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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 117-119

Crystal structure of N-hy­dr­oxy­picolinamide monohydrate

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aDepartment of Chemistry, National Taras Shevchenko University of Kyiv, Volodymyrska Street 64, 01601 Kiev, Ukraine, and bSSI "Institute for Single Crystals", National Academy of Sciences of Ukraine, Lenina ave. 60, Kharkiv 61001, Ukraine
*Correspondence e-mail: safyanova_inna@mail.ru

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 20 November 2015; accepted 23 December 2015; online 6 January 2016)

The crystal structure of the title compound, C6H6N2O2·H2O, consists of N-hy­droxy­picolinamide and water mol­ecules connected through O—H⋯O and N—H⋯N hydrogen bonds. The O—H⋯O inter­actions and ππ stacking inter­actions between the pyridine rings [centroid–centroid distance = 3.427 (1) Å] organize the components into columns extending along the b axis and the N—H⋯N hydrogen bonds link these columns into a two-dimensional framework parallel to (100). The N-hy­droxy­picolinamide mol­ecule adopts a strongly flattened conformation and only the O—H group H atom deviates significantly from the mol­ecule best plane. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6 (2)°. The conformation about the hydroxamic group C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E.

1. Chemical context

Hydroxamic acids (HA) are weak organic acids with the general formula R—C(=O)—NH—OH. HA can exist as keto and imino­(enol) tautomers with two isomers, E and Z, for each form, and in the zwitterionic form (see Scheme below). They have found broad application in coordination chemistry due to their diversity and comparatively facile synthesis (Świątek-Kozłowska et al., 2000[Świątek-Kozłowska, J., Fritsky, I. O., Dobosz, A., Karaczyn, A., Dudarenko, N. M., Sliva, T. Yu., Gumienna-Kontecka, E. & Jerzykiewicz, L. (2000). J. Chem. Soc. Dalton Trans. pp. 4064-4068.]; Dobosz et al., 1999[Dobosz, A., Dudarenko, N. M., Fritsky, I. O., Głowiak, T., Karaczyn, A., Kozłowski, H., Sliva, T. Yu. & Świątek-Kozłowska, J. (1999). J. Chem. Soc. Dalton Trans. pp. 743-750.]). In addition, they exhibit biological activities related to their enzyme-inhibitory properties (Marmion et al., 2013[Marmion, C. J., Parker, J. P. & Nolan, K. B. (2013). Comprehensive Inorganic Chemistry II: From Elements to Applications, edited by J. Reedijk & K. Poeppelmeier, Vol. 3, pp. 684-708. Amsterdam: Elsevier.]). HAs are widely used in coordination and supra­molecular chemistry as scaffolds in the preparation of metallacrowns (Seda et al., 2007[Seda, S. H., Janczak, J. & Lisowski, J. (2007). Eur. J. Inorg. Chem. pp. 3015-3022.]; Jankolovits et al., 2013[Jankolovits, J., Kampf, J. W. & Pecoraro, V. L. (2013). Inorg. Chem. 52, 5063-5076.]; Safyanova et al., 2015[Safyanova, I. S., Golenya, I. A., Pavlenko, V. A., Gumienna-Kontecka, E., Pekhnyo, V. I., Bon, V. V. & Fritsky, I. O. (2015). Z. Anorg. Allg. Chem. 641, 2326-2332.]) and as building blocks of coordination polymers (Gumienna-Kontecka et al., 2007[Gumienna-Kontecka, E., Golenya, I. A., Dudarenko, N. M., Dobosz, A., Haukka, M., Fritsky, I. O. & Świątek-Kozłowska, J. (2007). New J. Chem. 31, 1798-1805.]; Golenya et al., 2014[Golenya, I. A., Gumienna-Kontecka, E., Haukka, M., Korsun, O. M., Kalugin, O. N. & Fritsky, I. O. (2014). CrystEngComm, 16, 1904-1918.]; Pavlishchuk et al., 2010[Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Thompson, L. K., Fritsky, I. O., Addison, A. W. & Hunter, A. D. (2010). Eur. J. Inorg. Chem. pp. 4851-4858.], 2011[Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Shvets, O. V., Fritsky, I. O., Lofland, S. E., Addison, A. W. & Hunter, A. D. (2011). Eur. J. Inorg. Chem. pp. 4826-4836.]).

[Scheme 2]

N-Hy­droxy­picolinamide, known also as picoline-2-hydroxamic acid (o-PicHA), has been used extensively for the synthesis of polynuclear complexes, especially in the synthesis of diverse metallacrowns (Stemmler et al., 1999[Stemmler, A. J., Kampf, J. W., Kirk, M. L., Atasi, B. H. & Pecoraro, V. L. (1999). Inorg. Chem. 38, 2807-2817.]; Seda et al., 2007[Seda, S. H., Janczak, J. & Lisowski, J. (2007). Eur. J. Inorg. Chem. pp. 3015-3022.]; Jankolovits et al., 2013[Jankolovits, J., Kampf, J. W. & Pecoraro, V. L. (2013). Inorg. Chem. 52, 5063-5076.]; Golenya et al., 2012[Golenya, I. A., Gumienna-Kontecka, E., Boyko, A. N., Haukka, M. & Fritsky, I. O. (2012). Inorg. Chem. 51, 6221-6227.]; Gumienna-Kontecka et al., 2013[Gumienna-Kontecka, E., Golenya, I. A., Szebesczyk, A., Haukka, M., Krämer, R. & Fritsky, I. O. (2013). Inorg. Chem. 52, 7633-7644.]). Presently, the Cambridge Structural Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) contains more than 20 entries of coordination compounds based on N-hy­droxy­picolinamide.

Our inter­est in N-hy­droxy­picolinamide stems also from the fact that in the course of synthesis of the title and related compounds from 2-picolinic acid esters (Hynes, 1970[Hynes, J. B. (1970). J. Med. Chem. 13, 1235-1237.]), the products are frequently contaminated with impurities that result from hydrolysis of the ester or hydroxamic groups to the carb­oxy­lic group. Structural information about the title compound will be helpful in controlling the purity of the synthesised ligand by powder diffraction.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title compound is presented in Fig. 1[link]. The crystal structure of the title compound consists of an N-hy­droxy­picolinamide mol­ecule in the Z-keto tautomeric form in agreement with the C=O and C—N bond lengths [1.234  (2) and 1.325 (2) Å, respectively] and a water mol­ecule. The N-hy­droxy­picolinamide mol­ecule adopts a strongly flattened conformation and only the O—H group H atom deviates significantly from the mol­ecular best plane. The maximum deviation from this plane for non-hydrogen atom is 0.083 (1) Å for O1 and the hydroxyl group H2 atom is displaced from the mean plane by 0.80 (1) Å in the direction of the water mol­ecule. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6 (2)°. The configuration about the hydroxamic group C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E [torsion angles O2—N2—C6—O1 −0.4 (3)°, N1—C1—C6—O1 175.6 (2)°].

[Figure 1]
Figure 1
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius. The dashed line indicates a hydrogen bond.

3. Supra­molecular features

The mol­ecular components of the title compound are connected by O—H⋯O and N—H⋯N hydrogen bonds (Table 1[link]) into a two-dimensional framework parallel to (100) (Fig. 2[link]). The O—H⋯O inter­actions and ππ stacking inter­actions between the pyridine rings [centroid–centroid distance 3.427 (1) Å] organize the crystal components into columns extending along the b axis while the N—H⋯N hydrogen bonds link these columns into a two-dimensional framework parallel to (100) (Fig.2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O1W 0.82 1.86 2.656 (2) 163
N2—H2A⋯N1i 0.86 2.31 3.010 (2) 139
O1W—H1WA⋯O1ii 0.85 2.14 2.976 (2) 168
O1W—H1WB⋯O1iii 0.85 1.94 2.788 (2) 173
Symmetry codes: (i) [-x+1, y, -z+{\script{1\over 2}}]; (ii) x, y+1, z; (iii) -x+1, -y+1, -z+1.
[Figure 2]
Figure 2
A packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) revealed two crystal structures of isomeric pyridine hydroxamic acids and the crystal structure of 2,6-pyridinedi­hydroxamic acid (Golenya et al., 2007[Golenya, I. A., Haukka, M., Fritsky, I. O. & Gumienna-Kontecka, E. (2007). Acta Cryst. E63, o1515-o1517.]; Makhmudova et al., 2001[Makhmudova, N. K., Kadyrova, Z. Ch., Del'yaridi, E. A. & Sharipov, Kh. T. (2001). Russ. J. Org. Chem. 37, 866-868.]; Griffith et al., 2008[Griffith, D., Chopra, A., Müller-Bunz, H. & Marmion, C. (2008). Dalton Trans. 48, 6933-6939.]).

5. Synthesis and crystallization

The title compound was obtained by the reaction of methyl 2-picolinate and hydroxyl­amine in methanol solution according to a reported procedure (Hynes, 1970[Hynes, J. B. (1970). J. Med. Chem. 13, 1235-1237.]). Colorless crystals suitable for X-ray diffraction were obtained from a methanol solution by slow evaporation at room temperature (yield 79%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The crystal was modelled as a non-merohedral twin with the volume ratio of two twin domains refined at 89:19. The C—H, N—H and O—H hydrogen atoms of the organic mol­ecule were found from the difference Fourier maps but for further calculations they were positioned geometrically and constrained to ride on their parent atoms with C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.82 Å, and with Uiso = 1.2Ueq(C,N) or Uiso = 1.5Ueq(O). The H atoms of the water mol­ecule were located in the difference Fourier maps, the O—H distances standardized to 0.85 Å and refined in riding-model approximation with Uiso(H) = 1.5Ueq(O).

Table 2
Experimental details

Crystal data
Chemical formula C6H6N2O2·H2O
Mr 156.14
Crystal system, space group Monoclinic, C2/c
Temperature (K) 298
a, b, c (Å) 18.7471 (13), 3.8129 (4), 20.4813 (17)
β (°) 100.570 (7)
V3) 1439.2 (2)
Z 8
Radiation type Mo Kα
μ (mm−1) 0.12
Crystal size (mm) 0.4 × 0.4 × 0.1
 
Data collection
Diffractometer Agilent Xcalibur, Sapphire3
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.476, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 2491, 1401, 1053
Rint 0.037
(sin θ/λ)max−1) 0.617
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.143, 0.99
No. of reflections 1401
No. of parameters 102
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.19, −0.25
Computer programs: CrysAlis PRO (Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Supporting information


Chemical context top

Hydroxamic acids (HA) are weak organic acids with the general formula R—C(O)—NH—OH. HA can exist as keto and imino­(enol) tautomers with two isomers, E and Z, for each form, and in the zwitterionic form (see Scheme below). They have found broad application in coordination chemistry due to their diversity and comparatively facile synthesis (Świątek-Kozłowska et al., 2000; Dobosz et al., 1999). In addition, they exhibit biological activities related to their enzyme-inhibitory properties (Marmion et al., 2013). HA are widely used in coordination and supra­molecular chemistry as scaffolds in the preparation of metallacrowns (Seda et al., 2007; Jankolovits et al., 2013; Safyanova et al., 2015) and as building blocks of coordination polymers (Gumienna-Kontecka et al., 2007; Golenya et al., 2014; Pavlishchuk et al., 2010, 2011).

N-Hy­droxy­picolinamide, known also as picoline-2-hydroxamic acid (o-PicHA), has been used extensively for the synthesis of polynuclear complexes, especially in the synthesis of diverse metallacrowns (Stemmler et al., 1999; Seda et al., 2007; Jankolovits et al., 2013; Golenya et al., 2012; Gumienna-Kontecka et al., 2013). Presently, the Cambridge Structural Database (Groom & Allen, 2014) contains more than 20 entries of coordination compounds based on N-hy­droxy­picolinamide.

Our inter­est in N-hy­droxy­picolinamide stems also from the fact that in the course of synthesis of the title and related compounds from 2-picolinic acid esters (Hynes, 1970), the products are frequently contaminated with impurities that result from hydrolysis of the ester or hydroxamic groups to the carb­oxy­lic group. Structural information about the title compound will be helpful in controlling the purity of the synthesized ligand by powder diffraction.

Structural commentary top

The molecular structure of the title compound is presented in Fig. 1. The crystal structure of the title compound consists of an N-hy­droxy­picolinamide molecule in the Z-keto tautomeric form and a water molecule. The N-hy­droxy­picolinamide molecule adopts a strongly flattened conformation and only the O—H group H atom deviates significantly from the molecular best plane. The maximum deviation from this plane for non-hydrogen atom is 0.083 (1) Å for O1 and the hydroxyl group H2 atom is displaced from the mean plane by 0.80 (1) Å in the direction of the water molecule. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6 (2)°. The configuration about the hydroxamic group C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E [torsion angles O2—N2—C6—O1 − 0.4 (3)°, N1—C1—C6—O1 175.6 (2)°].

Supra­molecular features top

The molecular components of the title compound are connected by O—H···O and N—H···N hydrogen bonds (Table 1) into a two-dimensional framework parallel to (100) (Fig. 2). The O—H···O inter­actions and ππ stacking inter­actions between the pyridine rings [centroid–centroid distance 3.427 (1) Å] organize the crystal components into columns extending along the b axis while the N—H···N hydrogen bonds link these columns into a two-dimensional framework parallel to (100) (Fig.2).

Database survey top

A search of the Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen, 2014) reveals two crystal structures of isomeric pyridine hydroxamic acids and the crystal structure of 2,6-pyridinedi­hydroxamic acid (Golenya et al., 2007; Makhmudova et al., 2001; Griffith et al., 2008).

Synthesis and crystallization top

The title compound was obtained by the reaction of methyl 2-picolinate and hydroxyl­amine in methanol according to a reported procedure (Hynes, 1970). Colorless crystals suitable for X-ray diffraction were obtained from a methanol solution by slow evaporation at room temperature (yield 79%).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal was refined as a non-merohedral twin with the volume ratio of two twin domains refined at 89:19. The C—H, N—H and O—H hydrogen atoms of the organic molecule were found from the difference Fourier maps but for further calculations they were positioned geometrically and constrained to ride on their parent atoms with C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.82 Å, and with Uiso = 1.2Ueq(C,N) or Uiso = 1.5Ueq(O). The H atoms of the water molecule were located in the difference Fourier maps, the O—H distances standardized to 0.85 Å and refined in riding-model approximation with Uiso(H) = 1.5Ueq(O).

Structure description top

Hydroxamic acids (HA) are weak organic acids with the general formula R—C(O)—NH—OH. HA can exist as keto and imino­(enol) tautomers with two isomers, E and Z, for each form, and in the zwitterionic form (see Scheme below). They have found broad application in coordination chemistry due to their diversity and comparatively facile synthesis (Świątek-Kozłowska et al., 2000; Dobosz et al., 1999). In addition, they exhibit biological activities related to their enzyme-inhibitory properties (Marmion et al., 2013). HA are widely used in coordination and supra­molecular chemistry as scaffolds in the preparation of metallacrowns (Seda et al., 2007; Jankolovits et al., 2013; Safyanova et al., 2015) and as building blocks of coordination polymers (Gumienna-Kontecka et al., 2007; Golenya et al., 2014; Pavlishchuk et al., 2010, 2011).

N-Hy­droxy­picolinamide, known also as picoline-2-hydroxamic acid (o-PicHA), has been used extensively for the synthesis of polynuclear complexes, especially in the synthesis of diverse metallacrowns (Stemmler et al., 1999; Seda et al., 2007; Jankolovits et al., 2013; Golenya et al., 2012; Gumienna-Kontecka et al., 2013). Presently, the Cambridge Structural Database (Groom & Allen, 2014) contains more than 20 entries of coordination compounds based on N-hy­droxy­picolinamide.

Our inter­est in N-hy­droxy­picolinamide stems also from the fact that in the course of synthesis of the title and related compounds from 2-picolinic acid esters (Hynes, 1970), the products are frequently contaminated with impurities that result from hydrolysis of the ester or hydroxamic groups to the carb­oxy­lic group. Structural information about the title compound will be helpful in controlling the purity of the synthesized ligand by powder diffraction.

The molecular structure of the title compound is presented in Fig. 1. The crystal structure of the title compound consists of an N-hy­droxy­picolinamide molecule in the Z-keto tautomeric form and a water molecule. The N-hy­droxy­picolinamide molecule adopts a strongly flattened conformation and only the O—H group H atom deviates significantly from the molecular best plane. The maximum deviation from this plane for non-hydrogen atom is 0.083 (1) Å for O1 and the hydroxyl group H2 atom is displaced from the mean plane by 0.80 (1) Å in the direction of the water molecule. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6 (2)°. The configuration about the hydroxamic group C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E [torsion angles O2—N2—C6—O1 − 0.4 (3)°, N1—C1—C6—O1 175.6 (2)°].

The molecular components of the title compound are connected by O—H···O and N—H···N hydrogen bonds (Table 1) into a two-dimensional framework parallel to (100) (Fig. 2). The O—H···O inter­actions and ππ stacking inter­actions between the pyridine rings [centroid–centroid distance 3.427 (1) Å] organize the crystal components into columns extending along the b axis while the N—H···N hydrogen bonds link these columns into a two-dimensional framework parallel to (100) (Fig.2).

A search of the Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen, 2014) reveals two crystal structures of isomeric pyridine hydroxamic acids and the crystal structure of 2,6-pyridinedi­hydroxamic acid (Golenya et al., 2007; Makhmudova et al., 2001; Griffith et al., 2008).

Synthesis and crystallization top

The title compound was obtained by the reaction of methyl 2-picolinate and hydroxyl­amine in methanol according to a reported procedure (Hynes, 1970). Colorless crystals suitable for X-ray diffraction were obtained from a methanol solution by slow evaporation at room temperature (yield 79%).

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal was refined as a non-merohedral twin with the volume ratio of two twin domains refined at 89:19. The C—H, N—H and O—H hydrogen atoms of the organic molecule were found from the difference Fourier maps but for further calculations they were positioned geometrically and constrained to ride on their parent atoms with C—H = 0.93 Å, N—H = 0.86 Å and O—H = 0.82 Å, and with Uiso = 1.2Ueq(C,N) or Uiso = 1.5Ueq(O). The H atoms of the water molecule were located in the difference Fourier maps, the O—H distances standardized to 0.85 Å and refined in riding-model approximation with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius. The dashed line indicates a hydrogen bond.
[Figure 2] Fig. 2. A packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
N-Hydroxypyridine-2-carboxamide monohydrate top
Crystal data top
C6H6N2O2·H2ODx = 1.441 Mg m3
Mr = 156.14Melting point: 393 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 18.7471 (13) ÅCell parameters from 893 reflections
b = 3.8129 (4) Åθ = 4.1–29.0°
c = 20.4813 (17) ŵ = 0.12 mm1
β = 100.570 (7)°T = 298 K
V = 1439.2 (2) Å3Plate, clear colourless
Z = 80.4 × 0.4 × 0.1 mm
F(000) = 656
Data collection top
Agilent Xcalibur, Sapphire3
diffractometer
1401 independent reflections
Radiation source: Enhance (Mo) X-ray Source1053 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 16.1827 pixels mm-1θmax = 26.0°, θmin = 3.3°
ω scansh = 2222
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
k = 44
Tmin = 0.476, Tmax = 1.000l = 2424
2491 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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0751P)2]
where P = (Fo2 + 2Fc2)/3
1401 reflections(Δ/σ)max < 0.001
102 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C6H6N2O2·H2OV = 1439.2 (2) Å3
Mr = 156.14Z = 8
Monoclinic, C2/cMo Kα radiation
a = 18.7471 (13) ŵ = 0.12 mm1
b = 3.8129 (4) ÅT = 298 K
c = 20.4813 (17) Å0.4 × 0.4 × 0.1 mm
β = 100.570 (7)°
Data collection top
Agilent Xcalibur, Sapphire3
diffractometer
1401 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
1053 reflections with I > 2σ(I)
Tmin = 0.476, Tmax = 1.000Rint = 0.037
2491 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 0.99Δρmax = 0.19 e Å3
1401 reflectionsΔρmin = 0.25 e Å3
102 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. Refined as a 2-component twin. 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
O10.52649 (8)0.3700 (4)0.43254 (7)0.0468 (5)
O20.40179 (7)0.5190 (5)0.35109 (7)0.0506 (5)
H20.39160.64290.38080.076*
N10.59448 (9)0.8106 (5)0.30306 (8)0.0366 (5)
N20.46909 (9)0.6163 (5)0.33806 (8)0.0410 (5)
H2A0.47220.73050.30250.049*
C10.59810 (10)0.6575 (5)0.36271 (9)0.0323 (5)
C20.66231 (11)0.6152 (6)0.40743 (11)0.0428 (6)
H2B0.66280.51190.44870.051*
C30.72601 (11)0.7308 (6)0.38915 (13)0.0519 (7)
H30.77030.70300.41780.062*
C40.72296 (11)0.8863 (6)0.32857 (13)0.0482 (6)
H40.76500.96560.31540.058*
C50.65653 (12)0.9234 (6)0.28737 (11)0.0434 (6)
H50.65491.03270.24650.052*
C60.52864 (10)0.5321 (6)0.38079 (9)0.0332 (5)
O1W0.39862 (8)0.9488 (5)0.45255 (8)0.0501 (5)
H1WA0.43081.09380.44550.075*
H1WB0.42020.83510.48610.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0447 (8)0.0657 (11)0.0287 (8)0.0009 (7)0.0035 (6)0.0147 (7)
O20.0332 (8)0.0832 (13)0.0350 (9)0.0121 (8)0.0051 (6)0.0062 (8)
N10.0370 (9)0.0465 (11)0.0267 (9)0.0051 (8)0.0069 (7)0.0036 (8)
N20.0307 (9)0.0670 (13)0.0252 (9)0.0038 (8)0.0048 (7)0.0107 (9)
C10.0344 (10)0.0371 (11)0.0252 (10)0.0012 (8)0.0047 (8)0.0061 (8)
C20.0369 (11)0.0543 (14)0.0347 (12)0.0052 (9)0.0000 (9)0.0030 (11)
C30.0322 (11)0.0640 (17)0.0554 (16)0.0028 (11)0.0027 (10)0.0116 (13)
C40.0351 (11)0.0569 (15)0.0552 (15)0.0091 (10)0.0156 (10)0.0148 (12)
C50.0435 (12)0.0538 (15)0.0348 (12)0.0062 (11)0.0121 (9)0.0047 (11)
C60.0359 (11)0.0409 (12)0.0224 (10)0.0012 (9)0.0043 (8)0.0013 (9)
O1W0.0408 (8)0.0687 (11)0.0404 (9)0.0044 (8)0.0068 (7)0.0163 (8)
Geometric parameters (Å, º) top
O1—C61.234 (2)C2—C31.387 (3)
O2—N21.387 (2)C2—H2B0.9300
O2—H20.8200C3—C41.367 (3)
N1—C51.334 (3)C3—H30.9300
N1—C11.344 (3)C4—C51.378 (3)
N2—C61.325 (2)C4—H40.9300
N2—H2A0.8600C5—H50.9300
C1—C21.382 (3)O1W—H1WA0.8503
C1—C61.496 (3)O1W—H1WB0.8499
N2—O2—H2109.5C4—C3—H3120.4
C5—N1—C1117.26 (17)C2—C3—H3120.4
C6—N2—O2119.60 (16)C3—C4—C5118.9 (2)
C6—N2—H2A120.2C3—C4—H4120.6
O2—N2—H2A120.2C5—C4—H4120.6
N1—C1—C2123.08 (19)N1—C5—C4123.4 (2)
N1—C1—C6117.54 (16)N1—C5—H5118.3
C2—C1—C6119.38 (18)C4—C5—H5118.3
C1—C2—C3118.2 (2)O1—C6—N2122.15 (18)
C1—C2—H2B120.9O1—C6—C1122.66 (17)
C3—C2—H2B120.9N2—C6—C1115.17 (17)
C4—C3—C2119.2 (2)H1WA—O1W—H1WB102.7
C5—N1—C1—C20.3 (3)C3—C4—C5—N11.0 (4)
C5—N1—C1—C6179.67 (17)O2—N2—C6—O10.4 (3)
N1—C1—C2—C31.2 (3)O2—N2—C6—C1178.54 (17)
C6—C1—C2—C3179.4 (2)N1—C1—C6—O1175.6 (2)
C1—C2—C3—C41.0 (3)C2—C1—C6—O15.0 (3)
C2—C3—C4—C50.0 (4)N1—C1—C6—N26.2 (3)
C1—N1—C5—C40.8 (3)C2—C1—C6—N2173.20 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1W0.821.862.656 (2)163
N2—H2A···N1i0.862.313.010 (2)139
O1W—H1WA···O1ii0.852.142.976 (2)168
O1W—H1WB···O1iii0.851.942.788 (2)173
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y+1, z; (iii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1W0.821.862.656 (2)162.5
N2—H2A···N1i0.862.313.010 (2)138.7
O1W—H1WA···O1ii0.852.142.976 (2)168.3
O1W—H1WB···O1iii0.851.942.788 (2)173.0
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y+1, z; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC6H6N2O2·H2O
Mr156.14
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)18.7471 (13), 3.8129 (4), 20.4813 (17)
β (°) 100.570 (7)
V3)1439.2 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.4 × 0.4 × 0.1
Data collection
DiffractometerAgilent Xcalibur, Sapphire3
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.476, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
2491, 1401, 1053
Rint0.037
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.143, 0.99
No. of reflections1401
No. of parameters102
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.25

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

Financial support from the European Community's Seventh Framework Programme (FP7/2007–2013) under grant agreement PIRSES-GA-2013–611488 is gratefully acknowledged. KAO acknowledges for the DAAD fellowship (Leonhard-Euler-Programm).

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Volume 72| Part 2| February 2016| Pages 117-119
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