N,N'-Bis(2-amino-benz-yl)ethane-1,2-diaminium dinitrate.

In the title salt, C16H24N4 (2+)·2NO3 (-), both the cation and anion are placed in general positions, although the cation displays non-crystallographic inversion symmetry, with the aliphatic chain extended in an all-trans conformation. The benzene rings are almost parallel, with a dihedral angle between their mean planes of 3.3 (6)°. The nitrate ions are placed in the vicinity of the protonated amine groups, forming efficient N-H⋯O inter-ion hydrogen bonds. Each nitrate ion in the asymmetric unit bridges two symmetry-related cations, forming an R 4 (4)(18) ring, a common motif in organic ammonium nitrate salts. This results in the formation of chains along [010] with alternating cations and anions. The neutral amine groups are involved in slightly weaker N-H⋯O hydrogen bonds with the nitrate O atoms, and there are also a number of C-H⋯O hydrogen bonds present. The resulting supra-molecular structure is based on a two-dimensional network extending in the ab plane.

Related literature

For the structure of the free neutral amine, see: Rodríguez de Barbarín et al. (2007 ▶). For the p-toluene­sulfonate salt of the title cation, see: Garza Rodríguez et al. (2011 ▶). For related di­ammonium nitrate salts featuring (18) motifs, see: Liu et al. (2007 ▶); Yang et al. (2007 ▶). For supra­molecular motifs nomenclature, see: Etter (1990 ▶). For the synthesis of the title salt, see: Garza Rodríguez (2010 ▶).

Experimental

Crystal data

C16H24N4 2+·2NO3 −

M = 396.41

Orthorhombic,

a = 11.041 (5) Å

b = 5.760 (4) Å

c = 30.069 (13) Å

V = 1912.1 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.60 × 0.20 × 0.20 mm

Data collection

Siemens P4 diffractometer

4371 measured reflections

2473 independent reflections

1501 reflections with I > 2σ(I)

R int = 0.053

3 standard reflections every 97 reflections intensity decay: 1.5%

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.180

S = 1.61

2473 reflections

278 parameters

13 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.31 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813027475/rk2415sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813027475/rk2415Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813027475/rk2415Isup3.cml

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

C16H24N42+·2NO3−	Dx = 1.377 Mg m−3
Mr = 396.41	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 75 reflections
a = 11.041 (5) Å	θ = 4.9–11.7°
b = 5.760 (4) Å	µ = 0.11 mm−1
c = 30.069 (13) Å	T = 298 K
V = 1912.1 (18) Å3	Needle, colourless
Z = 4	0.60 × 0.20 × 0.20 mm
F(000) = 840

Siemens P4 diffractometer	Rint = 0.053
Radiation source: fine-focus sealed tube, FN4	θmax = 25.5°, θmin = 2.7°
Graphite monochromator	h = −13→13
2θ/ω–scans	k = −3→6
4371 measured reflections	l = −36→36
2473 independent reflections	3 standard reflections every 97 reflections
1501 reflections with I > 2σ(I)	intensity decay: 1.5%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.180	w = 1/[σ2(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3
S = 1.61	(Δ/σ)max < 0.001
2473 reflections	Δρmax = 0.34 e Å−3
278 parameters	Δρmin = −0.31 e Å−3
13 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.010 (2)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
N1	0.9978 (7)	1.1615 (13)	0.1913 (3)	0.083 (2)
H1A	1.023 (9)	1.261 (14)	0.171 (2)	0.124*
H1B	1.038 (8)	1.148 (19)	0.2170 (18)	0.124*
C2	0.9002 (7)	1.0332 (13)	0.1770 (3)	0.0616 (19)
C3	0.8321 (9)	1.1154 (15)	0.1408 (3)	0.077 (2)
H3A	0.8541	1.2543	0.1272	0.092*
C4	0.7348 (9)	0.9958 (16)	0.1251 (3)	0.087 (3)
H4A	0.6902	1.0542	0.1014	0.104*
C5	0.7024 (8)	0.7886 (18)	0.1444 (3)	0.080 (2)
H5A	0.6364	0.7049	0.1339	0.096*
C6	0.7699 (7)	0.7072 (16)	0.1797 (2)	0.067 (2)
H6A	0.7485	0.5667	0.1928	0.080*
C7	0.8672 (7)	0.8267 (13)	0.1961 (2)	0.0564 (18)
C8	0.9347 (6)	0.7329 (14)	0.2354 (2)	0.0545 (18)
H8A	0.9438	0.5662	0.2322	0.065*
H8B	1.0150	0.8010	0.2363	0.065*
N9	0.8705 (4)	0.7843 (10)	0.27754 (19)	0.0485 (13)
H9A	0.846 (6)	0.937 (5)	0.284 (3)	0.073*
H9B	0.795 (4)	0.706 (10)	0.276 (3)	0.073*
C10	0.9427 (5)	0.7325 (13)	0.3181 (2)	0.0492 (15)
H10A	1.0124	0.8346	0.3195	0.059*
H10B	0.9715	0.5734	0.3171	0.059*
C11	0.8645 (5)	0.7674 (13)	0.3583 (2)	0.0474 (14)
H11A	0.8372	0.9274	0.3597	0.057*
H11B	0.7937	0.6679	0.3566	0.057*
N12	0.9349 (4)	0.7109 (11)	0.39831 (19)	0.0489 (13)
H12A	0.960 (5)	0.559 (5)	0.398 (3)	0.073*
H12B	0.999 (4)	0.810 (9)	0.397 (3)	0.073*
C13	0.8723 (7)	0.7589 (13)	0.4415 (2)	0.0559 (18)
H13A	0.7905	0.6976	0.4406	0.067*
H13B	0.8674	0.9252	0.4463	0.067*
C14	0.9406 (7)	0.6483 (14)	0.4791 (2)	0.056 (2)
C15	1.0413 (8)	0.7526 (16)	0.4955 (2)	0.073 (2)
H15A	1.0652	0.8941	0.4835	0.087*
C16	1.1096 (9)	0.658 (2)	0.5293 (3)	0.093 (3)
H16A	1.1798	0.7300	0.5392	0.112*
C17	1.0704 (10)	0.451 (2)	0.5479 (3)	0.094 (3)
H17A	1.1137	0.3844	0.5711	0.113*
C18	0.9691 (9)	0.3471 (17)	0.5323 (3)	0.085 (3)
H18A	0.9439	0.2083	0.5451	0.102*
C19	0.9016 (7)	0.4411 (14)	0.4977 (3)	0.066 (2)
N20	0.7978 (8)	0.3323 (14)	0.4831 (3)	0.086 (2)
H20A	0.786 (10)	0.185 (8)	0.493 (3)	0.128*
H20B	0.764 (9)	0.363 (17)	0.4563 (19)	0.128*
N21	0.7142 (5)	0.2743 (11)	0.2797 (2)	0.0550 (14)
O22	0.6509 (5)	0.1048 (10)	0.2738 (2)	0.093 (2)
O23	0.8219 (4)	0.2579 (8)	0.28670 (19)	0.0729 (15)
O24	0.6674 (4)	0.4708 (9)	0.27685 (19)	0.0735 (15)
N25	1.0910 (5)	0.2211 (10)	0.3951 (2)	0.0556 (14)
O26	1.1542 (5)	0.3900 (10)	0.3991 (3)	0.099 (2)
O27	0.9825 (4)	0.2383 (9)	0.38897 (19)	0.0702 (16)
O28	1.1372 (5)	0.0215 (9)	0.3989 (2)	0.0750 (14)

	U11	U22	U33	U12	U13	U23
N1	0.097 (5)	0.055 (5)	0.095 (5)	−0.021 (4)	−0.007 (4)	0.007 (4)
C2	0.077 (5)	0.041 (4)	0.066 (4)	−0.003 (4)	0.006 (4)	0.001 (4)
C3	0.110 (7)	0.055 (5)	0.066 (4)	−0.006 (5)	−0.004 (5)	0.010 (4)
C4	0.104 (7)	0.085 (7)	0.071 (5)	−0.002 (7)	−0.015 (5)	0.011 (5)
C5	0.074 (5)	0.100 (7)	0.067 (4)	−0.016 (5)	−0.012 (4)	−0.002 (5)
C6	0.063 (4)	0.069 (6)	0.068 (5)	−0.007 (4)	−0.006 (4)	0.000 (4)
C7	0.061 (4)	0.051 (5)	0.057 (4)	0.001 (4)	0.005 (3)	0.006 (4)
C8	0.060 (4)	0.047 (4)	0.057 (4)	0.003 (4)	0.009 (3)	0.002 (4)
N9	0.051 (3)	0.036 (3)	0.058 (3)	0.005 (3)	−0.006 (3)	−0.002 (3)
C10	0.048 (4)	0.039 (4)	0.061 (4)	0.000 (3)	−0.003 (3)	0.002 (4)
C11	0.048 (3)	0.040 (4)	0.054 (3)	0.003 (3)	−0.005 (3)	0.003 (4)
N12	0.053 (3)	0.037 (3)	0.056 (3)	0.006 (3)	0.003 (3)	0.003 (3)
C13	0.064 (4)	0.042 (4)	0.062 (4)	0.001 (4)	0.005 (3)	0.008 (4)
C14	0.066 (5)	0.047 (5)	0.054 (4)	0.000 (4)	0.001 (3)	−0.004 (4)
C15	0.080 (5)	0.079 (6)	0.059 (4)	−0.002 (5)	−0.005 (4)	−0.007 (5)
C16	0.089 (6)	0.119 (9)	0.071 (5)	−0.003 (6)	−0.009 (5)	−0.016 (6)
C17	0.102 (7)	0.120 (9)	0.060 (5)	0.040 (7)	−0.005 (5)	−0.006 (6)
C18	0.114 (7)	0.077 (7)	0.062 (5)	0.026 (6)	0.015 (5)	0.014 (5)
C19	0.082 (5)	0.050 (5)	0.065 (4)	0.010 (4)	0.012 (4)	−0.002 (4)
N20	0.096 (6)	0.057 (5)	0.103 (5)	−0.015 (5)	0.002 (5)	0.009 (4)
N21	0.050 (3)	0.041 (4)	0.074 (3)	0.005 (3)	0.001 (3)	0.005 (4)
O22	0.077 (4)	0.049 (3)	0.151 (6)	−0.016 (3)	−0.005 (4)	−0.003 (4)
O23	0.051 (3)	0.043 (3)	0.125 (4)	0.000 (3)	−0.014 (3)	−0.004 (4)
O24	0.063 (3)	0.047 (3)	0.111 (4)	0.015 (3)	0.002 (3)	0.004 (3)
N25	0.054 (3)	0.037 (4)	0.075 (3)	0.005 (3)	0.003 (3)	0.001 (4)
O26	0.074 (4)	0.050 (4)	0.174 (6)	−0.023 (3)	−0.001 (4)	0.005 (5)
O27	0.055 (3)	0.039 (3)	0.116 (4)	0.004 (3)	−0.013 (3)	0.008 (4)
O28	0.067 (3)	0.045 (3)	0.113 (4)	0.014 (3)	0.001 (3)	0.005 (3)

N1—C2	1.376 (10)	N12—C13	1.498 (9)
N1—H1A	0.89 (2)	N12—H12A	0.92 (2)
N1—H1B	0.90 (2)	N12—H12B	0.91 (2)
C2—C7	1.371 (9)	C13—C14	1.500 (10)
C2—C3	1.405 (11)	C13—H13A	0.9700
C3—C4	1.360 (12)	C13—H13B	0.9700
C3—H3A	0.9300	C14—C15	1.356 (11)
C4—C5	1.374 (12)	C14—C19	1.386 (11)
C4—H4A	0.9300	C15—C16	1.378 (12)
C5—C6	1.379 (11)	C15—H15A	0.9300
C5—H5A	0.9300	C16—C17	1.382 (15)
C6—C7	1.368 (10)	C16—H16A	0.9300
C6—H6A	0.9300	C17—C18	1.354 (12)
C7—C8	1.497 (10)	C17—H17A	0.9300
C8—N9	1.482 (8)	C18—C19	1.389 (12)
C8—H8A	0.9700	C18—H18A	0.9300
C8—H8B	0.9700	C19—N20	1.378 (11)
N9—C10	1.486 (8)	N20—H20A	0.91 (2)
N9—H9A	0.94 (2)	N20—H20B	0.91 (2)
N9—H9B	0.95 (2)	N21—O23	1.212 (6)
C10—C11	1.501 (8)	N21—O22	1.213 (7)
C10—H10A	0.9700	N21—O24	1.247 (7)
C10—H10B	0.9700	N25—O26	1.203 (7)
C11—N12	1.468 (9)	N25—O27	1.215 (7)
C11—H11A	0.9700	N25—O28	1.263 (7)
C11—H11B	0.9700
C2—N1—H1A	112 (6)	N12—C11—H11B	109.9
C2—N1—H1B	128 (6)	C10—C11—H11B	109.9
H1A—N1—H1B	120 (5)	H11A—C11—H11B	108.3
C7—C2—N1	122.8 (7)	C11—N12—C13	115.1 (5)
C7—C2—C3	118.4 (7)	C11—N12—H12A	112 (5)
N1—C2—C3	118.8 (8)	C13—N12—H12A	109 (5)
C4—C3—C2	121.3 (8)	C11—N12—H12B	104 (5)
C4—C3—H3A	119.3	C13—N12—H12B	106 (5)
C2—C3—H3A	119.3	H12A—N12—H12B	111 (4)
C3—C4—C5	120.0 (8)	N12—C13—C14	110.1 (6)
C3—C4—H4A	120.0	N12—C13—H13A	109.6
C5—C4—H4A	120.0	C14—C13—H13A	109.6
C4—C5—C6	118.7 (9)	N12—C13—H13B	109.6
C4—C5—H5A	120.7	C14—C13—H13B	109.6
C6—C5—H5A	120.7	H13A—C13—H13B	108.2
C7—C6—C5	122.0 (9)	C15—C14—C19	119.3 (8)
C7—C6—H6A	119.0	C15—C14—C13	119.9 (7)
C5—C6—H6A	119.0	C19—C14—C13	120.8 (7)
C6—C7—C2	119.6 (7)	C14—C15—C16	122.7 (9)
C6—C7—C8	119.6 (7)	C14—C15—H15A	118.6
C2—C7—C8	120.8 (7)	C16—C15—H15A	118.6
N9—C8—C7	111.4 (5)	C15—C16—C17	117.9 (10)
N9—C8—H8A	109.3	C15—C16—H16A	121.1
C7—C8—H8A	109.3	C17—C16—H16A	121.1
N9—C8—H8B	109.3	C18—C17—C16	120.0 (9)
C7—C8—H8B	109.3	C18—C17—H17A	120.0
H8A—C8—H8B	108.0	C16—C17—H17A	120.0
C8—N9—C10	113.9 (5)	C17—C18—C19	121.9 (9)
C8—N9—H9A	120 (5)	C17—C18—H18A	119.0
C10—N9—H9A	100 (5)	C19—C18—H18A	119.0
C8—N9—H9B	107 (5)	N20—C19—C14	121.5 (8)
C10—N9—H9B	114 (5)	N20—C19—C18	120.4 (9)
H9A—N9—H9B	102 (4)	C14—C19—C18	118.1 (8)
N9—C10—C11	109.0 (4)	C19—N20—H20A	116 (6)
N9—C10—H10A	109.9	C19—N20—H20B	122 (6)
C11—C10—H10A	109.9	H20A—N20—H20B	115 (5)
N9—C10—H10B	109.9	O23—N21—O22	121.8 (6)
C11—C10—H10B	109.9	O23—N21—O24	119.3 (6)
H10A—C10—H10B	108.3	O22—N21—O24	118.8 (6)
N12—C11—C10	109.0 (4)	O26—N25—O27	121.4 (6)
N12—C11—H11A	109.9	O26—N25—O28	119.5 (6)
C10—C11—H11A	109.9	O27—N25—O28	119.1 (6)
C7—C2—C3—C4	0.8 (12)	C10—C11—N12—C13	174.5 (5)
N1—C2—C3—C4	179.9 (9)	C11—N12—C13—C14	167.8 (7)
C2—C3—C4—C5	−1.0 (14)	N12—C13—C14—C15	79.3 (9)
C3—C4—C5—C6	0.4 (14)	N12—C13—C14—C19	−101.3 (7)
C4—C5—C6—C7	0.2 (13)	C19—C14—C15—C16	2.1 (12)
C5—C6—C7—C2	−0.4 (12)	C13—C14—C15—C16	−178.5 (7)
C5—C6—C7—C8	178.2 (7)	C14—C15—C16—C17	−2.2 (13)
N1—C2—C7—C6	−179.2 (7)	C15—C16—C17—C18	1.2 (13)
C3—C2—C7—C6	−0.1 (11)	C16—C17—C18—C19	0.0 (13)
N1—C2—C7—C8	2.2 (11)	C15—C14—C19—N20	177.9 (8)
C3—C2—C7—C8	−178.7 (7)	C13—C14—C19—N20	−1.6 (11)
C6—C7—C8—N9	−79.6 (9)	C15—C14—C19—C18	−0.8 (11)
C2—C7—C8—N9	99.1 (7)	C13—C14—C19—C18	179.8 (7)
C7—C8—N9—C10	−169.9 (6)	C17—C18—C19—N20	−178.9 (8)
C8—N9—C10—C11	−174.2 (6)	C17—C18—C19—C14	−0.2 (12)
N9—C10—C11—N12	178.7 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9A···O23i	0.94 (4)	1.87 (3)	2.794 (8)	167 (7)
N9—H9B···O24	0.95 (5)	1.96 (5)	2.879 (7)	164 (5)
N12—H12A···O27	0.92 (3)	1.88 (3)	2.787 (8)	168 (8)
N12—H12B···O28i	0.91 (5)	1.95 (5)	2.862 (8)	176 (9)
N1—H1B···O22ii	0.90 (7)	2.55 (8)	3.290 (11)	141 (9)
N1—H1B···O24ii	0.90 (7)	2.40 (7)	3.272 (10)	166 (9)
N9—H9A···O22i	0.94 (4)	2.38 (6)	3.050 (8)	128 (5)
N12—H12A···O26	0.92 (3)	2.36 (5)	3.046 (8)	132 (4)
N12—H12B···O27i	0.91 (5)	2.49 (5)	3.096 (8)	125 (4)
N20—H20B···O26iii	0.91 (7)	2.56 (8)	3.246 (12)	133 (8)
N20—H20B···O28iii	0.91 (7)	2.32 (8)	3.204 (11)	165 (8)
C8—H8B···O24ii	0.97	2.46	3.327 (9)	149
C10—H10A···O24ii	0.97	2.41	3.258 (8)	145
C10—H10B···O22iv	0.97	2.58	3.291 (9)	130
C11—H11A···O27i	0.97	2.56	3.147 (9)	119
C11—H11A···O26v	0.97	2.57	3.285 (9)	131
C11—H11B···O28iii	0.97	2.41	3.249 (9)	145
C13—H13A···O28iii	0.97	2.46	3.315 (10)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9A⋯O23i	0.94 (4)	1.87 (3)	2.794 (8)	167 (7)
N9—H9B⋯O24	0.95 (5)	1.96 (5)	2.879 (7)	164 (5)
N12—H12A⋯O27	0.92 (3)	1.88 (3)	2.787 (8)	168 (8)
N12—H12B⋯O28i	0.91 (5)	1.95 (5)	2.862 (8)	176 (9)
N1—H1B⋯O22ii	0.90 (7)	2.55 (8)	3.290 (11)	141 (9)
N1—H1B⋯O24ii	0.90 (7)	2.40 (7)	3.272 (10)	166 (9)
N9—H9A⋯O22i	0.94 (4)	2.38 (6)	3.050 (8)	128 (5)
N12—H12A⋯O26	0.92 (3)	2.36 (5)	3.046 (8)	132 (4)
N12—H12B⋯O27i	0.91 (5)	2.49 (5)	3.096 (8)	125 (4)
N20—H20B⋯O26iii	0.91 (7)	2.56 (8)	3.246 (12)	133 (8)
N20—H20B⋯O28iii	0.91 (7)	2.32 (8)	3.204 (11)	165 (8)
C8—H8B⋯O24ii	0.97	2.46	3.327 (9)	149
C10—H10A⋯O24ii	0.97	2.41	3.258 (8)	145
C10—H10B⋯O22iv	0.97	2.58	3.291 (9)	130
C11—H11A⋯O27i	0.97	2.56	3.147 (9)	119
C11—H11A⋯O26v	0.97	2.57	3.285 (9)	131
C11—H11B⋯O28iii	0.97	2.41	3.249 (9)	145
C13—H13A⋯O28iii	0.97	2.46	3.315 (10)	147

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