Orthophthalaldehyde (
o-phthalaldehyde, OPA) is an aromatic dialdehyde bearing two electron-withdrawing carbonyl groups. The reactions of OPA with primary amines are broadly applied for the synthesis of important heterocyclic compounds with biological relevance. A number of such reactions have been investigated recently and several structures of condensation products have been reported, however, the complex reaction mechanism is still not fully understood and comprises concurrent as well as consecutive reactions. The reaction products depend on the primary amine which reacts with OPA, the reaction environment (solvent) and the proportion of the reactants. The title molecule, C
11H
13NO, the product of the reaction of OPA with isopropylamine, contains a five-membered pyrrole C
4N ring with a carbonyl substituent, which forms part of the isoindolinone unit. Though this pyrrole ring contains one C atom in the
sp3-hybridized state, it is fairly planar. The title molecule has been compared with similar structures retrieved from the Cambridge Structural Database in order to study this phenomenon. The planarity of this fragment has been explained by the presence of partially delocalized C—C, C—N and C—O bonds, and by an inner angle in the planar pentagonal ring (∼108°), which is close to the ideal tetrahedral value for the
sp3-hybridized state of the constituent C atom. Due to this propitious angle, this C atom can be present in states intermediate between
sp3- and
sp2-hybridized in different structures, while still maintaining the planarity of the ring. There are only weak intermolecular C—H
O hydrogen bonds and C—H
π-electron ring interactions in the structure. In particular, it is the pyrrole ring which is involved in these interactions.
Supporting information
CCDC reference: 1482614
Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: JANA2006 (Petříček et al., 2014),
Origin6.1 (OriginLab Corporation, 2000) and
PLATON (Spek, 2009); software used to prepare material for publication: JANA2006 (Petříček et al., 2014).
2-Isopropyl-2,3-dihydro-1
H-isoindol-1-one
top
Crystal data top
C11H13NO | F(000) = 188 |
Mr = 175.2 | Dx = 1.240 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: P 2yb | Cell parameters from 6393 reflections |
a = 6.2155 (2) Å | θ = 5.1–66.9° |
b = 8.7681 (3) Å | µ = 0.63 mm−1 |
c = 8.9686 (3) Å | T = 121 K |
β = 106.140 (3)° | Prism, orange |
V = 469.51 (3) Å3 | 0.33 × 0.23 × 0.19 mm |
Z = 2 | |
Data collection top
Rigaku Oxford Diffraction Xcalibur (Atlas2, Gemini ultra) diffractometer | 1677 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance Ultra (Cu) X-ray Source | 1654 reflections with I > 3σ(I) |
Mirror monochromator | Rint = 0.027 |
Detector resolution: 5.1783 pixels mm-1 | θmax = 67.0°, θmin = 5.1° |
ω scans | h = −7→7 |
Absorption correction: analytical (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | k = −10→10 |
Tmin = 0.86, Tmax = 0.915 | l = −10→10 |
7682 measured reflections | |
Refinement top
Refinement on F2 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
R[F > 3σ(F)] = 0.025 | (Δ/σ)max = 0.009 |
wR(F) = 0.068 | Δρmax = 0.11 e Å−3 |
S = 2.16 | Δρmin = −0.09 e Å−3 |
1677 reflections | Extinction correction: B-C type 1 Lorentzian isotropic (Becker & Coppens, 1974) |
129 parameters | Extinction coefficient: 850 (140) |
1 restraint | Absolute structure: 775 of Friedel pairs used in the refinement |
44 constraints | Absolute structure parameter: 0.1 (2) |
H atoms treated by a mixture of independent and constrained refinement | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.31713 (18) | 0.58682 (13) | 0.17724 (13) | 0.0210 (4) | |
C2 | 0.1315 (2) | 0.56320 (14) | 0.05039 (13) | 0.0259 (4) | |
H2 | −0.00796 | 0.61094 | 0.043979 | 0.0311* | |
C3 | 0.1580 (2) | 0.46724 (14) | −0.06641 (14) | 0.0302 (4) | |
H3 | 0.034313 | 0.447504 | −0.154017 | 0.0362* | |
C4 | 0.3642 (2) | 0.39975 (15) | −0.05616 (15) | 0.0311 (4) | |
H4 | 0.379095 | 0.335359 | −0.137898 | 0.0374* | |
C5 | 0.5491 (2) | 0.42419 (14) | 0.07079 (14) | 0.0270 (4) | |
H5 | 0.689288 | 0.377556 | 0.07688 | 0.0323* | |
C6 | 0.52213 (19) | 0.51893 (13) | 0.18818 (13) | 0.0219 (4) | |
C7 | 0.68645 (18) | 0.56549 (14) | 0.33849 (13) | 0.0220 (4) | |
H7a | 0.737 (2) | 0.4754 (15) | 0.4043 (16) | 0.0264* | |
H7b | 0.819 (2) | 0.6199 (16) | 0.3256 (16) | 0.0264* | |
N1 | 0.55194 (15) | 0.66769 (11) | 0.40555 (11) | 0.0213 (3) | |
C8 | 0.33519 (18) | 0.67937 (13) | 0.31837 (13) | 0.0210 (4) | |
O1 | 0.18721 (13) | 0.75238 (10) | 0.35327 (10) | 0.0265 (3) | |
C9 | 0.62791 (19) | 0.73006 (14) | 0.56327 (13) | 0.0238 (4) | |
H9 | 0.539 (3) | 0.8222 (19) | 0.5605 (17) | 0.0286* | |
C10 | 0.5737 (2) | 0.61960 (16) | 0.67849 (14) | 0.0321 (4) | |
H10a | 0.629202 | 0.661002 | 0.78372 | 0.0481* | |
H10b | 0.411173 | 0.605373 | 0.653313 | 0.0481* | |
H10c | 0.645855 | 0.521245 | 0.672698 | 0.0481* | |
C11 | 0.8742 (2) | 0.77187 (19) | 0.60473 (16) | 0.0395 (5) | |
H11a | 0.918082 | 0.820251 | 0.707257 | 0.0593* | |
H11b | 0.963623 | 0.679459 | 0.606601 | 0.0593* | |
H11c | 0.900108 | 0.842903 | 0.527142 | 0.0593* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0245 (6) | 0.0194 (6) | 0.0193 (5) | −0.0024 (5) | 0.0063 (4) | 0.0035 (5) |
C2 | 0.0257 (6) | 0.0260 (7) | 0.0238 (6) | −0.0018 (5) | 0.0031 (5) | 0.0027 (5) |
C3 | 0.0356 (7) | 0.0284 (7) | 0.0222 (6) | −0.0042 (6) | 0.0007 (5) | 0.0008 (5) |
C4 | 0.0450 (7) | 0.0251 (7) | 0.0232 (6) | −0.0042 (5) | 0.0093 (5) | −0.0031 (5) |
C5 | 0.0330 (7) | 0.0232 (7) | 0.0260 (6) | 0.0012 (5) | 0.0104 (5) | −0.0005 (5) |
C6 | 0.0252 (5) | 0.0200 (6) | 0.0214 (6) | −0.0021 (5) | 0.0079 (4) | 0.0024 (5) |
C7 | 0.0212 (6) | 0.0231 (6) | 0.0220 (6) | 0.0017 (5) | 0.0066 (5) | −0.0013 (5) |
N1 | 0.0214 (5) | 0.0235 (5) | 0.0191 (5) | 0.0011 (4) | 0.0057 (4) | −0.0023 (4) |
C8 | 0.0221 (5) | 0.0199 (6) | 0.0211 (6) | −0.0011 (5) | 0.0063 (4) | 0.0028 (5) |
O1 | 0.0231 (4) | 0.0295 (5) | 0.0275 (4) | 0.0040 (4) | 0.0082 (3) | −0.0002 (4) |
C9 | 0.0249 (6) | 0.0253 (6) | 0.0202 (6) | 0.0013 (5) | 0.0044 (5) | −0.0048 (5) |
C10 | 0.0395 (7) | 0.0357 (8) | 0.0208 (6) | 0.0036 (6) | 0.0081 (5) | 0.0016 (5) |
C11 | 0.0303 (7) | 0.0541 (10) | 0.0328 (7) | −0.0099 (7) | 0.0065 (5) | −0.0162 (7) |
Geometric parameters (Å, º) top
C1—C2 | 1.3922 (14) | C7—N1 | 1.4639 (17) |
C1—C6 | 1.3850 (17) | N1—C8 | 1.3606 (13) |
C1—C8 | 1.4812 (17) | N1—C9 | 1.4668 (15) |
C2—H2 | 0.95 | C8—O1 | 1.2304 (15) |
C2—C3 | 1.3886 (18) | C9—H9 | 0.975 (17) |
C3—H3 | 0.95 | C9—C10 | 1.5209 (19) |
C3—C4 | 1.391 (2) | C9—C11 | 1.5165 (18) |
C4—H4 | 0.95 | C10—H10a | 0.98 |
C4—C5 | 1.3914 (17) | C10—H10b | 0.98 |
C5—H5 | 0.95 | C10—H10c | 0.98 |
C5—C6 | 1.3874 (18) | C11—H11a | 0.98 |
C6—C7 | 1.5039 (15) | C11—H11b | 0.98 |
C7—H7a | 0.984 (13) | C11—H11c | 0.98 |
C7—H7b | 0.988 (14) | | |
| | | |
C2—C1—C6 | 122.07 (11) | C7—N1—C8 | 113.41 (9) |
C2—C1—C8 | 128.94 (11) | C7—N1—C9 | 123.84 (8) |
C6—C1—C8 | 108.98 (9) | C8—N1—C9 | 121.87 (10) |
C1—C2—H2 | 121.26 | C1—C8—N1 | 106.11 (10) |
C1—C2—C3 | 117.49 (11) | C1—C8—O1 | 128.17 (9) |
H2—C2—C3 | 121.26 | N1—C8—O1 | 125.72 (11) |
C2—C3—H3 | 119.73 | N1—C9—H9 | 104.8 (8) |
C2—C3—C4 | 120.53 (11) | N1—C9—C10 | 110.19 (10) |
H3—C3—C4 | 119.73 | N1—C9—C11 | 111.04 (11) |
C3—C4—H4 | 119.17 | H9—C9—C10 | 108.3 (10) |
C3—C4—C5 | 121.66 (13) | H9—C9—C11 | 109.4 (9) |
H4—C4—C5 | 119.17 | C10—C9—C11 | 112.73 (10) |
C4—C5—H5 | 121.1 | C9—C10—H10a | 109.47 |
C4—C5—C6 | 117.80 (12) | C9—C10—H10b | 109.47 |
H5—C5—C6 | 121.1 | C9—C10—H10c | 109.47 |
C1—C6—C5 | 120.44 (10) | H10a—C10—H10b | 109.47 |
C1—C6—C7 | 109.21 (10) | H10a—C10—H10c | 109.47 |
C5—C6—C7 | 130.35 (11) | H10b—C10—H10c | 109.47 |
C6—C7—H7a | 110.1 (7) | C9—C11—H11a | 109.47 |
C6—C7—H7b | 114.0 (8) | C9—C11—H11b | 109.47 |
C6—C7—N1 | 102.20 (9) | C9—C11—H11c | 109.47 |
H7a—C7—H7b | 108.6 (11) | H11a—C11—H11b | 109.47 |
H7a—C7—N1 | 111.7 (9) | H11a—C11—H11c | 109.47 |
H7b—C7—N1 | 110.1 (8) | H11b—C11—H11c | 109.47 |
Hydrogen-bond geometry (Å, º) topCg1 is a centroid of the C1/C6/C7/N1/C8 pyrrole ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.95 | 2.58 | 3.4209 (15) | 148 |
C7—H7b···O1ii | 0.986 (13) | 2.517 (13) | 3.4873 (15) | 168.0 (11) |
C9—H9···O1 | 0.975 (17) | 2.520 (17) | 2.8671 (15) | 100.8 (11) |
C4—H4···Cg1iii | 0.95 | 2.69 | 3.6014 (14) | 160 |
C9—H9···Cg1iv | 0.975 (17) | 2.850 (16) | 3.6821 (13) | 143.9 (12) |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z; (iv) −x+1, y+1/2, −z+1. |
The bond lengths and bond orders for selected bonds in the
isoindolinone moiety of the title molecule; for the designation of the bonds,
see Fig. 3. topBond | Designation | Bond length (Å) | Bond order |
C1—C6 | D1 | 1.3850 (17) | 1.61 |
C1—C2 | D2 | 1.3922 (14) | 1.57 |
C5—C6 | D3 | 1.3874 (18) | 1.59 |
C2—C3 | D4 | 1.3886 (18) | 1.59 |
C4—C5 | D5 | 1.3914 (17) | 1.58 |
C3—C4 | D6 | 1.391 (2) | 1.58 |
C1—C8 | D7 | 1.4812 (17) | 1.23 |
C6—C7 | D8 | 1.5039 (15) | 1.16 |
C7—N1 | D9 | 1.4639 (17) | 1.06 |
C8—N1 | D10 | 1.3606 (13) | 1.38 |
C8—O1 | D11 | 1.2304 (15) | 1.79 |
N1—C9 | D12 | 1.4668 (15) | 1.05 |
The empirical bond orders for C—C, C—N and C—O (see Fig. 4) topBond order | C—C (Å) | C—N (Å) | C—O (Å) |
1 | 1.54a | 1.462b | 1.435f |
1.333 | | | 1.291g |
1.5 | 1.39a | 1.3362c | 1.251h |
2 | 1.35a | 1.253d | 1.217i |
3 | 1.20a | 1.122e | |
Notes and references: (a) Cram & Hammond (1969);
(b) trimethylamine (Dobrzycki et al., 2015; CSD refcode
DUHJIB);
(c) pyridine (Mootz & Wussow, 1981; PYRDNA01);
(d) azobenzene (Harada & Ogawa, 2004; AZOBEN12);
(e) acetonitrile in
catena-bis(µ2-acetato-O,O')tris[µ2-1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene]bis[(µ2-thiocyanato-S,S)(µ2-thiocyanato-N,S)(thiocyanato-S)]tetramercury(II)
acetonitrile solvate (Mahmoudi et al., 2009; DOMYUA);
(f) determined from 58 counts from a CSD search
for dimethyl ether;
(g) determined from 115 counts from a CSD search for carbonate;
(h) determined from 21960 counts from a CSD search for the carboxylate
group;
(i) determined from 8049 counts from a CSD search for an acetone
molecule. |