4-Acetyl­anilinium perchlorate

In the title compound, C₈H₁₀NO⁺·ClO₄⁻, the ions are connected in a three-dimensional hydrogen-bonded network via N—H...O hydrogen bonds, with four characteristic graph-set motifs: C(8), C₂²(6), R₄²(10) and R₄⁴(12).

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.137
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

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Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        Cl1

Alert level C
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        N31

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The molecular structure of compound (I), C₈H₁₀NO⁺ ClO₄^-, is shown in Figure 1. The asymmetric unit consists of 4-acetylanilinium cation with protonated amino group and perchlorate anion. All bond lengths and bond angles correspond to the geometry parameters expected for atom types and the type of hybridization (Allen et al., 1987).

The ions are connected in three-dimensional hydrogen-bonded network via N–H···O hydrogen bonds. All ammonium group H atoms are involved in the hydrogen bonding with three O-atoms of neighbouring perchlorate anion and O-atom of carbonyl group of neighbouring cation, with four-centred geometry motif observed. Four characteristic graph-set motifs can be recognized: C₁¹(8), C₂²(6), R₄²(10) and R₄⁴(12) in the notation of Bernstein et al. (1995). Both ten- and twelve-membered ring moieties [R₄²(10) and R₄⁴(12)] are formed of two 4-acetylanilinium cations and two perchlorate anion. The centre of twelve-membered ring is situated on a crystallographic centre of symmetry. The aggregation of two ring moieties results in infinite one-dimensional chains spreading along the a axis, with intercalated array of perchlorate ions, Fig. 2. Two infinite one-dimensional chains are detected with the donor participations of H31A in C(8) motif and H31B and H31C in C₂²(6) graph-set motif.

Related literature

For related literature, see: Bernstein et al. (1995); Athimoolam & Natarajan (2006); Cinčić & Kaitner (2007). For bond-length data, see: Allen et al. (1987).

S2. Experimental

Single crystals of compound (I) were obtained by slow evaporation method. A solution of 100 mg 4'-aminoacetophenone dissolved in 2 ml of 2-propanol was heated at 70 °C. The clear solution was obtained, added to the 3 ml of perchloric acid (60%) and then left at room temperature. The crystals of (I) were collected by vacuum filtration, washed with cold acetone and dried in air.

S3. Refinement

All N-bound H atoms were located in difference Fourier map and their positions and isotropic parameters were refined. Aromatic and methyl H atoms were placed in calculated positions and treated as riding on their parent C atoms, with C—H = 0.93 Å, U_iso(H) = 1.2U_eq(C) for Csp² and C—H = 0.96 Å, U_ĩso(H) = 1.5U_eq(C) for Csp³, respectively.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST97 (Nardelli, 1995).

Figures

	Fig. 1. The asymetric unit of (I), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. A view of the one-dimensional hydrogen-bonded chain along c axis showing the aggregation of two different hydrogen-bonding motifs, R4^2(10) and R4^4(12). Hydrogen bonds are drawn as red dotted lines.

4-Acetylanilinium perchlorate

Crystal data

C8H10NO^+·ClO4^−	Z = 4
Mr = 235.62	F(000) = 488
Monoclinic, P21/c	Dx = 1.522 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.0287 (2) Å	µ = 0.37 mm^−1
b = 18.9091 (3) Å	T = 295 K
c = 7.1327 (2) Å	Prisms, colourles
β = 108.248 (2)°	0.55 × 0.25 × 0.17 mm
V = 1028.40 (4) Å^3

Data collection

Oxford Diffraction Xcalibur CCD diffractometer	2240 independent reflections
Radiation source: fine-focus sealed tube	1879 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ω scans	θmax = 27.0°, θmin = 4.0°
Absorption correction: analytical (Alcock, 1970)	h = −10→10
Tmin = 0.845, Tmax = 0.943	k = −24→23
10153 measured reflections	l = −9→9

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.137	w = 1/[σ^2(Fo^2) + (0.0754P)^2 + 0.4245P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
2240 reflections	Δρmax = 0.42 e Å^−3
150 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (6)

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	0.35257 (7)	0.05725 (3)	0.73397 (7)	0.0458 (2)
O1	0.3640 (3)	0.11005 (10)	0.8786 (3)	0.0785 (6)
O2	0.5188 (2)	0.04870 (10)	0.6992 (3)	0.0637 (5)
O3	0.3092 (3)	−0.00828 (10)	0.8051 (4)	0.0811 (7)
O4	0.2255 (4)	0.07531 (19)	0.5542 (4)	0.1239 (12)
O5	1.18693 (19)	0.30662 (9)	0.6715 (3)	0.0641 (5)
N31	0.4986 (2)	0.11924 (9)	0.3228 (3)	0.0416 (4)
C1	0.8949 (2)	0.27357 (9)	0.5168 (3)	0.0357 (4)
C2	0.7219 (2)	0.29362 (10)	0.4321 (3)	0.0398 (4)
H2	0.6932	0.3414	0.4174	0.048*
C3	0.5910 (2)	0.24323 (10)	0.3689 (3)	0.0404 (4)
H3	0.4746	0.2567	0.3128	0.048*
C4	0.6366 (2)	0.17271 (9)	0.3909 (2)	0.0346 (4)
C5	0.8088 (2)	0.15104 (10)	0.4759 (3)	0.0398 (4)
H5	0.8370	0.1032	0.4901	0.048*
C6	0.9370 (2)	0.20189 (10)	0.5388 (3)	0.0396 (4)
H6	1.0531	0.1882	0.5967	0.048*
C7	1.0388 (2)	0.32664 (10)	0.5850 (3)	0.0417 (4)
C8	1.0006 (3)	0.40387 (11)	0.5470 (4)	0.0550 (6)
H8A	1.1086	0.4300	0.5855	0.082*
H8B	0.9275	0.4199	0.6222	0.082*
H8C	0.9412	0.4112	0.4090	0.082*
H31A	0.397 (4)	0.1386 (18)	0.273 (5)	0.082 (10)*
H31B	0.494 (4)	0.0911 (16)	0.418 (4)	0.064 (8)*
H31C	0.525 (4)	0.0918 (17)	0.244 (4)	0.066 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0520 (3)	0.0391 (3)	0.0475 (3)	0.00303 (18)	0.0174 (2)	−0.00315 (18)
O1	0.0997 (15)	0.0607 (11)	0.0927 (14)	−0.0199 (10)	0.0556 (12)	−0.0335 (10)
O2	0.0633 (11)	0.0677 (11)	0.0711 (11)	−0.0006 (8)	0.0368 (9)	0.0008 (8)
O3	0.0843 (14)	0.0478 (10)	0.1317 (19)	−0.0144 (9)	0.0631 (14)	−0.0071 (11)
O4	0.113 (2)	0.171 (3)	0.0716 (15)	0.075 (2)	0.0057 (14)	0.0108 (16)
O5	0.0356 (8)	0.0511 (9)	0.0917 (13)	−0.0021 (6)	0.0002 (8)	0.0031 (8)
N31	0.0382 (8)	0.0370 (8)	0.0492 (10)	−0.0004 (7)	0.0131 (7)	0.0003 (7)
C1	0.0327 (8)	0.0371 (9)	0.0369 (8)	0.0021 (7)	0.0103 (7)	0.0008 (7)
C2	0.0377 (9)	0.0326 (9)	0.0487 (10)	0.0065 (7)	0.0128 (8)	0.0039 (7)
C3	0.0319 (8)	0.0386 (9)	0.0485 (10)	0.0053 (7)	0.0095 (7)	0.0033 (8)
C4	0.0339 (8)	0.0367 (9)	0.0335 (8)	0.0009 (7)	0.0108 (7)	0.0008 (7)
C5	0.0389 (9)	0.0336 (9)	0.0446 (10)	0.0067 (7)	0.0096 (8)	0.0030 (7)
C6	0.0323 (9)	0.0394 (9)	0.0434 (10)	0.0080 (7)	0.0063 (7)	0.0018 (7)
C7	0.0365 (9)	0.0412 (10)	0.0475 (10)	0.0001 (7)	0.0132 (8)	−0.0006 (8)
C8	0.0468 (11)	0.0400 (11)	0.0767 (15)	−0.0015 (8)	0.0172 (11)	−0.0025 (10)

Geometric parameters (Å, º)

Cl1—O4	1.408 (2)	C2—C3	1.385 (3)
Cl1—O1	1.4180 (18)	C2—H2	0.9300
Cl1—O3	1.4228 (19)	C3—C4	1.379 (3)
Cl1—O2	1.4404 (18)	C3—H3	0.9300
O5—C7	1.216 (2)	C4—C5	1.386 (2)
N31—C4	1.466 (2)	C5—C6	1.378 (3)
N31—H31A	0.86 (3)	C5—H5	0.9300
N31—H31B	0.88 (3)	C6—H6	0.9300
N31—H31C	0.84 (3)	C7—C8	1.499 (3)
C1—C2	1.383 (2)	C8—H8A	0.9600
C1—C6	1.394 (3)	C8—H8B	0.9600
C1—C7	1.492 (3)	C8—H8C	0.9600
O4—Cl1—O1	110.80 (16)	C2—C3—H3	120.6
O4—Cl1—O3	110.34 (19)	C3—C4—C5	121.91 (17)
O1—Cl1—O3	108.72 (13)	C3—C4—N31	118.89 (16)
O4—Cl1—O2	108.46 (15)	C5—C4—N31	119.19 (16)
O1—Cl1—O2	110.60 (12)	C6—C5—C4	118.53 (17)
O3—Cl1—O2	107.87 (11)	C6—C5—H5	120.7
C4—N31—H31A	111 (2)	C4—C5—H5	120.7
C4—N31—H31B	112.0 (19)	C5—C6—C1	120.78 (16)
H31A—N31—H31B	108 (3)	C5—C6—H6	119.6
C4—N31—H31C	109 (2)	C1—C6—H6	119.6
H31A—N31—H31C	113 (3)	O5—C7—C1	119.37 (18)
H31B—N31—H31C	103 (3)	O5—C7—C8	120.48 (18)
C2—C1—C6	119.40 (17)	C1—C7—C8	120.16 (17)
C2—C1—C7	121.82 (17)	C7—C8—H8A	109.5
C6—C1—C7	118.78 (16)	C7—C8—H8B	109.5
C1—C2—C3	120.62 (17)	H8A—C8—H8B	109.5
C1—C2—H2	119.7	C7—C8—H8C	109.5
C3—C2—H2	119.7	H8A—C8—H8C	109.5
C4—C3—C2	118.75 (16)	H8B—C8—H8C	109.5
C4—C3—H3	120.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N31—H31B···O2	0.87 (3)	2.11 (3)	2.957 (3)	163 (3)
N31—H31A···O5^i	0.86 (3)	1.92 (3)	2.775 (2)	173 (3)
N31—H31C···O1^ii	0.84 (3)	2.54 (3)	3.015 (3)	116 (2)
N31—H31C···O3^iii	0.84 (3)	2.16 (3)	2.915 (3)	149 (3)

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