Formation of ladders from R44(8) and R66(12) rings in 8-hydroxy­quinolinium chloride monohydrate: comparisons with the supra­molecular arrangements in related salts

Skakle, J.M.S.; Wardell, J.L.; Wardell, S.M.S.V.

doi:10.1107/S0108270106013473

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 6| June 2006| Pages o312-o314

doi:10.1107/S0108270106013473

Formation of ladders from R₄⁴(8) and R₆⁶(12) rings in 8-hydroxyquinolinium chloride monohydrate: comparisons with the supramolecular arrangements in related salts

Janet M. S. Skakle,^a ^* James L. Wardell ^b and Solange M. S. V. Wardell ^c

^aDepartment of Chemistry, College of Physical Sciences, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartamento de Química Inorgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, and ^cFundação Oswaldo Cruz, Instituto de Tecnología en Fármacos, Departamento de Síntese Orgânica, Manguinhos, CEP 21041250 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: j.skakle@abdn.ac.uk

(Received 3 April 2006; accepted 13 April 2006; online 16 May 2006)

Molecules of the title compound, C₉H₈NO⁺·Cl⁻·H₂O, are linked into two rings by strong hydrogen bonding via the free water molecules and the Cl⁻ anions. The two hydrogen-bonded rings are joined to give a corrugated chain along [001]. Comparisons with other 8-hydroxyquinoline-based salts are also presented, highlighting similar ring structures in a 1:1 salt with Kemp's triacid (r-1,c-3,c-5-trimethylcyclohexane-1,3,5-tricarboxylic acid) and in 8-hydroxy-1-methylquinolinium chloride monohydrate.

Comment

In a continuation of our interest in the supermolecular arrangements of organic molecules, we now report the crystal structure of hydrated 8-hydroxyquinolinium chloride, 8-HOQH⁺·Cl⁻. The title compound, (I), was isolated from a reaction mixture consisting of 2-chloronicotinoyl chloride and 8-hydroxyquinoline, 8-HOQ, in acetone, followed by recrystallization of the reaction residues from ethanol. Clearly, the water present in the solvent(s) had led to hydrolysis of the acyl chloride with formation of hydrogen chloride, which then formed the salt with 8-hydroxyquinoline.

Compound (I) crystallizes in the space group P $[\overline{1}]$ and, for convenience, the reference positions of the free Cl atoms and water molecules were chosen to give the most direct hydrogen-bonding scheme (Fig. 1 and Table 1). The hydrogen bonding was analysed with the aid of PLATON (Spek, 2003 ).

The 8-HOQ molecule is protonated at the N atom (8-HOQH⁺) and is very nearly planar; the angle between the fused rings is 0.32 (6)° and the Cremer & Pople (1975 ) total puckering amplitude, Q, is 0.0247 (17) Å.

The intramolecular N⁺—H⋯O hydrogen bond in 8-HOQH⁺ has been observed in other 8-hydroxyquinolinium and related cations. In 7-iodo-8-hydroxyquinoline-5-sulfonic acid (Balasubramanian & Muthiah, 1996 ) and in an 8-hydroxyquinolinium salicylate–salicyclic acid complex, 8-HOQH⁺·C₇H₅O₃⁻·C₇H₆O₃ (Jebamony & Thomas Muthiah, 1998 ), this hydrogen bond was observed to result in an enhancement of the internal angle at the nitrogen centre. This interaction has also been highlighted in the crystal structures of 8-hydroxyquinoline-5-sulfonic acid dihydrate (Banerjee et al., 1984 ), 8-hydroxy-7-nitroquinoline-5-sulfonic acid monohydrate (Balasubramanian & Thomas Muthiah, 1996 ) and 8-hydroxyquinolinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, 8-HOQH⁺·C₇H₅O₆S⁻·H₂O (Smith et al., 2004 ).

The solvent water molecules and free chloride ions lead to a number of intra- and intermolecular hydrogen bonds (Table 1). Taking these entities alone first, the water molecule at (x, y, z) participates in O1W—H1WA⋯Cl1 and O1W—H1WB⋯Cl1ⁱⁱ hydrogen bonds [symmetry code: (ii) −x + 1, −y, −z − 1], forming small R₄⁴(8) rings (Bernstein et al., 1995 ). This type of interaction is identical to that observed in 8-hydroxy-1-methylquinolinium chloride monohydrate (Rømming & Uggerud, 1983 ) and the isostructural iodide (Barczyński et al., 2006 ), both of which also crystallize in P $[\overline{1}]$ . In these latter structures, however, the methyl substitution at the N atom hinders further strong hydrogen-bonding interactions, and thus this centrosymmetric R₄⁴(8) dimer is the only motif observed.

In (I), another ring forms from a combination of hydrogen bonds [O1—H1A⋯O1W, O1W—H1WA⋯Cl1, N1—H1⋯Cl1ⁱ and N1—H1⋯O1; symmetry code: (i) −x + 1, −y, −z]. Together, these form an R₆⁶(12) dimeric ring centred at ( $[1\over2]$ , 0, 0) (Fig. 2).

The two rings join to form a polymeric ladder along [001] (Fig. 3a); viewed in the orientation shown in Fig. 3(a), the ladder appears flat, but viewed along the direction of the ladder, it can be seen that the molecules hydrogen bond in a chair-like configuration (Fig. 3b). The interactions forming this ladder are similar to those observed in the structure of 8-HOQH⁺·KTA⁻ (KTA is Kemp's triacid, r-1,c-3,c-5-trimethylcyclohexane-1,3,5-tricarboxylic acid), in which a polymeric chain forms via the carboxylate groups of KTA and the hydroxy and N⁺H groups of 8-HOQH⁺, leading to similar dimeric R₆⁶(12) rings which then form chains via the symmetric KTA molecule (Smith et al., 2000 ). The presence of the intramolecular N⁺—H⋯O hydrogen bond in 8-HOQH⁺ was not shown in the cited work, but the effect of this intramolecular bond is to provide a `short-cut' in the ring by providing an extra hydrogen bond, shortening the ring from R⁴₄(18) to R⁶₆(12).

There is also similarity with 8-HOQH⁺·C₇H₅O₆S⁻·H₂O (Smith et al., 2004), in that the hydroxy group of the 8-HOQH⁺ ion acts as a donor to the free water molecule. In this case, the water molecule then goes on to act as a donor to O atoms from the sulfonate group, as does the carboxylate group, forming a three-dimensional network.

The hydrogen-bonding scheme in 8-HOQH⁺ salicylate–salicyclic acid, 8-HOQH⁺·C₇H₅O₃⁻·C₇H₆O₃, was described in terms of the interactions present but not in terms of the symmetry of these interactions (Jebamony & Thomas Muthiah, 1998). Two of the hydrogen bonds described are between molecules in the same asymmetric unit and do not lead to any continuity of the structure. The other three intermolecular interactions described occur between molecules at (x, y, z) and (−x + 1, −y + 1, −z + 1), forming an isolated dimer. Thus, no chain or network structure is formed in this compound.

The crystal structure of 8-HOQ 2,4,5-trichlorophenol (Singh et al., 2001 ) shows an interesting phenomenon. The asymmetric unit consists of two molecules of 2,4,5-trichlorophenol and two of 8-HOQ. In one of these latter molecules, the H atom is located at the hetero-N atom, whereas in the other it is at the hydroxy group; thus, neither molecule is protonated as in the present study. The intramolecular N—H⋯O bond in the 8-HOQ molecule is still observed; hydrogen-bonded chains are supported by a number of intramolecular hydrogen bonds involving both forms of the 8-HOQ molecule, with the unprotonated N and O atoms acting as acceptors.

Figure 1
The molecule of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as circles of arbitrary radii and hydrogen bonds are shown as broken lines.

Figure 2
Part of the crystal structure of the title compound, showing the formation of an R₆⁶(12) ring. Displacement ellipsoids are shown at the 50% probability level, H atoms are shown as circles of arbitrary radii and dashed lines indicate hydrogen bonds. [Symmetry code: (i) −x + 1, −y, −z.]

Figure 3
Part of the crystal structure of the title compound, showing (a) the formation of `ladders' and (b) the relative conformation of the molecules in the `ladder' formed from the two hydrogen-bonded rings. Displacement ellipsoids are shown at the 50% probability level, H atoms are shown as circles of arbitrary radii and dashed lines indicate hydrogen bonds. [Symmetry code: (ii) −x + 1, −y, −z − 1.]

Experimental

A solution of equimolar (2.0 mmol) 2-chloronicotinoyl chloride and 8-hydroxyquinoline in acetone (30 ml) was refluxed for 20 min; all volatiles were removed under vacuum and the residue was taken up in EtOH. Crystals of the title compound were deposited slowly. IR: 3500–2200 (KBr, with spike at 3327), 1631, 1602, 1552, 1500, 1472, 1398, 1300, 1268, 1220, 1205, 1098, 1059, 999, 661, 821, 756, 711, 523, 578, 540, 488, 412 cm⁻¹.

Crystal data

C₉H₈NO⁺·Cl⁻·H₂O
M_r = 199.63
Triclinic, $[P \overline 1]$
a = 7.2865 (3) Å
b = 8.2885 (4) Å
c = 8.4596 (3) Å
α = 78.328 (2)°
β = 86.105 (2)°
γ = 66.388 (2)°
V = 458.41 (3) Å³
Z = 2
D_x = 1.446 Mg m⁻³
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 120 (2) K
Shard, light orange
0.36 × 0.20 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.802, T_max = 0.928
9570 measured reflections
2098 independent reflections
1835 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.14
2098 reflections
131 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0351P)² + 0.18P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O1W	0.84	1.80	2.6329 (15)	174
N1—H1⋯O1	0.89 (2)	2.35 (2)	2.7050 (16)	103.7 (15)
N1—H1⋯Cl1ⁱ	0.89 (2)	2.37 (2)	3.1048 (13)	140.2 (17)
O1W—H1WA⋯Cl1ⁱⁱ	0.82 (2)	2.30 (3)	3.1245 (13)	176 (2)
O1W—H1WB⋯Cl1	0.79 (2)	2.36 (3)	3.1550 (14)	175 (2)
Symmetry codes: (i) -x+1, -y, -z; (ii) -x+1, -y, -z-1.

The space groups P1 and P $[\overline{1}]$ were possible; P $[\overline{1}]$ was selected and confirmed by the structure analysis. All H atoms were located from difference maps, and the parameters of water and NH H atoms were refined freely. All other H atoms were treated as riding, with C—H distances of 0.95 Å, O—H distances of 0.84 Å and U_iso(H) values of 1.2U_eq(C) or 1.5U_eq(O).

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; 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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106013473/sk3016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106013473/sk3016Isup2.hkl

Comment top

In a continuation of our interests in the supermolecular arrangements of organic molecules, we now report the crystal structure of hydrated 8-hydroxyquinolinium chloride, 8-HOQH⁺·Cl⁻. The title compound, (I), was isolated from a reaction mixture consisting of 2-chloronicotinoyl chloride and 8-hydroxyquinoline, 8-HOQ, in acetone, followed by recrystallization of the reaction residues from ethanol. Clearly, the water present in the solvent(s) had led to hydrolysis of the acyl chloride with formation of hydrogen chloride, which then formed the salt with 8-hydroxyquinoline.

Compound (I) crystallizes in space group P1, and for convenience the reference positions of the free Cl atoms and water molecules were chosen to give the most direct hydrogen-bonding scheme (Fig. 1 and Table 1). The hydrogen bonding was analysed with the aid of PLATON (Spek, 2003).

The 8-HOQ molecule is protonated at the N atom (C₉H₈NO⁺) and is very near planar; the angle between the fused rings is 0.32 (6)° and the Cremer & Pople (1975) total puckering amplitude Q is 0.0247 (17) Å.

The intramolecular N⁺—H···O hydrogen bond in 8-HOQH⁺ has been observed in other 8-hydroxyquinolinium and related cations. In 7-iodo-8-hydroxyquinoline-5-sulfonic acid (Balasubramanian & Muthiah, 1996) and in an 8-hydroxyquinolinium salicylate–salicyclic acid complex 8-HOQH⁺·C₇H₅O₃⁻·C₇H₆O₃ (Jebamony & Thomas Muthiah, 1998), this hydrogen bond was observed to result in an enhancement of the internal angle at the N centre. This interaction has also been highlighted in the crystal structures of 8-hydroxyquinoline-5-sulfonic acid dihydrate (Banerjee et al., 1984), 8-hydroxy-7-nitroquinoline-5-sulfonic acid monohydrate (Balasubramanian & Thomas Muthiah, 1996) and 8-hydroxyquinolinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, 8-HOQH⁺·C₇H₅O₆S⁻·H₂O (Smith et al., 2004).

The solvent water and free chloride ions lead to a number of intra- and intermolecular hydrogen bonds (Table 1). Taking these entities alone first, the water molecule at (x, y, z) participates in O1W—H1WA···Cl1 and O1W—H1WB···Cl1ⁱⁱ hydrogen bonds [symmetry code: (ii) −x + 1, −y, −z − 1], forming small R₄⁴(8) rings (Bernstein et al., 1995). This type of interaction is identical to that observed in 8-hydroxy-1-methylquinolonium chloride monohydrate, (Rømming & Uggerud, 1983) and the isostructural iodide (Barczyński et al., 2006), both of which also crystallize in P1. In these latter structures, however, the methyl substitution at the N atom hinders further strong hydrogen-bonding interactions, and thus this centrosymmetric R₄⁴(8) dimer is the only motif observed.

In (I), another ring forms from a combination of hydrogen bonds [O1—H1A···O1W, O1W—H1WA···Cl1, N1—H1···Cl1ⁱ and N1—H1···O1 [symmetry code: (i) −x + 1, −y, −z]. Together, these form an R₆⁶(12) dimeric ring centred at (1/2, 0, 0) (Fig. 2).

The two rings join to form a polymeric ladder along [001] (Fig. 3a); viewed in this orientation, the ladder appears flat, but viewed along the direction of the ladder, it can be seen that the molecules hydrogen bond in a chair-like configuration (Fig. 3b). The interactions forming this ladder are similar to those observed in the structure of 8-HOQH⁺·KTA⁻ (KTA is Kemp's triacid, r-1,c-3,c-5-trimethylcyclohexane-1,3,5-tricarboxylic acid), in which a polymeric chain forms via the carboxylate groups of KTA and the hydroxy and N⁺/H groups of 8-HOQH⁺, leading to similar dimeric R₆⁶(12) rings which then form chains via the symmetric KTA molecule (Smith et al., 2000). The presence of the intramolecular N⁺—H···O hydrogen bond in 8-HOQH⁺ was not shown in the cited work, but shortens the ring slightly (from 18 constituent atoms to 12).

There is also similarity with 8-HOQH⁺·C₇H₅O₆S⁻·H₂O (Smith et al., 2004) in that the hydroxy group of 8-HOQH⁺ acts as a donor to the free water molecule. In this case, the water molecule then goes on to act as a donor to O atoms from the sulfonate group, as does the carboxylate group, forming a three-dimensional network.

The hydrogen-bonding scheme in 8-HOQH⁺ salicylate–salicyclic acid, 8-HOQH⁺·C₇H₅O₃⁻·C₇H₆O₃, was described in terms of the interactions present but not in terms of the symmetry of these interactions (Jebamony & Thomas Muthiah, 1998). Two of the hydrogen bonds described are between molecules in the same asymmetric unit and do not lead to any continuity of the structure. The other three of the intermolecular interactions described occur between molecules at (x, y, z) and at (−x + 1, −y + 1, −z + 1), forming an isolated dimer. Thus no chain or network structure is formed in this compound.

The crystal structure of 8-HOQ 2,4,5-trichlorophenol (Singh et al., 2001) shows an interesting phenomenon. The asymmetric unit consists of two molecules of 2,4,5-trichlorophenol and two of 8-HOQ. In one of these latter molecules, the H atom is located at the hetero-N atom, whereas in the other it is at the hydroxy group; thus neither molecule is protonated as in the present study. The intramolecular N—H···O bond in the 8-HOQ molecule is still observed; hydrogen-bonded chains are supported by a number of intramolecular hydrogen bonds involving both forms of the 8-HOQ molecule, with the unprotonated N and O atoms acting as acceptors.

Experimental top

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; 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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. : The molecule of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as circles of arbitrary radii and hydrogen bonds as broken lines.
	Fig. 2. : Part of the crystal structure of the title compound, showing the formation of an R₆⁶(12) ring. Displacement ellipsoids are shown at the 50% level, H atoms are shown as circles of arbitrary radii and dashed lines indicate hydrogen bonds. [Symmetry code: (i) −x + 1, −y, −z.]
	Fig. 3. : Part of the crystal structure of the title compound, showing (a) the formation of `ladders' and (b) the relative conformation of the molecules in the `ladder' formed from the two hydrogen-bonded rings. Displacement ellipsoids are shown at the 50% level, H atoms are shown as circles of arbitrary radii and dashed lines indicate hydrogen bonds. [Symmetry code: (ii) −x + 1, −y, −z − 1.]

8-hydroxyquinolinium chloride monohydrate top

Crystal data top

C₉H₈NO⁺·Cl⁻·H₂O	Z = 2
M_r = 199.63	F(000) = 208
Triclinic, P1	D_x = 1.446 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2865 (3) Å	Cell parameters from 2046 reflections
b = 8.2885 (4) Å	θ = 2.9–27.5°
c = 8.4596 (3) Å	µ = 0.38 mm⁻¹
α = 78.328 (2)°	T = 120 K
β = 86.105 (2)°	Shard, light orange
γ = 66.388 (2)°	0.36 × 0.20 × 0.14 mm
V = 458.41 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	2098 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1835 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.7°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
T_min = 0.802, T_max = 0.928	l = −10→10
9570 measured 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)] = 0.033	Hydrogen site location: difference Fourier map
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0351P)² + 0.18P] where P = (F_o² + 2F_c²)/3
2098 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₉H₈NO⁺·Cl⁻·H₂O	γ = 66.388 (2)°
M_r = 199.63	V = 458.41 (3) Å³
Triclinic, P1	Z = 2
a = 7.2865 (3) Å	Mo Kα radiation
b = 8.2885 (4) Å	µ = 0.38 mm⁻¹
c = 8.4596 (3) Å	T = 120 K
α = 78.328 (2)°	0.36 × 0.20 × 0.14 mm
β = 86.105 (2)°

Data collection top

Nonius KappaCCD diffractometer	2098 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1835 reflections with I > 2σ(I)
T_min = 0.802, T_max = 0.928	R_int = 0.031
9570 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.32 e Å⁻³
2098 reflections	Δρ_min = −0.28 e Å⁻³
131 parameters

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 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) top

	x	y	z	U_iso*/U_eq
Cl1	0.17820 (5)	0.10183 (5)	−0.36696 (4)	0.02224 (13)
N1	0.82589 (18)	0.25417 (18)	0.16555 (14)	0.0184 (3)
H1	0.833 (3)	0.143 (3)	0.172 (2)	0.039 (6)*
C2	0.8616 (2)	0.3020 (2)	0.29698 (17)	0.0215 (3)
H2	0.8999	0.2165	0.3949	0.026*
C3	0.8431 (2)	0.4769 (2)	0.29222 (18)	0.0234 (3)
H3	0.8704	0.5106	0.3860	0.028*
C4	0.7853 (2)	0.5996 (2)	0.15110 (18)	0.0212 (3)
H4	0.7713	0.7193	0.1475	0.025*
C4A	0.7462 (2)	0.55025 (19)	0.01067 (17)	0.0179 (3)
C5	0.6851 (2)	0.6717 (2)	−0.13813 (18)	0.0223 (3)
H5	0.6664	0.7934	−0.1472	0.027*
C6	0.6533 (2)	0.6117 (2)	−0.26893 (18)	0.0240 (3)
H6	0.6134	0.6932	−0.3690	0.029*
C7	0.6781 (2)	0.4328 (2)	−0.25901 (17)	0.0208 (3)
H7	0.6563	0.3952	−0.3524	0.025*
C8	0.7336 (2)	0.3114 (2)	−0.11544 (17)	0.0178 (3)
O1	0.75513 (17)	0.13843 (14)	−0.09175 (12)	0.0227 (2)
H1A	0.7184	0.1190	−0.1754	0.034*
C8A	0.7695 (2)	0.37084 (19)	0.02019 (16)	0.0163 (3)
O1W	0.6131 (2)	0.09370 (16)	−0.35024 (14)	0.0260 (3)
H1WA	0.674 (3)	0.041 (3)	−0.423 (3)	0.043 (6)*
H1WB	0.505 (4)	0.091 (3)	−0.349 (3)	0.043 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0263 (2)	0.0219 (2)	0.01917 (19)	−0.00936 (15)	−0.00190 (13)	−0.00486 (14)
N1	0.0183 (6)	0.0197 (7)	0.0182 (6)	−0.0084 (5)	−0.0022 (5)	−0.0028 (5)
C2	0.0191 (7)	0.0288 (8)	0.0171 (7)	−0.0101 (6)	−0.0026 (5)	−0.0031 (6)
C3	0.0207 (8)	0.0329 (9)	0.0230 (7)	−0.0136 (7)	0.0007 (6)	−0.0130 (6)
C4	0.0180 (7)	0.0221 (8)	0.0277 (8)	−0.0095 (6)	0.0037 (6)	−0.0113 (6)
C4A	0.0131 (7)	0.0186 (7)	0.0222 (7)	−0.0061 (6)	0.0026 (5)	−0.0055 (6)
C5	0.0202 (7)	0.0170 (7)	0.0273 (8)	−0.0069 (6)	0.0026 (6)	−0.0008 (6)
C6	0.0203 (8)	0.0256 (8)	0.0205 (7)	−0.0068 (7)	0.0008 (6)	0.0030 (6)
C7	0.0186 (7)	0.0272 (8)	0.0165 (7)	−0.0087 (6)	0.0008 (5)	−0.0049 (6)
C8	0.0158 (7)	0.0195 (7)	0.0188 (7)	−0.0070 (6)	0.0018 (5)	−0.0055 (6)
O1	0.0312 (6)	0.0206 (6)	0.0196 (5)	−0.0124 (5)	−0.0035 (4)	−0.0050 (4)
C8A	0.0146 (7)	0.0184 (7)	0.0159 (7)	−0.0068 (6)	0.0005 (5)	−0.0029 (5)
O1W	0.0280 (7)	0.0319 (7)	0.0230 (6)	−0.0135 (5)	0.0003 (5)	−0.0121 (5)

Geometric parameters (Å, º) top

N1—C2	1.3272 (19)	C5—C6	1.369 (2)
N1—C8A	1.3730 (18)	C5—H5	0.9500
N1—H1	0.89 (2)	C6—C7	1.405 (2)
C2—C3	1.394 (2)	C6—H6	0.9500
C2—H2	0.9500	C7—C8	1.377 (2)
C3—C4	1.368 (2)	C7—H7	0.9500
C3—H3	0.9500	C8—O1	1.3525 (18)
C4—C4A	1.412 (2)	C8—C8A	1.414 (2)
C4—H4	0.9500	O1—H1A	0.8400
C4A—C8A	1.413 (2)	O1W—H1WA	0.82 (2)
C4A—C5	1.414 (2)	O1W—H1WB	0.79 (2)

C2—N1—C8A	122.87 (14)	C6—C5—H5	120.4
C2—N1—H1	119.1 (13)	C4A—C5—H5	120.4
C8A—N1—H1	118.0 (13)	C5—C6—C7	121.75 (14)
N1—C2—C3	120.43 (14)	C5—C6—H6	119.1
N1—C2—H2	119.8	C7—C6—H6	119.1
C3—C2—H2	119.8	C8—C7—C6	120.73 (14)
C4—C3—C2	119.31 (14)	C8—C7—H7	119.6
C4—C3—H3	120.3	C6—C7—H7	119.6
C2—C3—H3	120.3	O1—C8—C7	125.40 (13)
C3—C4—C4A	120.72 (14)	O1—C8—C8A	116.44 (12)
C3—C4—H4	119.6	C7—C8—C8A	118.16 (14)
C4A—C4—H4	119.6	C8—O1—H1A	109.5
C4—C4A—C8A	118.13 (13)	N1—C8A—C4A	118.54 (13)
C4—C4A—C5	123.11 (14)	N1—C8A—C8	120.10 (13)
C8A—C4A—C5	118.76 (13)	C4A—C8A—C8	121.36 (13)
C6—C5—C4A	119.23 (14)	H1WA—O1W—H1WB	105 (2)

C8A—N1—C2—C3	−0.1 (2)	C2—N1—C8A—C4A	−0.8 (2)
N1—C2—C3—C4	0.8 (2)	C2—N1—C8A—C8	−179.98 (13)
C2—C3—C4—C4A	−0.6 (2)	C4—C4A—C8A—N1	1.0 (2)
C3—C4—C4A—C8A	−0.3 (2)	C5—C4A—C8A—N1	−179.01 (12)
C3—C4—C4A—C5	179.67 (14)	C4—C4A—C8A—C8	−179.83 (13)
C4—C4A—C5—C6	179.05 (14)	C5—C4A—C8A—C8	0.2 (2)
C8A—C4A—C5—C6	−1.0 (2)	O1—C8—C8A—N1	0.9 (2)
C4A—C5—C6—C7	0.5 (2)	C7—C8—C8A—N1	−179.78 (13)
C5—C6—C7—C8	0.7 (2)	O1—C8—C8A—C4A	−178.25 (12)
C6—C7—C8—O1	177.72 (13)	C7—C8—C8A—C4A	1.0 (2)
C6—C7—C8—C8A	−1.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O1W	0.84	1.80	2.6329 (15)	174
N1—H1···O1	0.89 (2)	2.35 (2)	2.7050 (16)	103.7 (15)
N1—H1···Cl1ⁱ	0.89 (2)	2.37 (2)	3.1048 (13)	140.2 (17)
O1W—H1WA···Cl1ⁱⁱ	0.82 (2)	2.30 (3)	3.1245 (13)	176 (2)
O1W—H1WB···Cl1	0.79 (2)	2.36 (3)	3.1550 (14)	175 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₈NO⁺·Cl⁻·H₂O
M_r	199.63
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	7.2865 (3), 8.2885 (4), 8.4596 (3)
α, β, γ (°)	78.328 (2), 86.105 (2), 66.388 (2)
V (Å³)	458.41 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.36 × 0.20 × 0.14

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.802, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	9570, 2098, 1835
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.14
No. of reflections	2098
No. of parameters	131
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.28

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O1W	0.84	1.80	2.6329 (15)	173.9
N1—H1···O1	0.89 (2)	2.35 (2)	2.7050 (16)	103.7 (15)
N1—H1···Cl1ⁱ	0.89 (2)	2.37 (2)	3.1048 (13)	140.2 (17)
O1W—H1WA···Cl1ⁱⁱ	0.82 (2)	2.30 (3)	3.1245 (13)	176 (2)
O1W—H1WB···Cl1	0.79 (2)	2.36 (3)	3.1550 (14)	175 (2)

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

Acknowledgements

We are indebted to the EPSRC for the use of both the Chemical Database Service at Daresbury, primarily for access to the Cambridge Structural Database (Fletcher et al., 1996 ), and the X-ray service at the University of Southampton for data collection. We thank CNPq, Brazil, for financial support.

References

Balasubramanian, T. & Muthiah, P. T. (1996). Acta Cryst. C52, 2072–2073. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Balasubramanian, T. & Thomas Muthiah, P. (1996). Acta Cryst. C52, 1017–1019. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Banerjee, T., Basak, A. K., Mazumdar, S. K. & Chaudhuri, S. (1984). Acta Cryst. C40, 507–509. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Barczyński, P., Komasa, A., Ratajczak-Sitarz, M., Katrusiak, A. & Brzezinski, B. (2006). J. Mol. Struct. In the press. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746–749. CrossRef CAS Web of Science Google Scholar
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Jebamony, J. R. & Thomas Muthiah, P. (1998). Acta Cryst. C54, 539–540. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. 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
Rømming, C. & Uggerud, E. (1983). Acta Chem. Scand. Ser. B, 37, 791–795. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Singh, N. B., Srivastava, A. & Fröhlich, R. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 838–842. CrossRef Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2000). Chem. Commun. pp. 2349–2350. Web of Science CrossRef Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2004). Acta Cryst. C60, o575–o581. Web of Science CSD CrossRef CAS IUCr Journals 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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Volume 62| Part 6| June 2006| Pages o312-o314

doi:10.1107/S0108270106013473

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