2-Amino-3-hydroxy-4-phenyl­thia­zol­ium chloride: π-stacked hydrogen-bonded chains of edge-fused R_{\bf 4}^{\bf 2}(11) rings

Glidewell, C.; Low, J.N.; Skakle, J.M.S.; Wardell, J.L.

doi:10.1107/S0108270104004780

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 4| April 2004| Pages o273-o275

doi:10.1107/S0108270104004780

2-Amino-3-hydroxy-4-phenylthiazolium chloride: π-stacked hydrogen-bonded chains of edge-fused R $[_{\bf 4}^{\bf 2}]$ (11) rings

Christopher Glidewell,^a ^* John N. Low,^b Janet M. S. Skakle ^b and James L. Wardell ^c

^aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 23 February 2004; accepted 2 March 2004; online 31 March 2004)

In the title compound, C₉H₉N₂OS⁺·Cl⁻, the cations exhibit amidinium-type delocalization of the positive charge. The ions are linked by one O—H⋯Cl hydrogen bond and two N—H⋯Cl hydrogen bonds into chains of edge-fused [R_4^2] (11) rings. The chains are linked into sheets by a π–π stacking interaction.

Comment

Masaki et al. (1966 ) reported the preparation of 3-hydroxy-4-phenyl-2(3H)-thiazolimine, from the condensation reaction of the oxime of bromomethyl phenyl ketone, BrCH₂C(Ph)=NOH, with barium thiocyanate, and these authors characterized the heterocycle as the picrate salt. The mass spectrum of the title compound, the hydrochloride salt (I), was reported by Entenmann (1975 ) as exhibiting a significant peak assigned to [M − 16]⁺, corresponding to the loss of an O atom, which suggested that the O atom was not protonated. In solution, the picrate salt was reported to give a positive phenol test with iron(III) chloride. However, in neither report was the constitution of the cation definitively established; in particular, neither report gave any indication of the solid-state structure, and hence the determination now reported was undertaken.

Compound (I) consists of an ion pair containing a short O—H⋯Cl hydrogen bond (Fig. 1, and Tables 1 and 2). In the cation, the heterocyclic ring is planar, as expected, and the dihedral angle between this plane and the plane of the benzene ring is 41.9 (2)°. There are considerable differences between the corresponding pairs of exocyclic angles at atoms C2, N3 and C4. The very small interbond angle at atom S1 is also notable. The C2—N2 and C2—N3 bonds are similar in length and both are significantly shorter than the N3—C4 bond. The bond orders, calculated using the recent recalibration by Kotelevskii & Prezhdo (2001 ) of the original equation relating bond order to bond length (Gordy, 1947 ), for the C2—N2, C2—N3 and C3—N4 bonds are 1.77, 1.72 and 1.33, respectively, suggesting amidinium-type delocalization of the positive charge between atoms N2 and N3, as indicated in the scheme below.

The amine group acts as a double donor in N—H⋯Cl hydrogen bonds involving two different anions (Table 2). In the shorter and more nearly linear of these two interactions, amine atom N2 acts as a hydrogen-bond donor, via atom H2A, to atom Cl1 at (x, y − 1, z), so generating by translation a C₂¹(7) chain (Bernstein et al., 1995 ) running parallel to the [010] direction (Fig. 2). Four chains of this type pass through each unit cell and these chains are linked into pairs by the second N—H⋯Cl hydrogen bond. In this interaction, atom N2 acts as a hydrogen-bond donor, this time via atom H2B, to atom Cl1 at ( $[{1 \over 2}]$ − x, y − $[1\over 2]$ , $[{1 \over 2}]$ − z), so forming a C₂¹(4) chain generated by the 2₁ screw axis along ( $[1\over 4]$ , y, $[1\over 4]$ ) (Fig. 2). The combination of the C₂¹(4) and C₂¹(7) motifs then produces a chain of edge-fused [R_4^2] (11) rings. This chain of rings, containing the 2₁ axis along ( $[1\over 4]$ , y, $[1\over 4]$ ), lies within the domain 0 < x < $[1\over 2]$ , and a second chain, related to the first by inversion and containing the 2₁ axis along ( $[3\over 4]$ , y, $[3\over 4]$ ), lies in the domain $[{1 \over 2}]$ < x < 1.

The only direction-specific interaction between adjacent chains of rings is a weak π–π stacking interaction between the heterocyclic rings of the cations related by a centre of symmetry. These rings are parallel, with an interplanar spacing of 3.631 (2) Å. The ring-centroid separation is 3.778 (2) Å, corresponding to a centroid offset of 1.044 (2) Å. These cations at (x, y, z) and (1 − x, 1 − y, 1 − z) lie, respectively, in the chains of rings along ( $[1\over 4]$ , y, $[1\over 4]$ ) and ( $[3\over 4]$ , −y, $[3\over 4]$ ), so that propagation of this stacking interaction links the chain into a (10 $[\overline 1]$ ) sheet. However, there are no π–π stacking interactions involving the phenyl ring, nor are there any C—H⋯π(arene) hydrogen bonds.

As well as acting as a threefold acceptor of hydrogen bonds, the anion at (x, y, z) also forms a short contact with the S atom of the molecule at (1 − x, 1 − y, 1 − z). This S⋯Cl distance is 3.3275 (7) Å, somewhat less than the sum of the van der Waals radii (3.50 Å; Bondi, 1964 ). The overall coordination polyhedron at atom Cl1, including the secondary bond (Alcock, 1972 ) involving the S atom, takes the form of a distorted trigonal bipyramid of VSEPR (valence-shell electron-pair repulsion) type MX₄E (Gillespie, 1972 ; Gillespie & Hargittai, 1991 ; Burdett, 1997 ), where X represents a bonding pair of electrons at the central atom M (here M = Cl) and E represents the equatorial lone pair of non-bonding electrons (Fig. 3). The angles at atom Cl1 are as follows: O3⋯Cl1⋯N2* = 110.79 (5)°, O3⋯Cl1⋯N2# = 78.64 (5)°, O3⋯Cl1⋯S1$ = 91.92 (3)°, N2*⋯Cl1⋯N2# = 92.69 (5)°, N2*⋯Cl1⋯S1$ = 109.99 (4)° and N2#⋯Cl1⋯S1$ = 157.30 (4)°, where atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (x, y + 1, z), ( $[{1 \over 2}]$ − x, $[{1 \over 2}]$ + y, $[{1 \over 2}]$ − z) and (1 − x, 1 − y, 1 − z), respectively.

Figure 1
The independent ions in (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of (I

), showing the formation of a chain of edge-fused [R_4^2]

(11) rings along the b axis. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (x, y − 1, z), ( $[{1 \over 2}]$ − x, y − $[{1 \over 2}]$ , $[{1 \over 2}]$ − z), (x, y + 1, z) and ( $[{1 \over 2}]$ − x, $[{1 \over 2}]$ + y, $[{1 \over 2}]$ − z), respectively.

Figure 3
Part of the crystal structure of (I

), showing the coordination at the anion. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign ($) are at the symmetry positions (x, y + 1, z), ( $[{1 \over 2}]$ − x, $[{1 \over 2}]$ + y, $[{1 \over 2}]$ − z) and (1 − x, 1 − y, 1 − z), respectively.

Experimental

The neutral heterocycle 3-hydroxy-2-imino-4-phenylthiazole was prepared according to the method reported by Masaki et al. (1966). The hydrochloride salt, (I), was prepared by treating the neutral heterocycle in ethanol solution with aqueous HCl (6 mol dm⁻³) and was recrystallized from ethanol. Compound (I) slowly darkened on heating and decomposed before melting.

Crystal data

C₉H₉N₂OS⁺·Cl⁻
M_r = 228.69
Monoclinic, P2₁/n
a = 9.2663 (5) Å
b = 7.0716 (4) Å
c = 15.461 (1) Å
β = 90.194 (2)°
V = 1013.12 (10) Å³
Z = 4
D_x = 1.499 Mg m⁻³
Mo Kα radiation
Cell parameters from 2247 reflections
θ = 3.2–27.4°
μ = 0.55 mm⁻¹
T = 120 (2) K
Plate, colourless
0.32 × 0.24 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995 , 1997 ) T_min = 0.827, T_max = 0.934
9736 measured reflections
2247 independent reflections
1751 reflections with I > 2σ(I)
R_int = 0.067
θ_max = 27.4°
h = −11 → 11
k = −8 → 9
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 1.04
2247 reflections
128 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0703P)² + 0.159P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S1—C2	1.718 (2)
C2—N3	1.330 (3)
N3—C4	1.405 (3)
C4—C5	1.341 (3)
C5—S1	1.737 (2)
C2—N2	1.321 (3)
N3—O3	1.377 (2)
C4—C41	1.476 (3)

S1—C2—N3	110.64 (15)
C2—N3—C4	116.04 (18)
N3—C4—C5	110.03 (19)
C4—C5—S1	113.00 (17)
C5—S1—C2	90.29 (11)
S1—C2—N2	125.72 (17)
N2—C2—N3	123.58 (19)
C2—N3—O3	119.73 (17)
O3—N3—C4	124.22 (17)
N3—C4—C41	121.81 (19)
C5—C4—C41	128.2 (2)

N3—C4—C41—C42	−139.2 (2)
C5—C4—C41—C42	40.7 (3)
N3—C4—C41—C46	43.1 (3)
C5—C4—C41—C46	−136.9 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯Cl1	0.84	2.11	2.929 (2)	167
N2—H2A⋯Cl1ⁱ	0.88	2.30	3.131 (2)	157
N2—H2B⋯Cl1ⁱⁱ	0.88	2.46	3.217 (2)	145
Symmetry codes: (i) x,y-1,z; (ii) $[{1\over 2}-x,y-{1\over 2},{1\over 2}-z]$ .

All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 Å, N—H distances of 0.88 Å and an O—H distance of 0.84 Å.

Data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270104004780/ob1172sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104004780/ob1172Isup2.fcf

Comment top

Masaki et al. (1966) reported the preparation of 3-hydroxy-4-phenyl-2(3H)-thiazolimine, from the condensation reaction of the oxime of bromomethyl phenyl ketone, BrCH₂C(Ph)=NOH, with barium thiocyanate, and characterized the heterocycle as the picrate salt. The mass spectrum of the title compound, the hydrochloride salt (I), was reported by Entenmann (1975) as exhibiting a significant peak assigned to [M-16]⁺, corresponding to loss of an O atom, which suggested that the O atom was not protonated. In solution, the picrate salt was reported to give a positive phenol test with iron(III) chloride. However, in neither report was the constitution of the cation definitively established; in particular, neither report gave any indication of the solid-state structure, and hence the determination now reported was undertaken.

Compound (I) consists of an ion pair containing a short O—H···Cl hydrogen bond (Fig. 1, and Tables 1 and 2). In the cation, the heterocyclic ring is planar, as expected, and the dihedral angle between this plane and the Ph ring is 41.9 (2)°. There is considerable variation within the corresponding pairs of exocyclic angles at atoms C2, N3 and C4. The very small interbond angle at atom S1 is also notable. The C2—N2 and C2—N3 bonds are similar in length and both are significantly shorter than the N3—C4 bond. The bond orders, calculated using the recent recalibration by Kotelevskii & Prezhdo (2001) of the original equation relating bond order to bond length (Gordy, 1947), for the C2—N2, C2—N3 and C3—N4 bonds are 1.77, 1.72 and 1.33, respectively, suggesting amidinium-type delocalization of the positive charge between atoms N2 and N3, as indicated in the scheme.

The amine group acts as a double donor in N—H···Cl hydrogen bonds involving two different anions (Table 2). In the shorter and more nearly linear of these two interactions, amine atom N2 acts as a hydrogen-bond donor, via atom H2A, to atom Cl at (x, y − 1, z), so generating by translation a C¹₂(7) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 2). Four chains of this type pass through each unit cell and they are linked into pairs by the second N—H···Cl hydrogen bond. In this interaction, atom N2 acts as a hydrogen-bond donor, this type via atom H2B, to atom Cl at (1/2 − x, y − 1/2, 1/2 − z), so forming a C¹₂(4) chain generated by the 2₁ screw axis along (1/4, y, 1/4) (Fig. 2). The combination of the C¹₂(4) and C¹₂(7) motifs then produces a chain of edge-fused R²₄(11) rings. This chain of rings, containing the 2₁ axis along (1/4, y, 1/4), lies within the domain 0 < x < 1/2, and a second chain, related to the first by inversion and containing the 2₁ axis along (3/4, y, 3/4), lies in the domain 1/2 < x < 1.

The only direction-specific interaction between adjacent chains of rings is a weak π···π stacking interaction between the heterocyclic rings of the cations related by a center of symmetry. These rings are parallel, with an interplanar spacing of 3.631 (2) Å. The ring-centroid separation is 3.778 (2) Å, corresponding to a centroid offset of 1.044 (2) Å. These cations at (x, y, z) and (1 − x, 1 − y, 1 − z) lie, respectively, in the chains of rings along (1/4, y, 1/4) and (3/4, −y, 3/4), so that propagation of this stacking interaction links the chain into a (10–1) sheet. However, there are no π···π stacking interactions involving the phenyl ring, nor are there any C—H···π(arene) hydrogen bonds.

As well as acting as a threefold acceptor of hydrogen bonds, the anion at (x, y, z) also forms a short contact with the S atom of the molecule at (1 − x, 1 − y, 1 − z). This S···Cl distance is 3.3275 (7) Å, somewhat below the sum of the van der Waals radii (3.50 Å; Bondi, 1964). The overall coordination polyhedron at atom Cl, including the secondary bond (Alcock, 1972) involving the S atom, takes the form of a distorted trigonal bipyramid of VSEPR (Gillespie, 1972; Gillespie & Hargittai, 1991; Burdett, 1997) type MX₄E, where X represents a bonding pair of electrons at the central atom, M (here M = Cl), and E represents the equatorial lone pair of non-bonding electrons (Fig. 3). The angles at atom Cl1 are as follows: O3···Cl1···N2^* = 110.79 (5)°, O3···Cl1···N2^# = 78.64 (5)°, O3···Cl1···S1^? = 91.92 (3)°, N2^*···Cl1···N2^# = 92.69 (5)°, N2^*···Cl1···Si^? = 109.99 (4)° and N2^#···Cl1···S1^? = 157.30 (4)°, where atoms marked with an asterisk (*), a hash (#) or a dollar sign () are at the symmetry positions (x, y + 1, z), (1/2 − x, 1/2 + y, 1/2 − z) and $ = (1 − x, 1 − y, 1 − z), resepctively.

Experimental top

The neutral heterocycle 2-imino-3-hydroxy-4-phenylthiazole was prepared according to the method reported by Masaki et al. (1966). The hydrochloride salt, (I), was prepared by treating the neutral heterocycle in ethanol solution with 6 mol dm⁻³ aqueous HCl, and (I) was recrystallized from ethanol. Compound (I) slowly darkened on heating and decomposed before melting.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The independent ions in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a chain of edge-fused R²₄(11) rings along the b axis. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign () or an ampersand (&) are at the symmetry positions (x, y − 1, z), (1/2 − x, y − 1/2, 1/2 − z), (x, y + 1, z) and (1/2 − x, 1/2 + y, 1/2 − z), respectively.
	Fig. 3. Part of the crystal structure of (I), showing the coordination at the anion. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or a dollar sign () are at the symmetry positions (x, y + 1, z), (1/2 − x, 1/2 + y, 1/2 − z) and (1 − x, 1 − y, 1 − z), respectively.

2-Amino-3-hydroxy-4-phenylthiazolium chloride top

Crystal data top

C₉H₉N₂OS⁺·Cl⁻	F(000) = 472
M_r = 228.69	D_x = 1.499 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2247 reflections
a = 9.2663 (5) Å	θ = 3.2–27.4°
b = 7.0716 (4) Å	µ = 0.55 mm⁻¹
c = 15.461 (1) Å	T = 120 K
β = 90.194 (2)°	Plate, colourless
V = 1013.12 (10) Å³	0.32 × 0.24 × 0.12 mm
Z = 4

Data collection top

KappaCCD diffractometer	2247 independent reflections
Radiation source: rotating anode	1751 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ϕ scans, and ω scans with κ offsets	θ_max = 27.4°, θ_min = 3.2°
Absorption correction: multi-scan (SORTAV; Blessing 1995, 1997)	h = −11→11
T_min = 0.827, T_max = 0.934	k = −8→9
9736 measured reflections	l = −19→19

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0703P)² + 0.159P] where P = (F_o² + 2F_c²)/3
2247 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₉H₉N₂OS⁺·Cl⁻	V = 1013.12 (10) Å³
M_r = 228.69	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.2663 (5) Å	µ = 0.55 mm⁻¹
b = 7.0716 (4) Å	T = 120 K
c = 15.461 (1) Å	0.32 × 0.24 × 0.12 mm
β = 90.194 (2)°

Data collection top

KappaCCD diffractometer	2247 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing 1995, 1997)	1751 reflections with I > 2σ(I)
T_min = 0.827, T_max = 0.934	R_int = 0.067
9736 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	Δρ_max = 0.53 e Å⁻³
2247 reflections	Δρ_min = −0.41 e Å⁻³
128 parameters

Special details top

Refinement. The space group P2₁/n was uniquely assigned from the systematic absences.

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

	x	y	z	U_iso*/U_eq
S1	0.38910 (6)	0.22878 (8)	0.50432 (3)	0.02526 (19)
C2	0.3016 (2)	0.3484 (3)	0.42286 (13)	0.0216 (5)
N2	0.2959 (2)	0.2964 (3)	0.34083 (12)	0.0264 (4)
N3	0.24406 (19)	0.5079 (2)	0.45261 (11)	0.0217 (4)
O3	0.16664 (16)	0.6230 (2)	0.39757 (9)	0.0265 (4)
C4	0.2658 (2)	0.5452 (3)	0.54098 (13)	0.0229 (5)
C5	0.3437 (2)	0.4061 (3)	0.57711 (14)	0.0256 (5)
C41	0.2075 (2)	0.7165 (3)	0.58266 (14)	0.0221 (5)
C42	0.2927 (2)	0.8124 (3)	0.64260 (13)	0.0251 (5)
C43	0.2390 (2)	0.9687 (3)	0.68564 (14)	0.0274 (5)
C44	0.1001 (2)	1.0312 (3)	0.66872 (14)	0.0301 (6)
C45	0.0152 (3)	0.9379 (3)	0.60891 (15)	0.0307 (5)
C46	0.0680 (3)	0.7809 (3)	0.56603 (15)	0.0272 (5)
Cl1	0.39250 (6)	0.87277 (8)	0.33083 (3)	0.02775 (19)
H2A	0.3358	0.1893	0.3245	0.032*
H2B	0.2523	0.3689	0.3026	0.032*
H3	0.2207	0.7086	0.3785	0.040*
H5	0.3713	0.4046	0.6363	0.031*
H42	0.3882	0.7703	0.6540	0.030*
H43	0.2974	1.0331	0.7268	0.033*
H44	0.0632	1.1385	0.6983	0.036*
H45	−0.0798	0.9815	0.5972	0.037*
H46	0.0090	0.7169	0.5251	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0326 (3)	0.0234 (3)	0.0197 (3)	0.0063 (2)	−0.0034 (2)	0.0027 (2)
C2	0.0218 (11)	0.0206 (11)	0.0225 (11)	−0.0007 (9)	−0.0049 (8)	0.0026 (9)
N2	0.0360 (11)	0.0237 (10)	0.0195 (9)	0.0058 (9)	−0.0073 (8)	0.0002 (8)
N3	0.0254 (9)	0.0196 (10)	0.0201 (9)	0.0030 (8)	−0.0068 (7)	0.0033 (7)
O3	0.0310 (9)	0.0235 (9)	0.0247 (8)	0.0042 (7)	−0.0097 (7)	0.0051 (6)
C4	0.0243 (11)	0.0245 (12)	0.0199 (10)	−0.0007 (9)	−0.0013 (8)	0.0022 (9)
C5	0.0303 (12)	0.0262 (12)	0.0204 (11)	0.0038 (10)	−0.0012 (9)	0.0004 (9)
C41	0.0260 (11)	0.0199 (11)	0.0203 (10)	−0.0001 (9)	−0.0009 (8)	0.0022 (8)
C42	0.0273 (11)	0.0282 (12)	0.0196 (11)	0.0009 (10)	−0.0017 (9)	0.0041 (9)
C43	0.0336 (13)	0.0292 (13)	0.0196 (11)	−0.0032 (10)	−0.0022 (9)	−0.0013 (9)
C44	0.0398 (14)	0.0238 (13)	0.0267 (12)	0.0028 (10)	0.0052 (10)	−0.0012 (9)
C45	0.0296 (12)	0.0283 (13)	0.0342 (13)	0.0059 (11)	0.0001 (10)	0.0008 (10)
C46	0.0271 (12)	0.0257 (13)	0.0289 (12)	−0.0014 (10)	−0.0037 (10)	−0.0006 (10)
Cl1	0.0331 (3)	0.0245 (3)	0.0255 (3)	0.0016 (2)	−0.0097 (2)	0.0011 (2)

Geometric parameters (Å, º) top

S1—C2	1.718 (2)	C41—C42	1.392 (3)
C2—N3	1.330 (3)	C41—C46	1.393 (3)
N3—C4	1.405 (3)	C42—C43	1.383 (3)
C4—C5	1.341 (3)	C42—H42	0.95
C5—S1	1.737 (2)	C43—C44	1.385 (3)
C2—N2	1.321 (3)	C43—H43	0.95
N3—O3	1.377 (2)	C44—C45	1.380 (3)
C4—C41	1.476 (3)	C44—H44	0.95
N2—H2A	0.88	C45—C46	1.383 (3)
N2—H2B	0.88	C45—H45	0.95
O3—H3	0.84	C46—H46	0.95
C5—H5	0.95

S1—C2—N3	110.64 (15)	C42—C41—C4	118.9 (2)
C2—N3—C4	116.04 (18)	C46—C41—C4	121.9 (2)
N3—C4—C5	110.03 (19)	C43—C42—C41	120.4 (2)
C4—C5—S1	113.00 (17)	C43—C42—H42	119.8
C5—S1—C2	90.29 (11)	C41—C42—H42	119.8
S1—C2—N2	125.72 (17)	C42—C43—C44	120.0 (2)
N2—C2—N3	123.58 (19)	C42—C43—H43	120.0
C2—N3—O3	119.73 (17)	C44—C43—H43	120.0
O3—N3—C4	124.22 (17)	C45—C44—C43	120.1 (2)
N3—C4—C41	121.81 (19)	C45—C44—H44	120.0
C5—C4—C41	128.2 (2)	C43—C44—H44	120.0
C2—N2—H2A	120.0	C44—C45—C46	120.2 (2)
C2—N2—H2B	120.0	C44—C45—H45	119.9
H2A—N2—H2B	120.0	C46—C45—H45	119.9
N3—O3—H3	109.5	C45—C46—C41	120.2 (2)
C4—C5—H5	123.5	C45—C46—H46	119.9
S1—C5—H5	123.5	C41—C46—H46	119.9
C42—C41—C46	119.2 (2)

C5—S1—C2—N2	176.8 (2)	N3—C4—C41—C42	−139.2 (2)
C5—S1—C2—N3	−0.42 (16)	C5—C4—C41—C42	40.7 (3)
N2—C2—N3—O3	3.9 (3)	N3—C4—C41—C46	43.1 (3)
S1—C2—N3—O3	−178.81 (14)	C5—C4—C41—C46	−136.9 (2)
N2—C2—N3—C4	−177.18 (19)	C46—C41—C42—C43	0.6 (3)
S1—C2—N3—C4	0.2 (2)	C4—C41—C42—C43	−177.19 (19)
C2—N3—C4—C5	0.3 (3)	C41—C42—C43—C44	−0.4 (3)
O3—N3—C4—C5	179.21 (18)	C42—C43—C44—C45	0.0 (3)
C2—N3—C4—C41	−179.73 (19)	C43—C44—C45—C46	0.4 (4)
O3—N3—C4—C41	−0.8 (3)	C44—C45—C46—C41	−0.2 (3)
N3—C4—C5—S1	−0.6 (2)	C42—C41—C46—C45	−0.2 (3)
C41—C4—C5—S1	179.41 (18)	C4—C41—C46—C45	177.46 (19)
C2—S1—C5—C4	0.61 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···Cl1	0.84	2.11	2.929 (2)	167
N2—H2A···Cl1ⁱ	0.88	2.30	3.131 (2)	157
N2—H2B···Cl1ⁱⁱ	0.88	2.46	3.217 (2)	145

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

Experimental details

Crystal data
Chemical formula	C₉H₉N₂OS⁺·Cl⁻
M_r	228.69
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	9.2663 (5), 7.0716 (4), 15.461 (1)
β (°)	90.194 (2)
V (Å³)	1013.12 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.32 × 0.24 × 0.12

Data collection
Diffractometer	KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing 1995, 1997)
T_min, T_max	0.827, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	9736, 2247, 1751
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.119, 1.04
No. of reflections	2247
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.41

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top

S1—C2	1.718 (2)	C5—S1	1.737 (2)
C2—N3	1.330 (3)	C2—N2	1.321 (3)
N3—C4	1.405 (3)	N3—O3	1.377 (2)
C4—C5	1.341 (3)	C4—C41	1.476 (3)

S1—C2—N3	110.64 (15)	N2—C2—N3	123.58 (19)
C2—N3—C4	116.04 (18)	C2—N3—O3	119.73 (17)
N3—C4—C5	110.03 (19)	O3—N3—C4	124.22 (17)
C4—C5—S1	113.00 (17)	N3—C4—C41	121.81 (19)
C5—S1—C2	90.29 (11)	C5—C4—C41	128.2 (2)
S1—C2—N2	125.72 (17)

N3—C4—C41—C42	−139.2 (2)	N3—C4—C41—C46	43.1 (3)
C5—C4—C41—C42	40.7 (3)	C5—C4—C41—C46	−136.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···Cl1	0.84	2.11	2.929 (2)	167
N2—H2A···Cl1ⁱ	0.88	2.30	3.131 (2)	157
N2—H2B···Cl1ⁱⁱ	0.88	2.46	3.217 (2)	145

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

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants that have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

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Volume 60| Part 4| April 2004| Pages o273-o275

doi:10.1107/S0108270104004780

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

2-Amino-3-hy­droxy-4-phenyl­thia­zol­ium chloride: π-stacked hydrogen-bonded chains of edge-fused R(11) rings

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-Amino-3-hydroxy-4-phenylthiazolium chloride: π-stacked hydrogen-bonded chains of edge-fused R $[_{\bf 4}^{\bf 2}]$ (11) rings