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

Nguyen, D.M.; Desikan, V.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2056989015012402

organic compounds

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

Dalena M. Nguyen,^a Vasumathi Desikan,^a James A. Golen ^b and David R. Manke ^b ^*

^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.

Keywords: crystal structure; hydrogen bonding; pyridones.

CCDC reference: 1409189

1. Related literature

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 ).

2. Experimental

2.1. Crystal data

C₇H₉NO·0.5H₂O
M_r = 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 ) T_min = 0.554, T_max = 0.754
11786 measured reflections
1366 independent reflections
1352 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack x determined using 611 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 .
Absolute structure parameter: 0.05 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT; 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 and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1409189

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012402/ff2139sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012402/ff2139Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015012402/ff2139Isup3.cml

checkCIF report

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 U_eq 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 U_eq 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 U_eq 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

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

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

	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.
	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·0.5H₂O	F(000) = 568
M_r = 132.16	D_x = 1.266 Mg m⁻³
Orthorhombic, Aba2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: A 2 -2ac	Cell parameters from 9829 reflections
a = 12.4859 (17) Å	θ = 7.1–72.4°
b = 14.3697 (19) Å	µ = 0.73 mm⁻¹
c = 7.732 (1) Å	T = 120 K
V = 1387.3 (3) Å³	NEEDLE, colourless
Z = 8	0.5 × 0.1 × 0.1 mm

Data collection top

Bruker Venture D8 CMOS diffractometer	1366 independent reflections
Radiation source: microfocus Cu	1352 reflections with I > 2σ(I)
HELIOS MX monochromator	R_int = 0.060
φ and ω scans	θ_max = 72.4°, θ_min = 7.1°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −15→15
T_min = 0.554, T_max = 0.754	k = −17→17
11786 measured reflections	l = −9→9

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0453P)² + 0.3383P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.15 e Å⁻³
1366 reflections	Δρ_min = −0.19 e Å⁻³
95 parameters	Absolute structure: Flack x determined using 611 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013.
3 restraints	Absolute structure parameter: 0.05 (12)

Crystal data top

C₇H₉NO·0.5H₂O	V = 1387.3 (3) Å³
M_r = 132.16	Z = 8
Orthorhombic, Aba2	Cu Kα radiation
a = 12.4859 (17) Å	µ = 0.73 mm⁻¹
b = 14.3697 (19) Å	T = 120 K
c = 7.732 (1) Å	0.5 × 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)
T_min = 0.554, T_max = 0.754	R_int = 0.060
11786 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	Δρ_max = 0.15 e Å⁻³
S = 1.09	Δρ_min = −0.19 e Å⁻³
1366 reflections	Absolute structure: Flack x determined using 611 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013.
95 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
O1	0.47723 (9)	0.33620 (8)	0.49203 (19)	0.0287 (3)
O2	0.5000	0.5000	0.6889 (3)	0.0399 (5)
N1	0.16883 (11)	0.24949 (11)	0.4446 (2)	0.0215 (3)
C3	0.35308 (14)	0.22232 (12)	0.3962 (2)	0.0234 (4)
H3	0.4083	0.1841	0.3504	0.028*
C2	0.24877 (14)	0.19343 (12)	0.3853 (2)	0.0222 (4)
C4	0.38007 (12)	0.30864 (12)	0.4748 (2)	0.0226 (4)
C7	0.09367 (14)	0.39066 (13)	0.5690 (3)	0.0265 (4)
H7A	0.0630	0.4210	0.4669	0.040*
H7B	0.1158	0.4381	0.6527	0.040*
H7C	0.0399	0.3499	0.6218	0.040*
C6	0.18900 (13)	0.33399 (11)	0.5164 (2)	0.0217 (4)
C1	0.21576 (15)	0.10115 (12)	0.3125 (3)	0.0270 (4)
H1A	0.1736	0.0672	0.3988	0.040*
H1B	0.2797	0.0650	0.2828	0.040*
H1C	0.1724	0.1109	0.2085	0.040*
C5	0.29237 (13)	0.36395 (12)	0.5339 (2)	0.0229 (4)
H5	0.3061	0.4226	0.5862	0.027*
H2	0.4956 (19)	0.4524 (12)	0.621 (3)	0.034*
H1	0.1043 (9)	0.2265 (14)	0.444 (4)	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0205 (5)	0.0250 (6)	0.0405 (8)	−0.0007 (5)	−0.0004 (6)	−0.0028 (6)
O2	0.0553 (14)	0.0318 (11)	0.0324 (11)	−0.0147 (10)	0.000	0.000
N1	0.0206 (6)	0.0206 (7)	0.0234 (7)	−0.0014 (5)	0.0004 (6)	0.0008 (6)
C3	0.0240 (8)	0.0215 (8)	0.0246 (8)	0.0035 (6)	0.0014 (7)	0.0012 (8)
C2	0.0268 (8)	0.0193 (8)	0.0205 (7)	0.0009 (6)	−0.0014 (7)	0.0022 (7)
C4	0.0229 (8)	0.0208 (8)	0.0241 (9)	0.0003 (6)	−0.0011 (7)	0.0038 (8)
C7	0.0245 (8)	0.0243 (8)	0.0309 (10)	0.0025 (7)	−0.0008 (7)	−0.0041 (8)
C6	0.0244 (8)	0.0196 (8)	0.0213 (8)	0.0009 (6)	−0.0012 (7)	0.0019 (7)
C1	0.0309 (9)	0.0216 (8)	0.0284 (10)	−0.0005 (7)	−0.0007 (8)	−0.0012 (8)
C5	0.0255 (8)	0.0174 (7)	0.0258 (8)	−0.0004 (6)	−0.0006 (7)	0.0004 (7)

Geometric parameters (Å, º) top

O1—C4	1.283 (2)	C7—H7A	0.9800
O2—H2	0.862 (7)	C7—H7B	0.9800
N1—C2	1.362 (2)	C7—H7C	0.9800
N1—C6	1.359 (2)	C7—C6	1.498 (2)
N1—H1	0.871 (7)	C6—C5	1.367 (2)
C3—H3	0.9500	C1—H1A	0.9800
C3—C2	1.370 (2)	C1—H1B	0.9800
C3—C4	1.422 (3)	C1—H1C	0.9800
C2—C1	1.498 (2)	C5—H5	0.9500
C4—C5	1.428 (2)

C2—N1—H1	116.8 (15)	C6—C7—H7A	109.5
C6—N1—C2	122.02 (14)	C6—C7—H7B	109.5
C6—N1—H1	120.9 (16)	C6—C7—H7C	109.5
C2—C3—H3	119.5	N1—C6—C7	116.70 (14)
C2—C3—C4	121.06 (16)	N1—C6—C5	119.79 (15)
C4—C3—H3	119.5	C5—C6—C7	123.49 (16)
N1—C2—C3	119.80 (16)	C2—C1—H1A	109.5
N1—C2—C1	116.63 (15)	C2—C1—H1B	109.5
C3—C2—C1	123.57 (16)	C2—C1—H1C	109.5
O1—C4—C3	122.52 (15)	H1A—C1—H1B	109.5
O1—C4—C5	121.34 (16)	H1A—C1—H1C	109.5
C3—C4—C5	116.14 (15)	H1B—C1—H1C	109.5
H7A—C7—H7B	109.5	C4—C5—H5	119.4
H7A—C7—H7C	109.5	C6—C5—C4	121.12 (16)
H7B—C7—H7C	109.5	C6—C5—H5	119.4

O1—C4—C5—C6	−179.53 (17)	C2—C3—C4—C5	−2.6 (3)
N1—C6—C5—C4	1.2 (3)	C4—C3—C2—N1	2.5 (3)
C3—C4—C5—C6	0.7 (3)	C4—C3—C2—C1	−176.66 (16)
C2—N1—C6—C7	177.28 (17)	C7—C6—C5—C4	−177.33 (17)
C2—N1—C6—C5	−1.4 (3)	C6—N1—C2—C3	−0.5 (3)
C2—C3—C4—O1	177.66 (16)	C6—N1—C2—C1	178.74 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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−1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.862 (7)	1.960 (8)	2.8174 (17)	173 (2)
N1—H1···O1ⁱ	0.871 (7)	1.862 (9)	2.7154 (18)	166 (3)

Symmetry code: (i) x−1/2, −y+1/2, z.

Acknowledgements

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

References

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 8| August 2015| Page o533

https://doi.org/10.1107/S2056989015012402

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