Crystal structures of two unexpected products of vicinal di­amines left to crystallize in acetone

Dival, B.; Pitinato, L.; Develly, L.; Oliveira, W.X.C.

doi:10.1107/S2053229624007320

crystallography in latin america

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 9| September 2024| Pages 497-504

https://doi.org/10.1107/S2053229624007320

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Crystal structures of two unexpected products of vicinal diamines left to crystallize in acetone

Bruno Dival,^a Leonardo Pitinato,^a Letícia Develly ^a and Willian X. C. Oliveira ^a ^*

^aDepartamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, Av. Pres. Antônio Carlos, 6627 Pampulha, 31270-901 Belo Horizonte, Minas Gerais, Brazil
^*Correspondence e-mail: wxcoliveira@ufmg.br

Edited by A. Lemmerer, University of the Witwatersrand, South Africa (Received 31 May 2024; accepted 23 July 2024; online 23 August 2024)

This article is part of the collection Crystallography in Latin America: a vibrant community

Herein we report the crystal structures of two benzodiazepines obtained by reacting N,N′-(4,5-diamino-1,2-phenylene)bis(4-methylbenzenesulfonamide) (1) or 4,5-(4-methylbenzenesulfonamido)benzene-1,2-diaminium dichloride (1·2HCl) with acetone, giving 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine, C₂₆H₃₀N₄O₄S₂ (2), and 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepin-1-ium chloride 0.3-hydrate, C₂₆H₃₁N₄O₄S₂⁺·Cl⁻·0.3H₂O (3). Compounds 2 and 3 were first obtained in attempts to recrystallize 1 and 1·2HCl using acetone as solvent. This solvent reacted with the vicinal diamines present in the molecular structures, forming a 5H-1,5-benzodiazepine ring. In the crystal structure of 2, the seven-membered ring of benzodiazepine adopts a boat-like conformation, while upon protonation, observed in the crystal structure of 3, it adopts an envelope-like conformation. In both crystalline compounds, the tosylamide N atoms are not in resonance with the arene ring, mainly due to hydrogen bonds and steric hindrance caused by the large vicinal groups in the aromatic ring. At a supramolecular level, the crystal structure is maintained by a combination of hydrogen bonds and hydrophobic interactions. In 2, amine-to-tosyl N—H⋯O and amide-to-imine N—H⋯N hydrogen bonds can be observed. In contrast, in 3, the chloride counter-ion and water molecule result in most of the hydrogen bonds being of the amide-to-chloride and ammonium-to-chloride N—H⋯Cl types, while the amine interacts with the tosyl group, as seen in 2. In conclusion, we report the synthesis of 1, 1·2HCl and 2, as well as their chemical characterization. For 2, two synthetic methods are described, i.e. solvent-mediated crystallization and synthesis via a more efficient and cleaner route as a polycrystalline material. Salt 3 was only obtained as presented, with only a few crystals being formed.

Keywords: vicinal; solvent reactions; crystallization; benzodiazepine; diamine; crystal structure.

CCDC references: 2358756; 2358757

1. Introduction

In an attempt to obtain single crystals, it is very common to try to dissolve the studied material in various solvents. Usually, the solvents selected for recrystallization are those commonly found in the chemistry laboratory (e.g. water, ethanol, acetone, acetonitrile, chloroform, dimethylformamide, etc.). In general, the solvent is inert, but some solvents can react with the dissolved material, resulting in unexpected products. It is possible to perform a retrosynthetic analysis of a desired material by analyzing the crystal structure of the product obtained, although this may limit its further use. Generally, reactions where the solvent acts as a reactant are solvolysis (Nath et al., 2014 ; Simões et al., 2013a ), cyclization (Odame et al., 2013 ), ligand displacement (Yu et al., 2020 ) and crystal-to-crystal conversions (Wu et al., 2013 ; Li et al., 2020 ; Simões et al., 2013b ). Most often, these reactions occur when the solvent is water-rich and/or contains reactive organic groups, such as carbonyl groups.

Among the common solvents that contain carbonyl groups in their molecular structure, acetone stands out due to how easy it is to manipulate. It is not just an innocent solvent, as it can react with dissolved compounds (Kumar et al., 2006 ). An aldol condensation is highly likely to occur resulting in the formation of 4-hydroxy-4-methylpentan-2-one, also known as diacetone alcohol (DAA). DAA is present in relatively large amounts in pure acetone, constituting around 12% by weight at 20 °C (Podrebarac et al., 1997 ), catalyzed by the presence of a basic solute, which facilitates proton abstraction. The same behaviour is observed with acidic solutes, but in this case, DAA undergoes dehydration catalyzed by the acid, forming 4-methylpent-3-en-2-one, or mesityl oxide. This behaviour is shown in Fig. 1.

Figure 1
The diacetone alcohol (DAA) formation mechanism in the presence of a base (top) and the DAA dehydration mechanism catalyzed by an acid (bottom).

Although acetone can react with acidic and basic solutes, DAA and mesityl oxide are less reactive, as they are stabilized by intermolecular hydrogen bonds and electron delocalization in the α,β-unsaturated ketone, respectively. Other reactions with these compounds are observed in situations where the product has another stabilizing effect, such as ring formation (Climent et al., 2009 ). For example, DAA-rich acetone can react with dissolved vicinal aromatic diamines, forming a seven-membered ring. When the diamine used is o-phenylenediamine or its derivatives, cyclization leads to the formation of 5H-1,5-benzodiazepine (Kuo et al., 2008 ; Climent et al., 2009; Pozarentzi et al., 2002 ). However, it is reported that for vicinal diamines with electron-withdrawing groups, such as 1,2-dinitro-4,5-phenylenediamine, the formation of single crystals from acetone occurs without the occurrence of a reaction (Siri & Braunstein, 2005 ). Coordinated diamines have shown resistance to solutions containing acetone (Dhakal et al., 2023 ).

In this article, we present the crystal structures of two products obtained during attempts to grow single crystals of N,N′-(4,5-diamino-1,2-phenylene)bis(4-methylbenzenesulfonamide) (1) and its dihydrochloric acid salt 4,5-(4-methylbenzenesulfonamido)benzene-1,2-diaminium dichloride (1·2HCl) from acetone, namely, 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine (2) and 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepin-1-ium chloride 0.3-hydrate (3). The molecular structures of 1, 2 and 3 are shown in Fig. 2.

Figure 2
The molecular structures of (a) 1, (b) 2, showing commonly used ring labelling in benzodiazepines, and (c) 3.

2. Experimental

All solvents and materials were used as received without further purification. 1,2-Bis(4-methylbenzenesulfonamido)-4,5-dinitrobenzene was synthesized as described in the literature (Rombouts et al., 2014 ).

2.1. Materials synthesis

2.1.1. General procedure for the reduction of 1,2-bis(4-methylbenzenesulfonamido)-4,5-dinitrobenzene

In a 50 ml round-bottomed flask, 1,2-bis(4-methylbenzenesulfonamido)-4,5-dinitrobenzene (350 mg, 0.69 mmol) and metallic tin (200 mg, 1.68 mmol) were added to a mixture of ethanol and concentrated hydrochloric acid (37%) (16 ml, 1:1 v/v). The suspension was placed on a magnetic stirrer at 90 °C and refluxed for 3 h. Upon completion of the reaction, a light-beige solid precipitated. The contents of the flask were transferred to a plastic tube and centrifuged for 10 min at 6000 rpm to separate the solid from the solution.

2.1.2. N,N′-(4,5-Diamino-1,2-phenylene)bis(4-methylbenzenesulfonamide) (1)

Following the general procedure, the supernatant was discarded, the residual solid suspended in ethyl acetate (20 ml), transferred to a separating funnel and washed with water (2 × 20 ml), followed by a wash with brine (20 ml). The organic phase obtained was then dried with anhydrous sodium sulfate and evaporated under reduced pressure, resulting in an ochre-coloured solid (yield: 68%, 0.203 g, 0.48 mmol; m.p. 181–182 °C). ¹H NMR [ppm, DMSO-d₆ (dimethyl sulfoxide-d₆)]: δ 2.35 (s, 6H, CH₃-tosyl), 4.54 (s, 4H, NH₂), 6.14 (s, 2H, CH-phenyl), 7.32 (d, 4H, CH-tosyl), 8.52 (s, 2H, NH-tosylamide) ¹³C NMR (ppm, dept signal): δ 21.50(+), 111.30(+), 120.51, 127.40(+), 129.91(+), 134.08, 136.74, 143.48. IR (cm⁻¹): 3371 and 3258 [ν(N—H)]; 3058 and 3030 [ν(C—H)]; 2970, 2948, 2926 and 2808 [ν(CH₃) + ν(N—H)]; 1659 and 1626 [δ(N—H)]; 1593 [ν(C=C)]; 1384 and 1155 (ν_sim and ν_assim SO₂).

2.1.3. 4,5-(4-Methylbenzenesulfonamido)benzene-1,2-diaminium dichloride (1·2HCl)

Following the general procedure, the supernatant was discarded, the solid suspended in a mixture of ethanol and hydrochloric acid (3.0 ml, 1:1 v/v), and recentrifuged to eliminate tin salts. The beige solid was left to dry under low pressure for 24 h [yield: 89%, 0.261 g, 0.584 mmol; m.p. 207 °C (decomposition)]. ¹H NMR (ppm, DMSO-d₆): δ 2.34 (s, 6H, CH₃-tosyl), 6.70 (s, 2H, H-phenyl), 7.33 (d, 4H, aromatic H-tosyl), 7.58 (d, 4H, aromatic H-tosyl), 9.09 (s, 2H, NH-tosylamide). ¹³C NMR (ppm, dept signal): δ 21.05(+), 111.52(+), 120.74, 126.96(+), 129.50(+), 132.67, 136.26, 143.14. IR (cm⁻¹): 3136 [ν(N—H)]; 3033 [ν(C—H)]; 2926, 2835, 2770 and 2569 [ν(CH₃) + ν(N—H)]; 1635 [δ(N—H)]; 1588 [ν(C=C)]; 1346 and 1154 (ν_sim and ν_assim SO₂).

2.1.4. 2,2,4-Trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine (2)

Single crystals of 2 were first obtained by dissolving 1 (5.0 mg) in acetone (10 ml) and allowing it to evaporate at room temperature in an open vial. A few small plate-like crystals of 2 appeared alongside a very viscous amber liquid when the solvent was evaporated. To obtain it on a larger scale, 1·2HCl (197 mg, 0.380 mmol) was dissolved in acetone (50 ml) and triethylamine (750 µl, 5.38 mmol) was added. After 1 h, a light-yellow powder precipitated. This powder, composed mostly of (Et₃NH)Cl, was filtered off and the solution was evaporated to dryness in a rotatory evaporator. The resulting pale-yellow powder was washed with a small amount of water and left to dry at low pressure and room temperature for 24 h [yield: 41%, 98.0 mg, 0.186 mmol; m.p. 209 °C (decomposition)]. ¹H NMR (ppm, DMSO-d₆): δ 1.12 (s, 6H, CH₃-tosyl), 2.06 (s, 2H, CH₂-benzodiazepine), 2.11 (s, 3H, CH₃-imine), 2.35 (s, 6H, CH₃-amine), 5.00 (s, 1H, NH-benzodiazepine), 6.45 (s, 1H, benzodiazepine aromatic C—H), 6.58 (s, 1H, benzodiazepine aromatic C—H), 7.33 (d, 4H, aromatic tosyl), 7.52 (d, 2H, aromatic tosyl), 7.62 (d, 2H, aromatic tosyl), 8.86 (s, 2H, NH-tosylamide). ¹³C NMR (ppm, dept signal): δ 21.00(+), 29.35(+), 29.73(+), 45.56(−), 65.45, 114.30(+), 120.59, 124.23(+), 126.87(+), 127.13(+), 128.40, 129.49(+), 129.58(+), 135.85, 136.15, 138.22, 143.31, 143.45, 171.35. IR (cm⁻¹): 3335, 3322 [ν(N—H)]; 3065 and 3021 [ν(C—H)]; 2966, 2921, 2859 [ν(CH₃) + ν(CH₂)]; 2653 [ν(N—H)]; 1728 [ν(C—N)]; 1640 [δ(N—H)]; 1595 [ν(C=C)]; 1325 and 1157 (ν_sim and ν_assim SO₂).

2.1.5. 2,2,4-Trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepin-1-ium chloride 0.3-hydrate (3)

Up to this point, compound 3 had only been obtained as single crystals by dissolving 1·2HCl (5.0 mg) in acetone (7.0 ml). The resulting solution was left to crystallize and, after 2 d, a few small plate-like crystals of 3 appeared alongside a very viscous dark liquid.

2.2. Single-crystal X-ray diffraction

X-ray diffraction data collections on single crystals of 2 and 3 were made with a Rigaku Synergy diffractometer using Cu Kα radiation (λ = 1.54184 Å) at LabCri (Laboratório de Cristalografia da UFMG). Measurements were performed at 293 K, as shown in Table 1. The crystallization water molecule in 3 had its occupancy freely refined and the final occupancy found was around 0.30. At the final refinement step, it was fixed at this value for convergence purposes. For 3, the benzodiazepinium methylene (C3), methyl (C5 and C6) and ammonium (N2) groups have multiple possible positions, the latter being split over two positions and the others over three. H atoms were located in difference maps and included as fixed contributions according to the riding model (Johnson, 1971 ). The difference maps for 2 and 3 revealed two possible positions for the H atoms in the imine methyl group (C1); thus, they were added over two positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic C atoms, C—H = 0.97 Å and U_iso(H) = 1.5U_eq(C) for methyl groups, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene C atoms, and N—H = 0.90 Å and U_iso(H) = 1.2U_eq(N) for aromatic amide, imine and ammonium N atoms. For the crystallization water molecule, the H atoms were added using its solid-state geometry (Kuhs & Lehmann, 1981 ), with O—H = 1.00 Å and U_iso(H) = 1.5U_eq(O).

Table 1
Experimental details

Experiments were carried out at 293 K with Cu Kα radiation using a Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector. The absorption correction was Gaussian (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ). H atoms were treated by a mixture of independent and constrained refinement.

	2	3
Crystal data
Chemical formula	C₂₆H₃₀N₄O₄S₂	C₂₆H₃₁N₄O₄S₂⁺·Cl1·0.3H₂O
M_r	526.66	568.52
Crystal system, space group	Monoclinic, C2/c	Monoclinic, P2₁/c
a, b, c (Å)	30.0416 (9), 9.7018 (1), 24.0984 (7)	12.0993 (2), 13.4307 (2), 17.3586 (3)
β (°)	129.744 (5)	103.667 (2)
V (Å³)	5400.6 (4)	2740.94 (8)
Z	8	4
μ (mm⁻¹)	2.10	3.00
Crystal size (mm)	0.19 × 0.07 × 0.06	0.19 × 0.15 × 0.03

Data collection
T_min, T_max	0.603, 1.000	0.498, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	76569, 4942, 3970	24340, 5837, 4787
R_int	0.069	0.039
(sin θ/λ)_max (Å⁻¹)	0.602	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.126, 1.07	0.041, 0.121, 1.07
No. of reflections	4942	5837
No. of parameters	334	433
No. of restraints	9	74
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.34	0.30, −0.27
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SUPERFLIP (Palatinus et al., 2007 ), SHELXL2019 (Sheldrick, 2015 ) and Mercury (Macrae et al., 2020).

All the figures were obtained using Mercury software (Macrae et al., 2020 ), and images of both structures with atomic displacements are shown in Fig. S1 of the supporting information.

Polycrystalline X-ray diffraction data for 2 were recorded on a PanAnlaytical Emperian in θ–θ mode using ca 20 mg of material compacted in a rotatory silicon sample holder and Cu Kα radiation. The experimental and calculated diffraction patterns obtained from the CIF using Mercury software (Macrae et al., 2020) are shown in Fig. S11 in the supporting information.

2.3. Chemical characterizations

NMR analysis (¹H, ¹³C and DEPT-135) was conducted using a Bruker Avance III 400, operating at 400 MHz for ¹H. Approximately 30 mg of each compound was dissolved in DMSO-d₆ (700 µl) with 0.03% v/v of tetramethylsilane (TMS) as the internal standard (Figs. S3–S11 in the supporting information). IR spectra were recorded on a PerkinElmer FT–IR GX spectrometer in ATR (attenuated total reflectance) mode, with a resolution of 4 cm⁻¹ (Figs. S12–S14 in the supporting information).

3. Results and discussion

3.1. Crystal structure description

Compound 2 crystallizes in the centrosymmetric monoclinic space group C2/c. It consists of a 5H-benzodiazepine group with methyl substitutions at positions 2 (C2) and 4 (C4) (see the benzodiazepine labelling scheme in Fig. 2), with position 4 being doubly substituted. Additionally, positions 8 (C9) and 9 (C10) are substituted by N-tosylamido groups, which are linked to the aromatic ring through the N atoms. The crystalline form does not include any solvent molecules. The crystal structure of 2 with the atom labelling is depicted in Fig. 3.

Figure 3
The crystal structure of 2 with the atomic labelling.

The seven-membered ring in the benzodiazepine part in 2 has a boat-like conformation; atoms C2, C4, N1 and N2 are almost coplanar, while atoms C3, C7 and C12 are all on the same side of this plane (see Fig. 4). In this ring, the imine group is easily found, with an N1—C2 bond length of 1.282 (2) Å and an N2—C4 bond length of 1.486 (2) Å. The first is typical for imines, while the second is slightly shorter than expected for single C—N bonds, mainly due to resonance with the benzodiazepine aromatic ring. To achieve this boat-type conformation, atoms N1 and N2 deviate from the arene ring, both deviating out of plane to the same side of the arene mean plane. The atom–plane distances are 0.223 (3) Å for N1 and 0.1044 (18) Å for N2. Atom N1 presents a greater deviation because it is involved in a double bond with C2, presenting greater hindrance and more rigorous restrictions to accommodate the boat-like conformation.

Figure 4
(a) Side view of the benzodiazepine portion of 2, showcasing its boat-like conformation. The atoms highlighted as orange spheres show those that are participating in the boat-like conformation. (b) Ideal boat-like conformation for a seven-membered ring.

The tosylamide groups are almost perpendicular to the benzodiazepine aromatic ring, with angles between the amide planes and the aromatic ring of 60.33 (15) and 82.94 (12)° for atoms N3 and N4, respectively. Each N atom points to a different side of the arene plane, with torsion angles around the N—C bond of −100.64 (19) (C9—C10—N4—S2) and −121.32 (18)° (C10—C9—N3—S1). This indicates that hydrogen bonds predominate over the resonance of nitrogen with the aromatic ring. Atoms N3 and N4 deviate from the aromatic-ring mean plane by 0.046 (3) and −0.115 (3) Å, respectively, due to these torsions. Consequently, the tosylamide N—H group is involved in intramolecular interactions with various geometric restrictions, interacting with the sulfonamide O atom (N3—H3⋯O3; see Table 2).

Table 2
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O3	0.90 (1)	2.59 (2)	3.267 (3)	133 (2)
N4—H4⋯N1ⁱ	0.90 (1)	1.97 (1)	2.860 (2)	167 (2)
C1—H1B⋯C16ⁱ	0.96	2.76	3.584 (4)	145
C1—H1B⋯C17ⁱ	0.96	2.82	3.600 (4)	139
C1—H1C⋯O4ⁱ	0.96	2.59	3.434 (4)	147
C26—H26B⋯C16ⁱ	0.96	3.19	4.094 (5)	157
N2—H2⋯O2ⁱⁱ	0.93 (1)	2.40 (1)	3.253 (2)	153 (1)
C14—H14⋯O1ⁱⁱⁱ	0.93	2.45	3.356 (3)	165
C1—H1A⋯O4^iv	0.96	2.34	3.293 (3)	176
Symmetry codes: (i) ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

The crystal packing of 2 is mainly ruled by hydrogen bonds. One of the amides (N4) is involved in a hydrogen bond with a free N atom of benzodiazepine [N1ⁱ; symmetry code: (i) −x + 1, −y + 1, −z], resulting in a supramolecular dimer. There is also a weak C1—H1C⋯O4ⁱ hydrogen bond, which is shown in Fig. 5(a) (see also Table 2). It was found that, due to the torsion angles around the N—S tosylamide group, the molecule has a groove that is filled with the tosyl aromatic ring of the supramolecular dimer's partner molecule. In this cavity, C—H⋯C_ar (ar is aromatic) interactions can be observed where the aromatic ring (C13–C18) is surrounded by two methyl groups, one from the benzodiazepine imine group (C1) and the other from the tosyl substituent (C26). This occurs reciprocally, as the surrounded molecule also includes the surrounding molecule in its groove. This interaction is shown in Fig. 5(b). All hydrogen bonds are detailed in Table 2.

Figure 5
(a) Dimeric hydrogen bonds in 2, shown as blue dotted lines, involving a tosylamide N—H group as donor and the imine N atom as acceptor. C—H⋯O interactions between methyl groups and sulfonamide O atoms are shown as green dotted lines. The aromatic rings of the tosyl groups have been omitted for better visualization. (b) Methyl C—H⋯C_ar interactions in the dimeric unit, viewed along the hydrogen bonds. O atoms and all H atoms, except for those in the methyl substituents of the tosyl groups and in the imine groups, have been omitted. [Symmetry code: (i) −x + 1, −y + 1, −z.]

The interactions between dimers extend along the crystallographic c direction via hydrogen bonds. The N2 atom of the benzodiazepine interacts with atom O2ⁱⁱ [symmetry code: (ii) −x + 1, y, −z + $[{1\over 2}]$ ] of a neighbouring sulfonamide group (see Fig. 6), forming a supramolecular chain. To achieve interactions in all three dimensions, the supramolecular chains interact along the crystallographic a and b directions via C—H⋯O interactions involving both tosyl groups [C1—H1C⋯O4ⁱ and C14—H14⋯O1ⁱⁱⁱ; symmetry code: (iii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z], as well as hydrophobic contacts between the aliphatic benzodiazepine C5 and C6 methyl groups and the tosyl groups (see Fig. S3 in the supporting information).

Figure 6
(a) Hydrogen bonding between molecules from adjacent supramolecular chains in 2, involving benzodiazepine amine and tosyl O atoms. [Symmetry code: (ii) −x + 1, y, −z + $[{1\over 2}]$ .] (b) Supramolecular interactions between the chains along the crystallographic c axis, viewed along the supramolecular chain.

For compound 3, the crystal structure will be described in comparison with that of 2, since their molecular structures are very similar. It crystallizes in the centrosymmetric monoclinic space group P2₁/c and consists of a 2,2,4-trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine molecule protonated at the N1 atom, with a chloride anion as counter-ion and a water molecule. The crystal structure is shown in Fig. 7. The water molecule is found with an incomplete occupancy. The refined occupancy is 0.3 water molecules per benzodiazepinium chloride unit.

Figure 7
The crystal structure of 3 with the atomic labelling. Atoms N2, C3, C5 and C6 are disordered and the presented components highlight the closest to the ideal envelope-like conformation. The chloride ion and crystallization water molecule have been omitted for better visualization.

The benzodiazepine portion in hydrated salt 3 adopts an envelope-like conformation (see Fig. 8), with atoms C2, C4, N1, N2, C7 and C12 almost in the same plane, while only atom C3 is raised from the mean plane formed by those atoms. Within this ring, the C—N bond lengths are very close to those observed in 2, with an N1—C2 bond length of 1.277 (2) Å and an N2—C4 bond length of 1.421 (9) Å [and N2A—C4 = 1.431 (8) Å]. Protonation of benzodiazepine does not change the imine characteristics or the aromatic amine bond length. In the envelope-like conformation, atoms N1 and N2 deviate slightly from the plane of the arene ring, with the distances between these atoms and the mean plane being 0.158 (3) Å for N1 and 0.047 (5) Å for N2 [0.2530 (3) Å for N2A]. This possibly occurs as a result of the imine now having to accommodate another atom, thus requiring it to be parallel to the arene ring to avoid axial interactions.

Figure 8
(a) Side view of the benzodiazepine portion of 3, showcasing its envelope-like conformation. The atoms highlighted as orange spheres are those participating in the envelope-like conformation. (b) The ideal envelope-like conformation for a seven-membered ring.

In 3, similar to 2, the tosylamide groups show low electronic resonance with the benzodiazepine aromatic ring due to the large torsion around it, resulting in a relatively large angle between the amides and the aromatic ring. The angle between the N3-containing amide (C9/N3/S1 mean plane) and the arene ring (atoms C7–C12) is 46.24 (19)°, and that with the N4 atom (C10/N4/S2 mean plane) is 63.40 (16)°. Both amide N atoms in 3 are pointing to the same side of the arene plane (in contrast to 2) caused by the hydrogen-bond interaction with the chloride anion. The torsion angles around the N—S bond are 135.23 (19) (C9—N3—S1—C13) and 116.6 (2)° (C10—N4—S2—C20). This means that the hydrogen bonds in this compound lead to a lower bulk energy and restrict the resonance of the N atoms with the arene ring. Atoms N3 and N4 deviate from the plane of the aromatic ring by 0.046 (3) and −0.115 (3) Å, respectively, also as a result of these torsions.

The crystal packing of 3 is strongly influenced by hydrogen bonds involving the chloride anion. The chloride anion plays a key role in the supramolecular interactions, connecting two benzodiazepine units [N3—H3⋯Cl1, N4—H4⋯Cl1 and N1—H1⋯Cl1ⁱ; symmetry code: (i) −x + 1, −y + 1, −z] and the water molecule (O5—H5G⋯Cl1). The hydrogen bonds around the chloride anion form two fused rings, one with eight components and the other with seven, in addition to a discrete interaction. This motif is defined as R₂²(8) R₂¹(7)D (Etter et al., 1990 ), where a discrete interaction occurs between the chloride and the iminium group (N1ⁱ) of a second benzodiazepine unit. The sum of the hydrogen bonds involving chloride anions leads to a dimeric motif. Furthermore, the aromatic amine (N2) connects the dimeric units by interacting with the adjacent tosyl O atom [O3ⁱⁱ; symmetry code: (ii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ] in a discrete way. All mentioned hydrogen bonds are shown in Fig. 9 and listed in Table 3. The combination of these hydrogen bonds forms a two-dimensional (2D) supramolecular polymer parallel to the bc crystallographic plane that is layered up to the a crystallographic axis via weak hydrogen bonds relative to the aromatic tosyl C—H and iminium methyl groups interacting with sulfonyl O atoms of neighbouring tosyl groups [C21—H21⋯O1ⁱⁱⁱ and C1—H1A⋯O4^iv; symmetry codes: (iii) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x − 1, y, z]. These are supported by several hydrophobic interactions, mainly involving the toluene substituent of the tosyl groups [C26—H26B⋯C14^v, C19—H19B⋯C14^vi and C19—H19B⋯C15^vi; symmetry codes: (v) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (vi) x − 2, −y + 1, −z + 1].

Table 3
Hydrogen-bond geometry (Å, °) for 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Cl1	0.95 (1)	2.28 (1)	3.2256 (15)	177 (1)
N4—H4⋯Cl1	0.94 (1)	2.25 (1)	3.1685 (15)	166 (2)
N1—H1⋯Cl1ⁱ	0.90 (1)	2.19 (1)	3.0834 (16)	175 (2)
N2A—H2A⋯O3ⁱⁱ	0.90 (1)	2.28 (4)	3.111 (18)	154 (5)
O5—H5G⋯Cl1	1.01 (1)	2.05 (2)	3.050 (8)	170 (10)
O5—H5F⋯O2	1.00 (1)	2.02 (4)	2.921 (9)	148 (7)
C21—H21⋯O1ⁱⁱⁱ	0.93	2.58	3.482 (3)	163
C1—H1A⋯O4^iv	0.96	2.31	3.218 (3)	157
C26—H26B⋯C14^v	0.96	3.41	3.896 (5)	114
C19—H19B⋯C14^vi	0.96	2.85	3.664 (5)	143
C19—H19B⋯C15^vi	0.96	2.73	3.458 (6)	133
Symmetry codes: (i) ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}]$ , $[-z+{\script{1\over 2}}]$ ; (iv) ; (v) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) .

Figure 9
The hydrogen-bond net in 3, featuring the Etter R₂²(8) R₂¹(7)D motif around the Cl atom and showing the atom labelling. The tosyl aromatic rings have been omitted for better visualization. [Symmetry codes: (i) −x + 1, −y + 1, −z; (ii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ .]

3.2. Cyclization reaction with the solvent

Both 1 and 1·2HCl have tosylamide groups in para positions relative to the amines, which are very weak electron-density donors. Moreover, 1·2HCl has its amine groups protonated. Therefore, a low probability of these compounds reacting with acetone can be expected. The ability to form benzodiazepines from recrystallization in acetone might be associated with the fact that 1 partially acts as a base, promoting the cyclization reaction with free diamines. In contrast, 1·2HCl is a strong acid that, in this solvent, is deprotonated, acidifying the solution and thus leading to cyclization with the diamine fraction fully deprotonated. This may explain both the low yields of 2 and 3, and the presence of a viscous liquid between their single crystals. This thick liquid is likely a combination of unreacted diamine, its conjugate acid, along with DAA and mesityl oxide. The last two are liquids with high boiling points and their quantities are increased in the presence of basic or acidic solutes. To evaluate this, compound 2 was synthesized adding a weak base to the diamine solution, in this case, triethylamine. In the mentioned reaction, the benzodiazepine derivative was isolated in significant yield, corroborating that 1 acts as a base in this reaction during crystallization tests. In conclusion, it appears that only strong electron-withdrawing substituents on the aromatic ring of vicinal diamines can make them weakly basic enough to avoid reaction with acetone, as seen with 1,2-dinitro-4,5-phenylenediamine, which can be crystallized from an acetone-rich solution (Siri & Braunstein, 2005). Aromatic diamines with electron-withdrawing substituents can still form benzodiazepines with acetone on addition of a strong acid or base (Heravi et al. 2007 ; Nardi et al., 2011 ).

4. Conclusions

This article has demonstrated how a solvent, acetone in this case, can be reactive and is not innocent in crystallization processes. The reported case shows its incompatibility with vicinal aromatic diamines when they are substituted with a weak electron-density donor, such as tosylamide, which produced benzodiazepines. Compounds 1 and 1·2HCl were dissolved in acetone, producing 2 and 3, respectively. They were firstly obtained in very low yield, as single crystals, but we report the synthesis of 2 on a larger scale, using a base to promote the cyclization. Attempts to obtain salt 3 from 1·2HCl on a large scale in acidic acetone solution did not lead to the desired product in excessive quantity, corroborating the dehydration of diacetone alcohol to mesityl oxide, which most likely does not participate in the formation of benzodiazepine.

Supporting information

CCDC references: 2358756; 2358757

Crystal structure: contains datablocks 2, 3, global. DOI: https://doi.org/10.1107/S2053229624007320/ef3057sup1.cif

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2053229624007320/ef30572sup2.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2053229624007320/ef30573sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229624007320/ef30572sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229624007320/ef30573sup5.cml

Ellipsoid plots, packing diagrams and spectra. DOI: https://doi.org/10.1107/S2053229624007320/ef3057sup6.pdf

Computing details top

2,2,4-Trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine (2) top

Crystal data top

C₂₆H₃₀N₄O₄S₂	F(000) = 2224
M_r = 526.66	D_x = 1.295 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 30.0416 (9) Å	Cell parameters from 17655 reflections
b = 9.7018 (1) Å	θ = 3.7–73.4°
c = 24.0984 (7) Å	µ = 2.10 mm⁻¹
β = 129.744 (5)°	T = 293 K
V = 5400.6 (4) Å³	Needle, yellow
Z = 8	0.19 × 0.07 × 0.06 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	4942 independent reflections
Radiation source: micro-focus sealed X-ray tube	3970 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.069
ω scans	θ_max = 68.2°, θ_min = 3.8°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	h = −36→36
T_min = 0.603, T_max = 1.000	k = −11→11
76569 measured reflections	l = −29→29

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0632P)² + 2.9523P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4942 reflections	Δρ_max = 0.41 e Å⁻³
334 parameters	Δρ_min = −0.34 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.

Refinement. Data integration and scaling of the reflections for all compounds was conducted with the CRYSALIS suite (Rigaku, 2022). Final unit cell parameters were based on the fitting of all reflections? positions. Analytical absorption corrections and the space group identification were executed using the CRYSALIS suite (Rigaku, 2022). The structures of all compounds were solved by direct methods using the SUPERFLIP program (Palatinus et al., 2007).

For each compound, the positions of all atoms could be unambiguously assigned on consecutive difference Fourier maps. Refinements were performed using SHELXL (Sheldrick, 2015) based on F² through full-matrix least square routine. All non-hydrogen atoms were refined with anisotropic atomic displacement parameters.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.71423 (9)	0.4329 (3)	0.19402 (12)	0.0680 (6)
H1A	0.748099	0.382180	0.231771	0.102*	0.5
H1B	0.712625	0.439205	0.153013	0.102*	0.5
H1C	0.715882	0.523891	0.210925	0.102*	0.5
H1D	0.702971	0.514671	0.165368	0.102*	0.5
H1E	0.738446	0.457646	0.244126	0.102*	0.5
H1F	0.735188	0.372960	0.186215	0.102*	0.5
C2	0.66158 (8)	0.3607 (2)	0.17283 (10)	0.0488 (4)
C3	0.66800 (8)	0.2267 (2)	0.20855 (10)	0.0513 (5)
H3A	0.706441	0.190225	0.232322	0.062*
H3B	0.640257	0.161156	0.171684	0.062*
C4	0.65887 (8)	0.2389 (2)	0.26430 (9)	0.0484 (4)
C5	0.71114 (9)	0.3070 (3)	0.33294 (11)	0.0679 (6)
H5A	0.744875	0.251282	0.353661	0.102*
H5B	0.716995	0.396575	0.321630	0.102*
H5C	0.704515	0.316115	0.366814	0.102*
C6	0.64897 (11)	0.0963 (2)	0.28054 (13)	0.0682 (6)
H6A	0.682163	0.039472	0.299776	0.102*
H6B	0.643105	0.103426	0.315199	0.102*
H6C	0.615391	0.055690	0.236924	0.102*
C7	0.55854 (8)	0.31690 (18)	0.15961 (9)	0.0436 (4)
C8	0.50567 (8)	0.2786 (2)	0.14068 (10)	0.0486 (4)
H8	0.503867	0.252706	0.176358	0.058*
C9	0.45640 (8)	0.27889 (19)	0.06986 (10)	0.0465 (4)
C10	0.45868 (8)	0.31373 (18)	0.01528 (9)	0.0438 (4)
C11	0.51167 (8)	0.34938 (19)	0.03504 (9)	0.0444 (4)
H11	0.513870	0.371146	−0.000732	0.053*
C12	0.56160 (7)	0.35358 (19)	0.10667 (9)	0.0427 (4)
C13	0.33911 (9)	0.4654 (2)	0.02408 (11)	0.0591 (5)
C14	0.28100 (10)	0.4917 (3)	−0.01446 (13)	0.0736 (7)
H14	0.257394	0.427948	−0.015412	0.088*
C15	0.25843 (13)	0.6157 (3)	−0.05191 (16)	0.0919 (9)
H15	0.219378	0.634561	−0.077511	0.110*
C16	0.29200 (17)	0.7107 (3)	−0.05218 (17)	0.0916 (9)
C17	0.34921 (16)	0.6808 (3)	−0.01489 (19)	0.0909 (9)
H17	0.372295	0.742935	−0.015821	0.109*
C18	0.37328 (12)	0.5608 (3)	0.02388 (16)	0.0780 (7)
H18	0.412529	0.543677	0.049999	0.094*
C19	0.2659 (2)	0.8455 (4)	−0.0940 (2)	0.1455 (17)
H19A	0.225538	0.848871	−0.116638	0.218*
H19B	0.285586	0.921905	−0.061396	0.218*
H19C	0.270076	0.850652	−0.130220	0.218*
C20	0.43894 (10)	0.1860 (2)	−0.12497 (11)	0.0632 (6)
C21	0.48001 (12)	0.0821 (3)	−0.09237 (14)	0.0790 (7)
H21	0.480013	0.015334	−0.064689	0.095*
C22	0.52097 (13)	0.0788 (3)	−0.10140 (17)	0.0924 (9)
H22	0.548284	0.008389	−0.079624	0.111*
C23	0.52286 (14)	0.1764 (4)	−0.14163 (16)	0.0905 (9)
C24	0.48214 (14)	0.2816 (3)	−0.17212 (16)	0.0909 (9)
H24	0.483135	0.350438	−0.198185	0.109*
C25	0.44044 (12)	0.2867 (3)	−0.16476 (13)	0.0751 (7)
H25	0.413262	0.357449	−0.186358	0.090*
C26	0.56767 (18)	0.1675 (5)	−0.1511 (2)	0.1352 (16)
H26A	0.562704	0.242966	−0.180352	0.203*
H26B	0.605636	0.171689	−0.104721	0.203*
H26C	0.563253	0.082000	−0.174247	0.203*
N1	0.61176 (6)	0.41314 (17)	0.12280 (8)	0.0475 (4)
N2	0.60800 (7)	0.32881 (17)	0.23443 (8)	0.0499 (4)
H2	0.59383 (15)	0.3100 (8)	0.25826 (17)	0.060*
N3	0.40186 (7)	0.23456 (19)	0.04887 (9)	0.0558 (4)
H3	0.3770 (8)	0.206 (2)	0.0027 (4)	0.067*
N4	0.40591 (7)	0.32307 (17)	−0.05841 (8)	0.0503 (4)
H4	0.3964 (7)	0.4083 (5)	−0.0781 (5)	0.060*
O1	0.32280 (7)	0.2228 (2)	0.05207 (11)	0.0861 (6)
O2	0.41265 (7)	0.3463 (2)	0.14866 (8)	0.0839 (5)
O3	0.39019 (9)	0.07239 (18)	−0.07875 (11)	0.0930 (6)
O4	0.33343 (7)	0.2375 (2)	−0.18079 (9)	0.0909 (6)
S1	0.36929 (2)	0.31189 (6)	0.07423 (3)	0.06194 (18)
S2	0.38699 (2)	0.19603 (6)	−0.11374 (3)	0.06646 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0374 (10)	0.0943 (17)	0.0613 (12)	−0.0013 (10)	0.0265 (10)	0.0116 (12)
C2	0.0371 (9)	0.0644 (12)	0.0416 (9)	0.0026 (8)	0.0237 (8)	0.0026 (8)
C3	0.0434 (10)	0.0588 (12)	0.0463 (10)	0.0100 (9)	0.0262 (9)	0.0040 (8)
C4	0.0413 (10)	0.0580 (11)	0.0385 (9)	0.0044 (8)	0.0220 (8)	0.0050 (8)
C5	0.0471 (12)	0.0961 (18)	0.0439 (11)	−0.0032 (11)	0.0215 (10)	−0.0054 (11)
C6	0.0698 (14)	0.0670 (14)	0.0662 (13)	0.0073 (11)	0.0428 (12)	0.0137 (11)
C7	0.0381 (9)	0.0481 (10)	0.0416 (9)	0.0037 (7)	0.0242 (8)	0.0008 (7)
C8	0.0445 (10)	0.0599 (11)	0.0463 (10)	0.0047 (8)	0.0313 (9)	0.0075 (8)
C9	0.0382 (9)	0.0495 (10)	0.0525 (10)	−0.0005 (8)	0.0293 (9)	0.0034 (8)
C10	0.0356 (9)	0.0476 (10)	0.0401 (9)	0.0005 (7)	0.0205 (8)	0.0013 (7)
C11	0.0391 (9)	0.0521 (10)	0.0399 (9)	−0.0002 (8)	0.0243 (8)	0.0037 (8)
C12	0.0360 (9)	0.0475 (10)	0.0413 (9)	0.0004 (7)	0.0231 (8)	0.0018 (7)
C13	0.0508 (11)	0.0724 (14)	0.0584 (12)	−0.0019 (10)	0.0368 (10)	−0.0062 (10)
C14	0.0533 (13)	0.0841 (17)	0.0733 (15)	0.0012 (12)	0.0358 (12)	−0.0070 (13)
C15	0.0704 (17)	0.098 (2)	0.0825 (18)	0.0249 (16)	0.0376 (15)	−0.0003 (16)
C16	0.119 (3)	0.0717 (17)	0.090 (2)	0.0168 (18)	0.070 (2)	0.0034 (14)
C17	0.114 (3)	0.0690 (17)	0.115 (2)	0.0007 (16)	0.085 (2)	0.0013 (15)
C18	0.0742 (16)	0.0747 (16)	0.0983 (19)	−0.0039 (13)	0.0612 (16)	−0.0024 (14)
C19	0.196 (5)	0.098 (3)	0.147 (4)	0.062 (3)	0.112 (4)	0.039 (2)
C20	0.0641 (14)	0.0605 (13)	0.0468 (11)	−0.0013 (10)	0.0270 (10)	−0.0106 (9)
C21	0.0810 (17)	0.0591 (14)	0.0716 (15)	0.0039 (12)	0.0370 (14)	−0.0016 (11)
C22	0.0811 (19)	0.0809 (19)	0.091 (2)	0.0200 (15)	0.0439 (17)	−0.0080 (16)
C23	0.088 (2)	0.109 (2)	0.0741 (17)	0.0166 (17)	0.0517 (16)	−0.0078 (16)
C24	0.104 (2)	0.106 (2)	0.0770 (17)	0.0195 (18)	0.0642 (17)	0.0119 (16)
C25	0.0814 (17)	0.0794 (16)	0.0606 (14)	0.0176 (13)	0.0437 (13)	0.0072 (12)
C26	0.116 (3)	0.201 (5)	0.111 (3)	0.034 (3)	0.082 (3)	−0.008 (3)
N1	0.0352 (8)	0.0597 (9)	0.0427 (8)	−0.0015 (7)	0.0227 (7)	0.0040 (7)
N2	0.0413 (8)	0.0666 (10)	0.0376 (8)	0.0053 (7)	0.0234 (7)	0.0006 (7)
N3	0.0410 (9)	0.0674 (11)	0.0582 (10)	−0.0059 (8)	0.0314 (8)	0.0007 (8)
N4	0.0369 (8)	0.0565 (10)	0.0431 (8)	−0.0031 (7)	0.0189 (7)	0.0008 (7)
O1	0.0602 (10)	0.1048 (14)	0.1098 (14)	−0.0049 (9)	0.0619 (11)	0.0222 (11)
O2	0.0597 (10)	0.1425 (17)	0.0554 (9)	0.0101 (10)	0.0396 (8)	0.0065 (10)
O3	0.1036 (14)	0.0680 (11)	0.0985 (13)	−0.0360 (10)	0.0605 (12)	−0.0145 (10)
O4	0.0485 (9)	0.1245 (15)	0.0551 (9)	−0.0182 (10)	0.0125 (8)	−0.0205 (10)
S1	0.0451 (3)	0.0872 (4)	0.0618 (3)	0.0008 (2)	0.0380 (3)	0.0107 (3)
S2	0.0538 (3)	0.0693 (4)	0.0535 (3)	−0.0189 (2)	0.0238 (3)	−0.0126 (2)

Geometric parameters (Å, º) top

C1—C2	1.490 (3)	C14—C15	1.393 (4)
C1—H1A	0.9600	C14—H14	0.9300
C1—H1B	0.9600	C15—C16	1.369 (5)
C1—H1C	0.9600	C15—H15	0.9300
C1—H1D	0.9600	C16—C17	1.368 (5)
C1—H1E	0.9600	C16—C19	1.527 (5)
C1—H1F	0.9600	C17—C18	1.373 (4)
C2—N1	1.283 (2)	C17—H17	0.9300
C2—C3	1.502 (3)	C18—H18	0.9300
C3—C4	1.538 (3)	C19—H19A	0.9600
C3—H3A	0.9700	C19—H19B	0.9600
C3—H3B	0.9700	C19—H19C	0.9600
C4—N2	1.486 (2)	C20—C21	1.384 (3)
C4—C6	1.519 (3)	C20—C25	1.390 (4)
C4—C5	1.522 (3)	C20—S2	1.749 (3)
C5—H5A	0.9600	C21—C22	1.380 (4)
C5—H5B	0.9600	C21—H21	0.9300
C5—H5C	0.9600	C22—C23	1.382 (5)
C6—H6A	0.9600	C22—H22	0.9300
C6—H6B	0.9600	C23—C24	1.389 (4)
C6—H6C	0.9600	C23—C26	1.505 (5)
C7—C12	1.383 (3)	C24—C25	1.374 (4)
C7—C8	1.394 (3)	C24—H24	0.9300
C7—N2	1.431 (2)	C25—H25	0.9300
C8—C9	1.369 (3)	C26—H26A	0.9600
C8—H8	0.9300	C26—H26B	0.9600
C9—C10	1.402 (3)	C26—H26C	0.9600
C9—N3	1.437 (2)	N2—H2	0.926 (2)
C10—C11	1.382 (3)	N3—S1	1.6305 (19)
C10—N4	1.440 (2)	N3—H3	0.899 (2)
C11—C12	1.386 (2)	N4—S2	1.6282 (17)
C11—H11	0.9300	N4—H4	0.904 (2)
C12—N1	1.416 (2)	O1—S1	1.4243 (17)
C13—C14	1.379 (3)	O2—S1	1.4274 (17)
C13—C18	1.385 (3)	O3—S2	1.4336 (19)
C13—S1	1.761 (2)	O4—S2	1.4275 (18)

C2—C1—H1A	109.5	C16—C15—H15	119.0
C2—C1—H1B	109.5	C14—C15—H15	119.0
H1A—C1—H1B	109.5	C17—C16—C15	118.3 (3)
C2—C1—H1C	109.5	C17—C16—C19	121.0 (4)
H1A—C1—H1C	109.5	C15—C16—C19	120.7 (4)
H1B—C1—H1C	109.5	C16—C17—C18	121.4 (3)
C2—C1—H1D	109.5	C16—C17—H17	119.3
C2—C1—H1E	109.5	C18—C17—H17	119.3
H1D—C1—H1E	109.5	C17—C18—C13	120.0 (3)
C2—C1—H1F	109.5	C17—C18—H18	120.0
H1D—C1—H1F	109.5	C13—C18—H18	120.0
H1E—C1—H1F	109.5	C16—C19—H19A	109.5
N1—C2—C1	118.73 (19)	C16—C19—H19B	109.5
N1—C2—C3	121.80 (17)	H19A—C19—H19B	109.5
C1—C2—C3	119.43 (17)	C16—C19—H19C	109.5
C2—C3—C4	113.85 (16)	H19A—C19—H19C	109.5
C2—C3—H3A	108.8	H19B—C19—H19C	109.5
C4—C3—H3A	108.8	C21—C20—C25	119.6 (3)
C2—C3—H3B	108.8	C21—C20—S2	120.8 (2)
C4—C3—H3B	108.8	C25—C20—S2	119.55 (19)
H3A—C3—H3B	107.7	C22—C21—C20	119.2 (3)
N2—C4—C6	110.45 (17)	C22—C21—H21	120.4
N2—C4—C5	107.38 (17)	C20—C21—H21	120.4
C6—C4—C5	110.58 (17)	C21—C22—C23	122.4 (3)
N2—C4—C3	108.95 (14)	C21—C22—H22	118.8
C6—C4—C3	109.17 (18)	C23—C22—H22	118.8
C5—C4—C3	110.28 (17)	C22—C23—C24	117.2 (3)
C4—C5—H5A	109.5	C22—C23—C26	120.6 (3)
C4—C5—H5B	109.5	C24—C23—C26	122.2 (3)
H5A—C5—H5B	109.5	C25—C24—C23	121.7 (3)
C4—C5—H5C	109.5	C25—C24—H24	119.1
H5A—C5—H5C	109.5	C23—C24—H24	119.1
H5B—C5—H5C	109.5	C24—C25—C20	119.9 (3)
C4—C6—H6A	109.5	C24—C25—H25	120.1
C4—C6—H6B	109.5	C20—C25—H25	120.1
H6A—C6—H6B	109.5	C23—C26—H26A	109.5
C4—C6—H6C	109.5	C23—C26—H26B	109.5
H6A—C6—H6C	109.5	H26A—C26—H26B	109.5
H6B—C6—H6C	109.5	C23—C26—H26C	109.5
C12—C7—C8	120.05 (16)	H26A—C26—H26C	109.5
C12—C7—N2	120.93 (16)	H26B—C26—H26C	109.5
C8—C7—N2	118.80 (16)	C2—N1—C12	119.57 (16)
C9—C8—C7	120.35 (17)	C7—N2—C4	118.74 (15)
C9—C8—H8	119.8	C7—N2—H2	104.3 (3)
C7—C8—H8	119.8	C4—N2—H2	108.8 (3)
C8—C9—C10	120.51 (17)	C9—N3—S1	123.55 (15)
C8—C9—N3	121.27 (17)	C9—N3—H3	112.6 (16)
C10—C9—N3	118.08 (16)	S1—N3—H3	112.4 (16)
C11—C10—C9	118.27 (16)	C10—N4—S2	119.65 (13)
C11—C10—N4	121.76 (16)	C10—N4—H4	115.7 (7)
C9—C10—N4	119.75 (16)	S2—N4—H4	115.8 (7)
C10—C11—C12	121.84 (17)	O1—S1—O2	120.08 (12)
C10—C11—H11	119.1	O1—S1—N3	105.07 (11)
C12—C11—H11	119.1	O2—S1—N3	107.10 (10)
C7—C12—C11	118.95 (17)	O1—S1—C13	107.74 (11)
C7—C12—N1	122.57 (16)	O2—S1—C13	108.70 (12)
C11—C12—N1	117.92 (16)	N3—S1—C13	107.52 (10)
C14—C13—C18	119.8 (2)	O4—S2—O3	120.33 (12)
C14—C13—S1	119.55 (19)	O4—S2—N4	105.31 (11)
C18—C13—S1	120.68 (18)	O3—S2—N4	107.14 (10)
C13—C14—C15	118.6 (3)	O4—S2—C20	108.19 (12)
C13—C14—H14	120.7	O3—S2—C20	108.26 (13)
C15—C14—H14	120.7	N4—S2—C20	106.86 (9)
C16—C15—C14	122.0 (3)

N1—C2—C3—C4	−77.0 (2)	C26—C23—C24—C25	178.2 (3)
C1—C2—C3—C4	105.2 (2)	C23—C24—C25—C20	1.1 (4)
C2—C3—C4—N2	43.0 (2)	C21—C20—C25—C24	0.7 (4)
C2—C3—C4—C6	163.73 (17)	S2—C20—C25—C24	178.2 (2)
C2—C3—C4—C5	−74.6 (2)	C1—C2—N1—C12	−173.93 (18)
C12—C7—C8—C9	−0.9 (3)	C3—C2—N1—C12	8.2 (3)
N2—C7—C8—C9	173.77 (17)	C7—C12—N1—C2	46.0 (3)
C7—C8—C9—C10	1.9 (3)	C11—C12—N1—C2	−142.70 (19)
C7—C8—C9—N3	177.50 (18)	C12—C7—N2—C4	−66.2 (2)
C8—C9—C10—C11	−0.9 (3)	C8—C7—N2—C4	119.17 (19)
N3—C9—C10—C11	−176.63 (17)	C6—C4—N2—C7	−80.7 (2)
C8—C9—C10—N4	−175.58 (17)	C5—C4—N2—C7	158.70 (17)
N3—C9—C10—N4	8.7 (3)	C3—C4—N2—C7	39.3 (2)
C9—C10—C11—C12	−1.1 (3)	C8—C9—N3—S1	63.0 (2)
N4—C10—C11—C12	173.48 (17)	C10—C9—N3—S1	−121.29 (18)
C8—C7—C12—C11	−1.0 (3)	C11—C10—N4—S2	84.8 (2)
N2—C7—C12—C11	−175.60 (17)	C9—C10—N4—S2	−100.66 (19)
C8—C7—C12—N1	170.16 (17)	C9—N3—S1—O1	−170.52 (16)
N2—C7—C12—N1	−4.4 (3)	C9—N3—S1—O2	−41.78 (19)
C10—C11—C12—C7	2.0 (3)	C9—N3—S1—C13	74.90 (18)
C10—C11—C12—N1	−169.54 (17)	C14—C13—S1—O1	13.3 (2)
C18—C13—C14—C15	−1.0 (4)	C18—C13—S1—O1	−167.7 (2)
S1—C13—C14—C15	178.0 (2)	C14—C13—S1—O2	−118.3 (2)
C13—C14—C15—C16	0.8 (4)	C18—C13—S1—O2	60.7 (2)
C14—C15—C16—C17	0.7 (5)	C14—C13—S1—N3	126.10 (19)
C14—C15—C16—C19	179.8 (3)	C18—C13—S1—N3	−54.9 (2)
C15—C16—C17—C18	−2.0 (5)	C10—N4—S2—O4	179.53 (15)
C19—C16—C17—C18	178.8 (3)	C10—N4—S2—O3	50.30 (18)
C16—C17—C18—C13	1.9 (4)	C10—N4—S2—C20	−65.56 (17)
C14—C13—C18—C17	−0.3 (4)	C21—C20—S2—O4	−141.53 (19)
S1—C13—C18—C17	−179.3 (2)	C25—C20—S2—O4	41.1 (2)
C25—C20—C21—C22	−1.5 (4)	C21—C20—S2—O3	−9.6 (2)
S2—C20—C21—C22	−178.9 (2)	C25—C20—S2—O3	173.00 (18)
C20—C21—C22—C23	0.4 (4)	C21—C20—S2—N4	105.52 (19)
C21—C22—C23—C24	1.3 (5)	C25—C20—S2—N4	−71.9 (2)
C21—C22—C23—C26	−179.0 (3)	C10—C9—N3—S1	−121.29 (18)
C22—C23—C24—C25	−2.0 (5)	C9—C10—N4—S2	−100.66 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O3	0.90 (1)	2.59 (2)	3.268 (3)	133 (2)
N4—H4···N1ⁱ	0.90 (1)	1.97 (1)	2.861 (2)	168 (2)
C1—H1B···C16ⁱ	0.96	2.76	3.584 (4)	145
C1—H1B···C17ⁱ	0.96	2.82	3.600 (4)	139
C1—H1C···O4ⁱ	0.96	2.59	3.434 (4)	147
C26—H26B···C16ⁱ	0.96	3.19	4.094 (5)	157
N2—H2···O2ⁱⁱ	0.93 (1)	2.40 (1)	3.254 (2)	154 (1)
C14—H14···O1ⁱⁱⁱ	0.93	2.45	3.356 (3)	165
C1—H1A···O4^iv	0.96	2.34	3.293 (3)	176

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

2,2,4-Trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepin-1-ium chloride 0.3-hydrate (3) top

Crystal data top

C₂₆H₃₁N₄O₄S₂⁺·Cl1·0.3H₂O	F(000) = 1196
M_r = 568.52	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 12.0993 (2) Å	Cell parameters from 11735 reflections
b = 13.4307 (2) Å	θ = 3.7–78.1°
c = 17.3586 (3) Å	µ = 3.00 mm⁻¹
β = 103.667 (2)°	T = 293 K
V = 2740.94 (8) Å³	Plate, yellow
Z = 4	0.19 × 0.15 × 0.03 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	5837 independent reflections
Radiation source: micro-focus sealed X-ray tube	4787 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.039
ω scans	θ_max = 79.7°, θ_min = 3.8°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	h = −15→15
T_min = 0.498, T_max = 1.000	k = −16→7
24340 measured reflections	l = −22→22

Refinement top

Refinement on F²	74 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0649P)² + 0.3926P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.015
5837 reflections	Δρ_max = 0.30 e Å⁻³
433 parameters	Δρ_min = −0.27 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.04460 (19)	0.3882 (2)	0.09107 (17)	0.0742 (6)
H1A	−0.015804	0.388415	0.118334	0.111*	0.5
H1B	0.019237	0.420183	0.040507	0.111*	0.5
H1C	0.066036	0.320784	0.083382	0.111*	0.5
H1D	0.062117	0.364506	0.043148	0.111*	0.5
H1E	0.027075	0.332738	0.120975	0.111*	0.5
H1F	−0.019723	0.432137	0.078100	0.111*	0.5
C2	0.14379 (18)	0.44258 (16)	0.13885 (14)	0.0599 (5)
C3	0.1294 (14)	0.4818 (9)	0.2175 (9)	0.059 (3)	0.364 (17)
H3A	0.050608	0.473207	0.219651	0.071*	0.364 (17)
H3B	0.175548	0.441728	0.259518	0.071*	0.364 (17)
C3A	0.0868 (10)	0.5267 (10)	0.1747 (9)	0.064 (3)	0.180 (5)
H3A1	0.047021	0.569168	0.131827	0.077*	0.180 (5)
H3A2	0.030002	0.497480	0.199000	0.077*	0.180 (5)
C3B	0.1594 (10)	0.4767 (6)	0.2242 (5)	0.0511 (19)	0.456 (17)
H3B1	0.098010	0.449776	0.245138	0.061*	0.456 (17)
H3B2	0.230207	0.449748	0.255518	0.061*	0.456 (17)
C4	0.16105 (19)	0.58891 (16)	0.23335 (15)	0.0637 (5)
C5	0.160 (2)	0.6065 (14)	0.3199 (9)	0.098 (5)	0.364 (17)
H5A	0.085465	0.591680	0.327628	0.148*	0.364 (17)
H5B	0.214878	0.564095	0.353204	0.148*	0.364 (17)
H5C	0.177976	0.674851	0.333414	0.148*	0.364 (17)
C5A	0.102 (3)	0.663 (2)	0.2679 (17)	0.095 (6)	0.180 (5)
H5A1	0.035509	0.634659	0.279510	0.142*	0.180 (5)
H5A2	0.151599	0.687524	0.315978	0.142*	0.180 (5)
H5A3	0.081045	0.717436	0.231304	0.142*	0.180 (5)
C5B	0.1203 (12)	0.6346 (10)	0.3010 (8)	0.086 (5)	0.456 (17)
H5B1	0.126479	0.705777	0.298946	0.129*	0.456 (17)
H5B2	0.042331	0.616501	0.296779	0.129*	0.456 (17)
H5B3	0.166122	0.610673	0.350427	0.129*	0.456 (17)
C6	0.0531 (10)	0.6370 (15)	0.1759 (13)	0.114 (5)	0.364 (17)
H6A	−0.014321	0.603944	0.182677	0.171*	0.364 (17)
H6B	0.049146	0.706407	0.188296	0.171*	0.364 (17)
H6C	0.058977	0.629908	0.122030	0.171*	0.364 (17)
C6A	0.2172 (14)	0.4997 (10)	0.2991 (8)	0.083 (5)	0.180 (5)
H6A1	0.157272	0.465640	0.315987	0.124*	0.180 (5)
H6A2	0.258472	0.453089	0.274655	0.124*	0.180 (5)
H6A3	0.267893	0.529531	0.344157	0.124*	0.180 (5)
C6B	0.0909 (13)	0.6463 (11)	0.1561 (9)	0.122 (5)	0.456 (17)
H6B1	0.112350	0.621123	0.109966	0.183*	0.456 (17)
H6B2	0.010915	0.636005	0.150740	0.183*	0.456 (17)
H6B3	0.107417	0.716267	0.161363	0.183*	0.456 (17)
C7	0.35175 (15)	0.58189 (13)	0.19626 (11)	0.0459 (4)
C8	0.45823 (15)	0.62927 (12)	0.21358 (11)	0.0456 (4)
H8	0.468949	0.684508	0.246821	0.055*
C9	0.54745 (14)	0.59709 (12)	0.18321 (9)	0.0403 (3)
C10	0.53355 (14)	0.51243 (12)	0.13425 (10)	0.0417 (3)
C11	0.42854 (15)	0.46747 (12)	0.11424 (10)	0.0447 (4)
H11	0.417572	0.413641	0.079560	0.054*
C12	0.33801 (14)	0.50047 (12)	0.14461 (10)	0.0423 (3)
C13	0.77760 (17)	0.58891 (16)	0.33833 (13)	0.0586 (5)
C14	0.7695 (3)	0.5834 (3)	0.41662 (16)	0.0881 (8)
H14	0.729795	0.631795	0.437442	0.106*
C15	0.8207 (3)	0.5059 (3)	0.4629 (2)	0.1119 (12)
H15	0.816008	0.502556	0.515528	0.134*
C16	0.8792 (3)	0.4326 (3)	0.4332 (2)	0.0973 (10)
C17	0.8859 (2)	0.4391 (2)	0.3547 (2)	0.0872 (8)
H17	0.925397	0.390577	0.333908	0.105*
C18	0.8346 (2)	0.51710 (17)	0.30679 (15)	0.0673 (5)
H18	0.838731	0.520575	0.254040	0.081*
C19	0.9379 (4)	0.3478 (3)	0.4859 (3)	0.1435 (18)
H19A	0.973946	0.304107	0.455528	0.215*
H19B	0.994052	0.374706	0.529457	0.215*
H19C	0.882461	0.311159	0.505937	0.215*
C20	0.62321 (17)	0.28371 (13)	0.04958 (11)	0.0510 (4)
C21	0.5324 (2)	0.22358 (19)	0.05155 (16)	0.0746 (7)
H21	0.498160	0.225991	0.094159	0.089*
C22	0.4927 (3)	0.1591 (2)	−0.0113 (2)	0.0888 (8)
H22	0.430333	0.118866	−0.010632	0.107*
C23	0.5426 (3)	0.15274 (19)	−0.07427 (15)	0.0775 (7)
C24	0.6339 (3)	0.21332 (17)	−0.07439 (14)	0.0771 (7)
H24	0.669421	0.209681	−0.116350	0.093*
C25	0.6739 (2)	0.27929 (15)	−0.01361 (13)	0.0648 (6)
H25	0.734959	0.320747	−0.015115	0.078*
C26	0.4980 (4)	0.0818 (3)	−0.1427 (2)	0.1213 (14)
H26A	0.543353	0.087731	−0.180952	0.182*
H26B	0.501983	0.014724	−0.123110	0.182*
H26C	0.420395	0.098117	−0.167197	0.182*
N1	0.23353 (13)	0.45073 (11)	0.11264 (9)	0.0478 (3)
H1	0.2338 (19)	0.4203 (15)	0.0665 (8)	0.057*
N2	0.2767 (12)	0.616 (2)	0.242 (2)	0.059 (4)	0.46 (8)
H2	0.308 (4)	0.666 (4)	0.274 (3)	0.061 (17)*	0.46 (8)
N2A	0.2612 (15)	0.6303 (8)	0.216 (2)	0.054 (3)	0.54 (8)
H2A	0.281 (4)	0.689 (2)	0.240 (4)	0.056 (14)*	0.54 (8)
N3	0.65085 (13)	0.65168 (11)	0.19616 (9)	0.0461 (3)
H3	0.6907 (11)	0.6490 (14)	0.1552 (6)	0.055*
N4	0.62609 (13)	0.47384 (11)	0.10581 (10)	0.0494 (3)
H4	0.6666 (13)	0.5179 (8)	0.0810 (12)	0.059*
O1	0.64945 (13)	0.74462 (12)	0.32091 (9)	0.0679 (4)
O2	0.81601 (13)	0.74603 (11)	0.26263 (10)	0.0647 (4)
O3	0.64571 (13)	0.32884 (11)	0.19698 (8)	0.0588 (3)
O4	0.79906 (12)	0.37377 (12)	0.13173 (11)	0.0703 (4)
S1	0.72286 (4)	0.69330 (3)	0.28105 (3)	0.05025 (13)
S2	0.68051 (4)	0.36448 (3)	0.12885 (3)	0.04832 (13)
Cl1	0.77582 (6)	0.64137 (5)	0.05150 (3)	0.0808 (2)
O5	0.8361 (12)	0.8495 (6)	0.1186 (6)	0.145 (4)	0.3
H5F	0.845 (16)	0.837 (9)	0.1767 (14)	0.217*	0.3
H5G	0.812 (16)	0.785 (5)	0.090 (5)	0.217*	0.3

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0443 (11)	0.0913 (16)	0.0869 (17)	−0.0177 (11)	0.0154 (11)	−0.0042 (13)
C2	0.0508 (10)	0.0610 (11)	0.0722 (13)	−0.0108 (9)	0.0231 (10)	−0.0090 (9)
C3	0.052 (7)	0.065 (4)	0.069 (4)	−0.010 (4)	0.028 (4)	−0.008 (3)
C3A	0.047 (5)	0.071 (5)	0.078 (6)	0.004 (4)	0.021 (5)	−0.013 (5)
C3B	0.041 (4)	0.058 (3)	0.060 (3)	−0.008 (2)	0.022 (3)	0.007 (2)
C4	0.0493 (11)	0.0647 (12)	0.0854 (15)	−0.0077 (9)	0.0324 (11)	−0.0138 (10)
C5	0.155 (13)	0.064 (8)	0.097 (7)	−0.034 (8)	0.072 (8)	−0.028 (5)
C5A	0.105 (11)	0.090 (12)	0.121 (13)	−0.034 (10)	0.090 (11)	−0.012 (10)
C5B	0.096 (7)	0.071 (9)	0.121 (9)	−0.025 (6)	0.085 (8)	−0.028 (7)
C6	0.046 (5)	0.079 (6)	0.209 (13)	0.020 (5)	0.012 (7)	0.002 (6)
C6A	0.104 (12)	0.082 (9)	0.074 (9)	−0.014 (8)	0.042 (9)	−0.014 (7)
C6B	0.066 (7)	0.074 (5)	0.195 (11)	0.028 (6)	−0.028 (7)	−0.002 (6)
C7	0.0399 (8)	0.0469 (8)	0.0531 (9)	0.0004 (7)	0.0155 (7)	−0.0015 (7)
C8	0.0425 (9)	0.0449 (8)	0.0505 (9)	−0.0014 (7)	0.0133 (7)	−0.0060 (7)
C9	0.0364 (8)	0.0438 (8)	0.0402 (8)	−0.0005 (6)	0.0081 (6)	0.0027 (6)
C10	0.0378 (8)	0.0448 (8)	0.0443 (8)	0.0012 (6)	0.0131 (7)	0.0008 (6)
C11	0.0430 (9)	0.0445 (8)	0.0474 (9)	−0.0023 (7)	0.0126 (7)	−0.0039 (7)
C12	0.0350 (8)	0.0449 (8)	0.0466 (9)	−0.0025 (6)	0.0089 (7)	0.0015 (7)
C13	0.0458 (10)	0.0680 (12)	0.0574 (11)	−0.0094 (9)	0.0031 (9)	0.0001 (9)
C14	0.0862 (19)	0.117 (2)	0.0585 (13)	0.0072 (16)	0.0119 (13)	0.0091 (14)
C15	0.116 (3)	0.143 (3)	0.0682 (17)	0.006 (2)	0.0053 (17)	0.0305 (19)
C16	0.0831 (19)	0.095 (2)	0.096 (2)	−0.0129 (16)	−0.0138 (17)	0.0302 (17)
C17	0.0715 (16)	0.0658 (14)	0.114 (2)	−0.0009 (12)	0.0012 (15)	0.0073 (14)
C18	0.0613 (12)	0.0619 (12)	0.0745 (14)	−0.0022 (10)	0.0076 (11)	0.0012 (10)
C19	0.123 (3)	0.128 (3)	0.151 (4)	−0.009 (3)	−0.027 (3)	0.067 (3)
C20	0.0546 (10)	0.0469 (9)	0.0538 (10)	0.0097 (8)	0.0170 (8)	−0.0003 (7)
C21	0.0700 (15)	0.0812 (15)	0.0793 (15)	−0.0171 (12)	0.0313 (13)	−0.0241 (12)
C22	0.0756 (17)	0.0878 (17)	0.101 (2)	−0.0160 (14)	0.0172 (15)	−0.0305 (16)
C23	0.099 (2)	0.0662 (13)	0.0595 (13)	0.0223 (13)	0.0024 (13)	−0.0118 (11)
C24	0.118 (2)	0.0617 (12)	0.0573 (12)	0.0185 (14)	0.0316 (14)	0.0023 (10)
C25	0.0870 (16)	0.0518 (10)	0.0634 (12)	0.0080 (10)	0.0336 (12)	0.0064 (9)
C26	0.168 (4)	0.098 (2)	0.081 (2)	0.020 (2)	−0.004 (2)	−0.0343 (17)
N1	0.0393 (7)	0.0534 (8)	0.0512 (8)	−0.0047 (6)	0.0117 (6)	−0.0044 (6)
N2	0.047 (3)	0.069 (6)	0.067 (8)	−0.005 (3)	0.025 (4)	−0.022 (5)
N2A	0.051 (3)	0.045 (3)	0.075 (8)	−0.005 (2)	0.032 (4)	−0.009 (3)
N3	0.0399 (7)	0.0539 (8)	0.0457 (8)	−0.0062 (6)	0.0128 (6)	−0.0045 (6)
N4	0.0462 (8)	0.0460 (7)	0.0628 (9)	−0.0011 (6)	0.0261 (7)	−0.0019 (6)
O1	0.0584 (9)	0.0778 (9)	0.0680 (9)	0.0007 (7)	0.0163 (7)	−0.0254 (7)
O2	0.0539 (8)	0.0638 (8)	0.0754 (10)	−0.0187 (7)	0.0136 (7)	−0.0066 (7)
O3	0.0634 (9)	0.0612 (7)	0.0532 (7)	0.0051 (6)	0.0169 (7)	0.0038 (6)
O4	0.0397 (7)	0.0790 (9)	0.0943 (12)	0.0061 (7)	0.0201 (7)	−0.0029 (8)
S1	0.0423 (2)	0.0536 (2)	0.0542 (3)	−0.00587 (17)	0.01008 (18)	−0.00933 (18)
S2	0.0398 (2)	0.0520 (2)	0.0550 (3)	0.00360 (17)	0.01484 (18)	−0.00086 (18)
Cl1	0.0862 (4)	0.1064 (4)	0.0587 (3)	−0.0452 (3)	0.0346 (3)	−0.0196 (3)
O5	0.239 (13)	0.091 (5)	0.124 (7)	−0.054 (7)	0.082 (8)	−0.020 (5)

Geometric parameters (Å, º) top

C1—C2	1.480 (3)	C8—H8	0.9300
C1—H1A	0.9600	C9—C10	1.406 (2)
C1—H1B	0.9600	C9—N3	1.421 (2)
C1—H1C	0.9600	C10—C11	1.375 (2)
C1—H1D	0.9600	C10—N4	1.424 (2)
C1—H1E	0.9600	C11—C12	1.395 (2)
C1—H1F	0.9600	C11—H11	0.9300
C2—N1	1.277 (3)	C12—N1	1.421 (2)
C2—C3	1.511 (11)	C13—C18	1.372 (3)
C2—C3B	1.519 (9)	C13—C14	1.387 (3)
C2—C3A	1.530 (10)	C13—S1	1.756 (2)
C3—C4	1.498 (11)	C14—C15	1.371 (5)
C3—H3A	0.9700	C14—H14	0.9300
C3—H3B	0.9700	C15—C16	1.381 (5)
C3A—C4	1.453 (11)	C15—H15	0.9300
C3A—H3A1	0.9700	C16—C17	1.386 (5)
C3A—H3A2	0.9700	C16—C19	1.528 (5)
C3B—C4	1.515 (9)	C17—C18	1.390 (4)
C3B—H3B1	0.9700	C17—H17	0.9300
C3B—H3B2	0.9700	C18—H18	0.9300
C4—N2	1.421 (10)	C19—H19A	0.9600
C4—N2A	1.431 (8)	C19—H19B	0.9600
C4—C5A	1.44 (3)	C19—H19C	0.9600
C4—C5B	1.508 (8)	C20—C21	1.370 (3)
C4—C5	1.525 (12)	C20—C25	1.379 (3)
C4—C6	1.582 (11)	C20—S2	1.761 (2)
C4—C6B	1.605 (10)	C21—C22	1.387 (4)
C4—C6A	1.683 (13)	C21—H21	0.9300
C5—H5A	0.9600	C22—C23	1.371 (4)
C5—H5B	0.9600	C22—H22	0.9300
C5—H5C	0.9600	C23—C24	1.373 (4)
C5A—H5A1	0.9600	C23—C26	1.519 (4)
C5A—H5A2	0.9600	C24—C25	1.375 (3)
C5A—H5A3	0.9600	C24—H24	0.9300
C5B—H5B1	0.9600	C25—H25	0.9300
C5B—H5B2	0.9600	C26—H26A	0.9600
C5B—H5B3	0.9600	C26—H26B	0.9600
C6—H6A	0.9600	C26—H26C	0.9600
C6—H6B	0.9600	N1—H1	0.899 (9)
C6—H6C	0.9600	N2—H2	0.901 (10)
C6A—H6A1	0.9600	N2A—H2A	0.901 (10)
C6A—H6A2	0.9600	N3—S1	1.6237 (15)
C6A—H6A3	0.9600	N3—H3	0.949 (7)
C6B—H6B1	0.9600	N4—S2	1.6207 (16)
C6B—H6B2	0.9600	N4—H4	0.936 (7)
C6B—H6B3	0.9600	O1—S1	1.4259 (15)
C7—N2A	1.382 (10)	O2—S1	1.4297 (14)
C7—C12	1.399 (2)	O3—S2	1.4283 (14)
C7—C8	1.404 (2)	O4—S2	1.4289 (15)
C7—N2	1.413 (13)	O5—H5F	1.003 (10)
C8—C9	1.378 (2)	O5—H5G	1.006 (10)

C2—C1—H1A	109.5	C8—C7—N2	114.2 (5)
C2—C1—H1B	109.5	C9—C8—C7	122.55 (16)
H1A—C1—H1B	109.5	C9—C8—H8	118.7
C2—C1—H1C	109.5	C7—C8—H8	118.7
H1A—C1—H1C	109.5	C8—C9—C10	119.50 (15)
H1B—C1—H1C	109.5	C8—C9—N3	121.17 (15)
C2—C1—H1D	109.5	C10—C9—N3	119.20 (14)
C2—C1—H1E	109.5	C11—C10—C9	118.64 (15)
H1D—C1—H1E	109.5	C11—C10—N4	120.53 (15)
C2—C1—H1F	109.5	C9—C10—N4	120.83 (15)
H1D—C1—H1F	109.5	C10—C11—C12	121.74 (16)
H1E—C1—H1F	109.5	C10—C11—H11	119.1
N1—C2—C1	119.2 (2)	C12—C11—H11	119.1
N1—C2—C3	125.5 (6)	C11—C12—C7	120.36 (15)
C1—C2—C3	115.3 (6)	C11—C12—N1	114.10 (15)
N1—C2—C3B	113.7 (5)	C7—C12—N1	125.28 (15)
C1—C2—C3B	126.3 (4)	C18—C13—C14	120.8 (2)
N1—C2—C3A	125.8 (5)	C18—C13—S1	119.54 (18)
C1—C2—C3A	102.0 (5)	C14—C13—S1	119.5 (2)
C4—C3—C2	115.0 (9)	C15—C14—C13	119.2 (3)
C4—C3—H3A	108.5	C15—C14—H14	120.4
C2—C3—H3A	108.5	C13—C14—H14	120.4
C4—C3—H3B	108.5	C14—C15—C16	121.6 (3)
C2—C3—H3B	108.5	C14—C15—H15	119.2
H3A—C3—H3B	107.5	C16—C15—H15	119.2
C4—C3A—C2	116.5 (8)	C15—C16—C17	118.4 (3)
C4—C3A—H3A1	108.2	C15—C16—C19	120.9 (4)
C2—C3A—H3A1	108.2	C17—C16—C19	120.6 (4)
C4—C3A—H3A2	108.2	C16—C17—C18	120.9 (3)
C2—C3A—H3A2	108.2	C16—C17—H17	119.5
H3A1—C3A—H3A2	107.3	C18—C17—H17	119.5
C4—C3B—C2	113.4 (6)	C13—C18—C17	119.1 (3)
C4—C3B—H3B1	108.9	C13—C18—H18	120.5
C2—C3B—H3B1	108.9	C17—C18—H18	120.5
C4—C3B—H3B2	108.9	C16—C19—H19A	109.5
C2—C3B—H3B2	108.9	C16—C19—H19B	109.5
H3B1—C3B—H3B2	107.7	H19A—C19—H19B	109.5
N2A—C4—C5A	110.3 (11)	C16—C19—H19C	109.5
N2A—C4—C3A	119.2 (13)	H19A—C19—H19C	109.5
C5A—C4—C3A	114.1 (15)	H19B—C19—H19C	109.5
N2—C4—C3	118.0 (12)	C21—C20—C25	120.3 (2)
C5B—C4—C3B	119.2 (7)	C21—C20—S2	120.89 (16)
N2—C4—C5	95.7 (15)	C25—C20—S2	118.76 (17)
C3—C4—C5	105.6 (9)	C20—C21—C22	118.7 (2)
N2—C4—C6	127.3 (19)	C20—C21—H21	120.7
C3—C4—C6	98.0 (11)	C22—C21—H21	120.7
C5—C4—C6	111.0 (11)	C23—C22—C21	122.0 (3)
C5B—C4—C6B	104.4 (8)	C23—C22—H22	119.0
C3B—C4—C6B	113.5 (7)	C21—C22—H22	119.0
N2A—C4—C6A	101.3 (12)	C22—C23—C24	118.1 (2)
C5A—C4—C6A	111.8 (12)	C22—C23—C26	121.3 (3)
C3A—C4—C6A	98.6 (8)	C24—C23—C26	120.6 (3)
C4—C5—H5A	109.5	C23—C24—C25	121.2 (2)
C4—C5—H5B	109.5	C23—C24—H24	119.4
H5A—C5—H5B	109.5	C25—C24—H24	119.4
C4—C5—H5C	109.5	C24—C25—C20	119.7 (2)
H5A—C5—H5C	109.5	C24—C25—H25	120.1
H5B—C5—H5C	109.5	C20—C25—H25	120.1
C4—C5A—H5A1	109.5	C23—C26—H26A	109.5
C4—C5A—H5A2	109.5	C23—C26—H26B	109.5
H5A1—C5A—H5A2	109.5	H26A—C26—H26B	109.5
C4—C5A—H5A3	109.5	C23—C26—H26C	109.5
H5A1—C5A—H5A3	109.5	H26A—C26—H26C	109.5
H5A2—C5A—H5A3	109.5	H26B—C26—H26C	109.5
C4—C5B—H5B1	109.5	C2—N1—C12	130.82 (17)
C4—C5B—H5B2	109.5	C2—N1—H1	117.4 (14)
H5B1—C5B—H5B2	109.5	C12—N1—H1	111.8 (14)
C4—C5B—H5B3	109.5	C7—N2—C4	127.3 (10)
H5B1—C5B—H5B3	109.5	C7—N2—H2	112 (3)
H5B2—C5B—H5B3	109.5	C4—N2—H2	121 (3)
C4—C6—H6A	109.5	C7—N2A—C4	129.0 (8)
C4—C6—H6B	109.5	C7—N2A—H2A	113 (2)
H6A—C6—H6B	109.5	C4—N2A—H2A	113 (2)
C4—C6—H6C	109.5	C9—N3—S1	125.77 (12)
H6A—C6—H6C	109.5	C9—N3—H3	116.5 (7)
H6B—C6—H6C	109.5	S1—N3—H3	115.7 (7)
C4—C6A—H6A1	109.5	C10—N4—S2	123.45 (12)
C4—C6A—H6A2	109.5	C10—N4—H4	118.0 (7)
H6A1—C6A—H6A2	109.5	S2—N4—H4	117.4 (7)
C4—C6A—H6A3	109.5	O1—S1—O2	118.91 (10)
H6A1—C6A—H6A3	109.5	O1—S1—N3	110.15 (9)
H6A2—C6A—H6A3	109.5	O2—S1—N3	104.47 (9)
C4—C6B—H6B1	109.5	O1—S1—C13	107.83 (11)
C4—C6B—H6B2	109.5	O2—S1—C13	108.09 (10)
H6B1—C6B—H6B2	109.5	N3—S1—C13	106.79 (9)
C4—C6B—H6B3	109.5	O3—S2—O4	119.35 (10)
H6B1—C6B—H6B3	109.5	O3—S2—N4	109.02 (8)
H6B2—C6B—H6B3	109.5	O4—S2—N4	105.98 (9)
N2A—C7—C12	122.9 (10)	O3—S2—C20	107.58 (9)
N2A—C7—C8	118.3 (7)	O4—S2—C20	106.72 (10)
C12—C7—C8	117.10 (15)	N4—S2—C20	107.67 (9)
C12—C7—N2	128.2 (5)	H5F—O5—H5G	107 (2)

N1—C2—C3—C4	51.1 (15)	C21—C22—C23—C24	−0.6 (5)
C1—C2—C3—C4	−130.7 (9)	C21—C22—C23—C26	−179.9 (3)
N1—C2—C3A—C4	−46.8 (14)	C22—C23—C24—C25	−0.6 (4)
C1—C2—C3A—C4	173.1 (9)	C26—C23—C24—C25	178.7 (3)
N1—C2—C3B—C4	76.3 (8)	C23—C24—C25—C20	1.3 (4)
C1—C2—C3B—C4	−114.2 (6)	C21—C20—C25—C24	−0.8 (3)
C2—C3A—C4—N2A	49.8 (16)	S2—C20—C25—C24	176.93 (18)
C2—C3A—C4—C5A	−177.0 (12)	C1—C2—N1—C12	178.0 (2)
C2—C3A—C4—C6A	−58.3 (12)	C3—C2—N1—C12	−3.9 (9)
C2—C3—C4—N2	−65 (2)	C3B—C2—N1—C12	−11.7 (5)
C2—C3—C4—C5	−170.4 (16)	C3A—C2—N1—C12	43.9 (8)
C2—C3—C4—C6	75.1 (15)	C11—C12—N1—C2	160.1 (2)
C2—C3B—C4—C5B	151.0 (10)	C7—C12—N1—C2	−25.7 (3)
C2—C3B—C4—C6B	27.3 (14)	C12—C7—N2—C4	−14 (5)
N2A—C7—C8—C9	−167.0 (15)	C8—C7—N2—C4	174 (3)
C12—C7—C8—C9	−1.4 (3)	C3—C4—N2—C7	41 (4)
N2—C7—C8—C9	171.2 (19)	C5—C4—N2—C7	152 (4)
C7—C8—C9—C10	−1.4 (3)	C6—C4—N2—C7	−86 (4)
C7—C8—C9—N3	174.40 (16)	C12—C7—N2A—C4	42 (4)
C8—C9—C10—C11	3.8 (2)	C8—C7—N2A—C4	−153 (2)
N3—C9—C10—C11	−172.07 (15)	C5A—C4—N2A—C7	167 (3)
C8—C9—C10—N4	−176.23 (16)	C3A—C4—N2A—C7	−59 (3)
N3—C9—C10—N4	7.9 (2)	C6A—C4—N2A—C7	48 (3)
C9—C10—C11—C12	−3.5 (3)	C8—C9—N3—S1	48.9 (2)
N4—C10—C11—C12	176.55 (16)	C10—C9—N3—S1	−135.36 (15)
C10—C11—C12—C7	0.6 (3)	C11—C10—N4—S2	−63.7 (2)
C10—C11—C12—N1	175.10 (16)	C9—C10—N4—S2	116.33 (16)
N2A—C7—C12—C11	166.7 (13)	C9—N3—S1—O1	−48.84 (18)
C8—C7—C12—C11	1.8 (3)	C9—N3—S1—O2	−177.63 (15)
N2—C7—C12—C11	−170 (2)	C9—N3—S1—C13	67.99 (17)
N2A—C7—C12—N1	−7.1 (14)	C18—C13—S1—O1	168.47 (17)
C8—C7—C12—N1	−172.00 (16)	C14—C13—S1—O1	−15.9 (2)
N2—C7—C12—N1	17 (2)	C18—C13—S1—O2	−61.8 (2)
C18—C13—C14—C15	1.0 (4)	C14—C13—S1—O2	113.8 (2)
S1—C13—C14—C15	−174.6 (3)	C18—C13—S1—N3	50.1 (2)
C13—C14—C15—C16	−0.7 (6)	C14—C13—S1—N3	−134.3 (2)
C14—C15—C16—C17	0.4 (6)	C10—N4—S2—O3	−16.93 (18)
C14—C15—C16—C19	178.7 (3)	C10—N4—S2—O4	−146.59 (16)
C15—C16—C17—C18	−0.4 (5)	C10—N4—S2—C20	99.50 (16)
C19—C16—C17—C18	−178.8 (3)	C21—C20—S2—O3	20.1 (2)
C14—C13—C18—C17	−1.0 (4)	C25—C20—S2—O3	−157.57 (16)
S1—C13—C18—C17	174.57 (18)	C21—C20—S2—O4	149.3 (2)
C16—C17—C18—C13	0.7 (4)	C25—C20—S2—O4	−28.37 (19)
C25—C20—C21—C22	−0.4 (4)	C21—C20—S2—N4	−97.3 (2)
S2—C20—C21—C22	−178.0 (2)	C25—C20—S2—N4	85.05 (18)
C20—C21—C22—C23	1.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl1	0.95 (1)	2.28 (1)	3.2256 (15)	177 (1)
N4—H4···Cl1	0.94 (1)	2.25 (1)	3.1686 (15)	166 (2)
N1—H1···Cl1ⁱ	0.90 (1)	2.19 (1)	3.0837 (16)	174 (2)
N2—H2···O3ⁱⁱ	0.90 (1)	2.28 (4)	3.114 (19)	154 (6)
N2A—H2A···O3ⁱⁱ	0.90 (1)	2.25 (2)	3.142 (17)	173 (4)
O5—H5G···Cl1	1.01 (1)	2.05 (2)	3.050 (8)	170 (10)
O5—H5F···O2	1.00 (1)	2.02 (4)	2.921 (9)	148 (7)
C21—H21···O1ⁱⁱⁱ	0.93	2.58	3.482 (3)	163
C1—H1A···O4^iv	0.96	2.31	3.218 (3)	157
C26—H26B···C14^v	0.96	3.41	3.896 (5)	114
C19—H19B···C14^vi	0.96	2.85	3.664 (5)	143
C19—H19B···C15^vi	0.96	2.73	3.458 (6)	133

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

Acknowledgements

The authors are thankful to CNPQ, FAPEMIG and PRPq-UFMG for financial support, and to CAPES for scholarships. They are also thankful to LabCri (http://www.labcri.ufmg.br/) for providing the single-crystal and polycrystalline diffraction facilities, and the Bioanalytical Facility NEPS–DQ (https://ne.qui.ufmg.br) for all chemical characterizations.

Funding information

Funding for this research was provided by: Conselho Nacional de Desenvolvimento Cientfico e Tecnolgico (award No. 420443/2018-5); Fundação de Amparo Pesquisa do Estado de Minas Gerais (award Nos. APQ-01948-22 and APQ-05311-23).

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Volume 80| Part 9| September 2024| Pages 497-504

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crystallography in latin america\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of two unexpected products of vicinal di­amines left to crystallize in acetone

1. Introduction

2. Experimental

2.1. Materials synthesis

2.1.1. General procedure for the reduction of 1,2-bis­(4-methyl­ben­zene­sul­fon­am­ido)-4,5-di­nitro­ben­zene

2.1.2. N,N′-(4,5-Di­amino-1,2-phenyl­ene)bis­(4-methyl­ben­zene­sul­fon­am­ide) (1)

2.1.3. 4,5-(4-Methyl­ben­zene­sul­fon­am­ido)­ben­zene-1,2-di­am­inium dichloride (1·2HCl)

2.1.4. 2,2,4-Trimethyl-8,9-bis­(4-methyl­ben­zene­sul­fon­am­ido)-2,3-di­hydro-5H-1,5-ben­zo­di­az­e­pine (2)

2.1.5. 2,2,4-Trimethyl-8,9-bis­(4-methyl­ben­zene­sul­fon­am­ido)-2,3-di­hydro-5H-1,5-ben­zo­di­az­e­pin-1-ium chloride 0.3-hydrate (3)

2.2. Single-crystal X-ray diffraction

2.3. Chemical characterizations

3. Results and discussion

3.1. Crystal structure description

3.2. Cyclization reaction with the solvent

4. Conclusions

Supporting information

Acknowledgements

Funding information

References

crystallography in latin america

Crystal structures of two unexpected products of vicinal diamines left to crystallize in acetone

2.1.1. General procedure for the reduction of 1,2-bis(4-methylbenzenesulfonamido)-4,5-dinitrobenzene

2.1.2. N,N′-(4,5-Diamino-1,2-phenylene)bis(4-methylbenzenesulfonamide) (1)

2.1.3. 4,5-(4-Methylbenzenesulfonamido)benzene-1,2-diaminium dichloride (1·2HCl)

2.1.4. 2,2,4-Trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepine (2)

2.1.5. 2,2,4-Trimethyl-8,9-bis(4-methylbenzenesulfonamido)-2,3-dihydro-5H-1,5-benzodiazepin-1-ium chloride 0.3-hydrate (3)