Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025718/fl2132sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025718/fl2132Isup2.hkl |
CCDC reference: 654863
Key indicators
- Single-crystal X-ray study
- T = 90 K
- Mean (C-C)= 0.003 Å
- R factor = 0.049
- wR factor = 0.138
- Data-to-parameter ratio = 20.4
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
Pyridine (3.78 g, 47.8 mmol) was introduced to a round bottom flask containing 2-chloronicotinic acid (7.32 g, 46 mmol) and 2,4,6-trimethylaniline (6.55 g, 48.5 mmol), followed by addition of p-toluenesulfonic acid (1.2 g, 6.98 mmol) dissovled in 20 ml of water. The solution was then refluxed overnight. After workup, both the desired product, 2-[(2,4,6-trimethylphenyl)amino]-3-pyridinecarboxylic acid, and some by-products, including the title compound, were obtained. Crystals of the title compound were grown from methanol solution by slow evaporation.
The title compound, (I), was a by-product during our attempts to synthesize 2-[(2,4,6-trimethylphenyl)amino]-3-pyridinecarboxylic acid, a potential anti-inflammatory compound (Ting et al., 1990).
The asymmetric unit of the crystal I (Fig. 1) consists of a 2,4,6-trimethylbenzenaminium cation and a chloride anion·In the crystal of I, all the available hydrogen bonding donors and acceptors are involved in the three-dimensional hydrogen bonding network. The molecules in the crystal form columns with a width of two molecules along the a axis through N—H···Cl hydrogen bonds (Table 1). The N—H···Cl hydrogen bonds link pairs of molecules around a center of symmetry and further connect these pairs of molecules in the [1 0 0] direction. Moreover, the aromatic rings on each side of the columns are stacked face-to-face, suggesting π-π stacking may provide additional stablitity to the crystal structure (Fig. 2).
For related literature, see: Ting et al. (1990).
Data collection: COLLECT (Nonius, 2002); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local programs.
Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms). | |
Fig. 2. A packing diagram of (I) along a axis. |
C9H14N+·Cl− | F(000) = 368 |
Mr = 171.66 | Dx = 1.233 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 4.811 (1) Å | Cell parameters from 2207 reflections |
b = 15.373 (3) Å | θ = 1.0–27.5° |
c = 12.509 (2) Å | µ = 0.35 mm−1 |
β = 90.99 (3)° | T = 90 K |
V = 925.0 (3) Å3 | Thick needle, colorless |
Z = 4 | 0.40 × 0.13 × 0.03 mm |
Nonius KappaCCD area-detector diffractometer | 2121 independent reflections |
Radiation source: fine-focus sealed tube | 1453 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 18 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans at fixed χ = 55° | h = −6→6 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −19→19 |
Tmin = 0.873, Tmax = 0.990 | l = −16→16 |
4000 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0771P)2] where P = (Fo2 + 2Fc2)/3 |
2121 reflections | (Δ/σ)max < 0.001 |
104 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C9H14N+·Cl− | V = 925.0 (3) Å3 |
Mr = 171.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.811 (1) Å | µ = 0.35 mm−1 |
b = 15.373 (3) Å | T = 90 K |
c = 12.509 (2) Å | 0.40 × 0.13 × 0.03 mm |
β = 90.99 (3)° |
Nonius KappaCCD area-detector diffractometer | 2121 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 1453 reflections with I > 2σ(I) |
Tmin = 0.873, Tmax = 0.990 | Rint = 0.046 |
4000 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.64 e Å−3 |
2121 reflections | Δρmin = −0.35 e Å−3 |
104 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6201 (5) | 0.08520 (15) | 0.23416 (18) | 0.0171 (5) | |
C2 | 0.4224 (5) | 0.03061 (15) | 0.27942 (17) | 0.0175 (5) | |
C3 | 0.3333 (5) | 0.05229 (15) | 0.38169 (17) | 0.0199 (5) | |
H3 | 0.2016 | 0.0158 | 0.4153 | 0.024* | |
C4 | 0.4299 (5) | 0.12513 (14) | 0.43603 (18) | 0.0181 (5) | |
C5 | 0.6277 (5) | 0.17733 (15) | 0.38738 (17) | 0.0179 (5) | |
H5 | 0.6980 | 0.2268 | 0.4244 | 0.021* | |
C6 | 0.7249 (4) | 0.15857 (15) | 0.28554 (18) | 0.0161 (5) | |
C7 | 0.3084 (5) | −0.04773 (16) | 0.22143 (19) | 0.0229 (6) | |
H7A | 0.4541 | −0.0920 | 0.2161 | 0.034* | |
H7B | 0.2455 | −0.0307 | 0.1495 | 0.034* | |
H7C | 0.1515 | −0.0715 | 0.2609 | 0.034* | |
C8 | 0.3174 (5) | 0.14835 (17) | 0.54347 (19) | 0.0249 (6) | |
H8A | 0.4618 | 0.1780 | 0.5860 | 0.037* | |
H8B | 0.2601 | 0.0953 | 0.5805 | 0.037* | |
H8C | 0.1568 | 0.1870 | 0.5341 | 0.037* | |
C9 | 0.9377 (5) | 0.21750 (15) | 0.23440 (19) | 0.0210 (6) | |
H9A | 1.1011 | 0.1832 | 0.2150 | 0.031* | |
H9B | 0.9933 | 0.2631 | 0.2851 | 0.031* | |
H9C | 0.8561 | 0.2442 | 0.1700 | 0.031* | |
N1 | 0.7035 (4) | 0.06625 (12) | 0.12322 (13) | 0.0173 (5) | |
H1A | 0.5682 | 0.0848 | 0.0769 | 0.026* | |
H1B | 0.7285 | 0.0079 | 0.1154 | 0.026* | |
H1C | 0.8653 | 0.0944 | 0.1092 | 0.026* | |
Cl1 | 0.20588 (11) | 0.12054 (4) | −0.02006 (4) | 0.0188 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0180 (12) | 0.0185 (12) | 0.0147 (11) | 0.0054 (10) | 0.0009 (9) | −0.0003 (10) |
C2 | 0.0176 (12) | 0.0165 (12) | 0.0184 (12) | 0.0023 (10) | 0.0002 (9) | 0.0019 (10) |
C3 | 0.0255 (13) | 0.0158 (12) | 0.0186 (12) | 0.0018 (10) | 0.0037 (10) | 0.0049 (10) |
C4 | 0.0230 (13) | 0.0167 (12) | 0.0146 (11) | 0.0066 (10) | −0.0002 (9) | 0.0012 (10) |
C5 | 0.0225 (13) | 0.0152 (12) | 0.0158 (12) | 0.0032 (10) | −0.0026 (10) | −0.0015 (9) |
C6 | 0.0159 (12) | 0.0142 (12) | 0.0182 (12) | 0.0041 (10) | −0.0014 (9) | −0.0005 (10) |
C7 | 0.0243 (13) | 0.0199 (13) | 0.0246 (13) | −0.0044 (11) | 0.0045 (10) | −0.0003 (11) |
C8 | 0.0363 (16) | 0.0207 (13) | 0.0179 (12) | 0.0035 (11) | 0.0053 (11) | −0.0005 (10) |
C9 | 0.0224 (13) | 0.0180 (13) | 0.0226 (13) | 0.0007 (10) | 0.0033 (10) | −0.0020 (11) |
N1 | 0.0185 (10) | 0.0160 (10) | 0.0174 (10) | −0.0014 (8) | 0.0021 (8) | −0.0015 (8) |
Cl1 | 0.0212 (3) | 0.0177 (3) | 0.0177 (3) | −0.0002 (2) | 0.0026 (2) | −0.0009 (2) |
C1—C6 | 1.389 (3) | C7—H7A | 0.9800 |
C1—C2 | 1.396 (3) | C7—H7B | 0.9800 |
C1—N1 | 1.480 (3) | C7—H7C | 0.9800 |
C2—C3 | 1.397 (3) | C8—H8A | 0.9800 |
C2—C7 | 1.504 (3) | C8—H8B | 0.9800 |
C3—C4 | 1.386 (3) | C8—H8C | 0.9800 |
C3—H3 | 0.9500 | C9—H9A | 0.9800 |
C4—C5 | 1.393 (3) | C9—H9B | 0.9800 |
C4—C8 | 1.501 (3) | C9—H9C | 0.9800 |
C5—C6 | 1.395 (3) | N1—H1A | 0.9100 |
C5—H5 | 0.9500 | N1—H1B | 0.9100 |
C6—C9 | 1.517 (3) | N1—H1C | 0.9100 |
C6—C1—C2 | 123.0 (2) | C2—C7—H7C | 109.5 |
C6—C1—N1 | 119.44 (19) | H7A—C7—H7C | 109.5 |
C2—C1—N1 | 117.4 (2) | H7B—C7—H7C | 109.5 |
C1—C2—C3 | 116.8 (2) | C4—C8—H8A | 109.5 |
C1—C2—C7 | 122.06 (19) | C4—C8—H8B | 109.5 |
C3—C2—C7 | 121.2 (2) | H8A—C8—H8B | 109.5 |
C4—C3—C2 | 122.4 (2) | C4—C8—H8C | 109.5 |
C4—C3—H3 | 118.8 | H8A—C8—H8C | 109.5 |
C2—C3—H3 | 118.8 | H8B—C8—H8C | 109.5 |
C3—C4—C5 | 118.5 (2) | C6—C9—H9A | 109.5 |
C3—C4—C8 | 120.6 (2) | C6—C9—H9B | 109.5 |
C5—C4—C8 | 120.9 (2) | H9A—C9—H9B | 109.5 |
C4—C5—C6 | 121.5 (2) | C6—C9—H9C | 109.5 |
C4—C5—H5 | 119.3 | H9A—C9—H9C | 109.5 |
C6—C5—H5 | 119.3 | H9B—C9—H9C | 109.5 |
C1—C6—C5 | 117.8 (2) | C1—N1—H1A | 109.5 |
C1—C6—C9 | 122.2 (2) | C1—N1—H1B | 109.5 |
C5—C6—C9 | 120.1 (2) | H1A—N1—H1B | 109.5 |
C2—C7—H7A | 109.5 | C1—N1—H1C | 109.5 |
C2—C7—H7B | 109.5 | H1A—N1—H1C | 109.5 |
H7A—C7—H7B | 109.5 | H1B—N1—H1C | 109.5 |
C6—C1—C2—C3 | −0.8 (3) | C3—C4—C5—C6 | 1.1 (3) |
N1—C1—C2—C3 | −176.3 (2) | C8—C4—C5—C6 | −177.2 (2) |
C6—C1—C2—C7 | 179.0 (2) | C2—C1—C6—C5 | 0.5 (3) |
N1—C1—C2—C7 | 3.5 (3) | N1—C1—C6—C5 | 175.93 (19) |
C1—C2—C3—C4 | 1.2 (3) | C2—C1—C6—C9 | −179.4 (2) |
C7—C2—C3—C4 | −178.5 (2) | N1—C1—C6—C9 | −4.0 (3) |
C2—C3—C4—C5 | −1.4 (3) | C4—C5—C6—C1 | −0.7 (3) |
C2—C3—C4—C8 | 176.9 (2) | C4—C5—C6—C9 | 179.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1 | 0.91 | 2.18 | 3.081 (2) | 172 |
N1—H1B···Cl1i | 0.91 | 2.33 | 3.181 (2) | 155 |
N1—H1C···Cl1ii | 0.91 | 2.36 | 3.146 (2) | 145 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C9H14N+·Cl− |
Mr | 171.66 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 90 |
a, b, c (Å) | 4.811 (1), 15.373 (3), 12.509 (2) |
β (°) | 90.99 (3) |
V (Å3) | 925.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.40 × 0.13 × 0.03 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.873, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4000, 2121, 1453 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.138, 1.04 |
No. of reflections | 2121 |
No. of parameters | 104 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.35 |
Computer programs: COLLECT (Nonius, 2002), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1995), SHELXL97 and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1 | 0.91 | 2.18 | 3.081 (2) | 172.4 |
N1—H1B···Cl1i | 0.91 | 2.33 | 3.181 (2) | 155.4 |
N1—H1C···Cl1ii | 0.91 | 2.36 | 3.146 (2) | 145.1 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y, z. |
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The title compound, (I), was a by-product during our attempts to synthesize 2-[(2,4,6-trimethylphenyl)amino]-3-pyridinecarboxylic acid, a potential anti-inflammatory compound (Ting et al., 1990).
The asymmetric unit of the crystal I (Fig. 1) consists of a 2,4,6-trimethylbenzenaminium cation and a chloride anion·In the crystal of I, all the available hydrogen bonding donors and acceptors are involved in the three-dimensional hydrogen bonding network. The molecules in the crystal form columns with a width of two molecules along the a axis through N—H···Cl hydrogen bonds (Table 1). The N—H···Cl hydrogen bonds link pairs of molecules around a center of symmetry and further connect these pairs of molecules in the [1 0 0] direction. Moreover, the aromatic rings on each side of the columns are stacked face-to-face, suggesting π-π stacking may provide additional stablitity to the crystal structure (Fig. 2).