(E)-2-(2-Fluoro­benzyl­idene)butanoic acid

Niaz, M.; Tahir, M.N.; Zia-ur-Rehman; Ali, S.; Khan, I.U.

doi:10.1107/S1600536808007149

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o733

doi:10.1107/S1600536808007149

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(E)-2-(2-Fluorobenzylidene)butanoic acid

Muhammad Niaz,^a M. Nawaz Tahir,^b ^* Zia-ur-Rehman,^a Saqib Ali ^a and Islam Ullah Khan ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bDepartment of Physics, University of Sargodha, Sagrodha, Pakistan, and ^cDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 16 January 2008; accepted 15 March 2008; online 20 March 2008)

In the crystal structure of the title compound, C₁₁H₁₁FO₂, the methine CH forms an intramolecular hydrogen bond with the carboxyl O atom. The molecules form dimers through hydrogen bonding between carboxyl groups. These dimers are linked to each other by C—H⋯O contacts between the benzene and carbonyl groups of adjoining molecules. In addition, there are weak intermolecular C—H⋯F contacts.

Related literature

For related literature, see: Burns & Hagaman (1993 ); Burt (2004 ); Forgó et al. (2005 ); Hertog et al. (1995 ); Muhammad et al. (2007 ). For details of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₁H₁₁FO₂
M_r = 194.20
Monoclinic, P 2₁ /c
a = 4.1895 (4) Å
b = 17.4362 (19) Å
c = 13.8134 (15) Å
β = 96.719 (3)°
V = 1002.12 (18) Å³
Z = 4
Mo Kα radiation radiation
μ = 0.10 mm⁻¹
T = 296 (2) K
0.25 × 0.18 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.935, T_max = 0.958
8632 measured reflections
2981 independent reflections
1704 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.164
S = 1.04
2981 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.97 (2)	1.66 (2)	2.6325 (18)	177.7 (12)
C3—H3⋯O1	0.93	2.32	2.713 (2)	105
C6—H6⋯O2ⁱⁱ	0.93	2.53	3.421 (2)	160
C8—H8⋯F1ⁱⁱⁱ	0.93	2.55	3.266 (2)	134 (1)
Symmetry codes: (i) -x+2, -y, -z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808007149/bv2091sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007149/bv2091Isup2.hkl

checkCIF report

Comment top

Cinnamic acid derivatives are well known for their antibacterial, antifungal antiparasitic (Burt, 2004), and antitumor activity (Hertog et al., 1995). They are also used in the shikmic acid metabolic pathways of higher plants (Forgó et al., 2005).

In the structure of the title compound (I), there are two C-atoms between the carboxylate and 2-fluorophenyl C-atoms. A search of CCDC (Allen, 2002) shows that a structure of 2-amino-2-(2-fluorophenyl)acetic acid (Burns et al., 1993) has been published in which there is only a single C-atom between carboxylate and phenyl ring. Moreover, there is no structure of this kind with a different position for the F-atom.

The C1=O2 bond distance [1.2301 (18) Å], is significantly shorter than the C1—O1 distance [1.3006 (18) Å]. The C1—O1 bond lengthened due to the formation of intramolecular and intermolecular H-bonds. The value of C2=C3 is 1.334 (2) Å. The phenyl ring bond distances are in the normal range but the C4—C5—C6 bond angle is 124.27 (18)°, due to the influence of the F substituent attached to C5. The dihedral angle between the planes formed by (O1, C1, and O2) and (C2, C10, and C11) is 80.97 (18)°, and the dihedral angles between these planes and the phenyl ring are 52.88 (10)° and 67.17 (15)° respectively. The molecules are stabilized by intramolecular and intermolecular H-bonds. The title compound forms dimers through H-bonding, O1—H1···O2ⁱ [symmetry code i = -x + 2, -y, -z] as shown in Fig 2. These dimers are linked to each other through a C6—H6···O2ⁱⁱ interaction [symmetry code ii = -x + 1, y + 1/2, -z + 1/2]. Details of the H-bonding are given in Table 1. In addition there is a weak C8—H8···F1ⁱⁱⁱ intermolecular interaction [symmetry code iii = x, 1/2 - y, 1/2 + z] with a distance 3.2658 (25) Å between C8 and F1ⁱⁱⁱ.

Related literature top

For related literature, see: Burns & Hagaman (1993); Burt (2004); Forgó et al. (2005); Hertog et al. (1995); Muhammad et al. (2007). For details of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Compound (I) was synthesized as reported earlier (Niaz, et al., 2007). A mixture of 2-fluorobenzaldehyde (1.05 ml, 10 mmol), ethylmalonic acid (2.64 g, 20 mmol) and piperidine (1.98 ml, 20 mmol) in a pyridine (12.5 ml) solution was heated on a steam-bath for 24 h. The reaction mixture was cooled and added to a mixture of 25 ml of concentrated HCl and 50 g of ice. The precipitate formed in the acidified mixture was filtered off and washed with ice-cold water. The product was recrystallized from ethanol. The yield was 65%, m.p. 94 °C.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. ORTEP drawing of the title compound, C₁₁H₁₁F₁O₂ with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.
	Fig. 2. The packing figure (PLATON: Spek, 2003) which shows the dimeric nature of the compound owing to inter molecular hydrogen bonding and also showing a link between dimers.

(E)-2-(2-Fluorobenzylidene)butanoic acid top

Crystal data top

C₁₁H₁₁FO₂	F(000) = 408
M_r = 194.20	D_x = 1.287 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2981 reflections
a = 4.1895 (4) Å	θ = 2.3–30.6°
b = 17.4362 (19) Å	µ = 0.10 mm⁻¹
c = 13.8134 (15) Å	T = 296 K
β = 96.719 (3)°	Prismatic, colourless
V = 1002.12 (18) Å³	0.25 × 0.18 × 0.12 mm
Z = 4

Data collection top

Bruker KappaAPEXII CCD diffractometer	2981 independent reflections
Radiation source: fine-focus sealed tube	1704 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 7.2 pixels mm^-1	θ_max = 30.6°, θ_min = 2.3°
ω scans	h = −5→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −24→23
T_min = 0.935, T_max = 0.958	l = −19→19
8632 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0731P)² + 0.1527P] where P = (F_o² + 2F_c²)/3
2981 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₁H₁₁FO₂	V = 1002.12 (18) Å³
M_r = 194.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.1895 (4) Å	µ = 0.10 mm⁻¹
b = 17.4362 (19) Å	T = 296 K
c = 13.8134 (15) Å	0.25 × 0.18 × 0.12 mm
β = 96.719 (3)°

Data collection top

Bruker KappaAPEXII CCD diffractometer	2981 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1704 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.958	R_int = 0.026
8632 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.41 e Å⁻³
2981 reflections	Δρ_min = −0.22 e Å⁻³
131 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
F1	0.5705 (5)	0.28288 (7)	0.22076 (10)	0.1113 (6)
O1	1.0669 (3)	0.08331 (7)	0.07503 (9)	0.0575 (4)
H1	1.104 (5)	0.0617 (11)	0.0126 (15)	0.069*
O2	0.8191 (3)	−0.02692 (7)	0.09434 (9)	0.0609 (4)
C1	0.8986 (4)	0.03770 (8)	0.12367 (11)	0.0406 (4)
C2	0.8045 (3)	0.06721 (8)	0.21699 (11)	0.0394 (4)
C3	0.8530 (4)	0.14131 (9)	0.23791 (12)	0.0443 (4)
H3	0.9555	0.1699	0.1938	0.053*
C4	0.7616 (4)	0.18258 (9)	0.32326 (11)	0.0449 (4)
C5	0.6226 (5)	0.25413 (10)	0.31195 (13)	0.0593 (5)
C6	0.5260 (6)	0.29671 (11)	0.38672 (16)	0.0705 (6)
H6	0.4286	0.3443	0.3749	0.085*
C7	0.5763 (6)	0.26755 (11)	0.47922 (15)	0.0659 (6)
H7	0.5120	0.2953	0.5311	0.079*
C8	0.7214 (5)	0.19750 (12)	0.49543 (14)	0.0691 (6)
H8	0.7586	0.1781	0.5585	0.083*
C9	0.8126 (5)	0.15554 (11)	0.41831 (13)	0.0601 (5)
H9	0.9105	0.1081	0.4304	0.072*
C10	0.6348 (4)	0.01081 (9)	0.27580 (12)	0.0458 (4)
H10A	0.4779	−0.0170	0.2319	0.055*
H10B	0.5185	0.0392	0.3209	0.055*
C11	0.8524 (5)	−0.04706 (11)	0.33354 (14)	0.0614 (5)
H11A	0.7248	−0.0808	0.3682	0.092*
H11B	1.0041	−0.0205	0.3791	0.092*
H11C	0.9657	−0.0764	0.2897	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.2170 (19)	0.0646 (8)	0.0569 (8)	0.0505 (10)	0.0350 (9)	0.0161 (6)
O1	0.0854 (9)	0.0450 (7)	0.0468 (7)	−0.0124 (6)	0.0275 (6)	−0.0072 (5)
O2	0.0912 (10)	0.0434 (7)	0.0528 (7)	−0.0149 (6)	0.0288 (7)	−0.0118 (5)
C1	0.0485 (8)	0.0360 (8)	0.0382 (8)	0.0015 (6)	0.0091 (7)	0.0007 (6)
C2	0.0426 (8)	0.0401 (8)	0.0357 (7)	0.0046 (6)	0.0061 (6)	0.0003 (6)
C3	0.0549 (9)	0.0404 (8)	0.0382 (8)	0.0029 (6)	0.0085 (7)	−0.0005 (6)
C4	0.0575 (10)	0.0386 (8)	0.0393 (8)	0.0012 (7)	0.0088 (7)	−0.0041 (6)
C5	0.0947 (14)	0.0413 (9)	0.0438 (10)	0.0086 (9)	0.0156 (9)	0.0029 (7)
C6	0.1047 (17)	0.0438 (10)	0.0653 (13)	0.0165 (10)	0.0194 (12)	−0.0084 (9)
C7	0.0898 (15)	0.0588 (12)	0.0521 (11)	0.0015 (10)	0.0203 (10)	−0.0183 (9)
C8	0.0999 (16)	0.0685 (13)	0.0391 (9)	0.0122 (11)	0.0095 (10)	−0.0042 (9)
C9	0.0866 (14)	0.0525 (10)	0.0406 (9)	0.0170 (9)	0.0047 (9)	−0.0027 (8)
C10	0.0478 (9)	0.0460 (9)	0.0456 (9)	−0.0026 (7)	0.0136 (7)	−0.0018 (7)
C11	0.0694 (12)	0.0513 (10)	0.0654 (12)	−0.0014 (8)	0.0163 (10)	0.0179 (9)

Geometric parameters (Å, º) top

F1—C5	1.350 (2)	C6—H6	0.9300
O1—C1	1.3006 (18)	C7—C8	1.371 (3)
O1—H1	0.97 (2)	C7—H7	0.9300
O2—C1	1.2301 (18)	C8—C9	1.383 (2)
C1—C2	1.483 (2)	C8—H8	0.9300
C2—C3	1.334 (2)	C9—H9	0.9300
C2—C10	1.506 (2)	C10—C11	1.521 (2)
C3—C4	1.470 (2)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.378 (2)	C11—H11A	0.9600
C4—C9	1.388 (2)	C11—H11B	0.9600
C5—C6	1.371 (3)	C11—H11C	0.9600
C6—C7	1.368 (3)

C1—O1—H1	112.0 (12)	C6—C7—H7	120.0
O2—C1—O1	122.15 (14)	C8—C7—H7	120.0
O2—C1—C2	120.97 (14)	C7—C8—C9	120.19 (18)
O1—C1—C2	116.88 (13)	C7—C8—H8	119.9
C3—C2—C1	118.35 (14)	C9—C8—H8	119.9
C3—C2—C10	125.80 (14)	C8—C9—C4	121.56 (17)
C1—C2—C10	115.63 (13)	C8—C9—H9	119.2
C2—C3—C4	126.91 (15)	C4—C9—H9	119.2
C2—C3—H3	116.5	C2—C10—C11	115.09 (14)
C4—C3—H3	116.5	C2—C10—H10A	108.5
C5—C4—C9	115.53 (15)	C11—C10—H10A	108.5
C5—C4—C3	119.92 (15)	C2—C10—H10B	108.5
C9—C4—C3	124.53 (14)	C11—C10—H10B	108.5
F1—C5—C6	118.18 (17)	H10A—C10—H10B	107.5
F1—C5—C4	117.52 (16)	C10—C11—H11A	109.5
C6—C5—C4	124.27 (18)	C10—C11—H11B	109.5
C7—C6—C5	118.38 (18)	H11A—C11—H11B	109.5
C7—C6—H6	120.8	C10—C11—H11C	109.5
C5—C6—H6	120.8	H11A—C11—H11C	109.5
C6—C7—C8	120.03 (18)	H11B—C11—H11C	109.5

O2—C1—C2—C3	−169.70 (16)	C3—C4—C5—C6	179.3 (2)
O1—C1—C2—C3	10.1 (2)	F1—C5—C6—C7	179.6 (2)
O2—C1—C2—C10	5.2 (2)	C4—C5—C6—C7	1.5 (4)
O1—C1—C2—C10	−174.93 (14)	C5—C6—C7—C8	0.3 (4)
C1—C2—C3—C4	176.46 (15)	C6—C7—C8—C9	−1.0 (4)
C10—C2—C3—C4	2.1 (3)	C7—C8—C9—C4	0.1 (3)
C2—C3—C4—C5	−136.30 (19)	C5—C4—C9—C8	1.5 (3)
C2—C3—C4—C9	45.5 (3)	C3—C4—C9—C8	179.80 (19)
C9—C4—C5—F1	179.57 (19)	C3—C2—C10—C11	−106.93 (19)
C3—C4—C5—F1	1.2 (3)	C1—C2—C10—C11	78.57 (19)
C9—C4—C5—C6	−2.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.97 (2)	1.66 (2)	2.6325 (18)	177.7 (12)
C3—H3···O1	0.93	2.32	2.713 (2)	105
C6—H6···O2ⁱⁱ	0.93	2.53	3.421 (2)	160
C8—H8···F1ⁱⁱⁱ	0.93	2.55	3.266 (2)	134 (1)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁FO₂
M_r	194.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	4.1895 (4), 17.4362 (19), 13.8134 (15)
β (°)	96.719 (3)
V (Å³)	1002.12 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.18 × 0.12

Data collection
Diffractometer	Bruker KappaAPEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.935, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	8632, 2981, 1704
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.717

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.164, 1.04
No. of reflections	2981
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.22

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.97 (2)	1.66 (2)	2.6325 (18)	177.7 (12)
C3—H3···O1	0.93	2.32	2.713 (2)	105
C6—H6···O2ⁱⁱ	0.93	2.53	3.421 (2)	160
C8—H8···F1ⁱⁱⁱ	0.93	2.55	3.266 (2)	133.67 (12)

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

Acknowledgements

The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, for funding the purchase of the diffractometer and Bana International, Karachi, Pakistan, for technical support.

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