4-Methyl­anilinium 2-carboxyacetate

Suresh, S.; Pandi, P.; Akilan, R.; Kumar, R.M.; Chakkaravarthi, G.

doi:10.1107/S2414314618017145

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 12| December 2018| x181714

https://doi.org/10.1107/S2414314618017145

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4-Methylanilinium 2-carboxyacetate

S. Suresh,^a P. Pandi,^b R. Akilan,^c R. Mohan Kumar ^a ^* and G. Chakkaravarthi ^d ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics, Panimalar Engineering College, Chennai 600 123, India, ^cDepartment of Physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and ^dDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: mohan66@hotmail.com, chakkaravarthi_2005@yahoo.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 26 November 2018; accepted 3 December 2018; online 14 December 2018)

In the crystal of the title salt, C₇H₁₀N⁺·C₃H₃O₄⁻, the cations are linked to the anions via N—H⋯O and trifurcated N—H⋯(O,O,O) hydrogen bonds. The anions are linked into [010] chains by O—H⋯O hydrogen bonds. Taken together, these interactions generate (100) sheets.

Keywords: molecular salt; crystal structure; hydrogen bonding.

CCDC reference: 1882756

Structure description

Organic salts containing strong intermolecular hydrogen bonds have attracted attention as materials that may display ferroelectric–paraelectric phase transitions (Huang et al. 1999 ; Zhang et al. 2001 ). We report herein the synthesis and the crystal structure of the title salt (Fig. 1). Its geometric parameters are comparable with those of reported similar structures (Benali-Cherif et al., 2007 , 2009 ; Kalaiyarasi et al., 2017 ; Suresh et al., 2017 ; Wang, 2012 ).

Figure 1
The molecular structure of the title molecular salt, with the atom labelling and 30% probability displacement ellipsoids.

The asymmetric unit of the title salt (Fig. 1) contains a 4-methylanilinium cation and a carboxyacetate anion linked by an N1—H1C⋯O1 hydrogen bond (Table 1). In the crystal, the cations are linked to the anions via N—H⋯O and trifurcated N—H⋯(O,O,O) hydrogen bonds (Fig. 2, Table 1). The anions are linked into [010] chains by O—H⋯O hydrogen bonds. Taken together, these interactions generate (100) sheets.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.89	1.96	2.846 (2)	172
N1—H1B⋯O1ⁱⁱ	0.89	1.91	2.789 (2)	169
N1—H1C⋯O1	0.89	2.40	3.041 (2)	130
N1—H1C⋯O2ⁱⁱⁱ	0.89	2.47	2.980 (2)	117
N1—H1C⋯O3ⁱⁱⁱ	0.89	2.21	2.871 (2)	131
O3—H3A⋯O2^iv	0.87 (1)	1.67 (1)	2.5350 (19)	175 (2)
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+2; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The crystal packing of the title molecular salt viewed along the a axis. The hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Synthesis and crystallization

p-Toluidine (1.33 g) and malonic acid (1.30 g) were taken in a 1:1 ratio and dissolved in water at room temperature. The aqueous solution was stirred continuously for 6 h to obtain a transparent solution which was filtered and kept for slow evaporation. Crystals suitable for X-ray diffraction analysis were obtained after a period of one month.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·C₃H₃O₄⁻
M_r	211.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	12.996 (3), 9.2813 (19), 8.665 (2)
β (°)	105.503 (7)
V (Å³)	1007.1 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.678, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7352, 1766, 1282
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.05
No. of reflections	1766
No. of parameters	141
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXT2016 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1882756

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618017145/bt4079sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618017145/bt4079Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618017145/bt4079Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXT2016 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

4-Methylanilinium 2-carboxyacetate top

Crystal data top

C₇H₁₀N⁺·C₃H₃O₄⁻	F(000) = 448
M_r = 211.21	D_x = 1.393 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.996 (3) Å	Cell parameters from 2586 reflections
b = 9.2813 (19) Å	θ = 2.7–27.1°
c = 8.665 (2) Å	µ = 0.11 mm⁻¹
β = 105.503 (7)°	T = 295 K
V = 1007.1 (4) Å³	Block, colourless
Z = 4	0.24 × 0.22 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1282 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.031
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 25.0°, θ_min = 2.7°
T_min = 0.678, T_max = 0.746	h = −15→15
7352 measured reflections	k = −11→10
1766 independent reflections	l = −10→10

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0494P)² + 0.3929P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1766 reflections	Δρ_max = 0.21 e Å⁻³
141 parameters	Δρ_min = −0.19 e Å⁻³

Special details top

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. All H atoms were located in a difference map. The coordinates of the H atom bonded to O were refined with U(H) set to 1.5U_eq(O). H atoms bonded to C and N were refined using a riding model with U(H) set to 1.2U_eq(C) for the methylene group and 1.5U_eq(C,N) for the methyl and the NH₃ group. Both of them were allowed to rotate but not to tip.

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

	x	y	z	U_iso*/U_eq
C1	0.02784 (18)	0.2864 (3)	0.8804 (3)	0.0459 (6)
C2	0.05733 (19)	0.1495 (3)	0.9312 (3)	0.0575 (8)
H2	0.009107	0.074666	0.896510	0.069*
C3	0.15679 (18)	0.1185 (2)	1.0327 (3)	0.0526 (7)
H3	0.174453	0.024333	1.065946	0.063*
C4	0.22828 (15)	0.2265 (2)	1.0833 (2)	0.0279 (5)
C5	0.20331 (19)	0.3638 (2)	1.0313 (3)	0.0527 (7)
H5	0.252962	0.437536	1.063048	0.063*
C6	0.1029 (2)	0.3927 (3)	0.9305 (3)	0.0654 (9)
H6	0.085992	0.486688	0.895849	0.078*
C7	−0.0826 (2)	0.3149 (3)	0.7724 (4)	0.0721 (9)
H7A	−0.083796	0.293072	0.663661	0.108*
H7B	−0.100685	0.414418	0.780352	0.108*
H7C	−0.133570	0.255254	0.804694	0.108*
C8	0.40281 (15)	−0.05466 (19)	0.8494 (2)	0.0235 (5)
C9	0.38105 (16)	−0.1849 (2)	0.9427 (2)	0.0268 (5)
H9A	0.424395	−0.176610	1.052432	0.032*
H9B	0.306807	−0.182213	0.944691	0.032*
C10	0.40283 (16)	−0.32853 (19)	0.8784 (2)	0.0253 (5)
N1	0.33326 (13)	0.19495 (17)	1.1900 (2)	0.0309 (4)
H1A	0.331546	0.109900	1.236679	0.046*
H1B	0.350879	0.263146	1.264632	0.046*
H1C	0.381413	0.192567	1.133796	0.046*
O1	0.37677 (11)	0.06550 (14)	0.89126 (17)	0.0345 (4)
O2	0.44594 (12)	−0.07617 (13)	0.73668 (17)	0.0327 (4)
O3	0.50449 (11)	−0.35675 (14)	0.90227 (17)	0.0325 (4)
H3A	0.5173 (18)	−0.4328 (17)	0.852 (2)	0.049*
O4	0.33156 (11)	−0.41000 (15)	0.81073 (19)	0.0395 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0363 (13)	0.0460 (14)	0.0477 (15)	0.0015 (11)	−0.0024 (11)	0.0024 (11)
C2	0.0397 (14)	0.0407 (15)	0.080 (2)	−0.0133 (11)	−0.0052 (14)	0.0067 (13)
C3	0.0361 (13)	0.0300 (12)	0.081 (2)	−0.0041 (10)	−0.0025 (13)	0.0090 (12)
C4	0.0252 (11)	0.0264 (11)	0.0320 (11)	0.0024 (8)	0.0073 (9)	0.0001 (9)
C5	0.0493 (15)	0.0311 (13)	0.0623 (17)	−0.0078 (11)	−0.0119 (13)	0.0033 (12)
C6	0.0616 (17)	0.0336 (14)	0.078 (2)	0.0027 (12)	−0.0207 (16)	0.0105 (13)
C7	0.0498 (17)	0.0668 (19)	0.081 (2)	0.0030 (14)	−0.0155 (16)	0.0079 (16)
C8	0.0224 (10)	0.0206 (10)	0.0247 (10)	−0.0008 (8)	0.0011 (9)	−0.0013 (8)
C9	0.0299 (11)	0.0232 (10)	0.0291 (11)	0.0002 (8)	0.0111 (9)	−0.0007 (8)
C10	0.0309 (11)	0.0205 (10)	0.0255 (11)	−0.0024 (9)	0.0094 (9)	0.0054 (8)
N1	0.0274 (9)	0.0244 (9)	0.0410 (11)	−0.0006 (7)	0.0090 (8)	0.0020 (8)
O1	0.0441 (9)	0.0204 (7)	0.0398 (9)	0.0065 (6)	0.0122 (7)	−0.0011 (6)
O2	0.0465 (9)	0.0232 (7)	0.0331 (8)	−0.0009 (6)	0.0187 (7)	0.0001 (6)
O3	0.0338 (8)	0.0205 (7)	0.0441 (9)	−0.0009 (6)	0.0121 (7)	−0.0032 (6)
O4	0.0361 (9)	0.0257 (8)	0.0530 (10)	−0.0061 (7)	0.0056 (8)	−0.0073 (7)

Geometric parameters (Å, º) top

C1—C2	1.366 (3)	C7—H7C	0.9600
C1—C6	1.373 (3)	C8—O1	1.247 (2)
C1—C7	1.513 (3)	C8—O2	1.265 (2)
C2—C3	1.385 (3)	C8—C9	1.522 (3)
C2—H2	0.9300	C9—C10	1.501 (3)
C3—C4	1.357 (3)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.362 (3)	C10—O4	1.218 (2)
C4—N1	1.459 (2)	C10—O3	1.308 (2)
C5—C6	1.389 (3)	N1—H1A	0.8900
C5—H5	0.9300	N1—H1B	0.8900
C6—H6	0.9300	N1—H1C	0.8900
C7—H7A	0.9600	O3—H3A	0.868 (10)
C7—H7B	0.9600

C2—C1—C6	116.8 (2)	H7A—C7—H7C	109.5
C2—C1—C7	120.0 (2)	H7B—C7—H7C	109.5
C6—C1—C7	123.1 (2)	O1—C8—O2	125.19 (18)
C1—C2—C3	122.1 (2)	O1—C8—C9	116.89 (18)
C1—C2—H2	118.9	O2—C8—C9	117.92 (16)
C3—C2—H2	118.9	C10—C9—C8	115.34 (16)
C4—C3—C2	119.6 (2)	C10—C9—H9A	108.4
C4—C3—H3	120.2	C8—C9—H9A	108.4
C2—C3—H3	120.2	C10—C9—H9B	108.4
C3—C4—C5	120.2 (2)	C8—C9—H9B	108.4
C3—C4—N1	120.01 (18)	H9A—C9—H9B	107.5
C5—C4—N1	119.81 (18)	O4—C10—O3	123.91 (18)
C4—C5—C6	119.3 (2)	O4—C10—C9	122.39 (18)
C4—C5—H5	120.4	O3—C10—C9	113.70 (16)
C6—C5—H5	120.4	C4—N1—H1A	109.5
C1—C6—C5	122.0 (2)	C4—N1—H1B	109.5
C1—C6—H6	119.0	H1A—N1—H1B	109.5
C5—C6—H6	119.0	C4—N1—H1C	109.5
C1—C7—H7A	109.5	H1A—N1—H1C	109.5
C1—C7—H7B	109.5	H1B—N1—H1C	109.5
H7A—C7—H7B	109.5	C10—O3—H3A	113.8 (16)
C1—C7—H7C	109.5

C6—C1—C2—C3	2.1 (4)	C2—C1—C6—C5	−1.6 (5)
C7—C1—C2—C3	−178.7 (3)	C7—C1—C6—C5	179.2 (3)
C1—C2—C3—C4	−0.5 (5)	C4—C5—C6—C1	−0.4 (5)
C2—C3—C4—C5	−1.6 (4)	O1—C8—C9—C10	173.92 (16)
C2—C3—C4—N1	−179.9 (2)	O2—C8—C9—C10	−6.4 (2)
C3—C4—C5—C6	2.1 (4)	C8—C9—C10—O4	−107.8 (2)
N1—C4—C5—C6	−179.6 (2)	C8—C9—C10—O3	72.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.89	1.96	2.846 (2)	172
N1—H1B···O1ⁱⁱ	0.89	1.91	2.789 (2)	169
N1—H1C···O1	0.89	2.40	3.041 (2)	130
N1—H1C···O2ⁱⁱⁱ	0.89	2.47	2.980 (2)	117
N1—H1C···O3ⁱⁱⁱ	0.89	2.21	2.871 (2)	131
O3—H3A···O2^iv	0.87 (1)	1.67 (1)	2.5350 (19)	175 (2)

Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, −y, −z+2; (iv) −x+1, y−1/2, −z+3/2.

Acknowledgements

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

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