organic compounds
Ethylenediammonium chloride thiocyanate
aLaboratoire de Génie des Matériaux et Environnement, École Nationale d'Ingénieurs de Sfax, BP 1173, Sfax, Tunisia, and bService commun d'analyse par diffraction des rayons X, Université de Brest, 6, Avenue Victor Le Gorgeu, CS 93837, F-29238 Brest cedex 3, France
*Correspondence e-mail: slah.kamoun@gmail.com
In the ethylenediammonium dication of the title salt, C2H10N22+·Cl−·SCN−, the N—C—C—N torsion angle is 72.09 (12)°. In the crystal, an extensive three-dimensional hydrogen-bonding network, formed by N—H⋯Cl and N—H⋯N hydrogen bonds, holds all the ions together.
Related literature
For the crystal structures of related compounds, see: Kamoun et al. (1989); Chen (2009). For details of the synthesis of thiocyanic acid, see: Bartlett et al. (1969). For protonic conductivity and dielectric relaxation in ethylendiammonium salts, see: Karoui et al. (2013).
Experimental
Crystal data
|
Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg et al., 1999) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536813008830/cv5396sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008830/cv5396Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813008830/cv5396Isup3.cdx
The title compound has been obtained as crystalline solid in the reaction of ethylenediamine with an aqueous acidic mixture of hydrochloric acid and thiocyanic acid (1/1 ratio). Thiocyanic acid was prepared using the published procedure (Bartlett et al., 1969). After a slow solvent evaporation yellow crystals suitable for X-ray analysis were obtained.They were washed with diethyl ether and dried over P2O5.
The H atoms were positioned geometrically (the C—H and N—H bonds were respectively fixed at 0.96 and 0.89), and allowed to ride on their parent atoms, with Uiso(H) = 1.2 Ueq(C, N).
As an extension of our earlier study on protonic conductivity and dielectric relaxation in ethylenediammonium salts (Karoui et al., 2013), we report herein the molecular structure of the title compound, (I), which is a new organic halide-pseudohalide compound.
In (I) (Fig. 1), the
consists of one diprotonated ethylenediammonium cation, one Cl- and one SCN- anions. In this atomic arrangement, the organic group has no internal symmetry. In fact, the mean length of the C—N bonds: 1.4816 (14) Å is lower than that of the C—C bonds:1.5054 (15) Å. The [C2H10N2]2+ dication shows an eclipsed conformation with a N–C–C–N torsion angle of 72.09 (12)°. The main geometrical features of this group are similar to that reported for others ethylenediammonium halides (Chen, 2009) and phosphates (Kamoun et al.,1989). The thiocyanate ion, present as a monodentate ligand, is almost linear with an angle of 178.48 (11)° and an average C–S and C–N bond lengths of 1.6358 (12) Å and 1.1573 (16) Å, respectively.In the
the ethylenediammonium cations are linked to the chloride and thiocyanate anions by means of five medium N—H···Cl and two weak N—H···N(CS) intermolecular hydrogen bonds (Table 1) to form a three-dimensional network (Fig. 2). The N···Cl and N···N(CS) distances range from 3.1982 (9) to 3.3543 (10) Å and 2.8533 (14) Å to 3.1106 (17) Å, respectively. The sum of Van der Waal's radii of N and Cl, and N and O are 3.3 Å and 2.9 Å, respectively.For the crystal structures of related compounds, see: Kamoun et al. (1989); Chen (2009). For details of the synthesis of thiocyanic acid, see: Bartlett et al. (1969). For protonic conductivity and dielectric relaxation in ethylendiammonium salts, see: Karoui et al. (2013).
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg et al., 1999) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).Fig. 1. A content of asymmetric unit of (I) showing the atomic-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms represented by small spheres of arbitrary radii. | |
Fig. 2. A portion of the crystal packing viewed approximately down the b axis and showing hydrogen bonds as dashed lines. |
C2H10N22+·Cl−·SCN− | F(000) = 164 |
Mr = 155.65 | Cell parameters from 3445 reflections |
Triclinic, P1 | Dx = 1.422 Mg m−3 Dm = 1.398 Mg m−3 Dm measured by flotation |
Hall symbol: -P 1 | Melting point: 443 K |
a = 6.2726 (2) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 6.3462 (2) Å | Cell parameters from 5534 reflections |
c = 9.1745 (3) Å | θ = 3.2–44.7° |
α = 92.436 (3)° | µ = 0.72 mm−1 |
β = 92.193 (3)° | T = 293 K |
γ = 94.341 (3)° | Parallelipipedic, light yellow |
V = 363.52 (2) Å3 | 0.50 × 0.42 × 0.17 mm |
Z = 2 |
Agilent Xcalibur (Sapphire2) diffractometer | 2189 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1947 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 8.3622 pixels mm-1 | θmax = 30.5°, θmin = 3.2° |
ω scans | h = −5→8 |
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012) | k = −9→9 |
Tmin = 0.737, Tmax = 0.887 | l = −13→13 |
6396 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0383P)2 + 0.0716P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2189 reflections | Δρmax = 0.40 e Å−3 |
74 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.294 (15) |
Primary atom site location: structure-invariant direct methods |
C2H10N22+·Cl−·SCN− | γ = 94.341 (3)° |
Mr = 155.65 | V = 363.52 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.2726 (2) Å | Mo Kα radiation |
b = 6.3462 (2) Å | µ = 0.72 mm−1 |
c = 9.1745 (3) Å | T = 293 K |
α = 92.436 (3)° | 0.50 × 0.42 × 0.17 mm |
β = 92.193 (3)° |
Agilent Xcalibur (Sapphire2) diffractometer | 2189 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012) | 1947 reflections with I > 2σ(I) |
Tmin = 0.737, Tmax = 0.887 | Rint = 0.018 |
6396 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.40 e Å−3 |
2189 reflections | Δρmin = −0.25 e Å−3 |
74 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 | ||
Cl1 | 0.19093 (4) | 0.72470 (4) | 0.47679 (3) | 0.02934 (10) | |
S1 | 0.68519 (5) | 0.78130 (5) | 0.20850 (3) | 0.03649 (10) | |
C1 | 0.45634 (19) | 0.73609 (17) | 0.11677 (11) | 0.0294 (2) | |
N1 | 0.2924 (2) | 0.7024 (2) | 0.05464 (13) | 0.0458 (3) | |
N2 | 0.31015 (15) | 0.22026 (15) | 0.43178 (10) | 0.0305 (2) | |
H2A | 0.4348 | 0.2481 | 0.4811 | 0.046* | |
H2B | 0.2590 | 0.0888 | 0.4473 | 0.046* | |
H2C | 0.2178 | 0.3109 | 0.4619 | 0.046* | |
C2 | 0.34163 (16) | 0.24184 (17) | 0.27393 (12) | 0.0288 (2) | |
H2D | 0.4449 | 0.1449 | 0.2424 | 0.035* | |
H2E | 0.4007 | 0.3844 | 0.2582 | 0.035* | |
C3 | 0.13799 (19) | 0.19753 (19) | 0.18191 (12) | 0.0322 (2) | |
H3E | 0.1733 | 0.1811 | 0.0803 | 0.039* | |
H3D | 0.0665 | 0.0651 | 0.2095 | 0.039* | |
N3 | −0.01089 (16) | 0.36715 (17) | 0.19736 (11) | 0.0345 (2) | |
H3A | −0.1283 | 0.3334 | 0.1412 | 0.052* | |
H3B | 0.0525 | 0.4885 | 0.1701 | 0.052* | |
H3C | −0.0462 | 0.3812 | 0.2901 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02482 (13) | 0.02877 (14) | 0.03390 (15) | −0.00093 (8) | 0.00252 (9) | −0.00075 (9) |
S1 | 0.02975 (16) | 0.04342 (18) | 0.03524 (17) | −0.00037 (11) | −0.00273 (11) | −0.00101 (12) |
C1 | 0.0356 (5) | 0.0265 (5) | 0.0262 (5) | 0.0033 (4) | −0.0003 (4) | 0.0020 (3) |
N1 | 0.0446 (6) | 0.0482 (6) | 0.0434 (6) | 0.0040 (5) | −0.0144 (5) | 0.0008 (5) |
N2 | 0.0269 (4) | 0.0339 (5) | 0.0312 (4) | 0.0058 (3) | −0.0035 (3) | 0.0048 (3) |
C2 | 0.0229 (4) | 0.0312 (5) | 0.0329 (5) | 0.0040 (4) | 0.0042 (4) | 0.0030 (4) |
C3 | 0.0337 (5) | 0.0347 (5) | 0.0275 (5) | 0.0027 (4) | −0.0009 (4) | −0.0066 (4) |
N3 | 0.0291 (4) | 0.0447 (5) | 0.0296 (5) | 0.0075 (4) | −0.0064 (3) | 0.0002 (4) |
S1—C1 | 1.6358 (12) | C2—H2E | 0.9700 |
C1—N1 | 1.1573 (16) | C3—N3 | 1.4834 (15) |
N2—C2 | 1.4798 (14) | C3—H3E | 0.9700 |
N2—H2A | 0.8900 | C3—H3D | 0.9700 |
N2—H2B | 0.8900 | N3—H3A | 0.8900 |
N2—H2C | 0.8900 | N3—H3B | 0.8900 |
C2—C3 | 1.5054 (15) | N3—H3C | 0.8900 |
C2—H2D | 0.9700 | ||
N1—C1—S1 | 178.48 (11) | N3—C3—C2 | 112.98 (9) |
C2—N2—H2A | 109.5 | N3—C3—H3E | 109.0 |
C2—N2—H2B | 109.5 | C2—C3—H3E | 109.0 |
H2A—N2—H2B | 109.5 | N3—C3—H3D | 109.0 |
C2—N2—H2C | 109.5 | C2—C3—H3D | 109.0 |
H2A—N2—H2C | 109.5 | H3E—C3—H3D | 107.8 |
H2B—N2—H2C | 109.5 | C3—N3—H3A | 109.5 |
N2—C2—C3 | 113.06 (9) | C3—N3—H3B | 109.5 |
N2—C2—H2D | 109.0 | H3A—N3—H3B | 109.5 |
C3—C2—H2D | 109.0 | C3—N3—H3C | 109.5 |
N2—C2—H2E | 109.0 | H3A—N3—H3C | 109.5 |
C3—C2—H2E | 109.0 | H3B—N3—H3C | 109.5 |
H2D—C2—H2E | 107.8 | ||
N2—C2—C3—N3 | 72.09 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1i | 0.89 | 2.36 | 3.1982 (9) | 158 |
N2—H2B···Cl1ii | 0.89 | 2.35 | 3.2246 (10) | 169 |
N2—H2C···Cl1iii | 0.89 | 2.64 | 3.3237 (10) | 134 |
N3—H3C···Cl1iii | 0.89 | 2.46 | 3.2953 (11) | 158 |
N3—H3A···N1iv | 0.89 | 2.03 | 2.8533 (14) | 153 |
N2—H2C···Cl1 | 0.89 | 2.64 | 3.3543 (10) | 138 |
N3—H3B···N1 | 0.89 | 2.27 | 3.1106 (17) | 157 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x, −y+1, −z+1; (iv) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C2H10N22+·Cl−·SCN− |
Mr | 155.65 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.2726 (2), 6.3462 (2), 9.1745 (3) |
α, β, γ (°) | 92.436 (3), 92.193 (3), 94.341 (3) |
V (Å3) | 363.52 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.50 × 0.42 × 0.17 |
Data collection | |
Diffractometer | Agilent Xcalibur (Sapphire2) |
Absorption correction | Multi-scan (CrysAlis RED; Agilent, 2012) |
Tmin, Tmax | 0.737, 0.887 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6396, 2189, 1947 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.072, 1.08 |
No. of reflections | 2189 |
No. of parameters | 74 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.25 |
Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg et al., 1999) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1i | 0.89 | 2.36 | 3.1982 (9) | 157.7 |
N2—H2B···Cl1ii | 0.89 | 2.35 | 3.2246 (10) | 168.8 |
N2—H2C···Cl1iii | 0.89 | 2.64 | 3.3237 (10) | 134.3 |
N3—H3C···Cl1iii | 0.89 | 2.46 | 3.2953 (11) | 157.5 |
N3—H3A···N1iv | 0.89 | 2.03 | 2.8533 (14) | 153.0 |
N2—H2C···Cl1 | 0.89 | 2.64 | 3.3543 (10) | 137.7 |
N3—H3B···N1 | 0.89 | 2.27 | 3.1106 (17) | 156.9 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x, −y+1, −z+1; (iv) −x, −y+1, −z. |
Acknowledgements
The authors gratefully acknowledge the support of the Tunisian Ministry of Higher Education and Scientific Research.
References
Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England. Google Scholar
Bartlett, H. E., Jurriaanse, A. & De Haas, K. (1969). Can. J. Chem. 47, 16, 2981–2986. Google Scholar
Brandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Chen, L.-Z. (2009). Acta Cryst. E65, o2625. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Kamoun, S., Jouini, A., Kamoun, M. & Daoud, A. (1989). Acta Cryst. C45, 481–482. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Karoui, S., Kamoun, S. & Jouini, A. (2013). J. Solid State Chem. 197, 60–68. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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.
As an extension of our earlier study on protonic conductivity and dielectric relaxation in ethylenediammonium salts (Karoui et al., 2013), we report herein the molecular structure of the title compound, (I), which is a new organic halide-pseudohalide compound.
In (I) (Fig. 1), the asymmetric unit consists of one diprotonated ethylenediammonium cation, one Cl- and one SCN- anions. In this atomic arrangement, the organic group has no internal symmetry. In fact, the mean length of the C—N bonds: 1.4816 (14) Å is lower than that of the C—C bonds:1.5054 (15) Å. The [C2H10N2]2+ dication shows an eclipsed conformation with a N–C–C–N torsion angle of 72.09 (12)°. The main geometrical features of this group are similar to that reported for others ethylenediammonium halides (Chen, 2009) and phosphates (Kamoun et al.,1989). The thiocyanate ion, present as a monodentate ligand, is almost linear with an angle of 178.48 (11)° and an average C–S and C–N bond lengths of 1.6358 (12) Å and 1.1573 (16) Å, respectively.
In the crystal structure, the ethylenediammonium cations are linked to the chloride and thiocyanate anions by means of five medium N—H···Cl and two weak N—H···N(CS) intermolecular hydrogen bonds (Table 1) to form a three-dimensional network (Fig. 2). The N···Cl and N···N(CS) distances range from 3.1982 (9) to 3.3543 (10) Å and 2.8533 (14) Å to 3.1106 (17) Å, respectively. The sum of Van der Waal's radii of N and Cl, and N and O are 3.3 Å and 2.9 Å, respectively.