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

doi:10.1107/S1600536809027445

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)

Xiaohui Zhu^a^*

^aSchool of Chemistry and Chemical Engineering, Taishan Medical University, 271016 Taian, Shandong, People’s Republic of China

Correspondence e-mail: zhuxh007/at/163.com

Received June 25, 2009; Accepted July 13, 2009.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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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

); Gielen et al. (1992

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

Experimental

Crystal data

2C₇H₂F₄O₂·C₁₀H₈N₂
M _r = 544.36
Monoclinic,
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
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Siemens, 1996

); cell refinement: SAINT (Siemens, 1996

); 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: SHELXTL.

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Click here to view.^{(16K, cif)}

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

Click here to view.^{(93K, 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·C₁₀H₈N₂	F(000) = 548
M_r = 544.36	D_x = 1.671 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.6517 (7) Å	Cell parameters from 1438 reflections
b = 8.3419 (14) Å	θ = 3.2–23.9°
c = 19.5310 (11) Å	µ = 0.16 mm⁻¹
β = 93.181 (2)°	T = 298 K
V = 1082.1 (2) Å³	Block, colourless
Z = 2	0.45 × 0.43 × 0.24 mm

Data collection

Bruker SMART APEX diffractometer	1107 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
graphite	θ_max = 25.0°, θ_min = 2.1°
and ω scans	h = −6→7
5243 measured reflections	k = −7→9
1888 independent reflections	l = −22→23

Refinement

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.062P)² + 0.1216P] where P = (F_o² + 2F_c²)/3
1888 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

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)

	x	y	z	U_iso*/U_eq
F2	0.7895 (2)	0.12908 (19)	0.19446 (8)	0.0718 (5)
C2	0.5194 (3)	0.1029 (3)	0.34972 (12)	0.0468 (6)
C3	0.5693 (3)	0.1433 (3)	0.28441 (12)	0.0489 (6)
O1	0.2294 (3)	0.2650 (2)	0.34704 (9)	0.0694 (6)
H1	0.1322	0.2933	0.3681	0.104*
C10	0.5879 (3)	0.4735 (3)	0.48110 (12)	0.0470 (6)
F3	1.0440 (2)	−0.05674 (19)	0.27137 (8)	0.0749 (5)
C7	0.6499 (4)	0.0052 (3)	0.38789 (13)	0.0534 (7)
H7	0.6191	−0.0250	0.4319	0.064*
F1	0.4516 (2)	0.2331 (2)	0.24231 (8)	0.0806 (5)
C5	0.8729 (3)	−0.0054 (3)	0.29677 (13)	0.0508 (6)
N1	0.9175 (3)	0.3732 (3)	0.40908 (11)	0.0588 (6)
C4	0.7454 (4)	0.0890 (3)	0.25813 (13)	0.0517 (7)
C6	0.8238 (4)	−0.0474 (3)	0.36163 (13)	0.0553 (7)
C1	0.3355 (4)	0.1634 (3)	0.38353 (15)	0.0559 (7)
O2	0.2975 (3)	0.1188 (3)	0.43978 (11)	0.0916 (7)
F4	0.9521 (2)	−0.1423 (2)	0.39827 (9)	0.0884 (6)
C9	0.6276 (4)	0.5363 (3)	0.41783 (14)	0.0641 (8)
H9	0.5431	0.6140	0.3978	0.077*
C8	0.7922 (4)	0.4839 (4)	0.38453 (15)	0.0683 (8)
H8	0.8163	0.5293	0.3423	0.082*
C11	0.7186 (4)	0.3584 (4)	0.50629 (14)	0.0705 (8)
H11	0.6988	0.3110	0.5485	0.085*
C12	0.8799 (4)	0.3124 (4)	0.46918 (15)	0.0723 (8)
H12	0.9665	0.2343	0.4877	0.087*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F2	0.0840 (11)	0.0793 (10)	0.0551 (9)	0.0070 (8)	0.0311 (8)	0.0059 (8)
C2	0.0446 (13)	0.0492 (14)	0.0477 (14)	−0.0005 (11)	0.0116 (11)	−0.0041 (11)
C3	0.0489 (14)	0.0480 (14)	0.0505 (15)	0.0057 (11)	0.0087 (12)	0.0008 (12)
O1	0.0577 (11)	0.0810 (13)	0.0721 (13)	0.0203 (10)	0.0250 (9)	0.0034 (11)
C10	0.0375 (12)	0.0598 (15)	0.0440 (13)	−0.0011 (11)	0.0045 (10)	−0.0094 (12)
F3	0.0574 (9)	0.0898 (12)	0.0803 (11)	0.0176 (8)	0.0280 (8)	−0.0038 (9)
C7	0.0533 (15)	0.0590 (16)	0.0492 (15)	0.0012 (13)	0.0143 (12)	0.0037 (12)
F1	0.0824 (11)	0.0976 (13)	0.0633 (11)	0.0354 (10)	0.0166 (8)	0.0160 (9)
C5	0.0439 (14)	0.0535 (16)	0.0564 (15)	0.0039 (12)	0.0158 (12)	−0.0068 (12)
N1	0.0457 (12)	0.0711 (15)	0.0604 (15)	0.0057 (11)	0.0119 (10)	−0.0101 (12)
C4	0.0582 (15)	0.0520 (15)	0.0467 (15)	−0.0042 (12)	0.0208 (13)	−0.0020 (12)
C6	0.0542 (15)	0.0574 (16)	0.0546 (16)	0.0096 (13)	0.0045 (13)	0.0031 (13)
C1	0.0462 (14)	0.0623 (17)	0.0605 (18)	0.0011 (13)	0.0154 (13)	−0.0058 (14)
O2	0.0743 (13)	0.1325 (18)	0.0718 (14)	0.0290 (13)	0.0381 (11)	0.0212 (13)
F4	0.0800 (11)	0.1119 (14)	0.0742 (12)	0.0383 (10)	0.0110 (9)	0.0204 (10)
C9	0.0581 (16)	0.0693 (18)	0.0671 (18)	0.0151 (14)	0.0220 (14)	0.0075 (15)
C8	0.0649 (18)	0.0769 (19)	0.0662 (18)	0.0088 (16)	0.0311 (15)	0.0075 (16)
C11	0.0585 (16)	0.107 (2)	0.0469 (16)	0.0271 (17)	0.0120 (12)	0.0057 (15)
C12	0.0583 (17)	0.103 (2)	0.0563 (18)	0.0269 (16)	0.0065 (14)	−0.0013 (17)

Geometric parameters (Å, °)

F2—C4	1.336 (3)	C7—H7	0.9300
C2—C3	1.378 (3)	C5—C4	1.356 (3)
C2—C7	1.379 (3)	C5—C6	1.371 (3)
C2—C1	1.509 (3)	N1—C12	1.315 (3)
C3—F1	1.334 (3)	N1—C8	1.317 (3)
C3—C4	1.381 (3)	C6—F4	1.341 (3)
O1—C1	1.292 (3)	C1—O2	1.200 (3)
O1—H1	0.8200	C9—C8	1.375 (3)
C10—C11	1.368 (3)	C9—H9	0.9300
C10—C9	1.381 (4)	C8—H8	0.9300
C10—C10ⁱ	1.484 (4)	C11—C12	1.382 (3)
F3—C5	1.337 (2)	C11—H11	0.9300
C7—C6	1.364 (3)	C12—H12	0.9300

C3—C2—C7	117.9 (2)	C5—C4—C3	120.1 (2)
C3—C2—C1	124.5 (2)	F4—C6—C7	121.1 (2)
C7—C2—C1	117.5 (2)	F4—C6—C5	117.8 (2)
F1—C3—C2	123.0 (2)	C7—C6—C5	121.0 (2)
F1—C3—C4	115.9 (2)	O2—C1—O1	124.9 (2)
C2—C3—C4	121.1 (2)	O2—C1—C2	121.0 (3)
C1—O1—H1	109.5	O1—C1—C2	114.2 (2)
C11—C10—C9	116.0 (2)	C8—C9—C10	119.9 (3)
C11—C10—C10ⁱ	122.2 (3)	C8—C9—H9	120.0
C9—C10—C10ⁱ	121.8 (3)	C10—C9—H9	120.0
C6—C7—C2	120.6 (2)	N1—C8—C9	123.7 (3)
C6—C7—H7	119.7	N1—C8—H8	118.1
C2—C7—H7	119.7	C9—C8—H8	118.1
F3—C5—C4	119.9 (2)	C10—C11—C12	120.2 (3)
F3—C5—C6	120.8 (2)	C10—C11—H11	119.9
C4—C5—C6	119.3 (2)	C12—C11—H11	119.9
C12—N1—C8	116.6 (2)	N1—C12—C11	123.6 (3)
F2—C4—C5	120.0 (2)	N1—C12—H12	118.2
F2—C4—C3	119.9 (2)	C11—C12—H12	118.2

C7—C2—C3—F1	178.0 (2)	F3—C5—C6—F4	−0.5 (4)
C1—C2—C3—F1	−4.4 (4)	C4—C5—C6—F4	179.3 (2)
C7—C2—C3—C4	−0.6 (4)	F3—C5—C6—C7	179.7 (2)
C1—C2—C3—C4	176.9 (2)	C4—C5—C6—C7	−0.5 (4)
C3—C2—C7—C6	0.8 (4)	C3—C2—C1—O2	177.4 (3)
C1—C2—C7—C6	−176.9 (2)	C7—C2—C1—O2	−5.1 (4)
F3—C5—C4—F2	0.8 (4)	C3—C2—C1—O1	−3.2 (4)
C6—C5—C4—F2	−179.0 (2)	C7—C2—C1—O1	174.3 (2)
F3—C5—C4—C3	−179.5 (2)	C11—C10—C9—C8	−0.8 (4)
C6—C5—C4—C3	0.7 (4)	C10ⁱ—C10—C9—C8	179.9 (3)
F1—C3—C4—F2	0.8 (3)	C12—N1—C8—C9	−0.5 (4)
C2—C3—C4—F2	179.6 (2)	C10—C9—C8—N1	0.8 (5)
F1—C3—C4—C5	−178.9 (2)	C9—C10—C11—C12	0.6 (4)
C2—C3—C4—C5	−0.1 (4)	C10ⁱ—C10—C11—C12	179.8 (3)
C2—C7—C6—F4	179.9 (2)	C8—N1—C12—C11	0.2 (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···A	D—H	H···A	D···A	D—H···A
C12—H12···F4ⁱⁱ	0.93	2.39	3.105 (3)	134
C8—H8···F3ⁱⁱⁱ	0.93	2.56	3.308 (3)	138
O1—H1···N1^iv	0.82	1.80	2.620 (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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