Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045291/gg2022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045291/gg2022Isup2.hkl |
CCDC reference: 663821
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- Disorder in main residue
- R factor = 0.039
- wR factor = 0.117
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT430_ALERT_2_B Short Inter D...A Contact O3 .. O5 .. 2.82 Ang.
Author Response: O13 is a presumably hydrogen-bond donor of the minor constituent of the disordered molecule. Therefore the pertinent hydrogen to the O13 could not be localized. |
PROBLEM: PLAT041_ALERT_1_C: Calc. and Rep. SumFormula Strings Differ .... ? RESPONSE: This is due to wrong interpretation by PLATON. This is due to wrong interpretation by PLATON. There are two independent molecules in the structure. PROBLEM: PLAT042_ALERT_1_C: Calc. and Rep. MoietyFormula Strings Differ .... ? RESPONSE: This is due to wrong interpretation by PLATON. This is due to wrong interpretation by PLATON. There are two independent molecules in the structure. PROBLEM: PLAT045_ALERT_1_C: Calculated and Reported Z Differ by ............ 0.50 Ratio RESPONSE: This is due to wrong interpretation by PLATON. This is due to wrong interpretation by PLATON. There are two independent molecules in the structure. PROBLEM: PLAT068_ALERT_1_C: Reported F000 Differs from Calcd (or Missing)... ? RESPONSE: This is due to the fact some hydrogens of the This is due to the fact some hydrogens of the minor part of the disordered molecules could not be localized. PROBLEM: PLAT309_ALERT_2_C: Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........ O13 RESPONSE: O13 is a presumably hydrogen-bond donor of the minor O13 is a presumably hydrogen-bond donor of the minor constituent of the disordered molecule. It bears a hydrogen that could not be localized. PROBLEM: PLAT720_ALERT_4_C: Number of Unusual/Non-Standard Label(s) ........ 24 RESPONSE: The corresponding atoms in the independent molecules The corresponding atoms in the independent molecules have the corresponding labels.
Alert level C GOODF01_ALERT_2_C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 2.090 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT087_ALERT_2_C Unsatisfactory S value (Too High) .............. 2.09 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 20 Ang. PLAT301_ALERT_3_C Main Residue Disorder ......................... 7.00 Perc. PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........ O5
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C10 H11 N1 O2 Atom count from the _atom_site data: C10 H10.95809 N1 O2 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G ALERT: check formula stoichiometry or atom site occupancies. From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C10 H11 N1 O2 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 40.00 40.00 0.00 H 44.00 43.83 0.17 N 4.00 4.00 0.00 O 8.00 8.00 0.00 PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
2.33 g of phthalaldehyde were dissolved in 120 ml of dry acetonitrile. 1.3 ml of ethanolamine was added dropwise to the mixture while stirring. The mixture was stirred for 4 h and then it was evaporated to dryness under reduced pressure. The residue was chromatographed on a column of silica gel in CHCl3:C2H5OH (10%). All reaction steps were performed at room temperature.
At least two products were produced by the reaction. Column chromatography afforded 308 mg of the title compound, (I) 252 mg after its recrystallization from toluene, as well as 256 mg of 2-(2''-hydroxyethyl)-3-(3'-hydroxy-1'H,3'H-benzo[c]furan)-1'-yl- 1H,3H-benzo[c]pyrrol-1-one, (II), the yield of which was 150 mg after its recrystallization from CHCl3-n-C6H14 (Urban et al., 2007). The major part of a mixture are polymers.
In the vicinity of C10 and O2 atoms were maxima on a difference Fourier map (0.40 and 0.80 e Å-3, respectively). These maxima were assigned to the disordered C11 and O5 atoms. These atoms have the respective counterparts of C10 and O2. Since the refined occupational parameters of C11 and O5 were so low (0.0840 (15)) the corresponding H atoms were situated into idealized positions with regard to C11 but could not be assigned to O5.
Otherwise all of the H atoms were discernible in the difference Fourier map. All the H atoms were constrained to the riding-hydrogen formalism with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.2Ueq(O). The C—H distances were constrained to 0.93 and 0.97 Å for aryl and methylene H atoms, respectively.
The O—H distances were restrained to 0.820 (1) Å while the C11—O5 distances were restrained to 1.400 (1) Å.
The occupational parameters of C10, H10a, H10b, O2 as well as H2O were set to be equal while each of the occupational parameters of O5 and C11, H11a and H11b was a complement to 1 of the former occupational parameters. The displacement parameters of the disordered pairs of the atoms O2, O5 and C10, C11 were also constrained to be equal.
Our research project deals with chemical and electrochemical properties of diketones (Zuman, 2004). As a part of this study, we observed that a main product of the reaction of orthophthalaldehyde with amines in low concentrations about 10 -3 mol/l is reducible about 0.5 V more negatively than the parent dialdehyde. In order to study this reaction as well as in order to identify the product (an isoindoline derivative is expected to be formed) the reaction of phthalaldehyde with kolamine (2-aminoethanol) was carried out.
In ethanol, however, the reaction results in a mixture of non-separable, viscous, probably polymeric compounds. On the other hand, the reaction in acetonitrile leads to two minor products together with formation of a non-separable mixture. The minor products were isolated, purified, crystallized and analyzed by NMR and single-crystal X-ray diffraction.
One of these compounds was identified as 2-(2-hydroxyetyl)-1H,3H benzo[c]pyrrol-1-one, (I), that is here reported while the second compound was identified as (3R*,1'S*,3'R*)-2-(2''-hydroxyethyl)-3- (3'-hydroxy-1'H,3'H- benzo[c]furan)-1'-yl-1H,3H-benzo[c]pyrrol-1-one, (II), (Urban et al., 2007).
The dihedral angles between the pyrrole and the attached phenyl rings in the isoindoline rings are 0.47 (4) and 0.94 (4)° for the moieties containing N1 and N2 atoms, respectively.
The reaction pathways are clearly affected by concentrations of the components and by the composition of the reaction solvent, several simultaneous reactions seem to occur.
The formation of the title compound (I) in acetonitrile proceeds most probably via an intramolecular Cannizzaro reaction simultaneously with the addition of kolamine and cyclization. In the case od the second compound (Urban et al., 2007), acyloin condensation of two molecules takes place, followed by acetalization on one ring, whereas the second one undergoes a reaction analogous to the formation the title compound. Since these two isolated compounds are minor products, the main reaction pathway should be different. Its further investigation is currently being performed.
A referee pointed that there may also be an alternative way of preparation of the title compound (I) following Grigg et al. (1985). This other way was confirmed experimentally: 500 mg of phthalaldehyde and 228 mg of ethanolamine were dissolved in 7 ml of acetic acid. The mixture was refluxed for 10 minutes and then it was evaporated to dryness. The residue was dissolved in ethanol, treated with active coal and filtered. Evaporation and crystallization of the residue from toluene gave the product (318 mg) as colourless crystals.
A crystal from the prepared batch by the latter way was selected and put on a four-circle single-crystal diffractometer. A trial measurement at room temperature confirmed the identity of the sample whose largest size did not exceed 0.3 mm. The lattice parameters at 291 (1) K were determined as: 8.7940 (11), 9.8820 (13), 10.5320 (13) Å, 103.699 (6), 90.394 (8), 96.788 (7)°.
From the lattice parameters at 291 and 150 K it is seen that the unit-cell dimensions are susceptible to thermal expansion.
Final remark: A referee pointed out that many isoindoline derivatives display biological as well as pharmaceutical activity (Mukherjee et al., 2000).
For related literature, see: Zuman (2004); Grigg et al. (1985); Urban et al. (2007). For the biological activity of isoindolines, see: Mukherjee et al. (2000).
Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: JANA2000 (Petříček et al., 2000); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: JANA2000 (Petříček et al., 2000).
C10H11NO2 | Z = 4 |
Mr = 177.2 | F(000) = 375 |
Triclinic, P1 | Dx = 1.363 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7122 (2) Å | Cell parameters from 3960 reflections |
b = 9.8523 (2) Å | θ = 1–27.5° |
c = 10.4304 (2) Å | µ = 0.10 mm−1 |
α = 103.2549 (14)° | T = 150 K |
β = 90.6852 (14)° | Block, colourless |
γ = 97.4368 (12)° | 0.5 × 0.4 × 0.3 mm |
V = 863.31 (3) Å3 |
Nonius KappaCCD diffractometer | 3497 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 27.6°, θmin = 2.0° |
Detector resolution: 9.091 pixels mm-1 | h = −11→11 |
φ and ω scans | k = −12→12 |
25935 measured reflections | l = −13→13 |
3987 independent reflections |
Refinement on F2 | 82 constraints |
R[F > 3σ(F)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F) = 0.117 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 2.09 | (Δ/σ)max = 0.006 |
3987 reflections | Δρmax = 0.20 e Å−3 |
248 parameters | Δρmin = −0.17 e Å−3 |
3 restraints |
C10H11NO2 | γ = 97.4368 (12)° |
Mr = 177.2 | V = 863.31 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.7122 (2) Å | Mo Kα radiation |
b = 9.8523 (2) Å | µ = 0.10 mm−1 |
c = 10.4304 (2) Å | T = 150 K |
α = 103.2549 (14)° | 0.5 × 0.4 × 0.3 mm |
β = 90.6852 (14)° |
Nonius KappaCCD diffractometer | 3497 reflections with I > 2σ(I) |
25935 measured reflections | Rint = 0.028 |
3987 independent reflections |
R[F > 3σ(F)] = 0.039 | 3 restraints |
wR(F) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 2.09 | Δρmax = 0.20 e Å−3 |
3987 reflections | Δρmin = −0.17 e Å−3 |
248 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.09039 (11) | 0.54687 (10) | 0.19174 (9) | 0.0217 (3) | |
C2 | 0.20064 (12) | 0.38058 (11) | 0.03797 (10) | 0.0235 (3) | |
C3 | 0.05043 (12) | 0.28378 (10) | 0.19853 (10) | 0.0266 (3) | |
H3 | −0.011958 | 0.2959 | 0.270909 | 0.0319* | |
C4 | 0.17827 (13) | 0.13502 (11) | 0.02850 (11) | 0.0325 (4) | |
H4 | 0.201956 | 0.04596 | −0.0109 | 0.039* | |
C5 | 0.08718 (13) | 0.15208 (11) | 0.13875 (11) | 0.0311 (4) | |
H5 | 0.050678 | 0.075085 | 0.172648 | 0.0374* | |
C6 | 0.23476 (12) | 0.24811 (11) | −0.02417 (11) | 0.0288 (3) | |
H6 | 0.2936 | 0.235532 | −0.098737 | 0.0345* | |
C7 | 0.10948 (11) | 0.39686 (10) | 0.14716 (9) | 0.0218 (3) | |
C8 | 0.24652 (12) | 0.52148 (10) | 0.00785 (10) | 0.0247 (3) | |
H8a | 0.357847 | 0.547079 | 0.021077 | 0.0296* | |
H8b | 0.20396 | 0.520935 | −0.078651 | 0.0296* | |
C9 | 0.17687 (12) | 0.76534 (10) | 0.11899 (10) | 0.0267 (3) | |
H9a | 0.077343 | 0.795184 | 0.143598 | 0.032* | |
H9b | 0.194941 | 0.784578 | 0.032896 | 0.032* | |
C10 | 0.30195 (14) | 0.85174 (13) | 0.21711 (13) | 0.0268 (4) | 0.9162 (15) |
H10a | 0.295036 | 0.951035 | 0.226832 | 0.0321* | 0.9162 (15) |
H10b | 0.284511 | 0.831731 | 0.302999 | 0.0321* | 0.9162 (15) |
O1 | 0.01510 (9) | 0.60081 (8) | 0.28583 (7) | 0.0296 (3) | |
O2 | 0.45202 (10) | 0.82422 (9) | 0.17828 (10) | 0.0357 (3) | 0.9162 (15) |
H2o | 0.4719 (18) | 0.7569 (10) | 0.2063 (13) | 0.0428* | 0.9162 (15) |
N1 | 0.16865 (10) | 0.61482 (8) | 0.10924 (8) | 0.0231 (3) | |
C12 | 0.59562 (12) | 0.54190 (10) | 0.32247 (10) | 0.0235 (3) | |
C13 | 0.70896 (12) | 0.38520 (11) | 0.41794 (10) | 0.0237 (3) | |
C14 | 0.56705 (12) | 0.27575 (11) | 0.21063 (10) | 0.0269 (3) | |
H14 | 0.507605 | 0.282416 | 0.138239 | 0.0323* | |
C15 | 0.69513 (13) | 0.13760 (11) | 0.33140 (11) | 0.0319 (4) | |
H15 | 0.720178 | 0.050302 | 0.337532 | 0.0383* | |
C16 | 0.60609 (13) | 0.14733 (11) | 0.22324 (11) | 0.0306 (4) | |
H16 | 0.572119 | 0.066686 | 0.158326 | 0.0367* | |
C17 | 0.74732 (13) | 0.25632 (11) | 0.43052 (11) | 0.0290 (4) | |
H17 | 0.806252 | 0.249711 | 0.503227 | 0.0348* | |
C18 | 0.61995 (12) | 0.39388 (10) | 0.30999 (10) | 0.0227 (3) | |
C19 | 0.75049 (12) | 0.52996 (11) | 0.50452 (10) | 0.0266 (3) | |
H19a | 0.706391 | 0.533355 | 0.589969 | 0.0319* | |
H19b | 0.861669 | 0.557213 | 0.505998 | 0.0319* | |
C20 | 0.67537 (13) | 0.76766 (11) | 0.48737 (10) | 0.0293 (4) | |
H20a | 0.639369 | 0.784698 | 0.57656 | 0.0351* | |
H20b | 0.601402 | 0.80254 | 0.437042 | 0.0351* | |
C21 | 0.83428 (13) | 0.85111 (11) | 0.48665 (10) | 0.0286 (3) | |
H21a | 0.83231 | 0.948073 | 0.533276 | 0.0343* | |
H21b | 0.90867 | 0.814951 | 0.535436 | 0.0343* | |
O3 | 0.51825 (9) | 0.58785 (8) | 0.24628 (8) | 0.0334 (3) | |
O4 | 0.88505 (10) | 0.84720 (8) | 0.35795 (8) | 0.0365 (3) | |
H4o | 0.9190 (15) | 0.7724 (7) | 0.3314 (13) | 0.0438* | |
N2 | 0.67238 (10) | 0.61715 (9) | 0.43529 (8) | 0.0245 (3) | |
O5 | 0.3877 (11) | 0.8415 (9) | 0.2889 (9) | 0.0357 (3) | 0.0838 (15) |
C11 | 0.3327 (18) | 0.8496 (16) | 0.1646 (10) | 0.0268 (4) | 0.0838 (15) |
H11a | 0.40835 | 0.82158 | 0.099667 | 0.0321* | 0.0838 (15) |
H11b | 0.329506 | 0.947375 | 0.163376 | 0.0321* | 0.0838 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0204 (5) | 0.0222 (5) | 0.0221 (5) | 0.0032 (4) | −0.0018 (4) | 0.0044 (4) |
C2 | 0.0200 (5) | 0.0260 (5) | 0.0229 (5) | 0.0034 (4) | −0.0041 (4) | 0.0025 (4) |
C3 | 0.0288 (6) | 0.0256 (5) | 0.0251 (5) | 0.0008 (4) | −0.0027 (4) | 0.0070 (4) |
C4 | 0.0306 (6) | 0.0221 (5) | 0.0405 (6) | 0.0070 (5) | −0.0094 (5) | −0.0029 (5) |
C5 | 0.0328 (6) | 0.0225 (5) | 0.0372 (6) | 0.0001 (5) | −0.0099 (5) | 0.0077 (5) |
C6 | 0.0246 (6) | 0.0293 (6) | 0.0285 (5) | 0.0062 (4) | −0.0025 (4) | −0.0025 (4) |
C7 | 0.0208 (5) | 0.0214 (5) | 0.0221 (5) | 0.0028 (4) | −0.0038 (4) | 0.0032 (4) |
C8 | 0.0227 (5) | 0.0287 (5) | 0.0225 (5) | 0.0043 (4) | 0.0019 (4) | 0.0054 (4) |
C9 | 0.0265 (6) | 0.0227 (5) | 0.0343 (6) | 0.0059 (4) | −0.0001 (4) | 0.0123 (4) |
C10 | 0.0270 (7) | 0.0210 (5) | 0.0337 (7) | 0.0046 (5) | 0.0033 (5) | 0.0085 (5) |
O1 | 0.0330 (4) | 0.0266 (4) | 0.0290 (4) | 0.0076 (3) | 0.0079 (3) | 0.0038 (3) |
O2 | 0.0228 (5) | 0.0241 (5) | 0.0642 (6) | 0.0037 (4) | 0.0016 (4) | 0.0185 (4) |
N1 | 0.0242 (5) | 0.0211 (4) | 0.0250 (4) | 0.0041 (3) | 0.0010 (3) | 0.0064 (3) |
C12 | 0.0209 (5) | 0.0232 (5) | 0.0271 (5) | 0.0021 (4) | 0.0015 (4) | 0.0079 (4) |
C13 | 0.0213 (5) | 0.0266 (5) | 0.0256 (5) | 0.0035 (4) | 0.0054 (4) | 0.0107 (4) |
C14 | 0.0261 (6) | 0.0258 (5) | 0.0281 (6) | −0.0001 (4) | 0.0005 (4) | 0.0069 (4) |
C15 | 0.0333 (6) | 0.0230 (5) | 0.0444 (7) | 0.0064 (5) | 0.0110 (5) | 0.0163 (5) |
C16 | 0.0318 (6) | 0.0217 (5) | 0.0365 (6) | −0.0010 (4) | 0.0076 (5) | 0.0055 (4) |
C17 | 0.0276 (6) | 0.0325 (6) | 0.0327 (6) | 0.0066 (5) | 0.0046 (5) | 0.0177 (5) |
C18 | 0.0213 (5) | 0.0216 (5) | 0.0265 (5) | 0.0019 (4) | 0.0037 (4) | 0.0088 (4) |
C19 | 0.0256 (6) | 0.0304 (6) | 0.0246 (5) | 0.0047 (4) | 0.0009 (4) | 0.0079 (4) |
C20 | 0.0293 (6) | 0.0237 (5) | 0.0326 (6) | 0.0059 (4) | 0.0051 (5) | 0.0006 (4) |
C21 | 0.0318 (6) | 0.0234 (5) | 0.0290 (6) | 0.0037 (4) | 0.0030 (4) | 0.0028 (4) |
O3 | 0.0361 (5) | 0.0276 (4) | 0.0383 (5) | 0.0077 (3) | −0.0093 (3) | 0.0102 (3) |
O4 | 0.0492 (5) | 0.0259 (4) | 0.0379 (5) | 0.0116 (4) | 0.0156 (4) | 0.0101 (3) |
N2 | 0.0245 (5) | 0.0216 (4) | 0.0268 (5) | 0.0039 (3) | 0.0002 (3) | 0.0040 (3) |
O5 | 0.0228 (5) | 0.0241 (5) | 0.0642 (6) | 0.0037 (4) | 0.0016 (4) | 0.0185 (4) |
C11 | 0.0270 (7) | 0.0210 (5) | 0.0337 (7) | 0.0046 (5) | 0.0033 (5) | 0.0085 (5) |
C1—C7 | 1.4760 (14) | C21—O4 | 1.4121 (14) |
C1—O1 | 1.2419 (12) | O5—C11 | 1.400 (16) |
C1—N1 | 1.3468 (13) | C3—H3 | 0.93 |
C2—C6 | 1.3888 (14) | C4—H4 | 0.93 |
C2—C7 | 1.3873 (14) | C5—H5 | 0.93 |
C2—C8 | 1.4982 (15) | C6—H6 | 0.93 |
C3—C5 | 1.3842 (15) | C8—H8a | 0.97 |
C3—C7 | 1.3874 (15) | C8—H8b | 0.97 |
C4—C5 | 1.3958 (16) | C9—H9a | 0.97 |
C4—C6 | 1.3895 (17) | C9—H9b | 0.97 |
C8—N1 | 1.4687 (13) | C10—H10a | 0.97 |
C9—C10 | 1.5143 (15) | C10—H10b | 0.97 |
C9—N1 | 1.4552 (13) | O2—H2o | 0.820 (12) |
C9—C11 | 1.507 (14) | C14—H14 | 0.93 |
C10—O2 | 1.4146 (15) | C15—H15 | 0.93 |
C12—C18 | 1.4773 (15) | C16—H16 | 0.93 |
C12—O3 | 1.2337 (14) | C17—H17 | 0.93 |
C12—N2 | 1.3544 (12) | C19—H19a | 0.97 |
C13—C17 | 1.3880 (16) | C19—H19b | 0.97 |
C13—C18 | 1.3845 (15) | C20—H20a | 0.97 |
C13—C19 | 1.4995 (13) | C20—H20b | 0.97 |
C14—C16 | 1.3859 (16) | C21—H21a | 0.97 |
C14—C18 | 1.3919 (12) | C21—H21b | 0.97 |
C15—C16 | 1.3898 (17) | O4—H4o | 0.820 (9) |
C15—C17 | 1.3930 (14) | O5—H10b | 0.909 (9) |
C19—N2 | 1.4651 (15) | C11—H11a | 0.97 |
C20—C21 | 1.5170 (15) | C11—H11b | 0.97 |
C20—N2 | 1.4543 (13) | ||
C7—C1—O1 | 127.04 (9) | C17—C13—C19 | 130.72 (10) |
C7—C1—N1 | 106.80 (8) | C18—C13—C19 | 108.91 (9) |
O1—C1—N1 | 126.15 (9) | C16—C14—C18 | 117.63 (10) |
C6—C2—C7 | 120.21 (10) | C16—C15—C17 | 121.09 (11) |
C6—C2—C8 | 130.77 (10) | C14—C16—C15 | 120.90 (9) |
C7—C2—C8 | 109.02 (9) | C13—C17—C15 | 118.16 (10) |
C5—C3—C7 | 117.97 (10) | C12—C18—C13 | 108.93 (8) |
C5—C4—C6 | 121.58 (10) | C12—C18—C14 | 129.22 (10) |
C3—C5—C4 | 120.26 (11) | C13—C18—C14 | 121.85 (10) |
C2—C6—C4 | 117.96 (10) | C13—C19—N2 | 102.64 (8) |
C1—C7—C2 | 108.74 (9) | C21—C20—N2 | 113.33 (9) |
C1—C7—C3 | 129.27 (9) | C20—C21—O4 | 112.68 (8) |
C2—C7—C3 | 121.99 (9) | C12—N2—C19 | 112.86 (8) |
C2—C8—N1 | 102.33 (8) | C12—N2—C20 | 124.93 (9) |
C10—C9—N1 | 112.90 (10) | C19—N2—C20 | 122.18 (8) |
N1—C9—C11 | 115.0 (6) | C9—C11—O5 | 115.3 (10) |
C9—C10—O2 | 112.09 (10) | C10—C11—O2 | 106.5 (17) |
C9—C10—O5 | 141.7 (5) | H8a—C8—H8b | 115.78 |
O5—C10—C11 | 108.4 (15) | H9a—C9—H9b | 105.81 |
C1—N1—C8 | 113.09 (8) | H10a—C10—H10b | 106.72 |
C1—N1—C9 | 123.93 (8) | H2o—O2—H11a | 127.0 |
C8—N1—C9 | 122.98 (8) | H19a—C19—H19b | 115.53 |
C18—C12—O3 | 126.75 (8) | H20a—C20—H20b | 105.32 |
C18—C12—N2 | 106.64 (9) | H21a—C21—H21b | 106.06 |
O3—C12—N2 | 126.60 (9) | H11a—C11—H11b | 102.9 |
C17—C13—C18 | 120.36 (9) |
Experimental details
Crystal data | |
Chemical formula | C10H11NO2 |
Mr | 177.2 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 8.7122 (2), 9.8523 (2), 10.4304 (2) |
α, β, γ (°) | 103.2549 (14), 90.6852 (14), 97.4368 (12) |
V (Å3) | 863.31 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25935, 3987, 3497 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F > 3σ(F)], wR(F), S | 0.039, 0.117, 2.09 |
No. of reflections | 3987 |
No. of parameters | 248 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.17 |
Computer programs: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), JANA2000 (Petříček et al., 2000), PLATON (Spek, 2003).
D-H···A/Cg | D-H | H···A/Cg | D···A/Cg | D-H···A/Cg |
O2-H2O···O3 | 0.820 (11) | 1.897 (11) | 2.7120 (12) | 172.1 (13) |
O4-H4O···O1i | 0.820 (10) | 1.947 (10) | 2.7636 (11) | 173.6 (12) |
C6-H6···O2ii | 0.93 | 2.47 | 3.2590 (14) | 143 |
C16-H16···O2iii | 0.93 | 2.54 | 3.2171 (14) | 130 |
C20-H20b···O3 | 0.97 | 2.57 | 2.9296 (13) | 102 |
C9-H9a···Cg1iv | 0.98 | 2.97 | 3.4442 (11) | 112 |
C3-H3···Cg2v | 0.98 | 2.92 | 3.6643 (11) | 138 |
C20-H20a···Cg2vi | 0.98 | 2.84 | 3.5668 (12) | 132 |
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z; (iii) x, y-1, z; (iv) -x, -y+1, -z; (v) x-1, y, z; (vi) -x+1, -y+1, -z+1. |
Our research project deals with chemical and electrochemical properties of diketones (Zuman, 2004). As a part of this study, we observed that a main product of the reaction of orthophthalaldehyde with amines in low concentrations about 10 -3 mol/l is reducible about 0.5 V more negatively than the parent dialdehyde. In order to study this reaction as well as in order to identify the product (an isoindoline derivative is expected to be formed) the reaction of phthalaldehyde with kolamine (2-aminoethanol) was carried out.
In ethanol, however, the reaction results in a mixture of non-separable, viscous, probably polymeric compounds. On the other hand, the reaction in acetonitrile leads to two minor products together with formation of a non-separable mixture. The minor products were isolated, purified, crystallized and analyzed by NMR and single-crystal X-ray diffraction.
One of these compounds was identified as 2-(2-hydroxyetyl)-1H,3H benzo[c]pyrrol-1-one, (I), that is here reported while the second compound was identified as (3R*,1'S*,3'R*)-2-(2''-hydroxyethyl)-3- (3'-hydroxy-1'H,3'H- benzo[c]furan)-1'-yl-1H,3H-benzo[c]pyrrol-1-one, (II), (Urban et al., 2007).
The dihedral angles between the pyrrole and the attached phenyl rings in the isoindoline rings are 0.47 (4) and 0.94 (4)° for the moieties containing N1 and N2 atoms, respectively.
The reaction pathways are clearly affected by concentrations of the components and by the composition of the reaction solvent, several simultaneous reactions seem to occur.
The formation of the title compound (I) in acetonitrile proceeds most probably via an intramolecular Cannizzaro reaction simultaneously with the addition of kolamine and cyclization. In the case od the second compound (Urban et al., 2007), acyloin condensation of two molecules takes place, followed by acetalization on one ring, whereas the second one undergoes a reaction analogous to the formation the title compound. Since these two isolated compounds are minor products, the main reaction pathway should be different. Its further investigation is currently being performed.
A referee pointed that there may also be an alternative way of preparation of the title compound (I) following Grigg et al. (1985). This other way was confirmed experimentally: 500 mg of phthalaldehyde and 228 mg of ethanolamine were dissolved in 7 ml of acetic acid. The mixture was refluxed for 10 minutes and then it was evaporated to dryness. The residue was dissolved in ethanol, treated with active coal and filtered. Evaporation and crystallization of the residue from toluene gave the product (318 mg) as colourless crystals.
A crystal from the prepared batch by the latter way was selected and put on a four-circle single-crystal diffractometer. A trial measurement at room temperature confirmed the identity of the sample whose largest size did not exceed 0.3 mm. The lattice parameters at 291 (1) K were determined as: 8.7940 (11), 9.8820 (13), 10.5320 (13) Å, 103.699 (6), 90.394 (8), 96.788 (7)°.
From the lattice parameters at 291 and 150 K it is seen that the unit-cell dimensions are susceptible to thermal expansion.
Final remark: A referee pointed out that many isoindoline derivatives display biological as well as pharmaceutical activity (Mukherjee et al., 2000).