2,4-Di­aryl­pyrroles: synthesis, characterization and crystallographic insights

Farfán-Paredes, M.; Santillan, R.

doi:10.1107/S2053229624007277

crystallography in latin america

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 9| September 2024| Pages 472-477

https://doi.org/10.1107/S2053229624007277

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2,4-Diarylpyrroles: synthesis, characterization and crystallographic insights

Mónica Farfán-Paredes ^a ^* and Rosa Santillan ^a

^aDepartamento de Química, Centro de Investigación y de Estudios Avanzados del IPN, 07360, Apartado Postal 14-740, CDMX, Mexico
^*Correspondence e-mail: monica.farfan@cinvestav.mx

Edited by M. Rosales-Hoz, Cinvestav, Mexico (Received 8 June 2024; accepted 22 July 2024; online 8 August 2024)

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

Three 2,4-diarylpyrroles were synthesized starting from 4-nitrobutanones and the crystal structures of two derivatives were analysed. These are 4-(4-methoxyphenyl)-2-(thiophen-2-yl)-1H-pyrrole, C₁₅H₁₃NOS, and 3-(4-bromophenyl)-2-nitroso-5-phenyl-1H-pyrrole, C₁₆H₁₁BrN₂O. Although pyrroles without substituents at the α-position with respect to the N atom are very air sensitive and tend to polymerize, we succeeded in growing an adequate crystal for X-ray diffraction analysis. Further derivatization using sodium nitrite afforded a nitrosyl pyrrole derivative, which crystallized in the triclinic space group P $[\overline{1}]$ with Z = 6. Thus, herein we report the first crystal structure of a nitrosyl pyrrole. Interestingly, the co-operative hydrogen bonds in this NO-substituted pyrrole lead to a trimeric structure with bifurcated halogen bonds at the ends, forming a two-dimensional (2D) layer with interstitial voids having a radius of 5 Å, similar to some reported macrocyclic porphyrins.

Keywords: pyrrole; hydrogen bond; halogen bond; heterocycle; crystal structure; interstitial void.

CCDC references: 2361143; 2361144

1. Introduction

Pyrrole, a five-membered aromatic heterocyclic ring, serves as a pivotal building block for numerous biologically active compounds (Sajesh et al., 2013 ). While it oxidizes readily to a black colour when exposed to air, pyrrole exhibits lower basicity compared to aliphatic amines and other aromatic compounds. Pyrrole analogues are found in various natural products and co-factors, including vitamin B12, bile pigments and porphyrins (Carcel et al., 2004 ; Osman et al., 2021 ; Senge et al., 2010 ). Pyrrole derivatives exhibit a wide array of pharmacological activities, including anticancer, antimalarial, antituberculosis, antiviral, antibacterial, anti-Parkinsonian and anti-Alzheimer's effects (Domagala et al., 2015 ). Their diverse biological functions make pyrrole an essential target in drug discovery and development (Ganesh et al., 2024 ).

Incorporating heterocyclic moieties into pyrrole scaffolds results in synergistic effects and increased bioactivity, leading to the development of diverse pyrrole analogues. Nitrogen heterocycles are of considerable importance due to their ability to act as ligands in coordination chemistry; in addition, the pyrrolic N—H group can act as a hydrogen donor in supramolecular interactions with different heteroatoms (Guo et al., 2016 ). We have recently explored the synthesis and characterization of 2,4-disubstituted pyrroles, which have become essential building blocks to obtain dipyrromethanes and azadipyrromethenes for a wide variety of optical applications (Rogers, 1943 ; Poirel et al., 2012 ). One of the pyrroles was converted to the corresponding 2-nitroso-3,5-diaryl derivatives by reaction with sodium nitrite. All new compounds were characterized by spectroscopic techniques and X-ray diffraction analysis. To our knowledge, few X-ray crystal structures of these pyrrole derivatives (Chang et al., 2021 ; Chen et al., 2012 ; Chethan et al., 2020 )) have been reported. The crystal structure of a stable nitrosyl pyrrole is reported for the first-time [3-(4-bromophenyl)-2-nitroso-5-phenyl-1H-pyrrole, 4], evidencing that the introduction of the NO group increases the hydrogen-bond interactions, leading to a trimeric structure with an interesting 2D arrangement. The crystal structure of the intermediate 4-(4-methoxyphenyl)-2-(thiophen-2-yl)-1H-pyrrole, 3a, is also reported (Fig. 1).

Figure 1
Synthetic methodology for the preparation of 2,4-diarylpyrroles 3a/3b and nitrosyl pyrrole 4.

2. Experimental

The chemicals used for the synthesis were of reagent grade and were used without further purification. Solvents were distilled using standard procedures. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL 500 spectrometer. Chemical shifts (δ) for ¹H and ¹³C NMR spectra are referenced relative to the residual protonated solvent and are given in parts per million (ppm) and the coupling constants (J) are given in Hertz (Hz). IR spectra were recorded on a VARIAN 640-IR FT–IR spectrometer. High-resolution mass spectra were acquired on a Thermo Fisher Scientific Omnitrap LC–MS instrument. Thermogravimetric analysis was performed with an SDT instrument Q600 in the temperature range 25–200 °C, with a heating rate of 2 °C min⁻¹ under a nitrogen atmosphere.

2.1. Synthesis and crystallization

α,β-Unsaturated ketones, also known as chalcones 1a/1b and diarylnitrobutanones 2a/2b, were synthesized following the methodology reported by O'Shea (Hall et al., 2005 ); the spectroscopic data are in accordance with the literature [Jeong & Lee (2019 ) for 1a, Li et al. (2019 ) for 2a and Hall et al. (2005) for 1b and 2b]. Fig. 1 shows the synthetic procedure for the pyrroles starting from the corresponding chalcones. To synthesize pyrrole 3a, the corresponding diarylnitrobutanone 2a was deprotonated with potassium hydroxide in methanol/tetrahydrofuran (MeOH/THF), then hydrolysis with sulfuric acid gave the 1-keto-4-dimethyl acetal, and deprotection and condensation with ammonium acetate in acetic acid provided the 2,4-diarylpyrrole 3a in 20% yield after purification. The same procedure was used to obtain pyrrole 3b, starting from the disubstituted nitrobutanone 2b, with a 60% yield, and the spectra agree with the literature (Hall et al., 2005). Nitrosyl pyrrole 4 was synthesized starting from 3b, following a described synthetic procedure using NaNO₂ in the presence of HCl (Hall et al., 2005). After chromatographic purification over silica gel, nitrosyl pyrrole 4 was isolated as a green solid in 83% yield.

Pyrrole 3a was crystallized from hexane/ethyl acetate and nitrosyl pyrrole 4 was crystallized from hexane/acetone/dichloromethane. Crystals of 3a are air sensitive and become green after 2 d, so the sample must be collected immediately after crystallization because the green colour is indicative of decomposition, as evidenced by NMR spectroscopy. In the case of 4, the crystals were stable and an adequate single crystal of the sample was obtained by slow evaporation of the solvent.

2.1.1. Preparation of 4-(4-methoxyphenyl)-2-(thiophen-2-yl)-1H-pyrrole (3a)

A stirred solution of diaryl nitro ketone 2a (2 mmol) in MeOH/THF (1:2 v/v) at room temperature was treated with KOH (10 mmol). After 1 h, the mixture was added dropwise to a solution of H₂SO₄ (4 ml) in MeOH (10 ml) at 0 °C, the solution was allowed to warm to room temperature and was stirred for a further 1 h. Water and ice were added, and the mixture was neutralized with aqueous 4 M NaOH and extracted with dichloromethane. The organic phase was dried over Na₂SO₄ and evaporated to provide the dimethyl acetal intermediate, which was carried forward to the next stage without further purification. The acetal was treated with acetic acid (5 ml) and NH₄OAc (10 mmol), and the resulting mixture was heated at 100 °C for 1 h. The reaction was cooled to room temperature, ice was added and the mixture was carefully neutralized with aqueous 4 M NaOH and extracted with dichloromethane. The combined extracts were washed with water, dried over Na₂SO₄ and evaporated. The product was purified by column chromatography on silica gel (previously deactivated) using hexane/ethyl acetate (9:1 v/v), affording the pyrrole as yellow crystals (20% yield; m.p. 169 °C). ¹H NMR (500 MHz, DMSO-d₆): δ (ppm) 11.39 (s, 1H, NH), 7.50 (d, J = 8.6 Hz, 2H, H-9), 7.33 (d, J = 4.6 Hz, 1H, H-1), 7.25 (d, J = 3.4 Hz, 1H, H-3), 7.19 (bs, 1H, H-13), 7.04 (dd, J = 4.6, 3.4 Hz, 1H, H-2), 6.89 (d, J = 8.6 Hz, 2H, H-10), 6.62 (bs, 1H, H-6), 3.74 (s, 3H, H-12). ¹³C NMR (125 MHz, DMSO-d₆): δ (ppm) 157.20, 136.28, 128.14, 127.81, 126.97, 125.63, 124.47, 122.65, 120.80, 115.36, 114.04, 103.29, 55.03. FT–IR (cm⁻¹): 3401 ν(N—H), 3101 ν(C—H) (thiophene); 2832 (sp³-C—H), 1583 ν(C=C). ESI–HRMS: m/z calculated for C₁₅H₁₄NOS [M + H]⁺: 256.0796; found: 256.0782, error: 5 ppm.

2.1.2. Preparation of 3-(4-bromophenyl)-2-nitroso-5-phenyl-1H-pyrrole (4)

To a stirred solution of pyrrole 3b (1 mmol) in EtOH (15 ml) was added concentrated HCl (0.2 ml), followed by the addition of aqueous NaNO₂ (1.2 mmol in 2 ml of H₂O). The reaction mixture was stirred for 30 min and cooled to 0 °C, and another portion of concentrated HCl (1 ml) was added. The solution was stirred for 1 h. The product was extracted with dichloromethane (DCM), washed with water, and the organic layer was dried over Na₂SO₄ and evaporated. The solid was dissolved in a minimum quantity of EtOH, an excess of aqueous NaOAc and ice was added, and the solution was stirred for 1 h. The resulting solid was collected by filtration and purified by column chromatography on silica gel using hexane/acetone (85:15 v/v), affording the pyrrole as green crystals (83% yield; m.p. 159–161 °C). ¹H NMR (500 MHz, CDCl₃): δ (ppm) 8.04 (d, J = 8.0 Hz, 2H, H-10), 7.81 (d, J = 7.9 Hz, 2H, H-3), 7.60 (d, J = 8.0 Hz, 2H, H-9), 7.50 (m, 3H, H-1, H-2), 7.10 (s, 1H, H-6). ¹³C NMR (101 MHz, CDCl₃): δ (ppm) 162.54, 147.59, 140.19, 132.12, 131.46, 131.15, 130.95, 129.51, 129.00, 127.04, 124.40, 112.38. FT–IR (cm⁻¹): 3438 ν(N—H), 1587 ν(N=O), 1454 ν(C—NO). ESI–HRMS: m/z calculated for C₁₆H₁₂BrN₂O [M + H]⁺: 327.0133; found: 327.0143, error: 3 ppm.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were set geometrically and constrained to ride on their associated atoms. For nitrosyl pyrrole 4, the crystal structure data were analysed with PLATON (Spek, 2020 ) and treated using the SQUEEZE routine (Spek, 2015 ).

Table 1
Experimental details

Experiments were carried out with Mo Kα radiation using a Bruker APEXII diffractometer. Absorption was corrected for by multi-scan methods (SADABS; Bruker, 2016 ). H atoms were treated by a mixture of independent and constrained refinement.

	3a	4
Crystal data
Chemical formula	C₁₅H₁₃NOS	C₁₆H₁₁BrN₂O + [solvent]
M_r	255.32	327.18
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P $[\overline{1}]$
Temperature (K)	296	297
a, b, c (Å)	7.4695 (11), 5.7626 (7), 28.907 (4)	10.2533 (19), 14.689 (3), 17.003 (3)
α, β, γ (°)	90, 93.662 (5), 90	104.713 (6), 91.812 (6), 101.544 (6)
V (Å³)	1241.7 (3)	2417.5 (8)
Z	4	6
μ (mm⁻¹)	0.25	2.55
Crystal size (mm)	0.29 × 0.15 × 0.06	0.23 × 0.19 × 0.14

Data collection
T_min, T_max	0.702, 0.746	0.666, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	52264, 2985, 1981	134671, 11584, 6774
R_int	0.075	0.082
(sin θ/λ)_max (Å⁻¹)	0.690	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.208, 1.04	0.056, 0.175, 1.03
No. of reflections	2985	11584
No. of parameters	195	547
No. of restraints	177	0
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.60	0.59, −0.69
Computer programs: APEX2 (Bruker, 2016), SAINT (Bruker, 2016), SORTAV (Blessing, 1995 ), SHELXT (Sheldrick, 2015a ), SHELXL2019 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ) and WinGX (Farrugia, 2012).

3. Results and discussion

Despite the sensitivity of pyrrole 3a, it was possible to obtain an adequate crystal for X-ray diffraction analysis. The compound crystallized in the monoclinic space group P2₁/c with Z = 4. The molecule is nearly planar, with dihedral angles between the pyrrole and thiophene planes of 1.30° (N1—C1—C12—C13), and between the pyrrole and arene planes of 6.69° (C4—C3—C5—C10). The molecular structure with the corresponding numbering of atoms is shown in Fig. 2.

Figure 2
The molecular structure of pyrrole 3a, with displacement ellipsoids drawn at the 30% probability level.

Compound 3a showed disorder in the thiophene unit which was treated over two sites. Appropriate restraints and constraints on the displacement parameters were added to ensure that the structure approximated normal behaviour. The crystal packing shows hydrogen bonding between the thienyl moiety and the O atom of the methoxy group (C14—H⋯O1, with H14⋯O2 = 2.64 Å and C14—H14⋯O2 = 163°) that maintains a linear arrangement along the c axis, and C13—H⋯π interactions that maintain the packing along the crystallographic a axis, with the molecules in an antiparallel disposition (Fig. 3). The antiparallel arrangement of the molecules generates zigzag layers, as shown in Fig. 4.

Figure 3
The crystal packing of pyrrole 3a, with a linear arrangement along the crystallographic c axis.

Figure 4
Zigzag layers observed in the crystal packing of pyrrole 3a.

Nitrosyl pyrrole 4 crystallized in the triclinic space group P $[\overline{1}]$ with Z = 6. Three individual molecules are found within the asymmetric unit (Fig. 5). The dihedral angle between the planes of the pyrrole and phenyl rings is 11.45° (N1—C4—C5—C6), and between the pyrrole and 4-bromophenyl planes is 35.61° (C3—C2—C11—C16). The arrangement of nitrosyl pyrrole 4 is quite interesting because of the high number of interactions present in the crystal. The strongest hydrogen bond is N3—H3A⋯O1, with H⋯O = 2.10 Å and N—H⋯O = 171°, but there are also C—H⋯O (mean H⋯O = 2.68 Å and mean C—H⋯O = 155°) and C—H⋯N (mean H⋯N = 2.48 Å and mean C—H⋯N = 152°) hydrogen bonds that maintain the packing between three molecules with the nitrosyl groups pointing towards the centre of the motif (Table 2). The N and O atoms of the nitrosyl group participate as acceptors, and there are bifurcated hydrogen bonds. Additionally, bifurcated Br⋯Br halogen bonds, with a mean distance of 3.63 Å, maintain the motifs in a 2D planar arrangement, as shown in Fig. 6. The 2D layers are held together by π–π interactions in a slip-stacked geometry, with a distance of 3.34 Å between the planes (Fig. 7). The expanded arrangement of the 2D layers forms voids in the shape of triangles where solvent molecules can be embedded (Fig. 8). Refinement of 4 proceeded smoothly to an R value of 12%. However, there was disordered solvent present in the lattice. Assessment of the structure and use of the SQUEEZE routine facilitated a final convergence with an R factor of 5.6%. The crystal structure contains solvent channels that are ∼18% of the unit-cell volume (441 Å³ of the unit-cell volume of 2417 Å³). The SQUEEZE results revealed 103 electrons in the solvent-accessible volume, the possible solvent trapped in the voids may be acetone.

Table 2
Hydrogen-bond geometry (Å, °) for 4

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.86	2.10	2.957 (5)	177
N3—H3A⋯O1	0.86	2.10	2.956 (5)	171
N5—H5⋯O2	0.86	2.16	3.009 (5)	169
C6—H6⋯N6	0.93	2.53	3.294 (6)	139
C26—H26⋯N2	0.93	2.43	3.338 (7)	165
C38—H38⋯N4	0.93	2.48	3.331 (6)	153
C6—H6⋯O3	0.93	2.69	3.505 (6)	146
C26—H26⋯O1	0.93	2.43	3.543 (6)	165
C38—H38⋯O2	0.93	2.72	3.564 (6)	151

Figure 5
The molecular structure of pyrrole 4, with displacement ellipsoids drawn at the 30% probability level.

Figure 6
Hydrogen and halogen bonds leading to the 2D layer in compound 4.

Figure 7
The molecules of pyrrole 4 forming π–π interactions with a slip-stacked geometry and a distance between the planes of 3.34 Å.

Figure 8
2D arrangement in (a) capped sticks and (b) space-filling representations, showing the voids in the lattice of pyrrole 4.

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements of compound 4 indicated no significant solvent loss until the onset of melting at 159159 °C. The TGA and DSC diagrams are available in the supporting information.

In the literature, there is a report on a cyclo[n]pyrrole that forms a macrocycle with all the pyrrole N—H groups pointing inwards towards the centre of the cavity. The largest radius r = 4.6 Å involves the N atoms and is larger than the previous congeners (Bui et al., 2013 ). Generally, the size of the macrocyclic cavity is a key parameter that defines many of the properties of expanded porphyrins. In the nitrosyl pyrrole presented here, the 2D lattice has a cavity with similar radius (r = 5 Å) (Fig. 9), but, in this case, there are only C—H groups instead of N—H groups as in pyrrolic macrocycles; thus, this cavity can accommodate molecules through weak interactions.

Figure 9
Representation of the radii that define the cavity in the arrangement of 4.

4. Summary conclusions

In summary, we have provided crystallographic structural evidence of a 2,4-diarylpyrrole and a nitrosyl pyrrole. The first showed a linear arrangement along the crystallographic c axis without involving the pyrrolic N—H group in the intermolecular interactions, while the nitrosyl pyrrole showed multiple hydrogen bonds involving the pyrrolic N—H group in strong hydrogen bonds. The N and O atoms of the nitrosyl group participate as acceptors and these intermolecular interactions maintain the nitrosyl groups pointing inwards towards the centre of three molecules. This motif is extended by Br⋯Br halogen bonds which form a 2D structure with interstitial voids having a radius of 5 Å.

Supporting information

CCDC references: 2361143; 2361144

Crystal structure: contains datablocks 3a, 4, global. DOI: https://doi.org/10.1107/S2053229624007277/zo3053sup1.cif

Structure factors: contains datablock 3a. DOI: https://doi.org/10.1107/S2053229624007277/zo30533asup2.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2053229624007277/zo30534sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229624007277/zo30533asup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229624007277/zo30534sup5.cml

NMR spectra, DSC curves and geometry information. DOI: https://doi.org/10.1107/S2053229624007277/zo3053sup6.pdf

Computing details top

4-(4-Methoxyphenyl)-2-(thiophen-2-yl)-1H-pyrrole (3a) top

Crystal data top

C₁₅H₁₃NOS	F(000) = 536
M_r = 255.32	D_x = 1.366 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9266 reflections
a = 7.4695 (11) Å	θ = 2.7–24.9°
b = 5.7626 (7) Å	µ = 0.25 mm⁻¹
c = 28.907 (4) Å	T = 296 K
β = 93.662 (5)°	Plate, yellow
V = 1241.7 (3) Å³	0.29 × 0.15 × 0.06 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2985 independent reflections
Radiation source: sealed x-ray tube	1981 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
φ or ω oscillation scans	θ_max = 29.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −9→9
T_min = 0.702, T_max = 0.746	k = −7→7
52264 measured reflections	l = −39→37

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.071	w = 1/[σ²(F_o²) + (0.1237P)² + 0.3542P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.208	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.57 e Å⁻³
2985 reflections	Δρ_min = −0.59 e Å⁻³
195 parameters	Extinction correction: SHELXL2019 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
177 restraints	Extinction coefficient: 0.113 (13)
0 constraints

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)
O2	0.8488 (3)	0.4150 (3)	0.44624 (6)	0.0627 (5)
C1	0.7263 (3)	0.2441 (4)	0.17693 (9)	0.0462 (6)
C2	0.6970 (3)	0.3508 (4)	0.21820 (8)	0.0470 (6)
H2	0.643701	0.495168	0.221474	0.056*
C3	0.7615 (3)	0.2045 (4)	0.25504 (8)	0.0437 (5)
C4	0.8265 (4)	0.0098 (4)	0.23438 (9)	0.0562 (7)
H4	0.876483	−0.118433	0.249863	0.067*
C5	0.7738 (3)	0.2574 (4)	0.30487 (8)	0.0438 (6)
C6	0.6995 (3)	0.4580 (4)	0.32227 (9)	0.0497 (6)
H6	0.63354	0.555533	0.302013	0.06*
C7	0.7205 (3)	0.5179 (4)	0.36887 (9)	0.0520 (6)
H7	0.668373	0.652678	0.379539	0.062*
C8	0.8194 (3)	0.3754 (4)	0.39915 (8)	0.0478 (6)
C9	0.8950 (3)	0.1751 (4)	0.38279 (9)	0.0532 (6)
H9	0.961225	0.078386	0.403156	0.064*
C10	0.8730 (3)	0.1179 (4)	0.33661 (9)	0.0502 (6)
H10	0.925533	−0.017198	0.326245	0.06*
C11	0.7810 (5)	0.6229 (5)	0.46406 (11)	0.0725 (8)
H11A	0.829792	0.752819	0.448315	0.109*
H11B	0.814548	0.633209	0.496613	0.109*
H11C	0.652637	0.624096	0.459379	0.109*
N1	0.8057 (3)	0.0353 (4)	0.18772 (8)	0.0575 (6)
H1	0.821 (5)	−0.058 (6)	0.1711 (13)	0.086*
C12	0.699 (4)	0.341 (4)	0.1314 (4)	0.041 (3)	0.5
C13	0.766 (3)	0.207 (3)	0.0898 (5)	0.0593 (15)	0.5
H13	0.828894	0.068114	0.090437	0.071*	0.5
C14	0.7077 (18)	0.3477 (18)	0.0486 (5)	0.0593 (15)	0.5
H14	0.730966	0.305849	0.018525	0.071*	0.5
C15	0.618 (2)	0.541 (2)	0.0589 (3)	0.063 (2)	0.5
H15	0.576746	0.650797	0.037139	0.075*	0.5
S1	0.5896 (8)	0.5614 (8)	0.11682 (18)	0.0691 (7)	0.5
C12A	0.694 (5)	0.306 (4)	0.1276 (4)	0.048 (4)	0.5
C13A	0.611 (3)	0.543 (3)	0.1195 (6)	0.0593 (15)	0.5
H13A	0.574746	0.647517	0.141495	0.071*	0.5
C14A	0.602 (2)	0.569 (3)	0.0685 (4)	0.0593 (15)	0.5
H14A	0.54185	0.691536	0.053536	0.071*	0.5
C15A	0.6868 (17)	0.4046 (15)	0.0452 (4)	0.0575 (18)	0.5
H15A	0.698297	0.404653	0.013303	0.069*	0.5
S1A	0.7714 (6)	0.1927 (7)	0.08301 (10)	0.0504 (5)	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0738 (13)	0.0640 (11)	0.0503 (10)	0.0101 (10)	0.0038 (9)	0.0027 (8)
C1	0.0381 (11)	0.0441 (12)	0.0566 (14)	−0.0047 (9)	0.0043 (10)	−0.0024 (10)
C2	0.0434 (12)	0.0429 (11)	0.0547 (14)	0.0011 (9)	0.0035 (10)	−0.0010 (10)
C3	0.0364 (11)	0.0412 (11)	0.0537 (13)	−0.0017 (9)	0.0047 (9)	0.0011 (9)
C4	0.0593 (15)	0.0466 (13)	0.0625 (16)	0.0107 (11)	0.0029 (12)	−0.0004 (11)
C5	0.0360 (11)	0.0397 (11)	0.0564 (14)	−0.0008 (9)	0.0074 (9)	0.0063 (10)
C6	0.0485 (13)	0.0474 (13)	0.0533 (14)	0.0122 (10)	0.0036 (10)	0.0054 (10)
C7	0.0515 (14)	0.0462 (12)	0.0586 (15)	0.0095 (10)	0.0070 (11)	0.0032 (10)
C8	0.0442 (12)	0.0492 (12)	0.0504 (13)	0.0007 (10)	0.0069 (10)	0.0053 (10)
C9	0.0514 (14)	0.0476 (13)	0.0606 (15)	0.0091 (10)	0.0026 (11)	0.0126 (11)
C10	0.0508 (13)	0.0411 (11)	0.0591 (15)	0.0092 (10)	0.0075 (11)	0.0037 (10)
C11	0.087 (2)	0.0721 (18)	0.0593 (17)	0.0114 (16)	0.0148 (15)	−0.0067 (14)
N1	0.0662 (14)	0.0498 (12)	0.0567 (14)	0.0092 (10)	0.0053 (11)	−0.0085 (9)
C12	0.037 (5)	0.036 (5)	0.049 (4)	−0.008 (5)	0.001 (3)	−0.015 (3)
C13	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C14	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C15	0.075 (5)	0.065 (5)	0.047 (4)	−0.004 (4)	−0.009 (4)	0.011 (4)
S1	0.0677 (17)	0.0677 (13)	0.0712 (13)	0.0068 (9)	−0.0013 (11)	0.0083 (10)
C12A	0.046 (5)	0.048 (8)	0.051 (4)	−0.018 (5)	0.005 (5)	−0.007 (5)
C13A	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C14A	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C15A	0.069 (4)	0.049 (5)	0.054 (3)	0.005 (4)	−0.003 (3)	0.001 (3)
S1A	0.0583 (9)	0.0494 (9)	0.0439 (11)	0.0004 (7)	0.0058 (8)	−0.0096 (8)

Geometric parameters (Å, º) top

O2—C8	1.384 (3)	C10—H10	0.93
O2—C11	1.411 (3)	C11—H11A	0.96
C1—N1	1.368 (3)	C11—H11B	0.96
C1—C2	1.372 (3)	C11—H11C	0.96
C1—C12	1.433 (8)	N1—H1	0.73 (4)
C1—C12A	1.474 (9)	C12—C13	1.54 (2)
C2—C3	1.418 (3)	C12—S1	1.554 (18)
C2—H2	0.93	C13—C14	1.482 (17)
C3—C4	1.374 (3)	C13—H13	0.93
C3—C5	1.469 (3)	C14—C15	1.344 (8)
C4—N1	1.356 (4)	C14—H14	0.93
C4—H4	0.93	C15—S1	1.705 (8)
C5—C6	1.390 (3)	C15—H15	0.93
C5—C10	1.396 (3)	C12A—C13A	1.51 (2)
C6—C7	1.390 (4)	C12A—S1A	1.59 (2)
C6—H6	0.93	C13A—C14A	1.481 (16)
C7—C8	1.380 (3)	C13A—H13A	0.93
C7—H7	0.93	C14A—C15A	1.344 (8)
C8—C9	1.381 (3)	C14A—H14A	0.93
C9—C10	1.375 (4)	C15A—S1A	1.732 (7)
C9—H9	0.93	C15A—H15A	0.93

C8—O2—C11	117.5 (2)	O2—C11—H11B	109.5
N1—C1—C2	106.7 (2)	H11A—C11—H11B	109.5
N1—C1—C12	125.9 (9)	O2—C11—H11C	109.5
C2—C1—C12	127.1 (9)	H11A—C11—H11C	109.5
N1—C1—C12A	118.4 (10)	H11B—C11—H11C	109.5
C2—C1—C12A	134.9 (10)	C4—N1—C1	110.0 (2)
C1—C2—C3	108.7 (2)	C4—N1—H1	124 (3)
C1—C2—H2	125.6	C1—N1—H1	125 (3)
C3—C2—H2	125.6	C1—C12—C13	119.3 (15)
C4—C3—C2	105.7 (2)	C1—C12—S1	127.5 (15)
C4—C3—C5	126.4 (2)	C13—C12—S1	112.9 (7)
C2—C3—C5	127.6 (2)	C14—C13—C12	105.2 (14)
N1—C4—C3	108.8 (2)	C14—C13—H13	127.4
N1—C4—H4	125.6	C12—C13—H13	127.4
C3—C4—H4	125.6	C15—C14—C13	113.5 (15)
C6—C5—C10	116.6 (2)	C15—C14—H14	123.2
C6—C5—C3	121.7 (2)	C13—C14—H14	123.2
C10—C5—C3	121.5 (2)	C14—C15—S1	111.6 (12)
C7—C6—C5	122.3 (2)	C14—C15—H15	124.2
C7—C6—H6	118.8	S1—C15—H15	124.2
C5—C6—H6	118.8	C12—S1—C15	96.5 (8)
C8—C7—C6	119.3 (2)	C1—C12A—C13A	114.2 (16)
C8—C7—H7	120.4	C1—C12A—S1A	129.7 (17)
C6—C7—H7	120.4	C13A—C12A—S1A	114.4 (7)
C7—C8—C9	119.6 (2)	C14A—C13A—C12A	103.9 (14)
C7—C8—O2	124.8 (2)	C14A—C13A—H13A	128.1
C9—C8—O2	115.6 (2)	C12A—C13A—H13A	128.1
C10—C9—C8	120.5 (2)	C15A—C14A—C13A	115.8 (15)
C10—C9—H9	119.8	C15A—C14A—H14A	122.1
C8—C9—H9	119.8	C13A—C14A—H14A	122.1
C9—C10—C5	121.7 (2)	C14A—C15A—S1A	110.1 (13)
C9—C10—H10	119.1	C14A—C15A—H15A	124.9
C5—C10—H10	119.1	S1A—C15A—H15A	124.9
O2—C11—H11A	109.5	C12A—S1A—C15A	94.9 (7)

N1—C1—C2—C3	0.5 (3)	C12—C1—N1—C4	173.4 (18)
C12—C1—C2—C3	−172.9 (18)	C12A—C1—N1—C4	179.3 (17)
C12A—C1—C2—C3	−179 (2)	N1—C1—C12—C13	−1 (3)
C1—C2—C3—C4	−0.8 (3)	C2—C1—C12—C13	171.1 (16)
C1—C2—C3—C5	173.6 (2)	N1—C1—C12—S1	171.8 (17)
C2—C3—C4—N1	0.8 (3)	C2—C1—C12—S1	−16 (4)
C5—C3—C4—N1	−173.7 (2)	C1—C12—C13—C14	177 (2)
C4—C3—C5—C6	−178.5 (2)	S1—C12—C13—C14	3 (3)
C2—C3—C5—C6	8.2 (4)	C12—C13—C14—C15	0 (2)
C4—C3—C5—C10	6.7 (4)	C13—C14—C15—S1	−2.6 (16)
C2—C3—C5—C10	−166.6 (2)	C1—C12—S1—C15	−177 (3)
C10—C5—C6—C7	−0.6 (4)	C13—C12—S1—C15	−4 (2)
C3—C5—C6—C7	−175.6 (2)	C14—C15—S1—C12	4.0 (18)
C5—C6—C7—C8	0.5 (4)	N1—C1—C12A—C13A	−178.1 (18)
C6—C7—C8—C9	−0.4 (4)	C2—C1—C12A—C13A	1 (4)
C6—C7—C8—O2	−179.5 (2)	N1—C1—C12A—S1A	−14 (4)
C11—O2—C8—C7	−3.7 (4)	C2—C1—C12A—S1A	165.0 (15)
C11—O2—C8—C9	177.2 (2)	C1—C12A—C13A—C14A	177 (2)
C7—C8—C9—C10	0.3 (4)	S1A—C12A—C13A—C14A	10 (3)
O2—C8—C9—C10	179.5 (2)	C12A—C13A—C14A—C15A	−9 (3)
C8—C9—C10—C5	−0.4 (4)	C13A—C14A—C15A—S1A	4.2 (18)
C6—C5—C10—C9	0.5 (4)	C1—C12A—S1A—C15A	−171 (3)
C3—C5—C10—C9	175.5 (2)	C13A—C12A—S1A—C15A	−8 (3)
C3—C4—N1—C1	−0.5 (3)	C14A—C15A—S1A—C12A	2.1 (17)
C2—C1—N1—C4	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···S1Abⁱ	0.93	3	3.821 (5)	148
C14a—H14a···O2ⁱⁱ	0.93	2.64	3.544 (14)	163

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

3-(4-Bromophenyl)-2-nitroso-5-phenyl-1H-pyrrole (4) top

Crystal data top

C₁₆H₁₁BrN₂O⁺[solvent]	Z = 6
M_r = 327.18	F(000) = 984
Triclinic, P1	D_x = 1.348 Mg m⁻³
a = 10.2533 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.689 (3) Å	Cell parameters from 9924 reflections
c = 17.003 (3) Å	θ = 2.2–25.0°
α = 104.713 (6)°	µ = 2.55 mm⁻¹
β = 91.812 (6)°	T = 297 K
γ = 101.544 (6)°	Prism, green
V = 2417.5 (8) Å³	0.23 × 0.19 × 0.14 mm

Data collection top

Bruker APEXII diffractometer	6774 reflections with I > 2σ(I)
Radiation source: sealed x-ray tube	R_int = 0.082
φ or ω oscillation scans	θ_max = 27.9°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −13→13
T_min = 0.666, T_max = 0.746	k = −19→19
134671 measured reflections	l = −22→22
11584 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.175	w = 1/[σ²(F_o²) + (0.083P)² + 2.0664P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
11584 reflections	Δρ_max = 0.59 e Å⁻³
547 parameters	Δρ_min = −0.69 e Å⁻³

Special details top

Refinement. X-ray crystallographic data was obtained using a Bruker APEXII diffractometer with a CCD area detector (Mo Kα = 0.71073 Å, monochromator: graphite). Indexing, data integration and reduction were carried out using APEX5. All reflection data set were corrected for polarization effects. The structures were solved in the WinGX (Farrugia, 2012) suite of programs by intrinsic phasing using SHELXT (Sheldrick, 2015b) and refined using full-matrix least-squares/difference Fourier techniques on F² using SHELXL (Sheldrick, 2015b). All non-H atoms were refined using anisotropic displacement parameters. H atoms were set geometrically and constrained to ride on their associated atoms. Mercury (Macrae et al., 2020) and ORTEP-3 (Farrugia, 2012) programs were used to prepare artwork representations. For the nitrosylpyrrole 4, crystal structure data was analysed with PLATON (Spek, 2020) and treated using the SQUEEZE routine (Spek, 2015). Table 1 summarizes crystallographic data and structure refinement details. The crystal structures have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under numbers 2361143 (3a) and 2361144 (4). Copies can be obtained on request, free of charge via www.ccdc.cam.ac.uk/data_request/cif or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223-336-033 or email: deposit@ccdc.cam.ac.uk).

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

	x	y	z	U_iso*/U_eq
Br2	−0.08774 (5)	0.83243 (4)	0.07627 (3)	0.07290 (17)
O1	0.5893 (3)	0.5229 (3)	0.3902 (2)	0.0746 (9)
N1	0.7207 (3)	0.3801 (2)	0.3834 (2)	0.0524 (8)
H1	0.675942	0.370253	0.337264	0.070 (14)*
O2	0.4417 (3)	0.5365 (2)	0.23024 (19)	0.0694 (8)
N2	0.6565 (4)	0.5269 (3)	0.4560 (2)	0.0599 (9)
O3	0.5655 (4)	0.3533 (3)	0.22658 (19)	0.0781 (10)
N3	0.4408 (3)	0.6705 (2)	0.3723 (2)	0.0535 (8)
H3A	0.491460	0.632948	0.380118	0.055 (12)*
N4	0.3655 (4)	0.5943 (3)	0.2278 (2)	0.0586 (9)
C4	0.8035 (4)	0.3256 (3)	0.3998 (2)	0.0509 (9)
N5	0.4513 (3)	0.3696 (3)	0.0866 (2)	0.0551 (8)
H5	0.436773	0.414550	0.126733	0.050 (12)*
C5	0.8339 (4)	0.2431 (3)	0.3414 (2)	0.0517 (10)
N6	0.5761 (4)	0.2899 (3)	0.1613 (2)	0.0615 (9)
C6	0.7506 (5)	0.1935 (3)	0.2713 (3)	0.0657 (12)
H6	0.672650	0.213203	0.260610	0.093 (18)*
C7	0.7825 (6)	0.1156 (4)	0.2174 (3)	0.0752 (14)
H7	0.726092	0.082734	0.170558	0.090*
C8	0.8970 (6)	0.0867 (4)	0.2326 (3)	0.0835 (16)
H8	0.916699	0.032853	0.196704	0.100*
C10	0.9503 (5)	0.2133 (4)	0.3546 (3)	0.0790 (15)
H10	1.008040	0.245748	0.400944	0.095*
C9	0.9815 (6)	0.1348 (4)	0.2987 (4)	0.0933 (19)
H9	1.060823	0.115707	0.307250	0.112*
C2	0.8050 (4)	0.4434 (3)	0.5154 (2)	0.0503 (9)
C3	0.8561 (4)	0.3645 (3)	0.4816 (2)	0.0537 (10)
H3	0.916215	0.340440	0.508433	0.064*
Br3	0.78367 (6)	−0.10641 (4)	−0.10174 (3)	0.07482 (18)
Br1	0.93593 (6)	0.68790 (4)	0.87090 (3)	0.07679 (18)
C1	0.7187 (4)	0.4539 (3)	0.4515 (2)	0.0514 (9)
C15	0.7772 (4)	0.6114 (3)	0.7204 (3)	0.0594 (11)
H15	0.717292	0.646307	0.746492	0.071*
C11	0.8340 (4)	0.5039 (3)	0.5999 (2)	0.0488 (9)
C12	0.9543 (4)	0.5076 (3)	0.6431 (3)	0.0570 (10)
H12	1.014629	0.472724	0.617435	0.068*
C13	0.9854 (4)	0.5626 (3)	0.7240 (3)	0.0607 (11)
H13	1.065614	0.564701	0.752222	0.073*
C14	0.8958 (4)	0.6132 (3)	0.7608 (2)	0.0549 (10)
C19	0.3331 (4)	0.7910 (3)	0.3921 (3)	0.0597 (11)
H19	0.304133	0.846355	0.417710	0.072*
C20	0.4206 (4)	0.7480 (3)	0.4276 (2)	0.0533 (10)
C21	0.4867 (4)	0.7827 (3)	0.5110 (3)	0.0559 (10)
C22	0.4693 (6)	0.8697 (4)	0.5629 (3)	0.0826 (16)
H22	0.412080	0.903277	0.544723	0.099*
C23	0.5339 (6)	0.9066 (4)	0.6393 (4)	0.0945 (19)
H23	0.522190	0.965085	0.671926	0.113*
C24	0.6159 (6)	0.8569 (5)	0.6675 (3)	0.0867 (17)
H24	0.658950	0.881183	0.719796	0.104*
C25	0.6346 (6)	0.7728 (4)	0.6197 (3)	0.0921 (18)
H25	0.691335	0.739823	0.639148	0.111*
C26	0.5697 (5)	0.7348 (4)	0.5414 (3)	0.0771 (15)
H26	0.582746	0.676319	0.509423	0.15 (3)*
C27	0.2070 (4)	0.7571 (3)	0.2526 (3)	0.0541 (10)
C28	0.2025 (5)	0.8520 (3)	0.2565 (3)	0.0725 (14)
H28	0.259026	0.901227	0.295722	0.087*
C29	0.1170 (5)	0.8762 (4)	0.2042 (3)	0.0729 (14)
H29	0.116050	0.940214	0.207445	0.087*
C30	0.0336 (4)	0.8020 (3)	0.1474 (3)	0.0576 (11)
C31	0.0339 (5)	0.7077 (3)	0.1418 (3)	0.0670 (12)
H31	−0.024196	0.658826	0.103272	0.080*
C32	0.1211 (5)	0.6856 (3)	0.1940 (3)	0.0658 (12)
H32	0.122096	0.621354	0.189660	0.079*
C33	0.5197 (4)	0.2997 (3)	0.0929 (3)	0.0528 (10)
C34	0.5222 (4)	0.2399 (3)	0.0133 (3)	0.0522 (10)
C35	0.4521 (4)	0.2754 (3)	−0.0387 (3)	0.0554 (10)
H35	0.435154	0.249895	−0.094879	0.067*
C36	0.4108 (4)	0.3565 (3)	0.0079 (2)	0.0522 (10)
C37	0.3393 (4)	0.4196 (3)	−0.0220 (3)	0.0552 (10)
C38	0.2857 (5)	0.4895 (4)	0.0295 (3)	0.0737 (14)
H38	0.293182	0.497464	0.085569	0.077 (15)*
C39	0.2206 (6)	0.5477 (4)	−0.0036 (3)	0.0815 (15)
H39	0.186430	0.595278	0.031320	0.098*
C40	0.2056 (5)	0.5370 (4)	−0.0848 (3)	0.0744 (14)
H40	0.157868	0.574628	−0.105366	0.089*
C41	0.2612 (5)	0.4703 (4)	−0.1367 (3)	0.0763 (14)
H41	0.254315	0.464447	−0.192492	0.092*
C42	0.3272 (5)	0.4121 (3)	−0.1060 (3)	0.0664 (12)
H42	0.364422	0.366969	−0.141686	0.080*
C43	0.5850 (4)	0.1570 (3)	−0.0115 (3)	0.0534 (10)
C44	0.7070 (4)	0.1543 (3)	0.0248 (3)	0.0586 (11)
H44	0.749689	0.205816	0.067868	0.070*
C45	0.7657 (4)	0.0771 (3)	−0.0016 (3)	0.0623 (11)
H45	0.847393	0.076283	0.023337	0.075*
C46	0.7029 (4)	0.0009 (3)	−0.0651 (3)	0.0547 (10)
C47	0.5820 (5)	0.0005 (3)	−0.1032 (3)	0.0633 (12)
H47	0.540250	−0.051404	−0.146205	0.076*
C48	0.5247 (4)	0.0782 (3)	−0.0763 (3)	0.0593 (11)
H48	0.443354	0.078566	−0.101862	0.071*
C16	0.7475 (4)	0.5568 (3)	0.6398 (3)	0.0573 (11)
H16	0.667349	0.555923	0.612201	0.069*
C17	0.3660 (4)	0.6610 (3)	0.3003 (2)	0.0519 (10)
C18	0.2973 (4)	0.7374 (3)	0.3129 (3)	0.0553 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br2	0.0766 (3)	0.0829 (3)	0.0596 (3)	0.0334 (3)	−0.0150 (2)	0.0098 (2)
O1	0.082 (2)	0.082 (2)	0.0625 (19)	0.0403 (18)	−0.0196 (17)	0.0095 (17)
N1	0.0536 (19)	0.055 (2)	0.0489 (19)	0.0203 (16)	−0.0061 (15)	0.0083 (15)
O2	0.083 (2)	0.071 (2)	0.0567 (18)	0.0339 (18)	0.0022 (16)	0.0082 (15)
N2	0.064 (2)	0.064 (2)	0.053 (2)	0.0251 (18)	−0.0076 (17)	0.0105 (17)
O3	0.104 (3)	0.085 (2)	0.0485 (18)	0.047 (2)	−0.0134 (17)	0.0066 (17)
N3	0.060 (2)	0.053 (2)	0.0471 (19)	0.0200 (17)	−0.0017 (16)	0.0078 (16)
N4	0.067 (2)	0.058 (2)	0.051 (2)	0.0208 (18)	0.0032 (17)	0.0089 (17)
C4	0.049 (2)	0.054 (2)	0.049 (2)	0.0153 (18)	−0.0041 (18)	0.0110 (18)
N5	0.062 (2)	0.055 (2)	0.0487 (19)	0.0197 (17)	−0.0069 (16)	0.0090 (16)
C5	0.060 (2)	0.049 (2)	0.047 (2)	0.0187 (19)	−0.0019 (18)	0.0111 (18)
N6	0.075 (2)	0.061 (2)	0.050 (2)	0.0248 (19)	−0.0061 (18)	0.0112 (18)
C6	0.083 (3)	0.061 (3)	0.054 (3)	0.028 (2)	−0.012 (2)	0.008 (2)
C7	0.097 (4)	0.062 (3)	0.060 (3)	0.025 (3)	−0.014 (3)	0.001 (2)
C8	0.096 (4)	0.069 (3)	0.079 (4)	0.035 (3)	0.003 (3)	−0.004 (3)
C10	0.072 (3)	0.080 (3)	0.077 (3)	0.034 (3)	−0.015 (3)	−0.005 (3)
C9	0.086 (4)	0.091 (4)	0.091 (4)	0.051 (3)	−0.018 (3)	−0.018 (3)
C2	0.052 (2)	0.053 (2)	0.045 (2)	0.0133 (18)	−0.0031 (17)	0.0102 (18)
C3	0.055 (2)	0.062 (3)	0.047 (2)	0.021 (2)	−0.0056 (18)	0.0142 (19)
Br3	0.0921 (4)	0.0769 (3)	0.0643 (3)	0.0490 (3)	0.0009 (2)	0.0114 (2)
Br1	0.0966 (4)	0.0837 (4)	0.0482 (3)	0.0407 (3)	−0.0121 (2)	0.0000 (2)
C1	0.051 (2)	0.054 (2)	0.050 (2)	0.0181 (19)	−0.0022 (18)	0.0112 (18)
C15	0.062 (3)	0.066 (3)	0.055 (2)	0.028 (2)	0.004 (2)	0.013 (2)
C11	0.053 (2)	0.049 (2)	0.046 (2)	0.0148 (18)	0.0004 (17)	0.0118 (17)
C12	0.056 (2)	0.066 (3)	0.050 (2)	0.026 (2)	−0.0034 (19)	0.008 (2)
C13	0.057 (2)	0.074 (3)	0.052 (2)	0.025 (2)	−0.008 (2)	0.012 (2)
C14	0.068 (3)	0.055 (2)	0.043 (2)	0.019 (2)	−0.0020 (19)	0.0115 (18)
C19	0.065 (3)	0.053 (2)	0.060 (3)	0.025 (2)	−0.002 (2)	0.006 (2)
C20	0.056 (2)	0.060 (3)	0.043 (2)	0.013 (2)	−0.0026 (18)	0.0126 (19)
C21	0.064 (3)	0.057 (2)	0.047 (2)	0.020 (2)	0.0004 (19)	0.0097 (19)
C22	0.090 (4)	0.090 (4)	0.062 (3)	0.046 (3)	−0.017 (3)	−0.008 (3)
C23	0.100 (4)	0.092 (4)	0.076 (4)	0.049 (3)	−0.016 (3)	−0.024 (3)
C24	0.097 (4)	0.110 (4)	0.047 (3)	0.033 (3)	−0.019 (3)	0.005 (3)
C25	0.119 (5)	0.089 (4)	0.070 (3)	0.042 (4)	−0.032 (3)	0.014 (3)
C26	0.100 (4)	0.073 (3)	0.058 (3)	0.036 (3)	−0.017 (3)	0.007 (2)
C27	0.056 (2)	0.056 (2)	0.051 (2)	0.018 (2)	−0.0032 (19)	0.0110 (19)
C28	0.080 (3)	0.058 (3)	0.070 (3)	0.013 (2)	−0.028 (2)	0.006 (2)
C29	0.086 (3)	0.058 (3)	0.073 (3)	0.022 (2)	−0.021 (3)	0.013 (2)
C30	0.058 (2)	0.070 (3)	0.046 (2)	0.022 (2)	0.0002 (19)	0.012 (2)
C31	0.066 (3)	0.061 (3)	0.065 (3)	0.017 (2)	−0.013 (2)	0.001 (2)
C32	0.074 (3)	0.052 (2)	0.067 (3)	0.020 (2)	−0.013 (2)	0.003 (2)
C33	0.057 (2)	0.052 (2)	0.051 (2)	0.0180 (19)	−0.0050 (19)	0.0132 (18)
C34	0.052 (2)	0.049 (2)	0.050 (2)	0.0103 (18)	−0.0075 (18)	0.0061 (18)
C35	0.062 (3)	0.052 (2)	0.051 (2)	0.019 (2)	−0.0100 (19)	0.0072 (19)
C36	0.056 (2)	0.049 (2)	0.050 (2)	0.0113 (18)	−0.0101 (18)	0.0116 (18)
C37	0.056 (2)	0.050 (2)	0.057 (2)	0.0151 (19)	−0.0117 (19)	0.0085 (19)
C38	0.089 (3)	0.074 (3)	0.058 (3)	0.037 (3)	−0.014 (2)	0.004 (2)
C39	0.104 (4)	0.077 (3)	0.071 (3)	0.052 (3)	−0.006 (3)	0.010 (3)
C40	0.080 (3)	0.071 (3)	0.077 (3)	0.029 (3)	−0.019 (3)	0.021 (3)
C41	0.092 (4)	0.080 (3)	0.064 (3)	0.030 (3)	−0.012 (3)	0.025 (3)
C42	0.079 (3)	0.066 (3)	0.058 (3)	0.030 (2)	−0.002 (2)	0.012 (2)
C43	0.056 (2)	0.050 (2)	0.055 (2)	0.0176 (19)	−0.0022 (19)	0.0109 (19)
C44	0.056 (2)	0.052 (2)	0.062 (3)	0.0136 (19)	−0.009 (2)	0.005 (2)
C45	0.053 (2)	0.077 (3)	0.061 (3)	0.027 (2)	−0.005 (2)	0.015 (2)
C46	0.064 (3)	0.055 (2)	0.050 (2)	0.027 (2)	0.0024 (19)	0.0118 (19)
C47	0.077 (3)	0.058 (3)	0.051 (2)	0.027 (2)	−0.010 (2)	0.001 (2)
C48	0.064 (3)	0.060 (3)	0.051 (2)	0.023 (2)	−0.016 (2)	0.005 (2)
C16	0.055 (2)	0.064 (3)	0.052 (2)	0.020 (2)	−0.0079 (19)	0.010 (2)
C17	0.055 (2)	0.056 (2)	0.044 (2)	0.0142 (19)	−0.0029 (18)	0.0118 (18)
C18	0.060 (2)	0.051 (2)	0.053 (2)	0.0153 (19)	−0.0015 (19)	0.0089 (19)

Geometric parameters (Å, º) top

Br2—C30	1.901 (4)	C19—C20	1.397 (6)
O1—N2	1.277 (4)	C20—C21	1.471 (6)
N1—C4	1.346 (5)	C21—C26	1.372 (6)
N1—C1	1.374 (5)	C21—C22	1.404 (6)
O2—N4	1.270 (5)	C22—C23	1.365 (7)
N2—C1	1.341 (5)	C23—C24	1.366 (8)
O3—N6	1.279 (5)	C24—C25	1.348 (8)
N3—C20	1.337 (5)	C25—C26	1.395 (7)
N3—C17	1.385 (5)	C27—C32	1.384 (6)
N4—C17	1.365 (5)	C27—C28	1.389 (6)
C4—C3	1.405 (5)	C27—C18	1.480 (6)
C4—C5	1.453 (6)	C28—C29	1.386 (6)
N5—C36	1.342 (5)	C29—C30	1.376 (6)
N5—C33	1.378 (5)	C30—C31	1.365 (6)
C5—C10	1.381 (6)	C31—C32	1.380 (6)
C5—C6	1.388 (6)	C33—C34	1.417 (6)
N6—C33	1.335 (5)	C34—C35	1.383 (6)
C6—C7	1.376 (7)	C34—C43	1.465 (6)
C7—C8	1.365 (7)	C35—C36	1.403 (6)
C8—C9	1.343 (7)	C36—C37	1.464 (6)
C10—C9	1.396 (7)	C37—C38	1.386 (6)
C2—C3	1.368 (6)	C37—C42	1.404 (6)
C2—C1	1.437 (5)	C38—C39	1.393 (7)
C2—C11	1.470 (5)	C39—C40	1.349 (7)
Br3—C46	1.901 (4)	C40—C41	1.370 (7)
Br1—C14	1.898 (4)	C41—C42	1.377 (6)
C15—C14	1.371 (6)	C43—C44	1.391 (6)
C15—C16	1.389 (6)	C43—C48	1.399 (6)
C11—C16	1.378 (6)	C44—C45	1.372 (6)
C11—C12	1.400 (6)	C45—C46	1.373 (6)
C12—C13	1.398 (6)	C46—C47	1.379 (6)
C13—C14	1.365 (6)	C47—C48	1.370 (6)
C19—C18	1.372 (6)	C17—C18	1.415 (6)

C4—N1—C1	109.6 (3)	C32—C27—C28	117.3 (4)
O1—N2—C1	114.7 (4)	C32—C27—C18	123.6 (4)
C20—N3—C17	108.3 (3)	C28—C27—C18	119.0 (4)
O2—N4—C17	114.0 (3)	C29—C28—C27	122.5 (4)
N1—C4—C3	107.8 (4)	C30—C29—C28	117.5 (4)
N1—C4—C5	125.0 (4)	C31—C30—C29	122.0 (4)
C3—C4—C5	127.2 (4)	C31—C30—Br2	119.3 (3)
C36—N5—C33	109.1 (4)	C29—C30—Br2	118.7 (3)
C10—C5—C6	118.3 (4)	C30—C31—C32	119.3 (4)
C10—C5—C4	119.5 (4)	C31—C32—C27	121.3 (4)
C6—C5—C4	122.1 (4)	N6—C33—N5	126.6 (4)
O3—N6—C33	115.4 (4)	N6—C33—C34	125.4 (4)
C7—C6—C5	120.5 (4)	N5—C33—C34	108.0 (3)
C8—C7—C6	120.0 (5)	C35—C34—C33	106.1 (4)
C9—C8—C7	120.9 (5)	C35—C34—C43	125.5 (4)
C5—C10—C9	120.2 (5)	C33—C34—C43	128.4 (4)
C8—C9—C10	120.0 (5)	C34—C35—C36	108.3 (4)
C3—C2—C1	105.8 (3)	N5—C36—C35	108.4 (4)
C3—C2—C11	126.3 (4)	N5—C36—C37	124.3 (4)
C1—C2—C11	128.0 (4)	C35—C36—C37	127.3 (4)
C2—C3—C4	109.3 (3)	C38—C37—C42	117.7 (4)
N2—C1—N1	126.4 (4)	C38—C37—C36	122.8 (4)
N2—C1—C2	125.8 (4)	C42—C37—C36	119.4 (4)
N1—C1—C2	107.5 (3)	C37—C38—C39	119.4 (5)
C14—C15—C16	119.2 (4)	C40—C39—C38	122.0 (5)
C16—C11—C12	117.6 (4)	C39—C40—C41	119.7 (5)
C16—C11—C2	123.3 (4)	C40—C41—C42	119.9 (5)
C12—C11—C2	119.1 (4)	C41—C42—C37	121.3 (5)
C13—C12—C11	121.2 (4)	C44—C43—C48	117.5 (4)
C14—C13—C12	118.7 (4)	C44—C43—C34	122.5 (4)
C13—C14—C15	121.6 (4)	C48—C43—C34	120.0 (4)
C13—C14—Br1	119.3 (3)	C45—C44—C43	121.2 (4)
C15—C14—Br1	119.0 (3)	C44—C45—C46	119.5 (4)
C18—C19—C20	108.3 (4)	C45—C46—C47	121.4 (4)
N3—C20—C19	109.2 (4)	C45—C46—Br3	119.7 (3)
N3—C20—C21	123.9 (4)	C47—C46—Br3	119.0 (3)
C19—C20—C21	126.9 (4)	C48—C47—C46	118.5 (4)
C26—C21—C22	116.8 (4)	C47—C48—C43	122.0 (4)
C26—C21—C20	122.9 (4)	C11—C16—C15	121.6 (4)
C22—C21—C20	120.3 (4)	N4—C17—N3	126.3 (4)
C23—C22—C21	122.0 (5)	N4—C17—C18	125.4 (4)
C22—C23—C24	119.6 (5)	N3—C17—C18	108.1 (3)
C25—C24—C23	120.2 (5)	C19—C18—C17	106.2 (4)
C24—C25—C26	120.7 (5)	C19—C18—C27	126.6 (4)
C21—C26—C25	120.7 (5)	C17—C18—C27	127.2 (4)

C1—N1—C4—C3	0.6 (5)	C30—C31—C32—C27	0.9 (8)
C1—N1—C4—C5	−177.8 (4)	C28—C27—C32—C31	−0.4 (7)
N1—C4—C5—C10	157.7 (5)	C18—C27—C32—C31	176.6 (4)
C3—C4—C5—C10	−20.4 (7)	O3—N6—C33—N5	−0.9 (7)
N1—C4—C5—C6	−21.0 (7)	O3—N6—C33—C34	178.1 (4)
C3—C4—C5—C6	160.8 (5)	C36—N5—C33—N6	179.3 (4)
C10—C5—C6—C7	1.3 (7)	C36—N5—C33—C34	0.2 (5)
C4—C5—C6—C7	−179.9 (5)	N6—C33—C34—C35	179.9 (4)
C5—C6—C7—C8	−0.2 (8)	N5—C33—C34—C35	−1.1 (5)
C6—C7—C8—C9	−1.8 (9)	N6—C33—C34—C43	−0.2 (7)
C6—C5—C10—C9	−0.6 (8)	N5—C33—C34—C43	178.9 (4)
C4—C5—C10—C9	−179.4 (5)	C33—C34—C35—C36	1.5 (5)
C7—C8—C9—C10	2.5 (10)	C43—C34—C35—C36	−178.4 (4)
C5—C10—C9—C8	−1.3 (10)	C33—N5—C36—C35	0.7 (5)
C1—C2—C3—C4	−0.7 (5)	C33—N5—C36—C37	−177.6 (4)
C11—C2—C3—C4	179.4 (4)	C34—C35—C36—N5	−1.4 (5)
N1—C4—C3—C2	0.1 (5)	C34—C35—C36—C37	176.9 (4)
C5—C4—C3—C2	178.5 (4)	N5—C36—C37—C38	−11.7 (7)
O1—N2—C1—N1	3.0 (6)	C35—C36—C37—C38	170.3 (5)
O1—N2—C1—C2	177.2 (4)	N5—C36—C37—C42	166.3 (4)
C4—N1—C1—N2	174.1 (4)	C35—C36—C37—C42	−11.8 (7)
C4—N1—C1—C2	−1.0 (5)	C42—C37—C38—C39	1.2 (7)
C3—C2—C1—N2	−174.1 (4)	C36—C37—C38—C39	179.1 (5)
C11—C2—C1—N2	5.9 (7)	C37—C38—C39—C40	1.3 (9)
C3—C2—C1—N1	1.0 (5)	C38—C39—C40—C41	−3.2 (9)
C11—C2—C1—N1	−179.0 (4)	C39—C40—C41—C42	2.6 (9)
C3—C2—C11—C16	−154.4 (4)	C40—C41—C42—C37	−0.2 (8)
C1—C2—C11—C16	25.7 (7)	C38—C37—C42—C41	−1.7 (7)
C3—C2—C11—C12	24.7 (7)	C36—C37—C42—C41	−179.8 (5)
C1—C2—C11—C12	−155.3 (4)	C35—C34—C43—C44	142.3 (5)
C16—C11—C12—C13	0.3 (7)	C33—C34—C43—C44	−37.6 (7)
C2—C11—C12—C13	−178.8 (4)	C35—C34—C43—C48	−35.1 (7)
C11—C12—C13—C14	0.1 (7)	C33—C34—C43—C48	145.0 (5)
C12—C13—C14—C15	−0.2 (7)	C48—C43—C44—C45	−0.3 (7)
C12—C13—C14—Br1	179.7 (3)	C34—C43—C44—C45	−177.7 (4)
C16—C15—C14—C13	−0.1 (7)	C43—C44—C45—C46	0.0 (7)
C16—C15—C14—Br1	180.0 (3)	C44—C45—C46—C47	0.2 (7)
C17—N3—C20—C19	−0.6 (5)	C44—C45—C46—Br3	−179.9 (4)
C17—N3—C20—C21	−178.1 (4)	C45—C46—C47—C48	−0.1 (7)
C18—C19—C20—N3	0.8 (5)	Br3—C46—C47—C48	−180.0 (4)
C18—C19—C20—C21	178.2 (4)	C46—C47—C48—C43	−0.3 (7)
N3—C20—C21—C26	−4.1 (7)	C44—C43—C48—C47	0.5 (7)
C19—C20—C21—C26	178.8 (5)	C34—C43—C48—C47	177.9 (4)
N3—C20—C21—C22	174.2 (5)	C12—C11—C16—C15	−0.6 (7)
C19—C20—C21—C22	−2.9 (7)	C2—C11—C16—C15	178.5 (4)
C26—C21—C22—C23	1.5 (9)	C14—C15—C16—C11	0.5 (7)
C20—C21—C22—C23	−176.9 (6)	O2—N4—C17—N3	0.7 (6)
C21—C22—C23—C24	−1.5 (10)	O2—N4—C17—C18	175.6 (4)
C22—C23—C24—C25	1.1 (11)	C20—N3—C17—N4	175.8 (4)
C23—C24—C25—C26	−0.7 (10)	C20—N3—C17—C18	0.2 (5)
C22—C21—C26—C25	−1.1 (8)	C20—C19—C18—C17	−0.6 (5)
C20—C21—C26—C25	177.2 (5)	C20—C19—C18—C27	−179.5 (4)
C24—C25—C26—C21	0.8 (10)	N4—C17—C18—C19	−175.4 (4)
C32—C27—C28—C29	−0.4 (8)	N3—C17—C18—C19	0.3 (5)
C18—C27—C28—C29	−177.6 (5)	N4—C17—C18—C27	3.5 (7)
C27—C28—C29—C30	0.6 (8)	N3—C17—C18—C27	179.2 (4)
C28—C29—C30—C31	−0.1 (8)	C32—C27—C18—C19	−145.2 (5)
C28—C29—C30—Br2	178.6 (4)	C28—C27—C18—C19	31.8 (7)
C29—C30—C31—C32	−0.7 (8)	C32—C27—C18—C17	36.1 (7)
Br2—C30—C31—C32	−179.4 (4)	C28—C27—C18—C17	−146.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	2.10	2.957 (5)	177
N3—H3A···O1	0.86	2.10	2.956 (5)	171
N5—H5···O2	0.86	2.16	3.009 (5)	169
C6—H6···N6	0.93	2.53	3.294 (6)	139
C26—H26···N2	0.93	2.43	3.338 (7)	165
C38—H38···N4	0.93	2.48	3.331 (6)	153
C6—H6···O3	0.93	2.69	3.505 (6)	146
C26—H26···O1	0.93	2.43	3.543 (6)	165
C38—H38···O2	0.93	2.72	3.564 (6)	151

Acknowledgements

The authors thanks Marco Leyva for collecting the crystals and crystallographic support. MFP acknowledges CONAHCYT for a postdoctoral fellowship.

Funding information

The following funding is acknowledged: Consejo Nacional de Ciencia y Tecnología (scholarship No. CVU 580380 to Mónica Farfán-Paredes).

References

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