The crystal structure of 2-[(2-oxo-2H-chromen-4-yl)oxy]acetic acid dimethylsulfoxide monosolvate is described and the intermolecular contacts in the crystal analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.
Keywords: crystal structure, chromen, acetamide, pyran, dimethyl sulfoxide, hydrogen bonding, C—H⋯π interactions, offset π–π interactions, Hirshfeld surface analysis
Abstract
The title compound, C11H8O5·(CH3)2SO, is a new coumarin derivative. The asymmetric unit contains two coumarin molecules (A and B) and two dimethylsulfoxide solvent molecules (A and B). The dihedral angle between the pyran and benzene rings in the chromene moiety is 3.56 (2)° for molecule A and 1.83 (2)° for molecule B. In molecule A, the dimethyl sulfoxide sulfur atom is disordered over two positions with a refined occupancy ratio of 0.782 (5):0.218 (5). In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains running along the c-axis direction. The chains are linked by C—H⋯O hydrogen bonds, forming layers parallel to the ac plane. In addition, there are also C—H⋯π and π–π interactions present within the layers. The intermolecular contacts in the crystal have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots, which indicate that the most important contributions to the packing are from H⋯H (33.9%) and O⋯H/H⋯O (41.2%) contacts.
Chemical context
Coumarin and its derivatives represent one of the most active classes of compounds, possessing a wide spectrum of biological activity. The synthesis, and pharmacological and other properties of coumarin derivatives have been studied intensively and reviewed (Syed Abuthahir et al., 2019 ▸; Kumar et al., 2015 ▸; Kubrak et al., 2017 ▸; Srikrishna et al., 2018 ▸; Venugopala et al., 2013 ▸). Many of these compounds have proven to be active as antibacterial, antifungal, anti-inflammatory, anticoagulant, anti-HIV and antitumor agents (Govindhan, Subramanian, Chennakesava Rao et al., 2015 ▸; Govindhan, Subramanian, Sridharan et al., 2015 ▸). Sulfur-containing isocoumarins (Henderson & Hill, 1982 ▸), fluorine-containing isocoumarins (Babar et al., 2008 ▸) and chlorine-containing isocoumarins (Abid et al., 2008 ▸) have also been studied. In view of the importance of their natural occurrence, biological, pharmacological and medicinal activities, and their use as synthetic intermediates, we have synthesized the title derivative 2-[(2-oxo-2H-chromen-4-yl)oxy]acetic acid dimethyl sulfoxide monosolvate, and report herein on its crystal structure and Hirshfeld surface analysis.
Structural commentary
The molecular structure and conformation of the two independent molecules, A and B in the asymmetric unit, are shown in Fig. 1 ▸. The bond lengths and angles in both molecules are very similar. The normal probability plot analyses (International Tables for X-ray Crystallography, 1974, Vol. IV, pp. 293–309) for both bond lengths and angles show that the differences between the two symmetry-independent molecules are of a statistical nature. The structural overlay of the two molecules is shown in Fig. 2 ▸ (r.m.s. deviation = 0.098 Å).
Figure 1.
The molecular structure of the compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
Figure 2.
A view of the molecule overlay of inverted molecule B (red) on molecule A (blue), with an r.m.s. deviation of 0.126 Å.
The 1H-isochromene moiety is planar (r.m.s. deviation = 0.001 Å for molecule A and 0.015 Å for molecule B) and atoms O2A and O2B deviate from this mean plane by 0.007 (3) and 0.039 (3) Å, respectively. The dihedral angle between the pyran and benzene rings in the chromene moiety is 3.56 (16)° for molecule A and 1.83 (16)° for molecule B; this value is in agreement with those found in analogous coumarin derivatives (Dobson & Gerkin, 1996 ▸; Kokila et al., 1996 ▸). In molecule A, the dimethyl sulfoxide sulfur atom is disordered over two positions with refined occupancies of 0.782 (5) and 0.218 (5).
The title compound exhibits structural similarities with those of two new coumarin derivatives: 2-(4-{2-[(2-oxo-2H-chromen-4-yl)oxy]acetyl}piperazin-1-yl)acetamide (Govindhan, Subramanian, Chennakesava Rao et al., 2015 ▸) and N-(2,4-dimethoxybenzyl)-2-[(2-oxo-2H-chromen-4-yl)oxy]acetamide (Syed Abuthahir et al., 2019 ▸).
Supramolecular features
The crystal structure features O—H⋯O and C—H⋯O hydrogen bonds (Table 1 ▸; Fig. 3 ▸). In the crystal, the A and B molecules are linked by O—H⋯O hydrogen bonds, forming chains running along the c-axis direction. The chains are linked by C—H⋯O hydrogen bonds, forming layers parallel to the ac plane. C—H⋯π (Table 1 ▸) and π–π interactions are present within the layers. The observed π–π interactions involve the pyran ring of the chromene ring system and the benzene ring [Cg1⋯Cg3iv = 3.864 (2), Cg1⋯Cg4iv = 3.509 (2) and Cg2⋯Cg3iv 3.572 (2) Å where Cg1, Cg2, Cg3 and Cg4 are the centroids of rings O1A/C1A/C6A–C9A, C1A–C6A, O1B/C1B/C6B–C9B, and C1B–C6B, respectively; symmetry code: (iv) x, 1 + y, z].
Table 1. Hydrogen-bond geometry (Å, °).
Cg2 is the centroid of the C1A–C6A ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O4A—H4A1⋯O6A | 0.82 | 1.82 | 2.621 (5) | 167 |
| O4B—H4B1⋯S1B i | 0.82 | 2.70 | 3.479 (3) | 159 |
| O4B—H4B1⋯O6B i | 0.82 | 1.78 | 2.595 (4) | 169 |
| C10B—H10A⋯O2A | 0.97 | 2.49 | 3.423 (4) | 161 |
| C10B—H10B⋯O6B ii | 0.97 | 2.37 | 3.266 (4) | 153 |
| C10A—H10C⋯O6A iii | 0.97 | 2.38 | 3.330 (5) | 165 |
| C10A—H10D⋯O2B | 0.97 | 2.40 | 3.324 (4) | 159 |
| C4B—H4B⋯Cg2i | 0.93 | 2.88 | 3.552 (3) | 130 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Figure 3.
A view along the b axis of the crystal packing of the title compound. The hydrogen bonds (Table 1 ▸) are shown as dashed lines, and H atoms not involved in hydrogen bonding have been omitted.
Hirshfeld surface analysis
A recent article by Tiekink and collaborators (Tan et al., 2019 ▸) reviews and describes the uses and utility of Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ▸), and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ▸), to analyse intermolecular contacts in crystals. The various calculations for the title compound were performed with CrystalExplorer17 (Turner et al., 2017 ▸).
The Hirshfeld surface of the title compound mapped over d norm is shown in Fig. 4 ▸, and the intermolecular contacts are illustrated in Fig. 5 ▸. They are colour-mapped with the normalized contact distance, d norm, ranging from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii). The d norm surface was mapped over a fixed colour scale of 0.774 (red) to 1.381 (blue) for the title compound, where the red spots indicate the intermolecular contacts involved in the hydrogen bonding.
Figure 4.
The Hirshfeld surface of the title compound, mapped over d norm.
Figure 5.
A view of the Hirshfeld surface mapped over d norm, showing the various intermolecular contacts in the crystal of the title compound.
The fingerprint plots are given in Fig. 6 ▸. They reveal that the principal intermolecular contacts are H⋯H at 33.9% (Fig. 6 ▸ b) and O⋯H/H⋯O at 41.2% (Fig. 6 ▸ c), followed by the C⋯H/H⋯C contacts at 9.6% (Fig. 6 ▸ d), C⋯C contacts at 6.3% (Fig. 6 ▸ e) and S⋯H/H⋯S contacts at 3.9% (Fig. 6 ▸ f).
Figure 6.
(a) The full two-dimensional fingerprint plot for the title compound, and those delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C, (e) C⋯C and (f) S⋯H/H⋯S contacts.
Database survey
A search of the Cambridge Structural Database (Web CSD version 5.39; March 9, 2018; Groom et al., 2016 ▸) gave more than 35 hits for both linear and angular pyranocoumarin (psoralene class) structures. They include seselin (amyrolin) [refcodes AMYROL (Kato, 1970 ▸) and AMYROL01 (Bauri et al., 2006 ▸)], 2,3-dihydroxy-9-hydroxy-2(1-hydroxy-1-methylethyl)-7H-furo-[3,2-g][1]-benzopyran-7-one monohydrate (FUGVOS; Thailambal & Pattabhi, 1987 ▸), bromohydroxyseselin (XARQAL; Bauri et al., 2017a ▸), dibromomomethoxyseselin (VAPKOP; Bauri et al., 2017b ▸), and a number of structures with various substituents at C3 and C4, many of which are natural products.
Intramolecular C—H⋯O short contacts similar to those in the title compound are found in five compounds in the CSD: 1-(1-pyrrolidinylcarbonyl)cyclopropyl sulfamate (LISLAB; Morin et al., 2007 ▸), 2-[3′-(4"-chlorophenyl)-4′,6′-dimethoxyindol-7′-yl]glyoxyl-1-pyrrolidine (PEQHAU; Black et al., 1997 ▸), [2-hydroxy-5-(2-hydroxybenzoyl)phenyl](pyrrolidin-1-yl)methanone (QIBBEJ; Holtz et al., 2007 ▸), 2-methoxy-1-(1-pyrrolidinylcarbonyl)naphthalene (SIHNAZ; Sakamoto et al., 2007 ▸) and (4S,5S)-4,5-bis(pyrrolidinylcarbonyl)-2,2-dimethyl-1,3-dioxolane (TAJDIR; Garcia et al., 1991 ▸).
Synthesis and crystallization
A solution of lithium hydroxide (0.24 g, 1.2 mol eq.) in water (4 mL) was added to ethyl 2-(2-oxo-2H-chromen-4-yloxy) acetate (2.0 g, 1.0 mol eq.) in THF (10 mL) at 273 K and stirred at 273 K for 1 h. Completion of the reaction was confirmed by TLC (mobile phase ethyl acetate/hexane) and THF was distilled off using a rotavapor. The obtained solution was washed with ethyl acetate (20 mL). The aqueous layer was acidified with 2N HCl (pH 1.0–2.0) and the obtained solid was filtered, washed with hexane and dried under vacuum to give as white solid. The purified compound was recrystallized using dimethyl sulfoxide as solvent.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms were positioned geometrically and constrained to ride on their parent atoms: C—H = 0.93–0.97Å with U iso(H) = 1.5U eq(C-methyl) or 1.2U eq(C) for other H atoms. In molecule A, the sulfur atom of the sulfinyldimethane group is disordered over two positions with refined occupancies of 0.782 (5) and 0.218 (5). In the final cycles of refinement, five outliers were omitted.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C11H8O5·C2H6OS |
| M r | 298.30 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 23.1461 (12), 8.2631 (4), 14.6374 (8) |
| β (°) | 97.687 (4) |
| V (Å3) | 2774.4 (2) |
| Z | 8 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.26 |
| Crystal size (mm) | 0.25 × 0.18 × 0.12 |
| Data collection | |
| Diffractometer | Bruker Kappa APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2008 ▸) |
| T min, T max | 0.742, 0.852 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 25798, 6824, 2743 |
| R int | 0.119 |
| (sin θ/λ)max (Å−1) | 0.666 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.063, 0.208, 0.87 |
| No. of reflections | 6824 |
| No. of parameters | 376 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.69, −0.42 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019009447/vm2218sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009447/vm2218Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989019009447/vm2218Isup3.cml
CCDC reference: 1891495
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors are grateful to the SAIF, IIT Madras, for the data collection.
supplementary crystallographic information
Crystal data
| C11H8O5·C2H6OS | F(000) = 1248 |
| Mr = 298.30 | Dx = 1.428 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 23.1461 (12) Å | Cell parameters from 6824 reflections |
| b = 8.2631 (4) Å | θ = 1.8–28.3° |
| c = 14.6374 (8) Å | µ = 0.26 mm−1 |
| β = 97.687 (4)° | T = 293 K |
| V = 2774.4 (2) Å3 | Block, colourless |
| Z = 8 | 0.25 × 0.18 × 0.12 mm |
Data collection
| Bruker Kappa APEXII CCD diffractometer | 2743 reflections with I > 2σ(I) |
| ω and φ scans | Rint = 0.119 |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 28.3°, θmin = 1.8° |
| Tmin = 0.742, Tmax = 0.852 | h = −30→30 |
| 25798 measured reflections | k = −10→10 |
| 6824 independent reflections | l = −19→19 |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
| wR(F2) = 0.208 | w = 1/[σ2(Fo2) + (0.1053P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.87 | (Δ/σ)max < 0.001 |
| 6824 reflections | Δρmax = 0.69 e Å−3 |
| 376 parameters | Δρmin = −0.41 e Å−3 |
Special details
| 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C13A | −0.04399 (18) | 0.4312 (5) | 0.3443 (3) | 0.0728 (13) | |
| H13A | −0.070292 | 0.463777 | 0.386381 | 0.109* | |
| H13B | −0.039226 | 0.315849 | 0.346833 | 0.109* | |
| H13C | −0.059577 | 0.462937 | 0.282872 | 0.109* | |
| C13B | 0.4520 (2) | 0.3039 (6) | 0.5340 (4) | 0.0918 (16) | |
| H13D | 0.491305 | 0.265054 | 0.546953 | 0.138* | |
| H13E | 0.427430 | 0.243383 | 0.569514 | 0.138* | |
| H13F | 0.450767 | 0.416386 | 0.550058 | 0.138* | |
| C12B | 0.4320 (2) | 0.0677 (5) | 0.4079 (4) | 0.0834 (15) | |
| H12A | 0.419331 | 0.033276 | 0.345850 | 0.125* | |
| H12B | 0.407847 | 0.018839 | 0.448683 | 0.125* | |
| H12C | 0.471795 | 0.035236 | 0.425574 | 0.125* | |
| S1B | 0.42683 (4) | 0.27960 (14) | 0.41469 (9) | 0.0666 (4) | |
| C8B | 0.27020 (14) | 0.7563 (4) | 0.6754 (2) | 0.0410 (9) | |
| H8B | 0.286314 | 0.852257 | 0.657309 | 0.049* | |
| C8A | 0.22217 (14) | 1.1613 (4) | 0.5296 (2) | 0.0388 (8) | |
| H8A | 0.206427 | 1.062620 | 0.544340 | 0.047* | |
| C1A | 0.21016 (13) | 1.4456 (4) | 0.4892 (2) | 0.0343 (8) | |
| C1B | 0.28007 (13) | 0.4732 (4) | 0.7173 (2) | 0.0365 (8) | |
| C9A | 0.18699 (13) | 1.2921 (4) | 0.5157 (2) | 0.0356 (8) | |
| C6B | 0.22279 (14) | 0.4729 (4) | 0.7336 (2) | 0.0374 (8) | |
| C7B | 0.21038 (14) | 0.7526 (4) | 0.6883 (3) | 0.0408 (9) | |
| C6A | 0.26854 (14) | 1.4507 (4) | 0.4786 (2) | 0.0374 (8) | |
| C9B | 0.30397 (13) | 0.6232 (4) | 0.6888 (2) | 0.0350 (8) | |
| C10B | 0.39088 (14) | 0.7553 (4) | 0.6567 (3) | 0.0450 (9) | |
| H10A | 0.365842 | 0.821170 | 0.613063 | 0.054* | |
| H10B | 0.425039 | 0.726291 | 0.628436 | 0.054* | |
| C7A | 0.28261 (15) | 1.1714 (4) | 0.5224 (3) | 0.0425 (9) | |
| C3A | 0.20154 (16) | 1.7230 (4) | 0.4385 (3) | 0.0486 (10) | |
| H3A | 0.179056 | 1.815309 | 0.424815 | 0.058* | |
| C4A | 0.25956 (17) | 1.7231 (4) | 0.4274 (3) | 0.0502 (10) | |
| H4A | 0.275975 | 1.815759 | 0.405586 | 0.060* | |
| C5A | 0.29396 (15) | 1.5876 (4) | 0.4480 (3) | 0.0451 (9) | |
| H5A | 0.333355 | 1.588921 | 0.441346 | 0.054* | |
| C11B | 0.40938 (15) | 0.8519 (4) | 0.7420 (3) | 0.0484 (10) | |
| C5B | 0.19577 (16) | 0.3353 (4) | 0.7620 (3) | 0.0469 (9) | |
| H5B | 0.157087 | 0.338287 | 0.772786 | 0.056* | |
| C3B | 0.28513 (17) | 0.1906 (4) | 0.7585 (3) | 0.0496 (10) | |
| H3B | 0.306236 | 0.094800 | 0.767083 | 0.060* | |
| C11A | 0.08288 (14) | 1.0434 (4) | 0.4690 (3) | 0.0436 (9) | |
| C4B | 0.22748 (17) | 0.1949 (4) | 0.7737 (3) | 0.0501 (10) | |
| H4B | 0.209965 | 0.101248 | 0.792202 | 0.060* | |
| C2A | 0.17680 (15) | 1.5856 (4) | 0.4699 (2) | 0.0423 (9) | |
| H2A | 0.137684 | 1.586033 | 0.478387 | 0.051* | |
| C2B | 0.31131 (15) | 0.3286 (4) | 0.7305 (2) | 0.0429 (9) | |
| H2B | 0.350099 | 0.325359 | 0.720247 | 0.052* | |
| C12A | 0.05788 (19) | 0.4705 (5) | 0.2783 (3) | 0.0771 (14) | |
| H12D | 0.063612 | 0.355485 | 0.278054 | 0.116* | |
| H12E | 0.033342 | 0.502275 | 0.223138 | 0.116* | |
| H12F | 0.094887 | 0.524054 | 0.281072 | 0.116* | |
| C10A | 0.10247 (14) | 1.1508 (4) | 0.5512 (3) | 0.0421 (9) | |
| H10C | 0.068964 | 1.179268 | 0.581190 | 0.050* | |
| H10D | 0.129589 | 1.091455 | 0.595162 | 0.050* | |
| O2B | 0.17604 (10) | 0.8632 (3) | 0.6759 (2) | 0.0583 (7) | |
| O2A | 0.30431 (9) | 1.3180 (3) | 0.49654 (17) | 0.0443 (6) | |
| O3B | 0.36054 (9) | 0.6118 (3) | 0.67566 (17) | 0.0447 (6) | |
| O1A | 0.31786 (11) | 1.0636 (3) | 0.5349 (2) | 0.0623 (8) | |
| O1B | 0.18850 (9) | 0.6100 (3) | 0.71963 (17) | 0.0455 (6) | |
| O3A | 0.13002 (9) | 1.2960 (2) | 0.52488 (17) | 0.0422 (6) | |
| O4A | 0.06268 (12) | 0.9068 (3) | 0.49773 (19) | 0.0586 (8) | |
| H4A1 | 0.050295 | 0.850621 | 0.453194 | 0.088* | |
| O4B | 0.43802 (13) | 0.9821 (3) | 0.7219 (2) | 0.0710 (9) | |
| H4B1 | 0.445425 | 1.038184 | 0.768236 | 0.106* | |
| O7B | 0.47513 (11) | 0.3440 (3) | 0.3654 (2) | 0.0764 (10) | |
| O6A | 0.01623 (13) | 0.6980 (4) | 0.3745 (3) | 0.0979 (13) | |
| O5B | 0.39977 (12) | 0.8143 (4) | 0.8178 (2) | 0.0682 (9) | |
| O5A | 0.08491 (13) | 1.0796 (4) | 0.3906 (2) | 0.0718 (9) | |
| S1A | 0.02436 (6) | 0.52545 (19) | 0.37557 (13) | 0.0507 (6) | 0.782 (5) |
| S1'A | 0.0025 (3) | 0.5829 (7) | 0.3230 (5) | 0.057 (2) | 0.218 (5) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C13A | 0.067 (3) | 0.069 (3) | 0.085 (4) | −0.020 (2) | 0.016 (2) | −0.009 (3) |
| C13B | 0.086 (3) | 0.094 (4) | 0.090 (4) | −0.016 (3) | −0.010 (3) | −0.007 (3) |
| C12B | 0.088 (3) | 0.070 (3) | 0.090 (4) | −0.011 (3) | 0.001 (3) | 0.004 (3) |
| S1B | 0.0449 (6) | 0.0689 (7) | 0.0854 (10) | 0.0084 (5) | 0.0070 (6) | 0.0063 (6) |
| C8B | 0.0393 (18) | 0.0338 (18) | 0.051 (3) | −0.0033 (15) | 0.0085 (16) | 0.0001 (17) |
| C8A | 0.0399 (18) | 0.0315 (17) | 0.045 (2) | −0.0033 (14) | 0.0075 (16) | 0.0018 (16) |
| C1A | 0.0360 (17) | 0.0355 (18) | 0.032 (2) | 0.0010 (14) | 0.0049 (15) | −0.0044 (15) |
| C1B | 0.0380 (18) | 0.0345 (18) | 0.036 (2) | −0.0004 (15) | 0.0007 (15) | −0.0001 (16) |
| C9A | 0.0353 (17) | 0.0366 (19) | 0.035 (2) | −0.0010 (14) | 0.0033 (15) | −0.0007 (15) |
| C6B | 0.0432 (19) | 0.0366 (18) | 0.032 (2) | −0.0007 (15) | 0.0052 (16) | −0.0041 (16) |
| C7B | 0.0416 (19) | 0.039 (2) | 0.042 (2) | −0.0008 (16) | 0.0051 (16) | −0.0021 (17) |
| C6A | 0.0445 (19) | 0.0345 (18) | 0.033 (2) | −0.0015 (15) | 0.0059 (16) | −0.0057 (16) |
| C9B | 0.0328 (16) | 0.0382 (18) | 0.033 (2) | 0.0004 (14) | 0.0028 (15) | −0.0073 (16) |
| C10B | 0.0347 (17) | 0.043 (2) | 0.059 (3) | −0.0011 (16) | 0.0159 (17) | 0.0030 (19) |
| C7A | 0.0432 (19) | 0.040 (2) | 0.044 (2) | 0.0032 (16) | 0.0033 (17) | −0.0044 (17) |
| C3A | 0.057 (2) | 0.041 (2) | 0.048 (3) | 0.0097 (18) | 0.0062 (19) | 0.0031 (18) |
| C4A | 0.071 (3) | 0.039 (2) | 0.041 (3) | −0.0134 (19) | 0.011 (2) | 0.0038 (18) |
| C5A | 0.047 (2) | 0.045 (2) | 0.045 (3) | −0.0090 (17) | 0.0108 (18) | −0.0043 (18) |
| C11B | 0.0358 (19) | 0.042 (2) | 0.069 (3) | −0.0054 (16) | 0.014 (2) | −0.004 (2) |
| C5B | 0.050 (2) | 0.051 (2) | 0.040 (3) | −0.0126 (18) | 0.0074 (17) | 0.0001 (18) |
| C3B | 0.066 (3) | 0.038 (2) | 0.042 (3) | 0.0018 (18) | −0.0043 (19) | 0.0061 (18) |
| C11A | 0.0343 (18) | 0.044 (2) | 0.053 (3) | −0.0022 (16) | 0.0095 (18) | 0.000 (2) |
| C4B | 0.070 (3) | 0.041 (2) | 0.038 (3) | −0.0132 (19) | 0.0029 (19) | 0.0051 (17) |
| C2A | 0.0445 (19) | 0.041 (2) | 0.041 (2) | 0.0018 (16) | 0.0038 (17) | 0.0004 (17) |
| C2B | 0.0436 (19) | 0.042 (2) | 0.042 (2) | 0.0022 (16) | 0.0001 (17) | −0.0009 (17) |
| C12A | 0.070 (3) | 0.076 (3) | 0.092 (4) | −0.003 (2) | 0.034 (3) | −0.030 (3) |
| C10A | 0.0368 (18) | 0.0411 (19) | 0.050 (3) | −0.0006 (15) | 0.0109 (17) | 0.0002 (18) |
| O2B | 0.0477 (15) | 0.0467 (15) | 0.081 (2) | 0.0112 (12) | 0.0088 (14) | 0.0038 (14) |
| O2A | 0.0367 (12) | 0.0435 (14) | 0.0539 (18) | 0.0010 (10) | 0.0101 (11) | 0.0052 (12) |
| O3B | 0.0342 (13) | 0.0378 (13) | 0.0629 (19) | −0.0018 (10) | 0.0094 (12) | 0.0006 (12) |
| O1A | 0.0475 (15) | 0.0520 (16) | 0.088 (2) | 0.0149 (13) | 0.0105 (14) | 0.0099 (15) |
| O1B | 0.0392 (13) | 0.0430 (14) | 0.0561 (18) | 0.0005 (11) | 0.0123 (12) | 0.0030 (12) |
| O3A | 0.0340 (12) | 0.0348 (13) | 0.0583 (18) | 0.0003 (10) | 0.0085 (11) | 0.0034 (11) |
| O4A | 0.0630 (17) | 0.0405 (15) | 0.072 (2) | −0.0125 (13) | 0.0081 (15) | −0.0035 (14) |
| O4B | 0.0748 (19) | 0.0550 (17) | 0.085 (2) | −0.0232 (15) | 0.0173 (18) | −0.0107 (16) |
| O7B | 0.0494 (16) | 0.074 (2) | 0.110 (3) | 0.0176 (14) | 0.0238 (16) | 0.0302 (18) |
| O6A | 0.074 (2) | 0.073 (2) | 0.153 (4) | −0.0240 (17) | 0.040 (2) | −0.065 (2) |
| O5B | 0.074 (2) | 0.074 (2) | 0.058 (2) | −0.0207 (15) | 0.0138 (16) | −0.0042 (17) |
| O5A | 0.089 (2) | 0.079 (2) | 0.049 (2) | −0.0262 (17) | 0.0148 (17) | −0.0035 (17) |
| S1A | 0.0455 (8) | 0.0497 (9) | 0.0550 (13) | 0.0045 (6) | −0.0008 (7) | −0.0059 (8) |
| S1'A | 0.059 (3) | 0.049 (3) | 0.061 (5) | 0.004 (3) | 0.002 (3) | 0.007 (3) |
Geometric parameters (Å, º)
| C13A—S1'A | 1.708 (6) | C10B—H10A | 0.9700 |
| C13A—S1A | 1.768 (4) | C10B—H10B | 0.9700 |
| C13A—H13A | 0.9600 | C7A—O1A | 1.205 (4) |
| C13A—H13B | 0.9600 | C7A—O2A | 1.384 (4) |
| C13A—H13C | 0.9600 | C3A—C2A | 1.378 (5) |
| C13B—S1B | 1.777 (5) | C3A—C4A | 1.374 (5) |
| C13B—H13D | 0.9600 | C3A—H3A | 0.9300 |
| C13B—H13E | 0.9600 | C4A—C5A | 1.384 (5) |
| C13B—H13F | 0.9600 | C4A—H4A | 0.9300 |
| C12B—S1B | 1.759 (5) | C5A—H5A | 0.9300 |
| C12B—H12A | 0.9600 | C11B—O5B | 1.201 (5) |
| C12B—H12B | 0.9600 | C11B—O4B | 1.317 (4) |
| C12B—H12C | 0.9600 | C5B—C4B | 1.372 (5) |
| S1B—O7B | 1.506 (3) | C5B—H5B | 0.9300 |
| C8B—C9B | 1.348 (4) | C3B—C2B | 1.379 (5) |
| C8B—C7B | 1.423 (4) | C3B—C4B | 1.383 (5) |
| C8B—H8B | 0.9300 | C3B—H3B | 0.9300 |
| C8A—C9A | 1.352 (4) | C11A—O5A | 1.193 (4) |
| C8A—C7A | 1.420 (4) | C11A—O4A | 1.312 (4) |
| C8A—H8A | 0.9300 | C11A—C10A | 1.515 (5) |
| C1A—C6A | 1.382 (4) | C4B—H4B | 0.9300 |
| C1A—C2A | 1.399 (4) | C2A—H2A | 0.9300 |
| C1A—C9A | 1.449 (4) | C2B—H2B | 0.9300 |
| C1B—C6B | 1.378 (4) | C12A—S1'A | 1.776 (7) |
| C1B—C2B | 1.396 (4) | C12A—S1A | 1.769 (4) |
| C1B—C9B | 1.441 (5) | C12A—H12D | 0.9600 |
| C9A—O3A | 1.344 (4) | C12A—H12E | 0.9600 |
| C6B—C5B | 1.388 (5) | C12A—H12F | 0.9600 |
| C6B—O1B | 1.383 (4) | C10A—O3A | 1.436 (4) |
| C7B—O2B | 1.209 (4) | C10A—H10C | 0.9700 |
| C7B—O1B | 1.384 (4) | C10A—H10D | 0.9700 |
| C6A—C5A | 1.377 (5) | O4A—H4A1 | 0.8200 |
| C6A—O2A | 1.378 (4) | O4B—H4B1 | 0.8200 |
| C9B—O3B | 1.352 (3) | O6A—S1'A | 1.229 (6) |
| C10B—O3B | 1.424 (4) | O6A—S1A | 1.438 (3) |
| C10B—C11B | 1.496 (5) | ||
| S1A—C13A—H13A | 109.5 | O2A—C7A—C8A | 118.0 (3) |
| S1A—C13A—H13B | 109.5 | C2A—C3A—C4A | 119.8 (3) |
| H13A—C13A—H13B | 109.5 | C2A—C3A—H3A | 120.1 |
| S1A—C13A—H13C | 109.5 | C4A—C3A—H3A | 120.1 |
| H13A—C13A—H13C | 109.5 | C3A—C4A—C5A | 121.1 (3) |
| H13B—C13A—H13C | 109.5 | C3A—C4A—H4A | 119.4 |
| S1B—C13B—H13D | 109.5 | C5A—C4A—H4A | 119.4 |
| S1B—C13B—H13E | 109.5 | C6A—C5A—C4A | 118.5 (3) |
| H13D—C13B—H13E | 109.5 | C6A—C5A—H5A | 120.8 |
| S1B—C13B—H13F | 109.5 | C4A—C5A—H5A | 120.8 |
| H13D—C13B—H13F | 109.5 | O5B—C11B—O4B | 125.3 (4) |
| H13E—C13B—H13F | 109.5 | O5B—C11B—C10B | 124.4 (3) |
| S1B—C12B—H12A | 109.5 | O4B—C11B—C10B | 110.3 (4) |
| S1B—C12B—H12B | 109.5 | C4B—C5B—C6B | 118.4 (3) |
| H12A—C12B—H12B | 109.5 | C4B—C5B—H5B | 120.8 |
| S1B—C12B—H12C | 109.5 | C6B—C5B—H5B | 120.8 |
| H12A—C12B—H12C | 109.5 | C2B—C3B—C4B | 119.9 (3) |
| H12B—C12B—H12C | 109.5 | C2B—C3B—H3B | 120.0 |
| O7B—S1B—C12B | 105.3 (2) | C4B—C3B—H3B | 120.0 |
| O7B—S1B—C13B | 105.3 (2) | O5A—C11A—O4A | 125.8 (4) |
| C12B—S1B—C13B | 98.7 (2) | O5A—C11A—C10A | 124.8 (3) |
| C9B—C8B—C7B | 121.3 (3) | O4A—C11A—C10A | 109.3 (4) |
| C9B—C8B—H8B | 119.4 | C5B—C4B—C3B | 120.9 (3) |
| C7B—C8B—H8B | 119.4 | C5B—C4B—H4B | 119.6 |
| C9A—C8A—C7A | 121.4 (3) | C3B—C4B—H4B | 119.6 |
| C9A—C8A—H8A | 119.3 | C3A—C2A—C1A | 120.4 (3) |
| C7A—C8A—H8A | 119.3 | C3A—C2A—H2A | 119.8 |
| C6A—C1A—C2A | 118.3 (3) | C1A—C2A—H2A | 119.8 |
| C6A—C1A—C9A | 117.4 (3) | C3B—C2B—C1B | 120.6 (3) |
| C2A—C1A—C9A | 124.3 (3) | C3B—C2B—H2B | 119.7 |
| C6B—C1B—C2B | 117.8 (3) | C1B—C2B—H2B | 119.7 |
| C6B—C1B—C9B | 117.8 (3) | S1A—C12A—H12D | 109.5 |
| C2B—C1B—C9B | 124.3 (3) | S1A—C12A—H12E | 109.5 |
| O3A—C9A—C8A | 125.7 (3) | H12D—C12A—H12E | 109.5 |
| O3A—C9A—C1A | 114.1 (3) | S1A—C12A—H12F | 109.5 |
| C8A—C9A—C1A | 120.2 (3) | H12D—C12A—H12F | 109.5 |
| C1B—C6B—C5B | 122.4 (3) | H12E—C12A—H12F | 109.5 |
| C1B—C6B—O1B | 121.3 (3) | O3A—C10A—C11A | 111.9 (3) |
| C5B—C6B—O1B | 116.3 (3) | O3A—C10A—H10C | 109.2 |
| O2B—C7B—O1B | 115.5 (3) | C11A—C10A—H10C | 109.2 |
| O2B—C7B—C8B | 126.6 (3) | O3A—C10A—H10D | 109.2 |
| O1B—C7B—C8B | 117.9 (3) | C11A—C10A—H10D | 109.2 |
| C5A—C6A—O2A | 116.3 (3) | H10C—C10A—H10D | 107.9 |
| C5A—C6A—C1A | 121.9 (3) | C6A—O2A—C7A | 121.2 (3) |
| O2A—C6A—C1A | 121.7 (3) | C9B—O3B—C10B | 118.8 (2) |
| C8B—C9B—O3B | 126.1 (3) | C7B—O1B—C6B | 121.2 (3) |
| C8B—C9B—C1B | 120.4 (3) | C9A—O3A—C10A | 118.9 (2) |
| O3B—C9B—C1B | 113.4 (3) | C11A—O4A—H4A1 | 109.5 |
| O3B—C10B—C11B | 112.0 (3) | C11B—O4B—H4B1 | 109.5 |
| O3B—C10B—H10A | 109.2 | O6A—S1A—C12A | 108.5 (2) |
| C11B—C10B—H10A | 109.2 | O6A—S1A—C13A | 108.8 (2) |
| O3B—C10B—H10B | 109.2 | C12A—S1A—C13A | 98.8 (2) |
| C11B—C10B—H10B | 109.2 | O6A—S1'A—C13A | 124.9 (5) |
| H10A—C10B—H10B | 107.9 | O6A—S1'A—C12A | 119.4 (5) |
| O1A—C7A—O2A | 115.2 (3) | C13A—S1'A—C12A | 100.8 (3) |
| O1A—C7A—C8A | 126.8 (3) | ||
| C7A—C8A—C9A—O3A | −177.0 (3) | O3B—C10B—C11B—O5B | −0.3 (5) |
| C7A—C8A—C9A—C1A | 2.4 (5) | O3B—C10B—C11B—O4B | 179.0 (3) |
| C6A—C1A—C9A—O3A | 179.9 (3) | C1B—C6B—C5B—C4B | −0.2 (5) |
| C2A—C1A—C9A—O3A | −3.1 (5) | O1B—C6B—C5B—C4B | 177.8 (3) |
| C6A—C1A—C9A—C8A | 0.5 (5) | C6B—C5B—C4B—C3B | 0.6 (6) |
| C2A—C1A—C9A—C8A | 177.5 (3) | C2B—C3B—C4B—C5B | −0.4 (6) |
| C2B—C1B—C6B—C5B | −0.2 (5) | C4A—C3A—C2A—C1A | −1.0 (6) |
| C9B—C1B—C6B—C5B | −179.4 (3) | C6A—C1A—C2A—C3A | 1.9 (5) |
| C2B—C1B—C6B—O1B | −178.2 (3) | C9A—C1A—C2A—C3A | −175.0 (3) |
| C9B—C1B—C6B—O1B | 2.6 (5) | C4B—C3B—C2B—C1B | 0.0 (5) |
| C9B—C8B—C7B—O2B | −178.0 (4) | C6B—C1B—C2B—C3B | 0.3 (5) |
| C9B—C8B—C7B—O1B | 3.1 (5) | C9B—C1B—C2B—C3B | 179.5 (3) |
| C2A—C1A—C6A—C5A | −1.4 (5) | O5A—C11A—C10A—O3A | −6.4 (5) |
| C9A—C1A—C6A—C5A | 175.8 (3) | O4A—C11A—C10A—O3A | 174.6 (3) |
| C2A—C1A—C6A—O2A | 179.8 (3) | C5A—C6A—O2A—C7A | −176.2 (3) |
| C9A—C1A—C6A—O2A | −3.1 (5) | C1A—C6A—O2A—C7A | 2.8 (5) |
| C7B—C8B—C9B—O3B | 177.7 (3) | O1A—C7A—O2A—C6A | 179.0 (3) |
| C7B—C8B—C9B—C1B | −0.3 (5) | C8A—C7A—O2A—C6A | 0.2 (5) |
| C6B—C1B—C9B—C8B | −2.6 (5) | C8B—C9B—O3B—C10B | 8.3 (5) |
| C2B—C1B—C9B—C8B | 178.2 (3) | C1B—C9B—O3B—C10B | −173.6 (3) |
| C6B—C1B—C9B—O3B | 179.2 (3) | C11B—C10B—O3B—C9B | 78.5 (4) |
| C2B—C1B—C9B—O3B | 0.0 (5) | O2B—C7B—O1B—C6B | 177.8 (3) |
| C9A—C8A—C7A—O1A | 178.7 (4) | C8B—C7B—O1B—C6B | −3.1 (5) |
| C9A—C8A—C7A—O2A | −2.7 (5) | C1B—C6B—O1B—C7B | 0.3 (5) |
| C2A—C3A—C4A—C5A | −0.6 (6) | C5B—C6B—O1B—C7B | −177.8 (3) |
| O2A—C6A—C5A—C4A | 178.8 (3) | C8A—C9A—O3A—C10A | −0.4 (5) |
| C1A—C6A—C5A—C4A | −0.1 (5) | C1A—C9A—O3A—C10A | −179.8 (3) |
| C3A—C4A—C5A—C6A | 1.1 (6) | C11A—C10A—O3A—C9A | −84.3 (3) |
Hydrogen-bond geometry (Å, º)
Cg1 is the centroid of the C1A–C6A ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4A—H4A1···O6A | 0.82 | 1.82 | 2.621 (5) | 167 |
| O4B—H4B1···S1Bi | 0.82 | 2.70 | 3.479 (3) | 159 |
| O4B—H4B1···O7Bi | 0.82 | 1.78 | 2.595 (4) | 169 |
| C10B—H10A···O1A | 0.97 | 2.49 | 3.423 (4) | 161 |
| C10B—H10B···O7Bii | 0.97 | 2.37 | 3.266 (4) | 153 |
| C10A—H10C···O6Aiii | 0.97 | 2.38 | 3.330 (5) | 165 |
| C10A—H10D···O2B | 0.97 | 2.40 | 3.324 (4) | 159 |
| C4B—H4B···Cg1i | 0.93 | 2.88 | 3.552 (3) | 130 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+2, −z+1.
References
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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) global, I. DOI: 10.1107/S2056989019009447/vm2218sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009447/vm2218Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989019009447/vm2218Isup3.cml
CCDC reference: 1891495
Additional supporting information: crystallographic information; 3D view; checkCIF report