3-(Ammonio­meth­yl)pyridinium dibromide

Ali, B.F.; Al-Far, R.; Haddad, S.F.

doi:10.1107/S1600536812040937

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3066

doi:10.1107/S1600536812040937

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3-(Ammoniomethyl)pyridinium dibromide

Basem F. Ali,^a ^* Rawhi Al-Far ^b and Salim F. Haddad ^c

^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

(Received 6 September 2012; accepted 28 September 2012; online 3 October 2012)

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 N_py—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

C₆H₁₀N₂⁺·2Br⁻
M_r = 269.96
Monoclinic, P 2₁ /c
a = 11.1588 (6) Å
b = 9.3902 (5) Å
c = 9.3833 (5) Å
β = 113.092 (6)°
V = 904.44 (9) Å³
Z = 4
Mo Kα radiation
μ = 8.90 mm⁻¹
T = 293 K
0.23 × 0.18 × 0.12 mm

Data collection

Agilent Xcalibur EOS diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.143, T_max = 0.343
4032 measured reflections
2401 independent reflections
1641 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.070
S = 1.02
2401 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯Br2^iv	0.93	2.89	3.619 (4)	136
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+2; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2011); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536812040937/im2401sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812040937/im2401Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812040937/im2401Isup3.cml

checkCIF report

Comment top

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 N_py—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 C_1g···C_1g (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.

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: 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).

Figures top

	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.

'3-(Ammoniomethyl)pyridinium dibromide' top

Crystal data top

C₆H₁₀N₂⁺·2Br⁻	F(000) = 520
M_r = 269.96	D_x = 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

Data collection top

Agilent Xcalibur EOS diffractometer	2401 independent reflections
Radiation source: fine-focus sealed tube	1641 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.0534 pixels mm^-1	θ_max = 29.0°, θ_min = 3.3°
ω scans	h = −14→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −6→12
T_min = 0.143, T_max = 0.343	l = −12→11
4032 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0252P)²] where P = (F_o² + 2F_c²)/3
2401 reflections	(Δ/σ)_max = 0.001
92 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₆H₁₀N₂⁺·2Br⁻	V = 904.44 (9) Å³
M_r = 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)°

Data collection top

Agilent Xcalibur EOS diffractometer	2401 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1641 reflections with I > 2σ(I)
T_min = 0.143, T_max = 0.343	R_int = 0.027
4032 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.02	Δρ_max = 0.60 e Å⁻³
2401 reflections	Δρ_min = −0.50 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Br2^iv	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⁻
M_r	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)
T_min, T_max	0.143, 0.343
No. of measured, independent and observed [I > 2σ(I)] reflections	4032, 2401, 1641
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.50

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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···Br2^iv	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).

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