6H,13H-5,12:7,14-Di­methano­di­naphtho­[2,3-d:2,3-i][1,3,6,8]tetra­azecine

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⋯π inter­actions into columns along [110].

Related literature

For chemical background to the synthesis of the title compound, see: Volpp (1962). For related structures, see: Murray-Rust & Smith (1975); Rivera et al. (2009, 2011). For bond-length data, see: Allen et al. (1987).

Experimental

Crystal data

• C₂₄H₂₀N₄

• M_r = 364.5

• Tetragonal,

• a = 7.1996 (2) Å

• c = 17.4511 (5) Å

• V = 904.56 (6) ų

• Z = 2

• Cu Kα radiation

• μ = 0.63 mm⁻¹

• T = 120 K

• 0.45 × 0.22 × 0.15 mm

Data collection

• Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) T_min = 0.50, T_max = 0.90

• 4873 measured reflections

• 273 independent reflections

• 268 reflections with I > 3σ(I)

• R_int = 0.025

Refinement

• R[F² > 2σ(F²)] = 0.027

• wR(F²) = 0.077

• S = 1.85

• 273 reflections

• 51 parameters

• Only H-atom coordinates refined

• Δρ_max = 0.08 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯Cg2^i	1.042 (18)	2.648 (14)	3.6921 (14)	178.2 (15)
C5—H5⋯Cg1^i	1.047 (18)	2.652 (14)	3.6979 (14)	178.0 (16)
Symmetry code: (i) .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Supporting information

S1. Comment

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].

Related literature

For chemical background to the synthesis of the title compound, see: Volpp (1962). For related structures, see: Murray-Rust & Smith (1975); Rivera et al. (2009, 2011). For bond-length data, see: Allen et al. (1987).

S2. Experimental

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.

S3. Refinement

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×U_eq 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.

Computing details

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).

Figures

	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.
	Fig. 2. Packing of the molecules of the title compound view along b axis.

1,12,14,25- tetraazaheptacyclo[12.12.1.1^12,25.0^2,11.0^4,9.0^15,24.0^17,22]octacosa- 2,4(9),5,7,10,15,17 (22),18,20,23-decaene

Crystal data

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) Å^3	Irregular shape, yellow
Z = 2	0.45 × 0.22 × 0.15 mm
F(000) = 384

Data collection

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

Refinement on F^2	4 constraints
R[F > 3σ(F)] = 0.027	Only H-atom coordinates refined
wR(F) = 0.077	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0016I^2)
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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

N1—C1	1.4680 (13)	C3—H3	1.042 (18)
N1—C1^i	1.4680 (13)	C4—C4^iii	1.428 (2)
N1—C2	1.437 (2)	C4—C5	1.420 (2)
C1—H1	1.027 (13)	C5—C6	1.365 (2)
C1—H1^ii	1.027 (13)	C5—H5	1.047 (18)
C2—C2^iii	1.4292 (17)	C6—C6^iii	1.4106 (18)
C2—C3	1.370 (2)	C6—H6	0.97 (2)
C3—C4	1.417 (2)
C1—N1—C1^i	115.64 (9)	C2—C3—C4	120.94 (12)
C1—N1—C2	113.00 (8)	C2—C3—H3	116.7 (11)
C1^i—N1—C2	113.00 (8)	C4—C3—H3	122.3 (11)
N1—C1—N1^iv	118.44 (11)	C3—C4—C4^iii	118.99 (14)
N1—C1—H1	107.8 (7)	C3—C4—C5	122.26 (13)
N1—C1—H1^ii	105.1 (7)	C4^iii—C4—C5	118.74 (14)
N1^iv—C1—H1	105.1 (7)	C4—C5—C6	120.80 (13)
N1^iv—C1—H1^ii	107.8 (7)	C4—C5—H5	117.5 (11)
H1—C1—H1^ii	112.7 (11)	C6—C5—H5	121.7 (11)
N1—C2—C2^iii	119.50 (13)	C5—C6—C6^iii	120.46 (14)
N1—C2—C3	120.43 (11)	C5—C6—H6	121.7 (10)
C2^iii—C2—C3	120.06 (14)	C6^iii—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.

Hydrogen-bond geometry (Å, º)

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···Cg2^v	1.042 (18)	2.648 (14)	3.6921 (14)	178.2 (15)
C5—H5···Cg1^v	1.047 (18)	2.652 (14)	3.6979 (14)	178.0 (16)

Symmetry code: (v) −y+1/2, x−1/2, −z+1/2.