4-Nitro­phenyl 4-hy­droxy-3-methyl­benzoate

S Sreenivasa; H C Devarajegowda; H T Srinivasa; Vijith Kumar; B S Palakshamurthy

doi:10.1107/S1600536812048271

. 2012 Nov 30;68(Pt 12):o3490. doi: 10.1107/S1600536812048271

4-Nitrophenyl 4-hydroxy-3-methylbenzoate

S Sreenivasa ^a, H C Devarajegowda ^b,^*, H T Srinivasa ^c, Vijith Kumar ^d, B S Palakshamurthy ^b

PMCID: PMC3589062 PMID: 23476298

Abstract

The asymmetric unit of the title compound, C₁₄H₁₁NO₅, contains two independent molecules in which the dihedral angles between the benzene rings are 89.27 (16) and 77.14 (12)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating C(8) chains propagating in [010] for one molecule and [001] C(8) chains for the other. The chains are connected by C—H⋯O hydrogen bonds and π–π interactions [shortest centroid–centroid distance = 3.5908 (12)°], generating a three-dimensional network.

Related literature

For general background to aromatic nitro groups, see: Ghosh et al. (2012 ▶); Sugiyama et al. (2002 ▶).

Experimental

Crystal data

C₁₄H₁₁NO₅
M _r = 273.24
Monoclinic,
a = 42.313 (6) Å
b = 8.0047 (11) Å
c = 16.1078 (18) Å
β = 105.819 (4)°
V = 5249.2 (12) Å³
Z = 16
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: ψ scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.975, T _max = 0.983
28460 measured reflections
4602 independent reflections
3349 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.143
S = 1.02
4602 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(22.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812048271/hb6999sup1.cif

e-68-o3490-sup1.cif^{(22.5KB, cif)}

Click here for additional data file.^{(221KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048271/hb6999Isup2.hkl

e-68-o3490-Isup2.hkl^{(221KB, hkl)}

Click here for additional data file.^{(5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812048271/hb6999Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯O2A ⁱ	0.82	1.94	2.753 (2)	172
O1B—H1B⋯O2B ⁱⁱ	0.82	1.94	2.727 (3)	160
C7B—H7B1⋯O4A ⁱⁱⁱ	0.96	2.50	3.418 (3)	159
C12A—H12A⋯O2A ⁱ	0.93	2.54	3.245 (2)	132
C19B—H19B⋯O5A ^iv	0.93	2.58	3.476 (4)	163

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors thank Professor T. N. Guru Row, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, and G. B. Sadananda, Department of Studies and Research in Physics, U.C.S. Tumkur University, Tumkur for their help and suggestions.

supplementary crystallographic information

Comment

Electron withdrawing nitro group is an important structural element having good synthetic value in organic synthesis to achieve a wide variety of natural and biological active molecules (Ghosh et al., 2012). Formation of two-component molecular crystals from nitro benzoic acid and aromatic or heterocyclic bases leads to discovery of new functional solid materials for nonlinear optics (Sugiyama et al., 2002).

The asymmetric unit of 4-Nitrophenyl 4-hydroxy-3-methylbenzoate crystallographically two independent molecules are shown in Fig.1. Each independent molecule (a and b) is approximately perpendicular to each other; the dihedral angle is 89.17 (14)°. The dihedral angles between the benzene rings in the two molecules [(C8a–C13a and C15a–C20a) and C8b–C13b and C15b–C20b)] are 89.27 (16)° and 77.14 (12)° respectively. The crystal structure features O—H···O and C—H···O interactions (Table 1) and π—π interactions.

Experimental

A mixture of 4-nitrophenol (0.100 g, 0.072 mol) and 4-hydroxy-3-methylbenzoic acid (0.109 g, 0.072 mol) and dicyclohexyldicarbodimide (0.150 g, 0.11 mol) in 1 ml of dry dimethylsufoxide (DMSO) was irradiated under microwave (600 MHz) for 5 x 60sec. Reaction was monitored by TLC, after completion of reaction; the reaction mixture was poured into ice cold, dilute hydrochloric acid which precipitated as ester. The crude product was filtered through Buckner funnel with vacuum, washed with water, crude precipitate was stirred for 1 hr with a saturated sodium bicarbonate solution to remove excess acid. The ester was again collected by filtration, washed repeatedly with water, air dried, and then repeatedly crystallized to get colourless plates from an ethanol-chloroform solvent mixture.