4-Acetyl­pyridinium perchlorate

Abstract

In the crystal of the title mol­ecular salt, C₇H₈NO⁺·ClO₄ ⁻, the ions are linked by N—H⋯O hydrogen bonds, resulting in chains propagating in [010]. The packing is reinforced by C—H⋯O inter­actions.

Related literature

For the synthesis, see: Piner (1934 ▶).

Experimental

Crystal data

• C₇H₈NO⁺·ClO₄ ⁻

• M _r = 221.59

• Monoclinic,

• a = 5.4657 (11) Å

• b = 12.621 (3) Å

• c = 13.490 (3) Å

• β = 97.88 (3)°

• V = 921.8 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.41 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 = 0.921, T _max = 0.921

• 9446 measured reflections

• 2108 independent reflections

• 1619 reflections with I > 2σ(I)

• R _int = 0.049

Refinement

• R[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 0.167

• S = 1.06

• 2108 reflections

• 127 parameters

• 7 restraints

• H-atom parameters constrained

• Δρ_max = 0.65 e Å⁻³

• Δρ_min = −0.90 e Å⁻³

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: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86	2.14	2.896 (5)	146
C1—H1B⋯O5ii	0.93	2.49	2.963 (5)	112
C2—H2A⋯O3iii	0.93	2.59	3.435 (6)	151
C5—H5A⋯O4i	0.93	2.46	3.332 (6)	156
C7—H7B⋯O3iii	0.96	2.58	3.488 (6)	158

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

The asymmetric unit of the title compound contains a 4-Acetylpyridinium cation and a perchlorate anion (Fig 1). The bond length of O5—C6 and C6—C7 are 1.202 (5)Å and 1.492 (6)Å respectively, and the average bond length of Cl—O is 1.428 (3) Å. The N—H···O and C—H···O hydrogen bonding (Table 1) (N1—H···O1 2.896 (5) Å, C1—H···O5 2.963 (5) Å) make great contribution to the stability of the crystal structure and link the molecules to chains along the b axis (Fig 2).

Experimental

4-Acetylpyridine was obtained according to the method described by Piner (1934) and colourless prisms of (I) were recrystallised from ethanol.

Refinement

The positional parameters of all the H atoms were calculated geometrically and refined as riding with U_iso(H) = 1.2U_eq(carrier).

Figures

Fig. 1.

The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level (all H atoms have been omitted for clarity).

Fig. 2.

A view of the packing of (I) showing chains along the b axis. Dashed lines indicate hydrogen bonds.

Crystal data

C7H8NO+·ClO4−	F(000) = 456
Mr = 221.59	Dx = 1.597 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4087 reflections
a = 5.4657 (11) Å	θ = 3.1–27.6°
b = 12.621 (3) Å	µ = 0.41 mm−1
c = 13.490 (3) Å	T = 298 K
β = 97.88 (3)°	Prism, colourless
V = 921.8 (4) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	2108 independent reflections
Radiation source: fine-focus sealed tube	1619 reflections with I > 2σ(I)
graphite	Rint = 0.049
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
Tmin = 0.921, Tmax = 0.921	l = −17→17
9446 measured reflections

Refinement

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0688P)2 + 0.9865P] where P = (Fo2 + 2Fc2)/3
2108 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.65 e Å−3
7 restraints	Δρmin = −0.90 e Å−3

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
Cl1	0.13491 (18)	0.20125 (8)	0.11005 (7)	0.0477 (3)
O5	0.3901 (6)	0.6009 (3)	0.1267 (2)	0.0640 (9)
C2	0.7259 (7)	0.3883 (3)	0.2591 (3)	0.0472 (9)
H2A	0.8394	0.3735	0.2155	0.057*
C6	0.5616 (7)	0.5419 (3)	0.1489 (3)	0.0442 (9)
C3	0.5618 (7)	0.4719 (3)	0.2396 (3)	0.0395 (8)
C4	0.3922 (7)	0.4908 (4)	0.3048 (3)	0.0495 (10)
H4A	0.2785	0.5457	0.2926	0.059*
C7	0.7761 (9)	0.5359 (4)	0.0917 (3)	0.0584 (11)
H7A	0.7509	0.5840	0.0361	0.088*
H7B	0.7913	0.4650	0.0676	0.088*
H7C	0.9244	0.5550	0.1347	0.088*
O4	0.0611 (7)	0.0968 (3)	0.0755 (3)	0.0790 (11)
O3	−0.0390 (8)	0.2749 (3)	0.0608 (3)	0.0814 (11)
O2	0.1393 (7)	0.2069 (3)	0.2155 (2)	0.0809 (12)
C5	0.3935 (8)	0.4281 (4)	0.3873 (3)	0.0589 (12)
H5A	0.2811	0.4403	0.4320	0.071*
N1	0.5561 (8)	0.3493 (3)	0.4037 (3)	0.0607 (10)
H1A	0.5546	0.3108	0.4562	0.073*
O1	0.3763 (6)	0.2204 (3)	0.0851 (2)	0.0645 (6)
C1	0.7196 (9)	0.3275 (4)	0.3430 (3)	0.0575 (11)
H1B	0.8296	0.2716	0.3571	0.069*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0506 (6)	0.0518 (6)	0.0440 (5)	0.0087 (4)	0.0186 (4)	0.0039 (4)
O5	0.065 (2)	0.064 (2)	0.062 (2)	0.0170 (16)	0.0035 (15)	0.0069 (15)
C2	0.051 (2)	0.043 (2)	0.050 (2)	0.0003 (17)	0.0159 (18)	−0.0036 (17)
C6	0.049 (2)	0.042 (2)	0.041 (2)	−0.0013 (17)	0.0036 (17)	−0.0046 (16)
C3	0.0386 (18)	0.0403 (19)	0.0396 (18)	−0.0047 (15)	0.0058 (15)	−0.0044 (15)
C4	0.042 (2)	0.056 (2)	0.052 (2)	0.0015 (18)	0.0117 (17)	−0.0060 (19)
C7	0.066 (3)	0.067 (3)	0.045 (2)	−0.002 (2)	0.017 (2)	0.009 (2)
O4	0.085 (3)	0.060 (2)	0.097 (3)	−0.0072 (19)	0.032 (2)	−0.0063 (19)
O3	0.100 (3)	0.079 (2)	0.065 (2)	0.037 (2)	0.009 (2)	0.0155 (18)
O2	0.094 (3)	0.109 (3)	0.0421 (18)	0.030 (2)	0.0173 (17)	0.0069 (17)
C5	0.054 (3)	0.075 (3)	0.051 (2)	−0.014 (2)	0.020 (2)	−0.006 (2)
N1	0.073 (3)	0.058 (2)	0.052 (2)	−0.016 (2)	0.0125 (19)	0.0106 (18)
O1	0.0571 (11)	0.0787 (12)	0.0614 (11)	0.0010 (10)	0.0210 (10)	−0.0032 (10)
C1	0.067 (3)	0.046 (2)	0.060 (3)	0.000 (2)	0.011 (2)	0.007 (2)

Geometric parameters (Å, °)

Cl1—O2	1.421 (3)	C4—C5	1.365 (6)
Cl1—O1	1.427 (3)	C4—H4A	0.9300
Cl1—O3	1.427 (3)	C7—H7A	0.9600
Cl1—O4	1.437 (4)	C7—H7B	0.9600
O5—C6	1.202 (5)	C7—H7C	0.9600
C2—C1	1.372 (6)	C5—N1	1.332 (6)
C2—C3	1.386 (5)	C5—H5A	0.9300
C2—H2A	0.9300	N1—C1	1.321 (6)
C6—C7	1.492 (6)	N1—H1A	0.8600
C6—C3	1.509 (5)	C1—H1B	0.9300
C3—C4	1.384 (5)
O2—Cl1—O1	109.8 (2)	C3—C4—H4A	120.4
O2—Cl1—O3	110.7 (2)	C6—C7—H7A	109.5
O1—Cl1—O3	111.0 (2)	C6—C7—H7B	109.5
O2—Cl1—O4	109.6 (2)	H7A—C7—H7B	109.5
O1—Cl1—O4	107.8 (2)	C6—C7—H7C	109.5
O3—Cl1—O4	107.9 (2)	H7A—C7—H7C	109.5
C1—C2—C3	119.5 (4)	H7B—C7—H7C	109.5
C1—C2—H2A	120.2	N1—C5—C4	119.8 (4)
C3—C2—H2A	120.2	N1—C5—H5A	120.1
O5—C6—C7	123.0 (4)	C4—C5—H5A	120.1
O5—C6—C3	118.6 (4)	C1—N1—C5	123.1 (4)
C7—C6—C3	118.4 (3)	C1—N1—H1A	118.5
C4—C3—C2	118.9 (4)	C5—N1—H1A	118.5
C4—C3—C6	119.2 (3)	N1—C1—C2	119.4 (4)
C2—C3—C6	121.9 (3)	N1—C1—H1B	120.3
C5—C4—C3	119.3 (4)	C2—C1—H1B	120.3
C5—C4—H4A	120.4
C1—C2—C3—C4	−1.1 (6)	C2—C3—C4—C5	1.1 (6)
C1—C2—C3—C6	179.5 (4)	C6—C3—C4—C5	−179.4 (4)
O5—C6—C3—C4	−12.0 (5)	C3—C4—C5—N1	−0.4 (6)
C7—C6—C3—C4	167.1 (4)	C4—C5—N1—C1	−0.3 (7)
O5—C6—C3—C2	167.4 (4)	C5—N1—C1—C2	0.3 (7)
C7—C6—C3—C2	−13.4 (5)	C3—C2—C1—N1	0.4 (6)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.86	2.14	2.896 (5)	146
C1—H1B···O5ii	0.93	2.49	2.963 (5)	112
C2—H2A···O3iii	0.93	2.59	3.435 (6)	151
C5—H5A···O4i	0.93	2.46	3.332 (6)	156
C7—H7B···O3iii	0.96	2.58	3.488 (6)	158

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