Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703499X/pv2019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703499X/pv2019Isup2.hkl |
CCDC reference: 657822
The title compound was obtained from the reaction of Me2NH with 1,3,5-trichloro-1-thia-2,4,6-triazine, a reaction which was previously reported to be very susceptible to hydrolysis (Ramakrishna et al., 1999), as the only tractable product. Colourless blocks were obtained and a crystal was mounted on a glass fibre in Paratone oil and diffraction data was collected at 173 (2) K. Refinement proceeded normally, but in view of the interest in intermolecular C—H···Cl- contacts, it was decided to freely refine all the H atom positions, after they were located using the HFIX command in SHELXTL, with the temperature factors set at 1.5 × the attached methyl and 1.2 × CH2 carbons. A similar approach was taken by (Clark et al., 1994).
There is considerable interest in the structural chemistry of iminium ions, in large part because they can be the cationic components of ionic liquids. The structure presented here may be compared to that of the [Me2N=CH2]Cl (Burg, 1989) and [Me2N=CH2]Br (Clark et al., 1994) structures which are reported in the literature (Refcodes VAPREJ and LILLOH, respectively; Allen, 2002). There is a short contact between the iminium carbon atom and the Cl- anion of 2.973 (1) Å. Interestingly, a similar interaction is seen in the dimethylmethyleniminium bromide, but not in the dimethyleneiminium chloride salt. Mayr, et al. have shown that specific cation-anion interactions in iminium halides (C—H···Hal- hydrogen bonds) may be responsible for the different products that iminium ions with different counterions give in reactions with alkynes and allylsilanes (Mayr et al., 1997). C—H···Hal- bonds rather than equilibria between ionic and covalent moieties are responsible for the anion dependence of the NMR chemical shifts of iminium ions (Mayr et al., 1997).
Structures of [Me2N═CH2]+ ions with Cl- (Burg, 1989), Br- and I- (Clark et al., 1994), and [NiBr4]- (Hitchcock et al., 2003) counter-ions have been published. Strong evidence has been obtained for intermolecular C—H···Cl- interactions in the title compound from a detailed NMR investigation (Mayr et al., 1997).
For related literature, see: Allen (2002); Ramakrishna et al. (1999).
Data collection: SMART (Bruker, 2006); cell refinement: SMART; data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXSTL (Sheldrick, 2003); program(s) used to refine structure: SHELXTL (Sheldrick, 2003); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2007).
C5H12N+·Cl− | F(000) = 264 |
Mr = 121.61 | Dx = 1.154 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2yn | Cell parameters from 7168 reflections |
a = 6.6023 (4) Å | θ = 2.6–28.6° |
b = 15.7426 (10) Å | µ = 0.44 mm−1 |
c = 7.0057 (4) Å | T = 173 K |
β = 106.021 (1)° | Block, colourless |
V = 699.87 (7) Å3 | 0.46 × 0.28 × 0.25 mm |
Z = 4 |
Bruker APEX II CCD area-detector diffractometer | 1500 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 27.1°, θmin = 2.6° |
φ and ω scans | h = −8→8 |
7666 measured reflections | k = −20→20 |
1544 independent reflections | l = −8→8 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | Only H-atom coordinates refined |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0289P)2 + 0.1779P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1544 reflections | Δρmax = 0.29 e Å−3 |
101 parameters | Δρmin = −0.16 e Å−3 |
12 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.036 (3) |
C5H12N+·Cl− | V = 699.87 (7) Å3 |
Mr = 121.61 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.6023 (4) Å | µ = 0.44 mm−1 |
b = 15.7426 (10) Å | T = 173 K |
c = 7.0057 (4) Å | 0.46 × 0.28 × 0.25 mm |
β = 106.021 (1)° |
Bruker APEX II CCD area-detector diffractometer | 1500 reflections with I > 2σ(I) |
7666 measured reflections | Rint = 0.013 |
1544 independent reflections |
R[F2 > 2σ(F2)] = 0.021 | 12 restraints |
wR(F2) = 0.058 | Only H-atom coordinates refined |
S = 1.06 | Δρmax = 0.29 e Å−3 |
1544 reflections | Δρmin = −0.16 e Å−3 |
101 parameters |
Geometry. All e.s.d.'s 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. |
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 | ||
Cl1 | 0.22927 (3) | 0.601617 (15) | 0.36447 (3) | 0.02793 (10) | |
C1 | 1.12954 (18) | 0.72306 (8) | 0.8063 (2) | 0.0445 (3) | |
H1A | 1.041 (2) | 0.7606 (10) | 0.846 (3) | 0.067* | |
H1B | 1.123 (3) | 0.7328 (11) | 0.661 (2) | 0.067* | |
H1C | 1.274 (2) | 0.7299 (10) | 0.890 (2) | 0.067* | |
C5 | 0.67421 (19) | 0.59059 (8) | 0.98303 (18) | 0.0368 (3) | |
H5A | 0.806 (2) | 0.5944 (9) | 1.090 (2) | 0.055* | |
H5B | 0.649 (2) | 0.5315 (9) | 0.937 (2) | 0.055* | |
H5C | 0.555 (2) | 0.6072 (9) | 1.038 (2) | 0.055* | |
C4 | 0.67811 (15) | 0.64901 (6) | 0.81260 (15) | 0.0272 (2) | |
H4A | 0.5433 (18) | 0.6488 (8) | 0.7100 (17) | 0.033* | |
H4B | 0.7143 (19) | 0.7068 (7) | 0.8580 (18) | 0.033* | |
C2 | 1.06293 (14) | 0.63213 (7) | 0.82196 (15) | 0.0270 (2) | |
H2A | 1.142 (2) | 0.5943 (7) | 0.7609 (19) | 0.032* | |
H2B | 1.080 (2) | 0.6142 (8) | 0.9549 (17) | 0.032* | |
C6 | 0.78309 (16) | 0.58266 (6) | 0.54673 (15) | 0.0262 (2) | |
H6A | 0.8909 (18) | 0.5658 (8) | 0.4865 (18) | 0.031* | |
H6B | 0.6375 (18) | 0.5758 (8) | 0.4823 (18) | 0.031* | |
N1 | 0.83797 (12) | 0.62006 (5) | 0.71424 (12) | 0.02214 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02520 (14) | 0.03059 (15) | 0.02709 (15) | −0.00273 (8) | 0.00568 (9) | −0.00059 (8) |
C1 | 0.0278 (5) | 0.0331 (6) | 0.0677 (8) | −0.0042 (4) | 0.0050 (5) | −0.0157 (6) |
C5 | 0.0366 (6) | 0.0413 (6) | 0.0376 (6) | −0.0005 (5) | 0.0184 (5) | 0.0048 (5) |
C4 | 0.0254 (5) | 0.0267 (5) | 0.0308 (5) | 0.0027 (4) | 0.0101 (4) | −0.0018 (4) |
C2 | 0.0210 (4) | 0.0325 (5) | 0.0252 (5) | 0.0032 (4) | 0.0027 (3) | 0.0013 (4) |
C6 | 0.0271 (5) | 0.0243 (4) | 0.0267 (5) | 0.0001 (4) | 0.0068 (4) | 0.0016 (4) |
N1 | 0.0216 (4) | 0.0194 (3) | 0.0251 (4) | 0.0017 (3) | 0.0058 (3) | 0.0027 (3) |
C1—C2 | 1.5105 (16) | C4—H4A | 0.978 (11) |
C1—H1A | 0.930 (14) | C4—H4B | 0.971 (11) |
C1—H1B | 1.016 (14) | C2—N1 | 1.4808 (12) |
C1—H1C | 0.976 (14) | C2—H2A | 0.968 (11) |
C5—C4 | 1.5130 (15) | C2—H2B | 0.949 (11) |
C5—H5A | 0.981 (13) | C6—N1 | 1.2729 (13) |
C5—H5B | 0.983 (13) | C6—H6A | 0.960 (11) |
C5—H5C | 1.000 (13) | C6—H6B | 0.949 (11) |
C4—N1 | 1.4826 (12) | ||
C6···Cl1i | 2.973 (1) | H2B···Cl1iii | 2.772 (12) |
H6B···Cl1 | 2.623 (11) | H4A···Cl1 | 2.817 (11) |
H6A···Cl1ii | 2.664 (11) | H5A···Cl1iii | 2.925 (14) |
C2—C1—H1A | 111.1 (11) | N1—C4—H4B | 107.3 (7) |
C2—C1—H1B | 106.4 (10) | C5—C4—H4B | 111.5 (7) |
H1A—C1—H1B | 110.4 (14) | H4A—C4—H4B | 109.6 (10) |
C2—C1—H1C | 108.5 (10) | N1—C2—C1 | 110.84 (8) |
H1A—C1—H1C | 110.1 (14) | N1—C2—H2A | 106.6 (8) |
H1B—C1—H1C | 110.3 (14) | C1—C2—H2A | 110.3 (7) |
C4—C5—H5A | 111.3 (9) | N1—C2—H2B | 107.2 (8) |
C4—C5—H5B | 110.8 (9) | C1—C2—H2B | 113.2 (8) |
H5A—C5—H5B | 110.0 (13) | H2A—C2—H2B | 108.5 (11) |
C4—C5—H5C | 109.4 (9) | N1—C6—H6A | 118.4 (8) |
H5A—C5—H5C | 108.2 (13) | N1—C6—H6B | 119.0 (8) |
H5B—C5—H5C | 107.1 (13) | H6A—C6—H6B | 122.4 (11) |
N1—C4—C5 | 110.45 (8) | C6—N1—C2 | 121.29 (8) |
N1—C4—H4A | 106.1 (7) | C6—N1—C4 | 120.84 (8) |
C5—C4—H4A | 111.6 (8) | C2—N1—C4 | 117.79 (8) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C5H12N+·Cl− |
Mr | 121.61 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 6.6023 (4), 15.7426 (10), 7.0057 (4) |
β (°) | 106.021 (1) |
V (Å3) | 699.87 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.46 × 0.28 × 0.25 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7666, 1544, 1500 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.058, 1.06 |
No. of reflections | 1544 |
No. of parameters | 101 |
No. of restraints | 12 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.29, −0.16 |
Computer programs: SMART (Bruker, 2006), SMART, SAINT (Bruker, 2006), SHELXSTL (Sheldrick, 2003), SHELXTL (Sheldrick, 2003), Mercury (Macrae et al., 2006), publCIF (Westrip, 2007).
C4—N1 | 1.4826 (12) | C6—N1 | 1.2729 (13) |
C2—N1 | 1.4808 (12) | ||
C6···Cl1i | 2.973 (1) | H2B···Cl1iii | 2.772 (12) |
H6B···Cl1 | 2.623 (11) | H4A···Cl1 | 2.817 (11) |
H6A···Cl1ii | 2.664 (11) | H5A···Cl1iii | 2.925 (14) |
C6—N1—C2 | 121.29 (8) | C2—N1—C4 | 117.79 (8) |
C6—N1—C4 | 120.84 (8) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) x−1, y, z−1. |
There is considerable interest in the structural chemistry of iminium ions, in large part because they can be the cationic components of ionic liquids. The structure presented here may be compared to that of the [Me2N=CH2]Cl (Burg, 1989) and [Me2N=CH2]Br (Clark et al., 1994) structures which are reported in the literature (Refcodes VAPREJ and LILLOH, respectively; Allen, 2002). There is a short contact between the iminium carbon atom and the Cl- anion of 2.973 (1) Å. Interestingly, a similar interaction is seen in the dimethylmethyleniminium bromide, but not in the dimethyleneiminium chloride salt. Mayr, et al. have shown that specific cation-anion interactions in iminium halides (C—H···Hal- hydrogen bonds) may be responsible for the different products that iminium ions with different counterions give in reactions with alkynes and allylsilanes (Mayr et al., 1997). C—H···Hal- bonds rather than equilibria between ionic and covalent moieties are responsible for the anion dependence of the NMR chemical shifts of iminium ions (Mayr et al., 1997).