research communications
accessMolecular and of (Z)-N-allyl-3-(allylimino)-3H-isoindol-1-amine
aNational Taras Shevchenko University of Kyiv, Faculty of Chemistry, 64/13, Volodymyrs'ka str., 01601, Kyiv, Ukraine, and bInstitute of Organic Chemistry, NAS of Ukraine, Akademik Kukhar Street 5, Kyiv 02094, Ukraine
*Correspondence e-mail: [email protected]
The 3-imino-3H-isoindol-1-amine tautomeric form of (Z)-N-allyl-3-(allylimino)-3H-isoindol-1-amine, C14H15N3, was confirmed by a single-crystal X-ray diffraction study. The distribution of electron density within the —NH—C=N—C=N— conjugated fragment corresponds to that found in previously studied N,N′-disubstituted 3-imino-3H-isoindol-1-amines. The two molecules in the asymmetric unit of the title compound differ in the conformation of the allyl substituents. In one of these molecules, the two allyl fragments are disordered over two sets of sites in 0.628 (7):0.372 (7) and 0.755 (5):0.245 (5) ratios. In the crystal, the two unique molecules are arranged alternately in infinite chains parallel to [001] due to the formation of intermolecular N—H⋯N hydrogen bonds.
Keywords: crystal structure; 3-imino-3H-isoindol-1-amine derivatives; tautomerism; disorder; hydrogen-bonding.
CCDC reference: 2586660
1. Chemical context
Since the first synthesis and characterisation of 3-imino-3H-isoindole-1-amine and its N,N′-disubstituted derivatives (Elvidge & Linstead, 1952
; Clark et al., 1953
), these compounds have been of interest as important intermediates in the synthesis of phthalocyanines and related compounds. They also exhibit structural features attributable to the presence of the conjugation fragment –NH—C=N–C=N–, in which tautomeric migration of the hydrogen atom between the exo- and endocyclic nitrogen atoms can occur. This is evident from the presence of two tautomeric forms, viz. 3-imino-3H-isoindol-1-amine A and isoindoline-1,3-diimine B (Fig. 1
), which, depending on whether they are in the solid state or in solution, the medium and the substituents on the exocyclic nitrogen atoms, can occur both as the starting compound and as N,N′-disubstituted derivatives (Negrebetskii et al., 1983
; Spiessens & Anteunis, 1984a
; Zhang et al., 2004a
).
| | Figure 1 Zwitterionic and tautomeric forms of compound 1. |
Additionally, the presence of an exocyclic C=N double bond leads to the occurrence of Z/E (Negrebetskii et al., 1983
; Spiessens & Anteunis, 1984b
; Zhang et al., 2004b
). In the solid state and in solution, both in the parent compound and in the N,N′-substituted derivatives, a significant polarization of the C=N bonds is realized, resulting in a significant contribution of the resonance structure C (Fig. 1
; Shishkin et al., 2013
).
A series of N,N′-dialkyl-substituted derivatives were synthesized using Siegl's method from phthalonitrile and primary amines (Siegl, 1977
; Tamgho et al., 2013
). As part of our investigations into N,N′-disubstituted derivatives of 3-imino-3H-isoindol-1-amine, we synthesized the title compound, (Z)-N-allyl-3-(allylimino)-3H-isoindol-1-amine, C14H15N3 (1), by the reaction of 1,1,3-trichloro-1H-isoindole with N-allylamine, and report here its molecular and crystal structure.
2. Structural commentary
Two molecules (1a and 1b) are present in the asymmetric unit (Fig. 2
). Analysis of bond lengths in the –N3H—C8=N1—C1=N2– fragment (Table 1
) revealed that both molecules exist in the tautomeric form A (Fig. 1
) in the crystal. The C1—N2 and N1—C8 bond lengths are close to the mean value of 1.313 Å for Csp2=N(2) bonds (Bürgi & Dunitz, 1994
; the number in brackets indicates the number of bonds formed by the nitrogen atom), while the C1—N1 and C8—N3 bonds are comparable to the mean values of Csp2–N(2) and Csp2–N(3) bonds (1.376 Å and 1.339 Å; Bürgi & Dunitz, 1994
), respectively. Molecules 1a and 1b differ in the conformation of their allyl substituents. In molecule 1b, both allyl groups are arranged nearly orthogonal to the bicyclic fragment (the C1B—N2B—C9B—C10B and C8B—N3B—C12B—C13B torsion angles are −78.5 (3) and 82.1 (3)°). The terminal –Csp2=CH2 groups are rotated around the C9—C10 and C12—C13 single bonds [the N2B—C9B—C10B—C11B and N3B—C12B—C13B—C14B torsion angles are −116.6 (3) and 117.5 (4)°]. In molecule 1a, both allyl groups are disordered over two sets of sites due to rotation around the N2A—C9A or N3A—C12A bonds. The ratio of the conformers a and c for the C9–C10–C11 allyl group is 0.372 (7):0.628 (7), while the ratio of the conformers a and c for the C12–C13–C14 allyl group is 0.755 (5):0.245 (5). In conformer 1a_a, the –Csp2=CH2 group is found in the ap-conformation relative to the C1A—N2A endocyclic bond and the C10=C11 double bond is turned in relation to the N2A—C9A bond [the C1A—N2A—C9A—C10A and N2A—C9A—C10A—C11A torsion angles are 175.7 (7) and −137 (1)°]. In conformer 1a_c, the –Csp2=CH2 fragment is found in the ac-conformation relative to the C1A—N2A endocyclic bond, and its double bond is rotated around the C9C—C10C bond [the C1A—N2A—C9C—C10C and N2A—C9C—C10C—C11C torsion angles are 137.1 (5) and 149.6 (7)°]. The –C13=C14 fragment is arranged orthogonal in the two conformers [1a_a and 1a_c, the C8A—N3A—C12A—C13A and C8A— N3A—C12A—C13C torsion angles are −81.6 (4) and −96.8 (7)°] and the double bond is rotated around the C12A—C13A/C13C bond [the N3A—C12A—C13A—C14A and N3A—C12A—C13C—C14C torsion angles are −14.4 (6) and 142 (2)°].
| ||||||||||||||||||||
| Figure 2 Molecular structure of compound 1 with molecules a and b present in the (top row); displacement ellipsoids are drawn at the 50% probability level. Overlay of molecules 1a_major_component/1b (left) and 1a_minor_component/1b (right); molecule 1b is shown in blue, 1a_major_component in green and 1a_minor_component in red (bottom row). |
3. Supramolecular features
The title compound contains an NH group, which acts as a hydrogen donor, and two nitrogen atoms, N1 and N2, which are capable of acting as hydrogen acceptors. However, one of these potential hydrogen acceptors, the N1 atom, is not available for hydrogen bonding due to the presence of bulky substituents at the neighboring atoms. As a result, only N3—H⋯N2 hydrogen bonds are found in the crystal (Table 2
). These bonds form infinite chains parallel to [001], in which molecules 1a and 1b alternate (Fig. 3
). In addition to the classical N—H⋯N hydrogen bonds, only one weak C10—H⋯π(C6) intermolecular interaction is found in the crystal phase (Table 2
). Despite the presence of an electron-rich bicyclic moiety in the molecule, no stacking interactions are observed in the crystal.
| |||||||||||||||||||||||||||
| | Figure 3 Chains of molecules 1a and 1b extending parallel to [001]. Intermolecular hydrogen bonds N—H⋯N are shown as blue dashed lines. |
4. Database survey
A search of the Cambridge Structure Database (CSD, version 6.00, last update April 2025; Groom et al., 2016
) revealed 40 structures containing the 3-imino-3H-isoindol-1-amine fragment. The N,N′-unsubstituted derivatives of 3-imino-3H-isoindol-1-amine (structures EGAKIK, EGAKOQ (Al-Shewiki et al., 2024
), EXUQAP, EXUQET (Zhang et al., 2004a
), JARFAM (Lo & Ng, 2016
), TIPVEV (Engle et al., 2013
)) proved to be the closest to the compound under study. The distribution of electron density within the –NH–C=N—C=N– fragment is identical in all these structures.
5. Synthesis and crystallization
Compound 1 was synthesized according to a literature procedure (Hordiyenko et al., 2009
, 2022
). 1,1,3-Trichloro-1H-isoindole (1.1 g, 5 mmol) was dissolved in anhydrous dioxane (5 ml), then N-allylamine (1.42 g, 25 mmol) was added dropwise upon stirring and cooling. A red oil formed, then the dioxane was evaporated under reduced pressure and the residual oil was washed with water (2 × 10 ml). After standing for one week in air, the oil crystallized in form of red crystals; yield 1.06 g (95%). Colourless single crystals were obtained by slow evaporation of a methanolic solution of compound 1.
1H NMR spectrum (400 MHz, CDCl3), d, ppm (J, Hz), A form (93%): 4.42 (d, J = 5.2 Hz, 4H, CH2), 5.14 (d, J = 10.0 Hz, 2H, cis-CH=), 5.27 (d, J = 17.2 Hz, 2H, trans-CH=), 6.06 (m, 2H, CH2—CH=), 6.5 (br s, 1H, NH), 7.38 (m, 2H, CHAr), 7.38 (m, 2H, CHAr). 1H NMR spectrum (400 MHz, CDCl3), d, ppm (J, Hz), B form (7%): 4.33 (d, J = 5.2 Hz, 4H, CH2), 7.33 (d, J = 7.6 Hz, 1H, CHAr), 7.45–7.61 (m, 2H, CHAr), 7.83 (d, J = 8.4 Hz, 1H, CHAr).
1H NMR spectrum (400 MHz, DMSO-d6), d, ppm (J, Hz), A form (90%): 4.30 (br s, 4H, CH2), 5.86 (d, J = 10.0 Hz, 2H, cis-CH=), 5.23 (d, J = 16.8 Hz, 2H, trans-CH=), 5.99–6.06 (m, 2H, CH2-CH=), 7.48–7.50 (m, 2H, CHAr), 7.74–7.82 (m, 2H, CHAr). 1H NMR spectrum (400 MHz, CDCl3), d, ppm (J, Hz), B form (10%): 4.22 (br s, 4H, CH2), 5.86 (m, 2H, CH2—CH=), 7.69–7.71 (m, 2H, CHAr), 7.89 (m, 2H, CHAr).
13C NMR spectrum (100 MHz, CDCl3), d, ppm: 49.5 (CH2), 116.7, 117.6, 120.7, 121.9, 125.7, 129.4, 130.3, 135.0, 137.4, 167.1.
LC-MS: RT (min), m/z (%) = 0.951, 226.2 [68%, (M + H)+]; 1.019, 226.2 [21%, (M + H)+]. The presence of two independent peaks at m/z 226 but different retention times may be considered as a presence of two tautomeric forms A/B in a 3:1 ratio in solution during LS-MS analysis (RP C18, of solvent H2O/CH3CN:1/99 to H2O/CH3CN:0/100, 0.1% formic acid). The 1H NMR spectra of compound 1 in CDCl3 and DMSO-d6 revealed two sets of resonances at room temperature corresponding to the A and B tautomers in a 90:10 ratio.
6. Refinement
Crystal data, data collection and structure details are summarized in Table 3
. Hydrogen atoms were placed at calculated positions and refined as riding with Uiso(H) = 1.2Ueq(C/N). The site occupation factors of the disordered allyl groups of molecule A were refined as 0.628 (7):0.372 (7) and 0.755 (5):0.245 (5). The restrictions on the bonds lengths in the disordered fragments were applied as Csp2—Csp3 = 1.510 (2) Å, N(2)—Csp3 = 1.470 (2) Å, Csp2=Csp2 = 1.340 (2) Å.
|
Supporting information
CCDC reference: 2586660
contains datablock I. DOI: https://doi.org/10.1107/S2056989026009448/wm5805sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989026009448/wm5805Isup3.hkl
| C14H15N3 | Z = 4 |
| Mr = 225.29 | F(000) = 480 |
| Triclinic, P1 | Dx = 1.177 Mg m−3 |
| a = 9.2429 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 11.1785 (8) Å | Cell parameters from 3958 reflections |
| c = 13.8791 (11) Å | θ = 3.1–32.5° |
| α = 73.461 (7)° | µ = 0.07 mm−1 |
| β = 87.231 (6)° | T = 293 K |
| γ = 67.950 (6)° | Bar, colourless |
| V = 1271.36 (17) Å3 | 0.27 × 0.23 × 0.12 mm |
| Xcalibur, Sapphire3 diffractometer | 4463 independent reflections |
| Radiation source: Enhance (Mo) X-ray Source | 2711 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.024 |
| Detector resolution: 16.1827 pixels mm-1 | θmax = 25.0°, θmin = 3.1° |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2024) | k = −13→13 |
| Tmin = 0.806, Tmax = 1.000 | l = −16→14 |
| 9706 measured reflections |
| Refinement on F2 | 118 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
| wR(F2) = 0.190 | w = 1/[σ2(Fo2) + (0.1125P)2 + 0.0092P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 4463 reflections | Δρmax = 0.32 e Å−3 |
| 324 parameters | Δρmin = −0.25 e Å−3 |
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. |
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 > 2σ(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 | Occ. (<1) | |
| C1A | 0.8690 (3) | 0.2668 (3) | 0.87377 (17) | 0.0533 (6) | |
| C2A | 1.0230 (3) | 0.1639 (3) | 0.92144 (17) | 0.0498 (6) | |
| C3A | 1.1469 (3) | 0.0757 (3) | 0.8868 (2) | 0.0654 (7) | |
| H3A | 1.145361 | 0.072323 | 0.820719 | 0.078* | |
| C4A | 1.2744 (3) | −0.0079 (3) | 0.9542 (2) | 0.0761 (8) | |
| H4A | 1.360437 | −0.067995 | 0.932452 | 0.091* | |
| C5A | 1.2771 (3) | −0.0045 (3) | 1.0520 (2) | 0.0761 (8) | |
| H5A | 1.364199 | −0.062658 | 1.095489 | 0.091* | |
| C6A | 1.1526 (3) | 0.0840 (3) | 1.08696 (19) | 0.0625 (7) | |
| H6A | 1.154191 | 0.086940 | 1.153171 | 0.075* | |
| C7A | 1.0260 (3) | 0.1675 (2) | 1.02036 (16) | 0.0498 (6) | |
| C8A | 0.8735 (3) | 0.2710 (3) | 1.02921 (16) | 0.0501 (6) | |
| C9A | 0.6704 (11) | 0.4090 (15) | 0.7545 (8) | 0.0947 (15) | 0.372 (7) |
| H9AA | 0.673228 | 0.485475 | 0.773082 | 0.114* | 0.372 (7) |
| H9AB | 0.592084 | 0.380871 | 0.792578 | 0.114* | 0.372 (7) |
| C9C | 0.6654 (5) | 0.3983 (8) | 0.7465 (6) | 0.0947 (15) | 0.628 (7) |
| H9CA | 0.626343 | 0.445630 | 0.796838 | 0.114* | 0.628 (7) |
| H9CB | 0.597534 | 0.351483 | 0.741757 | 0.114* | 0.628 (7) |
| C10A | 0.6249 (14) | 0.4511 (9) | 0.6435 (8) | 0.0758 (15) | 0.372 (7) |
| H10A | 0.639887 | 0.390099 | 0.606722 | 0.091* | 0.372 (7) |
| C10C | 0.6553 (7) | 0.5003 (8) | 0.6464 (4) | 0.0758 (15) | 0.628 (7) |
| H10C | 0.738294 | 0.527023 | 0.625014 | 0.091* | 0.628 (7) |
| C11A | 0.561 (2) | 0.5848 (9) | 0.6032 (16) | 0.118 (2) | 0.372 (7) |
| H11A | 0.548419 | 0.641511 | 0.643313 | 0.142* | 0.372 (7) |
| H11B | 0.528734 | 0.621055 | 0.535090 | 0.142* | 0.372 (7) |
| C11C | 0.5214 (10) | 0.5504 (9) | 0.5897 (8) | 0.118 (2) | 0.628 (7) |
| H11C | 0.440144 | 0.521994 | 0.612675 | 0.142* | 0.628 (7) |
| H11D | 0.509519 | 0.613615 | 0.527226 | 0.142* | 0.628 (7) |
| C12A | 0.6832 (3) | 0.4077 (3) | 1.1195 (2) | 0.0706 (8) | |
| H12A | 0.657782 | 0.388953 | 1.189409 | 0.085* | 0.755 (5) |
| H12B | 0.604924 | 0.397485 | 1.081890 | 0.085* | 0.755 (5) |
| H12C | 0.640908 | 0.385769 | 1.184547 | 0.085* | 0.245 (5) |
| H12D | 0.607482 | 0.423377 | 1.066716 | 0.085* | 0.245 (5) |
| C13A | 0.6637 (5) | 0.5536 (3) | 1.0836 (4) | 0.0832 (13) | 0.755 (5) |
| H13A | 0.563932 | 0.620544 | 1.073333 | 0.100* | 0.755 (5) |
| C13C | 0.7305 (18) | 0.5270 (9) | 1.1046 (15) | 0.0832 (13) | 0.245 (5) |
| H13C | 0.828096 | 0.501113 | 1.136619 | 0.100* | 0.245 (5) |
| C14A | 0.7880 (6) | 0.5875 (6) | 1.0664 (4) | 0.1021 (16) | 0.755 (5) |
| H14A | 0.887964 | 0.520776 | 1.076508 | 0.123* | 0.755 (5) |
| H14B | 0.774927 | 0.677829 | 1.044197 | 0.123* | 0.755 (5) |
| C14C | 0.671 (2) | 0.6595 (10) | 1.0582 (12) | 0.1021 (16) | 0.245 (5) |
| H14C | 0.573313 | 0.698699 | 1.023136 | 0.123* | 0.245 (5) |
| H14D | 0.726839 | 0.712478 | 1.060940 | 0.123* | 0.245 (5) |
| N1A | 0.7836 (2) | 0.3261 (2) | 0.94508 (13) | 0.0565 (6) | |
| N2A | 0.8244 (2) | 0.2976 (2) | 0.78095 (15) | 0.0697 (7) | |
| N3A | 0.8308 (2) | 0.3045 (2) | 1.11342 (14) | 0.0602 (6) | |
| H3AA | 0.893866 | 0.262979 | 1.166402 | 0.072* | |
| C1B | 0.9921 (3) | 0.7527 (2) | 0.62943 (17) | 0.0500 (6) | |
| C2B | 1.1034 (3) | 0.8152 (2) | 0.58141 (17) | 0.0504 (6) | |
| C3B | 1.1871 (3) | 0.8759 (3) | 0.6156 (2) | 0.0641 (7) | |
| H3B | 1.182357 | 0.881374 | 0.681332 | 0.077* | |
| C4B | 1.2780 (3) | 0.9283 (3) | 0.5487 (2) | 0.0741 (8) | |
| H4B | 1.335851 | 0.969657 | 0.569866 | 0.089* | |
| C5B | 1.2853 (3) | 0.9209 (3) | 0.4514 (2) | 0.0777 (9) | |
| H5B | 1.348551 | 0.956736 | 0.408388 | 0.093* | |
| C6B | 1.2003 (3) | 0.8612 (3) | 0.4158 (2) | 0.0658 (7) | |
| H6B | 1.203870 | 0.857206 | 0.349727 | 0.079* | |
| C7B | 1.1099 (3) | 0.8079 (2) | 0.48381 (17) | 0.0517 (6) | |
| C8B | 1.0025 (3) | 0.7416 (2) | 0.47508 (16) | 0.0502 (6) | |
| C9B | 0.8490 (3) | 0.6725 (3) | 0.75785 (19) | 0.0697 (8) | |
| H9BA | 0.860705 | 0.640276 | 0.830822 | 0.084* | |
| H9BB | 0.873532 | 0.595217 | 0.732486 | 0.084* | |
| C10B | 0.6827 (3) | 0.7664 (3) | 0.7253 (2) | 0.0769 (9) | |
| H10B | 0.655008 | 0.799253 | 0.656490 | 0.092* | |
| C11B | 0.5723 (4) | 0.8062 (4) | 0.7867 (2) | 0.1039 (12) | |
| H11E | 0.595419 | 0.775551 | 0.855943 | 0.125* | |
| H11F | 0.471758 | 0.864697 | 0.760468 | 0.125* | |
| C12B | 0.8705 (3) | 0.6500 (3) | 0.3842 (2) | 0.0742 (8) | |
| H12E | 0.880430 | 0.579368 | 0.446271 | 0.089* | |
| H12F | 0.898313 | 0.608766 | 0.329684 | 0.089* | |
| C13B | 0.7045 (3) | 0.7495 (3) | 0.3651 (2) | 0.0847 (9) | |
| H13B | 0.663717 | 0.791653 | 0.414733 | 0.102* | |
| C14B | 0.6106 (5) | 0.7831 (5) | 0.2852 (2) | 0.1256 (16) | |
| H14E | 0.645866 | 0.743682 | 0.233435 | 0.151* | |
| H14F | 0.509075 | 0.846147 | 0.280447 | 0.151* | |
| N1B | 0.9340 (2) | 0.7106 (2) | 0.55896 (14) | 0.0522 (5) | |
| N2B | 0.9588 (2) | 0.7386 (2) | 0.72120 (14) | 0.0602 (6) | |
| N3B | 0.9767 (2) | 0.7162 (2) | 0.39151 (15) | 0.0627 (6) | |
| H3BA | 1.024627 | 0.739824 | 0.339276 | 0.075* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1A | 0.0485 (13) | 0.0702 (17) | 0.0390 (12) | −0.0187 (12) | 0.0054 (9) | −0.0179 (11) |
| C2A | 0.0461 (13) | 0.0585 (15) | 0.0442 (12) | −0.0187 (11) | 0.0069 (9) | −0.0162 (10) |
| C3A | 0.0592 (16) | 0.0738 (19) | 0.0588 (15) | −0.0158 (14) | 0.0124 (12) | −0.0265 (13) |
| C4A | 0.0556 (16) | 0.075 (2) | 0.0812 (19) | −0.0059 (15) | 0.0107 (13) | −0.0251 (15) |
| C5A | 0.0551 (16) | 0.082 (2) | 0.0680 (17) | −0.0090 (15) | −0.0064 (13) | −0.0085 (15) |
| C6A | 0.0588 (15) | 0.0705 (18) | 0.0499 (14) | −0.0187 (14) | −0.0028 (11) | −0.0117 (12) |
| C7A | 0.0487 (13) | 0.0586 (15) | 0.0434 (12) | −0.0224 (12) | 0.0049 (9) | −0.0139 (10) |
| C8A | 0.0521 (13) | 0.0601 (15) | 0.0383 (12) | −0.0211 (12) | 0.0053 (10) | −0.0151 (10) |
| C9A | 0.0527 (16) | 0.164 (4) | 0.0454 (17) | −0.0086 (19) | −0.0001 (12) | −0.0402 (18) |
| C9C | 0.0527 (16) | 0.164 (4) | 0.0454 (17) | −0.0086 (19) | −0.0001 (12) | −0.0402 (18) |
| C10A | 0.068 (3) | 0.076 (4) | 0.082 (2) | −0.017 (3) | −0.011 (2) | −0.033 (3) |
| C10C | 0.068 (3) | 0.076 (4) | 0.082 (2) | −0.017 (3) | −0.011 (2) | −0.033 (3) |
| C11A | 0.133 (6) | 0.092 (4) | 0.107 (4) | −0.028 (4) | −0.048 (3) | −0.007 (4) |
| C11C | 0.133 (6) | 0.092 (4) | 0.107 (4) | −0.028 (4) | −0.048 (3) | −0.007 (4) |
| C12A | 0.0700 (18) | 0.0767 (18) | 0.0576 (16) | −0.0169 (15) | 0.0222 (13) | −0.0260 (14) |
| C13A | 0.081 (4) | 0.075 (2) | 0.074 (3) | −0.013 (2) | 0.005 (3) | −0.017 (2) |
| C13C | 0.081 (4) | 0.075 (2) | 0.074 (3) | −0.013 (2) | 0.005 (3) | −0.017 (2) |
| C14A | 0.103 (4) | 0.081 (3) | 0.111 (3) | −0.034 (3) | 0.002 (3) | −0.011 (3) |
| C14C | 0.103 (4) | 0.081 (3) | 0.111 (3) | −0.034 (3) | 0.002 (3) | −0.011 (3) |
| N1A | 0.0505 (11) | 0.0710 (14) | 0.0400 (11) | −0.0123 (11) | 0.0047 (8) | −0.0187 (10) |
| N2A | 0.0534 (12) | 0.1011 (18) | 0.0439 (12) | −0.0137 (12) | 0.0035 (9) | −0.0261 (11) |
| N3A | 0.0615 (13) | 0.0763 (15) | 0.0399 (11) | −0.0198 (12) | 0.0053 (9) | −0.0211 (10) |
| C1B | 0.0462 (13) | 0.0520 (14) | 0.0451 (12) | −0.0106 (11) | 0.0013 (10) | −0.0146 (10) |
| C2B | 0.0408 (13) | 0.0518 (15) | 0.0506 (13) | −0.0087 (11) | −0.0001 (10) | −0.0145 (11) |
| C3B | 0.0553 (16) | 0.0673 (18) | 0.0704 (17) | −0.0195 (14) | 0.0000 (12) | −0.0251 (14) |
| C4B | 0.0521 (16) | 0.0679 (19) | 0.102 (2) | −0.0213 (15) | 0.0017 (15) | −0.0256 (17) |
| C5B | 0.0523 (16) | 0.073 (2) | 0.092 (2) | −0.0205 (15) | 0.0135 (14) | −0.0051 (16) |
| C6B | 0.0507 (15) | 0.0722 (19) | 0.0605 (15) | −0.0140 (14) | 0.0114 (12) | −0.0120 (13) |
| C7B | 0.0383 (12) | 0.0535 (15) | 0.0501 (13) | −0.0054 (11) | 0.0016 (9) | −0.0113 (11) |
| C8B | 0.0426 (13) | 0.0551 (15) | 0.0430 (12) | −0.0060 (11) | 0.0012 (10) | −0.0161 (11) |
| C9B | 0.0729 (17) | 0.085 (2) | 0.0475 (14) | −0.0314 (16) | 0.0082 (12) | −0.0114 (13) |
| C10B | 0.0752 (18) | 0.095 (2) | 0.0640 (17) | −0.0407 (18) | 0.0056 (14) | −0.0159 (15) |
| C11B | 0.082 (2) | 0.143 (4) | 0.083 (2) | −0.034 (2) | 0.0184 (18) | −0.041 (2) |
| C12B | 0.0806 (19) | 0.078 (2) | 0.0699 (18) | −0.0240 (16) | 0.0003 (14) | −0.0380 (15) |
| C13B | 0.0755 (19) | 0.103 (3) | 0.085 (2) | −0.0395 (19) | 0.0081 (16) | −0.0331 (19) |
| C14B | 0.093 (3) | 0.179 (5) | 0.097 (3) | −0.047 (3) | −0.007 (2) | −0.030 (3) |
| N1B | 0.0524 (12) | 0.0598 (13) | 0.0439 (10) | −0.0181 (10) | 0.0036 (8) | −0.0182 (9) |
| N2B | 0.0567 (13) | 0.0809 (16) | 0.0404 (11) | −0.0228 (12) | 0.0039 (9) | −0.0183 (10) |
| N3B | 0.0572 (13) | 0.0813 (16) | 0.0474 (12) | −0.0194 (12) | 0.0056 (9) | −0.0252 (11) |
| C1A—C2A | 1.488 (3) | C13C—H13C | 0.9300 |
| C1A—N1A | 1.396 (3) | C13C—C14C | 1.339 (2) |
| C1A—N2A | 1.281 (3) | C14A—H14A | 0.9300 |
| C2A—C3A | 1.372 (4) | C14A—H14B | 0.9300 |
| C2A—C7A | 1.387 (3) | C14C—H14C | 0.9300 |
| C3A—H3A | 0.9300 | C14C—H14D | 0.9300 |
| C3A—C4A | 1.385 (4) | N3A—H3AA | 0.8600 |
| C4A—H4A | 0.9300 | C1B—C2B | 1.483 (3) |
| C4A—C5A | 1.372 (4) | C1B—N1B | 1.403 (3) |
| C5A—H5A | 0.9300 | C1B—N2B | 1.275 (3) |
| C5A—C6A | 1.379 (4) | C2B—C3B | 1.377 (4) |
| C6A—H6A | 0.9300 | C2B—C7B | 1.377 (3) |
| C6A—C7A | 1.374 (3) | C3B—H3B | 0.9300 |
| C7A—C8A | 1.476 (4) | C3B—C4B | 1.377 (4) |
| C8A—N1A | 1.317 (3) | C4B—H4B | 0.9300 |
| C8A—N3A | 1.325 (3) | C4B—C5B | 1.373 (4) |
| C9A—H9AA | 0.9700 | C5B—H5B | 0.9300 |
| C9A—H9AB | 0.9700 | C5B—C6B | 1.386 (4) |
| C9A—C10A | 1.508 (2) | C6B—H6B | 0.9300 |
| C9A—N2A | 1.473 (2) | C6B—C7B | 1.386 (3) |
| C9C—H9CA | 0.9700 | C7B—C8B | 1.472 (3) |
| C9C—H9CB | 0.9700 | C8B—N1B | 1.319 (3) |
| C9C—C10C | 1.507 (2) | C8B—N3B | 1.322 (3) |
| C9C—N2A | 1.475 (2) | C9B—H9BA | 0.9700 |
| C10A—H10A | 0.9300 | C9B—H9BB | 0.9700 |
| C10A—C11A | 1.338 (2) | C9B—C10B | 1.5012 (19) |
| C10C—H10C | 0.9300 | C9B—N2B | 1.460 (3) |
| C10C—C11C | 1.337 (2) | C10B—H10B | 0.9300 |
| C11A—H11A | 0.9300 | C10B—C11B | 1.3254 (19) |
| C11A—H11B | 0.9300 | C11B—H11E | 0.9300 |
| C11C—H11C | 0.9300 | C11B—H11F | 0.9300 |
| C11C—H11D | 0.9300 | C12B—H12E | 0.9700 |
| C12A—H12A | 0.9700 | C12B—H12F | 0.9700 |
| C12A—H12B | 0.9700 | C12B—C13B | 1.5006 (19) |
| C12A—H12C | 0.9700 | C12B—N3B | 1.456 (3) |
| C12A—H12D | 0.9700 | C13B—H13B | 0.9300 |
| C12A—C13A | 1.505 (2) | C13B—C14B | 1.3178 (19) |
| C12A—C13C | 1.511 (2) | C14B—H14E | 0.9300 |
| C12A—N3A | 1.436 (3) | C14B—H14F | 0.9300 |
| C13A—H13A | 0.9300 | N3B—H3BA | 0.8600 |
| C13A—C14A | 1.330 (2) | ||
| N1A—C1A—C2A | 109.48 (19) | C13A—C14A—H14A | 120.0 |
| N2A—C1A—C2A | 124.8 (2) | C13A—C14A—H14B | 120.0 |
| N2A—C1A—N1A | 125.7 (2) | H14A—C14A—H14B | 120.0 |
| C3A—C2A—C1A | 133.3 (2) | C13C—C14C—H14C | 120.0 |
| C3A—C2A—C7A | 120.8 (2) | C13C—C14C—H14D | 120.0 |
| C7A—C2A—C1A | 105.9 (2) | H14C—C14C—H14D | 120.0 |
| C2A—C3A—H3A | 121.3 | C8A—N1A—C1A | 106.5 (2) |
| C2A—C3A—C4A | 117.4 (3) | C1A—N2A—C9A | 112.3 (5) |
| C4A—C3A—H3A | 121.3 | C1A—N2A—C9C | 118.0 (4) |
| C3A—C4A—H4A | 119.1 | C8A—N3A—C12A | 122.4 (2) |
| C5A—C4A—C3A | 121.7 (3) | C8A—N3A—H3AA | 118.8 |
| C5A—C4A—H4A | 119.1 | C12A—N3A—H3AA | 118.8 |
| C4A—C5A—H5A | 119.5 | N1B—C1B—C2B | 109.3 (2) |
| C4A—C5A—C6A | 121.0 (3) | N2B—C1B—C2B | 124.1 (2) |
| C6A—C5A—H5A | 119.5 | N2B—C1B—N1B | 126.5 (2) |
| C5A—C6A—H6A | 121.2 | C3B—C2B—C1B | 132.6 (2) |
| C7A—C6A—C5A | 117.6 (3) | C7B—C2B—C1B | 106.2 (2) |
| C7A—C6A—H6A | 121.2 | C7B—C2B—C3B | 121.2 (2) |
| C2A—C7A—C8A | 104.9 (2) | C2B—C3B—H3B | 121.2 |
| C6A—C7A—C2A | 121.5 (2) | C4B—C3B—C2B | 117.5 (3) |
| C6A—C7A—C8A | 133.6 (2) | C4B—C3B—H3B | 121.2 |
| N1A—C8A—C7A | 113.2 (2) | C3B—C4B—H4B | 119.2 |
| N1A—C8A—N3A | 123.3 (2) | C5B—C4B—C3B | 121.6 (3) |
| N3A—C8A—C7A | 123.5 (2) | C5B—C4B—H4B | 119.2 |
| H9AA—C9A—H9AB | 108.0 | C4B—C5B—H5B | 119.3 |
| C10A—C9A—H9AA | 109.3 | C4B—C5B—C6B | 121.5 (3) |
| C10A—C9A—H9AB | 109.3 | C6B—C5B—H5B | 119.3 |
| N2A—C9A—H9AA | 109.3 | C5B—C6B—H6B | 121.7 |
| N2A—C9A—H9AB | 109.3 | C7B—C6B—C5B | 116.7 (3) |
| N2A—C9A—C10A | 111.6 (6) | C7B—C6B—H6B | 121.7 |
| H9CA—C9C—H9CB | 107.6 | C2B—C7B—C6B | 121.6 (2) |
| C10C—C9C—H9CA | 108.7 | C2B—C7B—C8B | 105.2 (2) |
| C10C—C9C—H9CB | 108.7 | C6B—C7B—C8B | 133.1 (2) |
| N2A—C9C—H9CA | 108.7 | N1B—C8B—C7B | 113.1 (2) |
| N2A—C9C—H9CB | 108.7 | N1B—C8B—N3B | 123.4 (2) |
| N2A—C9C—C10C | 114.3 (5) | N3B—C8B—C7B | 123.4 (2) |
| C9A—C10A—H10A | 123.3 | H9BA—C9B—H9BB | 107.9 |
| C11A—C10A—C9A | 113.3 (14) | C10B—C9B—H9BA | 109.3 |
| C11A—C10A—H10A | 123.3 | C10B—C9B—H9BB | 109.3 |
| C9C—C10C—H10C | 121.6 | N2B—C9B—H9BA | 109.3 |
| C11C—C10C—C9C | 116.8 (7) | N2B—C9B—H9BB | 109.3 |
| C11C—C10C—H10C | 121.6 | N2B—C9B—C10B | 111.7 (2) |
| C10A—C11A—H11A | 120.0 | C9B—C10B—H10B | 117.4 |
| C10A—C11A—H11B | 120.0 | C11B—C10B—C9B | 125.2 (3) |
| H11A—C11A—H11B | 120.0 | C11B—C10B—H10B | 117.4 |
| C10C—C11C—H11C | 120.0 | C10B—C11B—H11E | 120.0 |
| C10C—C11C—H11D | 120.0 | C10B—C11B—H11F | 120.0 |
| H11C—C11C—H11D | 120.0 | H11E—C11B—H11F | 120.0 |
| H12A—C12A—H12B | 106.9 | H12E—C12B—H12F | 108.1 |
| H12C—C12A—H12D | 109.4 | C13B—C12B—H12E | 109.5 |
| C13A—C12A—H12A | 107.3 | C13B—C12B—H12F | 109.5 |
| C13A—C12A—H12B | 107.3 | N3B—C12B—H12E | 109.5 |
| C13C—C12A—H12C | 111.6 | N3B—C12B—H12F | 109.5 |
| C13C—C12A—H12D | 111.6 | N3B—C12B—C13B | 110.7 (2) |
| N3A—C12A—H12A | 107.3 | C12B—C13B—H13B | 116.7 |
| N3A—C12A—H12B | 107.3 | C14B—C13B—C12B | 126.5 (3) |
| N3A—C12A—H12C | 111.6 | C14B—C13B—H13B | 116.7 |
| N3A—C12A—H12D | 111.6 | C13B—C14B—H14E | 120.0 |
| N3A—C12A—C13A | 120.0 (3) | C13B—C14B—H14F | 120.0 |
| N3A—C12A—C13C | 100.9 (7) | H14E—C14B—H14F | 120.0 |
| C12A—C13A—H13A | 119.7 | C8B—N1B—C1B | 106.1 (2) |
| C14A—C13A—C12A | 120.5 (4) | C1B—N2B—C9B | 117.6 (2) |
| C14A—C13A—H13A | 119.7 | C8B—N3B—C12B | 122.8 (2) |
| C12A—C13C—H13C | 111.2 | C8B—N3B—H3BA | 118.6 |
| C14C—C13C—C12A | 137.6 (13) | C12B—N3B—H3BA | 118.6 |
| C14C—C13C—H13C | 111.2 | ||
| C1A—C2A—C3A—C4A | −179.8 (3) | N3A—C8A—N1A—C1A | 179.2 (2) |
| C1A—C2A—C7A—C6A | 179.7 (2) | N3A—C12A—C13A—C14A | −14.3 (7) |
| C1A—C2A—C7A—C8A | 0.7 (2) | N3A—C12A—C13C—C14C | 142 (2) |
| C2A—C1A—N1A—C8A | 1.6 (3) | C1B—C2B—C3B—C4B | −177.9 (2) |
| C2A—C1A—N2A—C9A | −176.4 (9) | C1B—C2B—C7B—C6B | 178.1 (2) |
| C2A—C1A—N2A—C9C | 177.6 (5) | C1B—C2B—C7B—C8B | 0.1 (2) |
| C2A—C3A—C4A—C5A | 0.6 (4) | C2B—C1B—N1B—C8B | 0.7 (3) |
| C2A—C7A—C8A—N1A | 0.3 (3) | C2B—C1B—N2B—C9B | −178.8 (2) |
| C2A—C7A—C8A—N3A | 179.9 (2) | C2B—C3B—C4B—C5B | 0.2 (4) |
| C3A—C2A—C7A—C6A | 0.2 (4) | C2B—C7B—C8B—N1B | 0.4 (3) |
| C3A—C2A—C7A—C8A | −178.8 (2) | C2B—C7B—C8B—N3B | −180.0 (2) |
| C3A—C4A—C5A—C6A | −0.6 (5) | C3B—C2B—C7B—C6B | −0.1 (4) |
| C4A—C5A—C6A—C7A | 0.4 (4) | C3B—C2B—C7B—C8B | −178.0 (2) |
| C5A—C6A—C7A—C2A | −0.2 (4) | C3B—C4B—C5B—C6B | 0.5 (4) |
| C5A—C6A—C7A—C8A | 178.6 (3) | C4B—C5B—C6B—C7B | −0.9 (4) |
| C6A—C7A—C8A—N1A | −178.6 (2) | C5B—C6B—C7B—C2B | 0.7 (4) |
| C6A—C7A—C8A—N3A | 1.1 (4) | C5B—C6B—C7B—C8B | 178.0 (3) |
| C7A—C2A—C3A—C4A | −0.5 (4) | C6B—C7B—C8B—N1B | −177.3 (3) |
| C7A—C8A—N1A—C1A | −1.2 (3) | C6B—C7B—C8B—N3B | 2.4 (4) |
| C7A—C8A—N3A—C12A | 178.5 (2) | C7B—C2B—C3B—C4B | −0.4 (4) |
| C10A—C9A—N2A—C1A | 175.7 (11) | C7B—C8B—N1B—C1B | −0.7 (3) |
| C10C—C9C—N2A—C1A | 137.2 (6) | C7B—C8B—N3B—C12B | 179.8 (2) |
| C13A—C12A—N3A—C8A | −81.7 (4) | C10B—C9B—N2B—C1B | −78.5 (3) |
| C13C—C12A—N3A—C8A | −96.9 (8) | C13B—C12B—N3B—C8B | 82.1 (3) |
| N1A—C1A—C2A—C3A | 178.0 (3) | N1B—C1B—C2B—C3B | 177.3 (3) |
| N1A—C1A—C2A—C7A | −1.4 (3) | N1B—C1B—C2B—C7B | −0.5 (3) |
| N1A—C1A—N2A—C9A | 1.8 (9) | N1B—C1B—N2B—C9B | −0.1 (4) |
| N1A—C1A—N2A—C9C | −4.2 (6) | N1B—C8B—N3B—C12B | −0.6 (4) |
| N1A—C8A—N3A—C12A | −1.9 (4) | N2B—C1B—C2B—C3B | −3.8 (4) |
| N2A—C1A—C2A—C3A | −3.6 (5) | N2B—C1B—C2B—C7B | 178.4 (2) |
| N2A—C1A—C2A—C7A | 177.0 (2) | N2B—C1B—N1B—C8B | −178.2 (2) |
| N2A—C1A—N1A—C8A | −176.8 (2) | N2B—C9B—C10B—C11B | −116.7 (4) |
| N2A—C9A—C10A—C11A | −137.5 (15) | N3B—C8B—N1B—C1B | 179.7 (2) |
| N2A—C9C—C10C—C11C | 149.7 (9) | N3B—C12B—C13B—C14B | 117.5 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10A—H10A···C6Bi | 0.93 | 2.74 | 3.571 (12) | 149 |
| N3A—H3AA···N2Bii | 0.86 | 2.11 | 2.895 (3) | 151 |
| N3B—H3BA···N2Ai | 0.86 | 2.15 | 2.951 (3) | 154 |
| Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z+2. |
| Bond | Molecule 1a | Molecule 1b |
| C1—N2 | 1.281 (3) | 1.275 (3) |
| C1—N1 | 1.395 (3) | 1.403 (4) |
| N1—C8 | 1.317 (3) | 1.319 (3) |
| C8—N3 | 1.325 (3) | 1.322 (3) |
Acknowledgements
The authors are grateful to the FAIRE programme provided by the Cambridge Crystallographic Data Centre (CCDC) for the opportunity to use the Cambridge Structural Database (CSD) and associated software.
References
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