N,N'-Bis(2-amino-benz-yl)ethane-1,2-diaminium bis-(4-methyl-benzene-sulfonate).

The title salt, C(16)H(24)N(4) (2+)·2C(7)H(7)O(3)S(-), crystallizes with the dication situated on an inversion center and the anion in a general position. The cation contains two ammonium and two free amine groups, and the observed conformation for the chain linking the benzene rings is different from that found in the free tetra-amine and in the fully protonated tetra-amine. All amine and ammonium H atoms of the cation form hydrogen bonds with eight symmetry-related anions, using the sulfonate O atoms as acceptors. This arrangement for the ions precludes any π-π contacts between benzene rings in the crystal.

Related literature

For reviews on applications of macrocyclic systems, see: Vigato & Tamburini (2004 ▶); Radecka-Paryzek et al. (2005 ▶). For their acid-catalysed synthesis using p-toluene­sulfonic acid, see: Ionkin et al. (2008 ▶). For the structures of the free mol­ecule and the fully protonated cation corresponding to the title cation, see: Rodríguez de Barbarín et al. (2007 ▶) and Garza Rodríguez et al. (2009 ▶, 2011 ▶), respectively.

Experimental

Crystal data

C16H24N4 2+·2C7H7O3S−

M = 614.76

Triclinic,

a = 5.753 (2) Å

b = 9.512 (3) Å

c = 14.493 (5) Å

α = 101.40 (2)°

β = 100.06 (3)°

γ = 97.80 (3)°

V = 753.6 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.23 mm−1

T = 298 K

0.60 × 0.16 × 0.16 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T min = 0.512, T max = 0.594

3505 measured reflections

2650 independent reflections

2234 reflections with I > 2σ(I)

R int = 0.091

2 standard reflections every 98 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.162

S = 1.29

2650 reflections

204 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.34 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 datablock(s) I, global. DOI: 10.1107/S1600536811045879/fj2471sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045879/fj2471Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811045879/fj2471Isup3.mol

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

C16H24N42+·2C7H7O3S−	Z = 1
Mr = 614.76	F(000) = 326
Triclinic, P1	Dx = 1.355 Mg m−3
Hall symbol: -P 1	Melting point: 458 K
a = 5.753 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.512 (3) Å	Cell parameters from 53 reflections
c = 14.493 (5) Å	θ = 4.8–12.3°
α = 101.40 (2)°	µ = 0.23 mm−1
β = 100.06 (3)°	T = 298 K
γ = 97.80 (3)°	Needle, colourless
V = 753.6 (5) Å3	0.60 × 0.16 × 0.16 mm

Siemens P4 diffractometer	2234 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.091
graphite	θmax = 25.1°, θmin = 2.2°
2θ/ω scans	h = −6→1
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −11→11
Tmin = 0.512, Tmax = 0.594	l = −17→17
3505 measured reflections	2 standard reflections every 98 reflections
2650 independent reflections	intensity decay: 1%

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.162	w = 1/[σ2(Fo2) + (0.0785P)2 + 0.0881P] where P = (Fo2 + 2Fc2)/3
S = 1.29	(Δ/σ)max = 0.001
2650 reflections	Δρmax = 0.39 e Å−3
204 parameters	Δρmin = −0.34 e Å−3
4 restraints	Extinction correction: SHELXTL-Plus (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.098 (15)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
N1	0.3160 (5)	0.8765 (2)	0.87317 (17)	0.0649 (6)
H11	0.204 (5)	0.933 (3)	0.867 (3)	0.097*
H12	0.457 (4)	0.939 (3)	0.897 (2)	0.097*
C1	0.3118 (4)	0.7634 (3)	0.79652 (17)	0.0496 (5)
C2	0.1190 (5)	0.7221 (3)	0.71864 (19)	0.0593 (6)
H2A	−0.0057	0.7749	0.7166	0.071*
C3	0.1086 (6)	0.6054 (3)	0.6448 (2)	0.0688 (7)
H3A	−0.0235	0.5793	0.5939	0.083*
C4	0.2906 (6)	0.5270 (3)	0.6453 (2)	0.0716 (8)
H4A	0.2850	0.4487	0.5945	0.086*
C5	0.4818 (5)	0.5656 (3)	0.72205 (19)	0.0618 (7)
H5A	0.6057	0.5121	0.7227	0.074*
C6	0.4955 (4)	0.6815 (2)	0.79821 (17)	0.0500 (6)
C7	0.6967 (4)	0.7159 (3)	0.88352 (18)	0.0569 (6)
H7A	0.7604	0.8195	0.8990	0.068*
H7B	0.8240	0.6642	0.8679	0.068*
N8	0.6196 (3)	0.6745 (2)	0.96988 (14)	0.0498 (5)
H81	0.524 (5)	0.733 (3)	0.995 (2)	0.075*
H82	0.749 (3)	0.700 (3)	1.0198 (15)	0.075*
C9	0.5193 (5)	0.5189 (3)	0.95362 (18)	0.0566 (6)
H9A	0.6282	0.4608	0.9270	0.068*
H9B	0.3678	0.4963	0.9075	0.068*
S1	0.81511 (10)	0.18163 (7)	0.85656 (4)	0.0543 (3)
O1	0.9816 (4)	0.3162 (3)	0.89311 (16)	0.0927 (8)
O2	0.9253 (5)	0.0558 (3)	0.85049 (17)	0.0967 (8)
O3	0.6275 (4)	0.1732 (3)	0.90879 (14)	0.0786 (6)
C10	0.6800 (4)	0.1845 (2)	0.73869 (17)	0.0488 (6)
C11	0.8130 (5)	0.2400 (3)	0.67923 (18)	0.0572 (6)
H11A	0.9744	0.2800	0.7023	0.069*
C12	0.7067 (5)	0.2359 (3)	0.5859 (2)	0.0647 (7)
H12A	0.7988	0.2732	0.5467	0.078*
C13	0.4679 (5)	0.1784 (3)	0.54872 (19)	0.0587 (6)
C14	0.3383 (5)	0.1247 (3)	0.6094 (2)	0.0640 (7)
H14A	0.1766	0.0852	0.5863	0.077*
C15	0.4404 (4)	0.1275 (3)	0.70353 (19)	0.0580 (6)
H15A	0.3478	0.0911	0.7430	0.070*
C16	0.3535 (6)	0.1760 (4)	0.4471 (2)	0.0793 (9)
H16A	0.3956	0.2703	0.4341	0.119*
H16B	0.1824	0.1518	0.4384	0.119*
H16C	0.4092	0.1045	0.4037	0.119*

	U11	U22	U33	U12	U13	U23
N1	0.0860 (16)	0.0610 (14)	0.0559 (13)	0.0284 (12)	0.0228 (12)	0.0149 (11)
C1	0.0595 (13)	0.0503 (12)	0.0476 (13)	0.0149 (10)	0.0192 (10)	0.0202 (10)
C2	0.0606 (14)	0.0688 (16)	0.0572 (15)	0.0215 (12)	0.0131 (11)	0.0270 (13)
C3	0.0760 (17)	0.0695 (17)	0.0579 (16)	0.0132 (14)	0.0021 (13)	0.0175 (13)
C4	0.098 (2)	0.0614 (16)	0.0552 (16)	0.0206 (15)	0.0156 (15)	0.0083 (13)
C5	0.0751 (16)	0.0615 (15)	0.0611 (16)	0.0279 (13)	0.0250 (13)	0.0220 (12)
C6	0.0559 (13)	0.0521 (13)	0.0514 (13)	0.0148 (10)	0.0186 (10)	0.0236 (10)
C7	0.0516 (13)	0.0674 (15)	0.0587 (15)	0.0095 (11)	0.0165 (11)	0.0266 (12)
N8	0.0484 (10)	0.0550 (11)	0.0495 (12)	0.0109 (8)	0.0114 (8)	0.0177 (9)
C9	0.0661 (14)	0.0558 (14)	0.0510 (14)	0.0082 (11)	0.0143 (11)	0.0189 (11)
S1	0.0529 (4)	0.0600 (4)	0.0533 (4)	0.0159 (3)	0.0100 (3)	0.0175 (3)
O1	0.0863 (14)	0.0916 (16)	0.0797 (15)	−0.0221 (12)	−0.0219 (11)	0.0317 (12)
O2	0.1200 (19)	0.1028 (18)	0.0909 (16)	0.0728 (16)	0.0241 (14)	0.0392 (14)
O3	0.0748 (12)	0.1109 (17)	0.0519 (11)	0.0177 (12)	0.0235 (9)	0.0130 (10)
C10	0.0497 (12)	0.0487 (12)	0.0517 (13)	0.0177 (10)	0.0141 (10)	0.0112 (10)
C11	0.0548 (13)	0.0621 (15)	0.0584 (15)	0.0122 (11)	0.0178 (11)	0.0156 (11)
C12	0.0761 (17)	0.0680 (16)	0.0573 (16)	0.0164 (13)	0.0224 (13)	0.0215 (13)
C13	0.0716 (16)	0.0553 (14)	0.0526 (14)	0.0250 (12)	0.0104 (12)	0.0130 (11)
C14	0.0554 (14)	0.0754 (17)	0.0600 (16)	0.0168 (12)	0.0056 (11)	0.0148 (13)
C15	0.0511 (13)	0.0703 (16)	0.0576 (15)	0.0143 (11)	0.0152 (11)	0.0201 (12)
C16	0.105 (2)	0.0776 (19)	0.0568 (17)	0.0340 (18)	0.0050 (16)	0.0165 (14)

N1—C1	1.380 (3)	C9—H9A	0.9700
N1—H11	0.896 (10)	C9—H9B	0.9700
N1—H12	0.907 (10)	S1—O2	1.423 (2)
C1—C2	1.388 (4)	S1—O3	1.425 (2)
C1—C6	1.395 (3)	S1—O1	1.435 (2)
C2—C3	1.367 (4)	S1—C10	1.756 (3)
C2—H2A	0.9300	C10—C15	1.377 (4)
C3—C4	1.365 (4)	C10—C11	1.381 (3)
C3—H3A	0.9300	C11—C12	1.374 (4)
C4—C5	1.373 (4)	C11—H11A	0.9300
C4—H4A	0.9300	C12—C13	1.378 (4)
C5—C6	1.380 (4)	C12—H12A	0.9300
C5—H5A	0.9300	C13—C14	1.376 (4)
C6—C7	1.487 (4)	C13—C16	1.500 (4)
C7—N8	1.503 (3)	C14—C15	1.381 (4)
C7—H7A	0.9700	C14—H14A	0.9300
C7—H7B	0.9700	C15—H15A	0.9300
N8—C9	1.471 (3)	C16—H16A	0.9600
N8—H81	0.905 (10)	C16—H16B	0.9600
N8—H82	0.912 (10)	C16—H16C	0.9600
C9—C9i	1.503 (5)
C1—N1—H11	118 (2)	C9i—C9—H9A	109.6
C1—N1—H12	117 (2)	N8—C9—H9B	109.6
H11—N1—H12	105 (3)	C9i—C9—H9B	109.6
N1—C1—C2	121.3 (2)	H9A—C9—H9B	108.1
N1—C1—C6	120.5 (2)	O2—S1—O3	111.59 (15)
C2—C1—C6	118.1 (2)	O2—S1—O1	113.75 (17)
C3—C2—C1	121.5 (2)	O3—S1—O1	111.44 (16)
C3—C2—H2A	119.3	O2—S1—C10	107.00 (13)
C1—C2—H2A	119.3	O3—S1—C10	106.50 (12)
C4—C3—C2	120.5 (3)	O1—S1—C10	106.03 (12)
C4—C3—H3A	119.7	C15—C10—C11	119.1 (2)
C2—C3—H3A	119.7	C15—C10—S1	120.15 (19)
C3—C4—C5	118.8 (3)	C11—C10—S1	120.71 (19)
C3—C4—H4A	120.6	C12—C11—C10	120.0 (3)
C5—C4—H4A	120.6	C12—C11—H11A	120.0
C4—C5—C6	121.9 (2)	C10—C11—H11A	120.0
C4—C5—H5A	119.1	C11—C12—C13	122.1 (3)
C6—C5—H5A	119.1	C11—C12—H12A	119.0
C5—C6—C1	119.1 (2)	C13—C12—H12A	119.0
C5—C6—C7	121.1 (2)	C12—C13—C14	117.0 (3)
C1—C6—C7	119.7 (2)	C12—C13—C16	121.5 (3)
C6—C7—N8	112.20 (19)	C14—C13—C16	121.4 (3)
C6—C7—H7A	109.2	C13—C14—C15	122.1 (3)
N8—C7—H7A	109.2	C13—C14—H14A	118.9
C6—C7—H7B	109.2	C15—C14—H14A	118.9
N8—C7—H7B	109.2	C10—C15—C14	119.7 (2)
H7A—C7—H7B	107.9	C10—C15—H15A	120.2
C9—N8—C7	113.4 (2)	C14—C15—H15A	120.2
C9—N8—H81	113 (2)	C13—C16—H16A	109.5
C7—N8—H81	112.8 (19)	C13—C16—H16B	109.5
C9—N8—H82	110.1 (19)	H16A—C16—H16B	109.5
C7—N8—H82	108.0 (19)	C13—C16—H16C	109.5
H81—N8—H82	99 (3)	H16A—C16—H16C	109.5
N8—C9—C9i	110.5 (3)	H16B—C16—H16C	109.5
N8—C9—H9A	109.6
N1—C1—C2—C3	−176.7 (2)	O3—S1—C10—C15	−23.7 (2)
C6—C1—C2—C3	−0.6 (4)	O1—S1—C10—C15	−142.5 (2)
C1—C2—C3—C4	−0.8 (4)	O2—S1—C10—C11	−82.4 (2)
C2—C3—C4—C5	1.2 (4)	O3—S1—C10—C11	158.2 (2)
C3—C4—C5—C6	−0.3 (4)	O1—S1—C10—C11	39.4 (2)
C4—C5—C6—C1	−1.1 (4)	C15—C10—C11—C12	−0.9 (4)
C4—C5—C6—C7	176.1 (2)	S1—C10—C11—C12	177.31 (19)
N1—C1—C6—C5	177.6 (2)	C10—C11—C12—C13	0.3 (4)
C2—C1—C6—C5	1.5 (3)	C11—C12—C13—C14	0.1 (4)
N1—C1—C6—C7	0.3 (3)	C11—C12—C13—C16	179.3 (2)
C2—C1—C6—C7	−175.8 (2)	C12—C13—C14—C15	0.0 (4)
C5—C6—C7—N8	−106.2 (3)	C16—C13—C14—C15	−179.3 (2)
C1—C6—C7—N8	71.0 (3)	C11—C10—C15—C14	1.0 (4)
C6—C7—N8—C9	58.7 (3)	S1—C10—C15—C14	−177.23 (19)
C7—N8—C9—C9i	171.5 (2)	C13—C14—C15—C10	−0.5 (4)
O2—S1—C10—C15	95.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2ii	0.90 (1)	2.12 (1)	3.012 (3)	177 (3)
N1—H12···O3iii	0.91 (1)	2.27 (3)	3.028 (4)	141 (3)
N8—H81···O3i	0.91 (1)	1.91 (2)	2.763 (3)	157 (3)
N8—H82···O1iv	0.91 (1)	1.86 (1)	2.739 (3)	160 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2i	0.90 (1)	2.12 (1)	3.012 (3)	177 (3)
N1—H12⋯O3ii	0.91 (1)	2.27 (3)	3.028 (4)	141 (3)
N8—H81⋯O3iii	0.91 (1)	1.91 (2)	2.763 (3)	157 (3)
N8—H82⋯O1iv	0.91 (1)	1.86 (1)	2.739 (3)	160 (3)

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