Crystal structure of 2,5-di­methyl­anilinium salicylate

A Mani; P Praveen Kumar; G Chakkaravarthi

doi:10.1107/S2056989015014401

. 2015 Aug 6;71(Pt 9):o643–o644. doi: 10.1107/S2056989015014401

Crystal structure of 2,5-dimethylanilinium salicylate

A Mani ^a, P Praveen Kumar ^b,^*, G Chakkaravarthi ^c,^*

PMCID: PMC4555438 PMID: 26396881

Abstract

The title molecular salt, C₈H₁₂N⁺·C₇H₅O₃ ⁻ arose from the proton-transfer reaction between 2,5-xylidine and salicylic acid. In the anion, the dihedral angle between the planes of the aromatic ring and the –CO₂ ⁻ group is 11.08 (8)°; this near planarity is consolidated by an intramolecular O—H⋯O hydrogen bond. In the crystal, the components are connected by N—H⋯O hydrogen bonds, with all three O atoms in the anion acting as acceptors; the result is a [100] chain. The structure also features weak C—H⋯O bonds and aromatic π–π stacking [centroid-to-centroid distance = 3.7416 (10) Å] interactions, which lead to a three-dimensional network.

Keywords: crystal structure, hydrogen bonding, aromatic π–π stacking interactions

Related literature

For related structures, see: Fun et al. (2011 ▸); Mathlouthi et al. (2014 ▸); Smirani & Rzaigui (2009 ▸).

Experimental

Crystal data

C₈H₁₂N⁺·C₇H₅O₃ ⁻
M _r = 259.30
Monoclinic,
a = 6.9645 (5) Å
b = 20.6924 (14) Å
c = 9.2920 (7) Å
β = 95.738 (3)°
V = 1332.38 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.26 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.977, T _max = 0.982
17007 measured reflections
3384 independent reflections
2339 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.134
S = 1.01
3384 reflections
178 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: SAINT (Bruker, 2004 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014401/hb7474sup1.cif

e-71-0o643-sup1.cif^{(23KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014401/hb7474Isup2.hkl

e-71-0o643-Isup2.hkl^{(162.6KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015014401/hb7474Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S2056989015014401/hb7474fig1.tif

The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.

Click here for additional data file.^{(1.2MB, tif)}

a . DOI: 10.1107/S2056989015014401/hb7474fig2.tif

The packing of (I), viewed down a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

CCDC reference: 1415922

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O3H3AO2	0.83(1)	1.77(1)	2.5282(15)	151(2)
N1H1AO1ⁱ	0.89	1.80	2.6809(17)	169
N1H1BO2ⁱⁱ	0.89	1.92	2.7998(16)	168
N1H1CO3ⁱⁱⁱ	0.89	2.08	2.9654(17)	171
C5H5O1^iv	0.93	2.58	3.237(2)	128

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

Acknowledgments

The authors thank the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

S1. Structural commentary

We herewith report the crystal structure of the title compound, (I), (Fig. 1). The geometric parameters of the title compound (I) (Fig. 1) are comparable with the reported structures [Fun et al., 2011; Mathlouthi et al., 2014; Smirani & Rzaigui,(2009)].

The conformation of the anion is stabilized by a weak O—H···O (Table 1) hydrogen bond. In the crystal structure, the adjacent anions and cations are linked by medium-strength N—H···O (Table 1) hydrogen bonds which link the anions and cations into infinite chain along [100] and these chains are further influenced by C—H···O hydrogen bond (Table 1 & Fig. 2) and π–π [Cg2···Cg2ⁱ distance 3.7416 (10)Å; (i) 1-x, -y,1-z; Cg2 is the centroid of (C1—C6) ring] interactions to form a three dimensional network.

S2. Synthesis and crystallization

A mixture of 2,5-xylidine and salicylic acid dissolved in ethanol (molar ratio 1:1:1) was stirred for 3 h and then kept at room temperature. The saturated solution was allowed to evaporating slowly at room temperature. After the evaporation period of three weeks, colourless blocks were recovered.

S3. Refinement

H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for CH, N—H = 0.89Å and Uiso(H) = 1.5Ueq(N) for NH₃, C—H = 0.96Å and Uiso(H) = 1.5Ueq(C) for CH₃. H atom for hydroxyl group was fixed from Fourier map and refined with Uiso(H) = 1.5Ueq(O) and O—H distance was restraint to 0.82 (1)Å.