2-Amino­ethanaminium iodide

Kennedy, A.R.; Okoth, M.O.

doi:10.1107/S160053681202065X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1731

doi:10.1107/S160053681202065X

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2-Aminoethanaminium iodide

Alan R. Kennedy ^a and Maurice O. Okoth ^b ^*

^aDepartment of Pure & Applied Chemistry, WestCHEM, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland, and ^bDepartment of Chemistry and Biochemistry, Chepkoilel University College, PO Box 1125-30100, Eldoret, Kenya
^*Correspondence e-mail: okothmdo@mu.ac.ke

(Received 24 April 2012; accepted 7 May 2012; online 16 May 2012)

The title salt, [NH₃CH₂CH₂NH₂]⁺·I⁻, has an array structure based on strong intermolecular N—H⋯N hydrogen bonding formed between the ammonium and amine groups of adjacent cations. This interaction gives a helical chain of cations that runs parallel to the b axis. The four remaining NH group H atoms all form hydrogen bonds to the iodide anion, and these iodide anions lie in channels parallel to the cation–cation chains.

Related literature

For syntheses and structures of salt forms of the related ethylene-1,2-diammonium, see: Chen (2009 ); Saidi et al. (2011 ). For a structural example of a complex of ethylene-1,2-diammonium, see: Zhang et al. (2006 ). For the synthesis that gave the title compound as a by-product, see: Kennedy et al. (2011 ). For C–N bond length changes in another monoprotonated symmetrical diamine, see: Craig et al. (2012 ).

Experimental

Crystal data

C₂H₉N₂⁺·I⁻
M_r = 188.01
Orthorhombic, P b c a
a = 8.1380 (2) Å
b = 8.6259 (2) Å
c = 16.7854 (6) Å
V = 1178.29 (6) Å³
Z = 8
Mo Kα radiation
μ = 5.29 mm⁻¹
T = 123 K
0.28 × 0.08 × 0.04 mm

Data collection

Oxford Diffraction Gemini S diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.405, T_max = 0.805
13735 measured reflections
1675 independent reflections
1405 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.035
S = 1.08
1675 reflections
83 parameters
All H-atom parameters refined
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2ⁱ	1.06 (2)	1.75 (2)	2.805 (2)	173.0 (19)
N1—H2N⋯I1	0.882 (19)	3.231 (18)	3.6502 (14)	111.6 (13)
N1—H2N⋯I1ⁱⁱ	0.882 (19)	2.820 (19)	3.6047 (14)	148.9 (15)
N1—H3N⋯I1ⁱⁱⁱ	0.84 (2)	2.78 (2)	3.5713 (16)	157.9 (16)
N2—H4N⋯I1^iv	0.84 (2)	2.96 (2)	3.7346 (16)	155.5 (16)
N2—H5N⋯I1^v	0.866 (19)	3.152 (19)	3.9328 (15)	151.2 (14)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y, -z+1; (v) x+1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681202065X/br2201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202065X/br2201Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202065X/br2201Isup3.cml

checkCIF report

Comment top

Despite the common use of ethylene-1,2-diamine as a ligand, there are suprisingly few metal containing crystal structures that feature its cationic form ethylene-1,2-diammonium (for an example see Zhang et al., 2006) and only two structures of simple salt forms of ethylene-1,2-diammonium (Chen, 2009; Saidi et al., 2011). There appears to be no previous reports of structures that contain the singley protonated cation, NH₃CH₂CH₂NH₂.

Crystals of ethylene-2-amine-1-ammonium iodide (I) were recovered whilst trying to replicate the synthesis of the macrocyclic species 5,7,7,12,14,14-hexamethyl-4,8-diaza-1,11 -diazoniocyclotetradeca-4,11-diene diiodide, the first step of which is addition of HI to ethylene-1,2-diamine in ethanol (Kennedy et al., 2011). Investigation of the structure cleary showed that the base is protonated at only one site, see Figure 1. This is confirmed by location and independent refinement of the hydrogen atoms and by the slight lengthening of the C1—N1 bond as compared to the C2—N2 bond (compare 1.484 (2) and 1.467 (2) Å). Similar differences are seen in other symmetrical diamines that have been monoprotonated (see for example Craig et al., 2012).

Atom H1N is a hydrogen bond donor that interacts with N2 to form the relatively short cation to cation hydrogen bond that gives the one dimensional helical chain running in the b direction, as shown in Figure 2. The four other N—H hydrogen atoms all interact with the iodide anion (N···I range 3.5713 (16) to 3.9328 (15) Å), see Table 1 for details. These interactions combine to give the packing motif shown in Figure 3, with channels of anions parallel to the b direction and thus also parallel to the cation-cation hydrogen bonded chains.

Related literature top

For syntheses and structures of salt forms of the related ethylene-1,2-diammonium, see: Chen (2009); Saidi et al. (2011). For a structural example of a complex of ethylene-1,2-diammonium, see: Zhang et al. (2006). For the synthesis that gave the title compound as a by-product, see: Kennedy et al. (2011). For C–N bond length changes in another monoprotonated symmetrical diamine, see: Craig et al. (2012).

Experimental top

Crystals of (I) were obtained from ethanol solution.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level with H-atoms drawn as spheres of arbitary size.
	Fig. 2. Hydrogen bonding forms helical, one-dimensional chains of cations that propagate in the crystallographic b direction.
	Fig. 3. Packing in (I) viewed along the b direction.

2-Aminoethanaminium iodide top

Crystal data top

C₂H₉N₂⁺·I⁻	F(000) = 704
M_r = 188.01	D_x = 2.120 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7738 reflections
a = 8.1380 (2) Å	θ = 3.4–30.4°
b = 8.6259 (2) Å	µ = 5.29 mm⁻¹
c = 16.7854 (6) Å	T = 123 K
V = 1178.29 (6) Å³	Cut needle, colourless
Z = 8	0.28 × 0.08 × 0.04 mm

Data collection top

Oxford Diffraction Gemini S diffractometer	1675 independent reflections
Radiation source: fine-focus sealed tube	1405 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 30.5°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −11→11
T_min = 0.405, T_max = 0.805	k = −12→12
13735 measured reflections	l = −23→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.016	All H-atom parameters refined
wR(F²) = 0.035	w = 1/[σ²(F_o²) + (0.0188P)² + 0.0175P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.003
1675 reflections	Δρ_max = 0.58 e Å⁻³
83 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00618 (17)

Crystal data top

C₂H₉N₂⁺·I⁻	V = 1178.29 (6) Å³
M_r = 188.01	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.1380 (2) Å	µ = 5.29 mm⁻¹
b = 8.6259 (2) Å	T = 123 K
c = 16.7854 (6) Å	0.28 × 0.08 × 0.04 mm

Data collection top

Oxford Diffraction Gemini S diffractometer	1675 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1405 reflections with I > 2σ(I)
T_min = 0.405, T_max = 0.805	R_int = 0.025
13735 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.035	All H-atom parameters refined
S = 1.08	Δρ_max = 0.58 e Å⁻³
1675 reflections	Δρ_min = −0.39 e Å⁻³
83 parameters

Special details top

Experimental. Absorption correction: CrysAlis PRO (Oxford Diffraction, 2010). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
I1	0.153737 (12)	0.243717 (9)	0.639779 (7)	0.01478 (5)
N1	0.57239 (17)	0.09977 (16)	0.66467 (10)	0.0152 (3)
N2	0.91366 (18)	−0.12957 (16)	0.57234 (10)	0.0166 (3)
C1	0.72638 (19)	0.00806 (18)	0.65975 (11)	0.0156 (3)
C2	0.7645 (2)	−0.03399 (18)	0.57391 (10)	0.0164 (3)
H1	0.720 (2)	−0.083 (2)	0.6923 (11)	0.022 (5)*
H2	0.812 (2)	0.073 (2)	0.6768 (12)	0.025 (5)*
H3	0.677 (2)	−0.0965 (19)	0.5534 (11)	0.020 (5)*
H4	0.771 (2)	0.0590 (19)	0.5396 (11)	0.018 (4)*
H1N	0.573 (3)	0.206 (3)	0.6334 (13)	0.030 (5)*
H2N	0.487 (2)	0.042 (2)	0.6523 (12)	0.027 (5)*
H3N	0.561 (2)	0.131 (2)	0.7119 (12)	0.028 (6)*
H4N	0.932 (2)	−0.161 (2)	0.5259 (13)	0.029 (5)*
H5N	0.998 (2)	−0.073 (2)	0.5848 (13)	0.029 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01452 (7)	0.01487 (7)	0.01494 (8)	0.00109 (3)	−0.00020 (4)	−0.00022 (4)
N1	0.0146 (7)	0.0161 (7)	0.0150 (8)	−0.0014 (5)	0.0018 (6)	−0.0016 (5)
N2	0.0151 (7)	0.0194 (7)	0.0152 (8)	0.0000 (5)	0.0019 (6)	−0.0009 (6)
C1	0.0140 (8)	0.0188 (8)	0.0141 (8)	−0.0001 (6)	−0.0006 (6)	0.0007 (6)
C2	0.0164 (8)	0.0191 (7)	0.0136 (8)	0.0010 (6)	0.0007 (7)	0.0010 (6)

Geometric parameters (Å, º) top

N1—C1	1.484 (2)	N2—H5N	0.866 (19)
N1—H1N	1.06 (2)	C1—C2	1.518 (2)
N1—H2N	0.882 (19)	C1—H1	0.959 (18)
N1—H3N	0.84 (2)	C1—H2	0.937 (19)
N2—C2	1.467 (2)	C2—H3	0.959 (17)
N2—H4N	0.84 (2)	C2—H4	0.989 (18)

C1—N1—H1N	115.5 (12)	C2—C1—H1	110.8 (11)
C1—N1—H2N	110.4 (12)	N1—C1—H2	107.0 (11)
H1N—N1—H2N	112.4 (17)	C2—C1—H2	106.3 (13)
C1—N1—H3N	108.5 (13)	H1—C1—H2	110.7 (18)
H1N—N1—H3N	100.7 (16)	N2—C2—C1	108.70 (14)
H2N—N1—H3N	108.6 (17)	N2—C2—H3	107.1 (10)
C2—N2—H4N	110.2 (13)	C1—C2—H3	108.8 (11)
C2—N2—H5N	109.6 (12)	N2—C2—H4	113.8 (10)
H4N—N2—H5N	105.2 (18)	C1—C2—H4	111.7 (11)
N1—C1—C2	110.67 (14)	H3—C2—H4	106.6 (15)
N1—C1—H1	111.2 (11)

N1—C1—C2—N2	−177.75 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2ⁱ	1.06 (2)	1.75 (2)	2.805 (2)	173.0 (19)
N1—H2N···I1	0.882 (19)	3.231 (18)	3.6502 (14)	111.6 (13)
N1—H2N···I1ⁱⁱ	0.882 (19)	2.820 (19)	3.6047 (14)	148.9 (15)
N1—H3N···I1ⁱⁱⁱ	0.84 (2)	2.78 (2)	3.5713 (16)	157.9 (16)
N2—H4N···I1^iv	0.84 (2)	2.96 (2)	3.7346 (16)	155.5 (16)
N2—H5N···I1^v	0.866 (19)	3.152 (19)	3.9328 (15)	151.2 (14)

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+1/2, y−1/2, z; (iii) x+1/2, y, −z+3/2; (iv) −x+1, −y, −z+1; (v) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂H₉N₂⁺·I⁻
M_r	188.01
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	8.1380 (2), 8.6259 (2), 16.7854 (6)
V (Å³)	1178.29 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.29
Crystal size (mm)	0.28 × 0.08 × 0.04

Data collection
Diffractometer	Oxford Diffraction Gemini S diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.405, 0.805
No. of measured, independent and observed [I > 2σ(I)] reflections	13735, 1675, 1405
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.713

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.035, 1.08
No. of reflections	1675
No. of parameters	83
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.39

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and X-SEED (Barbour, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2ⁱ	1.06 (2)	1.75 (2)	2.805 (2)	173.0 (19)
N1—H2N···I1	0.882 (19)	3.231 (18)	3.6502 (14)	111.6 (13)
N1—H2N···I1ⁱⁱ	0.882 (19)	2.820 (19)	3.6047 (14)	148.9 (15)
N1—H3N···I1ⁱⁱⁱ	0.84 (2)	2.78 (2)	3.5713 (16)	157.9 (16)
N2—H4N···I1^iv	0.84 (2)	2.96 (2)	3.7346 (16)	155.5 (16)
N2—H5N···I1^v	0.866 (19)	3.152 (19)	3.9328 (15)	151.2 (14)

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+1/2, y−1/2, z; (iii) x+1/2, y, −z+3/2; (iv) −x+1, −y, −z+1; (v) x+1, y, z.

Acknowledgements

MOO thanks the Commonwealth Scholarship Commission and the British Council for funding and Moi University for sabbatical leave.

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