Home The crystal structure of 3-aminopropan-1-aminium iodide, C3H11N2I
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The crystal structure of 3-aminopropan-1-aminium iodide, C3H11N2I

  • Charmaine Arderne EMAIL logo and Kyle F. Batchelor
Published/Copyright: March 22, 2017

Abstract

C3H11N2I, monoclinic, P21/n (no. 14), a = 5.0152(2) Å, b = 10.1470(4) Å, c = 14.1852(5) Å, β = 96.501(2)°, V = 717.23(5) Å3, Z = 4, Rgt(F) = 0.0174, wRref(F2) = 0.0411, T = 100 K.

CCDC no.:: 1487923

The asymmetric unit of the title crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Colourless plate
Size:0.36 × 0.20 × 0.12 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:43.6 cm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω
2θmax, completeness:57°, >99%
N(hkl)measured, N(hkl)unique, Rint:14021, 1788, 0.033
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1521
N(param)refined:76
Programs:OLEX2 [1], SHELX [2], [3], [4], Bruker programs [5]
Table 2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
I10.86390(3)0.17593(2)0.40609(2)0.04220(8)
N10.6414(4)0.07619(19)0.63924(16)0.0444(4)
H1A0.725(6)0.068(3)0.6989(13)0.079(10)*
H1B0.527(5)0.011(2)0.626(2)0.080(10)*
H1C0.763(5)0.080(3)0.5981(16)0.069(9)*
N20.6425(5)0.5615(2)0.66808(17)0.0538(5)
H2A0.544(5)0.630(2)0.654(2)0.065(9)*
H2B0.780(4)0.563(3)0.6352(19)0.065(9)*
C10.4779(5)0.4449(2)0.63954(17)0.0454(5)
H1D0.4044990.4531090.5735490.054*
H1E0.3294710.4392370.6776450.054*
C20.6476(4)0.32019(19)0.65273(17)0.0389(5)
H2C0.7341980.3163270.7173730.047*
H2D0.7864100.3225160.6103940.047*
C30.4744(5)0.1978(2)0.63201(17)0.0410(5)
H3A0.3421470.1927880.6767860.049*
H3B0.3794350.2041820.5686900.049*

Source of material

The 3-aminopropan-1-aminium iodide was prepared by adding propan-1,3-diamine (0.050 g, 0.832 mmol) to 57% hydriodic acid (3 mL, 39.87 mmol) in a sample vial. The mixture was then refluxed at 363 K for 2 h. The solution was cooled slowly at 2 K⋅h−1 to room temperature. Colourless crystals of 3-aminopropan-1-aminium iodide were collected for the single-crystal X-ray study.

Experimental details

H-atoms were placed in geometrically idealized positions, with C—H = 0.93–0.99 Å, and were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for methylene H atoms. The methylene H atoms were initially located in a difference Fourier map, but since they were not involved in any hydrogen-bonding interactions they were placed in idealized positions as described above and refined as rotating groups. H atoms at N atoms were also located in a difference Fourier map and, since they are involved in hydrogen bonding, the positions and isotropic displacement parameters of these atoms were allowed to refine freely. Their distances were restrained with the DFIX instruction (in SHELX [2, 3] ) to 0.88 Å with an allowed restrained s. u. of 0.015.

Comment

The crystal structure of 3-aminopropan-1-aminium iodide was determined as part of our ongoing study of the structural characteristics and noncovalent interactions of inorganic-organic hybrid materials. A search of the Cambridge Structural Database (CSD, Version 5.37, May 2016 update; [6]) revealed that this compound had not been determined previously, so it is presented here.

Interestingly, only one of the amine groups was protonated in the synthesis of 3-aminopropan-1-aminium iodide. A similar phenonemon is evident for at least two related structures – these being 2-aminoethanaminium iodide (CSD code: PAWBEW [7]) and 7-aminoheptan-1-aminium iodide (CSD code: ABAMAT [8]). This structure is also a rare example of an α-aminium-ω-aminoalkane that does not show any disorder in the crystal structure.

The asymmetric unit of the title compound consists of one 3-amino-1-propanaminium cation and one iodide anion. The bond lengths and angles within the organic cation are; with C—C bond lengths of 1.524 Å and 1.525 Å respectively and slightly shorter C—N distances of 1.473 Å and 1.488 Å respectively, as expected; and bond angles ranging from 110.21° to 110.98°, as expected.

There is also extensive hydrogen bonding evident with the shortest and strongest hydrogen bond being evident from the N1 atom of the aminium side of the cation to the N2 atom of the amino group on an adjacent cation indicating N—H⋅⋅⋅N hydrogen bonding (N⋅⋅⋅N distance = 2.828(3) Å, N—H⋅⋅⋅N angle = 172(3)°). This interaction forms a helical chain of cations that run along the b axis. There are five remaining interactions consisting of charge-assisted N—H⋅⋅⋅I bonds. The iodide anions lie in channels parallel to the cation-cation chains. These hydrogen bonds connect the helical chains into a three-dimensional network that can be classified using graph sets [9] to build a ring motif in the inorganic (hydrophilic) region with graph set R24(8) and a ring motif R34(12) that includes the alkyl chains and the iodide anions in an alternating fashion. According to the generally accepted classification [10], the N—H⋅⋅⋅N hydrogen bonds can be described as medium-strong bonds, while the N—H⋅⋅⋅I hydrogen bonds can be described as being weakly, charge-assisted.

Acknowledgement

The authors extend their appreciation for financial support for the research project from the University of Johannesburg Research Centre for Synthesis and Catalysis. We also acknowledge support for the publication fee by the University of Johannesburg Staff Research and Publications fund.

References

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Received: 2016-12-5
Accepted: 2017-2-24
Published Online: 2017-3-22
Published in Print: 2017-5-24

©2017 Charmaine Arderne et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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