research communications
Structural, Hirshfeld surface and three-dimensional interaction-energy studies of 1,3,5-triethyl 2-amino-3,5-dicyano-4,6-bis(4-fluorophenyl)cyclohex-1-ene-1,3,5-tricarboxylate
aDepartment of Physics, Adichunchanagiri Institute of Technology, Chikkamagaluru 577102, Karnataka, India, bDepartment of Physics, Rajeev Institute of Technology, Hassan 573201, Karnataka, India, cDepartment of Physics, Government Engineering College, Bedarapura, Chamarajanagara 571313, Karnataka, India, and dAlkem Laboratories Ltd, R&D Centre, Industrial Estate, 4th Phase, Bangalore, Karnataka, India
*Correspondence e-mail: bnlphysics@gmail.com
In the title compound, C29H27F2N3O6, which crystallizes in the monoclinic P21/c, the cyclohexenone ring is puckered and adopts an The features various intermolecular interactions, such as N—H⋯O, C—H⋯N and C—H⋯O. These interactions were investigated using Hirshfeld surface analysis and the three-dimensional interaction energies were calculated using the B3LYP/6–31 G(d,p) energy density model.
Keywords: single-crystal XRD; envelope conformation; Hirshfeld surfaces; three-dimensional interaction energies.
CCDC reference: 2202315
1. Chemical context
Organic compounds containing hetero atoms such as fluorine, nitrogen, sulfur and oxygen exhibit significant biological activities such as antioxidant (Fu et al., 2010), insecticidal (Carbonnelle et al., 2005), antibacterial, antifungal (Sener et al., 2000), anti-inflammatory (Khanum et al., 2004), anticonvulsant, analgesic and antitumor (Kushwaha et al., 2011). These compounds find a wide range of applications in the fields of agriculture and biochemistry as well as in the pharmaceuticals industry. Hence, hetero organic compounds have attracted the attention of chemists with the aim of designing and synthesizing new organic compounds. The title compound was synthesized, its structure was studied by X-ray diffraction techniques and a computational analysis was performed to understand the intermolecular interactions.
2. Structural commentary
In the title compound (Fig. 1), the cyclohexenone ring (C1–C6) is puckered [maximum puckering amplitude Q = 0.554 (4) (3) Å and exhibits an on atom C2 (Cremer & Pople, 1975). The bond lengths and bond angles agree with those of previously reported related compounds (Gunasekaran et al., 2009; Mertsalov et al., 2021; Chandana et al., 2021; Ganesha, Sreenatha et al., 2023; Ganesha, Nizamuddin et al., 2023; Ganesha et al., 2022; Sreenatha et al., 2018, 2020, 2022; Lakshminarayana et al., 2009, 2010, 2022; Madan Kumar et al., 2018; HariPrasada et al., 2023). The dihedral angle between the mean plane of the cyclohexenone (C1–C6) and fluorobenzene rings (C7–C12 and C17–C22) are 62.3 (2) and 84.9 (2)°, respectively, confirming the non-planarity of the molecule and also the equatorial orientation of the rings. The carboxylate group at the C2 position is oriented +syn-clinical, --anti-clinical, +anti-clinical and –syn-clinical to the mean plane of the C1–C6 ring with torsion angles C1—C2—C13—O2 = 50.3 (4)°, C1—C2—C13—O1 = −131.3 (4)°, C3—C2—C13—O1 = 110.6 (4)° and C3—C2—C13—O2 = −67.8 (4)°. The orientation of other two carboxylate groups at the C4 and C5 positions are described by the torsion angles C1—C6—C27—O6 = −15.4 (5)° (–syn-periplanar), C1—C6—C27—O5 = 167.2 (4)° (+anti-periplanar), C5—C6—C27—O5 = −17.2 (6)° (–anti-periplanar), C5—C6—C27—O6 = 160.1 (3)° (+anti-periplanar) and C3—C4—C23—O3 = 44.9 (5)° (+syn-clinal), C3—C4—C23—O4 = −136.4 (3)° (–anti-clinal), C5—C4—C23—O3 = −75.8 (4)° (–syn-clinal), C5—C4—C23—O4 = 102.9 (3)° (+anti-clinal). The orientation is due to the intermolecular N—H⋯O and C—H⋯O interactions.
3. Supramolecular features
In the crystal, the molecules are held together by an intermolecular interactions of the types N1—H2N⋯O1, C14—H14B⋯N3, and C24—H24B⋯O3 (Table 1), enclosing an R22(10) closed ring motif, propagating along the [101] direction (Figs. 2 and 3).
4. Database survey
A survey of the Cambridge Structural Database (CSD version 5.41, update of November 2022; Groom et al., 2016) reveals one nearly comparable derivative, triethyl 2-(5-nitro-2H-indazol-2-yl)propane-1,2,3-tricarboxylate (NUPQAS; Boulhaoua et al., 2015) in which intermolecular C—H⋯O and C—H⋯N bonds are observed.
5. Hirshfeld surfaces and 2D fingerprint calculations
The Hirshfeld surface (HS) mapped over dnorm was generated using CrystalExplorer17.5 (Spackman et al., 2009) with a colour scale of −0.3124 a.u. for red to +1.7877 a.u. for blue. The area and volume of the dnorm surface are 681.46 Å2 and 527.71 Å3, respectively. The front and rear views of the Hirshfeld surface mapped over dnorm are depicted in Fig. 4. The bright-red circular spots on dnorm indicates the presence of intermolecular N1—H2N⋯O1, C14—H14B⋯N3 and C24—H24B⋯O3 interactions. The percentage contribution from different intermolecular interactions towards the formation of a three dimensional Hirshfeld surface (HS) was computed using two-dimensional fingerprint calculations (Fig. 5). The results showed that the H⋯H (40.1%) contacts make the major contribution to the crystal packing, while the C⋯H (11.2%), N⋯H (14.7%), H⋯F (16.3%), H⋯O (14.5%) contacts also make a significant contribution to the total area of the HS surface.
6. Three-dimensional-framework analysis of interaction energies
CrystalExplorer 17.5 software calculates interaction energies between crystal molecular pairs. Energy calculations were carried out using the B3LYP/6-31G(d,p) basis set within a default radius of 3.8 Å (Turner et al., 2015, 2017; Gavezzotti, 2002; Grimme, 2006). The interaction of different molecules with the reference molecule (black ball-and-stick model at the centre) in the cluster of energy frameworks is depicted in Fig. 6. Fig. 7 depicts the energy frameworks, visualizing the strength of the interactions, with the Coulombic, dispersion and total energies shown in red, green and blue, respectively. The radii of the cylinders connecting the centroids of the molecules indicate the relative strengths of the interaction energies. A table of interaction energies in component form is given in the table in Fig. 6. The highest total interaction energy (Etot = −67.4 kJ mol−1) is associated with a pair of yellow molecules with the short centroid distance R = 9.29 Å with rotational symmetry −x, y + , −z + , while the lowest total interaction energy (Etot = −17.6 kJ mol−1) was observed for a pair of green molecules interacting at the longer centroid distance R = 12.86 Å; this is in accordance with the classical laws of electrostatics. In each of the energy terms, the dispersion component is dominant over the others.
7. Synthesis and crystallization
Piperidine (6 mmol) was added to ethyl cyanoacetate (30 mmol) and the mixture was stirred for 10 min. Then 4-fluorobenzaldehyde (20 mmol) was added dropwise and during the addition, the temperature of the reaction mass rose to 333 K (it should not be cooled), and the mass was stirred for 30 min. The temperature slowly came down to 293–298 K over 30 min. The progress of the reaction was monitored by TLC and found to be complete. Methylene chloride (30 ml) and water (20 ml) were added and the mixture was stirred for 10 min. The organic layer was separated and washed with sat. aq. NaCl solution and dried over anhydrous Na2SO4, then concentrated under reduced pressure to get the crude product. This was purified by silica gel using n-heptane/ethyl acetate as The mixture was quenched in cold water and the organic layer was extracted with ethyl acetate, washed with 5% sodium bicarbonate solution, and dried over anhydrous sodium sulfate. Slow evaporation of the solvent lead to crystals of the title compound, which were recrystallized from ethanol solution.
8. Refinement
Crystal data, data collection and structure . H atoms were placed at idealized positions and allowed to ride on their parent atoms with C—H distances in the range 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms).
details are summarized in Table 2Supporting information
CCDC reference: 2202315
https://doi.org/10.1107/S2056989023003134/ex2065sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023003134/ex2065Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023003134/ex2065Isup3.cml
Data collection: APEX3 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXL2018/3 (Sheldrick, 2015b); software used to prepare material for publication: PLATON (Spek, 2020).C29H27F2N3O6 | F(000) = 1152 |
Mr = 551.53 | Dx = 1.328 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.0884 (11) Å | Cell parameters from 3477 reflections |
b = 17.0492 (16) Å | θ = 2.9–25.1° |
c = 13.5966 (11) Å | µ = 0.10 mm−1 |
β = 100.008 (3)° | T = 297 K |
V = 2759.6 (4) Å3 | Block, colorless |
Z = 4 | 0.14 × 0.09 × 0.04 mm |
Bruker Kappa APEXIII PHOTON II diffractometer | Rint = 0.141 |
Radiation source: fine focus sealed tube | θmax = 25.0°, θmin = 2.9° |
φ and ω scans | h = −14→14 |
52965 measured reflections | k = −20→20 |
4869 independent reflections | l = −16→15 |
3477 reflections with I > 2σ(I) |
Refinement on F2 | 47 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.214 | w = 1/[σ2(Fo2) + (0.095P)2 + 2.1236P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
4869 reflections | Δρmax = 0.32 e Å−3 |
386 parameters | Δρmin = −0.30 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 | Occ. (<1) | |
C1 | 0.7198 (3) | 0.2207 (2) | 0.2001 (3) | 0.0240 (8) | |
H1 | 0.727769 | 0.231041 | 0.130783 | 0.029* | |
C2 | 0.6104 (3) | 0.2626 (2) | 0.2181 (2) | 0.0235 (8) | |
C3 | 0.5101 (3) | 0.2230 (2) | 0.1488 (2) | 0.0234 (8) | |
H3 | 0.532115 | 0.221020 | 0.082740 | 0.028* | |
C4 | 0.4967 (3) | 0.1361 (2) | 0.1785 (3) | 0.0253 (8) | |
C5 | 0.6106 (3) | 0.0939 (2) | 0.2085 (3) | 0.0285 (8) | |
C6 | 0.7102 (3) | 0.1323 (2) | 0.2112 (3) | 0.0264 (8) | |
C7 | 0.8219 (3) | 0.2567 (2) | 0.2671 (3) | 0.0286 (8) | |
C8 | 0.8565 (3) | 0.2338 (2) | 0.3650 (3) | 0.0403 (10) | |
H8 | 0.817146 | 0.194409 | 0.391282 | 0.048* | |
C9 | 0.9480 (4) | 0.2679 (3) | 0.4252 (4) | 0.0531 (12) | |
H9 | 0.970380 | 0.252113 | 0.491150 | 0.064* | |
C10 | 1.0048 (4) | 0.3258 (3) | 0.3841 (4) | 0.0601 (14) | |
C11 | 0.9741 (4) | 0.3508 (3) | 0.2875 (4) | 0.0521 (13) | |
H11 | 1.013665 | 0.390343 | 0.261732 | 0.062* | |
C12 | 0.8822 (3) | 0.3153 (2) | 0.2293 (3) | 0.0378 (10) | |
H12 | 0.860441 | 0.331096 | 0.163341 | 0.045* | |
C13 | 0.6100 (3) | 0.3501 (2) | 0.1913 (3) | 0.0290 (8) | |
C14 | 0.6296 (6) | 0.4404 (3) | 0.0641 (5) | 0.085 (2) | |
H14A | 0.553966 | 0.451275 | 0.029724 | 0.102* | |
H14B | 0.646142 | 0.476250 | 0.120125 | 0.102* | |
C15 | 0.7038 (9) | 0.4537 (4) | −0.0001 (7) | 0.143 (4) | |
H15A | 0.697339 | 0.507096 | −0.022647 | 0.215* | |
H15B | 0.779025 | 0.444078 | 0.033956 | 0.215* | |
H15C | 0.686851 | 0.419104 | −0.056445 | 0.215* | |
C16 | 0.6009 (3) | 0.2580 (2) | 0.3251 (3) | 0.0282 (8) | |
C17 | 0.3999 (3) | 0.2679 (2) | 0.1335 (3) | 0.0255 (8) | |
C18 | 0.3455 (3) | 0.2816 (3) | 0.0369 (3) | 0.0428 (11) | |
H18 | 0.378204 | 0.264155 | −0.016208 | 0.051* | |
C19 | 0.2441 (4) | 0.3203 (3) | 0.0172 (4) | 0.0556 (13) | |
H19 | 0.208054 | 0.328936 | −0.048125 | 0.067* | |
C20 | 0.1976 (3) | 0.3458 (3) | 0.0969 (4) | 0.0489 (12) | |
C21 | 0.2487 (3) | 0.3355 (2) | 0.1932 (4) | 0.0430 (11) | |
H21 | 0.215853 | 0.354255 | 0.245598 | 0.052* | |
C22 | 0.3500 (3) | 0.2967 (2) | 0.2117 (3) | 0.0352 (9) | |
H22 | 0.385888 | 0.289508 | 0.277302 | 0.042* | |
C23 | 0.4342 (3) | 0.0933 (2) | 0.0843 (3) | 0.0303 (9) | |
C24 | 0.2967 (4) | −0.0024 (3) | 0.0223 (4) | 0.0538 (13) | |
H24A | 0.268639 | 0.030494 | −0.034869 | 0.065* | |
H24B | 0.348193 | −0.040468 | 0.002475 | 0.065* | |
C25 | 0.2039 (5) | −0.0422 (4) | 0.0563 (4) | 0.0697 (16) | |
H25A | 0.164771 | −0.074136 | 0.003303 | 0.105* | |
H25B | 0.232526 | −0.074708 | 0.112636 | 0.105* | |
H25C | 0.153279 | −0.004020 | 0.075435 | 0.105* | |
C26 | 0.4322 (3) | 0.1278 (2) | 0.2620 (3) | 0.0312 (9) | |
C27 | 0.8120 (3) | 0.0845 (2) | 0.2178 (3) | 0.0356 (9) | |
C28 | 0.998 (3) | 0.084 (2) | 0.1734 (17) | 0.058 (5) | 0.345 (12) |
H28A | 1.029815 | 0.108563 | 0.120192 | 0.070* | 0.345 (12) |
H28B | 0.984697 | 0.029090 | 0.158581 | 0.070* | 0.345 (12) |
C29 | 1.0710 (15) | 0.0958 (13) | 0.2720 (15) | 0.084 (5) | 0.345 (12) |
H29A | 1.142674 | 0.071719 | 0.271532 | 0.126* | 0.345 (12) |
H29B | 1.081077 | 0.150867 | 0.285153 | 0.126* | 0.345 (12) |
H29C | 1.036386 | 0.072146 | 0.323178 | 0.126* | 0.345 (12) |
C28' | 1.0074 (13) | 0.0836 (10) | 0.2141 (11) | 0.063 (3) | 0.655 (12) |
H28C | 1.016442 | 0.061117 | 0.280600 | 0.076* | 0.655 (12) |
H28D | 1.013141 | 0.041797 | 0.166848 | 0.076* | 0.655 (12) |
C29' | 1.0950 (6) | 0.1438 (6) | 0.2095 (8) | 0.070 (3) | 0.655 (12) |
H29D | 1.167949 | 0.120150 | 0.225539 | 0.105* | 0.655 (12) |
H29E | 1.085169 | 0.165536 | 0.143452 | 0.105* | 0.655 (12) |
H29F | 1.088455 | 0.184765 | 0.256673 | 0.105* | 0.655 (12) |
F1 | 1.0955 (3) | 0.3596 (2) | 0.4425 (3) | 0.0998 (13) | |
F2 | 0.0967 (2) | 0.3833 (2) | 0.0775 (3) | 0.0818 (10) | |
N1 | 0.5985 (3) | 0.01657 (19) | 0.2255 (3) | 0.0421 (9) | |
H1N | 0.658 (3) | −0.013 (2) | 0.240 (3) | 0.050* | |
H2N | 0.536 (2) | −0.010 (2) | 0.215 (3) | 0.050* | |
N2 | 0.5956 (3) | 0.2536 (2) | 0.4077 (3) | 0.0475 (10) | |
N3 | 0.3848 (3) | 0.1197 (2) | 0.3262 (3) | 0.0478 (10) | |
O1 | 0.5874 (3) | 0.40133 (16) | 0.2450 (2) | 0.0477 (8) | |
O2 | 0.6346 (3) | 0.36003 (16) | 0.1017 (2) | 0.0444 (8) | |
O3 | 0.4589 (3) | 0.10243 (19) | 0.0037 (2) | 0.0515 (9) | |
O4 | 0.3547 (2) | 0.04598 (17) | 0.10520 (19) | 0.0394 (7) | |
O5 | 0.8213 (3) | 0.01601 (17) | 0.2428 (3) | 0.0567 (9) | |
O6 | 0.8963 (2) | 0.12367 (16) | 0.1887 (2) | 0.0464 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0252 (19) | 0.0198 (18) | 0.0296 (19) | 0.0023 (15) | 0.0116 (15) | −0.0003 (15) |
C2 | 0.0297 (19) | 0.0174 (17) | 0.0250 (18) | 0.0007 (15) | 0.0095 (15) | 0.0000 (14) |
C3 | 0.0286 (19) | 0.0199 (18) | 0.0238 (18) | 0.0012 (15) | 0.0109 (15) | −0.0016 (14) |
C4 | 0.0258 (19) | 0.0227 (19) | 0.0297 (19) | 0.0009 (15) | 0.0112 (15) | 0.0006 (15) |
C5 | 0.035 (2) | 0.0190 (18) | 0.033 (2) | −0.0016 (16) | 0.0098 (16) | −0.0033 (15) |
C6 | 0.031 (2) | 0.0200 (18) | 0.0295 (19) | 0.0007 (16) | 0.0084 (15) | −0.0031 (15) |
C7 | 0.0266 (19) | 0.0179 (18) | 0.042 (2) | 0.0016 (15) | 0.0066 (16) | −0.0019 (16) |
C8 | 0.038 (2) | 0.028 (2) | 0.054 (3) | −0.0041 (18) | 0.006 (2) | −0.0009 (19) |
C9 | 0.043 (3) | 0.055 (3) | 0.057 (3) | 0.001 (2) | −0.005 (2) | −0.010 (2) |
C10 | 0.035 (3) | 0.054 (3) | 0.089 (4) | −0.007 (2) | 0.003 (3) | −0.030 (3) |
C11 | 0.035 (2) | 0.031 (2) | 0.094 (4) | −0.012 (2) | 0.023 (3) | −0.015 (2) |
C12 | 0.031 (2) | 0.028 (2) | 0.057 (3) | 0.0002 (18) | 0.0158 (19) | 0.0007 (19) |
C13 | 0.0242 (19) | 0.0237 (19) | 0.040 (2) | −0.0014 (16) | 0.0065 (16) | −0.0012 (17) |
C14 | 0.125 (5) | 0.039 (3) | 0.102 (5) | 0.024 (3) | 0.049 (4) | 0.042 (3) |
C15 | 0.218 (10) | 0.061 (4) | 0.180 (8) | 0.010 (5) | 0.113 (8) | 0.055 (5) |
C16 | 0.027 (2) | 0.025 (2) | 0.033 (2) | 0.0031 (15) | 0.0077 (16) | −0.0020 (16) |
C17 | 0.0251 (19) | 0.0210 (18) | 0.031 (2) | −0.0038 (15) | 0.0060 (15) | 0.0016 (15) |
C18 | 0.040 (2) | 0.050 (3) | 0.038 (2) | 0.009 (2) | 0.0066 (19) | 0.002 (2) |
C19 | 0.046 (3) | 0.070 (3) | 0.047 (3) | 0.014 (3) | −0.002 (2) | 0.011 (2) |
C20 | 0.025 (2) | 0.042 (3) | 0.078 (4) | 0.0076 (19) | 0.001 (2) | 0.004 (2) |
C21 | 0.030 (2) | 0.036 (2) | 0.065 (3) | 0.0027 (19) | 0.016 (2) | −0.007 (2) |
C22 | 0.031 (2) | 0.034 (2) | 0.042 (2) | 0.0045 (18) | 0.0097 (18) | −0.0013 (18) |
C23 | 0.029 (2) | 0.025 (2) | 0.038 (2) | −0.0019 (16) | 0.0098 (17) | −0.0040 (16) |
C24 | 0.048 (3) | 0.061 (3) | 0.054 (3) | −0.024 (2) | 0.013 (2) | −0.032 (2) |
C25 | 0.064 (3) | 0.075 (4) | 0.068 (3) | −0.037 (3) | 0.005 (3) | −0.005 (3) |
C26 | 0.034 (2) | 0.0210 (19) | 0.040 (2) | −0.0043 (16) | 0.0117 (18) | −0.0006 (16) |
C27 | 0.036 (2) | 0.019 (2) | 0.052 (3) | 0.0042 (17) | 0.0066 (19) | −0.0006 (18) |
C28 | 0.021 (6) | 0.054 (6) | 0.100 (12) | 0.014 (5) | 0.010 (9) | −0.010 (10) |
C29 | 0.043 (8) | 0.086 (10) | 0.118 (11) | −0.001 (8) | 0.000 (8) | −0.017 (9) |
C28' | 0.027 (5) | 0.057 (4) | 0.105 (10) | 0.012 (4) | 0.008 (7) | −0.008 (8) |
C29' | 0.031 (4) | 0.075 (6) | 0.105 (7) | −0.002 (4) | 0.011 (4) | −0.003 (5) |
F1 | 0.058 (2) | 0.097 (3) | 0.131 (3) | −0.0340 (19) | −0.0192 (19) | −0.035 (2) |
F2 | 0.0386 (16) | 0.087 (2) | 0.115 (3) | 0.0305 (16) | 0.0012 (16) | −0.003 (2) |
N1 | 0.036 (2) | 0.0187 (18) | 0.072 (3) | −0.0024 (15) | 0.0125 (19) | 0.0036 (17) |
N2 | 0.056 (2) | 0.055 (2) | 0.034 (2) | 0.0074 (19) | 0.0148 (17) | 0.0013 (17) |
N3 | 0.060 (2) | 0.046 (2) | 0.045 (2) | −0.0092 (19) | 0.030 (2) | −0.0024 (17) |
O1 | 0.064 (2) | 0.0228 (15) | 0.059 (2) | 0.0075 (14) | 0.0186 (16) | −0.0112 (14) |
O2 | 0.064 (2) | 0.0279 (15) | 0.0453 (17) | 0.0084 (14) | 0.0213 (15) | 0.0111 (13) |
O3 | 0.063 (2) | 0.059 (2) | 0.0383 (17) | −0.0270 (17) | 0.0225 (15) | −0.0144 (15) |
O4 | 0.0377 (16) | 0.0429 (16) | 0.0396 (16) | −0.0169 (13) | 0.0127 (12) | −0.0084 (13) |
O5 | 0.0423 (18) | 0.0280 (17) | 0.100 (3) | 0.0084 (14) | 0.0130 (17) | 0.0077 (16) |
O6 | 0.0277 (15) | 0.0306 (15) | 0.085 (2) | 0.0050 (12) | 0.0201 (15) | −0.0051 (15) |
C1—C6 | 1.520 (5) | C17—C22 | 1.399 (5) |
C1—C7 | 1.530 (5) | C18—C19 | 1.377 (6) |
C1—C2 | 1.559 (5) | C18—H18 | 0.9300 |
C1—H1 | 0.9800 | C19—C20 | 1.375 (7) |
C2—C16 | 1.480 (5) | C19—H19 | 0.9300 |
C2—C13 | 1.535 (5) | C20—C21 | 1.359 (6) |
C2—C3 | 1.555 (5) | C20—F2 | 1.362 (5) |
C3—C17 | 1.520 (5) | C21—C22 | 1.375 (6) |
C3—C4 | 1.551 (5) | C21—H21 | 0.9300 |
C3—H3 | 0.9800 | C22—H22 | 0.9300 |
C4—C26 | 1.491 (5) | C23—O3 | 1.194 (4) |
C4—C5 | 1.545 (5) | C23—O4 | 1.322 (4) |
C4—C23 | 1.552 (5) | C24—C25 | 1.453 (6) |
C5—N1 | 1.351 (5) | C24—O4 | 1.472 (5) |
C5—C6 | 1.365 (5) | C24—H24A | 0.9700 |
C6—C27 | 1.466 (5) | C24—H24B | 0.9700 |
C7—C8 | 1.380 (6) | C25—H25A | 0.9600 |
C7—C12 | 1.387 (5) | C25—H25B | 0.9600 |
C8—C9 | 1.385 (6) | C25—H25C | 0.9600 |
C8—H8 | 0.9300 | C26—N3 | 1.133 (5) |
C9—C10 | 1.376 (7) | C27—O5 | 1.216 (5) |
C9—H9 | 0.9300 | C27—O6 | 1.334 (5) |
C10—F1 | 1.365 (5) | C28—O6 | 1.45 (3) |
C10—C11 | 1.369 (7) | C28—C29 | 1.484 (18) |
C11—C12 | 1.386 (6) | C28—H28A | 0.9700 |
C11—H11 | 0.9300 | C28—H28B | 0.9700 |
C12—H12 | 0.9300 | C29—H29A | 0.9600 |
C13—O1 | 1.200 (4) | C29—H29B | 0.9600 |
C13—O2 | 1.314 (4) | C29—H29C | 0.9600 |
C14—C15 | 1.375 (8) | C28'—C29' | 1.484 (14) |
C14—O2 | 1.460 (5) | C28'—O6 | 1.494 (18) |
C14—H14A | 0.9700 | C28'—H28C | 0.9700 |
C14—H14B | 0.9700 | C28'—H28D | 0.9700 |
C15—H15A | 0.9600 | C29'—H29D | 0.9600 |
C15—H15B | 0.9600 | C29'—H29E | 0.9600 |
C15—H15C | 0.9600 | C29'—H29F | 0.9600 |
C16—N2 | 1.139 (5) | N1—H1N | 0.874 (19) |
C17—C18 | 1.383 (5) | N1—H2N | 0.875 (19) |
C6—C1—C7 | 113.9 (3) | C22—C17—C3 | 123.8 (3) |
C6—C1—C2 | 110.9 (3) | C19—C18—C17 | 121.7 (4) |
C7—C1—C2 | 109.9 (3) | C19—C18—H18 | 119.1 |
C6—C1—H1 | 107.2 | C17—C18—H18 | 119.1 |
C7—C1—H1 | 107.2 | C20—C19—C18 | 118.0 (4) |
C2—C1—H1 | 107.2 | C20—C19—H19 | 121.0 |
C16—C2—C13 | 106.7 (3) | C18—C19—H19 | 121.0 |
C16—C2—C3 | 112.8 (3) | C21—C20—F2 | 119.2 (4) |
C13—C2—C3 | 107.9 (3) | C21—C20—C19 | 122.6 (4) |
C16—C2—C1 | 110.1 (3) | F2—C20—C19 | 118.1 (4) |
C13—C2—C1 | 112.1 (3) | C20—C21—C22 | 118.6 (4) |
C3—C2—C1 | 107.4 (3) | C20—C21—H21 | 120.7 |
C17—C3—C4 | 112.8 (3) | C22—C21—H21 | 120.7 |
C17—C3—C2 | 115.9 (3) | C21—C22—C17 | 121.2 (4) |
C4—C3—C2 | 111.2 (3) | C21—C22—H22 | 119.4 |
C17—C3—H3 | 105.3 | C17—C22—H22 | 119.4 |
C4—C3—H3 | 105.3 | O3—C23—O4 | 125.7 (4) |
C2—C3—H3 | 105.3 | O3—C23—C4 | 122.1 (3) |
C26—C4—C5 | 108.3 (3) | O4—C23—C4 | 112.1 (3) |
C26—C4—C3 | 112.4 (3) | C25—C24—O4 | 108.0 (4) |
C5—C4—C3 | 112.6 (3) | C25—C24—H24A | 110.1 |
C26—C4—C23 | 109.9 (3) | O4—C24—H24A | 110.1 |
C5—C4—C23 | 106.4 (3) | C25—C24—H24B | 110.1 |
C3—C4—C23 | 107.0 (3) | O4—C24—H24B | 110.1 |
N1—C5—C6 | 125.8 (4) | H24A—C24—H24B | 108.4 |
N1—C5—C4 | 112.4 (3) | C24—C25—H25A | 109.5 |
C6—C5—C4 | 121.7 (3) | C24—C25—H25B | 109.5 |
C5—C6—C27 | 117.6 (3) | H25A—C25—H25B | 109.5 |
C5—C6—C1 | 123.7 (3) | C24—C25—H25C | 109.5 |
C27—C6—C1 | 118.6 (3) | H25A—C25—H25C | 109.5 |
C8—C7—C12 | 118.0 (4) | H25B—C25—H25C | 109.5 |
C8—C7—C1 | 122.6 (3) | N3—C26—C4 | 178.2 (4) |
C12—C7—C1 | 119.3 (4) | O5—C27—O6 | 121.7 (4) |
C7—C8—C9 | 121.9 (4) | O5—C27—C6 | 125.9 (4) |
C7—C8—H8 | 119.0 | O6—C27—C6 | 112.4 (3) |
C9—C8—H8 | 119.0 | O6—C28—C29 | 101.3 (19) |
C10—C9—C8 | 117.7 (5) | O6—C28—H28A | 111.5 |
C10—C9—H9 | 121.2 | C29—C28—H28A | 111.5 |
C8—C9—H9 | 121.2 | O6—C28—H28B | 111.5 |
F1—C10—C11 | 118.9 (5) | C29—C28—H28B | 111.5 |
F1—C10—C9 | 118.3 (5) | H28A—C28—H28B | 109.3 |
C11—C10—C9 | 122.8 (4) | C28—C29—H29A | 109.5 |
C10—C11—C12 | 117.9 (4) | C28—C29—H29B | 109.5 |
C10—C11—H11 | 121.0 | H29A—C29—H29B | 109.5 |
C12—C11—H11 | 121.0 | C28—C29—H29C | 109.5 |
C11—C12—C7 | 121.6 (4) | H29A—C29—H29C | 109.5 |
C11—C12—H12 | 119.2 | H29B—C29—H29C | 109.5 |
C7—C12—H12 | 119.2 | C29'—C28'—O6 | 107.0 (12) |
O1—C13—O2 | 125.6 (4) | C29'—C28'—H28C | 110.3 |
O1—C13—C2 | 123.7 (3) | O6—C28'—H28C | 110.3 |
O2—C13—C2 | 110.7 (3) | C29'—C28'—H28D | 110.3 |
C15—C14—O2 | 112.7 (5) | O6—C28'—H28D | 110.3 |
C15—C14—H14A | 109.1 | H28C—C28'—H28D | 108.6 |
O2—C14—H14A | 109.1 | C28'—C29'—H29D | 109.5 |
C15—C14—H14B | 109.1 | C28'—C29'—H29E | 109.5 |
O2—C14—H14B | 109.1 | H29D—C29'—H29E | 109.5 |
H14A—C14—H14B | 107.8 | C28'—C29'—H29F | 109.5 |
C14—C15—H15A | 109.5 | H29D—C29'—H29F | 109.5 |
C14—C15—H15B | 109.5 | H29E—C29'—H29F | 109.5 |
H15A—C15—H15B | 109.5 | C5—N1—H1N | 120 (3) |
C14—C15—H15C | 109.5 | C5—N1—H2N | 127 (3) |
H15A—C15—H15C | 109.5 | H1N—N1—H2N | 113 (4) |
H15B—C15—H15C | 109.5 | C13—O2—C14 | 116.3 (4) |
N2—C16—C2 | 178.5 (4) | C23—O4—C24 | 116.4 (3) |
C18—C17—C22 | 117.8 (3) | C27—O6—C28 | 121.5 (14) |
C18—C17—C3 | 118.4 (3) | C27—O6—C28' | 113.9 (6) |
C6—C1—C2—C16 | 70.5 (4) | C8—C7—C12—C11 | −0.5 (6) |
C7—C1—C2—C16 | −56.4 (4) | C1—C7—C12—C11 | 178.8 (3) |
C6—C1—C2—C13 | −171.0 (3) | C16—C2—C13—O1 | −10.8 (5) |
C7—C1—C2—C13 | 62.1 (4) | C3—C2—C13—O1 | 110.6 (4) |
C6—C1—C2—C3 | −52.6 (4) | C1—C2—C13—O1 | −131.3 (4) |
C7—C1—C2—C3 | −179.6 (3) | C16—C2—C13—O2 | 170.8 (3) |
C16—C2—C3—C17 | 74.3 (4) | C3—C2—C13—O2 | −67.8 (4) |
C13—C2—C3—C17 | −43.3 (4) | C1—C2—C13—O2 | 50.3 (4) |
C1—C2—C3—C17 | −164.3 (3) | C4—C3—C17—C18 | −102.1 (4) |
C16—C2—C3—C4 | −56.4 (4) | C2—C3—C17—C18 | 128.1 (4) |
C13—C2—C3—C4 | −173.9 (3) | C4—C3—C17—C22 | 78.1 (4) |
C1—C2—C3—C4 | 65.1 (3) | C2—C3—C17—C22 | −51.8 (5) |
C17—C3—C4—C26 | −49.1 (4) | C22—C17—C18—C19 | −1.7 (6) |
C2—C3—C4—C26 | 83.1 (4) | C3—C17—C18—C19 | 178.5 (4) |
C17—C3—C4—C5 | −171.8 (3) | C17—C18—C19—C20 | 0.3 (7) |
C2—C3—C4—C5 | −39.6 (4) | C18—C19—C20—C21 | 1.2 (7) |
C17—C3—C4—C23 | 71.6 (3) | C18—C19—C20—F2 | −179.2 (4) |
C2—C3—C4—C23 | −156.2 (3) | F2—C20—C21—C22 | 179.2 (4) |
C26—C4—C5—N1 | 60.7 (4) | C19—C20—C21—C22 | −1.2 (7) |
C3—C4—C5—N1 | −174.3 (3) | C20—C21—C22—C17 | −0.3 (6) |
C23—C4—C5—N1 | −57.4 (4) | C18—C17—C22—C21 | 1.7 (6) |
C26—C4—C5—C6 | −122.6 (4) | C3—C17—C22—C21 | −178.5 (4) |
C3—C4—C5—C6 | 2.4 (5) | C26—C4—C23—O3 | 167.2 (4) |
C23—C4—C5—C6 | 119.3 (4) | C5—C4—C23—O3 | −75.7 (5) |
N1—C5—C6—C27 | 10.0 (6) | C3—C4—C23—O3 | 44.9 (5) |
C4—C5—C6—C27 | −166.2 (3) | C26—C4—C23—O4 | −14.0 (4) |
N1—C5—C6—C1 | −174.7 (4) | C5—C4—C23—O4 | 103.0 (3) |
C4—C5—C6—C1 | 9.1 (5) | C3—C4—C23—O4 | −136.4 (3) |
C7—C1—C6—C5 | 142.1 (3) | C5—C6—C27—O5 | −17.2 (6) |
C2—C1—C6—C5 | 17.4 (5) | C1—C6—C27—O5 | 167.2 (4) |
C7—C1—C6—C27 | −42.7 (4) | C5—C6—C27—O6 | 160.1 (3) |
C2—C1—C6—C27 | −167.4 (3) | C1—C6—C27—O6 | −15.4 (5) |
C6—C1—C7—C8 | −41.2 (5) | O1—C13—O2—C14 | −2.4 (6) |
C2—C1—C7—C8 | 84.0 (4) | C2—C13—O2—C14 | 176.0 (4) |
C6—C1—C7—C12 | 139.5 (3) | C15—C14—O2—C13 | 150.1 (7) |
C2—C1—C7—C12 | −95.3 (4) | O3—C23—O4—C24 | 3.5 (6) |
C12—C7—C8—C9 | 0.4 (6) | C4—C23—O4—C24 | −175.1 (3) |
C1—C7—C8—C9 | −179.0 (4) | C25—C24—O4—C23 | −172.8 (4) |
C7—C8—C9—C10 | −0.3 (7) | O5—C27—O6—C28 | 7.9 (11) |
C8—C9—C10—F1 | −179.7 (4) | C6—C27—O6—C28 | −169.6 (10) |
C8—C9—C10—C11 | 0.3 (7) | O5—C27—O6—C28' | −14.7 (9) |
F1—C10—C11—C12 | 179.5 (4) | C6—C27—O6—C28' | 167.8 (7) |
C9—C10—C11—C12 | −0.5 (7) | C29—C28—O6—C27 | −94 (2) |
C10—C11—C12—C7 | 0.6 (6) | C29'—C28'—O6—C27 | −161.1 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14B···N3i | 0.97 | 2.60 | 3.420 (7) | 143 |
C24—H24B···O3ii | 0.97 | 2.58 | 3.483 (6) | 156 |
N1—H1N···O5 | 0.87 (2) | 2.03 (4) | 2.662 (5) | 128 (4) |
N1—H2N···O1iii | 0.88 (2) | 2.25 (3) | 3.064 (4) | 155 (4) |
N1—H2N···O4 | 0.88 (2) | 2.61 (4) | 3.152 (5) | 121 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y, −z; (iii) −x+1, y−1/2, −z+1/2. |
Acknowledgements
The authors are thankful for Department of Physics, Adichunchanagiri Institute of Technology, Chikkamagaluru, Karnataka, India, for support and also thank the SAIF, IIT Madras, Chennai-36,Tamil Nadu, India, for the data collection.
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