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2,3,4,5,6-Penta­fluoro­phenol (pFp), unlike phenol, forms cocrystals with the weak heteroaromatic base phenazine (phz). Two types of cocrystals were prepared, (I) with a high content of pFp, 2,3,4,5,6-penta­fluoro­phenol-phenazine (5/1), 5C6HF5O·C12H8N2, and (II) with a 2:1 pFp-phz molar ratio, 2,3,4,5,6-penta­fluoro­phenol-phenazine (2/1), 2C6HF5O·C12H8N2. In both forms, homostacks are formed by the hetero­cyclic base and phenol mol­ecules and no ar­yl-perfluoroaryl stacking inter­actions occur. The arrangement of the mol­ecules in the crystal of (I) is determined by strong O-H...N and O-H...O hydrogen bonds, weak O-H...F, C-H...F and C-H...O inter­actions, [pi]-[pi] stacking inter­actions between the phz mol­ecules and C-F...[pi]F inter­actions within the pFp stacks. Among the specific inter­actions in (II) are a strong O-H...N hydrogen bond, weak C-H...F inter­actions and [pi]-[pi] stacking inter­actions between the phz mol­ecules. In (I) and (II), the heterocyclic mol­ecules are located around inversion centres and one of the symmetry-independent pFp mol­ecules in (I) is disordered about an inversion centre. Remarkably, similar structural fragments consisting of six pFp stacks can be identified in cocrystal (I) and in the known ortho­rhom­bic polymorph of pFp with Z' = 3 [Gdaniec (2007). CrystEngComm, 9, 286-288].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111027843/su3067sup1.cif
Contains datablocks II, global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111027843/su3067Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111027843/su3067IIsup3.hkl
Contains datablock II

CCDC references: 846635; 846636

Comment top

Phenazine (phz), a diazaaromatic weak base, is considered to be a good supramolecular substrate as it can easily form complexes via metal coordination, hydrogen bonding and halogen bonding. The recognition process of phz can also occur via the use of weaker interactions involving its aromatic π system and C—H groups, thus making prediction of the stoichiometry and packing mode of its complexes more difficult. This fact is best illustrated by the molecular complexes formed by phz with polyphenols. Cocrystallization of phz with hydroquinone (HQ) and naphthalene-1,5-diol affords cocrystals in a 2:1 molar ratio, and cocrystals of stoichiometry 3:1 are formed with biphenyl-4,4'-diol (Thalladi et al., 2000), i.e. the stoichiometry of these cocrystals does not conform with simple considerations of the hydrogen-bond requirements of the cocrystal components. In turn, with phloroglucinol (phl) three nonsolvated crystalline forms of phz–phl molar ratio 2:1, 7:4 and 3:2 are obtained (Sarma et al., 2008), and only in this last cocrystal are the numbers of donor O—H groups and N-atom acceptors balanced. Importantly, all the above cocrystals share similar structural features, namely the main network is constructed from phz stacks and the phenolic molecules are accommodated in channels, where they interact with phz by O—H···N hydrogen bonds, weak nonclassical hydrogen bonds and edge-to-face aromatic interactions.

Edge-to-face interactions are of primary importance in the formation of these channel-type structures (Thalladi et al., 2000; Kadzewski & Gdaniec, 2006). Altering these interactions by lowering the electron density of the aromatic ring of the diphenol, through the exchange of C—H groups with C—F groups, destroys this channel-type structural motif and promotes the formation of mixed π-stacks (Czapik & Gdaniec, 2010), by analogy with the robust Ar—ArF packing motif found in arene–perfluoroarene systems (Collings et al., 2002, and references therein).

Structural and chemical information related to cocrystallization of phz with polyphenols is abundant in the literature. However, no information is available on cocrystallization attempts with phenol itself. As our crystallization efforts reveal, this is most probably due to the negative outcome of these experiments, as we too were unable to cocrystallize these two compounds, despite numerous trials and a variety of applied conditions. Instead, we were more successful with 2,3,4,5,6-pentafluorophenol (pFp), which is nearly five pKa units more acidic than phenol (5.50 for pFp versus 9.95 for phenol), and we obtained two types of pFp–phz cocrystals with component ratios 5:1, (I), and 2:1, (II). Form (I), which is highly unstable in air, was obtained when phenazine was dissolved in molten pFp (m.p. 305 K), or from an n-heptane solution containing phz and a large excess of pFp. The stable form, (II), was obtained when phz and pFp were dissolved in n-heptane in a 1:2 molar ratio. When crystals of (I) where immersed in a drop of perfluoropolyether, slow growth of (II) on the crystals of (I) was observed, with a complete transformation occurring overnight. The identitification of the crystals formed after this transformation as form (II) was determined by the measurement of the unit-cell parameters for a few single crystals resulting from the transformation.

The molecular structure of the molecules in cocrystal (I), together with the atom-numbering scheme, is shown in Fig. 1. The asymmetric unit of (I) consists of one-half of the centrosymmetric phz molecule and 2.5 molecules of pFp, labelled A, B and C. One of the pFp molecules is disordered about an inversion centre over two practically completely overlapping positions, i.e. the phenolic O atom and one of the F atoms are located with equal occupancy at the same position. Identification of the OH group of the disordered pFp molecule was based mostly on molecular geometric features, namely it was expected that the endocyclic angle at the C atoms attached to the electron-donating OH group would be smaller than 120° (Domenicano et al., 1975). As the C1C—C2C—C3C angle of 119.21 (19)° is significantly smaller than the remaining two angles [C1C—C3C—C2Ci = 120.32 (18)° and C3C—C1C—C2Ci = 120.42 (19)°; symmetry code: (i) -x + 1, -y + 2, -z + 1], it was concluded that the OH group is attached to atom C2C. In turn, analysis of the intermolecular contacts of the disordered pFp molecule indicated atoms C2C or C1C as the possible substitution sites. The two short intermolecular F1C···F3A(-x + 1/2, y + 1/2, -z + 1/2) and F2C···F4B contacts of 2.791 (2) and 2.948 (2) Å, respectively, might represent an O—H···F interaction. However, the latter, longer, contact appears to be more adequate for a generally weak O—H···F hydrogen bond, as the low propensity of organic fluorine to participate in classical hydrogen bonding is nowadays well recognized (Reichenbächer et al., 2005, and references therein). Location of the OH group in the remaining two pFp molecules was straightforward and confirmed by the analysis of pFp molecular geometry and intermolecular interactions.

The crystal packing of (I), viewed along the b axis, is shown in Fig. 2. The phz molecules are arranged via ππ interactions into stacks that are completely surrounded by eight stacks formed separately by the three symmetry-independent pFp molecules. All the stacks extend along [010] and the centroid-to-centroid distance between the benzene ring centroids for all pFp stacks is 4.5223 (2) Å, i.e. equal to the unit-cell parameter b. This value indicates significant slipping of the pFp molecules in the stacks and scant overlapping of their aromatic π-systems. Instead, to optimize electrostatic interactions, F atoms are located above and below the electron-defficient aromatic ring of pFp, with C—F···Cg distances in the range 3.264–3.309 Å for stacks composed of pFp molecules A and C, and 3.502–3.515 Å for stacks of B molecules. The stacks formed by phz molecules are also slipped, although in this case the slipping leads to an overlap of the π-systems of the electron-deficient pyrazine fragment and the electron-rich benzene fragment, with a centroid-to-centroid distance of 3.791 Å. However, the slipping of phz molecules in the stack is too small to expose one of the phz benzene rings for aryl–perfluoroaryl interactions, and the Ar—ArF synthon is not observed in (I). Strong O—H···N and O—H···O hydrogen bonds connect the phz molecules and pFp molecules A and B into centrosymmetric heteropentamers, with A molecules acting as donors in an O—H···N interaction and as acceptors in an O—H···O hydrogen bond (Table 1 and Fig. 2). Molecule A, which forms a dihedral angle of 72.25 (8)° with the phz molecule, is additionally involved in a C—H···F interaction with another phz molecule (Table 1), thus bridging two neighbouring molecules in the phz stack. Each of the phz C—H groups forms a short contact with the electronegative O or F atoms of the pFp molecules (Table 1).

Owing to the high pFp content in phz–pFp (5/1) cocrystal, (I), we decided to check whether any similar structural motif could be identified between the crystal packing of pFp molecules in this cocrystal and in the polymorphic forms of pFp. In fact, as shown in Fig. 3, in the orthorhombic P212121 pFp polymorph (Gdaniec, 2007), which like (I) contains three symmetry-independent molecules, a group of six pFp stacks with an arrangement strongly resembling that of the six stacks in (I) can be identified. The stacks in the orthorhombic polymorph are slightly more slipped than in (I), as the distance between the benzene ring centroids increases to 5.1398 (9) Å, i.e. it is ca 0.6 Å longer than in cocrystal (I). The arrangement of these stacks is mostly directed by close-packing forces and not by strong intermolecular interactions, as the helical hydrogen-bond motif observed in the orthorhombic polymorph of pFp is no longer present in (I), and the O—H···O interactions join only two pairs of stacks within this hexameric stack cluster.

The molecular structure of the molecules in (II) is shown in Fig. 4. The asymmetric unit of this (2/1) cocrystal consists of one-half of a phz molecule and one pFp molecule. The crystal components are connected into discrete heterotrimers via O—H···N hydrogen bonding (Table 2 and Fig. 5), and the stoichiometry of (II) agrees with that predicted from hydrogen-bonding considerations. The O—H···N hydrogen bond between the phenol molecule and the heteroaromatic base is longer in (II) than in (I), probably reflecting the absence of a cooperative effect on hydrogen bonding in the former. Nevertheless, the geometry of the O1A—H1A···N1 interaction in both cocrystals is in the range of hydrogen bonds formed by phz with strong carboxylic and dihalogenoanilic acids (Pedireddi et al., 1996; Senthil Kumar et al., 2002; Gdaniec & Połoński, 2007; Gotoh et al., 2007; Kumai et al., 2007). As in (I), the phz molecules in (II) are arranged into π-stacks extending along the a axis and are completely surrounded by stacks of pFp molecules (Fig. 5). The dihedral angles formed between the mean planes of the phz molecules and those of the pFp molecules in adjacent stacks are 83.48 (3) and 4.49 (8)°, respectively, with the pFp molecules in the latter case being virtually coplanar with the heteroaromatic base. In effect, the crystal structure of (II) can be seen as composed of slightly corrugated (001) molecular layers, composed of nearly parallel aromatic molecules (Fig. 5b), with face-to-face stacking interactions arranging the heterocyclic molecules into homostacks and C—H···F interactions directing the packing of pFp molecules relative to phz. As in (I), the Ar—ArF stacking synthon is not observed in this cocrystal, as the closest distance between the centroids of the fluorinated phenyl ring and the phz benzene ring is ca 4.597 Å.

In summary, in the 5:1 and 2:1 cocrystals formed by pFp and phz, each heterocyclic molecule is linked via strong O—H···N hydrogen bonds to two pFp molecules strongly inclined to the phz mean plane. The pFp and phz molecules form separate strongly slipped stacks and no aryl–perfluoroaryl interactions are observed. The absence of the Ar—ArF stacking synthon in the two crystalline forms is quite unexpected, given that this robust synthon is present in cocrystals formed by 2,3,5,6-tetrafluorohydroquinone with phz and quinoxaline (Czapik & Gdaniec, 2010), and in 1:1 cocrystals formed by phz with pentafluoroiodobenzene via C—I···N halogen bonds (Cinčić et al., 2008).

Related literature top

For related literature, see: Cinčić et al. (2008); Collings et al. (2002); Czapik & Gdaniec (2010); Domenicano et al. (1975); Gdaniec (2007); Gdaniec & Połoński (2007); Gotoh et al. (2007); Kadzewski & Gdaniec (2006); Kumai et al. (2007); Pedireddi et al. (1996); Reichenbächer et al. (2005); Sarma et al. (2008); Senthil Kumar, Kuduva & Desiraju (2002); Thalladi et al. (2000).

Experimental top

Phenazine (phz) and 2,3,4,5,6-pentafluorophenol (pFp) were purchased from Aldrich. Yellow rhomboid cocrystals of (I) were obtained by dissolving phz in molten pFp or by adding phenazine to a solution of a ten molar excess of pFp in n-heptane. Needle-shaped crystals of the more stable form, (II), were obtained from an n-heptane solution containing phz and pFp in a 1:2 molar ratio. Form (II) was also obtained by slow decomposition of (I).

Refinement top

All H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.95 Å, and were refined as riding on their carrier atoms, with Uiso(H) = 1.2Ueq(C). The H atoms of the O—H groups, except for H2C in (I), were located in electron-density difference maps and freely refined. In (I), atoms O2C and F2C were given an occupancy of 0.5 and were refined as having identical coordinates and displacement parameters. Atom H2C was located in an electron-density difference map and the O2C—H2C distance constrained to 0.85 Å. It was refined as riding on O2C, with Uiso(H) = 1.2Ueq(O)

Computing details top

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The components of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines and only atoms in the asymmetric unit are labelled.
[Figure 2] Fig. 2. The crystal packing of (I), viewed along the b axis. O, F and N atoms are represented as spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The similar fragments of the crystal structures consisting of six stacks of pFp molecules, (a) (I) and (b) the orthorhombic polymorph (Gdaniec, 2007).
[Figure 4] Fig. 4. The components of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. Only atoms in the asymmetric unit cell are labelled.
[Figure 5] Fig. 5. The crystal packing of (II), viewed along the a axis. O, F and N atoms are represented as spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
(I) 2,3,4,5,6-pentafluorophenol–phenazine (5/1) top
Crystal data top
5C6HF5O·C12H8N2F(000) = 1088
Mr = 1100.54Dx = 1.842 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ynCell parameters from 1638 reflections
a = 16.1015 (7) Åθ = 3.4–56.6°
b = 4.5223 (2) ŵ = 1.82 mm1
c = 27.4753 (12) ÅT = 130 K
β = 97.315 (4)°Prism, yellow
V = 1984.35 (15) Å30.2 × 0.05 × 0.03 mm
Z = 2
Data collection top
Oxford SuperNova
diffractometer
4098 independent reflections
Radiation source: Nova Cu X-ray Source3460 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.035
ω scansθmax = 76.6°, θmin = 3.2°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 2019
Tmin = 0.671, Tmax = 1.000k = 54
13006 measured reflectionsl = 3334
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0645P)2 + 0.593P]
where P = (Fo2 + 2Fc2)/3
4098 reflections(Δ/σ)max < 0.001
342 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
5C6HF5O·C12H8N2V = 1984.35 (15) Å3
Mr = 1100.54Z = 2
Monoclinic, P21/nCu Kα radiation
a = 16.1015 (7) ŵ = 1.82 mm1
b = 4.5223 (2) ÅT = 130 K
c = 27.4753 (12) Å0.2 × 0.05 × 0.03 mm
β = 97.315 (4)°
Data collection top
Oxford SuperNova
diffractometer
4098 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
3460 reflections with I > 2σ(I)
Tmin = 0.671, Tmax = 1.000Rint = 0.035
13006 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.27 e Å3
4098 reflectionsΔρmin = 0.26 e Å3
342 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.46750 (9)0.0873 (3)0.04301 (5)0.0265 (3)
C20.53374 (10)0.0948 (4)0.04505 (6)0.0263 (3)
C30.57197 (12)0.2024 (4)0.09113 (6)0.0345 (4)
H30.55060.14600.12040.041*
C40.63905 (12)0.3859 (5)0.09324 (7)0.0402 (5)
H40.66430.45690.12420.048*
C50.43300 (10)0.1837 (4)0.00133 (6)0.0260 (3)
C60.36263 (11)0.3749 (4)0.00517 (7)0.0338 (4)
H60.33980.43430.02350.041*
C70.32796 (12)0.4731 (5)0.04998 (7)0.0397 (4)
H70.28100.60180.05230.048*
O1A0.41726 (8)0.2525 (3)0.12785 (4)0.0326 (3)
H1A0.4259 (19)0.186 (7)0.0983 (12)0.086 (10)*
F2A0.31296 (7)0.1673 (3)0.07556 (4)0.0383 (3)
F3A0.16114 (7)0.2883 (2)0.10186 (4)0.0363 (3)
F4A0.10460 (7)0.0113 (2)0.17736 (4)0.0372 (3)
F5A0.20255 (6)0.4366 (2)0.22530 (3)0.0328 (2)
F6A0.35776 (6)0.5436 (2)0.20135 (3)0.0310 (2)
C1A0.33918 (10)0.1912 (4)0.13791 (6)0.0251 (3)
C2A0.28644 (11)0.0171 (4)0.11310 (6)0.0270 (4)
C3A0.20859 (11)0.0785 (4)0.12605 (6)0.0276 (4)
C4A0.18002 (10)0.0710 (4)0.16426 (6)0.0269 (3)
C5A0.23054 (11)0.2843 (4)0.18903 (6)0.0255 (3)
C6A0.30897 (10)0.3388 (4)0.17637 (5)0.0243 (3)
O1B0.55409 (9)0.4472 (4)0.18868 (5)0.0427 (4)
H1B0.5079 (19)0.374 (7)0.1768 (11)0.076 (9)*
F2B0.46806 (7)0.0542 (3)0.24287 (4)0.0418 (3)
F3B0.51478 (8)0.0064 (3)0.34095 (4)0.0488 (3)
F4B0.64597 (10)0.3099 (3)0.38614 (4)0.0608 (4)
F5B0.73003 (8)0.6878 (3)0.33262 (5)0.0586 (4)
F6B0.68262 (7)0.7523 (3)0.23533 (5)0.0472 (3)
C1B0.57390 (11)0.4058 (4)0.23734 (6)0.0301 (4)
C2B0.53249 (11)0.2137 (4)0.26516 (6)0.0303 (4)
C3B0.55610 (12)0.1797 (4)0.31484 (7)0.0334 (4)
C4B0.62270 (13)0.3403 (5)0.33746 (7)0.0381 (4)
C5B0.66516 (12)0.5306 (4)0.31077 (7)0.0377 (4)
C6B0.64082 (11)0.5635 (4)0.26092 (7)0.0328 (4)
F1C0.47372 (8)0.5849 (3)0.42814 (4)0.0514 (3)
F2C0.63056 (8)0.8047 (3)0.45430 (5)0.0492 (3)0.50
O2C'0.63056 (8)0.8047 (3)0.45430 (5)0.0492 (3)0.50
H1C0.61310.65770.43660.059*0.50
F3C0.65595 (7)1.2258 (3)0.52524 (4)0.0489 (3)
C1C0.48623 (12)0.7905 (4)0.46366 (6)0.0368 (4)
C2C0.56587 (12)0.9018 (5)0.47641 (7)0.0381 (4)
C3C0.57900 (12)1.1134 (5)0.51284 (7)0.0364 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0285 (7)0.0316 (7)0.0203 (6)0.0017 (6)0.0065 (5)0.0015 (6)
C20.0286 (8)0.0298 (8)0.0210 (7)0.0004 (7)0.0053 (6)0.0011 (6)
C30.0366 (9)0.0458 (11)0.0217 (8)0.0042 (8)0.0063 (7)0.0028 (8)
C40.0389 (10)0.0532 (12)0.0283 (9)0.0108 (9)0.0031 (8)0.0088 (9)
C50.0285 (8)0.0293 (8)0.0208 (7)0.0008 (7)0.0054 (6)0.0008 (6)
C60.0338 (9)0.0387 (10)0.0307 (9)0.0068 (8)0.0107 (7)0.0006 (8)
C70.0339 (9)0.0476 (12)0.0380 (10)0.0127 (9)0.0068 (8)0.0054 (9)
O1A0.0302 (6)0.0483 (8)0.0204 (6)0.0017 (6)0.0072 (5)0.0072 (5)
F2A0.0457 (6)0.0421 (6)0.0280 (5)0.0015 (5)0.0079 (4)0.0155 (5)
F3A0.0405 (6)0.0303 (5)0.0356 (5)0.0048 (5)0.0057 (4)0.0058 (4)
F4A0.0307 (5)0.0434 (6)0.0389 (6)0.0039 (5)0.0095 (4)0.0029 (5)
F5A0.0389 (6)0.0368 (6)0.0248 (5)0.0026 (5)0.0125 (4)0.0057 (4)
F6A0.0368 (5)0.0339 (6)0.0222 (5)0.0058 (4)0.0034 (4)0.0079 (4)
C1A0.0293 (8)0.0287 (8)0.0173 (7)0.0021 (7)0.0028 (6)0.0020 (6)
C2A0.0362 (9)0.0277 (8)0.0169 (7)0.0059 (7)0.0025 (6)0.0039 (6)
C3A0.0338 (9)0.0239 (8)0.0233 (8)0.0003 (7)0.0032 (6)0.0008 (6)
C4A0.0282 (8)0.0281 (8)0.0247 (8)0.0013 (7)0.0042 (6)0.0060 (7)
C5A0.0341 (8)0.0255 (8)0.0175 (7)0.0050 (7)0.0058 (6)0.0015 (6)
C6A0.0313 (8)0.0248 (8)0.0162 (7)0.0002 (7)0.0002 (6)0.0002 (6)
O1B0.0375 (7)0.0640 (10)0.0263 (6)0.0116 (7)0.0023 (5)0.0065 (6)
F2B0.0355 (6)0.0452 (7)0.0440 (6)0.0116 (5)0.0019 (5)0.0006 (5)
F3B0.0589 (8)0.0465 (7)0.0436 (7)0.0014 (6)0.0169 (6)0.0170 (5)
F4B0.0814 (10)0.0699 (9)0.0277 (6)0.0060 (8)0.0068 (6)0.0002 (6)
F5B0.0544 (8)0.0534 (8)0.0613 (8)0.0111 (6)0.0182 (6)0.0138 (7)
F6B0.0375 (6)0.0473 (7)0.0573 (7)0.0118 (5)0.0077 (5)0.0095 (6)
C1B0.0271 (8)0.0350 (9)0.0284 (8)0.0004 (7)0.0050 (7)0.0011 (7)
C2B0.0282 (8)0.0309 (9)0.0320 (9)0.0005 (7)0.0040 (7)0.0008 (7)
C3B0.0396 (10)0.0293 (9)0.0331 (9)0.0057 (8)0.0111 (8)0.0054 (7)
C4B0.0488 (11)0.0389 (10)0.0250 (8)0.0095 (9)0.0020 (8)0.0017 (8)
C5B0.0350 (9)0.0335 (10)0.0417 (10)0.0012 (8)0.0062 (8)0.0079 (8)
C6B0.0296 (8)0.0304 (9)0.0386 (9)0.0009 (7)0.0059 (7)0.0015 (8)
F1C0.0619 (8)0.0515 (7)0.0385 (6)0.0129 (6)0.0022 (6)0.0084 (6)
F2C0.0435 (7)0.0571 (9)0.0483 (8)0.0037 (6)0.0113 (6)0.0021 (7)
O2C'0.0435 (7)0.0571 (9)0.0483 (8)0.0037 (6)0.0113 (6)0.0021 (7)
F3C0.0392 (6)0.0590 (8)0.0453 (7)0.0174 (6)0.0065 (5)0.0062 (6)
C1C0.0448 (11)0.0369 (10)0.0266 (9)0.0068 (8)0.0039 (8)0.0042 (7)
C2C0.0387 (10)0.0438 (11)0.0307 (9)0.0027 (9)0.0003 (8)0.0081 (8)
C3C0.0351 (9)0.0404 (10)0.0309 (9)0.0103 (8)0.0068 (7)0.0098 (8)
Geometric parameters (Å, º) top
N1—C21.343 (2)C3A—C4A1.376 (2)
N1—C51.345 (2)C4A—C5A1.384 (2)
C2—C31.421 (2)C5A—C6A1.374 (2)
C2—C5i1.433 (2)O1B—C1B1.348 (2)
C3—C41.357 (3)O1B—H1B0.84 (3)
C3—H30.9500F2B—C2B1.345 (2)
C4—C7i1.418 (3)F3B—C3B1.337 (2)
C4—H40.9500F4B—C4B1.349 (2)
C5—C61.419 (2)F5B—C5B1.341 (2)
C5—C2i1.433 (2)F6B—C6B1.340 (2)
C6—C71.360 (3)C1B—C6B1.383 (3)
C6—H60.9500C1B—C2B1.383 (2)
C7—C4i1.418 (3)C2B—C3B1.378 (3)
C7—H70.9500C3B—C4B1.376 (3)
O1A—C1A1.350 (2)C4B—C5B1.369 (3)
O1A—H1A0.89 (3)C5B—C6B1.384 (3)
F2A—C2A1.3491 (18)F1C—C1C1.344 (2)
F3A—C3A1.3404 (19)F2C—C2C1.345 (2)
F4A—C4A1.3374 (19)F2C—H1C0.8501
F5A—C5A1.3360 (18)F3C—C3C1.343 (2)
F6A—C6A1.3450 (18)C1C—C3Cii1.372 (3)
C1A—C2A1.388 (2)C1C—C2C1.381 (3)
C1A—C6A1.389 (2)C2C—C3C1.381 (3)
C2A—C3A1.374 (2)C3C—C1Cii1.372 (3)
C2—N1—C5118.06 (14)C6A—C5A—C4A120.14 (15)
N1—C2—C3119.90 (15)F6A—C6A—C5A119.34 (14)
N1—C2—C5i121.09 (15)F6A—C6A—C1A118.75 (14)
C3—C2—C5i119.01 (16)C5A—C6A—C1A121.90 (15)
C4—C3—C2119.95 (16)C1B—O1B—H1B115 (2)
C4—C3—H3120.0O1B—C1B—C6B117.72 (16)
C2—C3—H3120.0O1B—C1B—C2B124.44 (16)
C3—C4—C7i121.01 (17)C6B—C1B—C2B117.83 (16)
C3—C4—H4119.5F2B—C2B—C3B119.40 (16)
C7i—C4—H4119.5F2B—C2B—C1B118.88 (15)
N1—C5—C6119.90 (15)C3B—C2B—C1B121.71 (17)
N1—C5—C2i120.85 (15)F3B—C3B—C4B120.16 (17)
C6—C5—C2i119.25 (15)F3B—C3B—C2B120.55 (17)
C7—C6—C5119.88 (16)C4B—C3B—C2B119.30 (17)
C7—C6—H6120.1F4B—C4B—C5B120.04 (19)
C5—C6—H6120.1F4B—C4B—C3B119.73 (19)
C6—C7—C4i120.90 (18)C5B—C4B—C3B120.24 (17)
C6—C7—H7119.5F5B—C5B—C4B120.49 (18)
C4i—C7—H7119.5F5B—C5B—C6B119.51 (19)
C1A—O1A—H1A112 (2)C4B—C5B—C6B120.00 (17)
O1A—C1A—C2A124.50 (15)F6B—C6B—C1B119.75 (17)
O1A—C1A—C6A118.85 (15)F6B—C6B—C5B119.33 (17)
C2A—C1A—C6A116.63 (15)C1B—C6B—C5B120.92 (17)
F2A—C2A—C3A118.96 (15)C2C—F2C—H1C107.1
F2A—C2A—C1A118.94 (15)F1C—C1C—C3Cii120.52 (18)
C3A—C2A—C1A122.10 (15)F1C—C1C—C2C119.01 (19)
F3A—C3A—C2A119.72 (15)C3Cii—C1C—C2C120.47 (19)
F3A—C3A—C4A120.08 (16)F2C—C2C—C1C120.94 (19)
C2A—C3A—C4A120.19 (15)F2C—C2C—C3C119.85 (18)
F4A—C4A—C3A120.63 (16)C1C—C2C—C3C119.21 (19)
F4A—C4A—C5A120.35 (15)F3C—C3C—C1Cii119.84 (18)
C3A—C4A—C5A119.02 (16)F3C—C3C—C2C119.84 (19)
F5A—C5A—C6A120.30 (15)C1Cii—C3C—C2C120.32 (18)
F5A—C5A—C4A119.56 (15)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N10.89 (3)1.79 (3)2.6693 (18)167 (3)
O1B—H1B···O1A0.84 (3)1.93 (3)2.7358 (19)159 (3)
O2C—H1C···F4B0.852.212.948 (2)146
C6—H6···F2Aiii0.952.373.209 (2)147
C7—H7···F2C/O2Civ0.952.493.350 (2)151
C4—H4···F5Bv0.952.523.349 (2)145
C4—H4···O1Bvi0.952.703.199 (2)114
C3—H3···O1Bvi0.952.623.158 (2)116
Symmetry codes: (iii) x, y+1, z; (iv) x1/2, y+3/2, z1/2; (v) x+3/2, y3/2, z+1/2; (vi) x, y1, z.
(II) 2,3,4,5,6-pentafluorophenol–phenazine (2/1) top
Crystal data top
2C6HF5O·C12H8N2F(000) = 548
Mr = 548.34Dx = 1.715 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ynCell parameters from 766 reflections
a = 4.9045 (3) Åθ = 3.5–36.7°
b = 17.1342 (10) ŵ = 1.53 mm1
c = 12.6397 (6) ÅT = 130 K
β = 90.931 (5)°Needle, yellow
V = 1062.03 (10) Å30.4 × 0.02 × 0.02 mm
Z = 2
Data collection top
Oxford SuperNova
diffractometer
2186 independent reflections
Radiation source: Nova Cu X-ray Source1939 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.039
ω scansθmax = 76.4°, θmin = 4.4°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 56
Tmin = 0.366, Tmax = 1.000k = 2021
10876 measured reflectionsl = 1515
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0693P)2 + 0.4475P]
where P = (Fo2 + 2Fc2)/3
2186 reflections(Δ/σ)max = 0.001
176 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
2C6HF5O·C12H8N2V = 1062.03 (10) Å3
Mr = 548.34Z = 2
Monoclinic, P21/nCu Kα radiation
a = 4.9045 (3) ŵ = 1.53 mm1
b = 17.1342 (10) ÅT = 130 K
c = 12.6397 (6) Å0.4 × 0.02 × 0.02 mm
β = 90.931 (5)°
Data collection top
Oxford SuperNova
diffractometer
2186 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
1939 reflections with I > 2σ(I)
Tmin = 0.366, Tmax = 1.000Rint = 0.039
10876 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.126H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.22 e Å3
2186 reflectionsΔρmin = 0.29 e Å3
176 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5692 (3)0.47309 (8)0.60219 (10)0.0280 (3)
C20.3726 (3)0.52675 (9)0.58729 (12)0.0277 (3)
C30.2287 (4)0.55680 (10)0.67487 (13)0.0339 (4)
H30.27090.53890.74440.041*
C40.0303 (4)0.61123 (11)0.65930 (15)0.0391 (4)
H40.06490.63110.71840.047*
C50.6965 (3)0.44559 (9)0.51709 (12)0.0279 (3)
C60.9056 (4)0.38864 (10)0.52960 (14)0.0333 (4)
H60.95330.36990.59820.040*
C71.0369 (4)0.36105 (10)0.44369 (16)0.0388 (4)
H71.17540.32270.45250.047*
O1A0.7405 (3)0.43417 (8)0.80095 (10)0.0376 (3)
H1A0.686 (6)0.4419 (16)0.735 (2)0.067 (8)*
F2A0.3504 (2)0.33406 (6)0.71111 (7)0.0406 (3)
F3A0.0011 (2)0.25622 (6)0.83397 (9)0.0419 (3)
F4A0.0300 (2)0.27108 (7)1.04879 (9)0.0473 (3)
F5A0.4192 (3)0.36459 (8)1.13705 (8)0.0514 (3)
F6A0.7618 (2)0.44587 (6)1.01470 (8)0.0410 (3)
C1A0.5628 (3)0.39347 (9)0.85879 (12)0.0294 (4)
C2A0.3664 (4)0.34346 (10)0.81657 (12)0.0306 (4)
C3A0.1879 (4)0.30303 (9)0.87859 (13)0.0318 (4)
C4A0.2037 (4)0.31034 (10)0.98751 (14)0.0342 (4)
C5A0.4003 (4)0.35782 (11)1.03161 (13)0.0347 (4)
C6A0.5757 (4)0.39901 (10)0.96887 (13)0.0313 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0297 (7)0.0321 (7)0.0223 (6)0.0029 (5)0.0007 (5)0.0024 (5)
C20.0279 (8)0.0308 (8)0.0244 (7)0.0041 (6)0.0017 (6)0.0007 (6)
C30.0344 (9)0.0405 (9)0.0270 (8)0.0045 (7)0.0041 (7)0.0049 (6)
C40.0374 (10)0.0416 (9)0.0386 (9)0.0030 (7)0.0097 (7)0.0106 (7)
C50.0300 (8)0.0288 (7)0.0248 (7)0.0041 (6)0.0001 (6)0.0002 (6)
C60.0317 (9)0.0326 (8)0.0355 (9)0.0009 (7)0.0013 (7)0.0026 (7)
C70.0337 (9)0.0337 (9)0.0491 (10)0.0000 (7)0.0024 (8)0.0046 (7)
O1A0.0381 (7)0.0476 (7)0.0269 (6)0.0088 (5)0.0021 (5)0.0097 (5)
F2A0.0495 (7)0.0502 (6)0.0220 (5)0.0069 (5)0.0031 (4)0.0001 (4)
F3A0.0415 (6)0.0410 (6)0.0430 (6)0.0095 (5)0.0028 (5)0.0004 (5)
F4A0.0480 (7)0.0553 (7)0.0391 (6)0.0073 (5)0.0125 (5)0.0108 (5)
F5A0.0631 (8)0.0699 (8)0.0215 (5)0.0063 (6)0.0063 (5)0.0031 (5)
F6A0.0454 (6)0.0453 (6)0.0322 (5)0.0064 (5)0.0055 (5)0.0046 (4)
C1A0.0305 (8)0.0312 (8)0.0265 (8)0.0028 (6)0.0013 (6)0.0037 (6)
C2A0.0355 (9)0.0333 (8)0.0229 (7)0.0035 (7)0.0010 (6)0.0016 (6)
C3A0.0323 (9)0.0303 (8)0.0327 (9)0.0004 (6)0.0003 (7)0.0003 (6)
C4A0.0347 (9)0.0363 (9)0.0317 (8)0.0024 (7)0.0081 (7)0.0060 (7)
C5A0.0401 (10)0.0415 (9)0.0226 (8)0.0055 (7)0.0031 (7)0.0006 (6)
C6A0.0336 (9)0.0329 (8)0.0274 (8)0.0015 (6)0.0018 (6)0.0019 (6)
Geometric parameters (Å, º) top
N1—C51.338 (2)O1A—C1A1.342 (2)
N1—C21.343 (2)O1A—H1A0.88 (3)
C2—C31.419 (2)F2A—C2A1.3437 (18)
C2—C5i1.437 (2)F3A—C3A1.343 (2)
C3—C41.360 (3)F4A—C4A1.341 (2)
C3—H30.9500F5A—C5A1.3395 (19)
C4—C7i1.419 (3)F6A—C6A1.340 (2)
C4—H40.9500C1A—C2A1.390 (2)
C5—C61.422 (2)C1A—C6A1.395 (2)
C5—C2i1.437 (2)C2A—C3A1.372 (2)
C6—C71.356 (3)C3A—C4A1.383 (2)
C6—H60.9500C4A—C5A1.373 (3)
C7—C4i1.419 (3)C5A—C6A1.374 (3)
C7—H70.9500
C5—N1—C2118.14 (14)C1A—O1A—H1A113.7 (19)
N1—C2—C3120.26 (15)O1A—C1A—C2A124.30 (15)
N1—C2—C5i120.83 (15)O1A—C1A—C6A119.27 (15)
C3—C2—C5i118.90 (16)C2A—C1A—C6A116.41 (15)
C4—C3—C2119.99 (16)F2A—C2A—C3A118.61 (15)
C4—C3—H3120.0F2A—C2A—C1A118.94 (15)
C2—C3—H3120.0C3A—C2A—C1A122.46 (15)
C3—C4—C7i121.14 (16)F3A—C3A—C2A120.26 (15)
C3—C4—H4119.4F3A—C3A—C4A119.94 (15)
C7i—C4—H4119.4C2A—C3A—C4A119.80 (16)
N1—C5—C6119.82 (15)F4A—C4A—C5A120.74 (16)
N1—C5—C2i121.02 (15)F4A—C4A—C3A120.23 (17)
C6—C5—C2i119.16 (15)C5A—C4A—C3A119.03 (16)
C7—C6—C5120.05 (16)F5A—C5A—C4A119.46 (16)
C7—C6—H6120.0F5A—C5A—C6A119.73 (16)
C5—C6—H6120.0C4A—C5A—C6A120.80 (15)
C6—C7—C4i120.76 (17)F6A—C6A—C5A119.11 (14)
C6—C7—H7119.6F6A—C6A—C1A119.41 (15)
C4i—C7—H7119.6C5A—C6A—C1A121.47 (16)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N10.88 (3)1.85 (3)2.7192 (18)172 (3)
C4—H4···F5Aii0.952.543.441 (2)158
C6—H6···F2Aiii0.952.473.276 (2)142
Symmetry codes: (ii) x, y+1, z+2; (iii) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formula5C6HF5O·C12H8N22C6HF5O·C12H8N2
Mr1100.54548.34
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)130130
a, b, c (Å)16.1015 (7), 4.5223 (2), 27.4753 (12)4.9045 (3), 17.1342 (10), 12.6397 (6)
β (°) 97.315 (4) 90.931 (5)
V3)1984.35 (15)1062.03 (10)
Z22
Radiation typeCu KαCu Kα
µ (mm1)1.821.53
Crystal size (mm)0.2 × 0.05 × 0.030.4 × 0.02 × 0.02
Data collection
DiffractometerOxford SuperNova
diffractometer
Oxford SuperNova
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.671, 1.0000.366, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
13006, 4098, 3460 10876, 2186, 1939
Rint0.0350.039
(sin θ/λ)max1)0.6310.630
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.08 0.043, 0.126, 1.11
No. of reflections40982186
No. of parameters342176
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.260.22, 0.29

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N10.89 (3)1.79 (3)2.6693 (18)167 (3)
O1B—H1B···O1A0.84 (3)1.93 (3)2.7358 (19)159 (3)
O2C'—H1C···F4B0.852.212.948 (2)146
C6—H6···F2Ai0.952.373.209 (2)147
C7—H7···F2C/O2Cii0.952.493.350 (2)151
C4—H4···F5Biii0.952.523.349 (2)145
C4—H4···O1Biv0.952.703.199 (2)114
C3—H3···O1Biv0.952.623.158 (2)116
Symmetry codes: (i) x, y+1, z; (ii) x1/2, y+3/2, z1/2; (iii) x+3/2, y3/2, z+1/2; (iv) x, y1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N10.88 (3)1.85 (3)2.7192 (18)172 (3)
C4—H4···F5Ai0.952.543.441 (2)158
C6—H6···F2Aii0.952.473.276 (2)142
Symmetry codes: (i) x, y+1, z+2; (ii) x+1, y, z.
 

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