Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001398/wn6001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001398/wn6001Isup2.hkl |
CCDC reference: 159767
The title compound was synthesized according to the literature method of Butler & NiBhradaigh (1994). Crystals suitable for X-ray diffraction were grown from dichloromethane/pentane (1:1).
It was possible to positionally refine all H-atom positions in this crystal structure. However, as `free' refinement yielded a final position which was close (within the bounds of experimental error) to the calculated positions, we ultimately refined the H atoms riding on their relevant parent atoms.
Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CELDIM in CAD-4-PC Software; data reduction: XCAD (McArdle & Higgins, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEX (McArdle, 1995).
C28H32N16 | Z = 1 |
Mr = 592.70 | F(000) = 312 |
Triclinic, P1 | Dx = 1.367 Mg m−3 |
a = 7.170 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 10.241 (3) Å | Cell parameters from 25 reflections |
c = 10.729 (3) Å | θ = 13.9–17.7° |
α = 77.25 (3)° | µ = 0.09 mm−1 |
β = 74.89 (3)° | T = 293 K |
γ = 73.47 (3)° | Block, colourless |
V = 719.9 (4) Å3 | 0.35 × 0.30 × 0.30 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.010 |
Radiation source: fine-focus sealed tube | θmax = 24.0°, θmin = 2.1° |
Graphite monochromator | h = 0→8 |
θ/2θ scans | k = −11→11 |
2441 measured reflections | l = −11→12 |
2238 independent reflections | 1 standard reflections every 80 reflections |
1674 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0714P)2 + 0.0022P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2238 reflections | Δρmax = 0.17 e Å−3 |
200 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Extinction correction: SHELXL93, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0608 (71) |
C28H32N16 | γ = 73.47 (3)° |
Mr = 592.70 | V = 719.9 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.170 (2) Å | Mo Kα radiation |
b = 10.241 (3) Å | µ = 0.09 mm−1 |
c = 10.729 (3) Å | T = 293 K |
α = 77.25 (3)° | 0.35 × 0.30 × 0.30 mm |
β = 74.89 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.010 |
2441 measured reflections | θmax = 24.0° |
2238 independent reflections | 1 standard reflections every 80 reflections |
1674 reflections with I > 2σ(I) | intensity decay: none |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.17 e Å−3 |
2238 reflections | Δρmin = −0.13 e Å−3 |
200 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2292 (2) | 0.31148 (15) | 0.60411 (13) | 0.0527 (4) | |
N2 | 0.2397 (2) | 0.43564 (15) | 0.53809 (14) | 0.0559 (4) | |
N3 | 0.2452 (2) | 0.43014 (14) | 0.41642 (14) | 0.0498 (4) | |
N4 | 0.2409 (2) | 0.30851 (14) | 0.39627 (13) | 0.0501 (4) | |
N5 | 0.8191 (2) | 0.87060 (13) | 0.04860 (12) | 0.0450 (4) | |
N6 | 0.7094 (2) | 0.93678 (14) | 0.14675 (13) | 0.0456 (4) | |
N7 | 1.0277 (2) | 0.86172 (15) | 0.15889 (13) | 0.0492 (4) | |
N8 | 1.0089 (2) | 0.8249 (2) | 0.05300 (13) | 0.0516 (4) | |
C1 | 0.2314 (2) | 0.0877 (2) | 0.54015 (15) | 0.0398 (4) | |
C2 | 0.2699 (2) | 0.0224 (2) | 0.4327 (2) | 0.0477 (4) | |
H2 | 0.2921 | 0.0728 | 0.3490 | 0.057* | |
C3 | 0.2757 (3) | −0.1152 (2) | 0.4474 (2) | 0.0547 (5) | |
H3 | 0.2993 | −0.1565 | 0.3739 | 0.066* | |
C4 | 0.2469 (3) | −0.1926 (2) | 0.5705 (2) | 0.0556 (5) | |
H4 | 0.2513 | −0.2859 | 0.5806 | 0.067* | |
C5 | 0.2115 (2) | −0.1294 (2) | 0.6784 (2) | 0.0500 (5) | |
H5 | 0.1941 | −0.1815 | 0.7614 | 0.060* | |
C6 | 0.2014 (2) | 0.0102 (2) | 0.6658 (2) | 0.0408 (4) | |
C7 | 0.2308 (2) | 0.2356 (2) | 0.51581 (14) | 0.0408 (4) | |
C8 | 0.2703 (3) | 0.5443 (2) | 0.3086 (2) | 0.0582 (5) | |
H8A | 0.2363 | 0.6298 | 0.3435 | 0.070* | |
H8B | 0.1807 | 0.5534 | 0.2516 | 0.070* | |
C9 | 0.4837 (3) | 0.5195 (2) | 0.2303 (2) | 0.0549 (5) | |
H9A | 0.5718 | 0.5112 | 0.2881 | 0.066* | |
H9B | 0.5173 | 0.4326 | 0.1981 | 0.066* | |
C10 | 0.5207 (3) | 0.6315 (2) | 0.1161 (2) | 0.0547 (5) | |
H10A | 0.4839 | 0.7194 | 0.1471 | 0.066* | |
H10B | 0.4380 | 0.6376 | 0.0555 | 0.066* | |
C11 | 0.7370 (3) | 0.6029 (2) | 0.0461 (2) | 0.0552 (5) | |
H11A | 0.7743 | 0.5116 | 0.0220 | 0.066* | |
H11B | 0.8171 | 0.6014 | 0.1069 | 0.066* | |
C12 | 0.7894 (3) | 0.7052 (2) | −0.0763 (2) | 0.0589 (5) | |
H12A | 0.9314 | 0.6781 | −0.1116 | 0.071* | |
H12B | 0.7215 | 0.6990 | −0.1413 | 0.071* | |
C13 | 0.7366 (3) | 0.8532 (2) | −0.0557 (2) | 0.0529 (5) | |
H13A | 0.7864 | 0.9092 | −0.1364 | 0.063* | |
H13B | 0.5929 | 0.8859 | −0.0345 | 0.063* | |
C14 | 0.1567 (2) | 0.0712 (2) | 0.78545 (14) | 0.0401 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0734 (10) | 0.0496 (9) | 0.0382 (8) | −0.0257 (7) | −0.0058 (7) | −0.0059 (7) |
N2 | 0.0742 (11) | 0.0500 (9) | 0.0452 (9) | −0.0238 (7) | −0.0042 (7) | −0.0092 (7) |
N3 | 0.0604 (9) | 0.0440 (8) | 0.0444 (8) | −0.0192 (7) | −0.0048 (6) | −0.0044 (6) |
N4 | 0.0668 (10) | 0.0451 (8) | 0.0401 (8) | −0.0198 (7) | −0.0110 (7) | −0.0024 (6) |
N5 | 0.0532 (9) | 0.0438 (8) | 0.0376 (7) | −0.0147 (6) | −0.0107 (6) | −0.0004 (6) |
N6 | 0.0470 (8) | 0.0505 (8) | 0.0393 (8) | −0.0126 (6) | −0.0094 (6) | −0.0056 (6) |
N7 | 0.0461 (8) | 0.0565 (9) | 0.0438 (8) | −0.0109 (7) | −0.0097 (6) | −0.0069 (7) |
N8 | 0.0498 (9) | 0.0584 (9) | 0.0445 (8) | −0.0114 (7) | −0.0075 (6) | −0.0086 (7) |
C1 | 0.0382 (9) | 0.0440 (9) | 0.0388 (9) | −0.0127 (7) | −0.0091 (7) | −0.0047 (7) |
C2 | 0.0542 (10) | 0.0520 (10) | 0.0397 (9) | −0.0167 (8) | −0.0118 (7) | −0.0057 (7) |
C3 | 0.0610 (11) | 0.0540 (11) | 0.0548 (11) | −0.0132 (8) | −0.0148 (8) | −0.0180 (9) |
C4 | 0.0587 (12) | 0.0410 (9) | 0.0698 (13) | −0.0123 (8) | −0.0179 (9) | −0.0086 (9) |
C5 | 0.0524 (10) | 0.0464 (10) | 0.0494 (11) | −0.0152 (8) | −0.0125 (8) | 0.0025 (8) |
C6 | 0.0357 (8) | 0.0437 (9) | 0.0431 (9) | −0.0118 (7) | −0.0097 (7) | −0.0023 (7) |
C7 | 0.0406 (9) | 0.0472 (9) | 0.0364 (9) | −0.0156 (7) | −0.0064 (7) | −0.0056 (7) |
C8 | 0.0745 (13) | 0.0425 (10) | 0.0513 (11) | −0.0182 (8) | −0.0058 (9) | 0.0017 (8) |
C9 | 0.0591 (11) | 0.0491 (10) | 0.0564 (11) | −0.0204 (8) | −0.0122 (9) | 0.0017 (8) |
C10 | 0.0612 (11) | 0.0477 (10) | 0.0518 (11) | −0.0154 (8) | −0.0087 (8) | −0.0021 (8) |
C11 | 0.0607 (12) | 0.0470 (10) | 0.0565 (11) | −0.0173 (8) | −0.0059 (9) | −0.0079 (8) |
C12 | 0.0685 (12) | 0.0636 (12) | 0.0470 (10) | −0.0250 (10) | −0.0031 (9) | −0.0126 (9) |
C13 | 0.0689 (12) | 0.0566 (11) | 0.0384 (9) | −0.0233 (9) | −0.0188 (8) | 0.0014 (8) |
C14 | 0.0434 (9) | 0.0410 (8) | 0.0349 (8) | −0.0148 (7) | −0.0093 (7) | 0.0031 (7) |
N1—N2 | 1.324 (2) | C1—C7 | 1.479 (2) |
N1—C7 | 1.347 (2) | C2—C3 | 1.372 (2) |
N2—N3 | 1.309 (2) | C3—C4 | 1.380 (3) |
N3—N4 | 1.320 (2) | C4—C5 | 1.381 (2) |
N3—C8 | 1.467 (2) | C5—C6 | 1.388 (2) |
N4—C7 | 1.329 (2) | C6—C14 | 1.472 (2) |
N5—N8 | 1.318 (2) | C8—C9 | 1.522 (2) |
N5—N6 | 1.329 (2) | C9—C10 | 1.506 (2) |
N5—C13 | 1.458 (2) | C10—C11 | 1.512 (2) |
N6i—C14 | 1.323 (2) | C11—C12 | 1.524 (3) |
N7—N8 | 1.322 (2) | C12—C13 | 1.506 (3) |
N7i—C14 | 1.352 (2) | C14i—N6 | 1.323 (2) |
C1—C2 | 1.387 (2) | C14i—N7 | 1.352 (2) |
C1—C6 | 1.403 (2) | ||
N2—N1—C7 | 106.1 (1) | C3—C4—C5 | 119.0 (2) |
N3—N2—N1 | 106.1 (1) | C4—C5—C6 | 121.6 (2) |
N2—N3—N4 | 114.2 (1) | C5—C6—C1 | 118.9 (2) |
N2—N3—C8 | 123.7 (1) | C5—C6—C14 | 118.5 (1) |
N4—N3—C8 | 122.0 (1) | C1—C6—C14 | 122.7 (1) |
N3—N4—C7 | 102.0 (1) | N4—C7—N1 | 111.8 (1) |
N8—N5—N6 | 113.9 (1) | N4—C7—C1 | 121.3 (1) |
N8—N5—C13 | 123.3 (1) | N1—C7—C1 | 126.9 (1) |
N6—N5—C13 | 122.8 (1) | N3—C8—C9 | 110.8 (2) |
C14i—N6—N5 | 101.9 (1) | C10—C9—C8 | 114.0 (2) |
N8—N7—C14i | 106.1 (1) | C9—C10—C11 | 111.1 (2) |
N5—N8—N7 | 106.0 (1) | C10—C11—C12 | 115.7 (2) |
C2—C1—C6 | 118.9 (1) | C13—C12—C11 | 114.9 (2) |
C2—C1—C7 | 117.9 (1) | N5—C13—C12 | 112.4 (2) |
C6—C1—C7 | 123.2 (1) | N6i—C14—N7i | 112.1 (1) |
C3—C2—C1 | 121.3 (2) | N6i—C14—C6 | 124.1 (1) |
C2—C3—C4 | 120.4 (2) | N7i—C14—C6 | 123.8 (1) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C28H32N16 |
Mr | 592.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.170 (2), 10.241 (3), 10.729 (3) |
α, β, γ (°) | 77.25 (3), 74.89 (3), 73.47 (3) |
V (Å3) | 719.9 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2441, 2238, 1674 |
Rint | 0.010 |
θmax (°) | 24.0 |
(sin θ/λ)max (Å−1) | 0.571 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.08 |
No. of reflections | 2238 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.13 |
Computer programs: CAD-4-PC Software (Enraf-Nonius, 1992), CELDIM in CAD-4-PC Software, XCAD (McArdle & Higgins, 1995), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEX (McArdle, 1995).
We have been interested for some time in the synthesis of compounds with multiple tetrazole fragments (Bethel et al., 1999; Bhandari et al., 1999; Butler et al., 1992; Butler & Fleming, 1997; Butler & NíBhrádaigh, 1994). One of us (RNB) has succeeded in generating tetratetrazole macrocyles of general formula (I) which include an apparent cavity of variable dimensions tailored by both the length and flexibility of the bridging groups X and Y (Butler & NíBhrádaigh, 1994; Butler et al., 1992; Butler & Fleming, 1997). Such macrocycles represent an extension of other work which has led to the isolation of polyazole macrocycles containing pyrazole (Tarrago et al., 1988) and triazole (Gal et al., 1985; Cabezon et al., 1995).
The structure of diorthobenzenotetra(5',2'-tetrazolo)[5'-(2)–2'-(6)]cyclophane [(I), X = 1,2-C6H4, Y = (CH2)6] is now reported (Fig. 1). The molecule is centrosymmetric about the inversion centre at 1/2, 1/2, 1/2, which is intrinsic in the space-group symmetry. Of central importance is the rectangular nature of the macrocyle cavity, which measures ca 11.228 (3) (C14—N5') by 5.678 (4) Å (C8—C8'), which is the first structure of a macrocycle containing four sub-tetrazole rings surrounding such a feature. Cyclophanes with two tetrazole rings have been reported (Ried & Aboul-Fetouh, 1988; Ried et al., 1989; Bethel et al., 1999), but such systems do not constitute a cavity. The central void depicted in Fig. 1 is more apparent than real, as a space-filling representation (Fig. 2) illustrates. While there is clearly a void channel running parallel to, and between, the (CH2)6 chains, the orientations of the potentially coordinating tetrazole units are orthogonal to this channel. Much smaller voids are evident between pairs of tetrazoles attached to the same C6H4 unit (Fig. 2), though nitrogen lone pairs from each heterocycle are approximately at right angles to each other (see below) and are not oriented for concerted metal-ion complexation.
Of the two unique tetrazoles, one is essentially coplanar with the phenyl group to which it is attached (torsion angle between ring planes 9.58°), while the other is approximately orthogonal (torsion angle 97.51°). This allows symmetry-related pairs of tetrazoles to adopt cofacial orientations with respect to each other across opposite sides of the rectangle. In other structures containing tetrazoles bonded at the ortho positions of a six-membered aromatic system, the two heterocycles are also found to be twisted with respect to the central ring (Bethel at al., 1999). In one case, 2-(1,2)benzo-1(5,1),3(5,2)-bistetrazolocyclodecaphane, the twist angles (7.7 and 85.6°) are very similar to those found in the title compound (Ried & Aboul-Fetouh, 1988). Overall the macrocyle exists in a chair conformation with the -(CH2)6– linkages adopting a surprisingly rigid linear conformation (Fig. 1). Such a structure has been predicted by energy minimization calculations for the more rigid analogue of the title compound, (I) (X = 1,3-C6H4, Y = 1,4-C6H4), but was not anticipated for the title compound (Butler & Fleming, 1997).