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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1886.
Published online 2009 July 18. doi:  10.1107/S1600536809027445
PMCID: PMC2977157

2,3,4,5-Tetra­fluoro­benzoic acid–4,4′-bipyridine (2/1)

Abstract

The asymmetric unit of the title compound, 2C7H2F4O2·C10H8N2, contains one mol­ecule of 2,3,4,5-tetra­fluoro­benzoic acid (tfb) and half of a centrosymmetric 4,4′-bipyridine mol­ecule. Inter­molecular O—H(...)N hydrogen bonds link two tfb mol­ecules and one 4,4′-bipyridine mol­ecule into a trimer. Weak inter­molecular C—H(...)F inter­actions assemble these trimers into a three-dimensional network structure.

Related literature

For complexes with fluorated carboxyl­ates, see: Ma et al. (2006 [triangle]); Gielen et al. (1992 [triangle]).

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Object name is e-65-o1886-scheme1.jpg

Experimental

Crystal data

  • 2C7H2F4O2·C10H8N2
  • M r = 544.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1886-efi1.jpg
  • a = 6.6517 (7) Å
  • b = 8.3419 (14) Å
  • c = 19.5310 (11) Å
  • β = 93.181 (2)°
  • V = 1082.1 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 298 K
  • 0.45 × 0.43 × 0.24 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 5243 measured reflections
  • 1888 independent reflections
  • 1107 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.123
  • S = 1.00
  • 1888 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027445/cv2583sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027445/cv2583Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The 2,3,4,5-tetrafluorobenzoic acid has been intensively studied in biological systems and metal complexes which can considerably increase their biological activities because of the presence of fluorine atom (Ma et al., 2006; Gielen et al., 1992). In view of this, we have selected this ligand and acetate cube in the presence of 4,4'-bipyrimidine as co-ligand to continue the study of fluorated metal compounds. The title compound (Fig. 1) has been obtained as by-side product.

In the crystal, intermolecular O—H···N hydrogen bonds (Table 1) link two molecules of 2,3,4,5-tetrafluorobenzoic acid and one 4,4'-bipyridine molecule into trimer. Weak intermolecular C—H···F interactions (Table 1) assemble further these trimers into three-dimensional network structure.

Experimental

All reagents and solvents were used without further purification. This complex was synthesized by the hydrothermal method from a mixture of an methanol solution of 2,3,4,5-tetrafluorobenzoic acid that had been neutralized with sodium hydroxide, 4,4'-bipyrimidine,acetate cube and water in a airtight vessel. The solution was heated at 313 K for 3 d. After reaction, the vessel was cooled slowly down to room temperature to give transparent brown crystals. The block-like crystals were collected and washed with distilled methanol and dried in air (78% yield). Elemental analysis-found:C,52.88%,2.27%,5.36%; calc.for C12H6F4NO2: C,52.95%,H,2.22%,N,5.15%. The elemental analyses were performed with PERKIN ELMER MODEL 2400 SERIES II.

Figures

Fig. 1.
The content of asymmetric unit of the title compound, with atomic numbering and 50% probability displacement ellipsoids [symmetry code: (A) 1-x, 1-y, 1-z].

Crystal data

2C7H2F4O2·C10H8N2F(000) = 548
Mr = 544.36Dx = 1.671 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.6517 (7) ÅCell parameters from 1438 reflections
b = 8.3419 (14) Åθ = 3.2–23.9°
c = 19.5310 (11) ŵ = 0.16 mm1
β = 93.181 (2)°T = 298 K
V = 1082.1 (2) Å3Block, colourless
Z = 20.45 × 0.43 × 0.24 mm

Data collection

Bruker SMART APEX diffractometer1107 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
graphiteθmax = 25.0°, θmin = 2.1°
[var phi] and ω scansh = −6→7
5243 measured reflectionsk = −7→9
1888 independent reflectionsl = −22→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.062P)2 + 0.1216P] where P = (Fo2 + 2Fc2)/3
1888 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.15 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
F20.7895 (2)0.12908 (19)0.19446 (8)0.0718 (5)
C20.5194 (3)0.1029 (3)0.34972 (12)0.0468 (6)
C30.5693 (3)0.1433 (3)0.28441 (12)0.0489 (6)
O10.2294 (3)0.2650 (2)0.34704 (9)0.0694 (6)
H10.13220.29330.36810.104*
C100.5879 (3)0.4735 (3)0.48110 (12)0.0470 (6)
F31.0440 (2)−0.05674 (19)0.27137 (8)0.0749 (5)
C70.6499 (4)0.0052 (3)0.38789 (13)0.0534 (7)
H70.6191−0.02500.43190.064*
F10.4516 (2)0.2331 (2)0.24231 (8)0.0806 (5)
C50.8729 (3)−0.0054 (3)0.29677 (13)0.0508 (6)
N10.9175 (3)0.3732 (3)0.40908 (11)0.0588 (6)
C40.7454 (4)0.0890 (3)0.25813 (13)0.0517 (7)
C60.8238 (4)−0.0474 (3)0.36163 (13)0.0553 (7)
C10.3355 (4)0.1634 (3)0.38353 (15)0.0559 (7)
O20.2975 (3)0.1188 (3)0.43978 (11)0.0916 (7)
F40.9521 (2)−0.1423 (2)0.39827 (9)0.0884 (6)
C90.6276 (4)0.5363 (3)0.41783 (14)0.0641 (8)
H90.54310.61400.39780.077*
C80.7922 (4)0.4839 (4)0.38453 (15)0.0683 (8)
H80.81630.52930.34230.082*
C110.7186 (4)0.3584 (4)0.50629 (14)0.0705 (8)
H110.69880.31100.54850.085*
C120.8799 (4)0.3124 (4)0.46918 (15)0.0723 (8)
H120.96650.23430.48770.087*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F20.0840 (11)0.0793 (10)0.0551 (9)0.0070 (8)0.0311 (8)0.0059 (8)
C20.0446 (13)0.0492 (14)0.0477 (14)−0.0005 (11)0.0116 (11)−0.0041 (11)
C30.0489 (14)0.0480 (14)0.0505 (15)0.0057 (11)0.0087 (12)0.0008 (12)
O10.0577 (11)0.0810 (13)0.0721 (13)0.0203 (10)0.0250 (9)0.0034 (11)
C100.0375 (12)0.0598 (15)0.0440 (13)−0.0011 (11)0.0045 (10)−0.0094 (12)
F30.0574 (9)0.0898 (12)0.0803 (11)0.0176 (8)0.0280 (8)−0.0038 (9)
C70.0533 (15)0.0590 (16)0.0492 (15)0.0012 (13)0.0143 (12)0.0037 (12)
F10.0824 (11)0.0976 (13)0.0633 (11)0.0354 (10)0.0166 (8)0.0160 (9)
C50.0439 (14)0.0535 (16)0.0564 (15)0.0039 (12)0.0158 (12)−0.0068 (12)
N10.0457 (12)0.0711 (15)0.0604 (15)0.0057 (11)0.0119 (10)−0.0101 (12)
C40.0582 (15)0.0520 (15)0.0467 (15)−0.0042 (12)0.0208 (13)−0.0020 (12)
C60.0542 (15)0.0574 (16)0.0546 (16)0.0096 (13)0.0045 (13)0.0031 (13)
C10.0462 (14)0.0623 (17)0.0605 (18)0.0011 (13)0.0154 (13)−0.0058 (14)
O20.0743 (13)0.1325 (18)0.0718 (14)0.0290 (13)0.0381 (11)0.0212 (13)
F40.0800 (11)0.1119 (14)0.0742 (12)0.0383 (10)0.0110 (9)0.0204 (10)
C90.0581 (16)0.0693 (18)0.0671 (18)0.0151 (14)0.0220 (14)0.0075 (15)
C80.0649 (18)0.0769 (19)0.0662 (18)0.0088 (16)0.0311 (15)0.0075 (16)
C110.0585 (16)0.107 (2)0.0469 (16)0.0271 (17)0.0120 (12)0.0057 (15)
C120.0583 (17)0.103 (2)0.0563 (18)0.0269 (16)0.0065 (14)−0.0013 (17)

Geometric parameters (Å, °)

F2—C41.336 (3)C7—H70.9300
C2—C31.378 (3)C5—C41.356 (3)
C2—C71.379 (3)C5—C61.371 (3)
C2—C11.509 (3)N1—C121.315 (3)
C3—F11.334 (3)N1—C81.317 (3)
C3—C41.381 (3)C6—F41.341 (3)
O1—C11.292 (3)C1—O21.200 (3)
O1—H10.8200C9—C81.375 (3)
C10—C111.368 (3)C9—H90.9300
C10—C91.381 (4)C8—H80.9300
C10—C10i1.484 (4)C11—C121.382 (3)
F3—C51.337 (2)C11—H110.9300
C7—C61.364 (3)C12—H120.9300
C3—C2—C7117.9 (2)C5—C4—C3120.1 (2)
C3—C2—C1124.5 (2)F4—C6—C7121.1 (2)
C7—C2—C1117.5 (2)F4—C6—C5117.8 (2)
F1—C3—C2123.0 (2)C7—C6—C5121.0 (2)
F1—C3—C4115.9 (2)O2—C1—O1124.9 (2)
C2—C3—C4121.1 (2)O2—C1—C2121.0 (3)
C1—O1—H1109.5O1—C1—C2114.2 (2)
C11—C10—C9116.0 (2)C8—C9—C10119.9 (3)
C11—C10—C10i122.2 (3)C8—C9—H9120.0
C9—C10—C10i121.8 (3)C10—C9—H9120.0
C6—C7—C2120.6 (2)N1—C8—C9123.7 (3)
C6—C7—H7119.7N1—C8—H8118.1
C2—C7—H7119.7C9—C8—H8118.1
F3—C5—C4119.9 (2)C10—C11—C12120.2 (3)
F3—C5—C6120.8 (2)C10—C11—H11119.9
C4—C5—C6119.3 (2)C12—C11—H11119.9
C12—N1—C8116.6 (2)N1—C12—C11123.6 (3)
F2—C4—C5120.0 (2)N1—C12—H12118.2
F2—C4—C3119.9 (2)C11—C12—H12118.2
C7—C2—C3—F1178.0 (2)F3—C5—C6—F4−0.5 (4)
C1—C2—C3—F1−4.4 (4)C4—C5—C6—F4179.3 (2)
C7—C2—C3—C4−0.6 (4)F3—C5—C6—C7179.7 (2)
C1—C2—C3—C4176.9 (2)C4—C5—C6—C7−0.5 (4)
C3—C2—C7—C60.8 (4)C3—C2—C1—O2177.4 (3)
C1—C2—C7—C6−176.9 (2)C7—C2—C1—O2−5.1 (4)
F3—C5—C4—F20.8 (4)C3—C2—C1—O1−3.2 (4)
C6—C5—C4—F2−179.0 (2)C7—C2—C1—O1174.3 (2)
F3—C5—C4—C3−179.5 (2)C11—C10—C9—C8−0.8 (4)
C6—C5—C4—C30.7 (4)C10i—C10—C9—C8179.9 (3)
F1—C3—C4—F20.8 (3)C12—N1—C8—C9−0.5 (4)
C2—C3—C4—F2179.6 (2)C10—C9—C8—N10.8 (5)
F1—C3—C4—C5−178.9 (2)C9—C10—C11—C120.6 (4)
C2—C3—C4—C5−0.1 (4)C10i—C10—C11—C12179.8 (3)
C2—C7—C6—F4179.9 (2)C8—N1—C12—C110.2 (4)
C2—C7—C6—C5−0.3 (4)C10—C11—C12—N1−0.3 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C12—H12···F4ii0.932.393.105 (3)134
C8—H8···F3iii0.932.563.308 (3)138
O1—H1···N1iv0.821.802.620 (2)174

Symmetry codes: (ii) −x+2, −y, −z+1; (iii) −x+2, y+1/2, −z+1/2; (iv) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2583).

References

  • Gielen, M., Boualam, M., Meriem, A., Mahieu, B., Biesemans, M. & Willem, R. (1992). Heteroat. Chem.3, 449–452.
  • Ma, C. L., Sun, J. S. & Zhang, R. F. (2006). J. Organomet. Chem.691, 5885—5898.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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