research communications
3.8]undecane
and Hirshfeld surface analysis of 2,4,6,11-tetrakis(4-fluorophenyl)-9-oxa-1,5-diazatricyclo[5.3.1.0aDepartment of Chemistry, The Gandhigram Rural Institute – Deemed to be University, Gandhigram 624302, Tamilnadu, India, and bSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India
*Correspondence e-mail: msundargri@gmail.com
The title compound, C32H26F4N2O, crystallizes in the monoclinic P21/n with four molecules in the The compound was prepared by the NaBH4 reduction of 4,8,9,10-tetrakis(4-fluorophenyl)-1,3-diazaadamantan-6-one in chloroform and ethanol as solvent. The piperidine rings exhibit chair and boat conformations, and all four fluorophenyl groups are oriented in the equatorial direction. The features C—H⋯F hydrogen bonds, C—H⋯π, N—H⋯π and π–π interactions. Hirshfeld surface and two-dimensional fingerprint analysis show that van der Waals interactions constitute a major contribution to the intermolecular interactions, with H⋯H contacts accounting for 37.9% of the surface.
Keywords: crystal structure; diazabicyclo bispidine; quinuclidine ring; Hirshfeld surface analysis; Fluorophenyl; π-π stacking interactions.
CCDC reference: 1854381
1. Chemical context
Molecules containing a bispidine nucleus are of great interest due to their presence in a wide variety of naturally occurring ). The biological activities of the molecule depend crucially on the stereochemistry and conformation of the compound, and hence studies on the stereochemistry of the molecules are interesting. The title compound contains four fluorophenyl groups and hence the investigation also looked for any weak interactions involving fluorine which are of current interest (Hathwar et al., 2014). Moreover, Das et al. (2017) have recently discussed the role of halogens in stabilizing stacking patterns.
and various biologically active molecules (Jeyaraman & Avila, 19812. Structural commentary
An ORTEP view of the title compound is shown in Fig. 1. The N2/C7/C8/C24–C26 piperidine ring adopts a chair conformation with puckering parameters Q = 0.6178 (19) Å, θ = 176.85 (18)°, φ = 25 (3)° while the N1/C9/C8/C24/C25/C17 piperidine ring [puckering parameters Q = 0.8564 (18) Å, θ = 89.49 (12)°, φ = 178.52 (12)°] adopts a boat conformation. The oxygen-containing quinuclidine ring system (C8/C9/N1/C17/C25/C24/O1/C16) also adopts a boat conformation, with puckering parameters Q = 0.7817 (18) Å, θ = 91.23 (13)°, φ = 121.27 (13)° for the C8/C9/N1/C16/O1/C24 ring and Q = 0.7867 (18) Å, θ = 89.40 (13)°, φ = 297.43 (3)° for the C17/C25/C24/O1/C16/N1 ring. The fluorophenyl groups at C7 and C26 subtend a dihedral angle of 29.45 (1)° and are oriented equatorially with respect to the N2/C7/C8/C24–C26 piperidine ring with torsion angles C6—C7—C8—C24 = −179.72 (14)° and C24—C25—C26—C27 = 176.10 (14)°. The other two fluorophenyl groups at C9 and C17 subtend a dihedral angle of 21.85 (1)° and are oriented equatorially with respect to the N1/C9/C8/C24/C25/C17 piperidine ring, with torsion angles C10—C9—C8—C24 = 125.64 (15)° and C18—C17—C25—C24 = −128.24 (15)°.
3. Supramolecular features
In the crystal, several C—H⋯F hydrogen bonds occur. Screw-related molecules are linked by C32—H32⋯F4iii and C1—H1⋯F4iii hydrogen bonds with F4 acting as a bifurcated acceptor (Table 1). The molecules are further linked by C31—H31⋯F1i and C8—H8⋯F3ii hydrogen bonds (Fig. 2). An N—H⋯π interaction is present along with intra- and intermolecular C—H⋯π interactions (Table 1, Figs. 2 and 3). Weak π–π stacking interactions occur between the fluorophenyl groups [Cg6v⋯Cg7vi = 4.0665 (12) Å; symmetry code: (vi) 1 − x, 1 − y, 1 − z; Cg6 and Cg7 are the centroids of the C10–C15 and C18–C23 rings respectively). Overall, these interactions generate a three-dimensional supramolecular architecture.
4. Hirshfeld surface analysis
Hirshfeld surface analysis and fingerprint plots, here generated with Crystal Explorer (Hirshfeld, 1977; Wolff et al., 2012; Turner et al., 2017), show the various intermolecular interactions present in crystal structures (Wiedemann & Kohl, 2017; Tarahhomi et al., 2013). Fig. 4 shows the Hirshfeld surface of the title compound mapped over dnorm where the intense red spots indicate regions of donor–acceptor interactions (Cárdenas-Valenzuela et al., 2018; Atioğlu et al., 2018) and represent the fluorine, carbon and hydrogen atoms involved. Fig. 5 shows the two-dimensional fingerprint plots, which quantify the contribution of each kind of interaction to the surface formation (McKinnon et al., 2007). The largest contribution to the surface of 37.9% is from H⋯H contacts, while C⋯H contacts contribute 22.4%; these represent van der Waals interactions present in the crystal. Intermolecular hydrogen-bonding interactions (F⋯H/H⋯F contacts) contribute 29.2%.
5. Database survey
Diazabicyclic compounds with different substituents on the aromatic rings have been reported in the literature: 2,4,6,8-tetrakis(4-ethylphenyl)-3,7-diazabicyclo-[3.3.1]-nonan-9-one [(I); Rajesh et al., 2010], 2,4,6,8-tetrakis(4-bromophenyl)-3,7diazabicyclo-[3.3.1]-nonan-9-one [(II); Loh et al., 2010], 2,4,6,8-tetrakis(2-methoxyphenyl)-3,7-diazabicyclo[3.3.1]nonan-9-one [(III); Fun et al., 2009], 2,4,6,8-tetrakis(4-fluorophenyl)-3,7-diazabicyclo[3.3.1]nonan-9-one [(IV); Natarajan et al., 2008]. Compounds (I), (II) and (III) crystallize in P21/c, while compound (IV) crystallizes in C2/c. The piperidine rings in all of these compounds adopt chair–boat conformations with an equatorial orientation of the aryl rings. In the crystal of (I), molecules are linked via C—H⋯O hydrogen bonds, forming helical supramolecular chains along the b-axis direction. In (II), the molecules are connected through C—H⋯O and N—H⋯O hydrogen bonds, forming chains propagating along the c-axis direction, and C—H⋯π interactions also occur. The supramolecular structure of compound (III) features C—H⋯N hydrogen bonds, which link the molecules along the b-axis direction, and C—H⋯π interactions. In (IV), the molecules are linked into a two-dimensional network by N—H⋯O, C—H⋯F and C—H⋯O hydrogen bonds and the crystal packing is further supported by N—H⋯π and C—H⋯π interactions.
Further background to the synthesis and stereochemistry of 3,7-diazabicyclo[3.3.1]nonan-9-ones and their derivatives can be seen in reports of the following structures: chlorophenyl-1,3-diazaadamantan-6-one (Krishnakumar et al., 2001), tetraphenyl-1,3-diazaadamantan-6-one (Subha Nandhini et al., 2002), fluorophenyl-1,3-diazatricyclo[3.3.1.1]decan-6-one (Natarajan et al., 2009) and bispidine oxime (Parthiban et al., 2010).
Weak C—H⋯F hydrogen bonds with similar bond lengths and bond angles to those in the title compound have been reported in the crystal structures of N-(3,5-difluorophenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximide and N-(2,4,6-trifluorophenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximide (Schwarzer & Weber, 2011), 2,3,5,6-tetrafluorobenzene-1,4-diol quinoxaline (Czapik & Gdaniec, 2010) and 2,3-difluoro-N-(4-pyridyl)benzamide (McMahon et al., 2008). N—H⋯π interactions are present in the structures discussed by Fun et al. (2009) and Thirumurugan et al. (1999) while C—H⋯π interactions are present in the structures discussed by Selvanayagam et al. (2015), Muralikrishna et al. (2012) and Girisha et al. (2017).
6. Synthesis and crystallization
The title compound was synthesized in three steps starting from 4-fluorobenzaldehyde, acetone and ammonium acetate. 4,8,9,10-Tetrakis(4-fluorophenyl)-1,3-diazaadamantan-6-one (1 mmol) dissolved in chloroform and NaBH4 (1 mmol) dissolved in ethanol were mixed, transferred to a closed container and stirred at 278–283 K. The reaction was monitored by TLC, and after complete disappearance of the ketone the resulting mixture was filtered. The solvent was evaporated and washed with cold water to obtain the resulting product. The crude product was recrystallized from a chloroform–ethanol (1:2 v:v) mixture by the solvent diffusion method.
7. Refinement
Crystal data, data collection and structure . Carbon-bound hydrogen atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and refined in the riding-model approximation with Uiso(H) = 1.2–1.5Ueq(C).
details are summarized in Table 2
|
Supporting information
CCDC reference: 1854381
https://doi.org/10.1107/S2056989018016122/dx2010sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018016122/dx2010Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989018016122/dx2010Isup3.cml
Data collection: APEX3 (Bruker, 2016); cell
APEX3 and SAINT (Bruker, 2016); data reduction: SAINT and XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009), Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010); software used to prepare material for publication: PLATON (Spek, 2009).C32H26F4N2O | F(000) = 1104 |
Mr = 530.55 | Dx = 1.372 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.5712 (8) Å | Cell parameters from 9987 reflections |
b = 9.5161 (6) Å | θ = 2.9–27.2° |
c = 20.1543 (13) Å | µ = 0.10 mm−1 |
β = 99.357 (2)° | T = 296 K |
V = 2568.2 (3) Å3 | Block, colourless |
Z = 4 | 0.15 × 0.10 × 0.10 mm |
Bruker Kappa APEX3 CMOS diffractometer | 4510 independent reflections |
Radiation source: fine-focus sealed tube | 3456 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω and φ scan | θmax = 25.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −16→15 |
Tmin = 0.711, Tmax = 0.746 | k = −11→11 |
45339 measured reflections | l = −23→23 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0488P)2 + 1.0821P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
4510 reflections | Δρmax = 0.17 e Å−3 |
356 parameters | Δρmin = −0.23 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 | ||
F4 | 0.36854 (15) | −0.15750 (19) | 0.84036 (7) | 0.1037 (6) | |
F2 | 0.14924 (11) | 0.80017 (13) | 0.32630 (7) | 0.0749 (4) | |
F1 | −0.19168 (9) | 0.36154 (18) | 0.39919 (8) | 0.0810 (5) | |
F3 | 0.71306 (11) | 0.37803 (19) | 0.77538 (7) | 0.0862 (5) | |
O1 | 0.43408 (9) | 0.18807 (14) | 0.44967 (6) | 0.0460 (3) | |
N1 | 0.36706 (10) | 0.34033 (15) | 0.52679 (7) | 0.0333 (3) | |
N2 | 0.19955 (12) | 0.05682 (16) | 0.54676 (7) | 0.0367 (4) | |
C30 | 0.3505 (2) | −0.1210 (3) | 0.77425 (11) | 0.0666 (7) | |
C31 | 0.28511 (19) | −0.0145 (3) | 0.75434 (11) | 0.0629 (6) | |
H31 | 0.2534 | 0.0331 | 0.7852 | 0.075* | |
C32 | 0.26722 (16) | 0.0210 (2) | 0.68670 (10) | 0.0490 (5) | |
H32 | 0.2230 | 0.0935 | 0.6722 | 0.059* | |
C27 | 0.31384 (14) | −0.04937 (19) | 0.64048 (9) | 0.0391 (4) | |
C26 | 0.29591 (13) | −0.01240 (18) | 0.56657 (9) | 0.0375 (4) | |
H26 | 0.2955 | −0.0998 | 0.5408 | 0.045* | |
C25 | 0.37815 (13) | 0.08331 (18) | 0.54726 (9) | 0.0365 (4) | |
H25 | 0.4432 | 0.0374 | 0.5596 | 0.044* | |
C17 | 0.38155 (13) | 0.23122 (18) | 0.58041 (8) | 0.0341 (4) | |
H17 | 0.3236 | 0.2370 | 0.6036 | 0.041* | |
C9 | 0.26532 (12) | 0.32453 (17) | 0.48748 (8) | 0.0306 (4) | |
H9 | 0.2189 | 0.3244 | 0.5200 | 0.037* | |
C10 | 0.23762 (12) | 0.44986 (18) | 0.44154 (8) | 0.0324 (4) | |
C15 | 0.28174 (13) | 0.58030 (19) | 0.45697 (9) | 0.0388 (4) | |
H15 | 0.3311 | 0.5892 | 0.4945 | 0.047* | |
C14 | 0.25352 (15) | 0.6971 (2) | 0.41748 (10) | 0.0461 (5) | |
H14 | 0.2852 | 0.7830 | 0.4273 | 0.055* | |
C13 | 0.17844 (16) | 0.6839 (2) | 0.36394 (11) | 0.0487 (5) | |
C3 | −0.10442 (14) | 0.2911 (2) | 0.41805 (11) | 0.0526 (5) | |
C4 | −0.06943 (15) | 0.2070 (2) | 0.37201 (11) | 0.0541 (6) | |
H4 | −0.1041 | 0.1985 | 0.3284 | 0.065* | |
C5 | 0.01920 (15) | 0.1348 (2) | 0.39199 (9) | 0.0449 (5) | |
H5 | 0.0435 | 0.0761 | 0.3615 | 0.054* | |
C6 | 0.07241 (13) | 0.14846 (18) | 0.45673 (8) | 0.0354 (4) | |
C1 | 0.03230 (13) | 0.2329 (2) | 0.50172 (9) | 0.0415 (5) | |
H1 | 0.0656 | 0.2412 | 0.5457 | 0.050* | |
C2 | −0.05616 (15) | 0.3051 (2) | 0.48247 (11) | 0.0505 (5) | |
H2 | −0.0822 | 0.3620 | 0.5129 | 0.061* | |
C7 | 0.17436 (13) | 0.08262 (18) | 0.47433 (9) | 0.0352 (4) | |
H7 | 0.1742 | −0.0074 | 0.4507 | 0.042* | |
C8 | 0.25592 (12) | 0.17776 (17) | 0.45258 (8) | 0.0323 (4) | |
H8 | 0.2418 | 0.1909 | 0.4037 | 0.039* | |
C24 | 0.35693 (13) | 0.10568 (18) | 0.47129 (9) | 0.0379 (4) | |
H24 | 0.3543 | 0.0139 | 0.4490 | 0.045* | |
C18 | 0.47282 (13) | 0.2657 (2) | 0.63240 (9) | 0.0402 (4) | |
C19 | 0.49034 (16) | 0.4052 (2) | 0.65186 (10) | 0.0540 (5) | |
H19 | 0.4467 | 0.4744 | 0.6322 | 0.065* | |
C20 | 0.57105 (18) | 0.4435 (3) | 0.69963 (11) | 0.0631 (6) | |
H20 | 0.5824 | 0.5372 | 0.7116 | 0.076* | |
C21 | 0.63320 (16) | 0.3411 (3) | 0.72859 (10) | 0.0586 (6) | |
C22 | 0.61911 (16) | 0.2029 (3) | 0.71244 (11) | 0.0593 (6) | |
H22 | 0.6625 | 0.1349 | 0.7335 | 0.071* | |
C23 | 0.53842 (15) | 0.1652 (2) | 0.66377 (10) | 0.0508 (5) | |
H23 | 0.5284 | 0.0711 | 0.6521 | 0.061* | |
C16 | 0.44100 (13) | 0.3227 (2) | 0.48368 (10) | 0.0407 (4) | |
H16A | 0.5069 | 0.3319 | 0.5104 | 0.049* | |
H16B | 0.4332 | 0.3970 | 0.4503 | 0.049* | |
C12 | 0.13179 (16) | 0.5590 (2) | 0.34729 (10) | 0.0517 (5) | |
H12 | 0.0805 | 0.5524 | 0.3107 | 0.062* | |
C11 | 0.16255 (14) | 0.4425 (2) | 0.38611 (10) | 0.0439 (5) | |
H11 | 0.1319 | 0.3565 | 0.3747 | 0.053* | |
C29 | 0.39832 (19) | −0.1925 (3) | 0.73059 (13) | 0.0674 (7) | |
H29 | 0.4427 | −0.2645 | 0.7457 | 0.081* | |
C28 | 0.37981 (16) | −0.1566 (2) | 0.66327 (11) | 0.0538 (5) | |
H28 | 0.4120 | −0.2049 | 0.6329 | 0.065* | |
H2A | 0.1518 (16) | 0.002 (2) | 0.5589 (10) | 0.057 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F4 | 0.1449 (15) | 0.1113 (13) | 0.0448 (8) | −0.0144 (12) | −0.0148 (9) | 0.0298 (8) |
F2 | 0.0972 (10) | 0.0440 (7) | 0.0797 (9) | 0.0120 (7) | 0.0024 (8) | 0.0233 (7) |
F1 | 0.0451 (7) | 0.1086 (12) | 0.0845 (10) | 0.0120 (8) | −0.0037 (7) | 0.0280 (9) |
F3 | 0.0702 (9) | 0.1238 (13) | 0.0541 (8) | −0.0221 (9) | −0.0216 (7) | −0.0030 (8) |
O1 | 0.0436 (7) | 0.0487 (8) | 0.0510 (8) | 0.0015 (6) | 0.0231 (6) | −0.0002 (6) |
N1 | 0.0292 (7) | 0.0343 (8) | 0.0361 (8) | −0.0024 (6) | 0.0042 (6) | 0.0022 (6) |
N2 | 0.0369 (8) | 0.0373 (8) | 0.0358 (8) | −0.0050 (7) | 0.0058 (7) | 0.0065 (7) |
C30 | 0.0842 (17) | 0.0705 (16) | 0.0392 (12) | −0.0193 (14) | −0.0072 (12) | 0.0161 (12) |
C31 | 0.0797 (16) | 0.0687 (15) | 0.0387 (12) | −0.0088 (13) | 0.0051 (11) | 0.0017 (11) |
C32 | 0.0574 (12) | 0.0465 (11) | 0.0418 (11) | −0.0018 (10) | 0.0040 (9) | 0.0031 (9) |
C27 | 0.0430 (10) | 0.0343 (10) | 0.0384 (10) | −0.0062 (8) | 0.0014 (8) | 0.0045 (8) |
C26 | 0.0456 (10) | 0.0289 (9) | 0.0374 (10) | 0.0002 (8) | 0.0048 (8) | 0.0006 (8) |
C25 | 0.0355 (9) | 0.0344 (9) | 0.0403 (10) | 0.0045 (8) | 0.0082 (8) | 0.0014 (8) |
C17 | 0.0312 (9) | 0.0348 (9) | 0.0361 (9) | −0.0009 (7) | 0.0050 (7) | 0.0015 (8) |
C9 | 0.0288 (9) | 0.0298 (9) | 0.0332 (9) | −0.0028 (7) | 0.0054 (7) | −0.0014 (7) |
C10 | 0.0309 (9) | 0.0318 (9) | 0.0352 (9) | −0.0008 (7) | 0.0071 (7) | −0.0001 (7) |
C15 | 0.0362 (10) | 0.0370 (10) | 0.0425 (10) | −0.0027 (8) | 0.0048 (8) | −0.0042 (8) |
C14 | 0.0531 (12) | 0.0292 (9) | 0.0575 (12) | −0.0037 (9) | 0.0137 (10) | −0.0021 (9) |
C13 | 0.0606 (13) | 0.0354 (10) | 0.0507 (12) | 0.0085 (9) | 0.0111 (10) | 0.0114 (9) |
C3 | 0.0327 (10) | 0.0652 (14) | 0.0579 (13) | −0.0047 (10) | 0.0008 (9) | 0.0164 (11) |
C4 | 0.0461 (12) | 0.0692 (14) | 0.0419 (11) | −0.0212 (11) | −0.0077 (9) | 0.0118 (11) |
C5 | 0.0489 (11) | 0.0487 (11) | 0.0358 (10) | −0.0169 (9) | 0.0032 (8) | −0.0011 (9) |
C6 | 0.0359 (9) | 0.0358 (9) | 0.0335 (9) | −0.0123 (8) | 0.0028 (7) | 0.0024 (8) |
C1 | 0.0361 (10) | 0.0538 (12) | 0.0340 (10) | −0.0063 (9) | 0.0038 (8) | 0.0005 (9) |
C2 | 0.0390 (11) | 0.0628 (13) | 0.0504 (12) | 0.0003 (10) | 0.0096 (9) | 0.0035 (10) |
C7 | 0.0419 (10) | 0.0290 (9) | 0.0344 (9) | −0.0055 (8) | 0.0053 (8) | −0.0032 (7) |
C8 | 0.0380 (10) | 0.0320 (9) | 0.0273 (8) | −0.0023 (7) | 0.0066 (7) | −0.0002 (7) |
C24 | 0.0416 (10) | 0.0319 (9) | 0.0427 (10) | −0.0007 (8) | 0.0148 (8) | −0.0039 (8) |
C18 | 0.0373 (10) | 0.0484 (11) | 0.0347 (10) | −0.0038 (8) | 0.0055 (8) | 0.0036 (9) |
C19 | 0.0564 (13) | 0.0536 (13) | 0.0476 (12) | 0.0015 (10) | −0.0054 (10) | −0.0073 (10) |
C20 | 0.0687 (15) | 0.0675 (15) | 0.0482 (13) | −0.0104 (12) | −0.0056 (11) | −0.0130 (11) |
C21 | 0.0504 (13) | 0.0873 (18) | 0.0347 (11) | −0.0140 (12) | −0.0034 (9) | 0.0008 (11) |
C22 | 0.0484 (12) | 0.0773 (17) | 0.0479 (12) | −0.0026 (11) | −0.0051 (10) | 0.0197 (12) |
C23 | 0.0480 (12) | 0.0522 (12) | 0.0492 (12) | −0.0047 (10) | −0.0006 (9) | 0.0116 (10) |
C16 | 0.0345 (10) | 0.0416 (10) | 0.0471 (11) | −0.0026 (8) | 0.0100 (8) | 0.0053 (9) |
C12 | 0.0570 (13) | 0.0461 (12) | 0.0469 (12) | 0.0017 (10) | −0.0068 (10) | 0.0057 (9) |
C11 | 0.0474 (11) | 0.0350 (10) | 0.0464 (11) | −0.0068 (8) | −0.0016 (9) | 0.0021 (8) |
C29 | 0.0718 (16) | 0.0562 (14) | 0.0665 (16) | 0.0019 (12) | −0.0117 (13) | 0.0235 (12) |
C28 | 0.0581 (13) | 0.0465 (12) | 0.0543 (13) | 0.0040 (10) | 0.0016 (10) | 0.0114 (10) |
F4—C30 | 1.360 (2) | C13—C12 | 1.362 (3) |
F2—C13 | 1.364 (2) | C3—C2 | 1.362 (3) |
F1—C3 | 1.360 (2) | C3—C4 | 1.367 (3) |
F3—C21 | 1.362 (2) | C4—C5 | 1.387 (3) |
O1—C24 | 1.431 (2) | C4—H4 | 0.9300 |
O1—C16 | 1.449 (2) | C5—C6 | 1.391 (3) |
N1—C16 | 1.440 (2) | C5—H5 | 0.9300 |
N1—C9 | 1.484 (2) | C6—C1 | 1.387 (3) |
N1—C17 | 1.488 (2) | C6—C7 | 1.508 (3) |
N2—C26 | 1.461 (2) | C1—C2 | 1.383 (3) |
N2—C7 | 1.465 (2) | C1—H1 | 0.9300 |
N2—H2A | 0.89 (2) | C2—H2 | 0.9300 |
C30—C29 | 1.358 (4) | C7—C8 | 1.548 (2) |
C30—C31 | 1.364 (4) | C7—H7 | 0.9800 |
C31—C32 | 1.387 (3) | C8—C24 | 1.524 (2) |
C31—H31 | 0.9300 | C8—H8 | 0.9800 |
C32—C27 | 1.381 (3) | C24—H24 | 0.9800 |
C32—H32 | 0.9300 | C18—C23 | 1.387 (3) |
C27—C28 | 1.385 (3) | C18—C19 | 1.394 (3) |
C27—C26 | 1.511 (2) | C19—C20 | 1.384 (3) |
C26—C25 | 1.539 (2) | C19—H19 | 0.9300 |
C26—H26 | 0.9800 | C20—C21 | 1.357 (3) |
C25—C24 | 1.526 (2) | C20—H20 | 0.9300 |
C25—C17 | 1.555 (2) | C21—C22 | 1.361 (3) |
C25—H25 | 0.9800 | C22—C23 | 1.393 (3) |
C17—C18 | 1.522 (2) | C22—H22 | 0.9300 |
C17—H17 | 0.9800 | C23—H23 | 0.9300 |
C9—C10 | 1.519 (2) | C16—H16A | 0.9700 |
C9—C8 | 1.560 (2) | C16—H16B | 0.9700 |
C9—H9 | 0.9800 | C12—C11 | 1.382 (3) |
C10—C11 | 1.386 (3) | C12—H12 | 0.9300 |
C10—C15 | 1.391 (2) | C11—H11 | 0.9300 |
C15—C14 | 1.384 (3) | C29—C28 | 1.382 (3) |
C15—H15 | 0.9300 | C29—H29 | 0.9300 |
C14—C13 | 1.364 (3) | C28—H28 | 0.9300 |
C14—H14 | 0.9300 | ||
C24—O1—C16 | 109.55 (12) | C1—C6—C5 | 117.92 (17) |
C16—N1—C9 | 110.20 (14) | C1—C6—C7 | 121.96 (15) |
C16—N1—C17 | 109.51 (14) | C5—C6—C7 | 119.91 (17) |
C9—N1—C17 | 108.58 (12) | C2—C1—C6 | 121.29 (18) |
C26—N2—C7 | 113.67 (14) | C2—C1—H1 | 119.4 |
C26—N2—H2A | 108.7 (14) | C6—C1—H1 | 119.4 |
C7—N2—H2A | 107.9 (14) | C3—C2—C1 | 118.7 (2) |
C29—C30—F4 | 118.5 (2) | C3—C2—H2 | 120.7 |
C29—C30—C31 | 122.6 (2) | C1—C2—H2 | 120.7 |
F4—C30—C31 | 118.9 (3) | N2—C7—C6 | 111.15 (14) |
C30—C31—C32 | 118.1 (2) | N2—C7—C8 | 108.58 (14) |
C30—C31—H31 | 120.9 | C6—C7—C8 | 111.19 (14) |
C32—C31—H31 | 120.9 | N2—C7—H7 | 108.6 |
C27—C32—C31 | 121.3 (2) | C6—C7—H7 | 108.6 |
C27—C32—H32 | 119.4 | C8—C7—H7 | 108.6 |
C31—C32—H32 | 119.4 | C24—C8—C7 | 108.82 (14) |
C32—C27—C28 | 118.39 (18) | C24—C8—C9 | 106.68 (13) |
C32—C27—C26 | 122.27 (17) | C7—C8—C9 | 113.95 (13) |
C28—C27—C26 | 119.34 (17) | C24—C8—H8 | 109.1 |
N2—C26—C27 | 111.59 (15) | C7—C8—H8 | 109.1 |
N2—C26—C25 | 108.53 (14) | C9—C8—H8 | 109.1 |
C27—C26—C25 | 112.33 (15) | O1—C24—C8 | 110.56 (14) |
N2—C26—H26 | 108.1 | O1—C24—C25 | 110.71 (14) |
C27—C26—H26 | 108.1 | C8—C24—C25 | 109.05 (14) |
C25—C26—H26 | 108.1 | O1—C24—H24 | 108.8 |
C24—C25—C26 | 108.06 (14) | C8—C24—H24 | 108.8 |
C24—C25—C17 | 106.99 (14) | C25—C24—H24 | 108.8 |
C26—C25—C17 | 113.51 (14) | C23—C18—C19 | 117.44 (18) |
C24—C25—H25 | 109.4 | C23—C18—C17 | 123.74 (18) |
C26—C25—H25 | 109.4 | C19—C18—C17 | 118.77 (17) |
C17—C25—H25 | 109.4 | C20—C19—C18 | 121.7 (2) |
N1—C17—C18 | 110.25 (14) | C20—C19—H19 | 119.1 |
N1—C17—C25 | 109.16 (13) | C18—C19—H19 | 119.1 |
C18—C17—C25 | 117.03 (15) | C21—C20—C19 | 118.5 (2) |
N1—C17—H17 | 106.6 | C21—C20—H20 | 120.8 |
C18—C17—H17 | 106.6 | C19—C20—H20 | 120.8 |
C25—C17—H17 | 106.6 | C20—C21—C22 | 122.5 (2) |
N1—C9—C10 | 111.25 (13) | C20—C21—F3 | 118.8 (2) |
N1—C9—C8 | 109.41 (13) | C22—C21—F3 | 118.7 (2) |
C10—C9—C8 | 115.73 (13) | C21—C22—C23 | 118.8 (2) |
N1—C9—H9 | 106.6 | C21—C22—H22 | 120.6 |
C10—C9—H9 | 106.6 | C23—C22—H22 | 120.6 |
C8—C9—H9 | 106.6 | C18—C23—C22 | 121.1 (2) |
C11—C10—C15 | 117.29 (16) | C18—C23—H23 | 119.5 |
C11—C10—C9 | 121.89 (15) | C22—C23—H23 | 119.5 |
C15—C10—C9 | 120.62 (15) | N1—C16—O1 | 112.99 (14) |
C14—C15—C10 | 121.28 (17) | N1—C16—H16A | 109.0 |
C14—C15—H15 | 119.4 | O1—C16—H16A | 109.0 |
C10—C15—H15 | 119.4 | N1—C16—H16B | 109.0 |
C13—C14—C15 | 118.81 (18) | O1—C16—H16B | 109.0 |
C13—C14—H14 | 120.6 | H16A—C16—H16B | 107.8 |
C15—C14—H14 | 120.6 | C13—C12—C11 | 118.35 (19) |
C12—C13—F2 | 119.30 (19) | C13—C12—H12 | 120.8 |
C12—C13—C14 | 122.19 (18) | C11—C12—H12 | 120.8 |
F2—C13—C14 | 118.50 (18) | C12—C11—C10 | 122.04 (18) |
F1—C3—C2 | 118.7 (2) | C12—C11—H11 | 119.0 |
F1—C3—C4 | 118.78 (19) | C10—C11—H11 | 119.0 |
C2—C3—C4 | 122.5 (2) | C30—C29—C28 | 118.8 (2) |
C3—C4—C5 | 118.24 (19) | C30—C29—H29 | 120.6 |
C3—C4—H4 | 120.9 | C28—C29—H29 | 120.6 |
C5—C4—H4 | 120.9 | C29—C28—C27 | 120.8 (2) |
C4—C5—C6 | 121.31 (19) | C29—C28—H28 | 119.6 |
C4—C5—H5 | 119.3 | C27—C28—H28 | 119.6 |
C6—C5—H5 | 119.3 | ||
C29—C30—C31—C32 | 0.1 (4) | C5—C6—C7—N2 | −156.40 (16) |
F4—C30—C31—C32 | −179.7 (2) | C1—C6—C7—C8 | −92.14 (19) |
C30—C31—C32—C27 | 0.1 (3) | C5—C6—C7—C8 | 82.51 (19) |
C31—C32—C27—C28 | −0.3 (3) | N2—C7—C8—C24 | 57.70 (17) |
C31—C32—C27—C26 | −179.76 (19) | C6—C7—C8—C24 | −179.72 (14) |
C7—N2—C26—C27 | −174.43 (14) | N2—C7—C8—C9 | −61.20 (18) |
C7—N2—C26—C25 | 61.26 (18) | C6—C7—C8—C9 | 61.39 (18) |
C32—C27—C26—N2 | −23.9 (2) | N1—C9—C8—C24 | −0.98 (17) |
C28—C27—C26—N2 | 156.61 (17) | C10—C9—C8—C24 | 125.64 (15) |
C32—C27—C26—C25 | 98.2 (2) | N1—C9—C8—C7 | 119.13 (15) |
C28—C27—C26—C25 | −81.2 (2) | C10—C9—C8—C7 | −114.26 (16) |
N2—C26—C25—C24 | −60.04 (18) | C16—O1—C24—C8 | 62.17 (18) |
C27—C26—C25—C24 | 176.10 (14) | C16—O1—C24—C25 | −58.79 (18) |
N2—C26—C25—C17 | 58.46 (19) | C7—C8—C24—O1 | 177.82 (13) |
C27—C26—C25—C17 | −65.41 (19) | C9—C8—C24—O1 | −58.83 (17) |
C16—N1—C17—C18 | 73.99 (17) | C7—C8—C24—C25 | −60.24 (18) |
C9—N1—C17—C18 | −165.64 (14) | C9—C8—C24—C25 | 63.11 (17) |
C16—N1—C17—C25 | −55.89 (17) | C26—C25—C24—O1 | −176.91 (13) |
C9—N1—C17—C25 | 64.48 (16) | C17—C25—C24—O1 | 60.51 (17) |
C24—C25—C17—N1 | −2.18 (18) | C26—C25—C24—C8 | 61.24 (18) |
C26—C25—C17—N1 | −121.29 (15) | C17—C25—C24—C8 | −61.34 (17) |
C24—C25—C17—C18 | −128.24 (15) | N1—C17—C18—C23 | −142.50 (18) |
C26—C25—C17—C18 | 112.65 (17) | C25—C17—C18—C23 | −17.0 (3) |
C16—N1—C9—C10 | −71.76 (17) | N1—C17—C18—C19 | 40.0 (2) |
C17—N1—C9—C10 | 168.30 (13) | C25—C17—C18—C19 | 165.47 (17) |
C16—N1—C9—C8 | 57.36 (17) | C23—C18—C19—C20 | 1.3 (3) |
C17—N1—C9—C8 | −62.58 (16) | C17—C18—C19—C20 | 178.99 (19) |
N1—C9—C10—C11 | 159.75 (16) | C18—C19—C20—C21 | −1.1 (4) |
C8—C9—C10—C11 | 34.1 (2) | C19—C20—C21—C22 | 0.0 (4) |
N1—C9—C10—C15 | −25.5 (2) | C19—C20—C21—F3 | 179.7 (2) |
C8—C9—C10—C15 | −151.19 (16) | C20—C21—C22—C23 | 0.7 (4) |
C11—C10—C15—C14 | −1.6 (3) | F3—C21—C22—C23 | −178.93 (18) |
C9—C10—C15—C14 | −176.61 (16) | C19—C18—C23—C22 | −0.5 (3) |
C10—C15—C14—C13 | 2.4 (3) | C17—C18—C23—C22 | −178.11 (18) |
C15—C14—C13—C12 | −1.4 (3) | C21—C22—C23—C18 | −0.4 (3) |
C15—C14—C13—F2 | 178.30 (17) | C9—N1—C16—O1 | −57.81 (19) |
F1—C3—C4—C5 | −179.50 (17) | C17—N1—C16—O1 | 61.56 (18) |
C2—C3—C4—C5 | −0.7 (3) | C24—O1—C16—N1 | −2.7 (2) |
C3—C4—C5—C6 | −0.9 (3) | F2—C13—C12—C11 | −179.99 (19) |
C4—C5—C6—C1 | 2.2 (3) | C14—C13—C12—C11 | −0.3 (3) |
C4—C5—C6—C7 | −172.63 (17) | C13—C12—C11—C10 | 1.1 (3) |
C5—C6—C1—C2 | −2.0 (3) | C15—C10—C11—C12 | −0.1 (3) |
C7—C6—C1—C2 | 172.73 (17) | C9—C10—C11—C12 | 174.80 (18) |
F1—C3—C2—C1 | 179.71 (18) | F4—C30—C29—C28 | 179.6 (2) |
C4—C3—C2—C1 | 0.9 (3) | C31—C30—C29—C28 | −0.3 (4) |
C6—C1—C2—C3 | 0.5 (3) | C30—C29—C28—C27 | 0.1 (3) |
C26—N2—C7—C6 | 177.57 (14) | C32—C27—C28—C29 | 0.2 (3) |
C26—N2—C7—C8 | −59.82 (18) | C26—C27—C28—C29 | 179.65 (19) |
C1—C6—C7—N2 | 28.9 (2) |
Cg5 and Cg6 are the centroids of the C1–C6 and C10–C15 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C31—H31···F1i | 0.93 | 2.51 | 3.231 (3) | 135 |
C8—H8···F3ii | 0.98 | 2.64 | 3.564 (2) | 158 |
C32—H32···F4iii | 0.93 | 2.66 | 3.567 (3) | 162 |
C1—H1···F4iii | 0.93 | 2.51 | 3.411 (2) | 161 |
N2—H2A···Cg5iv | 0.89 | 2.80 (2) | 3.6594 (18) | 161.7 (17) |
C2—H2···Cg6v | 0.93 | 2.68 | 3.552 (2) | 156 |
C11—H11···Cg5 | 0.93 | 2.87 | 3.514 (2) | 128 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x, −y, −z+1; (v) −x, −y+1, −z+1. |
Acknowledgements
The authors thank the DST and the SAIF, IIT Madras for X-ray crystallography facilities. They also thank Dr P. T. Muthiah (UGC-Emeritus Fellow) School of Chemistry, Bharathidasan University, Trichy and Dr M. Arunachalam, Department of Chemistry, The Gandhigram Rural Institute, for their helpful comments.
Funding information
The authors thank the University Grants Commission, New Delhi, for a Major Research Project [MRP; grant No. 42-358/2013 (SR)]) and a UGC-Special Assistance Programme (SAP).
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