Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300998X/dn6071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680300998X/dn6071Isup2.hkl |
CCDC reference: 214825
Key indicators
- Single-crystal X-ray study
- T = 220 K
- Mean (C-C) = 0.003 Å
- R factor = 0.050
- wR factor = 0.141
- Data-to-parameter ratio = 8.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 69.95 From the CIF: _reflns_number_total 643 Count of symmetry unique reflns 645 Completeness (_total/calc) 99.69% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
Phenol (2.50 g, 26.6 mmol) and pentaerythrityl tetratosylate (4.00 g, 5.31 mmol) were added to Cs2CO3 (4.33 g, 13.3 mmol) in N,N'-dimethylformamide (20 ml), and the mixture was heated at 413 K for 24 h. Water was then added, the resulting mixture was extracted with diethyl ether, and the organic phase was washed with water and dried over anhydrous MgSO4. Evaporation of solvent under reduced pressure left a residue which was filtered over silica gel using chloroform as eluent and then crystallized from benzene/hexane to give crystals of the title coupound (1.25 g, 2.84 mmol, 53%).
As no atom types with Z > Si are present, the Friedel pairs were merged and the absolute structure could not be defined. H atoms were rided to idealized positions with their isotropic displacement parameters fixed to 1.2 Ueq of the equivalent isotropic displacement parameter of the atoms to which they are bonded.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C29H28O4 | Dx = 1.156 Mg m−3 |
Mr = 440.51 | Melting point: 113 K |
Tetragonal, I4 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: I -4 | Cell parameters from 2339 reflections |
a = 12.2242 (3) Å | θ = 5.1–69.7° |
c = 8.4655 (3) Å | µ = 0.61 mm−1 |
V = 1265.01 (6) Å3 | T = 220 K |
Z = 2 | Block, colorless |
F(000) = 468 | 0.20 × 0.15 × 0.15 mm |
Bruker AXS SMART 2K/Platform diffractometer | 643 independent reflections |
Radiation source: Sealed Tube | 613 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 5.5 pixels mm-1 | θmax = 70.0°, θmin = 5.1° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.896, Tmax = 0.913 | l = −10→10 |
3443 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.1128P)2 + 0.0245P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
643 reflections | Δρmax = 0.15 e Å−3 |
76 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (2) |
C29H28O4 | Z = 2 |
Mr = 440.51 | Cu Kα radiation |
Tetragonal, I4 | µ = 0.61 mm−1 |
a = 12.2242 (3) Å | T = 220 K |
c = 8.4655 (3) Å | 0.20 × 0.15 × 0.15 mm |
V = 1265.01 (6) Å3 |
Bruker AXS SMART 2K/Platform diffractometer | 643 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 613 reflections with I > 2σ(I) |
Tmin = 0.896, Tmax = 0.913 | Rint = 0.059 |
3443 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.15 e Å−3 |
643 reflections | Δρmin = −0.20 e Å−3 |
76 parameters |
Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis. |
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. Angle CCC1 87.77 (0.05) C7 - C1 - C7_$1 Angle CCC2 121.30 (0.03) C7 - C1 - C7_$2 Angle CCC3 121.30 (0.03) C7 - C1 - C7_$3 Distance LH1 2.7845 (0.036) C6 - H9_$4 Angle ALH1 150.69 (2.93) C6 - H9_$4 - C9_$4 Distance LH2 3.1582 (0.036) H6 - C5_$5 Angle ALH2 133.41 (2.55) C6 - H6 - C5_$5 Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 7.0504 (0.0120) x − 6.9471 (0.0128) y − 4.9678 (0.0073) z = 6.6087 (0.0137) * 0.0093 (0.0017) C4 * −0.0056 (0.0016) C5 * −0.0020 (0.0017) C6 * 0.0059 (0.0020) C7 * −0.0021 (0.0023) C8 * −0.0055 (0.0020) C9 Rms deviation of fitted atoms = 0.0056 |
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 | ||
C1 | 0.0000 | −1.0000 | 0.0000 | 0.0504 (10) | |
C2 | −0.10139 (18) | −1.01889 (18) | −0.1018 (3) | 0.0523 (7) | |
H2A | −0.0921 | −1.0850 | −0.1659 | 0.063* | |
H2B | −0.1659 | −1.0285 | −0.0345 | 0.063* | |
O3 | −0.11545 (14) | −0.92649 (13) | −0.2012 (2) | 0.0592 (6) | |
C4 | −0.19684 (17) | −0.93000 (18) | −0.3110 (3) | 0.0483 (6) | |
C5 | −0.27891 (17) | −1.00814 (18) | −0.3152 (3) | 0.0522 (6) | |
H5 | −0.2816 | −1.0638 | −0.2387 | 0.063* | |
C6 | −0.35678 (18) | −1.0033 (2) | −0.4333 (4) | 0.0619 (7) | |
H6 | −0.4122 | −1.0565 | −0.4368 | 0.074* | |
C7 | −0.3549 (2) | −0.9222 (3) | −0.5455 (4) | 0.0687 (8) | |
H7 | −0.4080 | −0.9202 | −0.6258 | 0.082* | |
C8 | −0.2732 (3) | −0.8431 (3) | −0.5386 (4) | 0.0726 (9) | |
H8 | −0.2714 | −0.7868 | −0.6142 | 0.087* | |
C9 | −0.1953 (2) | −0.8468 (2) | −0.4222 (4) | 0.0647 (8) | |
H9 | −0.1407 | −0.7927 | −0.4178 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0529 (13) | 0.0529 (13) | 0.045 (2) | 0.000 | 0.000 | 0.000 |
C2 | 0.0533 (11) | 0.0528 (11) | 0.0507 (14) | −0.0065 (8) | −0.0010 (11) | 0.0035 (10) |
O3 | 0.0704 (10) | 0.0584 (9) | 0.0486 (11) | −0.0173 (7) | −0.0122 (9) | 0.0092 (8) |
C4 | 0.0528 (10) | 0.0554 (11) | 0.0365 (12) | −0.0014 (8) | 0.0037 (10) | −0.0021 (10) |
C5 | 0.0501 (10) | 0.0524 (11) | 0.0541 (13) | 0.0026 (7) | 0.0055 (11) | −0.0034 (11) |
C6 | 0.0460 (10) | 0.0712 (14) | 0.0686 (18) | 0.0037 (9) | −0.0043 (12) | −0.0082 (13) |
C7 | 0.0530 (12) | 0.0950 (18) | 0.0580 (16) | 0.0104 (11) | −0.0062 (11) | −0.0024 (15) |
C8 | 0.0746 (15) | 0.0926 (18) | 0.0507 (16) | 0.0053 (13) | 0.0021 (13) | 0.0196 (15) |
C9 | 0.0676 (14) | 0.0759 (15) | 0.0506 (16) | −0.0111 (11) | 0.0013 (12) | 0.0140 (12) |
C1—C2 | 1.527 (2) | C5—C6 | 1.382 (4) |
C1—C2i | 1.527 (2) | C5—H5 | 0.94 |
C1—C2ii | 1.527 (2) | C6—C7 | 1.373 (4) |
C1—C2iii | 1.527 (2) | C6—H6 | 0.94 |
C2—O3 | 1.419 (3) | C7—C8 | 1.392 (5) |
C2—H2a | 0.98 | C7—H7 | 0.94 |
C2—H2b | 0.98 | C8—C9 | 1.371 (4) |
O3—C4 | 1.362 (3) | C8—H8 | 0.94 |
C4—C5 | 1.386 (3) | C9—H9 | 0.94 |
C4—C9 | 1.386 (3) | ||
C2i—C1—C2 | 108.58 (9) | C6—C5—C4 | 119.2 (2) |
C2i—C1—C2ii | 108.58 (9) | C6—C5—H5 | 120.4 |
C2—C1—C2ii | 111.27 (19) | C4—C5—H5 | 120.4 |
C2i—C1—C2iii | 111.27 (19) | C7—C6—C5 | 121.4 (2) |
C2—C1—C2iii | 108.58 (9) | C7—C6—H6 | 119.3 |
C2ii—C1—C2iii | 108.58 (9) | C5—C6—H6 | 119.3 |
O3—C2—C1 | 108.23 (15) | C6—C7—C8 | 119.0 (3) |
O3—C2—H2A | 110.1 | C6—C7—H7 | 120.5 |
C1—C2—H2A | 110.1 | C8—C7—H7 | 120.5 |
O3—C2—H2B | 110.1 | C9—C8—C7 | 120.4 (3) |
C1—C2—H2B | 110.1 | C9—C8—H8 | 119.8 |
H2A—C2—H2B | 108.4 | C7—C8—H8 | 119.8 |
C4—O3—C2 | 117.91 (16) | C8—C9—C4 | 120.2 (2) |
O3—C4—C5 | 124.6 (2) | C8—C9—H9 | 119.9 |
O3—C4—C9 | 115.50 (19) | C4—C9—H9 | 119.9 |
C5—C4—C9 | 119.9 (2) | ||
C2i—C1—C2—O3 | 61.53 (10) | C9—C4—C5—C6 | 1.6 (4) |
C2ii—C1—C2—O3 | −57.91 (13) | C4—C5—C6—C7 | −0.5 (4) |
C2iii—C1—C2—O3 | −177.36 (18) | C5—C6—C7—C8 | −0.6 (4) |
C1—C2—O3—C4 | 175.05 (17) | C6—C7—C8—C9 | 0.6 (5) |
C2—O3—C4—C5 | 11.9 (3) | C7—C8—C9—C4 | 0.5 (5) |
C2—O3—C4—C9 | −169.3 (2) | O3—C4—C9—C8 | 179.6 (3) |
O3—C4—C5—C6 | −179.7 (2) | C5—C4—C9—C8 | −1.6 (4) |
Symmetry codes: (i) y+1, −x−1, −z; (ii) −x, −y−2, z; (iii) −y−1, x−1, −z. |
Experimental details
Crystal data | |
Chemical formula | C29H28O4 |
Mr | 440.51 |
Crystal system, space group | Tetragonal, I4 |
Temperature (K) | 220 |
a, c (Å) | 12.2242 (3), 8.4655 (3) |
V (Å3) | 1265.01 (6) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.20 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Bruker AXS SMART 2K/Platform diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.896, 0.913 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3443, 643, 613 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.141, 1.08 |
No. of reflections | 643 |
No. of parameters | 76 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.20 |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999b), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1997), SHELXTL.
C1—C2 | 1.527 (2) | C5—C6 | 1.382 (4) |
C2—O3 | 1.419 (3) | C6—C7 | 1.373 (4) |
O3—C4 | 1.362 (3) | C7—C8 | 1.392 (5) |
C4—C5 | 1.386 (3) | C8—C9 | 1.371 (4) |
C4—C9 | 1.386 (3) | ||
C2i—C1—C2 | 108.58 (9) | C5—C4—C9 | 119.9 (2) |
C2—C1—C2ii | 111.27 (19) | C6—C5—C4 | 119.2 (2) |
O3—C2—C1 | 108.23 (15) | C7—C6—C5 | 121.4 (2) |
C4—O3—C2 | 117.91 (16) | C6—C7—C8 | 119.0 (3) |
O3—C4—C5 | 124.6 (2) | C9—C8—C7 | 120.4 (3) |
O3—C4—C9 | 115.50 (19) | C8—C9—C4 | 120.2 (2) |
C2i—C1—C2—O3 | 61.53 (10) | C9—C4—C5—C6 | 1.6 (4) |
C2ii—C1—C2—O3 | −57.91 (13) | C4—C5—C6—C7 | −0.5 (4) |
C2iii—C1—C2—O3 | −177.36 (18) | C5—C6—C7—C8 | −0.6 (4) |
C1—C2—O3—C4 | 175.05 (17) | C6—C7—C8—C9 | 0.6 (5) |
C2—O3—C4—C5 | 11.9 (3) | C7—C8—C9—C4 | 0.5 (5) |
C2—O3—C4—C9 | −169.3 (2) | O3—C4—C9—C8 | 179.6 (3) |
O3—C4—C5—C6 | −179.7 (2) | C5—C4—C9—C8 | −1.6 (4) |
Symmetry codes: (i) y+1, −x−1, −z; (ii) −x, −y−2, z; (iii) −y−1, x−1, −z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Derivatives of tetraphenylmethane have been widely used as tetrahedral building blocks for molecular construction, leading to supramolecular networks, dendrimers, polymers, nanoscale structures, optoelectronic materials, liquid crystals, and other materials (Fournier, Maris et al., 2003; Fournier, Wang & Wuest, 2003). The title compound, (I), offers a related subunit that is easier to make and more flexible. In the course of studying its use as a building block in supramolecular assembly, we investigated its structure to identify the preferred conformation, analyze the principal intermolecular interactions, and obtain detailed geometric information.
The title compound has been previously synthesized by the reaction of alkali salts of phenol with pentaerythrityl tetrabromide (Backer & Dijken, 1936) or with pentaerythrityl tetratosylate (Shostakovskii et al., 1965). We made the compound by a modification of the second route, obtained crystals from benzene/hexane, and determined their structure (Figs. 1–3). Our data confirm and significantly refine the major features of a very early structural approximation, using crystals grown from benzene/petroleum ether (Beintema et al., 1935).
The two independent C2—C1—C2 angles at the central atom C1, which are 108.52 (8) and 111.39 (16)°, are somewhat closer to the ideal tetrahedral value than those of tetraphenylmethane, which are approximately 107 and 111° (Robbins et al., 1975). In addition, the arms connecting the central C atom to the phenyl groups are nearly fully extended, as shown by the torsion angle C1—C2—O3—C4 [175.08 (15)°]. However, the two independent C7–C1–C7 angles defined by the central C atom and the para positions of the phenyl groups have the values 87.77 (5) and 121.30 (3)°, showing that the overall molecule deviates significantly from tetrahedral geometry.
Cohesion in the crystal arises from van der Waals contacts and multiple edge-to-face phenyl–phenyl interactions. Each phenyl group participates in four of these interactions involving three neighboring molecules. Two of the four phenyl–phenyl interactions define part of a twofold embrace (Dance & Scudder, 1995), giving rise to chains along the c axis (Fig. 3). In these embraces, the shortest H···C distances) 2.79 Å, with C–H···C angles of 150°) are between the H atom attached to C9 of one phenyl group and C6 of the other. The remaining two edge-to-face phenyl–phenyl interactions of each phenyl group involve neighbors in adjacent chains. In these interactions, the shortest H···C distances (3.16 Å, with C–H···C angles of 133°) are between the H atom attached to C6 of one phenyl group and C5 of the other.