organic compounds
6-Methyl-2-[(6-methylpyridin-2-yl)amino]pyridinium chloride chloroform monosolvate
aInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: mklass@ac.uni-kiel.de
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
Structure description
The title compound is shown in Fig. 1. The hydrogen bonding (Table 1) in the is illustrated in Fig. 2.
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 .
details are summarized in Table 2
|
Structural data
CCDC reference: 1443905
10.1107/S2414314615024670/hb4005sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314615024670/hb4005Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314615024670/hb4005Isup3.cml
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.
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 Ueq(H) = 1.2 Ueq(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 Ueq(H) = 1.2 Ueq(N) using a riding model.
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.
The title compound is shown in Fig. 1. The hydrogen bonding (Table 1) in the
is illustrated in Fig. 2.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.
Data collection: X-AREA (Stoe, 2008); cell
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).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. |
C12H12N3+·Cl−·CH3Cl | Z = 2 |
Mr = 355.08 | F(000) = 364 |
Triclinic, P1 | Dx = 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 |
Stoe IPDS-2 diffractometer | 2885 reflections with I > 2σ(I) |
ω scan | Rint = 0.029 |
Absorption correction: numerical (X-RED and X-SHAPE; Stoe, 2008) | θmax = 27.0°, θmin = 1.7° |
Tmin = 0.802, Tmax = 0.941 | h = −9→9 |
11648 measured reflections | k = −12→12 |
3487 independent reflections | l = −14→16 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0529P)2 + 0.1904P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.100 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.37 e Å−3 |
3487 reflections | Δρmin = −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) |
C12H12N3+·Cl−·CH3Cl | γ = 72.582 (4)° |
Mr = 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)° |
Stoe IPDS-2 diffractometer | 3487 independent reflections |
Absorption correction: numerical (X-RED and X-SHAPE; Stoe, 2008) | 2885 reflections with I > 2σ(I) |
Tmin = 0.802, Tmax = 0.941 | Rint = 0.029 |
11648 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.37 e Å−3 |
3487 reflections | Δρmin = −0.50 e Å−3 |
184 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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. |
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 |
Mr | 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) |
Tmin, Tmax | 0.802, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11648, 3487, 2885 |
Rint | 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 |
Δρmax, Δρmin (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
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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
Silberg, J., Schareina, T., Kempe, R., Wurst, K. & Buchmeiser, M. R. (2001). J. Organomet. Chem. 622, 6–18. Web of Science CSD CrossRef CAS Google Scholar
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
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.