Download citation
Download citation
link to html
The synthesis of the title Tröger's base analogue, C23H22N6, was undertaken in order to study the influence of a methyl substituent on the structure. Minor differences were found in the bond lengths of the title structure in comparison with the values for free pyrazole and for the first pyrazolic Tröger's base reported in the literature. There are two mol­ecules of opposite chirality in the asymmetric unit and the packing in the lattice is characterized by a non-crystallographic n-glide plane relating these mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012531/sx1110sup1.cif
Contains datablocks II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012531/sx1110IIsup2.hkl
Contains datablock II

CCDC reference: 162564

Comment top

As part of an ongoing study of the reactivity of pyrazole derivatives as activated aromatic precursors (Quiroga et al., 1999), the synthesis of fused amino-heterocycle systems was undertaken to obtain a compound with a five-membered aromatic ring: a new Tröger's base. The molecular structure of 3,4,7,8-bis(1-phenylpyrazol)-1,5-methylene-1,5-diazacyclooctane, the first pyrazolic Tröger's base, has been reported in the literature (Cudero et al., 1997). In the Cambridge Structural Database (Allen et al., 1991), this compound has the refcode NIMHIA. Tröger's bases are concave chiral molecules with interesting structural properties. Several Tröger's base analogues with potential applications in the design of synthetic enzymes, artificial receptor systems, selective organic catalysts and reagents (Cowart et al., 1988; Adrian, Jr. & Wilcox, 1992), chelating and biomimetic systems (Wilcox, 1985; Crossley et al., 1995) and metal complexes with catalytic activity (Goldberg et al., 1995) have been reported. The title Tröger's base, (II), was synthesized from 5-amino-3-methyl-1-phenyl pyrazole, (I), by reaction with formaldehyde. \sch

Compound (II) has a folded structure wherein the two N atoms and the three methylene carbons form a hingelike bridge between the two pyrazole rings. Comparing the bond lengths of the free molecule of pyrazole (Larsen et al., 1970) with the pyrazole moiety in the title compound, it was found that the N—N bond length changes from 1.334 and 1.338 Å in the free molecule to 1.374 (2) Å for N1—N2, 1.380 (2) Å, for N6—N7, 1.375 (2) Å for N31—N32 and 1.377 (2) Å for N36—N37 in the title compound. The C—N bond length in the free molecule of pyrazole changes from 1.325 and 1.339 Å to 1.358 (3) Å for N1—C10a, 1.371 (3) for N6—C5a, 1.359 (2) for N31—C40a and 1.371 (2) Å for N36—C35a in the title structure. Values of the bond angles of the pyrazole ring of the free molecule and values of the bond angles of the pyrazole moiety of compound (II) are similar. When bond lengths and bond angles of the eight-membered ring in the structure NIMHIA are compared to bond lengths and bond angles of same ring in the title structure, minor differences in these values were found. The other bond lengths values of phenyl and pyrazole rings of the NIMHIA structure are very close to those values in the title structure. The tetrahydropyrimidin backbone adopts a half chair conformation (Cremer & Pople, 1975). This conformation is similar to that in NIMHIA. In Tröger's bases, the dihedral angle, formed by the least-squares planes containing aryl substituent rings, varies from 92° to 104° (Wilcox et al., 1987). This same dihedral angle in the NIMHIA structure containing pyrazole rings has a value of 96.4 (4)° while in compound (II) are 85.95 (7) and 86.82 (9)°. There are two molecules o fopposite chirality in the asymmetric unit and the packing in the lattice is characterized by a non-crystallographic n-glide plane relating these molecules. These molecules also exhibit dyad symmetry. The equation found for the glide plane is 0.0178x + 0.0006y + 0.9998z - 5.1954 = 0 and the translations are approximately (a+b)/2. Fig. 2 shows the packing with the two independent enantiomers related by the pseudo n glide plane.

Related literature top

For related literature, see: Adrian & Wilcox (1992); Allen et al. (1991); Cowart et al. (1988); Cremer & Pople (1975); Crossley et al. (1995); Cudero et al. (1997); Goldberg & Alper (1995); Larsen et al. (1970); Quiroga et al. (1999); Sheldrick (1997); Wilcox (1985); Wilcox et al. (1987).

Experimental top

5-Amino-3-methyl-1-phenyl-pyrazole, (I) (2.89 mmol), formaldehyde 37% (4.5 mmol) and acetic acid (0.2 ml) in ethanol (10 ml) were heated at 323 K for 5 min and monitored by thin-layer chromatography. After cooling, crystals were obtained, filtered off and recrystalized from ethanol [yield 53%; m.p. 551 (1) K]. Spectroscopic analysis: 1H and 13C NMR, MS and elemental analysis. 1H NMR (300 MHz, DMSO -d6), (δ, p.p.m.): 1.92 (6H, s), 3.56 [2H, d, J = 15.7 Hz], 4.26 [2H, d, J = 15.7 Hz], 4.31 (2H, s), 7.29 [2H, t, J = 7.4 Hz], 7.50 [4H, br.t, J = 7.9 Hz], 7.96 [4H, d, J = 8.7 Hz]; 13C NMR (75 MHz, DMSO -d6), (δ, p.p.m.): 12.1 (C-16, C-17), 47.4 (C-4, C-9), 67.5 (C-15), 104.3, 119.7, 125.5, 129.3, 139.2, 144.7, 144.9; MS (70 eV), m/e (%): 382 (100), 354 (23), 198 (53), 77 (30); C23H22N6 (382.46): calcd. C 72.19, H 5.81, N 22.01; found C 72.13, H 5.82, N 22.05.

Refinement top

The aryl, methyl and methylenic H atoms were added at calculated positions. The H atoms treated with a riding model with SHELXL97 (Sheldrick, 1997) defaults (C—H 0.93–0.97 Å) were not refined.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A ZORTEP (Zsolnai, 1995) plot of the title compound with the atomic labelling scheme. Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radii. The atom labels indicate the presence of the pseudo n-glide plane.
[Figure 2] Fig. 2. A ZORTEP stereoscopic view of the title compound showing the packing diagram with two independent enantiomers related by a non-crystallographic n-glide plane.
(II) top
Crystal data top
C23H22N6F(000) = 808
Mr = 382.46Dx = 1.290 Mg m3
Triclinic, P1Melting point: 393 K
a = 11.224 (1) ÅMo Kα radiation, λ = 0.71069 Å
b = 13.650 (1) ÅCell parameters from 17 reflections
c = 14.110 (1) Åθ = 20.5–22.5°
α = 75.270 (2)°µ = 0.08 mm1
β = 73.070 (2)°T = 293 K
γ = 76.270 (2)°Transparent prisms, colourless
V = 1968.7 (3) Å30.20 × 0.15 × 0.12 mm
Z = 4
Data collection top
Rigaku AFC7S
diffractometer
Rint = 0.091
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 2.2°
Graphite monochromatorh = 1313
ω/2θ scansk = 160
7664 measured reflectionsl = 1716
7332 independent reflections3 standard reflections every 150 reflections
4249 reflections with I > 2σ(I) intensity decay: 3.6%
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H atoms treated by a mixture of independent and constrained refinement
S = 1.02Calculated w = 1/[σ2(Fo2) + (0.0738P)2 + 0.0251P]
where P = (Fo2 + 2Fc2)/3
7332 reflections(Δ/σ)max < 0.001
570 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C23H22N6γ = 76.270 (2)°
Mr = 382.46V = 1968.7 (3) Å3
Triclinic, P1Z = 4
a = 11.224 (1) ÅMo Kα radiation
b = 13.650 (1) ŵ = 0.08 mm1
c = 14.110 (1) ÅT = 293 K
α = 75.270 (2)°0.20 × 0.15 × 0.12 mm
β = 73.070 (2)°
Data collection top
Rigaku AFC7S
diffractometer
Rint = 0.091
7664 measured reflections3 standard reflections every 150 reflections
7332 independent reflections intensity decay: 3.6%
4249 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.141H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.17 e Å3
7332 reflectionsΔρmin = 0.23 e Å3
570 parameters
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
xyzUiso*/Ueq
N10.16530 (16)0.88309 (13)0.43637 (13)0.0482 (4)
N20.22728 (17)0.95533 (15)0.44375 (14)0.0565 (5)
C30.2711 (2)1.00200 (18)0.34865 (18)0.0532 (5)
C3A0.23639 (18)0.96234 (16)0.27955 (16)0.0456 (5)
C40.25174 (19)0.98986 (17)0.16708 (16)0.0489 (5)
H410.23321.06400.14550.053 (6)*
H420.33840.96580.13300.057 (6)*
N50.16390 (15)0.94134 (13)0.13979 (12)0.0469 (4)
C5A0.03748 (18)0.99199 (15)0.16578 (14)0.0421 (5)
N60.01459 (15)1.08203 (13)0.11151 (12)0.0459 (4)
N70.13973 (16)1.11021 (14)0.15972 (13)0.0496 (4)
C80.16285 (18)1.03730 (16)0.24076 (15)0.0456 (5)
C8A0.05489 (18)0.96013 (15)0.24827 (15)0.0429 (5)
C90.02889 (18)0.86386 (16)0.32385 (16)0.0469 (5)
H910.06230.87760.39170.045 (5)*
H920.07020.81160.31790.048 (5)*
N100.11016 (15)0.82642 (12)0.30538 (12)0.0452 (4)
C10A0.16926 (18)0.88772 (15)0.33821 (15)0.0425 (5)
C150.1670 (2)0.83437 (16)0.19604 (16)0.0504 (5)
H1510.25420.79900.18590.043 (5)*
H1520.12210.79990.16880.059 (6)*
C160.3433 (3)1.0882 (2)0.3274 (2)0.0784 (8)
H1610.36321.09130.38810.144 (14)*
H1620.29261.15220.30410.168 (18)*
H1630.42021.07600.27630.152 (16)*
C170.2905 (2)1.04182 (18)0.31298 (18)0.0572 (6)
H1710.34411.10530.29250.064 (7)*
H1720.28231.03810.37970.091 (9)*
H1730.32720.98500.31310.076 (8)*
C180.10585 (19)0.81778 (17)0.52437 (15)0.0475 (5)
C190.0415 (2)0.8563 (2)0.61018 (18)0.0630 (6)
H190.03760.92480.61140.084 (9)*
C200.0168 (3)0.7921 (3)0.6940 (2)0.0784 (8)
H200.05840.81690.75280.083 (8)*
C210.0143 (3)0.6921 (3)0.6917 (2)0.0791 (8)
H210.05680.65000.74790.095 (9)*
C220.0515 (2)0.6539 (2)0.60580 (19)0.0719 (7)
H220.05390.58560.60450.070 (8)*
C230.1133 (2)0.71577 (18)0.52235 (17)0.0583 (6)
H230.15970.68950.46520.085 (8)*
C240.03833 (19)1.14399 (17)0.01828 (15)0.0465 (5)
C250.1455 (2)1.1038 (2)0.04826 (16)0.0593 (6)
H250.18461.03570.03220.073 (8)*
C260.1936 (3)1.1663 (2)0.13895 (17)0.0676 (7)
H260.26631.14010.18340.089 (9)*
C270.1353 (3)1.2667 (2)0.16430 (19)0.0696 (7)
H270.16871.30830.22510.084 (8)*
C280.0271 (3)1.3048 (2)0.09863 (19)0.0717 (7)
H280.01381.37200.11620.103 (10)*
C290.0216 (2)1.24479 (18)0.00716 (18)0.0602 (6)
H290.09401.27170.03710.076*
N310.64128 (16)0.37172 (13)0.04055 (12)0.0490 (4)
N320.70257 (18)0.44389 (14)0.03196 (13)0.0570 (5)
C330.7494 (2)0.48927 (17)0.01786 (16)0.0546 (6)
C33A0.71959 (19)0.44904 (15)0.12253 (15)0.0473 (5)
C340.7416 (2)0.47491 (17)0.21237 (16)0.0500 (5)
H3410.82900.44920.21540.051 (6)*
H3420.72550.54900.20610.058 (6)*
N350.65622 (16)0.42776 (12)0.30635 (12)0.0456 (4)
C35A0.53044 (19)0.48049 (15)0.31739 (14)0.0430 (5)
N360.48362 (16)0.57113 (13)0.35117 (12)0.0464 (4)
N370.35803 (16)0.60266 (14)0.34987 (14)0.0528 (5)
C380.3283 (2)0.53033 (17)0.31812 (15)0.0492 (5)
C38A0.43365 (19)0.45174 (15)0.29628 (14)0.0452 (5)
C390.4540 (2)0.35577 (16)0.25608 (16)0.0493 (5)
H3910.41230.30430.30780.055 (6)*
H3920.41750.37090.19840.045 (5)*
N400.59152 (16)0.31553 (12)0.22529 (12)0.0462 (4)
C40A0.65002 (18)0.37518 (15)0.13366 (14)0.0429 (5)
C450.6547 (2)0.32114 (15)0.30189 (16)0.0510 (5)
H4510.61150.28700.36780.053 (6)*
H4520.74110.28440.28660.046 (6)*
C460.8210 (3)0.5756 (2)0.0379 (2)0.0776 (8)
H4610.91020.54930.05110.129 (13)*
H4620.80070.62700.00250.140 (14)*
H4630.79770.60570.10080.126 (13)*
C470.1978 (2)0.5399 (2)0.3060 (2)0.0674 (7)
H4710.14450.59890.33090.116 (11)*
H4720.16410.47910.34350.109 (11)*
H4730.20090.54800.23570.115 (11)*
C480.58348 (19)0.30512 (16)0.01262 (14)0.0450 (5)
C490.5254 (2)0.34092 (19)0.06645 (17)0.0588 (6)
H490.52520.40830.10240.081 (8)*
C500.4674 (2)0.2755 (2)0.0917 (2)0.0692 (7)
H500.42890.29890.14540.106 (10)*
C510.4664 (2)0.1768 (2)0.03826 (19)0.0641 (6)
H510.42460.13410.05400.077 (8)*
C520.5268 (2)0.14081 (19)0.03842 (19)0.0628 (6)
H520.52730.07320.07380.072 (8)*
C530.5872 (2)0.20394 (17)0.06376 (17)0.0571 (6)
H530.63000.17870.11480.063 (7)*
C540.5431 (2)0.63194 (16)0.38489 (15)0.0461 (5)
C550.6505 (2)0.58929 (18)0.42038 (16)0.0557 (6)
H550.68490.51990.42300.056 (6)*
C560.7061 (2)0.6517 (2)0.45198 (17)0.0647 (6)
H560.77970.62410.47410.057 (7)*
C570.6541 (3)0.7537 (2)0.45109 (18)0.0691 (7)
H570.69210.79470.47280.081 (8)*
C580.5465 (3)0.7943 (2)0.4182 (2)0.0715 (7)
H580.51070.86310.41830.081 (8)*
C590.4902 (2)0.73471 (18)0.38497 (19)0.0621 (6)
H590.41690.76320.36260.089 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0530 (10)0.0521 (10)0.0455 (10)0.0106 (8)0.0158 (8)0.0148 (8)
N20.0589 (11)0.0630 (12)0.0592 (12)0.0159 (9)0.0196 (9)0.0220 (10)
C30.0492 (13)0.0587 (13)0.0584 (14)0.0119 (11)0.0169 (11)0.0167 (11)
C3A0.0371 (11)0.0516 (12)0.0507 (12)0.0068 (9)0.0098 (9)0.0167 (10)
C40.0391 (11)0.0570 (14)0.0492 (12)0.0087 (10)0.0041 (9)0.0157 (10)
N50.0458 (10)0.0520 (10)0.0436 (10)0.0057 (8)0.0090 (8)0.0161 (8)
C5A0.0417 (11)0.0499 (12)0.0386 (10)0.0078 (9)0.0119 (9)0.0134 (9)
N60.0417 (10)0.0555 (11)0.0388 (9)0.0092 (8)0.0093 (7)0.0067 (8)
N70.0420 (10)0.0586 (11)0.0452 (10)0.0089 (8)0.0092 (8)0.0070 (9)
C80.0409 (11)0.0528 (12)0.0454 (12)0.0102 (10)0.0106 (9)0.0120 (10)
C8A0.0426 (11)0.0486 (11)0.0415 (11)0.0109 (9)0.0132 (9)0.0096 (9)
C90.0445 (11)0.0533 (12)0.0483 (12)0.0148 (10)0.0135 (9)0.0115 (10)
N100.0483 (10)0.0434 (9)0.0475 (10)0.0057 (8)0.0143 (8)0.0148 (8)
C10A0.0394 (11)0.0451 (11)0.0444 (11)0.0031 (9)0.0114 (9)0.0143 (9)
C150.0558 (13)0.0502 (12)0.0507 (12)0.0021 (10)0.0166 (10)0.0225 (10)
C160.0801 (19)0.091 (2)0.083 (2)0.0428 (17)0.0240 (17)0.0212 (17)
C170.0461 (12)0.0605 (15)0.0586 (15)0.0086 (11)0.0086 (11)0.0064 (11)
C180.0427 (11)0.0566 (13)0.0429 (11)0.0033 (10)0.0128 (9)0.0122 (10)
C190.0638 (15)0.0714 (17)0.0538 (14)0.0002 (13)0.0118 (12)0.0268 (12)
C200.0710 (18)0.105 (2)0.0486 (15)0.0000 (16)0.0019 (13)0.0263 (16)
C210.0676 (17)0.101 (2)0.0522 (16)0.0178 (16)0.0018 (13)0.0003 (16)
C220.0769 (18)0.0659 (17)0.0634 (17)0.0144 (14)0.0076 (14)0.0058 (13)
C230.0643 (15)0.0568 (14)0.0474 (13)0.0069 (11)0.0040 (11)0.0135 (11)
C240.0506 (12)0.0576 (13)0.0371 (11)0.0209 (10)0.0115 (9)0.0084 (10)
C250.0600 (14)0.0760 (17)0.0417 (12)0.0167 (13)0.0060 (11)0.0145 (12)
C260.0684 (16)0.099 (2)0.0412 (13)0.0339 (15)0.0041 (12)0.0170 (14)
C270.0890 (19)0.0847 (19)0.0454 (14)0.0509 (16)0.0131 (14)0.0018 (14)
C280.092 (2)0.0659 (17)0.0580 (16)0.0326 (15)0.0165 (15)0.0013 (13)
C290.0660 (15)0.0606 (15)0.0542 (14)0.0193 (12)0.0118 (12)0.0079 (11)
N310.0597 (11)0.0488 (10)0.0369 (9)0.0153 (9)0.0059 (8)0.0071 (8)
N320.0692 (12)0.0582 (11)0.0385 (10)0.0214 (10)0.0015 (9)0.0050 (9)
C330.0591 (14)0.0548 (13)0.0444 (12)0.0171 (11)0.0002 (10)0.0088 (10)
C33A0.0516 (12)0.0437 (11)0.0425 (12)0.0081 (10)0.0050 (9)0.0095 (9)
C340.0488 (13)0.0488 (13)0.0508 (12)0.0102 (10)0.0073 (10)0.0115 (10)
N350.0535 (10)0.0428 (9)0.0403 (9)0.0069 (8)0.0118 (8)0.0091 (7)
C35A0.0524 (12)0.0386 (10)0.0349 (10)0.0087 (9)0.0054 (9)0.0074 (8)
N360.0484 (10)0.0462 (10)0.0445 (10)0.0069 (8)0.0077 (8)0.0145 (8)
N370.0501 (11)0.0530 (11)0.0556 (11)0.0057 (9)0.0099 (9)0.0182 (9)
C380.0519 (13)0.0528 (12)0.0405 (11)0.0128 (10)0.0035 (9)0.0108 (10)
C38A0.0521 (12)0.0448 (11)0.0371 (11)0.0143 (10)0.0033 (9)0.0085 (9)
C390.0561 (13)0.0492 (12)0.0425 (11)0.0179 (10)0.0040 (10)0.0104 (10)
N400.0592 (11)0.0389 (9)0.0378 (9)0.0096 (8)0.0080 (8)0.0068 (7)
C40A0.0488 (12)0.0393 (10)0.0366 (11)0.0040 (9)0.0065 (9)0.0087 (9)
C450.0660 (14)0.0404 (11)0.0414 (12)0.0046 (10)0.0125 (10)0.0044 (9)
C460.094 (2)0.0782 (18)0.0554 (16)0.0438 (16)0.0040 (14)0.0025 (15)
C470.0526 (14)0.0811 (18)0.0730 (18)0.0118 (14)0.0129 (12)0.0262 (15)
C480.0474 (12)0.0473 (12)0.0374 (11)0.0040 (9)0.0069 (9)0.0113 (9)
C490.0626 (15)0.0556 (14)0.0546 (14)0.0038 (11)0.0193 (12)0.0054 (11)
C500.0687 (16)0.0806 (19)0.0640 (16)0.0003 (14)0.0317 (14)0.0188 (14)
C510.0580 (14)0.0746 (17)0.0673 (16)0.0109 (13)0.0164 (12)0.0270 (14)
C520.0806 (17)0.0509 (14)0.0613 (15)0.0137 (12)0.0188 (13)0.0155 (12)
C530.0769 (16)0.0488 (13)0.0490 (13)0.0074 (11)0.0244 (12)0.0086 (10)
C540.0542 (13)0.0467 (12)0.0360 (11)0.0155 (10)0.0033 (9)0.0087 (9)
C550.0727 (16)0.0537 (14)0.0449 (12)0.0158 (12)0.0170 (11)0.0094 (10)
C560.0716 (17)0.0797 (18)0.0497 (14)0.0219 (14)0.0187 (12)0.0124 (12)
C570.0846 (19)0.0738 (18)0.0574 (15)0.0386 (15)0.0015 (13)0.0236 (13)
C580.0798 (19)0.0551 (15)0.0827 (19)0.0213 (14)0.0073 (15)0.0251 (14)
C590.0645 (15)0.0510 (14)0.0719 (16)0.0137 (12)0.0100 (13)0.0190 (12)
Geometric parameters (Å, º) top
N1—C10A1.358 (3)N31—C40A1.359 (2)
N1—N21.374 (2)N31—N321.375 (2)
N1—C181.421 (3)N31—C481.419 (3)
N2—C31.333 (3)N32—C331.321 (3)
C3—C3A1.409 (3)C33—C33A1.408 (3)
C3—C161.504 (3)C33—C461.504 (3)
C3A—C10A1.365 (3)C33A—C40A1.368 (3)
C3A—C41.503 (3)C33A—C341.498 (3)
C4—N51.490 (3)C34—N351.487 (3)
C4—H410.9700C34—H3410.9700
C4—H420.9700C34—H3420.9700
N5—C5A1.409 (2)N35—C35A1.408 (3)
N5—C151.472 (3)N35—C451.477 (3)
C5A—C8A1.368 (3)C35A—C38A1.369 (3)
C5A—N61.371 (3)C35A—N361.371 (2)
N6—N71.380 (2)N36—N371.377 (2)
N6—C241.420 (2)N36—C541.418 (3)
N7—C81.318 (3)N37—C381.325 (3)
C8—C8A1.415 (3)C38—C38A1.414 (3)
C8—C171.495 (3)C38—C471.495 (3)
C8A—C91.495 (3)C38A—C391.500 (3)
C9—N101.489 (2)C39—N401.484 (3)
C9—H910.9700C39—H3910.9700
C9—H920.9700C39—H3920.9700
N10—C10A1.412 (2)N40—C40A1.410 (2)
N10—C151.474 (3)N40—C451.480 (3)
C15—H1510.9700C45—H4510.9700
C15—H1520.9700C45—H4520.9700
C16—H1610.9600C46—H4610.9600
C16—H1620.9600C46—H4620.9600
C16—H1630.9600C46—H4630.9600
C17—H1710.9600C47—H4710.9600
C17—H1720.9600C47—H4720.9600
C17—H1730.9600C47—H4730.9600
C18—C191.378 (3)C48—C491.379 (3)
C18—C231.382 (3)C48—C531.383 (3)
C19—C201.374 (4)C49—C501.386 (3)
C19—H190.9300C49—H490.9300
C20—C211.366 (4)C50—C511.367 (4)
C20—H200.9300C50—H500.9300
C21—C221.380 (4)C51—C521.368 (3)
C21—H210.9300C51—H510.9300
C22—C231.371 (3)C52—C531.380 (3)
C22—H220.9300C52—H520.9300
C23—H230.9300C53—H530.9300
C24—C251.385 (3)C54—C551.384 (3)
C24—C291.387 (3)C54—C591.387 (3)
C25—C261.385 (3)C55—C561.386 (3)
C25—H250.9300C55—H550.9300
C26—C271.376 (4)C56—C571.374 (4)
C26—H260.9300C56—H560.9300
C27—C281.376 (4)C57—C581.364 (4)
C27—H270.9300C57—H570.9300
C28—C291.378 (3)C58—C591.375 (3)
C28—H280.9300C58—H580.9300
C29—H290.9300C59—H590.9300
C10A—N1—N2110.55 (17)C40A—N31—N32110.32 (16)
C10A—N1—C18128.67 (17)C40A—N31—C48129.27 (17)
N2—N1—C18120.76 (16)N32—N31—C48120.39 (16)
C3—N2—N1105.01 (16)C33—N32—N31105.19 (17)
N2—C3—C3A111.51 (19)N32—C33—C33A111.99 (19)
N2—C3—C16119.9 (2)N32—C33—C46120.0 (2)
C3A—C3—C16128.5 (2)C33A—C33—C46128.0 (2)
C10A—C3A—C3104.69 (19)C40A—C33A—C33104.34 (18)
C10A—C3A—C4120.96 (18)C40A—C33A—C34121.21 (18)
C3—C3A—C4134.2 (2)C33—C33A—C34134.33 (19)
N5—C4—C3A109.42 (16)N35—C34—C33A109.73 (16)
N5—C4—H41109.8N35—C34—H341109.7
C3A—C4—H41109.8C33A—C34—H341109.7
N5—C4—H42109.8N35—C34—H342109.7
C3A—C4—H42109.8C33A—C34—H342109.7
H41—C4—H42108.2H341—C34—H342108.2
C5A—N5—C15106.57 (16)C35A—N35—C45106.56 (16)
C5A—N5—C4111.97 (15)C35A—N35—C34111.79 (16)
C15—N5—C4109.74 (16)C45—N35—C34109.53 (16)
C8A—C5A—N6108.02 (17)C38A—C35A—N36107.79 (18)
C8A—C5A—N5126.46 (19)C38A—C35A—N35126.79 (18)
N6—C5A—N5125.52 (18)N36—C35A—N35125.43 (18)
C5A—N6—N7109.93 (16)C35A—N36—N37110.16 (16)
C5A—N6—C24130.77 (17)C35A—N36—C54130.64 (18)
N7—N6—C24119.28 (16)N37—N36—C54119.20 (16)
C8—N7—N6105.58 (16)C38—N37—N36105.63 (16)
N7—C8—C8A111.92 (17)N37—C38—C38A111.46 (19)
N7—C8—C17121.06 (19)N37—C38—C47120.5 (2)
C8A—C8—C17127.02 (19)C38A—C38—C47128.0 (2)
C5A—C8A—C8104.53 (18)C35A—C38A—C38104.94 (18)
C5A—C8A—C9121.65 (18)C35A—C38A—C39121.32 (19)
C8—C8A—C9133.80 (18)C38—C38A—C39133.71 (19)
N10—C9—C8A109.36 (16)N40—C39—C38A109.64 (16)
N10—C9—H91109.8N40—C39—H391109.7
C8A—C9—H91109.8C38A—C39—H391109.7
N10—C9—H92109.8N40—C39—H392109.7
C8A—C9—H92109.8C38A—C39—H392109.7
H91—C9—H92108.3H391—C39—H392108.2
C10A—N10—C15106.30 (16)C40A—N40—C45106.19 (16)
C10A—N10—C9111.22 (15)C40A—N40—C39111.50 (15)
C15—N10—C9109.95 (16)C45—N40—C39110.11 (16)
N1—C10A—C3A108.22 (17)N31—C40A—C33A108.15 (17)
N1—C10A—N10124.60 (18)N31—C40A—N40124.97 (18)
C3A—C10A—N10127.16 (18)C33A—C40A—N40126.82 (18)
N5—C15—N10113.19 (16)N35—C45—N40113.06 (16)
N5—C15—H151108.9N35—C45—H451109.0
N10—C15—H151108.9N40—C45—H451109.0
N5—C15—H152108.9N35—C45—H452109.0
N10—C15—H152108.9N40—C45—H452109.0
H151—C15—H152107.8H451—C45—H452107.8
C3—C16—H161109.5C33—C46—H461109.5
C3—C16—H162109.5C33—C46—H462109.5
H161—C16—H162109.5H461—C46—H462109.5
C3—C16—H163109.5C33—C46—H463109.5
H161—C16—H163109.5H461—C46—H463109.5
H162—C16—H163109.5H462—C46—H463109.5
C8—C17—H171109.5C38—C47—H471109.5
C8—C17—H172109.5C38—C47—H472109.5
H171—C17—H172109.5H471—C47—H472109.5
C8—C17—H173109.5C38—C47—H473109.5
H171—C17—H173109.5H471—C47—H473109.5
H172—C17—H173109.5H472—C47—H473109.5
C19—C18—C23120.8 (2)C49—C48—C53120.1 (2)
C19—C18—N1120.1 (2)C49—C48—N31119.96 (19)
C23—C18—N1119.11 (19)C53—C48—N31119.90 (19)
C20—C19—C18119.1 (2)C48—C49—C50119.3 (2)
C20—C19—H19120.5C48—C49—H49120.3
C18—C19—H19120.5C50—C49—H49120.3
C21—C20—C19120.7 (2)C51—C50—C49120.5 (2)
C21—C20—H20119.6C51—C50—H50119.8
C19—C20—H20119.6C49—C50—H50119.8
C20—C21—C22119.8 (3)C50—C51—C52120.0 (2)
C20—C21—H21120.1C50—C51—H51120.0
C22—C21—H21120.1C52—C51—H51120.0
C23—C22—C21120.4 (3)C51—C52—C53120.6 (2)
C23—C22—H22119.8C51—C52—H52119.7
C21—C22—H22119.8C53—C52—H52119.7
C22—C23—C18119.1 (2)C52—C53—C48119.4 (2)
C22—C23—H23120.5C52—C53—H53120.3
C18—C23—H23120.5C48—C53—H53120.3
C25—C24—C29120.2 (2)C55—C54—C59119.9 (2)
C25—C24—N6120.8 (2)C55—C54—N36120.81 (19)
C29—C24—N6118.96 (19)C59—C54—N36119.3 (2)
C26—C25—C24119.2 (2)C54—C55—C56118.9 (2)
C26—C25—H25120.4C54—C55—H55120.5
C24—C25—H25120.4C56—C55—H55120.5
C27—C26—C25121.0 (3)C57—C56—C55121.0 (2)
C27—C26—H26119.5C57—C56—H56119.5
C25—C26—H26119.5C55—C56—H56119.5
C28—C27—C26119.2 (2)C58—C57—C56119.5 (2)
C28—C27—H27120.4C58—C57—H57120.2
C26—C27—H27120.4C56—C57—H57120.2
C27—C28—C29121.0 (3)C57—C58—C59120.8 (3)
C27—C28—H28119.5C57—C58—H58119.6
C29—C28—H28119.5C59—C58—H58119.6
C28—C29—C24119.4 (2)C58—C59—C54119.8 (3)
C28—C29—H29120.3C58—C59—H59120.1
C24—C29—H29120.3C54—C59—H59120.1
C10A—N1—N2—C31.4 (2)C40A—N31—N32—C330.9 (2)
C18—N1—N2—C3179.93 (18)C48—N31—N32—C33177.46 (19)
N1—N2—C3—C3A1.1 (2)N31—N32—C33—C33A0.4 (2)
N1—N2—C3—C16179.0 (2)N31—N32—C33—C46178.5 (2)
N2—C3—C3A—C10A0.5 (2)N32—C33—C33A—C40A0.2 (3)
C16—C3—C3A—C10A178.1 (2)C46—C33—C33A—C40A177.7 (2)
N2—C3—C3A—C4175.2 (2)N32—C33—C33A—C34176.1 (2)
C16—C3—C3A—C42.5 (4)C46—C33—C33A—C341.8 (4)
C10A—C3A—C4—N511.7 (3)C40A—C33A—C34—N3512.5 (3)
C3—C3A—C4—N5163.4 (2)C33—C33A—C34—N35162.9 (2)
C3A—C4—N5—C5A74.4 (2)C33A—C34—N35—C35A74.2 (2)
C3A—C4—N5—C1543.7 (2)C33A—C34—N35—C4543.7 (2)
C15—N5—C5A—C8A18.5 (3)C45—N35—C35A—C38A18.9 (3)
C4—N5—C5A—C8A101.5 (2)C34—N35—C35A—C38A100.7 (2)
C15—N5—C5A—N6160.79 (18)C45—N35—C35A—N36161.47 (18)
C4—N5—C5A—N679.2 (2)C34—N35—C35A—N3678.9 (2)
C8A—C5A—N6—N71.5 (2)C38A—C35A—N36—N371.4 (2)
N5—C5A—N6—N7179.10 (17)N35—C35A—N36—N37178.27 (17)
C8A—C5A—N6—C24176.95 (18)C38A—C35A—N36—C54178.46 (19)
N5—C5A—N6—C242.5 (3)N35—C35A—N36—C541.8 (3)
C5A—N6—N7—C81.0 (2)C35A—N36—N37—C381.6 (2)
C24—N6—N7—C8177.65 (17)C54—N36—N37—C38178.30 (17)
N6—N7—C8—C8A0.1 (2)N36—N37—C38—C38A1.2 (2)
N6—N7—C8—C17179.67 (18)N36—N37—C38—C47179.16 (19)
N6—C5A—C8A—C81.3 (2)N36—C35A—C38A—C380.7 (2)
N5—C5A—C8A—C8179.27 (18)N35—C35A—C38A—C38179.02 (19)
N6—C5A—C8A—C9179.69 (17)N36—C35A—C38A—C39179.15 (17)
N5—C5A—C8A—C90.9 (3)N35—C35A—C38A—C390.5 (3)
N7—C8—C8A—C5A0.7 (2)N37—C38—C38A—C35A0.3 (2)
C17—C8—C8A—C5A178.8 (2)C47—C38—C38A—C35A178.1 (2)
N7—C8—C8A—C9178.8 (2)N37—C38—C38A—C39177.9 (2)
C17—C8—C8A—C90.7 (4)C47—C38—C38A—C390.1 (4)
C5A—C8A—C9—N1011.5 (3)C35A—C38A—C39—N4011.6 (3)
C8—C8A—C9—N10166.3 (2)C38—C38A—C39—N40166.4 (2)
C8A—C9—N10—C10A74.5 (2)C38A—C39—N40—C40A74.8 (2)
C8A—C9—N10—C1543.0 (2)C38A—C39—N40—C4542.8 (2)
N2—N1—C10A—C3A1.1 (2)N32—N31—C40A—C33A1.1 (2)
C18—N1—C10A—C3A179.69 (18)C48—N31—C40A—C33A177.12 (19)
N2—N1—C10A—N10177.42 (17)N32—N31—C40A—N40176.21 (18)
C18—N1—C10A—N101.2 (3)C48—N31—C40A—N405.6 (3)
C3—C3A—C10A—N10.4 (2)C33—C33A—C40A—N310.7 (2)
C4—C3A—C10A—N1176.77 (17)C34—C33A—C40A—N31177.30 (18)
C3—C3A—C10A—N10178.09 (19)C33—C33A—C40A—N40176.46 (19)
C4—C3A—C10A—N101.7 (3)C34—C33A—C40A—N400.1 (3)
C15—N10—C10A—N1164.31 (18)C45—N40—C40A—N31164.07 (19)
C9—N10—C10A—N176.0 (2)C39—N40—C40A—N3176.0 (2)
C15—N10—C10A—C3A17.4 (3)C45—N40—C40A—C33A19.2 (3)
C9—N10—C10A—C3A102.2 (2)C39—N40—C40A—C33A100.8 (2)
C5A—N5—C15—N1052.4 (2)C35A—N35—C45—N4052.2 (2)
C4—N5—C15—N1069.0 (2)C34—N35—C45—N4068.9 (2)
C10A—N10—C15—N552.0 (2)C40A—N40—C45—N3552.8 (2)
C9—N10—C15—N568.5 (2)C39—N40—C45—N3568.0 (2)
C10A—N1—C18—C19139.0 (2)C40A—N31—C48—C49145.9 (2)
N2—N1—C18—C1939.5 (3)N32—N31—C48—C4936.1 (3)
C10A—N1—C18—C2340.9 (3)C40A—N31—C48—C5335.1 (3)
N2—N1—C18—C23140.7 (2)N32—N31—C48—C53142.9 (2)
C23—C18—C19—C200.7 (4)C53—C48—C49—C502.1 (3)
N1—C18—C19—C20179.1 (2)N31—C48—C49—C50178.9 (2)
C18—C19—C20—C211.8 (4)C48—C49—C50—C510.7 (4)
C19—C20—C21—C222.5 (4)C49—C50—C51—C522.4 (4)
C20—C21—C22—C230.7 (4)C50—C51—C52—C531.2 (4)
C21—C22—C23—C181.9 (4)C51—C52—C53—C481.6 (4)
C19—C18—C23—C222.6 (3)C49—C48—C53—C523.3 (3)
N1—C18—C23—C22177.3 (2)N31—C48—C53—C52177.7 (2)
C5A—N6—C24—C2519.9 (3)C35A—N36—C54—C5522.3 (3)
N7—N6—C24—C25158.41 (19)N37—N36—C54—C55157.59 (19)
C5A—N6—C24—C29162.5 (2)C35A—N36—C54—C59159.7 (2)
N7—N6—C24—C2919.3 (3)N37—N36—C54—C5920.5 (3)
C29—C24—C25—C261.7 (3)C59—C54—C55—C562.4 (3)
N6—C24—C25—C26179.34 (19)N36—C54—C55—C56179.57 (19)
C24—C25—C26—C271.1 (3)C54—C55—C56—C571.8 (3)
C25—C26—C27—C280.5 (4)C55—C56—C57—C580.3 (4)
C26—C27—C28—C291.6 (4)C56—C57—C58—C590.7 (4)
C27—C28—C29—C241.1 (4)C57—C58—C59—C540.1 (4)
C25—C24—C29—C280.6 (3)C55—C54—C59—C581.5 (3)
N6—C24—C29—C28178.32 (19)N36—C54—C59—C58179.5 (2)

Experimental details

Crystal data
Chemical formulaC23H22N6
Mr382.46
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)11.224 (1), 13.650 (1), 14.110 (1)
α, β, γ (°)75.270 (2), 73.070 (2), 76.270 (2)
V3)1968.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.20 × 0.15 × 0.12
Data collection
DiffractometerRigaku AFC7S
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7664, 7332, 4249
Rint0.091
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.141, 1.02
No. of reflections7332
No. of parameters570
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.23

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1995), SHELXL97.

Selected geometric parameters (Å, º) top
C4—N51.490 (3)C34—N351.487 (3)
N5—C5A1.409 (2)N35—C35A1.408 (3)
N5—C151.472 (3)N35—C451.477 (3)
C9—N101.489 (2)C39—N401.484 (3)
N10—C10A1.412 (2)N40—C40A1.410 (2)
N10—C151.474 (3)N40—C451.480 (3)
C5A—N5—C4111.97 (15)C35A—N35—C34111.79 (16)
C10A—N10—C9111.22 (15)C40A—N40—C39111.50 (15)
N5—C15—N10113.19 (16)N35—C45—N40113.06 (16)
C4—N5—C5A—N679.2 (2)C34—N35—C35A—N3678.9 (2)
C9—N10—C10A—N176.0 (2)C39—N40—C40A—N3176.0 (2)
N2—N1—C18—C1939.5 (3)N32—N31—C48—C4936.1 (3)
N7—N6—C24—C2919.3 (3)N37—N36—C54—C5920.5 (3)
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds