research communications
and Hirshfeld surface analysis of 3-({4-[(4-cyanophenoxy)carbonyl]phenoxy}carbonyl)phenyl 4-(benzyloxy)-3-chlorobenzoate
aDepartment of Physics, ACS College of Engineering, Bangalore, Karnataka-560074, India, bDepartment of Physics, Government First Grade College, Magadi, Karnataka-562120, India, cRaman Research Institute, C. V. Raman Avenue, Sadashivanagar, Bangalore, Karnataka, India, and dDepartment of PG Studies and Research in Physics, Albert Einstein Block, UCS, Tumkur University, Tumkur, Karnataka-572103, India
*Correspondence e-mail: anilphy1234@gmail.com
The title compound, C35H22ClNO7, is a non-liquid crystal with a bent-shaped molecule. The dihedral angles between adjacent aromatic rings in the molecule (starting from the cyanobenzene ring) are 72.61 (2), 87.69 (4), 64.08 (2) and 88.23 (2)°, indicating that adjacent rings are close to perpendicular to each other. In the crystal, the molecules are linked by weak C—H⋯N and C—H⋯π interactions, thereby forming a two-dimensional supramolecular architecture in the ac plane. The most important contributions to the crystal packing arise from H⋯H (59.3%), S⋯H (27.4%) and O⋯H (7.5%) interactions, as determined by a Hirshfeld surface analysis.
Keywords: crystal structure; Hirshfeld surface; energy framework.
CCDC reference: 2023150
1. Chemical context
Banana/bent-shaped liquid crystals (LCs) are of great interest in the field of display materials. In particular, the –CN groups at the terminal end (Walba et al., 2000; Reddy & Sadashiva, 2004) of banana-shaped LCs have been linked to their bent or bow (twisted) anisometric phase with C2v symmetry. Furthermore, they exhibit polar order, and spontaneous polarization in the fluid phase. We have reported the crystal structures of LC intermediates and found that benzyloxy group-substituted molecules are prone to be hydrophobic (Kashi et al., 2012; Al-Eryani et al., 2011). Benzyloxy group-substituted molecules also play a significant role in synthesizing bent-shaped LCs and non-LCs (Palakshamurthy et al., 2012). Hence, it is useful to study benzyloxy group-substituted bent-shaped molecules to understand the structural properties and the relationship between LCs and crystal structures.
In a continuation of this work, we investigated the title molecule, which possesses five aromatic rings with three ester groups and a benzyloxy group at one terminal end, presumably making the molecule highly polar. Furthermore, it has a chloro group at one side and a cyano group at the opposite terminal end of the molecule, inducing an unsymmetrical structure (Hartung et al., 2000). The molecule was subjected to LC characterization studies, but it did not show any LC properties, which may be due to the absence of a flexible alkyl chain. The title compound was synthesized according to the procedure described by Sadashiva et al. (2002) and its is reported herein.
2. Structural commentary
The molecular structure of the title compound is shown in Fig. 1. The dihedral angles between the aromatic rings are as follows: A/B = 64.08 (2), A/C= 29.75 (2), A/D = 87.69 (4), A/E = 16.07 (3), B/C = 88.23 (2), B/D = 87.88 (4), B/E = 68.87 (4), C/D = 82.27 (3), E/D = 72.61 (2) and C/E = 37.46 (4)°, where A, B, C, D and E are the C1–C6, C23–C28, C30–C35, C8–C13 and C15–C20, rings, respectively. The torsion angles associated with the benzyloxy group are −7.2 (3) (C15—O4—C14—O3), −3.1 (3) (C8—O2—C7—O1) and −0.7 (2)° (C3—O6—C22—O5). Three short intramolecular C—H⋯O contacts (Table 1) may influence the molecular conformation.
3. Supramolecular features
In the crystal, the molecules are linked by weak C—H⋯N hydrogen bonds and weak C—H⋯π interactions (Table 1) to generate a two-dimensional supramolecular architecture propagating in the ac plane as shown in Fig. 2. Furthermore, the molecules are linked by centrosymmetric aromatic π–π stacking interactions with Cg4⋯Cg4 and Cg3⋯Cg3 = 3.6387 (10) Å (slippage = 1.086 Å) and 3.7740 (10) (slippage = 1.407 Å), respectively, as shown in Fig. 3 (Cg4 is the centroid of the C23–C28 ring and Cg3 is the centroid of the C15–C20 ring).
4. Database survey
A search of the Cambridge Structural Database (CSD, version 5.42, update of November 2020; Groom et al., 2016) for molecules containing the (4-cyanophenoxy)carbonyl fragment resulted in four matches with CSD refcodes EWUSIA (Srinivasa et al., 2015), IBUXOV (Ji et al., 2017), IBUXUB (Yingchun et al., 2016) and OCUTIS (Yingchun et al., 2016). In all these structures there is a 4-cyanophenoxy grouping at the one end of the molecule, similar to the title compound. In IBUXOV, IBUXUB and OCUTIS the same core exists at both ends of the molecule. Sometimes the presence of a –CN group at both terminals of the molecule induces liquid-crystal properties.
In EWUSIA, the dihedral angles between the cyanobenzoate ring and the first neighbouring benzene ring, and between the second neighbour and the first and second benzene rings are 50.47 (2), 10.15 (3) and 50.02 (5)° compared to 72.61 (2), 16.06 (2) and 87.69 (4)° in the title molecule. In IBUXOV, the dihedral angles between the rings (cyanobenzoate ring and the neighbouring benzene ring) are 69.45 (2) and 64.20 (3)°, and 73.60 (3) and 84.16 (3)° between the adjacent cyanobenzoate and benzene rings themselves. In IBUXUB, the dihedral angles between the rings (cyanobenzoate and the neighbouring benzene ring) are 69.68 (2) and 74.28 (4)°, and 48.87 (2) and 89.88 (4)° between the cyanobenzoate and benzene rings. In OCUTIS, the dihedral angles between adjacent cyanobenzoate and benzene rings are 81.21 (4) and 54.43 (2)° compared to angles between the cyanobenzoate and benzene rings of 55.02 (3) and 84.20 (3)°.
5. Hirshfeld surface analysis
CrystalExplorer17.5 (Turner et al., 2017) was used to perform the Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) to further quantify the various intermolecular interactions. The Hirshfeld surface mapped over dnorm is illustrated in Fig. 4 and the associated two-dimensional fingerprint plots in Fig. 5. The major contributions to the are from H⋯H (26.9%), C⋯H (27.2%) and O⋯H (19.6%) contacts. In Figs. 6 and 7, the red spots on the dnorm and de surfaces represent the C—H⋯π interactions.
6. Synthesis and crystallization
4-[(4-Cyanophenoxy)carbonyl]phenyl 3-hydroxybenzoate (1 mmol) and 4-(benzyloxy)-3-chlorobenzoic acid (1.2 mmol) were dissolved in dry chloroform (50 ml). After the addition of N,N-dicyclohexylcarbodiimide (1.2 mmol) and a catalytic amount of 4-(N,N-dimethylamino)pyridine (DMAP), the mixture was stirred at room temperature for about 12 h. The dicyclohexylurea that precipitated was filtered off and the filtrate diluted with chloroform. This solution was washed with 2% aqueous acetic acid solution (10 ml) and 5% ice-cold sodium hydroxide solution (10 ml) and finally washed with water and dried over anhydrous sodium sulfate. The crude residue obtained was chromatographed on silica gel using chloroform as an Removal of solvent from the afforded the white target material, which was crystallized from a mixture of chloroform and acetonitrile. Single crystals in the form of colourless prisms suitable for diffraction studies were grown from a solution in ethyl alcohol by slow evaporation.
IR (nujol) λmax: 3105, 3080, 2237, 1738, 1733, 1614, 1523, 1452, 1253, 1054 cm−1; 1H NMR (500 MHz, CDCl3) δ H: 8.22 (m, 3H, Ar—H) , 8.19 (m, 3H, Ar-H), 8.02 (m, 2H, Ar—H), 7.98–7.30 (m, 7H, Ar—H), 6.99 (m, 5H, Ar—H), 5.22 (s, 2H, Ar—O—CH2–) ppm; 13C NMR (125 MHz, CDCl3) δ: 165.2, 159.8, 154.6, 153.7, 151.2, 136.7, 132.6, 130.2, 129, 128.9, 128.6, 127.6, 127.1, 126.8, 123.9, 122.3, 121.3, 112.4 ppm. Micro elemental analysis calculated for C35H22ClNO7; C, 69.60; H, 3.67; Cl, 5.87; N, 2.32; found C, 69.68; H, 3.72; Cl, 5.91; N, 2.35%.
7. Refinement
Crystal data, data collection and structure . Atoms H2, H4 and H6 were fully refined. Other H atoms were positioned with idealized geometry and refined using a riding model with C—H = 0.93–0.97 Å and Uiso(H) = 1.2–1.5Ueq(C).
details are summarized in Table 2
|
Supporting information
CCDC reference: 2023150
https://doi.org/10.1107/S2056989022008441/hb8019sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022008441/hb8019Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989022008441/hb8019Isup3.cml
Data collection: APEX2 (Bruker, 2017),; cell
SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL (Sheldrick, 2015b).C35H22ClNO7 | F(000) = 624 |
Mr = 603.98 | Prism |
Triclinic, P1 | Dx = 1.357 Mg m−3 |
Hall symbol: -P 1 | Melting point: 445 K |
a = 8.0202 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.8474 (2) Å | Cell parameters from 5212 reflections |
c = 19.4712 (4) Å | θ = 1.0–25.0° |
α = 95.422 (1)° | µ = 0.18 mm−1 |
β = 94.693 (1)° | T = 296 K |
γ = 103.857 (1)° | Prism, colourless |
V = 1477.66 (5) Å3 | 0.19 × 0.18 × 0.16 mm |
Z = 2 |
Bruker SMART APEXII CCD diffractometer | 5207 independent reflections |
Radiation source: fine-focus sealed tube | 4255 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 2.06 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2017) | k = −11→11 |
Tmin = 0.966, Tmax = 0.971 | l = −23→23 |
25466 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0619P)2 + 0.2788P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
5207 reflections | Δρmax = 0.26 e Å−3 |
410 parameters | Δρmin = −0.32 e Å−3 |
6 restraints | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0158 (18) |
Primary atom site location: structure-invariant direct methods |
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 | ||
O7 | 0.66155 (14) | 1.37557 (12) | 1.06583 (6) | 0.0604 (3) | |
O6 | 0.23387 (14) | 0.91624 (11) | 0.82866 (6) | 0.0562 (3) | |
O2 | 0.31260 (15) | 0.47851 (13) | 0.70608 (7) | 0.0701 (4) | |
O4 | 0.70509 (18) | 0.04285 (14) | 0.58733 (6) | 0.0691 (4) | |
O5 | 0.07952 (16) | 0.85138 (14) | 0.91636 (6) | 0.0683 (4) | |
O3 | 0.6173 (2) | −0.06006 (17) | 0.67969 (8) | 0.0920 (5) | |
O1 | 0.06206 (16) | 0.37006 (13) | 0.64386 (7) | 0.0734 (4) | |
N1 | 1.2423 (3) | −0.3715 (2) | 0.52599 (11) | 0.0906 (6) | |
C33 | 1.1312 (3) | 1.7706 (3) | 1.18897 (11) | 0.0805 (6) | |
H33 | 1.200300 | 1.842548 | 1.220743 | 0.097* | |
C34 | 1.1522 (3) | 1.6373 (3) | 1.18768 (11) | 0.0812 (6) | |
H34 | 1.235250 | 1.618164 | 1.218912 | 0.097* | |
C35 | 1.0499 (3) | 1.5295 (2) | 1.13982 (10) | 0.0710 (5) | |
H35 | 1.066616 | 1.439064 | 1.138300 | 0.085* | |
C30 | 0.9239 (2) | 1.55720 (18) | 1.09471 (8) | 0.0561 (4) | |
C29 | 0.8184 (2) | 1.44647 (19) | 1.03988 (9) | 0.0652 (5) | |
H29A | 0.790624 | 1.489441 | 0.999036 | 0.078* | |
H29B | 0.883975 | 1.378979 | 1.026758 | 0.078* | |
C26 | 0.5546 (2) | 1.27075 (17) | 1.02142 (8) | 0.0496 (4) | |
C25 | 0.5822 (2) | 1.23457 (18) | 0.95365 (9) | 0.0599 (4) | |
H25 | 0.678848 | 1.285319 | 0.935657 | 0.072* | |
C24 | 0.4681 (2) | 1.12408 (17) | 0.91246 (8) | 0.0550 (4) | |
H24 | 0.488830 | 1.101130 | 0.867042 | 0.066* | |
C23 | 0.32400 (19) | 1.04740 (15) | 0.93774 (8) | 0.0456 (3) | |
C22 | 0.19929 (19) | 0.92835 (16) | 0.89583 (8) | 0.0472 (4) | |
C3 | 0.1246 (2) | 0.80725 (15) | 0.78186 (8) | 0.0476 (4) | |
C2 | 0.1912 (2) | 0.69862 (16) | 0.75737 (8) | 0.0479 (4) | |
C1 | 0.08826 (19) | 0.59329 (16) | 0.70854 (7) | 0.0449 (3) | |
C7 | 0.1464 (2) | 0.46904 (17) | 0.68174 (8) | 0.0517 (4) | |
C8 | 0.3800 (2) | 0.36353 (18) | 0.68774 (9) | 0.0577 (4) | |
C13 | 0.4822 (2) | 0.37070 (19) | 0.63451 (10) | 0.0608 (4) | |
H13 | 0.499046 | 0.447392 | 0.609152 | 0.073* | |
C12 | 0.5600 (2) | 0.26220 (18) | 0.61907 (9) | 0.0572 (4) | |
H12 | 0.630774 | 0.266133 | 0.583388 | 0.069* | |
C11 | 0.53291 (19) | 0.14754 (17) | 0.65663 (8) | 0.0494 (4) | |
C14 | 0.6184 (2) | 0.03171 (19) | 0.64397 (9) | 0.0551 (4) | |
C15 | 0.8124 (2) | −0.04890 (18) | 0.57562 (9) | 0.0566 (4) | |
C20 | 0.9844 (2) | 0.00167 (19) | 0.59635 (10) | 0.0654 (5) | |
H20 | 1.027213 | 0.091840 | 0.619681 | 0.078* | |
C19 | 1.0936 (2) | −0.08343 (19) | 0.58204 (10) | 0.0657 (5) | |
H19 | 1.211388 | −0.050869 | 0.595875 | 0.079* | |
C18 | 1.0288 (2) | −0.21700 (18) | 0.54721 (9) | 0.0564 (4) | |
C21 | 1.1458 (3) | −0.3048 (2) | 0.53442 (10) | 0.0671 (5) | |
C27 | 0.40785 (19) | 1.19401 (19) | 1.04630 (8) | 0.0526 (4) | |
C28 | 0.29494 (19) | 1.08363 (18) | 1.00565 (8) | 0.0530 (4) | |
H28 | 0.198360 | 1.032683 | 1.023589 | 0.064* | |
C9 | 0.3515 (2) | 0.2511 (2) | 0.72563 (10) | 0.0674 (5) | |
H9 | 0.281420 | 0.248249 | 0.761511 | 0.081* | |
C10 | 0.4279 (2) | 0.1426 (2) | 0.70986 (9) | 0.0615 (4) | |
H10 | 0.408968 | 0.065641 | 0.735040 | 0.074* | |
C17 | 0.8540 (2) | −0.26542 (19) | 0.52624 (9) | 0.0621 (5) | |
H17 | 0.810392 | −0.354934 | 0.502276 | 0.074* | |
C16 | 0.7448 (2) | −0.18100 (19) | 0.54090 (9) | 0.0632 (5) | |
H16 | 0.626763 | −0.212940 | 0.527475 | 0.076* | |
C6 | −0.0776 (2) | 0.59977 (17) | 0.68582 (8) | 0.0501 (4) | |
C5 | −0.1410 (2) | 0.71063 (18) | 0.71118 (9) | 0.0558 (4) | |
H5 | −0.252302 | 0.714786 | 0.695759 | 0.067* | |
C4 | −0.0391 (2) | 0.81545 (17) | 0.75948 (9) | 0.0538 (4) | |
C31 | 0.9056 (3) | 1.6916 (2) | 1.09726 (13) | 0.0897 (7) | |
H31 | 0.821394 | 1.711933 | 1.066993 | 0.108* | |
C32 | 1.0097 (3) | 1.7978 (3) | 1.14393 (15) | 0.1065 (9) | |
H32 | 0.996215 | 1.889094 | 1.144422 | 0.128* | |
Cl | 0.37075 (6) | 1.23731 (8) | 1.13083 (2) | 0.0967 (2) | |
H6 | −0.146 (2) | 0.5267 (19) | 0.6546 (9) | 0.057 (5)* | |
H2 | 0.303 (2) | 0.6937 (18) | 0.7740 (9) | 0.061 (5)* | |
H4 | −0.080 (2) | 0.8914 (19) | 0.7778 (9) | 0.057 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O7 | 0.0531 (6) | 0.0670 (7) | 0.0505 (6) | 0.0008 (5) | 0.0086 (5) | −0.0123 (5) |
O6 | 0.0596 (7) | 0.0465 (6) | 0.0544 (6) | 0.0017 (5) | 0.0134 (5) | −0.0115 (5) |
O2 | 0.0542 (7) | 0.0636 (8) | 0.0892 (9) | 0.0284 (6) | −0.0096 (6) | −0.0289 (6) |
O4 | 0.0899 (9) | 0.0714 (8) | 0.0624 (7) | 0.0493 (7) | 0.0188 (6) | 0.0061 (6) |
O5 | 0.0600 (7) | 0.0755 (8) | 0.0566 (7) | −0.0063 (6) | 0.0056 (6) | 0.0044 (6) |
O3 | 0.1290 (13) | 0.0867 (10) | 0.0914 (10) | 0.0694 (10) | 0.0423 (9) | 0.0305 (9) |
O1 | 0.0672 (8) | 0.0598 (8) | 0.0861 (9) | 0.0257 (6) | −0.0185 (7) | −0.0296 (7) |
N1 | 0.0917 (13) | 0.0785 (12) | 0.1191 (16) | 0.0446 (10) | 0.0413 (11) | 0.0130 (11) |
C33 | 0.0729 (13) | 0.0866 (16) | 0.0667 (12) | 0.0043 (11) | −0.0038 (10) | −0.0185 (11) |
C34 | 0.0696 (12) | 0.0989 (17) | 0.0638 (12) | −0.0017 (11) | −0.0122 (9) | 0.0277 (11) |
C35 | 0.0744 (12) | 0.0626 (11) | 0.0720 (12) | 0.0052 (9) | 0.0026 (10) | 0.0236 (9) |
C30 | 0.0519 (9) | 0.0587 (10) | 0.0518 (9) | 0.0056 (7) | 0.0090 (7) | −0.0046 (7) |
C29 | 0.0636 (10) | 0.0634 (11) | 0.0573 (10) | −0.0031 (8) | 0.0135 (8) | −0.0061 (8) |
C26 | 0.0488 (8) | 0.0514 (9) | 0.0461 (8) | 0.0120 (7) | 0.0033 (6) | −0.0037 (7) |
C25 | 0.0622 (10) | 0.0569 (10) | 0.0510 (9) | −0.0031 (8) | 0.0164 (8) | −0.0036 (7) |
C24 | 0.0620 (10) | 0.0524 (9) | 0.0458 (8) | 0.0062 (7) | 0.0139 (7) | −0.0049 (7) |
C23 | 0.0461 (8) | 0.0443 (8) | 0.0471 (8) | 0.0146 (6) | 0.0034 (6) | 0.0019 (6) |
C22 | 0.0464 (8) | 0.0473 (8) | 0.0490 (8) | 0.0142 (7) | 0.0053 (7) | 0.0046 (7) |
C3 | 0.0507 (8) | 0.0411 (8) | 0.0476 (8) | 0.0066 (6) | 0.0103 (7) | −0.0032 (6) |
C2 | 0.0439 (8) | 0.0497 (9) | 0.0487 (8) | 0.0123 (7) | 0.0051 (7) | −0.0034 (7) |
C1 | 0.0470 (8) | 0.0447 (8) | 0.0433 (8) | 0.0145 (6) | 0.0046 (6) | −0.0011 (6) |
C7 | 0.0513 (9) | 0.0517 (9) | 0.0515 (9) | 0.0187 (7) | −0.0001 (7) | −0.0068 (7) |
C8 | 0.0485 (9) | 0.0568 (10) | 0.0656 (10) | 0.0224 (7) | −0.0064 (8) | −0.0173 (8) |
C13 | 0.0616 (10) | 0.0555 (10) | 0.0678 (11) | 0.0238 (8) | 0.0021 (8) | 0.0005 (8) |
C12 | 0.0581 (10) | 0.0600 (10) | 0.0575 (9) | 0.0249 (8) | 0.0076 (8) | −0.0016 (8) |
C11 | 0.0477 (8) | 0.0524 (9) | 0.0474 (8) | 0.0189 (7) | −0.0041 (6) | −0.0060 (7) |
C14 | 0.0588 (10) | 0.0564 (10) | 0.0518 (9) | 0.0239 (8) | −0.0010 (7) | −0.0045 (8) |
C15 | 0.0700 (11) | 0.0565 (10) | 0.0516 (9) | 0.0327 (8) | 0.0109 (8) | 0.0006 (7) |
C20 | 0.0719 (12) | 0.0497 (10) | 0.0717 (11) | 0.0170 (8) | 0.0076 (9) | −0.0112 (8) |
C19 | 0.0564 (10) | 0.0588 (11) | 0.0800 (12) | 0.0158 (8) | 0.0080 (9) | −0.0055 (9) |
C18 | 0.0646 (10) | 0.0527 (10) | 0.0578 (9) | 0.0240 (8) | 0.0177 (8) | 0.0026 (8) |
C21 | 0.0734 (12) | 0.0601 (11) | 0.0766 (12) | 0.0275 (9) | 0.0263 (10) | 0.0079 (9) |
C27 | 0.0433 (8) | 0.0724 (11) | 0.0414 (8) | 0.0163 (7) | 0.0051 (6) | −0.0021 (7) |
C28 | 0.0406 (8) | 0.0688 (10) | 0.0467 (8) | 0.0082 (7) | 0.0061 (6) | 0.0052 (7) |
C9 | 0.0664 (11) | 0.0776 (13) | 0.0630 (11) | 0.0300 (9) | 0.0144 (9) | −0.0054 (10) |
C10 | 0.0645 (10) | 0.0645 (11) | 0.0591 (10) | 0.0247 (8) | 0.0076 (8) | 0.0028 (8) |
C17 | 0.0723 (11) | 0.0507 (10) | 0.0618 (10) | 0.0198 (8) | 0.0057 (8) | −0.0105 (8) |
C16 | 0.0602 (10) | 0.0657 (11) | 0.0629 (10) | 0.0224 (8) | −0.0004 (8) | −0.0083 (9) |
C6 | 0.0513 (9) | 0.0478 (9) | 0.0492 (8) | 0.0137 (7) | −0.0005 (7) | −0.0029 (7) |
C5 | 0.0518 (9) | 0.0562 (10) | 0.0623 (10) | 0.0225 (7) | 0.0017 (7) | 0.0016 (8) |
C4 | 0.0614 (10) | 0.0446 (9) | 0.0594 (10) | 0.0215 (7) | 0.0121 (8) | −0.0013 (7) |
C31 | 0.0782 (14) | 0.0788 (14) | 0.1071 (17) | 0.0395 (11) | −0.0310 (12) | −0.0313 (12) |
C32 | 0.0958 (17) | 0.0809 (15) | 0.133 (2) | 0.0416 (13) | −0.0338 (16) | −0.0495 (15) |
Cl | 0.0578 (3) | 0.1601 (6) | 0.0491 (3) | −0.0054 (3) | 0.0139 (2) | −0.0263 (3) |
O7—C26 | 1.3545 (19) | C1—C6 | 1.385 (2) |
O7—C29 | 1.441 (2) | C1—C7 | 1.476 (2) |
O6—C22 | 1.3591 (19) | C8—C13 | 1.370 (3) |
O6—C3 | 1.4086 (17) | C8—C9 | 1.372 (3) |
O2—C7 | 1.3563 (19) | C13—C12 | 1.382 (2) |
O2—C8 | 1.396 (2) | C13—H13 | 0.9300 |
O4—C14 | 1.350 (2) | C12—C11 | 1.386 (2) |
O4—C15 | 1.4052 (19) | C12—H12 | 0.9300 |
O5—C22 | 1.1953 (19) | C11—C10 | 1.385 (2) |
O3—C14 | 1.190 (2) | C11—C14 | 1.477 (2) |
O1—C7 | 1.1909 (19) | C15—C20 | 1.363 (3) |
N1—C21 | 1.141 (2) | C15—C16 | 1.371 (2) |
C33—C32 | 1.349 (3) | C20—C19 | 1.376 (3) |
C33—C34 | 1.360 (3) | C20—H20 | 0.9300 |
C33—H33 | 0.9300 | C19—C18 | 1.381 (2) |
C34—C35 | 1.393 (3) | C19—H19 | 0.9300 |
C34—H34 | 0.9300 | C18—C17 | 1.382 (3) |
C35—C30 | 1.378 (3) | C18—C21 | 1.441 (2) |
C35—H35 | 0.9300 | C27—C28 | 1.370 (2) |
C30—C31 | 1.363 (3) | C27—Cl | 1.7284 (15) |
C30—C29 | 1.495 (2) | C28—H28 | 0.9300 |
C29—H29A | 0.9700 | C9—C10 | 1.376 (3) |
C29—H29B | 0.9700 | C9—H9 | 0.9300 |
C26—C25 | 1.384 (2) | C10—H10 | 0.9300 |
C26—C27 | 1.388 (2) | C17—C16 | 1.372 (2) |
C25—C24 | 1.379 (2) | C17—H17 | 0.9300 |
C25—H25 | 0.9300 | C16—H16 | 0.9300 |
C24—C23 | 1.376 (2) | C6—C5 | 1.378 (2) |
C24—H24 | 0.9300 | C6—H6 | 0.929 (18) |
C23—C28 | 1.390 (2) | C5—C4 | 1.380 (2) |
C23—C22 | 1.471 (2) | C5—H5 | 0.9300 |
C3—C2 | 1.369 (2) | C4—H4 | 0.940 (18) |
C3—C4 | 1.373 (2) | C31—C32 | 1.376 (3) |
C2—C1 | 1.392 (2) | C31—H31 | 0.9300 |
C2—H2 | 0.944 (18) | C32—H32 | 0.9300 |
C26—O7—C29 | 115.72 (12) | C8—C13—H13 | 120.5 |
C22—O6—C3 | 118.29 (12) | C12—C13—H13 | 120.5 |
C7—O2—C8 | 117.25 (12) | C13—C12—C11 | 120.16 (16) |
C14—O4—C15 | 117.53 (13) | C13—C12—H12 | 119.9 |
C32—C33—C34 | 119.68 (19) | C11—C12—H12 | 119.9 |
C32—C33—H33 | 120.2 | C10—C11—C12 | 119.62 (15) |
C34—C33—H33 | 120.2 | C10—C11—C14 | 118.11 (16) |
C33—C34—C35 | 120.33 (19) | C12—C11—C14 | 122.22 (15) |
C33—C34—H34 | 119.8 | O3—C14—O4 | 122.49 (15) |
C35—C34—H34 | 119.8 | O3—C14—O4 | 122.49 (15) |
C30—C35—C34 | 119.8 (2) | O3—C14—C11 | 125.25 (16) |
C30—C35—H35 | 120.1 | O4—C14—C11 | 112.23 (15) |
C34—C35—H35 | 120.1 | O4—C14—C11 | 112.23 (15) |
C31—C30—C35 | 118.56 (17) | C20—C15—C16 | 122.31 (16) |
C31—C30—C29 | 119.80 (18) | C20—C15—O4 | 117.50 (16) |
C35—C30—C29 | 121.44 (18) | C16—C15—O4 | 120.08 (16) |
O7—C29—C30 | 109.61 (13) | C20—C15—O4 | 117.50 (16) |
O7—C29—H29A | 109.7 | C16—C15—O4 | 120.08 (16) |
C30—C29—H29A | 109.7 | C15—C20—C19 | 118.63 (16) |
O7—C29—H29B | 109.7 | C15—C20—H20 | 120.7 |
C30—C29—H29B | 109.7 | C19—C20—H20 | 120.7 |
H29A—C29—H29B | 108.2 | C20—C19—C18 | 120.22 (17) |
O7—C26—C25 | 124.66 (14) | C20—C19—H19 | 119.9 |
O7—C26—C27 | 117.23 (13) | C18—C19—H19 | 119.9 |
C25—C26—C27 | 118.10 (14) | C19—C18—C17 | 120.04 (16) |
C24—C25—C26 | 120.76 (15) | C19—C18—C21 | 118.90 (17) |
C24—C25—H25 | 119.6 | C17—C18—C21 | 121.06 (16) |
C26—C25—H25 | 119.6 | N1—C21—C18 | 177.7 (2) |
C23—C24—C25 | 120.81 (14) | C28—C27—C26 | 121.24 (14) |
C23—C24—H24 | 119.6 | C28—C27—Cl | 119.84 (12) |
C25—C24—H24 | 119.6 | C26—C27—Cl | 118.91 (12) |
C24—C23—C28 | 118.75 (14) | C27—C28—C23 | 120.32 (14) |
C24—C23—C22 | 122.69 (14) | C27—C28—H28 | 119.8 |
C28—C23—C22 | 118.56 (14) | C23—C28—H28 | 119.8 |
O5—C22—O6 | 122.68 (14) | C8—C9—C10 | 119.15 (17) |
O5—C22—O6 | 122.68 (14) | C8—C9—H9 | 120.4 |
O5—C22—C23 | 125.70 (14) | C10—C9—H9 | 120.4 |
O6—C22—C23 | 111.61 (13) | C9—C10—C11 | 120.26 (18) |
O6—C22—C23 | 111.61 (13) | C9—C10—H10 | 119.9 |
C2—C3—C4 | 122.09 (14) | C11—C10—H10 | 119.9 |
C2—C3—O6 | 117.58 (14) | C16—C17—C18 | 119.79 (16) |
C4—C3—O6 | 120.24 (14) | C16—C17—H17 | 120.1 |
C2—C3—O6 | 117.58 (14) | C18—C17—H17 | 120.1 |
C4—C3—O6 | 120.24 (14) | C15—C16—C17 | 119.01 (17) |
C3—C2—C1 | 118.53 (15) | C15—C16—H16 | 120.5 |
C3—C2—H2 | 120.9 (11) | C17—C16—H16 | 120.5 |
C1—C2—H2 | 120.5 (11) | C5—C6—C1 | 120.23 (15) |
C6—C1—C2 | 119.99 (14) | C5—C6—H6 | 120.9 (11) |
C6—C1—C7 | 117.75 (14) | C1—C6—H6 | 118.8 (11) |
C2—C1—C7 | 122.20 (14) | C6—C5—C4 | 119.93 (15) |
O1—C7—O2 | 122.12 (14) | C6—C5—H5 | 120.0 |
O1—C7—O2 | 122.12 (14) | C4—C5—H5 | 120.0 |
O1—C7—C1 | 126.23 (15) | C3—C4—C5 | 119.21 (15) |
O2—C7—C1 | 111.65 (13) | C3—C4—H4 | 119.5 (11) |
O2—C7—C1 | 111.65 (13) | C5—C4—H4 | 121.3 (11) |
C13—C8—C9 | 121.82 (16) | C30—C31—C32 | 121.0 (2) |
C13—C8—O2 | 118.33 (17) | C30—C31—H31 | 119.5 |
C9—C8—O2 | 119.73 (16) | C32—C31—H31 | 119.5 |
C13—C8—O2 | 118.33 (17) | C33—C32—C31 | 120.6 (2) |
C9—C8—O2 | 119.73 (16) | C33—C32—H32 | 119.7 |
C8—C13—C12 | 118.98 (17) | C31—C32—H32 | 119.7 |
C32—C33—C34—C35 | 0.5 (4) | C15—O4—C14—C11 | 170.88 (14) |
C33—C34—C35—C30 | −1.6 (3) | C10—C11—C14—O3 | −7.1 (3) |
C34—C35—C30—C31 | 1.5 (3) | C12—C11—C14—O3 | 170.25 (19) |
C34—C35—C30—C29 | 176.40 (17) | C10—C11—C14—O4 | 174.84 (15) |
C26—O7—C29—C30 | −179.10 (15) | C12—C11—C14—O4 | −7.8 (2) |
C31—C30—C29—O7 | −92.2 (2) | C10—C11—C14—O4 | 174.84 (15) |
C35—C30—C29—O7 | 93.0 (2) | C12—C11—C14—O4 | −7.8 (2) |
C29—O7—C26—C25 | −3.6 (3) | C14—O4—C15—C20 | −98.2 (2) |
C29—O7—C26—C27 | 175.84 (15) | C14—O4—C15—C16 | 85.5 (2) |
O7—C26—C25—C24 | 178.60 (17) | C16—C15—C20—C19 | −0.3 (3) |
C27—C26—C25—C24 | −0.9 (3) | O4—C15—C20—C19 | −176.45 (16) |
C26—C25—C24—C23 | 0.1 (3) | O4—C15—C20—C19 | −176.45 (16) |
C25—C24—C23—C28 | 0.2 (3) | C15—C20—C19—C18 | 0.2 (3) |
C25—C24—C23—C22 | −179.69 (16) | C20—C19—C18—C17 | 0.4 (3) |
C3—O6—C22—O5 | −0.7 (2) | C20—C19—C18—C21 | −178.57 (18) |
C3—O6—C22—C23 | −179.61 (13) | O7—C26—C27—C28 | −178.18 (15) |
C24—C23—C22—O5 | 173.94 (17) | C25—C26—C27—C28 | 1.3 (3) |
C28—C23—C22—O5 | −6.0 (3) | O7—C26—C27—Cl | 0.5 (2) |
C24—C23—C22—O6 | −7.2 (2) | C25—C26—C27—Cl | 179.98 (14) |
C28—C23—C22—O6 | 172.84 (14) | C26—C27—C28—C23 | −1.0 (3) |
C24—C23—C22—O6 | −7.2 (2) | Cl—C27—C28—C23 | −179.65 (13) |
C28—C23—C22—O6 | 172.84 (14) | C24—C23—C28—C27 | 0.2 (2) |
C22—O6—C3—C2 | −110.45 (16) | C22—C23—C28—C27 | −179.86 (15) |
C22—O6—C3—C4 | 72.9 (2) | C13—C8—C9—C10 | 0.1 (3) |
C4—C3—C2—C1 | −0.3 (2) | O2—C8—C9—C10 | −175.81 (15) |
O6—C3—C2—C1 | −176.95 (13) | O2—C8—C9—C10 | −175.81 (15) |
O6—C3—C2—C1 | −176.95 (13) | C8—C9—C10—C11 | 0.3 (3) |
C3—C2—C1—C6 | −0.1 (2) | C12—C11—C10—C9 | −0.3 (3) |
C3—C2—C1—C7 | −177.12 (15) | C14—C11—C10—C9 | 177.15 (16) |
C8—O2—C7—O1 | −3.1 (3) | C19—C18—C17—C16 | −0.8 (3) |
C8—O2—C7—C1 | 176.36 (15) | C21—C18—C17—C16 | 178.11 (17) |
C6—C1—C7—O1 | −2.8 (3) | C20—C15—C16—C17 | −0.2 (3) |
C2—C1—C7—O1 | 174.35 (17) | O4—C15—C16—C17 | 175.92 (16) |
C6—C1—C7—O2 | 177.76 (14) | O4—C15—C16—C17 | 175.92 (16) |
C2—C1—C7—O2 | −5.1 (2) | C18—C17—C16—C15 | 0.7 (3) |
C6—C1—C7—O2 | 177.76 (14) | C2—C1—C6—C5 | 0.3 (2) |
C2—C1—C7—O2 | −5.1 (2) | C7—C1—C6—C5 | 177.48 (15) |
C7—O2—C8—C13 | 99.95 (19) | C1—C6—C5—C4 | −0.1 (3) |
C7—O2—C8—C9 | −84.0 (2) | C2—C3—C4—C5 | 0.5 (3) |
C9—C8—C13—C12 | −0.6 (3) | O6—C3—C4—C5 | 177.03 (14) |
O2—C8—C13—C12 | 175.35 (14) | O6—C3—C4—C5 | 177.03 (14) |
O2—C8—C13—C12 | 175.35 (14) | C6—C5—C4—C3 | −0.3 (3) |
C8—C13—C12—C11 | 0.7 (2) | C35—C30—C31—C32 | −0.3 (4) |
C13—C12—C11—C10 | −0.2 (2) | C29—C30—C31—C32 | −175.3 (2) |
C13—C12—C11—C14 | −177.55 (15) | C34—C33—C32—C31 | 0.7 (4) |
C15—O4—C14—O3 | −7.2 (3) | C30—C31—C32—C33 | −0.9 (4) |
Cg4 and cg5 are the centroids of the C23–C28 and C30–C35 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2 | 0.944 (18) | 2.411 (17) | 2.7213 (19) | 98.9 (12) |
C12—H12···O4 | 0.93 | 2.42 | 2.733 (2) | 100 |
C24—H24···O6 | 0.93 | 2.40 | 2.721 (2) | 100 |
C17—H17···N1i | 0.93 | 2.62 | 3.504 (3) | 158 |
C25—H25···Cg5ii | 0.93 | 2.86 | 3.744 (2) | 158 |
C31—H31···Cg4iii | 0.93 | 2.82 | 3.702 (3) | 158 |
Symmetry codes: (i) −x+2, −y−1, −z+1; (ii) −x, −y−1, −z; (iii) −x+1, −y−1, −z. |
Funding information
The authors thank the Vision Group on Science and Technology, Government of Karnataka, for the award of a major project under the CISEE scheme (reference No. VGST/CISEE/GRD-319/2014–15) to carry out this work at the Department of PG Studies and Research in Physics, UCS, Tumkur University.
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