Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033648/at2338sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033648/at2338Isup2.hkl |
CCDC reference: 657739
All experiments were carried out under dry argon or nitrogen using standard Schlenk techniques. 0.385 g (1.45 mmol) (C6F5)B(NMe2)2, 0.350 g (1.45 mmol) 3,5-(CF3)2PzH and 0.585 g (2.9 mmol) K[3,5-(CF3)2Pz] were solved in 9 ml THF. After stirring for 4 days at room temperature. The solvent was removed in vacuo. Thereby we obtained colourless crystals of the title compound (I) from the residual oil as a side product of the reaction of K[3,5-(CF3)2Pz] and 3,5-(CF3)2PzH with C6F5B(NMe2)2.
H atoms bonded to C were refined using a riding model with fixed individual displacement parameters [U(H) = 1.2 Ueq(C) or U(H) = 1.5 Ueq(Cmethyl)] with C—H ranging from 0.95Å to 0.98 Å. The H atoms bonded to N were located in a difference map and refined freely.
Tris(1-pyrazolyl)borates ("scorpionates") were invented by Trofimenko more than 30 years ago and are today well established as ligands in coordination chemistry (Trofimenko, 1993). The degree of steric crowding around the boron center appears to be an important factor influencing the stability of scorpionates. The results of earlier studies and investigations in our group have shown that the scorpinates R'B(3-Rpz)3- (II) and R'B(3,5-R2pz)3- (III) decompose much more easily when R and R' are bulky (Bieller et al. 2006, Graziani et al. 2002). We have now discovered that (I) was obtained as a side product of the reaction between K[3,5-(CF3)2Pz] and 3,5-(CF3)2PzH on the one side and C6F5B(NMe2)2 on the other side. Geometric parameters of the title compound (I) (Fig. 1) are in the usual ranges. In the crystal, anions and cations form centrosymmetric dimers linked by N—H···N hydrogen bonds (Fig. 2).
For related literature, see: Bieller et al. (2006); Graziani et al. (2002); Trofimenko (1993).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
C2H8N+·C5HF6N2− | F(000) = 504 |
Mr = 249.17 | Dx = 1.517 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5427 reflections |
a = 5.9507 (11) Å | θ = 3.5–25.1° |
b = 15.4492 (19) Å | µ = 0.17 mm−1 |
c = 11.8647 (18) Å | T = 173 K |
β = 90.362 (13)° | Needle, colourless |
V = 1090.7 (3) Å3 | 0.25 × 0.12 × 0.12 mm |
Z = 4 |
Stoe IPDSII two-circle diffractometer | 1287 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.062 |
Graphite monochromator | θmax = 25.0°, θmin = 3.4° |
ω scans | h = −7→7 |
8093 measured reflections | k = −18→17 |
1911 independent reflections | l = −13→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1128P)2] where P = (Fo2 + 2Fc2)/3 |
1911 reflections | (Δ/σ)max < 0.001 |
153 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C2H8N+·C5HF6N2− | V = 1090.7 (3) Å3 |
Mr = 249.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.9507 (11) Å | µ = 0.17 mm−1 |
b = 15.4492 (19) Å | T = 173 K |
c = 11.8647 (18) Å | 0.25 × 0.12 × 0.12 mm |
β = 90.362 (13)° |
Stoe IPDSII two-circle diffractometer | 1287 reflections with I > 2σ(I) |
8093 measured reflections | Rint = 0.062 |
1911 independent reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.30 e Å−3 |
1911 reflections | Δρmin = −0.36 e Å−3 |
153 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2583 (4) | 0.55360 (16) | 0.3472 (2) | 0.0434 (7) | |
N2 | 0.3744 (4) | 0.48549 (17) | 0.3036 (2) | 0.0423 (6) | |
N3 | 0.3413 (4) | 0.62168 (17) | 0.5653 (3) | 0.0411 (6) | |
H3A | 0.322 (6) | 0.598 (3) | 0.497 (4) | 0.060 (11)* | |
H3B | 0.451 (7) | 0.586 (3) | 0.612 (3) | 0.060 (10)* | |
C1 | 0.1235 (5) | 0.5846 (2) | 0.2647 (3) | 0.0436 (8) | |
C2 | 0.1473 (6) | 0.5373 (2) | 0.1658 (3) | 0.0473 (8) | |
H2 | 0.0727 | 0.5450 | 0.0954 | 0.057* | |
C3 | 0.3069 (5) | 0.4762 (2) | 0.1955 (3) | 0.0434 (7) | |
C4 | −0.0324 (6) | 0.6564 (2) | 0.2881 (3) | 0.0549 (9) | |
C5 | 0.4053 (6) | 0.4066 (2) | 0.1254 (3) | 0.0543 (9) | |
C31 | 0.1198 (6) | 0.6163 (3) | 0.6213 (4) | 0.0584 (10) | |
H31A | 0.0687 | 0.5560 | 0.6218 | 0.088* | |
H31B | 0.0107 | 0.6519 | 0.5800 | 0.088* | |
H31C | 0.1334 | 0.6374 | 0.6989 | 0.088* | |
C32 | 0.4315 (6) | 0.7110 (2) | 0.5599 (3) | 0.0538 (9) | |
H32A | 0.5774 | 0.7104 | 0.5221 | 0.081* | |
H32B | 0.4500 | 0.7338 | 0.6365 | 0.081* | |
H32C | 0.3267 | 0.7478 | 0.5176 | 0.081* | |
F41 | −0.1977 (5) | 0.63381 (18) | 0.3586 (3) | 0.0956 (10) | |
F42 | −0.1288 (5) | 0.68795 (18) | 0.1954 (2) | 0.0934 (10) | |
F43 | 0.0655 (5) | 0.72381 (15) | 0.3391 (2) | 0.0815 (8) | |
F51 | 0.2993 (6) | 0.3963 (2) | 0.0282 (2) | 0.1060 (12) | |
F52 | 0.6212 (5) | 0.4206 (2) | 0.0986 (3) | 0.0970 (10) | |
F53 | 0.4094 (5) | 0.32993 (14) | 0.1768 (2) | 0.0803 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0449 (14) | 0.0413 (14) | 0.0442 (16) | 0.0022 (11) | 0.0044 (12) | −0.0043 (11) |
N2 | 0.0438 (13) | 0.0425 (14) | 0.0409 (15) | 0.0030 (11) | 0.0046 (11) | −0.0013 (11) |
N3 | 0.0421 (14) | 0.0421 (14) | 0.0391 (16) | 0.0015 (11) | 0.0029 (12) | −0.0019 (12) |
C1 | 0.0451 (17) | 0.0436 (17) | 0.0422 (19) | 0.0023 (13) | −0.0005 (14) | 0.0047 (13) |
C2 | 0.0528 (19) | 0.0509 (18) | 0.0380 (18) | 0.0020 (15) | −0.0044 (14) | 0.0033 (14) |
C3 | 0.0498 (17) | 0.0429 (17) | 0.0375 (18) | 0.0003 (13) | 0.0026 (13) | 0.0017 (13) |
C4 | 0.056 (2) | 0.052 (2) | 0.057 (2) | 0.0114 (16) | −0.0082 (17) | −0.0055 (17) |
C5 | 0.068 (2) | 0.055 (2) | 0.040 (2) | 0.0085 (17) | 0.0063 (16) | −0.0007 (15) |
C31 | 0.0456 (18) | 0.066 (2) | 0.064 (2) | −0.0067 (16) | 0.0150 (16) | 0.0052 (18) |
C32 | 0.053 (2) | 0.0518 (19) | 0.057 (2) | −0.0080 (16) | 0.0023 (17) | 0.0020 (16) |
F41 | 0.0723 (16) | 0.0850 (18) | 0.130 (3) | 0.0210 (13) | 0.0406 (17) | 0.0022 (16) |
F42 | 0.113 (2) | 0.0882 (18) | 0.0785 (19) | 0.0518 (16) | −0.0357 (16) | −0.0122 (14) |
F43 | 0.0949 (18) | 0.0526 (13) | 0.0967 (19) | 0.0166 (12) | −0.0201 (14) | −0.0215 (12) |
F51 | 0.145 (3) | 0.114 (2) | 0.0582 (17) | 0.060 (2) | −0.0348 (16) | −0.0388 (15) |
F52 | 0.0852 (18) | 0.099 (2) | 0.108 (2) | 0.0051 (15) | 0.0506 (16) | −0.0257 (16) |
F53 | 0.127 (2) | 0.0465 (12) | 0.0674 (16) | 0.0130 (13) | 0.0239 (15) | −0.0008 (10) |
N1—C1 | 1.350 (4) | C4—F42 | 1.330 (4) |
N1—N2 | 1.363 (4) | C4—F43 | 1.336 (4) |
N2—C3 | 1.349 (4) | C4—F41 | 1.342 (5) |
N3—C31 | 1.482 (4) | C5—F51 | 1.321 (4) |
N3—C32 | 1.482 (4) | C5—F53 | 1.332 (4) |
N3—H3A | 0.90 (4) | C5—F52 | 1.343 (4) |
N3—H3B | 1.02 (4) | C31—H31A | 0.9800 |
C1—C2 | 1.391 (5) | C31—H31B | 0.9800 |
C1—C4 | 1.474 (5) | C31—H31C | 0.9800 |
C2—C3 | 1.383 (5) | C32—H32A | 0.9800 |
C2—H2 | 0.9500 | C32—H32B | 0.9800 |
C3—C5 | 1.481 (5) | C32—H32C | 0.9800 |
C1—N1—N2 | 107.4 (2) | F43—C4—C1 | 113.5 (3) |
C3—N2—N1 | 107.2 (2) | F41—C4—C1 | 112.7 (3) |
C31—N3—C32 | 113.3 (3) | F51—C5—F53 | 107.4 (3) |
C31—N3—H3A | 106 (2) | F51—C5—F52 | 105.4 (3) |
C32—N3—H3A | 112 (3) | F53—C5—F52 | 103.7 (3) |
C31—N3—H3B | 107 (2) | F51—C5—C3 | 112.9 (3) |
C32—N3—H3B | 107 (2) | F53—C5—C3 | 113.3 (3) |
H3A—N3—H3B | 110 (3) | F52—C5—C3 | 113.5 (3) |
N1—C1—C2 | 111.3 (3) | N3—C31—H31A | 109.5 |
N1—C1—C4 | 120.2 (3) | N3—C31—H31B | 109.5 |
C2—C1—C4 | 128.5 (3) | H31A—C31—H31B | 109.5 |
C3—C2—C1 | 102.5 (3) | N3—C31—H31C | 109.5 |
C3—C2—H2 | 128.7 | H31A—C31—H31C | 109.5 |
C1—C2—H2 | 128.7 | H31B—C31—H31C | 109.5 |
N2—C3—C2 | 111.7 (3) | N3—C32—H32A | 109.5 |
N2—C3—C5 | 119.6 (3) | N3—C32—H32B | 109.5 |
C2—C3—C5 | 128.7 (3) | H32A—C32—H32B | 109.5 |
F42—C4—F43 | 105.9 (3) | N3—C32—H32C | 109.5 |
F42—C4—F41 | 107.3 (3) | H32A—C32—H32C | 109.5 |
F43—C4—F41 | 103.9 (3) | H32B—C32—H32C | 109.5 |
F42—C4—C1 | 112.9 (3) | ||
C1—N1—N2—C3 | −0.3 (3) | N1—C1—C4—F43 | 50.2 (5) |
N2—N1—C1—C2 | 0.4 (4) | C2—C1—C4—F43 | −133.8 (4) |
N2—N1—C1—C4 | 177.0 (3) | N1—C1—C4—F41 | −67.5 (4) |
N1—C1—C2—C3 | −0.3 (4) | C2—C1—C4—F41 | 108.4 (4) |
C4—C1—C2—C3 | −176.5 (3) | N2—C3—C5—F51 | 169.9 (3) |
N1—N2—C3—C2 | 0.1 (3) | C2—C3—C5—F51 | −10.5 (5) |
N1—N2—C3—C5 | 179.9 (3) | N2—C3—C5—F53 | 47.5 (5) |
C1—C2—C3—N2 | 0.1 (4) | C2—C3—C5—F53 | −132.8 (4) |
C1—C2—C3—C5 | −179.6 (3) | N2—C3—C5—F52 | −70.3 (4) |
N1—C1—C4—F42 | 170.7 (3) | C2—C3—C5—F52 | 109.3 (4) |
C2—C1—C4—F42 | −13.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N1 | 0.90 (4) | 1.94 (5) | 2.834 (4) | 175 (4) |
N3—H3B···N2i | 1.02 (4) | 1.81 (4) | 2.826 (4) | 175 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C2H8N+·C5HF6N2− |
Mr | 249.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 5.9507 (11), 15.4492 (19), 11.8647 (18) |
β (°) | 90.362 (13) |
V (Å3) | 1090.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.25 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8093, 1911, 1287 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.191, 1.02 |
No. of reflections | 1911 |
No. of parameters | 153 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.36 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97 and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···N1 | 0.90 (4) | 1.94 (5) | 2.834 (4) | 175 (4) |
N3—H3B···N2i | 1.02 (4) | 1.81 (4) | 2.826 (4) | 175 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Tris(1-pyrazolyl)borates ("scorpionates") were invented by Trofimenko more than 30 years ago and are today well established as ligands in coordination chemistry (Trofimenko, 1993). The degree of steric crowding around the boron center appears to be an important factor influencing the stability of scorpionates. The results of earlier studies and investigations in our group have shown that the scorpinates R'B(3-Rpz)3- (II) and R'B(3,5-R2pz)3- (III) decompose much more easily when R and R' are bulky (Bieller et al. 2006, Graziani et al. 2002). We have now discovered that (I) was obtained as a side product of the reaction between K[3,5-(CF3)2Pz] and 3,5-(CF3)2PzH on the one side and C6F5B(NMe2)2 on the other side. Geometric parameters of the title compound (I) (Fig. 1) are in the usual ranges. In the crystal, anions and cations form centrosymmetric dimers linked by N—H···N hydrogen bonds (Fig. 2).