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

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Ethyl­enediaminium hemioxalate thio­cyanate

aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
*Correspondence e-mail: bohari@ukm.my

(Received 1 February 2010; accepted 14 February 2010; online 20 February 2010)

In the title compound, C2H10N22+·0.5(C2O4)2−·NCS, the ethyl­enediaminium dication adopts a (+)-synclinal conformation with an N—C—C—N torsion angle of 62.64 (15)°. The oxalate dianion lies across an inversion centre. In the crystal structure, the ions are linked through N—H⋯N, N—H⋯O and C—H⋯S hydrogen bonds, leading to the formation of a three-dimensional network.

Related literature

For related structures, see: Barnes et al. (1998[Barnes, J. C., Longhurst, R. W. & Weakley, T. J. R. (1998). Acta Cryst. C54, 1347-1351.]); Smith et al. (2006[Smith, G., Wermuth, U. D., Young, D. J. & Healy, P. C. (2006). Acta Cryst. E62, o3124-o3126.]); Seidel et al. (2008[Seidel, R. W., Winter, M. V. & Oppel, I. M. (2008). Acta Cryst. E64, o181.]); Tang et al. (2009[Tang, Z., Xu, M., Zhang, H.-C. & Feng, H. (2009). Acta Cryst. E65, o1670.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C2H10N22+·0.5C2O42−·NCS

  • Mr = 164.21

  • Triclinic, [P \overline 1]

  • a = 6.4044 (19) Å

  • b = 6.6199 (19) Å

  • c = 9.377 (3) Å

  • α = 80.799 (5)°

  • β = 81.179 (5)°

  • γ = 74.452 (5)°

  • V = 375.5 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.38 mm−1

  • T = 298 K

  • 0.43 × 0.41 × 0.35 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.854, Tmax = 0.879

  • 5091 measured reflections

  • 1867 independent reflections

  • 1718 reflections with I > 2σ(I)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.095

  • S = 1.06

  • 1867 reflections

  • 94 parameters

  • H-atom parameters constrained

  • Δρmax = 0.51 e Å−3

  • Δρmin = −0.52 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2B⋯N1 0.89 2.11 2.986 (2) 169
N3—H3A⋯O2 0.89 2.02 2.8685 (17) 158
C3—H3E⋯S1 0.97 2.77 3.7294 (18) 169
N2—H2A⋯N1i 0.89 2.05 2.899 (2) 159
N2—H2C⋯O1ii 0.89 1.95 2.8337 (18) 172
N3—H3B⋯O1iii 0.89 2.02 2.9078 (17) 174
N3—H3C⋯O1ii 0.89 2.40 3.0465 (18) 129
N3—H3C⋯O2iv 0.89 1.99 2.8189 (18) 154
C4—H4B⋯S1v 0.97 2.68 3.4495 (18) 136
Symmetry codes: (i) -x+1, -y+2, -z; (ii) x, y+1, z; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z+1; (v) x-1, y+1, z.

Data collection: SMART (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995[Nardelli, M. (1995). J. Appl. Cryst. 28, 659.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Aqueous solution of ethylenediamine and oxalic acid regardless of their stiochiometric ratio was reported to give ethylenediammonium bis(monohydrogen oxalate) monohydrate (II) (Barnes et al., 1998). However, the same reaction but in the presence of ammonium thiocyanate was found to give an ethylenediammonium hemioxalate thiocynate, the title compound, (I, Fig.1), indicating that the oxalic acid has been completely deprotonated.

The centrosymmetric oxalate anion is planar as commonly observed in many oxalate salts (Tang et al., 2009; Seidel et al., 2008). The C—O bond lengths are quite similar indicating a delocalisation of electron about the O—C—O bond as observed in (II) and N-[2-(2-chlorophenyl)-2-hydroxyethyl]-propann-2-aminium hemioxalate (III) (Tang et al., 2009). The ethylenediaminium ion in this salt is not planar but twisted with a N3—C3—C4—N2 torsion angle of 62.64 (15)°. In compound (II), and ethylenediammonium pyridine-2,5-dicarboxylate dihydrate (IV) (Smith et al., 2006), the ethylenediammonium cation is centrosymmetric and has an extended conformation with a N—C—C—N torsion angle of 180°. The thiocyanate anion is linear. The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable with those in (II), (III) and (IV).

In the crystal structure, the molecules are linked by N—H···N, N—H···O and C—H···S hydrogen bonds (Table 1) forming a three-dimemsional network (Fig. 2).

Related literature top

For related structures, see: Barnes et al. (1998); Smith et al. (2006); Seidel et al. (2008); Tang et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

An aqueous solution (10 ml) of ammonium thiocyanate (0.152 g, 2 mmol) was added into a beaker containing oxalate acid (0.126 g, 1 mmol) and ethylenediamine (2 mmol) in distilled water (40 ml). After one week of evaporation at room temperature, colourless crystals of the title compound were obtained (yield 92%; m.p. 457.1-458.3 K).

Refinement top

After their location in a difference map, the methylene and ammonium H-atoms were positioned geometrically [N–H = 0.89 Å and C–H = 0.97 Å] and allowed to ride on the parent atoms, with Uiso(H) = 1.2Ueq(C,N). A rotating group model was used for the ammonium group.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms in the dianion are related to other labelled atoms in it by the symmetry operation (1 - x, -y, 1 - z).
[Figure 2] Fig. 2. Packing diagram of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines.
Ethylenediaminium hemioxalate thiocyanate top
Crystal data top
C2H10N22+·0.5C2O42·NCSZ = 2
Mr = 164.21F(000) = 174
Triclinic, P1Dx = 1.452 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.4044 (19) ÅCell parameters from 3525 reflections
b = 6.6199 (19) Åθ = 2.2–28.3°
c = 9.377 (3) ŵ = 0.38 mm1
α = 80.799 (5)°T = 298 K
β = 81.179 (5)°Block, colourless
γ = 74.452 (5)°0.43 × 0.41 × 0.35 mm
V = 375.5 (2) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1867 independent reflections
Radiation source: fine-focus sealed tube1718 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 83.66 pixels mm-1θmax = 28.3°, θmin = 2.2°
ω scanh = 88
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 88
Tmin = 0.854, Tmax = 0.879l = 1212
5091 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)] = 0.034H-atom parameters constrained
wR(F2) = 0.095 w = 1/[σ2(Fo2) + (0.0453P)2 + 0.1426P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1867 reflectionsΔρmax = 0.51 e Å3
94 parametersΔρmin = 0.52 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.41 (2)
Crystal data top
C2H10N22+·0.5C2O42·NCSγ = 74.452 (5)°
Mr = 164.21V = 375.5 (2) Å3
Triclinic, P1Z = 2
a = 6.4044 (19) ÅMo Kα radiation
b = 6.6199 (19) ŵ = 0.38 mm1
c = 9.377 (3) ÅT = 298 K
α = 80.799 (5)°0.43 × 0.41 × 0.35 mm
β = 81.179 (5)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1867 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1718 reflections with I > 2σ(I)
Tmin = 0.854, Tmax = 0.879Rint = 0.017
5091 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.06Δρmax = 0.51 e Å3
1867 reflectionsΔρmin = 0.52 e Å3
94 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O10.23176 (14)0.09074 (15)0.45456 (11)0.0325 (2)
O20.41295 (15)0.23958 (14)0.57426 (10)0.0309 (2)
C10.39758 (18)0.09557 (17)0.50846 (12)0.0232 (2)
S10.76420 (7)0.30131 (6)0.20864 (5)0.04886 (18)
N10.7143 (2)0.7005 (2)0.04926 (17)0.0521 (4)
C20.7374 (2)0.5334 (2)0.11335 (15)0.0362 (3)
N20.2850 (2)0.94792 (18)0.17891 (12)0.0346 (3)
H2A0.24771.06050.11350.041*
H2B0.41900.87360.15130.041*
H2C0.28190.98980.26500.041*
N30.18949 (17)0.64628 (17)0.44290 (12)0.0287 (2)
H3A0.22410.52230.49810.034*
H3B0.05740.71880.47600.034*
H3C0.28680.71910.44600.034*
C30.1898 (2)0.6105 (2)0.29020 (15)0.0316 (3)
H3D0.08770.52640.28810.038*
H3E0.33400.53110.25480.038*
C40.1284 (2)0.8139 (2)0.19058 (15)0.0356 (3)
H4A0.12130.78130.09450.043*
H4B0.01570.89320.22620.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0227 (4)0.0324 (5)0.0425 (5)0.0015 (3)0.0087 (4)0.0100 (4)
O20.0302 (5)0.0241 (4)0.0388 (5)0.0025 (3)0.0072 (4)0.0091 (4)
C10.0220 (5)0.0207 (5)0.0251 (5)0.0035 (4)0.0018 (4)0.0013 (4)
S10.0510 (3)0.0346 (2)0.0483 (3)0.00328 (17)0.00029 (18)0.00231 (16)
N10.0485 (8)0.0464 (8)0.0511 (8)0.0062 (6)0.0010 (6)0.0098 (6)
C20.0303 (6)0.0399 (7)0.0327 (7)0.0011 (5)0.0009 (5)0.0037 (5)
N20.0409 (6)0.0288 (5)0.0300 (5)0.0051 (5)0.0044 (4)0.0023 (4)
N30.0267 (5)0.0258 (5)0.0341 (6)0.0077 (4)0.0060 (4)0.0002 (4)
C30.0323 (6)0.0261 (6)0.0353 (7)0.0050 (5)0.0018 (5)0.0067 (5)
C40.0396 (7)0.0336 (7)0.0332 (7)0.0053 (5)0.0116 (5)0.0031 (5)
Geometric parameters (Å, º) top
O1—C11.2539 (15)N3—C31.4879 (18)
O2—C11.2474 (15)N3—H3A0.89
C1—C1i1.568 (2)N3—H3B0.89
S1—C21.6295 (16)N3—H3C0.89
N1—C21.155 (2)C3—C41.5054 (19)
N2—C41.4890 (19)C3—H3D0.97
N2—H2A0.89C3—H3E0.97
N2—H2B0.89C4—H4A0.97
N2—H2C0.89C4—H4B0.97
O2—C1—O1125.46 (11)H3A—N3—H3C109.5
O2—C1—C1i117.42 (13)H3B—N3—H3C109.5
O1—C1—C1i117.12 (13)N3—C3—C4112.50 (11)
N1—C2—S1177.95 (14)N3—C3—H3D109.1
C4—N2—H2A109.5C4—C3—H3D109.1
C4—N2—H2B109.5N3—C3—H3E109.1
H2A—N2—H2B109.5C4—C3—H3E109.1
C4—N2—H2C109.5H3D—C3—H3E107.8
H2A—N2—H2C109.5N2—C4—C3113.05 (11)
H2B—N2—H2C109.5N2—C4—H4A109.0
C3—N3—H3A109.5C3—C4—H4A109.0
C3—N3—H3B109.5N2—C4—H4B109.0
H3A—N3—H3B109.5C3—C4—H4B109.0
C3—N3—H3C109.5H4A—C4—H4B107.8
N3—C3—C4—N262.64 (15)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N10.892.112.986 (2)169
N3—H3A···O20.892.022.8685 (17)158
C3—H3E···S10.972.773.7294 (18)169
N2—H2A···N1ii0.892.052.899 (2)159
N2—H2C···O1iii0.891.952.8337 (18)172
N3—H3B···O1iv0.892.022.9078 (17)174
N3—H3C···O1iii0.892.403.0465 (18)129
N3—H3C···O2v0.891.992.8189 (18)154
C4—H4B···S1vi0.972.683.4495 (18)136
Symmetry codes: (ii) x+1, y+2, z; (iii) x, y+1, z; (iv) x, y+1, z+1; (v) x+1, y+1, z+1; (vi) x1, y+1, z.

Experimental details

Crystal data
Chemical formulaC2H10N22+·0.5C2O42·NCS
Mr164.21
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)6.4044 (19), 6.6199 (19), 9.377 (3)
α, β, γ (°)80.799 (5), 81.179 (5), 74.452 (5)
V3)375.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.43 × 0.41 × 0.35
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.854, 0.879
No. of measured, independent and
observed [I > 2σ(I)] reflections
5091, 1867, 1718
Rint0.017
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.095, 1.06
No. of reflections1867
No. of parameters94
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.51, 0.52

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N10.892.112.986 (2)169
N3—H3A···O20.892.022.8685 (17)158
C3—H3E···S10.972.773.7294 (18)169
N2—H2A···N1i0.892.052.899 (2)159
N2—H2C···O1ii0.891.952.8337 (18)172
N3—H3B···O1iii0.892.022.9078 (17)174
N3—H3C···O1ii0.892.403.0465 (18)129
N3—H3C···O2iv0.891.992.8189 (18)154
C4—H4B···S1v0.972.683.4495 (18)136
Symmetry codes: (i) x+1, y+2, z; (ii) x, y+1, z; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1; (v) x1, y+1, z.
 

Acknowledgements

The authors thank the Malaysian Government and Universiti Kebangsaan Malaysia for the research grant No. UKM-GUP-NBT-68–27-110.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationBarnes, J. C., Longhurst, R. W. & Weakley, T. J. R. (1998). Acta Cryst. C54, 1347–1351.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationNardelli, M. (1995). J. Appl. Cryst. 28, 659.  CrossRef IUCr Journals Google Scholar
First citationSeidel, R. W., Winter, M. V. & Oppel, I. M. (2008). Acta Cryst. E64, o181.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
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First citationSiemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSmith, G., Wermuth, U. D., Young, D. J. & Healy, P. C. (2006). Acta Cryst. E62, o3124–o3126.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTang, Z., Xu, M., Zhang, H.-C. & Feng, H. (2009). Acta Cryst. E65, o1670.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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