Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038044/hk2304sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038044/hk2304Isup2.hkl |
CCDC reference: 660224
Under nitrogen atmosphere, a mixture of bisphenol A (7.5 g, 33 mmol) and anhydrous potassium carbonate (2.2 g, 16 mmol) in dry acetonitrile (75 ml) were stirred for half an hour at room temperature. Subsequently benzyl chloride (8.2 g, 66 mmol) and potassium iodide (0.6 g, 3.6 mmol) were added to the reaction mixture, which was then refluxed for another 3 h, in inert atmosphere. The mixture was cooled to room temperature, filtrated and the solvent was removed under reduced pressure. The crude product was purified with n-hexane solution. Crystals of (I) suitable for X-ray diffraction were recrystallized by slow evaporation of acetone.
H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Chiral Co(salen) complexes are widely used in the hydrolytic kinetic resolution of terminal epoxides, such as epichlorohydrin (Annis & Jacobsen, 1999). Bisphenols, such as bisphenol A, are useful as starting materials for the synthesis of salicylaldehyde (Ready & Jacobsen, 2001), especially in the synthesis of polymeric salen complexes (Mi-ae & Geon, 2003). The title compound, (I), was obtained unintentionally as the product of an attempted synthesis of a new chiral cobalt salen catalyst. We report herein the crystal structure of (I).
The asymmetric unit of the title compound, (I), contains one half molecule (Fig. 1), in which C14 atom lies on the twofold rotation axis. The bond lengths and angles are generally within normal ranges (Allen et al., 1987).
The rings A (C1—C6) and B (C8—C13) are, of course, planar and the dihedral angle between them is 76.5 (3)°.
In the crystal structure, intermolecular C—H···π interactions involving ring A (Table1), linking the molecules (Fig. 2, where cg1 is the centroid of ring A), seem to be effective in the stabilization of the structure.
For general background, see: Annis & Jacobsen (1999); Ready & Jacobsen (2001); Mi-ae & Geon (2003). For bond-length data, see: Allen et al. (1987).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
C29H28O2 | F(000) = 872 |
Mr = 408.51 | Dx = 1.193 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 18.808 (4) Å | θ = 9–13° |
b = 6.3900 (13) Å | µ = 0.07 mm−1 |
c = 18.925 (4) Å | T = 298 K |
β = 90.97 (3)° | Block, colorless |
V = 2274.1 (8) Å3 | 0.40 × 0.30 × 0.30 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 1558 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 26.0°, θmin = 2.2° |
ω/2θ scans | h = −22→22 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→7 |
Tmin = 0.966, Tmax = 0.978 | l = 0→23 |
2918 measured reflections | 3 standard reflections every 200 reflections |
2227 independent reflections | intensity decay: none |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0537P)2 + 0.7301P] where P = (Fo2 + 2Fc2)/3 |
2227 reflections | (Δ/σ)max < 0.001 |
142 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
C29H28O2 | V = 2274.1 (8) Å3 |
Mr = 408.51 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.808 (4) Å | µ = 0.07 mm−1 |
b = 6.3900 (13) Å | T = 298 K |
c = 18.925 (4) Å | 0.40 × 0.30 × 0.30 mm |
β = 90.97 (3)° |
Enraf–Nonius CAD-4 diffractometer | 1558 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.040 |
Tmin = 0.966, Tmax = 0.978 | 3 standard reflections every 200 reflections |
2918 measured reflections | intensity decay: none |
2227 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.13 e Å−3 |
2227 reflections | Δρmin = −0.13 e Å−3 |
142 parameters |
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. 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 | ||
O1 | 0.23856 (6) | 0.1080 (2) | 0.36046 (6) | 0.0573 (4) | |
C1 | 0.43148 (10) | −0.2644 (4) | 0.48738 (12) | 0.0712 (6) | |
H1 | 0.4754 | −0.3060 | 0.5057 | 0.085* | |
C2 | 0.40194 (11) | −0.0813 (4) | 0.50883 (13) | 0.0766 (6) | |
H2 | 0.4255 | 0.0019 | 0.5420 | 0.092* | |
C3 | 0.33710 (10) | −0.0191 (3) | 0.48132 (12) | 0.0694 (6) | |
H3 | 0.3173 | 0.1061 | 0.4964 | 0.083* | |
C4 | 0.30101 (9) | −0.1383 (3) | 0.43194 (10) | 0.0551 (5) | |
C5 | 0.33134 (11) | −0.3246 (3) | 0.41111 (10) | 0.0688 (6) | |
H5 | 0.3079 | −0.4089 | 0.3781 | 0.083* | |
C6 | 0.39667 (11) | −0.3867 (4) | 0.43914 (11) | 0.0746 (6) | |
H6 | 0.4168 | −0.5124 | 0.4249 | 0.090* | |
C7 | 0.22947 (9) | −0.0712 (3) | 0.40375 (11) | 0.0659 (6) | |
H7A | 0.2080 | −0.1836 | 0.3763 | 0.079* | |
H7B | 0.1983 | −0.0383 | 0.4426 | 0.079* | |
C8 | 0.17851 (8) | 0.2026 (3) | 0.33329 (8) | 0.0446 (4) | |
C9 | 0.10960 (9) | 0.1519 (3) | 0.35085 (9) | 0.0522 (5) | |
H9 | 0.1010 | 0.0431 | 0.3822 | 0.063* | |
C10 | 0.05346 (8) | 0.2643 (3) | 0.32147 (9) | 0.0515 (4) | |
H10 | 0.0073 | 0.2276 | 0.3333 | 0.062* | |
C11 | 0.06324 (8) | 0.4287 (2) | 0.27526 (8) | 0.0411 (4) | |
C12 | 0.13292 (9) | 0.4733 (3) | 0.25751 (9) | 0.0530 (5) | |
H12 | 0.1416 | 0.5804 | 0.2255 | 0.064* | |
C13 | 0.18954 (9) | 0.3632 (3) | 0.28597 (9) | 0.0559 (5) | |
H13 | 0.2356 | 0.3974 | 0.2732 | 0.067* | |
C14 | 0.0000 | 0.5628 (4) | 0.2500 | 0.0472 (6) | |
C15 | −0.02072 (10) | 0.7045 (3) | 0.31224 (11) | 0.0697 (6) | |
H15A | −0.0571 | 0.8003 | 0.2970 | 0.105* | |
H15B | 0.0202 | 0.7815 | 0.3284 | 0.105* | |
H15C | −0.0382 | 0.6197 | 0.3501 | 0.105* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0413 (6) | 0.0677 (8) | 0.0629 (7) | 0.0058 (6) | −0.0017 (5) | 0.0181 (7) |
C1 | 0.0481 (11) | 0.0874 (16) | 0.0779 (14) | 0.0098 (11) | −0.0046 (10) | 0.0149 (13) |
C2 | 0.0629 (13) | 0.0765 (14) | 0.0896 (15) | −0.0036 (12) | −0.0204 (11) | 0.0023 (13) |
C3 | 0.0600 (12) | 0.0576 (12) | 0.0903 (15) | 0.0061 (10) | −0.0081 (11) | −0.0012 (11) |
C4 | 0.0478 (10) | 0.0609 (12) | 0.0566 (11) | 0.0027 (9) | −0.0028 (8) | 0.0118 (9) |
C5 | 0.0747 (13) | 0.0755 (14) | 0.0560 (11) | 0.0100 (11) | −0.0072 (9) | −0.0065 (11) |
C6 | 0.0708 (13) | 0.0808 (15) | 0.0725 (14) | 0.0305 (12) | 0.0074 (11) | 0.0029 (12) |
C7 | 0.0518 (11) | 0.0687 (13) | 0.0768 (13) | 0.0020 (10) | −0.0090 (9) | 0.0218 (11) |
C8 | 0.0411 (9) | 0.0500 (10) | 0.0427 (8) | 0.0034 (7) | −0.0041 (7) | −0.0008 (8) |
C9 | 0.0466 (9) | 0.0532 (10) | 0.0566 (10) | −0.0050 (8) | −0.0052 (8) | 0.0175 (9) |
C10 | 0.0379 (8) | 0.0553 (11) | 0.0612 (11) | −0.0059 (8) | −0.0028 (7) | 0.0130 (9) |
C11 | 0.0424 (9) | 0.0401 (9) | 0.0408 (8) | −0.0042 (7) | −0.0041 (7) | −0.0019 (7) |
C12 | 0.0503 (10) | 0.0558 (11) | 0.0529 (10) | −0.0034 (8) | 0.0011 (8) | 0.0163 (9) |
C13 | 0.0400 (9) | 0.0685 (12) | 0.0594 (11) | −0.0025 (9) | 0.0037 (8) | 0.0149 (10) |
C14 | 0.0469 (13) | 0.0385 (12) | 0.0558 (14) | 0.000 | −0.0077 (10) | 0.000 |
C15 | 0.0620 (12) | 0.0571 (12) | 0.0894 (15) | 0.0054 (10) | −0.0155 (10) | −0.0279 (11) |
C1—C2 | 1.360 (3) | C8—C9 | 1.382 (2) |
C1—C6 | 1.361 (3) | C9—C10 | 1.386 (2) |
C1—H1 | 0.9300 | C9—H9 | 0.9300 |
C2—C3 | 1.376 (3) | C10—C11 | 1.381 (2) |
C2—H2 | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.376 (3) | C11—C12 | 1.388 (2) |
C3—H3 | 0.9300 | C11—C14 | 1.536 (2) |
C4—C5 | 1.381 (3) | C12—C13 | 1.378 (2) |
C4—C7 | 1.501 (2) | C12—H12 | 0.9300 |
C5—C6 | 1.388 (3) | C13—H13 | 0.9300 |
C5—H5 | 0.9300 | C14—C11i | 1.536 (2) |
C6—H6 | 0.9300 | C14—C15i | 1.541 (2) |
C7—O1 | 1.420 (2) | C14—C15 | 1.541 (2) |
C7—H7A | 0.9700 | C15—H15A | 0.9600 |
C7—H7B | 0.9700 | C15—H15B | 0.9600 |
C8—O1 | 1.3731 (18) | C15—H15C | 0.9600 |
C8—C13 | 1.380 (2) | ||
C2—C1—C6 | 119.99 (19) | C8—C9—H9 | 120.2 |
C2—C1—H1 | 120.0 | C10—C9—H9 | 120.2 |
C6—C1—H1 | 120.0 | C11—C10—C9 | 122.65 (15) |
C1—C2—C3 | 119.9 (2) | C11—C10—H10 | 118.7 |
C1—C2—H2 | 120.0 | C9—C10—H10 | 118.7 |
C3—C2—H2 | 120.0 | C10—C11—C12 | 116.49 (15) |
C4—C3—C2 | 121.4 (2) | C10—C11—C14 | 120.71 (13) |
C4—C3—H3 | 119.3 | C12—C11—C14 | 122.65 (14) |
C2—C3—H3 | 119.3 | C13—C12—C11 | 121.80 (16) |
C3—C4—C5 | 118.03 (17) | C13—C12—H12 | 119.1 |
C3—C4—C7 | 120.83 (18) | C11—C12—H12 | 119.1 |
C5—C4—C7 | 121.10 (18) | C12—C13—C8 | 120.63 (15) |
C4—C5—C6 | 120.31 (19) | C12—C13—H13 | 119.7 |
C4—C5—H5 | 119.8 | C8—C13—H13 | 119.7 |
C6—C5—H5 | 119.8 | C11i—C14—C11 | 112.16 (18) |
C1—C6—C5 | 120.3 (2) | C11i—C14—C15i | 107.12 (9) |
C1—C6—H6 | 119.8 | C11—C14—C15i | 111.17 (9) |
C5—C6—H6 | 119.8 | C11i—C14—C15 | 111.17 (9) |
O1—C7—C4 | 108.61 (15) | C11—C14—C15 | 107.12 (9) |
O1—C7—H7A | 110.0 | C15i—C14—C15 | 108.1 (2) |
C4—C7—H7A | 110.0 | C14—C15—H15A | 109.5 |
O1—C7—H7B | 110.0 | C14—C15—H15B | 109.5 |
C4—C7—H7B | 110.0 | H15A—C15—H15B | 109.5 |
H7A—C7—H7B | 108.3 | C14—C15—H15C | 109.5 |
O1—C8—C13 | 116.00 (14) | H15A—C15—H15C | 109.5 |
O1—C8—C9 | 125.14 (15) | H15B—C15—H15C | 109.5 |
C13—C8—C9 | 118.84 (15) | C8—O1—C7 | 117.69 (13) |
C8—C9—C10 | 119.56 (16) | ||
C6—C1—C2—C3 | −0.5 (3) | C10—C11—C12—C13 | −1.7 (3) |
C1—C2—C3—C4 | −0.2 (3) | C14—C11—C12—C13 | 173.81 (15) |
C2—C3—C4—C5 | 0.8 (3) | C11—C12—C13—C8 | 0.3 (3) |
C2—C3—C4—C7 | 178.4 (2) | O1—C8—C13—C12 | −177.72 (16) |
C3—C4—C5—C6 | −0.6 (3) | C9—C8—C13—C12 | 1.0 (3) |
C7—C4—C5—C6 | −178.30 (19) | C10—C11—C14—C11i | −48.19 (12) |
C2—C1—C6—C5 | 0.6 (3) | C12—C11—C14—C11i | 136.45 (17) |
C4—C5—C6—C1 | 0.0 (3) | C10—C11—C14—C15i | −168.10 (15) |
C3—C4—C7—O1 | 69.8 (2) | C12—C11—C14—C15i | 16.5 (2) |
C5—C4—C7—O1 | −112.6 (2) | C10—C11—C14—C15 | 74.1 (2) |
O1—C8—C9—C10 | 177.77 (16) | C12—C11—C14—C15 | −101.31 (17) |
C13—C8—C9—C10 | −0.8 (3) | C13—C8—O1—C7 | −173.80 (16) |
C8—C9—C10—C11 | −0.7 (3) | C9—C8—O1—C7 | 7.6 (3) |
C9—C10—C11—C12 | 1.9 (3) | C4—C7—O1—C8 | −175.67 (15) |
C9—C10—C11—C14 | −173.71 (16) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7B···Cg1ii | 0.97 | 2.78 | 3.488 (2) | 131 |
Symmetry code: (ii) −x+1/2, −y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C29H28O2 |
Mr | 408.51 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 18.808 (4), 6.3900 (13), 18.925 (4) |
β (°) | 90.97 (3) |
V (Å3) | 2274.1 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.40 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.966, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2918, 2227, 1558 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.123, 1.05 |
No. of reflections | 2227 |
No. of parameters | 142 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.13 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7B···Cg1i | 0.97 | 2.78 | 3.488 (2) | 131 |
Symmetry code: (i) −x+1/2, −y−1/2, −z+1. |
Chiral Co(salen) complexes are widely used in the hydrolytic kinetic resolution of terminal epoxides, such as epichlorohydrin (Annis & Jacobsen, 1999). Bisphenols, such as bisphenol A, are useful as starting materials for the synthesis of salicylaldehyde (Ready & Jacobsen, 2001), especially in the synthesis of polymeric salen complexes (Mi-ae & Geon, 2003). The title compound, (I), was obtained unintentionally as the product of an attempted synthesis of a new chiral cobalt salen catalyst. We report herein the crystal structure of (I).
The asymmetric unit of the title compound, (I), contains one half molecule (Fig. 1), in which C14 atom lies on the twofold rotation axis. The bond lengths and angles are generally within normal ranges (Allen et al., 1987).
The rings A (C1—C6) and B (C8—C13) are, of course, planar and the dihedral angle between them is 76.5 (3)°.
In the crystal structure, intermolecular C—H···π interactions involving ring A (Table1), linking the molecules (Fig. 2, where cg1 is the centroid of ring A), seem to be effective in the stabilization of the structure.