Crystal structure of catena-poly[bis(glycol-1k2 0 , 0 ' ) - ( μ2 tetrafluoroterephthalato)zinc(II)], Zn(C8F4O4)(C2H6O2)2

C12H12F4O8Z11, triclinic, PI (no. 2), a = 5.1044(7) Â, b = 8.808(1) Â, c = 9.384(1) Â, a = 116.500(1), β = 95.646(2)°, γ = 93.160(2)°, V= 373.4 À 3 ,Z= 1, Rgí(F) = 0.024, wRteffF) = 0.066, T= 296 Κ. Source of material By placing a CH3OH solution (10 ml) of tetrafluoroterephthalic acid (tfbdc, 23.8 mg, 0.1 mmol) at the bottom of a straight glass tube and then carefully added a buffer of glycol (10 ml), above which a CH3OH solution (10 ml) containing ZnCk (13.6 mg, 0.1 mmol) was placed in this tube. The resulting slow diffusion of solvents across the boundary layer results in excellent colorless block-shaped crystals growing there over a period of two weeks. Experimental details H atoms bound to methylene carbon atoms were assigned to calculated positions with d(C—H) = 0.97 Â and refined using a riding model, with t/iso(H) =1.2 Ueq(C). Hydroxyl H atoms were positioned geometrically with d(0—H) = 0.84 Â and t/iso(H) = 1 . 5 t / e q ( 0 ) . Discussion The design and synthesis of metal-organic frameworks constructed from transition metal ions and 1,4-benzenedicaiboxylic acid (1,4-H2BDC) ligand have attracted intensive attention in recent years because of their intriguing structural topologies and tailor-made applications as functional solid materials [1-3]. Recent studies have shown the remarkable analogy of 1,4-B DC-type ligands with bulky methyl [4], fluorine [5], chlorine [6] or bromine [7] groups, since they not only provide astonishing thermal and chemical stability and stereo-chemical characteristics, but also prevent interpénétration phenomena of resultant polymeric networks. In the asymmetric unit, one Ζη ion lying on an inversion center [at (0 0 A)] is coordinated by six oxygen atoms in a nearly ideal octahedral configuration. The Zn ion is chelated by four O atoms from two glycol molecules in the equatorial plane and two axial O atoms from two centrosymmetric tetrafluoroterephthalate (tfbdc) ligands. Because of the steric hindrance of the fluorine atoms located at the ortho positions of carboxylate, the rotation angle of tetrafluorined phenyl ring relative to carboxylate is 47.3(2)°, which is quite similar to that of a recent reported Mn-tfbdc polymer [8], Each tfbdc anion bridges two Zn centers in a bismonodentate fashion to afford a linear chain along the [ 111 ] with adjacent Zn ·Ζη separation of 11.503(1) Â. Within the polymeric chain, one hydroxyl of the glycol molecule is involved in the strong intramolecular 04—H402 bond (i = -x,-y+2,-z+ 1) to the uncoordinated 0 2 atom of tfbdc moiety. Moreover, intermolecular 03-H3 01" bonds (ii = x-1 ,y,z) connect adjoining chains into a two-dimensional network. Table 1. Data collection and handling. Crystal: Wavelength: μ· Diffractometer, scan mode: 20max: N(hkl)measured, N(hkl)unique: Criterion for /ote, N(hkl)gi. N(param)KfaK¿: Program: colorless block, size 0.30 χ 0.30 χ 0.32 mm Mo Ka radiation (0.71073 Â) 17.33 cm" Broker SMART APEX CCD, φ/ω 55.04° 3233,1718 /obs > 2 a(Iobs), 1668 115 SHELXTL [9] * Correspondence author (e-mail: hemingyangjpu@yahoo.com) 620 Zn(C8F404)(C2H602)2 Table 2. Atomic coordinates and displacement parameters (in Â). Table 2. Continued. Atom Site X y Ζ fiso Atom Site X y ζ U,so H(5A) 2« -0.3726 1.1938 0.3599 0.023 H(6B) 2i 0.0153 1.2758 0.2885 0.022 H(5B) 2 Í -0.3757 1.0766 0.1746 0.023 H(3) 21 -0.4467 0.9268 0.3133 0.024 H(6A) 2 i 0.0829 1.0863 0.2068 0.022 H(4) 2/ 0.0914 1.2784 0.5190 0.023 Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ i/u t/22 t/33 Í/12 ί/13 Uiì Zn(l) lb 0 0 Vi 0.0126(2) 0.0112(2) 0.0126(2) 0.0025(1) 0.0044(1) 0.0053(1) C(l) 2i 0.1911(3) 0.6729(2) 0.2647(2) 0.0127(7) 0.0140(8) 0.0134(8) 0.0024(6) 0.0018(6) 0.0050(7) C(2) 2i 0.3489(3) 0.5838(2) 0.1273(2) 0.0148(7) 0.0111(7) 0.0112(7) 0.0009(6) 0.0035(6) 0.0025(6) C(3) 2i 0.4817(3) 0.4447(2) 0.1142(2) 0.0190(8) 0.0135(8) 0.0139(8) 0.0018(6) 0.0039(6) 0.0072(7) C(4) 2 i 0.6281(3) 0.3640(2) -0.0091(2) 0.0172(8) 0.0108(7) 0.0165(8) 0.0040(6) 0.0041(6) 0.0056(7) C(5) 2 i -0.2851(4) 1.1058(2) 0.2808(2) 0.0178(8) 0.0208(9) 0.0230(9) 0.0018(7) 0.0030(7) 0.0143(8) C(6) 2 i 0.0034(4) 1.1688(2) 0.2950(2) 0.0190(8) 0.0199(8) 0.0195(9) 0.0006(7) 0.0052(7) 0.0121(7) F(l) li 0.4768(2) 0.3905(1) 0.2273(1) 0.0310(6) 0.0238(6) 0.0209(6) 0.0117(5) 0.0131(5) 0.0158(5) F(2) 2i 0.7561(2) 0.2327(1) -0.0119(1) 0.0316(6) 0.0191(5) 0.0210(6) 0.0146(5) 0.0105(5) 0.0116(5) 0(1) 2 i 0.2342(2) 0.8360(2) 0.3365(2) 0.0148(6) 0.0117(6) 0.0162(6) 0.0026(4) 0.0060(5) 0.0045(5) 0(2) 2i 0.0357(3) 0.5834(2) 0.2971(2) 0.0219(6) 0.0148(6) 0.0203(7) 0.0002(5) 0.0102(5) 0.0051(5) 0(3) 2/ -0.2903(2) 0.9570(2) 0.3083(2) 0.0142(6) 0.0157(6) 0.0185(6) -0.0008(5) 0.0026(5) 0.0091(5) 0(4) 2i 0.1462(2) 1.1937(2) 0.4465(2) 0.0154(6) 0.0133(6) 0.0169(6) 0.0016(4) 0.0047(5) 0.0063(5) Acknowledgment. The authors thank the Center for Testing and Analysis at Yangzhou University for support.