2-Acetyl­anilinium chloride

Prasath, R.; Bhavana, P.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811004739

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o623

doi:10.1107/S1600536811004739

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2-Acetylanilinium chloride

R. Prasath,^a P. Bhavana,^a ‡ Seik Weng Ng ^b and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, BITS, Pilani – K. K. Birla Goa Campus, Goa 403 726, India, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 7 February 2011; accepted 8 February 2011; online 12 February 2011)

The cation of the title salt, C₈H₁₀NO⁺·Cl⁻, is essentially planar [C—C—C—C torsion angle = 4.6 (2)°], the conformation being stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, centrosymmetric aggregates are formed via N—H⋯Cl hydrogen bonds. These dimeric aggregates are sustained in the crystal packing by a combination of C—H⋯Cl, C—H⋯O and C—O⋯π [O⋯ring centroid(benzene ring) = 3.1871 (13) and 3.3787 (13) Å] interactions.

Related literature

For background to structural studies of quinoline derivatives, see: Kaiser et al. (2009 ).

Experimental

Crystal data

C₈H₁₀NO⁺·Cl⁻
M_r = 171.62
Monoclinic, P 2₁ /c
a = 4.8979 (1) Å
b = 15.8136 (4) Å
c = 10.8203 (3) Å
β = 102.569 (3)°
V = 817.98 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.920, T_max = 1.000
3262 measured reflections
1436 independent reflections
1256 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.07
1436 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯Cl1	0.95 (2)	2.23 (2)	3.1463 (15)	163 (2)
N1—H2n⋯Cl1ⁱ	0.92 (2)	2.24 (2)	3.1366 (15)	165 (2)
N1—H3n⋯O1	0.87 (2)	1.95 (2)	2.6778 (18)	140 (2)
C5—H5⋯Cl1ⁱⁱ	0.95	2.73	3.5332 (18)	142
C6—H6⋯O1ⁱⁱⁱ	0.95	2.59	3.2496 (19)	127
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004739/hg2797sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004739/hg2797Isup2.hkl

checkCIF report

Comment top

The title salt, (I), was obtained as an unexpected product during the attempted synthesis of a quinoline derivative, investigated as a part of an on-going programme into the synthesis and structural chemistry of quinolines of interest owing to their putative anti-malarial activity (Kaiser et al., 2009).

Ionic (I), Fig. 1, comprises a 2-acetylanilinium cation and a chloride anion. The cation is essentially planar with the acetyl group only slightly twisted out of the plane of the benzene ring to which it is connected, the C1–C2–C3–C4 torsion angle = 4.6 (2) °. The observed conformation is stabilized by an intramolecular N–H···O hydrogen bond, Table 1.

In the crystal packing, centrosymmetrically related molecules are connected into a supramolecular dimer via N–H···Cl hydrogen bonds, Table 1 and Fig. 2. The dimeric aggregates are arranged into layers in the ac plane via a combination of C–H···O, Table 1, and C—O···π contacts [C2–O1···Cg(C3—C8)ⁱ = 3.1871 (13) Å with the angle at O1 = 96.44 (10) ° for i: 1 + x, y, z; and C2–O1···Cg(C3—C8)ⁱⁱ = 3.3787 (13) Å with the angle at O1 = 98.36 (9) ° for ii: x, 1/2 - y, -1/2 + z]. The presence of C–H···Cl interactions, Table 1, contributes to the stability of the structure along the b axis, Fig. 3.

Related literature top

For background to structural studies of quinoline derivatives, see: Kaiser et al. (2009).

Experimental top

A mixture of 2-aminoacetophenone (0.01 M), acetophenone (0.01 M) and a catalytic amount of conc. HCl was heated on a water bath for 10 min. The resultant solid was filtered, dried and purified by column chromatography using a 1:5 mixture of ethyl acetate and hexane. Re-crystallization was by slow evaporation of an acetone solution of (I) which yielded colourless needles. M.pt. 421–423 K. Yield: 66%. The X-ray study showed that the original 2-aminoacetophenone had been protonated and crystallized as a chloride salt.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The constituent ions of salt (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular dimer in (I) mediated by N–H···Cl hydrogen bonding, shown as orange dashed lines.
	Fig. 3. Unit-cell contents shown in projection down the a axis in (I). The N–H···Cl hydrogen bonding, and C–H···Cl, C–H···O and C–O···π contacts are shown as orange, blue, pink, and purple dashed lines, respectively.

2-Acetylanilinium chloride top

Crystal data top

C₈H₁₀NO⁺·Cl⁻	F(000) = 360
M_r = 171.62	D_x = 1.394 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2016 reflections
a = 4.8979 (1) Å	θ = 2.3–29.1°
b = 15.8136 (4) Å	µ = 0.41 mm⁻¹
c = 10.8203 (3) Å	T = 100 K
β = 102.569 (3)°	Pris,, colourless
V = 817.98 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	1436 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1256 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.019
Detector resolution: 10.4041 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω scans	h = −5→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −18→17
T_min = 0.920, T_max = 1.000	l = −10→12
3262 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0393P)² + 0.2093P] where P = (F_o² + 2F_c²)/3
1436 reflections	(Δ/σ)_max = 0.001
113 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₁₀NO⁺·Cl⁻	V = 817.98 (3) Å³
M_r = 171.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8979 (1) Å	µ = 0.41 mm⁻¹
b = 15.8136 (4) Å	T = 100 K
c = 10.8203 (3) Å	0.30 × 0.25 × 0.20 mm
β = 102.569 (3)°

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	1436 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1256 reflections with I > 2σ(I)
T_min = 0.920, T_max = 1.000	R_int = 0.019
3262 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.20 e Å⁻³
1436 reflections	Δρ_min = −0.27 e Å⁻³
113 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
Cl1	0.10927 (9)	0.47141 (2)	0.83017 (4)	0.02647 (17)
O1	0.8706 (2)	0.23737 (7)	0.91735 (11)	0.0277 (3)
N1	0.6529 (3)	0.38178 (9)	0.98223 (14)	0.0210 (3)
H1N	0.508 (4)	0.4081 (12)	0.9220 (19)	0.036 (5)*
H2N	0.753 (4)	0.4233 (13)	1.0322 (19)	0.033 (5)*
H3N	0.759 (4)	0.3532 (12)	0.9418 (19)	0.034 (5)*
C1	0.7572 (5)	0.10071 (11)	0.97971 (19)	0.0377 (5)
H1A	0.8665	0.0826	0.9186	0.057*
H1B	0.5674	0.0776	0.9552	0.057*
H1C	0.8466	0.0800	1.0642	0.057*
C2	0.7435 (3)	0.19573 (10)	0.98154 (15)	0.0233 (4)
C3	0.5701 (3)	0.23753 (10)	1.06204 (15)	0.0197 (4)
C4	0.4392 (4)	0.18953 (10)	1.14121 (16)	0.0238 (4)
H4	0.4639	0.1299	1.1444	0.029*
C5	0.2751 (4)	0.22678 (11)	1.21474 (16)	0.0253 (4)
H5	0.1875	0.1928	1.2673	0.030*
C6	0.2381 (3)	0.31345 (10)	1.21206 (16)	0.0240 (4)
H6	0.1249	0.3391	1.2626	0.029*
C7	0.3663 (3)	0.36268 (10)	1.13559 (15)	0.0219 (4)
H7	0.3423	0.4223	1.1337	0.026*
C8	0.5289 (3)	0.32504 (10)	1.06211 (15)	0.0185 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0285 (3)	0.0215 (3)	0.0298 (3)	0.00177 (17)	0.00704 (19)	−0.00224 (17)
O1	0.0280 (7)	0.0299 (7)	0.0275 (7)	0.0043 (5)	0.0113 (6)	−0.0002 (5)
N1	0.0222 (8)	0.0193 (8)	0.0235 (8)	−0.0005 (7)	0.0091 (7)	0.0013 (7)
C1	0.0527 (13)	0.0241 (10)	0.0401 (12)	0.0081 (9)	0.0182 (10)	−0.0017 (9)
C2	0.0230 (9)	0.0236 (9)	0.0212 (9)	0.0040 (7)	0.0003 (7)	−0.0008 (7)
C3	0.0173 (8)	0.0210 (9)	0.0199 (8)	0.0010 (7)	0.0016 (7)	0.0006 (7)
C4	0.0251 (9)	0.0188 (9)	0.0262 (9)	0.0001 (7)	0.0027 (7)	0.0048 (7)
C5	0.0226 (9)	0.0300 (10)	0.0238 (9)	−0.0034 (8)	0.0060 (7)	0.0067 (8)
C6	0.0196 (9)	0.0304 (10)	0.0232 (9)	0.0015 (7)	0.0073 (7)	−0.0005 (8)
C7	0.0205 (9)	0.0191 (9)	0.0264 (9)	0.0015 (7)	0.0058 (7)	−0.0005 (7)
C8	0.0158 (8)	0.0205 (8)	0.0190 (8)	−0.0017 (6)	0.0031 (7)	0.0017 (7)

Geometric parameters (Å, º) top

O1—C2	1.221 (2)	C3—C8	1.399 (2)
N1—C8	1.466 (2)	C3—C4	1.400 (2)
N1—H1N	0.95 (2)	C4—C5	1.380 (2)
N1—H2N	0.92 (2)	C4—H4	0.9500
N1—H3N	0.87 (2)	C5—C6	1.382 (2)
C1—C2	1.504 (2)	C5—H5	0.9500
C1—H1A	0.9800	C6—C7	1.383 (2)
C1—H1B	0.9800	C6—H6	0.9500
C1—H1C	0.9800	C7—C8	1.377 (2)
C2—C3	1.496 (2)	C7—H7	0.9500

C8—N1—H1N	109.3 (12)	C4—C3—C2	120.68 (15)
C8—N1—H2N	108.9 (12)	C5—C4—C3	121.54 (15)
H1N—N1—H2N	108.2 (16)	C5—C4—H4	119.2
C8—N1—H3N	110.2 (13)	C3—C4—H4	119.2
H1N—N1—H3N	108.7 (18)	C4—C5—C6	120.10 (16)
H2N—N1—H3N	111.5 (18)	C4—C5—H5	120.0
C2—C1—H1A	109.5	C6—C5—H5	120.0
C2—C1—H1B	109.5	C5—C6—C7	119.76 (16)
H1A—C1—H1B	109.5	C5—C6—H6	120.1
C2—C1—H1C	109.5	C7—C6—H6	120.1
H1A—C1—H1C	109.5	C8—C7—C6	119.82 (15)
H1B—C1—H1C	109.5	C8—C7—H7	120.1
O1—C2—C3	121.12 (15)	C6—C7—H7	120.1
O1—C2—C1	120.10 (16)	C7—C8—C3	121.98 (15)
C3—C2—C1	118.77 (15)	C7—C8—N1	116.21 (14)
C8—C3—C4	116.80 (15)	C3—C8—N1	121.80 (14)
C8—C3—C2	122.52 (14)

O1—C2—C3—C8	4.3 (2)	C5—C6—C7—C8	0.3 (2)
C1—C2—C3—C8	−175.12 (16)	C6—C7—C8—C3	−0.1 (2)
O1—C2—C3—C4	−176.05 (15)	C6—C7—C8—N1	178.95 (14)
C1—C2—C3—C4	4.6 (2)	C4—C3—C8—C7	−0.4 (2)
C8—C3—C4—C5	0.7 (2)	C2—C3—C8—C7	179.28 (15)
C2—C3—C4—C5	−179.04 (15)	C4—C3—C8—N1	−179.37 (15)
C3—C4—C5—C6	−0.4 (3)	C2—C3—C8—N1	0.3 (2)
C4—C5—C6—C7	−0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···Cl1	0.95 (2)	2.23 (2)	3.1463 (15)	163 (2)
N1—H2n···Cl1ⁱ	0.92 (2)	2.24 (2)	3.1366 (15)	165 (2)
N1—H3n···O1	0.87 (2)	1.95 (2)	2.6778 (18)	140 (2)
C5—H5···Cl1ⁱⁱ	0.95	2.73	3.5332 (18)	142
C6—H6···O1ⁱⁱⁱ	0.95	2.59	3.2496 (19)	127

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀NO⁺·Cl⁻
M_r	171.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	4.8979 (1), 15.8136 (4), 10.8203 (3)
β (°)	102.569 (3)
V (Å³)	817.98 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.920, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3262, 1436, 1256
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.07
No. of reflections	1436
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.27

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···Cl1	0.95 (2)	2.23 (2)	3.1463 (15)	162.9 (17)
N1—H2n···Cl1ⁱ	0.92 (2)	2.24 (2)	3.1366 (15)	165.0 (17)
N1—H3n···O1	0.87 (2)	1.946 (19)	2.6778 (18)	140.3 (18)
C5—H5···Cl1ⁱⁱ	0.95	2.73	3.5332 (18)	142
C6—H6···O1ⁱⁱⁱ	0.95	2.59	3.2496 (19)	127

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

Footnotes

‡Additional correspondence author, e-mail: juliebhavana@gmail.com.

Acknowledgements

PB acknowledges the Department of Science and Technology (DST), India, for a research grant (SR/FTP/CS-57/2007). The authors thank the University of Malaya for supporting this study.

References

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