4-Methyl­anilinium 3-carb­oxy-2-hy­droxy­propano­ate

Kalaiyarasi, S.; Devi, S.R.; Akilan, R.; Kumar, R.M.; Chakkaravarthi, G.

doi:10.1107/S241431461601525X

organic compounds

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ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161525

doi:10.1107/S241431461601525X

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4-Methylanilinium 3-carboxy-2-hydroxypropanoate

S. Kalaiyarasi,^a S. Reena Devi,^a R. Akilan,^b R. Mohan Kumar ^a ^* and G. Chakkaravarthi ^c ^*

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

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 23 September 2016; accepted 28 September 2016; online 30 September 2016)

The title molecular salt, C₇H₁₀N⁺·C₄H₅O₅⁻, contains a 4-methylanilinium cation and a 3-carboxy-2-hydroxypropanoate (hydrogen 2-hydroxysuccinate) anion in the asymmetric unit. The cation is protonated at the amine N atom and the anion is deprotonated at one of the hydroxy O atoms of the carboxylic acid groups. An O—H⋯O hydrogen bond in the anion generates an S(5) graph-set motif. An N—H⋯O hydrogen bond links the anion and cation in the asymmetric unit. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link adjacent anions and cations, forming a two-dimensional network parallel to the ac plane and enclosing R₂³(12), R₂³(14) and R₃²(10) ring motifs.

Keywords: crystal structure; molecular salt; hydrogen bonding; 4-methylanilinium; 2-hydroxysuccinate.

CCDC reference: 1498051

Structure description

Succinic acid derivatives are mostly used as food and pharmaceutical chemicals (Sauer et al., 2008 ). We report the synthesis and the crystal structure of the title molecular salt (Fig. 1), which contains a 4-methylanilinium cation and 2-hydroxysuccinate anion in the asymmetric unit. Geometrical parameters are comparable with those for the reported structures of 4-methylanilinium nitrate (Benali-Cherif et al., 2009 ) and 2-hydroxysuccinate salts (Fleck et al., 2001 ).

Figure 1
The molecular structure of the title molecular salt, showing the atom labelling and 30% probability displacement ellipsoids. The dashed line represents the intramolecular hydrogen bond.

The cation is protonated at amine atom N1 and the anion is deprotonated at hydroxy atom O2. An N1—H1A⋯O5 hydrogen bond links the anion and cation while an O5—H5A⋯O1 hydrogen bond generates an S(5) graph-set motif in the anion (Fig. 1 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1	0.82 (1)	2.12 (3)	2.6101 (15)	119 (2)
N1—H1A⋯O5	0.87 (1)	1.98 (1)	2.8381 (18)	172 (2)
N1—H1B⋯O1ⁱ	0.87 (1)	1.88 (1)	2.7328 (18)	168 (2)
N1—H1C⋯O2ⁱⁱ	0.87 (1)	2.01 (1)	2.8736 (19)	170 (2)
O3—H3A⋯O2ⁱ	0.83 (1)	1.75 (1)	2.5830 (16)	179 (3)
O5—H5A⋯O4ⁱⁱⁱ	0.82 (1)	2.26 (2)	2.8088 (18)	125 (2)
Symmetry codes: (i) x-1, y, z; (ii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

In the crystal structure, N—H⋯O and O—H⋯O hydrogen bonds link adjacent anions and cations into infinite two-dimensional networks along the ac plane (Table 1 and Fig. 2). The inter-ionic N1—H1B⋯O1ⁱ, N1—H1A⋯O5ⁱⁱ and O3—H3A⋯O2ⁱ hydrogen bonds generate an R₂³(12) ring motif, the N1—H1B⋯O1ⁱ, N1—H1C⋯O2ⁱⁱ and O5—H5A⋯O4ⁱ hydrogen bonds generate an R₂³(14) ring motif and the N1—H1A⋯O5, N1—H1C⋯O2ⁱⁱ, O5—H5A⋯O4ⁱⁱⁱ and O3—H3A⋯O2ⁱ hydrogen bonds generate an R₃²(10) ring motif (Fig. 3; for symmetry codes, see Table 1).

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

Figure 3
A partial view of the crystal packing showing the ring motifs. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Synthesis and crystallization

The title compound was synthesized from the raw materials p-toluidine and DL-malic acid which were taken in 1:1 ratio and dissolved in water at ambient temperature. The aqueous solution was continuously stirred for six h to prepare a homogeneous solution. After a transparent solution was obtained, it was filtered and kept for slow evaporation. Crystals suitable for X-ray diffraction were obtained after a period of five weeks.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·C₄H₅O₅⁻
M_r	241.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.4849 (8), 16.1306 (16), 10.4904 (10)
β (°)	109.234 (3)
V (Å³)	1195.9 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.686, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	19297, 3403, 2078
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.700

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.136, 1.03
No. of reflections	3403
No. of parameters	173
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1498051

Crystal structure: contains datablocks I, global. DOI: 10.1107/S241431461601525X/vm4015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461601525X/vm4015Isup2.hkl

Supporting information file. DOI: 10.1107/S241431461601525X/vm4015Isup3.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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

4-Methylanilinium 3-carboxy-2-hydroxypropanoate top

Crystal data top

C₇H₁₀N⁺·C₄H₅O₅⁻	F(000) = 512
M_r = 241.24	D_x = 1.340 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4849 (8) Å	Cell parameters from 5534 reflections
b = 16.1306 (16) Å	θ = 2.4–29.6°
c = 10.4904 (10) Å	µ = 0.11 mm⁻¹
β = 109.234 (3)°	T = 295 K
V = 1195.9 (2) Å³	Block, colourless
Z = 4	0.26 × 0.22 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2078 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.047
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 29.9°, θ_min = 2.4°
T_min = 0.686, T_max = 0.746	h = −10→10
19297 measured reflections	k = −22→22
3403 independent reflections	l = −14→14

Refinement top

Refinement on F²	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.055P)² + 0.3504P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3403 reflections	Δρ_max = 0.37 e Å⁻³
173 parameters	Δρ_min = −0.20 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.

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

	x	y	z	U_iso*/U_eq
C1	0.2423 (3)	0.50050 (12)	0.9996 (2)	0.0447 (5)
C2	0.2804 (3)	0.58051 (13)	1.04649 (19)	0.0498 (5)
H2	0.322596	0.590187	1.139054	0.060*
C3	0.2574 (3)	0.64649 (12)	0.95917 (17)	0.0436 (4)
H3	0.284307	0.700093	0.992660	0.052*
C4	0.1946 (2)	0.63270 (10)	0.82288 (16)	0.0297 (4)
C5	0.1539 (3)	0.55398 (12)	0.77248 (19)	0.0463 (5)
H5	0.110417	0.544643	0.679829	0.056*
C6	0.1787 (3)	0.48874 (13)	0.8621 (2)	0.0544 (5)
H6	0.151451	0.435215	0.828325	0.065*
C7	0.2706 (3)	0.42870 (15)	1.0955 (3)	0.0683 (7)
H7A	0.267825	0.448194	1.181262	0.102*
H7B	0.390753	0.403169	1.106808	0.102*
H7C	0.171438	0.388864	1.059646	0.102*
C8	0.8664 (2)	0.81546 (11)	0.87375 (15)	0.0300 (4)
C9	0.6854 (2)	0.80756 (11)	0.91036 (16)	0.0329 (4)
H9	0.711761	0.770807	0.988796	0.039*
C10	0.6193 (2)	0.88973 (11)	0.94679 (19)	0.0372 (4)
H10A	0.591569	0.927381	0.870639	0.045*
H10B	0.717729	0.914278	1.022132	0.045*
C11	0.4433 (2)	0.87581 (10)	0.98457 (16)	0.0307 (4)
N1	0.16966 (19)	0.70315 (10)	0.73151 (15)	0.0324 (3)
O1	0.86759 (15)	0.78284 (8)	0.76746 (12)	0.0398 (3)
O2	1.00180 (15)	0.85307 (9)	0.95801 (11)	0.0443 (3)
O3	0.28940 (16)	0.90265 (10)	0.89417 (13)	0.0509 (4)
O4	0.44432 (17)	0.84089 (9)	1.08584 (13)	0.0495 (4)
O5	0.53901 (15)	0.77145 (8)	0.80248 (12)	0.0405 (3)
H1A	0.2777 (18)	0.7287 (12)	0.753 (2)	0.052 (6)*
H1B	0.080 (2)	0.7348 (11)	0.739 (2)	0.050 (6)*
H1C	0.131 (3)	0.6877 (13)	0.6475 (11)	0.058 (6)*
H3A	0.197 (3)	0.8863 (16)	0.915 (3)	0.087*
H5A	0.589 (3)	0.7479 (16)	0.754 (2)	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0391 (10)	0.0430 (11)	0.0527 (12)	0.0069 (8)	0.0160 (8)	0.0088 (9)
C2	0.0566 (12)	0.0563 (13)	0.0313 (9)	−0.0025 (10)	0.0073 (8)	0.0025 (9)
C3	0.0539 (11)	0.0403 (11)	0.0338 (9)	−0.0078 (8)	0.0109 (8)	−0.0075 (8)
C4	0.0236 (7)	0.0348 (9)	0.0322 (8)	0.0010 (6)	0.0111 (6)	−0.0015 (7)
C5	0.0604 (12)	0.0433 (11)	0.0345 (9)	−0.0009 (9)	0.0146 (8)	−0.0094 (8)
C6	0.0715 (14)	0.0345 (11)	0.0581 (13)	−0.0012 (10)	0.0226 (11)	−0.0069 (9)
C7	0.0657 (14)	0.0611 (15)	0.0812 (17)	0.0157 (12)	0.0284 (13)	0.0325 (13)
C8	0.0191 (7)	0.0424 (10)	0.0295 (8)	0.0041 (6)	0.0091 (6)	0.0049 (7)
C9	0.0231 (7)	0.0430 (10)	0.0347 (8)	−0.0027 (7)	0.0123 (6)	−0.0018 (7)
C10	0.0259 (8)	0.0443 (10)	0.0453 (10)	−0.0067 (7)	0.0169 (7)	−0.0082 (8)
C11	0.0255 (7)	0.0378 (9)	0.0317 (8)	−0.0023 (6)	0.0133 (6)	−0.0064 (7)
N1	0.0261 (7)	0.0411 (9)	0.0323 (8)	−0.0005 (6)	0.0129 (6)	−0.0015 (6)
O1	0.0312 (6)	0.0538 (8)	0.0394 (7)	0.0036 (5)	0.0184 (5)	−0.0043 (6)
O2	0.0219 (5)	0.0758 (10)	0.0357 (7)	−0.0091 (6)	0.0101 (5)	−0.0050 (6)
O3	0.0270 (6)	0.0840 (11)	0.0446 (7)	0.0028 (6)	0.0156 (5)	0.0187 (7)
O4	0.0343 (7)	0.0718 (10)	0.0437 (7)	0.0051 (6)	0.0145 (5)	0.0159 (7)
O5	0.0247 (6)	0.0522 (8)	0.0472 (7)	−0.0080 (5)	0.0152 (5)	−0.0180 (6)

Geometric parameters (Å, º) top

C1—C6	1.375 (3)	C8—O2	1.2596 (19)
C1—C2	1.377 (3)	C8—C9	1.530 (2)
C1—C7	1.503 (3)	C9—O5	1.4155 (19)
C2—C3	1.378 (3)	C9—C10	1.508 (2)
C2—H2	0.9300	C9—H9	0.9800
C3—C4	1.368 (2)	C10—C11	1.512 (2)
C3—H3	0.9300	C10—H10A	0.9700
C4—C5	1.371 (3)	C10—H10B	0.9700
C4—N1	1.458 (2)	C11—O4	1.200 (2)
C5—C6	1.382 (3)	C11—O3	1.302 (2)
C5—H5	0.9300	N1—H1A	0.868 (9)
C6—H6	0.9300	N1—H1B	0.868 (9)
C7—H7A	0.9600	N1—H1C	0.869 (9)
C7—H7B	0.9600	O3—H3A	0.831 (10)
C7—H7C	0.9600	O5—H5A	0.816 (10)
C8—O1	1.2357 (19)

C6—C1—C2	117.62 (18)	O1—C8—C9	117.47 (14)
C6—C1—C7	121.3 (2)	O2—C8—C9	116.00 (14)
C2—C1—C7	121.06 (19)	O5—C9—C10	109.40 (13)
C1—C2—C3	121.37 (18)	O5—C9—C8	110.47 (13)
C1—C2—H2	119.3	C10—C9—C8	112.47 (14)
C3—C2—H2	119.3	O5—C9—H9	108.1
C4—C3—C2	119.60 (17)	C10—C9—H9	108.1
C4—C3—H3	120.2	C8—C9—H9	108.1
C2—C3—H3	120.2	C9—C10—C11	108.84 (14)
C3—C4—C5	120.66 (17)	C9—C10—H10A	109.9
C3—C4—N1	119.05 (15)	C11—C10—H10A	109.9
C5—C4—N1	120.28 (15)	C9—C10—H10B	109.9
C4—C5—C6	118.69 (17)	C11—C10—H10B	109.9
C4—C5—H5	120.7	H10A—C10—H10B	108.3
C6—C5—H5	120.7	O4—C11—O3	123.16 (14)
C1—C6—C5	122.06 (19)	O4—C11—C10	123.35 (15)
C1—C6—H6	119.0	O3—C11—C10	113.45 (15)
C5—C6—H6	119.0	C4—N1—H1A	107.0 (14)
C1—C7—H7A	109.5	C4—N1—H1B	109.3 (14)
C1—C7—H7B	109.5	H1A—N1—H1B	112 (2)
H7A—C7—H7B	109.5	C4—N1—H1C	111.8 (15)
C1—C7—H7C	109.5	H1A—N1—H1C	111 (2)
H7A—C7—H7C	109.5	H1B—N1—H1C	105.1 (19)
H7B—C7—H7C	109.5	C11—O3—H3A	108.4 (19)
O1—C8—O2	126.49 (14)	C9—O5—H5A	107 (2)

C6—C1—C2—C3	−0.6 (3)	C4—C5—C6—C1	0.1 (3)
C7—C1—C2—C3	179.1 (2)	O1—C8—C9—O5	−7.5 (2)
C1—C2—C3—C4	0.3 (3)	O2—C8—C9—O5	174.38 (14)
C2—C3—C4—C5	0.2 (3)	O1—C8—C9—C10	−130.05 (16)
C2—C3—C4—N1	179.61 (17)	O2—C8—C9—C10	51.8 (2)
C3—C4—C5—C6	−0.4 (3)	O5—C9—C10—C11	58.19 (18)
N1—C4—C5—C6	−179.80 (17)	C8—C9—C10—C11	−178.66 (13)
C2—C1—C6—C5	0.3 (3)	C9—C10—C11—O4	69.8 (2)
C7—C1—C6—C5	−179.3 (2)	C9—C10—C11—O3	−107.77 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1	0.82 (1)	2.12 (3)	2.6101 (15)	119 (2)
N1—H1A···O5	0.87 (1)	1.98 (1)	2.8381 (18)	172 (2)
N1—H1B···O1ⁱ	0.87 (1)	1.88 (1)	2.7328 (18)	168 (2)
N1—H1C···O2ⁱⁱ	0.87 (1)	2.01 (1)	2.8736 (19)	170 (2)
O3—H3A···O2ⁱ	0.83 (1)	1.75 (1)	2.5830 (16)	179 (3)
O5—H5A···O4ⁱⁱⁱ	0.82 (1)	2.26 (2)	2.8088 (18)	125 (2)

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

Acknowledgements

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

References

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