Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016406/qa0198sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016406/qa0198Isup2.hkl |
CCDC reference: 140870
The title compound was prepared by the dropwise addition of 1,3,5-trimethyl-2,4,6-tris(bromomethyl)benzene to 1,3,5-trimethyl-2,4,6-tri(imidazolymethyl) benzene in highly diluted acetonitrile solutions at 348 K and recrystallized from water.
The absorption correction is given by the experimental fact, so it is appropriate. The difference between expected and reported Tmax/Tmin may be caused by the fact that the single-crystal is not quite perfect or the measurement of the crystal size is not very precise. The water H atoms H1A and H1B were refined.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).
C33H39N63+·3Br−·2H2O | Dx = 1.602 Mg m−3 |
Mr = 795.46 | Melting point > 573 K |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
a = 9.855 (2) Å | Cell parameters from 29 reflections |
b = 17.306 (3) Å | θ = 3.2–16.4° |
c = 10.607 (2) Å | µ = 3.71 mm−1 |
β = 114.29 (1)° | T = 296 K |
V = 1648.9 (5) Å3 | Flake, colourless |
Z = 2 | 0.56 × 0.40 × 0.28 mm |
F(000) = 808 |
Siemens P4 diffractometer | 2006 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 25°, θmin = 2.1° |
ω scans | h = 0→11 |
Absorption correction: empirical (using intensity measurements) (SHELXTL; Siemems, 1994) | k = −1→20 |
Tmin = 0.227, Tmax = 0.354 | l = −12→11 |
3533 measured reflections | 3 standard reflections every 97 reflections |
2989 independent reflections | intensity decay: 5.4% |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0376P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max = 0.001 |
2989 reflections | Δρmax = 0.41 e Å−3 |
217 parameters | Δρmin = −0.45 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (4) |
C33H39N63+·3Br−·2H2O | V = 1648.9 (5) Å3 |
Mr = 795.46 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 9.855 (2) Å | µ = 3.71 mm−1 |
b = 17.306 (3) Å | T = 296 K |
c = 10.607 (2) Å | 0.56 × 0.40 × 0.28 mm |
β = 114.29 (1)° |
Siemens P4 diffractometer | 2006 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (SHELXTL; Siemems, 1994) | Rint = 0.022 |
Tmin = 0.227, Tmax = 0.354 | 3 standard reflections every 97 reflections |
3533 measured reflections | intensity decay: 5.4% |
2989 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 3 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.41 e Å−3 |
2989 reflections | Δρmin = −0.45 e Å−3 |
217 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.60411 (4) | −0.04704 (2) | 0.27542 (4) | 0.03738 (14) | |
Br2 | 0.68478 (8) | 0.2500 | 0.34559 (7) | 0.0586 (2) | |
N1 | 0.3727 (3) | 0.18781 (15) | 0.0343 (3) | 0.0246 (6) | |
N2 | 0.0796 (3) | 0.18738 (16) | 0.4093 (3) | 0.0294 (7) | |
N3 | −0.2540 (3) | 0.18748 (15) | −0.2009 (3) | 0.0266 (7) | |
C1 | 0.4272 (3) | 0.21116 (18) | −0.0585 (3) | 0.0289 (8) | |
H1 | 0.4585 | 0.1793 | −0.1119 | 0.035* | |
C2 | 0.3421 (5) | 0.2500 | 0.0904 (5) | 0.0282 (12) | |
H2 | 0.3052 | 0.2500 | 0.1582 | 0.034* | |
C3 | 0.3499 (4) | 0.10763 (18) | 0.0691 (4) | 0.0285 (9) | |
H3A | 0.4301 | 0.0928 | 0.1561 | 0.034* | |
H3B | 0.3507 | 0.0728 | −0.0022 | 0.034* | |
C4 | 0.1563 (4) | 0.2112 (2) | 0.5422 (4) | 0.0477 (11) | |
H4 | 0.2007 | 0.1795 | 0.6192 | 0.057* | |
C5 | 0.0334 (6) | 0.2500 | 0.3306 (5) | 0.0332 (13) | |
H5 | −0.0224 | 0.2500 | 0.2354 | 0.040* | |
C6 | 0.0517 (4) | 0.10673 (18) | 0.3586 (4) | 0.0334 (9) | |
H6A | −0.0453 | 0.0902 | 0.3513 | 0.040* | |
H6B | 0.1262 | 0.0730 | 0.4238 | 0.040* | |
C7 | −0.3782 (4) | 0.2114 (2) | −0.3113 (3) | 0.0414 (10) | |
H7 | −0.4500 | 0.1797 | −0.3751 | 0.050* | |
C8 | −0.1814 (6) | 0.2500 | −0.1362 (5) | 0.0328 (13) | |
H8 | −0.0928 | 0.2500 | −0.0571 | 0.039* | |
C9 | −0.2092 (4) | 0.10568 (18) | −0.1630 (4) | 0.0295 (9) | |
H9A | −0.1926 | 0.0807 | −0.2373 | 0.035* | |
H9B | −0.2885 | 0.0783 | −0.1502 | 0.035* | |
C10 | 0.2014 (4) | 0.10158 (17) | 0.0810 (4) | 0.0231 (8) | |
C11 | 0.1973 (4) | 0.10027 (18) | 0.2113 (4) | 0.0249 (8) | |
C12 | 0.0575 (4) | 0.10082 (17) | 0.2187 (4) | 0.0252 (8) | |
C13 | −0.0758 (4) | 0.10057 (17) | 0.0980 (4) | 0.0258 (8) | |
C14 | −0.0678 (4) | 0.10195 (17) | −0.0305 (4) | 0.0258 (8) | |
C15 | 0.0699 (4) | 0.10317 (17) | −0.0407 (3) | 0.0246 (8) | |
C16 | 0.0764 (4) | 0.1110 (2) | −0.1794 (4) | 0.0380 (10) | |
H16A | 0.0599 | 0.1639 | −0.2088 | 0.046* | |
H16B | 0.0009 | 0.0791 | −0.2457 | 0.046* | |
H16C | 0.1725 | 0.0948 | −0.1722 | 0.046* | |
C17 | 0.3393 (4) | 0.1013 (2) | 0.3419 (4) | 0.0405 (10) | |
H17A | 0.3919 | 0.0536 | 0.3499 | 0.049* | |
H17B | 0.3157 | 0.1075 | 0.4206 | 0.049* | |
H17C | 0.4007 | 0.1436 | 0.3382 | 0.049* | |
C18 | −0.2246 (4) | 0.1027 (2) | 0.1085 (4) | 0.0411 (10) | |
H18A | −0.2336 | 0.0582 | 0.1585 | 0.049* | |
H18B | −0.3035 | 0.1026 | 0.0173 | 0.049* | |
H18C | −0.2308 | 0.1488 | 0.1563 | 0.049* | |
O | 0.7795 (5) | 0.0838 (3) | 0.5175 (4) | 0.0864 (12) | |
H1A | 0.727 (6) | 0.050 (2) | 0.456 (5) | 0.12 (2)* | |
H1B | 0.749 (6) | 0.1280 (15) | 0.490 (5) | 0.11 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0415 (2) | 0.0325 (2) | 0.0391 (2) | 0.0034 (2) | 0.01750 (18) | −0.0009 (2) |
Br2 | 0.0587 (5) | 0.0560 (4) | 0.0591 (5) | 0.000 | 0.0222 (4) | 0.000 |
N1 | 0.0242 (15) | 0.0233 (15) | 0.0270 (16) | 0.0021 (13) | 0.0112 (13) | −0.0005 (13) |
N2 | 0.0365 (17) | 0.0279 (16) | 0.0287 (16) | 0.0022 (14) | 0.0183 (15) | 0.0015 (14) |
N3 | 0.0247 (16) | 0.0249 (15) | 0.0254 (16) | −0.0004 (14) | 0.0054 (14) | −0.0010 (14) |
C1 | 0.0297 (19) | 0.0325 (18) | 0.0298 (19) | −0.0001 (16) | 0.0175 (17) | −0.0006 (16) |
C2 | 0.030 (3) | 0.030 (3) | 0.028 (3) | 0.000 | 0.016 (3) | 0.000 |
C3 | 0.033 (2) | 0.0192 (17) | 0.032 (2) | 0.0037 (16) | 0.0124 (18) | 0.0017 (16) |
C4 | 0.075 (3) | 0.044 (2) | 0.018 (2) | 0.002 (2) | 0.014 (2) | 0.0042 (18) |
C5 | 0.046 (4) | 0.026 (3) | 0.026 (3) | 0.000 | 0.013 (3) | 0.000 |
C6 | 0.041 (2) | 0.0252 (19) | 0.036 (2) | −0.0013 (17) | 0.017 (2) | 0.0021 (17) |
C7 | 0.035 (2) | 0.037 (2) | 0.029 (2) | −0.0045 (18) | −0.0104 (18) | −0.0018 (17) |
C8 | 0.029 (3) | 0.026 (3) | 0.032 (3) | 0.000 | 0.002 (3) | 0.000 |
C9 | 0.031 (2) | 0.0199 (18) | 0.034 (2) | −0.0016 (16) | 0.0095 (18) | −0.0030 (16) |
C10 | 0.0250 (19) | 0.0159 (16) | 0.031 (2) | 0.0018 (14) | 0.0143 (17) | 0.0039 (15) |
C11 | 0.025 (2) | 0.0186 (18) | 0.029 (2) | 0.0029 (15) | 0.0101 (17) | 0.0042 (15) |
C12 | 0.035 (2) | 0.0170 (17) | 0.027 (2) | 0.0011 (15) | 0.0156 (17) | 0.0025 (15) |
C13 | 0.030 (2) | 0.0142 (17) | 0.035 (2) | 0.0018 (15) | 0.0145 (18) | 0.0039 (15) |
C14 | 0.031 (2) | 0.0134 (16) | 0.029 (2) | −0.0004 (15) | 0.0082 (17) | −0.0004 (15) |
C15 | 0.028 (2) | 0.0164 (17) | 0.027 (2) | −0.0001 (15) | 0.0102 (17) | 0.0009 (15) |
C16 | 0.037 (2) | 0.042 (2) | 0.033 (2) | −0.0016 (19) | 0.0123 (19) | 0.0013 (19) |
C17 | 0.036 (2) | 0.051 (2) | 0.033 (2) | 0.004 (2) | 0.0123 (19) | 0.0009 (19) |
C18 | 0.032 (2) | 0.050 (2) | 0.043 (2) | 0.0026 (19) | 0.017 (2) | 0.001 (2) |
O | 0.110 (3) | 0.064 (2) | 0.049 (2) | −0.007 (3) | −0.004 (2) | −0.004 (2) |
N1—C2 | 1.323 (4) | C6—C12 | 1.511 (5) |
N1—C1 | 1.362 (4) | C7—C7i | 1.335 (7) |
N1—C3 | 1.477 (4) | C8—N3i | 1.323 (4) |
N2—C5 | 1.329 (4) | C9—C14 | 1.520 (5) |
N2—C4 | 1.361 (4) | C10—C11 | 1.400 (4) |
N2—C6 | 1.480 (4) | C10—C15 | 1.404 (4) |
N3—C8 | 1.323 (4) | C11—C12 | 1.412 (5) |
N3—C7 | 1.365 (4) | C11—C17 | 1.511 (5) |
N3—C9 | 1.488 (4) | C12—C13 | 1.408 (5) |
C1—C1i | 1.344 (6) | C13—C14 | 1.397 (5) |
C2—N1i | 1.323 (4) | C13—C18 | 1.516 (5) |
C3—C10 | 1.524 (5) | C14—C15 | 1.404 (5) |
C4—C4i | 1.343 (7) | C15—C16 | 1.505 (5) |
C5—N2i | 1.329 (4) | ||
C2—N1—C1 | 108.3 (3) | C11—C10—C15 | 121.2 (3) |
C2—N1—C3 | 124.5 (3) | C11—C10—C3 | 120.1 (3) |
C1—N1—C3 | 127.2 (3) | C15—C10—C3 | 118.6 (3) |
C5—N2—C4 | 107.7 (3) | C10—C11—C12 | 118.7 (3) |
C5—N2—C6 | 125.2 (3) | C10—C11—C17 | 120.9 (3) |
C4—N2—C6 | 127.1 (3) | C12—C11—C17 | 120.4 (3) |
C8—N3—C7 | 107.4 (3) | C13—C12—C11 | 121.1 (3) |
C8—N3—C9 | 126.9 (3) | C13—C12—C6 | 119.7 (3) |
C7—N3—C9 | 125.6 (3) | C11—C12—C6 | 119.1 (3) |
C1i—C1—N1 | 107.25 (17) | C14—C13—C12 | 118.8 (3) |
N1—C2—N1i | 108.9 (4) | C14—C13—C18 | 121.0 (3) |
N1—C3—C10 | 109.6 (3) | C12—C13—C18 | 120.1 (3) |
C4i—C4—N2 | 107.6 (2) | C13—C14—C15 | 121.3 (3) |
N2i—C5—N2 | 109.3 (4) | C13—C14—C9 | 120.3 (3) |
N2—C6—C12 | 110.1 (3) | C15—C14—C9 | 118.4 (3) |
C7i—C7—N3 | 107.69 (19) | C10—C15—C14 | 119.0 (3) |
N3—C8—N3i | 109.8 (4) | C10—C15—C16 | 120.4 (3) |
N3—C9—C14 | 110.3 (3) | C14—C15—C16 | 120.5 (3) |
C2—N1—C1—C1i | −0.7 (3) | C10—C11—C12—C13 | 1.7 (5) |
C3—N1—C1—C1i | 179.2 (3) | C17—C11—C12—C13 | 179.4 (3) |
C1—N1—C2—N1i | 1.2 (5) | C10—C11—C12—C6 | −174.5 (3) |
C3—N1—C2—N1i | −178.8 (2) | C17—C11—C12—C6 | 3.2 (5) |
C2—N1—C3—C10 | 42.2 (5) | N2—C6—C12—C13 | −99.0 (4) |
C1—N1—C3—C10 | −137.7 (3) | N2—C6—C12—C11 | 77.3 (4) |
C5—N2—C4—C4i | −0.4 (3) | C11—C12—C13—C14 | −1.8 (5) |
C6—N2—C4—C4i | 179.4 (3) | C6—C12—C13—C14 | 174.4 (3) |
C4—N2—C5—N2i | 0.6 (6) | C11—C12—C13—C18 | −178.8 (3) |
C6—N2—C5—N2i | −179.2 (3) | C6—C12—C13—C18 | −2.6 (5) |
C5—N2—C6—C12 | 36.3 (5) | C12—C13—C14—C15 | 0.3 (5) |
C4—N2—C6—C12 | −143.3 (4) | C18—C13—C14—C15 | 177.3 (3) |
C8—N3—C7—C7i | 0.1 (3) | C12—C13—C14—C9 | −177.0 (3) |
C9—N3—C7—C7i | −179.2 (3) | C18—C13—C14—C9 | 0.0 (5) |
C7—N3—C8—N3i | −0.2 (5) | N3—C9—C14—C13 | 88.2 (4) |
C9—N3—C8—N3i | 179.1 (2) | N3—C9—C14—C15 | −89.2 (4) |
C8—N3—C9—C14 | 3.1 (5) | C11—C10—C15—C14 | −1.2 (5) |
C7—N3—C9—C14 | −177.7 (3) | C3—C10—C15—C14 | −176.5 (3) |
N1—C3—C10—C11 | −101.5 (3) | C11—C10—C15—C16 | 175.1 (3) |
N1—C3—C10—C15 | 73.8 (4) | C3—C10—C15—C16 | −0.2 (4) |
C15—C10—C11—C12 | −0.2 (5) | C13—C14—C15—C10 | 1.2 (5) |
C3—C10—C11—C12 | 175.0 (3) | C9—C14—C15—C10 | 178.5 (3) |
C15—C10—C11—C17 | −177.9 (3) | C13—C14—C15—C16 | −175.2 (3) |
C3—C10—C11—C17 | −2.6 (5) | C9—C14—C15—C16 | 2.2 (5) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O—H1A···Br1 | 0.87 (3) | 2.46 (3) | 3.326 (4) | 173 (5) |
O—H1B···Br2 | 0.83 (2) | 2.53 (3) | 3.326 (4) | 161 (5) |
Experimental details
Crystal data | |
Chemical formula | C33H39N63+·3Br−·2H2O |
Mr | 795.46 |
Crystal system, space group | Monoclinic, P21/m |
Temperature (K) | 296 |
a, b, c (Å) | 9.855 (2), 17.306 (3), 10.607 (2) |
β (°) | 114.29 (1) |
V (Å3) | 1648.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.71 |
Crystal size (mm) | 0.56 × 0.40 × 0.28 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (SHELXTL; Siemems, 1994) |
Tmin, Tmax | 0.227, 0.354 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3533, 2989, 2006 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.073, 0.88 |
No. of reflections | 2989 |
No. of parameters | 217 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.45 |
Computer programs: XSCANS (Siemens, 1996), SHELXTL (Siemens, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O—H1A···Br1 | 0.87 (3) | 2.46 (3) | 3.326 (4) | 173 (5) |
O—H1B···Br2 | 0.83 (2) | 2.53 (3) | 3.326 (4) | 161 (5) |
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The molecular recognition and catalysis properties of cyclophanes have received considerable attention in recent years (Lehn, 1995). It is worthwhile pursuing to design and prepare suitable macrocyclic ligands with fine features. Following our work on imidazole-containing macrocycles (Liu et al., 1999; Lou et al., 1995), for the first time, we synthesize the new type of cyclophane in which two benzene rings are triply bridged by imidazoliums, (I). The compound has Cs symmetry. The parallel capping benzene rings are 5.144 Å apart. The three imidazolium rings are not arranged symmetrically, the angles of them are 54.0, 99.1 and 153.2°, and the distances of the three 2-carbons of the imidazoliums are 4.703, 4.711 and 4.514 Å. The shape of the compound makes it suitable to form exclusive or inclusive complexes with small anions.
Different from the case of [14]metacyclo-bis-(1,3)imidazolophanium dichloride dihydrate (Alcalde et al., 1999), the halogen anions form hydrogen bonds with water rather than with imidazolophanium.