organic compounds
3-(Ammoniomethyl)pyridinium dibromide
aDepartment of Chemistry, Al al-Bayt University, Mafraq 25113, Jordan, bFaculty of Science and IT, Al-Balqa'a Applied University, Salt, Jordan, and cDepartment of Chemistry, The University of Jordan, Amman 11942, Jordan
*Correspondence e-mail: bfali@aabu.edu.jo
In the title salt, C6H10N22+·2Br−, the non-H atoms of the 3-methylpyridinium unit of the cation are almost coplanar (r.m.s. deviation = 0.0052 Å). In the crystal, the dications and Br anions are linked by a combination of six hydrogen bonds, viz. one Npy—H⋯Br, two C—H⋯Br and three H2N–H⋯Br, into supramolecular layers, parallel to the bc plane, composed of alternating R24(10) and R24(8) loops. Weak π–π interactions between cationic rings with centroid–centroid distances of 3.891 (2) Å are also observed.
Related literature
For non-covalent interactions, see: Allen et al. (1997); Desiraju (1997); Dolling et al. (2001); Gould et al. (1985); Hunter (1994); Hunter & Sanders (1990); Panunto et al. (1987); Robinson et al. (2000); Singh & Thornton (1990). For standard bond lengths, see: Allen et al. (1987). For graph-set notation, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812040937/im2401sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812040937/im2401Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812040937/im2401Isup3.cml
The title compound was obtained unintentionally as the product of an attempted synthesis of a halo-stannate(II) organic-inorganic hybrids, using slow evaporation of an ethanolic hot mixture of solution of SnCl2.2H2O (1 mmol) and Br2(l) and solution of 3-methylaminopyridine (1 mmol) with 2 ml of HBr at room temperature. Crystals were grown from ethanol upon cooling and slow evaporation (yield: 78%). A suitable block shaped crystal cut from a larger colorless crystal was epoxy mounted on a glass fiber and the data collected at room temperature.
Hydrogen atoms were positioned geometrically, with N—H = 0.86 – 0.89 Å, C—H = 0.93 – 0.97 Å for aromatic H and C—H = 0.96 Å for methyl H, and constrained to ride on their parent atoms, Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 (Sheldrick, 2008).Fig. 1. Molecular configuration of the 3-(ammoniomethyl)pyridinium cation and the bromide anions in the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Cation···anion interactions assembled supramolecular layers parallel to bc plane. N—H···Br and C—H···Br hydrogen bonding interactions appears as dotted lines. |
C6H10N2+·2Br− | F(000) = 520 |
Mr = 269.96 | Dx = 1.983 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 400 reflections |
a = 11.1588 (6) Å | θ = 3.4–28.8° |
b = 9.3902 (5) Å | µ = 8.90 mm−1 |
c = 9.3833 (5) Å | T = 293 K |
β = 113.092 (6)° | Block, colorless |
V = 904.44 (9) Å3 | 0.23 × 0.18 × 0.12 mm |
Z = 4 |
Agilent Xcalibur EOS diffractometer | 2401 independent reflections |
Radiation source: fine-focus sealed tube | 1641 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 16.0534 pixels mm-1 | θmax = 29.0°, θmin = 3.3° |
ω scans | h = −14→15 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −6→12 |
Tmin = 0.143, Tmax = 0.343 | l = −12→11 |
4032 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0252P)2] where P = (Fo2 + 2Fc2)/3 |
2401 reflections | (Δ/σ)max = 0.001 |
92 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
C6H10N2+·2Br− | V = 904.44 (9) Å3 |
Mr = 269.96 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1588 (6) Å | µ = 8.90 mm−1 |
b = 9.3902 (5) Å | T = 293 K |
c = 9.3833 (5) Å | 0.23 × 0.18 × 0.12 mm |
β = 113.092 (6)° |
Agilent Xcalibur EOS diffractometer | 2401 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 1641 reflections with I > 2σ(I) |
Tmin = 0.143, Tmax = 0.343 | Rint = 0.027 |
4032 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.60 e Å−3 |
2401 reflections | Δρmin = −0.50 e Å−3 |
92 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.05938 (4) | 0.77590 (4) | 1.03996 (4) | 0.03142 (12) | |
N1 | 0.6363 (3) | 0.4773 (4) | 0.3288 (3) | 0.0351 (8) | |
H1A | 0.6244 | 0.5040 | 0.2366 | 0.042* | |
Br2 | 0.69216 (3) | 0.57502 (5) | 0.03324 (4) | 0.03665 (14) | |
N2 | 0.9797 (3) | 0.5140 (3) | 0.7751 (3) | 0.0315 (8) | |
H2B | 1.0386 | 0.5659 | 0.8489 | 0.047* | |
H2C | 1.0002 | 0.5105 | 0.6926 | 0.047* | |
H2D | 0.9785 | 0.4262 | 0.8102 | 0.047* | |
C2 | 0.7269 (3) | 0.5432 (4) | 0.4486 (4) | 0.0295 (9) | |
H2A | 0.7761 | 0.6162 | 0.4315 | 0.035* | |
C3 | 0.7476 (3) | 0.5032 (4) | 0.5971 (4) | 0.0271 (9) | |
C4 | 0.6744 (3) | 0.3937 (4) | 0.6182 (4) | 0.0325 (9) | |
H4A | 0.6875 | 0.3647 | 0.7180 | 0.039* | |
C5 | 0.5817 (4) | 0.3262 (5) | 0.4923 (4) | 0.0399 (10) | |
H5A | 0.5326 | 0.2515 | 0.5062 | 0.048* | |
C6 | 0.5634 (4) | 0.3716 (5) | 0.3462 (4) | 0.0392 (10) | |
H6A | 0.5005 | 0.3288 | 0.2597 | 0.047* | |
C7 | 0.8494 (3) | 0.5797 (4) | 0.7313 (4) | 0.0321 (9) | |
H7A | 0.8533 | 0.6786 | 0.7036 | 0.039* | |
H7B | 0.8247 | 0.5774 | 0.8196 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0375 (2) | 0.0275 (2) | 0.0308 (2) | −0.00378 (18) | 0.01508 (16) | −0.00248 (17) |
N1 | 0.0401 (19) | 0.042 (2) | 0.0205 (15) | 0.0105 (18) | 0.0088 (14) | 0.0037 (15) |
Br2 | 0.0324 (2) | 0.0465 (3) | 0.0321 (2) | 0.0023 (2) | 0.01373 (16) | 0.00552 (19) |
N2 | 0.0290 (16) | 0.035 (2) | 0.0273 (15) | −0.0019 (16) | 0.0080 (13) | 0.0035 (15) |
C2 | 0.0294 (19) | 0.031 (2) | 0.033 (2) | 0.0020 (18) | 0.0170 (16) | 0.0029 (18) |
C3 | 0.0222 (18) | 0.033 (2) | 0.0257 (18) | 0.0061 (18) | 0.0095 (15) | 0.0018 (17) |
C4 | 0.0285 (19) | 0.041 (3) | 0.0271 (19) | −0.0018 (19) | 0.0098 (15) | 0.0064 (19) |
C5 | 0.033 (2) | 0.041 (3) | 0.044 (2) | −0.009 (2) | 0.0128 (18) | 0.003 (2) |
C6 | 0.032 (2) | 0.043 (3) | 0.033 (2) | −0.001 (2) | 0.0021 (17) | −0.007 (2) |
C7 | 0.031 (2) | 0.034 (3) | 0.0305 (19) | 0.0019 (19) | 0.0120 (16) | −0.0033 (18) |
N1—C6 | 1.333 (5) | C3—C4 | 1.375 (5) |
N1—C2 | 1.333 (4) | C3—C7 | 1.507 (5) |
N1—H1A | 0.8600 | C4—C5 | 1.382 (5) |
N2—C7 | 1.482 (4) | C4—H4A | 0.9300 |
N2—H2B | 0.8900 | C5—C6 | 1.373 (5) |
N2—H2C | 0.8900 | C5—H5A | 0.9300 |
N2—H2D | 0.8900 | C6—H6A | 0.9300 |
C2—C3 | 1.372 (5) | C7—H7A | 0.9700 |
C2—H2A | 0.9300 | C7—H7B | 0.9700 |
C6—N1—C2 | 122.7 (3) | C3—C4—C5 | 120.5 (3) |
C6—N1—H1A | 118.6 | C3—C4—H4A | 119.8 |
C2—N1—H1A | 118.6 | C5—C4—H4A | 119.8 |
C7—N2—H2B | 109.5 | C6—C5—C4 | 118.7 (4) |
C7—N2—H2C | 109.5 | C6—C5—H5A | 120.7 |
H2B—N2—H2C | 109.5 | C4—C5—H5A | 120.7 |
C7—N2—H2D | 109.5 | N1—C6—C5 | 119.6 (4) |
H2B—N2—H2D | 109.5 | N1—C6—H6A | 120.2 |
H2C—N2—H2D | 109.5 | C5—C6—H6A | 120.2 |
N1—C2—C3 | 119.9 (4) | N2—C7—C3 | 111.7 (3) |
N1—C2—H2A | 120.1 | N2—C7—H7A | 109.3 |
C3—C2—H2A | 120.1 | C3—C7—H7A | 109.3 |
C2—C3—C4 | 118.6 (3) | N2—C7—H7B | 109.3 |
C2—C3—C7 | 119.3 (3) | C3—C7—H7B | 109.3 |
C4—C3—C7 | 122.1 (3) | H7A—C7—H7B | 107.9 |
C6—N1—C2—C3 | −0.3 (6) | C3—C4—C5—C6 | −0.6 (6) |
N1—C2—C3—C4 | 0.9 (5) | C2—N1—C6—C5 | −0.6 (6) |
N1—C2—C3—C7 | −179.4 (3) | C4—C5—C6—N1 | 1.1 (6) |
C2—C3—C4—C5 | −0.4 (6) | C2—C3—C7—N2 | −87.9 (4) |
C7—C3—C4—C5 | 179.8 (4) | C4—C3—C7—N2 | 91.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···Br1 | 0.89 | 2.61 | 3.358 (3) | 142 |
N2—H2C···Br1i | 0.89 | 2.69 | 3.330 (3) | 130 |
N2—H2D···Br1ii | 0.89 | 2.49 | 3.348 (3) | 161 |
N1—H1A···Br2 | 0.86 | 2.41 | 3.206 (3) | 155 |
C5—H5A···Br2iii | 0.93 | 2.91 | 3.793 (4) | 160 |
C6—H6A···Br2iv | 0.93 | 2.89 | 3.619 (4) | 136 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C6H10N2+·2Br− |
Mr | 269.96 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.1588 (6), 9.3902 (5), 9.3833 (5) |
β (°) | 113.092 (6) |
V (Å3) | 904.44 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.90 |
Crystal size (mm) | 0.23 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Agilent Xcalibur EOS diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.143, 0.343 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4032, 2401, 1641 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.070, 1.02 |
No. of reflections | 2401 |
No. of parameters | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.50 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···Br1 | 0.89 | 2.61 | 3.358 (3) | 141.8 |
N2—H2C···Br1i | 0.89 | 2.69 | 3.330 (3) | 129.5 |
N2—H2D···Br1ii | 0.89 | 2.49 | 3.348 (3) | 160.7 |
N1—H1A···Br2 | 0.86 | 2.41 | 3.206 (3) | 155.0 |
C5—H5A···Br2iii | 0.93 | 2.91 | 3.793 (4) | 159.8 |
C6—H6A···Br2iv | 0.93 | 2.89 | 3.619 (4) | 136.0 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z. |
Acknowledgements
The structure was determined at the Hamdi Mango Center for Scientific Research at the University of Jordan, Amman. RA-F would like to thank Al-Balqa'a Applied University (Jordan) for financial support (sabbatical leave).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Non-covalent interactions play an important role in organizing structural units in both natural and artificial systems (Desiraju, 1997). They exercise important effects on the organization and properties of many materials in areas such as biology (Hunter, 1994), crystal engineering (Allen et al., 1997, Dolling et al., 2001) and material science (Panunto et al., 1987, Robinson et al., 2000). We herein report the molecular structure of the salt, 3-(ammoniomethyl)pyridinium dibromide, along with it's supramolecular crystal structure.
In the title salt (Fig. 1) bond lengths (Allen et al., 1987) and angles of the dication are within normal ranges. The unit (N1/C2/C3/C4/C5/C6/C7) of the independent cation is planar with r.m.s.d = 0.0052 (2) Å. The ammonium group largely deviates by 1.369 (7) Å out of this plane. The 3-methylammonium groups attached to the pyridinium ring through C3 shows a torsion angle of -87.9 (4)° for C2—C3—C7—N2.
The crystal packing involves extensive cation···anion interactions. These interactions assemble cations and anions into supramolecular layers parallel to the bc plane (Fig. 2) via N—H···Br and C—H···Br hydrogen bonding interactions of the types Npy—H···Br, H2N—H···Br, and C—H···Br (Table 1). These layers are composed of alternating R24(10) [two bromide anions and two (py)C/N—H units of two cations] and R24(8) [two bromide anions and two ammonium groups via two H atoms each] graph set motifs (Bernstein et al., 1995). Interlayer interactions are established through the third hydrogen of the ammonium group with a bromide anion of a next layer (Fig. 2).
The cations also interact to some extent by offset face-to-face interactions along the a-axis, adding extra lattice stability. This is evident by the centroid separation distances C1g···C1g (1 - x, 1 - y, 1 - z) of 3.891 (2) Å. The observed centroids separation distance is in accordance with those of calculated and the experimentally observed stacked (offset-face-to-face) interaction modes (Gould et al., 1985, Hunter & Sanders, 1990, Hunter, 1994, Singh & Thornton, 1990). The N—H···Br and C—H···Br hydrogen bonding and aryl···aryl interactions consolidate to from a three-dimensional network.