Home The crystal structure of 2-phenyl-4,6-bis(prop-2-yn-1-yloxy)-1,3,5-triazine, C15H11N3O2
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The crystal structure of 2-phenyl-4,6-bis(prop-2-yn-1-yloxy)-1,3,5-triazine, C15H11N3O2

  • Jin Li ORCID logo , Yan Chen , Ziqing Wu , Yali Liu , Dachuan Yin EMAIL logo and Zhenyu Zuo
Published/Copyright: December 13, 2019

Abstract

C15H11N3O2, triclinic, P1̄ (no. 2), a = 8.4680(5) Å, b = 9.7578(5) Å, c = 10.2101(6) Å, α = 104.578(5)°, β = 111.882(6)°, γ = 106.589(5)°, V = 686.77(8) Å3, Z = 2, Rgt(F) = 0.0394, wRref(F2) = 0.1261, T = 250(2) K.

CCDC no.: 1956210

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Yellow block
Size:0.18 × 0.16 × 0.12 mm
Wavelength:Cu Kα radiation (1.54184 Å)
μ:0.72 mm−1
Diffractometer, scan mode:SuperNova, ω
θmax, completeness:76.5°, >99%
N(hkl)measured, N(hkl)unique, Rint:6581, 2857, 0.013
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2328
N(param)refined:182
Programs:CrysAlisPRO [1], SHELX [2]
Table 2:

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

AtomxyzUiso*/Ueq
O10.26180(14)0.89380(11)0.61705(11)0.0687(3)
O20.62462(13)0.72655(10)0.92966(10)0.0631(3)
N10.22943(15)0.64959(12)0.51991(12)0.0562(3)
N20.45351(15)0.81844(12)0.78189(12)0.0563(3)
N30.41981(14)0.55814(11)0.67794(11)0.0531(3)
C10.0410(2)0.34891(18)0.27641(15)0.0683(4)
H1−0.00120.42560.26080.082*
C2−0.0468(2)0.1998(2)0.15944(17)0.0851(5)
H2−0.14850.17590.06460.102*
C30.0144(3)0.0876(2)0.1819(2)0.0892(6)
H3−0.0463−0.01300.10270.107*
C40.1634(3)0.12125(19)0.3189(2)0.0849(5)
H40.20520.04400.33320.102*
C50.2528(2)0.26881(16)0.43661(18)0.0690(4)
H50.35530.29160.53050.083*
C60.19101(17)0.38337(14)0.41604(14)0.0551(3)
C70.28490(16)0.53931(13)0.54374(13)0.0498(3)
C80.49416(17)0.69758(14)0.78949(13)0.0516(3)
C90.32045(18)0.78521(15)0.64352(15)0.0547(3)
C100.3547(2)1.04671(16)0.74137(19)0.0701(4)
H10A0.38531.03560.83950.084*
H10B0.26981.09850.72690.084*
C110.5252(2)1.14199(18)0.7470(2)0.0739(4)
C120.6599(3)1.2194(2)0.7483(3)0.1089(7)
H120.76831.28170.74940.131*
C130.6787(2)0.60103(16)0.94380(15)0.0637(4)
H13A0.74870.58580.88790.076*
H13B0.56720.50330.90110.076*
C140.79587(19)0.64587(17)1.10754(16)0.0640(4)
C150.8877(2)0.6802(2)1.23930(18)0.0789(5)
H150.96140.70771.34510.095*

Source of material

To ethyl ether (150 mL), were added Mg (3.84 g, 0.160 mol) and I2 (1.02 g, 0.004 mol) under the atmosphere of N2. After the mixture was stirred for 10 min, bromobenzene (25 g, 0.160 mol) was added dropwisely. When Mg disappeared, the reaction mixture was refluxed for 30 min and then cooled to −15 °C. To the above solution of PhMgBr was added a solution of 2,4,6-trichloro-1,3,5-triazine (32 g, 0.175 mol) in tetrahydrofuran in 30 min. After 2 h, the reaction was quenched by 20 mL of ethanol. The final mixture was filtered and the filtrate was evaporated to get a yellow solid, which was purified by chromatography on silica gel to get the 2,4-dichloro-6-phenyl-1,3,5-triazine (27.85 g, yield 77%) as a white solid. To the solution of 2,4-dichloro-6-phenyl-1,3,5-triazine (4.52 g, 0.02 mol) in 120 mL of tetrahydrofuran was added K2CO3 (5.52 g, 0.04 mol) and prop-2-yn-1-ol (2.25 g, 0.04 mol). The reaction system was refluxed for 24 h and then filtered to get a brown solution. The solvent was evaporated under reduced pressure to get a yellow solid which was purified by chromatography on silica gel to afford 2-chloro-4-(prop-2-yn-1-yloxy)-6-phenyl-1,3,5-triazine as a light yellow solid. (2.75 g, 52%). 1H-NMR (400 MHz, chloroform-d)): δ [ppm] 7.59(d, J = 8 Hz, 2H), 7.53–7.49 (m, 3H), 5.15 (s, 4H), 2.57 (s, 2H). The crystals were obtained by recrystallization from ethyl acetate at room temperature.

Experimental details

The hydrogen atoms were placed at calculated positions as riding atoms.

Comment

As an important unsaturated unit, the ethynyl group can be used to construct big π-conjugated systems, which can be widely applied into organic electronics, such as high performance organic field-effect transistors [3], [4], organic solar cells [5], organic light-emitting materials [6], organic liquid crystal materials [7] and so on. The s-triazine (1,3,5-triazine) ring is a remarkable building block to generate supramolecular interactions and an important unit to construct various nonlinear optical devices [8]. So designing and synthesizing of novel triazine derivatives with ethynyl conjugated units is a charming direction in organic synthesis. The structure of the title compound was characterized by 1H-NMR and X-ray diffraction.

In the title molecule, the typical bond length [9] of C1—C6, O1—C10, N3—C7 and C11—C12 are 1.3872(19) Å, 1.4451(17) Å, 1.3428(15) Å and 1.167(3) Å, respectively. The torsion angle of C5—C6—C7—N3 is 4°, which demonstrated that the benzene ring and the 1,3,5-triazine ring are not exactly in the same plane (cf. the figure). Similar to the packing of other triazines weak non-classical hydrogen bonds [10] were observed. In the molecular packing, there are obvious π-π stacking interactions between the adjacent aromatic moieties. The distance between adjacent aromatic moieties is less than 3.447 Å.

Funding source: National Key R&D program of China

Award Identifier / Grant number: 2018YFC1706903

Funding source: Shaanxi Key Laboratory of Basic and New Herbal Medicament Research

Award Identifier / Grant number: 2017KF05

Award Identifier / Grant number: 19JS019

Award Identifier / Grant number: 81403101

Funding source: Subject Innovation Team of Shaanxi University of Chinese Medicine

Award Identifier / Grant number: 2019-YL11

Funding source: Key Discipline of TCM Pharmaceutical Engineering in Shaanxi Administration of Traditional Chinese Medicine

Award Identifier / Grant number: 303061107

Award Identifier / Grant number: 132018004

Funding statement: We acknowledge the supports by National Key R&D program of China (2018YFC1706903), the Project of Shaanxi Key Laboratory of Basic and New Herbal Medicament Research (NO: 2017KF05) (NO: 19JS019), the National Natural Science Foundation of China (NO: 81403101), the Subject Innovation Team of Shaanxi University of Chinese Medicine (NO. 2019-YL11), Key Discipline of TCM Pharmaceutical Engineering in Shaanxi Administration of Traditional Chinese Medicine (NO: 303061107) (NO: 132018004).

References

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Received: 2019-09-29
Accepted: 2019-11-22
Published Online: 2019-12-13
Published in Print: 2020-02-25

©2019 Jin Li et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.

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  75. Crystal structure of η6-p-cymene-iodido-(N-isopropyl-1-(pyridin-2-yl)methanimine-κ2N,N′)ruthenium(II) hexafluorophosphate(V), C19H26IN2F6Ru
  76. Crystal structure of 6-iodo-3-phenyl-2-propylquinazolin-4(3H)-one, C17H15IN2O
  77. Low temperature redetermination of the crystal structure of catena-poly[[tri-4-fluorobenzyltin(IV)]μ2-pyridine-4-carboxylato-κ2N:O], {C27H22F3NO2Sn}n
  78. Crystal structure of bis(2-propyl-1H-benzo[d]imidazol-3-ium) tetrachloridozincate(II), C10H13Cl4N2Zn
  79. The crystal structure of (Z)-3-hydrazono-5-nitroindolin-2-one – dimethyl sulfoxide (1/1), C8H6N4O3
  80. Crystal structure of bis-[N-(1-pyrazin-2-yl-ethylidene)-cyanoacetic acid-hydrazonato-κ3O,N,N′)]-zinc(II), C18H16N10O2Zn
  81. Crystal structure and photochromism of 1-(2,5-dimethyl-3-thienyl)-2-[2-methyl-5-(benzaldoxime)-3-thienyl] perfluorocyclopentene, C23H17F6NOS2
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