supplementary materials
Ethylenediammonium dichloroiodide chloride
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.
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.
H atoms were placed in calculated positions with C—H = 0.97 Å and N—H
= 0.89 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C)
and 1.5Ueq(N).
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).
Ethylenediammonium dichloroiodide chloride
top
Crystal data top
| C2H10N22+·Cl2I−·Cl− | F(000) = 1680 |
| Mr = 295.37 | Dx = 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 | Rint = 0.034 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
| ω scans | h = −11→11 |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005) | k = −20→20 |
| Tmin = 0.230, Tmax = 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(Fo2) + (0.0271P)2]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 3106 reflections | Δρmax = 0.92 e Å−3 |
| 114 parameters | Δρmin = −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 |
| Mr = 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) |
| Tmin = 0.230, Tmax = 0.301 | Rint = 0.034 |
| 13418 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
| wR(F2) = 0.056 | Δρmax = 0.92 e Å−3 |
| S = 1.10 | Δρmin = −0.65 e Å−3 |
| 3106 reflections | Absolute structure: ? |
| 114 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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, °) 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···Cl4iv | 0.89 | 2.38 | 3.232 (3) | 161 |
| N2—H2B···Cl5v | 0.89 | 2.26 | 3.123 (3) | 162 |
| N2—H2C···Cl3iv | 0.89 | 2.40 | 3.246 (3) | 159 |
| N3—H3A···Cl3vi | 0.89 | 2.42 | 3.297 (2) | 167 |
| N3—H3B···Cl5 | 0.89 | 2.32 | 3.144 (3) | 154 |
| N3—H3C···Cl1iv | 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. |
Table 1
Hydrogen-bond geometry (Å, °) top
| 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···Cl3iv | 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+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. |
This work was supported by a start-up grant from Jiangsu University of Science
and Technology, China.
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![[Figure 1]](./xu2588fig1thm.gif)
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).