2-[Bis(2-amino­ethyl)amino]ethanaminium chloride dichloro­methane solvate

Reichvilser, M.M.; Ossiander, T.; Klüfers, P.; Mayer, P.

doi:10.1107/S1600536808039652

organic compounds

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Volume 64| Part 12| December 2008| Page o2500

doi:10.1107/S1600536808039652

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2-[Bis(2-aminoethyl)amino]ethanaminium chloride dichloromethane solvate

Moritz M. Reichvilser,^a Tanja Ossiander,^a Peter Klüfers ^a ^* and Peter Mayer ^a

^aLudwig-Maximilians-Universität, Department Chemie und Biochemie, Butenandtstrasse 5–13 (Haus D), 81377 München, Germany
^*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 20 November 2008; accepted 25 November 2008; online 29 November 2008)

In the title compound, C₆H₁₉N₄⁺·Cl⁻·CH₂Cl₂, the non-H atoms of the ammonium ion show non-crystallographic C₃ symmetry. The chloride ion is embedded in a framework of seven crystallographically independent hydrogen bonds (five N—H⋯Cl and two C—H⋯Cl), which form layers parallel to the (100) plane. Two N---H...N bonds also occur.

Related literature

For the crystal structure of N,N,N-tris(2-ammonioethyl)amine trichloride, see: Rasmussen & Hazell (1963 ); Hazell & Rasmussen (1968 ); Ilioudis et al. (2000 ).

Experimental

Crystal data

C₆H₁₉N₄⁺·Cl⁻·CH₂Cl₂
M_r = 267.63
Monoclinic, P 2₁ /c
a = 12.1512 (4) Å
b = 8.5686 (2) Å
c = 13.5497 (3) Å
β = 104.273 (2)°
V = 1367.23 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 200 (2) K
0.17 × 0.17 × 0.17 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: none
10639 measured reflections
3130 independent reflections
2431 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 1.03
3130 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯Cl1	0.94	2.54	3.3897 (17)	151
N2—H2⋯Cl1ⁱ	0.97	2.58	3.4402 (16)	148
N3—H3⋯Cl1ⁱⁱ	0.88	2.57	3.4013 (16)	159
N3—H4⋯Cl1	0.96	2.55	3.4203 (17)	150
N4—H5⋯Cl1	0.90	2.42	3.2562 (15)	153
N4—H6⋯N3ⁱⁱⁱ	0.93	1.96	2.862 (2)	165
N4—H7⋯N2^iv	1.02	1.73	2.746 (2)	171
C4—H14⋯Cl1ⁱⁱⁱ	0.99	2.82	3.7014 (18)	149
C7—H21⋯Cl1ⁱ	0.99	2.54	3.482 (3)	160
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z; (iv) -x+1, -y+1, -z.

Data collection: COLLECT (Hooft, 2004 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); 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: SHELXL97, PLATON (Spek, 200 ) and Mercury (Macrae et al., 2006 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039652/zl2162sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039652/zl2162Isup2.hkl

checkCIF report

Comment top

The title compounds molecular structure is shown in Fig. 1. The ammonium ion does not exhibit any crystallographic symmetry but, excluding the hydrogen atoms, it shows non-crystallographic C₃ symmetry.

It has to be assumed that the chloride ion is formed by a nucleophilic substitution reaction between a part of the tris(2-aminoethyl)amine and the solvent dichloromethane.

In the crystal structure, hydrogen bonds between the ammonium and chloride ions and the solvate molecule form two-dimensional networks parallel to the (100) plane (see Fig. 2). The chloride ion is embedded in a framework of seven crystallographically independent hydrogen bonds (see Fig. 3).

Related literature top

For the crystal structure of N,N,N-tris(2-ammonioethyl)amine trichloride, see: Rasmussen & Hazell (1963); Hazell & Rasmussen (1968); Ilioudis et al. (2000).

Experimental top

Crystals of the title compound were obtained from a solution of tris(2-aminoethyl)amine (0.15 g, 5.0 mmol) and trimethylborate (0.52 g, 5.0 mmol) in dichloromethane (10 ml) upon slow evaporation of the solvent at room temperature.

Computing details top

Data collection: COLLECT (Hooft, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); 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: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 200) and Mercury (Macrae et al., 2006).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
	Fig. 2. The packing and the hydrogen-bonded layers in the title compound, viewed along [0 1 0].
	Fig. 3. Hydrogen bonding to Cl1. [Symmetry codes: (i) 1 - x, 1/2 + y, 1/2 - z; (ii) 1 - x, -1/2 + y, 1/2 - z; (iii) 1 - x, -y, -z.]

2-[Bis(2-aminoethyl)amino]ethanaminium chloride dichloromethane solvate top

Crystal data top

C₆H₁₉N₄⁺·Cl⁻·CH₂Cl₂	F(000) = 568
M_r = 267.63	D_x = 1.300 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17190 reflections
a = 12.1512 (4) Å	θ = 3.1–27.5°
b = 8.5686 (2) Å	µ = 0.65 mm⁻¹
c = 13.5497 (3) Å	T = 200 K
β = 104.273 (2)°	Block, colourless
V = 1367.23 (6) Å³	0.17 × 0.17 × 0.17 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	2431 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.030
MONTEL, graded multilayered X-ray optics monochromator	θ_max = 27.5°, θ_min = 3.2°
Detector resolution: 9 pixels mm^-1	h = −15→15
ϕ and ω scans	k = −11→10
10639 measured reflections	l = −17→17
3130 independent reflections

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0471P)² + 0.7878P] where P = (F_o² + 2F_c²)/3
3130 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₆H₁₉N₄⁺·Cl⁻·CH₂Cl₂	V = 1367.23 (6) Å³
M_r = 267.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1512 (4) Å	µ = 0.65 mm⁻¹
b = 8.5686 (2) Å	T = 200 K
c = 13.5497 (3) Å	0.17 × 0.17 × 0.17 mm
β = 104.273 (2)°

Data collection top

Nonius KappaCCD area-detector diffractometer	2431 reflections with I > 2σ(I)
10639 measured reflections	R_int = 0.030
3130 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	Δρ_max = 0.51 e Å⁻³
3130 reflections	Δρ_min = −0.57 e Å⁻³
127 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 > 2σ(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
N1	0.28042 (13)	0.26045 (16)	−0.00985 (11)	0.0291 (3)
N2	0.40189 (14)	0.52948 (18)	0.11822 (12)	0.0355 (4)
H1	0.4350	0.4312	0.1169	0.043*
H2	0.3888	0.5495	0.1846	0.043*
N3	0.36750 (14)	0.01291 (18)	0.14123 (12)	0.0347 (4)
H3	0.3757	−0.0326	0.2006	0.042*
H4	0.4111	0.1080	0.1487	0.042*
N4	0.48946 (13)	0.20788 (18)	−0.07457 (11)	0.0324 (3)
H5	0.4973	0.2055	−0.0066	0.039*
H6	0.5435	0.1373	−0.0843	0.039*
H7	0.5240	0.3119	−0.0890	0.039*
C1	0.22269 (16)	0.3910 (2)	0.02691 (15)	0.0362 (4)
H8	0.2052	0.3602	0.0918	0.043*
H9	0.1497	0.4113	−0.0232	0.043*
C2	0.29173 (17)	0.5407 (2)	0.04382 (15)	0.0364 (4)
H10	0.3049	0.5746	−0.0222	0.044*
H11	0.2462	0.6228	0.0666	0.044*
C3	0.28825 (16)	0.2874 (2)	−0.11498 (13)	0.0342 (4)
H12	0.3085	0.3979	−0.1226	0.041*
H13	0.2132	0.2678	−0.1621	0.041*
C4	0.37594 (16)	0.1831 (2)	−0.14384 (13)	0.0343 (4)
H14	0.3534	0.0725	−0.1405	0.041*
H15	0.3792	0.2058	−0.2147	0.041*
C5	0.22065 (16)	0.1131 (2)	−0.00284 (14)	0.0355 (4)
H16	0.2424	0.0354	−0.0487	0.043*
H17	0.1378	0.1309	−0.0268	0.043*
C6	0.24633 (17)	0.0466 (2)	0.10427 (14)	0.0362 (4)
H18	0.2230	0.1224	0.1504	0.043*
H19	0.2022	−0.0505	0.1044	0.043*
Cl2	0.03789 (6)	0.73386 (9)	0.38860 (6)	0.0703 (2)
Cl3	0.07369 (8)	0.62211 (16)	0.19725 (8)	0.1163 (4)
C7	0.1040 (2)	0.7685 (3)	0.2895 (2)	0.0630 (7)
H20	0.0780	0.8702	0.2574	0.076*
H21	0.1871	0.7746	0.3178	0.076*
Cl1	0.60198 (4)	0.24526 (5)	0.16855 (3)	0.03439 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0323 (8)	0.0290 (7)	0.0272 (7)	−0.0003 (6)	0.0093 (6)	0.0019 (6)
N2	0.0442 (9)	0.0298 (8)	0.0320 (8)	0.0009 (7)	0.0082 (7)	−0.0019 (6)
N3	0.0409 (9)	0.0321 (8)	0.0333 (8)	0.0032 (7)	0.0132 (7)	0.0056 (6)
N4	0.0375 (8)	0.0331 (8)	0.0276 (7)	0.0026 (7)	0.0101 (6)	0.0001 (6)
C1	0.0329 (10)	0.0361 (10)	0.0412 (10)	0.0026 (8)	0.0123 (8)	−0.0008 (8)
C2	0.0398 (10)	0.0306 (9)	0.0403 (10)	0.0042 (8)	0.0127 (8)	0.0019 (8)
C3	0.0372 (10)	0.0371 (10)	0.0285 (9)	0.0024 (8)	0.0082 (8)	0.0051 (7)
C4	0.0394 (10)	0.0344 (10)	0.0296 (9)	−0.0016 (8)	0.0095 (8)	−0.0031 (7)
C5	0.0350 (10)	0.0347 (10)	0.0355 (9)	−0.0069 (8)	0.0065 (8)	0.0000 (8)
C6	0.0383 (10)	0.0352 (10)	0.0382 (10)	−0.0026 (8)	0.0151 (8)	0.0037 (8)
Cl2	0.0586 (4)	0.0835 (5)	0.0745 (4)	0.0079 (3)	0.0269 (3)	0.0044 (3)
Cl3	0.0780 (6)	0.1752 (11)	0.1012 (7)	−0.0436 (6)	0.0326 (5)	−0.0730 (7)
C7	0.0437 (13)	0.0711 (17)	0.0787 (18)	−0.0073 (12)	0.0239 (13)	−0.0116 (14)
Cl1	0.0357 (3)	0.0366 (3)	0.0302 (2)	−0.00045 (18)	0.00691 (17)	−0.00011 (17)

Geometric parameters (Å, º) top

N1—C3	1.469 (2)	C2—H10	0.9900
N1—C1	1.471 (2)	C2—H11	0.9900
N1—C5	1.471 (2)	C3—C4	1.514 (3)
N2—C2	1.467 (2)	C3—H12	0.9900
N2—H1	0.9358	C3—H13	0.9900
N2—H2	0.9660	C4—H14	0.9900
N3—C6	1.462 (2)	C4—H15	0.9900
N3—H3	0.8776	C5—C6	1.518 (3)
N3—H4	0.9638	C5—H16	0.9900
N4—C4	1.480 (2)	C5—H17	0.9900
N4—H5	0.9019	C6—H18	0.9900
N4—H6	0.9265	C6—H19	0.9900
N4—H7	1.0244	Cl2—C7	1.751 (3)
C1—C2	1.519 (3)	Cl3—C7	1.745 (3)
C1—H8	0.9900	C7—H20	0.9900
C1—H9	0.9900	C7—H21	0.9900

C3—N1—C1	111.05 (14)	C4—C3—H12	109.2
C3—N1—C5	110.38 (14)	N1—C3—H13	109.2
C1—N1—C5	110.28 (14)	C4—C3—H13	109.2
C2—N2—H1	111.7	H12—C3—H13	107.9
C2—N2—H2	107.2	N4—C4—C3	110.89 (15)
H1—N2—H2	110.4	N4—C4—H14	109.5
C6—N3—H3	106.2	C3—C4—H14	109.5
C6—N3—H4	110.5	N4—C4—H15	109.5
H3—N3—H4	110.1	C3—C4—H15	109.5
C4—N4—H5	119.5	H14—C4—H15	108.0
C4—N4—H6	113.5	N1—C5—C6	113.30 (15)
H5—N4—H6	103.3	N1—C5—H16	108.9
C4—N4—H7	111.5	C6—C5—H16	108.9
H5—N4—H7	105.6	N1—C5—H17	108.9
H6—N4—H7	101.7	C6—C5—H17	108.9
N1—C1—C2	113.68 (15)	H16—C5—H17	107.7
N1—C1—H8	108.8	N3—C6—C5	110.71 (15)
C2—C1—H8	108.8	N3—C6—H18	109.5
N1—C1—H9	108.8	C5—C6—H18	109.5
C2—C1—H9	108.8	N3—C6—H19	109.5
H8—C1—H9	107.7	C5—C6—H19	109.5
N2—C2—C1	115.12 (15)	H18—C6—H19	108.1
N2—C2—H10	108.5	Cl3—C7—Cl2	111.83 (15)
C1—C2—H10	108.5	Cl3—C7—H20	109.2
N2—C2—H11	108.5	Cl2—C7—H20	109.2
C1—C2—H11	108.5	Cl3—C7—H21	109.2
H10—C2—H11	107.5	Cl2—C7—H21	109.2
N1—C3—C4	112.06 (15)	H20—C7—H21	107.9
N1—C3—H12	109.2

C3—N1—C1—C2	−69.7 (2)	N1—C3—C4—N4	−58.4 (2)
C5—N1—C1—C2	167.57 (15)	C3—N1—C5—C6	158.47 (16)
N1—C1—C2—N2	−59.7 (2)	C1—N1—C5—C6	−78.5 (2)
C1—N1—C3—C4	162.77 (15)	N1—C5—C6—N3	−60.7 (2)
C5—N1—C3—C4	−74.60 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···Cl1	0.94	2.54	3.3897 (17)	151
N2—H2···Cl1ⁱ	0.97	2.58	3.4402 (16)	148
N3—H3···Cl1ⁱⁱ	0.88	2.57	3.4013 (16)	159
N3—H4···Cl1	0.96	2.55	3.4203 (17)	150
N4—H5···Cl1	0.90	2.42	3.2562 (15)	153
N4—H6···N3ⁱⁱⁱ	0.93	1.96	2.862 (2)	165
N4—H7···N2^iv	1.02	1.73	2.746 (2)	171
C4—H14···Cl1ⁱⁱⁱ	0.99	2.82	3.7014 (18)	149
C7—H21···Cl1ⁱ	0.99	2.54	3.482 (3)	160

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

Experimental details

Crystal data
Chemical formula	C₆H₁₉N₄⁺·Cl⁻·CH₂Cl₂
M_r	267.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	12.1512 (4), 8.5686 (2), 13.5497 (3)
β (°)	104.273 (2)
V (Å³)	1367.23 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.17 × 0.17 × 0.17

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10639, 3130, 2431
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.03
No. of reflections	3130
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.57

Computer programs: COLLECT (Hooft, 2004), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 200) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···Cl1	0.94	2.54	3.3897 (17)	151
N2—H2···Cl1ⁱ	0.97	2.58	3.4402 (16)	148
N3—H3···Cl1ⁱⁱ	0.88	2.57	3.4013 (16)	159
N3—H4···Cl1	0.96	2.55	3.4203 (17)	150
N4—H5···Cl1	0.90	2.42	3.2562 (15)	153
N4—H6···N3ⁱⁱⁱ	0.93	1.96	2.862 (2)	165
N4—H7···N2^iv	1.02	1.73	2.746 (2)	171
C4—H14···Cl1ⁱⁱⁱ	0.99	2.82	3.7014 (18)	149
C7—H21···Cl1ⁱ	0.99	2.54	3.482 (3)	160

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

Acknowledgements

MMR thanks the Fonds der Chemischen Industrie (FCI) for a PhD fellowship.

References

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