research communications
Syntheses and crystal structures of three salts of sparfloxacin, one incorporating extended tapes of fused pentagonal water assemblies
aDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysore-570 005, India, bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, and cDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
*Correspondence e-mail: Passion49432005@gmail.com, yathirajan@hotmail.com
Three organic salts of sparfloxacin, a difluorinated third-generation fluoroquinolone antibiotic, have been synthesized and their crystal structures determined. The salts, sparfloxacinium 4-nitrobenzoate dihydrate, C19H23F2N4O3+·C7H4NO4−·2H2O (I), sparfloxacinium 2-phenylacetate, C19H23F2N4O3+·C8H7O2− (II), and sparfloxacinium 4-methylbenzoate trihydrate, C19H23F2N4O3+·C8H7O2−·3H2O (III), exhibit similar inter-species packing interactions. The overall crystal structures each, however, have their own distinct characteristics, which are described here along with a Hirshfeld surface analysis of the various atom–atom contacts involving the sparfloxacinium cations. In the of III, an extended supramolecular tape of edge-fused hydrogen-bonded water pentagons was found. These pentagonal water and tape motifs are compared to related constructs in a broad selection of structure types, ranging from macromolecules to small molecules, and exotic `ice' formations on clean metal surfaces.
1. Chemical context
Fluoroquinolones are highly effective antibiotics that have many advantageous pharmacokinetic properties, including high oral bioavailability, large volume of distribution, and broad-spectrum antimicrobial activity (Jain et al., 2002; Marona et al., 2001; Faria et al., 2006). A critical review of fluoroquinolones was given by Zhanel et al., 2002. Sparfloxacin, 5-amino-1-cyclopropyl-7-(cis-3,5-dimethyl-1-piperazinyl)-6,8-difluoro-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, C19H22F2N4O3, is a difluorinated third-generation fluoroquinolone antibiotic and is one of the most important and successful classes of man-made antibacterials used in the treatment of lung infections, urinary tract infections, and cutaneous allergy. A structural investigation of sparfloxacin using and MNDO semi-empirical molecular orbital calculations was published by Abd El-Kareem et al. (2018). The photodegradation of sparfloxacin and isolation of its degradation products by preparative HPLC was published by Salgado et al. (2005). Nanoparticles of Ag–TiO2 for photocatalytic degradation of sparfloxacin was reported by Kulkarni et al. (2018). Newly validated UV spectrophotometric methods for the determination of sparfloxacin in tablets was described by Sowjanya et al. (2020). The electrostatic properties of nine fluoroquinolone antibiotics derived directly from their crystal structures was given by Holstein et al. (2012). Reviews of sparfloxacin (Schentag, 2000), its antibacterial activity, pharmacokinetic properties, clinical efficacy, and tolerability in lower respiratory tract infections (Goa et al., 1997), as well as a review of its penetration into the lower respiratory tract and sinuses (Wise & Honeybourne, 1996) have also been published.
In view of the importance of floxacin drugs, particularly sparfloxacin, the present paper reports the crystal structures of three sparfloxacin salts with organic anions: sparfloxacinium 4-nitrobenzoate dihydrate (I), sparfloxacinium 2-phenylacetate (II) and sparfloxacinium 4-methylbenzoate trihydrate (III). A serendipitous extended tape of fused water pentagons in III is also described.
2. Structural commentary
Reactions between sparfloxacin and 4-nitrobenzoic acid, phenylacetic acid, and 4-methylbenzoic acid yielded the three salts sparfloxacinium 4-nitrobenzoate (I), sparfloxacinium 2-phenylacetate (II), and sparfloxacinium 4-methylbenzoate (III) (see Scheme). Crystals of I (Fig. 1) form as a dihydrate, with a chain of disordered water molecules occupying channels parallel to the a-axis. In II (Fig. 2), the crystals are solvent free. Compound III (Fig. 3) crystallizes as a trihydrate, with the water molecules in channels parallel to the b-axis (section 3, Supramolecular details). Within each salt, the sparfloxacinium cations are structurally similar and have no unusual bond lengths or angles. The dihydroquinoline ring system plus the attached amino, carboxyl, and fluorine atoms are essentially planar (r.m.s. deviations are: I = 0.0744 Å, II = 0.0505 Å and III = 0.0496 Å), with the largest deviations being 0.1901 (8) Å for F1 in I, 0.1392 (8) Å for O2 in II, and 0.1343 (8) for F1 in III. A pair of intramolecular hydrogen bonds (Tables 1–3), O2—H2O⋯O3 and N2—H2NB⋯O3, each form S(6) ring motifs that are preserved in all three structures. The main differences in the cations result from variations in the orientation of the dimethyl piperazine rings, the C6—C7—N3—C10 torsion angles being 60.12 (16)° in I, 39.09 (16)° in II, and −30.9 (2)° in III. By contrast, there is much less variation of the cyclopropyl orientations: C1—N1—C16—C17 torsion angles are 105.99 (15)°, 103.20 (12)°, and 102.71 (15)° for I, II, and III, respectively. The similarities and differences are highlighted in a least-squares-fit overlay of the three cations (Fig. 4).
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In the chosen asymmetric units for each structure, anion placement was selected (amongst symmetry equivalents) so as to form the shortest hydrogen bond between the cationic N4 and the carboxylate O4 of their respective anions (Tables 1–3). In I and III, these involve the equatorial hydrogen (H4NA), i.e., N4—H4NA⋯O4, having donor—acceptor distances of 2.7666 (15) Å in I and 2.6722 (16) Å in III. By contrast, in II, the shortest hydrogen bond for N4 involves the axial hydrogen (H4NB), i.e., N4—H4NB⋯O4 at 2.7122 (12) Å.
3. Supramolecular features
The crystal packing in I, II, and III share a few of types of supramolecular features, including extensive hydrogen bonding and π–π stacking of their quinoline ring systems. Nevertheless, within each structure, the specific interactions lead to distinct structural motifs.
In I, pairs of N4—H4NA⋯O4 and N4—H4NB⋯O4inv (inv = −x + 1, −y + 1, −z + 1) hydrogen bonds (Table 1) form R42(8) ring motifs (Fig. 5) with their inversion-related counterparts, in which the anion O4 atom is a bifurcated acceptor. Hydrogen bonding to the water channel is complicated by the inherent disorder within the water chains, but there is clear evidence of an O1W—H1W1⋯O5 hydrogen bond to the 4-nitrobenzoate anion (Table 1, Fig. 5). In II, a similar R42(8) ring motif (Fig. 6), to that in I, with bifurcated acceptor O4, is built from N4—H4NB⋯O4 and N4—H4NA⋯O4inv hydrogen bonds (Table 2). Structure III features a hydrogen-bonded R44(12) ring motif formed from N4—H4NA⋯O4 and N4—H4NB⋯O5inv hydrogen bonds of cation/anion pairs (Table 3, Fig. 7). For each structure, additional strong intermolecular N—H⋯O hydrogen bonds connect the NH2 amine group to a water molecule (in I and III) or to an anion (in II) (Tables 1–3). The hydrogen-bonded water structure in III is especially intricate, and will be described separately (vide infra).
Inversion-related quinoline ring systems in I π–π stack to give two different interplanar spacings: 3.3789 (14) Å (via −x, −y, −z + 2) and 3.3901 (14) Å (via −x + 1, −y, −z + 2) for the mean planes through N1,C1–C9,O3, leading to columns of cations along the a-axis (Fig. 8). In II, stacking of inversion-related (−x + 2, −y, −z + 2) cations gives an interplanar spacing of 3.3413 (11) Å, but does not lead to extended columns because the offset to adjacent pairs is too great (Fig. 9). In III, π–π stacking again leads to extended columns, this time parallel to the b-axis (Fig. 10), with interplanar spacings of 3.3452 (15) Å (via −x, −y + 2, −z + 1) and 3.4677 (14) Å (via −x, −y + 1, −z + 1).
Atom–atom contact coverages obtained from Hirshfeld surface 2D fingerprint plots calculated using CrystalExplorer (Spackman et al., 2021) for the sparfloxacinium cations in I, II, and III are given in the supporting information (Figs. S1–S3) and summarized in Table 4. In all three salts, the predominant contacts are between H⋯H, H⋯O/O⋯H, and H⋯C/C⋯H.
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In the structure of III, the three water molecules hydrogen bond to n-glide-related copies (Table 3) to form cyclic five-membered slightly puckered pentagonal ring structures. These water pentagons are edge-fused to form extended ribbon- or tape-like chains that propagate parallel to the b-axis by further hydrogen bonding to n-glide- and translation-related water molecules. The tapes hydrogen bond to the sparfloxacinium cation as both donor (O1W—H2W1⋯O1iii) and acceptor (N2—H2NA⋯O2Wii) and to the anion as a donor (O2W—H2W2⋯O4) (symmetry codes as per Table 3). Two views of these supramolecular water-tape structures are shown in Fig. 11. A few other instances of similar pentagonal water assemblies are known. These are compared to those of III, along with some additional background information, in section 4 (Database survey and related literature).
4. Database survey and related literature
A search of the Cambridge Structure Database (CSD version 5.43 with all updates through September 2022; Groom et al., 2016) for the keyword `sparfloxacin' returned (ignoring duplicates) 29 records. Of these, 11 are complexes with metals and have few structural characteristics in common with I, II, or III other than the presence of ligated sparfloxacin molecules. Of the remaining 18 entries, 12 are salts and all but one are co-crystals, hydrates and/or solvates. CSD entry JEKMOB (Miyamoto et al., 1990) corresponds to pure sparfloxacin, while COQWOU (Sivalakshmidevi et al., 2000) is a trihydrate of sparfloxacin. Four entries, UXEPUK, UXEQEV, UXEQAR, and UXEQIZ (Gunnam et al., 2016) are sparfloxacin co-crystallized with methyl, ethyl, propyl, and isobutyl para-hydroxybenzoic acids, respectively. The remaining 12 structures are sparfloxacinium salts, five of which have inorganic counter-anions [CIBYIW (BF4−; Shingnapurkar et al., 2007), GALFEH (Br−; Golovnev & Vasil'ev, 2016), JADGON and JADGUT (CdBr42− and ZnBr42−; Vasil'ev & Golovnev, 2015), and YOBCUP (CuBr4−; Vasil'ev & Golovnev, 2014)]. Of the seven entries with organic counter-anions, GAPCUZ and GAPDAG (Zhang et al., 2022) are salts with pyrocatechuic acid that differ in their occluded solvent, while IJEBIL, IJEBOR, IJEBUX, IJECAE, and IJEDIN (Djalò et al., 2021) have 2-(carboxymethyl)-2-hydroxybutanedioate, pyridine-3-carboxylate, 3-carboxybenzoate, 3-carboxyprop-2-enoate, and 2-aminobenzoate anions respectively. The crystal structures of some closely related compounds, viz., bis(lomefloxacin) 1,4-benzenedicarboxylate dihydrate (XEWSOI; Zhou et al., 2006), gatifloxacin hydrochloride (HOTTOA; Yu et al., 2009), lomefloxacinium picrate (IKAPIU; Jasinski et al., 2011) and lomefloxacin chloride dihydrate (LATPON; Holstein et al., 2012) have also been reported.
Assemblies of water having pentagonal structural units are not uncommon. They are ubiquitous in the clathrate hydrates (see e.g., Englezos, 1993), but are far less common in other structure types. They have been reported in studies of small proteins [e.g., crambin (refcode 1CRN in PDB; Teeter, 1984), BPTI (refcode 1BPI; Parkin et al., 1996); PDB = Protein Data Bank (Berman et al., 2000)] and collagen (Bella et al., 1995), and in small molecules, including a hexahydrate of pinacol (CSD code PINOLH01; Hao et al., 2005), amongst others. A few extended linear water–pentagon tapes similar to those in III have also been reported, e.g., L-leucyl-L-alanine tetrahydrate (CSD code RAVMOQ; Görbitz, 1997); trans-4,4′-azopyridine dioxide tetrahydrate (WAGMOH; Ma et al., 2004), a CuII-based MOF (OFUYOE02; Mukherjee et al., 2011), and a Co(cyclam)Cl2 complex (REFDUD; Jana et al., 2012). In RAVMOQ, the pentagons have similar regularity to those in III but the tapes are considerably more buckled, while in WAGMOH and OFUYOE02 the pentagons/tapes are both severely distorted/buckled relative to those in III. In REFDUD, the tapes of pentagons are further linked into extended layers. Water pentagons are also believed to play a role in ice nucleation (see e.g. Pirzadeh et al., 2011 and references therein). Indeed, an exotic mono-periodic form of `ice' consisting of a linear array of fused water pentagons, reported to nucleate on the (110) surface of copper at temperatures between 100 and 140 K (Carrasco et al., 2009), bears a striking resemblance to the water-pentagon tape in III.
5. Synthesis and crystallization
Sparfloxacin (a gift from Recon Healthcare, Bengaluru) (100 mg, 0.255 mmol) was dissolved in methanol (10 ml) and water (1 ml) under constant stirring at 333 K for 30 min. Equimolar solutions of either 4-nitrobenzoic acid (43 mg, 0.255 mmol), phenylacetic acid (35 mg, 0.255 mmol), or 4-methylbenzoic acid (35 mg, 0.255 mmol) in methanol (10 ml) and acetonitrile (10 ml) were added separately to the solutions of sparfloxacin and stirring was continued for 60 min at 333 K. The mixtures were then cooled to room temperature. X-ray quality crystals were formed by slow evaporation over fifteen days. The melting points were 511–514 K (I), 485–488 K (II) and 498–503 K (III). A generalized reaction scheme for the three salts of sparfloxacin is given in Fig. 12.
6. Data collection and structure refinement
Crystal data, data collection, and structure . At 90 K, crystals of I gave diffraction with satellite reflections, suggesting modulation of the structure. On warming, the satellites diminished, and were absent at the data collection temperature of 250 (1) K. The water molecules in I were extensively disordered. The SQUEEZE routine in PLATON (Spek, 2015) suggested the presence of ∼40e− in the cell `voids', corresponding to two water molecules per Thus, a hydrate model consisting of two major components [occupancies 0.688 (3) for O1W and 0.608 (3) for O2W] and two minor parts for each major [occupancies 0.185 (3), 0.127 (3), 0.265 (3), and 0.128 (3) for O1W′, O1W", O2W′, and O2W", respectively] was built from difference-map peaks. Hydrogen atoms on these partial-occupancy fragments were placed so as to make reasonable hydrogen bonds, but other than H1W1 and H1W2, their presence is solely to ensure a correct atom count. Occupancies for these disordered waters were restrained using SUMP and their Uij restrained with SIMU in SHELXL (Sheldrick, 2015b). Crystals of II and III presented no such problems. All non-disordered hydrogen atoms were found in difference-Fourier maps, but those bound to carbon were subsequently included in the using riding models, with constrained distances set to SHELXL defaults [0.99 Å (R3CH), 0.94 Å (Csp2H), 0.98 Å (R2CH2), 0.97 Å (RCH3) in I and 1.00 Å (R3CH), 0.95 Å (Csp2H), 0.99 Å (R2CH2), 0.98 Å (RCH3) in II and III]. Uiso(H) values for carbon-bound hydrogens were set to 1.2Ueq or 1.5Ueq (CH3) of the parent atom. The OH and NH hydrogen atoms were refined freely (as per Fábry, 2018), aside from the minor-component water hydrogens of I, which were fixed and had Uiso(H) set to 1.5Ueq of their water oxygen.
details are given in Table 5
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Supporting information
https://doi.org/10.1107/S2056989022011239/vm2274sup1.cif
contains datablocks I, II, III, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022011239/vm2274Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989022011239/vm2274IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989022011239/vm2274IIIsup4.hkl
Hirshfeld surface fingerprint plots for I. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup5.png
Hirshfeld surface fingerprint plots for II. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup6.png
Hirshfeld surface fingerprint plots for III. DOI: https://doi.org/10.1107/S2056989022011239/vm2274sup7.png
For all structures, data collection: APEX3 (Bruker, 2016); cell
APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).C19H23F2N4O3+·C7H4NO4−·2H2O | Z = 2 |
Mr = 595.56 | F(000) = 624 |
Triclinic, P1 | Dx = 1.459 Mg m−3 |
a = 7.5736 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.1809 (9) Å | Cell parameters from 9803 reflections |
c = 13.8947 (9) Å | θ = 2.8–27.5° |
α = 85.658 (2)° | µ = 0.12 mm−1 |
β = 82.316 (2)° | T = 250 K |
γ = 81.108 (2)° | Cut block, yellow |
V = 1355.94 (15) Å3 | 0.33 × 0.31 × 0.27 mm |
Bruker D8 Venture dual source diffractometer | 6210 independent reflections |
Radiation source: microsource | 4944 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.033 |
φ and ω scans | θmax = 27.6°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −9→9 |
Tmin = 0.930, Tmax = 0.971 | k = −17→17 |
45287 measured reflections | l = −17→18 |
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)] = 0.039 | Hydrogen site location: mixed |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0419P)2 + 0.4829P] where P = (Fo2 + 2Fc2)/3 |
6210 reflections | (Δ/σ)max = 0.001 |
443 parameters | Δρmax = 0.27 e Å−3 |
46 restraints | Δρmin = −0.22 e Å−3 |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998). The crystals appeared to become modulated (doubled cell, some satellite reflections) when cooled to 90K. Visual inspection of crystal integrity and diffraction quality vs temperature established a safe temperature for data collection of -23° C. |
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. |
Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1W | 1.0080 (5) | 0.43691 (14) | 0.13115 (13) | 0.0767 (9) | 0.688 (3) |
H1W1 | 0.989672 | 0.457266 | 0.185755 | 0.115* | 0.688 (3) |
H2W1 | 1.079647 | 0.467749 | 0.098119 | 0.115* | 0.688 (3) |
O1W' | 0.8676 (14) | 0.4128 (5) | 0.1178 (6) | 0.070 (3) | 0.185 (3) |
H5W1 | 0.868139 | 0.425647 | 0.174506 | 0.105* | 0.185 (3) |
H6W1 | 0.860698 | 0.433812 | 0.056840 | 0.105* | 0.185 (3) |
O2W | 0.7704 (6) | 0.4430 (2) | −0.0090 (2) | 0.0987 (12) | 0.607 (3) |
H1W2 | 0.795334 | 0.431906 | 0.047015 | 0.148* | 0.607 (3) |
H2W2 | 0.794277 | 0.387475 | −0.034142 | 0.148* | 0.607 (3) |
O2W' | 0.6241 (18) | 0.4587 (10) | 0.0029 (7) | 0.148 (4) | 0.265 (3) |
H3W2 | 0.591257 | 0.540477 | −0.008066 | 0.222* | 0.265 (3) |
H4W2 | 0.611625 | 0.429007 | 0.056105 | 0.222* | 0.265 (3) |
O1W" | 1.1155 (10) | 0.5163 (6) | 0.1538 (6) | 0.035 (2) | 0.127 (2) |
H3W1 | 1.079941 | 0.501309 | 0.210951 | 0.053* | 0.127 (2) |
H4W1 | 1.058065 | 0.486154 | 0.122076 | 0.053* | 0.127 (2) |
O2W" | 0.4728 (18) | 0.3998 (9) | 0.0386 (7) | 0.071 (4) | 0.128 (3) |
H5W2 | 0.458449 | 0.355478 | 0.002884 | 0.107* | 0.128 (3) |
H6W2 | 0.421442 | 0.383063 | 0.092059 | 0.107* | 0.128 (3) |
F1 | 0.52757 (11) | 0.05643 (6) | 0.77813 (6) | 0.0371 (2) | |
F2 | 0.18695 (13) | 0.33665 (6) | 0.93914 (6) | 0.0439 (2) | |
O1 | 0.17039 (17) | −0.28135 (8) | 1.13520 (8) | 0.0491 (3) | |
O2 | 0.04706 (18) | −0.15414 (10) | 1.22784 (8) | 0.0531 (3) | |
H2O | 0.038 (3) | −0.080 (2) | 1.2189 (18) | 0.092 (8)* | |
O3 | 0.05728 (15) | 0.02882 (8) | 1.16122 (7) | 0.0410 (2) | |
N1 | 0.36989 (15) | −0.08370 (8) | 0.91686 (8) | 0.0278 (2) | |
N2 | 0.06988 (19) | 0.21803 (10) | 1.08748 (9) | 0.0408 (3) | |
H2NA | 0.054 (3) | 0.2860 (17) | 1.0912 (15) | 0.068 (6)* | |
H2NB | 0.028 (3) | 0.1740 (15) | 1.1371 (14) | 0.056 (5)* | |
N3 | 0.42835 (16) | 0.25859 (8) | 0.77468 (8) | 0.0312 (2) | |
N4 | 0.53893 (17) | 0.38569 (8) | 0.61030 (8) | 0.0302 (2) | |
H4NA | 0.627 (2) | 0.4111 (13) | 0.5620 (13) | 0.047 (5)* | |
H4NB | 0.433 (2) | 0.4245 (13) | 0.5980 (12) | 0.045 (5)* | |
C1 | 0.30722 (18) | −0.14548 (10) | 0.99045 (9) | 0.0299 (3) | |
H1 | 0.337777 | −0.216882 | 0.985064 | 0.036* | |
C2 | 0.20213 (18) | −0.11166 (10) | 1.07257 (9) | 0.0304 (3) | |
C3 | 0.15347 (17) | −0.00419 (10) | 1.08473 (9) | 0.0292 (3) | |
C4 | 0.22010 (17) | 0.06439 (10) | 1.00629 (9) | 0.0266 (3) | |
C5 | 0.33138 (16) | 0.02359 (9) | 0.92265 (9) | 0.0250 (2) | |
C6 | 0.40038 (17) | 0.0912 (1) | 0.85124 (9) | 0.0269 (3) | |
C7 | 0.35467 (17) | 0.1980 (1) | 0.85219 (9) | 0.0275 (3) | |
C8 | 0.24335 (18) | 0.23468 (10) | 0.93348 (10) | 0.0305 (3) | |
C9 | 0.17783 (18) | 0.17274 (10) | 1.01162 (9) | 0.0292 (3) | |
C10 | 0.38665 (19) | 0.24164 (10) | 0.67695 (9) | 0.0313 (3) | |
H10A | 0.270121 | 0.281690 | 0.666003 | 0.038* | |
H10B | 0.378584 | 0.168737 | 0.672166 | 0.038* | |
C11 | 0.53265 (18) | 0.27401 (9) | 0.60029 (9) | 0.0297 (3) | |
H11 | 0.649781 | 0.234195 | 0.613369 | 0.036* | |
C12 | 0.5777 (2) | 0.40582 (10) | 0.71004 (10) | 0.0333 (3) | |
H12 | 0.697490 | 0.367927 | 0.720892 | 0.040* | |
C13 | 0.4360 (2) | 0.36726 (10) | 0.78632 (10) | 0.0336 (3) | |
H13A | 0.465625 | 0.375773 | 0.851484 | 0.040* | |
H13B | 0.318020 | 0.407835 | 0.779453 | 0.040* | |
C14 | 0.5807 (3) | 0.51991 (11) | 0.71586 (12) | 0.0502 (4) | |
H14A | 0.608301 | 0.532920 | 0.779579 | 0.075* | |
H14B | 0.463712 | 0.557707 | 0.705381 | 0.075* | |
H14C | 0.671827 | 0.542109 | 0.666327 | 0.075* | |
C15 | 0.5023 (2) | 0.25721 (12) | 0.49722 (10) | 0.0389 (3) | |
H15A | 0.498785 | 0.184777 | 0.490906 | 0.058* | |
H15B | 0.599751 | 0.279189 | 0.451824 | 0.058* | |
H15C | 0.388849 | 0.296912 | 0.483088 | 0.058* | |
C16 | 0.4737 (2) | −0.12999 (10) | 0.83077 (10) | 0.0334 (3) | |
H16 | 0.603900 | −0.124621 | 0.821780 | 0.040* | |
C17 | 0.3878 (2) | −0.12486 (13) | 0.73970 (11) | 0.0475 (4) | |
H17A | 0.262288 | −0.091945 | 0.741442 | 0.057* | |
H17B | 0.463252 | −0.114810 | 0.677711 | 0.057* | |
C18 | 0.4245 (3) | −0.22495 (13) | 0.79618 (13) | 0.0575 (5) | |
H18A | 0.321508 | −0.253376 | 0.832512 | 0.069* | |
H18B | 0.522463 | −0.276239 | 0.768785 | 0.069* | |
C19 | 0.1399 (2) | −0.18977 (11) | 1.14682 (10) | 0.0378 (3) | |
O4 | 0.75064 (14) | 0.48408 (8) | 0.46618 (8) | 0.0416 (3) | |
O5 | 0.9197 (2) | 0.49587 (10) | 0.32356 (9) | 0.0704 (4) | |
O6 | 1.2405 (3) | −0.02164 (11) | 0.40432 (12) | 0.0886 (5) | |
O7 | 1.2235 (3) | 0.00344 (12) | 0.55450 (12) | 0.0933 (6) | |
N5 | 1.20030 (19) | 0.03305 (10) | 0.47204 (11) | 0.0486 (3) | |
C20 | 1.11515 (19) | 0.13962 (10) | 0.45442 (11) | 0.0349 (3) | |
C21 | 1.1012 (2) | 0.17648 (12) | 0.35967 (11) | 0.0441 (4) | |
H21 | 1.140867 | 0.133723 | 0.307551 | 0.053* | |
C22 | 1.0273 (2) | 0.27779 (12) | 0.34355 (11) | 0.0431 (4) | |
H22 | 1.018655 | 0.304761 | 0.279485 | 0.052* | |
C23 | 0.96571 (18) | 0.34046 (11) | 0.42053 (10) | 0.0328 (3) | |
C24 | 0.98225 (19) | 0.30048 (11) | 0.51504 (10) | 0.0338 (3) | |
H24 | 0.942055 | 0.342696 | 0.567518 | 0.041* | |
C25 | 1.05718 (19) | 0.19935 (11) | 0.53262 (10) | 0.0355 (3) | |
H25 | 1.068158 | 0.172163 | 0.596423 | 0.043* | |
C26 | 0.8742 (2) | 0.44884 (11) | 0.40125 (11) | 0.0384 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.150 (3) | 0.0352 (10) | 0.035 (1) | 0.0000 (13) | 0.0110 (12) | −0.0034 (7) |
O1W' | 0.089 (6) | 0.032 (4) | 0.074 (5) | 0.014 (4) | 0.023 (5) | −0.007 (3) |
O2W | 0.138 (3) | 0.0614 (17) | 0.093 (2) | 0.0114 (19) | −0.015 (2) | −0.0300 (15) |
O2W' | 0.152 (9) | 0.198 (11) | 0.103 (6) | −0.014 (9) | −0.021 (7) | −0.076 (7) |
O1W" | 0.035 (4) | 0.035 (4) | 0.034 (4) | −0.003 (3) | −0.005 (3) | 0.009 (3) |
O2W" | 0.107 (10) | 0.067 (7) | 0.043 (6) | −0.021 (7) | −0.003 (6) | −0.022 (5) |
F1 | 0.0448 (5) | 0.0298 (4) | 0.0315 (4) | −0.0027 (3) | 0.0113 (3) | −0.0035 (3) |
F2 | 0.0602 (6) | 0.0226 (4) | 0.0418 (5) | 0.0027 (4) | 0.0092 (4) | −0.0022 (3) |
O1 | 0.0692 (8) | 0.0342 (6) | 0.0456 (6) | −0.0145 (5) | −0.0130 (6) | 0.0113 (5) |
O2 | 0.0740 (8) | 0.0489 (7) | 0.0341 (6) | −0.0190 (6) | 0.0073 (5) | 0.0082 (5) |
O3 | 0.0515 (6) | 0.0395 (6) | 0.0280 (5) | −0.0064 (5) | 0.0082 (4) | −0.0004 (4) |
N1 | 0.0335 (6) | 0.0228 (5) | 0.0262 (5) | −0.0020 (4) | −0.0033 (4) | −0.0010 (4) |
N2 | 0.0544 (8) | 0.0304 (7) | 0.0321 (6) | −0.0001 (6) | 0.0092 (6) | −0.0048 (5) |
N3 | 0.0459 (7) | 0.0243 (5) | 0.0237 (5) | −0.0093 (5) | −0.0011 (5) | 0.0003 (4) |
N4 | 0.0354 (6) | 0.0231 (5) | 0.0296 (6) | −0.0018 (5) | 0.0000 (5) | 0.0031 (4) |
C1 | 0.0362 (7) | 0.0242 (6) | 0.0301 (7) | −0.0048 (5) | −0.0095 (5) | 0.0028 (5) |
C2 | 0.0346 (7) | 0.0310 (7) | 0.0271 (6) | −0.0078 (5) | −0.0085 (5) | 0.0046 (5) |
C3 | 0.0298 (6) | 0.0341 (7) | 0.0241 (6) | −0.0052 (5) | −0.0050 (5) | 0.0006 (5) |
C4 | 0.0286 (6) | 0.0270 (6) | 0.0240 (6) | −0.0032 (5) | −0.0048 (5) | −0.0003 (5) |
C5 | 0.0272 (6) | 0.0227 (6) | 0.0252 (6) | −0.0024 (5) | −0.0056 (5) | −0.0009 (5) |
C6 | 0.0299 (6) | 0.0271 (6) | 0.0225 (6) | −0.0023 (5) | 0.0001 (5) | −0.0034 (5) |
C7 | 0.0323 (6) | 0.0259 (6) | 0.0241 (6) | −0.0049 (5) | −0.0037 (5) | 0.0008 (5) |
C8 | 0.0373 (7) | 0.0215 (6) | 0.0311 (7) | −0.0002 (5) | −0.0023 (5) | −0.0018 (5) |
C9 | 0.0329 (7) | 0.0292 (6) | 0.0244 (6) | −0.0012 (5) | −0.0028 (5) | −0.0027 (5) |
C10 | 0.0409 (7) | 0.0279 (6) | 0.0252 (6) | −0.0075 (5) | −0.0032 (5) | 0.0005 (5) |
C11 | 0.0369 (7) | 0.0224 (6) | 0.0278 (6) | −0.0015 (5) | −0.0011 (5) | 0.0003 (5) |
C12 | 0.0443 (8) | 0.0249 (6) | 0.0306 (7) | −0.0076 (6) | −0.0030 (6) | 0.0001 (5) |
C13 | 0.0468 (8) | 0.0234 (6) | 0.0298 (7) | −0.0060 (6) | −0.0001 (6) | −0.0013 (5) |
C14 | 0.0772 (12) | 0.0299 (8) | 0.0452 (9) | −0.0202 (8) | 0.0012 (8) | −0.0020 (6) |
C15 | 0.0495 (9) | 0.0399 (8) | 0.0272 (7) | −0.0107 (7) | 0.0000 (6) | −0.0014 (6) |
C16 | 0.0397 (7) | 0.0263 (6) | 0.0318 (7) | −0.0006 (5) | 0.0011 (6) | −0.0050 (5) |
C17 | 0.0602 (10) | 0.0509 (9) | 0.0329 (8) | −0.0105 (8) | −0.0027 (7) | −0.0126 (7) |
C18 | 0.0856 (13) | 0.0344 (8) | 0.0513 (10) | −0.0160 (8) | 0.0122 (9) | −0.0163 (7) |
C19 | 0.0442 (8) | 0.0379 (8) | 0.0332 (7) | −0.0117 (6) | −0.0110 (6) | 0.0085 (6) |
O4 | 0.0427 (6) | 0.0327 (5) | 0.0423 (6) | 0.0030 (4) | 0.0069 (5) | 0.0031 (4) |
O5 | 0.0889 (10) | 0.0538 (8) | 0.0475 (7) | 0.0188 (7) | 0.0197 (7) | 0.0213 (6) |
O6 | 0.1316 (15) | 0.0443 (8) | 0.0737 (10) | 0.0239 (8) | 0.0071 (10) | −0.0100 (7) |
O7 | 0.1428 (16) | 0.0572 (9) | 0.0674 (10) | 0.0305 (9) | −0.0285 (10) | 0.0123 (7) |
N5 | 0.0492 (8) | 0.0353 (7) | 0.0557 (9) | 0.0007 (6) | 0.0019 (6) | 0.0043 (6) |
C20 | 0.0325 (7) | 0.0303 (7) | 0.0399 (8) | −0.0023 (5) | −0.0014 (6) | 0.0016 (6) |
C21 | 0.0546 (9) | 0.0396 (8) | 0.0343 (8) | 0.0008 (7) | 0.0020 (7) | −0.0066 (6) |
C22 | 0.0552 (9) | 0.0434 (8) | 0.0261 (7) | 0.0026 (7) | −0.0018 (6) | 0.0017 (6) |
C23 | 0.0307 (7) | 0.0337 (7) | 0.0315 (7) | −0.0016 (5) | 0.0001 (5) | 0.0017 (5) |
C24 | 0.0347 (7) | 0.0374 (7) | 0.0274 (7) | −0.0014 (6) | −0.0011 (5) | −0.0030 (5) |
C25 | 0.0352 (7) | 0.0390 (8) | 0.0308 (7) | −0.0037 (6) | −0.0045 (6) | 0.0042 (6) |
C26 | 0.0412 (8) | 0.0357 (8) | 0.0342 (7) | 0.0012 (6) | −0.0004 (6) | 0.0036 (6) |
O1W—O1W' | 1.196 (10) | C6—C7 | 1.3973 (18) |
O1W—H1W1 | 0.8112 | C7—C8 | 1.3865 (18) |
O1W—H2W1 | 0.8024 | C8—C9 | 1.3923 (18) |
O1W—H5W1 | 1.1709 | C10—C11 | 1.5170 (18) |
O1W'—H5W1 | 0.8189 | C10—H10A | 0.9800 |
O1W'—H6W1 | 0.8767 | C10—H10B | 0.9800 |
O1W'—H1W2 | 1.1808 | C11—C15 | 1.5182 (19) |
O2W—H6W1 | 1.2013 | C11—H11 | 0.9900 |
O2W—H1W2 | 0.8218 | C12—C14 | 1.5157 (19) |
O2W—H2W2 | 0.8195 | C12—C13 | 1.5223 (19) |
O2W'—H3W2 | 1.0717 | C12—H12 | 0.9900 |
O2W'—H4W2 | 0.8116 | C13—H13A | 0.9800 |
O1W"—H3W1 | 0.8237 | C13—H13B | 0.9800 |
O1W"—H4W1 | 0.8198 | C14—H14A | 0.9700 |
O2W"—H5W2 | 0.8223 | C14—H14B | 0.9700 |
O2W"—H6W2 | 0.8224 | C14—H14C | 0.9700 |
F1—C6 | 1.3573 (14) | C15—H15A | 0.9700 |
F2—C8 | 1.3508 (14) | C15—H15B | 0.9700 |
O1—C19 | 1.2124 (18) | C15—H15C | 0.9700 |
O2—C19 | 1.3224 (19) | C16—C18 | 1.490 (2) |
O2—H2O | 0.97 (3) | C16—C17 | 1.491 (2) |
O3—C3 | 1.2705 (16) | C16—H16 | 0.9900 |
N1—C1 | 1.3408 (16) | C17—C18 | 1.491 (2) |
N1—C5 | 1.4053 (16) | C17—H17A | 0.9800 |
N1—C16 | 1.4601 (16) | C17—H17B | 0.9800 |
N2—C9 | 1.3601 (17) | C18—H18A | 0.9800 |
N2—H2NA | 0.89 (2) | C18—H18B | 0.9800 |
N2—H2NB | 0.92 (2) | O4—C26 | 1.2682 (17) |
N3—C7 | 1.3986 (16) | O5—C26 | 1.2384 (18) |
N3—C13 | 1.4644 (16) | O6—N5 | 1.207 (2) |
N3—C10 | 1.4751 (17) | O7—N5 | 1.209 (2) |
N4—C11 | 1.4975 (16) | N5—C20 | 1.4694 (18) |
N4—C12 | 1.5053 (18) | C20—C25 | 1.374 (2) |
N4—H4NA | 0.960 (18) | C20—C21 | 1.380 (2) |
N4—H4NB | 0.913 (18) | C21—C22 | 1.380 (2) |
C1—C2 | 1.3633 (19) | C21—H21 | 0.9400 |
C1—H1 | 0.9400 | C22—C23 | 1.388 (2) |
C2—C3 | 1.4245 (19) | C22—H22 | 0.9400 |
C2—C19 | 1.4852 (18) | C23—C24 | 1.3916 (19) |
C3—C4 | 1.4506 (17) | C23—C26 | 1.5095 (19) |
C4—C9 | 1.4199 (18) | C24—C25 | 1.383 (2) |
C4—C5 | 1.4292 (17) | C24—H24 | 0.9400 |
C5—C6 | 1.3867 (17) | C25—H25 | 0.9400 |
O1W'—O1W—H1W1 | 104.5 | C10—C11—H11 | 108.7 |
O1W'—O1W—H2W1 | 133.2 | C15—C11—H11 | 108.7 |
H1W1—O1W—H2W1 | 110.0 | N4—C12—C14 | 109.29 (11) |
O1W'—O1W—H5W1 | 40.5 | N4—C12—C13 | 109.42 (11) |
H1W1—O1W—H5W1 | 64.5 | C14—C12—C13 | 111.47 (12) |
H2W1—O1W—H5W1 | 156.0 | N4—C12—H12 | 108.9 |
O1W—O1W'—H5W1 | 68.1 | C14—C12—H12 | 108.9 |
O1W—O1W'—H6W1 | 102.1 | C13—C12—H12 | 108.9 |
H5W1—O1W'—H6W1 | 150.1 | N3—C13—C12 | 110.13 (11) |
O1W—O1W'—H1W2 | 126.7 | N3—C13—H13A | 109.6 |
H5W1—O1W'—H1W2 | 146.3 | C12—C13—H13A | 109.6 |
H6W1—O1W'—H1W2 | 25.0 | N3—C13—H13B | 109.6 |
H6W1—O2W—H1W2 | 21.9 | C12—C13—H13B | 109.6 |
H6W1—O2W—H2W2 | 104.5 | H13A—C13—H13B | 108.1 |
H1W2—O2W—H2W2 | 106.0 | C12—C14—H14A | 109.5 |
H3W2—O2W'—H4W2 | 122.7 | C12—C14—H14B | 109.5 |
H3W1—O1W"—H4W1 | 104.8 | H14A—C14—H14B | 109.5 |
H5W2—O2W"—H6W2 | 104.4 | C12—C14—H14C | 109.5 |
C19—O2—H2O | 105.3 (14) | H14A—C14—H14C | 109.5 |
C1—N1—C5 | 119.87 (11) | H14B—C14—H14C | 109.5 |
C1—N1—C16 | 118.82 (11) | C11—C15—H15A | 109.5 |
C5—N1—C16 | 121.29 (10) | C11—C15—H15B | 109.5 |
C9—N2—H2NA | 120.4 (14) | H15A—C15—H15B | 109.5 |
C9—N2—H2NB | 115.8 (12) | C11—C15—H15C | 109.5 |
H2NA—N2—H2NB | 123.3 (18) | H15A—C15—H15C | 109.5 |
C7—N3—C13 | 120.17 (11) | H15B—C15—H15C | 109.5 |
C7—N3—C10 | 116.79 (11) | N1—C16—C18 | 119.56 (13) |
C13—N3—C10 | 111.65 (10) | N1—C16—C17 | 118.95 (12) |
C11—N4—C12 | 111.82 (10) | C18—C16—C17 | 60.01 (11) |
C11—N4—H4NA | 111.3 (10) | N1—C16—H16 | 115.6 |
C12—N4—H4NA | 109.6 (11) | C18—C16—H16 | 115.6 |
C11—N4—H4NB | 110.7 (11) | C17—C16—H16 | 115.6 |
C12—N4—H4NB | 109.2 (11) | C18—C17—C16 | 59.96 (11) |
H4NA—N4—H4NB | 104.0 (14) | C18—C17—H17A | 117.8 |
N1—C1—C2 | 124.37 (12) | C16—C17—H17A | 117.8 |
N1—C1—H1 | 117.8 | C18—C17—H17B | 117.8 |
C2—C1—H1 | 117.8 | C16—C17—H17B | 117.8 |
C1—C2—C3 | 120.03 (12) | H17A—C17—H17B | 114.9 |
C1—C2—C19 | 118.03 (12) | C16—C18—C17 | 60.03 (10) |
C3—C2—C19 | 121.93 (12) | C16—C18—H18A | 117.8 |
O3—C3—C2 | 120.95 (12) | C17—C18—H18A | 117.8 |
O3—C3—C4 | 122.34 (12) | C16—C18—H18B | 117.8 |
C2—C3—C4 | 116.71 (11) | C17—C18—H18B | 117.8 |
C9—C4—C5 | 118.93 (11) | H18A—C18—H18B | 114.9 |
C9—C4—C3 | 120.79 (11) | O1—C19—O2 | 120.84 (13) |
C5—C4—C3 | 120.28 (11) | O1—C19—C2 | 122.93 (14) |
C6—C5—N1 | 122.45 (11) | O2—C19—C2 | 116.23 (13) |
C6—C5—C4 | 118.84 (11) | O6—N5—O7 | 122.86 (15) |
N1—C5—C4 | 118.70 (11) | O6—N5—C20 | 118.87 (15) |
F1—C6—C5 | 120.87 (11) | O7—N5—C20 | 118.25 (14) |
F1—C6—C7 | 115.55 (11) | C25—C20—C21 | 122.68 (13) |
C5—C6—C7 | 123.46 (11) | C25—C20—N5 | 118.74 (13) |
C8—C7—C6 | 115.87 (11) | C21—C20—N5 | 118.56 (13) |
C8—C7—N3 | 125.60 (12) | C22—C21—C20 | 118.18 (14) |
C6—C7—N3 | 118.49 (11) | C22—C21—H21 | 120.9 |
F2—C8—C7 | 119.99 (11) | C20—C21—H21 | 120.9 |
F2—C8—C9 | 115.54 (11) | C21—C22—C23 | 120.96 (14) |
C7—C8—C9 | 124.44 (12) | C21—C22—H22 | 119.5 |
N2—C9—C8 | 118.91 (12) | C23—C22—H22 | 119.5 |
N2—C9—C4 | 122.81 (12) | C22—C23—C24 | 119.14 (13) |
C8—C9—C4 | 118.21 (11) | C22—C23—C26 | 119.83 (13) |
N3—C10—C11 | 109.88 (11) | C24—C23—C26 | 120.96 (13) |
N3—C10—H10A | 109.7 | C25—C24—C23 | 120.74 (13) |
C11—C10—H10A | 109.7 | C25—C24—H24 | 119.6 |
N3—C10—H10B | 109.7 | C23—C24—H24 | 119.6 |
C11—C10—H10B | 109.7 | C20—C25—C24 | 118.29 (13) |
H10A—C10—H10B | 108.2 | C20—C25—H25 | 120.9 |
N4—C11—C10 | 107.6 (1) | C24—C25—H25 | 120.9 |
N4—C11—C15 | 109.68 (11) | O5—C26—O4 | 124.62 (14) |
C10—C11—C15 | 113.43 (12) | O5—C26—C23 | 118.92 (13) |
N4—C11—H11 | 108.7 | O4—C26—C23 | 116.44 (12) |
C5—N1—C1—C2 | 1.5 (2) | C5—C4—C9—C8 | 1.62 (18) |
C16—N1—C1—C2 | −176.94 (13) | C3—C4—C9—C8 | −179.06 (12) |
N1—C1—C2—C3 | −0.6 (2) | C7—N3—C10—C11 | −155.08 (11) |
N1—C1—C2—C19 | 178.70 (12) | C13—N3—C10—C11 | 61.19 (14) |
C1—C2—C3—O3 | −179.23 (13) | C12—N4—C11—C10 | 58.92 (14) |
C19—C2—C3—O3 | 1.5 (2) | C12—N4—C11—C15 | −177.27 (11) |
C1—C2—C3—C4 | 0.35 (18) | N3—C10—C11—N4 | −59.62 (14) |
C19—C2—C3—C4 | −178.93 (12) | N3—C10—C11—C15 | 178.88 (11) |
O3—C3—C4—C9 | −0.8 (2) | C11—N4—C12—C14 | −179.49 (12) |
C2—C3—C4—C9 | 179.66 (12) | C11—N4—C12—C13 | −57.18 (14) |
O3—C3—C4—C5 | 178.54 (12) | C7—N3—C13—C12 | 159.20 (12) |
C2—C3—C4—C5 | −1.03 (18) | C10—N3—C13—C12 | −58.45 (15) |
C1—N1—C5—C6 | 176.48 (12) | N4—C12—C13—N3 | 55.29 (15) |
C16—N1—C5—C6 | −5.09 (19) | C14—C12—C13—N3 | 176.29 (13) |
C1—N1—C5—C4 | −2.13 (17) | C1—N1—C16—C18 | 36.0 (2) |
C16—N1—C5—C4 | 176.30 (12) | C5—N1—C16—C18 | −142.40 (14) |
C9—C4—C5—C6 | 2.57 (18) | C1—N1—C16—C17 | 105.99 (15) |
C3—C4—C5—C6 | −176.75 (12) | C5—N1—C16—C17 | −72.46 (17) |
C9—C4—C5—N1 | −178.76 (11) | N1—C16—C17—C18 | −109.38 (15) |
C3—C4—C5—N1 | 1.92 (18) | N1—C16—C18—C17 | 108.37 (15) |
N1—C5—C6—F1 | −8.58 (19) | C1—C2—C19—O1 | −4.0 (2) |
C4—C5—C6—F1 | 170.03 (11) | C3—C2—C19—O1 | 175.27 (14) |
N1—C5—C6—C7 | 175.64 (12) | C1—C2—C19—O2 | 176.23 (13) |
C4—C5—C6—C7 | −5.75 (19) | C3—C2—C19—O2 | −4.5 (2) |
F1—C6—C7—C8 | −171.68 (11) | O6—N5—C20—C25 | 175.16 (17) |
C5—C6—C7—C8 | 4.30 (19) | O7—N5—C20—C25 | −3.3 (2) |
F1—C6—C7—N3 | 5.98 (18) | O6—N5—C20—C21 | −6.6 (2) |
C5—C6—C7—N3 | −178.03 (12) | O7—N5—C20—C21 | 174.94 (18) |
C13—N3—C7—C8 | 18.0 (2) | C25—C20—C21—C22 | 0.6 (2) |
C10—N3—C7—C8 | −122.47 (14) | N5—C20—C21—C22 | −177.55 (15) |
C13—N3—C7—C6 | −159.38 (12) | C20—C21—C22—C23 | −1.2 (3) |
C10—N3—C7—C6 | 60.12 (16) | C21—C22—C23—C24 | 1.2 (2) |
C6—C7—C8—F2 | −177.64 (12) | C21—C22—C23—C26 | −175.88 (15) |
N3—C7—C8—F2 | 4.9 (2) | C22—C23—C24—C25 | −0.7 (2) |
C6—C7—C8—C9 | 0.3 (2) | C26—C23—C24—C25 | 176.36 (13) |
N3—C7—C8—C9 | −177.18 (13) | C21—C20—C25—C24 | −0.1 (2) |
F2—C8—C9—N2 | −2.18 (19) | N5—C20—C25—C24 | 178.04 (13) |
C7—C8—C9—N2 | 179.79 (13) | C23—C24—C25—C20 | 0.2 (2) |
F2—C8—C9—C4 | 174.87 (11) | C22—C23—C26—O5 | −31.0 (2) |
C7—C8—C9—C4 | −3.2 (2) | C24—C23—C26—O5 | 151.92 (17) |
C5—C4—C9—N2 | 178.55 (13) | C22—C23—C26—O4 | 147.01 (15) |
C3—C4—C9—N2 | −2.1 (2) | C24—C23—C26—O4 | −30.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3 | 0.97 (3) | 1.60 (3) | 2.5257 (15) | 157 (2) |
N2—H2NB···O3 | 0.92 (2) | 1.901 (19) | 2.6343 (17) | 135.0 (16) |
N4—H4NA···O4 | 0.960 (18) | 1.824 (18) | 2.7666 (15) | 166.4 (15) |
O1W—H1W1···O5 | 0.81 | 2.00 | 2.806 (2) | 173 |
O2W—H1W2···O1W | 0.82 | 2.12 | 2.811 (5) | 141 |
O1W—H2W1···O2Wi | 0.80 | 2.01 | 2.803 (5) | 172 |
O2W—H2W2···O1ii | 0.82 | 2.02 | 2.807 (3) | 161 |
N2—H2NA···O1Wiii | 0.89 (2) | 2.07 (2) | 2.947 (2) | 167.8 (19) |
N4—H4NB···O4iv | 0.913 (18) | 1.957 (18) | 2.8405 (16) | 162.5 (15) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y, −z+1; (iii) x−1, y, z+1; (iv) −x+1, −y+1, −z+1. |
C19H23F2N4O3+·C8H7O2− | Z = 2 |
Mr = 528.55 | F(000) = 556 |
Triclinic, P1 | Dx = 1.428 Mg m−3 |
a = 10.0222 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.1145 (4) Å | Cell parameters from 9186 reflections |
c = 13.5255 (5) Å | θ = 3.0–27.5° |
α = 69.606 (2)° | µ = 0.11 mm−1 |
β = 73.032 (2)° | T = 90 K |
γ = 83.747 (2)° | Irregular block, pale yellow |
V = 1229.15 (9) Å3 | 0.34 × 0.28 × 0.26 mm |
Bruker D8 Venture dual source diffractometer | 5639 independent reflections |
Radiation source: microsource | 5029 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.038 |
φ and ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −12→12 |
Tmin = 0.914, Tmax = 0.959 | k = −12→13 |
41293 measured reflections | l = −17→17 |
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)] = 0.034 | Hydrogen site location: mixed |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.5792P] where P = (Fo2 + 2Fc2)/3 |
5639 reflections | (Δ/σ)max = 0.002 |
365 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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. |
Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.70792 (7) | 0.00637 (7) | 0.83721 (5) | 0.01777 (15) | |
F2 | 0.63127 (7) | 0.35650 (7) | 1.00282 (5) | 0.01665 (14) | |
O1 | 1.05409 (8) | −0.41085 (8) | 1.22035 (7) | 0.01857 (17) | |
O2 | 1.00723 (10) | −0.25755 (9) | 1.31012 (7) | 0.02240 (19) | |
H2O | 0.970 (2) | −0.164 (2) | 1.2943 (16) | 0.051 (5)* | |
O3 | 0.89918 (9) | −0.02316 (8) | 1.22819 (6) | 0.01721 (17) | |
N1 | 0.84402 (9) | −0.17056 (9) | 0.99535 (7) | 0.01228 (18) | |
N2 | 0.77272 (12) | 0.21351 (11) | 1.14682 (8) | 0.0201 (2) | |
H2NA | 0.7380 (17) | 0.2964 (18) | 1.1458 (13) | 0.029 (4)* | |
H2NB | 0.8144 (17) | 0.1606 (17) | 1.1985 (13) | 0.027 (4)* | |
N3 | 0.59393 (10) | 0.26309 (10) | 0.84423 (7) | 0.01448 (19) | |
N4 | 0.58386 (10) | 0.38019 (10) | 0.62261 (7) | 0.01321 (18) | |
H4NA | 0.6191 (17) | 0.3897 (17) | 0.5467 (13) | 0.029 (4)* | |
H4NB | 0.5030 (16) | 0.4386 (16) | 0.6268 (12) | 0.023 (4)* | |
C1 | 0.91214 (11) | −0.24536 (11) | 1.06947 (9) | 0.0133 (2) | |
H1 | 0.950209 | −0.334367 | 1.065994 | 0.016* | |
C2 | 0.93024 (11) | −0.20187 (11) | 1.14943 (8) | 0.0134 (2) | |
C3 | 0.88013 (11) | −0.06613 (11) | 1.15534 (8) | 0.0129 (2) | |
C4 | 0.80895 (11) | 0.01794 (11) | 1.07502 (8) | 0.0123 (2) | |
C5 | 0.78917 (11) | −0.03613 (11) | 0.99549 (8) | 0.0119 (2) | |
C6 | 0.71912 (11) | 0.04728 (11) | 0.91986 (8) | 0.0131 (2) | |
C7 | 0.66418 (11) | 0.18133 (11) | 0.91898 (8) | 0.0128 (2) | |
C8 | 0.68554 (11) | 0.22948 (11) | 0.99773 (9) | 0.0135 (2) | |
C9 | 0.75685 (11) | 0.15531 (11) | 1.07451 (8) | 0.0131 (2) | |
C10 | 0.49686 (11) | 0.20780 (11) | 0.80689 (8) | 0.0137 (2) | |
H10A | 0.405327 | 0.255422 | 0.822658 | 0.016* | |
H10B | 0.483568 | 0.105862 | 0.848679 | 0.016* | |
C11 | 0.54638 (11) | 0.22823 (11) | 0.68460 (8) | 0.0132 (2) | |
H11 | 0.630826 | 0.167958 | 0.670230 | 0.016* | |
C12 | 0.68765 (11) | 0.43180 (11) | 0.66142 (9) | 0.0149 (2) | |
H12 | 0.775319 | 0.374507 | 0.651603 | 0.018* | |
C13 | 0.62643 (12) | 0.41177 (11) | 0.78307 (9) | 0.0145 (2) | |
H13A | 0.694316 | 0.443183 | 0.810613 | 0.017* | |
H13B | 0.540560 | 0.469619 | 0.793619 | 0.017* | |
C14 | 0.72062 (14) | 0.58531 (13) | 0.59395 (10) | 0.0242 (3) | |
H14A | 0.755513 | 0.594990 | 0.516135 | 0.036* | |
H14B | 0.791838 | 0.617518 | 0.616781 | 0.036* | |
H14C | 0.635807 | 0.642584 | 0.605345 | 0.036* | |
C15 | 0.43375 (12) | 0.18919 (12) | 0.64521 (9) | 0.0176 (2) | |
H15A | 0.466770 | 0.208543 | 0.565850 | 0.026* | |
H15B | 0.349399 | 0.245187 | 0.662023 | 0.026* | |
H15C | 0.412447 | 0.088674 | 0.682358 | 0.026* | |
C16 | 0.83214 (11) | −0.23184 (11) | 0.91487 (8) | 0.0139 (2) | |
H16 | 0.885555 | −0.182759 | 0.837347 | 0.017* | |
C17 | 0.69701 (12) | −0.29534 (12) | 0.92921 (9) | 0.0190 (2) | |
H17A | 0.668119 | −0.282994 | 0.862478 | 0.023* | |
H17B | 0.619520 | −0.295690 | 0.994438 | 0.023* | |
C18 | 0.82133 (13) | −0.38861 (12) | 0.94729 (9) | 0.0189 (2) | |
H18A | 0.820179 | −0.446110 | 1.023612 | 0.023* | |
H18B | 0.868786 | −0.433412 | 0.891632 | 0.023* | |
C19 | 1.00275 (11) | −0.29946 (12) | 1.22819 (9) | 0.0153 (2) | |
O4 | 0.35788 (9) | 0.55031 (9) | 0.60167 (6) | 0.01934 (18) | |
O5 | 0.29414 (9) | 0.53584 (9) | 0.77723 (7) | 0.02231 (19) | |
C20 | 0.18020 (11) | 0.80365 (11) | 0.56629 (9) | 0.0143 (2) | |
C21 | 0.27729 (12) | 0.89939 (12) | 0.55673 (9) | 0.0183 (2) | |
H21 | 0.327649 | 0.877691 | 0.610123 | 0.022* | |
C22 | 0.30119 (13) | 1.02595 (13) | 0.47016 (10) | 0.0221 (2) | |
H22 | 0.367933 | 1.090038 | 0.464389 | 0.026* | |
C23 | 0.22759 (13) | 1.05909 (12) | 0.39183 (9) | 0.0213 (2) | |
H23 | 0.243173 | 1.146127 | 0.332936 | 0.026* | |
C24 | 0.13151 (12) | 0.96463 (12) | 0.40009 (9) | 0.0194 (2) | |
H24 | 0.081044 | 0.986744 | 0.346737 | 0.023* | |
C25 | 0.10881 (12) | 0.83743 (12) | 0.48642 (9) | 0.0164 (2) | |
H25 | 0.043610 | 0.772607 | 0.490962 | 0.020* | |
C26 | 0.14869 (11) | 0.66952 (12) | 0.66354 (9) | 0.0157 (2) | |
H26A | 0.083521 | 0.612589 | 0.652443 | 0.019* | |
H26B | 0.100571 | 0.694457 | 0.729885 | 0.019* | |
C27 | 0.27658 (11) | 0.57882 (11) | 0.68409 (9) | 0.0142 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0263 (4) | 0.0183 (3) | 0.0142 (3) | 0.0045 (3) | −0.0104 (3) | −0.0093 (3) |
F2 | 0.0211 (3) | 0.0131 (3) | 0.0188 (3) | 0.0042 (2) | −0.0083 (3) | −0.0079 (3) |
O1 | 0.0188 (4) | 0.0148 (4) | 0.0223 (4) | 0.0014 (3) | −0.0083 (3) | −0.0047 (3) |
O2 | 0.0312 (5) | 0.0204 (4) | 0.0215 (4) | 0.0064 (4) | −0.0166 (4) | −0.0083 (3) |
O3 | 0.0221 (4) | 0.0179 (4) | 0.0160 (4) | 0.0021 (3) | −0.0099 (3) | −0.0077 (3) |
N1 | 0.0138 (4) | 0.0119 (4) | 0.0115 (4) | −0.0007 (3) | −0.0029 (3) | −0.0045 (3) |
N2 | 0.0308 (6) | 0.0160 (5) | 0.0210 (5) | 0.0070 (4) | −0.0152 (4) | −0.0106 (4) |
N3 | 0.0179 (5) | 0.0123 (4) | 0.0139 (4) | −0.0017 (3) | −0.0078 (4) | −0.0020 (3) |
N4 | 0.0144 (4) | 0.0134 (4) | 0.0109 (4) | 0.0004 (3) | −0.0036 (3) | −0.0031 (3) |
C1 | 0.0114 (5) | 0.0126 (5) | 0.0139 (5) | −0.0008 (4) | −0.0016 (4) | −0.0032 (4) |
C2 | 0.0127 (5) | 0.0135 (5) | 0.0127 (5) | −0.0013 (4) | −0.0031 (4) | −0.0027 (4) |
C3 | 0.0116 (5) | 0.0147 (5) | 0.0117 (5) | −0.0026 (4) | −0.0016 (4) | −0.0038 (4) |
C4 | 0.0123 (5) | 0.0134 (5) | 0.0107 (5) | −0.0015 (4) | −0.0023 (4) | −0.0038 (4) |
C5 | 0.0120 (5) | 0.0115 (5) | 0.0109 (5) | −0.0014 (4) | −0.0011 (4) | −0.0036 (4) |
C6 | 0.0151 (5) | 0.0157 (5) | 0.0100 (5) | −0.0015 (4) | −0.0031 (4) | −0.0059 (4) |
C7 | 0.0117 (5) | 0.0141 (5) | 0.0108 (5) | −0.0018 (4) | −0.0020 (4) | −0.0025 (4) |
C8 | 0.0146 (5) | 0.0112 (5) | 0.0142 (5) | 0.0008 (4) | −0.0026 (4) | −0.0048 (4) |
C9 | 0.0140 (5) | 0.0141 (5) | 0.0113 (5) | −0.0013 (4) | −0.0026 (4) | −0.0047 (4) |
C10 | 0.0132 (5) | 0.0157 (5) | 0.0125 (5) | −0.0012 (4) | −0.0038 (4) | −0.0042 (4) |
C11 | 0.0142 (5) | 0.0124 (5) | 0.0126 (5) | 0.0002 (4) | −0.0035 (4) | −0.0040 (4) |
C12 | 0.0147 (5) | 0.0151 (5) | 0.0145 (5) | −0.0014 (4) | −0.0056 (4) | −0.0028 (4) |
C13 | 0.0173 (5) | 0.0120 (5) | 0.0145 (5) | 0.0002 (4) | −0.0063 (4) | −0.0033 (4) |
C14 | 0.0316 (7) | 0.0180 (6) | 0.0206 (6) | −0.0087 (5) | −0.0097 (5) | 0.0011 (5) |
C15 | 0.0189 (5) | 0.0206 (6) | 0.0152 (5) | −0.0025 (4) | −0.0057 (4) | −0.0068 (4) |
C16 | 0.0179 (5) | 0.0135 (5) | 0.0114 (5) | −0.0007 (4) | −0.0032 (4) | −0.0058 (4) |
C17 | 0.0203 (6) | 0.0218 (6) | 0.0178 (5) | −0.0047 (4) | −0.0043 (4) | −0.0093 (4) |
C18 | 0.0276 (6) | 0.0138 (5) | 0.0169 (5) | −0.0023 (4) | −0.0063 (4) | −0.0062 (4) |
C19 | 0.0133 (5) | 0.0157 (5) | 0.0156 (5) | −0.0021 (4) | −0.0047 (4) | −0.0026 (4) |
O4 | 0.0206 (4) | 0.0220 (4) | 0.0134 (4) | 0.0070 (3) | −0.0039 (3) | −0.0063 (3) |
O5 | 0.0283 (5) | 0.0249 (4) | 0.0148 (4) | 0.0089 (4) | −0.0089 (3) | −0.0082 (3) |
C20 | 0.0147 (5) | 0.0138 (5) | 0.0140 (5) | 0.0033 (4) | −0.0021 (4) | −0.0065 (4) |
C21 | 0.0213 (6) | 0.0183 (5) | 0.0170 (5) | −0.0004 (4) | −0.0063 (4) | −0.0070 (4) |
C22 | 0.0279 (6) | 0.0171 (5) | 0.0217 (6) | −0.0041 (5) | −0.0044 (5) | −0.0078 (5) |
C23 | 0.0303 (6) | 0.0140 (5) | 0.0159 (5) | 0.0031 (5) | −0.0031 (5) | −0.0038 (4) |
C24 | 0.0217 (6) | 0.0215 (6) | 0.0149 (5) | 0.0076 (4) | −0.0064 (4) | −0.0071 (4) |
C25 | 0.0149 (5) | 0.0186 (5) | 0.0166 (5) | 0.0023 (4) | −0.0033 (4) | −0.0085 (4) |
C26 | 0.0144 (5) | 0.0163 (5) | 0.0147 (5) | 0.0009 (4) | −0.0030 (4) | −0.0041 (4) |
C27 | 0.0158 (5) | 0.0117 (5) | 0.0144 (5) | −0.0006 (4) | −0.0033 (4) | −0.0041 (4) |
F1—C6 | 1.3562 (11) | C12—C13 | 1.5266 (15) |
F2—C8 | 1.3560 (12) | C12—H12 | 1.0000 |
O1—C19 | 1.2126 (14) | C13—H13A | 0.9900 |
O2—C19 | 1.3304 (14) | C13—H13B | 0.9900 |
O2—H2O | 0.95 (2) | C14—H14A | 0.9800 |
O3—C3 | 1.2738 (13) | C14—H14B | 0.9800 |
N1—C1 | 1.3423 (14) | C14—H14C | 0.9800 |
N1—C5 | 1.4104 (13) | C15—H15A | 0.9800 |
N1—C16 | 1.4646 (13) | C15—H15B | 0.9800 |
N2—C9 | 1.3567 (14) | C15—H15C | 0.9800 |
N2—H2NA | 0.869 (17) | C16—C17 | 1.4945 (15) |
N2—H2NB | 0.900 (17) | C16—C18 | 1.4978 (15) |
N3—C7 | 1.3812 (14) | C16—H16 | 1.0000 |
N3—C10 | 1.4548 (13) | C17—C18 | 1.5044 (17) |
N3—C13 | 1.4609 (13) | C17—H17A | 0.9900 |
N4—C11 | 1.5000 (13) | C17—H17B | 0.9900 |
N4—C12 | 1.5026 (13) | C18—H18A | 0.9900 |
N4—H4NA | 0.956 (16) | C18—H18B | 0.9900 |
N4—H4NB | 0.949 (16) | O4—C27 | 1.2777 (13) |
C1—C2 | 1.3636 (15) | O5—C27 | 1.2401 (13) |
C1—H1 | 0.9500 | C20—C25 | 1.3916 (15) |
C2—C3 | 1.4305 (15) | C20—C21 | 1.3949 (16) |
C2—C19 | 1.4833 (15) | C20—C26 | 1.5091 (15) |
C3—C4 | 1.4452 (14) | C21—C22 | 1.3876 (17) |
C4—C9 | 1.4285 (15) | C21—H21 | 0.9500 |
C4—C5 | 1.4329 (14) | C22—C23 | 1.3906 (18) |
C5—C6 | 1.3927 (15) | C22—H22 | 0.9500 |
C6—C7 | 1.4041 (15) | C23—C24 | 1.3841 (18) |
C7—C8 | 1.3910 (14) | C23—H23 | 0.9500 |
C8—C9 | 1.3877 (15) | C24—C25 | 1.3900 (16) |
C10—C11 | 1.5264 (14) | C24—H24 | 0.9500 |
C10—H10A | 0.9900 | C25—H25 | 0.9500 |
C10—H10B | 0.9900 | C26—C27 | 1.5283 (15) |
C11—C15 | 1.5194 (15) | C26—H26A | 0.9900 |
C11—H11 | 1.0000 | C26—H26B | 0.9900 |
C12—C14 | 1.5169 (15) | ||
C19—O2—H2O | 105.6 (12) | N3—C13—H13B | 109.8 |
C1—N1—C5 | 119.83 (9) | C12—C13—H13B | 109.8 |
C1—N1—C16 | 117.94 (9) | H13A—C13—H13B | 108.2 |
C5—N1—C16 | 122.22 (9) | C12—C14—H14A | 109.5 |
C9—N2—H2NA | 120.6 (11) | C12—C14—H14B | 109.5 |
C9—N2—H2NB | 117.6 (10) | H14A—C14—H14B | 109.5 |
H2NA—N2—H2NB | 121.7 (14) | C12—C14—H14C | 109.5 |
C7—N3—C10 | 124.24 (9) | H14A—C14—H14C | 109.5 |
C7—N3—C13 | 122.03 (9) | H14B—C14—H14C | 109.5 |
C10—N3—C13 | 113.16 (8) | C11—C15—H15A | 109.5 |
C11—N4—C12 | 112.99 (8) | C11—C15—H15B | 109.5 |
C11—N4—H4NA | 107.3 (10) | H15A—C15—H15B | 109.5 |
C12—N4—H4NA | 111.1 (10) | C11—C15—H15C | 109.5 |
C11—N4—H4NB | 110.9 (9) | H15A—C15—H15C | 109.5 |
C12—N4—H4NB | 109.4 (9) | H15B—C15—H15C | 109.5 |
H4NA—N4—H4NB | 104.9 (13) | N1—C16—C17 | 119.36 (9) |
N1—C1—C2 | 124.25 (10) | N1—C16—C18 | 119.26 (9) |
N1—C1—H1 | 117.9 | C17—C16—C18 | 60.36 (8) |
C2—C1—H1 | 117.9 | N1—C16—H16 | 115.6 |
C1—C2—C3 | 120.08 (10) | C17—C16—H16 | 115.6 |
C1—C2—C19 | 117.76 (10) | C18—C16—H16 | 115.6 |
C3—C2—C19 | 122.16 (10) | C16—C17—C18 | 59.93 (7) |
O3—C3—C2 | 120.62 (10) | C16—C17—H17A | 117.8 |
O3—C3—C4 | 122.58 (10) | C18—C17—H17A | 117.8 |
C2—C3—C4 | 116.80 (9) | C16—C17—H17B | 117.8 |
C9—C4—C5 | 119.35 (9) | C18—C17—H17B | 117.8 |
C9—C4—C3 | 120.38 (9) | H17A—C17—H17B | 114.9 |
C5—C4—C3 | 120.28 (9) | C16—C18—C17 | 59.71 (7) |
C6—C5—N1 | 122.53 (9) | C16—C18—H18A | 117.8 |
C6—C5—C4 | 118.75 (9) | C17—C18—H18A | 117.8 |
N1—C5—C4 | 118.71 (9) | C16—C18—H18B | 117.8 |
F1—C6—C5 | 121.11 (9) | C17—C18—H18B | 117.8 |
F1—C6—C7 | 115.64 (9) | H18A—C18—H18B | 114.9 |
C5—C6—C7 | 123.12 (9) | O1—C19—O2 | 121.36 (10) |
N3—C7—C8 | 121.0 (1) | O1—C19—C2 | 123.17 (10) |
N3—C7—C6 | 122.83 (9) | O2—C19—C2 | 115.47 (10) |
C8—C7—C6 | 116.17 (9) | C25—C20—C21 | 118.45 (10) |
F2—C8—C9 | 116.52 (9) | C25—C20—C26 | 120.7 (1) |
F2—C8—C7 | 118.76 (9) | C21—C20—C26 | 120.8 (1) |
C9—C8—C7 | 124.71 (10) | C22—C21—C20 | 120.78 (11) |
N2—C9—C8 | 119.61 (10) | C22—C21—H21 | 119.6 |
N2—C9—C4 | 122.51 (10) | C20—C21—H21 | 119.6 |
C8—C9—C4 | 117.87 (9) | C21—C22—C23 | 120.09 (11) |
N3—C10—C11 | 112.99 (9) | C21—C22—H22 | 120.0 |
N3—C10—H10A | 109.0 | C23—C22—H22 | 120.0 |
C11—C10—H10A | 109.0 | C24—C23—C22 | 119.67 (11) |
N3—C10—H10B | 109.0 | C24—C23—H23 | 120.2 |
C11—C10—H10B | 109.0 | C22—C23—H23 | 120.2 |
H10A—C10—H10B | 107.8 | C23—C24—C25 | 120.03 (11) |
N4—C11—C15 | 108.99 (9) | C23—C24—H24 | 120.0 |
N4—C11—C10 | 108.68 (8) | C25—C24—H24 | 120.0 |
C15—C11—C10 | 111.49 (9) | C24—C25—C20 | 120.96 (11) |
N4—C11—H11 | 109.2 | C24—C25—H25 | 119.5 |
C15—C11—H11 | 109.2 | C20—C25—H25 | 119.5 |
C10—C11—H11 | 109.2 | C20—C26—C27 | 114.65 (9) |
N4—C12—C14 | 109.52 (9) | C20—C26—H26A | 108.6 |
N4—C12—C13 | 108.54 (9) | C27—C26—H26A | 108.6 |
C14—C12—C13 | 111.62 (9) | C20—C26—H26B | 108.6 |
N4—C12—H12 | 109.0 | C27—C26—H26B | 108.6 |
C14—C12—H12 | 109.0 | H26A—C26—H26B | 107.6 |
C13—C12—H12 | 109.0 | O5—C27—O4 | 124.4 (1) |
N3—C13—C12 | 109.59 (9) | O5—C27—C26 | 119.62 (10) |
N3—C13—H13A | 109.8 | O4—C27—C26 | 115.97 (9) |
C12—C13—H13A | 109.8 | ||
C5—N1—C1—C2 | 1.77 (16) | C7—C8—C9—C4 | −1.82 (16) |
C16—N1—C1—C2 | −179.51 (10) | C5—C4—C9—N2 | −179.51 (10) |
N1—C1—C2—C3 | −2.65 (17) | C3—C4—C9—N2 | 0.89 (16) |
N1—C1—C2—C19 | 177.40 (9) | C5—C4—C9—C8 | 1.59 (15) |
C1—C2—C3—O3 | −178.44 (10) | C3—C4—C9—C8 | −178.01 (9) |
C19—C2—C3—O3 | 1.50 (16) | C7—N3—C10—C11 | −116.00 (11) |
C1—C2—C3—C4 | 1.16 (15) | C13—N3—C10—C11 | 55.53 (12) |
C19—C2—C3—C4 | −178.89 (9) | C12—N4—C11—C15 | 175.95 (9) |
O3—C3—C4—C9 | 0.20 (16) | C12—N4—C11—C10 | 54.26 (11) |
C2—C3—C4—C9 | −179.39 (9) | N3—C10—C11—N4 | −51.50 (11) |
O3—C3—C4—C5 | −179.40 (9) | N3—C10—C11—C15 | −171.65 (9) |
C2—C3—C4—C5 | 1.01 (15) | C11—N4—C12—C14 | 179.47 (9) |
C1—N1—C5—C6 | 179.14 (10) | C11—N4—C12—C13 | −58.45 (11) |
C16—N1—C5—C6 | 0.48 (15) | C7—N3—C13—C12 | 113.64 (11) |
C1—N1—C5—C4 | 0.54 (14) | C10—N3—C13—C12 | −58.10 (12) |
C16—N1—C5—C4 | −178.13 (9) | N4—C12—C13—N3 | 58.10 (11) |
C9—C4—C5—C6 | −0.12 (15) | C14—C12—C13—N3 | 178.90 (9) |
C3—C4—C5—C6 | 179.48 (9) | C1—N1—C16—C17 | 103.20 (12) |
C9—C4—C5—N1 | 178.54 (9) | C5—N1—C16—C17 | −78.11 (13) |
C3—C4—C5—N1 | −1.86 (15) | C1—N1—C16—C18 | 32.78 (14) |
N1—C5—C6—F1 | −4.25 (16) | C5—N1—C16—C18 | −148.53 (10) |
C4—C5—C6—F1 | 174.35 (9) | N1—C16—C17—C18 | −108.97 (11) |
N1—C5—C6—C7 | −179.91 (9) | N1—C16—C18—C17 | 109.14 (11) |
C4—C5—C6—C7 | −1.31 (16) | C1—C2—C19—O1 | 4.97 (16) |
C10—N3—C7—C8 | −141.61 (11) | C3—C2—C19—O1 | −174.97 (10) |
C13—N3—C7—C8 | 47.59 (15) | C1—C2—C19—O2 | −174.44 (10) |
C10—N3—C7—C6 | 39.09 (16) | C3—C2—C19—O2 | 5.62 (15) |
C13—N3—C7—C6 | −131.71 (11) | C25—C20—C21—C22 | 0.59 (17) |
F1—C6—C7—N3 | 4.61 (15) | C26—C20—C21—C22 | −176.77 (10) |
C5—C6—C7—N3 | −179.52 (10) | C20—C21—C22—C23 | 0.31 (18) |
F1—C6—C7—C8 | −174.73 (9) | C21—C22—C23—C24 | −0.65 (18) |
C5—C6—C7—C8 | 1.15 (16) | C22—C23—C24—C25 | 0.07 (17) |
N3—C7—C8—F2 | 2.55 (15) | C23—C24—C25—C20 | 0.85 (17) |
C6—C7—C8—F2 | −178.11 (9) | C21—C20—C25—C24 | −1.17 (16) |
N3—C7—C8—C9 | −178.87 (10) | C26—C20—C25—C24 | 176.2 (1) |
C6—C7—C8—C9 | 0.47 (16) | C25—C20—C26—C27 | 128.84 (11) |
F2—C8—C9—N2 | −2.14 (15) | C21—C20—C26—C27 | −53.85 (14) |
C7—C8—C9—N2 | 179.25 (10) | C20—C26—C27—O5 | 130.02 (11) |
F2—C8—C9—C4 | 176.79 (9) | C20—C26—C27—O4 | −51.32 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3 | 0.95 (2) | 1.61 (2) | 2.5162 (12) | 157.3 (18) |
N2—H2NB···O3 | 0.900 (17) | 1.917 (16) | 2.6200 (13) | 133.6 (14) |
N4—H4NB···O4 | 0.949 (16) | 1.781 (16) | 2.7122 (12) | 166.3 (13) |
N2—H2NA···O5i | 0.869 (17) | 2.232 (17) | 2.9958 (13) | 146.5 (14) |
N4—H4NA···O4ii | 0.956 (16) | 1.834 (16) | 2.7580 (12) | 161.8 (14) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1. |
C19H23F2N4O3+·C8H7O2−·3H2O | F(000) = 1232 |
Mr = 582.60 | Dx = 1.411 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 18.4423 (9) Å | Cell parameters from 9800 reflections |
b = 7.0694 (3) Å | θ = 2.9–27.5° |
c = 21.0669 (10) Å | µ = 0.11 mm−1 |
β = 93.252 (2)° | T = 90 K |
V = 2742.2 (2) Å3 | Tablet, pale yellow |
Z = 4 | 0.19 × 0.15 × 0.04 mm |
Bruker D8 Venture dual source diffractometer | 6296 independent reflections |
Radiation source: microsource | 5086 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.043 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −23→23 |
Tmin = 0.894, Tmax = 0.959 | k = −9→9 |
44990 measured reflections | l = −27→27 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.040P)2 + 1.6577P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
6296 reflections | Δρmax = 0.31 e Å−3 |
418 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL-2019/2 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0021 (5) |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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. |
Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.16930 (4) | 0.64545 (14) | 0.41384 (4) | 0.0232 (2) | |
F2 | 0.19188 (4) | 0.74700 (13) | 0.63429 (4) | 0.0213 (2) | |
O1 | −0.20441 (5) | 0.79723 (16) | 0.41468 (5) | 0.0235 (2) | |
O2 | −0.19618 (5) | 0.87221 (15) | 0.51703 (5) | 0.0202 (2) | |
H2O | −0.1594 (12) | 0.877 (3) | 0.5482 (10) | 0.044 (6)* | |
O3 | −0.07638 (5) | 0.84435 (15) | 0.57818 (5) | 0.0189 (2) | |
N1 | 0.01575 (6) | 0.68755 (17) | 0.41300 (5) | 0.0142 (2) | |
N2 | 0.05167 (7) | 0.8265 (2) | 0.64025 (6) | 0.0213 (3) | |
H2NA | 0.0811 (11) | 0.828 (3) | 0.6762 (10) | 0.034 (5)* | |
H2NB | 0.0031 (12) | 0.843 (3) | 0.6419 (10) | 0.042 (6)* | |
N3 | 0.25676 (6) | 0.66015 (18) | 0.52407 (6) | 0.0177 (3) | |
N4 | 0.40460 (6) | 0.56168 (18) | 0.54358 (6) | 0.0147 (2) | |
H4NA | 0.4412 (10) | 0.495 (3) | 0.5696 (9) | 0.029 (5)* | |
H4NB | 0.4268 (10) | 0.618 (3) | 0.5108 (10) | 0.034 (5)* | |
C1 | −0.05565 (7) | 0.7201 (2) | 0.41541 (7) | 0.0152 (3) | |
H1 | −0.085398 | 0.704074 | 0.377484 | 0.018* | |
C2 | −0.08820 (7) | 0.7749 (2) | 0.46899 (7) | 0.0151 (3) | |
C3 | −0.04622 (7) | 0.79463 (19) | 0.52777 (7) | 0.0147 (3) | |
C4 | 0.03060 (7) | 0.75619 (19) | 0.52685 (7) | 0.0140 (3) | |
C5 | 0.06170 (7) | 0.70427 (19) | 0.46870 (6) | 0.0138 (3) | |
C6 | 0.13643 (7) | 0.6767 (2) | 0.46875 (7) | 0.0152 (3) | |
C7 | 0.18246 (7) | 0.6910 (2) | 0.52359 (7) | 0.0152 (3) | |
C8 | 0.15010 (7) | 0.7376 (2) | 0.57941 (7) | 0.0161 (3) | |
C9 | 0.07665 (7) | 0.7750 (2) | 0.58355 (7) | 0.0151 (3) | |
C10 | 0.28872 (7) | 0.5277 (2) | 0.48072 (7) | 0.0161 (3) | |
H10A | 0.307178 | 0.597178 | 0.444152 | 0.019* | |
H10B | 0.251383 | 0.436797 | 0.464287 | 0.019* | |
C11 | 0.35064 (7) | 0.4220 (2) | 0.51562 (7) | 0.0155 (3) | |
H11 | 0.330677 | 0.346821 | 0.550866 | 0.019* | |
C12 | 0.37170 (7) | 0.7063 (2) | 0.58566 (7) | 0.0156 (3) | |
H12 | 0.353367 | 0.640709 | 0.623632 | 0.019* | |
C13 | 0.30834 (7) | 0.8012 (2) | 0.54943 (7) | 0.0160 (3) | |
H13A | 0.283667 | 0.887997 | 0.578133 | 0.019* | |
H13B | 0.326437 | 0.876885 | 0.514093 | 0.019* | |
C14 | 0.43038 (8) | 0.8463 (2) | 0.60792 (7) | 0.0209 (3) | |
H14A | 0.449360 | 0.909818 | 0.570983 | 0.031* | |
H14B | 0.469877 | 0.778736 | 0.631283 | 0.031* | |
H14C | 0.409720 | 0.940576 | 0.635826 | 0.031* | |
C15 | 0.38846 (8) | 0.2884 (2) | 0.47176 (7) | 0.0206 (3) | |
H15A | 0.353957 | 0.192234 | 0.455446 | 0.031* | |
H15B | 0.429211 | 0.226688 | 0.495390 | 0.031* | |
H15C | 0.406627 | 0.360047 | 0.436145 | 0.031* | |
C16 | 0.04298 (7) | 0.6192 (2) | 0.35325 (7) | 0.0163 (3) | |
H16 | 0.062144 | 0.486827 | 0.354403 | 0.020* | |
C17 | 0.08061 (8) | 0.7518 (2) | 0.31081 (7) | 0.0218 (3) | |
H17A | 0.122153 | 0.702225 | 0.288103 | 0.026* | |
H17B | 0.085039 | 0.885832 | 0.324048 | 0.026* | |
C18 | 0.00625 (8) | 0.6788 (3) | 0.29126 (7) | 0.0264 (4) | |
H18A | −0.035058 | 0.767882 | 0.292530 | 0.032* | |
H18B | 0.002063 | 0.584243 | 0.256578 | 0.032* | |
C19 | −0.16741 (7) | 0.8147 (2) | 0.46384 (7) | 0.0173 (3) | |
O4 | 0.48721 (6) | 0.37218 (16) | 0.63034 (5) | 0.0225 (2) | |
O5 | 0.55454 (5) | 0.23301 (15) | 0.55920 (5) | 0.0191 (2) | |
C20 | 0.59698 (7) | 0.2240 (2) | 0.66740 (7) | 0.0146 (3) | |
C21 | 0.58790 (8) | 0.2764 (2) | 0.73007 (7) | 0.0169 (3) | |
H21 | 0.544617 | 0.338837 | 0.740721 | 0.020* | |
C22 | 0.64159 (8) | 0.2383 (2) | 0.77720 (7) | 0.0171 (3) | |
H22 | 0.634344 | 0.274197 | 0.819832 | 0.021* | |
C23 | 0.70593 (8) | 0.1483 (2) | 0.76303 (7) | 0.0166 (3) | |
C24 | 0.71450 (8) | 0.0948 (2) | 0.70020 (7) | 0.0173 (3) | |
H24 | 0.757892 | 0.033059 | 0.689484 | 0.021* | |
C25 | 0.66076 (8) | 0.1303 (2) | 0.65326 (7) | 0.0172 (3) | |
H25 | 0.667292 | 0.090469 | 0.610891 | 0.021* | |
C26 | 0.54199 (7) | 0.2778 (2) | 0.61474 (7) | 0.0159 (3) | |
C27 | 0.76456 (8) | 0.1112 (2) | 0.81411 (7) | 0.0209 (3) | |
H27A | 0.765320 | −0.023819 | 0.824717 | 0.031* | |
H27B | 0.754839 | 0.184994 | 0.852067 | 0.031* | |
H27C | 0.811717 | 0.148138 | 0.798799 | 0.031* | |
O1W | 0.29379 (6) | 0.11084 (17) | 0.69541 (6) | 0.0268 (3) | |
H1W1 | 0.3314 (14) | 0.219 (4) | 0.7047 (12) | 0.064 (7)* | |
H2W1 | 0.2678 (15) | 0.150 (4) | 0.6565 (14) | 0.077 (9)* | |
O2W | 0.39349 (6) | 0.39000 (18) | 0.72635 (5) | 0.0236 (2) | |
H1W2 | 0.3732 (13) | 0.510 (4) | 0.7276 (11) | 0.060 (7)* | |
H2W2 | 0.4297 (13) | 0.386 (4) | 0.6967 (12) | 0.058 (7)* | |
O3W | 0.32955 (6) | 0.73767 (19) | 0.74222 (6) | 0.0302 (3) | |
H1W3 | 0.2830 (13) | 0.702 (4) | 0.7636 (11) | 0.057 (7)* | |
H2W3 | 0.3180 (17) | 0.868 (5) | 0.7265 (15) | 0.100 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0146 (4) | 0.0418 (6) | 0.0133 (4) | 0.0048 (4) | 0.0013 (3) | −0.0019 (4) |
F2 | 0.0176 (4) | 0.0310 (5) | 0.0147 (4) | 0.0010 (4) | −0.0054 (3) | −0.0021 (4) |
O1 | 0.0155 (5) | 0.0304 (6) | 0.0241 (6) | 0.0022 (5) | −0.0036 (4) | −0.0007 (5) |
O2 | 0.0143 (5) | 0.0240 (6) | 0.0224 (6) | 0.0014 (4) | 0.0015 (4) | 0.0000 (4) |
O3 | 0.0168 (5) | 0.0245 (6) | 0.0157 (5) | 0.0019 (4) | 0.0030 (4) | 0.0003 (4) |
N1 | 0.0139 (5) | 0.0158 (6) | 0.0127 (6) | 0.0002 (5) | −0.0002 (4) | 0.0003 (5) |
N2 | 0.0174 (6) | 0.0331 (8) | 0.0132 (6) | 0.0015 (6) | 0.0001 (5) | −0.0029 (5) |
N3 | 0.0124 (5) | 0.0200 (6) | 0.0204 (6) | 0.0009 (5) | −0.0019 (5) | −0.0050 (5) |
N4 | 0.0131 (5) | 0.0173 (6) | 0.0136 (6) | 0.0009 (5) | −0.0008 (5) | −0.0009 (5) |
C1 | 0.0140 (6) | 0.0134 (6) | 0.0176 (7) | −0.0004 (5) | −0.0028 (5) | 0.0021 (5) |
C2 | 0.0130 (6) | 0.0147 (7) | 0.0174 (7) | 0.0001 (5) | −0.0002 (5) | 0.0024 (5) |
C3 | 0.0160 (6) | 0.0111 (6) | 0.0171 (7) | −0.0008 (5) | 0.0006 (5) | 0.0031 (5) |
C4 | 0.0145 (6) | 0.0122 (6) | 0.0152 (7) | −0.0007 (5) | 0.0001 (5) | 0.0012 (5) |
C5 | 0.0144 (6) | 0.0127 (6) | 0.0139 (7) | −0.0013 (5) | −0.0015 (5) | 0.0016 (5) |
C6 | 0.0158 (6) | 0.0172 (7) | 0.0127 (6) | 0.0003 (5) | 0.0024 (5) | 0.0001 (5) |
C7 | 0.0130 (6) | 0.0141 (7) | 0.0182 (7) | 0.0004 (5) | −0.0010 (5) | 0.0010 (5) |
C8 | 0.0166 (7) | 0.0180 (7) | 0.0132 (7) | −0.0010 (5) | −0.0047 (5) | 0.0011 (5) |
C9 | 0.0168 (7) | 0.0143 (7) | 0.0142 (7) | −0.0012 (5) | 0.0003 (5) | 0.0012 (5) |
C10 | 0.0147 (6) | 0.0175 (7) | 0.0160 (7) | −0.0004 (5) | −0.0013 (5) | −0.0029 (6) |
C11 | 0.0143 (6) | 0.0149 (7) | 0.0171 (7) | −0.0013 (5) | −0.0007 (5) | −0.0003 (5) |
C12 | 0.0148 (6) | 0.0191 (7) | 0.0127 (6) | 0.0007 (6) | 0.0003 (5) | −0.0021 (6) |
C13 | 0.0143 (6) | 0.0164 (7) | 0.0171 (7) | −0.0002 (5) | −0.0009 (5) | −0.0022 (6) |
C14 | 0.0158 (7) | 0.0251 (8) | 0.0215 (8) | −0.0008 (6) | −0.0019 (6) | −0.0067 (6) |
C15 | 0.0199 (7) | 0.0189 (7) | 0.0229 (8) | 0.0025 (6) | −0.0007 (6) | −0.0042 (6) |
C16 | 0.0163 (6) | 0.0177 (7) | 0.0147 (7) | 0.0017 (5) | −0.0008 (5) | −0.0020 (5) |
C17 | 0.0234 (7) | 0.0245 (8) | 0.0180 (7) | 0.0036 (6) | 0.0040 (6) | 0.0041 (6) |
C18 | 0.0223 (7) | 0.0419 (10) | 0.0148 (7) | 0.0071 (7) | −0.0009 (6) | 0.0002 (7) |
C19 | 0.0154 (7) | 0.0166 (7) | 0.0200 (7) | −0.0004 (6) | 0.0015 (5) | 0.0021 (6) |
O4 | 0.0197 (5) | 0.0300 (6) | 0.0174 (5) | 0.0076 (5) | −0.0009 (4) | 0.0015 (5) |
O5 | 0.0201 (5) | 0.0236 (6) | 0.0135 (5) | −0.0011 (4) | −0.0011 (4) | 0.0008 (4) |
C20 | 0.0158 (6) | 0.0138 (6) | 0.0139 (7) | −0.0016 (5) | −0.0008 (5) | 0.0012 (5) |
C21 | 0.0153 (6) | 0.0191 (7) | 0.0164 (7) | 0.0003 (6) | 0.0013 (5) | 0.0005 (6) |
C22 | 0.0199 (7) | 0.0180 (7) | 0.0135 (7) | −0.0009 (6) | 0.0010 (5) | 0.0003 (6) |
C23 | 0.0185 (7) | 0.0137 (7) | 0.0172 (7) | −0.0014 (5) | −0.0015 (5) | 0.0032 (5) |
C24 | 0.0176 (7) | 0.0149 (7) | 0.0194 (7) | 0.0030 (6) | 0.0007 (6) | 0.0010 (6) |
C25 | 0.0211 (7) | 0.0151 (7) | 0.0152 (7) | −0.0003 (6) | 0.0012 (5) | −0.0004 (6) |
C26 | 0.0160 (6) | 0.0158 (7) | 0.0159 (7) | −0.0024 (5) | −0.0002 (5) | 0.0027 (5) |
C27 | 0.0225 (7) | 0.0212 (7) | 0.0184 (7) | 0.0025 (6) | −0.0041 (6) | 0.0018 (6) |
O1W | 0.0254 (6) | 0.0285 (6) | 0.0262 (6) | 0.0007 (5) | −0.0017 (5) | −0.0008 (5) |
O2W | 0.0219 (5) | 0.0287 (6) | 0.0201 (6) | 0.0018 (5) | 0.0008 (4) | 0.0019 (5) |
O3W | 0.0257 (6) | 0.0307 (7) | 0.0349 (7) | 0.0040 (5) | 0.0072 (5) | 0.0039 (5) |
F1—C6 | 1.3541 (16) | C13—H13B | 0.9900 |
F2—C8 | 1.3540 (15) | C14—H14A | 0.9800 |
O1—C19 | 1.2138 (18) | C14—H14B | 0.9800 |
O2—C19 | 1.3305 (18) | C14—H14C | 0.9800 |
O2—H2O | 0.92 (2) | C15—H15A | 0.9800 |
O3—C3 | 1.2758 (17) | C15—H15B | 0.9800 |
N1—C1 | 1.3404 (17) | C15—H15C | 0.9800 |
N1—C5 | 1.4129 (17) | C16—C17 | 1.493 (2) |
N1—C16 | 1.4636 (18) | C16—C18 | 1.497 (2) |
N2—C9 | 1.3542 (19) | C16—H16 | 1.0000 |
N2—H2NA | 0.91 (2) | C17—C18 | 1.501 (2) |
N2—H2NB | 0.91 (2) | C17—H17A | 0.9900 |
N3—C7 | 1.3870 (17) | C17—H17B | 0.9900 |
N3—C10 | 1.4558 (18) | C18—H18A | 0.9900 |
N3—C13 | 1.4585 (18) | C18—H18B | 0.9900 |
N4—C11 | 1.4987 (18) | O4—C26 | 1.2692 (18) |
N4—C12 | 1.5036 (18) | O5—C26 | 1.2465 (17) |
N4—H4NA | 0.967 (19) | C20—C21 | 1.391 (2) |
N4—H4NB | 0.91 (2) | C20—C25 | 1.397 (2) |
C1—C2 | 1.364 (2) | C20—C26 | 1.5089 (19) |
C1—H1 | 0.9500 | C21—C22 | 1.388 (2) |
C2—C3 | 1.4296 (19) | C21—H21 | 0.9500 |
C2—C19 | 1.4855 (19) | C22—C23 | 1.394 (2) |
C3—C4 | 1.4438 (19) | C22—H22 | 0.9500 |
C4—C5 | 1.4298 (19) | C23—C24 | 1.394 (2) |
C4—C9 | 1.4321 (19) | C23—C27 | 1.5045 (19) |
C5—C6 | 1.3920 (19) | C24—C25 | 1.383 (2) |
C6—C7 | 1.3980 (19) | C24—H24 | 0.9500 |
C7—C8 | 1.388 (2) | C25—H25 | 0.9500 |
C8—C9 | 1.3877 (19) | C27—H27A | 0.9800 |
C10—C11 | 1.5193 (19) | C27—H27B | 0.9800 |
C10—H10A | 0.9900 | C27—H27C | 0.9800 |
C10—H10B | 0.9900 | O1W—H1W1 | 1.04 (3) |
C11—C15 | 1.518 (2) | O1W—H2W1 | 0.96 (3) |
C11—H11 | 1.0000 | O2W—H1W2 | 0.93 (3) |
C12—C13 | 1.5155 (19) | O2W—H2W2 | 0.94 (3) |
C12—C14 | 1.521 (2) | O3W—H1W3 | 1.02 (3) |
C12—H12 | 1.0000 | O3W—H2W3 | 1.00 (4) |
C13—H13A | 0.9900 | ||
C19—O2—H2O | 107.5 (14) | C12—C13—H13B | 109.6 |
C1—N1—C5 | 119.89 (12) | H13A—C13—H13B | 108.1 |
C1—N1—C16 | 118.36 (11) | C12—C14—H14A | 109.5 |
C5—N1—C16 | 121.53 (11) | C12—C14—H14B | 109.5 |
C9—N2—H2NA | 121.5 (12) | H14A—C14—H14B | 109.5 |
C9—N2—H2NB | 117.1 (13) | C12—C14—H14C | 109.5 |
H2NA—N2—H2NB | 120.8 (18) | H14A—C14—H14C | 109.5 |
C7—N3—C10 | 122.11 (12) | H14B—C14—H14C | 109.5 |
C7—N3—C13 | 121.25 (12) | C11—C15—H15A | 109.5 |
C10—N3—C13 | 113.00 (11) | C11—C15—H15B | 109.5 |
C11—N4—C12 | 113.50 (11) | H15A—C15—H15B | 109.5 |
C11—N4—H4NA | 109.2 (11) | C11—C15—H15C | 109.5 |
C12—N4—H4NA | 106.8 (11) | H15A—C15—H15C | 109.5 |
C11—N4—H4NB | 107.8 (12) | H15B—C15—H15C | 109.5 |
C12—N4—H4NB | 111.4 (13) | N1—C16—C17 | 120.10 (13) |
H4NA—N4—H4NB | 108.1 (16) | N1—C16—C18 | 119.79 (12) |
N1—C1—C2 | 124.01 (13) | C17—C16—C18 | 60.25 (10) |
N1—C1—H1 | 118.0 | N1—C16—H16 | 115.2 |
C2—C1—H1 | 118.0 | C17—C16—H16 | 115.2 |
C1—C2—C3 | 120.15 (12) | C18—C16—H16 | 115.2 |
C1—C2—C19 | 118.06 (13) | C16—C17—C18 | 60.0 (1) |
C3—C2—C19 | 121.78 (13) | C16—C17—H17A | 117.8 |
O3—C3—C2 | 120.51 (12) | C18—C17—H17A | 117.8 |
O3—C3—C4 | 122.51 (13) | C16—C17—H17B | 117.8 |
C2—C3—C4 | 116.98 (12) | C18—C17—H17B | 117.8 |
C5—C4—C9 | 119.40 (12) | H17A—C17—H17B | 114.9 |
C5—C4—C3 | 120.09 (12) | C16—C18—C17 | 59.75 (10) |
C9—C4—C3 | 120.49 (13) | C16—C18—H18A | 117.8 |
C6—C5—N1 | 122.42 (12) | C17—C18—H18A | 117.8 |
C6—C5—C4 | 118.73 (12) | C16—C18—H18B | 117.8 |
N1—C5—C4 | 118.83 (12) | C17—C18—H18B | 117.8 |
F1—C6—C5 | 120.90 (12) | H18A—C18—H18B | 114.9 |
F1—C6—C7 | 115.95 (12) | O1—C19—O2 | 121.19 (13) |
C5—C6—C7 | 123.03 (13) | O1—C19—C2 | 123.08 (13) |
N3—C7—C8 | 120.21 (12) | O2—C19—C2 | 115.72 (12) |
N3—C7—C6 | 123.22 (13) | C21—C20—C25 | 118.51 (13) |
C8—C7—C6 | 116.57 (12) | C21—C20—C26 | 121.24 (13) |
F2—C8—C9 | 116.56 (12) | C25—C20—C26 | 120.12 (13) |
F2—C8—C7 | 118.93 (12) | C22—C21—C20 | 120.52 (13) |
C9—C8—C7 | 124.51 (13) | C22—C21—H21 | 119.7 |
N2—C9—C8 | 119.27 (13) | C20—C21—H21 | 119.7 |
N2—C9—C4 | 123.04 (13) | C21—C22—C23 | 121.13 (13) |
C8—C9—C4 | 117.69 (13) | C21—C22—H22 | 119.4 |
N3—C10—C11 | 109.43 (11) | C23—C22—H22 | 119.4 |
N3—C10—H10A | 109.8 | C22—C23—C24 | 118.09 (13) |
C11—C10—H10A | 109.8 | C22—C23—C27 | 120.84 (13) |
N3—C10—H10B | 109.8 | C24—C23—C27 | 121.07 (13) |
C11—C10—H10B | 109.8 | C25—C24—C23 | 120.97 (13) |
H10A—C10—H10B | 108.2 | C25—C24—H24 | 119.5 |
N4—C11—C15 | 109.35 (11) | C23—C24—H24 | 119.5 |
N4—C11—C10 | 109.27 (11) | C24—C25—C20 | 120.76 (13) |
C15—C11—C10 | 111.72 (12) | C24—C25—H25 | 119.6 |
N4—C11—H11 | 108.8 | C20—C25—H25 | 119.6 |
C15—C11—H11 | 108.8 | O5—C26—O4 | 124.71 (13) |
C10—C11—H11 | 108.8 | O5—C26—C20 | 118.24 (13) |
N4—C12—C13 | 109.24 (11) | O4—C26—C20 | 117.00 (12) |
N4—C12—C14 | 108.69 (11) | C23—C27—H27A | 109.5 |
C13—C12—C14 | 112.46 (12) | C23—C27—H27B | 109.5 |
N4—C12—H12 | 108.8 | H27A—C27—H27B | 109.5 |
C13—C12—H12 | 108.8 | C23—C27—H27C | 109.5 |
C14—C12—H12 | 108.8 | H27A—C27—H27C | 109.5 |
N3—C13—C12 | 110.49 (12) | H27B—C27—H27C | 109.5 |
N3—C13—H13A | 109.6 | H1W1—O1W—H2W1 | 104 (2) |
C12—C13—H13A | 109.6 | H1W2—O2W—H2W2 | 110 (2) |
N3—C13—H13B | 109.6 | H1W3—O3W—H2W3 | 102 (2) |
C5—N1—C1—C2 | 1.9 (2) | C5—C4—C9—N2 | 178.94 (13) |
C16—N1—C1—C2 | 176.62 (13) | C3—C4—C9—N2 | 0.8 (2) |
N1—C1—C2—C3 | −2.2 (2) | C5—C4—C9—C8 | −1.3 (2) |
N1—C1—C2—C19 | 177.15 (13) | C3—C4—C9—C8 | −179.45 (13) |
C1—C2—C3—O3 | −179.45 (13) | C7—N3—C10—C11 | −140.81 (13) |
C19—C2—C3—O3 | 1.3 (2) | C13—N3—C10—C11 | 60.49 (15) |
C1—C2—C3—C4 | 0.6 (2) | C12—N4—C11—C15 | 177.44 (12) |
C19—C2—C3—C4 | −178.66 (12) | C12—N4—C11—C10 | 54.87 (15) |
O3—C3—C4—C5 | −178.86 (13) | N3—C10—C11—N4 | −56.09 (15) |
C2—C3—C4—C5 | 1.06 (19) | N3—C10—C11—C15 | −177.22 (12) |
O3—C3—C4—C9 | −0.7 (2) | C11—N4—C12—C13 | −53.64 (15) |
C2—C3—C4—C9 | 179.20 (13) | C11—N4—C12—C14 | −176.68 (12) |
C1—N1—C5—C6 | −178.40 (13) | C7—N3—C13—C12 | 141.28 (13) |
C16—N1—C5—C6 | 7.0 (2) | C10—N3—C13—C12 | −59.81 (16) |
C1—N1—C5—C4 | −0.05 (19) | N4—C12—C13—N3 | 54.01 (15) |
C16—N1—C5—C4 | −174.64 (12) | C14—C12—C13—N3 | 174.77 (12) |
C9—C4—C5—C6 | −1.1 (2) | C1—N1—C16—C17 | 102.71 (15) |
C3—C4—C5—C6 | 177.05 (13) | C5—N1—C16—C17 | −82.62 (17) |
C9—C4—C5—N1 | −179.52 (12) | C1—N1—C16—C18 | 31.9 (2) |
C3—C4—C5—N1 | −1.36 (19) | C5—N1—C16—C18 | −153.41 (14) |
N1—C5—C6—F1 | 4.8 (2) | N1—C16—C17—C18 | −109.28 (15) |
C4—C5—C6—F1 | −173.55 (12) | N1—C16—C18—C17 | 109.78 (15) |
N1—C5—C6—C7 | −179.38 (13) | C1—C2—C19—O1 | 1.4 (2) |
C4—C5—C6—C7 | 2.3 (2) | C3—C2—C19—O1 | −179.26 (14) |
C10—N3—C7—C8 | 148.72 (14) | C1—C2—C19—O2 | −178.35 (13) |
C13—N3—C7—C8 | −54.31 (19) | C3—C2—C19—O2 | 1.0 (2) |
C10—N3—C7—C6 | −30.9 (2) | C25—C20—C21—C22 | 0.8 (2) |
C13—N3—C7—C6 | 126.05 (15) | C26—C20—C21—C22 | −175.08 (13) |
F1—C6—C7—N3 | −5.2 (2) | C20—C21—C22—C23 | 0.5 (2) |
C5—C6—C7—N3 | 178.76 (13) | C21—C22—C23—C24 | −1.0 (2) |
F1—C6—C7—C8 | 175.12 (12) | C21—C22—C23—C27 | 178.68 (14) |
C5—C6—C7—C8 | −0.9 (2) | C22—C23—C24—C25 | 0.1 (2) |
N3—C7—C8—F2 | −1.9 (2) | C27—C23—C24—C25 | −179.53 (14) |
C6—C7—C8—F2 | 177.78 (12) | C23—C24—C25—C20 | 1.2 (2) |
N3—C7—C8—C9 | 178.56 (13) | C21—C20—C25—C24 | −1.6 (2) |
C6—C7—C8—C9 | −1.8 (2) | C26—C20—C25—C24 | 174.28 (13) |
F2—C8—C9—N2 | 3.0 (2) | C21—C20—C26—O5 | 177.27 (13) |
C7—C8—C9—N2 | −177.39 (14) | C25—C20—C26—O5 | 1.5 (2) |
F2—C8—C9—C4 | −176.72 (12) | C21—C20—C26—O4 | −0.3 (2) |
C7—C8—C9—C4 | 2.8 (2) | C25—C20—C26—O4 | −176.07 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O3 | 0.92 (2) | 1.64 (2) | 2.5014 (14) | 155 (2) |
N2—H2NB···O3 | 0.91 (2) | 1.93 (2) | 2.6367 (17) | 133.4 (18) |
N4—H4NA···O4 | 0.967 (19) | 1.73 (2) | 2.6722 (16) | 164.1 (17) |
N4—H4NB···O5i | 0.91 (2) | 1.86 (2) | 2.7473 (16) | 163.0 (18) |
N2—H2NA···O2Wii | 0.91 (2) | 2.12 (2) | 2.9664 (17) | 153.9 (17) |
O2W—H2W2···O4 | 0.94 (3) | 1.80 (3) | 2.7371 (16) | 171 (2) |
O1W—H1W1···O2W | 1.04 (3) | 1.71 (3) | 2.7503 (17) | 175 (2) |
O2W—H1W2···O3W | 0.93 (3) | 1.83 (3) | 2.7546 (18) | 171 (2) |
O1W—H2W1···O1iii | 0.96 (3) | 1.89 (3) | 2.8434 (16) | 171 (2) |
O3W—H1W3···O1Wii | 1.02 (3) | 1.82 (3) | 2.8362 (17) | 173 (2) |
O3W—H2W3···O1Wiv | 1.00 (4) | 1.88 (4) | 2.8798 (18) | 178 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x, −y+1, −z+1; (iv) x, y+1, z. |
Atom contacts | I | II | III |
H···H | 41.2 | 40.3 | 48.0 |
H···O | 28.8 | 25.5 | 23.4 |
H···C | 10.0 | 15.5 | 7.9 |
C···C | 6.0 | 4.6 | 7.7 |
H···F | 3.5 | 7.7 | 5.7 |
O···F | 2.6 | 0.2 | 1.3 |
C···O | 2.3 | 1.4 | 2.5 |
H···N | 1.6 | 3.0 | 1.5 |
Heterogeneous contact types here include the reciprocal interactions, e.g., "H···O" represents "H···O/O···H". All other fractions of atom-contact coverages were negligible. |
Acknowledgements
One of the authors (HJS) is grateful to the University of Mysore for research facilities. HSY also thanks UGC for a BSR Faculty fellowship for three years.
Funding information
Funding for this research was provided by: NSF (MRI CHE1625732) and the University of Kentucky (Bruker D8 Venture diffractometer) to SP.
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