Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040548/lh2480sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040548/lh2480Isup2.hkl |
CCDC reference: 660324
To a solution of the crown conformer of CTV oxime (10,15-dihydro-2,3,7,8,12,13-hexamethoxy-5H-tribenzo[a,d,g]cyclononen-5-oxime, 200 mg, 0.417 mmol) in 4 ml diethyl ether and 1 ml of dichloromethane at 273 K was added thionyl chloride (1.88 g, 15.8 mmol) dropwise over 1 minute. The reaction mixture was stirred for 5 minutes at 273 K, then poured over ice and extracted with methylene chloride. The organic layer was washed successively with saturated aqueous sodium bicarbonate, water and brine, and then dried over sodium sulfate. Concentration gave a residue which was chromatographed on silica gel eluting with ethyl acetate/methylene chloride (30/70) to afford 0.028 g of a solid which was recrystallized from toluene/dichloromethane to give 0.023 g (23%) of the product as red-bronze crystals.
The crystal under investigation was found to be non-merohedrally twinned. The orientation matrices for the two components were identified using the program Cell_Now (Sheldrick, 2004), and the two components were integrated using Saint+ (Bruker, 2003), resulting in a total of 40178 reflections. 12959 reflections (5474 unique) involved component 1 only (mean I/sigma = 5.5), 12616 reflections (5374 unique ones) involved component 2 only (mean I/sigma = 3.7), and 14603 reflections (7998 unique ones) involved both components (mean I/sigma = 6.4). The exact twin matrix identified by the integration program was found to be 0.99876 - 0.00396 - 0.00012, 0.00212 0.99889 0.00875, -0.00309 - 0.11163 0.99795, which is for this structure equivalent to a 180° rotation around the reciprocal axis [1 0 0].
The data were corrected for absorption using Twinabs (Bruker, 2003), and the structure was solved using direct methods with only the non-overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of component 1 (including the overlapping ones) below a d-spacing threshold of 3/4, resulting in a BASF value of 0.312 (2). Due to "twin pairing errors" in Saint+ (equivalent reflections being counted as overlapping for one reflection, but as not overlapping for an eqivalent one) no accurate Rint value can be given. This also results in an incomplete merging of equivalent reflections in Twinabs, thus resulting in too many independent reflections. (Herbst-Irmer, 2006)
Hydrogen atoms were added in calculated positions with C—H distances of 0.95, 0.99 and 0.98 Å for aromatic, methylene and methyl H atoms, respectively, and were refined with Uiso(H) = x Ueq(C) (x = 1.2 for C—H and CH2, 1.5 for CH3).
The s.u. values of the cell parameters are taken from the software recognizing that the values are unreasonably small (Herbstein, 2000).
The crown-shaped [1.1.1]orthocyclophane cyclotriveratrylene (CTV, hexamethoxy tribenzocyclononene) molecule has been employed extensively as a scaffold in supramolecular chemistry (Collet, 1987). We are interested in new apex-modified derivatives of CTV and recently reported the isolation of the crown and saddle conformers of CTV oxime (Lutz et al., 2007). In the course of studying the Beckmann rearrangement of this molecule we observed the unexpected formation of the title compound, resulting from a Beckmann rearrangement followed by an intramolecular electrophilic aromatic addition and subsequent demethylation (Fig. 1). Studies of the reaction conditions and mechanism will be discussed in detail in a separate publication.
The title compound was crystallized from methylene chloride/toluene as its toluene solvate (Figure 2). The red needle-like crystals were heavily intergrown, and the crystal that was finally selected for single-crystal data collection was found to be non-merohedrally twinned with two twin components in a ratio of 0.688 (2) to 0.312 (2) (See experimental refinement section for details of unit cell determination, data workup, refinement, and type of twinning).
The compound shows an unusual helical arrangement of three six-membered rings that are all connected at the central carbon atom C6. The helix effectively performs one full turn around C6, and the thread pitch, as defined by the distance of the terminal atoms C2 and C20 of the helix, is 4.98 (3) Å. The angles around C6 are between 104.7 (2) and 115.2 (2)°. The middle ring, a cyclohexa-2,4-dienimine with C6 being the only saturated atom in the ring, is nearly planar with an r.m.s. deviation from the mean plane of only 0.035 Å. The other two rings have conformations best described as between envelope and screw-boat (Boeyens, 1978) with puckering amplitudes of 0.527 (2) and 0.544 (2) Å, respectively (Cremer & Pople, 1975).
The packing of the title compound, illustrated in Figure 3, seems to be dominated by a combination of simple dispersion forces, and weak interactions of the methoxy methyl hydrogen bonds with both neigboring oxygen atoms and aromatic rings. All methoxy groups are involved in at least one C—H···O hydrogen bond or C—H···π contact, and all aromatic rings act as an acceptor to one or two methoxy CH3 groups.
For the use of crown-shaped [1.1.1]orthocyclophane cyclotriveratrylene (CTV, hexamethoxy tribenzocyclononene) as a scaffold in supramolecular chemistry, see: Collet (1987). For crown and saddle conformers of CTV oxime, see: Lutz et al. (2007).
For related literature, see: Boeyens (1978); Cremer & Pople (1975); Herbst-Irmer (2006); Herbstein (2000).
Data collection: SMART (Bruker, 2002); cell refinement: CELL_NOW (Sheldrick, 2004) and SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
C26H25NO6·C7H8 | F(000) = 1144 |
Mr = 539.60 | Dx = 1.300 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6322 reflections |
a = 14.952 (4) Å | θ = 3.0–30.5° |
b = 7.1736 (18) Å | µ = 0.09 mm−1 |
c = 25.787 (6) Å | T = 100 K |
β = 94.571 (7)° | Rod, red |
V = 2757.1 (12) Å3 | 0.60 × 0.19 × 0.09 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 10641 independent reflections |
Radiation source: fine-focus sealed tube | 7887 reflections with I > 2σ(I) |
Graphite monochromator | Rint = not defined due to twin pairing errors, Herbst-Irmer, 2006 |
ω scans | θmax = 28.3°, θmin = 1.4° |
Absorption correction: multi-scan (TWINABS; Bruker, 2003) | h = −19→19 |
Tmin = 0.773, Tmax = 1.000 | k = 0→9 |
40178 measured reflections | l = 0→34 |
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) = 0.199 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0913P)2 + 1.3281P] where P = (Fo2 + 2Fc2)/3 |
10641 reflections | (Δ/σ)max < 0.001 |
368 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C26H25NO6·C7H8 | V = 2757.1 (12) Å3 |
Mr = 539.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.952 (4) Å | µ = 0.09 mm−1 |
b = 7.1736 (18) Å | T = 100 K |
c = 25.787 (6) Å | 0.60 × 0.19 × 0.09 mm |
β = 94.571 (7)° |
Bruker SMART APEX CCD diffractometer | 10641 independent reflections |
Absorption correction: multi-scan (TWINABS; Bruker, 2003) | 7887 reflections with I > 2σ(I) |
Tmin = 0.773, Tmax = 1.000 | Rint = not defined due to twin pairing errors, Herbst-Irmer, 2006 |
40178 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.67 e Å−3 |
10641 reflections | Δρmin = −0.25 e Å−3 |
368 parameters |
Experimental. The crystal under investigation was found to be non-merohedrally twinned. The orientation matrices for the two components were identified using the program Cell_Now, and the two components were integrated using Saint, resulting in a total of 40178 reflections. 12959 reflections (5474 unique ones) involved component 1 only (mean I/sigma = 5.5), 12616 reflections (5374 unique ones) involved component 2 only (mean I/sigma = 3.7), and 14603 reflections (7998 unique ones) involved both components (mean I/sigma = 6.4). The exact twin matrix identified by the integration program was found to be 0.99876 - 0.00396 - 0.00012, 0.00212 0.99889 0.00875, -0.00309 - 0.11163 0.99795. The data were corrected for absorption using twinabs, and the structure was solved using direct methods with only the non-overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of component 1 (including the overlapping ones) below a d-spacing threshold of 3/4, resulting in a BASF value of 0.312 (2). |
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 | ||
C1 | 0.36910 (14) | 0.6758 (3) | 0.48902 (8) | 0.0190 (4) | |
H1A | 0.3447 | 0.5551 | 0.4757 | 0.023* | |
H1B | 0.4282 | 0.6947 | 0.4751 | 0.023* | |
C2 | 0.38116 (14) | 0.6689 (3) | 0.54776 (8) | 0.0202 (4) | |
C3 | 0.38050 (14) | 0.8509 (3) | 0.57581 (8) | 0.0193 (4) | |
C4 | 0.36991 (14) | 1.0121 (3) | 0.54819 (8) | 0.0192 (4) | |
H4 | 0.3771 | 1.1280 | 0.5659 | 0.023* | |
C5 | 0.34790 (13) | 1.0112 (3) | 0.49225 (7) | 0.0164 (4) | |
C6 | 0.30468 (14) | 0.8353 (3) | 0.46952 (7) | 0.0161 (4) | |
C7 | 0.21107 (14) | 0.7989 (3) | 0.48916 (8) | 0.0175 (4) | |
H7A | 0.2157 | 0.7918 | 0.5276 | 0.021* | |
H7B | 0.1696 | 0.9016 | 0.4782 | 0.021* | |
C8 | 0.17650 (14) | 0.6175 (3) | 0.46620 (8) | 0.0174 (4) | |
C9 | 0.12927 (14) | 0.4885 (3) | 0.49419 (8) | 0.0193 (4) | |
H9 | 0.1164 | 0.5165 | 0.5288 | 0.023* | |
C10 | 0.10097 (14) | 0.3203 (3) | 0.47201 (8) | 0.0191 (4) | |
C11 | 0.11910 (14) | 0.2807 (3) | 0.42046 (8) | 0.0183 (4) | |
C12 | 0.16534 (13) | 0.4081 (3) | 0.39220 (7) | 0.0169 (4) | |
H12 | 0.1769 | 0.3814 | 0.3573 | 0.020* | |
C13 | 0.19494 (13) | 0.5765 (3) | 0.41539 (7) | 0.0165 (4) | |
C14 | 0.28966 (13) | 0.8315 (3) | 0.40988 (7) | 0.0156 (4) | |
C15 | 0.32871 (13) | 0.9817 (3) | 0.37944 (7) | 0.0159 (4) | |
C16 | 0.32393 (13) | 0.9731 (3) | 0.32478 (7) | 0.0159 (4) | |
H16 | 0.2972 | 0.8679 | 0.3074 | 0.019* | |
C17 | 0.35782 (13) | 1.1168 (3) | 0.29594 (8) | 0.0160 (4) | |
C18 | 0.39549 (13) | 1.2758 (3) | 0.32219 (8) | 0.0167 (4) | |
C19 | 0.39815 (13) | 1.2865 (3) | 0.37567 (8) | 0.0172 (4) | |
H19 | 0.4221 | 1.3948 | 0.3929 | 0.021* | |
C20 | 0.36590 (13) | 1.1392 (3) | 0.40523 (8) | 0.0156 (4) | |
C21 | 0.37340 (14) | 1.1502 (3) | 0.46147 (8) | 0.0180 (4) | |
H21 | 0.3974 | 1.2606 | 0.4774 | 0.022* | |
C22 | 0.41041 (17) | 1.0041 (3) | 0.65651 (8) | 0.0256 (5) | |
H22A | 0.4633 | 1.0682 | 0.6452 | 0.038* | |
H22B | 0.4197 | 0.9764 | 0.6938 | 0.038* | |
H22C | 0.3576 | 1.0843 | 0.6501 | 0.038* | |
C23 | 0.05158 (16) | 0.2025 (3) | 0.55146 (8) | 0.0254 (5) | |
H23A | 0.1125 | 0.2149 | 0.5681 | 0.038* | |
H23B | 0.0231 | 0.0913 | 0.5649 | 0.038* | |
H23C | 0.0164 | 0.3131 | 0.5590 | 0.038* | |
C24 | 0.09328 (15) | 0.0706 (3) | 0.34878 (8) | 0.0221 (5) | |
H24A | 0.0601 | 0.1665 | 0.3281 | 0.033* | |
H24B | 0.0664 | −0.0517 | 0.3408 | 0.033* | |
H24C | 0.1560 | 0.0701 | 0.3403 | 0.033* | |
C25 | 0.32396 (16) | 0.9605 (3) | 0.21512 (8) | 0.0251 (5) | |
H25A | 0.3573 | 0.8492 | 0.2274 | 0.038* | |
H25B | 0.3303 | 0.9779 | 0.1779 | 0.038* | |
H25C | 0.2604 | 0.9451 | 0.2208 | 0.038* | |
C26 | 0.46204 (15) | 1.5756 (3) | 0.31657 (8) | 0.0209 (5) | |
H26A | 0.4142 | 1.6355 | 0.3344 | 0.031* | |
H26B | 0.4837 | 1.6616 | 0.2908 | 0.031* | |
H26C | 0.5116 | 1.5426 | 0.3421 | 0.031* | |
C27 | 0.14872 (15) | 0.6018 (3) | 0.21337 (8) | 0.0239 (5) | |
C28 | 0.14841 (16) | 0.6401 (4) | 0.16066 (9) | 0.0299 (6) | |
H28 | 0.1748 | 0.5535 | 0.1385 | 0.036* | |
C29 | 0.11040 (18) | 0.8023 (4) | 0.13957 (9) | 0.0365 (6) | |
H29 | 0.1103 | 0.8252 | 0.1033 | 0.044* | |
C30 | 0.07272 (17) | 0.9308 (4) | 0.17138 (10) | 0.0335 (6) | |
H30 | 0.0471 | 1.0426 | 0.1571 | 0.040* | |
C31 | 0.07257 (16) | 0.8953 (3) | 0.22406 (9) | 0.0271 (5) | |
H31 | 0.0467 | 0.9829 | 0.2461 | 0.033* | |
C32 | 0.11011 (15) | 0.7325 (3) | 0.24480 (8) | 0.0233 (5) | |
H32 | 0.1095 | 0.7094 | 0.2810 | 0.028* | |
C33 | 0.18935 (19) | 0.4249 (4) | 0.23630 (10) | 0.0384 (6) | |
H33A | 0.2126 | 0.3497 | 0.2086 | 0.058* | |
H33B | 0.1434 | 0.3541 | 0.2529 | 0.058* | |
H33C | 0.2385 | 0.4561 | 0.2623 | 0.058* | |
N1 | 0.24151 (11) | 0.7050 (2) | 0.38542 (6) | 0.0174 (4) | |
O1 | 0.39663 (10) | 0.8337 (2) | 0.62800 (5) | 0.0222 (3) | |
O2 | 0.35886 (10) | 1.1202 (2) | 0.24319 (5) | 0.0203 (3) | |
O3 | 0.42770 (10) | 1.4094 (2) | 0.29075 (5) | 0.0210 (3) | |
O4 | 0.08931 (10) | 0.1096 (2) | 0.40264 (5) | 0.0222 (3) | |
O5 | 0.05546 (10) | 0.1852 (2) | 0.49660 (5) | 0.0239 (4) | |
O6 | 0.39527 (12) | 0.5216 (2) | 0.57117 (6) | 0.0308 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0221 (11) | 0.0138 (10) | 0.0210 (10) | 0.0001 (9) | 0.0014 (8) | −0.0018 (8) |
C2 | 0.0192 (11) | 0.0185 (11) | 0.0225 (11) | −0.0013 (9) | −0.0014 (8) | 0.0001 (8) |
C3 | 0.0202 (11) | 0.0192 (11) | 0.0184 (10) | −0.0038 (9) | 0.0018 (8) | −0.0013 (8) |
C4 | 0.0223 (11) | 0.0151 (10) | 0.0204 (10) | −0.0038 (9) | 0.0031 (8) | −0.0028 (8) |
C5 | 0.0171 (10) | 0.0131 (10) | 0.0193 (10) | −0.0005 (8) | 0.0027 (8) | −0.0030 (8) |
C6 | 0.0193 (10) | 0.0131 (10) | 0.0160 (9) | −0.0019 (9) | 0.0018 (8) | 0.0002 (7) |
C7 | 0.0206 (10) | 0.0148 (10) | 0.0176 (10) | −0.0014 (9) | 0.0043 (8) | −0.0029 (8) |
C8 | 0.0168 (10) | 0.0150 (10) | 0.0203 (10) | 0.0002 (9) | 0.0017 (8) | −0.0009 (8) |
C9 | 0.0238 (11) | 0.0180 (10) | 0.0167 (10) | −0.0026 (9) | 0.0065 (8) | −0.0021 (8) |
C10 | 0.0201 (10) | 0.0166 (10) | 0.0207 (10) | −0.0026 (9) | 0.0027 (8) | 0.0034 (8) |
C11 | 0.0195 (10) | 0.0128 (10) | 0.0224 (10) | −0.0032 (9) | −0.0002 (8) | 0.0000 (8) |
C12 | 0.0187 (10) | 0.0166 (10) | 0.0156 (9) | −0.0003 (9) | 0.0023 (8) | 0.0009 (8) |
C13 | 0.0163 (10) | 0.0148 (10) | 0.0182 (10) | −0.0013 (9) | −0.0009 (8) | 0.0027 (8) |
C14 | 0.0160 (10) | 0.0123 (10) | 0.0187 (10) | 0.0019 (8) | 0.0019 (8) | −0.0021 (8) |
C15 | 0.0144 (10) | 0.0141 (10) | 0.0195 (10) | −0.0004 (8) | 0.0026 (7) | 0.0020 (8) |
C16 | 0.0145 (9) | 0.0126 (10) | 0.0207 (10) | −0.0009 (8) | 0.0019 (8) | −0.0002 (8) |
C17 | 0.0138 (10) | 0.0160 (10) | 0.0182 (9) | 0.0013 (8) | 0.0024 (7) | −0.0001 (8) |
C18 | 0.0143 (10) | 0.0144 (10) | 0.0214 (10) | −0.0003 (8) | 0.0025 (8) | 0.0022 (8) |
C19 | 0.0161 (10) | 0.0110 (9) | 0.0245 (10) | −0.0013 (8) | 0.0011 (8) | 0.0005 (8) |
C20 | 0.0145 (10) | 0.0113 (9) | 0.0212 (10) | −0.0003 (8) | 0.0022 (8) | 0.0007 (7) |
C21 | 0.0206 (10) | 0.0134 (10) | 0.0200 (10) | −0.0023 (9) | 0.0022 (8) | −0.0018 (8) |
C22 | 0.0352 (13) | 0.0216 (11) | 0.0198 (11) | −0.0029 (11) | 0.0004 (9) | −0.0048 (9) |
C23 | 0.0306 (12) | 0.0254 (12) | 0.0206 (11) | −0.0101 (10) | 0.0048 (9) | 0.0028 (9) |
C24 | 0.0235 (11) | 0.0203 (11) | 0.0226 (11) | −0.0030 (10) | 0.0022 (8) | −0.0042 (8) |
C25 | 0.0303 (13) | 0.0249 (12) | 0.0203 (11) | −0.0060 (10) | 0.0025 (9) | −0.0032 (9) |
C26 | 0.0236 (11) | 0.0143 (10) | 0.0252 (11) | −0.0039 (9) | 0.0048 (9) | 0.0007 (8) |
C27 | 0.0211 (11) | 0.0230 (12) | 0.0275 (12) | −0.0040 (10) | 0.0018 (9) | −0.0001 (9) |
C28 | 0.0273 (13) | 0.0334 (14) | 0.0301 (12) | −0.0003 (11) | 0.0088 (10) | −0.0058 (10) |
C29 | 0.0406 (15) | 0.0467 (16) | 0.0224 (12) | −0.0016 (13) | 0.0046 (10) | 0.0100 (11) |
C30 | 0.0327 (14) | 0.0270 (13) | 0.0403 (14) | 0.0006 (12) | −0.0007 (11) | 0.0076 (11) |
C31 | 0.0268 (12) | 0.0220 (12) | 0.0323 (12) | 0.0001 (10) | 0.0013 (10) | −0.0058 (10) |
C32 | 0.0235 (11) | 0.0270 (12) | 0.0194 (10) | −0.0029 (10) | 0.0023 (8) | −0.0010 (9) |
C33 | 0.0398 (15) | 0.0315 (14) | 0.0447 (15) | 0.0056 (13) | 0.0085 (12) | 0.0043 (12) |
N1 | 0.0189 (9) | 0.0140 (9) | 0.0198 (9) | −0.0025 (7) | 0.0038 (7) | 0.0005 (7) |
O1 | 0.0296 (8) | 0.0186 (8) | 0.0180 (7) | −0.0058 (7) | 0.0000 (6) | −0.0002 (6) |
O2 | 0.0255 (8) | 0.0187 (8) | 0.0173 (7) | −0.0054 (7) | 0.0050 (6) | −0.0007 (6) |
O3 | 0.0257 (8) | 0.0169 (8) | 0.0210 (7) | −0.0071 (7) | 0.0050 (6) | 0.0016 (6) |
O4 | 0.0301 (9) | 0.0165 (8) | 0.0204 (7) | −0.0082 (7) | 0.0040 (6) | −0.0021 (6) |
O5 | 0.0323 (9) | 0.0193 (8) | 0.0212 (7) | −0.0089 (7) | 0.0085 (6) | 0.0006 (6) |
O6 | 0.0452 (11) | 0.0174 (8) | 0.0282 (9) | −0.0005 (8) | −0.0069 (7) | 0.0044 (7) |
C1—C2 | 1.512 (3) | C19—H19 | 0.9500 |
C1—C6 | 1.553 (3) | C20—C21 | 1.448 (3) |
C1—H1A | 0.9900 | C21—H21 | 0.9500 |
C1—H1B | 0.9900 | C22—O1 | 1.433 (2) |
C2—O6 | 1.227 (2) | C22—H22A | 0.9800 |
C2—C3 | 1.493 (3) | C22—H22B | 0.9800 |
C3—O1 | 1.354 (2) | C22—H22C | 0.9800 |
C3—C4 | 1.361 (3) | C23—O5 | 1.426 (2) |
C4—C5 | 1.454 (3) | C23—H23A | 0.9800 |
C4—H4 | 0.9500 | C23—H23B | 0.9800 |
C5—C21 | 1.348 (3) | C23—H23C | 0.9800 |
C5—C6 | 1.515 (3) | C24—O4 | 1.423 (2) |
C6—C14 | 1.537 (3) | C24—H24A | 0.9800 |
C6—C7 | 1.548 (3) | C24—H24B | 0.9800 |
C7—C8 | 1.504 (3) | C24—H24C | 0.9800 |
C7—H7A | 0.9900 | C25—O2 | 1.431 (2) |
C7—H7B | 0.9900 | C25—H25A | 0.9800 |
C8—C13 | 1.392 (3) | C25—H25B | 0.9800 |
C8—C9 | 1.399 (3) | C25—H25C | 0.9800 |
C9—C10 | 1.387 (3) | C26—O3 | 1.440 (2) |
C9—H9 | 0.9500 | C26—H26A | 0.9800 |
C10—O5 | 1.369 (2) | C26—H26B | 0.9800 |
C10—C11 | 1.407 (3) | C26—H26C | 0.9800 |
C11—O4 | 1.372 (2) | C27—C28 | 1.386 (3) |
C11—C12 | 1.387 (3) | C27—C32 | 1.394 (3) |
C12—C13 | 1.404 (3) | C27—C33 | 1.507 (3) |
C12—H12 | 0.9500 | C28—C29 | 1.387 (3) |
C13—N1 | 1.420 (2) | C28—H28 | 0.9500 |
C14—N1 | 1.291 (3) | C29—C30 | 1.383 (4) |
C14—C15 | 1.480 (3) | C29—H29 | 0.9500 |
C15—C20 | 1.403 (3) | C30—C31 | 1.382 (3) |
C15—C16 | 1.407 (3) | C30—H30 | 0.9500 |
C16—C17 | 1.390 (3) | C31—C32 | 1.385 (3) |
C16—H16 | 0.9500 | C31—H31 | 0.9500 |
C17—O2 | 1.362 (2) | C32—H32 | 0.9500 |
C17—C18 | 1.420 (3) | C33—H33A | 0.9800 |
C18—O3 | 1.368 (2) | C33—H33B | 0.9800 |
C18—C19 | 1.379 (3) | C33—H33C | 0.9800 |
C19—C20 | 1.411 (3) | ||
C2—C1—C6 | 111.71 (16) | C15—C20—C19 | 119.14 (18) |
C2—C1—H1A | 109.3 | C15—C20—C21 | 120.99 (18) |
C6—C1—H1A | 109.3 | C19—C20—C21 | 119.86 (18) |
C2—C1—H1B | 109.3 | C5—C21—C20 | 123.13 (19) |
C6—C1—H1B | 109.3 | C5—C21—H21 | 118.4 |
H1A—C1—H1B | 107.9 | C20—C21—H21 | 118.4 |
O6—C2—C3 | 121.48 (19) | O1—C22—H22A | 109.5 |
O6—C2—C1 | 121.57 (19) | O1—C22—H22B | 109.5 |
C3—C2—C1 | 116.85 (18) | H22A—C22—H22B | 109.5 |
O1—C3—C4 | 127.01 (19) | O1—C22—H22C | 109.5 |
O1—C3—C2 | 113.21 (18) | H22A—C22—H22C | 109.5 |
C4—C3—C2 | 119.65 (18) | H22B—C22—H22C | 109.5 |
C3—C4—C5 | 121.56 (19) | O5—C23—H23A | 109.5 |
C3—C4—H4 | 119.2 | O5—C23—H23B | 109.5 |
C5—C4—H4 | 119.2 | H23A—C23—H23B | 109.5 |
C21—C5—C4 | 121.93 (19) | O5—C23—H23C | 109.5 |
C21—C5—C6 | 121.36 (17) | H23A—C23—H23C | 109.5 |
C4—C5—C6 | 116.32 (17) | H23B—C23—H23C | 109.5 |
C5—C6—C14 | 115.20 (16) | O4—C24—H24A | 109.5 |
C5—C6—C7 | 112.52 (16) | O4—C24—H24B | 109.5 |
C14—C6—C7 | 105.10 (16) | H24A—C24—H24B | 109.5 |
C5—C6—C1 | 104.72 (16) | O4—C24—H24C | 109.5 |
C14—C6—C1 | 110.39 (16) | H24A—C24—H24C | 109.5 |
C7—C6—C1 | 108.88 (16) | H24B—C24—H24C | 109.5 |
C8—C7—C6 | 107.96 (16) | O2—C25—H25A | 109.5 |
C8—C7—H7A | 110.1 | O2—C25—H25B | 109.5 |
C6—C7—H7A | 110.1 | H25A—C25—H25B | 109.5 |
C8—C7—H7B | 110.1 | O2—C25—H25C | 109.5 |
C6—C7—H7B | 110.1 | H25A—C25—H25C | 109.5 |
H7A—C7—H7B | 108.4 | H25B—C25—H25C | 109.5 |
C13—C8—C9 | 119.48 (19) | O3—C26—H26A | 109.5 |
C13—C8—C7 | 117.74 (18) | O3—C26—H26B | 109.5 |
C9—C8—C7 | 122.76 (17) | H26A—C26—H26B | 109.5 |
C10—C9—C8 | 120.85 (18) | O3—C26—H26C | 109.5 |
C10—C9—H9 | 119.6 | H26A—C26—H26C | 109.5 |
C8—C9—H9 | 119.6 | H26B—C26—H26C | 109.5 |
O5—C10—C9 | 124.88 (18) | C28—C27—C32 | 117.9 (2) |
O5—C10—C11 | 115.76 (18) | C28—C27—C33 | 121.4 (2) |
C9—C10—C11 | 119.36 (18) | C32—C27—C33 | 120.7 (2) |
O4—C11—C12 | 125.11 (18) | C27—C28—C29 | 121.3 (2) |
O4—C11—C10 | 114.56 (17) | C27—C28—H28 | 119.3 |
C12—C11—C10 | 120.31 (19) | C29—C28—H28 | 119.3 |
C11—C12—C13 | 119.77 (18) | C30—C29—C28 | 120.0 (2) |
C11—C12—H12 | 120.1 | C30—C29—H29 | 120.0 |
C13—C12—H12 | 120.1 | C28—C29—H29 | 120.0 |
C8—C13—C12 | 120.21 (18) | C31—C30—C29 | 119.5 (2) |
C8—C13—N1 | 121.20 (18) | C31—C30—H30 | 120.2 |
C12—C13—N1 | 118.56 (17) | C29—C30—H30 | 120.2 |
N1—C14—C15 | 118.74 (17) | C30—C31—C32 | 120.2 (2) |
N1—C14—C6 | 122.18 (18) | C30—C31—H31 | 119.9 |
C15—C14—C6 | 119.04 (17) | C32—C31—H31 | 119.9 |
C20—C15—C16 | 119.78 (18) | C31—C32—C27 | 121.1 (2) |
C20—C15—C14 | 119.54 (17) | C31—C32—H32 | 119.5 |
C16—C15—C14 | 120.57 (18) | C27—C32—H32 | 119.5 |
C17—C16—C15 | 120.79 (18) | C27—C33—H33A | 109.5 |
C17—C16—H16 | 119.6 | C27—C33—H33B | 109.5 |
C15—C16—H16 | 119.6 | H33A—C33—H33B | 109.5 |
O2—C17—C16 | 125.53 (18) | C27—C33—H33C | 109.5 |
O2—C17—C18 | 115.24 (17) | H33A—C33—H33C | 109.5 |
C16—C17—C18 | 119.23 (18) | H33B—C33—H33C | 109.5 |
O3—C18—C19 | 124.78 (18) | C14—N1—C13 | 117.94 (17) |
O3—C18—C17 | 115.18 (17) | C3—O1—C22 | 116.05 (16) |
C19—C18—C17 | 120.04 (18) | C17—O2—C25 | 117.29 (15) |
C18—C19—C20 | 120.98 (19) | C18—O3—C26 | 115.81 (15) |
C18—C19—H19 | 119.5 | C11—O4—C24 | 117.74 (16) |
C20—C19—H19 | 119.5 | C10—O5—C23 | 117.31 (16) |
C6—C1—C2—O6 | 148.9 (2) | N1—C14—C15—C20 | 167.52 (18) |
C6—C1—C2—C3 | −34.6 (3) | C6—C14—C15—C20 | −10.2 (3) |
O6—C2—C3—O1 | −0.1 (3) | N1—C14—C15—C16 | −8.6 (3) |
C1—C2—C3—O1 | −176.55 (17) | C6—C14—C15—C16 | 173.70 (18) |
O6—C2—C3—C4 | 176.1 (2) | C20—C15—C16—C17 | 1.7 (3) |
C1—C2—C3—C4 | −0.4 (3) | C14—C15—C16—C17 | 177.83 (18) |
O1—C3—C4—C5 | −176.57 (19) | C15—C16—C17—O2 | 178.08 (18) |
C2—C3—C4—C5 | 7.9 (3) | C15—C16—C17—C18 | −1.6 (3) |
C3—C4—C5—C21 | −151.1 (2) | O2—C17—C18—O3 | −0.2 (3) |
C3—C4—C5—C6 | 21.7 (3) | C16—C17—C18—O3 | 179.55 (18) |
C21—C5—C6—C14 | −2.0 (3) | O2—C17—C18—C19 | −179.77 (18) |
C4—C5—C6—C14 | −174.90 (17) | C16—C17—C18—C19 | 0.0 (3) |
C21—C5—C6—C7 | −122.5 (2) | O3—C18—C19—C20 | −177.93 (18) |
C4—C5—C6—C7 | 64.6 (2) | C17—C18—C19—C20 | 1.6 (3) |
C21—C5—C6—C1 | 119.4 (2) | C16—C15—C20—C19 | −0.1 (3) |
C4—C5—C6—C1 | −53.5 (2) | C14—C15—C20—C19 | −176.29 (18) |
C2—C1—C6—C5 | 58.7 (2) | C16—C15—C20—C21 | −178.69 (19) |
C2—C1—C6—C14 | −176.78 (17) | C14—C15—C20—C21 | 5.1 (3) |
C2—C1—C6—C7 | −61.9 (2) | C18—C19—C20—C15 | −1.5 (3) |
C5—C6—C7—C8 | −177.45 (16) | C18—C19—C20—C21 | 177.05 (19) |
C14—C6—C7—C8 | 56.4 (2) | C4—C5—C21—C20 | 169.34 (19) |
C1—C6—C7—C8 | −61.8 (2) | C6—C5—C21—C20 | −3.2 (3) |
C6—C7—C8—C13 | −37.5 (2) | C15—C20—C21—C5 | 1.7 (3) |
C6—C7—C8—C9 | 140.8 (2) | C19—C20—C21—C5 | −176.8 (2) |
C13—C8—C9—C10 | 0.2 (3) | C32—C27—C28—C29 | −0.5 (3) |
C7—C8—C9—C10 | −178.02 (19) | C33—C27—C28—C29 | 179.5 (2) |
C8—C9—C10—O5 | 179.2 (2) | C27—C28—C29—C30 | 0.7 (4) |
C8—C9—C10—C11 | −0.9 (3) | C28—C29—C30—C31 | −0.6 (4) |
O5—C10—C11—O4 | −0.9 (3) | C29—C30—C31—C32 | 0.2 (4) |
C9—C10—C11—O4 | 179.11 (18) | C30—C31—C32—C27 | 0.1 (3) |
O5—C10—C11—C12 | −179.63 (18) | C28—C27—C32—C31 | 0.0 (3) |
C9—C10—C11—C12 | 0.4 (3) | C33—C27—C32—C31 | −180.0 (2) |
O4—C11—C12—C13 | −177.92 (19) | C15—C14—N1—C13 | −171.83 (17) |
C10—C11—C12—C13 | 0.7 (3) | C6—C14—N1—C13 | 5.8 (3) |
C9—C8—C13—C12 | 0.8 (3) | C8—C13—N1—C14 | 20.8 (3) |
C7—C8—C13—C12 | 179.18 (18) | C12—C13—N1—C14 | −160.95 (18) |
C9—C8—C13—N1 | 179.03 (19) | C4—C3—O1—C22 | −4.9 (3) |
C7—C8—C13—N1 | −2.6 (3) | C2—C3—O1—C22 | 170.91 (18) |
C11—C12—C13—C8 | −1.3 (3) | C16—C17—O2—C25 | −1.5 (3) |
C11—C12—C13—N1 | −179.52 (18) | C18—C17—O2—C25 | 178.24 (17) |
C5—C6—C14—N1 | −169.12 (18) | C19—C18—O3—C26 | −3.4 (3) |
C7—C6—C14—N1 | −44.7 (2) | C17—C18—O3—C26 | 177.01 (17) |
C1—C6—C14—N1 | 72.6 (2) | C12—C11—O4—C24 | −10.4 (3) |
C5—C6—C14—C15 | 8.5 (3) | C10—C11—O4—C24 | 170.96 (18) |
C7—C6—C14—C15 | 132.91 (18) | C9—C10—O5—C23 | −12.3 (3) |
C1—C6—C14—C15 | −109.8 (2) | C11—C10—O5—C23 | 167.70 (19) |
Experimental details
Crystal data | |
Chemical formula | C26H25NO6·C7H8 |
Mr | 539.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 14.952 (4), 7.1736 (18), 25.787 (6) |
β (°) | 94.571 (7) |
V (Å3) | 2757.1 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.60 × 0.19 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (TWINABS; Bruker, 2003) |
Tmin, Tmax | 0.773, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40178, 10641, 7887 |
Rint | not defined due to twin pairing errors, Herbst-Irmer, 2006 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.199, 1.08 |
No. of reflections | 10641 |
No. of parameters | 368 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.25 |
Computer programs: SMART (Bruker, 2002), CELL_NOW (Sheldrick, 2004) and SAINT-Plus (Bruker, 2003), SAINT-Plus (Bruker, 2003), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23B···O4i | 0.98 | 2.41 | 3.354 (3) | 160.4 |
C26—H26B···O2ii | 0.98 | 2.59 | 3.210 (3) | 120.9 |
C26—H26C···O6iii | 0.98 | 2.58 | 3.526 (3) | 162.2 |
C12—H12···Cg2iV | 0.95 | 3.3199 | 3.780 (2) | 112.02 |
C22—H22A···Cg2iii | 0.98 | 2.9687 | 3.557 (3) | 119.73 |
C23—H23C···Cg1v | 0.98 | 2.9869 | 3.902 (3) | 155.82 |
C24—H24A···Cg3vi | 0.98 | 2.6627 | 3.447 (3) | 137.12 |
C25—H25C···Cg3 | 0.98 | 2.6327 | 3.487 (3) | 145.87 |
Cg1 denotes the centroid of ring C8–C13, Cg2 that of C15–C20, and Cg3 that of C27–C32. Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, y+1/2, -z+1/2; (iii) -x+1, -y+2, -z+1; (iv) x, y-1, z; (v) -x, -y+1, -z+1; (vi) -x, y-1/2, -z+1/2. |
The crown-shaped [1.1.1]orthocyclophane cyclotriveratrylene (CTV, hexamethoxy tribenzocyclononene) molecule has been employed extensively as a scaffold in supramolecular chemistry (Collet, 1987). We are interested in new apex-modified derivatives of CTV and recently reported the isolation of the crown and saddle conformers of CTV oxime (Lutz et al., 2007). In the course of studying the Beckmann rearrangement of this molecule we observed the unexpected formation of the title compound, resulting from a Beckmann rearrangement followed by an intramolecular electrophilic aromatic addition and subsequent demethylation (Fig. 1). Studies of the reaction conditions and mechanism will be discussed in detail in a separate publication.
The title compound was crystallized from methylene chloride/toluene as its toluene solvate (Figure 2). The red needle-like crystals were heavily intergrown, and the crystal that was finally selected for single-crystal data collection was found to be non-merohedrally twinned with two twin components in a ratio of 0.688 (2) to 0.312 (2) (See experimental refinement section for details of unit cell determination, data workup, refinement, and type of twinning).
The compound shows an unusual helical arrangement of three six-membered rings that are all connected at the central carbon atom C6. The helix effectively performs one full turn around C6, and the thread pitch, as defined by the distance of the terminal atoms C2 and C20 of the helix, is 4.98 (3) Å. The angles around C6 are between 104.7 (2) and 115.2 (2)°. The middle ring, a cyclohexa-2,4-dienimine with C6 being the only saturated atom in the ring, is nearly planar with an r.m.s. deviation from the mean plane of only 0.035 Å. The other two rings have conformations best described as between envelope and screw-boat (Boeyens, 1978) with puckering amplitudes of 0.527 (2) and 0.544 (2) Å, respectively (Cremer & Pople, 1975).
The packing of the title compound, illustrated in Figure 3, seems to be dominated by a combination of simple dispersion forces, and weak interactions of the methoxy methyl hydrogen bonds with both neigboring oxygen atoms and aromatic rings. All methoxy groups are involved in at least one C—H···O hydrogen bond or C—H···π contact, and all aromatic rings act as an acceptor to one or two methoxy CH3 groups.