Crystal structure of 2,5-di-methyl-anilinium salicylate.

The title mol-ecular 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 intra-molecular 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] inter-actions, which lead to a three-dimensional network.

Related literature

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

Experimental

Crystal data

C8H12N+·C7H5O3 −

M = 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

Δρmax = 0.22 e Å−3

Δρmin = −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.

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

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

Click here for additional data file.

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

Click here for additional data file.

. 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.

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

C8H12N+·C7H5O3−	F(000) = 552
Mr = 259.30	Dx = 1.293 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4550 reflections
a = 6.9645 (5) Å	θ = 2.4–28.1°
b = 20.6924 (14) Å	µ = 0.09 mm−1
c = 9.2920 (7) Å	T = 295 K
β = 95.738 (3)°	Block, colourless
V = 1332.38 (17) Å3	0.26 × 0.24 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3384 independent reflections
Radiation source: fine-focus sealed tube	2339 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω and φ scan	θmax = 28.7°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
Tmin = 0.977, Tmax = 0.982	k = −27→27
17007 measured reflections	l = −12→12

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.3396P] where P = (Fo2 + 2Fc2)/3
3384 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.22 e Å−3
1 restraint	Δρmin = −0.21 e Å−3

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. 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
C1	0.52627 (19)	0.05604 (7)	0.67259 (15)	0.0271 (3)
C2	0.5588 (2)	0.09450 (8)	0.55505 (17)	0.0371 (4)
H2	0.6825	0.1100	0.5463	0.045*
C3	0.4109 (3)	0.11016 (9)	0.45114 (18)	0.0474 (4)
H3	0.4352	0.1350	0.3715	0.057*
C4	0.2267 (3)	0.08870 (9)	0.46651 (18)	0.0467 (4)
H4	0.1260	0.1002	0.3979	0.056*
C5	0.1897 (2)	0.05073 (9)	0.58152 (18)	0.0405 (4)
H5	0.0646	0.0369	0.5911	0.049*
C6	0.3394 (2)	0.03300 (7)	0.68349 (16)	0.0303 (3)
C7	0.6859 (2)	0.04029 (7)	0.78590 (16)	0.0303 (3)
C8	0.01106 (19)	0.35845 (7)	0.60141 (15)	0.0281 (3)
C9	−0.1341 (2)	0.33448 (7)	0.67764 (16)	0.0326 (3)
H9	−0.2289	0.3622	0.7052	0.039*
C10	−0.1397 (2)	0.26951 (8)	0.71351 (18)	0.0384 (4)
C11	0.0036 (3)	0.23006 (8)	0.6699 (2)	0.0471 (4)
H11	0.0023	0.1862	0.6914	0.057*
C12	0.1487 (3)	0.25462 (8)	0.5951 (2)	0.0484 (5)
H12	0.2440	0.2268	0.5686	0.058*
C13	0.1568 (2)	0.31966 (8)	0.55812 (18)	0.0367 (4)
C14	0.3146 (3)	0.34526 (9)	0.4753 (2)	0.0562 (5)
H14A	0.2589	0.3651	0.3874	0.084*
H14B	0.3971	0.3104	0.4524	0.084*
H14C	0.3886	0.3767	0.5329	0.084*
C15	−0.2965 (3)	0.24282 (9)	0.7963 (2)	0.0571 (5)
H15A	−0.2783	0.1971	0.8094	0.086*
H15B	−0.4198	0.2507	0.7433	0.086*
H15C	−0.2917	0.2635	0.8890	0.086*
N1	0.00494 (17)	0.42673 (5)	0.56098 (14)	0.0306 (3)
H1A	−0.0346	0.4304	0.4673	0.046*
H1B	0.1223	0.4438	0.5785	0.046*
H1C	−0.0766	0.4475	0.6126	0.046*
O1	0.84427 (15)	0.06900 (6)	0.78665 (13)	0.0441 (3)
O2	0.65428 (15)	−0.00223 (6)	0.87917 (13)	0.0431 (3)
O3	0.29811 (16)	−0.00571 (6)	0.79399 (13)	0.0469 (3)
H3A	0.402 (2)	−0.0124 (11)	0.844 (2)	0.070*

	U11	U22	U33	U12	U13	U23
C1	0.0274 (7)	0.0264 (7)	0.0274 (7)	0.0019 (5)	0.0017 (6)	−0.0008 (5)
C2	0.0388 (8)	0.0367 (8)	0.0365 (8)	−0.0016 (7)	0.0067 (7)	0.0049 (7)
C3	0.0619 (12)	0.0442 (10)	0.0355 (9)	0.0061 (8)	0.0017 (8)	0.0117 (7)
C4	0.0468 (10)	0.0568 (11)	0.0337 (9)	0.0155 (8)	−0.0099 (7)	0.0011 (8)
C5	0.0291 (8)	0.0546 (10)	0.0365 (9)	0.0022 (7)	−0.0037 (7)	−0.0051 (7)
C6	0.0287 (7)	0.0336 (7)	0.0284 (7)	−0.0007 (6)	0.0021 (6)	0.0000 (6)
C7	0.0257 (7)	0.0345 (8)	0.0308 (7)	0.0014 (6)	0.0036 (6)	0.0004 (6)
C8	0.0281 (7)	0.0252 (7)	0.0296 (7)	0.0024 (5)	−0.0032 (6)	−0.0023 (6)
C9	0.0293 (7)	0.0318 (7)	0.0365 (8)	0.0021 (6)	0.0017 (6)	−0.0035 (6)
C10	0.0423 (9)	0.0350 (8)	0.0371 (8)	−0.0039 (7)	0.0005 (7)	0.0021 (7)
C11	0.0547 (11)	0.0282 (8)	0.0579 (11)	0.0044 (7)	0.0025 (9)	0.0050 (8)
C12	0.0450 (10)	0.0346 (9)	0.0659 (12)	0.0127 (7)	0.0066 (9)	−0.0058 (8)
C13	0.0338 (8)	0.0335 (8)	0.0431 (9)	0.0033 (6)	0.0050 (7)	−0.0046 (7)
C14	0.0482 (11)	0.0482 (10)	0.0763 (14)	0.0038 (8)	0.0272 (10)	−0.0080 (10)
C15	0.0622 (12)	0.0484 (11)	0.0629 (12)	−0.0095 (9)	0.0165 (10)	0.0084 (9)
N1	0.0274 (6)	0.0268 (6)	0.0370 (7)	0.0000 (5)	0.0003 (5)	−0.0015 (5)
O1	0.0278 (6)	0.0586 (7)	0.0452 (7)	−0.0091 (5)	−0.0002 (5)	0.0057 (6)
O2	0.0305 (6)	0.0545 (7)	0.0429 (6)	−0.0005 (5)	−0.0028 (5)	0.0203 (5)
O3	0.0300 (6)	0.0659 (8)	0.0436 (7)	−0.0128 (5)	−0.0013 (5)	0.0194 (6)

C1—C2	1.388 (2)	C9—H9	0.9300
C1—C6	1.399 (2)	C10—C11	1.381 (2)
C1—C7	1.4886 (19)	C10—C15	1.502 (3)
C2—C3	1.378 (2)	C11—C12	1.379 (3)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.379 (3)	C12—C13	1.392 (2)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.371 (2)	C13—C14	1.500 (2)
C4—H4	0.9300	C14—H14A	0.9600
C5—C6	1.386 (2)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600
C6—O3	1.3556 (18)	C15—H15A	0.9600
C7—O1	1.2524 (17)	C15—H15B	0.9600
C7—O2	1.2696 (18)	C15—H15C	0.9600
C8—C9	1.383 (2)	N1—H1A	0.8900
C8—C13	1.385 (2)	N1—H1B	0.8900
C8—N1	1.4615 (18)	N1—H1C	0.8900
C9—C10	1.387 (2)	O3—H3A	0.829 (10)
C2—C1—C6	118.59 (13)	C9—C10—C15	121.27 (15)
C2—C1—C7	120.85 (13)	C12—C11—C10	121.15 (15)
C6—C1—C7	120.55 (13)	C12—C11—H11	119.4
C3—C2—C1	121.10 (15)	C10—C11—H11	119.4
C3—C2—H2	119.4	C11—C12—C13	122.07 (15)
C1—C2—H2	119.4	C11—C12—H12	119.0
C2—C3—C4	119.33 (16)	C13—C12—H12	119.0
C2—C3—H3	120.3	C8—C13—C12	116.06 (15)
C4—C3—H3	120.3	C8—C13—C14	122.70 (14)
C5—C4—C3	120.96 (15)	C12—C13—C14	121.23 (15)
C5—C4—H4	119.5	C13—C14—H14A	109.5
C3—C4—H4	119.5	C13—C14—H14B	109.5
C4—C5—C6	119.82 (15)	H14A—C14—H14B	109.5
C4—C5—H5	120.1	C13—C14—H14C	109.5
C6—C5—H5	120.1	H14A—C14—H14C	109.5
O3—C6—C5	118.17 (13)	H14B—C14—H14C	109.5
O3—C6—C1	121.70 (12)	C10—C15—H15A	109.5
C5—C6—C1	120.12 (14)	C10—C15—H15B	109.5
O1—C7—O2	122.51 (13)	H15A—C15—H15B	109.5
O1—C7—C1	119.68 (13)	C10—C15—H15C	109.5
O2—C7—C1	117.81 (12)	H15A—C15—H15C	109.5
C9—C8—C13	122.38 (14)	H15B—C15—H15C	109.5
C9—C8—N1	118.31 (12)	C8—N1—H1A	109.5
C13—C8—N1	119.27 (13)	C8—N1—H1B	109.5
C8—C9—C10	120.71 (14)	H1A—N1—H1B	109.5
C8—C9—H9	119.6	C8—N1—H1C	109.5
C10—C9—H9	119.6	H1A—N1—H1C	109.5
C11—C10—C9	117.62 (15)	H1B—N1—H1C	109.5
C11—C10—C15	121.10 (15)	C6—O3—H3A	106.5 (16)
C6—C1—C2—C3	0.3 (2)	C6—C1—C7—O2	10.7 (2)
C7—C1—C2—C3	−178.85 (15)	C13—C8—C9—C10	−0.4 (2)
C1—C2—C3—C4	1.8 (3)	N1—C8—C9—C10	177.30 (13)
C2—C3—C4—C5	−1.7 (3)	C8—C9—C10—C11	−0.2 (2)
C3—C4—C5—C6	−0.6 (3)	C8—C9—C10—C15	−179.99 (15)
C4—C5—C6—O3	−178.60 (15)	C9—C10—C11—C12	0.9 (3)
C4—C5—C6—C1	2.7 (2)	C15—C10—C11—C12	−179.39 (17)
C2—C1—C6—O3	178.81 (14)	C10—C11—C12—C13	−0.9 (3)
C7—C1—C6—O3	−2.0 (2)	C9—C8—C13—C12	0.4 (2)
C2—C1—C6—C5	−2.6 (2)	N1—C8—C13—C12	−177.30 (14)
C7—C1—C6—C5	176.58 (14)	C9—C8—C13—C14	179.91 (15)
C2—C1—C7—O1	10.0 (2)	N1—C8—C13—C14	2.3 (2)
C6—C1—C7—O1	−169.13 (14)	C11—C12—C13—C8	0.3 (3)
C2—C1—C7—O2	−170.18 (14)	C11—C12—C13—C14	−179.29 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.83 (1)	1.77 (1)	2.5282 (15)	151 (2)
N1—H1A···O1i	0.89	1.80	2.6809 (17)	169
N1—H1B···O2ii	0.89	1.92	2.7998 (16)	168
N1—H1C···O3iii	0.89	2.08	2.9654 (17)	171
C5—H5···O1iv	0.93	2.58	3.237 (2)	128

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
C5H5O1iv	0.93	2.58	3.237(2)	128

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