Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104033657/fa1108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104033657/fa1108Isup2.hkl |
CCDC reference: 264804
Single crystals of (H2L)(ClO4)2 suitable for X-ray crystallography were grown by addition of a dilute solution of perchloric acid in acetonitrile to a solution of [Pb(L)](ClO4)2 0.5H2O in the same solvent (molar ratio 2:1), followed by slow diffusion of diethyl ether into the resultant solution.
The O atoms of one perchlorate anion were disordered (site-occupancy factor 0.5 for atoms O5A, O6A, O5B and O6B). 42 restraints were imposed and applied to the Cl—O bonds of the perchlorate anion. Atom H1N, which is involved in an intramolecular hydrogen bond, was found in a difference electron-density map and then refined riding on the coordinates of atom N1. The positions of all other H atoms were calculated geometrically and a riding model was used in their refinement, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C). Please check added text.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C33H43N5O42+·2ClO4− | F(000) = 1624 |
Mr = 772.62 | Dx = 1.374 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 951 reflections |
a = 9.5092 (2) Å | θ = 2.9–28.2° |
b = 19.1979 (2) Å | µ = 0.24 mm−1 |
c = 20.6024 (5) Å | T = 298 K |
β = 96.880 (1)° | Block-like, colourless |
V = 3734.02 (13) Å3 | 0.40 × 0.35 × 0.30 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 4630 independent reflections |
Radiation source: fine-focus sealed tube | 2771 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.910, Tmax = 0.931 | k = −23→25 |
13616 measured reflections | l = −21→27 |
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)] = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.214 | w = 1/[σ2(Fo2) + (0.101P)2 + 2.7759P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
4630 reflections | Δρmax = 0.66 e Å−3 |
262 parameters | Δρmin = −0.59 e Å−3 |
42 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0030 (7) |
C33H43N5O42+·2ClO4− | V = 3734.02 (13) Å3 |
Mr = 772.62 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.5092 (2) Å | µ = 0.24 mm−1 |
b = 19.1979 (2) Å | T = 298 K |
c = 20.6024 (5) Å | 0.40 × 0.35 × 0.30 mm |
β = 96.880 (1)° |
Siemens SMART CCD area-detector diffractometer | 4630 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2771 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.931 | Rint = 0.033 |
13616 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 42 restraints |
wR(F2) = 0.214 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.66 e Å−3 |
4630 reflections | Δρmin = −0.59 e Å−3 |
262 parameters |
Experimental. Data were collected using a Bruker SMART CCD based diffractometer operating at room temperature. Data were measured using phi–omega scans of 0.3 degrees per frame for 10 s. A total of 1321 frames were collected. The first 50 frames were recollected at the end of the measurement. |
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 | Occ. (<1) | |
Cl1 | 0.5000 | 0.0000 | 0.5000 | 0.0839 (5) | |
N1 | 0.7818 (3) | 0.15351 (12) | 0.65871 (12) | 0.0480 (6) | |
H1N | 0.866 (3) | 0.1740 (15) | 0.6690 (14) | 0.045 (8)* | |
O1 | 0.6776 (2) | 0.12211 (12) | 0.79851 (11) | 0.0662 (6) | |
C1 | 1.0000 | 0.4646 (2) | 0.7500 | 0.0716 (14) | |
H1 | 1.0000 | 0.5130 | 0.7500 | 0.086* | |
O2 | 1.0385 (2) | 0.08667 (11) | 0.65184 (11) | 0.0589 (6) | |
N2 | 0.9614 (2) | 0.25529 (12) | 0.62443 (10) | 0.0458 (6) | |
C2 | 1.0038 (4) | 0.42756 (16) | 0.69360 (16) | 0.0636 (9) | |
H2 | 1.0079 | 0.4508 | 0.6542 | 0.076* | |
Cl2 | 0.0000 | 0.12911 (7) | 0.2500 | 0.1179 (8) | |
O3 | −0.0987 (6) | 0.0885 (3) | 0.2730 (2) | 0.195 (3) | |
O4 | 0.0523 (9) | 0.1703 (3) | 0.2990 (3) | 0.250 (3) | |
N3 | 1.0000 | 0.31829 (15) | 0.7500 | 0.0454 (7) | |
C3 | 1.0015 (3) | 0.35532 (15) | 0.69512 (13) | 0.0494 (7) | |
C4 | 0.9968 (3) | 0.31833 (15) | 0.63209 (13) | 0.0534 (7) | |
H4 | 1.0212 | 0.3428 | 0.5961 | 0.064* | |
O5A | 0.6111 (9) | 0.0222 (4) | 0.4623 (3) | 0.121 (3) | 0.5 |
O6A | 0.5307 (11) | 0.0255 (4) | 0.5609 (3) | 0.109 (3) | 0.5 |
O5B | 0.3751 (11) | 0.0091 (7) | 0.4625 (7) | 0.182 (6) | 0.5 |
O6B | 0.5286 (8) | −0.0780 (3) | 0.5039 (3) | 0.113 (3) | 0.5 |
C5 | 0.9559 (3) | 0.22416 (15) | 0.56137 (13) | 0.0485 (7) | |
C6 | 1.0558 (4) | 0.23595 (19) | 0.51909 (15) | 0.0634 (8) | |
H6 | 1.1293 | 0.2673 | 0.5302 | 0.076* | |
C7 | 1.0458 (4) | 0.2005 (2) | 0.45964 (17) | 0.0748 (10) | |
H7 | 1.1127 | 0.2086 | 0.4311 | 0.090* | |
C8 | 0.9390 (5) | 0.1541 (2) | 0.44289 (17) | 0.0790 (11) | |
H8 | 0.9332 | 0.1307 | 0.4032 | 0.095* | |
C9 | 0.8397 (4) | 0.14216 (18) | 0.48519 (17) | 0.0703 (10) | |
H9 | 0.7670 | 0.1105 | 0.4736 | 0.084* | |
C10 | 0.8463 (3) | 0.17655 (15) | 0.54461 (14) | 0.0528 (7) | |
C11 | 0.7312 (3) | 0.16729 (17) | 0.58765 (15) | 0.0575 (8) | |
H11A | 0.6715 | 0.1288 | 0.5709 | 0.069* | |
H11B | 0.6731 | 0.2089 | 0.5848 | 0.069* | |
C12 | 0.6853 (3) | 0.18867 (18) | 0.70118 (16) | 0.0595 (8) | |
H12A | 0.6774 | 0.2375 | 0.6892 | 0.071* | |
H12B | 0.5917 | 0.1682 | 0.6924 | 0.071* | |
C13 | 0.7330 (3) | 0.18359 (17) | 0.77315 (16) | 0.0599 (8) | |
H13A | 0.8357 | 0.1827 | 0.7806 | 0.072* | |
H13B | 0.7004 | 0.2240 | 0.7953 | 0.072* | |
C14 | 0.7251 (4) | 0.1113 (2) | 0.86613 (17) | 0.0726 (10) | |
H14A | 0.6463 | 0.0948 | 0.8878 | 0.087* | |
H14B | 0.7562 | 0.1554 | 0.8858 | 0.087* | |
C15 | 0.8040 (3) | 0.07773 (16) | 0.67470 (17) | 0.0600 (8) | |
H15A | 0.7153 | 0.0530 | 0.6640 | 0.072* | |
H15B | 0.8325 | 0.0727 | 0.7213 | 0.072* | |
C16 | 0.9148 (4) | 0.04578 (16) | 0.63783 (18) | 0.0628 (8) | |
H16A | 0.9332 | −0.0020 | 0.6518 | 0.075* | |
H16B | 0.8836 | 0.0460 | 0.5913 | 0.075* | |
C17 | 1.1568 (4) | 0.0602 (2) | 0.62295 (19) | 0.0724 (10) | |
H17A | 1.1308 | 0.0531 | 0.5765 | 0.087* | |
H17B | 1.1862 | 0.0158 | 0.6426 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1164 (12) | 0.0894 (10) | 0.0459 (6) | −0.0572 (8) | 0.0100 (7) | −0.0073 (6) |
N1 | 0.0417 (12) | 0.0476 (13) | 0.0536 (14) | −0.0071 (10) | 0.0015 (10) | 0.0013 (11) |
O1 | 0.0546 (12) | 0.0776 (16) | 0.0673 (15) | −0.0174 (11) | 0.0105 (11) | 0.0074 (11) |
C1 | 0.115 (4) | 0.037 (2) | 0.063 (3) | 0.000 | 0.009 (3) | 0.000 |
O2 | 0.0565 (12) | 0.0527 (12) | 0.0680 (14) | 0.0043 (10) | 0.0097 (10) | −0.0114 (10) |
N2 | 0.0511 (13) | 0.0466 (13) | 0.0390 (12) | −0.0058 (10) | 0.0030 (10) | −0.0024 (9) |
C2 | 0.097 (2) | 0.0437 (16) | 0.0496 (17) | −0.0106 (16) | 0.0054 (16) | 0.0055 (13) |
Cl2 | 0.233 (2) | 0.0484 (7) | 0.0882 (11) | 0.000 | 0.0853 (13) | 0.000 |
O3 | 0.205 (5) | 0.223 (5) | 0.149 (4) | −0.102 (4) | −0.010 (3) | 0.077 (4) |
O4 | 0.366 (7) | 0.206 (5) | 0.208 (4) | −0.158 (5) | 0.166 (5) | −0.130 (4) |
N3 | 0.0579 (19) | 0.0367 (16) | 0.0406 (17) | 0.000 | 0.0022 (14) | 0.000 |
C3 | 0.0633 (17) | 0.0426 (15) | 0.0416 (15) | −0.0102 (12) | 0.0034 (12) | 0.0006 (11) |
C4 | 0.0737 (19) | 0.0485 (16) | 0.0374 (14) | −0.0133 (14) | 0.0046 (13) | 0.0007 (12) |
O5A | 0.178 (7) | 0.095 (5) | 0.106 (5) | −0.042 (5) | 0.078 (5) | 0.001 (4) |
O6A | 0.147 (7) | 0.121 (6) | 0.060 (4) | −0.027 (5) | 0.019 (4) | −0.025 (3) |
O5B | 0.124 (8) | 0.191 (10) | 0.213 (13) | −0.024 (7) | −0.056 (8) | 0.030 (9) |
O6B | 0.170 (7) | 0.072 (4) | 0.098 (5) | −0.040 (4) | 0.015 (4) | 0.003 (3) |
C5 | 0.0571 (16) | 0.0492 (15) | 0.0377 (14) | −0.0036 (13) | −0.0001 (12) | −0.0027 (11) |
C6 | 0.068 (2) | 0.075 (2) | 0.0481 (17) | −0.0084 (17) | 0.0073 (15) | −0.0041 (15) |
C7 | 0.088 (3) | 0.088 (3) | 0.0504 (19) | 0.006 (2) | 0.0179 (18) | −0.0049 (18) |
C8 | 0.110 (3) | 0.076 (2) | 0.0499 (19) | 0.005 (2) | 0.004 (2) | −0.0163 (17) |
C9 | 0.092 (3) | 0.058 (2) | 0.056 (2) | −0.0075 (18) | −0.0094 (18) | −0.0101 (15) |
C10 | 0.0627 (18) | 0.0472 (16) | 0.0455 (16) | −0.0019 (13) | −0.0061 (13) | −0.0016 (12) |
C11 | 0.0512 (16) | 0.0605 (18) | 0.0572 (18) | −0.0087 (14) | −0.0088 (13) | 0.0020 (14) |
C12 | 0.0475 (16) | 0.0629 (19) | 0.069 (2) | 0.0061 (14) | 0.0117 (14) | 0.0041 (15) |
C13 | 0.0538 (17) | 0.0609 (19) | 0.067 (2) | −0.0038 (15) | 0.0153 (15) | −0.0005 (15) |
C14 | 0.060 (2) | 0.099 (3) | 0.062 (2) | −0.0094 (19) | 0.0176 (16) | 0.0110 (19) |
C15 | 0.0630 (19) | 0.0471 (17) | 0.070 (2) | −0.0068 (14) | 0.0082 (16) | 0.0061 (14) |
C16 | 0.075 (2) | 0.0417 (16) | 0.072 (2) | −0.0026 (14) | 0.0067 (17) | −0.0028 (14) |
C17 | 0.072 (2) | 0.079 (2) | 0.067 (2) | 0.0140 (19) | 0.0122 (17) | −0.0169 (18) |
Cl1—O6A | 1.346 (5) | C6—C7 | 1.394 (5) |
Cl1—O5A | 1.448 (6) | C6—H6 | 0.9300 |
Cl1—O5B | 1.348 (8) | C7—C8 | 1.364 (6) |
Cl1—O6B | 1.522 (6) | C7—H7 | 0.9300 |
N1—C15 | 1.501 (4) | C8—C9 | 1.379 (6) |
N1—C12 | 1.501 (4) | C8—H8 | 0.9300 |
N1—C11 | 1.509 (4) | C9—C10 | 1.386 (4) |
N1—N1i | 5.257 (5) | C9—H9 | 0.9300 |
N1—H1N | 0.89 (3) | C10—C11 | 1.500 (4) |
O1—C13 | 1.418 (4) | C11—H11A | 0.9700 |
O1—C14 | 1.427 (4) | C11—H11B | 0.9700 |
C1—C2 | 1.366 (4) | C12—C13 | 1.501 (4) |
C1—H1 | 0.9300 | C12—H12A | 0.9700 |
O2—C16 | 1.414 (4) | C12—H12B | 0.9700 |
O2—C17 | 1.428 (4) | C13—H13A | 0.9700 |
N2—C4 | 1.261 (3) | C13—H13B | 0.9700 |
N2—C5 | 1.425 (3) | C14—C17i | 1.488 (5) |
N2—N2i | 5.138 (4) | C14—H14A | 0.9700 |
C2—C3 | 1.387 (4) | C14—H14B | 0.9700 |
C2—H2 | 0.9300 | C15—C16 | 1.502 (5) |
Cl2—O4 | 1.331 (5) | C15—H15A | 0.9700 |
Cl2—O3 | 1.350 (4) | C15—H15B | 0.9700 |
N3—C3 | 1.337 (3) | C16—H16A | 0.9700 |
C3—C4 | 1.476 (4) | C16—H16B | 0.9700 |
C4—H4 | 0.9300 | C17—C14i | 1.488 (5) |
C5—C6 | 1.383 (4) | C17—H17A | 0.9700 |
C5—C10 | 1.398 (4) | C17—H17B | 0.9700 |
O6A—Cl1—O5B | 124.4 (6) | C10—C9—H9 | 119.4 |
O6A—Cl1—O5A | 107.6 (5) | C9—C10—C5 | 118.9 (3) |
O5B—Cl1—O5A | 107.7 (7) | C9—C10—C11 | 120.4 (3) |
O6A—Cl1—O6B | 107.0 (5) | C5—C10—C11 | 120.4 (3) |
O5B—Cl1—O6B | 107.2 (6) | C10—C11—N1 | 115.1 (2) |
O5A—Cl1—O6B | 100.4 (4) | C10—C11—H11A | 108.5 |
C15—N1—C12 | 112.8 (2) | N1—C11—H11A | 108.5 |
C15—N1—C11 | 113.8 (2) | C10—C11—H11B | 108.5 |
C12—N1—C11 | 109.9 (2) | N1—C11—H11B | 108.5 |
C15—N1—H1N | 106.1 (18) | H11A—C11—H11B | 107.5 |
C12—N1—H1N | 104.8 (18) | C13—C12—N1 | 114.4 (2) |
C11—N1—H1N | 108.9 (18) | C13—C12—H12A | 108.7 |
C13—O1—C14 | 113.1 (3) | N1—C12—H12A | 108.7 |
C2—C1—C2i | 117.3 (4) | C13—C12—H12B | 108.7 |
C2—C1—H1 | 121.3 | N1—C12—H12B | 108.7 |
C2i—C1—H1 | 121.3 | H12A—C12—H12B | 107.6 |
C16—O2—C17 | 113.3 (2) | O1—C13—C12 | 109.7 (3) |
C4—N2—C5 | 119.8 (2) | O1—C13—H13A | 109.7 |
C1—C2—C3 | 119.9 (3) | C12—C13—H13A | 109.7 |
C1—C2—H2 | 120.0 | O1—C13—H13B | 109.7 |
C3—C2—H2 | 120.0 | C12—C13—H13B | 109.7 |
O4—Cl2—O4ii | 107.2 (7) | H13A—C13—H13B | 108.2 |
O4—Cl2—O3ii | 113.4 (4) | O1—C14—C17i | 112.9 (3) |
O4—Cl2—O3 | 106.8 (3) | O1—C14—H14A | 109.0 |
O3ii—Cl2—O3 | 109.4 (6) | C17i—C14—H14A | 109.0 |
C3—N3—C3i | 115.8 (3) | O1—C14—H14B | 109.0 |
N3—C3—C2 | 123.5 (3) | C17i—C14—H14B | 109.0 |
N3—C3—C4 | 119.1 (2) | H14A—C14—H14B | 107.8 |
C2—C3—C4 | 117.4 (3) | N1—C15—C16 | 111.9 (3) |
N2—C4—C3 | 123.5 (3) | N1—C15—H15A | 109.2 |
N2—C4—H4 | 118.3 | C16—C15—H15A | 109.2 |
C3—C4—H4 | 118.3 | N1—C15—H15B | 109.2 |
C6—C5—C10 | 120.0 (3) | C16—C15—H15B | 109.2 |
C6—C5—N2 | 123.6 (3) | H15A—C15—H15B | 107.9 |
C10—C5—N2 | 116.4 (3) | O2—C16—C15 | 106.7 (2) |
C5—C6—C7 | 119.6 (3) | O2—C16—H16A | 110.4 |
C5—C6—H6 | 120.2 | C15—C16—H16A | 110.4 |
C7—C6—H6 | 120.2 | O2—C16—H16B | 110.4 |
C8—C7—C6 | 120.8 (3) | C15—C16—H16B | 110.4 |
C8—C7—H7 | 119.6 | H16A—C16—H16B | 108.6 |
C6—C7—H7 | 119.6 | O2—C17—C14i | 108.7 (3) |
C7—C8—C9 | 119.6 (3) | O2—C17—H17A | 109.9 |
C7—C8—H8 | 120.2 | C14i—C17—H17A | 109.9 |
C9—C8—H8 | 120.2 | O2—C17—H17B | 109.9 |
C8—C9—C10 | 121.1 (3) | C14i—C17—H17B | 109.9 |
C8—C9—H9 | 119.4 | H17A—C17—H17B | 108.3 |
C2i—C1—C2—C3 | 1.0 (2) | N2—C5—C10—C9 | −177.0 (3) |
C3i—N3—C3—C2 | 1.1 (3) | C6—C5—C10—C11 | −175.4 (3) |
C3i—N3—C3—C4 | −177.3 (3) | N2—C5—C10—C11 | 8.1 (4) |
C1—C2—C3—N3 | −2.1 (5) | C9—C10—C11—N1 | 133.2 (3) |
C1—C2—C3—C4 | 176.3 (3) | C5—C10—C11—N1 | −51.9 (4) |
C5—N2—C4—C3 | 178.2 (3) | C15—N1—C11—C10 | −88.6 (3) |
N2i—N2—C4—C3 | −14.8 (3) | C12—N1—C11—C10 | 143.8 (3) |
N3—C3—C4—N2 | 15.7 (5) | C15—N1—C12—C13 | 57.0 (3) |
C2—C3—C4—N2 | −162.8 (3) | C11—N1—C12—C13 | −174.9 (3) |
C4—N2—C5—C6 | 41.0 (4) | C14—O1—C13—C12 | 176.5 (3) |
C4—N2—C5—C10 | −142.6 (3) | N1—C12—C13—O1 | −88.8 (3) |
C10—C5—C6—C7 | 0.5 (5) | C13—O1—C14—C17i | −99.8 (4) |
N2—C5—C6—C7 | 176.8 (3) | C12—N1—C15—C16 | −172.7 (3) |
C5—C6—C7—C8 | −0.3 (6) | C11—N1—C15—C16 | 61.2 (3) |
C6—C7—C8—C9 | 0.1 (6) | N1i—N1—C15—C16 | −84.2 (2) |
C7—C8—C9—C10 | 0.0 (6) | C17—O2—C16—C15 | 176.6 (3) |
C8—C9—C10—C5 | 0.1 (5) | N1—C15—C16—O2 | 55.1 (3) |
C8—C9—C10—C11 | 175.1 (3) | C16—O2—C17—C14i | 173.2 (3) |
C6—C5—C10—C9 | −0.4 (5) | N2—C4—C3—N3 | 15.7 (5) |
Symmetry codes: (i) −x+2, y, −z+3/2; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.89 (3) | 2.07 (3) | 2.743 (3) | 131 (2) |
Experimental details
Crystal data | |
Chemical formula | C33H43N5O42+·2ClO4− |
Mr | 772.62 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.5092 (2), 19.1979 (2), 20.6024 (5) |
β (°) | 96.880 (1) |
V (Å3) | 3734.02 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.40 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.910, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13616, 4630, 2771 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.214, 1.06 |
No. of reflections | 4630 |
No. of parameters | 262 |
No. of restraints | 42 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.59 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL.
N1—C15 | 1.501 (4) | O1—C14 | 1.427 (4) |
N1—C12 | 1.501 (4) | N2—C4 | 1.261 (3) |
N1—C11 | 1.509 (4) | N2—C5 | 1.425 (3) |
O1—C13 | 1.418 (4) | ||
C15—N1—C12 | 112.8 (2) | C16—O2—C17 | 113.3 (2) |
C15—N1—C11 | 113.8 (2) | C4—N2—C5 | 119.8 (2) |
C12—N1—C11 | 109.9 (2) | N2—C4—C3 | 123.5 (3) |
C13—O1—C14 | 113.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2 | 0.89 (3) | 2.07 (3) | 2.743 (3) | 131 (2) |
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Macrocyclic compounds have been studied extensively from many different points of view, such as molecular recognition, artificial catalysis and supramolecular structure. Our current research interest in this field includes the design of novel macrobicyclic architectures. According to the number of connecting bridges used for their construction and the nature of the subunits used as building blocks, two different kinds of macrobicyclic structures may be envisaged, namely axial macrobicycles, which result from a coaxial arrangement of two tripodal subunits linked by three bridges, and lateral macrobicycles, which are dissymmetrical molecules structurally based on the combination of two different binding units, one chelating and one macrocyclic (Lehn, 1980). We have reported a novel family of Schiff base lateral macrobicycles containing two different binding units, namely a rigid unsaturated N2X set (X = N or O) and a flexible cyclic N2On set linked by aromatic bridges (Esteban et al., 1999). These macrobicycles are structurally derived from bibracchial lariat ethers incorporating pendant aniline moieties, and constitute the first examples of lateral macrobicycles containing imine groups. This type of Schiff base lateral macrobicyclic architecture cannot be prepared by direct reaction between the organic precursors. However, some metal ions can template the corresponding reactions, thereby allowing access to the desired macrobicycles in high yields (Platas-Iglesias et al., 2003), although in all cases the metal ion acts as a permanent template, remaining trapped in the macrobicyclic cavity. Thus, to date, all the X-ray crystal structures described for this type of lateral macrobicycle correspond to their metal-coordinated form. We have found that addition of perchloric acid to the Pb complex of L causes the demetallation of the complex, yielding the macrobicycle L in its protonated form, (H2L)(ClO4)2, (I). Here, we describe the structure of (I), which represents the first X-ray structure determination of an uncoordinated Schiff base lateral macrobicycle.
The asymmetric unit of (I) comprises a half-molecule of the cation (H2L)2+, and half molecules of two crystallographically independent perchlorate anions. The cation and one of the anions (Cl2) are located on twofold axes, while the second perchlorate is situated on a centre of symmetry, with half-occupied disordered O sites. Fig. 1 shows the structure of (I), while selected bond lengths and angles are given in Table 1. The bond lengths and angles do not show any significant deviation from the expected values. The N2═C4 distance of 1.261 (3) Å is consistent with an imine group, and the bond angle of 119.8 (2)° for C4—N2—C5 confirms the sp2 character of atom N2.
The conformation of the macrobicycle L in (I) is conditioned by two strong intramolecular hydrogen-bonding interactions involving the pivot and imine N atoms [N2···N1 2.743 (3) Å; Table 2], and in fact this conformation is quite different from that observed when a metal ion is placed inside its cavity (Avecilla et al., 2003). The lateral aromatic rings of (H2L)2+ form a dihedral angle of 85.32 (9)°, whereas the plane of the pyridine ring forms a dihedral angle of 54.87 (10)° with the plane containing the benzene ring. The imine groups are not coplanar with the pyridine moiety, as indicated by the dihedral angle N2—C4—C3—N3 of 15.7 (5)°. This deviation from planarity is considerably greater than that found in the corresponding Ba complex (Avecilla et al., 2003). Moreover, the fold of the macrobicycle causes an important approach between the two pivot N atoms [N1···N1A 5.257 (5) Å], which are 6.384 (4) Å apart when a Ba ion is trapped in the macrobicyclic cavity (Avecilla et al., 2003). Moreover, the distance between the two imine N atoms (N2 and N2A) is 5.138 (4) Å, ca 0.35 Å longer than that found in [Ba(L)]2+.