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Acta Cryst. (2009). E65, o2438    [ doi:10.1107/S1600536809034783 ]

4,4'-Bipyridine-2,3,4,5,6-pentafluorobenzoic acid (1/2)

X. Zhang, L. Wang, C. Ge, Y. Men and R. Zhang

Abstract top

In the title 1:2 adduct, C10H8N2·2C7HF5O2, the complete 4,4'-bipyridine molecule is generated by a crystallographic twofold axis. The components of the adduct are linked by intermolecular O-H...N hydrogen bonds and further connected by a combination of C-H...O, C-H...F and F...F [2.859 (2) Å] interactions.

Comment top

Weak interactions involving fluorine is of great interest and importance in producing new suppramolecular assemblies. Fluorine can provide C—H···F, N—H···F hydrogen bonds (e.g. Chopra & Row, 2008) as well as C—F···F and C—F···π interactions (e.g. Choudhury & Row, 2004). in crystal engineering. Fluorine derivatives have generated a wide variety of crystal structures. The title molecular complex is composed of 4,4'-bipyridine and 2,3,4,5,6-pentafluorobenzoic acid with the molar ratio of 1:2 to form a basic unit. The components are linked by O—H···N hdrogen bond (O2···N1 2.602 (2) Å, O2—H2···N1 176 °) (Fig. 1). C9—H9···O1 weak hydrogen bond further strengthen the connection (Table 1). Intermolecular C10—H10···O1(symmery code: -x + 1, -y + 1, -z + 1), C12—H12···F5, C13—H13···F5 (symmery code: x, -y + 2, z + 1/2) hydrogen bonds and F1···F3 [2.859 (2) Å, symmery code: x, -y, -1/2 + z] interaction link these units further.

Related literature top

For further discussion of intermolecular interactions involving fluorine atoms, see, for example: Chopra & Row (2008); Choudhury & Row (2004).

Experimental top

A solution of 4,4'-bipyridine (2 mmol) in ethanol (5 ml) was added into 2,3,4,5,6-pentafluorobenzoic acid (4 mmol) in ethanol(20 ml). The mixture was refluxed with stirring for 10 min. The resultant solution was filtered. Colourless blocks of (I) were formed after a few days of slow evaporation of the solvent at room temperature.

Refinement top

All H atoms were placed in calculated positions and included in a riding-model approximation, with C—H = 0.93 Å, O—H = 0.82Å and Uiso(H)= 1.2Ueq(C) or 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of title adduct. Displacement ellipsoids are drawn at the 30% probability level. Atoms with the suffic A are generated by the symmetry operation (1–x, y, 3/2–z).
4,4'-Bipyridine–2,3,4,5,6-pentafluorobenzoic acid (1/2) top
Crystal data top
C10H8N2·2C7HF5O2F(000) = 1160
Mr = 580.34Dx = 1.714 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 187 reflections
a = 17.910 (3) Åθ = 2.2–22.0°
b = 10.7016 (19) ŵ = 0.17 mm−1
c = 13.498 (3) ÅT = 296 K
β = 119.631 (3)°BLOCK, colorless
V = 2248.8 (7) Å30.30 × 0.28 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2695 independent reflections
Radiation source: fine-focus sealed tube2060 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 28.2°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −23→22
Tmin = 0.946, Tmax = 0.974k = −14→11
6884 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0524P)2 + 1.397P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2695 reflectionsΔρmax = 0.25 e Å−3
183 parametersΔρmin = −0.18 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0039 (7)
Crystal data top
C10H8N2·2C7HF5O2V = 2248.8 (7) Å3
Mr = 580.34Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.910 (3) ŵ = 0.17 mm−1
b = 10.7016 (19) ÅT = 296 K
c = 13.498 (3) Å0.30 × 0.28 × 0.20 mm
β = 119.631 (3)°
Data collection top
Bruker SMART CCD
diffractometer		2695 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2060 reflections with I > 2σ(I)
Tmin = 0.946, Tmax = 0.974Rint = 0.022
6884 measured reflectionsθmax = 28.2°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.25 e Å−3
S = 1.05Δρmin = −0.18 e Å−3
2695 reflectionsAbsolute structure: ?
183 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
C100.49615 (12)0.70420 (16)0.63825 (14)0.0565 (4)
H100.52080.63300.68180.068*
C120.44977 (12)0.91468 (15)0.61897 (14)0.0541 (4)
H120.44290.98900.64930.065*
C130.42370 (13)0.90600 (16)0.50439 (14)0.0578 (5)
H130.39840.97550.45840.069*
C90.46907 (12)0.70404 (16)0.52338 (15)0.0574 (4)
H90.47620.63160.49100.069*
C110.48637 (10)0.81117 (13)0.68843 (12)0.0430 (3)
N10.43312 (9)0.80276 (13)0.45658 (11)0.0516 (4)
F10.31878 (9)0.41200 (10)0.13362 (9)0.0756 (4)
F50.38044 (8)0.81354 (10)0.04501 (10)0.0727 (4)
F20.24519 (9)0.35110 (11)−0.08528 (10)0.0807 (4)
O20.38410 (9)0.76706 (11)0.24230 (10)0.0624 (4)
H20.40190.77810.31050.094*
F40.30691 (9)0.74859 (12)−0.17270 (10)0.0802 (4)
F30.23514 (9)0.51811 (12)−0.24105 (8)0.0766 (4)
C20.35217 (10)0.61682 (14)0.09940 (12)0.0442 (3)
C30.31759 (11)0.49867 (15)0.06163 (13)0.0490 (4)
O10.42833 (13)0.57290 (14)0.29718 (11)0.0921 (6)
C70.34739 (11)0.69832 (14)0.01702 (14)0.0475 (4)
C40.27894 (12)0.46524 (15)−0.05187 (14)0.0529 (4)
C50.27456 (11)0.54934 (17)−0.13111 (13)0.0524 (4)
C10.39257 (11)0.65043 (16)0.22420 (13)0.0512 (4)
C60.30987 (12)0.66596 (16)−0.09672 (14)0.0527 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C100.0778 (12)0.0382 (8)0.0439 (9)0.0111 (8)0.0227 (8)0.0021 (6)
C120.0787 (11)0.0355 (8)0.0413 (8)0.0068 (8)0.0244 (8)−0.0005 (6)
C130.0836 (12)0.0384 (8)0.0409 (8)0.0075 (8)0.0229 (8)0.0029 (7)
C90.0754 (11)0.0435 (9)0.0466 (9)0.0083 (8)0.0250 (8)−0.0065 (7)
C110.0513 (8)0.0341 (7)0.0379 (8)−0.0014 (6)0.0177 (6)−0.0004 (6)
N10.0633 (8)0.0464 (8)0.0388 (7)0.0000 (6)0.0205 (6)−0.0036 (5)
F10.1289 (11)0.0458 (6)0.0587 (6)−0.0090 (6)0.0515 (7)0.0036 (5)
F50.1063 (9)0.0427 (6)0.0662 (7)−0.0179 (6)0.0403 (7)−0.0041 (5)
F20.1197 (10)0.0498 (6)0.0704 (7)−0.0246 (7)0.0454 (7)−0.0210 (5)
O20.0914 (9)0.0431 (6)0.0387 (6)0.0117 (6)0.0214 (6)−0.0040 (5)
F40.1189 (10)0.0679 (8)0.0561 (6)0.0000 (7)0.0450 (7)0.0184 (6)
F30.1011 (9)0.0798 (8)0.0386 (5)−0.0019 (7)0.0268 (6)−0.0116 (5)
C20.0529 (8)0.0380 (7)0.0384 (7)0.0070 (6)0.0200 (7)−0.0006 (6)
C30.0690 (10)0.0380 (8)0.0429 (8)0.0035 (7)0.0298 (8)0.0024 (6)
O10.1500 (15)0.0554 (8)0.0406 (7)0.0404 (9)0.0239 (8)0.0032 (6)
C70.0571 (9)0.0352 (7)0.0473 (8)0.0003 (7)0.0236 (7)−0.0007 (6)
C40.0691 (11)0.0394 (8)0.0505 (9)−0.0048 (7)0.0298 (8)−0.0087 (7)
C50.0616 (10)0.0552 (10)0.0365 (8)0.0046 (8)0.0213 (7)−0.0049 (7)
C10.0627 (10)0.0439 (9)0.0390 (8)0.0103 (7)0.0190 (7)−0.0018 (6)
C60.0677 (10)0.0478 (9)0.0440 (8)0.0054 (8)0.0287 (8)0.0088 (7)
Geometric parameters (Å, °) top
C10—C91.377 (2)F2—C41.3383 (19)
C10—C111.385 (2)O2—C11.295 (2)
C10—H100.9300O2—H20.8200
C12—C131.380 (2)F4—C61.3352 (19)
C12—C111.389 (2)F3—C51.3328 (18)
C12—H120.9300C2—C71.382 (2)
C13—N11.332 (2)C2—C31.389 (2)
C13—H130.9300C2—C11.512 (2)
C9—N11.330 (2)C3—C41.380 (2)
C9—H90.9300O1—C11.202 (2)
C11—C11i1.483 (3)C7—C61.381 (2)
F1—C31.3358 (18)C4—C51.370 (2)
F5—C71.3388 (18)C5—C61.372 (3)
C9—C10—C11119.51 (15)C3—C2—C1120.42 (14)
C9—C10—H10120.2F1—C3—C4116.50 (15)
C11—C10—H10120.2F1—C3—C2121.41 (14)
C13—C12—C11119.23 (15)C4—C3—C2122.08 (15)
C13—C12—H12120.4F5—C7—C6116.66 (14)
C11—C12—H12120.4F5—C7—C2120.75 (14)
N1—C13—C12123.04 (15)C6—C7—C2122.59 (15)
N1—C13—H13118.5F2—C4—C5119.63 (15)
C12—C13—H13118.5F2—C4—C3120.38 (15)
N1—C9—C10123.05 (16)C5—C4—C3119.99 (16)
N1—C9—H9118.5F3—C5—C4119.92 (16)
C10—C9—H9118.5F3—C5—C6120.44 (16)
C10—C11—C12117.44 (14)C4—C5—C6119.63 (15)
C10—C11—C11i119.81 (10)O1—C1—O2125.12 (15)
C12—C11—C11i122.74 (10)O1—C1—C2121.09 (15)
C9—N1—C13117.73 (14)O2—C1—C2113.78 (14)
C1—O2—H2109.5F4—C6—C5120.39 (15)
C7—C2—C3116.11 (14)F4—C6—C7120.03 (16)
C7—C2—C1123.47 (15)C5—C6—C7119.57 (15)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.782.602 (2)176
C9—H9···O10.932.403.102 (2)132
C10—H10···O1ii0.932.353.196 (2)152
C12—H12···F5iii0.932.483.126 (2)127
C13—H13···F5iii0.932.633.214 (2)121
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, −y+2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.782.602 (2)176
C9—H9···O10.932.403.102 (2)132
C10—H10···O1i0.932.353.196 (2)152
C12—H12···F5ii0.932.483.126 (2)127
C13—H13···F5ii0.932.633.214 (2)121
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+2, z+1/2.
Acknowledgements top

This work was supported by the Project of the Provincial Key Laboratory of Liaoning Province, China (No. 2008S104), the Project for Innovation Teams of Liaoning Province, China (No. 2007 T052) and the Doctoral Start-up Project of Liaoning University.

references
References top

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Chopra, D. & Row, T. N. G. (2008). CrystEngComm, 10, 54–67.

Choudhury, A. R. & Row, T. N. G. (2004). Cryst. Growth Des. 4, 47–52 .

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.