organic compounds
N1,N2-Dimethylethane-1,2-diaminium dichloride
aDepartment of Chemistry 0212, Virginia Tech, Blacksburg, VA 24061, USA
*Correspondence e-mail: jmerola@vt.edu
The cation of the title salt, C4H14N22+·2Cl−, is located on a crystallographic inversion center and is bisected by a mirror plane, with one quarter of the C4H14N22+·2Cl− formula unit being crystallographically unique. he chloride ions also sit on a mirror plane. The conformation of the cation is a regular straight-chain conformation with all non-H atoms in anti positions. In the crystal, hydrogen bonding between N—H groups and chloride anions yields a zigzag ladder-type structure along [010].
CCDC reference: 982975
Related literature
For the N1,N2-dimethylethane-1,2-diaminium dithiocyanate (CCDC: 662389), see: Wolstenholme et al. (2008), of ethane-1,2-diaminium]chloride (CCDC: 790989), see: Liu et al. (2010), of N1,N1,N2,N2-tetramethylethane-1,2-diaminium dichloride, see: Schneider & Schier (2004; CCDC: 247442) and Kabak et al., 2000; CCDC: 142944) and of N1,N1,N2-trimethylethylenediammonium dichloride, see: Errington et al. (2001). The most recent description of the Cambridge Crystallographic Database can be found in Groom & Allen (2014).
ofExperimental
Crystal data
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Data collection: XSCANS (Siemens, 1996); cell XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.
Supporting information
CCDC reference: 982975
10.1107/S1600536814001627/zl2574sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814001627/zl2574Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814001627/zl2574Isup3.mol
Supporting information file. DOI: 10.1107/S1600536814001627/zl2574Isup4.cml
The crystal used in this experiment was obtained from a reaction between [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene)(0.100 g) and N1,N2-ethane-1,2-diamine (0.200 g) in dichloromethane solution. After stirring at room temperature overnight, the solvent was removed under reduced pressure to yield 0.147 g of a white powder. Some of the powder was dissolved in dichloromethane and allowed to evaporate slowly in a vial with the serum cap punctured with a needle. Upon evaporation of all of the solvent, most of the solid was a powder with only a few nicely shaped crystals in the mixture. A crystal was chosen and epoxied onto a thin quartz fiber and placed in a goniometer. Apparently, on sitting, some amount of decomposition occurred to yield the free diamine as well as the generation of hydrogen chloride resulting in the formation of the title compound.
All hydrogen atoms in the structure were located by difference map and all parameters not fixed by location on a
(mirror plane) were refined. N—H bonds are 0.94 (2) Å (Table 1) and are identical by symmetry (mirror plane and inversion center).Ethane-1,2-diaminium cations and N-alkyl substituted variants play a large role in structural chemistry as counter-ions for quite a number of anions and anionic complexes. A search of the Cambridge Crystallographic Database shows hundreds of structures in which some form of ethane-1,2-diaminium salt serves as the cation (Groom & Allen, 2014). There are many fewer examples of simple halide salts of these dications and there are no simple halide salts of the [N1,N2-dimethylethane-1,2-diaminium] moiety. This report discusses the structure of [N1,N2-dimethylethane-1,2-diaminium]chloride and the hydrogen-bonding motif set up in the lattice. While the N1,N2-ethylenediaminium cation has been structurally characterized as the thiocyanate salt (Wolstenholme et al., 2008) as well as with a number of metal complex anions, the structure of the chloride salt has not been determined previously.
The title compound crystallizes in the C2/m
and the molecule is located on a crystallographic inversion center and is bisected by a mirror plane, with one quarter of a molecule of [C4H14N2]2+ 2Cl- being crystallographically unique. Figure 1 shows the thermal ellipsoid plot of the and Figure 2 shows the thermal ellipsoid plot of the entire molecule with atoms labeled with name and that generates them. The diaminium cation adopts a classical linear geometry with all heavy atoms lying in a plane and all bond angles being ± one degree from the ideal tetrahedrality.The presence of two hydrogen atoms on each nitrogen atom leads to a ladder hydrogen-bonding motif with each N—H bonding to a chloride anion. Figure 3 shows a view down the c-axis showing the ladder arrangement while figure 4 shows the same arrangement down the a-axis.
Other ethanediaminium chlorides have been structurally characterized, but all have very different hydrogen bonding motifs. Obviously, hexamethylethylenediaminium chloride has no N—H groups and therefore, no H-bonding, so the lack of a chloride ion comparison for that dication is not important. The unsubstituted ethylenediaminium chloride, having 3 N—H hydrogen bonds to the chloride ion has a more complex, three-dimensional H-bonding network (Liu et al., 2010). The [N1,N1,N2,N2-tetramethylethane-1,2-diaminium]chloride structure, with only one N—H per nitrogen atom, shows clear hydrogen-bonding, but there is no extended lattice structure, just isolated N—H···Cl bonds (Schneider & Schier, 2004) and (Kabak et al., 2000). The trimethyl compound, [N1,N1,N2-trimethyldiaminium chloride has a complicated structure with two different conformations of the dication in the
each hydrogen-bonding to the chloride ions in different ways and yielding an iregular motif (Errington et al., 2001).For the
of N1,N2-dimethylethane-1,2-diaminium dithiocyanate (CCDC: 662389), see: Wolstenholme et al. (2008), of ethane-1,2-diaminium]chloride (CCDC: 790989), see: Liu et al. (2010), of N1,N1,N2,N2-tetramethylethane-1,2-diaminium dichloride, see: Schneider & Schier (2004; CCDC: 247442) and Kabak et al., 2000; CCDC: 142944) and of N1,N1,N2-trimethylethylenediammonium dichloride, see: Errington et al. (2001). The most recent description of the Cambridge Crystallographic Database can be found in Groom & Allen (2014).Data collection: XSCANS (Siemens, 1996); cell
XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C4H14N22+·2Cl− | F(000) = 172 |
Mr = 161.07 | Dx = 1.180 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 18.108 (2) Å | Cell parameters from 35 reflections |
b = 5.104 (1) Å | θ = 2.2–20° |
c = 5.080 (1) Å | µ = 0.64 mm−1 |
β = 105.09 (3)° | T = 293 K |
V = 453.32 (14) Å3 | Irregular, clear colourless |
Z = 2 | 0.4 × 0.2 × 0.2 mm |
Siemens P4 diffractometer | Rint = 0.022 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.3° |
Graphite monochromator | h = −1→21 |
ω scans | k = −1→6 |
590 measured reflections | l = −6→5 |
443 independent reflections | 3 standard reflections every 300 reflections |
398 reflections with I > 2σ(I) | intensity decay: 0.0(1) |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0266P)2 + 0.2719P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
443 reflections | Δρmax = 0.24 e Å−3 |
41 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: iterative | Extinction coefficient: 0.041 (6) |
C4H14N22+·2Cl− | V = 453.32 (14) Å3 |
Mr = 161.07 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 18.108 (2) Å | µ = 0.64 mm−1 |
b = 5.104 (1) Å | T = 293 K |
c = 5.080 (1) Å | 0.4 × 0.2 × 0.2 mm |
β = 105.09 (3)° |
Siemens P4 diffractometer | Rint = 0.022 |
590 measured reflections | 3 standard reflections every 300 reflections |
443 independent reflections | intensity decay: 0.0(1) |
398 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.070 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.24 e Å−3 |
443 reflections | Δρmin = −0.15 e Å−3 |
41 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.60591 (11) | 0.0000 | 0.0428 (4) | 0.0381 (5) | |
H1 | 0.6075 (10) | −0.149 (4) | −0.066 (4) | 0.055 (5)* | |
C1 | 0.67523 (16) | 0.0000 | 0.2769 (7) | 0.0564 (8) | |
H1A | 0.7175 (18) | 0.0000 | 0.198 (6) | 0.067 (9)* | |
H1B | 0.6737 (13) | −0.167 (5) | 0.385 (4) | 0.078 (7)* | |
C2 | 0.53327 (13) | 0.0000 | 0.1259 (5) | 0.0393 (6) | |
H2 | 0.5317 (9) | −0.153 (4) | 0.234 (3) | 0.045 (5)* | |
Cl1 | 0.61356 (4) | −0.5000 | −0.28640 (13) | 0.0501 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0376 (11) | 0.0323 (11) | 0.0462 (12) | 0.000 | 0.0143 (9) | 0.000 |
C1 | 0.0378 (15) | 0.067 (2) | 0.0617 (17) | 0.000 | 0.0088 (13) | 0.000 |
C2 | 0.0383 (13) | 0.0409 (14) | 0.0402 (13) | 0.000 | 0.0130 (10) | 0.000 |
Cl1 | 0.0634 (5) | 0.0343 (4) | 0.0576 (4) | 0.000 | 0.0246 (3) | 0.000 |
N1—H1 | 0.94 (2) | C1—H1B | 1.02 (2) |
N1—C1 | 1.488 (3) | C2—C2i | 1.511 (5) |
N1—C2 | 1.482 (3) | C2—H2 | 0.960 (18) |
C1—H1A | 0.95 (3) | Cl1—Cl1ii | 0.0000 (13) |
C1—N1—H1 | 108.6 (11) | H1A—C1—H1B | 111.5 (15) |
C2—N1—H1 | 109.3 (11) | N1—C2—C2i | 109.3 (2) |
C2—N1—C1 | 113.5 (2) | N1—C2—H2 | 108.8 (10) |
N1—C1—H1A | 105.4 (18) | C2i—C2—H2 | 110.4 (10) |
N1—C1—H1B | 107.2 (13) | ||
C1—N1—C2—C2i | 180.0 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, −y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1ii | 0.94 (2) | 2.13 (2) | 3.0741 (13) | 176.2 (17) |
Symmetry code: (ii) x, −y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.94 (2) | 2.13 (2) | 3.0741 (13) | 176.2 (17) |
Symmetry code: (i) x, −y−1, z. |
Acknowledgements
The Virginia Tech Subvention Fund is gratefully acknowledged for covering the open-access fee.
References
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Errington, W., Somasunderam, U. & Willey, G. R. (2001). Acta Cryst. C57, 190–191. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. Engl. 53, 662–671. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kabak, M., Elerman, Y., Ünaleroglu, C., Mert, Y. & Durlu, T. N. (2000). Acta Cryst. C56, e66–e67. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Liu, Y.-P., Di, Y.-Y., He, D.-H., Kong, Y.-X., Yang, W.-W. & Dan, W.-Y. (2010). J. Chem. Thermodyn. 42, 513–517. Web of Science CSD CrossRef CAS Google Scholar
Schneider, D. & Schier, A. (2004). Z. Naturforsch. Teil B, 59, 1395–1399. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Wolstenholme, D. J., Weigand, J. J., Cameron, E. M. & Cameron, T. S. (2008). Phys. Chem. Chem. Phys. 10, 3569–3577. Web of Science CrossRef PubMed CAS Google Scholar
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Ethane-1,2-diaminium cations and N-alkyl substituted variants play a large role in structural chemistry as counter-ions for quite a number of anions and anionic complexes. A search of the Cambridge Crystallographic Database shows hundreds of structures in which some form of ethane-1,2-diaminium salt serves as the cation (Groom & Allen, 2014). There are many fewer examples of simple halide salts of these dications and there are no simple halide salts of the [N1,N2-dimethylethane-1,2-diaminium] moiety. This report discusses the structure of [N1,N2-dimethylethane-1,2-diaminium]chloride and the hydrogen-bonding motif set up in the lattice. While the N1,N2-ethylenediaminium cation has been structurally characterized as the thiocyanate salt (Wolstenholme et al., 2008) as well as with a number of metal complex anions, the structure of the chloride salt has not been determined previously.
The title compound crystallizes in the C2/m space group and the molecule is located on a crystallographic inversion center and is bisected by a mirror plane, with one quarter of a molecule of [C4H14N2]2+ 2Cl- being crystallographically unique. Figure 1 shows the thermal ellipsoid plot of the asymmetric unit and Figure 2 shows the thermal ellipsoid plot of the entire molecule with atoms labeled with name and symmetry operation that generates them. The diaminium cation adopts a classical linear geometry with all heavy atoms lying in a plane and all bond angles being ± one degree from the ideal tetrahedrality.
The presence of two hydrogen atoms on each nitrogen atom leads to a ladder hydrogen-bonding motif with each N—H bonding to a chloride anion. Figure 3 shows a view down the c-axis showing the ladder arrangement while figure 4 shows the same arrangement down the a-axis.
Other ethanediaminium chlorides have been structurally characterized, but all have very different hydrogen bonding motifs. Obviously, hexamethylethylenediaminium chloride has no N—H groups and therefore, no H-bonding, so the lack of a chloride ion comparison for that dication is not important. The unsubstituted ethylenediaminium chloride, having 3 N—H hydrogen bonds to the chloride ion has a more complex, three-dimensional H-bonding network (Liu et al., 2010). The [N1,N1,N2,N2-tetramethylethane-1,2-diaminium]chloride structure, with only one N—H per nitrogen atom, shows clear hydrogen-bonding, but there is no extended lattice structure, just isolated N—H···Cl bonds (Schneider & Schier, 2004) and (Kabak et al., 2000). The trimethyl compound, [N1,N1,N2-trimethyldiaminium chloride has a complicated structure with two different conformations of the dication in the asymmetric unit, each hydrogen-bonding to the chloride ions in different ways and yielding an iregular motif (Errington et al., 2001).