N,N′,N′′,N′′′-Tetrakis(1-naphthyl­methyl)-1,4,8,11-tetra­aza­cyclo­tetra­decane

Molecules of the title compound, C₅₄H₅₆N₄, are centrosymmetric and adopt a conformation with two naphthyl­methyl groups above the cyclam ring and the remaining two below. Packing with intermolecular π–π interaction between naphthalene planes is observed.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.052
• wR factor = 0.163
• Data-to-parameter ratio = 19.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSMU_01  Alert C The ratio of given/expected absorption coefficient lies
          outside the range 0.99 <> 1.01
          Calculated value of mu =     0.068
          Value of mu given      =     0.070


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The development of photoinduced electron transfer (PET) systems for guest cations has gained much attention for their potential application to nanoscale devices for cation sensors and switches (Lehn, 1995). Recently we have reported the complexation and fluorescence behaviour of several PET fluoroionophores (Kubo & Sakurai, 2000). As an approach to the manipulation of PET sensors, we have investigated the complexation behaviour of the title compound (1) in the presence of metal salts using fluorescence spectroscopy. The compound (1) (when excited at 282 nm) gave a broad emission band at 460 nm in addition to an emission band at 337 nm. The intramolecular exciplex and excimer formation should be responsible for the appearance of the former band. The fluorescence intensitiy at 337 nm of (1) was reduced to approximately 1/80 of that of 1-methylnaphthalene. Complexation of (1) with Zn²⁺ increased the fluorescence intensity of the host by a factor of 8.1 (Kubo et al., 1998). However, the structures of (1) and its complexes have not been elucidated. We now report the structure of (1) with the aim of contributing to a deeper understanding of PET systems.

Cyclic tetraamines such as cyclam and their derivatives can occur in several conformations. For instance, in [14]aneN4 or R4[14]aneN4 macrocycles with alternating five- and six-membered chelating rings a total of five combinations, such as four trans (I–IV) and one cis (V) configurations, can be produced (Lydon, 1989). The crystal structure of (1) shows the conformation with two adjacent naphthylmethyl groups above the cyclam ring and the remaining two below the cyclam ring; the trans-IV configuration (Bosnich et al., 1965) on a crystallographic centre of symmetry, is similar to that found in N,N',N'',N'''-tetramethyl-1,4,8,11-cyclam (Willey et al., 1993) and N,N',N'',N'''-[4'-p-tolyl-(2,2':6',2''-terpyridyl)]-1,4,8,11-cyclam (Padilla-Tosta et al., 2000). The angle of the intersection between the least-squares planes A (defined by C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10) and B (defined by C21, C22, C23, C24, C25, N1, and N2), is 99.6 (1)°, while that between the least-squares planes B and C (defined by C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20) is 69.6 (1)°.

The intermolecular distance between naphthalene rings is 3.428 (6) Å for C16—C17ⁱ (i: symmetry code 3/2 - x, 1/2 - y, 1 - z) which is within the range associated with π—π interaction [3.3–3.8 Å] (Prout et al., 1973a,b,c; Nakasuji et al., 1986, 1987; Lide, 1990; Hunter & Sanders, 1990; Munakata et al., 1994).

The N1···N1ⁱⁱ and N2···N2ⁱⁱ (ii: 1 - x, -y, -z) transannular distances are 4.90 Å and 5.63 Å, respectively. From the sum [1.5 + 1.5=3.0 Å] of van der Waals radii (Lide, 1990) of two N atoms, the cavity size of (1) is estimated as a smaller value than 1.9 Å, while the Zn²⁺ diameter for six coordination is 1.76 Å (Shannon, 1976). The cavity of (1) fits with Zn²⁺ cation. As a result, the PET fluoroionophore (1) exhibits high Zn²⁺ selectivity.

S2. Experimental

The compound (1) was synthesized by the N-alkylation of 1,4,8,11-tetraazacyclotetradecane with 1-chloromethylnaphthalene in tetrahydrofuran-triethylamine (Kubo et al., 1998). The single crystals of (1) were obtained by recrystallization from chloroform.

S3. Refinement

All H atoms were located at ideal positions and were included in refinement, but restrained to ride on the atom to which they are bonded. U_iso of H atoms were held fixed to 1.2 times U_eq of the parent atoms.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Molecular structure of (1) showing 50% probability displacement ellipsoids. H atoms are omitted.
	Fig. 2. Two molecules showing the close intermolecular contact between C16 and C17(3/2 - x, 1/2 - y, 1 - z).

(1)

Crystal data

C54H56N4	F(000) = 816
Mr = 761.02	Dx = 1.171 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 11.609 (5) Å	Cell parameters from 17 reflections
b = 18.907 (5) Å	θ = 9.5–18.1°
c = 9.878 (5) Å	µ = 0.07 mm^−1
β = 95.462 (5)°	T = 296 K
V = 2158.3 (15) Å^3	Prism, colourless
Z = 2	0.35 × 0.30 × 0.25 mm

Data collection

Enraf-Nonius CAD4 diffractometer	1450 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.060
Graphite monochromator	θmax = 28.0°, θmin = 2.8°
ω–2θ scans	h = −15→0
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968)	k = 0→24
Tmin = 0.952, Tmax = 1.000	l = −12→13
5426 measured reflections	3 standard reflections every 120 min
5183 independent reflections	intensity decay: 2.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.163	H-atom parameters constrained
S = 0.87	w = 1/[σ^2(Fo^2) + (0.057P)^2] where P = (Fo^2 + 2Fc^2)/3
5183 reflections	(Δ/σ)max = 0.004
262 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

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. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based 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. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.3121 (2)	0.05827 (13)	0.0076 (2)	0.0517 (7)
N2	0.6838 (2)	0.09182 (13)	0.0833 (2)	0.0545 (7)
C1	0.2253 (3)	0.13761 (17)	−0.1773 (3)	0.0600 (8)
C2	0.1578 (3)	0.1966 (2)	−0.1733 (3)	0.0815 (11)
H2	0.1032	0.1988	−0.1104	0.098*
C3	0.1684 (4)	0.2536 (2)	−0.2613 (4)	0.1012 (14)
H3	0.1210	0.2930	−0.2565	0.121*
C4	0.2474 (4)	0.2516 (2)	−0.3535 (4)	0.0997 (14)
H4	0.2543	0.2899	−0.4113	0.120*
C5	0.3194 (4)	0.19219 (19)	−0.3628 (4)	0.0723 (10)
C6	0.4000 (4)	0.1882 (2)	−0.4605 (4)	0.0939 (13)
H6	0.4075	0.2261	−0.5191	0.113*
C7	0.4668 (4)	0.1300 (3)	−0.4701 (4)	0.0909 (13)
H7	0.5200	0.1282	−0.5346	0.109*
C8	0.4557 (3)	0.0730 (2)	−0.3836 (3)	0.0773 (11)
H8	0.5017	0.0332	−0.3911	0.093*
C9	0.3787 (3)	0.07438 (17)	−0.2879 (3)	0.0616 (9)
H9	0.3727	0.0357	−0.2310	0.074*
C10	0.3082 (3)	0.13385 (18)	−0.2747 (3)	0.0568 (8)
C11	0.8528 (3)	0.15078 (17)	0.2157 (3)	0.0602 (9)
C12	0.9450 (3)	0.18090 (17)	0.1626 (4)	0.0756 (10)
H12	0.9335	0.2032	0.0784	0.091*
C13	1.0564 (4)	0.17953 (19)	0.2303 (5)	0.0886 (12)
H13	1.1182	0.1986	0.1892	0.106*
C14	1.0739 (3)	0.1507 (2)	0.3546 (5)	0.0851 (12)
H14	1.1476	0.1517	0.4005	0.102*
C15	0.9824 (3)	0.11903 (18)	0.4170 (4)	0.0658 (9)
C16	0.9982 (4)	0.0900 (2)	0.5493 (4)	0.0892 (12)
H16	1.0707	0.0922	0.5980	0.107*
C17	0.9099 (4)	0.0591 (2)	0.6061 (4)	0.0969 (13)
H17	0.9221	0.0402	0.6932	0.116*
C18	0.8014 (4)	0.0555 (2)	0.5355 (4)	0.0862 (12)
H18	0.7412	0.0335	0.5750	0.103*
C19	0.7816 (3)	0.08408 (17)	0.4081 (3)	0.0683 (10)
H19	0.7081	0.0809	0.3619	0.082*
C20	0.8702 (3)	0.11803 (16)	0.3461 (3)	0.0569 (8)
C21	0.3556 (3)	0.11911 (16)	0.0889 (3)	0.0597 (9)
H21A	0.3089	0.1252	0.1645	0.072*
H21B	0.3473	0.1614	0.0333	0.072*
C22	0.4820 (2)	0.11107 (16)	0.1442 (3)	0.0566 (8)
H22A	0.5053	0.1522	0.1989	0.068*
H22B	0.4899	0.0698	0.2028	0.068*
C23	0.5622 (3)	0.10323 (17)	0.0322 (3)	0.0623 (9)
H23A	0.5361	0.0636	−0.0252	0.075*
H23B	0.5568	0.1455	−0.0236	0.075*
C24	0.7531 (3)	0.06846 (16)	−0.0259 (3)	0.0667 (9)
H24A	0.8326	0.0624	0.0121	0.080*
H24B	0.7521	0.1056	−0.0937	0.080*
C25	0.7129 (3)	0.00008 (16)	−0.0965 (3)	0.0622 (9)
H25A	0.6436	0.0101	−0.1563	0.075*
H25B	0.7721	−0.0152	−0.1530	0.075*
C26	0.2080 (3)	0.07629 (17)	−0.0830 (3)	0.0626 (9)
H26A	0.1458	0.0879	−0.0278	0.075*
H26B	0.1842	0.0351	−0.1372	0.075*
C27	0.7342 (3)	0.15755 (16)	0.1425 (3)	0.0660 (9)
H27A	0.6827	0.1761	0.2056	0.079*
H27B	0.7373	0.1920	0.0701	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0585 (17)	0.0524 (16)	0.0432 (14)	0.0026 (14)	−0.0004 (13)	−0.0009 (13)
N2	0.0562 (17)	0.0531 (16)	0.0541 (16)	0.0029 (14)	0.0054 (14)	−0.0063 (13)
C1	0.065 (2)	0.061 (2)	0.0501 (19)	0.008 (2)	−0.0132 (18)	−0.0023 (18)
C2	0.098 (3)	0.082 (3)	0.059 (2)	0.034 (2)	−0.017 (2)	−0.012 (2)
C3	0.148 (4)	0.072 (3)	0.075 (3)	0.041 (3)	−0.031 (3)	−0.006 (3)
C4	0.158 (4)	0.063 (3)	0.071 (3)	0.007 (3)	−0.027 (3)	0.008 (2)
C5	0.097 (3)	0.062 (3)	0.054 (2)	−0.012 (2)	−0.018 (2)	0.003 (2)
C6	0.111 (4)	0.103 (4)	0.063 (3)	−0.036 (3)	−0.015 (3)	0.022 (3)
C7	0.091 (3)	0.129 (4)	0.052 (2)	−0.021 (3)	0.005 (2)	0.007 (3)
C8	0.082 (3)	0.102 (3)	0.0471 (19)	0.007 (2)	0.0038 (19)	−0.007 (2)
C9	0.072 (2)	0.065 (2)	0.0471 (19)	0.005 (2)	−0.0003 (18)	−0.0026 (17)
C10	0.064 (2)	0.057 (2)	0.0457 (18)	−0.0007 (19)	−0.0146 (17)	−0.0018 (17)
C11	0.056 (2)	0.050 (2)	0.075 (2)	−0.0021 (18)	0.008 (2)	−0.0099 (18)
C12	0.075 (3)	0.058 (2)	0.095 (3)	−0.006 (2)	0.012 (2)	−0.002 (2)
C13	0.074 (3)	0.070 (3)	0.125 (4)	−0.018 (2)	0.024 (3)	−0.009 (3)
C14	0.054 (2)	0.084 (3)	0.116 (3)	−0.009 (2)	0.001 (3)	−0.031 (3)
C15	0.054 (2)	0.069 (2)	0.073 (3)	−0.004 (2)	0.000 (2)	−0.017 (2)
C16	0.072 (3)	0.114 (3)	0.077 (3)	0.001 (3)	−0.015 (2)	−0.026 (2)
C17	0.099 (3)	0.123 (4)	0.067 (3)	0.004 (3)	−0.001 (3)	−0.003 (3)
C18	0.083 (3)	0.110 (3)	0.065 (2)	−0.010 (3)	0.008 (2)	0.003 (2)
C19	0.059 (2)	0.076 (2)	0.069 (2)	−0.006 (2)	0.0029 (19)	−0.0107 (19)
C20	0.052 (2)	0.053 (2)	0.066 (2)	−0.0030 (18)	0.0054 (19)	−0.0178 (18)
C21	0.062 (2)	0.063 (2)	0.0519 (19)	0.0124 (19)	−0.0042 (16)	−0.0087 (17)
C22	0.061 (2)	0.058 (2)	0.0486 (18)	0.0059 (17)	−0.0061 (16)	−0.0018 (16)
C23	0.061 (2)	0.075 (2)	0.0494 (19)	0.0057 (18)	−0.0009 (17)	0.0039 (16)
C24	0.076 (2)	0.062 (2)	0.064 (2)	0.0025 (19)	0.0152 (19)	0.0029 (18)
C25	0.070 (2)	0.066 (2)	0.0521 (19)	0.0065 (19)	0.0130 (17)	−0.0029 (18)
C26	0.055 (2)	0.073 (2)	0.059 (2)	0.0061 (18)	0.0002 (17)	−0.0067 (18)
C27	0.070 (2)	0.050 (2)	0.078 (2)	0.0037 (18)	0.006 (2)	0.0025 (18)

Geometric parameters (Å, º)

N1—C25^i	1.457 (3)	C9—C10	1.404 (4)
N1—C21	1.465 (3)	C11—C12	1.360 (4)
N1—C26	1.474 (3)	C11—C20	1.427 (4)
N2—C23	1.470 (3)	C11—C27	1.499 (4)
N2—C27	1.471 (3)	C12—C13	1.399 (5)
N2—C24	1.473 (3)	C13—C14	1.341 (5)
C1—C2	1.365 (4)	C14—C15	1.411 (4)
C1—C10	1.426 (4)	C15—C16	1.414 (5)
C1—C26	1.513 (4)	C15—C20	1.419 (4)
C2—C3	1.397 (5)	C16—C17	1.347 (5)
C3—C4	1.353 (5)	C17—C18	1.383 (5)
C4—C5	1.409 (5)	C18—C19	1.369 (4)
C5—C6	1.409 (5)	C19—C20	1.402 (4)
C5—C10	1.418 (4)	C21—C22	1.524 (4)
C6—C7	1.355 (5)	C22—C23	1.519 (4)
C7—C8	1.389 (5)	C24—C25	1.521 (4)
C8—C9	1.362 (4)	C25—N1^i	1.456 (3)
C25^i—N1—C21	110.0 (2)	C12—C11—C27	119.9 (3)
C25^i—N1—C26	110.0 (2)	C20—C11—C27	121.1 (3)
C21—N1—C26	111.8 (2)	C11—C12—C13	122.2 (4)
C23—N2—C27	110.2 (2)	C14—C13—C12	119.8 (4)
C23—N2—C24	111.5 (2)	C13—C14—C15	121.2 (4)
C27—N2—C24	108.7 (2)	C14—C15—C16	122.2 (4)
C2—C1—C10	119.1 (3)	C14—C15—C20	118.9 (4)
C2—C1—C26	119.8 (3)	C16—C15—C20	118.9 (3)
C10—C1—C26	121.0 (3)	C17—C16—C15	121.1 (4)
C1—C2—C3	121.8 (4)	C16—C17—C18	120.3 (4)
C4—C3—C2	120.2 (4)	C19—C18—C17	120.6 (4)
C3—C4—C5	120.6 (4)	C18—C19—C20	121.1 (3)
C4—C5—C6	121.6 (4)	C19—C20—C15	117.9 (3)
C4—C5—C10	119.4 (4)	C19—C20—C11	123.1 (3)
C6—C5—C10	119.0 (4)	C15—C20—C11	118.9 (3)
C7—C6—C5	120.8 (4)	N1—C21—C22	112.8 (2)
C6—C7—C8	120.0 (4)	C23—C22—C21	112.6 (2)
C9—C8—C7	121.2 (4)	N2—C23—C22	113.6 (2)
C8—C9—C10	120.4 (3)	N2—C24—C25	115.2 (2)
C9—C10—C5	118.5 (3)	N1^i—C25—C24	116.0 (2)
C9—C10—C1	122.6 (3)	N1—C26—C1	113.7 (3)
C5—C10—C1	118.8 (3)	N2—C27—C11	115.6 (3)
C12—C11—C20	118.8 (3)
C10—C1—C2—C3	−0.6 (5)	C16—C17—C18—C19	−1.0 (6)
C26—C1—C2—C3	−178.1 (3)	C17—C18—C19—C20	−0.4 (5)
C1—C2—C3—C4	−0.3 (6)	C18—C19—C20—C15	2.8 (5)
C2—C3—C4—C5	0.4 (6)	C18—C19—C20—C11	−177.7 (3)
C3—C4—C5—C6	178.2 (4)	C14—C15—C20—C19	177.8 (3)
C3—C4—C5—C10	0.2 (5)	C16—C15—C20—C19	−3.9 (5)
C4—C5—C6—C7	−178.5 (4)	C14—C15—C20—C11	−1.7 (4)
C10—C5—C6—C7	−0.5 (5)	C16—C15—C20—C11	176.6 (3)
C5—C6—C7—C8	0.4 (6)	C12—C11—C20—C19	−178.4 (3)
C6—C7—C8—C9	−0.2 (6)	C27—C11—C20—C19	6.6 (5)
C7—C8—C9—C10	0.1 (5)	C12—C11—C20—C15	1.1 (4)
C8—C9—C10—C5	−0.1 (4)	C27—C11—C20—C15	−173.9 (3)
C8—C9—C10—C1	179.2 (3)	C25^i—N1—C21—C22	77.8 (3)
C4—C5—C10—C9	178.4 (3)	C26—N1—C21—C22	−159.8 (2)
C6—C5—C10—C9	0.3 (4)	N1—C21—C22—C23	60.2 (3)
C4—C5—C10—C1	−1.0 (4)	C27—N2—C23—C22	−72.3 (3)
C6—C5—C10—C1	−179.1 (3)	C24—N2—C23—C22	167.0 (2)
C2—C1—C10—C9	−178.2 (3)	C21—C22—C23—N2	−177.1 (3)
C26—C1—C10—C9	−0.7 (4)	C23—N2—C24—C25	−59.2 (3)
C2—C1—C10—C5	1.2 (4)	C27—N2—C24—C25	179.2 (3)
C26—C1—C10—C5	178.7 (3)	N2—C24—C25—N1^i	−47.0 (4)
C20—C11—C12—C13	1.4 (5)	C25^i—N1—C26—C1	178.8 (2)
C27—C11—C12—C13	176.4 (3)	C21—N1—C26—C1	56.3 (3)
C11—C12—C13—C14	−3.2 (6)	C2—C1—C26—N1	−121.2 (3)
C12—C13—C14—C15	2.5 (6)	C10—C1—C26—N1	61.3 (4)
C13—C14—C15—C16	−178.3 (4)	C23—N2—C27—C11	171.8 (3)
C13—C14—C15—C20	−0.2 (5)	C24—N2—C27—C11	−65.7 (3)
C14—C15—C16—C17	−179.1 (4)	C12—C11—C27—N2	111.2 (3)
C20—C15—C16—C17	2.7 (5)	C20—C11—C27—N2	−73.9 (4)
C15—C16—C17—C18	−0.2 (6)

Symmetry code: (i) −x+1, −y, −z.