2,2′-[(4,6-Dinitro-1,3-phenyl­ene)dioxy]diacetic acid hemihydrate

Ma, D.-S.; Zhang, X.-M.; Zhang, H.; Mu, D.; Hou, G.-F.

doi:10.1107/S1600536809036253

2,2′-[(4,6-Dinitro-1,3-phenylene)dioxy]diacetic acid hemihydrate

D.-S. Ma, X.-M. Zhang, H. Zhang, D. Mu and G.-F. Hou

The skeletons of both independent molecules of the carboxylic acid hemihydrate, C₁₀H₈N₂O₁₀·0.5H₂O, are approximately planar [maximum deviations 0.642 (3) and 0.468 (1) Å]. The deviations arise from the twisting of the nitro groups with respect to the aromatic rings [dihedral angles = 3.24 (2) and 27.01 (1), and 7.87 (1) and 16.37 (2)° in the two molecules]. The crystal structure features intermolecular O—H

O hydrogen bonds, which the link the dicarboxylic acid and water molecules into a supramolecular layer network.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809036253/ng2635sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809036253/ng2635Isup2.hkl Contains datablock I

CCDC reference: 750700

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.004 Å
R factor = 0.054
wR factor = 0.172
Data-to-parameter ratio = 11.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N1

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O19    --  N4      ..       5.26 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.37
PLAT432_ALERT_2_C Short Inter X...Y Contact  O20    ..  C1      ..       2.97 Ang.
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT480_ALERT_4_C Long H...A H-Bond Reported H21    ..  O10     ..       2.66 Ang.

Alert level G
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............          3 Times

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Flexible aromatic carboxylic acid with oxygen is a kind of biological activity of the organic carboxylic acid, not only in agriculture, such as plant growth regulators and herbicides it is applied, but also it is important to the synthesis of some organic medicine centre body. Compared with other rigid carboxylic acid ligands, such flexible aromatic carboxylic acid have highly plasticity and spatial configuration of, so it provides a rich and colorful way to identify and assemble for constructing a novel topological network structure with the special physical and chemical properties (Coronado et al., 2000; Gao et al., 2006). In this paper, we report the synthesis and crystal structures of a new flexible aromatic carboxylic acid compound.

In the crystal structure, the skeletons of the two dicarboxylic acid molecules are all approximately co-planar with the largest deviation being 0.642 (3) Å, 0.4681 Å from O8 and O15 for molecule C1–C10 and molecule C11–C20, respectively (Figure 1). This deviations are caused by the twisting of the nitro groups with the benzene planes.

There are six symmetry-independent 'active' H atoms in the crystal structure, all of them participate in hydrogen bonds, which link the dicarboxylic acid and water molecules into a two-dimensional layer supramolecular network (Table 1, Figure 2).

Related literature top

For general background to the use of flexible aromatic carboxylic acid ligands, see: Coronado et al. (2000). For the synthesis and related structures, see: Gao et al. (2006)

Experimental top

The synthesis of target product is as follows: chlorine acetic acid (51.6 g, 0.54 mol), sodalye(21.8 g, 0.54 mol) were dissolved into 200 ml distilled water with stirring. The mixture was heated to refluxed for 6 h, then the pH value was adjusted to about 2.0 by using 3 M hydrochloric acid. After cooling to the room temperature, 10.8 g (27%) yellow precipitate was obtained. The 10.8 g above yellow product was dissolved into 100 ml concentrated sulfuric acid with stirring, and then the mixture of nitric acid (9.45 g, 0.15 mol) and sulfuric acid (20.58 g, 0.21 mol) was dropped into the above solution with keeping the reaction trmperature under 0 ° C for 1 h. The mixture was poured into 500 ml water solution. The crude product was recrystallized from 100 ml water solution, 4.2 g yellow needle crystal was obtained (30%).

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 three-dimensional supramolecular network. Dashed lines indicate the hydrogen-bonding interactions and no involving H atoms have been omitted.

2,2'-[(4,6-Dinitro-1,3-phenylene)dioxy]diacetic acid hemihydrate top

Crystal data top

C₁₀H₈N₂O₁₀·0.5H₂O	F(000) = 1336
M_r = 325.19	D_x = 1.668 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13902 reflections
a = 7.3873 (15) Å	θ = 3.0–27.4°
b = 25.918 (5) Å	µ = 0.16 mm⁻¹
c = 13.711 (3) Å	T = 291 K
β = 99.43 (3)°	Block, colorless
V = 2589.7 (9) Å³	0.25 × 0.21 × 0.20 mm
Z = 8

Data collection top

Rigaku RAXIS-RAPID diffractometer	4552 independent reflections
Radiation source: fine-focus sealed tube	3197 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scan	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.962, T_max = 0.970	k = −30→30
19619 measured reflections	l = −16→16

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.099P)² + 0.8965P] where P = (F_o² + 2F_c²)/3
4552 reflections	(Δ/σ)_max < 0.001
410 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₀H₈N₂O₁₀·0.5H₂O	V = 2589.7 (9) Å³
M_r = 325.19	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.3873 (15) Å	µ = 0.16 mm⁻¹
b = 25.918 (5) Å	T = 291 K
c = 13.711 (3) Å	0.25 × 0.21 × 0.20 mm
β = 99.43 (3)°

Data collection top

Rigaku RAXIS-RAPID diffractometer	4552 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3197 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.970	R_int = 0.046
19619 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.03	Δρ_max = 0.42 e Å⁻³
4552 reflections	Δρ_min = −0.30 e Å⁻³
410 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	1.0310 (4)	−0.05466 (12)	0.0762 (2)	0.0453 (7)
C2	0.8978 (5)	−0.03824 (14)	0.1436 (3)	0.0567 (9)
H2A	0.7756	−0.0337	0.1062	0.068*
H2B	0.8927	−0.0639	0.1946	0.068*
C3	0.8704 (4)	0.03522 (12)	0.2451 (2)	0.0424 (7)
C4	0.7138 (4)	0.01642 (12)	0.2754 (2)	0.0455 (8)
H4	0.6713	−0.0162	0.2548	0.055*
C5	0.6181 (4)	0.04510 (11)	0.3361 (2)	0.0393 (7)
C6	0.6824 (4)	0.09461 (11)	0.3636 (2)	0.0416 (7)
C7	0.8398 (4)	0.11370 (11)	0.3348 (2)	0.0442 (7)
H7	0.8811	0.1466	0.3544	0.053*
C8	0.9353 (4)	0.08438 (11)	0.2776 (2)	0.0415 (7)
C9	0.3957 (4)	−0.02105 (11)	0.3406 (3)	0.0486 (8)
H9A	0.4864	−0.0476	0.3611	0.058*
H9B	0.3611	−0.0226	0.2693	0.058*
C10	0.2310 (4)	−0.02900 (12)	0.3895 (3)	0.0481 (8)
C11	1.0980 (4)	0.38191 (11)	0.5469 (2)	0.0425 (7)
C12	0.9397 (4)	0.34925 (11)	0.5686 (2)	0.0423 (7)
H12A	0.8560	0.3699	0.6000	0.051*
H12B	0.8726	0.3349	0.5080	0.051*
C13	0.9082 (4)	0.27089 (11)	0.6568 (2)	0.0358 (6)
C14	0.7269 (4)	0.26400 (11)	0.6126 (2)	0.0368 (6)
H14	0.6759	0.2870	0.5636	0.044*
C15	0.6187 (3)	0.22418 (10)	0.6385 (2)	0.0327 (6)
C16	0.6953 (4)	0.19013 (10)	0.7146 (2)	0.0354 (6)
C17	0.8751 (4)	0.19648 (11)	0.7588 (2)	0.0372 (7)
H17	0.9256	0.1737	0.8083	0.045*
C18	0.9820 (4)	0.23571 (11)	0.7313 (2)	0.0370 (7)
C19	0.3662 (4)	0.25045 (11)	0.5203 (2)	0.0385 (7)
H19A	0.4391	0.2513	0.4676	0.046*
H19B	0.3623	0.2850	0.5472	0.046*
C20	0.1761 (4)	0.23215 (12)	0.4812 (2)	0.0433 (7)
N1	1.1037 (4)	0.10698 (12)	0.2527 (2)	0.0560 (7)
N2	0.5870 (4)	0.12895 (10)	0.4221 (2)	0.0542 (7)
N3	1.1684 (3)	0.23969 (10)	0.78400 (19)	0.0430 (6)
N4	0.5927 (4)	0.14953 (9)	0.75239 (19)	0.0444 (6)
O1	1.1678 (3)	−0.03181 (8)	0.06594 (18)	0.0536 (6)
O2	0.9765 (3)	−0.09865 (9)	0.03349 (19)	0.0604 (7)
H2	1.0469	−0.1072	−0.0041	0.091*
O3	0.9670 (3)	0.00887 (9)	0.18550 (19)	0.0589 (7)
O4	0.1546 (4)	−0.07382 (9)	0.3654 (2)	0.0720 (8)
H5	0.0629	−0.0771	0.3914	0.108*
O5	0.1750 (3)	0.00126 (10)	0.4427 (2)	0.0687 (8)
O6	0.4686 (3)	0.02851 (8)	0.36993 (17)	0.0509 (6)
O7	1.1969 (5)	0.08272 (13)	0.2060 (3)	0.1029 (12)
O8	1.1449 (5)	0.14971 (13)	0.2799 (4)	0.1298 (17)
O9	0.6063 (5)	0.17479 (10)	0.4134 (3)	0.0998 (12)
O10	0.4939 (4)	0.11086 (10)	0.4787 (3)	0.0919 (11)
O11	1.2585 (3)	0.36932 (9)	0.56650 (17)	0.0533 (6)
O12	1.0395 (3)	0.42478 (9)	0.5016 (2)	0.0614 (7)
H12	1.1271	0.4410	0.4877	0.092*
O13	1.0174 (3)	0.30879 (8)	0.63347 (16)	0.0463 (5)
O14	0.0992 (3)	0.26513 (11)	0.4130 (2)	0.0704 (8)
H15	−0.0088	0.2573	0.3954	0.106*
O15	0.1017 (3)	0.19503 (9)	0.5074 (2)	0.0635 (7)
O16	0.4453 (2)	0.21590 (7)	0.59524 (14)	0.0391 (5)
O17	1.2814 (3)	0.26610 (9)	0.75223 (18)	0.0541 (6)
O18	1.2051 (3)	0.21598 (11)	0.86301 (18)	0.0644 (7)
O19	0.4279 (4)	0.14545 (11)	0.7251 (2)	0.0824 (9)
O20	0.6744 (4)	0.12010 (10)	0.8133 (2)	0.0701 (7)
O21	0.1450 (4)	0.08578 (9)	0.5660 (2)	0.0706 (8)
H21	0.1745	0.1146	0.5437	0.106*
H22	0.1744	0.0616	0.5298	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0422 (17)	0.0467 (17)	0.0464 (19)	0.0058 (14)	0.0056 (14)	−0.0020 (15)
C2	0.050 (2)	0.061 (2)	0.064 (2)	0.0008 (16)	0.0214 (17)	−0.0124 (18)
C3	0.0395 (16)	0.0499 (17)	0.0399 (17)	0.0061 (13)	0.0127 (14)	0.0010 (14)
C4	0.0448 (18)	0.0434 (17)	0.0512 (19)	−0.0052 (13)	0.0161 (15)	−0.0092 (14)
C5	0.0367 (16)	0.0395 (16)	0.0446 (17)	−0.0044 (12)	0.0150 (14)	−0.0017 (13)
C6	0.0417 (17)	0.0380 (16)	0.0481 (18)	−0.0023 (12)	0.0164 (14)	−0.0013 (13)
C7	0.0448 (17)	0.0366 (15)	0.0530 (19)	−0.0034 (13)	0.0137 (15)	0.0028 (14)
C8	0.0369 (16)	0.0439 (16)	0.0450 (18)	−0.0030 (12)	0.0103 (14)	0.0060 (14)
C9	0.0491 (18)	0.0380 (16)	0.063 (2)	−0.0102 (14)	0.0229 (16)	−0.0099 (15)
C10	0.0440 (18)	0.0471 (18)	0.056 (2)	−0.0073 (14)	0.0173 (16)	−0.0031 (16)
C11	0.0497 (19)	0.0412 (16)	0.0380 (17)	0.0002 (14)	0.0117 (14)	−0.0012 (13)
C12	0.0350 (16)	0.0485 (17)	0.0439 (18)	0.0029 (13)	0.0076 (13)	0.0062 (14)
C13	0.0329 (14)	0.0438 (16)	0.0311 (15)	−0.0027 (12)	0.0063 (12)	−0.0004 (12)
C14	0.0311 (14)	0.0457 (16)	0.0323 (15)	0.0034 (12)	0.0018 (12)	0.0060 (12)
C15	0.0294 (14)	0.0392 (15)	0.0288 (14)	0.0033 (11)	0.0026 (11)	−0.0027 (12)
C16	0.0347 (15)	0.0413 (15)	0.0302 (15)	−0.0010 (12)	0.0054 (12)	−0.0036 (12)
C17	0.0383 (16)	0.0424 (16)	0.0296 (15)	0.0054 (13)	0.0017 (12)	0.0039 (12)
C18	0.0302 (14)	0.0486 (17)	0.0309 (15)	0.0055 (12)	0.0010 (12)	−0.0008 (13)
C19	0.0275 (14)	0.0447 (16)	0.0423 (17)	0.0020 (12)	0.0024 (13)	0.0064 (13)
C20	0.0322 (15)	0.0522 (18)	0.0440 (18)	0.0007 (13)	0.0018 (13)	0.0071 (15)
N1	0.0427 (15)	0.0607 (18)	0.069 (2)	−0.0023 (13)	0.0232 (15)	0.0033 (15)
N2	0.0590 (17)	0.0394 (15)	0.071 (2)	−0.0066 (12)	0.0303 (16)	−0.0094 (14)
N3	0.0350 (13)	0.0550 (16)	0.0370 (15)	0.0061 (12)	−0.0002 (11)	−0.0025 (12)
N4	0.0571 (17)	0.0395 (14)	0.0356 (14)	0.0016 (12)	0.0045 (12)	0.0036 (11)
O1	0.0496 (14)	0.0502 (13)	0.0646 (16)	0.0048 (11)	0.0201 (12)	−0.0022 (11)
O2	0.0475 (13)	0.0690 (16)	0.0656 (17)	0.0010 (12)	0.0125 (12)	−0.0206 (13)
O3	0.0515 (14)	0.0615 (14)	0.0712 (17)	−0.0060 (11)	0.0322 (13)	−0.0211 (12)
O4	0.0710 (17)	0.0559 (15)	0.100 (2)	−0.0295 (12)	0.0460 (16)	−0.0189 (14)
O5	0.0614 (15)	0.0644 (15)	0.091 (2)	−0.0169 (12)	0.0435 (15)	−0.0233 (14)
O6	0.0466 (12)	0.0433 (12)	0.0700 (16)	−0.0127 (9)	0.0306 (12)	−0.0147 (11)
O7	0.089 (2)	0.101 (2)	0.139 (3)	−0.0308 (18)	0.079 (2)	−0.030 (2)
O8	0.102 (3)	0.082 (2)	0.231 (5)	−0.0489 (19)	0.101 (3)	−0.049 (3)
O9	0.141 (3)	0.0386 (14)	0.143 (3)	−0.0031 (15)	0.094 (3)	−0.0108 (16)
O10	0.116 (2)	0.0620 (16)	0.120 (3)	−0.0231 (16)	0.084 (2)	−0.0273 (16)
O11	0.0384 (13)	0.0601 (14)	0.0604 (15)	−0.0059 (10)	0.0056 (11)	0.0149 (11)
O12	0.0579 (14)	0.0512 (14)	0.0796 (18)	0.0063 (11)	0.0249 (14)	0.0197 (12)
O13	0.0321 (11)	0.0547 (13)	0.0513 (13)	−0.0040 (9)	0.0041 (9)	0.0157 (10)
O14	0.0390 (13)	0.0869 (18)	0.0759 (18)	−0.0118 (12)	−0.0185 (13)	0.0336 (15)
O15	0.0473 (14)	0.0642 (15)	0.0754 (18)	−0.0129 (12)	−0.0010 (12)	0.0166 (13)
O16	0.0299 (10)	0.0479 (11)	0.0377 (11)	−0.0010 (8)	0.0006 (8)	0.0080 (9)
O17	0.0318 (11)	0.0679 (15)	0.0616 (15)	−0.0030 (10)	0.0045 (11)	0.0026 (12)
O18	0.0487 (14)	0.0928 (19)	0.0454 (14)	0.0050 (13)	−0.0107 (11)	0.0178 (13)
O19	0.0506 (16)	0.0870 (19)	0.101 (2)	−0.0264 (13)	−0.0121 (15)	0.0424 (17)
O20	0.0700 (17)	0.0651 (15)	0.0722 (18)	−0.0028 (13)	0.0029 (14)	0.0330 (14)
O21	0.0716 (17)	0.0585 (14)	0.089 (2)	−0.0213 (12)	0.0331 (15)	−0.0060 (14)

Geometric parameters (Å, º) top

C1—O1	1.199 (4)	C13—C14	1.389 (4)
C1—O2	1.314 (4)	C13—C18	1.410 (4)
C1—C2	1.517 (4)	C14—C15	1.387 (4)
C2—O3	1.409 (4)	C14—H14	0.9300
C2—H2A	0.9700	C15—O16	1.338 (3)
C2—H2B	0.9700	C15—C16	1.412 (4)
C3—O3	1.355 (3)	C16—C17	1.376 (4)
C3—C4	1.380 (4)	C16—N4	1.441 (4)
C3—C8	1.408 (4)	C17—C18	1.377 (4)
C4—C5	1.392 (4)	C17—H17	0.9300
C4—H4	0.9300	C18—N3	1.450 (4)
C5—O6	1.337 (3)	C19—O16	1.414 (3)
C5—C6	1.398 (4)	C19—C20	1.496 (4)
C6—C7	1.379 (4)	C19—H19A	0.9700
C6—N2	1.455 (4)	C19—H19B	0.9700
C7—C8	1.369 (4)	C20—O15	1.192 (4)
C7—H7	0.9300	C20—O14	1.324 (4)
C8—N1	1.465 (4)	N1—O8	1.192 (4)
C9—O6	1.425 (3)	N1—O7	1.194 (4)
C9—C10	1.497 (4)	N2—O9	1.205 (3)
C9—H9A	0.9700	N2—O10	1.213 (4)
C9—H9B	0.9700	N3—O17	1.214 (3)
C10—O5	1.190 (4)	N3—O18	1.236 (3)
C10—O4	1.310 (4)	N4—O20	1.216 (3)
C11—O11	1.217 (4)	N4—O19	1.218 (4)
C11—O12	1.311 (4)	O2—H2	0.8200
C11—C12	1.512 (4)	O4—H5	0.8200
C12—O13	1.433 (3)	O12—H12	0.8200
C12—H12A	0.9700	O14—H15	0.8200
C12—H12B	0.9700	O21—H21	0.8500
C13—O13	1.343 (3)	O21—H22	0.8501

O1—C1—O2	125.4 (3)	C14—C13—C18	117.6 (2)
O1—C1—C2	125.2 (3)	C15—C14—C13	122.6 (3)
O2—C1—C2	109.4 (3)	C15—C14—H14	118.7
O3—C2—C1	105.3 (3)	C13—C14—H14	118.7
O3—C2—H2A	110.7	O16—C15—C14	123.7 (2)
C1—C2—H2A	110.7	O16—C15—C16	117.8 (2)
O3—C2—H2B	110.7	C14—C15—C16	118.5 (2)
C1—C2—H2B	110.7	C17—C16—C15	119.4 (2)
H2A—C2—H2B	108.8	C17—C16—N4	117.1 (3)
O3—C3—C4	123.6 (3)	C15—C16—N4	123.4 (2)
O3—C3—C8	117.5 (3)	C16—C17—C18	121.6 (3)
C4—C3—C8	118.9 (3)	C16—C17—H17	119.2
C3—C4—C5	121.6 (3)	C18—C17—H17	119.2
C3—C4—H4	119.2	C17—C18—C13	120.3 (3)
C5—C4—H4	119.2	C17—C18—N3	117.2 (3)
O6—C5—C4	124.4 (3)	C13—C18—N3	122.5 (3)
O6—C5—C6	117.8 (2)	O16—C19—C20	108.1 (2)
C4—C5—C6	117.9 (2)	O16—C19—H19A	110.1
C7—C6—C5	121.2 (3)	C20—C19—H19A	110.1
C7—C6—N2	116.4 (3)	O16—C19—H19B	110.1
C5—C6—N2	122.4 (2)	C20—C19—H19B	110.1
C8—C7—C6	120.2 (3)	H19A—C19—H19B	108.4
C8—C7—H7	119.9	O15—C20—O14	124.6 (3)
C6—C7—H7	119.9	O15—C20—C19	126.9 (3)
C7—C8—C3	120.2 (3)	O14—C20—C19	108.5 (3)
C7—C8—N1	116.7 (3)	O8—N1—O7	121.1 (3)
C3—C8—N1	123.1 (3)	O8—N1—C8	118.8 (3)
O6—C9—C10	107.2 (2)	O7—N1—C8	120.1 (3)
O6—C9—H9A	110.3	O9—N2—O10	122.2 (3)
C10—C9—H9A	110.3	O9—N2—C6	118.3 (3)
O6—C9—H9B	110.3	O10—N2—C6	119.6 (3)
C10—C9—H9B	110.3	O17—N3—O18	122.0 (3)
H9A—C9—H9B	108.5	O17—N3—C18	120.9 (3)
O5—C10—O4	124.1 (3)	O18—N3—C18	117.1 (3)
O5—C10—C9	125.0 (3)	O20—N4—O19	121.0 (3)
O4—C10—C9	110.9 (3)	O20—N4—C16	118.3 (3)
O11—C11—O12	124.4 (3)	O19—N4—C16	120.7 (3)
O11—C11—C12	124.3 (3)	C1—O2—H2	109.5
O12—C11—C12	111.2 (3)	C3—O3—C2	119.4 (2)
O13—C12—C11	106.7 (2)	C10—O4—H5	109.5
O13—C12—H12A	110.4	C5—O6—C9	119.2 (2)
C11—C12—H12A	110.4	C11—O12—H12	109.5
O13—C12—H12B	110.4	C13—O13—C12	119.2 (2)
C11—C12—H12B	110.4	C20—O14—H15	109.5
H12A—C12—H12B	108.6	C15—O16—C19	118.2 (2)
O13—C13—C14	124.3 (3)	H21—O21—H22	109.5
O13—C13—C18	118.0 (2)

O1—C1—C2—O3	2.2 (5)	O13—C13—C18—C17	179.3 (2)
O2—C1—C2—O3	−179.9 (3)	C14—C13—C18—C17	−0.6 (4)
O3—C3—C4—C5	−179.4 (3)	O13—C13—C18—N3	1.2 (4)
C8—C3—C4—C5	0.7 (5)	C14—C13—C18—N3	−178.7 (2)
C3—C4—C5—O6	−178.2 (3)	O16—C19—C20—O15	−0.2 (5)
C3—C4—C5—C6	1.9 (5)	O16—C19—C20—O14	178.2 (3)
O6—C5—C6—C7	177.5 (3)	C7—C8—N1—O8	−2.7 (5)
C4—C5—C6—C7	−2.6 (5)	C3—C8—N1—O8	177.0 (4)
O6—C5—C6—N2	−3.5 (5)	C7—C8—N1—O7	177.4 (4)
C4—C5—C6—N2	176.4 (3)	C3—C8—N1—O7	−2.9 (5)
C5—C6—C7—C8	0.7 (5)	C7—C6—N2—O9	25.6 (5)
N2—C6—C7—C8	−178.4 (3)	C5—C6—N2—O9	−153.5 (4)
C6—C7—C8—C3	2.0 (5)	C7—C6—N2—O10	−153.2 (3)
C6—C7—C8—N1	−178.3 (3)	C5—C6—N2—O10	27.7 (5)
O3—C3—C8—C7	177.5 (3)	C17—C18—N3—O17	165.4 (3)
C4—C3—C8—C7	−2.7 (5)	C13—C18—N3—O17	−16.5 (4)
O3—C3—C8—N1	−2.2 (5)	C17—C18—N3—O18	−16.1 (4)
C4—C3—C8—N1	177.6 (3)	C13—C18—N3—O18	162.1 (3)
O6—C9—C10—O5	0.0 (5)	C17—C16—N4—O20	−7.4 (4)
O6—C9—C10—O4	179.4 (3)	C15—C16—N4—O20	175.1 (3)
O11—C11—C12—O13	12.5 (4)	C17—C16—N4—O19	171.4 (3)
O12—C11—C12—O13	−169.4 (3)	C15—C16—N4—O19	−6.1 (4)
O13—C13—C14—C15	179.7 (3)	C4—C3—O3—C2	6.2 (5)
C18—C13—C14—C15	−0.4 (4)	C8—C3—O3—C2	−174.0 (3)
C13—C14—C15—O16	−178.2 (2)	C1—C2—O3—C3	175.8 (3)
C13—C14—C15—C16	1.5 (4)	C4—C5—O6—C9	−2.1 (5)
O16—C15—C16—C17	178.0 (2)	C6—C5—O6—C9	177.8 (3)
C14—C15—C16—C17	−1.7 (4)	C10—C9—O6—C5	179.9 (3)
O16—C15—C16—N4	−4.5 (4)	C14—C13—O13—C12	8.7 (4)
C14—C15—C16—N4	175.7 (2)	C18—C13—O13—C12	−171.2 (3)
C15—C16—C17—C18	0.8 (4)	C11—C12—O13—C13	−173.3 (2)
N4—C16—C17—C18	−176.9 (2)	C14—C15—O16—C19	−1.6 (4)
C16—C17—C18—C13	0.4 (4)	C16—C15—O16—C19	178.7 (2)
C16—C17—C18—N3	178.6 (2)	C20—C19—O16—C15	178.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O11ⁱ	0.82	1.89	2.698 (3)	168
O4—H5···O21ⁱⁱ	0.82	1.74	2.562 (3)	174
O12—H12···O1ⁱⁱⁱ	0.82	1.92	2.730 (3)	168
O14—H15···O18^iv	0.82	2.20	2.921 (3)	147
O14—H15···O17^iv	0.82	2.37	3.055 (3)	141
O21—H21···O15	0.85	2.19	2.947 (4)	148
O21—H21···O10	0.85	2.66	3.084 (4)	113
O21—H22···O5	0.85	1.97	2.798 (4)	165

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x, −y, −z+1; (iii) −x+5/2, y+1/2, −z+1/2; (iv) x−3/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂O₁₀·0.5H₂O
M_r	325.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	7.3873 (15), 25.918 (5), 13.711 (3)
β (°)	99.43 (3)
V (Å³)	2589.7 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.25 × 0.21 × 0.20

Data collection
Diffractometer	Rigaku RAXIS-RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.962, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	19619, 4552, 3197
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.172, 1.03
No. of reflections	4552
No. of parameters	410
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.30

Computer programs: RAPID-AUTO (Rigaku 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).