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Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2016 Feb 3;72(Pt 3):283–286. doi: 10.1107/S2056989016001614

Crystal structure of 3-{5-[3-(4-fluoro­phen­yl)-1-isopropyl-1H-indol-2-yl]-1H-pyrazol-1-yl}indolin-2-one ethanol monosolvate

Md Lutfor Rahman a,*, Ajaykumar D Kulkarni b, Mashitah Mohd Yusoff a, Huey Chong Kwong c, Ching Kheng Quah d
PMCID: PMC4778816  PMID: 27006787

The title compound crystallizes as a 1:1 ethanol solvate, with the pyrazole ring almost normal to both of the indol-2-one ring and indole rings. In the crystal, mol­ecules are linked by pairs of N—H⋯O and O—H⋯O hydrogen bonds, forming an inversion mol­ecule–solvate dimer with an Inline graphic(12) ring motif.

Keywords: crystal structure, indol-2-one, pyrazole, indole, Schiff base, N—H⋯O and O—H⋯O hydrogen bonds, C—H⋯π inter­actions

Abstract

The title indolin-2-one compound, C28H23FN4O·C2H6O, crystallizes as a 1:1 ethanol solvate. The ethanol mol­ecule is disordered over two positions with refined site occupancies of 0.560 (14) and 0.440 (14). The pyrazole ring makes dihedral angles of 84.16 (10) and 85.33 (9)° with the indolin-2-one and indole rings, respectively, whereas the dihedral angle between indolin-2-one and indole rings is 57.30 (7)°. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming an inversion mol­ecule–solvate 2:2 dimer with R 4 4(12) ring motifs. The crystal structure is consolidated by π–π inter­action between pairs of inversion-related indolin-2-one rings [inter­planar spacing = 3.599 (2) Å].

Chemical context  

Heterocyclic compounds containing the pyrazolone nucleus, indole, and its derivatives play an important role in biological activities. The synthesis and biological activity of some new indole derivatives containing a pyrazole moiety have been reported (Raju et al., 2013 ▸). Pyrazole and its analogues have been found to exhibit industrial and biologically active applications (el-Kashef et al., 2000 ▸; Taha et al., 2001 ▸; Brzozowski & Sączewski,, 2002 ▸). Consequently, synthesis of indole derivatives has been a major topic in organic and medicinal chemistry over the past few decades. Nitro­gen-containing heterocycles are universal systems in nature and are consequently considered as privileged structures in drug discovery (Raju et al., 2013 ▸). A literature survey shows that some pyrazoles plays an essential role in biologically active compounds and also in medicinal chemistry (Penning et al., 2006 ▸), exhibiting phenomena such as anti­bacterial (Pevarello et al., 2006 ▸), anti­fungal, anti­viral (Meghashyam et al., 2011 ▸), anti-oxidant (Singarave & Sarkkarai, 2011 ▸), anti-inflammatory (Mana et al., 2010 ▸), and anti­cancer (Pathak et al., 2010 ▸) effects etc. Certain indole derivatives have also been reported to exhibit wide-spectrum activities such as anti­parkinsonian and anti­convulsant effects (Siddiqui et al., 2008 ▸; Archana et al., 2002 ▸). In addition, pyrazoles have played a crucial role in the development of theory in heterocyclic chemistry, and are also used extensively as useful synthons in organic synthesis. Isatin, an endogenous indole and its derivatives have been shown to exhibit a wide range of biological activities (Daisley & Shah, 1984 ▸; Pandeya et al., 1999 ▸). In addition, the biological significance of fluvastatin, an indole derivative, is well established (Repič et al., 2001 ▸). As part of our studies in this area, we now present a pyrazole as a central unit linked with 3-[3-(4-fluoro­phen­yl)-1-iso­propyl­indolin-2-yl]acryl­aldehyde and 3-hydrazonoindolin-2-one, synthesized according to a procedure reported in the literature (Elkanzi, 2013 ▸).graphic file with name e-72-00283-scheme1.jpg

Structural commentary  

The asymmetric unit of the title compound (Fig. 1 ▸) comprises of a 3-{5-[3-(4-fluoro­phen­yl)-1-isopropyl-1H-indol-2-yl]-1H-pyrazol-1-yl}indolin-2-one and an ethanol solvent mol­ecule. The pyrrolidin-2-one ring has an essentially planar conformation, with maximum deviation from the mean plane of the ring of 0.04 (2) Å at C25. The pyrazole ring is almost planar [maximum deviation of ±0.006 (2) Å for atoms N2 and C15], as are the fluoro­phenyl [maximum deviation of ± 0.011 (2) Å for atoms C10 and C13] and indole [maximum deviation of ± 0.0019 (2) Å for atom C14] rings. The connecting pyrazole ring is almost normal to both indol-2-one and indole rings with dihedral angles of 84.16 (10)° and 85.33 (9)°, respectively, while the indole and fluoro­phenyl rings are tilted toward one another by 40.74 (8)°. The bond lengths and angles in the fluoro­phenyl-indole moiety of the title mol­ecule are comparable to those of previously reported compounds (Kulkarni et al., 2015a ▸,b ▸).

Figure 1.

Figure 1

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The mol­ecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Only the major component of the disordered ethanol solvent mol­ecule is shown.

Supra­molecular features  

In the crystal, the main mol­ecules and ethanol solvate mol­ecules are linked via pairs of N4—H1N1⋯O2 and O2—H1O2⋯O1 hydrogen bonds (Table 1 ▸), forming an inversion-related mol­ecule-solvate 2:2 dimer with an Inline graphic(12) ring motif (Fig. 2 ▸) (Bernstein et al., 1995 ▸). The crystal structure also features π–π inter­actions between pairs of inversion-related (1 − x, 1 − y, 1 − z) indolin-2-one rings with an inter­planar spacing of 3.599 (2) Å.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N4—H1N1⋯O2i 0.85 (2) 1.92 (3) 2.750 (19) 165 (2)
O2—H1O2⋯O1ii 0.98 (9) 1.67 (9) 2.650 (2) 172 (11)
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Symmetry codes: (i) Inline graphic; (ii) Inline graphic.

Figure 2.

Figure 2

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The crystal packing of the title compound viewed along the b axis. The N—H⋯O and O—H⋯O hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Database survey  

A search of the Cambridge Structural Database (CSD, Version 35.6, last update May 2015; Groom & Allen, 2014 ▸) using 4-(λ1-azan­yl)-5-methyl-2,4-di­hydro-3H-1,2,4-triazole-3-thione as the main skeleton, revealed the presence of 57 structures containing the triazole-thione moiety but only four structures containing the fluvastatin nucleus. These include 5-[3-(4-fluoro­phen­yl)-1-isopropyl-1H-indol-2-yl]-1-(X)penta-2,4-diene-1-one, where X = 4-nitro­phenyl (NUHNAH), 2-hy­droxy­phenyl (NUHNEL), 4-meth­oxy­phenyl (NUHNIP) and 4-chloro­phenyl (NUHNOV) (Kalalbandi et al., 2015 ▸). In these four compounds, the 4-fluoro­phenyl ring of the fluvastatin nucleus is inclined to the indole ring by dihedral angles ranging from ca 46.66 to 68.59°, compared to 40.74 (8)° for the title compound.

Synthesis and crystallization  

The title compound was synthesized by refluxing a hot methano­lic solution (30 mL) of 3-(3-(4-fluoro­phen­yl)-1-iso­propyl­indolin-2-yl)acryl­aldehyde (0.01mol) and a hot methano­lic solution (30 mL) of 3-hydrazonoeindolin-2-one (0.01mol) for 5 h with addition of 4 drops of conc. hydro­chloric acid (Ajaykumar et al., 2009 ▸). The product obtained after evaporation of the solvent was filtered, washed with cold MeOH and recrystallized from ETOH. The single crystal used for the crystal analysis was grown by the slow evaporation of a solution in chloro­form–ethanol (1:1). Yield (m.p.): 78% (551 K). 1HNMR (CDCl3) in p.p.m.: 7.94 (s, 1H, NH, indole), 7.76 (d, 1H, Ar-H), 7.72 (m, 2H, Ar–H), 7.37 (m, 2H, Ar-H), 7.32 (t, 1H, Ar-H), 7.20 (t, 1H, Ar-H), 7.13 (d, 1H, Ar-H), 7.10 (d, 2H, Ar-H), 6.77 (t, 1H, Ar-H), 6.70 (d, 1H, Ar-H), 6.67 (d, 1H, pyrazole), 5.48 (d, 2H, pyrazole), 5.37 (s, 1H, indole), 4.73 (m, 1H, isoprop­yl), 1.73 (m, 6H, meth­yl). IR (KBr) cm−1: 3250 (N—H, indole), 2827 (–CH3), 1720 (C=O, ketone), 1618 (C=C, Ar), 1520 (C—C, Ar), 1469 (–CH3), 1221 (C—N).

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The ethanol mol­ecule is disordered over two positions with refined site occupancies of 0.560 (14): 0.440 (14). The disorder components were restrained to have similar geometry. The N-bound H atom was located in a difference Fourier map and freely refined. The C-bound H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model with U iso(H) = 1.5U eq(C-meth­yl) and 1.2U eq(C) for other H atoms.

Table 2. Experimental details.

Crystal data
Chemical formula C28H23FN4O·C2H6O
M r 496.57
Crystal system, space group Triclinic, P Inline graphic
Temperature (K) 297
a, b, c (Å) 9.9754 (8), 10.2139 (8), 14.0294 (11)
α, β, γ (°) 75.7386 (15), 71.0062 (14), 83.1264 (14)
V (Å3) 1308.73 (18)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.42 × 0.22 × 0.22
 
Data collection
Diffractometer Bruker APEXII DUO CCD area detector
Absorption correction Multi-scan (SADABS; Bruker, 2009 ▸)
T min, T max 0.884, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections 32072, 5778, 3733
R int 0.032
(sin θ/λ)max (Å−1) 0.650
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.057, 0.130, 1.21
No. of reflections 5778
No. of parameters 375
No. of restraints 3
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.15, −0.19
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Computer programs: APEX2 (Bruker, 2009 ▸), SAINT (Bruker, 2009 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2013 (Sheldrick, 2015 ▸), Mercury (Macrae et al., 2008 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016001614/pk2572sup1.cif

e-72-00283-sup1.cif (1MB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016001614/pk2572Isup2.hkl

e-72-00283-Isup2.hkl (316.7KB, hkl)
Click here for additional data file. (9.7KB, cml)

Supporting information file. DOI: 10.1107/S2056989016001614/pk2572Isup3.cml

CCDC reference: 1450044

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

This research was supported by a PRGS Research Grant (No. RDU 130121).

supplementary crystallographic information

Crystal data

C28H23FN4O·C2H6O Z = 2
Mr = 496.57 F(000) = 524
Triclinic, P1 Dx = 1.260 Mg m−3
a = 9.9754 (8) Å Mo Kα radiation, λ = 0.71073 Å
b = 10.2139 (8) Å Cell parameters from 9792 reflections
c = 14.0294 (11) Å θ = 2.3–27.6°
α = 75.7386 (15)° µ = 0.09 mm−1
β = 71.0062 (14)° T = 297 K
γ = 83.1264 (14)° Block, colourless
V = 1308.73 (18) Å3 0.42 × 0.22 × 0.22 mm
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Data collection

Bruker APEXII DUO CCD area-detector diffractometer 5778 independent reflections
Radiation source: fine-focus sealed tube 3733 reflections with I > 2σ(I)
Graphite monochromator Rint = 0.032
φ and ω scans θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009) h = −12→12
Tmin = 0.884, Tmax = 0.955 k = −13→13
32072 measured reflections l = −18→18
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Refinement

Refinement on F2 3 restraints
Least-squares matrix: full Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.057 H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130 w = 1/[σ2(Fo2) + (0.0361P)2 + 0.3328P] where P = (Fo2 + 2Fc2)/3
S = 1.21 (Δ/σ)max < 0.001
5778 reflections Δρmax = 0.15 e Å−3
375 parameters Δρmin = −0.19 e Å−3
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Special details

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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq Occ. (<1)
F1 0.95103 (15) 0.08376 (14) 0.14670 (13) 0.0965 (5)
N1 0.37863 (16) 0.67252 (16) 0.16316 (12) 0.0496 (4)
H1N1 0.596 (2) 0.795 (2) 0.5053 (16) 0.059*
N2 0.66480 (15) 0.68580 (15) 0.23475 (11) 0.0477 (4)
N3 0.77904 (17) 0.76065 (17) 0.21225 (13) 0.0571 (4)
N4 0.5929 (2) 0.7342 (2) 0.47443 (14) 0.0662 (5)
O1 0.47523 (17) 0.85895 (18) 0.36321 (13) 0.0801 (5)
C1 0.28456 (19) 0.5768 (2) 0.17372 (14) 0.0500 (5)
C2 0.1405 (2) 0.5909 (3) 0.18238 (16) 0.0638 (6)
H2A 0.0924 0.6749 0.1806 0.077*
C3 0.0725 (2) 0.4771 (3) 0.19350 (18) 0.0732 (7)
H3A −0.0236 0.4841 0.1996 0.088*
C4 0.1431 (2) 0.3511 (3) 0.19594 (18) 0.0706 (6)
H4A 0.0935 0.2756 0.2038 0.085*
C5 0.2849 (2) 0.3364 (2) 0.18689 (16) 0.0587 (5)
H5A 0.3316 0.2518 0.1882 0.070*
C6 0.35815 (19) 0.45041 (19) 0.17569 (13) 0.0468 (4)
C7 0.50280 (18) 0.47104 (18) 0.16459 (13) 0.0436 (4)
C8 0.62068 (19) 0.36889 (18) 0.16080 (14) 0.0452 (4)
C9 0.6011 (2) 0.2407 (2) 0.22518 (16) 0.0565 (5)
H9A 0.5122 0.2197 0.2725 0.068*
C10 0.7109 (2) 0.1441 (2) 0.22023 (19) 0.0671 (6)
H10A 0.6964 0.0579 0.2624 0.081*
C11 0.8413 (2) 0.1780 (2) 0.15208 (19) 0.0640 (6)
C12 0.8657 (2) 0.3021 (2) 0.08737 (18) 0.0613 (5)
H12A 0.9556 0.3225 0.0416 0.074*
C13 0.75482 (19) 0.3966 (2) 0.09108 (16) 0.0522 (5)
H13A 0.7699 0.4809 0.0460 0.063*
C14 0.51043 (18) 0.60667 (18) 0.15671 (13) 0.0432 (4)
C15 0.63180 (18) 0.68060 (17) 0.14957 (14) 0.0428 (4)
C16 0.7318 (2) 0.75366 (19) 0.06796 (15) 0.0547 (5)
H16A 0.7398 0.7686 −0.0018 0.066*
C17 0.8187 (2) 0.8008 (2) 0.11080 (16) 0.0549 (5)
H17A 0.8957 0.8543 0.0725 0.066*
C18 0.5866 (2) 0.6370 (2) 0.34278 (14) 0.0502 (5)
H18A 0.5028 0.5904 0.3490 0.060*
C19 0.6725 (2) 0.5487 (2) 0.40595 (14) 0.0523 (5)
C20 0.7444 (2) 0.4273 (2) 0.39863 (18) 0.0666 (6)
H20A 0.7423 0.3823 0.3490 0.080*
C21 0.8208 (3) 0.3727 (3) 0.4674 (2) 0.0833 (7)
H21A 0.8715 0.2906 0.4632 0.100*
C22 0.8225 (3) 0.4381 (3) 0.5413 (2) 0.0877 (8)
H22A 0.8746 0.3998 0.5863 0.105*
C23 0.7486 (3) 0.5592 (3) 0.55029 (17) 0.0770 (7)
H23A 0.7489 0.6030 0.6010 0.092*
C24 0.6745 (2) 0.6130 (2) 0.48173 (15) 0.0583 (5)
C25 0.5419 (2) 0.7586 (2) 0.39376 (17) 0.0593 (5)
C26 0.3559 (2) 0.8204 (2) 0.14204 (17) 0.0607 (5)
H26A 0.4430 0.8576 0.1401 0.073*
C27 0.2370 (3) 0.8682 (3) 0.2271 (2) 0.0910 (8)
H27A 0.2350 0.9651 0.2145 0.137*
H27B 0.2526 0.8299 0.2925 0.137*
H27C 0.1480 0.8401 0.2281 0.137*
C28 0.3389 (3) 0.8721 (3) 0.0352 (2) 0.0960 (9)
H28A 0.3347 0.9691 0.0190 0.144*
H28B 0.2529 0.8400 0.0341 0.144*
H28C 0.4183 0.8397 −0.0149 0.144*
O2 0.3483 (14) 0.060 (2) 0.4525 (12) 0.115 (5) 0.560 (14)
H1O2 0.401 (10) −0.016 (8) 0.423 (8) 0.138* 0.560 (14)
C29 0.1962 (7) 0.0616 (11) 0.4632 (7) 0.088 (2) 0.560 (14)
H29A 0.1654 0.1480 0.4274 0.106* 0.560 (14)
H29B 0.1769 −0.0096 0.4353 0.106* 0.560 (14)
C30 0.1250 (16) 0.039 (2) 0.5740 (8) 0.186 (9) 0.560 (14)
H30A 0.0243 0.0400 0.5871 0.279* 0.560 (14)
H30B 0.1468 0.1100 0.6001 0.279* 0.560 (14)
H30C 0.1569 −0.0464 0.6078 0.279* 0.560 (14)
O2A 0.3340 (15) 0.080 (2) 0.4359 (12) 0.077 (3) 0.440 (14)
H2O2 0.384 (13) 0.024 (9) 0.415 (9) 0.092* 0.440 (14)
C29A 0.2173 (11) −0.0028 (13) 0.5152 (12) 0.101 (4) 0.440 (14)
H29C 0.1718 −0.0491 0.4822 0.121* 0.440 (14)
H29D 0.2550 −0.0699 0.5632 0.121* 0.440 (14)
C30A 0.1171 (11) 0.089 (2) 0.5688 (13) 0.128 (6) 0.440 (14)
H30D 0.0319 0.0425 0.6102 0.192* 0.440 (14)
H30E 0.0953 0.1644 0.5194 0.192* 0.440 (14)
H30F 0.1573 0.1195 0.6124 0.192* 0.440 (14)
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
F1 0.0752 (9) 0.0731 (9) 0.1446 (14) 0.0267 (7) −0.0456 (9) −0.0283 (9)
N1 0.0461 (9) 0.0524 (9) 0.0552 (9) 0.0063 (8) −0.0226 (7) −0.0154 (7)
N2 0.0442 (9) 0.0535 (9) 0.0478 (9) −0.0089 (7) −0.0156 (7) −0.0103 (7)
N3 0.0507 (10) 0.0629 (11) 0.0610 (11) −0.0173 (8) −0.0171 (8) −0.0129 (8)
N4 0.0666 (12) 0.0836 (14) 0.0578 (11) −0.0107 (10) −0.0164 (9) −0.0328 (10)
O1 0.0743 (11) 0.0801 (11) 0.0922 (12) 0.0141 (9) −0.0286 (9) −0.0347 (10)
C1 0.0439 (11) 0.0653 (12) 0.0441 (10) 0.0005 (9) −0.0173 (8) −0.0139 (9)
C2 0.0469 (12) 0.0835 (16) 0.0632 (13) 0.0037 (11) −0.0217 (10) −0.0167 (11)
C3 0.0428 (12) 0.110 (2) 0.0685 (15) −0.0097 (13) −0.0182 (11) −0.0177 (14)
C4 0.0574 (14) 0.0905 (18) 0.0691 (15) −0.0241 (13) −0.0209 (11) −0.0151 (12)
C5 0.0551 (12) 0.0682 (13) 0.0579 (12) −0.0115 (10) −0.0187 (10) −0.0172 (10)
C6 0.0435 (10) 0.0590 (12) 0.0415 (10) −0.0048 (9) −0.0152 (8) −0.0136 (8)
C7 0.0439 (10) 0.0496 (10) 0.0415 (10) −0.0010 (8) −0.0165 (8) −0.0139 (8)
C8 0.0456 (10) 0.0481 (11) 0.0489 (11) −0.0003 (8) −0.0200 (8) −0.0168 (9)
C9 0.0552 (12) 0.0539 (12) 0.0599 (12) −0.0033 (10) −0.0186 (10) −0.0103 (10)
C10 0.0733 (15) 0.0502 (12) 0.0804 (16) 0.0023 (11) −0.0345 (13) −0.0066 (11)
C11 0.0553 (13) 0.0572 (13) 0.0909 (17) 0.0167 (11) −0.0365 (12) −0.0273 (12)
C12 0.0465 (12) 0.0613 (13) 0.0792 (15) 0.0015 (10) −0.0182 (10) −0.0244 (12)
C13 0.0480 (11) 0.0476 (11) 0.0623 (12) −0.0003 (9) −0.0169 (9) −0.0156 (9)
C14 0.0428 (10) 0.0486 (10) 0.0417 (10) 0.0023 (8) −0.0172 (8) −0.0126 (8)
C15 0.0440 (10) 0.0412 (10) 0.0469 (10) 0.0044 (8) −0.0189 (8) −0.0131 (8)
C16 0.0605 (12) 0.0545 (12) 0.0474 (11) −0.0048 (10) −0.0153 (10) −0.0085 (9)
C17 0.0509 (11) 0.0497 (11) 0.0587 (13) −0.0071 (9) −0.0102 (10) −0.0091 (9)
C18 0.0468 (11) 0.0604 (12) 0.0463 (11) −0.0129 (9) −0.0132 (9) −0.0133 (9)
C19 0.0498 (11) 0.0611 (12) 0.0459 (11) −0.0156 (10) −0.0143 (9) −0.0056 (9)
C20 0.0711 (14) 0.0623 (14) 0.0647 (14) −0.0098 (12) −0.0221 (12) −0.0062 (11)
C21 0.0802 (17) 0.0738 (16) 0.0876 (19) −0.0054 (13) −0.0323 (15) 0.0069 (14)
C22 0.0842 (18) 0.106 (2) 0.0709 (17) −0.0246 (17) −0.0405 (14) 0.0165 (16)
C23 0.0804 (17) 0.104 (2) 0.0514 (13) −0.0295 (15) −0.0261 (12) −0.0049 (13)
C24 0.0553 (12) 0.0755 (15) 0.0457 (11) −0.0182 (11) −0.0141 (9) −0.0107 (10)
C25 0.0486 (12) 0.0704 (14) 0.0597 (13) −0.0066 (11) −0.0112 (10) −0.0215 (11)
C26 0.0644 (13) 0.0514 (12) 0.0739 (14) 0.0118 (10) −0.0336 (11) −0.0173 (10)
C27 0.0857 (18) 0.0839 (18) 0.113 (2) 0.0301 (15) −0.0360 (16) −0.0465 (16)
C28 0.133 (2) 0.0728 (17) 0.090 (2) 0.0009 (16) −0.0625 (19) 0.0015 (14)
O2 0.070 (5) 0.111 (9) 0.192 (12) 0.006 (4) −0.033 (6) −0.099 (9)
C29 0.081 (5) 0.095 (5) 0.094 (5) −0.007 (3) −0.031 (4) −0.025 (4)
C30 0.175 (13) 0.31 (2) 0.089 (7) −0.110 (12) −0.025 (7) −0.046 (9)
O2A 0.064 (7) 0.082 (5) 0.085 (4) −0.007 (5) −0.006 (4) −0.041 (3)
C29A 0.089 (7) 0.106 (8) 0.109 (9) −0.013 (5) −0.018 (6) −0.038 (7)
C30A 0.041 (5) 0.148 (9) 0.186 (14) −0.015 (5) 0.006 (6) −0.071 (8)
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Geometric parameters (Å, º)

F1—C11 1.364 (2) C17—H17A 0.9300
N1—C1 1.384 (2) C18—C19 1.500 (3)
N1—C14 1.389 (2) C18—C25 1.532 (3)
N1—C26 1.470 (2) C18—H18A 0.9800
N2—C15 1.353 (2) C19—C20 1.365 (3)
N2—N3 1.356 (2) C19—C24 1.386 (3)
N2—C18 1.451 (2) C20—C21 1.391 (3)
N3—C17 1.317 (2) C20—H20A 0.9300
N4—C25 1.344 (3) C21—C22 1.370 (4)
N4—C24 1.399 (3) C21—H21A 0.9300
N4—H1N1 0.85 (2) C22—C23 1.374 (4)
O1—C25 1.218 (3) C22—H22A 0.9300
C1—C2 1.395 (3) C23—C24 1.371 (3)
C1—C6 1.406 (3) C23—H23A 0.9300
C2—C3 1.367 (3) C26—C27 1.515 (3)
C2—H2A 0.9300 C26—C28 1.519 (3)
C3—C4 1.389 (3) C26—H26A 0.9800
C3—H3A 0.9300 C27—H27A 0.9600
C4—C5 1.371 (3) C27—H27B 0.9600
C4—H4A 0.9300 C27—H27C 0.9600
C5—C6 1.398 (3) C28—H28A 0.9600
C5—H5A 0.9300 C28—H28B 0.9600
C6—C7 1.436 (2) C28—H28C 0.9600
C7—C14 1.372 (2) O2—C29 1.474 (13)
C7—C8 1.472 (2) O2—H1O2 0.99 (9)
C8—C13 1.389 (3) C29—C30 1.456 (12)
C8—C9 1.390 (3) C29—H29A 0.9700
C9—C10 1.380 (3) C29—H29B 0.9700
C9—H9A 0.9300 C30—H30A 0.9600
C10—C11 1.364 (3) C30—H30B 0.9600
C10—H10A 0.9300 C30—H30C 0.9600
C11—C12 1.361 (3) O2A—C29A 1.497 (13)
C12—C13 1.375 (3) O2A—H2O2 0.76 (10)
C12—H12A 0.9300 C29A—C30A 1.438 (14)
C13—H13A 0.9300 C29A—H29C 0.9700
C14—C15 1.466 (2) C29A—H29D 0.9700
C15—C16 1.370 (3) C30A—H30D 0.9600
C16—C17 1.388 (3) C30A—H30E 0.9600
C16—H16A 0.9300 C30A—H30F 0.9600
C1—N1—C14 107.55 (15) C25—C18—H18A 110.2
C1—N1—C26 127.68 (16) C20—C19—C24 120.1 (2)
C14—N1—C26 123.80 (16) C20—C19—C18 131.91 (19)
C15—N2—N3 112.64 (15) C24—C19—C18 107.96 (18)
C15—N2—C18 129.00 (15) C19—C20—C21 118.2 (2)
N3—N2—C18 117.92 (15) C19—C20—H20A 120.9
C17—N3—N2 104.16 (15) C21—C20—H20A 120.9
C25—N4—C24 111.97 (18) C22—C21—C20 120.9 (3)
C25—N4—H1N1 122.7 (14) C22—C21—H21A 119.5
C24—N4—H1N1 122.9 (14) C20—C21—H21A 119.5
N1—C1—C2 130.23 (19) C21—C22—C23 121.3 (2)
N1—C1—C6 108.26 (15) C21—C22—H22A 119.4
C2—C1—C6 121.50 (19) C23—C22—H22A 119.4
C3—C2—C1 117.7 (2) C24—C23—C22 117.5 (2)
C3—C2—H2A 121.2 C24—C23—H23A 121.3
C1—C2—H2A 121.2 C22—C23—H23A 121.3
C2—C3—C4 121.7 (2) C23—C24—C19 122.0 (2)
C2—C3—H3A 119.1 C23—C24—N4 128.3 (2)
C4—C3—H3A 119.1 C19—C24—N4 109.66 (18)
C5—C4—C3 121.0 (2) O1—C25—N4 127.7 (2)
C5—C4—H4A 119.5 O1—C25—C18 124.8 (2)
C3—C4—H4A 119.5 N4—C25—C18 107.5 (2)
C4—C5—C6 119.0 (2) N1—C26—C27 112.74 (19)
C4—C5—H5A 120.5 N1—C26—C28 110.06 (18)
C6—C5—H5A 120.5 C27—C26—C28 113.7 (2)
C5—C6—C1 119.09 (17) N1—C26—H26A 106.6
C5—C6—C7 133.46 (18) C27—C26—H26A 106.6
C1—C6—C7 107.45 (16) C28—C26—H26A 106.6
C14—C7—C6 106.08 (15) C26—C27—H27A 109.5
C14—C7—C8 126.39 (16) C26—C27—H27B 109.5
C6—C7—C8 127.53 (16) H27A—C27—H27B 109.5
C13—C8—C9 117.72 (17) C26—C27—H27C 109.5
C13—C8—C7 121.00 (17) H27A—C27—H27C 109.5
C9—C8—C7 121.27 (17) H27B—C27—H27C 109.5
C10—C9—C8 121.3 (2) C26—C28—H28A 109.5
C10—C9—H9A 119.4 C26—C28—H28B 109.5
C8—C9—H9A 119.4 H28A—C28—H28B 109.5
C11—C10—C9 118.5 (2) C26—C28—H28C 109.5
C11—C10—H10A 120.8 H28A—C28—H28C 109.5
C9—C10—H10A 120.8 H28B—C28—H28C 109.5
C12—C11—F1 118.5 (2) C29—O2—H1O2 111 (6)
C12—C11—C10 122.39 (19) C30—C29—O2 104.6 (11)
F1—C11—C10 119.1 (2) C30—C29—H29A 110.8
C11—C12—C13 118.7 (2) O2—C29—H29A 110.8
C11—C12—H12A 120.7 C30—C29—H29B 110.8
C13—C12—H12A 120.7 O2—C29—H29B 110.8
C12—C13—C8 121.40 (19) H29A—C29—H29B 108.9
C12—C13—H13A 119.3 C29—C30—H30A 109.5
C8—C13—H13A 119.3 C29—C30—H30B 109.5
C7—C14—N1 110.64 (16) H30A—C30—H30B 109.5
C7—C14—C15 128.66 (16) C29—C30—H30C 109.5
N1—C14—C15 120.57 (15) H30A—C30—H30C 109.5
N2—C15—C16 105.47 (16) H30B—C30—H30C 109.5
N2—C15—C14 121.55 (16) C29A—O2A—H2O2 99 (10)
C16—C15—C14 132.98 (17) C30A—C29A—O2A 107.1 (13)
C15—C16—C17 105.79 (18) C30A—C29A—H29C 110.3
C15—C16—H16A 127.1 O2A—C29A—H29C 110.3
C17—C16—H16A 127.1 C30A—C29A—H29D 110.3
N3—C17—C16 111.93 (18) O2A—C29A—H29D 110.3
N3—C17—H17A 124.0 H29C—C29A—H29D 108.5
C16—C17—H17A 124.0 C29A—C30A—H30D 109.5
N2—C18—C19 114.71 (15) C29A—C30A—H30E 109.5
N2—C18—C25 108.29 (16) H30D—C30A—H30E 109.5
C19—C18—C25 102.81 (16) C29A—C30A—H30F 109.5
N2—C18—H18A 110.2 H30D—C30A—H30F 109.5
C19—C18—H18A 110.2 H30E—C30A—H30F 109.5
C15—N2—N3—C17 −0.9 (2) N3—N2—C15—C16 1.2 (2)
C18—N2—N3—C17 −174.05 (16) C18—N2—C15—C16 173.39 (17)
C14—N1—C1—C2 −179.41 (19) N3—N2—C15—C14 −179.04 (15)
C26—N1—C1—C2 −10.4 (3) C18—N2—C15—C14 −6.9 (3)
C14—N1—C1—C6 1.1 (2) C7—C14—C15—N2 −82.5 (2)
C26—N1—C1—C6 170.05 (17) N1—C14—C15—N2 93.0 (2)
N1—C1—C2—C3 −179.1 (2) C7—C14—C15—C16 97.1 (3)
C6—C1—C2—C3 0.4 (3) N1—C14—C15—C16 −87.3 (2)
C1—C2—C3—C4 −0.2 (3) N2—C15—C16—C17 −1.0 (2)
C2—C3—C4—C5 −0.2 (4) C14—C15—C16—C17 179.33 (18)
C3—C4—C5—C6 0.4 (3) N2—N3—C17—C16 0.3 (2)
C4—C5—C6—C1 −0.2 (3) C15—C16—C17—N3 0.5 (2)
C4—C5—C6—C7 180.0 (2) C15—N2—C18—C19 129.10 (19)
N1—C1—C6—C5 179.39 (16) N3—N2—C18—C19 −59.1 (2)
C2—C1—C6—C5 −0.2 (3) C15—N2—C18—C25 −116.7 (2)
N1—C1—C6—C7 −0.7 (2) N3—N2—C18—C25 55.1 (2)
C2—C1—C6—C7 179.69 (17) N2—C18—C19—C20 −61.1 (3)
C5—C6—C7—C14 180.0 (2) C25—C18—C19—C20 −178.4 (2)
C1—C6—C7—C14 0.11 (19) N2—C18—C19—C24 117.45 (18)
C5—C6—C7—C8 0.8 (3) C25—C18—C19—C24 0.1 (2)
C1—C6—C7—C8 −179.11 (17) C24—C19—C20—C21 −1.3 (3)
C14—C7—C8—C13 −40.8 (3) C18—C19—C20—C21 177.1 (2)
C6—C7—C8—C13 138.22 (19) C19—C20—C21—C22 0.8 (4)
C14—C7—C8—C9 140.51 (19) C20—C21—C22—C23 0.2 (4)
C6—C7—C8—C9 −40.4 (3) C21—C22—C23—C24 −0.8 (4)
C13—C8—C9—C10 0.0 (3) C22—C23—C24—C19 0.3 (3)
C7—C8—C9—C10 178.73 (18) C22—C23—C24—N4 −179.4 (2)
C8—C9—C10—C11 1.6 (3) C20—C19—C24—C23 0.8 (3)
C9—C10—C11—C12 −1.7 (3) C18—C19—C24—C23 −177.95 (19)
C9—C10—C11—F1 179.68 (19) C20—C19—C24—N4 −179.49 (18)
F1—C11—C12—C13 178.76 (18) C18—C19—C24—N4 1.8 (2)
C10—C11—C12—C13 0.1 (3) C25—N4—C24—C23 176.4 (2)
C11—C12—C13—C8 1.6 (3) C25—N4—C24—C19 −3.3 (2)
C9—C8—C13—C12 −1.7 (3) C24—N4—C25—O1 −175.0 (2)
C7—C8—C13—C12 179.65 (17) C24—N4—C25—C18 3.3 (2)
C6—C7—C14—N1 0.55 (19) N2—C18—C25—O1 54.6 (3)
C8—C7—C14—N1 179.78 (16) C19—C18—C25—O1 176.3 (2)
C6—C7—C14—C15 176.46 (17) N2—C18—C25—N4 −123.82 (18)
C8—C7—C14—C15 −4.3 (3) C19—C18—C25—N4 −2.0 (2)
C1—N1—C14—C7 −1.0 (2) C1—N1—C26—C27 62.8 (3)
C26—N1—C14—C7 −170.54 (16) C14—N1—C26—C27 −129.9 (2)
C1—N1—C14—C15 −177.30 (15) C1—N1—C26—C28 −65.4 (3)
C26—N1—C14—C15 13.2 (3) C14—N1—C26—C28 102.0 (2)
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Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
N4—H1N1···O2i 0.85 (2) 1.92 (3) 2.750 (19) 165 (2)
O2—H1O2···O1ii 0.98 (9) 1.67 (9) 2.650 (2) 172 (11)
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Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z.

References

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016001614/pk2572sup1.cif

e-72-00283-sup1.cif (1MB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016001614/pk2572Isup2.hkl

e-72-00283-Isup2.hkl (316.7KB, hkl)
Click here for additional data file. (9.7KB, cml)

Supporting information file. DOI: 10.1107/S2056989016001614/pk2572Isup3.cml

CCDC reference: 1450044

Additional supporting information: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography

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