Crystal structures of three 4-substituted-2,2′-bipyridines synthesized by Sonogashira and Suzuki–Miyaura cross-coupling reactions

Luong Thi Thu, T.; Nguyen Bich, N.; Nguyen, H.; Van Meervelt, L.

doi:10.1107/S2056989017004662

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ISSN: 2056-9890

Volume 73| Part 4| April 2017| Pages 610-615

https://doi.org/10.1107/S2056989017004662

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Crystal structures of three 4-substituted-2,2′-bipyridines synthesized by Sonogashira and Suzuki–Miyaura cross-coupling reactions

Thuy Luong Thi Thu,^a Ngan Nguyen Bich,^a Hien Nguyen ^a and Luc Van Meervelt ^b ^*

^aDepartment of Chemistry, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam, and ^bDepartment of Chemistry, KU Leuven, Biomolecular Architecture, Celestijnenlaan 200F, Leuven (Heverlee), B-3001, Belgium
^*Correspondence e-mail: luc.vanmeervelt@kuleuven.be

Edited by G. Smith, Queensland University of Technology, Australia (Received 3 March 2017; accepted 24 March 2017; online 31 March 2017)

Facile synthetic routes for three 4-substituted 2,2′-bipyridine derivatives, 4-[2-(4-methylphenyl)ethynyl]-2,2′-bipyridine, C₁₉H₁₄N₂, (I), 4-[2-(pyridin-3-yl)ethynyl]-2,2′-bipyridine, C₁₇H₁₁N₃, (II), and 4-(indol-4-yl)-2,2′-bipyridine, C₁₈H₁₃N₃, (III), via Sonogashira and Suzuki–Miyaura cross-coupling reactions, respectively, are described. As indicated by X-ray analysis, the 2,2′-bipyridine core, the ethylene linkage and the substituents of (I) and (II) are almost planar [dihedral angles between the two ring systems: 8.98 (5) and 9.90 (6)° for the two molecules of (I) in the asymmetric unit and 2.66 (14)° for (II)], allowing π-conjugation. On the contrary, in (III), the indole substituent ring is rotated significantly out of the bipyridine plane [dihedral angle = 55.82 (3)°], due to steric hindrance. The crystal packings of (I) and (II) are dominated by π–π interactions, resulting in layers of molecules parallel to (30-2) in (I) and columns of molecules along the a axis in (II). The packing of (III) exhibits zigzag chains of molecules along the c axis interacting through N—H⋯N hydrogen bonds and π–π interactions. The contributions of unknown disordered solvent molecules to the diffraction intensities in (II) were removed with the SQUEEZE [Spek (2015 ). Acta Cryst. C71, 9–18] algorithm of PLATON. The given chemical formula and other crystal data do not take into account these solvent molecules.

Keywords: crystal structure; dye-sensitized solar cells; 2,2′-bipyridine; palladium-catalyzed; Sonogashira cross-coupling; Suzuki–Miyaura cross-coupling.

CCDC references: 1540011; 1540010; 1540009

1. Chemical context

The bidentate ligand 2,2′-bipyridine (Bpy) is one of the most studied chelate systems and has found applications in various fields, including catalysis (Kitanosono et al., 2015 ; Song et al., 2015 ), chemosensors for metal ions (Al Abdel Hamid et al., 2011 ), electroluminescent devices (Li et al., 2000 ), and molecular shuttles (Lewis et al., 2016 ). In particular, as a result of their unique photophysical characteristics, 2,2′-bipyridine derivatives are used in the synthesis of photosensitizers (Grätzel, 2003 , Grätzel, 2009 ; Chen et al., 2012 ; Nguyen et al., 2015 ). In order to fine tune its properties, great efforts have been made to develop new synthetic methods for functionalization of this bidentate ligand by introducing various substituents (Kaes et al., 2000 ; Newkome et al., 2004 ; Ortiz et al., 2013 ; Norris et al., 2013 ).

In this paper, we report on the synthesis of three 4-substituted 2,2′-bipyridine derivatives, namely 4-(4-methylphenylethynyl)-2,2′-bipyridine, C₁₉H₁₄N₂, (I), 4-(pyridin-3-ylethynyl)-2,2′-bipyridine, C₁₇H₁₁N₃, (II) and 4-(indol-4-yl)-2,2′-bipyridine, C₁₈H₁₃N₃, (III), obtained from the Sonogashira (Sonogashira et al., 1975 ; Sonogashira, 2002 ; Negishi & de Meijere, 2002 ) and Suzuki–Miyaura (Miyaura & Suzuki, 1979 ; Suzuki, 1999 ; Kumar et al., 2014 ; Blangetti et al., 2013 ) cross-coupling reactions of 4-bromo-2,2′-bipyridine. The ethynyl bridge in (I) and (II) was introduced to decrease the steric hindrance between the pyridine ring and the aromatic substituent and at the same time to extend the π-conjugation. The crystal structures as well as geometry and the molecular arrangement in the crystals of (I), (II) and (III) are reported herein.

2. Structural commentary

The structures of the three 4-substituted 2,2′-bipyridines (I), (II), and (III) were elucidated by ¹H and ¹³C NMR spectroscopy using d₁-chloroform as solvent (see Synthesis and crystallization). The ¹H NMR spectra of the three compounds show typical proton resonances and splitting patterns of the Bpy core. The proton resonances of the introduced alkyne or the heteroarene moiety are easily recognized. In the ¹³C NMR spectrum of (I) and (II), the two resonance signals at about 94.3 and 86.5 p.p.m. prove the 2,2′-bipyridine and the tolyl or pyridine substituent to be connected by a C≡C linker. These signals typical for Csp carbons are not observed in the ¹³C NMR spectrum of (III) as the heterocycle is directly attached to the 2,2′-bipyridine core.

The molecular conformations of the compounds (I), (II) and (III) determined in the X-ray structural analysis are shown in Fig. 1. The asymmetric unit of (I) (Fig. 1a) consists of two molecules with similar conformational features (r.m.s deviation = 0.120 Å) and are linked by a C—H⋯N hydrogen bond (Table 1). As expected, the aromatic substituents introduced via an ethylene bridge in (I) (Fig. 1a) and (II) (Fig. 1b) are essentially coplanar with the 2,2′-bipyridine core, as indicated by the dihedral angles between the aromatic moieties, viz. 8.98 (5) and 9.90 (6)° in (I) and 2.66 (14)° in (II). On the other hand, the indole moiety and the bipyridyl ring are out of plane in (III) (Fig. 1c) in order to reduce the van de Waals repulsion between H5 with H19 and H3 with H17, the dihedral angle between the mean planes of the bipyridine core and indole ring being 55.82 (3)°.

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N28	0.95	2.53	3.472 (2)	169
C26—H26⋯N7ⁱ	0.95	2.55	3.487 (3)	171
Symmetry code: (i) x, y+1, z.

Figure 1
View of the asymmetric unit of (a) (I)

, (b) (II)

, and (c) (III)

showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level.

The 2,2′-bipyridyl groups in the three compounds exhibit trans conformations and the pyridine rings are essentially co-planar, as indicated by the dihedral angles between the best planes through the two pyridine rings, viz. 3.40 (9) and 10.81 (9)° in (I), 0.4 (2)° in (II) and 11.66 (7)° in (III). These values are within the range 0.8–28.5° observed for the 2,2′-bipyridine derivatives substituted at the 4-position with an aromatic substituent (Table 4). All of these structural characteristics are consistent with those in our previous report (Nguyen et al., 2014 ).

Table 4
4-Substituted 2,2′-bipyridines present in the Cambridge Structural Database^a

The dihedral angle py–py is defined as the angle between the best planes through both pyridine rings and the dihedral angle py–Ar is defined as the angle between the best planes through the 4-substituted pyridine and the aromatic substituent.

4-Substituent	CSD refcode	Dihedral angle py–py (°)	Dihedral angle py–Ar (°)	Reference
(substituted) phenyl	EWOYEW	0.8	9.1	Ramakrishnan et al. (2016 )
	EWOXIZ	7.8/28.5/12.5	35.8/32.8/40.8	Ramakrishnan et al. (2016)
	ZOZRIF	6.6	24.5	Wang et al. (1996 )
	RIPQUC	15.7	42.9	Cargill Thompson et al. (1997 )
triazine	MULRUI	14.2/3.7/18.5	8.1/6.1/25.2	Laramée-Milette et al. (2015 )
(substituted) naphthalene	EWOXUL	2.8/10.8/1.8	6.0/26.1/32.9	Ramakrishnan et al. (2016)
	EWOYIA	18.2/20.8	34.8/31.7	Ramakrishnan et al. (2016)
	OKAGOX	23.0/9.6	44.6/39.3	He et al. (2011 )
2,2′-bipyridine	TEBGAI	3.2/2.7	0.0/0.0	Honey & Steel (1991 )
anthracene	EWOWUK	4.0	73.8	Ramakrishnan et al. (2016)
phenanthrene	EWOXAR	5.2	64.8	Ramakrishnan et al. (2016)
	EWOXEV	11.1	53.1	Ramakrishnan et al. (2016)
pyrene	EWOXOF	4.0	51.6	Ramakrishnan et al. (2016)
Note: (a) Groom et al. (2016).

In conclusion, we have described facile synthetic procedures for 4-alkynylated and 4-arylated 2,2′-bipyridines by means of the Sonogashira and Suzuki–Miyaura cross-coupling reactions of 4-bromo-2,2′-bipyridine. Based on this strategy, two novel 4-alkynylbipyridines and one 4-aryl-2,2′-bipyridine were synthesized whose structures were partially elucidated by NMR spectroscopic methods. In addition, the X-ray structural analysis revealed the planarity of the 4-alkynylbipyridines as the triple-bond linker separates the bipyridine and the introduced aromatic parts. This provides a hint for fine-tuning the electronic properties of this ligand by introducing suitable substituents. On the other hand, the introduced heterocyclic ring in compound (III), formed via Suzuki–Miyaura cross-coupling is twisted from the 2,2′-bipyridine ring due to the van der Waals repulsive force of the hydrogen atoms in close proximity.

3. Supramolecular features

The crystal packing of (I) is dominated by π_pyridine–π_pyridine and π_pyridine–π_phenyl stacking interactions [Fig. 2; Cg1⋯Cg3ⁱ = 3.7769 (11) and Cg4⋯Cg5ⁱⁱ = 3.8707 (11) Å; Cg1, Cg3, Cg4 and Cg5 are the centroids of the N1/C2–C6, C15–C20, N22/C23–27 and N28/C29–C33 rings, respectively; symmetry codes: (i) −x, −y, −z; (ii) −x, −y + 1, −z]. The molecules lie in layers parallel to (30 $[\overline{2}]$ ) and within these planes, neighboring molecules interact with each other through C—H⋯N hydrogen bonds (Table 1).

Figure 2
Partial crystal packing of (I)

showing C—H⋯N (blue dotted lines) and π–π (gray dotted lines) interactions. [Symmetry codes: (i) −x, −y, −z; (ii) −x, −y + 1, −z; (iii) x, y + 1, z].

Similarly, π–π interactions between the pyridine rings of (II) result in columms of molecules along the a-axis direction [Cg1⋯Cg1ⁱ = Cg2⋯Cg2ⁱ = Cg3⋯Cg3ⁱ = 3.7436 (3) Å; Cg1, Cg2, and Cg3 are centroids of the N1/C2–C6; N7/C7–C12 and N15/C16–C20 rings, respectively; symmetry code: (i) x + 1, y, z]. Neighboring columns interact by C—H⋯N hydrogen bonds (Fig. 3, Table 2). In between the columns, large voids (375 Å³) contain disordered solvent molecules.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N7ⁱ	0.95	2.55	3.475 (5)	163
C18—H18⋯N1ⁱⁱ	0.95	2.60	3.509 (5)	161
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Figure 3
Crystal packing of (II)

viewed along the a axis. C—H⋯N hydrogen bonds between neighboring columns of stacked molecules are shown as blue dotted lines. Voids are contoured (green grid) at 0.2 Å away from the molecular surface resulting in a total void volume of 375 Å³. [Symmetry codes: (i) x − 1, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (ii) x + 1, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ].

The molecules in the crystal packing of (III) are arranged in zigzag chains running along the c axis by hydrogen-bonding interactions in a head-to-tail manner between N13—H13⋯N7ⁱ [symmetry code: (i) x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ; Table 3, Fig. 4]. These chains interact by π–π stacking between pyridine rings [Cg2⋯Cg3ⁱ = 3.6920 (8) Å; Cg2 and Cg3 are the centroids of the N1/C2–C6 and N7/C8–C12 rings, respectively; symmetry code: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ] and C—H⋯π interactions (Table 3).

Table 3
Hydrogen-bond geometry (Å, °) for (III)

Cg1, Cg2, Cg3 and Cg4 are the centroids of rings N13/C14–C16/C21, N1/C2–C6, N7/C8–C12 and C16–C21, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13⋯N7ⁱ	0.88	2.22	3.002 (2)	148
C14—H14⋯N1ⁱⁱ	0.95	2.39	3.336 (2)	176
C5—H5⋯Cg1ⁱⁱⁱ	0.95	2.58	3.3371 (14)	137
C6—H6⋯Cg4ⁱⁱⁱ	0.95	2.78	3.5268 (14)	136
C11—H11⋯Cg4^iv	0.95	2.56	3.3548 (15)	141
C17—H17⋯Cg2^v	0.95	2.85	3.6555 (15)	143
C20—H20⋯Cg3^vi	0.95	2.86	3.5814 (16)	133
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z+1; (vi) -x, -y+1, -z+1.

Figure 4
Crystal packing of (III)

showing N—H⋯N hydrogen bonds (blue dotted lines) and π–π (gray dotted lines) interactions·[Symmetry codes: (i) x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iii) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ ; (iv) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ].

4. Database survey

An extension of the π-conjugated system of 2,2′-bipyridine can be obtained by the introduction of an aromatic substituent. A search in the Cambridge Structural Database (CSD, Version 5.38, last update February 2017; Groom et al., 2016 ) for crystal structures of 2,2′-bipyridine derivatives substituted at the 4-position with an aromatic substituent resulted in 13 unique hits (excluding organometallic compounds) with substituents ranging from smaller phenyl and triazine rings to bipyridine, naphthalene, anthracene and phenanthrene to a larger pyrene ring (Table 4). However, it is evident from the dihedral angle between the best planes through pyridine and its aromatic 4-substituent (varying from 0.0 to 73.8°) that the degree of extension of the π-conjugated system depends on the steric hindrance of the substituent and the π–π interactions in the crystal packing.

5. Synthesis and crystallization

The compound 4-bromo-2,2′-bipyridine was prepared using literature procedures (Egbe et al., 2001 ). The alkynylated and arylated Bpy derivatives (I), (II), and (III) were prepared by the palladium-catalyzed Sonogashira and the palladium-catalyzed Suzuki–Miyaura cross-coupling reactions.

(a) Synthesis of 4-(4-methylphenylethynyl)-2,2′-bipyridine (I) by the Sonogashira reaction: Toluene (4.0 ml) was deaerated by exchanging between a vacuum and a stream of argon (3 times). To this argon-saturated solution were added 4-bromo-2,2′-bipyridine (59 mg, 0.25 mmol, 1.0 equiv), Pd(PPh₃)₄ (28.5 mg, 0.025 mmol, 10 mol%) and CuI (10 mg, 0.050 mmol, 20 mol%). The pale-yellow mixture obtained was degassed again as described above. To the reaction mixture, a solution of p-tolylacetylene (34.8 mg, 0.3 mmol, 1.2 equiv) in argon-saturated toluene (1.0 ml) was added dropwise over 15 minutes. The reaction mixture was heated at 323 K for 4 h. The reaction mixture turned reddish brown when the cross-coupling completed as indicated by TLC (EtOAc:n-hexane 1:4, v/v). The reaction mixture was diluted with EtOAc, washed with water (3 times), dried over anhydrous Na₂SO₄, and concentrated under reduced pressure. The residue was purified by SiO₂ column chromatography to furnish the 4-alkynated 2,2′-bipyridine (I) as a brownish yellow solid (43 mg, 64%). M.p. 365–367 K; ¹H NMR (CDCl₃, 500 MHz): δ (p.p.m.) 8.70 (dt, J = 4.5 Hz and 0.5 Hz, 1 H), 8.65 (d, J = 5.0 Hz, 1 H), 8.52 (s, 1 H), 8.40 (dd, J = 8.0 Hz and 0.5 Hz, 1 H), 7.82 (td, J = 7.5 Hz and 1.5 Hz, 1 H), 7.45 (d, J = 8 Hz, 2 H, Ar), 7.38 (dd, J = 5.0 Hz and 1.0 Hz, 1 H), 7.32 (m, 1 H), 7.19 (d, J = 8 Hz, 2 H, Ar), 2.38 (s, 3 H, –CH₃). ¹³C NMR (CDCl₃, 125 MHz): δ(p.p.m.) 156.2, 155.6, 149.2, 149.1, 139.5, 137.0, 132.7, 131.8, 129.2, 125.2, 123.9, 123.2, 121.1, 119.2, 94.3 and 86.5 (C≡C), 21.6 (–CH₃). Besides the desired cross-coupling product, a small amount of the Glaser homo-coupling by-product was also observed. Single crystals of (I) suitable for X-ray structure analysis were obtained by recrystallization from chloroform.

(b) 4-(Pyridine-3-ylethynyl)-2,2′-bipyridine (II): Following the same procedure for (I), except that no CuI co-catalyst was used, (II) was obtained from 4-bromo-2,2′-bipyridine (59 mg, 0.25 mmol, 1.0 equiv) and pyridine-3-ylacetylene (31 mg, 0.3 mmol, 1.2 equiv) after 4 h at 373 K as a white solid (50 mg, 78%). M.p. 398–400 K; ¹H NMR (CDCl₃, 500 MHz): δ (p.p.m.) 8.81 (s, 1 H), 8.71 (s, 2 H), 8.62 (dd, J = 5.0 Hz and 1.0 Hz, 1 H), 8.57 (s, 1 H), 8.43 (d, J = 7.5 Hz, 1 H), 7.85 (m, 2 H), 7.42 (d, J = 8.0 Hz, 1 H), 7.33 (m, 2 H). ¹³C NMR (CDCl₃, 125 MHz): δ(p.p.m.) 156.3, 155.3, 152.4, 149.4, 149.3, 149.2, 138.7, 137.0, 131.6, 125.1, 124.0, 123.2, 123.2, 121.2, 119.5, 90.2 (C≡C). Single crystals of (II) suitable for X-ray structure analysis were obtained by recrystallization from ethyl acetate.

(c) Synthesis of 4-(1H-indol-4-yl)-2,2′-bipyridine (III) by the Suzuki–Miyaura reaction: Toluene was degassed by exchanging between a vacuum and a stream of argon (3 times). 5-Bromo-2,2′-bipyridine (58 mg, 0.25 mmol, 1.0 equiv) and Pd(Ph₃P)₄ (28.8 mg, 0.025 mmol, 10 mol%) were dissolved in this degassed toluene (4 mL). To the obtained solution, H₂O (1 ml), K₃PO₄ (105.5 mg, 0.5 mmol, 2.0 equiv), and 1H-indol-4-ylboronic acid (48.3 mg, 0.3 mmol, 1.2 equiv) were added. The reaction was stirred vigorously under an argon atmosphere at 383 K until TLC (n-hexane–ethyl acetate 95:5,v/v) indicated the complete consumption of the starting material. The reaction mixture was filtered to remove insoluble particles. The filtrate was washed several times with H₂O, dried over Na₂SO₄, and concentrated under reduced pressure by rotary evaporation. The residue was purified by SiO₂ column chromatography (n-hexane–ethyl acetate 97:3, v/v) to furnish the desired 4-arylated 2,2′-bipyridine (III) as a yellow solid (32.5 mg, 48%). M.p. 356–357 K; ¹H NMR (CDCl₃, 500 MHz): δ (p.p.m.) 8.86 (br s, 1 H, NH indole), 8.74 (m, 2 H), 8.70 (d, J = 5.0 Hz, 1 H), 8.45 (d, J = 8.0 Hz, 1 H), 8.04 (t, J = 1.0 Hz, 1 H), 7.83 (td, J = 7.5 Hz and 2.0 Hz, 1 H), 7.60 (dd, J = 5.0 Hz and 2.0 Hz, 1 H), 7.55 (dd, J = 8.0 Hz and 2.0 Hz, 1 H), 7.42 (d, J = 7.5 Hz, 1 H), 7.31 (m, 1 H), 7.22 (t, J = 3.0 Hz, 1 H), 6.61 (t, J 2.0 Hz, 1 H). ¹³C NMR (CDCl₃, 125 MHz)) : δ(p.p.m.) 156.5, 156.3, 150.7, 149.4, 149.1, 136.9, 136.4, 129.9, 128.5, 125.3, 123.7, 121.7, 121.4, 121.3, 119.6, 119.2, 111.6, 103.2. Single crystals of (III) suitable for X-ray structure analysis were obtained by recrystallization from chloroform.

6. Structure solution and refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The structures of (I) and (III) were solved using SHELXS97 (Sheldrick, 2008 ) and for (II) by charge flipping using Olex2.solve (Bourhis et al., 2015 ). All hydrogen atoms were placed in idealized positions and refined in a riding mode with U_iso(H) = 1.2 times those of their parent atoms (1.5 times for methyl groups), with C—H distances of 0.95 Å (aromatic) and 0.98 Å (CH₃) and N—H distances of 0.88 Å.

Table 5
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₉H₁₄N₂	C₁₇H₁₁N₃	C₁₈H₁₃N₃
M_r	270.32	257.29	271.31
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	100	100	100
a, b, c (Å)	9.8697 (7), 12.6040 (7), 22.8414 (13)	3.7436 (3), 34.146 (3), 10.7528 (9)	9.6951 (6), 12.0142 (7), 12.0376 (9)
β (°)	97.890 (6)	94.799 (8)	109.552 (8)
V (Å³)	2814.5 (3)	1369.7 (2)	1321.28 (15)
Z	8	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.08	0.08	0.08
Crystal size (mm)	0.30 × 0.15 × 0.10	0.40 × 0.10 × 0.10	0.35 × 0.35 × 0.20

Data collection
Diffractometer	Agilent SuperNova (single source at offset, Eos detector)	Agilent SuperNova (single source at offset, Eos detector)	Agilent SuperNova (single source at offset, Eos detector)
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.552, 1.000	0.695, 1.000	0.993, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12597, 5747, 3728	4235, 1926, 1645	8569, 2692, 2363
R_int	0.025	0.022	0.023
θ_max (°)	26.4	23.3	26.4
(sin θ/λ)_max (Å⁻¹)	0.625	0.555	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.146, 1.04	0.083, 0.208, 1.15	0.038, 0.095, 1.06
No. of reflections	5747	1926	2692
No. of parameters	381	181	190
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22	0.44, −0.29	0.21, −0.23
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS97 (Sheldrick, 2008), Olex2.solve (Bourhis et al., 2015), SHELXL2014 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

For (II) a region of electron density amounting to the scattering from approximately 10.7 carbon atoms, apparently disordered in channels between columns of stacking molecules, was removed with the SQUEEZE routine of PLATON (Spek, 2015) after it proved impossible to identify it with any reasonable solvent molecule. A suggestion of possible twinning generated by PLATON (Spek, 2009 ) was further checked but subsequent refinement did not improve and was neglected.

Supporting information

CCDC references: 1540011; 1540010; 1540009

Crystal structure: contains datablocks global, II, III, I. DOI: https://doi.org/10.1107/S2056989017004662/zs2378sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017004662/zs2378Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017004662/zs2378IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989017004662/zs2378IIIsup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017004662/zs2378Isup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989017004662/zs2378IIsup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989017004662/zs2378IIIsup7.cml

checkCIF report

Computing details top

For all compounds, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I), (III); Olex2.solve (Bourhis et al., 2015) for (II). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for (I), (III); SHELXL (Sheldrick, 2015) for (II). For all compounds, molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(I) 4-[2-(4-Methylphenyl)ethynyl]-2,2'-bipyridine top

Crystal data top

C₁₉H₁₄N₂	D_x = 1.276 Mg m⁻³
M_r = 270.32	Melting point = 365–367 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.8697 (7) Å	Cell parameters from 2955 reflections
b = 12.6040 (7) Å	θ = 3.0–28.1°
c = 22.8414 (13) Å	µ = 0.08 mm⁻¹
β = 97.890 (6)°	T = 100 K
V = 2814.5 (3) Å³	Block, orange-colourless
Z = 8	0.30 × 0.15 × 0.10 mm
F(000) = 1136

Data collection top

Agilent SuperNova (single source at offset, Eos detector) diffractometer	5747 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3728 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 15.9631 pixels mm^-1	θ_max = 26.4°, θ_min = 2.7°
ω scans	h = −12→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −15→15
T_min = 0.552, T_max = 1.000	l = −25→28
12597 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0565P)² + 0.7915P] where P = (F_o² + 2F_c²)/3
5747 reflections	(Δ/σ)_max < 0.001
381 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1D	0.44761 (19)	0.30825 (17)	0.43143 (8)	0.0253 (5)
N22	0.21628 (16)	0.57648 (13)	0.03346 (7)	0.0249 (4)
C23	0.20493 (18)	0.47210 (15)	0.04431 (8)	0.0208 (4)
C24	0.23091 (18)	0.42918 (16)	0.10057 (8)	0.0219 (4)
H24	0.2225	0.3549	0.1063	0.026*
C25	0.26964 (18)	0.49598 (16)	0.14880 (8)	0.0219 (4)
C26	0.28021 (19)	0.60404 (16)	0.13795 (9)	0.0258 (5)
H26	0.3057	0.6525	0.1694	0.031*
C27	0.2527 (2)	0.63910 (16)	0.08023 (9)	0.0277 (5)
H27	0.2603	0.7130	0.0733	0.033*
N28	0.15236 (16)	0.29935 (12)	0.00260 (7)	0.0233 (4)
C29	0.16089 (18)	0.40394 (15)	−0.00772 (8)	0.0209 (4)
C30	0.1289 (2)	0.44677 (16)	−0.06415 (8)	0.0265 (5)
H30	0.1377	0.5208	−0.0705	0.032*
C31	0.0845 (2)	0.38021 (16)	−0.11061 (9)	0.0300 (5)
H31	0.0618	0.4079	−0.1494	0.036*
C32	0.0731 (2)	0.27292 (17)	−0.10025 (9)	0.0281 (5)
H32	0.0420	0.2252	−0.1314	0.034*
C33	0.1085 (2)	0.23716 (16)	−0.04304 (9)	0.0252 (5)
H33	0.1009	0.1633	−0.0359	0.030*
C34	0.29879 (19)	0.45398 (16)	0.20791 (8)	0.0233 (5)
C35	0.32897 (18)	0.41970 (16)	0.25663 (8)	0.0226 (4)
C36	0.36776 (18)	0.38063 (16)	0.31578 (8)	0.0214 (4)
C37	0.38186 (19)	0.27264 (16)	0.32746 (9)	0.0251 (5)
H37	0.3647	0.2228	0.2961	0.030*
C38	0.4208 (2)	0.23774 (16)	0.38463 (9)	0.0275 (5)
H38	0.4294	0.1637	0.3921	0.033*
C39	0.4325 (2)	0.41597 (17)	0.41955 (8)	0.0284 (5)
H39	0.4490	0.4656	0.4510	0.034*
C40	0.3939 (2)	0.45209 (17)	0.36263 (8)	0.0271 (5)
H40	0.3851	0.5261	0.3553	0.033*
C41	0.4909 (2)	0.26987 (19)	0.49369 (9)	0.0352 (5)
H41A	0.5829	0.2963	0.5079	0.053*
H41B	0.4913	0.1921	0.4942	0.053*
H41C	0.4265	0.2962	0.5194	0.053*
N1	0.30594 (16)	0.07848 (13)	0.21333 (7)	0.0237 (4)
C2	0.29537 (18)	−0.02679 (15)	0.20395 (8)	0.0197 (4)
C3	0.25839 (18)	−0.07017 (16)	0.14808 (8)	0.0209 (4)
H3	0.2505	−0.1449	0.1432	0.025*
C4	0.23300 (18)	−0.00324 (16)	0.09931 (8)	0.0212 (4)
C5	0.24522 (18)	0.10603 (16)	0.10882 (8)	0.0240 (5)
H5	0.2296	0.1547	0.0768	0.029*
C6	0.28062 (19)	0.14124 (15)	0.16604 (8)	0.0245 (4)
H6	0.2875	0.2157	0.1723	0.029*
N7	0.34111 (16)	−0.19977 (13)	0.24599 (7)	0.0231 (4)
C8	0.32952 (18)	−0.09575 (15)	0.25668 (8)	0.0202 (4)
C9	0.3519 (2)	−0.05342 (16)	0.31331 (8)	0.0258 (5)
H9	0.3407	0.0204	0.3195	0.031*
C10	0.3908 (2)	−0.12057 (17)	0.36064 (8)	0.0285 (5)
H10	0.4065	−0.0936	0.3998	0.034*
C11	0.4063 (2)	−0.22683 (17)	0.34999 (9)	0.0290 (5)
H11	0.4345	−0.2745	0.3815	0.035*
C12	0.3800 (2)	−0.26281 (17)	0.29244 (9)	0.0284 (5)
H12	0.3901	−0.3365	0.2854	0.034*
C13	0.19552 (19)	−0.04592 (15)	0.04086 (8)	0.0216 (4)
C14	0.16254 (19)	−0.08025 (16)	−0.00793 (8)	0.0231 (4)
C15	0.12182 (18)	−0.12154 (16)	−0.06645 (8)	0.0220 (4)
C16	0.10184 (19)	−0.22989 (16)	−0.07588 (9)	0.0243 (4)
H16	0.1163	−0.2779	−0.0436	0.029*
C17	0.06086 (19)	−0.26739 (16)	−0.13242 (9)	0.0250 (5)
H17	0.0462	−0.3414	−0.1382	0.030*
C18	0.04061 (19)	−0.20031 (16)	−0.18071 (8)	0.0253 (5)
C19	0.06191 (19)	−0.09226 (16)	−0.17123 (8)	0.0265 (5)
H19	0.0494	−0.0449	−0.2039	0.032*
C20	0.10105 (19)	−0.05250 (16)	−0.11494 (8)	0.0250 (5)
H20	0.1138	0.0217	−0.1092	0.030*
C21	−0.0027 (2)	−0.24223 (17)	−0.24197 (9)	0.0319 (5)
H21A	−0.0892	−0.2089	−0.2587	0.048*
H21B	−0.0150	−0.3193	−0.2403	0.048*
H21C	0.0678	−0.2258	−0.2669	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1D	0.0183 (10)	0.0412 (13)	0.0158 (10)	−0.0012 (9)	0.0007 (8)	0.0047 (9)
N22	0.0308 (9)	0.0233 (9)	0.0196 (9)	−0.0029 (7)	0.0002 (7)	0.0013 (7)
C23	0.0205 (10)	0.0229 (11)	0.0185 (10)	0.0015 (8)	0.0005 (8)	0.0026 (8)
C24	0.0234 (10)	0.0223 (11)	0.0191 (10)	0.0009 (8)	−0.0001 (8)	0.0033 (8)
C25	0.0204 (10)	0.0272 (11)	0.0173 (10)	0.0007 (8)	0.0001 (8)	0.0015 (8)
C26	0.0295 (11)	0.0274 (11)	0.0195 (10)	−0.0028 (9)	−0.0006 (8)	−0.0028 (9)
C27	0.0366 (12)	0.0235 (11)	0.0220 (11)	−0.0024 (9)	0.0003 (9)	0.0027 (9)
N28	0.0273 (9)	0.0238 (9)	0.0184 (9)	0.0004 (7)	0.0014 (7)	0.0011 (7)
C29	0.0195 (10)	0.0248 (11)	0.0182 (10)	0.0022 (8)	0.0016 (8)	0.0025 (8)
C30	0.0332 (12)	0.0243 (11)	0.0206 (11)	−0.0001 (9)	−0.0017 (9)	0.0039 (8)
C31	0.0387 (12)	0.0337 (12)	0.0158 (10)	0.0006 (10)	−0.0026 (9)	0.0034 (9)
C32	0.0319 (11)	0.0318 (11)	0.0194 (11)	−0.0021 (9)	−0.0002 (9)	−0.0033 (9)
C33	0.0302 (11)	0.0238 (11)	0.0205 (11)	−0.0006 (9)	0.0002 (9)	0.0008 (8)
C34	0.0224 (10)	0.0288 (12)	0.0179 (11)	−0.0003 (8)	−0.0001 (8)	0.0001 (9)
C35	0.0209 (10)	0.0275 (11)	0.0191 (10)	0.0006 (8)	0.0012 (8)	−0.0017 (9)
C36	0.0181 (9)	0.0307 (11)	0.0150 (9)	0.0004 (8)	0.0011 (7)	0.0011 (8)
C37	0.0259 (10)	0.0305 (11)	0.0180 (11)	−0.0007 (9)	0.0003 (8)	−0.0006 (9)
C38	0.0297 (11)	0.0290 (12)	0.0229 (12)	−0.0009 (9)	0.0002 (9)	0.0041 (9)
C39	0.0308 (11)	0.0375 (13)	0.0165 (10)	0.0004 (9)	0.0019 (8)	−0.0050 (9)
C40	0.0299 (11)	0.0295 (12)	0.0214 (11)	0.0023 (9)	0.0014 (9)	−0.0004 (9)
C41	0.0327 (12)	0.0542 (15)	0.0180 (11)	−0.0016 (11)	0.0005 (9)	0.0055 (10)
N1	0.0274 (9)	0.0238 (9)	0.0190 (9)	−0.0005 (7)	−0.0003 (7)	0.0004 (7)
C2	0.0163 (9)	0.0252 (11)	0.0174 (10)	0.0006 (8)	0.0016 (7)	0.0010 (8)
C3	0.0217 (10)	0.0221 (11)	0.0185 (10)	0.0004 (8)	0.0013 (8)	0.0016 (8)
C4	0.0168 (9)	0.0291 (11)	0.0176 (10)	−0.0002 (8)	0.0027 (7)	0.0010 (8)
C5	0.0240 (10)	0.0261 (11)	0.0209 (10)	0.0001 (8)	−0.0009 (8)	0.0056 (8)
C6	0.0286 (11)	0.0199 (10)	0.0239 (11)	−0.0009 (8)	−0.0005 (8)	0.0031 (8)
N7	0.0272 (9)	0.0227 (9)	0.0189 (9)	0.0003 (7)	0.0012 (7)	0.0024 (7)
C8	0.0183 (9)	0.0246 (11)	0.0176 (10)	−0.0009 (8)	0.0016 (7)	0.0012 (8)
C9	0.0328 (11)	0.0258 (11)	0.0181 (10)	−0.0006 (9)	0.0015 (8)	−0.0016 (8)
C10	0.0360 (12)	0.0342 (12)	0.0147 (10)	−0.0028 (9)	0.0008 (9)	−0.0002 (9)
C11	0.0322 (12)	0.0363 (12)	0.0176 (11)	0.0021 (10)	0.0000 (9)	0.0070 (9)
C12	0.0352 (12)	0.0279 (12)	0.0215 (12)	0.0042 (9)	0.0013 (9)	0.0047 (9)
C13	0.0212 (10)	0.0244 (11)	0.0185 (10)	0.0003 (8)	0.0004 (8)	0.0054 (8)
C14	0.0221 (10)	0.0265 (11)	0.0203 (11)	0.0024 (8)	0.0016 (8)	0.0048 (9)
C15	0.0179 (9)	0.0314 (12)	0.0160 (10)	0.0006 (8)	0.0004 (8)	0.0003 (8)
C16	0.0245 (10)	0.0298 (11)	0.0179 (10)	0.0028 (9)	0.0007 (8)	0.0034 (9)
C17	0.0256 (11)	0.0276 (11)	0.0213 (11)	0.0009 (9)	0.0014 (8)	0.0010 (9)
C18	0.0203 (10)	0.0353 (12)	0.0196 (10)	0.0012 (9)	0.0006 (8)	−0.0003 (9)
C19	0.0266 (11)	0.0349 (12)	0.0175 (10)	−0.0002 (9)	0.0005 (8)	0.0069 (9)
C20	0.0254 (10)	0.0280 (11)	0.0214 (11)	0.0001 (8)	0.0025 (8)	0.0019 (8)
C21	0.0346 (12)	0.0403 (13)	0.0190 (12)	0.0007 (10)	−0.0025 (9)	0.0000 (9)

Geometric parameters (Å, º) top

C1D—C38	1.387 (3)	N1—C2	1.346 (2)
C1D—C39	1.389 (3)	N1—C6	1.335 (2)
C1D—C41	1.507 (3)	C2—C3	1.390 (3)
N22—C23	1.346 (2)	C2—C8	1.486 (3)
N22—C27	1.337 (2)	C3—H3	0.9500
C23—C24	1.385 (3)	C3—C4	1.392 (3)
C23—C29	1.482 (3)	C4—C5	1.397 (3)
C24—H24	0.9500	C4—C13	1.440 (3)
C24—C25	1.398 (3)	C5—H5	0.9500
C25—C26	1.391 (3)	C5—C6	1.379 (3)
C25—C34	1.442 (3)	C6—H6	0.9500
C26—H26	0.9500	N7—C8	1.341 (2)
C26—C27	1.382 (3)	N7—C12	1.339 (2)
C27—H27	0.9500	C8—C9	1.389 (3)
N28—C29	1.344 (2)	C9—H9	0.9500
N28—C33	1.328 (2)	C9—C10	1.385 (3)
C29—C30	1.393 (3)	C10—H10	0.9500
C30—H30	0.9500	C10—C11	1.374 (3)
C30—C31	1.376 (3)	C11—H11	0.9500
C31—H31	0.9500	C11—C12	1.381 (3)
C31—C32	1.380 (3)	C12—H12	0.9500
C32—H32	0.9500	C13—C14	1.198 (3)
C32—C33	1.381 (3)	C14—C15	1.439 (3)
C33—H33	0.9500	C15—C16	1.392 (3)
C34—C35	1.193 (3)	C15—C20	1.401 (3)
C35—C36	1.440 (3)	C16—H16	0.9500
C36—C37	1.390 (3)	C16—C17	1.383 (3)
C36—C40	1.396 (3)	C17—H17	0.9500
C37—H37	0.9500	C17—C18	1.382 (3)
C37—C38	1.381 (3)	C18—C19	1.390 (3)
C38—H38	0.9500	C18—C21	1.502 (3)
C39—H39	0.9500	C19—H19	0.9500
C39—C40	1.381 (3)	C19—C20	1.385 (3)
C40—H40	0.9500	C20—H20	0.9500
C41—H41A	0.9800	C21—H21A	0.9800
C41—H41B	0.9800	C21—H21B	0.9800
C41—H41C	0.9800	C21—H21C	0.9800

C38—C1D—C39	118.15 (18)	C6—N1—C2	116.97 (16)
C38—C1D—C41	121.38 (19)	N1—C2—C3	122.60 (17)
C39—C1D—C41	120.47 (19)	N1—C2—C8	116.32 (16)
C27—N22—C23	116.74 (16)	C3—C2—C8	121.05 (18)
N22—C23—C24	122.87 (18)	C2—C3—H3	120.3
N22—C23—C29	116.20 (16)	C2—C3—C4	119.46 (19)
C24—C23—C29	120.93 (17)	C4—C3—H3	120.3
C23—C24—H24	120.3	C3—C4—C5	118.08 (18)
C23—C24—C25	119.46 (18)	C3—C4—C13	120.70 (18)
C25—C24—H24	120.3	C5—C4—C13	121.22 (17)
C24—C25—C34	120.98 (18)	C4—C5—H5	121.0
C26—C25—C24	117.94 (17)	C6—C5—C4	118.03 (18)
C26—C25—C34	121.07 (18)	C6—C5—H5	121.0
C25—C26—H26	120.9	N1—C6—C5	124.84 (19)
C27—C26—C25	118.26 (18)	N1—C6—H6	117.6
C27—C26—H26	120.9	C5—C6—H6	117.6
N22—C27—C26	124.72 (19)	C12—N7—C8	117.27 (17)
N22—C27—H27	117.6	N7—C8—C2	116.08 (16)
C26—C27—H27	117.6	N7—C8—C9	122.57 (17)
C33—N28—C29	117.57 (16)	C9—C8—C2	121.31 (18)
N28—C29—C23	116.51 (16)	C8—C9—H9	120.5
N28—C29—C30	122.05 (18)	C10—C9—C8	118.94 (19)
C30—C29—C23	121.43 (17)	C10—C9—H9	120.5
C29—C30—H30	120.5	C9—C10—H10	120.6
C31—C30—C29	119.01 (19)	C11—C10—C9	118.90 (18)
C31—C30—H30	120.5	C11—C10—H10	120.6
C30—C31—H31	120.3	C10—C11—H11	120.7
C30—C31—C32	119.32 (19)	C10—C11—C12	118.55 (19)
C32—C31—H31	120.3	C12—C11—H11	120.7
C31—C32—H32	121.1	N7—C12—C11	123.7 (2)
C31—C32—C33	117.79 (19)	N7—C12—H12	118.1
C33—C32—H32	121.1	C11—C12—H12	118.1
N28—C33—C32	124.24 (19)	C14—C13—C4	178.9 (2)
N28—C33—H33	117.9	C13—C14—C15	179.5 (2)
C32—C33—H33	117.9	C16—C15—C14	120.93 (18)
C35—C34—C25	177.1 (2)	C16—C15—C20	118.98 (18)
C34—C35—C36	178.5 (2)	C20—C15—C14	120.09 (18)
C37—C36—C35	121.45 (18)	C15—C16—H16	120.1
C37—C36—C40	118.79 (18)	C17—C16—C15	119.80 (18)
C40—C36—C35	119.75 (18)	C17—C16—H16	120.1
C36—C37—H37	120.0	C16—C17—H17	119.1
C38—C37—C36	120.05 (19)	C18—C17—C16	121.87 (19)
C38—C37—H37	120.0	C18—C17—H17	119.1
C1D—C38—H38	119.2	C17—C18—C19	118.20 (18)
C37—C38—C1D	121.55 (19)	C17—C18—C21	121.32 (19)
C37—C38—H38	119.2	C19—C18—C21	120.49 (18)
C1D—C39—H39	119.5	C18—C19—H19	119.5
C40—C39—C1D	120.98 (19)	C20—C19—C18	121.07 (18)
C40—C39—H39	119.5	C20—C19—H19	119.5
C36—C40—H40	119.8	C15—C20—H20	120.0
C39—C40—C36	120.49 (19)	C19—C20—C15	120.07 (19)
C39—C40—H40	119.8	C19—C20—H20	120.0
C1D—C41—H41A	109.5	C18—C21—H21A	109.5
C1D—C41—H41B	109.5	C18—C21—H21B	109.5
C1D—C41—H41C	109.5	C18—C21—H21C	109.5
H41A—C41—H41B	109.5	H21A—C21—H21B	109.5
H41A—C41—H41C	109.5	H21A—C21—H21C	109.5
H41B—C41—H41C	109.5	H21B—C21—H21C	109.5

C1D—C39—C40—C36	0.7 (3)	N1—C2—C3—C4	1.0 (3)
N22—C23—C24—C25	0.5 (3)	N1—C2—C8—N7	−169.28 (16)
N22—C23—C29—N28	178.53 (16)	N1—C2—C8—C9	8.8 (3)
N22—C23—C29—C30	−2.1 (3)	C2—N1—C6—C5	−0.2 (3)
C23—N22—C27—C26	0.6 (3)	C2—C3—C4—C5	−0.4 (3)
C23—C24—C25—C26	0.1 (3)	C2—C3—C4—C13	179.53 (17)
C23—C24—C25—C34	−179.39 (17)	C2—C8—C9—C10	−176.47 (17)
C23—C29—C30—C31	−177.98 (18)	C3—C2—C8—N7	9.0 (2)
C24—C23—C29—N28	−2.1 (3)	C3—C2—C8—C9	−172.87 (17)
C24—C23—C29—C30	177.27 (18)	C3—C4—C5—C6	−0.5 (3)
C24—C25—C26—C27	−0.4 (3)	C4—C5—C6—N1	0.9 (3)
C25—C26—C27—N22	0.0 (3)	C6—N1—C2—C3	−0.7 (3)
C27—N22—C23—C24	−0.9 (3)	C6—N1—C2—C8	177.53 (16)
C27—N22—C23—C29	178.43 (17)	N7—C8—C9—C10	1.5 (3)
N28—C29—C30—C31	1.4 (3)	C8—C2—C3—C4	−177.15 (16)
C29—C23—C24—C25	−178.73 (17)	C8—N7—C12—C11	1.0 (3)
C29—N28—C33—C32	1.0 (3)	C8—C9—C10—C11	0.2 (3)
C29—C30—C31—C32	−0.2 (3)	C9—C10—C11—C12	−1.1 (3)
C30—C31—C32—C33	−0.5 (3)	C10—C11—C12—N7	0.6 (3)
C31—C32—C33—N28	0.1 (3)	C12—N7—C8—C2	176.01 (16)
C33—N28—C29—C23	177.68 (16)	C12—N7—C8—C9	−2.1 (3)
C33—N28—C29—C30	−1.7 (3)	C13—C4—C5—C6	179.59 (17)
C34—C25—C26—C27	179.12 (18)	C14—C15—C16—C17	179.10 (17)
C35—C36—C37—C38	179.24 (18)	C14—C15—C20—C19	179.98 (17)
C35—C36—C40—C39	−179.36 (18)	C15—C16—C17—C18	0.9 (3)
C36—C37—C38—C1D	−0.5 (3)	C16—C15—C20—C19	−0.3 (3)
C37—C36—C40—C39	−0.3 (3)	C16—C17—C18—C19	−0.3 (3)
C38—C1D—C39—C40	−0.9 (3)	C16—C17—C18—C21	179.44 (18)
C39—C1D—C38—C37	0.8 (3)	C17—C18—C19—C20	−0.6 (3)
C40—C36—C37—C38	0.2 (3)	C18—C19—C20—C15	0.9 (3)
C41—C1D—C38—C37	−179.64 (18)	C20—C15—C16—C17	−0.6 (3)
C41—C1D—C39—C40	179.53 (18)	C21—C18—C19—C20	179.61 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N28	0.95	2.53	3.472 (2)	169
C26—H26···N7ⁱ	0.95	2.55	3.487 (3)	171

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

(II) 4-[2-(Pyridin-3-yl)ethynyl]-2,2'-bipyridine top

Crystal data top

C₁₇H₁₁N₃	F(000) = 536
M_r = 257.29	D_x = 1.248 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.7436 (3) Å	Cell parameters from 1697 reflections
b = 34.146 (3) Å	θ = 3.5–28.7°
c = 10.7528 (9) Å	µ = 0.08 mm⁻¹
β = 94.799 (8)°	T = 100 K
V = 1369.7 (2) Å³	Needle, colourless
Z = 4	0.40 × 0.10 × 0.10 mm

Data collection top

Agilent SuperNova (single source at offset, Eos detector) diffractometer	1926 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1645 reflections with I > 2σ(I)
Detector resolution: 15.9631 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 23.3°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −4→4
T_min = 0.695, T_max = 1.000	k = −37→33
4235 measured reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.083	H-atom parameters constrained
wR(F²) = 0.208	w = 1/[σ²(F_o²) + (0.0696P)² + 4.7923P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
1926 reflections	Δρ_max = 0.44 e Å⁻³
181 parameters	Δρ_min = −0.29 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
N1	0.2656 (9)	0.68966 (10)	0.2378 (3)	0.0167 (8)
C2	0.4386 (11)	0.69652 (11)	0.3508 (4)	0.0147 (9)
C3	0.5026 (11)	0.73404 (11)	0.3962 (4)	0.0154 (9)
H3	0.6208	0.7378	0.4770	0.018*
C4	0.3928 (11)	0.76640 (12)	0.3231 (4)	0.0150 (9)
C5	0.2126 (11)	0.75954 (12)	0.2070 (4)	0.0166 (10)
H5	0.1294	0.7807	0.1548	0.020*
C6	0.1571 (11)	0.72098 (12)	0.1693 (4)	0.0170 (10)
H6	0.0343	0.7165	0.0897	0.020*
N7	0.7312 (9)	0.66830 (10)	0.5380 (3)	0.0168 (8)
C8	0.5578 (11)	0.66142 (11)	0.4254 (4)	0.0142 (9)
C9	0.4899 (11)	0.62361 (12)	0.3803 (4)	0.0177 (10)
H9	0.3668	0.6197	0.3004	0.021*
C10	0.6034 (12)	0.59197 (12)	0.4530 (4)	0.0187 (10)
H10	0.5582	0.5660	0.4244	0.022*
C11	0.7850 (11)	0.59893 (12)	0.5686 (4)	0.0176 (10)
H11	0.8691	0.5778	0.6206	0.021*
C12	0.8406 (11)	0.63710 (12)	0.6063 (4)	0.0186 (10)
H12	0.9646	0.6416	0.6857	0.022*
C13	0.4658 (11)	0.80521 (12)	0.3695 (4)	0.0150 (9)
C14	0.5307 (11)	0.83770 (12)	0.4099 (4)	0.0168 (10)
N15	0.5621 (10)	0.94601 (10)	0.4131 (3)	0.0185 (9)
C16	0.5068 (11)	0.90884 (12)	0.3788 (4)	0.0176 (10)
H16	0.3938	0.9039	0.2979	0.021*
C17	0.6047 (11)	0.87675 (11)	0.4544 (4)	0.0153 (9)
C18	0.7784 (11)	0.88416 (12)	0.5721 (4)	0.0170 (10)
H18	0.8565	0.8632	0.6258	0.020*
C19	0.8344 (11)	0.92252 (12)	0.6090 (4)	0.0197 (10)
H19	0.9457	0.9284	0.6895	0.024*
C20	0.7262 (11)	0.95225 (12)	0.5273 (4)	0.0200 (10)
H20	0.7701	0.9785	0.5533	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0152 (19)	0.0180 (19)	0.0163 (19)	−0.0010 (15)	−0.0013 (15)	−0.0006 (15)
C2	0.012 (2)	0.019 (2)	0.013 (2)	−0.0016 (18)	0.0030 (17)	−0.0006 (17)
C3	0.013 (2)	0.019 (2)	0.014 (2)	−0.0009 (18)	0.0014 (18)	−0.0006 (17)
C4	0.011 (2)	0.019 (2)	0.015 (2)	0.0016 (18)	0.0023 (17)	0.0005 (17)
C5	0.021 (2)	0.017 (2)	0.013 (2)	−0.0011 (18)	0.0048 (18)	0.0021 (16)
C6	0.017 (2)	0.021 (2)	0.013 (2)	0.0005 (18)	0.0021 (18)	−0.0003 (17)
N7	0.0190 (19)	0.0156 (19)	0.016 (2)	0.0019 (15)	0.0035 (15)	0.0008 (14)
C8	0.014 (2)	0.017 (2)	0.012 (2)	−0.0003 (17)	0.0029 (17)	−0.0003 (16)
C9	0.018 (2)	0.019 (2)	0.016 (2)	−0.0015 (18)	0.0005 (18)	−0.0038 (17)
C10	0.020 (2)	0.012 (2)	0.025 (2)	−0.0013 (18)	0.0066 (19)	−0.0031 (18)
C11	0.014 (2)	0.017 (2)	0.022 (2)	0.0028 (18)	0.0035 (19)	0.0048 (18)
C12	0.020 (2)	0.021 (2)	0.015 (2)	0.0047 (18)	0.0038 (18)	0.0017 (18)
C13	0.014 (2)	0.018 (2)	0.013 (2)	−0.0015 (18)	0.0024 (17)	0.0029 (18)
C14	0.014 (2)	0.020 (2)	0.016 (2)	0.0016 (18)	0.0020 (18)	0.0024 (18)
N15	0.024 (2)	0.0155 (18)	0.016 (2)	0.0005 (16)	0.0045 (16)	0.0019 (14)
C16	0.015 (2)	0.023 (2)	0.016 (2)	0.0004 (18)	0.0068 (18)	−0.0005 (18)
C17	0.016 (2)	0.015 (2)	0.016 (2)	0.0022 (18)	0.0057 (18)	−0.0006 (17)
C18	0.014 (2)	0.016 (2)	0.021 (2)	0.0029 (18)	0.0018 (18)	0.0047 (17)
C19	0.019 (2)	0.021 (2)	0.018 (2)	−0.0005 (19)	−0.0010 (19)	−0.0014 (18)
C20	0.021 (2)	0.015 (2)	0.024 (3)	0.0008 (18)	0.003 (2)	−0.0004 (18)

Geometric parameters (Å, º) top

N1—C2	1.348 (5)	C10—C11	1.387 (6)
N1—C6	1.342 (5)	C11—H11	0.9500
C2—C3	1.385 (6)	C11—C12	1.375 (6)
C2—C8	1.490 (6)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.209 (6)
C3—C4	1.398 (6)	C14—C17	1.436 (6)
C4—C5	1.388 (6)	N15—C16	1.333 (5)
C4—C13	1.434 (6)	N15—C20	1.344 (6)
C5—H5	0.9500	C16—H16	0.9500
C5—C6	1.388 (6)	C16—C17	1.395 (6)
C6—H6	0.9500	C17—C18	1.397 (6)
N7—C8	1.345 (5)	C18—H18	0.9500
N7—C12	1.338 (5)	C18—C19	1.380 (6)
C8—C9	1.395 (6)	C19—H19	0.9500
C9—H9	0.9500	C19—C20	1.381 (6)
C9—C10	1.379 (6)	C20—H20	0.9500
C10—H10	0.9500

C6—N1—C2	117.1 (3)	C11—C10—H10	120.7
N1—C2—C3	122.3 (4)	C10—C11—H11	120.7
N1—C2—C8	116.4 (3)	C12—C11—C10	118.5 (4)
C3—C2—C8	121.2 (4)	C12—C11—H11	120.7
C2—C3—H3	120.0	N7—C12—C11	124.1 (4)
C2—C3—C4	119.9 (4)	N7—C12—H12	117.9
C4—C3—H3	120.0	C11—C12—H12	117.9
C3—C4—C13	119.8 (4)	C14—C13—C4	179.1 (4)
C5—C4—C3	118.0 (4)	C13—C14—C17	178.4 (4)
C5—C4—C13	122.2 (4)	C16—N15—C20	116.9 (4)
C4—C5—H5	120.9	N15—C16—H16	118.0
C4—C5—C6	118.2 (4)	N15—C16—C17	124.0 (4)
C6—C5—H5	120.9	C17—C16—H16	118.0
N1—C6—C5	124.4 (4)	C16—C17—C14	120.1 (4)
N1—C6—H6	117.8	C16—C17—C18	117.8 (4)
C5—C6—H6	117.8	C18—C17—C14	122.2 (4)
C12—N7—C8	117.2 (3)	C17—C18—H18	120.7
N7—C8—C2	116.4 (3)	C19—C18—C17	118.7 (4)
N7—C8—C9	122.3 (4)	C19—C18—H18	120.7
C9—C8—C2	121.3 (4)	C18—C19—H19	120.5
C8—C9—H9	120.3	C18—C19—C20	119.1 (4)
C10—C9—C8	119.3 (4)	C20—C19—H19	120.5
C10—C9—H9	120.3	N15—C20—C19	123.5 (4)
C9—C10—H10	120.7	N15—C20—H20	118.2
C9—C10—C11	118.6 (4)	C19—C20—H20	118.2

N1—C2—C3—C4	−1.3 (6)	C8—N7—C12—C11	−0.4 (6)
N1—C2—C8—N7	179.9 (3)	C8—C9—C10—C11	−0.6 (6)
N1—C2—C8—C9	−0.5 (6)	C9—C10—C11—C12	0.7 (6)
C2—N1—C6—C5	0.2 (6)	C10—C11—C12—N7	−0.2 (7)
C2—C3—C4—C5	1.7 (6)	C12—N7—C8—C2	−179.9 (3)
C2—C3—C4—C13	−178.8 (4)	C12—N7—C8—C9	0.5 (6)
C2—C8—C9—C10	−179.6 (4)	C13—C4—C5—C6	179.3 (4)
C3—C2—C8—N7	−0.4 (6)	C14—C17—C18—C19	−178.9 (4)
C3—C2—C8—C9	179.3 (4)	N15—C16—C17—C14	179.3 (4)
C3—C4—C5—C6	−1.1 (6)	N15—C16—C17—C18	−1.5 (6)
C4—C5—C6—N1	0.2 (6)	C16—N15—C20—C19	−0.6 (6)
C6—N1—C2—C3	0.4 (6)	C16—C17—C18—C19	1.9 (6)
C6—N1—C2—C8	−179.9 (3)	C17—C18—C19—C20	−1.8 (6)
N7—C8—C9—C10	0.0 (6)	C18—C19—C20—N15	1.1 (7)
C8—C2—C3—C4	178.9 (4)	C20—N15—C16—C17	0.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N7ⁱ	0.95	2.55	3.475 (5)	163
C18—H18···N1ⁱⁱ	0.95	2.60	3.509 (5)	161

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x+1, −y+3/2, z+1/2.

(III) 4-(Indol-4-yl)-2,2'-bipyridine top

Crystal data top

C₁₈H₁₃N₃	D_x = 1.364 Mg m⁻³
M_r = 271.31	Melting point = 398–400 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6951 (6) Å	Cell parameters from 4854 reflections
b = 12.0142 (7) Å	θ = 3.5–29.1°
c = 12.0376 (9) Å	µ = 0.08 mm⁻¹
β = 109.552 (8)°	T = 100 K
V = 1321.28 (15) Å³	Block, orange
Z = 4	0.35 × 0.35 × 0.20 mm
F(000) = 568

Data collection top

Agilent SuperNova (single source at offset, Eos detector) diffractometer	2692 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2363 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.023
Detector resolution: 15.9631 pixels mm^-1	θ_max = 26.4°, θ_min = 2.8°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −13→15
T_min = 0.993, T_max = 1.000	l = −15→11
8569 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0344P)² + 0.7137P] where P = (F_o² + 2F_c²)/3
2692 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
N1	0.31593 (11)	0.25441 (9)	0.52186 (10)	0.0149 (2)
C2	0.25581 (13)	0.33233 (11)	0.43923 (11)	0.0136 (3)
C3	0.26375 (13)	0.44551 (11)	0.46516 (11)	0.0143 (3)
H3	0.2241	0.4982	0.4039	0.017*
C4	0.33001 (13)	0.48165 (11)	0.58118 (11)	0.0140 (3)
C5	0.39151 (13)	0.40081 (11)	0.66627 (11)	0.0155 (3)
H5	0.4381	0.4211	0.7464	0.019*
C6	0.38351 (14)	0.29005 (11)	0.63189 (11)	0.0154 (3)
H6	0.4290	0.2361	0.6904	0.018*
N7	0.12564 (12)	0.36675 (9)	0.23212 (10)	0.0173 (3)
C8	0.17196 (13)	0.29055 (11)	0.31882 (11)	0.0143 (3)
C9	0.14054 (14)	0.17732 (11)	0.29891 (12)	0.0169 (3)
H9	0.1737	0.1253	0.3617	0.020*
C10	0.06031 (14)	0.14199 (11)	0.18635 (12)	0.0186 (3)
H10	0.0385	0.0653	0.1709	0.022*
C11	0.01227 (14)	0.21922 (12)	0.09662 (12)	0.0183 (3)
H11	−0.0428	0.1971	0.0186	0.022*
C12	0.04713 (14)	0.33039 (12)	0.12420 (12)	0.0181 (3)
H12	0.0133	0.3838	0.0628	0.022*
N13	0.25953 (12)	0.93647 (9)	0.65298 (10)	0.0172 (3)
H13	0.2204	0.9745	0.6974	0.021*
C14	0.31571 (14)	0.98129 (11)	0.57170 (12)	0.0182 (3)
H14	0.3184	1.0585	0.5553	0.022*
C15	0.36687 (14)	0.89859 (11)	0.51831 (12)	0.0170 (3)
H15	0.4112	0.9076	0.4594	0.020*
C16	0.34102 (13)	0.79562 (11)	0.56791 (11)	0.0143 (3)
C17	0.36292 (13)	0.68330 (11)	0.54613 (11)	0.0142 (3)
H17	0.4045	0.6637	0.4877	0.017*
C18	0.32337 (13)	0.60125 (11)	0.61069 (11)	0.0139 (3)
C19	0.26479 (14)	0.63113 (11)	0.69974 (11)	0.0149 (3)
H19	0.2429	0.5742	0.7460	0.018*
C20	0.23857 (14)	0.74072 (11)	0.72121 (11)	0.0156 (3)
H20	0.1974	0.7597	0.7801	0.019*
C21	0.27468 (13)	0.82248 (11)	0.65331 (11)	0.0146 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0145 (5)	0.0133 (5)	0.0168 (6)	0.0003 (4)	0.0051 (4)	0.0009 (4)
C2	0.0121 (6)	0.0143 (6)	0.0149 (6)	0.0002 (5)	0.0054 (5)	0.0004 (5)
C3	0.0150 (6)	0.0130 (6)	0.0143 (6)	0.0006 (5)	0.0040 (5)	0.0019 (5)
C4	0.0121 (6)	0.0140 (6)	0.0169 (7)	−0.0011 (5)	0.0061 (5)	0.0003 (5)
C5	0.0132 (6)	0.0176 (7)	0.0143 (6)	−0.0012 (5)	0.0026 (5)	−0.0004 (5)
C6	0.0138 (6)	0.0148 (6)	0.0167 (6)	0.0018 (5)	0.0041 (5)	0.0035 (5)
N7	0.0182 (5)	0.0159 (6)	0.0166 (6)	−0.0010 (4)	0.0045 (4)	0.0009 (5)
C8	0.0132 (6)	0.0148 (6)	0.0158 (6)	0.0007 (5)	0.0060 (5)	−0.0003 (5)
C9	0.0165 (6)	0.0142 (7)	0.0193 (7)	0.0014 (5)	0.0050 (5)	0.0006 (5)
C10	0.0146 (6)	0.0155 (7)	0.0244 (7)	−0.0004 (5)	0.0050 (5)	−0.0052 (6)
C11	0.0133 (6)	0.0244 (7)	0.0165 (7)	−0.0009 (5)	0.0039 (5)	−0.0053 (6)
C12	0.0183 (6)	0.0196 (7)	0.0156 (7)	0.0005 (5)	0.0044 (5)	0.0018 (5)
N13	0.0210 (6)	0.0122 (6)	0.0171 (6)	0.0021 (5)	0.0049 (4)	−0.0019 (4)
C14	0.0223 (7)	0.0124 (6)	0.0164 (7)	−0.0016 (5)	0.0017 (5)	0.0015 (5)
C15	0.0208 (6)	0.0147 (6)	0.0142 (6)	−0.0029 (5)	0.0040 (5)	0.0010 (5)
C16	0.0134 (6)	0.0151 (6)	0.0118 (6)	−0.0013 (5)	0.0007 (5)	−0.0005 (5)
C17	0.0137 (6)	0.0145 (6)	0.0133 (6)	−0.0003 (5)	0.0031 (5)	−0.0015 (5)
C18	0.0118 (6)	0.0143 (6)	0.0130 (6)	−0.0001 (5)	0.0009 (5)	−0.0009 (5)
C19	0.0161 (6)	0.0149 (6)	0.0128 (6)	−0.0024 (5)	0.0036 (5)	0.0007 (5)
C20	0.0153 (6)	0.0184 (7)	0.0133 (6)	−0.0003 (5)	0.0050 (5)	−0.0018 (5)
C21	0.0140 (6)	0.0128 (6)	0.0141 (6)	0.0003 (5)	0.0006 (5)	−0.0025 (5)

Geometric parameters (Å, º) top

N1—C2	1.3481 (17)	C11—C12	1.3904 (19)
N1—C6	1.3365 (17)	C12—H12	0.9500
C2—C3	1.3915 (18)	N13—H13	0.8800
C2—C8	1.4916 (18)	N13—C14	1.3786 (18)
C3—H3	0.9500	N13—C21	1.3773 (17)
C3—C4	1.3969 (18)	C14—H14	0.9500
C4—C5	1.3925 (18)	C14—C15	1.3637 (19)
C4—C18	1.4867 (18)	C15—H15	0.9500
C5—H5	0.9500	C15—C16	1.4318 (18)
C5—C6	1.3880 (18)	C16—C17	1.4043 (18)
C6—H6	0.9500	C16—C21	1.4202 (18)
N7—C8	1.3473 (17)	C17—H17	0.9500
N7—C12	1.3401 (17)	C17—C18	1.3864 (18)
C8—C9	1.3972 (18)	C18—C19	1.4170 (18)
C9—H9	0.9500	C19—H19	0.9500
C9—C10	1.3841 (19)	C19—C20	1.3817 (18)
C10—H10	0.9500	C20—H20	0.9500
C10—C11	1.381 (2)	C20—C21	1.3953 (19)
C11—H11	0.9500

C6—N1—C2	117.14 (11)	N7—C12—H12	118.0
N1—C2—C3	122.36 (12)	C11—C12—H12	118.0
N1—C2—C8	116.34 (11)	C14—N13—H13	125.6
C3—C2—C8	121.20 (11)	C21—N13—H13	125.6
C2—C3—H3	120.0	C21—N13—C14	108.87 (11)
C2—C3—C4	120.03 (12)	N13—C14—H14	125.0
C4—C3—H3	120.0	C15—C14—N13	110.02 (12)
C3—C4—C18	119.81 (11)	C15—C14—H14	125.0
C5—C4—C3	117.33 (12)	C14—C15—H15	126.5
C5—C4—C18	122.72 (12)	C14—C15—C16	106.91 (12)
C4—C5—H5	120.6	C16—C15—H15	126.5
C6—C5—C4	118.81 (12)	C17—C16—C15	133.94 (12)
C6—C5—H5	120.6	C17—C16—C21	119.13 (12)
N1—C6—C5	124.24 (12)	C21—C16—C15	106.88 (11)
N1—C6—H6	117.9	C16—C17—H17	120.3
C5—C6—H6	117.9	C18—C17—C16	119.41 (12)
C12—N7—C8	117.60 (12)	C18—C17—H17	120.3
N7—C8—C2	117.13 (11)	C17—C18—C4	120.74 (12)
N7—C8—C9	122.12 (12)	C17—C18—C19	120.00 (12)
C9—C8—C2	120.73 (12)	C19—C18—C4	119.07 (11)
C8—C9—H9	120.5	C18—C19—H19	119.1
C10—C9—C8	119.03 (13)	C20—C19—C18	121.89 (12)
C10—C9—H9	120.5	C20—C19—H19	119.1
C9—C10—H10	120.3	C19—C20—H20	121.2
C11—C10—C9	119.44 (13)	C19—C20—C21	117.60 (12)
C11—C10—H10	120.3	C21—C20—H20	121.2
C10—C11—H11	121.1	N13—C21—C16	107.31 (11)
C10—C11—C12	117.85 (12)	N13—C21—C20	130.87 (12)
C12—C11—H11	121.1	C20—C21—C16	121.82 (12)
N7—C12—C11	123.95 (13)

N1—C2—C3—C4	−2.97 (19)	C10—C11—C12—N7	0.7 (2)
N1—C2—C8—N7	−172.50 (11)	C12—N7—C8—C2	−178.40 (11)
N1—C2—C8—C9	9.08 (17)	C12—N7—C8—C9	0.00 (19)
C2—N1—C6—C5	2.00 (19)	N13—C14—C15—C16	0.34 (15)
C2—C3—C4—C5	2.62 (18)	C14—N13—C21—C16	−0.78 (14)
C2—C3—C4—C18	−173.06 (11)	C14—N13—C21—C20	178.21 (13)
C2—C8—C9—C10	178.90 (12)	C14—C15—C16—C17	176.75 (14)
C3—C2—C8—N7	10.94 (18)	C14—C15—C16—C21	−0.80 (14)
C3—C2—C8—C9	−167.48 (12)	C15—C16—C17—C18	−179.18 (13)
C3—C4—C5—C6	−0.18 (18)	C15—C16—C21—N13	0.97 (14)
C3—C4—C18—C17	−50.68 (17)	C15—C16—C21—C20	−178.13 (11)
C3—C4—C18—C19	124.26 (13)	C16—C17—C18—C4	173.34 (11)
C4—C5—C6—N1	−2.2 (2)	C16—C17—C18—C19	−1.55 (18)
C4—C18—C19—C20	−171.75 (11)	C17—C16—C21—N13	−177.02 (11)
C5—C4—C18—C17	133.88 (13)	C17—C16—C21—C20	3.88 (18)
C5—C4—C18—C19	−51.18 (17)	C17—C18—C19—C20	3.23 (19)
C6—N1—C2—C3	0.64 (18)	C18—C4—C5—C6	175.36 (11)
C6—N1—C2—C8	−175.87 (11)	C18—C19—C20—C21	−1.27 (19)
N7—C8—C9—C10	0.56 (19)	C19—C20—C21—N13	178.86 (13)
C8—C2—C3—C4	173.38 (11)	C19—C20—C21—C16	−2.28 (18)
C8—N7—C12—C11	−0.6 (2)	C21—N13—C14—C15	0.28 (15)
C8—C9—C10—C11	−0.48 (19)	C21—C16—C17—C18	−1.86 (18)
C9—C10—C11—C12	−0.12 (19)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of rings N13/C14–C16/C21, N1/C2–C6, N7/C8–C12 and C16–C21, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···N7ⁱ	0.88	2.22	3.002 (2)	148
C14—H14···N1ⁱⁱ	0.95	2.39	3.336 (2)	176
C5—H5···Cg1ⁱⁱⁱ	0.95	2.58	3.3371 (14)	137
C6—H6···Cg4ⁱⁱⁱ	0.95	2.78	3.5268 (14)	136
C11—H11···Cg4^iv	0.95	2.56	3.3548 (15)	141
C17—H17···Cg2^v	0.95	2.85	3.6555 (15)	143
C20—H20···Cg3^vi	0.95	2.86	3.5814 (16)	133

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x, y−1/2, −z+1/2; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1.

4-Substituted 2,2'-bipyridines present in the Cambridge Structural Database^a top

The dihedral angle Py–Py is defined as the angle between the best planes through both pyridine rings and the dihedral angle Py–Ar is defined as the angle between the best planes through the 4-substituted pyridine and the aromatic substituent.

4-Substituent	CSD refcode	Dihedral angle Py–Py (°)	Dihedral angle Py–Ar (°)	Reference
(substituted) phenyl	EWOYEW	0.8	9.1	Ramakrishnan et al. (2016)
	EWOXIZ	7.8/28.5/12.5	35.8/32.8/40.8	Ramakrishnan et al. (2016)
	ZOZRIF	6.6	24.5	Wang et al. (1996)
	RIPQUC	15.7	42.9	Cargill Thompson et al. (1997)
triazine	MULRUI	14.2/3.7/18.5	8.1/6.1/25.2	Laramée-Milette et al. (2015)
(substituted) naphthalene	EWOXUL	2.8/10.8/1.8	6.0/26.1/32.9	Ramakrishnan et al. (2016)
	EWOYIA	18.2/20.8	34.8/31.7	Ramakrishnan et al. (2016)
	OKAGOX	23.0/9.6	44.6/39.3	He et al. (2011)
2,2'-bipyridine	TEBGAI	3.2/2.7	0.0/0.0	Honey & Steel (1991)
anthracene	EWOWUK	4.0	73.8	Ramakrishnan et al. (2016)
phenanthrene	EWOXAR	5.2	64.8	Ramakrishnan et al. (2016)
	EWOXEV	11.1	53.1	Ramakrishnan et al. (2016)
pyrene	EWOXOF	4.0	51.6	Ramakrishnan et al. (2016)

Note: (a) Groom et al. (2016).

Acknowledgements

The Hercules Foundation is thanked for supporting the purchase of the diffractometer.

Funding information

Funding for this research was provided by: Hercules Foundation (Belgium) (award No. AKUL/09/0035).

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Volume 73| Part 4| April 2017| Pages 610-615

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of three 4-substituted-2,2′-bi­pyridines synthesized by Sonogashira and Suzuki–Miyaura cross-coupling reactions

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Structure solution and refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Crystal structures of three 4-substituted-2,2′-bipyridines synthesized by Sonogashira and Suzuki–Miyaura cross-coupling reactions

3. Supramolecular features