2-Oxo-2 H -chromen-4-yl 4-methoxybenzoate

Akoun Abou, Abdoulaye Djandé, Grégoire Danger, Adama Saba, Rita Kakou-Yao

► To cite this version:

Akoun Abou, Abdoulaye Djandé, Grégoire Danger, Adama Saba, Rita Kakou-Yao. 2-Oxo-2 H -chromen-4-yl 4-methoxybenzoate. Acta Crystallographica Section E: Structure Reports Online [2001-2014], 2012, 68 (12), pp.o3438-o3439. 10.1107/S1600536812047666. hal-03332572

HAL Id: hal-03332572

https://hal.science/hal-03332572

Submitted on 22 Sep 2021

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
## 2-Oxo-2H-chromen-4-yl 4-methoxybenzoate

Akoun Abou,ª* Abdoulaye Djandé,ᵇ Grégoire Danger,ᶜ Adama Sabaᵇ and Rita Kakou-Yaoª

ªLaboratoire de Cristallographie et Physique Moléculaire, UFR SSMT, Université de Cocody, 22 BP 582 Abidjan 22, Côte d'Ivoire, ᵇLaboratoire de Chimie Bio-organique et de Phytochimie, Université de Ouagadougou, 03 BP 7021 Ouagadougou 03, Burkina Faso, and ᶜLaboratoire de Physique des Interactions Ioniques et Moléculaires, Equipe-Spectrométries et Dynamique Moléculaire, Centre Saint Jérôme, Université de Provence, 13397 Marseille, France
Correspondence e-mail: abou_akoun@yahoo.fr

Received 8 November 2012; accepted 20 November 2012

Key indicators: single-crystal X-ray study; *T* = 298 K; mean *σ*(C–C) = 0.004 Å; *R* factor = 0.066; *wR* factor = 0.163; data-to-parameter ratio = 13.7.

In the title molecule, C₁₇H₁₂O₅, the chromen-2-one ring and the 4-methoxybenzoate side chain are inclined to one another at a dihedral angle of 69.82 (9)°. The crystal structure features parallel sheets of centrosymmetric R₂(6) dimers joined by a C(7) chain, resulting in centrosymmetric tetramers of hydrogen-bonded molecules with graph-set motif R₄(40). These centrosymmetric tetramers are connected by a pair of hydrogen bonds described by an R₂(8) ring motif and a C(7) chain via C—H···O interactions. In the structure, there are also π–π stacking interactions between chromene benzene and the six-membered heterocyclic rings [centroid–centroid distance = 3.691 (2) Å] and weak C=O···π interactions [O···(ring centroid) distance = 3.357 (3) Å].

### Related literature

For the biological activity of coumarin derivatives, see: Basagnouda *et al.* (2009); Vukovic *et al.* (2010); Emmanuel-Giota *et al.* (2001); Marchenko *et al.* (2006). For hydrogen-bond motifs, see: Bernstein *et al.* (1995). For π–π stacking interactions, see: Janiak (2000).

<figure><img src="image_2.png" /></figure>

### Experimental

#### Crystal data

<table><tr><td>C<sub>17</sub>H<sub>12</sub>O<sub>5</sub></td><td>γ = 81.893 (1)°</td></tr><tr><td>M<sub>r</sub> = 296.27</td><td>V = 686.8 (3) Å<sup>3</sup></td></tr><tr><td>Triclinic, <i>P</i>1</td><td>Z = 2</td></tr><tr><td><i>a</i> = 4.371 (1) Å</td><td>Mo Kα radiation</td></tr><tr><td><i>b</i> = 10.535 (4) Å</td><td>μ = 0.11 mm<sup>-1</sup></td></tr><tr><td><i>c</i> = 15.193 (2) Å</td><td><i>T</i> = 298 K</td></tr><tr><td>α = 85.218 (3)°</td><td>0.25 × 0.15 × 0.04 mm</td></tr><tr><td>β = 83.688 (2)°</td><td></td></tr></table>

#### Data collection

<table><tr><td>Nonius KappaCCD diffractometer</td><td>1540 reflections with <i>I</i> > 2σ(<i>I</i>)</td></tr><tr><td>5683 measured reflections</td><td><i>R</i><sub>int</sub> = 0.055</td></tr><tr><td>2731 independent reflections</td><td></td></tr></table>

#### Refinement

<table><caption>**Table 1**
Hydrogen-bond geometry (Å, °).</caption><tr><td><i>R</i>[<i>F</i><sup>2</sup> > 2σ(<i>F</i><sup>2</sup>)] = 0.066</td><td>200 parameters</td></tr><tr><td><i>wR</i>(<i>F</i><sup>2</sup>) = 0.163</td><td>H-atom parameters constrained</td></tr><tr><td><i>S</i> = 1.11</td><td>Δρ<sub>max</sub> = 0.17 e Å<sup>-3</sup></td></tr><tr><td>2731 reflections</td><td>Δρ<sub>min</sub> = -0.23 e Å<sup>-3</sup></td></tr></table>

<table><thead><tr><th><i>D</i>–<i>H</i>···<i>A</i></th><th><i>D</i>–<i>H</i></th><th><i>H</i>···<i>A</i></th><th><i>D</i>···<i>A</i></th><th><i>D</i>–<i>H</i>···<i>A</i></th></tr></thead><tbody><tr><td>C8–H8···O2<sup>i</sup></td><td>0.93</td><td>2.48</td><td>3.407 (4)</td><td>173</td></tr><tr><td>C2–H2···O4<sup>ii</sup></td><td>0.93</td><td>2.49</td><td>3.340 (4)</td><td>151</td></tr><tr><td>C17–H17B···O5<sup>iii</sup></td><td>0.96</td><td>2.59</td><td>3.461 (4)</td><td>151</td></tr></tbody></table>

Symmetry codes: (i) $-x - 1, -y, -z + 1$; (ii) $x + 1, y, z$; (iii) $-x + 2, -y - 1, -z$.

Data collection: **COLLECT** (Hooft, 1998); cell refinement: **DENZO/SCALEPACK** (Otwinowski & Minor, 1997); data reduction: **DENZO/SCALEPACK**; program(s) used to solve structure: **SIR2004** (Burla *et al.*, 2005); program(s) used to refine structure: **SHELXL97** (Sheldrick, 2008); molecular graphics: **PLATON** (Spek, 2009); software used to prepare material for publication: **SHELXL97**, **publCIF** (Westrip, 2010) and **WinGX** (Farrugia, 2012).

The authors thank the Spectropôle Service of the Faculty of Sciences and Techniques of Saint Jérôme (France) for the use of the diffractometer and the NMR spectrometer.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2245).
References

Basanagouda, M., Kulkarni, M. V., Sharma, D., Gupta, V. K., Sandhyarani, P. & Rasal, V. P. (2009). *J. Chem. Sci.* **121**, 485–495.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). *Angew. Chem. Int. Ed. Engl.* **34**, 1555–1573.

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). *J. Appl. Cryst.* **38**, 381–388.

Emmanuel-Giota, A. A., Fylaktakidou, K. C., Hadjipavlou-Litina, D. J., Litinas, K. E. & Nicolaides, D. N. (2001). *J. Heterocycl. Chem.* **38**, 717–722.

Farrugia, L. J. (2012). *J. Appl. Cryst.* **45**, 849–854.

Hooft, R. (1998). *COLLECT*. Nonius BV, Delft, The Netherlands.

Janiak, C. (2000). *J. Chem. Soc. Dalton Trans.* pp. 3885–3896.

Marchenko, M. M., Kopyl'chuk, G. P., Shmarakov, I. A., Ketsa, O. V. & Kushnir, V. M. (2006). *Pharm. Chem. J.* **40**, 296–297.

Otwinowski, Z. & Minor, W. (1997). *Methods in Enzymology*, Vol. 276, *Macromolecular Crystallography*, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (2008). *Acta Cryst.* **A64**, 112–122.

Spek, A. L. (2009). *Acta Cryst.* **D65**, 148–155.

Vukovic, N., Sukdolak, S., Solujic, S. & Niciforovic, N. (2010). *Arch. Pharm. Res.* **33**, 5–15.

Westrip, S. P. (2010). *J. Appl. Cryst.* **43**, 920–925.
supporting information

*Acta Cryst.* (2012). **E68**, o3438–o3439 [doi:10.1107/S1600536812047666]

2-Oxo-2H-chromen-4-yl 4-methoxybenzoate

Akoun Abou, Abdoulaye Djandé, Grégoire Danger, Adama Saba and Rita Kakou-Yao

S1. Comment

Coumarin constitutes one of the major classes of naturally occurring compounds and interest in its chemistry continues unabated because of its usefulness as a biologically active agent. It also represents the core structure of several molecules of pharmaceutical importance. Coumarin and its derivatives have been reported to serve as anti-bacterial (Basanagouda *et al.*, 2009), anti-oxidant (Vukovic *et al.*, 2010), anti-inflammatory (Emmanuel-Giota *et al.*, 2001) and anti-tumour agents (Marchenko, *et al.*, 2006). Therefore, the synthesis of new coumarin derivatives is of considerable interest. In order to study the influence of new substituents on the activity of the coumarin derivatives, the title compound, the ester $C_{17}H_{12}O_5$ has been synthesized and its molecular and crystal structure is reported herein.

In the title compound (Fig. 1), the side chain is tilted with respect to the chromen-2-one ring with torsion angles C1—C9—O3—C10 = -76.3 (4)° and C8—C9—O3—C10 = 107.7 (3)°. The dihedral angle between the chromene ring and the side chain is 69.82 (9) °.

In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) generate hydrogen-bonding motifs ranging from a chain to various rings. Indeed, in the methoxy group, an H atom of the methyl group (H17B) bonds to the oxygen atom of the same group on a neighbouring molecule (related by an inversion center) to form parallel sheets of centrosymmetric dimers [graph set $R_2^2(6)$ (Bernstein *et al.*, 1995)]. Also, a hydrogen of the chromene-benzene ring (H2) bonds to the oxygen atom of the carbonyl group of the side chain of a neighbouring molecule to form an infinite chain [graph set C(7)]. The combination of the C(7) chain and the $R_2^2(6)$ dimers results in a ring of hydrogen-bonded molecules described by the graph set $R_4^4(40)$ (Fig. 2). Further, the hydrogen of the six-membered heterocyclic ring bonds to the oxygen atom of the carbonyl group of the chromen-2-one moiety of an inversion-related neighbouring molecule to form a pair of hydrogen bonds [graph set $R_2^2(8)$]. The latter hydrogen bonds and the C(7) chain connect the $R_4^4(40)$ centrosymmetric tetramers, resulting in a supramolecular aggregation (Fig. 3) which is further consolidated by weak C=O···π interactions [O2···Cg1 (x - 1, y, z) = 3.357 (3) Å], where Cg1 is the centroid of the six-membered O containing ring, and π–π stacking between the chromene-benzene C1—C6 and the six-membered heterocyclic rings; in the latter, the centroid···centroid distance, [Cg2···Cg1 (x + 1, y, z) or Cg1···Cg2 (x - 1, y, z) = 3.691 (2) Å], is less than 3.8 Å, the maximum regarded as relevant for π–π interactions (Janiak, 2000) (Fig. 4).

S2. Experimental

To a solution of 4-methoxybenzoyl chloride (40 mmol) in dried tetrahydrofuran (150 ml), was added dried triethylamine (120 mmol) and 4-hydroxycoumarin (40 mmol) in small portions over 30 min. The mixture was then refluxed for 3 h and poured in 300 ml of chloroform. The solution was acidified with dilute hydrochloric acid until the pH was 2–3. The organic layer was extracted, washed with water, dried over $MgSO_4$ and the solvent removed. The crude product was recrystallized from chloroform. Colourless crystals of the title compound were obtained in a good yield (84%); m.p. 421–422 K. ¹H NMR (Bruker TOPSPIN, CDCl₃, 400 MHz, p.p.m.) δ: 6.63 (s, 1H, H8); 7.43 (d, 1H, H2); 7.33 (t.d, 1H, H3);
7.61 (t,d,1H, H4); 7.73 (d, 1H, H5); 8.2 (d, 2H, H12 and H16); 7.05 (d, 2H, H13 and H15); 3.93 (s, 3H, CH3). ¹³C NMR (Bruker TOPSPIN, CDCl3, 100 MHz, p.p.m.) δ: 162 (C7); 108 (C8); 161 (C9); 127 (C2); 124 (C3); 117 (C4); 126 (C5); 153 (C6); 115 (C1); 165 (C10); 160 (C11); 133 (C12 and C16); 113 (C13 and C15); 120 (C14); 55 (C17).

S3. Refinement

H atoms were placed in calculated positions [C—H = 0.93 (aromatic) or 0.96 Å (methyl group)] and refined using a riding model approximation with *U*<sub>iso</sub>(H) constrained to 1.2 (aromatic) or 1.5 (methyl) times *U*<sub>eq</sub> of the respective parent atom. The five reflections (1 - 5 17), (0 - 1 1), (0 0 1), (0 1 0), (1 0 1) were found to have too low intensities, caused by a systematic error, probably by shielding by the beam stop interference. They were omitted from the refinement.

<figure><img src="image_3.png" /><figcaption>**Figure 1**</figcaption></figure>

The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
<figure><img src="image_4.png" /><figcaption>Figure 2</figcaption></figure>

The crystal packing, viewed down the *c* axis, showing parallel sheets of centrosymmetric *R*₂²(6) dimers linked by an infinite *C*(7) chain to form a centrosymmetric *R*₄⁴(40) tetramers. The dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.
<figure><img src="image_5.png" /><figcaption>Figure 3</figcaption></figure>

The crystal packing, viewed down the *c* axis, showing the supramolecular aggregation formed by the propagation of the centrosymmetric *R*₄*(40) tetramers via C—H···O hydrogen bonds. The dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.
<figure><img src="image_6.png" /><figcaption>**Figure 4**</figcaption></figure>

A view of the crystal packing, showing C=O···π and π-π stacking interactions (dashed lines). The green dots are centroids of rings. H atoms have been omitted.

**2-Oxo-2H-chromen-4-yl 4-methoxybenzoate**

*Crystal data*

$C_{17}H_{12}O_5$

$M_r = 296.27$

Triclinic, $P\bar{1}$

Hall symbol: -P 1

$a = 4.371 (1) Å$

$b = 10.535 (4) Å$

$c = 15.193 (2) Å$

$\alpha = 85.218 (3)°$

$\beta = 83.688 (2)°$

$\gamma = 81.893 (1)°$

$V = 686.8 (3) Å^3$

$Z = 2$

$F(000) = 308$

$D_x = 1.433 \text{ Mg m}^{-3}$

Melting point = 421–422 K

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 5683 reflections

$\theta = 2.3–27.0°$

$\mu = 0.11 \text{ mm}^{-1}$

$T = 298 K$

Prism, colourless

$0.25 \times 0.15 \times 0.04 \text{ mm}$
## Data collection

Nonius KappaCCD 1540 reflections with $I > 2\sigma(I)$
diffractometer $R_{int} = 0.055$

Radiation source: fine-focus sealed tube $\theta_{max} = 27.0^{\circ}$, $\theta_{min} = 2.3^{\circ}$

Graphite monochromator $h = 0 \rightarrow 5$

$\varphi$ and $\omega$ scans $k = -12 \rightarrow 13$

5683 measured reflections $l = -18 \rightarrow 19$

2731 independent reflections

## Refinement

Refinement on $F^2$ Secondary atom site location: difference Fourier
Least-squares matrix: full map

$R[F^2 > 2\sigma(F^2)] = 0.066$ Hydrogen site location: inferred from

$wR(F^2) = 0.163$ neighbouring sites

$S = 1.11$ H-atom parameters constrained

2731 reflections $w = 1/[\sigma^2(F_o^2) + (0.0324P)^2 + 0.5861P]$

200 parameters where $P = (F_o^2 + 2F_c^2)/3$

0 restraints $(\Delta/\sigma)_{max} < 0.001$

48 constraints $\Delta\rho_{max} = 0.17$ e Å$^{-3}$

## Special details

**Geometry.** All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

**Refinement.** Refinement of $F^2$ against ALL reflections. The weighted R-factor $wR$ and goodness of fit $S$ are based on $F^2$, conventional R-factors $R$ are based on $F$, with $F$ set to zero for negative $F^2$. The threshold expression of $F^2 > 2\sigma(F^2)$ is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on $F^2$ 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 (Å$^2$)

<table><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th></tr></thead><tbody><tr><td>O3</td><td>0.1598 (5)</td><td>0.05340 (19)</td><td>0.31179 (13)</td><td>0.0542 (6)</td></tr><tr><td>O1</td><td>-0.3230 (5)</td><td>0.3325 (2)</td><td>0.47003 (14)</td><td>0.0528 (6)</td></tr><tr><td>O2</td><td>-0.5808 (6)</td><td>0.1879 (2)</td><td>0.54685 (17)</td><td>0.0722 (7)</td></tr><tr><td>C11</td><td>0.2683 (7)</td><td>-0.0573 (3)</td><td>0.1811 (2)</td><td>0.0447 (7)</td></tr><tr><td>O4</td><td>-0.1068 (6)</td><td>0.1288 (2)</td><td>0.19569 (15)</td><td>0.0656 (7)</td></tr><tr><td>O5</td><td>0.7433 (6)</td><td>-0.3598 (2)</td><td>0.04518 (16)</td><td>0.0702 (7)</td></tr><tr><td>C5</td><td>-0.0670 (8)</td><td>0.4966 (3)</td><td>0.3926 (2)</td><td>0.0525 (8)</td></tr><tr><td>H5</td><td>-0.1839</td><td>0.5552</td><td>0.4297</td><td>0.063*</td></tr><tr><td>C9</td><td>-0.0098 (7)</td><td>0.1490 (3)</td><td>0.3629 (2)</td><td>0.0459 (8)</td></tr><tr><td>C1</td><td>0.0601 (7)</td><td>0.2784 (3)</td><td>0.3473 (2)</td><td>0.0443 (7)</td></tr><tr><td>C6</td><td>-0.1068 (7)</td><td>0.3679 (3)</td><td>0.4027 (2)</td><td>0.0455 (8)</td></tr><tr><td>C14</td><td>0.5790 (7)</td><td>-0.2567 (3)</td><td>0.0861 (2)</td><td>0.0512 (8)</td></tr><tr><td>C10</td><td>0.0876 (8)</td><td>0.0505 (3)</td><td>0.2267 (2)</td><td>0.0500 (8)</td></tr><tr><td>C4</td><td>0.1473 (8)</td><td>0.5360 (3)</td><td>0.3273 (2)</td><td>0.0586 (9)</td></tr><tr><td>H4</td><td>0.1758</td><td>0.6222</td><td>0.3199</td><td>0.070*</td></tr><tr><td>C7</td><td>-0.3849 (8)</td><td>0.2081 (3)</td><td>0.4861 (2)</td><td>0.0532 (8)</td></tr><tr><td>C12</td><td>0.4725 (7)</td><td>-0.1501 (3)</td><td>0.2215 (2)</td><td>0.0510 (8)</td></tr></tbody></table>
<table><tr><td>H12</td><td>0.5054</td><td>-0.1455</td><td>0.2805</td><td>0.061*</td></tr><tr><td>C15</td><td>0.3792 (8)</td><td>-0.1649 (3)</td><td>0.0454 (2)</td><td>0.0612 (10)</td></tr><tr><td>H15</td><td>0.3468</td><td>-0.1691</td><td>-0.0138</td><td>0.073*</td></tr><tr><td>C8</td><td>-0.2172 (8)</td><td>0.1147 (3)</td><td>0.4278 (2)</td><td>0.0520 (8)</td></tr><tr><td>H8</td><td>-0.2550</td><td>0.0296</td><td>0.4359</td><td>0.062*</td></tr><tr><td>C13</td><td>0.6278 (8)</td><td>-0.2498 (3)</td><td>0.1738 (2)</td><td>0.0565 (9)</td></tr><tr><td>H13</td><td>0.7656</td><td>-0.3125</td><td>0.2008</td><td>0.068*</td></tr><tr><td>C16</td><td>0.2264 (8)</td><td>-0.0658 (3)</td><td>0.0939 (2)</td><td>0.0618 (10)</td></tr><tr><td>H16</td><td>0.0905</td><td>-0.0027</td><td>0.0665</td><td>0.074*</td></tr><tr><td>C3</td><td>0.3223 (8)</td><td>0.4490 (3)</td><td>0.2719 (2)</td><td>0.0585 (9)</td></tr><tr><td>H3</td><td>0.4692</td><td>0.4768</td><td>0.2283</td><td>0.070*</td></tr><tr><td>C2</td><td>0.2795 (7)</td><td>0.3217 (3)</td><td>0.2813 (2)</td><td>0.0525 (8)</td></tr><tr><td>H2</td><td>0.3965</td><td>0.2639</td><td>0.2437</td><td>0.063*</td></tr><tr><td>C17</td><td>0.7156 (10)</td><td>-0.3667 (4)</td><td>-0.0473 (2)</td><td>0.0784 (12)</td></tr><tr><td>H17A</td><td>0.5023</td><td>-0.3692</td><td>-0.0560</td><td>0.118*</td></tr><tr><td>H17B</td><td>0.8401</td><td>-0.4429</td><td>-0.0680</td><td>0.118*</td></tr><tr><td>H17C</td><td>0.7859</td><td>-0.2924</td><td>-0.0800</td><td>0.118*</td></tr></table>

Atomic displacement parameters (Å²)

<table><thead><tr><th></th><th>U<sup>11</sup></th><th>U<sup>22</sup></th><th>U<sup>33</sup></th><th>U<sup>12</sup></th><th>U<sup>13</sup></th><th>U<sup>23</sup></th></tr></thead><tbody><tr><td>O3</td><td>0.0695 (15)</td><td>0.0459 (12)</td><td>0.0453 (13)</td><td>0.0091 (10)</td><td>-0.0096 (11)</td><td>-0.0155 (10)</td></tr><tr><td>O1</td><td>0.0634 (14)</td><td>0.0459 (13)</td><td>0.0478 (13)</td><td>-0.0031 (10)</td><td>0.0020 (11)</td><td>-0.0138 (10)</td></tr><tr><td>O2</td><td>0.0892 (19)</td><td>0.0661 (16)</td><td>0.0575 (16)</td><td>-0.0115 (13)</td><td>0.0144 (14)</td><td>-0.0096 (12)</td></tr><tr><td>C11</td><td>0.0515 (19)</td><td>0.0393 (17)</td><td>0.0429 (18)</td><td>-0.0017 (13)</td><td>-0.0024 (14)</td><td>-0.0103 (14)</td></tr><tr><td>O4</td><td>0.0724 (16)</td><td>0.0624 (15)</td><td>0.0601 (15)</td><td>0.0189 (12)</td><td>-0.0207 (13)</td><td>-0.0215 (12)</td></tr><tr><td>O5</td><td>0.0938 (19)</td><td>0.0529 (14)</td><td>0.0594 (16)</td><td>0.0174 (13)</td><td>-0.0090 (13)</td><td>-0.0219 (12)</td></tr><tr><td>C5</td><td>0.060 (2)</td><td>0.0451 (19)</td><td>0.054 (2)</td><td>0.0007 (15)</td><td>-0.0131 (17)</td><td>-0.0166 (15)</td></tr><tr><td>C9</td><td>0.057 (2)</td><td>0.0391 (17)</td><td>0.0418 (18)</td><td>0.0060 (14)</td><td>-0.0117 (16)</td><td>-0.0130 (14)</td></tr><tr><td>C1</td><td>0.0482 (18)</td><td>0.0443 (18)</td><td>0.0404 (17)</td><td>0.0026 (14)</td><td>-0.0096 (14)</td><td>-0.0106 (14)</td></tr><tr><td>C6</td><td>0.0508 (19)</td><td>0.0458 (18)</td><td>0.0407 (18)</td><td>-0.0030 (14)</td><td>-0.0080 (15)</td><td>-0.0095 (14)</td></tr><tr><td>C14</td><td>0.060 (2)</td><td>0.0394 (17)</td><td>0.053 (2)</td><td>0.0007 (15)</td><td>-0.0023 (16)</td><td>-0.0139 (15)</td></tr><tr><td>C10</td><td>0.055 (2)</td><td>0.0488 (19)</td><td>0.047 (2)</td><td>-0.0023 (16)</td><td>-0.0085 (16)</td><td>-0.0116 (15)</td></tr><tr><td>C4</td><td>0.070 (2)</td><td>0.047 (2)</td><td>0.061 (2)</td><td>-0.0107 (17)</td><td>-0.0139 (19)</td><td>-0.0028 (17)</td></tr><tr><td>C7</td><td>0.065 (2)</td><td>0.049 (2)</td><td>0.045 (2)</td><td>-0.0026 (16)</td><td>-0.0074 (17)</td><td>-0.0086 (15)</td></tr><tr><td>C12</td><td>0.063 (2)</td><td>0.0443 (18)</td><td>0.0452 (19)</td><td>-0.0020 (15)</td><td>-0.0084 (16)</td><td>-0.0076 (15)</td></tr><tr><td>C15</td><td>0.077 (2)</td><td>0.059 (2)</td><td>0.047 (2)</td><td>0.0108 (18)</td><td>-0.0159 (18)</td><td>-0.0186 (17)</td></tr><tr><td>C8</td><td>0.066 (2)</td><td>0.0430 (18)</td><td>0.0464 (19)</td><td>-0.0012 (15)</td><td>-0.0070 (17)</td><td>-0.0073 (15)</td></tr><tr><td>C13</td><td>0.071 (2)</td><td>0.0420 (18)</td><td>0.053 (2)</td><td>0.0105 (16)</td><td>-0.0108 (17)</td><td>-0.0073 (16)</td></tr><tr><td>C16</td><td>0.078 (2)</td><td>0.054 (2)</td><td>0.051 (2)</td><td>0.0165 (17)</td><td>-0.0171 (18)</td><td>-0.0157 (17)</td></tr><tr><td>C3</td><td>0.065 (2)</td><td>0.062 (2)</td><td>0.051 (2)</td><td>-0.0137 (17)</td><td>-0.0056 (17)</td><td>-0.0051 (17)</td></tr><tr><td>C2</td><td>0.056 (2)</td><td>0.057 (2)</td><td>0.0447 (19)</td><td>0.0012 (16)</td><td>-0.0072 (16)</td><td>-0.0129 (15)</td></tr><tr><td>C17</td><td>0.103 (3)</td><td>0.071 (3)</td><td>0.057 (2)</td><td>0.015 (2)</td><td>-0.006 (2)</td><td>-0.029 (2)</td></tr></tbody></table>

Geometric parameters (Å, °)

<table><tr><td>O3—C10</td><td>1.368 (4)</td><td>C14—C15</td><td>1.365 (4)</td></tr><tr><td>O3—C9</td><td>1.400 (3)</td><td>C14—C13</td><td>1.381 (4)</td></tr></table>
<table>
  <tbody>
    <tr>
      <td>O1—C7</td>
      <td>1.373 (4)</td>
      <td>C4—C3</td>
      <td>1.387 (5)</td>
    </tr>
    <tr>
      <td>O1—C6</td>
      <td>1.379 (4)</td>
      <td>C4—H4</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>O2—C7</td>
      <td>1.214 (4)</td>
      <td>C7—C8</td>
      <td>1.445 (4)</td>
    </tr>
    <tr>
      <td>C11—C16</td>
      <td>1.369 (4)</td>
      <td>C12—C13</td>
      <td>1.381 (4)</td>
    </tr>
    <tr>
      <td>C11—C12</td>
      <td>1.380 (4)</td>
      <td>C12—H12</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>C11—C10</td>
      <td>1.467 (4)</td>
      <td>C15—C16</td>
      <td>1.379 (4)</td>
    </tr>
    <tr>
      <td>O4—C10</td>
      <td>1.204 (4)</td>
      <td>C15—H15</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>O5—C14</td>
      <td>1.370 (3)</td>
      <td>C8—H8</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>O5—C17</td>
      <td>1.433 (4)</td>
      <td>C13—H13</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>C5—C4</td>
      <td>1.368 (4)</td>
      <td>C16—H16</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>C5—C6</td>
      <td>1.385 (4)</td>
      <td>C3—C2</td>
      <td>1.373 (4)</td>
    </tr>
    <tr>
      <td>C5—H5</td>
      <td>0.9300</td>
      <td>C3—H3</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>C9—C8</td>
      <td>1.327 (4)</td>
      <td>C2—H2</td>
      <td>0.9300</td>
    </tr>
    <tr>
      <td>C9—C1</td>
      <td>1.434 (4)</td>
      <td>C17—H17A</td>
      <td>0.9600</td>
    </tr>
    <tr>
      <td>C1—C6</td>
      <td>1.391 (4)</td>
      <td>C17—H17B</td>
      <td>0.9600</td>
    </tr>
    <tr>
      <td>C1—C2</td>
      <td>1.403 (4)</td>
      <td>C17—H17C</td>
      <td>0.9600</td>
    </tr>
    <tr>
      <td>C10—O3—C9</td>
      <td>117.2 (2)</td>
      <td>O1—C7—C8</td>
      <td>116.9 (3)</td>
    </tr>
    <tr>
      <td>C7—O1—C6</td>
      <td>122.2 (2)</td>
      <td>C11—C12—C13</td>
      <td>119.6 (3)</td>
    </tr>
    <tr>
      <td>C16—C11—C12</td>
      <td>119.0 (3)</td>
      <td>C11—C12—H12</td>
      <td>120.2</td>
    </tr>
    <tr>
      <td>C16—C11—C10</td>
      <td>117.4 (3)</td>
      <td>C13—C12—H12</td>
      <td>120.2</td>
    </tr>
    <tr>
      <td>C12—C11—C10</td>
      <td>123.6 (3)</td>
      <td>C14—C15—C16</td>
      <td>118.4 (3)</td>
    </tr>
    <tr>
      <td>C14—O5—C17</td>
      <td>117.5 (3)</td>
      <td>C14—C15—H15</td>
      <td>120.8</td>
    </tr>
    <tr>
      <td>C4—C5—C6</td>
      <td>118.9 (3)</td>
      <td>C16—C15—H15</td>
      <td>120.8</td>
    </tr>
    <tr>
      <td>C4—C5—H5</td>
      <td>120.6</td>
      <td>C9—C8—C7</td>
      <td>120.8 (3)</td>
    </tr>
    <tr>
      <td>C6—C5—H5</td>
      <td>120.6</td>
      <td>C9—C8—H8</td>
      <td>119.6</td>
    </tr>
    <tr>
      <td>C8—C9—O3</td>
      <td>118.5 (3)</td>
      <td>C7—C8—H8</td>
      <td>119.6</td>
    </tr>
    <tr>
      <td>C8—C9—C1</td>
      <td>122.3 (3)</td>
      <td>C12—C13—C14</td>
      <td>120.2 (3)</td>
    </tr>
    <tr>
      <td>O3—C9—C1</td>
      <td>119.1 (3)</td>
      <td>C12—C13—H13</td>
      <td>119.9</td>
    </tr>
    <tr>
      <td>C6—C1—C2</td>
      <td>117.9 (3)</td>
      <td>C14—C13—H13</td>
      <td>119.9</td>
    </tr>
    <tr>
      <td>C6—C1—C9</td>
      <td>116.4 (3)</td>
      <td>C11—C16—C15</td>
      <td>122.1 (3)</td>
    </tr>
    <tr>
      <td>C2—C1—C9</td>
      <td>125.7 (3)</td>
      <td>C11—C16—H16</td>
      <td>118.9</td>
    </tr>
    <tr>
      <td>O1—C6—C5</td>
      <td>116.8 (3)</td>
      <td>C15—C16—H16</td>
      <td>118.9</td>
    </tr>
    <tr>
      <td>O1—C6—C1</td>
      <td>121.3 (3)</td>
      <td>C2—C3—C4</td>
      <td>120.2 (3)</td>
    </tr>
    <tr>
      <td>C5—C6—C1</td>
      <td>121.9 (3)</td>
      <td>C2—C3—H3</td>
      <td>119.9</td>
    </tr>
    <tr>
      <td>C15—C14—O5</td>
      <td>123.9 (3)</td>
      <td>C4—C3—H3</td>
      <td>119.9</td>
    </tr>
    <tr>
      <td>C15—C14—C13</td>
      <td>120.6 (3)</td>
      <td>C3—C2—C1</td>
      <td>120.4 (3)</td>
    </tr>
    <tr>
      <td>O5—C14—C13</td>
      <td>115.5 (3)</td>
      <td>C3—C2—H2</td>
      <td>119.8</td>
    </tr>
    <tr>
      <td>O4—C10—O3</td>
      <td>121.8 (3)</td>
      <td>C1—C2—H2</td>
      <td>119.8</td>
    </tr>
    <tr>
      <td>O4—C10—C11</td>
      <td>125.8 (3)</td>
      <td>O5—C17—H17A</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>O3—C10—C11</td>
      <td>112.4 (3)</td>
      <td>O5—C17—H17B</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>C5—C4—C3</td>
      <td>120.8 (3)</td>
      <td>H17A—C17—H17B</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>C5—C4—H4</td>
      <td>119.6</td>
      <td>O5—C17—H17C</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>C3—C4—H4</td>
      <td>119.6</td>
      <td>H17A—C17—H17C</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>O2—C7—O1</td>
      <td>116.6 (3)</td>
      <td>H17B—C17—H17C</td>
      <td>109.5</td>
    </tr>
    <tr>
      <td>O2—C7—C8</td>
      <td>126.4 (3)</td>
      <td></td>
      <td></td>
    </tr>
    <tr>
      <td>C10—O3—C9—C8</td>
      <td>107.7 (3)</td>
      <td>C6—C5—C4—C3</td>
      <td>0.0 (5)</td>
    </tr>
  </tbody>
</table>
<table><caption>Hydrogen-bond geometry (Å, °)</caption><tr><td>C10—O3—C9—C1</td><td>-76.3 (4)</td><td>C6—O1—C7—O2</td><td>-179.7 (3)</td></tr><tr><td>C8—C9—C1—C6</td><td>-1.4 (4)</td><td>C6—O1—C7—C8</td><td>-1.3 (4)</td></tr><tr><td>O3—C9—C1—C6</td><td>-177.3 (3)</td><td>C16—C11—C12—C13</td><td>-0.6 (5)</td></tr><tr><td>C8—C9—C1—C2</td><td>178.8 (3)</td><td>C10—C11—C12—C13</td><td>178.6 (3)</td></tr><tr><td>O3—C9—C1—C2</td><td>2.9 (5)</td><td>O5—C14—C15—C16</td><td>179.8 (3)</td></tr><tr><td>C7—O1—C6—C5</td><td>179.5 (3)</td><td>C13—C14—C15—C16</td><td>-0.3 (5)</td></tr><tr><td>C7—O1—C6—C1</td><td>0.1 (4)</td><td>O3—C9—C8—C7</td><td>176.2 (3)</td></tr><tr><td>C4—C5—C6—O1</td><td>179.4 (3)</td><td>C1—C9—C8—C7</td><td>0.3 (5)</td></tr><tr><td>C4—C5—C6—C1</td><td>-1.3 (5)</td><td>O2—C7—C8—C9</td><td>179.3 (3)</td></tr><tr><td>C2—C1—C6—O1</td><td>-179.0 (3)</td><td>O1—C7—C8—C9</td><td>1.1 (5)</td></tr><tr><td>C9—C1—C6—O1</td><td>1.2 (4)</td><td>C11—C12—C13—C14</td><td>0.0 (5)</td></tr><tr><td>C2—C1—C6—C5</td><td>1.7 (4)</td><td>C15—C14—C13—C12</td><td>0.5 (5)</td></tr><tr><td>C9—C1—C6—C5</td><td>-178.1 (3)</td><td>O5—C14—C13—C12</td><td>-179.7 (3)</td></tr><tr><td>C17—O5—C14—C15</td><td>3.8 (5)</td><td>C12—C11—C16—C15</td><td>0.7 (5)</td></tr><tr><td>C17—O5—C14—C13</td><td>-176.1 (3)</td><td>C10—C11—C16—C15</td><td>-178.5 (3)</td></tr><tr><td>C9—O3—C10—O4</td><td>2.2 (5)</td><td>C14—C15—C16—C11</td><td>-0.3 (6)</td></tr><tr><td>C9—O3—C10—C11</td><td>-177.0 (3)</td><td>C5—C4—C3—C2</td><td>0.9 (5)</td></tr><tr><td>C16—C11—C10—O4</td><td>4.1 (5)</td><td>C4—C3—C2—C1</td><td>-0.5 (5)</td></tr><tr><td>C12—C11—C10—O4</td><td>-175.1 (3)</td><td>C6—C1—C2—C3</td><td>-0.8 (5)</td></tr><tr><td>C16—C11—C10—O3</td><td>-176.7 (3)</td><td>C9—C1—C2—C3</td><td>179.0 (3)</td></tr><tr><td>C12—C11—C10—O3</td><td>4.1 (4)</td><td></td><td></td></tr></table>

<table><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>C8—H8···O2<sup>i</sup></td><td>0.93</td><td>2.48</td><td>3.407 (4)</td><td>173</td></tr><tr><td>C2—H2···O4<sup>ii</sup></td><td>0.93</td><td>2.49</td><td>3.340 (4)</td><td>151</td></tr><tr><td>C17—H17B···O5<sup>iii</sup></td><td>0.96</td><td>2.59</td><td>3.461 (4)</td><td>151</td></tr></tbody></table>

Symmetry codes: (i) $-x-1, -y, -z+1$; (ii) $x+1, y, z$; (iii) $-x+2, -y-1, -z$.