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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o229.
Published online 2007 December 12. doi:  10.1107/S1600536807064872
PMCID: PMC2915290

(Z)-N-[2-(Dimethyl­ammonio)eth­yl]thio­acetamide chloride

Abstract

The thio­amide and quaternary amine parts of the title compound, C6H15N2S+·Cl, are mutually almost perpendicular, the dihedral angle being 80.6 (7)°. The thio­amide group is planar and adopts a Z conformation, whereas the amine end of the cation is in an extended conformation. In the supra­molecular structure, mol­ecules are linked into centrosymmetric dimers by two hydrogen bonds: N—Hamine(...)Cl and N—Hthio­amide(...)Cl.

Related literature

For details of the synthesis, see Spychała (2000 [triangle], 2003 [triangle]). For bond-length data, see: Allen (2002 [triangle]).

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Object name is e-64-0o229-scheme1.jpg

Experimental

Crystal data

  • C6H15N2S+·Cl
  • M r = 182.71
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o229-efi1.jpg
  • a = 5.9935 (2) Å
  • b = 7.7461 (3) Å
  • c = 10.8253 (4) Å
  • α = 79.489 (3)°
  • β = 79.796 (3)°
  • γ = 87.863 (3)°
  • V = 486.32 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.55 mm−1
  • T = 292 (2) K
  • 0.6 × 0.2 × 0.2 mm

Data collection

  • Kuma KM-4 CCD diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 [triangle]) T min = 0.785, T max = 1.000 (expected range = 0.704–0.897)
  • 4065 measured reflections
  • 2332 independent reflections
  • 1988 reflections with I > 2σ(I)
  • R int = 0.008

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.089
  • S = 1.06
  • 2332 reflections
  • 127 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: Stereochemical Workstation Operation Manual (Siemens 1989 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064872/ng2404sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064872/ng2404Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by funds from Adam Mickiewicz University, Faculty of Chemistry.

supplementary crystallographic information

Comment

The structure of the title compound (I), is shown below. Dimensions are available in the archived CIF.

The asymmetric unit of the title compound, (I), consists of one [C6H15N2S]+cation and one chloride anion (Fig.1). The thioamide group is in Z configuration, its bond lengths are in agreement with the literature (Allen, 2002). The thioamide group is flat, the appropriate torsion angles adopt values close to 0° or 180° [S(5)—C(5)—N(4)—C(3) = τ1 = -0.5 (2)°, C(51)—C(5)—N(4)—C(3) = τ2 = -179.6 (1)°]. The quarternary amine end of the molecule is associated with conformational flexibility and it is apparent that the amine chain is in an almost extended conformation [C(12)—N(1)—C(2)—C(3) = τ3 = 177.0 (1)°] and moreover, it lies in a plane that is nearly orthogonal to the thioamide plane, the dihedral angle between the least-squares planes is 80.6 (7)°. On the other hand, the amine and thioamide functions are mutually gauche oriented [N(1)—C(2)—C(3)—N(4) = τ4 = 62.3 (2)°]. This conformation of the molecule causes some steric stress which is released by thioamide bond angles distortion from ideal values of 120°, e.g. the bond angles adopt values as follows: C(5)—N(4)—C(3) is 125.0 (1)°, S(5)—C(5)—N(4) 124.0 (1)°, C(3)—N(4)—H(4) 114.9 (1)°, C(51)—C(5)—N(4) 114.7 (1)°, although the sum of bond angles around C(5) and N(4) equals 360°. This diversity in bond angles seems to be the general property of amide and thioamide groups. The molecular conformation is stabilized by the intermolecular hydrogen bonds N—H···Cl which give rise to centrosymmetric dimers formation (Fig. 1). Each cation in the dimer participates in two hydrogen bonds to two chloride anions, N+H(amine)···Cl- and NH(thioamide)···Cl-.

In supramolecular structure the dimers are ordered along the [010] direction one after the another thus forming alternate hydrophilic and hydrophobic segments. In the hydrophilic segments the chloride anions that interact with the cations via hydrogen bonds are located, whereas the hydrophobic segments are formed by two ribbons connected by van der Waals forces. Along the third direction, [100], the cations form stacks as the most efficient close packing motifs with the chloride anions forming columns in the channels of the close packing achieved by the cations.

Experimental

Starting from thioacetamide and the appropriate diaminoalkane, the title compound was obtained by the transamination Wallach reaction by refluxing the reaction mixture in ethanol. The reaction was carried out under literature conditions described in the previous papers (Spychała 2000, 2003). Solvent: 2-propanol / diethyl ether. Single crystals were grown from the hot solution by slow cooling.

Refinement

Hydrogen atoms were found from difference Fourier maps and refined except hydrogen atoms of three methyl groups, which were constrained to ride on their parent atom. The N—H distances were restrained to 0.88±0.01 Å.

Figures

Fig. 1.
Dimer of (I) generated by N+—H(amine)···Cl- and N—H(thioamide)···Cl- hydrogen bonds (dashed lines). A view along the [100] direction, (Macrae et al., 2006).

Crystal data

C6H15N2S+·ClZ = 2
Mr = 182.71F000 = 196
Triclinic, P1Dx = 1.248 Mg m3
a = 5.9935 (2) ÅMo Kα radiation λ = 0.71073 Å
b = 7.7461 (3) ÅCell parameters from 2792 reflections
c = 10.8253 (4) Åθ = 2.7–29.6º
α = 79.489 (3)ºµ = 0.55 mm1
β = 79.796 (3)ºT = 292 (2) K
γ = 87.863 (3)ºBlock, colourless
V = 486.32 (3) Å30.6 × 0.2 × 0.2 mm

Data collection

Kuma KM-4 CCD diffractometer2332 independent reflections
Radiation source: fine-focus sealed tube1988 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.008
Detector resolution: 8.1929 pixels mm-1θmax = 29.7º
T = 292(2) Kθmin = 3.0º
ω–scanh = −8→6
Absorption correction: multi-scanCrysAlis RED (Oxford Diffraction, 2007)k = −10→10
Tmin = 0.785, Tmax = 1.000l = −14→11
4065 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089  w = 1/[σ2(Fo2) + (0.0493P)2 + 0.0911P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2332 reflectionsΔρmax = 0.36 e Å3
127 parametersΔρmin = −0.27 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

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

xyzUiso*/Ueq
Cl10.74439 (6)0.68184 (5)0.92798 (3)0.04695 (12)
N10.43953 (18)0.72292 (15)0.72918 (10)0.0369 (2)
C110.6186 (3)0.7621 (2)0.61349 (16)0.0529 (4)
H11A0.71430.66090.60680.073 (6)*
H11B0.70810.85930.62010.077 (7)*
H11C0.54890.79150.53900.070 (6)*
C120.3063 (3)0.8834 (2)0.75207 (18)0.0564 (4)
H12A0.40210.96610.77330.066 (6)*
H12C0.18220.85260.82120.062 (5)*
H12B0.24850.93510.67640.062 (5)*
C20.2817 (2)0.5793 (2)0.72500 (14)0.0401 (3)
C30.3998 (2)0.4127 (2)0.69463 (14)0.0417 (3)
N40.5321 (2)0.33438 (15)0.79089 (10)0.0377 (2)
C50.7308 (2)0.25637 (17)0.76729 (13)0.0368 (3)
C510.8327 (3)0.1849 (2)0.88345 (16)0.0541 (4)
H51A0.79440.06310.91140.134 (12)*
H51B0.77430.24910.95030.148 (13)*
H51C0.99450.19680.86300.127 (10)*
S50.86290 (6)0.23364 (6)0.62085 (4)0.05189 (14)
H10.511 (3)0.691 (2)0.7946 (13)0.052 (5)*
H2A0.180 (3)0.564 (2)0.8055 (18)0.052 (5)*
H2B0.192 (3)0.622 (2)0.6625 (17)0.046 (4)*
H3A0.290 (3)0.329 (2)0.6874 (17)0.055 (5)*
H3B0.502 (3)0.432 (2)0.6142 (17)0.043 (4)*
H40.468 (3)0.338 (2)0.8684 (10)0.048 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.03632 (18)0.0692 (3)0.03689 (19)−0.00237 (15)−0.00751 (13)−0.01194 (16)
N10.0340 (5)0.0447 (6)0.0327 (5)0.0040 (4)−0.0078 (4)−0.0072 (4)
C110.0460 (8)0.0653 (10)0.0444 (8)−0.0118 (7)0.0021 (6)−0.0092 (7)
C120.0601 (10)0.0474 (9)0.0606 (10)0.0114 (7)−0.0097 (8)−0.0103 (7)
C20.0302 (6)0.0497 (8)0.0408 (7)0.0019 (5)−0.0089 (5)−0.0064 (6)
C30.0405 (7)0.0499 (8)0.0383 (7)−0.0007 (6)−0.0128 (6)−0.0113 (6)
N40.0425 (6)0.0418 (6)0.0291 (5)0.0026 (5)−0.0063 (4)−0.0079 (4)
C50.0394 (6)0.0379 (7)0.0347 (6)−0.0031 (5)−0.0083 (5)−0.0080 (5)
C510.0602 (10)0.0614 (11)0.0432 (8)0.0134 (8)−0.0188 (7)−0.0091 (7)
S50.0402 (2)0.0778 (3)0.0386 (2)0.00595 (17)−0.00335 (15)−0.01740 (18)

Geometric parameters (Å, °)

N1—C121.488 (2)C2—H2B0.943 (18)
N1—C111.4908 (18)C3—N41.4519 (18)
N1—C21.4988 (18)C3—H3A0.963 (19)
N1—H10.883 (9)C3—H3B0.962 (18)
C11—H11A0.9600N4—C51.3206 (18)
C11—H11B0.9600N4—H40.863 (9)
C11—H11C0.9600C5—C511.501 (2)
C12—H12A0.9600C5—S51.6786 (14)
C12—H12C0.9600C51—H51A0.9600
C12—H12B0.9600C51—H51B0.9600
C2—C31.510 (2)C51—H51C0.9600
C2—H2A0.960 (19)
C12—N1—C11111.02 (13)N1—C2—H2B107.7 (10)
C12—N1—C2109.51 (11)C3—C2—H2B109.2 (10)
C11—N1—C2113.73 (11)H2A—C2—H2B106.1 (15)
C12—N1—H1106.7 (12)N4—C3—C2112.06 (12)
C11—N1—H1106.5 (12)N4—C3—H3A109.3 (11)
C2—N1—H1109.1 (12)C2—C3—H3A109.9 (11)
N1—C11—H11A109.5N4—C3—H3B106.9 (10)
N1—C11—H11B109.5C2—C3—H3B112.5 (10)
H11A—C11—H11B109.5H3A—C3—H3B105.9 (15)
N1—C11—H11C109.5C5—N4—C3124.90 (12)
H11A—C11—H11C109.5C5—N4—H4120.4 (12)
H11B—C11—H11C109.5C3—N4—H4114.6 (12)
N1—C12—H12A109.5N4—C5—C51114.66 (12)
N1—C12—H12C109.5N4—C5—S5124.05 (10)
H12A—C12—H12C109.5C51—C5—S5121.28 (11)
N1—C12—H12B109.5C5—C51—H51A109.5
H12A—C12—H12B109.5C5—C51—H51B109.5
H12C—C12—H12B109.5H51A—C51—H51B109.5
N1—C2—C3114.08 (11)C5—C51—H51C109.5
N1—C2—H2A105.4 (11)H51A—C51—H51C109.5
C3—C2—H2A113.9 (11)H51B—C51—H51C109.5
C12—N1—C2—C3176.67 (13)C3—N4—C5—C51−179.64 (14)
C11—N1—C2—C351.81 (16)C3—N4—C5—S5−0.5 (2)
N1—C2—C3—N462.34 (16)S5—C5—N4—H4177.1 (14)
C2—C3—N4—C5−142.40 (13)C51—C5—N4—H4−2.1 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.883 (9)2.174 (10)3.0285 (11)162.9 (16)
N4—H4···Cl1i0.863 (9)2.325 (10)3.1801 (12)171.0 (16)

Symmetry codes: (i) −x+1, −y+1, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2404).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED Versions 1.171.32.5. Oxford Diffraction Poland, Wrocław, Poland.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Siemens (1989). Stereochemical Workstation Operation Manual Release 3.4. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Spychała, J. (2000). Tetrahedron, 56, 7981–7986.
  • Spychała, J. (2003). Magn. Reson. Chem.41, 169–176.

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