Crystal structure of N1-phenyl-N4-[(E)-(pyren-1-yl)methyl­idene]benzene-1,4-di­amine

Faizi, M.S.H.; Prisyazhnaya, E.V.

doi:10.1107/S2056989015001814

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ISSN: 2056-9890

Volume 71| Part 3| March 2015| Pages 261-263

doi:10.1107/S2056989015001814

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Crystal structure of N¹-phenyl-N⁴-[(E)-(pyren-1-yl)methylidene]benzene-1,4-diamine

Md. Serajul Haque Faizi ^a and Elena V. Prisyazhnaya ^b ^*

^aDepartment of Chemistry, Indian Institute of Technology Kanpur, Kanpur, UP 208 016, India, and ^bDepartment of Chemistry, Kyiv National University of Construction and Architecture, Povitroflotsky Avenue 31, 03680 Kiev, Ukraine
^*Correspondence e-mail: eprisyazhnaya@ukr.net

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 22 January 2015; accepted 27 January 2015; online 7 February 2015)

In the title compound, C₂₉H₂₀N₂, the dihedral angles subtended by the central p-phenylenediamine ring with respect to the mean plane of the terminal pyrenyl ring system (r.m.s. deviation = 0.027 Å) and the terminal N-phenyl ring are 29.34 (4) and 43.43 (7)°, respectively. The conformation about the C=N bond is E. In the crystal, molecules are linked by N—H⋯π and C—H⋯π interactions forming chains propagating along the [10-2] direction. These chains are linked via π–π interactions [inter-centroid distances are in the range 3.5569 (11)–3.708 (1) Å], forming slabs lying parallel to (30-4).

Keywords: crystal structure; N-phenyl-p-phenylenediamine; 1-pyrenecarboxaldehyde; PMBD; Schiff base; N—H⋯π and C—H⋯π interactions; π–π interactions.

CCDC reference: 1045835

1. Chemical context

Schiff bases often exhibit various biological activities, and in many cases have been shown to have antibacterial, anticancer, anti-inflammatory and antitoxic properties (Lozier et al., 1975 ). They are used as anion sensors (Dalapati et al., 2011 ), as non-linear optical compounds (Sun et al., 2012 ) and as versatile polynuclear ligands for multinuclear magnetic exchange clusters (Moroz et al., 2012 ). The pyrene unit is one of the most commonly used fluorophores due to its strong luminescence and chemical stability (Aoki et al., 1991 ; Nishizawa et al., 1999 ; van der Veen et al., 2000 ). Another interesting feature of the pyrene unit is the π–π interaction between pyrene aromatic rings in the crystal packing, which can permit the formation of highly ordered molecular aggregates in the solid state by architecturally controlled self-assembly (Desiraju et al., 1989 ; Munakata et al., 1994 ). Pyrene is a commonly used fluorophore due to its unusual fluorescent properties: intense fluorescence signals, vibronic band dependence with the media (Karpovich & Blanchard, 1995 ), and use in fluorescence sensors (Bell & Hext, 2004 ) and excimer formation (Lodeiro et al., 2006 ). As a result of these particular properties and because of its chemical stability, it is also employed as a probe for solid-state studies (Corma et al., 2002 ) and polymer association (Seixas de Melo et al., 2003 ). We report herein on the crystal structure of the title compound, synthesized by the condensation reaction of 1-pyrenecarboxaldehyde and N-phenyl-p-phenylenediamine.

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. The compound is non-planar, the dihedral angles between the central benzene ring (C7–C12) and the terminal phenyl ring (C1–C6) and the mean plane of the pyrenyl ring system (C14–C29; r.m.s. deviation = 0.027 Å) being 43.43 (9) and 29.33 (7)°, respectively. The conformation about the C13=N2 bond is E with a C10—N2—C13—C14 torsion angle of 178.13 (15)°.

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 40% probability level.

3. Supramolecular features

In the crystal, molecules are connected via N—H⋯π and C—H⋯π interactions forming zigzag chains propagating along [10 $[\overline{2}]$ ]; see Table 1 and Fig. 2. These chains are linked via π–π interactions involving inversion-related pyrenyl rings, forming two-dimensional networks lying parallel to (30 $[\overline{4}]$ ); see Fig. 3. The inter-centroid distances are 3.7051 (11), 3.708 (1), 3.6905 (11) and 3.5569 (11) Å for π–π interactions involving Cg3⋯Cg5ⁱⁱ, Cg3⋯Cg6ⁱⁱ, Cg4⋯Cg6ⁱⁱ and Cg6⋯Cg6ⁱⁱ, respectively, where Cg3, Cg4, Cg5 and Cg6 are the centroids of the C14–C17/C28–C27, C17–C20/C28–C29, C20–C24/C29 and C24–C29 rings, respectively [symmetry code: (ii) = −x + 1, −y, −z]. Interaction Cg6⋯Cg6ⁱⁱ is a slipped parallel π–π interaction with an interplanar distance of 3.3614 (7) Å and a slippage of 1.163 Å.

Table 1
N—H⋯π and C—H⋯π interactions (Å, °)

Cg5 and Cg6 are the centroids of the C20–C24/C29 and C24–C29 rings, respectively, in the pyrenyl ring system.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cg5ⁱ	0.89 (2)	2.80 (2)	3.6524 (19)	163 (2)
C6—H6⋯Cg6ⁱ	0.99 (2)	2.76 (2)	3.631 (2)	147 (1)
Symmetry code: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
A view along the b axis of the zigzag chain in the crystal of the title compound. The C—H⋯π and N—H⋯π interactions are shown as dashed lines (see Table 1

for details).

Figure 3
A view along the b axis of the crystal packing of the title compound. The C—H⋯π, N—H⋯π and π–π interactions are shown as dashed lines (see Table 1

for details).

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; last update November 2014; Groom & Allen, 2014 ) gave 20 hits for Schiff bases derived from pyrene-1-carbaldehyde. A search for Schiff base compounds involving N-phenyl-p-phenylenediamine gave three hits. Of these three compounds, N¹-phenyl-N⁴-(quinolin-2-ylmethylene)benzene-1,4-diamine {synonym: N-phenyl-4-[(quinolin-2-ylmethylene)amino]aniline; WOJJIQ; Faizi et al., 2014 } is the most similar to the title compound. Here the dihedral angles between the central benzene ring and the terminal phenyl ring and the quinoline ring system (r.m.s. deviation = 0.027 Å) are 44.72 (7) and 9.02 (4)°, respectively. In the title compound, the dihedral angles between the central benzene ring and the terminal phenyl ring and the pyrenyl ring system (r.m.s. deviation = 0.027 Å) are 43.43 (9) and 29.33 (7)°, respectively.

5. Synthesis and crystallization

80 mg (0.435 mmol) of N-phenyl-p-phenylenediamine were dissolved in 10 ml of absolute ethanol. To this solution, 100 mg (0.435 mmol) of pyrene-1-carbaldehyde in 5 ml of absolute ethanol was added dropwise under stirring. The mixture was stirred for 10 min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2h. The resulting yellow precipitate was recovered by filtration, washed several times with small portions of ice-cold ethanol and then with diethyl ether to give 150 mg (87%) of the title compound. Yellow block-like crystals suitable for X-ray analysis were obtained within 3 days by slow evaporation of a solution in MeOH.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH and C-bound H atoms were located from difference Fourier maps and freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₉H₂₀N₂
M_r	396.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.0433 (6), 12.2700 (5), 13.4981 (7)
β (°)	114.269 (2)
V (Å³)	1969.34 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.18 × 0.14 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004 )
T_min, T_max	0.986, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	19561, 4882, 3015
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.136, 1.02
No. of reflections	4882
No. of parameters	360
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.31
Computer programs: SMART and SAINT (Bruker, 2003 ), SIR97 (Altomare et al., 1999 ), DIAMOND (Brandenberg & Putz, 2006 ), Mercury (Macrae et al., 2008 ), SHELXL97 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1045835

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015001814/su5072sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015001814/su5072Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015001814/su5072Isup3.cml

checkCIF report

Chemical context top

Schiff bases often exhibit various biological activities, and in many cases have been shown to have antibacterial, anticancer, anti-inflammatory and antitoxic properties (Lozier et al., 1975). They are used as anion sensors (Dalapati et al., 2011), as non-linear optical compounds (Sun et al., 2012) and as versatile polynuclear ligands for multinuclear magnetic exchange clusters (Moroz et al., 2012). The pyrene unit is one of the most commonly used fluorophores due to its strong luminescence and chemical stability (Aoki et al., 1991; Nishizawa et al., 1999; van der Veen et al., 2000). Another interesting feature of the pyrene unit is the π–π interaction between pyrene aromatic rings in the crystal packing, which can permit the formation of highly ordered molecular aggregates in the solid state by architecturally controlled self-assembly (Desiraju et al., 1989; Munakata et al., 1994). Pyrene is a commonly used fluorophore due to its unusual fluorescent properties: intense fluorescence signals, vibronic band dependence with the media (Karpovich & Blanchard, 1995), and use in fluorescence sensors (Bell & Hext, 2004) and excimer formation (Lodeiro et al., 2006). As a result of these particular properties and because of its chemical stability, it is also employed as a probe for solid-state studies (Corma et al., 2002) and polymer association (Seixas de Melo et al., 2003). We report herein on the crystal structure of the title compound, synthesized by the condensation reaction of 1-pyrenecarboxaldehyde and N-phenyl-p-phenylenediamine.

Structural commentary top

The molecular structure of the title compound is illustrated in Fig. 1. The compound is non-planar, the dihedral angles between the central benzene ring (C7–C12) and the terminal phenyl ring (C1–C6) and the mean plane of the pyrenyl ring system (C14–C29; r.m.s. deviation = 0.027 Å) being 43.43 (9) and 29.33 (7)°, respectively. The conformation about the C13═N2 bond is E with a C10—N2—C13—C14 torsion angle of 178.13 (15)°.

Supramolecular features top

In the crystal, molecules are connected via N—H···π and C—H···π interactions forming zigzag chains propagating along [102]; see Table 1 and Fig 2. These chains are linked via π–π interactions involving inversion-related pyrenyl rings, forming two-dimensional networks lying parallel to (304); see Fig. 3. The inter-centroid distances are 3.7051 (11), 3.708 (1), 3.6905 (11) and 3.5569 (11) Å for π–π interactions involving Cg3···Cg5ⁱ, Cg3···Cg6ⁱ, Cg4···Cg6ⁱ and Cg6···Cg6ⁱ, respectively, where Cg3, Cg4, Cg5 and Cg6 are the centroids of the C14–C17/C28–C27, C17–C20/C28–C29, C20–C24/C29 and C24–C29 rings, respectively [symmetry code: (i) = -x + 1, -y, -z]. Interaction Cg6···Cg6ⁱ is a slipped parallel π–π interaction with an interplanar distance of 3.3614 (7) Å and a slippage of 1.163 Å.

Database survey top

A search of the Cambridge Structural Database (Version 5.36; last update November 2014; Groom & Allen, 2014) gave 20 hits for Schiff bases derived from pyrene-1-carbaldehyde. A search for Schiff base compounds involving N-phenyl-p-phenylenediamine gave three hits. Of these three compounds, N¹-phenyl-N⁴ -(quinolin-2-ylmethylene)benzene-1,4-diamine {synonym: N-phenyl-4-[(quinolin-2-ylmethylene)amino]aniline; WOJJIQ; Faizi et al., 2014} is the most similar to the title compound. Here the dihedral angles between the central benzene ring and the terminal phenyl ring and the quinoline ring system (r.m.s. deviation = 0.027 Å) are 44.72 (7) and 9.02 (4)°, respectively. In the title compound, the dihedral angles between the central benzene ring and the terminal phenyl ring and the pyrenyl ring system (r.m.s. deviation = 0.027 Å) are 43.43 (9) and 29.33 (7)°, respectively.

Synthesis and crystallization top

80 mg (0.435 mmol) of N-phenyl-p-phenylenediamine were dissolved in 10 ml of absolute ethanol. To this solution, 100 mg (0.435 mmol) of pyrene-1-carbaldehyde in 5 ml of absolute ethanol was added dropwise under stirring. The mixture was stirred for 10 min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2h. The resulting yellow precipitate was recovered by filtration, washed several times with small portions of ice-cold ethanol and then with diethyl ether to give 150 mg (87%) of the title compound. Yellow block-like crystals suitable for X-ray analysis was obtained within 3 days by slow evaporation of a solution in MeOH.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH and C-bound H atoms were located from difference Fourier maps and freely refined.

Related literature top

For related literature, see: Aoki et al. (1991); Bell & Hext (2004); Corma et al. (2002); Dalapati et al. (2011); Desiraju & Gavezzotti (1989); Faizi et al. (2014); Groom & Allen (2014); Karpovich & Blanchard (1995); Lodeiro et al. (2006); Lozier et al. (1975); Moroz et al. (2012); Munakata et al. (1994); Nishizawa et al. (1999); Seixas de Melo, Costa, Miguel, Lindman & Schillén (2003); Sun et al. (2012); van der Veen et al. (2000).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenberg & Putz, 2006) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A view along the b axis of the zigzag chain in the crystal of the title compound. The C—H···π and N—H···π interactions are shown as dashed lines (see Table 1 for details).
	Fig. 3. A view along the b axis of the crystal packing of the title compound. The C—H···π, N—H···π and π–π interactions are shown as dashed lines (see Table 1 for details).

N¹-Phenyl-N⁴-[(E)-(pyren-1-yl)methylidene]benzene-1,4-diamine top

Crystal data top

C₂₉H₂₀N₂	F(000) = 832
M_r = 396.47	D_x = 1.337 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4765 reflections
a = 13.0433 (6) Å	θ = 2.5–28.1°
b = 12.2700 (5) Å	µ = 0.08 mm⁻¹
c = 13.4981 (7) Å	T = 100 K
β = 114.269 (2)°	Block, yellow
V = 1969.34 (16) Å³	0.18 × 0.14 × 0.12 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	4882 independent reflections
Radiation source: fine-focus sealed tube	3015 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→17
T_min = 0.986, T_max = 0.991	k = −15→16
19561 measured reflections	l = −18→17

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0618P)² + 0.3614P] where P = (F_o² + 2F_c²)/3
4882 reflections	(Δ/σ)_max < 0.001
360 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₂₉H₂₀N₂	V = 1969.34 (16) Å³
M_r = 396.47	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.0433 (6) Å	µ = 0.08 mm⁻¹
b = 12.2700 (5) Å	T = 100 K
c = 13.4981 (7) Å	0.18 × 0.14 × 0.12 mm
β = 114.269 (2)°

Data collection top

Bruker APEXII CCD diffractometer	4882 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3015 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.991	R_int = 0.058
19561 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.136	All H-atom parameters refined
S = 1.02	Δρ_max = 0.27 e Å⁻³
4882 reflections	Δρ_min = −0.31 e Å⁻³
360 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.

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
N2	0.81481 (12)	0.07101 (12)	0.38507 (11)	0.0234 (4)
C27	0.53428 (14)	0.02897 (14)	0.16435 (13)	0.0185 (4)
C17	0.49949 (14)	−0.16939 (14)	0.13951 (13)	0.0209 (4)
C29	0.35640 (14)	−0.04116 (14)	0.02242 (13)	0.0185 (4)
C14	0.64048 (14)	0.00667 (14)	0.24975 (13)	0.0192 (4)
C20	0.28576 (14)	−0.13001 (14)	−0.03213 (13)	0.0209 (4)
C15	0.67242 (15)	−0.10188 (15)	0.27839 (14)	0.0223 (4)
C10	0.89081 (14)	0.15581 (14)	0.43730 (13)	0.0216 (4)
C13	0.71978 (14)	0.09325 (15)	0.30778 (13)	0.0211 (4)
N1	1.12616 (13)	0.39778 (14)	0.60829 (12)	0.0289 (4)
C6	1.28287 (16)	0.47750 (15)	0.75618 (15)	0.0262 (4)
C18	0.42695 (15)	−0.25720 (15)	0.08151 (15)	0.0237 (4)
C28	0.46352 (13)	−0.06019 (14)	0.10921 (12)	0.0177 (4)
C23	0.21349 (15)	0.08409 (15)	−0.09503 (13)	0.0223 (4)
C25	0.39177 (15)	0.15502 (15)	0.04656 (13)	0.0207 (4)
C24	0.31949 (14)	0.06726 (14)	−0.00974 (13)	0.0186 (4)
C1	1.18326 (14)	0.41717 (14)	0.71999 (13)	0.0218 (4)
C16	0.60457 (15)	−0.18739 (15)	0.22482 (14)	0.0227 (4)
C21	0.18068 (15)	−0.10853 (15)	−0.11566 (14)	0.0227 (4)
C19	0.32537 (15)	−0.23874 (15)	0.00075 (15)	0.0248 (4)
C8	1.04477 (14)	0.21599 (15)	0.60259 (14)	0.0225 (4)
C2	1.14291 (15)	0.38326 (15)	0.79601 (14)	0.0218 (4)
C26	0.49341 (14)	0.13708 (15)	0.12909 (13)	0.0205 (4)
C3	1.20224 (16)	0.40741 (15)	0.90521 (14)	0.0243 (4)
C22	0.14500 (15)	−0.00301 (15)	−0.14681 (14)	0.0242 (4)
C9	0.96797 (14)	0.13737 (16)	0.54378 (14)	0.0224 (4)
C4	1.30180 (16)	0.46528 (15)	0.94087 (15)	0.0277 (4)
C7	1.04841 (14)	0.31582 (15)	0.55524 (14)	0.0230 (4)
C12	0.97321 (15)	0.33348 (16)	0.44705 (14)	0.0255 (4)
C5	1.34123 (17)	0.50082 (16)	0.86574 (15)	0.0288 (5)
C11	0.89664 (15)	0.25524 (16)	0.38926 (14)	0.0251 (4)
H1A	1.1460 (18)	0.4403 (18)	0.5660 (18)	0.047 (7)*
H11	0.8478 (13)	0.2685 (13)	0.3158 (14)	0.018 (4)*
H15	0.7446 (15)	−0.1160 (14)	0.3384 (14)	0.023 (5)*
H9	0.9661 (14)	0.0706 (15)	0.5772 (14)	0.021 (5)*
H8	1.0955 (14)	0.2013 (14)	0.6739 (14)	0.021 (5)*
H16	0.6282 (14)	−0.2600 (15)	0.2463 (14)	0.021 (5)*
H6	1.3112 (15)	0.5027 (15)	0.7024 (15)	0.030 (5)*
H2	1.0753 (15)	0.3456 (14)	0.7734 (13)	0.020 (5)*
H12	0.9774 (15)	0.4012 (16)	0.4143 (14)	0.028 (5)*
H3	1.1711 (16)	0.3855 (15)	0.9576 (16)	0.034 (5)*
H26	0.5406 (14)	0.1991 (15)	0.1644 (14)	0.021 (5)*
H22	0.0715 (15)	0.0126 (14)	−0.2071 (14)	0.020 (5)*
H18	0.4536 (14)	−0.3307 (15)	0.1048 (13)	0.022 (5)*
H4	1.3450 (15)	0.4810 (14)	1.0175 (15)	0.029 (5)*
H23	0.1887 (15)	0.1603 (15)	−0.1163 (14)	0.026 (5)*
H5	1.4111 (17)	0.5434 (16)	0.8905 (16)	0.041 (6)*
H21	0.1325 (14)	−0.1709 (14)	−0.1498 (13)	0.018 (4)*
H19	0.2740 (15)	−0.2977 (15)	−0.0384 (15)	0.030 (5)*
H13	0.6979 (14)	0.1714 (15)	0.2880 (14)	0.024 (5)*
H25	0.3679 (14)	0.2288 (15)	0.0244 (14)	0.022 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0218 (8)	0.0270 (9)	0.0196 (7)	−0.0022 (7)	0.0067 (6)	−0.0027 (6)
C27	0.0209 (9)	0.0220 (10)	0.0159 (8)	0.0004 (7)	0.0110 (7)	−0.0008 (7)
C17	0.0223 (9)	0.0228 (10)	0.0225 (9)	0.0006 (8)	0.0142 (8)	0.0022 (7)
C29	0.0200 (9)	0.0212 (10)	0.0184 (8)	−0.0007 (7)	0.0119 (7)	−0.0010 (7)
C14	0.0199 (9)	0.0241 (10)	0.0161 (8)	0.0012 (7)	0.0099 (7)	−0.0009 (7)
C20	0.0212 (9)	0.0233 (10)	0.0222 (9)	−0.0035 (8)	0.0131 (7)	−0.0016 (7)
C15	0.0207 (9)	0.0289 (11)	0.0177 (9)	0.0035 (8)	0.0084 (7)	0.0027 (8)
C10	0.0176 (9)	0.0247 (10)	0.0227 (9)	0.0010 (8)	0.0087 (7)	−0.0021 (7)
C13	0.0223 (9)	0.0237 (10)	0.0191 (8)	0.0021 (8)	0.0103 (7)	−0.0016 (7)
N1	0.0320 (9)	0.0360 (10)	0.0192 (8)	−0.0125 (8)	0.0109 (7)	−0.0018 (7)
C6	0.0296 (10)	0.0274 (11)	0.0268 (9)	−0.0048 (9)	0.0170 (8)	−0.0038 (8)
C18	0.0284 (10)	0.0182 (10)	0.0294 (9)	−0.0011 (8)	0.0168 (8)	0.0022 (8)
C28	0.0198 (9)	0.0203 (10)	0.0164 (8)	0.0002 (7)	0.0111 (7)	0.0004 (7)
C23	0.0236 (9)	0.0247 (10)	0.0194 (9)	0.0042 (8)	0.0095 (7)	0.0025 (8)
C25	0.0252 (9)	0.0185 (10)	0.0205 (9)	0.0038 (8)	0.0115 (8)	0.0006 (7)
C24	0.0201 (9)	0.0223 (10)	0.0166 (8)	−0.0005 (8)	0.0108 (7)	−0.0016 (7)
C1	0.0224 (9)	0.0218 (10)	0.0206 (8)	0.0015 (8)	0.0081 (7)	−0.0006 (7)
C16	0.0259 (10)	0.0198 (10)	0.0242 (9)	0.0032 (8)	0.0122 (8)	0.0055 (8)
C21	0.0210 (9)	0.0273 (11)	0.0221 (9)	−0.0059 (8)	0.0112 (8)	−0.0052 (8)
C19	0.0267 (10)	0.0217 (10)	0.0304 (10)	−0.0070 (9)	0.0163 (8)	−0.0041 (8)
C8	0.0186 (9)	0.0290 (11)	0.0181 (9)	0.0043 (8)	0.0057 (7)	−0.0007 (8)
C2	0.0192 (9)	0.0209 (10)	0.0243 (9)	0.0017 (8)	0.0080 (8)	0.0002 (7)
C26	0.0235 (9)	0.0191 (10)	0.0199 (9)	−0.0018 (8)	0.0100 (8)	−0.0027 (7)
C3	0.0295 (10)	0.0214 (10)	0.0240 (9)	0.0037 (8)	0.0131 (8)	0.0007 (8)
C22	0.0194 (9)	0.0331 (11)	0.0190 (9)	−0.0004 (8)	0.0069 (7)	−0.0008 (8)
C9	0.0216 (9)	0.0223 (10)	0.0228 (9)	0.0027 (8)	0.0086 (8)	0.0005 (8)
C4	0.0317 (11)	0.0263 (11)	0.0201 (9)	0.0004 (9)	0.0057 (8)	−0.0055 (8)
C7	0.0214 (9)	0.0294 (11)	0.0206 (8)	−0.0029 (8)	0.0109 (7)	−0.0051 (8)
C12	0.0264 (10)	0.0286 (11)	0.0227 (9)	−0.0009 (9)	0.0113 (8)	0.0024 (8)
C5	0.0262 (10)	0.0277 (11)	0.0306 (10)	−0.0054 (9)	0.0097 (9)	−0.0091 (8)
C11	0.0212 (9)	0.0345 (11)	0.0169 (8)	−0.0004 (9)	0.0052 (7)	−0.0002 (8)

Geometric parameters (Å, º) top

N2—C13	1.279 (2)	C23—C22	1.384 (3)
N2—C10	1.410 (2)	C23—C24	1.404 (2)
C27—C14	1.418 (2)	C23—H23	0.992 (18)
C27—C28	1.428 (2)	C25—C26	1.354 (2)
C27—C26	1.436 (2)	C25—C24	1.427 (2)
C17—C16	1.399 (2)	C25—H25	0.964 (18)
C17—C28	1.423 (2)	C1—C2	1.395 (2)
C17—C18	1.435 (2)	C16—H16	0.949 (18)
C29—C24	1.421 (2)	C21—C22	1.382 (3)
C29—C20	1.422 (2)	C21—H21	0.977 (17)
C29—C28	1.426 (2)	C19—H19	0.980 (19)
C14—C15	1.402 (2)	C8—C9	1.382 (2)
C14—C13	1.465 (2)	C8—C7	1.391 (3)
C20—C21	1.396 (2)	C8—H8	0.934 (17)
C20—C19	1.434 (3)	C2—C3	1.386 (2)
C15—C16	1.371 (3)	C2—H2	0.928 (18)
C15—H15	0.972 (17)	C26—H26	0.972 (18)
C10—C9	1.393 (2)	C3—C4	1.381 (3)
C10—C11	1.398 (3)	C3—H3	0.99 (2)
C13—H13	1.004 (18)	C22—H22	0.988 (17)
N1—C7	1.398 (2)	C9—H9	0.941 (18)
N1—C1	1.401 (2)	C4—C5	1.383 (3)
N1—H1A	0.89 (2)	C4—H4	0.972 (18)
C6—C5	1.387 (3)	C7—C12	1.401 (2)
C6—C1	1.397 (2)	C12—C11	1.374 (3)
C6—H6	0.990 (19)	C12—H12	0.954 (19)
C18—C19	1.344 (2)	C5—H5	0.98 (2)
C18—H18	0.971 (18)	C11—H11	0.947 (16)

C13—N2—C10	119.79 (15)	C2—C1—C6	118.58 (16)
C14—C27—C28	118.84 (15)	C2—C1—N1	123.14 (16)
C14—C27—C26	123.60 (16)	C6—C1—N1	118.22 (16)
C28—C27—C26	117.57 (15)	C15—C16—C17	120.99 (17)
C16—C17—C28	118.76 (16)	C15—C16—H16	120.0 (10)
C16—C17—C18	122.26 (16)	C17—C16—H16	119.0 (10)
C28—C17—C18	118.98 (15)	C22—C21—C20	121.25 (17)
C24—C29—C20	119.58 (15)	C22—C21—H21	121.3 (9)
C24—C29—C28	119.93 (15)	C20—C21—H21	117.5 (10)
C20—C29—C28	120.49 (16)	C18—C19—C20	121.16 (17)
C15—C14—C27	119.20 (16)	C18—C19—H19	122.7 (11)
C15—C14—C13	118.50 (15)	C20—C19—H19	116.2 (11)
C27—C14—C13	122.28 (16)	C9—C8—C7	120.27 (16)
C21—C20—C29	119.05 (16)	C9—C8—H8	119.8 (11)
C21—C20—C19	122.34 (16)	C7—C8—H8	120.0 (11)
C29—C20—C19	118.61 (16)	C3—C2—C1	120.25 (18)
C16—C15—C14	121.83 (16)	C3—C2—H2	119.7 (11)
C16—C15—H15	119.8 (10)	C1—C2—H2	120.0 (11)
C14—C15—H15	118.4 (10)	C25—C26—C27	121.84 (17)
C9—C10—C11	117.78 (16)	C25—C26—H26	119.0 (10)
C9—C10—N2	117.22 (16)	C27—C26—H26	119.1 (10)
C11—C10—N2	124.96 (15)	C4—C3—C2	120.95 (18)
N2—C13—C14	121.06 (17)	C4—C3—H3	119.7 (11)
N2—C13—H13	119.6 (10)	C2—C3—H3	119.3 (11)
C14—C13—H13	119.3 (10)	C21—C22—C23	120.21 (16)
C7—N1—C1	128.77 (17)	C21—C22—H22	121.6 (10)
C7—N1—H1A	115.8 (14)	C23—C22—H22	118.2 (10)
C1—N1—H1A	115.2 (14)	C8—C9—C10	121.67 (18)
C5—C6—C1	120.40 (18)	C8—C9—H9	119.2 (10)
C5—C6—H6	120.7 (11)	C10—C9—H9	119.1 (11)
C1—C6—H6	118.9 (11)	C3—C4—C5	119.10 (17)
C19—C18—C17	121.66 (18)	C3—C4—H4	121.5 (11)
C19—C18—H18	121.4 (10)	C5—C4—H4	119.4 (11)
C17—C18—H18	116.9 (10)	C8—C7—N1	123.53 (16)
C17—C28—C27	120.37 (15)	C8—C7—C12	118.25 (16)
C17—C28—C29	119.10 (15)	N1—C7—C12	118.16 (17)
C27—C28—C29	120.53 (15)	C11—C12—C7	121.18 (18)
C22—C23—C24	120.94 (17)	C11—C12—H12	120.8 (11)
C22—C23—H23	121.0 (10)	C7—C12—H12	118.0 (11)
C24—C23—H23	118.0 (10)	C4—C5—C6	120.69 (18)
C26—C25—C24	121.64 (17)	C4—C5—H5	119.4 (12)
C26—C25—H25	119.3 (10)	C6—C5—H5	119.9 (12)
C24—C25—H25	119.0 (10)	C12—C11—C10	120.79 (16)
C23—C24—C29	118.96 (16)	C12—C11—H11	119.6 (10)
C23—C24—C25	122.55 (16)	C10—C11—H11	119.6 (10)
C29—C24—C25	118.50 (15)

C28—C27—C14—C15	−0.7 (2)	C26—C25—C24—C29	−0.1 (2)
C26—C27—C14—C15	179.71 (15)	C5—C6—C1—C2	1.4 (3)
C28—C27—C14—C13	177.73 (15)	C5—C6—C1—N1	178.65 (17)
C26—C27—C14—C13	−1.9 (3)	C7—N1—C1—C2	−24.6 (3)
C24—C29—C20—C21	−0.7 (2)	C7—N1—C1—C6	158.27 (18)
C28—C29—C20—C21	179.03 (15)	C14—C15—C16—C17	−0.7 (3)
C24—C29—C20—C19	179.20 (15)	C28—C17—C16—C15	−0.3 (3)
C28—C29—C20—C19	−1.1 (2)	C18—C17—C16—C15	179.62 (17)
C27—C14—C15—C16	1.2 (3)	C29—C20—C21—C22	0.8 (3)
C13—C14—C15—C16	−177.34 (16)	C19—C20—C21—C22	−179.15 (16)
C13—N2—C10—C9	154.37 (16)	C17—C18—C19—C20	1.0 (3)
C13—N2—C10—C11	−27.7 (3)	C21—C20—C19—C18	−179.97 (17)
C10—N2—C13—C14	178.13 (15)	C29—C20—C19—C18	0.1 (3)
C15—C14—C13—N2	−2.0 (2)	C6—C1—C2—C3	−1.3 (3)
C27—C14—C13—N2	179.52 (16)	N1—C1—C2—C3	−178.42 (17)
C16—C17—C18—C19	178.95 (17)	C24—C25—C26—C27	0.2 (3)
C28—C17—C18—C19	−1.2 (3)	C14—C27—C26—C25	179.47 (16)
C16—C17—C28—C27	0.7 (2)	C28—C27—C26—C25	−0.1 (2)
C18—C17—C28—C27	−179.21 (15)	C1—C2—C3—C4	0.1 (3)
C16—C17—C28—C29	−179.90 (15)	C20—C21—C22—C23	−0.1 (3)
C18—C17—C28—C29	0.2 (2)	C24—C23—C22—C21	−0.6 (3)
C14—C27—C28—C17	−0.2 (2)	C7—C8—C9—C10	−1.4 (3)
C26—C27—C28—C17	179.41 (15)	C11—C10—C9—C8	2.9 (3)
C14—C27—C28—C29	−179.59 (15)	N2—C10—C9—C8	−178.95 (15)
C26—C27—C28—C29	0.0 (2)	C2—C3—C4—C5	1.1 (3)
C24—C29—C28—C17	−179.38 (15)	C9—C8—C7—N1	−177.74 (17)
C20—C29—C28—C17	0.9 (2)	C9—C8—C7—C12	−0.5 (3)
C24—C29—C28—C27	0.0 (2)	C1—N1—C7—C8	−25.3 (3)
C20—C29—C28—C27	−179.71 (15)	C1—N1—C7—C12	157.42 (18)
C22—C23—C24—C29	0.6 (2)	C8—C7—C12—C11	0.9 (3)
C22—C23—C24—C25	−179.12 (16)	N1—C7—C12—C11	178.29 (17)
C20—C29—C24—C23	0.1 (2)	C3—C4—C5—C6	−1.0 (3)
C28—C29—C24—C23	−179.69 (15)	C1—C6—C5—C4	−0.3 (3)
C20—C29—C24—C25	179.77 (15)	C7—C12—C11—C10	0.6 (3)
C28—C29—C24—C25	0.0 (2)	C9—C10—C11—C12	−2.5 (3)
C26—C25—C24—C23	179.57 (16)	N2—C10—C11—C12	179.53 (17)

Hydrogen-bond geometry (Å, º) top

Cg5 and Cg6 are the centroids of the C20–C24/C29 and C24–C29 rings, respectively, in the pyrenyl ring system.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cg5ⁱ	0.89 (2)	2.80 (2)	3.6524 (19)	163 (2)
C6—H6···Cg6ⁱ	0.99 (2)	2.76 (2)	3.631 (2)	147 (1)

Symmetry code: (i) x+1, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg5 and Cg6 are the centroids of the C20–C24/C29 and C24–C29 rings, respectively, in the pyrenyl ring system.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cg5ⁱ	0.89 (2)	2.80 (2)	3.6524 (19)	163 (2)
C6—H6···Cg6ⁱ	0.99 (2)	2.76 (2)	3.631 (2)	147 (1)

Symmetry code: (i) x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₉H₂₀N₂
M_r	396.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.0433 (6), 12.2700 (5), 13.4981 (7)
β (°)	114.269 (2)
V (Å³)	1969.34 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.18 × 0.14 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.986, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	19561, 4882, 3015
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.136, 1.02
No. of reflections	4882
No. of parameters	360
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.31

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SIR97 (Altomare et al., 1999), DIAMOND (Brandenberg & Putz, 2006) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2015) and PLATON (Spek, 2009).

Acknowledgements

The authors are grateful to the National Taras Shevchenko University, Department of Chemistry, Volodymyrska Str. 64, 01601 Kyiv, Ukraine, for financial support.

References

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Volume 71| Part 3| March 2015| Pages 261-263

doi:10.1107/S2056989015001814

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