N,N′-Dicyclo­hexyl­ethyl­enediammonium dichloride

Lechner, B.-D.; Merzweiler, K.

doi:10.1107/S1600536809052222

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o122

doi:10.1107/S1600536809052222

Open

access

N,N′-Dicyclohexylethylenediammonium dichloride

Bob-Dan Lechner ^a and Kurt Merzweiler ^a ^*

^aInstitut für Chemie, Naturwissenschaftliche Fakulät II, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Str. 2, 06120 Halle, Germany
^*Correspondence e-mail: kurt.merzweiler@chemie.uni-halle.de

(Received 4 November 2009; accepted 4 December 2009; online 12 December 2009)

In the title compound, C₁₄H₃₀N₂²⁺·2Cl⁻, the N,N′-dicyclohexylethylenediammonium cation posseses crystallographic $[\overline{1}]$ symmetry, and thus the compound crystallizes with two formula units per unit cell. In the crystal, the cations and anions are linked by N—H⋯Cl hydrogen bonds, giving a two-dimensional network with {6,3} topology.

Related literature

For the crystal structures of cyclohexylammonium derivatives, see Smith et al. (1994 ); Martell & Zaworotko (1991 ). For the crystal structure of an iridium complex with the N,N′-dicyclohexylethylenediamine ligand, see: Greulich et al. (2002 ). For a review of hydrogen bonding, see Steiner (2002 ). N,N′-dicyclohexylethylenediamine was prepared according to Denk et al. (2003 ). For the topology of {6,3} ring systems and three-dimensional polyhedra and networks, see: Wells & Sharpe (1963 ).

Experimental

Crystal data

C₁₄H₃₀N₂²⁺·2Cl⁻
M_r = 297.30
Monoclinic, P 2₁ /c
a = 11.551 (3) Å
b = 6.785 (2) Å
c = 10.8434 (17) Å
β = 91.892 (15)°
V = 849.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 K
0.65 × 0.28 × 0.12 mm

Data collection

Stoe STADI4 diffractometer
3349 measured reflections
1675 independent reflections
1430 reflections with I > 2σ(I)
R_int = 0.036
2 standard reflections every 120 min
intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.089
S = 1.10
1675 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H4⋯Cl	0.91 (2)	2.20 (2)	3.1088 (16)	175.8 (18)
N—H3⋯Clⁱ	0.84 (2)	2.30 (2)	3.1250 (16)	168.8 (18)
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: STADI4 (Stoe & Cie, 1996 ); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052222/si2221sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052222/si2221Isup2.hkl

checkCIF report

Comment top

Compared to other N,N'-disubstituted ethylenediamine compounds RNH-CH₂CH₂—NHR (R = Me, Ph, etc.) N,N'-Dicyclohexylethylenediamine derivatives have been studied only rarely by X-ray diffraction. One of the few examples is the Iridium complex [Cp*(CyNHCH₂CH₂NHCy)HIr][H₃BCN] (Greulich et al., 2002).

The crystal structure of the title compound (Fig. 1) consists of [CyNH₂CH₂CH₂NH₂Cy]²⁺ cations and Cl^-anions. The [CyNH₂CH₂CH₂NH₂Cy]²⁺cations exhibit crystallographic 1 symmetry and thus an exactly staggered conformation with a N—C—C—N torsion angle of 180 ° is observed. The N atoms display a distorted tetrahedral coordination with H—N—C angles of 108.6 to 111.2 and a C—N—C angle of 114.50 (1)°. The cyclohexyl groups adopt a chair conformation (Fig. 2) as it was observed in [Cp*(CyNHCH₂CH₂NHCy)HIr][H₃BCN] (Greulich et al., 2002). Both hydrogen atoms of the NH₂ groups are involved in hydrogen bridges to neighbouring Cl^- anions. The NH···Cl distances of 2.20 (2) and 2.30 (2) Å are comparable to those found in other cyclohexylammonium derivatives like [CyNH₃]Cl (2.187–2.35.4 Å) (Smith et al., 1994) and [CyNH₃]₂(AlCl₄)Cl (2.305–2.478 Å) (Martell & Zaworotko, 1991) respectively. The N—H···Cl angles of 169 (2)° and 176 (2)° are in the expected range for hydrogen bridges of moderate strength (Steiner, 2002).

On balance each [CyNH₂CH₂CH₂NH₂Cy]²⁺ cation forms four N—H···Cl bridges to neighbouring Cl^- anions and each Cl^- anion acts as H-acceptor for two NH hydrogen atoms. As a result of the hydrogen bonding between [CyNH₂CH₂CH₂NH₂Cy]²⁺ cations and Cl^- anions a two-dimensional layer structure is formed. The layers consist of puckered C₄H₈N₆Cl₄ rings that are interconnected to give a honeycomb arrangement with {6,3} net topology (Wells & Sharpe, 1963).

Related literature top

For the crystal structures of cyclohexylammonium derivatives, see Smith et al. (1994); Martell & Zaworotko (1991). For the crystal structure of an iridium complex with the N,N'-dicyclohexylethylenediamine ligand, see: Greulich et al. (2002). For a review of hydrogen bonding, see Steiner (2002). N,N'-dicyclohexylethylenediamine was prepared according to Denk et al. (2003). For the topology of {6,3} ring systems and three-dimensional polyhedra and networks, see: Wells & Sharpe (1963).

Experimental top

An excess of hydrochloric acid was added dropwise to a solution of N,N'-Dicyclohexylethylenediamine monohydrate (1.11 g, 5 mmol) prepared by standard techniques (Denk et al., 2003) in a ethanol/water mixture(10:1, 20 ml) and stirred for 6 h at 140 °C in an autoclave. The mixture was slowly cooled to ambient temperature and colourless plate-like crystals were obtained. Spectroscopic data: ¹H NMR (D₂O, 500 MHz, 298 K, p.p.m.): δ 1.07–1.99 (m, 20 H, CH_2,Cy), 3.09 (m, 2H, CH), 3.32 (s, 4H, CH₂); ¹³C NMR (D₂O, 125 MHz, 298 K, p.p.m.): δ 23.7 (s, CH₂, Cy: C4, C6), 24.3 (s, CH₂, Cy: C5), 26.7 (s, CH₂, Cy: C3, C7), 40.0 (s, CH₂), 57.934 (s, CH, Cy).

Computing details top

Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4 (Stoe & Cie, 1996); data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the [CyNH₂CH₂CH₂NH₂Cy]²⁺ cation with surrounding Cl^- anions. The asymmetric unit is shown by filled bonds. Thermal ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) -x, -y, -z; (ii) -x, -1/2 + y, 1.5 - z; (iii) x, 1.5 - y, -1/2 + z
	Fig. 2. Part of the layer structure formed by hydrogen bonded [CyNH₂CH₂CH₂NH₂Cy]²⁺ cations and Cl^- anions. Cyclohexyl groups are omitted for clarity.

N,N'-Dicyclohexylethylenediammonium dichloride top

Crystal data top

C₁₄H₃₀N₂²⁺·2Cl⁻	F(000) = 324
M_r = 297.30	D_x = 1.163 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 22 reflections
a = 11.551 (3) Å	θ = 10.2–14.6°
b = 6.785 (2) Å	µ = 0.37 mm⁻¹
c = 10.8434 (17) Å	T = 293 K
β = 91.892 (15)°	Plate, colourless
V = 849.3 (4) Å³	0.65 × 0.28 × 0.12 mm
Z = 2

Data collection top

Stoe STADI4 diffractometer	R_int = 0.036
Radiation source: fine-focus sealed tube	θ_max = 26.1°, θ_min = 1.8°
Graphite monochromator	h = −14→14
2θ/ω scans	k = −8→0
3349 measured reflections	l = −13→13
1675 independent reflections	2 standard reflections every 120 min
1430 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0304P)² + 0.223P] where P = (F_o² + 2F_c²)/3
1675 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₄H₃₀N₂²⁺·2Cl⁻	V = 849.3 (4) Å³
M_r = 297.30	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.551 (3) Å	µ = 0.37 mm⁻¹
b = 6.785 (2) Å	T = 293 K
c = 10.8434 (17) Å	0.65 × 0.28 × 0.12 mm
β = 91.892 (15)°

Data collection top

Stoe STADI4 diffractometer	R_int = 0.036
3349 measured reflections	2 standard reflections every 120 min
1675 independent reflections	intensity decay: none
1430 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.23 e Å⁻³
1675 reflections	Δρ_min = −0.28 e Å⁻³
142 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	0.05608 (15)	0.4477 (3)	0.48641 (16)	0.0404 (4)
H2	0.1138 (18)	0.537 (3)	0.4631 (19)	0.054 (6)*
H1	0.0449 (18)	0.353 (3)	0.419 (2)	0.059 (6)*
C2	0.21086 (13)	0.2307 (2)	0.58171 (14)	0.0342 (3)
H5	0.2039 (14)	0.163 (3)	0.5053 (16)	0.038 (4)*
C3	0.22533 (16)	0.0777 (3)	0.6834 (2)	0.0478 (5)
H6	0.2248 (18)	0.147 (3)	0.763 (2)	0.059 (6)*
H7	0.1619 (18)	−0.009 (4)	0.6755 (18)	0.058 (6)*
C4	0.33978 (18)	−0.0313 (3)	0.6726 (3)	0.0574 (5)
H8	0.3397 (19)	−0.095 (3)	0.596 (2)	0.063 (7)*
H9	0.346 (2)	−0.123 (4)	0.738 (2)	0.069 (7)*
C5	0.44122 (17)	0.1104 (3)	0.6751 (2)	0.0513 (5)
H10	0.4456 (18)	0.173 (3)	0.757 (2)	0.064 (6)*
H11	0.516 (2)	0.045 (3)	0.668 (2)	0.068 (6)*
C6	0.42621 (16)	0.2660 (3)	0.5755 (2)	0.0522 (5)
H12	0.4254 (18)	0.198 (3)	0.497 (2)	0.064 (6)*
H13	0.492 (2)	0.354 (4)	0.581 (2)	0.075 (7)*
C7	0.31115 (15)	0.3757 (3)	0.58388 (18)	0.0419 (4)
H14	0.3073 (17)	0.447 (3)	0.6637 (19)	0.054 (6)*
H15	0.3005 (17)	0.466 (3)	0.5188 (18)	0.053 (6)*
N	0.09763 (12)	0.3358 (2)	0.59677 (13)	0.0335 (3)
H4	0.1015 (17)	0.416 (3)	0.6647 (19)	0.052 (6)*
H3	0.0454 (17)	0.257 (3)	0.6169 (17)	0.045 (5)*
Cl	0.12073 (4)	0.59342 (7)	0.83342 (4)	0.04938 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0421 (9)	0.0418 (9)	0.0375 (8)	0.0074 (8)	0.0039 (7)	0.0097 (7)
C2	0.0376 (8)	0.0297 (8)	0.0351 (8)	0.0025 (6)	−0.0004 (6)	−0.0027 (6)
C3	0.0413 (10)	0.0349 (9)	0.0670 (13)	−0.0006 (8)	−0.0007 (8)	0.0165 (9)
C4	0.0521 (11)	0.0354 (9)	0.0838 (16)	0.0089 (9)	−0.0074 (10)	0.0073 (11)
C5	0.0405 (10)	0.0492 (11)	0.0638 (12)	0.0098 (8)	−0.0038 (8)	0.0007 (9)
C6	0.0391 (9)	0.0583 (12)	0.0596 (12)	0.0033 (9)	0.0088 (8)	0.0046 (10)
C7	0.0383 (9)	0.0361 (9)	0.0514 (10)	−0.0011 (7)	0.0039 (7)	0.0081 (8)
N	0.0338 (7)	0.0314 (7)	0.0352 (7)	−0.0018 (6)	0.0011 (5)	0.0043 (6)
Cl	0.0569 (3)	0.0446 (3)	0.0467 (3)	0.0160 (2)	0.00215 (19)	−0.00631 (19)

Geometric parameters (Å, º) top

C1—N	1.484 (2)	C4—H8	0.94 (2)
C1—C1ⁱ	1.514 (3)	C4—H9	0.95 (2)
C1—H2	0.94 (2)	C5—C6	1.516 (3)
C1—H1	0.98 (2)	C5—H10	0.98 (2)
C2—N	1.503 (2)	C5—H11	0.98 (2)
C2—C7	1.519 (2)	C6—C7	1.529 (2)
C2—C3	1.519 (2)	C6—H12	0.97 (2)
C2—H5	0.948 (18)	C6—H13	0.97 (3)
C3—C4	1.523 (3)	C7—H14	0.99 (2)
C3—H6	0.98 (2)	C7—H15	0.94 (2)
C3—H7	0.94 (2)	N—H4	0.91 (2)
C4—C5	1.515 (3)	N—H3	0.84 (2)

N—C1—C1ⁱ	109.80 (17)	C4—C5—C6	111.01 (17)
N—C1—H2	109.4 (13)	C4—C5—H10	108.0 (13)
C1ⁱ—C1—H2	111.7 (12)	C6—C5—H10	109.9 (13)
N—C1—H1	107.3 (13)	C4—C5—H11	113.4 (14)
C1ⁱ—C1—H1	111.1 (12)	C6—C5—H11	109.8 (13)
H2—C1—H1	107.4 (17)	H10—C5—H11	104.5 (18)
N—C2—C7	110.89 (13)	C5—C6—C7	112.07 (16)
N—C2—C3	108.69 (13)	C5—C6—H12	107.2 (13)
C7—C2—C3	111.44 (15)	C7—C6—H12	107.4 (13)
N—C2—H5	106.0 (10)	C5—C6—H13	108.4 (14)
C7—C2—H5	111.7 (10)	C7—C6—H13	112.4 (14)
C3—C2—H5	107.9 (11)	H12—C6—H13	109.2 (18)
C2—C3—C4	110.54 (17)	C2—C7—C6	110.34 (15)
C2—C3—H6	108.0 (12)	C2—C7—H14	105.8 (12)
C4—C3—H6	109.2 (12)	C6—C7—H14	110.7 (12)
C2—C3—H7	107.1 (13)	C2—C7—H15	109.3 (12)
C4—C3—H7	111.5 (13)	C6—C7—H15	111.5 (12)
H6—C3—H7	110.5 (17)	H14—C7—H15	109.1 (17)
C5—C4—C3	111.30 (17)	C1—N—C2	114.50 (13)
C5—C4—H8	106.8 (14)	C1—N—H4	110.6 (12)
C3—C4—H8	108.5 (14)	C2—N—H4	110.5 (13)
C5—C4—H9	111.3 (14)	C1—N—H3	108.6 (13)
C3—C4—H9	107.9 (14)	C2—N—H3	111.1 (13)
H8—C4—H9	111 (2)	H4—N—H3	100.6 (17)

N—C2—C3—C4	−179.40 (16)	C3—C2—C7—C6	55.7 (2)
C7—C2—C3—C4	−56.9 (2)	C5—C6—C7—C2	−54.8 (2)
C2—C3—C4—C5	56.5 (3)	C1ⁱ—C1—N—C2	−178.21 (18)
C3—C4—C5—C6	−55.5 (3)	C7—C2—N—C1	73.57 (19)
C4—C5—C6—C7	54.9 (2)	C3—C2—N—C1	−163.61 (15)
N—C2—C7—C6	176.95 (14)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H4···Cl	0.91 (2)	2.20 (2)	3.1088 (16)	175.8 (18)
N—H3···Clⁱⁱ	0.84 (2)	2.30 (2)	3.1250 (16)	168.8 (18)

Symmetry code: (ii) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₃₀N₂²⁺·2Cl⁻
M_r	297.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.551 (3), 6.785 (2), 10.8434 (17)
β (°)	91.892 (15)
V (Å³)	849.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.65 × 0.28 × 0.12

Data collection
Diffractometer	Stoe STADI4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3349, 1675, 1430
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.10
No. of reflections	1675
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.28

Computer programs: STADI4 (Stoe & Cie, 1996), X-RED (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H4···Cl	0.91 (2)	2.20 (2)	3.1088 (16)	175.8 (18)
N—H3···Clⁱ	0.84 (2)	2.30 (2)	3.1250 (16)	168.8 (18)

Symmetry code: (i) −x, y−1/2, −z+3/2.

References

Brandenburg, K. (2009). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Denk, M. K., Krause, M. J., Niyogi, D. F. & Gill, N. K. (2003). Tetrahedron, 59, 7565–7570. Web of Science CrossRef CAS Google Scholar
Greulich, S., Klein, A., Knödler, A. & Kaim, W. (2002). Organometallics, 21, 765–769. Web of Science CSD CrossRef CAS Google Scholar
Martell, J. M. & Zaworotko, M. (1991). J. Chem. Soc. Dalton Trans. pp. 1495–1498. CSD CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, H. W., Mastropaolo, D., Camerman, A. & Camerman, N. (1994). J. Chem. Crystallogr. 24, 239–242. CSD CrossRef CAS Web of Science Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48–76. Web of Science CrossRef CAS Google Scholar
Stoe & Cie, (1996). STADI4 and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wells, A. F. & Sharpe, R. R. (1963). Acta Cryst. 16, 857–871. CrossRef CAS IUCr Journals Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o122

doi:10.1107/S1600536809052222

Open

access