Ethyl­enediammonium dichloro­iodide chloride

Chen, L.-Z.

doi:10.1107/S1600536809039038

organic compounds

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Volume 65| Part 11| November 2009| Page o2625

https://doi.org/10.1107/S1600536809039038

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Ethylenediammonium dichloroiodide chloride

Li-Zhuang Chen ^a ^*

^aSchool of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

(Received 13 August 2009; accepted 25 September 2009; online 3 October 2009)

The asymmetric unit of the crystal structure of the title compound, C₂H₁₀N₂²⁺·Cl₂I⁻·Cl⁻, contains two ethylenediammonium cations, two [ICl₂]⁻ anions and two Cl⁻ anions, of which one cation, one [ICl₂]⁻ anion and one Cl⁻ anion have site symmetry 2, with the mid-point of the C—C bond of the cation, the I atom of [ICl₂]⁻ anion and the Cl⁻ anion located on the twofold rotation axes. The two independent cations show different conformations, the N—C—C—N torsion angles being 160.1 (2) and −73.1 (4)°. The crystal structure is stabilized by extensive intermolecular N—H⋯Cl hydrogen bonding.

Related literature

For general background to combining protonated aromatic nitrogen bases with halide or polyhalide ions, see: Tucker & Kroon (1973 ); Bandoli et al. (1978 ). For Cl—I bond lengths and Cl–I–Cl bond angles, see: Lang et al. (2000 ); Wang et al. (1999a ,b ).

Experimental

Crystal data

C₂H₁₀N₂²⁺·Cl₂I⁻·Cl⁻
M_r = 295.37
Monoclinic, C 2/c
a = 8.565 (2) Å
b = 16.2186 (15) Å
c = 19.9631 (16) Å
β = 101.164 (16)°
V = 2720.8 (7) Å³
Z = 12
Mo Kα radiation
μ = 4.34 mm⁻¹
T = 293 K
0.36 × 0.30 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.230, T_max = 0.301
13418 measured reflections
3106 independent reflections
2821 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.056
S = 1.10
3106 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.89	2.65	3.410 (3)	144
N1—H1A⋯Cl3ⁱ	0.89	2.76	3.341 (3)	124
N1—H1B⋯Cl4	0.89	2.27	3.136 (2)	164
N1—H1C⋯Cl5ⁱ	0.89	2.27	3.148 (3)	168
N2—H2A⋯Cl4ⁱⁱ	0.89	2.38	3.232 (3)	161
N2—H2B⋯Cl5ⁱⁱⁱ	0.89	2.26	3.123 (3)	162
N2—H2C⋯Cl3ⁱⁱ	0.89	2.40	3.246 (3)	159
N3—H3A⋯Cl3^iv	0.89	2.42	3.297 (2)	167
N3—H3B⋯Cl5	0.89	2.32	3.144 (3)	154
N3—H3C⋯Cl1ⁱⁱ	0.89	2.49	3.319 (2)	155
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) x+1, y, z; (iv) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039038/xu2588sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039038/xu2588Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to combining protonated aromatic nitrogen bases with halide or polyhalide ions due to their interesting structural features (Tucker & Kroon, 1973; Bandoli et al., 1978). In our laboratory, a compound containing diprotonated ethylenediamine and ICl₂ anions has been synthesized, its crystal structure is reported herein.

The asymmetric unit of the title compound, [C₂H₁₀N₂]²⁺.[ICl₂]^-.Cl^-, (Fig. 1) consists of two diprotonated ethylenediammonium cations, two [ICl₂]^- anions and two Cl^- anions. The dichloroiodide anion Cl1–I1–Cl1A has site symmetry 2 and is linear with Cl1—I1—Cl1A bond angle of 179.55 (4). The Cl1—I1 bond length is similar to the values of 2.5417 (11) to 2.5575 (10) Å reported by (Wang et al., 1999a,b). In Cl2—I2—Cl3 anion, the I2—Cl3 bond length of 2.6790 (9) Å is longer than I2—Cl2 bond length of 2.4518 (10) Å. The Cl2—I2—Cl3 is also nearly linear, the Cl2—I2—Cl3 bond angle being 178.30 (3)°. The nearly linear Cl—I—Cl bonds are similar to those reported by Lang et al. (2000) and Wang et al. (1999a,b). The two independent cations show the different conformations, the N-C-C-N torsion angles being 160.1 (2) and -73.1 (4)°. The crystal structure is stabilized by intermolecular N—H···Cl hydrogen bonds (Fig. 2).

Related literature top

For general background to combining protonated aromatic

nitrogen bases with halide or polyhalide ions, see: Tucker & Kroon (1973); Bandoli et al. (1978). For Cl—I bond lengths and Cl–I–Cl bond angles, see: Lang et al. (2000); Wang et al. (1999a,b).

Experimental top

KI (0.33 g) and I₂ (0.5 g) were dissolved in a mixed solution of ethanol (30 ml) and concentrated hydrochloric acid (10 ml, 36%). On addition of ethylenediamine (0.60 g) to the above solution, the mixture was stirred for 2 h, then filtered. The filtrate was left at room temperature to allow the solvent to evaporate. Yellow transparent block crystals were obtained after two weeks.

Structure description top

For general background to combining protonated aromatic

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The structure of the title compound with atom labels. Displacement ellipsoids were drawn at the 40% probability level [symmetry code: (i) -x, y, -z+1/2; (ii) 2-x, y, -z+1/2].

Ethylenediammonium dichloroiodide chloride top

Crystal data top

C₂H₁₀N₂²⁺·Cl₂I⁻·Cl⁻	F(000) = 1680
M_r = 295.37	D_x = 2.163 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2821 reflections
a = 8.565 (2) Å	θ = 2.5–27.5°
b = 16.2186 (15) Å	µ = 4.34 mm⁻¹
c = 19.9631 (16) Å	T = 293 K
β = 101.164 (16)°	Block, yellow
V = 2720.8 (7) Å³	0.36 × 0.30 × 0.28 mm
Z = 12

Data collection top

Rigaku SCXmini diffractometer	3106 independent reflections
Radiation source: fine-focus sealed tube	2821 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −20→20
T_min = 0.230, T_max = 0.301	l = −25→25
13418 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)] = 0.023	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0271P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3106 reflections	Δρ_max = 0.92 e Å⁻³
114 parameters	Δρ_min = −0.65 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00017 (4)

Crystal data top

C₂H₁₀N₂²⁺·Cl₂I⁻·Cl⁻	V = 2720.8 (7) Å³
M_r = 295.37	Z = 12
Monoclinic, C2/c	Mo Kα radiation
a = 8.565 (2) Å	µ = 4.34 mm⁻¹
b = 16.2186 (15) Å	T = 293 K
c = 19.9631 (16) Å	0.36 × 0.30 × 0.28 mm
β = 101.164 (16)°

Data collection top

Rigaku SCXmini diffractometer	3106 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2821 reflections with I > 2σ(I)
T_min = 0.230, T_max = 0.301	R_int = 0.034
13418 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.056	H-atom parameters constrained
S = 1.10	Δρ_max = 0.92 e Å⁻³
3106 reflections	Δρ_min = −0.65 e Å⁻³
114 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
C1	0.9115 (3)	0.1716 (2)	0.24029 (15)	0.0472 (8)
H1D	0.8758	0.2243	0.2199	0.057*
H1E	0.8778	0.1289	0.2065	0.057*
C2	1.0658 (4)	0.8169 (2)	0.43343 (16)	0.0412 (7)
H2D	1.0988	0.8492	0.4747	0.049*
H2E	1.1129	0.7626	0.4416	0.049*
C3	0.8881 (4)	0.80844 (18)	0.41979 (16)	0.0415 (7)
H3D	0.8539	0.7849	0.3747	0.050*
H3E	0.8592	0.7700	0.4526	0.050*
Cl1	0.30378 (10)	0.45106 (5)	0.26597 (4)	0.04654 (19)
Cl2	1.16812 (9)	0.58195 (6)	0.42064 (4)	0.04530 (19)
Cl3	0.57256 (8)	0.54598 (5)	0.41952 (3)	0.03576 (16)
Cl4	0.5000	0.23483 (7)	0.2500	0.0401 (2)
Cl5	0.47720 (9)	0.79063 (5)	0.40942 (4)	0.04283 (18)
I1	0.0000	0.450435 (17)	0.2500	0.03375 (8)
I2	0.88263 (2)	0.564990 (11)	0.418170 (9)	0.02956 (7)
N1	0.8379 (3)	0.15711 (16)	0.29954 (12)	0.0395 (6)
H1A	0.8485	0.1042	0.3114	0.059*
H1B	0.7351	0.1700	0.2890	0.059*
H1C	0.8855	0.1883	0.3342	0.059*
N2	1.1282 (3)	0.85669 (15)	0.37681 (12)	0.0384 (6)
H2A	1.0820	0.8342	0.3372	0.058*
H2B	1.2330	0.8492	0.3832	0.058*
H2C	1.1069	0.9104	0.3762	0.058*
N3	0.8007 (3)	0.88669 (15)	0.42352 (12)	0.0382 (6)
H3A	0.8401	0.9123	0.4626	0.057*
H3B	0.6981	0.8759	0.4216	0.057*
H3C	0.8115	0.9189	0.3886	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0272 (16)	0.084 (3)	0.0303 (15)	−0.0052 (16)	0.0042 (13)	0.0027 (16)
C2	0.0345 (17)	0.0478 (18)	0.0391 (16)	0.0067 (13)	0.0013 (13)	0.0026 (14)
C3	0.0399 (18)	0.0322 (16)	0.0529 (19)	−0.0026 (12)	0.0100 (15)	0.0020 (14)
Cl1	0.0356 (4)	0.0628 (5)	0.0405 (4)	0.0103 (4)	0.0056 (3)	0.0010 (4)
Cl2	0.0291 (4)	0.0586 (5)	0.0487 (4)	−0.0054 (3)	0.0089 (3)	0.0000 (4)
Cl3	0.0263 (3)	0.0409 (4)	0.0391 (4)	0.0016 (3)	0.0038 (3)	−0.0005 (3)
Cl4	0.0340 (5)	0.0407 (6)	0.0420 (6)	0.000	−0.0016 (4)	0.000
Cl5	0.0300 (4)	0.0488 (4)	0.0488 (4)	−0.0043 (3)	0.0055 (3)	−0.0040 (3)
I1	0.03698 (16)	0.03827 (15)	0.02565 (13)	0.000	0.00517 (11)	0.000
I2	0.02793 (11)	0.03197 (11)	0.02788 (10)	0.00081 (7)	0.00317 (7)	−0.00044 (7)
N1	0.0337 (13)	0.0450 (15)	0.0410 (14)	0.0042 (11)	0.0099 (11)	0.0038 (11)
N2	0.0295 (13)	0.0401 (14)	0.0463 (14)	0.0023 (10)	0.0090 (11)	−0.0025 (11)
N3	0.0310 (13)	0.0435 (14)	0.0413 (14)	−0.0039 (11)	0.0103 (11)	−0.0044 (11)

Geometric parameters (Å, º) top

C1—N1	1.463 (4)	Cl2—I2	2.4518 (10)
C1—C1ⁱ	1.491 (6)	Cl3—I2	2.6790 (9)
C1—H1D	0.9700	I1—Cl1ⁱⁱ	2.5595 (10)
C1—H1E	0.9700	N1—H1A	0.8900
C2—N2	1.488 (4)	N1—H1B	0.8900
C2—C3	1.499 (4)	N1—H1C	0.8900
C2—H2D	0.9700	N2—H2A	0.8900
C2—H2E	0.9700	N2—H2B	0.8900
C3—N3	1.483 (4)	N2—H2C	0.8900
C3—H3D	0.9700	N3—H3A	0.8900
C3—H3E	0.9700	N3—H3B	0.8900
Cl1—I1	2.5595 (10)	N3—H3C	0.8900

N1—C1—C1ⁱ	111.4 (3)	Cl2—I2—Cl3	178.30 (3)
N1—C1—H1D	109.3	C1—N1—H1A	109.5
C1ⁱ—C1—H1D	109.3	C1—N1—H1B	109.5
N1—C1—H1E	109.3	H1A—N1—H1B	109.5
C1ⁱ—C1—H1E	109.3	C1—N1—H1C	109.5
H1D—C1—H1E	108.0	H1A—N1—H1C	109.5
N2—C2—C3	113.8 (3)	H1B—N1—H1C	109.5
N2—C2—H2D	108.8	C2—N2—H2A	109.5
C3—C2—H2D	108.8	C2—N2—H2B	109.5
N2—C2—H2E	108.8	H2A—N2—H2B	109.5
C3—C2—H2E	108.8	C2—N2—H2C	109.5
H2D—C2—H2E	107.7	H2A—N2—H2C	109.5
N3—C3—C2	114.7 (3)	H2B—N2—H2C	109.5
N3—C3—H3D	108.6	C3—N3—H3A	109.5
C2—C3—H3D	108.6	C3—N3—H3B	109.5
N3—C3—H3E	108.6	H3A—N3—H3B	109.5
C2—C3—H3E	108.6	C3—N3—H3C	109.5
H3D—C3—H3E	107.6	H3A—N3—H3C	109.5
Cl1—I1—Cl1ⁱⁱ	179.55 (4)	H3B—N3—H3C	109.5

Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱⁱⁱ	0.89	2.65	3.410 (3)	144
N1—H1A···Cl3ⁱⁱⁱ	0.89	2.76	3.341 (3)	124
N1—H1B···Cl4	0.89	2.27	3.136 (2)	164
N1—H1C···Cl5ⁱⁱⁱ	0.89	2.27	3.148 (3)	168
N2—H2A···Cl4^iv	0.89	2.38	3.232 (3)	161
N2—H2B···Cl5^v	0.89	2.26	3.123 (3)	162
N2—H2C···Cl3^iv	0.89	2.40	3.246 (3)	159
N3—H3A···Cl3^vi	0.89	2.42	3.297 (2)	167
N3—H3B···Cl5	0.89	2.32	3.144 (3)	154
N3—H3C···Cl1^iv	0.89	2.49	3.319 (2)	155

Symmetry codes: (iii) x+1/2, y−1/2, z; (iv) x+1/2, y+1/2, z; (v) x+1, y, z; (vi) −x+3/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·Cl₂I⁻·Cl⁻
M_r	295.37
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	8.565 (2), 16.2186 (15), 19.9631 (16)
β (°)	101.164 (16)
V (Å³)	2720.8 (7)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	4.34
Crystal size (mm)	0.36 × 0.30 × 0.28

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.230, 0.301
No. of measured, independent and observed [I > 2σ(I)] reflections	13418, 3106, 2821
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.056, 1.10
No. of reflections	3106
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.65

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.89	2.65	3.410 (3)	144.3
N1—H1A···Cl3ⁱ	0.89	2.76	3.341 (3)	123.9
N1—H1B···Cl4	0.89	2.27	3.136 (2)	163.9
N1—H1C···Cl5ⁱ	0.89	2.27	3.148 (3)	167.5
N2—H2A···Cl4ⁱⁱ	0.89	2.38	3.232 (3)	161.0
N2—H2B···Cl5ⁱⁱⁱ	0.89	2.26	3.123 (3)	162.0
N2—H2C···Cl3ⁱⁱ	0.89	2.40	3.246 (3)	158.5
N3—H3A···Cl3^iv	0.89	2.42	3.297 (2)	167.0
N3—H3B···Cl5	0.89	2.32	3.144 (3)	154.4
N3—H3C···Cl1ⁱⁱ	0.89	2.49	3.319 (2)	154.8

Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x+1/2, y+1/2, z; (iii) x+1, y, z; (iv) −x+3/2, −y+3/2, −z+1.

Acknowledgements

This work was supported by a start-up grant from Jiangsu University of Science and Technology, China.

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