Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800017323/cf6002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800017323/cf60021sup2.hkl |
CCDC reference: 155852
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.
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. Uiso of H atoms were held fixed to 1.2 times Ueq of the parent atoms.
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).
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) Å3 | Prism, colourless |
Z = 2 | 0.35 × 0.30 × 0.25 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.057P)2] where P = (Fo2 + 2Fc2)/3 |
5183 reflections | (Δ/σ)max = 0.004 |
262 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C54H56N4 | V = 2158.3 (15) Å3 |
Mr = 761.02 | Z = 2 |
Monoclinic, P21/a | Mo Kα radiation |
a = 11.609 (5) Å | µ = 0.07 mm−1 |
b = 18.907 (5) Å | T = 296 K |
c = 9.878 (5) Å | 0.35 × 0.30 × 0.25 mm |
β = 95.462 (5)° |
Enraf-Nonius CAD4 diffractometer | 1450 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | Rint = 0.060 |
Tmin = 0.952, Tmax = 1.000 | 3 standard reflections every 120 min |
5426 measured reflections | intensity decay: 2.0% |
5183 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.13 e Å−3 |
5183 reflections | Δρmin = −0.14 e Å−3 |
262 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
N1—C25i | 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—N1i | 1.456 (3) |
C25i—N1—C21 | 110.0 (2) | C12—C11—C27 | 119.9 (3) |
C25i—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) | N1i—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) | C25i—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—N1i | −47.0 (4) |
C20—C11—C12—C13 | 1.4 (5) | C25i—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. |
Experimental details
Crystal data | |
Chemical formula | C54H56N4 |
Mr | 761.02 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 296 |
a, b, c (Å) | 11.609 (5), 18.907 (5), 9.878 (5) |
β (°) | 95.462 (5) |
V (Å3) | 2158.3 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scans (North et al., 1968) |
Tmin, Tmax | 0.952, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5426, 5183, 1450 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.163, 0.87 |
No. of reflections | 5183 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.14 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), MolEN (Fair, 1990), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), Xtal_GX (Hall & du Boulay, 1995).
N1—C25i | 1.457 (3) | N2—C24 | 1.473 (3) |
N1—C21 | 1.465 (3) | C21—C22 | 1.524 (4) |
N1—C26 | 1.474 (3) | C22—C23 | 1.519 (4) |
N2—C23 | 1.470 (3) | C24—C25 | 1.521 (4) |
N2—C27 | 1.471 (3) | ||
C25i—N1—C21—C22 | 77.8 (3) | C21—C22—C23—N2 | −177.1 (3) |
C26—N1—C21—C22 | −159.8 (2) | C23—N2—C24—C25 | −59.2 (3) |
N1—C21—C22—C23 | 60.2 (3) | C27—N2—C24—C25 | 179.2 (3) |
C24—N2—C23—C22 | 167.0 (2) | N2—C24—C25—N1i | −47.0 (4) |
Symmetry code: (i) −x+1, −y, −z. |
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.