Wei Chen, Mian Ji and Shiyong Yang

Crystal structure of bis(2-fluoro-4-nitrophenyl) terephthalate C20H10F2N2O8

De Gruyter | 2016

Abstract

C20H10F2N2O8, triclinic, P1̅, a = 9.0557(19) Å, b = 9.2766(17) Å, c = 12.641(3) Å, α = 109.115(11)°, β = 97.058(11)°, γ = 108.767(11)°, V = 918.6(3) Å3, Z = 2, Rgt(F) = 0.0537, wRref(F2) = 0.1416, T = 173 K.

The crystal structure is shown in the figure, Tables 13 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal: Colorless, block, size 0.15×0.37×0.45 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 1.39 cm−1
Diffractometer, scan mode: Saturn724+ CCD, ω scans at fixed χ = 45%
2θmax: 54.98°
N(hkl)measured, N(hkl)unique: 10700, 4154
N(param)refined: 289
Programs: OLEX2 [3], SHELX [4]
Table 2

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

Atom Site x y z Uiso
H(2) 2i 0.1808 0.0372 0.6850 0.041
H(3) 2i 0.2485 0.1009 0.5288 0.038
H(6) 2i −0.0650 0.3348 0.7351 0.046
H(9) 2i 0.1176 0.2493 0.2427 0.033
H(10) 2i 0.1460 0.2992 0.0771 0.033
H(12) 2i 0.4733 0.7581 0.2723 0.036
H(13) 2i 0.4495 0.7054 0.4377 0.037
H(16) 2i 0.6688 0.8623 0.0263 0.036
H(17) 2i 0.7087 0.9399 −0.1292 0.038
H(19) 2i 0.2282 0.7495 −0.2639 0.040
Table 3

Atomic displacement parameters (Å2).

Atom Site x y z U11 U22 U33 U12 U13 U23
F(1) 2i −0.0049(2) 0.4315(2) 0.5729(1) 0.090(1) 0.098(1) 0.085(1) 0.072(1) 0.0561(9) 0.072(1)
F(2) 2i 0.1463(1) 0.6494(2) −0.1064(1) 0.0317(6) 0.0686(8) 0.0446(7) 0.0164(6) 0.0144(5) 0.0304(6)
O(1) 2i −0.0730(2) 0.2082(2) 0.8731(1) 0.0461(9) 0.076(1) 0.0362(8) 0.0071(8) 0.0186(7) 0.0282(8)
O(2) 2i 0.0575(2) 0.0453(2) 0.8467(1) 0.067(1) 0.0406(8) 0.0364(8) −0.0037(7) −0.0035(7) 0.0259(7)
O(3) 2i 0.1641(2) 0.2887(2) 0.4438(1) 0.0422(7) 0.0323(7) 0.0247(6) 0.0053(5) 0.0123(5) 0.0152(5)
O(4) 2i 0.3512(2) 0.5399(2) 0.5600(1) 0.0401(7) 0.0346(7) 0.0240(6) 0.0077(6) 0.0072(5) 0.0134(5)
O(5) 2i 0.2976(2) 0.4469(2) −0.0446(1) 0.0416(7) 0.0324(7) 0.0241(6) 0.0080(5) 0.0094(5) 0.0116(5)
O(6) 2i 0.4035(2) 0.7197(2) 0.0683(1) 0.0391(7) 0.0287(6) 0.0233(6) 0.0110(5) 0.0118(5) 0.0145(5)
O(7) 2i 0.6314(2) 0.9288(2) −0.3263(1) 0.065(1) 0.059(1) 0.0427(8) 0.0174(8) 0.0309(8) 0.0292(8)
O(8) 2i 0.3839(2) 0.9071(2) −0.3645(1) 0.082(1) 0.0544(9) 0.0389(8) 0.0408(9) 0.0230(8) 0.0305(7)
N(1) 2i 0.0085(2) 0.1422(2) 0.8210(1) 0.0377(9) 0.0390(9) 0.0260(8) −0.0096(7) −0.0015(6) 0.0167(7)
N(2) 2i 0.4981(2) 0.8992(2) −0.3070(1) 0.064(1) 0.0320(8) 0.0311(8) 0.0223(8) 0.0220(8) 0.0180(7)
C(1) 2i 0.0529(2) 0.1806(2) 0.7223(1) 0.0286(8) 0.0328(9) 0.0242(8) −0.0015(7) 0.0025(6) 0.0154(7)
C(2) 2i 0.1457(2) 0.1097(2) 0.6633(2) 0.0332(9) 0.0310(9) 0.0339(9) 0.0058(7) 0.0014(7) 0.0177(7)
C(3) 2i 0.1865(2) 0.1481(2) 0.5705(2) 0.0300(8) 0.0297(8) 0.0306(9) 0.0059(7) 0.0063(7) 0.0123(7)
C(4) 2i 0.1340(2) 0.2566(2) 0.5411(1) 0.0323(9) 0.0311(8) 0.0237(8) 0.0049(7) 0.0084(6) 0.0145(7)
C(5) 2i 0.0420(3) 0.3254(3) 0.6029(2) 0.046(1) 0.045(1) 0.042(1) 0.0238(9) 0.0198(9) 0.0299(9)
C(6) 2i −0.0017(2) 0.2887(3) 0.6943(2) 0.042(1) 0.047(1) 0.038(1) 0.0191(9) 0.0213(8) 0.0240(9)
C(7) 2i 0.2739(2) 0.4432(2) 0.4648(1) 0.0265(8) 0.0286(8) 0.0268(8) 0.0117(6) 0.0105(6) 0.0145(7)
C(8) 2i 0.2836(2) 0.4707(2) 0.3560(1) 0.0247(7) 0.0288(8) 0.0240(7) 0.0112(6) 0.0098(6) 0.0144(6)
C(9) 2i 0.1906(2) 0.3501(2) 0.2483(1) 0.0292(8) 0.0264(8) 0.0277(8) 0.0072(7) 0.0105(6) 0.0124(7)
C(10) 2i 0.2070(2) 0.3804(2) 0.1494(1) 0.0293(8) 0.0285(8) 0.0222(8) 0.0076(7) 0.0065(6) 0.0092(6)
C(11) 2i 0.3147(2) 0.5324(2) 0.1581(1) 0.0247(7) 0.0291(8) 0.0246(8) 0.0110(6) 0.0087(6) 0.0145(6)
C(12) 2i 0.4040(2) 0.6554(2) 0.2664(2) 0.0315(8) 0.0278(8) 0.0276(8) 0.0039(7) 0.0066(7) 0.0141(7)
C(13) 2i 0.3892(2) 0.6241(2) 0.3653(2) 0.0318(8) 0.0305(9) 0.0227(8) 0.0041(7) 0.0041(6) 0.0108(7)
C(14) 2i 0.3340(2) 0.5556(2) 0.0489(1) 0.0252(8) 0.0286(8) 0.0253(8) 0.0087(6) 0.0070(6) 0.0127(7)
C(15) 2i 0.4261(2) 0.7572(2) −0.0281(1) 0.0366(9) 0.0278(8) 0.0235(8) 0.0149(7) 0.0134(7) 0.0133(7)
C(16) 2i 0.5811(2) 0.8388(2) −0.0322(2) 0.0348(9) 0.0286(8) 0.0302(8) 0.0128(7) 0.0111(7) 0.0137(7)
C(17) 2i 0.6051(2) 0.8857(2) −0.1246(2) 0.0376(9) 0.0285(8) 0.0352(9) 0.0127(7) 0.0182(7) 0.0159(7)
C(18) 2i 0.4724(2) 0.8500(2) −0.2090(2) 0.049(1) 0.0284(8) 0.0273(8) 0.0198(8) 0.0197(7) 0.0156(7)
C(19) 2i 0.3159(2) 0.7708(2) −0.2061(2) 0.042(1) 0.0369(9) 0.0262(8) 0.0207(8) 0.0099(7) 0.0144(7)
C(20) 2i 0.2952(2) 0.7248(2) −0.1142(2) 0.0324(9) 0.0355(9) 0.0302(8) 0.0144(7) 0.0140(7) 0.0158(7)

Source of material

4-Nitro-2-fluoro benzene (11 mmol, 1.73 g) and triethyl amine (10 mL) were first dissolved in anhydrous DMF (25 mL) into a three-necked flask, and then a solution of terephthaloyl chloride (5 mmol, 1.02 g) in DMF was added dropwise. After the feeding was ended, the mixture reacted at room temperature for 2 h and heated to 60°C for another 2 h. The contents of the flask was cooled and poured into an excess of water-ethanol (v/v = 1/1) to precipitate. After isolation by filtration, the white precipitate was recrystallized from acetonitrile to provide colorless needles. The obtained product was dried under vacuum at 150oC overnight. Yield: 85%, melting point: 200oC. Elemental analysis (%): calculated for C20H10F2N2O8: C, 54.07; H, 2.27; N, 6.31%; Found: C,54.26; H, 2.34; N, 6.29.

Experimental details

The hydrogen atoms were refined using riding model with Uiso(H) = 1.2Ueq.

Discussion

The title compound bis (2-fluoro-4-nitrophenyl) terephthalate can be used as an intermediate during the synthesis of corresponding diamine, which acts as a monomer for the preparation of polyimide films. Aromatic polyimides have been widely utilized and usually applied to a variety of electric, microelectronic, and optoelectronic devices due to their combined excellent properties, such as considerably high glass transition temperatures, high resistance to chemicals, good dielectric and mechanical properties [1]. However, even such combined properties of conventional polyimides are not sufficient for rapid progress of electronic device technologies. The recent trends are prepared to develop multi-functional polyimides achieving many application-dependent target properties simultaneously. In addition to the properties mentioned above, other properties are also desired such as lower linear coefficients of thermal expansion, lower extents of moisture uptakes, low coefficients of humidity expansion and sufficient toughness. The ester linkages in the title compound contribute to the stiffness of the structure, consequently reducing CTE of the derived PIs [2]. The introduction of fluoro groups also decreases water absorption of the polyimide films. The title crystal structure is build up by the roughly centrosymmetric C20H10F2N2O8 molecule. The dihedral angle of the benzene ring 1 (C1—C6) and the benzene ring 2 (C8—C13) is 74.8o, and the dihedral angle of the benzene ring 2 and benzene ring 3 (C15—C20) is 45.4o.

Acknowledgements:

This work is financially supported by National Basic Research Program of China (No. 2014CB643604).

References

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