Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030667/dn6255sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030667/dn6255Isup2.hkl |
CCDC reference: 287553
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.004 Å
- R factor = 0.031
- wR factor = 0.066
- Data-to-parameter ratio = 18.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
To a solution of 4-ethoxy-3-iodobenzaldehyde (2 mmol), prepared according to the method of Harapanhalli et al. (1996), and (3,5-dimethoxyphenyl)acetic acid (2 mmol) in acetic anhydride (10 ml), triethylamine (4 mmol) was added dropwise and the solution was stirred at 363 K for 6 h. Water (6 ml) was then added and the reaction was allowed to continue for 30 min, after which K2CO3 (8 mmol) in water (10 ml) was added dropwise and the reaction warmed to 333 K. The reaction was stirred for an additional 30 min, then cooled to 283 K, and acidified to pH 3 with 6 M HCl. The aqueous solution was extracted with CH2Cl2 (3 × 15 ml), and the organic phases were combined, washed with brine (3 × 15 ml), and dried. The solution was then concentrated under reduced pressure and the residue was recrystallized from ethanol to afford compound (I) (yield: 80%, m.p. 480 K). 1H NMR (d6-DMSO, 200 MHz): δ 7.61 (s, 1H), 7.53 (s, 1H), 7.12 (d, 1H), 6.85 (d, 1H), 6.52 (s, 1H), 6.31 (s, 2H), 4.06 (q, J = 6.6 Hz, 2H), 3.71 (s, 6H), 1.31 (t, J = 6.6 Hz, 3H). HR–MS (ESI), calculated for C19H19IO5: [M+Na]+ 477.0169; found: 477.0188. Crystals suitable for single-crystal X-ray diffraction were obtained by evaporation of an ethanol solution at 298 K.
All H atoms were initially located in a difference Fourier map but they were treated as riding on their parent atoms, with C—H distances of 0.99 (CH2), 0.98 (CH3) and 0.95 Å (aromatic), and an O—H distance of 0.84 Å, with Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(C,O).
Data collection: ASTRO (Bruker, 1997); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C19H19IO5 | F(000) = 904 |
Mr = 454.26 | Dx = 1.624 Mg m−3 |
Monoclinic, P21/n | Melting point: 480 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 12.688 (2) Å | Cell parameters from 978 reflections |
b = 11.1649 (19) Å | θ = 3.1–27.9° |
c = 14.229 (2) Å | µ = 1.75 mm−1 |
β = 112.861 (2)° | T = 193 K |
V = 1857.4 (5) Å3 | Chunk, yellow |
Z = 4 | 0.20 × 0.16 × 0.12 mm |
Bruker CCD diffractometer | 4310 independent reflections |
Radiation source: normal-focus sealed tube | 4085 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
Detector resolution: 836.6 pixels mm-1 | θmax = 27.9°, θmin = 1.8° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→14 |
Tmin = 0.665, Tmax = 0.811 | l = −18→17 |
11524 measured reflections |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0209P)2 + 1.9018P] where P = (Fo2 + 2Fc2)/3 |
4310 reflections | (Δ/σ)max = 0.001 |
230 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
C19H19IO5 | V = 1857.4 (5) Å3 |
Mr = 454.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.688 (2) Å | µ = 1.75 mm−1 |
b = 11.1649 (19) Å | T = 193 K |
c = 14.229 (2) Å | 0.20 × 0.16 × 0.12 mm |
β = 112.861 (2)° |
Bruker CCD diffractometer | 4310 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4085 reflections with I > 2σ(I) |
Tmin = 0.665, Tmax = 0.811 | Rint = 0.015 |
11524 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.20 | Δρmax = 0.94 e Å−3 |
4310 reflections | Δρmin = −0.85 e Å−3 |
230 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 | ||
I1 | 0.253688 (14) | 0.575415 (16) | 0.837858 (14) | 0.03562 (7) | |
O1 | 0.49958 (15) | 0.67215 (17) | 0.94443 (14) | 0.0343 (4) | |
O2 | 0.43602 (16) | 0.10649 (19) | 0.55353 (18) | 0.0440 (5) | |
H2 | 0.4245 | 0.0479 | 0.5137 | 0.066* | |
O3 | 0.61220 (15) | 0.08982 (17) | 0.55559 (15) | 0.0361 (4) | |
O4 | 0.98142 (15) | 0.22074 (19) | 0.83432 (16) | 0.0432 (5) | |
O5 | 0.83786 (18) | 0.55924 (18) | 0.61824 (17) | 0.0449 (5) | |
C1 | 0.5418 (2) | 0.1423 (2) | 0.5816 (2) | 0.0291 (5) | |
C2 | 0.57425 (19) | 0.2496 (2) | 0.64783 (19) | 0.0269 (5) | |
C3 | 0.4985 (2) | 0.2936 (2) | 0.6837 (2) | 0.0289 (5) | |
H3 | 0.4261 | 0.2548 | 0.6579 | 0.035* | |
C4 | 0.69177 (19) | 0.2987 (2) | 0.67223 (18) | 0.0261 (5) | |
C5 | 0.7855 (2) | 0.2388 (2) | 0.7398 (2) | 0.0299 (5) | |
H5 | 0.7759 | 0.1646 | 0.7681 | 0.036* | |
C6 | 0.8948 (2) | 0.2876 (2) | 0.7665 (2) | 0.0311 (5) | |
C7 | 0.9093 (2) | 0.3950 (2) | 0.7253 (2) | 0.0320 (6) | |
H7 | 0.9835 | 0.4287 | 0.7443 | 0.038* | |
C8 | 0.8138 (2) | 0.4540 (2) | 0.6555 (2) | 0.0318 (5) | |
C9 | 0.7046 (2) | 0.4069 (2) | 0.6284 (2) | 0.0296 (5) | |
H9 | 0.6399 | 0.4475 | 0.5810 | 0.036* | |
C10 | 0.5079 (2) | 0.3904 (2) | 0.75544 (19) | 0.0271 (5) | |
C11 | 0.4065 (2) | 0.4285 (2) | 0.76369 (19) | 0.0273 (5) | |
H11 | 0.3365 | 0.3896 | 0.7245 | 0.033* | |
C12 | 0.4062 (2) | 0.5213 (2) | 0.82762 (18) | 0.0255 (5) | |
C13 | 0.5083 (2) | 0.5790 (2) | 0.88722 (18) | 0.0265 (5) | |
C14 | 0.6101 (2) | 0.5385 (2) | 0.88278 (19) | 0.0283 (5) | |
H14 | 0.6804 | 0.5745 | 0.9249 | 0.034* | |
C15 | 0.6098 (2) | 0.4465 (2) | 0.8179 (2) | 0.0289 (5) | |
H15 | 0.6801 | 0.4207 | 0.8156 | 0.035* | |
C16 | 1.0956 (2) | 0.2541 (3) | 0.8506 (2) | 0.0455 (7) | |
H16A | 1.1036 | 0.2584 | 0.7849 | 0.068* | |
H16B | 1.1489 | 0.1943 | 0.8941 | 0.068* | |
H16C | 1.1128 | 0.3325 | 0.8841 | 0.068* | |
C17 | 0.7481 (3) | 0.6147 (3) | 0.5354 (3) | 0.0539 (8) | |
H17A | 0.7190 | 0.5586 | 0.4780 | 0.081* | |
H17B | 0.7774 | 0.6867 | 0.5143 | 0.081* | |
H17C | 0.6860 | 0.6369 | 0.5568 | 0.081* | |
C18 | 0.6015 (2) | 0.7377 (2) | 1.0031 (2) | 0.0324 (5) | |
H18A | 0.6439 | 0.7597 | 0.9601 | 0.039* | |
H18B | 0.6521 | 0.6889 | 1.0612 | 0.039* | |
C19 | 0.5628 (3) | 0.8482 (3) | 1.0409 (3) | 0.0554 (9) | |
H19A | 0.5106 | 0.8940 | 0.9827 | 0.083* | |
H19B | 0.6294 | 0.8976 | 1.0797 | 0.083* | |
H19C | 0.5232 | 0.8250 | 1.0851 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.02552 (9) | 0.03776 (11) | 0.04726 (11) | 0.00453 (7) | 0.01816 (7) | −0.00501 (8) |
O1 | 0.0298 (9) | 0.0317 (10) | 0.0417 (10) | −0.0009 (7) | 0.0143 (8) | −0.0135 (8) |
O2 | 0.0282 (9) | 0.0435 (12) | 0.0662 (14) | −0.0145 (8) | 0.0248 (9) | −0.0311 (10) |
O3 | 0.0278 (9) | 0.0349 (10) | 0.0497 (11) | −0.0055 (7) | 0.0194 (8) | −0.0168 (9) |
O4 | 0.0243 (9) | 0.0451 (12) | 0.0520 (12) | −0.0019 (8) | 0.0060 (8) | 0.0048 (10) |
O5 | 0.0454 (12) | 0.0363 (11) | 0.0540 (13) | −0.0110 (9) | 0.0205 (10) | 0.0064 (9) |
C1 | 0.0240 (11) | 0.0301 (13) | 0.0356 (13) | −0.0036 (10) | 0.0141 (10) | −0.0068 (11) |
C2 | 0.0230 (11) | 0.0242 (12) | 0.0345 (12) | −0.0047 (9) | 0.0123 (10) | −0.0076 (10) |
C3 | 0.0234 (11) | 0.0284 (13) | 0.0361 (13) | −0.0039 (9) | 0.0128 (10) | −0.0064 (10) |
C4 | 0.0240 (11) | 0.0270 (12) | 0.0307 (12) | −0.0039 (9) | 0.0143 (10) | −0.0097 (10) |
C5 | 0.0289 (12) | 0.0260 (12) | 0.0376 (13) | −0.0032 (10) | 0.0161 (10) | −0.0035 (10) |
C6 | 0.0259 (11) | 0.0329 (14) | 0.0348 (13) | −0.0013 (10) | 0.0121 (10) | −0.0060 (11) |
C7 | 0.0254 (11) | 0.0345 (14) | 0.0383 (14) | −0.0089 (10) | 0.0147 (11) | −0.0080 (11) |
C8 | 0.0366 (13) | 0.0279 (13) | 0.0366 (14) | −0.0059 (10) | 0.0206 (11) | −0.0045 (10) |
C9 | 0.0280 (12) | 0.0290 (13) | 0.0336 (13) | 0.0004 (10) | 0.0139 (10) | −0.0040 (10) |
C10 | 0.0252 (11) | 0.0255 (12) | 0.0343 (13) | −0.0023 (9) | 0.0154 (10) | −0.0039 (10) |
C11 | 0.0220 (11) | 0.0274 (12) | 0.0339 (12) | −0.0035 (9) | 0.0124 (10) | −0.0018 (10) |
C12 | 0.0236 (11) | 0.0241 (12) | 0.0305 (12) | 0.0016 (9) | 0.0126 (9) | 0.0013 (9) |
C13 | 0.0287 (11) | 0.0239 (12) | 0.0289 (12) | 0.0005 (9) | 0.0134 (10) | 0.0001 (10) |
C14 | 0.0237 (11) | 0.0298 (13) | 0.0318 (12) | −0.0037 (9) | 0.0114 (10) | −0.0046 (10) |
C15 | 0.0230 (11) | 0.0312 (13) | 0.0357 (13) | −0.0014 (9) | 0.0151 (10) | −0.0047 (10) |
C16 | 0.0249 (12) | 0.0517 (19) | 0.0533 (18) | −0.0018 (12) | 0.0080 (12) | −0.0072 (15) |
C17 | 0.065 (2) | 0.0438 (18) | 0.0518 (19) | −0.0043 (16) | 0.0211 (17) | 0.0133 (15) |
C18 | 0.0340 (13) | 0.0282 (13) | 0.0312 (13) | −0.0030 (10) | 0.0087 (11) | −0.0039 (10) |
C19 | 0.057 (2) | 0.0393 (18) | 0.062 (2) | 0.0012 (15) | 0.0143 (17) | −0.0228 (16) |
I1—C12 | 2.086 (2) | C9—H9 | 0.9500 |
O1—C13 | 1.352 (3) | C10—C15 | 1.400 (3) |
O1—C18 | 1.437 (3) | C10—C11 | 1.403 (3) |
O2—C1 | 1.306 (3) | C11—C12 | 1.380 (3) |
O2—H2 | 0.8400 | C11—H11 | 0.9500 |
O3—C1 | 1.239 (3) | C12—C13 | 1.399 (3) |
O4—C6 | 1.369 (3) | C13—C14 | 1.392 (3) |
O4—C16 | 1.425 (3) | C14—C15 | 1.380 (3) |
O5—C8 | 1.371 (3) | C14—H14 | 0.9500 |
O5—C17 | 1.424 (4) | C15—H15 | 0.9500 |
C1—C2 | 1.480 (3) | C16—H16A | 0.9800 |
C2—C3 | 1.345 (3) | C16—H16B | 0.9800 |
C2—C4 | 1.497 (3) | C16—H16C | 0.9800 |
C3—C10 | 1.459 (3) | C17—H17A | 0.9800 |
C3—H3 | 0.9500 | C17—H17B | 0.9800 |
C4—C5 | 1.377 (4) | C17—H17C | 0.9800 |
C4—C9 | 1.398 (4) | C18—C19 | 1.502 (4) |
C5—C6 | 1.398 (3) | C18—H18A | 0.9900 |
C5—H5 | 0.9500 | C18—H18B | 0.9900 |
C6—C7 | 1.378 (4) | C19—H19A | 0.9800 |
C7—C8 | 1.398 (4) | C19—H19B | 0.9800 |
C7—H7 | 0.9500 | C19—H19C | 0.9800 |
C8—C9 | 1.390 (4) | ||
C13—O1—C18 | 118.42 (19) | C11—C12—C13 | 120.4 (2) |
C1—O2—H2 | 109.5 | C11—C12—I1 | 120.20 (17) |
C6—O4—C16 | 117.4 (2) | C13—C12—I1 | 119.35 (17) |
C8—O5—C17 | 117.8 (2) | O1—C13—C14 | 124.9 (2) |
O3—C1—O2 | 122.6 (2) | O1—C13—C12 | 116.5 (2) |
O3—C1—C2 | 121.3 (2) | C14—C13—C12 | 118.6 (2) |
O2—C1—C2 | 116.2 (2) | C15—C14—C13 | 120.7 (2) |
C3—C2—C1 | 118.3 (2) | C15—C14—H14 | 119.7 |
C3—C2—C4 | 124.9 (2) | C13—C14—H14 | 119.7 |
C1—C2—C4 | 116.7 (2) | C14—C15—C10 | 121.3 (2) |
C2—C3—C10 | 131.3 (2) | C14—C15—H15 | 119.3 |
C2—C3—H3 | 114.4 | C10—C15—H15 | 119.3 |
C10—C3—H3 | 114.4 | O4—C16—H16A | 109.5 |
C5—C4—C9 | 120.8 (2) | O4—C16—H16B | 109.5 |
C5—C4—C2 | 119.8 (2) | H16A—C16—H16B | 109.5 |
C9—C4—C2 | 119.4 (2) | O4—C16—H16C | 109.5 |
C4—C5—C6 | 119.8 (2) | H16A—C16—H16C | 109.5 |
C4—C5—H5 | 120.1 | H16B—C16—H16C | 109.5 |
C6—C5—H5 | 120.1 | O5—C17—H17A | 109.5 |
O4—C6—C7 | 124.8 (2) | O5—C17—H17B | 109.5 |
O4—C6—C5 | 114.8 (2) | H17A—C17—H17B | 109.5 |
C7—C6—C5 | 120.4 (2) | O5—C17—H17C | 109.5 |
C6—C7—C8 | 119.4 (2) | H17A—C17—H17C | 109.5 |
C6—C7—H7 | 120.3 | H17B—C17—H17C | 109.5 |
C8—C7—H7 | 120.3 | O1—C18—C19 | 106.3 (2) |
O5—C8—C9 | 124.4 (3) | O1—C18—H18A | 110.5 |
O5—C8—C7 | 114.7 (2) | C19—C18—H18A | 110.5 |
C9—C8—C7 | 120.9 (2) | O1—C18—H18B | 110.5 |
C8—C9—C4 | 118.7 (2) | C19—C18—H18B | 110.5 |
C8—C9—H9 | 120.7 | H18A—C18—H18B | 108.7 |
C4—C9—H9 | 120.7 | C18—C19—H19A | 109.5 |
C15—C10—C11 | 117.5 (2) | C18—C19—H19B | 109.5 |
C15—C10—C3 | 125.5 (2) | H19A—C19—H19B | 109.5 |
C11—C10—C3 | 117.0 (2) | C18—C19—H19C | 109.5 |
C12—C11—C10 | 121.3 (2) | H19A—C19—H19C | 109.5 |
C12—C11—H11 | 119.3 | H19B—C19—H19C | 109.5 |
C10—C11—H11 | 119.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.84 | 1.79 | 2.617 (3) | 169 |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C19H19IO5 |
Mr | 454.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 193 |
a, b, c (Å) | 12.688 (2), 11.1649 (19), 14.229 (2) |
β (°) | 112.861 (2) |
V (Å3) | 1857.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.75 |
Crystal size (mm) | 0.20 × 0.16 × 0.12 |
Data collection | |
Diffractometer | Bruker CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.665, 0.811 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11524, 4310, 4085 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.066, 1.20 |
No. of reflections | 4310 |
No. of parameters | 230 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.94, −0.85 |
Computer programs: ASTRO (Bruker, 1997), SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.84 | 1.79 | 2.617 (3) | 169 |
Symmetry code: (i) −x+1, −y, −z+1. |
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Since the position of an Auger electron emitter (e.g. 77Br, 123I and 125I) vis-à-vis DNA is of paramount importance for its DNA double-strand-break yield and toxicity (Kassis, 2004), the development of a carrier molecule locating the Auger electron emitter in close proximity to the nuclear DNA of cells is of high interest. We have recently focused on the synthesis of Hoechst-skeleton-based ligands, designed by in silico methods (Chen et al., 2004a,b), with predictable iodine-to-DNA distances. The title compound, (I), has been produced as an important intermediate, and its conformation has been determined by X-ray structure analysis and is presented in this report.
As shown in Fig. 1, the orientation of the two benzene rings is cis, thus clearly demonstrating that the conformation of compound (I) is E. The C1—C2—C3—C10 and C2—C3—C10—C11 torsion angles are 174.7 (3) and 169.0 (3)°, respectively, and indicate that the iodine-substited benzene ring and the acrylic acid group are nearly coplanar, whereas the dimethoxy-substituted benzene ring crosses this plane with the dihedral angle 72.50 (7)° between planes C4–C9 and C10–C15. In the crystal structure, strong intermolecular O—H···O hydrogen bonds (Table 1) connect the molecules producing distinct dimers arranged around inversion center (Fig. 2).