6-Methyl-2-[(6-methyl­pyridin-2-yl)amino]­pyridinium chloride chloro­form monosolvate

Klass, M.; Näther, C.; Tuczek, F.

doi:10.1107/S2414314615024670

organic compounds

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ISSN: 2414-3146

Volume 1| Part 1| January 2016| x152467

doi:10.1107/S2414314615024670

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6-Methyl-2-[(6-methylpyridin-2-yl)amino]pyridinium chloride chloroform monosolvate

Michaela Klass,^a ^* Christian Näther ^a and Felix Tuczek ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: mklass@ac.uni-kiel.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 December 2015; accepted 22 December 2015; online 12 January 2016)

In the title solvated molecular salt, C₁₂H₁₄N₃⁺·Cl⁻·CHCl₃, the aromatic rings of the cation are nearly coplanar [dihedral angle = 6.30 (5)°] and an intramolecular N—H⋯N hydrogen bond occurs. In the crystal, the chloride ion accepts an N—H⋯Cl hydrogen bond from the cation and a C—H⋯Cl interaction from the solvent molecule. These trimeric units are linked by cation-to-anion C—H⋯Cl interactions into chains that propagate in the [001] direction.

Keywords: crystal structure; chloroform solvate; hydrogen bonding.

CCDC reference: 1443905

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Chemical scheme

Structure description

The title compound is shown in Fig. 1. The hydrogen bonding (Table 1) in the crystal structure is illustrated in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3n⋯N1	0.88	1.92	2.602 (2)	133
N2—H2N⋯Cl1	0.88	2.20	3.0771 (15)	177
C5—H5⋯Cl2ⁱ	0.95	2.92	3.7969 (19)	154
C13—H13⋯Cl1	1.00	2.42	3.396 (2)	164
Symmetry code: (i) -x+1, -y+1, -z.

Figure 1
Part of the crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Hydrogen bonding is shown as dashed lines.

Figure 2
Crystal structure of the title compound with view along the crystallographic a axis. Hydrogen bonding is shown as dashed lines.

For the related crystal structures of 2-(pyridin-1-ylamino)pyridinium iodide chloroform monosolvatesolvate, of 2-(pyridin-1-ylamino)pyridinium chloride dihydrate and of 2-(pyridin-1-ylamino)pyridinium chloride monohydrate, see: Chernychev et al. (2014 ) and Bock et al. (1998 ), respectively.

Synthesis and crystallization

Bis-(6-methylpyridin-2-yl)amine was synthesized according to the procedure given by Silberg et al. (2001 ). The compound was dissolved in dilute hydrochloric acid and extracted with dichloromethane. After solvent removal it was recrystallized from chloroform solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₃⁺·Cl⁻·CH₃Cl
M_r	355.08
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	170
a, b, c (Å)	7.0474 (3), 9.7775 (5), 12.8695 (6)
α, β, γ (°)	71.744 (3), 89.177 (4), 72.582 (4)
V (Å³)	800.44 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.73
Crystal size (mm)	0.14 × 0.10 × 0.06

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe, 2008 )
T_min, T_max	0.802, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	11648, 3487, 2885
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 1.07
No. of reflections	3487
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.50
Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1443905

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314615024670/hb4005sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314615024670/hb4005Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314615024670/hb4005Isup3.cml

checkCIF report

Synthesis and Crystallization top

Bis-(6-methyl-pyridin-2-yl)amine was synthesized according to the procedure given by Silberg et al. (2001). The compound was dissolved in dilute hydrochloric acid and extracted with dichloromethane. After solvent removal it was recrystallized from chloroform solution.

Refinement top

The C—H H and the N—H H atom attached to N3 atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropic with U_eq(H) = 1.2 U_eq(C,N) (1.5 for methyl H atoms and the N—H H atom) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.98 Å for methyl and N—H = 0.88 Å for the N—H H atom. The N—H H atom attached to N2 was located in difference map, its bond lengths set to an ideal value of N—H = 0.88 Å and finally it was refined isotropic with U_eq(H) = 1.2 U_eq(N) using a riding model.

Related literature top

For the related crystal structures of 2-(pyridin-1yl–amino)pyridinium iodide chloroform solvate, of 2-(pyridin-1yl–amino)pyridinium chloride dihydrate and of 2-(pyridin-1yl–amino)pyridinium chloride monohydrate solvate, see: Chernychev et al. (2014) and Bock et al. (1998), respectively.

Experimental top

Structure description top

The title compound is shown in Fig. 1. The hydrogen bonding (Table 1) in the crystal structure is illustrated in Fig. 2.

Computing details top

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Part of the crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. Hydrogen bonding is shown as dashed lines.
	Fig. 2. Crystal structure of the title compound with view along the crystallographic a axis. Hydrogen bonding is shown as dashed lines.

6-Methyl-2-[(6-methylpyridin-2-yl)amino]pyridinium chloride chloroform monosolvate top

Crystal data top

C₁₂H₁₂N₃⁺·Cl⁻·CH₃Cl	Z = 2
M_r = 355.08	F(000) = 364
Triclinic, P1	D_x = 1.473 Mg m⁻³
a = 7.0474 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7775 (5) Å	Cell parameters from 11648 reflections
c = 12.8695 (6) Å	θ = 1.7–27.0°
α = 71.744 (3)°	µ = 0.73 mm⁻¹
β = 89.177 (4)°	T = 170 K
γ = 72.582 (4)°	Block, colorless
V = 800.44 (7) Å³	0.14 × 0.10 × 0.06 mm

Data collection top

Stoe IPDS-2 diffractometer	2885 reflections with I > 2σ(I)
ω scan	R_int = 0.029
Absorption correction: numerical (X-RED and X-SHAPE; Stoe, 2008)	θ_max = 27.0°, θ_min = 1.7°
T_min = 0.802, T_max = 0.941	h = −9→9
11648 measured reflections	k = −12→12
3487 independent reflections	l = −14→16

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0529P)² + 0.1904P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.100	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.37 e Å⁻³
3487 reflections	Δρ_min = −0.50 e Å⁻³
184 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.012 (4)

Crystal data top

C₁₂H₁₂N₃⁺·Cl⁻·CH₃Cl	γ = 72.582 (4)°
M_r = 355.08	V = 800.44 (7) Å³
Triclinic, P1	Z = 2
a = 7.0474 (3) Å	Mo Kα radiation
b = 9.7775 (5) Å	µ = 0.73 mm⁻¹
c = 12.8695 (6) Å	T = 170 K
α = 71.744 (3)°	0.14 × 0.10 × 0.06 mm
β = 89.177 (4)°

Data collection top

Stoe IPDS-2 diffractometer	3487 independent reflections
Absorption correction: numerical (X-RED and X-SHAPE; Stoe, 2008)	2885 reflections with I > 2σ(I)
T_min = 0.802, T_max = 0.941	R_int = 0.029
11648 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.07	Δρ_max = 0.37 e Å⁻³
3487 reflections	Δρ_min = −0.50 e Å⁻³
184 parameters

Special details top

Experimental. X-RED and X-SHAPE (STOE, 2008)

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
C1	0.2170 (2)	0.56775 (18)	0.42537 (14)	0.0307 (3)
N1	0.1363 (2)	0.62988 (15)	0.50101 (12)	0.0311 (3)
C2	0.0123 (2)	0.77434 (18)	0.46826 (15)	0.0329 (4)
C3	−0.0301 (3)	0.85842 (19)	0.35861 (16)	0.0375 (4)
H3	−0.1169	0.9598	0.3365	0.045*
C4	0.0558 (3)	0.7931 (2)	0.28052 (16)	0.0382 (4)
H4	0.0282	0.8501	0.2046	0.046*
C5	0.1808 (3)	0.6459 (2)	0.31318 (15)	0.0347 (4)
H5	0.2401	0.5993	0.2610	0.042*
C6	−0.0711 (3)	0.8329 (2)	0.55911 (17)	0.0401 (4)
H6A	−0.1584	0.7759	0.5979	0.060*
H6B	−0.1480	0.9405	0.5284	0.060*
H6C	0.0386	0.8208	0.6106	0.060*
N2	0.3428 (2)	0.41937 (15)	0.46120 (12)	0.0324 (3)
H2N	0.3963	0.3812	0.4102	0.049*
C7	0.3893 (2)	0.32334 (18)	0.56621 (14)	0.0313 (3)
N3	0.3260 (2)	0.37459 (15)	0.64998 (12)	0.0318 (3)
H3N	0.2560	0.4706	0.6350	0.038*
C8	0.3655 (3)	0.2848 (2)	0.75685 (15)	0.0355 (4)
C9	0.4732 (3)	0.1354 (2)	0.78009 (16)	0.0398 (4)
H9	0.5021	0.0704	0.8541	0.048*
C10	0.5407 (3)	0.0785 (2)	0.69463 (17)	0.0403 (4)
H10	0.6145	−0.0255	0.7109	0.048*
C11	0.5014 (3)	0.17111 (19)	0.58816 (16)	0.0363 (4)
H11	0.5492	0.1331	0.5301	0.044*
C12	0.2855 (3)	0.3610 (2)	0.83920 (16)	0.0458 (4)
H12A	0.3130	0.2857	0.9129	0.069*
H12B	0.1410	0.4092	0.8227	0.069*
H12C	0.3498	0.4380	0.8362	0.069*
Cl1	0.53676 (8)	0.27483 (5)	0.28940 (4)	0.04733 (15)
C13	0.8018 (3)	0.2797 (2)	0.06653 (17)	0.0480 (5)
H13	0.7065	0.2978	0.1227	0.058*
Cl2	0.74696 (8)	0.44562 (6)	−0.04674 (4)	0.05151 (16)
Cl3	1.04500 (10)	0.23050 (10)	0.12560 (6)	0.0780 (2)
Cl4	0.77072 (12)	0.13078 (7)	0.02606 (6)	0.0723 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0285 (8)	0.0325 (8)	0.0352 (9)	−0.0113 (6)	0.0055 (7)	−0.0147 (7)
N1	0.0294 (7)	0.0312 (7)	0.0359 (7)	−0.0096 (5)	0.0065 (6)	−0.0154 (6)
C2	0.0285 (8)	0.0302 (8)	0.0432 (10)	−0.0098 (6)	0.0051 (7)	−0.0157 (7)
C3	0.0335 (9)	0.0324 (8)	0.0453 (10)	−0.0100 (7)	0.0010 (7)	−0.0111 (7)
C4	0.0387 (9)	0.0394 (9)	0.0355 (9)	−0.0142 (7)	0.0002 (7)	−0.0089 (7)
C5	0.0360 (9)	0.0390 (9)	0.0328 (9)	−0.0137 (7)	0.0062 (7)	−0.0147 (7)
C6	0.0390 (9)	0.0353 (9)	0.0512 (11)	−0.0103 (7)	0.0107 (8)	−0.0226 (8)
N2	0.0344 (7)	0.0325 (7)	0.0325 (7)	−0.0080 (6)	0.0078 (6)	−0.0160 (6)
C7	0.0281 (8)	0.0330 (8)	0.0365 (9)	−0.0108 (6)	0.0058 (7)	−0.0152 (7)
N3	0.0317 (7)	0.0306 (7)	0.0348 (7)	−0.0094 (5)	0.0061 (6)	−0.0133 (6)
C8	0.0327 (8)	0.0396 (9)	0.0360 (9)	−0.0145 (7)	0.0045 (7)	−0.0116 (7)
C9	0.0381 (9)	0.0383 (9)	0.0392 (10)	−0.0121 (7)	−0.0003 (8)	−0.0070 (8)
C10	0.0364 (9)	0.0323 (8)	0.0499 (11)	−0.0077 (7)	−0.0013 (8)	−0.0128 (8)
C11	0.0314 (8)	0.0346 (8)	0.0451 (10)	−0.0074 (7)	0.0024 (7)	−0.0186 (8)
C12	0.0497 (11)	0.0521 (11)	0.0367 (10)	−0.0149 (9)	0.0095 (8)	−0.0168 (9)
Cl1	0.0594 (3)	0.0437 (3)	0.0439 (3)	−0.0157 (2)	0.0212 (2)	−0.0220 (2)
C13	0.0480 (11)	0.0542 (11)	0.0368 (10)	−0.0102 (9)	0.0081 (8)	−0.0135 (9)
Cl2	0.0574 (3)	0.0499 (3)	0.0397 (3)	−0.0087 (2)	0.0098 (2)	−0.0119 (2)
Cl3	0.0540 (4)	0.1047 (5)	0.0553 (4)	−0.0188 (3)	−0.0076 (3)	−0.0035 (3)
Cl4	0.0938 (5)	0.0535 (3)	0.0663 (4)	−0.0184 (3)	0.0004 (4)	−0.0188 (3)

Geometric parameters (Å, º) top

C1—N1	1.337 (2)	C7—C11	1.399 (2)
C1—N2	1.388 (2)	N3—C8	1.359 (2)
C1—C5	1.391 (2)	N3—H3N	0.8800
N1—C2	1.355 (2)	C8—C9	1.366 (3)
C2—C3	1.376 (3)	C8—C12	1.491 (3)
C2—C6	1.496 (3)	C9—C10	1.398 (3)
C3—C4	1.392 (3)	C9—H9	0.9500
C3—H3	0.9500	C10—C11	1.363 (3)
C4—C5	1.377 (3)	C10—H10	0.9500
C4—H4	0.9500	C11—H11	0.9500
C5—H5	0.9500	C12—H12A	0.9800
C6—H6A	0.9800	C12—H12B	0.9800
C6—H6B	0.9800	C12—H12C	0.9800
C6—H6C	0.9800	C13—Cl3	1.749 (2)
N2—C7	1.360 (2)	C13—Cl2	1.751 (2)
N2—H2N	0.8800	C13—Cl4	1.763 (2)
C7—N3	1.343 (2)	C13—H13	1.0000

N1—C1—N2	118.11 (15)	C7—N3—C8	122.93 (15)
N1—C1—C5	122.75 (15)	C7—N3—H3N	118.5
N2—C1—C5	119.14 (15)	C8—N3—H3N	118.5
C1—N1—C2	119.32 (15)	N3—C8—C9	118.58 (17)
N1—C2—C3	121.07 (16)	N3—C8—C12	115.71 (16)
N1—C2—C6	115.17 (16)	C9—C8—C12	125.71 (18)
C3—C2—C6	123.76 (16)	C8—C9—C10	119.86 (18)
C2—C3—C4	119.17 (16)	C8—C9—H9	120.1
C2—C3—H3	120.4	C10—C9—H9	120.1
C4—C3—H3	120.4	C11—C10—C9	120.55 (17)
C5—C4—C3	120.08 (17)	C11—C10—H10	119.7
C5—C4—H4	120.0	C9—C10—H10	119.7
C3—C4—H4	120.0	C10—C11—C7	118.61 (17)
C4—C5—C1	117.60 (16)	C10—C11—H11	120.7
C4—C5—H5	121.2	C7—C11—H11	120.7
C1—C5—H5	121.2	C8—C12—H12A	109.5
C2—C6—H6A	109.5	C8—C12—H12B	109.5
C2—C6—H6B	109.5	H12A—C12—H12B	109.5
H6A—C6—H6B	109.5	C8—C12—H12C	109.5
C2—C6—H6C	109.5	H12A—C12—H12C	109.5
H6A—C6—H6C	109.5	H12B—C12—H12C	109.5
H6B—C6—H6C	109.5	Cl3—C13—Cl2	111.00 (12)
C7—N2—C1	127.70 (14)	Cl3—C13—Cl4	110.30 (12)
C7—N2—H2N	115.6	Cl2—C13—Cl4	109.85 (12)
C1—N2—H2N	116.7	Cl3—C13—H13	108.5
N3—C7—N2	119.76 (15)	Cl2—C13—H13	108.5
N3—C7—C11	119.47 (16)	Cl4—C13—H13	108.5
N2—C7—C11	120.77 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3n···N1	0.88	1.92	2.602 (2)	133
N2—H2N···Cl1	0.88	2.20	3.0771 (15)	177
C5—H5···Cl2ⁱ	0.95	2.92	3.7969 (19)	154
C13—H13···Cl1	1.00	2.42	3.396 (2)	164

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3n···N1	0.88	1.92	2.602 (2)	133
N2—H2N···Cl1	0.88	2.20	3.0771 (15)	177
C5—H5···Cl2ⁱ	0.95	2.92	3.7969 (19)	154
C13—H13···Cl1	1.00	2.42	3.396 (2)	164

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₃⁺·Cl⁻·CH₃Cl
M_r	355.08
Crystal system, space group	Triclinic, P1
Temperature (K)	170
a, b, c (Å)	7.0474 (3), 9.7775 (5), 12.8695 (6)
α, β, γ (°)	71.744 (3), 89.177 (4), 72.582 (4)
V (Å³)	800.44 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.14 × 0.10 × 0.06

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe, 2008)
T_min, T_max	0.802, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	11648, 3487, 2885
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.100, 1.07
No. of reflections	3487
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.50

Computer programs: X-AREA (Stoe, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the DFG (SFB 677 Function by Switching). We gratefully acknowledge financial support by the State of Schleswig–Holstein.

References

Bock, H., Schödel, H., Van, T. T. H., Dienelt, R. & Gluth, M. (1998). J. Prakt. Chem. 340, 722–732. Web of Science CSD CrossRef CAS Google Scholar
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Chernychev, A. N., Morozov, D., Mutanen, J., Kukushkin, V. Y., Groenhof, G. & Haukka, M. (2014). J. Mater. Chem. C2, 8285–8294. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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Stoe (2008). X-AREA, X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Methyl-2-[(6-methyl­pyridin-2-yl)amino]­pyridinium chloride chloro­form monosolvate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

6-Methyl-2-[(6-methylpyridin-2-yl)amino]pyridinium chloride chloroform monosolvate