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

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ISSN: 2056-9890

Crystal structure of 2,6-di­methyl-4-pyridone hemihydrate

aDepartment of Science & Math, Massasoit Community College, 1 Massasoit Boulevard, Brockton, MA 02302, USA, and bDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
*Correspondence e-mail: dmanke@umassd.edu

Edited by K. Fejfarova, Institute of Macromolecular Chemistry, AS CR, v.v.i, Czech Republic (Received 25 June 2015; accepted 29 June 2015; online 4 July 2015)

The title compound (systematic name: 2,6-dimethyl-1H-pyridin-4-one hemihydrate), C7H9NO·0.5H2O, has a single planar mol­ecule in the asymmetric unit with the non-H atoms possessing a mean deviation from planarity of 0.021 Å. There is also half of a water mol­ecule present in the asymmetric unit. In the crystal, infinite (001) sheets are formed by N—H⋯O and O—H⋯O hydrogen bonds.

1. Related literature

For the crystal structure of the parent 4-pyridone, see: Jones (2001[Jones, P. G. (2001). Acta Cryst. C57, 880-882.]); Tyl et al. (2008[Tyl, A., Nowak, M. & Kusz, J. (2008). Acta Cryst. C64, o661-o664.]). For the title compound bound to zirconium, see: Castillo et al. (1987[Castillo, S., Herault, V. & Declercq, J.-P. (1987). Acta Cryst. C43, 1530-1533.]). For the structure of a chloro-substituted variant of the title compound, see: Boer (1972[Boer, F. P. (1972). Acta Cryst. B28, 3200-3206.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C7H9NO·0.5H2O

  • Mr = 132.16

  • Orthorhombic, A b a 2

  • a = 12.4859 (17) Å

  • b = 14.3697 (19) Å

  • c = 7.732 (1) Å

  • V = 1387.3 (3) Å3

  • Z = 8

  • Cu Kα radiation

  • μ = 0.73 mm−1

  • T = 120 K

  • 0.5 × 0.1 × 0.1 mm

2.2. Data collection

  • Bruker Venture D8 CMOS diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.554, Tmax = 0.754

  • 11786 measured reflections

  • 1366 independent reflections

  • 1352 reflections with I > 2σ(I)

  • Rint = 0.060

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.078

  • S = 1.09

  • 1366 reflections

  • 95 parameters

  • 3 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.15 e Å−3

  • Δρmin = −0.19 e Å−3

  • Absolute structure: Flack x determined using 611 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.].

  • Absolute structure parameter: 0.05 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O1 0.86 (1) 1.96 (1) 2.8174 (17) 173 (2)
N1—H1⋯O1i 0.87 (1) 1.86 (1) 2.7154 (18) 166 (3)
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z].

Data collection: APEX2 (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: 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.]); software used to prepare material for publication: OLEX2 and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The structure of the title compound shows that 2,6-di­methyl-4-hy­droxy­pyridine takes the pyridone form in the solid state. Though the title compound has not been crystallographically characterized, a structure of the molecule bound to zirconium has been reported (Castillo et al., 1987) with similar bond distances and angles observed. The parent 4-pyridone has been structurally characterized (Tyl et al., 2008) and exhibits similar chains linked by head-to-tail N–H···O hydrogen bonds, which are also observed in the close derivative Clopidol (Boer, 1972). While the title compound crystallizes in a 2:1 ratio of pyridone to water, the hydrate of the parent molecule crystallizes in a 5:6 ratio (Jones, 2001).

The molecular structure of the title compound is shown in Figure 1. The molecule is near planar with the non-hydrogen atoms possessing a mean deviation from the plane of 0.021 Å. Head-to-tail N1–H1···O1 hydrogen bonding leads to chains that are further linked by O2–H2···O1 hydrogen bonds with water molecules in the crystal to form two-dimensional (001) sheets. The packing of the title compound indicating hydrogen bonding is shown in Figure 2.

Experimental top

A commercial sample (Oakwood Chemical) of 4-hy­droxy­pyridine was used for the crystallization. Crystals suitable for single crystal X-ray analysis were grown by slow evaporation of a methanol solution.

Refinement top

All non-hydrogen atoms were refined anisotropically (XL) by full matrix least squares on F2. Hydrogen atoms H1 and H2 were found from a Fourier difference map. H1 was refined at a fixed distance of 0.87 (0.005) Å and an isotropic displacement parameter 1.20 times Ueq of the parent N atom. H2 was refined at a fixed distance of 0.86 (0.005) Å and an isotropic displacement parameter 1.50 times Ueq of the parent O atom. The remaining hydrogen atoms were placed in calculated positions and then refined with riding models with C—H lengths of 0.98 Å for (CH3) and 0.95 Å for (CH) with isotropic displacement parameters set to 1.20 times Ueq of the parent C atoms.

Related literature top

For the crystal structure of the parent 4-pyridone, see: Jones (2001); Tyl et al. (2008). For the title compound bound to zirconium, see: Castillo et al. (1987). For the structure of a chloro-substituted variant of the title compound, see: Boer (1972).

Structure description top

The structure of the title compound shows that 2,6-di­methyl-4-hy­droxy­pyridine takes the pyridone form in the solid state. Though the title compound has not been crystallographically characterized, a structure of the molecule bound to zirconium has been reported (Castillo et al., 1987) with similar bond distances and angles observed. The parent 4-pyridone has been structurally characterized (Tyl et al., 2008) and exhibits similar chains linked by head-to-tail N–H···O hydrogen bonds, which are also observed in the close derivative Clopidol (Boer, 1972). While the title compound crystallizes in a 2:1 ratio of pyridone to water, the hydrate of the parent molecule crystallizes in a 5:6 ratio (Jones, 2001).

The molecular structure of the title compound is shown in Figure 1. The molecule is near planar with the non-hydrogen atoms possessing a mean deviation from the plane of 0.021 Å. Head-to-tail N1–H1···O1 hydrogen bonding leads to chains that are further linked by O2–H2···O1 hydrogen bonds with water molecules in the crystal to form two-dimensional (001) sheets. The packing of the title compound indicating hydrogen bonding is shown in Figure 2.

A commercial sample (Oakwood Chemical) of 4-hy­droxy­pyridine was used for the crystallization. Crystals suitable for single crystal X-ray analysis were grown by slow evaporation of a methanol solution.

For the crystal structure of the parent 4-pyridone, see: Jones (2001); Tyl et al. (2008). For the title compound bound to zirconium, see: Castillo et al. (1987). For the structure of a chloro-substituted variant of the title compound, see: Boer (1972).

Refinement details top

All non-hydrogen atoms were refined anisotropically (XL) by full matrix least squares on F2. Hydrogen atoms H1 and H2 were found from a Fourier difference map. H1 was refined at a fixed distance of 0.87 (0.005) Å and an isotropic displacement parameter 1.20 times Ueq of the parent N atom. H2 was refined at a fixed distance of 0.86 (0.005) Å and an isotropic displacement parameter 1.50 times Ueq of the parent O atom. The remaining hydrogen atoms were placed in calculated positions and then refined with riding models with C—H lengths of 0.98 Å for (CH3) and 0.95 Å for (CH) with isotropic displacement parameters set to 1.20 times Ueq of the parent C atoms.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.
[Figure 2] Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.
2,6-Dimethyl-1H-pyridin-4-one hemihydrate top
Crystal data top
C7H9NO·0.5H2OF(000) = 568
Mr = 132.16Dx = 1.266 Mg m3
Orthorhombic, Aba2Cu Kα radiation, λ = 1.54178 Å
Hall symbol: A 2 -2acCell parameters from 9829 reflections
a = 12.4859 (17) Åθ = 7.1–72.4°
b = 14.3697 (19) ŵ = 0.73 mm1
c = 7.732 (1) ÅT = 120 K
V = 1387.3 (3) Å3NEEDLE, colourless
Z = 80.5 × 0.1 × 0.1 mm
Data collection top
Bruker Venture D8 CMOS
diffractometer
1366 independent reflections
Radiation source: microfocus Cu1352 reflections with I > 2σ(I)
HELIOS MX monochromatorRint = 0.060
φ and ω scansθmax = 72.4°, θmin = 7.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 1515
Tmin = 0.554, Tmax = 0.754k = 1717
11786 measured reflectionsl = 99
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.0453P)2 + 0.3383P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.078(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.15 e Å3
1366 reflectionsΔρmin = 0.19 e Å3
95 parametersAbsolute structure: Flack x determined using 611 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013.
3 restraintsAbsolute structure parameter: 0.05 (12)
Crystal data top
C7H9NO·0.5H2OV = 1387.3 (3) Å3
Mr = 132.16Z = 8
Orthorhombic, Aba2Cu Kα radiation
a = 12.4859 (17) ŵ = 0.73 mm1
b = 14.3697 (19) ÅT = 120 K
c = 7.732 (1) Å0.5 × 0.1 × 0.1 mm
Data collection top
Bruker Venture D8 CMOS
diffractometer
1366 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
1352 reflections with I > 2σ(I)
Tmin = 0.554, Tmax = 0.754Rint = 0.060
11786 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078Δρmax = 0.15 e Å3
S = 1.09Δρmin = 0.19 e Å3
1366 reflectionsAbsolute structure: Flack x determined using 611 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013.
95 parametersAbsolute structure parameter: 0.05 (12)
3 restraints
Special details top

Experimental. Absorption correction: SADABS-2014/4 (Bruker,2014) was used for absorption correction. wR2(int) was 0.1440 before and 0.0881 after correction. The Ratio of minimum to maximum transmission is 0.7350. The λ/2 correction factor is 0.00150.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.47723 (9)0.33620 (8)0.49203 (19)0.0287 (3)
O20.50000.50000.6889 (3)0.0399 (5)
N10.16883 (11)0.24949 (11)0.4446 (2)0.0215 (3)
C30.35308 (14)0.22232 (12)0.3962 (2)0.0234 (4)
H30.40830.18410.35040.028*
C20.24877 (14)0.19343 (12)0.3853 (2)0.0222 (4)
C40.38007 (12)0.30864 (12)0.4748 (2)0.0226 (4)
C70.09367 (14)0.39066 (13)0.5690 (3)0.0265 (4)
H7A0.06300.42100.46690.040*
H7B0.11580.43810.65270.040*
H7C0.03990.34990.62180.040*
C60.18900 (13)0.33399 (11)0.5164 (2)0.0217 (4)
C10.21576 (15)0.10115 (12)0.3125 (3)0.0270 (4)
H1A0.17360.06720.39880.040*
H1B0.27970.06500.28280.040*
H1C0.17240.11090.20850.040*
C50.29237 (13)0.36395 (12)0.5339 (2)0.0229 (4)
H50.30610.42260.58620.027*
H20.4956 (19)0.4524 (12)0.621 (3)0.034*
H10.1043 (9)0.2265 (14)0.444 (4)0.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0205 (5)0.0250 (6)0.0405 (8)0.0007 (5)0.0004 (6)0.0028 (6)
O20.0553 (14)0.0318 (11)0.0324 (11)0.0147 (10)0.0000.000
N10.0206 (6)0.0206 (7)0.0234 (7)0.0014 (5)0.0004 (6)0.0008 (6)
C30.0240 (8)0.0215 (8)0.0246 (8)0.0035 (6)0.0014 (7)0.0012 (8)
C20.0268 (8)0.0193 (8)0.0205 (7)0.0009 (6)0.0014 (7)0.0022 (7)
C40.0229 (8)0.0208 (8)0.0241 (9)0.0003 (6)0.0011 (7)0.0038 (8)
C70.0245 (8)0.0243 (8)0.0309 (10)0.0025 (7)0.0008 (7)0.0041 (8)
C60.0244 (8)0.0196 (8)0.0213 (8)0.0009 (6)0.0012 (7)0.0019 (7)
C10.0309 (9)0.0216 (8)0.0284 (10)0.0005 (7)0.0007 (8)0.0012 (8)
C50.0255 (8)0.0174 (7)0.0258 (8)0.0004 (6)0.0006 (7)0.0004 (7)
Geometric parameters (Å, º) top
O1—C41.283 (2)C7—H7A0.9800
O2—H20.862 (7)C7—H7B0.9800
N1—C21.362 (2)C7—H7C0.9800
N1—C61.359 (2)C7—C61.498 (2)
N1—H10.871 (7)C6—C51.367 (2)
C3—H30.9500C1—H1A0.9800
C3—C21.370 (2)C1—H1B0.9800
C3—C41.422 (3)C1—H1C0.9800
C2—C11.498 (2)C5—H50.9500
C4—C51.428 (2)
C2—N1—H1116.8 (15)C6—C7—H7A109.5
C6—N1—C2122.02 (14)C6—C7—H7B109.5
C6—N1—H1120.9 (16)C6—C7—H7C109.5
C2—C3—H3119.5N1—C6—C7116.70 (14)
C2—C3—C4121.06 (16)N1—C6—C5119.79 (15)
C4—C3—H3119.5C5—C6—C7123.49 (16)
N1—C2—C3119.80 (16)C2—C1—H1A109.5
N1—C2—C1116.63 (15)C2—C1—H1B109.5
C3—C2—C1123.57 (16)C2—C1—H1C109.5
O1—C4—C3122.52 (15)H1A—C1—H1B109.5
O1—C4—C5121.34 (16)H1A—C1—H1C109.5
C3—C4—C5116.14 (15)H1B—C1—H1C109.5
H7A—C7—H7B109.5C4—C5—H5119.4
H7A—C7—H7C109.5C6—C5—C4121.12 (16)
H7B—C7—H7C109.5C6—C5—H5119.4
O1—C4—C5—C6179.53 (17)C2—C3—C4—C52.6 (3)
N1—C6—C5—C41.2 (3)C4—C3—C2—N12.5 (3)
C3—C4—C5—C60.7 (3)C4—C3—C2—C1176.66 (16)
C2—N1—C6—C7177.28 (17)C7—C6—C5—C4177.33 (17)
C2—N1—C6—C51.4 (3)C6—N1—C2—C30.5 (3)
C2—C3—C4—O1177.66 (16)C6—N1—C2—C1178.74 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.86 (1)1.96 (1)2.8174 (17)173 (2)
N1—H1···O1i0.87 (1)1.86 (1)2.7154 (18)166 (3)
Symmetry code: (i) x1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.862 (7)1.960 (8)2.8174 (17)173 (2)
N1—H1···O1i0.871 (7)1.862 (9)2.7154 (18)166 (3)
Symmetry code: (i) x1/2, y+1/2, z.
 

Acknowledgements

We greatly acknowledge support from the National Science Foundation (CHE-1429086).

References

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