Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003889/ob6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003889/ob6032Isup2.hkl |
CCDC reference: 162811
1,4-Bis(salicyloxy)butane (m.p. 374 K) was prepared from the reaction of salicylaldehyde (12.2 g, 100 mmol), sodium hydroxide (6.0 g, 150 mmol) and 1,4-dibromobutane (15.3 g, 71 mmol) in boiling ethanol (150 ml). Compound (I) was obtained from the reaction of 1,4-bis(salicyloxy)butane (0.50 g, 1.67 mmol) in ethanol (100 ml) and 1,3-diaminopropane (0.21 ml, 2.45 mmol) in ethanol (50 ml) with argon passing over the reaction mixture and it was refluxed for 5 h. The solvent was evaporated and the residue was crystallized from ethyl acetate [yield 0.31 g (62%), m.p. 440 K].
The H atoms were positioned geometrically with C—H distances of 0.96 and 0.93 Å for CH3 and CH, respectively, and a riding model was used during the refinement.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976).
Fig. 1. An ORTEPII (Johnson, 1976) drawing of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C21H24N2O2 | F(000) = 724 |
Mr = 336.43 | Dx = 1.255 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.231 (8) Å | Cell parameters from 25 reflections |
b = 15.6630 (14) Å | θ = 10–18° |
c = 8.206 (4) Å | µ = 0.08 mm−1 |
β = 103.044 (8)° | T = 293 K |
V = 1781.9 (13) Å3 | Block-like, colourless |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
Enraf-Nonius CAD-4 diffractometer | 1468 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 26.3°, θmin = 2.6° |
ω/2θ scans | h = −17→17 |
Absorption correction: ψ scans (MolEN; Fair, 1990) | k = −19→19 |
Tmin = 0.975, Tmax = 0.984 | l = −10→0 |
3554 measured reflections | 3 standard reflections every 120 min |
1816 independent reflections | intensity decay: 1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | Only H-atom displacement parameters refined |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0488P)2 + 0.3494P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1816 reflections | Δρmax = 0.14 e Å−3 |
127 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.063 (3) |
C21H24N2O2 | V = 1781.9 (13) Å3 |
Mr = 336.43 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.231 (8) Å | µ = 0.08 mm−1 |
b = 15.6630 (14) Å | T = 293 K |
c = 8.206 (4) Å | 0.30 × 0.25 × 0.20 mm |
β = 103.044 (8)° |
Enraf-Nonius CAD-4 diffractometer | 1468 reflections with I > 2σ(I) |
Absorption correction: ψ scans (MolEN; Fair, 1990) | Rint = 0.034 |
Tmin = 0.975, Tmax = 0.984 | 3 standard reflections every 120 min |
3554 measured reflections | intensity decay: 1% |
1816 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.106 | Only H-atom displacement parameters refined |
S = 1.06 | Δρmax = 0.14 e Å−3 |
1816 reflections | Δρmin = −0.15 e Å−3 |
127 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 | ||
O1 | 0.13740 (5) | 0.49049 (5) | 0.25488 (12) | 0.0515 (3) | |
N1 | 0.14349 (6) | 0.23658 (6) | 0.30725 (12) | 0.0448 (3) | |
C9 | 0.21554 (7) | 0.45222 (7) | 0.21602 (14) | 0.0417 (3) | |
C4 | 0.21878 (7) | 0.36282 (7) | 0.23047 (13) | 0.0392 (3) | |
C3 | 0.14552 (7) | 0.31686 (7) | 0.29760 (13) | 0.0396 (3) | |
H31 | 0.0989 | 0.3483 | 0.3344 | 0.054 (4)* | |
C7 | 0.36222 (9) | 0.45047 (8) | 0.11910 (17) | 0.0551 (3) | |
H71 | 0.4107 | 0.4797 | 0.0830 | 0.069 (4)* | |
C10 | 0.13676 (8) | 0.58169 (7) | 0.27145 (15) | 0.0448 (3) | |
H101 | 0.1388 | 0.6089 | 0.1661 | 0.053 (4)* | |
H102 | 0.1920 | 0.6006 | 0.3559 | 0.048 (3)* | |
C5 | 0.29414 (8) | 0.31938 (8) | 0.18443 (15) | 0.0458 (3) | |
H51 | 0.2966 | 0.2601 | 0.1916 | 0.054 (4)* | |
C2 | 0.06875 (8) | 0.19826 (7) | 0.37952 (14) | 0.0441 (3) | |
H21 | 0.0331 | 0.2429 | 0.4210 | 0.048 (3)* | |
H22 | 0.0985 | 0.1622 | 0.4732 | 0.049 (3)* | |
C6 | 0.36528 (9) | 0.36251 (8) | 0.12842 (16) | 0.0540 (3) | |
H61 | 0.4149 | 0.3326 | 0.0972 | 0.070 (4)* | |
C11 | 0.04434 (8) | 0.60372 (7) | 0.32230 (15) | 0.0461 (3) | |
H111 | 0.0510 | 0.6598 | 0.3738 | 0.056 (4)* | |
H112 | 0.0343 | 0.5630 | 0.4058 | 0.055 (4)* | |
C1 | 0.0000 | 0.14535 (9) | 0.2500 | 0.0410 (4) | |
H11 | −0.0374 | 0.1088 | 0.3069 | 0.045 (3)* | |
C8 | 0.28829 (8) | 0.49578 (8) | 0.16253 (16) | 0.0509 (3) | |
H81 | 0.2872 | 0.5551 | 0.1561 | 0.055 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0404 (5) | 0.0348 (4) | 0.0850 (6) | −0.0048 (3) | 0.0262 (4) | −0.0088 (4) |
N1 | 0.0400 (5) | 0.0412 (5) | 0.0545 (6) | −0.0019 (4) | 0.0135 (4) | −0.0035 (4) |
C9 | 0.0349 (5) | 0.0429 (6) | 0.0481 (6) | −0.0053 (4) | 0.0109 (4) | −0.0107 (4) |
C4 | 0.0339 (5) | 0.0423 (6) | 0.0405 (5) | −0.0039 (4) | 0.0066 (4) | −0.0076 (4) |
C3 | 0.0357 (5) | 0.0418 (6) | 0.0410 (6) | −0.0008 (4) | 0.0080 (4) | −0.0072 (4) |
C7 | 0.0430 (6) | 0.0617 (8) | 0.0663 (8) | −0.0136 (6) | 0.0242 (6) | −0.0126 (6) |
C10 | 0.0433 (6) | 0.0344 (6) | 0.0572 (7) | −0.0046 (5) | 0.0127 (5) | −0.0034 (5) |
C5 | 0.0424 (6) | 0.0448 (6) | 0.0510 (7) | 0.0015 (5) | 0.0119 (5) | −0.0069 (5) |
C2 | 0.0457 (6) | 0.0434 (6) | 0.0448 (6) | 0.0000 (5) | 0.0139 (5) | 0.0021 (5) |
C6 | 0.0417 (6) | 0.0614 (8) | 0.0630 (7) | 0.0008 (5) | 0.0207 (5) | −0.0139 (6) |
C11 | 0.0474 (7) | 0.0390 (6) | 0.0529 (7) | −0.0001 (5) | 0.0135 (5) | −0.0068 (5) |
C1 | 0.0439 (8) | 0.0316 (7) | 0.0511 (9) | 0.000 | 0.0180 (7) | 0.000 |
C8 | 0.0450 (7) | 0.0456 (7) | 0.0650 (8) | −0.0124 (5) | 0.0184 (6) | −0.0109 (5) |
O1—C9 | 1.3629 (14) | C10—H102 | 0.9700 |
O1—C10 | 1.4350 (13) | C5—C6 | 1.3793 (17) |
N1—C3 | 1.2607 (14) | C5—H51 | 0.9300 |
N1—C2 | 1.4587 (15) | C2—C1 | 1.5181 (14) |
C9—C8 | 1.3912 (16) | C2—H21 | 0.9700 |
C9—C4 | 1.4052 (16) | C2—H22 | 0.9700 |
C4—C5 | 1.3924 (16) | C6—H61 | 0.9300 |
C4—C3 | 1.4724 (16) | C11—C11i | 1.525 (2) |
C3—H31 | 0.9300 | C11—H111 | 0.9700 |
C7—C6 | 1.3799 (19) | C11—H112 | 0.9700 |
C7—C8 | 1.3808 (17) | C1—C2i | 1.5181 (14) |
C7—H71 | 0.9300 | C1—H11 | 0.9700 |
C10—C11 | 1.5069 (18) | C8—H81 | 0.9300 |
C10—H101 | 0.9700 | ||
C9—O1—C10 | 118.88 (8) | C4—C5—H51 | 119.4 |
C3—N1—C2 | 117.71 (10) | N1—C2—C1 | 110.72 (9) |
O1—C9—C8 | 124.24 (11) | N1—C2—H21 | 109.5 |
O1—C9—C4 | 115.57 (9) | C1—C2—H21 | 109.5 |
C8—C9—C4 | 120.18 (10) | N1—C2—H22 | 109.5 |
C5—C4—C9 | 118.47 (10) | C1—C2—H22 | 109.5 |
C5—C4—C3 | 121.09 (10) | H21—C2—H22 | 108.1 |
C9—C4—C3 | 120.41 (9) | C5—C6—C7 | 119.42 (11) |
N1—C3—C4 | 122.64 (10) | C5—C6—H61 | 120.3 |
N1—C3—H31 | 118.7 | C7—C6—H61 | 120.3 |
C4—C3—H31 | 118.7 | C10—C11—C11i | 113.92 (12) |
C6—C7—C8 | 121.01 (11) | C10—C11—H111 | 108.8 |
C6—C7—H71 | 119.5 | C11i—C11—H111 | 108.8 |
C8—C7—H71 | 119.5 | C10—C11—H112 | 108.8 |
O1—C10—C11 | 106.19 (9) | C11i—C11—H112 | 108.8 |
O1—C10—H101 | 110.5 | H111—C11—H112 | 107.7 |
C11—C10—H101 | 110.5 | C2—C1—C2i | 113.81 (13) |
O1—C10—H102 | 110.5 | C2—C1—H11 | 108.8 |
C11—C10—H102 | 110.5 | C2i—C1—H11 | 108.8 |
H101—C10—H102 | 108.7 | C7—C8—C9 | 119.61 (12) |
C6—C5—C4 | 121.28 (11) | C7—C8—H81 | 120.2 |
C6—C5—H51 | 119.4 | C9—C8—H81 | 120.2 |
C10—O1—C9—C8 | −11.67 (16) | C3—C4—C5—C6 | −177.12 (10) |
C10—O1—C9—C4 | 169.33 (10) | C3—N1—C2—C1 | 115.50 (11) |
O1—C9—C4—C5 | 176.77 (10) | C4—C5—C6—C7 | 0.55 (18) |
C8—C9—C4—C5 | −2.28 (15) | C8—C7—C6—C5 | −1.0 (2) |
O1—C9—C4—C3 | −5.03 (14) | O1—C10—C11—C11i | −79.17 (9) |
C8—C9—C4—C3 | 175.92 (10) | N1—C2—C1—C2i | −73.83 (8) |
C2—N1—C3—C4 | 178.64 (9) | C6—C7—C8—C9 | −0.21 (19) |
C5—C4—C3—N1 | −4.47 (16) | O1—C9—C8—C7 | −177.09 (11) |
C9—C4—C3—N1 | 177.37 (10) | C4—C9—C8—C7 | 1.87 (17) |
C9—O1—C10—C11 | −177.35 (9) | C10—C11—C11i—C10i | 151.00 (10) |
C9—C4—C5—C6 | 1.07 (16) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C21H24N2O2 |
Mr | 336.43 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.231 (8), 15.6630 (14), 8.206 (4) |
β (°) | 103.044 (8) |
V (Å3) | 1781.9 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scans (MolEN; Fair, 1990) |
Tmin, Tmax | 0.975, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3554, 1816, 1468 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.106, 1.06 |
No. of reflections | 1816 |
No. of parameters | 127 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
O1—C9 | 1.3629 (14) | C4—C3 | 1.4724 (16) |
O1—C10 | 1.4350 (13) | C10—C11 | 1.5069 (18) |
N1—C3 | 1.2607 (14) | C2—C1 | 1.5181 (14) |
N1—C2 | 1.4587 (15) | C11—C11i | 1.525 (2) |
C9—C4 | 1.4052 (16) | ||
C9—O1—C10 | 118.88 (8) | N1—C3—C4 | 122.64 (10) |
C3—N1—C2 | 117.71 (10) | O1—C10—C11 | 106.19 (9) |
O1—C9—C8 | 124.24 (11) | N1—C2—C1 | 110.72 (9) |
O1—C9—C4 | 115.57 (9) | C10—C11—C11i | 113.92 (12) |
C5—C4—C3 | 121.09 (10) | C2—C1—C2i | 113.81 (13) |
C9—C4—C3 | 120.41 (9) | ||
C2—N1—C3—C4 | 178.64 (9) | O1—C10—C11—C11i | −79.17 (9) |
C9—O1—C10—C11 | −177.35 (9) | N1—C2—C1—C2i | −73.83 (8) |
C3—N1—C2—C1 | 115.50 (11) | C10—C11—C11i—C10i | 151.00 (10) |
Symmetry code: (i) −x, y, −z+1/2. |
Over the last two decades, macrocyclic multidentate Schiff base NxOy (where x = 2,3 and y = 2,3) donor-type ligands have been investigated as potential metal-ion-selective ionophores (Lindoy et al., 1993; Esteban et al., 2000). In particular, macrocycles have been widely studied as complexation agents for alkaline, alkaline-earth and transition-metal ion (especially lanthanides) recognition with particular metal-ion binding applications (e.g. selective extraction of heavy and precious metals) are of great interest in environmental, inorganic and coordination chemistry (Lindoy, 1997; Hayvalı et al., 1999; Vicente et al., 2000). Some Schiff base complexes have also been used in catalytic reduction reactions (Tafesh & Weiguny, 1996). In addition, a series of investigations have also involved the synthetic, thermodynamic and structural properties of selective complex formation of a number of transition metal ions (Fenton et al., 1987; Adam et al., 1994a). In literature, there are only a very limited number of reports about the structures of the free macrocyclic multidentate N2O2 and N2O3 donor-type ligands (Chia et al., 1991; Hökelek et al., 1999a,b; Hökelek, Akduran, Kaya & Kılıç, 2000). In 1994, Adam and co-workers synthesized the reduction product (the multidentate diamine, N2O2) from the reaction of 1,4-bis(salicyloxy)butane, 1,3-diaminopropane and sodium borohydride, without isolating the title compound (Adam et al., 1994b). The title compound, (I), may be a potential metal-ion selective reagent for lanthanides, alkaline and alkaline-earth metal ions. The structure determination of (I) was carried out in order to estimate the relative macrocyclic ring hole size and to understand the effects of the macrocyclic ring on the C═N imine bond and C—N═C bond angle.
As shown in Fig. 1, molecule (I) has a crystallographic twofold axis. The intramolecular C1···C11 [7.219 (3) Å], N1···N1i [3.978 (2) Å], O1···O1i [3.894 (3) Å] and N1···O1i [5.580 (3) Å] distances may indicate the hole size of the ligand cavity [symmetry code: (i) -x, y, 1/2 - z]. The C1···C11 distance is larger than the N···N distance in the potassium complex of substituted diaza-18-crown-6 (6.253 Å; Gandour et al., 1986). The relative macrocyclic inner hole size, estimated as twice the mean distance of the donor atoms from their centroid is approximately 2.08 Å, using the `modified covalent radii' of the Nsp2 (0.66 Å) and Osp3 (0.76 Å) atoms as in the literature method (Goodwin et al., 1982; Adam et al., 1983; Drummond et al., 1982). The inner hole size of (I) (2.08 Å), which is a 17-membered macro-ring, can be compared with the 16- (1.57 Å) and 19-membered (2.53 Å) multidentate ligand hole sizes (Hökelek, Akduran, Kaya & Kılıç, 2000).
The C═N imine bond length [1.2607 (14) Å] and C—N═C imine bond angle [117.71 (10)°] are smaller than the corresponding values in salicylaldimine and naphthaldimine Schiff base ligands (Yıldız et al., 1998; Hökelek et al., 2001). In naphthaldimine and salicylaldimine Schiff bases, intramolecular hydrogen bonding is observed, which causes a lengthening of the C═N imine bond and an increase in the C—N═C bond angle (Yıldız et al., 1998; Hökelek, Kılıç, Işıklan & Toy, 2000). C═N imine bond lengthening is also observed in the Schiff base complexes (Fernández-G et al., 1986; Calligaris et al., 1972).