3,12-Diaza-6,9-diazo­nia-2,13-dioxotetra­decane bis­(perchlorate)

Abstract

The crystal structure of the title diprotonated diacetyl­triethyl­ene­tetra­mine (DAT) perchorate salt, C₁₀H₂₄N₄O₂ ²⁺·2ClO₄ ⁻, can be described as a three-dimensional assembly of alternating layers consisting of diprotonated diacetyl­triethyl­ene­tetra­mine (H₂DAT)²⁺ strands along [100] and the anionic species ClO₄ ⁻. The (H₂DAT)²⁺ cations in the strands are connected via N—H⋯O hydrogen bonding between the acetyl groups and the amine groups of neighbouring (H₂DAT)²⁺ cations. Layers of (H₂DAT)²⁺ strands and perchlorate anions are connected by a network of hydrogen bonds between the NH and NH₂ groups and the O atoms of the perchlorate anion. The asymmetric unit consits of one perchlorate anion in a general position, as well as of one cation that is located on a center of inversion.

Related literature

For background to pharmaceutical chelating agents in the treatment of diabetes, see: Cooper et al. (2004 ▶); Gong et al. (2006 ▶, 2008 ▶); Jüllig et al. (2007 ▶); Lu et al. (2010 ▶). For the detection of a new group of TETA metabolites, see: Lu et al. (2007 ▶). For the preparation and characterization of DAT mono- and dihydro­chloride salts, see: Jonas et al. (2006 ▶); Wichmann et al. (2011 ▶). For related structures, see: Elaoud et al. (1999 ▶); Fu et al. (2005 ▶); Ilioudis et al. (2000 ▶, 2002 ▶); Ilioudis & Steed (2003 ▶); Wichmann et al. (2007 ▶).

Experimental

Crystal data

• C₁₀H₂₄N₄O₂ ²⁺·2ClO₄ ⁻

• M _r = 431.23

• Monoclinic,

• a = 6.0888 (5) Å

• b = 10.9415 (9) Å

• c = 14.8160 (11) Å

• β = 110.846 (6)°

• V = 922.44 (13) ų

• Z = 2

• Mo Kα radiation

• μ = 0.41 mm⁻¹

• T = 150 K

• 0.45 × 0.35 × 0.17 mm

Data collection

• Stoe IPDS II diffractometer

• Absorption correction: numerical (X-RED32; Stoe & Cie, 2001 ▶) T _min = 0.837, T _max = 0.936

• 11528 measured reflections

• 2113 independent reflections

• 1624 reflections with I > 2σ(I)

• R _int = 0.114

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.087

• S = 1.03

• 2113 reflections

• 120 parameters

• H-atom parameters constrained

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.42 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: VESTA (Momma & Izumi, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O4	0.88	2.12	2.989 (2)	167
N6—H6A⋯O1i	0.92	1.77	2.6745 (19)	168
N6—H6B⋯O2ii	0.92	2.13	2.9265 (17)	145
N6—H6B⋯O5ii	0.92	2.40	3.2141 (19)	147

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

As part of a larger project focusing on TETA and its metabolites as pharmaceutical chelating agents in Diabetes treatment (Cooper et al., 2004, Gong et al. 2006, 2008, Jüllig et al. 2007, Lu et al. 2010), we previously published the detection of a new group of TETA metabolites, N¹-Monoacetyltriethylenetetramine (MAT) and the N¹, N¹⁰-Diacetyltriethylenetetramine (DAT) (Lu et al. 2007), as well as just recently the development of a new selective synthetic route and the characterization of the DAT mono- and dihydrochloride salts (Wichmann et al., 2011).

TETA and its metabolites belong into the polyamine family, ambivalent and multidentate ligands, which are well known for their ability to form a variety of interesting open-chain, macrocyclic and three-dimensional architectures. TETA salts exist in variable protonation states with different anionic species (Ilioudis, et al. 2000, 2002, 2003, Elaoud et al. 1999, Fu et al. 2005, Wichmann et al. 2007). Therefore, we investigated the metabolite forms MAT and DAT towards their protonation and complexation behaviour (Wichmann et al., 2011). The obtained crystal structure of the new DAT salt [(H₂DAT) * 2 ClO₄] is described in this paper.

The (H₂DAT)²⁺ cations are arranged as a linear symmetric chain with the terminal NH—CO—CH₃ groups in trans-position to each other (Fig. 1).

The crystal structure consists of a three-dimensional-network, containing alternating assembly of two-dimensional-layers of (H₂DAT)²⁺ cations (Fig. 2) and the ClO₄^- anions. The (H₂DAT)²⁺ cations form linear strands along [100] (Fig. 3), connected via hydrogen bonding between the acetyl groups and the amine groups of neighbouring (H₂DAT)²⁺ cations, with a C2=O1 ··· H6A/N6 distance of 1.767 (1) Å. These linear strands of the (H₂DAT)²⁺ cations form two-dimensional-layers in the (001) plane. However, the two-dimensional-layers of (H₂DAT)²⁺ cations and the perchlorate anions were stabilized by a network of intermolecular hydrogen bonds between the NH– and NH₂-groups and the oxygen atoms of the perchlorate anion, with N6—H6B···O2—Cl1—O4···H3—N3 between 2.126 (1) Å and 2.125 (1) Å, (Table 1). The terminal NH-groups of a (H₂DAT)²⁺ cation binds to an O-atom of a perchlorate anion, which itself bound to an internal NH-group of another (H₂DAT)²⁺ cation and vice versa. Therefore each (H₂DAT)²⁺ cation is connected to four different (H₂DAT)²⁺ cations, two from the above and two from the below layer.

Experimental

The DAT * 2 HCl powder material was synthesized by CarboGen, Switzerland according to literature procedure (Jonas et al. 2006, Wichmann et al. 2011). Cu(ClO₄)₂ is commercially available and was used as received. Crystals of the title compound were grown by slow evaporation of an aqueous solution of DAT * 2 HCl and Cu(ClO₄)₂ in stoichiometric ratio in water over a period of 6 weeks.

Refinement

H atoms bonded to C and N atoms were positioned geometrically (C—H = 0.98–0.99 Å, N—H = 0.88–0.92 Å) and refined using a riding-model approximation, with U_iso(H) = 1.5 U_eq(C, N).

Figures

Fig. 1.

Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 75% probabiliyt level. [symmetry code: (i) -x, -y - z + 1].

Fig. 2.

Crystal structure of the title compound with view along the a axis. Hydrogen bonding interactions are shown as dashed lines.

Fig. 3.

The strands of (H2DAT)2+ cations viewed along the a axis. The dashed bonds indicate the hydrogen bonds.

Crystal data

C10H24N4O22+·2ClO4−	F(000) = 452
Mr = 431.23	Dx = 1.553 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12054 reflections
a = 6.0888 (5) Å	θ = 4.7–59.0°
b = 10.9415 (9) Å	µ = 0.41 mm−1
c = 14.8160 (11) Å	T = 150 K
β = 110.846 (6)°	Not regular, colourless
V = 922.44 (13) Å3	0.45 × 0.35 × 0.17 mm
Z = 2

Data collection

Stoe IPDS II diffractometer	2113 independent reflections
Radiation source: fine-focus sealed tube	1624 reflections with I > 2σ(I)
graphite	Rint = 0.114
Image plate detector scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: numerical (X-RED32; Stoe & Cie, 2001)	h = −7→6
Tmin = 0.837, Tmax = 0.936	k = −14→14
11528 measured reflections	l = −19→19

Refinement

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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0435P)2 + 0.0412P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2113 reflections	Δρmax = 0.38 e Å−3
120 parameters	Δρmin = −0.42 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0082 (19)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.7492 (2)	−0.27758 (14)	0.49858 (8)	0.0292 (3)
N3	0.4849 (2)	−0.35281 (14)	0.55667 (8)	0.0203 (3)
H3	0.4552	−0.3783	0.6075	0.030*
N6	0.1286 (2)	−0.15588 (13)	0.49690 (8)	0.0180 (3)
H6A	0.0102	−0.2008	0.5058	0.027*
H6B	0.2493	−0.1497	0.5556	0.027*
C1	0.8854 (3)	−0.3315 (2)	0.66635 (12)	0.0306 (4)
H1A	0.9869	−0.4013	0.6669	0.046*
H1B	0.8082	−0.3455	0.7133	0.046*
H1C	0.9805	−0.2570	0.6835	0.046*
C2	0.7025 (3)	−0.31761 (17)	0.56731 (10)	0.0212 (3)
C4	0.2944 (3)	−0.35009 (17)	0.46258 (10)	0.0218 (4)
H4A	0.1589	−0.3965	0.4668	0.033*
H4B	0.3476	−0.3914	0.4145	0.033*
C5	0.2149 (3)	−0.22157 (17)	0.42777 (10)	0.0211 (3)
H5A	0.3478	−0.1757	0.4205	0.032*
H5B	0.0875	−0.2255	0.3637	0.032*
C7	0.0392 (3)	−0.03159 (17)	0.46280 (11)	0.0230 (4)
H7A	−0.0947	−0.0376	0.4008	0.035*
H7B	0.1647	0.0169	0.4518	0.035*
Cl1	0.43802 (6)	−0.55724 (4)	0.77065 (2)	0.02264 (14)
O2	0.4296 (2)	−0.55967 (14)	0.86654 (8)	0.0337 (3)
O3	0.2285 (3)	−0.60503 (17)	0.70295 (10)	0.0478 (4)
O4	0.4650 (3)	−0.43253 (15)	0.74660 (10)	0.0461 (4)
O5	0.6382 (3)	−0.62675 (18)	0.77258 (10)	0.0507 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0253 (6)	0.0377 (9)	0.0282 (5)	−0.0049 (6)	0.0139 (5)	−0.0020 (5)
N3	0.0192 (6)	0.0211 (8)	0.0200 (6)	0.0012 (6)	0.0062 (5)	0.0024 (5)
N6	0.0164 (6)	0.0183 (7)	0.0180 (5)	0.0012 (6)	0.0044 (4)	0.0009 (5)
C1	0.0222 (8)	0.0346 (12)	0.0290 (8)	0.0027 (8)	0.0020 (6)	0.0014 (8)
C2	0.0204 (7)	0.0180 (9)	0.0251 (7)	0.0018 (7)	0.0081 (6)	−0.0024 (6)
C4	0.0192 (7)	0.0211 (9)	0.0226 (7)	−0.0001 (7)	0.0041 (5)	−0.0031 (6)
C5	0.0214 (7)	0.0231 (9)	0.0185 (6)	0.0032 (7)	0.0069 (5)	0.0001 (6)
C7	0.0251 (8)	0.0201 (9)	0.0265 (7)	0.0083 (7)	0.0124 (6)	0.0060 (6)
Cl1	0.0200 (2)	0.0276 (2)	0.01913 (18)	0.00163 (17)	0.00557 (13)	0.00246 (15)
O2	0.0382 (7)	0.0424 (9)	0.0237 (6)	0.0036 (7)	0.0150 (5)	0.0075 (5)
O3	0.0355 (8)	0.0518 (11)	0.0400 (7)	−0.0072 (8)	−0.0063 (6)	−0.0065 (7)
O4	0.0564 (9)	0.0378 (10)	0.0441 (7)	−0.0072 (8)	0.0180 (7)	0.0166 (7)
O5	0.0381 (8)	0.0661 (13)	0.0463 (8)	0.0256 (8)	0.0130 (6)	−0.0092 (8)

Geometric parameters (Å, °)

O1—C2	1.231 (2)	C4—C5	1.517 (2)
N3—C2	1.334 (2)	C4—H4A	0.9900
N3—C4	1.4622 (17)	C4—H4B	0.9900
N3—H3	0.8800	C5—H5A	0.9900
N6—C7	1.485 (2)	C5—H5B	0.9900
N6—C5	1.492 (2)	C7—C7i	1.515 (3)
N6—H6A	0.9200	C7—H7A	0.9900
N6—H6B	0.9200	C7—H7B	0.9900
C1—C2	1.501 (2)	Cl1—O3	1.4129 (13)
C1—H1A	0.9800	Cl1—O5	1.4284 (15)
C1—H1B	0.9800	Cl1—O4	1.4344 (16)
C1—H1C	0.9800	Cl1—O2	1.4401 (12)
C2—N3—C4	121.60 (13)	N3—C4—H4B	109.0
C2—N3—H3	119.2	C5—C4—H4B	109.0
C4—N3—H3	119.2	H4A—C4—H4B	107.8
C7—N6—C5	112.56 (12)	N6—C5—C4	111.17 (13)
C7—N6—H6A	109.1	N6—C5—H5A	109.4
C5—N6—H6A	109.1	C4—C5—H5A	109.4
C7—N6—H6B	109.1	N6—C5—H5B	109.4
C5—N6—H6B	109.1	C4—C5—H5B	109.4
H6A—N6—H6B	107.8	H5A—C5—H5B	108.0
C2—C1—H1A	109.5	N6—C7—C7i	110.03 (16)
C2—C1—H1B	109.5	N6—C7—H7A	109.7
H1A—C1—H1B	109.5	C7i—C7—H7A	109.7
C2—C1—H1C	109.5	N6—C7—H7B	109.7
H1A—C1—H1C	109.5	C7i—C7—H7B	109.7
H1B—C1—H1C	109.5	H7A—C7—H7B	108.2
O1—C2—N3	121.11 (13)	O3—Cl1—O5	111.45 (11)
O1—C2—C1	122.39 (15)	O3—Cl1—O4	109.27 (10)
N3—C2—C1	116.49 (14)	O5—Cl1—O4	109.82 (11)
N3—C4—C5	113.08 (13)	O3—Cl1—O2	110.69 (9)
N3—C4—H4A	109.0	O5—Cl1—O2	107.47 (8)
C5—C4—H4A	109.0	O4—Cl1—O2	108.06 (10)

Symmetry codes: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4	0.88	2.12	2.989 (2)	167
N6—H6A···O1ii	0.92	1.77	2.6745 (19)	168
N6—H6B···O2iii	0.92	2.13	2.9265 (17)	145
N6—H6B···O5iii	0.92	2.40	3.2141 (19)	147

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