Crystal structure of 1,3-bis­(1,3-dioxoisoindolin-1-yl)urea dihydrate: a urea-based anion receptor

Medrano, F.; Lujano, S.; Godoy-Alcántar, C.; Tlahuext, H.

doi:10.1107/S1600536814022144

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Volume 70| Part 11| November 2014| Pages 373-375

doi:10.1107/S1600536814022144

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Crystal structure of 1,3-bis(1,3-dioxoisoindolin-1-yl)urea dihydrate: a urea-based anion receptor

Felipe Medrano,^a ^* Sergio Lujano,^a Carolina Godoy-Alcántar ^a and Hugo Tlahuext ^a

^aCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001 Col., Chamilpa, CP 62209, Cuernavaca, Mexico
^*Correspondence e-mail: fmedrano@uaem.mx

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 September 2014; accepted 7 October 2014; online 24 October 2014)

The whole molecule of the title compound, C₁₇H₁₀N₄O₅·2H₂O, is generated by twofold rotation symmetry and it crystallized as a dihydrate. The planes of the phthalimide moieties and the urea unit are almost normal to one another, with a dihedral angle of 78.62 (9)°. In the crystal, molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional framework structure. The crystal packing also features C—H⋯O hydrogen bonds and slipped parallel π–π interactions [centroid–centroid distance = 3.6746 (15) Å] involving the benzene rings of neighbouring phthalimide moieties.

Keywords: crystal structure; isoindoline; urea; phthalimides; protection of primary amines; urea-based anion receptor.

CCDC reference: 1027988

1. Chemical context

Hydrogen bonding and π–π interactions are two of the principal forces which determine structure, self-assembly and recognition in some chemical and biological systems (Lehn, 1990 ). A variety of urea-based anion receptors of varying complexity and sophistication have been synthesised (Amendola et al., 2010 ). It has been shown that the efficiency of urea as a receptor subunit depends on the presence of two proximate polarised N—H fragments, capable of (i) chelating a spherical anion or (ii) donating two parallel hydrogen bonds to the O atoms of a carboxylate or of an inorganic oxoanion. A review of the biological activity of phthalimides has been published by Sharma et al. (2010 ) and a review of its the supramolecular chemistry by Barooah & Baruah (2007 ). Phthalimides and isoindolines have been shown to possess photophysical properties and have applications as colourimetric and other types of anion sensors (Griesbeck & Schieffer, 2003 ; Griesbeck et al., 2007 , 2010 ; Devaraj & Kandaswamy, 2013 ). In our ongoing research on 1,3-dioxoisoindolines as anion receptors (Lujano, 2012 ), we report herein on the synthesis and crystal structure of the title urea-based anion receptor.

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. The molecule is located on a crystallographic twofold rotation axis that bisects the central C9=O3 bond. The planes of the phthalimide unit (N1/C1–C8) and the urea unit [N2—C9(=O3)—N2] are almost normal to one another, with a dihedral angle of 78.62 (9)°. The planes of the symmetry-related phthalimide moieties [N1/C1–C8 and N1ⁱ/C1ⁱ–C8ⁱ; symmetry code: (i) −x, y, −z + $[{1\over 2}]$ ] are inclined to one another by 73.53 (7)°.

Figure 1
The molecular structure of the title molecule, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Atoms with the suffix A are generated by the symmetry operator (−x, y, −z + $[{1\over 2}]$ ) and the symmetry-related water molecule is not shown.

3. Supramolecular features

In the crystal, molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional framework structure (Table 1 and Fig. 2). The solvent water molecules, which occupy general positions, take part in the hydrogen-bonding network (Table 1 and Figs. 2 and 3). The O atom of the water molecules, O4, is an acceptor of one H atom and simultaneously a donor of their two H atoms and enclose R₄⁴(24) and R₃³(15) ring motifs (Table 1 and Fig. 3). The crystal packing is reinforced by C—H⋯O hydrogen bonds, and slipped parallel π–π interactions (Fig. 4) involving benzene rings of neighbouring phthalimide moieties [Cg⋯Cgⁱ = 3.6746 (15) Å; normal distance = 3.3931 (9) Å; slippage = 1.411 Å; Cg is the centroid of the C1–C6 ring; symmetry code: (i) −x + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , −z + 2].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4ⁱ	0.87 (2)	1.96 (2)	2.811 (3)	167 (2)
O4—H4A⋯O1ⁱⁱ	0.85 (1)	2.11 (1)	2.891 (3)	154 (3)
O4—H4B⋯O2ⁱⁱⁱ	0.85 (2)	2.01 (2)	2.850 (3)	175 (3)
C3—H3⋯O1^iv	0.93	2.56	3.447 (3)	160
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+1, -z+2; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1

for details. C-bound H atoms have been omitted for clarity.

Figure 3
A view of the crystal packing of the title compound. The hydrogen bonds (dashed lines; see Table 1

for details) enclose R₄⁴(24) and R₃³(15) ring motifs.

Figure 4
Two molecules of the title compound showing the offset π–π interactions involving the benzene rings of neighbouring phthalimide moieties (dashed line).

4. Synthesis and crystallization

Carbohydrazide (0.5 g, 5.5 mmol) and phthalic anhydride (1.64 g, 11 mmol) were dissolved in dimethyl sulfoxide (15 ml) and refluxed for 6 h at 323 K. The solvent was removed under reduced pressure in a rotatory evaporator and the pale-yellow solid residue was washed with water and dried under vacuum. The product was recrystallized from water/ethanol (30:70 v/v) to give colourless prismatic crystals suitable for X-ray diffraction analysis (m.p. 491–493 K). ¹H NMR (200 MHz, DMSO-d₆, Me₄Si): δ 9.25 (2H, N—H), 7.80 (8H, Ar). ¹³C NMR (50 MHz, DMSO-d₆, Me₄Si): δ 165.2 (C7, C8, C7′, C8′), 154.7 (C9), 135.0 (C5, C2, C5′, C2′), 129.4 (C1, C6, C1′, C6′), 123.5 (C3, C4, C3′, C4′). MS (FAB⁺): m/z (%) 349 (M—H, 25).

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH group and water molecule H atoms were located in a difference Fourier map and refined with distance restraints N—H = 0.86 (1) Å and O—H = 0.84 (1) Å, and with U_iso(H) = 1.2U_eq(N) and 1.5U_eq(O). C-bound H atoms were positioned geometrically and constrained using a riding-model approximation, with C—H = 0.93 Å andU_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₀N₄O₅·2H₂O
M_r	386.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.268 (3), 7.8053 (16), 14.729 (3)
β (°)	102.097 (3)
V (Å³)	1716.3 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.40 × 0.32 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.954, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	7038, 1529, 1414
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.130, 1.12
No. of reflections	1529
No. of parameters	141
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.25
Computer programs: SMART and SAINT-Plus (Bruker, 2001 ), SHELXS97, SHELXL97 and SHELXTL-NT (Sheldrick, 2008 ), DIAMOND (Brandenburg, 1997 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1027988

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022144/su2791sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022144/su2791Isup2.hkl

checkCIF report

Chemical context top

Hydrogen bonding and π–π interactions are two of the principal forces which determine structure, self-assembly and recognition in some chemical and biological systems (Lehn, 1990). A variety of urea-based anion receptors of varying complexity and sophistication have been synthesised (Amendola et al., 2010). It has been shown that the efficiency of urea as a receptor subunit depends on the presence of two proximate polarised N—H fragments, capable of (i) chelating a spherical anion or (ii) donating two parallel hydrogen bonds to the O atoms of a carboxylate or of an inorganic oxoanion. A review of the biological activity of phthalimides has been published by Sharma et al. (2010) and a review of its the supramolecular chemistry by Barooah & Baruah (2007). Phthalimides and isoindolines have been shown to possess photophysical properties and have applications as colourimetric and other types of anion sensors (Griesbeck & Schieffer, 2003; Griesbeck et al., 2007, 2010; Devaraj & Kandaswamy, 2013). In our ongoing research on 1,3-dioxoisoindolines as anion receptors (Lujano, 2012), we report herein on the synthesis and crystal structure of the title urea-based anion receptor.

Synthesis and crystallization top

Carbohydrazide (0.5 g, 5.5 mmol) and phthalic anhydride (1.64 g, 11 mmol) were dissolved in dimethyl sulfoxide (15 ml) and refluxed for 6 h at 323 K. The solvent was removed under reduced pressure in a rotatory evaporator and the pale-yellow solid residue was washed with water and dried under vacuum. The product was recrystallized from water/ethanol (30:70 v/v) to give colourless prismatic crystals suitable for X-ray diffraction analysis (m.p. 491–493 K). ¹H NMR (200 MHz, DMSO-d_6, Me₄Si): δ 9.25 (2H, N—H), 7.80 (8H, Ar). ¹³C NMR (50 MHz, DMSO-d₆, Me₄Si): δ 165.2 (C7, C8, C7', C8'), 154.7 (C9), 135.0 (C5, C2, C5', C2'), 129.4 (C1, C6, C1', C6'), 123.5 (C3, C4, C3', C4'). MS (FAB⁺): m/z (%) 349 (M—H, 25).

Structural commentary top

The molecular structure of the title compound is illustrated in Fig. 1. The molecule is located on a crystallographic twofold rotation axis that bisects the central C9═O3 bond. The planes of the phthalimide unit (N1/C1–C8) and the urea unit [N2—C9(═O3)—N2] are almost normal to one another, with a dihedral angle of 78.62 (9)°. The planes of the symmetry-related phthalimide moieties [N1/C1–C8 and N1ⁱ/C1ⁱ–C8ⁱ; symmetry code: (i) -x, y, -z+1/2] are inclined to one another by 73.53 (7)°.

Supramolecular features top

In the crystal, molecules are linked by N—H···O and O—H···O hydrogen bonds, forming a three-dimensional framework structure (Table 1 and Fig. 2). The solvent water molecules, which occupy general positions, take part in the hydrogen-bonding network (Table 1 and Figs. 2 and 3). The O atom of the water molecules, O4, is an acceptor of one H atom and simultaneously a donor of their two H atoms and enclose R₄⁴(24) and R₃³(15) ring motifs (Table 1 and Fig. 3). The crystal packing is reinforced by C—H···O hydrogen bonds, and slipped parallel π–π interactions (Fig. 4) involving benzene rings of neighbouring phthalimide moieties [Cg···Cgⁱ = 3.6746 (15) Å; normal distance = 3.3931 (9) Å; slippage = 1.411 Å; Cg is the centroid of the C1–C6 ring; symmetry code: (i) -x+3/2, -y+1/2, -z+2].

Refinement details top

Related literature top

For related literature, see: Amendola et al. (2010); Barooah & Baruah (2007); Devaraj & Kandaswamy (2013); Griesbeck & Schieffer (2003); Griesbeck et al. (2007, 2010); Lehn (1990); Lujano (2012); Sharma et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

The molecular structure of the title molecule, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Atoms with the suffix A are generated by the symmetry operator (-x, y, -z+1/2) and the symmetry-related water molecule is not shown.

A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details. C-bound H atoms have been omitted for clarity.

A view of the crystal packing of the title compound. The hydrogen bonds (dashed lines; see Table 1 for details) enclose R₄⁴(24) and R₃³(15) ring motifs.

Two molecules of the title compound showing the offset π–π interactions involving the benzene rings of neighbouring phthalimide moieties (dashed line).

1,3-Bis(1,3-dioxoisoindolin-1-yl)urea dihydrate top

Crystal data top

C₁₇H₁₀N₄O₅·2H₂O	F(000) = 800
M_r = 386.32	D_x = 1.495 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5032 reflections
a = 15.268 (3) Å	θ = 2.6–28.1°
b = 7.8053 (16) Å	µ = 0.12 mm⁻¹
c = 14.729 (3) Å	T = 293 K
β = 102.097 (3)°	Prism, colourless
V = 1716.3 (6) Å³	0.40 × 0.32 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1529 independent reflections
Radiation source: fine-focus sealed tube	1414 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 8.3 pixels mm^-1	θ_max = 25.1°, θ_min = 2.7°
phi and ω scans	h = −17→18
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.954, T_max = 0.973	l = −17→17
7038 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0524P)² + 1.5592P] where P = (F_o² + 2F_c²)/3
1529 reflections	(Δ/σ)_max = 0.001
141 parameters	Δρ_max = 0.37 e Å⁻³
4 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₇H₁₀N₄O₅·2H₂O	V = 1716.3 (6) Å³
M_r = 386.32	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.268 (3) Å	µ = 0.12 mm⁻¹
b = 7.8053 (16) Å	T = 293 K
c = 14.729 (3) Å	0.40 × 0.32 × 0.23 mm
β = 102.097 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1529 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1414 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.973	R_int = 0.035
7038 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	4 restraints
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.37 e Å⁻³
1529 reflections	Δρ_min = −0.25 e Å⁻³
141 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
O1	1.04237 (9)	0.1919 (2)	1.00070 (10)	0.0522 (4)
O2	0.79568 (10)	0.2183 (3)	0.76586 (10)	0.0646 (5)
O3	1.0000	0.3375 (3)	0.7500	0.0527 (6)
O4	0.89221 (13)	0.7577 (3)	0.80226 (14)	0.0780 (6)
N1	0.92631 (11)	0.1729 (2)	0.87283 (11)	0.0453 (5)
N2	0.97120 (12)	0.0845 (2)	0.81541 (12)	0.0477 (5)
C1	0.82495 (13)	0.3490 (3)	0.91942 (14)	0.0424 (5)
C2	0.75114 (14)	0.4447 (3)	0.92811 (17)	0.0528 (6)
H2	0.7014	0.4533	0.8795	0.063*
C3	0.75383 (16)	0.5273 (3)	1.01160 (18)	0.0589 (6)
H3	0.7050	0.5926	1.0193	0.071*
C4	0.82743 (16)	0.5149 (3)	1.08370 (19)	0.0611 (6)
H4	0.8270	0.5716	1.1392	0.073*
C5	0.90231 (15)	0.4194 (3)	1.07526 (16)	0.0515 (6)
C6	0.89956 (12)	0.3377 (2)	0.99210 (13)	0.0398 (5)
C7	0.96745 (13)	0.2286 (3)	0.96152 (13)	0.0392 (5)
C8	0.84162 (14)	0.2441 (3)	0.84167 (14)	0.0458 (5)
C9	1.0000	0.1824 (4)	0.7500	0.0416 (7)
H5	0.9532 (16)	0.412 (3)	1.1262 (17)	0.057 (6)*
H2A	0.9521 (17)	−0.0195 (17)	0.8048 (18)	0.068*
H4B	0.8366 (8)	0.741 (4)	0.784 (2)	0.085*
H4A	0.905 (2)	0.740 (4)	0.8601 (8)	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0329 (8)	0.0684 (10)	0.0520 (9)	0.0035 (7)	0.0018 (6)	0.0030 (7)
O2	0.0456 (9)	0.1021 (14)	0.0418 (9)	−0.0006 (9)	−0.0005 (7)	0.0028 (8)
O3	0.0514 (13)	0.0556 (14)	0.0510 (12)	0.000	0.0105 (10)	0.000
O4	0.0571 (11)	0.0918 (14)	0.0762 (13)	−0.0158 (10)	−0.0063 (10)	0.0090 (11)
N1	0.0363 (9)	0.0633 (11)	0.0374 (9)	0.0055 (8)	0.0104 (7)	0.0008 (8)
N2	0.0495 (10)	0.0558 (11)	0.0418 (9)	−0.0005 (9)	0.0185 (8)	−0.0018 (8)
C1	0.0345 (10)	0.0471 (11)	0.0467 (11)	−0.0009 (9)	0.0108 (8)	0.0104 (9)
C2	0.0372 (11)	0.0571 (13)	0.0648 (14)	0.0039 (10)	0.0122 (10)	0.0169 (11)
C3	0.0480 (13)	0.0474 (13)	0.0889 (18)	0.0033 (10)	0.0314 (13)	0.0017 (12)
C4	0.0578 (15)	0.0566 (14)	0.0747 (15)	−0.0090 (11)	0.0273 (12)	−0.0181 (12)
C5	0.0443 (12)	0.0560 (13)	0.0548 (13)	−0.0088 (10)	0.0117 (10)	−0.0102 (10)
C6	0.0323 (10)	0.0427 (10)	0.0452 (11)	−0.0050 (8)	0.0100 (8)	0.0044 (8)
C7	0.0325 (10)	0.0469 (11)	0.0379 (10)	−0.0038 (8)	0.0069 (8)	0.0056 (8)
C8	0.0358 (11)	0.0636 (13)	0.0376 (11)	−0.0025 (9)	0.0070 (9)	0.0094 (9)
C9	0.0323 (14)	0.0539 (18)	0.0371 (14)	0.000	0.0039 (11)	0.000

Geometric parameters (Å, º) top

O1—C7	1.203 (2)	C1—C8	1.472 (3)
O2—C8	1.205 (2)	C2—C3	1.381 (3)
O3—C9	1.210 (4)	C2—H2	0.9300
O4—H4B	0.846 (10)	C3—C4	1.378 (3)
O4—H4A	0.844 (10)	C3—H3	0.9300
N1—N2	1.380 (2)	C4—C5	1.392 (3)
N1—C8	1.394 (3)	C4—H4	0.9300
N1—C7	1.395 (3)	C5—C6	1.374 (3)
N2—C9	1.373 (2)	C5—H5	0.96 (2)
N2—H2A	0.865 (10)	C6—C7	1.483 (3)
C1—C2	1.380 (3)	C9—N2ⁱ	1.373 (2)
C1—C6	1.393 (3)

H4B—O4—H4A	108 (3)	C3—C4—H4	119.3
N2—N1—C8	122.91 (16)	C5—C4—H4	119.3
N2—N1—C7	123.07 (16)	C6—C5—C4	117.1 (2)
C8—N1—C7	112.88 (17)	C6—C5—H5	122.4 (14)
C9—N2—N1	115.14 (19)	C4—C5—H5	120.5 (14)
C9—N2—H2A	122.8 (18)	C5—C6—C1	121.5 (2)
N1—N2—H2A	112.8 (18)	C5—C6—C7	130.16 (19)
C2—C1—C6	121.0 (2)	C1—C6—C7	108.31 (17)
C2—C1—C8	130.59 (19)	O1—C7—N1	124.85 (19)
C6—C1—C8	108.40 (17)	O1—C7—C6	130.25 (19)
C1—C2—C3	117.6 (2)	N1—C7—C6	104.90 (16)
C1—C2—H2	121.2	O2—C8—N1	123.9 (2)
C3—C2—H2	121.2	O2—C8—C1	130.7 (2)
C4—C3—C2	121.4 (2)	N1—C8—C1	105.38 (16)
C4—C3—H3	119.3	O3—C9—N2ⁱ	123.86 (13)
C2—C3—H3	119.3	O3—C9—N2	123.86 (13)
C3—C4—C5	121.4 (2)	N2ⁱ—C9—N2	112.3 (3)

C8—N1—N2—C9	69.0 (2)	C8—N1—C7—C6	3.9 (2)
C7—N1—N2—C9	−97.9 (2)	C5—C6—C7—O1	−3.6 (4)
C6—C1—C2—C3	−0.5 (3)	C1—C6—C7—O1	176.4 (2)
C8—C1—C2—C3	178.3 (2)	C5—C6—C7—N1	176.7 (2)
C1—C2—C3—C4	0.0 (3)	C1—C6—C7—N1	−3.3 (2)
C2—C3—C4—C5	0.3 (4)	N2—N1—C8—O2	9.2 (3)
C3—C4—C5—C6	−0.2 (3)	C7—N1—C8—O2	177.3 (2)
C4—C5—C6—C1	−0.3 (3)	N2—N1—C8—C1	−171.03 (18)
C4—C5—C6—C7	179.7 (2)	C7—N1—C8—C1	−2.9 (2)
C2—C1—C6—C5	0.7 (3)	C2—C1—C8—O2	1.4 (4)
C8—C1—C6—C5	−178.36 (19)	C6—C1—C8—O2	−179.6 (2)
C2—C1—C6—C7	−179.32 (18)	C2—C1—C8—N1	−178.3 (2)
C8—C1—C6—C7	1.6 (2)	C6—C1—C8—N1	0.7 (2)
N2—N1—C7—O1	−7.7 (3)	N1—N2—C9—O3	11.43 (18)
C8—N1—C7—O1	−175.81 (19)	N1—N2—C9—N2ⁱ	−168.57 (18)
N2—N1—C7—C6	171.95 (17)

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ⁱⁱ	0.87 (2)	1.96 (2)	2.811 (3)	167 (2)
O4—H4A···O1ⁱⁱⁱ	0.85 (1)	2.11 (1)	2.891 (3)	154 (3)
O4—H4B···O2^iv	0.85 (2)	2.01 (2)	2.850 (3)	175 (3)
C3—H3···O1^v	0.93	2.56	3.447 (3)	160

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ⁱ	0.866 (15)	1.962 (17)	2.811 (3)	167 (2)
O4—H4A···O1ⁱⁱ	0.845 (12)	2.108 (14)	2.891 (3)	154 (3)
O4—H4B···O2ⁱⁱⁱ	0.845 (16)	2.007 (17)	2.850 (3)	175 (3)
C3—H3···O1^iv	0.93	2.56	3.447 (3)	160

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₀N₄O₅·2H₂O
M_r	386.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	15.268 (3), 7.8053 (16), 14.729 (3)
β (°)	102.097 (3)
V (Å³)	1716.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.40 × 0.32 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.954, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	7038, 1529, 1414
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.130, 1.12
No. of reflections	1529
No. of parameters	141
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.25

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1997) and PLATON (Spek, 2009), SHELXTL-NT (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the Consejo Nacional de Ciencia y Tecnología (CONACyT) under grant No. 49997Q.

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