N,N'-Bis(2-ammonio-benz-yl)ethane-1,2-diammonium-nitrate-perchlorate (1/1.5/2.5).

The title compound, C(16)H(26)N(4) (4+)·2.5ClO(4) (-)·1.5NO(3) (-), is an organic salt in which the cation is a fully protonated tetra-mine. The cation lies on an inversion center and, as a consequence, both benzene rings are parallel. The central chain is found in an all-trans arrangement, a conformation different from that observed in the crystal structure of the non-protonated mol-ecule. The charges are balanced by a mixture of nitrate and perchlorate ions. One site is occupied by an ordered perchlorate ion, while the other contains both nitrate and perchlorate ions, with occupancies of 0.75 and 0.25, respectively. In the crystal, the NH(2) (+) groups of the cation form N-H⋯O hydrogen bonds with the anions. The NH(3) (+) groups also behave as donor groups, allowing the building of chains along [100], alternating cations and disordered anions being connected via N-H⋯O hydrogen bonds.

Related literature

For the structure of the free tetra­mine, see: Rodríguez de Barbarín et al. (2007 ▶). For the use of polyaza ligands for depolymerization of poly(ethyl­ene terephthalate), see: Carta et al. (2003 ▶); Parra et al. (2004 ▶); Pohorely et al. (2006 ▶).

Experimental

Crystal data

C16H26N4 4+·2.5ClO4 −·1.5NO3 −

M = 616.05

Monoclinic,

a = 8.427 (3) Å

b = 12.637 (3) Å

c = 11.834 (3) Å

β = 106.97 (2)°

V = 1205.4 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.41 mm−1

T = 298 K

0.6 × 0.4 × 0.4 mm

Data collection

Siemens P4 diffractometer

Absorption correction: none

6392 measured reflections

2125 independent reflections

1757 reflections with I > 2σ(I)

R int = 0.057

3 standard reflections every 97 reflections intensity decay: <1%

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.119

S = 1.14

2125 reflections

218 parameters

8 restraints

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.27 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL-Plus.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680904519X/vm2008sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904519X/vm2008Isup2.hkl

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

C16H26N44+·2.5ClO4−·1.5NO3−	F(000) = 638
Mr = 616.05	Dx = 1.697 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 73 reflections
a = 8.427 (3) Å	θ = 5.0–12.4°
b = 12.637 (3) Å	µ = 0.41 mm−1
c = 11.834 (3) Å	T = 298 K
β = 106.97 (2)°	Irregular, pale yellow
V = 1205.4 (6) Å3	0.6 × 0.4 × 0.4 mm
Z = 2

Siemens P4 diffractometer	Rint = 0.057
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 2.4°
graphite	h = −10→10
ω scans	k = −15→15
6392 measured reflections	l = −14→14
2125 independent reflections	3 standard reflections every 97 reflections
1757 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0221P)2 + 1.6735P] where P = (Fo2 + 2Fc2)/3
2125 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.25 e Å−3
8 restraints	Δρmin = −0.27 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	−0.1084 (4)	0.6532 (2)	0.2742 (2)	0.0430 (7)
H1A	−0.2090	0.6242	0.2538	0.065*
H1B	−0.1163	0.7215	0.2897	0.065*
H1C	−0.0445	0.6208	0.3381	0.065*
C2	−0.0347 (4)	0.6416 (2)	0.1763 (3)	0.0326 (7)
C3	−0.1440 (4)	0.6359 (2)	0.0652 (3)	0.0399 (8)
H3A	−0.2578	0.6371	0.0546	0.048*
C4	−0.0826 (5)	0.6283 (2)	−0.0310 (3)	0.0434 (8)
H4A	−0.1553	0.6235	−0.1070	0.052*
C5	0.0852 (5)	0.6280 (3)	−0.0143 (3)	0.0430 (8)
H5A	0.1263	0.6245	−0.0791	0.052*
C6	0.1929 (4)	0.6327 (2)	0.0979 (3)	0.0394 (8)
H6A	0.3066	0.6313	0.1082	0.047*
C7	0.1348 (4)	0.6396 (2)	0.1969 (3)	0.0311 (7)
C8	0.2604 (4)	0.6487 (2)	0.3159 (3)	0.0371 (7)
H8A	0.2095	0.6834	0.3696	0.044*
H8B	0.3513	0.6928	0.3091	0.044*
N9	0.3283 (3)	0.5437 (2)	0.3671 (2)	0.0350 (6)
H9A	0.2457	0.5053	0.3806	0.042*
H9B	0.3660	0.5085	0.3140	0.042*
C10	0.4644 (4)	0.5534 (3)	0.4787 (3)	0.0380 (8)
H10A	0.4225	0.5862	0.5384	0.046*
H10B	0.5509	0.5985	0.4662	0.046*
Cl1	−0.00237 (10)	0.35712 (6)	0.40133 (7)	0.0396 (2)
O1	−0.1221 (4)	0.3829 (3)	0.4604 (3)	0.0752 (9)
O2	0.0116 (4)	0.4419 (2)	0.3253 (2)	0.0643 (8)
O3	0.1540 (4)	0.3438 (2)	0.4887 (2)	0.0648 (8)
O4	−0.0495 (4)	0.2635 (2)	0.3332 (3)	0.0647 (8)
Cl2	0.5512 (9)	0.4371 (6)	0.1804 (8)	0.0358 (15)	0.25
O5	0.587 (4)	0.5336 (15)	0.244 (2)	0.039 (7)	0.25
O6	0.5011 (19)	0.4701 (12)	0.0603 (8)	0.083 (4)	0.25
O7	0.415 (4)	0.394 (4)	0.211 (4)	0.083 (14)	0.25
O8	0.675 (2)	0.3628 (14)	0.186 (2)	0.052 (5)	0.25
N11	0.5525 (14)	0.4327 (9)	0.2076 (9)	0.068 (4)	0.75
O12	0.5925 (19)	0.5250 (7)	0.2380 (11)	0.071 (4)	0.75
O13	0.4469 (14)	0.3860 (9)	0.2416 (13)	0.056 (2)	0.75
O14	0.6277 (12)	0.3811 (8)	0.1526 (9)	0.099 (3)	0.75

	U11	U22	U33	U12	U13	U23
N1	0.0417 (16)	0.0511 (17)	0.0434 (15)	0.0065 (14)	0.0236 (13)	0.0043 (13)
C2	0.0406 (18)	0.0254 (14)	0.0364 (16)	0.0035 (13)	0.0186 (14)	0.0037 (13)
C3	0.0373 (18)	0.0331 (16)	0.0472 (19)	0.0030 (14)	0.0089 (15)	0.0045 (15)
C4	0.062 (2)	0.0306 (16)	0.0344 (17)	0.0060 (16)	0.0086 (16)	0.0029 (14)
C5	0.065 (3)	0.0361 (18)	0.0336 (17)	0.0020 (17)	0.0231 (17)	0.0038 (14)
C6	0.0451 (19)	0.0333 (16)	0.0475 (18)	−0.0014 (15)	0.0255 (16)	0.0056 (15)
C7	0.0393 (18)	0.0221 (14)	0.0347 (15)	−0.0016 (13)	0.0153 (13)	0.0033 (12)
C8	0.0392 (18)	0.0305 (16)	0.0421 (17)	−0.0037 (14)	0.0128 (15)	−0.0009 (14)
N9	0.0333 (15)	0.0368 (14)	0.0337 (13)	−0.0012 (11)	0.0081 (12)	−0.0022 (11)
C10	0.0333 (18)	0.0418 (18)	0.0355 (17)	−0.0007 (14)	0.0047 (14)	−0.0050 (14)
Cl1	0.0461 (5)	0.0334 (4)	0.0467 (5)	−0.0010 (4)	0.0250 (4)	0.0020 (3)
O1	0.069 (2)	0.088 (2)	0.089 (2)	0.0045 (17)	0.0545 (18)	−0.0055 (18)
O2	0.084 (2)	0.0519 (16)	0.0603 (16)	−0.0161 (15)	0.0263 (15)	0.0158 (13)
O3	0.0577 (18)	0.0691 (18)	0.0606 (16)	0.0068 (15)	0.0065 (14)	−0.0013 (14)
O4	0.0669 (19)	0.0407 (14)	0.086 (2)	−0.0074 (13)	0.0213 (16)	−0.0149 (14)
Cl2	0.028 (3)	0.033 (3)	0.051 (3)	−0.006 (2)	0.018 (2)	−0.007 (2)
O5	0.039 (13)	0.049 (16)	0.039 (9)	0.007 (10)	0.026 (9)	0.002 (9)
O6	0.105 (11)	0.110 (10)	0.037 (6)	−0.004 (9)	0.027 (7)	0.017 (7)
O7	0.059 (14)	0.12 (2)	0.08 (3)	−0.036 (15)	0.030 (17)	−0.020 (16)
O8	0.029 (7)	0.032 (6)	0.094 (12)	0.010 (6)	0.019 (7)	−0.005 (7)
N11	0.070 (6)	0.079 (7)	0.060 (6)	0.024 (5)	0.026 (4)	−0.002 (4)
O12	0.082 (8)	0.029 (4)	0.118 (7)	−0.005 (4)	0.055 (6)	−0.006 (4)
O13	0.060 (5)	0.052 (3)	0.062 (6)	−0.016 (3)	0.028 (5)	−0.003 (3)
O14	0.104 (7)	0.097 (5)	0.122 (8)	0.031 (4)	0.075 (6)	−0.015 (5)

N1—C2	1.473 (4)	N9—C10	1.480 (4)
N1—H1A	0.8900	N9—H9A	0.9000
N1—H1B	0.8900	N9—H9B	0.9000
N1—H1C	0.8900	C10—C10i	1.503 (6)
C2—C3	1.369 (4)	C10—H10A	0.9700
C2—C7	1.378 (4)	C10—H10B	0.9700
C3—C4	1.385 (5)	Cl1—O4	1.421 (3)
C3—H3A	0.9300	Cl1—O1	1.423 (3)
C4—C5	1.369 (5)	Cl1—O2	1.426 (3)
C4—H4A	0.9300	Cl1—O3	1.428 (3)
C5—C6	1.374 (5)	Cl2—O8	1.389 (9)
C5—H5A	0.9300	Cl2—O7	1.409 (10)
C6—C7	1.398 (4)	Cl2—O5	1.417 (10)
C6—H6A	0.9300	Cl2—O6	1.422 (9)
C7—C8	1.498 (4)	N11—O14	1.222 (8)
C8—N9	1.501 (4)	N11—O13	1.229 (8)
C8—H8A	0.9700	N11—O12	1.238 (8)
C8—H8B	0.9700
C2—N1—H1A	109.5	H8A—C8—H8B	107.8
C2—N1—H1B	109.5	C10—N9—C8	113.1 (2)
H1A—N1—H1B	109.5	C10—N9—H9A	109.0
C2—N1—H1C	109.5	C8—N9—H9A	109.0
H1A—N1—H1C	109.5	C10—N9—H9B	109.0
H1B—N1—H1C	109.5	C8—N9—H9B	109.0
C3—C2—C7	122.8 (3)	H9A—N9—H9B	107.8
C3—C2—N1	116.1 (3)	N9—C10—C10i	110.7 (3)
C7—C2—N1	121.0 (3)	N9—C10—H10A	109.5
C2—C3—C4	119.0 (3)	C10i—C10—H10A	109.5
C2—C3—H3A	120.5	N9—C10—H10B	109.5
C4—C3—H3A	120.5	C10i—C10—H10B	109.5
C5—C4—C3	120.0 (3)	H10A—C10—H10B	108.1
C5—C4—H4A	120.0	O4—Cl1—O1	110.36 (19)
C3—C4—H4A	120.0	O4—Cl1—O2	109.21 (17)
C4—C5—C6	120.2 (3)	O1—Cl1—O2	109.82 (19)
C4—C5—H5A	119.9	O4—Cl1—O3	111.00 (17)
C6—C5—H5A	119.9	O1—Cl1—O3	107.96 (19)
C5—C6—C7	121.2 (3)	O2—Cl1—O3	108.46 (19)
C5—C6—H6A	119.4	O8—Cl2—O7	112 (2)
C7—C6—H6A	119.4	O8—Cl2—O5	121.0 (17)
C2—C7—C6	116.8 (3)	O7—Cl2—O5	105 (3)
C2—C7—C8	125.2 (3)	O8—Cl2—O6	104.3 (13)
C6—C7—C8	117.9 (3)	O7—Cl2—O6	110 (2)
C7—C8—N9	113.2 (2)	O5—Cl2—O6	103.4 (13)
C7—C8—H8A	108.9	O14—N11—O13	117.1 (12)
N9—C8—H8A	108.9	O14—N11—O12	121.2 (12)
C7—C8—H8B	108.9	O13—N11—O12	121.3 (12)
N9—C8—H8B	108.9
C7—C2—C3—C4	−0.3 (5)	C5—C6—C7—C2	−0.1 (4)
N1—C2—C3—C4	178.0 (3)	C5—C6—C7—C8	−177.7 (3)
C2—C3—C4—C5	−0.8 (5)	C2—C7—C8—N9	98.7 (3)
C3—C4—C5—C6	1.5 (5)	C6—C7—C8—N9	−83.9 (3)
C4—C5—C6—C7	−1.0 (5)	C7—C8—N9—C10	174.1 (3)
C3—C2—C7—C6	0.7 (4)	C8—N9—C10—C10i	−175.9 (3)
N1—C2—C7—C6	−177.5 (3)	O8—Cl2—O6—O6ii	−79 (5)
C3—C2—C7—C8	178.2 (3)	O7—Cl2—O6—O6ii	160 (6)
N1—C2—C7—C8	−0.1 (4)	O5—Cl2—O6—O6ii	48 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2	0.89	2.32	2.856 (4)	118
N1—H1B···O13iii	0.89	2.61	3.270 (13)	132
N9—H9B···O5	0.90	2.27	2.96 (3)	133
N9—H9B···O12	0.90	2.35	3.055 (15)	136
N9—H9A···O2	0.90	2.05	2.872 (4)	151
N9—H9A···O3	0.90	2.64	3.441 (4)	149
N9—H9B···O7	0.90	2.02	2.89 (5)	163
N9—H9B···O13	0.90	1.98	2.836 (13)	157
N1—H1A···O5iv	0.89	2.04	2.91 (3)	165
N1—H1A···O12iv	0.89	2.05	2.920 (13)	164
N1—H1B···O8iii	0.89	1.90	2.78 (2)	170
N1—H1B···O14iii	0.89	2.14	3.026 (11)	174
N1—H1C···O1v	0.89	2.39	3.207 (4)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9A⋯O2	0.90	2.05	2.872 (4)	151
N9—H9B⋯O7	0.90	2.02	2.89 (5)	163
N9—H9B⋯O13	0.90	1.98	2.836 (13)	157
N1—H1A⋯O5i	0.89	2.04	2.91 (3)	165
N1—H1A⋯O12i	0.89	2.05	2.920 (13)	164
N1—H1B⋯O8ii	0.89	1.90	2.78 (2)	170
N1—H1B⋯O14ii	0.89	2.14	3.026 (11)	174
N1—H1C⋯O1iii	0.89	2.39	3.207 (4)	153

Symmetry codes: (i) ; (ii) ; (iii) .