784 (8) | 0.74702 (7) | 0.22233 (5) | 0.02333 (17) | |
O1 | 0.7646 (2) | 0.54183 (18) | 0.18553 (13) | 0.0302 (4) | |
H1 | 0.7257 | 0.5863 | 0.1537 | 0.045* | |
O2 | 0.75599 (19) | 0.24697 (16) | −0.17905 (13) | 0.0254 (4) | |
O3 | 0.49024 (19) | 0.69992 (17) | 0.13786 (13) | 0.0260 (4) | |
N1 | 0.9600 (3) | 0.3049 (2) | 0.12183 (17) | 0.0306 (5) | |
N2 | 0.6701 (2) | 0.61316 (19) | 0.03971 (15) | 0.0230 (4) | |
C1 | 0.8957 (3) | 0.3828 (3) | 0.17146 (19) | 0.0292 (6) | |
C2 | 0.8220 (3) | 0.4631 (2) | 0.12955 (18) | 0.0244 (5) | |
C3 | 0.8101 (3) | 0.4583 (2) | 0.03194 (18) | 0.0221 (5) | |
C4 | 0.8774 (3) | 0.3740 (2) | −0.01919 (18) | 0.0233 (5) | |
C5 | 0.9512 (3) | 0.3025 (2) | 0.0296 (2) | 0.0279 (6) | |
H5 | 0.9991 | 0.2479 | −0.0046 | 0.033* | |
C6 | 0.9035 (4) | 0.3833 (3) | 0.2737 (2) | 0.0458 (8) | |
H6A | 0.9479 | 0.3153 | 0.2887 | 0.069* | |
H6B | 0.8078 | 0.3715 | 0.2837 | 0.069* | |
H6C | 0.9597 | 0.4635 | 0.3158 | 0.069* | |
C7 | 0.7281 (3) | 0.5382 (2) | −0.01164 (18) | 0.0227 (5) | |
H7 | 0.7177 | 0.5347 | −0.0777 | 0.027* | |
C8 | 0.8687 (3) | 0.3516 (2) | −0.12524 (19) | 0.0256 (5) | |
H8A | 0.8517 | 0.4273 | −0.1459 | 0.031* | |
H8B | 0.9595 | 0.3345 | −0.1378 | 0.031* | |
C9 | 0.5879 (3) | 0.6924 (2) | 0.00303 (18) | 0.0230 (5) | |
C10 | 0.4977 (3) | 0.7404 (2) | 0.05728 (18) | 0.0225 (5) | |
C11 | 0.4162 (3) | 0.8214 (2) | 0.0269 (2) | 0.0273 (6) | |
H11 | 0.3564 | 0.8548 | 0.0641 | 0.033* | |
C12 | 0.4223 (3) | 0.8534 (2) | −0.0580 (2) | 0.0300 (6) | |
H12 | 0.3648 | 0.9073 | −0.0794 | 0.036* | |
C13 | 0.5112 (3) | 0.8077 (3) | −0.1116 (2) | 0.0325 (6) | |
H13 | 0.5151 | 0.8301 | −0.1695 | 0.039* | |
C14 | 0.5947 (3) | 0.7289 (3) | −0.0806 (2) | 0.0289 (6) | |
H14 | 0.6576 | 0.6993 | −0.1168 | 0.035* | |
C15 | 0.4068 (3) | 0.6253 (2) | 0.28974 (19) | 0.0272 (6) | |
C16 | 0.4871 (3) | 0.5331 (3) | 0.2805 (2) | 0.0355 (7) | |
H16 | 0.5501 | 0.5331 | 0.2398 | 0.043* | |
C17 | 0.4764 (4) | 0.4414 (3) | 0.3299 (2) | 0.0456 (8) | |
H17 | 0.5321 | 0.3795 | 0.3230 | 0.055* | |
C18 | 0.3851 (4) | 0.4399 (3) | 0.3890 (2) | 0.0464 (8) | |
H18 | 0.3772 | 0.3768 | 0.4223 | 0.056* | |
C19 | 0.3055 (4) | 0.5306 (4) | 0.3995 (2) | 0.0485 (8) | |
H19 | 0.2429 | 0.5304 | 0.4405 | 0.058* | |
C20 | 0.3164 (4) | 0.6220 (3) | 0.3505 (2) | 0.0407 (7) | |
H20 | 0.2610 | 0.6840 | 0.3585 | 0.049* | |
C21 | 0.4954 (3) | 0.9093 (2) | 0.29126 (19) | 0.0263 (5) | |
C22 | 0.6293 (4) | 0.9606 (3) | 0.2866 (2) | 0.0445 (8) | |
H22 | 0.6755 | 0.9125 | 0.2459 | 0.053* | |
C23 | 0.6980 (4) | 1.0810 (3) | 0.3400 (3) | 0.0525 (9) | |
H23 | 0.7901 | 1.1144 | 0.3358 | 0.063* | |
C24 | 0.6330 (4) | 1.1509 (3) | 0.3983 (3) | 0.0466 (8) | |
H24 | 0.6799 | 1.2330 | 0.4353 | 0.056* | |
C25 | 0.5015 (4) | 1.1036 (4) | 0.4034 (3) | 0.0670 (12) | |
H25 | 0.4562 | 1.1531 | 0.4438 | 0.080* | |
C26 | 0.4319 (4) | 0.9835 (3) | 0.3503 (3) | 0.0551 (10) | |
H26 | 0.3393 | 0.9519 | 0.3547 | 0.066* | |
C27 | 1.0270 (3) | 0.0594 (3) | 0.1747 (2) | 0.0359 (7) | |
H27 | 0.9915 | 0.1322 | 0.1572 | 0.043* | |
Cl1 | 0.88490 (10) | −0.07058 (9) | 0.13523 (7) | 0.0545 (2) | |
Cl2 | 1.16119 (9) | 0.03107 (9) | 0.11692 (7) | 0.0524 (2) | |
Cl3 | 1.09058 (11) | 0.09797 (9) | 0.30019 (6) | 0.0538 (2) | |
C28 | 0.8845 (4) | 0.7219 (3) | 0.4064 (2) | 0.0460 (8) | |
H28 | 0.8334 | 0.6530 | 0.3480 | 0.055* | |
Cl4A | 0.7605 (3) | 0.7944 (4) | 0.45433 (12) | 0.0590 (7) | 0.739 (11) |
Cl5A | 0.9835 (4) | 0.6569 (2) | 0.49168 (15) | 0.0449 (5) | 0.739 (11) |
Cl6A | 1.0098 (4) | 0.8238 (4) | 0.3757 (3) | 0.0964 (10) | 0.739 (11) |
Cl4B | 0.7961 (10) | 0.8394 (9) | 0.4523 (5) | 0.0694 (18) | 0.261 (11) |
Cl5B | 0.9414 (9) | 0.6478 (7) | 0.4918 (5) | 0.0435 (14) | 0.261 (11) |
Cl6B | 0.9858 (8) | 0.8023 (7) | 0.3529 (5) | 0.0538 (17) | 0.261 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0247 (4) | 0.0214 (4) | 0.0237 (4) | 0.0059 (3) | 0.0060 (3) | 0.0049 (3) |
O1 | 0.0381 (11) | 0.0319 (11) | 0.0235 (9) | 0.0173 (9) | 0.0085 (8) | 0.0058 (8) |
O2 | 0.0240 (9) | 0.0231 (9) | 0.0259 (9) | 0.0045 (7) | 0.0041 (7) | 0.0022 (7) |
O3 | 0.0314 (10) | 0.0244 (9) | 0.0265 (10) | 0.0101 (8) | 0.0101 (8) | 0.0098 (7) |
N1 | 0.0340 (13) | 0.0253 (12) | 0.0312 (12) | 0.0108 (10) | 0.0033 (10) | 0.0060 (9) |
N2 | 0.0221 (11) | 0.0207 (10) | 0.0257 (11) | 0.0051 (8) | 0.0043 (9) | 0.0059 (8) |
C1 | 0.0331 (15) | 0.0263 (14) | 0.0258 (13) | 0.0082 (11) | 0.0016 (11) | 0.0055 (11) |
C2 | 0.0247 (13) | 0.0212 (12) | 0.0240 (13) | 0.0028 (10) | 0.0034 (10) | 0.0029 (10) |
C3 | 0.0199 (12) | 0.0183 (12) | 0.0249 (13) | 0.0013 (9) | 0.0031 (10) | 0.0032 (10) |
C4 | 0.0212 (12) | 0.0205 (12) | 0.0251 (13) | 0.0010 (10) | 0.0049 (10) | 0.0027 (10) |
C5 | 0.0276 (14) | 0.0213 (13) | 0.0324 (14) | 0.0065 (10) | 0.0064 (11) | 0.0026 (11) |
C6 | 0.069 (2) | 0.048 (2) | 0.0267 (15) | 0.0298 (17) | 0.0080 (15) | 0.0130 (14) |
C7 | 0.0224 (13) | 0.0203 (12) | 0.0229 (12) | 0.0016 (10) | 0.0031 (10) | 0.0049 (10) |
C8 | 0.0243 (13) | 0.0231 (13) | 0.0277 (13) | 0.0040 (10) | 0.0068 (10) | 0.0032 (10) |
C9 | 0.0229 (13) | 0.0181 (12) | 0.0250 (13) | 0.0029 (9) | 0.0014 (10) | 0.0049 (10) |
C10 | 0.0229 (13) | 0.0181 (12) | 0.0238 (12) | 0.0009 (9) | 0.0041 (10) | 0.0038 (9) |
C11 | 0.0260 (14) | 0.0220 (13) | 0.0346 (15) | 0.0058 (10) | 0.0076 (11) | 0.0083 (11) |
C12 | 0.0302 (15) | 0.0222 (13) | 0.0376 (15) | 0.0067 (11) | 0.0029 (12) | 0.0119 (11) |
C13 | 0.0404 (17) | 0.0306 (15) | 0.0286 (14) | 0.0067 (12) | 0.0074 (12) | 0.0136 (12) |
C14 | 0.0337 (15) | 0.0283 (14) | 0.0278 (14) | 0.0088 (11) | 0.0110 (11) | 0.0086 (11) |
C15 | 0.0277 (14) | 0.0264 (14) | 0.0247 (13) | 0.0030 (11) | 0.0032 (11) | 0.0059 (10) |
C16 | 0.0398 (17) | 0.0360 (16) | 0.0366 (16) | 0.0130 (13) | 0.0130 (13) | 0.0148 (13) |
C17 | 0.062 (2) | 0.0389 (18) | 0.0443 (19) | 0.0213 (16) | 0.0134 (16) | 0.0198 (15) |
C18 | 0.066 (2) | 0.0386 (18) | 0.0364 (17) | 0.0049 (16) | 0.0103 (16) | 0.0189 (14) |
C19 | 0.056 (2) | 0.057 (2) | 0.0415 (19) | 0.0114 (17) | 0.0238 (16) | 0.0223 (16) |
C20 | 0.0487 (19) | 0.0459 (19) | 0.0376 (17) | 0.0195 (15) | 0.0198 (15) | 0.0167 (14) |
C21 | 0.0271 (14) | 0.0249 (13) | 0.0260 (13) | 0.0073 (11) | 0.0030 (11) | 0.0067 (10) |
C22 | 0.0408 (18) | 0.0389 (17) | 0.0490 (19) | −0.0013 (14) | 0.0213 (15) | −0.0011 (15) |
C23 | 0.042 (2) | 0.0424 (19) | 0.061 (2) | −0.0114 (15) | 0.0145 (17) | 0.0021 (17) |
C24 | 0.050 (2) | 0.0270 (16) | 0.050 (2) | −0.0013 (14) | 0.0017 (16) | 0.0006 (14) |
C25 | 0.059 (2) | 0.0407 (19) | 0.088 (3) | 0.0083 (17) | 0.031 (2) | −0.0194 (19) |
C26 | 0.0391 (18) | 0.0397 (18) | 0.078 (2) | 0.0035 (14) | 0.0256 (17) | −0.0092 (17) |
C27 | 0.0429 (17) | 0.0337 (16) | 0.0371 (16) | 0.0168 (13) | 0.0141 (13) | 0.0118 (13) |
Cl1 | 0.0489 (5) | 0.0575 (5) | 0.0541 (5) | 0.0015 (4) | 0.0250 (4) | 0.0039 (4) |
Cl2 | 0.0475 (5) | 0.0516 (5) | 0.0648 (5) | 0.0118 (4) | 0.0289 (4) | 0.0137 (4) |
Cl3 | 0.0656 (5) | 0.0547 (5) | 0.0400 (4) | 0.0184 (4) | 0.0073 (4) | 0.0119 (4) |
C28 | 0.056 (2) | 0.049 (2) | 0.0309 (16) | 0.0113 (16) | 0.0061 (15) | 0.0120 (14) |
Cl4A | 0.0505 (9) | 0.0732 (12) | 0.0538 (8) | 0.0194 (8) | 0.0102 (6) | 0.0158 (7) |
Cl5A | 0.0490 (10) | 0.0475 (8) | 0.0372 (7) | 0.0103 (7) | 0.0035 (7) | 0.0156 (5) |
Cl6A | 0.0993 (14) | 0.1004 (14) | 0.1016 (15) | −0.0004 (9) | 0.0286 (10) | 0.0619 (11) |
Cl4B | 0.069 (2) | 0.069 (2) | 0.071 (2) | 0.0206 (13) | 0.0150 (11) | 0.0179 (12) |
Cl5B | 0.0456 (19) | 0.0456 (17) | 0.0402 (16) | 0.0078 (12) | 0.0106 (12) | 0.0144 (10) |
Cl6B | 0.057 (2) | 0.056 (2) | 0.0489 (19) | 0.0023 (11) | 0.0145 (11) | 0.0203 (12) |
Si1—O2i | 1.6310 (19) | C13—H13 | 0.9500 |
Si1—O3 | 1.6591 (19) | C14—H14 | 0.9500 |
Si1—C21 | 1.852 (3) | C15—C20 | 1.392 (4) |
Si1—C15 | 1.859 (3) | C15—C16 | 1.395 (4) |
O1—C2 | 1.344 (3) | C16—C17 | 1.391 (4) |
O1—H1 | 0.8400 | C16—H16 | 0.9500 |
O2—C8 | 1.439 (3) | C17—C18 | 1.378 (5) |
O2—Si1i | 1.6310 (19) | C17—H17 | 0.9500 |
O3—C10 | 1.376 (3) | C18—C19 | 1.379 (5) |
N1—C1 | 1.334 (4) | C18—H18 | 0.9500 |
N1—C5 | 1.339 (4) | C19—C20 | 1.383 (5) |
N2—C7 | 1.285 (3) | C19—H19 | 0.9500 |
N2—C9 | 1.412 (3) | C20—H20 | 0.9500 |
C1—C2 | 1.408 (4) | C21—C26 | 1.381 (4) |
C1—C6 | 1.494 (4) | C21—C22 | 1.383 (4) |
C2—C3 | 1.409 (4) | C22—C23 | 1.389 (5) |
C3—C4 | 1.409 (4) | C22—H22 | 0.9500 |
C3—C7 | 1.460 (3) | C23—C24 | 1.359 (5) |
C4—C5 | 1.382 (4) | C23—H23 | 0.9500 |
C4—C8 | 1.511 (4) | C24—C25 | 1.351 (5) |
C5—H5 | 0.9500 | C24—H24 | 0.9500 |
C6—H6A | 0.9800 | C25—C26 | 1.388 (5) |
C6—H6B | 0.9800 | C25—H25 | 0.9500 |
C6—H6C | 0.9800 | C26—H26 | 0.9500 |
C7—H7 | 0.9500 | C27—Cl2 | 1.749 (3) |
C8—H8A | 0.9900 | C27—Cl3 | 1.759 (3) |
C8—H8B | 0.9900 | C27—Cl1 | 1.760 (3) |
C9—C14 | 1.395 (4) | C27—H27 | 1.0000 |
C9—C10 | 1.404 (4) | C28—Cl6B | 1.676 (8) |
C10—C11 | 1.388 (4) | C28—Cl5B | 1.705 (8) |
C11—C12 | 1.388 (4) | C28—Cl4A | 1.751 (4) |
C11—H11 | 0.9500 | C28—Cl6A | 1.755 (5) |
C12—C13 | 1.380 (4) | C28—Cl4B | 1.776 (7) |
C12—H12 | 0.9500 | C28—Cl5A | 1.785 (4) |
C13—C14 | 1.384 (4) | C28—H28 | 1.0000 |
O2i—Si1—O3 | 113.09 (10) | C20—C15—Si1 | 118.4 (2) |
O2i—Si1—C21 | 105.25 (11) | C16—C15—Si1 | 124.1 (2) |
O3—Si1—C21 | 109.07 (11) | C17—C16—C15 | 121.1 (3) |
O2i—Si1—C15 | 107.75 (11) | C17—C16—H16 | 119.5 |
O3—Si1—C15 | 104.87 (11) | C15—C16—H16 | 119.5 |
C21—Si1—C15 | 117.06 (12) | C18—C17—C16 | 120.2 (3) |
C2—O1—H1 | 109.5 | C18—C17—H17 | 119.9 |
C8—O2—Si1i | 126.29 (16) | C16—C17—H17 | 119.9 |
C10—O3—Si1 | 129.71 (16) | C17—C18—C19 | 119.6 (3) |
C1—N1—C5 | 118.5 (2) | C17—C18—H18 | 120.2 |
C7—N2—C9 | 123.4 (2) | C19—C18—H18 | 120.2 |
N1—C1—C2 | 121.5 (2) | C18—C19—C20 | 120.1 (3) |
N1—C1—C6 | 118.3 (2) | C18—C19—H19 | 119.9 |
C2—C1—C6 | 120.2 (3) | C20—C19—H19 | 119.9 |
O1—C2—C1 | 117.7 (2) | C19—C20—C15 | 121.6 (3) |
O1—C2—C3 | 122.4 (2) | C19—C20—H20 | 119.2 |
C1—C2—C3 | 119.9 (2) | C15—C20—H20 | 119.2 |
C2—C3—C4 | 117.4 (2) | C26—C21—C22 | 117.1 (3) |
C2—C3—C7 | 119.3 (2) | C26—C21—Si1 | 122.0 (2) |
C4—C3—C7 | 123.3 (2) | C22—C21—Si1 | 120.9 (2) |
C5—C4—C3 | 118.1 (2) | C21—C22—C23 | 121.5 (3) |
C5—C4—C8 | 117.4 (2) | C21—C22—H22 | 119.2 |
C3—C4—C8 | 124.5 (2) | C23—C22—H22 | 119.2 |
N1—C5—C4 | 124.6 (2) | C24—C23—C22 | 119.8 (3) |
N1—C5—H5 | 117.7 | C24—C23—H23 | 120.1 |
C4—C5—H5 | 117.7 | C22—C23—H23 | 120.1 |
C1—C6—H6A | 109.5 | C25—C24—C23 | 119.9 (3) |
C1—C6—H6B | 109.5 | C25—C24—H24 | 120.0 |
H6A—C6—H6B | 109.5 | C23—C24—H24 | 120.0 |
C1—C6—H6C | 109.5 | C24—C25—C26 | 120.8 (3) |
H6A—C6—H6C | 109.5 | C24—C25—H25 | 119.6 |
H6B—C6—H6C | 109.5 | C26—C25—H25 | 119.6 |
N2—C7—C3 | 119.7 (2) | C21—C26—C25 | 120.9 (3) |
N2—C7—H7 | 120.1 | C21—C26—H26 | 119.6 |
C3—C7—H7 | 120.1 | C25—C26—H26 | 119.6 |
O2—C8—C4 | 110.2 (2) | Cl2—C27—Cl3 | 111.41 (17) |
O2—C8—H8A | 109.6 | Cl2—C27—Cl1 | 110.61 (17) |
C4—C8—H8A | 109.6 | Cl3—C27—Cl1 | 110.63 (17) |
O2—C8—H8B | 109.6 | Cl2—C27—H27 | 108.0 |
C4—C8—H8B | 109.6 | Cl3—C27—H27 | 108.0 |
H8A—C8—H8B | 108.1 | Cl1—C27—H27 | 108.0 |
C14—C9—C10 | 118.7 (2) | Cl6B—C28—Cl5B | 126.5 (5) |
C14—C9—N2 | 124.4 (2) | Cl6B—C28—Cl4A | 117.4 (3) |
C10—C9—N2 | 116.9 (2) | Cl5B—C28—Cl4A | 100.8 (3) |
O3—C10—C11 | 122.5 (2) | Cl5B—C28—Cl6A | 118.7 (4) |
O3—C10—C9 | 117.4 (2) | Cl4A—C28—Cl6A | 113.9 (3) |
C11—C10—C9 | 120.1 (2) | Cl6B—C28—Cl4B | 99.4 (5) |
C12—C11—C10 | 119.9 (3) | Cl5B—C28—Cl4B | 110.3 (3) |
C12—C11—H11 | 120.0 | Cl6A—C28—Cl4B | 95.0 (4) |
C10—C11—H11 | 120.0 | Cl6B—C28—Cl5A | 113.1 (4) |
C13—C12—C11 | 120.5 (3) | Cl4A—C28—Cl5A | 110.5 (2) |
C13—C12—H12 | 119.7 | Cl6A—C28—Cl5A | 105.7 (3) |
C11—C12—H12 | 119.7 | Cl4B—C28—Cl5A | 116.7 (3) |
C12—C13—C14 | 119.7 (3) | Cl6B—C28—H28 | 96.9 |
C12—C13—H13 | 120.1 | Cl5B—C28—H28 | 105.0 |
C14—C13—H13 | 120.1 | Cl4A—C28—H28 | 108.9 |
C13—C14—C9 | 120.9 (3) | Cl6A—C28—H28 | 108.9 |
C13—C14—H14 | 119.5 | Cl4B—C28—H28 | 119.6 |
C9—C14—H14 | 119.5 | Cl5A—C28—H28 | 108.9 |
C20—C15—C16 | 117.4 (3) | ||
O2i—Si1—O3—C10 | 49.2 (2) | C9—C10—C11—C12 | 0.9 (4) |
C21—Si1—O3—C10 | −67.6 (2) | C10—C11—C12—C13 | −1.4 (4) |
C15—Si1—O3—C10 | 166.3 (2) | C11—C12—C13—C14 | 0.2 (4) |
C5—N1—C1—C2 | −1.1 (4) | C12—C13—C14—C9 | 1.6 (4) |
C5—N1—C1—C6 | 178.8 (3) | C10—C9—C14—C13 | −2.1 (4) |
N1—C1—C2—O1 | −177.7 (2) | N2—C9—C14—C13 | −179.5 (2) |
C6—C1—C2—O1 | 2.4 (4) | O2i—Si1—C15—C20 | −44.2 (3) |
N1—C1—C2—C3 | 2.7 (4) | O3—Si1—C15—C20 | −164.9 (2) |
C6—C1—C2—C3 | −177.3 (3) | C21—Si1—C15—C20 | 74.1 (3) |
O1—C2—C3—C4 | 178.6 (2) | O2i—Si1—C15—C16 | 133.1 (2) |
C1—C2—C3—C4 | −1.8 (4) | O3—Si1—C15—C16 | 12.4 (3) |
O1—C2—C3—C7 | −2.3 (4) | C21—Si1—C15—C16 | −108.6 (3) |
C1—C2—C3—C7 | 177.3 (2) | C20—C15—C16—C17 | 0.3 (5) |
C2—C3—C4—C5 | −0.4 (3) | Si1—C15—C16—C17 | −177.0 (3) |
C7—C3—C4—C5 | −179.5 (2) | C15—C16—C17—C18 | 0.2 (5) |
C2—C3—C4—C8 | 176.4 (2) | C16—C17—C18—C19 | −0.6 (5) |
C7—C3—C4—C8 | −2.6 (4) | C17—C18—C19—C20 | 0.4 (6) |
C1—N1—C5—C4 | −1.3 (4) | C18—C19—C20—C15 | 0.1 (6) |
C3—C4—C5—N1 | 2.1 (4) | C16—C15—C20—C19 | −0.4 (5) |
C8—C4—C5—N1 | −175.0 (2) | Si1—C15—C20—C19 | 177.1 (3) |
C9—N2—C7—C3 | −179.2 (2) | O2i—Si1—C21—C26 | 42.7 (3) |
C2—C3—C7—N2 | 1.2 (4) | O3—Si1—C21—C26 | 164.3 (3) |
C4—C3—C7—N2 | −179.7 (2) | C15—Si1—C21—C26 | −76.9 (3) |
Si1i—O2—C8—C4 | 90.4 (2) | O2i—Si1—C21—C22 | −138.3 (3) |
C5—C4—C8—O2 | 83.2 (3) | O3—Si1—C21—C22 | −16.6 (3) |
C3—C4—C8—O2 | −93.7 (3) | C15—Si1—C21—C22 | 102.1 (3) |
C7—N2—C9—C14 | −21.0 (4) | C26—C21—C22—C23 | 0.9 (5) |
C7—N2—C9—C10 | 161.5 (2) | Si1—C21—C22—C23 | −178.2 (3) |
Si1—O3—C10—C11 | −9.1 (4) | C21—C22—C23—C24 | −0.2 (6) |
Si1—O3—C10—C9 | 173.52 (18) | C22—C23—C24—C25 | −0.6 (6) |
C14—C9—C10—O3 | 178.2 (2) | C23—C24—C25—C26 | 0.5 (7) |
N2—C9—C10—O3 | −4.2 (3) | C22—C21—C26—C25 | −0.9 (6) |
C14—C9—C10—C11 | 0.8 (4) | Si1—C21—C26—C25 | 178.1 (3) |
N2—C9—C10—C11 | 178.4 (2) | C24—C25—C26—C21 | 0.2 (7) |
O3—C10—C11—C12 | −176.3 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.84 | 1.77 | 2.511 (3) | 147 |
C27—H27···N1 | 1.00 | 2.16 | 3.149 (4) | 168 |
C28—H28···O1 | 1.00 | 2.35 | 3.295 (4) | 158 |
Experimental details
Crystal data | |
Chemical formula | C52H44N4O6Si2·4CHCl3 |
Mr | 1354.56 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 153 |
a, b, c (Å) | 9.8831 (3), 11.2094 (3), 14.7584 (4) |
α, β, γ (°) | 102.853 (2), 101.899 (1), 98.733 (1) |
V (Å3) | 1525.91 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.33 × 0.30 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.818, 0.873 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14146, 6493, 5116 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.114, 1.07 |
No. of reflections | 6493 |
No. of parameters | 391 |
No. of restraints | 126 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.44 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.84 | 1.77 | 2.511 (3) | 146.9 |
C27—H27···N1 | 1.00 | 2.16 | 3.149 (4) | 168.2 |
C28—H28···O1 | 1.00 | 2.35 | 3.295 (4) | 158.1 |
Carbon-based macrocycles are used frequently as hosts for molecular-recognition processes (Weber & Vögtle, 1996). The macrocycle provides the necessary preorganization of the host for the inclusion process (König, Rödel, Bubenitschek, Jones & Thondorf, 1995). The incorporation of other main group elements into the macrocycles gives these compounds new binding properties (König, Rödel, Bubenitschek & Jones, 1995). Earlier work has shown the coordinative ability of silicon (Jung & Xia, 1988), phosporous (Caminade & Majoral, 1994) and tin (Blanda et al., 1989) as bridging atoms in macrocycles. During our work on silicon complexes with tridentate O,N,O-ligands of Schiff base type, we used pyridoxal as a component of the ligand system. The reaction of pyridoxal hydrocloride with o-aminophenole in the presence of sodium methanolate gives the polydentate ligand, (I). There are numerous potential docking sites in the ligand molecule: the pyridine N atom, one aliphatic and two phenolic hydroxyl groups, and the imino N atom. The presence of diverse functional groups in (I) makes it difficult to predict the molecular structure of the reaction product with halogenosilanes. It was our initial goal to prepare a pentacoordinate silicon complex like (II). Surprisingly, the macrocyclic silicon compound, (III), was obtained from the reaction of (I) with Ph2SiCl2 in tetrahydrofuran in the presence of NEt3 as a supporting base to remove the hydrogen chloride which is formed during the reaction. The first hint of the formation of a tetracoordinate silicon complex was found in the 29Si NMR spectrum: compound (III) has a single resonance signal at -32.8 p.p.m. The 1H and 13C NMR spectra did not give further information apart from the presence of the ligand system including one hydroxyl group.
Crystallization of (III) from a chloroform solution over several weeks at 278 K yielded single crystals of the title chloroform solvate, (III).4CHCl3, which crystallizes in the triclinic space group P1 with half of the macrocycle and two molecules of CHCl3 in the asymmetric unit (Fig. 1). The macrocycle is thus generated by a crystallographic inversion centre (Fig. 2). The Si atom is bound to the two phenyl groups, to phenolic atom O3 and to the aliphatic O atom from the next ligand molecule, thus forming a macrocycle (Fig. 2). The Si—O bonds are short (Table 1), but in the range for comparable Si—O bonds (Wagler et al., 2005; Böhme et al., 2006; Böhme & Günther, 2007; Böhme & Foehn, 2007). The coordination geometry around Si is distorted tetrahedral, with bond angles between 104.9 (1) and 117.1 (1)° (Table 1). The O2Si(Ph)2 moiety is a common structural motif. Some macrocycles with a similar distorted tetrahedral coordination environment at Si have been described earlier (Cragg et al., 1991; Rezzonico et al. 1998; Gómez & Farfán, 1999). The rather large bond angles at O (Table 1) are explained by the ionic character of the Si—O bonds (Gillespie & Johnson, 1997).
Two planes can be used to characterize the conformation of the dianion of the ligand molecule, (II). The plane of the C9–C14 phenyl ring makes an angle of 17.5 (2)° with the plane of the pyridine ring (C1–C5/N1). Nearly planar with this latter ring is the six-membered pseudo-ring (Fig. 1) consisting of atoms H1/O1/C2/C3/C7/N2 [at an angle of 2.1 (1)° to the pyridine ring]. The planarity of the six-membered pseudo-ring is caused by a strong intramolecular O—H···N interaction (entry 1, Table 2). The formation of hydrogen bonds between the imine N atom and an ortho hydroxyl group is a feature which is often observed in Schiff bases with o-hydroxy groups (Hökelek et al., 2004; Filarowski et al., 1999).
Two independent chloroform molecules are incorporated into the crystal structure. Contacts with the disordered Cl atoms of the C28-based solvate (Fig. 1) are not considered important for crystal structure formation. The non-disordered solvate shows only one very weak chlorine contact (C22—H22···Cl1 2.90 Å and 144°) but is bound to the guest via a C28—H28···O1 intermolecular contact (entry 3, Table 2). The other guest is connected to the host via a C—H···N contact (Fig. 3; entry 2, Table 2). One C8—H8A···π contact between one of the aliphatic H atoms, H8A, and the pyridine unit is localized with an H-to-centre distance of 2.94 Å and a C8—H8A···Cg angle of 109°, where Cg is the centre of the C1–C5/N1 ring at the symmetry position (2-x, 1-y, -z). This contact forms intermolecular chains of the host molecule along the crystallographic a axis (not shown in Fig. 3). These intermolecular contacts of weak to moderate strength in the crystal structure of (III).4CHCl3 indicate potential coordination sites for interactions with other guest molecules.
Numerous potential bonding sites in the ligand system, along with the cavity of the macrocycle, provide promise for (III) as a host molecule in supramolecular recognition processes. Furthermore, the available OH, azomethine-N and pyridine-N groups could be useful for the construction of nanostructures via complexation with transition metals (Leininger et al., 2000).