supplementary materials


im2276 scheme

Acta Cryst. (2011). E67, o1165-o1166    [ doi:10.1107/S1600536811013286 ]

2-{(E)-N-[2-(1H-Inden-3-yl)ethyl]iminomethyl}-1H-imidazole

Z. Li, C. Tian, W. Nie and M. V. Borzov

Abstract top

The asymmetric unit of the title compound, C15H15N3, contains two crystallographically independent molecules with very similar geometries. The imidazole and indenyl planes are approximately orthogonal, making dihedral angles of 88.21 (9) and 83.08 (9)%deg; in the two independent molecules. In the crystal, the imidazole units are linked by N-H...N hydrogen bonds into chains parallel to the 101) plane stretched in the diagonal direction [translation vector (\overline{1},1,0); C(4) motif]. Within a chain, there are two types of symmetrically non-equivalent alternating H-bonds which slightly differ in their parameters.

Comment top

1H-Imidazol(in)-2-yl side-chain functionalized cyclopentadiene-type (Cp) ligands were introduced into the organometallic chemistry, and, particularly into that of the Group 4 transition metals, not long ago (Krut'ko et al., 2006; Nie et al., 2008; Wang et al., 2009; Sun et al., 2009; Sun et al., 2010; Ge et al., 2010). All these compounds are usually considered to be prospective precursors for catalytic systems capable to effectively polymerize ethylene and α-olefins. However, in all of these previously reported ligands, the Cp- and imidazol-2-yl groups are linked by a C1– or C2-hydrocarbon bridge. Incorporating into the bridge another heteroatom groups capable of coordination towards a metal centre presents, this way, a logical step forward in the ligand design development. This contribution reports the first structural characterization of a potent tridentate ligand of the type where Cp- (1H-inden-3-yl) and 1H-imidazol-2-yl groups are connected with a bridge with a CN imino-function.

The achiral title compound, C15H15N3, I, was prepared by a condensation reaction of 2-(1H-inden-3-yl)ethanamine and 1H-imidazol-2-carbaldehyde. It crystallizes in a chiral space group P212121, with the c-axis of the lattice being very long comparatively to the others [51.909 (4) Å]. The asymmetric unit of I is presented by two crystallographically independent molecules with very close geometries (see Fig. 1). Imidazole moieties of the asymmetric unit are linked by NH···N hydrogen bonds and the units assemble in chains parallel to a0b plane stretched in the diagonal direction [translation vector (–1,1,0); C(4) motif; see Fig. 2]. Within a chain, these hydrogen bonds slightly alternate (see Table).

Both indenyl groups are planar within 0.03 Å and nearly parallel one to each other [interplane angle 1.44 (6)°]. Within the independent molecules, the imidazole and indenyl r. m. s. planes are approximately orthogonal [interplane angles 88.21 (9) and 96.92 (9)°]. However, the imidazole rings in the units form a noticible interplane angle [7.43 (11)°] what could be a result of their mutual hydrogen binding. The same binding could also be a reason of noticible twisting of the CN fragments in respect to the imidazole ring planes [torsion angles 7.5 (4) and 7.3 (4)°].

Analysis of the Cambridge Structural database [CSD; Version 5.27, release May 2009; Allen, 2002; 317 entries, 483 fragments] reveals that the observed C N distances in I [1.251 (4) and 1.253 (4) Å] are close to the median value for CN bond in Schiff bases derived from primary aliphatic amines and aromatic (and/or heteroaromatic) aldehydes (1.27 Å). As for the 1H-inden-3-yl and 1H-imidazol-2-yl groups, all the bond lengths and angles are within normal ranges (for references, see Related literature section).

Related literature top

For the structural parameters of 3-organyl substituted 1H-indenes (organic structures only), see: Sun et al. (2010) and references cited therein. For the structural parameters of 2-organyl-1H-imidazoles (organic structures only, not bi- or oligocyclic, non-ionic, recent publications only), see: Lassalle-Kaiser et al. (2006). For the structural parameters of Li, Ti, and Zr complexes derived from 1H-imidazol(in)-2-yl side-chain-functionalized cyclopentadienes see: Krut'ko et al. (2006); Nie et al. (2008); Wang et al. (2009); Ge et al. (2010). For the structural parameters of 1H-imidazol(in)-2-yl side-chain-functionalized 3-substituted 1H-indene and Li-indenide, see: Sun et al. (2009, 2010). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen (2002). For preparation of 2-(1H-inden-3-yl)ethanamine, see: Winter et al. (1967).

Experimental top

Methanol was refluxed with Mg powder until the metal dissolved and then distilled from over Mg(OMe)2. 1H-Imidazol-2-carbaldehyde was purchased from Fluka. 2-(1H-inden-3-yl)ethanamine was prepared as described by Winter et al., 1967.

Compound I: Solutions of 2-(1H-inden-3-yl)ethanamine (1.56 g, 10 mmol) and 1H-imidazol-2-carbaldehyde (0.96 g, 10 mmol) in anhydrous methanol (total amount 20 ml) were mixed under stirring at 253 K, the reaction mixture was kept at this temperature for 6 h and then cooled down to 233 K. The solution was removed from the wthite thin-crystalline precipitate with a canula. The precipitate was washed with small portions of cold diethyl ether and dried on the high-vacuum line what gave 1.85 g (78%) of I. Single crystal of I suitable for the X-ray diffraction analysis was prepared by re-crystallization from anhydrous methanol (slow evaporation, ambient temperature).

Refinement top

Non-H atoms were refined anisotropically. All H atoms except of the ones located at nitrogen atom of the imidazole groups were treated as riding atoms with distances C—H = 0.97 (CH2), 0.93 Å (CArH), and Uiso(H) = 1.2 Ueq(C), and 1.2 Ueq(C), respectively. H atoms at N atoms were found from the difference Fourier synthesis and refined isotropically. Despite of the fact that an achiral compound I crystallizes in a chiral space group P212121, neither the absolute structure determination nor approval of the inversion twinning was possible due to evident reasons (Mo-Kα radiation with no atoms heavier than nitrogen). Thus, the refinement for I was preformed with the Friedel opposites merged (MERG 3 instruction).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. Asymmetric unit of the compound I with labelling and thermal ellipsoids at the 50% probability level. Hydrogen bond is depicted as a dashed line.
[Figure 2] Fig. 2. Chain-assembling of the molecules of I. Prospective view along c-axis. Only atoms participating in the hydrogen bond formation are labeled. Hydrogen bonds are depicted as dashed lines.
2-{(E)-N-[2-(1H-Inden-3-yl)ethyl]iminomethyl}-1H- imidazole top
Crystal data top
C15H15N3F(000) = 1008
Mr = 237.30Dx = 1.239 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 8457 reflections
a = 5.8827 (5) Åθ = 2.4–28.2°
b = 8.3326 (7) ŵ = 0.08 mm1
c = 51.909 (4) ÅT = 296 K
V = 2544.5 (4) Å3Block, colourless
Z = 80.36 × 0.22 × 0.14 mm
Data collection top
Bruker SMART APEXII
diffractometer
2939 independent reflections
Radiation source: fine-focus sealed tube2328 reflections with I > 2σ(I)
graphiteRint = 0.041
Detector resolution: 8.333 pixels mm-1θmax = 26.0°, θmin = 2.4°
φ and ω scansh = 75
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1010
Tmin = 0.973, Tmax = 0.990l = 6461
13315 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.057P)2 + 0.4576P]
where P = (Fo2 + 2Fc2)/3
2939 reflections(Δ/σ)max = 0.001
333 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C15H15N3V = 2544.5 (4) Å3
Mr = 237.30Z = 8
Orthorhombic, P212121Mo Kα radiation
a = 5.8827 (5) ŵ = 0.08 mm1
b = 8.3326 (7) ÅT = 296 K
c = 51.909 (4) Å0.36 × 0.22 × 0.14 mm
Data collection top
Bruker SMART APEXII
diffractometer
2939 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2328 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.990Rint = 0.041
13315 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.113Δρmax = 0.14 e Å3
S = 1.03Δρmin = 0.21 e Å3
2939 reflectionsAbsolute structure: ?
333 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. — NMR spectra were recorded on a Varian INOVA-400 instrument in CDCl3 at 298 K. For 1H and 13C{1H} spectra, the TMS resonances (δH = 0.0 and δC = 0.0) were used as internal reference standards. — Chromato-mass spectrum was measured on Agilent 6890 Series GC system equipped with HP 5973 mass-selective detector. — 1H NMR: δ = 2.93 (m, 2 H, Indenyl—CH2), 3.34 (m, 2 H, CH2 in indene), 3.95 (m, 2 H, NCH2), 6.27 (m, 1 H, CCH in indene), 7.15 (br s, 2 H, HCCH in imidazole), 7.21, 7.30, 7.38, 7.46 (all m, all 1 H, CH in benzene ring of indene), 8.22 (m, 1 H, HCN). — 13C{1H} NMR: δ = 29.02 (Indenyl—CH2), 37.78 (NCH2), 59.13 (CH2 in indene), 118.70 ( CH in indene), 118.23, 130.60 (both br, HCCH in imidazole), 123.79, 124.68, 125.98, 129.24 (CH in benzene ring of indene), 141.38 (C in indene), 144.24, 144.88 (C in benzene ring of indene), 152.86 (HCN). — EI MS (70 eV) m/z (%): 237 (8) [M], 141 (9) [benztropilium], 128 (28) [benzpentafulvene], 115 (13) [indenilium], 109 (100) [C5H7N3], 108 (36) [C5H6N3], 82 (25) [C4H6N2], 81 (82) [C4H5N2].

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.6784 (5)0.2550 (3)0.62194 (4)0.0481 (6)
H1A0.616 (7)0.334 (5)0.6273 (7)0.092 (15)*
N2A0.9145 (4)0.0506 (3)0.61856 (4)0.0490 (6)
N3A0.9748 (5)0.3849 (3)0.66146 (4)0.0510 (6)
C1A0.8760 (5)0.1896 (3)0.63011 (5)0.0439 (7)
C2A0.5871 (6)0.1520 (4)0.60450 (5)0.0549 (8)
H2A0.45120.16450.59560.066*
C3A0.7330 (5)0.0284 (4)0.60277 (5)0.0534 (8)
H3A0.71250.06040.59220.064*
C4A1.0258 (5)0.2616 (4)0.64897 (5)0.0478 (7)
H4A1.16640.21410.65190.057*
C5A1.1416 (6)0.4457 (4)0.67957 (5)0.0556 (8)
H5AA1.16850.55870.67620.067*
H5AB1.28410.38890.67720.067*
C6A1.0601 (5)0.4243 (4)0.70698 (5)0.0510 (8)
H6AA0.91120.47310.70860.061*
H6AB1.04370.31050.71040.061*
C7A1.2152 (5)0.4959 (3)0.72690 (5)0.0407 (6)
C8A1.4034 (5)0.5814 (4)0.72351 (5)0.0518 (7)
H8A1.46620.60500.70750.062*
C9A1.5019 (6)0.6351 (4)0.74873 (7)0.0600 (8)
H9AA1.65600.59590.75090.072*
H9AB1.50160.75120.75010.072*
C10A1.3448 (5)0.5610 (3)0.76792 (5)0.0463 (7)
C11A1.1729 (5)0.4801 (3)0.75462 (5)0.0393 (6)
C12A1.0062 (5)0.3973 (3)0.76790 (5)0.0500 (7)
H12A0.89360.34190.75900.060*
C13A1.0092 (7)0.3980 (4)0.79442 (5)0.0621 (9)
H13A0.89670.34410.80360.074*
C14A1.1783 (7)0.4783 (5)0.80745 (6)0.0680 (10)
H14A1.17960.47660.82540.082*
C15A1.3455 (7)0.5612 (4)0.79457 (6)0.0654 (10)
H15A1.45720.61640.80360.078*
N1B0.2511 (4)0.7865 (3)0.62860 (4)0.0468 (6)
H1B0.143 (6)0.860 (4)0.6239 (6)0.071 (11)*
N2B0.4626 (4)0.5689 (3)0.62951 (4)0.0510 (6)
N3B0.0309 (5)0.6341 (3)0.59023 (4)0.0513 (6)
C1B0.2802 (5)0.6370 (4)0.61924 (5)0.0443 (7)
C2B0.4232 (5)0.8149 (4)0.64549 (5)0.0541 (8)
H2B0.44740.90810.65490.065*
C3B0.5514 (5)0.6812 (4)0.64584 (5)0.0527 (8)
H3B0.68160.66730.65570.063*
C4B0.1292 (5)0.5614 (4)0.60103 (5)0.0473 (7)
H4B0.15180.45360.59710.057*
C5B0.1762 (6)0.5435 (4)0.57281 (5)0.0577 (8)
H5BA0.33370.55750.57780.069*
H5BB0.13990.43020.57410.069*
C6B0.1461 (5)0.5976 (4)0.54526 (5)0.0497 (7)
H6BA0.16540.71310.54440.060*
H6BB0.00770.57310.53980.060*
C7B0.3092 (5)0.5204 (3)0.52707 (5)0.0414 (6)
C8B0.4903 (5)0.4293 (4)0.53233 (5)0.0529 (7)
H8B0.53590.40180.54890.063*
C9B0.6111 (5)0.3769 (4)0.50844 (6)0.0560 (8)
H9BA0.61340.26090.50700.067*
H9BB0.76580.41700.50810.067*
C10B0.4709 (5)0.4507 (3)0.48763 (5)0.0459 (7)
C11B0.2911 (4)0.5363 (3)0.49889 (5)0.0388 (6)
C12B0.1338 (5)0.6134 (4)0.48353 (5)0.0507 (7)
H12B0.01440.67060.49080.061*
C13B0.1569 (6)0.6040 (4)0.45713 (6)0.0631 (9)
H13B0.05170.65580.44670.076*
C14B0.3317 (6)0.5201 (4)0.44599 (6)0.0642 (9)
H14B0.34370.51540.42810.077*
C15B0.4900 (6)0.4426 (4)0.46121 (6)0.0578 (8)
H15B0.60850.38540.45370.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0537 (16)0.0473 (15)0.0431 (12)0.0049 (13)0.0006 (12)0.0032 (11)
N2A0.0555 (15)0.0510 (14)0.0405 (11)0.0040 (13)0.0006 (11)0.0071 (11)
N3A0.0610 (16)0.0558 (15)0.0361 (10)0.0018 (14)0.0071 (12)0.0014 (11)
C1A0.0502 (16)0.0463 (16)0.0352 (12)0.0020 (14)0.0010 (13)0.0042 (12)
C2A0.0556 (18)0.060 (2)0.0493 (15)0.0018 (17)0.0098 (15)0.0027 (14)
C3A0.0610 (18)0.0567 (19)0.0425 (14)0.0020 (17)0.0021 (14)0.0092 (14)
C4A0.0515 (17)0.0516 (17)0.0404 (13)0.0030 (15)0.0016 (14)0.0024 (13)
C5A0.0615 (19)0.057 (2)0.0488 (15)0.0048 (17)0.0009 (15)0.0056 (14)
C6A0.0495 (17)0.060 (2)0.0429 (13)0.0078 (16)0.0047 (13)0.0053 (13)
C7A0.0378 (14)0.0359 (14)0.0485 (14)0.0015 (13)0.0039 (12)0.0006 (12)
C8A0.0460 (16)0.0516 (18)0.0578 (16)0.0050 (15)0.0026 (14)0.0062 (14)
C9A0.0421 (15)0.0497 (17)0.088 (2)0.0053 (15)0.0163 (16)0.0005 (16)
C10A0.0431 (15)0.0377 (15)0.0582 (16)0.0068 (14)0.0153 (14)0.0095 (13)
C11A0.0414 (15)0.0312 (13)0.0453 (13)0.0047 (12)0.0065 (12)0.0030 (11)
C12A0.0539 (17)0.0439 (16)0.0521 (15)0.0039 (15)0.0037 (15)0.0002 (13)
C13A0.076 (2)0.062 (2)0.0486 (15)0.007 (2)0.0017 (17)0.0053 (15)
C14A0.088 (3)0.072 (2)0.0447 (16)0.022 (2)0.0061 (18)0.0082 (16)
C15A0.073 (2)0.060 (2)0.0635 (19)0.010 (2)0.0289 (18)0.0162 (17)
N1B0.0498 (15)0.0462 (14)0.0445 (12)0.0052 (13)0.0047 (12)0.0026 (11)
N2B0.0510 (15)0.0540 (15)0.0480 (12)0.0078 (13)0.0008 (12)0.0008 (12)
N3B0.0612 (15)0.0544 (15)0.0384 (11)0.0022 (14)0.0042 (12)0.0049 (11)
C1B0.0484 (16)0.0462 (16)0.0382 (12)0.0013 (14)0.0033 (13)0.0007 (12)
C2B0.0565 (19)0.0560 (19)0.0498 (15)0.0073 (17)0.0081 (15)0.0078 (14)
C3B0.0495 (17)0.062 (2)0.0464 (15)0.0006 (16)0.0071 (14)0.0015 (14)
C4B0.0630 (18)0.0413 (15)0.0376 (13)0.0011 (15)0.0012 (13)0.0026 (12)
C5B0.0613 (19)0.063 (2)0.0486 (15)0.0129 (18)0.0072 (15)0.0007 (14)
C6B0.0500 (17)0.0567 (18)0.0422 (13)0.0045 (15)0.0042 (13)0.0030 (13)
C7B0.0404 (14)0.0396 (15)0.0442 (13)0.0017 (13)0.0025 (12)0.0034 (12)
C8B0.0511 (17)0.0542 (18)0.0532 (15)0.0044 (16)0.0016 (14)0.0039 (14)
C9B0.0413 (16)0.0535 (18)0.0732 (19)0.0068 (15)0.0060 (15)0.0093 (15)
C10B0.0419 (15)0.0378 (14)0.0580 (15)0.0063 (13)0.0094 (14)0.0076 (13)
C11B0.0378 (13)0.0297 (13)0.0489 (14)0.0034 (12)0.0062 (12)0.0042 (11)
C12B0.0501 (17)0.0502 (17)0.0520 (15)0.0043 (16)0.0040 (14)0.0018 (13)
C13B0.067 (2)0.071 (2)0.0509 (16)0.000 (2)0.0056 (16)0.0003 (16)
C14B0.072 (2)0.074 (2)0.0472 (15)0.014 (2)0.0115 (17)0.0101 (16)
C15B0.0548 (18)0.0578 (19)0.0608 (17)0.0079 (17)0.0197 (16)0.0173 (15)
Geometric parameters (Å, °) top
N1A—C1A1.352 (4)N1B—C1B1.348 (4)
N1A—C2A1.358 (4)N1B—C2B1.360 (4)
N1A—H1A0.80 (4)N1B—H1B0.92 (4)
N2A—C1A1.324 (4)N2B—C1B1.326 (4)
N2A—C3A1.359 (4)N2B—C3B1.366 (4)
N3A—C4A1.251 (3)N3B—C4B1.253 (4)
N3A—C5A1.451 (4)N3B—C5B1.456 (4)
C1A—C4A1.448 (4)C1B—C4B1.442 (4)
C2A—C3A1.344 (4)C2B—C3B1.345 (4)
C2A—H2A0.9300C2B—H2B0.9300
C3A—H3A0.9300C3B—H3B0.9300
C4A—H4A0.9300C4B—H4B0.9300
C5A—C6A1.512 (4)C5B—C6B1.510 (4)
C5A—H5AA0.9700C5B—H5BA0.9700
C5A—H5AB0.9700C5B—H5BB0.9700
C6A—C7A1.502 (4)C6B—C7B1.492 (4)
C6A—H6AA0.9700C6B—H6BA0.9700
C6A—H6AB0.9700C6B—H6BB0.9700
C7A—C8A1.328 (4)C7B—C8B1.336 (4)
C7A—C11A1.466 (3)C7B—C11B1.473 (3)
C8A—C9A1.500 (4)C8B—C9B1.495 (4)
C8A—H8A0.9300C8B—H8B0.9300
C9A—C10A1.492 (5)C9B—C10B1.491 (4)
C9A—H9AA0.9700C9B—H9BA0.9700
C9A—H9AB0.9700C9B—H9BB0.9700
C10A—C15A1.383 (4)C10B—C15B1.377 (4)
C10A—C11A1.397 (4)C10B—C11B1.403 (4)
C11A—C12A1.383 (4)C11B—C12B1.380 (4)
C12A—C13A1.377 (4)C12B—C13B1.379 (4)
C12A—H12A0.9300C12B—H12B0.9300
C13A—C14A1.377 (5)C13B—C14B1.371 (5)
C13A—H13A0.9300C13B—H13B0.9300
C14A—C15A1.375 (5)C14B—C15B1.382 (5)
C14A—H14A0.9300C14B—H14B0.9300
C15A—H15A0.9300C15B—H15B0.9300
C1A—N1A—C2A107.1 (3)C1B—N1B—C2B107.4 (3)
C1A—N1A—H1A128 (3)C1B—N1B—H1B128 (2)
C2A—N1A—H1A124 (3)C2B—N1B—H1B125 (2)
C1A—N2A—C3A104.9 (3)C1B—N2B—C3B105.4 (3)
C4A—N3A—C5A117.4 (3)C4B—N3B—C5B118.0 (3)
N2A—C1A—N1A111.0 (3)N2B—C1B—N1B110.6 (3)
N2A—C1A—C4A124.4 (3)N2B—C1B—C4B125.1 (3)
N1A—C1A—C4A124.7 (3)N1B—C1B—C4B124.2 (3)
C3A—C2A—N1A106.0 (3)C3B—C2B—N1B106.4 (3)
C3A—C2A—H2A127.0C3B—C2B—H2B126.8
N1A—C2A—H2A127.0N1B—C2B—H2B126.8
C2A—C3A—N2A110.9 (3)C2B—C3B—N2B110.1 (3)
C2A—C3A—H3A124.5C2B—C3B—H3B124.9
N2A—C3A—H3A124.5N2B—C3B—H3B124.9
N3A—C4A—C1A123.0 (3)N3B—C4B—C1B123.0 (3)
N3A—C4A—H4A118.5N3B—C4B—H4B118.5
C1A—C4A—H4A118.5C1B—C4B—H4B118.5
N3A—C5A—C6A110.7 (2)N3B—C5B—C6B111.4 (3)
N3A—C5A—H5AA109.5N3B—C5B—H5BA109.4
C6A—C5A—H5AA109.5C6B—C5B—H5BA109.4
N3A—C5A—H5AB109.5N3B—C5B—H5BB109.4
C6A—C5A—H5AB109.5C6B—C5B—H5BB109.4
H5AA—C5A—H5AB108.1H5BA—C5B—H5BB108.0
C7A—C6A—C5A114.1 (2)C7B—C6B—C5B113.3 (3)
C7A—C6A—H6AA108.7C7B—C6B—H6BA108.9
C5A—C6A—H6AA108.7C5B—C6B—H6BA108.9
C7A—C6A—H6AB108.7C7B—C6B—H6BB108.9
C5A—C6A—H6AB108.7C5B—C6B—H6BB108.9
H6AA—C6A—H6AB107.6H6BA—C6B—H6BB107.7
C8A—C7A—C11A108.6 (3)C8B—C7B—C11B108.2 (2)
C8A—C7A—C6A128.9 (3)C8B—C7B—C6B128.9 (2)
C11A—C7A—C6A122.5 (2)C11B—C7B—C6B122.9 (2)
C7A—C8A—C9A111.5 (3)C7B—C8B—C9B112.0 (3)
C7A—C8A—H8A124.3C7B—C8B—H8B124.0
C9A—C8A—H8A124.3C9B—C8B—H8B124.0
C10A—C9A—C8A102.7 (3)C10B—C9B—C8B102.6 (2)
C10A—C9A—H9AA111.2C10B—C9B—H9BA111.2
C8A—C9A—H9AA111.2C8B—C9B—H9BA111.2
C10A—C9A—H9AB111.2C10B—C9B—H9BB111.2
C8A—C9A—H9AB111.2C8B—C9B—H9BB111.2
H9AA—C9A—H9AB109.1H9BA—C9B—H9BB109.2
C15A—C10A—C11A119.8 (3)C15B—C10B—C11B120.1 (3)
C15A—C10A—C9A131.7 (3)C15B—C10B—C9B131.0 (3)
C11A—C10A—C9A108.5 (2)C11B—C10B—C9B108.9 (2)
C12A—C11A—C10A120.5 (2)C12B—C11B—C10B120.1 (2)
C12A—C11A—C7A130.8 (3)C12B—C11B—C7B131.6 (3)
C10A—C11A—C7A108.6 (2)C10B—C11B—C7B108.3 (2)
C13A—C12A—C11A119.2 (3)C13B—C12B—C11B118.8 (3)
C13A—C12A—H12A120.4C13B—C12B—H12B120.6
C11A—C12A—H12A120.4C11B—C12B—H12B120.6
C14A—C13A—C12A120.2 (3)C14B—C13B—C12B121.5 (3)
C14A—C13A—H13A119.9C14B—C13B—H13B119.3
C12A—C13A—H13A119.9C12B—C13B—H13B119.3
C15A—C14A—C13A121.5 (3)C13B—C14B—C15B120.2 (3)
C15A—C14A—H14A119.3C13B—C14B—H14B119.9
C13A—C14A—H14A119.3C15B—C14B—H14B119.9
C14A—C15A—C10A118.9 (3)C10B—C15B—C14B119.4 (3)
C14A—C15A—H15A120.5C10B—C15B—H15B120.3
C10A—C15A—H15A120.5C14B—C15B—H15B120.3
C3A—N2A—C1A—N1A0.4 (3)C3B—N2B—C1B—N1B0.4 (3)
C3A—N2A—C1A—C4A179.5 (3)C3B—N2B—C1B—C4B178.9 (3)
C2A—N1A—C1A—N2A0.3 (3)C2B—N1B—C1B—N2B0.2 (3)
C2A—N1A—C1A—C4A179.6 (3)C2B—N1B—C1B—C4B178.8 (3)
C1A—N1A—C2A—C3A0.1 (3)C1B—N1B—C2B—C3B0.0 (3)
N1A—C2A—C3A—N2A0.2 (3)N1B—C2B—C3B—N2B0.2 (3)
C1A—N2A—C3A—C2A0.4 (3)C1B—N2B—C3B—C2B0.4 (3)
C5A—N3A—C4A—C1A179.3 (2)C5B—N3B—C4B—C1B178.1 (3)
N2A—C1A—C4A—N3A172.7 (3)N2B—C1B—C4B—N3B174.1 (3)
N1A—C1A—C4A—N3A7.3 (4)N1B—C1B—C4B—N3B7.5 (4)
C4A—N3A—C5A—C6A111.5 (3)C4B—N3B—C5B—C6B112.1 (3)
N3A—C5A—C6A—C7A175.5 (3)N3B—C5B—C6B—C7B173.8 (3)
C5A—C6A—C7A—C8A4.2 (5)C5B—C6B—C7B—C8B9.4 (5)
C5A—C6A—C7A—C11A176.5 (3)C5B—C6B—C7B—C11B170.9 (3)
C11A—C7A—C8A—C9A1.6 (3)C11B—C7B—C8B—C9B0.4 (3)
C6A—C7A—C8A—C9A177.8 (3)C6B—C7B—C8B—C9B179.3 (3)
C7A—C8A—C9A—C10A2.2 (3)C7B—C8B—C9B—C10B0.5 (3)
C8A—C9A—C10A—C15A178.0 (3)C8B—C9B—C10B—C15B177.8 (3)
C8A—C9A—C10A—C11A2.0 (3)C8B—C9B—C10B—C11B0.3 (3)
C15A—C10A—C11A—C12A1.4 (4)C15B—C10B—C11B—C12B0.4 (4)
C9A—C10A—C11A—C12A178.6 (3)C9B—C10B—C11B—C12B178.8 (3)
C15A—C10A—C11A—C7A178.8 (3)C15B—C10B—C11B—C7B178.3 (3)
C9A—C10A—C11A—C7A1.2 (3)C9B—C10B—C11B—C7B0.1 (3)
C8A—C7A—C11A—C12A176.8 (3)C8B—C7B—C11B—C12B178.2 (3)
C6A—C7A—C11A—C12A3.8 (5)C6B—C7B—C11B—C12B2.0 (5)
C8A—C7A—C11A—C10A0.2 (3)C8B—C7B—C11B—C10B0.2 (3)
C6A—C7A—C11A—C10A179.2 (3)C6B—C7B—C11B—C10B179.6 (3)
C10A—C11A—C12A—C13A1.2 (4)C10B—C11B—C12B—C13B0.1 (4)
C7A—C11A—C12A—C13A177.9 (3)C7B—C11B—C12B—C13B178.1 (3)
C11A—C12A—C13A—C14A0.9 (5)C11B—C12B—C13B—C14B0.1 (5)
C12A—C13A—C14A—C15A0.9 (5)C12B—C13B—C14B—C15B0.1 (5)
C13A—C14A—C15A—C10A1.1 (5)C11B—C10B—C15B—C14B0.4 (4)
C11A—C10A—C15A—C14A1.3 (5)C9B—C10B—C15B—C14B178.3 (3)
C9A—C10A—C15A—C14A178.7 (3)C13B—C14B—C15B—C10B0.1 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···N2B0.80 (4)2.16 (4)2.935 (4)162 (4)
N1B—H1B···N2Ai0.92 (4)2.10 (4)3.006 (4)170 (3)
Symmetry codes: (i) x−1, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···N2B0.80 (4)2.16 (4)2.935 (4)162 (4)
N1B—H1B···N2Ai0.92 (4)2.10 (4)3.006 (4)170 (3)
Symmetry codes: (i) x−1, y+1, z.
Acknowledgements top

Financial support from the National Natural Science Foundation of China (project Nos. 20702041 and 21072157) and the Shaanxi Province Administration of Foreign Experts Bureau Foundation (grant No. 20106100079) is gratefully acknowledged. The authors are thankful to Mr Wang Minchang and Mr Su Pengfei (Xi'an Modern Chemistry Research Institute) for their help in carrying out the NMR spectroscopic and X-ray diffraction experiments.

references
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