supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, o2060    [ doi:10.1107/S1600536808031334 ]

(m-Phenylenedimethylene)diammonium dichloride

H. Cheng and H. Li

Abstract top

The asymmetric unit of the title compound, C8H14N22+·2Cl-, contains one and a half of the dications and three chloride anions. The half molecule is completed by crystallographic twofold symmetry with two C atoms lying on the rotation axis. The two ammonium groups in each cation adopt a trans conformation with respect ot the benzene ring. The ammonium groups and chloride anions are involved in the formation of a three-dimensional N-H...Cl hydrogen-bonding network, which stabilizes the crystal packing.

Comment top

The diamine compounds are important in biologically active natural products (Pasini & Zunino, 1987; Otsuka et al., 1990), in medicinal chemistry (Michalson & Smuszkovicz, 1989; Reedijk, 1996). They are also used as chiral auxiliaries and chiral ligands in asymmetric catalysis (Blaser, 1992; Soai & Niwa, 1992; Jacobsen, 1993; Kolb et al., 1994). Herewith we present the title diamine compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal. Two amino groups in the dications adopt trans-conformation and each amino group form three N—H···Cl hydrogen bonds (Table 1) to stabilize the crystal packing.

Related literature top

For related literature, see: Pasini & Zunino (1987); Otsuka et al. (1990); Michalson & Smuszkovicz (1989); Reedijk (1996); Blaser (1992); Soai & Niwa (1992); Jacobsen (1993); Kolb et al. (1994). [From the Section Editors: It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···." etc. Please revise this section as indicated.]

Experimental top

1,3-Phenylenedimethanamine was dissolved in ethanol, then 1N HCl was dropped to the solution. Colourless, block-like crystals of (I) suitable for X-ray data collection were obtained by slow evaporation of ethanol at 283 K.

Refinement top

All H atoms were initially located in a difference Fourier map. C-bound H atoms were placed in idealized positions (C—H = 0.93–0.97 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C). Amino H atoms were refined with bond restraint of N—H = 0.88 (3) Å and constrained displacement parameter Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by spheres of arbitrary radius.
(m-Phenylenedimethylene)diammonium dichloride top
Crystal data top
C8H14N22+·2Cl−F(000) = 1320
Mr = 209.11Dx = 1.337 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -c/2ycCell parameters from 6157 reflections
a = 27.5859 (18) Åθ = 2.8–27.8°
b = 13.1594 (14) ŵ = 0.58 mm−1
c = 8.8324 (6) ÅT = 298 K
β = 103.539 (1)°Block, colourless
V = 3117.2 (4) Å30.20 × 0.10 × 0.10 mm
Z = 12
Data collection top
Bruker SMART CCD area-detector
diffractometer		3066 independent reflections
Radiation source: fine-focus sealed tube2615 reflections with I > 2σ(I)
graphiteRint = 0.103
φ and ω scansθmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		h = −33→33
Tmin = 0.894, Tmax = 0.945k = −14→16
14623 measured reflectionsl = −10→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0717P)2]
where P = (Fo2 + 2Fc2)/3
3066 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.36 e Å−3
9 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C8H14N22+·2Cl−V = 3117.2 (4) Å3
Mr = 209.11Z = 12
Monoclinic, C2/cMo Kα radiation
a = 27.5859 (18) ŵ = 0.58 mm−1
b = 13.1594 (14) ÅT = 298 K
c = 8.8324 (6) Å0.20 × 0.10 × 0.10 mm
β = 103.539 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3066 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		2615 reflections with I > 2σ(I)
Tmin = 0.894, Tmax = 0.945Rint = 0.103
14623 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118Δρmax = 0.36 e Å−3
S = 1.06Δρmin = −0.31 e Å−3
3066 reflectionsAbsolute structure: ?
191 parametersFlack parameter: ?
9 restraintsRogers parameter: ?
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 > 2sigma(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
C10.27771 (7)0.50258 (14)−0.0022 (2)0.0355 (4)
C20.26673 (7)0.60114 (16)0.0327 (2)0.0414 (5)
H20.28560.65470.00890.050*
C30.22778 (7)0.62046 (16)0.1031 (2)0.0438 (5)
H30.22060.68700.12610.053*
C40.19964 (7)0.54155 (16)0.1392 (2)0.0398 (5)
H40.17350.55490.18650.048*
C50.21012 (6)0.44213 (14)0.1052 (2)0.0341 (4)
C60.24907 (7)0.42332 (14)0.0342 (2)0.0355 (4)
H60.25610.35690.01060.043*
C70.31958 (8)0.48207 (17)−0.0814 (2)0.0447 (5)
H7A0.31180.4215−0.14500.054*
H7B0.32200.5384−0.15000.054*
C80.18156 (7)0.35486 (16)0.1535 (3)0.0458 (5)
H8A0.19950.29220.14690.055*
H8B0.18020.36420.26130.055*
C90.00722 (7)0.23186 (15)0.6209 (2)0.0349 (4)
C100.00730 (8)0.12695 (16)0.6221 (3)0.0466 (5)
H100.01230.09150.53600.056*
C110.00000.0741 (2)0.75000.0553 (8)
H110.00000.00340.75000.066*
C120.00000.2839 (2)0.75000.0349 (6)
H120.00000.35460.75000.042*
C130.01564 (8)0.28914 (19)0.4806 (3)0.0483 (5)
H13A0.01000.24390.39150.058*
H13B−0.00810.34460.45610.058*
Cl10.08043 (2)0.50782 (4)0.76455 (6)0.04504 (18)
Cl20.35181 (2)0.28315 (4)0.23278 (6)0.04852 (19)
Cl30.094656 (19)0.15614 (4)0.24153 (6)0.04295 (18)
N10.36851 (6)0.46791 (14)0.0298 (2)0.0375 (4)
H1C0.3787 (8)0.5257 (13)0.078 (3)0.045*
H1A0.3894 (7)0.4518 (17)−0.025 (2)0.045*
H1B0.3683 (8)0.4230 (15)0.102 (2)0.045*
N20.13028 (7)0.34496 (14)0.0574 (2)0.0433 (4)
H2A0.1269 (9)0.3278 (17)−0.036 (2)0.052*
H2B0.1123 (8)0.3989 (15)0.050 (3)0.052*
H2C0.1129 (8)0.2921 (15)0.090 (3)0.052*
N30.06651 (7)0.32989 (15)0.5100 (2)0.0433 (4)
H3C0.0906 (7)0.2890 (16)0.557 (3)0.052*
H3A0.0729 (8)0.3619 (17)0.430 (2)0.052*
H3B0.0690 (8)0.3733 (16)0.587 (2)0.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0337 (10)0.0412 (11)0.0320 (10)0.0014 (8)0.0086 (8)0.0026 (8)
C20.0419 (11)0.0340 (11)0.0477 (11)−0.0020 (9)0.0093 (9)0.0080 (9)
C30.0437 (11)0.0300 (11)0.0564 (13)0.0065 (9)0.0093 (10)0.0010 (9)
C40.0348 (10)0.0394 (11)0.0465 (11)0.0074 (8)0.0121 (9)0.0002 (9)
C50.0312 (9)0.0350 (11)0.0351 (10)−0.0009 (8)0.0060 (8)0.0031 (8)
C60.0383 (10)0.0304 (10)0.0373 (10)0.0049 (8)0.0080 (8)−0.0016 (8)
C70.0441 (12)0.0572 (14)0.0357 (11)0.0029 (10)0.0155 (10)0.0038 (9)
C80.0410 (11)0.0424 (12)0.0537 (13)−0.0015 (9)0.0106 (10)0.0110 (10)
C90.0297 (9)0.0420 (12)0.0345 (10)−0.0004 (8)0.0103 (8)0.0021 (8)
C100.0534 (12)0.0404 (13)0.0487 (13)0.0014 (10)0.0174 (10)−0.0118 (10)
C110.070 (2)0.0306 (16)0.067 (2)0.0000.0181 (18)0.000
C120.0321 (13)0.0293 (14)0.0460 (16)0.0000.0148 (12)0.000
C130.0415 (11)0.0678 (16)0.0373 (11)−0.0028 (10)0.0126 (9)0.0077 (10)
Cl10.0547 (3)0.0370 (3)0.0492 (3)−0.0046 (2)0.0237 (3)−0.0082 (2)
Cl20.0507 (3)0.0449 (3)0.0514 (3)0.0066 (2)0.0148 (3)0.0119 (2)
Cl30.0483 (3)0.0368 (3)0.0480 (3)0.0090 (2)0.0199 (3)0.0070 (2)
N10.0371 (9)0.0345 (9)0.0450 (10)−0.0037 (7)0.0179 (8)−0.0048 (7)
N20.0414 (10)0.0364 (10)0.0530 (11)−0.0058 (8)0.0132 (9)0.0012 (8)
N30.0455 (10)0.0417 (11)0.0438 (11)−0.0037 (8)0.0130 (9)0.0101 (8)
Geometric parameters (Å, °) top
C1—C21.383 (3)C9—C131.514 (3)
C1—C61.391 (3)C10—C111.381 (3)
C1—C71.508 (3)C10—H100.9300
C2—C31.385 (3)C11—C10i1.381 (3)
C2—H20.9300C11—H110.9300
C3—C41.378 (3)C12—C9i1.384 (2)
C3—H30.9300C12—H120.9300
C4—C51.388 (3)C13—N31.468 (3)
C4—H40.9300C13—H13A0.9700
C5—C61.387 (2)C13—H13B0.9700
C5—C81.510 (3)N1—H1C0.884 (15)
C6—H60.9300N1—H1A0.858 (16)
C7—N11.483 (3)N1—H1B0.869 (15)
C7—H7A0.9700N2—H2A0.842 (16)
C7—H7B0.9700N2—H2B0.860 (16)
C8—N21.475 (3)N2—H2C0.927 (16)
C8—H8A0.9700N3—H3C0.880 (17)
C8—H8B0.9700N3—H3A0.877 (16)
C9—C101.381 (3)N3—H3B0.878 (16)
C9—C121.384 (2)
C2—C1—C6119.05 (17)C9—C10—C11120.7 (2)
C2—C1—C7120.19 (17)C9—C10—H10119.7
C6—C1—C7120.75 (17)C11—C10—H10119.7
C1—C2—C3120.39 (18)C10—C11—C10i119.5 (3)
C1—C2—H2119.8C10—C11—H11120.2
C3—C2—H2119.8C10i—C11—H11120.2
C4—C3—C2120.25 (19)C9—C12—C9i120.6 (3)
C4—C3—H3119.9C9—C12—H12119.7
C2—C3—H3119.9C9i—C12—H12119.7
C3—C4—C5120.21 (17)N3—C13—C9111.14 (18)
C3—C4—H4119.9N3—C13—H13A109.4
C5—C4—H4119.9C9—C13—H13A109.4
C6—C5—C4119.26 (17)N3—C13—H13B109.4
C6—C5—C8120.17 (17)C9—C13—H13B109.4
C4—C5—C8120.46 (17)H13A—C13—H13B108.0
C5—C6—C1120.85 (17)C7—N1—H1C110.3 (15)
C5—C6—H6119.6C7—N1—H1A106.6 (15)
C1—C6—H6119.6H1C—N1—H1A108 (2)
N1—C7—C1113.13 (16)C7—N1—H1B114.1 (14)
N1—C7—H7A109.0H1C—N1—H1B107 (2)
C1—C7—H7A109.0H1A—N1—H1B111 (2)
N1—C7—H7B109.0C8—N2—H2A117.4 (18)
C1—C7—H7B109.0C8—N2—H2B115.4 (16)
H7A—C7—H7B107.8H2A—N2—H2B103 (2)
N2—C8—C5113.48 (17)C8—N2—H2C112.6 (15)
N2—C8—H8A108.9H2A—N2—H2C99 (2)
C5—C8—H8A108.9H2B—N2—H2C108 (2)
N2—C8—H8B108.9C13—N3—H3C116.4 (16)
C5—C8—H8B108.9C13—N3—H3A113.4 (16)
H8A—C8—H8B107.7H3C—N3—H3A114 (2)
C10—C9—C12119.27 (18)C13—N3—H3B105.8 (15)
C10—C9—C13120.27 (18)H3C—N3—H3B97 (2)
C12—C9—C13120.5 (2)H3A—N3—H3B109 (2)
C6—C1—C2—C30.0 (3)C6—C1—C7—N1−92.2 (2)
C7—C1—C2—C3178.93 (19)C6—C5—C8—N2−109.5 (2)
C1—C2—C3—C40.1 (3)C4—C5—C8—N274.2 (2)
C2—C3—C4—C50.0 (3)C12—C9—C10—C110.4 (3)
C3—C4—C5—C6−0.2 (3)C13—C9—C10—C11179.56 (17)
C3—C4—C5—C8176.14 (19)C9—C10—C11—C10i−0.18 (13)
C4—C5—C6—C10.4 (3)C10—C9—C12—C9i−0.18 (13)
C8—C5—C6—C1−175.99 (18)C13—C9—C12—C9i−179.4 (2)
C2—C1—C6—C5−0.3 (3)C10—C9—C13—N3−103.1 (2)
C7—C1—C6—C5−179.17 (18)C12—C9—C13—N376.1 (2)
C2—C1—C7—N188.9 (2)
Symmetry codes: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···Cl10.88 (2)2.34 (2)3.206 (2)170 (2)
N2—H2C···Cl30.93 (2)2.36 (2)3.2453 (19)160 (2)
N1—H1B···Cl20.87 (2)2.28 (2)3.1186 (18)163 (2)
N3—H3C···Cl2ii0.88 (2)2.34 (2)3.171 (2)157 (2)
N2—H2B···Cl1iii0.86 (2)2.58 (2)3.189 (2)129 (2)
N1—H1C···Cl3iv0.88 (2)2.34 (2)3.2071 (18)166 (2)
N2—H2A···Cl2v0.84 (2)2.44 (2)3.201 (2)150 (2)
N1—H1A···Cl3v0.86 (2)2.51 (2)3.2527 (17)146 (2)
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) x, −y+1, z−1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1/2, −y+1/2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···Cl10.88 (2)2.34 (2)3.206 (2)170 (2)
N2—H2C···Cl30.93 (2)2.36 (2)3.2453 (19)160 (2)
N1—H1B···Cl20.87 (2)2.28 (2)3.1186 (18)163 (2)
N3—H3C···Cl2i0.88 (2)2.34 (2)3.171 (2)157 (2)
N2—H2B···Cl1ii0.86 (2)2.58 (2)3.189 (2)129 (2)
N1—H1C···Cl3iii0.88 (2)2.34 (2)3.2071 (18)166 (2)
N2—H2A···Cl2iv0.84 (2)2.44 (2)3.201 (2)150 (2)
N1—H1A···Cl3iv0.86 (2)2.51 (2)3.2527 (17)146 (2)
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y+1, z−1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x+1/2, −y+1/2, −z.
Acknowledgements top

The authors are grateful to Xiangfan University for financial support.

references
References top

Blaser, H. U. (1992). Chem. Rev. 92, 935–952.

Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Jacobsen, E. N. (1993). Catalytic Asymmetric Synthesis, pp. 159–??? [Please give final page number]. New York: VCH.

Kolb, H. C., VanNieuwenhze, M. S. & Sharpless, K. B. (1994). Chem. Rev. 94, 2483–2547.

Michalson, E. T. & Smuszkovicz, J. (1989). Prog. Drug. Res. 33, 135.

Otsuka, M., Masuda, T., Haupt, A., Ohno, M., Shiraki, T., Sugiura, Y. & Maeda, K. (1990). J. Am. Chem. Soc. 112, 838–845.

Pasini, A. & Zunino, F. (1987). Angew. Chem. Int. Ed. Engl. 26, 615–624.

Reedijk, J. J. (1996). J. Chem. Soc. Chem. Commun. pp. 801–806.

Sheldrick, G. M. (1997). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Soai, K. & Niwa, S. (1992). Chem. Rev. 92, 833–856.