Acta Cryst. (2012). E68, o1061 [ doi:10.1107/S1600536812010185 ]
In the title compound, C24H20N4, obtained through the condensation of naphthalene-2,3-diamine with formaldehyde in methanol, the molecule is located on a special position of site symmetry -4. Due to symmetry considerations, the aromatic rings are strictly perpendicular to each other. In the crystal, molecules are linked by pairs of C-H
![[pi]](/logos/entities/pi_rmgif.gif)
interactions into columns along [110].
A solution of naphthalene-2,3-diamine (158 mg, 1 mmol) in methanol (10 ml) was added dropwise at 273 K to 5 ml of 37% aqueous formaldehyde. The reaction mixture was stirring at this temperature for 1 h and its completion was monitored by TLC. After completion, the contents were poured over cold water (10 ml). The resultant solid was isolated by filtration, washed with cold water, dried in vacuum and recrystallized from ethyl acetate to give the title compound with 28% yield. The melting point of the title structure is 484 K.
1H NMR (δ, 400 MHz, CDCl3): 4.55, 7.52, 7.74, 7.86. 13C NMR (δ, 100 MHz, CDCl3): 70.2, 125.6, 126.2, 127.7, 133.0, 151.9.
The H atoms atoms were found in difference Fourier maps and their coordinates were refined freely. The isotropic atomic displacement parameters of hydrogen atoms were evaluated as 1.2×Ueq of the parent atom. As the structure contains only light atoms, the Friedel-pair reflections were merged and the Flack parameter has not been determined.
Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).
![[Figure 1]](./bg2445fig1thm.gif)
| Fig. 1. A view of (I) with the numbering scheme, displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) 1 + y,1 - x,-z; (ii) 2 - x,-y,z; (iii) 1 - y,-1 + x,-z. |
![[Figure 2]](./bg2445fig2thm.gif)
| Fig. 2. Packing of the molecules of the title compound view along b axis. |
| C24H20N4 | Dx = 1.338 Mg m−3 |
| Mr = 364.5 | Cu Kα radiation, λ = 1.5418 Å |
| Tetragonal, I42m | Cell parameters from 3581 reflections |
| Hall symbol: I -4 2 | θ = 5.1–67.0° |
| a = 7.1996 (2) Å | µ = 0.63 mm−1 |
| c = 17.4511 (5) Å | T = 120 K |
| V = 904.56 (6) Å3 | Irregular shape, yellow |
| Z = 2 | 0.45 × 0.22 × 0.15 mm |
| F(000) = 384 |
| Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector | 273 independent reflections |
| Radiation source: Enhance Ultra (Cu) X-ray Source | 268 reflections with I > 3σ(I) |
| Mirror monochromator | Rint = 0.025 |
| Detector resolution: 10.3784 pixels mm-1 | θmax = 67.1°, θmin = 5.1° |
| Rotation method, ω scans | h = −8→8 |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −8→8 |
| Tmin = 0.50, Tmax = 0.90 | l = −20→20 |
| 4873 measured reflections |
| Refinement on F2 | 4 constraints |
| R[F2 > 2σ(F2)] = 0.027 | Only H-atom coordinates refined |
| wR(F2) = 0.077 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
| S = 1.85 | (Δ/σ)max = 0.003 |
| 273 reflections | Δρmax = 0.08 e Å−3 |
| 51 parameters | Δρmin = −0.15 e Å−3 |
| 0 restraints |
| C24H20N4 | Z = 2 |
| Mr = 364.5 | Cu Kα radiation |
| Tetragonal, I42m | µ = 0.63 mm−1 |
| a = 7.1996 (2) Å | T = 120 K |
| c = 17.4511 (5) Å | 0.45 × 0.22 × 0.15 mm |
| V = 904.56 (6) Å3 |
| Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector | 273 independent reflections |
| Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 268 reflections with I > 3σ(I) |
| Tmin = 0.50, Tmax = 0.90 | Rint = 0.025 |
| 4873 measured reflections | θmax = 67.1° |
| R[F2 > 2σ(F2)] = 0.027 | Only H-atom coordinates refined |
| wR(F2) = 0.077 | Δρmax = 0.08 e Å−3 |
| S = 1.85 | Δρmin = −0.15 e Å−3 |
| 273 reflections | Absolute structure: ? |
| 51 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement. The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program. |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.86029 (13) | 0.13971 (13) | 0.04360 (8) | 0.0180 (4) | |
| C1 | 0.7560 (2) | 0 | 0 | 0.0187 (4) | |
| C2 | 0.92982 (16) | 0.07018 (16) | 0.11529 (9) | 0.0175 (4) | |
| C3 | 0.86239 (18) | 0.13761 (18) | 0.18326 (11) | 0.0194 (4) | |
| C4 | 0.9299 (2) | 0.0701 (2) | 0.25428 (9) | 0.0181 (4) | |
| C5 | 0.86279 (18) | 0.13721 (18) | 0.32562 (11) | 0.0221 (4) | |
| C6 | 0.93073 (18) | 0.06927 (18) | 0.39302 (9) | 0.0222 (4) | |
| H1 | 0.677 (2) | 0.0686 (18) | −0.0400 (7) | 0.0225* | |
| H3 | 0.760 (2) | 0.240 (2) | 0.1798 (11) | 0.0233* | |
| H5 | 0.760 (2) | 0.240 (2) | 0.3243 (12) | 0.0265* | |
| H6 | 0.886 (2) | 0.114 (2) | 0.4421 (13) | 0.0266* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0174 (5) | 0.0174 (5) | 0.0191 (8) | 0.0016 (7) | 0.0002 (4) | −0.0002 (4) |
| C1 | 0.0152 (8) | 0.0201 (8) | 0.0210 (7) | 0 | 0 | 0.0003 (7) |
| C2 | 0.0158 (5) | 0.0158 (5) | 0.0208 (9) | 0.0001 (7) | −0.0016 (5) | 0.0016 (5) |
| C3 | 0.0174 (6) | 0.0174 (6) | 0.0235 (10) | 0.0026 (7) | 0.0007 (5) | −0.0007 (5) |
| C4 | 0.0168 (6) | 0.0168 (6) | 0.0208 (8) | −0.0015 (7) | −0.0008 (5) | 0.0008 (5) |
| C5 | 0.0211 (6) | 0.0211 (6) | 0.0240 (10) | 0.0031 (8) | 0.0002 (4) | −0.0002 (4) |
| C6 | 0.0234 (6) | 0.0234 (6) | 0.0196 (7) | 0.0012 (8) | 0.0007 (5) | −0.0007 (5) |
| N1—C1 | 1.4680 (13) | C3—H3 | 1.042 (18) |
| N1—C1i | 1.4680 (13) | C4—C4iii | 1.428 (2) |
| N1—C2 | 1.437 (2) | C4—C5 | 1.420 (2) |
| C1—H1 | 1.027 (13) | C5—C6 | 1.365 (2) |
| C1—H1ii | 1.027 (13) | C5—H5 | 1.047 (18) |
| C2—C2iii | 1.4292 (17) | C6—C6iii | 1.4106 (18) |
| C2—C3 | 1.370 (2) | C6—H6 | 0.97 (2) |
| C3—C4 | 1.417 (2) | ||
| C1—N1—C1i | 115.64 (9) | C2—C3—C4 | 120.94 (12) |
| C1—N1—C2 | 113.00 (8) | C2—C3—H3 | 116.7 (11) |
| C1i—N1—C2 | 113.00 (8) | C4—C3—H3 | 122.3 (11) |
| N1—C1—N1iv | 118.44 (11) | C3—C4—C4iii | 118.99 (14) |
| N1—C1—H1 | 107.8 (7) | C3—C4—C5 | 122.26 (13) |
| N1—C1—H1ii | 105.1 (7) | C4iii—C4—C5 | 118.74 (14) |
| N1iv—C1—H1 | 105.1 (7) | C4—C5—C6 | 120.80 (13) |
| N1iv—C1—H1ii | 107.8 (7) | C4—C5—H5 | 117.5 (11) |
| H1—C1—H1ii | 112.7 (11) | C6—C5—H5 | 121.7 (11) |
| N1—C2—C2iii | 119.50 (13) | C5—C6—C6iii | 120.46 (14) |
| N1—C2—C3 | 120.43 (11) | C5—C6—H6 | 121.7 (10) |
| C2iii—C2—C3 | 120.06 (14) | C6iii—C6—H6 | 117.8 (10) |
| Symmetry codes: (i) y+1, −x+1, −z; (ii) x, −y, −z; (iii) −x+2, −y, z; (iv) −y+1, x−1, −z. |
| Cg1 and Cg2 are the centroids of the C2–C4/C2'–C4' and C4–C6/C4'–C6' rings, respectively. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···Cg2v | 1.042 (18) | 2.648 (14) | 3.6921 (14) | 178.2 (15) |
| C5—H5···Cg1v | 1.047 (18) | 2.652 (14) | 3.6979 (14) | 178.0 (16) |
| Symmetry code: (v) −y+1/2, x−1/2, −z+1/2. |
| Cg1 and Cg2 are the centroids of the C2–C4/C2'–C4' and C4–C6/C4'–C6' rings, respectively. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···Cg2i | 1.042 (18) | 2.648 (14) | 3.6921 (14) | 178.2 (15) |
| C5—H5···Cg1i | 1.047 (18) | 2.652 (14) | 3.6979 (14) | 178.0 (16) |
| Symmetry code: (i) −y+1/2, x−1/2, −z+1/2. |
We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work, as well as the Institutional research plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae project of the Academy of Sciences of the Czech Republic.
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Brandenburg, K. & Putz, H. (2005). DIAMOND Crystal Impact, Bonn, Germany.
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.
Murray-Rust, P. & Smith, I. (1975). Acta Cryst. B31, 587–589.
Petříček, V., Dušek, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Prague, Czech Republic.
Rivera, A., Maldonado, M., Ríos-Motta, J., Fejfarová, K. & Dušek, M. (2011). Acta Cryst. E67, o2395.
Rivera, A., Maldonado, M., Ríos-Motta, J., González-Salas, D. & Dacunha-Marinho, B. (2009). Acta Cryst. E65, o2553.
Volpp, G. (1962). Chem. Ber. 95, 1493–1494.
We have as a general goal the design and synthesis of new macrocyclic saturated ring-fused aminals, of considerable interest as useful intermediates for the synthesis of N-containing heterocyclic compounds. These aminals comprise a family of preformed electrophilic reagents which have been utilized in condensation reactions with electron-rich aromatic compounds in a variant of the Mannich reaction. These ring-fused aminals are frequently prepared by reaction of 1,2-diamines with formaldehyde (Volpp, 1962). By an analogous route we prepared for the first time 6H,13H-5,12:7,14-dimethanodinaphtho[2,3-d:2,3-i][1,3,6,8]tetraazecine (I).
The molecular structure and atom-numbering scheme for (I) are shown in Fig. 1. Unlike the related structures, which crystallized in orthorhombic space groups Aba2 (Rivera et al., 2009, 2011) and Pbcn (Murray-Rust & Smith, 1975), the title compound (I) crystallizes in the tetragonal I42m space group with one quarter-molecule in the asymmetric unit (located on a special position of site symmetry 4). The X-ray structure of I shows similar features to other ring-fused aminals. So, the bond lengths and angles are normal (Allen et al., 1987) and similar to those observed for related structures (Murray-Rust & Smith, 1975; Rivera et al., 2009; Rivera et al., 2011).
Due to symmetry considerations the aromatic rings are strictly perpendicular to each other. In the crystal packing (Fig. 2), the molecules are linked by a pair of C—H···π interactions (Table 1) into columns along [110].