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

Zhu, X.

doi:10.1107/S1600536809027445

organic compounds

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Volume 65| Part 8| August 2009| Page o1886

doi:10.1107/S1600536809027445

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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@163.com

(Received 25 June 2009; accepted 13 July 2009; online 18 July 2009)

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 ).

Experimental

Crystal data

2C₇H₂F₄O₂·C₁₀H₈N₂
M_r = 544.36
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.037
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯F4ⁱ	0.93	2.39	3.105 (3)	134
C8—H8⋯F3ⁱⁱ	0.93	2.56	3.308 (3)	138
O1—H1⋯N1ⁱⁱⁱ	0.82	1.80	2.620 (2)	174
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z.

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

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].

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

Crystal data top

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 top

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

Refinement top

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

Crystal data top

2C₇H₂F₄O₂·C₁₀H₈N₂	V = 1082.1 (2) Å³
M_r = 544.36	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6517 (7) Å	µ = 0.16 mm⁻¹
b = 8.3419 (14) Å	T = 298 K
c = 19.5310 (11) Å	0.45 × 0.43 × 0.24 mm
β = 93.181 (2)°

Data collection top

Bruker SMART APEX diffractometer	1107 reflections with I > 2σ(I)
5243 measured reflections	R_int = 0.031
1888 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
1888 reflections	Δρ_min = −0.15 e Å⁻³
172 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
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) top

	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, º) top

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 code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	2C₇H₂F₄O₂·C₁₀H₈N₂
M_r	544.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.6517 (7), 8.3419 (14), 19.5310 (11)
β (°)	93.181 (2)
V (Å³)	1082.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.45 × 0.43 × 0.24

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5243, 1888, 1107
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.123, 1.00
No. of reflections	1888
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.15

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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
C12—H12···F4ⁱ	0.93	2.39	3.105 (3)	133.7
C8—H8···F3ⁱⁱ	0.93	2.56	3.308 (3)	138.2
O1—H1···N1ⁱⁱⁱ	0.82	1.80	2.620 (2)	174.2

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

References

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

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doi:10.1107/S1600536809027445

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