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

Qiang, Y.-X.; Zhu, S.-R.; Shao, M.

doi:10.1107/S1600536811013675

organic compounds

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Volume 67| Part 5| May 2011| Page o1174

doi:10.1107/S1600536811013675

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

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

^aDepartment of Chemistry, Shanghai University, Shanghai 200444, People's Republic of China, and ^bInstrumental Analysis Center, Shanghai University, Shanghai 200444, People's Republic of China
^*Correspondence e-mail: shourongzhu@shu.edu.cn

(Received 18 March 2011; accepted 12 April 2011; online 22 April 2011)

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, C c
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[F² > 2σ(F²)] = 0.030
wR(F²) = 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

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z-1]$ ; (iv) x, y-1, z.

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. H-bonds in the title compound. Purple bonds are H-Bond.
	Fig. 3. Crystal packing diagram of the title compound.

N,N'-Dicarboxy-N,N'-dicarboxylato(m- phenylene)dimethanaminium monohydrate top

Crystal data top

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

Data collection top

Bruker APEXII CCD diffractometer	1891 independent reflections
Radiation source: fine-focus sealed tube	1701 reflections with I > 2σ(I)
Graphite monochromator	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 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)] = 0.030	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

Crystal data top

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

Data collection top

Bruker APEXII CCD diffractometer	1891 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1701 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.988	R_int = 0.020
4927 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	2 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.13 e Å⁻³
1891 reflections	Δρ_min = −0.15 e Å⁻³
252 parameters

Special details top

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.

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

	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₆H₂₀N₂O₈·H₂O
M_r	386.36
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	22.491 (3), 5.4342 (7), 14.3118 (19)
β (°)	106.788 (2)
V (Å³)	1674.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.975, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4927, 1891, 1701
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.069, 0.97
No. of reflections	1891
No. of parameters	252
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.15

Computer programs: APEX2 (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

Acknowledgements

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

References

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