A newly synthesized N,N′-dipropyl-substituted isoindigo derivative, namely, 1-propyl-3-(1-propyl-1,2-dihydro-2-oxo-3H-indol-3-ylidene)-1,3-dihydro-2H-indol-2-one, C22H22N2O2, was found to have three polymorphic forms (denoted Forms I, II and III) under various crystallization conditions. Crystal structure analysis indicated that Form III had a significantly different molecular conformation from the other two polymorphs. Their different packing arrangements were correlated with differences in the intermolecular interactions. Thermal measurements revealed that Forms I and II are enantiotropically related, and Form II exhibits thermally dynamic behaviour.
Supporting information
CCDC references: 2321827; 2321826; 2321825
1-Propyl-3-(1-propyl-1,2-dihydro-2-oxo-3
H-indol-3-ylidene)-1,3-dihydro-2
H-indol-2-one (Form_I)
top
Crystal data top
C22H22N2O2 | F(000) = 368 |
Mr = 346.41 | Dx = 1.301 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 12.8456 (2) Å | Cell parameters from 3025 reflections |
b = 5.5803 (1) Å | θ = 4.7–74.5° |
c = 16.7446 (3) Å | µ = 0.67 mm−1 |
β = 132.566 (1)° | T = 223 K |
V = 884.01 (3) Å3 | Block, dull dark red |
Z = 2 | 0.40 × 0.30 × 0.25 mm |
Data collection top
XtaLAB AFC12 (RINC) Kappa dual home/near diffractometer | 1535 reflections with I > 2σ(I) |
Radiation source: micro-focus sealed X-ray tube, Rigaku (Cu) X-ray Source | Rint = 0.069 |
Mirror monochromator | θmax = 75.1°, θmin = 4.7° |
Detector resolution: 5.8140 pixels mm-1 | h = −15→14 |
ω scans | k = −6→6 |
4261 measured reflections | l = −20→19 |
1759 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.0893P)2 + 0.062P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.159 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.19 e Å−3 |
1759 reflections | Δρmin = −0.17 e Å−3 |
120 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.011 (2) |
Primary atom site location: dual | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.22087 (11) | 0.0744 (2) | 0.33166 (9) | 0.0655 (4) | |
N1 | 0.29921 (13) | 0.3704 (2) | 0.45455 (10) | 0.0508 (4) | |
C8 | 0.53039 (15) | 0.2622 (2) | 0.59591 (11) | 0.0468 (4) | |
C3 | 0.42327 (16) | 0.4276 (2) | 0.55897 (12) | 0.0480 (4) | |
C2 | 0.31708 (15) | 0.1689 (3) | 0.41834 (11) | 0.0484 (4) | |
C1 | 0.47079 (14) | 0.0931 (2) | 0.50603 (11) | 0.0452 (4) | |
C4 | 0.44401 (19) | 0.6179 (3) | 0.62170 (13) | 0.0565 (4) | |
H4 | 0.371094 | 0.727811 | 0.594458 | 0.068* | |
C7 | 0.66029 (17) | 0.2889 (3) | 0.70122 (13) | 0.0602 (5) | |
H7 | 0.733899 | 0.179727 | 0.729554 | 0.072* | |
C9 | 0.16559 (18) | 0.4990 (3) | 0.39196 (13) | 0.0610 (5) | |
H9a | 0.101931 | 0.444850 | 0.316426 | 0.073* | |
H9b | 0.182921 | 0.670472 | 0.392998 | 0.073* | |
C5 | 0.5742 (2) | 0.6412 (3) | 0.72484 (14) | 0.0631 (5) | |
H5 | 0.591110 | 0.768971 | 0.768911 | 0.076* | |
C10 | 0.09383 (17) | 0.4630 (4) | 0.43456 (14) | 0.0675 (5) | |
H10a | 0.154600 | 0.528010 | 0.508246 | 0.081* | |
H10b | 0.005120 | 0.553621 | 0.389069 | 0.081* | |
C6 | 0.68017 (19) | 0.4786 (4) | 0.76408 (14) | 0.0676 (5) | |
H6 | 0.768099 | 0.496358 | 0.835170 | 0.081* | |
C11 | 0.0625 (2) | 0.2049 (4) | 0.43661 (16) | 0.0774 (6) | |
H11a | −0.001595 | 0.141334 | 0.363410 | 0.116* | |
H11b | 0.019037 | 0.193115 | 0.466394 | 0.116* | |
H11c | 0.149734 | 0.113673 | 0.481351 | 0.116* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0506 (6) | 0.0680 (8) | 0.0541 (7) | −0.0041 (5) | 0.0260 (6) | −0.0160 (5) |
N1 | 0.0541 (7) | 0.0454 (7) | 0.0507 (7) | −0.0022 (5) | 0.0345 (6) | −0.0011 (5) |
C8 | 0.0523 (8) | 0.0481 (8) | 0.0485 (8) | −0.0122 (6) | 0.0375 (7) | −0.0076 (6) |
C3 | 0.0583 (8) | 0.0430 (7) | 0.0505 (8) | −0.0095 (6) | 0.0399 (7) | −0.0021 (6) |
C2 | 0.0503 (7) | 0.0489 (7) | 0.0456 (8) | −0.0072 (6) | 0.0323 (7) | −0.0045 (6) |
C1 | 0.0470 (7) | 0.0475 (7) | 0.0438 (7) | −0.0108 (5) | 0.0318 (6) | −0.0055 (5) |
C4 | 0.0731 (10) | 0.0441 (8) | 0.0621 (10) | −0.0056 (7) | 0.0496 (9) | −0.0047 (6) |
C7 | 0.0535 (8) | 0.0740 (11) | 0.0523 (9) | −0.0095 (7) | 0.0354 (8) | −0.0180 (7) |
C9 | 0.0655 (10) | 0.0515 (9) | 0.0554 (9) | 0.0098 (7) | 0.0367 (8) | 0.0088 (7) |
C5 | 0.0798 (11) | 0.0580 (9) | 0.0645 (10) | −0.0177 (8) | 0.0540 (10) | −0.0198 (8) |
C10 | 0.0570 (9) | 0.0762 (12) | 0.0590 (10) | 0.0139 (8) | 0.0351 (9) | 0.0023 (8) |
C6 | 0.0619 (9) | 0.0839 (12) | 0.0547 (9) | −0.0176 (9) | 0.0386 (8) | −0.0266 (9) |
C11 | 0.0660 (10) | 0.0950 (15) | 0.0712 (12) | −0.0013 (10) | 0.0464 (10) | 0.0076 (10) |
Geometric parameters (Å, º) top
O1—C2 | 1.2186 (17) | C7—C6 | 1.389 (2) |
N1—C3 | 1.3889 (18) | C9—H9a | 0.9800 |
N1—C2 | 1.369 (2) | C9—H9b | 0.9800 |
N1—C9 | 1.4579 (19) | C9—C10 | 1.513 (3) |
C8—C3 | 1.406 (2) | C5—H5 | 0.9400 |
C8—C1 | 1.4775 (18) | C5—C6 | 1.377 (3) |
C8—C7 | 1.391 (2) | C10—H10a | 0.9800 |
C3—C4 | 1.387 (2) | C10—H10b | 0.9800 |
C2—C1 | 1.5203 (19) | C10—C11 | 1.502 (3) |
C1—C1i | 1.374 (3) | C6—H6 | 0.9400 |
C4—H4 | 0.9400 | C11—H11a | 0.9700 |
C4—C5 | 1.375 (2) | C11—H11b | 0.9700 |
C7—H7 | 0.9400 | C11—H11c | 0.9700 |
| | | |
C3—N1—C9 | 125.61 (13) | N1—C9—C10 | 113.10 (13) |
C2—N1—C3 | 110.67 (12) | H9a—C9—H9b | 107.8 |
C2—N1—C9 | 123.68 (13) | C10—C9—H9a | 109.0 |
C3—C8—C1 | 107.02 (12) | C10—C9—H9b | 109.0 |
C7—C8—C3 | 117.72 (13) | C4—C5—H5 | 119.8 |
C7—C8—C1 | 135.27 (14) | C4—C5—C6 | 120.46 (15) |
N1—C3—C8 | 110.56 (12) | C6—C5—H5 | 119.8 |
C4—C3—N1 | 126.76 (15) | C9—C10—H10a | 108.9 |
C4—C3—C8 | 122.69 (15) | C9—C10—H10b | 108.9 |
O1—C2—N1 | 122.96 (14) | H10a—C10—H10b | 107.7 |
O1—C2—C1 | 129.67 (14) | C11—C10—C9 | 113.36 (15) |
N1—C2—C1 | 107.35 (12) | C11—C10—H10a | 108.9 |
C8—C1—C2 | 104.23 (12) | C11—C10—H10b | 108.9 |
C1i—C1—C8 | 132.41 (16) | C7—C6—H6 | 119.2 |
C1i—C1—C2 | 123.36 (15) | C5—C6—C7 | 121.64 (16) |
C3—C4—H4 | 120.9 | C5—C6—H6 | 119.2 |
C5—C4—C3 | 118.10 (16) | C10—C11—H11a | 109.5 |
C5—C4—H4 | 120.9 | C10—C11—H11b | 109.5 |
C8—C7—H7 | 120.3 | C10—C11—H11c | 109.5 |
C6—C7—C8 | 119.36 (16) | H11a—C11—H11b | 109.5 |
C6—C7—H7 | 120.3 | H11a—C11—H11c | 109.5 |
N1—C9—H9a | 109.0 | H11b—C11—H11c | 109.5 |
N1—C9—H9b | 109.0 | | |
| | | |
O1—C2—C1—C8 | −173.83 (15) | C2—N1—C3—C8 | 0.43 (16) |
O1—C2—C1—C1i | 6.9 (3) | C2—N1—C3—C4 | −179.26 (13) |
N1—C3—C4—C5 | 178.34 (13) | C2—N1—C9—C10 | 106.74 (17) |
N1—C2—C1—C8 | 4.26 (15) | C1—C8—C3—N1 | 2.40 (15) |
N1—C2—C1—C1i | −175.04 (15) | C1—C8—C3—C4 | −177.90 (13) |
N1—C9—C10—C11 | −58.6 (2) | C1—C8—C7—C6 | 178.58 (16) |
C8—C3—C4—C5 | −1.3 (2) | C4—C5—C6—C7 | 0.8 (3) |
C8—C7—C6—C5 | 0.1 (3) | C7—C8—C3—N1 | −177.50 (12) |
C3—N1—C2—O1 | 175.25 (13) | C7—C8—C3—C4 | 2.2 (2) |
C3—N1—C2—C1 | −3.00 (16) | C7—C8—C1—C2 | 175.91 (16) |
C3—N1—C9—C10 | −70.85 (19) | C7—C8—C1—C1i | −4.9 (3) |
C3—C8—C1—C2 | −3.97 (14) | C9—N1—C3—C8 | 178.28 (13) |
C3—C8—C1—C1i | 175.25 (18) | C9—N1—C3—C4 | −1.4 (2) |
C3—C8—C7—C6 | −1.6 (2) | C9—N1—C2—O1 | −2.7 (2) |
C3—C4—C5—C6 | −0.2 (2) | C9—N1—C2—C1 | 179.10 (12) |
Symmetry code: (i) −x+1, −y, −z+1. |
1-Propyl-3-(1-propyl-1,2-dihydro-2-oxo-3
H-indol-3-ylidene)-1,3-dihydro-2
H-indol-2-one (Form_II)
top
Crystal data top
C22H22N2O2 | F(000) = 1472 |
Mr = 346.41 | Dx = 1.308 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54184 Å |
a = 35.4947 (9) Å | Cell parameters from 5948 reflections |
b = 5.5238 (1) Å | θ = 4.8–74.3° |
c = 18.9927 (4) Å | µ = 0.67 mm−1 |
β = 109.151 (2)° | T = 223 K |
V = 3517.73 (14) Å3 | Needle, dull dark red |
Z = 8 | 1 × 0.11 × 0.06 mm |
Data collection top
XtaLAB AFC12 (RINC) Kappa dual offset/far diffractometer | 3518 independent reflections |
Radiation source: micro-focus sealed X-ray tube, Rigaku (Cu) X-ray Source | 3113 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.034 |
Detector resolution: 5.8140 pixels mm-1 | θmax = 75.2°, θmin = 4.8° |
ω scans | h = −43→44 |
Absorption correction: multi-scan CrysAlis PRO; Rigaku OD, 2019) | k = −6→6 |
Tmin = 0.817, Tmax = 1.000 | l = −23→23 |
9278 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.1061P)2 + 0.5262P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.152 | (Δ/σ)max = 0.002 |
S = 1.05 | Δρmax = 0.25 e Å−3 |
3518 reflections | Δρmin = −0.23 e Å−3 |
238 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00101 (15) |
Primary atom site location: dual | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.63730 (3) | 0.27171 (19) | 0.83154 (5) | 0.0592 (3) | |
O2 | 0.61174 (3) | 0.3533 (2) | 0.53628 (5) | 0.0612 (3) | |
N1 | 0.59659 (3) | −0.03824 (19) | 0.77483 (5) | 0.0443 (3) | |
N2 | 0.65393 (3) | 0.65684 (19) | 0.59344 (6) | 0.0464 (3) | |
C1 | 0.61464 (3) | 0.2200 (2) | 0.69428 (6) | 0.0399 (3) | |
C3 | 0.57628 (3) | −0.1136 (2) | 0.70218 (6) | 0.0409 (3) | |
C12 | 0.63529 (3) | 0.4009 (2) | 0.67389 (6) | 0.0404 (3) | |
C8 | 0.58551 (3) | 0.0398 (2) | 0.65104 (6) | 0.0408 (3) | |
C19 | 0.66452 (3) | 0.5806 (2) | 0.71726 (6) | 0.0425 (3) | |
C2 | 0.61876 (3) | 0.1628 (2) | 0.77486 (6) | 0.0427 (3) | |
C14 | 0.67413 (3) | 0.7322 (2) | 0.66610 (7) | 0.0428 (3) | |
C13 | 0.63096 (3) | 0.4584 (2) | 0.59320 (6) | 0.0441 (3) | |
C4 | 0.55074 (4) | −0.3089 (2) | 0.68118 (7) | 0.0498 (3) | |
H4 | 0.545783 | −0.410194 | 0.716932 | 0.060* | |
C15 | 0.69986 (4) | 0.9271 (2) | 0.68733 (8) | 0.0524 (3) | |
H15 | 0.705352 | 1.026099 | 0.651616 | 0.063* | |
C9 | 0.59376 (4) | −0.1501 (2) | 0.84255 (7) | 0.0533 (3) | |
H9a | 0.614651 | −0.082747 | 0.885665 | 0.064* | |
H9b | 0.598716 | −0.324246 | 0.840964 | 0.064* | |
C5 | 0.53267 (4) | −0.3505 (3) | 0.60557 (8) | 0.0567 (4) | |
H5 | 0.515196 | −0.482301 | 0.589425 | 0.068* | |
C20 | 0.65649 (4) | 0.7721 (3) | 0.52599 (8) | 0.0553 (3) | |
H20a | 0.653714 | 0.947611 | 0.530119 | 0.066* | |
H20b | 0.634229 | 0.715933 | 0.483179 | 0.066* | |
C18 | 0.68318 (4) | 0.6282 (3) | 0.79280 (7) | 0.0562 (4) | |
H18 | 0.678186 | 0.528895 | 0.828967 | 0.067* | |
C21 | 0.69528 (4) | 0.7197 (3) | 0.51183 (8) | 0.0599 (4) | |
H21a | 0.695629 | 0.808848 | 0.467433 | 0.072* | |
H21b | 0.717537 | 0.778549 | 0.554199 | 0.072* | |
C16 | 0.71731 (4) | 0.9719 (3) | 0.76299 (9) | 0.0573 (4) | |
H16 | 0.734693 | 1.104116 | 0.779136 | 0.069* | |
C7 | 0.56636 (4) | −0.0063 (3) | 0.57552 (7) | 0.0583 (4) | |
H7 | 0.571152 | 0.093440 | 0.539268 | 0.070* | |
C17 | 0.70924 (4) | 0.8234 (3) | 0.81446 (8) | 0.0620 (4) | |
H17 | 0.721639 | 0.854567 | 0.865511 | 0.074* | |
C6 | 0.54018 (4) | −0.2000 (3) | 0.55412 (8) | 0.0643 (4) | |
H6 | 0.527256 | −0.229012 | 0.503099 | 0.077* | |
C10 | 0.55374 (5) | −0.1129 (3) | 0.85314 (8) | 0.0595 (4) | |
H10a | 0.533327 | −0.198164 | 0.813272 | 0.071* | |
H10b | 0.554550 | −0.186347 | 0.900585 | 0.071* | |
C22 | 0.70128 (5) | 0.4536 (3) | 0.50062 (9) | 0.0657 (4) | |
H22a | 0.678971 | 0.393025 | 0.459609 | 0.099* | |
H22b | 0.702922 | 0.365674 | 0.545738 | 0.099* | |
H22c | 0.725787 | 0.431252 | 0.489311 | 0.099* | |
C11 | 0.54160 (6) | 0.1482 (3) | 0.85300 (10) | 0.0745 (5) | |
H11a | 0.540499 | 0.222691 | 0.806111 | 0.112* | |
H11b | 0.560937 | 0.232889 | 0.893774 | 0.112* | |
H11c | 0.515533 | 0.157367 | 0.859010 | 0.112* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0704 (6) | 0.0688 (6) | 0.0370 (5) | −0.0232 (5) | 0.0155 (4) | −0.0157 (4) |
O2 | 0.0734 (6) | 0.0706 (6) | 0.0389 (5) | −0.0244 (5) | 0.0175 (4) | −0.0125 (4) |
N1 | 0.0477 (5) | 0.0472 (6) | 0.0369 (5) | −0.0041 (4) | 0.0121 (4) | −0.0052 (4) |
N2 | 0.0477 (6) | 0.0458 (6) | 0.0428 (5) | −0.0025 (4) | 0.0109 (4) | −0.0008 (4) |
C1 | 0.0353 (5) | 0.0495 (6) | 0.0360 (5) | −0.0022 (4) | 0.0133 (4) | −0.0120 (4) |
C3 | 0.0367 (5) | 0.0431 (6) | 0.0418 (6) | 0.0019 (4) | 0.0116 (5) | −0.0101 (5) |
C12 | 0.0357 (5) | 0.0492 (6) | 0.0368 (5) | −0.0018 (4) | 0.0127 (4) | −0.0119 (4) |
C8 | 0.0353 (5) | 0.0495 (6) | 0.0392 (6) | −0.0031 (4) | 0.0145 (4) | −0.0123 (5) |
C19 | 0.0339 (5) | 0.0488 (6) | 0.0458 (6) | −0.0018 (4) | 0.0146 (5) | −0.0129 (5) |
C2 | 0.0413 (6) | 0.0492 (6) | 0.0381 (6) | −0.0026 (5) | 0.0135 (5) | −0.0097 (5) |
C14 | 0.0366 (5) | 0.0406 (6) | 0.0490 (6) | 0.0040 (4) | 0.0110 (5) | −0.0061 (5) |
C13 | 0.0435 (6) | 0.0487 (6) | 0.0407 (6) | −0.0020 (5) | 0.0147 (5) | −0.0065 (5) |
C4 | 0.0509 (7) | 0.0448 (6) | 0.0528 (7) | −0.0048 (5) | 0.0155 (6) | −0.0076 (5) |
C15 | 0.0483 (7) | 0.0410 (6) | 0.0633 (8) | −0.0017 (5) | 0.0121 (6) | −0.0028 (5) |
C9 | 0.0627 (8) | 0.0504 (7) | 0.0414 (6) | −0.0034 (6) | 0.0097 (5) | 0.0033 (5) |
C5 | 0.0521 (7) | 0.0577 (8) | 0.0586 (8) | −0.0152 (6) | 0.0161 (6) | −0.0209 (6) |
C20 | 0.0611 (8) | 0.0486 (7) | 0.0498 (7) | −0.0004 (6) | 0.0096 (6) | 0.0095 (5) |
C18 | 0.0485 (7) | 0.0756 (9) | 0.0454 (7) | −0.0186 (6) | 0.0167 (5) | −0.0175 (6) |
C21 | 0.0626 (8) | 0.0685 (9) | 0.0475 (7) | −0.0128 (7) | 0.0166 (6) | 0.0108 (6) |
C16 | 0.0461 (7) | 0.0512 (7) | 0.0699 (9) | −0.0088 (5) | 0.0125 (6) | −0.0165 (6) |
C7 | 0.0562 (7) | 0.0798 (10) | 0.0390 (6) | −0.0240 (7) | 0.0159 (5) | −0.0161 (6) |
C17 | 0.0510 (7) | 0.0780 (10) | 0.0540 (7) | −0.0191 (7) | 0.0130 (6) | −0.0240 (7) |
C6 | 0.0608 (8) | 0.0847 (10) | 0.0450 (7) | −0.0269 (7) | 0.0144 (6) | −0.0250 (7) |
C10 | 0.0691 (9) | 0.0686 (9) | 0.0432 (6) | −0.0131 (7) | 0.0219 (6) | 0.0024 (6) |
C22 | 0.0649 (8) | 0.0777 (10) | 0.0577 (8) | 0.0049 (7) | 0.0245 (7) | 0.0069 (7) |
C11 | 0.0768 (10) | 0.0855 (11) | 0.0705 (10) | 0.0061 (9) | 0.0368 (8) | −0.0027 (8) |
Geometric parameters (Å, º) top
O1—C2 | 1.2201 (14) | C5—H5 | 0.9400 |
O2—C13 | 1.2196 (15) | C5—C6 | 1.374 (2) |
N1—C3 | 1.3944 (14) | C20—H20a | 0.9800 |
N1—C2 | 1.3608 (16) | C20—H20b | 0.9800 |
N1—C9 | 1.4599 (16) | C20—C21 | 1.515 (2) |
N2—C14 | 1.3938 (15) | C18—H18 | 0.9400 |
N2—C13 | 1.3651 (16) | C18—C17 | 1.3923 (19) |
N2—C20 | 1.4599 (17) | C21—H21a | 0.9800 |
C1—C12 | 1.3679 (18) | C21—H21b | 0.9800 |
C1—C8 | 1.4757 (15) | C21—C22 | 1.510 (2) |
C1—C2 | 1.5222 (15) | C16—H16 | 0.9400 |
C3—C8 | 1.4064 (17) | C16—C17 | 1.376 (2) |
C3—C4 | 1.3810 (17) | C7—H7 | 0.9400 |
C12—C19 | 1.4763 (15) | C7—C6 | 1.3876 (19) |
C12—C13 | 1.5226 (16) | C17—H17 | 0.9400 |
C8—C7 | 1.3944 (16) | C6—H6 | 0.9400 |
C19—C14 | 1.4068 (18) | C10—H10a | 0.9800 |
C19—C18 | 1.3938 (16) | C10—H10b | 0.9800 |
C14—C15 | 1.3839 (17) | C10—C11 | 1.505 (2) |
C4—H4 | 0.9400 | C22—H22a | 0.9700 |
C4—C5 | 1.3864 (18) | C22—H22b | 0.9700 |
C15—H15 | 0.9400 | C22—H22c | 0.9700 |
C15—C16 | 1.388 (2) | C11—H11a | 0.9700 |
C9—H9a | 0.9800 | C11—H11b | 0.9700 |
C9—H9b | 0.9800 | C11—H11c | 0.9700 |
C9—C10 | 1.513 (2) | | |
| | | |
C3—N1—C9 | 125.64 (10) | N2—C20—H20a | 108.9 |
C2—N1—C3 | 110.82 (10) | N2—C20—H20b | 108.9 |
C2—N1—C9 | 123.50 (10) | N2—C20—C21 | 113.22 (11) |
C14—N2—C20 | 125.36 (11) | H20a—C20—H20b | 107.7 |
C13—N2—C14 | 110.82 (10) | C21—C20—H20a | 108.9 |
C13—N2—C20 | 123.81 (10) | C21—C20—H20b | 108.9 |
C12—C1—C8 | 132.67 (10) | C19—C18—H18 | 120.1 |
C12—C1—C2 | 123.55 (10) | C17—C18—C19 | 119.70 (13) |
C8—C1—C2 | 103.77 (10) | C17—C18—H18 | 120.1 |
N1—C3—C8 | 109.96 (10) | C20—C21—H21a | 109.0 |
C4—C3—N1 | 126.62 (12) | C20—C21—H21b | 109.0 |
C4—C3—C8 | 123.41 (11) | H21a—C21—H21b | 107.8 |
C1—C12—C19 | 132.58 (10) | C22—C21—C20 | 112.92 (12) |
C1—C12—C13 | 123.42 (10) | C22—C21—H21a | 109.0 |
C19—C12—C13 | 103.99 (10) | C22—C21—H21b | 109.0 |
C3—C8—C1 | 107.56 (9) | C15—C16—H16 | 119.9 |
C7—C8—C1 | 135.38 (11) | C17—C16—C15 | 120.19 (12) |
C7—C8—C3 | 117.06 (11) | C17—C16—H16 | 119.9 |
C14—C19—C12 | 107.46 (10) | C8—C7—H7 | 120.1 |
C18—C19—C12 | 135.31 (12) | C6—C7—C8 | 119.72 (13) |
C18—C19—C14 | 117.24 (11) | C6—C7—H7 | 120.1 |
O1—C2—N1 | 123.17 (11) | C18—C17—H17 | 119.2 |
O1—C2—C1 | 129.10 (12) | C16—C17—C18 | 121.66 (13) |
N1—C2—C1 | 107.71 (9) | C16—C17—H17 | 119.2 |
N2—C14—C19 | 110.11 (10) | C5—C6—C7 | 121.72 (13) |
C15—C14—N2 | 126.63 (12) | C5—C6—H6 | 119.1 |
C15—C14—C19 | 123.26 (12) | C7—C6—H6 | 119.1 |
O2—C13—N2 | 123.02 (11) | C9—C10—H10a | 108.7 |
O2—C13—C12 | 129.43 (12) | C9—C10—H10b | 108.7 |
N2—C13—C12 | 107.54 (9) | H10a—C10—H10b | 107.6 |
C3—C4—H4 | 121.1 | C11—C10—C9 | 114.26 (13) |
C3—C4—C5 | 117.75 (13) | C11—C10—H10a | 108.7 |
C5—C4—H4 | 121.1 | C11—C10—H10b | 108.7 |
C14—C15—H15 | 121.0 | C21—C22—H22a | 109.5 |
C14—C15—C16 | 117.91 (13) | C21—C22—H22b | 109.5 |
C16—C15—H15 | 121.0 | C21—C22—H22c | 109.5 |
N1—C9—H9a | 108.9 | H22a—C22—H22b | 109.5 |
N1—C9—H9b | 108.9 | H22a—C22—H22c | 109.5 |
N1—C9—C10 | 113.50 (11) | H22b—C22—H22c | 109.5 |
H9a—C9—H9b | 107.7 | C10—C11—H11a | 109.5 |
C10—C9—H9a | 108.9 | C10—C11—H11b | 109.5 |
C10—C9—H9b | 108.9 | C10—C11—H11c | 109.5 |
C4—C5—H5 | 119.9 | H11a—C11—H11b | 109.5 |
C6—C5—C4 | 120.29 (12) | H11a—C11—H11c | 109.5 |
C6—C5—H5 | 119.9 | H11b—C11—H11c | 109.5 |
| | | |
N1—C3—C8—C1 | 1.87 (13) | C19—C18—C17—C16 | −0.2 (2) |
N1—C3—C8—C7 | −177.73 (10) | C2—N1—C3—C8 | 0.99 (13) |
N1—C3—C4—C5 | 178.52 (11) | C2—N1—C3—C4 | −179.19 (11) |
N1—C9—C10—C11 | −55.90 (16) | C2—N1—C9—C10 | 108.04 (14) |
N2—C14—C15—C16 | −179.64 (11) | C2—C1—C12—C19 | −0.6 (2) |
N2—C20—C21—C22 | 61.62 (16) | C2—C1—C12—C13 | −179.70 (10) |
C1—C12—C19—C14 | −176.47 (12) | C2—C1—C8—C3 | −3.63 (12) |
C1—C12—C19—C18 | 3.4 (2) | C2—C1—C8—C7 | 175.86 (14) |
C1—C12—C13—O2 | −4.8 (2) | C14—N2—C13—O2 | −176.90 (12) |
C1—C12—C13—N2 | 176.40 (11) | C14—N2—C13—C12 | 2.01 (13) |
C1—C8—C7—C6 | 179.22 (13) | C14—N2—C20—C21 | 74.72 (16) |
C3—N1—C2—O1 | 175.40 (11) | C14—C19—C18—C17 | 1.68 (19) |
C3—N1—C2—C1 | −3.32 (13) | C14—C15—C16—C17 | 0.7 (2) |
C3—N1—C9—C10 | −69.30 (16) | C13—N2—C14—C19 | −0.23 (13) |
C3—C8—C7—C6 | −1.3 (2) | C13—N2—C14—C15 | −179.78 (11) |
C3—C4—C5—C6 | −0.2 (2) | C13—N2—C20—C21 | −105.42 (14) |
C12—C1—C8—C3 | 175.66 (12) | C13—C12—C19—C14 | 2.74 (12) |
C12—C1—C8—C7 | −4.8 (2) | C13—C12—C19—C18 | −177.36 (14) |
C12—C1—C2—O1 | 6.3 (2) | C4—C3—C8—C1 | −177.96 (10) |
C12—C1—C2—N1 | −175.13 (11) | C4—C3—C8—C7 | 2.44 (18) |
C12—C19—C14—N2 | −1.71 (12) | C4—C5—C6—C7 | 1.3 (2) |
C12—C19—C14—C15 | 177.86 (10) | C15—C16—C17—C18 | −1.1 (2) |
C12—C19—C18—C17 | −178.21 (13) | C9—N1—C3—C8 | 178.61 (11) |
C8—C1—C12—C19 | −179.78 (11) | C9—N1—C3—C4 | −1.56 (19) |
C8—C1—C12—C13 | 1.1 (2) | C9—N1—C2—O1 | −2.29 (19) |
C8—C1—C2—O1 | −174.38 (12) | C9—N1—C2—C1 | 178.99 (11) |
C8—C1—C2—N1 | 4.25 (12) | C20—N2—C14—C19 | 179.65 (11) |
C8—C3—C4—C5 | −1.68 (19) | C20—N2—C14—C15 | 0.10 (19) |
C8—C7—C6—C5 | −0.5 (2) | C20—N2—C13—O2 | 3.22 (19) |
C19—C12—C13—O2 | 175.91 (13) | C20—N2—C13—C12 | −177.87 (11) |
C19—C12—C13—N2 | −2.91 (12) | C18—C19—C14—N2 | 178.38 (10) |
C19—C14—C15—C16 | 0.87 (18) | C18—C19—C14—C15 | −2.06 (17) |
1-Propyl-3-(1-propyl-1,2-dihydro-2-oxo-3
H-indol-3-ylidene)-1,3-dihydro-2
H-indol-2-one (Form_III)
top
Crystal data top
C22H22N2O2 | F(000) = 736 |
Mr = 346.41 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 15.0486 (2) Å | Cell parameters from 6130 reflections |
b = 9.1347 (1) Å | θ = 4.8–74.8° |
c = 18.5227 (2) Å | µ = 0.67 mm−1 |
β = 136.112 (1)° | T = 223 K |
V = 1765.16 (4) Å3 | Block, dull light red |
Z = 4 | 0.20 × 0.17 × 0.13 mm |
Data collection top
XtaLAB AFC12 (RINC) Kappa dual home/near diffractometer | 3541 independent reflections |
Radiation source: micro-focus sealed X-ray tube, Rigaku (Cu) X-ray Source | 3072 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.025 |
Detector resolution: 5.8140 pixels mm-1 | θmax = 75.2°, θmin = 4.2° |
ω scans | h = −18→18 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019) | k = −11→5 |
Tmin = 0.270, Tmax = 1.000 | l = −23→23 |
11608 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | w = 1/[σ2(Fo2) + (0.0642P)2 + 0.5231P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.136 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.60 e Å−3 |
3541 reflections | Δρmin = −0.43 e Å−3 |
266 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0030 (4) |
Primary atom site location: dual | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O2 | 0.23797 (11) | 0.83302 (14) | 0.20951 (9) | 0.0484 (3) | |
N2 | 0.44626 (12) | 0.89716 (14) | 0.35540 (10) | 0.0393 (3) | |
O1 | 0.33942 (14) | 0.65392 (19) | 0.53117 (10) | 0.0677 (4) | |
C8 | 0.14714 (14) | 0.57916 (16) | 0.26462 (12) | 0.0368 (3) | |
C12 | 0.35609 (14) | 0.73178 (16) | 0.38287 (11) | 0.0351 (3) | |
N1 | 0.16264 (16) | 0.5227 (2) | 0.39373 (12) | 0.0625 (5) | |
C13 | 0.33529 (14) | 0.82124 (17) | 0.30243 (12) | 0.0367 (3) | |
C7 | 0.09157 (15) | 0.56846 (19) | 0.16416 (12) | 0.0424 (4) | |
H7 | 0.125079 | 0.621893 | 0.144730 | 0.051* | |
C14 | 0.53824 (14) | 0.86304 (17) | 0.46145 (12) | 0.0378 (3) | |
C19 | 0.48756 (14) | 0.76297 (17) | 0.48174 (11) | 0.0364 (3) | |
C1 | 0.26442 (14) | 0.64715 (17) | 0.36099 (11) | 0.0369 (3) | |
C3 | 0.09339 (16) | 0.4978 (2) | 0.28983 (13) | 0.0469 (4) | |
C18 | 0.56864 (16) | 0.70665 (19) | 0.58220 (12) | 0.0446 (4) | |
H18 | 0.538450 | 0.635999 | 0.597272 | 0.053* | |
C20 | 0.46824 (16) | 0.99641 (18) | 0.30784 (13) | 0.0437 (4) | |
H20a | 0.509764 | 1.085523 | 0.350064 | 0.052* | |
H20b | 0.385449 | 1.024448 | 0.238538 | 0.052* | |
C15 | 0.66253 (16) | 0.91414 (19) | 0.53859 (13) | 0.0463 (4) | |
H15 | 0.693892 | 0.983553 | 0.523914 | 0.056* | |
C17 | 0.69373 (17) | 0.7556 (2) | 0.65941 (13) | 0.0509 (4) | |
H17 | 0.748607 | 0.717774 | 0.727208 | 0.061* | |
C21 | 0.55149 (18) | 0.92896 (19) | 0.29769 (14) | 0.0470 (4) | |
H21a | 0.627135 | 0.883807 | 0.364082 | 0.056* | |
H21b | 0.503011 | 0.851881 | 0.244634 | 0.056* | |
C6 | −0.01393 (16) | 0.4781 (2) | 0.09277 (14) | 0.0492 (4) | |
H6 | −0.051994 | 0.471295 | 0.024608 | 0.059* | |
C2 | 0.26739 (17) | 0.6085 (2) | 0.44193 (13) | 0.0502 (4) | |
C5 | −0.06388 (17) | 0.3982 (2) | 0.11984 (15) | 0.0511 (4) | |
H5 | −0.134876 | 0.337005 | 0.070232 | 0.061* | |
C16 | 0.73933 (16) | 0.8598 (2) | 0.63815 (14) | 0.0518 (4) | |
H16 | 0.823886 | 0.894024 | 0.692341 | 0.062* | |
C4 | −0.01076 (18) | 0.4070 (2) | 0.21950 (15) | 0.0550 (5) | |
H4 | −0.044649 | 0.352837 | 0.238359 | 0.066* | |
C22 | 0.5941 (2) | 1.0418 (2) | 0.26803 (16) | 0.0547 (5) | |
H22a | 0.519561 | 1.082888 | 0.200501 | 0.082* | |
H22b | 0.649266 | 0.995890 | 0.264799 | 0.082* | |
H22c | 0.640785 | 1.119231 | 0.319753 | 0.082* | |
C11A | 0.1301 (6) | 0.3169 (6) | 0.5520 (5) | 0.0550 (12) | 0.7275 |
H11Aa | 0.038093 | 0.301503 | 0.499288 | 0.082* | 0.7275 |
H11Ab | 0.151957 | 0.399504 | 0.595360 | 0.082* | 0.7275 |
H11Ac | 0.173286 | 0.229872 | 0.594796 | 0.082* | 0.7275 |
C9A | 0.1175 (2) | 0.4927 (3) | 0.4413 (2) | 0.0439 (5) | 0.7275 |
H9Aa | 0.023635 | 0.488604 | 0.386875 | 0.053* | 0.7275 |
H9Ab | 0.144626 | 0.572028 | 0.489367 | 0.053* | 0.7275 |
C10A | 0.1717 (2) | 0.3479 (3) | 0.5002 (2) | 0.0457 (5) | 0.7275 |
H10Aa | 0.142531 | 0.268421 | 0.451592 | 0.055* | 0.7275 |
H10Ab | 0.265477 | 0.351115 | 0.553044 | 0.055* | 0.7275 |
C9B | 0.1753 (8) | 0.3899 (10) | 0.4603 (7) | 0.0623 (18) | 0.2725 |
H9Ba | 0.139070 | 0.297641 | 0.421392 | 0.075* | 0.2725 |
H9Bb | 0.263954 | 0.374566 | 0.528039 | 0.075* | 0.2725 |
C11B | 0.0968 (17) | 0.3611 (17) | 0.5390 (14) | 0.063 (4) | 0.2725 |
H11Ba | 0.112163 | 0.259522 | 0.535379 | 0.094* | 0.2725 |
H11Bb | 0.014179 | 0.369729 | 0.514252 | 0.094* | 0.2725 |
H11Bc | 0.163616 | 0.394731 | 0.610530 | 0.094* | 0.2725 |
C10B | 0.0975 (10) | 0.4561 (11) | 0.4698 (8) | 0.074 (2) | 0.2725 |
H10Ba | 0.009619 | 0.467213 | 0.400451 | 0.089* | 0.2725 |
H10Bb | 0.130901 | 0.553734 | 0.500562 | 0.089* | 0.2725 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0432 (6) | 0.0516 (7) | 0.0412 (6) | 0.0008 (5) | 0.0273 (5) | 0.0099 (5) |
N2 | 0.0395 (7) | 0.0402 (7) | 0.0426 (7) | 0.0012 (5) | 0.0311 (6) | 0.0057 (5) |
O1 | 0.0655 (8) | 0.0988 (11) | 0.0477 (7) | −0.0218 (8) | 0.0438 (7) | −0.0090 (7) |
C8 | 0.0367 (7) | 0.0354 (7) | 0.0430 (8) | 0.0036 (6) | 0.0303 (7) | 0.0036 (6) |
C12 | 0.0379 (7) | 0.0344 (7) | 0.0384 (7) | 0.0061 (6) | 0.0293 (7) | 0.0045 (6) |
N1 | 0.0636 (10) | 0.0812 (12) | 0.0517 (9) | −0.0219 (9) | 0.0445 (8) | −0.0012 (8) |
C13 | 0.0373 (7) | 0.0363 (7) | 0.0409 (8) | 0.0037 (6) | 0.0296 (7) | 0.0048 (6) |
C7 | 0.0409 (8) | 0.0456 (9) | 0.0443 (8) | 0.0008 (7) | 0.0319 (7) | 0.0007 (7) |
C14 | 0.0388 (8) | 0.0364 (8) | 0.0416 (8) | 0.0039 (6) | 0.0301 (7) | 0.0009 (6) |
C19 | 0.0381 (7) | 0.0349 (7) | 0.0397 (8) | 0.0040 (6) | 0.0292 (7) | 0.0017 (6) |
C1 | 0.0402 (8) | 0.0360 (8) | 0.0400 (8) | 0.0042 (6) | 0.0307 (7) | 0.0044 (6) |
C3 | 0.0471 (9) | 0.0492 (9) | 0.0495 (9) | −0.0037 (7) | 0.0366 (8) | 0.0020 (7) |
C18 | 0.0470 (9) | 0.0446 (9) | 0.0425 (8) | 0.0063 (7) | 0.0324 (8) | 0.0058 (7) |
C20 | 0.0473 (9) | 0.0399 (8) | 0.0518 (9) | 0.0013 (7) | 0.0383 (8) | 0.0079 (7) |
C15 | 0.0416 (8) | 0.0463 (9) | 0.0512 (9) | −0.0034 (7) | 0.0336 (8) | −0.0032 (7) |
C17 | 0.0457 (9) | 0.0560 (10) | 0.0392 (8) | 0.0091 (8) | 0.0267 (8) | 0.0036 (7) |
C21 | 0.0589 (10) | 0.0384 (8) | 0.0584 (10) | −0.0009 (7) | 0.0471 (9) | 0.0009 (7) |
C6 | 0.0438 (9) | 0.0552 (10) | 0.0470 (9) | −0.0029 (8) | 0.0322 (8) | −0.0070 (8) |
C2 | 0.0505 (9) | 0.0609 (11) | 0.0447 (9) | −0.0073 (8) | 0.0361 (8) | 0.0019 (8) |
C5 | 0.0425 (9) | 0.0467 (9) | 0.0581 (10) | −0.0046 (7) | 0.0343 (8) | −0.0070 (8) |
C16 | 0.0378 (8) | 0.0585 (11) | 0.0467 (9) | −0.0019 (8) | 0.0263 (8) | −0.0076 (8) |
C4 | 0.0529 (10) | 0.0533 (10) | 0.0633 (11) | −0.0095 (8) | 0.0433 (10) | 0.0015 (8) |
C22 | 0.0659 (11) | 0.0499 (10) | 0.0714 (12) | −0.0060 (9) | 0.0572 (11) | −0.0021 (9) |
C11A | 0.068 (3) | 0.054 (3) | 0.0531 (18) | −0.0091 (18) | 0.047 (2) | 0.0009 (18) |
C9A | 0.0483 (12) | 0.0481 (14) | 0.0536 (13) | 0.0058 (11) | 0.0428 (12) | 0.0124 (11) |
C10A | 0.0528 (13) | 0.0421 (13) | 0.0495 (13) | −0.0008 (10) | 0.0393 (12) | 0.0083 (10) |
C9B | 0.058 (4) | 0.060 (5) | 0.064 (5) | 0.000 (4) | 0.042 (4) | 0.008 (4) |
C11B | 0.090 (10) | 0.067 (10) | 0.078 (8) | −0.012 (6) | 0.076 (9) | −0.004 (7) |
C10B | 0.087 (6) | 0.071 (6) | 0.082 (6) | 0.011 (5) | 0.067 (5) | 0.010 (5) |
Geometric parameters (Å, º) top
O2—C13 | 1.2188 (18) | C21—H21a | 0.9800 |
N2—C13 | 1.368 (2) | C21—H21b | 0.9800 |
N2—C14 | 1.3973 (19) | C21—C22 | 1.511 (2) |
N2—C20 | 1.4586 (19) | C6—H6 | 0.9400 |
O1—C2 | 1.223 (2) | C6—C5 | 1.375 (3) |
C8—C7 | 1.389 (2) | C5—H5 | 0.9400 |
C8—C1 | 1.465 (2) | C5—C4 | 1.388 (3) |
C8—C3 | 1.403 (2) | C16—H16 | 0.9400 |
C12—C13 | 1.521 (2) | C4—H4 | 0.9400 |
C12—C19 | 1.458 (2) | C22—H22a | 0.9700 |
C12—C1 | 1.364 (2) | C22—H22b | 0.9700 |
N1—C3 | 1.397 (2) | C22—H22c | 0.9700 |
N1—C2 | 1.366 (2) | C11A—H11Aa | 0.9700 |
N1—C9A | 1.476 (3) | C11A—H11Ab | 0.9700 |
N1—C9B | 1.641 (9) | C11A—H11Ac | 0.9700 |
C7—H7 | 0.9400 | C11A—C10A | 1.503 (7) |
C7—C6 | 1.387 (2) | C9A—H9Aa | 0.9800 |
C14—C19 | 1.404 (2) | C9A—H9Ab | 0.9800 |
C14—C15 | 1.381 (2) | C9A—C10A | 1.524 (3) |
C19—C18 | 1.394 (2) | C10A—H10Aa | 0.9800 |
C1—C2 | 1.509 (2) | C10A—H10Ab | 0.9800 |
C3—C4 | 1.378 (2) | C9B—H9Ba | 0.9800 |
C18—H18 | 0.9400 | C9B—H9Bb | 0.9800 |
C18—C17 | 1.381 (2) | C9B—C10B | 1.436 (12) |
C20—H20a | 0.9800 | C11B—H11Ba | 0.9700 |
C20—H20b | 0.9800 | C11B—H11Bb | 0.9700 |
C20—C21 | 1.525 (2) | C11B—H11Bc | 0.9700 |
C15—H15 | 0.9400 | C11B—C10B | 1.555 (19) |
C15—C16 | 1.382 (2) | C10B—H10Ba | 0.9800 |
C17—H17 | 0.9400 | C10B—H10Bb | 0.9800 |
C17—C16 | 1.386 (3) | | |
| | | |
C13—N2—C14 | 110.83 (12) | C5—C6—H6 | 119.4 |
C13—N2—C20 | 124.96 (13) | O1—C2—N1 | 123.97 (16) |
C14—N2—C20 | 124.17 (13) | O1—C2—C1 | 128.76 (16) |
C7—C8—C1 | 134.09 (14) | N1—C2—C1 | 106.90 (14) |
C7—C8—C3 | 118.27 (15) | C6—C5—H5 | 119.6 |
C3—C8—C1 | 107.24 (13) | C6—C5—C4 | 120.81 (16) |
C19—C12—C13 | 105.09 (13) | C4—C5—H5 | 119.6 |
C1—C12—C13 | 124.30 (13) | C15—C16—C17 | 121.10 (16) |
C1—C12—C19 | 130.57 (14) | C15—C16—H16 | 119.4 |
C3—N1—C9A | 125.81 (17) | C17—C16—H16 | 119.4 |
C3—N1—C9B | 118.8 (3) | C3—C4—C5 | 117.68 (17) |
C2—N1—C3 | 110.97 (14) | C3—C4—H4 | 121.2 |
C2—N1—C9A | 121.83 (17) | C5—C4—H4 | 121.2 |
C2—N1—C9B | 118.6 (3) | C21—C22—H22a | 109.5 |
O2—C13—N2 | 124.85 (14) | C21—C22—H22b | 109.5 |
O2—C13—C12 | 128.34 (14) | C21—C22—H22c | 109.5 |
N2—C13—C12 | 106.67 (12) | H22a—C22—H22b | 109.5 |
C8—C7—H7 | 120.4 | H22a—C22—H22c | 109.5 |
C6—C7—C8 | 119.30 (15) | H22b—C22—H22c | 109.5 |
C6—C7—H7 | 120.4 | H11Aa—C11A—H11Ab | 109.5 |
N2—C14—C19 | 110.04 (13) | H11Aa—C11A—H11Ac | 109.5 |
C15—C14—N2 | 127.60 (15) | H11Ab—C11A—H11Ac | 109.5 |
C15—C14—C19 | 122.36 (15) | C10A—C11A—H11Aa | 109.5 |
C14—C19—C12 | 107.34 (13) | C10A—C11A—H11Ab | 109.5 |
C18—C19—C12 | 133.97 (15) | C10A—C11A—H11Ac | 109.5 |
C18—C19—C14 | 118.42 (14) | N1—C9A—H9Aa | 109.6 |
C8—C1—C2 | 104.98 (13) | N1—C9A—H9Ab | 109.6 |
C12—C1—C8 | 132.45 (14) | N1—C9A—C10A | 110.5 (2) |
C12—C1—C2 | 122.55 (14) | H9Aa—C9A—H9Ab | 108.1 |
N1—C3—C8 | 109.58 (15) | C10A—C9A—H9Aa | 109.6 |
C4—C3—C8 | 122.68 (16) | C10A—C9A—H9Ab | 109.6 |
C4—C3—N1 | 127.72 (16) | C11A—C10A—C9A | 111.5 (3) |
C19—C18—H18 | 120.3 | C11A—C10A—H10Aa | 109.3 |
C17—C18—C19 | 119.41 (16) | C11A—C10A—H10Ab | 109.3 |
C17—C18—H18 | 120.3 | C9A—C10A—H10Aa | 109.3 |
N2—C20—H20a | 109.0 | C9A—C10A—H10Ab | 109.3 |
N2—C20—H20b | 109.0 | H10Aa—C10A—H10Ab | 108.0 |
N2—C20—C21 | 112.80 (13) | N1—C9B—H9Ba | 112.4 |
H20a—C20—H20b | 107.8 | N1—C9B—H9Bb | 112.4 |
C21—C20—H20a | 109.0 | H9Ba—C9B—H9Bb | 110.0 |
C21—C20—H20b | 109.0 | C10B—C9B—N1 | 96.7 (7) |
C14—C15—H15 | 121.1 | C10B—C9B—H9Ba | 112.4 |
C14—C15—C16 | 117.76 (16) | C10B—C9B—H9Bb | 112.4 |
C16—C15—H15 | 121.1 | H11Ba—C11B—H11Bb | 109.5 |
C18—C17—H17 | 119.6 | H11Ba—C11B—H11Bc | 109.5 |
C18—C17—C16 | 120.83 (16) | H11Bb—C11B—H11Bc | 109.5 |
C16—C17—H17 | 119.6 | C10B—C11B—H11Ba | 109.5 |
C20—C21—H21a | 109.3 | C10B—C11B—H11Bb | 109.5 |
C20—C21—H21b | 109.3 | C10B—C11B—H11Bc | 109.5 |
H21a—C21—H21b | 107.9 | C9B—C10B—C11B | 110.9 (9) |
C22—C21—C20 | 111.76 (14) | C9B—C10B—H10Ba | 109.5 |
C22—C21—H21a | 109.3 | C9B—C10B—H10Bb | 109.5 |
C22—C21—H21b | 109.3 | C11B—C10B—H10Ba | 109.5 |
C7—C6—H6 | 119.4 | C11B—C10B—H10Bb | 109.5 |
C5—C6—C7 | 121.25 (16) | H10Ba—C10B—H10Bb | 108.1 |
| | | |
N2—C14—C19—C12 | 0.10 (17) | C19—C18—C17—C16 | 0.0 (3) |
N2—C14—C19—C18 | 174.91 (13) | C1—C8—C7—C6 | 171.43 (16) |
N2—C14—C15—C16 | −176.81 (16) | C1—C8—C3—N1 | 6.02 (19) |
N2—C20—C21—C22 | −168.95 (15) | C1—C8—C3—C4 | −172.98 (17) |
C8—C7—C6—C5 | −0.4 (3) | C1—C12—C13—O2 | 0.5 (3) |
C8—C1—C2—O1 | −171.2 (2) | C1—C12—C13—N2 | 176.38 (14) |
C8—C1—C2—N1 | 1.87 (19) | C1—C12—C19—C14 | −176.90 (15) |
C8—C3—C4—C5 | −0.6 (3) | C1—C12—C19—C18 | 9.4 (3) |
C12—C19—C18—C17 | 176.12 (17) | C3—C8—C7—C6 | −0.3 (2) |
C12—C1—C2—O1 | 7.2 (3) | C3—C8—C1—C12 | 176.99 (16) |
C12—C1—C2—N1 | −179.66 (16) | C3—C8—C1—C2 | −4.75 (17) |
N1—C3—C4—C5 | −179.38 (19) | C3—N1—C2—O1 | 175.3 (2) |
N1—C9A—C10A—C11A | 178.3 (3) | C3—N1—C2—C1 | 1.8 (2) |
N1—C9B—C10B—C11B | −175.5 (10) | C3—N1—C9A—C10A | 99.3 (3) |
C13—N2—C14—C19 | −1.20 (18) | C3—N1—C9B—C10B | −111.3 (6) |
C13—N2—C14—C15 | 177.82 (15) | C18—C17—C16—C15 | −2.2 (3) |
C13—N2—C20—C21 | −103.14 (18) | C20—N2—C13—O2 | −4.4 (2) |
C13—C12—C19—C14 | 0.89 (16) | C20—N2—C13—C12 | 179.61 (14) |
C13—C12—C19—C18 | −172.76 (17) | C20—N2—C14—C19 | −179.12 (14) |
C13—C12—C1—C8 | 22.6 (3) | C20—N2—C14—C15 | −0.1 (3) |
C13—C12—C1—C2 | −155.44 (15) | C15—C14—C19—C12 | −178.97 (14) |
C7—C8—C1—C12 | 4.7 (3) | C15—C14—C19—C18 | −4.2 (2) |
C7—C8—C1—C2 | −177.09 (18) | C6—C5—C4—C3 | −0.2 (3) |
C7—C8—C3—N1 | 179.79 (16) | C2—N1—C3—C8 | −5.0 (2) |
C7—C8—C3—C4 | 0.8 (3) | C2—N1—C3—C4 | 174.0 (2) |
C7—C6—C5—C4 | 0.7 (3) | C2—N1—C9A—C10A | −95.4 (3) |
C14—N2—C13—O2 | 177.74 (15) | C2—N1—C9B—C10B | 108.8 (6) |
C14—N2—C13—C12 | 1.71 (16) | C9A—N1—C3—C8 | 161.66 (19) |
C14—N2—C20—C21 | 74.5 (2) | C9A—N1—C3—C4 | −19.4 (3) |
C14—C19—C18—C17 | 3.0 (2) | C9A—N1—C2—O1 | 8.0 (3) |
C14—C15—C16—C17 | 1.1 (3) | C9A—N1—C2—C1 | −165.48 (18) |
C19—C12—C13—O2 | −177.43 (16) | C9B—N1—C3—C8 | −147.7 (4) |
C19—C12—C13—N2 | −1.59 (15) | C9B—N1—C3—C4 | 31.2 (4) |
C19—C12—C1—C8 | −160.02 (16) | C9B—N1—C2—O1 | −41.9 (5) |
C19—C12—C1—C2 | 22.0 (3) | C9B—N1—C2—C1 | 144.6 (4) |
C19—C14—C15—C16 | 2.1 (2) | | |
Various crystallization conditions and the obtained crystals with different
shape topNo. | Method | Crystallization solvent | Crystallization temperature | Obtained crystal (shape) | No. of samples obtained/tried |
1 | 1 | MeOH | 278 K | A (Plate) | 12/18*, 0/62** |
2 | 2 | CHCl3 / EtOH | 298 K | B (Block) | 1/36 |
3 | 2 | CHCl3 / PE | 298 K | C (Needle) | 48/48 |
4 | 2 | Et2O / MeOH | 298 K | D (Needle) | 3/3 |
5 | 1 | MeOH | 278 K | E (Block) | 29/29 |
Methods 1 and 2 represent the recrystallisation and liquid–vapour diffusion
methods, respectively. Notes: (*) first attempt in run 1; (**) subsequent
attempts for run 1. |
Characteristic torsion angles of Forms I, II and III top | Form I | Form II | Form III |
The orientation of propyl groups | Opposite | Opposite | Same |
N1—C9—C10—C11 | -58.57 | -55.92 | 178.37 (A parts) |
| | | -175.54 (B parts) |
C2—N1—C9—C10 | 106.75 | 108.06 | -95.44 (A parts) |
| | | 108.77 (B parts) |
C3—N1—C9—C10 | -70.86 | -69.29 | 99.34 (A parts) |
| | | -111.30 (B parts) |
N2—C20—C21—C22 | 58.57 | 61.64 | -168.96 |
C13—N2—C20—C21 | -106.75 | -105.43 | -103.13 |
C14—N2—C20—C21 | 70.86 | 74.71 | 74.49 |
Results of lattice energy calculations (kJ mol-1) for Forms I, II and III top | Total energy* | Most stable pair | Second stable pair | Third stable pair |
Form I | -191.7 | -87.6 (22.8%) | -20.4 (5.3%) | - |
Form II | -189.9 | -87.6 (23.1%) | -26.5 (7.0%) | -19.4 (5.1%) |
Form III A parts | -189.0 | -70.1 (18.5%) | -65.6 (17.4%) | -34.2 (9.0%) |
Form III B parts | -180.4 | -69.9 (19.4%) | -65.4 (18.1.%) | -35.5 (9.9%) |
Note: (*) the total energy of all molecular pairs is the sum of the points of
all calculated molecular pairs. Half of the total energy corresponds to the
lattice energy. |