Conformational polymorphism in a Schiff-base macrocyclic organic ligand: an experimental and theoretical study

Lo Presti, L.; Soave, R.; Longhi, M.; Ortoleva, E.

doi:10.1107/S0108768110029514

Conformational polymorphism in a Schiff-base macrocyclic organic ligand: an experimental and theoretical study

L. Lo Presti, R. Soave, M. Longhi and E. Ortoleva

Polymorphism in the highly flexible organic Schiff-base macrocycle ligand 3,6,9,17,20,23-hexa-azapentacyclo(23.3.1.1^11,15.0^2,6.0^16,20)triaconta-1(29),9,11,13,15(30),23,25,27-octaene (DIEN, C₂₄H₃₀N₆) has been studied by single-crystal X-ray diffraction and both solid-state and gas-phase density functional theory (DFT) calculations. In the literature, only solvated structures of the title compound are known. Two new polymorphs and a new solvated form of DIEN, all obtained from the same solvent with different crystallization conditions, are presented for the first time. They all have $P\bar 1$ symmetry, with the macrocycle positioned on inversion centres. The two unsolvated polymorphic forms differ in the number of molecules in the asymmetric unit Z′, density and cohesive energy. Theoretical results confirm that the most stable form is (II°), with Z′ = 1.5. Two distinct molecular conformations have been found, named `endo' or `exo' according to the orientation of the imine N atoms, which can be directed towards the interior or the exterior of the macrocycle. The endo arrangement is ubiquitous in the solid state and is shared by two independent molecules which constitute an invariant supramolecular synthon in all the known crystal forms of DIEN. It is also the most stable arrangement in the gas phase. The exo form, on the other hand, appears only in phase (II°), which contains both the conformers. Similarities and differences among the occurring packing motifs, as well as solvent effects, are discussed with the aid of Hirshfeld surface fingerprint plots and correlated to the results of the energy analysis. A possible interconversion path in the gas phase between the endo and the exo conformers has been found by DFT calculations; it consists of a two-step mechanism with activation energies of the order of 30–40 kJ mol⁻¹. These findings have been related to the empirical evidence that the most stable phase (II°) is also the last appearing one, in accordance with Ostwald's rule.

Keywords: macrocycle Schiff-base ligand; conformational polymorphism; periodic and gas-phase DFT calculations; solvent effects; crystal packing; interaction energy; reaction path.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768110029514/ps5007sup1.cif Contains datablocks dienII, dienI, dienSOLV
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768110029514/ps5007dienIIsup2.hkl Contains datablock dienII
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768110029514/ps5007dienIsup3.hkl Contains datablock dienI
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768110029514/ps5007dienSOLVsup4.hkl Contains datablock dienSOLV
	Portable Document Format (PDF) file https://doi.org/10.1107/S0108768110029514/ps5007sup5.pdf Extra tables and figures

CCDC references: 798612; 798613; 798614

Computing details top

Data collection: Saint+ for dienI. Cell refinement: Saint+ for dienI. Data reduction: Saint+ for dienI. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for dienI. For all structures, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

3,6,9,17,20,23-hexa-azapentacyclo(23.3.1.1^11,15.0^2,6.0^16,20)triaconta-1 (29),9,11,13,15(30),23,25,27-octaene (dienII) top

Crystal data top

C₂₄H₃₀N₆	Z = 3
M_r = 402.54	F(000) = 648
Triclinic, P1	D_x = 1.239 Mg m⁻³
Hall symbol: -P1	Melting point: 460.65 K
a = 9.697 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2426 (12) Å	Cell parameters from 2864 reflections
c = 13.9365 (14) Å	θ = 2.4–19.4°
α = 87.182 (2)°	µ = 0.08 mm⁻¹
β = 81.257 (2)°	T = 293 K
γ = 82.062 (2)°	Prism, colourless
V = 1618.9 (3) Å³	0.23 × 0.20 × 0.05 mm

Data collection top

Bruker AXS Smart diffractometer	7448 independent reflections
Radiation source: fine-focus sealed tube	3646 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: empirical (using intensity measurements) SADABS-2007/4	h = −12→12
T_min = 0.936, T_max = 0.943	k = −15→15
48844 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0746P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
7448 reflections	Δρ_max = 0.30 e Å⁻³
419 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (12)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1A	0.8391 (2)	0.18721 (15)	0.95126 (14)	0.0441 (5)
N2A	0.81056 (18)	0.16370 (14)	1.16504 (13)	0.0385 (5)
N3A	0.7985 (2)	0.0614 (2)	1.30955 (16)	0.0508 (6)
C1A	0.9672 (2)	−0.09261 (18)	0.77200 (16)	0.0391 (5)
C2A	0.8642 (2)	−0.1276 (2)	0.72710 (17)	0.0480 (6)
H1A	0.8889	−0.1838	0.6826	0.058*
C3A	0.7259 (3)	−0.0810 (2)	0.74694 (19)	0.0548 (7)
H2A	0.6577	−0.1065	0.7167	0.066*
C4A	0.6882 (2)	0.0034 (2)	0.81158 (18)	0.0504 (6)
H3A	0.5946	0.0345	0.8252	0.060*
C5A	0.7897 (2)	0.04214 (18)	0.85650 (16)	0.0403 (6)
C6A	0.9279 (2)	−0.00719 (18)	0.83685 (16)	0.0399 (6)
H4A	0.9960	0.0173	0.8677	0.048*
C7A	0.7508 (2)	0.13528 (19)	0.92295 (17)	0.0445 (6)
H5A	0.6559	0.1565	0.9449	0.053*
C8A	0.7872 (3)	0.27892 (18)	1.01636 (18)	0.0481 (6)
H6A	0.6855	0.2849	1.0314	0.058*
H7A	0.8111	0.3473	0.9842	0.058*
C9A	0.8509 (3)	0.26154 (19)	1.10945 (17)	0.0470 (6)
H9A	0.9527	0.2541	1.0939	0.056*
H8A	0.8207	0.3259	1.1491	0.056*
C10A	0.6609 (2)	0.1733 (2)	1.20412 (19)	0.0512 (6)
H11A	0.6059	0.1566	1.1554	0.061*
H10A	0.6264	0.2470	1.2272	0.061*
C11A	0.6540 (2)	0.0889 (2)	1.28722 (18)	0.0537 (7)
H12A	0.5916	0.1193	1.3434	0.064*
H13A	0.6195	0.0236	1.2685	0.064*
C12A	0.8802 (2)	0.13907 (19)	1.25109 (16)	0.0428 (6)
H14A	0.8727	0.2069	1.2872	0.051*
H3AN	0.828 (3)	0.001 (2)	1.2879 (18)	0.050 (9)*
N1B	0.2129 (2)	0.45589 (15)	1.09065 (14)	0.0436 (5)
N2B	0.25635 (18)	0.29282 (14)	0.93544 (13)	0.0379 (4)
N3B	0.1778 (2)	0.17443 (16)	0.83722 (15)	0.0476 (5)
C1B	0.1764 (2)	0.36881 (18)	0.78198 (16)	0.0383 (5)
C2B	0.2204 (2)	0.3936 (2)	0.68484 (17)	0.0465 (6)
H1B	0.3000	0.3526	0.6520	0.056*
C3B	0.1477 (3)	0.4784 (2)	0.63637 (18)	0.0522 (7)
H2B	0.1779	0.4942	0.5712	0.063*
C4B	−0.0305 (3)	0.4606 (2)	1.31517 (18)	0.0475 (6)
H3B	0.0179	0.4032	1.3479	0.057*
C5B	0.0168 (2)	0.48331 (18)	1.21793 (17)	0.0389 (5)
C6B	−0.0587 (2)	0.56826 (18)	1.17016 (17)	0.0403 (6)
H4B	−0.0296	0.5831	1.1047	0.048*
C7B	0.1490 (2)	0.42378 (18)	1.17002 (18)	0.0428 (6)
H5B	0.1872	0.3594	1.1997	0.051*
C8B	0.3485 (2)	0.3951 (2)	1.05405 (17)	0.0466 (6)
H7B	0.3635	0.3273	1.0923	0.056*
H6B	0.4225	0.4388	1.0607	0.056*
C9B	0.3559 (2)	0.36807 (19)	0.94838 (17)	0.0444 (6)
H9B	0.3357	0.4357	0.9109	0.053*
H8B	0.4506	0.3347	0.9239	0.053*
C10B	0.2860 (2)	0.18373 (18)	0.97946 (18)	0.0474 (6)
H10B	0.2467	0.1828	1.0477	0.057*
H11B	0.3866	0.1604	0.9732	0.057*
C11B	0.2161 (3)	0.1100 (2)	0.92328 (19)	0.0601 (7)
H13B	0.2803	0.0442	0.9040	0.072*
H12B	0.1328	0.0879	0.9629	0.072*
C12B	0.2500 (2)	0.27207 (18)	0.83334 (16)	0.0408 (6)
H14B	0.3461	0.2543	0.7992	0.049*
H3BN	0.087 (2)	0.1962 (19)	0.8419 (17)	0.051 (8)*
N1C	0.6626 (2)	0.51097 (16)	0.67012 (16)	0.0540 (6)
N2C	0.7902 (2)	0.28738 (16)	0.59202 (15)	0.0533 (6)
N3C	0.8036 (2)	0.10513 (17)	0.53711 (18)	0.0584 (6)
C1C	0.5807 (2)	0.22568 (19)	0.53569 (17)	0.0439 (6)
C2C	0.4762 (3)	0.1576 (2)	0.54429 (18)	0.0523 (7)
H1C	0.4841	0.0935	0.5829	0.063*
C3C	0.3610 (3)	0.1833 (2)	0.4966 (2)	0.0566 (7)
H2C	0.2927	0.1360	0.5024	0.068*
C5C	0.4492 (2)	0.34851 (19)	0.43037 (17)	0.0444 (6)
C4C	0.3464 (3)	0.2786 (2)	0.44036 (19)	0.0518 (7)
H3C	0.2677	0.2961	0.4091	0.062*
C6C	0.5654 (2)	0.32036 (19)	0.47781 (17)	0.0463 (6)
H4C	0.6350	0.3665	0.4705	0.056*
C7C	0.5610 (3)	0.5475 (2)	0.62778 (18)	0.0506 (6)
H5C	0.4863	0.5064	0.6332	0.061*
C8C	0.6581 (3)	0.4055 (2)	0.72317 (19)	0.0580 (7)
H7C	0.5746	0.3747	0.7132	0.070*
H6C	0.6524	0.4169	0.7921	0.070*
C9C	0.7879 (3)	0.3249 (2)	0.6893 (2)	0.0635 (8)
H8C	0.8711	0.3602	0.6910	0.076*
H9C	0.7915	0.2616	0.7340	0.076*
C10C	0.9342 (3)	0.2484 (3)	0.5425 (3)	0.0851 (10)
H10C	0.9472	0.2765	0.4759	0.102*
H11C	1.0048	0.2723	0.5761	0.102*
C11C	0.9439 (3)	0.1281 (3)	0.5457 (2)	0.0804 (9)
H13C	1.0117	0.0968	0.4924	0.097*
H12C	0.9720	0.0978	0.6064	0.097*
C12C	0.7088 (2)	0.19465 (19)	0.58627 (18)	0.0478 (6)
H14C	0.6769	0.1690	0.6526	0.057*
H3CN	0.799 (3)	0.106 (3)	0.465 (2)	0.101 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0456 (12)	0.0395 (11)	0.0457 (12)	−0.0022 (9)	−0.0056 (9)	0.0005 (9)
N2A	0.0359 (11)	0.0370 (11)	0.0427 (11)	−0.0055 (8)	−0.0046 (9)	−0.0017 (9)
N3A	0.0456 (13)	0.0580 (16)	0.0453 (13)	−0.0043 (12)	0.0003 (10)	0.0033 (12)
C1A	0.0409 (13)	0.0371 (13)	0.0405 (13)	−0.0076 (10)	−0.0089 (11)	0.0020 (11)
C2A	0.0483 (15)	0.0497 (15)	0.0485 (15)	−0.0100 (12)	−0.0114 (12)	−0.0045 (12)
C3A	0.0466 (16)	0.0619 (17)	0.0620 (18)	−0.0142 (13)	−0.0206 (13)	−0.0038 (14)
C4A	0.0383 (14)	0.0558 (16)	0.0581 (17)	−0.0049 (12)	−0.0132 (12)	0.0038 (13)
C5A	0.0387 (13)	0.0395 (13)	0.0430 (14)	−0.0073 (11)	−0.0071 (11)	0.0061 (11)
C6A	0.0369 (13)	0.0415 (13)	0.0440 (14)	−0.0085 (11)	−0.0121 (11)	0.0005 (11)
C7A	0.0393 (13)	0.0426 (14)	0.0495 (15)	−0.0010 (11)	−0.0059 (12)	0.0060 (12)
C8A	0.0536 (15)	0.0319 (13)	0.0556 (16)	−0.0004 (11)	−0.0041 (12)	0.0023 (11)
C9A	0.0493 (15)	0.0362 (13)	0.0555 (16)	−0.0062 (11)	−0.0057 (12)	−0.0041 (12)
C10A	0.0393 (14)	0.0523 (16)	0.0594 (17)	−0.0020 (12)	−0.0032 (12)	−0.0007 (13)
C11A	0.0435 (15)	0.0661 (18)	0.0499 (16)	−0.0081 (13)	−0.0007 (12)	−0.0018 (13)
C12A	0.0455 (14)	0.0412 (14)	0.0420 (14)	−0.0051 (11)	−0.0066 (11)	−0.0068 (11)
N1B	0.0462 (12)	0.0365 (11)	0.0474 (13)	−0.0023 (9)	−0.0064 (10)	−0.0033 (9)
N2B	0.0400 (11)	0.0319 (10)	0.0424 (11)	−0.0059 (8)	−0.0068 (9)	0.0000 (8)
N3B	0.0570 (15)	0.0354 (12)	0.0534 (14)	−0.0082 (11)	−0.0150 (11)	−0.0014 (10)
C1B	0.0420 (13)	0.0339 (12)	0.0396 (14)	−0.0079 (10)	−0.0048 (11)	−0.0033 (10)
C2B	0.0464 (14)	0.0516 (15)	0.0407 (14)	−0.0105 (12)	0.0009 (11)	−0.0039 (12)
C3B	0.0614 (17)	0.0565 (17)	0.0386 (15)	−0.0162 (14)	−0.0029 (13)	0.0095 (13)
C4B	0.0547 (16)	0.0414 (14)	0.0475 (16)	−0.0108 (12)	−0.0098 (13)	0.0082 (12)
C5B	0.0421 (13)	0.0338 (13)	0.0432 (14)	−0.0108 (10)	−0.0090 (11)	0.0006 (11)
C6B	0.0467 (14)	0.0394 (13)	0.0359 (13)	−0.0090 (11)	−0.0065 (11)	0.0006 (11)
C7B	0.0491 (15)	0.0305 (13)	0.0508 (16)	−0.0054 (11)	−0.0141 (12)	−0.0007 (11)
C8B	0.0423 (14)	0.0437 (14)	0.0552 (16)	−0.0060 (11)	−0.0102 (12)	−0.0046 (12)
C9B	0.0403 (13)	0.0417 (14)	0.0511 (15)	−0.0078 (11)	−0.0044 (11)	−0.0012 (11)
C10B	0.0455 (14)	0.0404 (14)	0.0562 (16)	−0.0040 (11)	−0.0103 (12)	0.0045 (12)
C11B	0.082 (2)	0.0408 (15)	0.0615 (18)	−0.0125 (14)	−0.0215 (15)	0.0033 (13)
C12B	0.0379 (13)	0.0392 (13)	0.0440 (14)	−0.0043 (10)	−0.0010 (11)	−0.0052 (11)
N1C	0.0603 (14)	0.0414 (12)	0.0618 (14)	−0.0049 (10)	−0.0159 (12)	−0.0015 (11)
N2C	0.0636 (14)	0.0411 (12)	0.0594 (14)	−0.0119 (10)	−0.0176 (11)	−0.0041 (10)
N3C	0.0654 (16)	0.0454 (13)	0.0644 (16)	0.0020 (11)	−0.0156 (13)	−0.0074 (12)
C1C	0.0495 (15)	0.0415 (14)	0.0398 (14)	−0.0072 (11)	−0.0019 (11)	−0.0054 (11)
C2C	0.0585 (17)	0.0422 (15)	0.0542 (16)	−0.0110 (13)	0.0015 (13)	−0.0004 (12)
C3C	0.0491 (16)	0.0510 (17)	0.0702 (19)	−0.0169 (13)	0.0013 (14)	−0.0112 (14)
C5C	0.0460 (14)	0.0412 (14)	0.0460 (15)	−0.0052 (11)	−0.0053 (12)	−0.0069 (11)
C4C	0.0465 (15)	0.0512 (16)	0.0594 (17)	−0.0090 (12)	−0.0081 (12)	−0.0103 (13)
C6C	0.0480 (15)	0.0405 (14)	0.0517 (15)	−0.0121 (11)	−0.0048 (12)	−0.0052 (12)
C7C	0.0501 (16)	0.0465 (15)	0.0570 (17)	−0.0106 (12)	−0.0074 (13)	−0.0075 (13)
C8C	0.0731 (19)	0.0546 (17)	0.0478 (16)	−0.0126 (14)	−0.0109 (14)	0.0013 (13)
C9C	0.087 (2)	0.0483 (16)	0.0636 (19)	−0.0110 (15)	−0.0370 (16)	0.0044 (14)
C10C	0.065 (2)	0.068 (2)	0.120 (3)	−0.0163 (17)	0.0007 (19)	0.001 (2)
C11C	0.065 (2)	0.086 (2)	0.090 (2)	0.0009 (17)	−0.0180 (17)	−0.0096 (19)
C12C	0.0580 (16)	0.0421 (14)	0.0437 (15)	−0.0110 (12)	−0.0066 (12)	0.0036 (12)

Geometric parameters (Å, º) top

N1A—C7A	1.253 (3)	C4B—H3B	0.9300
N1A—C8A	1.464 (3)	C5B—C6B	1.390 (3)
N2A—C9A	1.461 (3)	C5B—C7B	1.466 (3)
N2A—C10A	1.462 (3)	C6B—C1Bⁱⁱ	1.385 (3)
N2A—C12A	1.463 (3)	C6B—H4B	0.9300
N3A—C12A	1.460 (3)	C7B—H5B	0.9300
N3A—C11A	1.472 (3)	C8B—C9B	1.514 (3)
N3A—H3AN	0.81 (2)	C8B—H7B	0.9700
C1A—C2A	1.381 (3)	C8B—H6B	0.9700
C1A—C6A	1.391 (3)	C9B—H9B	0.9700
C1A—C12Aⁱ	1.503 (3)	C9B—H8B	0.9700
C2A—C3A	1.376 (3)	C10B—C11B	1.512 (3)
C2A—H1A	0.9300	C10B—H10B	0.9700
C3A—C4A	1.379 (3)	C10B—H11B	0.9700
C3A—H2A	0.9300	C11B—H13B	0.9700
C4A—C5A	1.389 (3)	C11B—H12B	0.9700
C4A—H3A	0.9300	C12B—H14B	0.9800
C5A—C6A	1.384 (3)	N1C—C7C	1.244 (3)
C5A—C7A	1.476 (3)	N1C—C8C	1.459 (3)
C6A—H4A	0.9300	N2C—C9C	1.450 (3)
C7A—H5A	0.9300	N2C—C12C	1.481 (3)
C8A—C9A	1.514 (3)	N2C—C10C	1.486 (3)
C8A—H6A	0.9700	N3C—C11C	1.450 (3)
C8A—H7A	0.9700	N3C—C12C	1.456 (3)
C9A—H9A	0.9700	N3C—H3CN	1.01 (3)
C9A—H8A	0.9700	C1C—C6C	1.383 (3)
C10A—C11A	1.514 (3)	C1C—C2C	1.387 (3)
C10A—H11A	0.9700	C1C—C12C	1.514 (3)
C10A—H10A	0.9700	C2C—C3C	1.378 (3)
C11A—H12A	0.9700	C2C—H1C	0.9300
C11A—H13A	0.9700	C3C—C4C	1.376 (4)
C12A—C1Aⁱ	1.503 (3)	C3C—H2C	0.9300
C12A—H14A	0.9800	C5C—C6C	1.386 (3)
N1B—C7B	1.256 (3)	C5C—C4C	1.388 (3)
N1B—C8B	1.451 (3)	C5C—C7Cⁱⁱⁱ	1.475 (3)
N2B—C10B	1.453 (3)	C4C—H3C	0.9300
N2B—C9B	1.459 (3)	C6C—H4C	0.9300
N2B—C12B	1.469 (3)	C7C—C5Cⁱⁱⁱ	1.475 (3)
N3B—C12B	1.462 (3)	C7C—H5C	0.9300
N3B—C11B	1.470 (3)	C8C—C9C	1.517 (4)
N3B—H3BN	0.88 (2)	C8C—H7C	0.9700
C1B—C6Bⁱⁱ	1.385 (3)	C8C—H6C	0.9700
C1B—C2B	1.388 (3)	C9C—H8C	0.9700
C1B—C12B	1.504 (3)	C9C—H9C	0.9700
C2B—C3B	1.380 (3)	C10C—C11C	1.462 (4)
C2B—H1B	0.9300	C10C—H10C	0.9700
C3B—C4Bⁱⁱ	1.374 (3)	C10C—H11C	0.9700
C3B—H2B	0.9300	C11C—H13C	0.9700
C4B—C3Bⁱⁱ	1.374 (3)	C11C—H12C	0.9700
C4B—C5B	1.391 (3)	C12C—H14C	0.9800

C7A—N1A—C8A	118.2 (2)	N1B—C8B—H7B	109.4
C9A—N2A—C10A	113.51 (18)	C9B—C8B—H7B	109.4
C9A—N2A—C12A	113.62 (17)	N1B—C8B—H6B	109.4
C10A—N2A—C12A	103.57 (18)	C9B—C8B—H6B	109.4
C12A—N3A—C11A	105.51 (19)	H7B—C8B—H6B	108.0
C12A—N3A—H3AN	105.9 (19)	N2B—C9B—C8B	111.80 (19)
C11A—N3A—H3AN	107.0 (18)	N2B—C9B—H9B	109.3
C2A—C1A—C6A	118.2 (2)	C8B—C9B—H9B	109.3
C2A—C1A—C12Aⁱ	122.3 (2)	N2B—C9B—H8B	109.3
C6A—C1A—C12Aⁱ	119.40 (19)	C8B—C9B—H8B	109.3
C3A—C2A—C1A	121.2 (2)	H9B—C9B—H8B	107.9
C3A—C2A—H1A	119.4	N2B—C10B—C11B	104.39 (19)
C1A—C2A—H1A	119.4	N2B—C10B—H10B	110.9
C2A—C3A—C4A	120.0 (2)	C11B—C10B—H10B	110.9
C2A—C3A—H2A	120.0	N2B—C10B—H11B	110.9
C4A—C3A—H2A	120.0	C11B—C10B—H11B	110.9
C3A—C4A—C5A	120.2 (2)	H10B—C10B—H11B	108.9
C3A—C4A—H3A	119.9	N3B—C11B—C10B	106.80 (19)
C5A—C4A—H3A	119.9	N3B—C11B—H13B	110.4
C6A—C5A—C4A	118.8 (2)	C10B—C11B—H13B	110.4
C6A—C5A—C7A	120.7 (2)	N3B—C11B—H12B	110.4
C4A—C5A—C7A	120.4 (2)	C10B—C11B—H12B	110.4
C5A—C6A—C1A	121.5 (2)	H13B—C11B—H12B	108.6
C5A—C6A—H4A	119.3	N3B—C12B—N2B	104.52 (18)
C1A—C6A—H4A	119.3	N3B—C12B—C1B	112.34 (18)
N1A—C7A—C5A	123.4 (2)	N2B—C12B—C1B	112.99 (18)
N1A—C7A—H5A	118.3	N3B—C12B—H14B	108.9
C5A—C7A—H5A	118.3	N2B—C12B—H14B	108.9
N1A—C8A—C9A	110.77 (18)	C1B—C12B—H14B	108.9
N1A—C8A—H6A	109.5	C7C—N1C—C8C	118.0 (2)
C9A—C8A—H6A	109.5	C9C—N2C—C12C	114.8 (2)
N1A—C8A—H7A	109.5	C9C—N2C—C10C	113.3 (2)
C9A—C8A—H7A	109.5	C12C—N2C—C10C	104.9 (2)
H6A—C8A—H7A	108.1	C11C—N3C—C12C	105.1 (2)
N2A—C9A—C8A	112.27 (19)	C11C—N3C—H3CN	105.8 (18)
N2A—C9A—H9A	109.1	C12C—N3C—H3CN	112.3 (18)
C8A—C9A—H9A	109.1	C6C—C1C—C2C	117.8 (2)
N2A—C9A—H8A	109.1	C6C—C1C—C12C	121.7 (2)
C8A—C9A—H8A	109.1	C2C—C1C—C12C	120.5 (2)
H9A—C9A—H8A	107.9	C3C—C2C—C1C	121.1 (2)
N2A—C10A—C11A	103.83 (18)	C3C—C2C—H1C	119.5
N2A—C10A—H11A	111.0	C1C—C2C—H1C	119.5
C11A—C10A—H11A	111.0	C4C—C3C—C2C	120.3 (2)
N2A—C10A—H10A	111.0	C4C—C3C—H2C	119.8
C11A—C10A—H10A	111.0	C2C—C3C—H2C	119.8
H11A—C10A—H10A	109.0	C6C—C5C—C4C	118.8 (2)
N3A—C11A—C10A	106.37 (19)	C6C—C5C—C7Cⁱⁱⁱ	118.5 (2)
N3A—C11A—H12A	110.5	C4C—C5C—C7Cⁱⁱⁱ	122.6 (2)
C10A—C11A—H12A	110.5	C3C—C4C—C5C	120.0 (2)
N3A—C11A—H13A	110.5	C3C—C4C—H3C	120.0
C10A—C11A—H13A	110.5	C5C—C4C—H3C	120.0
H12A—C11A—H13A	108.6	C1C—C6C—C5C	122.0 (2)
N3A—C12A—N2A	104.75 (18)	C1C—C6C—H4C	119.0
N3A—C12A—C1Aⁱ	111.70 (19)	C5C—C6C—H4C	119.0
N2A—C12A—C1Aⁱ	113.56 (19)	N1C—C7C—C5Cⁱⁱⁱ	124.6 (2)
N3A—C12A—H14A	108.9	N1C—C7C—H5C	117.7
N2A—C12A—H14A	108.9	C5Cⁱⁱⁱ—C7C—H5C	117.7
C1Aⁱ—C12A—H14A	108.9	N1C—C8C—C9C	110.9 (2)
C7B—N1B—C8B	118.0 (2)	N1C—C8C—H7C	109.5
C10B—N2B—C9B	114.23 (18)	C9C—C8C—H7C	109.5
C10B—N2B—C12B	104.44 (17)	N1C—C8C—H6C	109.5
C9B—N2B—C12B	113.91 (18)	C9C—C8C—H6C	109.5
C12B—N3B—C11B	105.25 (18)	H7C—C8C—H6C	108.0
C12B—N3B—H3BN	108.4 (16)	N2C—C9C—C8C	112.8 (2)
C11B—N3B—H3BN	112.5 (16)	N2C—C9C—H8C	109.0
C6Bⁱⁱ—C1B—C2B	118.7 (2)	C8C—C9C—H8C	109.0
C6Bⁱⁱ—C1B—C12B	120.3 (2)	N2C—C9C—H9C	109.0
C2B—C1B—C12B	121.0 (2)	C8C—C9C—H9C	109.0
C3B—C2B—C1B	120.9 (2)	H8C—C9C—H9C	107.8
C3B—C2B—H1B	119.6	C11C—C10C—N2C	105.0 (2)
C1B—C2B—H1B	119.6	C11C—C10C—H10C	110.7
C4Bⁱⁱ—C3B—C2B	119.7 (2)	N2C—C10C—H10C	110.7
C4Bⁱⁱ—C3B—H2B	120.2	C11C—C10C—H11C	110.7
C2B—C3B—H2B	120.2	N2C—C10C—H11C	110.7
C3Bⁱⁱ—C4B—C5B	121.0 (2)	H10C—C10C—H11C	108.8
C3Bⁱⁱ—C4B—H3B	119.5	N3C—C11C—C10C	105.1 (2)
C5B—C4B—H3B	119.5	N3C—C11C—H13C	110.7
C6B—C5B—C4B	118.4 (2)	C10C—C11C—H13C	110.7
C6B—C5B—C7B	121.4 (2)	N3C—C11C—H12C	110.7
C4B—C5B—C7B	120.1 (2)	C10C—C11C—H12C	110.7
C1Bⁱⁱ—C6B—C5B	121.4 (2)	H13C—C11C—H12C	108.8
C1Bⁱⁱ—C6B—H4B	119.3	N3C—C12C—N2C	107.90 (19)
C5B—C6B—H4B	119.3	N3C—C12C—C1C	110.8 (2)
N1B—C7B—C5B	123.0 (2)	N2C—C12C—C1C	113.55 (19)
N1B—C7B—H5B	118.5	N3C—C12C—H14C	108.1
C5B—C7B—H5B	118.5	N2C—C12C—H14C	108.1
N1B—C8B—C9B	110.99 (19)	C1C—C12C—H14C	108.1

C6A—C1A—C2A—C3A	−1.1 (3)	C12B—N2B—C10B—C11B	−31.3 (2)
C12Aⁱ—C1A—C2A—C3A	−177.6 (2)	C12B—N3B—C11B—C10B	11.5 (3)
C1A—C2A—C3A—C4A	1.0 (4)	N2B—C10B—C11B—N3B	12.3 (3)
C2A—C3A—C4A—C5A	0.3 (4)	C11B—N3B—C12B—N2B	−31.0 (2)
C3A—C4A—C5A—C6A	−1.5 (4)	C11B—N3B—C12B—C1B	−153.9 (2)
C3A—C4A—C5A—C7A	177.7 (2)	C10B—N2B—C12B—N3B	39.3 (2)
C4A—C5A—C6A—C1A	1.3 (3)	C9B—N2B—C12B—N3B	164.60 (18)
C7A—C5A—C6A—C1A	−177.9 (2)	C10B—N2B—C12B—C1B	161.74 (18)
C2A—C1A—C6A—C5A	0.0 (3)	C9B—N2B—C12B—C1B	−73.0 (2)
C12Aⁱ—C1A—C6A—C5A	176.6 (2)	C6Bⁱⁱ—C1B—C12B—N3B	79.3 (3)
C8A—N1A—C7A—C5A	179.3 (2)	C2B—C1B—C12B—N3B	−97.5 (2)
C6A—C5A—C7A—N1A	13.0 (4)	C6Bⁱⁱ—C1B—C12B—N2B	−38.6 (3)
C4A—C5A—C7A—N1A	−166.2 (2)	C2B—C1B—C12B—N2B	144.5 (2)
C7A—N1A—C8A—C9A	123.4 (2)	C6C—C1C—C2C—C3C	0.1 (4)
C10A—N2A—C9A—C8A	−67.1 (2)	C12C—C1C—C2C—C3C	−178.2 (2)
C12A—N2A—C9A—C8A	174.93 (18)	C1C—C2C—C3C—C4C	−1.0 (4)
N1A—C8A—C9A—N2A	−63.2 (3)	C2C—C3C—C4C—C5C	1.0 (4)
C9A—N2A—C10A—C11A	−158.55 (19)	C6C—C5C—C4C—C3C	0.0 (4)
C12A—N2A—C10A—C11A	−34.9 (2)	C7Cⁱⁱⁱ—C5C—C4C—C3C	−179.2 (2)
C12A—N3A—C11A—C10A	7.8 (3)	C2C—C1C—C6C—C5C	0.8 (3)
N2A—C10A—C11A—N3A	16.8 (3)	C12C—C1C—C6C—C5C	179.2 (2)
C11A—N3A—C12A—N2A	−29.8 (2)	C4C—C5C—C6C—C1C	−0.9 (4)
C11A—N3A—C12A—C1Aⁱ	−153.1 (2)	C7Cⁱⁱⁱ—C5C—C6C—C1C	178.3 (2)
C9A—N2A—C12A—N3A	164.32 (18)	C8C—N1C—C7C—C5Cⁱⁱⁱ	−178.7 (2)
C10A—N2A—C12A—N3A	40.7 (2)	C7C—N1C—C8C—C9C	125.3 (2)
C9A—N2A—C12A—C1Aⁱ	−73.5 (2)	C12C—N2C—C9C—C8C	−83.3 (3)
C10A—N2A—C12A—C1Aⁱ	162.86 (19)	C10C—N2C—C9C—C8C	156.3 (2)
C6Bⁱⁱ—C1B—C2B—C3B	−0.7 (3)	N1C—C8C—C9C—N2C	−70.0 (3)
C12B—C1B—C2B—C3B	176.2 (2)	C9C—N2C—C10C—C11C	104.5 (3)
C1B—C2B—C3B—C4Bⁱⁱ	0.2 (4)	C12C—N2C—C10C—C11C	−21.5 (3)
C3Bⁱⁱ—C4B—C5B—C6B	−1.1 (3)	C12C—N3C—C11C—C10C	−33.4 (3)
C3Bⁱⁱ—C4B—C5B—C7B	174.5 (2)	N2C—C10C—C11C—N3C	34.2 (3)
C4B—C5B—C6B—C1Bⁱⁱ	1.6 (3)	C11C—N3C—C12C—N2C	19.8 (3)
C7B—C5B—C6B—C1Bⁱⁱ	−174.0 (2)	C11C—N3C—C12C—C1C	144.7 (2)
C8B—N1B—C7B—C5B	175.16 (19)	C9C—N2C—C12C—N3C	−123.9 (2)
C6B—C5B—C7B—N1B	11.5 (3)	C10C—N2C—C12C—N3C	1.2 (3)
C4B—C5B—C7B—N1B	−164.0 (2)	C9C—N2C—C12C—C1C	112.9 (2)
C7B—N1B—C8B—C9B	131.4 (2)	C10C—N2C—C12C—C1C	−122.0 (2)
C10B—N2B—C9B—C8B	−65.5 (2)	C6C—C1C—C12C—N3C	−104.6 (3)
C12B—N2B—C9B—C8B	174.61 (18)	C2C—C1C—C12C—N3C	73.8 (3)
N1B—C8B—C9B—N2B	−65.1 (2)	C6C—C1C—C12C—N2C	17.1 (3)
C9B—N2B—C10B—C11B	−156.4 (2)	C2C—C1C—C12C—N2C	−164.6 (2)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3AN···N3B^iv	0.81 (2)	2.84 (3)	3.582 (3)	152 (2)
N3B—H3BN···N1A^v	0.88 (2)	2.66 (2)	3.411 (3)	145 (2)
N3C—H3CN···N3A^vi	1.01 (3)	2.26 (3)	3.251 (3)	165 (3)

Symmetry codes: (iv) −x+1, −y, −z+2; (v) x−1, y, z; (vi) x, y, z−1.

3,6,9,17,20,23-hexa-azapentacyclo(23.3.1.1^11,15.0^2,6.0^16,20)triaconta -1(29),9,11,13,15(30),23,25,27-octaene (dienI) top

Crystal data top

C₂₄H₃₀N₆	Z = 2
M_r = 402.54	F(000) = 432
Triclinic, P1	D_x = 1.202 Mg m⁻³
Hall symbol: -P1	Melting point: 452.65 K
a = 9.8236 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9337 (3) Å	Cell parameters from 6041 reflections
c = 12.1088 (4) Å	θ = 2.6–21.0°
α = 92.421 (3)°	µ = 0.07 mm⁻¹
β = 98.770 (3)°	T = 293 K
γ = 107.011 (3)°	Needle, colourless
V = 1112.00 (6) Å³	0.7 × 0.2 × 0.2 mm

Data collection top

Bruker AXS Smart diffractometer	5093 independent reflections
Radiation source: fine-focus sealed tube	2892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: empirical (using intensity measurements) SADABS-2007/4	h = −12→12
T_min = 0.944, T_max = 1.000	k = −12→12
24298 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0616P)² + 0.1036P] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max < 0.001
5093 reflections	Δρ_max = 0.15 e Å⁻³
280 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (2)

Special details top

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

	x	y	z	U_iso*/U_eq
N1A	0.59739 (15)	0.37365 (14)	0.84376 (12)	0.0537 (4)
N2A	0.28090 (14)	0.23121 (12)	0.82664 (10)	0.0482 (3)
N3A	0.07047 (19)	0.14924 (17)	0.90088 (18)	0.0717 (5)
C1A	0.86361 (17)	0.60584 (16)	1.14389 (13)	0.0477 (4)
C2A	0.96506 (18)	0.54808 (19)	1.19875 (15)	0.0598 (5)
H1A	1.0301	0.5982	1.2613	0.072*
C3A	0.9700 (2)	0.4170 (2)	1.16102 (17)	0.0685 (5)
H2A	1.0370	0.3783	1.1990	0.082*
C4A	0.8761 (2)	0.34363 (19)	1.06750 (16)	0.0612 (5)
H3A	0.8808	0.2557	1.0420	0.073*
C5A	0.77433 (17)	0.39923 (16)	1.01062 (13)	0.0479 (4)
C6A	0.76823 (17)	0.52949 (16)	1.05092 (13)	0.0479 (4)
H4A	0.6985	0.5664	1.0147	0.057*
C7A	0.67695 (19)	0.32152 (17)	0.90881 (15)	0.0544 (4)
H5A	0.6740	0.2285	0.8915	0.065*
C8A	0.50560 (19)	0.28601 (18)	0.74533 (15)	0.0597 (5)
H6A	0.5068	0.1892	0.7505	0.072*
H7A	0.5437	0.3187	0.6787	0.072*
C9A	0.35187 (19)	0.29036 (18)	0.73463 (14)	0.0562 (4)
H9A	0.3516	0.3877	0.7317	0.067*
H8A	0.2968	0.2382	0.6645	0.067*
C10A	0.2563 (2)	0.07956 (17)	0.83051 (16)	0.0646 (5)
H11A	0.3424	0.0602	0.8677	0.078*
H10A	0.2286	0.0312	0.7555	0.078*
C11A	0.1338 (2)	0.03370 (18)	0.89737 (16)	0.0677 (5)
H12A	0.0621	−0.0524	0.8612	0.081*
H13A	0.1706	0.0165	0.9727	0.081*
C12A	0.13614 (17)	0.24632 (16)	0.82295 (14)	0.0539 (4)
H14A	0.0805	0.2158	0.7471	0.065*
H3AN	0.095 (3)	0.189 (3)	0.967 (2)	0.111 (10)*
N1B	0.30522 (14)	0.65258 (15)	0.48635 (11)	0.0543 (4)
N2B	0.52391 (13)	0.76335 (12)	0.69058 (10)	0.0446 (3)
N3B	0.68840 (15)	0.73588 (18)	0.84043 (12)	0.0563 (4)
C1B	0.23332 (15)	0.23059 (16)	0.34292 (13)	0.0445 (4)
C2B	0.11263 (17)	0.12944 (18)	0.36607 (15)	0.0553 (4)
H1B	0.0871	0.0377	0.3323	0.066*
C3B	0.02994 (18)	0.1637 (2)	0.43883 (16)	0.0623 (5)
H2B	−0.0508	0.0951	0.4538	0.075*
C4B	0.06651 (17)	0.29813 (19)	0.48882 (14)	0.0558 (4)
H3B	0.0103	0.3202	0.5378	0.067*
C5B	0.18682 (16)	0.40270 (17)	0.46749 (13)	0.0468 (4)
C6B	0.26959 (16)	0.36580 (16)	0.39439 (12)	0.0456 (4)
H4B	0.3511	0.4340	0.3800	0.055*
C7B	0.22151 (17)	0.54650 (18)	0.52017 (13)	0.0514 (4)
H5B	0.1796	0.5604	0.5819	0.062*
C8B	0.33063 (18)	0.78997 (18)	0.54635 (15)	0.0567 (4)
H7B	0.2680	0.7809	0.6020	0.068*
H6B	0.3077	0.8548	0.4941	0.068*
C9B	0.48637 (18)	0.84825 (16)	0.60338 (14)	0.0529 (4)
H9B	0.5485	0.8524	0.5478	0.063*
H8B	0.5035	0.9439	0.6360	0.063*
C10B	0.4551 (2)	0.76651 (19)	0.78873 (14)	0.0613 (5)
H10B	0.3594	0.6983	0.7766	0.074*
H11B	0.4469	0.8598	0.8059	0.074*
C11B	0.5536 (2)	0.7288 (2)	0.88196 (15)	0.0707 (5)
H13B	0.5730	0.7948	0.9479	0.085*
H12B	0.5091	0.6343	0.9018	0.085*
C12B	0.67855 (16)	0.80594 (16)	0.73740 (13)	0.0485 (4)
H14B	0.7122	0.9084	0.7568	0.058*
H3BN	0.686 (2)	0.648 (2)	0.8194 (16)	0.076 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0587 (9)	0.0509 (8)	0.0550 (9)	0.0191 (7)	0.0163 (7)	−0.0008 (7)
N2A	0.0584 (8)	0.0430 (7)	0.0466 (8)	0.0193 (6)	0.0113 (6)	0.0036 (6)
N3A	0.0757 (11)	0.0524 (10)	0.0916 (15)	0.0161 (8)	0.0313 (10)	0.0180 (10)
C1A	0.0485 (9)	0.0509 (9)	0.0488 (10)	0.0185 (8)	0.0145 (8)	0.0125 (8)
C2A	0.0564 (11)	0.0745 (12)	0.0551 (11)	0.0278 (9)	0.0120 (9)	0.0126 (9)
C3A	0.0675 (12)	0.0816 (14)	0.0720 (13)	0.0450 (11)	0.0120 (11)	0.0177 (11)
C4A	0.0722 (12)	0.0569 (10)	0.0724 (13)	0.0388 (10)	0.0255 (11)	0.0168 (10)
C5A	0.0537 (10)	0.0458 (9)	0.0530 (10)	0.0213 (8)	0.0216 (8)	0.0122 (8)
C6A	0.0524 (10)	0.0463 (9)	0.0523 (10)	0.0227 (7)	0.0139 (8)	0.0118 (8)
C7A	0.0671 (11)	0.0431 (9)	0.0629 (11)	0.0245 (8)	0.0263 (10)	0.0052 (8)
C8A	0.0688 (12)	0.0593 (11)	0.0537 (11)	0.0199 (9)	0.0198 (9)	−0.0051 (9)
C9A	0.0680 (12)	0.0586 (10)	0.0443 (10)	0.0220 (9)	0.0116 (8)	0.0017 (8)
C10A	0.0847 (13)	0.0462 (10)	0.0644 (12)	0.0248 (9)	0.0094 (10)	−0.0006 (9)
C11A	0.0823 (14)	0.0484 (10)	0.0668 (12)	0.0125 (9)	0.0099 (11)	0.0078 (9)
C12A	0.0537 (10)	0.0520 (10)	0.0541 (10)	0.0148 (8)	0.0069 (8)	0.0027 (8)
N1B	0.0529 (9)	0.0599 (9)	0.0538 (9)	0.0223 (7)	0.0109 (7)	0.0028 (7)
N2B	0.0456 (8)	0.0471 (7)	0.0462 (8)	0.0193 (6)	0.0127 (6)	0.0069 (6)
N3B	0.0595 (9)	0.0673 (10)	0.0453 (8)	0.0239 (8)	0.0096 (7)	0.0058 (8)
C1B	0.0386 (9)	0.0473 (9)	0.0463 (9)	0.0123 (7)	0.0043 (7)	0.0077 (7)
C2B	0.0448 (10)	0.0515 (10)	0.0668 (11)	0.0119 (8)	0.0051 (9)	0.0108 (8)
C3B	0.0431 (10)	0.0653 (12)	0.0810 (13)	0.0137 (8)	0.0188 (9)	0.0248 (10)
C4B	0.0448 (10)	0.0758 (12)	0.0576 (11)	0.0281 (9)	0.0178 (8)	0.0224 (9)
C5B	0.0414 (9)	0.0600 (10)	0.0433 (9)	0.0215 (8)	0.0068 (7)	0.0108 (8)
C6B	0.0380 (8)	0.0518 (10)	0.0480 (9)	0.0123 (7)	0.0116 (7)	0.0098 (8)
C7B	0.0503 (10)	0.0692 (12)	0.0439 (10)	0.0300 (9)	0.0116 (8)	0.0073 (9)
C8B	0.0576 (11)	0.0611 (11)	0.0593 (11)	0.0309 (8)	0.0081 (9)	0.0059 (9)
C9B	0.0599 (11)	0.0469 (9)	0.0564 (10)	0.0219 (8)	0.0118 (8)	0.0080 (8)
C10B	0.0690 (12)	0.0689 (11)	0.0588 (11)	0.0343 (9)	0.0228 (9)	0.0088 (9)
C11B	0.0674 (12)	0.1010 (15)	0.0522 (11)	0.0343 (11)	0.0175 (10)	0.0105 (10)
C12B	0.0496 (10)	0.0443 (9)	0.0500 (10)	0.0128 (7)	0.0079 (8)	0.0001 (7)

Geometric parameters (Å, º) top

N1A—C7A	1.258 (2)	N1B—C7B	1.260 (2)
N1A—C8A	1.455 (2)	N1B—C8B	1.454 (2)
N2A—C9A	1.458 (2)	N2B—C9B	1.4494 (19)
N2A—C10A	1.4582 (19)	N2B—C10B	1.4578 (19)
N2A—C12A	1.467 (2)	N2B—C12B	1.4660 (19)
N3A—C11A	1.459 (2)	N3B—C12B	1.458 (2)
N3A—C12A	1.461 (2)	N3B—C11B	1.471 (2)
N3A—H3AN	0.84 (2)	N3B—H3BN	0.891 (19)
C1A—C6A	1.382 (2)	C1B—C6B	1.379 (2)
C1A—C2A	1.389 (2)	C1B—C2B	1.386 (2)
C1A—C12Aⁱ	1.505 (2)	C1B—C12Bⁱⁱ	1.496 (2)
C2A—C3A	1.378 (2)	C2B—C3B	1.381 (2)
C2A—H1A	0.9300	C2B—H1B	0.9300
C3A—C4A	1.372 (3)	C3B—C4B	1.365 (2)
C3A—H2A	0.9300	C3B—H2B	0.9300
C4A—C5A	1.387 (2)	C4B—C5B	1.393 (2)
C4A—H3A	0.9300	C4B—H3B	0.9300
C5A—C6A	1.385 (2)	C5B—C6B	1.395 (2)
C5A—C7A	1.469 (2)	C5B—C7B	1.461 (2)
C6A—H4A	0.9300	C6B—H4B	0.9300
C7A—H5A	0.9300	C7B—H5B	0.9300
C8A—C9A	1.509 (2)	C8B—C9B	1.509 (2)
C8A—H6A	0.9700	C8B—H7B	0.9700
C8A—H7A	0.9700	C8B—H6B	0.9700
C9A—H9A	0.9700	C9B—H9B	0.9700
C9A—H8A	0.9700	C9B—H8B	0.9700
C10A—C11A	1.523 (3)	C10B—C11B	1.505 (2)
C10A—H11A	0.9700	C10B—H10B	0.9700
C10A—H10A	0.9700	C10B—H11B	0.9700
C11A—H12A	0.9700	C11B—H13B	0.9700
C11A—H13A	0.9700	C11B—H12B	0.9700
C12A—C1Aⁱ	1.505 (2)	C12B—C1Bⁱⁱ	1.496 (2)
C12A—H14A	0.9800	C12B—H14B	0.9800

C7A—N1A—C8A	118.63 (14)	C7B—N1B—C8B	117.87 (14)
C9A—N2A—C10A	114.31 (13)	C9B—N2B—C10B	114.97 (12)
C9A—N2A—C12A	113.95 (13)	C9B—N2B—C12B	113.76 (12)
C10A—N2A—C12A	103.39 (13)	C10B—N2B—C12B	103.79 (12)
C11A—N3A—C12A	105.64 (15)	C12B—N3B—C11B	104.68 (13)
C11A—N3A—H3AN	107.2 (17)	C12B—N3B—H3BN	105.8 (12)
C12A—N3A—H3AN	110.0 (17)	C11B—N3B—H3BN	108.1 (12)
C6A—C1A—C2A	118.72 (15)	C6B—C1B—C2B	118.73 (15)
C6A—C1A—C12Aⁱ	119.50 (14)	C6B—C1B—C12Bⁱⁱ	120.67 (13)
C2A—C1A—C12Aⁱ	121.56 (15)	C2B—C1B—C12Bⁱⁱ	120.60 (15)
C3A—C2A—C1A	120.43 (17)	C3B—C2B—C1B	120.60 (16)
C3A—C2A—H1A	119.8	C3B—C2B—H1B	119.7
C1A—C2A—H1A	119.8	C1B—C2B—H1B	119.7
C4A—C3A—C2A	120.13 (17)	C4B—C3B—C2B	120.12 (16)
C4A—C3A—H2A	119.9	C4B—C3B—H2B	119.9
C2A—C3A—H2A	119.9	C2B—C3B—H2B	119.9
C3A—C4A—C5A	120.66 (16)	C3B—C4B—C5B	120.94 (15)
C3A—C4A—H3A	119.7	C3B—C4B—H3B	119.5
C5A—C4A—H3A	119.7	C5B—C4B—H3B	119.5
C6A—C5A—C4A	118.66 (16)	C4B—C5B—C6B	118.10 (15)
C6A—C5A—C7A	121.11 (15)	C4B—C5B—C7B	119.76 (15)
C4A—C5A—C7A	120.22 (15)	C6B—C5B—C7B	122.14 (14)
C1A—C6A—C5A	121.38 (15)	C1B—C6B—C5B	121.50 (14)
C1A—C6A—H4A	119.3	C1B—C6B—H4B	119.2
C5A—C6A—H4A	119.3	C5B—C6B—H4B	119.2
N1A—C7A—C5A	123.75 (15)	N1B—C7B—C5B	123.39 (15)
N1A—C7A—H5A	118.1	N1B—C7B—H5B	118.3
C5A—C7A—H5A	118.1	C5B—C7B—H5B	118.3
N1A—C8A—C9A	111.65 (13)	N1B—C8B—C9B	110.46 (12)
N1A—C8A—H6A	109.3	N1B—C8B—H7B	109.6
C9A—C8A—H6A	109.3	C9B—C8B—H7B	109.6
N1A—C8A—H7A	109.3	N1B—C8B—H6B	109.6
C9A—C8A—H7A	109.3	C9B—C8B—H6B	109.6
H6A—C8A—H7A	108.0	H7B—C8B—H6B	108.1
N2A—C9A—C8A	113.29 (14)	N2B—C9B—C8B	112.40 (13)
N2A—C9A—H9A	108.9	N2B—C9B—H9B	109.1
C8A—C9A—H9A	108.9	C8B—C9B—H9B	109.1
N2A—C9A—H8A	108.9	N2B—C9B—H8B	109.1
C8A—C9A—H8A	108.9	C8B—C9B—H8B	109.1
H9A—C9A—H8A	107.7	H9B—C9B—H8B	107.9
N2A—C10A—C11A	104.16 (13)	N2B—C10B—C11B	104.54 (13)
N2A—C10A—H11A	110.9	N2B—C10B—H10B	110.8
C11A—C10A—H11A	110.9	C11B—C10B—H10B	110.8
N2A—C10A—H10A	110.9	N2B—C10B—H11B	110.8
C11A—C10A—H10A	110.9	C11B—C10B—H11B	110.8
H11A—C10A—H10A	108.9	H10B—C10B—H11B	108.9
N3A—C11A—C10A	106.41 (14)	N3B—C11B—C10B	107.01 (14)
N3A—C11A—H12A	110.4	N3B—C11B—H13B	110.3
C10A—C11A—H12A	110.4	C10B—C11B—H13B	110.3
N3A—C11A—H13A	110.4	N3B—C11B—H12B	110.3
C10A—C11A—H13A	110.4	C10B—C11B—H12B	110.3
H12A—C11A—H13A	108.6	H13B—C11B—H12B	108.6
N3A—C12A—N2A	104.86 (13)	N3B—C12B—N2B	105.03 (12)
N3A—C12A—C1Aⁱ	110.33 (14)	N3B—C12B—C1Bⁱⁱ	112.94 (13)
N2A—C12A—C1Aⁱ	113.97 (13)	N2B—C12B—C1Bⁱⁱ	112.54 (13)
N3A—C12A—H14A	109.2	N3B—C12B—H14B	108.7
N2A—C12A—H14A	109.2	N2B—C12B—H14B	108.7
C1Aⁱ—C12A—H14A	109.2	C1Bⁱⁱ—C12B—H14B	108.7

C6A—C1A—C2A—C3A	−0.1 (2)	C6B—C1B—C2B—C3B	0.3 (2)
C12Aⁱ—C1A—C2A—C3A	−174.68 (15)	C12Bⁱⁱ—C1B—C2B—C3B	−178.95 (14)
C1A—C2A—C3A—C4A	1.2 (3)	C1B—C2B—C3B—C4B	0.0 (3)
C2A—C3A—C4A—C5A	−0.7 (3)	C2B—C3B—C4B—C5B	0.1 (3)
C3A—C4A—C5A—C6A	−0.8 (2)	C3B—C4B—C5B—C6B	−0.6 (2)
C3A—C4A—C5A—C7A	178.33 (16)	C3B—C4B—C5B—C7B	178.59 (15)
C2A—C1A—C6A—C5A	−1.5 (2)	C2B—C1B—C6B—C5B	−0.8 (2)
C12Aⁱ—C1A—C6A—C5A	173.23 (14)	C12Bⁱⁱ—C1B—C6B—C5B	178.48 (13)
C4A—C5A—C6A—C1A	1.9 (2)	C4B—C5B—C6B—C1B	0.9 (2)
C7A—C5A—C6A—C1A	−177.21 (14)	C7B—C5B—C6B—C1B	−178.21 (14)
C8A—N1A—C7A—C5A	179.92 (14)	C8B—N1B—C7B—C5B	180.00 (13)
C6A—C5A—C7A—N1A	10.1 (2)	C4B—C5B—C7B—N1B	−162.76 (15)
C4A—C5A—C7A—N1A	−169.01 (15)	C6B—C5B—C7B—N1B	16.4 (2)
C7A—N1A—C8A—C9A	130.93 (16)	C7B—N1B—C8B—C9B	114.46 (17)
C10A—N2A—C9A—C8A	−66.68 (18)	C10B—N2B—C9B—C8B	−68.19 (18)
C12A—N2A—C9A—C8A	174.72 (12)	C12B—N2B—C9B—C8B	172.33 (12)
N1A—C8A—C9A—N2A	−64.07 (18)	N1B—C8B—C9B—N2B	−64.90 (18)
C9A—N2A—C10A—C11A	−157.90 (14)	C9B—N2B—C10B—C11B	−156.11 (14)
C12A—N2A—C10A—C11A	−33.47 (16)	C12B—N2B—C10B—C11B	−31.23 (17)
C12A—N3A—C11A—C10A	9.4 (2)	C12B—N3B—C11B—C10B	12.09 (19)
N2A—C10A—C11A—N3A	15.08 (19)	N2B—C10B—C11B—N3B	12.0 (2)
C11A—N3A—C12A—N2A	−30.59 (19)	C11B—N3B—C12B—N2B	−31.79 (17)
C11A—N3A—C12A—C1Aⁱ	−153.72 (15)	C11B—N3B—C12B—C1Bⁱⁱ	−154.80 (14)
C9A—N2A—C12A—N3A	164.95 (14)	C9B—N2B—C12B—N3B	165.42 (12)
C10A—N2A—C12A—N3A	40.29 (17)	C10B—N2B—C12B—N3B	39.77 (15)
C9A—N2A—C12A—C1Aⁱ	−74.30 (17)	C9B—N2B—C12B—C1Bⁱⁱ	−71.32 (16)
C10A—N2A—C12A—C1Aⁱ	161.04 (14)	C10B—N2B—C12B—C1Bⁱⁱ	163.03 (13)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3B—H3BN···N1A	0.891 (19)	2.652 (19)	3.448 (2)	149.3 (16)
N3A—H3AN···N3Bⁱ	0.84 (2)	2.82 (2)	3.547 (3)	146 (2)

Symmetry code: (i) −x+1, −y+1, −z+2.

'3,6,9,17,20,23-hexa-azapentacyclo(23.3.1.1^11,15.0^2,6.0^16,20)triaconta -1(29),9,11,13,15(30),23,25,27-octaene (dienSOLV) top

Crystal data top

3(C₂₄H₃₀N₆)·2(C₂H₃N)·0.68(O)	Z = 1
M_r = 1300.67	F(000) = 697.6
Triclinic, P1	D_x = 1.185 Mg m⁻³
Hall symbol: -P1	Melting point: 417.15 K
a = 12.2369 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5634 (13) Å	Cell parameters from 1136 reflections
c = 13.0094 (14) Å	θ = 2.2–19.5°
α = 87.378 (3)°	µ = 0.07 mm⁻¹
β = 68.153 (3)°	T = 293 K
γ = 79.441 (3)°	Plate, colourless
V = 1824.4 (3) Å³	0.23 × 0.15 × 0.03 mm

Data collection top

Bruker AXS Smart diffractometer	2729 reflections with I > 2σ(I)
ω scans	R_int = 0.101
Absorption correction: empirical (using intensity measurements) SADABS-2007/4	θ_max = 27.5°, θ_min = 1.7°
T_min = 0.850, T_max = 1.000	h = −15→15
22307 measured reflections	k = −15→16
8389 independent reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0464P)²] where P = (F_o² + 2F_c²)/3
S = 0.87	(Δ/σ)_max = 0.046
8389 reflections	Δρ_max = 0.20 e Å⁻³
449 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (8)

Special details top

Experimental. The anisotropic refinement of the thermal parameters of the disordered methyl C70 atom in SOLV was attempted, but it was judged negatively: at the end of this refinement, the U_eq value of C701 was twice the corresponding value of C702 (0.22131 versus. 0.11774 Å²), and SHELX suggested to split the C701 atom into two new positions as its thermal ellipsoid resulted to be enormously elongated. Therefore, this refinement was discarded. We have also tried to constrain the ADP values of C701 and C702 to be equal with the EADP instruction: at the end of this refinement SHELX didn't provide any suggestion for the splitting (nor for C701 or C702), but the refined site occupation factors strongly correlated with ADP's (max. correlation coefficient: -0.927). This was not surprising, as it is well known that thermal motion may easily correlate with disorder: low-temperature experiments would be needed to deeply investigate the disorder in this DIEN solvated structure, at the same time provided unbiased (or, probably, less-biased) estimation of the solvent thermal motion. Considering the quality of the current RT data set, we believe that any attempt to describe as anisotropic the thermal motion of this methyl carbon would be quite dangerous, due to the correlations among the ADP's and the corresponding occupation coefficients that model the disorder. Therefore, we adopted an isotropic model for the C70 disordered atom.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedCal angle Cetween two l.s. planes) aCe estimated using the full covaCiance matCix. The cell e.s.d.'s aCe taken into account individually in the estimation of e.s.d.'s in distances, angles and toCsion angles; coCCelations Cetween e.s.d.'s in cell paCameteCs aCe only used when they aCe defined Cy cCystal symmetCy. An appCoximate (isotCopic) tCeatment of cell e.s.d.'s is used foC estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.4090 (9)	0.1166 (9)	0.1751 (8)	0.166 (6)*	0.342 (7)
C701	0.5540 (12)	0.903 (2)	0.2732 (14)	0.100 (5)*	0.46 (3)
H70A	0.5871	0.8881	0.1948	0.149*	0.46 (3)
H70B	0.6099	0.8687	0.3056	0.149*	0.46 (3)
H70C	0.5384	0.9799	0.2867	0.149*	0.46 (3)
C702	0.5758 (8)	0.8506 (14)	0.2417 (9)	0.082 (4)*	0.54 (3)
H70D	0.6028	0.7786	0.2100	0.122*	0.54 (3)
H70E	0.6245	0.8639	0.2814	0.122*	0.54 (3)
H70F	0.5819	0.9020	0.1838	0.122*	0.54 (3)
C71	0.4457 (4)	0.8625 (4)	0.3211 (3)	0.0905 (14)
N90	0.3527 (4)	0.8533 (4)	0.3691 (3)	0.1233 (15)
C3B	0.4258 (3)	0.4065 (3)	−0.0520 (3)	0.0769 (11)
H2B	0.5018	0.4114	−0.0547	0.092*
C3C	0.9039 (4)	0.8907 (3)	0.5562 (3)	0.0661 (10)
H2C	0.8968	0.9580	0.5875	0.079*
C3A	0.3241 (3)	0.8558 (3)	−0.3482 (3)	0.0768 (11)
H2A	0.3647	0.8192	−0.4161	0.092*
C4B	0.3780 (3)	0.4694 (3)	−0.1199 (3)	0.0697 (10)
H3B	0.4213	0.5173	−0.1676	0.084*
C4C	1.0157 (3)	0.8297 (3)	0.5013 (3)	0.0602 (9)
H3C	1.0839	0.8565	0.4952	0.072*
C4A	0.2422 (3)	0.9487 (3)	−0.3404 (2)	0.0652 (10)
H3A	0.2278	0.9751	−0.4030	0.078*
C5B	0.2656 (3)	0.4614 (3)	−0.1174 (2)	0.0542 (9)
C5C	1.0272 (3)	0.7284 (2)	0.4550 (2)	0.0462 (8)
C5A	0.1812 (3)	1.0033 (2)	−0.2396 (2)	0.0462 (8)
C6B	0.2007 (3)	0.3918 (2)	−0.0434 (2)	0.0539 (9)
H4B	0.1245	0.3873	−0.0403	0.065*
C6C	0.9246 (3)	0.6909 (2)	0.4653 (2)	0.0487 (8)
H4C	0.9315	0.6231	0.4351	0.058*
C6A	0.2030 (3)	0.9610 (2)	−0.1474 (2)	0.0481 (8)
H4A	0.1606	0.9965	−0.0792	0.058*
C1B	0.2481 (3)	0.3290 (3)	0.0257 (2)	0.0514 (8)
C1C	0.8113 (3)	0.7511 (3)	0.5191 (2)	0.0491 (8)
C1A	0.2850 (3)	0.8684 (2)	−0.1532 (2)	0.0482 (8)
C2B	0.3613 (3)	0.3362 (3)	0.0203 (3)	0.0644 (10)
H1B	0.3944	0.2935	0.0655	0.077*
C2C	0.8030 (3)	0.8518 (3)	0.5644 (3)	0.0609 (9)
H1C	0.7280	0.8935	0.6009	0.073*
C2A	0.3463 (3)	0.8163 (3)	−0.2556 (3)	0.0656 (10)
H1A	0.4030	0.7540	−0.2621	0.079*
C12B	0.1794 (3)	0.2508 (3)	0.1027 (2)	0.0527 (8)
H14B	0.2147	0.2297	0.1587	0.063*
C12C	0.7006 (3)	0.7099 (2)	0.5278 (2)	0.0523 (8)
H14C	0.6309	0.7561	0.5812	0.063*
C12A	0.3131 (3)	0.8308 (3)	−0.0529 (2)	0.0582 (9)
H14A	0.3642	0.7590	−0.0694	0.070*
C11B	0.0759 (3)	0.1107 (3)	0.1205 (3)	0.0769 (11)
H12B	0.1008	0.0510	0.1615	0.092*
H13B	0.0342	0.0848	0.0789	0.092*
C11C	0.6001 (3)	0.6319 (3)	0.4420 (3)	0.0715 (11)
H12C	0.6212	0.5878	0.3758	0.086*
H13C	0.5189	0.6711	0.4609	0.086*
C11A	0.3538 (3)	0.8873 (3)	0.0945 (3)	0.0839 (12)
H13A	0.3312	0.9559	0.1347	0.101*
H12A	0.4251	0.8470	0.1035	0.101*
C10B	−0.0050 (3)	0.2019 (2)	0.1988 (2)	0.0522 (8)
H10B	−0.0846	0.2136	0.1966	0.063*
H11B	−0.0106	0.1864	0.2741	0.063*
C10C	0.6106 (3)	0.5613 (3)	0.5373 (3)	0.0676 (10)
H11C	0.5351	0.5713	0.6001	0.081*
H10C	0.6336	0.4854	0.5146	0.081*
C10A	0.2518 (3)	0.8227 (3)	0.1371 (3)	0.0739 (11)
H10A	0.2808	0.7489	0.1524	0.089*
H11A	0.1894	0.8562	0.2041	0.089*
C9B	0.0302 (3)	0.3753 (2)	0.2467 (2)	0.0560 (9)
H9B	0.0779	0.4311	0.2162	0.067*
H8B	0.0562	0.3392	0.3034	0.067*
C9C	0.6884 (3)	0.5873 (2)	0.6811 (2)	0.0554 (9)
H8C	0.6078	0.6213	0.7267	0.066*
H9C	0.7436	0.6259	0.6949	0.066*
C9A	0.1477 (3)	0.7349 (2)	0.0463 (2)	0.0577 (9)
H8A	0.2020	0.6676	0.0445	0.069*
H9A	0.1301	0.7368	−0.0207	0.069*
C8B	−0.1000 (3)	0.4278 (3)	0.2992 (2)	0.0633 (10)
H6B	−0.1491	0.3722	0.3233	0.076*
H7B	−0.1117	0.4708	0.3638	0.076*
C8C	0.7105 (3)	0.4713 (3)	0.7150 (3)	0.0638 (10)
H6C	0.6918	0.4693	0.7943	0.077*
H7C	0.6582	0.4313	0.6983	0.077*
C8A	0.0328 (3)	0.7359 (2)	0.1455 (2)	0.0590 (9)
H7A	−0.0003	0.6721	0.1426	0.071*
H6A	0.0492	0.7343	0.2130	0.071*
C7B	−0.2185 (3)	0.4745 (3)	0.1940 (3)	0.0595 (10)
H5B	−0.2513	0.4140	0.2248	0.071*
C7C	1.1475 (3)	0.6662 (3)	0.3964 (3)	0.0538 (9)
H5C	1.2132	0.6918	0.3987	0.065*
C7A	0.0951 (3)	1.1045 (2)	−0.2309 (3)	0.0515 (8)
H5A	0.0703	1.1232	−0.2897	0.062*
N2B	0.0515 (2)	0.29680 (19)	0.15904 (18)	0.0452 (6)
N2C	0.7029 (2)	0.59711 (19)	0.5653 (2)	0.0502 (7)
N2A	0.2071 (2)	0.8249 (2)	0.04661 (19)	0.0515 (7)
N3B	0.1803 (2)	0.1538 (2)	0.0451 (2)	0.0611 (8)
N3C	0.6830 (3)	0.7075 (2)	0.4234 (2)	0.0675 (9)
N3A	0.3755 (3)	0.9049 (3)	−0.0236 (3)	0.0801 (10)
N1B	−0.1367 (3)	0.4970 (2)	0.2201 (2)	0.0608 (8)
N1C	1.1651 (2)	0.5796 (2)	0.3431 (2)	0.0570 (7)
N1A	−0.0538 (2)	0.8334 (2)	0.1463 (2)	0.0556 (7)
H3BN	0.169 (3)	0.176 (2)	−0.016 (2)	0.071 (7)*
H3AN	0.340 (3)	0.968 (3)	−0.023 (3)	0.071 (7)*
H3CN	0.753 (3)	0.678 (2)	0.371 (2)	0.071 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C71	0.091 (3)	0.126 (4)	0.075 (3)	−0.053 (3)	−0.042 (3)	0.036 (3)
N90	0.109 (3)	0.182 (4)	0.086 (3)	−0.064 (3)	−0.030 (2)	0.017 (3)
C3B	0.047 (2)	0.094 (3)	0.086 (3)	−0.024 (2)	−0.014 (2)	−0.004 (2)
C3C	0.093 (3)	0.042 (2)	0.065 (2)	−0.022 (2)	−0.028 (2)	0.0073 (18)
C3A	0.084 (3)	0.078 (3)	0.044 (2)	0.008 (2)	−0.006 (2)	−0.004 (2)
C4B	0.050 (2)	0.068 (3)	0.079 (3)	−0.0232 (19)	−0.004 (2)	0.002 (2)
C4C	0.076 (3)	0.057 (2)	0.057 (2)	−0.030 (2)	−0.030 (2)	0.0186 (18)
C4A	0.077 (3)	0.072 (3)	0.037 (2)	−0.004 (2)	−0.0151 (18)	0.0079 (18)
C5B	0.054 (2)	0.052 (2)	0.049 (2)	−0.0146 (18)	−0.0071 (17)	−0.0021 (17)
C5C	0.057 (2)	0.043 (2)	0.0423 (18)	−0.0174 (17)	−0.0193 (16)	0.0146 (15)
C5A	0.0466 (18)	0.049 (2)	0.0423 (19)	−0.0074 (16)	−0.0166 (15)	0.0043 (16)
C6B	0.0476 (19)	0.058 (2)	0.054 (2)	−0.0156 (17)	−0.0133 (17)	−0.0014 (17)
C6C	0.054 (2)	0.0449 (19)	0.0483 (19)	−0.0119 (17)	−0.0192 (16)	0.0059 (16)
C6A	0.053 (2)	0.050 (2)	0.0385 (18)	−0.0085 (17)	−0.0137 (15)	0.0016 (16)
C1B	0.0417 (19)	0.059 (2)	0.051 (2)	−0.0123 (17)	−0.0112 (16)	−0.0043 (17)
C1C	0.050 (2)	0.046 (2)	0.0465 (19)	−0.0076 (17)	−0.0146 (16)	0.0097 (16)
C1A	0.0444 (18)	0.050 (2)	0.0427 (19)	−0.0039 (16)	−0.0103 (15)	0.0017 (16)
C2B	0.048 (2)	0.079 (3)	0.063 (2)	−0.017 (2)	−0.0148 (18)	0.001 (2)
C2C	0.073 (3)	0.041 (2)	0.058 (2)	−0.0033 (19)	−0.0171 (19)	0.0072 (17)
C2A	0.056 (2)	0.067 (2)	0.055 (2)	0.0089 (18)	−0.0085 (18)	0.0009 (19)
C12B	0.050 (2)	0.064 (2)	0.0466 (19)	−0.0125 (17)	−0.0207 (16)	0.0060 (18)
C12C	0.0436 (19)	0.054 (2)	0.053 (2)	0.0022 (16)	−0.0153 (16)	−0.0012 (17)
C12A	0.056 (2)	0.062 (2)	0.055 (2)	−0.0054 (18)	−0.0213 (18)	0.0057 (18)
C11B	0.076 (3)	0.056 (2)	0.076 (2)	−0.016 (2)	0.000 (2)	−0.001 (2)
C11C	0.052 (2)	0.089 (3)	0.069 (2)	0.004 (2)	−0.0227 (19)	−0.019 (2)
C11A	0.089 (3)	0.103 (3)	0.074 (3)	−0.012 (3)	−0.049 (2)	0.004 (2)
C10B	0.055 (2)	0.057 (2)	0.0447 (19)	−0.0170 (17)	−0.0152 (16)	0.0037 (16)
C10C	0.055 (2)	0.073 (3)	0.078 (3)	−0.0160 (19)	−0.024 (2)	−0.006 (2)
C10A	0.088 (3)	0.076 (3)	0.059 (2)	−0.005 (2)	−0.034 (2)	0.010 (2)
C9B	0.069 (2)	0.058 (2)	0.0446 (19)	−0.0198 (18)	−0.0213 (17)	0.0019 (17)
C9C	0.0422 (19)	0.061 (2)	0.053 (2)	−0.0099 (16)	−0.0070 (16)	0.0078 (17)
C9A	0.068 (2)	0.043 (2)	0.056 (2)	0.0021 (18)	−0.0214 (18)	0.0021 (17)
C8B	0.077 (3)	0.059 (2)	0.045 (2)	−0.0115 (19)	−0.0127 (18)	−0.0027 (18)
C8C	0.046 (2)	0.068 (2)	0.064 (2)	−0.0141 (18)	−0.0046 (17)	0.0161 (19)
C8A	0.064 (2)	0.051 (2)	0.055 (2)	−0.0010 (18)	−0.0191 (18)	0.0102 (17)
C7B	0.065 (2)	0.046 (2)	0.053 (2)	−0.0169 (19)	−0.0030 (19)	−0.0010 (17)
C7C	0.046 (2)	0.061 (2)	0.059 (2)	−0.0221 (18)	−0.0210 (17)	0.0210 (19)
C7A	0.058 (2)	0.053 (2)	0.0438 (19)	−0.0115 (17)	−0.0193 (16)	0.0134 (17)
N2B	0.0472 (15)	0.0479 (16)	0.0397 (14)	−0.0147 (13)	−0.0126 (12)	0.0021 (13)
N2C	0.0422 (15)	0.0502 (17)	0.0561 (17)	−0.0095 (13)	−0.0158 (13)	0.0051 (13)
N2A	0.0607 (18)	0.0514 (17)	0.0419 (15)	−0.0024 (14)	−0.0223 (14)	0.0052 (13)
N3B	0.0609 (19)	0.0515 (19)	0.059 (2)	−0.0099 (15)	−0.0091 (16)	0.0007 (16)
N3C	0.059 (2)	0.079 (2)	0.065 (2)	−0.0058 (18)	−0.0282 (17)	0.0087 (17)
N3A	0.078 (2)	0.099 (3)	0.078 (2)	−0.027 (2)	−0.0426 (19)	0.019 (2)
N1B	0.067 (2)	0.0519 (18)	0.0567 (18)	−0.0127 (15)	−0.0145 (16)	0.0021 (14)
N1C	0.0441 (16)	0.0564 (18)	0.0660 (18)	−0.0113 (14)	−0.0158 (14)	0.0153 (15)
N1A	0.0585 (17)	0.0534 (18)	0.0500 (17)	−0.0043 (14)	−0.0180 (14)	0.0071 (14)

Geometric parameters (Å, º) top

C701—C71	1.418 (10)	C11B—N3B	1.470 (4)
C701—H70A	0.9600	C11B—C10B	1.506 (4)
C701—H70B	0.9600	C11B—H12B	0.9700
C701—H70C	0.9600	C11B—H13B	0.9700
C702—C71	1.526 (10)	C11C—N3C	1.462 (4)
C702—H70D	0.9600	C11C—C10C	1.522 (4)
C702—H70E	0.9600	C11C—H12C	0.9700
C702—H70F	0.9600	C11C—H13C	0.9700
C71—N90	1.100 (4)	C11A—N3A	1.472 (4)
C3B—C4B	1.378 (4)	C11A—C10A	1.529 (4)
C3B—C2B	1.385 (4)	C11A—H13A	0.9700
C3B—H2B	0.9300	C11A—H12A	0.9700
C3C—C2C	1.376 (4)	C10B—N2B	1.465 (3)
C3C—C4C	1.381 (4)	C10B—H10B	0.9700
C3C—H2C	0.9300	C10B—H11B	0.9700
C3A—C4A	1.373 (4)	C10C—N2C	1.456 (4)
C3A—C2A	1.381 (4)	C10C—H11C	0.9700
C3A—H2A	0.9300	C10C—H10C	0.9700
C4B—C5B	1.386 (4)	C10A—N2A	1.468 (4)
C4B—H3B	0.9300	C10A—H10A	0.9700
C4C—C5C	1.394 (4)	C10A—H11A	0.9700
C4C—H3C	0.9300	C9B—N2B	1.459 (3)
C4A—C5A	1.383 (4)	C9B—C8B	1.512 (4)
C4A—H3A	0.9300	C9B—H9B	0.9700
C5B—C6B	1.389 (4)	C9B—H8B	0.9700
C5B—C7Bⁱ	1.469 (4)	C9C—N2C	1.452 (3)
C5C—C6C	1.380 (4)	C9C—C8C	1.508 (4)
C5C—C7C	1.468 (4)	C9C—H8C	0.9700
C5A—C6A	1.386 (4)	C9C—H9C	0.9700
C5A—C7A	1.474 (4)	C9A—N2A	1.453 (4)
C6B—C1B	1.387 (4)	C9A—C8A	1.513 (4)
C6B—H4B	0.9300	C9A—H8A	0.9700
C6C—C1C	1.388 (4)	C9A—H9A	0.9700
C6C—H4C	0.9300	C8B—N1B	1.462 (4)
C6A—C1A	1.374 (4)	C8B—H6B	0.9700
C6A—H4A	0.9300	C8B—H7B	0.9700
C1B—C2B	1.379 (4)	C8C—N1Cⁱⁱ	1.459 (3)
C1B—C12B	1.504 (4)	C8C—H6C	0.9700
C1C—C2C	1.391 (4)	C8C—H7C	0.9700
C1C—C12C	1.501 (4)	C8A—N1A	1.463 (3)
C1A—C2A	1.387 (4)	C8A—H7A	0.9700
C1A—C12A	1.504 (4)	C8A—H6A	0.9700
C2B—H1B	0.9300	C7B—N1B	1.250 (4)
C2C—H1C	0.9300	C7B—C5Bⁱ	1.469 (4)
C2A—H1A	0.9300	C7B—H5B	0.9300
C12B—N3B	1.456 (4)	C7C—N1C	1.258 (4)
C12B—N2B	1.474 (3)	C7C—H5C	0.9300
C12B—H14B	0.9800	C7A—N1Aⁱⁱⁱ	1.263 (3)
C12C—N3C	1.455 (4)	C7A—H5A	0.9300
C12C—N2C	1.476 (3)	N3B—H3BN	0.88 (3)
C12C—H14C	0.9800	N3C—H3CN	0.90 (3)
C12A—N3A	1.451 (4)	N3A—H3AN	0.83 (3)
C12A—N2A	1.463 (3)	N1C—C8Cⁱⁱ	1.459 (3)
C12A—H14A	0.9800	N1A—C7Aⁱⁱⁱ	1.263 (3)

C71—C701—H70A	109.5	C10C—C11C—H12C	110.4
C71—C701—H70C	109.5	N3C—C11C—H13C	110.4
H70A—C701—H70C	109.5	C10C—C11C—H13C	110.4
C71—C701—H70B	109.4	H12C—C11C—H13C	108.6
H70A—C701—H70B	109.5	N3A—C11A—C10A	106.1 (3)
H70C—C701—H70B	109.5	N3A—C11A—H13A	110.5
C71—C702—H70D	109.5	C10A—C11A—H13A	110.5
C71—C702—H70E	109.5	N3A—C11A—H12A	110.5
H70D—C702—H70E	109.5	C10A—C11A—H12A	110.5
C71—C702—H70F	109.5	H13A—C11A—H12A	108.7
H70D—C702—H70F	109.5	N2B—C10B—C11B	104.8 (2)
H70E—C702—H70F	109.5	N2B—C10B—H10B	110.8
N90—C71—C701	164.2 (13)	C11B—C10B—H10B	110.8
N90—C71—C702	166.7 (9)	N2B—C10B—H11B	110.8
C701—C71—C702	28.9 (6)	C11B—C10B—H11B	110.8
C4B—C3B—C2B	120.3 (3)	H10B—C10B—H11B	108.9
C4B—C3B—H2B	119.9	N2C—C10C—C11C	105.0 (3)
C2B—C3B—H2B	119.8	N2C—C10C—H11C	110.8
C2C—C3C—C4C	119.8 (3)	C11C—C10C—H11C	110.8
C2C—C3C—H2C	120.1	N2C—C10C—H10C	110.8
C4C—C3C—H2C	120.1	C11C—C10C—H10C	110.8
C4A—C3A—C2A	120.3 (3)	H11C—C10C—H10C	108.8
C4A—C3A—H2A	119.9	N2A—C10A—C11A	104.5 (3)
C2A—C3A—H2A	119.9	N2A—C10A—H10A	110.9
C3B—C4B—C5B	120.1 (3)	C11A—C10A—H10A	110.9
C3B—C4B—H3B	119.9	N2A—C10A—H11A	110.9
C5B—C4B—H3B	119.9	C11A—C10A—H11A	110.9
C3C—C4C—C5C	120.5 (3)	H10A—C10A—H11A	108.9
C3C—C4C—H3C	119.7	N2B—C9B—C8B	112.6 (3)
C5C—C4C—H3C	119.7	N2B—C9B—H9B	109.1
C3A—C4A—C5A	120.1 (3)	C8B—C9B—H9B	109.1
C3A—C4A—H3A	119.9	N2B—C9B—H8B	109.1
C5A—C4A—H3A	119.9	C8B—C9B—H8B	109.1
C4B—C5B—C6B	119.2 (3)	H9B—C9B—H8B	107.8
C4B—C5B—C7Bⁱ	119.3 (3)	N2C—C9C—C8C	113.0 (3)
C6B—C5B—C7Bⁱ	121.5 (3)	N2C—C9C—H8C	109.0
C6C—C5C—C4C	118.5 (3)	C8C—C9C—H8C	109.0
C6C—C5C—C7C	122.4 (3)	N2C—C9C—H9C	109.0
C4C—C5C—C7C	119.1 (3)	C8C—C9C—H9C	109.0
C4A—C5A—C6A	118.6 (3)	H8C—C9C—H9C	107.8
C4A—C5A—C7A	120.5 (3)	N2A—C9A—C8A	113.5 (3)
C6A—C5A—C7A	120.9 (3)	N2A—C9A—H8A	108.9
C1B—C6B—C5B	120.8 (3)	C8A—C9A—H8A	108.9
C1B—C6B—H4B	119.6	N2A—C9A—H9A	108.9
C5B—C6B—H4B	119.6	C8A—C9A—H9A	108.9
C5C—C6C—C1C	122.1 (3)	H8A—C9A—H9A	107.7
C5C—C6C—H4C	119.0	N1B—C8B—C9B	110.4 (3)
C1C—C6C—H4C	119.0	N1B—C8B—H6B	109.6
C1A—C6A—C5A	122.4 (3)	C9B—C8B—H6B	109.6
C1A—C6A—H4A	118.8	N1B—C8B—H7B	109.6
C5A—C6A—H4A	118.8	C9B—C8B—H7B	109.6
C2B—C1B—C6B	119.2 (3)	H6B—C8B—H7B	108.1
C2B—C1B—C12B	120.1 (3)	N1Cⁱⁱ—C8C—C9C	110.8 (2)
C6B—C1B—C12B	120.7 (3)	N1Cⁱⁱ—C8C—H6C	109.5
C6C—C1C—C2C	118.0 (3)	C9C—C8C—H6C	109.5
C6C—C1C—C12C	121.4 (3)	N1Cⁱⁱ—C8C—H7C	109.5
C2C—C1C—C12C	120.6 (3)	C9C—C8C—H7C	109.5
C6A—C1A—C2A	117.8 (3)	H6C—C8C—H7C	108.1
C6A—C1A—C12A	120.4 (3)	N1A—C8A—C9A	110.1 (2)
C2A—C1A—C12A	121.6 (3)	N1A—C8A—H7A	109.6
C1B—C2B—C3B	120.3 (3)	C9A—C8A—H7A	109.6
C1B—C2B—H1B	119.8	N1A—C8A—H6A	109.6
C3B—C2B—H1B	119.8	C9A—C8A—H6A	109.6
C3C—C2C—C1C	121.1 (3)	H7A—C8A—H6A	108.2
C3C—C2C—H1C	119.4	N1B—C7B—C5Bⁱ	123.5 (3)
C1C—C2C—H1C	119.4	N1B—C7B—H5B	118.2
C3A—C2A—C1A	120.8 (3)	C5Bⁱ—C7B—H5B	118.2
C3A—C2A—H1A	119.6	N1C—C7C—C5C	122.6 (3)
C1A—C2A—H1A	119.6	N1C—C7C—H5C	118.7
N3B—C12B—N2B	104.6 (2)	C5C—C7C—H5C	118.7
N3B—C12B—C1B	112.5 (2)	N1Aⁱⁱⁱ—C7A—C5A	122.4 (3)
N2B—C12B—C1B	112.7 (3)	N1Aⁱⁱⁱ—C7A—H5A	118.8
N3B—C12B—H14B	109.0	C5A—C7A—H5A	118.8
N2B—C12B—H14B	109.0	C9B—N2B—C10B	113.6 (2)
C1B—C12B—H14B	109.0	C9B—N2B—C12B	112.7 (2)
N3C—C12C—N2C	104.4 (3)	C10B—N2B—C12B	104.1 (2)
N3C—C12C—C1C	114.0 (3)	C9C—N2C—C10C	115.0 (2)
N2C—C12C—C1C	112.2 (2)	C9C—N2C—C12C	112.9 (2)
N3C—C12C—H14C	108.7	C10C—N2C—C12C	104.1 (2)
N2C—C12C—H14C	108.7	C9A—N2A—C12A	114.5 (2)
C1C—C12C—H14C	108.7	C9A—N2A—C10A	113.8 (2)
N3A—C12A—N2A	105.3 (3)	C12A—N2A—C10A	103.6 (2)
N3A—C12A—C1A	110.9 (3)	C12B—N3B—C11B	104.0 (2)
N2A—C12A—C1A	113.8 (3)	C12B—N3B—H3BN	106 (2)
N3A—C12A—H14A	108.9	C11B—N3B—H3BN	110 (2)
N2A—C12A—H14A	108.9	C12C—N3C—C11C	104.0 (3)
C1A—C12A—H14A	108.9	C12C—N3C—H3CN	108 (2)
N3B—C11B—C10B	107.2 (3)	C11C—N3C—H3CN	108 (2)
N3B—C11B—H12B	110.3	C12A—N3A—C11A	105.2 (3)
C10B—C11B—H12B	110.3	C12A—N3A—H3AN	109 (3)
N3B—C11B—H13B	110.3	C11A—N3A—H3AN	102 (2)
C10B—C11B—H13B	110.3	C7B—N1B—C8B	118.0 (3)
H12B—C11B—H13B	108.5	C7C—N1C—C8Cⁱⁱ	116.7 (3)
N3C—C11C—C10C	106.6 (3)	C7Aⁱⁱⁱ—N1A—C8A	117.9 (3)
N3C—C11C—H12C	110.4

C2B—C3B—C4B—C5B	−0.9 (5)	N2B—C9B—C8B—N1B	−67.7 (3)
C2C—C3C—C4C—C5C	−0.6 (5)	N2C—C9C—C8C—N1Cⁱⁱ	64.9 (4)
C2A—C3A—C4A—C5A	−0.2 (5)	N2A—C9A—C8A—N1A	62.3 (3)
C3B—C4B—C5B—C6B	1.9 (5)	C6C—C5C—C7C—N1C	6.7 (5)
C3B—C4B—C5B—C7Bⁱ	−177.2 (3)	C4C—C5C—C7C—N1C	−172.6 (3)
C3C—C4C—C5C—C6C	0.1 (4)	C4A—C5A—C7A—N1Aⁱⁱⁱ	−167.1 (3)
C3C—C4C—C5C—C7C	179.4 (3)	C6A—C5A—C7A—N1Aⁱⁱⁱ	12.8 (4)
C3A—C4A—C5A—C6A	−1.2 (5)	C8B—C9B—N2B—C10B	−65.7 (3)
C3A—C4A—C5A—C7A	178.7 (3)	C8B—C9B—N2B—C12B	176.2 (2)
C4B—C5B—C6B—C1B	−1.4 (4)	C11B—C10B—N2B—C9B	−149.5 (3)
C7Bⁱ—C5B—C6B—C1B	177.7 (3)	C11B—C10B—N2B—C12B	−26.5 (3)
C4C—C5C—C6C—C1C	0.5 (4)	N3B—C12B—N2B—C9B	162.9 (2)
C7C—C5C—C6C—C1C	−178.8 (3)	C1B—C12B—N2B—C9B	−74.5 (3)
C4A—C5A—C6A—C1A	1.6 (4)	N3B—C12B—N2B—C10B	39.4 (3)
C7A—C5A—C6A—C1A	−178.2 (3)	C1B—C12B—N2B—C10B	162.0 (2)
C5B—C6B—C1B—C2B	−0.1 (4)	C8C—C9C—N2C—C10C	70.0 (3)
C5B—C6B—C1B—C12B	−177.8 (3)	C8C—C9C—N2C—C12C	−170.7 (2)
C5C—C6C—C1C—C2C	−0.6 (4)	C11C—C10C—N2C—C9C	149.1 (2)
C5C—C6C—C1C—C12C	179.0 (3)	C11C—C10C—N2C—C12C	25.1 (3)
C5A—C6A—C1A—C2A	−0.6 (4)	N3C—C12C—N2C—C9C	−164.9 (2)
C5A—C6A—C1A—C12A	174.8 (3)	C1C—C12C—N2C—C9C	71.2 (3)
C6B—C1B—C2B—C3B	1.1 (5)	N3C—C12C—N2C—C10C	−39.5 (3)
C12B—C1B—C2B—C3B	178.8 (3)	C1C—C12C—N2C—C10C	−163.5 (3)
C4B—C3B—C2B—C1B	−0.6 (5)	C8A—C9A—N2A—C12A	−175.2 (2)
C4C—C3C—C2C—C1C	0.5 (5)	C8A—C9A—N2A—C10A	65.9 (3)
C6C—C1C—C2C—C3C	0.1 (4)	N3A—C12A—N2A—C9A	−164.8 (3)
C12C—C1C—C2C—C3C	−179.5 (3)	C1A—C12A—N2A—C9A	73.5 (3)
C4A—C3A—C2A—C1A	1.2 (5)	N3A—C12A—N2A—C10A	−40.3 (3)
C6A—C1A—C2A—C3A	−0.8 (5)	C1A—C12A—N2A—C10A	−162.0 (3)
C12A—C1A—C2A—C3A	−176.2 (3)	C11A—C10A—N2A—C9A	155.3 (3)
C2B—C1B—C12B—N3B	−102.6 (3)	C11A—C10A—N2A—C12A	30.3 (3)
C6B—C1B—C12B—N3B	75.1 (4)	N2B—C12B—N3B—C11B	−36.0 (3)
C2B—C1B—C12B—N2B	139.4 (3)	C1B—C12B—N3B—C11B	−158.6 (3)
C6B—C1B—C12B—N2B	−42.9 (4)	C10B—C11B—N3B—C12B	19.2 (3)
C6C—C1C—C12C—N3C	−70.4 (4)	N2C—C12C—N3C—C11C	37.7 (3)
C2C—C1C—C12C—N3C	109.2 (3)	C1C—C12C—N3C—C11C	160.5 (3)
C6C—C1C—C12C—N2C	48.1 (4)	C10C—C11C—N3C—C12C	−21.7 (3)
C2C—C1C—C12C—N2C	−132.4 (3)	N2A—C12A—N3A—C11A	33.7 (3)
C6A—C1A—C12A—N3A	−68.1 (4)	C1A—C12A—N3A—C11A	157.3 (3)
C2A—C1A—C12A—N3A	107.2 (4)	C10A—C11A—N3A—C12A	−14.2 (4)
C6A—C1A—C12A—N2A	50.4 (4)	C5Bⁱ—C7B—N1B—C8B	178.7 (2)
C2A—C1A—C12A—N2A	−134.3 (3)	C9B—C8B—N1B—C7B	118.9 (3)
N3B—C11B—C10B—N2B	4.8 (3)	C5C—C7C—N1C—C8Cⁱⁱ	177.5 (3)
N3C—C11C—C10C—N2C	−2.3 (3)	C9A—C8A—N1A—C7Aⁱⁱⁱ	−122.8 (3)
N3A—C11A—C10A—N2A	−10.1 (4)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3B—H3BN···N1Aⁱ	0.88 (3)	2.60 (3)	3.371 (4)	147 (3)
N3C—H3CN···N1B^iv	0.90 (3)	2.86 (3)	3.608 (4)	142 (3)
N3A—H3AN···N3B^v	0.83 (3)	2.70 (3)	3.495 (4)	161 (3)

Symmetry codes: (i) −x, −y+1, −z; (iv) x+1, y, z; (v) x, y+1, z.

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