Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001507/cf6041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001507/cf6041Isup2.hkl |
CCDC reference: 159756
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.056
- wR factor = 0.185
- Data-to-parameter ratio = 9.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.99 From the CIF: _reflns_number_total 1540 Count of symmetry unique reflns 1540 Completeness (_total/calc) 100.00% 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 WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
A warm solution of pyridinium salt (3) (Ferguson & McAlees, 1990) (3.47 g, 10.0 mmol) in water (20 ml) was treated with an aqueous solution (25 ml) containing Me2NH2+.Cl- (9.00 g, 110 mmol) and sodium hydroxide (3.0 g, 75 mmol). A dark purple–brown precipitate formed immediately. Ethanol (20 ml) was added and the mixture was stirred and heated at the reflux for 2.5 h, then solvent was distilled to remove most of the ethanol. The resulting dark mixture was allowed to cool overnight and was then filtered to give an olive–brown solid (1.58 g after washing and drying; mainly 2,4-dinitroaniline) which was washed with warm water (3 × 10 ml). The combined filtrate and washings were washed with chloroform (3 × 30 ml) and treated with an aqueous solution (10 ml) of NH4+.PF6- (1.63 g, 10.0 mmol), whereupon a light yellow precipitate appeared. The aqueous mixture was then extracted with CH2Cl2(3 × 30 ml), and the combined extracts were dried (Na2SO4) and evaporated to leave an orange-yellow solid (1.89 g). Crystallization of this material from methanol gave (4) (0.70 g) as well formed straw-yellow prisms (m.p. 396.5–397.0 K). Concentration of the mother liquors and prolonged standing gave a further 0.51 g. of this material [total yield 42% based on (1)]. 1H NMR (CD3CN, 400 MHz) δ = 2.22 (s, C—Me), 3.01, 3.16, 3.23, 3.24 (each s, N—Me), 5.10 (d, J = 12.1 Hz, C2—H) and 7.74 (d, J = 12.1 Hz, C3—H).
Molecule (1) crystallized in the orthorhombic system; space group P212121 from the systematic absences. No Friedel reflections were collected and the resulting Flack (1983) parameter [0.5 (3)] is indeterminate. H atoms were treated as riding atoms with C—H distances of 0.93 and 0.96 Å. The methyl groups at C11, C12 and C21 were each modelled using six H sites, each with occupancy 1/2, mutually offset by 60°.
Data collection: CAD-4-PC Software (Nonius, 1992); cell refinement: SET4 and CELDIM (Nonius, 1992); data reduction: HELENA in PLATON (Spek, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 2001).
C8H17N2+·PF6− | Dx = 1.410 Mg m−3 |
Mr = 286.21 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 7.470 (4) Å | θ = 10.0–14.5° |
b = 11.110 (3) Å | µ = 0.26 mm−1 |
c = 16.242 (3) Å | T = 293 K |
V = 1348.0 (8) Å3 | Plate, yellow |
Z = 4 | 0.50 × 0.50 × 0.35 mm |
F(000) = 592 |
Nonius CAD-4 diffractometer | Rint = 0.0 |
Radiation source: fine-focus sealed X-ray tube | θmax = 26.0°, θmin = 2.2° |
Graphite monochromator | h = −9→0 |
θ/2θ scans | k = −13→0 |
1540 measured reflections | l = −20→0 |
1540 independent reflections | 3 standard reflections every 120 min |
1042 reflections with I > 2σ(1) | intensity decay: 1.0% |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.185 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1171P)2 + 0.3108P] where P = (Fo2 + 2Fc2)/3 |
1540 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C8H17N2+·PF6− | V = 1348.0 (8) Å3 |
Mr = 286.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.470 (4) Å | µ = 0.26 mm−1 |
b = 11.110 (3) Å | T = 293 K |
c = 16.242 (3) Å | 0.50 × 0.50 × 0.35 mm |
Nonius CAD-4 diffractometer | Rint = 0.0 |
1540 measured reflections | 3 standard reflections every 120 min |
1540 independent reflections | intensity decay: 1.0% |
1042 reflections with I > 2σ(1) |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.185 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
1540 reflections | Δρmin = −0.23 e Å−3 |
156 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.7944(0.0231) x + 8.0662 (0.0177) y + 7.5288 (0.0880) z = 7.4539 (0.0138) 3.79 (2)x + 8.066 (18)y + 7.52 (9)z = 7.454 (14) * -0.015 (2) N1 * 0.014 (3) C2 * 0.016 (4) C3 * -0.014 (3) C4 * -0.001 (3) N5 0.032 (8) C11 - 0.156 (14) C12 0.120 (14) C21 - 0.021 (9) C51 0.069 (13) C52 Rms deviation of fitted atoms = 0.0133 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 1.0805 (6) | 0.2672 (4) | 0.1572 (3) | 0.0751 (11) | |
N5 | 0.6198 (6) | 0.5486 (4) | 0.0899 (3) | 0.0748 (11) | |
C2 | 0.9329 (7) | 0.3237 (4) | 0.1750 (3) | 0.0652 (11) | |
C3 | 0.8570 (7) | 0.4091 (4) | 0.1220 (3) | 0.0663 (11) | |
H3 | 0.9182 | 0.4281 | 0.0739 | 0.080* | |
C4 | 0.6973 (7) | 0.4664 (4) | 0.1371 (3) | 0.0690 (12) | |
H4 | 0.6377 | 0.4455 | 0.1852 | 0.083* | |
C11 | 1.1677 (9) | 0.1800 (5) | 0.2130 (4) | 0.0981 (18) | |
H11A | 1.2747 | 0.1497 | 0.1876 | 0.147* | 0.50 |
H11B | 1.0873 | 0.1144 | 0.2238 | 0.147* | 0.50 |
H11C | 1.1979 | 0.2192 | 0.2638 | 0.147* | 0.50 |
H11D | 1.0986 | 0.1725 | 0.2625 | 0.147* | 0.50 |
H11E | 1.2859 | 0.2077 | 0.2263 | 0.147* | 0.50 |
H11F | 1.1754 | 0.1030 | 0.1863 | 0.147* | 0.50 |
C12 | 1.1693 (10) | 0.2820 (6) | 0.0779 (4) | 0.114 (2) | |
H12A | 1.2754 | 0.2333 | 0.0765 | 0.171* | 0.50 |
H12B | 1.2011 | 0.3650 | 0.0704 | 0.171* | 0.50 |
H12C | 1.0898 | 0.2574 | 0.0346 | 0.171* | 0.50 |
H12D | 1.1021 | 0.3371 | 0.0445 | 0.171* | 0.50 |
H12E | 1.1764 | 0.2055 | 0.0506 | 0.171* | 0.50 |
H12F | 1.2878 | 0.3130 | 0.0864 | 0.171* | 0.50 |
C21 | 0.8494 (8) | 0.2985 (5) | 0.2581 (3) | 0.0862 (16) | |
H21A | 0.9180 | 0.2381 | 0.2862 | 0.129* | 0.50 |
H21B | 0.7290 | 0.2704 | 0.2507 | 0.129* | 0.50 |
H21C | 0.8483 | 0.3710 | 0.2902 | 0.129* | 0.50 |
H21D | 0.7455 | 0.3483 | 0.2652 | 0.129* | 0.50 |
H21E | 0.9346 | 0.3159 | 0.3008 | 0.129* | 0.50 |
H21F | 0.8153 | 0.2153 | 0.2612 | 0.129* | 0.50 |
C51 | 0.4534 (8) | 0.6023 (6) | 0.1135 (4) | 0.0957 (18) | |
H51A | 0.4207 | 0.5749 | 0.1675 | 0.144* | |
H51B | 0.3621 | 0.5797 | 0.0749 | 0.144* | |
H51C | 0.4658 | 0.6883 | 0.1139 | 0.144* | |
C52 | 0.6994 (9) | 0.5909 (6) | 0.0136 (4) | 0.0981 (18) | |
H52A | 0.8191 | 0.6184 | 0.0241 | 0.147* | |
H52B | 0.6294 | 0.6561 | −0.0080 | 0.147* | |
H52C | 0.7024 | 0.5263 | −0.0256 | 0.147* | |
P1 | 0.31494 (19) | 0.48016 (14) | 0.37157 (9) | 0.0784 (5) | |
F1 | 0.3907 (8) | 0.4626 (6) | 0.4610 (3) | 0.163 (2) | |
F2 | 0.2151 (8) | 0.3568 (4) | 0.3859 (3) | 0.1371 (17) | |
F3 | 0.1537 (7) | 0.5496 (4) | 0.4130 (3) | 0.1397 (18) | |
F4 | 0.4054 (9) | 0.6049 (5) | 0.3572 (4) | 0.196 (3) | |
F5 | 0.4763 (9) | 0.4145 (7) | 0.3339 (4) | 0.201 (3) | |
F6 | 0.2231 (9) | 0.4921 (5) | 0.2850 (3) | 0.157 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.076 (3) | 0.060 (2) | 0.089 (3) | 0.001 (2) | −0.001 (2) | −0.002 (2) |
N5 | 0.076 (2) | 0.074 (2) | 0.075 (2) | 0.011 (2) | −0.003 (2) | −0.006 (2) |
C2 | 0.065 (3) | 0.056 (2) | 0.074 (3) | −0.004 (2) | 0.001 (2) | −0.009 (2) |
C3 | 0.066 (2) | 0.062 (2) | 0.071 (3) | 0.000 (2) | 0.002 (2) | −0.004 (2) |
C4 | 0.067 (2) | 0.072 (3) | 0.068 (3) | −0.007 (2) | 0.001 (2) | −0.012 (2) |
C11 | 0.103 (4) | 0.083 (3) | 0.109 (4) | 0.022 (4) | −0.011 (4) | 0.000 (3) |
C12 | 0.113 (5) | 0.105 (4) | 0.124 (5) | 0.033 (5) | 0.045 (5) | 0.016 (4) |
C21 | 0.085 (3) | 0.090 (4) | 0.084 (3) | 0.002 (3) | 0.014 (3) | 0.006 (3) |
C51 | 0.081 (3) | 0.106 (4) | 0.099 (4) | 0.017 (4) | 0.001 (3) | −0.004 (3) |
C52 | 0.097 (4) | 0.104 (4) | 0.093 (4) | 0.014 (4) | 0.011 (4) | 0.013 (3) |
P1 | 0.0699 (7) | 0.0848 (8) | 0.0807 (8) | 0.0021 (8) | −0.0014 (7) | −0.0021 (7) |
F1 | 0.147 (4) | 0.218 (5) | 0.123 (3) | 0.037 (5) | −0.054 (3) | −0.012 (3) |
F2 | 0.181 (4) | 0.100 (2) | 0.130 (3) | −0.028 (3) | −0.004 (4) | 0.022 (2) |
F3 | 0.119 (3) | 0.140 (4) | 0.161 (4) | 0.043 (3) | 0.024 (3) | 0.002 (3) |
F4 | 0.152 (5) | 0.130 (4) | 0.305 (8) | −0.062 (4) | 0.033 (6) | −0.006 (5) |
F5 | 0.173 (5) | 0.210 (6) | 0.219 (6) | 0.085 (5) | 0.106 (5) | 0.017 (5) |
F6 | 0.218 (5) | 0.158 (4) | 0.094 (2) | −0.030 (5) | −0.028 (3) | 0.025 (3) |
N1—C2 | 1.301 (6) | C12—H12E | 0.960 |
N1—C11 | 1.478 (7) | C12—H12F | 0.960 |
N1—C12 | 1.458 (7) | C21—H21A | 0.960 |
N5—C4 | 1.325 (7) | C21—H21B | 0.960 |
N5—C51 | 1.431 (7) | C21—H21C | 0.960 |
N5—C52 | 1.452 (7) | C21—H21D | 0.960 |
C2—C3 | 1.401 (7) | C21—H21E | 0.960 |
C2—C21 | 1.513 (7) | C21—H21F | 0.960 |
C3—C4 | 1.374 (7) | C51—H51A | 0.960 |
C3—H3 | 0.930 | C51—H51B | 0.960 |
C4—H4 | 0.930 | C51—H51C | 0.960 |
C11—H11A | 0.960 | C52—H52A | 0.960 |
C11—H11B | 0.960 | C52—H52B | 0.960 |
C11—H11C | 0.960 | C52—H52C | 0.960 |
C11—H11D | 0.960 | P1—F5 | 1.536 (5) |
C11—H11E | 0.960 | P1—F4 | 1.559 (5) |
C11—H11F | 0.960 | P1—F6 | 1.570 (5) |
C12—H12A | 0.960 | P1—F1 | 1.571 (4) |
C12—H12B | 0.960 | P1—F2 | 1.578 (5) |
C12—H12C | 0.960 | P1—F3 | 1.581 (5) |
C12—H12D | 0.960 | ||
C2—N1—C12 | 121.8 (5) | C2—C21—H21A | 109.5 |
C2—N1—C11 | 123.6 (5) | C2—C21—H21B | 109.5 |
C12—N1—C11 | 114.5 (5) | H21A—C21—H21B | 109.5 |
C4—N5—C51 | 120.8 (5) | C2—C21—H21C | 109.5 |
C4—N5—C52 | 122.5 (5) | H21A—C21—H21C | 109.5 |
C51—N5—C52 | 116.7 (5) | H21B—C21—H21C | 109.5 |
N1—C2—C3 | 122.2 (5) | C2—C21—H21D | 109.5 |
N1—C2—C21 | 117.3 (5) | C2—C21—H21E | 109.5 |
C3—C2—C21 | 120.4 (4) | H21D—C21—H21E | 109.5 |
C4—C3—C2 | 123.8 (5) | C2—C21—H21F | 109.5 |
C4—C3—H3 | 118.1 | H21D—C21—H21F | 109.5 |
C2—C3—H3 | 118.1 | H21E—C21—H21F | 109.5 |
N5—C4—C3 | 126.6 (5) | N5—C51—H51A | 109.5 |
N5—C4—H4 | 116.7 | N5—C51—H51B | 109.5 |
C3—C4—H4 | 116.7 | H51A—C51—H51B | 109.5 |
N1—C11—H11A | 109.5 | N5—C51—H51C | 109.5 |
N1—C11—H11B | 109.5 | H51A—C51—H51C | 109.5 |
H11A—C11—H11B | 109.5 | H51B—C51—H51C | 109.5 |
N1—C11—H11C | 109.5 | N5—C52—H52A | 109.5 |
H11A—C11—H11C | 109.5 | N5—C52—H52B | 109.5 |
H11B—C11—H11C | 109.5 | H52A—C52—H52B | 109.5 |
N1—C11—H11D | 109.5 | N5—C52—H52C | 109.5 |
N1—C11—H11E | 109.5 | H52A—C52—H52C | 109.5 |
H11D—C11—H11E | 109.5 | H52B—C52—H52C | 109.5 |
N1—C11—H11F | 109.5 | F5—P1—F4 | 91.3 (4) |
H11D—C11—H11F | 109.5 | F5—P1—F6 | 91.5 (4) |
H11E—C11—H11F | 109.5 | F4—P1—F6 | 88.9 (3) |
N1—C12—H12A | 109.5 | F5—P1—F1 | 91.5 (4) |
N1—C12—H12B | 109.5 | F4—P1—F1 | 95.3 (4) |
H12A—C12—H12B | 109.5 | F6—P1—F1 | 174.8 (3) |
N1—C12—H12C | 109.5 | F5—P1—F2 | 91.0 (3) |
H12A—C12—H12C | 109.5 | F4—P1—F2 | 177.5 (3) |
H12B—C12—H12C | 109.5 | F6—P1—F2 | 90.0 (3) |
N1—C12—H12D | 109.5 | F1—P1—F2 | 85.7 (3) |
N1—C12—H12E | 109.5 | F5—P1—F3 | 177.8 (4) |
H12D—C12—H12E | 109.5 | F4—P1—F3 | 87.7 (3) |
N1—C12—H12F | 109.5 | F6—P1—F3 | 90.4 (3) |
H12D—C12—H12F | 109.5 | F1—P1—F3 | 86.7 (3) |
H12E—C12—H12F | 109.5 | F2—P1—F3 | 90.1 (3) |
C12—N1—C2—C3 | −5.0 (7) | C21—C2—C3—C4 | −6.3 (7) |
C11—N1—C2—C3 | 177.6 (5) | C51—N5—C4—C3 | −179.3 (5) |
C12—N1—C2—C21 | 178.1 (5) | C52—N5—C4—C3 | −0.9 (8) |
C11—N1—C2—C21 | 0.8 (7) | C2—C3—C4—N5 | 179.3 (5) |
N1—C2—C3—C4 | 177.0 (4) |
Experimental details
Crystal data | |
Chemical formula | C8H17N2+·PF6− |
Mr | 286.21 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.470 (4), 11.110 (3), 16.242 (3) |
V (Å3) | 1348.0 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.50 × 0.50 × 0.35 |
Data collection | |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(1)] reflections | 1540, 1540, 1042 |
Rint | 0.0 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.185, 1.03 |
No. of reflections | 1540 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Computer programs: CAD-4-PC Software (Nonius, 1992), SET4 and CELDIM (Nonius, 1992), HELENA in PLATON (Spek, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2001), SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 2001).
N1—C2 | 1.301 (6) | N5—C52 | 1.452 (7) |
N1—C11 | 1.478 (7) | C2—C3 | 1.401 (7) |
N1—C12 | 1.458 (7) | C2—C21 | 1.513 (7) |
N5—C4 | 1.325 (7) | C3—C4 | 1.374 (7) |
N5—C51 | 1.431 (7) |
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Salts of the title cation have been prepared and characterized (Arnold & Zemlinka, 1959; Arnold, 1973), but a search of the Cambridge Structural Database (Allen & Kennard, 1993) shows that there have apparently been no crystal structure reports. The title salt, (1), was obtained as a by-product in the course of attempts to prepare the pyrrole-substituted pentamethinecyanine derivative (2).
The X-ray structural investigation of (1) shows the presence of discrete fully delocalized cations and hexafluorophosphate anions with unexceptional dimensions. The delocalized moiety (N1/C2/C3/C4/N5) of the cation is close to planar [maximum deviation 0.016 (4) Å for C3], and it adopts an all-trans configuration as has been suggested by others on the basis of NMR studies (Filleux-Blanchard et al., 1974) and found for the related cation [Me2N(CH)3NMe2]+ in 1,3-bis(dimethylamino)trimethinium perchlorate (Matthews et al., 1973; Sieber et al., 1974). The C atoms of all five methyl substituents also lie close to the N1/C2/C3/C4/N5 plane of the cation [maximum deviation 0.156 (14) Å for C12].