4-Aza­niumyl-2,2,6,6-tetra­methyl­piperidin-1-ium dinitrate

Chebbi, H.; Ben Smail, R.; Zid, M.F.

doi:10.1107/S1600536814009787

organic compounds

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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o642

doi:10.1107/S1600536814009787

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4-Azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dinitrate

Hammouda Chebbi,^a,^b ^* Ridha Ben Smail ^c,^b and Mohamed Faouzi Zid ^b

^aInstitut Préparatoire aux Etudes d'Ingénieurs de Monastir, Avenue Ibn-El-Jazzar, 5019 Monastir, Tunisia, ^bLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, 2092 El Manar II, Tunis, Tunisia, and ^cInstitut Préparatoire aux Etudes d'Ingénieurs de Nabeul, Campus Universitaire Mrazka, 8000 Nabeul, Tunisia
^*Correspondence e-mail: chebhamouda@yahoo.fr

Edited by C. Näther, Universität Kiel, Germany (Received 11 April 2014; accepted 30 April 2014; online 10 May 2014)

In the crystal structure of the title salt, C₉H₂₂N₂²⁺·2NO₃⁻, the piperidine ring of the dication adopts a chair conformation and the orientation of the C—NH₃ bond is equatorial. The ions are linked by normal and bifurcated N—H⋯O hydrogen bonds in R₂²(6), two R₄²(8) and R₃⁴(14) graf-set motifs, generating a three-dimensional network.

CCDC reference: 1000438

Related literature

For related structures, see: Chebbi & Driss (2001 ); El Glaoui, Mrad, Jenneau & Ben Nasr (2010 ); Mrad et al. (2009 ); Huang & Deng (2007 ). For hydrogen bonding and graph-set motifs, see: Jeffrey (1997 ); Bernstein et al. (1995 ); Etter et al. (1990 ). For ring-puckering parameters, see: Cremer & Pople (1975 ); Spek (2009 ).

Experimental

Crystal data

C₉H₂₂N₂²⁺·2NO₃⁻
M_r = 282.31
Monoclinic, P 2₁ /n
a = 10.367 (2) Å
b = 11.054 (1) Å
c = 13.167 (2) Å
β = 112.45 (2)°
V = 1394.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.45 × 0.30 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.860, T_max = 0.978
2849 measured reflections
2731 independent reflections
1908 reflections with I > 2σ(I)
R_int = 0.017
2 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.121
S = 1.05
2731 reflections
261 parameters
All H-atom parameters refined
Δρ_max = 0.24 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⋯O1ⁱ	0.93 (2)	1.99 (2)	2.868 (2)	156.9 (19)
N1—H1B⋯O1ⁱⁱ	0.87 (2)	1.97 (2)	2.772 (2)	152.9 (19)
N2—H2A⋯O4	0.90 (3)	2.24 (3)	2.964 (3)	137 (2)
N2—H2A⋯O2ⁱⁱⁱ	0.90 (3)	2.48 (3)	3.034 (3)	120 (2)
N2—H2B⋯O4ⁱⁱⁱ	0.93 (3)	2.03 (3)	2.928 (3)	161 (2)
N2—H2B⋯O3ⁱⁱⁱ	0.93 (3)	2.59 (3)	3.030 (3)	109 (2)
N2—H2C⋯O5ⁱ	0.88 (3)	2.03 (3)	2.910 (3)	172 (2)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+2, -z.

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ; Macíček & Yordanov, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1000438

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814009787/nc2324sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009787/nc2324Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009787/nc2324Isup3.cml

checkCIF report

Comment top

The title compound, C₉H₂₂N₂²⁺·2NO₃^-, was synthesized unexpectedly from 4-amino-2,2,6,6-tetramethylpiperidine, bismuth(III) nitrate pentahydrate and nitric acid. We report in this paper it's structure; its homologues obtained with chlorate, phosphate and tetrachlorozincate anions has been described previously (Huang & Deng, 2007; Mrad et al., 2009; El Glaoui et al., 2010).

The asymmetric unit of the title compound contains one 4-azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dication and two nitrate anions (Fig. 1) with all atoms are located on general Wykoff position 4 e.

The piperidine ring adopts a chair conformation, with puckering parameters (calculated with PLATON (Spek, 2009)): Q = 0.535 Å, Θ = 6.63 ° and Φ = 205.565 ° (Cremer & Pople, 1975). This conformation has also been noticed in other 4-azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium salts (Chebbi & Driss, 2001; Huang & Deng, 2007; Mrad et al., 2009; El Glaoui et al., 2010).

The three-dimensional extensive hydrogen-bonding network is built and linked through moderate hydrogen-bond interactions (Table 1) (Jeffrey, 1997) between the NH₃ and NH₂ groups of the dications and the nitrate anions, located in the vicinity of the protonated amine groups. Each organic entity is bounded to six different nitrate anions through seven N—H···O hydrogen bonds (Fig. 2). Indeed, N1—H1A···O1, N2—H2C···O5, N2—H2A···O2 and bifurcated N2—H2B···O3(O4) hydrogen bonds (Table 1) link dications and anions into chains along [010] direction, which generate R₃⁴(14) and R₂²(6) ring motifs (Etter et al., 1990; Bernstein, et al., 1995) (Fig. 3). These chains are interconnected by N1—H1B···O1 and N2—H2A···O4 hydrogen bonds (Table 1),which generate two sets of R₄²(8) ring motifs (Fig. 2). This arrangement results in the formation of a complicated three-dimensional network.

Related literature top

For related structures, see: Chebbi & Driss (2001); El Glaoui, Mrad, Jenneau & Ben Nasr (2010); Mrad et al. (2009); Huang & Deng (2007). For hydrogen bonding and graph-set motifs, see: Jeffrey (1997); Bernstein et al. (1995); Etter et al. (1990). For ring-puckering parameters, see: Cremer & Pople (1975); Spek (2009).

Experimental top

The title compound was prepared by dissolving 0.096 mmol (0.36 g) of bismuth(III) nitrate pentahydrate in 20 ml of distilled water; 0.096 mmol (0.15 g) of 4-amino-2,2,6,6-tetramethylpiperidine in 15 ml of ethanol (96%) and 1 ml of concentred nitric acid were then added. The mixture was stirred for 20 minutes and the solution is allowed to stand at room temperature. Dark brown crystals were obtained after 5 days of slow evaporation of the solvent. The X-ray analysis proves that the trivalent bismuth is not part of the structure and that the obtained phase is C₉H₂₂N₂²⁺·2NO₃^-.

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Asymmetric unit of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are presented at the 50% probability level. H atoms are shown as sticks.
	Fig. 2. Crystal structure of the title compound with view along the b axis, showing the formation of two sets of R₄²(8) hydrogen-bonding motifs. Hydrogen bonds are represented by dashed lines. H atoms not involved in hydrogen bonding and –CH₃ groups of 4-azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dication have been omitted for clarity.
	Fig. 3. A perspective view of one chain of the title compound, showing R₂²(6) and R₃⁴(14) rings along [010] direction. Hydrogen bonds are represented by dashed lines. H atoms not involved in hydrogen bonding and –CH₃ groups of 4-azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dication have been omitted for clarity. Symmetry codes: (iv) x - 1/2, -y + 3/2, z + 1/2; (v) x - 1, y, z; (vi) -x + 1, -y + 2, -z.

4-Azaniumyl-2,2,6,6-tetramethylpiperidin-1-ium dinitrate top

Crystal data top

C₉H₂₂N₂²⁺·2NO₃⁻	F(000) = 608
M_r = 282.31	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.367 (2) Å	θ = 10–15°
b = 11.054 (1) Å	µ = 0.11 mm⁻¹
c = 13.167 (2) Å	T = 298 K
β = 112.45 (2)°	Prism, dark brown
V = 1394.5 (4) Å³	0.45 × 0.30 × 0.25 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1908 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 26.0°, θ_min = 2.5°
ω/2θ scans	h = −11→12
Absorption correction: ψ scan (North et al., 1968)	k = −13→0
T_min = 0.860, T_max = 0.978	l = −16→0
2849 measured reflections	2 standard reflections every 120 min
2731 independent reflections	intensity decay: 1.0%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	All H-atom parameters refined
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0508P)² + 0.3472P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2731 reflections	Δρ_max = 0.24 e Å⁻³
261 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (3)

Crystal data top

C₉H₂₂N₂²⁺·2NO₃⁻	V = 1394.5 (4) Å³
M_r = 282.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.367 (2) Å	µ = 0.11 mm⁻¹
b = 11.054 (1) Å	T = 298 K
c = 13.167 (2) Å	0.45 × 0.30 × 0.25 mm
β = 112.45 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1908 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.017
T_min = 0.860, T_max = 0.978	2 standard reflections every 120 min
2849 measured reflections	intensity decay: 1.0%
2731 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.121	All H-atom parameters refined
S = 1.05	Δρ_max = 0.24 e Å⁻³
2731 reflections	Δρ_min = −0.15 e Å⁻³
261 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
N1	0.65815 (16)	0.64785 (14)	0.03529 (14)	0.0327 (4)
H1A	0.607 (2)	0.614 (2)	−0.0322 (19)	0.051 (6)*
H1B	0.636 (2)	0.6145 (19)	0.0858 (17)	0.041 (6)*
N2	0.8793 (2)	0.8680 (2)	−0.10476 (17)	0.0459 (5)
H2A	0.972 (3)	0.854 (2)	−0.085 (2)	0.072 (8)*
H2B	0.857 (3)	0.950 (3)	−0.109 (2)	0.076 (9)*
H2C	0.838 (3)	0.834 (2)	−0.170 (2)	0.059 (7)*
C1	0.80955 (19)	0.61008 (17)	0.06283 (15)	0.0356 (5)
C2	0.8620 (2)	0.67784 (19)	−0.01499 (17)	0.0392 (5)
H2D	0.959 (2)	0.666 (2)	0.0075 (17)	0.050 (6)*
H2E	0.820 (2)	0.6457 (19)	−0.0867 (18)	0.047 (6)*
C3	0.8315 (2)	0.81240 (18)	−0.02154 (16)	0.0360 (5)
H3	0.881 (2)	0.8515 (17)	0.0414 (16)	0.034 (5)*
C4	0.6767 (2)	0.8365 (2)	−0.05477 (18)	0.0396 (5)
H4A	0.627 (2)	0.8029 (18)	−0.1287 (18)	0.044 (6)*
H4B	0.660 (2)	0.921 (2)	−0.0601 (17)	0.046 (6)*
C5	0.6175 (2)	0.78055 (17)	0.02436 (16)	0.0366 (5)
C6	0.8059 (3)	0.4739 (2)	0.0425 (3)	0.0533 (6)
H6A	0.759 (3)	0.455 (2)	−0.032 (2)	0.067 (8)*
H6B	0.772 (3)	0.431 (2)	0.091 (2)	0.068 (8)*
H6C	0.899 (3)	0.449 (3)	0.060 (2)	0.082 (9)*
C7	0.8987 (3)	0.6347 (3)	0.18384 (18)	0.0512 (6)
H7A	0.848 (3)	0.609 (3)	0.229 (2)	0.088 (9)*
H7B	0.922 (3)	0.721 (3)	0.201 (2)	0.075 (8)*
H7C	0.983 (3)	0.587 (2)	0.201 (2)	0.072 (8)*
C8	0.6690 (3)	0.8427 (2)	0.1367 (2)	0.0530 (6)
H8A	0.625 (3)	0.921 (3)	0.127 (2)	0.075 (8)*
H8B	0.774 (3)	0.854 (2)	0.1702 (19)	0.062 (7)*
H8C	0.640 (2)	0.798 (2)	0.186 (2)	0.059 (7)*
C9	0.4579 (2)	0.7821 (2)	−0.0251 (2)	0.0513 (6)
H9A	0.430 (3)	0.867 (3)	−0.038 (2)	0.072 (8)*
H9B	0.425 (2)	0.742 (2)	0.0249 (19)	0.052 (6)*
H9C	0.423 (3)	0.732 (2)	−0.099 (2)	0.068 (7)*
N3	0.97658 (17)	1.01245 (16)	0.27175 (13)	0.0414 (4)
O1	0.96306 (16)	0.99288 (15)	0.36111 (11)	0.0581 (5)
O2	0.9133 (2)	1.09726 (19)	0.21402 (16)	0.0806 (6)
O3	1.0499 (2)	0.94507 (17)	0.24364 (15)	0.0735 (6)
N4	1.24475 (18)	0.83006 (17)	0.15347 (14)	0.0452 (4)
O4	1.16626 (17)	0.87793 (16)	0.06514 (12)	0.0578 (5)
O5	1.2237 (2)	0.72440 (15)	0.17517 (14)	0.0692 (5)
O6	1.34062 (19)	0.88941 (19)	0.21907 (14)	0.0779 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0349 (9)	0.0339 (9)	0.0300 (8)	−0.0027 (7)	0.0131 (7)	0.0000 (7)
N2	0.0492 (12)	0.0511 (13)	0.0432 (11)	−0.0107 (10)	0.0242 (9)	0.0002 (9)
C1	0.0318 (10)	0.0372 (11)	0.0366 (10)	0.0014 (8)	0.0115 (8)	0.0010 (8)
C2	0.0348 (11)	0.0467 (12)	0.0383 (11)	0.0011 (9)	0.0165 (9)	−0.0018 (9)
C3	0.0367 (10)	0.0423 (11)	0.0298 (10)	−0.0076 (9)	0.0136 (8)	−0.0026 (9)
C4	0.0411 (11)	0.0366 (12)	0.0404 (11)	0.0002 (9)	0.0149 (9)	0.0060 (9)
C5	0.0392 (11)	0.0316 (10)	0.0409 (11)	0.0008 (8)	0.0176 (9)	0.0004 (8)
C6	0.0536 (15)	0.0400 (13)	0.0697 (17)	0.0061 (11)	0.0273 (14)	0.0030 (12)
C7	0.0458 (13)	0.0594 (16)	0.0384 (12)	0.0019 (12)	0.0049 (10)	0.0069 (11)
C8	0.0714 (17)	0.0443 (14)	0.0518 (14)	−0.0047 (12)	0.0332 (13)	−0.0113 (11)
C9	0.0405 (12)	0.0452 (14)	0.0740 (17)	0.0067 (11)	0.0284 (12)	0.0114 (13)
N3	0.0442 (10)	0.0464 (10)	0.0364 (9)	−0.0044 (8)	0.0184 (8)	−0.0020 (8)
O1	0.0696 (11)	0.0758 (12)	0.0380 (8)	0.0214 (9)	0.0308 (8)	0.0116 (8)
O2	0.0791 (13)	0.0862 (14)	0.0787 (13)	0.0209 (11)	0.0326 (10)	0.0404 (11)
O3	0.0933 (13)	0.0714 (12)	0.0814 (13)	0.0112 (10)	0.0620 (11)	−0.0097 (10)
N4	0.0438 (10)	0.0528 (12)	0.0404 (10)	0.0018 (9)	0.0178 (8)	0.0005 (9)
O4	0.0591 (10)	0.0670 (11)	0.0409 (8)	0.0074 (8)	0.0121 (7)	0.0089 (8)
O5	0.0950 (14)	0.0465 (10)	0.0616 (11)	−0.0037 (9)	0.0247 (10)	0.0053 (8)
O6	0.0676 (12)	0.0939 (15)	0.0564 (10)	−0.0306 (11)	0.0061 (9)	−0.0065 (10)

Geometric parameters (Å, º) top

N1—C5	1.518 (2)	C5—C8	1.530 (3)
N1—C1	1.528 (2)	C6—H6A	0.94 (3)
N1—H1A	0.93 (2)	C6—H6B	0.97 (3)
N1—H1B	0.87 (2)	C6—H6C	0.95 (3)
N2—C3	1.496 (2)	C7—H7A	0.97 (3)
N2—H2A	0.90 (3)	C7—H7B	0.99 (3)
N2—H2B	0.93 (3)	C7—H7C	0.97 (3)
N2—H2C	0.88 (3)	C8—H8A	0.97 (3)
C1—C2	1.527 (3)	C8—H8B	1.01 (2)
C1—C6	1.527 (3)	C8—H8C	0.95 (3)
C1—C7	1.530 (3)	C9—H9A	0.98 (3)
C2—C3	1.516 (3)	C9—H9B	0.95 (2)
C2—H2D	0.94 (2)	C9—H9C	1.05 (3)
C2—H2E	0.95 (2)	N3—O3	1.219 (2)
C3—C4	1.517 (3)	N3—O2	1.227 (2)
C3—H3	0.90 (2)	N3—O1	1.256 (2)
C4—C5	1.527 (3)	N4—O6	1.228 (2)
C4—H4A	0.98 (2)	N4—O5	1.241 (2)
C4—H4B	0.95 (2)	N4—O4	1.254 (2)
C5—C9	1.530 (3)

C5—N1—C1	120.63 (14)	N1—C5—C4	106.67 (15)
C5—N1—H1A	105.5 (14)	N1—C5—C9	105.52 (16)
C1—N1—H1A	106.3 (14)	C4—C5—C9	110.84 (17)
C5—N1—H1B	109.7 (14)	N1—C5—C8	111.14 (17)
C1—N1—H1B	104.7 (14)	C4—C5—C8	113.24 (18)
H1A—N1—H1B	109.7 (19)	C9—C5—C8	109.1 (2)
C3—N2—H2A	109.4 (16)	C1—C6—H6A	111.5 (16)
C3—N2—H2B	107.5 (17)	C1—C6—H6B	111.3 (15)
H2A—N2—H2B	113 (2)	H6A—C6—H6B	114 (2)
C3—N2—H2C	111.5 (16)	C1—C6—H6C	107.1 (17)
H2A—N2—H2C	106 (2)	H6A—C6—H6C	105 (2)
H2B—N2—H2C	109 (2)	H6B—C6—H6C	107 (2)
C2—C1—C6	110.92 (18)	C1—C7—H7A	109.7 (17)
C2—C1—N1	107.66 (15)	C1—C7—H7B	113.9 (15)
C6—C1—N1	105.86 (17)	H7A—C7—H7B	106 (2)
C2—C1—C7	112.54 (18)	C1—C7—H7C	106.3 (15)
C6—C1—C7	108.8 (2)	H7A—C7—H7C	110 (2)
N1—C1—C7	110.82 (17)	H7B—C7—H7C	111 (2)
C3—C2—C1	113.53 (16)	C5—C8—H8A	107.8 (15)
C3—C2—H2D	109.4 (14)	C5—C8—H8B	113.4 (13)
C1—C2—H2D	109.2 (13)	H8A—C8—H8B	109 (2)
C3—C2—H2E	107.8 (13)	C5—C8—H8C	110.5 (14)
C1—C2—H2E	109.8 (13)	H8A—C8—H8C	107 (2)
H2D—C2—H2E	107.0 (18)	H8B—C8—H8C	109 (2)
N2—C3—C2	108.91 (17)	C5—C9—H9A	106.6 (15)
N2—C3—C4	109.06 (17)	C5—C9—H9B	108.1 (14)
C2—C3—C4	111.33 (17)	H9A—C9—H9B	114 (2)
N2—C3—H3	104.1 (12)	C5—C9—H9C	108.5 (14)
C2—C3—H3	112.6 (12)	H9A—C9—H9C	112 (2)
C4—C3—H3	110.5 (12)	H9B—C9—H9C	107.9 (19)
C3—C4—C5	112.84 (16)	O3—N3—O2	121.79 (19)
C3—C4—H4A	108.2 (12)	O3—N3—O1	119.03 (18)
C5—C4—H4A	109.2 (12)	O2—N3—O1	119.16 (18)
C3—C4—H4B	110.0 (13)	O6—N4—O5	120.45 (19)
C5—C4—H4B	109.7 (13)	O6—N4—O4	119.4 (2)
H4A—C4—H4B	106.7 (17)	O5—N4—O4	120.12 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.93 (2)	1.99 (2)	2.868 (2)	156.9 (19)
N1—H1B···O1ⁱⁱ	0.87 (2)	1.97 (2)	2.772 (2)	152.9 (19)
N2—H2A···O4	0.90 (3)	2.24 (3)	2.964 (3)	137 (2)
N2—H2A···O2ⁱⁱⁱ	0.90 (3)	2.48 (3)	3.034 (3)	120 (2)
N2—H2B···O4ⁱⁱⁱ	0.93 (3)	2.03 (3)	2.928 (3)	161 (2)
N2—H2B···O3ⁱⁱⁱ	0.93 (3)	2.59 (3)	3.030 (3)	109 (2)
N2—H2C···O5ⁱ	0.88 (3)	2.03 (3)	2.910 (3)	172 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.93 (2)	1.99 (2)	2.868 (2)	156.9 (19)
N1—H1B···O1ⁱⁱ	0.87 (2)	1.97 (2)	2.772 (2)	152.9 (19)
N2—H2A···O4	0.90 (3)	2.24 (3)	2.964 (3)	137 (2)
N2—H2A···O2ⁱⁱⁱ	0.90 (3)	2.48 (3)	3.034 (3)	120 (2)
N2—H2B···O4ⁱⁱⁱ	0.93 (3)	2.03 (3)	2.928 (3)	161 (2)
N2—H2B···O3ⁱⁱⁱ	0.93 (3)	2.59 (3)	3.030 (3)	109 (2)
N2—H2C···O5ⁱ	0.88 (3)	2.03 (3)	2.910 (3)	172 (2)

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

Acknowledgements

The authors thank Professor Dr Ahmed Driss for many helpful discussions.

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