4-Ethyl­anilinium 2-carb­oxy­acetate

Wu, D.-H.; Wu, Q.-Q.

doi:10.1107/S1600536810029648

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2160

https://doi.org/10.1107/S1600536810029648

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4-Ethylanilinium 2-carboxyacetate

De-Hong Wu ^a ^* and Qi-Qi Wu ^a

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wudh1971@sohu.com

(Received 12 July 2010; accepted 26 July 2010; online 31 July 2010)

In the crystal structure of the title compound, C₈H₁₂N⁺·C₃H₃O₄⁻, the hydrogen malonate anions are linked into infinite chains parallel to the b axis by intermolecular O—H⋯O hydrogen bonds of the type COO⁻⋯HO₂C in a head-to-tail fashion. The 4-ethylanilinium cations link adjacent anion chains by intermolecular N—H⋯O hydrogen bonds into a two-dimensional network parallel to the b and c axes.

Related literature

For background to molecular–ionic compounds, see: Czupiński et al. (2002 ); Katrusiak & Szafrański (2006 ); Chen (2009 ); Wang (2010 ).

Experimental

Crystal data

C₈H₁₂N⁺·C₃H₃O₄⁻
M_r = 225.24
Monoclinic, P 2₁ /c
a = 13.439 (3) Å
b = 9.2914 (19) Å
c = 8.8827 (18) Å
β = 99.177 (10)°
V = 1095.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 291 K
0.36 × 0.32 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.963, T_max = 0.971
11013 measured reflections
2510 independent reflections
1995 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.161
S = 1.05
2510 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.89	2.08	2.777 (2)	134
N1—H1B⋯O1ⁱ	0.89	2.57	3.200 (3)	129
N1—H1B⋯O2ⁱⁱ	0.89	2.27	2.930 (2)	131
N1—H1C⋯O3ⁱⁱⁱ	0.89	2.31	2.815 (2)	116
N1—H1A⋯O4ⁱⁱ	0.89	2.28	2.885 (2)	125
O4—H4⋯O2^iv	0.91	1.64	2.532 (2)	167
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810029648/kj2151sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029648/kj2151Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to simple molecular–ionic crystals containing organic cations and anions due to the tunability of their special structural features and their interesting physical properties (Czupiński et al., 2002; Katrusiak & Szafrański, 2006). For similar structures, see: Chen, 2009; Wang, 2010. The title compound has been synthesized in our laboratory and its crystal structure is reported here.

The asymmetric unit of the title compound consists of one 4-ethylanilinium cation and one hydrogen malonate anion (Fig 1), in which complete transfer of a single H atom from the acid component to the basic component has occurred. In the crystal structure, the hydrogen malonate anions are linked into one-dimensional infinite chains parallel to b-axis by intermolecular O—H···O hydrogen bonds of the type COO^-···HO₂C in a "head-to-tail" fashion. The 4-ethylanilinium cations link adjacent anion chains by intermolecular N—H···O hydrogen bonds into a two-dimensional network running parallel to the b and c-axes .(Fig 2). Hydrogen bonds of intermolecular N—H···O and O—H···O make great contribution to the stability of the crystal structure (Table 1).

Related literature top

For background to molecular–ionic compounds, see: Czupiński et al. (2002); Katrusiak & Szafrański (2006); Chen (2009); Wang (2010).

Experimental top

1.04 g (10 mmol) malonic acid hydrate was dissolved in 50 ml ethanol, to which 1.21 g (10 mmol) 4-ethybenzenamine was added to afford a solution without any precipitation under stirring at ambient temperature. Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of the above solution after 3 days in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature range between 93 K and 362 K (m.p. 99 ^oC).

Structure description top

For background to molecular–ionic compounds, see: Czupiński et al. (2002); Katrusiak & Szafrański (2006); Chen (2009); Wang (2010).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

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

4-Ethylanilinium 2-carboxyacetate top

Crystal data top

C₈H₁₂N⁺·C₃H₃O₄⁻	F(000) = 480
M_r = 225.24	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9421 reflections
a = 13.439 (3) Å	θ = 3.1–27.6°
b = 9.2914 (19) Å	µ = 0.10 mm⁻¹
c = 8.8827 (18) Å	T = 291 K
β = 99.177 (10)°	Block, colorless
V = 1095.0 (4) Å³	0.36 × 0.32 × 0.28 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2510 independent reflections
Radiation source: fine-focus sealed tube	1995 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.963, T_max = 0.971	l = −11→11
11013 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0682P)² + 0.8364P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2510 reflections	Δρ_max = 0.42 e Å⁻³
147 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (5)

Crystal data top

C₈H₁₂N⁺·C₃H₃O₄⁻	V = 1095.0 (4) Å³
M_r = 225.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.439 (3) Å	µ = 0.10 mm⁻¹
b = 9.2914 (19) Å	T = 291 K
c = 8.8827 (18) Å	0.36 × 0.32 × 0.28 mm
β = 99.177 (10)°

Data collection top

Rigaku SCXmini diffractometer	2510 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1995 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.971	R_int = 0.042
11013 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.05	Δρ_max = 0.42 e Å⁻³
2510 reflections	Δρ_min = −0.43 e Å⁻³
147 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	0.90859 (14)	0.4455 (2)	0.0928 (2)	0.0260 (4)
C2	0.89084 (16)	0.3160 (2)	−0.0141 (2)	0.0290 (5)
H2A	0.8213	0.3177	−0.0645	0.035*
H2B	0.9332	0.3261	−0.0923	0.035*
C3	0.91163 (15)	0.1717 (2)	0.0613 (2)	0.0265 (4)
C4	0.3837 (2)	0.7987 (4)	0.3598 (4)	0.0718 (10)
H4A	0.3281	0.7797	0.4124	0.108*
H4B	0.3704	0.7573	0.2595	0.108*
H4C	0.3926	0.9008	0.3517	0.108*
C5	0.4769 (2)	0.7341 (4)	0.4458 (3)	0.0605 (8)
H5A	0.4657	0.6316	0.4555	0.073*
H5B	0.4877	0.7745	0.5478	0.073*
C6	0.57213 (18)	0.7548 (3)	0.3778 (3)	0.0405 (6)
C7	0.63668 (19)	0.6409 (3)	0.3677 (3)	0.0442 (6)
H7A	0.6205	0.5508	0.4025	0.053*
C8	0.72484 (18)	0.6569 (2)	0.3073 (3)	0.0388 (5)
H8A	0.7669	0.5785	0.3006	0.047*
C9	0.74915 (15)	0.7901 (2)	0.2574 (2)	0.0300 (5)
C10	0.68750 (17)	0.9066 (2)	0.2664 (3)	0.0388 (5)
H10A	0.7046	0.9967	0.2328	0.047*
C11	0.59904 (19)	0.8877 (3)	0.3267 (3)	0.0453 (6)
H11A	0.5570	0.9662	0.3327	0.054*
N1	0.84388 (13)	0.80909 (19)	0.1986 (2)	0.0347 (5)
H1A	0.8755	0.7249	0.1992	0.052*
H1B	0.8828	0.8714	0.2571	0.052*
H1C	0.8311	0.8426	0.1036	0.052*
O1	0.88090 (13)	0.56380 (16)	0.03767 (19)	0.0412 (4)
O2	0.95091 (12)	0.42353 (15)	0.22859 (17)	0.0352 (4)
O3	0.84347 (12)	0.08947 (16)	0.0783 (2)	0.0413 (4)
O4	1.00669 (11)	0.14348 (15)	0.10516 (18)	0.0337 (4)
H4	1.0153	0.0579	0.1549	0.105 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0251 (9)	0.0210 (9)	0.0323 (10)	−0.0010 (7)	0.0058 (8)	0.0015 (7)
C2	0.0335 (11)	0.0246 (10)	0.0277 (10)	−0.0018 (8)	0.0011 (8)	0.0019 (8)
C3	0.0333 (11)	0.0210 (9)	0.0261 (10)	−0.0025 (8)	0.0072 (8)	−0.0048 (7)
C4	0.0498 (17)	0.083 (2)	0.088 (2)	−0.0032 (16)	0.0301 (17)	0.0124 (19)
C5	0.0609 (18)	0.071 (2)	0.0559 (17)	0.0003 (15)	0.0279 (14)	0.0118 (15)
C6	0.0422 (13)	0.0461 (14)	0.0340 (11)	−0.0037 (10)	0.0088 (10)	0.0026 (10)
C7	0.0531 (15)	0.0344 (12)	0.0463 (14)	−0.0079 (11)	0.0117 (11)	0.0074 (10)
C8	0.0417 (13)	0.0267 (11)	0.0481 (13)	−0.0004 (9)	0.0074 (10)	0.0040 (9)
C9	0.0277 (10)	0.0285 (10)	0.0316 (10)	−0.0039 (8)	−0.0019 (8)	−0.0002 (8)
C10	0.0370 (12)	0.0269 (11)	0.0514 (14)	−0.0021 (9)	0.0037 (10)	0.0037 (9)
C11	0.0422 (13)	0.0398 (13)	0.0543 (15)	0.0065 (10)	0.0091 (11)	0.0003 (11)
N1	0.0280 (9)	0.0244 (9)	0.0497 (11)	−0.0017 (7)	0.0003 (8)	0.0051 (8)
O1	0.0511 (10)	0.0242 (8)	0.0454 (9)	0.0081 (7)	−0.0010 (7)	0.0041 (7)
O2	0.0499 (9)	0.0225 (7)	0.0305 (8)	0.0008 (6)	−0.0021 (7)	−0.0014 (6)
O3	0.0363 (9)	0.0264 (8)	0.0626 (11)	−0.0054 (6)	0.0118 (8)	0.0058 (7)
O4	0.0328 (8)	0.0222 (7)	0.0445 (9)	−0.0023 (6)	0.0010 (6)	0.0024 (6)

Geometric parameters (Å, º) top

C1—O1	1.237 (2)	C6—C7	1.381 (4)
C1—O2	1.265 (2)	C6—C11	1.383 (3)
C1—C2	1.528 (3)	C7—C8	1.384 (3)
C2—C3	1.505 (3)	C7—H7A	0.9300
C2—H2A	0.9700	C8—C9	1.372 (3)
C2—H2B	0.9700	C8—H8A	0.9300
C3—O3	1.220 (2)	C9—C10	1.373 (3)
C3—O4	1.301 (2)	C9—N1	1.462 (3)
C4—C5	1.485 (5)	C10—C11	1.390 (3)
C4—H4A	0.9600	C10—H10A	0.9300
C4—H4B	0.9600	C11—H11A	0.9300
C4—H4C	0.9600	N1—H1A	0.8900
C5—C6	1.512 (4)	N1—H1B	0.8900
C5—H5A	0.9700	N1—H1C	0.8900
C5—H5B	0.9700	O4—H4	0.9084

O1—C1—O2	125.59 (19)	C7—C6—C5	120.6 (2)
O1—C1—C2	116.51 (18)	C11—C6—C5	121.8 (2)
O2—C1—C2	117.89 (17)	C6—C7—C8	121.9 (2)
C3—C2—C1	115.15 (16)	C6—C7—H7A	119.1
C3—C2—H2A	108.5	C8—C7—H7A	119.1
C1—C2—H2A	108.5	C9—C8—C7	119.0 (2)
C3—C2—H2B	108.5	C9—C8—H8A	120.5
C1—C2—H2B	108.5	C7—C8—H8A	120.5
H2A—C2—H2B	107.5	C8—C9—C10	121.0 (2)
O3—C3—O4	123.86 (19)	C8—C9—N1	119.35 (19)
O3—C3—C2	121.53 (19)	C10—C9—N1	119.61 (19)
O4—C3—C2	114.60 (17)	C9—C10—C11	119.0 (2)
C5—C4—H4A	109.5	C9—C10—H10A	120.5
C5—C4—H4B	109.5	C11—C10—H10A	120.5
H4A—C4—H4B	109.5	C6—C11—C10	121.6 (2)
C5—C4—H4C	109.5	C6—C11—H11A	119.2
H4A—C4—H4C	109.5	C10—C11—H11A	119.2
H4B—C4—H4C	109.5	C9—N1—H1A	109.5
C4—C5—C6	116.2 (2)	C9—N1—H1B	109.5
C4—C5—H5A	108.2	H1A—N1—H1B	109.5
C6—C5—H5A	108.2	C9—N1—H1C	109.5
C4—C5—H5B	108.2	H1A—N1—H1C	109.5
C6—C5—H5B	108.2	H1B—N1—H1C	109.5
H5A—C5—H5B	107.4	C3—O4—H4	111.3
C7—C6—C11	117.6 (2)

O1—C1—C2—C3	−171.71 (18)	C6—C7—C8—C9	0.6 (4)
O2—C1—C2—C3	9.0 (3)	C7—C8—C9—C10	−0.1 (3)
C1—C2—C3—O3	108.1 (2)	C7—C8—C9—N1	177.8 (2)
C1—C2—C3—O4	−72.1 (2)	C8—C9—C10—C11	−0.3 (3)
C4—C5—C6—C7	−134.2 (3)	N1—C9—C10—C11	−178.2 (2)
C4—C5—C6—C11	47.1 (4)	C7—C6—C11—C10	0.3 (4)
C11—C6—C7—C8	−0.7 (4)	C5—C6—C11—C10	179.0 (2)
C5—C6—C7—C8	−179.4 (3)	C9—C10—C11—C6	0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.89	2.08	2.777 (2)	134
N1—H1B···O1ⁱ	0.89	2.57	3.200 (3)	129
N1—H1B···O2ⁱⁱ	0.89	2.27	2.930 (2)	131
N1—H1C···O3ⁱⁱⁱ	0.89	2.31	2.815 (2)	116
N1—H1A···O4ⁱⁱ	0.89	2.28	2.885 (2)	125
O4—H4···O2^iv	0.91	1.64	2.532 (2)	167

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·C₃H₃O₄⁻
M_r	225.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	13.439 (3), 9.2914 (19), 8.8827 (18)
β (°)	99.177 (10)
V (Å³)	1095.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.36 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.963, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	11013, 2510, 1995
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.161, 1.05
No. of reflections	2510
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.43

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.89	2.08	2.777 (2)	134.1
N1—H1B···O1ⁱ	0.89	2.57	3.200 (3)	128.6
N1—H1B···O2ⁱⁱ	0.89	2.27	2.930 (2)	130.7
N1—H1C···O3ⁱⁱⁱ	0.89	2.31	2.815 (2)	115.6
N1—H1A···O4ⁱⁱ	0.89	2.28	2.885 (2)	124.6
O4—H4···O2^iv	0.91	1.64	2.532 (2)	167.2

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

Acknowledgements

D-HW thanks the China Postdoctoral Science Foundation funded project (20090451147), Jiangsu Planned Projects for Postdoctoral Research Funds (0802003B) and the SEU Major Postdoctoral Research Funds (3212000901) for financial support.

References

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