N,N′-Dicarb­oxy-N,N′-dicarboxyl­ato(m-phenyl­ene)dimethanaminium monohydrate

Yu-Xing Qiang; Shou-Rong Zhu; Min Shao

doi:10.1107/S1600536811013675

. 2011 Apr 22;67(Pt 5):o1174. doi: 10.1107/S1600536811013675

N,N′-Dicarboxy-N,N′-dicarboxylato(m-phenylene)dimethanaminium monohydrate

Yu-Xing Qiang ^a, Shou-Rong Zhu ^a,^*, Min Shao ^b

PMCID: PMC3089206 PMID: 21754479

Abstract

In the title inner salt, C₁₆H₂₀N₂O₈·H₂O, two of four carboxyl groups are deprotonated, while the two imine groups are protonated. The two iminodiacetate groups are located on the same side of the benzene ring plane. Extensive intermolecular O—H⋯O and N—H⋯O hydrogen bonds occur in the crystal.

Related literature

The title compound tends to form dinuclear metal complexes, which are capable of dioxygen activation, see: Furutachi et al. (2003 ▶); Zhao et al. (2008a ▶,b ▶). For the structures of aromatic-substituted iminodiacetic acids, see: Choquesillo-Lazarte et al. (2002 ▶); Sánchez-Moreno et al. (2003 ▶).

Experimental

Crystal data

C₁₆H₂₀N₂O₈·H₂O
M _r = 386.36
Monoclinic,
a = 22.491 (3) Å
b = 5.4342 (7) Å
c = 14.3118 (19) Å
β = 106.788 (2)°
V = 1674.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.975, T _max = 0.988
4927 measured reflections
1891 independent reflections
1701 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.069
S = 0.97
1891 reflections
252 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013675/xu5178sup1.cif

e-67-o1174-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013675/xu5178Isup2.hkl

e-67-o1174-Isup2.hkl^{(93.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O8ⁱ	0.96 (3)	2.46 (3)	3.216 (3)	135 (2)
N2—H2A⋯O6ⁱⁱ	0.97 (3)	2.03 (3)	2.896 (3)	148 (2)
O1W—H1WB⋯O8ⁱⁱ	0.85	2.02	2.847 (3)	165
O1W—H1WA⋯O7	0.85	1.88	2.729 (3)	174
O4—H4A⋯O1Wⁱⁱⁱ	0.85	1.71	2.552 (3)	171
O5—H5A⋯O1^iv	0.85	1.65	2.472 (3)	161

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

This research was supported by the National Natural Science Foundation of China (grant Nos. 20971084 and 20801035).

supplementary crystallographic information

Comment

The title compound tends to form dinuclear complexes with transition metal ions. The dinuclear complexes are capable for dioxygen activation (Furutachi et al., 2003; Zhao et al., 2008a). Structures of their dinuclear complexes have been reported. As a part of serial structural investigation of dioxygen activation by dinuclear complexes, the title compound was prepared in the laboratory and its X-ray structure is presented here.

The molecular structure of the title compound is shown in Fig.1. The compound is not symmetry as the scheme. The asymmetric moiety contains a whole molecule. There are two protons bind to two carboxylate group (O4 and O5). Two protons bind to the imino nitrogen atom N1 and N2 with N—H distances of 0.960 (27) and 0.968 (27)Å respectively, which is 0.1 Å longer than O—H distances (0.851 (2) Å. Different from its zinc(II) complex, the two iminodiacetic moiety are in the opposite side with respect to the central benzyl ring (Zhao et al., 2008a). The phenyl group, [C1/C2/C3/C4/C5/C6]and methylene C7 and C12 are in the same plane, but the N1/C7/C1 and N2/C12/C3 planes are almost perpendicular to the phenyl plane with dihedral angle of 89.4 (3) and 88.6 (3)° respectively, which is comparable to those in N-(p-nitrobenzyl)iminodiacetic acid (Sánchez-Moreno et al., 2003), but quite different from the almost coplanar geometry in N-(2-pyridylmethyl)iminodiacetic acid (Choquesillo-Lazarte et al., 2002). N1/C7/C1 and N2/C12/C3 planes have a dihydral angle of 59.7 (1)°. The bond lengths and angles are in normal ranges and comparable to the above mentioned compounds and its complex (Zhao et al., 2008a; Zhao et al., 2008b). In the compound, the two carboxylate for both iminoaiacetic group are far away with C(9)—C(11) and C(14)—C(16) diantances at 4.089 (3) and 4.667 (3)Å respectively. There are intermolecular H-bonds in the compound. No intramolecular H-bond found in the compound(Fig.2).This is quite different from N-(p-nitrobenzyl) iminodiacetic acid (Sánchez-Moreno et al., 2003) and N-(2-pyridylmethyl)iminodiacetic acid (Choquesillo-Lazarte et al., 2002). In these literatures, there is a proton binding to the imino nitrogen atom. There are N—H···O intramolecular H-bonds. In the title compound, carboxyalte O6/C14/O5 from other molecule links the molecules via O1 and N2 through H—bond to form a pseudo 15–membered ring [H5a/O5/C14/O6/H2a/N2/C12/C3/C2/C1/C7/N1/C10/C11/O1] (Fig.2). O5—H5A···O1ii has the shortest distance of 2.472 (3)Å in all H—bonds. N—H···O H—bond is much weaker than corresponding O—H···O H—bond. It is the intermolecular H-bonds that bind adjacent molecules as shown in Fig. 3 and table 2.

Experimental

To a mixture of bromoacetic acid (41.816 g, 0.30 mol) and lithium hydroxide monohydrate (12.627 g, 0.30 mol) in water (100 ml) containing phenolphthalein was added m-xylenediamine (10.0 g, 73.4 mmol). The reaction mixture was stirred at 70°C for 3 h and during the reaction, pH was maintained at 10 by addition of lithium hydroxide monohydrate (12.627 g, 0.30 mol). After the mixture cooled to ambient temperature, the solution was made acidic (pH = 1) by addition of conc. HCl to give white powder. Yield: 24.3 g (84%).

0.0194 g (0.05 mmol) of the white powder was added 0.5 ml 0.1 mol/L KOH solution, then 5 ml sub-boiled water was added to give a clear solution. Gradually add 0.1 mol/L HNO₃, to adjust the pH of the solution to 5. The solution was allowed to stand at room temperature for 3 days. Colorless block crystals suitable for crystal diffraction were obtained.