Ethane-1,2-diaminium (R)-2-[4-(1-carboxyl­atoeth­oxy)phen­oxy]acetate

Ren, C.-Y.; Hou, G.-F.; Yu, Y.-H.; Gao, J.-S.

doi:10.1107/S1600536811054535

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o223

doi:10.1107/S1600536811054535

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Ethane-1,2-diaminium (R)-2-[4-(1-carboxylatoethoxy)phenoxy]acetate

Chang-Yue Ren,^a Guang-Feng Hou,^a Ying-Hui Yu ^a and Jin-Sheng Gao ^a ^*

^aEngineering Research Center of Pesticides of Heilongjiang University, Heilongjiang University, Harbin 150050, People's Republic of China, and College of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 4 December 2011; accepted 19 December 2011; online 23 December 2011)

In the title compound, C₂H₁₀N₂²⁺·C₁₁H₁₀O₆²⁻, the two acetate groups of the cation form dihedral angles of 74.2 (4) and 63.9 (5)° with the central benzene ring. In the crystal, N—H⋯O hydrogen bonds link the cations and anions into layers parallel to the ab plane.

Related literature

For the synthesis of the title chiral carboxylic acid, see: Bezwada et al. (2007 ). For the structure of a similar achiral carboxylic acid, see: Gong et al. (2010 ).

Experimental

Crystal data

C₂H₁₀N₂²⁺·C₁₁H₁₀O₆²⁻
M_r = 300.31
Monoclinic, P 2₁
a = 10.066 (2) Å
b = 6.7887 (14) Å
c = 11.050 (2) Å
β = 99.30 (3)°
V = 745.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.62 × 0.10 × 0.06 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.937, T_max = 0.994
7250 measured reflections
3288 independent reflections
1855 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.176
S = 1.01
3288 reflections
209 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H33⋯O2ⁱ	0.90 (1)	1.86 (2)	2.736 (5)	164 (4)
N1—H32⋯O3	0.91 (1)	1.88 (1)	2.784 (5)	174 (5)
N1—H31⋯O3ⁱⁱ	0.90 (1)	1.94 (3)	2.764 (5)	150 (5)
N2—H34⋯O5	0.90 (1)	1.86 (2)	2.736 (5)	166 (5)
N2—H35⋯O5ⁱⁱⁱ	0.90 (1)	1.94 (3)	2.748 (5)	148 (5)
N2—H36⋯O6^iv	0.90 (1)	1.84 (1)	2.736 (5)	172 (5)
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y-{\script{1\over 2}}, -z]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811054535/cv5213sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054535/cv5213Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054535/cv5213Isup3.cml

checkCIF report

Comment top

The chiral ligands became one of the focus in supramolecular research due to their wide applications in catalytic and pharmaceutical industry. There are many reports about aromatic carboxylic acid, such as 4-carboxyphenoxyacetic acid (Gong et al., 2010). However, structural reports about chiral carboxylic acids are rare. Herein, we report the synthesis and structure of a new chiral aromatic carboxylic acid derivative.

The asymmertric unit of title compound contains one (R)-2-(4-(1-carboxyethoxy)phenoxy)acetate anion and one ethane-1,2-diaminium cation (Fig. 1). Two acetate groups of the anion twist towards the same side of the benzenyl plane with the torsion angles of 105.8 (4) and 116.1 (5) °, respectively. A double layers structure parallel to the ab plane is built up by N—H···O hydrogen bonds linking the anions and cations (Fig. 2, Table 1).

Related literature top

For the synthesis of the title chiral carboxylic acid, see: Bezwada et al. (2007). For the structure of a similar achiral carboxylic acid, see: Gong et al. (2010).

Experimental top

(R)-2-(4-(carboxymethoxy)phenoxy)propanoic acid was prepared by the reaction of R-(+)-2-(4-hydroxy-phenoxy)propionic acid and methyl chloroacetate under alkaline condition (Bezwada et al., 2007). (R)-2-(4-(carboxymethoxy)phenoxy)propanoic acid (0.048 g, 0.2 mmol) and ethylenediamine (1 mL, 0.2 mol / L) were dissolved in ethanol (15 mL). After stirring for 1 hour, the solution was filtered, and the filtrate was allowed to stand in a desiccator at room temperature for a few days. Colourless block crystals of title compound were obtained.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
	Fig. 2. A partial packing view showing the intermolecular hydrogen bonds as dashed lines.

Ethane-1,2-diaminium (R)-2-[4-(1-carboxylatoethoxy)phenoxy]acetate top

Crystal data top

C₂H₁₀N₂²⁺·C₁₁H₁₀O₆²⁻	F(000) = 320
M_r = 300.31	D_x = 1.338 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4706 reflections
a = 10.066 (2) Å	θ = 3.0–27.6°
b = 6.7887 (14) Å	µ = 0.11 mm⁻¹
c = 11.050 (2) Å	T = 293 K
β = 99.30 (3)°	Needle, colorless
V = 745.2 (3) Å³	0.62 × 0.10 × 0.06 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	3288 independent reflections
Radiation source: fine-focus sealed tube	1855 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scan	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→12
T_min = 0.937, T_max = 0.994	k = −8→8
7250 measured reflections	l = −14→14

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.081P)²] where P = (F_o² + 2F_c²)/3
3288 reflections	(Δ/σ)_max < 0.001
209 parameters	Δρ_max = 0.40 e Å⁻³
7 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂H₁₀N₂²⁺·C₁₁H₁₀O₆²⁻	V = 745.2 (3) Å³
M_r = 300.31	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 10.066 (2) Å	µ = 0.11 mm⁻¹
b = 6.7887 (14) Å	T = 293 K
c = 11.050 (2) Å	0.62 × 0.10 × 0.06 mm
β = 99.30 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3288 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1855 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.994	R_int = 0.066
7250 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	7 restraints
wR(F²) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.40 e Å⁻³
3288 reflections	Δρ_min = −0.21 e Å⁻³
209 parameters

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. 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.

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

	x	y	z	U_iso*/U_eq
C1	0.2605 (4)	0.7401 (6)	0.3560 (4)	0.0435 (9)
C2	0.3465 (5)	0.8903 (5)	0.3366 (4)	0.0501 (11)
H2	0.3145	1.0187	0.3261	0.060*
C3	0.4808 (4)	0.8504 (6)	0.3325 (4)	0.0505 (11)
H3	0.5387	0.9525	0.3199	0.061*
C4	0.5296 (4)	0.6592 (6)	0.3471 (4)	0.0481 (10)
C5	0.4409 (4)	0.5082 (6)	0.3668 (4)	0.0508 (11)
H5	0.4718	0.3790	0.3761	0.061*
C6	0.3102 (5)	0.5494 (6)	0.3723 (4)	0.0506 (10)
H6	0.2528	0.4481	0.3872	0.061*
C7	0.0731 (4)	0.9589 (6)	0.3553 (4)	0.0491 (10)
H7	0.1321	1.0400	0.4148	0.059*
C8	0.0612 (4)	1.0535 (6)	0.2292 (4)	0.0462 (10)
C9	−0.0588 (6)	0.9415 (10)	0.3946 (6)	0.0858 (17)
H9A	−0.0492	0.8721	0.4712	0.129*
H9B	−0.1191	0.8704	0.3337	0.129*
H9C	−0.0945	1.0705	0.4045	0.129*
C10	0.7100 (5)	0.4428 (7)	0.3237 (4)	0.0550 (11)
H10A	0.6920	0.3635	0.3922	0.066*
H10B	0.8068	0.4469	0.3267	0.066*
C11	0.6471 (4)	0.3445 (6)	0.2061 (4)	0.0477 (10)
C12	0.2339 (4)	0.5461 (6)	0.0488 (4)	0.0479 (10)
H12A	0.3012	0.5738	0.1200	0.057*
H12B	0.2407	0.6461	−0.0126	0.057*
C13	0.2592 (4)	0.3446 (6)	−0.0019 (4)	0.0519 (11)
H13A	0.2658	0.2478	0.0634	0.062*
H13B	0.1838	0.3085	−0.0642	0.062*
N1	0.0972 (3)	0.5515 (5)	0.0840 (3)	0.0455 (8)
H31	0.025 (3)	0.541 (8)	0.024 (3)	0.068*
H32	0.086 (5)	0.678 (3)	0.106 (4)	0.068*
H33	0.066 (4)	0.455 (5)	0.128 (4)	0.068*
N2	0.3835 (4)	0.3422 (5)	−0.0555 (3)	0.0475 (8)
H34	0.446 (4)	0.367 (8)	0.010 (3)	0.071*
H35	0.392 (5)	0.237 (5)	−0.103 (4)	0.071*
H36	0.369 (5)	0.441 (5)	−0.111 (4)	0.071*
O1	0.1245 (3)	0.7630 (4)	0.3592 (3)	0.0525 (8)
O2	0.0518 (4)	1.2367 (4)	0.2264 (3)	0.0759 (11)
O3	0.0581 (3)	0.9464 (4)	0.1361 (3)	0.0542 (7)
O4	0.6629 (3)	0.6369 (4)	0.3379 (3)	0.0578 (8)
O5	0.5970 (3)	0.4524 (4)	0.1170 (3)	0.0576 (8)
O6	0.6516 (4)	0.1649 (5)	0.2056 (3)	0.0761 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.057 (3)	0.043 (2)	0.032 (2)	−0.006 (2)	0.0121 (18)	−0.0019 (17)
C2	0.075 (3)	0.0274 (19)	0.047 (3)	−0.0075 (18)	0.009 (2)	−0.0032 (16)
C3	0.058 (3)	0.044 (2)	0.051 (3)	−0.010 (2)	0.013 (2)	−0.008 (2)
C4	0.062 (3)	0.042 (2)	0.040 (2)	−0.007 (2)	0.005 (2)	−0.0107 (19)
C5	0.065 (3)	0.050 (3)	0.038 (2)	−0.001 (2)	0.011 (2)	0.0002 (18)
C6	0.068 (3)	0.040 (2)	0.045 (3)	−0.012 (2)	0.011 (2)	0.001 (2)
C7	0.057 (2)	0.047 (2)	0.048 (3)	−0.005 (2)	0.020 (2)	−0.002 (2)
C8	0.051 (2)	0.038 (2)	0.052 (3)	−0.004 (2)	0.014 (2)	0.0020 (19)
C9	0.085 (4)	0.080 (4)	0.100 (5)	0.011 (3)	0.038 (3)	0.022 (3)
C10	0.061 (3)	0.051 (2)	0.053 (3)	0.001 (2)	0.009 (2)	−0.005 (2)
C11	0.063 (3)	0.042 (2)	0.040 (3)	−0.006 (2)	0.013 (2)	0.001 (2)
C12	0.058 (3)	0.045 (2)	0.041 (2)	−0.003 (2)	0.0112 (19)	−0.004 (2)
C13	0.053 (3)	0.046 (2)	0.059 (3)	−0.0021 (19)	0.014 (2)	−0.009 (2)
N1	0.052 (2)	0.0373 (17)	0.048 (2)	0.0015 (17)	0.0123 (16)	−0.0024 (17)
N2	0.057 (2)	0.0417 (18)	0.043 (2)	0.0041 (18)	0.0071 (17)	−0.0041 (16)
O1	0.0629 (18)	0.0382 (14)	0.060 (2)	0.0010 (14)	0.0213 (15)	0.0086 (13)
O2	0.118 (3)	0.0369 (17)	0.079 (3)	−0.0101 (18)	0.033 (2)	0.0051 (15)
O3	0.0700 (19)	0.0511 (16)	0.0407 (18)	0.0024 (15)	0.0066 (14)	−0.0018 (14)
O4	0.0515 (17)	0.0547 (18)	0.067 (2)	−0.0070 (15)	0.0098 (15)	−0.0218 (15)
O5	0.076 (2)	0.0496 (16)	0.0442 (18)	−0.0125 (16)	0.0013 (15)	0.0015 (15)
O6	0.125 (3)	0.0359 (17)	0.072 (2)	−0.0122 (19)	0.027 (2)	−0.0036 (15)

Geometric parameters (Å, º) top

C1—C2	1.377 (6)	C9—H9C	0.9600
C1—O1	1.384 (5)	C10—O4	1.418 (5)
C1—C6	1.389 (6)	C10—C11	1.507 (6)
C2—C3	1.387 (6)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.387 (6)	C11—O6	1.221 (5)
C3—H3	0.9300	C11—O5	1.264 (5)
C4—O4	1.371 (5)	C12—N1	1.489 (5)
C4—C5	1.399 (6)	C12—C13	1.516 (5)
C5—C6	1.356 (6)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—H6	0.9300	C13—N2	1.468 (6)
C7—O1	1.426 (5)	C13—H13A	0.9700
C7—C9	1.467 (6)	C13—H13B	0.9700
C7—C8	1.522 (6)	N1—H31	0.904 (10)
C7—H7	0.9800	N1—H32	0.907 (10)
C8—O2	1.247 (5)	N1—H33	0.900 (10)
C8—O3	1.256 (5)	N2—H34	0.898 (10)
C9—H9A	0.9600	N2—H35	0.900 (10)
C9—H9B	0.9600	N2—H36	0.900 (10)

C2—C1—O1	124.8 (4)	O4—C10—H10A	108.8
C2—C1—C6	119.2 (4)	C11—C10—H10A	108.8
O1—C1—C6	116.0 (4)	O4—C10—H10B	108.8
C1—C2—C3	120.1 (4)	C11—C10—H10B	108.8
C1—C2—H2	120.0	H10A—C10—H10B	107.7
C3—C2—H2	120.0	O6—C11—O5	125.9 (4)
C2—C3—C4	120.5 (4)	O6—C11—C10	115.8 (4)
C2—C3—H3	119.7	O5—C11—C10	118.3 (4)
C4—C3—H3	119.7	N1—C12—C13	109.6 (3)
O4—C4—C3	115.3 (4)	N1—C12—H12A	109.7
O4—C4—C5	126.0 (4)	C13—C12—H12A	109.7
C3—C4—C5	118.8 (4)	N1—C12—H12B	109.7
C6—C5—C4	120.2 (4)	C13—C12—H12B	109.7
C6—C5—H5	119.9	H12A—C12—H12B	108.2
C4—C5—H5	119.9	N2—C13—C12	111.3 (3)
C5—C6—C1	121.2 (4)	N2—C13—H13A	109.4
C5—C6—H6	119.4	C12—C13—H13A	109.4
C1—C6—H6	119.4	N2—C13—H13B	109.4
O1—C7—C9	104.9 (4)	C12—C13—H13B	109.4
O1—C7—C8	113.3 (4)	H13A—C13—H13B	108.0
C9—C7—C8	111.3 (4)	C12—N1—H31	119 (3)
O1—C7—H7	109.0	C12—N1—H32	105 (3)
C9—C7—H7	109.0	H31—N1—H32	99 (4)
C8—C7—H7	109.0	C12—N1—H33	122 (3)
O2—C8—O3	124.5 (4)	H31—N1—H33	91 (4)
O2—C8—C7	116.0 (4)	H32—N1—H33	118 (5)
O3—C8—C7	119.6 (4)	C13—N2—H34	102 (3)
C7—C9—H9A	109.5	C13—N2—H35	114 (3)
C7—C9—H9B	109.5	H34—N2—H35	120 (5)
H9A—C9—H9B	109.5	C13—N2—H36	102 (3)
C7—C9—H9C	109.5	H34—N2—H36	115 (5)
H9A—C9—H9C	109.5	H35—N2—H36	102 (4)
H9B—C9—H9C	109.5	C1—O1—C7	117.4 (3)
O4—C10—C11	113.9 (4)	C4—O4—C10	117.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H33···O2ⁱ	0.90 (1)	1.86 (2)	2.736 (5)	164 (4)
N1—H32···O3	0.91 (1)	1.88 (1)	2.784 (5)	174 (5)
N1—H31···O3ⁱⁱ	0.90 (1)	1.94 (3)	2.764 (5)	150 (5)
N2—H34···O5	0.90 (1)	1.86 (2)	2.736 (5)	166 (5)
N2—H35···O5ⁱⁱⁱ	0.90 (1)	1.94 (3)	2.748 (5)	148 (5)
N2—H36···O6^iv	0.90 (1)	1.84 (1)	2.736 (5)	172 (5)

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

Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·C₁₁H₁₀O₆²⁻
M_r	300.31
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	10.066 (2), 6.7887 (14), 11.050 (2)
β (°)	99.30 (3)
V (Å³)	745.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.62 × 0.10 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.937, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	7250, 3288, 1855
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.176, 1.01
No. of reflections	3288
No. of parameters	209
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.21

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), 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—H33···O2ⁱ	0.900 (10)	1.858 (17)	2.736 (5)	164 (4)
N1—H32···O3	0.907 (10)	1.880 (12)	2.784 (5)	174 (5)
N1—H31···O3ⁱⁱ	0.904 (10)	1.94 (3)	2.764 (5)	150 (5)
N2—H34···O5	0.898 (10)	1.858 (17)	2.736 (5)	166 (5)
N2—H35···O5ⁱⁱⁱ	0.900 (10)	1.94 (3)	2.748 (5)	148 (5)
N2—H36···O6^iv	0.900 (10)	1.841 (14)	2.736 (5)	172 (5)

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

Acknowledgements

The authors thank the Project of Innovation Service Platform of Heilongjiang Province (PG09J001) and Heilongjiang University for supporting this work.

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