2,4,6-Trimethyl­anilinium 2-carb­oxy­ethano­ate

Rong, T.

doi:10.1107/S1600536811025578

organic compounds

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Volume 67| Part 8| August 2011| Page o1921

doi:10.1107/S1600536811025578

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2,4,6-Trimethylanilinium 2-carboxyethanoate

Tao Rong ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: rongtao198806@163.com

(Received 24 June 2011; accepted 29 June 2011; online 6 July 2011)

The anion of the title molecular salt, C₉H₁₄N⁺·C₃H₃O₄⁻, features an intramolecular O—H⋯O hydrogen bond. In the crystal, intermolecular N—H⋯O interactions link each cation to three different anions.

Related literature

For general background to ferroelectric organic frameworks, see: Ye et al. (2006 , 2009 ); Fu et al. (2007 ). For phase transition of ferroelectric materials, see: Zhang et al. (2008 ); Zhao et al. (2008 ).

Experimental

Crystal data

C₉H₁₄N⁺·C₃H₃O₄⁻
M_r = 239.27
Orthorhombic, P b c n
a = 13.732 (3) Å
b = 7.8522 (16) Å
c = 23.124 (5) Å
V = 2493.3 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.981, T_max = 0.981
23089 measured reflections
2856 independent reflections
1643 reflections with I > 2σ(I)
R_int = 0.096

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.166
S = 1.05
2856 reflections
162 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.99 (4)	1.46 (4)	2.421 (3)	160 (3)
N1—H1A⋯O4ⁱ	0.89	2.02	2.879 (3)	162
N1—H1A⋯O3ⁱ	0.89	2.51	3.248 (3)	140
N1—H1B⋯O1ⁱⁱ	0.89	2.09	2.826 (3)	140
N1—H1B⋯O4ⁱⁱⁱ	0.89	2.58	3.075 (3)	116
N1—H1C⋯O2^iv	0.89	1.92	2.798 (3)	167
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025578/bt5560sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025578/bt5560Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025578/bt5560Isup3.cml

checkCIF report

Comment top

In the crystal structure, one hydrogen –bonding network of N-H···O hydrogen bonds which established between ammonium groups and hydrogen malonateions, and one kind of intramolecular hydrogen bond O3—H···O1 which established between O3 and O1 contribute to the stability of crystal packing.

In the structure, atom N1 is hydrogen bonded to O atoms of hydrogen malonate ions through hydrogen bonds.

The study of ferroelectric materials has received much attention. Some materials have predominantly dielectric-ferroelectric properties. The title compound was studied as part of our work to obtain potential ferroelectric phase-transition materials (Ye et al., 2006; Fu et al., 2007; Zhao et al. 2008; Zhang et al., 2008; Ye et al., 2009). Unluckily, the compound has no dielectric anomalies in the temperature range 93–453 K, suggesting that it might be only a paraelectric.

Related literature top

For general background to ferroelectric organic frameworks, see: Ye et al. (2006, 2009); Fu et al. (2007). F for phase transition of ferroelectric materials, see: Zhang et al. (2008); Zhao et al. (2008).

Experimental top

For the preparation of the title compound, the Malonate(0.5 g) was added to the ehanol solution of the 2,4,6-trimethylaniline, The resulting precipitate was filtered. Colorless crystals suitable for X-ray analysis were formed after several weeks by solw evaporation of the solvent at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme.Displacement ellipsoids are drawn at the 30%
	Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

2,4,6-Trimethylanilinium 2-carboxyethanoate top

Crystal data top

C₉H₁₄N⁺·C₃H₃O₄⁻	F(000) = 1024
M_r = 239.27	D_x = 1.275 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2856 reflections
a = 13.732 (3) Å	θ = 3.0–27.5°
b = 7.8522 (16) Å	µ = 0.10 mm⁻¹
c = 23.124 (5) Å	T = 293 K
V = 2493.3 (9) Å³	Prism, colourless
Z = 8	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2856 independent reflections
Radiation source: fine-focus sealed tube	1643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.096
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.981, T_max = 0.981	l = −30→30
23089 measured reflections

Refinement top

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0663P)² + 0.8663P] where P = (F_o² + 2F_c²)/3
2856 reflections	(Δ/σ)_max = 0.006
162 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₉H₁₄N⁺·C₃H₃O₄⁻	V = 2493.3 (9) Å³
M_r = 239.27	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 13.732 (3) Å	µ = 0.10 mm⁻¹
b = 7.8522 (16) Å	T = 293 K
c = 23.124 (5) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	2856 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1643 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.981	R_int = 0.096
23089 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.22 e Å⁻³
2856 reflections	Δρ_min = −0.25 e Å⁻³
162 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

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

	x	y	z	U_iso*/U_eq
C1	0.4717 (2)	0.2519 (3)	0.49208 (11)	0.0488 (7)
C2	0.5594 (2)	0.2379 (3)	0.52056 (11)	0.0504 (7)
H2	0.6161	0.2628	0.5003	0.060*
C3	0.56763 (18)	0.1886 (3)	0.57795 (10)	0.0390 (6)
C4	0.48162 (17)	0.1522 (3)	0.60667 (9)	0.0309 (5)
C5	0.39102 (18)	0.1613 (3)	0.58021 (10)	0.0385 (6)
C6	0.3885 (2)	0.2122 (4)	0.52297 (11)	0.0507 (7)
H6	0.3285	0.2200	0.5045	0.061*
C7	0.4666 (3)	0.3072 (4)	0.42944 (12)	0.0738 (10)
H7A	0.4639	0.4292	0.4275	0.111*
H7B	0.4093	0.2601	0.4118	0.111*
H7C	0.5233	0.2673	0.4093	0.111*
C8	0.6659 (2)	0.1771 (5)	0.60677 (13)	0.0646 (9)
H8A	0.7156	0.2095	0.5798	0.097*
H8B	0.6770	0.0623	0.6194	0.097*
H8C	0.6675	0.2523	0.6395	0.097*
C9	0.2980 (2)	0.1207 (4)	0.61237 (13)	0.0593 (8)
H9A	0.3004	0.0055	0.6262	0.089*
H9B	0.2434	0.1337	0.5868	0.089*
H9C	0.2910	0.1971	0.6445	0.089*
C10	0.11880 (17)	1.0449 (3)	0.23443 (10)	0.0344 (6)
C11	0.15426 (18)	0.9020 (3)	0.27175 (10)	0.0364 (6)
H11A	0.1284	0.9190	0.3104	0.044*
H11B	0.2246	0.9107	0.2744	0.044*
C12	0.12942 (17)	0.7225 (3)	0.25311 (13)	0.0401 (6)
H3	0.092 (3)	0.881 (5)	0.1813 (14)	0.093 (12)*
N1	0.48497 (14)	0.1025 (2)	0.66800 (8)	0.0331 (5)
H1A	0.4588	0.1847	0.6895	0.050*
H1B	0.5466	0.0862	0.6786	0.050*
H1C	0.4515	0.0065	0.6730	0.050*
O1	0.13547 (14)	0.6067 (2)	0.28835 (10)	0.0624 (6)
O2	0.10416 (16)	0.7039 (2)	0.19982 (9)	0.0600 (6)
O3	0.08869 (16)	1.0069 (3)	0.18287 (8)	0.0581 (6)
O4	0.11846 (14)	1.1927 (2)	0.25102 (8)	0.0512 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.070 (2)	0.0448 (16)	0.0310 (15)	0.0047 (15)	0.0011 (13)	0.0036 (12)
C2	0.0576 (18)	0.0562 (18)	0.0374 (16)	−0.0033 (15)	0.0122 (13)	0.0065 (13)
C3	0.0417 (14)	0.0415 (15)	0.0338 (14)	−0.0005 (12)	0.0037 (11)	0.0027 (11)
C4	0.0416 (14)	0.0245 (12)	0.0267 (12)	0.0015 (10)	0.0033 (10)	0.0006 (9)
C5	0.0404 (15)	0.0372 (14)	0.0379 (15)	0.0017 (12)	−0.0008 (11)	0.0031 (11)
C6	0.0525 (17)	0.0608 (18)	0.0387 (16)	0.0050 (14)	−0.0126 (13)	0.0068 (13)
C7	0.112 (3)	0.078 (2)	0.0314 (16)	0.006 (2)	−0.0023 (16)	0.0119 (16)
C8	0.0426 (16)	0.096 (3)	0.0556 (19)	−0.0059 (17)	0.0061 (14)	0.0155 (17)
C9	0.0401 (16)	0.079 (2)	0.0588 (19)	−0.0012 (16)	0.0002 (13)	0.0134 (16)
C10	0.0336 (13)	0.0334 (14)	0.0363 (14)	0.0009 (11)	0.0002 (11)	0.0007 (11)
C11	0.0395 (13)	0.0313 (13)	0.0386 (14)	−0.0022 (11)	−0.0035 (11)	0.0027 (11)
C12	0.0257 (12)	0.0301 (13)	0.0644 (19)	−0.0020 (11)	0.0089 (12)	0.0039 (13)
N1	0.0402 (11)	0.0301 (10)	0.0288 (11)	0.0024 (9)	0.0028 (8)	0.0020 (9)
O1	0.0539 (13)	0.0328 (11)	0.1006 (17)	0.0015 (9)	0.0110 (11)	0.0256 (11)
O2	0.0772 (15)	0.0394 (11)	0.0633 (14)	−0.0112 (10)	−0.0046 (11)	−0.0167 (10)
O3	0.0844 (15)	0.0489 (13)	0.0410 (12)	0.0060 (11)	−0.0167 (10)	0.0007 (9)
O4	0.0643 (13)	0.0296 (10)	0.0596 (12)	0.0075 (9)	−0.0051 (9)	−0.0011 (9)

Geometric parameters (Å, º) top

C1—C2	1.376 (4)	C8—H8C	0.9600
C1—C6	1.384 (4)	C9—H9A	0.9600
C1—C7	1.514 (4)	C9—H9B	0.9600
C2—C3	1.387 (3)	C9—H9C	0.9600
C2—H2	0.9300	C10—O4	1.222 (3)
C3—C4	1.385 (3)	C10—O3	1.297 (3)
C3—C8	1.507 (4)	C10—C11	1.497 (3)
C4—C5	1.388 (3)	C11—C12	1.513 (3)
C4—N1	1.472 (3)	C11—H11A	0.9700
C5—C6	1.383 (3)	C11—H11B	0.9700
C5—C9	1.512 (4)	C12—O1	1.224 (3)
C6—H6	0.9300	C12—O2	1.289 (3)
C7—H7A	0.9600	N1—H1A	0.8900
C7—H7B	0.9600	N1—H1B	0.8900
C7—H7C	0.9600	N1—H1C	0.8900
C8—H8A	0.9600	O3—H3	0.99 (4)
C8—H8B	0.9600

C2—C1—C6	117.2 (2)	H8A—C8—H8C	109.5
C2—C1—C7	121.4 (3)	H8B—C8—H8C	109.5
C6—C1—C7	121.3 (3)	C5—C9—H9A	109.5
C1—C2—C3	123.5 (3)	C5—C9—H9B	109.5
C1—C2—H2	118.3	H9A—C9—H9B	109.5
C3—C2—H2	118.3	C5—C9—H9C	109.5
C4—C3—C2	116.5 (2)	H9A—C9—H9C	109.5
C4—C3—C8	122.6 (2)	H9B—C9—H9C	109.5
C2—C3—C8	120.9 (2)	O4—C10—O3	120.4 (2)
C3—C4—C5	122.8 (2)	O4—C10—C11	122.1 (2)
C3—C4—N1	119.4 (2)	O3—C10—C11	117.5 (2)
C5—C4—N1	117.8 (2)	C10—C11—C12	117.4 (2)
C6—C5—C4	117.3 (2)	C10—C11—H11A	107.9
C6—C5—C9	120.7 (2)	C12—C11—H11A	107.9
C4—C5—C9	122.0 (2)	C10—C11—H11B	107.9
C5—C6—C1	122.6 (2)	C12—C11—H11B	107.9
C5—C6—H6	118.7	H11A—C11—H11B	107.2
C1—C6—H6	118.7	O1—C12—O2	124.8 (3)
C1—C7—H7A	109.5	O1—C12—C11	119.2 (3)
C1—C7—H7B	109.5	O2—C12—C11	116.0 (2)
H7A—C7—H7B	109.5	C4—N1—H1A	109.5
C1—C7—H7C	109.5	C4—N1—H1B	109.5
H7A—C7—H7C	109.5	H1A—N1—H1B	109.5
H7B—C7—H7C	109.5	C4—N1—H1C	109.5
C3—C8—H8A	109.5	H1A—N1—H1C	109.5
C3—C8—H8B	109.5	H1B—N1—H1C	109.5
H8A—C8—H8B	109.5	C10—O3—H3	105 (2)
C3—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.99 (4)	1.46 (4)	2.421 (3)	160 (3)
N1—H1A···O4ⁱ	0.89	2.02	2.879 (3)	162
N1—H1A···O3ⁱ	0.89	2.51	3.248 (3)	140
N1—H1B···O1ⁱⁱ	0.89	2.09	2.826 (3)	140
N1—H1B···O4ⁱⁱⁱ	0.89	2.58	3.075 (3)	116
N1—H1C···O2^iv	0.89	1.92	2.798 (3)	167

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

Experimental details

Crystal data
Chemical formula	C₉H₁₄N⁺·C₃H₃O₄⁻
M_r	239.27
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	13.732 (3), 7.8522 (16), 23.124 (5)
V (Å³)	2493.3 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.981, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	23089, 2856, 1643
R_int	0.096
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.166, 1.05
No. of reflections	2856
No. of parameters	162
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.99 (4)	1.46 (4)	2.421 (3)	160 (3)
N1—H1A···O4ⁱ	0.89	2.02	2.879 (3)	162
N1—H1A···O3ⁱ	0.89	2.51	3.248 (3)	140
N1—H1B···O1ⁱⁱ	0.89	2.09	2.826 (3)	140
N1—H1B···O4ⁱⁱⁱ	0.89	2.58	3.075 (3)	116
N1—H1C···O2^iv	0.89	1.92	2.798 (3)	167

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

Acknowledgements

The author is grateful to the starter fund of Southeast University, Nanjing, People's Republic of China.

References

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