7,16-Dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, C
26H
38N
2O
4, (I), crystallizes in space group
P2
1/
c, with two independent molecules adopting different conformations. The `free' crowns adopt a typical `parallelogram' shape, in which two methylene groups are turned inward toward the center of the ring and the benzyl groups splay out from the ring. In 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane bis(tetrafluoroborate) monohydrate, C
26H
40N
2O
42+·2BF
4−·H
2O, (II), the macrocycle is centrosymmetric, and the protonated N atoms adopt an
endo–
endo orientation that is stabilized by a bifurcated N—H
O hydrogen bond, where the O atoms of the macrocycle act as hydrogen-bond acceptors. The phenyl groups of the benzyl side arms are turned above and below the macrocycle; C—H
π interactions between the phenyl substituents and two macrocyclic methylene H atoms govern the overall conformation of the macrocycle. Bridging tetrafluoroborate anions link the macrocyclic cations
via weak C—H
F hydrogen bonds into channels running along [100], which are filled by the weakly hydrogen-bonded water molecules.
Supporting information
CCDC references: 268125; 268126
Compound (I) was prepared according to the procedure of Gustowski et al. (1987). To obtain complex (II), compound (I) (244 mg, 0.1 mmol) was dissolved in methanol (5 ml). The reaction mixture was allowed to stand until crystals were deposited. These were filtered off and dried from a 1:1 mixture of methanol and ethyl acetate to yield colourless transparent crystals (m.p. 441–443 K). Analysis calculated for C26H42B2F8N2O5: C 49.1, H 6.65, F 23.9, N 4.4%; found: C 49.0, H 6.7, F 23.9, N 4.4%.
All non-H atoms except O1W were refined with anisotropic displacement parameters. C-bound H atoms in (I) and in the [(I)H2]2+ ion in (II) were placed in calculated positions and treated using a riding model. The N-bound H atom was located in the difference Fourier map and refined [Uiso(H) = 1.5Ueq(N)]. After the refinement, the difference Fourier map revealed a peak of 0.8 e Å3. The reasonable O···F distances permit the conclusion that this is caused by a water molecule partially occupying the disordering position around an inversion center. The refined site occupancy is 0.102 (6). Because this value is so low, atom O1W was refined with an isotropic displacement parameter and its H atoms were not localized.
For both compounds, data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (I); ORTEP for Windows (Farrugia, 1997) for (II). For both compounds, software used to prepare material for publication: SHELXL97.
(I) 7,16-Dibenzyl-1,4,10,13-tetraoxo-7,16-diazacyclooctadecane
top
Crystal data top
C26H38N2O4 | F(000) = 1920 |
Mr = 442.58 | Dx = 1.183 Mg m−3 |
Monoclinic, P21/c | Melting point = 80–81 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 16.993 (3) Å | Cell parameters from 15860 reflections |
b = 22.455 (5) Å | θ = 1–27.5° |
c = 13.391 (3) Å | µ = 0.08 mm−1 |
β = 103.48 (3)° | T = 123 K |
V = 4968.9 (18) Å3 | Prism, colorless |
Z = 8 | 0.20 × 0.20 × 0.15 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 5565 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.060 |
Graphite monochromator | θmax = 25.0°, θmin = 1.5° |
ϕ and ω scans | h = −20→19 |
25950 measured reflections | k = −26→20 |
8591 independent reflections | l = −15→15 |
Refinement top
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)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0426P)2 + 2.1759P] where P = (Fo2 + 2Fc2)/3 |
8591 reflections | (Δ/σ)max < 0.001 |
577 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C26H38N2O4 | V = 4968.9 (18) Å3 |
Mr = 442.58 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.993 (3) Å | µ = 0.08 mm−1 |
b = 22.455 (5) Å | T = 123 K |
c = 13.391 (3) Å | 0.20 × 0.20 × 0.15 mm |
β = 103.48 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 5565 reflections with I > 2σ(I) |
25950 measured reflections | Rint = 0.060 |
8591 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.16 e Å−3 |
8591 reflections | Δρmin = −0.20 e Å−3 |
577 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.31647 (10) | 0.48690 (8) | 0.77816 (12) | 0.0295 (4) | |
O2A | 0.32949 (11) | 0.58759 (8) | 0.65103 (15) | 0.0341 (5) | |
O3A | 0.18061 (10) | 0.76219 (8) | 0.70437 (12) | 0.0299 (4) | |
O4A | 0.16561 (11) | 0.66046 (7) | 0.82920 (14) | 0.0327 (5) | |
N1A | 0.33722 (13) | 0.74940 (9) | 0.61298 (17) | 0.0321 (6) | |
N2A | 0.16319 (13) | 0.49944 (9) | 0.87585 (16) | 0.0280 (5) | |
C1A | 0.34281 (17) | 0.48398 (12) | 0.6852 (2) | 0.0333 (7) | |
H1A | 0.2967 | 0.4789 | 0.6276 | 0.040* | |
H2A | 0.3787 | 0.4502 | 0.6869 | 0.040* | |
C2A | 0.38626 (17) | 0.54048 (12) | 0.6730 (2) | 0.0336 (7) | |
H3A | 0.4264 | 0.5491 | 0.7357 | 0.040* | |
H4A | 0.4138 | 0.5363 | 0.6176 | 0.040* | |
C3A | 0.36838 (17) | 0.64349 (12) | 0.6488 (2) | 0.0373 (7) | |
H5A | 0.4036 | 0.6421 | 0.6014 | 0.045* | |
H6A | 0.4008 | 0.6533 | 0.7165 | 0.045* | |
C4A | 0.30315 (17) | 0.68949 (12) | 0.6146 (2) | 0.0341 (7) | |
H7A | 0.2719 | 0.6795 | 0.5464 | 0.041* | |
H8A | 0.2669 | 0.6890 | 0.6608 | 0.041* | |
C5A | 0.27586 (17) | 0.79606 (11) | 0.6108 (2) | 0.0351 (7) | |
H9A | 0.2299 | 0.7879 | 0.5542 | 0.042* | |
H10A | 0.2986 | 0.8340 | 0.5972 | 0.042* | |
C6A | 0.24612 (16) | 0.80162 (12) | 0.7073 (2) | 0.0343 (7) | |
H11A | 0.2897 | 0.7924 | 0.7662 | 0.041* | |
H12A | 0.2288 | 0.8422 | 0.7146 | 0.041* | |
C7A | 0.15124 (17) | 0.76389 (12) | 0.7953 (2) | 0.0333 (7) | |
H13A | 0.1145 | 0.7972 | 0.7928 | 0.040* | |
H14A | 0.1959 | 0.7688 | 0.8548 | 0.040* | |
C8A | 0.10820 (16) | 0.70673 (11) | 0.8032 (2) | 0.0346 (7) | |
H15A | 0.0772 | 0.7101 | 0.8553 | 0.042* | |
H16A | 0.0710 | 0.6979 | 0.7381 | 0.042* | |
C9A | 0.12900 (17) | 0.60378 (12) | 0.8290 (2) | 0.0348 (7) | |
H17A | 0.1004 | 0.5931 | 0.7599 | 0.042* | |
H18A | 0.0906 | 0.6043 | 0.8724 | 0.042* | |
C10A | 0.19554 (16) | 0.55964 (11) | 0.8694 (2) | 0.0303 (7) | |
H19A | 0.2328 | 0.5590 | 0.8245 | 0.036* | |
H20A | 0.2254 | 0.5721 | 0.9370 | 0.036* | |
C11A | 0.22521 (16) | 0.45374 (11) | 0.8789 (2) | 0.0306 (7) | |
H21A | 0.2042 | 0.4158 | 0.8958 | 0.037* | |
H22A | 0.2719 | 0.4635 | 0.9334 | 0.037* | |
C12A | 0.25209 (16) | 0.44700 (12) | 0.7804 (2) | 0.0319 (7) | |
H23A | 0.2698 | 0.4064 | 0.7741 | 0.038* | |
H24A | 0.2070 | 0.4551 | 0.7227 | 0.038* | |
C13A | 0.37386 (18) | 0.75676 (12) | 0.5243 (2) | 0.0389 (8) | |
H25A | 0.3313 | 0.7576 | 0.4618 | 0.047* | |
H26A | 0.4082 | 0.7227 | 0.5204 | 0.047* | |
C14A | 0.42324 (16) | 0.81264 (11) | 0.53063 (19) | 0.0267 (6) | |
C15A | 0.49294 (17) | 0.81931 (12) | 0.6077 (2) | 0.0322 (7) | |
H27A | 0.5097 | 0.7887 | 0.6547 | 0.039* | |
C16A | 0.53764 (17) | 0.87124 (13) | 0.6151 (2) | 0.0380 (8) | |
H28A | 0.5844 | 0.8753 | 0.6670 | 0.046* | |
C17A | 0.5139 (2) | 0.91669 (13) | 0.5469 (3) | 0.0438 (8) | |
H29A | 0.5442 | 0.9515 | 0.5525 | 0.053* | |
C18A | 0.4449 (2) | 0.91071 (12) | 0.4699 (2) | 0.0420 (8) | |
H30A | 0.4284 | 0.9416 | 0.4235 | 0.050* | |
C19A | 0.39999 (17) | 0.85903 (12) | 0.4616 (2) | 0.0342 (7) | |
H31A | 0.3536 | 0.8552 | 0.4091 | 0.041* | |
C20A | 0.12965 (17) | 0.49423 (12) | 0.9676 (2) | 0.0338 (7) | |
H32A | 0.0965 | 0.5289 | 0.9717 | 0.041* | |
H33A | 0.1738 | 0.4939 | 1.0284 | 0.041* | |
C21A | 0.07939 (16) | 0.43893 (11) | 0.96698 (19) | 0.0260 (6) | |
C22A | 0.00916 (17) | 0.43062 (12) | 0.8919 (2) | 0.0320 (7) | |
H34A | −0.0075 | 0.4598 | 0.8422 | 0.038* | |
C23A | −0.03653 (18) | 0.37957 (13) | 0.8894 (2) | 0.0399 (8) | |
H35A | −0.0834 | 0.3746 | 0.8380 | 0.048* | |
C24A | −0.01325 (19) | 0.33641 (13) | 0.9621 (2) | 0.0417 (8) | |
H36A | −0.0440 | 0.3020 | 0.9602 | 0.050* | |
C37A | 0.0558 (2) | 0.34403 (13) | 1.0382 (2) | 0.0424 (8) | |
H37A | 0.0717 | 0.3149 | 1.0882 | 0.051* | |
C26A | 0.10168 (17) | 0.39512 (12) | 1.0404 (2) | 0.0317 (7) | |
H38A | 0.1483 | 0.4000 | 1.0922 | 0.038* | |
O1B | 0.31633 (10) | −0.04976 (8) | 0.77152 (13) | 0.0316 (5) | |
O2B | 0.34062 (11) | 0.06650 (8) | 0.67021 (14) | 0.0341 (5) | |
O3B | 0.18303 (10) | 0.29611 (8) | 0.74470 (13) | 0.0340 (5) | |
O4B | 0.16241 (11) | 0.18223 (8) | 0.85237 (14) | 0.0349 (5) | |
N1B | 0.34427 (13) | 0.22939 (9) | 0.64219 (15) | 0.0266 (5) | |
N2B | 0.15719 (13) | 0.01904 (9) | 0.87505 (16) | 0.0282 (5) | |
C1B | 0.34946 (16) | −0.03975 (11) | 0.6848 (2) | 0.0303 (7) | |
H1B | 0.3059 | −0.0397 | 0.6233 | 0.036* | |
H2B | 0.3856 | −0.0723 | 0.6790 | 0.036* | |
C2B | 0.39509 (16) | 0.01783 (11) | 0.6902 (2) | 0.0321 (7) | |
H3B | 0.4306 | 0.0222 | 0.7579 | 0.039* | |
H4B | 0.4282 | 0.0174 | 0.6402 | 0.039* | |
C3B | 0.37977 (16) | 0.12274 (11) | 0.6762 (2) | 0.0321 (7) | |
H5B | 0.4190 | 0.1230 | 0.6340 | 0.038* | |
H6B | 0.4075 | 0.1314 | 0.7466 | 0.038* | |
C4B | 0.31436 (16) | 0.16795 (11) | 0.6378 (2) | 0.0298 (7) | |
H7B | 0.2879 | 0.1585 | 0.5673 | 0.036* | |
H8B | 0.2742 | 0.1651 | 0.6785 | 0.036* | |
C5B | 0.27805 (16) | 0.27076 (11) | 0.64653 (19) | 0.0280 (6) | |
H9B | 0.2294 | 0.2586 | 0.5971 | 0.034* | |
H10B | 0.2923 | 0.3105 | 0.6283 | 0.034* | |
C6B | 0.26169 (15) | 0.27190 (11) | 0.75257 (19) | 0.0283 (6) | |
H11B | 0.2645 | 0.2319 | 0.7804 | 0.034* | |
H12B | 0.3019 | 0.2962 | 0.7980 | 0.034* | |
C7B | 0.15266 (16) | 0.28830 (11) | 0.83403 (19) | 0.0288 (6) | |
H13B | 0.1164 | 0.3210 | 0.8388 | 0.035* | |
H14B | 0.1975 | 0.2900 | 0.8940 | 0.035* | |
C8B | 0.10843 (16) | 0.23088 (11) | 0.8354 (2) | 0.0316 (7) | |
H15B | 0.0789 | 0.2321 | 0.8892 | 0.038* | |
H16B | 0.0696 | 0.2257 | 0.7703 | 0.038* | |
C9B | 0.12264 (17) | 0.12622 (11) | 0.8498 (2) | 0.0345 (7) | |
H17B | 0.0918 | 0.1176 | 0.7808 | 0.041* | |
H18B | 0.0859 | 0.1266 | 0.8955 | 0.041* | |
C10B | 0.18743 (17) | 0.08028 (11) | 0.8840 (2) | 0.0330 (7) | |
H19B | 0.2274 | 0.0844 | 0.8433 | 0.040* | |
H20B | 0.2143 | 0.0879 | 0.9551 | 0.040* | |
C11B | 0.22341 (16) | −0.02259 (12) | 0.8707 (2) | 0.0301 (7) | |
H21B | 0.2088 | −0.0624 | 0.8880 | 0.036* | |
H22B | 0.2720 | −0.0108 | 0.9206 | 0.036* | |
C12B | 0.23962 (15) | −0.02274 (11) | 0.76498 (19) | 0.0271 (6) | |
H23B | 0.1978 | −0.0449 | 0.7180 | 0.032* | |
H24B | 0.2398 | 0.0177 | 0.7396 | 0.032* | |
C13B | 0.37679 (17) | 0.24093 (12) | 0.5514 (2) | 0.0327 (7) | |
H25B | 0.3324 | 0.2404 | 0.4908 | 0.039* | |
H26B | 0.4134 | 0.2089 | 0.5445 | 0.039* | |
C14B | 0.42119 (16) | 0.29933 (11) | 0.55467 (19) | 0.0263 (6) | |
C15B | 0.49579 (17) | 0.30769 (12) | 0.6218 (2) | 0.0313 (7) | |
H27B | 0.5181 | 0.2774 | 0.6671 | 0.038* | |
C16B | 0.53716 (17) | 0.36054 (13) | 0.6221 (2) | 0.0383 (8) | |
H28B | 0.5875 | 0.3655 | 0.6669 | 0.046* | |
C17B | 0.5046 (2) | 0.40571 (13) | 0.5572 (2) | 0.0424 (8) | |
H29B | 0.5324 | 0.4415 | 0.5587 | 0.051* | |
C18B | 0.4305 (2) | 0.39830 (13) | 0.4892 (2) | 0.0406 (8) | |
H30B | 0.4085 | 0.4288 | 0.4444 | 0.049* | |
C19B | 0.38929 (18) | 0.34512 (12) | 0.4882 (2) | 0.0349 (7) | |
H31B | 0.3395 | 0.3400 | 0.4423 | 0.042* | |
C20B | 0.12090 (17) | 0.00511 (12) | 0.9621 (2) | 0.0347 (7) | |
H32B | 0.0828 | 0.0363 | 0.9680 | 0.042* | |
H33B | 0.1632 | 0.0051 | 1.0248 | 0.042* | |
C21B | 0.07784 (16) | −0.05376 (11) | 0.95276 (19) | 0.0246 (6) | |
C22B | 0.00526 (16) | −0.06144 (12) | 0.88114 (19) | 0.0282 (7) | |
H34B | −0.0167 | −0.0299 | 0.8386 | 0.034* | |
C23B | −0.03493 (18) | −0.11533 (13) | 0.8722 (2) | 0.0349 (7) | |
H35B | −0.0834 | −0.1199 | 0.8234 | 0.042* | |
C24B | −0.00373 (18) | −0.16211 (13) | 0.9349 (2) | 0.0378 (8) | |
H36B | −0.0312 | −0.1983 | 0.9289 | 0.045* | |
C25B | 0.06828 (19) | −0.15542 (12) | 1.0066 (2) | 0.0398 (8) | |
H37B | 0.0899 | −0.1871 | 1.0488 | 0.048* | |
C26B | 0.10844 (17) | −0.10137 (12) | 1.0157 (2) | 0.0319 (7) | |
H38B | 0.1567 | −0.0969 | 1.0649 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0285 (11) | 0.0324 (11) | 0.0302 (10) | −0.0029 (8) | 0.0122 (9) | −0.0012 (8) |
O2A | 0.0271 (11) | 0.0247 (12) | 0.0526 (12) | 0.0022 (8) | 0.0139 (9) | 0.0049 (9) |
O3A | 0.0286 (11) | 0.0313 (11) | 0.0334 (11) | −0.0064 (8) | 0.0148 (9) | −0.0012 (8) |
O4A | 0.0293 (11) | 0.0213 (11) | 0.0491 (12) | 0.0018 (8) | 0.0122 (9) | 0.0052 (8) |
N1A | 0.0352 (14) | 0.0222 (14) | 0.0464 (15) | −0.0054 (10) | 0.0250 (12) | −0.0025 (10) |
N2A | 0.0318 (14) | 0.0212 (13) | 0.0363 (13) | −0.0021 (10) | 0.0190 (11) | −0.0010 (9) |
C1A | 0.0399 (18) | 0.0329 (18) | 0.0324 (16) | 0.0089 (13) | 0.0191 (14) | 0.0021 (12) |
C2A | 0.0321 (17) | 0.0367 (19) | 0.0385 (17) | 0.0071 (13) | 0.0212 (14) | 0.0076 (13) |
C3A | 0.0354 (18) | 0.0326 (18) | 0.0473 (18) | −0.0045 (14) | 0.0162 (15) | 0.0036 (13) |
C4A | 0.0303 (17) | 0.0294 (17) | 0.0479 (18) | −0.0035 (13) | 0.0198 (14) | −0.0023 (13) |
C5A | 0.0383 (18) | 0.0226 (17) | 0.0506 (18) | −0.0056 (13) | 0.0231 (15) | 0.0026 (13) |
C6A | 0.0298 (17) | 0.0273 (17) | 0.0496 (18) | −0.0045 (12) | 0.0170 (14) | −0.0062 (13) |
C7A | 0.0401 (18) | 0.0312 (18) | 0.0323 (16) | 0.0102 (13) | 0.0164 (14) | 0.0029 (12) |
C8A | 0.0313 (17) | 0.0324 (18) | 0.0468 (18) | 0.0117 (13) | 0.0225 (14) | 0.0106 (13) |
C9A | 0.0328 (18) | 0.0301 (18) | 0.0449 (18) | −0.0037 (13) | 0.0159 (14) | 0.0031 (13) |
C10A | 0.0304 (16) | 0.0252 (17) | 0.0395 (16) | −0.0033 (12) | 0.0167 (13) | 0.0004 (12) |
C11A | 0.0294 (16) | 0.0267 (17) | 0.0374 (16) | −0.0019 (12) | 0.0112 (13) | 0.0051 (12) |
C12A | 0.0325 (17) | 0.0236 (16) | 0.0421 (17) | −0.0025 (12) | 0.0139 (14) | −0.0037 (12) |
C13A | 0.043 (2) | 0.0356 (19) | 0.0456 (18) | −0.0100 (14) | 0.0264 (16) | −0.0092 (14) |
C14A | 0.0305 (17) | 0.0246 (16) | 0.0310 (16) | −0.0029 (12) | 0.0195 (14) | −0.0059 (12) |
C15A | 0.0399 (19) | 0.0278 (17) | 0.0316 (16) | 0.0049 (13) | 0.0139 (14) | −0.0012 (12) |
C16A | 0.0240 (17) | 0.044 (2) | 0.0491 (19) | −0.0028 (14) | 0.0153 (15) | −0.0161 (15) |
C17A | 0.047 (2) | 0.0290 (19) | 0.067 (2) | −0.0105 (15) | 0.0359 (19) | −0.0140 (16) |
C18A | 0.063 (2) | 0.0252 (18) | 0.049 (2) | 0.0051 (15) | 0.0361 (19) | 0.0072 (13) |
C19A | 0.0368 (18) | 0.0402 (19) | 0.0289 (16) | 0.0055 (14) | 0.0142 (14) | 0.0006 (13) |
C20A | 0.0422 (19) | 0.0288 (17) | 0.0356 (16) | −0.0120 (13) | 0.0196 (14) | −0.0072 (12) |
C21A | 0.0289 (17) | 0.0250 (16) | 0.0289 (15) | −0.0023 (12) | 0.0163 (13) | −0.0046 (12) |
C22A | 0.0330 (18) | 0.0321 (18) | 0.0346 (16) | 0.0045 (13) | 0.0151 (14) | −0.0004 (12) |
C23A | 0.0290 (18) | 0.045 (2) | 0.0471 (19) | −0.0066 (15) | 0.0124 (15) | −0.0198 (16) |
C24A | 0.048 (2) | 0.0286 (19) | 0.061 (2) | −0.0146 (15) | 0.0380 (18) | −0.0133 (15) |
C37A | 0.060 (2) | 0.0311 (19) | 0.0451 (19) | −0.0014 (15) | 0.0304 (18) | 0.0056 (14) |
C26A | 0.0328 (17) | 0.0338 (18) | 0.0310 (16) | −0.0025 (13) | 0.0124 (13) | −0.0011 (13) |
O1B | 0.0265 (11) | 0.0350 (12) | 0.0375 (11) | 0.0094 (8) | 0.0161 (9) | 0.0110 (8) |
O2B | 0.0299 (11) | 0.0190 (11) | 0.0568 (13) | −0.0029 (8) | 0.0167 (10) | 0.0003 (9) |
O3B | 0.0292 (11) | 0.0397 (12) | 0.0383 (11) | 0.0117 (9) | 0.0182 (9) | 0.0107 (9) |
O4B | 0.0286 (11) | 0.0245 (12) | 0.0562 (13) | −0.0006 (9) | 0.0193 (10) | −0.0002 (9) |
N1B | 0.0271 (13) | 0.0232 (13) | 0.0342 (13) | −0.0017 (10) | 0.0166 (11) | −0.0033 (9) |
N2B | 0.0266 (13) | 0.0236 (14) | 0.0408 (14) | −0.0056 (10) | 0.0207 (11) | −0.0035 (10) |
C1B | 0.0336 (17) | 0.0276 (17) | 0.0333 (16) | 0.0063 (12) | 0.0153 (14) | 0.0021 (12) |
C2B | 0.0302 (17) | 0.0300 (18) | 0.0396 (17) | 0.0046 (13) | 0.0154 (14) | 0.0013 (12) |
C3B | 0.0311 (17) | 0.0282 (18) | 0.0404 (17) | −0.0057 (13) | 0.0155 (14) | −0.0024 (13) |
C4B | 0.0277 (16) | 0.0266 (17) | 0.0383 (16) | −0.0030 (12) | 0.0141 (13) | −0.0037 (12) |
C5B | 0.0304 (16) | 0.0246 (16) | 0.0305 (15) | 0.0010 (12) | 0.0100 (13) | 0.0036 (11) |
C6B | 0.0252 (15) | 0.0238 (16) | 0.0382 (16) | 0.0017 (11) | 0.0121 (13) | 0.0021 (12) |
C7B | 0.0280 (16) | 0.0291 (17) | 0.0330 (15) | 0.0080 (12) | 0.0145 (13) | 0.0028 (12) |
C8B | 0.0258 (16) | 0.0319 (18) | 0.0402 (17) | 0.0039 (13) | 0.0138 (13) | −0.0010 (13) |
C9B | 0.0351 (17) | 0.0261 (18) | 0.0481 (18) | −0.0041 (13) | 0.0215 (14) | −0.0019 (13) |
C10B | 0.0337 (17) | 0.0238 (17) | 0.0468 (18) | −0.0052 (13) | 0.0202 (15) | −0.0020 (12) |
C11B | 0.0277 (16) | 0.0262 (17) | 0.0396 (17) | −0.0019 (12) | 0.0145 (13) | 0.0012 (12) |
C12B | 0.0202 (15) | 0.0258 (16) | 0.0370 (16) | 0.0013 (11) | 0.0102 (12) | 0.0004 (12) |
C13B | 0.0369 (18) | 0.0302 (17) | 0.0354 (16) | −0.0074 (13) | 0.0174 (14) | −0.0089 (12) |
C14B | 0.0297 (17) | 0.0269 (17) | 0.0280 (15) | −0.0013 (12) | 0.0188 (13) | −0.0054 (12) |
C15B | 0.0336 (18) | 0.0306 (18) | 0.0303 (16) | 0.0012 (13) | 0.0086 (14) | −0.0031 (12) |
C16B | 0.0277 (18) | 0.044 (2) | 0.0451 (18) | −0.0074 (14) | 0.0132 (14) | −0.0163 (15) |
C17B | 0.054 (2) | 0.0301 (19) | 0.055 (2) | −0.0169 (15) | 0.0370 (19) | −0.0135 (15) |
C18B | 0.059 (2) | 0.0320 (19) | 0.0358 (18) | 0.0064 (16) | 0.0223 (17) | 0.0065 (13) |
C19B | 0.0353 (18) | 0.0361 (19) | 0.0340 (16) | −0.0005 (14) | 0.0097 (14) | −0.0038 (13) |
C20B | 0.0382 (18) | 0.0317 (18) | 0.0400 (17) | −0.0079 (13) | 0.0208 (15) | −0.0083 (13) |
C21B | 0.0246 (16) | 0.0254 (16) | 0.0290 (15) | −0.0045 (12) | 0.0168 (13) | −0.0045 (12) |
C22B | 0.0294 (17) | 0.0294 (17) | 0.0293 (15) | 0.0024 (13) | 0.0141 (13) | −0.0003 (12) |
C23B | 0.0342 (19) | 0.037 (2) | 0.0357 (17) | −0.0058 (14) | 0.0129 (14) | −0.0139 (14) |
C24B | 0.042 (2) | 0.0283 (18) | 0.0500 (19) | −0.0122 (14) | 0.0250 (16) | −0.0100 (14) |
C25B | 0.053 (2) | 0.0278 (18) | 0.0450 (19) | 0.0034 (15) | 0.0247 (17) | 0.0093 (13) |
C26B | 0.0304 (17) | 0.0377 (19) | 0.0290 (16) | −0.0008 (13) | 0.0094 (13) | 0.0007 (13) |
Geometric parameters (Å, º) top
O1A—C1A | 1.419 (3) | O1B—C1B | 1.422 (3) |
O1A—C12A | 1.420 (3) | O1B—C12B | 1.422 (3) |
O2A—C2A | 1.416 (3) | O2B—C2B | 1.417 (3) |
O2A—C3A | 1.422 (3) | O2B—C3B | 1.421 (3) |
O3A—C6A | 1.416 (3) | O3B—C7B | 1.420 (3) |
O3A—C7A | 1.420 (3) | O3B—C6B | 1.424 (3) |
O4A—C8A | 1.412 (3) | O4B—C8B | 1.410 (3) |
O4A—C9A | 1.416 (3) | O4B—C9B | 1.424 (3) |
N1A—C4A | 1.467 (3) | N1B—C4B | 1.467 (3) |
N1A—C13A | 1.474 (3) | N1B—C5B | 1.471 (3) |
N1A—C5A | 1.474 (3) | N1B—C13B | 1.471 (3) |
N2A—C11A | 1.465 (3) | N2B—C10B | 1.463 (3) |
N2A—C10A | 1.469 (3) | N2B—C20B | 1.474 (3) |
N2A—C20A | 1.475 (3) | N2B—C11B | 1.475 (3) |
C1A—C2A | 1.496 (4) | C1B—C2B | 1.501 (4) |
C1A—H1A | 0.9700 | C1B—H1B | 0.9700 |
C1A—H2A | 0.9700 | C1B—H2B | 0.9700 |
C2A—H3A | 0.9700 | C2B—H3B | 0.9700 |
C2A—H4A | 0.9700 | C2B—H4B | 0.9700 |
C3A—C4A | 1.506 (4) | C3B—C4B | 1.505 (4) |
C3A—H5A | 0.9700 | C3B—H5B | 0.9700 |
C3A—H6A | 0.9700 | C3B—H6B | 0.9700 |
C4A—H7A | 0.9700 | C4B—H7B | 0.9700 |
C4A—H8A | 0.9700 | C4B—H8B | 0.9700 |
C5A—C6A | 1.499 (4) | C5B—C6B | 1.509 (3) |
C5A—H9A | 0.9700 | C5B—H9B | 0.9700 |
C5A—H10A | 0.9700 | C5B—H10B | 0.9700 |
C6A—H11A | 0.9700 | C6B—H11B | 0.9700 |
C6A—H12A | 0.9700 | C6B—H12B | 0.9700 |
C7A—C8A | 1.493 (4) | C7B—C8B | 1.494 (4) |
C7A—H13A | 0.9700 | C7B—H13B | 0.9700 |
C7A—H14A | 0.9700 | C7B—H14B | 0.9700 |
C8A—H15A | 0.9700 | C8B—H15B | 0.9700 |
C8A—H16A | 0.9700 | C8B—H16B | 0.9700 |
C9A—C10A | 1.506 (4) | C9B—C10B | 1.500 (4) |
C9A—H17A | 0.9700 | C9B—H17B | 0.9700 |
C9A—H18A | 0.9700 | C9B—H18B | 0.9700 |
C10A—H19A | 0.9700 | C10B—H19B | 0.9700 |
C10A—H20A | 0.9700 | C10B—H20B | 0.9700 |
C11A—C12A | 1.501 (3) | C11B—C12B | 1.504 (3) |
C11A—H21A | 0.9700 | C11B—H21B | 0.9700 |
C11A—H22A | 0.9700 | C11B—H22B | 0.9700 |
C12A—H23A | 0.9700 | C12B—H23B | 0.9700 |
C12A—H24A | 0.9700 | C12B—H24B | 0.9700 |
C13A—C14A | 1.501 (4) | C13B—C14B | 1.508 (4) |
C13A—H25A | 0.9700 | C13B—H25B | 0.9700 |
C13A—H26A | 0.9700 | C13B—H26B | 0.9700 |
C14A—C15A | 1.386 (4) | C14B—C19B | 1.385 (4) |
C14A—C19A | 1.387 (4) | C14B—C15B | 1.386 (4) |
C15A—C16A | 1.383 (4) | C15B—C16B | 1.379 (4) |
C15A—H27A | 0.9300 | C15B—H27B | 0.9300 |
C16A—C17A | 1.366 (4) | C16B—C17B | 1.366 (4) |
C16A—H28A | 0.9300 | C16B—H28B | 0.9300 |
C17A—C18A | 1.376 (4) | C17B—C18B | 1.381 (4) |
C17A—H29A | 0.9300 | C17B—H29B | 0.9300 |
C18A—C19A | 1.379 (4) | C18B—C19B | 1.383 (4) |
C18A—H30A | 0.9300 | C18B—H30B | 0.9300 |
C19A—H31A | 0.9300 | C19B—H31B | 0.9300 |
C20A—C21A | 1.506 (3) | C20B—C21B | 1.502 (4) |
C20A—H32A | 0.9700 | C20B—H32B | 0.9700 |
C20A—H33A | 0.9700 | C20B—H33B | 0.9700 |
C21A—C26A | 1.380 (4) | C21B—C22B | 1.385 (4) |
C21A—C22A | 1.383 (4) | C21B—C26B | 1.386 (4) |
C22A—C23A | 1.381 (4) | C22B—C23B | 1.381 (4) |
C22A—H34A | 0.9300 | C22B—H34B | 0.9300 |
C23A—C24A | 1.365 (4) | C23B—C24B | 1.372 (4) |
C23A—H35A | 0.9300 | C23B—H35B | 0.9300 |
C24A—C37A | 1.374 (4) | C24B—C25B | 1.377 (4) |
C24A—H36A | 0.9300 | C24B—H36B | 0.9300 |
C37A—C26A | 1.384 (4) | C25B—C26B | 1.384 (4) |
C37A—H37A | 0.9300 | C25B—H37B | 0.9300 |
C26A—H38A | 0.9300 | C26B—H38B | 0.9300 |
| | | |
C1A—O1A—C12A | 113.03 (19) | C1B—O1B—C12B | 114.46 (19) |
C2A—O2A—C3A | 111.5 (2) | C2B—O2B—C3B | 113.5 (2) |
C6A—O3A—C7A | 113.0 (2) | C7B—O3B—C6B | 114.19 (19) |
C8A—O4A—C9A | 112.5 (2) | C8B—O4B—C9B | 113.1 (2) |
C4A—N1A—C13A | 110.9 (2) | C4B—N1B—C5B | 109.5 (2) |
C4A—N1A—C5A | 111.9 (2) | C4B—N1B—C13B | 109.03 (19) |
C13A—N1A—C5A | 109.5 (2) | C5B—N1B—C13B | 111.1 (2) |
C11A—N2A—C10A | 111.7 (2) | C10B—N2B—C20B | 109.8 (2) |
C11A—N2A—C20A | 109.7 (2) | C10B—N2B—C11B | 110.0 (2) |
C10A—N2A—C20A | 110.15 (19) | C20B—N2B—C11B | 111.1 (2) |
O1A—C1A—C2A | 108.7 (2) | O1B—C1B—C2B | 113.3 (2) |
O1A—C1A—H1A | 109.9 | O1B—C1B—H1B | 108.9 |
C2A—C1A—H1A | 109.9 | C2B—C1B—H1B | 108.9 |
O1A—C1A—H2A | 109.9 | O1B—C1B—H2B | 108.9 |
C2A—C1A—H2A | 109.9 | C2B—C1B—H2B | 108.9 |
H1A—C1A—H2A | 108.3 | H1B—C1B—H2B | 107.7 |
O2A—C2A—C1A | 109.1 (2) | O2B—C2B—C1B | 110.4 (2) |
O2A—C2A—H3A | 109.9 | O2B—C2B—H3B | 109.6 |
C1A—C2A—H3A | 109.9 | C1B—C2B—H3B | 109.6 |
O2A—C2A—H4A | 109.9 | O2B—C2B—H4B | 109.6 |
C1A—C2A—H4A | 109.9 | C1B—C2B—H4B | 109.6 |
H3A—C2A—H4A | 108.3 | H3B—C2B—H4B | 108.1 |
O2A—C3A—C4A | 107.4 (2) | O2B—C3B—C4B | 106.3 (2) |
O2A—C3A—H5A | 110.2 | O2B—C3B—H5B | 110.5 |
C4A—C3A—H5A | 110.2 | C4B—C3B—H5B | 110.5 |
O2A—C3A—H6A | 110.2 | O2B—C3B—H6B | 110.5 |
C4A—C3A—H6A | 110.2 | C4B—C3B—H6B | 110.5 |
H5A—C3A—H6A | 108.5 | H5B—C3B—H6B | 108.7 |
N1A—C4A—C3A | 111.6 (2) | N1B—C4B—C3B | 113.5 (2) |
N1A—C4A—H7A | 109.3 | N1B—C4B—H7B | 108.9 |
C3A—C4A—H7A | 109.3 | C3B—C4B—H7B | 108.9 |
N1A—C4A—H8A | 109.3 | N1B—C4B—H8B | 108.9 |
C3A—C4A—H8A | 109.3 | C3B—C4B—H8B | 108.9 |
H7A—C4A—H8A | 108.0 | H7B—C4B—H8B | 107.7 |
N1A—C5A—C6A | 114.9 (2) | N1B—C5B—C6B | 111.0 (2) |
N1A—C5A—H9A | 108.5 | N1B—C5B—H9B | 109.4 |
C6A—C5A—H9A | 108.5 | C6B—C5B—H9B | 109.4 |
N1A—C5A—H10A | 108.5 | N1B—C5B—H10B | 109.4 |
C6A—C5A—H10A | 108.5 | C6B—C5B—H10B | 109.4 |
H9A—C5A—H10A | 107.5 | H9B—C5B—H10B | 108.0 |
O3A—C6A—C5A | 110.2 (2) | O3B—C6B—C5B | 108.2 (2) |
O3A—C6A—H11A | 109.6 | O3B—C6B—H11B | 110.1 |
C5A—C6A—H11A | 109.6 | C5B—C6B—H11B | 110.1 |
O3A—C6A—H12A | 109.6 | O3B—C6B—H12B | 110.1 |
C5A—C6A—H12A | 109.6 | C5B—C6B—H12B | 110.1 |
H11A—C6A—H12A | 108.1 | H11B—C6B—H12B | 108.4 |
O3A—C7A—C8A | 108.2 (2) | O3B—C7B—C8B | 113.5 (2) |
O3A—C7A—H13A | 110.0 | O3B—C7B—H13B | 108.9 |
C8A—C7A—H13A | 110.1 | C8B—C7B—H13B | 108.9 |
O3A—C7A—H14A | 110.1 | O3B—C7B—H14B | 108.9 |
C8A—C7A—H14A | 110.1 | C8B—C7B—H14B | 108.9 |
H13A—C7A—H14A | 108.4 | H13B—C7B—H14B | 107.7 |
O4A—C8A—C7A | 109.2 (2) | O4B—C8B—C7B | 111.1 (2) |
O4A—C8A—H15A | 109.8 | O4B—C8B—H15B | 109.4 |
C7A—C8A—H15A | 109.8 | C7B—C8B—H15B | 109.4 |
O4A—C8A—H16A | 109.8 | O4B—C8B—H16B | 109.4 |
C7A—C8A—H16A | 109.8 | C7B—C8B—H16B | 109.4 |
H15A—C8A—H16A | 108.3 | H15B—C8B—H16B | 108.0 |
O4A—C9A—C10A | 107.3 (2) | O4B—C9B—C10B | 106.8 (2) |
O4A—C9A—H17A | 110.2 | O4B—C9B—H17B | 110.4 |
C10A—C9A—H17A | 110.2 | C10B—C9B—H17B | 110.4 |
O4A—C9A—H18A | 110.2 | O4B—C9B—H18B | 110.4 |
C10A—C9A—H18A | 110.2 | C10B—C9B—H18B | 110.4 |
H17A—C9A—H18A | 108.5 | H17B—C9B—H18B | 108.6 |
N2A—C10A—C9A | 111.5 (2) | N2B—C10B—C9B | 113.7 (2) |
N2A—C10A—H19A | 109.3 | N2B—C10B—H19B | 108.8 |
C9A—C10A—H19A | 109.3 | C9B—C10B—H19B | 108.8 |
N2A—C10A—H20A | 109.3 | N2B—C10B—H20B | 108.8 |
C9A—C10A—H20A | 109.3 | C9B—C10B—H20B | 108.8 |
H19A—C10A—H20A | 108.0 | H19B—C10B—H20B | 107.7 |
N2A—C11A—C12A | 114.3 (2) | N2B—C11B—C12B | 110.3 (2) |
N2A—C11A—H21A | 108.7 | N2B—C11B—H21B | 109.6 |
C12A—C11A—H21A | 108.7 | C12B—C11B—H21B | 109.6 |
N2A—C11A—H22A | 108.7 | N2B—C11B—H22B | 109.6 |
C12A—C11A—H22A | 108.7 | C12B—C11B—H22B | 109.6 |
H21A—C11A—H22A | 107.6 | H21B—C11B—H22B | 108.1 |
O1A—C12A—C11A | 110.4 (2) | O1B—C12B—C11B | 108.0 (2) |
O1A—C12A—H23A | 109.6 | O1B—C12B—H23B | 110.1 |
C11A—C12A—H23A | 109.6 | C11B—C12B—H23B | 110.1 |
O1A—C12A—H24A | 109.6 | O1B—C12B—H24B | 110.1 |
C11A—C12A—H24A | 109.6 | C11B—C12B—H24B | 110.1 |
H23A—C12A—H24A | 108.1 | H23B—C12B—H24B | 108.4 |
N1A—C13A—C14A | 112.6 (2) | N1B—C13B—C14B | 114.2 (2) |
N1A—C13A—H25A | 109.1 | N1B—C13B—H25B | 108.7 |
C14A—C13A—H25A | 109.1 | C14B—C13B—H25B | 108.7 |
N1A—C13A—H26A | 109.1 | N1B—C13B—H26B | 108.7 |
C14A—C13A—H26A | 109.1 | C14B—C13B—H26B | 108.7 |
H25A—C13A—H26A | 107.8 | H25B—C13B—H26B | 107.6 |
C15A—C14A—C19A | 118.4 (3) | C19B—C14B—C15B | 118.6 (3) |
C15A—C14A—C13A | 120.1 (2) | C19B—C14B—C13B | 120.6 (3) |
C19A—C14A—C13A | 121.4 (3) | C15B—C14B—C13B | 120.8 (2) |
C16A—C15A—C14A | 120.3 (3) | C16B—C15B—C14B | 120.5 (3) |
C16A—C15A—H27A | 119.9 | C16B—C15B—H27B | 119.8 |
C14A—C15A—H27A | 119.9 | C14B—C15B—H27B | 119.8 |
C17A—C16A—C15A | 120.7 (3) | C17B—C16B—C15B | 120.4 (3) |
C17A—C16A—H28A | 119.6 | C17B—C16B—H28B | 119.8 |
C15A—C16A—H28A | 119.6 | C15B—C16B—H28B | 119.8 |
C16A—C17A—C18A | 119.7 (3) | C16B—C17B—C18B | 120.1 (3) |
C16A—C17A—H29A | 120.2 | C16B—C17B—H29B | 119.9 |
C18A—C17A—H29A | 120.2 | C18B—C17B—H29B | 119.9 |
C17A—C18A—C19A | 120.1 (3) | C17B—C18B—C19B | 119.5 (3) |
C17A—C18A—H30A | 119.9 | C17B—C18B—H30B | 120.2 |
C19A—C18A—H30A | 119.9 | C19B—C18B—H30B | 120.2 |
C18A—C19A—C14A | 120.8 (3) | C18B—C19B—C14B | 120.9 (3) |
C18A—C19A—H31A | 119.6 | C18B—C19B—H31B | 119.6 |
C14A—C19A—H31A | 119.6 | C14B—C19B—H31B | 119.6 |
N2A—C20A—C21A | 112.9 (2) | N2B—C20B—C21B | 114.0 (2) |
N2A—C20A—H32A | 109.0 | N2B—C20B—H32B | 108.8 |
C21A—C20A—H32A | 109.0 | C21B—C20B—H32B | 108.8 |
N2A—C20A—H33A | 109.0 | N2B—C20B—H33B | 108.8 |
C21A—C20A—H33A | 109.0 | C21B—C20B—H33B | 108.8 |
H32A—C20A—H33A | 107.8 | H32B—C20B—H33B | 107.7 |
C26A—C21A—C22A | 118.0 (3) | C22B—C21B—C26B | 118.2 (2) |
C26A—C21A—C20A | 121.5 (3) | C22B—C21B—C20B | 120.3 (2) |
C22A—C21A—C20A | 120.5 (2) | C26B—C21B—C20B | 121.5 (3) |
C23A—C22A—C21A | 121.0 (3) | C23B—C22B—C21B | 120.8 (3) |
C23A—C22A—H34A | 119.5 | C23B—C22B—H34B | 119.6 |
C21A—C22A—H34A | 119.5 | C21B—C22B—H34B | 119.6 |
C24A—C23A—C22A | 120.3 (3) | C24B—C23B—C22B | 120.3 (3) |
C24A—C23A—H35A | 119.8 | C24B—C23B—H35B | 119.8 |
C22A—C23A—H35A | 119.8 | C22B—C23B—H35B | 119.8 |
C23A—C24A—C37A | 119.7 (3) | C23B—C24B—C25B | 119.8 (3) |
C23A—C24A—H36A | 120.1 | C23B—C24B—H36B | 120.1 |
C37A—C24A—H36A | 120.1 | C25B—C24B—H36B | 120.1 |
C24A—C37A—C26A | 119.9 (3) | C24B—C25B—C26B | 119.8 (3) |
C24A—C37A—H37A | 120.0 | C24B—C25B—H37B | 120.1 |
C26A—C37A—H37A | 120.0 | C26B—C25B—H37B | 120.1 |
C21A—C26A—C37A | 121.1 (3) | C25B—C26B—C21B | 121.0 (3) |
C21A—C26A—H38A | 119.5 | C25B—C26B—H38B | 119.5 |
C37A—C26A—H38A | 119.5 | C21B—C26B—H38B | 119.5 |
| | | |
O1A—C1A—C2A—O2A | −70.7 (3) | O1B—C1B—C2B—O2B | −74.7 (3) |
C1A—C2A—O2A—C3A | 174.2 (2) | C1B—C2B—O2B—C3B | 178.7 (2) |
C2A—O2A—C3A—C4A | 174.4 (2) | C2B—O2B—C3B—C4B | 171.7 (2) |
O2A—C3A—C4A—N1A | 178.1 (2) | O2B—C3B—C4B—N1B | 178.0 (2) |
C3A—C4A—N1A—C5A | −162.6 (2) | C3B—C4B—N1B—C5B | −156.1 (2) |
C4A—N1A—C5A—C6A | 68.6 (3) | C4B—N1B—C5B—C6B | 76.6 (3) |
N1A—C5A—C6A—O3A | −87.2 (3) | N1B—C5B—C6B—O3B | −161.3 (2) |
C5A—C6A—O3A—C7A | 178.1 (2) | C5B—C6B—O3B—C7B | 167.3 (2) |
C6A—O3A—C7A—C8A | −157.6 (2) | C6B—O3B—C7B—C8B | −88.1 (3) |
O3A—C7A—C8A—O4A | 72.4 (3) | O3B—C7B—C8B—O4B | 72.1 (3) |
C7A—C8A—O4A—C9A | −174.7 (2) | C7B—C8B—O4B—C9B | −177.4 (2) |
C8A—O4A—C9A—C10A | −173.6 (2) | C8B—O4B—C9B—C10B | −171.9 (2) |
O4A—C9A—C10A—N2A | 177.9 (2) | O4B—C9B—C10B—N2B | −173.7 (2) |
C9A—C10A—N2A—C11A | 159.7 (2) | C9B—C10B—N2B—C11B | 158.2 (2) |
C10A—N2A—C11A—C12A | −68.9 (3) | C10B—N2B—C11B—C12B | −78.4 (3) |
N2A—C11A—C12A—O1A | 87.8 (3) | N2B—C11B—C12B—O1B | 164.1 (2) |
C11A—C12A—O1A—C1A | −178.1 (2) | C11B—C12B—O1B—C1B | −164.7 (2) |
C12A—O1A—C1A—C2A | 159.1 (2) | C12B—O1B—C1B—C2B | 85.0 (3) |
(II)
N,
N'-dibenzyl-1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane bis tetrafluoroborate monohydrate
top
Crystal data top
C26H40N2O42+·2BF4−·H2O | Z = 1 |
Mr = 621.48 | F(000) = 326 |
Triclinic, P1 | Dx = 1.342 Mg m−3 |
Hall symbol: -P 1 | Melting point = 168–170 K |
a = 7.9290 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3870 (6) Å | Cell parameters from 3035 reflections |
c = 11.6070 (7) Å | θ = 1–27.5° |
α = 69.342 (4)° | µ = 0.12 mm−1 |
β = 72.226 (4)° | T = 123 K |
γ = 81.480 (4)° | Prism, colorless |
V = 768.98 (9) Å3 | 0.25 × 0.20 × 0.20 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2159 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ϕ and ω scans | h = −9→9 |
4974 measured reflections | k = −11→11 |
2660 independent reflections | l = −13→13 |
Refinement top
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0604P)2 + 0.1724P] where P = (Fo2 + 2Fc2)/3 |
2660 reflections | (Δ/σ)max = 0.002 |
198 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C26H40N2O42+·2BF4−·H2O | γ = 81.480 (4)° |
Mr = 621.48 | V = 768.98 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.9290 (6) Å | Mo Kα radiation |
b = 9.3870 (6) Å | µ = 0.12 mm−1 |
c = 11.6070 (7) Å | T = 123 K |
α = 69.342 (4)° | 0.25 × 0.20 × 0.20 mm |
β = 72.226 (4)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2159 reflections with I > 2σ(I) |
4974 measured reflections | Rint = 0.027 |
2660 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.18 e Å−3 |
2660 reflections | Δρmin = −0.25 e Å−3 |
198 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.63995 (18) | 0.00507 (14) | −0.26512 (13) | 0.0255 (3) | |
H1N | 0.599 (2) | −0.008 (2) | −0.1798 (19) | 0.038* | |
C2 | 0.3942 (2) | 0.13891 (18) | 0.28211 (16) | 0.0309 (4) | |
H2A | 0.3304 | 0.1384 | 0.3701 | 0.037* | |
H2B | 0.5226 | 0.1431 | 0.2705 | 0.037* | |
C3 | 0.3336 (2) | 0.27758 (18) | 0.18699 (15) | 0.0296 (4) | |
H3A | 0.2026 | 0.2854 | 0.2075 | 0.036* | |
H3B | 0.3753 | 0.3713 | 0.1882 | 0.036* | |
O4 | 0.40852 (15) | 0.25841 (12) | 0.06524 (10) | 0.0308 (3) | |
C5 | 0.3292 (2) | 0.36037 (18) | −0.03014 (15) | 0.0311 (4) | |
H5A | 0.3513 | 0.4670 | −0.0438 | 0.037* | |
H5B | 0.1994 | 0.3487 | −0.0019 | 0.037* | |
C6 | 0.4078 (2) | 0.32474 (18) | −0.15215 (16) | 0.0326 (4) | |
H6A | 0.3621 | 0.4001 | −0.2215 | 0.039* | |
H6B | 0.5384 | 0.3296 | −0.1774 | 0.039* | |
O7 | 0.36008 (15) | 0.17417 (12) | −0.13226 (10) | 0.0317 (3) | |
C8 | 0.3523 (2) | 0.1520 (2) | −0.24600 (16) | 0.0348 (4) | |
H8A | 0.2846 | 0.2389 | −0.2924 | 0.042* | |
H8B | 0.2891 | 0.0581 | −0.2227 | 0.042* | |
C9 | 0.5357 (2) | 0.13856 (18) | −0.33235 (15) | 0.0307 (4) | |
H9A | 0.5264 | 0.1253 | −0.4111 | 0.037* | |
H9B | 0.5981 | 0.2333 | −0.3575 | 0.037* | |
C10 | 0.8355 (2) | 0.03204 (17) | −0.30300 (15) | 0.0270 (4) | |
H10A | 0.9002 | −0.0650 | −0.2690 | 0.032* | |
H10B | 0.8808 | 0.0672 | −0.3975 | 0.032* | |
C11 | 0.8701 (2) | 0.14913 (17) | −0.25252 (14) | 0.0247 (4) | |
C12 | 0.9169 (2) | 0.29523 (18) | −0.33387 (15) | 0.0312 (4) | |
H12A | 0.9283 | 0.3218 | −0.4227 | 0.037* | |
C13 | 0.9470 (2) | 0.40214 (18) | −0.28615 (17) | 0.0347 (4) | |
H13A | 0.9785 | 0.5019 | −0.3421 | 0.042* | |
C14 | 0.9311 (2) | 0.36360 (19) | −0.15688 (17) | 0.0338 (4) | |
H14A | 0.9528 | 0.4367 | −0.1242 | 0.041* | |
C15 | 0.8839 (2) | 0.2191 (2) | −0.07526 (16) | 0.0338 (4) | |
H15A | 0.8720 | 0.1931 | 0.0136 | 0.041* | |
C16 | 0.8539 (2) | 0.11163 (18) | −0.12296 (15) | 0.0291 (4) | |
H16A | 0.8221 | 0.0120 | −0.0667 | 0.035* | |
B1 | 0.7890 (3) | 0.2304 (2) | 0.33341 (18) | 0.0291 (4) | |
F1 | 0.86572 (15) | 0.26613 (14) | 0.20294 (9) | 0.0513 (3) | |
F2 | 0.63511 (14) | 0.31951 (11) | 0.35620 (10) | 0.0448 (3) | |
F3 | 0.74774 (14) | 0.07671 (10) | 0.38617 (10) | 0.0418 (3) | |
F4 | 0.90924 (14) | 0.25270 (11) | 0.39029 (9) | 0.0382 (3) | |
O1W | 0.372 (2) | 0.4751 (17) | 0.5008 (14) | 0.064 (7)* | 0.102 (6) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0273 (8) | 0.0249 (7) | 0.0253 (7) | −0.0001 (6) | −0.0062 (6) | −0.0107 (6) |
C2 | 0.0332 (10) | 0.0306 (9) | 0.0347 (9) | −0.0047 (7) | −0.0096 (7) | −0.0161 (7) |
C3 | 0.0328 (10) | 0.0272 (8) | 0.0313 (9) | −0.0038 (7) | −0.0054 (7) | −0.0142 (7) |
O4 | 0.0301 (7) | 0.0311 (6) | 0.0287 (6) | 0.0047 (5) | −0.0054 (5) | −0.0114 (5) |
C5 | 0.0330 (10) | 0.0248 (8) | 0.0313 (9) | 0.0017 (7) | −0.0057 (7) | −0.0082 (7) |
C6 | 0.0358 (10) | 0.0240 (8) | 0.0316 (9) | −0.0006 (7) | −0.0040 (7) | −0.0063 (7) |
O7 | 0.0359 (7) | 0.0277 (6) | 0.0300 (6) | −0.0026 (5) | −0.0037 (5) | −0.0116 (5) |
C8 | 0.0328 (11) | 0.0394 (10) | 0.0359 (9) | 0.0048 (8) | −0.0111 (8) | −0.0177 (8) |
C9 | 0.0336 (10) | 0.0304 (9) | 0.0277 (9) | 0.0049 (7) | −0.0101 (7) | −0.0103 (7) |
C10 | 0.0244 (9) | 0.0257 (8) | 0.0302 (8) | −0.0008 (7) | −0.0028 (7) | −0.0123 (7) |
C11 | 0.0206 (9) | 0.0246 (8) | 0.0288 (8) | 0.0008 (6) | −0.0034 (6) | −0.0122 (7) |
C12 | 0.0343 (10) | 0.0285 (9) | 0.0288 (9) | −0.0021 (7) | −0.0046 (7) | −0.0102 (7) |
C13 | 0.0377 (11) | 0.0226 (8) | 0.0434 (10) | −0.0019 (7) | −0.0098 (8) | −0.0109 (7) |
C14 | 0.0304 (10) | 0.0331 (9) | 0.0473 (11) | 0.0046 (7) | −0.0130 (8) | −0.0247 (8) |
C15 | 0.0328 (10) | 0.0420 (10) | 0.0307 (9) | 0.0034 (8) | −0.0102 (7) | −0.0173 (8) |
C16 | 0.0270 (10) | 0.0270 (8) | 0.0310 (9) | −0.0013 (7) | −0.0057 (7) | −0.0084 (7) |
B1 | 0.0309 (11) | 0.0293 (10) | 0.0298 (10) | −0.0024 (8) | −0.0052 (8) | −0.0154 (8) |
F1 | 0.0532 (8) | 0.0721 (8) | 0.0283 (6) | 0.0016 (6) | −0.0084 (5) | −0.0203 (5) |
F2 | 0.0420 (7) | 0.0322 (6) | 0.0514 (6) | 0.0076 (5) | −0.0057 (5) | −0.0130 (5) |
F3 | 0.0384 (7) | 0.0283 (5) | 0.0654 (7) | −0.0016 (4) | −0.0191 (5) | −0.0190 (5) |
F4 | 0.0471 (7) | 0.0388 (6) | 0.0351 (5) | −0.0129 (5) | −0.0120 (5) | −0.0147 (4) |
Geometric parameters (Å, º) top
N1—C9 | 1.503 (2) | C8—H8B | 0.9900 |
N1—C2i | 1.506 (2) | C9—H9A | 0.9900 |
N1—C10 | 1.511 (2) | C9—H9B | 0.9900 |
N1—H1N | 0.911 (19) | C10—C11 | 1.506 (2) |
C2—C3 | 1.506 (2) | C10—H10A | 0.9900 |
C2—N1i | 1.506 (2) | C10—H10B | 0.9900 |
C2—H2A | 0.9900 | C11—C16 | 1.387 (2) |
C2—H2B | 0.9900 | C11—C12 | 1.390 (2) |
C3—O4 | 1.4204 (18) | C12—C13 | 1.384 (2) |
C3—H3A | 0.9900 | C12—H12A | 0.9500 |
C3—H3B | 0.9900 | C13—C14 | 1.383 (3) |
O4—C5 | 1.427 (2) | C13—H13A | 0.9500 |
C5—C6 | 1.497 (2) | C14—C15 | 1.380 (2) |
C5—H5A | 0.9900 | C14—H14A | 0.9500 |
C5—H5B | 0.9900 | C15—C16 | 1.388 (2) |
C6—O7 | 1.4384 (19) | C15—H15A | 0.9500 |
C6—H6A | 0.9900 | C16—H16A | 0.9500 |
C6—H6B | 0.9900 | B1—F2 | 1.384 (2) |
O7—C8 | 1.428 (2) | B1—F1 | 1.384 (2) |
C8—C9 | 1.510 (2) | B1—F4 | 1.389 (2) |
C8—H8A | 0.9900 | B1—F3 | 1.399 (2) |
| | | |
C9—N1—C2i | 110.74 (13) | H8A—C8—H8B | 108.0 |
C9—N1—C10 | 112.99 (12) | N1—C9—C8 | 110.48 (13) |
C2i—N1—C10 | 112.23 (12) | N1—C9—H9A | 109.6 |
C9—N1—H1N | 107.2 (12) | C8—C9—H9A | 109.6 |
C2i—N1—H1N | 106.6 (11) | N1—C9—H9B | 109.6 |
C10—N1—H1N | 106.7 (12) | C8—C9—H9B | 109.6 |
C3—C2—N1i | 110.96 (13) | H9A—C9—H9B | 108.1 |
C3—C2—H2A | 109.4 | C11—C10—N1 | 111.42 (12) |
N1i—C2—H2A | 109.4 | C11—C10—H10A | 109.3 |
C3—C2—H2B | 109.4 | N1—C10—H10A | 109.3 |
N1i—C2—H2B | 109.4 | C11—C10—H10B | 109.3 |
H2A—C2—H2B | 108.0 | N1—C10—H10B | 109.3 |
O4—C3—C2 | 106.18 (12) | H10A—C10—H10B | 108.0 |
O4—C3—H3A | 110.5 | C16—C11—C12 | 119.29 (15) |
C2—C3—H3A | 110.5 | C16—C11—C10 | 119.76 (14) |
O4—C3—H3B | 110.5 | C12—C11—C10 | 120.95 (14) |
C2—C3—H3B | 110.5 | C13—C12—C11 | 120.39 (15) |
H3A—C3—H3B | 108.7 | C13—C12—H12A | 119.8 |
C3—O4—C5 | 112.73 (12) | C11—C12—H12A | 119.8 |
O4—C5—C6 | 108.82 (13) | C14—C13—C12 | 119.93 (15) |
O4—C5—H5A | 109.9 | C14—C13—H13A | 120.0 |
C6—C5—H5A | 109.9 | C12—C13—H13A | 120.0 |
O4—C5—H5B | 109.9 | C15—C14—C13 | 120.12 (16) |
C6—C5—H5B | 109.9 | C15—C14—H14A | 119.9 |
H5A—C5—H5B | 108.3 | C13—C14—H14A | 119.9 |
O7—C6—C5 | 108.55 (13) | C14—C15—C16 | 120.04 (15) |
O7—C6—H6A | 110.0 | C14—C15—H15A | 120.0 |
C5—C6—H6A | 110.0 | C16—C15—H15A | 120.0 |
O7—C6—H6B | 110.0 | C11—C16—C15 | 120.23 (15) |
C5—C6—H6B | 110.0 | C11—C16—H16A | 119.9 |
H6A—C6—H6B | 108.4 | C15—C16—H16A | 119.9 |
C8—O7—C6 | 113.76 (12) | F2—B1—F1 | 109.83 (15) |
O7—C8—C9 | 111.22 (15) | F2—B1—F4 | 110.94 (14) |
O7—C8—H8A | 109.4 | F1—B1—F4 | 109.28 (15) |
C9—C8—H8A | 109.4 | F2—B1—F3 | 109.12 (14) |
O7—C8—H8B | 109.4 | F1—B1—F3 | 109.59 (14) |
C9—C8—H8B | 109.4 | F4—B1—F3 | 108.05 (15) |
| | | |
N1i—C2—C3—O4 | −50.1 (2) | C6—O7—C8—C9 | 74.0 (2) |
C2—C3—O4—C5 | 165.4 (1) | O7—C8—C9—N1 | 60.3 (2) |
C3—O4—C5—C6 | −176.2 (1) | C8—C9—N1—C2i | 86.8 (2) |
O4—C5—C6—O7 | 64.6 (2) | C9—N1—C2i—C3i | −164.0 (1) |
C5—C6—O7—C8 | 152.6 (1) | | |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4i | 0.91 (2) | 2.25 (2) | 2.709 (2) | 110.2 (14) |
N1—H1N···O7 | 0.91 (2) | 2.43 (2) | 2.901 (2) | 112.6 (14) |
C2—H2B···F3 | 0.99 | 2.43 | 3.278 (2) | 143 |
C10—H10B···F4ii | 0.99 | 2.43 | 3.345 (2) | 154 |
C12—H12A···F4ii | 0.95 | 2.53 | 3.383 (2) | 150 |
C13—H13A···F4iii | 0.95 | 2.41 | 3.279 (2) | 152 |
C15—H15A···F1 | 0.95 | 2.51 | 3.368 (2) | 151 |
C16—H16A···O7i | 0.95 | 2.52 | 3.395 (2) | 154 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y, z−1; (iii) −x+2, −y+1, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C26H38N2O4 | C26H40N2O42+·2BF4−·H2O |
Mr | 442.58 | 621.48 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 123 | 123 |
a, b, c (Å) | 16.993 (3), 22.455 (5), 13.391 (3) | 7.9290 (6), 9.3870 (6), 11.6070 (7) |
α, β, γ (°) | 90, 103.48 (3), 90 | 69.342 (4), 72.226 (4), 81.480 (4) |
V (Å3) | 4968.9 (18) | 768.98 (9) |
Z | 8 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.12 |
Crystal size (mm) | 0.20 × 0.20 × 0.15 | 0.25 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25950, 8591, 5565 | 4974, 2660, 2159 |
Rint | 0.060 | 0.027 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.141, 1.10 | 0.041, 0.102, 1.04 |
No. of reflections | 8591 | 2660 |
No. of parameters | 577 | 198 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 | 0.18, −0.25 |
Selected torsion angles (º) for (I) topO1A—C1A—C2A—O2A | −70.7 (3) | O1B—C1B—C2B—O2B | −74.7 (3) |
C1A—C2A—O2A—C3A | 174.2 (2) | C1B—C2B—O2B—C3B | 178.7 (2) |
C2A—O2A—C3A—C4A | 174.4 (2) | C2B—O2B—C3B—C4B | 171.7 (2) |
O2A—C3A—C4A—N1A | 178.1 (2) | O2B—C3B—C4B—N1B | 178.0 (2) |
C3A—C4A—N1A—C5A | −162.6 (2) | C3B—C4B—N1B—C5B | −156.1 (2) |
C4A—N1A—C5A—C6A | 68.6 (3) | C4B—N1B—C5B—C6B | 76.6 (3) |
N1A—C5A—C6A—O3A | −87.2 (3) | N1B—C5B—C6B—O3B | −161.3 (2) |
C5A—C6A—O3A—C7A | 178.1 (2) | C5B—C6B—O3B—C7B | 167.3 (2) |
C6A—O3A—C7A—C8A | −157.6 (2) | C6B—O3B—C7B—C8B | −88.1 (3) |
O3A—C7A—C8A—O4A | 72.4 (3) | O3B—C7B—C8B—O4B | 72.1 (3) |
C7A—C8A—O4A—C9A | −174.7 (2) | C7B—C8B—O4B—C9B | −177.4 (2) |
C8A—O4A—C9A—C10A | −173.6 (2) | C8B—O4B—C9B—C10B | −171.9 (2) |
O4A—C9A—C10A—N2A | 177.9 (2) | O4B—C9B—C10B—N2B | −173.7 (2) |
C9A—C10A—N2A—C11A | 159.7 (2) | C9B—C10B—N2B—C11B | 158.2 (2) |
C10A—N2A—C11A—C12A | −68.9 (3) | C10B—N2B—C11B—C12B | −78.4 (3) |
N2A—C11A—C12A—O1A | 87.8 (3) | N2B—C11B—C12B—O1B | 164.1 (2) |
C11A—C12A—O1A—C1A | −178.1 (2) | C11B—C12B—O1B—C1B | −164.7 (2) |
C12A—O1A—C1A—C2A | 159.1 (2) | C12B—O1B—C1B—C2B | 85.0 (3) |
Selected torsion angles (º) for (II) topN1i—C2—C3—O4 | −50.1 (2) | C6—O7—C8—C9 | 74.0 (2) |
C2—C3—O4—C5 | 165.4 (1) | O7—C8—C9—N1 | 60.3 (2) |
C3—O4—C5—C6 | −176.2 (1) | C8—C9—N1—C2i | 86.8 (2) |
O4—C5—C6—O7 | 64.6 (2) | C9—N1—C2i—C3i | −164.0 (1) |
C5—C6—O7—C8 | 152.6 (1) | | |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4i | 0.91 (2) | 2.25 (2) | 2.709 (2) | 110.2 (14) |
N1—H1N···O7 | 0.91 (2) | 2.43 (2) | 2.901 (2) | 112.6 (14) |
C2—H2B···F3 | 0.99 | 2.43 | 3.278 (2) | 143 |
C10—H10B···F4ii | 0.99 | 2.43 | 3.345 (2) | 154 |
C12—H12A···F4ii | 0.95 | 2.53 | 3.383 (2) | 150 |
C13—H13A···F4iii | 0.95 | 2.41 | 3.279 (2) | 152 |
C15—H15A···F1 | 0.95 | 2.51 | 3.368 (2) | 151 |
C16—H16A···O7i | 0.95 | 2.52 | 3.395 (2) | 154 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y, z−1; (iii) −x+2, −y+1, −z. |
The ability of crown ethers to form the host–guest complexes with normally unstable or volatile species is well known (Bott et al., 1991; Chuit et al., 1993; Feinberg et al., 1993). We have previously showed that the classic crown ethers (18-crown-6, isomers of dicyclohexyl-18-crown-6) provide the opportunity to hold harmful gaseous (SiF4; Simonov et al., 1994) or low-melting substances (BF3·H2O; Fonari et al., 1997) in the form of hydrogen-bonded molecular or ionic complexes.
A general method of synthesis of host–guest-type complexes of boron–fluoro complexes with crown ethers, based on the interaction of boron trifluoride etherate, BF3·OEt2, with the corresponding ligand in the atmosphere and not protected from moisture, has been developed (Gelmboldt et al., 1995; Simonov et al., 1995). This method was further elaborated for the preparation of complexes based on azamacrocycles (Fonari et al., 1999; Lipkowski et al., 2001). On the basis of these studies, it was shown that the composition of the `guest', the product of hydrolytic transformations of BF3·OEt2, is dictated by the nature of the macrocycle. Crown ethers offering different extents of shielding of the macrocyclic cavity stabilize either molecular (BF3·H2O) or ionic (H3O+·BF4−) complexes, while azamacrocycles, which are easily protonated in the acidic medium?, form complexes exclusively with the tetrafluoroborate anions. The components are linked in the crystal via a diverse system of O—H···O and N—H···F hydrogen bonds.
As part of our investigation of the coordination abilities of boron trifuoride with crown ethers and their derivatives, we focus here on an N,N'-dibenzyl-1,4,10,13-tetraoxo-7,16-diazacyclooctadecane, (I). Compound (I) contains a mixed N,O-atom donor function that could provide diverse possibilities for the realisation of hydrogen bonds with neutral boron trifluoride molecules or with the tetrafluoroborate anion. C—H···π ?interactions may also contribute to? the conformational stability of the macrocycle.
The Cambridge Structural Database (CSD; Allen, 2002) contains data for two single-crystal X-ray determinations of (I), carried out in ambient conditions [T = 295 K; CSD refcodes XESSUJ (Arnold et al., 1988) and XESSUJ01 (Fewings et al., 1999)]. Both determinations are in space group C2/c, with similar unit-cell dimensions but with high R factors. The unit-cell parameters for both compounds [a = 19.487 (6) Å, b = 11.259 (2) Å, c = 13.656 (5) Å and β = 121.10 (3)° for XESSUJ, and a = 19.479 (2) Å, b = 11.235 (3) Å, c = 17.038 (3) Å and β = 136.68 (0)° for XESSUJ01] can be easily transformed to the same unit cell as (I)?, with dimensions a = 13.656 Å, b = 11.259 Å, c = 17.068 Å and β = 102.14° for XESSUJ, and a = 13.668 Å, b = 11.235 Å, c = 17.038 Å and β = 102.11° for XESSUJ01 using the transformation matrixes (0 0 1 / 0 1 0 / 1 0 1) and (−1 0 − 1 / 0 − 1 0 / 0 0 1), respectively. In the new setting, both structures again belong to space group C2/c, so XESSUJ and XESSUJ01 report the same structure, as confirmed by the practically ideal superposition of these molecules.
In our experiment, carried out at 123 K, the unit-cell dimensions [a = 16.993 (3) Å and c = 13.391 (3) Å] are close to the calculated c and a parameters of the new setting, although in an inverted order and with the reduction explained by the low-temperature conditions of the experiment, while the b parameter [b = 22.455 (5) Å] is about two times longer. We found a structure solution in space group P21/c. The phase transition and the structure of (I) are assumed to correspond to a low-temperature phase with lower symmetry. Fig. 1 shows the asymmetric unit, containing two independent crown molecules (molecules a and b), which differ essentially in their conformations. This difference is clearly evident from Fig. 2, which depicts the superposition of molecules a and b. The lack of inversion centers in the two molecules is evidenced by the values of the dihedral angles between the planes of the aromatic rings C14–C19 and C21–C26 [3.6 (2) and 4.4 (2)° in molecules a and b, respectively], which deviate from 0°, as expected in a molecule imposed on an inversion center. The `free' crowns adopt the typical `parallelogram' shape, in which two methylene moities turn inward toward the center of the ring. The shortest intramolecular distances across the cavity are the C4···O4 and C10···O2 distances, being 4.157 (3) and 4.151 (3) Å in molecule a, and 4.299 (3) and of 4.306 (3) Å in molecule b; the longest distances are the C1···C7 and C5···C11 distnaces, being 7.384 (4) and of 8.611 (4) Å in molecule a, and 8.518 (4) and 7.387 (4) Å in molecule b.
Each conformer in (I) is very close to being centrosymmetric, as shown by the torsion angles in Table 1. The torsion angles run in the following sequence in molecules a and b, respectively: agaaaa-ggaa-gaaaa and gaa-ggaaaa-gaag-gaaaa [anticlockwise, beginning from the C4—N1—C5—C6 angle, where g denotes gauche (+60 to +120°), −g denotes gauche (−60 to −120°) and a denotes antiperiplanar (+\-120 to +\- 180°)]. The differences in the values of the angles that are situated in the macrocycle in the same positions relative to the centres of the rings (the point of the intersection of three trans-annular O···O distances) for molecules a and b range from 0° for the C5—C6—O3—C7 and C11—C12—O1—C1 angles, up to 2.1° for the C6—O3—C7—C8 and C12—O1—C1—C2 angles in molecule a, and ranges from 0.2° for the C2—O2—C3—C4 and C8—O4—C9—C10 angles, up to 3.1° for the C6—O3—C7—C8 and C12—O1—C1—C2 angles in molecule b.
Our calculations of the torsion angles in the independent part of the centrosymmetric molecule of XESSUJ revealed the following sequence (anticlockwise, running from the C4—N1—C5—C6 angle to the C9—C10—N2—C11 angle): −73.1, 107.7, −179.1, 139.2, −69.4, 171.8, 173.2, 177.1 and −159.2°. These values are close to the inverse of the torsion pattern given in Table 1. The common point is a sequence of four anti torsion angles that is typical for the pure phases of oxygen-containing crown ethers, for example 18-crown-6 (Maverick et al., 1980) and cis-trans-cis-dicyclohexano-18-crown-6 (Kravtsov et al., 2002). The benzyl side arms splay out from the crown rather than lying below and above the macrocyclic plane. Surprisingly, there does not appear to be any intermolecular π stacking in (I).
The centrosymmetric formula unit of (II) is shown in Fig. 3. The slight distortion of the BF4− tetrahedron is indicated by the B—F distances being in the range 1.384 (2)–1.399 (2) Å and the F—B—F angles being in the range 108.03 (16)–111.01 (15)°.
The twofold protonated macrocyclic cation, C26H40N2O42+, exhibits crystallographically imposed Ci symmetry. The protonated N atoms adopt an endo–endo orientation that is stabilized by three-center N—H···O hydrogen bonds of 2.709 (2) and 2.901 (2) Å, where the O atoms of the macrocycle act as hydrogen-bond acceptors (Table 2). The 18-membered macrocyclic cavity exhibits a degree of rigidity and adopts a chair conformation, with the O atoms lying exactly in one plane and the N atoms deviating 1.609 (2) Å above and below this plane. This rigidity probably stems from the intramolecular N—H···O hydrogen bonds, and from the presence of C—H···π interactions between two methylene H atoms and the aromatic subunits, and a C—H···O intramolecular hydrogen bond of 3.395 (2) Å (Table 2 and Fig. 3). These interactions effectively anchor the ring into its present conformation, and turn the phenyl groups of the benzyl side-arms above and below the macrocycle in such a way that the dihedral angle between the plane of the aromatic ring and the plane of the crown O atoms is 42.70 (5)°. The C···Cg1 and H···Cg1 (Cg1 is the centroid of the C11–C16 ring) distances of 3.758 (2) and 2.82 Å, and the C—H···Cg1 angle of 164°, suggest the presence of strong π···H interactions at the center of aromatic ring (Braga et al., 1998). Both of these types of intramolecular interaction in this dication have been noted for the series of lanthanoid complexes (Evans et al., 2002) and seem to be reasonable in [(I)H2]I8 (Gaballa et al., 2004). The involvement of methylene H atoms in these interactions is unusual in the light of possible competition with, for example, water H atoms.
The conformation of the macrocyclic cavity strongly deviates from that of the `free' macrocycle; the corresponding torsion angles are listed in Table 3. Inspection of the torsion angles (absolute values 50–87 and 152–176°) reveals that the macrocycle is characterized by partial conformations [(anti, gauche, anti), (anti, gauche, anti) and (gauche, gauche, gauche)] of the N1—C2—C3—O4, O4—C5—C6—O7 and O7—C8—C9—N1' subunits. The shape and conformation of the macrocyclic cation in (II) is close to that found in its complex with octaiodide (Gaballa et al., 2004) and in the neodymium complex [(I)H2][Nd(NO3)5(H2O)] (Saleh, et al., 1998). Protonation of the azacrown ether and the above-mentioned intramolecular interactions close the cavity against the inclusion of neutral (water) or charged (BF4−) species that appear to occupy the outer space of the crowns.
BF4− anions fulfill bridging functions, and in the bc plane they bind the macrocyclic cations via multiple weak C—H···F hydrogen bonds with the formation of the channels propagated along the a direction. The shortest C—H···F contacts range from 3.278 (2) to 3.395 (2) Å and are summarized in Table 2, both aromatic and aliphatic H atoms being involved in these interactions. Water molecules are held in the center of the channel, as seen from Fig. 4, and because of the weak O—H···F hydrogen bond (O···F = 2.83 A%) they are disordered around the inversion center. As shown above, the idealized stoichiometry of the [(I)H2]·2BF4·H2O complex is 1:2:1, whilst really only about 20% of the water content of each complex appears to be retained in the crystal lattice.