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The title compound is a salt, 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2
11,14]triaconta-1(26),11(29),12,14(30),24,27-hexaene–3,5-dinitrobenzoic acid–methanol (1/4/2), C
24H
42N
64+·4C
7H
3N
2O
6−·2CH
4O, in which the cation lies across a centre of inversion and one of the two independent anions is positionally disordered over two sets of atom sites having equal occupancy. The components are linked by four types of N—H
O hydrogen bond [N
O 2.674 (2)–2.815 (2) Å; N—H
O 149–163°] and one type of O—H
O hydrogen bond in which the acceptor is disordered over two closely adjacent sites [O
O 2.67 (4) and 2.75 (4) Å; O—H
O 172 and 173°], forming centrosymmetric seven-component aggregates.
Supporting information
CCDC reference: 158265
The macrocycle (I) was prepared using published procedures (Chen & Martell,
1991; Comba et al., 1996). The macrocycle, and 3,5-dinitrobenzoic acid,
were separately dissolved in methanol, and then these solutions were mixed to
give a molar ratio of macrocycle to acid of 1:2; the mixture was then set
aside to crystallize, producing analytically pure (1). Analysis: found C 49.0,
H 4.7, N 15.0%; C54H62N14O26 requires C 49.0, H 4.7, N 14.8%. Crystals
suitable for single-crystal X-ray diffraction were selected directly from the
analytical sample.
Compound (1) crystallized in the monoclinic system; space group
C2/c or Cc from the systematic absences;
C2/c was assumed. It soon became apparent from peaks in
difference maps and ellipsoid shapes that one of the dinitrobenzoic acid
molecules was either slightly disordered in its volume element, or that the
space group should be Cc and not C2/c. As subsequent
refinement in Cc led to unsatisfactory ellipsoid shapes and geometry
details for many of the atoms, this approach was abandoned and refinement
continued in C2/c. The disorder was carefully modelled using
planar hexagons for the benzene rings and using the SAME command in the
SHELXL97 refinement to ensure that both components of the disorder had
similar geometries; the atoms of the disordered molecule are O31—C37 and
O41—C47. Refining the disordered model with tied occupancy factors led to
values of 0.54 (3) and 0.46 (3), not significantly different from equal
occupancy; in the final cycles the occcupancies of the disordered atoms were
fixed at 0.5. A l l H atoms involved in hydrogen bonding were clearly revealed
in difference maps; all H atoms were treated as riding atoms with C—H 0.95
to 0.99 Å, N—H 0.92 Å, O—H 0.84 Å. Examination of the structure with
PLATON (Spek, 2000) showed that there were no solvent-accessible voids
in the crystal lattice.
Data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 (Gabe et al., 1989) and SHELXL97 (Sheldrick, 1997); molecular graphics: NRCVAX96, ORTEP (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
3,6,9,16,19,22-Hexa-azatricyclo[22.2.2.2
11,14]triconta-
1(26),11 (29),12,14 (30),24,27-hexaene–3,5-dinitrobenzoic acid–methanol
(1/4/2)
top
Crystal data top
C24H42N64+·4C7H3N2O6−·2CH4O | F(000) = 2768 |
Mr = 1323.18 | Dx = 1.446 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.6342 (7) Å | Cell parameters from 19757 reflections |
b = 11.7501 (2) Å | θ = 2.6–30.0° |
c = 21.4967 (7) Å | µ = 0.12 mm−1 |
β = 102.397 (1)° | T = 150 K |
V = 6077.2 (3) Å3 | Block, colourless |
Z = 4 | 0.27 × 0.25 × 0.16 mm |
Data collection top
Kappa-CCD diffractometer | 8760 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 5934 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ scans and ω scans with κ offsets | θmax = 30.0°, θmin = 2.6° |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | h = 0→34 |
Tmin = 0.969, Tmax = 0.982 | k = 0→16 |
19757 measured reflections | l = −30→29 |
Refinement top
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)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0486P)2 + 5.3065P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
8760 reflections | Δρmax = 0.53 e Å−3 |
448 parameters | Δρmin = −0.43 e Å−3 |
54 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00067 (17) |
Crystal data top
C24H42N64+·4C7H3N2O6−·2CH4O | V = 6077.2 (3) Å3 |
Mr = 1323.18 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.6342 (7) Å | µ = 0.12 mm−1 |
b = 11.7501 (2) Å | T = 150 K |
c = 21.4967 (7) Å | 0.27 × 0.25 × 0.16 mm |
β = 102.397 (1)° | |
Data collection top
Kappa-CCD diffractometer | 8760 independent reflections |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | 5934 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.982 | Rint = 0.026 |
19757 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 54 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.53 e Å−3 |
8760 reflections | Δρmin = −0.43 e Å−3 |
448 parameters | |
Special details top
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm
[Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891]which effectively
corrects for absorption effects. High redundancy data were used in the scaling
program hence the 'multi-scan' code word was used. No transmission
coefficients are available from the program (only scale factors for each
frame). The scale factors in the experimental table are calculated from the
'size' command in the SHELXL97 input file. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N8 | 0.17482 (5) | 0.36466 (11) | −0.19969 (6) | 0.0214 (3) | |
N11 | 0.08358 (6) | 0.44525 (12) | −0.15244 (6) | 0.0250 (3) | |
N14 | 0.09545 (5) | 0.37158 (11) | −0.01941 (6) | 0.0203 (3) | |
C1 | 0.35895 (7) | 0.18968 (15) | −0.09224 (7) | 0.0261 (3) | |
C2 | 0.35723 (7) | 0.30757 (15) | −0.09678 (9) | 0.0331 (4) | |
C3 | 0.31457 (7) | 0.36108 (15) | −0.13908 (9) | 0.0319 (4) | |
C4 | 0.27285 (7) | 0.29795 (14) | −0.17799 (8) | 0.0257 (3) | |
C5 | 0.27454 (7) | 0.18024 (15) | −0.17328 (8) | 0.0298 (4) | |
C6 | 0.31725 (7) | 0.12662 (15) | −0.13065 (8) | 0.0292 (4) | |
C7 | 0.22699 (7) | 0.35751 (16) | −0.22419 (8) | 0.0295 (4) | |
C9 | 0.13213 (7) | 0.43888 (14) | −0.24003 (8) | 0.0252 (3) | |
C10 | 0.07729 (7) | 0.42458 (15) | −0.22036 (8) | 0.0266 (3) | |
C12 | 0.03673 (6) | 0.40401 (14) | −0.12788 (8) | 0.0245 (3) | |
C13 | 0.04456 (6) | 0.42690 (13) | −0.05763 (7) | 0.0230 (3) | |
C15 | 0.09231 (7) | 0.36750 (16) | 0.04927 (8) | 0.0290 (4) | |
O21 | 0.21455 (5) | 0.50836 (11) | −0.10152 (6) | 0.0369 (3) | |
O22 | 0.18626 (5) | 0.50095 (10) | −0.00891 (6) | 0.0324 (3) | |
O23 | 0.30218 (7) | 0.67360 (18) | 0.17860 (7) | 0.0656 (5) | |
O24 | 0.37433 (6) | 0.77274 (12) | 0.17179 (7) | 0.0466 (4) | |
O25 | 0.41779 (6) | 0.83679 (13) | −0.03275 (8) | 0.0520 (4) | |
O26 | 0.35892 (8) | 0.78649 (18) | −0.11686 (8) | 0.0741 (6) | |
N23 | 0.33431 (7) | 0.71275 (14) | 0.14849 (8) | 0.0368 (4) | |
N25 | 0.37604 (7) | 0.78653 (13) | −0.05973 (9) | 0.0382 (4) | |
C21 | 0.26814 (6) | 0.60204 (13) | −0.01244 (8) | 0.0221 (3) | |
C22 | 0.27982 (7) | 0.61929 (13) | 0.05279 (8) | 0.0243 (3) | |
C23 | 0.32428 (7) | 0.68868 (14) | 0.08004 (8) | 0.0259 (3) | |
C24 | 0.35743 (7) | 0.74178 (14) | 0.04491 (9) | 0.0273 (4) | |
C25 | 0.34411 (7) | 0.72352 (14) | −0.02010 (8) | 0.0263 (3) | |
C26 | 0.30075 (7) | 0.65473 (13) | −0.04950 (8) | 0.0245 (3) | |
C27 | 0.21849 (7) | 0.52967 (13) | −0.04411 (8) | 0.0250 (3) | |
O51 | 0.13197 (6) | 0.17955 (13) | −0.07721 (8) | 0.0501 (4) | |
C52 | 0.18950 (8) | 0.18341 (17) | −0.05248 (10) | 0.0382 (4) | |
O31 | 0.109 (3) | 0.026 (5) | −0.1756 (11) | 0.046 (3) | 0.50 |
O32 | 0.125 (3) | 0.164 (4) | −0.242 (2) | 0.044 (3) | 0.50 |
O33 | −0.013 (2) | 0.176 (2) | −0.448 (2) | 0.042 (4) | 0.50 |
O34 | −0.0591 (16) | 0.024 (3) | −0.4835 (15) | 0.041 (4) | 0.50 |
O35 | −0.0132 (15) | −0.331 (2) | −0.3740 (12) | 0.0327 (9) | 0.50 |
O36 | 0.06511 (12) | −0.3411 (2) | −0.30487 (13) | 0.0400 (4) | 0.50 |
N33 | −0.0261 (8) | 0.0766 (17) | −0.4429 (7) | 0.0287 (19) | 0.50 |
N35 | 0.02760 (14) | −0.2873 (3) | −0.33845 (17) | 0.0262 (6) | 0.50 |
C31 | 0.0680 (3) | 0.0100 (5) | −0.2860 (4) | 0.0299 (4) | 0.50 |
C32 | 0.0360 (3) | 0.0721 (4) | −0.3357 (5) | 0.0201 (8) | 0.50 |
C33 | 0.0014 (3) | 0.0161 (7) | −0.3859 (4) | 0.0187 (9) | 0.50 |
C34 | −0.0012 (2) | −0.1021 (7) | −0.3865 (3) | 0.0295 (4) | 0.50 |
C35 | 0.0308 (2) | −0.1642 (4) | −0.3369 (3) | 0.0216 (8) | 0.50 |
C36 | 0.0654 (2) | −0.1082 (5) | −0.2866 (3) | 0.0245 (9) | 0.50 |
C37 | 0.1040 (12) | 0.072 (2) | −0.2289 (10) | 0.0325 (13) | 0.50 |
O41 | 0.106 (3) | 0.032 (5) | −0.1736 (11) | 0.046 (3) | 0.50 |
O42 | 0.121 (3) | 0.170 (4) | −0.240 (2) | 0.044 (3) | 0.50 |
O43 | −0.007 (2) | 0.176 (2) | −0.453 (2) | 0.042 (4) | 0.50 |
O44 | −0.0521 (16) | 0.023 (3) | −0.4874 (15) | 0.041 (4) | 0.50 |
O45 | −0.0109 (15) | −0.327 (2) | −0.3744 (12) | 0.0327 (9) | 0.50 |
O46 | 0.01862 (12) | −0.3199 (2) | −0.27186 (13) | 0.0400 (4) | 0.50 |
N43 | −0.0176 (8) | 0.0746 (17) | −0.4481 (7) | 0.0287 (19) | 0.50 |
N45 | 0.00775 (14) | −0.2750 (3) | −0.32428 (17) | 0.0262 (6) | 0.50 |
C41 | 0.0655 (3) | 0.0152 (6) | −0.2840 (4) | 0.0299 (4) | 0.50 |
C42 | 0.0458 (3) | 0.0714 (5) | −0.3414 (5) | 0.0201 (8) | 0.50 |
C43 | 0.0119 (3) | 0.0145 (7) | −0.3918 (4) | 0.0187 (9) | 0.50 |
C44 | −0.0024 (2) | −0.0985 (7) | −0.3849 (3) | 0.0295 (4) | 0.50 |
C45 | 0.0172 (2) | −0.1547 (4) | −0.3276 (3) | 0.0216 (8) | 0.50 |
C46 | 0.0512 (2) | −0.0978 (5) | −0.2771 (3) | 0.0245 (9) | 0.50 |
C47 | 0.1010 (12) | 0.078 (2) | −0.2269 (10) | 0.0325 (13) | 0.50 |
H8A | 0.1604 | 0.2927 | −0.1983 | 0.026* | |
H8B | 0.1830 | 0.3929 | −0.1588 | 0.026* | |
H11 | 0.0875 | 0.5222 | −0.1449 | 0.030* | |
H14A | 0.1264 | 0.4120 | −0.0238 | 0.024* | |
H14B | 0.0985 | 0.2989 | −0.0342 | 0.024* | |
H2 | 0.3855 | 0.3518 | −0.0707 | 0.040* | |
H3 | 0.3138 | 0.4418 | −0.1416 | 0.038* | |
H5 | 0.2463 | 0.1360 | −0.1994 | 0.036* | |
H6 | 0.3179 | 0.0459 | −0.1278 | 0.035* | |
H7A | 0.2393 | 0.4353 | −0.2322 | 0.035* | |
H7B | 0.2194 | 0.3159 | −0.2652 | 0.035* | |
H9A | 0.1279 | 0.4179 | −0.2854 | 0.030* | |
H9B | 0.1441 | 0.5194 | −0.2349 | 0.030* | |
H10A | 0.0498 | 0.4786 | −0.2446 | 0.032* | |
H10B | 0.0632 | 0.3464 | −0.2306 | 0.032* | |
H12A | 0.0324 | 0.3211 | −0.1357 | 0.029* | |
H12B | 0.0023 | 0.4419 | −0.1508 | 0.029* | |
H13A | 0.0471 | 0.5101 | −0.0503 | 0.028* | |
H13B | 0.0116 | 0.3987 | −0.0428 | 0.028* | |
H15A | 0.0579 | 0.3268 | 0.0529 | 0.035* | |
H15B | 0.0894 | 0.4463 | 0.0645 | 0.035* | |
H22 | 0.2577 | 0.5842 | 0.0786 | 0.029* | |
H24 | 0.3879 | 0.7885 | 0.0643 | 0.033* | |
H26 | 0.2933 | 0.6435 | −0.0943 | 0.029* | |
H51 | 0.1253 | 0.1371 | −0.1094 | 0.075* | |
H52A | 0.2017 | 0.2629 | −0.0477 | 0.057* | |
H52B | 0.2089 | 0.1443 | −0.0816 | 0.057* | |
H52C | 0.1981 | 0.1457 | −0.0108 | 0.057* | |
H32 | 0.0378 | 0.1529 | −0.3353 | 0.024* | 0.50 |
H34 | −0.0249 | −0.1404 | −0.4209 | 0.035* | 0.50 |
H36 | 0.0873 | −0.1507 | −0.2527 | 0.029* | 0.50 |
H42 | 0.0556 | 0.1486 | −0.3461 | 0.024* | 0.50 |
H44 | −0.0257 | −0.1374 | −0.4193 | 0.035* | 0.50 |
H46 | 0.0646 | −0.1362 | −0.2380 | 0.029* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N8 | 0.0219 (6) | 0.0219 (7) | 0.0190 (6) | −0.0018 (5) | 0.0014 (5) | −0.0007 (5) |
N11 | 0.0248 (7) | 0.0266 (7) | 0.0230 (7) | −0.0052 (5) | 0.0037 (5) | −0.0028 (5) |
N14 | 0.0182 (6) | 0.0211 (6) | 0.0215 (6) | −0.0012 (5) | 0.0036 (5) | 0.0003 (5) |
C1 | 0.0245 (8) | 0.0354 (9) | 0.0182 (8) | 0.0038 (7) | 0.0039 (6) | 0.0011 (6) |
C2 | 0.0276 (9) | 0.0343 (10) | 0.0326 (10) | −0.0016 (7) | −0.0040 (7) | −0.0040 (7) |
C3 | 0.0302 (9) | 0.0294 (9) | 0.0339 (10) | 0.0004 (7) | 0.0020 (7) | −0.0006 (7) |
C4 | 0.0224 (8) | 0.0339 (9) | 0.0215 (8) | 0.0035 (6) | 0.0065 (6) | 0.0027 (6) |
C5 | 0.0264 (8) | 0.0352 (10) | 0.0255 (9) | −0.0035 (7) | 0.0003 (7) | −0.0033 (7) |
C6 | 0.0311 (9) | 0.0286 (9) | 0.0270 (9) | 0.0004 (7) | 0.0043 (7) | 0.0005 (7) |
C7 | 0.0250 (8) | 0.0402 (10) | 0.0231 (8) | 0.0031 (7) | 0.0045 (7) | 0.0046 (7) |
C9 | 0.0262 (8) | 0.0270 (8) | 0.0206 (8) | 0.0037 (6) | 0.0011 (6) | 0.0038 (6) |
C10 | 0.0241 (8) | 0.0311 (9) | 0.0222 (8) | 0.0015 (6) | −0.0007 (6) | −0.0006 (6) |
C12 | 0.0207 (7) | 0.0253 (8) | 0.0252 (8) | −0.0016 (6) | −0.0002 (6) | 0.0017 (6) |
C13 | 0.0189 (7) | 0.0240 (8) | 0.0250 (8) | 0.0016 (6) | 0.0022 (6) | 0.0034 (6) |
C15 | 0.0245 (8) | 0.0405 (10) | 0.0220 (8) | 0.0061 (7) | 0.0054 (7) | 0.0021 (7) |
O21 | 0.0329 (7) | 0.0451 (8) | 0.0320 (7) | −0.0130 (6) | 0.0058 (6) | −0.0147 (6) |
O22 | 0.0266 (6) | 0.0358 (7) | 0.0342 (7) | −0.0118 (5) | 0.0053 (5) | −0.0014 (5) |
O23 | 0.0502 (10) | 0.1188 (15) | 0.0305 (8) | −0.0182 (10) | 0.0147 (7) | −0.0186 (9) |
O24 | 0.0514 (9) | 0.0411 (8) | 0.0365 (8) | −0.0043 (7) | −0.0145 (7) | −0.0078 (6) |
O25 | 0.0381 (8) | 0.0525 (9) | 0.0723 (11) | −0.0243 (7) | 0.0270 (8) | −0.0210 (8) |
O26 | 0.0772 (13) | 0.1034 (15) | 0.0424 (10) | −0.0467 (11) | 0.0142 (9) | 0.0126 (9) |
N23 | 0.0318 (8) | 0.0458 (9) | 0.0294 (8) | 0.0033 (7) | −0.0009 (7) | −0.0091 (7) |
N25 | 0.0337 (8) | 0.0343 (9) | 0.0507 (11) | −0.0116 (7) | 0.0178 (8) | −0.0046 (7) |
C21 | 0.0200 (7) | 0.0191 (7) | 0.0265 (8) | 0.0005 (6) | 0.0035 (6) | −0.0016 (6) |
C22 | 0.0227 (8) | 0.0238 (8) | 0.0262 (8) | −0.0002 (6) | 0.0047 (6) | −0.0005 (6) |
C23 | 0.0233 (8) | 0.0286 (9) | 0.0238 (8) | 0.0030 (6) | 0.0003 (6) | −0.0056 (6) |
C24 | 0.0191 (7) | 0.0249 (8) | 0.0361 (9) | −0.0008 (6) | 0.0019 (7) | −0.0080 (7) |
C25 | 0.0221 (8) | 0.0235 (8) | 0.0344 (9) | −0.0023 (6) | 0.0087 (7) | −0.0032 (7) |
C26 | 0.0244 (8) | 0.0226 (8) | 0.0265 (8) | −0.0002 (6) | 0.0056 (6) | −0.0033 (6) |
C27 | 0.0210 (7) | 0.0205 (8) | 0.0315 (9) | −0.0022 (6) | 0.0010 (7) | −0.0031 (6) |
O51 | 0.0355 (8) | 0.0545 (9) | 0.0554 (10) | 0.0090 (6) | −0.0009 (7) | −0.0278 (7) |
C52 | 0.0343 (10) | 0.0400 (11) | 0.0400 (11) | 0.0060 (8) | 0.0075 (8) | −0.0016 (8) |
O31 | 0.062 (6) | 0.037 (4) | 0.0313 (12) | −0.015 (4) | −0.004 (2) | −0.0024 (18) |
O32 | 0.056 (6) | 0.029 (3) | 0.043 (2) | −0.017 (4) | −0.001 (3) | −0.005 (2) |
O33 | 0.061 (8) | 0.0232 (7) | 0.040 (4) | 0.007 (2) | 0.007 (5) | 0.0064 (15) |
O34 | 0.043 (7) | 0.0387 (12) | 0.033 (3) | 0.009 (4) | −0.008 (4) | −0.0009 (19) |
O35 | 0.038 (2) | 0.0250 (14) | 0.0333 (7) | −0.0084 (11) | 0.0036 (10) | −0.0072 (9) |
O36 | 0.0535 (12) | 0.0242 (9) | 0.0373 (11) | −0.0017 (8) | −0.0015 (8) | 0.0064 (8) |
N33 | 0.033 (5) | 0.0257 (10) | 0.027 (2) | 0.011 (2) | 0.007 (2) | 0.0012 (15) |
N35 | 0.0334 (19) | 0.0210 (10) | 0.0239 (14) | −0.0011 (12) | 0.0055 (10) | −0.0010 (9) |
C31 | 0.0340 (10) | 0.0238 (10) | 0.0291 (10) | −0.0061 (8) | 0.0006 (8) | −0.0025 (7) |
C32 | 0.018 (3) | 0.0192 (8) | 0.0272 (17) | −0.0001 (9) | 0.0146 (15) | −0.0023 (7) |
C33 | 0.013 (3) | 0.0241 (9) | 0.0227 (15) | 0.0056 (13) | 0.0122 (13) | 0.0004 (9) |
C34 | 0.0322 (9) | 0.0265 (9) | 0.0265 (9) | −0.0043 (7) | −0.0008 (7) | −0.0006 (7) |
C35 | 0.022 (2) | 0.0189 (11) | 0.0248 (19) | −0.0018 (14) | 0.0079 (14) | −0.0034 (10) |
C36 | 0.024 (2) | 0.0257 (14) | 0.0233 (18) | −0.0016 (16) | 0.0050 (14) | −0.0006 (12) |
C37 | 0.036 (2) | 0.025 (2) | 0.0337 (13) | −0.0042 (18) | −0.0004 (14) | −0.0061 (10) |
O41 | 0.062 (6) | 0.037 (4) | 0.0313 (12) | −0.015 (4) | −0.004 (2) | −0.0024 (18) |
O42 | 0.056 (6) | 0.029 (3) | 0.043 (2) | −0.017 (4) | −0.001 (3) | −0.005 (2) |
O43 | 0.061 (8) | 0.0232 (7) | 0.040 (4) | 0.007 (2) | 0.007 (5) | 0.0064 (15) |
O44 | 0.043 (7) | 0.0387 (12) | 0.033 (3) | 0.009 (4) | −0.008 (4) | −0.0009 (19) |
O45 | 0.038 (2) | 0.0250 (14) | 0.0333 (7) | −0.0084 (11) | 0.0036 (10) | −0.0072 (9) |
O46 | 0.0535 (12) | 0.0242 (9) | 0.0373 (11) | −0.0017 (8) | −0.0015 (8) | 0.0064 (8) |
N43 | 0.033 (5) | 0.0257 (10) | 0.027 (2) | 0.011 (2) | 0.007 (2) | 0.0012 (15) |
N45 | 0.0334 (19) | 0.0210 (10) | 0.0239 (14) | −0.0011 (12) | 0.0055 (10) | −0.0010 (9) |
C41 | 0.0340 (10) | 0.0238 (10) | 0.0291 (10) | −0.0061 (8) | 0.0006 (8) | −0.0025 (7) |
C42 | 0.018 (3) | 0.0192 (8) | 0.0272 (17) | −0.0001 (9) | 0.0146 (15) | −0.0023 (7) |
C43 | 0.013 (3) | 0.0241 (9) | 0.0227 (15) | 0.0056 (13) | 0.0122 (13) | 0.0004 (9) |
C44 | 0.0322 (9) | 0.0265 (9) | 0.0265 (9) | −0.0043 (7) | −0.0008 (7) | −0.0006 (7) |
C45 | 0.022 (2) | 0.0189 (11) | 0.0248 (19) | −0.0018 (14) | 0.0079 (14) | −0.0034 (10) |
C46 | 0.024 (2) | 0.0257 (14) | 0.0233 (18) | −0.0016 (16) | 0.0050 (14) | −0.0006 (12) |
C47 | 0.036 (2) | 0.025 (2) | 0.0337 (13) | −0.0042 (18) | −0.0004 (14) | −0.0061 (10) |
Geometric parameters (Å, º) top
N8—C7 | 1.492 (2) | C22—C23 | 1.390 (2) |
N8—C9 | 1.492 (2) | C22—H22 | 0.95 |
N8—H8A | 0.92 | C23—C24 | 1.375 (2) |
N8—H8B | 0.92 | C24—C25 | 1.382 (2) |
N11—C10 | 1.455 (2) | C24—H24 | 0.95 |
N11—C12 | 1.452 (2) | C25—C26 | 1.380 (2) |
N11—H11 | 0.92 | C26—H26 | 0.95 |
N14—C13 | 1.492 (2) | O51—C52 | 1.404 (2) |
N14—C15 | 1.496 (2) | O51—H51 | 0.84 |
N14—H14A | 0.92 | C52—H52A | 0.98 |
N14—H14B | 0.92 | C52—H52B | 0.98 |
C1—C6 | 1.386 (2) | C52—H52C | 0.98 |
C1—C2 | 1.389 (3) | O31—C37 | 1.248 (10) |
C1—C15i | 1.507 (2) | O32—C37 | 1.248 (10) |
C2—C3 | 1.384 (2) | O33—N33 | 1.229 (10) |
C2—H2 | 0.95 | O34—N33 | 1.223 (10) |
C3—C4 | 1.392 (2) | O35—N35 | 1.235 (15) |
C3—H3 | 0.95 | O36—N35 | 1.220 (4) |
C4—C5 | 1.387 (2) | N33—C33 | 1.451 (8) |
C4—C7 | 1.507 (2) | N35—C35 | 1.448 (6) |
C5—C6 | 1.389 (2) | C31—C32 | 1.39 |
C5—H5 | 0.95 | C31—C36 | 1.39 |
C6—H6 | 0.95 | C31—C37 | 1.537 (9) |
C7—H7A | 0.99 | C32—C33 | 1.39 |
C7—H7B | 0.99 | C32—H32 | 0.95 |
C9—C10 | 1.509 (2) | C33—C34 | 1.39 |
C9—H9A | 0.99 | C34—C35 | 1.39 |
C9—H9B | 0.99 | C34—H34 | 0.95 |
C10—H10A | 0.99 | C35—C36 | 1.39 |
C10—H10B | 0.99 | C36—H36 | 0.95 |
C12—C13 | 1.505 (2) | O41—C47 | 1.248 (10) |
C12—H12A | 0.99 | O42—C47 | 1.248 (10) |
C12—H12B | 0.99 | O43—N43 | 1.227 (10) |
C13—H13A | 0.99 | O44—N43 | 1.225 (10) |
C13—H13B | 0.99 | O45—N45 | 1.235 (15) |
C15—C1i | 1.507 (2) | O46—N45 | 1.221 (4) |
C15—H15A | 0.99 | N43—C43 | 1.453 (8) |
C15—H15B | 0.99 | N45—C45 | 1.438 (6) |
O21—C27 | 1.242 (2) | C41—C42 | 1.39 |
O22—C27 | 1.255 (2) | C41—C46 | 1.39 |
O23—N23 | 1.215 (2) | C41—C47 | 1.537 (9) |
O24—N23 | 1.228 (2) | C42—C43 | 1.39 |
O25—N25 | 1.219 (2) | C42—H42 | 0.95 |
O26—N25 | 1.210 (2) | C43—C44 | 1.39 |
N23—C23 | 1.466 (2) | C44—C45 | 1.39 |
N25—C25 | 1.476 (2) | C44—H44 | 0.95 |
C21—C22 | 1.384 (2) | C45—C46 | 1.39 |
C21—C26 | 1.392 (2) | C46—H46 | 0.95 |
C21—C27 | 1.525 (2) | | |
| | | |
C9—N8—C7 | 112.37 (12) | C21—C22—C23 | 119.10 (15) |
C9—N8—H8A | 109.1 | C21—C22—H22 | 120.5 |
C7—N8—H8A | 109.1 | C23—C22—H22 | 120.5 |
C9—N8—H8B | 109.1 | C22—C23—C24 | 122.81 (15) |
C7—N8—H8B | 109.1 | C24—C23—N23 | 118.13 (15) |
H8A—N8—H8B | 107.9 | C22—C23—N23 | 118.94 (15) |
C12—N11—C10 | 112.80 (13) | C23—C24—C25 | 116.41 (15) |
C12—N11—H11 | 109.0 | C23—C24—H24 | 121.8 |
C10—N11—H11 | 109.0 | C25—C24—H24 | 121.8 |
C13—N14—C15 | 110.01 (12) | C24—C25—C26 | 123.13 (16) |
C13—N14—H14A | 109.7 | C26—C25—N25 | 119.04 (16) |
C15—N14—H14A | 109.7 | C24—C25—N25 | 117.73 (15) |
C13—N14—H14B | 109.7 | C25—C26—C21 | 118.91 (15) |
C15—N14—H14B | 109.7 | C25—C26—H26 | 120.5 |
H14A—N14—H14B | 108.2 | C21—C26—H26 | 120.5 |
C6—C1—C2 | 118.93 (15) | O21—C27—C21 | 116.11 (14) |
C6—C1—C15i | 121.18 (16) | O22—C27—C21 | 115.55 (15) |
C2—C1—C15i | 119.76 (15) | C52—O51—H51 | 109.5 |
C3—C2—C1 | 120.45 (16) | O51—C52—H52A | 109.5 |
C3—C2—H2 | 119.8 | O51—C52—H52B | 109.5 |
C1—C2—H2 | 119.8 | H52A—C52—H52B | 109.5 |
C2—C3—C4 | 120.75 (16) | O51—C52—H52C | 109.5 |
C2—C3—H3 | 119.6 | H52A—C52—H52C | 109.5 |
C4—C3—H3 | 119.6 | H52B—C52—H52C | 109.5 |
C5—C4—C3 | 118.74 (15) | O34—N33—O33 | 124.0 (16) |
C5—C4—C7 | 121.19 (15) | O34—N33—C33 | 118.4 (15) |
C3—C4—C7 | 120.07 (15) | O33—N33—C33 | 117.5 (15) |
C4—C5—C6 | 120.47 (16) | O36—N35—O35 | 124.3 (14) |
C4—C5—H5 | 119.8 | O36—N35—C35 | 118.3 (4) |
C6—C5—H5 | 119.8 | O35—N35—C35 | 117.4 (14) |
C1—C6—C5 | 120.66 (16) | C32—C31—C36 | 120 |
C1—C6—H6 | 119.7 | C32—C31—C37 | 119.9 (10) |
C5—C6—H6 | 119.7 | C36—C31—C37 | 120.0 (10) |
N8—C7—C4 | 111.96 (13) | C33—C32—C31 | 120 |
N8—C7—H7A | 109.2 | C33—C32—H32 | 120 |
C4—C7—H7A | 109.2 | C31—C32—H32 | 120 |
N8—C7—H7B | 109.2 | C32—C33—C34 | 120 |
C4—C7—H7B | 109.2 | C32—C33—N33 | 121.4 (9) |
H7A—C7—H7B | 107.9 | C34—C33—N33 | 118.0 (9) |
N8—C9—C10 | 109.49 (13) | C33—C34—C35 | 120 |
N8—C9—H9A | 109.8 | C33—C34—H34 | 120 |
C10—C9—H9A | 109.8 | C35—C34—H34 | 120 |
N8—C9—H9B | 109.8 | C36—C35—C34 | 120 |
C10—C9—H9B | 109.8 | C36—C35—N35 | 120.8 (4) |
H9A—C9—H9B | 108.2 | C34—C35—N35 | 119.2 (4) |
N11—C10—C9 | 110.71 (13) | C35—C36—C31 | 120 |
N11—C10—H10A | 109.5 | C35—C36—H36 | 120 |
C9—C10—H10A | 109.5 | C31—C36—H36 | 120 |
N11—C10—H10B | 109.5 | O32—C37—O31 | 127.6 (17) |
C9—C10—H10B | 109.5 | O32—C37—C31 | 115.4 (14) |
H10A—C10—H10B | 108.1 | O31—C37—C31 | 117.0 (14) |
N11—C12—C13 | 111.38 (13) | O44—N43—O43 | 123.7 (16) |
N11—C12—H12A | 109.4 | O44—N43—C43 | 118.7 (15) |
C13—C12—H12A | 109.4 | O43—N43—C43 | 117.6 (15) |
N11—C12—H12B | 109.4 | O46—N45—O45 | 124.1 (14) |
C13—C12—H12B | 109.4 | O46—N45—C45 | 117.7 (4) |
H12A—C12—H12B | 108.0 | O45—N45—C45 | 118.2 (14) |
N14—C13—C12 | 112.72 (13) | C42—C41—C46 | 120 |
N14—C13—H13A | 109.0 | C42—C41—C47 | 120.6 (10) |
C12—C13—H13A | 109.0 | C46—C41—C47 | 119.3 (10) |
N14—C13—H13B | 109.0 | C43—C42—C41 | 120 |
C12—C13—H13B | 109.0 | C43—C42—H42 | 120 |
H13A—C13—H13B | 107.8 | C41—C42—H42 | 120 |
N14—C15—C1i | 114.59 (13) | C42—C43—C44 | 120 |
N14—C15—H15A | 108.6 | C42—C43—N43 | 121.7 (9) |
C1i—C15—H15A | 108.6 | C44—C43—N43 | 117.4 (9) |
N14—C15—H15B | 108.6 | C45—C44—C43 | 120 |
C1i—C15—H15B | 108.6 | C45—C44—H44 | 120 |
H15A—C15—H15B | 107.6 | C43—C44—H44 | 120 |
O21—C27—O22 | 128.32 (15) | C46—C45—C44 | 120 |
O23—N23—O24 | 123.89 (17) | C46—C45—N45 | 120.8 (5) |
O23—N23—C23 | 118.22 (15) | C44—C45—N45 | 118.8 (4) |
O24—N23—C23 | 117.89 (16) | C45—C46—C41 | 120 |
O25—N25—O26 | 123.88 (17) | C45—C46—H46 | 120 |
O26—N25—C25 | 118.21 (15) | C41—C46—H46 | 120 |
O25—N25—C25 | 117.90 (17) | O42—C47—O41 | 127.6 (17) |
C22—C21—C26 | 119.64 (14) | O42—C47—C41 | 115.5 (14) |
C22—C21—C27 | 120.41 (14) | O41—C47—C41 | 116.8 (14) |
C26—C21—C27 | 119.90 (14) | | |
| | | |
C6—C1—C2—C3 | −0.1 (3) | C31—C32—C33—C34 | 0.0 |
C15i—C1—C2—C3 | 175.82 (16) | C31—C32—C33—N33 | −170.6 (9) |
C1—C2—C3—C4 | −0.3 (3) | O34—N33—C33—C32 | −175 (3) |
C2—C3—C4—C5 | 0.5 (3) | O33—N33—C33—C32 | 8 (3) |
C2—C3—C4—C7 | −179.46 (17) | O33—N33—C33—C34 | −162 (3) |
C3—C4—C5—C6 | −0.2 (3) | O34—N33—C33—C34 | 14 (3) |
C7—C4—C5—C6 | 179.69 (16) | C32—C33—C34—C35 | 0.0 |
C2—C1—C6—C5 | 0.3 (3) | N33—C33—C34—C35 | 170.9 (9) |
C15i—C1—C6—C5 | −175.52 (16) | C33—C34—C35—C36 | 0.0 |
C4—C5—C6—C1 | −0.2 (3) | C33—C34—C35—N35 | −179.8 (4) |
C3—C4—C7—N8 | −100.88 (18) | O36—N35—C35—C36 | −18.5 (5) |
C4—C7—N8—C9 | 171.03 (14) | O35—N35—C35—C36 | 161 (2) |
C5—C4—C7—N8 | 79.2 (2) | O35—N35—C35—C34 | −19 (2) |
C7—N8—C9—C10 | 169.19 (13) | O36—N35—C35—C34 | 161.3 (3) |
N8—C9—C10—N11 | 54.38 (17) | C34—C35—C36—C31 | 0.0 |
C9—C10—N11—C12 | −164.64 (13) | N35—C35—C36—C31 | 179.8 (4) |
C10—N11—C12—C13 | −179.92 (13) | C32—C31—C36—C35 | 0.0 |
N11—C12—C13—N14 | −59.59 (17) | C37—C31—C36—C35 | 176.9 (15) |
C12—C13—N14—C15 | −163.25 (13) | C32—C31—C37—O31 | 145 (4) |
C13—N14—C15—C1i | 178.45 (14) | C32—C31—C37—O32 | −35 (4) |
N14—C15—C1i—C2i | −81.8 (2) | C36—C31—C37—O32 | 149 (4) |
C26—C21—C22—C23 | −0.4 (2) | C36—C31—C37—O31 | −32 (4) |
C27—C21—C22—C23 | −177.91 (14) | C46—C41—C42—C43 | 0.0 |
C21—C22—C23—C24 | 0.2 (2) | C47—C41—C42—C43 | −177.3 (15) |
C21—C22—C23—N23 | 176.06 (14) | C41—C42—C43—C44 | 0.0 |
O23—N23—C23—C24 | 173.9 (2) | C41—C42—C43—N43 | 168.8 (9) |
O24—N23—C23—C24 | −5.1 (2) | O44—N43—C43—C42 | −171 (3) |
O23—N23—C23—C22 | −2.2 (3) | O43—N43—C43—C42 | 8 (3) |
O24—N23—C23—C22 | 178.84 (16) | O43—N43—C43—C44 | 177 (3) |
C22—C23—C24—C25 | 0.5 (2) | O44—N43—C43—C44 | −2 (3) |
N23—C23—C24—C25 | −175.39 (14) | C42—C43—C44—C45 | 0.0 |
C23—C24—C25—C26 | −1.1 (2) | N43—C43—C44—C45 | −169.2 (9) |
C23—C24—C25—N25 | 175.21 (15) | C43—C44—C45—C46 | 0.0 |
O26—N25—C25—C26 | 8.8 (3) | C43—C44—C45—N45 | −172.1 (3) |
O25—N25—C25—C26 | −172.14 (16) | O46—N45—C45—C46 | 17.5 (5) |
O25—N25—C25—C24 | 11.4 (2) | O45—N45—C45—C46 | −163 (2) |
O26—N25—C25—C24 | −167.7 (2) | O45—N45—C45—C44 | 9 (2) |
C24—C25—C26—C21 | 0.9 (2) | O46—N45—C45—C44 | −170.4 (3) |
N25—C25—C26—C21 | −175.32 (14) | C44—C45—C46—C41 | 0.0 |
C22—C21—C26—C25 | −0.2 (2) | N45—C45—C46—C41 | 172.0 (3) |
C27—C21—C26—C25 | 177.40 (14) | C42—C41—C46—C45 | 0.0 |
C22—C21—C27—O21 | −172.4 (2) | C47—C41—C46—C45 | 177.4 (15) |
C26—C21—C27—O21 | 10.0 (2) | C42—C41—C47—O41 | 163 (4) |
C22—C21—C27—O22 | 8.8 (2) | C42—C41—C47—O42 | −17 (4) |
C26—C21—C27—O22 | −168.78 (15) | C46—C41—C47—O42 | 166 (4) |
C36—C31—C32—C33 | 0.0 | C46—C41—C47—O41 | −14 (4) |
C37—C31—C32—C33 | −176.9 (15) | | |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8A···O32 | 0.92 | 1.89 | 2.72 (5) | 149 |
N8—H8A···O42 | 0.92 | 1.86 | 2.69 (5) | 150 |
N8—H8B···O21 | 0.92 | 1.88 | 2.716 (2) | 149 |
N14—H14A···O22 | 0.92 | 1.78 | 2.674 (2) | 163 |
N14—H14B···O51 | 0.92 | 1.96 | 2.815 (2) | 155 |
O51—H51···O31 | 0.84 | 1.91 | 2.75 (4) | 173 |
O51—H51···O41 | 0.84 | 1.84 | 2.67 (4) | 172 |
C36—H36···O24i | 0.95 | 2.30 | 3.234 (6) | 169 |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
Experimental details
Crystal data |
Chemical formula | C24H42N64+·4C7H3N2O6−·2CH4O |
Mr | 1323.18 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 24.6342 (7), 11.7501 (2), 21.4967 (7) |
β (°) | 102.397 (1) |
V (Å3) | 6077.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.27 × 0.25 × 0.16 |
|
Data collection |
Diffractometer | Kappa-CCD diffractometer |
Absorption correction | Multi-scan DENZO-SMN (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.969, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19757, 8760, 5934 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.137, 1.04 |
No. of reflections | 8760 |
No. of parameters | 448 |
No. of restraints | 54 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.43 |
Selected geometric parameters (Å, º) topN8—C7 | 1.492 (2) | O23—N23 | 1.215 (2) |
N8—C9 | 1.492 (2) | O24—N23 | 1.228 (2) |
N11—C10 | 1.455 (2) | O25—N25 | 1.219 (2) |
N11—C12 | 1.452 (2) | O26—N25 | 1.210 (2) |
N14—C13 | 1.492 (2) | N23—C23 | 1.466 (2) |
N14—C15 | 1.496 (2) | N25—C25 | 1.476 (2) |
O21—C27 | 1.242 (2) | O51—C52 | 1.404 (2) |
O22—C27 | 1.255 (2) | | |
| | | |
O21—C27—O22 | 128.32 (15) | C22—C21—C26 | 119.64 (14) |
O23—N23—O24 | 123.89 (17) | C22—C23—C24 | 122.81 (15) |
O25—N25—O26 | 123.88 (17) | C24—C25—C26 | 123.13 (16) |
| | | |
C3—C4—C7—N8 | −100.88 (18) | C22—C21—C27—O21 | −172.4 (2) |
C4—C7—N8—C9 | 171.03 (14) | C22—C21—C27—O22 | 8.8 (2) |
C7—N8—C9—C10 | 169.19 (13) | O33—N33—C33—C34 | −162 (3) |
N8—C9—C10—N11 | 54.38 (17) | O34—N33—C33—C34 | 14 (3) |
C9—C10—N11—C12 | −164.64 (13) | O35—N35—C35—C34 | −19 (2) |
C10—N11—C12—C13 | −179.92 (13) | O36—N35—C35—C34 | 161.3 (3) |
N11—C12—C13—N14 | −59.59 (17) | C32—C31—C37—O31 | 145 (4) |
C12—C13—N14—C15 | −163.25 (13) | C32—C31—C37—O32 | −35 (4) |
C13—N14—C15—C1i | 178.45 (14) | O43—N43—C43—C44 | 177 (3) |
N14—C15—C1i—C2i | −81.8 (2) | O44—N43—C43—C44 | −2 (3) |
O23—N23—C23—C24 | 173.9 (2) | O45—N45—C45—C44 | 9 (2) |
O24—N23—C23—C24 | −5.1 (2) | O46—N45—C45—C44 | −170.4 (3) |
O25—N25—C25—C24 | 11.4 (2) | C42—C41—C47—O41 | 163 (4) |
O26—N25—C25—C24 | −167.7 (2) | C42—C41—C47—O42 | −17 (4) |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8A···O32 | 0.92 | 1.89 | 2.72 (5) | 149 |
N8—H8A···O42 | 0.92 | 1.86 | 2.69 (5) | 150 |
N8—H8B···O21 | 0.92 | 1.88 | 2.716 (2) | 149 |
N14—H14A···O22 | 0.92 | 1.78 | 2.674 (2) | 163 |
N14—H14B···O51 | 0.92 | 1.96 | 2.815 (2) | 155 |
O51—H51···O31 | 0.84 | 1.91 | 2.75 (4) | 173 |
O51—H51···O41 | 0.84 | 1.84 | 2.67 (4) | 172 |
C36—H36···O24i | 0.95 | 2.30 | 3.234 (6) | 169 |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
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The salt-type adducts formed between the hexa-aza macrocycle (I) (C24H38N6) and the bisphenols 4,4'-sulfonyldiphenol and 4,4'-biphenol are characterized by three salient features: proton transfer leads to formation of the dication (II), C24H40N62+, in which only the central N atoms of the aliphatic chain are protonated; the cation (II) is centrosymmetric, but can adopt a range of widely-different conformations having rather similar energies and, indeed, two different cation conformations co-exist in each of these adducts giving a total of four distinct conformers overall; and extensive hydrogen bonding links the components into continuous arrays, which are two-dimensional in the 4,4'-sulfonyldiphenol adduct and three-dimensional in the adduct with 4,4'-biphenol (Glidewell et al., 2000). \sch
Extending our study of the macrocycle (I) we have now characterized a methanol-solvated adduct (1) formed with 3,5-dinitrobenzoic acid, which differs from the bisphenol adducts in all material respects. The title compound is a salt C24H42N64+·4(O2N)2C6H3COO-·2CH3OH: the cation lies across a centre of inversion in C2/c, chosen for the sake of convenience as that at (1/4, 1/4, 0). The two independent anions lie in general positions, and one of them is positionally disordered over two sets of sites having equal occupancy (see experimental section): the unique methanol also lies in a general position. Because the coordinates of corresponding atoms in the two sets of sites defining the disordered anion are extremely similar, apart from one of the nitro groups (containing N35/N45), only one orientation of the anion need be considered in the structure description: in particular, the hydrogen-bonding characteristics of the alternative atom sites O31/O41 and O32/O42 are very similar (Table 2). The H atoms are all ordered such that the cation is protonated at the four N atoms adjacent to the p-xylenyl units (III): this pattern of protonation differs from that observed previously in bisphenol adducts, but it is entirely consistent with the behaviour of the macrocycle (I) in aqueous solution. In those conditions, the macrocycle exhibits four protonation constants in the range 7.9 < log K < 8.7, with two others in the range 2.9 < log K < 3.9: the two weakly basic N atoms were assigned as the central pair in the aliphatic chains, and this assignment was supported by studies of the 13C chemical shifts as a function of pH (Clifford, 1997).
In the aliphatic portion of the centrosymmetric cation [C24H42N6]4+ there is almost perfect staggering about all of the C—C and C—N bonds, with the antiperiplanar (ap) torsional angles all within 18° of 180°, and the synclinal (sc) torsional angles both within 6° of ±60° (Table 1, Fig. 1). However, this conformation differs markedly from the four conformers previously observed for the cation C24H40N62+: in particular, the eight torsional angles in the aliphatic chain from C7 to C15 exhibit the pattern ap, ap, sc, ap, ap, sc, ap, ap so that the overall conformation is close to C2 h (2/m) symmetry. Most of the observed conformers of (II) have only Ci symmetry: the one conformer which is close to C2 h symmetry exhibits a pattern of torsional angles in the aliphatic chain different from that observed here, namely ap, sc, sc, ap, ap, sc, sc, ap. A necessary condition for near C2 h symmetry is that the pattern of torsional angles from C7 to N11 is repeated from C15 to N11 but with opposite signs for the corresponding angles in the two domains.
Within the cation there is a clear difference between the C—N bond lengths involving protonated and unprotonated N atoms (Table 1): the observed ranges here are very similar to those for the corresponding types of bond in the cation (II). For comparison, the mean values for C—N bonds of the general types (C*)2-NH and (C*)2-NH2+ are 1.469 Å and 1.494 Å, respectively (Allen et al., 1987). The trigonally trisubstituted anion carries three formally similar substituents: however, there is no orientation disorder resulting from this, and the two types of –XO2 substituent (X = C, N) are readily distinguished in terms of the X—O and exocyclic C—X distances (Table 1). It is noteworthy that for the anion without positional disorder, the interior C—C—C angles ipso to the substituents provide clear evidence for the strong electron withdrawing behaviour of the –NO2 substituent, while –CO2- appears to be neither an electron donor nor an electron acceptor (Domenicano & Murray-Rust, 1979). Also noteworthy is the fact that only the carboxylate O atoms are effective acceptors in N—H···O hydrogen bonds. The degree of twist of the substituents out of the plane of the adjacent aryl ring varies between near planarity for the N43 nitro group to 35 (4)° for the C37 carboxylate group: no clear pattern is evident.
The tetra-protonated cation (III) contains ten N—H bonds, and its skeletal conformation means that there are no intramolecular N—H···N hydrogen bonds. Rather, there are five N—H bonds on each face potentially available for intermolecular hydrogen-bond formation (Table 2), but the unprotonated N11 acts neither as hydrogen-bond donor nor as hydrogen-bond acceptor. On one face of the macrocycle N8 and N14 act as donors (via H8B and H14A) to O21 and O22, respectively, forming paired N—H···O hydrogen bonds reminiscent of those formed between the dication of the tetra-aza macrocycle meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (tet-a) and aromatic carboxylate anions (Lough et al., 2000). On the opposite face, N8 (via H8A) again acts as a donor to a carboxylate O, in this case O32 in the second independent anion, but N14 is a donor (via H14B) to the methanol O51, which in turn acts as a donor (via H51) to O31, the other carboxylate O in the same anion. Thus, on one face an R22(12) motif is formed, while on the other an R33(14) ring is present. By means of these two cyclic motifs, four molecular components are linked together: since the cation lies across a centre of inversion, the entire molecular aggregate contains no fewer than seven components: one cation, four anions, and two neutral methanol molecules. The composition of one aggregate thus provides a precise microcosm of the overall stoichiometry of the adduct (1). The only significant C—H···O hydrogen bond in the structure (Table 2) lies within this aggregate: C36 in one of the anions acts as donor to nitro-group O24 in the other anion on the same face of the macrocycle.
The isomeric cation (IV) in the salt C24H42N64+·H2P2O72-·2Br-·5.2H2O has neither crystallographic nor even approximate symmetry, but all ten of the N—H bonds participate in the hydrogen bonding: seven N—H···O hydrogen bonds are formed to three different diphosphate cations, two N—H···O hydrogen bonds are formed to water molecules, and there is an N—H···Br hydrogen bond (Nation et al., 1996).
There are four of the seven-component aggregates in each unit cell, but there are no significant hydrogen bonds between them. There are, however, weak π···π stacking interactions leading to linking of the aggregates along the [010] direction. Anions containing O21 at (x, y, z) and (0.5 - x, 1.5 - y, -z) are components of the supramolecular aggregate centred at (1/4, 1.25, 0) and these anions exhibit aromatic π···π stacking interactions: the perpendicular distance between the ring planes is 3.291 (4) Å and the centroid offset is 1.257 (4) Å. Four of these [010] stacks run through each unit cell.