Crystal structure of di­ethyl­ammonium aniline-4-sulfonate anilinium-4-sulfonate

Toure, A.; Diop, L.; Diop, C.A.K.; Oliver, A.G.

doi:10.1107/S2056989016018041

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ISSN: 2056-9890

Volume 72| Part 12| December 2016| Pages 1830-1832

https://doi.org/10.1107/S2056989016018041

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Crystal structure of diethylammonium aniline-4-sulfonate anilinium-4-sulfonate

Assane Toure,^a Libasse Diop,^a ^* Cheikh Abdoul Khadir Diop ^a and Allen G. Oliver ^b

^aLaboratoire de Chimie Minérale et Analytique, Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ^bDepartment of Chemistry and Biochemistry, University of Notre Dame, 246 Nieuwland, Science Hall, Notre Dame, IN 46557-5670, USA
^*Correspondence e-mail: dlibasse@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 October 2016; accepted 9 November 2016; online 18 November 2016)

The title compound, C₄H₁₂N⁺·C₆H₆NO₃S⁻·C₆H₇NO₃S, consists of an ion pair and a zwitterionic neutral molecule. The cation adopts an extended conformation [C—C—N—C torsion angles = 177.1 (3) and −178.4 (3)°]. In the crystal, the components are linked by N—H⋯O and N—H⋯N hydrogen bonds, generating a three-dimensional network, which is consolidated by weak C—H⋯O interactions.

Keywords: crystal structure; diethylammonium cation; anilinesulfonic zwitterion; anilinesulfonate; hydrogen bonds; three-dimensional structure.

CCDC reference: 1515845

1. Chemical context

Acids such as sulfuric, nitric, oxalic, phosphoric, substituted sulfonic, etc. when mixed in water with amines give acidic or neutral salts that may be soluble in organic solvents: this solubility allows for the study of their interactions with metal halides, acetates, nitrates, perchlorates, etc, which yield new adducts and complexes in which the conjugate anion of the acid behaves as a ligand, usually coordinating the metal ion (Najafi et al., 2011a ,b ; Ittyachan et al., 2016 ; Majeed & Wendt, 2016 ).

We report here the synthesis and structure of the product arising from the mixing of diethylamine and anilinesulfonic acid solutions, which contains a combination of ions and a zwitterion. In terms of other compounds containing both the anilinesulfonate anion and its zwitterionic form, aniliniumsulfonate, to date only the 4-aminopyridinium salt has been reported (Fun et al., 2008 ).

2. Structural commentary

There is one diethylammonium cation, one anilinesulfonate anion and one zwitterionic aniliniumsulfonate molecule in the asymmetric unit (Fig. 1). The individual molecules are unremarkable with bond distances and angles typical of their type. The cation adopts an extended conformation [C1—C2—N1—C3 and C2—N1—C3—C4 torsion angles = 177.1 (3) and −178.4 (3)°, respectively].

Figure 1
The molecular structure of the title compound. Displacement ellipsoids depicted at the 50% probability level and H atoms as spheres of an arbitrary radius. Hydrogen bonds are represented by light-blue dashed lines.

3. Supramolecular features

The zwitterionic aniliniumsulfonate and the anilinesulfonate anion are connected through N2—H2NA⋯O4ⁱ, N2—H2NB⋯O5ⁱⁱ, N2—H2NC⋯N3ⁱⁱⁱ, N3—H3NA⋯O1^iv and N3—H3NB⋯O3^v hydrogen bonds (Table 1) giving sheet-like bi-layers that lie parallel to the bc plane [symmetry codes: (i) −x + 1, y − $[{1\over 2}]$ , −z + 1; (ii) −x + 1, y + $[{1\over 2}]$ , −z + 1; (iii) x − 1, y, z − 1; (iv) −x + 1, y + $[{1\over 2}]$ , −z + 2; (v) −x + 1, y − $[{1\over 2}]$ , −z + 2]. The bi-layers are then linked through N1—H1NA⋯O2, N1—H1NB⋯O5 and N1—H1NB⋯O6 hydrogen bonds, yielding a three-dimensional network (Fig. 2). Some weak C—H⋯O (C3—H3A⋯O3^vi, C6—H6⋯O3^vi and C9—H9⋯O1^vii) interactions consolidate the packing in the crystal [symmetry codes: (vi) x, y − 1, z; (vii) −x, y + $[{1\over 2}]$ , −z + 1]. Examination of the packing reveals layers of diethyl ammonium cation sandwiched between bi-layers of aniline sulfate moieties. The key hydrogen bonds establishing the three-dimensional array are the contacts to sulfonate oxygen atoms and the N2⋯N3 aniline interactions. All amine hydrogen atoms form good hydrogen-bond contacts to neighboring hydrogen-bond acceptor atoms.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O2	0.96 (3)	1.79 (4)	2.748 (4)	175 (3)
N1—H1NB⋯O5	0.90 (3)	2.45 (3)	3.019 (4)	122 (3)
N1—H1NB⋯O6	0.90 (3)	2.03 (4)	2.920 (4)	173 (3)
N2—H2NA⋯O4ⁱ	0.94 (2)	1.88 (2)	2.794 (4)	165 (3)
N2—H2NB⋯O5ⁱⁱ	0.94 (2)	1.85 (2)	2.778 (3)	171 (3)
N2—H2NC⋯N3ⁱⁱⁱ	0.97 (2)	1.85 (2)	2.812 (4)	178 (4)
N3—H3NA⋯O1^iv	0.83 (4)	2.21 (4)	2.998 (4)	157 (3)
N3—H3NB⋯O3^v	0.79 (3)	2.23 (3)	2.997 (4)	164 (3)
C3—H3A⋯O3^vi	0.99	2.48	3.338 (4)	145
C6—H6⋯O3^vi	0.95	2.65	3.507 (4)	151
C9—H9⋯O1^vii	0.95	2.59	3.517 (4)	165
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (iii) x-1, y, z-1; (iv) $[-x+1, y+{\script{1\over 2}}, -z+2]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (vi) x, y-1, z; (vii) $[-x, y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Packing diagram, viewed along the b axis. Hydrogen bonds are represented by light-blue dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 5.37 + one update; Groom et al., 2016 ) shows 46 hits concerning the anilinesulfonate anion, three containing aniliniumsulfonate and one hit with both (Fun et al., 2008), while 303 hits concern the diethylammonium ion.

5. Synthesis and crystallization

Dimethyl amine was mixed in water with aniline sulfonic acid in a 1:1 ratio. Colorless block-like crystals were obtained on allowing the water to evaporate at 333 K.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms bonded to carbon were included in geometrically calculated positions and allowed to ride on the parent atom. All amine hydrogen atoms were located in a difference Fourier map and refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₁₂N⁺·C₆H₆NO₃S⁻·C₆H₇NO₃S
M_r	419.51
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	120
a, b, c (Å)	11.419 (3), 5.6731 (16), 15.226 (4)
β (°)	95.530 (4)
V (Å³)	981.8 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.22 × 0.19 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.781, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	18906, 4911, 4228
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.077, 0.98
No. of reflections	4911
No. of parameters	274
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.38
Absolute structure	Flack x determined using 1632 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.03 (6)
Computer programs: APEX3 and SAINT (Bruker, 2015 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

As the molecules are achiral, only the correct enantiomorph of the space group was determined: this was determined by comparison of intensities of Friedel pairs of reflections yielding a Flack x parameter of 0.03 (6) (Parsons et al., 2013 ) and a Hooft y parameter of 0.04 (6) (Hooft et al., 2008 ).

Supporting information

CCDC reference: 1515845

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018041/hb7622sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016018041/hb7622Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016018041/hb7622Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Diethylammonium aniline-4-sulfonate anilinium-4-sulfonate top

Crystal data top

C₄H₁₂N⁺·C₆H₆NO₃S⁻·C₆H₇NO₃S	F(000) = 444
M_r = 419.51	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 11.419 (3) Å	Cell parameters from 4341 reflections
b = 5.6731 (16) Å	θ = 2.7–24.5°
c = 15.226 (4) Å	µ = 0.31 mm⁻¹
β = 95.530 (4)°	T = 120 K
V = 981.8 (5) Å³	Plate, colorless
Z = 2	0.22 × 0.19 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	4911 independent reflections
Radiation source: fine-focus sealed tube	4228 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 8.33 pixels mm^-1	θ_max = 28.4°, θ_min = 1.3°
combination of ω and φ–scans	h = −15→15
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −7→7
T_min = 0.781, T_max = 0.931	l = −20→20
18906 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0303P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.001
4911 reflections	Δρ_max = 0.29 e Å⁻³
274 parameters	Δρ_min = −0.38 e Å⁻³
4 restraints	Absolute structure: Flack x determined using 1632 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: real-space vector search	Absolute structure parameter: 0.03 (6)

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
N1	0.5053 (3)	0.0636 (5)	0.74539 (18)	0.0247 (7)
H1NA	0.437 (3)	0.156 (6)	0.727 (2)	0.033 (10)*
H1NB	0.566 (3)	0.160 (6)	0.761 (2)	0.031 (11)*
C1	0.4529 (3)	0.0950 (8)	0.8976 (2)	0.0461 (11)
H1A	0.4323	0.0039	0.9486	0.069*
H1B	0.3869	0.1973	0.8767	0.069*
H1C	0.5224	0.1918	0.9148	0.069*
C2	0.4791 (3)	−0.0698 (7)	0.8253 (2)	0.0365 (10)
H2A	0.5474	−0.1696	0.8458	0.044*
H2B	0.4106	−0.1743	0.8104	0.044*
C3	0.5386 (3)	−0.0861 (7)	0.6708 (2)	0.0336 (9)
H3A	0.4730	−0.1938	0.6512	0.040*
H3B	0.6083	−0.1829	0.6907	0.040*
C4	0.5661 (3)	0.0694 (8)	0.5950 (2)	0.0459 (11)
H4A	0.5848	−0.0291	0.5453	0.069*
H4B	0.6337	0.1699	0.6138	0.069*
H4C	0.4977	0.1683	0.5767	0.069*
S1	0.21877 (6)	0.48653 (13)	0.65278 (5)	0.01702 (18)
O1	0.11341 (17)	0.4576 (4)	0.69828 (12)	0.0192 (5)
O2	0.3108 (2)	0.3205 (4)	0.68312 (15)	0.0281 (6)
O3	0.25973 (19)	0.7296 (4)	0.65346 (13)	0.0221 (5)
N2	0.0854 (2)	0.2713 (5)	0.27136 (16)	0.0166 (6)
H2NA	0.088 (3)	0.109 (4)	0.2598 (18)	0.017 (8)*
H2NB	0.144 (2)	0.338 (6)	0.239 (2)	0.027 (10)*
H2NC	0.010 (2)	0.341 (7)	0.252 (2)	0.051 (12)*
C5	0.1782 (3)	0.4162 (6)	0.54039 (19)	0.0152 (7)
C6	0.2099 (3)	0.2003 (5)	0.50528 (19)	0.0180 (7)
H6	0.2527	0.0874	0.5416	0.022*
C7	0.1781 (3)	0.1530 (6)	0.41663 (19)	0.0181 (7)
H7	0.1995	0.0075	0.3917	0.022*
C8	0.1153 (3)	0.3183 (5)	0.36490 (19)	0.0149 (7)
C9	0.0805 (3)	0.5306 (5)	0.39992 (19)	0.0162 (6)
H9	0.0359	0.6415	0.3639	0.019*
C10	0.1122 (3)	0.5774 (5)	0.48805 (19)	0.0161 (7)
H10	0.0886	0.7213	0.5130	0.019*
S2	0.78723 (7)	0.26125 (13)	0.83062 (5)	0.01669 (18)
O4	0.89636 (19)	0.3121 (4)	0.79229 (13)	0.0194 (5)
O5	0.75682 (17)	0.0109 (4)	0.82423 (12)	0.0173 (5)
O6	0.68960 (19)	0.4094 (4)	0.79409 (14)	0.0231 (5)
N3	0.8696 (3)	0.4851 (6)	1.21318 (17)	0.0194 (6)
H3NA	0.874 (3)	0.630 (7)	1.223 (2)	0.028 (11)*
H3NB	0.824 (3)	0.430 (6)	1.244 (2)	0.020 (10)*
C11	0.8122 (3)	0.3252 (5)	0.94423 (19)	0.0146 (7)
C12	0.7796 (3)	0.1654 (5)	1.00663 (19)	0.0181 (7)
H12	0.7445	0.0197	0.9881	0.022*
C13	0.7982 (3)	0.2179 (5)	1.09560 (18)	0.0178 (7)
H13	0.7767	0.1071	1.1380	0.021*
C14	0.8485 (3)	0.4330 (5)	1.12326 (19)	0.0159 (7)
C15	0.8832 (3)	0.5891 (5)	1.06041 (19)	0.0190 (7)
H15	0.9198	0.7337	1.0787	0.023*
C16	0.8650 (3)	0.5360 (5)	0.9717 (2)	0.0201 (7)
H16	0.8889	0.6444	0.9293	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0186 (16)	0.0267 (17)	0.0282 (16)	0.0017 (13)	−0.0008 (13)	0.0020 (13)
C1	0.033 (2)	0.077 (3)	0.029 (2)	−0.013 (2)	0.0030 (18)	0.004 (2)
C2	0.0242 (19)	0.043 (3)	0.041 (2)	−0.0057 (18)	−0.0012 (17)	0.0136 (19)
C3	0.0192 (19)	0.039 (2)	0.042 (2)	0.0001 (16)	−0.0021 (16)	−0.0131 (18)
C4	0.034 (2)	0.068 (3)	0.036 (2)	0.005 (2)	0.0077 (19)	−0.006 (2)
S1	0.0176 (4)	0.0183 (4)	0.0148 (4)	0.0014 (3)	−0.0006 (3)	−0.0003 (3)
O1	0.0206 (12)	0.0203 (13)	0.0174 (11)	−0.0024 (10)	0.0057 (9)	−0.0005 (10)
O2	0.0288 (14)	0.0326 (15)	0.0214 (12)	0.0145 (11)	−0.0059 (10)	−0.0002 (10)
O3	0.0275 (13)	0.0213 (13)	0.0176 (11)	−0.0072 (11)	0.0022 (9)	−0.0037 (10)
N2	0.0222 (15)	0.0139 (14)	0.0139 (13)	−0.0004 (13)	0.0023 (11)	−0.0005 (12)
C5	0.0141 (16)	0.0172 (17)	0.0147 (15)	−0.0027 (13)	0.0027 (12)	0.0000 (12)
C6	0.0194 (17)	0.0157 (16)	0.0186 (15)	0.0026 (13)	0.0008 (13)	0.0012 (12)
C7	0.0203 (17)	0.0145 (15)	0.0198 (16)	0.0004 (13)	0.0030 (14)	−0.0026 (13)
C8	0.0153 (16)	0.0178 (17)	0.0120 (15)	−0.0033 (12)	0.0029 (12)	−0.0001 (12)
C9	0.0169 (15)	0.0143 (16)	0.0172 (15)	0.0007 (12)	0.0000 (12)	0.0037 (12)
C10	0.0195 (17)	0.0131 (15)	0.0162 (15)	0.0003 (12)	0.0037 (13)	−0.0008 (12)
S2	0.0195 (4)	0.0154 (4)	0.0149 (4)	0.0007 (3)	0.0008 (3)	−0.0002 (3)
O4	0.0218 (12)	0.0188 (13)	0.0182 (11)	−0.0011 (10)	0.0047 (9)	0.0008 (9)
O5	0.0218 (11)	0.0144 (11)	0.0161 (10)	−0.0019 (10)	0.0027 (9)	−0.0019 (9)
O6	0.0261 (13)	0.0218 (13)	0.0201 (12)	0.0053 (10)	−0.0037 (10)	−0.0001 (9)
N3	0.0260 (16)	0.0171 (15)	0.0152 (13)	−0.0031 (14)	0.0023 (12)	−0.0007 (13)
C11	0.0155 (16)	0.0155 (17)	0.0127 (15)	0.0033 (12)	0.0011 (12)	0.0009 (12)
C12	0.0189 (17)	0.0142 (15)	0.0213 (16)	−0.0004 (13)	0.0020 (13)	−0.0005 (12)
C13	0.0215 (17)	0.0162 (16)	0.0162 (15)	−0.0003 (13)	0.0037 (13)	0.0025 (12)
C14	0.0170 (16)	0.0167 (17)	0.0141 (15)	0.0053 (13)	0.0022 (12)	−0.0019 (12)
C15	0.0206 (17)	0.0144 (16)	0.0214 (16)	−0.0019 (13)	−0.0009 (14)	−0.0016 (13)
C16	0.0228 (17)	0.0183 (18)	0.0191 (16)	−0.0019 (13)	0.0019 (13)	0.0034 (13)

Geometric parameters (Å, º) top

N1—C2	1.488 (4)	C6—C7	1.390 (4)
N1—C3	1.497 (4)	C6—H6	0.9500
N1—H1NA	0.96 (3)	C7—C8	1.380 (4)
N1—H1NB	0.90 (3)	C7—H7	0.9500
C1—C2	1.496 (5)	C8—C9	1.390 (4)
C1—H1A	0.9800	C9—C10	1.381 (4)
C1—H1B	0.9800	C9—H9	0.9500
C1—H1C	0.9800	C10—H10	0.9500
C2—H2A	0.9900	S2—O4	1.455 (2)
C2—H2B	0.9900	S2—O6	1.462 (2)
C3—C4	1.510 (5)	S2—O5	1.463 (2)
C3—H3A	0.9900	S2—C11	1.763 (3)
C3—H3B	0.9900	N3—C14	1.399 (4)
C4—H4A	0.9800	N3—H3NA	0.83 (4)
C4—H4B	0.9800	N3—H3NB	0.79 (3)
C4—H4C	0.9800	C11—C16	1.386 (4)
S1—O2	1.453 (2)	C11—C12	1.389 (4)
S1—O1	1.454 (2)	C12—C13	1.383 (4)
S1—O3	1.456 (2)	C12—H12	0.9500
S1—C5	1.775 (3)	C13—C14	1.397 (4)
N2—C8	1.457 (4)	C13—H13	0.9500
N2—H2NA	0.94 (2)	C14—C15	1.389 (4)
N2—H2NB	0.94 (2)	C15—C16	1.380 (4)
N2—H2NC	0.97 (2)	C15—H15	0.9500
C5—C10	1.387 (4)	C16—H16	0.9500
C5—C6	1.398 (4)

C2—N1—C3	114.7 (3)	C6—C5—S1	120.8 (2)
C2—N1—H1NA	107 (2)	C7—C6—C5	119.2 (3)
C3—N1—H1NA	110 (2)	C7—C6—H6	120.4
C2—N1—H1NB	108 (2)	C5—C6—H6	120.4
C3—N1—H1NB	107 (2)	C8—C7—C6	119.7 (3)
H1NA—N1—H1NB	109 (3)	C8—C7—H7	120.1
C2—C1—H1A	109.5	C6—C7—H7	120.1
C2—C1—H1B	109.5	C7—C8—C9	121.4 (3)
H1A—C1—H1B	109.5	C7—C8—N2	119.6 (3)
C2—C1—H1C	109.5	C9—C8—N2	119.0 (3)
H1A—C1—H1C	109.5	C10—C9—C8	118.8 (3)
H1B—C1—H1C	109.5	C10—C9—H9	120.6
N1—C2—C1	110.7 (3)	C8—C9—H9	120.6
N1—C2—H2A	109.5	C9—C10—C5	120.5 (3)
C1—C2—H2A	109.5	C9—C10—H10	119.7
N1—C2—H2B	109.5	C5—C10—H10	119.7
C1—C2—H2B	109.5	O4—S2—O6	112.61 (13)
H2A—C2—H2B	108.1	O4—S2—O5	111.89 (13)
N1—C3—C4	109.6 (3)	O6—S2—O5	111.41 (13)
N1—C3—H3A	109.7	O4—S2—C11	106.81 (14)
C4—C3—H3A	109.7	O6—S2—C11	107.45 (14)
N1—C3—H3B	109.7	O5—S2—C11	106.25 (14)
C4—C3—H3B	109.7	C14—N3—H3NA	112 (2)
H3A—C3—H3B	108.2	C14—N3—H3NB	115 (2)
C3—C4—H4A	109.5	H3NA—N3—H3NB	109 (3)
C3—C4—H4B	109.5	C16—C11—C12	119.6 (3)
H4A—C4—H4B	109.5	C16—C11—S2	119.9 (2)
C3—C4—H4C	109.5	C12—C11—S2	120.5 (2)
H4A—C4—H4C	109.5	C13—C12—C11	120.2 (3)
H4B—C4—H4C	109.5	C13—C12—H12	119.9
O2—S1—O1	112.42 (14)	C11—C12—H12	119.9
O2—S1—O3	112.94 (15)	C12—C13—C14	120.2 (3)
O1—S1—O3	112.55 (13)	C12—C13—H13	119.9
O2—S1—C5	105.94 (14)	C14—C13—H13	119.9
O1—S1—C5	106.42 (13)	C15—C14—C13	119.1 (3)
O3—S1—C5	105.88 (14)	C15—C14—N3	120.4 (3)
C8—N2—H2NA	110.7 (18)	C13—C14—N3	120.5 (3)
C8—N2—H2NB	109 (2)	C16—C15—C14	120.6 (3)
H2NA—N2—H2NB	105 (3)	C16—C15—H15	119.7
C8—N2—H2NC	110 (2)	C14—C15—H15	119.7
H2NA—N2—H2NC	113 (3)	C15—C16—C11	120.2 (3)
H2NB—N2—H2NC	109 (3)	C15—C16—H16	119.9
C10—C5—C6	120.3 (3)	C11—C16—H16	119.9
C10—C5—S1	118.9 (2)

C3—N1—C2—C1	177.1 (3)	S1—C5—C10—C9	178.9 (2)
C2—N1—C3—C4	−178.4 (3)	O4—S2—C11—C16	47.7 (3)
O2—S1—C5—C10	−165.1 (2)	O6—S2—C11—C16	−73.4 (3)
O1—S1—C5—C10	75.1 (3)	O5—S2—C11—C16	167.2 (2)
O3—S1—C5—C10	−44.9 (3)	O4—S2—C11—C12	−132.1 (3)
O2—S1—C5—C6	16.1 (3)	O6—S2—C11—C12	106.9 (3)
O1—S1—C5—C6	−103.7 (3)	O5—S2—C11—C12	−12.5 (3)
O3—S1—C5—C6	136.3 (2)	C16—C11—C12—C13	1.0 (4)
C10—C5—C6—C7	2.2 (4)	S2—C11—C12—C13	−179.3 (2)
S1—C5—C6—C7	−179.0 (2)	C11—C12—C13—C14	0.8 (4)
C5—C6—C7—C8	−0.4 (4)	C12—C13—C14—C15	−2.3 (4)
C6—C7—C8—C9	−1.4 (5)	C12—C13—C14—N3	−178.8 (3)
C6—C7—C8—N2	178.0 (3)	C13—C14—C15—C16	2.0 (4)
C7—C8—C9—C10	1.4 (4)	N3—C14—C15—C16	178.5 (3)
N2—C8—C9—C10	−178.0 (3)	C14—C15—C16—C11	−0.2 (5)
C8—C9—C10—C5	0.5 (4)	C12—C11—C16—C15	−1.3 (4)
C6—C5—C10—C9	−2.3 (4)	S2—C11—C16—C15	179.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O2	0.96 (3)	1.79 (4)	2.748 (4)	175 (3)
N1—H1NB···O5	0.90 (3)	2.45 (3)	3.019 (4)	122 (3)
N1—H1NB···O6	0.90 (3)	2.03 (4)	2.920 (4)	173 (3)
N2—H2NA···O4ⁱ	0.94 (2)	1.88 (2)	2.794 (4)	165 (3)
N2—H2NB···O5ⁱⁱ	0.94 (2)	1.85 (2)	2.778 (3)	171 (3)
N2—H2NC···N3ⁱⁱⁱ	0.97 (2)	1.85 (2)	2.812 (4)	178 (4)
N3—H3NA···O1^iv	0.83 (4)	2.21 (4)	2.998 (4)	157 (3)
N3—H3NB···O3^v	0.79 (3)	2.23 (3)	2.997 (4)	164 (3)
C3—H3A···O3^vi	0.99	2.48	3.338 (4)	145
C6—H6···O3^vi	0.95	2.65	3.507 (4)	151
C9—H9···O1^vii	0.95	2.59	3.517 (4)	165

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

Acknowledgements

The authors acknowledge the Cheikh Anta Diop University of Dakar (Sénégal) and the University of Notre Dame (USA) for financial support.

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