A new (monohydrate) form of 3,5-di­carb­oxy­anilinium nitrate: crystal structure and Hirshfeld surface analysis

Boutebdja, M.; Benarous, N.; Boulkedid, A.L.; Lehleh, A.; Beghidja, A.

doi:10.1107/S2056989022010167

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ISSN: 2056-9890

Volume 78| Part 12| December 2022| Pages 1151-1155

https://doi.org/10.1107/S2056989022010167

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A new (monohydrate) form of 3,5-dicarboxyanilinium nitrate: crystal structure and Hirshfeld surface analysis

Mehdi Boutebdja,^a,^b ^* Nesrine Benarous,^a Ahlem Linda Boulkedid,^a Asma Lehleh ^a and Adel Beghidja ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Frères Mentouri Constantine 1, 25017 Constantine, Algeria, and ^bLaboratoire de Technologie des Matériaux Avancés, École Nationale Polytechnique de Constantine Nouvelle Ville Universitaire, Ali Mendjeli, Constantine 25000, Algeria
^*Correspondence e-mail: mboutebdja@gmail.com

Edited by A. S. Batsanov, University of Durham, United Kingdom (Received 31 August 2022; accepted 20 October 2022; online 1 November 2022)

The title compound, C₈H₈NO₄⁺·NO₃⁻·H₂O, crystallizes in the same space group (P2₁/c) as the previously reported dihydrate form [Liang & Zhu (2010 ). Acta Cryst. E66, o667], but with two formula units per asymmetric unit instead of one. In the crystal, the components are linked into a three-dimensional network by classical intermolecular O—H⋯O and N—H⋯O hydrogen bonds and π–π stacking interactions. A Hirshfeld surface (HS) analysis indicated that the most important contributions to the crystal packing are from H⋯O/O⋯H (52.4%), H⋯H (13.9%) and C⋯C (11.2%) for one cation and H⋯O/O⋯H (46.3%), H⋯H (20%) and O⋯C/C⋯O (10.6%) for the other.

Keywords: 5-aminoisophtalic acid; X-ray diffraction; crystal structure; Hirshfeld surface.

CCDC reference: 2215274

1. Chemical context

The amphoteric 5-aminoisophtalic acid (5-AIP) has a well known ability to form supramolecular assemblies with metal ions (Xin et al., 2021 ; Luo et al., 2011 ). As a result, it can operate like nodes similar to natural amino acids (Singh et al., 2019 ) (Fig. 1). In addition, 5-AIP may self-assemble as a result of many hydrogen-bonding patterns. It forms salts with a Brønsted acid or base and its structural characteristics enable it to take on a variety of ionic forms (Nath & Baruah, 2012 ; McGuire et al., 2016 ). Herein, we report on the synthesis and crystal structure of a new 3,5-dicarboxyanilinium nitrate hydrate, (I).

Figure 1
Different neutral and ionic forms of 5-aminoisophthalic acid

2. Structural commentary

Compound (I) differs from the previously reported crystal form of 3,5-dicarboxyanilinium nitrate (Liang & Zhu, 2010) by containing one water molecule per formula unit, instead of two. The asymmetric unit comprises two formula units, i.e., two 3,5-dicarboxylanilinium cations (A and B), two nitrate anions (A and B) and two water molecules (Fig. 2a). All bond distances and angles fall within normal ranges as compared to similar molecules (Wang & Zhang, 2006 ; Dobson & Gerkin, 1998 ; Nath & Baruah, 2012; Singh et al., 2019; Cai et al., 2020 ). The cations have similar conformations that differ mainly in the opposite orientations of one carboxylic group, as seen by the torsion angles C5—C4—C8—O3 of 6.0 (2)° in cation A and −178.43 (18)° in cation B. Mogul (Bruno et al., 2004 ) based on the Cambridge Structural Database (version 2022.2.0; Groom et al., 2016 ), indicated the single character of the C6—N1 bonds [1.457 (2) Å for A and 1.462 (2) Å for B], which have lengths close to the median of the 2198 found fragments of the same chemical nature. The C=O double bonds in the carboxylic groups [1.202 (2) to 1.241 (2) Å] are shorter than the C—O single bonds [1.285 (2) to 1.322 (2) Å, Table 1]. The planarity of the cations varies slightly: the dihedral angles between the carboxylic group planes (C1, O1, O2) and (C8, O3, O4) and the ring plane are 7.85 (9) and 5.90 (9)°, respectively, in cation A, 5.93 (2) and 2.68 (2)° in cation B; all non-hydrogen atoms are coplanar within 0.083 Å in cation A and 0.052 Å in B.

Table 1
Selected geometric parameters (Å, °)

C6A—N1A	1.457 (2)	N1B—C6B	1.463 (2)
O1A—C1A	1.286 (2)	O1B—C1B	1.285 (2)
O2A—C1A	1.237 (2)	O2B—C1B	1.241 (2)
O3A—C8A	1.322 (2)	O3B—C8B	1.305 (2)
O4A—C8A	1.202 (2)	O4B—C8B	1.203 (2)

O2A—C1A—O1A	124.42 (17)	O2B—C1B—O1B	123.59 (17)
O4A—C8A—O3A	124.00 (16)	O4B—C8B—O3B	124.69 (18)

Figure 2
(a) ORTEP view of the asymmetric unit of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed cyan lines. (b) Histogram comparing the C—N bond lengths generating using Mogul.

3. Supramolecular features

An extensive network of moderate-to-strong N—H⋯O and O—H⋯O hydrogen bonds (Steiner, 2002 ) exists in the crystal structure of (I) (Table 2). The supramolecular motif can be described as two-dimensional layers that extend parallel to the crystallographic (101) plane (Fig. 3a). In each layer, the 3,5-dicarboxyanilinium A cations and the nitrate A anions are linked through bifurcated hydrogen bonds, forming chains of R₁²(4) rings that propagate parallel to the b axis (Fig. 3a,b). In addition, the 3,5-dicarboxyanilinium B cations and water molecules form chains of R₆⁶(22) ring motifs that also extend along the b-axis direction (Fig. 3a,c,d). These two types of chains are interconnected via dimeric O—H⋯O hydrogen bonds, which occur between one of the carboxylate groups of each of the A and B cations (within the asymmetric unit as defined here) and enclosing an R₂²(8) graph-set motif (Fig. 3a,e). Furthermore, we can distinguish, as illustrated in Fig. 4, that the nitrate B anions are involved in the formation of alternating R₆⁶(26) and R₈⁸(34) ring motifs, generating ribbons that propagate along the a-axis direction, which in turn leads to the formation of a three-dimensional supramolecular network.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2WA⋯O4B	0.93 (4)	2.11 (4)	2.911 (3)	143 (3)
O2W—H2WB⋯O1Bⁱ	0.88 (4)	2.14 (4)	2.913 (2)	147 (3)
O3A—H3A⋯O5A	0.94 (3)	1.80 (3)	2.7399 (19)	173 (2)
O3B—H3B⋯O1W	0.86 (3)	1.76 (3)	2.604 (2)	165 (3)
O1W—H1WA⋯O2Wⁱⁱ	0.81 (3)	1.97 (3)	2.772 (2)	173 (3)
O1W—H1WB⋯O6Bⁱⁱⁱ	0.88 (3)	1.88 (3)	2.762 (2)	175 (3)
C7A—H7A⋯O5B^iv	0.93	2.54	3.236 (2)	131
N1B—H1BA⋯O7A^v	0.94 (2)	2.01 (2)	2.938 (2)	173 (2)
N1B—H1BB⋯O5B	0.90 (2)	1.96 (2)	2.842 (2)	168 (2)
N1B—H1BC⋯O2W^vi	0.86 (3)	2.64 (2)	3.056 (3)	111.2 (17)
N1B—H1BC⋯O1W^vi	0.86 (3)	2.00 (3)	2.841 (2)	165 (2)
N1A—H1AA⋯O6A^vii	0.81 (3)	2.38 (3)	3.104 (3)	150 (2)
N1A—H1AA⋯O5A^vii	0.81 (3)	2.32 (3)	3.070 (2)	154 (2)
N1A—H1AB⋯O7B^iv	0.90 (2)	2.25 (2)	2.934 (2)	132.1 (18)
N1A—H1AB⋯O5B^iv	0.90 (2)	2.12 (2)	2.992 (2)	162.9 (19)
N1A—H1AC⋯O5A^viii	0.86 (2)	2.34 (2)	3.000 (2)	133.8 (19)
N1A—H1AC⋯O7A^viii	0.86 (2)	2.10 (3)	2.942 (2)	167 (2)
O1A—H1A⋯O2B	0.77 (4)	1.91 (4)	2.669 (2)	174 (4)
O1B—H1B⋯O2A	0.82 (3)	1.85 (3)	2.662 (2)	170 (3)
Symmetry codes: (i) ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) ; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+2, y-{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[x, -y+{\script{7\over 2}}, z+{\script{1\over 2}}]$ ; (viii) .

Figure 3
(a) Partial packing of (I)

showing the two-dimensional layers (viewed down the c and b axes); (b) the R₁²(4) motif formed by a N—H⋯O bifurcated hydrogen bond; (c) and (d) the R₆⁶(22) motifs formed by a combination of N—H⋯O and O—H⋯O hydrogen bonds; (e) the dimeric R₂²(8) motifs formed by O—H⋯O hydrogen bonds.

Figure 4
Partial packing of (I)

showing the ribbons formed by alternating R₆⁶(26) and R₈⁸(34) ring motifs.

Further examination reveals that the cohesion in the crystal structure is enhanced by offset or slipped π–π stacking interactions, involving the aromatic rings of the A and B cations, which appear in the direction of the crystallographic a axis (Fig. 5). Two parallel rings A contact with a centroid-to-centroid distance Cg1⋯Cg1(2 − x, 3 − y, 1 − z) of 3.6768 (9) Å, while rings A and B (forming an interplanar angle of 11.81°) contact with a Cg1⋯Cg2(x, 1 + y, z) distance of 3.7960 (9) Å. Note that the former π–π stacking interaction reinforces the R₂²(8) ring described earlier.

Figure 5
Part of the crystal structure of (I)

showing the π–π stacking interactions, which appear parallel to the a axis.

4. Hirshfeld surface analysis

In order to visualize and quantify the intermolecular interactions in compound (I), we carried out a Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009 ) using CrystalExplorer21 (Spackman et al., 2021 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) mapped in color with a normalized contact distance, d_norm, varying from red through white to blue depending on the distances compared to the sum of the van der Waals radii. The Hirshfeld surfaces mapped over d_norm, were calculated separately for cations A and B using a standard high surface resolution (Fig. 6a). The red spots correspond to contacts shorter than the van der Waals radii sum of the closest atoms and relate to the presence of O—H⋯O and N—H⋯O hydrogen bonds in the crystal structure, whereas the faint-red spots (highlighted by red circles for clarity) represent weaker C—H⋯O interactions. The presence of characteristic red and blue triangles on the shape-index surface (Fig. 6b) clearly suggest the presence of π–π interactions between the neighboring organic cations and the curvedness plots (Fig. 6c) show flat surface patches characteristic of planar stacking.

Figure 6
The Hirshfeld surfaces of the organic cations A and B mapped over: (a) d_norm in the range −0.7489 to 1.2298 a.u., (b) shape-index and (c) curvedness.

The overall two-dimensional fingerprint plot and those delineated into O⋯H/H⋯O, H⋯H, C⋯C, O⋯C/C⋯O, O⋯O and C⋯H/H⋯C contacts for cations A and B are shown in Fig. 7 and their relative contributions to the HS are illustrated graphically in Fig. 8. The most important contributions for both cations come from H⋯O/O⋯H contacts (52.4% for cation A and 46.3% for B), with characteristic `spikes' in the plots related to the presence of strong O—H⋯O and N—H⋯O hydrogen bonds. The second most important are H⋯H contacts, contributing 13.9% and 20% for cations A and B, respectively. These are followed for cation A by C⋯C contacts (11.2%), but for cation B by O⋯C/C⋯O contacts (10.6%), other contacts making less significant contributions.

Figure 7
Two-dimensional fingerprint plots of (I)

, showing the percentage contributions of all contacts and those delineated into O⋯H/H⋯O, H⋯H, C⋯C, O⋯C/C⋯O, O⋯O and C⋯H/H⋯C contacts for the A and B organic cations.

Figure 8
Percentage contributions of contacts to the Hirshfeld surface in the cations of (I)

5. Database survey

The Cambridge Structural Database (Version 2022.2.0 updated to June 2022; Groom et al., 2016), was searched for structures with carboxyl–carboxyl R₂²(8) graph-set motifs using ConQuest (Bruno et al., 2002 ) for all searches, and filters were applied to ensure that only organic compounds and non-disordered molecules were included. In addition, the searches were also limited to structures with low R-factor values (R < 0.05). The results of the searches were analyzed using Mercury (CSD Version 2022.2.0; Macrae et al., 2020 ).

The geometries of O—H⋯O hydrogen bonds from an analysis of 2883 crystal structures deposited in the CSD are illustrated in Fig. 9. The relationship between the H⋯O distances and O—H⋯O angles is shown as a two-dimensional plot, the O⋯O distances being indicated by the color of the data points. The angle tends to increase as the O⋯O and H⋯O distances decrease. The greatest density of observed hydrogen bonds occurs in the range of 1.3–1.9 Å for the H⋯O distance, 2.6–2.8 Å for the O⋯O distances (indicated by green data points) and 160–180° for the O—H⋯O angle.

Figure 9
Scatterplot of O—H⋯O angle (°) against H⋯O distance (Å) for carboxylic acid to carboxylic acid type hydrogen bonds, with the O⋯O distance (Å) shown using a color scale (bottom).

6. Synthesis and crystallization

5-Aminoisophthalic acid (0.181 g, 1 mmol) dissolved in methanol (10 mL) was added under stirring to a methanolic solution of Er(NO₃)₃·5H₂O (0.110 g, 0.25 mmol). After several minutes of stirring, a brighter orange precipitate appeared and was filtered. After slowly evaporating the filtrate over one week, colorless single crystals of the title compound suitable for X-ray diffraction analysis were isolated.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atoms of the ammonium NH₃⁺, carboxylic acid groups COOH and water molecules were localized in difference-Fourier maps and refined with U_iso(H) set to 1.5U_eq(O) or 1.2U_eq(N). The C-bound H atoms were placed in calculated positions with a C—H distance of 0.93 Å and refined using a riding model with fixed isotropic displacement parameters [U_iso(H) = 1.2U_eq(C)].

Table 3
Experimental details

Crystal data
Chemical formula	C₈H₈NO₄⁺·NO₃⁻·H₂O
M_r	262.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.7026 (4), 8.5449 (2), 16.9929 (4)
β (°)	92.800 (2)
V (Å³)	2132.31 (9)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.15
Crystal size (mm)	0.14 × 0.12 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.627, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	20897, 4881, 3653
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.142, 1.02
No. of reflections	4881
No. of parameters	368
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.36
Computer programs: BIS, APEX2 and SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2215274

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010167/zv2018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010167/zv2018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022010167/zv2018Isup3.cml

checkCIF report

Computing details top

Data collection: BIS (Bruker, 2014), APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3,5-Dicarboxyanilinium nitrate monohydrate top

Crystal data top

C₈H₈NO₄⁺·NO₃⁻·H₂O	F(000) = 1088
M_r = 262.18	D_x = 1.633 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7026 (4) Å	Cell parameters from 5578 reflections
b = 8.5449 (2) Å	θ = 2.4–28.9°
c = 16.9929 (4) Å	µ = 0.15 mm⁻¹
β = 92.800 (2)°	T = 298 K
V = 2132.31 (9) Å³	Plate, colorless
Z = 8	0.14 × 0.12 × 0.1 mm

Data collection top

Bruker APEXII CCD diffractometer	3653 reflections with I > 2σ(I)
Mirror optics monochromator	R_int = 0.069
φ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −18→19
T_min = 0.627, T_max = 0.746	k = −11→10
20897 measured reflections	l = −22→20
4881 independent reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: other
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: mixed
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0742P)² + 0.5757P] where P = (F_o² + 2F_c²)/3
4881 reflections	(Δ/σ)_max = 0.001
368 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
N1B	0.67893 (13)	0.3682 (2)	0.28611 (10)	0.0301 (4)
O1A	0.82519 (13)	1.17198 (18)	0.43486 (9)	0.0423 (4)
O2W	0.58027 (15)	−0.0690 (2)	0.65998 (12)	0.0603 (5)
H2WA	0.546 (3)	−0.012 (5)	0.622 (2)	0.090*
H2WB	0.615 (3)	−0.127 (4)	0.631 (2)	0.090*
O3A	0.97439 (10)	1.86406 (16)	0.43414 (8)	0.0346 (3)
H3A	0.9913 (18)	1.922 (3)	0.3898 (16)	0.052*
O2A	0.78909 (12)	1.14271 (17)	0.56010 (9)	0.0452 (4)
O4A	0.92628 (11)	1.69085 (17)	0.34332 (8)	0.0396 (4)
O3B	0.56209 (12)	0.38877 (19)	0.62141 (9)	0.0465 (4)
H3B	0.539 (2)	0.324 (4)	0.6536 (18)	0.070*
O1B	0.70854 (12)	0.86590 (18)	0.53880 (9)	0.0418 (4)
O4B	0.55015 (15)	0.17909 (18)	0.54420 (10)	0.0574 (5)
O2B	0.75437 (11)	0.88596 (16)	0.41625 (8)	0.0362 (3)
O6A	1.10763 (13)	1.85507 (18)	0.24130 (10)	0.0503 (4)
O5A	1.03844 (10)	2.02758 (17)	0.30967 (9)	0.0380 (4)
O7A	1.18270 (10)	2.05003 (17)	0.29317 (9)	0.0389 (4)
O1W	0.49992 (10)	0.22720 (19)	0.73709 (9)	0.0357 (3)
H1WA	0.4800 (19)	0.284 (3)	0.7699 (16)	0.053*
H1WB	0.4622 (19)	0.147 (3)	0.7312 (15)	0.053*
O7B	0.70536 (11)	−0.14901 (17)	0.22552 (10)	0.0450 (4)
O5B	0.76172 (10)	0.07156 (17)	0.26536 (9)	0.0403 (4)
O6B	0.62322 (10)	0.01340 (18)	0.28938 (9)	0.0410 (4)
N2A	1.11052 (12)	1.97532 (18)	0.28112 (9)	0.0295 (4)
N2B	0.69618 (11)	−0.02251 (18)	0.25969 (10)	0.0299 (4)
C1A	0.82076 (13)	1.2200 (2)	0.50630 (11)	0.0254 (4)
C2A	0.85560 (12)	1.3807 (2)	0.52255 (10)	0.0225 (4)
C3A	0.88063 (11)	1.4777 (2)	0.46159 (10)	0.0218 (4)
H3AA	0.876949	1.441662	0.409886	0.026*
C4A	0.91116 (11)	1.62859 (19)	0.47816 (10)	0.0206 (3)
C8A	0.93717 (12)	1.7299 (2)	0.41105 (10)	0.0244 (4)
C5A	0.91825 (12)	1.68168 (19)	0.55568 (10)	0.0219 (3)
H5A	0.939205	1.782250	0.567040	0.026*
C6A	0.89382 (11)	1.5833 (2)	0.61539 (10)	0.0212 (3)
N1A	0.90040 (13)	1.6379 (2)	0.69669 (9)	0.0267 (3)
C7A	0.86173 (12)	1.4334 (2)	0.59991 (10)	0.0230 (4)
H7A	0.844537	1.369037	0.640745	0.028*
C8B	0.57193 (14)	0.3132 (2)	0.55560 (12)	0.0321 (4)
C4B	0.61297 (13)	0.4121 (2)	0.49363 (11)	0.0268 (4)
C3B	0.64094 (13)	0.5653 (2)	0.51020 (11)	0.0261 (4)
H3BA	0.633618	0.607888	0.559853	0.031*
C2B	0.67981 (12)	0.6536 (2)	0.45190 (11)	0.0236 (4)
C1B	0.71606 (12)	0.8134 (2)	0.46854 (11)	0.0254 (4)
C7B	0.69130 (12)	0.5897 (2)	0.37756 (10)	0.0244 (4)
H7B	0.716729	0.648905	0.338290	0.029*
C6B	0.66436 (12)	0.4375 (2)	0.36321 (10)	0.0240 (4)
C5B	0.62522 (13)	0.3476 (2)	0.42002 (11)	0.0271 (4)
H5B	0.607314	0.245226	0.409039	0.033*
H1B	0.7317 (17)	0.954 (3)	0.5397 (14)	0.041*
H1BA	0.7200 (16)	0.426 (3)	0.2570 (13)	0.033*
H1BB	0.7054 (15)	0.273 (3)	0.2872 (13)	0.033*
H1BC	0.6263 (18)	0.350 (3)	0.2638 (13)	0.033*
H1AA	0.9473 (17)	1.618 (3)	0.7214 (13)	0.033*
H1AB	0.8549 (16)	1.593 (3)	0.7224 (13)	0.033*
H1AC	0.8850 (15)	1.734 (3)	0.7023 (13)	0.033*
H1A	0.804 (3)	1.090 (5)	0.433 (2)	0.087 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1B	0.0342 (9)	0.0260 (9)	0.0305 (9)	−0.0018 (7)	0.0048 (7)	−0.0073 (7)
O1A	0.0685 (11)	0.0235 (8)	0.0348 (8)	−0.0118 (7)	0.0009 (7)	−0.0098 (6)
O2W	0.0750 (14)	0.0476 (11)	0.0614 (12)	0.0152 (9)	0.0353 (10)	0.0080 (9)
O3A	0.0509 (9)	0.0253 (7)	0.0279 (7)	−0.0142 (6)	0.0051 (6)	0.0020 (6)
O2A	0.0679 (11)	0.0298 (8)	0.0381 (8)	−0.0217 (7)	0.0046 (7)	0.0034 (6)
O4A	0.0628 (10)	0.0343 (8)	0.0219 (7)	−0.0123 (7)	0.0033 (6)	0.0008 (6)
O3B	0.0690 (11)	0.0400 (9)	0.0318 (8)	−0.0176 (8)	0.0154 (7)	0.0013 (7)
O1B	0.0616 (10)	0.0277 (8)	0.0375 (8)	−0.0182 (7)	0.0179 (7)	−0.0130 (6)
O4B	0.0931 (14)	0.0302 (9)	0.0507 (10)	−0.0227 (8)	0.0230 (9)	0.0021 (7)
O2B	0.0534 (9)	0.0237 (7)	0.0320 (7)	−0.0118 (6)	0.0081 (6)	−0.0002 (5)
O6A	0.0677 (12)	0.0278 (8)	0.0560 (10)	0.0005 (7)	0.0081 (8)	−0.0119 (7)
O5A	0.0419 (8)	0.0315 (8)	0.0419 (8)	0.0004 (6)	0.0170 (6)	0.0065 (6)
O7A	0.0353 (8)	0.0388 (8)	0.0425 (9)	−0.0050 (6)	0.0013 (6)	0.0046 (6)
O1W	0.0359 (8)	0.0355 (8)	0.0365 (8)	−0.0048 (6)	0.0102 (6)	−0.0007 (6)
O7B	0.0558 (10)	0.0263 (8)	0.0541 (10)	0.0004 (7)	0.0153 (8)	−0.0108 (7)
O5B	0.0417 (9)	0.0335 (8)	0.0467 (9)	−0.0101 (6)	0.0127 (7)	−0.0036 (6)
O6B	0.0338 (8)	0.0393 (8)	0.0508 (9)	0.0046 (6)	0.0117 (7)	−0.0038 (7)
N2A	0.0394 (9)	0.0220 (8)	0.0273 (8)	−0.0009 (7)	0.0050 (6)	0.0059 (6)
N2B	0.0354 (9)	0.0247 (8)	0.0298 (8)	0.0019 (7)	0.0050 (6)	0.0011 (6)
C1A	0.0306 (9)	0.0202 (9)	0.0254 (9)	−0.0024 (7)	0.0009 (7)	−0.0008 (7)
C2A	0.0251 (9)	0.0176 (8)	0.0248 (9)	−0.0016 (6)	0.0005 (6)	0.0004 (6)
C3A	0.0233 (8)	0.0218 (8)	0.0202 (8)	−0.0007 (6)	−0.0006 (6)	−0.0023 (6)
C4A	0.0219 (8)	0.0199 (8)	0.0202 (8)	0.0008 (6)	0.0012 (6)	0.0019 (6)
C8A	0.0286 (9)	0.0210 (9)	0.0236 (9)	−0.0010 (7)	0.0022 (7)	0.0024 (7)
C5A	0.0253 (9)	0.0166 (8)	0.0236 (8)	−0.0017 (6)	0.0007 (6)	−0.0017 (6)
C6A	0.0229 (8)	0.0219 (8)	0.0188 (8)	0.0020 (6)	0.0013 (6)	−0.0025 (6)
N1A	0.0345 (9)	0.0258 (8)	0.0200 (8)	−0.0003 (7)	0.0030 (6)	−0.0031 (6)
C7A	0.0267 (9)	0.0198 (8)	0.0227 (8)	−0.0010 (7)	0.0032 (7)	0.0011 (6)
C8B	0.0361 (11)	0.0265 (10)	0.0339 (10)	−0.0055 (8)	0.0040 (8)	0.0051 (8)
C4B	0.0291 (9)	0.0212 (9)	0.0303 (9)	−0.0025 (7)	0.0017 (7)	0.0032 (7)
C3B	0.0282 (9)	0.0232 (9)	0.0273 (9)	−0.0019 (7)	0.0038 (7)	−0.0018 (7)
C2B	0.0230 (9)	0.0189 (8)	0.0288 (9)	−0.0012 (7)	0.0010 (7)	−0.0017 (7)
C1B	0.0281 (9)	0.0206 (8)	0.0277 (9)	0.0000 (7)	0.0027 (7)	−0.0018 (7)
C7B	0.0280 (9)	0.0189 (9)	0.0264 (9)	−0.0001 (7)	0.0034 (7)	0.0010 (7)
C6B	0.0247 (9)	0.0219 (9)	0.0254 (9)	−0.0004 (7)	0.0003 (7)	−0.0033 (7)
C5B	0.0300 (9)	0.0187 (8)	0.0324 (10)	−0.0045 (7)	0.0005 (7)	−0.0009 (7)

Geometric parameters (Å, º) top

C6A—N1A	1.457 (2)	O6B—N2B	1.246 (2)
N1B—H1BA	0.94 (2)	C1A—C2A	1.486 (2)
N1B—H1BB	0.90 (2)	C2A—C3A	1.390 (2)
N1B—H1BC	0.86 (3)	C2A—C7A	1.388 (2)
O1A—C1A	1.286 (2)	C3A—H3AA	0.9300
O2A—C1A	1.237 (2)	C3A—C4A	1.390 (2)
O1A—H1A	0.77 (4)	C4A—C8A	1.496 (2)
O2W—H2WA	0.93 (4)	C4A—C5A	1.392 (2)
O2W—H2WB	0.88 (4)	C5A—H5A	0.9300
O3A—H3A	0.94 (3)	C5A—C6A	1.379 (2)
O3A—C8A	1.322 (2)	C6A—C7A	1.386 (2)
O4A—C8A	1.202 (2)	N1A—H1AA	0.81 (3)
N1B—C6B	1.463 (2)	N1A—H1AB	0.90 (2)
O1B—C1B	1.285 (2)	N1A—H1AC	0.86 (2)
O2B—C1B	1.241 (2)	C7A—H7A	0.9300
O3B—H3B	0.86 (3)	C8B—C4B	1.499 (2)
O3B—C8B	1.305 (2)	C4B—C3B	1.397 (3)
O1B—H1B	0.82 (3)	C4B—C5B	1.386 (3)
O4B—C8B	1.203 (2)	C3B—H3BA	0.9300
O6A—N2A	1.230 (2)	C3B—C2B	1.390 (2)
O5A—N2A	1.268 (2)	C2B—C1B	1.488 (2)
O7A—N2A	1.247 (2)	C2B—C7B	1.394 (2)
O1W—H1WA	0.81 (3)	C7B—H7B	0.9300
O1W—H1WB	0.88 (3)	C7B—C6B	1.378 (2)
O7B—N2B	1.237 (2)	C6B—C5B	1.381 (2)
O5B—N2B	1.255 (2)	C5B—H5B	0.9300

C6B—N1B—H1BA	112.8 (13)	C5A—C6A—N1A	119.66 (15)
C6B—N1B—H1BB	115.3 (14)	C5A—C6A—C7A	121.50 (15)
C6B—N1B—H1BC	107.5 (15)	C7A—C6A—N1A	118.84 (15)
H1BA—N1B—H1BB	101.1 (19)	C6A—N1A—H1AA	116.1 (16)
H1BA—N1B—H1BC	117 (2)	C6A—N1A—H1AB	107.9 (14)
H1BB—N1B—H1BC	103 (2)	C6A—N1A—H1AC	114.0 (15)
C1A—O1A—H1A	107 (3)	H1AA—N1A—H1AB	107 (2)
H2WA—O2W—H2WB	103 (3)	H1AA—N1A—H1AC	112 (2)
C8A—O3A—H3A	109.6 (16)	H1AB—N1A—H1AC	98 (2)
C8B—O3B—H3B	107 (2)	C2A—C7A—H7A	120.5
C1B—O1B—H1B	106.3 (17)	C6A—C7A—C2A	119.04 (16)
H1WA—O1W—H1WB	107 (3)	C6A—C7A—H7A	120.5
O6A—N2A—O5A	119.84 (18)	O3B—C8B—C4B	112.86 (16)
O6A—N2A—O7A	121.63 (17)	O2B—C1B—O1B	123.59 (17)
O7A—N2A—O5A	118.51 (16)	O4B—C8B—O3B	124.69 (18)
O7B—N2B—O5B	119.63 (16)	O4B—C8B—C4B	122.45 (18)
O7B—N2B—O6B	121.39 (17)	C3B—C4B—C8B	120.73 (17)
O6B—N2B—O5B	118.97 (16)	C5B—C4B—C8B	118.98 (16)
O1A—C1A—C2A	115.93 (16)	C5B—C4B—C3B	120.27 (16)
O2A—C1A—O1A	124.42 (17)	C4B—C3B—H3BA	120.3
O2A—C1A—C2A	119.64 (16)	C2B—C3B—C4B	119.49 (17)
C3A—C2A—C1A	120.90 (16)	C2B—C3B—H3BA	120.3
C7A—C2A—C1A	118.78 (15)	C3B—C2B—C1B	121.24 (16)
C7A—C2A—C3A	120.32 (16)	C3B—C2B—C7B	120.38 (16)
C2A—C3A—H3AA	120.1	C7B—C2B—C1B	118.24 (16)
C4A—C3A—C2A	119.79 (15)	O1B—C1B—C2B	116.78 (16)
C4A—C3A—H3AA	120.1	O2B—C1B—C2B	119.57 (16)
C3A—C4A—C8A	118.33 (15)	C2B—C7B—H7B	120.6
C3A—C4A—C5A	120.17 (15)	C6B—C7B—C2B	118.89 (16)
C5A—C4A—C8A	121.49 (15)	C6B—C7B—H7B	120.6
O3A—C8A—C4A	113.16 (15)	C7B—C6B—N1B	119.14 (16)
O4A—C8A—O3A	124.00 (16)	C7B—C6B—C5B	121.83 (16)
O4A—C8A—C4A	122.84 (16)	C5B—C6B—N1B	119.03 (16)
C4A—C5A—H5A	120.4	C4B—C5B—H5B	120.4
C6A—C5A—C4A	119.17 (15)	C6B—C5B—C4B	119.13 (16)
C6A—C5A—H5A	120.4	C6B—C5B—H5B	120.4

N1B—C6B—C5B—C4B	178.76 (17)	C5A—C4A—C8A—O3A	6.0 (2)
O1A—C1A—C2A—C3A	7.5 (3)	C5A—C4A—C8A—O4A	−175.09 (18)
O1A—C1A—C2A—C7A	−173.26 (17)	C5A—C6A—C7A—C2A	1.1 (3)
O2A—C1A—C2A—C3A	−171.65 (18)	N1A—C6A—C7A—C2A	−179.81 (16)
O2A—C1A—C2A—C7A	7.6 (3)	C7A—C2A—C3A—C4A	−0.6 (3)
O3B—C8B—C4B—C3B	3.4 (3)	C8B—C4B—C3B—C2B	179.20 (17)
O3B—C8B—C4B—C5B	−178.43 (18)	C8B—C4B—C5B—C6B	−178.95 (17)
O4B—C8B—C4B—C3B	−177.3 (2)	C4B—C3B—C2B—C1B	−175.94 (17)
O4B—C8B—C4B—C5B	0.9 (3)	C4B—C3B—C2B—C7B	−0.3 (3)
C1A—C2A—C3A—C4A	178.62 (16)	C3B—C4B—C5B—C6B	−0.8 (3)
C1A—C2A—C7A—C6A	−179.75 (16)	C3B—C2B—C1B—O1B	−0.9 (3)
C2A—C3A—C4A—C8A	−179.76 (16)	C3B—C2B—C1B—O2B	176.44 (18)
C2A—C3A—C4A—C5A	1.2 (3)	C3B—C2B—C7B—C6B	−0.6 (3)
C3A—C2A—C7A—C6A	−0.5 (3)	C2B—C7B—C6B—N1B	−178.06 (17)
C3A—C4A—C8A—O3A	−173.07 (16)	C2B—C7B—C6B—C5B	0.9 (3)
C3A—C4A—C8A—O4A	5.8 (3)	C1B—C2B—C7B—C6B	175.10 (16)
C3A—C4A—C5A—C6A	−0.6 (3)	C7B—C2B—C1B—O1B	−176.57 (17)
C4A—C5A—C6A—N1A	−179.61 (16)	C7B—C2B—C1B—O2B	0.7 (3)
C4A—C5A—C6A—C7A	−0.5 (3)	C7B—C6B—C5B—C4B	−0.2 (3)
C8A—C4A—C5A—C6A	−179.67 (16)	C5B—C4B—C3B—C2B	1.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WA···O4B	0.93 (4)	2.11 (4)	2.911 (3)	143 (3)
O2W—H2WB···O1Bⁱ	0.88 (4)	2.14 (4)	2.913 (2)	147 (3)
O2W—H2WB···O7Bⁱⁱ	0.88 (4)	2.79 (4)	3.198 (3)	110 (3)
O3A—H3A···O5A	0.94 (3)	1.80 (3)	2.7399 (19)	173 (2)
O3B—H3B···O1W	0.86 (3)	1.76 (3)	2.604 (2)	165 (3)
O1W—H1WA···O2Wⁱⁱⁱ	0.81 (3)	1.97 (3)	2.772 (2)	173 (3)
O1W—H1WB···O7B^iv	0.88 (3)	2.60 (3)	3.185 (2)	124 (2)
O1W—H1WB···O6B^iv	0.88 (3)	1.88 (3)	2.762 (2)	175 (3)
C7A—H7A···O5B^v	0.93	2.54	3.236 (2)	131
N1B—H1BA···O6A^vi	0.94 (2)	2.60 (2)	3.197 (3)	121.7 (17)
N1B—H1BA···O7A^vi	0.94 (2)	2.01 (2)	2.938 (2)	173 (2)
N1B—H1BB···O5B	0.90 (2)	1.96 (2)	2.842 (2)	168 (2)
N1B—H1BB···O6B	0.90 (2)	2.53 (2)	3.142 (2)	125.9 (18)
N1B—H1BC···O2W^vii	0.86 (3)	2.64 (2)	3.056 (3)	111.2 (17)
N1B—H1BC···O1W^vii	0.86 (3)	2.00 (3)	2.841 (2)	165 (2)
N1A—H1AA···O6A^viii	0.81 (3)	2.38 (3)	3.104 (3)	150 (2)
N1A—H1AA···O5A^viii	0.81 (3)	2.32 (3)	3.070 (2)	154 (2)
N1A—H1AB···O7B^v	0.90 (2)	2.25 (2)	2.934 (2)	132.1 (18)
N1A—H1AB···O5B^v	0.90 (2)	2.12 (2)	2.992 (2)	162.9 (19)
N1A—H1AC···O4A^viii	0.86 (2)	2.53 (2)	2.899 (2)	107.3 (17)
N1A—H1AC···O5A^ix	0.86 (2)	2.34 (2)	3.000 (2)	133.8 (19)
N1A—H1AC···O7A^ix	0.86 (2)	2.10 (3)	2.942 (2)	167 (2)
O1A—H1A···O2B	0.77 (4)	1.91 (4)	2.669 (2)	174 (4)
O1B—H1B···O2A	0.82 (3)	1.85 (3)	2.662 (2)	170 (3)

Symmetry codes: (i) x, y−1, z; (ii) x, −y−1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, −y, −z+1; (v) x, −y+3/2, z+1/2; (vi) −x+2, y−3/2, −z+1/2; (vii) x, −y+1/2, z−1/2; (viii) x, −y+7/2, z+1/2; (ix) −x+2, −y+4, −z+1.

Funding information

The authors acknowledge the Algerian Ministry of Higher Education and Scientific Research, the Algerian Directorate-General for Scientific Research and Technological Development for support.

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