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In the title compound, 2C10H14N4·3C6HF5O, one of the penta­fluoro­phenol mol­ecules resides on a mirror plane bisecting the O...F axis. The components aggregate by N—H...N, N—H...O and O—H...N hydrogen bonds involving equal disordering of the H atoms into mol­ecular ensembles based on a 2:1 pyrazole–phenol cyclic pattern [O...N = 2.7768 (16) Å and N...N = 2.859 (2) Å], crosslinked into one-dimensional columns via hydrogen bonding between the outer pyrazole groups and additional penta­fluoro­phenol mol­ecules. The latter yields a 1:1 pyrazole–phenol catemer with alternating strong O—H...N [2.5975 (16) Å] and weaker N—H...O [2.8719 (17) Å] hydrogen bonds. This is the first reported mol­ecular adduct of a penta­fluorinated phenol and a nitro­gen base, and suggests the utility of highly acidic phenols and pyrazoles for developing hydrogen-bonded cocrystals.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108013632/gg3148sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108013632/gg3148Isup2.hkl
Contains datablock I

CCDC reference: 692667

Comment top

N-unsubstituted pyrazoles provide rich and versatile possibilities for engineering of hydrogen-bonded solids (Desiraju, 1989), since the molecular frame combines bond donor (NH) and acceptor (N) sites for self-association (Foces-Foces et al., 2000) or for exploitation of characteristic interactions in multicomponent systems. Thus, the hydrogen-bonding functionalities of pyrazoles and phenols complement each other, and these species commonly cocrystallize forming binary adducts in which the components are rationally integrated by NH···O and OH···N bonding (Boldog et al., 2004). Such incorporation of a strong OH bond-donor unit within the pyrazole catemer is interesting in view of the solid-state tautomerism of pyrazoles [e.g. N—H···N to N···H—N; Aguilar-Parrilla et al., 1992] as a tool for enhancing the strength of partial bonding contributions (Steiner, 2002) and the promotion of the proton dynamics leading to a long-range fast proton transfer. Therefore, it is of interest to explore whether the highly acidic phenols are applicable for the design of molecular adducts with pyrazoles and if the catemeric motif dominates the structure over the formation of different cyclic patterns. In this context we examined 3,3',5,5'-tetramethyl-4,4'-bipyrazole (Me4bpz), the only pyrazole exhibiting catemer/trimer supramolecular isomerism (Boldog et al., 2003), and pentafluorophenol, where the acidity is comparable to that of carbonic acids (pKa = 5.50 versus pKa = 9.95 for phenol).

Compound (I) is the first structurally examined genuine molecular adduct formed by pentafluorophenol and a nitrogen base, unlike the ionic pentafluorophenolate of highly basic 1,8-bis(dimethylamino)naphthalene (Odiaga et al., 1992). The asymmetric unit of (I) includes molecular components lying in general positions and a molecule of pentafluorophenol, with the O2—F8 axis located on a mirror plane (Fig. 1). The primary interaction of the pyrazole and phenol functions occurs by means of NH···N, NH···O and OH···N hydrogen bonding that yields a combination of two distinct supramolecular motifs.

Firstly, two pyrazole and one phenol groups form a rare cyclic pattern, which is related to characteristic pyrazole trimers (Foces-Foces et al., 2000) from the substitution of one pyrazole unit for phenol. A similar hydrogen-bonded cycle incorporating a water molecule was observed for a series of isostructural adducts (Me4bpz)3(H2O)(L) (L is acetone, ethylacetate and tetrahydrofuran) (Boldog et al., 2001). Since two bipyrazole molecules of the (Me4bpz)2(C6F5OH) cyclic unit are related by a mirror plane [symmetry code: (i) x, -y + 3/2, z], the donor and acceptor sites of the hydrogen bond are not distinguishable and the H atoms are equally disordered over two positions (Fig. 1). Accordingly, both N···O separations are equivalent by symmetry [N4···O2 = 2.7768 (16) Å] and they are intermediate between the values for NH···O (2.92 Å) and OH···N (2.70 Å) bonds in a 1:1 adduct of 3,5-dimethylpyrazole and phenol (Boldog et al., 2004). The C6F5OH unit is oriented at 30.69 (5)° to the plane of two pyrazole rings, while the bipyrazole molecule has a twisted conformation with a dihedral angle between the two pyrazole groups of 72.16 (6)° [torsion angle C1—C2—C7—C8 72.8 (2)°].

Secondly, the hydrogen bonding between the outer pyrazole groups and second pentafluorophenol molecule yields the infinite alterating motif –A(BA)n–, which may be viewed as a typical pyrazole catemer expanded by inclusion of a second component. Successive aggregates of (Me4bpz)2(C6F5OH) are related by a 21 axis [symmetry code: (iii) x + 1/2, -y + 3/2, -z + 1/2] and the phenol linkers provide integration of the units into columns along the x-axis direction (Figs. 2 and 3). There is a clear differentiation in the N···O separations, suggesting two distinct types of hydrogen bonding and ordering of the H atoms. The first indicates a strong interaction [O1H···N1 = 2.5975 (16) Å], while for the bond involving the pyrazole NH donor the N and O atoms are much more distal [N2H···O1ii = 2.8719 (17) Å; symmetry code: (ii) x - 1/2, y, -z + 1/2]. The only precedent for an OH···N interaction of fluorinated phenols is a 2.64 Å intermolecular bond in 4'-(4-hydroxy-2,3,5,6-tetrafluorophenyl)-2,2':6',2''-terpyridine (Constable et al., 2003).

Ordering of the H atoms in the catemer is supported by the internal angles involving the N atoms [C1—N1—N2 = 105.46 (12)° and N1—N2—C3 = 112.50 (12)°], which are most sensitive to the tautomerism of pyrazole (Alkorta et al., 1999). Such differentiation agrees with the C—N—N(H) and C—N(H)—N angles (104.0–106.7° and 111.1–113.0°, respectively) for hydrogen-bonded Me4bpz structures (Table 2), while convergence of these parameters is a positive sign for the disordering of the H atoms, as occurs for the cyclic pattern in (Me4bpz)2(C6F5OH).

Several types of weaker interactions are also relevant in the crystal packing. Along the catemer, the pentafluorophenol molecules are situated almost parallel to each other [symmetry code: (iv) x + 1/2, y, -z + 1/2; Fig. 2] and afford a weak slipped ππ stack with an intercentroid distance of 3.588 (2) Å and an interplanar angle of 12.13 (4)°. Interdigitation of the columns (Fig. 3) leads to close contacts between the C6–C8/N3/N4 pyrazole ring and atom F7v [symmetry code: (v) x + 1/2, y, -z + 3/2], situated almost exactly above the ring centroid [π···Fv = 3.287 (2) Å, with the F···π axis making an angle to the aromatic plane of 85.2°]. Such stacking commonly occurs for N-heterocycles and negatively polarized atoms, and is especially characteristic for the most electron-deficient azines and counter-anions (Schottel et al., 2008). The short C10···F3vi separations [3.288 (2) Å; symmetry code: (vi) -x + 3/2, -y + 1, z + 1/2] may be attributed to very weak CH···F bonding (H···F3vi = 2.59 Å and C10H···F3vi = 129°) (Desiraju & Steiner, 1999).

In conclusion, (I) suggests the utility of pyrazoles and highly acidic fluorinated phenols as complementary components for developing of hydrogen-bonded cocrystals. The efficient hydorgen-bond donor properties of C6F5OH allow its integration within either cyclic or infinite supramolecular pyrazole motifs. The (pz)2(C6F5OH) cycle displays disordering of the NH and OH H atoms, while along the two-component catemer the H atoms are ordered and immobile.

Related literature top

For related literature, see: Aguilar-Parrilla, Gerd Scherer, Limbach, Foces-Foces, Cano, Smith, Toiron & Elguero (1992); Alkorta et al. (1999); Boldog et al. (2001, 2003, 2004); Constable et al. (2003); Desiraju (1989); Desiraju & Steiner (1999); Foces-Foces, Alkorta & Elguero (2000); Mosby (1957); Odiaga et al. (1992); Schottel et al. (2008); Steiner (2002).

Experimental top

Me4bpz was synthesized according to the method reported by Mosby (1957). Large colorless crystals of the molecular complex 2(Me4bpz):3(C6F5OH) were prepared by slow evaporation of a solution of Me4bpz (0.190 g, 1 mmol) and pentafluorophenol (0.184 g, 1 mmol) in 5 ml of methanol.

Refinement top

Methyl H atoms were treated as riding in geometrically idealized positions, with C—H distances of 0.97 Å and Uiso(H) values of 1.5Ueq(c), with equal idealized disordering of the H atoms bonded to atoms C4, C9 and C10. H atoms bonded to N and O atoms were located in difference maps and then their coordinates were fixed [with Uiso(H) = 1.5Ueq(O,N)], giving O—H distances of 0.90 and 0.92 Å and a range of N—H distances of 0.85–0.90 Å. H atoms bonded to atoms O2, N3 and N4 were included with partial occupancy factors of 0.5, considering a disordering scheme for hydrogen bonding within the cyclic pyrazole/phenol pattern.

Computing details top

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Version 1.700.00; Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-labeling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. Atoms O2, C17, C20 and F8 are located on a mirror plane and therefore the H atoms within the pyrazole/phenol cycle are equally disordered by symmetry. [Symmetry code: (i) -x, -y + 3/2, z.]
[Figure 2] Fig. 2. Interconnection of the [(Me4bpz)2(C6F5OH)] ensembles in (I) by hydrogen bonding involving the outer pyrazole and pentafluorophenol rings with the alternating [(pyrazole)/(phenol)]n catemer. Dashed lines indicate hydrogen bonds. H atoms have been omitted for clarity and N atoms are shaded grey. [Symmetry codes: (i) -x, -y + 3/2, z; (iv) x + 1/2, y, -z + 1/2.]
[Figure 3] Fig. 3. A view of (I) along the direction of the hydrogen-bonded columns, showing the interdigitation of the pentafluorophenyl groups (projection on a bc plane). F atoms have been omitted for clarity.
3,3',5,5'-Tetramethyl-4,4'-bipyrazole–pentafluorophenol (2/3) top
Crystal data top
2C10H14N4·3C6HF5ODx = 1.583 Mg m3
Mr = 932.71Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 13762 reflections
a = 6.9565 (7) Åθ = 2.9–27.1°
b = 41.727 (4) ŵ = 0.15 mm1
c = 13.4827 (15) ÅT = 213 K
V = 3913.6 (7) Å3Prism, colourless
Z = 40.27 × 0.20 × 0.20 mm
F(000) = 1896
Data collection top
Siemens SMART CCD area-detector
diffractometer
4321 independent reflections
Radiation source: fine-focus sealed tube3634 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 27.1°, θmin = 2.9°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.950, Tmax = 0.980k = 5252
13762 measured reflectionsl = 1117
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.05P)2 + 1.4524P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.003
4321 reflectionsΔρmax = 0.23 e Å3
297 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0075 (5)
Crystal data top
2C10H14N4·3C6HF5OV = 3913.6 (7) Å3
Mr = 932.71Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 6.9565 (7) ŵ = 0.15 mm1
b = 41.727 (4) ÅT = 213 K
c = 13.4827 (15) Å0.27 × 0.20 × 0.20 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
4321 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
3634 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.980Rint = 0.021
13762 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.03Δρmax = 0.23 e Å3
4321 reflectionsΔρmin = 0.20 e Å3
297 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)
O10.68836 (18)0.54889 (2)0.20901 (8)0.0415 (3)
H1O0.66520.56030.26440.062*
O20.7368 (3)0.75000.74202 (11)0.0479 (4)
H2O0.73890.76910.70770.072*0.50
F10.60871 (17)0.51829 (2)0.38835 (7)0.0497 (3)
F20.54018 (18)0.45460 (2)0.39266 (8)0.0576 (3)
F30.53489 (19)0.42018 (2)0.22198 (9)0.0642 (3)
F40.6130 (2)0.44968 (3)0.04682 (9)0.0668 (3)
F50.68483 (18)0.51374 (3)0.04262 (7)0.0564 (3)
F60.6845 (2)0.69375 (3)0.84399 (9)0.0699 (4)
F70.5884 (2)0.69377 (3)1.03717 (8)0.0681 (3)
F80.5383 (3)0.75001.13590 (10)0.0698 (5)
N10.6118 (2)0.58828 (3)0.35288 (9)0.0381 (3)
N20.4511 (2)0.58589 (3)0.40882 (9)0.0393 (3)
H2N0.36820.56960.39850.059*
N30.6310 (2)0.71574 (3)0.52143 (9)0.0361 (3)
H3N0.62710.73610.52410.054*0.50
N40.67858 (19)0.70069 (3)0.60702 (9)0.0360 (3)
H4N0.70290.71300.65960.054*0.50
C10.6902 (2)0.61636 (3)0.37706 (10)0.0349 (3)
C20.5769 (2)0.63196 (3)0.44871 (10)0.0331 (3)
C30.4244 (2)0.61152 (3)0.46714 (11)0.0367 (3)
C40.2582 (3)0.61434 (4)0.53581 (14)0.0506 (4)
H4A0.17770.59540.52990.076*0.50
H4B0.18380.63320.51890.076*0.50
H4C0.30450.61620.60340.076*0.50
H4D0.26630.63450.57160.076*0.50
H4E0.26020.59670.58250.076*0.50
H4F0.13950.61370.49810.076*0.50
C50.8707 (3)0.62766 (4)0.32933 (14)0.0515 (4)
H5A0.96500.61050.33000.077*
H5B0.92050.64600.36550.077*
H5C0.84420.63390.26130.077*
C60.6683 (2)0.66895 (3)0.59286 (10)0.0331 (3)
C70.6111 (2)0.66332 (3)0.49555 (10)0.0316 (3)
C80.5910 (2)0.69363 (3)0.45311 (11)0.0344 (3)
C90.5364 (3)0.70241 (4)0.34947 (12)0.0545 (5)
H9A0.53480.72560.34280.082*0.50
H9B0.40980.69390.33470.082*0.50
H9C0.62940.69340.30360.082*0.50
H9D0.51450.68310.31120.082*0.50
H9E0.63950.71470.31940.082*0.50
H9F0.41990.71520.35050.082*0.50
C100.7201 (3)0.64515 (4)0.67077 (12)0.0493 (4)
H10A0.75410.65630.73140.074*0.50
H10B0.82860.63250.64850.074*0.50
H10C0.61120.63120.68320.074*0.50
H10D0.70850.62370.64400.074*0.50
H10E0.63400.64750.72690.074*0.50
H10F0.85140.64880.69220.074*0.50
C110.6453 (2)0.49932 (4)0.12909 (12)0.0380 (3)
C120.6089 (2)0.46679 (4)0.13083 (13)0.0439 (4)
C130.5732 (2)0.45183 (3)0.21943 (14)0.0430 (4)
C140.5749 (2)0.46915 (4)0.30596 (12)0.0392 (3)
C150.6113 (2)0.50164 (3)0.30351 (11)0.0345 (3)
C160.6468 (2)0.51763 (3)0.21530 (11)0.0327 (3)
C170.6874 (3)0.75000.83805 (15)0.0401 (5)
C180.6626 (3)0.72189 (4)0.89067 (12)0.0432 (4)
C190.6133 (3)0.72169 (4)0.98965 (12)0.0434 (4)
C200.5883 (4)0.75001.03941 (16)0.0433 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0617 (7)0.0250 (5)0.0377 (5)0.0100 (5)0.0092 (5)0.0053 (4)
O20.0620 (11)0.0527 (9)0.0289 (7)0.0000.0033 (7)0.000
F10.0805 (7)0.0339 (5)0.0346 (5)0.0031 (5)0.0011 (5)0.0022 (4)
F20.0764 (8)0.0371 (5)0.0592 (6)0.0010 (5)0.0015 (5)0.0181 (5)
F30.0750 (8)0.0230 (4)0.0946 (9)0.0055 (5)0.0080 (7)0.0046 (5)
F40.0869 (9)0.0485 (6)0.0652 (7)0.0067 (6)0.0000 (6)0.0311 (5)
F50.0793 (8)0.0510 (6)0.0389 (5)0.0126 (5)0.0131 (5)0.0078 (4)
F60.1007 (10)0.0530 (7)0.0560 (6)0.0101 (6)0.0023 (6)0.0183 (5)
F70.0996 (9)0.0483 (6)0.0565 (6)0.0067 (6)0.0015 (6)0.0144 (5)
F80.1011 (14)0.0750 (11)0.0331 (7)0.0000.0164 (8)0.000
N10.0547 (8)0.0236 (6)0.0361 (6)0.0025 (5)0.0006 (6)0.0035 (5)
N20.0546 (8)0.0229 (6)0.0405 (7)0.0082 (5)0.0001 (6)0.0024 (5)
N30.0504 (8)0.0204 (5)0.0376 (6)0.0013 (5)0.0008 (6)0.0027 (5)
N40.0462 (7)0.0239 (6)0.0379 (6)0.0001 (5)0.0003 (5)0.0014 (5)
C10.0500 (9)0.0222 (6)0.0325 (7)0.0005 (6)0.0029 (6)0.0027 (5)
C20.0472 (8)0.0215 (6)0.0307 (7)0.0011 (6)0.0026 (6)0.0001 (5)
C30.0511 (9)0.0231 (6)0.0360 (7)0.0027 (6)0.0009 (7)0.0013 (5)
C40.0585 (11)0.0363 (8)0.0570 (10)0.0063 (8)0.0117 (8)0.0009 (7)
C50.0597 (11)0.0413 (9)0.0535 (10)0.0074 (8)0.0134 (9)0.0126 (8)
C60.0418 (8)0.0239 (6)0.0337 (7)0.0004 (6)0.0021 (6)0.0014 (5)
C70.0404 (8)0.0215 (6)0.0331 (7)0.0011 (5)0.0019 (6)0.0013 (5)
C80.0462 (8)0.0241 (7)0.0329 (7)0.0015 (6)0.0007 (6)0.0011 (5)
C90.0931 (15)0.0324 (8)0.0380 (8)0.0014 (9)0.0117 (9)0.0027 (6)
C100.0791 (13)0.0297 (8)0.0391 (8)0.0057 (8)0.0070 (8)0.0020 (6)
C110.0402 (8)0.0352 (8)0.0388 (8)0.0049 (6)0.0047 (6)0.0052 (6)
C120.0437 (9)0.0338 (8)0.0542 (9)0.0024 (7)0.0006 (8)0.0186 (7)
C130.0389 (8)0.0225 (6)0.0678 (11)0.0003 (6)0.0042 (8)0.0036 (7)
C140.0374 (8)0.0288 (7)0.0514 (9)0.0028 (6)0.0014 (7)0.0073 (6)
C150.0391 (8)0.0261 (7)0.0384 (8)0.0039 (6)0.0016 (6)0.0031 (6)
C160.0320 (7)0.0260 (7)0.0402 (8)0.0020 (5)0.0020 (6)0.0042 (6)
C170.0326 (11)0.0582 (14)0.0296 (10)0.0000.0037 (9)0.000
C180.0457 (9)0.0468 (9)0.0372 (8)0.0028 (7)0.0051 (7)0.0081 (7)
C190.0494 (10)0.0429 (9)0.0380 (8)0.0025 (7)0.0028 (7)0.0077 (7)
C200.0496 (13)0.0514 (14)0.0288 (10)0.0000.0017 (9)0.000
Geometric parameters (Å, º) top
O1—C161.3385 (17)C4—H4F0.9700
O1—H1O0.9005C5—H5A0.9700
O2—C171.340 (3)C5—H5B0.9700
O2—H2O0.9230C5—H5C0.9700
F1—C151.3384 (17)C6—C71.391 (2)
F2—C141.3393 (18)C6—C101.490 (2)
F3—C131.3476 (17)C7—C81.3954 (19)
F4—C121.3391 (18)C8—C91.494 (2)
F5—C111.3403 (19)C9—H9A0.9700
F6—C181.3407 (19)C9—H9B0.9700
F7—C191.3411 (19)C9—H9C0.9700
F8—C201.347 (3)C9—H9D0.9700
N1—C11.3331 (18)C9—H9E0.9700
N1—N21.353 (2)C9—H9F0.9700
N2—C31.3405 (19)C10—H10A0.9700
N2—H2N0.9028C10—H10B0.9700
N3—C81.3328 (18)C10—H10C0.9700
N3—N41.3548 (18)C10—H10D0.9700
N3—H3N0.8510C10—H10E0.9700
N4—C61.3398 (18)C10—H10F0.9700
N4—H4N0.8916C11—C121.381 (2)
C1—C21.406 (2)C11—C161.391 (2)
C1—C51.487 (2)C12—C131.371 (3)
C2—C31.384 (2)C13—C141.373 (2)
C2—C71.4721 (18)C14—C151.379 (2)
C3—C41.486 (2)C15—C161.386 (2)
C4—H4A0.9700C17—C181.382 (2)
C4—H4B0.9700C17—C18i1.382 (2)
C4—H4C0.9700C18—C191.378 (2)
C4—H4D0.9700C19—C201.369 (2)
C4—H4E0.9700C20—C19i1.369 (2)
C16—O1—H1O115.1C8—C9—H9C109.5
C17—O2—H2O119.2H9A—C9—H9C109.5
C1—N1—N2105.46 (12)H9B—C9—H9C109.5
C3—N2—N1112.50 (12)C8—C9—H9D109.5
C3—N2—H2N127.1C8—C9—H9E109.5
N1—N2—H2N119.9H9D—C9—H9E109.5
C8—N3—N4108.61 (11)C8—C9—H9F109.5
C8—N3—H3N135.5H9D—C9—H9F109.5
N4—N3—H3N115.8H9E—C9—H9F109.5
C6—N4—N3108.88 (12)C6—C10—H10A109.5
C6—N4—H4N133.9C6—C10—H10B109.5
N3—N4—H4N117.2H10A—C10—H10B109.5
N1—C1—C2110.23 (14)C6—C10—H10C109.5
N1—C1—C5121.20 (14)H10A—C10—H10C109.5
C2—C1—C5128.57 (13)H10B—C10—H10C109.5
C3—C2—C1105.53 (13)C6—C10—H10D109.5
C3—C2—C7126.47 (14)C6—C10—H10E109.5
C1—C2—C7128.00 (14)H10D—C10—H10E109.5
N2—C3—C2106.29 (14)C6—C10—H10F109.5
N2—C3—C4122.42 (14)H10D—C10—H10F109.5
C2—C3—C4131.29 (14)H10E—C10—H10F109.5
C3—C4—H4A109.5F5—C11—C12119.58 (14)
C3—C4—H4B109.5F5—C11—C16118.60 (13)
H4A—C4—H4B109.5C12—C11—C16121.80 (15)
C3—C4—H4C109.5F4—C12—C13119.89 (14)
H4A—C4—H4C109.5F4—C12—C11120.37 (16)
H4B—C4—H4C109.5C13—C12—C11119.72 (15)
C3—C4—H4D109.5F3—C13—C12120.29 (15)
C3—C4—H4E109.5F3—C13—C14119.75 (16)
H4D—C4—H4E109.5C12—C13—C14119.96 (14)
C3—C4—H4F109.5F2—C14—C13120.10 (14)
H4D—C4—H4F109.5F2—C14—C15119.97 (14)
H4E—C4—H4F109.5C13—C14—C15119.92 (15)
C1—C5—H5A109.5F1—C15—C14119.15 (14)
C1—C5—H5B109.5F1—C15—C16119.06 (12)
H5A—C5—H5B109.5C14—C15—C16121.77 (14)
C1—C5—H5C109.5O1—C16—C15124.20 (13)
H5A—C5—H5C109.5O1—C16—C11118.94 (13)
H5B—C5—H5C109.5C15—C16—C11116.82 (13)
N4—C6—C7108.47 (12)O2—C17—C18121.89 (10)
N4—C6—C10123.07 (13)O2—C17—C18i121.89 (10)
C7—C6—C10128.42 (13)C18—C17—C18i116.2 (2)
C6—C7—C8105.20 (12)F6—C18—C19118.54 (16)
C6—C7—C2126.95 (12)F6—C18—C17119.22 (15)
C8—C7—C2127.85 (13)C19—C18—C17122.23 (16)
N3—C8—C7108.84 (13)F7—C19—C20119.94 (15)
N3—C8—C9122.01 (13)F7—C19—C18119.99 (15)
C7—C8—C9129.15 (13)C20—C19—C18120.07 (16)
C8—C9—H9A109.5F8—C20—C19120.40 (10)
C8—C9—H9B109.5F8—C20—C19i120.40 (10)
H9A—C9—H9B109.5C19—C20—C19i119.2 (2)
C1—N1—N2—C30.31 (17)C16—C11—C12—C130.0 (3)
C8—N3—N4—C60.07 (18)F4—C12—C13—F32.5 (3)
N2—N1—C1—C20.33 (17)C11—C12—C13—F3179.10 (15)
N2—N1—C1—C5179.38 (14)F4—C12—C13—C14177.95 (16)
N1—C1—C2—C30.24 (17)C11—C12—C13—C140.5 (3)
C5—C1—C2—C3179.21 (16)F3—C13—C14—F20.5 (2)
N1—C1—C2—C7179.98 (14)C12—C13—C14—F2179.95 (15)
C5—C1—C2—C71.1 (3)F3—C13—C14—C15179.07 (15)
N1—N2—C3—C20.16 (18)C12—C13—C14—C150.5 (3)
N1—N2—C3—C4179.62 (15)F2—C14—C15—F10.9 (2)
C1—C2—C3—N20.05 (17)C13—C14—C15—F1178.67 (14)
C7—C2—C3—N2179.79 (14)F2—C14—C15—C16179.59 (14)
C1—C2—C3—C4179.34 (17)C13—C14—C15—C160.0 (2)
C7—C2—C3—C40.4 (3)F1—C15—C16—O13.3 (2)
N3—N4—C6—C70.47 (18)C14—C15—C16—O1177.95 (15)
N3—N4—C6—C10177.19 (15)F1—C15—C16—C11179.15 (14)
N4—C6—C7—C80.80 (17)C14—C15—C16—C110.4 (2)
C10—C6—C7—C8176.70 (17)F5—C11—C16—O10.3 (2)
N4—C6—C7—C2178.44 (15)C12—C11—C16—O1178.13 (15)
C10—C6—C7—C24.1 (3)F5—C11—C16—C15177.98 (14)
C3—C2—C7—C671.6 (2)C12—C11—C16—C150.5 (2)
C1—C2—C7—C6108.09 (19)O2—C17—C18—F61.5 (3)
C3—C2—C7—C8107.48 (19)C18i—C17—C18—F6179.96 (12)
C1—C2—C7—C872.8 (2)O2—C17—C18—C19179.46 (19)
N4—N3—C8—C70.59 (18)C18i—C17—C18—C190.9 (3)
N4—N3—C8—C9178.90 (16)F6—C18—C19—F70.0 (3)
C6—C7—C8—N30.85 (18)C17—C18—C19—F7179.11 (18)
C2—C7—C8—N3178.38 (15)F6—C18—C19—C20179.47 (19)
C6—C7—C8—C9178.59 (19)C17—C18—C19—C200.4 (3)
C2—C7—C8—C92.2 (3)F7—C19—C20—F80.1 (3)
F5—C11—C12—F40.0 (2)C18—C19—C20—F8179.4 (2)
C16—C11—C12—F4178.44 (15)F7—C19—C20—C19i179.66 (14)
F5—C11—C12—C13178.40 (15)C18—C19—C20—C19i0.2 (4)
Symmetry code: (i) x, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N10.901.712.5975 (16)168
O2—H2O···N4i0.921.902.7768 (16)158
N2—H2N···O1ii0.902.102.8719 (17)143
N3—H3N···N3i0.852.012.859 (2)176
N4—H4N···O20.891.922.7768 (16)161
Symmetry codes: (i) x, y+3/2, z; (ii) x1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formula2C10H14N4·3C6HF5O
Mr932.71
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)213
a, b, c (Å)6.9565 (7), 41.727 (4), 13.4827 (15)
V3)3913.6 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.27 × 0.20 × 0.20
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.950, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
13762, 4321, 3634
Rint0.021
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.106, 1.03
No. of reflections4321
No. of parameters297
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.20

Computer programs: SMART-NT (Bruker, 1998), SAINT-NT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Version 1.700.00; Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N10.901.712.5975 (16)168
O2—H2O···N4i0.921.902.7768 (16)158
N2—H2N···O1ii0.902.102.8719 (17)143
N3—H3N···N3i0.852.012.859 (2)176
N4—H4N···O20.891.922.7768 (16)161
Symmetry codes: (i) x, y+3/2, z; (ii) x1/2, y, z+1/2.
Representative hydrogen-bonded structures of Me4bpz, involving ordering or disordering of the pyrazole NH atoms. top
CompoundMotifC-N(H)-N (°)C-N-N(H) (°)Proton position
α-Me4bpzapz catemer113.0 (2)104.1 (2)ordered
β-Me4bpzapz catemer109.9 (2) and 108.0 (2)disordered
γ-Me4bpzbpz trimer111.2 (2)106.7 (2)ordered
(Me4bpz)(m-C6H4(OH)2)cNH···π112.85 (15)104.31 (15)ordered
catemer [(pz)(OH)]112.76 (17)104.80 (17)ordered
(Me4bpz)2(C6F5OH)3dcycle [(pz)2(OH)]108.61 (11) and 108.88 (12)disordered
catemer [(pz)(OH)]112.50 (12)105.46 (12)ordered
Notes: (a) Boldog et al. (2001); (b) Boldog et al. (2003); (c) Boldog et al. (2004); (d) this paper.
 

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