research communications
of 4-(anthracen-9-yl)pyridine
aDepartment of Nuclear Medicine, the Second Hospital of Anhui Medical University, Hefei 230601, People's Republic of China
*Correspondence e-mail: lifei007@139.com
The title compound, C19H13N, which crystallizes in the monoclinic C2/c with one half-molecule in the was synthesized by Suzuki–Miyaura cross-coupling reaction of 9-bromoanthracene with pyridin-4-ylboronic acid and purified by 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.
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 of a fluorescent monopyridine ligand, C19H13N.
2. Structural commentary
As shown in Fig. 1, single-crystal X-ray reveals that 4-(anthracen-9-yl)-pyridine crystallizes in the monoclinic C2/c with half molecule in the (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)°.
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 1 − x, y, − z.
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 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 using petroleum/ethyl acetate (3:1, v/v) as to give yellow solid 4-(anthracen-9-yl)pyridine (1.76 g, yield 69%).
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 . H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2Supporting information
CCDC reference: 2072800
https://doi.org/10.1107/S2056989021004710/dx2036sup1.cif
contains datablock I. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989021004710/dx2036Isup3.cml
Data collection: APEX3 (Bruker, 2018); cell
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).C19H13N | F(000) = 536 |
Mr = 255.30 | Dx = 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 |
Bruker APEXII CCD diffractometer | 1022 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.029 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 25.3°, θmin = 3.7° |
Tmin = 0.699, Tmax = 0.745 | h = −7→6 |
4703 measured reflections | k = −22→24 |
1144 independent reflections | l = −12→12 |
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(Fo2) + (0.0556P)2 + 0.3319P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
1144 reflections | Δρmax = 0.15 e Å−3 |
94 parameters | Δρmin = −0.14 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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 |
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. |
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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