organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

(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[Kamoun, S., Jouini, A., Kamoun, M. & Daoud, A. (1989). Acta Cryst. C45, 481-482.]); Chen (2009[Chen, L.-Z. (2009). Acta Cryst. E65, o2625.]). For details of the synthesis of thio­cyanic acid, see: Bartlett et al. (1969[Bartlett, H. E., Jurriaanse, A. & De Haas, K. (1969). Can. J. Chem. 47, 16, 2981-2986.]). For protonic conductivity and dielectric relaxation in ethyl­endi­ammonium salts, see: Karoui et al. (2013[Karoui, S., Kamoun, S. & Jouini, A. (2013). J. Solid State Chem. 197, 60-68.]).

[Scheme 1]

Experimental

Crystal data
  • C2H10N22+·Cl·SCN

  • Mr = 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[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]) Tmin = 0.737, Tmax = 0.887

  • 6396 measured reflections

  • 2189 independent reflections

  • 1947 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.072

  • S = 1.08

  • 2189 reflections

  • 74 parameters

  • H-atom parameters constrained

  • Δρmax = 0.40 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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.

Data collection: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg et al., 1999[Brandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and Mercury (Macrae et al., 2008[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.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

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).

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
[Figure 1] 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.
[Figure 2] 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·SCNF(000) = 164
Mr = 155.65Cell parameters from 3445 reflections
Triclinic, P1Dx = 1.422 Mg m3
Dm = 1.398 Mg m3
Dm measured by flotation
Hall symbol: -P 1Melting point: 443 K
a = 6.2726 (2) ÅMo Kα radiation, λ = 0.7107 Å
b = 6.3462 (2) ÅCell parameters from 5534 reflections
c = 9.1745 (3) Åθ = 3.2–44.7°
α = 92.436 (3)°µ = 0.72 mm1
β = 92.193 (3)°T = 293 K
γ = 94.341 (3)°Parallelipipedic, light yellow
V = 363.52 (2) Å30.50 × 0.42 × 0.17 mm
Z = 2
Data collection top
Agilent Xcalibur (Sapphire2)
diffractometer
2189 independent reflections
Radiation source: Enhance (Mo) X-ray Source1947 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
Detector resolution: 8.3622 pixels mm-1θmax = 30.5°, θmin = 3.2°
ω scansh = 58
Absorption correction: multi-scan
(CrysAlis RED; Agilent, 2012)
k = 99
Tmin = 0.737, Tmax = 0.887l = 1313
6396 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-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 reflectionsΔρmax = 0.40 e Å3
74 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.294 (15)
Primary atom site location: structure-invariant direct methods
Crystal data top
C2H10N22+·Cl·SCNγ = 94.341 (3)°
Mr = 155.65V = 363.52 (2) Å3
Triclinic, P1Z = 2
a = 6.2726 (2) ÅMo Kα radiation
b = 6.3462 (2) ŵ = 0.72 mm1
c = 9.1745 (3) ÅT = 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)
Tmin = 0.737, Tmax = 0.887Rint = 0.018
6396 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.08Δρmax = 0.40 e Å3
2189 reflectionsΔρmin = 0.25 e Å3
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
xyzUiso*/Ueq
Cl10.19093 (4)0.72470 (4)0.47679 (3)0.02934 (10)
S10.68519 (5)0.78130 (5)0.20850 (3)0.03649 (10)
C10.45634 (19)0.73609 (17)0.11677 (11)0.0294 (2)
N10.2924 (2)0.7024 (2)0.05464 (13)0.0458 (3)
N20.31015 (15)0.22026 (15)0.43178 (10)0.0305 (2)
H2A0.43480.24810.48110.046*
H2B0.25900.08880.44730.046*
H2C0.21780.31090.46190.046*
C20.34163 (16)0.24184 (17)0.27393 (12)0.0288 (2)
H2D0.44490.14490.24240.035*
H2E0.40070.38440.25820.035*
C30.13799 (19)0.19753 (19)0.18191 (12)0.0322 (2)
H3E0.17330.18110.08030.039*
H3D0.06650.06510.20950.039*
N30.01089 (16)0.36715 (17)0.19736 (11)0.0345 (2)
H3A0.12830.33340.14120.052*
H3B0.05250.48850.17010.052*
H3C0.04620.38120.29010.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02482 (13)0.02877 (14)0.03390 (15)0.00093 (8)0.00252 (9)0.00075 (9)
S10.02975 (16)0.04342 (18)0.03524 (17)0.00037 (11)0.00273 (11)0.00101 (12)
C10.0356 (5)0.0265 (5)0.0262 (5)0.0033 (4)0.0003 (4)0.0020 (3)
N10.0446 (6)0.0482 (6)0.0434 (6)0.0040 (5)0.0144 (5)0.0008 (5)
N20.0269 (4)0.0339 (5)0.0312 (4)0.0058 (3)0.0035 (3)0.0048 (3)
C20.0229 (4)0.0312 (5)0.0329 (5)0.0040 (4)0.0042 (4)0.0030 (4)
C30.0337 (5)0.0347 (5)0.0275 (5)0.0027 (4)0.0009 (4)0.0066 (4)
N30.0291 (4)0.0447 (5)0.0296 (5)0.0075 (4)0.0064 (3)0.0002 (4)
Geometric parameters (Å, º) top
S1—C11.6358 (12)C2—H2E0.9700
C1—N11.1573 (16)C3—N31.4834 (15)
N2—C21.4798 (14)C3—H3E0.9700
N2—H2A0.8900C3—H3D0.9700
N2—H2B0.8900N3—H3A0.8900
N2—H2C0.8900N3—H3B0.8900
C2—C31.5054 (15)N3—H3C0.8900
C2—H2D0.9700
N1—C1—S1178.48 (11)N3—C3—C2112.98 (9)
C2—N2—H2A109.5N3—C3—H3E109.0
C2—N2—H2B109.5C2—C3—H3E109.0
H2A—N2—H2B109.5N3—C3—H3D109.0
C2—N2—H2C109.5C2—C3—H3D109.0
H2A—N2—H2C109.5H3E—C3—H3D107.8
H2B—N2—H2C109.5C3—N3—H3A109.5
N2—C2—C3113.06 (9)C3—N3—H3B109.5
N2—C2—H2D109.0H3A—N3—H3B109.5
C3—C2—H2D109.0C3—N3—H3C109.5
N2—C2—H2E109.0H3A—N3—H3C109.5
C3—C2—H2E109.0H3B—N3—H3C109.5
H2D—C2—H2E107.8
N2—C2—C3—N372.09 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl1i0.892.363.1982 (9)158
N2—H2B···Cl1ii0.892.353.2246 (10)169
N2—H2C···Cl1iii0.892.643.3237 (10)134
N3—H3C···Cl1iii0.892.463.2953 (11)158
N3—H3A···N1iv0.892.032.8533 (14)153
N2—H2C···Cl10.892.643.3543 (10)138
N3—H3B···N10.892.273.1106 (17)157
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, z; (iii) x, y+1, z+1; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC2H10N22+·Cl·SCN
Mr155.65
Crystal system, space groupTriclinic, 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)
V3)363.52 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.72
Crystal size (mm)0.50 × 0.42 × 0.17
Data collection
DiffractometerAgilent Xcalibur (Sapphire2)
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Agilent, 2012)
Tmin, Tmax0.737, 0.887
No. of measured, independent and
observed [I > 2σ(I)] reflections
6396, 2189, 1947
Rint0.018
(sin θ/λ)max1)0.714
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.072, 1.08
No. of reflections2189
No. of parameters74
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···Cl1i0.892.363.1982 (9)157.7
N2—H2B···Cl1ii0.892.353.2246 (10)168.8
N2—H2C···Cl1iii0.892.643.3237 (10)134.3
N3—H3C···Cl1iii0.892.463.2953 (11)157.5
N3—H3A···N1iv0.892.032.8533 (14)153.0
N2—H2C···Cl10.892.643.3543 (10)137.7
N3—H3B···N10.892.273.1106 (17)156.9
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y1, 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

First citationAgilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England.
First citationBartlett, H. E., Jurriaanse, A. & De Haas, K. (1969). Can. J. Chem. 47, 16, 2981–2986.
First citationBrandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationChen, L.-Z. (2009). Acta Cryst. E65, o2625.  Web of Science CSD CrossRef IUCr Journals
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals
First citationKamoun, S., Jouini, A., Kamoun, M. & Daoud, A. (1989). Acta Cryst. C45, 481–482.  CSD CrossRef CAS Web of Science IUCr Journals
First citationKaroui, S., Kamoun, S. & Jouini, A. (2013). J. Solid State Chem. 197, 60–68.  Web of Science CSD CrossRef CAS
First citationMacrae, 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 CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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