Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015586/tk6039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015586/tk6039Isup2.hkl |
CCDC reference: 175376
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.002 Å
- R factor = 0.050
- wR factor = 0.114
- Data-to-parameter ratio = 22.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Sodium hydroxide (10% aq.) (10 ml) was added to 2,3,5,6,9,10,11,12-octahydro-8H-1,4,7,12-benzotrioxaazacyclotetradecine (50 mg, 0.20 mmol) dissolved in THF (10 ml). This mixture was allowed to stir for 10 min, benzoyl chloride (56 mg, 0.40 mmol) was added dropwise and the resulting mixture was allowed to stir for 24 h. The reaction was poured into water (50 ml) and extracted into CH2Cl2 (3 × 50 ml), dried (Na2SO4), filtered and the solvent was removed under reduced pressure to give a yellow oil. Excess benzoyl chloride was removed on the high vacuum pump. Column chromatography of the residue (SiO2, 20% EtOAc/hexane) gave amide (I) as a yellow oil which solidified on standing (70 mg, 99%). Dichloromethane (10 ml) was added to the amide and single crystals suitable for X-ray structure determination were obtained by slow evaporation of the solution; m.p: 415.4–417.6 K.
Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C21H25NO4 | F(000) = 760 |
Mr = 355.42 | Dx = 1.272 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25477 reflections |
a = 16.825 (1) Å | θ = 2.4–30.0° |
b = 13.550 (1) Å | µ = 0.09 mm−1 |
c = 8.173 (1) Å | T = 123 K |
β = 95.02 (1)° | Tabular, colourless |
V = 1856.1 (3) Å3 | 0.22 × 0.16 × 0.09 mm |
Z = 4 |
KappaCCD diffractometer | Rint = 0.056 |
CCD rotation images, thick slices scans | θmax = 30.1°, θmin = 2.4° |
25477 measured reflections | h = −23→23 |
5351 independent reflections | k = −18→18 |
3438 reflections with I > 2σ(I) | l = −11→11 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.0485P)2 + 0.2125P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.114 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.19 e Å−3 |
5351 reflections | Δρmin = −0.23 e Å−3 |
235 parameters |
C21H25NO4 | V = 1856.1 (3) Å3 |
Mr = 355.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.825 (1) Å | µ = 0.09 mm−1 |
b = 13.550 (1) Å | T = 123 K |
c = 8.173 (1) Å | 0.22 × 0.16 × 0.09 mm |
β = 95.02 (1)° |
KappaCCD diffractometer | 3438 reflections with I > 2σ(I) |
25477 measured reflections | Rint = 0.056 |
5351 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
5351 reflections | Δρmin = −0.23 e Å−3 |
235 parameters |
Experimental. 1H n.m.r. (CDCl3): δ 1.59–1.92 (m, 4H, H9,10), 3.44–3.53 (m, 1H), 3.54–3.68 (m, 6H), 3.80–3.86 (m, 2H), 3.94–3.99 (m, 1H), 4.21–4.28 (m, 1H) and 4.34–4.44 (m, 1H) (H2,3,5,6,8,11), 6.69–6.74 (m, 2H, H14,16), 6.88–6.91 (m, 1H, H15), 7.05–7.18 (m, 4H) and 7.22–7.29 (m, 2H)(H13,PhCH). 13C n.m.r. (CDCl3): δ 24.99 (C10); 27.49 (C9); 49.28 (C11); 67.04, 69.17, 69.54, 70.74 (C3,5,6,8); 71.07 (C2) 111.95 (C16); 120.46 (C13,14); 127.29, 127.84, 128.29, 129.07, 130.45 (C15, PhCH); 132.49 (C12a); 137.14 (PhC); 154.01 (C16a); 171.11 (C═O). |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.33270 (8) | −0.03036 (10) | 0.06246 (16) | 0.0273 (3) | |
C2 | 0.41424 (8) | −0.04709 (10) | 0.14610 (17) | 0.0280 (3) | |
C3 | 0.52608 (8) | 0.03753 (11) | 0.27160 (17) | 0.0308 (3) | |
C4 | 0.55638 (8) | 0.13789 (12) | 0.32476 (17) | 0.0348 (4) | |
C5 | 0.44193 (8) | 0.22314 (10) | 0.41630 (17) | 0.0293 (3) | |
C6 | 0.37354 (8) | 0.16489 (9) | 0.47678 (16) | 0.0237 (3) | |
C7 | 0.29531 (8) | 0.21973 (9) | 0.43657 (16) | 0.0250 (3) | |
C8 | 0.22182 (8) | 0.17255 (9) | 0.50053 (16) | 0.0241 (3) | |
C9 | 0.16537 (8) | 0.08104 (9) | 0.25157 (15) | 0.0197 (3) | |
C10 | 0.08929 (8) | 0.11721 (9) | 0.20970 (16) | 0.0246 (3) | |
C11 | 0.05658 (8) | 0.11546 (10) | 0.04824 (17) | 0.0282 (3) | |
C12 | 0.10080 (8) | 0.07750 (10) | −0.07209 (16) | 0.0275 (3) | |
C13 | 0.17758 (8) | 0.04255 (9) | −0.03383 (15) | 0.0237 (3) | |
C14 | 0.21060 (8) | 0.04539 (9) | 0.12799 (15) | 0.0200 (3) | |
C15 | 0.22114 (8) | −0.00879 (9) | 0.49285 (15) | 0.0205 (3) | |
C16 | 0.18803 (8) | −0.10093 (9) | 0.41167 (15) | 0.0214 (3) | |
C17 | 0.10606 (8) | −0.11350 (10) | 0.38082 (16) | 0.0260 (3) | |
C18 | 0.07552 (9) | −0.20174 (10) | 0.31630 (17) | 0.0322 (3) | |
C19 | 0.12668 (9) | −0.27634 (10) | 0.27956 (17) | 0.0336 (4) | |
C20 | 0.20844 (9) | −0.26434 (10) | 0.30790 (16) | 0.0304 (3) | |
C21 | 0.23918 (8) | −0.17713 (10) | 0.37636 (15) | 0.0247 (3) | |
N1 | 0.19814 (6) | 0.07855 (7) | 0.41986 (12) | 0.0197 (2) | |
O1 | 0.28600 (5) | 0.01530 (6) | 0.17972 (10) | 0.0230 (2) | |
O2 | 0.45117 (5) | 0.04608 (7) | 0.17720 (11) | 0.0270 (2) | |
O3 | 0.51846 (6) | 0.17873 (8) | 0.45874 (12) | 0.0338 (3) | |
O4 | 0.26358 (6) | −0.01290 (7) | 0.62335 (11) | 0.0258 (2) | |
H1A | 0.3357 | 0.013 | −0.0343 | 0.033* | |
H1B | 0.3084 | −0.0939 | 0.025 | 0.033* | |
H2A | 0.4104 | −0.0829 | 0.2507 | 0.034* | |
H2B | 0.4464 | −0.0874 | 0.0752 | 0.034* | |
H3A | 0.565 | 0.0051 | 0.2051 | 0.037* | |
H3B | 0.5201 | −0.0039 | 0.3695 | 0.037* | |
H4A | 0.6144 | 0.1333 | 0.3564 | 0.042* | |
H4B | 0.5486 | 0.1835 | 0.2301 | 0.042* | |
H5A | 0.4335 | 0.2295 | 0.2954 | 0.035* | |
H5B | 0.4418 | 0.2904 | 0.4636 | 0.035* | |
H6A | 0.3827 | 0.1552 | 0.597 | 0.028* | |
H6B | 0.3706 | 0.0991 | 0.4238 | 0.028* | |
H7A | 0.286 | 0.2259 | 0.3157 | 0.03* | |
H7B | 0.3011 | 0.2873 | 0.4822 | 0.03* | |
H8A | 0.2326 | 0.1609 | 0.62 | 0.029* | |
H8B | 0.1767 | 0.2194 | 0.4847 | 0.029* | |
H10 | 0.0592 | 0.1435 | 0.2927 | 0.03* | |
H11 | 0.0043 | 0.1401 | 0.0204 | 0.034* | |
H12 | 0.0782 | 0.0754 | −0.1827 | 0.033* | |
H13 | 0.2074 | 0.0168 | −0.1176 | 0.028* | |
H17 | 0.0709 | −0.0615 | 0.404 | 0.031* | |
H18 | 0.0195 | −0.2107 | 0.2975 | 0.039* | |
H19 | 0.1057 | −0.3365 | 0.2344 | 0.04* | |
H20 | 0.2434 | −0.3157 | 0.2806 | 0.036* | |
H21 | 0.2952 | −0.1695 | 0.3991 | 0.03* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0283 (8) | 0.0298 (7) | 0.0246 (7) | 0.0050 (6) | 0.0070 (6) | −0.0057 (6) |
C2 | 0.0288 (8) | 0.0281 (7) | 0.0279 (7) | 0.0072 (6) | 0.0067 (6) | −0.0005 (6) |
C3 | 0.0207 (7) | 0.0475 (9) | 0.0243 (7) | 0.0099 (6) | 0.0032 (6) | 0.0080 (6) |
C4 | 0.0199 (7) | 0.0554 (10) | 0.0291 (8) | −0.0003 (7) | 0.0018 (6) | 0.0074 (7) |
C5 | 0.0265 (8) | 0.0305 (7) | 0.0302 (7) | 0.0000 (6) | −0.0016 (6) | 0.0042 (6) |
C6 | 0.0266 (7) | 0.0214 (7) | 0.0226 (6) | −0.0014 (5) | −0.0006 (5) | 0.0004 (5) |
C7 | 0.0292 (8) | 0.0187 (6) | 0.0265 (7) | 0.0000 (5) | −0.0004 (6) | −0.0005 (5) |
C8 | 0.0275 (7) | 0.0203 (7) | 0.0244 (6) | 0.0029 (5) | 0.0019 (5) | −0.0056 (5) |
C9 | 0.0234 (7) | 0.0162 (6) | 0.0192 (6) | −0.0012 (5) | 0.0010 (5) | 0.0002 (5) |
C10 | 0.0245 (7) | 0.0225 (7) | 0.0270 (7) | 0.0022 (5) | 0.0036 (5) | −0.0001 (5) |
C11 | 0.0230 (7) | 0.0290 (7) | 0.0319 (7) | 0.0037 (6) | −0.0019 (6) | 0.0019 (6) |
C12 | 0.0317 (8) | 0.0272 (7) | 0.0221 (7) | −0.0004 (6) | −0.0050 (6) | 0.0012 (6) |
C13 | 0.0285 (8) | 0.0237 (7) | 0.0193 (6) | −0.0016 (5) | 0.0030 (5) | −0.0013 (5) |
C14 | 0.0203 (7) | 0.0179 (6) | 0.0217 (6) | −0.0013 (5) | 0.0012 (5) | 0.0014 (5) |
C15 | 0.0207 (7) | 0.0232 (7) | 0.0181 (6) | 0.0003 (5) | 0.0050 (5) | −0.0003 (5) |
C16 | 0.0283 (7) | 0.0205 (6) | 0.0154 (6) | −0.0011 (5) | 0.0015 (5) | 0.0025 (5) |
C17 | 0.0272 (7) | 0.0243 (7) | 0.0264 (7) | −0.0014 (6) | 0.0011 (6) | 0.0037 (6) |
C18 | 0.0336 (8) | 0.0290 (8) | 0.0324 (8) | −0.0086 (6) | −0.0063 (6) | 0.0053 (6) |
C19 | 0.0493 (10) | 0.0232 (7) | 0.0267 (7) | −0.0092 (7) | −0.0057 (7) | 0.0003 (6) |
C20 | 0.0473 (9) | 0.0217 (7) | 0.0221 (7) | 0.0040 (6) | 0.0031 (6) | 0.0007 (6) |
C21 | 0.0289 (8) | 0.0249 (7) | 0.0202 (6) | 0.0014 (5) | 0.0014 (5) | 0.0011 (5) |
N1 | 0.0231 (6) | 0.0181 (5) | 0.0180 (5) | 0.0012 (4) | 0.0016 (4) | −0.0019 (4) |
O1 | 0.0206 (5) | 0.0293 (5) | 0.0194 (4) | 0.0031 (4) | 0.0029 (4) | −0.0030 (4) |
O2 | 0.0220 (5) | 0.0322 (5) | 0.0265 (5) | 0.0042 (4) | 0.0004 (4) | 0.0051 (4) |
O3 | 0.0245 (6) | 0.0494 (7) | 0.0268 (5) | 0.0005 (4) | −0.0024 (4) | 0.0017 (5) |
O4 | 0.0300 (6) | 0.0270 (5) | 0.0197 (5) | −0.0001 (4) | −0.0014 (4) | −0.0001 (4) |
C1—O1 | 1.4320 (15) | C20—C21 | 1.3880 (19) |
C1—C2 | 1.4956 (19) | C1—H1A | 0.99 |
C2—O2 | 1.4201 (17) | C1—H1B | 0.99 |
C3—O2 | 1.4237 (16) | C2—H2A | 0.99 |
C3—C4 | 1.503 (2) | C2—H2B | 0.99 |
C4—O3 | 1.4265 (18) | C3—H3A | 0.99 |
C5—O3 | 1.4360 (16) | C3—H3B | 0.99 |
C5—C6 | 1.5135 (18) | C4—H4A | 0.99 |
C6—C7 | 1.5222 (18) | C4—H4B | 0.99 |
C7—C8 | 1.5244 (19) | C5—H5A | 0.99 |
C8—N1 | 1.4731 (16) | C5—H5B | 0.99 |
C9—C10 | 1.3852 (18) | C6—H6A | 0.99 |
C9—C14 | 1.4026 (18) | C6—H6B | 0.99 |
C9—N1 | 1.4367 (16) | C7—H7A | 0.99 |
C10—C11 | 1.3848 (18) | C7—H7B | 0.99 |
C11—C12 | 1.383 (2) | C8—H8A | 0.99 |
C12—C13 | 1.3856 (19) | C8—H8B | 0.99 |
C13—C14 | 1.3894 (17) | C10—H10 | 0.95 |
C14—O1 | 1.3640 (15) | C11—H11 | 0.95 |
C15—O4 | 1.2318 (15) | C12—H12 | 0.95 |
C15—N1 | 1.3659 (16) | C13—H13 | 0.95 |
C15—C16 | 1.4982 (18) | C17—H17 | 0.95 |
C16—C21 | 1.3905 (18) | C18—H18 | 0.95 |
C16—C17 | 1.3906 (18) | C19—H19 | 0.95 |
C17—C18 | 1.3871 (19) | C20—H20 | 0.95 |
C18—C19 | 1.378 (2) | C21—H21 | 0.95 |
C19—C20 | 1.384 (2) | ||
O1—C1—C2 | 107.14 (10) | O3—C4—H4A | 108.7 |
O2—C2—C1 | 108.45 (11) | C3—C4—H4A | 108.7 |
O2—C3—C4 | 110.17 (12) | O3—C4—H4B | 108.7 |
O3—C4—C3 | 114.19 (11) | C3—C4—H4B | 108.7 |
O3—C5—C6 | 113.19 (11) | O3—C5—H5A | 108.9 |
C5—C6—C7 | 110.04 (11) | C6—C5—H5A | 108.9 |
C6—C7—C8 | 115.67 (11) | O3—C5—H5B | 108.9 |
N1—C8—C7 | 113.88 (11) | C6—C5—H5B | 108.9 |
C10—C9—C14 | 119.46 (11) | C5—C6—H6A | 109.7 |
C10—C9—N1 | 120.92 (11) | C7—C6—H6A | 109.7 |
C14—C9—N1 | 119.62 (11) | C5—C6—H6B | 109.7 |
C11—C10—C9 | 120.73 (12) | C7—C6—H6B | 109.7 |
C12—C11—C10 | 119.35 (13) | C6—C7—H7A | 108.4 |
C11—C12—C13 | 121.03 (12) | C8—C7—H7A | 108.4 |
C12—C13—C14 | 119.51 (12) | C6—C7—H7B | 108.4 |
O1—C14—C13 | 124.78 (11) | C8—C7—H7B | 108.4 |
O1—C14—C9 | 115.35 (10) | N1—C8—H8A | 108.8 |
C13—C14—C9 | 119.87 (12) | C7—C8—H8A | 108.8 |
O4—C15—N1 | 122.54 (12) | N1—C8—H8B | 108.8 |
O4—C15—C16 | 120.71 (11) | C7—C8—H8B | 108.8 |
N1—C15—C16 | 116.64 (11) | C11—C10—H10 | 119.6 |
C21—C16—C17 | 119.57 (12) | C9—C10—H10 | 119.6 |
C21—C16—C15 | 119.85 (12) | C12—C11—H11 | 120.3 |
C17—C16—C15 | 120.46 (12) | C10—C11—H11 | 120.3 |
C18—C17—C16 | 120.20 (13) | C11—C12—H12 | 119.5 |
C19—C18—C17 | 119.84 (14) | C13—C12—H12 | 119.5 |
C18—C19—C20 | 120.53 (13) | C12—C13—H13 | 120.2 |
C19—C20—C21 | 119.82 (13) | C14—C13—H13 | 120.2 |
C20—C21—C16 | 120.02 (13) | C18—C17—H17 | 119.9 |
C15—N1—C9 | 120.59 (10) | C16—C17—H17 | 119.9 |
C15—N1—C8 | 119.90 (10) | C19—C18—H18 | 120.1 |
C9—N1—C8 | 118.31 (10) | C17—C18—H18 | 120.1 |
C14—O1—C1 | 118.14 (9) | C18—C19—H19 | 119.7 |
C2—O2—C3 | 112.17 (10) | C20—C19—H19 | 119.7 |
C4—O3—C5 | 115.40 (10) | C19—C20—H20 | 120.1 |
O1—C1—H1A | 110.3 | C21—C20—H20 | 120.1 |
C2—C1—H1A | 110.3 | C20—C21—H21 | 120 |
O1—C1—H1B | 110.3 | C16—C21—H21 | 120 |
C2—C1—H1B | 110.3 | H1A—C1—H1B | 108.5 |
O2—C2—H2A | 110 | H2A—C2—H2B | 108.4 |
C1—C2—H2A | 110 | H3A—C3—H3B | 108.1 |
O2—C2—H2B | 110 | H4A—C4—H4B | 107.6 |
C1—C2—H2B | 110 | H5A—C5—H5B | 107.8 |
O2—C3—H3A | 109.6 | H6A—C6—H6B | 108.2 |
C4—C3—H3A | 109.6 | H7A—C7—H7B | 107.4 |
O2—C3—H3B | 109.6 | H8A—C8—H8B | 107.7 |
C4—C3—H3B | 109.6 |
Experimental details
Crystal data | |
Chemical formula | C21H25NO4 |
Mr | 355.42 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 16.825 (1), 13.550 (1), 8.173 (1) |
β (°) | 95.02 (1) |
V (Å3) | 1856.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.22 × 0.16 × 0.09 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25477, 5351, 3438 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.706 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.114, 1.04 |
No. of reflections | 5351 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.23 |
Computer programs: COLLECT (Nonius, 1997-2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Incorporation of N-donor atoms into the macrocyclic framework of crown ethers gives aza-crown analogues which can display increased binding strength and selectivity towards transition and post-transition metal ions (Bradshaw et al., 1996). We have reported the preparation of a range of benzo-aza-crown ethers by a protocol involving reductive cyclization of nitroarenes bearing aldehyde-containing side chains (Ventrice et al., 1999, 2001). An X-ray structure determination of the benzoyl derivative, (I), was undertaken to establish the conformation of this compound (Fig. 1).