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ISSN: 2056-9890

Redetermination of 3-(ammonio­meth­yl)pyridinium dichloride

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: quzr@seu.edu.cn

(Received 28 June 2009; accepted 3 July 2009; online 11 July 2009)

The crystal structure of the title compound, C6H10N22+·2Cl, has been reported previously in the non-standard setting P21/a [Genet (1965[Genet, F. (1965). Bull. Soc. Fr. Mineral. Cristallogr. 88, 463-470.]). Bull. Soc. Fr. Miner. Crist. 88, 463–470], with an R value of 0.16. The current redetermination improves significantly the precision of the geometric parameters. In the crystal packing, cations and anions are linked by inter­molecular N—H⋯Cl and C—H⋯Cl hydrogen bonds into a three-dimensional network.

Related literature

For related structures, see: Genet (1965[Genet, F. (1965). Bull. Soc. Fr. Mineral. Cristallogr. 88, 463-470.]); Chtioui & Jouini (2004[Chtioui, A. & Jouini, A. (2004). J. Chem. Crystallogr. A34, 43-49.]); Long et al. (1997[Long, G. S., Wei, M. & Willett, R. D. (1997). Inorg. Chem. 36, 3102-3107.]).

[Scheme 1]

Experimental

Crystal data
  • C6H10N22+·2Cl

  • Mr = 181.06

  • Monoclinic, P 21 /c

  • a = 4.5874 (9) Å

  • b = 12.650 (3) Å

  • c = 14.814 (3) Å

  • β = 93.61 (3)°

  • V = 857.9 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.69 mm−1

  • T = 293 K

  • 0.50 × 0.45 × 0.15 mm

Data collection
  • Rigaku SCXmini diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.720, Tmax = 0.909

  • 8831 measured reflections

  • 1961 independent reflections

  • 1684 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.076

  • S = 1.08

  • 1961 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯Cl2i 0.89 2.35 3.1914 (16) 157
N1—H1B⋯Cl2ii 0.89 2.27 3.1206 (16) 159
N1—H1C⋯Cl1iii 0.89 2.28 3.1622 (16) 170
N2—H2⋯Cl1iv 0.86 2.25 3.0520 (16) 154
C3—H3⋯Cl2i 0.93 2.77 3.606 (2) 150
C6—H6A⋯Cl1v 0.97 2.74 3.676 (2) 163
C6—H6B⋯Cl2vi 0.97 2.82 3.700 (2) 152
Symmetry codes: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (iii) -x+1, -y+1, -z; (iv) x+1, y+1, z; (v) -x+2, -y+1, -z; (vi) [-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

Pyridin-3-ylmethanamine is a important ligand used in coordination chemistry. Recently, there has been an increased interest in the properties of layer perovskite structures because of their applications in high temperature superconductivity. Two general classes of M(II) halide layer perovskite structures exist, the ammoniummethylprididine series (Chtioui & Jouini, 2004) and the ammoniummethylprididinium series (Long et al., 1997). In the latter series, the asymmetrical dication bridges between layers, with both the NH3+ group and the pyridinium N—H group hydrogen bonding to the halide ions in the layer. The cation-layer interactions involve an ammonium group that hydrogen bonds to the perovskite layer (Long et al., 1997). We report herein the crystal structure of the title compound, which was prepared by the reaction of pyridin-3-ylmethanamine and hydrochloric acid. Its crystal structure has been reported previously in the non standard setting P21/a (Genet, 1965), with an R value of 0.16. The current redetermination improves significantly the precision of the geometric parameters.

The asymmetric unit of the title compound (Fig. 1) consists of a two independent chloride anions and a 3-(ammoniomethyl)pyridinium dication. In the cation, the plane through the C2/C6/N2 atoms is tilted by 68.13 (14)° with respect to the pyridine ring. In the crystal packing (Fig. 2), intermolecular N—H···Cl and C—H···Cl hydrogen bonds (Table 1) connect neighbouring cations and anions into a three-dimensional network.

Related literature top

For related structures, see: Genet (1965); Chtioui & Jouini (2004); Long et al. (1997).

Experimental top

A mixture of (pyridin-3-yl)methanamine (0.1 mol, 0.108 g) and HCl (0.2 mol, 0.73 g) were dissolved in water (10 ml). Colourless single crystals of the title compound suitable for X-ray analysis were obtained on slow evaporation of the solvent over a period of 48 h.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on their parent atoms, with C—H = 0.93-0.97 Å, N—H = 0.86-0.89 Å, and with Uiso(H) = 1.2 Ueq(C, N).

Computing details top

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 top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the a axis>. Hydrogen bonds are shown as dashed lines.
3-(ammoniomethyl)pyridinium dichloride top
Crystal data top
C6H10N22+·2ClF(000) = 376
Mr = 181.06Dx = 1.402 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8048 reflections
a = 4.5874 (9) Åθ = 3.1–27.5°
b = 12.650 (3) ŵ = 0.69 mm1
c = 14.814 (3) ÅT = 293 K
β = 93.61 (3)°Prism, colourless
V = 857.9 (3) Å30.50 × 0.45 × 0.15 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer
1961 independent reflections
Radiation source: fine-focus sealed tube1684 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 13.662 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scansh = 55
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1616
Tmin = 0.720, Tmax = 0.909l = 1919
8831 measured reflections
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0293P)2 + 0.274P]
where P = (Fo2 + 2Fc2)/3
1961 reflections(Δ/σ)max = 0.001
92 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C6H10N22+·2ClV = 857.9 (3) Å3
Mr = 181.06Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.5874 (9) ŵ = 0.69 mm1
b = 12.650 (3) ÅT = 293 K
c = 14.814 (3) Å0.50 × 0.45 × 0.15 mm
β = 93.61 (3)°
Data collection top
Rigaku SCXmini
diffractometer
1961 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1684 reflections with I > 2σ(I)
Tmin = 0.720, Tmax = 0.909Rint = 0.035
8831 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.08Δρmax = 0.21 e Å3
1961 reflectionsΔρmin = 0.19 e Å3
92 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
Cl20.34023 (9)0.98847 (3)0.37672 (3)0.03348 (13)
N10.9075 (3)0.64924 (10)0.01920 (10)0.0333 (3)
H1A0.78850.60980.01200.050*
H1B0.99050.60910.05980.050*
H1C0.80580.70070.04740.050*
C61.1364 (4)0.69588 (14)0.04332 (13)0.0365 (4)
H6A1.28880.72530.00840.044*
H6B1.22310.64050.08150.044*
C11.1087 (4)0.88417 (13)0.08977 (12)0.0337 (4)
H11.23490.90000.04490.040*
C50.8274 (4)0.94441 (14)0.20641 (12)0.0370 (4)
H50.76191.00050.24030.044*
C21.0214 (3)0.78119 (13)0.10227 (11)0.0293 (4)
C40.7351 (4)0.84350 (14)0.22213 (12)0.0371 (4)
H40.60600.83040.26680.045*
C30.8357 (4)0.76140 (14)0.17102 (12)0.0349 (4)
H30.77880.69240.18260.042*
Cl10.40819 (11)0.14752 (3)0.10233 (3)0.04427 (15)
N21.0124 (3)0.96146 (11)0.14194 (10)0.0367 (4)
H21.07241.02490.13360.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl20.0384 (2)0.0291 (2)0.0340 (2)0.00167 (16)0.01032 (17)0.00133 (16)
N10.0389 (8)0.0256 (7)0.0362 (8)0.0047 (6)0.0099 (6)0.0021 (6)
C60.0310 (9)0.0315 (9)0.0479 (11)0.0040 (7)0.0086 (8)0.0028 (8)
C10.0347 (9)0.0314 (9)0.0352 (9)0.0001 (7)0.0041 (7)0.0029 (7)
C50.0440 (10)0.0354 (10)0.0311 (9)0.0044 (8)0.0011 (8)0.0071 (7)
C20.0260 (8)0.0284 (8)0.0331 (9)0.0020 (6)0.0008 (7)0.0010 (7)
C40.0406 (10)0.0407 (10)0.0306 (9)0.0030 (8)0.0064 (8)0.0032 (7)
C30.0390 (10)0.0297 (9)0.0363 (10)0.0038 (7)0.0044 (8)0.0005 (7)
Cl10.0486 (3)0.0305 (2)0.0547 (3)0.00301 (18)0.0108 (2)0.00943 (19)
N20.0462 (9)0.0237 (7)0.0397 (9)0.0029 (6)0.0014 (7)0.0013 (6)
Geometric parameters (Å, º) top
N1—C61.478 (2)C1—H10.9300
N1—H1A0.8900C5—N21.334 (2)
N1—H1B0.8900C5—C41.369 (3)
N1—H1C0.8900C5—H50.9300
C6—C21.504 (2)C2—C31.391 (2)
C6—H6A0.9700C4—C31.382 (2)
C6—H6B0.9700C4—H40.9300
C1—N21.338 (2)C3—H30.9300
C1—C21.379 (2)N2—H20.8600
C6—N1—H1A109.5N2—C5—C4119.33 (16)
C6—N1—H1B109.5N2—C5—H5120.3
H1A—N1—H1B109.5C4—C5—H5120.3
C6—N1—H1C109.5C1—C2—C3117.69 (16)
H1A—N1—H1C109.5C1—C2—C6118.97 (16)
H1B—N1—H1C109.5C3—C2—C6123.31 (15)
N1—C6—C2112.88 (13)C5—C4—C3119.34 (17)
N1—C6—H6A109.0C5—C4—H4120.3
C2—C6—H6A109.0C3—C4—H4120.3
N1—C6—H6B109.0C4—C3—C2120.47 (16)
C2—C6—H6B109.0C4—C3—H3119.8
H6A—C6—H6B107.8C2—C3—H3119.8
N2—C1—C2120.23 (16)C5—N2—C1122.89 (15)
N2—C1—H1119.9C5—N2—H2118.6
C2—C1—H1119.9C1—N2—H2118.6
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl2i0.892.353.1914 (16)157
N1—H1B···Cl2ii0.892.273.1206 (16)159
N1—H1C···Cl1iii0.892.283.1622 (16)170
N2—H2···Cl1iv0.862.253.0520 (16)154
C3—H3···Cl2i0.932.773.606 (2)150
C6—H6A···Cl1v0.972.743.676 (2)163
C6—H6B···Cl2vi0.972.823.700 (2)152
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y+3/2, z1/2; (iii) x+1, y+1, z; (iv) x+1, y+1, z; (v) x+2, y+1, z; (vi) x+2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H10N22+·2Cl
Mr181.06
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)4.5874 (9), 12.650 (3), 14.814 (3)
β (°) 93.61 (3)
V3)857.9 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.69
Crystal size (mm)0.50 × 0.45 × 0.15
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.720, 0.909
No. of measured, independent and
observed [I > 2σ(I)] reflections
8831, 1961, 1684
Rint0.035
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.076, 1.08
No. of reflections1961
No. of parameters92
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl2i0.892.353.1914 (16)157
N1—H1B···Cl2ii0.892.273.1206 (16)159
N1—H1C···Cl1iii0.892.283.1622 (16)170
N2—H2···Cl1iv0.862.253.0520 (16)154
C3—H3···Cl2i0.932.773.606 (2)150
C6—H6A···Cl1v0.972.743.676 (2)163
C6—H6B···Cl2vi0.972.823.700 (2)152
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y+3/2, z1/2; (iii) x+1, y+1, z; (iv) x+1, y+1, z; (v) x+2, y+1, z; (vi) x+2, y1/2, z+1/2.
 

Acknowledgements

This work was supported by the Technical Fund Financing Projects (No. 9207042464 and 9207041482) from Southeast University to ZRQ.

References

First citationChtioui, A. & Jouini, A. (2004). J. Chem. Crystallogr. A34, 43–49.  Web of Science CSD CrossRef Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationGenet, F. (1965). Bull. Soc. Fr. Mineral. Cristallogr. 88, 463–470.  CAS Google Scholar
First citationLong, G. S., Wei, M. & Willett, R. D. (1997). Inorg. Chem. 36, 3102–3107.  CSD CrossRef PubMed CAS Web of Science Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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