2-Acet­amido-4-p-tolyl-1,3-thia­zole and 2-amino-4-p-tolyl-1,3-thia­zolium chloride dihydrate

Lynch, D.E.; McClenaghan, I.

doi:10.1107/S0108270104023418

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 11| November 2004| Pages o815-o817

doi:10.1107/S0108270104023418

2-Acetamido-4-p-tolyl-1,3-thiazole and 2-amino-4-p-tolyl-1,3-thiazolium chloride dihydrate

Daniel E. Lynch ^a ^* and Ian McClenaghan ^b

^aSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England, and ^bKey Organics Ltd, Highfield Industrial Estate, Camelford, Cornwall PL32 9QZ, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 23 August 2004; accepted 20 September 2004; online 22 October 2004)

The structures of 2-acetamido-4-tolyl-1,3-thiazole, C₁₂H₁₂N₂OS, (I), and 2-amino-4-tolyl-1,3-thiazolium chloride dihydrate, C₁₀H₁₁N₂S⁺·Cl⁻·2H₂O, (II), reveal that both molecules are essentially planar, with the respective dihedral angles between the benzene and thiazole rings being 2.9 (1) and 10.39 (7)°. Compound (I) associates via a single N—H⋯O interaction to form a flat alternate-facing hydrogen-bonded chain [graph-set C $[{_2^2}]$ (4)]. Compound (II) packs with the hydrogen-bonding associations of the Cl atoms and the water molecules creating a convoluted hydrogen-bonded ribbon made up of five-membered donor–acceptor rings, involving three water O atoms (with associated H atoms) and two Cl atoms. The thiazolium rings form stacked columns, aligned in the same direction as the hydrogen-bonded ribbons, of alternate-facing molecules that are also involved in the hydrogen-bonding network, linking to the Cl atoms and one of the water molecules. Subsequently, each Cl atom is the hydrogen-bond acceptor for five separate O/N—H associations.

Comment

2-Amino-4-phenyl-1,3-thiazole has both pharmaceutical and industrial applications (Au-Alvarez et al., 1999 ), including corrosion inhibition (Form et al., 1974 ); the structures of 2-amino-4-phenylthiazole and its hydrobromide hydrate salt are reported, respectively, in these two references. We have recently reviewed the structures of 2-amino-4-phenylthiazole derivatives in terms of their hydrogen-bonding patterns, specifically highlighting any involvement of the thiazole S atom (Lynch et al., 2002 ). Since that paper, the structures of two more derivatives have been reported (Bernes et al., 2002 ; Karanik et al., 2003 ). Several of the analogues that we reported in 2002, such as 2-amino-4-tolyl-1,3-thiazole, either packed quite simply as hydrogen-bonded R $[{_2^2}]$ (8) graph-set (Etter, 1990 ) dimers through N—H⋯N interactions or displayed packing networks containing these dimers. In the cases where molecules did not associate via N—H⋯N hydrogen bonds into dimers, and no other anions or water molecules were present, N—H⋯S interactions were observed. The molecular arrangements in both the Bernes et al. and Karanik et al. structures also included N—H⋯N dimers. As a continuation of our 2002 study into the packing modes of 2-amino-4-phenyl-1,3-thiazole derivatives, we have further determined the structures of 2-acetamido-4-tolyl-1,3-thiazole, (I), and 2-amino-4-tolyl-1,3-thiazolium chloride dihydrate, (II), and report them here. As seen in two structures discussed in our 2002 paper, the packing modes of 2-amino-4-phenyl-1,3-thiazoles with additional anions and/or water molecules differ from the structures of the thiazole molecules by themselves.

The structure of (I) consists of an essentially flat molecule (Fig. 1) which associates via a single N—H⋯O interaction, with alternate-facing molecules, to form a C $[{_2^2}]$ (4) graph-set hydrogen-bonded chain (Fig. 2). The N—H⋯O chain interaction (Table 1) is one of two typical motifs displayed by amide linkages, with the other being an N—H⋯O hydrogen-bonded R $[{_2^2}]$ (8) graph-set dimer (Desiraju, 1995 ). In other 2-acetamido-1,3-thiazole derivatives, of which there are four in the April 2004 version of the Cambridge Structural Database (CSD; Allen, 2002 ), none forms a hydrogen-bonded amide chain similar to (I). Instead, one, namely N-(5-nitro-2-thiazolyl)acetamide (Peeters et al., 1985 ), forms an R $[{_2^2}]$ (8) N—H⋯N hydrogen-bonded dimer, while the other three structures contain additional lattice elements, such as anions, cations and/or water molecules. Furthermore, of 12 2-acetamido-1,3,4-thiadiazole derivatives found in the CSD, only one, namely 2-acetamido-4-benzoyl-5,5-dimethyl-4,5-dihydro-1,3,4-thiadiazoline (Kuban & Schulz, 1987 ), packs with a hydrogen-bonded amide chain. Interestingly, this molecule contains a bulky substituent in the 4-position, similar to (I), whereas those molecules without such substituents predominantly pack as N—H⋯N dimers. In (I), the dihedral angle between the thiazole and phenyl rings is 2.9 (1)°. The comparative dihedral angle in 2-amino-4-tolylthiazole is 12.80 (8)°.

The structure of (II) consists of an essentially flat 2-amino-4-tolyl-1,3-thiazolium molecule, a Cl⁻ anion and two water molecules (Fig. 3), associated in a hydrogen-bonded network. The CSD reveals that there are seven previously reported 2-amino-1,3-thiazolium halide (either Cl⁻ or Br⁻) structures, with three of these being monohydrates; thus, (II) is unique in being the first reported dihydrate. In all of the reported structures, the halide anion associates with either N3 or N21, or both, although across these examples, all of the hydrate structures have N3⁺—H associating to a water O atom. Alternatively, in (II), the same Cl atom (details of hydrogen-bonding interactions are given in Table 2) associates with both N3 and N21, similar to the three non-hydrate structures, with the second H atom on N21 forming a hydrogen bond to a symmetry-equivalent water O atom [O1Wⁱⁱ, see Fig. 4; symmetry code: (ii) 1 − x, y − $[{1 \over 2}]$ , − $[{1 \over 2}]$ − z]. The Cl atom and the two water molecules associate via hydrogen-bonding interactions to construct a convoluted hydrogen-bonded ribbon network which runs in the a cell direction. This ribbon network is made up of five-membered donor–acceptor rings, involving three water O atoms (with associated H atoms) and two Cl atoms [Cl1, O1W, O2Wⁱⁱⁱ, Clⁱⁱⁱ and O2W in Fig. 4; R₃⁵(10) graph set; symmetry code: (iii) x − $[{1 \over 2}]$ , $[{3 \over 2}]$ − y, −z], fused along the O2W—H⋯Cl hydrogen bond. In addition to the hydrogen-bonding associations to Cl1 and O1W, the thiazolium molecules stack in a column co-directional with the anion–water ribbon. The thiazolium columns comprise alternate-facing molecules, with the perpendicular distances between thiazole–phenyl and phenyl–thiazole ring centroids being 3.60 (1) and 3.67 (1) Å, respectively, and with the closest contact distance being 3.35 (1) Å from C4⋯C42(x + $[{1 \over 2}]$ , $[{1 \over 2}]$ − y, −z).

For (II), the dihedral angle between the thiazole and phenyl rings is 10.39 (7)°, which compares with a value of 19 (1)° for 2-amino-4-phenyl-1,3-thiazolium bromide hydrate (Form et al., 1974) and 7.3 (2)° for 2-amino-4-naphthyl-1,3-thiazolium bromide (Lynch et al., 2002). Also noteworthy in (II) is the indication of a delocalized double bond across the N3—C2—N21 site, with distances of 1.322 (8) (C2—N21) and 1.342 (8) Å (C2—N3), compared with distances of 1.351 (2) and 1.309 (2) Å, respectively, for 2-amino-4-tolylthiazole. Similar distances of 1.30 (2) and 1.33 (2) Å, respectively, for 2-amino-4-phenyl-1,3-thiazolium bromide hydrate, and 1.347 (5) and 1.298 (5) Å for 2-amino-4-phenyl-1,3-thiazole itself [the dihedral angle in this molecule is 6.2 (3)°] are also noted. The hydrogen-bonding coordination surrounding the Cl atom is interesting, because without the N21—H21⋯Cl1 association, the remaining four-coordinate motif is pseudo-tetrahedral, with the H⋯Cl⋯H angles from H3 being 94 (3), 118 (3) and 122 (3)°, and the three remaining angles being 105 (3), 105 (3) and 110 (3)°. The addition of the N21—H21⋯Cl1 association thus creates a five-coordinate pseudo-face-capped tetrahedral arrangement, not observed amongst the seven previously reported 2-amino-1,3-thiazolium halide structures.

Figure 1
The molecular configuration and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2
A packing diagram for (I

), viewed down the a axis. [Symmetry code: (i) x + $[{1 \over 2}]$ , $[{1 \over 2}]$ − y, z − $[{1 \over 2}]$ .]

Figure 3
The molecular configuration and atom-numbering scheme for (II

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 4
A packing diagram for (II

). [Symmetry codes: (ii) 1 − x, y − $[{1 \over 2}]$ , − $[{1 \over 2}]$ − z; (iii) x − $[{1 \over 2}]$ , $[{3 \over 2}]$ − y, −z.]

Experimental

Both title compounds were obtained from Key Organics Ltd and crystals were grown from ethanol solutions. Data for (I) were collected at Station 9.8 of the Daresbury SRS (Cernik et al., 1997 ; Clegg, 2000 ). Data for (II) were collected at the EPSRC Crystallographic Service, Southampton.

Compound (I)

Crystal data

C₁₂H₁₂N₂OS
M_r = 232.30
Monoclinic, P2₁/n
a = 3.9541 (5) Å
b = 37.484 (5) Å
c = 7.7173 (9) Å
β = 99.338 (2)°
V = 1128.7 (2) Å³
Z = 4
D_x = 1.367 Mg m⁻³
Synchrotron radiation, λ = 0.6894 Å
Cell parameters from 1753 reflections
θ = 2.7–28.2°
μ = 0.27 mm⁻¹
T = 120 (2) K
Plate, colourless
0.050 × 0.030 × 0.002 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
ω rotation scans with narrow frames
6723 measured reflections
2407 independent reflections
1770 reflections with I > 2σ(I)
R_int = 0.040
θ_max = 26.0°
h = −5 → 2
k = −44 → 47
l = −9 → 9

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.126
S = 1.08
2407 reflections
151 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0604P)² + 0.4975P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯O22ⁱ	0.89 (3)	1.95 (3)	2.818 (3)	166 (3)
Symmetry code: (i) $[{\script{1\over 2}}+x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ .

Compound (II)

Crystal data

C₁₀H₁₁N₂S⁺·Cl⁻·2H₂O
M_r = 262.75
Orthorhombic, P2₁2₁2₁
a = 6.8815 (6) Å
b = 9.3072 (14) Å
c = 19.499 (3) Å
V = 1248.9 (3) Å³
Z = 4
D_x = 1.397 Mg m⁻³
Mo Kα radiation
Cell parameters from 2244 reflections
θ = 2.9–27.1°
μ = 0.46 mm⁻¹
T = 120 (2) K
Needle, colourless
0.35 × 0.02 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
9123 measured reflections
1441 independent reflections
1048 reflections with I > 2σ(I)
R_int = 0.156
θ_max = 26.0°
h = −8 → 8
k = −9 → 11
l = −23 → 24

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.152
S = 1.06
1441 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0775P)² + 0.1085P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 2
Hydrogen-bonding geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Cl1	0.88	2.32	3.126 (5)	151
N21—H21⋯Cl1	0.88	2.58	3.337 (6)	144
N21—H22⋯O1Wⁱⁱ	0.88	1.86	2.726 (7)	166
O1W—H11W⋯Cl1	0.88 (6)	2.26 (6)	3.136 (5)	178 (7)
O1W—H12W⋯O2Wⁱⁱⁱ	0.88 (5)	1.83 (3)	2.700 (7)	169 (8)
O2W—H22W⋯Cl1	0.88 (2)	2.35 (2)	3.214 (5)	167 (6)
O2W—H21W⋯Cl1ⁱⁱⁱ	0.88 (5)	2.29 (3)	3.151 (5)	166 (6)
Symmetry codes: (ii) $[1-x,y-{\script{1\over 2}},-{\script{1\over 2}}-z]$ ; (iii) $[x-{\script{1\over 2}},{\script{3\over 2}}-y,-z]$ .

All H atoms, except for the N—H atom in (I) and the water H atoms in (II), were included in the refinements at calculated positions in the riding-model approximation, with N—H distances of 0.88 Å and C—H distances of 0.95 (aromatic H atoms) and 0.98 Å (methyl H atoms), and with U_iso(H) = 1.25U_eq(C,N). The N—H atom in (I) was located in Fourier syntheses and both its positional and displacement parameters were refined. The water H atoms in (II) were also located in Fourier syntheses, but their positional and displacement parameters were refined with O—H distance restraints of 0.88 Å and H⋯H restraints of 1.4 Å. U_iso(H) values for the water H atoms were set equal to 1.25U_eq(O). Refinement of the absolute structure parameter (Flack, 1983 ) gave ambiguous results, indicating that the absolute structure of (II) could not be accurately determined from the diffraction data, even with the presence of a Cl atom; thus Friedel opposites were merged. For (II), the number of Friedel pairs is 837. The high R_int value was the result of weak high-angle data.

For compound (I), data collection, cell refinement and data reduction: SMART (Bruker, 2001 ). For compound (II), data collection and cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Nonius, 1998 ); data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT. For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, II, global. DOI: 10.1107/S0108270104023418/fa1090sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104023418/fa1090Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104023418/fa1090IIsup3.hkl

Comment top

2-Amino-4-phenyl-1,3-thiazole has both pharmaceutical and industrial applications (Au-Alvarez et al., 1999), including corrosion inhibition (Form et al., 1974); the structures of 2-amino-4-phenylthiazole and its hydrobromide hydrate salt are reported, respectively, in these two references. We have recently reviewed the structures of 2-amino-4-phenylthiazole derivatives in terms of their hydrogen-bonding patterns, specifically highlighting any involvement of the thiazole S atom (Lynch et al., 2002). Since that paper, the structures of two more derivatives have been reported (Bernes et al., 2002; Karanik et al., 2003). Several of the analogues that we reported in 2002, such as 2-amino-4-tolyl-1,3-thiazole, either packed quite simply as hydrogen-bonded R₂²(8) graph set (Etter, 1990) dimers through N—H···N interactions, or displayed packing networks containing these dimers. In the cases where molecules did not associate via N—H···N dimers, and no other anions or water molecules were present, N—H···S interactions were observed. The molecular arrangements in both the Bernes et al. and Karanik et al. structures also included N—H···N dimers. As a continuation of our 2002 study into the packing modes of 2-amino-4-phenyl-1,3-thiazole derivatives, we have further determined the structures of 2-acetamido-4-tolyl-1,3-thiazole, (I), and 2-amino-4-tolyl-1,3-thiazolium chloride dihydrate, (II), and report them here. As seen in two structures discussed in our 2002 paper, the packing modes of 2-amino-4-phenyl-1,3-thiazoles with additional anions and/or water molecules differ from the structures of the thiazole molecules by themselves. \sch

The structure of (I) consists of an essentially flat molecule (Fig. 1) which associates via a single N—H···O interaction, with alternate-facing molecules, to form a C₂²(4) graph set hydrogen-bonded chain (Fig. 2). The N—H···O chain interaction (Table 1) is one of two typical motifs displayed by amide linkages, with the other being an N—H···O hydrogen-bonded R₂²(8) graph set dimer (Desiraju, 1995). In other 2-acetamido-1,3-thiazole derivatives, of which there are four in the April 2004 version of the Cambridge Structural Database (CSD; Allen, 2002), none forms a hydrogen-bonded amide chain similar to (I). Instead, one, N-(5-nitro-2-thiazolyl)-acetamide (Peeters et al., 1985), forms an R₂²(8) N—H···N hydrogen-bonded dimer, while the other three structures contain additional lattice elements, such as anions, cations and/or water molecules. Furthermore, of 12 2-acetamido-1,3,4-thiadiazole derivatives found in the CSD, only one, 2-acetamido-4-benzoyl-5,5-dimethyl-4,5-dihydro-1,3,4-thiadiazoline (Kuban & Schulz, 1987), packs with a hydrogen-bonded amide chain. Interestingly, this molecule contains a bulky substituent in the 4-position, similar to (I), whereas those molecules without such substituents predominantly pack as N—H···N dimers. In (I), the dihedral angle between the thiazole and phenyl rings is 2.9 (1)°. The comparative dihedral angle in 2-amino-4-tolylthiazole is 12.80 (8)°.

The structure of (II) consists of an essentially flat 2-amino-4-tolyl-1,3-thiazolium molecule, a Cl⁻ anion and two water molecules (Fig. 3), associated in a hydrogen-bonded network. The CSD reveals that there are seven previously reported 2-amino-1,3-thiazolium halide (either Cl⁻ or Br⁻) structures, with three of these being monohydrates; thus (II) is unique in being the first reported dihydrate. In all of the reported structures, the halide anion associates with either N3 or N21, or both, although across these examples, all of the hydrate structures have N3⁺—H associating to a water O atom. Alternatively, in (II), the same Cl atom (details of hydrogen-bonding interactions in Table 2) associates to both N3 and N21, similar to three non-hydrate structures, with the second H atom from N21 forming a hydrogen bond to a symmetry-equivalent water O atom [O1Wⁱⁱ; Fig. 4; symmetry code: (ii) 1 − x, y − 1/2, 1/2 − z]. The Cl atom and the two water molecules associate, via hydrogen-bonding interactions, to construct a convoluted hydrogen-bonded ribbon network which runs in the a cell direction. This ribbon network is made up of five-membered donor-acceptor rings, involving three water O atoms (with associated H atoms) and two Cl atoms [Cl1, O1W, O2Wⁱⁱⁱ, Clⁱⁱⁱ and O2W in Fig. 4; R₃⁵(10) graph set; symmetry code: (iii) x − 1/2, 3/2 − y, −z], fused along the O2W—H···Cl hydrogen-bond. In addition to the hydrogen-bonding associations to Cl1 and O1W, the thiazolium molecules stack in a column co-directional with the anion-water ribbon. The thiazolium columns comprise alternate-facing molecules, with the perpendicular distances between thiazole-phenyl and phenyl-thiazole ring centroids being 3.60 (1) and 3.67 (1) Å, respectively, and with the closest contact distance being 3.35 (1) Å from C4 to C42(x + 1/2, 1/2 − y, −z).

For (II), the dihedral angle between the thiazole and phenyl rings is 10.39 (7)°, which compares with 19 (1)° for 2-amino-4-phenyl-1,3-thiazolium bromide hydrate (Form et al., 1974) and 7.3 (2)° for 2-amino-4-(naphthyl)-1,3-thiazolium bromide (Lynch et al., 2002). Also noteworthy in (II) is the indication of a delocalized double bond across the N3—C2—N21 site, with distances of 1.322 (8) (C2—N21) and 1.342 (8) Å (C2—N3), compared with distances of 1.351 (2) and 1.309 (2) Å, respectively, for 2-amino-4-tolylthiazole. Similar differences, of 1.30 (2) and 1.33 (2) Å, respectively, for 2-amino-4-phenyl-1,3-thiazolium bromide hydrate, and 1.347 (5) and 1.298 (5) Å, respectively, for 2-amino-4-phenyl-1,3-thiazole itself [dihedral angle in this molecule 6.2 (3)°], are also noted. The hydrogen-bonding coordination surrounding the Cl atom is interesting, because without the N21—H21···Cl1 association, the remaining four-coordinate motif is pseudo-tetrahedral, with H···Cl···H angles from H3 being 94 (3), 118 (3) and 122 (3)°, and the three remaining angles being 105 (3), 105 (3) and 110 (3)°. The addition of the N21—H21···Cl1 association thus creates a five-coordinate pseudo-face-capped tetrahedral arrangement, not observed amongst the seven previously reported 2-amino-1,3-thiazolium halide structures.

Experimental top

Both compounds were obtained from Key Organics Ltd., and crystals were grown from ethanol solutions.

Computing details top

Data collection: SMART (Bruker, 2001) for (I); DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (II). Cell refinement: SMART for (I); DENZO and COLLECT for (II). Data reduction: SMART for (I); DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular configuration and atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I), viewed down the a axis. [Symmetry code: (i) x + 1/2, 1/2 − y, z − 1/2.]
	Fig. 3. The molecular configuration and atom-numbering scheme for (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A packing diagram for (II). [Symmetry codes: (ii) 1 − x, y − 1/2, 1/2 − z; (iii) x − 1/2, 3/2 − y, −z.]

(I) 2-Acetamido-4-p-tolyl-1,3-thiazole top

Crystal data top

C₁₂H₁₂N₂OS	F(000) = 488
M_r = 232.30	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.6894 Å
Hall symbol: -P 2yn	Cell parameters from 1753 reflections
a = 3.9541 (5) Å	θ = 2.7–28.2°
b = 37.484 (5) Å	µ = 0.27 mm⁻¹
c = 7.7173 (9) Å	T = 120 K
β = 99.338 (2)°	Plate, colourless
V = 1128.7 (2) Å³	0.05 × 0.03 × 0.002 mm
Z = 4

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1770 reflections with I > 2σ(I)
Radiation source: Daresbury SRS Station 9.8 (Cernik et al., 1997; Clegg, 2000)	R_int = 0.040
Silicon 111 monochromator	θ_max = 26.0°, θ_min = 2.1°
Detector resolution: 8.192 pixels mm^-1	h = −5→2
ω rotation with narrow frames scans	k = −44→47
6723 measured reflections	l = −9→9
2407 independent reflections

Refinement top

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) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0604P)² + 0.4975P] where P = (F_o² + 2F_c²)/3
2407 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₂H₁₂N₂OS	V = 1128.7 (2) Å³
M_r = 232.30	Z = 4
Monoclinic, P2₁/n	Synchrotron radiation, λ = 0.6894 Å
a = 3.9541 (5) Å	µ = 0.27 mm⁻¹
b = 37.484 (5) Å	T = 120 K
c = 7.7173 (9) Å	0.05 × 0.03 × 0.002 mm
β = 99.338 (2)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1770 reflections with I > 2σ(I)
6723 measured reflections	R_int = 0.040
2407 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.32 e Å⁻³
2407 reflections	Δρ_min = −0.32 e Å⁻³
151 parameters

Special details top

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

3.4460 (0.0017) x − 2.8824 (0.0477) y + 2.5969 (0.0060) z = 3.7007 (0.0085)

* −0.0014 (0.0011) S1 * −0.0004 (0.0014) C2 * 0.0025 (0.0015) N3 * −0.0039 (0.0016) C4 * 0.0032 (0.0015) C5

Rms deviation of fitted atoms = 0.0026

3.5389 (0.0021) x − 2.3368 (0.0465) y + 2.2430 (0.0086) z = 3.6065 (0.0047)

Angle to previous plane (with approximate e.s.d.) = 2.91 (0.13)

* −0.0026 (0.0019) C41 * 0.0006 (0.0020) C42 * 0.0028 (0.0021) C43 * −0.0043 (0.0021) C44 * 0.0023 (0.0022) C45 * 0.0011 (0.0021) C46

Rms deviation of fitted atoms = 0.0026

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

	x	y	z	U_iso*/U_eq
S1	0.49456 (18)	0.165388 (17)	0.95180 (8)	0.02014 (19)
C2	0.6413 (6)	0.18746 (6)	0.7819 (3)	0.0175 (5)
N3	0.7199 (5)	0.16755 (5)	0.6567 (2)	0.0181 (4)
C4	0.6624 (7)	0.13189 (6)	0.6909 (3)	0.0180 (5)
C5	0.5445 (7)	0.12616 (7)	0.8438 (3)	0.0213 (6)
H5	0.4954	0.1033	0.8861	0.027*
N21	0.6790 (6)	0.22419 (5)	0.7745 (3)	0.0180 (5)
H21	0.761 (7)	0.2330 (7)	0.682 (4)	0.021 (7)*
C22	0.5850 (7)	0.24777 (7)	0.8913 (3)	0.0182 (5)
O22	0.4597 (5)	0.23738 (5)	1.0180 (2)	0.0229 (4)
C23	0.6423 (7)	0.28629 (6)	0.8541 (3)	0.0205 (5)
H231	0.5667	0.3010	0.9454	0.026*
H232	0.5110	0.2926	0.7394	0.026*
H233	0.8868	0.2904	0.8531	0.026*
C41	0.7322 (7)	0.10513 (6)	0.5611 (3)	0.0200 (5)
C42	0.8383 (8)	0.11578 (7)	0.4062 (3)	0.0261 (6)
H42	0.8681	0.1405	0.3852	0.033*
C43	0.9016 (8)	0.09101 (8)	0.2815 (4)	0.0282 (6)
H43	0.9750	0.0990	0.1769	0.035*
C44	0.8595 (7)	0.05489 (8)	0.3072 (4)	0.0284 (6)
C45	0.7557 (8)	0.04429 (7)	0.4627 (4)	0.0341 (7)
H45	0.7277	0.0196	0.4837	0.043*
C46	0.6919 (8)	0.06869 (7)	0.5884 (4)	0.0283 (6)
H46	0.6204	0.0606	0.6934	0.035*
C47	0.9250 (9)	0.02808 (8)	0.1707 (4)	0.0402 (8)
H471	1.1704	0.0226	0.1861	0.050*
H472	0.8508	0.0380	0.0532	0.050*
H473	0.7963	0.0062	0.1842	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0254 (4)	0.0209 (3)	0.0154 (3)	−0.0006 (3)	0.0069 (2)	0.0009 (2)
C2	0.0183 (13)	0.0202 (12)	0.0133 (11)	0.0005 (10)	0.0004 (9)	0.0012 (9)
N3	0.0205 (11)	0.0192 (10)	0.0145 (9)	0.0015 (9)	0.0026 (8)	−0.0003 (8)
C4	0.0202 (13)	0.0161 (12)	0.0170 (11)	−0.0001 (10)	0.0007 (10)	0.0008 (9)
C5	0.0270 (15)	0.0178 (12)	0.0195 (12)	−0.0007 (11)	0.0050 (11)	0.0001 (10)
N21	0.0240 (12)	0.0176 (10)	0.0134 (10)	0.0002 (9)	0.0061 (9)	0.0004 (8)
C22	0.0194 (13)	0.0207 (12)	0.0146 (11)	0.0017 (10)	0.0030 (10)	−0.0028 (9)
O22	0.0320 (11)	0.0223 (9)	0.0166 (9)	0.0003 (8)	0.0108 (8)	−0.0004 (7)
C23	0.0255 (14)	0.0184 (12)	0.0187 (12)	−0.0001 (10)	0.0066 (10)	−0.0011 (10)
C41	0.0201 (13)	0.0196 (13)	0.0193 (12)	0.0004 (10)	0.0003 (10)	−0.0025 (10)
C42	0.0361 (16)	0.0212 (13)	0.0211 (13)	0.0029 (12)	0.0047 (12)	−0.0023 (10)
C43	0.0319 (16)	0.0320 (15)	0.0198 (13)	0.0047 (12)	0.0014 (12)	−0.0045 (11)
C44	0.0260 (15)	0.0291 (15)	0.0286 (15)	0.0026 (12)	0.0001 (12)	−0.0103 (11)
C45	0.0379 (18)	0.0177 (14)	0.0469 (18)	−0.0007 (13)	0.0076 (15)	−0.0071 (12)
C46	0.0319 (16)	0.0226 (14)	0.0322 (15)	−0.0019 (12)	0.0103 (13)	−0.0006 (11)
C47	0.046 (2)	0.0356 (17)	0.0393 (18)	0.0028 (15)	0.0092 (16)	−0.0163 (13)

Geometric parameters (Å, º) top

S1—C5	1.717 (3)	C41—C42	1.388 (4)
S1—C2	1.728 (2)	C41—C46	1.395 (4)
C2—N3	1.298 (3)	C42—C43	1.389 (4)
C2—N21	1.387 (3)	C42—H42	0.95
N3—C4	1.388 (3)	C43—C44	1.382 (4)
C4—C5	1.354 (3)	C43—H43	0.95
C4—C41	1.475 (3)	C44—C45	1.388 (4)
C5—H5	0.95	C44—C47	1.508 (4)
N21—C22	1.357 (3)	C45—C46	1.386 (4)
N21—H21	0.89 (3)	C45—H45	0.95
C22—O22	1.229 (3)	C46—H46	0.95
C22—C23	1.496 (3)	C47—H471	0.98
C23—H231	0.98	C47—H472	0.98
C23—H232	0.98	C47—H473	0.98
C23—H233	0.98

C5—S1—C2	87.86 (12)	C42—C41—C4	120.3 (2)
N3—C2—N21	120.0 (2)	C46—C41—C4	121.6 (2)
N3—C2—S1	116.09 (18)	C43—C42—C41	121.2 (3)
N21—C2—S1	123.95 (18)	C43—C42—H42	119.4
C2—N3—C4	110.2 (2)	C41—C42—H42	119.4
C5—C4—N3	114.1 (2)	C44—C43—C42	121.1 (3)
C5—C4—C41	127.8 (2)	C44—C43—H43	119.5
N3—C4—C41	118.1 (2)	C42—C43—H43	119.5
C4—C5—S1	111.72 (19)	C43—C44—C45	117.6 (2)
C4—C5—H5	124.1	C43—C44—C47	121.0 (3)
S1—C5—H5	124.1	C45—C44—C47	121.4 (3)
C22—N21—C2	125.2 (2)	C46—C45—C44	122.0 (3)
C22—N21—H21	117.7 (18)	C46—C45—H45	119.0
C2—N21—H21	117.1 (18)	C44—C45—H45	119.0
O22—C22—N21	120.7 (2)	C45—C46—C41	120.1 (3)
O22—C22—C23	123.5 (2)	C45—C46—H46	119.9
N21—C22—C23	115.8 (2)	C41—C46—H46	119.9
C22—C23—H231	109.5	C44—C47—H471	109.5
C22—C23—H232	109.5	C44—C47—H472	109.5
H231—C23—H232	109.5	H471—C47—H472	109.5
C22—C23—H233	109.5	C44—C47—H473	109.5
H231—C23—H233	109.5	H471—C47—H473	109.5
H232—C23—H233	109.5	H472—C47—H473	109.5
C42—C41—C46	118.0 (2)

C5—S1—C2—N3	0.0 (2)	N3—C4—C41—C42	−2.7 (4)
C5—S1—C2—N21	−179.6 (2)	C5—C4—C41—C46	−2.5 (4)
N21—C2—N3—C4	−180.0 (2)	N3—C4—C41—C46	177.9 (2)
S1—C2—N3—C4	0.4 (3)	C46—C41—C42—C43	0.2 (4)
C2—N3—C4—C5	−0.7 (3)	C4—C41—C42—C43	−179.3 (3)
C2—N3—C4—C41	179.0 (2)	C41—C42—C43—C44	0.3 (4)
N3—C4—C5—S1	0.7 (3)	C42—C43—C44—C45	−0.7 (4)
C41—C4—C5—S1	−179.0 (2)	C42—C43—C44—C47	179.4 (3)
C2—S1—C5—C4	−0.4 (2)	C43—C44—C45—C46	0.7 (5)
N3—C2—N21—C22	175.6 (2)	C47—C44—C45—C46	−179.4 (3)
S1—C2—N21—C22	−4.8 (4)	C44—C45—C46—C41	−0.2 (5)
C2—N21—C22—O22	1.1 (4)	C42—C41—C46—C45	−0.3 (4)
C2—N21—C22—C23	−178.5 (2)	C4—C41—C46—C45	179.2 (3)
C5—C4—C41—C42	177.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O22ⁱ	0.89 (3)	1.95 (3)	2.818 (3)	166 (3)

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

(II) 2-amino-4-tolyl-1,3-thiazolium chloride dihydrate top

Crystal data top

C₁₀H₁₁N₂S⁺·Cl⁻·2H₂O	F(000) = 552
M_r = 262.75	D_x = 1.397 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2244 reflections
a = 6.8815 (6) Å	θ = 2.9–27.1°
b = 9.3072 (14) Å	µ = 0.46 mm⁻¹
c = 19.499 (3) Å	T = 120 K
V = 1248.9 (3) Å³	Needle, colourless
Z = 4	0.35 × 0.02 × 0.02 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	1048 reflections with I > 2σ(I)
Radiation source: Bruker Nonius FR591 rotating anode	R_int = 0.156
Graphite monochromator	θ_max = 26.0°, θ_min = 3.0°
Detector resolution: 9.091 pixels mm^-1	h = −8→8
ϕ and ω scans	k = −9→11
9123 measured reflections	l = −23→24
1441 independent reflections

Refinement top

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0775P)² + 0.1085P] where P = (F_o² + 2F_c²)/3
1441 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.44 e Å⁻³
6 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₁₀H₁₁N₂S⁺·Cl⁻·2H₂O	V = 1248.9 (3) Å³
M_r = 262.75	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.8815 (6) Å	µ = 0.46 mm⁻¹
b = 9.3072 (14) Å	T = 120 K
c = 19.499 (3) Å	0.35 × 0.02 × 0.02 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	1048 reflections with I > 2σ(I)
9123 measured reflections	R_int = 0.156
1441 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	6 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.44 e Å⁻³
1441 reflections	Δρ_min = −0.47 e Å⁻³
159 parameters

Special details top

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.8444 (0.0021) x + 0.9623 (0.0236) y − 0.1571 (0.0462) z = 4.5106 (0.0062)

* 0.0027 (0.0047) C41 * −0.0022 (0.0049) C42 * 0.0001 (0.0049) C43 * 0.0015 (0.0043) C44 * −0.0010 (0.0047) C45 * −0.0011 (0.0050) C46

Rms deviation of fitted atoms = 0.0016

6.8599 (0.0018) x − 0.7208 (0.0273) y − 0.3258 (0.0468) z = 4.2195 (0.0099)

Angle to previous plane (with approximate e.s.d.) = 10.39 (0.07)

* −0.0004 (0.0030) S1 * −0.0028 (0.0037) C2 * 0.0053 (0.0042) N3 * −0.0057 (0.0043) C4 * 0.0035 (0.0038) C5

Rms deviation of fitted atoms = 0.0040

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

	x	y	z	U_iso*/U_eq
S1	0.6173 (2)	0.10019 (18)	−0.17494 (9)	0.0381 (5)
N3	0.6432 (7)	0.2996 (5)	−0.0877 (3)	0.0312 (12)
H3	0.6547	0.3855	−0.0693	0.039*
N21	0.6430 (7)	0.3850 (6)	−0.2005 (3)	0.0354 (12)
H21	0.6521	0.4742	−0.1860	0.044*
H22	0.6383	0.3667	−0.2447	0.044*
C2	0.6365 (9)	0.2782 (7)	−0.1558 (3)	0.0339 (15)
C4	0.6302 (9)	0.1739 (6)	−0.0486 (3)	0.0295 (14)
C5	0.6176 (10)	0.0580 (7)	−0.0872 (3)	0.0398 (16)
H5	0.6096	−0.0370	−0.0696	0.050*
C41	0.6339 (9)	0.1855 (7)	0.0270 (3)	0.0309 (14)
C42	0.6516 (9)	0.0617 (7)	0.0679 (3)	0.0349 (15)
H42	0.6633	−0.0302	0.0471	0.044*
C43	0.6518 (9)	0.0744 (7)	0.1385 (3)	0.0355 (16)
H43	0.6643	−0.0097	0.1658	0.044*
C44	0.6342 (9)	0.2060 (7)	0.1704 (4)	0.0347 (14)
C45	0.6158 (9)	0.3280 (7)	0.1304 (3)	0.0327 (15)
H45	0.6031	0.4197	0.1514	0.041*
C46	0.6158 (9)	0.3156 (7)	0.0592 (3)	0.0335 (15)
H46	0.6030	0.3999	0.0321	0.042*
C47	0.6348 (10)	0.2194 (7)	0.2479 (3)	0.0392 (16)
H471	0.5830	0.1311	0.2683	0.049*
H472	0.5537	0.3011	0.2616	0.049*
H473	0.7682	0.2347	0.2640	0.049*
Cl1	0.6618 (2)	0.63450 (17)	−0.07781 (8)	0.0390 (5)
O1W	0.3448 (7)	0.7854 (6)	−0.1681 (2)	0.0447 (12)
H11W	0.432 (7)	0.741 (8)	−0.143 (3)	0.056*
H12W	0.240 (6)	0.787 (8)	−0.142 (3)	0.056*
O2W	0.5451 (7)	0.6804 (5)	0.0803 (3)	0.0437 (12)
H21W	0.447 (7)	0.739 (6)	0.086 (3)	0.055*
H22W	0.556 (10)	0.669 (8)	0.0358 (12)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0377 (9)	0.0418 (9)	0.0347 (9)	0.0028 (8)	−0.0041 (8)	−0.0082 (8)
N3	0.029 (3)	0.040 (3)	0.024 (3)	0.002 (2)	−0.002 (2)	−0.003 (2)
N21	0.037 (3)	0.042 (3)	0.027 (3)	−0.002 (3)	−0.002 (2)	−0.003 (2)
C2	0.028 (3)	0.046 (4)	0.027 (4)	−0.002 (3)	0.001 (3)	−0.009 (3)
C4	0.033 (3)	0.027 (3)	0.028 (3)	0.003 (3)	−0.004 (3)	0.000 (3)
C5	0.041 (4)	0.043 (4)	0.036 (4)	0.005 (3)	−0.002 (3)	0.006 (3)
C41	0.030 (3)	0.035 (4)	0.027 (3)	0.000 (3)	−0.001 (3)	0.000 (3)
C42	0.037 (4)	0.036 (4)	0.031 (4)	0.003 (3)	−0.005 (3)	−0.005 (3)
C43	0.030 (3)	0.037 (4)	0.039 (4)	0.004 (3)	0.004 (3)	0.010 (3)
C44	0.026 (3)	0.049 (4)	0.030 (3)	−0.001 (3)	0.002 (3)	0.004 (3)
C45	0.032 (3)	0.036 (4)	0.029 (3)	0.001 (3)	0.004 (3)	−0.007 (3)
C46	0.036 (4)	0.037 (4)	0.028 (3)	0.005 (3)	−0.003 (3)	0.006 (3)
C47	0.039 (4)	0.051 (4)	0.028 (4)	−0.002 (4)	0.008 (3)	0.005 (3)
Cl1	0.0406 (9)	0.0407 (9)	0.0357 (9)	−0.0016 (7)	−0.0011 (8)	0.0008 (8)
O1W	0.046 (3)	0.062 (3)	0.026 (3)	0.000 (3)	0.000 (2)	0.008 (2)
O2W	0.045 (3)	0.054 (3)	0.032 (3)	0.009 (2)	−0.002 (2)	−0.007 (3)

Geometric parameters (Å, º) top

S1—C2	1.704 (7)	C43—C44	1.379 (9)
S1—C5	1.755 (7)	C43—H43	0.95
N3—C2	1.342 (8)	C44—C45	1.383 (9)
N3—C4	1.400 (8)	C44—C47	1.516 (9)
N3—H3	0.88	C45—C46	1.395 (9)
N21—C2	1.322 (8)	C45—H45	0.95
N21—H21	0.88	C46—H46	0.95
N21—H22	0.88	C47—H471	0.98
C4—C5	1.318 (9)	C47—H472	0.98
C4—C41	1.479 (9)	C47—H473	0.98
C5—H5	0.95	O1W—H11W	0.88 (6)
C41—C46	1.369 (9)	O1W—H12W	0.88 (5)
C41—C42	1.407 (9)	O2W—H21W	0.88 (5)
C42—C43	1.382 (9)	O2W—H22W	0.88 (2)
C42—H42	0.95

C2—S1—C5	90.2 (3)	C41—C42—H42	120.2
C2—N3—C4	114.4 (5)	C42—C43—C44	121.7 (6)
C2—N3—H3	122.8	C42—C43—H43	119.2
C4—N3—H3	122.8	C44—C43—H43	119.2
C2—N21—H21	120.0	C43—C44—C45	118.9 (6)
C2—N21—H22	120.0	C43—C44—C47	121.5 (6)
H21—N21—H22	120.0	C45—C44—C47	119.6 (6)
N21—C2—N3	122.6 (6)	C44—C45—C46	119.6 (6)
N21—C2—S1	126.1 (5)	C44—C45—H45	120.2
N3—C2—S1	111.3 (5)	C46—C45—H45	120.2
C5—C4—N3	112.1 (5)	C41—C46—C45	121.9 (6)
C5—C4—C41	129.1 (6)	C41—C46—H46	119.0
N3—C4—C41	118.8 (5)	C45—C46—H46	119.0
C4—C5—S1	111.9 (5)	C44—C47—H471	109.5
C4—C5—H5	124.0	C44—C47—H472	109.5
S1—C5—H5	124.0	H471—C47—H472	109.5
C46—C41—C42	118.2 (6)	C44—C47—H473	109.5
C46—C41—C4	121.3 (6)	H471—C47—H473	109.5
C42—C41—C4	120.4 (5)	H472—C47—H473	109.5
C43—C42—C41	119.6 (6)	H11W—O1W—H12W	104 (3)
C43—C42—H42	120.2	H21W—O2W—H22W	105 (3)

C4—N3—C2—N21	178.7 (6)	N3—C4—C41—C42	−170.1 (6)
C4—N3—C2—S1	−0.9 (8)	C46—C41—C42—C43	−0.5 (10)
C5—S1—C2—N21	−179.2 (7)	C4—C41—C42—C43	−179.0 (6)
C5—S1—C2—N3	0.3 (5)	C41—C42—C43—C44	0.3 (11)
C2—N3—C4—C5	1.2 (9)	C42—C43—C44—C45	0.1 (10)
C2—N3—C4—C41	−179.3 (6)	C42—C43—C44—C47	−179.9 (6)
N3—C4—C5—S1	−1.0 (8)	C43—C44—C45—C46	−0.2 (10)
C41—C4—C5—S1	179.6 (6)	C47—C44—C45—C46	179.8 (6)
C2—S1—C5—C4	0.4 (6)	C42—C41—C46—C45	0.4 (10)
C5—C4—C41—C46	−169.2 (7)	C4—C41—C46—C45	178.9 (6)
N3—C4—C41—C46	11.4 (10)	C44—C45—C46—C41	−0.1 (11)
C5—C4—C41—C42	9.2 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl1	0.88	2.32	3.126 (5)	151
N21—H21···Cl1	0.88	2.58	3.337 (6)	144
N21—H22···O1Wⁱ	0.88	1.86	2.726 (7)	166
O1W—H11W···Cl1	0.88 (6)	2.26 (6)	3.136 (5)	178 (7)
O1W—H12W···O2Wⁱⁱ	0.88 (5)	1.83 (3)	2.700 (7)	169 (8)
O2W—H22W···Cl1	0.88 (2)	2.35 (2)	3.214 (5)	167 (6)
O2W—H21W···Cl1ⁱⁱ	0.88 (5)	2.29 (3)	3.151 (5)	166 (6)

Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) x−1/2, −y+3/2, −z.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₂H₁₂N₂OS	C₁₀H₁₁N₂S⁺·Cl⁻·2H₂O
M_r	232.30	262.75
Crystal system, space group	Monoclinic, P2₁/n	Orthorhombic, P2₁2₁2₁
Temperature (K)	120	120
a, b, c (Å)	3.9541 (5), 37.484 (5), 7.7173 (9)	6.8815 (6), 9.3072 (14), 19.499 (3)
α, β, γ (°)	90, 99.338 (2), 90	90, 90, 90
V (Å³)	1128.7 (2)	1248.9 (3)
Z	4	4
Radiation type	Synchrotron, λ = 0.6894 Å	Mo Kα
µ (mm⁻¹)	0.27	0.46
Crystal size (mm)	0.05 × 0.03 × 0.002	0.35 × 0.02 × 0.02

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6723, 2407, 1770	9123, 1441, 1048
R_int	0.040	0.156
(sin θ/λ)_max (Å⁻¹)	0.636	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.126, 1.08	0.063, 0.152, 1.06
No. of reflections	2407	1441
No. of parameters	151	159
No. of restraints	0	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32	0.44, −0.47

Computer programs: SMART (Bruker, 2001), DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), SMART, DENZO and COLLECT, DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O22ⁱ	0.89 (3)	1.95 (3)	2.818 (3)	166 (3)

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl1	0.88	2.32	3.126 (5)	151
N21—H21···Cl1	0.88	2.58	3.337 (6)	144
N21—H22···O1Wⁱ	0.88	1.86	2.726 (7)	166
O1W—H11W···Cl1	0.88 (6)	2.26 (6)	3.136 (5)	178 (7)
O1W—H12W···O2Wⁱⁱ	0.88 (5)	1.83 (3)	2.700 (7)	169 (8)
O2W—H22W···Cl1	0.88 (2)	2.35 (2)	3.214 (5)	167 (6)
O2W—H21W···Cl1ⁱⁱ	0.88 (5)	2.29 (3)	3.151 (5)	166 (6)

Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) x−1/2, −y+3/2, −z.

Acknowledgements

The authors thank the EPSRC National Crystallography Service, Southampton, and the EPSRC Chemical Database Service at Daresbury.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Au-Alvarez, O., Peterson, R. C., Acosta Crespo, A., Rodríguez Esteva, Y., Marquez Alvarez, H., Plutín Stiven, A. M. & Pomés Hernández, R. (1999). Acta Cryst. C55, 821–823. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bernès, S., Berros, M. I., Rodríguez de Barbarín, C. & Sánchez-Viesca, F. (2002). Acta Cryst. C58, o151–o153. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2001). SMART. Version 5.624. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cernik, R. J., Clegg, W., Catlow, C. R. A., Bushnell-Wye, G., Flaherty, J. V., Greaves, G. N., Burrows, I., Taylor, D. J., Teat, S. J. & Hamichi, M. (1997). J. Synchotron Rad. 4, 279–286; erratum, 7, 40. Google Scholar
Clegg, W. (2000). J. Chem. Soc. Dalton Trans. pp. 3223–3232. Web of Science CrossRef Google Scholar
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311–2327. CrossRef CAS Web of Science Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Form, G. R., Raper, E. S. & Downie, T. C. (1974). Acta Cryst. B30, 342–348. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Karanik, M., Patzel, M. & Liebscher, J. (2003). Synthesis, pp. 1201–1208. Google Scholar
Kuban, R.-J. & Schulz, B. (1987). Cryst. Res. Technol. 22, 799–802. CrossRef CAS Web of Science Google Scholar
Lynch, D. E., McClenaghan, I., Light, M. E. & Coles, S. J. (2002). Cryst. Eng. 5, 123–136. Web of Science CSD CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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. Google Scholar
Peeters, O. M., Blaton, N. M. & De Ranter, C. J. (1985). Acta Cryst. C41, 965–967. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2053-2296

Volume 60| Part 11| November 2004| Pages o815-o817

doi:10.1107/S0108270104023418

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Acet­amido-4-p-tolyl-1,3-thia­zole and 2-amino-4-p-tolyl-1,3-thia­zolium chloride dihydrate

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Acetamido-4-p-tolyl-1,3-thiazole and 2-amino-4-p-tolyl-1,3-thiazolium chloride dihydrate