research communications
Crystal structures and Hirshfeld surface analyses of 4,4′-{[1,3-phenylenebis(methylene)]bis(oxy)}bis(3-methoxybenzaldehyde) and 4,4′-{[(1,4-phenylenebis(methylene)]bis(oxy)}bis(3-methoxybenzaldehyde)
aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, bDepartment of Biophysics, All India Institute of Medical Sciences, New Delhi 110 029, India, and cDepartment of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
*Correspondence e-mail: gunaunom@gmail.com
The title compounds, C24H22O6 (I) and C24H22O6 (II), each crystallize with half a molecule in the The whole molecule of compound (I) is generated by twofold rotation symmetry, the twofold axis bisecting the central benzene ring. The whole molecule of compound (II) is generated by inversion symmetry, the central benzene ring being located on an inversion center. In (I), the outer benzene rings are inclined to each other by 59.96 (10)° and by 36.74 (9)° to the central benzene ring. The corresponding dihedral angles in (II) are 0.0 and 89.87 (12)°. In the crystal of (I), molecules are linked by C—H⋯O hydrogen bonds and C—H⋯π interactions, forming ribbons propagating along the [10] direction. In the crystal of (II), molecules are linked by C—H⋯O hydrogen bonds, forming a supramolecular framework. The Hirshfeld surface analyses indicate that for both compounds the H⋯H contacts are the most significant, followed by O⋯H/H⋯O and C⋯H/H⋯C contacts.
1. Chemical context
Vanillin, a phenolic compound, has been reported to offer neuroprotection against experimental Huntington's disease and global ischemia by virtue of its antioxidant, anti-inflammatory and antiapoptotic properties. Vanillin is a potential future therapeutic agent by virtue of its multiple pharmacological properties relevant to the treatment of neurodegenerative diseases (Dhanalakshmi et al., 2015). Structural elements of vanillin have been observed to show antifungal activity (Fitzgerald et al., 2005). Studies have revealed that the root and pod extracts of the plants Heiidesmus Indicus and vanilla planifola (plant-based food-flavouring agents) produce the fragrant phenolic compounds 2-hydroxy-4-methoxybenzaldehyde (MBALD) and 4-hydroxy-3-methoxybenzaldehyde (vanillin). These compounds have been shown to be effective in treating Alzheimer's disease and other neurological dysfunctions (Kundu & Mitra, 2013). Vanillin derivatives with various homocyclic or heterocyclic and hydrophobic or hydrophilic moieties have shown tyrosinase inhibitory activity (Ashraf et al., 2015). In view of the interest in such compounds we have synthesized 4,4′-{[1,3-phenylenebis(methylene)]bis(oxy)}bis(3-methoxybenzaldehyde) (I) and 4,4′-{[(1,4-phenylenebis(methylene)]bis(oxy)}bis(3-methoxybenzaldehyde) (II), and report herein on their crystal structures and Hirshfeld surface analyses.
2. Structural commentary
The molecular structure of compound (I) is shown in Fig. 1. The consists of half a molecule, the other half being generated by twofold rotation symmetry; the twofold axis bisects atoms C11 and C13 of the central benzene ring. The dihedral angle between the central benzene ring (C10–C13/C10′/C12′) and the outer benzene ring (C2–C7/C2′–C7′) is 36.74 (9)° [symmetry code: (') −x + 2, y, −z + ). The outer benzene rings are inclined to each other by 59.96 (10)°. The acetaldehyde and methoxymethane groups adopt extended conformations, as can be seen from the torsion angles C3—C2—C1—O1 = 180.0 (3)° and C5—C6—O2—C8 = −160.7 (3)°. Atoms C1 and O1 deviate from the plane of the benzene ring by 0.021 (2) and 0.034 (2) Å, respectively, while atoms O2 and C8 deviate from the plane of the benzene ring by −0.032 (2) and −0.471 (4)Å, respectively.
The molecular structure of compound (II) is shown in Fig. 2. The consists of half a molecule, the other half being generated by inversion symmetry; the central benzene ring being situated about the inversion center. The outer benzene rings are parallel to each other and normal to the central benzene ring with a dihedral angle of 89.87 (12)°. The methoxymethane and acetaldehyde groups adopt extended conformations, as can be seen from the torsion angles C5—C6—O2—C8 = 172.7 (2) Å and C7—C2—C1—O3 = −178.5 (3)°. Here, atoms O2 and C8 deviate from the plane of the benzene ring by −0.025 (2) and −0.211 (4) Å, respectively, while atoms C1 and O1 deviate from the plane of the benzene ring by 0.023 (3) and 0.056 (2) Å, respectively.
3. Supramolecular features
In the crystal of (I), molecules are linked by C3—H3⋯Oi hydrogen bonds forming ribbons propagating along the [10] direction (Table 1 and Fig. 3). Within the ribbons molecules are also linked by C—H⋯π interactions (Table 1), as shown in Fig. 4.
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In the crystal of (II), molecules are linked by C7—H7⋯O3i and C12—H12⋯O2ii hydrogen bonds (Table 2), forming a supramolecular framework, as shown in Fig. 5.
4. Hirshfeld surface analysis
The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007) were performed using CrystalExplorer17 (Turner et al., 2017).
The Hirshfeld surfaces of compounds (I) and (II) mapped over dnorm are given in Fig. 6a and 6b, respectively. Views of the intermolecular contacts in the crystals are shown in Figs. 7 and 8, for compounds (I) and (II), respectively. They are colour-mapped with the normalized contact distance, dnorm, 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 blue region represents the positive electrostatic potential over the surface. The dnorm surface was mapped over a colour scale in arbitrary units of −0.156 (red) to 1.705 (blue) for compound (I) and −0.207 (red) to 1.206 (blue) for compound (II), where the red spots indicate the intermolecular contacts involved in the hydrogen bonding.
The two-dimensional fingerprint plots [Fig. 9 for (I) and Fig. 10 for (II)] are deconvoluted to highlight atom-pair close contacts by which different atomic types, overlapping the full fingerprint plot can be separated based on different interaction types. For compound (I), intermolecular H⋯H contacts of 40.4% (Fig. 9b) are the most significant, followed by 29.1% for O⋯H/H⋯O (Fig. 9c), 26.4% for C⋯H/H⋯C (Fig. 9d) and 3.1% for C⋯C (Fig. 9e) contacts. In contrast, for compound (II) the H⋯H contacts at 42.2% (Fig. 10b) make a slightly higher contribution than in (I), while the C⋯H/H⋯C contacts at 23.6% (Fig. 10d) make a slightly lower contribution than in (I). The O⋯H/H⋯O contacts (Fig. 10c) in both compounds are similar; 29.1% in (I) cf. 29.0% in (II).
5. Database survey
A search of the Cambridge Structure Database (CSD, Version 5.40, February 2019; Groom et al., 2016) for similar compounds gave one hit for 1,3-bis[(2-methoxyphenoxy)methyl]benzene (CSD refcode KACQEL; Bryan et al., 2003) but no hits for a 1,4-derivative. In KACQEL, the central benzene ring is inclined to the outer benzene rings by 67.60 (4) and 72.68 (6)°, while the outer benzene rings are inclined to each other by 69.61 (6)°. In compound (I), the central benzene ring is inclined to the outer benzene ring(s) by 36.74 (9)°, while the outer benzene rings are inclined to each other by 59.96 (10)°. In compound (II), the corresponding dihedral angles are 89.87 (2) and 0.0°, respectively.
A search for 4-benzyloxy-3-methoxybenzaldehydes gave eight hits. Apart from 4-benzyloxy-3-methoxybenzaldehyde itself (vanillin benzyl ether: COBNUC; Gerkin, 1999), the other hits include the 4-nitrobenzyloxy derivative (VOHYUN; Li & Chen, 2008), the 4-fluorobenzyloxy derivative (POMQIT; Bernard-Gauthier & Schirrmacher, 2014) and the 4-chlorobenzyloxy derivative (WINROB; Liu et al., 2007). In VOHYUN, the 3-methoxybenzaldehyde ring is inclined to the 4-benzyloxy ring by 5.00 (11)°, while in COBNUC this dihedral angle is 78.11 (9)°. In POMQIT and WINROB, the corresponding dihedral angles are 69.02 (5) and 72.59 (19)°, respectively, similar to the values observed in KACQEL, viz. 67.60 (4) and 72.68 (6)°.
6. Synthesis and crystallization
Compound (I): To vanillin (0.63 g, 4.1 mmol) dissolved in 20 ml DMF was added potassium carbonate (1.7 g, 12.5 mmol) and the mixture was stirred at room temperature followed by addition of 1,3-bis(bromomethyl)benzene (0.5 g, 1.9 mmol). The reaction was allowed to proceed for 12 h. Then the reaction mixture was partitioned between water and ethyl acetate. The ethyl acetate layer was collected and concentrated under reduced pressure. The crude product obtained was recrystallized by using ethyl acetate. Colourless block-like crystals were obtained on slow evaporation of the solvent (98%).
Compound (II): To vanillin (0.63 g, 4.1 mmol) dissolved in 20 ml DMF, was added potassium carbonate (1.7 g, 12.5 mmol) and the mixture was stirred at room temperature followed by addition of 1,4-bis(bromomethyl)benzene (0.5 g, 1.9 mmol). The reaction was allowed to proceed for 12 h. After the reaction mixture was partitioned between water and ethyl acetate, the ethyl acetate layer was collected and concentrated under reduced pressure. The crude product was recrystallized by using ethyl acetate. Colourless block-like crystals were obtained on slow evaporation of the solvent (98%).
7. Refinement
Crystal data, data collection and structure . For both compounds, the hydrogen atoms were fixed geometrically and allowed to ride on their parent atoms: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(N,C) for other H atoms.
details are summarized in Table 3Supporting information
https://doi.org/10.1107/S2056989019006662/su5484sup1.cif
contains datablocks global, I, II. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019006662/su5484Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019006662/su5484IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019006662/su5484Isup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989019006662/su5484IIsup5.cml
For both structures, data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/4 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016/4 (Sheldrick, 2015) and PLATON (Spek, 2009).C24H22O6 | F(000) = 856 |
Mr = 406.41 | Dx = 1.296 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7026 (3) Å | Cell parameters from 2595 reflections |
b = 14.6628 (4) Å | θ = 2.3–28.4° |
c = 12.7512 (3) Å | µ = 0.09 mm−1 |
β = 107.863 (2)° | T = 293 K |
V = 2082.54 (9) Å3 | Block, colourless |
Z = 4 | 0.26 × 0.19 × 0.11 mm |
Bruker SMART APEXII area detector diffractometer | 1497 reflections with I > 2σ(I) |
ω and φ scans | Rint = 0.024 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 28.4°, θmin = 2.3° |
Tmin = 0.753, Tmax = 0.842 | h = −15→15 |
10081 measured reflections | k = −13→19 |
2595 independent reflections | l = −17→16 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0852P)2 + 0.5811P] where P = (Fo2 + 2Fc2)/3 |
2595 reflections | (Δ/σ)max < 0.001 |
138 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | 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 | ||
O3 | 0.93872 (11) | 0.15775 (9) | 0.04447 (9) | 0.0615 (4) | |
C10 | 0.94216 (16) | 0.02577 (13) | 0.15339 (13) | 0.0541 (5) | |
C9 | 0.87534 (17) | 0.07592 (13) | 0.05044 (14) | 0.0605 (5) | |
H9A | 0.869121 | 0.038180 | −0.013554 | 0.073* | |
H9B | 0.794849 | 0.090322 | 0.051631 | 0.073* | |
C2 | 0.81181 (18) | 0.33726 (15) | −0.21384 (14) | 0.0668 (6) | |
C5 | 0.89059 (16) | 0.21460 (13) | −0.04217 (12) | 0.0550 (5) | |
C4 | 0.78416 (17) | 0.19835 (14) | −0.12530 (14) | 0.0632 (5) | |
H4 | 0.739281 | 0.146221 | −0.124167 | 0.076* | |
C11 | 1.000000 | 0.07241 (18) | 0.250000 | 0.0563 (6) | |
H11 | 1.000000 | 0.135837 | 0.250002 | 0.068* | |
O2 | 1.05928 (15) | 0.30383 (11) | 0.04307 (12) | 0.0928 (6) | |
C3 | 0.74587 (18) | 0.26096 (15) | −0.20991 (14) | 0.0683 (6) | |
H3 | 0.673846 | 0.251044 | −0.265279 | 0.082* | |
C6 | 0.95715 (17) | 0.29375 (14) | −0.04386 (14) | 0.0648 (5) | |
C12 | 0.94372 (17) | −0.06856 (13) | 0.15437 (15) | 0.0621 (5) | |
H12 | 0.906532 | −0.100685 | 0.090051 | 0.075* | |
C13 | 1.000000 | −0.1151 (2) | 0.250000 | 0.0713 (8) | |
H13 | 1.000002 | −0.178546 | 0.249999 | 0.086* | |
O1 | 0.81947 (19) | 0.47012 (15) | −0.31880 (14) | 0.1063 (7) | |
C7 | 0.91931 (18) | 0.35402 (15) | −0.12987 (15) | 0.0691 (6) | |
H7 | 0.964657 | 0.405581 | −0.132429 | 0.083* | |
C1 | 0.7698 (2) | 0.4010 (2) | −0.30609 (17) | 0.0851 (7) | |
H1 | 0.698090 | 0.386782 | −0.359846 | 0.102* | |
C8 | 1.1085 (3) | 0.3927 (2) | 0.0642 (3) | 0.1509 (18) | |
H8A | 1.137086 | 0.411446 | 0.004552 | 0.226* | |
H8B | 1.173946 | 0.392483 | 0.131560 | 0.226* | |
H8C | 1.047747 | 0.434366 | 0.070672 | 0.226* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0645 (8) | 0.0617 (8) | 0.0401 (6) | −0.0032 (6) | −0.0109 (5) | 0.0053 (5) |
C10 | 0.0556 (10) | 0.0551 (11) | 0.0448 (8) | −0.0004 (8) | 0.0052 (7) | −0.0028 (7) |
C9 | 0.0664 (11) | 0.0584 (12) | 0.0413 (8) | −0.0049 (9) | −0.0060 (7) | −0.0057 (8) |
C2 | 0.0714 (12) | 0.0714 (14) | 0.0412 (9) | 0.0141 (10) | −0.0072 (8) | 0.0046 (8) |
C5 | 0.0586 (10) | 0.0587 (11) | 0.0342 (7) | 0.0051 (9) | −0.0057 (7) | −0.0016 (7) |
C4 | 0.0626 (11) | 0.0659 (13) | 0.0444 (9) | 0.0019 (9) | −0.0082 (8) | −0.0051 (8) |
C11 | 0.0637 (15) | 0.0482 (15) | 0.0437 (12) | 0.000 | −0.0031 (10) | 0.000 |
O2 | 0.0826 (10) | 0.0899 (12) | 0.0666 (9) | −0.0222 (8) | −0.0352 (7) | 0.0219 (7) |
C3 | 0.0660 (12) | 0.0761 (14) | 0.0416 (9) | 0.0075 (11) | −0.0145 (8) | −0.0031 (8) |
C6 | 0.0623 (11) | 0.0712 (14) | 0.0420 (9) | −0.0009 (9) | −0.0119 (8) | 0.0034 (8) |
C12 | 0.0711 (12) | 0.0556 (12) | 0.0541 (10) | −0.0039 (9) | 0.0110 (9) | −0.0113 (8) |
C13 | 0.090 (2) | 0.0497 (17) | 0.0703 (17) | 0.000 | 0.0194 (15) | 0.000 |
O1 | 0.1169 (15) | 0.0983 (14) | 0.0792 (11) | 0.0096 (11) | −0.0061 (10) | 0.0360 (10) |
C7 | 0.0709 (12) | 0.0692 (13) | 0.0496 (9) | −0.0004 (10) | −0.0076 (8) | 0.0088 (9) |
C1 | 0.0874 (16) | 0.0919 (18) | 0.0544 (11) | 0.0155 (14) | −0.0100 (10) | 0.0169 (11) |
C8 | 0.156 (3) | 0.125 (3) | 0.102 (2) | −0.072 (2) | −0.063 (2) | 0.0382 (19) |
O3—C5 | 1.360 (2) | C11—H11 | 0.9300 |
O3—C9 | 1.425 (2) | O2—C6 | 1.366 (2) |
C10—C12 | 1.383 (3) | O2—C8 | 1.416 (3) |
C10—C11 | 1.390 (2) | C3—H3 | 0.9300 |
C10—C9 | 1.499 (2) | C6—C7 | 1.372 (3) |
C9—H9A | 0.9700 | C12—C13 | 1.376 (2) |
C9—H9B | 0.9700 | C12—H12 | 0.9300 |
C2—C3 | 1.369 (3) | C13—C12i | 1.376 (2) |
C2—C7 | 1.401 (3) | C13—H13 | 0.9300 |
C2—C1 | 1.464 (3) | O1—C1 | 1.204 (3) |
C5—C4 | 1.386 (2) | C7—H7 | 0.9300 |
C5—C6 | 1.402 (3) | C1—H1 | 0.9300 |
C4—C3 | 1.382 (3) | C8—H8A | 0.9600 |
C4—H4 | 0.9300 | C8—H8B | 0.9600 |
C11—C10i | 1.390 (2) | C8—H8C | 0.9600 |
C5—O3—C9 | 117.82 (13) | C2—C3—H3 | 119.3 |
C12—C10—C11 | 118.85 (17) | C4—C3—H3 | 119.3 |
C12—C10—C9 | 120.03 (15) | O2—C6—C7 | 124.50 (19) |
C11—C10—C9 | 121.09 (17) | O2—C6—C5 | 115.42 (16) |
O3—C9—C10 | 108.65 (13) | C7—C6—C5 | 120.07 (16) |
O3—C9—H9A | 110.0 | C13—C12—C10 | 120.36 (18) |
C10—C9—H9A | 110.0 | C13—C12—H12 | 119.8 |
O3—C9—H9B | 110.0 | C10—C12—H12 | 119.8 |
C10—C9—H9B | 110.0 | C12—C13—C12i | 120.5 (3) |
H9A—C9—H9B | 108.3 | C12—C13—H13 | 119.7 |
C3—C2—C7 | 119.97 (17) | C12i—C13—H13 | 119.7 |
C3—C2—C1 | 119.81 (18) | C6—C7—C2 | 119.5 (2) |
C7—C2—C1 | 120.2 (2) | C6—C7—H7 | 120.3 |
O3—C5—C4 | 124.52 (18) | C2—C7—H7 | 120.3 |
O3—C5—C6 | 115.23 (14) | O1—C1—C2 | 126.1 (2) |
C4—C5—C6 | 120.25 (16) | O1—C1—H1 | 117.0 |
C3—C4—C5 | 118.9 (2) | C2—C1—H1 | 117.0 |
C3—C4—H4 | 120.6 | O2—C8—H8A | 109.5 |
C5—C4—H4 | 120.6 | O2—C8—H8B | 109.5 |
C10—C11—C10i | 121.0 (2) | H8A—C8—H8B | 109.5 |
C10—C11—H11 | 119.5 | O2—C8—H8C | 109.5 |
C10i—C11—H11 | 119.5 | H8A—C8—H8C | 109.5 |
C6—O2—C8 | 117.20 (18) | H8B—C8—H8C | 109.5 |
C2—C3—C4 | 121.33 (16) | ||
C5—O3—C9—C10 | −178.26 (15) | O3—C5—C6—O2 | −1.6 (3) |
C12—C10—C9—O3 | −145.60 (18) | C4—C5—C6—O2 | 178.78 (19) |
C11—C10—C9—O3 | 36.5 (2) | O3—C5—C6—C7 | 177.39 (17) |
C9—O3—C5—C4 | −0.1 (3) | C4—C5—C6—C7 | −2.2 (3) |
C9—O3—C5—C6 | −179.75 (17) | C11—C10—C12—C13 | 1.1 (3) |
O3—C5—C4—C3 | −178.96 (17) | C9—C10—C12—C13 | −176.87 (16) |
C6—C5—C4—C3 | 0.6 (3) | C10—C12—C13—C12i | −0.54 (13) |
C12—C10—C11—C10i | −0.52 (13) | O2—C6—C7—C2 | −179.0 (2) |
C9—C10—C11—C10i | 177.38 (19) | C5—C6—C7—C2 | 2.1 (3) |
C7—C2—C3—C4 | −1.2 (3) | C3—C2—C7—C6 | −0.4 (3) |
C1—C2—C3—C4 | 178.6 (2) | C1—C2—C7—C6 | 179.8 (2) |
C5—C4—C3—C2 | 1.1 (3) | C3—C2—C1—O1 | 180.0 (3) |
C8—O2—C6—C7 | 20.4 (4) | C7—C2—C1—O1 | −0.2 (4) |
C8—O2—C6—C5 | −160.7 (3) |
Symmetry code: (i) −x+2, y, −z+1/2. |
Cg1 is the centroid of the C2–C7 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2ii | 0.93 | 2.53 | 3.3723 (1) | 151 |
C9—H9B···Cg1iii | 0.97 | 2.81 | 3.7808 (1) | 144 |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+3/2, −y+1/2, −z. |
C24H22O6 | F(000) = 428 |
Mr = 406.41 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.6668 (5) Å | Cell parameters from 2488 reflections |
b = 7.7470 (3) Å | θ = 1.6–28.4° |
c = 10.4244 (4) Å | µ = 0.10 mm−1 |
β = 102.126 (2)° | T = 296 K |
V = 1000.12 (7) Å3 | Block, colourless |
Z = 2 | 0.24 × 0.19 × 0.14 mm |
Bruker SMART APEXII area detector diffractometer | 1764 reflections with I > 2σ(I) |
ω and φ scans | Rint = 0.028 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 28.4°, θmin = 1.6° |
Tmin = 0.741, Tmax = 0.863 | h = −16→11 |
9260 measured reflections | k = −10→10 |
2488 independent reflections | l = −13→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.190 | w = 1/[σ2(Fo2) + (0.067P)2 + 0.6516P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
2488 reflections | Δρmax = 0.21 e Å−3 |
138 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: (SHELXL-2016/4; Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.012 (4) |
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 | ||
O2 | 0.30136 (14) | 1.1675 (2) | 0.5834 (2) | 0.0541 (5) | |
O1 | 0.36397 (14) | 0.9305 (2) | 0.44499 (19) | 0.0523 (5) | |
C6 | 0.23878 (19) | 1.0232 (3) | 0.5659 (2) | 0.0420 (5) | |
C5 | 0.27247 (18) | 0.8936 (3) | 0.4887 (2) | 0.0418 (5) | |
C7 | 0.14955 (19) | 0.9951 (3) | 0.6183 (2) | 0.0443 (6) | |
H7 | 0.127746 | 1.079201 | 0.670885 | 0.053* | |
C4 | 0.2124 (2) | 0.7427 (3) | 0.4619 (3) | 0.0477 (6) | |
H4 | 0.233030 | 0.658649 | 0.408429 | 0.057* | |
C2 | 0.09122 (19) | 0.8417 (3) | 0.5933 (2) | 0.0450 (6) | |
O3 | −0.05970 (18) | 0.6894 (3) | 0.6395 (2) | 0.0730 (7) | |
C3 | 0.1222 (2) | 0.7173 (3) | 0.5146 (3) | 0.0493 (6) | |
H3 | 0.082419 | 0.616013 | 0.496873 | 0.059* | |
C10 | 0.45132 (19) | 0.6482 (3) | 0.4372 (2) | 0.0421 (5) | |
C9 | 0.4032 (2) | 0.8059 (3) | 0.3651 (3) | 0.0543 (7) | |
H9A | 0.457346 | 0.860256 | 0.325172 | 0.065* | |
H9B | 0.343984 | 0.770853 | 0.294866 | 0.065* | |
C11 | 0.5138 (2) | 0.6577 (3) | 0.5620 (3) | 0.0520 (7) | |
H11 | 0.523957 | 0.763637 | 0.604812 | 0.062* | |
C1 | −0.0040 (2) | 0.8164 (4) | 0.6514 (3) | 0.0582 (7) | |
H1 | −0.022677 | 0.906265 | 0.701458 | 0.070* | |
C8 | 0.2642 (3) | 1.3100 (3) | 0.6471 (4) | 0.0684 (9) | |
H8A | 0.193267 | 1.342179 | 0.600621 | 0.103* | |
H8B | 0.312586 | 1.405680 | 0.648261 | 0.103* | |
H8C | 0.261680 | 1.278595 | 0.735459 | 0.103* | |
C12 | 0.4386 (2) | 0.4880 (3) | 0.3760 (3) | 0.0526 (7) | |
H12 | 0.397133 | 0.479111 | 0.291377 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0558 (10) | 0.0340 (9) | 0.0740 (13) | −0.0046 (7) | 0.0172 (9) | −0.0053 (8) |
O1 | 0.0537 (10) | 0.0376 (9) | 0.0721 (12) | 0.0043 (8) | 0.0280 (9) | 0.0017 (8) |
C6 | 0.0461 (12) | 0.0313 (11) | 0.0468 (13) | 0.0027 (9) | 0.0058 (10) | 0.0020 (9) |
C5 | 0.0441 (12) | 0.0339 (11) | 0.0487 (13) | 0.0048 (9) | 0.0128 (10) | 0.0057 (9) |
C7 | 0.0468 (12) | 0.0398 (12) | 0.0473 (13) | 0.0049 (10) | 0.0124 (10) | −0.0013 (10) |
C4 | 0.0538 (14) | 0.0333 (12) | 0.0562 (15) | 0.0038 (10) | 0.0123 (11) | −0.0059 (10) |
C2 | 0.0458 (12) | 0.0413 (12) | 0.0476 (13) | 0.0020 (10) | 0.0087 (10) | 0.0062 (10) |
O3 | 0.0699 (13) | 0.0722 (14) | 0.0826 (15) | −0.0165 (11) | 0.0287 (11) | 0.0099 (12) |
C3 | 0.0470 (13) | 0.0375 (12) | 0.0618 (16) | −0.0029 (10) | 0.0076 (11) | 0.0005 (11) |
C10 | 0.0430 (12) | 0.0393 (12) | 0.0491 (13) | 0.0012 (9) | 0.0214 (10) | −0.0006 (10) |
C9 | 0.0628 (16) | 0.0485 (14) | 0.0588 (16) | 0.0096 (12) | 0.0293 (13) | 0.0075 (12) |
C11 | 0.0605 (15) | 0.0379 (13) | 0.0584 (16) | 0.0008 (11) | 0.0143 (12) | −0.0130 (11) |
C1 | 0.0573 (16) | 0.0614 (17) | 0.0589 (16) | −0.0015 (13) | 0.0188 (13) | 0.0042 (13) |
C8 | 0.0711 (19) | 0.0353 (13) | 0.097 (2) | 0.0009 (13) | 0.0129 (17) | −0.0173 (14) |
C12 | 0.0568 (15) | 0.0518 (15) | 0.0462 (14) | 0.0042 (12) | 0.0041 (11) | −0.0081 (11) |
O2—C6 | 1.361 (3) | C3—H3 | 0.9300 |
O2—C8 | 1.418 (3) | C10—C11 | 1.375 (4) |
O1—C5 | 1.362 (3) | C10—C12 | 1.390 (3) |
O1—C9 | 1.431 (3) | C10—C9 | 1.495 (3) |
C6—C7 | 1.372 (3) | C9—H9A | 0.9700 |
C6—C5 | 1.408 (3) | C9—H9B | 0.9700 |
C5—C4 | 1.390 (3) | C11—C12i | 1.376 (4) |
C7—C2 | 1.395 (3) | C11—H11 | 0.9300 |
C7—H7 | 0.9300 | C1—H1 | 0.9300 |
C4—C3 | 1.382 (4) | C8—H8A | 0.9600 |
C4—H4 | 0.9300 | C8—H8B | 0.9600 |
C2—C3 | 1.375 (4) | C8—H8C | 0.9600 |
C2—C1 | 1.472 (4) | C12—C11i | 1.376 (4) |
O3—C1 | 1.202 (3) | C12—H12 | 0.9300 |
C6—O2—C8 | 117.4 (2) | C12—C10—C9 | 120.2 (2) |
C5—O1—C9 | 118.51 (19) | O1—C9—C10 | 114.4 (2) |
O2—C6—C7 | 125.6 (2) | O1—C9—H9A | 108.7 |
O2—C6—C5 | 115.1 (2) | C10—C9—H9A | 108.7 |
C7—C6—C5 | 119.2 (2) | O1—C9—H9B | 108.7 |
O1—C5—C4 | 125.3 (2) | C10—C9—H9B | 108.7 |
O1—C5—C6 | 115.0 (2) | H9A—C9—H9B | 107.6 |
C4—C5—C6 | 119.7 (2) | C10—C11—C12i | 120.6 (2) |
C6—C7—C2 | 120.6 (2) | C10—C11—H11 | 119.7 |
C6—C7—H7 | 119.7 | C12i—C11—H11 | 119.7 |
C2—C7—H7 | 119.7 | O3—C1—C2 | 125.5 (3) |
C3—C4—C5 | 120.2 (2) | O3—C1—H1 | 117.3 |
C3—C4—H4 | 119.9 | C2—C1—H1 | 117.3 |
C5—C4—H4 | 119.9 | O2—C8—H8A | 109.5 |
C3—C2—C7 | 120.1 (2) | O2—C8—H8B | 109.5 |
C3—C2—C1 | 120.9 (2) | H8A—C8—H8B | 109.5 |
C7—C2—C1 | 119.0 (2) | O2—C8—H8C | 109.5 |
C2—C3—C4 | 120.0 (2) | H8A—C8—H8C | 109.5 |
C2—C3—H3 | 120.0 | H8B—C8—H8C | 109.5 |
C4—C3—H3 | 120.0 | C11i—C12—C10 | 121.4 (2) |
C11—C10—C12 | 118.0 (2) | C11i—C12—H12 | 119.3 |
C11—C10—C9 | 121.7 (2) | C10—C12—H12 | 119.3 |
C8—O2—C6—C7 | −8.4 (4) | C6—C7—C2—C1 | 180.0 (2) |
C8—O2—C6—C5 | 172.7 (2) | C7—C2—C3—C4 | 1.2 (4) |
C9—O1—C5—C4 | −0.1 (4) | C1—C2—C3—C4 | −179.4 (2) |
C9—O1—C5—C6 | −179.6 (2) | C5—C4—C3—C2 | 0.3 (4) |
O2—C6—C5—O1 | 1.2 (3) | C5—O1—C9—C10 | −71.7 (3) |
C7—C6—C5—O1 | −177.7 (2) | C11—C10—C9—O1 | −39.0 (3) |
O2—C6—C5—C4 | −178.3 (2) | C12—C10—C9—O1 | 144.6 (2) |
C7—C6—C5—C4 | 2.8 (3) | C12—C10—C11—C12i | −0.5 (4) |
O2—C6—C7—C2 | 179.8 (2) | C9—C10—C11—C12i | −176.9 (2) |
C5—C6—C7—C2 | −1.3 (3) | C3—C2—C1—O3 | 2.0 (4) |
O1—C5—C4—C3 | 178.3 (2) | C7—C2—C1—O3 | −178.5 (3) |
C6—C5—C4—C3 | −2.3 (4) | C11—C10—C12—C11i | 0.5 (4) |
C6—C7—C2—C3 | −0.6 (4) | C9—C10—C12—C11i | 177.0 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O3ii | 0.93 | 2.47 | 3.338 (1) | 156 |
C12—H12···O2iii | 0.93 | 2.52 | 3.399 (1) | 157 |
Symmetry codes: (ii) −x, y+1/2, −z+3/2; (iii) x, −y+3/2, z−1/2. |
Acknowledgements
The authors thank TBI X–ray facility, CAS in Crystallography and Biophysics, University of Madras, India for the data collection.
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