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On crystallization from CHCl3, CCl4, CH2ClCH2Cl and CHCl2CHCl2, 6-chloro-5-hydr­oxy-2-pyridone, C5H4ClNO2, (I), under­goes a tautomeric rearrangement to 6-chloro-2,5-di­hy­droxy­pyridine, (II). The resulting crystals, viz. 6-chloro-2,5-di­hy­droxy­pyridine chloro­form 0.125-solvate, C5H4ClNO2·0.125CHCl3, (IIa), 6-chloro-2,5-dihydroxy­pyridine carbon tetra­chloride 0.125-solvate, C5H4ClNO2.·0.125CCl4, (IIb), 6-chloro-2,5-di­hy­droxy­pyridine 1,2-dichloro­ethane solvate, C5H4ClNO2·C2H4Cl2, (IIc), and 6-chloro-2,5-dihydroxy­pyri­dine 1,1,2,2-tetra­chloro­ethane solvate, C5H4ClNO2·C2H2Cl4, (IId), have I41/a symmetry, and incorporate extensively disordered solvent in channels that run the length of the c axis. Upon gentle heating to 378 K in vacuo, these crystals sublime to form solvent-free crystals with P21/n symmetry that are exclusively the pyridone tautomer, (I). In these sublimed pyridone crystals, inversion-related mol­ecules form R22(8) dimers via pairs of N—H...O hydrogen bonds. The dimers are linked by O—H...O hydrogen bonds into R46(28) motifs, which join to form pleated sheets that stack along the a axis. In the channel-containing pyridine solvate crystals, viz. (IIa)–(IId), two independent host mol­ecules form an R22(8) dimer via a pair of O—H...N hydrogen bonds. One mol­ecule is further linked by O—H...O hydrogen bonds to two 41 screw-related equivalents to form a helical motif parallel to the c axis. The other independent mol­ecule is O—H...O hydrogen bonded to two \overline{4} related equivalents to form tetra­meric R44(28) rings. The dimers are π–π stacked with inversion-related dimers, which in turn stack the R44(28) rings along c to form continuous solvent-accessible channels. CHCl3, CCl4, CH2ClCH2Cl and CHCl2CHCl2 solvent mol­ecules are able to occupy these channels but are disordered by virtue of the \overline{4} site symmetry within the channels.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109036476/mx3019sup1.cif
Contains datablocks global, I, IIa, IIb, IIc, IId, IRT, IIdRT

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIasup3.hkl
Contains datablock IIa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIbsup4.hkl
Contains datablock IIb

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIcsup5.hkl
Contains datablock IIc

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIdsup6.hkl
Contains datablock IId

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IRTsup7.hkl
Contains datablock IRT

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270109036476/mx3019IIdRTsup8.hkl
Contains datablock IIdRT

CCDC references: 755988; 755989; 755990; 755991; 755992; 755993; 755994

Comment top

6-Chloro-5-hydroxy-2-pyridone, (I), was synthesized as part of a study of the Elbs oxidation of 2-pyridones (Behrman, 2008). The crude material contains some of the o-isomer, 6-chloro-2,3-dihydroxypyridine, but that can be removed by recrystallization from CHCl3. Elemental analysis of the crystals and their 1H NMR spectra showed the presence of approximately one CHCl3 guest for every eight of the pyridine host - an unusual ratio. Some small molecules are known to form large-diameter channels via elaborate hydrogen-bonding networks (see, for example, Glidewell et al., 2005; Hao et al., 2005), and this seemed a likely cause of the unusual guest:host ratio. Given the considerable current interest in crystal engineering, the potential applications of large solvent-accessible channels (Sisson et al., 2005; Maly et al., 2007, Comotti et al., 2009; Furukawa & Yaghi, 2009) and the influence of substituents at the 6-position on tautomerism in 2-pyridones (Almlöf et al., 1971; Kvick, 1976; Johnson, 1984), we undertook a study of (I) crystallized from a series of solvents. We report here the structure of the pyridine tautomer, 6-chloro-2,5-dihydroxypyridine, (II), as the chloroform solvate, (IIa), and the carbon tetrachloride solvate, (IIb). Solvate crystals grown from CH2ClCH2Cl, (IIc), and CHCl2CHCl2, (IId), were also obtained. Although the host-molecule framework is ostensibly the same in all four solvates, the disorder of the solvent was too severe in (IIc) and (IId) to be modelled in an acceptable way. Refined models of (IIc) and (IId) in which the solvent contribution was removed using SQUEEZE (PLATON; Spek, 2009) are given in the Supplementary Material. In addition to the low-temperature structures, room temperature structure determinations of (I) and (IId) were also performed. There were no substantive differences between these room-temperature structures and their low-temperature counterparts, other than the expected difference in volume, which was ca 2–3%, as is common for molecular crystals.

Attempts to anneal the disordered solvent or to drive the solvent from the channels at elevated temperatures (above ca 378 K) led to the collapse of the host framework and to sublimation growth of solvent-free crystals of the pyridone tautomer, (I) (Fig. 1). Bond lengths and angles in (I) (Table 1) are within the normal range (Allen et al., 1987). In these sublimed crystals, inversion-related molecules form R22(8) dimers (Bernstein et al., 1995) via pairs of N—H···O hydrogen bonds. Four such dimers are linked by O—H···O hydrogen bonds into R46(28) motifs, which combine to form extensive pleated sheets (Fig. 2) that stack along the a axis. Hydrogen-bond parameters for (I) are given in Table 2.

Crystals of (IIa), (IIb), (IIc) and (IId) are isostructural with regard to the host-molecule framework. The following description is based upon the structure of (IIa), but unless stated otherwise the general features apply to all four solvates. Bond lengths and angles (Table 3) in the two independent molecules (designated A and B in Fig. 3) are normal, and the molecules are largely flat [r.m.s. deviations from planarity are 0.027 (2) and 0.009 (2) Å, respectively, for all non-H atoms of A and B). Indeed, the only significant deviation from planarity is for atom H1A, which is almost syn with respect to the O1A—H1A hydroxyl group para to it, but twisted out of the plane of the ring by about 39°. This is a consequence of intermolecular hydrogen bonding of molecule A in a repeating C(2) chain motif to 41 screw-related equivalents, to form helices that propagate along c (Fig. 4). In molecule B, the corresponding torsion angle is only 4° out of planarity, and so strictly anti with respect to O2B—H2B. The B molecules are linked by O—H···O hydrogen bonds to 4 related equivalents to form large tetrameric R44(28) rings (Fig. 5). The two independent molecules (A helix-forming and B ring-forming) are linked in a pseudo inversion-related manner into planar R22(8) dimers by pairs of hydrogen bonds (O2A—H2A···N1B and O2B—H2B···N1A). These dimers are ππ stacked with inversion-related dimers [mean ππ spacing = 3.351 (3) Å], with concomitant stacking of the R44(28) rings along the c axis to form continuous solvent-accessible channels (Fig. 6). Solvent molecules of appropriate size (e.g. CHCl3, CCl4, CH2ClCH2Cl and CHCl2CHCl2) are able to occupy the channels, but are disordered as a consequence of the 4 symmetry. Crystals grown from either acetone or propan-2-ol were too small for conventional X-ray analysis, but gave 1H NMR spectra that suggested similar stoichiometry to (IIa), (IIb), (IIc) and (IId). Larger solvent molecules, such as chlorobenzene, gave tiny crystals that were far too small for diffraction studies, but that gave IR spectra identical to the sublimate, as distinct from the IR spectra of the solvated crystals.

We anticipated that since CCl4 is tetrahedral it might occupy the channels in an ordered fashion, but this was not the case. Indeed, it is the nature of the solvent within these solvate crystals that causes the most significant (albeit small) differences between them. Channel volumes differ slightly owing to the need to accomodate solvent molecules of different size. Estimates of channel volume per unit cell using PLATON (Spek, 2009), were 186.0, 187.5, 185.9 and 198.6 Å3 for (IIa), (IIb), (IIc) and (IId), respectively, at 90 K. For structures (IIa) and (IIb) it proved possible to model CHCl3 and CCl4 solvent molecules disordered on the 4 of Wyckoff site a in I41/a, such that the site is fully occupied overall. For (IIc) and (IId), although no satisfactory disorder model could be found, an estimate of the occupancy of the solvent channels was made via the electron count of the SQUEEZE routine in PLATON. To within a few percent, the 4 sites in each of (IIa), (IIb), (IIc) and (IId) appear to be fully occupied, giving a solvent:host ratio of 1:8. Alternative estimates based on NMR spectroscopy [600 MHz, 1H NMR, for (IIa), (IIc) and (IId); 800 MHz, 13C NMR for (IIb)] were less clear cut [1:8, 1:7, 1:12, 1:10.5 for (IIa), (IIb), (IIc) and (IId), respectively], but the sample treatment was necessarily very different for the NMR experiments.

Johnson (1984) gives a comprehensive summary of the factors which influence the tautomeric ratio for the 2-pyridone/2-hydroxypyridine system. Whereas the pyridone form predominates in the parent compound, a 6-chloro substituent shifts the equilibrium toward the hydroxyl form, both in solution and in the gas phase. Thus, changes in molecular environment within a crystal structure can easily favour one form or the other. In the present case, differences between the molecular structures of (I) and (IIa) (Tables 1 and 3) are largely as expected for pyridone–pyridine tautomerism. The C2—O1 carbonyl bond in (I) lengthens from 1.277 (2) Å upon hydrogen shift to 1.338 (2) and 1.348 (3) Å, respectively, for the hydroxyl groups of molecules A and B in (IIb). The lack of aromaticity in (I) is clearly evident in the alternation of C—C bond lengths around the ring, while the aromaticity in (II) is well displayed by the similarity in the C—C bond lengths. Although the R22(8) dimers in (I) and in (IIa), (IIb), (IIc) and (IId) are superficially similar in appearance, in (I) the pairs of hydrogen bonds are N—H···O interactions between molecules related by crystallographic inversion, while in (IIa), (IIb), (IIc) and (IId) they are O—H···N interactions and each molecule of the dimer is crystallographically unique. Average donor–acceptor distances within these dimers are slightly shorter for O—H···N at 2.716 (8) Å (for the eight hydrogen bonds of this type in the four pyridine structures), compared with the pyridone N—H···O distance of 2.7393 (18) Å in (I). The O—H···O donor–acceptor distances that link dimers in pyridines (IIa), (IIb), (IIc) and (IId) [average 2.734 (10) Å for four such bonds], where the acceptor is a hydroxyl O atom, are considerably longer than that in (I) [2.6507 (17) Å], where the acceptor is a carbonyl O atom.

Experimental top

The synthesis of (I) has been described previously (Behrman, 2008). Crystals suitable for X-ray diffraction analysis of each of the solvates were prepared as follows. For (IIa), from CHCl3: the crude material (200 mg) was dissolved in hot CHCl3 (9 ml). For (IIb), from CCl4: CHCl3-containing crystals (25 mg) were dissolved in boiling CCl4 (25 ml). For (IIc), from CH2ClCH2Cl: CHCl3-containing crystals (200 mg) were dissolved in boiling CH2ClCH2Cl (10 ml). For (IId), rom CHCl2CHCl2: CHCl3-containing crystals (50 mg) were dissolved in hot (not boiling) CHCl2CHCl2 (2.5 ml). In each case, crystals grew on cooling as pale-yellow needles. Small crystals of (I) formed on sublimation of the solvate crystals at 378 K and 0.5 mm Hg (1mm Hg = 133.322 Pa).

Crystals formed from all four solvents melt at 424–425 K (decomposition), as does the sublimate. This implies that solvent loss below the melting point occurs for all forms of (II), which then transforms to (I), thereby yielding a single melting point. All solvate crystals give identical IR spectra as mulls in Nujol: 1668, 1605, 1491, 1325, 1283, 1240, 1208, 1182, 1085, 912, 811, 691 cm-1. When these crystals are sublimed in vacuo, different IR spectra result: 1591, 1503, 1337, 1246, 1195, 1183, 1168, 1081, 910, 810, 693 cm-1. UV [1 × 10-4M aqueous HCl, λmax (nm), ε (M-1 cm-1)]: 301, 4900; 222, 5100; 330–340 (sh). The sublimate gives 301, 5700; 222, 5550, 330–340 (sh). Crystallization from chlorobenzene gives material with the same IR spectrum as the sublimate. The 1H NMR spectrum of the sublimate no longer shows evidence of solvent but is otherwise identical to that reported previously (Behrman, 2008). 1H NMR spectra of crystals grown from either acetone or propan-2-ol suggested stoichiometry similar to (IIa), (IIb), (IIc) and (IId) but the crystals were too small for X-ray analysis. Estimates of guest:host molecule ratios were made either by 600 MHz 1H NMR [(IIa), (IIc) and (IId)], or by 800 MHz 13C NMR with inverse gated 1H decoupling and a delay time of 8 s under the following conditions: 18 mg crystals, 15 mg Cr(acac)3, 0.6 ml CDCl3, 0.3 ml DMSO-d6 (Berger & Braun, 2004), as well as by disorder model refinement [(IIa) and (IIb)] and by a count of the number of electrons present within the channels of (IIa), (IIb), (IIc) and (IId) using SQUEEZE in PLATON (Spek, 2009).

Refinement top

H atoms in each of the structures were found in difference Fourier maps and subsequently placed in idealized positions, with C—H = 0.95 (CArH) or 1.00 Å [in the CHCl3 of (IIa)], N—H = 0.88 Å and O—H = 0.84 Å, and with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(O).

In (IIa) and (IIb), the solvent molecules are disordered on sites of 4 point symmetry. They required restraints on interatomic distances (SADI in SHELXL97; Sheldrick, 2008) to maintain a chemically sensible geometry, and on displacement parameters (SIMU in SHELXL97) to counteract distortion of the resulting ellipsoids caused by the symmetry of the solvent site. In (IIb), the CCl4 was split over two sites, each with occupancy 0.125. The corresponding atoms in each fragment were close enough to warrant use of the EADP constraint in addition to SIMU. In (IIc) and (IId), molecules of solvent were also disordered on sites of 4 symmetry, but suitable disorder models could not be found. In order to obtain a better quality refinement of the host-molecule framework, the SQUEEZE routine in PLATON (Spek, 2009) was used to remove the contribution from the disordered solvent.

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I), (IIa), (IIc), IRT, IIdRT; APEX2 (Bruker, 2006) for (IIb), (IId). Cell refinement: SCALEPACK (Otwinowski & Minor, 1997) for (I), (IIa), (IIc), IRT, IIdRT; APEX2 (Bruker, 2006) for (IIb), (IId). Data reduction: DENZO-SMN (Otwinowski & Minor, 1997) for (I), (IIa), (IIc), IRT, IIdRT; APEX2 (Bruker, 2006) for (IIb), (IId). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures for (I), (IIa), (IIb), (IIc), (IId), IRT; SHELXL97 (Sheldrick, 2008) and local procedures. for IIdRT.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacememt ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Hydrogen bonding in (I). The molecules form R22(8) dimers via pairs of N—H···O hydrogen bonds, and these are in turn linked via four sets of O—H···O hydrogen bonds to form R46(28) motifs which, together with the dimers, create pleated layers. Hydrogen bonds are represented as dashed lines.
[Figure 3] Fig. 3. The asymmetric unit of the chloroform solvate, (IIa), showing the atom-numbering scheme and the dimerization of the host molecules via hydrogen bonding (dashed lines). Displacememt ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The chloroform guest molecule sits on a site of 4 symmetry and is thus extensively disordered. The structures of the CCl4, CH2ClCH2Cl and CHCl2CHCl2 solvates, (IIb), (IIc) and (IId) are ostensibly the same, but the guest solvents in (IIc) and (IId) were too badly disordered to model.
[Figure 4] Fig. 4. Three turns of an extended hydrogen-bonded helix motif in (IIa), viewed perpendicular to the c axis. This helix propagates along the 41 screw axis, parallel to the crystallographic c axis, and includes only molecules of type A (Fig. 3). The CCl4, CH2ClCH2Cl and CHCl2CHCl2 solvates, (IIb), (IIc) and (IId), respectively, all have essentially the same structural feature. Bonds and atoms involved in the helix are drawn with solid colours. Dashed lines indicate continuation of the helix.
[Figure 5] Fig. 5. One of the large R44(28) O—H···O hydrogen-bonded rings in (IIa), viewed perpendicular to the bc plane. Atoms and bonds involved in the large rings are drawn with solid colours. Dashed lines represent O—H···N hydrogen bonds within R22(8) dimer pairs between molecules of type A (helix-forming) and type B (ring-forming). These ring structures stack along the c direction to form solvent-accessible channels. A disordered CHCl3 molecule is shown within the cavity.
[Figure 6] Fig. 6. A packing diagram for (IIa), viewed perpendicular to the bc plane, showing the presence of disordered guest solvent molecules within channels parallel to c. Crystals of (IIb), (IIc) and (IId) exhibit essentially identical packing.
(I) 6-Chloro-5-hydroxy-2-pyridone top
Crystal data top
C5H4ClNO2F(000) = 296
Mr = 145.54Dx = 1.670 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1401 reflections
a = 4.1960 (1) Åθ = 1.0–27.5°
b = 10.6058 (3) ŵ = 0.57 mm1
c = 13.0059 (4) ÅT = 90 K
β = 90.8559 (12)°Block, colourless
V = 578.72 (3) Å30.15 × 0.15 × 0.12 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
1124 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
Detector resolution: 9.1 pixels mm-1h = 55
ω scans at fixed χ = 55°k = 1113
7956 measured reflectionsl = 1616
1329 independent reflections
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0256P)2 + 0.4865P]
where P = (Fo2 + 2Fc2)/3
1329 reflections(Δ/σ)max = 0.001
83 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C5H4ClNO2V = 578.72 (3) Å3
Mr = 145.54Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.1960 (1) ŵ = 0.57 mm1
b = 10.6058 (3) ÅT = 90 K
c = 13.0059 (4) Å0.15 × 0.15 × 0.12 mm
β = 90.8559 (12)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1124 reflections with I > 2σ(I)
7956 measured reflectionsRint = 0.037
1329 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.12Δρmax = 0.28 e Å3
1329 reflectionsΔρmin = 0.26 e Å3
83 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 > 2σ(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
N10.7527 (3)0.39466 (14)0.42347 (10)0.0135 (3)
H10.81520.40630.48770.016*
C20.8634 (4)0.47507 (16)0.35071 (13)0.0144 (4)
C30.7474 (4)0.45377 (17)0.24818 (13)0.0154 (3)
H30.81500.50710.19400.019*
C40.5417 (4)0.35810 (17)0.22780 (13)0.0168 (4)
H40.46580.34640.15930.020*
C50.4369 (4)0.27523 (16)0.30544 (13)0.0148 (4)
C60.5503 (4)0.29713 (16)0.40244 (13)0.0142 (3)
O11.0593 (3)0.56173 (12)0.37709 (9)0.0170 (3)
O20.2272 (3)0.18022 (12)0.28759 (10)0.0188 (3)
H20.26610.14650.23070.028*
Cl10.44759 (11)0.20514 (4)0.50532 (3)0.02215 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0152 (7)0.0155 (7)0.0098 (6)0.0000 (6)0.0016 (5)0.0013 (6)
C20.0162 (8)0.0128 (8)0.0142 (8)0.0030 (6)0.0009 (6)0.0002 (6)
C30.0186 (8)0.0162 (9)0.0115 (8)0.0025 (7)0.0010 (6)0.0021 (7)
C40.0177 (8)0.0207 (9)0.0120 (8)0.0046 (7)0.0003 (6)0.0031 (7)
C50.0125 (8)0.0154 (9)0.0164 (8)0.0021 (6)0.0005 (6)0.0044 (7)
C60.0153 (8)0.0134 (8)0.0139 (8)0.0016 (7)0.0015 (6)0.0011 (7)
O10.0207 (6)0.0155 (6)0.0148 (6)0.0024 (5)0.0013 (5)0.0007 (5)
O20.0183 (6)0.0204 (7)0.0178 (6)0.0047 (5)0.0010 (5)0.0057 (5)
Cl10.0246 (3)0.0252 (3)0.0167 (2)0.00672 (18)0.00072 (17)0.00559 (18)
Geometric parameters (Å, º) top
N1—C21.361 (2)C4—C51.414 (2)
N1—C61.363 (2)C4—H40.9500
N1—H10.8800C5—O21.356 (2)
C2—O11.277 (2)C5—C61.362 (2)
C2—C31.431 (2)C6—Cl11.7162 (17)
C3—C41.356 (2)O2—H20.8400
C3—H30.9500
C2—N1—C6123.64 (14)C3—C4—H4119.0
C2—N1—H1118.2C5—C4—H4119.0
C6—N1—H1118.2O2—C5—C6120.16 (16)
O1—C2—N1119.31 (15)O2—C5—C4123.23 (15)
O1—C2—C3124.95 (15)C6—C5—C4116.59 (16)
N1—C2—C3115.74 (15)C5—C6—N1121.55 (16)
C4—C3—C2120.48 (16)C5—C6—Cl1122.48 (14)
C4—C3—H3119.8N1—C6—Cl1115.97 (12)
C2—C3—H3119.8C5—O2—H2109.5
C3—C4—C5121.98 (16)
C6—N1—C2—O1178.08 (15)O2—C5—C6—N1177.66 (15)
C6—N1—C2—C31.6 (2)C4—C5—C6—N10.5 (2)
O1—C2—C3—C4179.30 (16)O2—C5—C6—Cl12.1 (2)
N1—C2—C3—C40.3 (2)C4—C5—C6—Cl1179.81 (12)
C2—C3—C4—C50.8 (3)C2—N1—C6—C51.7 (3)
C3—C4—C5—O2178.80 (16)C2—N1—C6—Cl1178.57 (13)
C3—C4—C5—C60.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.881.862.7393 (18)177
O2—H2···O1ii0.841.832.6507 (17)166
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+3/2, y1/2, z+1/2.
(IIa) 6-Chloro-2,5-dihydroxypyridine chloroform 0.125-solvate top
Crystal data top
C5H4ClNO2·0.125CHCl3Dx = 1.667 Mg m3
Mr = 160.46Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3119 reflections
Hall symbol: -I 4adθ = 1.0–27.5°
a = 27.1736 (10) ŵ = 0.68 mm1
c = 6.9253 (2) ÅT = 90 K
V = 5113.7 (3) Å3Block cut from needle, pale yellow
Z = 320.20 × 0.18 × 0.18 mm
F(000) = 2600
Data collection top
Nonius KappaCCD area-detector
diffractometer
2924 independent reflections
Radiation source: fine-focus sealed tube1731 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.069
Detector resolution: 9.1 pixels mm-1θmax = 27.5°, θmin = 1.5°
ω scans at fixed χ = 55°h = 3535
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
k = 2424
Tmin = 0.877, Tmax = 0.888l = 58
12800 measured reflections
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0769P)2]
where P = (Fo2 + 2Fc2)/3
2924 reflections(Δ/σ)max = 0.001
198 parametersΔρmax = 0.53 e Å3
12 restraintsΔρmin = 0.44 e Å3
Crystal data top
C5H4ClNO2·0.125CHCl3Z = 32
Mr = 160.46Mo Kα radiation
Tetragonal, I41/aµ = 0.68 mm1
a = 27.1736 (10) ÅT = 90 K
c = 6.9253 (2) Å0.20 × 0.18 × 0.18 mm
V = 5113.7 (3) Å3
Data collection top
Nonius KappaCCD area-detector
diffractometer
2924 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
1731 reflections with I > 2σ(I)
Tmin = 0.877, Tmax = 0.888Rint = 0.069
12800 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05212 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 0.99Δρmax = 0.53 e Å3
2924 reflectionsΔρmin = 0.44 e Å3
198 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 > 2σ(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.

The chloroform solvent is disordered on a 4, and as such required restraints on interatomic distances (SADI in SHELXL97) to maintain a chemically sensible geometry, and on displacement parameters (SIMU in SHELXL97) to counteract the influence of the disorder. Quantitative 1H NMR spectroscopy indicated a ratio of pyridine:solvent of about 8:1, which was is good agreement with the amount required by full occupancy of the 4 sites within the channels of this crystal structure. A count of electrons (59.5 e) within the channels by the SQUEEZE routine in PLATON (Spek, 2003) also indicated full occupancy for the solvent sites.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N1A0.42002 (9)0.46883 (9)0.4204 (3)0.0177 (6)
C2A0.44769 (11)0.47793 (11)0.2654 (4)0.0195 (7)
C3A0.42923 (11)0.50030 (11)0.1000 (4)0.0191 (7)
H3A0.45000.50720.00700.023*
C4A0.38012 (12)0.51209 (11)0.0957 (4)0.0206 (7)
H4A0.36640.52720.01570.025*
C5A0.35031 (11)0.50183 (11)0.2551 (4)0.0175 (7)
C6A0.37214 (11)0.48039 (11)0.4116 (4)0.0182 (7)
O1A0.49568 (8)0.46619 (9)0.2699 (3)0.0278 (6)
H1A0.50210.45180.37420.042*
O2A0.30080 (7)0.51153 (8)0.2389 (3)0.0230 (5)
H2A0.28980.52100.34610.035*
Cl1A0.33779 (3)0.46810 (3)0.61766 (11)0.0208 (2)
N1B0.52399 (9)0.41149 (9)0.5796 (4)0.0197 (6)
C2B0.49708 (11)0.40275 (11)0.7368 (4)0.0206 (7)
C3B0.51585 (12)0.37849 (12)0.8973 (4)0.0240 (8)
H3B0.49580.37261.00740.029*
C4B0.56389 (12)0.36319 (11)0.8936 (4)0.0232 (7)
H4B0.57750.34661.00210.028*
C5B0.59301 (11)0.37184 (11)0.7306 (4)0.0194 (7)
C6B0.57061 (11)0.39608 (11)0.5798 (4)0.0193 (7)
O1B0.44964 (8)0.41806 (8)0.7360 (3)0.0251 (6)
H1B0.44400.43370.63380.038*
O2B0.64090 (8)0.35919 (9)0.7141 (3)0.0298 (6)
H2B0.64950.34300.81190.045*
Cl1B0.60408 (3)0.40782 (3)0.37067 (11)0.0230 (2)
C1S0.5269 (5)0.2395 (4)0.267 (2)0.033 (4)*0.25
H1S0.55180.23200.16420.039*0.25
Cl1S0.5185 (3)0.1854 (2)0.3863 (10)0.0471 (18)0.25
Cl2S0.47528 (19)0.25883 (18)0.1432 (10)0.0811 (19)0.25
Cl3S0.5522 (3)0.2856 (3)0.3983 (13)0.073 (3)0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0188 (14)0.0167 (14)0.0176 (14)0.0007 (10)0.0028 (11)0.0031 (11)
C2A0.0221 (18)0.0202 (17)0.0161 (17)0.0012 (13)0.0023 (14)0.0011 (13)
C3A0.0224 (18)0.0195 (17)0.0155 (17)0.0028 (13)0.0014 (13)0.0006 (13)
C4A0.0275 (19)0.0177 (16)0.0166 (17)0.0003 (13)0.0002 (14)0.0024 (13)
C5A0.0164 (17)0.0166 (16)0.0196 (16)0.0002 (12)0.0005 (13)0.0024 (13)
C6A0.0221 (17)0.0154 (16)0.0171 (17)0.0051 (12)0.0024 (14)0.0005 (13)
O1A0.0196 (13)0.0403 (15)0.0235 (13)0.0076 (10)0.0033 (10)0.0109 (11)
O2A0.0176 (12)0.0300 (13)0.0214 (13)0.0024 (9)0.0016 (10)0.0025 (10)
Cl1A0.0216 (4)0.0231 (4)0.0177 (4)0.0013 (3)0.0038 (3)0.0023 (3)
N1B0.0182 (14)0.0185 (14)0.0226 (14)0.0002 (11)0.0027 (12)0.0034 (12)
C2B0.0215 (18)0.0206 (18)0.0196 (17)0.0014 (13)0.0017 (14)0.0007 (14)
C3B0.0241 (18)0.0305 (19)0.0172 (17)0.0009 (14)0.0053 (15)0.0045 (15)
C4B0.0302 (19)0.0206 (17)0.0187 (17)0.0025 (14)0.0034 (15)0.0051 (14)
C5B0.0200 (17)0.0198 (17)0.0184 (17)0.0011 (13)0.0004 (13)0.0020 (14)
C6B0.0222 (17)0.0172 (16)0.0184 (16)0.0033 (13)0.0029 (13)0.0023 (14)
O1B0.0226 (13)0.0294 (13)0.0232 (13)0.0036 (9)0.0059 (10)0.0124 (10)
O2B0.0255 (13)0.0375 (15)0.0264 (13)0.0060 (10)0.0005 (11)0.0096 (11)
Cl1B0.0211 (4)0.0297 (5)0.0182 (4)0.0019 (3)0.0042 (3)0.0045 (3)
Cl1S0.073 (5)0.037 (3)0.031 (3)0.006 (3)0.010 (3)0.008 (2)
Cl2S0.060 (3)0.051 (3)0.133 (6)0.009 (2)0.062 (3)0.029 (3)
Cl3S0.090 (7)0.042 (4)0.087 (6)0.023 (4)0.025 (5)0.004 (4)
Geometric parameters (Å, º) top
N1A—C2A1.333 (4)C2B—O1B1.355 (4)
N1A—C6A1.340 (4)C2B—C3B1.390 (4)
C2A—O1A1.343 (3)C3B—C4B1.370 (4)
C2A—C3A1.391 (4)C3B—H3B0.9500
C3A—C4A1.373 (4)C4B—C5B1.399 (4)
C3A—H3A0.9500C4B—H4B0.9500
C4A—C5A1.397 (4)C5B—O2B1.351 (4)
C4A—H4A0.9500C5B—C6B1.376 (4)
C5A—C6A1.366 (4)C6B—Cl1B1.740 (3)
C5A—O2A1.375 (3)O1B—H1B0.8400
C6A—Cl1A1.738 (3)O2B—H2B0.8400
O1A—H1A0.8400C1S—Cl3S1.696 (11)
O2A—H2A0.8400C1S—Cl1S1.703 (11)
N1B—C2B1.333 (4)C1S—Cl2S1.726 (11)
N1B—C6B1.334 (4)C1S—H1S1.0000
C2A—N1A—C6A117.9 (3)O1B—C2B—C3B119.9 (3)
N1A—C2A—O1A119.0 (3)C4B—C3B—C2B118.6 (3)
N1A—C2A—C3A122.7 (3)C4B—C3B—H3B120.7
O1A—C2A—C3A118.2 (3)C2B—C3B—H3B120.7
C4A—C3A—C2A118.1 (3)C3B—C4B—C5B120.2 (3)
C4A—C3A—H3A121.0C3B—C4B—H4B119.9
C2A—C3A—H3A121.0C5B—C4B—H4B119.9
C3A—C4A—C5A120.0 (3)O2B—C5B—C6B118.9 (3)
C3A—C4A—H4A120.0O2B—C5B—C4B124.8 (3)
C5A—C4A—H4A120.0C6B—C5B—C4B116.3 (3)
C6A—C5A—O2A124.8 (3)N1B—C6B—C5B124.8 (3)
C6A—C5A—C4A117.4 (3)N1B—C6B—Cl1B116.0 (2)
O2A—C5A—C4A117.7 (3)C5B—C6B—Cl1B119.2 (2)
N1A—C6A—C5A123.9 (3)C2B—O1B—H1B109.5
N1A—C6A—Cl1A116.1 (2)C5B—O2B—H2B109.5
C5A—C6A—Cl1A120.0 (2)Cl3S—C1S—Cl1S115.5 (8)
C2A—O1A—H1A109.5Cl3S—C1S—Cl2S111.8 (7)
C5A—O2A—H2A109.5Cl1S—C1S—Cl2S113.3 (7)
C2B—N1B—C6B117.7 (3)Cl3S—C1S—H1S105.0
N1B—C2B—O1B117.7 (3)Cl1S—C1S—H1S105.0
N1B—C2B—C3B122.5 (3)Cl2S—C1S—H1S105.0
C6A—N1A—C2A—O1A179.3 (3)C6B—N1B—C2B—O1B179.5 (3)
C6A—N1A—C2A—C3A2.4 (4)C6B—N1B—C2B—C3B0.1 (4)
N1A—C2A—C3A—C4A1.9 (5)N1B—C2B—C3B—C4B0.2 (5)
O1A—C2A—C3A—C4A179.8 (3)O1B—C2B—C3B—C4B179.7 (3)
C2A—C3A—C4A—C5A0.4 (4)C2B—C3B—C4B—C5B0.2 (5)
C3A—C4A—C5A—C6A0.5 (4)C3B—C4B—C5B—O2B178.6 (3)
C3A—C4A—C5A—O2A176.0 (3)C3B—C4B—C5B—C6B0.1 (5)
C2A—N1A—C6A—C5A1.4 (4)C2B—N1B—C6B—C5B0.1 (4)
C2A—N1A—C6A—Cl1A179.7 (2)C2B—N1B—C6B—Cl1B179.4 (2)
O2A—C5A—C6A—N1A176.3 (3)O2B—C5B—C6B—N1B178.5 (3)
C4A—C5A—C6A—N1A0.0 (4)C4B—C5B—C6B—N1B0.1 (5)
O2A—C5A—C6A—Cl1A5.6 (4)O2B—C5B—C6B—Cl1B2.0 (4)
C4A—C5A—C6A—Cl1A178.2 (2)C4B—C5B—C6B—Cl1B179.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.892.721 (3)169
O2A—H2A···O2Ai0.841.892.647 (2)149
O1B—H1B···N1A0.841.882.707 (3)170
O2B—H2B···O1Bii0.841.892.723 (3)174
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
(IIb) 6-Chloro-2,5-dihydroxypyridine carbon tetrachloride 0.125-solvate top
Crystal data top
C5H4ClNO2·0.125CCl4Dx = 1.707 Mg m3
Mr = 164.77Cu Kα radiation, λ = 1.54178 Å
Tetragonal, I41/aCell parameters from 9933 reflections
Hall symbol: -I 4adθ = 3.3–68.3°
a = 27.1708 (4) ŵ = 6.62 mm1
c = 6.9458 (1) ÅT = 90 K
V = 5127.75 (13) Å3Needle, colourless
Z = 320.12 × 0.02 × 0.01 mm
F(000) = 2664
Data collection top
Bruker X8 Proteum
diffractometer
2344 independent reflections
Radiation source: fine-focus rotating anode2237 reflections with I > 2σ(I)
Graded multilayer optics monochromatorRint = 0.042
Detector resolution: 5.6 pixels mm-1θmax = 68.0°, θmin = 3.3°
ϕ and ω scansh = 3232
Absorption correction: multi-scan
(SADABS in APEX2; Bruker, 2006)
k = 3232
Tmin = 0.672, Tmax = 0.937l = 78
37025 measured reflections
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0491P)2 + 12.1459P]
where P = (Fo2 + 2Fc2)/3
2344 reflections(Δ/σ)max < 0.001
223 parametersΔρmax = 0.55 e Å3
63 restraintsΔρmin = 0.81 e Å3
Crystal data top
C5H4ClNO2·0.125CCl4Z = 32
Mr = 164.77Cu Kα radiation
Tetragonal, I41/aµ = 6.62 mm1
a = 27.1708 (4) ÅT = 90 K
c = 6.9458 (1) Å0.12 × 0.02 × 0.01 mm
V = 5127.75 (13) Å3
Data collection top
Bruker X8 Proteum
diffractometer
2344 independent reflections
Absorption correction: multi-scan
(SADABS in APEX2; Bruker, 2006)
2237 reflections with I > 2σ(I)
Tmin = 0.672, Tmax = 0.937Rint = 0.042
37025 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03463 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0491P)2 + 12.1459P]
where P = (Fo2 + 2Fc2)/3
2344 reflectionsΔρmax = 0.55 e Å3
223 parametersΔρmin = 0.81 e Å3
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 > 2σ(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.

The carbon tetrachloride solvent is disordered on a 4, and as such required restraints on interatomic distances (SADI in SHELXL97) to maintain a chemically sensible geometry and on displacement parameters (SIMU in SHELXL97) to counteract the influence of the disorder. The CCl4 was split over two sites, each with occupancy 0.125. The corresponding atoms in each fragment were close enough to warrant use of the EADP constraint in addition to SIMU. Quantitative 13C NMR spectroscopy indicated a ratio of pyridine:solvent of about 7:1, which is in good agreement with the amount required by full occupancy of the 4 sites within the channels of this crystal structure. A count of electrons (74.7 e) within the channels by the SQUEEZE routine in PLATON (Spek, 2003) also indicated full occupancy for the solvent sites.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N1A0.42009 (6)0.46889 (6)0.4207 (3)0.0164 (4)
C2A0.44786 (7)0.47826 (7)0.2661 (3)0.0176 (4)
C3A0.42893 (8)0.50055 (7)0.1005 (3)0.0177 (4)
H3A0.44960.50750.00650.021*
C4A0.38005 (8)0.51206 (7)0.0963 (3)0.0180 (4)
H4A0.36630.52700.01500.022*
C5A0.35011 (7)0.50192 (7)0.2548 (3)0.0170 (4)
C6A0.37236 (8)0.48054 (7)0.4121 (3)0.0163 (4)
O1A0.49565 (5)0.46650 (6)0.2699 (2)0.0242 (4)
H1A0.50180.45030.37010.036*
O2A0.30080 (5)0.51133 (6)0.2398 (2)0.0205 (3)
H2A0.28970.51980.34780.031*
Cl1A0.337915 (18)0.468164 (18)0.61718 (7)0.01895 (16)
N1B0.52401 (6)0.41179 (6)0.5796 (3)0.0170 (4)
C2B0.49704 (7)0.40343 (8)0.7367 (3)0.0183 (4)
C3B0.51594 (8)0.37910 (8)0.8967 (3)0.0211 (5)
H3B0.49600.37351.00700.025*
C4B0.56412 (8)0.36336 (8)0.8918 (3)0.0212 (5)
H4B0.57770.34670.99960.025*
C5B0.59303 (8)0.37185 (8)0.7288 (3)0.0186 (4)
C6B0.57058 (8)0.39612 (7)0.5778 (3)0.0171 (4)
O1B0.44977 (5)0.41855 (6)0.7365 (2)0.0231 (3)
H1B0.44380.43350.63330.035*
O2B0.64073 (6)0.35852 (6)0.7108 (2)0.0257 (4)
H2B0.65010.34460.81250.039*
Cl1B0.603645 (18)0.407700 (19)0.36973 (7)0.02072 (16)
C1S0.5022 (7)0.2620 (5)0.3477 (18)0.059 (3)*0.125
Cl1S0.4941 (8)0.2449 (5)0.1066 (13)0.079 (2)0.125
Cl2S0.4858 (6)0.2183 (6)0.5193 (17)0.098 (3)0.125
Cl3S0.5651 (9)0.2778 (14)0.378 (3)0.048 (3)0.125
Cl4S0.4668 (15)0.3161 (6)0.385 (3)0.0433 (18)0.125
C2S0.5025 (9)0.2552 (7)0.391 (2)0.059 (3)*0.125
Cl5S0.4862 (4)0.2234 (3)0.1840 (17)0.079 (2)0.125
Cl6S0.4941 (8)0.2273 (7)0.6125 (19)0.098 (3)0.125
Cl7S0.5653 (9)0.2709 (14)0.358 (3)0.048 (3)0.125
Cl8S0.4680 (16)0.3107 (7)0.381 (3)0.0433 (18)0.125
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0173 (8)0.0169 (8)0.0151 (8)0.0014 (6)0.0017 (7)0.0016 (7)
C2A0.0181 (10)0.0183 (10)0.0164 (10)0.0011 (8)0.0023 (8)0.0014 (8)
C3A0.0220 (10)0.0169 (10)0.0141 (10)0.0017 (8)0.0027 (8)0.0014 (8)
C4A0.0242 (11)0.0160 (10)0.0137 (10)0.0008 (8)0.0011 (8)0.0013 (8)
C5A0.0175 (10)0.0152 (9)0.0182 (10)0.0008 (7)0.0012 (8)0.0024 (8)
C6A0.0185 (10)0.0156 (9)0.0148 (10)0.0036 (8)0.0013 (8)0.0003 (8)
O1A0.0169 (7)0.0363 (9)0.0195 (8)0.0047 (6)0.0032 (6)0.0111 (7)
O2A0.0177 (7)0.0267 (8)0.0172 (7)0.0025 (6)0.0003 (6)0.0025 (6)
Cl1A0.0193 (3)0.0221 (3)0.0154 (3)0.00207 (17)0.00419 (18)0.00127 (18)
N1B0.0178 (8)0.0181 (8)0.0150 (8)0.0004 (7)0.0013 (7)0.0027 (7)
C2B0.0189 (10)0.0184 (10)0.0176 (10)0.0012 (8)0.0025 (8)0.0020 (8)
C3B0.0256 (11)0.0223 (11)0.0155 (10)0.0012 (8)0.0036 (8)0.0044 (8)
C4B0.0273 (11)0.0202 (10)0.0161 (10)0.0001 (8)0.0023 (9)0.0041 (8)
C5B0.0192 (10)0.0179 (10)0.0188 (10)0.0000 (8)0.0019 (8)0.0008 (8)
C6B0.0189 (10)0.0177 (10)0.0149 (10)0.0017 (8)0.0015 (8)0.0003 (8)
O1B0.0205 (8)0.0299 (8)0.0188 (8)0.0037 (6)0.0052 (6)0.0106 (6)
O2B0.0213 (8)0.0334 (9)0.0224 (8)0.0064 (6)0.0007 (6)0.0091 (7)
Cl1B0.0191 (3)0.0274 (3)0.0157 (3)0.00228 (19)0.00335 (18)0.00476 (19)
Cl1S0.092 (4)0.048 (4)0.098 (5)0.001 (4)0.039 (4)0.040 (4)
Cl2S0.095 (5)0.094 (5)0.106 (6)0.006 (4)0.032 (6)0.075 (5)
Cl3S0.019 (2)0.084 (8)0.041 (4)0.024 (3)0.012 (3)0.008 (4)
Cl4S0.028 (2)0.064 (4)0.038 (3)0.026 (3)0.0047 (16)0.002 (3)
Cl5S0.092 (4)0.048 (4)0.098 (5)0.001 (4)0.039 (4)0.040 (4)
Cl6S0.095 (5)0.094 (5)0.106 (6)0.006 (4)0.032 (6)0.075 (5)
Cl7S0.019 (2)0.084 (8)0.041 (4)0.024 (3)0.012 (3)0.008 (4)
Cl8S0.028 (2)0.064 (4)0.038 (3)0.026 (3)0.0047 (16)0.002 (3)
Geometric parameters (Å, º) top
N1A—C6A1.336 (3)N1B—C2B1.334 (3)
N1A—C2A1.337 (3)N1B—C6B1.335 (3)
C2A—O1A1.338 (2)C2B—O1B1.348 (3)
C2A—C3A1.398 (3)C2B—C3B1.392 (3)
C3A—C4A1.365 (3)C3B—C4B1.377 (3)
C3A—H3A0.9500C3B—H3B0.9500
C4A—C5A1.397 (3)C4B—C5B1.397 (3)
C4A—H4A0.9500C4B—H4B0.9500
C5A—O2A1.368 (2)C5B—O2B1.351 (3)
C5A—C6A1.377 (3)C5B—C6B1.381 (3)
C6A—Cl1A1.737 (2)C6B—Cl1B1.731 (2)
O1A—H1A0.8400O1B—H1B0.8400
O2A—H2A0.8400O2B—H2B0.8400
C6A—N1A—C2A117.82 (18)C2B—N1B—C6B118.29 (18)
N1A—C2A—O1A119.13 (18)N1B—C2B—O1B118.08 (18)
N1A—C2A—C3A122.41 (19)N1B—C2B—C3B122.12 (19)
O1A—C2A—C3A118.46 (18)O1B—C2B—C3B119.79 (19)
C4A—C3A—C2A118.35 (19)C4B—C3B—C2B118.6 (2)
C4A—C3A—H3A120.8C4B—C3B—H3B120.7
C2A—C3A—H3A120.8C2B—C3B—H3B120.7
C3A—C4A—C5A120.31 (19)C3B—C4B—C5B120.2 (2)
C3A—C4A—H4A119.8C3B—C4B—H4B119.9
C5A—C4A—H4A119.8C5B—C4B—H4B119.9
O2A—C5A—C6A124.69 (19)O2B—C5B—C6B118.79 (19)
O2A—C5A—C4A118.26 (18)O2B—C5B—C4B124.73 (19)
C6A—C5A—C4A116.95 (19)C6B—C5B—C4B116.47 (19)
N1A—C6A—C5A124.16 (19)N1B—C6B—C5B124.33 (19)
N1A—C6A—Cl1A116.13 (15)N1B—C6B—Cl1B116.22 (16)
C5A—C6A—Cl1A119.71 (16)C5B—C6B—Cl1B119.45 (16)
C2A—O1A—H1A109.5C2B—O1B—H1B109.5
C5A—O2A—H2A109.5C5B—O2B—H2B109.5
C6A—N1A—C2A—O1A179.29 (18)C6B—N1B—C2B—O1B178.86 (18)
C6A—N1A—C2A—C3A1.5 (3)C6B—N1B—C2B—C3B0.0 (3)
N1A—C2A—C3A—C4A1.4 (3)N1B—C2B—C3B—C4B0.1 (3)
O1A—C2A—C3A—C4A179.36 (19)O1B—C2B—C3B—C4B179.0 (2)
C2A—C3A—C4A—C5A0.4 (3)C2B—C3B—C4B—C5B0.0 (3)
C3A—C4A—C5A—O2A176.08 (18)C3B—C4B—C5B—O2B179.0 (2)
C3A—C4A—C5A—C6A0.5 (3)C3B—C4B—C5B—C6B0.3 (3)
C2A—N1A—C6A—C5A0.5 (3)C2B—N1B—C6B—C5B0.3 (3)
C2A—N1A—C6A—Cl1A179.46 (15)C2B—N1B—C6B—Cl1B179.65 (15)
O2A—C5A—C6A—N1A175.89 (18)O2B—C5B—C6B—N1B178.92 (19)
C4A—C5A—C6A—N1A0.4 (3)C4B—C5B—C6B—N1B0.4 (3)
O2A—C5A—C6A—Cl1A5.2 (3)O2B—C5B—C6B—Cl1B1.2 (3)
C4A—C5A—C6A—Cl1A178.44 (15)C4B—C5B—C6B—Cl1B179.51 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.892.726 (2)172
O2A—H2A···O2Ai0.841.902.6487 (15)148
O1B—H1B···N1A0.841.882.708 (2)171
O2B—H2B···O1Bii0.841.912.738 (2)168
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
(IIc) 6-Chloro-2,5-dihydroxypyridine 1,2 dichloroethane solvate top
Crystal data top
C5H4ClNO2Dx = 1.639 Mg m3
Mr = 157.91Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 6336 reflections
Hall symbol: -I 4adθ = 1.0–27.5°
a = 27.1149 (10) ŵ = 0.62 mm1
c = 6.9618 (2) ÅT = 90 K
V = 5118.4 (3) Å3Rod cut from needle, pale yellow
Z = 320.35 × 0.13 × 0.12 mm
F(000) = 2568
Data collection top
Nonius KappaCCD area-detector
diffractometer
2927 independent reflections
Radiation source: fine-focus sealed tube1964 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.087
Detector resolution: 9.1 pixels mm-1θmax = 27.5°, θmin = 1.5°
ω scans at fixed χ = 55°h = 3434
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
k = 3434
Tmin = 0.841, Tmax = 0.941l = 99
52191 measured reflections
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0797P)2]
where P = (Fo2 + 2Fc2)/3
2927 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.82 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C5H4ClNO2Z = 32
Mr = 157.91Mo Kα radiation
Tetragonal, I41/aµ = 0.62 mm1
a = 27.1149 (10) ÅT = 90 K
c = 6.9618 (2) Å0.35 × 0.13 × 0.12 mm
V = 5118.4 (3) Å3
Data collection top
Nonius KappaCCD area-detector
diffractometer
2927 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
1964 reflections with I > 2σ(I)
Tmin = 0.841, Tmax = 0.941Rint = 0.087
52191 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.01Δρmax = 0.82 e Å3
2927 reflectionsΔρmin = 0.36 e Å3
167 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 > 2σ(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.

Molecules of 1,2-dichloroethane were disordered on a site of 4 symmetry and were too badly disordered to decipher. Eventually it was decided to use SQUEEZE in PLATON (Spek, 2003) to remove the contribution from this disordered solvent. Quantitative 1H NMR spectroscopy indicated a ratio of pyridine:solvent of about 12:1, but this was (of necessity) obtained from a bulk sample rather than the single-crystal used for data collection. The SQUEEZE procedure indicated that 48.9 electrons were removed, which corresponds to essentially full solvent occupancy.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.42000 (7)0.46910 (7)0.4194 (3)0.0214 (5)
C2A0.44795 (9)0.47827 (9)0.2657 (4)0.0222 (6)
C3A0.42918 (9)0.50034 (9)0.0997 (4)0.0226 (6)
H3A0.44990.50690.00730.027*
C4A0.38012 (9)0.51223 (9)0.0957 (3)0.0215 (5)
H4A0.36640.52740.01520.026*
C5A0.35022 (8)0.50212 (8)0.2541 (3)0.0191 (5)
C6A0.37221 (8)0.48087 (8)0.4103 (3)0.0208 (5)
O1A0.49575 (6)0.46627 (7)0.2695 (3)0.0312 (5)
H1A0.50250.45300.37520.047*
O2A0.30059 (6)0.51174 (6)0.2376 (2)0.0237 (4)
H2A0.29000.52320.34170.036*
Cl1A0.33764 (2)0.46858 (2)0.61573 (9)0.02273 (19)
N1B0.52363 (7)0.41110 (7)0.5785 (3)0.0230 (5)
C2B0.49665 (9)0.40300 (9)0.7348 (4)0.0239 (6)
C3B0.51547 (9)0.37917 (9)0.8957 (4)0.0274 (6)
H3B0.49540.37361.00540.033*
C4B0.56381 (9)0.36379 (9)0.8927 (4)0.0263 (6)
H4B0.57740.34751.00130.032*
C5B0.59299 (8)0.37199 (9)0.7309 (4)0.0235 (6)
C6B0.57025 (9)0.39555 (8)0.5787 (4)0.0231 (6)
O1B0.44919 (6)0.41809 (7)0.7342 (3)0.0298 (5)
H1B0.44300.43250.63020.045*
O2B0.64076 (6)0.35911 (7)0.7147 (3)0.0319 (5)
H2B0.65000.34510.81600.048*
Cl1B0.60376 (2)0.40687 (2)0.37057 (9)0.0276 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0211 (11)0.0192 (10)0.0240 (12)0.0015 (8)0.0035 (9)0.0038 (9)
C2A0.0208 (12)0.0234 (13)0.0223 (14)0.0012 (10)0.0018 (10)0.0036 (10)
C3A0.0251 (13)0.0231 (13)0.0196 (14)0.0018 (10)0.0027 (10)0.0013 (10)
C4A0.0226 (13)0.0203 (12)0.0217 (14)0.0001 (10)0.0029 (10)0.0021 (10)
C5A0.0190 (12)0.0179 (12)0.0206 (13)0.0022 (9)0.0000 (10)0.0026 (10)
C6A0.0194 (12)0.0217 (12)0.0212 (14)0.0052 (10)0.0026 (10)0.0024 (10)
O1A0.0211 (9)0.0432 (12)0.0294 (11)0.0053 (8)0.0020 (8)0.0146 (9)
O2A0.0201 (9)0.0284 (10)0.0225 (10)0.0018 (7)0.0006 (7)0.0024 (8)
Cl1A0.0217 (3)0.0246 (3)0.0219 (4)0.0019 (2)0.0040 (2)0.0026 (2)
N1B0.0197 (11)0.0226 (10)0.0266 (12)0.0004 (8)0.0010 (9)0.0039 (9)
C2B0.0220 (13)0.0249 (14)0.0249 (15)0.0018 (10)0.0004 (11)0.0065 (11)
C3B0.0273 (14)0.0306 (14)0.0243 (15)0.0019 (11)0.0031 (11)0.0099 (11)
C4B0.0280 (14)0.0266 (14)0.0244 (15)0.0018 (11)0.0037 (11)0.0053 (11)
C5B0.0197 (13)0.0238 (13)0.0269 (15)0.0011 (10)0.0023 (11)0.0003 (11)
C6B0.0229 (13)0.0219 (12)0.0245 (14)0.0014 (10)0.0017 (11)0.0012 (11)
O1B0.0223 (9)0.0371 (11)0.0298 (12)0.0048 (7)0.0068 (8)0.0173 (9)
O2B0.0271 (10)0.0408 (12)0.0278 (11)0.0072 (8)0.0023 (8)0.0104 (9)
Cl1B0.0231 (3)0.0365 (4)0.0233 (4)0.0045 (3)0.0033 (3)0.0049 (3)
Geometric parameters (Å, º) top
N1A—C2A1.335 (3)N1B—C2B1.330 (3)
N1A—C6A1.336 (3)N1B—C6B1.332 (3)
C2A—O1A1.336 (3)C2B—O1B1.350 (3)
C2A—C3A1.397 (3)C2B—C3B1.390 (3)
C3A—C4A1.369 (3)C3B—C4B1.375 (3)
C3A—H3A0.9500C3B—H3B0.9500
C4A—C5A1.396 (3)C4B—C5B1.395 (3)
C4A—H4A0.9500C4B—H4B0.9500
C5A—C6A1.367 (3)C5B—O2B1.346 (3)
C5A—O2A1.376 (3)C5B—C6B1.382 (3)
C6A—Cl1A1.742 (2)C6B—Cl1B1.738 (3)
O1A—H1A0.8400O1B—H1B0.8400
O2A—H2A0.8400O2B—H2B0.8400
C2A—N1A—C6A117.9 (2)C2B—N1B—C6B117.9 (2)
N1A—C2A—O1A119.3 (2)N1B—C2B—O1B118.1 (2)
N1A—C2A—C3A122.4 (2)N1B—C2B—C3B122.3 (2)
O1A—C2A—C3A118.3 (2)O1B—C2B—C3B119.6 (2)
C4A—C3A—C2A118.2 (2)C4B—C3B—C2B118.6 (2)
C4A—C3A—H3A120.9C4B—C3B—H3B120.7
C2A—C3A—H3A120.9C2B—C3B—H3B120.7
C3A—C4A—C5A120.1 (2)C3B—C4B—C5B120.3 (2)
C3A—C4A—H4A119.9C3B—C4B—H4B119.8
C5A—C4A—H4A119.9C5B—C4B—H4B119.8
C6A—C5A—O2A124.9 (2)O2B—C5B—C6B119.0 (2)
C6A—C5A—C4A117.3 (2)O2B—C5B—C4B124.9 (2)
O2A—C5A—C4A117.7 (2)C6B—C5B—C4B116.1 (2)
N1A—C6A—C5A124.1 (2)N1B—C6B—C5B124.8 (2)
N1A—C6A—Cl1A115.92 (18)N1B—C6B—Cl1B116.05 (19)
C5A—C6A—Cl1A119.93 (18)C5B—C6B—Cl1B119.17 (19)
C2A—O1A—H1A109.5C2B—O1B—H1B109.5
C5A—O2A—H2A109.5C5B—O2B—H2B109.5
C6A—N1A—C2A—O1A179.1 (2)C6B—N1B—C2B—O1B179.1 (2)
C6A—N1A—C2A—C3A1.3 (3)C6B—N1B—C2B—C3B0.0 (4)
N1A—C2A—C3A—C4A0.8 (4)N1B—C2B—C3B—C4B0.4 (4)
O1A—C2A—C3A—C4A179.5 (2)O1B—C2B—C3B—C4B179.5 (2)
C2A—C3A—C4A—C5A0.3 (3)C2B—C3B—C4B—C5B0.1 (4)
C3A—C4A—C5A—C6A0.9 (3)C3B—C4B—C5B—O2B178.9 (2)
C3A—C4A—C5A—O2A175.7 (2)C3B—C4B—C5B—C6B0.5 (4)
C2A—N1A—C6A—C5A0.6 (3)C2B—N1B—C6B—C5B0.8 (4)
C2A—N1A—C6A—Cl1A179.45 (17)C2B—N1B—C6B—Cl1B179.77 (18)
O2A—C5A—C6A—N1A175.8 (2)O2B—C5B—C6B—N1B178.5 (2)
C4A—C5A—C6A—N1A0.5 (4)C4B—C5B—C6B—N1B1.0 (4)
O2A—C5A—C6A—Cl1A5.4 (3)O2B—C5B—C6B—Cl1B1.0 (3)
C4A—C5A—C6A—Cl1A178.36 (18)C4B—C5B—C6B—Cl1B179.55 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.902.727 (3)167
O2A—H2A···O2Ai0.841.882.6448 (17)150
O1B—H1B···N1A0.841.882.710 (3)170
O2B—H2B···O1Bii0.841.902.728 (2)168
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
(IId) 6-Chloro-2,5-dihydroxypyridine 1,1,2,2-tetrachloroethane solvate top
Crystal data top
C5H4ClNO2Dx = 1.715 Mg m3
Mr = 166.52Cu Kα radiation, λ = 1.54178 Å
Tetragonal, I41/aCell parameters from 9942 reflections
Hall symbol: -I 4adθ = 3.2–68.5°
a = 27.2426 (10) ŵ = 6.58 mm1
c = 6.9534 (3) ÅT = 90 K
V = 5160.5 (3) Å3Wedge cut from shard, pale yellow
Z = 320.12 × 0.05 × 0.03 mm
F(000) = 2696
Data collection top
Bruker X8 Proteum
diffractometer
2384 independent reflections
Radiation source: fine-focus rotating anode2212 reflections with I > 2σ(I)
Graded multilayer optics monochromatorRint = 0.047
Detector resolution: 5.6 pixels mm-1θmax = 68.5°, θmin = 3.2°
ϕ and ω scansh = 3232
Absorption correction: multi-scan
(SADABS in APEX2; Bruker, 2006)
k = 3232
Tmin = 0.598, Tmax = 0.874l = 88
36806 measured reflections
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0394P)2 + 11.959P]
where P = (Fo2 + 2Fc2)/3
2384 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C5H4ClNO2Z = 32
Mr = 166.52Cu Kα radiation
Tetragonal, I41/aµ = 6.58 mm1
a = 27.2426 (10) ÅT = 90 K
c = 6.9534 (3) Å0.12 × 0.05 × 0.03 mm
V = 5160.5 (3) Å3
Data collection top
Bruker X8 Proteum
diffractometer
2384 independent reflections
Absorption correction: multi-scan
(SADABS in APEX2; Bruker, 2006)
2212 reflections with I > 2σ(I)
Tmin = 0.598, Tmax = 0.874Rint = 0.047
36806 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0394P)2 + 11.959P]
where P = (Fo2 + 2Fc2)/3
2384 reflectionsΔρmax = 0.46 e Å3
167 parametersΔρmin = 0.36 e Å3
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 > 2σ(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.

Molecules of 1,1,2,2-tetrachloroethane were disordered on a site of 4 symmetry and were too badly disordered to decipher. Eventually it was decided to use SQUEEZE in PLATON (Spek, 2003) to remove the contribution from this disordered solvent. Quantitative 1H NMR spectroscopy gave a ratio of pyridine:solvent of about 10.5:1, but this was (of necessity) from a bulk sample rather than the single-crystal used for data collection. The SQUEEZE procedure indicated that 86.7 electrons were removed, which corresponds to essentially full solvent occupancy.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.41959 (6)0.46761 (6)0.4167 (2)0.0195 (4)
C2A0.44769 (7)0.47697 (7)0.2635 (3)0.0205 (4)
C3A0.42906 (8)0.49870 (7)0.0969 (3)0.0203 (4)
H3A0.44980.50550.00960.024*
C4A0.38019 (7)0.50996 (7)0.0910 (3)0.0194 (4)
H4A0.36660.52470.02070.023*
C5A0.35016 (7)0.49983 (7)0.2488 (3)0.0186 (4)
C6A0.37187 (7)0.47888 (7)0.4065 (3)0.0182 (4)
O1A0.49530 (5)0.46571 (6)0.2698 (2)0.0283 (4)
H1A0.50170.45200.37500.042*
O2A0.30093 (5)0.50920 (5)0.2325 (2)0.0221 (3)
H2A0.28970.51740.34030.033*
Cl1A0.337368 (17)0.466564 (17)0.61034 (7)0.02086 (15)
N1B0.52409 (6)0.41370 (6)0.5842 (3)0.0219 (4)
C2B0.49663 (7)0.40471 (8)0.7391 (3)0.0224 (4)
C3B0.51531 (8)0.38083 (8)0.8999 (3)0.0258 (5)
H3B0.49520.37501.00920.031*
C4B0.56349 (9)0.36582 (8)0.8969 (3)0.0263 (5)
H4B0.57690.34931.00510.032*
C5B0.59280 (8)0.37472 (8)0.7363 (3)0.0224 (4)
C6B0.57059 (8)0.39877 (8)0.5849 (3)0.0216 (4)
O1B0.44928 (5)0.41880 (6)0.7356 (2)0.0272 (3)
H1B0.44340.43330.63160.041*
O2B0.64029 (6)0.36158 (6)0.7201 (2)0.0303 (4)
H2B0.64880.34580.81840.045*
Cl1B0.604194 (18)0.411055 (19)0.37925 (7)0.02530 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0181 (8)0.0216 (8)0.0188 (8)0.0006 (6)0.0030 (7)0.0036 (7)
C2A0.0193 (10)0.0215 (10)0.0209 (10)0.0003 (7)0.0036 (8)0.0030 (8)
C3A0.0225 (10)0.0206 (10)0.0178 (10)0.0015 (8)0.0038 (8)0.0027 (8)
C4A0.0233 (10)0.0184 (9)0.0165 (9)0.0018 (8)0.0009 (8)0.0015 (7)
C5A0.0177 (9)0.0165 (9)0.0216 (10)0.0003 (7)0.0000 (8)0.0018 (8)
C6A0.0192 (9)0.0180 (9)0.0174 (9)0.0039 (7)0.0034 (8)0.0012 (7)
O1A0.0184 (7)0.0418 (9)0.0246 (8)0.0059 (6)0.0045 (6)0.0129 (7)
O2A0.0182 (7)0.0282 (8)0.0200 (7)0.0024 (6)0.0000 (6)0.0020 (6)
Cl1A0.0203 (2)0.0236 (3)0.0186 (2)0.00292 (17)0.00502 (17)0.00143 (17)
N1B0.0202 (8)0.0248 (9)0.0207 (9)0.0005 (7)0.0014 (7)0.0054 (7)
C2B0.0218 (10)0.0236 (10)0.0218 (10)0.0003 (8)0.0034 (8)0.0033 (8)
C3B0.0294 (11)0.0275 (11)0.0207 (10)0.0021 (9)0.0042 (9)0.0066 (8)
C4B0.0326 (12)0.0259 (11)0.0205 (10)0.0003 (9)0.0028 (9)0.0058 (8)
C5B0.0227 (10)0.0222 (10)0.0222 (10)0.0002 (8)0.0033 (8)0.0012 (8)
C6B0.0223 (10)0.0225 (10)0.0199 (10)0.0002 (8)0.0018 (8)0.0011 (8)
O1B0.0228 (7)0.0347 (8)0.0242 (8)0.0038 (6)0.0061 (6)0.0117 (6)
O2B0.0243 (8)0.0387 (9)0.0278 (8)0.0071 (6)0.0022 (6)0.0099 (7)
Cl1B0.0211 (3)0.0338 (3)0.0210 (3)0.00342 (19)0.00374 (18)0.00595 (19)
Geometric parameters (Å, º) top
N1A—C2A1.337 (3)N1B—C6B1.331 (3)
N1A—C6A1.338 (3)N1B—C2B1.334 (3)
C2A—O1A1.333 (2)C2B—O1B1.346 (3)
C2A—C3A1.396 (3)C2B—C3B1.390 (3)
C3A—C4A1.367 (3)C3B—C4B1.375 (3)
C3A—H3A0.9500C3B—H3B0.9500
C4A—C5A1.396 (3)C4B—C5B1.394 (3)
C4A—H4A0.9500C4B—H4B0.9500
C5A—O2A1.370 (2)C5B—O2B1.347 (3)
C5A—C6A1.370 (3)C5B—C6B1.380 (3)
C6A—Cl1A1.7336 (19)C6B—Cl1B1.730 (2)
O1A—H1A0.8400O1B—H1B0.8400
O2A—H2A0.8400O2B—H2B0.8400
C2A—N1A—C6A118.07 (17)C6B—N1B—C2B118.36 (18)
O1A—C2A—N1A119.14 (18)N1B—C2B—O1B118.06 (18)
O1A—C2A—C3A118.59 (18)N1B—C2B—C3B122.01 (19)
N1A—C2A—C3A122.27 (19)O1B—C2B—C3B119.92 (19)
C4A—C3A—C2A118.30 (18)C4B—C3B—C2B118.48 (19)
C4A—C3A—H3A120.9C4B—C3B—H3B120.8
C2A—C3A—H3A120.9C2B—C3B—H3B120.8
C3A—C4A—C5A120.19 (19)C3B—C4B—C5B120.5 (2)
C3A—C4A—H4A119.9C3B—C4B—H4B119.8
C5A—C4A—H4A119.9C5B—C4B—H4B119.8
O2A—C5A—C6A124.51 (18)O2B—C5B—C6B118.89 (19)
O2A—C5A—C4A118.14 (18)O2B—C5B—C4B124.82 (19)
C6A—C5A—C4A117.26 (18)C6B—C5B—C4B116.28 (19)
N1A—C6A—C5A123.90 (18)N1B—C6B—C5B124.40 (19)
N1A—C6A—Cl1A116.05 (15)N1B—C6B—Cl1B116.22 (16)
C5A—C6A—Cl1A120.04 (15)C5B—C6B—Cl1B119.37 (16)
C2A—O1A—H1A109.5C2B—O1B—H1B109.5
C5A—O2A—H2A109.5C5B—O2B—H2B109.5
C6A—N1A—C2A—O1A179.50 (18)C6B—N1B—C2B—O1B178.35 (19)
C6A—N1A—C2A—C3A1.2 (3)C6B—N1B—C2B—C3B0.6 (3)
O1A—C2A—C3A—C4A179.72 (19)N1B—C2B—C3B—C4B0.5 (3)
N1A—C2A—C3A—C4A1.0 (3)O1B—C2B—C3B—C4B178.4 (2)
C2A—C3A—C4A—C5A0.1 (3)C2B—C3B—C4B—C5B0.3 (3)
C3A—C4A—C5A—O2A176.40 (18)C3B—C4B—C5B—O2B179.8 (2)
C3A—C4A—C5A—C6A0.5 (3)C3B—C4B—C5B—C6B0.2 (3)
C2A—N1A—C6A—C5A0.6 (3)C2B—N1B—C6B—C5B0.5 (3)
C2A—N1A—C6A—Cl1A179.30 (15)C2B—N1B—C6B—Cl1B179.50 (16)
O2A—C5A—C6A—N1A176.40 (18)O2B—C5B—C6B—N1B179.7 (2)
C4A—C5A—C6A—N1A0.3 (3)C4B—C5B—C6B—N1B0.3 (3)
O2A—C5A—C6A—Cl1A4.9 (3)O2B—C5B—C6B—Cl1B0.3 (3)
C4A—C5A—C6A—Cl1A178.42 (15)C4B—C5B—C6B—Cl1B179.69 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.892.721 (2)169
O2A—H2A···O2Ai0.841.892.6453 (15)148
O1B—H1B···N1A0.841.882.709 (2)170
O2B—H2B···O1Bii0.841.912.746 (2)170
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
(IRT) 6-Chloro-5-hydroxy-2-pyridone top
Crystal data top
C5H4ClNO2F(000) = 296
Mr = 145.54Dx = 1.631 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1430 reflections
a = 4.2481 (1) Åθ = 1.0–27.5°
b = 10.7075 (2) ŵ = 0.56 mm1
c = 13.0362 (3) ÅT = 293 K
β = 91.2416 (11)°Block, colourless
V = 592.83 (2) Å30.15 × 0.10 × 0.10 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
930 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
Detector resolution: 9.1 pixels mm-1h = 55
ω scans at fixed χ = 55°k = 1313
8239 measured reflectionsl = 1616
1356 independent reflections
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0427P)2 + 0.2661P]
where P = (Fo2 + 2Fc2)/3
1356 reflections(Δ/σ)max < 0.001
83 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C5H4ClNO2V = 592.83 (2) Å3
Mr = 145.54Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.2481 (1) ŵ = 0.56 mm1
b = 10.7075 (2) ÅT = 293 K
c = 13.0362 (3) Å0.15 × 0.10 × 0.10 mm
β = 91.2416 (11)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
930 reflections with I > 2σ(I)
8239 measured reflectionsRint = 0.022
1356 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.03Δρmax = 0.22 e Å3
1356 reflectionsΔρmin = 0.34 e Å3
83 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 > 2σ(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
N10.7531 (4)0.39519 (16)0.42306 (12)0.0365 (4)
H10.81260.40720.48580.044*
C20.8612 (5)0.47464 (19)0.35078 (15)0.0377 (5)
C30.7456 (5)0.4530 (2)0.24871 (15)0.0408 (5)
H30.80820.50490.19570.049*
C40.5462 (5)0.3578 (2)0.22867 (15)0.0425 (5)
H40.47340.34590.16160.051*
C50.4442 (5)0.2759 (2)0.30531 (16)0.0392 (5)
C60.5560 (5)0.29753 (19)0.40232 (15)0.0377 (5)
O11.0526 (4)0.56135 (14)0.37712 (10)0.0447 (4)
O20.2389 (4)0.18119 (15)0.28727 (11)0.0516 (4)
H20.27720.14840.23210.077*
Cl10.45728 (16)0.20689 (6)0.50437 (5)0.0636 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0419 (9)0.0409 (10)0.0266 (8)0.0001 (8)0.0040 (7)0.0014 (7)
C20.0429 (11)0.0372 (11)0.0330 (10)0.0054 (9)0.0011 (8)0.0006 (9)
C30.0508 (12)0.0447 (12)0.0268 (10)0.0023 (11)0.0005 (8)0.0026 (9)
C40.0464 (12)0.0526 (13)0.0285 (10)0.0056 (11)0.0040 (8)0.0057 (9)
C50.0358 (11)0.0421 (12)0.0396 (11)0.0039 (9)0.0002 (8)0.0100 (9)
C60.0398 (11)0.0398 (11)0.0335 (10)0.0024 (9)0.0014 (8)0.0021 (9)
O10.0566 (9)0.0413 (8)0.0361 (8)0.0063 (7)0.0045 (7)0.0017 (7)
O20.0509 (9)0.0540 (10)0.0499 (10)0.0094 (8)0.0028 (7)0.0135 (7)
Cl10.0724 (5)0.0720 (5)0.0461 (3)0.0198 (3)0.0031 (3)0.0156 (3)
Geometric parameters (Å, º) top
N1—C21.357 (3)C4—C51.405 (3)
N1—C61.363 (3)C4—H40.9300
N1—H10.8600C5—O21.354 (2)
C2—O11.276 (2)C5—C61.361 (3)
C2—C31.427 (3)C6—Cl11.706 (2)
C3—C41.347 (3)O2—H20.8200
C3—H30.9300
C2—N1—C6123.99 (16)C3—C4—H4118.8
C2—N1—H1118.0C5—C4—H4118.8
C6—N1—H1118.0O2—C5—C6119.96 (19)
O1—C2—N1119.51 (17)O2—C5—C4123.45 (18)
O1—C2—C3124.99 (18)C6—C5—C4116.57 (19)
N1—C2—C3115.50 (18)C5—C6—N1121.04 (18)
C4—C3—C2120.41 (19)C5—C6—Cl1122.72 (17)
C4—C3—H3119.8N1—C6—Cl1116.24 (15)
C2—C3—H3119.8C5—O2—H2109.5
C3—C4—C5122.46 (18)
C6—N1—C2—O1177.96 (18)O2—C5—C6—N1177.40 (18)
C6—N1—C2—C32.2 (3)C4—C5—C6—N10.9 (3)
O1—C2—C3—C4179.3 (2)O2—C5—C6—Cl11.9 (3)
N1—C2—C3—C40.9 (3)C4—C5—C6—Cl1179.79 (15)
C2—C3—C4—C50.3 (3)C2—N1—C6—C52.3 (3)
C3—C4—C5—O2178.6 (2)C2—N1—C6—Cl1178.35 (16)
C3—C4—C5—C60.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.861.902.755 (2)178
O2—H2···O1ii0.821.862.666 (2)167
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+3/2, y1/2, z+1/2.
(IIdRT) 6-Chloro-2,5-dihydroxypyridine 1,1,2,2-tetrachloroethane solvate top
Crystal data top
C5H4ClNO2Dx = 1.663 Mg m3
Mr = 166.52Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 3298 reflections
Hall symbol: -I 4adθ = 1.0–27.5°
a = 27.4722 (2) ŵ = 0.70 mm1
c = 7.0495 (1) ÅT = 293 K
V = 5320.41 (9) Å3Irregular shard, pale yellow
Z = 320.22 × 0.11 × 0.06 mm
F(000) = 2696
Data collection top
Nonius KappaCCD area-detector
diffractometer
3045 independent reflections
Radiation source: fine-focus sealed tube2043 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 9.1 pixels mm-1θmax = 27.5°, θmin = 1.5°
ω scans at fixed χ = 55°h = 2424
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
k = 3535
Tmin = 0.899, Tmax = 0.971l = 99
61598 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.196 w = 1/[σ2(Fo2) + (0.1179P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.001
3045 reflectionsΔρmax = 0.63 e Å3
168 parametersΔρmin = 0.37 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0033 (5)
Crystal data top
C5H4ClNO2Z = 32
Mr = 166.52Mo Kα radiation
Tetragonal, I41/aµ = 0.70 mm1
a = 27.4722 (2) ÅT = 293 K
c = 7.0495 (1) Å0.22 × 0.11 × 0.06 mm
V = 5320.41 (9) Å3
Data collection top
Nonius KappaCCD area-detector
diffractometer
3045 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
2043 reflections with I > 2σ(I)
Tmin = 0.899, Tmax = 0.971Rint = 0.024
61598 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.196H-atom parameters constrained
S = 1.15Δρmax = 0.63 e Å3
3045 reflectionsΔρmin = 0.37 e Å3
168 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 > 2σ(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.

Molecules of 1,1,2,2-tetrachloroethane were disordered on a site of 4 symmetry and were too badly disordered to decipher. Eventually it was decided to use SQUEEZE in PLATON (Spek, 2003) to remove the contribution from this disordered solvent. Quantitative 1H NMR spectroscopy gave a ratio of pyridine:solvent of about 10.5:1, but this was (of necessity) from a bulk sample rather than the single-crystal used for data collection.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.41897 (8)0.46641 (8)0.4137 (3)0.0456 (5)
C2A0.44724 (9)0.47554 (9)0.2624 (4)0.0468 (7)
C3A0.42865 (11)0.49698 (10)0.0987 (4)0.0491 (7)
H3A0.44880.50360.00420.059*
C4A0.38020 (10)0.50814 (9)0.0922 (4)0.0471 (6)
H4A0.36710.52210.01660.057*
C5A0.35044 (9)0.49870 (9)0.2475 (4)0.0429 (6)
C6A0.37192 (9)0.47794 (9)0.4023 (4)0.0429 (6)
O1A0.49416 (7)0.46435 (9)0.2697 (3)0.0651 (6)
H1A0.49990.44990.36910.098*
O2A0.30163 (6)0.50815 (8)0.2304 (3)0.0540 (5)
H2A0.29100.51800.33220.081*
Cl1A0.33749 (2)0.46581 (3)0.60416 (10)0.0535 (3)
N1B0.52308 (8)0.41327 (8)0.5845 (3)0.0462 (5)
C2B0.49579 (10)0.40439 (10)0.7387 (4)0.0499 (7)
C3B0.51423 (11)0.38194 (12)0.8966 (4)0.0591 (8)
H3B0.49460.37651.00200.071*
C4B0.56188 (12)0.36762 (11)0.8970 (4)0.0608 (8)
H4B0.57470.35211.00310.073*
C5B0.59134 (10)0.37607 (10)0.7396 (4)0.0499 (7)
C6B0.56950 (10)0.39890 (9)0.5888 (4)0.0463 (6)
O1B0.44867 (7)0.41769 (8)0.7315 (3)0.0626 (6)
H1B0.44270.42930.62700.094*
O2B0.63876 (8)0.36357 (9)0.7273 (3)0.0727 (7)
H2B0.64760.35150.82780.109*
Cl1B0.60320 (3)0.41090 (3)0.38634 (11)0.0611 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0479 (12)0.0468 (12)0.0420 (13)0.0026 (9)0.0050 (10)0.0063 (10)
C2A0.0429 (14)0.0510 (15)0.0465 (16)0.0021 (11)0.0081 (11)0.0070 (12)
C3A0.0548 (16)0.0510 (15)0.0413 (15)0.0024 (12)0.0078 (12)0.0063 (12)
C4A0.0551 (16)0.0479 (14)0.0383 (15)0.0002 (12)0.0013 (12)0.0029 (11)
C5A0.0448 (14)0.0405 (13)0.0434 (15)0.0012 (10)0.0017 (11)0.0022 (11)
C6A0.0452 (14)0.0419 (13)0.0415 (14)0.0054 (10)0.0054 (11)0.0010 (11)
O1A0.0461 (11)0.0916 (16)0.0576 (14)0.0129 (10)0.0094 (9)0.0246 (12)
O2A0.0441 (10)0.0659 (12)0.0518 (12)0.0030 (9)0.0000 (9)0.0091 (10)
Cl1A0.0526 (4)0.0605 (5)0.0474 (5)0.0043 (3)0.0126 (3)0.0038 (3)
N1B0.0435 (12)0.0518 (12)0.0432 (12)0.0018 (10)0.0032 (10)0.0107 (10)
C2B0.0498 (15)0.0523 (15)0.0476 (16)0.0019 (12)0.0063 (12)0.0091 (13)
C3B0.0610 (18)0.0707 (19)0.0455 (17)0.0024 (15)0.0096 (14)0.0160 (14)
C4B0.072 (2)0.0656 (19)0.0453 (17)0.0016 (15)0.0056 (14)0.0138 (14)
C5B0.0495 (15)0.0485 (15)0.0517 (18)0.0029 (11)0.0021 (12)0.0054 (13)
C6B0.0506 (15)0.0462 (14)0.0421 (14)0.0020 (11)0.0043 (12)0.0019 (11)
O1B0.0537 (12)0.0787 (14)0.0553 (14)0.0083 (9)0.0158 (10)0.0266 (11)
O2B0.0577 (12)0.0887 (16)0.0716 (16)0.0131 (11)0.0056 (11)0.0264 (13)
Cl1B0.0518 (5)0.0778 (6)0.0538 (5)0.0066 (3)0.0108 (3)0.0126 (4)
Geometric parameters (Å, º) top
N1A—C6A1.333 (3)N1B—C6B1.335 (3)
N1A—C2A1.343 (3)N1B—C2B1.343 (3)
C2A—O1A1.326 (3)C2B—O1B1.346 (3)
C2A—C3A1.393 (4)C2B—C3B1.370 (4)
C3A—C4A1.366 (4)C3B—C4B1.367 (4)
C3A—H3A0.9300C3B—H3B0.9300
C4A—C5A1.391 (4)C4B—C5B1.393 (4)
C4A—H4A0.9300C4B—H4B0.9300
C5A—C6A1.365 (4)C5B—O2B1.350 (3)
C5A—O2A1.371 (3)C5B—C6B1.372 (4)
C6A—Cl1A1.741 (3)C6B—Cl1B1.733 (3)
O1A—H1A0.8200O1B—H1B0.8200
O2A—H2A0.8200O2B—H2B0.8200
C6A—N1A—C2A118.0 (2)C6B—N1B—C2B117.4 (2)
O1A—C2A—N1A119.2 (2)N1B—C2B—O1B117.2 (2)
O1A—C2A—C3A119.1 (2)N1B—C2B—C3B122.2 (3)
N1A—C2A—C3A121.7 (2)O1B—C2B—C3B120.6 (2)
C4A—C3A—C2A118.7 (2)C4B—C3B—C2B119.0 (3)
C4A—C3A—H3A120.7C4B—C3B—H3B120.5
C2A—C3A—H3A120.7C2B—C3B—H3B120.5
C3A—C4A—C5A120.3 (2)C3B—C4B—C5B120.5 (3)
C3A—C4A—H4A119.9C3B—C4B—H4B119.8
C5A—C4A—H4A119.9C5B—C4B—H4B119.8
C6A—C5A—O2A124.9 (2)O2B—C5B—C6B119.2 (2)
C6A—C5A—C4A117.0 (2)O2B—C5B—C4B124.7 (2)
O2A—C5A—C4A118.1 (2)C6B—C5B—C4B116.0 (3)
N1A—C6A—C5A124.5 (2)N1B—C6B—C5B124.8 (2)
N1A—C6A—Cl1A115.63 (19)N1B—C6B—Cl1B115.8 (2)
C5A—C6A—Cl1A119.9 (2)C5B—C6B—Cl1B119.4 (2)
C2A—O1A—H1A109.5C2B—O1B—H1B109.5
C5A—O2A—H2A109.5C5B—O2B—H2B109.5
C6A—N1A—C2A—O1A179.9 (2)C6B—N1B—C2B—O1B178.1 (2)
C6A—N1A—C2A—C3A0.9 (4)C6B—N1B—C2B—C3B0.6 (4)
O1A—C2A—C3A—C4A179.7 (3)N1B—C2B—C3B—C4B0.7 (5)
N1A—C2A—C3A—C4A1.1 (4)O1B—C2B—C3B—C4B178.1 (3)
C2A—C3A—C4A—C5A0.8 (4)C2B—C3B—C4B—C5B0.5 (5)
C3A—C4A—C5A—C6A0.3 (4)C3B—C4B—C5B—O2B179.6 (3)
C3A—C4A—C5A—O2A176.6 (2)C3B—C4B—C5B—C6B0.3 (4)
C2A—N1A—C6A—C5A0.4 (4)C2B—N1B—C6B—C5B0.5 (4)
C2A—N1A—C6A—Cl1A179.29 (19)C2B—N1B—C6B—Cl1B179.7 (2)
O2A—C5A—C6A—N1A176.1 (2)O2B—C5B—C6B—N1B179.6 (3)
C4A—C5A—C6A—N1A0.1 (4)C4B—C5B—C6B—N1B0.3 (4)
O2A—C5A—C6A—Cl1A5.0 (3)O2B—C5B—C6B—Cl1B0.2 (4)
C4A—C5A—C6A—Cl1A178.98 (19)C4B—C5B—C6B—Cl1B179.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.821.932.743 (3)171
O2A—H2A···O2Ai0.821.942.6887 (19)151
O1B—H1B···N1A0.821.932.734 (3)167
O2B—H2B···O1Bii0.822.002.788 (3)160
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.

Experimental details

(I)(IIa)(IIb)(IIc)
Crystal data
Chemical formulaC5H4ClNO2C5H4ClNO2·0.125CHCl3C5H4ClNO2·0.125CCl4C5H4ClNO2
Mr145.54160.46164.77157.91
Crystal system, space groupMonoclinic, P21/nTetragonal, I41/aTetragonal, I41/aTetragonal, I41/a
Temperature (K)90909090
a, b, c (Å)4.1960 (1), 10.6058 (3), 13.0059 (4)27.1736 (10), 27.1736 (10), 6.9253 (2)27.1708 (4), 27.1708 (4), 6.9458 (1)27.1149 (10), 27.1149 (10), 6.9618 (2)
α, β, γ (°)90, 90.8559 (12), 9090, 90, 9090, 90, 9090, 90, 90
V3)578.72 (3)5113.7 (3)5127.75 (13)5118.4 (3)
Z4323232
Radiation typeMo KαMo KαCu KαMo Kα
µ (mm1)0.570.686.620.62
Crystal size (mm)0.15 × 0.15 × 0.120.20 × 0.18 × 0.180.12 × 0.02 × 0.010.35 × 0.13 × 0.12
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Bruker X8 Proteum
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Multi-scan
(SADABS in APEX2; Bruker, 2006)
Multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.877, 0.8880.672, 0.9370.841, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
7956, 1329, 1124 12800, 2924, 1731 37025, 2344, 2237 52191, 2927, 1964
Rint0.0370.0690.0420.087
(sin θ/λ)max1)0.6490.6490.6010.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.081, 1.12 0.052, 0.146, 0.99 0.034, 0.092, 1.04 0.051, 0.133, 1.01
No. of reflections1329292423442927
No. of parameters83198223167
No. of restraints012630
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0256P)2 + 0.4865P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0769P)2]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0491P)2 + 12.1459P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0797P)2]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.28, 0.260.53, 0.440.55, 0.810.82, 0.36


(IId)(IRT)(IIdRT)
Crystal data
Chemical formulaC5H4ClNO2C5H4ClNO2C5H4ClNO2
Mr166.52145.54166.52
Crystal system, space groupTetragonal, I41/aMonoclinic, P21/nTetragonal, I41/a
Temperature (K)90293293
a, b, c (Å)27.2426 (10), 27.2426 (10), 6.9534 (3)4.2481 (1), 10.7075 (2), 13.0362 (3)27.4722 (2), 27.4722 (2), 7.0495 (1)
α, β, γ (°)90, 90, 9090, 91.2416 (11), 9090, 90, 90
V3)5160.5 (3)592.83 (2)5320.41 (9)
Z32432
Radiation typeCu KαMo KαMo Kα
µ (mm1)6.580.560.70
Crystal size (mm)0.12 × 0.05 × 0.030.15 × 0.10 × 0.100.22 × 0.11 × 0.06
Data collection
DiffractometerBruker X8 Proteum
diffractometer
Nonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS in APEX2; Bruker, 2006)
Multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.598, 0.8740.899, 0.971
No. of measured, independent and
observed [I > 2σ(I)] reflections
36806, 2384, 2212 8239, 1356, 930 61598, 3045, 2043
Rint0.0470.0220.024
(sin θ/λ)max1)0.6030.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.093, 1.09 0.040, 0.106, 1.03 0.059, 0.196, 1.15
No. of reflections238413563045
No. of parameters16783168
No. of restraints000
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0394P)2 + 11.959P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.0427P)2 + 0.2661P]
where P = (Fo2 + 2Fc2)/3
w = 1/[σ2(Fo2) + (0.1179P)2]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.46, 0.360.22, 0.340.63, 0.37

Computer programs: COLLECT (Nonius, 1998), APEX2 (Bruker, 2006), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures..

Selected geometric parameters (Å, º) for (I) top
N1—C21.361 (2)C4—C51.414 (2)
N1—C61.363 (2)C5—O21.356 (2)
C2—O11.277 (2)C5—C61.362 (2)
C2—C31.431 (2)C6—Cl11.7162 (17)
C3—C41.356 (2)
C2—N1—C6123.64 (14)O2—C5—C6120.16 (16)
O1—C2—N1119.31 (15)O2—C5—C4123.23 (15)
O1—C2—C3124.95 (15)C6—C5—C4116.59 (16)
N1—C2—C3115.74 (15)C5—C6—N1121.55 (16)
C4—C3—C2120.48 (16)C5—C6—Cl1122.48 (14)
C3—C4—C5121.98 (16)N1—C6—Cl1115.97 (12)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.881.862.7393 (18)177.4
O2—H2···O1ii0.841.832.6507 (17)166.0
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+3/2, y1/2, z+1/2.
Selected geometric parameters (Å, º) for (IIa) top
N1A—C2A1.333 (4)N1B—C2B1.333 (4)
N1A—C6A1.340 (4)N1B—C6B1.334 (4)
C2A—O1A1.343 (3)C2B—O1B1.355 (4)
C2A—C3A1.391 (4)C2B—C3B1.390 (4)
C3A—C4A1.373 (4)C3B—C4B1.370 (4)
C4A—C5A1.397 (4)C4B—C5B1.399 (4)
C5A—C6A1.366 (4)C5B—O2B1.351 (4)
C5A—O2A1.375 (3)C5B—C6B1.376 (4)
C6A—Cl1A1.738 (3)C6B—Cl1B1.740 (3)
C2A—N1A—C6A117.9 (3)C2B—N1B—C6B117.7 (3)
N1A—C2A—O1A119.0 (3)N1B—C2B—O1B117.7 (3)
N1A—C2A—C3A122.7 (3)N1B—C2B—C3B122.5 (3)
O1A—C2A—C3A118.2 (3)O1B—C2B—C3B119.9 (3)
C4A—C3A—C2A118.1 (3)C4B—C3B—C2B118.6 (3)
C3A—C4A—C5A120.0 (3)C3B—C4B—C5B120.2 (3)
C6A—C5A—O2A124.8 (3)O2B—C5B—C6B118.9 (3)
C6A—C5A—C4A117.4 (3)O2B—C5B—C4B124.8 (3)
O2A—C5A—C4A117.7 (3)C6B—C5B—C4B116.3 (3)
N1A—C6A—C5A123.9 (3)N1B—C6B—C5B124.8 (3)
N1A—C6A—Cl1A116.1 (2)N1B—C6B—Cl1B116.0 (2)
C5A—C6A—Cl1A120.0 (2)C5B—C6B—Cl1B119.2 (2)
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.892.721 (3)169.2
O2A—H2A···O2Ai0.841.892.647 (2)148.6
O1B—H1B···N1A0.841.882.707 (3)170.1
O2B—H2B···O1Bii0.841.892.723 (3)173.5
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.892.726 (2)172.0
O2A—H2A···O2Ai0.841.902.6487 (15)147.8
O1B—H1B···N1A0.841.882.708 (2)170.5
O2B—H2B···O1Bii0.841.912.738 (2)167.6
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
Hydrogen-bond geometry (Å, º) for (IIc) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.902.727 (3)166.8
O2A—H2A···O2Ai0.841.882.6448 (17)150.0
O1B—H1B···N1A0.841.882.710 (3)170.4
O2B—H2B···O1Bii0.841.902.728 (2)167.8
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
Hydrogen-bond geometry (Å, º) for (IId) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···N1B0.841.892.721 (2)169.4
O2A—H2A···O2Ai0.841.892.6453 (15)148.3
O1B—H1B···N1A0.841.882.709 (2)170.3
O2B—H2B···O1Bii0.841.912.746 (2)170.4
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+1/4, x+3/4, z+7/4.
 

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