3-Methyl-1,4-diphenyl-1H-pyrazolo­[3,4-b]quinoline

Szlachcic, P.; Danel, A.; Stadnicka, K.

doi:10.1107/S1600536810042935

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3009

https://doi.org/10.1107/S1600536810042935

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3-Methyl-1,4-diphenyl-1H-pyrazolo[3,4-b]quinoline

Paweł Szlachcic,^a ^* Andrzej Danel ^a and Katarzyna Stadnicka ^b

^aDepartment of Chemistry and Physics, Agricultural University, 30-149 Kraków, Poland, and ^bFaculty of Chemistry, Jagiellonian University, 30-060 Kraków, Poland
^*Correspondence e-mail: pszlachcic@ar.krakow.pl

(Received 30 September 2010; accepted 21 October 2010; online 31 October 2010)

In the title molecule, C₂₃H₁₇N₃, the phenyl substituents at positions 1 and 4 are twisted relative to the central core by 27.09 (5) and 66.62 (4)°, respectively. In the crystal, molecules are assembled into centrosymmetric dimers via π–π stacking interactions between the 1H-pyrazolo[3,4-b]quinoline units, with an interplanar distance of 3.601 (2) Å and by weak intermolecular C—H⋯N interactions.

Related literature

For the synthesis of 1,3 and 4-substituted 1H-pyrazolo[3,4-b]quinoline derivatives using Friedländer condensation, see: Danel (1996 ); Woo et al. (2002 ). For selected photophysical properties of 1H-pyrazolo[3,4-b]quinoline derivatives, see: Gondek et al. (2006 ). For related structures, see: Szlachcic & Stadnicka (2010 ); Szlachcic et al. (2010 ).

Experimental

Crystal data

C₂₃H₁₇N₃
M_r = 335.40
Triclinic, $[P \overline 1]$
a = 9.2120 (4) Å
b = 9.9377 (5) Å
c = 10.3440 (4) Å
α = 92.278 (2)°
β = 113.376 (2)°
γ = 90.152 (2)°
V = 868.37 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.50 × 0.42 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.963, T_max = 0.989
6556 measured reflections
4964 independent reflections
3285 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.139
S = 1.02
4964 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C46—H46⋯N9ⁱ	0.93	2.52	3.4164 (18)	163
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810042935/gk2306sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042935/gk2306Isup2.hkl

checkCIF report

Comment top

The title compound and other 1H-pyrazolo[3,4-b]quinoline (PQ) derivatives containing hydrogen, methyl or phenyl substituents and their combination, showed important photophysical properties (Gondek et al., 2006) which could be utilized in organic light-emitting diodes (OLED) fabrication. To synthesize 1,3,4-substituted PQ derivatives, a method of preparation introduced by Danel (1996) was used. The results of using the title compound in OLED preparation will be published elsewhere.

The shape of the title molecule is shown in Fig. 1. The core of the molecule, 1H-pyrazolo[3,4-b]quinoline, is planar and aromatic. The planes of phenyl substituents at positions 1 and 4 are twisted against the core moiety with the torsion angles N2—N1—C11—C16 = -15.7 (2) and C3a—C4—C41—C46 = 116.7 (2)°. The conformation of the molecule is stabilized by two intramolecular interactions of C—H···N type in which N2 and N9 atoms are acceptors.

The packing of the molecules (Fig. 2) is determined by one weak intermolecular hydrogen bond C46—H46···N9 (-x + 1, -y + 1, -z), and π-π interactions: with Cg1 (N1—N2—C3—C3a—C9a)···Cg3 (C4a—C5—C6—C7—C8—C8a at 1 - x, 1 - y, -z) = 3.731 and Cg2 (C3a—C4—C4a—C8a—N9—C9a)···Cg2 (C3a—C4—C4a—C8a—N9—C9a at 1 - x, 1 - y, -z) = 3.799 Å resulting in forming molecular dimers. The two C—H···π interactions are described by the geometry parameters (H···A /Å, D···A /Å, <DHA /°, respectively) given below:

C6—H6···Cg5 (C41—C42—C43—C44—C45—C46 at 2 - x, 1 - y, -z): 2.967, 3.750, 143;

C31—H31···Cg1 (N1—N2—C3—C3a—C9a at 1 - x, -y, -z): 3.172, 3.875, 132.

Related literature top

For the synthesis of 1,3 and 4-substituted 1H-pyrazolo[3,4-b]quinoline derivatives using Friedländer condensation, see: Danel (1996); Woo et al. (2002). For selected photophysical properties of 1H-pyrazolo[3,4-b]quinoline derivatives, see: Gondek et al. (2006). For related structures, see: Szlachcic & Stadnicka (2010); Szlachcic et al. (2010).

Experimental top

The title compound was synthesized using procedure already described in literature (Danel, 1996) from 2-aminobenzophenone and 5-methyl-2-phenyl-2,4-dihydro-pyrazol-3-one (10 mmol of each substrate, ethylene glycol as a solvent). The product was purified by flash chromatography on Al₂O₃ with chloroform as a solvent, followed by crystallization from toluene/petroleum ether to give 2.38 g (71% yield) of light-yellow crystalline solid, mp. 438–440 K. ¹H NMR (CDCl₃): δ 2.14 (s, 3H), 7.25–7.30 (m, 1H), 7.36 (ddd, J = 8.6, 6.7, 1.3 Hz, 1H), 7.44–7.47 (m, 2H), 7.52–7.60 (m, 5H). 7.71–7.77 (m, 2H), 8.20 (d, J = 8.4 Hz, 1H), 8.49–8.53 (m, 2H). ¹³C NMR (CDCl₃): δ 14.9, 116.3, 120.3, 123.6, 123.9, 124.9, 127.0, 128.3, 128.7, 129.0 (two signals), 129.7, 130.3, 135.0, 140.0, 143.8, 144.4, 148.5, 150.2. Single crystals suitable for X-ray diffraction were grown by slow evaporation from toluene solution at ambient conditions.

Structure description top

C6—H6···Cg5 (C41—C42—C43—C44—C45—C46 at 2 - x, 1 - y, -z): 2.967, 3.750, 143;

C31—H31···Cg1 (N1—N2—C3—C3a—C9a at 1 - x, -y, -z): 3.172, 3.875, 132.

For the synthesis of 1,3 and 4-substituted 1H-pyrazolo[3,4-b]quinoline derivatives using Friedländer condensation, see: Danel (1996); Woo et al. (2002). For selected photophysical properties of 1H-pyrazolo[3,4-b]quinoline derivatives, see: Gondek et al. (2006). For related structures, see: Szlachcic & Stadnicka (2010); Szlachcic et al. (2010).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The conformation of the 3-methyl-1,4-diphenyl-1H-pyrazolo[3,4-b]quinoline molecule with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The unit-cell contents of the title compound in projection along [001] showing molecular dimers formation.

3-Methyl-1,4-diphenyl-1H-pyrazolo[3,4-b]quinoline top

Crystal data top

C₂₃H₁₇N₃	Z = 2
M_r = 335.40	F(000) = 352
Triclinic, P1	D_x = 1.283 Mg m⁻³
Hall symbol: -P 1	Melting point = 438–440 K
a = 9.2120 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9377 (5) Å	Cell parameters from 2458 reflections
c = 10.3440 (4) Å	θ = 1.0–30.0°
α = 92.278 (2)°	µ = 0.08 mm⁻¹
β = 113.376 (2)°	T = 293 K
γ = 90.152 (2)°	Plate, green–yellow
V = 868.37 (7) Å³	0.50 × 0.42 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	4964 independent reflections
Radiation source: fine-focus sealed tube	3285 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.020
Detector resolution: 9 pixels mm^-1	θ_max = 30.0°, θ_min = 2.9°
φ and ο scans to fill Ewald sphere	h = −12→11
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	k = −13→7
T_min = 0.963, T_max = 0.989	l = −14→13
6556 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.054P)² + 0.1697P] where P = (F_o² + 2F_c²)/3
4964 reflections	(Δ/σ)_max < 0.001
236 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³
0 constraints

Crystal data top

C₂₃H₁₇N₃	γ = 90.152 (2)°
M_r = 335.40	V = 868.37 (7) Å³
Triclinic, P1	Z = 2
a = 9.2120 (4) Å	Mo Kα radiation
b = 9.9377 (5) Å	µ = 0.08 mm⁻¹
c = 10.3440 (4) Å	T = 293 K
α = 92.278 (2)°	0.50 × 0.42 × 0.15 mm
β = 113.376 (2)°

Data collection top

Nonius KappaCCD diffractometer	4964 independent reflections
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	3285 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.989	R_int = 0.020
6556 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.02	Δρ_max = 0.24 e Å⁻³
4964 reflections	Δρ_min = −0.17 e Å⁻³
236 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

	x	y	z	U_iso*/U_eq
N1	0.34388 (14)	0.18687 (11)	0.08010 (12)	0.0397 (3)
N2	0.28625 (15)	0.11194 (12)	−0.04633 (13)	0.0438 (3)
C3	0.37588 (17)	0.13841 (14)	−0.11453 (15)	0.0416 (3)
C3A	0.49700 (16)	0.23706 (13)	−0.03567 (14)	0.0351 (3)
C4	0.61386 (15)	0.31001 (13)	−0.05685 (14)	0.0344 (3)
C4A	0.70159 (15)	0.40697 (13)	0.05158 (14)	0.0345 (3)
C5	0.82339 (17)	0.49062 (14)	0.04416 (15)	0.0418 (3)
H5	0.8450	0.4851	−0.0364	0.050*
C6	0.90904 (18)	0.57853 (16)	0.15214 (17)	0.0478 (4)
H6	0.9870	0.6330	0.1441	0.057*
C7	0.88014 (19)	0.58731 (16)	0.27575 (17)	0.0514 (4)
H7	0.9402	0.6466	0.3497	0.062*
C8	0.76495 (18)	0.50976 (15)	0.28780 (16)	0.0464 (4)
H8	0.7476	0.5163	0.3704	0.056*
C8A	0.67061 (15)	0.41895 (13)	0.17655 (14)	0.0356 (3)
N9	0.55506 (13)	0.34765 (11)	0.19637 (12)	0.0381 (3)
C9A	0.47232 (15)	0.26467 (13)	0.08992 (14)	0.0343 (3)
C11	0.25132 (16)	0.19574 (13)	0.16186 (14)	0.0378 (3)
C12	0.31890 (19)	0.24076 (15)	0.30166 (16)	0.0487 (4)
H12	0.4260	0.2639	0.3436	0.058*
C13	0.2259 (2)	0.25117 (17)	0.37876 (19)	0.0579 (4)
H13	0.2706	0.2831	0.4723	0.069*
C14	0.0681 (2)	0.21477 (17)	0.3187 (2)	0.0591 (4)
H14	0.0064	0.2220	0.3712	0.071*
C15	0.00234 (19)	0.16761 (17)	0.18044 (19)	0.0553 (4)
H15	−0.1038	0.1413	0.1401	0.066*
C16	0.09222 (17)	0.15891 (15)	0.10080 (17)	0.0455 (3)
H16	0.0464	0.1285	0.0068	0.055*
C31	0.3400 (2)	0.06994 (18)	−0.25516 (17)	0.0578 (4)
H31A	0.4209	0.0063	−0.2477	0.087*
H31B	0.3365	0.1358	−0.3217	0.087*
H31C	0.2395	0.0237	−0.2866	0.087*
C41	0.64981 (16)	0.28577 (13)	−0.18381 (14)	0.0357 (3)
C42	0.70864 (19)	0.16239 (15)	−0.20626 (16)	0.0462 (4)
H42	0.7243	0.0953	−0.1421	0.055*
C43	0.7441 (2)	0.13829 (17)	−0.32315 (18)	0.0540 (4)
H43	0.7836	0.0555	−0.3371	0.065*
C44	0.72084 (19)	0.23688 (18)	−0.41857 (17)	0.0524 (4)
H44	0.7443	0.2207	−0.4973	0.063*
C45	0.66269 (18)	0.35998 (17)	−0.39743 (16)	0.0491 (4)
H45	0.6468	0.4265	−0.4622	0.059*
C46	0.62795 (17)	0.38491 (14)	−0.28066 (15)	0.0417 (3)
H46	0.5898	0.4684	−0.2667	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0428 (6)	0.0404 (6)	0.0370 (6)	−0.0120 (5)	0.0179 (5)	−0.0042 (5)
N2	0.0489 (7)	0.0417 (6)	0.0396 (6)	−0.0131 (5)	0.0172 (5)	−0.0058 (5)
C3	0.0461 (8)	0.0386 (7)	0.0390 (7)	−0.0073 (6)	0.0164 (6)	−0.0017 (6)
C3A	0.0399 (7)	0.0325 (6)	0.0335 (6)	−0.0019 (5)	0.0153 (6)	0.0008 (5)
C4	0.0363 (7)	0.0329 (6)	0.0353 (7)	0.0014 (5)	0.0156 (6)	0.0018 (5)
C4A	0.0342 (7)	0.0335 (6)	0.0375 (7)	−0.0004 (5)	0.0162 (6)	−0.0003 (5)
C5	0.0409 (8)	0.0449 (8)	0.0444 (8)	−0.0061 (6)	0.0223 (6)	−0.0029 (6)
C6	0.0417 (8)	0.0495 (8)	0.0561 (9)	−0.0134 (6)	0.0243 (7)	−0.0065 (7)
C7	0.0485 (9)	0.0547 (9)	0.0517 (9)	−0.0176 (7)	0.0225 (7)	−0.0156 (7)
C8	0.0461 (8)	0.0537 (8)	0.0429 (8)	−0.0131 (7)	0.0230 (7)	−0.0122 (7)
C8A	0.0351 (7)	0.0359 (6)	0.0372 (7)	−0.0031 (5)	0.0160 (6)	−0.0012 (5)
N9	0.0389 (6)	0.0401 (6)	0.0370 (6)	−0.0073 (5)	0.0173 (5)	−0.0032 (5)
C9A	0.0359 (7)	0.0331 (6)	0.0352 (6)	−0.0033 (5)	0.0155 (5)	0.0018 (5)
C11	0.0420 (7)	0.0326 (6)	0.0419 (7)	−0.0047 (5)	0.0198 (6)	0.0043 (6)
C12	0.0521 (9)	0.0529 (9)	0.0428 (8)	−0.0151 (7)	0.0210 (7)	−0.0023 (7)
C13	0.0749 (12)	0.0548 (9)	0.0531 (10)	−0.0144 (8)	0.0360 (9)	−0.0073 (8)
C14	0.0658 (11)	0.0563 (10)	0.0722 (12)	0.0003 (8)	0.0455 (10)	0.0011 (9)
C15	0.0425 (9)	0.0590 (10)	0.0689 (11)	−0.0006 (7)	0.0265 (8)	0.0083 (9)
C16	0.0411 (8)	0.0467 (8)	0.0467 (8)	−0.0052 (6)	0.0151 (7)	0.0040 (7)
C31	0.0659 (11)	0.0612 (10)	0.0460 (9)	−0.0213 (8)	0.0237 (8)	−0.0155 (8)
C41	0.0369 (7)	0.0365 (7)	0.0355 (7)	−0.0032 (5)	0.0167 (6)	−0.0012 (6)
C42	0.0563 (9)	0.0398 (7)	0.0454 (8)	0.0040 (6)	0.0235 (7)	0.0007 (6)
C43	0.0632 (10)	0.0498 (9)	0.0546 (10)	0.0061 (8)	0.0301 (8)	−0.0069 (8)
C44	0.0532 (9)	0.0675 (10)	0.0417 (8)	−0.0034 (8)	0.0256 (7)	−0.0085 (8)
C45	0.0523 (9)	0.0582 (9)	0.0403 (8)	−0.0035 (7)	0.0218 (7)	0.0067 (7)
C46	0.0453 (8)	0.0412 (7)	0.0421 (8)	0.0010 (6)	0.0212 (6)	0.0029 (6)

Geometric parameters (Å, º) top

N1—C9A	1.3790 (16)	C12—C13	1.385 (2)
N1—N2	1.3842 (16)	C12—H12	0.9300
N1—C11	1.4201 (17)	C13—C14	1.376 (3)
N2—C3	1.3132 (18)	C13—H13	0.9300
C3—C3A	1.4422 (19)	C14—C15	1.374 (3)
C3—C31	1.492 (2)	C14—H14	0.9300
C3A—C4	1.3885 (18)	C15—C16	1.381 (2)
C3A—C9A	1.4217 (18)	C15—H15	0.9300
C4—C4A	1.4249 (18)	C16—H16	0.9300
C4—C41	1.4876 (18)	C31—H31A	0.9600
C4A—C5	1.4228 (18)	C31—H31B	0.9600
C4A—C8A	1.4308 (18)	C31—H31C	0.9600
C5—C6	1.361 (2)	C41—C42	1.3898 (19)
C5—H5	0.9300	C41—C46	1.3907 (19)
C6—C7	1.405 (2)	C42—C43	1.384 (2)
C6—H6	0.9300	C42—H42	0.9300
C7—C8	1.358 (2)	C43—C44	1.375 (2)
C7—H7	0.9300	C43—H43	0.9300
C8—C8A	1.4190 (19)	C44—C45	1.381 (2)
C8—H8	0.9300	C44—H44	0.9300
C8A—N9	1.3631 (16)	C45—C46	1.381 (2)
N9—C9A	1.3160 (17)	C45—H45	0.9300
C11—C12	1.383 (2)	C46—H46	0.9300
C11—C16	1.3875 (19)

C9A—N1—N2	110.06 (11)	C11—C12—H12	120.3
C9A—N1—C11	129.37 (11)	C13—C12—H12	120.3
N2—N1—C11	119.07 (11)	C14—C13—C12	120.78 (16)
C3—N2—N1	108.04 (11)	C14—C13—H13	119.6
N2—C3—C3A	110.55 (12)	C12—C13—H13	119.6
N2—C3—C31	119.20 (13)	C15—C14—C13	119.47 (15)
C3A—C3—C31	130.23 (13)	C15—C14—H14	120.3
C4—C3A—C9A	118.45 (12)	C13—C14—H14	120.3
C4—C3A—C3	136.89 (13)	C14—C15—C16	120.71 (16)
C9A—C3A—C3	104.51 (11)	C14—C15—H15	119.6
C3A—C4—C4A	116.60 (12)	C16—C15—H15	119.6
C3A—C4—C41	122.02 (12)	C15—C16—C11	119.61 (15)
C4A—C4—C41	121.36 (11)	C15—C16—H16	120.2
C5—C4A—C4	123.14 (12)	C11—C16—H16	120.2
C5—C4A—C8A	117.71 (12)	C3—C31—H31A	109.5
C4—C4A—C8A	119.12 (11)	C3—C31—H31B	109.5
C6—C5—C4A	121.57 (13)	H31A—C31—H31B	109.5
C6—C5—H5	119.2	C3—C31—H31C	109.5
C4A—C5—H5	119.2	H31A—C31—H31C	109.5
C5—C6—C7	120.27 (13)	H31B—C31—H31C	109.5
C5—C6—H6	119.9	C42—C41—C46	118.74 (12)
C7—C6—H6	119.9	C42—C41—C4	119.81 (12)
C8—C7—C6	120.36 (14)	C46—C41—C4	121.45 (12)
C8—C7—H7	119.8	C43—C42—C41	120.68 (14)
C6—C7—H7	119.8	C43—C42—H42	119.7
C7—C8—C8A	121.18 (14)	C41—C42—H42	119.7
C7—C8—H8	119.4	C44—C43—C42	119.96 (14)
C8A—C8—H8	119.4	C44—C43—H43	120.0
N9—C8A—C8	117.20 (12)	C42—C43—H43	120.0
N9—C8A—C4A	123.94 (12)	C43—C44—C45	119.95 (14)
C8—C8A—C4A	118.86 (12)	C43—C44—H44	120.0
C9A—N9—C8A	114.32 (11)	C45—C44—H44	120.0
N9—C9A—N1	125.83 (12)	C46—C45—C44	120.36 (14)
N9—C9A—C3A	127.35 (12)	C46—C45—H45	119.8
N1—C9A—C3A	106.81 (11)	C44—C45—H45	119.8
C12—C11—C16	119.95 (13)	C45—C46—C41	120.30 (13)
C12—C11—N1	120.37 (13)	C45—C46—H46	119.9
C16—C11—N1	119.67 (13)	C41—C46—H46	119.9
C11—C12—C13	119.46 (15)

C9A—N1—N2—C3	1.12 (16)	C11—N1—C9A—N9	14.3 (2)
C11—N1—N2—C3	168.47 (12)	N2—N1—C9A—C3A	−0.24 (15)
N1—N2—C3—C3A	−1.54 (16)	C11—N1—C9A—C3A	−165.91 (13)
N1—N2—C3—C31	179.75 (13)	C4—C3A—C9A—N9	−4.6 (2)
N2—C3—C3A—C4	−173.86 (15)	C3—C3A—C9A—N9	179.13 (13)
C31—C3—C3A—C4	4.7 (3)	C4—C3A—C9A—N1	175.65 (12)
N2—C3—C3A—C9A	1.37 (16)	C3—C3A—C9A—N1	−0.64 (14)
C31—C3—C3A—C9A	179.90 (16)	C9A—N1—C11—C12	−31.2 (2)
C9A—C3A—C4—C4A	0.62 (18)	N2—N1—C11—C12	164.26 (12)
C3—C3A—C4—C4A	175.37 (15)	C9A—N1—C11—C16	148.85 (14)
C9A—C3A—C4—C41	178.75 (12)	N2—N1—C11—C16	−15.73 (19)
C3—C3A—C4—C41	−6.5 (2)	C16—C11—C12—C13	−1.3 (2)
C3A—C4—C4A—C5	−179.09 (13)	N1—C11—C12—C13	178.74 (13)
C41—C4—C4A—C5	2.8 (2)	C11—C12—C13—C14	1.3 (3)
C3A—C4—C4A—C8A	3.01 (18)	C12—C13—C14—C15	0.0 (3)
C41—C4—C4A—C8A	−175.13 (12)	C13—C14—C15—C16	−1.3 (3)
C4—C4A—C5—C6	−177.40 (14)	C14—C15—C16—C11	1.3 (2)
C8A—C4A—C5—C6	0.5 (2)	C12—C11—C16—C15	0.0 (2)
C4A—C5—C6—C7	0.9 (2)	N1—C11—C16—C15	−179.99 (13)
C5—C6—C7—C8	−1.0 (3)	C3A—C4—C41—C42	−64.18 (18)
C6—C7—C8—C8A	−0.4 (3)	C4A—C4—C41—C42	113.86 (15)
C7—C8—C8A—N9	−178.35 (14)	C3A—C4—C41—C46	116.72 (15)
C7—C8—C8A—C4A	1.8 (2)	C4A—C4—C41—C46	−65.24 (18)
C5—C4A—C8A—N9	178.31 (13)	C46—C41—C42—C43	−0.3 (2)
C4—C4A—C8A—N9	−3.7 (2)	C4—C41—C42—C43	−179.45 (14)
C5—C4A—C8A—C8	−1.87 (19)	C41—C42—C43—C44	−0.1 (2)
C4—C4A—C8A—C8	176.15 (13)	C42—C43—C44—C45	0.2 (3)
C8—C8A—N9—C9A	−179.62 (13)	C43—C44—C45—C46	0.1 (2)
C4A—C8A—N9—C9A	0.20 (19)	C44—C45—C46—C41	−0.6 (2)
C8A—N9—C9A—N1	−176.24 (12)	C42—C41—C46—C45	0.7 (2)
C8A—N9—C9A—C3A	4.0 (2)	C4—C41—C46—C45	179.80 (13)
N2—N1—C9A—N9	179.99 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N9	0.93	2.44	3.0012 (18)	119
C46—H46···N9ⁱ	0.93	2.52	3.4164 (18)	163
C16—H16···N2	0.93	2.48	2.799 (2)	100

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₂₃H₁₇N₃
M_r	335.40
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.2120 (4), 9.9377 (5), 10.3440 (4)
α, β, γ (°)	92.278 (2), 113.376 (2), 90.152 (2)
V (Å³)	868.37 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.42 × 0.15

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.963, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	6556, 4964, 3285
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.139, 1.02
No. of reflections	4964
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.17

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C46—H46···N9ⁱ	0.93	2.52	3.4164 (18)	163

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors are grateful to the Ministry of Science and Higher Education, Poland, for financial support of this work through grant No. N N204 216734.

References

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