Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026232/av3093sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026232/av3093Isup2.hkl |
CCDC reference: 654860
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.011 Å
- R factor = 0.051
- wR factor = 0.145
- Data-to-parameter ratio = 7.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.97 Deg. PLAT340_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ... 11
Alert level C PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ... 0.30 PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.00 PLAT128_ALERT_4_C Non-standard setting of Space group Pca21 .... Pc21b PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P1 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 24.97 From the CIF: _reflns_number_total 2170 Count of symmetry unique reflns 2172 Completeness (_total/calc) 99.91% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Recent years have witnessed an impressive revival of interest in bidentate β-diketiminate ligands, which have been known for more than four decades (Holm & O'Connor, 1971). β-Diketiminates are important spectator ligands by virtue of their strong binding to metals, their tunable and extensive steric demands, and their diversity of bonding modes (Bourget-Merle et al., 2002). For example, their steric and electronic properties can be readily tuned by an appropriate choice of starting materials used in their synthesis. They can form a conjugated π-system due to essential electron delocalization along the ligand. Recently, we have been interested in the synthesis of the new nonsymmetrical β-iminoamines and their coordination in their neutral form as β-diimine nickel complexes (Landolsi et al., 2002).
For related literature, see: Allen et al. (1992).
Compound (I) was obtained after recristallization of the cationic methallyl β-diimine Nickel complexes in methylene chloride with traces of acid. In fact the β-diimine precursors were synthesized by acid-catalysed condensation of benzoylacteone and 2-methylaniline in toluene using a Dean Stark apparatus. Crystals were obtained from a diluted solution in methylene chloride /n-hexane at 243 K.
Hydrogen atoms H2, HN1 and HN2 were located in a Fourier map and refined freely. All the other H atoms were placed in calculated positions and allowed to ride on their parent atoms. Uiso of H atoms are equal to 1.2 Uiso of the parent atom. We chose the non standard space group because when we chose the standard space group, we found problems in the structure resolution.
Recent years have witnessed an impressive revival of interest in bidentate β-diketiminate ligands, which have been known for more than four decades (Holm & O'Connor, 1971). β-Diketiminates are important spectator ligands by virtue of their strong binding to metals, their tunable and extensive steric demands, and their diversity of bonding modes (Bourget-Merle et al., 2002). For example, their steric and electronic properties can be readily tuned by an appropriate choice of starting materials used in their synthesis. They can form a conjugated π-system due to essential electron delocalization along the ligand. Recently, we have been interested in the synthesis of the new nonsymmetrical β-iminoamines and their coordination in their neutral form as β-diimine nickel complexes (Landolsi et al., 2002).
The crystal structure is composed of a cation (β-iminoamineH) and hexafluorophosphate anion with interionic interaction. The shortest F—C distance is F2—C13 [3.551 Å]. The hexafluorophosphate anion possesses an octahedral geometry, with P—F distances ranging from 1.523 to 1.585 Å. The cation adopts an open configuration with intramolecular interaction. The distance H2—N2 (2.366 Å) and H2—N1 (2.487 Å) are shorter than the sum of their van der Waals radii. The N—C [N1—C1 1.317 and N2—C3 1.340 Å] and the C—C [C2—C3 1.387 and C2—C1 1.388 Å] bond distances lie intermediate between the corresponding single and double-bond distances, which suggest significant delocalization within the π-system of the N—C—C—C—N backbone (Allen et al., 1992). The methyl and phenyl groups of the backbone adopt a syn orientation; the two aryl rings adopt a synperiplanar arrangement in order to minimize steric crowding.
Recent years have witnessed an impressive revival of interest in bidentate β-diketiminate ligands, which have been known for more than four decades (Holm & O'Connor, 1971). β-Diketiminates are important spectator ligands by virtue of their strong binding to metals, their tunable and extensive steric demands, and their diversity of bonding modes (Bourget-Merle et al., 2002). For example, their steric and electronic properties can be readily tuned by an appropriate choice of starting materials used in their synthesis. They can form a conjugated π-system due to essential electron delocalization along the ligand. Recently, we have been interested in the synthesis of the new nonsymmetrical β-iminoamines and their coordination in their neutral form as β-diimine nickel complexes (Landolsi et al., 2002).
For related literature, see: Allen et al. (1992).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary size. |
C24H25N2+·F6P− | F(000) = 1008 |
Mr = 486.43 | Dx = 1.355 Mg m−3 |
Orthorhombic, Pc21b | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2bc -2c | Cell parameters from 0 reflections |
a = 6.5352 (2) Å | θ = 0–0° |
b = 17.8580 (3) Å | µ = 0.18 mm−1 |
c = 20.4249 (3) Å | T = 293 K |
V = 2383.70 (9) Å3 | Prism, colourless |
Z = 4 | 0.35 × 0.23 × 0.23 mm |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.069 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.3° |
Graphite monochromator | h = −7→7 |
non–profiled ω scans | k = 0→21 |
4127 measured reflections | l = 0→24 |
2170 independent reflections | 2 standard reflections every 120 min |
1221 reflections with I > 2σ(I) | intensity decay: −2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.073P)2 + 0.2103P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.026 |
2170 reflections | Δρmax = 0.24 e Å−3 |
310 parameters | Δρmin = −0.23 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.1 (3) |
C24H25N2+·F6P− | V = 2383.70 (9) Å3 |
Mr = 486.43 | Z = 4 |
Orthorhombic, Pc21b | Mo Kα radiation |
a = 6.5352 (2) Å | µ = 0.18 mm−1 |
b = 17.8580 (3) Å | T = 293 K |
c = 20.4249 (3) Å | 0.35 × 0.23 × 0.23 mm |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.069 |
4127 measured reflections | 2 standard reflections every 120 min |
2170 independent reflections | intensity decay: −2% |
1221 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.145 | Δρmax = 0.24 e Å−3 |
S = 1.01 | Δρmin = −0.23 e Å−3 |
2170 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
310 parameters | Absolute structure parameter: 0.1 (3) |
1 restraint |
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 | ||
P1 | 0.4127 (3) | 1.09449 (11) | 0.65597 (9) | 0.0592 (5) | |
F1 | 0.1705 (6) | 1.0943 (4) | 0.6594 (3) | 0.122 (2) | |
F2 | 0.4234 (8) | 1.0619 (4) | 0.7256 (2) | 0.116 (2) | |
F3 | 0.6520 (7) | 1.0964 (4) | 0.6521 (3) | 0.130 (2) | |
F4 | 0.4089 (11) | 1.0144 (3) | 0.6304 (3) | 0.145 (3) | |
F5 | 0.4123 (12) | 1.1747 (3) | 0.6844 (5) | 0.183 (4) | |
F6 | 0.3998 (11) | 1.1268 (6) | 0.5861 (3) | 0.201 (4) | |
N1 | 0.9600 (9) | 0.7527 (3) | 0.8552 (3) | 0.0527 (15) | |
HN1 | 1.017 (11) | 0.710 (4) | 0.846 (3) | 0.063* | |
N2 | 0.7305 (8) | 0.9378 (3) | 0.9982 (3) | 0.0537 (15) | |
HN2 | 0.690 (10) | 0.954 (4) | 1.037 (4) | 0.064* | |
C1 | 0.8882 (10) | 0.7642 (3) | 0.9146 (3) | 0.0460 (15) | |
C2 | 0.8214 (10) | 0.8358 (3) | 0.9301 (3) | 0.0471 (16) | |
H2 | 0.835 (10) | 0.872 (4) | 0.903 (3) | 0.057* | |
C3 | 0.7419 (10) | 0.8638 (4) | 0.9881 (3) | 0.0531 (17) | |
C4 | 0.9014 (12) | 0.6988 (4) | 0.9598 (3) | 0.0604 (19) | |
H4A | 0.7756 | 0.6711 | 0.9582 | 0.073* | |
H4B | 0.9246 | 0.7162 | 1.0037 | 0.073* | |
H4C | 1.0125 | 0.6670 | 0.9467 | 0.073* | |
C5 | 0.6616 (10) | 0.8156 (4) | 1.0419 (3) | 0.0518 (17) | |
C6 | 0.7487 (12) | 0.8162 (5) | 1.1027 (3) | 0.070 (2) | |
H6 | 0.8540 | 0.8495 | 1.1120 | 0.084* | |
C7 | 0.6804 (15) | 0.7672 (5) | 1.1508 (3) | 0.085 (3) | |
H7 | 0.7430 | 0.7667 | 1.1917 | 0.102* | |
C8 | 0.5230 (14) | 0.7200 (5) | 1.1382 (4) | 0.077 (2) | |
H8 | 0.4765 | 0.6876 | 1.1706 | 0.092* | |
C9 | 0.4328 (12) | 0.7202 (5) | 1.0780 (4) | 0.076 (2) | |
H9 | 0.3247 | 0.6878 | 1.0696 | 0.091* | |
C10 | 0.4996 (12) | 0.7680 (4) | 1.0291 (3) | 0.067 (2) | |
H10 | 0.4365 | 0.7681 | 0.9883 | 0.081* | |
C11 | 0.8208 (11) | 0.9904 (4) | 0.9537 (3) | 0.0568 (18) | |
C12 | 0.7082 (13) | 1.0115 (4) | 0.8981 (4) | 0.069 (2) | |
H12 | 0.5737 | 0.9955 | 0.8929 | 0.084* | |
C13 | 0.7985 (17) | 1.0559 (4) | 0.8513 (4) | 0.079 (2) | |
H13 | 0.7266 | 1.0690 | 0.8137 | 0.095* | |
C14 | 0.9954 (18) | 1.0810 (5) | 0.8603 (5) | 0.084 (3) | |
H14 | 1.0554 | 1.1114 | 0.8287 | 0.101* | |
C15 | 1.1061 (14) | 1.0614 (4) | 0.9158 (5) | 0.079 (2) | |
H15 | 1.2383 | 1.0795 | 0.9216 | 0.095* | |
C16 | 1.0175 (12) | 1.0140 (4) | 0.9632 (3) | 0.0581 (18) | |
C17 | 1.1384 (14) | 0.9891 (5) | 1.0219 (4) | 0.088 (3) | |
H17A | 1.0631 | 1.0003 | 1.0611 | 0.106* | |
H17B | 1.2672 | 1.0149 | 1.0228 | 0.106* | |
H17C | 1.1622 | 0.9361 | 1.0193 | 0.106* | |
C18 | 0.9586 (11) | 0.8083 (3) | 0.8044 (3) | 0.0502 (17) | |
C19 | 0.7921 (12) | 0.8119 (5) | 0.7617 (4) | 0.067 (2) | |
H19 | 0.6913 | 0.7752 | 0.7633 | 0.080* | |
C20 | 0.7763 (15) | 0.8686 (6) | 0.7179 (4) | 0.088 (3) | |
H20 | 0.6637 | 0.8720 | 0.6903 | 0.106* | |
C21 | 0.9319 (17) | 0.9217 (5) | 0.7152 (4) | 0.085 (3) | |
H21 | 0.9236 | 0.9607 | 0.6852 | 0.102* | |
C22 | 1.0939 (15) | 0.9173 (4) | 0.7556 (4) | 0.074 (2) | |
H22 | 1.1956 | 0.9536 | 0.7525 | 0.088* | |
C23 | 1.1152 (12) | 0.8606 (4) | 0.8017 (3) | 0.0617 (19) | |
C24 | 1.2965 (12) | 0.8572 (5) | 0.8484 (4) | 0.089 (3) | |
H24A | 1.4163 | 0.8761 | 0.8268 | 0.106* | |
H24B | 1.3195 | 0.8062 | 0.8613 | 0.106* | |
H24C | 1.2679 | 0.8870 | 0.8864 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C24 | 0.063 (5) | 0.078 (6) | 0.125 (8) | −0.021 (4) | 0.007 (5) | −0.029 (6) |
P1 | 0.0545 (11) | 0.0530 (10) | 0.0701 (12) | −0.0028 (12) | −0.0011 (10) | 0.0105 (10) |
F1 | 0.057 (3) | 0.132 (4) | 0.176 (5) | 0.000 (4) | −0.009 (3) | 0.062 (4) |
N1 | 0.066 (4) | 0.033 (3) | 0.059 (4) | 0.001 (3) | 0.006 (3) | 0.000 (3) |
C3 | 0.050 (4) | 0.052 (4) | 0.057 (4) | −0.008 (3) | −0.003 (3) | −0.011 (4) |
C4 | 0.079 (5) | 0.046 (4) | 0.057 (4) | 0.005 (4) | 0.002 (4) | 0.002 (3) |
N2 | 0.058 (4) | 0.043 (3) | 0.060 (3) | −0.009 (3) | 0.013 (3) | −0.016 (3) |
C23 | 0.073 (5) | 0.051 (4) | 0.061 (4) | −0.006 (4) | 0.022 (4) | −0.016 (4) |
C9 | 0.069 (5) | 0.079 (5) | 0.079 (6) | −0.021 (5) | 0.006 (4) | 0.011 (5) |
C1 | 0.049 (4) | 0.043 (4) | 0.046 (4) | −0.007 (3) | 0.005 (3) | −0.004 (3) |
F2 | 0.103 (4) | 0.164 (6) | 0.080 (3) | −0.022 (4) | −0.016 (3) | 0.041 (3) |
F3 | 0.058 (3) | 0.158 (5) | 0.175 (5) | −0.005 (4) | 0.012 (3) | 0.058 (5) |
C15 | 0.080 (5) | 0.060 (5) | 0.098 (6) | −0.014 (5) | 0.026 (5) | −0.013 (5) |
C16 | 0.062 (5) | 0.048 (4) | 0.064 (4) | −0.007 (4) | 0.003 (4) | −0.011 (3) |
C6 | 0.090 (6) | 0.068 (5) | 0.052 (4) | −0.016 (5) | −0.004 (4) | −0.009 (4) |
C10 | 0.074 (5) | 0.071 (5) | 0.056 (4) | −0.016 (5) | 0.000 (4) | 0.011 (4) |
C13 | 0.122 (8) | 0.052 (4) | 0.063 (5) | 0.011 (5) | −0.008 (5) | 0.001 (4) |
C21 | 0.130 (9) | 0.071 (6) | 0.054 (5) | 0.010 (6) | 0.030 (6) | 0.016 (4) |
C8 | 0.108 (7) | 0.072 (5) | 0.051 (5) | −0.015 (5) | 0.020 (4) | −0.003 (4) |
F4 | 0.166 (7) | 0.095 (4) | 0.175 (6) | 0.007 (4) | −0.019 (5) | −0.051 (4) |
C19 | 0.073 (5) | 0.072 (5) | 0.055 (5) | −0.007 (4) | 0.001 (4) | 0.000 (4) |
C14 | 0.121 (7) | 0.060 (6) | 0.071 (6) | 0.000 (6) | 0.026 (5) | −0.001 (4) |
C18 | 0.061 (5) | 0.045 (4) | 0.044 (4) | −0.001 (3) | 0.019 (3) | −0.008 (3) |
C20 | 0.092 (7) | 0.109 (7) | 0.064 (5) | 0.007 (6) | −0.004 (5) | 0.018 (5) |
C2 | 0.061 (4) | 0.037 (3) | 0.043 (4) | −0.003 (3) | 0.015 (3) | −0.001 (3) |
C22 | 0.098 (6) | 0.057 (5) | 0.065 (5) | −0.017 (5) | 0.032 (5) | −0.004 (4) |
C5 | 0.056 (4) | 0.051 (4) | 0.049 (4) | −0.010 (3) | 0.009 (3) | −0.008 (3) |
C12 | 0.076 (5) | 0.050 (4) | 0.082 (5) | 0.008 (4) | 0.000 (4) | −0.018 (4) |
C11 | 0.068 (5) | 0.041 (4) | 0.062 (4) | 0.002 (4) | −0.001 (4) | −0.012 (4) |
C17 | 0.078 (6) | 0.085 (6) | 0.100 (7) | −0.012 (5) | −0.012 (5) | −0.009 (5) |
C7 | 0.127 (8) | 0.084 (6) | 0.043 (4) | −0.004 (6) | −0.012 (5) | −0.017 (5) |
F5 | 0.178 (8) | 0.073 (4) | 0.299 (10) | −0.005 (5) | −0.020 (7) | −0.062 (6) |
F6 | 0.132 (5) | 0.342 (13) | 0.129 (5) | −0.037 (7) | −0.016 (4) | 0.148 (7) |
C24—C23 | 1.522 (11) | C15—H15 | 0.9300 |
C24—H24A | 0.9600 | C16—C11 | 1.367 (10) |
C24—H24B | 0.9600 | C16—C17 | 1.504 (10) |
C24—H24C | 0.9600 | C6—C5 | 1.367 (9) |
P1—F4 | 1.523 (6) | C6—C7 | 1.389 (11) |
P1—F2 | 1.539 (5) | C6—H6 | 0.9300 |
P1—F6 | 1.541 (6) | C10—C5 | 1.382 (9) |
P1—F5 | 1.547 (6) | C10—H10 | 0.9300 |
P1—F3 | 1.566 (5) | C13—C14 | 1.374 (12) |
P1—F1 | 1.585 (5) | C13—C12 | 1.375 (11) |
N1—C1 | 1.317 (8) | C13—H13 | 0.9300 |
N1—C18 | 1.436 (8) | C21—C22 | 1.344 (11) |
N1—HN1 | 0.87 (7) | C21—C20 | 1.391 (13) |
C3—N2 | 1.340 (9) | C21—H21 | 0.9300 |
C3—C2 | 1.387 (9) | C8—C7 | 1.354 (12) |
C3—C5 | 1.492 (9) | C8—H8 | 0.9300 |
C4—C1 | 1.491 (8) | C19—C20 | 1.354 (11) |
C4—H4A | 0.9600 | C19—C18 | 1.396 (10) |
C4—H4B | 0.9600 | C19—H19 | 0.9300 |
C4—H4C | 0.9600 | C14—H14 | 0.9300 |
N2—C11 | 1.434 (9) | C20—H20 | 0.9300 |
N2—HN2 | 0.88 (7) | C2—H2 | 0.86 (7) |
C23—C18 | 1.387 (9) | C22—H22 | 0.9300 |
C23—C22 | 1.390 (10) | C12—C11 | 1.404 (10) |
C9—C8 | 1.364 (10) | C12—H12 | 0.9300 |
C9—C10 | 1.384 (9) | C17—H17A | 0.9600 |
C9—H9 | 0.9300 | C17—H17B | 0.9600 |
C1—C2 | 1.388 (9) | C17—H17C | 0.9600 |
C15—C14 | 1.389 (13) | C7—H7 | 0.9300 |
C15—C16 | 1.410 (10) | ||
C23—C24—H24A | 109.5 | C5—C6—C7 | 120.2 (7) |
C23—C24—H24B | 109.5 | C5—C6—H6 | 119.9 |
H24A—C24—H24B | 109.5 | C7—C6—H6 | 119.9 |
C23—C24—H24C | 109.5 | C5—C10—C9 | 118.9 (7) |
H24A—C24—H24C | 109.5 | C5—C10—H10 | 120.5 |
H24B—C24—H24C | 109.5 | C9—C10—H10 | 120.5 |
F4—P1—F2 | 87.9 (4) | C14—C13—C12 | 119.8 (8) |
F4—P1—F6 | 91.9 (6) | C14—C13—H13 | 120.1 |
F2—P1—F6 | 179.4 (4) | C12—C13—H13 | 120.1 |
F4—P1—F5 | 177.7 (5) | C22—C21—C20 | 120.8 (8) |
F2—P1—F5 | 90.2 (5) | C22—C21—H21 | 119.6 |
F6—P1—F5 | 90.1 (6) | C20—C21—H21 | 119.6 |
F4—P1—F3 | 91.1 (4) | C7—C8—C9 | 119.8 (7) |
F2—P1—F3 | 90.5 (3) | C7—C8—H8 | 120.1 |
F6—P1—F3 | 90.0 (4) | C9—C8—H8 | 120.1 |
F5—P1—F3 | 90.0 (5) | C20—C19—C18 | 120.4 (8) |
F4—P1—F1 | 89.8 (4) | C20—C19—H19 | 119.8 |
F2—P1—F1 | 90.2 (3) | C18—C19—H19 | 119.8 |
F6—P1—F1 | 89.2 (4) | C13—C14—C15 | 121.0 (8) |
F5—P1—F1 | 89.1 (4) | C13—C14—H14 | 119.5 |
F3—P1—F1 | 178.8 (4) | C15—C14—H14 | 119.5 |
C1—N1—C18 | 123.8 (6) | C23—C18—N1 | 119.3 (7) |
C1—N1—HN1 | 120 (5) | C19—C18—N1 | 119.3 (6) |
C18—N1—HN1 | 116 (5) | C19—C20—C21 | 118.7 (9) |
N2—C3—C2 | 120.5 (6) | C19—C20—H20 | 120.6 |
N2—C3—C5 | 115.9 (6) | C21—C20—H20 | 120.7 |
C2—C3—C5 | 123.5 (6) | C3—C2—C1 | 130.2 (6) |
C1—C4—H4A | 109.5 | C3—C2—H2 | 108 (5) |
C1—C4—H4B | 109.5 | C1—C2—H2 | 121 (5) |
H4A—C4—H4B | 109.5 | C21—C22—C23 | 122.5 (8) |
C1—C4—H4C | 109.5 | C21—C22—H22 | 118.8 |
H4A—C4—H4C | 109.5 | C23—C22—H22 | 118.8 |
H4B—C4—H4C | 109.5 | C6—C5—C10 | 119.7 (7) |
C3—N2—C11 | 121.7 (5) | C6—C5—C3 | 121.2 (6) |
C3—N2—HN2 | 118 (5) | C10—C5—C3 | 119.0 (6) |
C11—N2—HN2 | 119 (5) | C13—C12—C11 | 119.4 (8) |
C18—C23—C22 | 116.4 (8) | C13—C12—H12 | 120.3 |
C18—C23—C24 | 121.5 (7) | C11—C12—H12 | 120.3 |
C22—C23—C24 | 122.1 (7) | C16—C11—C12 | 121.7 (7) |
C8—C9—C10 | 121.1 (8) | C16—C11—N2 | 119.9 (7) |
C8—C9—H9 | 119.5 | C12—C11—N2 | 118.2 (7) |
C10—C9—H9 | 119.5 | C16—C17—H17A | 109.5 |
N1—C1—C2 | 117.8 (6) | C16—C17—H17B | 109.5 |
N1—C1—C4 | 115.4 (6) | H17A—C17—H17B | 109.5 |
C2—C1—C4 | 126.8 (6) | C16—C17—H17C | 109.5 |
C14—C15—C16 | 119.8 (8) | H17A—C17—H17C | 109.5 |
C14—C15—H15 | 120.1 | H17B—C17—H17C | 109.5 |
C16—C15—H15 | 120.1 | C8—C7—C6 | 120.1 (7) |
C11—C16—C15 | 118.3 (7) | C8—C7—H7 | 119.9 |
C11—C16—C17 | 121.0 (7) | C6—C7—H7 | 119.9 |
C15—C16—C17 | 120.6 (8) |
Experimental details
Crystal data | |
Chemical formula | C24H25N2+·F6P− |
Mr | 486.43 |
Crystal system, space group | Orthorhombic, Pc21b |
Temperature (K) | 293 |
a, b, c (Å) | 6.5352 (2), 17.8580 (3), 20.4249 (3) |
V (Å3) | 2383.70 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.35 × 0.23 × 0.23 |
Data collection | |
Diffractometer | Enraf–Nonius TurboCAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4127, 2170, 1221 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.145, 1.01 |
No. of reflections | 2170 |
No. of parameters | 310 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.23 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.1 (3) |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
N1—C1 | 1.317 (8) | C3—C5 | 1.492 (9) |
N1—C18 | 1.436 (8) | C4—C1 | 1.491 (8) |
C3—N2 | 1.340 (9) | N2—C11 | 1.434 (9) |
C3—C2 | 1.387 (9) | C1—C2 | 1.388 (9) |
C1—N1—C18 | 123.8 (6) | N1—C1—C2 | 117.8 (6) |
N2—C3—C2 | 120.5 (6) | N1—C1—C4 | 115.4 (6) |
N2—C3—C5 | 115.9 (6) | C3—C2—C1 | 130.2 (6) |
C3—N2—C11 | 121.7 (5) |
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Recent years have witnessed an impressive revival of interest in bidentate β-diketiminate ligands, which have been known for more than four decades (Holm & O'Connor, 1971). β-Diketiminates are important spectator ligands by virtue of their strong binding to metals, their tunable and extensive steric demands, and their diversity of bonding modes (Bourget-Merle et al., 2002). For example, their steric and electronic properties can be readily tuned by an appropriate choice of starting materials used in their synthesis. They can form a conjugated π-system due to essential electron delocalization along the ligand. Recently, we have been interested in the synthesis of the new nonsymmetrical β-iminoamines and their coordination in their neutral form as β-diimine nickel complexes (Landolsi et al., 2002).
The crystal structure is composed of a cation (β-iminoamineH) and hexafluorophosphate anion with interionic interaction. The shortest F—C distance is F2—C13 [3.551 Å]. The hexafluorophosphate anion possesses an octahedral geometry, with P—F distances ranging from 1.523 to 1.585 Å. The cation adopts an open configuration with intramolecular interaction. The distance H2—N2 (2.366 Å) and H2—N1 (2.487 Å) are shorter than the sum of their van der Waals radii. The N—C [N1—C1 1.317 and N2—C3 1.340 Å] and the C—C [C2—C3 1.387 and C2—C1 1.388 Å] bond distances lie intermediate between the corresponding single and double-bond distances, which suggest significant delocalization within the π-system of the N—C—C—C—N backbone (Allen et al., 1992). The methyl and phenyl groups of the backbone adopt a syn orientation; the two aryl rings adopt a synperiplanar arrangement in order to minimize steric crowding.