N,N'-Bis(2-aza-niumylbenz-yl)ethane-1,2-diaminium tetra-chloride.

The title compound, C(16)H(26)N(4) (4+)·4Cl(-), is based on a fully protonated tetra-amine. In the cation, both benzene rings are connected by an all-trans chain, and the rings are almost parallel, with an angle between the mean planes of 8.34 (12)°. The benzene rings are arranged in such a way that the NH(3) (+) substituents are oriented cis with respect to the central chain. This arrangement is a consequence of multiple N-H⋯Cl hydrogen bonds, involving all N-H groups in the cation and the four independent Cl(-) anions. These contacts have strengths ranging from weak to strong (based on H⋯Cl separations), and generate a complex three-dimensional crystal structure with no preferential crystallographic orientation for the contacts.

Related literature

For the structure of the free tetra­amine, see: Rodríguez de Barbarín et al. (2007 ▶). For related structures, see: Gakias et al. (2005 ▶); Garza Rodríguez et al. (2009 ▶, 2011 ▶). For the synthesis of the title hydro­chloride, see: Ansell et al. (1983 ▶); Gruenwedel (1968 ▶).

Experimental

Crystal data

C16H26N4 4+·4Cl−

M = 416.21

Triclinic,

a = 8.6827 (13) Å

b = 11.4831 (17) Å

c = 11.7317 (17) Å

α = 117.773 (10)°

β = 101.826 (14)°

γ = 94.387 (16)°

V = 992.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.60 mm−1

T = 298 K

0.40 × 0.22 × 0.18 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T min = 0.552, T max = 0.607

6618 measured reflections

4022 independent reflections

3185 reflections with I > 2σ(I)

R int = 0.029

2 standard reflections every 98 reflections intensity decay: 1.5%

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.090

S = 1.06

4022 reflections

219 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.26 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/S1600536811045880/fj2472sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045880/fj2472Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811045880/fj2472Isup3.mol

Supplementary material file. DOI: 10.1107/S1600536811045880/fj2472Isup4.cml

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

C16H26N44+·4Cl−	Z = 2
Mr = 416.21	F(000) = 436
Triclinic, P1	Dx = 1.392 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6827 (13) Å	Cell parameters from 100 reflections
b = 11.4831 (17) Å	θ = 4.8–12.4°
c = 11.7317 (17) Å	µ = 0.60 mm−1
α = 117.773 (10)°	T = 298 K
β = 101.826 (14)°	Irregular, yellow
γ = 94.387 (16)°	0.40 × 0.22 × 0.18 mm
V = 992.8 (3) Å3

Siemens P4 diffractometer	3185 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
graphite	θmax = 26.4°, θmin = 2.0°
ω scans	h = −10→5
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −13→13
Tmin = 0.552, Tmax = 0.607	l = −14→14
6618 measured reflections	2 standard reflections every 98 reflections
4022 independent reflections	intensity decay: 1.5%

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0329P)2 + 0.4207P] where P = (Fo2 + 2Fc2)/3
4022 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.26 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
Cl1	0.64430 (7)	0.88174 (6)	0.41424 (6)	0.04766 (16)
Cl2	1.08774 (6)	0.74843 (6)	0.69409 (5)	0.03914 (14)
Cl3	0.45844 (6)	0.37199 (6)	0.07026 (6)	0.04107 (14)
Cl4	0.25755 (6)	0.58183 (5)	0.34958 (5)	0.03896 (14)
N1	0.36517 (19)	0.85610 (16)	0.61340 (16)	0.0315 (4)
H1A	0.3793	0.7855	0.5426	0.047*
H1B	0.3539	0.9227	0.5954	0.047*
H1C	0.2774	0.8333	0.6324	0.047*
C2	0.5048 (2)	0.90023 (19)	0.72836 (18)	0.0273 (4)
C3	0.5098 (2)	1.0198 (2)	0.8409 (2)	0.0331 (4)
H3A	0.4282	1.0676	0.8404	0.040*
C4	0.6361 (3)	1.0679 (2)	0.95391 (19)	0.0357 (5)
H4A	0.6396	1.1480	1.0301	0.043*
C5	0.7571 (3)	0.9971 (2)	0.9539 (2)	0.0389 (5)
H5A	0.8440	1.0303	1.0293	0.047*
C6	0.7488 (2)	0.8769 (2)	0.8416 (2)	0.0346 (4)
H6A	0.8301	0.8290	0.8430	0.042*
C7	0.6222 (2)	0.82504 (19)	0.72644 (18)	0.0267 (4)
C8	0.6184 (2)	0.68997 (19)	0.61126 (19)	0.0288 (4)
H8A	0.5107	0.6538	0.5511	0.035*
H8B	0.6449	0.6291	0.6448	0.035*
N9	0.73471 (18)	0.69858 (16)	0.53534 (15)	0.0264 (3)
H9A	0.7130	0.7584	0.5081	0.032*
H9B	0.8349	0.7287	0.5905	0.032*
C10	0.7277 (2)	0.5675 (2)	0.41706 (19)	0.0324 (4)
H10A	0.6176	0.5286	0.3625	0.039*
H10B	0.7667	0.5060	0.4461	0.039*
C11	0.8301 (2)	0.5883 (2)	0.33596 (19)	0.0328 (4)
H11A	0.7965	0.6555	0.3135	0.039*
H11B	0.9415	0.6209	0.3886	0.039*
N12	0.81500 (19)	0.46002 (16)	0.21081 (15)	0.0279 (3)
H12A	0.7116	0.4172	0.1753	0.034*
H12B	0.8728	0.4068	0.2305	0.034*
C13	0.8726 (2)	0.48425 (19)	0.11018 (18)	0.0284 (4)
H13A	0.9760	0.5452	0.1541	0.034*
H13B	0.7979	0.5273	0.0770	0.034*
C14	0.8885 (2)	0.35751 (19)	−0.00620 (18)	0.0267 (4)
C15	1.0288 (2)	0.3081 (2)	0.0064 (2)	0.0326 (4)
H15A	1.1068	0.3510	0.0883	0.039*
C16	1.0547 (3)	0.1976 (2)	−0.0991 (2)	0.0392 (5)
H16A	1.1503	0.1675	−0.0886	0.047*
C17	0.9393 (3)	0.1313 (2)	−0.2207 (2)	0.0409 (5)
H17A	0.9566	0.0561	−0.2919	0.049*
C18	0.7979 (3)	0.1767 (2)	−0.2363 (2)	0.0351 (5)
H18A	0.7195	0.1322	−0.3179	0.042*
C19	0.7740 (2)	0.28834 (19)	−0.13001 (18)	0.0273 (4)
N20	0.62423 (19)	0.33434 (17)	−0.15287 (16)	0.0337 (4)
H20A	0.5555	0.2703	−0.2285	0.051*
H20B	0.6441	0.4080	−0.1592	0.051*
H20C	0.5819	0.3528	−0.0848	0.051*

	U11	U22	U33	U12	U13	U23
Cl1	0.0568 (3)	0.0335 (3)	0.0427 (3)	0.0081 (2)	−0.0071 (2)	0.0193 (2)
Cl2	0.0314 (3)	0.0470 (3)	0.0387 (3)	0.0066 (2)	0.0051 (2)	0.0229 (2)
Cl3	0.0302 (3)	0.0403 (3)	0.0467 (3)	0.0091 (2)	0.0124 (2)	0.0157 (2)
Cl4	0.0450 (3)	0.0356 (3)	0.0309 (3)	0.0085 (2)	0.0039 (2)	0.0146 (2)
N1	0.0307 (8)	0.0285 (9)	0.0344 (9)	0.0088 (7)	0.0062 (7)	0.0155 (7)
C2	0.0294 (9)	0.0283 (10)	0.0267 (9)	0.0065 (8)	0.0096 (7)	0.0146 (8)
C3	0.0380 (11)	0.0281 (10)	0.0352 (11)	0.0099 (8)	0.0145 (9)	0.0149 (9)
C4	0.0490 (12)	0.0269 (10)	0.0258 (10)	0.0045 (9)	0.0149 (9)	0.0074 (8)
C5	0.0411 (12)	0.0405 (12)	0.0281 (10)	0.0028 (9)	0.0028 (9)	0.0148 (9)
C6	0.0354 (11)	0.0372 (11)	0.0302 (10)	0.0109 (9)	0.0074 (8)	0.0158 (9)
C7	0.0296 (10)	0.0264 (10)	0.0257 (9)	0.0065 (8)	0.0097 (7)	0.0131 (8)
C8	0.0306 (10)	0.0284 (10)	0.0292 (10)	0.0099 (8)	0.0104 (8)	0.0141 (8)
N9	0.0275 (8)	0.0271 (8)	0.0228 (7)	0.0075 (6)	0.0053 (6)	0.0112 (7)
C10	0.0369 (11)	0.0286 (10)	0.0265 (9)	0.0091 (8)	0.0104 (8)	0.0085 (8)
C11	0.0356 (10)	0.0274 (10)	0.0286 (10)	0.0052 (8)	0.0105 (8)	0.0078 (8)
N12	0.0306 (8)	0.0273 (8)	0.0256 (8)	0.0083 (7)	0.0081 (6)	0.0123 (7)
C13	0.0292 (10)	0.0307 (10)	0.0236 (9)	0.0038 (8)	0.0070 (7)	0.0126 (8)
C14	0.0259 (9)	0.0289 (10)	0.0257 (9)	0.0046 (7)	0.0071 (7)	0.0139 (8)
C15	0.0276 (10)	0.0385 (11)	0.0310 (10)	0.0070 (8)	0.0044 (8)	0.0180 (9)
C16	0.0325 (11)	0.0432 (12)	0.0438 (12)	0.0153 (9)	0.0114 (9)	0.0216 (10)
C17	0.0486 (13)	0.0348 (12)	0.0370 (11)	0.0171 (10)	0.0182 (10)	0.0121 (10)
C18	0.0365 (11)	0.0370 (11)	0.0257 (10)	0.0058 (9)	0.0051 (8)	0.0122 (9)
C19	0.0270 (9)	0.0318 (10)	0.0263 (9)	0.0081 (8)	0.0084 (7)	0.0162 (8)
N20	0.0297 (9)	0.0356 (9)	0.0307 (9)	0.0081 (7)	0.0022 (7)	0.0146 (8)

N1—C2	1.464 (2)	C11—N12	1.490 (2)
N1—H1A	0.8900	C11—H11A	0.9700
N1—H1B	0.8900	C11—H11B	0.9700
N1—H1C	0.8900	N12—C13	1.499 (2)
C2—C3	1.382 (3)	N12—H12A	0.9000
C2—C7	1.383 (3)	N12—H12B	0.9000
C3—C4	1.376 (3)	C13—C14	1.502 (3)
C3—H3A	0.9300	C13—H13A	0.9700
C4—C5	1.377 (3)	C13—H13B	0.9700
C4—H4A	0.9300	C14—C15	1.392 (3)
C5—C6	1.378 (3)	C14—C19	1.393 (3)
C5—H5A	0.9300	C15—C16	1.374 (3)
C6—C7	1.389 (3)	C15—H15A	0.9300
C6—H6A	0.9300	C16—C17	1.380 (3)
C7—C8	1.501 (3)	C16—H16A	0.9300
C8—N9	1.503 (2)	C17—C18	1.381 (3)
C8—H8A	0.9700	C17—H17A	0.9300
C8—H8B	0.9700	C18—C19	1.378 (3)
N9—C10	1.484 (2)	C18—H18A	0.9300
N9—H9A	0.9000	C19—N20	1.462 (2)
N9—H9B	0.9000	N20—H20A	0.8900
C10—C11	1.510 (3)	N20—H20B	0.8900
C10—H10A	0.9700	N20—H20C	0.8900
C10—H10B	0.9700
C2—N1—H1A	109.5	N12—C11—C10	110.36 (16)
C2—N1—H1B	109.5	N12—C11—H11A	109.6
H1A—N1—H1B	109.5	C10—C11—H11A	109.6
C2—N1—H1C	109.5	N12—C11—H11B	109.6
H1A—N1—H1C	109.5	C10—C11—H11B	109.6
H1B—N1—H1C	109.5	H11A—C11—H11B	108.1
C3—C2—C7	121.74 (18)	C11—N12—C13	111.41 (15)
C3—C2—N1	115.98 (17)	C11—N12—H12A	109.3
C7—C2—N1	122.25 (17)	C13—N12—H12A	109.3
C4—C3—C2	119.74 (19)	C11—N12—H12B	109.3
C4—C3—H3A	120.1	C13—N12—H12B	109.3
C2—C3—H3A	120.1	H12A—N12—H12B	108.0
C3—C4—C5	119.89 (19)	N12—C13—C14	112.95 (15)
C3—C4—H4A	120.1	N12—C13—H13A	109.0
C5—C4—H4A	120.1	C14—C13—H13A	109.0
C4—C5—C6	119.60 (19)	N12—C13—H13B	109.0
C4—C5—H5A	120.2	C14—C13—H13B	109.0
C6—C5—H5A	120.2	H13A—C13—H13B	107.8
C5—C6—C7	121.89 (19)	C15—C14—C19	117.02 (17)
C5—C6—H6A	119.1	C15—C14—C13	118.84 (17)
C7—C6—H6A	119.1	C19—C14—C13	124.07 (17)
C2—C7—C6	117.10 (17)	C16—C15—C14	121.56 (18)
C2—C7—C8	124.54 (17)	C16—C15—H15A	119.2
C6—C7—C8	118.31 (17)	C14—C15—H15A	119.2
C7—C8—N9	111.55 (16)	C15—C16—C17	120.13 (19)
C7—C8—H8A	109.3	C15—C16—H16A	119.9
N9—C8—H8A	109.3	C17—C16—H16A	119.9
C7—C8—H8B	109.3	C16—C17—C18	119.84 (19)
N9—C8—H8B	109.3	C16—C17—H17A	120.1
H8A—C8—H8B	108.0	C18—C17—H17A	120.1
C10—N9—C8	112.63 (15)	C19—C18—C17	119.46 (19)
C10—N9—H9A	109.1	C19—C18—H18A	120.3
C8—N9—H9A	109.1	C17—C18—H18A	120.3
C10—N9—H9B	109.1	C18—C19—C14	121.98 (18)
C8—N9—H9B	109.1	C18—C19—N20	117.28 (17)
H9A—N9—H9B	107.8	C14—C19—N20	120.72 (16)
N9—C10—C11	109.22 (16)	C19—N20—H20A	109.5
N9—C10—H10A	109.8	C19—N20—H20B	109.5
C11—C10—H10A	109.8	H20A—N20—H20B	109.5
N9—C10—H10B	109.8	C19—N20—H20C	109.5
C11—C10—H10B	109.8	H20A—N20—H20C	109.5
H10A—C10—H10B	108.3	H20B—N20—H20C	109.5
C7—C2—C3—C4	1.4 (3)	C10—C11—N12—C13	162.72 (16)
N1—C2—C3—C4	179.35 (17)	C11—N12—C13—C14	169.22 (16)
C2—C3—C4—C5	0.4 (3)	N12—C13—C14—C15	−84.1 (2)
C3—C4—C5—C6	−1.6 (3)	N12—C13—C14—C19	99.1 (2)
C4—C5—C6—C7	1.0 (3)	C19—C14—C15—C16	1.2 (3)
C3—C2—C7—C6	−1.9 (3)	C13—C14—C15—C16	−175.81 (19)
N1—C2—C7—C6	−179.74 (17)	C14—C15—C16—C17	−1.1 (3)
C3—C2—C7—C8	175.54 (18)	C15—C16—C17—C18	0.4 (3)
N1—C2—C7—C8	−2.3 (3)	C16—C17—C18—C19	0.2 (3)
C5—C6—C7—C2	0.7 (3)	C17—C18—C19—C14	−0.1 (3)
C5—C6—C7—C8	−176.90 (19)	C17—C18—C19—N20	178.41 (19)
C2—C7—C8—N9	105.5 (2)	C15—C14—C19—C18	−0.6 (3)
C6—C7—C8—N9	−77.2 (2)	C13—C14—C19—C18	176.23 (18)
C7—C8—N9—C10	−177.27 (15)	C15—C14—C19—N20	−179.02 (17)
C8—N9—C10—C11	172.08 (16)	C13—C14—C19—N20	−2.2 (3)
N9—C10—C11—N12	−175.50 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4	0.89	2.33	3.1067 (18)	146.
N1—H1B···Cl1i	0.89	2.30	3.1798 (18)	170.
N1—H1C···Cl2ii	0.89	2.26	3.1301 (18)	167.
N9—H9A···Cl1	0.90	2.21	3.1046 (17)	172.
N9—H9B···Cl2	0.90	2.22	3.0968 (17)	165.
N12—H12A···Cl3	0.90	2.18	3.0333 (18)	159.
N12—H12B···Cl2iii	0.90	2.35	3.1779 (17)	153.
N20—H20A···Cl1iv	0.89	2.29	3.1764 (19)	173.
N20—H20B···Cl3iv	0.89	2.56	3.2305 (18)	133.
N20—H20C···Cl3	0.89	2.23	3.1139 (18)	173.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl4	0.89	2.33	3.1067 (18)	146
N1—H1B⋯Cl1i	0.89	2.30	3.1798 (18)	170
N1—H1C⋯Cl2ii	0.89	2.26	3.1301 (18)	167
N9—H9A⋯Cl1	0.90	2.21	3.1046 (17)	172
N9—H9B⋯Cl2	0.90	2.22	3.0968 (17)	165
N12—H12A⋯Cl3	0.90	2.18	3.0333 (18)	159
N12—H12B⋯Cl2iii	0.90	2.35	3.1779 (17)	153
N20—H20A⋯Cl1iv	0.89	2.29	3.1764 (19)	173
N20—H20B⋯Cl3iv	0.89	2.56	3.2305 (18)	133
N20—H20C⋯Cl3	0.89	2.23	3.1139 (18)	173

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