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Both 7-carboxyl­ato-8-hydroxy-2-methyl­quinolinium monohydrate, C11H9NO3·H2O, (I), and 7-carboxy-8-hydroxy-2-methyl­quinolinium chloride monohydrate, C11H10NO3+·Cl·H2O, (II), crystallize in the centrosymmetric P\overline 1 space group. Both compounds display an intramolecular O—H...O hydrogen bond involving the hydroxy group; this hydrogen bond is stronger in (I) due to its zwitterionic character [O...O = 2.4449 (11) Å in (I) and 2.5881 (12) Å in (II)]. In both crystal structures, the HN+ group participates in the stabilization of the structure via intermolecular hydrogen bonds with water mol­ecules [N...O = 2.7450 (12) Å in (I) and 2.8025 (14) Å in (II)]. In compound (II), a hydrogen-bond network connects the Cl anion to the carboxylic acid group [Cl...O = 2.9641 (11) Å] and to two water mol­ecules [Cl...O = 3.1485 (10) and 3.2744 (10) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104031403/dn1072sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104031403/dn1072Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104031403/dn1072IIsup3.hkl
Contains datablock II

CCDC references: 268111; 268112

Comment top

8-Hydroxy-2-methylquinoline-7-carboxylic acid, (1), is used as a starting subunit in the syntheses of polyhydroxylated styrylquinoline derivatives, (2), which are potent HIV-1 integrase inhibitors that block the replication of HIV-1 in cell culture at non-toxic concentrations (Mekouar et al., 1998). Zouhiri et al. (2000) have shown that, in vitro, the binding interactions between (2) and the HIV-1 integrase catalytic metallic sites (Mg2+, Mn2+) essentially involve the carboxy group. Therefore, the crystallization of (1) and its metallic complexes are of particular interest in order to investigate the interaction potency of such molecules. Compound (1) crystallizes from a mixture of water and acetic acid by slow evaporation at room temperature, giving rise to compound (I). Preliminary attempts to obtain a manganese complex of (1) by exchange with manganese chloride in the solid state failed and yielded 7-carboxy-8-hydroxy-2-methylquinolinium chloride monohydrate, (II). In the present study, we report the crystal structures at 100 K of compounds (I) and (II). \sch

Compound (1) crystallizes in the P1 space group with either one water molecule, giving (I), or one Cl anion and one water molecule in the asymmetric unit, giving (II) (Fig. 1).

In compound (I), the carboxylate group is ionized giving a zwitterionic character in the solid state. This was also observed for the unsolvated 8-hydoxyquinaldic acid molecule reported by Okabe & Muranishi (2002). However, in (II), the carboxy group is stabilized by an O—H···Cl hydrogen bond, with a donor–acceptor O1···Cl distance of 2.9641 (11) Å.

In both compounds, the quinoline N atom is protonated. Protonation of the N atom of (1) is characterized by the C2—N—C9 angle, which has values of 123.14 (8)° in (I) and 123.14 (10)° in (II), respectively. This is in agreement with the angles obtained, for instance, for quinolinium-4-carboxylate [122.7 (2)°; Dobson & Gerkin, 1999] or for 8-hydroxyquinolinium-2-carboxylate [123.2 (3)°; Okabe & Muranishi, 2002]. Conversely, unprotonated quinoline core molecules exhibit smaller angle values: 118.9 (2)° for 2-phenylquinoline-4-carboxylic acid (Blackburn et al., 1996) and 119.3 (1)° for quinoline-4-carboxylic (Dobson & Gerkin, 1998). These typical C—N—C angles were recently reported in the structure study of quinoline-2-carboxylic/quinolinium-2-carboxylate where both tautomeric forms co-crystallize (Dobrzynska & Jerzykiewicz, 2004).

Tables 2 and 4 give the hydrogen-bonding geometry for (I) and (II), respectively. The hydroxy and carboxy groups are linked by an O—H···O intramolecular hydrogen bond involving atom H31 (Fig. 1). However, there is a significant difference in the donor–acceptor distances [O3···O2 = 2.4449 (11) Å in (I) and O3···O2 = 2.5881 (12) Å in (II)] relating to the zwitterionic character of (I). In this compound, the hydrogen bond is actually a Resonance Assisted Hydrogen Bond (RAHB), leading to an intramolecular ring formed by atoms H31, O3, C8, C7, C12 and O2 (Fig. 1). As predicted from theoretical quantum calculations by Wojtulewski & Grabowski (2003), a significant change in the molecular geometry is expected since RAHBs belong to the strongest hydrogen-bonded systems: a short donor–acceptor O···O distance is combined with an equaliαtion of the C—O and CO bond lengths. This is not the case for compound (II), which exhibits a rather longer O2···O3 distance [2.5881 (12) Å]. Moreover, significant differences in the C—O and CO bond lengths are found between (I) [C8—O3 = 1.3328 (11) Å and C12—O2 = 1.2951 (12) Å] and (II) [C8—O3 = 1.3401 (13) Å and C12—O2 = 1.2280 (14) Å].

The crystal structures of the title compounds are stabilized by intermolecular N—H···O hydrogen bonds [N···Ow = 2.7450 (12) Å in (I) and N···Ow = 2.8025 (14) Å in (II)] involving the NH+ group and the water molecules. Carboxylate atoms O1 and O2 in (I) also participate in intermolecular hydrogen bonds with water molecules (Table 2). In compound (II), the Cl anion is engaged in three hydrogen bonds with O1 [Cl···O1 = 2.9641 (11) Å] and two water molecules [Cl···Ow = 3.1485 (10) and 3.2744 (10) Å] (Table 4). The differences in the interactions between molecules in the crystal lattices of (I) and (II) can also explain the slight distortion of the carboxyl groups with respect to the planar quinoline moiety, characterized by the C8—C7—C12—O2 torsion angles [−3.9 (1)° in (I) and −0.5 (2)° in (II)].

Fig. 2 shows how the molecules stack along the crystallographic a axis, with layers parallel to the bc plane. For both compounds, the distance between layers is 3.6 Å. The water molecules and Cl anions occupy the empty space and constitute a three-dimensional hydrogen-bond network connecting the quinoline rings. Due to the centers of inversion, the molecules have a head-to-tail arrangement. However, the two facing quinoline moieties are longitudinally shifted with respect to each other in both (I) and (II) because of the pπ–pπ electronic repulsion (Fig. 2).

Experimental top

Acid (1) was synthesized using the Kolbe reaction, as described by Meek & Fuchsman (1969) and by Polanski et al. (2002). Crystals of (I) were obtained by slow evaporation of a solution in water-acetic acid (1:4 v/v) at room temperature. Crystals of (II) were obtained by slow evaporation of a methanol solution with the addition of MnCl2·4H2O at room temperature. Both crystal samples are very unstable in air and were mounted in glass capillaries before the data collection, which was carried out at 100 K.

Refinement top

For both compounds, all H atoms were found from difference Fourier maps and refined with an isotropic displacement parameter.

Computing details top

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structures of (I) and (II), shown with 50% probability displacement ellipsoids for non-H atoms. Double dashed and dotted lines indicate intramolecular and intermolecular hydrogen bonds, respectively.
[Figure 2] Fig. 2. Packing diagrams for (I) and (II). Left column (view down a) and right column (view down c). H atoms have been omitted for clarity. Dashed lines indicate the intermolecular donor–acceptor networks.
(I) 8-Hydroxy-2-methylquinoline-7-carboxylic acid monohydrate top
Crystal data top
C11H9NO3·H2OZ = 2
Mr = 221.21F(000) = 232
Triclinic, P1Dx = 1.542 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6556 (7) ÅCell parameters from 2110 reflections
b = 7.8062 (8) Åθ = 2.2–30.1°
c = 9.669 (1) ŵ = 0.12 mm1
α = 75.043 (2)°T = 100 K
β = 86.534 (2)°Prism, yellow
γ = 79.042 (2)°0.40 × 0.30 × 0.20 mm
V = 476.45 (9) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2052 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.008
Graphite monochromatorθmax = 30.1°, θmin = 2.2°
ω scansh = 99
3364 measured reflectionsk = 1010
2364 independent reflectionsl = 013
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: difference Fourier map
wR(F2) = 0.109All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0746P)2 + 0.0491P]
where P = (Fo2 + 2Fc2)/3
2364 reflections(Δ/σ)max = 0.001
189 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C11H9NO3·H2Oγ = 79.042 (2)°
Mr = 221.21V = 476.45 (9) Å3
Triclinic, P1Z = 2
a = 6.6556 (7) ÅMo Kα radiation
b = 7.8062 (8) ŵ = 0.12 mm1
c = 9.669 (1) ÅT = 100 K
α = 75.043 (2)°0.40 × 0.30 × 0.20 mm
β = 86.534 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2052 reflections with I > 2σ(I)
3364 measured reflectionsRint = 0.008
2364 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.109All H-atom parameters refined
S = 1.05Δρmax = 0.44 e Å3
2364 reflectionsΔρmin = 0.24 e Å3
189 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
xyzUiso*/Ueq
C20.78729 (14)0.19129 (13)0.81555 (11)0.0125 (2)
C30.81738 (15)0.35224 (13)0.77026 (11)0.0144 (2)
C40.81565 (15)0.34664 (13)0.62766 (11)0.0139 (2)
C50.78612 (15)0.16421 (13)0.37397 (11)0.0135 (2)
C60.75746 (15)0.00336 (13)0.28072 (11)0.0128 (2)
C70.72336 (14)0.16290 (12)0.32882 (10)0.0109 (2)
C80.71830 (14)0.15343 (13)0.47521 (10)0.0104 (2)
C90.75309 (14)0.02043 (12)0.57276 (10)0.0105 (2)
C100.78608 (14)0.17894 (12)0.52316 (11)0.0118 (2)
C110.79301 (17)0.19091 (14)0.96917 (11)0.0177 (2)
C120.69288 (14)0.34441 (13)0.22357 (10)0.0122 (2)
H10.730 (2)0.066 (2)0.7513 (18)0.032 (4)*
H30.837 (2)0.467 (2)0.8448 (18)0.030 (4)*
H40.836 (2)0.455 (2)0.5954 (16)0.026 (4)*
H50.804 (2)0.2729 (19)0.3385 (16)0.022 (3)*
H60.760 (2)0.0218 (19)0.1796 (16)0.021 (3)*
H310.658 (3)0.404 (3)0.429 (2)0.060 (6)*
H1110.926 (3)0.169 (2)0.988 (2)0.046 (5)*
H1120.689 (3)0.095 (2)0.9918 (19)0.041 (5)*
H1130.772 (3)0.305 (3)1.029 (2)0.054 (5)*
HW10.669 (2)0.266 (2)0.9328 (19)0.028 (4)*
HW20.563 (3)0.326 (3)0.808 (2)0.046 (5)*
N0.75478 (12)0.03384 (11)0.71716 (9)0.01095 (18)
O10.70883 (13)0.35645 (10)0.09333 (8)0.01858 (19)
O20.65155 (11)0.48123 (9)0.27950 (8)0.01463 (18)
O30.68211 (11)0.29915 (9)0.52690 (8)0.01316 (17)
OW0.66319 (13)0.24405 (10)0.84906 (9)0.0198 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0101 (4)0.0124 (4)0.0137 (4)0.0019 (3)0.0002 (3)0.0011 (3)
C30.0138 (4)0.0102 (4)0.0178 (5)0.0020 (3)0.0011 (3)0.0009 (4)
C40.0125 (4)0.0100 (4)0.0195 (5)0.0018 (3)0.0014 (3)0.0039 (4)
C50.0136 (4)0.0121 (4)0.0168 (5)0.0020 (3)0.0001 (3)0.0072 (4)
C60.0124 (4)0.0149 (5)0.0129 (5)0.0025 (3)0.0004 (3)0.0067 (4)
C70.0105 (4)0.0105 (4)0.0119 (5)0.0016 (3)0.0008 (3)0.0032 (3)
C80.0094 (4)0.0098 (4)0.0126 (4)0.0016 (3)0.0006 (3)0.0041 (3)
C90.0096 (4)0.0105 (4)0.0118 (5)0.0022 (3)0.0002 (3)0.0032 (3)
C100.0099 (4)0.0099 (4)0.0159 (5)0.0019 (3)0.0004 (3)0.0038 (4)
C110.0225 (5)0.0163 (5)0.0128 (5)0.0023 (4)0.0003 (4)0.0017 (4)
C120.0103 (4)0.0128 (4)0.0132 (4)0.0014 (3)0.0015 (3)0.0032 (3)
N0.0113 (4)0.0095 (4)0.0121 (4)0.0014 (3)0.0002 (3)0.0030 (3)
O10.0264 (4)0.0172 (4)0.0112 (4)0.0026 (3)0.0015 (3)0.0026 (3)
O20.0197 (4)0.0107 (3)0.0129 (3)0.0009 (3)0.0016 (3)0.0029 (3)
O30.0192 (4)0.0082 (3)0.0126 (3)0.0008 (3)0.0010 (3)0.0046 (3)
OW0.0267 (4)0.0157 (4)0.0160 (4)0.0049 (3)0.0065 (3)0.0069 (3)
Geometric parameters (Å, º) top
C2—N1.3352 (12)C8—O31.3328 (11)
C2—C31.4100 (14)C8—C91.4253 (13)
C2—C111.4889 (14)C9—N1.3735 (12)
C3—C41.3688 (15)C9—C101.4141 (13)
C3—H30.984 (16)C11—H1110.971 (18)
C4—C101.4201 (13)C11—H1120.978 (18)
C4—H40.956 (16)C11—H1130.96 (2)
C5—C61.3702 (14)C12—O11.2379 (12)
C5—C101.4172 (14)C12—O21.2951 (12)
C5—H50.979 (15)N—H10.907 (17)
C6—C71.4133 (13)O3—H311.08 (2)
C6—H60.950 (15)OW—HW10.876 (18)
C7—C81.3969 (13)OW—HW20.87 (2)
C7—C121.5019 (13)
N—C2—C3118.86 (9)N—C9—C10119.60 (8)
N—C2—C11118.88 (9)N—C9—C8119.36 (8)
C3—C2—C11122.26 (9)C10—C9—C8121.04 (9)
C4—C3—C2120.40 (9)C9—C10—C5119.33 (9)
C4—C3—H3122.2 (9)C9—C10—C4117.41 (9)
C2—C3—H3117.4 (9)C5—C10—C4123.25 (9)
C3—C4—C10120.55 (9)C2—C11—H111108.2 (11)
C3—C4—H4121.3 (9)C2—C11—H112111.4 (10)
C10—C4—H4118.2 (9)H111—C11—H112107.9 (15)
C6—C5—C10119.28 (9)C2—C11—H113110.1 (11)
C6—C5—H5120.7 (8)H111—C11—H113109.9 (15)
C10—C5—H5120.1 (9)H112—C11—H113109.2 (16)
C5—C6—C7121.98 (9)O1—C12—O2124.27 (9)
C5—C6—H6123.2 (9)O1—C12—C7120.44 (9)
C7—C6—H6114.9 (9)O2—C12—C7115.29 (8)
C8—C7—C6120.26 (9)C2—N—C9123.14 (8)
C8—C7—C12119.18 (8)C2—N—H1115.9 (10)
C6—C7—C12120.57 (9)C9—N—H1121.0 (10)
O3—C8—C7122.93 (9)C12—O2—H31104.6 (8)
O3—C8—C9119.00 (9)C8—O3—H31100.7 (11)
C7—C8—C9118.08 (9)HW1—OW—HW2103.3 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H31···O21.08 (2)1.42 (2)2.4449 (11)157 (2)
N—H1···Ow0.91 (2)1.85 (2)2.7450 (12)170 (2)
Ow—Hw1···O1i0.87 (2)1.91 (2)2.7746 (12)168 (2)
Ow—Hw2···O2ii0.87 (2)1.92 (2)2.7863 (12)176 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+1, z+1.
(II) 7-carboxy-8-hydroxy-2-methylquinolinium chloride monohydrate top
Crystal data top
C11H10NO3+·Cl·H2OZ = 2
Mr = 257.67F(000) = 268
Triclinic, P1Dx = 1.538 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1089 (4) ÅCell parameters from 2975 reflections
b = 9.4102 (5) Åθ = 2.3–30.2°
c = 9.6230 (5) ŵ = 0.35 mm1
α = 96.719 (1)°T = 100 K
β = 110.184 (1)°Prism, white
γ = 107.941 (1)°0.60 × 0.30 × 0.20 mm
V = 556.57 (5) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2627 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.010
Graphite monochromatorθmax = 30.3°, θmin = 2.3°
ω scansh = 99
3978 measured reflectionsk = 128
2904 independent reflectionsl = 1312
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: difference Fourier map
wR(F2) = 0.086All H-atom parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.1462P]
where P = (Fo2 + 2Fc2)/3
2904 reflections(Δ/σ)max = 0.002
202 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C11H10NO3+·Cl·H2Oγ = 107.941 (1)°
Mr = 257.67V = 556.57 (5) Å3
Triclinic, P1Z = 2
a = 7.1089 (4) ÅMo Kα radiation
b = 9.4102 (5) ŵ = 0.35 mm1
c = 9.6230 (5) ÅT = 100 K
α = 96.719 (1)°0.60 × 0.30 × 0.20 mm
β = 110.184 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2627 reflections with I > 2σ(I)
3978 measured reflectionsRint = 0.010
2904 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.086All H-atom parameters refined
S = 1.08Δρmax = 0.43 e Å3
2904 reflectionsΔρmin = 0.23 e Å3
202 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
xyzUiso*/Ueq
C20.51807 (18)0.69963 (13)0.26054 (12)0.0130 (2)
C30.59355 (18)0.81641 (13)0.19077 (12)0.0140 (2)
C40.70536 (18)0.96635 (13)0.27376 (13)0.0133 (2)
C50.86469 (18)1.15942 (13)0.52474 (13)0.0132 (2)
C60.89649 (18)1.19039 (13)0.67549 (13)0.0132 (2)
C70.81901 (17)1.07035 (13)0.74203 (12)0.0119 (2)
C80.71063 (17)0.91830 (12)0.65502 (12)0.0117 (2)
C90.67491 (17)0.88688 (12)0.49811 (12)0.0111 (2)
C100.75085 (17)1.00612 (13)0.43216 (12)0.0117 (2)
C110.3932 (2)0.53534 (14)0.17359 (14)0.0177 (2)
C120.83898 (17)1.10360 (13)0.90190 (12)0.0132 (2)
Cl0.17327 (4)0.63087 (3)0.77817 (3)0.01637 (9)
H10.499 (3)0.669 (2)0.446 (2)0.045 (6)*
H30.564 (3)0.7853 (18)0.0829 (18)0.016 (4)*
H40.752 (3)1.047 (2)0.228 (2)0.026 (4)*
H50.914 (3)1.239 (2)0.480 (2)0.027 (4)*
H60.973 (2)1.2911 (18)0.7394 (18)0.015 (4)*
H110.920 (3)1.267 (2)1.061 (2)0.041 (5)*
H1110.503 (3)0.494 (2)0.159 (2)0.043 (5)*
H1120.322 (3)0.478 (2)0.228 (2)0.043 (5)*
H1130.293 (3)0.528 (2)0.077 (2)0.036 (5)*
H310.651 (3)0.838 (2)0.801 (2)0.042 (5)*
HW10.276 (3)0.552 (2)0.570 (2)0.039 (5)*
HW20.168 (4)0.475 (2)0.426 (2)0.037 (5)*
N0.55970 (15)0.73849 (11)0.40861 (10)0.01174 (18)
O10.93675 (15)1.25173 (10)0.97271 (10)0.01852 (19)
O20.76556 (14)1.00293 (10)0.96030 (9)0.01691 (18)
O30.63225 (14)0.79801 (10)0.70810 (10)0.01678 (18)
OW0.28687 (14)0.51444 (10)0.49358 (10)0.01639 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0133 (5)0.0155 (5)0.0116 (5)0.0068 (4)0.0053 (4)0.0035 (4)
C30.0160 (5)0.0185 (5)0.0105 (5)0.0078 (4)0.0068 (4)0.0052 (4)
C40.0140 (5)0.0160 (5)0.0133 (5)0.0068 (4)0.0074 (4)0.0068 (4)
C50.0136 (5)0.0126 (5)0.0149 (5)0.0047 (4)0.0071 (4)0.0059 (4)
C60.0130 (5)0.0125 (5)0.0144 (5)0.0049 (4)0.0056 (4)0.0036 (4)
C70.0116 (5)0.0142 (5)0.0104 (5)0.0053 (4)0.0045 (4)0.0035 (4)
C80.0123 (5)0.0130 (5)0.0118 (5)0.0054 (4)0.0060 (4)0.0054 (4)
C90.0114 (5)0.0117 (5)0.0111 (5)0.0048 (4)0.0050 (4)0.0034 (4)
C100.0115 (5)0.0143 (5)0.0122 (5)0.0062 (4)0.0061 (4)0.0052 (4)
C110.0225 (6)0.0146 (5)0.0131 (5)0.0049 (5)0.0062 (4)0.0022 (4)
C120.0122 (5)0.0157 (5)0.0113 (5)0.0058 (4)0.0041 (4)0.0029 (4)
Cl0.01958 (15)0.01797 (15)0.01216 (14)0.00671 (11)0.00752 (10)0.00327 (10)
N0.0132 (4)0.0115 (4)0.0111 (4)0.0044 (3)0.0054 (3)0.0037 (3)
O10.0228 (4)0.0158 (4)0.0137 (4)0.0026 (3)0.0088 (3)0.0001 (3)
O20.0218 (4)0.0174 (4)0.0123 (4)0.0064 (3)0.0082 (3)0.0050 (3)
O30.0243 (4)0.0132 (4)0.0121 (4)0.0033 (3)0.0092 (3)0.0051 (3)
OW0.0167 (4)0.0179 (4)0.0151 (4)0.0061 (3)0.0075 (3)0.0038 (3)
Geometric parameters (Å, º) top
C2—N1.3312 (14)C8—O31.3401 (13)
C2—C31.4158 (15)C8—C91.4200 (14)
C2—C111.4892 (16)C9—N1.3746 (14)
C3—C41.3666 (16)C9—C101.4082 (15)
C3—H30.973 (16)C11—H1111.02 (2)
C4—C101.4212 (15)C11—H1120.95 (2)
C4—H40.955 (18)C11—H1130.93 (2)
C5—C61.3692 (15)C12—O21.2280 (14)
C5—C101.4185 (15)C12—O11.3209 (14)
C5—H50.945 (18)N—H10.86 (2)
C6—C71.4208 (15)O1—H110.90 (2)
C6—H60.942 (16)O3—H310.88 (2)
C7—C81.3919 (15)OW—HW10.82 (2)
C7—C121.4812 (15)OW—HW20.81 (2)
N—C2—C3118.74 (10)N—C9—C10119.61 (10)
N—C2—C11119.09 (10)N—C9—C8119.42 (10)
C3—C2—C11122.16 (10)C10—C9—C8120.95 (10)
C4—C3—C2120.53 (10)C9—C10—C5119.11 (10)
C4—C3—H3122.0 (9)C9—C10—C4117.76 (10)
C2—C3—H3117.4 (9)C5—C10—C4123.11 (10)
C3—C4—C10120.18 (10)C2—C11—H111105.8 (12)
C3—C4—H4121.8 (11)C2—C11—H112111.3 (12)
C10—C4—H4118.0 (11)H111—C11—H112110.2 (16)
C6—C5—C10120.06 (10)C2—C11—H113111.0 (12)
C6—C5—H5121.0 (11)H111—C11—H113108.2 (16)
C10—C5—H5118.9 (10)H112—C11—H113110.2 (17)
C5—C6—C7120.90 (10)O2—C12—O1123.77 (10)
C5—C6—H6121.5 (9)O2—C12—C7122.80 (10)
C7—C6—H6117.6 (9)O1—C12—C7113.40 (10)
C8—C7—C6120.42 (10)C2—N—C9123.14 (10)
C8—C7—C12118.07 (10)C2—N—H1117.5 (14)
C6—C7—C12121.41 (10)C9—N—H1119.0 (14)
O3—C8—C7124.50 (10)C12—O1—H11109.2 (13)
O3—C8—C9116.94 (10)C8—O3—H31105.4 (14)
C7—C8—C9118.54 (10)HW1—OW—HW2108 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H1···Ow0.86 (2)1.97 (2)2.8025 (14)164 (2)
O1—H11···Cli0.90 (2)2.12 (2)2.9641 (11)155 (2)
O3—H31···O20.88 (2)1.80 (2)2.5881 (12)149 (2)
Ow—Hw1···Cl0.82 (2)2.47 (2)3.2744 (10)169 (2)
Ow—Hw2···Clii0.80 (2)2.35 (2)3.1485 (10)177 (2)
Symmetry codes: (i) x+1, y+2, z+2; (ii) x, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC11H9NO3·H2OC11H10NO3+·Cl·H2O
Mr221.21257.67
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)100100
a, b, c (Å)6.6556 (7), 7.8062 (8), 9.669 (1)7.1089 (4), 9.4102 (5), 9.6230 (5)
α, β, γ (°)75.043 (2), 86.534 (2), 79.042 (2)96.719 (1), 110.184 (1), 107.941 (1)
V3)476.45 (9)556.57 (5)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.120.35
Crystal size (mm)0.40 × 0.30 × 0.200.60 × 0.30 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3364, 2364, 2052 3978, 2904, 2627
Rint0.0080.010
(sin θ/λ)max1)0.7050.710
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.109, 1.05 0.030, 0.086, 1.08
No. of reflections23642904
No. of parameters189202
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.44, 0.240.43, 0.23

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SAINT-Plus, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Farrugia, 1999), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
C2—N1.3352 (12)C8—C91.4253 (13)
C2—C111.4889 (14)C9—N1.3735 (12)
C7—C81.3969 (13)C12—O11.2379 (12)
C7—C121.5019 (13)C12—O21.2951 (12)
C8—O31.3328 (11)
N—C2—C11118.88 (9)O1—C12—O2124.27 (9)
C8—C7—C12119.18 (8)O2—C12—C7115.29 (8)
O3—C8—C7122.93 (9)C2—N—C9123.14 (8)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O3—H31···O21.08 (2)1.42 (2)2.4449 (11)157 (2)
N—H1···Ow0.91 (2)1.85 (2)2.7450 (12)170 (2)
Ow—Hw1···O1i0.87 (2)1.91 (2)2.7746 (12)168 (2)
Ow—Hw2···O2ii0.87 (2)1.92 (2)2.7863 (12)176 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y+1, z+1.
Selected geometric parameters (Å, º) for (II) top
C2—N1.3312 (14)C8—C91.4200 (14)
C2—C111.4892 (16)C9—N1.3746 (14)
C7—C81.3919 (15)C12—O21.2280 (14)
C7—C121.4812 (15)C12—O11.3209 (14)
C8—O31.3401 (13)
N—C2—C11119.09 (10)O2—C12—O1123.77 (10)
C8—C7—C12118.07 (10)O2—C12—C7122.80 (10)
O3—C8—C7124.50 (10)C2—N—C9123.14 (10)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N—H1···Ow0.86 (2)1.97 (2)2.8025 (14)164 (2)
O1—H11···Cli0.90 (2)2.12 (2)2.9641 (11)155 (2)
O3—H31···O20.88 (2)1.80 (2)2.5881 (12)149 (2)
Ow—Hw1···Cl0.82 (2)2.47 (2)3.2744 (10)169 (2)
Ow—Hw2···Clii0.80 (2)2.35 (2)3.1485 (10)177 (2)
Symmetry codes: (i) x+1, y+2, z+2; (ii) x, y+1, z+1.
 

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