Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049173/hg2304sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049173/hg2304Isup2.hkl |
CCDC reference: 667352
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.006 Å
- R factor = 0.058
- wR factor = 0.065
- Data-to-parameter ratio = 8.4
checkCIF/PLATON results
No syntax errors found
Alert level C REFNR01_ALERT_3_C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5946 Proportion of unique data used 0.5863 Ratio reflections to parameters 8.3740 PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 8.37 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 27
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound (I) was isolated as a minor impurity in the synthesis of Tröger's base, using p-toluidine and paraformaldehyde in trifluoroacetic acid (TFA). p-Toluidine (30 g, 280 mmol) and p-formaldehyde (13.5 g,489 mmol) were dissolved in trifluoroacetic acid (300 ml) and stirred in the dark under an atmosphere of argon for 3 days before pouring the red reaction mixture over ice (200 g) and basifying the mixture with 26% ammonia solution (300 ml). The resultant yellow mixture was extracted with dichloromethane (3 x 80 ml) and the organic layers were combined before washing with saturated sodium carbonate solution (2 x 100 ml), brine (100 ml) and then drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the crude material was purified by column chromatography (silica gel, dichloromethane) to afford (I) as a white solid (1.55 g, 5%). Crystals of (I) were produced by slow evaporation of a 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.
Compound (I) was first reported as one of several products formed in the reaction of p-toluidine with aqueous formaldehyde solution in hydrochloric acid, in approximately 3% yield (Farrar, 1964). An analogous compound, with methoxy groups in place of the methyl groups, was proposed when p-anisidine was used instead of p-toluidine. Compound (I) was also obtained 26% yield from a 1:1 reaction of hexamethylene tetraamine and p-toluidine in trifluoroacetic acid (Johnson et al., 1993). These compounds are related to 3-phenyl-3,4-dihydroquinazolines that have been isolated as impurities in the synthesis of numerous Tröger's base analogues (von Walther & Bamberg, 1906; Eisner & Wagner, 1934; Maffei, 1928; Maffei, 1929; Wagner & Eisner, 1937; Smith, 1948; Becker et al., 1993; Bhuiyan et al., 2007).
The x-ray crystal structure reported here (Fig. 1) confirms the earlier stuctural assignments that have been proposed for compound (I). The tetrasubstituted aromatic ring forms the base of a cavity, with the 'walls' provided by the two p-di-substituted benzene rings.
For related literature, see: Becker et al. (1993); Bhuiyan et al. (2007); Eisner & Wagner (1934); Farrar (1964); Johnson et al. (1993); Maffei (1928, 1929); Smith & Schubert (1948); Walther & Bamberg (1906).
For related literature, see: Ibers & Hamilton (1974); Wagner & Eisner (1937).
Data collection: CAD-4 (Schagen et al., 1989); cell refinement: CAD-4 (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.
Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound, with ellipsoids at the 10% probability level. H atoms are drawn as spheres of arbitrary radius. | |
Fig. 2. The preparation of (I). |
C25H27N3 | Dx = 1.19 Mg m−3 |
Mr = 369.5 | Melting point: 421 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.035 (3) Å | Cell parameters from 11 reflections |
b = 20.805 (7) Å | θ = 10–11° |
c = 11.790 (3) Å | µ = 0.07 mm−1 |
β = 110.95 (1)° | T = 294 K |
V = 2070 (1) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.08 × 0.05 mm |
F(000) = 792.0 |
Enraf–Nonius CAD-4 diffractometer | θmax = 25° |
ω–2θ scans | h = −10→10 |
3813 measured reflections | k = 0→24 |
3628 independent reflections | l = 0→14 |
2127 reflections with I > 2σ(I) | 1 standard reflections every 30 min |
Rint = 0.023 | intensity decay: none |
Refinement on F | 0 restraints |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters not refined |
wR(F2) = 0.065 | w = 1/[σ2(F) + 0.0004F2] |
S = 1.85 | (Δ/σ)max = 0.002 |
2127 reflections | Δρmax = 0.33 e Å−3 |
254 parameters | Δρmin = −0.34 e Å−3 |
C25H27N3 | V = 2070 (1) Å3 |
Mr = 369.5 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.035 (3) Å | µ = 0.07 mm−1 |
b = 20.805 (7) Å | T = 294 K |
c = 11.790 (3) Å | 0.30 × 0.08 × 0.05 mm |
β = 110.95 (1)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.023 |
3813 measured reflections | 1 standard reflections every 30 min |
3628 independent reflections | intensity decay: none |
2127 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters not refined |
S = 1.85 | Δρmax = 0.33 e Å−3 |
2127 reflections | Δρmin = −0.34 e Å−3 |
254 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1834 (3) | 0.2545 (1) | 0.5530 (2) | 0.0630 (8) | |
N2 | −0.0410 (3) | 0.2116 (2) | 0.3932 (2) | 0.0674 (8) | |
N3 | 0.4565 (3) | 0.2671 (1) | 0.6746 (2) | 0.0629 (8) | |
C1 | 0.0391 (4) | 0.2186 (2) | 0.5239 (3) | 0.072 (1) | |
C2 | −0.0829 (4) | 0.2753 (2) | 0.3394 (3) | 0.075 (1) | |
C3 | 0.0602 (4) | 0.3184 (2) | 0.3720 (3) | 0.0606 (9) | |
C4 | 0.0696 (5) | 0.3696 (2) | 0.2992 (3) | 0.072 (1) | |
C5 | 0.2015 (6) | 0.4082 (2) | 0.3281 (3) | 0.078 (1) | |
C6 | 0.3297 (5) | 0.3954 (2) | 0.4353 (4) | 0.075 (1) | |
C7 | 0.3221 (4) | 0.3454 (2) | 0.5114 (3) | 0.0623 (9) | |
C8 | 0.4565 (4) | 0.3331 (2) | 0.6317 (3) | 0.072 (1) | |
C9 | 0.2996 (4) | 0.2530 (2) | 0.6763 (3) | 0.070 (1) | |
C10 | 0.1887 (4) | 0.3065 (2) | 0.4799 (3) | 0.0572 (8) | |
C11 | 0.2124 (6) | 0.4629 (2) | 0.2461 (4) | 0.118 (2) | |
C12 | 0.0224 (4) | 0.1667 (2) | 0.3334 (3) | 0.0596 (9) | |
C13 | −0.0610 (4) | 0.1534 (2) | 0.2092 (3) | 0.074 (1) | |
C14 | −0.0068 (5) | 0.1074 (2) | 0.1496 (3) | 0.076 (1) | |
C15 | 0.1288 (5) | 0.0722 (2) | 0.2063 (3) | 0.070 (1) | |
C16 | 0.2110 (4) | 0.0861 (2) | 0.3282 (3) | 0.071 (1) | |
C17 | 0.1597 (4) | 0.1323 (2) | 0.3897 (3) | 0.0645 (9) | |
C18 | 0.1839 (5) | 0.0208 (2) | 0.1407 (3) | 0.092 (1) | |
C19 | 0.5173 (3) | 0.2185 (2) | 0.6180 (3) | 0.0554 (8) | |
C20 | 0.5351 (4) | 0.1567 (2) | 0.6634 (3) | 0.0643 (9) | |
C21 | 0.5978 (4) | 0.1086 (2) | 0.6143 (3) | 0.071 (1) | |
C22 | 0.6484 (4) | 0.1206 (2) | 0.5163 (3) | 0.0671 (9) | |
C23 | 0.6312 (4) | 0.1823 (2) | 0.4732 (3) | 0.0620 (9) | |
C24 | 0.5658 (4) | 0.2311 (2) | 0.5200 (3) | 0.0573 (9) | |
C25 | 0.7166 (5) | 0.0679 (2) | 0.4629 (4) | 0.099 (1) | |
H1C1 | −0.0330 | 0.2414 | 0.5580 | 0.072 | |
H2C1 | 0.0644 | 0.1749 | 0.5613 | 0.072 | |
H1C2 | −0.1625 | 0.2951 | 0.3698 | 0.075 | |
H2C2 | −0.1300 | 0.2709 | 0.2490 | 0.075 | |
HC4 | −0.0227 | 0.3787 | 0.2233 | 0.072 | |
HC6 | 0.4274 | 0.4225 | 0.4573 | 0.075 | |
H1C8 | 0.4449 | 0.3632 | 0.6941 | 0.072 | |
H2C8 | 0.5596 | 0.3414 | 0.6208 | 0.072 | |
H1C9 | 0.2709 | 0.2859 | 0.7268 | 0.070 | |
H2C9 | 0.2999 | 0.2094 | 0.7119 | 0.070 | |
H1C11 | 0.2273 | 0.5044 | 0.2916 | 0.118 | |
H2C11 | 0.3044 | 0.4555 | 0.2196 | 0.118 | |
H3C11 | 0.1125 | 0.4648 | 0.1732 | 0.118 | |
HC13 | −0.1603 | 0.1777 | 0.1642 | 0.074 | |
HC14 | −0.0683 | 0.0992 | 0.0618 | 0.076 | |
HC16 | 0.3104 | 0.0618 | 0.3727 | 0.071 | |
HC17 | 0.2234 | 0.1410 | 0.4771 | 0.064 | |
H1C18 | 0.1362 | −0.0214 | 0.1499 | 0.092 | |
H2C18 | 0.1500 | 0.0319 | 0.0526 | 0.092 | |
H3C18 | 0.3021 | 0.0176 | 0.1760 | 0.092 | |
HC20 | 0.5017 | 0.1466 | 0.7337 | 0.064 | |
HC21 | 0.6077 | 0.0642 | 0.6488 | 0.071 | |
HC23 | 0.6676 | 0.1927 | 0.4046 | 0.062 | |
HC24 | 0.5533 | 0.2752 | 0.4839 | 0.057 | |
H1C25 | 0.7710 | 0.0358 | 0.5275 | 0.099 | |
H2C25 | 0.6295 | 0.0463 | 0.3960 | 0.099 | |
H3C25 | 0.7948 | 0.0866 | 0.4298 | 0.099 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.060 (2) | 0.093 (2) | 0.037 (2) | −0.004 (2) | 0.018 (1) | 0.007 (1) |
N2 | 0.060 (2) | 0.103 (2) | 0.044 (2) | −0.001 (2) | 0.023 (1) | 0.005 (2) |
N3 | 0.065 (2) | 0.080 (2) | 0.044 (2) | 0.002 (2) | 0.019 (1) | −0.010 (1) |
C1 | 0.066 (2) | 0.114 (3) | 0.045 (2) | −0.011 (2) | 0.032 (2) | −0.002 (2) |
C2 | 0.063 (2) | 0.111 (3) | 0.053 (2) | 0.014 (2) | 0.024 (2) | 0.002 (2) |
C3 | 0.062 (2) | 0.084 (3) | 0.042 (2) | 0.012 (2) | 0.027 (2) | −0.001 (2) |
C4 | 0.093 (3) | 0.088 (3) | 0.046 (2) | 0.025 (2) | 0.040 (2) | 0.009 (2) |
C5 | 0.110 (3) | 0.076 (3) | 0.069 (3) | 0.021 (3) | 0.059 (3) | 0.011 (2) |
C6 | 0.088 (3) | 0.074 (3) | 0.080 (3) | 0.005 (2) | 0.049 (2) | −0.001 (2) |
C7 | 0.070 (2) | 0.070 (2) | 0.055 (2) | 0.005 (2) | 0.031 (2) | −0.004 (2) |
C8 | 0.072 (3) | 0.076 (3) | 0.067 (2) | −0.001 (2) | 0.022 (2) | −0.018 (2) |
C9 | 0.067 (2) | 0.110 (3) | 0.036 (2) | 0.007 (2) | 0.022 (2) | −0.002 (2) |
C10 | 0.062 (2) | 0.075 (2) | 0.044 (2) | 0.008 (2) | 0.030 (2) | 0.002 (2) |
C11 | 0.177 (5) | 0.099 (3) | 0.102 (3) | 0.023 (3) | 0.081 (3) | 0.031 (3) |
C12 | 0.052 (2) | 0.086 (3) | 0.045 (2) | −0.010 (2) | 0.022 (2) | 0.006 (2) |
C13 | 0.062 (2) | 0.106 (3) | 0.046 (2) | −0.010 (2) | 0.009 (2) | 0.006 (2) |
C14 | 0.086 (3) | 0.097 (3) | 0.042 (2) | −0.015 (2) | 0.020 (2) | −0.003 (2) |
C15 | 0.085 (3) | 0.078 (3) | 0.050 (2) | −0.014 (2) | 0.028 (2) | 0.002 (2) |
C16 | 0.076 (3) | 0.080 (3) | 0.054 (2) | −0.009 (2) | 0.020 (2) | 0.001 (2) |
C17 | 0.066 (2) | 0.086 (3) | 0.039 (2) | −0.005 (2) | 0.015 (2) | 0.005 (2) |
C18 | 0.133 (4) | 0.082 (3) | 0.068 (2) | −0.008 (3) | 0.045 (3) | −0.004 (2) |
C19 | 0.049 (2) | 0.077 (2) | 0.037 (2) | 0.001 (2) | 0.011 (2) | −0.002 (2) |
C20 | 0.071 (2) | 0.079 (2) | 0.045 (2) | 0.002 (2) | 0.023 (2) | 0.006 (2) |
C21 | 0.083 (3) | 0.072 (3) | 0.058 (2) | 0.006 (2) | 0.024 (2) | 0.010 (2) |
C22 | 0.067 (2) | 0.077 (3) | 0.057 (2) | 0.003 (2) | 0.022 (2) | −0.007 (2) |
C23 | 0.060 (2) | 0.081 (3) | 0.047 (2) | −0.001 (2) | 0.022 (2) | −0.003 (2) |
C24 | 0.057 (2) | 0.072 (2) | 0.044 (2) | 0.002 (2) | 0.020 (2) | 0.005 (2) |
C25 | 0.119 (4) | 0.096 (3) | 0.094 (3) | 0.017 (3) | 0.051 (3) | −0.014 (2) |
N1—C1 | 1.434 (4) | C11—H3C11 | 1.000 |
N1—C9 | 1.458 (4) | C12—C13 | 1.414 (4) |
N1—C10 | 1.393 (4) | C12—C17 | 1.380 (4) |
N2—C1 | 1.457 (4) | C13—C14 | 1.377 (5) |
N2—C2 | 1.460 (4) | C13—HC13 | 1.000 |
N2—C12 | 1.409 (4) | C14—C15 | 1.378 (5) |
N3—C8 | 1.463 (4) | C14—HC14 | 1.000 |
N3—C9 | 1.455 (4) | C15—C16 | 1.392 (4) |
N3—C19 | 1.425 (4) | C15—C18 | 1.505 (5) |
C1—H1C1 | 1.000 | C16—C17 | 1.380 (4) |
C1—H2C1 | 1.000 | C16—HC16 | 1.000 |
C2—C3 | 1.506 (5) | C17—HC17 | 1.000 |
C2—H1C2 | 1.000 | C18—H1C18 | 1.000 |
C2—H2C2 | 1.000 | C18—H2C18 | 1.000 |
C3—C4 | 1.389 (4) | C18—H3C18 | 1.000 |
C3—C10 | 1.404 (4) | C19—C20 | 1.381 (4) |
C4—C5 | 1.375 (5) | C19—C24 | 1.399 (4) |
C4—HC4 | 1.000 | C20—C21 | 1.376 (4) |
C5—C6 | 1.401 (5) | C20—HC20 | 1.000 |
C5—C11 | 1.519 (5) | C21—C22 | 1.408 (4) |
C6—C7 | 1.392 (4) | C21—HC21 | 1.000 |
C6—HC6 | 1.000 | C22—C23 | 1.369 (4) |
C7—C8 | 1.523 (5) | C22—C25 | 1.502 (5) |
C7—C10 | 1.388 (4) | C23—C24 | 1.384 (4) |
C8—H1C8 | 1.000 | C23—HC23 | 1.000 |
C8—H2C8 | 1.000 | C24—HC24 | 1.000 |
C9—H1C9 | 1.000 | C25—H1C25 | 1.000 |
C9—H2C9 | 1.000 | C25—H2C25 | 1.000 |
C11—H1C11 | 1.000 | C25—H3C25 | 1.000 |
C11—H2C11 | 1.000 | ||
C1—N1—C9 | 119.7 (3) | C5—C11—H3C11 | 109.5 |
C1—N1—C10 | 119.1 (3) | H1C11—C11—H2C11 | 109.5 |
C9—N1—C10 | 117.5 (3) | H1C11—C11—H3C11 | 109.5 |
C1—N2—C2 | 108.8 (3) | H2C11—C11—H3C11 | 109.5 |
C1—N2—C12 | 117.3 (3) | N2—C12—C13 | 119.1 (3) |
C2—N2—C12 | 118.2 (2) | N2—C12—C17 | 124.1 (3) |
C8—N3—C9 | 108.3 (3) | C13—C12—C17 | 116.8 (3) |
C8—N3—C19 | 117.1 (3) | C12—C13—C14 | 120.6 (3) |
C9—N3—C19 | 113.8 (3) | C12—C13—HC13 | 119.7 |
N1—C1—N2 | 111.8 (2) | C14—C13—HC13 | 119.7 |
N1—C1—H1C1 | 108.9 | C13—C14—C15 | 122.6 (3) |
N1—C1—H2C1 | 108.9 | C13—C14—HC14 | 118.7 |
N2—C1—H1C1 | 108.9 | C15—C14—HC14 | 118.7 |
N2—C1—H2C1 | 108.9 | C14—C15—C16 | 116.4 (3) |
H1C1—C1—H2C1 | 109.5 | C14—C15—C18 | 121.9 (3) |
N2—C2—C3 | 111.4 (3) | C16—C15—C18 | 121.7 (4) |
N2—C2—H1C2 | 109.0 | C15—C16—C17 | 122.1 (3) |
N2—C2—H2C2 | 109.0 | C15—C16—HC16 | 118.9 |
C3—C2—H1C2 | 109.0 | C17—C16—HC16 | 118.9 |
C3—C2—H2C2 | 109.0 | C12—C17—C16 | 121.5 (3) |
H1C2—C2—H2C2 | 109.5 | C12—C17—HC17 | 119.3 |
C2—C3—C4 | 122.4 (3) | C16—C17—HC17 | 119.3 |
C2—C3—C10 | 118.8 (3) | C15—C18—H1C18 | 109.5 |
C4—C3—C10 | 118.8 (3) | C15—C18—H2C18 | 109.5 |
C3—C4—C5 | 122.3 (3) | C15—C18—H3C18 | 109.5 |
C3—C4—HC4 | 118.9 | H1C18—C18—H2C18 | 109.5 |
C5—C4—HC4 | 118.9 | H1C18—C18—H3C18 | 109.5 |
C4—C5—C6 | 118.5 (3) | H2C18—C18—H3C18 | 109.5 |
C4—C5—C11 | 121.8 (4) | N3—C19—C20 | 119.3 (3) |
C6—C5—C11 | 119.7 (4) | N3—C19—C24 | 122.8 (3) |
C5—C6—C7 | 120.5 (4) | C20—C19—C24 | 117.8 (3) |
C5—C6—HC6 | 119.7 | C19—C20—C21 | 121.5 (3) |
C7—C6—HC6 | 119.7 | C19—C20—HC20 | 119.2 |
C6—C7—C8 | 121.3 (3) | C21—C20—HC20 | 119.2 |
C6—C7—C10 | 120.1 (3) | C20—C21—C22 | 121.3 (3) |
C8—C7—C10 | 118.6 (3) | C20—C21—HC21 | 119.4 |
N3—C8—C7 | 112.4 (3) | C22—C21—HC21 | 119.4 |
N3—C8—H1C8 | 108.7 | C21—C22—C23 | 116.4 (3) |
N3—C8—H2C8 | 108.7 | C21—C22—C25 | 121.0 (3) |
C7—C8—H1C8 | 108.7 | C23—C22—C25 | 122.6 (3) |
C7—C8—H2C8 | 108.7 | C22—C23—C24 | 123.2 (3) |
H1C8—C8—H2C8 | 109.5 | C22—C23—HC23 | 118.4 |
N1—C9—N3 | 109.9 (3) | C24—C23—HC23 | 118.4 |
N1—C9—H1C9 | 109.4 | C19—C24—C23 | 119.8 (3) |
N1—C9—H2C9 | 109.4 | C19—C24—HC24 | 120.1 |
N3—C9—H1C9 | 109.4 | C23—C24—HC24 | 120.1 |
N3—C9—H2C9 | 109.4 | C22—C25—H1C25 | 109.5 |
H1C9—C9—H2C9 | 109.5 | C22—C25—H2C25 | 109.5 |
N1—C10—C3 | 119.8 (3) | C22—C25—H3C25 | 109.5 |
N1—C10—C7 | 120.4 (3) | H1C25—C25—H2C25 | 109.5 |
C3—C10—C7 | 119.8 (3) | H1C25—C25—H3C25 | 109.5 |
C5—C11—H1C11 | 109.5 | H2C25—C25—H3C25 | 109.5 |
C5—C11—H2C11 | 109.5 | ||
C9—N1—C1—N2 | −164.5 (3) | C6—C5—C11—H3C11 | 178.8 |
C9—N1—C1—H1C1 | 75.1 | C5—C6—C7—C8 | −176.6 (3) |
C9—N1—C1—H2C1 | −44.2 | C5—C6—C7—C10 | 1.9 (5) |
C10—N1—C1—N2 | 37.7 (4) | HC6—C6—C7—C8 | 3.4 |
C10—N1—C1—H1C1 | −82.7 | HC6—C6—C7—C10 | −178.1 |
C10—N1—C1—H2C1 | 158.0 | C6—C7—C8—N3 | −158.0 (3) |
C1—N1—C9—N3 | 155.0 (3) | C6—C7—C8—H1C8 | 81.5 |
C1—N1—C9—H1C9 | −84.9 | C6—C7—C8—H2C8 | −37.6 |
C1—N1—C9—H2C9 | 35.0 | C10—C7—C8—N3 | 23.5 (4) |
C10—N1—C9—N3 | −46.8 (4) | C10—C7—C8—H1C8 | −97.0 |
C10—N1—C9—H1C9 | 73.3 | C10—C7—C8—H2C8 | 143.9 |
C10—N1—C9—H2C9 | −166.9 | C6—C7—C10—N1 | 177.1 (3) |
C1—N1—C10—C3 | −7.2 (4) | C6—C7—C10—C3 | −1.2 (4) |
C1—N1—C10—C7 | 174.6 (3) | C8—C7—C10—N1 | −4.4 (4) |
C9—N1—C10—C3 | −165.5 (3) | C8—C7—C10—C3 | 177.4 (3) |
C9—N1—C10—C7 | 16.3 (4) | N2—C12—C13—C14 | −176.5 (3) |
C2—N2—C1—N1 | −61.7 (3) | N2—C12—C13—HC13 | 3.5 |
C2—N2—C1—H1C1 | 58.7 | C17—C12—C13—C14 | 0.9 (5) |
C2—N2—C1—H2C1 | 178.0 | C17—C12—C13—HC13 | −179.1 |
C12—N2—C1—N1 | 75.8 (4) | N2—C12—C17—C16 | 175.9 (3) |
C12—N2—C1—H1C1 | −163.9 | N2—C12—C17—HC17 | −4.1 |
C12—N2—C1—H2C1 | −44.6 | C13—C12—C17—C16 | −1.3 (5) |
C1—N2—C2—C3 | 55.2 (3) | C13—C12—C17—HC17 | 178.7 |
C1—N2—C2—H1C2 | −65.1 | C12—C13—C14—C15 | 0.2 (5) |
C1—N2—C2—H2C2 | 175.4 | C12—C13—C14—HC14 | −179.8 |
C12—N2—C2—C3 | −81.8 (3) | HC13—C13—C14—C15 | −179.8 |
C12—N2—C2—H1C2 | 157.9 | HC13—C13—C14—HC14 | 0.2 |
C12—N2—C2—H2C2 | 38.4 | C13—C14—C15—C16 | −0.8 (5) |
C1—N2—C12—C13 | 173.3 (3) | C13—C14—C15—C18 | 178.3 (3) |
C1—N2—C12—C17 | −3.9 (4) | HC14—C14—C15—C16 | 179.2 |
C2—N2—C12—C13 | −53.2 (4) | HC14—C14—C15—C18 | −1.7 |
C2—N2—C12—C17 | 129.6 (3) | C14—C15—C16—C17 | 0.3 (5) |
C9—N3—C8—C7 | −52.9 (3) | C14—C15—C16—HC16 | −179.7 |
C9—N3—C8—H1C8 | 67.6 | C18—C15—C16—C17 | −178.7 (3) |
C9—N3—C8—H2C8 | −173.3 | C18—C15—C16—HC16 | 1.3 |
C19—N3—C8—C7 | 77.5 (3) | C14—C15—C18—H1C18 | −90.0 |
C19—N3—C8—H1C8 | −162.1 | C14—C15—C18—H2C18 | 30.0 |
C19—N3—C8—H2C8 | −43.0 | C14—C15—C18—H3C18 | 150.0 |
C8—N3—C9—N1 | 64.6 (3) | C16—C15—C18—H1C18 | 89.0 |
C8—N3—C9—H1C9 | −55.5 | C16—C15—C18—H2C18 | −151.0 |
C8—N3—C9—H2C9 | −175.4 | C16—C15—C18—H3C18 | −31.0 |
C19—N3—C9—N1 | −67.5 (4) | C15—C16—C17—C12 | 0.8 (5) |
C19—N3—C9—H1C9 | 172.4 | C15—C16—C17—HC17 | −179.2 |
C19—N3—C9—H2C9 | 52.5 | HC16—C16—C17—C12 | −179.2 |
C8—N3—C19—C20 | 173.4 (3) | HC16—C16—C17—HC17 | 0.8 |
C8—N3—C19—C24 | −4.2 (4) | N3—C19—C20—C21 | −178.0 (3) |
C9—N3—C19—C20 | −58.9 (4) | N3—C19—C20—HC20 | 2.0 |
C9—N3—C19—C24 | 123.5 (3) | C24—C19—C20—C21 | −0.3 (5) |
N2—C2—C3—C4 | 153.9 (3) | C24—C19—C20—HC20 | 179.7 |
N2—C2—C3—C10 | −26.3 (4) | N3—C19—C24—C23 | 176.7 (3) |
H1C2—C2—C3—C4 | −85.8 | N3—C19—C24—HC24 | −3.3 |
H1C2—C2—C3—C10 | 94.0 | C20—C19—C24—C23 | −0.9 (4) |
H2C2—C2—C3—C4 | 33.6 | C20—C19—C24—HC24 | 179.1 |
H2C2—C2—C3—C10 | −146.5 | C19—C20—C21—C22 | 0.8 (5) |
C2—C3—C4—C5 | −178.9 (3) | C19—C20—C21—HC21 | −179.2 |
C2—C3—C4—HC4 | 1.1 | HC20—C20—C21—C22 | −179.2 |
C10—C3—C4—C5 | 1.3 (5) | HC20—C20—C21—HC21 | 0.8 |
C10—C3—C4—HC4 | −178.7 | C20—C21—C22—C23 | −0.2 (5) |
C2—C3—C10—N1 | 1.5 (4) | C20—C21—C22—C25 | −179.9 (3) |
C2—C3—C10—C7 | 179.8 (3) | HC21—C21—C22—C23 | 179.8 |
C4—C3—C10—N1 | −178.6 (3) | HC21—C21—C22—C25 | 0.1 |
C4—C3—C10—C7 | −0.4 (4) | C21—C22—C23—C24 | −1.0 (5) |
C3—C4—C5—C6 | −0.6 (5) | C21—C22—C23—HC23 | 179.0 |
C3—C4—C5—C11 | 178.2 (3) | C25—C22—C23—C24 | 178.7 (3) |
HC4—C4—C5—C6 | 179.4 | C25—C22—C23—HC23 | −1.3 |
HC4—C4—C5—C11 | −1.8 | C21—C22—C25—H1C25 | −30.0 |
C4—C5—C6—C7 | −1.0 (5) | C21—C22—C25—H2C25 | 90.0 |
C4—C5—C6—HC6 | 179.0 | C21—C22—C25—H3C25 | −150.0 |
C11—C5—C6—C7 | −179.9 (3) | C23—C22—C25—H1C25 | 150.3 |
C11—C5—C6—HC6 | 0.1 | C23—C22—C25—H2C25 | −89.7 |
C4—C5—C11—H1C11 | 120.0 | C23—C22—C25—H3C25 | 30.3 |
C4—C5—C11—H2C11 | −120.0 | C22—C23—C24—C19 | 1.6 (5) |
C4—C5—C11—H3C11 | 0.0 | C22—C23—C24—HC24 | −178.4 |
C6—C5—C11—H1C11 | −61.2 | HC23—C23—C24—C19 | −178.4 |
C6—C5—C11—H2C11 | 58.8 | HC23—C23—C24—HC24 | 1.6 |
Experimental details
Crystal data | |
Chemical formula | C25H27N3 |
Mr | 369.5 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 9.035 (3), 20.805 (7), 11.790 (3) |
β (°) | 110.95 (1) |
V (Å3) | 2070 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.30 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3813, 3628, 2127 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.065, 1.85 |
No. of reflections | 2127 |
No. of parameters | 254 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.33, −0.34 |
Computer programs: CAD-4 (Schagen et al., 1989), SIR92 (Altomare et al., 1994), RAELS (Rae, 1996), ORTEPII (Johnson, 1976), local programs.
Compound (I) was first reported as one of several products formed in the reaction of p-toluidine with aqueous formaldehyde solution in hydrochloric acid, in approximately 3% yield (Farrar, 1964). An analogous compound, with methoxy groups in place of the methyl groups, was proposed when p-anisidine was used instead of p-toluidine. Compound (I) was also obtained 26% yield from a 1:1 reaction of hexamethylene tetraamine and p-toluidine in trifluoroacetic acid (Johnson et al., 1993). These compounds are related to 3-phenyl-3,4-dihydroquinazolines that have been isolated as impurities in the synthesis of numerous Tröger's base analogues (von Walther & Bamberg, 1906; Eisner & Wagner, 1934; Maffei, 1928; Maffei, 1929; Wagner & Eisner, 1937; Smith, 1948; Becker et al., 1993; Bhuiyan et al., 2007).
The x-ray crystal structure reported here (Fig. 1) confirms the earlier stuctural assignments that have been proposed for compound (I). The tetrasubstituted aromatic ring forms the base of a cavity, with the 'walls' provided by the two p-di-substituted benzene rings.