Bis(2-amino-4-methyl-6-oxo-3,6-di­hydro­pyrimidin-1-ium) sulfate monohydrate

Soudani, S.; Wenger, E.; Jelsch, C.; Ben Nasr, C.

doi:10.1107/S1600536814012513

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 7| July 2014| Pages o747-o748

https://doi.org/10.1107/S1600536814012513

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Bis(2-amino-4-methyl-6-oxo-3,6-dihydropyrimidin-1-ium) sulfate monohydrate

Sarra Soudani,^a Emmanuel Wenger,^b Christian Jelsch ^b and Cherif Ben Nasr ^c ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, ^bCristallographie, Résonance Magnétique et Modélisations (CRM2), UMR CNRS 7036, Institut Jean Barriol, Université de Lorraine, BP 70239, Bd des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France, and ^cLaboratoire de Chimie des Matériaux, Faculté des sciences de Bizerte, 7021 Zarzouna, Tunisia
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 26 May 2014; accepted 29 May 2014; online 4 June 2014)

In the title hydrated molecular salt, 2C₅H₈N₃O⁺·SO₄²⁻·H₂O, the components are linked by N—H⋯O_s and O_w—H⋯O_s (s = sulphate, w = water) hydrogen bonds, generating a layer by a+b+c and 2a−b translations. The cations are arranged nearly in parallel and show displaced π–π stacking centroid–centroid distance = 4.661 (2) Å between adjacent layers.

CCDC reference: 1005732

Related literature

For the applications of oxoanion compounds, see: Vollano et al. (1984 ); Molloy (1988 ). For graph-set motifs, see: Bernstein et al. (1995 ). For the stability of the quinonic and phenolic form in polar solvents, see: Fragoso et al. (2010 ). For C—N single bond lengths, see: Yang et al. (1995 ); Grobelny et al. (1995 ). For the geometrical characteristics of the sulfate anion, see: Das et al. (2009 ); Norquist et al. (2005 ).

Experimental

Crystal data

2C₅H₈N₃O⁺·SO₄²⁻·H₂O
M_r = 366.36
Triclinic, $[P \overline 1]$
a = 6.797 (5) Å
b = 10.339 (6) Å
c = 12.110 (7) Å
α = 113.480 (5)°
β = 91.009 (7)°
γ = 98.906 (5)°
V = 768.2 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.27 × 0.19 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.92, T_max = 0.97
5784 measured reflections
5784 independent reflections
5347 reflections with I > 2σ(I)

Refinement

R[F² > 2σ(F²)] = 0.081
wR(F²) = 0.131
S = 1.35
5784 reflections
289 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O6ⁱ	0.87 (3)	2.02 (3)	2.856 (3)	161 (3)
N1—H1B⋯O4ⁱⁱ	0.83 (3)	2.01 (3)	2.847 (4)	178 (2)
N2—H2⋯O6ⁱⁱⁱ	0.91 (3)	1.88 (2)	2.749 (4)	161 (2)
N7—H7⋯O7ⁱⁱ	0.83 (3)	1.91 (3)	2.730 (4)	170 (3)
N11—H11A⋯O5ⁱⁱⁱ	0.87 (3)	1.91 (3)	2.782 (6)	178 (3)
N11—H11B⋯O5^iv	0.89 (3)	2.07 (3)	2.767 (3)	134 (2)
N12—H12⋯O8^iv	0.92 (3)	1.87 (3)	2.771 (4)	170 (3)
N17—H17⋯O4ⁱⁱⁱ	0.82 (3)	1.92 (3)	2.746 (6)	177 (3)
O8—H8A⋯O13^v	0.86 (3)	1.94 (3)	2.750 (5)	158 (3)
O8—H8B⋯O7	0.83 (3)	2.02 (3)	2.839 (4)	173 (3)
C4—H4⋯O3^vi	0.97 (2)	2.54 (2)	3.485 (3)	165 (2)
C6—H6C⋯O13ⁱⁱ	0.97	2.51	3.440 (3)	162 (2)
C16—H16A⋯O3^vii	0.95	2.58	3.499 (5)	163 (2)
Symmetry codes: (i) x-1, y-1, z; (ii) x, y-1, z; (iii) -x, -y+1, -z; (iv) x-1, y, z; (v) -x+1, -y+2, -z+1; (vi) -x, -y+1, -z+1; (vii) x+1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2012 ); 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 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1005732

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536814012513/bg2531sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012513/bg2531Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012513/bg2531Isup3.cml

checkCIF report

Comment top

Chemists and physicists of the solid state have shown an increasing interest in the study of oxoanion compounds containing organic cations in recent years owing to their applications in various fields (Vollano et al., 1984; Molloy, 1988). Here, we report the synthesis and the crystal structure of the title compound 2(C₅H₈N₃O), O₄S, H₂O. The asymmetric unit of this salt contains two molecules of 2-amino-6-methylpyrimidin-4-(1H)-one, one sulfate anion and one water molecule (Fig. 1). The two independent aromatic cycles of the asymmetric unit are nearly parallel as they form an angle of 5.8°. The shortest distance between non-H atoms of two cations in parallel displaced π- staking is d(O3···N17) = 3.375 (2) Å. When the two cation molecules are viewed along the two centroids, the 6 atom positions of the two cycles appear superposed after a rotation of 60° (Fig. 1). The crystal structure of the title material consists of a network of the different constituents connected by a set of hydrogen bonds (Table 1). Furthermore, in the crystal packing, the two cations are arranged in layers (Fig. 2). The sulfate anion forms the strongest interactions between two parallel layers, as each sulfate moiety interacts with the five cations via seven N—H···O hydrogen bonds. The hydrogen bond network in the cations layer is shown in Fig. 3. The water molecule is acceptor in one N—H···O hydrogen bond and donor in two O—H···O interactions with the sulfate anion and carbonyl group. In the atomic arrangement of the title compound, the sulfate anions are located close to the z=0 plane. Along the a diretion, they are interconnected via a same NH₂ group. In the crystal structure, various graph set motifs (Bernstein et al., 1995) are apparent including R₂⁴ (8) and R₃⁶ (8) loops (Fig. 4). An examination of Table 2 data shows that the distance values of C3—O3 (1.229 (2) Å) and C13—O13 (1.226 (2) Å) can be attributed as having clear double bond character indicating that the title compound is present as the keto tautomer of the 2-amino-6-methyl-4-pyrimidinol(sheme. 2). This observation agrees with the literature data which show that in polar solvents, the quinonic form is more stable than the phenolic one (Fragoso et al., 2010). The C—N bond distances of the NH₂ groups are C1—N1 (1.315 (2) Å), and C11—N11 (1.318 (2) Å) which are short for C—N single bonds, but still not quite as contracted as one would expect for a fully established C=N double bond. These bond length features are consistent with an imino resonance form as it is commonly found for a C—N single bond involving sp² hybridized C and N atoms, (Yang et al., 1995; Grobelny et al., 1995). The S—O bond lengths and the O—S—O bond angles in the sulfate anion are not perfectly equivalent (Das et al., 2009; Norquist et al., 2005), but vary with the environment around the O atoms. In the title compound, the S—O distances are spread between 1.4759 (14) and 1.4949 (16) Å. The O—S—O bond angles range from 108,97 (8) to 110.24 (9)°. All these geometrical parameters indicate relatively little distortion from a regular tetrahedron.

Related literature top

For the applications of oxoanion compounds, see: Vollano et al. (1984); Molloy (1988). For graph-set motifs, see: Bernstein et al. (1995). For the stability of the quinonic and phenolic form in polar solvent, see: Fragoso et al. (2010). For C—N single bond lengths, see: Yang et al. (1995); Grobelny et al. (1995). For the geometrical characteristics of the sulfate anion, see: Das et al. (2009); Norquist et al. (2005).

Experimental top

Commercial 2-amino-4-hydroxy-6-methylpyrimidine (50 mg, 0.4 mmol) dissolved in ethanol (10 ml) was slowly added under stirring to 0.05 mol of sulfuric acid in 20 ml of water. The obtained solution was left to stand at room temperature. The slow evaporation of solvent leads to the formation of colourless single crystals of (I), stable in air and suitable for X-ray diffraction analysis.

Structure description top

For the applications of oxoanion compounds, see: Vollano et al. (1984); Molloy (1988). For graph-set motifs, see: Bernstein et al. (1995). For the stability of the quinonic and phenolic form in polar solvent, see: Fragoso et al. (2010). For C—N single bond lengths, see: Yang et al. (1995); Grobelny et al. (1995). For the geometrical characteristics of the sulfate anion, see: Das et al. (2009); Norquist et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound, showing 50% probability thermal displacement ellipsoids and spheres for the H atoms.
	Fig. 2. View showing the planes formed by the two independant cations molecules. The sulfate anions form the strongest interactions between two parallel layers.
	Fig. 3. View perpendicular to Fig. 2 showing hydrogen bonds stabilizing the structure of the title material in the layer containing the cations.
	Fig. 4. View along the c-axis showing O—H···O and N—H···O hydrogen bonds forming two kinds of 8-membered rings.

Bis(2-amino-4-methyl-6-oxo-3,6-dihydropyrimidin-1-ium) sulfate monohydrate top

Crystal data top

2C₅H₈N₃O⁺·SO₄²⁻·H₂O	V = 768.2 (8) Å³
M_r = 366.36	Z = 2
Triclinic, P1	F(000) = 384
Hall symbol: -P 1	D_x = 1.584 Mg m⁻³
a = 6.797 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.339 (6) Å	θ = 2.2–33.4°
c = 12.110 (7) Å	µ = 0.26 mm⁻¹
α = 113.480 (5)°	T = 100 K
β = 91.009 (7)°	Prism, colourless
γ = 98.906 (5)°	0.27 × 0.19 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	5784 independent reflections
Radiation source: fine-focus sealed tube	5347 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.000
ω scans	θ_max = 33.1°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = 0→10
T_min = 0.92, T_max = 0.97	k = −15→15
5784 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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.35	w = 1/[σ²(F_o²) + (0.044P)² + 0.4148P] where P = (F_o² + 2F_c²)/3
5784 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.64 e Å⁻³
15 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

2C₅H₈N₃O⁺·SO₄²⁻·H₂O	γ = 98.906 (5)°
M_r = 366.36	V = 768.2 (8) Å³
Triclinic, P1	Z = 2
a = 6.797 (5) Å	Mo Kα radiation
b = 10.339 (6) Å	µ = 0.26 mm⁻¹
c = 12.110 (7) Å	T = 100 K
α = 113.480 (5)°	0.27 × 0.19 × 0.12 mm
β = 91.009 (7)°

Data collection top

Bruker APEXII CCD diffractometer	5784 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	5347 reflections with I > 2σ(I)
T_min = 0.92, T_max = 0.97	R_int = 0.000
5784 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	15 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.35	Δρ_max = 0.64 e Å⁻³
5784 reflections	Δρ_min = −0.38 e Å⁻³
289 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
S1	0.32594 (6)	0.79761 (4)	0.06036 (4)	0.00888 (9)
O4	0.10950 (17)	0.75634 (13)	0.01545 (11)	0.0129 (2)
O5	0.39545 (18)	0.67318 (13)	0.06868 (11)	0.0136 (2)
O6	0.44256 (18)	0.84309 (13)	−0.02448 (11)	0.0137 (2)
O7	0.34949 (19)	0.91648 (13)	0.18190 (11)	0.0161 (3)
C1	−0.1015 (2)	0.07187 (17)	0.18509 (14)	0.0097 (3)
N1	−0.1580 (2)	−0.04398 (16)	0.08537 (13)	0.0125 (3)
N2	−0.2110 (2)	0.17792 (15)	0.22132 (13)	0.0113 (3)
C3	−0.1599 (2)	0.30560 (18)	0.32540 (15)	0.0121 (3)
O3	−0.2627 (2)	0.39938 (14)	0.34694 (12)	0.0188 (3)
C4	0.0171 (3)	0.31382 (18)	0.39715 (15)	0.0128 (3)
C5	0.1275 (2)	0.20844 (17)	0.35890 (15)	0.0109 (3)
C6	0.3178 (3)	0.2130 (2)	0.42459 (17)	0.0171 (3)
N7	0.0687 (2)	0.08908 (15)	0.25224 (13)	0.0108 (3)
C11	−0.0959 (2)	0.61151 (17)	0.19155 (15)	0.0113 (3)
N11	−0.2643 (2)	0.58800 (17)	0.12550 (14)	0.0145 (3)
N12	−0.0358 (2)	0.73732 (16)	0.28733 (13)	0.0138 (3)
C13	0.1415 (3)	0.76947 (19)	0.36118 (16)	0.0151 (3)
O13	0.1845 (2)	0.88853 (14)	0.44418 (12)	0.0226 (3)
C14	0.2552 (3)	0.65558 (19)	0.33060 (16)	0.0153 (3)
C15	0.1953 (2)	0.53064 (18)	0.23358 (15)	0.0119 (3)
C16	0.3067 (3)	0.4085 (2)	0.18954 (17)	0.0149 (3)
N17	0.0195 (2)	0.51065 (15)	0.16497 (13)	0.0111 (3)
O8	0.6783 (2)	0.91155 (15)	0.32711 (12)	0.0190 (3)
H1A	−0.274 (4)	−0.063 (3)	0.046 (2)	0.020 (6)*
H1B	−0.082 (4)	−0.104 (3)	0.064 (2)	0.019 (6)*
H2	−0.310 (4)	0.173 (3)	0.168 (2)	0.028 (7)*
H4	0.060 (4)	0.398 (2)	0.472 (2)	0.019 (6)*
H6A	0.344 (3)	0.302 (3)	0.4979 (18)	0.032 (7)*
H6B	0.425 (2)	0.212 (3)	0.379 (2)	0.031 (7)*
H6C	0.306 (4)	0.130 (3)	0.444 (2)	0.038 (8)*
H7	0.143 (4)	0.028 (3)	0.230 (2)	0.029 (7)*
H11A	−0.303 (4)	0.505 (3)	0.065 (3)	0.029 (7)*
H11B	−0.337 (4)	0.657 (3)	0.143 (2)	0.026 (6)*
H12	−0.118 (4)	0.804 (3)	0.305 (2)	0.027 (6)*
H14	0.374 (4)	0.672 (3)	0.378 (2)	0.023 (6)*
H16A	0.417 (3)	0.424 (3)	0.245 (2)	0.031 (7)*
H16B	0.351 (3)	0.397 (2)	0.1108 (18)	0.024 (6)*
H16C	0.220 (4)	0.3214 (14)	0.178 (2)	0.021 (6)*
H17	−0.020 (4)	0.432 (3)	0.109 (3)	0.030 (7)*
H8A	0.694 (5)	0.983 (3)	0.396 (3)	0.041 (8)*
H8B	0.577 (4)	0.914 (3)	0.290 (3)	0.030 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.00752 (16)	0.00803 (17)	0.00983 (17)	0.00195 (12)	−0.00157 (12)	0.00220 (13)
O4	0.0068 (5)	0.0115 (5)	0.0166 (6)	0.0011 (4)	−0.0022 (4)	0.0021 (4)
O5	0.0146 (6)	0.0110 (5)	0.0163 (6)	0.0039 (4)	−0.0024 (5)	0.0062 (5)
O6	0.0106 (5)	0.0167 (6)	0.0154 (6)	0.0004 (4)	−0.0017 (4)	0.0090 (5)
O7	0.0152 (6)	0.0146 (6)	0.0124 (6)	0.0066 (5)	−0.0038 (5)	−0.0022 (4)
C1	0.0081 (6)	0.0115 (7)	0.0100 (7)	0.0016 (5)	0.0006 (5)	0.0048 (6)
N1	0.0091 (6)	0.0125 (6)	0.0126 (6)	0.0027 (5)	−0.0017 (5)	0.0015 (5)
N2	0.0098 (6)	0.0124 (6)	0.0113 (6)	0.0043 (5)	−0.0009 (5)	0.0034 (5)
C3	0.0113 (7)	0.0123 (7)	0.0119 (7)	0.0020 (6)	0.0001 (6)	0.0041 (6)
O3	0.0181 (6)	0.0157 (6)	0.0202 (6)	0.0088 (5)	−0.0010 (5)	0.0028 (5)
C4	0.0133 (7)	0.0115 (7)	0.0116 (7)	0.0019 (6)	−0.0020 (6)	0.0026 (6)
C5	0.0099 (7)	0.0110 (7)	0.0111 (7)	0.0000 (5)	−0.0015 (5)	0.0044 (6)
C6	0.0141 (8)	0.0163 (8)	0.0184 (8)	0.0029 (6)	−0.0066 (6)	0.0048 (7)
N7	0.0088 (6)	0.0101 (6)	0.0117 (6)	0.0030 (5)	−0.0013 (5)	0.0022 (5)
C11	0.0107 (7)	0.0110 (7)	0.0121 (7)	0.0009 (6)	0.0004 (6)	0.0051 (6)
N11	0.0112 (6)	0.0115 (6)	0.0186 (7)	0.0032 (5)	−0.0040 (5)	0.0037 (6)
N12	0.0143 (7)	0.0109 (6)	0.0132 (6)	0.0026 (5)	−0.0013 (5)	0.0019 (5)
C13	0.0162 (8)	0.0151 (8)	0.0122 (7)	0.0002 (6)	−0.0014 (6)	0.0048 (6)
O13	0.0290 (7)	0.0153 (6)	0.0152 (6)	−0.0003 (5)	−0.0051 (5)	−0.0007 (5)
C14	0.0135 (8)	0.0181 (8)	0.0128 (7)	0.0004 (6)	−0.0038 (6)	0.0056 (6)
C15	0.0092 (7)	0.0156 (7)	0.0129 (7)	0.0018 (6)	−0.0003 (6)	0.0081 (6)
C16	0.0111 (7)	0.0178 (8)	0.0173 (8)	0.0052 (6)	0.0008 (6)	0.0077 (7)
N17	0.0093 (6)	0.0100 (6)	0.0116 (6)	0.0015 (5)	−0.0019 (5)	0.0021 (5)
O8	0.0199 (7)	0.0198 (7)	0.0130 (6)	0.0092 (5)	−0.0041 (5)	0.0004 (5)

Geometric parameters (Å, º) top

S1—O5	1.4759 (14)	N7—H7	0.83 (3)
S1—O7	1.4805 (14)	C11—N11	1.318 (2)
S1—O6	1.4843 (14)	C11—N17	1.342 (2)
S1—O4	1.4949 (16)	C11—N12	1.349 (2)
C1—N1	1.315 (2)	N11—H11A	0.87 (3)
C1—N7	1.349 (2)	N11—H11B	0.89 (3)
C1—N2	1.353 (2)	N12—C13	1.402 (2)
N1—H1A	0.87 (3)	N12—H12	0.91 (3)
N1—H1B	0.83 (3)	C13—O13	1.226 (2)
N2—C3	1.403 (2)	C13—C14	1.437 (3)
N2—H2	0.91 (3)	C14—C15	1.351 (2)
C3—O3	1.229 (2)	C14—H14	0.94 (3)
C3—C4	1.443 (2)	C15—N17	1.383 (2)
C4—C5	1.352 (2)	C15—C16	1.492 (3)
C4—H4	0.97 (2)	C16—H16A	0.95 (2)
C5—N7	1.382 (2)	C16—H16B	0.972 (19)
C5—C6	1.491 (2)	C16—H16C	0.953 (19)
C6—H6A	0.98 (2)	N17—H17	0.83 (3)
C6—H6B	0.92 (2)	O8—H8A	0.86 (3)
C6—H6C	0.97 (2)	O8—H8B	0.82 (3)

O5—S1—O7	109.31 (8)	C1—N7—H7	120.5 (19)
O5—S1—O6	109.99 (8)	C5—N7—H7	117.9 (19)
O7—S1—O6	110.24 (9)	N11—C11—N17	120.64 (15)
O5—S1—O4	108.97 (8)	N11—C11—N12	120.77 (16)
O7—S1—O4	108.81 (7)	N17—C11—N12	118.59 (15)
O6—S1—O4	109.49 (8)	C11—N11—H11A	119.9 (18)
N1—C1—N7	120.88 (15)	C11—N11—H11B	119.6 (17)
N1—C1—N2	120.63 (15)	H11A—N11—H11B	120 (2)
N7—C1—N2	118.48 (15)	C11—N12—C13	123.73 (15)
C1—N1—H1A	122.7 (16)	C11—N12—H12	117.5 (17)
C1—N1—H1B	117.4 (17)	C13—N12—H12	118.8 (17)
H1A—N1—H1B	120 (2)	O13—C13—N12	118.40 (17)
C1—N2—C3	124.22 (14)	O13—C13—C14	126.54 (17)
C1—N2—H2	116.8 (17)	N12—C13—C14	115.06 (15)
C3—N2—H2	118.0 (17)	C15—C14—C13	120.77 (16)
O3—C3—N2	119.39 (15)	C15—C14—H14	121.2 (15)
O3—C3—C4	125.98 (16)	C13—C14—H14	118.0 (15)
N2—C3—C4	114.61 (14)	C14—C15—N17	119.59 (16)
C5—C4—C3	120.56 (15)	C14—C15—C16	125.40 (16)
C5—C4—H4	120.1 (14)	N17—C15—C16	115.00 (15)
C3—C4—H4	119.2 (14)	C15—C16—H16A	110.6 (13)
C4—C5—N7	120.36 (15)	C15—C16—H16B	109.0 (12)
C4—C5—C6	123.67 (15)	H16A—C16—H16B	111 (2)
N7—C5—C6	115.96 (15)	C15—C16—H16C	110.2 (12)
C5—C6—H6A	108.6 (13)	H16A—C16—H16C	110 (2)
C5—C6—H6B	112.1 (14)	H16B—C16—H16C	106 (2)
H6A—C6—H6B	108 (2)	C11—N17—C15	122.20 (15)
C5—C6—H6C	109.4 (14)	C11—N17—H17	119.0 (19)
H6A—C6—H6C	111 (2)	C15—N17—H17	118.7 (19)
H6B—C6—H6C	108 (2)	H8A—O8—H8B	108 (3)
C1—N7—C5	121.60 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O6ⁱ	0.87 (3)	2.02 (3)	2.856 (3)	161 (3)
N1—H1B···O4ⁱⁱ	0.83 (3)	2.01 (3)	2.847 (4)	178 (2)
N2—H2···O6ⁱⁱⁱ	0.91 (3)	1.88 (2)	2.749 (4)	161 (2)
N7—H7···O7ⁱⁱ	0.83 (3)	1.91 (3)	2.730 (4)	170 (3)
N11—H11A···O5ⁱⁱⁱ	0.87 (3)	1.91 (3)	2.782 (6)	178 (3)
N11—H11B···O5^iv	0.89 (3)	2.07 (3)	2.767 (3)	134 (2)
N12—H12···O8^iv	0.92 (3)	1.87 (3)	2.771 (4)	170 (3)
N17—H17···O4ⁱⁱⁱ	0.82 (3)	1.92 (3)	2.746 (6)	177 (3)
O8—H8A···O13^v	0.86 (3)	1.94 (3)	2.750 (5)	158 (3)
O8—H8B···O7	0.83 (3)	2.02 (3)	2.839 (4)	173 (3)
C4—H4···O3^vi	0.97 (2)	2.54 (2)	3.485 (3)	165 (2)
C6—H6C···O13ⁱⁱ	0.97	2.51	3.440 (3)	162 (2)
C16—H16A···O3^vii	0.95	2.58	3.499 (5)	163 (2)

Symmetry codes: (i) x−1, y−1, z; (ii) x, y−1, z; (iii) −x, −y+1, −z; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) −x, −y+1, −z+1; (vii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O6ⁱ	0.87 (3)	2.02 (3)	2.856 (3)	161 (3)
N1—H1B···O4ⁱⁱ	0.83 (3)	2.01 (3)	2.847 (4)	178 (2)
N2—H2···O6ⁱⁱⁱ	0.91 (3)	1.88 (2)	2.749 (4)	161 (2)
N7—H7···O7ⁱⁱ	0.83 (3)	1.91 (3)	2.730 (4)	170 (3)
N11—H11A···O5ⁱⁱⁱ	0.87 (3)	1.91 (3)	2.782 (6)	178 (3)
N11—H11B···O5^iv	0.89 (3)	2.07 (3)	2.767 (3)	134 (2)
N12—H12···O8^iv	0.92 (3)	1.87 (3)	2.771 (4)	170 (3)
N17—H17···O4ⁱⁱⁱ	0.82 (3)	1.92 (3)	2.746 (6)	177 (3)
O8—H8A···O13^v	0.86 (3)	1.94 (3)	2.750 (5)	158 (3)
O8—H8B···O7	0.83 (3)	2.02 (3)	2.839 (4)	173 (3)
C4—H4···O3^vi	0.97 (2)	2.54 (2)	3.485 (3)	165 (2)
C6—H6C···O13ⁱⁱ	0.968	2.51	3.440 (3)	162 (2)
C16—H16A···O3^vii	0.946	2.583	3.499 (5)	163 (2)

Symmetry codes: (i) x−1, y−1, z; (ii) x, y−1, z; (iii) −x, −y+1, −z; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) −x, −y+1, −z+1; (vii) x+1, y, z.

Acknowledgements

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia.

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