Literature DB >> 21754479

N,N'-Dicarb-oxy-N,N'-dicarboxyl-ato(m-phenyl-ene)dimethanaminium monohydrate.

Abstract

In the title inner salt, C(16)H(20)N(2)O(8)·H(2)O, two of four carboxyl groups are deprotonated, while the two imine groups are protonated. The two imino-diacetate groups are located on the same side of the benzene ring plane. Extensive inter-molecular O-H⋯O and N-H⋯O hydrogen bonds occur in the crystal.

Entities: CellLine Chemical Disease Gene

Year: 2011 PMID： 21754479 PMCID： PMC3089206 DOI： 10.1107/S1600536811013675

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

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 = 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 Δρmax = 0.13 e Å−3 Δρmin = −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. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013675/xu5178sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013675/xu5178Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₆H₂₀N₂O₈·H₂O	F(000) = 816
M_r = 386.36	D_x = 1.532 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1912 reflections
a = 22.491 (3) Å	θ = 3.0–27.3°
b = 5.4342 (7) Å	µ = 0.13 mm⁻¹
c = 14.3118 (19) Å	T = 296 K
β = 106.788 (2)°	Block, colorless
V = 1674.6 (4) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Bruker APEXII CCD diffractometer	1891 independent reflections
Radiation source: fine-focus sealed tube	1701 reflections with I > 2σ(I)
graphite	R_int = 0.020
φ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −28→18
T_min = 0.975, T_max = 0.988	k = −6→7
4927 measured reflections	l = −18→18

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0302P)² + 1.0337P] where P = (F_o² + 2F_c²)/3
1891 reflections	(Δ/σ)_max < 0.001
252 parameters	Δρ_max = 0.13 e Å⁻³
2 restraints	Δρ_min = −0.15 e Å⁻³

Experimental. Anal. Calcd for C₁₆H₂₂N₂O₉: C, 49.73; H, 5.64; N, 7.34%. Found: C, 49.69; H, 5.64; N, 7.34%. ¹H NMR (D₂O in the presence of K₂CO₃): d (p.p.m.) = 3.31 (8H, s, NCH₂CO₂), 3.95 (4H, s, PhCH₂N), 7.36 – 7.41 (4H, m, PhH).

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.

	x	y	z	U_iso*/U_eq
C1	0.48342 (11)	0.0785 (4)	0.53137 (16)	0.0231 (5)
C2	0.54217 (11)	−0.0180 (4)	0.57446 (17)	0.0240 (5)
H2	0.5537	−0.1655	0.5516	0.029*
C3	0.58405 (11)	0.1035 (5)	0.65160 (17)	0.0243 (5)
C4	0.56643 (12)	0.3244 (5)	0.68491 (17)	0.0281 (5)
H4	0.5944	0.4095	0.7352	0.034*
C5	0.50736 (13)	0.4184 (5)	0.64350 (18)	0.0296 (5)
H5	0.4955	0.5642	0.6671	0.036*
C6	0.46596 (12)	0.2960 (5)	0.56708 (18)	0.0272 (5)
H6	0.4264	0.3596	0.5396	0.033*
C7	0.43870 (11)	−0.0521 (5)	0.44711 (17)	0.0246 (5)
H7A	0.3971	−0.0390	0.4538	0.030*
H7B	0.4495	−0.2253	0.4495	0.030*
C8	0.39405 (12)	−0.0909 (5)	0.27035 (18)	0.0285 (5)
H8A	0.3588	−0.1388	0.2925	0.034*
H8B	0.4139	−0.2395	0.2567	0.034*
C9	0.37171 (11)	0.0596 (5)	0.17845 (18)	0.0286 (6)
C10	0.50246 (11)	0.0599 (4)	0.33451 (18)	0.0245 (5)
H10A	0.4991	0.0363	0.2660	0.029*
H10B	0.5276	−0.0724	0.3711	0.029*
C11	0.53354 (11)	0.3057 (4)	0.36863 (17)	0.0233 (5)
C12	0.64659 (11)	−0.0044 (5)	0.70305 (17)	0.0264 (5)
H12A	0.6431	−0.1823	0.7033	0.032*
H12B	0.6590	0.0508	0.7704	0.032*
C13	0.68289 (12)	−0.0009 (4)	0.55037 (17)	0.0257 (5)
H13A	0.7183	0.0447	0.5282	0.031*
H13B	0.6477	0.0960	0.5134	0.031*
C14	0.66863 (11)	−0.2693 (5)	0.52703 (18)	0.0258 (5)
C15	0.75870 (11)	−0.0232 (5)	0.71783 (18)	0.0283 (6)
H15A	0.7870	−0.0372	0.6781	0.034*
H15B	0.7541	−0.1851	0.7435	0.034*
C16	0.78576 (12)	0.1544 (5)	0.80242 (18)	0.0293 (5)
H1A	0.4248 (13)	0.219 (5)	0.347 (2)	0.028 (7)*
H2A	0.6999 (12)	0.244 (5)	0.658 (2)	0.029 (7)*
N1	0.43897 (9)	0.0518 (4)	0.34879 (14)	0.0228 (4)
N2	0.69672 (9)	0.0663 (4)	0.65600 (14)	0.0225 (4)
O1	0.59162 (8)	0.3058 (3)	0.37755 (12)	0.0295 (4)
O2	0.50164 (9)	0.4792 (3)	0.38026 (14)	0.0342 (4)
O3	0.38729 (10)	0.2699 (4)	0.17322 (15)	0.0441 (5)
O4	0.33302 (9)	−0.0662 (4)	0.10907 (14)	0.0411 (5)
H4A	0.3175	0.0277	0.0606	0.049*
O5	0.64514 (10)	−0.3008 (4)	0.43420 (13)	0.0401 (5)
H5A	0.6336	−0.4497	0.4230	0.048*
O6	0.67714 (10)	−0.4290 (3)	0.58908 (14)	0.0391 (5)
O7	0.76142 (10)	0.3614 (4)	0.79623 (14)	0.0398 (5)
O8	0.83165 (10)	0.0772 (4)	0.86778 (15)	0.0472 (6)
O1W	0.78493 (9)	0.6735 (4)	0.95209 (13)	0.0399 (5)
H1WA	0.7763	0.5697	0.9057	0.048*
H1WB	0.7988	0.8079	0.9363	0.048*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0222 (11)	0.0252 (12)	0.0219 (11)	−0.0016 (9)	0.0064 (9)	0.0030 (10)
C2	0.0241 (12)	0.0230 (12)	0.0252 (11)	0.0007 (10)	0.0076 (9)	−0.0015 (10)
C3	0.0229 (12)	0.0274 (12)	0.0223 (11)	−0.0007 (10)	0.0062 (9)	0.0013 (10)
C4	0.0319 (14)	0.0317 (14)	0.0206 (12)	−0.0044 (11)	0.0076 (10)	−0.0047 (10)
C5	0.0388 (14)	0.0238 (12)	0.0286 (13)	0.0033 (11)	0.0133 (11)	−0.0013 (10)
C6	0.0256 (12)	0.0297 (13)	0.0270 (13)	0.0054 (10)	0.0088 (10)	0.0041 (10)
C7	0.0213 (12)	0.0288 (13)	0.0228 (12)	−0.0038 (9)	0.0048 (9)	0.0009 (10)
C8	0.0267 (12)	0.0286 (14)	0.0267 (12)	−0.0083 (10)	0.0023 (10)	0.0008 (10)
C9	0.0224 (13)	0.0371 (15)	0.0253 (13)	−0.0012 (10)	0.0053 (10)	−0.0003 (10)
C10	0.0228 (12)	0.0233 (12)	0.0274 (12)	−0.0014 (10)	0.0074 (9)	−0.0005 (10)
C11	0.0282 (13)	0.0220 (11)	0.0186 (10)	−0.0014 (10)	0.0051 (9)	0.0018 (9)
C12	0.0247 (13)	0.0321 (13)	0.0210 (11)	−0.0007 (10)	0.0047 (10)	0.0010 (10)
C13	0.0272 (12)	0.0253 (12)	0.0225 (12)	−0.0023 (10)	0.0039 (9)	0.0020 (9)
C14	0.0232 (12)	0.0264 (12)	0.0268 (12)	0.0003 (10)	0.0056 (10)	0.0008 (10)
C15	0.0204 (12)	0.0309 (14)	0.0273 (13)	0.0025 (10)	−0.0032 (10)	−0.0017 (10)
C16	0.0266 (13)	0.0293 (13)	0.0287 (13)	−0.0069 (10)	0.0027 (10)	−0.0019 (11)
N1	0.0214 (10)	0.0227 (10)	0.0221 (10)	−0.0017 (8)	0.0031 (8)	0.0006 (8)
N2	0.0209 (10)	0.0196 (10)	0.0237 (10)	−0.0005 (8)	0.0012 (8)	−0.0008 (8)
O1	0.0246 (9)	0.0267 (9)	0.0342 (10)	−0.0039 (7)	0.0035 (7)	−0.0010 (8)
O2	0.0398 (11)	0.0212 (9)	0.0443 (11)	0.0007 (8)	0.0161 (9)	−0.0021 (8)
O3	0.0479 (12)	0.0371 (12)	0.0392 (12)	−0.0087 (10)	−0.0007 (9)	0.0086 (9)
O4	0.0414 (12)	0.0467 (12)	0.0265 (9)	−0.0075 (9)	−0.0039 (8)	0.0024 (9)
O5	0.0556 (13)	0.0334 (11)	0.0257 (9)	−0.0153 (9)	0.0030 (9)	−0.0036 (8)
O6	0.0559 (13)	0.0224 (9)	0.0333 (10)	0.0002 (9)	0.0037 (9)	0.0041 (8)
O7	0.0476 (12)	0.0297 (11)	0.0325 (10)	−0.0013 (9)	−0.0037 (8)	−0.0042 (8)
O8	0.0378 (11)	0.0477 (13)	0.0397 (11)	0.0021 (10)	−0.0149 (9)	−0.0032 (10)
O1W	0.0443 (12)	0.0452 (12)	0.0258 (9)	0.0013 (9)	0.0031 (8)	−0.0015 (9)

C1—C6	1.388 (3)	C10—H10B	0.9700
C1—C2	1.389 (3)	C11—O2	1.225 (3)
C1—C7	1.507 (3)	C11—O1	1.275 (3)
C2—C3	1.394 (3)	C12—N2	1.520 (3)
C2—H2	0.9300	C12—H12A	0.9700
C3—C4	1.391 (4)	C12—H12B	0.9700
C3—C12	1.505 (3)	C13—N2	1.498 (3)
C4—C5	1.387 (4)	C13—C14	1.510 (3)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.385 (4)	C13—H13B	0.9700
C5—H5	0.9300	C14—O6	1.216 (3)
C6—H6	0.9300	C14—O5	1.292 (3)
C7—N1	1.518 (3)	C15—N2	1.500 (3)
C7—H7A	0.9700	C15—C16	1.530 (3)
C7—H7B	0.9700	C15—H15A	0.9700
C8—N1	1.492 (3)	C15—H15B	0.9700
C8—C9	1.506 (4)	C16—O7	1.243 (3)
C8—H8A	0.9700	C16—O8	1.248 (3)
C8—H8B	0.9700	N1—H1A	0.96 (3)
C9—O3	1.204 (3)	N2—H2A	0.97 (3)
C9—O4	1.308 (3)	O4—H4A	0.8501
C10—N1	1.501 (3)	O5—H5A	0.8500
C10—C11	1.521 (3)	O1W—H1WA	0.8500
C10—H10A	0.9700	O1W—H1WB	0.8500

C6—C1—C2	119.5 (2)	O1—C11—C10	113.3 (2)
C6—C1—C7	120.1 (2)	C3—C12—N2	113.12 (19)
C2—C1—C7	120.4 (2)	C3—C12—H12A	109.0
C1—C2—C3	120.7 (2)	N2—C12—H12A	109.0
C1—C2—H2	119.6	C3—C12—H12B	109.0
C3—C2—H2	119.6	N2—C12—H12B	109.0
C4—C3—C2	119.1 (2)	H12A—C12—H12B	107.8
C4—C3—C12	119.1 (2)	N2—C13—C14	115.3 (2)
C2—C3—C12	121.7 (2)	N2—C13—H13A	108.4
C3—C4—C5	120.3 (2)	C14—C13—H13A	108.4
C3—C4—H4	119.9	N2—C13—H13B	108.4
C5—C4—H4	119.9	C14—C13—H13B	108.4
C6—C5—C4	120.2 (2)	H13A—C13—H13B	107.5
C6—C5—H5	119.9	O6—C14—O5	126.0 (2)
C4—C5—H5	119.9	O6—C14—C13	123.3 (2)
C5—C6—C1	120.2 (2)	O5—C14—C13	110.7 (2)
C5—C6—H6	119.9	N2—C15—C16	110.6 (2)
C1—C6—H6	119.9	N2—C15—H15A	109.5
C1—C7—N1	112.71 (19)	C16—C15—H15A	109.5
C1—C7—H7A	109.0	N2—C15—H15B	109.5
N1—C7—H7A	109.0	C16—C15—H15B	109.5
C1—C7—H7B	109.0	H15A—C15—H15B	108.1
N1—C7—H7B	109.0	O7—C16—O8	127.5 (2)
H7A—C7—H7B	107.8	O7—C16—C15	116.6 (2)
N1—C8—C9	111.0 (2)	O8—C16—C15	115.8 (2)
N1—C8—H8A	109.4	C8—N1—C10	112.15 (19)
C9—C8—H8A	109.4	C8—N1—C7	108.73 (18)
N1—C8—H8B	109.4	C10—N1—C7	113.33 (18)
C9—C8—H8B	109.4	C8—N1—H1A	109.1 (17)
H8A—C8—H8B	108.0	C10—N1—H1A	106.9 (16)
O3—C9—O4	126.2 (3)	C7—N1—H1A	106.4 (17)
O3—C9—C8	122.7 (2)	C15—N2—C13	113.76 (19)
O4—C9—C8	111.1 (2)	C15—N2—C12	109.77 (19)
N1—C10—C11	110.46 (19)	C13—N2—C12	114.90 (19)
N1—C10—H10A	109.6	C15—N2—H2A	104.9 (16)
C11—C10—H10A	109.6	C13—N2—H2A	105.7 (16)
N1—C10—H10B	109.6	C12—N2—H2A	107.0 (17)
C11—C10—H10B	109.6	C9—O4—H4A	109.4
H10A—C10—H10B	108.1	C14—O5—H5A	109.4
O2—C11—O1	127.5 (2)	H1WA—O1W—H1WB	112.4
O2—C11—C10	119.1 (2)

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

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

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

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Regioselective hydroxylation of the xylyl linker in a diiron(III) complex having a carboxylate-rich ligand with H2O2.

Authors: Hideki Furutachi; Mizue Murayama; Amane Shiohara; Satoshi Yamazaki; Shuhei Fujinami; Akira Uehara; Masatatsu Suzuki; Seiji Ogo; Yoshihito Watanabe; Yonezo Maeda
Journal: Chem Commun (Camb) Date: 2003-08-07 Impact factor: 6.222

2 in total