The whole molecule of the title diarylcarbonate is generated by mirror symmetry, the mirror bisecting the central benzene ring, and the carbonate groups adopt an s-cis-s-cis conformation. In the crystal, there are only weak C—H⋯O hydrogen bonds and offset π–π interactions present.
Keywords: crystal structure, diarylcarbonates, diphenylcarbonate, alcoholysis, offset π–π interactions, weak C—H⋯O interactions
Abstract
The whole molecule of the title compound, C20H14O6, is generated by mirror symmetry, the mirror bisecting the central benzene ring. The carbonate groups adopt an s-cis-s-cis conformation, with torsion angles of 58.7 (2) and 116.32 (15)°. The crystal structure of 1,3-phenylene bis(phenyl carbonate) contains no strong hydrogen bonds, though weak C—H⋯O and offset π–π interactions are observed, forming layers parallel to the ac plane.
Chemical context
Organic carbonates have a wide range of applications as polymers, surfactants, fuel additives, solvents for complex industrial syntheses and extractions, and even medical agents, dyes, and foodstuff (Shukla & Srivastava, 2017 ▸). They are commonly synthesized by treating alcohols with phosgene, a rather toxic reagent. Alternative preparatory methods include the reaction of alcohols and carbon monoxide in the presence of a catalyst, direct condensation of alcohols and carbon dioxide (Joe et al., 2012 ▸; Zhang et al. 2012 ▸; Zhao et al., 2009 ▸), or the alcoholysis of urea (Ball et al., 1980 ▸; Bhanage et al., 2003 ▸; Zhang et al., 2016 ▸; Mote & Ranade, 2017 ▸).
The bis(phenyl carbonate) structure reported herein was identified as an unexpected side product from the attempted recrystallization of 1-(m-phenol)-3-phenylurea from ethanol. We surmise this compound formed through a combination of intermolecular ‘self-alcoholysis’ reactions leading to a carbamate intermediate (Mote & Ranade, 2017 ▸), which subsequently over time yields the title compound, 1,3-phenylene bis(phenyl carbonate). Compared to the one-dimensional hydrogen-bonded chain motif so frequently seen in diarylurea crystals (Solomos et al., 2017 ▸; Capacci-Daniel et al., 2010 ▸, 2015 ▸, 2016 ▸), diaryl carbonates lack the ability to associate via strong intermolecular hydrogen bonds. Analysis of the relatively limited number of diaryl carbonate structures previously reported shows that the title compound shares some of the same structural features.
Structural commentary
The molecular structure of the title compound is shown in Fig. 1 ▸. The asymmetric unit consists of half a molecule, as atoms C9 and C11 sit on a mirror plane. The C7=O3 bond distance [1.1878 (18) Å] and the C7—O1 and C7—O2 bond distances [1.3446 (18) Å and 1.3442 (18) Å, respectively] are in good agreement with values reported for other carbonate structures (Cambridge Structural Database: Version 5.38, Groom et al., 2016 ▸). The aromatic rings are both s-cis to the carbonate group with C7—O1—C1—C6 and C7—O2—C8—C10 torsion angles of 58.7 (2) and 116.32 (15)°, respectively. The 1,3-substitution of the central aromatic ring imparts the molecule with a bent or ‘U-shape’ conformation and a significant net dipole moment.
Figure 1.
Molecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level. Unlabeled atoms are related to the labeled atoms by mirror symmetry (symmetry operation: x, −y + 
, z).
Supramolecular Features
The lengths of the unit-cell axes in the 1,3-phenylene bis(phenyl carbonate) structure are strikingly different. Molecules along the a-axis direction are related by glide symmetry and assemble into polar chains (Fig. 2 ▸). A short intermolecular C=O⋯H—C contact (2.59 Å; see Table 1 ▸) between molecules along this axis may favorably contribute to their assembly. The dipoles of adjacent chains in the ab plane adopt an antiparallel alignment, which leads to the very long b axis. The very short c axis reflects the offset π–π stacking between molecules that are related by translation (Fig. 3 ▸). Details: Cg1⋯Cg1i,ii = 3.822 (1) Å, interplanar distance = 3.438 (1) Å, with a slippage of 1.669 Å [Cg1 is the centroid of the phenyl ring C1–C6, symmetry codes: (i) x, y, z − 1; (ii) x, y, z + 1]; Cg2⋯Cg2iii,iv = 3.822 (1) Å, interplanar distance = 3.398 (1) Å, with a slippage of 1.749 Å [Cg2 is the centroid of the central benzene ring, symmetry codes: (iii) x, −y + , z − 1; (iv) x, −y + , z + 1).
Figure 2.
Crystal packing of the title compound viewed along the c axis, showing the antiparallel alignment of adjacent rows of molecules, which creates a long b axis of 31.548 (3) Å. The C—H⋯O hydrogen bonds (see Table 1 ▸) are shown as dashed line.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C10—H10⋯O3i | 0.95 | 2.59 | 3.2105 (8) | 123 |
Symmetry code: (i) 
.
Figure 3.
A partial view along the long b axis of 31.548 (3) Å of the crystal packing of the title compound, showing the π–π stacking interactions (dashed lines).
Database Survey
A search of the Cambridge Structural Database (CSD, Version 5.38 with May 2017 update: Groom et al., 2016 ▸) for organic diphenyl carbonates yielded 20 hits. Interestingly, most of the structures have unit-cell parameters with at least one considerably long axis. With a b-axis length of 31.548 (3) Å, the structure of 1,3-phenylene bis(phenyl carbonate) is consistent with this trend. Across the 20 structures, the C=O bond lengths range between 1.155 and 1.207 Å [average: 1.178 (11) Å], C—O bond lengths fall within 1.310 and 1.387 Å [average: 1.343 (9) Å], and O—C—O angles average 106 (1)°. However, torsion angles about the C—O—C—Carom bonds are extremely variable.
Only one other acyclic bis(phenyl carbonate) was identified in this search, 4,4′-isopropylidenediphenyl-bis(phenylcarbonate) (DINWOM10; Perez & Scaringe, 1987 ▸). The bond lengths and angles are in good agreement with our structure, with C=O = 1.152 and 1.173 Å; C—O = 1.326–1.337 Å and O—C—O = 106.6 and 105.5°. Also similar is the structure of diphenyl carbonate (ZZZPCA02; Hosten & Betz, 2014 ▸), with C=O = 1.188 Å; C—O = 1.343 and 1.337 Å; O—C—O = 104.85°. The aromatic torsion angles for diphenyl carbonate are also similar to the title compound, with C—O—C—C angles of 59.90 and 132.36°.
Synthesis and crystallization
Equimolar amounts of 3-aminophenol and phenyl isocyanate were added to benzene under nitrogen and stirred for 24 h. A white precipitate identified as 1-(m-phenol)-3-phenylurea was filtered, dried, and recrystallized in assorted organic solvents (ethanol, methanol, acetone, ethyl acetate, benzene, toluene, acetone:hexanes, acetonitrile). Slow evaporation of an ethanolic solution in a 1 dram vial, capped with pierced lids, yielded large colorless plates of 1,3-phenylene bis(phenyl carbonate). Needle-like crystals identified within the same vials corresponded to 1-(m-phenol)-3-phenylurea. The appearance of 1,3-phenylene bis(phenyl carbonate) crystals was not consistent across multiple recrystallization experiments, suggesting that select impurities and/or longer, delayed evaporation methods that favor non-equilibrium products may be needed to obtain this material.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms were included as riding idealized contributors with C—H = 0.95 Å and U iso(H) = 1.2U eq(C).
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C20H14O6 |
| M r | 350.31 |
| Crystal system, space group | Orthorhombic, P n m a |
| Temperature (K) | 100 |
| a, b, c (Å) | 12.9597 (12), 31.548 (3), 3.8219 (4) |
| V (Å3) | 1562.6 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.11 |
| Crystal size (mm) | 0.51 × 0.36 × 0.29 |
| Data collection | |
| Diffractometer | Bruker D8 Quest/Photon 100 |
| Absorption correction | Multi-scan (SADABS; Bruker, 2014 ▸) |
| T min, T max | 0.620, 0.746 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 16409, 1625, 1409 |
| R int | 0.044 |
| (sin θ/λ)max (Å−1) | 0.625 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.040, 0.093, 1.16 |
| No. of reflections | 1625 |
| No. of parameters | 121 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.22, −0.28 |
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017016772/su5407sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017016772/su5407Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989017016772/su5407Isup3.cml
CCDC reference: 1586885
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C20H14O6 | Dx = 1.489 Mg m−3 |
| Mr = 350.31 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pnma | Cell parameters from 6581 reflections |
| a = 12.9597 (12) Å | θ = 2.6–28.1° |
| b = 31.548 (3) Å | µ = 0.11 mm−1 |
| c = 3.8219 (4) Å | T = 100 K |
| V = 1562.6 (3) Å3 | Prism, colorless |
| Z = 4 | 0.51 × 0.36 × 0.29 mm |
| F(000) = 728 |
Data collection
| Bruker D8 Quest/Photon 100 diffractometer | 1625 independent reflections |
| Radiation source: microfocus sealed tube | 1409 reflections with I > 2σ(I) |
| Multilayer mirrors monochromator | Rint = 0.044 |
| profile data from φ and ω scans | θmax = 26.4°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −16→16 |
| Tmin = 0.620, Tmax = 0.746 | k = −39→39 |
| 16409 measured reflections | l = −4→4 |
Refinement
| 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.093 | H-atom parameters constrained |
| S = 1.16 | w = 1/[σ2(Fo2) + (0.0297P)2 + 1.0258P] where P = (Fo2 + 2Fc2)/3 |
| 1625 reflections | (Δ/σ)max < 0.001 |
| 121 parameters | Δρmax = 0.22 e Å−3 |
| 0 restraints | Δρmin = −0.28 e Å−3 |
Special details
| Experimental. One distinct cell was identified using APEX2 (Bruker, 2014). Four frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2014) then corrected for absorption by integration using SAINT/SADABS v2014/2 (Bruker, 2014) to sort, merge, and scale the combined data. No decay correction was applied. |
| 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. Structure was phased by direct methods (Sheldrick, 2015). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F2. The final map had no other significant features. A final analysis of variance between observed and calculated structure factors showed some dependence on amplitude and little dependence on resolution. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.53843 (8) | 0.37983 (3) | 0.6378 (3) | 0.0182 (3) | |
| O2 | 0.64043 (8) | 0.32686 (3) | 0.6752 (3) | 0.0176 (3) | |
| O3 | 0.49910 (8) | 0.32050 (3) | 0.3282 (3) | 0.0205 (3) | |
| C1 | 0.45214 (11) | 0.40226 (5) | 0.5132 (4) | 0.0149 (3) | |
| C2 | 0.47199 (12) | 0.44105 (5) | 0.3612 (4) | 0.0166 (3) | |
| H2 | 0.5410 | 0.4506 | 0.3305 | 0.020* | |
| C3 | 0.38982 (12) | 0.46595 (5) | 0.2539 (4) | 0.0185 (3) | |
| H3 | 0.4022 | 0.4928 | 0.1494 | 0.022* | |
| C4 | 0.28937 (12) | 0.45171 (5) | 0.2990 (4) | 0.0175 (3) | |
| H4 | 0.2331 | 0.4687 | 0.2238 | 0.021* | |
| C5 | 0.27117 (12) | 0.41276 (5) | 0.4532 (4) | 0.0178 (3) | |
| H5 | 0.2023 | 0.4031 | 0.4839 | 0.021* | |
| C6 | 0.35262 (12) | 0.38772 (5) | 0.5632 (4) | 0.0159 (3) | |
| H6 | 0.3404 | 0.3611 | 0.6710 | 0.019* | |
| C7 | 0.55226 (11) | 0.33988 (5) | 0.5243 (4) | 0.0144 (3) | |
| C8 | 0.68026 (11) | 0.28716 (5) | 0.5719 (4) | 0.0141 (3) | |
| C9 | 0.63026 (16) | 0.2500 | 0.6630 (6) | 0.0146 (4) | |
| H9 | 0.5657 | 0.2500 | 0.7808 | 0.018* | |
| C10 | 0.77487 (11) | 0.28802 (5) | 0.4077 (4) | 0.0152 (3) | |
| H10 | 0.8068 | 0.3143 | 0.3513 | 0.018* | |
| C11 | 0.82269 (16) | 0.2500 | 0.3264 (6) | 0.0159 (5) | |
| H11 | 0.8882 | 0.2500 | 0.2149 | 0.019* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0145 (5) | 0.0142 (5) | 0.0258 (7) | 0.0025 (4) | −0.0060 (5) | −0.0041 (5) |
| O2 | 0.0132 (5) | 0.0147 (5) | 0.0250 (6) | 0.0033 (4) | −0.0045 (5) | −0.0041 (5) |
| O3 | 0.0155 (5) | 0.0189 (6) | 0.0272 (6) | 0.0020 (4) | −0.0062 (5) | −0.0059 (5) |
| C1 | 0.0134 (7) | 0.0153 (7) | 0.0159 (8) | 0.0029 (6) | −0.0022 (6) | −0.0035 (6) |
| C2 | 0.0142 (7) | 0.0162 (8) | 0.0193 (8) | −0.0034 (6) | 0.0018 (6) | −0.0025 (6) |
| C3 | 0.0207 (8) | 0.0151 (7) | 0.0198 (8) | 0.0005 (6) | 0.0015 (7) | 0.0000 (6) |
| C4 | 0.0153 (7) | 0.0180 (8) | 0.0192 (8) | 0.0043 (6) | −0.0014 (6) | −0.0011 (7) |
| C5 | 0.0131 (7) | 0.0217 (8) | 0.0187 (8) | −0.0009 (6) | 0.0020 (6) | −0.0035 (7) |
| C6 | 0.0176 (8) | 0.0141 (7) | 0.0161 (8) | −0.0014 (6) | 0.0014 (6) | 0.0002 (6) |
| C7 | 0.0110 (7) | 0.0149 (7) | 0.0173 (8) | −0.0002 (5) | 0.0012 (6) | 0.0010 (6) |
| C8 | 0.0139 (7) | 0.0133 (8) | 0.0151 (7) | 0.0019 (6) | −0.0043 (6) | −0.0019 (6) |
| C9 | 0.0091 (10) | 0.0175 (11) | 0.0171 (11) | 0.000 | −0.0008 (8) | 0.000 |
| C10 | 0.0144 (7) | 0.0162 (8) | 0.0151 (7) | −0.0027 (6) | −0.0024 (6) | 0.0010 (6) |
| C11 | 0.0116 (10) | 0.0211 (11) | 0.0150 (11) | 0.000 | −0.0002 (8) | 0.000 |
Geometric parameters (Å, º)
| O1—C7 | 1.3446 (18) | C4—H4 | 0.9500 |
| O1—C1 | 1.4064 (18) | C5—C6 | 1.384 (2) |
| O2—C7 | 1.3442 (18) | C5—H5 | 0.9500 |
| O2—C8 | 1.4109 (18) | C6—H6 | 0.9500 |
| O3—C7 | 1.1878 (18) | C8—C10 | 1.377 (2) |
| C1—C2 | 1.379 (2) | C8—C9 | 1.3842 (19) |
| C1—C6 | 1.382 (2) | C9—C8i | 1.3841 (19) |
| C2—C3 | 1.385 (2) | C9—H9 | 0.9500 |
| C2—H2 | 0.9500 | C10—C11 | 1.3856 (18) |
| C3—C4 | 1.388 (2) | C10—H10 | 0.9500 |
| C3—H3 | 0.9500 | C11—C10i | 1.3856 (18) |
| C4—C5 | 1.383 (2) | C11—H11 | 0.9500 |
| C7—O1—C1 | 117.93 (12) | C1—C6—H6 | 120.6 |
| C7—O2—C8 | 117.53 (12) | C5—C6—H6 | 120.6 |
| C2—C1—C6 | 121.79 (14) | O3—C7—O2 | 127.33 (14) |
| C2—C1—O1 | 116.16 (13) | O3—C7—O1 | 127.50 (14) |
| C6—C1—O1 | 121.89 (14) | O2—C7—O1 | 105.16 (12) |
| C1—C2—C3 | 118.98 (14) | C10—C8—C9 | 123.23 (14) |
| C1—C2—H2 | 120.5 | C10—C8—O2 | 115.82 (13) |
| C3—C2—H2 | 120.5 | C9—C8—O2 | 120.67 (14) |
| C2—C3—C4 | 120.04 (15) | C8i—C9—C8 | 115.8 (2) |
| C2—C3—H3 | 120.0 | C8i—C9—H9 | 122.1 |
| C4—C3—H3 | 120.0 | C8—C9—H9 | 122.1 |
| C5—C4—C3 | 120.04 (14) | C8—C10—C11 | 118.90 (15) |
| C5—C4—H4 | 120.0 | C8—C10—H10 | 120.5 |
| C3—C4—H4 | 120.0 | C11—C10—H10 | 120.5 |
| C4—C5—C6 | 120.43 (14) | C10—C11—C10i | 119.9 (2) |
| C4—C5—H5 | 119.8 | C10—C11—H11 | 120.0 |
| C6—C5—H5 | 119.8 | C10i—C11—H11 | 120.0 |
| C1—C6—C5 | 118.71 (14) | ||
| C7—O1—C1—C2 | −125.86 (15) | C8—O2—C7—O1 | −173.24 (12) |
| C7—O1—C1—C6 | 58.7 (2) | C1—O1—C7—O3 | −0.4 (2) |
| C6—C1—C2—C3 | −0.4 (2) | C1—O1—C7—O2 | 178.35 (12) |
| O1—C1—C2—C3 | −175.82 (14) | C7—O2—C8—C10 | 116.32 (15) |
| C1—C2—C3—C4 | −0.2 (2) | C7—O2—C8—C9 | −69.5 (2) |
| C2—C3—C4—C5 | 0.4 (2) | C10—C8—C9—C8i | −1.4 (3) |
| C3—C4—C5—C6 | −0.1 (2) | O2—C8—C9—C8i | −175.11 (11) |
| C2—C1—C6—C5 | 0.8 (2) | C9—C8—C10—C11 | 0.5 (3) |
| O1—C1—C6—C5 | 175.92 (14) | O2—C8—C10—C11 | 174.47 (15) |
| C4—C5—C6—C1 | −0.5 (2) | C8—C10—C11—C10i | 0.5 (3) |
| C8—O2—C7—O3 | 5.6 (2) |
Symmetry code: (i) x, −y+1/2, z.
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10···O3ii | 0.95 | 2.59 | 3.2105 (8) | 123 |
Symmetry code: (ii) x+1/2, y, −z+1/2.
Funding Statement
This work was funded by National Science Foundation grant DMR-1609541. Achievement Rewards for College Scientists Foundation grant to M.A. Solomos.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017016772/su5407sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017016772/su5407Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989017016772/su5407Isup3.cml
CCDC reference: 1586885
Additional supporting information: crystallographic information; 3D view; checkCIF report