research communications
12-(3,4,5-Trimethoxyphenyl)-2,3,4,12-tetrahydro-1H-5-oxatetraphen-1-one: and Hirshfeld surface analysis
aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380 001, India, bCentre for Organic and Medicinal Chemistry, VIT University, Vellore, Tamil Nadu 632 014, India, and cResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: mmjotani@rediffmail.com, edwardt@sunway.edu.my
In the title compound, C26H24O5, the pyran ring has a flattened-boat conformation, with the 1,4-related ether O and methine C atoms lying 0.1205 (18) and 0.271 (2) Å, respectively, above the least-squares plane involving the doubly bonded C atoms (r.m.s deviation = 0.0208 Å). An is found for the cyclohexene ring, with the flap atom being the middle methylene C atom, lying 0.616 (2) Å out of the plane defined by the remaining atoms (r.m.s. deviation = 0.0173 Å). The fused four-ring system is approximately planar, with the dihedral angle between the least-squares planes through the cyclohexene and naphthyl rings being 10.78 (7)°. The trisubstituted benzene ring occupies a position almost perpendicular to the pyran ring [dihedral angle = 83.97 (4)°]. The most prominent feature of the packing is the formation of zigzag supramolecular chains mediated by aryl-C—H⋯O(methoxy) interactions; chains are connected into a three-dimensional architecture by methylene- and methyl-C—H⋯π interactions. The prevalence of C—H⋯O and C—H⋯π interactions is confirmed by an analysis of the Hirshfeld surface. A comparison with related structures suggests that the molecular conformation of the title compound is relatively robust with respect to varying substitution patterns at the methine C atom of the pyran ring.
Keywords: crystal structure; xanthene; conformation; Hirshfeld surface.
CCDC reference: 1479203
1. Chemical context
Xanthenes and benzoxanthenes are important bioactive compounds that possess a wide range of biological and therapeutic properties, such as analgesic (Hafez et al., 2008), antiviral and antibacterial and anti-inflammatory activities (Poupelin et al., 1978; Hideo & Teruomi, 1981; Asano et al., 1996; Matsumoto et al., 2005; Pinto et al., 2005; Woo et al., 2007; Pouli & Marakos, 2009). Some of these compounds have been used in photodynamic therapy (Ion, 1997). Further, due to their having desirable spectroscopic properties, some derivatives have been used as dyes in laser technologies (Menchen et al., 2003) and as pH-sensitive fluorescent materials for the visualization of biomolecules (Ahmad et al., 2002).
Various methods for the synthesis of tetrahydrobenzo[a]xanthen-11-ones have been reported (Knight & Stephens, 1989). These usually involve a three-component condensation of dimedone with an aromatic aldehyde and 2-naphthol. However, each of these procedures has some drawbacks, such as harsh reaction conditions, tedious work-up and low yields. Hence, the microwave-assisted ionic liquid-mediated synthesis of xanthenes from cyclohexane-1,3-dione, 3,4,5-trimethoxybenzaldehyde and 2-naphthol was attempted. The use of an ionic liquid, i.e. [1-butyl-3-methylimidazolium]PF6, and microwave irradiation afforded the title compound in high yield within 12 min (Iniyavan et al., 2015). The title compound is a potent anti-oxidant (Iniyavan et al., 2015) and herein its crystal and molecular structures are described, along with an analysis of its Hirshfeld surface in order to gain greater insight into the crystal packing, especially the role of weaker interactions.
2. Structural commentary
The central pyran ring in the title compound, (I), is flanked by both a cyclohexene ring and a naphthyl-fused ring system (Fig. 1). A trisubstituted benzene ring is connected to the aforementioned four-ring residue at the methine C7 atom. The pyran ring has a flattened boat conformation, with the 1,4-related O1 and C7 atoms lying 0.1205 (18) and 0.271 (2) Å to the same side of the plane (r.m.s. deviation of the fitted atoms = 0.0208 Å) defined by the C1=C6 [1.3431 (19) Å] and C8=C17 [1.3681 (19) Å] double bonds. To a first approximation, the cyclohexene ring has an with the C3 (flap) atom lying 0.616 (2) Å above the plane defined by the remaining atoms (r.m.s. deviation = 0.0173 Å). The atoms comprising the four-ring system are approximately coplanar, as seen in the dihedral angle between the best plane through the cyclohexene ring and naphthyl residue of 10.78 (7)°. The benzene ring occupies a position almost perpendicular to the previous residue, forming a dihedral angle of 83.97 (4)° with the best plane through the pyran ring. In the benzene ring, two methoxy groups are coplanar with the ring to which they are connected [the C20′—O20—C20—C19 and C22′—O22—C22—C23 torsion angles are 4.98 (19) and 0.51 (19)°, respectively], while the central substituent is approximately perpendicular to the ring lying over the naphthyl residue, i.e. C21′—O21—C21—C22 is 76.08 (16)°. Presumably, this conformation is adopted to reduce steric hindrance.
3. Supramolecular features
In the molecular packing of (I), supramolecular chains along the a axis are formed through the agency of relatively strong aryl-C16—H16⋯O(methoxy) interactions (Table 1). Being generated by glide symmetry, the topology of the chain is zigzag (Fig. 2a). The chains are connected into a three-dimensional architecture by a network of C—H⋯π(aryl) interactions (Table 1). The donor atoms are derived from methylene and methyl groups, with the acceptor rings being each of the aromatic rings and with the outer benzene ring participating in two such contacts (Fig. 2b).
4. Hirshfeld surface analysis
With the aid of the program Crystal Explorer (Wolff et al., 2012), Hirshfeld surfaces mapped over dnorm, de, curvedness and electrostatic potential were generated. The electrostatic potential was calculated with TONTO (Spackman et al., 2008; Jayatilaka et al., 2005), integrated in Crystal Explorer, using the as the starting geometry. The electrostatic potentials were mapped on the Hirshfeld surface using the STO-3G basis/Hartree–Fock level of theory over the range ±0.08 au. The contact distances di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enables the analysis of the intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of a two-dimensional fingerprint plot (McKinnon et al., 2004) provides a convenient summary of the intermolecular contacts in the crystal.
The bright-red spots at the aryl H16 and methoxy O20 atoms, visible on the Hirshfeld surface mapped over dnorm and labelled as `1' in Fig. 3, represent the donor and acceptor atoms for the intermolecular C—H⋯O interaction, respectively. On the surface mapped over electrostatic potential (Fig. 4), these interactions appear as the respective blue and red regions. The views of surfaces mapped over dnorm, de, electrostatic potential and shape-index (Figs. 3–6) highlight the significant role of C—H⋯π interactions in the packing. In particular, the involvement of the methoxy C22′—H group in two C—H⋯π interactions with the symmetry-related aryl rings (Table 1) are evident from the two faint-red spots near these atoms on the dnorm mapped surface, indicated with `2' in Fig. 3.
The corresponding regions on the Hirshfeld surface mapped over electrostatic potential (Fig. 4) appear as blue and light-red, respectively. The remaining C—H⋯π interactions, involving the methylene H2B and H4B atoms as donors, and the C8/C9/C14–C17 and C18–C23 rings as π-acceptors, are also evident from Fig. 4, through the appearance of respective blue and light-red regions near these atoms. The network of these C—H⋯π interactions are also recognized through the pale-orange spots present on the Hirshfeld surfaces mapped over de, highlighted within blue circles in Fig. 5, and as bright-red spots over the front side of shape-indexed surfaces identified with arrows in Fig. 6. The reciprocal of these C—H⋯π interactions, i.e. π⋯H—C, are also seen as blue spots on the shape-indexed surface in Fig. 6. The faint-red spots near the phenyl C23 atom on the surface mapped over dnorm, labelled as `3' in Fig. 3, indicate the presence of short interatomic C⋯H/H⋯C contacts in the crystal, Table 2.
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The overall two-dimensional fingerprint plot (Fig. 7a) and those delineated (McKinnon et al., 2007) into H⋯H, O⋯H/H⋯O and C⋯H/H⋯C contacts are illustrated in Figs. 7(b–d), respectively; their relative contributions are summarized in Table 3. The interatomic H⋯H contacts at distances greater than their van der Waals separation appear as scattered points in the greater part of the fingerprint plot (Fig. 7b), and makes the most significant contribution to the overall Hirshfeld surface, i.e. 49.3%. In the fingerprint plot delineated into O⋯H/H⋯O contacts, a pair of short spikes at de + di ∼ 2.4 Å, and the cluster of blue points aligned in pairs with (de + di)min ∼ 2.7 Å, identified with labels `1' and `2', respectively, in Fig. 7(c), corresponds to a 21.2% contribution to the Hirshfeld surface. These features reflect the presence of aryl-C16—H16⋯O(methoxy) interactions, as well as the short interatomic O⋯H/H⋯O contacts between carboxyl O2 and methylene H3B atoms (Table 2).
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The fingerprint plot delineated into C⋯H/H⋯C contacts, with a 28.1% contribution to the Hirshfeld surface, shows the points in the plot arranged in the form of two pairs of arrow-like shapes with their tips at de + di = 2.70 and 2.85 Å, labelled as `1' and `2' in Fig. 7(d), respectively. These features reflect the presence of C—H⋯π interactions and short interatomic C⋯H/H⋯C contacts (Table 3) in the crystal. The absence of π–π stacking interactions is consistent with their being no contribution from C⋯C contacts to the Hirshfeld surface (Table 3).
The final analysis of the molecular packing involves a relatively new descriptor, i.e. the enrichment ratio (ER) (Jelsch et al., 2014); data are collated in Table 4. The involvement of surface H atoms in C—H⋯π interactions and the presence of a number of interatomic C⋯H contacts (Table 3) yields an ER value for H⋯H contacts less than unity, i.e. 0.90. The presence of these interactions explains the enhanced ER value of 1.31 for C⋯H/H⋯C contacts, consistent with their high propensity to form in the molecular packing of (I). The O atoms comprise only 11.1% of the surface but provide a 21.2% contribution from O⋯H/H⋯O contacts to the Hirshfeld surface. Reflecting this, the ER value is 1.28, which is in the expected 1.2–1.6 range. Other contacts, namely C⋯C, O⋯O and C⋯O/O⋯C, show no propensity to form as reflected in their low ER values (Table 4).
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5. Database survey
There are two structures in the crystallographic literature (Groom et al., 2016) featuring the methine-substituted 2,3,4,12-tetrahydro-5-oxatetraphen-1-one residue, as in (I). In the most closely related structure, (II) (Sethukumar et al., 2012), with a 2-chlorobenzene ring at the methine C7 atom, an essentially similar conformation is found, as emphasized in the overlay diagram shown in Fig. 8. Here, the dihedral angle between the best plane through the cyclohexene ring and naphthyl residue is 7.50 (6)°, i.e. marginally less folded than in (I) where the angle was 10.78 (7)°. The angle between the least-squares planes through the pyran and benzene rings is 89.71 (6)°. Despite having a bulky 2-hydroxy-6-oxocyclohex-1-enyl residue at the methine C7 atom, rather than an aryl ring, the conformation in (III) (Akkurt et al., 2013) bears a close resemblance to those of (I) and (II). Thus, in (III), the cyclohexene/naphthyl dihedral angle is 16.26 (5)°, indicating a non-folded four-ring residue, and the pyran/cyclohexenyl dihedral angle is 85.57 (6)°. Clearly, the non-folded conformation of the 2,3,4,12-tetrahydro-5-oxatetraphen-1-one core and its orthogonal relationship to the methine C7-bound substituent in (I)–(III) is to a first robust.
6. Synthesis and crystallization
The title compound was prepared and characterized spectroscopically as per the literature (Iniyavan et al., 2015). Crystals for the X-ray study were obtained after 2 d of slow evaporation of a chloroform solution of (I) held at room temperature.
7. details
Crystal data, data collection and structure . Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and were included in the in the riding model approximation, with Uiso(H) set at 1.2–1.5Ueq(C).
details are summarized in Table 5
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Supporting information
CCDC reference: 1479203
https://doi.org/10.1107/S2056989016007775/hb7584sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016007775/hb7584Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989016007775/hb7584Isup3.cml
Data collection: CrysAlis PRO (Agilent, 2014); cell
CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C26H24O5 | Dx = 1.347 Mg m−3 |
Mr = 416.45 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 7968 reflections |
a = 9.2164 (5) Å | θ = 3.5–29.3° |
b = 20.3760 (9) Å | µ = 0.09 mm−1 |
c = 21.8731 (9) Å | T = 100 K |
V = 4107.6 (3) Å3 | Prism, colourless |
Z = 8 | 0.25 × 0.20 × 0.20 mm |
F(000) = 1760 |
Agilent Technologies SuperNova Dual diffractometer with an Atlas detector | 4664 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 3991 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.034 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ω scan | h = −9→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −26→24 |
Tmin = 0.855, Tmax = 1.000 | l = −28→25 |
23597 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0327P)2 + 3.0207P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4664 reflections | Δρmax = 0.34 e Å−3 |
283 parameters | Δρmin = −0.22 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.13499 (11) | 0.29394 (5) | 0.08369 (4) | 0.0202 (2) | |
O2 | 0.21599 (12) | 0.47795 (5) | −0.04262 (5) | 0.0249 (2) | |
O20 | 0.43308 (11) | 0.62718 (5) | 0.14235 (4) | 0.0215 (2) | |
O21 | 0.24076 (11) | 0.61119 (5) | 0.23202 (4) | 0.0204 (2) | |
O22 | 0.09183 (11) | 0.49986 (5) | 0.24461 (4) | 0.0202 (2) | |
C1 | 0.10078 (15) | 0.33649 (7) | 0.03771 (6) | 0.0181 (3) | |
C2 | −0.03608 (16) | 0.31688 (7) | 0.00588 (7) | 0.0223 (3) | |
H2A | −0.1058 | 0.2993 | 0.0362 | 0.027* | |
H2B | −0.0146 | 0.2817 | −0.0240 | 0.027* | |
C3 | −0.10412 (16) | 0.37501 (7) | −0.02719 (7) | 0.0236 (3) | |
H3A | −0.1826 | 0.3593 | −0.0544 | 0.028* | |
H3B | −0.1473 | 0.4054 | 0.0031 | 0.028* | |
C4 | 0.00918 (17) | 0.41132 (8) | −0.06483 (6) | 0.0249 (3) | |
H4A | 0.0396 | 0.3831 | −0.0994 | 0.030* | |
H4B | −0.0354 | 0.4514 | −0.0822 | 0.030* | |
C5 | 0.14184 (16) | 0.43053 (7) | −0.02839 (6) | 0.0188 (3) | |
C6 | 0.18328 (15) | 0.38862 (6) | 0.02343 (6) | 0.0172 (3) | |
C7 | 0.31954 (15) | 0.40554 (6) | 0.05870 (6) | 0.0159 (3) | |
H7 | 0.3968 | 0.4186 | 0.0290 | 0.019* | |
C8 | 0.37084 (15) | 0.34558 (6) | 0.09372 (6) | 0.0163 (3) | |
C9 | 0.51546 (15) | 0.34033 (6) | 0.11767 (6) | 0.0179 (3) | |
C10 | 0.62592 (16) | 0.38608 (7) | 0.10377 (6) | 0.0215 (3) | |
H10 | 0.6052 | 0.4217 | 0.0772 | 0.026* | |
C11 | 0.76293 (17) | 0.37994 (8) | 0.12805 (7) | 0.0261 (3) | |
H11 | 0.8356 | 0.4111 | 0.1179 | 0.031* | |
C12 | 0.79633 (17) | 0.32772 (8) | 0.16789 (7) | 0.0280 (3) | |
H12 | 0.8914 | 0.3236 | 0.1842 | 0.034* | |
C13 | 0.69162 (18) | 0.28293 (7) | 0.18297 (7) | 0.0267 (3) | |
H13 | 0.7142 | 0.2483 | 0.2104 | 0.032* | |
C14 | 0.55010 (16) | 0.28747 (7) | 0.15820 (6) | 0.0207 (3) | |
C15 | 0.44087 (16) | 0.24150 (7) | 0.17401 (7) | 0.0225 (3) | |
H15 | 0.4618 | 0.2079 | 0.2028 | 0.027* | |
C16 | 0.30631 (16) | 0.24481 (7) | 0.14842 (6) | 0.0196 (3) | |
H16 | 0.2349 | 0.2127 | 0.1578 | 0.024* | |
C17 | 0.27480 (15) | 0.29668 (7) | 0.10782 (6) | 0.0175 (3) | |
C18 | 0.29511 (14) | 0.46231 (6) | 0.10361 (6) | 0.0153 (3) | |
C19 | 0.37542 (15) | 0.51971 (6) | 0.09866 (6) | 0.0168 (3) | |
H19 | 0.4417 | 0.5253 | 0.0658 | 0.020* | |
C20 | 0.35832 (15) | 0.56922 (6) | 0.14226 (6) | 0.0168 (3) | |
C20' | 0.52664 (17) | 0.63990 (7) | 0.09194 (7) | 0.0244 (3) | |
H20A | 0.6011 | 0.6056 | 0.0897 | 0.037* | |
H20B | 0.5732 | 0.6827 | 0.0974 | 0.037* | |
H20C | 0.4700 | 0.6401 | 0.0540 | 0.037* | |
C21 | 0.26077 (15) | 0.56129 (6) | 0.19031 (6) | 0.0166 (3) | |
C21' | 0.30768 (18) | 0.59803 (7) | 0.29015 (6) | 0.0255 (3) | |
H21A | 0.2686 | 0.5571 | 0.3070 | 0.038* | |
H21B | 0.2872 | 0.6342 | 0.3183 | 0.038* | |
H21C | 0.4128 | 0.5938 | 0.2847 | 0.038* | |
C22 | 0.18044 (15) | 0.50332 (6) | 0.19494 (6) | 0.0162 (3) | |
C22' | 0.01074 (17) | 0.44121 (7) | 0.25262 (7) | 0.0225 (3) | |
H22A | −0.0589 | 0.4366 | 0.2190 | 0.034* | |
H22B | −0.0416 | 0.4431 | 0.2916 | 0.034* | |
H22C | 0.0768 | 0.4035 | 0.2528 | 0.034* | |
C23 | 0.19668 (15) | 0.45412 (6) | 0.15136 (6) | 0.0165 (3) | |
H23 | 0.1408 | 0.4151 | 0.1542 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0199 (5) | 0.0172 (5) | 0.0234 (5) | −0.0026 (4) | −0.0031 (4) | 0.0040 (4) |
O2 | 0.0296 (6) | 0.0215 (5) | 0.0237 (5) | −0.0001 (4) | 0.0005 (4) | 0.0052 (4) |
O20 | 0.0258 (6) | 0.0131 (4) | 0.0255 (5) | −0.0026 (4) | 0.0055 (4) | −0.0010 (4) |
O21 | 0.0282 (6) | 0.0143 (5) | 0.0187 (5) | 0.0031 (4) | 0.0013 (4) | −0.0022 (4) |
O22 | 0.0232 (5) | 0.0180 (5) | 0.0196 (5) | −0.0009 (4) | 0.0058 (4) | −0.0012 (4) |
C1 | 0.0210 (7) | 0.0167 (6) | 0.0167 (6) | 0.0021 (5) | −0.0013 (5) | −0.0011 (5) |
C2 | 0.0225 (7) | 0.0202 (7) | 0.0242 (7) | −0.0009 (6) | −0.0043 (6) | −0.0004 (5) |
C3 | 0.0222 (7) | 0.0250 (7) | 0.0237 (7) | 0.0020 (6) | −0.0055 (6) | 0.0003 (6) |
C4 | 0.0287 (8) | 0.0276 (7) | 0.0183 (7) | 0.0026 (6) | −0.0047 (6) | 0.0022 (6) |
C5 | 0.0223 (7) | 0.0190 (6) | 0.0151 (6) | 0.0042 (5) | 0.0019 (5) | −0.0009 (5) |
C6 | 0.0205 (7) | 0.0168 (6) | 0.0142 (6) | 0.0023 (5) | 0.0006 (5) | −0.0013 (5) |
C7 | 0.0183 (7) | 0.0141 (6) | 0.0153 (6) | −0.0003 (5) | 0.0004 (5) | 0.0005 (5) |
C8 | 0.0202 (7) | 0.0147 (6) | 0.0140 (6) | 0.0015 (5) | 0.0010 (5) | −0.0016 (5) |
C9 | 0.0206 (7) | 0.0157 (6) | 0.0173 (6) | 0.0015 (5) | 0.0001 (5) | −0.0032 (5) |
C10 | 0.0224 (7) | 0.0203 (7) | 0.0219 (7) | 0.0005 (6) | 0.0015 (6) | 0.0008 (5) |
C11 | 0.0244 (8) | 0.0258 (7) | 0.0282 (7) | −0.0028 (6) | −0.0001 (6) | −0.0013 (6) |
C12 | 0.0233 (8) | 0.0271 (8) | 0.0335 (8) | 0.0015 (6) | −0.0082 (7) | −0.0032 (6) |
C13 | 0.0316 (8) | 0.0188 (7) | 0.0295 (8) | 0.0028 (6) | −0.0068 (7) | −0.0012 (6) |
C14 | 0.0249 (7) | 0.0158 (6) | 0.0214 (6) | 0.0016 (5) | −0.0035 (6) | −0.0026 (5) |
C15 | 0.0279 (8) | 0.0167 (6) | 0.0229 (7) | 0.0027 (6) | −0.0017 (6) | 0.0029 (5) |
C16 | 0.0242 (7) | 0.0147 (6) | 0.0199 (6) | −0.0021 (5) | 0.0008 (6) | 0.0001 (5) |
C17 | 0.0193 (7) | 0.0161 (6) | 0.0170 (6) | 0.0013 (5) | −0.0012 (5) | −0.0019 (5) |
C18 | 0.0174 (6) | 0.0143 (6) | 0.0142 (6) | 0.0023 (5) | −0.0035 (5) | 0.0007 (5) |
C19 | 0.0183 (7) | 0.0161 (6) | 0.0159 (6) | 0.0012 (5) | 0.0007 (5) | 0.0024 (5) |
C20 | 0.0182 (7) | 0.0120 (6) | 0.0202 (6) | 0.0001 (5) | −0.0018 (5) | 0.0027 (5) |
C20' | 0.0243 (8) | 0.0181 (7) | 0.0308 (8) | −0.0026 (6) | 0.0075 (6) | 0.0012 (6) |
C21 | 0.0200 (7) | 0.0135 (6) | 0.0163 (6) | 0.0031 (5) | −0.0021 (5) | −0.0008 (5) |
C21' | 0.0353 (9) | 0.0205 (7) | 0.0206 (7) | 0.0008 (6) | −0.0035 (6) | −0.0049 (6) |
C22 | 0.0160 (6) | 0.0175 (6) | 0.0151 (6) | 0.0026 (5) | −0.0006 (5) | 0.0028 (5) |
C22' | 0.0231 (7) | 0.0207 (7) | 0.0238 (7) | −0.0019 (6) | 0.0068 (6) | 0.0018 (6) |
C23 | 0.0172 (7) | 0.0152 (6) | 0.0172 (6) | −0.0003 (5) | −0.0019 (5) | 0.0020 (5) |
O1—C1 | 1.3647 (16) | C10—H10 | 0.9500 |
O1—C17 | 1.3936 (17) | C11—C12 | 1.409 (2) |
O2—C5 | 1.2237 (17) | C11—H11 | 0.9500 |
O20—C20 | 1.3671 (16) | C12—C13 | 1.369 (2) |
O20—C20' | 1.4235 (17) | C12—H12 | 0.9500 |
O21—C21 | 1.3784 (15) | C13—C14 | 1.415 (2) |
O21—C21' | 1.4384 (17) | C13—H13 | 0.9500 |
O22—C22 | 1.3610 (16) | C14—C15 | 1.418 (2) |
O22—C22' | 1.4204 (16) | C15—C16 | 1.362 (2) |
C1—C6 | 1.3431 (19) | C15—H15 | 0.9500 |
C1—C2 | 1.495 (2) | C16—C17 | 1.4105 (19) |
C2—C3 | 1.523 (2) | C16—H16 | 0.9500 |
C2—H2A | 0.9900 | C18—C19 | 1.3884 (18) |
C2—H2B | 0.9900 | C18—C23 | 1.3934 (19) |
C3—C4 | 1.522 (2) | C19—C20 | 1.3972 (18) |
C3—H3A | 0.9900 | C19—H19 | 0.9500 |
C3—H3B | 0.9900 | C20—C21 | 1.3926 (19) |
C4—C5 | 1.511 (2) | C20'—H20A | 0.9800 |
C4—H4A | 0.9900 | C20'—H20B | 0.9800 |
C4—H4B | 0.9900 | C20'—H20C | 0.9800 |
C5—C6 | 1.4698 (18) | C21—C22 | 1.3978 (19) |
C6—C7 | 1.5136 (19) | C21'—H21A | 0.9800 |
C7—C8 | 1.5174 (18) | C21'—H21B | 0.9800 |
C7—C18 | 1.5342 (17) | C21'—H21C | 0.9800 |
C7—H7 | 1.0000 | C22—C23 | 1.3913 (18) |
C8—C17 | 1.3681 (19) | C22'—H22A | 0.9800 |
C8—C9 | 1.4361 (19) | C22'—H22B | 0.9800 |
C9—C10 | 1.413 (2) | C22'—H22C | 0.9800 |
C9—C14 | 1.4311 (19) | C23—H23 | 0.9500 |
C10—C11 | 1.376 (2) | ||
C1—O1—C17 | 117.86 (11) | C12—C13—C14 | 120.92 (14) |
C20—O20—C20' | 117.48 (11) | C12—C13—H13 | 119.5 |
C21—O21—C21' | 112.96 (10) | C14—C13—H13 | 119.5 |
C22—O22—C22' | 117.24 (11) | C13—C14—C15 | 121.18 (13) |
C6—C1—O1 | 122.89 (13) | C13—C14—C9 | 119.47 (13) |
C6—C1—C2 | 125.50 (13) | C15—C14—C9 | 119.34 (13) |
O1—C1—C2 | 111.61 (12) | C16—C15—C14 | 120.89 (13) |
C1—C2—C3 | 111.14 (12) | C16—C15—H15 | 119.6 |
C1—C2—H2A | 109.4 | C14—C15—H15 | 119.6 |
C3—C2—H2A | 109.4 | C15—C16—C17 | 118.90 (13) |
C1—C2—H2B | 109.4 | C15—C16—H16 | 120.6 |
C3—C2—H2B | 109.4 | C17—C16—H16 | 120.6 |
H2A—C2—H2B | 108.0 | C8—C17—O1 | 122.82 (12) |
C4—C3—C2 | 110.64 (13) | C8—C17—C16 | 123.67 (13) |
C4—C3—H3A | 109.5 | O1—C17—C16 | 113.51 (12) |
C2—C3—H3A | 109.5 | C19—C18—C23 | 120.43 (12) |
C4—C3—H3B | 109.5 | C19—C18—C7 | 120.46 (12) |
C2—C3—H3B | 109.5 | C23—C18—C7 | 119.03 (12) |
H3A—C3—H3B | 108.1 | C18—C19—C20 | 119.66 (12) |
C5—C4—C3 | 113.31 (12) | C18—C19—H19 | 120.2 |
C5—C4—H4A | 108.9 | C20—C19—H19 | 120.2 |
C3—C4—H4A | 108.9 | O20—C20—C21 | 115.12 (12) |
C5—C4—H4B | 108.9 | O20—C20—C19 | 124.60 (12) |
C3—C4—H4B | 108.9 | C21—C20—C19 | 120.28 (12) |
H4A—C4—H4B | 107.7 | O20—C20'—H20A | 109.5 |
O2—C5—C6 | 120.65 (13) | O20—C20'—H20B | 109.5 |
O2—C5—C4 | 121.49 (12) | H20A—C20'—H20B | 109.5 |
C6—C5—C4 | 117.81 (12) | O20—C20'—H20C | 109.5 |
C1—C6—C5 | 119.46 (13) | H20A—C20'—H20C | 109.5 |
C1—C6—C7 | 122.09 (12) | H20B—C20'—H20C | 109.5 |
C5—C6—C7 | 118.45 (12) | O21—C21—C20 | 120.02 (12) |
C6—C7—C8 | 109.41 (11) | O21—C21—C22 | 120.31 (12) |
C6—C7—C18 | 112.10 (11) | C20—C21—C22 | 119.65 (12) |
C8—C7—C18 | 109.24 (10) | O21—C21'—H21A | 109.5 |
C6—C7—H7 | 108.7 | O21—C21'—H21B | 109.5 |
C8—C7—H7 | 108.7 | H21A—C21'—H21B | 109.5 |
C18—C7—H7 | 108.7 | O21—C21'—H21C | 109.5 |
C17—C8—C9 | 117.65 (12) | H21A—C21'—H21C | 109.5 |
C17—C8—C7 | 119.91 (12) | H21B—C21'—H21C | 109.5 |
C9—C8—C7 | 122.23 (12) | O22—C22—C23 | 125.04 (12) |
C10—C9—C14 | 117.97 (13) | O22—C22—C21 | 114.79 (12) |
C10—C9—C8 | 122.74 (12) | C23—C22—C21 | 120.15 (12) |
C14—C9—C8 | 119.28 (13) | O22—C22'—H22A | 109.5 |
C11—C10—C9 | 121.20 (13) | O22—C22'—H22B | 109.5 |
C11—C10—H10 | 119.4 | H22A—C22'—H22B | 109.5 |
C9—C10—H10 | 119.4 | O22—C22'—H22C | 109.5 |
C10—C11—C12 | 120.53 (14) | H22A—C22'—H22C | 109.5 |
C10—C11—H11 | 119.7 | H22B—C22'—H22C | 109.5 |
C12—C11—H11 | 119.7 | C22—C23—C18 | 119.82 (12) |
C13—C12—C11 | 119.90 (14) | C22—C23—H23 | 120.1 |
C13—C12—H12 | 120.1 | C18—C23—H23 | 120.1 |
C11—C12—H12 | 120.1 | ||
C17—O1—C1—C6 | −13.87 (19) | C8—C9—C14—C15 | −0.18 (19) |
C17—O1—C1—C2 | 165.29 (11) | C13—C14—C15—C16 | −177.73 (13) |
C6—C1—C2—C3 | −22.4 (2) | C9—C14—C15—C16 | 3.8 (2) |
O1—C1—C2—C3 | 158.43 (12) | C14—C15—C16—C17 | −2.9 (2) |
C1—C2—C3—C4 | 48.01 (16) | C9—C8—C17—O1 | −175.23 (11) |
C2—C3—C4—C5 | −52.63 (16) | C7—C8—C17—O1 | 10.04 (19) |
C3—C4—C5—O2 | −153.03 (13) | C9—C8—C17—C16 | 5.5 (2) |
C3—C4—C5—C6 | 29.63 (18) | C7—C8—C17—C16 | −169.20 (12) |
O1—C1—C6—C5 | 177.52 (12) | C1—O1—C17—C8 | 9.55 (18) |
C2—C1—C6—C5 | −1.5 (2) | C1—O1—C17—C16 | −171.14 (11) |
O1—C1—C6—C7 | −1.8 (2) | C15—C16—C17—C8 | −2.0 (2) |
C2—C1—C6—C7 | 179.13 (13) | C15—C16—C17—O1 | 178.70 (12) |
O2—C5—C6—C1 | −179.34 (13) | C6—C7—C18—C19 | −120.36 (13) |
C4—C5—C6—C1 | −1.98 (19) | C8—C7—C18—C19 | 118.19 (13) |
O2—C5—C6—C7 | 0.03 (19) | C6—C7—C18—C23 | 62.98 (15) |
C4—C5—C6—C7 | 177.40 (12) | C8—C7—C18—C23 | −58.47 (16) |
C1—C6—C7—C8 | 19.27 (17) | C23—C18—C19—C20 | 0.7 (2) |
C5—C6—C7—C8 | −160.10 (11) | C7—C18—C19—C20 | −175.94 (12) |
C1—C6—C7—C18 | −102.08 (15) | C20'—O20—C20—C21 | −175.65 (12) |
C5—C6—C7—C18 | 78.55 (14) | C20'—O20—C20—C19 | 4.98 (19) |
C6—C7—C8—C17 | −22.82 (16) | C18—C19—C20—O20 | 179.03 (12) |
C18—C7—C8—C17 | 100.24 (14) | C18—C19—C20—C21 | −0.3 (2) |
C6—C7—C8—C9 | 162.70 (12) | C21'—O21—C21—C20 | −105.78 (14) |
C18—C7—C8—C9 | −74.24 (15) | C21'—O21—C21—C22 | 76.08 (16) |
C17—C8—C9—C10 | 176.82 (13) | O20—C20—C21—O21 | 2.79 (18) |
C7—C8—C9—C10 | −8.6 (2) | C19—C20—C21—O21 | −177.81 (12) |
C17—C8—C9—C14 | −4.30 (18) | O20—C20—C21—C22 | −179.06 (12) |
C7—C8—C9—C14 | 170.30 (12) | C19—C20—C21—C22 | 0.3 (2) |
C14—C9—C10—C11 | 0.4 (2) | C22'—O22—C22—C23 | 0.51 (19) |
C8—C9—C10—C11 | 179.30 (13) | C22'—O22—C22—C21 | −178.19 (12) |
C9—C10—C11—C12 | −0.4 (2) | O21—C21—C22—O22 | −3.82 (18) |
C10—C11—C12—C13 | −0.4 (2) | C20—C21—C22—O22 | 178.04 (12) |
C11—C12—C13—C14 | 1.2 (2) | O21—C21—C22—C23 | 177.42 (12) |
C12—C13—C14—C15 | −179.52 (14) | C20—C21—C22—C23 | −0.7 (2) |
C12—C13—C14—C9 | −1.1 (2) | O22—C22—C23—C18 | −177.55 (12) |
C10—C9—C14—C13 | 0.3 (2) | C21—C22—C23—C18 | 1.1 (2) |
C8—C9—C14—C13 | −178.63 (13) | C19—C18—C23—C22 | −1.1 (2) |
C10—C9—C14—C15 | 178.75 (13) | C7—C18—C23—C22 | 175.60 (12) |
Cg1, Cg2 and Cg3 are the centroids of the C8/C9/C14–C17, C18–C23 and C9–C14 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···O20i | 0.95 | 2.36 | 3.2604 (18) | 159 |
C2—H2B···Cg1ii | 0.99 | 2.92 | 3.8088 (16) | 150 |
C4—H4B···Cg2iii | 0.99 | 2.75 | 3.5605 (16) | 140 |
C22′—H22B···Cg2iv | 0.98 | 2.56 | 3.3918 (16) | 143 |
C22′—H22C···Cg3iv | 0.98 | 2.78 | 3.4332 (16) | 125 |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x−1/2, −y+1/2, −z; (iii) −x, −y+1, −z; (iv) x−3/2, y, −z−1/2. |
Contact | Contribution |
H···H | 49.9 |
O···H/H···O | 21.2 |
C···H/H···C | 28.1 |
C···O/O···C | 0.6 |
O···O | 0.2 |
C···C | 0.0 |
Interaction | Distance | Symmetry operation |
C23···H4B | 2.86 | -x, 1-y, -z |
C23···H22B | 2.72 | 1/2+x, y, 1/2-z |
C11···H2A | 2.86 | 1+x, y, z |
C11···H22A | 2.83 | 1+x, y, z |
O2···H3B | 2.61 | -x, 1-y, -z |
C12···H22A | 2.82 | 1+x, y, z |
C18···H22B | 2.77 | 1/2+x, y, 1/2-z |
C22···H22B | 2.86 | 1/2+x, y, 1/2-z |
C21'···H4A | 2.82 | 1/2-x, 1-y, 1/2+z |
Interaction | ER |
H···H | 0.90 |
O···H/H···O | 1.28 |
C···H/H···C | 1.31 |
C···C | 0.0 |
C···O/O···C | 0.19 |
O···O | 0.16 |
Acknowledgements
VIT University is thanked for providing facilities.
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