Ethyl­enedi­ammonium chloride thio­cyanate

Karoui, S.; Kamoun, S.; Michaud, F.

doi:10.1107/S1600536813008830

organic compounds

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Volume 69| Part 5| May 2013| Page o669

https://doi.org/10.1107/S1600536813008830

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Ethylenediammonium chloride thiocyanate

Sahel Karoui,^a Slaheddine Kamoun ^a ^* and François Michaud ^b

^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

(Received 23 March 2013; accepted 1 April 2013; online 5 April 2013)

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

C₂H₁₀N₂²⁺·Cl⁻·SCN⁻
M_r = 155.65
Triclinic, $[P \overline 1]$
a = 6.2726 (2) Å
b = 6.3462 (2) Å
c = 9.1745 (3) Å
α = 92.436 (3)°
β = 92.193 (3)°
γ = 94.341 (3)°
V = 363.52 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.50 × 0.42 × 0.17 mm

Data collection

Agilent Xcalibur (Sapphire2) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012 ) T_min = 0.737, T_max = 0.887
6396 measured reflections
2189 independent reflections
1947 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.072
S = 1.08
2189 reflections
74 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯N1^iv	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.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813008830/cv5396sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: 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).

Figures top

	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.

Ethylendiammonium chloride thiocyanate top

Crystal data top

C₂H₁₀N₂²⁺·Cl⁻·SCN⁻	F(000) = 164
M_r = 155.65	Cell parameters from 3445 reflections
Triclinic, P1	D_x = 1.422 Mg m⁻³ D_m = 1.398 Mg m⁻³ D_m 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

Data collection top

Agilent Xcalibur (Sapphire2) diffractometer	2189 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1947 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 8.3622 pixels mm^-1	θ_max = 30.5°, θ_min = 3.2°
ω scans	h = −5→8
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	k = −9→9
T_min = 0.737, T_max = 0.887	l = −13→13
6396 measured reflections

Refinement top

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(F_o²) + (0.0383P)² + 0.0716P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2189 reflections	Δρ_max = 0.40 e Å⁻³
74 parameters	Δρ_min = −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

Crystal data top

C₂H₁₀N₂²⁺·Cl⁻·SCN⁻	γ = 94.341 (3)°
M_r = 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)°

Data collection top

Agilent Xcalibur (Sapphire2) diffractometer	2189 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	1947 reflections with I > 2σ(I)
T_min = 0.737, T_max = 0.887	R_int = 0.018
6396 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.08	Δρ_max = 0.40 e Å⁻³
2189 reflections	Δρ_min = −0.25 e Å⁻³
74 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···N1^iv	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⁻
M_r	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)
T_min, T_max	0.737, 0.887
No. of measured, independent and observed [I > 2σ(I)] reflections	6396, 2189, 1947
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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···N1^iv	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.

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