
==== Front
IUCrdata
IUCrdata
IUCrData
IUCrData
2414-3146
International Union of Crystallography

hb4473
10.1107/S2414314624007521
IUCRBK
S2414314624007521
Data Reports
Redetermined structure of 4-(benz­yloxy)benzoic acid
C14H12O3
Song Qiuyi a
Long Sihui b*
a https://ror.org/04jcykh16 School of Chemical Engineering and Pharmacy Wuhan Institute of Technology,Wuhan Hubei 430205 People’s Republic of China
b https://ror.org/04jcykh16 School of Chemical Engineering and Pharmacy Wuhan Institute of Technology,Wuhan Hubei 430205 China
Harrison W. T. A. Editor
University of Aberdeen, United Kingdom
Correspondence e-mail: sihuilong@wit.edu.cn
8 2024
06 8 2024
06 8 2024
9 Pt 8 x240800 x24075221 5 2024
31 7 2024
© Song and Long 2024
2024
https://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
A full version of this article is available from Crystallography Journals Online.
The mol­ecules of the title compound form acid–acid homodimers in the crystal structure.

In the title compound, C14H14O3, the dihedral angle between the aromatic rings is 39.76 (9)°. In the crystal, the mol­ecules associate to form centrosymmetric acid–acid dimers linked by pairwise O—H⋯O hydrogen bonds. The precision of the geometric parameters in the present single-crystal study is about an order of magnitude better than the previous powder diffraction study [Chattopadhyay et al. (2013 ▸). CrystEngComm, 15, 1077–1085].

synthon
hydrogen bond
acid-acid dimer
crystal structure
==== Body
pmcStructure description

Non-steroidal anti-inflammatory drugs (NSAIDs) constitute approximately 5–10% of all prescribed medicines worldwide as anti­pyretic, anti-inflammatory and analgesic agents (Sohail et al., 2023 ▸). Moreover, they are found to have a protective role against various critical diseases, such as cancer and cardiovascular diseases (Prasher & Sharma, 2021 ▸). It is estimated that 30 million individuals use NSAIDs daily (Bhala et al., 2013 ▸).

As part of our studies in this area, the title compound (Fig. 1 ▸) was synthesized by a two-step reaction. The C1–C6 and C9–C14 aromatic rings subtend a dihedral angle of 39.76 (9)° and the linking C4—O3—C8—C9 bond has an anti conformation [torsion angle = −171.59 (12)°]. The short C4—O3 bond length of 1.3601 (16) Å indicates some conjugation of the O atom lone pair with the adjacent aromatic ring.

In the extended structure, mol­ecules pair up to form carb­oxy­lic acid–carb­oxy­lic acid hydrogen-bonded dimers (Table 1 ▸, Fig. 2 ▸). The crystal structure of the title compound was also solved from X-ray powder diffraction data (Chattopadhyay et al., 2013 ▸) with corresponding hydrogen-bond parameters of 1.94 Å and 176°, respectively, which deviate from those obtained in this study from single-crystal X-ray diffraction.

Synthesis and crystallization

The title compound was prepared by a two-step reaction (Fig. 3 ▸). The product was purified by column chromatography. Single crystals were obtained by slowly evaporating an ethanol solution of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314624007521/hb4473sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314624007521/hb4473Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314624007521/hb4473Isup3.cml

CCDC reference: 2374704

Additional supporting information: crystallographic information; 3D view; checkCIF report

QS thanks the Graduate Innovation Fund of WIT for financial support.

full crystallographic data

4-(Benzyloxy)benzoic acid Crystal data

C14H12O3	F(000) = 480	
Mr = 228.24	Dx = 1.348 Mg m−3	
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å	
a = 10.0564 (5) Å	Cell parameters from 5298 reflections	
b = 3.9985 (2) Å	θ = 2.1–29.8°	
c = 28.2235 (14) Å	µ = 0.10 mm−1	
β = 97.744 (5)°	T = 305 K	
V = 1124.54 (10) Å3	Block, clear light colourless	
Z = 4	0.16 × 0.15 × 0.13 mm	

4-(Benzyloxy)benzoic acid Data collection

XtaLAB Synergy R, DW system, HyPix diffractometer	2793 independent reflections	
Radiation source: Rotating-anode X-ray tube, Rigaku (Mo) X-ray Source	1996 reflections with I > 2σ(I)	
Mirror monochromator	Rint = 0.019	
Detector resolution: 10.0000 pixels mm-1	θmax = 30.8°, θmin = 2.1°	
ω scans	h = −12→13	
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −4→5	
Tmin = 0.875, Tmax = 1.000	l = −29→37	
10523 measured reflections		

4-(Benzyloxy)benzoic acid Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites	
Least-squares matrix: full	H-atom parameters constrained	
R[F2 > 2σ(F2)] = 0.044	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.1717P] where P = (Fo2 + 2Fc2)/3	
wR(F2) = 0.135	(Δ/σ)max < 0.001	
S = 1.08	Δρmax = 0.26 e Å−3	
2793 reflections	Δρmin = −0.19 e Å−3	
156 parameters	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4	
0 restraints	Extinction coefficient: 0.008 (2)	

4-(Benzyloxy)benzoic acid Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.	
Refinement. The positions of the H atom attached to O1 was obtained from a difference Fourier map. Other H atoms were positioned geometrically with C—H = 0.93 Å and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,O).	

4-(Benzyloxy)benzoic acid Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

	x	y	z	Uiso*/Ueq		
O3	0.35692 (9)	0.6152 (3)	0.36054 (4)	0.0557 (3)		
O2	0.94382 (10)	0.2255 (4)	0.45018 (4)	0.0666 (4)		
O1	0.83138 (10)	0.0288 (4)	0.50696 (4)	0.0658 (4)		
H1	0.906153	−0.043118	0.517133	0.099*		
C4	0.46870 (13)	0.5035 (4)	0.38859 (5)	0.0444 (3)		
C5	0.58913 (14)	0.5572 (4)	0.37085 (5)	0.0503 (4)		
H5	0.589311	0.663292	0.341539	0.060*		
C6	0.70792 (13)	0.4545 (4)	0.39638 (5)	0.0491 (4)		
H6	0.788198	0.490876	0.384244	0.059*		
C1	0.70890 (12)	0.2960 (4)	0.44041 (4)	0.0431 (3)		
C2	0.58902 (13)	0.2464 (4)	0.45795 (5)	0.0495 (4)		
H2	0.589103	0.142972	0.487473	0.059*		
C3	0.46833 (14)	0.3477 (4)	0.43243 (5)	0.0505 (4)		
H3	0.388052	0.311700	0.444589	0.061*		
C8	0.22907 (13)	0.5294 (4)	0.37376 (5)	0.0526 (4)		
H8A	0.216021	0.642645	0.403176	0.063*		
H8B	0.224207	0.290205	0.378971	0.063*		
C9	0.12226 (13)	0.6340 (3)	0.33413 (5)	0.0452 (3)		
C10	0.13472 (15)	0.5661 (4)	0.28683 (5)	0.0548 (4)		
H10	0.211545	0.460996	0.279204	0.066*		
C11	0.03322 (16)	0.6542 (4)	0.25081 (6)	0.0616 (4)		
H11	0.042281	0.608856	0.219082	0.074*		
C12	−0.08060 (15)	0.8081 (4)	0.26183 (6)	0.0625 (4)		
H12	−0.148833	0.865897	0.237618	0.075*		
C13	−0.09369 (15)	0.8766 (4)	0.30845 (6)	0.0623 (4)		
H13	−0.170991	0.980303	0.315929	0.075*		
C14	0.00810 (14)	0.7917 (4)	0.34459 (6)	0.0536 (4)		
H14	−0.000845	0.841711	0.376181	0.064*		
C7	0.83567 (13)	0.1772 (4)	0.46735 (5)	0.0467 (3)		

4-(Benzyloxy)benzoic acid Atomic displacement parameters (Å2)

	U11	U22	U33	U12	U13	U23	
O3	0.0376 (5)	0.0723 (7)	0.0548 (6)	−0.0030 (5)	−0.0018 (4)	0.0171 (5)	
O2	0.0403 (5)	0.1045 (10)	0.0549 (6)	0.0051 (6)	0.0064 (4)	0.0152 (6)	
O1	0.0449 (6)	0.0978 (9)	0.0527 (6)	0.0062 (6)	0.0000 (5)	0.0210 (6)	
C4	0.0394 (7)	0.0492 (8)	0.0425 (7)	−0.0025 (6)	−0.0015 (5)	0.0019 (6)	
C5	0.0461 (7)	0.0633 (9)	0.0407 (7)	−0.0034 (6)	0.0029 (6)	0.0094 (6)	
C6	0.0378 (7)	0.0648 (9)	0.0447 (7)	−0.0040 (6)	0.0056 (5)	0.0046 (6)	
C1	0.0390 (7)	0.0499 (8)	0.0392 (6)	−0.0014 (5)	0.0011 (5)	−0.0005 (5)	
C2	0.0434 (7)	0.0629 (9)	0.0417 (7)	−0.0008 (6)	0.0038 (5)	0.0089 (6)	
C3	0.0378 (7)	0.0644 (10)	0.0492 (8)	−0.0020 (6)	0.0058 (5)	0.0083 (7)	
C8	0.0405 (7)	0.0618 (9)	0.0546 (8)	−0.0032 (6)	0.0025 (6)	0.0103 (7)	
C9	0.0374 (6)	0.0455 (8)	0.0515 (8)	−0.0053 (5)	0.0019 (5)	0.0046 (6)	
C10	0.0462 (8)	0.0608 (10)	0.0573 (8)	0.0017 (7)	0.0068 (6)	−0.0025 (7)	
C11	0.0607 (9)	0.0722 (11)	0.0497 (8)	−0.0119 (8)	−0.0004 (7)	0.0001 (7)	
C12	0.0449 (8)	0.0691 (11)	0.0689 (10)	−0.0100 (7)	−0.0094 (7)	0.0173 (8)	
C13	0.0396 (7)	0.0666 (11)	0.0803 (11)	0.0039 (7)	0.0063 (7)	0.0117 (8)	
C14	0.0438 (7)	0.0609 (9)	0.0568 (8)	−0.0024 (7)	0.0090 (6)	0.0022 (7)	
C7	0.0406 (7)	0.0584 (9)	0.0403 (7)	−0.0004 (6)	0.0022 (5)	−0.0007 (6)	

4-(Benzyloxy)benzoic acid Geometric parameters (Å, º)

O3—C4	1.3601 (16)	C3—H3	0.9300	
O3—C8	1.4279 (17)	C8—H8A	0.9700	
O2—C7	1.2636 (17)	C8—H8B	0.9700	
O1—H1	0.8200	C8—C9	1.5019 (19)	
O1—C7	1.2716 (17)	C9—C10	1.384 (2)	
C4—C5	1.3881 (19)	C9—C14	1.376 (2)	
C4—C3	1.3857 (19)	C10—H10	0.9300	
C5—H5	0.9300	C10—C11	1.386 (2)	
C5—C6	1.3721 (19)	C11—H11	0.9300	
C6—H6	0.9300	C11—C12	1.372 (2)	
C6—C1	1.3937 (19)	C12—H12	0.9300	
C1—C2	1.3780 (18)	C12—C13	1.368 (2)	
C1—C7	1.4723 (18)	C13—H13	0.9300	
C2—H2	0.9300	C13—C14	1.386 (2)	
C2—C3	1.3858 (19)	C14—H14	0.9300	
				
C4—O3—C8	118.15 (11)	C9—C8—H8A	110.0	
C7—O1—H1	109.5	C9—C8—H8B	110.0	
O3—C4—C5	115.61 (12)	C10—C9—C8	121.00 (13)	
O3—C4—C3	124.46 (12)	C14—C9—C8	120.09 (13)	
C3—C4—C5	119.93 (12)	C14—C9—C10	118.89 (13)	
C4—C5—H5	119.9	C9—C10—H10	119.9	
C6—C5—C4	120.30 (12)	C9—C10—C11	120.29 (14)	
C6—C5—H5	119.9	C11—C10—H10	119.9	
C5—C6—H6	119.8	C10—C11—H11	119.9	
C5—C6—C1	120.36 (12)	C12—C11—C10	120.15 (15)	
C1—C6—H6	119.8	C12—C11—H11	119.9	
C6—C1—C7	120.58 (12)	C11—C12—H12	120.0	
C2—C1—C6	118.97 (12)	C13—C12—C11	119.97 (14)	
C2—C1—C7	120.44 (12)	C13—C12—H12	120.0	
C1—C2—H2	119.4	C12—C13—H13	120.0	
C1—C2—C3	121.23 (13)	C12—C13—C14	120.10 (15)	
C3—C2—H2	119.4	C14—C13—H13	120.0	
C4—C3—C2	119.21 (13)	C9—C14—C13	120.60 (14)	
C4—C3—H3	120.4	C9—C14—H14	119.7	
C2—C3—H3	120.4	C13—C14—H14	119.7	
O3—C8—H8A	110.0	O2—C7—O1	122.78 (12)	
O3—C8—H8B	110.0	O2—C7—C1	118.87 (12)	
O3—C8—C9	108.51 (11)	O1—C7—C1	118.36 (12)	
H8A—C8—H8B	108.4			
				
O3—C4—C5—C6	179.92 (14)	C2—C1—C7—O1	0.0 (2)	
O3—C4—C3—C2	−179.61 (14)	C3—C4—C5—C6	0.5 (2)	
O3—C8—C9—C10	45.48 (19)	C8—O3—C4—C5	172.07 (13)	
O3—C8—C9—C14	−136.32 (14)	C8—O3—C4—C3	−8.5 (2)	
C4—O3—C8—C9	−171.59 (12)	C8—C9—C10—C11	177.81 (14)	
C4—C5—C6—C1	−0.2 (2)	C8—C9—C14—C13	−177.25 (14)	
C5—C4—C3—C2	−0.2 (2)	C9—C10—C11—C12	−0.3 (3)	
C5—C6—C1—C2	−0.4 (2)	C10—C9—C14—C13	1.0 (2)	
C5—C6—C1—C7	178.37 (14)	C10—C11—C12—C13	0.4 (3)	
C6—C1—C2—C3	0.7 (2)	C11—C12—C13—C14	0.2 (3)	
C6—C1—C7—O2	0.9 (2)	C12—C13—C14—C9	−0.9 (2)	
C6—C1—C7—O1	−178.79 (15)	C14—C9—C10—C11	−0.4 (2)	
C1—C2—C3—C4	−0.4 (2)	C7—C1—C2—C3	−178.11 (14)	
C2—C1—C7—O2	179.73 (14)			

4-(Benzyloxy)benzoic acid Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A	
O1—H1···O2i	0.82	1.81	2.6213 (15)	169	

Symmetry code: (i) −x+2, −y, −z+1.

Figure 1 The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Figure 2 Packing of the mol­ecules in the title compound (for clarity, H atoms not involved in hydrogen bonding are omitted).

Figure 3 Synthesis of the title compound.

Table 1 Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A	
O1—H1⋯O2i	0.82	1.81	2.6213 (15)	169	
Symmetry code: (i) .

Table 2 Experimental details

Crystal data	
Chemical formula	C14H12O3	
M r	228.24	
Crystal system, space group	Monoclinic, P21/n	
Temperature (K)	305	
a, b, c (Å)	10.0564 (5), 3.9985 (2), 28.2235 (14)	
β (°)	97.744 (5)	
V (Å3)	1124.54 (10)	
Z	4	
Radiation type	Mo Kα	
μ (mm−1)	0.10	
Crystal size (mm)	0.16 × 0.15 × 0.13	
 	
Data collection	
Diffractometer	XtaLAB Synergy R, DW system, HyPix	
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 ▸)	
Tmin, Tmax	0.875, 1.000	
No. of measured, independent and observed [I > 2σ(I)] reflections	10523, 2793, 1996	
R int	0.019	
(sin θ/λ)max (Å−1)	0.721	
 	
Refinement	
R[F2 > 2σ(F2)], wR(F2), S	0.044, 0.135, 1.08	
No. of reflections	2793	
No. of parameters	156	
H-atom treatment	H-atom parameters constrained	
Δρmax, Δρmin (e Å−3)	0.26, −0.19	
Computer programs: CrysAlis PRO (Rigaku OD, 2022 ▸), SHELXT2018/3 (Sheldrick, 2015b ▸), SHELXL2018/3 (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).
==== Refs
References

Chattopadhyay, B., Das, U., Mukherjee, M. & Mukherjee, A. K. (2013). CrystEngComm, 15, 1077–1085.
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Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
Prasher, P. & Sharma, M. (2021). Drug Dev. Res. 82, 945–958.
Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
Sohail, R., Mathew, M., Patel, K. K., Reddy, S. A., Haider, Z., Naria, M., Habib, A., Abdin, Z. U., Chaudhry, W. R. & Akbar, A. (2023). Cureus, 15, e37080.
