4-Acetyl­pyridinium hydrogen sulfate

The crystal structure of the title compound, C₇H₈NO⁺·HSO₄⁻, consists of O—H⋯Ohydrogen-bonded extended chains of hydrogen sulfate anions. Each hydrogen sulfate anion is furthermore connected to one 4-acetyl­pyridinium cation via a hydrogen bond of the N—H⋯O type.

Related literature

For the synthesis of 4-acetyl­pyridine, see: Piner et al. (1934). For the crystal structure of an adduct of 4-acetyl­pyridine with penta­chloro­phenol, see: Majerz et al. (1991). For the crystal structures of Zn and Ni complexes of 4-acetyl­pyridine, see: Pang et al. (1994); Steffen et al. (1977).

Experimental

Crystal data

• C₇H₈NO⁺·HSO₄⁻

• M_r = 219.21

• Orthorhombic, P 2₁ 2₁ 2₁

• a = 4.6454 (9) Å

• b = 9.597 (2) Å

• c = 21.310 (4) Å

• V = 950.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.34 mm⁻¹

• T = 298 K

• 0.20 × 0.20 × 0.20 mm

Data collection

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) T_min = 0.935, T_max = 0.935

• 9843 measured reflections

• 2156 independent reflections

• 1622 reflections with I > 2σ(I)

• R_int = 0.077

Refinement

• R[F² > 2σ(F²)] = 0.053

• wR(F²) = 0.170

• S = 0.93

• 2156 reflections

• 129 parameters

• H-atom parameters constrained

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

• Absolute structure: Flack (1983), 860 Friedel pairs

• Flack parameter: 0.2 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O1^i	0.86	1.92	2.772 (5)	172
O3—H3⋯O2^ii	0.82	1.76	2.565 (5)	166
Symmetry codes: (i) ; (ii) x+1, y, z.

Data collection: CrystalClear (Rigaku, 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Supporting information

S1. Comment

4-Acetylpyridine may be used as a ligand in coordination compounds e.g. with Zn (Steffen & Palenik, 1977) or Ni (Pang et al., 1994). The crystal structure of 4-acetylpyridine together with pentachlorophenol is also known (Majerz et al., 1991).

The asymmetric unit of the title compound contains one 4-acetylpyridinium cation and one hydrogen sulfate anion (Fig 1). In the anion, the bond length of S1—O3 is 1.553 (6) Å compared to the average bond length of 1.438 (5) Å of the other S1—O bonds. It is therefore reasonable that the hydrogen atom of hydrogen sulfate is bonded to O3. The supramolecular structure consists of infinite chains of anions with one cation linked to each anion via an additional hydrogen bond (N1—H1B···O1 2.774 (8) Å, Fig 2).

Related literature

For the synthesis of 4-acetylpyridine, see: Piner et al. (1934). For the crystal structure of an adduct of 4-acetylpyridine with pentachlorophenol, see: Majerz et al. (1991). For the crystal structures of Zn and Ni complexes of 4-acetylpyridine, see: Pang et al. (1994); Steffen et al. (1977).

S2. Experimental

4-Acetylpyridine was obtained according to the method described by Piner (1934). Reaction of equimolar amounts of 4-acetylpyridine and H₂SO₄ produced a precipitate. This was filtered off, dried and dissolved in 96% ethanol from which single crystals were grown by slow evaporation of the solvent at room temperature.

S3. Refinement

The H atom connected to O3 was discernible from difference electron-density map. Nevertheless, it was placed to the ideal position, with S1—O3—H angle tetrahedral, allowing the H atom to ride on the immediately preceding atom O3 and rotate about the S1—O3 bond, refined in a riding atom approximation with a constrained bond length of O—H = 0.82 Å. Positional parameters of the other H atoms were calculated geometrically with C_ar–H = 0.93 Å and C_Me–H = 0.96 Å and were allowed to ride on the corresponding C atoms with U_iso(H) = 1.2 U_eq(C). In the absence of significant anomalous dispersion effects, 860 Friedel pairs were merged.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. Molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and all H atoms have been omitted for clarity.
	Fig. 2. Crystal packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

4-Acetylpyridinium hydrogen sulfate

Crystal data

C7H8NO^+·HSO4^−	F(000) = 456
Mr = 219.21	Dx = 1.533 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4231 reflections
a = 4.6454 (9) Å	θ = 3.6–27.6°
b = 9.597 (2) Å	µ = 0.34 mm^−1
c = 21.310 (4) Å	T = 298 K
V = 950.1 (3) Å^3	Prism, colourless
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer	2156 independent reflections
Radiation source: fine-focus sealed tube	1622 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.6°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.935, Tmax = 0.935	l = −27→27
9843 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.170	w = 1/[σ^2(Fo^2) + (0.1249P)^2 + 1.8027P] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
2156 reflections	Δρmax = 0.38 e Å^−3
129 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Absolute structure: Flack (1983), 860 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.9101 (2)	0.18577 (10)	0.16383 (5)	0.0475 (3)
O5	−0.0805 (8)	0.6665 (5)	0.03394 (17)	0.0853 (12)
O1	1.0236 (7)	0.3041 (3)	0.19787 (16)	0.0655 (9)
N1	0.6303 (8)	0.7352 (4)	0.20080 (17)	0.0573 (9)
H1B	0.7336	0.7648	0.2315	0.069*
C3	0.3084 (8)	0.6431 (4)	0.10302 (18)	0.0457 (9)
C1	0.4610 (10)	0.8250 (5)	0.1713 (2)	0.0614 (11)
H1A	0.4549	0.9175	0.1842	0.074*
C6	0.1250 (13)	0.5981 (6)	0.0476 (2)	0.0634 (13)
C5	0.6477 (10)	0.6005 (5)	0.1849 (2)	0.0548 (11)
H5A	0.7674	0.5403	0.2070	0.066*
C4	0.4852 (9)	0.5528 (5)	0.1353 (2)	0.0544 (11)
H4A	0.4949	0.4596	0.1236	0.065*
C2	0.2960 (10)	0.7819 (4)	0.1223 (2)	0.0546 (10)
H2A	0.1759	0.8446	0.1017	0.066*
O2	0.6532 (7)	0.2155 (4)	0.1291 (2)	0.0858 (12)
O3	1.1265 (8)	0.1454 (6)	0.1117 (2)	0.0968 (15)
H3	1.2838	0.1802	0.1194	0.145*
O4	0.8942 (13)	0.0646 (4)	0.2026 (2)	0.1068 (15)
C7	0.2139 (18)	0.4694 (7)	0.0132 (3)	0.106 (2)
H7A	0.0795	0.4510	−0.0200	0.160*
H7B	0.2166	0.3919	0.0417	0.160*
H7C	0.4026	0.4824	−0.0042	0.160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0356 (4)	0.0481 (5)	0.0588 (5)	−0.0017 (4)	−0.0011 (4)	−0.0066 (5)
O5	0.058 (2)	0.121 (3)	0.077 (2)	−0.004 (3)	−0.0169 (19)	0.008 (2)
O1	0.069 (2)	0.0471 (16)	0.080 (2)	0.0051 (15)	−0.0109 (17)	−0.0183 (15)
N1	0.046 (2)	0.073 (2)	0.0531 (19)	−0.0074 (18)	0.0000 (17)	−0.0004 (17)
C3	0.0372 (18)	0.054 (2)	0.0459 (19)	−0.0021 (16)	0.0076 (16)	0.0062 (17)
C1	0.063 (3)	0.049 (2)	0.072 (3)	−0.003 (2)	0.002 (2)	0.000 (2)
C6	0.059 (3)	0.083 (3)	0.048 (2)	−0.016 (3)	0.009 (2)	0.003 (2)
C5	0.044 (2)	0.066 (3)	0.054 (2)	0.007 (2)	−0.0010 (19)	0.0119 (19)
C4	0.060 (3)	0.045 (2)	0.058 (2)	0.0030 (19)	0.014 (2)	0.0029 (18)
C2	0.055 (2)	0.047 (2)	0.062 (2)	0.0078 (19)	0.001 (2)	0.0075 (19)
O2	0.0428 (18)	0.096 (3)	0.118 (3)	0.0099 (17)	−0.021 (2)	−0.021 (2)
O3	0.0471 (19)	0.145 (4)	0.098 (3)	−0.010 (2)	0.001 (2)	−0.060 (3)
O4	0.137 (4)	0.073 (2)	0.110 (3)	−0.039 (3)	−0.028 (3)	0.022 (2)
C7	0.128 (6)	0.110 (5)	0.081 (4)	0.002 (5)	−0.020 (4)	−0.039 (4)

Geometric parameters (Å, º)

S1—O4	1.429 (4)	C1—C2	1.360 (6)
S1—O2	1.433 (4)	C1—H1A	0.9300
S1—O1	1.447 (3)	C6—C7	1.495 (8)
S1—O3	1.547 (4)	C5—C4	1.378 (6)
O5—C6	1.194 (7)	C5—H5A	0.9300
N1—C1	1.325 (6)	C4—H4A	0.9300
N1—C5	1.339 (6)	C2—H2A	0.9300
N1—H1B	0.8600	O3—H3	0.8200
C3—C4	1.378 (6)	C7—H7A	0.9600
C3—C2	1.395 (6)	C7—H7B	0.9600
C3—C6	1.519 (6)	C7—H7C	0.9600
O4—S1—O2	114.7 (3)	C7—C6—C3	117.5 (5)
O4—S1—O1	111.6 (2)	N1—C5—C4	118.8 (4)
O2—S1—O1	113.9 (2)	N1—C5—H5A	120.6
O4—S1—O3	104.2 (3)	C4—C5—H5A	120.6
O2—S1—O3	102.7 (2)	C5—C4—C3	120.0 (4)
O1—S1—O3	108.7 (2)	C5—C4—H4A	120.0
C1—N1—C5	122.9 (4)	C3—C4—H4A	120.0
C1—N1—H1B	118.5	C1—C2—C3	119.5 (4)
C5—N1—H1B	118.5	C1—C2—H2A	120.2
C4—C3—C2	118.6 (4)	C3—C2—H2A	120.2
C4—C3—C6	123.0 (4)	S1—O3—H3	109.5
C2—C3—C6	118.5 (4)	C6—C7—H7A	109.5
N1—C1—C2	120.1 (4)	C6—C7—H7B	109.5
N1—C1—H1A	120.0	H7A—C7—H7B	109.5
C2—C1—H1A	120.0	C6—C7—H7C	109.5
O5—C6—C7	123.8 (5)	H7A—C7—H7C	109.5
O5—C6—C3	118.8 (5)	H7B—C7—H7C	109.5
C5—N1—C1—C2	−0.4 (7)	N1—C5—C4—C3	−0.1 (6)
C4—C3—C6—O5	157.9 (4)	C2—C3—C4—C5	−0.8 (6)
C2—C3—C6—O5	−21.8 (6)	C6—C3—C4—C5	179.5 (4)
C4—C3—C6—C7	−21.9 (6)	N1—C1—C2—C3	−0.5 (7)
C2—C3—C6—C7	158.4 (5)	C4—C3—C2—C1	1.1 (6)
C1—N1—C5—C4	0.7 (7)	C6—C3—C2—C1	−179.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1^i	0.86	1.92	2.772 (5)	172
O3—H3···O2^ii	0.82	1.76	2.565 (5)	166

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