data reports IUCrData (2016). 1, x161409 http://dx.doi.org/10.1107/S2414314616014097 1 of 3 A new alkaline earth metal tetrafluoro- terephthalate: [Ba(tfBDC)(DMF)(EtOH)] Daniel Smets, Miriam Sobieray and Uwe Ruschewitz* University of Cologne, Greinstrasse 6, D-50939 Cologne, Germany. *Correspondence e-mail: [email protected][Ba(C 8 F 4 O 4 )(C 3 H 7 NO)(C 2 H 5 OH)] or [Ba(tfBDC)(DMF)(EtOH)], where tfBDC 2= tetrafluoroterephthalate, DMF = dimethylformamide, EtOH = ethanol, systematic name poly[(dimethylformamide-1O)(ethanol-1O)(5 - 2,3,5,6-tetrafluorobenzenedicarboxylato-1:22 O 1 ;1:32 O 1 0 ;4O 4 ;5O 4 0 )barium(II)], has been synthesized by a diffusion controlled synthesis from an EtOH/DMF solution. In the crystal structure two crystallographically independent Ba 2+ cations are linked by two crystallographically distinct tfBDC 2anions to form a three-dimensional network structure. The coordination spheres of the first (CN = 8) and second (CN = 8) independent Ba cations are completed by the O atoms of DMF and EtOH molecules, with both EtOH molecules being disordered over two sets of sites (occupancy ratio 0.7:0.3 and 0.6:0.4, respectively). Structure description Despite the high interest in coordination polymers with tetrafluoroterephthalate (tfBDC 2) as a bridging ligand, only few alkaline earth metal tetrafluoroterephthalates have been reported up to now. Only in 2014, three calcium-based tetrafluoro- terephthalates were published, one of them crystallizing in the chiral space group P4 1 2 1 2 (Chen et al., 2014). Interesting pyrotechnical effects have been observed in several alkali and alkaline earth metal tetrafluoroterephthalates, and some of their crystal structures were examined (Blair et al., 2015). Ca(tfBDC)4H 2 O and Sr(tfBDC)4H 2 O were synthesized mechanochemically and their crystal structures were solved and refined from X-ray powder diffraction data (Al-Terkawi et al., 2016). Here we report the first barium- containing coordination polymer with tfBDC 2as bridging ligand. The asymmetric unit of [Ba(tfBDC)(DMF)(EtOH)] contains two crystallographically independent Ba 2+ cations, two symmetry-independent tfBDC 2anions, two dimethyl- formamide (DMF) and two ethanol (EtOH) molecules. Each Ba 2+ cation forms a BaO 8 Received 27 August 2016 Accepted 4 September 2016 Edited by M. Weil, Vienna University of Technology, Austria Keywords: barium; coordination polymer; crystal structure; tetrafluoroterephthalate. CCDC reference: 1502501 Structural data: full structural data are available from iucrdata.iucr.org ISSN 2414-3146
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A new alkaline earth metal tetrafluoroterephthalate: [Ba ... · 2of3Smets et al. [Ba(C 8F 4O 4)(C 3H 7NO)(C 2H 6O)] IUCrData (2016). 1, x161409 data reports polyhedron with six oxygen
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data reports
IUCrData (2016). 1, x161409 http://dx.doi.org/10.1107/S2414314616014097 1 of 3
A new alkaline earth metal tetrafluoro-terephthalate: [Ba(tfBDC)(DMF)(EtOH)]
Daniel Smets, Miriam Sobieray and Uwe Ruschewitz*
University of Cologne, Greinstrasse 6, D-50939 Cologne, Germany. *Correspondence e-mail:
2 of 3 Smets et al. � [Ba(C8F4O4)(C3H7NO)(C2H6O)] IUCrData (2016). 1, x161409
data reports
polyhedron with six oxygen atoms stemming from five
different tfBDC2� ligands (Figs. 1 and 2). The coordination
spheres are completed by one DMF and one EtOH molecule
for each polyhedron [Ba1—O = 2.677 (4)-2.886 (3) A; Ba2—O
= 2.603 (17)-2.867 (3) A]. The two independent EtOH mol-
ecules are each disordered over two sets of sites, and only one
of the two positions is shown in the figures. The observed Ba—
O distances are in good agreement with those in comparable
Ba2+ coordination polymers (Blair et al., 2015; Lo et al., 1998).
The BaO8 polyhedra are connected via common edges to
form zigzag chains along [010]. These chains are shown in
Fig. 3. Each chain contains only Ba1 or Ba2, respectively, as
highlighted in Fig. 3. The Ba1—O and Ba2—O chains are very
similar, but have a different orientation, as shown in Fig. 4.
The arrangement of the Ba—O chains resembles the motif of a
hexagonal rod packing. The tfBDC2� ligands interconnect
these chains in the (010) plane so that a three-dimensional
network structure is formed. The shortest Ba—Ba separations
within the chains are Ba1—Ba1 = 4.5122 (3) A and Ba2—Ba2
= 4.4999 (3) A. The distances between Ba2+ cations of
different chains exceed 9.5 A.
Each tfBDC2� linker coordinates to five Ba2+ cations. One
carboxylate group of each tfBDC2� linker (O19—C18—O18
Figure 2ORTEP plot of the coordination sphere around Ba2, drawn withdisplacement parameters at the 50% probability level. The BaO8
polyhedron is highlighted in light blue. Only one position of thedisordered EtOH molecule is shown. Colour code: see Fig. 1. [Symmetrycodes: (i) �x + 1, y + 1
2, �z + 32; (iii) x, �y + 3
2, z � 12; (iv) x, y + 1, z; (v) �x,
�y + 1, �z + 1; (vi) �x, y + 12, �z + 1
2; (viii) �x + 1, �y + 1, �z + 1.]
Figure 3View along [001] highlighting the zigzag chains of connected BaO8
polyhedra extending in the [010] direction. Only tfbdc2� ligands areshown and given in a wires/sticks representation. Colour code: see Fig. 1.
Figure 4View along [010] in direction of the Ba–O zigzag chains. tfbdc2� ligandsare shown in a wires/sticks representation, EtOH and DMF as ball andsticks. Colour code: see Fig. 1.
Figure 1ORTEP plot of the coordination sphere around Ba1, drawn withdisplacement parameters at the 50% probability level. The BaO8
polyhedron is highlighted in dark blue. Only one position of thedisordered EtOH molecule is shown. Colour code: Ba (silver), O (red), N(dark blue), F (green), C (dark grey), H (white). [Symmetry code: (i)�x + 1, y + 1
2, �z + 32.]
data reports
IUCrData (2016). 1, x161409 Smets et al. � [Ba(C8F4O4)(C3H7NO)(C2H6O)] 3 of 3
and O1—C1—O2) bridges two Ba2+ cations in a monodentate
fashion, whereas the other carboxylate groups (O11—C11—
O12 and O9—C9—O10) bridge three Ba2+ cations in a bis-
monodentate and chelating fashion. As found in many other
tetrafluoroterephthalates, the tfBDC2� linker is not planar,
with the carboxylate groups twisted out of the plane of the
benzene rings (Seidel et al., 2011). The respective torsion
angles are 51.3 (3)� / 64.4 (2)� for linker I (C1–C9) and
35.4 (2)� / 48.8 (2)� for linker II (C11–C18). Both ethanol
molecules are involved in hydrogen bonds, as indicated by the
short O� � �O distances: O50� � �O1 = 2.68 (1) A, O400� � �O30 =
2.55 (3) A, O40� � �O19 = 2.759 (8) A. Since these hydrogen
bonds only connect ethanol molecules to other oxygen atoms
within the same BaO8 coordination polyhedron, the three-
dimensional network structure of [Ba(tfBDC)(DMF)(EtOH)]
is entirely held together by coordinating bonds.
Synthesis and crystallization
In a snap-cap tube 61.4 mg (0.15 mmol, 1 eq.) BaI2�H2O and
Lo, S. M. F., Chui, S. S. Y. & Williams, I. D. (1998). Acta Cryst. C54,1846–1848.
Seidel, C., Ahlers, R. & Ruschewitz, U. (2011). Cryst. Growth Des. 11,5053–5063.
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.Stoe (2002). X-AREA, X-RED32, X-SHAPE. Stoe & Cie, Darmstadt,
Germany.Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Table 1Experimental details.
Crystal dataChemical formula [Ba(C8F4O4)(C3H7NO)(C2H6O)]Mr 492.58Crystal system, space group Monoclinic, P21/cTemperature (K) 293a, b, c (A) 21.4745 (8), 7.4295 (2),
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrainedw = 1/[σ2(Fo
2) + (0.0579P)2 + 2.4924P] where P = (Fo
2 + 2Fc2)/3
(Δ/σ)max = 0.001Δρmax = 1.82 e Å−3
Δρmin = −1.18 e Å−3
Special details
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.
data reports
data-2IUCrData (2016). 1, x161409
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)