2,2′,2′′,2′′′-(1,4-Phenyl­enedinitrilo)­tetra­acetic acid dihydrate

Yan, J.; Ma, L.; Zhu, M.; Zhang, X.; Ge, C.

doi:10.1107/S1600536812019095

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1623

doi:10.1107/S1600536812019095

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2,2′,2′′,2′′′-(1,4-Phenylenedinitrilo)tetraacetic acid dihydrate

Juanzhi Yan,^a,^b Ling Ma,^c Miaoli Zhu,^a ^* Xiangdong Zhang ^d and Chunhua Ge ^d ^*

^aInstitute of Molecular Science, Chemical Biology and Molecular Engineering Laboratory of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China, ^bEducation Institute of Taiyuan University, Taiyuan, Shanxi 030001, People's Republic of China, ^cDepartment of Biochemistry and Molecular Biology, Shanxi Medical University, Taiyuan, Shanxi 030001, People's Republic of China, and ^dCollege of Chemistry, Liaoning University, Shengyang 110036, People's Republic of China
^*Correspondence e-mail: miaoli@sxu.edu.cn, chhge@lnu.edu.cn

(Received 24 April 2012; accepted 27 April 2012; online 5 May 2012)

In the title compound, C₁₄H₁₆N₂O₈·2H₂O, the complete organic molecule is generated by crystallographic inversion symmetry. The dihedral angles between the aniline ring and the acetic acid groups are almost identical, viz. 82.61 (7) and 80.33 (7)°. In the crystal, O—H⋯O hydrogen bonds link the organic molecules and water molecules, forming zigzag chains the c axis. An intramolecular O—H⋯O hydrogen bond is also observed.

Related literature

For the crystal structures of metal complexes of the title compound, see: González et al. (1997 ); Hao, Li, Chen & Zhang (2006 ); Hao, Li, Chen, Zhang et al. (2006 ); Zhang et al. (2007 ). For synthetic details, see: Zhang et al. (2007).

Experimental

Crystal data

C₁₄H₁₆N₂O₈·2H₂O
M_r = 376.32
Triclinic, $[P \overline 1]$
a = 5.1446 (12) Å
b = 8.4165 (19) Å
c = 9.953 (2) Å
α = 76.656 (4)°
β = 88.177 (4)°
γ = 85.715 (4)°
V = 418.12 (16) Å³
Z = 1
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.975, T_max = 0.975
2170 measured reflections
1458 independent reflections
1136 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.119
S = 1.04
1458 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.15 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
O5—H5B⋯O2ⁱ	0.86	2.13	2.819 (3)	137
O5—H5A⋯O2ⁱⁱ	0.92	2.25	3.035 (3)	143
O4—H4⋯O5	0.82	1.78	2.597 (3)	171
O1—H1⋯O3	0.82	1.86	2.653 (2)	164
Symmetry codes: (i) x+1, y+1, z; (ii) -x+1, -y, -z+2.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and SHELXL97; software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812019095/wn2473sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019095/wn2473Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019095/wn2473Isup3.cml

checkCIF report

Comment top

In recent research, the 2,2',2'',2'''-(1,4-phenylenebis(azanetriyl))tetraacetic acid ligand (H₄dbta) formed metal complexes.(González et al., 1997; Hao,Li, Chen, Zhang et al., 2006; Hao, Li, Chen, & Zhang, 2006; Zhang, et al., 2007). We expected to synthesize zinc complexes by the reaction of H₄dbta with zinc chloride in water. However, colorless crystals of the title compound were obtained by evaporation of the solvent.

The crystal structure of the title compound, C₁₄H₁₆N₂O₈.2H₂O, is centrosymmetric. The structure of the complete organic molecule and on independent water molecule are shown in Fig. 1. The dihedral angle between the plane C1/C2/C3/N1 and the plane C4/C5/O1/O2 is 82.61 (7)°, that between the plane C1/C2/C3/N1 and the plane C6/C7/O3/O4 is 80.33 (7)°.

O—H···O hydrogen bonds link the organic molecules and water molecules, forming zigzag chains (Fig. 2) An intramolecular O—H···O hydrogen bond is also observed (Fig. 1 and Table 1).

Related literature top

For the crystal structures of metal complexes of the title compound, see: González et al. (1997); Hao, Li, Chen & Zhang (2006); Hao, Li, Chen, Zhang et al. (2006); Zhang et al. (2007). For synthetic details, see: Zhang et al. (2007).

Experimental top

All reagents were of analytical grade and used without further purification. 2,2',2'',2'''-(1,4-Phenylenebis(azanetriyl))tetraacetic acid(H₄dbta) was synthesized by a previously reported method (Zhang et al., 2007). H₄dbta (0.17 g,0.5 mmol) and ZnCl₂ (0.136 g, 1.0 mmol) were mixed in 15 mL of water. The pH value of the solution was adjusted to 1.0 by HCl. The clear solution was allowed to stand at 323 K for 8 h. It was then filtered and the filtrate was kept at 277 K , allowing slow evaporation. After several weeks, purple single crystals of the title compound were obtained. Yield: 28%.

Selected IR(KBr, cm^-1): 3455(s), 1723(s), 1656(s), 1527(s), 1446(m),1367(s), 1320(m), 1252(m), 1230(m), 1190(m), 972(m), 888(m), 806(m),736(m). The infrared spectra of the title compound near 3455 cm^-1 for O—H stretching frequency showed that water of solvation existed in the crystal structure. The strong band at 1723 cm^-1 corresponds to the C=O stretching frequency of the carboxyl group.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of the organic molecule and one independent water molecule, showing displacement ellipsoids drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius. The dashed lines represent hydrogen bonds. Symmetry code: i) 1 -x, -y, 1 - z.
	Fig. 2. The packing of the crystal structure, showing the zigzag chains and a wave-like layer formed by O—H···O hydrogen bonds (dotted lines). H atoms not involved in the hydrogen bond interactions have been omitted for clarity.

2,2',2'',2'''-(1,4-Phenylenedinitrilo)tetraacetic acid dihydrate top

Crystal data top

C₁₄H₁₆N₂O₈·2H₂O	Z = 1
M_r = 376.32	F(000) = 198
Triclinic, P1	D_x = 1.495 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1446 (12) Å	Cell parameters from 694 reflections
b = 8.4165 (19) Å	θ = 2.5–25.4°
c = 9.953 (2) Å	µ = 0.13 mm⁻¹
α = 76.656 (4)°	T = 298 K
β = 88.177 (4)°	Block, purple
γ = 85.715 (4)°	0.20 × 0.20 × 0.20 mm
V = 418.12 (16) Å³

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1458 independent reflections
Radiation source: fine-focus sealed tube	1136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −5→6
T_min = 0.975, T_max = 0.975	k = −9→9
2170 measured reflections	l = −7→11

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0562P)² + 0.147P] where P = (F_o² + 2F_c²)/3
1458 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₆N₂O₈·2H₂O	γ = 85.715 (4)°
M_r = 376.32	V = 418.12 (16) Å³
Triclinic, P1	Z = 1
a = 5.1446 (12) Å	Mo Kα radiation
b = 8.4165 (19) Å	µ = 0.13 mm⁻¹
c = 9.953 (2) Å	T = 298 K
α = 76.656 (4)°	0.20 × 0.20 × 0.20 mm
β = 88.177 (4)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1458 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	1136 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.975	R_int = 0.014
2170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	Δρ_max = 0.15 e Å⁻³
1458 reflections	Δρ_min = −0.21 e Å⁻³
120 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	0.2990 (4)	0.0540 (2)	0.58341 (19)	0.0294 (5)
C2	0.4610 (4)	0.1632 (2)	0.5005 (2)	0.0326 (5)
H2	0.4370	0.2740	0.4998	0.039*
C3	0.3429 (4)	−0.1104 (3)	0.5810 (2)	0.0322 (5)
H3	0.2384	−0.1866	0.6353	0.039*
C4	−0.0514 (4)	−0.0116 (3)	0.7566 (2)	0.0357 (5)
H4A	−0.1229	−0.0793	0.7021	0.043*
H4B	−0.1969	0.0462	0.7934	0.043*
C5	0.0940 (4)	−0.1225 (3)	0.8765 (2)	0.0361 (5)
C6	0.0618 (4)	0.2780 (3)	0.6670 (2)	0.0389 (5)
H6A	−0.1036	0.2976	0.7121	0.047*
H6B	0.0541	0.3419	0.5725	0.047*
C7	0.2789 (5)	0.3343 (3)	0.7411 (2)	0.0383 (5)
N1	0.1002 (3)	0.1069 (2)	0.66661 (17)	0.0324 (4)
O1	0.2911 (3)	−0.0650 (2)	0.92636 (16)	0.0483 (5)
H1	0.3127	0.0279	0.8814	0.072*
O2	0.0295 (4)	−0.2586 (2)	0.92856 (18)	0.0547 (5)
O3	0.4170 (3)	0.2397 (2)	0.82357 (17)	0.0483 (5)
O4	0.3047 (4)	0.4915 (2)	0.7071 (2)	0.0627 (6)
H4	0.4199	0.5141	0.7532	0.094*
O5	0.6861 (4)	0.5278 (3)	0.8597 (2)	0.0822 (7)
H5A	0.6992	0.4518	0.9430	0.123*
H5B	0.7121	0.6234	0.8727	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0321 (11)	0.0326 (11)	0.0241 (10)	−0.0036 (9)	−0.0052 (8)	−0.0065 (8)
C2	0.0418 (13)	0.0264 (11)	0.0300 (11)	−0.0033 (9)	−0.0028 (9)	−0.0069 (8)
C3	0.0368 (12)	0.0321 (11)	0.0280 (11)	−0.0099 (9)	−0.0011 (9)	−0.0052 (8)
C4	0.0328 (12)	0.0411 (13)	0.0347 (12)	−0.0073 (10)	0.0016 (9)	−0.0110 (10)
C5	0.0380 (13)	0.0375 (13)	0.0341 (12)	−0.0078 (10)	0.0018 (9)	−0.0097 (9)
C6	0.0370 (13)	0.0352 (12)	0.0437 (13)	0.0019 (10)	−0.0030 (10)	−0.0088 (10)
C7	0.0406 (13)	0.0338 (12)	0.0429 (13)	−0.0051 (10)	0.0081 (10)	−0.0139 (10)
N1	0.0328 (10)	0.0331 (10)	0.0321 (9)	−0.0034 (7)	0.0001 (7)	−0.0092 (7)
O1	0.0570 (11)	0.0431 (10)	0.0418 (9)	−0.0155 (8)	−0.0174 (8)	0.0026 (7)
O2	0.0653 (12)	0.0403 (10)	0.0558 (11)	−0.0186 (9)	−0.0060 (9)	−0.0004 (8)
O3	0.0539 (11)	0.0426 (10)	0.0487 (10)	−0.0109 (8)	−0.0130 (8)	−0.0069 (8)
O4	0.0733 (15)	0.0322 (10)	0.0833 (15)	−0.0093 (9)	−0.0134 (11)	−0.0115 (9)
O5	0.0968 (17)	0.0633 (14)	0.0892 (16)	−0.0345 (12)	−0.0230 (13)	−0.0107 (11)

Geometric parameters (Å, º) top

C1—C3	1.391 (3)	C5—O1	1.313 (3)
C1—C2	1.393 (3)	C6—N1	1.440 (3)
C1—N1	1.406 (3)	C6—C7	1.519 (3)
C2—C3ⁱ	1.385 (3)	C6—H6A	0.9700
C2—H2	0.9300	C6—H6B	0.9700
C3—C2ⁱ	1.385 (3)	C7—O3	1.210 (3)
C3—H3	0.9300	C7—O4	1.304 (3)
C4—N1	1.437 (3)	O1—H1	0.8200
C4—C5	1.514 (3)	O4—H4	0.8200
C4—H4A	0.9700	O5—H5A	0.9236
C4—H4B	0.9700	O5—H5B	0.8646
C5—O2	1.209 (3)

C3—C1—C2	117.08 (19)	O1—C5—C4	117.95 (19)
C3—C1—N1	121.21 (19)	N1—C6—C7	111.98 (18)
C2—C1—N1	121.71 (18)	N1—C6—H6A	109.2
C3ⁱ—C2—C1	121.50 (19)	C7—C6—H6A	109.2
C3ⁱ—C2—H2	119.3	N1—C6—H6B	109.2
C1—C2—H2	119.3	C7—C6—H6B	109.2
C2ⁱ—C3—C1	121.4 (2)	H6A—C6—H6B	107.9
C2ⁱ—C3—H3	119.3	O3—C7—O4	123.3 (2)
C1—C3—H3	119.3	O3—C7—C6	122.2 (2)
N1—C4—C5	115.57 (18)	O4—C7—C6	114.4 (2)
N1—C4—H4A	108.4	C1—N1—C4	119.59 (17)
C5—C4—H4A	108.4	C1—N1—C6	119.60 (17)
N1—C4—H4B	108.4	C4—N1—C6	120.69 (17)
C5—C4—H4B	108.4	C5—O1—H1	109.5
H4A—C4—H4B	107.5	C7—O4—H4	109.5
O2—C5—O1	120.0 (2)	H5A—O5—H5B	109.1
O2—C5—C4	122.0 (2)

C3—C1—C2—C3ⁱ	0.1 (3)	C3—C1—N1—C4	3.5 (3)
N1—C1—C2—C3ⁱ	179.81 (18)	C2—C1—N1—C4	−176.25 (18)
C2—C1—C3—C2ⁱ	−0.1 (3)	C3—C1—N1—C6	179.58 (18)
N1—C1—C3—C2ⁱ	−179.81 (18)	C2—C1—N1—C6	−0.1 (3)
N1—C4—C5—O2	−152.7 (2)	C5—C4—N1—C1	68.0 (2)
N1—C4—C5—O1	29.3 (3)	C5—C4—N1—C6	−108.1 (2)
N1—C6—C7—O3	−20.9 (3)	C7—C6—N1—C1	−71.6 (2)
N1—C6—C7—O4	158.3 (2)	C7—C6—N1—C4	104.5 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O2ⁱⁱ	0.86	2.13	2.819 (3)	137
O5—H5A···O2ⁱⁱⁱ	0.92	2.25	3.035 (3)	143
O4—H4···O5	0.82	1.78	2.597 (3)	171
O1—H1···O3	0.82	1.86	2.653 (2)	164

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂O₈·2H₂O
M_r	376.32
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.1446 (12), 8.4165 (19), 9.953 (2)
α, β, γ (°)	76.656 (4), 88.177 (4), 85.715 (4)
V (Å³)	418.12 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.975, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	2170, 1458, 1136
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.119, 1.04
No. of reflections	1458
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O2ⁱ	0.86	2.13	2.819 (3)	136.8
O5—H5A···O2ⁱⁱ	0.92	2.25	3.035 (3)	143.1
O4—H4···O5	0.82	1.78	2.597 (3)	170.5
O1—H1···O3	0.82	1.86	2.653 (2)	163.5

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

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 21171109), the Specialized Research Fund for the Doctoral Program of Higher Education (grant No. 20111401110002) and the Provincial Natural Science Foundation of Shanxi Province of China (grant No. 2010011011–2).

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