Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015742/bj1008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015742/bj1008Isup2.hkl |
CCDC reference: 159990
For related literature, see: Arai & Hida (1992); Boekelheide & Gall (1954); Boubekeur et al. (1989); Bradsher (1984); Brock & Dunitz (1982); Elix et al. (1971); Florencio et al. (1984); Glover & Jones (1958); Hensen et al. (1999); Johnson & Burnett (1996); Kobayashi et al. (1971); Maassarani & Pfeffer (1990); Miyadera & Iwai (1964).
Quinolizinium bromide was prepared according to the method of Glover & Jones (1958) with the modifications of Miyadera & Iwai (1964). The hexafluorophosphate salt was obtained from an aqueous solution of the bromide by treatment with ammonium hexafluorophosphate. Clear colourless needles of quinolizinium hexafluorophosphate, (I) (m.p. 272.5–273 K), were obatined by slow evaporation from acetonitrile.
All H atoms were refined isotropically. Atoms N5 and C9a were placed on the same site, each with occupancy 1/2, and refined with the same displacement parameters.
Data collection: Rigaku/AFC Diffractometer Control Software (Rigaku Corporation, 1995); cell refinement: Rigaku/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1994) and DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: TEXSAN.
Fig. 1. The molecular structure of the quinolizinium cation in (I) shown with 50% probability ellipsoids. H atoms are drawn as small spheres of arbitrary radii. |
C9H8N+·PF6− | Dx = 1.825 Mg m−3 |
Mr = 275.13 | Melting point = 272.5–273 K |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.7107 Å |
a = 8.505 (3) Å | Cell parameters from 25 reflections |
b = 9.541 (3) Å | θ = 14–15° |
c = 6.827 (2) Å | µ = 0.34 mm−1 |
β = 115.33 (3)° | T = 145 K |
V = 500.7 (3) Å3 | Needle-like, colourless |
Z = 2 | 0.44 × 0.30 × 0.20 mm |
F(000) = 276.00 |
Rigaku AFC-7R diffractometer | Rint = 0.015 |
Radiation source: Rigaku rotating anode | θmax = 27.5°, θmin = 3.3° |
Graphite monochromator | h = 0→11 |
ω/2θ scans | k = 0→12 |
656 measured reflections | l = −8→8 |
615 independent reflections | 3 standard reflections every 150 reflections |
562 reflections with I > 2σ(I) | intensity decay: −0.6% |
Refinement on F2 | All H-atom parameters refined |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0321P)2 + 0.3901P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.025 | (Δ/σ)max < 0.001 |
wR(F2) = 0.068 | Δρmax = 0.29 e Å−3 |
S = 1.09 | Δρmin = −0.32 e Å−3 |
562 reflections | Extinction correction: SHELXL93 (Sheldrick, 1993), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
54 parameters | Extinction coefficient: 0.020 |
1 restraint |
C9H8N+·PF6− | V = 500.7 (3) Å3 |
Mr = 275.13 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 8.505 (3) Å | µ = 0.34 mm−1 |
b = 9.541 (3) Å | T = 145 K |
c = 6.827 (2) Å | 0.44 × 0.30 × 0.20 mm |
β = 115.33 (3)° |
Rigaku AFC-7R diffractometer | Rint = 0.015 |
656 measured reflections | 3 standard reflections every 150 reflections |
615 independent reflections | intensity decay: −0.6% |
562 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.025 | 1 restraint |
wR(F2) = 0.068 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.29 e Å−3 |
562 reflections | Δρmin = −0.32 e Å−3 |
54 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. |
Refinement. Refinement based on F2 against all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2, conventional R-factors (R) are calculated 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. thus the refinement was done using all reflections. R-factors based on F2 are statistically about twice as large as those based on F, and R-factor based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
P1 | 1 | 0 | 3/2 | 0.0212 (2) | |
F1 | 0.9788 (2) | 0 | 1.2550 (2) | 0.0361 (3) | |
F2 | 1.1461 (1) | 0.11821 (9) | 1.5603 (2) | 0.0410 (3) | |
N5 | 1 | −0.4278 (2) | 1 | 0.0211 (3) | 0.50 |
C9a | 1 | −0.4278 (2) | 1 | 0.0211 (3) | 0.50 |
C1 | 0.9306 (2) | −0.3562 (1) | 1.1234 (2) | 0.0265 (3) | |
C2 | 0.8607 (2) | −0.4262 (2) | 1.2391 (2) | 0.0296 (3) | |
H1 | 0.934 (2) | −0.259 (2) | 1.119 (2) | 0.03610 (5)* | |
H2 | 0.812 (2) | −0.379 (2) | 1.318 (3) | 0.04139 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0218 (3) | 0.0199 (3) | 0.0217 (3) | 0 | 0.0092 (2) | 0 |
F1 | 0.0454 (7) | 0.0401 (7) | 0.0250 (6) | 0 | 0.0171 (5) | 0 |
F2 | 0.0411 (5) | 0.0390 (5) | 0.0466 (5) | −0.0187 (4) | 0.0223 (4) | −0.0105 (4) |
N5 | 0.0186 (7) | 0.0203 (8) | 0.0204 (7) | 0 | 0.0044 (6) | 0 |
C9a | 0.0186 (7) | 0.0203 (8) | 0.0204 (7) | 0 | 0.0044 (6) | 0 |
C1 | 0.0248 (6) | 0.0245 (6) | 0.0262 (6) | 0.0015 (5) | 0.0070 (5) | −0.0038 (5) |
C2 | 0.0259 (6) | 0.0377 (8) | 0.0244 (6) | 0.0023 (5) | 0.0100 (5) | −0.0048 (5) |
P1—F1 | 1.603 (1) | N5/C9a—N5/C9aiv | 1.378 (3) |
P1—F1i | 1.603 (1) | N5/C9a—C1 | 1.396 (2) |
P1—F2 | 1.5962 (9) | N5/C9a—C1v | 1.396 (2) |
P1—F2ii | 1.5962 (9) | C1—C2 | 1.352 (2) |
P1—F2i | 1.5962 (9) | C2—C2iv | 1.408 (3) |
P1—F2iii | 1.5962 (9) | ||
F2—P1—F2ii | 89.92 (7) | F2iii—P1—F1 | 90.19 (5) |
F2—P1—F2i | 180.0 | F2iii—P1—F1i | 89.81 (5) |
F2—P1—F2iii | 90.08 (7) | F1—P1—F1i | 180.0 |
F2—P1—F1 | 89.81 (5) | N5/C9aiv—N5/C9a—C1 | 119.31 (8) |
F2—P1—F1i | 90.19 (5) | N5/C9aiv—N5/C9a—C1v | 119.31 (8) |
F2ii—P1—F2i | 90.08 (7) | C1—N5/C9a—C1v | 121.4 (2) |
F2ii—P1—F2iii | 180.0 | H1—C1—C2 | 122 (1) |
F2ii—P1—F1 | 89.81 (5) | H1—C1—N5/C9a | 115 (1) |
F2ii—P1—F1i | 90.19 (5) | C2—C1—N5/C9a | 121.0 (1) |
F2i—P1—F2iii | 89.92 (7) | H2—C2—C1 | 121 (1) |
F2i—P1—F1 | 90.19 (5) | H2—C2—C2iv | 119 (1) |
F2i—P1—F1i | 89.81 (5) | C1—C2—C2iv | 119.65 (9) |
N5/C9aiv—N5/C9a—C1—C2 | −1.3 (1) | C1—N5/C9a—N5/C9aiv—C1iv | 0.0 |
N5/C9a—N5/C9aiv—C1vi—C2vi | 1.3 (1) | C1—N5/C9a—N5/C9aiv—C1vi | 180.0 |
N5/C9a—C1—C2—C2iv | 1.3 (1) | C1—N5/C9a—C1v—C2v | 178.7 (1) |
N5/C9a—C1v—C2v—C2vi | 1.3 (1) | C1—C2—C2iv—C1iv | 0.0 |
Symmetry codes: (i) −x+2, −y, −z+3; (ii) x, −y, z; (iii) −x+2, y, −z+3; (iv) x, −y−1, z; (v) −x+2, y, −z+2; (vi) −x+2, −y−1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C9H8N+·PF6− |
Mr | 275.13 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 145 |
a, b, c (Å) | 8.505 (3), 9.541 (3), 6.827 (2) |
β (°) | 115.33 (3) |
V (Å3) | 500.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.44 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 656, 615, 562 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.068, 1.09 |
No. of reflections | 562 |
No. of parameters | 54 |
No. of restraints | 1 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.29, −0.32 |
Computer programs: Rigaku/AFC Diffractometer Control Software (Rigaku Corporation, 1995), Rigaku/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1998), SIR92 (Altomare et al., 1994) and DIRDIF94 (Beurskens et al., 1994), SHELXL93 (Sheldrick, 1993), ORTEPIII (Johnson & Burnett, 1996), TEXSAN.
P1—F1 | 1.603 (1) | N5/C9a—C1 | 1.396 (2) |
P1—F2 | 1.5962 (9) | C1—C2 | 1.352 (2) |
N5/C9a—N5/C9ai | 1.378 (3) | C2—C2i | 1.408 (3) |
F2—P1—F2ii | 89.92 (7) | F1—P1—F1iii | 180.0 |
F2—P1—F2iii | 180.0 | N5/C9ai—N5/C9a—C1 | 119.31 (8) |
F2—P1—F2iv | 90.08 (7) | C1—N5/C9a—C1v | 121.4 (2) |
F2—P1—F1 | 89.81 (5) | C2—C1—N5/C9a | 121.0 (1) |
F2—P1—F1iii | 90.19 (5) | C1—C2—C2i | 119.65 (9) |
Symmetry codes: (i) x, −y−1, z; (ii) x, −y, z; (iii) −x+2, −y, −z+3; (iv) −x+2, y, −z+3; (v) −x+2, y, −z+2. |
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The quinolizinium ion, the newest of the benzenoid aromatic heterocyclic system having only a single N atom (Bradsher, 1984), and its derivatives form a novel class of compounds whose properties have not yet been studied extensively (Arai & Hida, 1992). The first synthesis of the parent quinolizinium cation was announced by Boekelheide & Gall (1954) and the cation has been assumed from its spectroscopic properties to have a planar structure resembling that of naphthalene (Boekelheide & Gall, 1954). A search of the Cambridge Crystallographic Database (ref?) shows that there have been four papers on single-crystal X-ray structure determinations of the azonia derivatives of polycyclic aromatics: fluoranthene (Boubekeur et al., 1989), 9-phenylanthracene (Maassarani & Pfeffer, 1990), 13-ethoxycarbonylbenzofluoranthene (Florencio et al., 1984) and 2-pyridyldiazaphenanthrene (Elix et al., 1971). No account of the structure of the parent quinolizinium cation has been found in the literature. We therefore decided to determine this structure in detail using the title hexafluorophosphate salt of the cation, (I). \sch
Data collection was undertaken at 145 K in order to minimize the thermal motion of the molecule. Analysis of a structure solution in space group C2 indicated a missing centre of symmetry. When refinement was attempted in the acentric space group, very high correlations were observed between the various parameters. For this reason, we considered a disordered structure in space group C2/m to be the correct solution. In this solution, the heterocyclic cation resides on a 2/m site (Wyckoff position d). The crystallographically imposed disorder causes the ring-shared carbon (C9a) and the ring-shared nitrogen (N5) to occupy a composite atomic site. The observed structure can be thought of as a statistical average between two orientations of the quinolizinium cation. The disorder observed in compound (I) seems to be a common feature in heterocycles which are isostructural with naphthalene. For example, disorder has also been found for quinoline (Kobayashi et al., 1971) and isoquinoline (Hensen et al., 1999).
An ORTEPIII drawing (Johnson & Burnett, 1996) of the cationic part of (I), together with the atomic numbering scheme, is shown in Fig. 1. The quinolizinium ring is planar: the maximum deviation from the best plane through the non-H atoms is for atom C1, which deviates by only 0.010 (1) Å. Bond lengths and angles are listed in Table 1. The most important structural differences between this aromatic cation and naphthalene (Brock & Dunitz, 1982) are contractions of the N—C bond lengths in (I), by 0.04 Å for N5—C9a and by 0.03 Å for N5/C9a—C1.