Crystal structure of di­benzyl­ammonium hydrogen (4-amino­phen­yl)arsonate monohydrate

Traoré, B.; Diallo, W.; Sidibé, M.; Diop, L.; Plasseraud, L.; Cattey, H.

doi:10.1107/S205698902300837X

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ISSN: 2056-9890

Volume 79| Part 11| November 2023| Pages 1003-1007

https://doi.org/10.1107/S205698902300837X

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Crystal structure of dibenzylammonium hydrogen (4-aminophenyl)arsonate monohydrate

Bocar Traoré,^a Waly Diallo,^a ^* Mamadou Sidibé,^a Libasse Diop,^a Laurent Plasseraud ^b and Hélène Cattey ^b ^*

^aLaboratoire de Chimie Minérale et Analytique (LACHIMIA), Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^bICMUB UMR 6302, Université de Bourgogne (UB), Faculté des Sciences, 9 avenue Alain Savary, 21000 DIJON, France
^*Correspondence e-mail: waly.diallo@ucad.edu.sn, hcattey@u-bourgogne.fr

Edited by G. Diaz de Delgado, Universidad de Los Andes Mérida, Venezuela (Received 12 April 2023; accepted 22 September 2023; online 5 October 2023)

This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.

The title salt, C₁₄H₁₆N⁺·C₆H₇AsNO₃⁻·H₂O or [(C₆H₅CH₂)₂NH₂][H₂NC₆H₄As(OH)O₂]·H₂O, (I), was synthesized by mixing an aqueous solution of (4-aminophenyl)arsonic acid with an ethanolic solution of dibenzylamine at room temperature. Compound I crystallizes in the monoclinic P2₁/c space group. The three components forming I are linked via N—H⋯O and O—H⋯O intermolecular hydrogen bonds, resulting in the propagation of an infinite zigzag chain. Additional weak interactions between neighbouring chains, such as π–π and N—H⋯O contacts, involving phenyl rings, –NH₂ and –As(OH)O₃ functions, and H₂O, respectively, lead to a three-dimensional network.

Keywords: crystal structure; group 15 - pnictogen elements; organic salt; phenylarsonic derivatives; hydrogen bonds; infinite chain.

CCDC reference: 2297206

1. Chemical context

Organoarsenic compounds have been known for a long time and sparked great interest when they were discovered. Tetramethyldiarsine (Me₂As-AsMe₂), commonly known as Cacodyl, was isolated in the middle of the 18^th century by Cadet de Glaussicourt (Garje & Jain, 1999 ). During the next century, in 1859, Antoine Béchamp reported the synthesis of p-arsanilic acid sodium salt (named Atoxyl) by reacting aniline with arsenic acid. This compound was employed for pharmaceutical applications, in particular against trypanosomal infection. Subsequently, in the early 20th century, Paul Ehrlich was inspired by this work to develop a new organoarsenic derivative, called Arsphenamine or Salvarsan (Ehrlich & Bertheim, 1907 ). This molecule has proved particularly effective in the treatment of syphilis and sleeping sickness (African Trypanosomiasis) and is considered as being the first chemotherapeutic agent (Williams, 2009 ). The use of organoarsenicals as medicines was subsequently abandoned in favour of penicillin, as they were found to be highly toxic to humans, causing significant side effects (including blindness). However, they have continued to be used, until recently, as feed additives and veterinary drugs, particularly in the livestock and poultry breeding industry, but with serious negative effects on the environment. Soil and groundwater contamination resulting from the excessive use of aromatic organoarsenic compounds is now a major environmental concern (Fei et al., 2018 ). Current investigations involving academics focus on improving analytical detection (Depalma et al., 2008 ; Yang et al., 2018 ) and remediation methods (Jun et al., 2015 ; Chen et al., 2022 ).

From a structural point of view, the crystal structure of phenylarsonic acid was first solved in the early 1960s (refcode ARSACP: Shimada, 1960 ). Since then, the X-ray structure for the zwitterionic form of p-arsanilic acid (p-ammoniophenylarsonate) has been determined (CUDSEZ: Shimada, 1961 ; CUDSEZ01: Nuttall & Hunter, 1996 ) as well as of the hydrated ammonium and sodium salt hydrates of 4-aminophenylarsonic acid (KOKWOY, KOKWUE: Smith & Wermuth, 2014 ). We report herein the structure of a new salt of 4-aminophenylarsonate, isolated from a mixture of (4-aminophenyl)arsonic acid and dibenzylamine and characterized as dibenzylammonium hydrogen (4-aminophenyl)arsonate monohydrate, [(C₆H₅CH₂)₂NH₂][H₂NC₆H₄As(OH)O₂]·H₂O (I).

2. Structural commentary

The asymmetric unit of the title salt, which is depicted in Fig. 1, comprises one dibenzylammonium cation [(C₆H₅CH₂)₂NH₂]⁺, one hydrogen (4-aminophenyl)arsonate anion [H₂NC₆H₅As(OH)O₂]⁻ and one water molecule of solvation. The three components of I are linked together through intermolecular N—H⋯O and O—H⋯O hydrogen bonds. The As atom of the anion is bonded to three O atoms and one carbon atom of the phenyl ring, describing a slightly distorted tetrahedral geometry [O1—As—C1 = 103.71 (6)°, O2—As—C1 = 110.47 (6)°, O3—As—C1 = 111.73 (6)°, O2—As—O1 = 110.71 (5)°, O3—As—O1 = 108.46 (5)°, O3—As—O2 = 111.48 (5)°]. The As—O bonds exhibit two distinct lengths: As—O1 = 1.7267 (10) Å, and As—O2 = 1.6730 (10) Å and As—O3 =1.6699 (10) Å, which can be considered to be identical. The As—O1 distance is consistent with the presence of a hydroxyl group (Yang et al., 2002 ), while the As—O2 and As—O3 distances, which are shorter, reflect rather a double-bond character. In the literature, based on a comparison of structural examples, the average length of the As—O bond is defined as 1.77 Å and that of the As=O bond as 1.67 Å (Nuttall & Hunter, 1996). The nature of the As=O2 and As=O3 double bonds implies that the negative charge is delocalized on the arsonate. The three oxygen atoms of the arsonate function are engaged in hydrogen bonding, the O1 and O2 atoms being linked head-to-tail [O1—H⋯O2^iv, D⋯A = 2.5444 (15) Å; symmetry code: (iv) −x, −y + 1, −z + 1, Table 1]. The length of the As—C1 bond [1.8955 (13) Å] is within the range of values measured for related compounds such as ammonium 4-nitrophenylarsonate (Yang et al., 2002) and guanidinium phenylarsonate (Smith & Wermuth, 2010 ). An amino group is positioned on the phenyl ring in the para position to the arsonate function. Both functional groups are contained in the plane of the phenyl ring. The negative charge of [H₂NC₆H₄As(OH)O₂]⁻ is compensated by the presence of one dibenzylammonium cation, [(C₆H₅CH₂)₂NH₂]⁺, whose NH₂⁺ group is hydrogen bonded to the oxygen atom O3 of the arsonate function [N1—H1A⋯O3, D⋯A = 2.6842 (16) Å, N1—H1B⋯O3ⁱⁱⁱ, D⋯A = 2.7260 (15) Å; symmetry code: (iii) −x + 1, −y + 1, −z + 1]. Moreover, the dibenzylammonium cation shows a syn–anti conformation, displaying C—C—N—C torsion angles of 57.65 (16)° and −178.14 (11)°, which are in the range of previous examples of X-ray structures involving [(C₆H₅CH₂)₂NH₂]⁺ (Trivedi & Dastidar, 2006 ). A water molecule (co-solvent of the reaction) participates in a hydrogen-bond interaction with the oxygen atom O2 of –As(OH)O₂⁻ [O4—H4A⋯O2^V, D⋯A = 2.8074 (18) Å; symmetry code: (v) 1 + x, y, z] completes the composition of salt I. From a spectroscopic point of view, the infrared spectrum of I (ATR mode) highlights ν(As—C) and ν(As—O) absorption bands, which are characteristic of the arsonate function (Cowen et al., 2008 ), at 1096 cm⁻¹ and between 925–690 cm⁻¹, respectively. The percentages of C, H, N and O determined by elemental analysis support the chemical composition of I, but show that the salt is partially dehydrated (see the Synthesis and crystallization section).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4ⁱ	0.84 (2)	2.37 (2)	3.165 (2)	158.0 (18)
N2—H2B⋯O1ⁱⁱ	0.83 (2)	2.25 (2)	3.0769 (17)	175.6 (18)
N1—H1A⋯O3	0.91	1.78	2.6842 (16)	172
N1—H1B⋯O3ⁱⁱⁱ	0.91	1.89	2.7260 (15)	151
O1—H1⋯O2^iv	0.83 (3)	1.73 (3)	2.5445 (15)	170 (3)
O4—H4A⋯O2^v	0.87	1.95	2.8074 (18)	169
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (iv) ; (v) x+1, y, z.

Figure 1
The molecular structure of I with displacement ellipsoids at the 30% probability level.The water molecule was found to be disordered over two positions, the minor part was omitted and the major part is represented with the following symmetry code: (i): −1 + x, y, z. Dotted lines indicate hydrogen bonds.

3. Supramolecular features

At the supramolecular stage, two levels of organization can be observed in the crystal structure of I:

(i) The propagation of one-dimensional zigzag chains along the a-axis direction resulting from the hydrogen-bonding interactions (Fig. 2). The NH₂ groups of two dibenzylammonium cations are involved in two independent hydrogen bonds, oriented perpendicularly [O3⋯N1⋯O3 = 92.63 (5)°], with the oxygen atoms O3 of two arsonate moieties [N1—H1A⋯O3 and N1—H1B⋯O3ⁱⁱⁱ, Table 1]. This leads to the formation of a tetrameric unit describing a four-membered ring (Fig. 3). These units are linked together by two additional and parallel hydrogen bonds involving two hydrogen (4-aminophenyl)arsonate anions [O1—H1⋯O2^iv, Table 1]. This creates a six-membered ring. In addition, the water molecule contained in I is also in hydrogen-bonding interaction with the oxygen atom O2 of the arsonate group [O4—H4A⋯O2^v, Table 1]. The 4-aminophenyl groups can be viewed as perpendicular to the chain axis and positioned alternately on either side of it.

Figure 2
Mercury representation (Macrae et al., 2020

; colour code: C = grey, N = blue, O = red, As = pink, H = white] of the infinite chain structure of I propagating along the a-axis direction via hydrogen bonds (dotted cyan lines).

Figure 3
Mercury representation (Macrae et al., 2020

; colour code: C = grey, N = blue, O = red, As = pink, H = white) highlighting the hydrogen-bonding network (cyan dotted lines) involving the components of I (the benzyl H atoms have been omitted for clarity).

(ii) The association of chains leading to a three-dimensional network and resulting from a combination of weak interactions (Fig. 4). Two types of π–π stacking interactions involving the phenyl rings of the dibenzylammonium cations can be described (Fig. 5): (a) centroid(C15–C20)–centroid (C15ⁱ–C20ⁱ) = 3.9384 (10) Å, interplanar distance = 3.4310 (18) Å, slip angle (angle between the normal to the plane and the centroid–centroid vector) = 29.4, corresponding to a slippage distance of 1.933 Å; symmetry code: (i) 1 − x, 2 − y, 1 − z; (b) centroid(C8–C13)–centroid(C15ⁱⁱ–C20ⁱⁱ) = 4.0178 (10) Å, interplanar distance = 3.5093 (6) Å, slip angle = 29.1°, corresponding to a slippage distance of 1.957 Å; symmetry code: (ii) 1 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z. In addition, the NH₂ groups located in the para position of C₆H₄As(OH)O₂, interact via hydrogen bonding with a water molecule [N2—H2A⋯O4¹ = 3.165 (2) Å] and the O1 oxygen atom of an adjacent –As(OH)O₂ function [N2—H2B⋯O1ⁱⁱ = 3.0769 (17) Å] (symmetry codes as in Table 1).

Figure 4
Arrangement of the chains in the crystal of I and along the b-axis, leading to a three-dimensional network (Mercury representation; Macrae et al., 2020

; colour code: C = grey, N = blue, O = red, As = pink, H = white). H atoms of phenyl and benzyl groups are omitted for clarity. The hydrogen bonds propagating the infinite chains are represented by dotted cyan lines.

Figure 5
View of the π–π stacking interactions between phenyl rings of the dibenzylammonium cations of I [along the a-axis, Mercury representation (Macrae et al., 2020

); colour code: C = grey, N = blue, H = white). H atoms of phenyl rings, anions and water molecules have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (WebCSD update 11/2022; Groom et al., 2016 ), revealed that, to date, there are relatively few X-ray structures exhibiting the isolated hydrogen phenylarsonate moiety, C₆H₅As(OH)O₂⁻. To our knowledge, eleven examples including this fragment have already been identified: ammonium 4-nitrophenylarsonate (AHILAE: Yang et al., 2002), guanidinium phenylarsonate guanidine dihydrate (DUSCIE: Smith & Wermuth, 2010), p-aminophenylarsonic acid (CUDSEZ: Shimada, 1961; CUDSEZ01: Nuttall & Hunter, 1996), ammonium hydrogen (4-aminophenyl)arsonate monohydrate (KOKWOY: Smith & Wermuth, 2014), 1-(4-hydroxy-2-methylphenyl)-2,4,6-triphenylpyridinium hydrogen o-arsanilate monohydrate (PAZRIS: Wojtas et al., 2006 ), tetrabutylammonium hydrogen phenylarsonate–phenylarsonic acid (QECBEH: Reck & Schmitt, 2012 ), 3-ammonio-4-hydroxyphenylarsonate (ROBDAO: Lloyd et al., 2008 ), hexaaquamanganese(II) bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate (UBURIV: Smith & Wermuth, 2016a ), hexaaqua-magnesium bis(hydrogen (4-aminophenyl)arsonate) tetrahydrate (UDAPIB: Smith & Wermuth, 2017a ), 2,3-dimethoxy-10-oxostrychnidin-19-ium hydrogen (4-aminophenyl)arsonate tetrahydrate (ULIROY: Smith & Wermuth, 2016b ), 2,4-diamino-5-(3,4,5-trimethoxybenzyl)pyrimidinium 4-hydroxy-3-nitrophenylarsonate monohydrate (XEMZIZ: Pan et al., 2006 ). In coordination chemistry, phenylarsonic acid and its derivatives constitute also suitable ligands to generate coordination polymers and heteropolyoxometalates in the presence of transition metals (Lesikar-Parrish et al., 2013 ), main-group metals (Xie et al., 2008 ), alkali metals (Smith & Wermuth, 2017a) and alkali-earth metal precursors (Smith & Wermuth, 2017b ). Regarding the dibenzylammonium cation, [(C₆H₅CH₂)₂NH₂]⁺, 117 hits incorporating such an entity were found in the Cambridge Structural Database.

5. Synthesis and crystallization

All chemicals were purchased from Sigma-Aldrich (Germany) and used without any further purification. (4-Aminophenyl)arsonic acid [H₂NC₆H₄As(OH)₂O] was prepared according to a previous work (Lewis & Cheetham, 1923 ), by reacting aniline (C₆H₅NH₂) and arsenic acid (As(OH)₃O). The title salt was obtained by neutralization of an aqueous solution (20 mL) of (4-aminophenyl)arsonic acid (2.15 g, 9.90 mmol) with dibenzylamine ((C₆H₅CH₂)₂NH) (3.90 g, 19.80 mmol) dissolved in 20 mL of ethanol. The mixture was stirred for about two h at room temperature (301 K). After three days of slow solvent evaporation, colourless prism-shaped crystals of [(C₆H₅CH₂)₂NH₂][H₂NC₆H₄As(OH)O₂]·H₂O (5.25 g, 64% yield), suitable for an X-ray crystallographic analysis, were collected from the solvent (m.p. 393 K). FT–IR (ATR, Bruker Alpha FTIR spectrometer, cm⁻¹): 3447, 3304, 3187, 1595, 1501, 1454, 1096, 923, 878, 825,752, 735, 695. Elemental analysis (Elemental Analyser, ThermoFisher FlashSmart CHNS/O) – analysis calculated for C₂₀H₂₃N₂O₃As·0.25H₂O (418.83), salt I partially dehydrated: C, 57.35; H, 5.66; N, 6.69; O, 12.41; found: C, 57.82; H, 5.61; N, 6.62; O, 12.37%.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. The asymmetric unit contains the dibenzylammonium hydrogen (4-aminophenyl)arsonate monohydrate. The water molecule was found disordered over two main positions with occupancy factors that converged to 0.94:0.06. Hence, the minor part of the water molecule was refined only isotropically and without the hydrogen atoms. The hydrogen atoms for the major component of the water molecule were refined geometrically as a rigid group (O—H = 0.87 Å) with U_iso(H) = 1.5U_eq(O). C-bound hydrogen atoms were placed at calculated positions [C—H = 0.95 Å (aromatic) or 0.99 Å (methylene group)] and H atoms of the NH₂ and OH terminal groups were placed geometrically (N—H = 0.83–0.84 Å, O—H = 0.83 Å) and refined as riding with U_iso(H) = 1.2U_eq(N, C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N⁺·C₆H₇AsNO₃⁻·H₂O
M_r	432.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.8242 (5), 10.6574 (6), 19.2507 (11)
β (°)	97.7500 (18)
V (Å³)	1997.15 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.73
Crystal size (mm)	0.5 × 0.25 × 0.18

Data collection
Diffractometer	Bruker D8 VENTURE
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.610, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	67932, 4584, 4119
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.054, 1.07
No. of reflections	4584
No. of parameters	261
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.21
Computer programs: APEX2 (Bruker, 2014 ), SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2297206

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698902300837X/dj2065sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300837X/dj2065Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902300837X/dj2065Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 V8.34A (Bruker, 2014); cell refinement: SAINT V8.34A (Bruker, 2013); data reduction: SAINT V8.34A (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

Dibenzylammonium hydrogen (4-aminophenyl)arsonate monohydrate top

Crystal data top

C₁₄H₁₆N⁺·C₆H₇AsNO₃⁻·H₂O	F(000) = 896
M_r = 432.34	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.8242 (5) Å	Cell parameters from 9824 reflections
b = 10.6574 (6) Å	θ = 2.8–27.5°
c = 19.2507 (11) Å	µ = 1.73 mm⁻¹
β = 97.7500 (18)°	T = 100 K
V = 1997.15 (19) Å³	Prism, clear light colourless
Z = 4	0.5 × 0.25 × 0.18 mm

Data collection top

Bruker D8 VENTURE diffractometer	4584 independent reflections
Radiation source: X-ray tube, Siemens KFF Mo 2K-90C	4119 reflections with I > 2σ(I)
TRIUMPH curved crystal monochromator	R_int = 0.037
Detector resolution: 1024 x 1024 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −13→13
T_min = 0.610, T_max = 0.746	l = −24→25
67932 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0228P)² + 1.3431P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4584 reflections	Δρ_max = 0.42 e Å⁻³
261 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints

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	Occ. (<1)
As	0.15165 (2)	0.51188 (2)	0.42563 (2)	0.01186 (5)
O1	0.04372 (11)	0.38487 (9)	0.42927 (6)	0.0184 (2)
O2	0.09995 (10)	0.63317 (9)	0.47065 (5)	0.0167 (2)
O3	0.31128 (10)	0.46779 (10)	0.45696 (5)	0.0176 (2)
N2	0.08041 (14)	0.62660 (14)	0.11336 (7)	0.0208 (3)
H2A	0.062 (2)	0.565 (2)	0.0867 (10)	0.025*
H2B	0.043 (2)	0.694 (2)	0.1009 (10)	0.025*
C1	0.13469 (13)	0.55046 (13)	0.32872 (7)	0.0126 (3)
C2	0.13667 (14)	0.45347 (13)	0.27999 (7)	0.0152 (3)
H2	0.149937	0.369445	0.295952	0.018*
C3	0.11956 (15)	0.47831 (14)	0.20880 (7)	0.0164 (3)
H3	0.121018	0.411363	0.176326	0.020*
C4	0.10001 (14)	0.60216 (14)	0.18428 (7)	0.0150 (3)
C5	0.10337 (14)	0.69966 (13)	0.23332 (8)	0.0166 (3)
H5	0.094757	0.784146	0.217604	0.020*
C6	0.11920 (14)	0.67391 (13)	0.30476 (7)	0.0150 (3)
H6	0.119468	0.740721	0.337450	0.018*
O4	0.94231 (17)	0.85325 (13)	0.45149 (7)	0.0389 (3)	0.94
H4A	0.999317	0.790435	0.455138	0.058*	0.94
H4B	0.870836	0.825432	0.468917	0.058*	0.94
N1	0.43532 (12)	0.63057 (11)	0.55144 (6)	0.0142 (2)
H1A	0.391629	0.570678	0.522995	0.017*
H1B	0.523283	0.604491	0.564385	0.017*
C7	0.36565 (15)	0.64208 (13)	0.61550 (7)	0.0156 (3)
H7A	0.268703	0.667011	0.601690	0.019*
H7B	0.411155	0.708549	0.646221	0.019*
C8	0.37054 (14)	0.52036 (13)	0.65533 (7)	0.0134 (3)
C9	0.49603 (15)	0.46656 (14)	0.68231 (8)	0.0167 (3)
H9	0.579319	0.506225	0.674660	0.020*
C10	0.50021 (15)	0.35571 (14)	0.72019 (8)	0.0194 (3)
H10	0.586162	0.319539	0.738161	0.023*
C11	0.37894 (16)	0.29743 (15)	0.73190 (8)	0.0227 (3)
H11	0.381734	0.221469	0.757878	0.027*
C12	0.25392 (16)	0.35050 (15)	0.70557 (9)	0.0251 (3)
H12	0.170863	0.311054	0.713808	0.030*
C13	0.24933 (15)	0.46135 (15)	0.66711 (8)	0.0200 (3)
H13	0.163208	0.496855	0.648829	0.024*
C14	0.43754 (16)	0.75047 (14)	0.51084 (8)	0.0194 (3)
H14A	0.342130	0.775473	0.493084	0.023*
H14B	0.486851	0.736507	0.469927	0.023*
C15	0.50659 (15)	0.85489 (14)	0.55510 (8)	0.0182 (3)
C16	0.42794 (16)	0.94873 (15)	0.57986 (8)	0.0220 (3)
H16	0.330863	0.947490	0.568182	0.026*
C17	0.49027 (19)	1.04468 (15)	0.62169 (9)	0.0277 (4)
H17	0.435865	1.108628	0.638562	0.033*
C18	0.6313 (2)	1.04676 (17)	0.63861 (9)	0.0322 (4)
H18	0.673979	1.112232	0.667157	0.039*
C19	0.71081 (18)	0.95354 (18)	0.61403 (10)	0.0323 (4)
H19	0.807876	0.955423	0.625699	0.039*
C20	0.64919 (16)	0.85748 (16)	0.57247 (9)	0.0249 (3)
H20	0.703946	0.793541	0.555854	0.030*
H1	0.002 (3)	0.386 (3)	0.4638 (14)	0.062 (8)*
O4B	0.729 (2)	0.7346 (18)	0.4434 (10)	0.026 (4)*	0.06

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As	0.01149 (7)	0.01330 (7)	0.01092 (7)	−0.00011 (5)	0.00195 (5)	−0.00127 (5)
O1	0.0235 (5)	0.0140 (5)	0.0192 (5)	−0.0066 (4)	0.0084 (4)	−0.0043 (4)
O2	0.0200 (5)	0.0125 (5)	0.0187 (5)	−0.0005 (4)	0.0070 (4)	−0.0030 (4)
O3	0.0143 (5)	0.0226 (5)	0.0150 (5)	0.0041 (4)	−0.0009 (4)	−0.0025 (4)
N2	0.0233 (7)	0.0235 (7)	0.0151 (6)	0.0019 (6)	0.0010 (5)	0.0037 (5)
C1	0.0096 (6)	0.0163 (6)	0.0119 (6)	−0.0005 (5)	0.0018 (5)	0.0004 (5)
C2	0.0157 (7)	0.0132 (6)	0.0164 (7)	0.0004 (5)	0.0011 (5)	0.0009 (5)
C3	0.0179 (7)	0.0164 (7)	0.0147 (7)	0.0000 (5)	0.0013 (5)	−0.0022 (5)
C4	0.0097 (6)	0.0198 (7)	0.0158 (7)	0.0003 (5)	0.0026 (5)	0.0029 (5)
C5	0.0149 (7)	0.0140 (6)	0.0211 (7)	0.0016 (5)	0.0035 (5)	0.0042 (5)
C6	0.0127 (6)	0.0147 (6)	0.0179 (7)	−0.0005 (5)	0.0035 (5)	−0.0018 (5)
O4	0.0569 (10)	0.0308 (7)	0.0304 (7)	0.0169 (7)	0.0104 (7)	0.0108 (6)
N1	0.0149 (6)	0.0140 (6)	0.0132 (6)	−0.0003 (4)	0.0007 (4)	0.0000 (4)
C7	0.0170 (7)	0.0144 (6)	0.0160 (7)	0.0009 (5)	0.0045 (5)	−0.0008 (5)
C8	0.0143 (6)	0.0137 (6)	0.0123 (6)	−0.0003 (5)	0.0023 (5)	−0.0020 (5)
C9	0.0129 (6)	0.0194 (7)	0.0181 (7)	−0.0015 (5)	0.0031 (5)	0.0003 (6)
C10	0.0160 (7)	0.0223 (7)	0.0198 (7)	0.0047 (6)	0.0016 (6)	0.0031 (6)
C11	0.0253 (8)	0.0182 (7)	0.0247 (8)	0.0005 (6)	0.0043 (6)	0.0059 (6)
C12	0.0172 (7)	0.0229 (8)	0.0354 (9)	−0.0053 (6)	0.0044 (7)	0.0068 (7)
C13	0.0119 (7)	0.0214 (7)	0.0260 (8)	−0.0005 (5)	−0.0001 (6)	0.0028 (6)
C14	0.0230 (8)	0.0187 (7)	0.0161 (7)	−0.0018 (6)	0.0010 (6)	0.0048 (6)
C15	0.0204 (7)	0.0173 (7)	0.0169 (7)	−0.0042 (6)	0.0022 (6)	0.0057 (6)
C16	0.0226 (8)	0.0191 (7)	0.0246 (8)	−0.0032 (6)	0.0050 (6)	0.0045 (6)
C17	0.0409 (10)	0.0180 (7)	0.0256 (8)	−0.0041 (7)	0.0095 (7)	0.0018 (6)
C18	0.0434 (10)	0.0244 (8)	0.0276 (9)	−0.0172 (8)	0.0004 (8)	0.0012 (7)
C19	0.0237 (8)	0.0356 (10)	0.0358 (10)	−0.0118 (7)	−0.0023 (7)	0.0051 (8)
C20	0.0207 (8)	0.0257 (8)	0.0283 (8)	−0.0022 (6)	0.0037 (6)	0.0044 (7)

Geometric parameters (Å, º) top

As—O1	1.7267 (10)	C7—C8	1.5044 (19)
As—O2	1.6730 (10)	C8—C9	1.395 (2)
As—O3	1.6699 (10)	C8—C13	1.392 (2)
As—C1	1.8955 (13)	C9—H9	0.9500
O1—H1	0.83 (3)	C9—C10	1.386 (2)
N2—H2A	0.84 (2)	C10—H10	0.9500
N2—H2B	0.83 (2)	C10—C11	1.389 (2)
N2—C4	1.3776 (19)	C11—H11	0.9500
C1—C2	1.3978 (19)	C11—C12	1.385 (2)
C1—C6	1.3957 (19)	C12—H12	0.9500
C2—H2	0.9500	C12—C13	1.392 (2)
C2—C3	1.384 (2)	C13—H13	0.9500
C3—H3	0.9500	C14—H14A	0.9900
C3—C4	1.406 (2)	C14—H14B	0.9900
C4—C5	1.401 (2)	C14—C15	1.506 (2)
C5—H5	0.9500	C15—C16	1.387 (2)
C5—C6	1.391 (2)	C15—C20	1.396 (2)
C6—H6	0.9500	C16—H16	0.9500
O4—H4A	0.8696	C16—C17	1.391 (2)
O4—H4B	0.8701	C17—H17	0.9500
N1—H1A	0.9100	C17—C18	1.380 (3)
N1—H1B	0.9100	C18—H18	0.9500
N1—C7	1.4939 (17)	C18—C19	1.386 (3)
N1—C14	1.4995 (18)	C19—H19	0.9500
C7—H7A	0.9900	C19—C20	1.387 (2)
C7—H7B	0.9900	C20—H20	0.9500

O1—As—C1	103.71 (6)	C13—C8—C7	120.22 (13)
O2—As—O1	110.71 (5)	C13—C8—C9	119.09 (13)
O2—As—C1	110.47 (6)	C8—C9—H9	119.7
O3—As—O1	108.46 (5)	C10—C9—C8	120.55 (13)
O3—As—O2	111.48 (5)	C10—C9—H9	119.7
O3—As—C1	111.73 (5)	C9—C10—H10	120.0
As—O1—H1	113.0 (19)	C9—C10—C11	120.09 (14)
H2A—N2—H2B	116.7 (18)	C11—C10—H10	120.0
C4—N2—H2A	116.7 (13)	C10—C11—H11	120.1
C4—N2—H2B	116.7 (13)	C12—C11—C10	119.73 (14)
C2—C1—As	119.52 (10)	C12—C11—H11	120.1
C6—C1—As	121.39 (10)	C11—C12—H12	119.8
C6—C1—C2	119.08 (13)	C11—C12—C13	120.33 (14)
C1—C2—H2	119.6	C13—C12—H12	119.8
C3—C2—C1	120.83 (13)	C8—C13—H13	119.9
C3—C2—H2	119.6	C12—C13—C8	120.20 (14)
C2—C3—H3	119.8	C12—C13—H13	119.9
C2—C3—C4	120.33 (13)	N1—C14—H14A	109.2
C4—C3—H3	119.8	N1—C14—H14B	109.2
N2—C4—C3	120.31 (13)	N1—C14—C15	111.83 (12)
N2—C4—C5	120.99 (13)	H14A—C14—H14B	107.9
C5—C4—C3	118.69 (13)	C15—C14—H14A	109.2
C4—C5—H5	119.7	C15—C14—H14B	109.2
C6—C5—C4	120.62 (13)	C16—C15—C14	119.86 (14)
C6—C5—H5	119.7	C16—C15—C20	119.40 (14)
C1—C6—H6	119.8	C20—C15—C14	120.73 (14)
C5—C6—C1	120.37 (13)	C15—C16—H16	119.8
C5—C6—H6	119.8	C15—C16—C17	120.45 (15)
H4A—O4—H4B	104.5	C17—C16—H16	119.8
H1A—N1—H1B	107.7	C16—C17—H17	120.1
C7—N1—H1A	108.8	C18—C17—C16	119.86 (16)
C7—N1—H1B	108.8	C18—C17—H17	120.1
C7—N1—C14	113.62 (11)	C17—C18—H18	119.9
C14—N1—H1A	108.8	C17—C18—C19	120.13 (16)
C14—N1—H1B	108.8	C19—C18—H18	119.9
N1—C7—H7A	109.4	C18—C19—H19	119.9
N1—C7—H7B	109.4	C18—C19—C20	120.25 (16)
N1—C7—C8	111.30 (11)	C20—C19—H19	119.9
H7A—C7—H7B	108.0	C15—C20—H20	120.0
C8—C7—H7A	109.4	C19—C20—C15	119.91 (16)
C8—C7—H7B	109.4	C19—C20—H20	120.0
C9—C8—C7	120.67 (13)

As—C1—C2—C3	177.66 (11)	N1—C14—C15—C20	74.49 (17)
As—C1—C6—C5	−178.33 (10)	C7—N1—C14—C15	57.65 (16)
O1—As—C1—C2	−44.30 (12)	C7—C8—C9—C10	178.70 (13)
O1—As—C1—C6	135.23 (11)	C7—C8—C13—C12	−178.27 (14)
O2—As—C1—C2	−162.96 (10)	C8—C9—C10—C11	−0.3 (2)
O2—As—C1—C6	16.57 (13)	C9—C8—C13—C12	0.3 (2)
O3—As—C1—C2	72.32 (12)	C9—C10—C11—C12	0.0 (2)
O3—As—C1—C6	−108.15 (11)	C10—C11—C12—C13	0.4 (3)
N2—C4—C5—C6	178.11 (13)	C11—C12—C13—C8	−0.6 (2)
C1—C2—C3—C4	0.1 (2)	C13—C8—C9—C10	0.2 (2)
C2—C1—C6—C5	1.2 (2)	C14—N1—C7—C8	−178.14 (11)
C2—C3—C4—N2	−178.78 (13)	C14—C15—C16—C17	179.01 (14)
C2—C3—C4—C5	2.3 (2)	C14—C15—C20—C19	−179.17 (15)
C3—C4—C5—C6	−3.0 (2)	C15—C16—C17—C18	0.1 (2)
C4—C5—C6—C1	1.3 (2)	C16—C15—C20—C19	−0.1 (2)
C6—C1—C2—C3	−1.9 (2)	C16—C17—C18—C19	0.0 (3)
N1—C7—C8—C9	60.72 (17)	C17—C18—C19—C20	−0.2 (3)
N1—C7—C8—C13	−120.76 (14)	C18—C19—C20—C15	0.2 (3)
N1—C14—C15—C16	−104.55 (16)	C20—C15—C16—C17	0.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ⁱ	0.84 (2)	2.37 (2)	3.165 (2)	158.0 (18)
N2—H2B···O1ⁱⁱ	0.83 (2)	2.25 (2)	3.0769 (17)	175.6 (18)
N1—H1A···O3	0.91	1.78	2.6842 (16)	172
N1—H1B···O3ⁱⁱⁱ	0.91	1.89	2.7260 (15)	151
O1—H1···O2^iv	0.83 (3)	1.73 (3)	2.5445 (15)	170 (3)
O4—H4A···O2^v	0.87	1.95	2.8074 (18)	169

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

Acknowledgements

The authors are grateful for general and financial support from the University Cheikh Anta Diop-Dakar (Senegal), the University of Bourgogne-Dijon (France) and the Centre National de la Recherche Scientifique (CNRS-France). They would like to thank in particular Ms T. Régnier for elemental analysis measurements.

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