Crystal structure of 3-ethynyl­benzoic acid

Venturini, C.; Ratel-Ramond, N.; Gourdon, A.

doi:10.1107/S2056989015016515

organic compounds

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Volume 71| Part 10| October 2015| Pages o750-o751

doi:10.1107/S2056989015016515

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Crystal structure of 3-ethynylbenzoic acid

Chiara Venturini,^a Nicolas Ratel-Ramond ^a and Andre Gourdon ^a ^*

^aCEMES–CNRS BP 94347, 29 Rue J. Marvig, 31055 Toulouse, France
^*Correspondence e-mail: andre.gourdon@cemes.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 26 August 2015; accepted 4 September 2015; online 12 September 2015)

In the title compound, C₉H₆O₂, the carboxylic acid group is almost in the plane of the benzene ring, making a dihedral angle of 2.49 (18)°. In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming classical acid–acid inversion dimers, with an R₂²(8) ring motif. The dimers are linked by pairs of C—H⋯O hydrogen bonds forming chains, enclosing R₂²(16) ring motifs, propagating along the c-axis direction.

Keywords: crystal structure; 3-ethynylbenzoic acid; hydrogen bonding.

CCDC reference: 1422308

1. Related literature

For the potential applications of terminal alkynes in crystal engineering, see: Dai et al. (2004 ). For the synthesis of the title compound, see: Bischoff et al. (2008 ). For the NMR spectrum of the title compound, see: Bleisch et al. (2014 ). For other syntheses of the title compound, see: Jones et al. (2008 ); Pawle et al. (2011 ). For the crystal structure of the 4-ethynyl benzoic acid methyl ester, see: Dai et al. (2004).

2. Experimental

2.1. Crystal data

C₉H₆O₂
M_r = 146.14
Triclinic, $[P \overline 1]$
a = 3.8630 (7) Å
b = 8.3000 (9) Å
c = 11.7490 (1) Å
α = 101.44°
β = 93.8°
γ = 99.83°
V = 361.84 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.9 × 0.4 × 0.1 mm

2.2. Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.664, T_max = 0.745
2719 measured reflections
1317 independent reflections
1086 reflections with I > 2σ(I)
R_int = 0.012

2.3. Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.117
S = 1.08
1317 reflections
124 parameters
All H-atom parameters refined
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	1.03 (2)	1.59 (2)	2.625 (2)	175 (2)
C9—H9⋯O2ⁱⁱ	0.96 (2)	2.50 (2)	3.386 (2)	153 (2)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SIR2011 (Burla et al., 2012 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1422308

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015016515/su5200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016515/su5200Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016515/su5200Isup3.cml

checkCIF report

Chemical context top

In recent years, the interest in compounds with an alkyne C≡CH bond has increased due to their versatility in coupling reactions such as Glaser-Hay or Sonogashira. At the same time the crystallography of terminal alkynes has become an intense field of study for the potential applications in crystal engineering (Dai et al., 2004). Additionally, the presence of a carboxylate group on these compounds makes them potential candidates for the formation of metal organic frameworks viz. MOFs. With these applications in mind, we have synthesized the title compound and report herein on its crystal structure.The synthesis of 4-ethynylbenzoic acid has been reported previously (Jones et al., 2008; Pawle et al., 2011), but not its crystal structure. Only the crystal structure of the ester, 4-ethynylmethylbenzoate, has been described previously (Dai et al., 2004).

Synthesis and crystallization top

3-ethynylbenzoic acid is commercially available. In this work it was obtained by saponification and acidification of the corresponding ester in methanol/water with lithium hydroxide, following the reported procedure (Bischoff et al., 2008). Vapor diffusion of dichlomethane/hexane afforded light yellow crystals. The NMR spectrum is in agreement with the literature values (Bleisch et al., 2014): ¹H-NMR (300 MHz, DMSO) 1H 13.22 (1H, s, O—H), 7.94-7.97 (2H, m, H6; H2), 7.73-7.71 (1H, m, H3), 7.53 (1H, t, J = 7.5 Hz, H7), 4.30 (1H, s, CHh). ¹³C-NMR (75 MHz, DMSO) 13C 166.4 (Ci), 135.8 (Cd), 132.2 (Ca), 131.3 (Ch), 129.7 (Cb), 129.2 (Cc), 122.1 (Ce), 82.5 (Cf), 81.69 (Cg).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All of the H atoms were located in difference Fourier maps and freely refined.

Related literature top

For the potential applications of terminal alkynes in crystal engineering, see: Dai et al. (2004). For the synthesis of the title compound, see: Bischoff et al. (2008). For the NMR spectrum of the title compound, see: Bleisch et al. (2014). For other syntheses of the title compound, see: Jones et al. (2008); Pawle et al. (2011). For the crystal structure of the ester, methyl 4-ethynylbenzoate [updated name OK?], see: Dai et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1).

3-Ethynylbenzoic acid top

Crystal data top

C₉H₆O₂	Z = 2
M_r = 146.14	F(000) = 152
Triclinic, P1	D_x = 1.341 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8630 (7) Å	Cell parameters from 1127 reflections
b = 8.3000 (9) Å	θ = 2.6–26.1°
c = 11.7490 (1) Å	µ = 0.10 mm⁻¹
α = 101.44°	T = 293 K
β = 93.8°	Parallelepiped, colourless
γ = 99.83°	0.9 × 0.4 × 0.1 mm
V = 361.84 (8) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	1317 independent reflections
Radiation source: sealed tube	1086 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
phi and ω scans	θ_max = 26.2°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −3→4
T_min = 0.664, T_max = 0.745	k = −10→10
2719 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	All H-atom parameters refined
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0649P)² + 0.035P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1317 reflections	Δρ_max = 0.13 e Å⁻³
124 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints

Crystal data top

C₉H₆O₂	γ = 99.83°
M_r = 146.14	V = 361.84 (8) Å³
Triclinic, P1	Z = 2
a = 3.8630 (7) Å	Mo Kα radiation
b = 8.3000 (9) Å	µ = 0.10 mm⁻¹
c = 11.7490 (1) Å	T = 293 K
α = 101.44°	0.9 × 0.4 × 0.1 mm
β = 93.8°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1317 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	1086 reflections with I > 2σ(I)
T_min = 0.664, T_max = 0.745	R_int = 0.012
2719 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.117	All H-atom parameters refined
S = 1.08	Δρ_max = 0.13 e Å⁻³
1317 reflections	Δρ_min = −0.13 e Å⁻³
124 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3420 (4)	0.18714 (15)	1.00233 (9)	0.0714 (5)
O2	0.4634 (3)	−0.00243 (13)	0.85678 (9)	0.0648 (4)
C1	0.2847 (3)	0.24041 (16)	0.81364 (11)	0.0432 (4)
C2	0.3024 (3)	0.18897 (16)	0.69499 (12)	0.0428 (4)
C3	0.2316 (3)	0.29147 (16)	0.61941 (12)	0.0434 (4)
C4	0.1418 (4)	0.44533 (18)	0.66466 (14)	0.0509 (5)
C5	0.1251 (4)	0.49579 (18)	0.78270 (14)	0.0558 (5)
C6	0.1965 (4)	0.39454 (18)	0.85767 (13)	0.0509 (5)
C7	0.3696 (4)	0.13271 (17)	0.89319 (12)	0.0477 (4)
C8	0.2570 (4)	0.23974 (16)	0.49657 (12)	0.0489 (5)
C9	0.2828 (5)	0.1985 (2)	0.39633 (14)	0.0629 (6)
H1	0.421 (7)	0.110 (3)	1.054 (2)	0.133 (9)*
H2	0.362 (4)	0.086 (2)	0.6622 (13)	0.050 (4)*
H4	0.088 (4)	0.519 (2)	0.6115 (14)	0.063 (4)*
H5	0.058 (4)	0.601 (2)	0.8124 (14)	0.069 (5)*
H6	0.188 (4)	0.429 (2)	0.9398 (16)	0.065 (5)*
H9	0.302 (5)	0.164 (2)	0.3144 (19)	0.087 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1157 (10)	0.0684 (7)	0.0382 (6)	0.0396 (7)	0.0105 (6)	0.0108 (5)
O2	0.1041 (9)	0.0569 (7)	0.0434 (6)	0.0361 (6)	0.0138 (5)	0.0146 (5)
C1	0.0424 (7)	0.0445 (7)	0.0430 (7)	0.0091 (5)	0.0044 (5)	0.0095 (5)
C2	0.0462 (8)	0.0391 (7)	0.0442 (7)	0.0111 (5)	0.0051 (5)	0.0090 (5)
C3	0.0393 (7)	0.0462 (7)	0.0459 (7)	0.0082 (5)	0.0036 (5)	0.0129 (5)
C4	0.0517 (8)	0.0463 (8)	0.0580 (9)	0.0138 (6)	0.0011 (6)	0.0165 (6)
C5	0.0599 (9)	0.0448 (8)	0.0634 (10)	0.0201 (6)	0.0027 (7)	0.0060 (7)
C6	0.0524 (8)	0.0512 (8)	0.0484 (8)	0.0155 (6)	0.0052 (6)	0.0041 (6)
C7	0.0566 (8)	0.0479 (7)	0.0399 (7)	0.0139 (6)	0.0064 (6)	0.0084 (6)
C8	0.0526 (8)	0.0485 (8)	0.0510 (9)	0.0148 (6)	0.0052 (6)	0.0189 (6)
C9	0.0827 (12)	0.0647 (10)	0.0483 (9)	0.0250 (8)	0.0116 (8)	0.0176 (7)

Geometric parameters (Å, º) top

O1—C7	1.2902 (18)	C4—C5	1.376 (2)
O2—C7	1.2415 (18)	C5—C6	1.378 (2)
O1—H1	1.03 (2)	C8—C9	1.175 (2)
C1—C2	1.3845 (19)	C2—H2	0.938 (16)
C1—C6	1.389 (2)	C4—H4	0.992 (16)
C1—C7	1.4735 (19)	C5—H5	0.959 (17)
C2—C3	1.3907 (19)	C6—H6	0.955 (18)
C3—C4	1.393 (2)	C9—H9	0.96 (2)
C3—C8	1.437 (2)

C7—O1—H1	112.4 (13)	O2—C7—C1	121.61 (12)
C2—C1—C7	119.56 (12)	O1—C7—C1	116.24 (13)
C6—C1—C7	120.24 (12)	C3—C8—C9	179.04 (17)
C2—C1—C6	120.17 (12)	C1—C2—H2	122.5 (9)
C1—C2—C3	120.08 (12)	C3—C2—H2	117.4 (9)
C2—C3—C8	120.12 (12)	C3—C4—H4	119.9 (9)
C4—C3—C8	120.72 (13)	C5—C4—H4	119.6 (9)
C2—C3—C4	119.15 (13)	C4—C5—H5	119.5 (10)
C3—C4—C5	120.48 (14)	C6—C5—H5	120.1 (10)
C4—C5—C6	120.39 (14)	C1—C6—H6	119.3 (10)
C1—C6—C5	119.73 (14)	C5—C6—H6	121.0 (10)
O1—C7—O2	122.16 (13)	C8—C9—H9	179.5 (19)

C6—C1—C2—C3	−0.05 (19)	C6—C1—C7—O2	−176.98 (14)
C7—C1—C2—C3	−178.37 (12)	C1—C2—C3—C4	−0.26 (19)
C2—C1—C6—C5	0.3 (2)	C1—C2—C3—C8	178.71 (12)
C7—C1—C6—C5	178.59 (14)	C2—C3—C4—C5	0.3 (2)
C2—C1—C7—O1	−178.90 (13)	C8—C3—C4—C5	−178.63 (14)
C2—C1—C7—O2	1.3 (2)	C3—C4—C5—C6	−0.1 (2)
C6—C1—C7—O1	2.8 (2)	C4—C5—C6—C1	−0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	1.03 (2)	1.59 (2)	2.625 (2)	175 (2)
C9—H9···O2ⁱⁱ	0.96 (2)	2.50 (2)	3.386 (2)	153 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	1.03 (2)	1.59 (2)	2.625 (2)	175 (2)
C9—H9···O2ⁱⁱ	0.96 (2)	2.50 (2)	3.386 (2)	153 (2)

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

Acknowledgements

Support from the ANR–DFG project ICMADS is gratefully acknowledged.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages o750-o751

doi:10.1107/S2056989015016515

Open

access