2-Pyridone: monoclinic polymorph

Arman, H.D.; Poplaukhin, P.; Tiekink, E.R.T.

doi:10.1107/S1600536809049496

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3187

doi:10.1107/S1600536809049496

Open

access

2-Pyridone: monoclinic polymorph

Hadi D. Arman,^a Pavel Poplaukhin ^b and Edward R. T. Tiekink ^c ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, ^bChemical Abstracts Service, 2540 Olentangy River Rd, Columbus, Ohio 43202, USA, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 19 November 2009; accepted 19 November 2009; online 25 November 2009)

The asymmetric unit in the title compound, C₅H₅NO, comprises two independent but virtually identical molecules of 2-pyridone, and represents a monoclinic polymorph of the previously reported orthorhombic (P2₁2₁2₁) form [Penfold (1953 ). Acta Cryst. 6, 591–600; Ohms et al. (1984 ). Z. Kristallogr. 169, 185–200; Yang & Craven (1998 ). Acta Cryst. B54, 912–920]. The independent molecules are linked into supramolecular dimers via eight-membered {⋯HNC(O)}₂ amide synthons in contrast to the helical supramolecular chains, mediated by {⋯HNC(O)} links, found in the orthorhombic form.

Related literature

For the structure of the orthorhombic form of 2-pyridone, see: Penfold (1953); Ohms et al. (1984); Yang & Craven (1998). For related studies of co-crystal formation, see: Broker & Tiekink (2007 ); Ellis et al. (2009 ). For analysis of the geometric structures, see: Spek (2009 ).

Experimental

Crystal data

C₅H₅NO
M_r = 95.10
Monoclinic, P 2₁ /n
a = 6.2027 (13) Å
b = 16.327 (4) Å
c = 9.1046 (18) Å
β = 92.242 (7)°
V = 921.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 98 K
0.44 × 0.39 × 0.15 mm

Data collection

Rigaku AFC12K/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.840, T_max = 1
6582 measured reflections
1903 independent reflections
1724 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.117
S = 1.10
1903 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O2	0.88	1.86	2.7450 (16)	177
N2—H2n⋯O1	0.88	1.92	2.7915 (16)	171
C2—H2⋯O1ⁱ	0.95	2.53	3.3943 (18)	150
C4—H4⋯O2ⁱⁱ	0.95	2.54	3.2989 (18)	137
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049496/hg2602sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049496/hg2602Isup2.hkl

checkCIF report

Comment top

Crystals of the monoclinic polymorph of 2-pyridone, (I), were isolated during an on-going study into the phenomenon of co-crystal formation (Broker & Tiekink, 2007; Ellis et al., 2009). The orthorhombic form of (I) has been characterized previously (Penfold, 1953; Ohms et al., 1984; Yang & Craven, 1998).

In (I), two independent molecules comprise the asymmetric unit, Fig. 1, and these are virtually identical as seen in the r.m.s. values for bond distances and angles of 0.0025 Å and 0.184 °, respectively (Spek, 2009). Each molecule is essentially planar with the maximum deviation of 0.0102 (14) Å found for the C2 atom in the N1-molecule and 0.0029 (14) Å for the C6 atom in the N2-molecule. The pattern of bond distances matches those in the previously determined orthorhombic form.

The crystal packing in (I) is sustained by eight-membered {···HNC(O)}₂ amide synthons whereby the two independent molecules are linked, Table 1 and Fig. 1. The dimeric aggregate is effectively planar with the dihedral between the two 2-pyridone rings being 7.88 (6) °, The dimers are connected into zigzag layers in the ac plane via C—H···O interactions, Table 1 and Fig. 2. The major difference between the two polymeric forms of 2-pyridone rests in the mode of association between the 2-pyridone molecules. In the orthorhombic form, the molecules are lined into supramolecular helical chains through a continuing sequence of {···HNC( O)} links.

Related literature top

For the structure of the orthorhombic form of 2-pyridone, see: Penfold (1953); Ohms et al. (1984); Yang & Craven (1998). For related studies of co-crystal formation, see: Broker & Tiekink (2007); Ellis et al. (2009). For analysis of the geometric structures, see: Spek (2009).

Experimental top

2-Hydroxypyridine (Fluka) was dissolved in chloroform and layered with hexanes. Large rod-like colourless crystals formed within a week.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Molecular structures of the two independent molecules comprising the asymmetric unit in (I), showing atom-labelling scheme and displacement ellipsoids at the 50% probability level. The molecules are connected by N–H···O hydrogen bonds (orange dashed lines).
	Fig. 2. View of the stacking of layers along the b axis in crystal structure of (I). Colour code: O, red; N, blue; C, grey; and H, green. The N–H···O hydrogen bonds (orange) and C–H···O contacts (green) are shown as dashed lines.

2-pyridone top

Crystal data top

C₅H₅NO	F(000) = 400
M_r = 95.10	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3046 reflections
a = 6.2027 (13) Å	θ = 3.3–40.2°
b = 16.327 (4) Å	µ = 0.10 mm⁻¹
c = 9.1046 (18) Å	T = 98 K
β = 92.242 (7)°	Prism, colourless
V = 921.3 (3) Å³	0.44 × 0.39 × 0.15 mm
Z = 8

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	1903 independent reflections
Radiation source: fine-focus sealed tube	1724 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 26.5°, θ_min = 2.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→5
T_min = 0.840, T_max = 1	k = −20→20
6582 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0583P)² + 0.275P] where P = (F_o² + 2F_c²)/3
1903 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₅H₅NO	V = 921.3 (3) Å³
M_r = 95.10	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2027 (13) Å	µ = 0.10 mm⁻¹
b = 16.327 (4) Å	T = 98 K
c = 9.1046 (18) Å	0.44 × 0.39 × 0.15 mm
β = 92.242 (7)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	1903 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1724 reflections with I > 2σ(I)
T_min = 0.840, T_max = 1	R_int = 0.037
6582 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.10	Δρ_max = 0.21 e Å⁻³
1903 reflections	Δρ_min = −0.22 e Å⁻³
127 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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

	x	y	z	U_iso*/U_eq
O1	0.27541 (14)	0.36020 (6)	0.47704 (10)	0.0239 (2)
N1	−0.07408 (17)	0.31779 (7)	0.48531 (12)	0.0201 (3)
H1N	−0.1007	0.3587	0.5450	0.024*
C1	0.1321 (2)	0.30993 (8)	0.43716 (14)	0.0195 (3)
C2	−0.2397 (2)	0.26660 (8)	0.44686 (15)	0.0232 (3)
H2	−0.3795	0.2769	0.4819	0.028*
C3	−0.2074 (2)	0.20065 (8)	0.35857 (15)	0.0236 (3)
H3	−0.3219	0.1641	0.3330	0.028*
C4	0.0019 (2)	0.18832 (8)	0.30615 (14)	0.0224 (3)
H4	0.0289	0.1426	0.2450	0.027*
C5	0.1649 (2)	0.24113 (8)	0.34226 (14)	0.0209 (3)
H5	0.3033	0.2324	0.3039	0.025*
O2	−0.14759 (15)	0.44304 (6)	0.67815 (11)	0.0263 (3)
N2	0.19925 (17)	0.48837 (7)	0.67120 (12)	0.0204 (3)
H2N	0.2238	0.4519	0.6027	0.024*
C6	−0.0049 (2)	0.49182 (8)	0.72495 (14)	0.0199 (3)
C7	−0.0344 (2)	0.55309 (8)	0.83511 (15)	0.0236 (3)
H7	−0.1717	0.5592	0.8765	0.028*
C8	0.1311 (2)	0.60263 (9)	0.88132 (16)	0.0267 (3)
H8	0.1078	0.6427	0.9547	0.032*
C9	0.3370 (2)	0.59536 (9)	0.82168 (17)	0.0276 (3)
H9	0.4526	0.6299	0.8539	0.033*
C10	0.3652 (2)	0.53746 (9)	0.71679 (15)	0.0243 (3)
H10	0.5022	0.5313	0.6751	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0186 (5)	0.0256 (5)	0.0277 (5)	−0.0021 (4)	0.0025 (4)	−0.0048 (4)
N1	0.0186 (6)	0.0198 (5)	0.0219 (5)	0.0010 (4)	0.0027 (4)	−0.0035 (4)
C1	0.0180 (6)	0.0210 (6)	0.0195 (6)	0.0012 (5)	0.0000 (5)	0.0018 (5)
C2	0.0178 (6)	0.0248 (7)	0.0272 (7)	−0.0013 (5)	0.0026 (5)	−0.0022 (5)
C3	0.0208 (7)	0.0220 (7)	0.0281 (7)	−0.0021 (5)	0.0013 (5)	−0.0036 (5)
C4	0.0244 (7)	0.0202 (6)	0.0227 (6)	0.0036 (5)	−0.0004 (5)	−0.0025 (5)
C5	0.0179 (6)	0.0239 (7)	0.0211 (6)	0.0031 (5)	0.0031 (5)	−0.0010 (5)
O2	0.0206 (5)	0.0245 (5)	0.0342 (5)	−0.0041 (4)	0.0062 (4)	−0.0078 (4)
N2	0.0209 (6)	0.0183 (5)	0.0221 (5)	−0.0003 (4)	0.0029 (4)	−0.0014 (4)
C6	0.0191 (6)	0.0183 (6)	0.0222 (6)	0.0011 (5)	0.0009 (5)	0.0029 (5)
C7	0.0212 (6)	0.0252 (7)	0.0245 (7)	0.0031 (5)	0.0025 (5)	−0.0007 (5)
C8	0.0268 (7)	0.0262 (7)	0.0270 (7)	0.0035 (5)	−0.0010 (6)	−0.0063 (5)
C9	0.0227 (7)	0.0256 (7)	0.0342 (8)	−0.0026 (5)	−0.0024 (6)	−0.0043 (6)
C10	0.0176 (6)	0.0251 (7)	0.0304 (7)	−0.0016 (5)	0.0015 (5)	0.0016 (6)

Geometric parameters (Å, º) top

O1—C1	1.2529 (16)	O2—C6	1.2530 (16)
N1—C2	1.3597 (17)	N2—C10	1.3567 (17)
N1—C1	1.3743 (17)	N2—C6	1.3762 (17)
N1—H1N	0.8800	N2—H2N	0.8800
C1—C5	1.4365 (18)	C6—C7	1.4335 (18)
C2—C3	1.3633 (19)	C7—C8	1.3607 (19)
C2—H2	0.9500	C7—H7	0.9500
C3—C4	1.4151 (18)	C8—C9	1.412 (2)
C3—H3	0.9500	C8—H8	0.9500
C4—C5	1.3590 (19)	C9—C10	1.360 (2)
C4—H4	0.9500	C9—H9	0.9500
C5—H5	0.9500	C10—H10	0.9500

C2—N1—C1	124.33 (11)	C10—N2—C6	124.37 (11)
C2—N1—H1N	117.8	C10—N2—H2N	117.8
C1—N1—H1N	117.8	C6—N2—H2N	117.8
O1—C1—N1	120.32 (11)	O2—C6—N2	120.04 (12)
O1—C1—C5	124.83 (12)	O2—C6—C7	124.99 (12)
N1—C1—C5	114.84 (11)	N2—C6—C7	114.96 (11)
N1—C2—C3	120.67 (12)	C8—C7—C6	121.03 (12)
N1—C2—H2	119.7	C8—C7—H7	119.5
C3—C2—H2	119.7	C6—C7—H7	119.5
C2—C3—C4	118.00 (12)	C7—C8—C9	120.93 (13)
C2—C3—H3	121.0	C7—C8—H8	119.5
C4—C3—H3	121.0	C9—C8—H8	119.5
C5—C4—C3	120.77 (12)	C10—C9—C8	118.12 (13)
C5—C4—H4	119.6	C10—C9—H9	120.9
C3—C4—H4	119.6	C8—C9—H9	120.9
C4—C5—C1	121.36 (12)	N2—C10—C9	120.59 (12)
C4—C5—H5	119.3	N2—C10—H10	119.7
C1—C5—H5	119.3	C9—C10—H10	119.7

C2—N1—C1—O1	179.47 (12)	C10—N2—C6—O2	−178.77 (12)
C2—N1—C1—C5	−1.04 (18)	C10—N2—C6—C7	0.61 (18)
C1—N1—C2—C3	2.1 (2)	O2—C6—C7—C8	178.83 (13)
N1—C2—C3—C4	−1.3 (2)	N2—C6—C7—C8	−0.51 (19)
C2—C3—C4—C5	−0.4 (2)	C6—C7—C8—C9	0.2 (2)
C3—C4—C5—C1	1.5 (2)	C7—C8—C9—C10	0.0 (2)
O1—C1—C5—C4	178.72 (12)	C6—N2—C10—C9	−0.4 (2)
N1—C1—C5—C4	−0.74 (18)	C8—C9—C10—N2	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2	0.88	1.86	2.7450 (16)	177
N2—H2n···O1	0.88	1.92	2.7915 (16)	171
C2—H2···O1ⁱ	0.95	2.53	3.3943 (18)	150
C4—H4···O2ⁱⁱ	0.95	2.54	3.2989 (18)	137

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₅H₅NO
M_r	95.10
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	98
a, b, c (Å)	6.2027 (13), 16.327 (4), 9.1046 (18)
β (°)	92.242 (7)
V (Å³)	921.3 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.44 × 0.39 × 0.15

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.840, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	6582, 1903, 1724
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.10
No. of reflections	1903
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2	0.88	1.86	2.7450 (16)	177
N2—H2n···O1	0.88	1.92	2.7915 (16)	171
C2—H2···O1ⁱ	0.95	2.53	3.3943 (18)	150
C4—H4···O2ⁱⁱ	0.95	2.54	3.2989 (18)	137

Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, z−1/2.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Broker, G. A. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 1096–1109. Web of Science CSD CrossRef CAS Google Scholar
Ellis, C. A., Miller, M. A., Spencer, J., Zukerman-Schpector, J. & Tiekink, E. R. T. (2009). CrystEngComm, 11, 1352–1361. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ohms, U., Guth, H., Hellner, E., Dannohl, H. & Schweig, A. (1984). Z. Kristallogr. 169, 185–200. CrossRef CAS Web of Science Google Scholar
Penfold, B. R. (1953). Acta Cryst. 6, 591–600. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Yang, H. W. & Craven, B. M. (1998). Acta Cryst. B54, 912–920. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3187

doi:10.1107/S1600536809049496

Open

access