Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050131/hg2306sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050131/hg2306Isup2.hkl |
CCDC reference: 667374
Naphthalene Tröger's base (100 mg, 0.311 mmol) was suspended in a mixture of trifluoroacetic anhydride (TFAA) (0.5 ml) and dichloromethane (1 ml) and stirred at room temperature in a closed vessel. The reaction was monitored by TLC. After 3 h all starting material had been consumed and the reaction was quenched with ice and basified with saturated sodium hydrogen carbonate solution. The cloudy mixture was extracted with dichloromethane (2 x 30 ml) and the organic layers were combined before being washed with brine, dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure, affording a colourless transparent solid. The residue (assumed to be the di-trifluoroacetylated disecondary amine) was dissolved in a mixture of ethanol (5 ml) and sodium hydroxide (100 mg) and stirred at room temperature for 12 h. Ethanol was removed under vacuum and the residue was taken up in a mixture of water (20 ml) and dichloromethane (20 ml). The organic layer was separated and the aqueous layer extracted with dichloromethane (20 ml). The combined organic layers were then washed with brine, dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The residue was chromatographed (silica gel, dichloromethane) to afford (I) (35 mg, 38%) as a white solid (the first major band eluted), m.p: 172.06 °C (DSC). Single crystals of (I) were grown by slow evaporation of a dichloromethane/methanol solution.
Refinement on F was by full-matrix least squares (RAELS) using anisotropic thermal parameters for non-hydrogen atoms. Hydrogen atoms were included in geometrically idealized positions calculated each cycle, with C—H distances of 1.00 Å, and were assigned thermal parameters equal to those of the parent atom. The NH protons were included in idealized positions after location in a difference fourier. The methanol was located in a difference fourier, and included as two independent anisotropic atoms. The H atoms were not located. This space group has a floating origin in the z direction, so to avoid a singular situation the z coordinate of one atom (N1) is fixed.
The syntheses of methylene bridged aromatic amines have been the subject of over 40 patents during the past 40 years, however, to the best of our knowledge the synthesis of (I) has not been previously reported. Compound (I) was obtained as an unexpected by-product in the removal of the apical methylene strap from naphthalene Tröger's base (Farrar, 1964; Tálas et al., 1998) using trifluoroacetic anhydride (Miyahara et al., 1999) as outlined in Fig. 2. Dinitrated analogues of (I), and various isomers thereof, have been reported (Morgan & Jones, 1923) and benzo analogues (Partridge & Vipond, 1962) have been used in the synthesis of organometallic complexes (Gibson et al., 1996) The asymmetric unit contains one half molecule of (I) and one half molecule of methanol, i.e., it is a 1:1 composition. The two naphthalene rings of (I) are oriented at almost 90 ° with respect to one another, and they are aligned in an anti-parallel fashion, such that the the two amino substituents are projected in opposite directions.
The molecular structure of (I) is shown in Fig. 1.
For related literature, see: Farrar (1964); Gibson et al. (1996); Ibers & Hamilton (1974); Miyahara et al. (1999); Morgan & Jones (1923); Partridge & Vipond (1962); Tálas et al. (1998).
Data collection: CAD-4 Software (Schagen et al., 1989); cell refinement: CAD-4 Software (Schagen et al., 1989); data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: RAELS (Rae, 1996); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: local programs.
C21H18N2·CH4O | Dx = 1.28 Mg m−3 |
Mr = 330.4 | Melting point: 445 K |
Orthorhombic, Ccc2 | Mo Kα radiation, λ = 0.71073 Å |
a = 13.020 (4) Å | Cell parameters from 11 reflections |
b = 26.448 (7) Å | θ = 11–13° |
c = 4.978 (2) Å | µ = 0.08 mm−1 |
V = 1714.2 (9) Å3 | T = 294 K |
Z = 4 | Prism, colourless |
F(000) = 704.0 | 0.30 × 0.12 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | h = 0→15 |
ω–2θ scans | k = 0→31 |
851 measured reflections | l = 0→5 |
851 independent reflections | 1 standard reflections every 30 min |
720 reflections with I > 2σ(I) | intensity decay: none |
θmax = 25° |
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(F) + 0.0004F2] |
wR(F2) = 0.065 | (Δ/σ)max = 0.002 |
S = 1.34 | Δρmax = 0.26 e Å−3 |
720 reflections | Δρmin = −0.23 e Å−3 |
118 parameters |
C21H18N2·CH4O | V = 1714.2 (9) Å3 |
Mr = 330.4 | Z = 4 |
Orthorhombic, Ccc2 | Mo Kα radiation |
a = 13.020 (4) Å | µ = 0.08 mm−1 |
b = 26.448 (7) Å | T = 294 K |
c = 4.978 (2) Å | 0.30 × 0.12 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 720 reflections with I > 2σ(I) |
851 measured reflections | 1 standard reflections every 30 min |
851 independent reflections | intensity decay: none |
R[F2 > 2σ(F2)] = 0.049 | 118 parameters |
wR(F2) = 0.065 | H-atom parameters not refined |
S = 1.34 | Δρmax = 0.26 e Å−3 |
720 reflections | Δρmin = −0.23 e Å−3 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.4225 (2) | 0.2517 (1) | 0.6709 | 0.0515 (7) | |
C1 | 0.3632 (2) | 0.2076 (1) | 0.6484 (8) | 0.0462 (8) | |
C2 | 0.3936 (2) | 0.1656 (1) | 0.8030 (9) | 0.0564 (9) | |
C3 | 0.3454 (3) | 0.1203 (1) | 0.7752 (10) | 0.064 (1) | |
C4 | 0.2654 (2) | 0.1137 (1) | 0.5882 (10) | 0.0574 (9) | |
C5 | 0.2174 (3) | 0.0660 (1) | 0.5540 (12) | 0.072 (1) | |
C6 | 0.1411 (3) | 0.0597 (2) | 0.3746 (13) | 0.080 (1) | |
C7 | 0.1081 (3) | 0.1006 (2) | 0.2175 (12) | 0.073 (1) | |
C8 | 0.1523 (3) | 0.1472 (1) | 0.2473 (9) | 0.062 (1) | |
C9 | 0.2335 (2) | 0.1558 (1) | 0.4327 (9) | 0.0491 (8) | |
C10 | 0.2820 (2) | 0.2038 (1) | 0.4677 (8) | 0.0441 (7) | |
C11 | 0.2500 | 0.2500 | 0.3067 (11) | 0.051 (1) | |
C1Me | 0.5000 | 0.0000 | 0.046 (6) | 0.168 (7) | |
O1Me | 0.4580 (6) | 0.0183 (3) | 0.296 (4) | 0.216 (9) | 0.5 |
H1N1 | 0.4835 | 0.2524 | 0.7930 | 0.052 | |
H2N1 | 0.4038 | 0.2824 | 0.5648 | 0.052 | |
HC2 | 0.4512 | 0.1691 | 0.9346 | 0.056 | |
HC3 | 0.3671 | 0.0912 | 0.8898 | 0.064 | |
HC5 | 0.2405 | 0.0366 | 0.6650 | 0.072 | |
HC6 | 0.1079 | 0.0258 | 0.3534 | 0.080 | |
HC7 | 0.0519 | 0.0957 | 0.0830 | 0.073 | |
HC8 | 0.1269 | 0.1760 | 0.1354 | 0.062 | |
H1C11 | 0.1906 | 0.2400 | 0.1907 | 0.051 | 0.5 |
H2C11 | 0.3094 | 0.2600 | 0.1907 | 0.051 | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.047 (1) | 0.063 (2) | 0.044 (2) | −0.003 (1) | −0.002 (1) | 0.000 (1) |
C1 | 0.042 (1) | 0.060 (2) | 0.038 (2) | 0.006 (1) | 0.005 (1) | −0.005 (2) |
C2 | 0.054 (2) | 0.068 (2) | 0.047 (2) | 0.006 (2) | −0.002 (2) | 0.006 (2) |
C3 | 0.065 (2) | 0.066 (2) | 0.062 (2) | 0.012 (2) | 0.000 (2) | 0.012 (2) |
C4 | 0.059 (2) | 0.057 (2) | 0.056 (2) | 0.005 (2) | 0.009 (2) | −0.001 (2) |
C5 | 0.070 (2) | 0.060 (2) | 0.086 (3) | 0.000 (2) | 0.015 (3) | −0.002 (2) |
C6 | 0.081 (3) | 0.065 (2) | 0.093 (3) | −0.013 (2) | 0.021 (3) | −0.021 (3) |
C7 | 0.072 (2) | 0.084 (2) | 0.065 (3) | −0.011 (2) | −0.002 (2) | −0.023 (2) |
C8 | 0.063 (2) | 0.077 (2) | 0.047 (2) | −0.005 (2) | −0.004 (2) | −0.007 (2) |
C9 | 0.047 (2) | 0.061 (2) | 0.039 (2) | 0.001 (1) | 0.008 (2) | −0.008 (2) |
C10 | 0.047 (2) | 0.053 (2) | 0.032 (2) | 0.005 (1) | 0.005 (1) | −0.002 (2) |
C11 | 0.058 (2) | 0.063 (3) | 0.032 (2) | −0.001 (2) | 0.0000 | 0.0000 |
C1Me | 0.141 (9) | 0.096 (7) | 0.267 (9) | 0.009 (7) | 0.0000 | 0.0000 |
O1Me | 0.145 (9) | 0.139 (9) | 0.363 (9) | −0.001 (7) | −0.002 (9) | 0.017 (9) |
N1—C1 | 1.402 (4) | C6—C7 | 1.404 (7) |
N1—H1N1 | 1.000 | C6—HC6 | 1.000 |
N1—H2N1 | 1.000 | C7—C8 | 1.368 (5) |
C1—C2 | 1.408 (4) | C7—HC7 | 1.000 |
C1—C10 | 1.392 (4) | C8—C9 | 1.422 (4) |
C2—C3 | 1.359 (5) | C8—HC8 | 1.000 |
C2—HC2 | 1.000 | C9—C10 | 1.427 (4) |
C3—C4 | 1.407 (5) | C10—C11 | 1.520 (4) |
C3—HC3 | 1.000 | C11—C10i | 1.520 (4) |
C4—C5 | 1.418 (5) | C11—H1C11 | 1.000 |
C4—C9 | 1.420 (5) | C11—H2C11 | 1.000 |
C5—C6 | 1.346 (7) | C1Me—O1Me | 1.443 (17) |
C5—HC5 | 1.000 | ||
C1—N1—H1N1 | 120.0 | C5—C6—HC6 | 120.1 |
C1—N1—H2N1 | 120.0 | C7—C6—HC6 | 120.1 |
H1N1—N1—H2N1 | 120.0 | C6—C7—C8 | 120.4 (4) |
N1—C1—C2 | 117.3 (3) | C6—C7—HC7 | 119.8 |
N1—C1—C10 | 122.0 (3) | C8—C7—HC7 | 119.8 |
C2—C1—C10 | 120.6 (3) | C7—C8—C9 | 121.9 (4) |
C1—C2—C3 | 120.7 (3) | C7—C8—HC8 | 119.1 |
C1—C2—HC2 | 119.7 | C9—C8—HC8 | 119.1 |
C3—C2—HC2 | 119.7 | C4—C9—C8 | 116.5 (3) |
C2—C3—C4 | 121.2 (3) | C4—C9—C10 | 120.1 (3) |
C2—C3—HC3 | 119.4 | C8—C9—C10 | 123.4 (3) |
C4—C3—HC3 | 119.4 | C1—C10—C9 | 118.7 (3) |
C3—C4—C5 | 121.1 (4) | C1—C10—C11 | 119.4 (2) |
C3—C4—C9 | 118.7 (3) | C9—C10—C11 | 121.9 (3) |
C5—C4—C9 | 120.2 (3) | C10—C11—C10i | 116.4 (4) |
C4—C5—C6 | 121.1 (4) | C10—C11—H1C11 | 107.7 |
C4—C5—HC5 | 119.4 | C10—C11—H2C11 | 107.7 |
C6—C5—HC5 | 119.4 | H1C11—C11—H2C11 | 109.5 |
C5—C6—C7 | 119.9 (4) |
Symmetry code: (i) −x+1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C21H18N2·CH4O |
Mr | 330.4 |
Crystal system, space group | Orthorhombic, Ccc2 |
Temperature (K) | 294 |
a, b, c (Å) | 13.020 (4), 26.448 (7), 4.978 (2) |
V (Å3) | 1714.2 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 851, 851, 720 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.065, 1.34 |
No. of reflections | 720 |
No. of parameters | 118 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.23 |
Computer programs: CAD-4 Software (Schagen et al., 1989), SIR92 (Altomare et al., 1994), RAELS (Rae, 1996), ORTEPII (Johnson, 1976), local programs.
The syntheses of methylene bridged aromatic amines have been the subject of over 40 patents during the past 40 years, however, to the best of our knowledge the synthesis of (I) has not been previously reported. Compound (I) was obtained as an unexpected by-product in the removal of the apical methylene strap from naphthalene Tröger's base (Farrar, 1964; Tálas et al., 1998) using trifluoroacetic anhydride (Miyahara et al., 1999) as outlined in Fig. 2. Dinitrated analogues of (I), and various isomers thereof, have been reported (Morgan & Jones, 1923) and benzo analogues (Partridge & Vipond, 1962) have been used in the synthesis of organometallic complexes (Gibson et al., 1996) The asymmetric unit contains one half molecule of (I) and one half molecule of methanol, i.e., it is a 1:1 composition. The two naphthalene rings of (I) are oriented at almost 90 ° with respect to one another, and they are aligned in an anti-parallel fashion, such that the the two amino substituents are projected in opposite directions.
The molecular structure of (I) is shown in Fig. 1.