Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013852/bm1377sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199013852/bm1377Isup2.hkl |
CCDC reference: 142760
The compound was prepared by the reaction of 2,6-dibromopyridine with 2.5 molar equivalents of potassium 3{5}-trifluoromethylpyrazolide in diglyme under N2 at 403 K for 5 d. The crude solid was isolated by quenching the cooled reaction mixture with water. Recrystallization was from CDCl3. Found: C 45.1; H 2.1; N 20.4%: Calculated for C13H7F6N5: C 45.0, H 2.0, N 20.2%.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.
Fig. 1. Molecular structure showing 50% probability displacement ellipsoids, showing the atom-numbering scheme employed. Symmetry code: (i) −x, y, −3/2 − z. |
C13H7F6N5 | F(000) = 696 |
Mr = 347.24 | Dx = 1.711 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.5849 (11) Å | Cell parameters from 8690 reflections |
b = 11.6404 (6) Å | θ = 2.3–27.5° |
c = 8.1150 (7) Å | µ = 0.17 mm−1 |
β = 113.738 (3)° | T = 150 K |
V = 1347.63 (17) Å3 | Block, colourless |
Z = 4 | 0.36 × 0.27 × 0.24 mm |
Nonius KappaCCD area detector diffractometer | 1534 independent reflections |
Radiation source: fine-focus sealed tube | 1116 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
area detector scans | h = −20→17 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −15→14 |
Tmin = 0.943, Tmax = 0.961 | l = −9→10 |
8690 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: located in Fourier map |
R[F2 > 2σ(F2)] = 0.047 | All H-atom parameters refined |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0701P)2 + 0.7815P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.01 |
1534 reflections | Δρmax = 0.30 e Å−3 |
125 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods |
C13H7F6N5 | V = 1347.63 (17) Å3 |
Mr = 347.24 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.5849 (11) Å | µ = 0.17 mm−1 |
b = 11.6404 (6) Å | T = 150 K |
c = 8.1150 (7) Å | 0.36 × 0.27 × 0.24 mm |
β = 113.738 (3)° |
Nonius KappaCCD area detector diffractometer | 1534 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1116 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 0.961 | Rint = 0.056 |
8690 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.139 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.30 e Å−3 |
1534 reflections | Δρmin = −0.27 e Å−3 |
125 parameters |
Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings The unit cell was refined using all data. |
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. Structure solution was achieved by direct methods using SHELXS97 (Sheldrick, 1990), while least squares refinement used SHELXL97 (Sheldrick, 1997). |
x | y | z | Uiso*/Ueq | ||
N1 | 0.0000 | 0.90938 (19) | −0.7500 | 0.0301 (5) | |
C2 | 0.06745 (12) | 0.97009 (15) | −0.6249 (2) | 0.0290 (4) | |
C3 | 0.07162 (13) | 1.08899 (17) | −0.6184 (3) | 0.0333 (5) | |
H3 | 0.1197 (16) | 1.1240 (18) | −0.529 (3) | 0.038 (6)* | |
C4 | 0.0000 | 1.1483 (2) | −0.7500 | 0.0343 (6) | |
H4 | 0.0000 | 1.233 (3) | −0.7500 | 0.035 (7)* | |
N5 | 0.13781 (10) | 0.90447 (14) | −0.4909 (2) | 0.0307 (4) | |
N6 | 0.21342 (11) | 0.95933 (13) | −0.3675 (2) | 0.0334 (4) | |
C7 | 0.26270 (13) | 0.87541 (15) | −0.2613 (3) | 0.0325 (5) | |
C8 | 0.22009 (13) | 0.76699 (17) | −0.3129 (3) | 0.0344 (5) | |
H8 | 0.2437 (16) | 0.693 (2) | −0.255 (3) | 0.049 (6)* | |
C9 | 0.13995 (13) | 0.78912 (16) | −0.4608 (3) | 0.0332 (5) | |
H9 | 0.0889 (15) | 0.7429 (18) | −0.537 (3) | 0.033 (5)* | |
C10 | 0.35415 (14) | 0.90242 (17) | −0.1116 (3) | 0.0377 (5) | |
F11 | 0.35959 (10) | 0.85857 (12) | 0.04485 (18) | 0.0583 (5) | |
F12 | 0.42573 (9) | 0.85687 (15) | −0.1378 (2) | 0.0719 (6) | |
F13 | 0.36999 (9) | 1.01383 (11) | −0.0842 (2) | 0.0638 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0245 (10) | 0.0333 (12) | 0.0300 (12) | 0.000 | 0.0082 (9) | 0.000 |
C2 | 0.0247 (9) | 0.0329 (10) | 0.0274 (10) | 0.0007 (7) | 0.0085 (8) | 0.0017 (7) |
C3 | 0.0288 (9) | 0.0334 (10) | 0.0314 (10) | −0.0034 (8) | 0.0056 (8) | −0.0023 (8) |
C4 | 0.0339 (14) | 0.0304 (14) | 0.0342 (15) | 0.000 | 0.0090 (12) | 0.000 |
N5 | 0.0256 (8) | 0.0312 (8) | 0.0299 (9) | −0.0007 (6) | 0.0057 (7) | 0.0007 (6) |
N6 | 0.0265 (8) | 0.0345 (9) | 0.0319 (9) | −0.0008 (6) | 0.0041 (7) | 0.0005 (6) |
C7 | 0.0283 (9) | 0.0323 (10) | 0.0323 (10) | 0.0020 (7) | 0.0076 (8) | 0.0014 (8) |
C8 | 0.0321 (9) | 0.0323 (10) | 0.0346 (11) | 0.0022 (8) | 0.0093 (8) | 0.0029 (8) |
C9 | 0.0298 (9) | 0.0306 (10) | 0.0350 (11) | −0.0013 (8) | 0.0086 (8) | 0.0004 (8) |
C10 | 0.0334 (10) | 0.0353 (11) | 0.0360 (11) | 0.0059 (8) | 0.0053 (8) | 0.0023 (8) |
F11 | 0.0579 (9) | 0.0625 (9) | 0.0369 (8) | −0.0007 (7) | 0.0006 (6) | 0.0085 (6) |
F12 | 0.0290 (7) | 0.1090 (13) | 0.0636 (11) | 0.0092 (7) | 0.0039 (7) | −0.0290 (9) |
F13 | 0.0503 (8) | 0.0374 (8) | 0.0665 (10) | −0.0062 (6) | −0.0153 (7) | 0.0038 (6) |
N1—C2 | 1.333 (2) | C7—C8 | 1.409 (3) |
C2—C3 | 1.386 (3) | C7—C10 | 1.487 (3) |
C2—N5 | 1.417 (2) | C8—H8 | 0.98 (2) |
C3—H3 | 0.90 (2) | C8—C9 | 1.364 (3) |
C3—C4 | 1.380 (2) | C9—H9 | 0.95 (2) |
C4—H4 | 0.98 (3) | C10—F13 | 1.322 (2) |
N5—N6 | 1.360 (2) | C10—F12 | 1.327 (2) |
N5—C9 | 1.363 (2) | C10—F11 | 1.339 (2) |
N6—C7 | 1.324 (2) | ||
C2—N1—C2i | 116.0 (2) | N6—C7—C10 | 119.31 (16) |
N1—C2—C3 | 124.69 (17) | C8—C7—C10 | 127.88 (17) |
N1—C2—N5 | 115.35 (17) | H8—C8—C9 | 128.4 (13) |
C3—C2—N5 | 119.96 (16) | H8—C8—C7 | 127.3 (13) |
H3—C3—C4 | 123.2 (14) | C9—C8—C7 | 104.32 (17) |
H3—C3—C2 | 119.5 (14) | H9—C9—C8 | 133.8 (12) |
C4—C3—C2 | 117.36 (18) | H9—C9—N5 | 119.2 (12) |
H4—C4—C3 | 120.03 (13) | C8—C9—N5 | 106.96 (16) |
C3i—C4—C3 | 119.9 (3) | F13—C10—F12 | 107.86 (18) |
N6—N5—C9 | 112.27 (15) | F13—C10—F11 | 106.15 (17) |
N6—N5—C2 | 119.05 (16) | F12—C10—F11 | 105.23 (17) |
C9—N5—C2 | 128.63 (15) | F13—C10—C7 | 113.42 (16) |
C7—N6—N5 | 103.68 (15) | F12—C10—C7 | 112.07 (17) |
N6—C7—C8 | 112.77 (17) | F11—C10—C7 | 111.60 (17) |
Symmetry code: (i) −x, y, −z−3/2. |
Experimental details
Crystal data | |
Chemical formula | C13H7F6N5 |
Mr | 347.24 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 15.5849 (11), 11.6404 (6), 8.1150 (7) |
β (°) | 113.738 (3) |
V (Å3) | 1347.63 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.36 × 0.27 × 0.24 |
Data collection | |
Diffractometer | Nonius KappaCCD area detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.943, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8690, 1534, 1116 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.139, 1.06 |
No. of reflections | 1534 |
No. of parameters | 125 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.30, −0.27 |
Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1996), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), local program.
N1—C2 | 1.333 (2) | N5—C9 | 1.363 (2) |
C2—C3 | 1.386 (3) | N6—C7 | 1.324 (2) |
C2—N5 | 1.417 (2) | C7—C8 | 1.409 (3) |
C3—C4 | 1.380 (2) | C7—C10 | 1.487 (3) |
N5—N6 | 1.360 (2) | C8—C9 | 1.364 (3) |
C2—N1—C2i | 116.0 (2) | C9—N5—C2 | 128.63 (15) |
N1—C2—C3 | 124.69 (17) | C7—N6—N5 | 103.68 (15) |
N1—C2—N5 | 115.35 (17) | N6—C7—C8 | 112.77 (17) |
C3—C2—N5 | 119.96 (16) | N6—C7—C10 | 119.31 (16) |
C4—C3—C2 | 117.36 (18) | C8—C7—C10 | 127.88 (17) |
C3i—C4—C3 | 119.9 (3) | C9—C8—C7 | 104.32 (17) |
N6—N5—C9 | 112.27 (15) | C8—C9—N5 | 106.96 (16) |
N6—N5—C2 | 119.05 (16) |
Symmetry code: (i) −x, y, −z−3/2. |
Metal complexes of 3,3''-disubstituted-2,6-dipyrazol-1-ylpyridines are finding increasing use in biomimetic chemistry (Blake et al., 1998), photochemistry (Jameson et al., 1989; Catelano et al., 1999) and as catalysts (Christenson et al., 1995). An attractive feature of these ligands is that the pyrazole substituents can be varied in a synthetically facile way (Jameson & Goldsby, 1990), so that the donor properties of the ligands, and the steric environment of a coordinated metal ion, can be intimately controlled. We are presently investigating the effects of distal ligand substitution on the electronic properties and solid state dynamic behaviour of [CuL2]2+ complexes, where L is a meridional tris-imine ligand (Solanki et al., 1998; Leech et al., 1999). As a part of this work, we have synthesized the title compound, (I).
The compound crystallizes in space group C2/c, with the molecule lying across the crystallographic C2 axis which passes through N1, C4 and H4. The pyridine and pyrazole rings of the molecule adopt a transoid disposition, as is observed for the unsubstituted derivative 2,6-dipyrazol-1-ylpyridine (Bessel et al., 1992) and are essentially coplanar, the dihedral angle between the least-squares planes of the two rings being 7.8 (2)°. The C7—C8 and C8—C9 distances are respectively 0.018 (4) and 0.016 (4) Å longer than the equivalent distances in the literature structure, reflecting the electron-withdrawing power of the CF3 substituents. All other metric parameters show minimal differences between the two structures. The structural indices of Llamas-Saiz et al. (1994) for this compound are ΔA(N) = 6.8°, 102ΔR(CN) = 3.9 Å, ΔA(C) = 5.8° and 102ΔR(CC) = 4.5 Å, all of which lie within the ranges previously observed for N-aryl and N-heterocyclic pyrazoles.
In the lattice, the molecules are arranged into columns generated by the c-glide operation. Adjacent molecules are strictly coplanar by symmetry and the interplanar distance is 3.46 Å. The centroids of the pyridine rings of adjacent molecules are offset by 2.22 Å, which is close to the ideal value for an attractive π–π stacking interaction (Hunter & Sanders, 1990). There are no unusually close intermolecular contacts between these stacks of molecules.