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The title compound, C29H28O4, was synthesized by a new method, crystallized from benzene/hexane, and its crystal structure determined. The mol­ecule adopts a distorted tetrahedral geometry, and each phenyl group forms four edge-to-face phenyl-phenyl interactions with three different neighboring mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300998X/dn6071sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680300998X/dn6071Isup2.hkl
Contains datablock I

CCDC reference: 214825

Key indicators

  • Single-crystal X-ray study
  • T = 220 K
  • Mean [sigma](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.

Comment top

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.

Experimental top

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%).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Displacement ellispsoids drawing of the structure of the title compound with the atom-numbering scheme. Ellipsoids are drawn at 30% probability level and H atoms are represented by spheres of arbitrary radius.
[Figure 2] Fig. 2. Packing diagram of the title compound. H atoms have been removed for clarity.
[Figure 3] Fig. 3. View of the chain parallel to the c axis (vertical) generated by phenyl–phenyl interactions.
1,3-diphenoxy-2,2-bis(phenoxymethyl)propane top
Crystal data top
C29H28O4Dx = 1.156 Mg m3
Mr = 440.51Melting point: 113 K
Tetragonal, I4Cu Kα radiation, λ = 1.54178 Å
Hall symbol: I -4Cell parameters from 2339 reflections
a = 12.2242 (3) Åθ = 5.1–69.7°
c = 8.4655 (3) ŵ = 0.61 mm1
V = 1265.01 (6) Å3T = 220 K
Z = 2Block, colorless
F(000) = 4680.20 × 0.15 × 0.15 mm
Data collection top
Bruker AXS SMART 2K/Platform
diffractometer
643 independent reflections
Radiation source: Sealed Tube613 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 5.5 pixels mm-1θmax = 70.0°, θmin = 5.1°
ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1414
Tmin = 0.896, Tmax = 0.913l = 1010
3443 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-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 reflectionsΔρmax = 0.15 e Å3
76 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.013 (2)
Crystal data top
C29H28O4Z = 2
Mr = 440.51Cu Kα radiation
Tetragonal, I4µ = 0.61 mm1
a = 12.2242 (3) ÅT = 220 K
c = 8.4655 (3) Å0.20 × 0.15 × 0.15 mm
V = 1265.01 (6) Å3
Data collection top
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 = 0.913Rint = 0.059
3443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.08Δρmax = 0.15 e Å3
643 reflectionsΔρmin = 0.20 e Å3
76 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.00001.00000.00000.0504 (10)
C20.10139 (18)1.01889 (18)0.1018 (3)0.0523 (7)
H2A0.09211.08500.16590.063*
H2B0.16591.02850.03450.063*
O30.11545 (14)0.92649 (13)0.2012 (2)0.0592 (6)
C40.19684 (17)0.93000 (18)0.3110 (3)0.0483 (6)
C50.27891 (17)1.00814 (18)0.3152 (3)0.0522 (6)
H50.28161.06380.23870.063*
C60.35678 (18)1.0033 (2)0.4333 (4)0.0619 (7)
H60.41221.05650.43680.074*
C70.3549 (2)0.9222 (3)0.5455 (4)0.0687 (8)
H70.40800.92020.62580.082*
C80.2732 (3)0.8431 (3)0.5386 (4)0.0726 (9)
H80.27140.78680.61420.087*
C90.1953 (2)0.8468 (2)0.4222 (4)0.0647 (8)
H90.14070.79270.41780.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0529 (13)0.0529 (13)0.045 (2)0.0000.0000.000
C20.0533 (11)0.0528 (11)0.0507 (14)0.0065 (8)0.0010 (11)0.0035 (10)
O30.0704 (10)0.0584 (9)0.0486 (11)0.0173 (7)0.0122 (9)0.0092 (8)
C40.0528 (10)0.0554 (11)0.0365 (12)0.0014 (8)0.0037 (10)0.0021 (10)
C50.0501 (10)0.0524 (11)0.0541 (13)0.0026 (7)0.0055 (11)0.0034 (11)
C60.0460 (10)0.0712 (14)0.0686 (18)0.0037 (9)0.0043 (12)0.0082 (13)
C70.0530 (12)0.0950 (18)0.0580 (16)0.0104 (11)0.0062 (11)0.0024 (15)
C80.0746 (15)0.0926 (18)0.0507 (16)0.0053 (13)0.0021 (13)0.0196 (15)
C90.0676 (14)0.0759 (15)0.0506 (16)0.0111 (11)0.0013 (12)0.0140 (12)
Geometric parameters (Å, º) top
C1—C21.527 (2)C5—C61.382 (4)
C1—C2i1.527 (2)C5—H50.94
C1—C2ii1.527 (2)C6—C71.373 (4)
C1—C2iii1.527 (2)C6—H60.94
C2—O31.419 (3)C7—C81.392 (5)
C2—H2a0.98C7—H70.94
C2—H2b0.98C8—C91.371 (4)
O3—C41.362 (3)C8—H80.94
C4—C51.386 (3)C9—H90.94
C4—C91.386 (3)
C2i—C1—C2108.58 (9)C6—C5—C4119.2 (2)
C2i—C1—C2ii108.58 (9)C6—C5—H5120.4
C2—C1—C2ii111.27 (19)C4—C5—H5120.4
C2i—C1—C2iii111.27 (19)C7—C6—C5121.4 (2)
C2—C1—C2iii108.58 (9)C7—C6—H6119.3
C2ii—C1—C2iii108.58 (9)C5—C6—H6119.3
O3—C2—C1108.23 (15)C6—C7—C8119.0 (3)
O3—C2—H2A110.1C6—C7—H7120.5
C1—C2—H2A110.1C8—C7—H7120.5
O3—C2—H2B110.1C9—C8—C7120.4 (3)
C1—C2—H2B110.1C9—C8—H8119.8
H2A—C2—H2B108.4C7—C8—H8119.8
C4—O3—C2117.91 (16)C8—C9—C4120.2 (2)
O3—C4—C5124.6 (2)C8—C9—H9119.9
O3—C4—C9115.50 (19)C4—C9—H9119.9
C5—C4—C9119.9 (2)
C2i—C1—C2—O361.53 (10)C9—C4—C5—C61.6 (4)
C2ii—C1—C2—O357.91 (13)C4—C5—C6—C70.5 (4)
C2iii—C1—C2—O3177.36 (18)C5—C6—C7—C80.6 (4)
C1—C2—O3—C4175.05 (17)C6—C7—C8—C90.6 (5)
C2—O3—C4—C511.9 (3)C7—C8—C9—C40.5 (5)
C2—O3—C4—C9169.3 (2)O3—C4—C9—C8179.6 (3)
O3—C4—C5—C6179.7 (2)C5—C4—C9—C81.6 (4)
Symmetry codes: (i) y+1, x1, z; (ii) x, y2, z; (iii) y1, x1, z.

Experimental details

Crystal data
Chemical formulaC29H28O4
Mr440.51
Crystal system, space groupTetragonal, I4
Temperature (K)220
a, c (Å)12.2242 (3), 8.4655 (3)
V3)1265.01 (6)
Z2
Radiation typeCu Kα
µ (mm1)0.61
Crystal size (mm)0.20 × 0.15 × 0.15
Data collection
DiffractometerBruker AXS SMART 2K/Platform
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.896, 0.913
No. of measured, independent and
observed [I > 2σ(I)] reflections
3443, 643, 613
Rint0.059
(sin θ/λ)max1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.141, 1.08
No. of reflections643
No. of parameters76
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
C1—C21.527 (2)C5—C61.382 (4)
C2—O31.419 (3)C6—C71.373 (4)
O3—C41.362 (3)C7—C81.392 (5)
C4—C51.386 (3)C8—C91.371 (4)
C4—C91.386 (3)
C2i—C1—C2108.58 (9)C5—C4—C9119.9 (2)
C2—C1—C2ii111.27 (19)C6—C5—C4119.2 (2)
O3—C2—C1108.23 (15)C7—C6—C5121.4 (2)
C4—O3—C2117.91 (16)C6—C7—C8119.0 (3)
O3—C4—C5124.6 (2)C9—C8—C7120.4 (3)
O3—C4—C9115.50 (19)C8—C9—C4120.2 (2)
C2i—C1—C2—O361.53 (10)C9—C4—C5—C61.6 (4)
C2ii—C1—C2—O357.91 (13)C4—C5—C6—C70.5 (4)
C2iii—C1—C2—O3177.36 (18)C5—C6—C7—C80.6 (4)
C1—C2—O3—C4175.05 (17)C6—C7—C8—C90.6 (5)
C2—O3—C4—C511.9 (3)C7—C8—C9—C40.5 (5)
C2—O3—C4—C9169.3 (2)O3—C4—C9—C8179.6 (3)
O3—C4—C5—C6179.7 (2)C5—C4—C9—C81.6 (4)
Symmetry codes: (i) y+1, x1, z; (ii) x, y2, z; (iii) y1, x1, z.
 

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