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In the title compound, C9H13N2O+·I, the dihedral angle between the aromatic ring and the N-acetyl group is 73.93 (8)°. In the crystal structure, the cation and anion inter­act by way of an N—H...I hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046090/lh2511sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046090/lh2511Isup2.hkl
Contains datablock I

CCDC reference: 667324

Key indicators

  • Single-crystal X-ray study
  • T = 93 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.019
  • wR factor = 0.047
  • Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT411_ALERT_2_C Short Inter H...H Contact H6A .. H6A .. 2.13 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 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

Comment top

The title compound, (I) (Fig. 1), is an intermediate in the synthesis of azacyanine dyes (Javet et al., 2007) The dihedral angle between the C1—C5/N1 pyrininium ring and the C7/C8/N2/O1 grouping in (I) is 73.93 (8)°. Otherwise, the geometry of (I) may be regarded as normal (Allen et al., 1995).

In the crystal of (I), an N—H···I hydrogen bond (Table 1) links the cation and the anion. A weak C—H···O interaction may also help to consolidate the packing, leading to [001] chains. There are no aromatic π-π stacking interactions in (I) as the closest centroid-centroid separation is greater than 4.37 Å.

Related literature top

For background, see: Javet et al. (2007). For reference structural data, see: Allen et al. (1995).

Experimental top

4-Aminomethylpyridine was aceylated with acetic anhydride in water, followed by methylation with CH3I in CH2Cl2, yielding yellow cubic blocks of (I) after solvent removal.

Refinement top

The N-bound hydrogen atom was located in a difference map and its position was freely refined with Uiso(H) = 1.2Ueq(N). The C-bound hydrogen atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not tip, to best fit the electron density.

Structure description top

The title compound, (I) (Fig. 1), is an intermediate in the synthesis of azacyanine dyes (Javet et al., 2007) The dihedral angle between the C1—C5/N1 pyrininium ring and the C7/C8/N2/O1 grouping in (I) is 73.93 (8)°. Otherwise, the geometry of (I) may be regarded as normal (Allen et al., 1995).

In the crystal of (I), an N—H···I hydrogen bond (Table 1) links the cation and the anion. A weak C—H···O interaction may also help to consolidate the packing, leading to [001] chains. There are no aromatic π-π stacking interactions in (I) as the closest centroid-centroid separation is greater than 4.37 Å.

For background, see: Javet et al. (2007). For reference structural data, see: Allen et al. (1995).

Computing details top

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); 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: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). The hydrogen bond is indicated by a double-dashed line.
4-(Acetylaminomethyl)-1-methylpyridinium iodide top
Crystal data top
C9H13N2O+·IZ = 4
Mr = 292.11F(000) = 568
Monoclinic, P21/cDx = 1.712 Mg m3
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.597 (2) ŵ = 2.79 mm1
b = 12.986 (3) ÅT = 93 K
c = 10.335 (3) ÅCube, yellow
β = 100.802 (5)°0.10 × 0.10 × 0.10 mm
V = 1133.4 (5) Å3
Data collection top
Rigaku Mercury CCD
diffractometer
1932 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 25.3°, θmin = 2.4°
ω and φ scansh = 910
6776 measured reflectionsk = 1514
2035 independent reflectionsl = 1112
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019Hydrogen site location: difmap and geom
wR(F2) = 0.048H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0262P)2 + 0.8567P]
where P = (Fo2 + 2Fc2)/3
2035 reflections(Δ/σ)max = 0.002
123 parametersΔρmax = 0.82 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C9H13N2O+·IV = 1133.4 (5) Å3
Mr = 292.11Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.597 (2) ŵ = 2.79 mm1
b = 12.986 (3) ÅT = 93 K
c = 10.335 (3) Å0.10 × 0.10 × 0.10 mm
β = 100.802 (5)°
Data collection top
Rigaku Mercury CCD
diffractometer
1932 reflections with I > 2σ(I)
6776 measured reflectionsRint = 0.023
2035 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.048H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.82 e Å3
2035 reflectionsΔρmin = 0.46 e Å3
123 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
xyzUiso*/Ueq
C10.1654 (3)0.42190 (17)0.5581 (2)0.0205 (5)
H10.17100.39760.47240.025*
C20.0883 (3)0.36517 (17)0.6378 (2)0.0196 (4)
H2A0.03950.30200.60660.024*
C30.1502 (3)0.48747 (17)0.8068 (2)0.0207 (5)
H30.14450.50940.89350.025*
C40.2286 (3)0.54695 (17)0.7301 (2)0.0202 (5)
H40.27780.60930.76400.024*
C50.2361 (2)0.51580 (16)0.6022 (2)0.0176 (4)
C60.3140 (3)0.57832 (18)0.5096 (2)0.0226 (5)
H6A0.38520.53260.47080.027*
H6B0.23090.60330.43680.027*
C70.3626 (3)0.76363 (17)0.5334 (2)0.0200 (5)
C80.4766 (3)0.84538 (18)0.5954 (3)0.0278 (5)
H8A0.54970.81610.67050.042*
H8B0.41760.90230.62570.042*
H8C0.53660.87110.53030.042*
C90.0093 (3)0.33746 (18)0.8422 (2)0.0255 (5)
H9A0.01770.26600.81130.038*
H9B0.11560.36680.83520.038*
H9C0.04550.33940.93430.038*
N10.0809 (2)0.39812 (12)0.76054 (19)0.0179 (4)
N20.4043 (2)0.66579 (14)0.5685 (2)0.0218 (4)
H20.485 (3)0.655 (2)0.617 (3)0.026*
O10.23978 (19)0.78412 (13)0.45526 (17)0.0281 (4)
I10.753932 (15)0.602150 (10)0.806080 (13)0.01921 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0250 (12)0.0206 (10)0.0147 (11)0.0018 (9)0.0008 (9)0.0032 (9)
C20.0237 (11)0.0155 (10)0.0178 (11)0.0024 (9)0.0006 (9)0.0033 (9)
C30.0208 (11)0.0238 (11)0.0155 (11)0.0028 (9)0.0016 (9)0.0045 (9)
C40.0203 (11)0.0170 (10)0.0212 (11)0.0014 (8)0.0020 (9)0.0068 (9)
C50.0149 (10)0.0173 (10)0.0183 (11)0.0051 (8)0.0031 (8)0.0005 (8)
C60.0224 (12)0.0222 (10)0.0219 (12)0.0002 (9)0.0010 (10)0.0007 (9)
C70.0195 (11)0.0221 (11)0.0196 (11)0.0011 (9)0.0070 (9)0.0024 (9)
C80.0269 (12)0.0206 (11)0.0360 (14)0.0033 (9)0.0061 (11)0.0019 (10)
C90.0291 (12)0.0270 (12)0.0194 (12)0.0006 (10)0.0020 (10)0.0044 (9)
N10.0176 (10)0.0191 (9)0.0150 (10)0.0035 (7)0.0017 (8)0.0010 (7)
N20.0178 (9)0.0202 (9)0.0243 (11)0.0003 (7)0.0039 (8)0.0027 (8)
O10.0246 (9)0.0277 (9)0.0300 (10)0.0024 (7)0.0002 (7)0.0102 (7)
I10.01935 (11)0.02071 (10)0.01594 (11)0.00113 (5)0.00091 (7)0.00050 (5)
Geometric parameters (Å, º) top
C1—C21.365 (3)C6—H6B0.9900
C1—C51.400 (3)C7—O11.232 (3)
C1—H10.9500C7—N21.351 (3)
C2—N11.352 (3)C7—C81.504 (3)
C2—H2A0.9500C8—H8A0.9800
C3—N11.350 (3)C8—H8B0.9800
C3—C41.371 (3)C8—H8C0.9800
C3—H30.9500C9—N11.476 (3)
C4—C51.395 (3)C9—H9A0.9800
C4—H40.9500C9—H9B0.9800
C5—C61.505 (3)C9—H9C0.9800
C6—N21.445 (3)N2—H20.79 (3)
C6—H6A0.9900
C2—C1—C5120.2 (2)O1—C7—N2122.1 (2)
C2—C1—H1119.9O1—C7—C8122.4 (2)
C5—C1—H1119.9N2—C7—C8115.5 (2)
N1—C2—C1120.6 (2)C7—C8—H8A109.5
N1—C2—H2A119.7C7—C8—H8B109.5
C1—C2—H2A119.7H8A—C8—H8B109.5
N1—C3—C4120.8 (2)C7—C8—H8C109.5
N1—C3—H3119.6H8A—C8—H8C109.5
C4—C3—H3119.6H8B—C8—H8C109.5
C3—C4—C5120.0 (2)N1—C9—H9A109.5
C3—C4—H4120.0N1—C9—H9B109.5
C5—C4—H4120.0H9A—C9—H9B109.5
C4—C5—C1117.8 (2)N1—C9—H9C109.5
C4—C5—C6123.5 (2)H9A—C9—H9C109.5
C1—C5—C6118.7 (2)H9B—C9—H9C109.5
N2—C6—C5115.13 (19)C3—N1—C2120.60 (19)
N2—C6—H6A108.5C3—N1—C9120.02 (19)
C5—C6—H6A108.5C2—N1—C9119.34 (18)
N2—C6—H6B108.5C7—N2—C6122.1 (2)
C5—C6—H6B108.5C7—N2—H2120 (2)
H6A—C6—H6B107.5C6—N2—H2118 (2)
C5—C1—C2—N10.8 (3)C4—C3—N1—C20.4 (3)
N1—C3—C4—C50.7 (3)C4—C3—N1—C9177.2 (2)
C3—C4—C5—C11.7 (3)C1—C2—N1—C30.3 (3)
C3—C4—C5—C6177.5 (2)C1—C2—N1—C9177.3 (2)
C2—C1—C5—C41.8 (3)O1—C7—N2—C64.6 (3)
C2—C1—C5—C6177.4 (2)C8—C7—N2—C6174.9 (2)
C4—C5—C6—N29.8 (3)C5—C6—N2—C7115.1 (2)
C1—C5—C6—N2171.05 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···I10.79 (3)2.81 (3)3.603 (2)174 (3)
C4—H4···O1i0.952.483.186 (3)131
Symmetry code: (i) x, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC9H13N2O+·I
Mr292.11
Crystal system, space groupMonoclinic, P21/c
Temperature (K)93
a, b, c (Å)8.597 (2), 12.986 (3), 10.335 (3)
β (°) 100.802 (5)
V3)1133.4 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.79
Crystal size (mm)0.10 × 0.10 × 0.10
Data collection
DiffractometerRigaku Mercury CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6776, 2035, 1932
Rint0.023
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.048, 1.04
No. of reflections2035
No. of parameters123
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.82, 0.46

Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···I10.79 (3)2.81 (3)3.603 (2)174 (3)
C4—H4···O1i0.952.483.186 (3)131
Symmetry code: (i) x, y+3/2, z+1/2.
 

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