4-Acetyl­pyridine–fumaric acid (2/1)

Xu, K.; Zhang, B.-Y.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536809020480

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1467

doi:10.1107/S1600536809020480

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4-Acetylpyridine–fumaric acid (2/1)

Kan Xu,^a Bing-Yu Zhang,^b Jing-Jing Nie ^b and Duan-Jun Xu ^b ^*

^aDepartment of Orthopaedics, Second Affiliated Hospital, School of Medicine, Zhejiang University, People's Republic of China, and ^bDepartment of Chemistry, Zhejiang University, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 26 May 2009; accepted 29 May 2009; online 6 June 2009)

In the crystal structure of the title cocrystal, 2C₇H₇NO·C₄H₄O₄, the complete fumaric acid molecule is generated by a crystallographic inversion centre. The two components of the cocrystal are linked by an O—H⋯N hydrogen bond.

Related literature

For biological and medicinal applications of 4-acetylpyridine and fumaric acid, see: Fidler et al. (2003 ); Thomas et al. (2007 ). For molecular complexes of neutral pyridine derivatives and neutral fumaric acid, see: Bowes et al. (2003 ); Aakeroy et al. (2002 , 2006 , 2007 ); Haynes et al. (2006 ); Bu et al. (2007 ). For literature on C—O bond distances in fumaric acid, see: Liu et al. (2003 ). For metal complexes of 4-acetylpyridine, see: Steffen & Palenik (1977 ); Pang et al. (1994 ). For a 4-acetylpyridinium salt, see: Kochel (2005 ).

Experimental

Crystal data

2C₇H₇NO·C₄H₄O₄
M_r = 358.34
Triclinic, $[P \overline 1]$
a = 3.9062 (5) Å
b = 8.6809 (13) Å
c = 13.0909 (18) Å
α = 87.925 (4)°
β = 89.941 (3)°
γ = 83.141 (4)°
V = 440.44 (11) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 K
0.30 × 0.11 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: none
3600 measured reflections
1589 independent reflections
798 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.143
S = 1.18
1589 reflections
124 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N1	0.98 (4)	1.64 (4)	2.599 (3)	166 (4)

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020480/ng2588sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020480/ng2588Isup2.hkl

checkCIF report

Comment top

The fumaric acid and acetylpyridine have been widely used in the biological and medicine fileds (Thomas et al. 2007; Fidler et al. 2003). In the medicine composition the carboxyl group of the fumaric acid is usually deprotonated while the pyridine derivatives are protonated. But some crystal structure determinations showed the neutral pyridine derivatives and fumaric acid in the crystal structures, i.e. the pyridine derivatives are not protonated while the fumaric acid is also not deprotonated in these crystal structures (Bowes et al. 2003; Aakeroy et al., 2002, 2006, 2007; Haynes et al. 2006; Bu et al. 2007). Herein we report the crystal structure of the new compound containing pyridine derivative and fumaric acid components.

The crystal structure of the title compond consists of fumaric acid and 4-acetylpyridine molecules (Fig. 1). The planar fumaric acid molecule is centrosymmetric with the mid-point of the C═C double bond located at an inversion center. The C8—O2 bond distance of 1.204 (3) Å is much shorter than the C8—O3 bond distance of 1.297 (3) Å, it suggests that the carboxyl group is not deprotonated in the crystal structure (Liu et al. 2003).

The acetylpyridine molecule is not protonated in the crystal structure, which contrasts with that found in the crystal structure of the 4-acetylpyridinium chloride (Kochel, 2005). The geometry data of the acetylpyridine is consistent with those found in metal complexes of acetylpyridine (Steffen & Palenik, 1977; Pang et al., 1994). The planar acetylpyridine molecule is twisted to the fumaric acid with a dihedral angle of 25.97 (11)° in the crystal structure.

The intermolecular classic O—H···N hydrogen bonding and weak C—H···O hydrogen bonding help to stabilize the crystal structure (Table 1).

Related literature top

For biological and medicinal applications of 4-acetylpyridine and fumaric acid, see: Fidler et al. (2003); Thomas et al. (2007). For molecular complexes of neutral pyridine derivatives and neutral fumaric acid, see: Bowes et al. (2003); Aakeroy et al. (2002, 2006, 2007); Haynes et al. (2006); Bu et al. (2007). For literature on C—O bond distances in fumaric acid, see: Liu et al. (2003). For metal complexes of 4-acetylpyridine, see: Steffen & Palenik (1977); Pang et al. (1994). For a 4-acetylpyridinium salt, see: Kochel (2005).

Experimental top

Reagents and solvent were used as purchased without further purification. 4-Acetylpyridine (2 mmol) and fumaric acid (1 mmol) were dissolved in water–ethanol (6 ml, 1:5) at room temperature. The single crystals were obtained from the solution after 3 d.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonding.

4-Acetylpyridine–fumaric acid (2/1) top

Crystal data top

2C₇H₇NO·C₄H₄O₄	Z = 1
M_r = 358.34	F(000) = 188
Triclinic, P1	D_x = 1.351 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.9062 (5) Å	Cell parameters from 2308 reflections
b = 8.6809 (13) Å	θ = 3.2–24.6°
c = 13.0909 (18) Å	µ = 0.10 mm⁻¹
α = 87.925 (4)°	T = 294 K
β = 89.941 (3)°	Needle, colourless
γ = 83.141 (4)°	0.30 × 0.11 × 0.08 mm
V = 440.44 (11) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	798 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 25.2°, θ_min = 3.1°
ω scans	h = −4→4
3600 measured reflections	k = −10→10
1589 independent reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.0527P)² + 0.048P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.001
1589 reflections	Δρ_max = 0.19 e Å⁻³
124 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (8)

Crystal data top

2C₇H₇NO·C₄H₄O₄	γ = 83.141 (4)°
M_r = 358.34	V = 440.44 (11) Å³
Triclinic, P1	Z = 1
a = 3.9062 (5) Å	Mo Kα radiation
b = 8.6809 (13) Å	µ = 0.10 mm⁻¹
c = 13.0909 (18) Å	T = 294 K
α = 87.925 (4)°	0.30 × 0.11 × 0.08 mm
β = 89.941 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	798 reflections with I > 2σ(I)
3600 measured reflections	R_int = 0.030
1589 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.19 e Å⁻³
1589 reflections	Δρ_min = −0.20 e Å⁻³
124 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 > 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

	x	y	z	U_iso*/U_eq
N1	0.4491 (6)	0.4588 (3)	0.69775 (18)	0.0630 (7)
O1	0.8832 (6)	0.7499 (3)	0.98158 (16)	0.0900 (8)
O2	0.1660 (6)	0.1037 (2)	0.67034 (15)	0.0775 (7)
O3	0.2584 (6)	0.2870 (3)	0.55473 (16)	0.0764 (7)
C1	0.5832 (8)	0.4178 (4)	0.7899 (2)	0.0733 (9)
H1	0.6122	0.3130	0.8097	0.088*
C2	0.6807 (7)	0.5230 (3)	0.8573 (2)	0.0651 (9)
H2	0.7765	0.4894	0.9204	0.078*
C3	0.6342 (6)	0.6786 (3)	0.82954 (19)	0.0494 (7)
C4	0.4891 (6)	0.7228 (3)	0.73526 (19)	0.0546 (7)
H4	0.4508	0.8270	0.7145	0.065*
C5	0.4019 (7)	0.6088 (4)	0.6724 (2)	0.0612 (8)
H5	0.3048	0.6391	0.6089	0.073*
C6	0.7453 (7)	0.7954 (3)	0.9018 (2)	0.0562 (8)
C7	0.6902 (7)	0.9624 (3)	0.8712 (2)	0.0653 (9)
H7A	0.7914	1.0212	0.9215	0.098*
H7B	0.4474	0.9961	0.8664	0.098*
H7C	0.7961	0.9784	0.8061	0.098*
C8	0.1658 (7)	0.1535 (3)	0.5833 (2)	0.0539 (7)
C9	0.0643 (7)	0.0651 (3)	0.4951 (2)	0.0561 (8)
H9	0.0951	0.1057	0.4295	0.067*
H3A	0.335 (9)	0.337 (5)	0.615 (3)	0.131 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0771 (16)	0.0500 (17)	0.0641 (16)	−0.0142 (12)	−0.0009 (13)	−0.0083 (13)
O1	0.1244 (18)	0.0731 (17)	0.0703 (14)	−0.0004 (13)	−0.0407 (14)	−0.0077 (12)
O2	0.1167 (18)	0.0640 (15)	0.0548 (13)	−0.0234 (12)	−0.0138 (12)	0.0004 (11)
O3	0.1198 (18)	0.0541 (15)	0.0607 (13)	−0.0313 (13)	−0.0048 (12)	−0.0076 (11)
C1	0.096 (2)	0.046 (2)	0.077 (2)	−0.0096 (17)	−0.0064 (19)	0.0019 (17)
C2	0.082 (2)	0.052 (2)	0.0610 (19)	−0.0053 (15)	−0.0123 (16)	0.0030 (15)
C3	0.0523 (15)	0.0448 (18)	0.0513 (16)	−0.0058 (12)	−0.0004 (13)	−0.0030 (13)
C4	0.0682 (17)	0.0451 (17)	0.0512 (16)	−0.0100 (13)	−0.0046 (14)	−0.0014 (13)
C5	0.0704 (18)	0.057 (2)	0.0566 (18)	−0.0100 (15)	−0.0086 (15)	−0.0024 (15)
C6	0.0577 (16)	0.057 (2)	0.0541 (18)	−0.0048 (13)	−0.0047 (14)	−0.0051 (14)
C7	0.0738 (19)	0.054 (2)	0.070 (2)	−0.0163 (15)	−0.0083 (16)	−0.0077 (16)
C8	0.0604 (16)	0.0446 (18)	0.0567 (18)	−0.0048 (13)	−0.0084 (14)	−0.0063 (14)
C9	0.0680 (17)	0.0469 (18)	0.0534 (16)	−0.0063 (13)	−0.0072 (14)	−0.0016 (14)

Geometric parameters (Å, º) top

N1—C5	1.323 (4)	C3—C6	1.512 (4)
N1—C1	1.335 (4)	C4—C5	1.383 (4)
O1—C6	1.207 (3)	C4—H4	0.9300
O2—C8	1.204 (3)	C5—H5	0.9300
O3—C8	1.297 (3)	C6—C7	1.481 (4)
O3—H3A	0.97 (4)	C7—H7A	0.9600
C1—C2	1.378 (4)	C7—H7B	0.9600
C1—H1	0.9300	C7—H7C	0.9600
C2—C3	1.377 (4)	C8—C9	1.488 (4)
C2—H2	0.9300	C9—C9ⁱ	1.293 (5)
C3—C4	1.381 (3)	C9—H9	0.9300

C5—N1—C1	117.3 (3)	C4—C5—H5	118.2
C8—O3—H3A	108 (2)	O1—C6—C7	121.8 (3)
N1—C1—C2	123.2 (3)	O1—C6—C3	119.3 (3)
N1—C1—H1	118.4	C7—C6—C3	118.9 (2)
C2—C1—H1	118.4	C6—C7—H7A	109.5
C3—C2—C1	118.9 (3)	C6—C7—H7B	109.5
C3—C2—H2	120.5	H7A—C7—H7B	109.5
C1—C2—H2	120.5	C6—C7—H7C	109.5
C2—C3—C4	118.4 (2)	H7A—C7—H7C	109.5
C2—C3—C6	119.6 (2)	H7B—C7—H7C	109.5
C4—C3—C6	122.0 (3)	O2—C8—O3	124.8 (3)
C3—C4—C5	118.6 (3)	O2—C8—C9	123.1 (3)
C3—C4—H4	120.7	O3—C8—C9	112.2 (3)
C5—C4—H4	120.7	C9ⁱ—C9—C8	123.6 (3)
N1—C5—C4	123.5 (3)	C9ⁱ—C9—H9	118.2
N1—C5—H5	118.2	C8—C9—H9	118.2

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N1	0.98 (4)	1.64 (4)	2.599 (3)	166 (4)
C4—H4···O2ⁱⁱ	0.93	2.57	3.471 (3)	164
C7—H7C···O2ⁱⁱⁱ	0.96	2.58	3.489 (3)	158

Symmetry codes: (ii) x, y+1, z; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	2C₇H₇NO·C₄H₄O₄
M_r	358.34
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	3.9062 (5), 8.6809 (13), 13.0909 (18)
α, β, γ (°)	87.925 (4), 89.941 (3), 83.141 (4)
V (Å³)	440.44 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.11 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3600, 1589, 798
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.143, 1.18
No. of reflections	1589
No. of parameters	124
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N1	0.98 (4)	1.64 (4)	2.599 (3)	166 (4)

Acknowledgements

The work was supported by the Scientific Foundation of the Department of Education of Zhejiang Province, China (grant No. Y200700867).

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