supplementary materials
4,6-Dimethyl-2-thioxo-1,2-dihydropyrimidin-3-ium chloride-thiourea (1/1)
Thiourea (2 g, 26 mmol) was reacted with 2,4-pentadione (2.6 g, 26 mmol) in
C3H6O (20 ml) solution, to give the corresponding 1:1 adduct after two
hour under refluxing. After cooling to room temperature, 3.4 ml HCl 10M
was added dropwise to the solution and the resulting mixture was refluxed for
one hour before left standing overnight. The filtrate gave yellowish crystal
suitable for X-ray analyses after four days of slow evaporation. Yield:
87.69%. m.p. 190±2 °C. Anal. Calc. for C7H13N4S2Cl (%): C, 33.26; H,
5.18; N, 22.16. Found: C, 33.37; H, 5.15; N, 22.25.
Selected IR data (cm-1, KBr pellet): 1599 (ν C═N), 1187 (ν C═S).
1H NMR (200 MHz, D2O, δ, p.p.m.): 2.40 (s, 6H, –CH3); 6.83 (s, 1H,
–CH). 13C NMR (200 MHz, D2O, δ, p.p.m.): 19.26 (–CH3); 118.32 (–CH);
168.02 (N═C); 172.90 (N═C—S—H).
The H atoms of the NH2 groups were located in the Fourier difference maps and
refined by riding motion. Others H atoms were placed geometrically and refined
with a riding model. Uiso(H) for H was assigned as 1.2Ueq of
the attached C atoms (1.5 for methyl C atoms).
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON/PLUTON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
4,6-Dimethyl-2-thioxo-1,2-dihydropyrimidin-3-ium chloride–thiourea (1/1)
top
Crystal data top
| C6H9N2S+·Cl–·CH4N2S | F000 = 528 |
| Mr = 252.78 | Dx = 1.393 Mg m−3 |
| Orthorhombic, Cmcm | Mo Kα radiation
λ = 0.71073 Å |
| Hall symbol: -C 2c 2 | Cell parameters from 653 reflections |
| a = 6.6459 (4) Å | θ = 1.0–25.4º |
| b = 21.6144 (14) Å | µ = 0.63 mm−1 |
| c = 8.3878 (5) Å | T = 293 K |
| V = 1204.88 (12) Å3 | Prism, yellow |
| Z = 4 | 0.10 × 0.10 × 0.10 mm |
Data collection top
| Nonius KappaCCD diffractometer | 447 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.024 |
| Monochromator: graphite | θmax = 25.3º |
| T = 293 K | θmin = 3.1º |
| φ scans | h = −7→7 |
| Absorption correction: none | k = −25→25 |
| 1080 measured reflections | l = −10→10 |
| 636 independent reflections | |
Refinement top
| 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)] = 0.055 | H-atom parameters constrained |
| wR(F2) = 0.175 | w = 1/[σ2(Fo2) + (0.1002P)2 + 1.9948P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.004 |
| 636 reflections | Δρmax = 0.44 e Å−3 |
| 49 parameters | Δρmin = −0.51 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
Crystal data top
| C6H9N2S+·Cl–·CH4N2S | V = 1204.88 (12) Å3 |
| Mr = 252.78 | Z = 4 |
| Orthorhombic, Cmcm | Mo Kα |
| a = 6.6459 (4) Å | µ = 0.63 mm−1 |
| b = 21.6144 (14) Å | T = 293 K |
| c = 8.3878 (5) Å | 0.10 × 0.10 × 0.10 mm |
Data collection top
| Nonius KappaCCD diffractometer | 636 independent reflections |
| Absorption correction: none | 447 reflections with I > 2σ(I) |
| 1080 measured reflections | Rint = 0.024 |
Refinement top
| R[F2 > 2σ(F2)] = 0.055 | 49 parameters |
| wR(F2) = 0.175 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.44 e Å−3 |
| 636 reflections | Δρmin = −0.51 e Å−3 |
Special details top
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 F^2^ against ALL reflections. The weighted
R-factor wR and goodness of fit S are based on
F^2^, conventional R-factors R are based on F,
with F set to zero for negative F^2^. The threshold expression
of F^2^ > σ(F^2^) is used only for calculating
R-factors(gt) etc. and is not relevant to the choice of
reflections for refinement. R-factors based on F^2^ 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) top| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| Cl1 | 0.0000 | 0.22960 (8) | 0.7500 | 0.0492 (6) | |
| S1 | 0.5000 | 0.32187 (9) | 0.7500 | 0.0582 (7) | |
| S2 | 0.0000 | −0.02324 (10) | 0.7500 | 0.1135 (15) | |
| N1 | 0.5000 | 0.21069 (18) | 0.6134 (5) | 0.0424 (10) | |
| H1 | 0.5000 | 0.2302 | 0.5240 | 0.051* | |
| N2 | 0.0000 | 0.0864 (2) | 0.6144 (5) | 0.0558 (12) | |
| H2A | 0.0000 | 0.1262 | 0.6154 | 0.067* | |
| H2B | 0.0000 | 0.0669 | 0.5251 | 0.067* | |
| C1 | 0.5000 | 0.1485 (2) | 0.6079 (6) | 0.0423 (11) | |
| C2 | 0.0000 | 0.0553 (4) | 0.7500 | 0.0526 (19) | |
| C3 | 0.5000 | 0.1172 (3) | 0.7500 | 0.0448 (17) | |
| H3 | 0.5000 | 0.0741 | 0.7500 | 0.054* | |
| C4 | 0.5000 | 0.2456 (3) | 0.7500 | 0.0431 (16) | |
| C5 | 0.5000 | 0.1187 (3) | 0.4493 (6) | 0.0589 (15) | |
| H5A | 0.5000 | 0.1499 | 0.3679 | 0.088* | |
| H5B | 0.3821 | 0.0934 | 0.4385 | 0.088* | 0.50 |
| H5C | 0.6179 | 0.0934 | 0.4385 | 0.088* | 0.50 |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0583 (11) | 0.0481 (11) | 0.0412 (10) | 0.000 | 0.000 | 0.000 |
| S1 | 0.0680 (13) | 0.0463 (11) | 0.0602 (14) | 0.000 | 0.000 | 0.000 |
| S2 | 0.267 (5) | 0.0420 (14) | 0.0316 (11) | 0.000 | 0.000 | 0.000 |
| N1 | 0.048 (2) | 0.052 (3) | 0.0276 (19) | 0.000 | 0.000 | 0.0029 (18) |
| N2 | 0.084 (3) | 0.053 (3) | 0.030 (2) | 0.000 | 0.000 | 0.0004 (19) |
| C1 | 0.048 (3) | 0.046 (3) | 0.033 (3) | 0.000 | 0.000 | 0.000 (2) |
| C2 | 0.078 (5) | 0.053 (4) | 0.027 (4) | 0.000 | 0.000 | 0.000 |
| C3 | 0.059 (4) | 0.041 (4) | 0.035 (4) | 0.000 | 0.000 | 0.000 |
| C4 | 0.036 (3) | 0.053 (4) | 0.040 (4) | 0.000 | 0.000 | 0.000 |
| C5 | 0.086 (4) | 0.063 (3) | 0.028 (3) | 0.000 | 0.000 | −0.007 (2) |
Geometric parameters (Å, °) top
| S1—C4 | 1.649 (7) | C1—C5 | 1.479 (7) |
| S2—C2 | 1.698 (8) | C2—N2i | 1.322 (6) |
| N1—C1 | 1.345 (6) | C3—C1i | 1.371 (6) |
| N1—C4 | 1.371 (5) | C3—H3 | 0.9300 |
| N1—H1 | 0.8600 | C4—N1i | 1.371 (5) |
| N2—C2 | 1.322 (6) | C5—H5A | 0.9600 |
| N2—H2A | 0.8600 | C5—H5B | 0.9600 |
| N2—H2B | 0.8600 | C5—H5C | 0.9600 |
| C1—C3 | 1.371 (6) | | |
| | | |
| C1—N1—C4 | 125.3 (4) | C1i—C3—C1 | 120.8 (6) |
| C1—N1—H1 | 117.4 | C1i—C3—H3 | 119.6 |
| C4—N1—H1 | 117.4 | C1—C3—H3 | 119.6 |
| C2—N2—H2A | 120.0 | N1i—C4—N1 | 113.3 (6) |
| C2—N2—H2B | 120.0 | N1i—C4—S1 | 123.3 (3) |
| H2A—N2—H2B | 120.0 | N1—C4—S1 | 123.3 (3) |
| N1—C1—C3 | 117.7 (5) | C1—C5—H5A | 109.5 |
| N1—C1—C5 | 117.8 (4) | C1—C5—H5B | 109.5 |
| C3—C1—C5 | 124.5 (5) | H5A—C5—H5B | 109.5 |
| N2i—C2—N2 | 118.8 (7) | C1—C5—H5C | 109.5 |
| N2i—C2—S2 | 120.6 (3) | H5A—C5—H5C | 109.5 |
| N2—C2—S2 | 120.6 (3) | H5B—C5—H5C | 109.5 |
| | | |
| C4—N1—C1—C3 | 0.000 (1) | C5—C1—C3—C1i | 180.0 |
| C4—N1—C1—C5 | 180.000 (1) | C1—N1—C4—N1i | 0.000 (2) |
| N1—C1—C3—C1i | 0.000 (2) | C1—N1—C4—S1 | 180.0 |
| Symmetry codes: (i) x, y, −z+3/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1ii | 0.86 | 2.46 | 3.310 (4) | 171 |
| N2—H2A···Cl1 | 0.86 | 2.50 | 3.297 (5) | 154 |
| N2—H2B···S2iii | 0.86 | 2.49 | 3.347 (5) | 173 |
| Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) −x, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1i | 0.86 | 2.46 | 3.310 (4) | 171 |
| N2—H2A···Cl1 | 0.86 | 2.50 | 3.297 (5) | 154 |
| N2—H2B···S2ii | 0.86 | 2.49 | 3.347 (5) | 173 |
| Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y, −z+1. |
The authors thank the Agence Universitaire de la Francophonie for financial
support (AUF-PSCI No. 6314PS804).
Arslan, H., Flörke, U. & Külcü, N. (2004). Acta Chim. Slov. 51, 787–792.
Hemamalini, M., Muthiah, P. T. & Lynch, D. E. (2005). Acta Cryst. E61, o4107–o4109.
Jianqiang, Q., Liufang, W., Yingqi, L., Yumin, S., Yinyue, W. & Xiaofei, J. (2006). J. Rare Earths, 24, 15–19.
Nonius (1998). COLLECT. Nonius BV, Delft, The Nederlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Seth, S. & Sur, H. (1995). Acta Cryst. C51, 487–489.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Cl hydrogen bonds. The amino groups of each thiourea adduct interact with the chloride anions through a pair of N-H![[Figure 1]](./er2066fig1thm.gif)
![[Figure 2]](./er2066fig2thm.gif)
The title compound, C6H9N2S.CH4N2SCl, was characterized by 1H and 13C NMR, solid-state IR and X-ray crystallographic techniques. The X-ray structure determination reveals that the compound crystallizes in the orthorhombic space group Cmcm with a protonated molecular moiety, a chloride anion and one thiourea adduct in the asymmetric unit. The molecular geometry is illustrated in Fig. 1. The C—S bond length of 1.649 (7) Å in the molecular adduct and 1.698 (8) Å in the thiourea are double bonds character and are comparable to those observed for 1-(biphenyl-4-carbonyl)-3-p-tolyl-thiourea [1.647 (3) Å for C—S (Arslan et al., 2004)]. The C—N bond lengths are in the range [1.322 (6)-1.371 (6) Å] and are shorter than the double C—N bond length (Hemamalini et al. <i/>, 2005). All atoms, except H5B and H5C, lie on a mirror plane, similar to the observed structure of 4,6-dimethylpyrimidine-2(1H</>)-thione (Seth & Sur, 1995). The molecular adduct forms hydrogen bonds with two chloride anions by N1—H1···Cl1(-x + 1/2, -y + 1/2, -z + 1) (Fig. 2). Each thiourea molecule is linked to two other thioura molecule by hydrogen bonds and one chloride anion respectively by N2—H2B···S2(-x, -y, -z + 1) and N2—H2A···Cl1 (Table. 2).