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Two different heterocycles, a pyrazole and an oxadiazine, are formed by the reactions of a common precursor, (2RS,3SR)-2,3-di­bromo-1,3-bis­(4-fluoro­phenyl)propan-1-one, with dif­ferent simple hydrazines. In 3,5-bis­(4-fluoro­phenyl)-1-phenyl-1H-pyrazole, C21H14F2N2, (I), formed using phenyl­hydrazine, there is some aromatic-type delocalization in the pyrazole ring, and the mol­ecules are linked into simple chains by a single C-H...[pi](arene) hydrogen bond. The reaction with 4-hy­droxy­benzo­hydrazide gives (5RS,6SR)-6-(4-fluorobenzoyl)-5-(4-fluoro­phenyl)-2-(4-hy­droxy­phenyl)-5,6-dihydro-4H-1,3,4-oxadiazine, which was crystallized from N,N-di­methyl­formamide to give the mono­solvate, C22H16F2N2O3·C3H7NO, (II), in which the solvent mol­ecule is disordered over two sets of atomic sites having occupancies of 0.557 (10) and 0.443 (10). The oxa­diazine mol­ecules in (II) are linked by a combination of N-H...N and C-H...O hydrogen bonds to form complex sheets, having the hydrogen bonds in the central layer and with the solvent mol­ecules attached at the outer faces by O-H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614017707/sk3555sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017707/sk3555Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017707/sk3555IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614017707/sk3555Isup4.cml
Supplementary material

CCDC references: 1017474; 1017475

Introduction top

Pyrazole derivatives occupy an important position in the design and synthesis of novel biologically active agents, as they display a wide range of biological activities such as anti­tumour, anti­bacterial, anti­fungal, anti­viral, anti­parasitic, anti­tubercular and insecticidal properties (Hes et al., 1978; Grosscurt et al., 1979; Amir et al., 2008). Some of these compounds also display anti­oxidant, anti-inflammatory and analgesic properties (Amir & Kumar, 2005; Sarojini et al., 2010). Oxadiazines are also associated with a variety of biological activities, including anti­bacterial, cardiovascular, plant-growth regulating, insecticidal, acaricidal, anti­convulsive, miticidal and nematocidal activities (Kornet, 1996; Khan et al., 2002). Hence, it is of inter­est to explore new routes to these heterocyclic systems, and here we report the synthesis and structural characteristics of examples of both heterocyclic systems, a pyrazole and an oxadiazine, respectively, derived from the reactions of a common precursor, 2,3-di­bromo-1,3-bis­(4-fluoro­phenyl)­propan-1-one, with different simple hydrazines. The di­bromo precursor was itself prepared by addition of molecular bromine to 1,3-bis­(4-fluoro­phenyl)­prop-2-en-1-one, where it is formed as a racemic mixture of the (2R,3S) and (2S,3R) diastereoisomers, as shown by the deposited atomic coordinates (Jasinski et al., 2010b), although the stereochemistry was not mentioned in the original structure report. This di­bromo­propanone reacts with phenyl­hydrazine to form 3,5-bis­(4-fluoro­phenyl)-1-phenyl-1H-pyrazole, (I), in a cyclization reaction mediated by an excess of base which involves the elimination of one molecule of water and two molecules of hydrogen bromide. However, with 4-hy­droxy­benzohydrazide, the oxadiazine derivative (5RS,6SR)-6-(4-fluoro­benzoyl)-5-(4-fluoro­phenyl)-2-(4-hy­droxy­phenyl)-5,6-di­hydro-4H-1,3,4-oxadiazine is formed, which on crystallization from N,N-di­methyl­formamide (DMF) forms a stoichiometric monosolvate, (II) (Fig. 2). The synthesis of a reduced analogue of (I), namely 3,5-bis­(4-fluoro­phenyl)-1-phenyl-4,5-di­hydro-1H-pyrazole, (III) (see scheme), prepared by a cyclo­addition reaction between 1,3-bis­(4-fluoro­phenyl)­prop-2-en-1-one and phenyl­hydrazine, has recently been described (Jasinski et al., 2010a). The purposes of the present study are the confirmation of the molecular constitutions of (I) and (II), in particular both the regiochemistry of the formation of the oxadiazine component (IIa) as opposed to the alternative isomeric form (IIb) (see scheme), and the stereochemistry of this component; the exploration of the supra­molecular assembly in both (I) and (II); and the comparison of (I) with its reduced analogue, (III).

Experimental top

Synthesis and crystallization top

For the synthesis of (I), a mixture of (2RS,3SR)-2,3-di­bromo-1,3-bis­(4-fluoro­phenyl)­propan-1-one (4.04 g, 0.01 mol), phenyl­hydrazine (1.08 g, 0.01 mol) and tri­ethyl­amine (3 ml) in ethanol (20 ml) was heated under reflux for 6 h. The reaction mixture was then cooled to ambient temperature and poured into ice-cold water. The resulting precipitate was collected by filtration and purified by recrystallization from ethanol, at ambient temperature and in the presence of air (yield 71%, m.p. 341–343 K). Spectroscopic analysis: IR (KBr, ν, cm-1): 3061 (Ar—H), 1597 (CN), 1219 (C—F); 1H NMR (DMSO-d6, δ, p.p.m.): 7.16 (s, 1H, pyrazole-H), 7.21–7.94 (m, 13H, Ar—H); LCMS: m/z 333.1 (M++1). Analysis, found: C 75.8, H 4.2, N 8.4%; C21H14F2N2 requires: C 75.9, H 4.2, N 8.4%.

For the synthesis of (II), a mixture of (2RS,3SR)-2,3-di­bromo-1,3- bis­(4-fluoro­phenyl)­propan-1-one (4.04 g, 0.01 mol), 4-hy­droxy­benzohydrazide (1.52 g, 0.01 mol) and tri­ethyl­amine (3 ml) in ethanol (15 ml) was heated under reflux for 8 h. The reaction mixture was then cooled to ambient temperature and poured into ice-cold water. The resulting solid was collected by filtration, dried and recrystallized from ethanol (yield 64%, m.p. 484–2487 K). Spectroscopic analysis: IR (KBr, ν, cm-1): 3267 (OH), 3074, 2937 (CH2), 1658 (CO), 1593 (CN), 1215 (C—F); 1H NMR (DMSO-d6, δ, p.p.m.): 4.33 (d, 1H, CH), 6.15(d, 1H, CH), 6.90 (s, 1H, NH), 6.72 - 8.03 (m, 12H, Ar—H), 9.64 (s, 1H, Ar—OH); LCMS: m/z 394.8 (M++1). Analysis, found: C 70.0, H 4.0, N 7.1%; C22H16F2N2O3 requires: C 67.0, H 4.1, N 7.1%. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in the presence of air, of a solution in DMF, yielding the monosolvate (II). [The order of these last two sentences implies that the analysis data all relate to the unsolvated ethanol-grown compound, (IIa). Is this correct?]

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms. C-bound H atoms were treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic, formyl and pyrazole), 0.98 (CH3) or 1.00 Å (aliphatic C—H), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other C-bound H atoms. The N- or O-bound H atoms in (II) were permitted to ride at the positions located in difference maps, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O), giving N—H and O—H distances of 0.91 and 0.92 Å, respectively. It was apparent that the DMF component in (II) was disordered over two sets of atomic sites with similar occupancies. The bond distances and the one-angle non-bonded distances in the minor orientation were constrained to be identical to the corresponding distances in the major orientation, subject to uncertainties of 0.005 and 0.01 Å, respectively, and the anisotropic displacement parameters of pairs of atoms occupying the same approximate volume of physical space were constrained to be equal. Under these conditions, free refinement of the site occupancies gave values of 0.552 (9) and 0.438 (9), respectively; accordingly, these occupancies were thereafter constrained to sum to unity, giving final values of 0.557 (10) and 0.443 (10).

Results and discussion top

In (I) (Fig. 1) the bond distances in the pyrazole ring (Table 2) provide evidence for some aromatic-type delocalization. Thus, the distances N1—C5 and N2—C3 differ by only ca 0.03 Å, even though these bonds are formally single and double, respectively. Similarly, the distances C3—C4 and C4—C5 differ by only ca 0.03 Å, although again these are formally single and double bonds, respectively. The molecular conformation of (I) can be specified in terms of three torsion angles (Table 2) defining the orientations of the three aryl rings relative to the central pyrazole ring. The dihedral angles between the pyrazole ring and the three aryl rings containing atoms C11, C31 and C51 are 55.88 (9), 23.69 (9) and 52.08 (9)°, respectively. The molecules of (I) therefore exhibit no inter­nal symmetry and they are thus conformationally chiral, although the centrosymmetric space group accommodates equal numbers of the two conformational enanti­omers.

Compound (II) crystallizes as a monosolvate with DMF (Fig. 2), in which the DMF component is disordered over two sets of atomic sites having similar but non-identical occupancies, viz. 0.557 (10) and 0.443 (10), respectively (see Refinement, sec2.2). There are two stereogenic centres in the oxadiazine component at atoms C5 and C6. The reference molecule was selected as one having the R configuration at atom C5 and, on this basis, the configuration at atom C6 is S. The centrosymmetric space group confirms that the oxadiazine component is present as a racemic mixture of the (5R,6S) and (5S,6R) diastereoisomers, as expected from the (2RS,3SR) stereochemistry of the di­bromo­propanone precursor. The ring-puckering parameters (Cremer & Pople, 1975), calculated for the atom sequence O1–C2–N3–N4–C5–C6, are Q = 0.5044 (15) Å, θ = 53.24 (16)° and φ = 238.0 (2)°. For an idealized envelope conformation, the ring-puckering angles (Boeyens, 1978) are θ = 54.7° and φ = (k × 60)°, where k represents an integer. The oxadiazine ring thus has an envelope conformation and the ring is folded across the line N4···C6. The distances within the oxadiazine ring (Table 4) are fully consistent with its oxidation level, with a clear distinction between the single and double C—N bonds, N4—C5 and C2—N3, respectively. The molecules are thus conformationally chiral, as well as configurationally chiral. The isolated yield of this component indicates that the isomeric form shown in (IIa) is, at the least, the dominant product, as opposed to (IIb), although the formation of a small proportion of this alternative isomer cannot be ruled out.

The molecules of (I) are linked by a single C—H···π(arene) hydrogen bond (Table 3). Molecules related by the c-glide plane at y = 1/2 are linked into a chain running parallel to the [001] direction (Fig. 3). Four chains pass through each unit cell but there are no direction-specific inter­actions between adjacent chains. Despite the presence of three independent aryl rings, no aromatic ππ stacking inter­actions are present in the crystal structure of (I).

The supra­molecular assembly of (II) is considerably more complex than that in (I). The independent molecular components are linked by O—H···O hydrogen bonds (Table 5 and Fig. 2), but the DMF component is not involved in any other direction-specific inter­molecular inter­actions, and its role may be principally that of occupying otherwise void spaces within the structure defined by the oxadiazine component. A combination of N—H···N and C—H···O hydrogen bonds (Table 5) links the oxadiazine molecules into complex sheets, from which the DMF molecules are simply pendent, and the formation of the sheet structure is readily analysed in terms of two simple substructures (Ferguson et al., 1998a,b; Gregson et al., 2000).

In the simpler of the two substructures, two inversion-related oxadiazine molecules are linked by symmetry-related N—H···N hydrogen bonds to form a cyclic centrosymmetric dimer characterized by an R22(6) (Bernstein et al., 1995) motif (Fig. 4). The reference dimer is centred at (1/2, 1/2, 1/2) and this finite zero-dimensional substructure can be regarded as a key building block in the sheet formation. In the second substructure, which is one-dimensional, oxadiazine molecules which are related by the 21 screw axis along (1/2, y, 1/4) are linked by two independent C—H···O hydrogen bonds to form a C(5)C(7)[R21(6)] chain of rings running parallel to the [010] direction (Fig. 5). The combination of these two substructures has the effect of directly linking the reference R22(6) dimer centred at (1/2, 1/2, 1/2) to the four symmetry-related dimers centred at (1/2, 0, 0), (1/2, 1, 0), (1/2, 0, 1) and (1/2, 1, 1), so leading to the formation of a sheet lying parallel to (100) (Fig. 6). Just one sheet of this type passes through each unit cell and the DMF components are pendent from it, on the outer faces of the sheet, while the hydrogen bonds linking the oxadiazine components lie in the central portion of the sheet (Fig. 7).

There are several inter­esting differences between (I), reported here, and its reduced analogue, (III) (Jasinski et al., 2010a). Firstly, (III) crystallizes in space group P21/c, whereas (I) crystallizes in C2/c. Secondly, the heterocyclic ring in (III) is folded into an envelope conformation across a line corresponding to N1···C4 in (I), while the corresponding ring in (I) is planar. Lastly, the molecules of (III) are linked by two independent C—H···π(arene) hydrogen bonds to form sheets parallel to (102), in contrast with the chains formed in (I).

Related literature top

For related literature, see: Amir & Kumar (2005); Amir et al. (2008); Bernstein et al. (1995); Boeyens (1978); Cremer & Pople (1975); Ferguson et al. (1998a, 1998b); Gregson et al. (2000); Grosscurt et al. (1979); Hes et al. (1978); Jasinski et al. (2010a, 2010b); Khan et al. (2002); Kornet (1996); Sarojini et al. (2010).

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The independent molecular components of (II), showing the (5R,6S) diastereoisomer of the oxadiazine component, the atom-labelling scheme and the O—H···O hydrogen bond (dashed line) to the major orientation of the DMF component. The occupancies of the two DMF orientations are 0.557 (1) and 0.443 (10). Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a chain parallel to [001] built from C—H···π(arene) hydrogen bonds (dashed lines). For the sake of clarity, H atoms not involved in the motif shown have been omitted.
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of a cyclic centrosymmetric R22(6) dimer. Hydrogen bonds are shown as dashed lines. For the sake of clarity, the unit-cell outline, the DMF components and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (-x + 1, -y + 1, -z + 1).
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a C(5)C(7)[R21(6) chain of rings running parallel to the [010] direction and built from C—H···O hydrogen bonds, shown as dashed lines. For the sake of clarity, the DMF components and H atoms not involved in the motif shown have been omitted.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (100). Hydrogen bonds are shown as dashed lines. For the sake of clarity, the DMF components and H atoms not involved in the motifs shown have been omitted.
[Figure 7] Fig. 7. A projection, along [010], of part of the crystal structure of (II), showing a cross-section of the (100) sheet with the hydrogen bonds linking the oxadiazine molecules in the central portion of the sheet and the DMF components on the outer faces of the sheet. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
(I) 3,5-Bis(4-fluorophenyl)-1-phenyl-1H-pyrazole top
Crystal data top
C21H14F2N2F(000) = 1376
Mr = 332.34Dx = 1.326 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54178 Å
a = 31.729 (2) ÅCell parameters from 3279 reflections
b = 10.4118 (7) Åθ = 4.5–74.0°
c = 10.1697 (6) ŵ = 0.78 mm1
β = 97.700 (7)°T = 123 K
V = 3329.3 (4) Å3Needle, colourless
Z = 80.53 × 0.18 × 0.06 mm
Data collection top
Agilent Xcalibur Eos Gemini
diffractometer
2550 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray SourceRint = 0.043
ω scansθmax = 68.0°, θmin = 4.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 3838
Tmin = 0.634, Tmax = 0.954k = 1212
5609 measured reflectionsl = 1212
3034 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.1381P)2]
where P = (Fo2 + 2Fc2)/3
3034 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C21H14F2N2V = 3329.3 (4) Å3
Mr = 332.34Z = 8
Monoclinic, C2/cCu Kα radiation
a = 31.729 (2) ŵ = 0.78 mm1
b = 10.4118 (7) ÅT = 123 K
c = 10.1697 (6) Å0.53 × 0.18 × 0.06 mm
β = 97.700 (7)°
Data collection top
Agilent Xcalibur Eos Gemini
diffractometer
3034 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2550 reflections with I > 2σ(I)
Tmin = 0.634, Tmax = 0.954Rint = 0.043
5609 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0660 restraints
wR(F2) = 0.174H-atom parameters constrained
S = 1.05Δρmax = 0.45 e Å3
3034 reflectionsΔρmin = 0.28 e Å3
226 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.13371 (4)0.44853 (14)0.35913 (13)0.0345 (4)
N20.16415 (4)0.49490 (14)0.28947 (13)0.0352 (4)
C30.18664 (5)0.39192 (16)0.26360 (15)0.0351 (4)
C40.17090 (5)0.28044 (17)0.31686 (15)0.0379 (4)
H40.18150.19550.31170.046*
C50.13705 (5)0.31896 (17)0.37802 (14)0.0357 (4)
C110.10308 (5)0.53422 (16)0.40305 (15)0.0340 (4)
C120.05987 (6)0.51085 (18)0.36792 (18)0.0419 (4)
H120.05050.43970.31330.050*
C130.03068 (6)0.5933 (2)0.41411 (19)0.0460 (5)
H130.00110.57830.39120.055*
C140.04453 (6)0.6975 (2)0.49341 (17)0.0449 (5)
H140.02440.75300.52540.054*
C150.08774 (6)0.72055 (19)0.52594 (16)0.0425 (4)
H150.09720.79270.57910.051*
C160.11720 (5)0.63877 (17)0.48114 (15)0.0370 (4)
H160.14680.65420.50370.044*
C310.22321 (6)0.40194 (17)0.18827 (15)0.0370 (4)
C320.22715 (5)0.50278 (18)0.10057 (16)0.0374 (4)
H320.20590.56760.08820.045*
C330.26193 (6)0.50909 (19)0.03120 (17)0.0435 (5)
H330.26460.57740.02900.052*
C340.29230 (6)0.4150 (2)0.05113 (18)0.0480 (5)
F340.32611 (4)0.42090 (15)0.01819 (14)0.0665 (4)
C350.28951 (7)0.3133 (2)0.13592 (19)0.0521 (5)
H350.31080.24870.14720.063*
C360.25471 (6)0.3080 (2)0.20418 (17)0.0450 (5)
H360.25220.23860.26330.054*
C510.10909 (5)0.24330 (17)0.45337 (15)0.0361 (4)
C520.08954 (6)0.13365 (18)0.39643 (16)0.0431 (4)
H520.09410.10970.30930.052*
C530.06364 (7)0.05875 (19)0.46407 (18)0.0452 (5)
H530.05020.01610.42480.054*
C540.05790 (6)0.09629 (18)0.59035 (16)0.0402 (4)
F540.03250 (4)0.02330 (12)0.65751 (11)0.0532 (4)
C550.07689 (6)0.20333 (19)0.65105 (16)0.0437 (4)
H550.07250.22580.73880.052*
C560.10252 (6)0.27784 (18)0.58130 (16)0.0415 (4)
H560.11570.35290.62100.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0408 (7)0.0413 (8)0.0216 (6)0.0010 (6)0.0055 (5)0.0031 (5)
N20.0392 (7)0.0447 (8)0.0220 (6)0.0001 (6)0.0054 (5)0.0022 (5)
C30.0426 (9)0.0429 (9)0.0194 (7)0.0006 (7)0.0023 (6)0.0011 (6)
C40.0490 (10)0.0410 (9)0.0239 (8)0.0024 (7)0.0055 (7)0.0001 (6)
C50.0462 (9)0.0407 (9)0.0200 (7)0.0009 (7)0.0037 (6)0.0006 (6)
C110.0421 (9)0.0405 (9)0.0201 (7)0.0012 (6)0.0069 (6)0.0062 (6)
C120.0445 (10)0.0457 (10)0.0348 (9)0.0029 (7)0.0030 (7)0.0062 (7)
C130.0383 (9)0.0566 (11)0.0440 (10)0.0010 (8)0.0089 (7)0.0130 (9)
C140.0493 (10)0.0578 (11)0.0305 (8)0.0125 (8)0.0157 (7)0.0105 (8)
C150.0545 (10)0.0494 (10)0.0244 (8)0.0049 (8)0.0089 (7)0.0000 (7)
C160.0414 (9)0.0472 (9)0.0225 (8)0.0010 (7)0.0042 (6)0.0023 (7)
C310.0435 (9)0.0464 (9)0.0208 (7)0.0012 (7)0.0035 (6)0.0020 (6)
C320.0405 (9)0.0470 (10)0.0242 (8)0.0009 (7)0.0027 (6)0.0003 (6)
C330.0483 (10)0.0559 (11)0.0264 (8)0.0072 (8)0.0049 (7)0.0014 (7)
C340.0454 (10)0.0680 (13)0.0327 (9)0.0014 (9)0.0133 (7)0.0058 (8)
F340.0576 (7)0.0897 (10)0.0585 (8)0.0045 (7)0.0301 (6)0.0034 (7)
C350.0549 (11)0.0621 (12)0.0411 (10)0.0130 (9)0.0127 (8)0.0009 (9)
C360.0553 (11)0.0503 (10)0.0309 (8)0.0079 (8)0.0112 (7)0.0030 (7)
C510.0444 (9)0.0411 (9)0.0231 (7)0.0016 (7)0.0053 (6)0.0027 (6)
C520.0614 (11)0.0464 (10)0.0231 (8)0.0058 (8)0.0110 (7)0.0024 (7)
C530.0599 (11)0.0453 (10)0.0307 (8)0.0106 (8)0.0070 (8)0.0001 (7)
C540.0443 (9)0.0496 (10)0.0275 (8)0.0003 (7)0.0075 (7)0.0090 (7)
F540.0597 (7)0.0669 (8)0.0351 (6)0.0119 (5)0.0142 (5)0.0100 (5)
C550.0565 (11)0.0540 (11)0.0223 (7)0.0019 (8)0.0115 (7)0.0003 (7)
C560.0544 (10)0.0440 (10)0.0259 (8)0.0030 (8)0.0052 (7)0.0034 (7)
Geometric parameters (Å, º) top
N1—N21.361 (2)C31—C321.394 (3)
N1—C111.434 (2)C32—C331.389 (3)
N2—C31.334 (2)C32—H320.9500
C3—C41.401 (2)C33—C341.370 (3)
C4—C51.371 (2)C33—H330.9500
C5—N11.365 (2)C34—F341.362 (2)
C3—C311.477 (2)C34—C351.376 (3)
C4—H40.9500C35—C361.382 (3)
C5—C511.476 (2)C35—H350.9500
C11—C161.386 (2)C36—H360.9500
C11—C121.391 (3)C51—C521.388 (3)
C12—C131.390 (3)C51—C561.392 (2)
C12—H120.9500C52—C531.381 (3)
C13—C141.387 (3)C52—H520.9500
C13—H130.9500C53—C541.378 (3)
C14—C151.388 (3)C53—H530.9500
C14—H140.9500C54—F541.357 (2)
C15—C161.386 (2)C54—C551.373 (3)
C15—H150.9500C55—C561.386 (3)
C16—H160.9500C55—H550.9500
C31—C361.392 (3)C56—H560.9500
N2—N1—C5112.14 (14)C33—C32—C31120.40 (17)
N2—N1—C11119.96 (14)C33—C32—H32119.8
C5—N1—C11127.90 (14)C31—C32—H32119.8
C3—N2—N1104.68 (14)C34—C33—C32118.82 (18)
N2—C3—C4111.22 (15)C34—C33—H33120.6
N2—C3—C31121.59 (16)C32—C33—H33120.6
C4—C3—C31127.20 (16)F34—C34—C33118.57 (19)
C5—C4—C3105.93 (15)F34—C34—C35118.73 (18)
C5—C4—H4127.0C33—C34—C35122.69 (17)
C3—C4—H4127.0C34—C35—C36117.93 (19)
N1—C5—C4106.03 (15)C34—C35—H35121.0
N1—C5—C51124.06 (15)C36—C35—H35121.0
C4—C5—C51129.89 (16)C35—C36—C31121.54 (19)
C16—C11—C12121.09 (16)C35—C36—H36119.2
C16—C11—N1119.11 (15)C31—C36—H36119.2
C12—C11—N1119.79 (16)C52—C51—C56119.19 (17)
C13—C12—C11118.90 (17)C52—C51—C5119.26 (15)
C13—C12—H12120.5C56—C51—C5121.54 (16)
C11—C12—H12120.5C53—C52—C51121.27 (16)
C14—C13—C12120.40 (17)C53—C52—H52119.4
C14—C13—H13119.8C51—C52—H52119.4
C12—C13—H13119.8C54—C53—C52117.76 (17)
C13—C14—C15119.97 (17)C54—C53—H53121.1
C13—C14—H14120.0C52—C53—H53121.1
C15—C14—H14120.0F54—C54—C55118.86 (16)
C16—C15—C14120.25 (18)F54—C54—C53118.16 (17)
C16—C15—H15119.9C55—C54—C53122.98 (17)
C14—C15—H15119.9C54—C55—C56118.45 (16)
C15—C16—C11119.38 (16)C54—C55—H55120.8
C15—C16—H16120.3C56—C55—H55120.8
C11—C16—H16120.3C55—C56—C51120.34 (17)
C36—C31—C32118.63 (16)C55—C56—H56119.8
C36—C31—C3119.45 (16)C51—C56—H56119.8
C32—C31—C3121.93 (16)
C5—N1—N2—C30.51 (16)N2—C3—C31—C3224.1 (2)
C11—N1—N2—C3179.46 (13)C4—C3—C31—C32156.25 (16)
N1—N2—C3—C40.32 (17)C36—C31—C32—C330.2 (2)
N1—N2—C3—C31179.94 (13)C3—C31—C32—C33179.90 (15)
N2—C3—C4—C50.02 (18)C31—C32—C33—C340.4 (3)
C31—C3—C4—C5179.75 (14)C32—C33—C34—F34179.32 (16)
N2—N1—C5—C40.50 (17)C32—C33—C34—C350.9 (3)
C11—N1—C5—C4179.46 (14)F34—C34—C35—C36179.20 (18)
N2—N1—C5—C51178.20 (13)C33—C34—C35—C360.8 (3)
C11—N1—C5—C511.8 (2)C34—C35—C36—C310.1 (3)
C3—C4—C5—N10.28 (16)C32—C31—C36—C350.4 (3)
C3—C4—C5—C51178.32 (15)C3—C31—C36—C35179.97 (17)
N2—N1—C11—C1656.22 (19)N1—C5—C51—C52129.37 (18)
C5—N1—C11—C16123.82 (17)C4—C5—C51—C5252.3 (2)
N2—N1—C11—C12124.34 (16)N1—C5—C51—C5651.9 (2)
C5—N1—C11—C1255.6 (2)C4—C5—C51—C56126.44 (19)
C16—C11—C12—C130.9 (3)C56—C51—C52—C530.2 (3)
N1—C11—C12—C13178.49 (15)C5—C51—C52—C53178.97 (17)
C11—C12—C13—C140.3 (3)C51—C52—C53—C540.1 (3)
C12—C13—C14—C150.7 (3)C52—C53—C54—F54179.98 (17)
C13—C14—C15—C161.0 (3)C52—C53—C54—C550.4 (3)
C14—C15—C16—C110.3 (3)F54—C54—C55—C56179.52 (16)
C12—C11—C16—C150.6 (2)C53—C54—C55—C560.9 (3)
N1—C11—C16—C15178.80 (14)C54—C55—C56—C510.8 (3)
N2—C3—C31—C36156.29 (16)C52—C51—C56—C550.2 (3)
C4—C3—C31—C3623.4 (2)C5—C51—C56—C55178.47 (16)
Hydrogen-bond geometry (Å, º) top
Cg1 represents the centroid of the C11–C16 ring.
D—H···AD—HH···AD···AD—H···A
C55—H55···Cg1i0.952.683.5674 (10)155
Symmetry code: (i) x, y+1, z+1/2.
(II) (5RS,6SR)-6-(4-Fluorobenzoyl)-5-(4-fluorophenyl)-2-(4-hydroxyphenyl)-5,6-dihydro-4H-1,3,4-oxadiazine N,N-dimethylformamide monosolvate top
Crystal data top
C22H16F2N2O3·C3H7NOF(000) = 976
Mr = 467.46Dx = 1.385 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 17.5182 (7) ÅCell parameters from 4487 reflections
b = 7.4306 (3) Åθ = 5.1–73.5°
c = 17.5595 (7) ŵ = 0.89 mm1
β = 101.252 (4)°T = 173 K
V = 2241.80 (16) Å3Block, colourless
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
Agilent Xcalibur Gemini
diffractometer with Ruby detector
4029 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray SourceRint = 0.042
ω scansθmax = 73.5°, θmin = 5.1°
Absorption correction: multi-scan
(CrysAlis RED; Agilent, 2012)
h = 2121
Tmin = 0.681, Tmax = 0.915k = 99
20862 measured reflectionsl = 2120
4492 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.147 w = 1/[σ2(Fo2) + (0.0828P)2 + 0.4962P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
4492 reflectionsΔρmax = 0.28 e Å3
328 parametersΔρmin = 0.22 e Å3
8 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2014), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0045 (5)
Crystal data top
C22H16F2N2O3·C3H7NOV = 2241.80 (16) Å3
Mr = 467.46Z = 4
Monoclinic, P21/cCu Kα radiation
a = 17.5182 (7) ŵ = 0.89 mm1
b = 7.4306 (3) ÅT = 173 K
c = 17.5595 (7) Å0.30 × 0.20 × 0.10 mm
β = 101.252 (4)°
Data collection top
Agilent Xcalibur Gemini
diffractometer with Ruby detector
4492 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Agilent, 2012)
4029 reflections with I > 2σ(I)
Tmin = 0.681, Tmax = 0.915Rint = 0.042
20862 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0488 restraints
wR(F2) = 0.147H-atom parameters constrained
S = 1.12Δρmax = 0.28 e Å3
4492 reflectionsΔρmin = 0.22 e Å3
328 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.54057 (6)0.09857 (15)0.38825 (6)0.0393 (3)
C20.56472 (8)0.18855 (19)0.45613 (7)0.0312 (3)
N30.52360 (7)0.29026 (18)0.49027 (7)0.0355 (3)
N40.44462 (7)0.31235 (18)0.45558 (7)0.0349 (3)
H40.43170.42370.47020.042*
C50.43087 (8)0.3059 (2)0.37062 (8)0.0304 (3)
H50.46140.40330.35110.036*
C60.46110 (8)0.1210 (2)0.35015 (8)0.0317 (3)
H60.42830.02270.36570.038*
C210.64783 (8)0.15928 (19)0.48957 (8)0.0312 (3)
C220.69582 (9)0.0605 (2)0.45070 (8)0.0347 (3)
H220.67460.00740.40200.042*
C230.77445 (9)0.0384 (2)0.48228 (9)0.0385 (4)
H230.80650.03000.45530.046*
C240.80613 (9)0.1164 (2)0.55345 (9)0.0385 (4)
C250.75867 (9)0.2159 (2)0.59270 (9)0.0386 (4)
H250.78010.26990.64120.046*
C260.68056 (9)0.2364 (2)0.56129 (8)0.0357 (3)
H260.64850.30370.58870.043*
O240.88326 (7)0.08818 (18)0.58294 (7)0.0498 (3)
H240.89500.11920.63460.075*
C510.34530 (8)0.33191 (19)0.33759 (8)0.0301 (3)
C520.28957 (9)0.2422 (2)0.36982 (8)0.0345 (3)
H520.30530.17170.41530.041*
C530.21092 (9)0.2545 (2)0.33622 (10)0.0416 (4)
H530.17260.19500.35850.050*
C540.19040 (9)0.3556 (2)0.26975 (10)0.0421 (4)
F540.11395 (6)0.36116 (18)0.23453 (7)0.0637 (4)
C550.24334 (9)0.4505 (2)0.23741 (9)0.0391 (4)
H550.22690.52220.19240.047*
C560.32151 (8)0.4392 (2)0.27214 (8)0.0338 (3)
H560.35910.50500.25110.041*
C670.46022 (8)0.1118 (2)0.26265 (8)0.0334 (3)
O670.51715 (6)0.16080 (18)0.23857 (6)0.0459 (3)
C610.38685 (8)0.0600 (2)0.20898 (8)0.0315 (3)
C620.32639 (9)0.0316 (2)0.23270 (8)0.0358 (3)
H620.33300.07420.28460.043*
C630.25645 (9)0.0616 (2)0.18153 (9)0.0405 (4)
H630.21490.12360.19760.049*
C640.24931 (9)0.0011 (2)0.10688 (9)0.0401 (4)
F640.18020 (6)0.02128 (17)0.05734 (6)0.0591 (3)
C650.30860 (10)0.0869 (2)0.08015 (8)0.0411 (4)
H650.30210.12470.02760.049*
C660.37782 (9)0.1169 (2)0.13173 (8)0.0366 (3)
H660.41950.17640.11470.044*
N710.9875 (6)0.1371 (15)0.8529 (7)0.052 (2)0.557 (10)
C710.958 (4)0.086 (5)0.7803 (9)0.0530 (18)0.557 (10)
H710.98280.02210.75540.064*0.5574
O710.918 (3)0.183 (5)0.7321 (12)0.0602 (19)0.557 (10)
C721.0460 (5)0.0279 (13)0.9027 (4)0.087 (2)0.557 (10)
H72A1.07040.05350.87060.131*0.557 (10)
H72B1.02120.04280.93820.131*0.557 (10)
H72C1.08570.10650.93270.131*0.557 (10)
C730.9538 (14)0.289 (2)0.8875 (13)0.056 (2)0.557 (10)
H73A0.91750.35340.84700.084*0.557 (10)
H73B0.99550.37110.91150.084*0.557 (10)
H73C0.92590.24520.92700.084*0.557 (10)
N810.9715 (9)0.1101 (19)0.8507 (9)0.052 (2)0.443 (10)
C810.956 (5)0.100 (7)0.7733 (12)0.0530 (18)0.443 (10)
H810.98280.00200.75540.064*0.4426
O810.914 (4)0.204 (7)0.7313 (15)0.0602 (19)0.443 (10)
C821.0095 (6)0.0389 (17)0.8974 (5)0.087 (2)0.443 (10)
H82A0.97370.09040.92800.131*0.443 (10)
H82B1.05630.00500.93230.131*0.443 (10)
H82C1.02400.13160.86310.131*0.443 (10)
C830.9660 (18)0.283 (2)0.8891 (17)0.056 (2)0.443 (10)
H83A1.01830.32550.91210.084*0.443 (10)
H83B0.93560.26800.93000.084*0.443 (10)
H83C0.94030.37080.85100.084*0.443 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0341 (5)0.0448 (6)0.0332 (5)0.0097 (4)0.0076 (4)0.0118 (4)
C20.0346 (7)0.0327 (7)0.0233 (6)0.0008 (5)0.0017 (5)0.0001 (5)
N30.0333 (6)0.0434 (7)0.0263 (5)0.0033 (5)0.0026 (5)0.0034 (5)
N40.0319 (6)0.0451 (7)0.0256 (6)0.0054 (5)0.0004 (5)0.0057 (5)
C50.0294 (7)0.0347 (8)0.0253 (6)0.0013 (5)0.0011 (5)0.0009 (5)
C60.0301 (7)0.0356 (8)0.0260 (6)0.0030 (5)0.0028 (5)0.0038 (5)
C210.0338 (7)0.0297 (7)0.0272 (6)0.0006 (5)0.0013 (5)0.0031 (5)
C220.0359 (7)0.0392 (8)0.0269 (6)0.0012 (6)0.0010 (5)0.0002 (5)
C230.0342 (7)0.0448 (9)0.0355 (7)0.0022 (6)0.0045 (6)0.0027 (6)
C240.0302 (7)0.0442 (9)0.0376 (8)0.0041 (6)0.0024 (6)0.0074 (6)
C250.0396 (8)0.0388 (8)0.0322 (7)0.0029 (6)0.0061 (6)0.0001 (6)
C260.0390 (8)0.0347 (8)0.0296 (7)0.0027 (6)0.0024 (6)0.0010 (5)
O240.0307 (6)0.0654 (8)0.0483 (7)0.0011 (5)0.0043 (5)0.0012 (6)
C510.0304 (7)0.0319 (7)0.0266 (6)0.0029 (5)0.0024 (5)0.0037 (5)
C520.0350 (7)0.0360 (8)0.0312 (7)0.0028 (6)0.0035 (5)0.0022 (6)
C530.0330 (8)0.0452 (9)0.0471 (8)0.0005 (6)0.0088 (6)0.0064 (7)
C540.0292 (7)0.0460 (9)0.0476 (9)0.0045 (6)0.0008 (6)0.0046 (7)
F540.0300 (5)0.0774 (8)0.0769 (8)0.0016 (5)0.0066 (5)0.0232 (6)
C550.0372 (8)0.0427 (9)0.0350 (7)0.0065 (6)0.0011 (6)0.0068 (6)
C560.0336 (7)0.0380 (8)0.0293 (6)0.0020 (6)0.0046 (5)0.0013 (6)
C670.0312 (7)0.0387 (8)0.0289 (7)0.0044 (5)0.0024 (5)0.0062 (5)
O670.0331 (6)0.0672 (8)0.0376 (6)0.0033 (5)0.0072 (4)0.0105 (5)
C610.0321 (7)0.0334 (7)0.0271 (6)0.0046 (5)0.0014 (5)0.0055 (5)
C620.0391 (8)0.0380 (8)0.0280 (7)0.0004 (6)0.0011 (6)0.0014 (6)
C630.0373 (8)0.0434 (9)0.0388 (8)0.0056 (6)0.0026 (6)0.0046 (6)
C640.0365 (8)0.0433 (9)0.0346 (7)0.0027 (6)0.0078 (6)0.0074 (6)
F640.0430 (6)0.0774 (8)0.0470 (6)0.0055 (5)0.0152 (5)0.0055 (5)
C650.0475 (9)0.0463 (9)0.0262 (7)0.0045 (7)0.0011 (6)0.0011 (6)
C660.0390 (8)0.0411 (8)0.0295 (7)0.0009 (6)0.0059 (6)0.0030 (6)
N710.040 (4)0.075 (3)0.0429 (10)0.015 (3)0.009 (2)0.0147 (18)
C710.048 (2)0.065 (5)0.046 (2)0.007 (3)0.011 (4)0.010 (3)
O710.048 (4)0.072 (7)0.0509 (8)0.005 (4)0.0125 (10)0.000 (2)
C720.085 (4)0.120 (6)0.0572 (17)0.054 (4)0.014 (3)0.030 (3)
C730.046 (6)0.0682 (16)0.0497 (12)0.0044 (16)0.001 (3)0.0016 (12)
N810.040 (4)0.075 (3)0.0429 (10)0.015 (3)0.009 (2)0.0147 (18)
C810.048 (2)0.065 (5)0.046 (2)0.007 (3)0.011 (4)0.010 (3)
O810.048 (4)0.072 (7)0.0509 (8)0.005 (4)0.0125 (10)0.000 (2)
C820.085 (4)0.120 (6)0.0572 (17)0.054 (4)0.014 (3)0.030 (3)
C830.046 (6)0.0682 (16)0.0497 (12)0.0044 (16)0.001 (3)0.0016 (12)
Geometric parameters (Å, º) top
O1—C21.3602 (16)C67—O671.2127 (19)
C2—N31.2718 (19)C67—C611.4886 (18)
C2—C211.4759 (18)C61—C621.389 (2)
N3—N41.4084 (16)C61—C661.400 (2)
N4—C51.4648 (17)C62—C631.389 (2)
N4—H40.9077C62—H620.9500
C5—C511.5104 (18)C63—C641.374 (2)
C5—C61.540 (2)C63—H630.9500
C6—O11.4318 (16)C64—F641.3561 (17)
C5—H51.0000C64—C651.377 (3)
C6—C671.5350 (18)C65—C661.383 (2)
C6—H61.0000C65—H650.9500
C21—C221.391 (2)C66—H660.9500
C21—C261.4004 (19)N71—C711.335 (13)
C22—C231.391 (2)N71—C721.456 (5)
C22—H220.9500N71—C731.460 (7)
C23—C241.391 (2)C71—O711.218 (5)
C23—H230.9500C71—H711.0524
C24—O241.3655 (18)C72—H72A0.9800
C24—C251.392 (2)C72—H72B0.9800
C25—C261.380 (2)C72—H72C0.9800
C25—H250.9500C73—H73A0.9800
C26—H260.9500C73—H73B0.9800
O24—H240.9198C73—H73C0.9800
C51—C521.390 (2)N81—C811.336 (14)
C51—C561.394 (2)N81—C821.459 (6)
C52—C531.392 (2)N81—C831.462 (8)
C52—H520.9500C81—O811.217 (7)
C53—C541.375 (2)C81—H810.9771
C53—H530.9500C82—H82A0.9800
C54—F541.3619 (17)C82—H82B0.9800
C54—C551.373 (2)C82—H82C0.9800
C55—C561.389 (2)C83—H83A0.9800
C55—H550.9500C83—H83B0.9800
C56—H560.9500C83—H83C0.9800
C2—O1—C6117.38 (11)O67—C67—C61121.62 (13)
N3—C2—O1126.67 (13)O67—C67—C6119.16 (13)
N3—C2—C21120.37 (12)C61—C67—C6118.95 (12)
O1—C2—C21112.96 (12)C62—C61—C66119.33 (13)
C2—N3—N4117.66 (11)C62—C61—C67123.46 (13)
N3—N4—C5112.91 (11)C66—C61—C67117.11 (13)
N3—N4—H4105.1C63—C62—C61120.84 (14)
C5—N4—H4108.5C63—C62—H62119.6
N4—C5—C51109.92 (11)C61—C62—H62119.6
N4—C5—C6105.74 (11)C64—C63—C62117.86 (15)
C51—C5—C6112.66 (11)C64—C63—H63121.1
N4—C5—H5109.5C62—C63—H63121.1
C51—C5—H5109.5F64—C64—C63118.30 (15)
C6—C5—H5109.5F64—C64—C65118.46 (14)
O1—C6—C67106.34 (11)C63—C64—C65123.24 (14)
O1—C6—C5110.02 (11)C64—C65—C66118.34 (14)
C67—C6—C5109.69 (12)C64—C65—H65120.8
O1—C6—H6110.2C66—C65—H65120.8
C67—C6—H6110.2C65—C66—C61120.33 (15)
C5—C6—H6110.2C65—C66—H66119.8
C22—C21—C26118.46 (13)C61—C66—H66119.8
C22—C21—C2121.76 (12)C71—N71—C72120.9 (5)
C26—C21—C2119.76 (13)C71—N71—C73120.1 (10)
C23—C22—C21120.86 (13)C72—N71—C73118.4 (4)
C23—C22—H22119.6O71—C71—N71124.2 (14)
C21—C22—H22119.6O71—C71—H71112.9
C22—C23—C24119.97 (15)N71—C71—H71119.8
C22—C23—H23120.0N71—C72—H72A109.5
C24—C23—H23120.0N71—C72—H72B109.5
O24—C24—C23117.93 (15)H72A—C72—H72B109.5
O24—C24—C25122.44 (14)N71—C72—H72C109.5
C23—C24—C25119.61 (14)H72A—C72—H72C109.5
C26—C25—C24120.14 (14)H72B—C72—H72C109.5
C26—C25—H25119.9N71—C73—H73A109.5
C24—C25—H25119.9N71—C73—H73B109.5
C25—C26—C21120.95 (14)H73A—C73—H73B109.5
C25—C26—H26119.5N71—C73—H73C109.5
C21—C26—H26119.5H73A—C73—H73C109.5
C24—O24—H24110.5H73B—C73—H73C109.5
C52—C51—C56119.27 (13)C81—N81—C82120.6 (5)
C52—C51—C5120.36 (12)C81—N81—C83119.9 (12)
C56—C51—C5120.30 (13)C82—N81—C83118.2 (4)
C51—C52—C53120.78 (13)O81—C81—N81124.1 (16)
C51—C52—H52119.6O81—C81—H81125.0
C53—C52—H52119.6N81—C81—H81110.9
C54—C53—C52117.94 (14)N81—C82—H82A109.5
C54—C53—H53121.0N81—C82—H82B109.5
C52—C53—H53121.0H82A—C82—H82B109.5
F54—C54—C55118.70 (14)N81—C82—H82C109.5
F54—C54—C53118.22 (15)H82A—C82—H82C109.5
C55—C54—C53123.08 (14)H82B—C82—H82C109.5
C54—C55—C56118.34 (14)N81—C83—H83A109.5
C54—C55—H55120.8N81—C83—H83B109.5
C56—C55—H55120.8H83A—C83—H83B109.5
C55—C56—C51120.50 (14)N81—C83—H83C109.5
C55—C56—H56119.8H83A—C83—H83C109.5
C51—C56—H56119.8H83B—C83—H83C109.5
C6—O1—C2—N30.8 (2)C5—C51—C52—C53175.08 (14)
C6—O1—C2—C21178.72 (12)C51—C52—C53—C541.0 (2)
O1—C2—N3—N40.7 (2)C52—C53—C54—F54176.92 (15)
C21—C2—N3—N4179.81 (12)C52—C53—C54—C553.0 (3)
C2—N3—N4—C532.99 (19)F54—C54—C55—C56177.81 (15)
N3—N4—C5—C51179.56 (12)C53—C54—C55—C562.1 (3)
N3—N4—C5—C658.58 (15)C54—C55—C56—C510.8 (2)
C2—O1—C6—C67146.49 (13)C52—C51—C56—C552.7 (2)
C2—O1—C6—C527.77 (17)C5—C51—C56—C55174.17 (13)
N4—C5—C6—O155.17 (14)O1—C6—C67—O6729.42 (19)
C51—C5—C6—O1175.24 (11)C5—C6—C67—O6789.51 (16)
N4—C5—C6—C67171.80 (11)O1—C6—C67—C61156.53 (12)
C51—C5—C6—C6768.12 (15)C5—C6—C67—C6184.54 (16)
N3—C2—C21—C22174.85 (14)O67—C67—C61—C62166.04 (15)
O1—C2—C21—C224.7 (2)C6—C67—C61—C6220.1 (2)
N3—C2—C21—C263.3 (2)O67—C67—C61—C6617.7 (2)
O1—C2—C21—C26177.09 (13)C6—C67—C61—C66156.23 (14)
C26—C21—C22—C230.1 (2)C66—C61—C62—C632.2 (2)
C2—C21—C22—C23178.30 (13)C67—C61—C62—C63173.97 (14)
C21—C22—C23—C240.3 (2)C61—C62—C63—C640.4 (2)
C22—C23—C24—O24178.72 (14)C62—C63—C64—F64177.43 (14)
C22—C23—C24—C250.1 (2)C62—C63—C64—C652.0 (3)
O24—C24—C25—C26178.23 (14)F64—C64—C65—C66177.10 (14)
C23—C24—C25—C260.3 (2)C63—C64—C65—C662.3 (3)
C24—C25—C26—C210.5 (2)C64—C65—C66—C610.3 (2)
C22—C21—C26—C250.3 (2)C62—C61—C66—C651.9 (2)
C2—C21—C26—C25177.91 (14)C67—C61—C66—C65174.55 (14)
N4—C5—C51—C5244.16 (18)C72—N71—C71—O71168 (6)
C6—C5—C51—C5273.48 (16)C73—N71—C71—O7121 (9)
N4—C5—C51—C56138.98 (14)C82—N81—C81—O81167 (7)
C6—C5—C51—C56103.38 (15)C83—N81—C81—O8126 (11)
C56—C51—C52—C531.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N3i0.912.323.1188 (19)146
O24—H24···O710.921.752.67 (3)179
O24—H24···O810.921.782.69 (3)174
C5—H5···O67ii1.002.553.4844 (19)155
C56—H56···O67ii0.952.433.3080 (18)153
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC21H14F2N2C22H16F2N2O3·C3H7NO
Mr332.34467.46
Crystal system, space groupMonoclinic, C2/cMonoclinic, P21/c
Temperature (K)123173
a, b, c (Å)31.729 (2), 10.4118 (7), 10.1697 (6)17.5182 (7), 7.4306 (3), 17.5595 (7)
β (°) 97.700 (7) 101.252 (4)
V3)3329.3 (4)2241.80 (16)
Z84
Radiation typeCu KαCu Kα
µ (mm1)0.780.89
Crystal size (mm)0.53 × 0.18 × 0.060.30 × 0.20 × 0.10
Data collection
DiffractometerAgilent Xcalibur Eos Gemini
diffractometer
Agilent Xcalibur Gemini
diffractometer with Ruby detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(CrysAlis RED; Agilent, 2012)
Tmin, Tmax0.634, 0.9540.681, 0.915
No. of measured, independent and
observed [I > 2σ(I)] reflections
5609, 3034, 2550 20862, 4492, 4029
Rint0.0430.042
(sin θ/λ)max1)0.6010.622
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.174, 1.05 0.048, 0.147, 1.12
No. of reflections30344492
No. of parameters226328
No. of restraints08
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.280.28, 0.22

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) for (I) top
N1—N21.361 (2)C4—C51.371 (2)
N2—C31.334 (2)C5—N11.365 (2)
C3—C41.401 (2)
N2—N1—C11—C12124.34 (16)C4—C5—C51—C5252.3 (2)
N2—C3—C31—C3224.1 (2)
Hydrogen-bond geometry (Å, º) for (I) top
Cg1 represents the centroid of the C11–C16 ring.
D—H···AD—HH···AD···AD—H···A
C55—H55···Cg1i0.952.683.5674 (10)155
Symmetry code: (i) x, y+1, z+1/2.
Selected geometric parameters (Å, º) for (II) top
O1—C21.3602 (16)N4—C51.4648 (17)
C2—N31.2718 (19)C5—C61.540 (2)
N3—N41.4084 (16)C6—O11.4318 (16)
O1—C2—C21—C224.7 (2)C5—C6—C67—C6184.54 (16)
N4—C5—C51—C5244.16 (18)C6—C67—C61—C6220.1 (2)
C5—C6—C67—O6789.51 (16)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N3i0.912.323.1188 (19)146
O24—H24···O710.921.752.67 (3)179
O24—H24···O810.921.782.69 (3)174
C5—H5···O67ii1.002.553.4844 (19)155
C56—H56···O67ii0.952.433.3080 (18)153
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1/2, z+1/2.
 

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