3,12-Diaza-6,9-diazo-nia-2,13-dioxotetra-decane bis-(perchlorate).

The crystal structure of the title diprotonated diacetyl-triethyl-ene-tetra-mine (DAT) perchorate salt, C(10)H(24)N(4)O(2) (2+)·2ClO(4) (-), can be described as a three-dimensional assembly of alternating layers consisting of diprotonated diacetyl-triethyl-ene-tetra-mine (H(2)DAT)(2+) strands along [100] and the anionic species ClO(4) (-). The (H(2)DAT)(2+) cations in the strands are connected via N-H⋯O hydrogen bonding between the acetyl groups and the amine groups of neighbouring (H(2)DAT)(2+) cations. Layers of (H(2)DAT)(2+) strands and perchlorate anions are connected by a network of hydrogen bonds between the NH and NH(2) 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 = 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) Å3

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

Δρmax = 0.38 e Å−3

Δρmin = −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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811055516/nc2261sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055516/nc2261Isup2.hkl

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

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

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 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)

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.

	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)

	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)

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)

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

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) .