A low-temperature determination of triethyl­ene­diaminium dichloride dihydrate

Lewis, T.C.; Tocher, D.A.

doi:10.1107/S1600536805019124

organic compounds

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ISSN: 2056-9890

Volume 61| Part 7| July 2005| Pages o2202-o2204

https://doi.org/10.1107/S1600536805019124

A low-temperature determination of triethylenediaminium dichloride dihydrate

Thomas C. Lewis ^a and Derek A. Tocher ^a ^*

^aDepartment of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, England
^*Correspondence e-mail: d.a.tocher@ucl.ac.uk

(Received 8 June 2005; accepted 15 June 2005; online 24 June 2005)

The structure determination at 150 K of triethylenediaminium dichloride dihydrate (also know as 1,4-diazaoniabicyclo[2.2.2]octane dichloride dihydrate), C₆H₁₄N₂²⁺·2Cl⁻·2H₂O, obtained as part of an experimental polymorph screen on guanine, is reported here. The packing consists of a hydrogen-bonded chain structure, with one of the water molecules of crystallization involved in weak O—H⋯Cl contacts.

Comment

Triethylenediamine, also known as 1,4-diazabicyclo[2.2.2]octane, is a strong base allowing protons to be removed from other compounds to give anionic intermediates. Triethylenediamine has two reported anhydrous polymorphs, a room-temperature phase (Nimmo & Lucas, 1976a ) and a high-temperature phase (Nimmo & Lucas, 1976b ). This high-temperature structure assumes a `plastic' phase, and is of interest as triethylenediamine is a one of a select group of globular molecules which undergo thermal transitions to plastic crystals because of the high degree of molecular mobility which can be achieved in the solid state (Weiss et al., 1964 ). There are also a number of co-crystals of triethylenediamine, including with hydroquinone (Mak et al., 1984 ), sulfate hemihydrate (Jayaraman et al., 2002 ), and bis(hydrogen oxalate) (Vaidhyanathan et al., 2001 ). In addition, there are also triethylenediamine salts, including the dihydrochloride (Kennedy et al., 1987 ) and hydrobromide (Katrusiak et al., 1999 ). In this paper, we report the dihydrochloride dihydrate salt, (I), of triethylenediamine.

In (I), atoms N1 and N2 are both protonated, with the molecule in a slightly twisted conformation, different from the symmetric cage-like structure present in the room-temperature anhydrous crystal structure of unprotonated triethylenediamine (Nimmo & Lucas, 1976a). The bond lengths and angles are within expected values (Allen et al., 1987 ), with the C–N bond lengths in the range 1.4942 (15)–1.5009 (15) Å, and the C—C bond lengths in the range 1.5227 (17)–1.5368 (16) Å.

The packing consists of a hydrogen-bonded chain structure (Fig. 2), with atom N2 hydrogen bonded to O2W, through an N—H⋯O hydrogen bond (Table 1). Water atom O2W acts as a hydrogen-bond donor to both Cl1 and Cl2, through O—H⋯Cl hydrogen bonds (Table 1). The ion Cl1 is also hydrogen bonded through an N—H⋯Cl interaction to the N1 amine group, forming the chain motif. The O1W water of crystallization forms weak hydrogen bonds to Cl2, as shown in Table 1.

Figure 1
View of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The packing in (I)

, showing the hydrogen-bonded chain structure. The hydrogen bonds with D⋯A > 3.2 Å have been omitted for clarity.

Experimental

As part of an experimental polymorph screen on guanine, (I) was obtained from a saturated solution of triethylenediamine in dilute hydrochloric acid, in which approximately 0.03 g of guanine was added in an attempt to crystallize this purine base. The solution was stirred, filtered, then evaporated at room temperature (10 ml solution, in 75 × 25 mm vessels). Colourless block-shaped crystals of (I) were formed over a number of weeks. It should also be noted that large block-shaped crystals of triethylenediamine dihydrochloride were also obtained (Kennedy et al., 1987).

Crystal data

C₆H₁₄N₂²⁺·2Cl⁻·2H₂O
M_r = 221.12
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1407 (8) Å
b = 8.7188 (10) Å
c = 16.8945 (19) Å
V = 1051.8 (2) Å³
Z = 4
D_x = 1.396 Mg m⁻³
Mo Kα radiation
Cell parameters from 7311 reflections
θ = 2.3–28.2°
μ = 0.59 mm⁻¹
T = 150 (2) K
Block, colourless
0.98 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEX diffractometer
Narrow-frame ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 1996 )T_min = 0.598, T_max = 0.887
9177 measured reflections
2508 independent reflections
2473 reflections with I > 2σ(I)
R_int = 0.027
θ_max = 28.2°
h = −9 → 9
k = −11 → 11
l = −22 → 22

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.053
S = 1.06
2508 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0284P)² + 0.1405P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: 0.01 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯Cl2	0.84 (2)	2.50 (2)	3.2848 (12)	156 (2)
O1W—H2W⋯Cl2ⁱ	0.83 (2)	2.54 (2)	3.3537 (11)	169 (2)
O2W—H3W⋯Cl2	0.83 (1)	2.30 (1)	3.1109 (10)	167 (2)
O2W—H4W⋯Cl1	0.84 (1)	2.22 (1)	3.0585 (10)	173 (2)
N1—H1⋯Cl1	0.91	2.16	3.0110 (11)	156
N2—H2⋯O2Wⁱⁱ	0.91	1.77	2.6634 (13)	168
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ .

The triethylenediaminium H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, whilst the water H atoms were refined, with O—H and H⋯H distance restraints of 0.84 Å and 1.33 (2) Å, respectively.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and MERCURY (Bruno et al., 2002 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805019124/dn6231sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805019124/dn6231Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97.

1,4-diazaoniabicyclo[2.2.2]octane dichloride dihydrate top

Crystal data top

C₆H₁₄N₂²⁺·2Cl⁻·2H₂O	F(000) = 472
M_r = 221.12	D_x = 1.396 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7311 reflections
a = 7.1407 (8) Å	θ = 2.3–28.2°
b = 8.7188 (10) Å	µ = 0.59 mm⁻¹
c = 16.8945 (19) Å	T = 150 K
V = 1051.8 (2) Å³	Block, colourless
Z = 4	0.98 × 0.24 × 0.21 mm

Data collection top

Bruker SMART APEX diffractometer	2508 independent reflections
Radiation source: fine-focus sealed tube	2473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω rotation with narrow frames scans	θ_max = 28.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.598, T_max = 0.887	k = −11→11
9177 measured reflections	l = −22→22

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)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.053	w = 1/[σ²(F_o²) + (0.0284P)² + 0.1405P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2508 reflections	Δρ_max = 0.27 e Å⁻³
121 parameters	Δρ_min = −0.16 e Å⁻³
6 restraints	Absolute structure: Flack 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (4)

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
Cl1	0.51446 (4)	−0.04577 (3)	0.554391 (16)	0.02113 (7)
Cl2	1.07647 (4)	0.17252 (4)	0.656610 (17)	0.02424 (8)
O1W	0.83585 (16)	0.30071 (12)	0.80854 (6)	0.0352 (2)
H1W	0.924 (3)	0.283 (2)	0.7773 (11)	0.053*
H2W	0.845 (3)	0.3922 (18)	0.8215 (12)	0.053*
O2W	0.74444 (14)	−0.03678 (11)	0.70705 (5)	0.0254 (2)
H3W	0.829 (2)	0.0263 (19)	0.7005 (10)	0.038*
H4W	0.674 (2)	−0.034 (2)	0.6671 (9)	0.038*
N1	0.16941 (14)	0.00540 (11)	0.45541 (6)	0.0185 (2)
H1	0.2499	−0.0034	0.4969	0.022*
N2	−0.05023 (13)	0.02830 (11)	0.34157 (5)	0.01770 (19)
H2	−0.1300	0.0367	0.2998	0.021*
C1	−0.01906 (17)	−0.05314 (13)	0.47979 (6)	0.0202 (2)
H1A	−0.0572	−0.0054	0.5291	0.024*
H1B	−0.0141	−0.1632	0.4878	0.024*
C2	−0.15987 (18)	−0.01430 (14)	0.41399 (7)	0.0198 (2)
H2A	−0.2391	−0.1022	0.4031	0.024*
H2B	−0.2389	0.0706	0.4302	0.024*
C3	0.15394 (18)	0.17045 (14)	0.43252 (7)	0.0206 (2)
H3A	0.2777	0.2146	0.4261	0.025*
H3B	0.0885	0.2273	0.4734	0.025*
C4	0.04533 (17)	0.17919 (13)	0.35432 (7)	0.0203 (2)
H4A	−0.0466	0.2610	0.3567	0.024*
H4B	0.1305	0.2003	0.3109	0.024*
C5	0.24379 (18)	−0.08551 (15)	0.38683 (8)	0.0253 (3)
H5A	0.2782	−0.1878	0.4041	0.030*
H5B	0.3542	−0.0361	0.3652	0.030*
C6	0.09099 (18)	−0.09438 (15)	0.32414 (7)	0.0224 (2)
H6A	0.1444	−0.0789	0.2719	0.027*
H6B	0.0317	−0.1944	0.3254	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02161 (13)	0.01921 (12)	0.02256 (13)	0.00056 (11)	−0.00470 (10)	−0.00008 (10)
Cl2	0.02123 (13)	0.02818 (14)	0.02332 (13)	−0.00414 (11)	0.00041 (11)	−0.00136 (11)
O1W	0.0358 (5)	0.0323 (6)	0.0376 (5)	−0.0077 (5)	0.0103 (5)	−0.0058 (4)
O2W	0.0263 (5)	0.0338 (5)	0.0159 (4)	−0.0065 (4)	0.0015 (3)	0.0022 (4)
N1	0.0194 (5)	0.0169 (4)	0.0191 (5)	0.0006 (4)	−0.0043 (4)	−0.0007 (4)
N2	0.0178 (4)	0.0209 (4)	0.0144 (4)	−0.0013 (4)	−0.0006 (3)	−0.0001 (3)
C1	0.0250 (6)	0.0190 (5)	0.0166 (5)	−0.0037 (5)	0.0006 (4)	0.0008 (4)
C2	0.0177 (5)	0.0242 (6)	0.0175 (5)	−0.0042 (5)	0.0031 (4)	−0.0004 (4)
C3	0.0227 (5)	0.0153 (5)	0.0237 (5)	−0.0044 (5)	−0.0036 (5)	0.0006 (4)
C4	0.0218 (5)	0.0178 (5)	0.0212 (5)	−0.0018 (4)	−0.0008 (4)	0.0032 (4)
C5	0.0215 (6)	0.0267 (6)	0.0277 (6)	0.0073 (5)	−0.0001 (5)	−0.0053 (5)
C6	0.0248 (6)	0.0230 (6)	0.0195 (5)	0.0027 (5)	0.0021 (5)	−0.0056 (4)

Geometric parameters (Å, º) top

O1W—H1W	0.836 (15)	C1—H1B	0.9700
O1W—H2W	0.829 (15)	C2—H2A	0.9700
O2W—H3W	0.827 (13)	C2—H2B	0.9700
O2W—H4W	0.841 (13)	C3—C4	1.5339 (16)
N1—C3	1.4942 (15)	C3—H3A	0.9700
N1—C1	1.4971 (15)	C3—H3B	0.9700
N1—C5	1.5009 (15)	C4—H4A	0.9700
N1—H1	0.9100	C4—H4B	0.9700
N2—C4	1.4976 (15)	C5—C6	1.5227 (17)
N2—C6	1.4992 (16)	C5—H5A	0.9700
N2—C2	1.4993 (14)	C5—H5B	0.9700
N2—H2	0.9100	C6—H6A	0.9700
C1—C2	1.5368 (16)	C6—H6B	0.9700
C1—H1A	0.9700

H1W—O1W—H2W	106.7 (17)	H2A—C2—H2B	108.5
H3W—O2W—H4W	108.0 (15)	N1—C3—C4	107.95 (9)
C3—N1—C1	109.46 (9)	N1—C3—H3A	110.1
C3—N1—C5	109.58 (9)	C4—C3—H3A	110.1
C1—N1—C5	110.52 (9)	N1—C3—H3B	110.1
C3—N1—H1	109.1	C4—C3—H3B	110.1
C1—N1—H1	109.1	H3A—C3—H3B	108.4
C5—N1—H1	109.1	N2—C4—C3	108.10 (9)
C4—N2—C6	110.40 (9)	N2—C4—H4A	110.1
C4—N2—C2	109.77 (9)	C3—C4—H4A	110.1
C6—N2—C2	109.56 (9)	N2—C4—H4B	110.1
C4—N2—H2	109.0	C3—C4—H4B	110.1
C6—N2—H2	109.0	H4A—C4—H4B	108.4
C2—N2—H2	109.0	N1—C5—C6	108.07 (9)
N1—C1—C2	108.30 (9)	N1—C5—H5A	110.1
N1—C1—H1A	110.0	C6—C5—H5A	110.1
C2—C1—H1A	110.0	N1—C5—H5B	110.1
N1—C1—H1B	110.0	C6—C5—H5B	110.1
C2—C1—H1B	110.0	H5A—C5—H5B	108.4
H1A—C1—H1B	108.4	N2—C6—C5	108.01 (9)
N2—C2—C1	107.65 (10)	N2—C6—H6A	110.1
N2—C2—H2A	110.2	C5—C6—H6A	110.1
C1—C2—H2A	110.2	N2—C6—H6B	110.1
N2—C2—H2B	110.2	C5—C6—H6B	110.1
C1—C2—H2B	110.2	H6A—C6—H6B	108.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···Cl2	0.84 (2)	2.50 (2)	3.2848 (12)	156 (2)
O1W—H2W···Cl2ⁱ	0.83 (2)	2.54 (2)	3.3537 (11)	169 (2)
O2W—H3W···Cl2	0.83 (1)	2.30 (1)	3.1109 (10)	167 (2)
O2W—H4W···Cl1	0.84 (1)	2.22 (1)	3.0585 (10)	173 (2)
N1—H1···Cl1	0.91	2.16	3.0110 (11)	156
N2—H2···O2Wⁱⁱ	0.91	1.77	2.6634 (13)	168

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

Acknowledgements

This research was supported by the EPSRC in funding a studentship for TCL. The authors acknowledge the Research Council's UK Basic Technology Programme for supporting `Control and Prediction of the Organic Solid State'. For more information on this work, see https://www.cposs.org.uk.

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