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

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

doi:10.1107/S1600536809034783

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2438

doi:10.1107/S1600536809034783

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

Xiangdong Zhang,^a ^* Lijuan Wang,^a Chunhua Ge,^a Yanmei Men ^a and Rui Zhang ^a

^aCollege of Chemistry, Liaoning University, Shenyang 110036, People's Republic of China
^*Correspondence e-mail: xdzhang@lnu.edu.cn

(Received 29 August 2009; accepted 30 August 2009; online 12 September 2009)

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.

Related literature

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

Experimental

Crystal data

C₁₀H₈N₂·2C₇HF₅O₂
M_r = 580.34
Monoclinic, C 2/c
a = 17.910 (3) Å
b = 10.7016 (19) Å
c = 13.498 (3) Å
β = 119.631 (3)°
V = 2248.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 296 K
0.30 × 0.28 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.946, T_max = 0.974
6884 measured reflections
2695 independent reflections
2060 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.120
S = 1.05
2695 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.82	1.78	2.602 (2)	176
C9—H9⋯O1	0.93	2.40	3.102 (2)	132
C10—H10⋯O1ⁱ	0.93	2.35	3.196 (2)	152
C12—H12⋯F5ⁱⁱ	0.93	2.48	3.126 (2)	127
C13—H13⋯F5ⁱⁱ	0.93	2.63	3.214 (2)	121
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034783/hb5082sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034783/hb5082Isup2.hkl

checkCIF report

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.

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

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

C₁₀H₈N₂·2C₇HF₅O₂	F(000) = 1160
M_r = 580.34	D_x = 1.714 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 187 reflections
a = 17.910 (3) Å	θ = 2.2–22.0°
b = 10.7016 (19) Å	µ = 0.17 mm⁻¹
c = 13.498 (3) Å	T = 296 K
β = 119.631 (3)°	BLOCK, colorless
V = 2248.8 (7) Å³	0.30 × 0.28 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2695 independent reflections
Radiation source: fine-focus sealed tube	2060 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 28.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −23→22
T_min = 0.946, T_max = 0.974	k = −14→11
6884 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0524P)² + 1.397P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2695 reflections	Δρ_max = 0.25 e Å⁻³
183 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (7)

Crystal data top

C₁₀H₈N₂·2C₇HF₅O₂	V = 2248.8 (7) Å³
M_r = 580.34	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.910 (3) Å	µ = 0.17 mm⁻¹
b = 10.7016 (19) Å	T = 296 K
c = 13.498 (3) Å	0.30 × 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)
T_min = 0.946, T_max = 0.974	R_int = 0.022
6884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
2695 reflections	Δρ_min = −0.18 e Å⁻³
183 parameters

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

	x	y	z	U_iso*/U_eq
C10	0.49615 (12)	0.70420 (16)	0.63825 (14)	0.0565 (4)
H10	0.5208	0.6330	0.6818	0.068*
C12	0.44977 (12)	0.91468 (15)	0.61897 (14)	0.0541 (4)
H12	0.4429	0.9890	0.6493	0.065*
C13	0.42370 (13)	0.90600 (16)	0.50439 (14)	0.0578 (5)
H13	0.3984	0.9755	0.4584	0.069*
C9	0.46907 (12)	0.70404 (16)	0.52338 (15)	0.0574 (4)
H9	0.4762	0.6316	0.4910	0.069*
C11	0.48637 (10)	0.81117 (13)	0.68843 (12)	0.0430 (3)
N1	0.43312 (9)	0.80276 (13)	0.45658 (11)	0.0516 (4)
F1	0.31878 (9)	0.41200 (10)	0.13362 (9)	0.0756 (4)
F5	0.38044 (8)	0.81354 (10)	0.04501 (10)	0.0727 (4)
F2	0.24519 (9)	0.35110 (11)	−0.08528 (10)	0.0807 (4)
O2	0.38410 (9)	0.76706 (11)	0.24230 (10)	0.0624 (4)
H2	0.4019	0.7781	0.3105	0.094*
F4	0.30691 (9)	0.74859 (12)	−0.17270 (10)	0.0802 (4)
F3	0.23514 (9)	0.51811 (12)	−0.24105 (8)	0.0766 (4)
C2	0.35217 (10)	0.61682 (14)	0.09940 (12)	0.0442 (3)
C3	0.31759 (11)	0.49867 (15)	0.06163 (13)	0.0490 (4)
O1	0.42833 (13)	0.57290 (14)	0.29718 (11)	0.0921 (6)
C7	0.34739 (11)	0.69832 (14)	0.01702 (14)	0.0475 (4)
C4	0.27894 (12)	0.46524 (15)	−0.05187 (14)	0.0529 (4)
C5	0.27456 (11)	0.54934 (17)	−0.13111 (13)	0.0524 (4)
C1	0.39257 (11)	0.65043 (16)	0.22420 (13)	0.0512 (4)
C6	0.30987 (12)	0.66596 (16)	−0.09672 (14)	0.0527 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C10	0.0778 (12)	0.0382 (8)	0.0439 (9)	0.0111 (8)	0.0227 (8)	0.0021 (6)
C12	0.0787 (11)	0.0355 (8)	0.0413 (8)	0.0068 (8)	0.0244 (8)	−0.0005 (6)
C13	0.0836 (12)	0.0384 (8)	0.0409 (8)	0.0075 (8)	0.0229 (8)	0.0029 (7)
C9	0.0754 (11)	0.0435 (9)	0.0466 (9)	0.0083 (8)	0.0250 (8)	−0.0065 (7)
C11	0.0513 (8)	0.0341 (7)	0.0379 (8)	−0.0014 (6)	0.0177 (6)	−0.0004 (6)
N1	0.0633 (8)	0.0464 (8)	0.0388 (7)	0.0000 (6)	0.0205 (6)	−0.0036 (5)
F1	0.1289 (11)	0.0458 (6)	0.0587 (6)	−0.0090 (6)	0.0515 (7)	0.0036 (5)
F5	0.1063 (9)	0.0427 (6)	0.0662 (7)	−0.0179 (6)	0.0403 (7)	−0.0041 (5)
F2	0.1197 (10)	0.0498 (6)	0.0704 (7)	−0.0246 (7)	0.0454 (7)	−0.0210 (5)
O2	0.0914 (9)	0.0431 (6)	0.0387 (6)	0.0117 (6)	0.0214 (6)	−0.0040 (5)
F4	0.1189 (10)	0.0679 (8)	0.0561 (6)	0.0000 (7)	0.0450 (7)	0.0184 (6)
F3	0.1011 (9)	0.0798 (8)	0.0386 (5)	−0.0019 (7)	0.0268 (6)	−0.0116 (5)
C2	0.0529 (8)	0.0380 (7)	0.0384 (7)	0.0070 (6)	0.0200 (7)	−0.0006 (6)
C3	0.0690 (10)	0.0380 (8)	0.0429 (8)	0.0035 (7)	0.0298 (8)	0.0024 (6)
O1	0.1500 (15)	0.0554 (8)	0.0406 (7)	0.0404 (9)	0.0239 (8)	0.0032 (6)
C7	0.0571 (9)	0.0352 (7)	0.0473 (8)	0.0003 (7)	0.0236 (7)	−0.0007 (6)
C4	0.0691 (11)	0.0394 (8)	0.0505 (9)	−0.0048 (7)	0.0298 (8)	−0.0087 (7)
C5	0.0616 (10)	0.0552 (10)	0.0365 (8)	0.0046 (8)	0.0213 (7)	−0.0049 (7)
C1	0.0627 (10)	0.0439 (9)	0.0390 (8)	0.0103 (7)	0.0190 (7)	−0.0018 (6)
C6	0.0677 (10)	0.0478 (9)	0.0440 (8)	0.0054 (8)	0.0287 (8)	0.0088 (7)

Geometric parameters (Å, º) top

C10—C9	1.377 (2)	F2—C4	1.3383 (19)
C10—C11	1.385 (2)	O2—C1	1.295 (2)
C10—H10	0.9300	O2—H2	0.8200
C12—C13	1.380 (2)	F4—C6	1.3352 (19)
C12—C11	1.389 (2)	F3—C5	1.3328 (18)
C12—H12	0.9300	C2—C7	1.382 (2)
C13—N1	1.332 (2)	C2—C3	1.389 (2)
C13—H13	0.9300	C2—C1	1.512 (2)
C9—N1	1.330 (2)	C3—C4	1.380 (2)
C9—H9	0.9300	O1—C1	1.202 (2)
C11—C11ⁱ	1.483 (3)	C7—C6	1.381 (2)
F1—C3	1.3358 (18)	C4—C5	1.370 (2)
F5—C7	1.3388 (18)	C5—C6	1.372 (3)

C9—C10—C11	119.51 (15)	C3—C2—C1	120.42 (14)
C9—C10—H10	120.2	F1—C3—C4	116.50 (15)
C11—C10—H10	120.2	F1—C3—C2	121.41 (14)
C13—C12—C11	119.23 (15)	C4—C3—C2	122.08 (15)
C13—C12—H12	120.4	F5—C7—C6	116.66 (14)
C11—C12—H12	120.4	F5—C7—C2	120.75 (14)
N1—C13—C12	123.04 (15)	C6—C7—C2	122.59 (15)
N1—C13—H13	118.5	F2—C4—C5	119.63 (15)
C12—C13—H13	118.5	F2—C4—C3	120.38 (15)
N1—C9—C10	123.05 (16)	C5—C4—C3	119.99 (16)
N1—C9—H9	118.5	F3—C5—C4	119.92 (16)
C10—C9—H9	118.5	F3—C5—C6	120.44 (16)
C10—C11—C12	117.44 (14)	C4—C5—C6	119.63 (15)
C10—C11—C11ⁱ	119.81 (10)	O1—C1—O2	125.12 (15)
C12—C11—C11ⁱ	122.74 (10)	O1—C1—C2	121.09 (15)
C9—N1—C13	117.73 (14)	O2—C1—C2	113.78 (14)
C1—O2—H2	109.5	F4—C6—C5	120.39 (15)
C7—C2—C3	116.11 (14)	F4—C6—C7	120.03 (16)
C7—C2—C1	123.47 (15)	C5—C6—C7	119.57 (15)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.78	2.602 (2)	176
C9—H9···O1	0.93	2.40	3.102 (2)	132
C10—H10···O1ⁱⁱ	0.93	2.35	3.196 (2)	152
C12—H12···F5ⁱⁱⁱ	0.93	2.48	3.126 (2)	127
C13—H13···F5ⁱⁱⁱ	0.93	2.63	3.214 (2)	121

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂·2C₇HF₅O₂
M_r	580.34
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	17.910 (3), 10.7016 (19), 13.498 (3)
β (°)	119.631 (3)
V (Å³)	2248.8 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.30 × 0.28 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.946, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	6884, 2695, 2060
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.120, 1.05
No. of reflections	2695
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.78	2.602 (2)	176
C9—H9···O1	0.93	2.40	3.102 (2)	132
C10—H10···O1ⁱ	0.93	2.35	3.196 (2)	152
C12—H12···F5ⁱⁱ	0.93	2.48	3.126 (2)	127
C13—H13···F5ⁱⁱ	0.93	2.63	3.214 (2)	121

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

Acknowledgements

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

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