Synthesis and comparative structural study of 2-(pyridin-2-yl)-1H-perimidine and its mono- and di-N-methyl­ated analogues

Kalle, P.; Tatarin, S.V.; Zakharov, A.Y.; Kiseleva, M.A.; Bezzubov, S.I.

doi:10.1107/S205698902100013X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 96-100

https://doi.org/10.1107/S205698902100013X

Open

access

Synthesis and comparative structural study of 2-(pyridin-2-yl)-1H-perimidine and its mono- and di-N-methylated analogues

Paulina Kalle,^a,^b Sergei V. Tatarin,^a,^b Alexander Yu. Zakharov,^b Marina A. Kiseleva ^a,^b and Stanislav I. Bezzubov ^b ^*

^aDepartment of Chemistry, Lomonosov Moscow State University, Lenin's Hills, 1-3, Moscow, 119991, Russian Federation, and ^bN.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky pr. 31, Moscow 119991, Russian Federation
^*Correspondence e-mail: bezzubov@igic.ras.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 December 2020; accepted 5 January 2021; online 8 January 2021)

The title compounds, 2-(pyridin-2-yl)-1H-perimidine (C₁₆H₁₁N₃; 1), 1-methyl-2-(pyridin-2-yl)-1H-perimidine (C₁₇H₁₃N₃; 2), and 1,3-dimethyl-2-(pyridin-2-yl)-1H-perimidinium iodide (C₁₈H₁₆N₃⁺·I⁻; 3) were synthesized under mild conditions and their structures were determined by ¹H NMR spectroscopy and single-crystal X-ray analysis. The N-methylation of the nitrogen atom(s) at the perimidine moiety results in a significant increase of the interplane angle between the pyridin-2-yl ring and the perimidine system. The unsubstituted perimidine (1) forms a weak intramolecular N—H⋯N bond that consolidates the molecular conformation. In the crystal structures of 1–3, the molecular entities all are assembled through π–π and C—H⋯π interactions.

Keywords: crystal structure; perimidine; π–π stacking; hydrogen-bonding; NMR study.

CCDC references: 2051714; 2032890; 2032889

1. Chemical context

Perimidines are fused nitrogen heterocyclic aromatics possessing equally a π-electron excess and a π-electron deficiency that determine their diverse reactivities as well as their unique optical and spectroscopic properties (Pozharskii et al., 2020 ). These compounds have attracted considerable attention over the past two decades because of their growing application in industrial chemistry (especially as dyes and pigments), as optoelectronics, in biotechnology and medicinal chemistry (Sahiba & Agarwal, 2020 ).

Herein, we report structural studies of 1-H-2-(pyridin-2-yl)perimidine (1) and its mono- and di-N-methylated analogues (2 and 3, respectively).

2. Structural commentary

The compositions and structures of the synthesized compounds were determined both by ¹H NMR spectroscopy (for assignment, see: Figs. S1–S3 in the supporting information) and single-crystal X-ray analysis. In all cases, the organic molecules occupy general positions and comprise an essentially flat perimidine system and the pyridyl ring. Depending on the number of N-substituents, the ring systems are twisted to a greater or lesser extent (Figs. 1–3 ). The unsubstituted molecule of 1 is almost planar with the dihedral angle between the aromatic parts as small as 1.60 (5)°, while the molecules of 2 and especially 3 show notably larger interplane angles [59.39 (8) and 87.21 (9)°, respectively] because of steric repulsion between the N-methyl group(s) and the pyridin-2-yl ring. The flat conformation of 1 may be stabilized by a weak intramolecular hydrogen bond between the perimidine N1—H1 donor group and the pyridyl N3 acceptor group [d(N1⋯N3) = 2.626 (2) Å, d(N1—H1) = 0.87 (2) Å, d(H1⋯N3) = 2.19 (2) Å, N1—H1⋯N3 = 110.9 (17)°] whereas in the molecular structure of 2 the pyridyl nitrogen atom participates in a weak intramolecular C12(sp³)—H12A⋯N3 contact [d(H12A⋯N3) = 2.46 (2) Å; C12⋯N3 = 3.059 (1) Å; C12—H12A⋯N3 = 120.8 (18)°]. Compound 3 is a salt and its crystal consists of doubly N-methylated perimidinium cations and iodide counter-ions combined mainly through Coulombic interactions.

Figure 1
The molecular structure of 1-H-2-(pyridin-2-yl)perimidine (1), with displacement ellipsoids drawn at the 50% probability level.

Figure 2
The molecular structure of 1-methyl-2-(pyridin-2-yl)perimidine (2), with displacement ellipsoids drawn at the 50% probability level.

Figure 3
The molecular structure of 1,3-dimethyl-2-(pyridin-2-yl)perimidinium iodide (3, only the cation is presented), with displacement ellipsoids drawn at the 50% probability level.

¹H NMR spectroscopic studies of 1–3 revealed correlations between the chemical shifts of some bands in the spectra and the mutual arrangement of the perimidine and pyridyl aromatics. In the ¹H NMR spectrum of 1 in CDCl₃, doublets at 6.36 and 6.91 ppm arise from the j and e protons, respectively, while the other protons of the perimidine core appear as complex multiplets in the range 7.06–7.25 ppm (Fig. S1). A similar set of bands (corresponding to the same protons) with slightly different chemical shifts can be found in the ¹H NMR spectrum of 2 (Fig. S2) whereas 1,3-dimethyl-2-(pyridin-2-yl)perimidinium iodide (3) demonstrates a reduced number of resonance signals (Fig. S3) because the protons of the fused benzene rings become equivalent. The latter results from the above arrangement of the pyridyl ring almost orthogonal to the perimidine system.

For compound 1, solvent-dependent resonance signals in the ¹H NMR spectrum were detected. In DMSO-d₆ as a solvent (Fig. S4), the characteristic doublets arising from the protons j and e are now closer (6.74 and 6.79 ppm, respectively) while the integrated intensity of the signal of the N—H proton becomes lower (0.77 ppm) which may result from a weakening of the intramolecular N—H⋯N hydrogen bond by the polar solvent.

3. Supramolecular features

In the crystal of 1, molecules are assembled through parallel displaced π–π stacking interactions between the flat pyridyl and perimidine fragments distant by 3.295 (4) Å (C5⋯N1–C11_centroid) and 3.302 (4) Å (N2⋯py_centroid), while the resulting offset stacks [centroid-to-centroid shift between the adjacent molecules in the stack 3.791 (4) Å] are grafted together in the resulting three-dimensional network by a C—H⋯π interaction [d(H⋯π) = 2.96 (2) Å] involving the pyridyl H15 atom and the centroid of the C2–C11 ring (Fig. 4). In contrast, two types of π–π interactions are found in the crystal of 2, one of which is a slipped stacking [centroid-to-centroid shift 1.645 (2) Å] between the perimidine units [d(C7⋯N1–C11_centroid) = 3.375 (2) Å, d(C9⋯N1–C11_centroid) = 3.774 (3) Å, d(C11⋯C6–C11_centroid) = 3.423 (2) Å] while the other is a pyridyl–pyridyl contact [distance between the C16 atom and the pyridyl ring 3.499 (3) Å] connecting the stacks together. Intermolecular contacts between the H12C atom and the C6–C11_centroid [3.17 (2) Å] and between the H14 atom and C2–C11_centroid [3.684 (19) Å] form a three-dimensional network in the crystal structure of 2 (Fig. 5). In the crystal structure of 3, there are π–π-bonded dimers [interplane distance 3.447 (3) Å between the perimidine moieties], which form dense layers via C—H⋯π interactions [d(H⋯π) = 3.132 (2) Å between the H18 atom and the centroid of the C6–C11 ring and 3.075 (2) Å between the H9 atom and the centroid of the pyridyl ring; Fig. 6]. The resulting cationic organic layers and anionic iodide layers alternate along the c axis.

Figure 4
Intermolecular contacts (Å) in the crystal of 1-H-2-(pyridin-2-yl)perimidine (1). Displacement ellipsoids are shown at the 50% probability level.

Figure 5
Intermolecular contacts (Å) in the crystal of 1-methyl-2-(pyridin-2-yl)perimidine (2). Displacement ellipsoids are shown at the 50% probability level.

Figure 6
Intermolecular contacts (Å) in the crystal of 1,3-dimethyl-2-(pyridin-2-yl)perimidinium iodide (3, only cations are presented). Displacement ellipsoids are shown at the 50% probability level.

4. Database survey

Though many perimidines have been prepared so far, fewer than 60 crystal structures of them (including a few of metal complexes) have been published (Pozharskii et al., 2020; Hill et al., 2018 ; Bahena et al., 2019 ; Booysen et al., 2016 ). Crystal structures of several 1,3-dimethyl-2-arylperimidinium iodides have been determined (Li et al., 2017 ). A comprehensive structural study of 2-arylperimidines (including those having intramolecular hydrogen bonds) has also been conducted (Foces-Foces et al., 1993 ; Llamas-Saiz et al., 1995 ).

5. Synthesis and crystallization

The title compounds were prepared as follows:

1-H-2-(pyridin-2-yl)perimidine (1).

A mixture of 1,8-diaminonaphthalene (4.523 g, 28.6 mmol), pyridin-2-ylcarboxaldehyde (2.72 ml, 28.6 mmol) and sodium metabisulfite (16.317 g, 85.8 mmol) in ethanol (50 ml) was refluxed under Ar for 4 h. The reaction mixture was evaporated to dryness, washed with water and redissolved in ethanol. Keeping the resulting solution in a freezer overnight gave a red powder, which was recrystallized from methylene chloride and dried in vacuo. Yield 6 g (86%). Single crystals suitable for X-ray analysis were grown by slow evaporation of the solvent from a solution of the substance in methylene chloride.

¹H NMR (CDCl₃, ppm, 400 MHz): δ 6.36 (d, J = 7.4 Hz, 1H, H_naph), 6.91 (d, J = 7.4 Hz, 1H, H_naph), 7.06–7.25 (m, 4H, H_naph), 7.44–7.47 (m, 1H, H_py), 7.88 (td, J₁ = 7.8 Hz, J₂ = 1.7 Hz, 1H, H_py), 8.44 (d, J = 7.6 Hz, 1H, H_py), 8.62–8.64 (m, 1H, H_py), 9.39 (br. s, 1H, N-H). See supplementary Fig. S1.

1-Methyl-2-(pyridin-2-yl)perimidine (2).

To a mixture of 1 (0.250 g, 1.02 mmol), solid KOH (0.057 g, 1.02 mmol) and anhydrous K₂CO₃ (0.141 g, 1.02 mmol) in anhydrous Ar-saturated acetonitrile methyl iodide (0.064 ml, 1.02 mmol) was added dropwise upon stirring and the resulting suspension was heated at 323 K for 3 h and then at r.t. for two days. The reaction mixture was evaporated to dryness and the crude product was purified by column chromatography (eluent hexane/ethyl acetate 1/1 v/v), recrystallized from a mixture of CH₂Cl₂/hexane and dried in vacuo. Yield 185 mg (70%). Single crystals suitable for X-ray analysis were grown by slow evaporation of the solvent from a solution of the substance in chloroform.

¹H NMR (CDCl₃, ppm, 400 MHz): δ 3.17 (s, 3H, N—CH₃), 6.32 (dd, J₁ = 7.2 Hz, J₂ = 1.0 Hz, 1H, H_naph), 6.94 (dd, J₁ = 7.3 Hz, J₂ = 1.0 Hz, 1H, H_naph), 7.17–7.32 (m, 4H, H_naph), 7.39–7.42 (m, 1H, H_py), 7.77–7.80 (m, 1H, H_py), 7.86–7.89 (m, 1H, H_py), 8.70 (m, 1H, H_py). See supplementary Fig. S2.

1,3-Dimethyl-2-(pyridin-2-yl)perimidinium iodide (3).

This compound was isolated from the above reaction mixture (synthesis of compound 2) as a side product (15 mg). Single crystals suitable for X-ray analysis were grown by slow evaporation of the solvent from a solution of the substance in ethanol.

¹H NMR (CDCl₃, ppm, 400 MHz): δ 3.34 (s, 6H, N—CH₃), 6.96 (d, J = 7.7 Hz, 2H, H_naph), 7.50 (m, 2H, H_naph), 7.60 (m, 2H, H_naph), 7.66–7.70 (m, 1H, H_py), 8.19 (td, J₁ = 7.8 Hz, J₂ = 1.7 Hz, 1H, H_py), 8.65–8.68 (m, 1H, H_py), 9.24–9.26 (m, 1H, H_py). See supplementary Fig. S3.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Hydrogen atoms in the structures of 1 and 2 were located from difference electron density maps and were refined freely. In the structure of 3, hydrogen atoms were placed in calculated positions and refined using a riding model [C—H = 0.94–0.97 Å with U_iso(H) = 1.2–1.5U_eq(C)].

Table 1
Experimental details

	(1)	(2)	(3)
Crystal data
Chemical formula	C₁₆H₁₁N₃	C₁₇H₁₃N₃	C₁₈H₁₆N₃⁺·I⁻
M_r	245.28	259.30	401.24
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/n
Temperature (K)	100	100	230
a, b, c (Å)	13.5479 (5), 5.0242 (2), 17.3881 (7)	7.5095 (2), 12.1216 (3), 13.5616 (4)	9.8821 (2), 9.7125 (2), 17.9839 (4)
β (°)	101.382 (2)	92.547 (1)	103.676 (1)
V (Å³)	1160.28 (8)	1233.25 (6)	1677.15 (6)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.09	0.09	1.91
Crystal size (mm)	0.42 × 0.1 × 0.08	0.34 × 0.12 × 0.11	0.32 × 0.18 × 0.13

Data collection
Diffractometer	Bruker D8 Venture	Bruker D8 Venture	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.684, 0.746	0.685, 0.746	0.668, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	16322, 2866, 2405	14029, 3280, 2803	28389, 4146, 3700
R_int	0.036	0.035	0.026
(sin θ/λ)_max (Å⁻¹)	0.667	0.682	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.140, 1.05	0.060, 0.146, 1.04	0.028, 0.067, 1.06
No. of reflections	2866	3280	4146
No. of parameters	216	233	201
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.33	0.45, −0.34	0.72, −0.46
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2051714; 2032890; 2032889

Crystal structure: contains datablocks 1, 2, 3. DOI: https://doi.org/10.1107/S205698902100013X/wm5594sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S205698902100013X/wm55941sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S205698902100013X/wm55942sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S205698902100013X/wm55943sup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698902100013X/wm55941sup5.mol

Supporting information file. DOI: https://doi.org/10.1107/S205698902100013X/wm55942sup6.mol

Supporting information file. DOI: https://doi.org/10.1107/S205698902100013X/wm55943sup7.mol

Supporting information file. DOI: https://doi.org/10.1107/S205698902100013X/wm55941sup8.cml

Supporting information file. DOI: https://doi.org/10.1107/S205698902100013X/wm55942sup9.cml

Supporting information file. DOI: https://doi.org/10.1107/S205698902100013X/wm55943sup10.cml

Fig. S1. NMR spectrum for 1. DOI: https://doi.org/10.1107/S205698902100013X/wm5594sup11.tif

Fig. S2. NMR spectrum for 2. DOI: https://doi.org/10.1107/S205698902100013X/wm5594sup12.tif

Fig. S3. NMR spectrum for 3. DOI: https://doi.org/10.1107/S205698902100013X/wm5594sup13.tif

Fig. S4. NMR spectrum for 1 in DMSO solvent. DOI: https://doi.org/10.1107/S205698902100013X/wm5594sup14.tif

checkCIF report

Computing details top

For all structures, data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

2-(Pyridin-2-yl)-1H-perimidine (1) top

Crystal data top

C₁₆H₁₁N₃	F(000) = 512
M_r = 245.28	D_x = 1.404 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5479 (5) Å	Cell parameters from 7163 reflections
b = 5.0242 (2) Å	θ = 3.1–28.3°
c = 17.3881 (7) Å	µ = 0.09 mm⁻¹
β = 101.382 (2)°	T = 100 K
V = 1160.28 (8) Å³	Needle, red
Z = 4	0.42 × 0.1 × 0.08 mm

Data collection top

Bruker D8 Venture diffractometer	2866 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec IµS microsource	2405 reflections with I > 2σ(I)
Focusing mirrors monochromator	R_int = 0.036
Detector resolution: 10.4 pixels mm^-1	θ_max = 28.3°, θ_min = 3.5°
ω–scan	h = −18→18
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −6→6
T_min = 0.684, T_max = 0.746	l = −23→22
16322 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	All H-atom parameters refined
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.057P)² + 1.1159P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2866 reflections	Δρ_max = 0.39 e Å⁻³
216 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
N1	0.67572 (10)	0.4402 (3)	0.27627 (8)	0.0154 (3)
N3	0.71391 (10)	0.0786 (3)	0.17704 (8)	0.0168 (3)
N2	0.84493 (10)	0.5837 (3)	0.30290 (8)	0.0155 (3)
C12	0.79419 (12)	0.2223 (3)	0.21158 (9)	0.0143 (3)
C10	0.64357 (12)	0.6204 (3)	0.32655 (9)	0.0149 (3)
C1	0.77359 (12)	0.4307 (3)	0.26757 (9)	0.0142 (3)
C2	0.81956 (12)	0.7734 (3)	0.35506 (9)	0.0150 (3)
C13	0.89068 (12)	0.1825 (3)	0.19733 (9)	0.0156 (3)
C3	0.89194 (13)	0.9430 (3)	0.39534 (9)	0.0174 (3)
C8	0.52046 (13)	0.8239 (4)	0.38981 (10)	0.0200 (4)
C16	0.72925 (13)	−0.1115 (3)	0.12658 (10)	0.0189 (4)
C15	0.82269 (13)	−0.1659 (3)	0.10900 (9)	0.0191 (4)
C9	0.54570 (12)	0.6318 (3)	0.33781 (9)	0.0182 (3)
C6	0.69204 (12)	0.9893 (3)	0.41877 (9)	0.0168 (3)
C5	0.76845 (13)	1.1625 (3)	0.45756 (9)	0.0186 (3)
C14	0.90460 (13)	−0.0168 (3)	0.14534 (10)	0.0181 (3)
C11	0.71827 (12)	0.7951 (3)	0.36697 (9)	0.0145 (3)
C7	0.59039 (13)	0.9992 (4)	0.42875 (10)	0.0201 (4)
C4	0.86549 (13)	1.1376 (3)	0.44599 (9)	0.0187 (4)
H3	0.9603 (15)	0.931 (4)	0.3862 (11)	0.020 (5)*
H13	0.9452 (16)	0.282 (4)	0.2226 (12)	0.024 (5)*
H8	0.4528 (16)	0.829 (4)	0.3965 (12)	0.024 (5)*
H14	0.9698 (17)	−0.050 (5)	0.1362 (13)	0.031 (6)*
H9	0.4957 (14)	0.510 (4)	0.3102 (11)	0.016 (5)*
H7	0.5720 (16)	1.125 (5)	0.4625 (13)	0.030 (6)*
H4	0.9168 (15)	1.252 (4)	0.4733 (12)	0.023 (5)*
H16	0.6709 (15)	−0.203 (4)	0.1022 (12)	0.024 (5)*
H1	0.6349 (17)	0.326 (5)	0.2490 (13)	0.032 (6)*
H5	0.7526 (14)	1.292 (4)	0.4910 (12)	0.019 (5)*
H15	0.8299 (15)	−0.302 (4)	0.0730 (12)	0.024 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0149 (6)	0.0159 (7)	0.0152 (6)	−0.0011 (5)	0.0022 (5)	−0.0026 (5)
N3	0.0164 (6)	0.0168 (7)	0.0166 (7)	−0.0005 (5)	0.0016 (5)	0.0003 (5)
N2	0.0172 (6)	0.0147 (7)	0.0147 (6)	0.0004 (5)	0.0033 (5)	0.0008 (5)
C12	0.0176 (7)	0.0129 (7)	0.0120 (7)	0.0013 (6)	0.0018 (6)	0.0024 (6)
C10	0.0172 (7)	0.0141 (7)	0.0128 (7)	0.0016 (6)	0.0016 (6)	0.0016 (6)
C1	0.0169 (7)	0.0127 (7)	0.0130 (7)	0.0016 (6)	0.0030 (6)	0.0023 (6)
C2	0.0183 (8)	0.0132 (7)	0.0135 (7)	0.0008 (6)	0.0034 (6)	0.0034 (6)
C13	0.0154 (7)	0.0155 (8)	0.0150 (7)	−0.0010 (6)	0.0011 (6)	−0.0002 (6)
C3	0.0194 (8)	0.0166 (8)	0.0158 (7)	−0.0012 (6)	0.0022 (6)	0.0024 (6)
C8	0.0166 (8)	0.0262 (9)	0.0177 (8)	0.0044 (7)	0.0047 (6)	0.0012 (7)
C16	0.0223 (8)	0.0160 (8)	0.0165 (8)	−0.0024 (7)	−0.0010 (6)	−0.0006 (6)
C15	0.0284 (9)	0.0142 (8)	0.0143 (7)	0.0027 (6)	0.0031 (6)	−0.0008 (6)
C9	0.0177 (8)	0.0197 (8)	0.0165 (8)	0.0013 (6)	0.0017 (6)	−0.0005 (6)
C6	0.0240 (8)	0.0141 (7)	0.0118 (7)	0.0020 (6)	0.0026 (6)	0.0025 (6)
C5	0.0288 (9)	0.0132 (8)	0.0135 (7)	0.0013 (7)	0.0035 (6)	−0.0006 (6)
C14	0.0181 (8)	0.0200 (8)	0.0167 (8)	0.0042 (6)	0.0044 (6)	0.0019 (6)
C11	0.0186 (8)	0.0129 (7)	0.0121 (7)	0.0014 (6)	0.0030 (6)	0.0026 (6)
C7	0.0248 (9)	0.0202 (8)	0.0162 (8)	0.0063 (7)	0.0059 (6)	−0.0017 (7)
C4	0.0260 (8)	0.0148 (8)	0.0137 (7)	−0.0047 (7)	−0.0002 (6)	0.0009 (6)

Geometric parameters (Å, º) top

N1—C10	1.387 (2)	C8—C9	1.410 (2)
N1—C1	1.365 (2)	C8—C7	1.371 (2)
N1—H1	0.87 (2)	C8—H8	0.95 (2)
N3—C12	1.344 (2)	C16—C15	1.387 (2)
N3—C16	1.341 (2)	C16—H16	0.94 (2)
N2—C1	1.292 (2)	C15—C14	1.384 (2)
N2—C2	1.404 (2)	C15—H15	0.94 (2)
C12—C1	1.493 (2)	C9—H9	0.97 (2)
C12—C13	1.392 (2)	C6—C5	1.417 (2)
C10—C9	1.379 (2)	C6—C11	1.420 (2)
C10—C11	1.417 (2)	C6—C7	1.422 (2)
C2—C3	1.381 (2)	C5—C4	1.374 (2)
C2—C11	1.432 (2)	C5—H5	0.93 (2)
C13—C14	1.387 (2)	C14—H14	0.94 (2)
C13—H13	0.93 (2)	C7—H7	0.93 (2)
C3—C4	1.409 (2)	C4—H4	0.95 (2)
C3—H3	0.97 (2)

C10—N1—H1	122.0 (15)	N3—C16—H16	114.7 (13)
C1—N1—C10	121.71 (14)	C15—C16—H16	121.8 (13)
C1—N1—H1	116.3 (15)	C16—C15—H15	120.4 (12)
C16—N3—C12	117.31 (14)	C14—C15—C16	118.52 (15)
C1—N2—C2	117.11 (14)	C14—C15—H15	121.0 (12)
N3—C12—C1	115.40 (14)	C10—C9—C8	118.76 (15)
N3—C12—C13	123.28 (15)	C10—C9—H9	120.1 (11)
C13—C12—C1	121.31 (14)	C8—C9—H9	121.1 (11)
N1—C10—C11	115.76 (14)	C5—C6—C11	118.24 (15)
C9—C10—N1	123.16 (15)	C5—C6—C7	123.66 (15)
C9—C10—C11	121.09 (15)	C11—C6—C7	118.11 (15)
N1—C1—C12	114.06 (14)	C6—C5—H5	119.6 (12)
N2—C1—N1	125.35 (15)	C4—C5—C6	120.29 (15)
N2—C1—C12	120.59 (14)	C4—C5—H5	120.2 (12)
N2—C2—C11	120.58 (14)	C13—C14—H14	119.4 (14)
C3—C2—N2	120.44 (14)	C15—C14—C13	119.24 (15)
C3—C2—C11	118.98 (15)	C15—C14—H14	121.4 (14)
C12—C13—H13	121.8 (13)	C10—C11—C2	119.48 (14)
C14—C13—C12	118.23 (15)	C10—C11—C6	119.78 (14)
C14—C13—H13	119.9 (13)	C6—C11—C2	120.74 (15)
C2—C3—C4	120.17 (15)	C8—C7—C6	120.58 (15)
C2—C3—H3	118.9 (12)	C8—C7—H7	120.3 (13)
C4—C3—H3	120.9 (12)	C6—C7—H7	119.2 (13)
C9—C8—H8	117.3 (13)	C3—C4—H4	118.7 (12)
C7—C8—C9	121.68 (15)	C5—C4—C3	121.57 (15)
C7—C8—H8	121.0 (13)	C5—C4—H4	119.8 (12)
N3—C16—C15	123.42 (15)

N1—C10—C9—C8	−179.50 (15)	C13—C12—C1—N1	−178.61 (14)
N1—C10—C11—C2	−1.0 (2)	C13—C12—C1—N2	1.6 (2)
N1—C10—C11—C6	179.00 (14)	C3—C2—C11—C10	−179.38 (14)
N3—C12—C1—N1	1.1 (2)	C3—C2—C11—C6	0.6 (2)
N3—C12—C1—N2	−178.67 (14)	C16—N3—C12—C1	−179.71 (13)
N3—C12—C13—C14	−0.5 (2)	C16—N3—C12—C13	0.0 (2)
N3—C16—C15—C14	0.1 (3)	C16—C15—C14—C13	−0.6 (2)
N2—C2—C3—C4	178.31 (14)	C9—C10—C11—C2	178.63 (15)
N2—C2—C11—C10	1.0 (2)	C9—C10—C11—C6	−1.3 (2)
N2—C2—C11—C6	−179.07 (14)	C9—C8—C7—C6	−1.1 (3)
C12—N3—C16—C15	0.2 (2)	C6—C5—C4—C3	0.5 (2)
C12—C13—C14—C15	0.8 (2)	C5—C6—C11—C10	−179.34 (14)
C10—N1—C1—N2	−0.8 (2)	C5—C6—C11—C2	0.7 (2)
C10—N1—C1—C12	179.41 (13)	C5—C6—C7—C8	−179.48 (16)
C1—N1—C10—C9	−178.72 (15)	C11—C10—C9—C8	0.8 (2)
C1—N1—C10—C11	1.0 (2)	C11—C2—C3—C4	−1.3 (2)
C1—N2—C2—C3	179.62 (14)	C11—C6—C5—C4	−1.3 (2)
C1—N2—C2—C11	−0.7 (2)	C11—C6—C7—C8	0.6 (2)
C1—C12—C13—C14	179.19 (14)	C7—C8—C9—C10	0.4 (3)
C2—N2—C1—N1	0.7 (2)	C7—C6—C5—C4	178.83 (16)
C2—N2—C1—C12	−179.58 (13)	C7—C6—C11—C10	0.6 (2)
C2—C3—C4—C5	0.8 (2)	C7—C6—C11—C2	−179.37 (14)

1-Methyl-2-(pyridin-2-yl)-1H-perimidine (2) top

Crystal data top

C₁₇H₁₃N₃	F(000) = 544
M_r = 259.30	D_x = 1.397 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.5095 (2) Å	Cell parameters from 5485 reflections
b = 12.1216 (3) Å	θ = 2.3–30.5°
c = 13.5616 (4) Å	µ = 0.09 mm⁻¹
β = 92.547 (1)°	T = 100 K
V = 1233.25 (6) Å³	Block, orange
Z = 4	0.34 × 0.12 × 0.11 mm

Data collection top

Bruker D8 Venture diffractometer	3280 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec IµS microsource	2803 reflections with I > 2σ(I)
Focusing mirrors monochromator	R_int = 0.035
Detector resolution: 10.4 pixels mm^-1	θ_max = 29.0°, θ_min = 2.3°
ω–scan	h = −10→10
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −15→16
T_min = 0.685, T_max = 0.746	l = −18→18
14029 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	All H-atom parameters refined
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.0706P)² + 0.7754P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3280 reflections	Δρ_max = 0.45 e Å⁻³
233 parameters	Δρ_min = −0.33 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
N2	0.76302 (17)	0.66381 (10)	0.66410 (9)	0.0173 (3)
N3	0.79159 (17)	0.88961 (10)	0.52437 (10)	0.0197 (3)
N1	0.69884 (16)	0.65068 (10)	0.49124 (9)	0.0153 (3)
C11	0.79946 (19)	0.48774 (12)	0.57893 (11)	0.0160 (3)
C1	0.71526 (19)	0.70642 (12)	0.57923 (11)	0.0155 (3)
C13	0.68606 (19)	0.82886 (12)	0.58029 (11)	0.0157 (3)
C2	0.80957 (19)	0.55209 (12)	0.66662 (11)	0.0166 (3)
C14	0.5640 (2)	0.87417 (13)	0.64331 (11)	0.0177 (3)
C6	0.85120 (19)	0.37474 (12)	0.58061 (12)	0.0187 (3)
C12	0.6294 (2)	0.70168 (13)	0.39951 (11)	0.0194 (3)
C3	0.8700 (2)	0.50420 (13)	0.75469 (12)	0.0208 (3)
C16	0.6670 (2)	1.05215 (13)	0.59611 (12)	0.0206 (3)
C15	0.5551 (2)	0.98867 (13)	0.65099 (12)	0.0200 (3)
C17	0.7802 (2)	0.99943 (13)	0.53330 (13)	0.0219 (3)
C9	0.7297 (2)	0.47699 (13)	0.40235 (12)	0.0202 (3)
C10	0.74095 (19)	0.53778 (12)	0.48835 (11)	0.0156 (3)
C5	0.9117 (2)	0.32879 (13)	0.67236 (13)	0.0218 (3)
C7	0.8416 (2)	0.31473 (12)	0.49048 (13)	0.0220 (3)
C4	0.9205 (2)	0.39232 (13)	0.75648 (13)	0.0226 (3)
C8	0.7817 (2)	0.36497 (13)	0.40491 (12)	0.0228 (3)
H12A	0.603 (3)	0.7776 (18)	0.4103 (15)	0.029 (5)*
H3	0.879 (3)	0.5482 (16)	0.8163 (15)	0.027 (5)*
H5	0.951 (3)	0.2505 (18)	0.6727 (15)	0.030 (5)*
H7	0.882 (3)	0.2398 (17)	0.4889 (14)	0.025 (5)*
H16	0.663 (3)	1.1313 (17)	0.5991 (14)	0.026 (5)*
H12B	0.723 (3)	0.7008 (16)	0.3497 (14)	0.023 (5)*
H4	0.961 (3)	0.3617 (18)	0.8184 (16)	0.033 (5)*
H17	0.856 (3)	1.0433 (17)	0.4948 (15)	0.028 (5)*
H9	0.695 (3)	0.5092 (17)	0.3402 (15)	0.026 (5)*
H12C	0.518 (3)	0.6600 (16)	0.3771 (14)	0.025 (5)*
H15	0.474 (3)	1.0204 (17)	0.6955 (15)	0.027 (5)*
H14	0.489 (3)	0.8271 (16)	0.6786 (14)	0.023 (5)*
H8	0.777 (3)	0.3237 (17)	0.3434 (16)	0.033 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0187 (6)	0.0155 (6)	0.0178 (6)	0.0007 (5)	0.0024 (5)	0.0012 (5)
N3	0.0193 (6)	0.0155 (6)	0.0248 (7)	0.0029 (5)	0.0045 (5)	0.0026 (5)
N1	0.0172 (6)	0.0128 (6)	0.0160 (6)	0.0024 (5)	0.0005 (5)	0.0006 (4)
C11	0.0123 (6)	0.0151 (7)	0.0208 (7)	−0.0008 (5)	0.0030 (5)	0.0023 (5)
C1	0.0130 (6)	0.0144 (6)	0.0192 (7)	0.0011 (5)	0.0023 (5)	−0.0003 (5)
C13	0.0146 (6)	0.0148 (6)	0.0174 (7)	0.0021 (5)	−0.0011 (5)	−0.0006 (5)
C2	0.0142 (6)	0.0158 (7)	0.0200 (7)	0.0003 (5)	0.0030 (5)	0.0025 (5)
C14	0.0162 (7)	0.0194 (7)	0.0175 (7)	0.0007 (6)	0.0009 (5)	−0.0003 (6)
C6	0.0143 (6)	0.0147 (7)	0.0274 (8)	−0.0006 (5)	0.0045 (6)	0.0027 (6)
C12	0.0207 (7)	0.0182 (7)	0.0189 (7)	0.0038 (6)	−0.0024 (6)	0.0013 (6)
C3	0.0200 (7)	0.0217 (8)	0.0206 (7)	−0.0001 (6)	0.0017 (6)	0.0040 (6)
C16	0.0174 (7)	0.0143 (7)	0.0299 (8)	0.0027 (6)	−0.0020 (6)	−0.0023 (6)
C15	0.0184 (7)	0.0216 (7)	0.0199 (7)	0.0046 (6)	−0.0006 (6)	−0.0045 (6)
C17	0.0188 (7)	0.0167 (7)	0.0304 (8)	0.0010 (6)	0.0030 (6)	0.0035 (6)
C9	0.0205 (7)	0.0184 (7)	0.0219 (7)	−0.0017 (6)	0.0026 (6)	−0.0019 (6)
C10	0.0135 (6)	0.0131 (6)	0.0205 (7)	−0.0004 (5)	0.0033 (5)	−0.0004 (5)
C5	0.0181 (7)	0.0144 (7)	0.0329 (8)	0.0011 (6)	0.0035 (6)	0.0076 (6)
C7	0.0217 (7)	0.0118 (7)	0.0330 (8)	−0.0003 (6)	0.0076 (6)	−0.0015 (6)
C4	0.0191 (7)	0.0223 (8)	0.0262 (8)	−0.0001 (6)	0.0010 (6)	0.0097 (6)
C8	0.0234 (8)	0.0190 (7)	0.0265 (8)	−0.0037 (6)	0.0066 (6)	−0.0070 (6)

Geometric parameters (Å, º) top

N2—C1	1.2974 (19)	C12—H12B	0.996 (19)
N2—C2	1.3986 (18)	C12—H12C	1.01 (2)
N3—C13	1.341 (2)	C3—C4	1.408 (2)
N3—C17	1.340 (2)	C3—H3	0.99 (2)
N1—C1	1.3720 (18)	C16—C15	1.381 (2)
N1—C12	1.4644 (18)	C16—C17	1.386 (2)
N1—C10	1.4055 (18)	C16—H16	0.96 (2)
C11—C2	1.421 (2)	C15—H15	0.96 (2)
C11—C6	1.424 (2)	C17—H17	0.95 (2)
C11—C10	1.422 (2)	C9—C10	1.379 (2)
C1—C13	1.5005 (19)	C9—C8	1.413 (2)
C13—C14	1.393 (2)	C9—H9	0.95 (2)
C2—C3	1.386 (2)	C5—C4	1.376 (2)
C14—C15	1.394 (2)	C5—H5	0.99 (2)
C14—H14	0.94 (2)	C7—C8	1.369 (2)
C6—C5	1.419 (2)	C7—H7	0.96 (2)
C6—C7	1.421 (2)	C4—H4	0.96 (2)
C12—H12A	0.95 (2)	C8—H8	0.97 (2)

C1—N2—C2	117.78 (13)	C2—C3—H3	120.6 (12)
C17—N3—C13	116.91 (13)	C4—C3—H3	119.6 (12)
C1—N1—C12	123.08 (12)	C15—C16—C17	118.60 (14)
C1—N1—C10	119.48 (12)	C15—C16—H16	120.9 (12)
C10—N1—C12	117.35 (12)	C17—C16—H16	120.4 (12)
C2—C11—C6	120.68 (13)	C14—C15—H15	118.8 (12)
C2—C11—C10	119.45 (13)	C16—C15—C14	118.81 (14)
C10—C11—C6	119.86 (14)	C16—C15—H15	122.3 (12)
N2—C1—N1	125.88 (13)	N3—C17—C16	123.87 (15)
N2—C1—C13	114.84 (13)	N3—C17—H17	117.6 (12)
N1—C1—C13	119.20 (12)	C16—C17—H17	118.5 (12)
N3—C13—C1	116.58 (13)	C10—C9—C8	119.10 (15)
N3—C13—C14	123.48 (14)	C10—C9—H9	122.2 (12)
C14—C13—C1	119.74 (13)	C8—C9—H9	118.6 (12)
N2—C2—C11	120.45 (13)	N1—C10—C11	116.90 (13)
C3—C2—N2	119.91 (14)	C9—C10—N1	122.59 (13)
C3—C2—C11	119.62 (14)	C9—C10—C11	120.51 (14)
C13—C14—C15	118.27 (14)	C6—C5—H5	117.5 (12)
C13—C14—H14	119.6 (12)	C4—C5—C6	120.59 (14)
C15—C14—H14	122.2 (12)	C4—C5—H5	121.9 (12)
C5—C6—C11	117.91 (14)	C6—C7—H7	120.0 (12)
C5—C6—C7	123.71 (14)	C8—C7—C6	120.24 (14)
C7—C6—C11	118.37 (14)	C8—C7—H7	119.7 (12)
N1—C12—H12A	110.2 (12)	C3—C4—H4	117.7 (13)
N1—C12—H12B	109.7 (11)	C5—C4—C3	121.47 (15)
N1—C12—H12C	107.6 (11)	C5—C4—H4	120.9 (13)
H12A—C12—H12B	105.7 (17)	C9—C8—H8	118.3 (12)
H12A—C12—H12C	110.7 (17)	C7—C8—C9	121.90 (14)
H12B—C12—H12C	113.0 (15)	C7—C8—H8	119.8 (12)
C2—C3—C4	119.73 (15)

N2—C1—C13—N3	118.34 (15)	C6—C11—C2—C3	−0.2 (2)
N2—C1—C13—C14	−56.73 (19)	C6—C11—C10—N1	−177.46 (12)
N2—C2—C3—C4	−178.61 (13)	C6—C11—C10—C9	1.6 (2)
N3—C13—C14—C15	−2.1 (2)	C6—C5—C4—C3	0.1 (2)
N1—C1—C13—N3	−58.57 (18)	C6—C7—C8—C9	0.7 (2)
N1—C1—C13—C14	126.37 (15)	C12—N1—C1—N2	174.50 (14)
C11—C2—C3—C4	−0.1 (2)	C12—N1—C1—C13	−9.0 (2)
C11—C6—C5—C4	−0.3 (2)	C12—N1—C10—C11	−176.81 (13)
C11—C6—C7—C8	−0.8 (2)	C12—N1—C10—C9	4.2 (2)
C1—N2—C2—C11	−1.7 (2)	C15—C16—C17—N3	−2.0 (2)
C1—N2—C2—C3	176.77 (14)	C17—N3—C13—C1	−172.77 (13)
C1—N1—C10—C11	−0.12 (19)	C17—N3—C13—C14	2.1 (2)
C1—N1—C10—C9	−179.15 (14)	C17—C16—C15—C14	1.9 (2)
C1—C13—C14—C15	172.63 (13)	C10—N1—C1—N2	−2.0 (2)
C13—N3—C17—C16	0.0 (2)	C10—N1—C1—C13	174.54 (12)
C13—C14—C15—C16	0.0 (2)	C10—C11—C2—N2	−0.2 (2)
C2—N2—C1—N1	2.9 (2)	C10—C11—C2—C3	−178.68 (13)
C2—N2—C1—C13	−173.79 (12)	C10—C11—C6—C5	178.90 (13)
C2—C11—C6—C5	0.4 (2)	C10—C11—C6—C7	−0.3 (2)
C2—C11—C6—C7	−178.86 (13)	C10—C9—C8—C7	0.6 (2)
C2—C11—C10—N1	1.1 (2)	C5—C6—C7—C8	−179.97 (15)
C2—C11—C10—C9	−179.87 (13)	C7—C6—C5—C4	178.87 (15)
C2—C3—C4—C5	0.2 (2)	C8—C9—C10—N1	177.31 (13)
C6—C11—C2—N2	178.32 (13)	C8—C9—C10—C11	−1.7 (2)

1,3-Dimethyl-2-(pyridin-2-yl)-1H-perimidinium iodide (3) top

Crystal data top

C₁₈H₁₆N₃⁺·I⁻	F(000) = 792
M_r = 401.24	D_x = 1.589 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.8821 (2) Å	Cell parameters from 9859 reflections
b = 9.7125 (2) Å	θ = 2.3–28.3°
c = 17.9839 (4) Å	µ = 1.91 mm⁻¹
β = 103.676 (1)°	T = 230 K
V = 1677.15 (6) Å³	Block, yellow
Z = 4	0.32 × 0.18 × 0.13 mm

Data collection top

Bruker SMART APEXII diffractometer	4146 independent reflections
Radiation source: fine-focus sealed X-ray tube, X-ray tube	3700 reflections with I > 2σ(I)
Mirror optics monochromator	R_int = 0.026
Detector resolution: 7.9 pixels mm^-1	θ_max = 28.4°, θ_min = 2.3°
ω scan	h = −13→13
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −12→12
T_min = 0.668, T_max = 0.746	l = −23→23
28389 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0273P)² + 1.1509P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4146 reflections	Δρ_max = 0.72 e Å⁻³
201 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.46311 (2)	0.43924 (2)	0.27610 (2)	0.05057 (7)
N2	0.70014 (19)	0.6145 (2)	0.48068 (10)	0.0417 (4)
C14	0.6404 (2)	0.8060 (2)	0.39271 (12)	0.0389 (4)
N1	0.78491 (17)	0.61380 (19)	0.37060 (10)	0.0380 (4)
C11	0.8424 (2)	0.4240 (2)	0.45912 (13)	0.0397 (4)
C15	0.5033 (2)	0.8101 (2)	0.35210 (14)	0.0475 (5)
H15	0.453130	0.728579	0.336938	0.057*
C1	0.7119 (2)	0.6712 (2)	0.41527 (12)	0.0377 (4)
N3	0.7182 (2)	0.9164 (2)	0.41510 (15)	0.0633 (6)
C2	0.7651 (2)	0.4869 (2)	0.50629 (13)	0.0425 (5)
C10	0.8527 (2)	0.4851 (2)	0.38939 (12)	0.0401 (4)
C3	0.7545 (3)	0.4271 (3)	0.57385 (16)	0.0573 (6)
H3	0.701812	0.469174	0.604759	0.069*
C6	0.9113 (2)	0.2971 (2)	0.48227 (15)	0.0494 (5)
C16	0.4421 (3)	0.9371 (3)	0.33438 (17)	0.0562 (6)
H16	0.348626	0.943924	0.307067	0.067*
C7	0.9857 (3)	0.2348 (3)	0.43274 (18)	0.0619 (7)
H7	1.031867	0.150768	0.446700	0.074*
C13	0.6248 (3)	0.6850 (3)	0.53130 (15)	0.0618 (7)
H13A	0.589318	0.772451	0.508734	0.093*
H13B	0.687651	0.701041	0.580789	0.093*
H13C	0.547719	0.628024	0.537689	0.093*
C8	0.9909 (3)	0.2948 (3)	0.36572 (18)	0.0646 (7)
H8	1.039315	0.250527	0.333392	0.078*
C17	0.5194 (3)	1.0531 (2)	0.35717 (18)	0.0600 (7)
H17	0.480165	1.141064	0.346141	0.072*
C12	0.7915 (3)	0.6767 (3)	0.29709 (13)	0.0525 (6)
H12A	0.741265	0.619574	0.255397	0.079*
H12B	0.887977	0.684564	0.294207	0.079*
H12C	0.749586	0.767565	0.293224	0.079*
C18	0.6552 (4)	1.0379 (3)	0.3964 (2)	0.0725 (9)
H18	0.707770	1.118127	0.411245	0.087*
C9	0.9255 (3)	0.4220 (3)	0.34300 (16)	0.0536 (6)
H9	0.931871	0.462969	0.296594	0.064*
C5	0.8993 (3)	0.2393 (3)	0.55276 (18)	0.0622 (7)
H5	0.944762	0.155928	0.569505	0.075*
C4	0.8238 (3)	0.3020 (3)	0.59604 (17)	0.0659 (8)
H4	0.817190	0.261112	0.642411	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.05271 (10)	0.04098 (9)	0.05737 (11)	−0.00419 (6)	0.01171 (7)	−0.01150 (6)
N2	0.0404 (9)	0.0444 (10)	0.0404 (9)	0.0032 (8)	0.0100 (7)	0.0044 (8)
C14	0.0395 (10)	0.0339 (10)	0.0430 (10)	−0.0019 (8)	0.0090 (8)	0.0019 (8)
N1	0.0339 (8)	0.0395 (9)	0.0389 (9)	−0.0004 (7)	0.0054 (7)	0.0043 (7)
C11	0.0312 (9)	0.0350 (10)	0.0467 (11)	−0.0059 (8)	−0.0029 (8)	0.0020 (8)
C15	0.0396 (11)	0.0363 (11)	0.0629 (14)	−0.0025 (9)	0.0049 (10)	0.0001 (10)
C1	0.0313 (9)	0.0375 (10)	0.0416 (10)	−0.0021 (8)	0.0035 (8)	0.0033 (8)
N3	0.0528 (12)	0.0445 (12)	0.0820 (16)	−0.0107 (10)	−0.0054 (11)	−0.0028 (11)
C2	0.0363 (10)	0.0416 (11)	0.0463 (11)	−0.0045 (9)	0.0031 (9)	0.0085 (9)
C10	0.0326 (10)	0.0401 (11)	0.0427 (11)	−0.0011 (8)	−0.0005 (8)	−0.0030 (9)
C3	0.0531 (14)	0.0652 (17)	0.0532 (14)	−0.0032 (12)	0.0118 (11)	0.0165 (12)
C6	0.0384 (11)	0.0356 (11)	0.0644 (14)	−0.0056 (9)	−0.0072 (10)	0.0028 (10)
C16	0.0457 (13)	0.0501 (14)	0.0697 (16)	0.0107 (11)	0.0079 (12)	0.0046 (12)
C7	0.0487 (14)	0.0378 (12)	0.088 (2)	0.0056 (11)	−0.0068 (13)	−0.0064 (12)
C13	0.0679 (16)	0.0709 (17)	0.0523 (14)	0.0169 (14)	0.0255 (12)	0.0077 (13)
C8	0.0539 (15)	0.0597 (16)	0.0761 (18)	0.0122 (13)	0.0072 (13)	−0.0189 (14)
C17	0.0728 (18)	0.0353 (12)	0.0735 (17)	0.0086 (11)	0.0201 (14)	0.0032 (11)
C12	0.0540 (13)	0.0605 (15)	0.0452 (12)	0.0073 (12)	0.0163 (10)	0.0136 (11)
C18	0.075 (2)	0.0353 (13)	0.099 (2)	−0.0130 (13)	0.0047 (17)	−0.0059 (13)
C9	0.0497 (13)	0.0563 (14)	0.0530 (13)	0.0056 (11)	0.0086 (11)	−0.0080 (11)
C5	0.0538 (14)	0.0416 (13)	0.0792 (18)	−0.0041 (11)	−0.0085 (13)	0.0203 (12)
C4	0.0599 (16)	0.0647 (17)	0.0673 (17)	−0.0064 (14)	0.0036 (13)	0.0311 (14)

Geometric parameters (Å, º) top

N2—C1	1.328 (3)	C6—C5	1.417 (4)
N2—C2	1.422 (3)	C16—H16	0.9400
N2—C13	1.474 (3)	C16—C17	1.369 (4)
C14—C15	1.379 (3)	C7—H7	0.9400
C14—C1	1.497 (3)	C7—C8	1.351 (4)
C14—N3	1.326 (3)	C13—H13A	0.9700
N1—C1	1.323 (3)	C13—H13B	0.9700
N1—C10	1.421 (3)	C13—H13C	0.9700
N1—C12	1.472 (3)	C8—H8	0.9400
C11—C2	1.408 (3)	C8—C9	1.409 (4)
C11—C10	1.413 (3)	C17—H17	0.9400
C11—C6	1.422 (3)	C17—C18	1.368 (4)
C15—H15	0.9400	C12—H12A	0.9700
C15—C16	1.378 (3)	C12—H12B	0.9700
N3—C18	1.339 (4)	C12—H12C	0.9700
C2—C3	1.373 (3)	C18—H18	0.9400
C10—C9	1.369 (3)	C9—H9	0.9400
C3—H3	0.9400	C5—H5	0.9400
C3—C4	1.405 (4)	C5—C4	1.345 (4)
C6—C7	1.417 (4)	C4—H4	0.9400

C1—N2—C2	121.39 (19)	C6—C7—H7	119.6
C1—N2—C13	121.1 (2)	C8—C7—C6	120.8 (2)
C2—N2—C13	117.40 (19)	C8—C7—H7	119.6
C15—C14—C1	120.71 (19)	N2—C13—H13A	109.5
N3—C14—C15	124.3 (2)	N2—C13—H13B	109.5
N3—C14—C1	114.99 (19)	N2—C13—H13C	109.5
C1—N1—C10	121.36 (18)	H13A—C13—H13B	109.5
C1—N1—C12	121.10 (18)	H13A—C13—H13C	109.5
C10—N1—C12	117.43 (18)	H13B—C13—H13C	109.5
C2—C11—C10	121.08 (19)	C7—C8—H8	119.2
C2—C11—C6	119.4 (2)	C7—C8—C9	121.7 (3)
C10—C11—C6	119.6 (2)	C9—C8—H8	119.2
C14—C15—H15	120.9	C16—C17—H17	120.8
C16—C15—C14	118.2 (2)	C18—C17—C16	118.4 (2)
C16—C15—H15	120.9	C18—C17—H17	120.8
N2—C1—C14	117.88 (19)	N1—C12—H12A	109.5
N1—C1—N2	122.52 (19)	N1—C12—H12B	109.5
N1—C1—C14	119.60 (18)	N1—C12—H12C	109.5
C14—N3—C18	115.8 (2)	H12A—C12—H12B	109.5
C11—C2—N2	116.78 (19)	H12A—C12—H12C	109.5
C3—C2—N2	122.2 (2)	H12B—C12—H12C	109.5
C3—C2—C11	121.0 (2)	N3—C18—C17	124.5 (2)
C11—C10—N1	116.85 (19)	N3—C18—H18	117.8
C9—C10—N1	122.4 (2)	C17—C18—H18	117.8
C9—C10—C11	120.8 (2)	C10—C9—C8	119.1 (3)
C2—C3—H3	120.6	C10—C9—H9	120.4
C2—C3—C4	118.9 (3)	C8—C9—H9	120.4
C4—C3—H3	120.6	C6—C5—H5	119.6
C7—C6—C11	118.0 (2)	C4—C5—C6	120.9 (2)
C5—C6—C11	118.0 (2)	C4—C5—H5	119.6
C5—C6—C7	123.9 (2)	C3—C4—H4	119.1
C15—C16—H16	120.5	C5—C4—C3	121.8 (3)
C17—C16—C15	118.9 (2)	C5—C4—H4	119.1
C17—C16—H16	120.5

N2—C2—C3—C4	−178.8 (2)	C2—C11—C6—C5	−0.2 (3)
C14—C15—C16—C17	0.4 (4)	C2—C3—C4—C5	−0.3 (4)
C14—N3—C18—C17	0.3 (5)	C10—N1—C1—N2	1.7 (3)
N1—C10—C9—C8	179.6 (2)	C10—N1—C1—C14	−179.10 (18)
C11—C2—C3—C4	0.7 (4)	C10—C11—C2—N2	−0.7 (3)
C11—C10—C9—C8	−0.2 (4)	C10—C11—C2—C3	179.7 (2)
C11—C6—C7—C8	0.2 (4)	C10—C11—C6—C7	−1.6 (3)
C11—C6—C5—C4	0.6 (4)	C10—C11—C6—C5	179.6 (2)
C15—C14—C1—N2	−87.1 (3)	C6—C11—C2—N2	179.11 (18)
C15—C14—C1—N1	93.6 (3)	C6—C11—C2—C3	−0.5 (3)
C15—C14—N3—C18	0.6 (4)	C6—C11—C10—N1	−178.17 (18)
C15—C16—C17—C18	0.4 (5)	C6—C11—C10—C9	1.6 (3)
C1—N2—C2—C11	0.2 (3)	C6—C7—C8—C9	1.2 (4)
C1—N2—C2—C3	179.7 (2)	C6—C5—C4—C3	−0.4 (4)
C1—C14—C15—C16	178.6 (2)	C16—C17—C18—N3	−0.8 (5)
C1—C14—N3—C18	−179.0 (3)	C7—C6—C5—C4	−178.1 (3)
C1—N1—C10—C11	−2.1 (3)	C7—C8—C9—C10	−1.3 (4)
C1—N1—C10—C9	178.1 (2)	C13—N2—C1—C14	−2.8 (3)
N3—C14—C15—C16	−1.0 (4)	C13—N2—C1—N1	176.4 (2)
N3—C14—C1—N2	92.5 (3)	C13—N2—C2—C11	−177.0 (2)
N3—C14—C1—N1	−86.8 (3)	C13—N2—C2—C3	2.6 (3)
C2—N2—C1—C14	−179.88 (18)	C12—N1—C1—N2	177.7 (2)
C2—N2—C1—N1	−0.6 (3)	C12—N1—C1—C14	−3.1 (3)
C2—C11—C10—N1	1.7 (3)	C12—N1—C10—C11	−178.33 (19)
C2—C11—C10—C9	−178.6 (2)	C12—N1—C10—C9	1.9 (3)
C2—C11—C6—C7	178.6 (2)	C5—C6—C7—C8	178.9 (3)

Acknowledgements

X-ray diffraction studies were performed at the Centre of Shared Equipment of IGIC RAS. Dr I. M. Vatsouro is acknowledged for assistance with the NMR measurements.

Funding information

Funding for this research was provided by: Presidential Grant Program (grant No. MK-1200.2020.3).

References

Bahena, E. N., Gijon, C. A. F., Fomine, S., Alexandrova, L. & Le Lagadec, R. (2019). Eur. J. Inorg. Chem. 3494–3502. Google Scholar
Booysen, I. N., Ebinumoliseh, I., Sithebe, S., Akerman, M. P. & Xulu, B. (2016). Polyhedron, 117, 755–760. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2017). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Foces-Foces, C., Llamas-Saiz, A. L., Claramunt, R. M., Sanz, D., Dotor, J. & Elguero, J. (1993). J. Cryst. Spec. Res. 23, 305–312. CAS Google Scholar
Hill, A. F., Ma, C., McQueen, C. M. A. & Ward, J. S. (2018). Dalton Trans. 47, 1577–1587. Web of Science CSD CrossRef CAS PubMed Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, Z.-Y., Zhang, M., Yuan, X.-Y. & Yuan, L. (2017). Z. Kristallogr. New Cryst. Struct. 232, 429–430. CSD CrossRef CAS Google Scholar
Llamas-Saiz, A. L., Foces-Foces, C., Sanz, D., Claramunt, R. M., Dotor, J., Elguero, J., Catalan, J. & del Valle, J. C. (1995). J. Chem. Soc., Perkin Trans. 2, 1389–1398. Google Scholar
Pozharskii, A. F., Gulevskaya, A. V., Claramunt, R. M., Alkorta, I. & Elguero, J. (2020). Russ. Chem. Rev. 89, 1204–1260. CrossRef Google Scholar
Sahiba, N. & Agarwal, S. (2020). Top. Curr. Chem. 378 article number 44. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 96-100

https://doi.org/10.1107/S205698902100013X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Synthesis and comparative structural study of 2-(pyridin-2-yl)-1H-perimidine and its mono- and di-N-methyl­ated analogues

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Synthesis and comparative structural study of 2-(pyridin-2-yl)-1H-perimidine and its mono- and di-N-methylated analogues

3. Supramolecular features