2-Amino­ethanaminium iodide

Abstract

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,

• a = 8.1380 (2) Å

• b = 8.6259 (2) Å

• c = 16.7854 (6) Å

• V = 1178.29 (6) ų

• 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 ▶) 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[F ² > 2σ(F ²)] = 0.016

• wR(F ²) = 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

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681202065X/br2201Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯I1iv	0.84 (2)	2.96 (2)	3.7346 (16)	155.5 (16)
N2—H5N⋯I1v	0.866 (19)	3.152 (19)	3.9328 (15)	151.2 (14)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

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.

Experimental

Crystals of (I) were obtained from ethanol solution.

Refinement

All the H-atoms were found through difference synthesis and refined isotropically. The N1 to H1N distance is 1.06 (2) Å. This forms part of the N—H···N hydrogen bond and may reflect some small degree of positional disorder over two sites.

Figures

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.

Crystal data

C2H9N2+·I−	F(000) = 704
Mr = 188.01	Dx = 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

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

Refinement

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(Fo2) + (0.0188P)2 + 0.0175P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.003
1675 reflections	Δρmax = 0.58 e Å−3
83 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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···I1iv	0.84 (2)	2.96 (2)	3.7346 (16)	155.5 (16)
N2—H5N···I1v	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.