Crystal structure of 4-(anthracen-9-yl)pyridine

Zhao, M.; Zhang, G.; Zhang, J.; Huang, S.; Liu, X.; Li, F.

doi:10.1107/S2056989021004710

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ISSN: 2056-9890

Volume 77| Part 6| June 2021| Pages 605-608

https://doi.org/10.1107/S2056989021004710

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Crystal structure of 4-(anthracen-9-yl)pyridine

Meng Zhao,^a Gang Zhang,^a Jingmiao Zhang,^a Shan Huang,^a Xiuxia Liu ^a and Fei Li ^a ^*

^aDepartment of Nuclear Medicine, the Second Hospital of Anhui Medical University, Hefei 230601, People's Republic of China
^*Correspondence e-mail: lifei007@139.com

Edited by D. Chopra, Indian Institute of Science Education and Research Bhopal, India (Received 31 March 2021; accepted 4 May 2021; online 11 May 2021)

The title compound, C₁₉H₁₃N, which crystallizes in the monoclinic C2/c space group with one half-molecule in the asymmetric unit, was synthesized by Suzuki–Miyaura cross-coupling reaction of 9-bromoanthracene with pyridin-4-ylboronic acid and purified by column chromatography on silica gel. Light-yellow crystals of 4-(anthracen-9-yl)-pyridine suitable for X-ray diffraction were collected by the solvent evaporation method. In the crystal, pairs of molecules are connected by intermolecular C—H⋯π (pyridine) interactions [d(H7⋯Cg) = 2.7391 (2) Å], forming cyclic centrosymmetric dimers, further resulting in an infinite one-dimensional linear chain along the c-axis direction. Weak face-to-face π–π stacking interactions [d(Cg⋯Cg) = 3.6061 (2) Å] link neighboring lamellar networks into the supramolecular structure.

Keywords: crystal structure; anthracene; C—H⋯π interactions; π–π stacking interactions.

CCDC reference: 2072800

1. Chemical context

Anthracene and its derivatives constitute a very famous class of fluorophores that have been widely used in the development of functional fluorescent chemosensors because of their intriguing photophysical properties and chemical stability (Martínez-Máñez et al., 2003 ). One of the most important steps in the rational molecule design of anthracene-based chemosensors is the judicious combination with functional chemical recognition moieties, which can be used for monitoring and quantifying of abnormal physiological changes at the subcellular level (Densil et al., 2018 ; Mondal et al., 2014 ; Anand et al., 2015 ; Shree et al., 2019 ). It has been found that 9,10-distyrylanthracene derivatives with restricted intramolecular rotations often lead to aggregation-induced emission characteristics (Lu et al., 2010 ). In recent years, there has been an increased effort to combine anthracene derivatives with N- or O-coordinated single ligands and other attractive mixed ligands in order to construct tunable fluorescent ligands (Dey et al., 2016 ; Yao et al., 2019 ). As part of our studies in this area, we report herein the synthesis and crystal structure of a fluorescent monopyridine ligand, C₁₉H₁₃N.

2. Structural commentary

As shown in Fig. 1, single-crystal X-ray diffraction analysis reveals that 4-(anthracen-9-yl)-pyridine crystallizes in the monoclinic C2/c space group with half molecule in the asymmetric unit (Table 1). In the structure of the title compound, the C–C bond lengths of the benzene ring range from 1.3534 (13) to 1.4352 (1) Å, and the C–N bond length is 1.3351 (11), which is comparable with the literature reported (Zhao et al., 2016 ). The bond angle of N1–C1–C2 is 124.161 (7)°, closed to the ideal bond angle of 120° for benzene ring. The pyridine ring is inclined to the benzene ring at a dihedral angle of 71.64 (4)°.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cgⁱ	0.93	2.74	3.5606 (12)	148
C7—H7⋯Cgⁱⁱ	0.93	2.74	3.5606 (12)	148
Symmetry codes: (i) ; (ii) $[x+1, -y+1, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of 4-(anthracen-9-yl)-pyridine with displacement ellipsoids at the 50% probability level. Symmetry code: (i) −x, y, $[1\over2]$ − z.

3. Supramolecular features

In the crystal, the hydrogen atom of anthracene ring contributes to the formation of a C7—H7⋯π contact with the pyridine ring (Table 1); the resulting cyclic centrosymmetric dimer is shown in Fig. 2. Subsequently, the paired C—H⋯π(pyridine) hydrogen-bonding interactions connect neighboring dimers, resulting in an infinite 1-D linear chain (Fig. 3), which is basis for extension of the dimensionality. As shown in Figs. 4 and 5, the crystal packing involves weak face-to-face π–π stacking interactions [d(Cg⋯Cg) = 3.6095 (7) Å] between two benzene rings related by the symmetry operation 1 − x, y, $[1\over2]$ − z.

Figure 2
The hydrogen-bonded centrosymmetric dimer along the c axis. Dashed lines indicate C—H⋯π interactions.

Figure 3
View of the 1-D chain-like structure of the title compound along the c axis.

Figure 4
Crystal packing projected via C—H⋯π and π–π stacking interactions.

Figure 5
π–π stacking interactions of molecules in the crystal structure of the title compound.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.41, update March 2021; Groom et al. 2016 ) revealed that this is the first example of a structurally characterized 4-(anthracen-9-yl)-pyridine. At the same time, a CSD search for compounds containing the 4-(anthracen-9-yl)-pyridine substructure identified only one compound, viz. Ag₁₂(SCH₂C₆H₅)₆(CF₃COO)₆(L₄)₆ [L₄ = 4-(anthracen-9-yl)-pyridine; Li et al., 2018 ] in which the pyridine ring of this compound is inclined to the benzene ring at a dihedral angle of 73.28°.

5. Synthesis and crystallization

4-(Anthracen-9-yl)-pyridine was synthesized by the Suzuki–Miyaura cross-coupling reaction according to a previously reported protocol (Zhao et al., 2019 ). As shown in Fig. 6, under a nitrogen atmosphere, 9-bromoanthracene (2.56 g, 10 mmol), pyridin-4-ylboronic acid (1.23 g, 10 mmol) and tetratriphenyl phosphine palladium (0.10 g, 0.1 mmol) were dissolved in toluene (90 mL) followed by the addition of potassium carbonate aqueous solution (22 wt%, 40 mL) under constant stirring. The reaction mixture was subsequently refluxed for 12 h, and the mixture was then further purified by column chromatography using petroleum/ethyl acetate (3:1, v/v) as eluent to give yellow solid 4-(anthracen-9-yl)pyridine (1.76 g, yield 69%).

Figure 6
Synthesis of 4-(anthracen-9-yl)-pyridine.

Crystals of 4-(anthracen-9-yl)-pyridine suitable for X-ray analysis were obtained by the solvent evaporation method. In detail, solid 4-(anthracen-9-yl)-pyridine (0.013 g, 0.05 mmol) was dissolved in 0.5 mL of dichloromethane and 5 mL of ethyl acetate. The mixture solvent was evaporated slowly at room temperature for about 2 weeks. Light-yellow crystals of 4-(anthracen-9-yl)-pyridine suitable for X-ray diffraction were collected.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃N
M_r	255.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	6.0777 (4), 20.9211 (16), 10.2574 (7)
β (°)	102.476 (3)
V (Å³)	1273.45 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.18 × 0.15 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.699, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	4703, 1144, 1022
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.105, 1.11
No. of reflections	1144
No. of parameters	94
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.14
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2015 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2072800

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021004710/dx2036sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989021004710/dx2036Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

4-(Anthracen-9-yl)pyridine top

Crystal data top

C₁₉H₁₃N	F(000) = 536
M_r = 255.30	D_x = 1.332 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.0777 (4) Å	Cell parameters from 2979 reflections
b = 20.9211 (16) Å	θ = 3.7–25.3°
c = 10.2574 (7) Å	µ = 0.08 mm⁻¹
β = 102.476 (3)°	T = 296 K
V = 1273.45 (16) Å³	Bulk, light yellow
Z = 4	0.18 × 0.15 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	1022 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 25.3°, θ_min = 3.7°
T_min = 0.699, T_max = 0.745	h = −7→6
4703 measured reflections	k = −22→24
1144 independent reflections	l = −12→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0556P)² + 0.3319P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1144 reflections	Δρ_max = 0.15 e Å⁻³
94 parameters	Δρ_min = −0.14 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.

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

	x	y	z	U_iso*/U_eq
N1	0.000000	0.36240 (5)	0.250000	0.0360 (4)
C1	0.12815 (18)	0.39626 (5)	0.18480 (11)	0.0359 (3)
H1	0.219495	0.374032	0.138423	0.043*
C2	0.13369 (17)	0.46237 (5)	0.18183 (10)	0.0324 (3)
H2	0.226472	0.483317	0.134422	0.039*
C3	0.000000	0.49724 (7)	0.250000	0.0266 (4)
C4	0.000000	0.56870 (6)	0.250000	0.0267 (4)
C5	0.18833 (15)	0.60220 (5)	0.32231 (9)	0.0279 (3)
C6	0.38307 (17)	0.57083 (5)	0.39762 (10)	0.0308 (3)
H6	0.387809	0.526405	0.399226	0.037*
C7	0.56176 (18)	0.60434 (5)	0.46706 (11)	0.0357 (3)
H7	0.686262	0.582594	0.515636	0.043*
C8	0.56061 (19)	0.67201 (5)	0.46633 (12)	0.0405 (3)
H8	0.683709	0.694491	0.514440	0.049*
C9	0.38025 (19)	0.70397 (5)	0.39555 (11)	0.0407 (4)
H9	0.381857	0.748415	0.394805	0.049*
C10	0.18747 (17)	0.67085 (5)	0.32198 (10)	0.0325 (3)
C11	0.000000	0.70319 (7)	0.250000	0.0371 (4)
H11	0.000002	0.747643	0.250003	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0410 (8)	0.0233 (7)	0.0417 (7)	0.000	0.0045 (6)	0.000
C1	0.0393 (6)	0.0281 (6)	0.0414 (6)	0.0039 (4)	0.0110 (5)	−0.0046 (4)
C2	0.0351 (6)	0.0280 (6)	0.0363 (6)	−0.0016 (4)	0.0123 (4)	−0.0006 (4)
C3	0.0274 (7)	0.0243 (7)	0.0269 (7)	0.000	0.0026 (5)	0.000
C4	0.0323 (8)	0.0235 (8)	0.0262 (7)	0.000	0.0108 (5)	0.000
C5	0.0328 (6)	0.0261 (6)	0.0268 (6)	−0.0010 (4)	0.0110 (4)	−0.0001 (3)
C6	0.0351 (6)	0.0260 (6)	0.0320 (6)	−0.0004 (4)	0.0085 (4)	0.0000 (4)
C7	0.0333 (6)	0.0362 (7)	0.0364 (6)	−0.0006 (4)	0.0050 (4)	0.0003 (4)
C8	0.0391 (7)	0.0359 (7)	0.0443 (7)	−0.0109 (5)	0.0039 (5)	−0.0035 (5)
C9	0.0479 (7)	0.0250 (6)	0.0473 (7)	−0.0073 (4)	0.0062 (6)	−0.0017 (4)
C10	0.0393 (7)	0.0255 (6)	0.0333 (6)	−0.0029 (4)	0.0091 (5)	−0.0004 (4)
C11	0.0467 (9)	0.0209 (7)	0.0427 (9)	0.000	0.0075 (7)	0.000

Geometric parameters (Å, º) top

N1—C1	1.3345 (12)	C6—H6	0.9300
N1—C1ⁱ	1.3345 (12)	C6—C7	1.3579 (15)
C1—H1	0.9300	C7—H7	0.9300
C1—C2	1.3840 (15)	C7—C8	1.4158 (16)
C2—H2	0.9300	C8—H8	0.9300
C2—C3	1.3881 (12)	C8—C9	1.3534 (16)
C3—C4	1.4951 (19)	C9—H9	0.9300
C4—C5ⁱ	1.4088 (12)	C9—C10	1.4284 (15)
C4—C5	1.4088 (12)	C10—C11	1.3920 (13)
C5—C6	1.4259 (14)	C11—H11	0.9300
C5—C10	1.4362 (16)

C1—N1—C1ⁱ	115.86 (12)	C7—C6—C5	121.52 (10)
N1—C1—H1	117.9	C7—C6—H6	119.2
N1—C1—C2	124.14 (10)	C6—C7—H7	119.6
C2—C1—H1	117.9	C6—C7—C8	120.73 (10)
C1—C2—H2	120.2	C8—C7—H7	119.6
C1—C2—C3	119.63 (10)	C7—C8—H8	120.0
C3—C2—H2	120.2	C9—C8—C7	119.95 (10)
C2ⁱ—C3—C2	116.60 (13)	C9—C8—H8	120.0
C2—C3—C4	121.70 (6)	C8—C9—H9	119.3
C2ⁱ—C3—C4	121.70 (6)	C8—C9—C10	121.38 (11)
C5ⁱ—C4—C3	119.84 (6)	C10—C9—H9	119.3
C5—C4—C3	119.83 (6)	C9—C10—C5	118.80 (9)
C5—C4—C5ⁱ	120.33 (13)	C11—C10—C5	119.30 (10)
C4—C5—C6	122.77 (10)	C11—C10—C9	121.90 (11)
C4—C5—C10	119.61 (9)	C10ⁱ—C11—C10	121.84 (14)
C6—C5—C10	117.62 (9)	C10ⁱ—C11—H11	119.1
C5—C6—H6	119.2	C10—C11—H11	119.1

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the pyridine ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cgⁱⁱ	0.93	2.74	3.5606 (12)	148
C7—H7···Cgⁱⁱⁱ	0.93	2.74	3.5606 (12)	148

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

Funding information

This work was supported by grants from the National Natural Science Foundation of China Incubation Program of the Second Hospital of Anhui Medical University (2020GQFY04) and Anhui Medical University Research Fund (2020xkj024).

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