Ethyl­enediaminium hemioxalate thio­cyanate

Narimani, L.; Yamin, B.M.

doi:10.1107/S1600536810005994

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o669

doi:10.1107/S1600536810005994

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Ethylenediaminium hemioxalate thiocyanate

Leila Narimani ^a and Bohari M. Yamin ^a ^*

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

Experimental

Crystal data

C₂H₁₀N₂²⁺·0.5C₂O₄²⁻·NCS⁻
M_r = 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 ) T_min = 0.854, T_max = 0.879
5091 measured reflections
1867 independent reflections
1718 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.095
S = 1.06
1867 reflections
94 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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⋯O2^iv	0.89	1.99	2.8189 (18)	154
C4—H4B⋯S1^v	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 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005994/ci5031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005994/ci5031Isup2.hkl

checkCIF report

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).

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

	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).
	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⁻·NCS⁻	Z = 2
M_r = 164.21	F(000) = 174
Triclinic, P1	D_x = 1.452 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4044 (19) Å	Cell parameters from 3525 reflections
b = 6.6199 (19) Å	θ = 2.2–28.3°
c = 9.377 (3) Å	µ = 0.38 mm⁻¹
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 tube	1718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 83.66 pixels mm^-1	θ_max = 28.3°, θ_min = 2.2°
ω scan	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→8
T_min = 0.854, T_max = 0.879	l = −12→12
5091 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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0453P)² + 0.1426P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1867 reflections	Δρ_max = 0.51 e Å⁻³
94 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.41 (2)

Crystal data top

C₂H₁₀N₂²⁺·0.5C₂O₄²⁻·NCS⁻	γ = 74.452 (5)°
M_r = 164.21	V = 375.5 (2) Å³
Triclinic, P1	Z = 2
a = 6.4044 (19) Å	Mo Kα radiation
b = 6.6199 (19) Å	µ = 0.38 mm⁻¹
c = 9.377 (3) Å	T = 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)
T_min = 0.854, T_max = 0.879	R_int = 0.017
5091 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.06	Δρ_max = 0.51 e Å⁻³
1867 reflections	Δρ_min = −0.52 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.23176 (14)	0.09074 (15)	0.45456 (11)	0.0325 (2)
O2	0.41295 (15)	0.23958 (14)	0.57426 (10)	0.0309 (2)
C1	0.39758 (18)	0.09557 (17)	0.50846 (12)	0.0232 (2)
S1	0.76420 (7)	0.30131 (6)	0.20864 (5)	0.04886 (18)
N1	0.7143 (2)	0.7005 (2)	0.04926 (17)	0.0521 (4)
C2	0.7374 (2)	0.5334 (2)	0.11335 (15)	0.0362 (3)
N2	0.2850 (2)	0.94792 (18)	0.17891 (12)	0.0346 (3)
H2A	0.2477	1.0605	0.1135	0.041*
H2B	0.4190	0.8736	0.1513	0.041*
H2C	0.2819	0.9898	0.2650	0.041*
N3	0.18949 (17)	0.64628 (17)	0.44290 (12)	0.0287 (2)
H3A	0.2241	0.5223	0.4981	0.034*
H3B	0.0574	0.7188	0.4760	0.034*
H3C	0.2868	0.7191	0.4460	0.034*
C3	0.1898 (2)	0.6105 (2)	0.29020 (15)	0.0316 (3)
H3D	0.0877	0.5264	0.2881	0.038*
H3E	0.3340	0.5311	0.2548	0.038*
C4	0.1284 (2)	0.8139 (2)	0.19058 (15)	0.0356 (3)
H4A	0.1213	0.7813	0.0945	0.043*
H4B	−0.0157	0.8932	0.2262	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0227 (4)	0.0324 (5)	0.0425 (5)	−0.0015 (3)	−0.0087 (4)	−0.0100 (4)
O2	0.0302 (5)	0.0241 (4)	0.0388 (5)	−0.0025 (3)	−0.0072 (4)	−0.0091 (4)
C1	0.0220 (5)	0.0207 (5)	0.0251 (5)	−0.0035 (4)	−0.0018 (4)	−0.0013 (4)
S1	0.0510 (3)	0.0346 (2)	0.0483 (3)	0.00328 (17)	0.00029 (18)	0.00231 (16)
N1	0.0485 (8)	0.0464 (8)	0.0511 (8)	−0.0062 (6)	−0.0010 (6)	0.0098 (6)
C2	0.0303 (6)	0.0399 (7)	0.0327 (7)	−0.0011 (5)	−0.0009 (5)	−0.0037 (5)
N2	0.0409 (6)	0.0288 (5)	0.0300 (5)	−0.0051 (5)	−0.0044 (4)	0.0023 (4)
N3	0.0267 (5)	0.0258 (5)	0.0341 (6)	−0.0077 (4)	−0.0060 (4)	−0.0002 (4)
C3	0.0323 (6)	0.0261 (6)	0.0353 (7)	−0.0050 (5)	−0.0018 (5)	−0.0067 (5)
C4	0.0396 (7)	0.0336 (7)	0.0332 (7)	−0.0053 (5)	−0.0116 (5)	−0.0031 (5)

Geometric parameters (Å, º) top

O1—C1	1.2539 (15)	N3—C3	1.4879 (18)
O2—C1	1.2474 (15)	N3—H3A	0.89
C1—C1ⁱ	1.568 (2)	N3—H3B	0.89
S1—C2	1.6295 (16)	N3—H3C	0.89
N1—C2	1.155 (2)	C3—C4	1.5054 (19)
N2—C4	1.4890 (19)	C3—H3D	0.97
N2—H2A	0.89	C3—H3E	0.97
N2—H2B	0.89	C4—H4A	0.97
N2—H2C	0.89	C4—H4B	0.97

O2—C1—O1	125.46 (11)	H3A—N3—H3C	109.5
O2—C1—C1ⁱ	117.42 (13)	H3B—N3—H3C	109.5
O1—C1—C1ⁱ	117.12 (13)	N3—C3—C4	112.50 (11)
N1—C2—S1	177.95 (14)	N3—C3—H3D	109.1
C4—N2—H2A	109.5	C4—C3—H3D	109.1
C4—N2—H2B	109.5	N3—C3—H3E	109.1
H2A—N2—H2B	109.5	C4—C3—H3E	109.1
C4—N2—H2C	109.5	H3D—C3—H3E	107.8
H2A—N2—H2C	109.5	N2—C4—C3	113.05 (11)
H2B—N2—H2C	109.5	N2—C4—H4A	109.0
C3—N3—H3A	109.5	C3—C4—H4A	109.0
C3—N3—H3B	109.5	N2—C4—H4B	109.0
H3A—N3—H3B	109.5	C3—C4—H4B	109.0
C3—N3—H3C	109.5	H4A—C4—H4B	107.8

N3—C3—C4—N2	62.64 (15)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···N1ⁱⁱ	0.89	2.05	2.899 (2)	159
N2—H2C···O1ⁱⁱⁱ	0.89	1.95	2.8337 (18)	172
N3—H3B···O1^iv	0.89	2.02	2.9078 (17)	174
N3—H3C···O1ⁱⁱⁱ	0.89	2.40	3.0465 (18)	129
N3—H3C···O2^v	0.89	1.99	2.8189 (18)	154
C4—H4B···S1^vi	0.97	2.68	3.4495 (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) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·0.5C₂O₄²⁻·NCS⁻
M_r	164.21
Crystal system, space group	Triclinic, 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)
V (Å³)	375.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.43 × 0.41 × 0.35

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.854, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	5091, 1867, 1718
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.06
No. of reflections	1867
No. of parameters	94
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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···O2^iv	0.89	1.99	2.8189 (18)	154
C4—H4B···S1^v	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.

Acknowledgements

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

References

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