research communications
N-(pyridin-2-ylmethyl)benzamide
and Hirshfeld surface analysis of 3-(cyclopropylmethoxy)-4-(difluoromethoxy)-aCAS in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
*Correspondence e-mail: mahes1287@gmail.com
The title compound, C18H18F2N2O3, crystallizes with two independent molecules (A and B) in the They differ essentially in the orientation of the pyridine ring with respect to the benzene ring; these two rings are inclined to each other by 53.3 (2)° in molecule A and by 72.9 (2)° in molecule B. The 3-(cyclopropylmethoxy) side chain has an extended conformation in both molecules. The two molecules are linked by a pair of C—H⋯O hydrogen bonds and two C—H⋯π interactions, forming an A–B unit. In the crystal, this unit is linked by N—H⋯O hydrogen bonds, forming a zigzag –A–B–A–B– chain along [001]. The chains are linked by C—H⋯N and C—H⋯F hydrogen bonds to form layers parallel to the ac plane. Finally, the layers are linked by a third C—H⋯π interaction, forming a three-dimensional structure. The major contributions to the Hirshfeld surface are those due to H⋯H contacts (39.7%), followed by F⋯H/H⋯F contacts (19.2%).
Keywords: crystal structure; benzamide; pyridine; cyclopropane; supramolecular features; hydrogen bonding; C—H⋯π interactions; Hirshfeld surface analysis.
CCDC reference: 1954107
1. Chemical context
et al., 2007; Jeschke, 2004; Leroux et al., 2005). show a broad spectrum of pharmacological properties, including antibacterial (Manojkumar et al. 2013a), anti-inflammatory, antioxidant, analgesic and antiviral activity (Manojkumar et al., 2013b). They also act as fungicides (Liu et al., 2004a), agaricides (Shiga et al., 2003) and insecticides (Liu et al., 2004b). Following our interest in such compounds, we report herein on the synthesis, and Hirshfeld surface analysis of the title compound, 3-(cyclopropylmethoxy)-4-(difluoromethoxy)-N-(pyridin-2-ylmethyl)benzamide.
containing trifluoromethyl substituents are important in both agrochemical research and pharmaceutical chemistry (Jeschke2. Structural commentary
The A and B; Fig. 1). The overall conformation of the A and B molecules differs in the orientation of the pyridine ring with respect to the benzene ring, as shown in the molecular overlap figure [Fig. 2; inverted molecule B (black) on molecule A (red), with an r.m.s. deviation of 0.641 Å]. The dihedral angle between the benzamide ring and the pyridine ring is 53.3 (2)° in molecule A and 72.9 (2)° in molecule B. The cyclopropane ring makes a dihedral angle of 57.7 (5)° with the benzene ring in molecule A and 58.7 (4)° in molecule B. The sum of the bond angles around atom N1 (359.9°) is in accordance with sp2 in both molecules. The bond lengths and bond angles in both molecules are comparable with those reported for a similar compound, 3-(cyclopropylmethoxy)-N-(3,5-dichloropyridin-4-yl)-4-(difluoromethoxy) benzamide (Viertelhaus et al., 2013), that crystallizes with three independent molecules in the asymmetric unit.
of the title compound contains two crystallographically independent molecules (3. Supramolecular features
In the crystal, the A and B molecules are linked by C—H⋯O and C—H⋯π interactions (Table 1 and Fig. 1), forming A-B units, which are in turn linked by N—H⋯O hydrogen bonds, forming chains propagating along the c-axis direction (Table 1 and Fig. 3). The chains are linked by C—H⋯O, C—H⋯N and C—H⋯F hydrogen bonds, forming layers lying parallel to the ac plane (Table 1 and Fig. 4). A third C—H⋯π interaction links the layers to form a supramolecular three-dimensional structure (Fig. 5).
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 4.0, last update May 2019; Groom et al., 2016) for the (cyclopropylmethoxy)benzene skeleton gave twelve hits for nine structures. Only three molecules resemble the title compound. The most similar is 3-(cyclopropylmethoxy)-N-(3,5-dichloropyridin-4-yl)-4-(difluoromethoxy) benzamide (CSD refcode PEDWOM; Viertelhaus et al., 2013). It is known as Roflumilast (trade names Daxas, Daliresp), a drug that has anti-inflammatory properties and is used in the treatment of chronic obstructive pulmonary disease (Hohlfeld et al., 2008). The authors (Viertelhaus et al., 2013) have made a variable temperature study of this compound (CSD entries PEDWOM at 100 K, PEDWOM01 at 343 K, PEDWOM02/PEDWOM03 at 298 K) in relation to a reversible single-crystal to single-crystal at 323 K. The compound crystallizes in the monoclinic P21/n with three independent molecules in the The high temperature phase at 343 K also crystallizes in P21/n but with only one molecule in the the length of the b axis being reduced by around a third. Here, the compound has a disordered difluoromethoxy group. The overall conformations of the molecules in all four entries (PEDWOM at 100 K, PEDWOM01 at 343 K, PEDWOM02/PEDWOM03 at 298 K) are very similar. Considering the low-temperature phase PEDWOM only, in each molecule the benzene and pyridine rings are positioned almost perpendicular to each other, with dihedral angles of 88.38 (14), 89.34 (14) and 84.72 (14)°, compared to 53.3 (2) and 72.9 (2)° for molecules A and B, respectively, in the title compound. In PEDWOM the cyclopropane ring makes dihedral angles of 55.43 (3), 49.6 (3) and 50.9 (3)° with the corresponding benzene ring. These dihedral angles are very similar to those observed in the title structure [57.7 (5)° in molecule A and 58.7 (4)° in molecule B]. In the second compound, methyl 3-(cyclopropylmethoxy)-4-hydroxybenzoate (DUSXOF; Hou et al., 2010), the cyclopropane ring is inclined to the benzene ring by 63.34 (10)°, while in the third compound, methyl 3,4-bis(cyclopropylmethoxy)benzoate (URAWEQ; Cheng et al., 2011), this dihedral angle is smaller at 45.49 (11)°.
5. Hirshfeld surface analysis
The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007) were performed with CrystalExplorer17 (Turner et al., 2017). The Hirshfeld surface mapped over dnorm in the colour range of −0.4869 to 1.4157 arbitrary units, and the intermolecular contacts are illustrated in Fig. 6. The red spots on the surface indicate the intermolecular contacts involved in hydrogen bonding (Table 1). The two-dimensional fingerprint plots are given in Fig. 7. They reveal that the principal intermolecular contacts are H⋯H at 39.7% (Fig. 7b), followed by F⋯H/ H⋯F at 19.2% (Fig. 7c), C⋯H/H⋯C at 16.6% (Fig. 7d), O⋯H/ H⋯O at 14.0% (Fig. 7e), N⋯H/H⋯N at 6.8% (Fig. 7f). Hence, the H⋯H and F⋯H/H⋯F intermolecular contacts are the most abundant in the crystal packing, and make the most significant contributions to the total Hirshfeld surfaces.
6. Synthesis and crystallization
A mixture of 4-(difluoromethyl)-3-hydroxybenzoic acid (2 mmol), (chloromethyl)cyclopropane (2 mmol) and 2-picolylamine (3 mmol) with PPh3 (0.2 mmol) in methanol were heated first to 393 K for 2 h in the presence of the inexpensive ionic liquid tetrabutylammonium bromide (TBAB). The reaction was monitored by TLC, and on completion the reaction mixture was allowed to cool to room temperature, then filtered to remove the insoluble solids. The filtered solid was then washed with dichloromethane. Excess solvents were removed under reduced pressure and the obtained crude product was purified by crystallization using 1:1 ratio of chloroform and methanol. Colourless block-like crystals were obtained after two days.
7. Refinement
Crystal data, data collection and structure . The NH H atoms were located in difference-Fourier maps and refined freely. The C-bound H atoms were positioned geometrically (C—H = 0.93—0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) =1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The of the molecules in the crystal are unknown; the refined to 0.6 (3).
details are summarized in Table 2
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Supporting information
CCDC reference: 1954107
https://doi.org/10.1107/S2056989019012866/su5514sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012866/su5514Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019012866/su5514Isup3.cml
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2013/1 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015) and PLATON (Spek, 2009).C18H18F2N2O3 | Dx = 1.345 Mg m−3 |
Mr = 348.34 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 8521 reflections |
a = 13.4775 (12) Å | θ = 1.5–28.4° |
b = 28.026 (3) Å | µ = 0.11 mm−1 |
c = 9.1085 (9) Å | T = 293 K |
V = 3440.5 (6) Å3 | BLOCK, colourless |
Z = 8 | 0.30 × 0.25 × 0.20 mm |
F(000) = 1456 |
Bruker SMART APEXII area-detector diffractometer | 5868 reflections with I > 2σ(I) |
ω and φ scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | θmax = 28.4°, θmin = 1.5° |
Tmin = 0.642, Tmax = 0.785 | h = −16→17 |
33263 measured reflections | k = −37→37 |
8521 independent reflections | l = −10→12 |
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)] = 0.053 | Hydrogen site location: mixed |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0901P)2 + 0.6343P] where P = (Fo2 + 2Fc2)/3 |
8521 reflections | (Δ/σ)max < 0.001 |
459 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.24 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 | ||
C3A | 0.6926 (5) | 0.85621 (17) | 0.0399 (6) | 0.0849 (15) | |
H3A | 0.760513 | 0.868025 | 0.052106 | 0.102* | |
C3B | 0.8930 (3) | 0.64609 (14) | 0.4443 (5) | 0.0594 (10) | |
H3B | 0.824697 | 0.634683 | 0.432638 | 0.071* | |
C1B | 0.9416 (4) | 0.63426 (16) | 0.5869 (5) | 0.0770 (14) | |
H1B1 | 0.988434 | 0.657112 | 0.626991 | 0.092* | |
H1B2 | 0.902904 | 0.617075 | 0.659464 | 0.092* | |
C1A | 0.6470 (6) | 0.8684 (2) | −0.0992 (6) | 0.0997 (19) | |
H1A1 | 0.686226 | 0.886135 | −0.169794 | 0.120* | |
H1A2 | 0.600245 | 0.845892 | −0.141389 | 0.120* | |
C2A | 0.6200 (6) | 0.8918 (2) | 0.0358 (7) | 0.111 (2) | |
H2A1 | 0.641359 | 0.924536 | 0.049262 | 0.134* | |
H2A2 | 0.555580 | 0.884387 | 0.077600 | 0.134* | |
C2B | 0.9698 (4) | 0.60887 (18) | 0.4527 (6) | 0.0821 (14) | |
H2B1 | 0.948720 | 0.575924 | 0.442855 | 0.098* | |
H2B2 | 1.034168 | 0.615922 | 0.410413 | 0.098* | |
C4B | 0.9158 (3) | 0.69265 (12) | 0.3746 (4) | 0.0533 (9) | |
H4B1 | 0.871794 | 0.717173 | 0.412054 | 0.064* | |
H4B2 | 0.983671 | 0.701907 | 0.395770 | 0.064* | |
C4A | 0.6728 (4) | 0.80972 (14) | 0.1111 (4) | 0.0599 (10) | |
H4A1 | 0.605344 | 0.799607 | 0.090866 | 0.072* | |
H4A2 | 0.717818 | 0.785685 | 0.073220 | 0.072* | |
C5A | 0.6758 (3) | 0.77698 (11) | 0.3535 (4) | 0.0421 (7) | |
C5B | 0.9153 (3) | 0.72633 (11) | 0.1320 (4) | 0.0418 (7) | |
C10A | 0.6486 (3) | 0.73121 (12) | 0.3097 (4) | 0.0423 (7) | |
H10A | 0.636984 | 0.725073 | 0.210853 | 0.051* | |
C10B | 0.9444 (3) | 0.77079 (12) | 0.1793 (4) | 0.0425 (7) | |
H10B | 0.956199 | 0.775829 | 0.278668 | 0.051* | |
C9A | 0.6385 (2) | 0.69462 (11) | 0.4113 (3) | 0.0398 (7) | |
C9B | 0.9564 (2) | 0.80857 (11) | 0.0804 (3) | 0.0393 (7) | |
C8B | 0.9374 (3) | 0.80117 (12) | −0.0676 (4) | 0.0443 (7) | |
H8B | 0.944975 | 0.825994 | −0.134414 | 0.053* | |
C8A | 0.6566 (3) | 0.70345 (12) | 0.5597 (4) | 0.0450 (8) | |
H8A | 0.649867 | 0.679050 | 0.628203 | 0.054* | |
C7A | 0.6847 (3) | 0.74862 (12) | 0.6046 (4) | 0.0467 (8) | |
H7A | 0.696901 | 0.754677 | 0.703354 | 0.056* | |
C7B | 0.9069 (3) | 0.75644 (12) | −0.1152 (4) | 0.0471 (8) | |
H7B | 0.894040 | 0.751332 | −0.214280 | 0.057* | |
C6A | 0.6947 (3) | 0.78472 (11) | 0.5024 (4) | 0.0428 (7) | |
C6B | 0.8957 (3) | 0.71980 (11) | −0.0171 (4) | 0.0441 (8) | |
C11B | 0.7764 (3) | 0.65960 (13) | −0.0361 (4) | 0.0556 (9) | |
H11B | 0.770549 | 0.653960 | 0.069771 | 0.067* | |
C11A | 0.8125 (3) | 0.84507 (12) | 0.5158 (4) | 0.0523 (9) | |
H11A | 0.820805 | 0.846015 | 0.408994 | 0.063* | |
C12A | 0.6111 (3) | 0.64577 (11) | 0.3570 (3) | 0.0399 (7) | |
C12B | 0.9851 (3) | 0.85610 (11) | 0.1403 (3) | 0.0394 (7) | |
C13B | 1.0486 (3) | 0.93630 (12) | 0.0893 (4) | 0.0527 (9) | |
H13A | 1.112422 | 0.944908 | 0.047812 | 0.063* | |
H13B | 1.053716 | 0.938497 | 0.195349 | 0.063* | |
C13A | 0.5474 (3) | 0.56661 (11) | 0.4218 (4) | 0.0504 (9) | |
H13C | 0.558990 | 0.560555 | 0.318366 | 0.060* | |
H13D | 0.477237 | 0.561821 | 0.440582 | 0.060* | |
C14A | 0.6056 (3) | 0.53127 (11) | 0.5106 (4) | 0.0468 (8) | |
C14B | 0.9714 (3) | 0.97029 (12) | 0.0361 (5) | 0.0574 (10) | |
C15A | 0.6971 (3) | 0.54131 (14) | 0.5656 (5) | 0.0604 (10) | |
H15A | 0.726593 | 0.570913 | 0.550449 | 0.072* | |
C15B | 0.8969 (5) | 0.9869 (2) | 0.1237 (8) | 0.0966 (18) | |
H15B | 0.893675 | 0.977774 | 0.221716 | 0.116* | |
C16A | 0.7455 (4) | 0.50557 (19) | 0.6458 (7) | 0.0808 (14) | |
H16A | 0.808325 | 0.511136 | 0.684333 | 0.097* | |
C16B | 0.8265 (6) | 1.0173 (3) | 0.0664 (11) | 0.128 (3) | |
H16B | 0.774980 | 1.029011 | 0.124056 | 0.154* | |
C17A | 0.7010 (5) | 0.46329 (18) | 0.6668 (7) | 0.0911 (17) | |
H17A | 0.732284 | 0.439371 | 0.720385 | 0.109* | |
C17B | 0.8351 (6) | 1.0297 (2) | −0.0794 (11) | 0.122 (3) | |
H17B | 0.787592 | 1.048970 | −0.124001 | 0.146* | |
C18A | 0.6109 (5) | 0.45618 (16) | 0.6094 (7) | 0.0910 (17) | |
H18A | 0.580764 | 0.426749 | 0.624739 | 0.109* | |
C18B | 0.9148 (6) | 1.0132 (2) | −0.1574 (7) | 0.108 (2) | |
H18B | 0.922244 | 1.023375 | −0.253996 | 0.130* | |
N1A | 0.5726 (3) | 0.61610 (10) | 0.4539 (3) | 0.0465 (7) | |
N1B | 1.0244 (3) | 0.88763 (10) | 0.0482 (4) | 0.0473 (7) | |
N2B | 0.9813 (4) | 0.98388 (15) | −0.1035 (4) | 0.0834 (13) | |
N2A | 0.5614 (3) | 0.48899 (12) | 0.5308 (5) | 0.0714 (10) | |
O1B | 0.9022 (2) | 0.68714 (8) | 0.2187 (3) | 0.0538 (6) | |
O1A | 0.6868 (2) | 0.81526 (8) | 0.2653 (3) | 0.0573 (7) | |
O2A | 0.7199 (2) | 0.83023 (8) | 0.5524 (3) | 0.0547 (7) | |
O2B | 0.8688 (2) | 0.67504 (9) | −0.0719 (3) | 0.0547 (7) | |
O3A | 0.6272 (2) | 0.63485 (8) | 0.2278 (3) | 0.0527 (6) | |
O3B | 0.9710 (2) | 0.86563 (9) | 0.2718 (3) | 0.0555 (7) | |
F2B | 0.7076 (2) | 0.69107 (10) | −0.0828 (3) | 0.0810 (8) | |
F1A | 0.8220 (3) | 0.88794 (10) | 0.5731 (5) | 0.1111 (12) | |
F2A | 0.8810 (2) | 0.81731 (11) | 0.5780 (4) | 0.0885 (9) | |
F1B | 0.7623 (3) | 0.61959 (10) | −0.1115 (4) | 0.0974 (10) | |
H1A | 0.552 (3) | 0.6261 (14) | 0.535 (5) | 0.053 (11)* | |
H1B | 1.040 (3) | 0.8804 (13) | −0.028 (4) | 0.039 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3A | 0.108 (4) | 0.075 (3) | 0.072 (3) | 0.002 (3) | −0.004 (3) | 0.018 (2) |
C3B | 0.059 (2) | 0.059 (2) | 0.060 (2) | −0.0020 (18) | 0.0005 (19) | 0.0089 (18) |
C1B | 0.107 (4) | 0.073 (3) | 0.051 (3) | −0.007 (2) | −0.003 (2) | 0.016 (2) |
C1A | 0.146 (6) | 0.095 (4) | 0.059 (3) | 0.009 (4) | −0.003 (3) | 0.021 (3) |
C2A | 0.140 (6) | 0.097 (4) | 0.097 (5) | 0.029 (4) | 0.011 (4) | 0.001 (3) |
C2B | 0.088 (4) | 0.071 (3) | 0.087 (4) | 0.017 (2) | 0.003 (3) | 0.019 (3) |
C4B | 0.064 (2) | 0.0516 (18) | 0.044 (2) | −0.0016 (17) | −0.0037 (17) | 0.0031 (16) |
C4A | 0.074 (3) | 0.058 (2) | 0.047 (2) | −0.0015 (19) | −0.0061 (19) | 0.0088 (17) |
C5A | 0.0406 (19) | 0.0444 (16) | 0.0414 (18) | 0.0031 (13) | 0.0003 (14) | 0.0035 (13) |
C5B | 0.0406 (18) | 0.0454 (15) | 0.0395 (18) | 0.0010 (13) | 0.0013 (13) | 0.0041 (13) |
C10A | 0.0437 (19) | 0.0486 (16) | 0.0346 (17) | 0.0018 (14) | −0.0049 (13) | 0.0002 (13) |
C10B | 0.045 (2) | 0.0489 (16) | 0.0334 (17) | 0.0004 (14) | −0.0027 (13) | 0.0028 (13) |
C9A | 0.0374 (17) | 0.0476 (15) | 0.0344 (16) | 0.0033 (13) | −0.0024 (13) | −0.0009 (13) |
C9B | 0.0331 (16) | 0.0482 (16) | 0.0365 (17) | 0.0019 (12) | 0.0008 (12) | 0.0013 (13) |
C8B | 0.0449 (18) | 0.0546 (17) | 0.0334 (17) | −0.0044 (14) | −0.0005 (13) | 0.0037 (14) |
C8A | 0.0497 (19) | 0.0513 (17) | 0.0341 (18) | −0.0008 (14) | 0.0002 (14) | 0.0031 (14) |
C7A | 0.049 (2) | 0.0578 (19) | 0.0330 (17) | −0.0058 (16) | −0.0019 (14) | −0.0040 (15) |
C7B | 0.047 (2) | 0.0619 (19) | 0.0323 (17) | −0.0067 (16) | −0.0003 (14) | −0.0025 (15) |
C6A | 0.0392 (19) | 0.0469 (16) | 0.0425 (19) | −0.0003 (13) | 0.0027 (14) | −0.0071 (14) |
C6B | 0.0366 (18) | 0.0520 (17) | 0.0437 (19) | −0.0042 (14) | 0.0038 (14) | −0.0079 (14) |
C11B | 0.062 (3) | 0.060 (2) | 0.045 (2) | −0.0165 (18) | −0.0007 (17) | 0.0005 (17) |
C11A | 0.052 (2) | 0.0510 (18) | 0.054 (2) | −0.0069 (16) | 0.0001 (17) | 0.0023 (16) |
C12A | 0.0417 (18) | 0.0445 (15) | 0.0337 (16) | 0.0048 (13) | −0.0034 (13) | 0.0018 (13) |
C12B | 0.0420 (18) | 0.0430 (15) | 0.0330 (16) | 0.0010 (13) | −0.0020 (13) | 0.0020 (13) |
C13B | 0.068 (3) | 0.0457 (17) | 0.044 (2) | −0.0066 (16) | −0.0037 (18) | 0.0005 (15) |
C13A | 0.062 (2) | 0.0428 (16) | 0.047 (2) | −0.0025 (15) | −0.0055 (17) | −0.0020 (14) |
C14A | 0.056 (2) | 0.0431 (16) | 0.0416 (19) | 0.0038 (15) | 0.0052 (15) | −0.0040 (14) |
C14B | 0.071 (3) | 0.0446 (17) | 0.057 (2) | −0.0013 (17) | 0.001 (2) | −0.0065 (16) |
C15A | 0.052 (2) | 0.065 (2) | 0.065 (3) | 0.0005 (18) | −0.0015 (19) | 0.0017 (19) |
C15B | 0.097 (4) | 0.093 (3) | 0.100 (4) | 0.018 (3) | 0.032 (4) | 0.019 (3) |
C16A | 0.060 (3) | 0.092 (3) | 0.090 (4) | 0.016 (2) | −0.011 (3) | 0.004 (3) |
C16B | 0.105 (5) | 0.116 (5) | 0.163 (8) | 0.044 (4) | 0.028 (5) | 0.004 (5) |
C17A | 0.116 (5) | 0.067 (3) | 0.091 (4) | 0.027 (3) | −0.020 (3) | 0.013 (3) |
C17B | 0.129 (6) | 0.094 (4) | 0.142 (7) | 0.048 (4) | −0.048 (5) | −0.014 (4) |
C18A | 0.121 (5) | 0.053 (2) | 0.099 (4) | −0.005 (3) | −0.022 (4) | 0.018 (2) |
C18B | 0.153 (7) | 0.098 (4) | 0.073 (4) | 0.053 (4) | −0.029 (4) | −0.003 (3) |
N1A | 0.0626 (19) | 0.0413 (13) | 0.0355 (16) | −0.0002 (13) | 0.0056 (13) | −0.0034 (12) |
N1B | 0.063 (2) | 0.0443 (14) | 0.0343 (16) | 0.0007 (13) | 0.0049 (14) | 0.0010 (13) |
N2B | 0.115 (4) | 0.083 (2) | 0.052 (2) | 0.035 (2) | −0.007 (2) | 0.002 (2) |
N2A | 0.086 (3) | 0.0524 (17) | 0.076 (3) | −0.0080 (17) | −0.015 (2) | 0.0087 (17) |
O1B | 0.0715 (19) | 0.0454 (12) | 0.0445 (14) | −0.0040 (12) | −0.0072 (12) | 0.0056 (10) |
O1A | 0.075 (2) | 0.0483 (13) | 0.0487 (15) | −0.0047 (12) | −0.0070 (13) | 0.0062 (11) |
O2A | 0.0512 (16) | 0.0537 (13) | 0.0593 (16) | −0.0064 (11) | 0.0102 (12) | −0.0142 (12) |
O2B | 0.0600 (17) | 0.0553 (13) | 0.0488 (15) | −0.0113 (11) | 0.0107 (12) | −0.0133 (11) |
O3A | 0.0662 (17) | 0.0570 (13) | 0.0349 (13) | −0.0037 (12) | 0.0031 (11) | −0.0057 (10) |
O3B | 0.0734 (19) | 0.0597 (14) | 0.0336 (13) | −0.0128 (13) | 0.0001 (12) | −0.0025 (11) |
F2B | 0.0607 (16) | 0.0891 (17) | 0.093 (2) | −0.0114 (13) | −0.0134 (14) | 0.0211 (15) |
F1A | 0.095 (2) | 0.0660 (15) | 0.172 (4) | −0.0286 (15) | 0.019 (2) | −0.0379 (19) |
F2A | 0.0591 (16) | 0.1027 (19) | 0.104 (2) | −0.0103 (14) | −0.0187 (15) | 0.0355 (17) |
F1B | 0.110 (2) | 0.0744 (16) | 0.108 (2) | −0.0407 (16) | 0.0166 (19) | −0.0294 (16) |
C3A—C2A | 1.397 (9) | C7B—H7B | 0.9300 |
C3A—C1A | 1.449 (8) | C6A—O2A | 1.396 (4) |
C3A—C4A | 1.479 (6) | C6B—O2B | 1.398 (4) |
C3A—H3A | 0.9800 | C11B—F1B | 1.329 (4) |
C3B—C2B | 1.471 (6) | C11B—F2B | 1.348 (5) |
C3B—C4B | 1.484 (5) | C11B—O2B | 1.359 (5) |
C3B—C1B | 1.492 (6) | C11B—H11B | 0.9800 |
C3B—H3B | 0.9800 | C11A—F1A | 1.316 (4) |
C1B—C2B | 1.465 (7) | C11A—F2A | 1.334 (5) |
C1B—H1B1 | 0.9700 | C11A—O2A | 1.357 (5) |
C1B—H1B2 | 0.9700 | C11A—H11A | 0.9800 |
C1A—C2A | 1.441 (8) | C12A—O3A | 1.235 (4) |
C1A—H1A1 | 0.9700 | C12A—N1A | 1.319 (4) |
C1A—H1A2 | 0.9700 | C12B—O3B | 1.242 (4) |
C2A—H2A1 | 0.9700 | C12B—N1B | 1.328 (4) |
C2A—H2A2 | 0.9700 | C13B—N1B | 1.452 (4) |
C2B—H2B1 | 0.9700 | C13B—C14B | 1.492 (6) |
C2B—H2B2 | 0.9700 | C13B—H13A | 0.9700 |
C4B—O1B | 1.440 (4) | C13B—H13B | 0.9700 |
C4B—H4B1 | 0.9700 | C13A—N1A | 1.458 (4) |
C4B—H4B2 | 0.9700 | C13A—C14A | 1.500 (5) |
C4A—O1A | 1.426 (5) | C13A—H13C | 0.9700 |
C4A—H4A1 | 0.9700 | C13A—H13D | 0.9700 |
C4A—H4A2 | 0.9700 | C14A—N2A | 1.339 (5) |
C5A—O1A | 1.349 (4) | C14A—C15A | 1.361 (6) |
C5A—C10A | 1.392 (5) | C14B—N2B | 1.333 (6) |
C5A—C6A | 1.397 (5) | C14B—C15B | 1.365 (7) |
C5B—O1B | 1.365 (4) | C15A—C16A | 1.400 (6) |
C5B—C10B | 1.375 (5) | C15A—H15A | 0.9300 |
C5B—C6B | 1.395 (5) | C15B—C16B | 1.378 (10) |
C10A—C9A | 1.388 (5) | C15B—H15B | 0.9300 |
C10A—H10A | 0.9300 | C16A—C17A | 1.342 (8) |
C10B—C9B | 1.399 (4) | C16A—H16A | 0.9300 |
C10B—H10B | 0.9300 | C16B—C17B | 1.378 (11) |
C9A—C8A | 1.396 (5) | C16B—H16B | 0.9300 |
C9A—C12A | 1.501 (4) | C17A—C18A | 1.337 (9) |
C9B—C8B | 1.388 (5) | C17A—H17A | 0.9300 |
C9B—C12B | 1.490 (4) | C17B—C18B | 1.369 (11) |
C8B—C7B | 1.389 (5) | C17B—H17B | 0.9300 |
C8B—H8B | 0.9300 | C18A—N2A | 1.343 (6) |
C8A—C7A | 1.383 (5) | C18A—H18A | 0.9300 |
C8A—H8A | 0.9300 | C18B—N2B | 1.312 (7) |
C7A—C6A | 1.381 (5) | C18B—H18B | 0.9300 |
C7A—H7A | 0.9300 | N1A—H1A | 0.83 (4) |
C7B—C6B | 1.370 (5) | N1B—H1B | 0.75 (4) |
C2A—C3A—C1A | 60.8 (4) | C7A—C6A—O2A | 118.2 (3) |
C2A—C3A—C4A | 120.9 (6) | C7A—C6A—C5A | 121.5 (3) |
C1A—C3A—C4A | 120.9 (5) | O2A—C6A—C5A | 120.2 (3) |
C2A—C3A—H3A | 114.6 | C7B—C6B—C5B | 121.1 (3) |
C1A—C3A—H3A | 114.6 | C7B—C6B—O2B | 117.9 (3) |
C4A—C3A—H3A | 114.6 | C5B—C6B—O2B | 121.0 (3) |
C2B—C3B—C4B | 120.0 (4) | F1B—C11B—F2B | 106.9 (3) |
C2B—C3B—C1B | 59.2 (3) | F1B—C11B—O2B | 106.0 (3) |
C4B—C3B—C1B | 118.5 (4) | F2B—C11B—O2B | 110.3 (3) |
C2B—C3B—H3B | 115.8 | F1B—C11B—H11B | 111.2 |
C4B—C3B—H3B | 115.8 | F2B—C11B—H11B | 111.2 |
C1B—C3B—H3B | 115.8 | O2B—C11B—H11B | 111.2 |
C2B—C1B—C3B | 59.7 (3) | F1A—C11A—F2A | 107.2 (4) |
C2B—C1B—H1B1 | 117.8 | F1A—C11A—O2A | 105.8 (3) |
C3B—C1B—H1B1 | 117.8 | F2A—C11A—O2A | 110.7 (3) |
C2B—C1B—H1B2 | 117.8 | F1A—C11A—H11A | 111.0 |
C3B—C1B—H1B2 | 117.8 | F2A—C11A—H11A | 111.0 |
H1B1—C1B—H1B2 | 114.9 | O2A—C11A—H11A | 111.0 |
C2A—C1A—C3A | 57.8 (4) | O3A—C12A—N1A | 123.4 (3) |
C2A—C1A—H1A1 | 118.0 | O3A—C12A—C9A | 119.8 (3) |
C3A—C1A—H1A1 | 118.0 | N1A—C12A—C9A | 116.8 (3) |
C2A—C1A—H1A2 | 118.0 | O3B—C12B—N1B | 121.8 (3) |
C3A—C1A—H1A2 | 118.0 | O3B—C12B—C9B | 120.3 (3) |
H1A1—C1A—H1A2 | 115.2 | N1B—C12B—C9B | 117.8 (3) |
C3A—C2A—C1A | 61.3 (4) | N1B—C13B—C14B | 111.1 (3) |
C3A—C2A—H2A1 | 117.6 | N1B—C13B—H13A | 109.4 |
C1A—C2A—H2A1 | 117.6 | C14B—C13B—H13A | 109.4 |
C3A—C2A—H2A2 | 117.6 | N1B—C13B—H13B | 109.4 |
C1A—C2A—H2A2 | 117.6 | C14B—C13B—H13B | 109.4 |
H2A1—C2A—H2A2 | 114.7 | H13A—C13B—H13B | 108.0 |
C1B—C2B—C3B | 61.1 (3) | N1A—C13A—C14A | 113.4 (3) |
C1B—C2B—H2B1 | 117.7 | N1A—C13A—H13C | 108.9 |
C3B—C2B—H2B1 | 117.7 | C14A—C13A—H13C | 108.9 |
C1B—C2B—H2B2 | 117.7 | N1A—C13A—H13D | 108.9 |
C3B—C2B—H2B2 | 117.7 | C14A—C13A—H13D | 108.9 |
H2B1—C2B—H2B2 | 114.8 | H13C—C13A—H13D | 107.7 |
O1B—C4B—C3B | 107.5 (3) | N2A—C14A—C15A | 122.4 (4) |
O1B—C4B—H4B1 | 110.2 | N2A—C14A—C13A | 115.2 (4) |
C3B—C4B—H4B1 | 110.2 | C15A—C14A—C13A | 122.4 (3) |
O1B—C4B—H4B2 | 110.2 | N2B—C14B—C15B | 122.2 (5) |
C3B—C4B—H4B2 | 110.2 | N2B—C14B—C13B | 115.0 (4) |
H4B1—C4B—H4B2 | 108.5 | C15B—C14B—C13B | 122.8 (4) |
O1A—C4A—C3A | 108.2 (4) | C14A—C15A—C16A | 117.8 (4) |
O1A—C4A—H4A1 | 110.1 | C14A—C15A—H15A | 121.1 |
C3A—C4A—H4A1 | 110.1 | C16A—C15A—H15A | 121.1 |
O1A—C4A—H4A2 | 110.1 | C14B—C15B—C16B | 119.8 (6) |
C3A—C4A—H4A2 | 110.1 | C14B—C15B—H15B | 120.1 |
H4A1—C4A—H4A2 | 108.4 | C16B—C15B—H15B | 120.1 |
O1A—C5A—C10A | 126.2 (3) | C17A—C16A—C15A | 119.9 (5) |
O1A—C5A—C6A | 115.8 (3) | C17A—C16A—H16A | 120.1 |
C10A—C5A—C6A | 118.0 (3) | C15A—C16A—H16A | 120.1 |
O1B—C5B—C10B | 125.8 (3) | C17B—C16B—C15B | 117.6 (7) |
O1B—C5B—C6B | 115.7 (3) | C17B—C16B—H16B | 121.2 |
C10B—C5B—C6B | 118.5 (3) | C15B—C16B—H16B | 121.2 |
C9A—C10A—C5A | 121.0 (3) | C18A—C17A—C16A | 118.8 (5) |
C9A—C10A—H10A | 119.5 | C18A—C17A—H17A | 120.6 |
C5A—C10A—H10A | 119.5 | C16A—C17A—H17A | 120.6 |
C5B—C10B—C9B | 121.1 (3) | C18B—C17B—C16B | 118.7 (6) |
C5B—C10B—H10B | 119.4 | C18B—C17B—H17B | 120.6 |
C9B—C10B—H10B | 119.4 | C16B—C17B—H17B | 120.6 |
C10A—C9A—C8A | 119.8 (3) | C17A—C18A—N2A | 123.9 (5) |
C10A—C9A—C12A | 118.6 (3) | C17A—C18A—H18A | 118.0 |
C8A—C9A—C12A | 121.6 (3) | N2A—C18A—H18A | 118.0 |
C8B—C9B—C10B | 119.4 (3) | N2B—C18B—C17B | 123.6 (6) |
C8B—C9B—C12B | 122.5 (3) | N2B—C18B—H18B | 118.2 |
C10B—C9B—C12B | 118.1 (3) | C17B—C18B—H18B | 118.2 |
C9B—C8B—C7B | 119.5 (3) | C12A—N1A—C13A | 123.9 (3) |
C9B—C8B—H8B | 120.2 | C12A—N1A—H1A | 121 (3) |
C7B—C8B—H8B | 120.2 | C13A—N1A—H1A | 115 (3) |
C7A—C8A—C9A | 119.8 (3) | C12B—N1B—C13B | 123.5 (3) |
C7A—C8A—H8A | 120.1 | C12B—N1B—H1B | 121 (3) |
C9A—C8A—H8A | 120.1 | C13B—N1B—H1B | 115 (3) |
C6A—C7A—C8A | 119.9 (3) | C18B—N2B—C14B | 117.9 (5) |
C6A—C7A—H7A | 120.1 | C14A—N2A—C18A | 117.2 (4) |
C8A—C7A—H7A | 120.1 | C5B—O1B—C4B | 117.9 (3) |
C6B—C7B—C8B | 120.4 (3) | C5A—O1A—C4A | 119.1 (3) |
C6B—C7B—H7B | 119.8 | C11A—O2A—C6A | 115.0 (3) |
C8B—C7B—H7B | 119.8 | C11B—O2B—C6B | 116.0 (3) |
C4B—C3B—C1B—C2B | −109.8 (5) | C10B—C9B—C12B—N1B | 160.6 (3) |
C4A—C3A—C1A—C2A | 110.6 (7) | N1A—C13A—C14A—N2A | 154.4 (4) |
C4A—C3A—C2A—C1A | −110.6 (7) | N1A—C13A—C14A—C15A | −26.1 (5) |
C4B—C3B—C2B—C1B | 107.3 (5) | N1B—C13B—C14B—N2B | −82.7 (4) |
C2B—C3B—C4B—O1B | 84.0 (5) | N1B—C13B—C14B—C15B | 98.2 (5) |
C1B—C3B—C4B—O1B | 153.0 (4) | N2A—C14A—C15A—C16A | 0.1 (6) |
C2A—C3A—C4A—O1A | −81.6 (7) | C13A—C14A—C15A—C16A | −179.4 (4) |
C1A—C3A—C4A—O1A | −153.9 (5) | N2B—C14B—C15B—C16B | 2.7 (10) |
O1A—C5A—C10A—C9A | −179.3 (3) | C13B—C14B—C15B—C16B | −178.3 (6) |
C6A—C5A—C10A—C9A | 1.3 (5) | C14A—C15A—C16A—C17A | −0.5 (8) |
O1B—C5B—C10B—C9B | 179.4 (3) | C14B—C15B—C16B—C17B | −0.1 (12) |
C6B—C5B—C10B—C9B | −1.4 (5) | C15A—C16A—C17A—C18A | 0.4 (9) |
C5A—C10A—C9A—C8A | −0.6 (5) | C15B—C16B—C17B—C18B | −3.0 (13) |
C5A—C10A—C9A—C12A | −178.7 (3) | C16A—C17A—C18A—N2A | 0.1 (10) |
C5B—C10B—C9B—C8B | 0.9 (5) | C16B—C17B—C18B—N2B | 3.9 (12) |
C5B—C10B—C9B—C12B | 178.2 (3) | O3A—C12A—N1A—C13A | 2.1 (6) |
C10B—C9B—C8B—C7B | −0.1 (5) | C9A—C12A—N1A—C13A | −176.3 (3) |
C12B—C9B—C8B—C7B | −177.3 (3) | C14A—C13A—N1A—C12A | 117.2 (4) |
C10A—C9A—C8A—C7A | −0.1 (5) | O3B—C12B—N1B—C13B | −3.8 (6) |
C12A—C9A—C8A—C7A | 177.9 (3) | C9B—C12B—N1B—C13B | 175.2 (3) |
C9A—C8A—C7A—C6A | 0.0 (5) | C14B—C13B—N1B—C12B | −101.4 (4) |
C9B—C8B—C7B—C6B | 0.0 (5) | C17B—C18B—N2B—C14B | −1.5 (11) |
C8A—C7A—C6A—O2A | 177.8 (3) | C15B—C14B—N2B—C18B | −1.9 (8) |
C8A—C7A—C6A—C5A | 0.8 (5) | C13B—C14B—N2B—C18B | 179.0 (5) |
O1A—C5A—C6A—C7A | 179.1 (3) | C15A—C14A—N2A—C18A | 0.3 (7) |
C10A—C5A—C6A—C7A | −1.5 (5) | C13A—C14A—N2A—C18A | 179.8 (5) |
O1A—C5A—C6A—O2A | 2.1 (5) | C17A—C18A—N2A—C14A | −0.4 (9) |
C10A—C5A—C6A—O2A | −178.4 (3) | C10B—C5B—O1B—C4B | 2.7 (5) |
C8B—C7B—C6B—C5B | −0.5 (5) | C6B—C5B—O1B—C4B | −176.5 (3) |
C8B—C7B—C6B—O2B | −177.4 (3) | C3B—C4B—O1B—C5B | 177.4 (3) |
O1B—C5B—C6B—C7B | −179.5 (3) | C10A—C5A—O1A—C4A | −2.0 (6) |
C10B—C5B—C6B—C7B | 1.2 (5) | C6A—C5A—O1A—C4A | 177.5 (3) |
O1B—C5B—C6B—O2B | −2.7 (5) | C3A—C4A—O1A—C5A | −178.0 (4) |
C10B—C5B—C6B—O2B | 178.1 (3) | F1A—C11A—O2A—C6A | −179.5 (3) |
C10A—C9A—C12A—O3A | 21.9 (5) | F2A—C11A—O2A—C6A | −63.7 (4) |
C8A—C9A—C12A—O3A | −156.1 (3) | C7A—C6A—O2A—C11A | 110.5 (4) |
C10A—C9A—C12A—N1A | −159.6 (3) | C5A—C6A—O2A—C11A | −72.5 (4) |
C8A—C9A—C12A—N1A | 22.4 (5) | F1B—C11B—O2B—C6B | 173.3 (3) |
C8B—C9B—C12B—O3B | 156.8 (3) | F2B—C11B—O2B—C6B | 58.0 (4) |
C10B—C9B—C12B—O3B | −20.3 (5) | C7B—C6B—O2B—C11B | −111.5 (4) |
C8B—C9B—C12B—N1B | −22.2 (5) | C5B—C6B—O2B—C11B | 71.5 (4) |
Cg2, Cg3 and Cg6 are the centroids of the N2A/C14A–C18A, C5A–C10A and C5B–C10B rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11A—H11A···O3B | 0.98 | 2.44 | 3.136 (5) | 128 |
C11B—H11B···O3A | 0.98 | 2.47 | 3.210 (5) | 132 |
C4B—H4B1···Cg3 | 0.97 | 2.87 | 3.689 (4) | 143 |
C4A—H4A2···Cg6 | 0.97 | 2.90 | 3.717 (5) | 143 |
N1A—H1A···O3Bi | 0.84 (4) | 2.08 (4) | 2.895 (4) | 163 (4) |
N1B—H1B···O3Aii | 0.75 (4) | 2.21 (4) | 2.939 (4) | 164 (4) |
C13A—H13C···N2Biii | 0.97 | 2.55 | 3.347 (5) | 140 |
C13A—H13D···F1Ai | 0.97 | 2.52 | 3.294 (6) | 136 |
C13B—H13B···Cg2iv | 0.97 | 2.73 | 3.748 (4) | 137 |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x+1/2, −y+3/2, −z; (iii) x−1/2, −y+3/2, −z; (iv) x+1/2, −y+3/2, −z+1. |
Acknowledgements
The authors thank the TBI Consultancy, CAS in Crystallography & Biophysics, University of Madras, India, for the data collection.
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